JP2019150973A - Gas barrier film, and sealing body - Google Patents

Abstract

To provide a gas barrier film which is high in an effect for preventing permeation of gas such as oxygen and water vapor and is excellent in gas barrier property, and is difficult to be broken against a tensile stress and has adequate flexibility and strength.SOLUTION: A gas barrier film has a laminate obtained by laminating a resin layer, a dissolution prevention layer and a gas barrier layer in this order, in which breaking elongation of the laminate is 2.0-9.0%.SELECTED DRAWING: None

Description

  The present invention relates to a gas barrier film and a sealing body in which an object to be sealed is sealed with the gas barrier film.

In recent years, organic EL elements have attracted attention as light-emitting elements that can emit light with high luminance by low-voltage direct current drive. However, the organic EL element has a problem that light emission characteristics such as light emission luminance, light emission efficiency, and light emission uniformity tend to deteriorate with time.
The problem of deterioration in performance over time, typified by organic EL elements, is a problem that generally applies to electronic members and optical members that are attracting attention in recent years. As this cause, it is thought that oxygen, moisture, etc. permeate the inside of the electronic member or the optical member, causing the performance deterioration.
As methods for dealing with this cause, several methods have been proposed in which an electronic member, an optical member, or the like, which becomes an object to be sealed, is sealed with a gas barrier sealing material having a layer structure.

  For example, Patent Document 1 discloses a gas barrier film having a cured resin layer and a gas barrier layer on at least one surface of the cured resin layer, and the cured resin layer has a glass transition temperature (Tg) of 140 ° C. or higher. A gas barrier film, which is a layer made of a cured product of a resin composition containing a resin (A) and a curable component (B), is disclosed.

WO2013 / 065812

  In recent years, for gas barrier films used for sealing materials, even if there is a sealed object with a curved surface, the shape follows the curved surface with appropriate flexibility and strength so that it can be properly sealed. There is a demand for a gas barrier film having excellent properties.

  However, the gas barrier film disclosed in Patent Document 1 focuses on obtaining solvent resistance, and lowers the gas barrier property by making the resin layer a cured resin layer using a specific forming material. Although the cause was eliminated and excellent gas barrier properties were obtained, there was room for improvement in obtaining moderate flexibility and strength.

  Therefore, the present invention has been made to solve the above-described problems, and has an excellent effect of preventing the permeation of gas such as oxygen and water vapor, is excellent in gas barrier properties, and is not easily broken against tensile stress. An object is to provide a gas barrier film having flexibility and strength.

As a result of intensive investigations in view of the above problems, the present inventor has a laminate with a dissolution preventing layer interposed between the resin layer and the gas barrier layer, and defines the breaking elongation of the laminate within a specific range. Thus, the present inventors have found that a gas barrier film having excellent gas barrier properties and appropriate flexibility and strength can be obtained, and has completed the present invention.
That is, the present invention is as follows.

[1] A gas barrier film having a laminate formed by laminating a resin layer, a dissolution preventing layer, and a gas barrier layer in this order, and the elongation at break of the laminate is 2.0 to 9.0%. Gas barrier film.
[2] The gas barrier film according to [1], wherein the resin layer is a layer formed from a resin composition containing a curable component (B).
[3] The gas barrier film according to [1] or [2], wherein the resin layer is a layer formed from a resin composition further containing a thermoplastic resin (A).
[4] The gas barrier film according to [3], wherein the thermoplastic resin (A) has a glass transition temperature (Tg) of 140 ° C. or higher.
[5] In the resin composition, the content ratio [(A) :( B)] of the thermoplastic resin (A) and the curable component (B) is 35:65 to 95: 5 by mass ratio. The gas barrier film according to any one of [2] to [4].
[6] The gas barrier film according to any one of [1] to [5], wherein the resin layer has a thickness of 1 to 40 μm.
[7] The gas barrier film according to any one of [1] to [6], wherein the dissolution preventing layer is a layer formed from a composition for a dissolution preventing layer containing a silicon compound.
[8] The gas barrier film according to any one of [1] to [7], wherein the dissolution preventing layer is substantially composed of an inorganic substance.
[9] The dissolution preventing layer is a layer formed of a composition for a dissolution preventing layer containing a curable component (B) and optionally containing a thermoplastic resin (A), and the composition for the dissolution preventing layer. In the product, the content ratio [(A) :( B)] of the thermoplastic resin (A) and the curable component (B) is 0: 100 to 34:66 by mass ratio. [8] The gas barrier film according to any one of [8].
[10] The gas barrier property according to any one of [1] to [9], wherein a ratio of the thickness of the resin layer to the thickness of the dissolution preventing layer is 0.005 or more and 0.15 or less. the film.
[11] The gas barrier film according to any one of [1] to [10], wherein the gas barrier layer is a layer formed from a gas barrier layer composition containing a silicon compound.
[12] The gas barrier film according to any one of [1] to [11], wherein the gas barrier layer is a layer formed by a modification treatment.
[13] Any of [1] to [12], wherein the laminate is a laminate obtained by laminating an adhesive layer on a surface of the gas barrier layer opposite to the surface in contact with the dissolution preventing layer. The gas barrier film according to any one of the above.
[14] A sealed object that is at least one selected from the group consisting of an organic EL element, an organic EL display element, an inorganic EL element, an inorganic EL display element, an electronic paper element, a liquid crystal display element, and a solar cell element. A sealed body formed by sealing with the gas-barrier film according to any one of [1] to [13].

  According to the present invention, a gas barrier film having a high effect of preventing permeation of gas such as oxygen and water vapor, excellent gas barrier properties, and having appropriate flexibility and strength that is difficult to break against tensile stress. Can be provided.

[Gas barrier film]
The gas barrier film of the present invention has a laminate formed by laminating a resin layer, a dissolution preventing layer, and a gas barrier layer in this order.
Here, “gas barrier property” refers to a characteristic that prevents permeation of gases such as oxygen and water vapor.

The gas barrier film of the present invention is not particularly limited as long as it is composed of a laminate in which a dissolution preventing layer is interposed between the resin layer and the gas barrier layer, and further, a surface in contact with the dissolution preventing layer; Can also be composed of a laminate formed by laminating an adhesive layer on the opposite gas barrier layer surface.
The gas barrier film of the present invention may have a configuration in which a release sheet is further laminated on the surface of the outermost layer such as a resin layer, a gas barrier layer, and an adhesive layer.

As a layer structure which the gas barrier film of this invention has, the aspect shown below is mentioned, for example.
First release sheet / resin layer / dissolution prevention layer / gas barrier layer / adhesive layer / second release sheet In the aspect of the layer configuration described above, the first release sheet and the second release sheet are the same or different. It may be a thing.
The aspect of the layer configuration described above represents a state before the gas barrier film is used as a sealing material.
When using a gas barrier film as a sealing material, usually the second release sheet is peeled and removed, and the exposed adhesive layer surface and the surface of the object to be sealed are bonded to obtain a sealed body It is. In addition, after the surface of the adhesive layer of the sealing material and the surface of the object to be sealed are adhered, the first release sheet is usually peeled and removed to expose the resin layer to have the layer configuration shown below. be able to.
-Resin layer / dissolution prevention layer / gas barrier layer / adhesive layer The first release sheet is a period until the first release sheet is peeled off when the resin layer does not have a sufficient function as a support for the gas barrier film. It functions as a support for the gas barrier film.

