JP5928634B2 - Gas barrier film and electronic device - Google Patents

Description

The present invention relates to a gas barrier film and an electronic device, and more specifically, a gas barrier film mainly used for an electronic device such as an organic electroluminescence (EL) element, a solar cell element, and a liquid crystal display element, and an electron using the same. It is about the device.

Conventionally, aluminum oxide, magnesium oxide,
A gas barrier film formed by laminating a plurality of layers including a thin film of a metal oxide such as silicon oxide is used to wrap an article that needs to block various gases such as water vapor and oxygen, such as food, industrial products, and pharmaceuticals. It is widely used in packaging applications to prevent such alterations.

In addition to packaging applications, development to flexible electronic devices such as flexible solar cell elements, organic electroluminescence (EL) elements, liquid crystal display elements, etc. has been demanded, and many studies have been made. However, these flexible electronic devices are required to have a gas barrier property at a glass substrate level, so that a gas barrier film having sufficient performance has not been obtained yet.

As a method for forming such a gas barrier film, tetraethoxysilane (TE
Chemical vapor deposition method (plasma CVD method: Chemical Vapor Depo) in which an organic silicon compound typified by OS is used to form a film on a substrate while being oxidized with oxygen plasma under reduced pressure.
gas phase methods such as a physical deposition method (vacuum evaporation method or sputtering method) in which metal Si is evaporated using a semiconductor laser and deposited on a substrate in the presence of oxygen are known.

These inorganic vapor deposition methods have been preferably applied to the formation of inorganic films such as silicon oxide, silicon nitride, and silicon oxynitride, and examination of the composition range of the inorganic film for obtaining good gas barrier properties. Many studies have been made on the layer structure including these inorganic films, but the composition range and layer structure in which the gas barrier property is particularly good have not been specified.

Furthermore, it is very difficult to form a film having no defects by the above-described vapor phase method. For example, it is necessary to extremely reduce the film forming rate to suppress the generation of defects. For this reason, at the industrial level where high productivity is required, the gas barrier property to the extent required for flexible electronic devices has not been obtained. Simply increase the thickness of the inorganic film by the vapor phase method,
Although examination of laminating | stacking multiple layers of inorganic films was also made, since a defect grows continuously or a crack increases on the contrary, the gas barrier property has not been improved.

In contrast, by forming multiple layers of inorganic films and organic films alternately by the vapor phase method, the total thickness of the inorganic film is ensured without continuously growing the defects, and the defect surface of each inorganic film is further improved. Studies have also been made on an increase in gas permeation path length due to different inward positions, that is, improvement of gas barrier properties due to a so-called maze effect. However, at present, the gas barrier property is not sufficient, and further, it is considered difficult to put into practical use from the viewpoint of cost because the process becomes complicated and the productivity is remarkably low.

As one of the methods for solving the above problems, studies have been made to improve the gas barrier properties by modifying the coating layer formed by applying a solution of an inorganic precursor compound and drying it by heat or light, In particular, studies have been made to develop a high gas barrier property by using polysilazane as an inorganic precursor compound.

Polysilazane is a compound having a basic structure of — (SiR ₂ —NR) —. When polysilazane is subjected to heat treatment or wet heat treatment in an oxidizing atmosphere, it changes into silicon oxide via silicon oxynitride. At this time, since direct substitution from nitrogen to oxygen is caused by oxygen or water vapor in the atmosphere, it changes to silicon oxide with relatively little volume shrinkage, and as a result, there are few defects in the film due to volume shrinkage. It is known that a precise film can be obtained. Further, in the treatment with polysilazane, a relatively dense silicon oxynitride film can also be obtained by controlling the oxidizing property of the atmosphere.

However, the formation of a dense silicon oxynitride film or silicon oxide film by thermal modification or wet heat modification of polysilazane requires a high temperature of 450 ° C. or higher, and cannot be applied to a flexible substrate such as plastic. It was.

As a means for solving such a problem, a method of forming a silicon oxynitride film or a silicon oxide film by applying vacuum ultraviolet light to a coating film formed from a polysilazane solution has been proposed.

Vacuum ultraviolet light (hereinafter referred to as “V”) having an energy larger than each interatomic bonding force of polysilazane.
Using light energy with a wavelength of 100 to 200 nm, also called UV and VUV light), the oxidation of oxygen and ozone proceeds while the atoms are directly cut by the action of photons called photon processes. By doing so, the silicon oxynitride film or the silicon oxide film can be formed at a relatively low temperature.

Non-Patent Document 1 discloses a method for producing a gas barrier film by irradiating a polysilazane coating film with VUV light using an excimer lamp.

Patent Document 1 discloses that a polysilazane coating film containing a basic catalyst is coated with VUV light and UV.
A method for producing a gas barrier film by irradiating light is disclosed. Moreover, in the Example of patent document 1, the example of the gas-barrier film which laminated | stacked three gas barrier layers formed by polysilazane application | coating, drying, and VUV light irradiation on the resin base material is also mentioned.

Furthermore, in Patent Document 2, two or more gas barrier layers obtained by irradiating VUV light on a polysilazane coating film having a film thickness of 250 nm or less are laminated on a resin base material having a smooth surface (surface Ra value is less than 12 nm). A gas barrier film is disclosed. Thus, by making the surface of the base material smooth, even if the polysilazane coating film is a thin layer, the protrusions on the surface of the base material are not exposed through the polysilazane coating film, and a certain degree of gas barrier property improvement effect is obtained. It is considered possible.

Furthermore, in Patent Document 3, a gas barrier layer obtained by providing a smoothing layer made of an organic-inorganic composite material as an anchor coat layer on a resin base material and irradiating the polysilazane coating film formed thereon with VUV light. A gas barrier film having the following is disclosed. Patent Document 3
Compared with the case where the polysilazane coating film is directly provided on the resin substrate surface due to the synergistic effect of improving the adhesiveness with the polysilazane due to the smoothness of the substrate surface and the organic-inorganic composite surface, the gas barrier film disclosed in A large improvement in gas barrier properties is observed.

Special table 2009-503157 JP 2009-255040 A JP 2011-143577 A

Leibniz Institute of Surface Modification Biological Report 2008/2009: P18-P21

However, in the techniques described in the above-mentioned non-patent documents and patent documents, it is difficult to sufficiently suppress the deterioration of the barrier property in a high-temperature and high-humidity environment, and stable for a long period as required for flexible electronic devices. There is concern about maintaining the gas barrier properties.

Therefore, it is possible to achieve both a very high gas barrier property required for flexible electronic devices and the like, and a durability capable of maintaining a high gas barrier property even in a high temperature and high humidity environment, and
There has been a demand for a gas barrier film having good productivity.

This invention is made | formed in view of the said subject, The objective is to provide the gas barrier property film which has the very outstanding gas barrier property and durability, and favorable productivity. Another object of the present invention is to provide an electronic device having excellent durability using the gas barrier film.

The above object of the present invention is achieved by the following configurations.
1. A base material, and a gas barrier layer formed by subjecting a layer containing polysilazane to vacuum ultraviolet irradiation,
Metal compound particles (A) 65 to 100% by mass, hydrophobic material (B) 0 to 35% by mass (provided between the base material and the gas barrier layer and having a particle diameter of 1 to 200 nm) ,
And (A) + (B) = 100% by mass), an anchor coat layer having hydrophobicity, and a gas barrier film.
2. The metal compound particles are colloidal silica particles, the above-mentioned 1. The gas barrier film according to 1.
3. The colloidal silica particles have a chain shape or a bead shape, as described in 2. above. The gas barrier film according to 1.
4). The metal compound particles are polyorganosiloxane particles or polyorganosilsesquioxane particles, as described in 1. above. The gas barrier film according to 1.
5. Above 1. ~ 4. An electronic device using the gas barrier film according to any one of the above.

According to the present invention, it has good productivity by forming by coating without using a vapor phase method,
A gas barrier film having very excellent gas barrier performance and durability, and an electronic device having excellent durability using the same can be provided.

It is a section schematic diagram of a gas barrier film concerning one embodiment of the present invention. It is a cross-sectional schematic diagram which shows an example of the vacuum ultraviolet irradiation apparatus used for this invention. 1 is a schematic cross-sectional view of an electronic device according to an embodiment of the present invention.

Hereinafter, although the form for implementing this invention is demonstrated in detail, the scope of the present invention is not restrained by these description. Embodiments other than the following examples can also be appropriately implemented within a range that does not impair the gist of the present invention.

In the present specification, “vacuum ultraviolet light”, “vacuum ultraviolet light”, “VUV”, and “VUV light” specifically mean light having a wavelength of 100 to 200 nm.
Further, “X to Y” indicating a range means “X or more and Y or less”.

As a result of intensive studies in view of the above problems, the present inventor has been arranged between a base material, a gas barrier layer obtained by subjecting a layer containing polysilazane to vacuum ultraviolet irradiation treatment, and the base material and the gas barrier layer. And the metal compound particle (A) whose particle diameter is 1-200 nm 65-100 mass%
And a hydrophobic material (B) 0 to 35% by mass (however, (A) + (B) = 100% by mass) and an anchor coat layer having a hydrophobic property, It has been found that a gas barrier film having excellent gas barrier performance and durability can be realized even by a coating method excellent in the present invention, and as soon as the present invention has been achieved.

With a conventional gas barrier film formed by irradiating a coating film containing polysilazane formed on a resin substrate with VUV light, a stable gas barrier property over a long period of time required for a flexible electronic device can be obtained. Was difficult. Regarding this problem, the present inventor conducted a detailed study focusing on the layer configuration and production conditions of the gas barrier film,
It has been found that, by improving the adhesion between the polysilazane coating and the substrate surface, and preventing the polysilazane coating from peeling off from the substrate, it is possible to suppress a decrease in gas barrier properties even in a high temperature and high humidity environment. .

In order to explain the mechanism of the effect of the above-described configuration of the present invention, first, the configuration and behavior of a gas barrier film using a general polysilazane coating will be described.

Since perhydropolysilazane has a Si—H structure, when the anchor coat layer formed on the substrate contains an inorganic component, for example, when it contains a silica component, it reacts with Si—OH present on the substrate surface. Thus, it is considered that Si—O—Si bonds are formed, and in the initial stage, the polysilazane coating film and the substrate surface are firmly bonded.

However, in a high temperature and high humidity environment, the Si—O—Si bond is hydrolyzed to form Si—O—.
It can be cut like HHO-Si. Furthermore, once cut Si—OH HO—S
Since water easily enters the gap of i, Si—O—Si bonds existing around the i are also sequentially broken by hydrolysis.

By such a mechanism, it is considered that the film obtained by treating the polysilazane coating film with VUV light partially peels off from the substrate surface, and the gas barrier property is further deteriorated.

On the other hand, as a result of various studies, the inventor made the anchor coat layer to be a layer having three-dimensionally continuous pores and hydrophobicity, so that the anchor coat layer and the polysilazane coating film It was found that a very strong physical bond presumed to be an interpenetrating structure of can be formed. Since this physical bond does not deteriorate even under high temperature and high humidity, it is considered that the gas barrier film having the above-described configuration can maintain the initial high gas barrier property over a long period of time.

On the other hand, since the anchor coat layer of the present invention has pores as described above, when the layer itself has high hydrophilicity, moisture in the atmosphere tends to aggregate in the pores, and the anchor coat layer has an excessive amount. Can retain moisture. Such moisture reacts with polysilazane when a liquid containing polysilazane is applied on the anchor coat layer, and as a result, hydrolysis of the polysilazane coating proceeds excessively, and there is a concern that gas barrier properties are lowered. Therefore, it becomes possible to prevent the anchor coat layer from retaining moisture by imparting hydrophobicity to the anchor coat layer. As a result, the gas barrier film of the present invention can maintain high gas barrier properties for a long period of time.

Thus, in the present invention, the anchor coat layer having the three-dimensionally continuous pores and the hydrophobic property is formed, and the gas barrier layer is formed thereon, thereby providing high gas barrier properties and durability. In addition, a gas barrier film having good productivity can be obtained.

In addition, said mechanism is based on estimation and this invention is not restrict | limited to the said mechanism at all.

  Hereinafter, the detail of the component of the gas barrier film of this invention is demonstrated.

《Gas barrier film》
As shown in FIG. 1, the gas barrier film of the present invention comprises a base material 1 as a support, a gas barrier layer 4 obtained by subjecting a layer containing polysilazane to vacuum ultraviolet irradiation treatment, a base material 1 and a gas barrier layer 4. Metal compound particles (A) 6 having a particle diameter of 1 to 200 nm disposed between
5 to 100% by mass, hydrophobic material (B) 0 to 35% by mass (provided that (A) + (B) = 1
00 mass%), and an anchor coat layer 12 having hydrophobicity.

In addition, if the gas barrier film has the anchor coat layer and the gas barrier layer on one side of the base material, the above-mentioned effects can be obtained, but the anchor coat layer and the gas barrier layer are formed on both sides of the base material. It may be the configuration.

〔Base material〕
The substrate used in the present invention is a long support and has a gas barrier layer (hereinafter also simply referred to as “barrier property”) described later (hereinafter also simply referred to as “barrier layer”). However, the present invention is not limited to these materials.

For example, polyacrylic acid ester, polymethacrylic acid ester, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN)
, Polyesters such as polycarbonate (PC) and polyarylate, and polyvinyl chloride (
PVC), polyethylene (PE), polypropylene (PP), polystyrene (PS), nylon (Ny), aromatic polyamide, polyether ether ketone, polysulfone, polyether sulfone, polyimide, polyetherimide, etc. Heat-resistant transparent film based on silsesquioxane having an organic-inorganic hybrid structure (for example, product name Sila-DEC (registered trademark); manufactured by Chisso Corporation, and product name Silplus (registered trademark)) And a resin film formed by laminating two or more layers of the resin.

In terms of cost and availability, polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), and the like are preferably used, and optical transparency, heat resistance, inorganic In terms of adhesion to the layer and the gas barrier layer, a heat-resistant transparent film having a basic skeleton of silsesquioxane having an organic-inorganic hybrid structure can be preferably used.

On the other hand, for example, when a gas barrier film is used for an electronic device application of a flexible display, the process temperature may exceed 200 ° C. in the array manufacturing process. In the case of roll-to-roll manufacturing, since a certain amount of tension is always applied to the substrate, when the substrate is placed at a high temperature and the substrate temperature rises, the substrate temperature will change to the glass transition point. If it exceeds 1, the elastic modulus of the base material rapidly decreases, and as a result, the base material is stretched by tension, and there is a concern that the gas barrier layer is damaged. Therefore, in such applications, the glass transition point is 150.
It is preferable to use a heat-resistant material having a temperature of 0 ° C. or higher as the substrate. For example, it is preferable to use a heat resistant transparent film having a basic skeleton of polyimide, polyetherimide, or silsesquioxane having an organic-inorganic hybrid structure. However, since the heat-resistant resin represented by these is non-crystalline, the water absorption is larger than that of crystalline PET and PEN, and the dimensional change of the substrate due to humidity becomes larger. There are concerns about damage. However, even when these heat-resistant materials are used as a base material, dimensional changes due to moisture absorption and desorption of the base film itself under severe conditions of high temperature and high humidity by forming a gas barrier layer on both sides Can be suppressed, and damage to the gas barrier layer can be suppressed. Therefore, it is one of the more preferable embodiments that a heat resistant material having a glass transition point of 150 ° C. or higher is used as a base material, and a gas barrier layer is formed on both surfaces of the base material.

The thickness of the substrate is preferably about 5.0 to 500 μm, more preferably 25 to 250 μm.
It is. Most preferably, it is 100-200 micrometers.

Moreover, it is preferable that a base material is transparent. In addition, “transparent” here means visible light (4
The light transmittance at (00 to 700 nm) is 80% or more.

Since the base material is transparent and the gas barrier layer formed on the base material is also transparent, a transparent gas barrier film can be obtained. Therefore, a transparent substrate such as an organic EL element can be obtained. Because.

In addition, the base material using the above-described resins or the like may be an unstretched film or a stretched film.

The base material used in the present invention can be produced by a conventionally known general method. For example, an unstretched substrate that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching.

In addition, unstretched base material is uniaxially stretched, tenter-type sequential biaxial stretch, tenter-type simultaneous biaxial stretch,
A stretched base material can be produced by stretching in the direction of the base material flow (vertical axis) or in the direction perpendicular to the base material flow direction (horizontal axis) by a known method such as tubular simultaneous biaxial stretching. it can.

The draw ratio in this case can be appropriately selected according to the resin that is the raw material of the substrate,
It is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction, respectively.

Furthermore, in order to improve the dimensional stability of the substrate in the stretched film, it is preferable to perform relaxation treatment after stretching.

  Moreover, in the base material which concerns on this invention, before forming a gas barrier layer, you may give the corona treatment to the surface.

As the surface roughness of the substrate used in the present invention, the 10-point average roughness Rz defined by JIS B 0601 (2001) is preferably in the range of 1 to 500 nm, and 5 to 40
More preferably, it is in the range of 0 nm. More preferably, it is the range of 300-350 nm.

Moreover, it is preferable that the centerline average roughness Ra prescribed | regulated by JISB0601 (2001) is in the range of 0.5-12 nm in the base-material surface, More preferably, it is 1-8n.
More preferably, it is in the range of m.

[Middle layer]
An intermediate layer may be further formed between the base material according to the present invention and the anchor coat layer. The intermediate layer is preferably a so-called easy adhesion layer that improves the adhesion between the substrate surface and the anchor coat layer. A commercially available substrate with an easy-adhesion layer can also be preferably used.

Materials used for the intermediate layer include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin,
Modified styrene resin, modified silicone resin, alkyl titanate, and the like can be used alone or in combination of two or more.

Conventionally known additives can be added to these intermediate layer forming materials. And said intermediate | middle layer can be formed by coating on a support body by well-known methods, such as a roll coat, a gravure coat, a knife coat, a dip coat, and a spray coat, and drying and removing a solvent, a diluent, etc. it can. The amount of the intermediate layer is preferably about 0.1 to 5.0 g / m ² (dry state).

The intermediate layer can also be formed by a vapor phase method such as physical vapor deposition or chemical vapor deposition. For example, as described in JP-A-2008-142941, an inorganic film mainly composed of silicon oxide can be formed for the purpose of improving adhesion and the like.

(Smooth layer)
In the gas barrier film of the present invention, the intermediate layer may be a smooth layer. The smooth layer used in the present invention flattens the rough surface of the transparent resin film support on which protrusions and the like exist,
Alternatively, it is provided to fill and flatten the irregularities and pinholes generated in the transparent inorganic compound layer by the protrusions present on the transparent resin film support. Such a smooth layer is basically produced by curing a photosensitive material or a thermosetting material.

As the photosensitive material of the smooth layer, for example, a resin composition containing an acrylate compound having a radical reactive unsaturated compound, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate, Polyester acrylate, polyether acrylate, polyethylene glycol acrylate,
Examples thereof include a resin composition in which a polyfunctional acrylate monomer such as glycerol methacrylate is dissolved. Specifically, a UV curable organic / inorganic hybrid hard coating material OPSTAR (registered trademark) series manufactured by JSR Corporation can be used. It is also possible to use any mixture of the above resin compositions, and any photosensitive resin containing a reactive monomer having at least one photopolymerizable unsaturated bond in the molecule can be used. There are no particular restrictions.

Specifically, as a thermosetting material, Tutprom series (Organic polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Coat, Nanohybrid silicone manufactured by Adeka, Unidick manufactured by DIC, Inc. Registered trademark) V-
8000 series, EPICLON (registered trademark) EXA-4710 (ultra-high heat resistant epoxy resin), various silicon resins manufactured by Shin-Etsu Chemical Co., Ltd., inorganic / organic nanocomposite material SSG coat manufactured by Nittobo Co., Ltd., acrylic polyol and isocyanate prepolymer And thermosetting urethane resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, and silicon resin. Among these, an epoxy resin-based material having heat resistance is particularly preferable.

The method for forming the smooth layer is not particularly limited, but is preferably formed by a wet coating method such as a spray method, a blade coating method, or a dip method, or a dry coating method such as a vapor deposition method.