[Laminate]
The laminate of the present invention is constituted by interposing a dissolution preventing layer between the resin layer and the gas barrier layer.
In the present invention, a component (for example, carbon atom) that inhibits the gas barrier property in the resin layer when the gas barrier layer is formed by interposing the dissolution preventing layer between the resin layer and the gas barrier layer is present in the gas barrier layer. It can prevent mixing.
As a specific situation, even when a gas barrier layer composition containing an organic solvent is used when the gas barrier layer is formed, the resin layer surface is affected by the organic solvent contained in the gas barrier layer composition due to the presence of the dissolution preventing layer. It is hard to receive, and it can prevent that the component of the resin layer surface melt | dissolves.
On the other hand, when the dissolution preventing layer is formed, when the dissolution preventing layer composition containing an organic solvent is used, the resin layer surface is affected by the organic solvent contained in the dissolution preventing layer composition. There is a possibility that the surface components will dissolve. However, even if the component on the surface of the resin layer is dissolved, due to the presence of the dissolution preventing layer, a component (for example, carbon atom) that hinders the gas barrier property in the resin layer when the gas barrier layer is formed may reach the gas barrier layer Intrusion can be prevented.

The water vapor permeability of the laminate constituting the gas barrier film of the present invention is preferably 0.10 (g / m ² / day) or less, more preferably 0.05 (g / m ² / day) or less, and still more preferably. Is 0.01 (g / m ² / day) or less.
In the present invention, when the water vapor transmission rate of the laminate is in the above range, a gas barrier film having excellent gas barrier properties with a high effect of preventing the permeation of gases such as oxygen and water vapor can be obtained.
Here, the “water vapor transmission rate” refers to a value measured in a high temperature and high humidity environment at 40 ° C. and a relative humidity of 90% using a water vapor transmission rate measuring device. A more specific measurement method will be described later. Based on the method of the embodiment.

The elongation at break of the laminate constituting the gas barrier film of the present invention is in the range of 2.0 to 9.0%, preferably 2.0 to 8.0%, more preferably 2.0 to 7. It is in the range of 0%.
When the elongation at break of the laminate is less than 2.0%, it is easy to break against tensile stress, and there is a possibility that appropriate flexibility cannot be obtained.
On the other hand, when the elongation at break of the laminate is more than 9.0%, it is difficult to break against tensile stress, but there is a possibility that an appropriate strength cannot be obtained.

Here, “breaking elongation” refers to a value measured according to JIS K7127.
More specifically, “breaking elongation” refers to a chuck after a tensile test when a laminate as a measurement sample is broken by performing a tensile test under a desired condition using a tensile tester with a distance between chucks of 100 mm. The distance Xmm is measured, and the value calculated by the following formula 1 is used.
In addition, the “distance between chucks” refers to a distance between gripping parts that grip a laminate that is a measurement sample in a tensile tester.

In the present invention, the method for adjusting the breaking elongation of the above laminate to the specified range (2.0 to 9.0%) of the present invention is not particularly limited, but for example, by considering the following matters: Can be adjusted.
In general, since the gas barrier layer is often formed of a thin film having a thickness of about 2 μm or less, the contribution to the breaking elongation of the laminate is greatly influenced by the physical characteristics of the resin layer.
-When a resin layer is a layer formed from the resin composition containing a thermoplastic resin (A) and a curable component (B), with respect to the quantity of a curable component (B), a thermoplastic resin ( As the amount of A) is relatively large (for example, the content ratio [(A) :( B)] of the thermoplastic resin (A) and the curable component (B)) is 35:65 by mass ratio or this When the mass ratio of the thermoplastic resin (A) is larger than that), the elongation at break of the laminate tends to be high.
-When the resin layer is a layer formed from a resin composition containing a thermoplastic resin (A) and a curable component (B), the reactive functionality of the curable component (B) in one molecule The smaller the number of groups and the larger the molecular weight of the curable component (B), the higher the breaking elongation of the laminate.

The in-plane retardation (retardation) of the laminate constituting the gas barrier film of the present invention is preferably 20 nm or less, more preferably 10 nm or less.
In the present invention, when the in-plane retardation (retardation) of the laminate is in the above range, for example, a gas barrier film is used for a sealing material for sealing an optical member such as an organic EL element. The light extraction efficiency can be improved.
The method for adjusting the in-plane retardation (retardation) of the laminate to the above range is not particularly limited. For example, the adjustment can be made by considering the following matters.
-In-plane retardation (retardation) is influenced by the anisotropy of the molecular orientation of the compound (especially polymer compound) contained in each layer. When the gas barrier layer or dissolution preventing layer is obtained by a normal production method, molecular orientation anisotropy does not occur, so the contribution to the in-plane retardation (retardation) of the gas barrier film is due to the physical properties of the resin layer and The influence of chemical properties is large.
In the case where the resin layer is obtained by extrusion film formation, the molecular orientation of the compound contained in the resin layer becomes isotropic and the in-plane retardation (retardation) value decreases by producing the resin layer without stretching.
When the resin layer is obtained by casting, the molecular orientation of the compound contained in the resin layer is usually isotropic, and the in-plane retardation (retardation) value decreases.

(1) Resin layer Since the gas barrier film of the present invention has a resin layer, damage and deterioration of the gas barrier layer can be suppressed.

The thickness of the resin layer is preferably 1 to 40 μm, more preferably 2 to 30 μm, still more preferably 3 to 20 μm, and still more preferably 3 to 15 μm.
When the thickness of the resin layer is in the above range, the resin layer can be used with a thickness thinner than that of a base film generally used for a gas barrier film. As a result, the total thickness of the entire gas barrier film can be reduced.
Therefore, the gas barrier film of the present invention can be suitably used for a sealing material that seals an object to be sealed (for example, a display element or the like) that requires a thin member.
Such a thin resin layer has a lower function as a support for a gas barrier film than a general base film, but the presence of a resin layer usually makes it a very thin gas barrier layer. The gas barrier film can be easily handled as compared with the gas barrier layer alone.
Moreover, when a gas barrier film is a layer structure which has a 1st peeling sheet as mentioned above by having a resin layer, a 1st peeling sheet can be peeled and removed efficiently and suitably.

The resin layer of the gas barrier film of the present invention can be formed from, for example, a resin composition containing a resin. From the viewpoint of adjusting the elongation at break of the above laminate to the range specified in the present invention, It is preferably formed from a resin composition containing a plastic resin (A) and a curable component (B).
Hereinafter, each component contained in a resin composition suitable as a resin layer forming material will be described.

<Thermoplastic resin (A)>
By including the thermoplastic resin (A), the resin composition described above can be easily formed into a resin layer having appropriate flexibility.
Here, the “thermoplastic resin (A)” refers to a resin having a property of being melted or softened by heating and solidifying when cooled.

Examples of the thermoplastic resin (A) include resins having an aromatic ring structure and resins having a ring structure such as an alicyclic structure, and resins having an aromatic ring structure are preferable.
As the resin having an aromatic ring structure, for example, a polysulfone resin, a polyarylate resin, a polycarbonate resin, and an alicyclic hydrocarbon resin are preferable, and among them, a polysulfone resin is preferable. The polysulfone resin may be a modified polysulfone resin.
Here, the “polysulfone resin” refers to a resin made of a polymer compound having a sulfone group (—SO ₂ —) in the main chain.
Examples of the polysulfone resin include resins made of a polymer compound having a repeating unit represented by the following (a) to (h).
Among these, as the polysulfone resin, polyethersulfone resin and polysulfone resin are preferable, and among them, polysulfone resin is more preferable.

The glass transition temperature (Tg) of the thermoplastic resin (A) is preferably 140 ° C. or higher, more preferably 160 ° C. or higher, and still more preferably 180 ° C. or higher.
Here, “glass transition temperature (Tg)” means tan δ (loss elastic modulus / loss) obtained by viscoelasticity measurement (frequency 11 Hz, temperature measurement rate 3 ° C./min. It refers to the temperature at the maximum point of storage modulus.
When the glass transition temperature (Tg) is in the above range, a resin layer having excellent heat resistance can be formed.