In the formation of the smooth layer, additives such as an antioxidant, an ultraviolet absorber, and a plasticizer can be added to the above-described photosensitive resin as necessary. In addition, regardless of the position where the smooth layer is laminated, in any smooth layer, an appropriate resin or additive may be used for improving the film formability and preventing the generation of pinholes in the film.

The smoothness of the smooth layer is preferably such that the center line average roughness Ra defined by JIS B 0601 (2001) is 0.5 to 12 nm. More preferably, it is 1 to 3 nm.
Moreover, it is preferable in the smooth layer surface that 10-point average roughness Rz prescribed | regulated by JISB0601 (2001) is 5-50 nm. More preferably, it is 10-40 nm.
When the value is smaller than this range, when the coating layer contacts the smoothing layer surface in a coating method such as a wire bar or a wireless bar at the stage of forming the coating layer described later, the coating property is impaired. There is. Moreover, when larger than this range, smoothing will become inadequate with respect to the surface roughness of a base material, and the meaning which provides a smooth layer will fade.

The thickness of the smooth layer is preferably in the range of 1 to 10 μm, and more preferably in the range of 2 to 7 μm.

[Bleed-out prevention layer]
As shown in FIG. 1, the base material of the gas barrier film of the present invention may have a bleed-out preventing layer 3 on the surface opposite to the surface on which the gas barrier layer 4 is provided.

The bleed-out prevention layer is provided for the purpose of suppressing a phenomenon that, when the film is heated, unreacted oligomers and the like are transferred from the film to the surface and contaminate the contact surface. The bleed-out prevention layer may basically have the same configuration as the smooth layer as long as it has this function.

The unsaturated organic compound having a polymerizable unsaturated group that can be contained as a hard coat agent in the bleed-out prevention layer is a polyunsaturated organic compound having two or more polymerizable unsaturated groups in the molecule. Alternatively, a monounsaturated organic compound having one polymerizable unsaturated group in the molecule can be exemplified.

As other additives, a matting agent may be contained. Matting agent has an average particle size of 0
. Inorganic particles of about 1 to 5 μm are preferred. As such inorganic particles, one or more of silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide and the like can be used in combination.

Here, the matting agent composed of inorganic particles is 2 per 100% by mass of the solid content of the hard coating agent.
% By mass or more, preferably 4% by mass or more, more preferably 6% by mass or more and 20% by mass or less,
It is desirable that they are mixed in a proportion of preferably 18% by mass or less, more preferably 16% by mass or less.

The bleed-out prevention layer may contain a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, a photopolymerization initiator and the like as other components of the hard coat agent and the mat agent.

The bleed-out prevention layer as described above is prepared as a coating solution by using a hard coating agent, a matting agent, and other components as necessary, and appropriately using a diluent solvent as necessary.
The coating solution can be formed by coating the surface of the support film by a conventionally known coating method and then curing it by irradiating with ionizing radiation.

As a material used in the bleed-out prevention layer, a UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) series manufactured by JSR Corporation may be mentioned.

As a method of irradiating with ionizing radiation, ultra-high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp,
Irradiate ultraviolet rays in a wavelength region of 100 to 400 nm, preferably 200 to 400 nm emitted from a carbon arc, metal halide lamp, etc., or irradiate an electron beam in a wavelength region of 100 nm or less emitted from a scanning or curtain type electron beam accelerator. This can be done.

The thickness of the bleed-out prevention layer is in the range of 1.0 to 10 μm from the viewpoint of improving the heat resistance of the film, facilitating the balance adjustment of the optical properties of the film, and adjusting the curl of the gas barrier film. More preferably, it is preferable to be in the range of 2 to 7 μm.

[Anchor coat layer]
In the present invention, the hydrophobic anchor coat layer is disposed between the gas barrier layer and the substrate. More specifically, the anchor coat layer is formed so that one surface is in contact with the gas barrier layer, and the other surface is formed in contact with a layer other than the gas barrier layer.

Furthermore, the anchor coat layer of the present invention includes metal compound particles (A) having a particle diameter of 1 to 200 nm. The form of the metal compound particles (A) includes (a) only hydrophilic metal compound particles. (B) a form containing only hydrophobic metal compound particles, and (c) a form containing both hydrophilic metal compound particles and hydrophobic metal compound particles. In the case of the form (a), the anchor coat layer according to the present invention contains a hydrophobic material (B). In the case of the forms (b) and (c), the anchor coat layer according to the present invention may or may not contain the hydrophobic material (B).

The anchor coat layer “has hydrophobicity” means that the total amount of the metal compound particles (A) and the hydrophobic material (B) is 100% by mass, and the hydrophobic metal compound is 0.1% by mass or more. Means including particles and / or hydrophobic material.

The metal compound particles (A) according to the present invention have a particle diameter in the range of 1 to 200 nm. Here, the particle diameter means the diameter when the metal compound particles (A) are spherical, and means the long diameter when the metal compound particles are not spherical. The particle diameter of the metal compound particles (A) is high magnification S
It shall be measured by EM observation, and more specifically, an average value obtained by measuring 100 particles by SEM observation shall be adopted.

When the particle diameter of the metal compound particles (A) is smaller than 1 nm, pores that are three-dimensionally continuous in the anchor coat layer cannot be formed, and the anchor coat layer and the gas barrier layer are difficult to adopt an interpenetrating structure. Therefore, the gas barrier layer is easily peeled from the substrate. Also,
When the particle diameter is larger than 200 nm, excessive irregularities are formed on the surface of the anchor coat layer,
There is a concern that the gas barrier property of the gas barrier layer is deteriorated.

Furthermore, when the particle diameter is in the range of 5 to 150 nm, it is more preferable because the balance between the expansion of the pore diameter and the smoothness of the surface of the anchor coat layer is improved, and when it is in the range of 10 to 130 nm, the pore diameter and the smoothness are further increased. This is more preferable because of a good balance.

The content of the metal compound particles (A) in the anchor coat layer is 65% by mass or more with respect to the total amount of the metal compound particles (A) and the hydrophobic material (B). In general, when spheres having a certain diameter are randomly filled, the volume filling rate is about 60% and the porosity is about 40%.
Therefore, when a layer is formed by applying a liquid in which spherical particles and a liquid binder are mixed, voids are not formed if the specific gravity of the particles and the binder is the same. The actual coating layer is not as simple as described above because it is affected in various ways. Therefore, as a result of intensive studies by the inventor,
It has been found that when the content of the metal compound particles in the anchor coat layer is 65% by mass or more, pores are formed on the surface of the anchor coat layer. The shape and size of the pores on the surface of the anchor coat layer can be confirmed, for example, by measuring the surface shape using AFM.

The content of the metal compound particles (A) is preferably 70% by mass or more, and more preferably 80% by mass or more from the viewpoint that the porosity of the anchor coat layer can be further increased.

In addition, it is preferable that a metal compound particle does not melt | dissolve substantially in the solvent of the coating liquid containing polysilazane. That is, the metal compound particles are preferably those that do not substantially dissolve in the solvent used when forming the gas barrier layer. Further, it is preferable that the metal compound particles alone form a film by bonding the particle contact portions during coating and drying.

  Hereinafter, the metal compound particles and the hydrophobic material will be described in detail.

(Hydrophilic metal compound particles)
Specific examples of the hydrophilic metal compound particles include the following hydrophilic metal compound particles, but are not limited thereto. The term “hydrophilic” refers to a material that is more easily dissolved in water than the “hydrophobic” material or particles described below.

Examples of the hydrophilic metal compound particles include colloidal silica particles, alumina sol particles, titania sol particles, and other metal oxide nanoparticle colloids. Among these, colloidal silica particles are particularly preferable. This is because colloidal silica has the advantage of high film-forming properties even under relatively low temperature drying conditions.

As the colloidal silica, any of a water-dispersed product and a solvent-dispersed product such as alcohol can be used. These are commercially available, for example, from Nissan Chemical Industries.

Specifically, as the commercially available colloidal silica manufactured by Nissan Chemical Industries, the following products can be preferably used.

Examples of water-dispersed alkaline colloidal silica stabilized with Na include Snowtex (registered trademark) 30 (particle diameter: 10 to 20 nm) and Snowtex (registered trademark) S (particle diameter: 8 to 1).
1 nm), SNOWTEX (registered trademark) XS (particle diameter 4 to 6 nm), SNOWTEX (registered trademark) 20 L (particle diameter 40 to 50 nm), SNOWTEX (registered trademark) XL (particle diameter 5)
0 to 60 nm) and Snowtex (registered trademark) ZL (particle diameter: 70 to 100 nm).

Examples of water-dispersed alkaline colloidal silica stabilized with ammonia include Snowtex (registered trademark) N (particle diameter: 10 to 20 nm), Snowtex (registered trademark) NS (particle diameter: 8 to 11 nm), and Snowtex (registered trademark). NXS (particle diameter 4-6 nm) can be mentioned.

As acid-type water-dispersed colloidal silica from which Na has been removed, SNOWTEX (registered trademark) O (particle diameter: 10 to 20 nm), SNOWTEX (registered trademark) OS (particle diameter: 8 to 11)
nm), Snowtex (registered trademark) OXS (particle diameter: 4 to 6 nm).

Moreover, as a special treatment type water-dispersed colloidal silica which is stable in a neutral range, SNOWTEX (registered trademark) C (particle diameter: 10 to 20 nm) can be exemplified.

As the solvent-dispersed colloidal silica, methanol silica sol (methanol dispersion, particle size 10 to 20 nm), IPA-ST (isopropanol dispersion, particle size 10 to 20 nm),
IPA-ST-ZL (isopropanol dispersion, particle size 70-100 nm) can be mentioned.

In the present invention, a colloidal silica having a chain shape or a bead shape (pearl necklace shape) formed by connecting substantially spherical particles can be preferably used. By using colloidal silica in the form of chain or bead, the film forming property of the anchor coat layer is improved, the porosity is also increased, and the adhesion between the anchor coat layer and the gas barrier layer is further improved.

Colloidal silica particles having a chain or bead shape can also be obtained as a commercial product manufactured by Nissan Chemical Industries, Ltd., for example. Specifically, the following products can be preferably used.

As chain colloidal silica, Na-stabilized water-dispersed alkaline colloidal silica Snowtex (registered trademark) UP (particle diameter: 40 to 100 nm), Na-removed acidic type water-dispersed colloidal silica Snowtex (registered) Trademark) OUP (particle diameter 40-1)
00 nm), IPA-ST-UP of solvent-dispersed colloidal silica (isopropanol dispersion,
Particle diameter of 40 to 100 nm).

As the beaded colloidal silica, Na-stabilized water-dispersed alkaline colloidal silica SNOWTEX (registered trademark) PS-S (particle diameter 80-120 nm), SNOWTEX (registered trademark) PS-M (particle diameter 80- 120 nm).

As described above, the hydrophilic metal compound particles exemplified above may be used singly or in combination of a plurality of kinds as long as they can be mixed.

When the hydrophilic metal compound particles are used, the content of the metal compound particles (A) and the hydrophobic material (B) is preferably 100% by mass, preferably 65 to 99.9% by mass, more preferably It is 70-99.5 mass%, More preferably, it is 80-99 mass%. If it is this range, sufficient hydrophobicity can be provided to an anchor coat layer, and aggregation of the water | moisture content in a pore can be suppressed.

(Hydrophobic material)
When the anchor coat layer contains only hydrophilic metal compound particles as the metal compound particles (A), the anchor coat layer contains a hydrophobic material.

Here, the hydrophobic material means a material that does not substantially dissolve in water among organic materials. Specifically, it is a material having a dissolution amount in water of 20 ° C./100 g of less than 0.1 g.

  Specific examples of the hydrophobic material include wax and resin.

More specific examples of the wax include, for example, paraffin, polyolefin, polyethylene wax, microcrystalline wax, fatty acid wax, and silicone oil. These preferably have a molecular weight of about 800 to 10,000. In addition, when the solvent of the coating solution for the anchor coat layer is aqueous, these waxes are oxidized to facilitate emulsification in the coating solution, and polarities such as hydroxyl groups, ester groups, carboxyl groups, aldehyde groups, peroxide groups, etc. Groups can also be introduced. Furthermore, for the purpose of lowering the softening point, these waxes are mixed with stearoamide, linolenic amide, lauryl amide, myristamide, hardened beef fatty acid amide, palmitoamide, oleic acid amide, rice sugar fatty acid amide, coconut fatty acid amide or these. It is also possible to add methylolated fatty acid amides, methylene bissteraloamide, ethylene bissteraroamide, and the like. Coumarone-indene resin, rosin-modified phenol resin, terpene-modified phenol resin, xylene resin, ketone resin, acrylic resin, ionomer, and copolymers of these resins can also be used.

Specific examples of the resin include, for example, diene (co) polymers such as polystyrene, polypropylene, polybutadiene, polyisoprene, and ethylene-butadiene copolymer, styrene-butadiene copolymer, methyl methacrylate-butadiene copolymer, and acrylonitrile. Synthetic rubber such as butadiene copolymer, polymethyl methacrylate, methyl methacrylate- (2
-Ethylhexyl acrylate) copolymer, methyl methacrylate-methacrylic acid copolymer, methyl acrylate- (N-methylolacrylamide) copolymer, (meth) acrylic (co) polymers such as polyacrylonitrile, polyvinyl acetate, vinyl acetate -Vinyl ester (co) polymers such as vinyl propionate copolymer, vinyl acetate-ethylene copolymer, vinyl acetate- (2-ethylhexyl acrylate) copolymer, polyvinyl chloride, polyvinylidene chloride, polystyrene, and the like The copolymer of these is mentioned. Of these, polystyrene, (meth) acrylic (co) polymer, vinyl ester (co) polymer, and synthetic rubber are preferably used.

These hydrophobic materials can be used singly or in combination of two or more. As the hydrophobic material, a synthetic product or a commercially available product may be used.

The content of the hydrophobic material is such that the form of (a) above, that is, when the anchor coat layer contains only hydrophilic metal compound particles as the metal compound particles (A), the metal compound particles (A) and the hydrophobic material ( The total amount of B) is preferably 100% by mass, preferably 0.1 to 35% by mass, more preferably 0.5 to 30% by mass, and still more preferably 1 to 20% by mass. If it is this range, sufficient hydrophobicity can be provided to an anchor coat layer, and the water aggregation to a pore can be suppressed.

(Hydrophobic metal compound particles)
The hydrophobic metal compound particles used in the present invention mean particles that are stably dispersed in a water-insoluble organic solvent and are not substantially dispersed in water. Specifically, “dispersing stably in a water-insoluble organic solvent” specifically means methyl ethyl ketone, methyl isobutyl ketone,
When hydrophobic metal compound particles are dispersed in one of the water-insoluble organic solvents selected from toluene, the dispersion state does not substantially cause sedimentation or aggregation even after standing at 20 ° C. for 24 hours. Means that In addition, “particles that are not substantially dispersed in water” means that water is added to a water-insoluble organic solvent in which hydrophobic metal compound particles are dispersed (at this time, the volume of the organic solvent and water). (The ratio is 50/50) When the water-insoluble organic solvent and water are separated by sufficiently stirring and mixing at 500 rpm for 10 minutes and then leaving to stand, the hydrophobic metal compound particles are substantially It means that it does not shift to the water phase.

Examples of such hydrophobic metal compound particles include particles obtained by coating the above-described hydrophilic metal compound particles with a hydrophobic material. The hydrophobic metal compound particles of this embodiment are, for example, a method of obtaining a hydrophobic silica sol by surface modification of a silica sol with a silane coupling agent in the presence of an amphiphilic organic solvent described in JP-A-2005-314197 And JP 20
By modifying the surface of nanoparticles composed of metal oxides, metalloid oxides, metal hydroxides, or metalloid hydroxides described in Japanese Patent Application No. 06-290725 with polysiloxane, the surface can be stabilized against a solvent. It can be obtained by a method for obtaining dispersed nanoparticles.

Further, polyorganosiloxane particles or polyorganosilsesquioxane particles can also be preferably used as the hydrophobic metal compound particles. In particular, having an organic group, and
A polyorganosiloxane or polyorganosilsesquioxane compound having a reactive group can be preferably used. Examples of reactive groups include Si—H, Si—OH,
Si-OR can be mentioned, Si-H and Si-OH are more preferable.

Specifically, as the polyorganosiloxane particles, the terminal represented by the following formula 1 is Si-H.
And polyorganosiloxane having a terminal represented by the following formula 2 having Si—OH or a polyorganosiloxane having Si—H in the side chain represented by the following formula 3.

  In said formula 1 and 2, n is the range of 1-100 each independently.

Moreover, in the said Formula 3, m is the range of 0-99 and n is the range of 1-100. n is
It is preferable that it is 30-100, and it is more preferable that it is 50-100.

Further, in the above formulas 1 to 3, the case where the organic group is methyl is shown. However, the organic group may be, for example, a phenyl group, and each organic group may be different.

Specific examples of the polyorganosiloxane include, but are not limited to, the compounds represented by the following S1 to S16.

Further, examples of the hydrophobic metal compound particles include cage-type polyorganosilsesquioxane. In order to further improve the adhesion and film-forming properties with the base material, Si-H and Si-
A cage-type polyorganosilsesquioxane having a reactive group such as OH is preferred. Specific examples of the cage-type polyorganosilsesquioxane include the following chemical formulas S17 to S1.
Although the compound represented by 9 is mentioned, it is not limited to these.

The hydrophobic metal compound particles can be used alone or in combination of two or more. In addition, as the hydrophobic metal compound particles, a synthetic product or a commercially available product may be used.
As an example of a commercial item, SP series made from Konishi Chemical Co., Ltd. can be mentioned, for example. Specifically, SP-1120 (H ₂ O) (organic group / methyl, particle diameter 20 nm), SP-1160 (H ₂ O) (organic group / methyl, particle diameter 60 nm), SP-
2160 (H ₂ O) (organic group / phenyl, particle diameter 60 nm), SP-4120 (H ₂ O) (
SP-1120 as organic group / vinyl, particle diameter 20 nm), methyl ethyl ketone dispersion
(MEK) (organic group / methyl, particle diameter 20 nm), SP-1160 (MEK) (organic group /
Methyl, particle diameter 60 nm), SP-6120 (MEK) (organic group / vinyl, particle diameter 20 n)
and polyorganosilsesquioxane particles such as m).

In the case where the anchor coat layer contains only hydrophobic metal compound particles, that is, in the case of the form (b) above, the hydrophobic material may or may not be used. This is because hydrophobicity can be imparted to the anchor coat layer without using a hydrophobic material. That is, the content in the case of using hydrophobic metal compound particles is in the range of 65 to 100% by mass, where the total amount of the metal compound particles (A) and the hydrophobic material (B) is 100% by mass. From the viewpoint that the porosity of the anchor coat layer can be further increased, the content is preferably 70 to 1.
It is 00 mass%, More preferably, it is 80-100 mass%.

The content of the hydrophobic metal compound particles when the hydrophobic metal compound particles and the above-described hydrophobic material are used in combination is 100% by mass of the total amount of the metal compound particles (A) and the hydrophobic material (B). As, it is 65-99.9 mass%, More preferably, it is 70-99.5 mass%, More preferably, it is 80-99 mass%.

Further, as in the form shown in (c) above, the hydrophilic metal compound particles and the hydrophobic metal compound particles may be used in combination. When used in combination, the hydrophobic material may or may not be used. Using the hydrophilic metal compound particles and the hydrophobic metal compound particles in combination,
And the content of the said hydrophilic metal compound particle when not using said hydrophobic material makes the whole metal compound particle 100 mass%, Preferably it is 65-99.9 mass%, More preferably, it is 70. It is -99.5 mass%, More preferably, it is 80-99 mass%.

The anchor coat layer may further contain other additives such as a known surfactant and pH adjuster. As a specific addition amount, the total amount of the metal compound particles and the hydrophobic material is 100% by mass.
It is preferable that it is the range of 0.01-1 mass% with respect to.

The method for forming the anchor coat layer is not particularly limited, but for example, metal compound particles,
If necessary, a hydrophobic material and other additives are dissolved or dispersed in a solvent to prepare a coating solution, and the coating solution is applied onto a substrate by a roll coating method, a flow coating method, an inkjet method, a spray coating. Examples thereof include a method of applying and drying by a method such as a method, a printing method, a dip coating method, a cast film forming method, a bar coating method and a gravure printing method.