The weight average molecular weight (Mw) of the thermoplastic resin (A) is usually 100,000 to 3,000,000, preferably 200,000 to 2,000,000, more preferably 500,000 to 2,000,000. It is.
The molecular weight distribution (Mw / Mn) of the thermoplastic resin (A) is preferably 1.0 to 5.0, more preferably 2.0 to 4.5.
Here, “weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)” refer to values in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

The content of the thermoplastic resin (A) is preferably 35 to 95% by mass, more preferably 40 to 85% by mass, and still more preferably 45 to 95% by mass with respect to the total amount (100% by mass) of the active ingredients of the resin composition. It is 75 mass%, More preferably, it is 50-70 mass%.
Here, the “active component of the resin composition” refers to a component excluding the solvent contained in the resin composition.
When the content of the thermoplastic resin (A) is in the above range, it becomes easier to obtain a gas barrier film having appropriate flexibility and strength that is difficult to break against tensile stress. .

<Curable component (B)>
A resin composition can be made into resin excellent in solvent resistance by containing a sclerosing | hardenable component (B).
Here, the “curable component (B)” is a component capable of causing (i) a controllable curing reaction, for example, a component that is cured by heating such as an epoxy resin, and (ii) having a polymerizable unsaturated bond. In addition, it refers to a component that generates a cured product by a polymerization reaction, or (iii) a component that generates a cured product by a cross-linking reaction between polymers generated by a polymerization reaction.

Among the above (i) to (iii), as the component (ii) having a polymerizable unsaturated bond and generating a cured product by a polymerization reaction (hereinafter also referred to as “polymerizable component (B1)”), for example, A monofunctional monomer or polymer having one polymerizable unsaturated bond, or a bifunctional or higher polyfunctional monomer or polymer having two or more polymerizable unsaturated bonds.
In addition, as a polymer which has a polymerizable unsaturated bond, the polymer which has a (meth) acryloyl group in the side chain of the acrylic polymer used as a urethane (meth) acrylate oligomer and a principal chain is mentioned, for example.
The polymerizable component (B1) is preferably a bifunctional or higher polyfunctional monomer or polymer, and more preferably a bifunctional or higher polyfunctional monomer.
Hereinafter, the polymerizable component (B1) will be described in detail by taking a bifunctional or higher polyfunctional monomer as an example.
As the bifunctional or higher polyfunctional monomer, for example, a bifunctional to hexafunctional (meth) acrylic acid derivative is preferable, and among them, a bifunctional (meth) acrylic acid derivative is preferable.
Examples of the bifunctional (meth) acrylic acid derivative include a compound represented by the following formula 1.

In Formula 1, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ² represents a divalent organic group.
Examples of the divalent organic group represented by R ² include a group represented by the following formula 2.

  In Formula 2, s represents an integer of 1 to 20, t represents an integer of 1 to 30, u and v each independently represent an integer of 1 to 30, and “-” at both ends represents a bond. To express.

Specific examples of the bifunctional (meth) acrylate acid derivatives represented by Formula 1 and Formula 2 include, for example, tricyclodecane dimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propoxylated ethoxylated bisphenol A Di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 9,9-bis [4- (2 -Acryloyloxyethoxy) phenyl] fluorene and the like.
Among these, those in which the divalent organic group represented by R ² in the above formula 1 has a tricyclodecane skeleton, such as tricyclodecane dimethanol di (meth) acrylate; propoxylated ethoxylated bisphenol A di ( In the above formula 1, a divalent organic group represented by R ² having a bisphenol skeleton, such as meth) acrylate and ethoxylated bisphenol A di (meth) acrylate; 9,9-bis [4- (2- In the formula 1, the divalent organic group represented by R ² has a 9,9-bisphenylfluorene skeleton, such as (acryloyloxyethoxy) phenyl] fluorene.

  The molecular weight of the curable component (B) is usually 3000 or less, preferably 200 to 2000, more preferably 200 to 1000.

The content of the curable component (B) is preferably 4 to 64% by mass, more preferably 14 to 59% by mass, and still more preferably based on the total amount (100% by mass) of the active ingredients of the resin composition described above. It is 24-54 mass%, More preferably, it is 29-49 mass%.
Here, the “active component of the resin composition” refers to a component excluding the solvent contained in the resin composition.
When the content of the curable component (B) is in the above range, it is possible to form a resin layer that is excellent in solvent resistance and hardly affected by the organic solvent contained in the composition for the dissolution preventing layer.

The resin layer is preferably a layer formed from a resin composition containing a thermoplastic resin (A) and a curable component (B).
The content ratio [(A) :( B)] of the thermoplastic resin (A) and the curable component (B) contained in the resin composition is a mass ratio, preferably 35:65 to 95: 5, More preferably, it is 40: 60-: 85: 15, More preferably, it is 45: 55-75: 25.
The content ratio [(A) :( B)] of the thermoplastic resin (A) and the curable component (B) is within the above range to prevent the components on the surface of the resin layer from dissolving. This makes it easy to adjust the breaking elongation of the laminate to the range defined in the present invention.

(Polymerization initiator)
When the resin composition contains a polymerizable component (B1), it is preferable to contain a polymerization initiator in the resin composition.
Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator.
Among these, as the polymerization initiator, a photopolymerization initiator is preferable, and specifically, an alkylphenone photopolymerization initiator, a phosphorus photopolymerization initiator, an oxime ester photopolymerization initiator, and a benzophenone photopolymerization initiator. Agents and thioxanthone photopolymerization initiators are preferable, and among them, phosphorus photopolymerization initiators are more preferable.

  Examples of phosphorus photopolymerization initiators include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and ethyl (2,4,6-trimethylbenzoyl). ) -Phenylphosphinate, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, and the like.

  The content of the polymerization initiator to be contained in the resin composition is preferably 0.2 to 6.2 parts by mass, more preferably 0.2 to 5.2 with respect to 100 parts by mass of the polymerizable component (B1). Part by mass, more preferably 0.2 to 4.2 parts by mass.

When the resin composition used in one embodiment of the present invention contains the polymerizable component (B1) as the curable component (B) and further contains a polymerization initiator, the thermoplastic resin (A) and the polymerizable component (B1) The total content of the polymerization initiator is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and still more preferably 90 to 100% by mass with respect to the total amount (100% by mass) of the active ingredients of the resin composition. 100% by mass.
Here, the “active component of the resin composition” refers to a component excluding the solvent contained in the resin composition.

(solvent)
It is preferable that the resin composition is in the form of a solution by adding a solvent from the viewpoint of easily adjusting the resin composition to properties suitable for application when the resin layer is formed by application.
The solvent is not particularly limited as long as it can dissolve or disperse the thermoplastic resin (A). For example, aliphatic hydrocarbon solvents such as n-hexane and n-heptane; toluene, xylene and the like Aromatic hydrocarbon solvents such as: dichloromethane, ethylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, monochlorobenzene and other halogenated hydrocarbon solvents; methanol, ethanol, propanol, butanol, propylene glycol monomethyl ether, etc. Alcohol solvents; ketone solvents such as acetone, methyl ethyl ketone, 2-pentanone, isophorone and cyclohexanone; ester solvents such as ethyl acetate and butyl acetate; cellosolv solvents such as ethyl cellosolve; ether solvents such as 1,3-dioxolane And the like.
Among these, as the solvent, a halogenated hydrocarbon solvent is preferable, and dichloromethane is particularly preferable.

  The amount of the solvent used for preparing the resin composition is such that the solid content concentration of the thermoplastic resin (A) is preferably 5 to 45% by mass, more preferably 5 to 35% by mass, and still more preferably 5 to 25% by mass. It may be used so that

(Other ingredients)
In addition to the thermoplastic resin (A), the curable component (B), the polymerization initiator (C), and the solvent, the resin composition may further contain other components as long as the effects of the present invention are not impaired. Good. Examples of other components include a plasticizer, an antioxidant, and an ultraviolet absorber.

According to the present invention, even if the component on the surface of the resin layer is dissolved, due to the presence of the dissolution preventing layer, a component that inhibits the gas barrier property in the resin layer when the gas barrier layer is formed (for example, carbon atom), Intrusion into the gas barrier layer can be prevented.
From this, even if the resin layer in the present invention has the property of being easily dissolved under the influence of the organic solvent, the breaking elongation of the above-mentioned laminate can be adjusted to the range specified in the present invention. As much as possible, it can be used as the resin layer of the present invention.

(2) Dissolution prevention layer The dissolution prevention layer in this invention is interposed between a resin layer and a gas barrier layer so that a gas barrier layer and a resin layer may not contact | connect directly.
In the present invention, a component (for example, carbon atom) that inhibits the gas barrier property in the resin layer when the gas barrier layer is formed by interposing the dissolution preventing layer between the resin layer and the gas barrier layer is present in the gas barrier layer. It can prevent mixing.
As a specific situation, even when a gas barrier layer composition containing an organic solvent is used when the gas barrier layer is formed, the resin layer surface is affected by the organic solvent contained in the gas barrier layer composition due to the presence of the dissolution preventing layer. It is hard to receive, and it can prevent that the component of the resin layer surface melt | dissolves.
On the other hand, when the dissolution preventing layer is formed, when the dissolution preventing layer composition containing an organic solvent is used, the resin layer surface is affected by the organic solvent contained in the dissolution preventing layer composition. There is a possibility that the surface components will dissolve. However, even if the component on the surface of the resin layer is dissolved, due to the presence of the dissolution preventing layer, a component (for example, carbon atom) that hinders the gas barrier property in the resin layer when the gas barrier layer is formed may reach the gas barrier layer. Intrusion can be prevented.
As a result, according to the present invention, it is possible to eliminate the cause of lowering the gas barrier property, so even if the resin layer has a characteristic of being easily dissolved under the influence of the organic solvent, the gas barrier property is lowered. Therefore, it is possible to obtain a gas barrier film having a high effect of preventing permeation of gases such as oxygen and water vapor and excellent gas barrier properties.

The thickness of the dissolution preventing layer is preferably 50 to 2000 nm, more preferably 100 to 1000 nm, and still more preferably 150 to 800 nm.
When the thickness of the dissolution preventing layer is in the above range, even when a gas barrier layer composition containing an organic solvent is used when the gas barrier layer is formed, the resin layer surface is used for the gas barrier layer due to the presence of the dissolution preventing layer. It is difficult to be affected by the organic solvent contained in the composition, and it is possible to suitably prevent the components on the resin layer surface from dissolving.

The ratio of the thickness of the resin layer to the thickness of the dissolution preventing layer is preferably 0.005 times or more and 0.15 times or less, more preferably 0.005 times or more and 0.08 times or less.
When the ratio of the thickness of the resin layer to the thickness of the dissolution preventing layer is in the above range, the influence of the dissolution preventing layer on the elongation at break of the laminate described above can be reduced.
The ratio of the thickness of the resin layer to the thickness of the dissolution preventing layer is preferably as small as possible. By making the lower limit value of the ratio of the thickness of the resin layer to the thickness of the dissolution preventing layer about 0.005 times, it is easy to suitably exhibit the function of the dissolution preventing layer while obtaining a thin resin layer. Become.

When the dissolution preventing layer of the gas barrier film of the present invention is a layer formed from the dissolution preventing layer composition, the dissolution preventing layer is preferably formed from a dissolution preventing layer composition containing a silicon compound.
Hereinafter, each component contained in the composition for a dissolution preventing layer suitable as a material for forming the dissolution preventing layer will be described.

(Silicon compound)
The composition for the dissolution preventing layer contains a silicon compound, so that when the gas barrier layer is formed, a component (for example, carbon atom) that inhibits the gas barrier property in the resin layer is mixed into the gas barrier layer. It becomes easy to prevent suitably.
Here, the “silicon compound” is not particularly limited as long as it is a compound containing a silicon atom, and it is an organic compound, an inorganic compound, a high molecular compound, or a low molecular compound. Also good.
The composition for the dissolution preventing layer in the present invention is the same composition as the composition for the gas barrier layer described later, from the viewpoint of improving the interlayer adhesion between the dissolution preventing layer and the gas barrier layer, and the refractive index difference between the two layers. It is preferable from the viewpoint of reducing.

Examples of the silicon compound include high molecular silicon compounds such as polyorganosiloxane compounds, polysilazane compounds, polysilane compounds, and polycarbosilane compounds; particles of silicon oxide, silicon nitride, silicon oxynitride, and the like.
Among these, high molecular silicon compounds such as polyorganosiloxane compounds, polysilazane compounds, polysilane compounds, and polycarbosilane compounds are preferred from the viewpoint of easily obtaining a dissolution preventing layer having a high silicon compound content, and among these, polysilazane compounds are preferred. preferable.
In view of improving the interlayer adhesion between the dissolution preventing layer and the gas barrier layer, the dissolution preventing layer composition of the present invention contains the same type of silicon compound as that contained in the gas barrier layer composition described later. Or from the viewpoint of reducing the difference in refractive index between the two layers.
For example, when the gas barrier layer composition contains a polysilazane compound as a silicon compound, the dissolution preventing layer composition preferably also contains a polysilazane compound.

  Here, the “polysilazane compound” may refer to a polymer having a repeating unit containing a —Si—N— bond (silazane bond) in the molecule. Specifically, the repeat is represented by the following formula 3. It refers to a polymer having units. In addition, the polysilazane compound represented by Formula 3 may be a polysilazane modified product.

  In Formula 3, n represents a repeating unit and represents an integer of 1 or more. Rx, Ry, and Rz each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, or unsubstituted Alternatively, it represents an aryl group having a substituent, an unsubstituted or substituted alkylsilyl group.

The polysilazane compound represented by Formula 3 is an organic polysilazane compound having at least one group containing a carbon atom other than a hydrogen atom among Rx, Ry, and Rz, and Rx, Ry, and Rz are all hydrogen atoms. A certain inorganic polysilazane compound is mentioned.
Among these, an inorganic polysilazane compound is preferable because it is not easily affected by the organic solvent contained in the gas barrier layer composition and a high effect of preventing the components on the resin layer surface from dissolving can be obtained. Perhydropolysilazane is preferred.

The dissolution preventing layer of the gas barrier film of the present invention is preferably substantially made of an inorganic material.
Here, “consisting essentially of an inorganic material” means that the content of the inorganic material is 90% by mass or more with respect to the total amount (100% by mass) of the dissolution preventing layer.
When the dissolution preventing layer is an inorganic layer formed by a gas phase method, or contains an inorganic substance such as a silicon compound in an amount of 90% by mass or more based on the total amount (100% by mass) of the active ingredients of the composition for the dissolution preventing layer. In the case of a layer formed from the composition for the dissolution preventing layer, it can be said that the dissolution preventing layer is substantially composed of an inorganic substance.
Here, “the active ingredient of the composition for the dissolution preventing layer” refers to a component excluding the solvent contained in the composition for the dissolution preventing layer.
Thereby, it becomes easy to suitably prevent a component (for example, carbon atom) that inhibits the gas barrier property in the resin layer from being mixed into the gas barrier layer when the gas barrier layer is formed. Furthermore, when the dissolution preventing layer is substantially composed of an inorganic substance, the water vapor permeability of the laminate constituting the gas barrier film is lower than that when the dissolution preventing layer substantially contains an organic substance, and oxygen, water vapor, etc. There is a tendency that the effect of preventing the permeation of gas is increased, that is, the gas barrier property is increased.
Here, “substantially contains an organic substance” means that the content of the organic substance exceeds 10% by mass with respect to the total amount (100% by mass) of the dissolution preventing layer.