When the solvent of the anchor coating layer coating solution is an organic solvent, the hydrophobic material is preferably added in a state dissolved in the coating solution. Specifically, the above wax or resin may be used by dissolving in an organic solvent. Moreover, the photosensitive material and thermosetting material which are used for the below-mentioned smooth layer can also be used.

When the anchor coating layer coating solution is aqueous, the hydrophobic material is preferably added in a state dispersed in the coating solution. Specifically, it is preferable to use an emulsion of wax or resin. Since the melting point or Tg of the wax or resin needs to be melted during general coating and drying, it is preferably 120 ° C. or lower, and more preferably 100 ° C. or lower. In addition, these dispersed particle sizes are set to 1 to obtain the composition uniformity of the anchor coat layer.
It is preferably μm or less, and more preferably 0.5 μm or less.

The amount of the anchor coat layer is preferably in the range of 0.05 to 5 g / m ² .
More preferably, it is in the range of 1 to ² g / m ² or less. By setting it to 0.05 g / m ² or more, it becomes possible to form a sufficiently thick adhesion region in which the gas barrier layer has penetrated into the voids of the anchor coat layer. By setting it to 5 g / m ² or less, there is no concern of forming an unnecessary thickness that does not contribute to the improvement of adhesion.

As mentioned above, although the aspect which apply | coats and forms an anchor coat layer with the coating liquid which mixed the metal compound particle and the hydrophobic material was described, the anchor coat layer of this invention formed the layer mainly based on the metal compound particle first. Then, it can be formed by overcoating a hydrophobic material. At this time, the hydrophobic material may be overcoated as a liquid dispersed or dissolved in a solvent. Alternatively, the hydrophobic material may be volatilized under reduced pressure if necessary and overcoated using a so-called gas phase method.

As the surface roughness of the anchor coat layer, the 10-point average roughness Rz defined by JIS B 0601 (2001) is preferably in the range of 1 to 500 nm, preferably 5 to 400 nm.
It is more preferable that it is in the range.

[Gas barrier layer]
The gas barrier layer according to the present invention is formed by subjecting a layer containing polysilazane to irradiation with vacuum ultraviolet rays.

(Polysilazane)
The “polysilazane” according to the present invention is a polymer having a silicon-nitrogen bond in the structure and is a polymer that is a precursor of silicon oxynitride, and those having the following structure are preferably used.

In the formula, R ₁ , R ₂ and R ₃ each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group.

In the present invention, perhydropolysilazane in which all of R ₁ , R _2, and R ₃ are hydrogen atoms is particularly preferred from the viewpoint of the denseness of the resulting gas barrier layer.

Perhydropolysilazane is presumed to have a linear structure and a structure in which a ring structure centered on a 6-membered ring and an 8-membered ring exists, and its molecular weight is about 600 to 2000 in terms of number average molecular weight (Mn).
It is a degree (polystyrene conversion by gel permeation chromatography) and is a liquid or solid substance.

Polysilazane is commercially available in the form of a solution dissolved in an organic solvent, and a commercially available product can be used as it is as a polysilazane-containing coating solution. Commercially available polysilazane solutions include NN120-20 and NAX120- manufactured by AZ Electronic Materials Co., Ltd.
20, NL120-20, and the like.

The gas barrier layer can be formed by applying a coating liquid containing polysilazane on the undercoat layer and drying it, and then irradiating with vacuum ultraviolet rays.

As an organic solvent for preparing a coating liquid containing polysilazane, it is preferable to avoid using an alcohol or water-containing one that easily reacts with polysilazane.

For example, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbon solvents, aliphatic ethers, ethers such as alicyclic ethers can be used, specifically, There are hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, ethers such as dibutyl ether, dioxane and tetrahydrofuran.

These organic solvents may be selected according to purposes such as the solubility of polysilazane and the evaporation rate of the solvent, and a plurality of organic solvents may be mixed.

The concentration of polysilazane in the coating liquid containing polysilazane varies depending on the film thickness of the gas barrier layer and the pot life of the coating liquid, but is preferably about 0.2 to 35% by mass.

In order to promote the modification to silicon oxynitride, the coating solution is coated with a metal catalyst such as an amine catalyst, a Pt compound such as Pt acetylacetonate, a Pd compound such as propionic acid Pd, or an Rh compound such as Rh acetylacetonate. It can also be added. In the present invention, it is particularly preferable to use an amine catalyst.

Specific amine catalysts include N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, N ′, N′-tetramethyl-1 , 3-Diaminopropane, N, N, N ′
, N′-tetramethyl-1,6-diaminohexane and the like.

The addition amount of these catalysts with respect to polysilazane is 0.1-10 mass% with respect to the whole coating liquid.
It is preferable that it is the range of 0.2-5 mass%, and it is preferable that it is the range of 0.2-5 mass%.
More preferably, it is the range of 5-2 mass%. By making the amount of catalyst addition within this range,
Excessive silanol formation due to a rapid progress of the reaction, a decrease in film density, an increase in film defects, and the like can be avoided.

Any appropriate method can be adopted as a method of applying the coating liquid containing polysilazane on the substrate.

Specific examples include a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a cast film forming method, a bar coating method, and a gravure printing method.

The thickness of the coating film can be appropriately set according to the purpose. For example, the thickness of the coating is preferably in the range of 50 nm to 2 μm, more preferably 100 nm to 1 as the thickness after drying.
. More preferably, it is in the range of 5 μm, and more preferably in the range of 250 nm to 1 μm.

The gas barrier layer according to the present invention is a step of irradiating a layer containing polysilazane with vacuum ultraviolet rays,
At least a portion of the polysilazane is modified to silicon oxynitride.

Here, the presumed mechanism in which the coating film containing polysilazane is modified in the vacuum ultraviolet ray irradiation step and becomes a specific composition of SiO _x N _y will be described by taking perhydropolysilazane as an example.

Perhydropolysilazane can be represented by the composition “— (SiH ₂ —NH) _n —”. S
In the case of iO _x N _y , x = 0 and y = 1. In order to satisfy x> 0, an external oxygen source is required. This is because (i) oxygen and moisture contained in the polysilazane coating solution, and (ii) oxygen taken into the coating film from the atmosphere during the coating and drying process. As an outgas from the substrate side due to oxygen, moisture, ozone, singlet oxygen taken into the coating film from the atmosphere in the vacuum ultraviolet irradiation process, (iv) heat applied in the vacuum ultraviolet irradiation process, etc. Oxygen and moisture moving into the coating film, (V) When the vacuum ultraviolet irradiation process is performed in a non-oxidizing atmosphere, when moving from the non-oxidizing atmosphere to the oxidizing atmosphere, Oxygen, moisture, etc. taken into the coating film become oxygen sources.

On the other hand, for y, the condition under which nitriding proceeds rather than the oxidation of Si is considered to be very special, so basically 1 is the upper limit.

Also, from the relationship of Si, O, and N bond, x and y are basically in the range of 2x + 3y ≦ 4. In the state of y = 0 where the oxidation has progressed completely, the coating film contains silanol groups, and there are cases where 2 <x <2.5.

The reaction mechanism presumed to produce silicon oxynitride and further silicon oxide from perhydropolysilazane in the vacuum ultraviolet irradiation step will be described below.

(I) Dehydrogenation and accompanying Si—N bond formation Si—H bonds and N—H bonds in perhydropolysilazane are relatively easily cleaved by excitation by vacuum ultraviolet irradiation, etc., and in an inert atmosphere, Si— Thought to recombine as N (
Si dangling bonds may be formed). That is, it is cured as a SiN _y composition without being oxidized. In this case, the polymer main chain is not broken. The breaking of Si—H bonds and N—H bonds is promoted by the presence of a catalyst and heating. The cut H is released out of the membrane as H ₂ .

(II) Formation of Si—O—Si Bonds by Hydrolysis / Dehydration Condensation Si—N bonds in perhydropolysilazane are hydrolyzed by water, and the polymer main chain is cleaved to form Si—OH. Two Si—OHs are dehydrated and condensed to form Si—O—Si bonds and harden. This is a reaction that occurs in the air, but during vacuum ultraviolet irradiation in an inert atmosphere, water vapor generated as outgas from the base material by the heat of irradiation is considered to be the main moisture source. If the moisture is excessive, Si-OH that cannot be dehydrated and condensed remains, and SiO
It becomes a cured film with a low gas barrier property shown by the composition of 2.1-2.3.

(III) Direct oxidation by singlet oxygen, formation of Si—O—Si bond When a suitable amount of oxygen is present in the atmosphere during irradiation with vacuum ultraviolet rays, singlet oxygen having a very strong oxidizing power is formed. H or N in perhydropolysilazane is replaced by O to replace Si-O-S.
Form an i-bond and cure. It is thought that recombination of the bond may occur due to cleavage of the polymer main chain.

(IV) Oxidation with Si-N bond cleavage by vacuum ultraviolet irradiation / excitation Since the energy of vacuum ultraviolet light is higher than the bond energy of Si-N in perhydropolysilazane, the Si-N bond is cleaved, and oxygen, It is considered that when an oxygen source such as ozone or water is present, it is oxidized to form a Si—O—Si bond or a Si—O—N bond. It is thought that recombination of the bond may occur due to cleavage of the polymer main chain.

Adjustment of the composition of the silicon oxynitride of the layer subjected to vacuum ultraviolet irradiation on the layer containing polysilazane is as follows:
The oxidation state can be controlled by appropriately combining the oxidation mechanisms (I) to (IV) described above.

In the vacuum ultraviolet irradiation process of the present invention, the illuminance of the vacuum ultraviolet light on the coating surface received by the polysilazane layer coating is preferably 30 to ²⁰⁰ mW / cm ² , and 50 to 160.
More preferably, it is mW / cm ² . If it is less than 30 mW / cm ^2, there is a concern that the reforming efficiency is greatly reduced, and if it exceeds 200 mW / cm ² , ablation occurs in the coating film,
There are concerns about damage to the substrate.

The amount of irradiation energy of vacuum ultraviolet rays on the polysilazane layer coating surface is 200 to 5000 m.
J / cm ² is preferable, and 500 to 3000 mJ / cm ² is more preferable. If it is less than 200 mJ / cm ^2, there is a concern that the modification will be insufficient, and 5000 mJ / cm ^2.
If it exceeds, there are concerns about cracking due to excessive modification and thermal deformation of the substrate.

As the vacuum ultraviolet light source, a rare gas excimer lamp is preferably used. Xe, Kr, A
The atoms of noble gases such as r and Ne are called inert gases because they are not chemically bonded to form molecules.

However, excited atoms of rare gases that have gained energy by discharge or the like can form molecules by combining with other atoms. When the rare gas is xenon,
e + Xe → Xe ^*
Xe ^* + 2Xe → Xe ₂ ^* + Xe
Xe ₂ ^* → Xe + Xe + hν (172 nm)
And when the excited excimer molecule Xe ₂ ^* transitions to the ground state, 172 nm
Excimer light is emitted.

A feature of the excimer lamp is that the radiation is concentrated on one wavelength, and since only the necessary light is not emitted, the efficiency is high. Further, since no extra light is emitted, the temperature of the object can be kept low. Furthermore, since it does not take time to start and restart,
Instant lighting and flashing are possible.

In order to obtain excimer light emission, a method using dielectric barrier discharge is known. In dielectric barrier discharge, a gas space is arranged between both electrodes via a dielectric such as transparent quartz, and several tens of k is applied to the electrodes.
A very thin micr that appears in a gas space by applying a high frequency high voltage of Hz and resembles lightning.
o discharge, which is a discharge, and when the micro discharge streamer reaches the tube wall (derivative), a charge accumulates on the dielectric surface.
The charge disappears.

This micro discharge spreads over the entire tube wall, and is a discharge that is repeatedly generated and extinguished. For this reason, flickering of light that can be confirmed with the naked eye occurs. Moreover, since a very high temperature streamer reaches a pipe wall directly locally, there is a possibility that deterioration of the pipe wall may be accelerated.

As a method for efficiently obtaining excimer light emission, electrodeless electric field discharge is possible in addition to dielectric barrier discharge. Electrodeless electric field discharge by capacitive coupling, also called RF discharge. The lamp and electrodes and their arrangement may be basically the same as for dielectric barrier discharge, but the high frequency applied between the two electrodes is lit at several MHz. Since the electrodeless field discharge can provide a spatially and temporally uniform discharge in this way, a long-life lamp without flickering can be obtained.

In the case of dielectric barrier discharge, micro discharge occurs only between the electrodes. Therefore, in order to cause discharge in the entire discharge space, the outer electrode covers the entire outer surface and transmits light to extract light to the outside. Must be a thing.

For this reason, an electrode in which a fine metal wire is formed in a net shape is used. Since this electrode uses as thin a line as possible so as not to block light, it is easily damaged by ozone generated by vacuum ultraviolet light in an oxygen atmosphere. In order to prevent this, it is necessary to provide an atmosphere of an inert gas such as nitrogen around the lamp, that is, the inside of the irradiation apparatus, and provide a synthetic quartz window to extract the irradiation light. Synthetic quartz windows are not only expensive consumables, but also cause light loss.

Since the double cylindrical lamp has an outer diameter of about 25 mm, the difference in distance to the irradiation surface cannot be ignored between the position directly below the lamp axis and the side surface of the lamp, resulting in a large difference in illuminance. Therefore, even if the lamps are closely arranged, a uniform illuminance distribution cannot be obtained. If the irradiation device is provided with a synthetic quartz window, the distance in the oxygen atmosphere can be made uniform, and a uniform illuminance distribution can be obtained.

When electrodeless field discharge is used, it is not necessary to make the external electrodes mesh. The glow discharge spreads over the entire discharge space simply by providing an external electrode on a part of the outer surface of the lamp. As the external electrode, an electrode that also serves as a light reflector made of an aluminum block is usually used on the back of the lamp. However, since the outer diameter of the lamp is as large as in the case of the dielectric barrier discharge, synthetic quartz is required to obtain a uniform illuminance distribution.

The biggest feature of the capillary excimer lamp is its simple structure. The quartz tube is closed at both ends, and only gas for excimer light emission is sealed inside.

The outer diameter of the tube of the thin tube lamp is about 6 nm to 12 mm, and if it is too thick, a high voltage is required for starting.

As the form of discharge, either dielectric barrier discharge or electrodeless field discharge can be used. The electrode may have a flat surface in contact with the lamp, but if the shape is matched to the curved surface of the lamp, the lamp can be firmly fixed and the discharge is more stable when the electrode is in close contact with the lamp. Also, if the curved surface is made into a mirror surface with aluminum, it also becomes a light reflector.

The Xe excimer lamp emits ultraviolet light having a short wavelength of 172 nm at a single wavelength, and thus has excellent luminous efficiency. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen.

Moreover, it is known that the energy of light having a short wavelength of 172 nm has a high ability to dissociate organic bonds. Due to the high energy of the active oxygen, ozone and ultraviolet radiation, the polysilazane layer can be modified in a short time.

Therefore, compared with low-pressure mercury lamps with wavelengths of 185 nm and 254 nm and plasma cleaning, it is possible to shorten the process time associated with high throughput, reduce the equipment area, and irradiate organic materials and plastic substrates that are easily damaged by heat. .

Since the excimer lamp has high light generation efficiency, it can be turned on with low power. In addition, light having a long wavelength that causes a temperature increase due to light is not emitted, and energy is irradiated in the ultraviolet region, that is, in a short wavelength, so that the increase in the surface temperature of the target object is suppressed. For this reason, it is suitable for flexible film materials such as PET that are easily affected by heat.

Oxygen is required for the reaction at the time of ultraviolet irradiation, but since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the ultraviolet irradiation process tends to decrease. It is preferable to carry out in a low state. That is, the oxygen concentration at the time of vacuum ultraviolet irradiation is
It is preferable to set it as 10-10000 ppm, More preferably, it is 50-5000 ppm.

As a gas that satisfies the irradiation atmosphere used at the time of irradiation with vacuum ultraviolet rays, a dry inert gas is preferable, and a dry nitrogen gas is particularly preferable from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.

The gas barrier layer according to the present invention may have a single layer structure or a multilayer structure of two or more layers.

[Overcoat layer]
An overcoat layer may be provided on the gas barrier layer according to the present invention.

(Material used for overcoat layer)
As the organic substance used for the overcoat layer, an organic resin such as an organic monomer, oligomer or polymer, or an organic-inorganic composite resin layer using a siloxane or silsesquioxane monomer, oligomer or polymer having an organic group is preferably used. Can do. These organic resins or organic-inorganic composite resins preferably have a polymerizable group or a crosslinkable group, contain these organic resins or organic-inorganic composite resins, and contain a polymerization initiator, a crosslinking agent, etc. as necessary. It is preferable to apply a light irradiation treatment or a heat treatment to the layer formed by coating from the organic resin composition coating solution to be cured. Here, the “crosslinkable group” is a group that can crosslink the binder polymer by a chemical reaction that occurs during light irradiation treatment or heat treatment. The chemical structure is not particularly limited as long as it is a group having such a function. Examples of the functional group capable of addition polymerization include cyclic ether groups such as an ethylenically unsaturated group and an epoxy group / oxetanyl group. Moreover, the functional group which can become a radical by light irradiation may be sufficient, and as such a crosslinkable group,
Examples thereof include a thiol group, a halogen atom, and an onium salt structure. Among these, an ethylenically unsaturated group is preferable and includes functional groups described in paragraphs 0130 to 0139 of JP2007-17948A.

Examples of organic-inorganic composite resins include “ORMOCER” in US Pat. No. 6,503,634.
An organic-inorganic composite resin described as “(registered trademark)” can also be preferably used.

The elastic modulus of the overcoat layer can be adjusted to a desired value by appropriately adjusting the structure of the organic resin, the density of the polymerizable group, the density of the crosslinkable group, the ratio of the crosslinking agent, and the curing conditions.

Specific examples of the organic resin composition include a resin composition containing an acrylate compound having a radical reactive unsaturated compound, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, and urethane acrylate. And a resin composition in which a polyfunctional acrylate monomer such as polyester acrylate, polyether acrylate, polyethylene glycol acrylate, or glycerol methacrylate is dissolved. It is also possible to use any mixture of the above resin compositions, and any photosensitive resin containing a reactive monomer having at least one photopolymerizable unsaturated bond in the molecule can be used. There are no particular restrictions.

Examples of the reactive monomer having at least one photopolymerizable unsaturated bond in the molecule include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n- Pentyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, allyl acrylate, benzyl acrylate,
Butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, 2-ethylhexyl acrylate,
Glycerol acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, phenoxyethyl acrylate,
Stearyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexadiol diacrylate, 1,3-propanediol acrylate, 1,4 -Cyclohexanediol diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate, tripropylene glycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, polyoxyethyltrimethylolpropane triacrylate, pentaerythritol triacrylate, Pentaerythritol tetraacrylate, ethylene oxide modified pentaerythritol triacrylate , Ethylene oxide modified pentaerythritol tetraacrylate, propion oxide modified pentaerythritol triacrylate, propion oxide modified pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyltrimethylolpropane triacrylate, butylene glycol diacrylate, 1,2,4 -Butanediol triacrylate, 2,2,
4-trimethyl-1,3-pentadiol diacrylate, diallyl fumarate, 1,1
0-decanediol dimethyl acrylate, pentaerythritol hexaacrylate,
And what changed said acrylate to methacrylate, (gamma) -methacryloxypropyl trimethoxysilane, 1-vinyl-2- pyrrolidone, etc. are mentioned. Said reactive monomer can be used as a 1 type, 2 or more types of mixture, or a mixture with another compound.

The composition of the photosensitive resin contains a photopolymerization initiator. Examples of the photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone, α-amino acetophenone, 4,4-dichloro. Benzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p- tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethyl ketal, benzylmethoxyethyl acetal, benzoy Methyl ether, benzoin butyl ether, anthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzylacetophenone, 2,6-bis (p-azide Benzylidene) cyclohexane, 2,6-bis (p-
Azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (
o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o
-Ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2
-(O-benzoyl) oxime, Michler's ketone, 2-methyl [4- (methylthio) phenyl] -2-monoforino-1-propane, 2-benzyl-2-dimethylamino-1- (
4-monoforinophenyl) -butanone-1, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphor Combinations of photoreducing dyes such as quinone, carbon tetrabromide, tribromophenylsulfone, benzoin peroxide, eosin, methylene blue, etc. and reducing agents such as ascorbic acid, triethanolamine, etc., these photopolymerization initiators Can be used singly or in combination of two or more.