The dissolution preventing layer may be modified or untreated as in the gas barrier layer described later.
However, when the dissolution preventing layer is formed from the composition for the dissolution preventing layer containing a silicon compound, the surface of the resin layer is affected by the organic solvent contained in the composition for the dissolution preventing layer. It is considered that the component dissolves and the component (for example, carbon atom) that inhibits the gas barrier property in the resin layer enters the dissolution preventing layer.
For this reason, even if the dissolution preventing layer is modified, the effect that the gas barrier property is imparted to the dissolution preventing layer may not be efficiently obtained.
Therefore, from the viewpoint of productivity, it is preferable not to modify the dissolution preventing layer. When the dissolution preventing layer composition contains only a polysilazane compound as a silicon compound, all the polysilazane compound is converted into silica glass (silicon oxide) unless the dissolution preventing layer is subjected to a modification treatment. Therefore, in this case, the dissolution preventing layer contains only silicon oxide as an inorganic substance and does not contain a nitride.

(Curing component, thermoplastic resin)
Moreover, it is preferable that the composition for dissolution prevention layers contains a hardening component.
Thereby, it becomes easy to suitably prevent a component (for example, carbon atom) that inhibits the gas barrier property in the resin layer from being mixed into the gas barrier layer.
As the curing component contained in the dissolution preventing layer composition, the same curable component (B) as that contained in the resin composition can be used.
Moreover, the composition for a dissolution preventing layer may contain a thermoplastic resin.
The thermoplastic resin contained in the composition for dissolution preventing layer can be the same as the thermoplastic resin (A) contained in the resin composition. Even if the composition for dissolution preventing layer does not contain the thermoplastic resin (A) or contains the thermoplastic resin (A), it is preferable to reduce the content thereof.
Specifically, the content ratio [(A) :( B)] of the thermoplastic resin (A) and the curable component (B) contained in the composition for the dissolution preventing layer is a mass ratio, preferably 0: 100 to 34:66, more preferably 0: 100 to 20:80.
When the content ratio [(A) :( B)] of the thermoplastic resin (A) and the curable component (B) is in the above range, the gas barrier property in the resin layer is formed when the gas barrier layer is formed. It becomes easy to suitably prevent components (for example, carbon atoms) that hinder the mixing into the gas barrier layer.

The composition for the dissolution preventing layer used in one embodiment of the present invention can contain an inorganic material such as silicon oxide particles (silica particles), and the total content of the thermoplastic resin (A), the curable component (B), and the inorganic material. The amount is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and still more preferably 90 to 100% by mass with respect to the total amount (100% by mass) of the active ingredients of the composition for dissolution preventing layer. .
Here, “the active ingredient of the composition for the dissolution preventing layer” refers to a component excluding the solvent contained in the composition for the dissolution preventing layer.
In addition, the composition for a dissolution prevention layer may contain a polymerizable component (B1) as the curable component (B), and may further contain a polymerization initiator.

(solvent)
From the viewpoint of making it easy to adjust the dissolution-preventing layer composition to a property suitable for coating when the dissolution-preventing layer is formed by coating, the dissolution-preventing layer composition may be in the form of a solution by adding a solvent. preferable.
The solvent is not particularly limited as long as it can dissolve or disperse the above-described silicon compound. For example, aliphatic hydrocarbon solvents such as n-hexane and n-heptane; aromatics such as toluene and xylene Group hydrocarbon solvents; halogenated hydrocarbon solvents such as dichloromethane, ethylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, monochlorobenzene; alcohols such as methanol, ethanol, propanol, butanol, propylene glycol monomethyl ether Solvents; ketone solvents such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, cyclohexanone; ester solvents such as ethyl acetate and butyl acetate; cellosolv solvents such as ethyl cellosolve; ether solvents such as 1,3-dioxolane; Is mentioned.
Among these, as the solvent, an aromatic hydrocarbon solvent and an alcohol solvent are preferable.

The amount of the solvent used for the preparation of the dissolution preventing layer composition is such that the concentration of the active ingredient in the dissolution preventing layer composition is preferably 5 to 50% by weight, more preferably 5 to 40% by weight, and even more preferably 10. What is necessary is just to use so that it may become ~ 30 mass%.
Here, “the active ingredient of the composition for dissolution preventing layer” refers to a component excluding the solvent contained in the composition for dissolution preventing layer.

(Other ingredients)
In addition to the silicon compound and the solvent, the dissolution preventing layer composition may further contain other components as long as the effects of the present invention are not impaired. Examples of other components include UV curable resins, curing agents, anti-aging agents, light stabilizers, and flame retardants.

(3) Gas barrier layer The gas barrier layer in this invention is laminated | stacked on an above-described dissolution prevention layer.
By having the gas barrier layer, the gas barrier film of the present invention can exhibit excellent gas barrier properties that are highly effective in preventing permeation of gases such as oxygen and water vapor. From the viewpoint of more efficiently obtaining the effect of improving the gas barrier property of the gas barrier film, the gas barrier layer is preferably laminated directly on the dissolution preventing layer without any other layer.

The thickness of the gas barrier layer is preferably 50 to 2000 nm, more preferably 50 to 1000 nm, and still more preferably 50 to 500 nm.
When the thickness of the gas barrier layer is in the above range, it is possible to exhibit excellent gas barrier properties that are highly effective in preventing permeation of gases such as oxygen and water vapor.

When the gas barrier layer of the gas barrier film of the present invention is a layer formed from the gas barrier layer composition, the gas barrier layer is preferably formed from the gas barrier layer composition containing a silicon compound.
Hereafter, each component contained in the composition for gas barrier layers suitable as a formation material of a gas barrier layer is described.

(Silicon compound)
The gas barrier layer composition can easily exhibit excellent gas barrier properties by containing a silicon compound.
The composition for the gas barrier layer in the present invention is the same composition as the composition for the dissolution preventing layer described above, from the viewpoint of improving the interlayer adhesion between the dissolution preventing layer and the gas barrier layer, and the refractive index difference between the two layers. It is preferable from the viewpoint of reducing.

Examples of the silicon compound include high molecular silicon compounds such as a polyorganosiloxane compound, a polysilazane compound, a polysilane compound, and a polycarbosilane compound in which a gas barrier layer having a high silicon compound content can be easily obtained.
Among these, a polysilazane compound is preferable from the viewpoint of obtaining a gas barrier film having high gas barrier properties.
From the viewpoint of improving the interlayer adhesion between the dissolution preventing layer and the gas barrier layer, the gas barrier layer composition in the present invention contains the same type of silicon compound as that contained in the dissolution preventing layer composition described above. Or from the viewpoint of reducing the difference in refractive index between the two layers.
For example, when the composition for a dissolution preventing layer contains a polysilazane compound as a silicon compound, the gas barrier layer composition preferably also contains a polysilazane compound.

  Here, the “polysilazane compound” may refer to a polymer having a repeating unit containing a —Si—N— bond (silazane bond) in the molecule. Specifically, the repeat is represented by the following formula 3. It refers to a polymer having units. In addition, the polysilazane compound represented by Formula 3 may be a polysilazane modified product.

  In Formula 3, n represents a repeating unit and represents an integer of 1 or more. Rx, Ry, and Rz each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, or unsubstituted Alternatively, it represents an aryl group having a substituent, an unsubstituted or substituted alkylsilyl group.