The overcoat layer can contain an inorganic material. Inclusion of an inorganic material generally leads to an increase in the elastic modulus of the overcoat layer. The elastic modulus of the overcoat layer can also be adjusted to a desired value by appropriately adjusting the content ratio of the inorganic material.

As the inorganic material, inorganic fine particles having a number average particle diameter of 1 to 200 nm are preferable, and inorganic fine particles having a number average particle diameter of 3 to 100 nm are more preferable. As the inorganic fine particles, metal oxides are preferable from the viewpoint of transparency.

There is no particular restriction as the metal _{oxide, SiO 2, Al 2 O 3} , TiO 2, ZrO 2, ZnO
, SnO ₂ , In ₂ O ₃ , BaO, SrO, CaO, MgO, VO ₂ , V ₂ O ₅ , CrO ₂ , M
_{oO 2, MoO 3, MnO 2} , Mn 2 O 3, WO 3, LiMn 2 O 4, Cd 2 SnO 4, CdIn 2
O ₄ , Zn ₂ SnO ₄ , ZnSnO ₃ , Zn ₂ In ₂ O ₅ , Cd ₂ SnO ₄ , CdIn ₂ O ₄ , Zn ₂
Examples thereof include SnO ₄ , ZnSnO ₃ , and Zn ₂ In ₂ O ₅ . These may be used alone or in combination of two or more.

In order to obtain a dispersion of inorganic fine particles, it may be adjusted according to recent academic papers, but commercially available inorganic fine particle dispersions can also be preferably used.

Specifically, Snowtex (registered trademark) series manufactured by Nissan Chemical Co., Ltd., organosilica sol, NANOBYK (registered trademark) series manufactured by Big Chemie Japan, Nanoph
Examples thereof include dispersions of various metal oxides such as NanoDur (registered trademark) manufactured by Ase Technologies.

  These inorganic fine particles can also be used after surface treatment.

As the inorganic material, mica groups such as natural mica and synthetic mica, and tabular fine particles such as talc, teniolite, montmorillonite, saponite, hectorite, zirconium phosphate represented by the formula 3MgO · 4SiO · H ₂ O may be used. it can.

Specifically, examples of the natural mica include muscovite, soda mica, phlogopite, biotite and sericite. As the synthetic mica, fluorine phlogopite KMg ₃ (AlSi ₃ O ₁₀ ) F ₂ ,
Non-swelling mica such as potassium tetrasilicon mica KMg _2.5 Si ₄ O ₁₀ ) F ₂ , and Na tetrasilicic mica NaMg _2.5 (Si ₄ O ₁₀ ) F ₂ , Na or Li teniolite (Na, Li) Mg ₂
Li (Si ₄ O ₁₀ ) F ₂ , montmorillonite-based Na or Li hectorite (Na, Li)
Examples thereof include swelling mica such as _1/8 Mg _2/5 Li _1/8 (Si ₄ O ₁₀ ) F ₂ . Synthetic smectite is also useful.

The ratio of the inorganic material in the overcoat layer is 10 with respect to the entire overcoat layer.
The range is preferably -95% by mass, and more preferably 20-90% by mass.

In the overcoat layer, a so-called coupling agent can be used alone or mixed with other materials. The coupling agent is not particularly limited, such as a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent, but a silane coupling agent is preferable from the viewpoint of the stability of the coating solution.

Specific examples of the silane coupling agent include halogen-containing silane coupling agents (2-chloroethyltrimethoxysilane, 2-chloroethyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane). Epoxy group-containing silane coupling agent [2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane,
3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidyloxyethyltriethoxysilane, 3
-Glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, etc.], amino group-containing silane coupling agents (2-aminoethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane) 2- [N- (2-aminoethyl) amino] ethyltrimethoxysilane, 3- [N-
(2-Aminoethyl) amino] propyltrimethoxysilane, 3- (2-aminoethyl)
Amino] propyltriethoxysilane, 3- [N- (2-aminoethyl) amino] propylmethyldimethoxysilane, etc.), mercapto group-containing silane coupling agents (2-mercaptoethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane) , 3-
Mercaptopropyltriethoxysilane), vinyl group-containing silane coupling agents (vinyltrimethoxysilane, vinyltriethoxysilane, etc.), (meth) acryloyl group-containing silane coupling agents (2-methacryloyloxyethyltrimethoxysilane, 2- Methacryloyloxyethyltriethoxysilane, 2-acryloyloxyethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, etc.). These silane coupling agents can be used alone or in combination of two or more.

The overcoat layer is blended with the above organic resin and inorganic material, and other components as necessary, and prepared as a coating solution with a diluting solvent used as necessary, and the coating solution is conventionally known on the substrate surface. It is preferable to form the film by applying the ionizing radiation and curing it by irradiating with ionizing radiation. As a method of irradiating with ionizing radiation, an ultra-high pressure mercury lamp,
1 emitted from high pressure mercury lamp, low pressure mercury lamp, carbon arc, metal halide lamp, etc.
Ultraviolet rays in a wavelength region of 00 to 400 nm, preferably 200 to 400 nm are irradiated. Alternatively, the irradiation can be performed by irradiating an electron beam having a wavelength region of 100 nm or less emitted from a scanning or curtain type electron beam accelerator.

The overcoat layer can also be cured by irradiation with the above-described excimer lamp. When the gas barrier layer and the overcoat layer are formed by coating on the same line, the overcoat layer is preferably cured by irradiation with an excimer lamp.

<< Use of gas barrier film >>
The gas barrier film of the present invention is mainly a package for electronic devices or the like, or a gas barrier film used for display materials such as organic EL elements, solar cells, and plastic substrates such as liquid crystals, and a resin base for various devices using the gas barrier film. It can be applied to materials and various device elements.

The gas barrier film of the present invention can be preferably applied as various sealing materials and films.

An organic photoelectric conversion element will be described as an example of an electronic device including the gas barrier film of the present invention.

(Organic photoelectric conversion element)
When the gas barrier film of the present invention is used for an organic photoelectric conversion element, the gas barrier film is preferably transparent, and this gas barrier film is also referred to as a substrate (also referred to as a support).
), And can receive sunlight from this surface side.

That is, on the gas barrier film of the present invention, for example, a transparent conductive thin film such as ITO can be provided as a transparent electrode to constitute a resin support for organic photoelectric conversion elements.

Then, using the ITO transparent conductive thin film provided on the organic photoelectric conversion element resin support as an anode, a porous semiconductor layer is provided thereon, and a cathode made of a metal film is formed to form an organic photoelectric conversion element. The organic photoelectric conversion element can be sealed by stacking the same or different sealing material thereon, adhering the gas barrier film support and the surroundings, and encapsulating the element. The influence of the gas such as oxygen and the element on the element can be sealed.

The resin support for an organic photoelectric conversion element is a ceramic layer of a gas barrier film formed in this manner (here, the ceramic layer includes a silicon oxide layer formed by modifying a polysilazane layer). It is obtained by forming a transparent conductive thin film on the top.

The transparent conductive thin film can be formed by using a vacuum deposition method, a sputtering method, or the like, or by a coating method such as a sol-gel method using a metal alkoxide such as indium or tin.

Moreover, as a film thickness of a transparent conductive thin film, the transparent conductive thin film of the range of 0.1-1000 nm is preferable.

  Subsequently, each layer of the organic photoelectric conversion element material which comprises an organic photoelectric conversion element is demonstrated.

(Configuration of organic photoelectric conversion element and solar cell)
The preferable aspect of an organic photoelectric conversion element and a solar cell is demonstrated. In addition, although the preferable aspect of the organic photoelectric conversion element which concerns on this invention is demonstrated in detail hereafter, the said solar cell has the said organic photoelectric conversion element as the structure, and the preferable structure of a solar cell is described similarly. be able to.

There is no restriction | limiting in particular as an organic photoelectric conversion element, A power generation layer (p
Also referred to as a layer in which a n-type semiconductor and an n-type semiconductor are mixed, a bulk heterojunction layer, or an i layer.
) At least one layer, and any element that generates current when irradiated with light may be used.

  The preferable specific example of the layer structure of an organic photoelectric conversion element is shown below.

(Ii) Anode / power generation layer / cathode (ii) Anode / hole transport layer / power generation layer / cathode (iii) Anode / hole transport layer / power generation layer / electron transport layer / cathode (iv) Anode / hole transport layer / P-type semiconductor layer / power generation layer / n-type semiconductor layer / electron transport layer / cathode (v) anode / hole transport layer / first power generation layer / electron transport layer / intermediate electrode / hole transport layer / second power generation layer / Electron transport layer / cathode.

Here, the power generation layer needs to contain a p-type semiconductor material capable of transporting holes and an n-type semiconductor material capable of transporting electrons. Alternatively, a bulk heterojunction in a mixed state in one layer may be manufactured, but a bulk heterojunction configuration is preferable because of higher photoelectric conversion efficiency. A p-type semiconductor material and an n-type semiconductor material used for the power generation layer will be described later.

Like the organic EL element, by sandwiching the power generation layer between the hole transport layer and the electron transport layer, the extraction efficiency of holes and electrons to the anode / cathode can be increased.
i) and (iii)) are preferred. In addition, the power generation layer itself also increases the rectification of holes and electrons (selection of carrier extraction), so that the power generation layer is sandwiched between layers of a p-type semiconductor material and a single n-type semiconductor material as in (iv). Configuration (also referred to as “p-i-n configuration”) may be used. Moreover, in order to improve the utilization efficiency of sunlight, the tandem configuration (configuration (v)) in which sunlight of different wavelengths is absorbed by each power generation layer may be employed.

  Below, the material which comprises these layers is described.

(Organic photoelectric conversion element material)
The material used for formation of the electric power generation layer of an organic photoelectric conversion element is demonstrated.