The polysilazane compound represented by Formula 3 is an organic polysilazane compound having at least one group containing a carbon atom other than a hydrogen atom among Rx, Ry, and Rz, and Rx, Ry, and Rz are all hydrogen atoms. A certain inorganic polysilazane compound is mentioned.
Among these, an inorganic polysilazane compound is preferable because a high effect of exhibiting excellent gas barrier properties is obtained, and specifically, perhydropolysilazane is preferable.

In the gas barrier layer composition used in one embodiment of the present invention, the content of the silicon compound is preferably 70 to 100% by mass, more preferably based on the total amount (100% by mass) of the active ingredients of the gas barrier layer composition. Is 80 to 100% by mass, more preferably 90 to 100% by mass.
Here, the “active ingredient of the gas barrier layer composition” refers to a component excluding the solvent contained in the gas barrier layer composition.

(solvent)
The gas barrier layer composition is preferably in the form of a solution by adding a solvent from the viewpoint of easily adjusting the gas barrier layer composition to properties suitable for coating when the gas barrier layer is formed by coating.
The solvent is not particularly limited as long as it can dissolve or disperse the above-described silicon compound, and the same solvent as the above-described composition for the dissolution preventing layer can be used, and an aromatic hydrocarbon solvent, Alcohol solvents are preferred.

The amount of the solvent used for the preparation of the gas barrier layer composition is such that the concentration of the active ingredient in the gas barrier layer composition is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and still more preferably 10 to 30%. What is necessary is just to use so that it may become mass%.
Here, the “active ingredient of the gas barrier layer composition” refers to a component excluding the solvent contained in the gas barrier layer composition.

(Other ingredients)
The composition for gas barrier layers may further contain other components in addition to the silicon compound and the solvent as long as the effects of the present invention are not impaired. Examples of other components include UV curable resins, curing agents, anti-aging agents, light stabilizers, and flame retardants.

The gas barrier layer in the present invention is preferably a layer formed by a modification treatment from the viewpoint of exhibiting excellent gas barrier properties.
As a method for modifying the gas barrier layer, for example, ion implantation treatment for modifying by implanting ions; plasma treatment for modifying by exposure to plasma; ultraviolet irradiation treatment for modifying by irradiating ultraviolet rays; Can be mentioned.
Among these, an ion implantation process is preferable as the gas barrier layer reforming process because the gas barrier layer can be efficiently reformed to the inside without roughening the surface of the gas barrier layer and excellent in gas barrier properties.

As ions used for the ion implantation treatment, ions of rare gases such as argon, helium, neon, krypton, and xenon are preferable, and among them, argon is preferable.
A method of implanting ions is not particularly limited, but a method of implanting ions in plasma (ion of plasma generation gas) is preferable because ion implantation can be easily performed.

In addition, as a method for modifying the gas barrier layer, an ultraviolet irradiation treatment that modifies by irradiating ultraviolet rays may be employed. Examples of the ultraviolet rays used for the ultraviolet irradiation treatment include vacuum ultraviolet light.
As the ultraviolet irradiation treatment for modifying by irradiation with vacuum ultraviolet light, for example, a method described in JP-A-2017-095758 can be employed.

(4) Adhesive layer The gas barrier film of the present invention is not particularly limited as long as it is composed of a laminate in which a dissolution preventing layer is interposed between the resin layer and the gas barrier layer. It can also be composed of a laminate formed by laminating an adhesive layer on the surface opposite to the surface in contact with the dissolution preventing layer, or on the surface of the resin layer opposite to the surface in contact with the dissolution preventing layer. It can also be comprised from the laminated body formed by laminating | stacking an adhesive bond layer.
When the gas barrier film of the present invention has an adhesive layer, the surface of the adhesive layer and the surface of the object to be sealed can be bonded to obtain a sealed body.

The adhesive layer which the gas barrier film of the present invention has is not particularly limited, and conventionally known adhesive layers can be used as long as the effects of the present invention are not impaired.
As a material which forms an adhesive bond layer, the composition for adhesive bond layers containing polyolefin resin and a thermosetting resin can be mentioned, for example.

The thickness of the adhesive layer is preferably 0.5 to 100 μm, more preferably 1 to 60 μm, and still more preferably 3 to 40 μm.
When the thickness of the said adhesive bond layer exists in the said range, when using the gas barrier film of this invention as a sealing material, it can use suitably.

(Production method of gas barrier film)
Although the production method of the gas barrier film in this invention is not specifically limited, For example, the method shown below is mentioned.
First, a resin composition is apply | coated on the peeling process surface of a peeling sheet, a coating film is formed, a coating film is dried on desired conditions, and a resin layer is formed on a peeling process surface. On this resin layer, the composition for a dissolution preventing layer is applied to form a coating film, and the coating film is dried under desired conditions to form a dissolution preventing layer on the resin layer.
In addition, when the composition for dissolution preventing layers contains a polysilazane compound, after drying the coating film, it is allowed to stand for several hours in a high temperature and high humidity environment (for example, 60 ° C., relative humidity 90%). A conversion treatment is preferably performed.
Then, the gas barrier layer composition is applied onto the dissolution preventing layer, a coating film is formed, the coating film is dried under a desired condition, a modification treatment is performed, and a gas barrier layer is formed on the dissolution preventing layer. Thus, a gas barrier film having a layer structure of release sheet / resin layer / dissolution prevention layer / gas barrier layer can be produced.

  Examples of the coating method of each composition described above include a solution method, for example, a die coating method, a spin coating method, a bar coating method, a dipping method, a roll coating method, a gravure coating method, a knife coating method, an air knife coating method, a roll. Examples thereof include a knife coating method, a screen printing method, a spray coating method, a gravure offset method, and a blade coating method.

When the dissolution preventing layer is an inorganic layer formed by a vapor phase method, examples of the vapor phase method include sputtering, vacuum vapor deposition (thermal vapor deposition, plasma vapor deposition), chemical vapor deposition, atomic layer deposition, etc. Is mentioned.
_Examples of the inorganic substance constituting the inorganic layer include an inorganic oxide (MO _x ), an inorganic nitride (MN _y ), an inorganic carbide (MC _z ), an inorganic oxide carbide (MO _x C _z ), and an inorganic nitride carbide (MN _y C _z). ), Inorganic oxynitride (MO _x N _y ), inorganic oxynitride carbide (MO _x N _y C _z ), and the like.
Here, “M” represents a metal element such as silicon, zinc, aluminum, magnesium, indium, calcium, zirconium, titanium, boron, hafnium, barium, or tin.
Moreover, the inorganic substance which comprises an inorganic layer may contain 2 or more types of different metal elements.
Examples of the metal belonging to the inorganic material include aluminum, magnesium, zinc, tin, and alloys composed of two or more of these. The inorganic layer may contain one kind of inorganic material or two or more kinds.

[Sealed body]
The sealing body of the present invention is formed by sealing an object to be sealed using the gas barrier film of the present invention as a sealing material. ADVANTAGE OF THE INVENTION According to this invention, the gas barrier film which is highly effective in preventing permeation | transmission of gas, such as oxygen and water vapor | steam, and was excellent in gas barrier property can be obtained. For this reason, it is possible to make it difficult for problems such as oxygen or water vapor or the like to enter the inside of the object to be sealed to deteriorate the performance of the object to be sealed.
Therefore, the sealing body of this invention can be used suitably for the use as which the performance maintenance of a to-be-sealed object is requested | required over a long period of time.
Examples of the object to be sealed include at least one selected from the group consisting of organic EL elements, organic EL display elements, inorganic EL elements, inorganic EL display elements, electronic paper elements, liquid crystal display elements, and solar cell elements. .

(Method for producing sealing body)
The method for producing the encapsulant of the present invention is not particularly limited. For example, when the gas barrier film of the present invention used as an encapsulant has the following mode, first the second release sheet is peeled and removed. Then, the surface of the exposed adhesive layer and the surface of the object to be sealed are bonded together and bonded under desired conditions to obtain a sealed body.
First release sheet / resin layer / dissolution prevention layer / gas barrier layer / adhesive layer / second release sheet Usually, the first release sheet is bonded to the surface of the adhesive layer and the surface of the object to be sealed. Is peeled off.
According to such a method for producing a sealing body, even when the resin layer does not have a sufficient function as a support for the gas barrier film, that is, when the thickness of the resin layer is very thin. However, since the first release sheet functions as a support for the gas barrier film until the first release sheet is peeled and removed, the resin layer is prevented from being broken or deformed, and the handleability is excellent.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples. Note that “parts” and “%” described below are “mass basis” unless otherwise specified.

Example 1
[Production of gas barrier film]
(1) Resin layer forming step As thermoplastic resin (A), 55 parts by mass of polysulfone resin (PSF) pellets (BASF, “ULTRASON S3010”, Tg = 180 ° C.) were dissolved in dichloromethane, and PSF A 15% solution was prepared.
To this solution, 45 parts by mass of tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., ADCP) as the curable component (B) and bis (2,4,6-trimethylbenzoyl) as the polymerization initiator ) -Phenylphosphine oxide (BASF, “Irgacure 819”) 1 part by mass was added and mixed to prepare a resin composition.

As a release sheet, on the non-treated surface of an easily adhesive-treated polyethylene terephthalate (PET) film (Toyobo Co., Ltd., “PET50A-4100”, thickness 50 μm), the resin composition prepared above was dried to a thickness of 10 μm. It was applied by a die coating method to form a coating film. The coating film was dried at 50 ° C. for 2 minutes and then at 140 ° C. for 2 minutes to dry the coating film.
Next, an untreated surface of an easy-adhesion-treated polyethylene terephthalate (PET) film (Toyobo Co., Ltd., “PET50A-4100”, thickness 50 μm) was laminated as a process sheet on the dried coating film.
Next, using a belt conveyor type ultraviolet irradiation device (product name: ECS-401GX, manufactured by Eye Graphics Co., Ltd.) and a high-pressure mercury lamp (product made by Eye Graphics Co., “H04-L41”) and the amount of ultraviolet light according to the following conditions A curing reaction was performed by irradiating ultraviolet rays through the process sheet with a meter (manufactured by Oak Manufacturing Co., Ltd., “UV-351”) to form a cured resin layer having a thickness of 10 μm on the release sheet.
<Conditions using high-pressure mercury lamp>
・ UV lamp height: 100mm
・ UV lamp output: 3kW
<Conditions using UV light meter>
Illuminance with a light wavelength of 365 nm: 400 mW / cm ²
・ Light intensity: 800 mJ / cm ²

(2) Formation process of dissolution prevention layer Then, the polyethylene terephthalate (PET) film used as a process sheet was peeled and removed.
And on the cured resin layer formed above, an inorganic polysilazane-based coating agent was applied as a dissolution preventing layer composition by a spin coating method, which is a solution method, to form a coating film. The thickness of the coating film was 200 nm.
Here, the above-mentioned “inorganic polysilazane coating agent” is a product obtained by adjusting the concentration of “Aquamica NL110-20 (main component: perhydropolysilazane)” manufactured by Merck Performance Materials to a 20 mass% solution with xylene. It is.
And by heating the obtained coating film at 120 ° C. for 1 minute, the coating film is dried, and further, in a high-temperature and high-humidity environment at 60 ° C. and a relative humidity of 90%, Conversion to silica glass (silicon oxide) was performed, and a dissolution preventing layer having a thickness of 200 nm was formed on the cured resin layer.

(3) Gas Barrier Layer Formation Step Next, an inorganic polysilazane coating agent was applied as a gas barrier layer composition on the dissolution preventing layer formed above by a spin coating method that is a solution method to form a coating film. . The thickness of the coating film was 100 nm.
Here, the above-mentioned “inorganic polysilazane coating agent” is a product obtained by adjusting the concentration of “Aquamica NL110-20 (main component: perhydropolysilazane)” manufactured by Merck Performance Materials to a 20 mass% solution with xylene. It is.
The obtained coating film was heated at 120 ° C. for 1 minute to dry the coating film, and a layer (inorganic polysilazane layer) containing an inorganic polysilazane compound having a thickness of 100 nm was formed on the dissolution preventing layer.
Next, on the surface of the formed inorganic polysilazane layer, using a plasma ion implantation apparatus (RF power supply: “RF56000” manufactured by JEOL Ltd., high voltage pulse power supply: “PV-3-HSHV-0835” manufactured by Kurita Seisakusho), Under the conditions shown below, the gas barrier film of Example 1 is subjected to a modification treatment by plasma ion implantation to form a gas barrier layer having a thickness of 100 nm and has a layer structure of release sheet / resin layer / dissolution prevention layer / gas barrier layer. Was made.
<Plasma ion implantation conditions>
-Chamber internal pressure: 0.2 Pa
-Plasma generation gas: Argon-Gas flow rate: 100 sccm
・ RF output: 1000W
・ RF frequency: 1000Hz
・ RF pulse width: 50 μsec ・ RF delay: 25 nsec ・ DC voltage: −10 kV
DC frequency: 1000Hz
DC pulse width: 5 μsec DC delay: 50 μsec Duty ratio: 0.5%
・ Processing time (ion implantation time): 200 seconds

(Example 2)
A gas barrier film of Example 2 was produced in the same manner as in Example 1 except that the dissolution preventing layer forming process of Example 1 was changed to the process shown below.
On the cured resin layer formed in the resin layer forming step of Example 1, silicon oxide was formed as a composition for the dissolution preventing layer by sputtering, which is a gas phase method, and dissolved to a thickness of 200 nm on the cured resin layer. A prevention layer was formed.

(Example 3)
A gas barrier film of Example 3 was produced in the same manner as in Example 1 except that the dissolution preventing layer forming process of Example 1 was changed to the process shown below.
On the cured resin layer formed in the resin layer forming step of Example 1, a silica sol-containing UV curable resin coating agent was applied as a dissolution preventing layer composition by a spin coating method, which is a solution method, and a coating film was formed. Formed. The thickness of the coating film was 200 nm.
Here, the “silica sol-containing UV curable resin coating agent” is “OPSTAR Z7530 manufactured by JSR, whose concentration is adjusted to a 5 mass% solution with propylene glycol monomethyl ether. The active ingredients of the “silica sol-containing UV curable resin coating agent” are composed of silica sol (silica particles), UV curable resin (polymerizable component), and a polymerization initiator.
And the coating film was dried by heating the obtained coating film at 70 degreeC for 1 minute.
Next, an untreated surface of an easy-adhesion-treated polyethylene terephthalate (PET) film (Toyobo Co., Ltd., “PET50A-4100”, thickness 50 μm) was laminated as a process sheet on the dried coating film.
Next, using a belt conveyor type ultraviolet irradiation device (product name: ECS-401GX, manufactured by Eye Graphics Co., Ltd.) and a high-pressure mercury lamp (product made by Eye Graphics Co., “H04-L41”) and the amount of ultraviolet light according to the following conditions A curing reaction was performed by irradiating ultraviolet rays through the process sheet with a meter (Oak Manufacturing Co., Ltd., “UV-351”) to form a dissolution preventing layer having a thickness of 200 nm on the cured resin layer.
<Conditions using high-pressure mercury lamp>
・ UV lamp height: 110mm
・ UV lamp output: 2.1kW
<Conditions using UV light meter>
Illuminance with a light wavelength of 365 nm: 260 mW / cm ²
・ Light intensity: 145 mJ / cm ²

(Comparative Example 1)
A gas barrier film of Comparative Example 1 was produced in the same manner as in Example 1 except that the dissolution preventing layer forming step of Example 1 was not performed.

(Comparative Example 2)
In the resin layer forming step of Example 1, the amount of pellets of the polysulfone resin (PSF), which is the thermoplastic resin (A), is changed from 55 parts by mass to 30 parts by mass to obtain the curable component (B). Comparative Example 2 was carried out in the same manner as in Example 1 except that the amount of tricyclodecane dimethanol diacrylate was changed from 45 parts by mass to 70 parts by mass, and the dissolution preventing layer was not formed in Example 1. A gas barrier film was prepared.

  For the gas barrier films prepared in Examples 1 to 3 and Comparative Examples 1 and 2 described above, (1) gas barrier property evaluation, (2) flexibility evaluation, and (3) optical isotropy by the following methods The evaluation of sex was performed, and the results are summarized in Table 1.

[Evaluation method]
(1) Evaluation of gas barrier properties Samples for measuring water vapor transmission rate were obtained by peeling off and removing the release sheets from the respective gas barrier films prepared in Examples 1 to 3 and Comparative Examples 1 and 2 described above. It was.
Using a water vapor transmission rate measurement device (manufactured by MOCON, “AQUATRAN”) for the measurement sample, the water vapor transmission rate (g / m) of the laminate in a high temperature and high humidity environment of 40 ° C. and a relative humidity of 90% ² / day). In addition, the detection lower limit value of the water vapor transmission rate measuring device is 0.0005 (g / m ² / day).
From the results of the water vapor transmission rate (g / m ² / day) measured in this way, the quality of the gas barrier property was evaluated according to the following criteria.
○ (Good): Water vapor transmission rate is 0.1 (g / m ² / day) or less × (No): Water vapor transmission rate exceeds 0.1 (g / m ² / day)

(2) Evaluation of flexibility and strength Each gas barrier film produced in Examples 1 to 3 and Comparative Examples 1 and 2 is cut into 15 mm × 150 mm test pieces, and a release sheet is peeled from each gas barrier film. The laminate was removed and used as a sample for measuring the elongation at break.
Using the tensile tester (Orientec Co., Ltd., “TENSILON RTA-100”) for the measurement sample, the chuck-to-chuck distance is set to 100 mm, and the tensile speed is set to 200 mm / min. Tensile tests were performed in an environment of ° C. and a relative humidity of 50%.
In addition, the “distance between chucks” refers to a distance between gripping parts that grip a laminate that is a measurement sample in a tensile tester.
The distance between chucks Xmm after the tensile test when the measurement sample was broken was measured, and the elongation at break (%) of the laminate was calculated according to the following formula 1.

From the result of the elongation at break (%) calculated in this way, the quality of flexibility was evaluated according to the following criteria.
○ (good): elongation at break of 2.0 to 9.0%
X (No): Elongation at break is less than 2.0%

(3) Evaluation of optical isotropy Each gas barrier film produced in Examples 1 to 3 and Comparative Examples 1 and 2 was cut into 40 mm × 40 mm test pieces, and a release sheet was peeled from each gas barrier film. The product obtained by removing the laminate was used as a sample for measuring in-plane retardation (retardation).
Using the phase difference measuring device (“KOBRA-WR” manufactured by Oji Scientific Instruments) for the measurement sample, the wavelength of the laminate was set to 589 nm, and the environment was 23 ° C. and the relative humidity was 50%. In-plane retardation (retardation) was measured.

(Summary of results)
From the evaluation results shown in Table 1, the following can be understood.
In the production of the gas barrier film of Comparative Example 1, the gas barrier film of Comparative Example 1 was formed when the gas barrier layer was formed because no dissolution preventing layer was interposed between the resin layer and the gas barrier layer. It has been speculated that a component (for example, carbon atom) that inhibits the gas barrier property in the resin cannot be prevented from being mixed into the gas barrier layer, and the gas barrier property is lowered.
In the production of the gas barrier film of Comparative Example 2, a dissolution preventing layer is not interposed between the resin layer and the gas barrier layer, and the breaking elongation of the laminate is within the range specified by the present invention (2.0 to 9.0). %)), It was found that the gas barrier film of Comparative Example 2 could not obtain appropriate flexibility.

On the other hand, in the production of each gas barrier film of Examples 1 to 3, a dissolution preventing layer is interposed between the resin layer and the gas barrier layer, and the range of elongation at break of the laminate is defined by the present invention. Due to the satisfaction, each of the gas barrier films of Examples 1 to 3 has a high effect of preventing permeation of gases such as oxygen and water vapor, is excellent in gas barrier properties, and is not easily broken against tensile stress. It was found to have flexibility and strength.
Furthermore, in Examples 1 and 2, it was found that the gas barrier property was low and the water vapor permeability was low due to the dissolution preventing layer being substantially made of an inorganic substance. On the other hand, in Example 3, since the composition for the dissolution preventing layer does not contain a thermoplastic resin, the gas barrier property is comparable to that of Comparative Example 2, which is considered to have a property that the component on the surface of the resin layer is difficult to dissolve. It turns out that it is obtained.

Claims (14)

A gas barrier film having a laminate formed by laminating a resin layer, a dissolution preventing layer, and a gas barrier layer in this order,
A gas barrier film, wherein the laminate has a breaking elongation of 2.0 to 9.0%.   The gas barrier film according to claim 1, wherein the resin layer is a layer formed from a resin composition containing a curable component (B).   The gas barrier film according to claim 1 or 2, wherein the resin layer is a layer formed from a resin composition further containing a thermoplastic resin (A).   The gas barrier film according to claim 3, wherein the glass transition temperature (Tg) of the thermoplastic resin (A) is 140 ° C or higher.   The content ratio [(A) :( B)] of the thermoplastic resin (A) and the curable component (B) in the resin composition is 35:65 to 95: 5 in mass ratio. The gas barrier film according to any one of 2 to 4.   The gas barrier film according to any one of claims 1 to 5, wherein the resin layer has a thickness of 1 to 40 µm.   The gas barrier film according to any one of claims 1 to 6, wherein the dissolution preventing layer is a layer formed from a composition for a dissolution preventing layer containing a silicon compound.   The gas barrier film according to any one of claims 1 to 7, wherein the dissolution preventing layer is substantially composed of an inorganic substance.   The dissolution preventing layer contains a curable component (B), and is optionally a layer formed from a composition for a dissolution preventing layer containing a thermoplastic component (A), and in the dissolution preventing layer composition, The content ratio [(A) :( B)] of the thermoplastic resin (A) and the curable component (B) is 0: 100 to 34:66 in mass ratio. The gas barrier film according to one item.   The gas barrier film according to any one of claims 1 to 9, wherein a ratio of the thickness of the resin layer to the thickness of the dissolution preventing layer is 0.005 times or more and 0.15 times or less.   The gas barrier film according to any one of claims 1 to 10, wherein the gas barrier layer is a layer formed from a composition for a gas barrier layer containing a silicon compound.   The gas barrier film according to claim 1, wherein the gas barrier layer is a layer formed by a modification treatment.   The said laminated body is a laminated body formed by laminating | stacking an adhesive bond layer on the surface on the opposite side to the surface which contact | connects the said melt | dissolution prevention layer in the said gas barrier layer. Gas barrier film.   An object to be sealed that is at least one selected from the group consisting of an organic EL element, an organic EL display element, an inorganic EL element, an inorganic EL display element, an electronic paper element, a liquid crystal display element, and a solar cell element. The sealing body formed by sealing with the gas-barrier film as described in any one of 1-13.