<P-type semiconductor material>
Examples of the p-type semiconductor material preferably used as the power generation layer (bulk heterojunction layer) of the organic photoelectric conversion element include various condensed polycyclic aromatic low molecular compounds and conjugated polymers / oligomers.

Examples of the condensed polycyclic aromatic low molecular weight compound include anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, ovalene, thacumanthracene, bisanthene, zeslen , Heptazethrene, pyranthrene, violanthene, isoviolanthene,
Compounds such as circobiphenyl and anthradithiophene, porphyrin, copper phthalocyanine, tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bisethylenetetrathiafulvalene (BEDTTTTF) -perchloric acid complex, and derivatives thereof And precursors.

Examples of the derivative having the above condensed polycycle include WO 03/16599 pamphlet, WO 03/28125 pamphlet, US Pat. No. 6,690,02.
No. 9, a pentacene derivative having a substituent described in JP-A No. 2004-107216 and the like, a pentacene precursor described in U.S. Patent Application Publication No. 2003/136964, J. Pat. Amer. Chem. Soc. , Vol127. No. 14.4986, J. MoI. A
mer. Chem. Soc. , Vol. 123, p9482; Amer. Chem.
Soc. , Vol. 130 (2008), no. 9, acene-based compounds substituted with a trialkylsilylethynyl group described in 2706 and the like.

Examples of the conjugated polymer include polythiophene such as poly-3-hexylthiophene (P3HT) and oligomers thereof, or Technical Digest of the th.
e International PVSEC-17, Fukuoka, Japan, 2
Polythiophene having a polymerizable group described in 007, P1225, Nature M
aterial, (2006) vol. 5, p328, a polythiophene-thienothiophene copolymer, a polythiophene-diketopyrrolopyrrole copolymer described in WO08 / 000664, and a polythiophene-thiazolothiazole copolymer described in Adv Mater, 2007p4160 , Nature Mat. vol. 6 (2
007), p497 described in PCPDTBT, etc., polypyrrole and its oligomer, polyaniline, polyphenylene and its oligomer, polyphenylene vinylene and its oligomer, polythienylene vinylene and its oligomer, polyacetylene, polydiacetylene, polysilane, Examples thereof include polymer materials such as σ-conjugated polymers such as polygermane.

In addition, as an oligomer material instead of a polymer material, α-sexual thiophene α, ω-dihexyl-α-sexual thiophene, α, ω-dihexyl-α-, which is a thiophene hexamer, is used.
Oligomers such as quinkethiophene and α, ω-bis (3-butoxypropyl) -α-sexualthiophene can be preferably used.

Among these compounds, a compound that is highly soluble in an organic solvent to the extent that a solution process is possible and that can produce a crystalline thin film and achieve high mobility after drying is preferable.

In addition, when the electron transport layer is formed on the power generation layer by coating, there is a problem that the electron transport layer solution dissolves the power generation layer. Therefore, a material that can be insolubilized after coating by a solution process may be used. .

Such materials include Technical Digest of the Int.
international PVSEC-17, Fukuoka, Japan, 2007,
Materials such as polythiophene having a polymerizable group described in P1225, which can be insolubilized by polymerizing and crosslinking the coating film after coating, or US Patent Application Publication No. 2003/136964, and JP-A-2008-16834 As described in the above, materials that can be insolubilized by reacting soluble substituents by applying energy such as heat can be used.

<N-type semiconductor material>
Although it does not specifically limit as an n-type semiconductor material used for a bulk heterojunction layer, For example, the perfluoro which substituted the hydrogen atom of p-type semiconductors, such as fullerene, octaazaporphyrin, perfluoropentacene, and perfluorophthalocyanine, with the fluorine atom body,
Examples include aromatic carboxylic acid anhydrides such as naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide, and polymer compounds containing the imidized product as a skeleton. it can.

However, fullerene derivatives that can perform charge separation with various p-type semiconductor materials at high speed and efficiently are preferable. Fullerene derivatives include fullerene C ₆₀ and fullerene C.
₇₀ , fullerene C ₇₆ , fullerene C ₇₈ , fullerene C ₈₄ , fullerene C ₂₄₀ , fullerene C ₅₄₀ , mixed fullerene, fullerene nanotubes, multi-walled nanotubes, single-walled nanotubes, nanohorns (conical), etc., and some of them are hydrogen Fullerenes substituted by atoms, halogen atoms, substituted or unsubstituted alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, cycloalkyl groups, silyl groups, ether groups, thioether groups, amino groups, silyl groups, etc. Derivatives can be mentioned.

Among them, [6,6] -phenyl C ₆₁ -butyric acid methyl ester (abbreviation PCB)
M), [6,6] - phenyl C ₆₁ - butyric acid -n- butyl ester (PCBN
B), [6,6] - phenyl C ₆₁ - butyric acid - isobutyl ester (PCBi
B), [6,6] - phenyl C ₆₁ - butyric acid -n- hexyl ester (PCB
H), Adv. Mater. , Vol. 20 (2008), p2116, etc.
-PCBM, aminated fullerene such as JP-A 2006-199674, JP-A 2008
No. -130889 and the like, and fullerene derivatives having a substituent and improved solubility, such as fullerene having a cyclic ether group such as US Pat. No. 7,329,709, are used. It is preferable.

(Hole transport layer / electron block layer)
In the organic photoelectric conversion element, a hole transport layer is provided between the bulk heterojunction layer and the anode, and charges generated in the bulk heterojunction layer can be taken out more efficiently. It is preferable to have.

As a material constituting these layers, for example, as a hole transport layer, PEDOT (poly-3,4-ethylenedioxythiophene) such as product name BaytronP (registered trademark) manufactured by Stark Vitec, polyaniline and its Doping material, WO 06/19270
Cyanide compounds described in No. Pamphlet etc. can be used.

Note that electrons generated in the bulk heterojunction layer do not flow to the anode side in the hole transport layer having a LUMO level shallower than the LUMO level of the n-type semiconductor material used for the bulk heterojunction layer. An electronic block function having a rectifying effect is provided.

Such a hole transport layer is also called an electron block layer, and it is preferable to use a hole transport layer having such a function. As such a material, a triarylamine compound described in JP-A-5-271166 or a metal oxide such as molybdenum oxide, nickel oxide, or tungsten oxide can be used.

Moreover, the layer which consists of a p-type semiconductor material single-piece | unit used for the bulk heterojunction layer can also be used. As a means for producing these layers, either a vacuum vapor deposition method or a solution coating method may be used, but a solution coating method is preferable. It is preferable to produce a coating film in the lower layer before producing the bulk heterojunction layer because it has the effect of leveling the application surface and reduces the influence of leakage and the like.

(Electron transport layer / hole blocking layer)
The organic photoelectric conversion element can take out electric charges generated in the bulk heterojunction layer more efficiently by installing an electron transport layer between the bulk heterojunction layer and the cathode. Therefore, it is preferable that the organic photoelectric conversion element has an electron transport layer.

As a material for the electron transport layer, a perfluoro body of a p-type semiconductor such as octaazaporphyrin, perfluoropentacene or perfluorophthalocyanine can be used, but a HOMO level of a p-type semiconductor material used for a bulk heterojunction layer. Deeper than HOM
The electron transport layer having an O level is given a hole blocking function having a rectifying effect so that holes generated in the bulk heterojunction layer do not flow to the cathode side.

Such an electron transport layer is also called a hole blocking layer, and it is preferable to use an electron transport layer having such a function.

Examples of such materials include phenanthrene compounds such as bathocuproine, n-type semiconductor materials such as naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide, and titanium oxide. N-type inorganic oxides such as zinc oxide and gallium oxide, and alkali metal compounds such as lithium fluoride, sodium fluoride, and cesium fluoride can be used.

A layer made of a single n-type semiconductor material used for the bulk heterojunction layer can also be used as the electron transport layer. As a means for producing these layers, either a vacuum vapor deposition method or a solution coating method may be used, but a solution coating method is preferable.

(Other layers)
For the purpose of improving energy conversion efficiency and improving the lifetime of the element, a structure having various intermediate layers in the element may be employed. Examples of the intermediate layer include a hole block layer, an electron block layer, a hole injection layer, an electron injection layer, an exciton block layer, a UV absorption layer, a light reflection layer, and a wavelength conversion layer.

(Transparent electrode (first electrode))
The transparent electrode is not particularly limited to a cathode and an anode, and can be selected depending on the element configuration, but preferably a transparent electrode is used as the anode. For example, when used as an anode, preferably 38
It is an electrode that transmits light of 0 to 800 nm.

As the material, for example, transparent conductive metal oxides such as indium tin oxide (ITO), SnO ₂ , and ZnO, metal thin films such as gold, silver, and platinum, metal nanowires, and carbon nanotubes can be used.

Also selected from the group consisting of derivatives of polypyrrole, polyaniline, polythiophene, polythienylene vinylene, polyazulene, polyisothianaphthene, polycarbazole, polyacetylene, polyphenylene, polyphenylene vinylene, polyacene, polyphenylacetylene, polydiacetylene and polynaphthalene. Conductive polymers can also be used. A plurality of these conductive compounds can be combined to form a transparent electrode.

(Counter electrode (second electrode))
The counter electrode may be a single layer of a conductive material, but in addition to a conductive material, a resin that holds these may be used in combination. The conductive material for the counter electrode has a small work function (4 eV or less)
A metal, an alloy, an electrically conductive compound and a mixture thereof are used as electrode materials.

Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.

Among these, from the viewpoint of electron extraction performance and durability against oxidation, etc., a mixture of these metals and a second metal which is a stable metal having a larger work function value than this, for example, a magnesium / silver mixture, magnesium / Aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.

The counter electrode can be produced by producing a thin film of these electrode materials by a method such as vapor deposition or sputtering. The film thickness is usually 10 nm to 5 μm, preferably 5
It is selected in the range of 0 to 200 nm.

If a metal material is used as the conductive material of the counter electrode, the light reaching the counter electrode side is reflected and reflected to the first electrode side, and this light can be reused and is absorbed again by the photoelectric conversion layer, and more photoelectric conversion is performed. Efficiency is improved and preferable.

The counter electrode may be a metal such as gold, silver, copper, platinum, rhodium, ruthenium, aluminum, magnesium, or indium, a nanoparticle made of carbon, a nanowire made of carbon, or a carbon nanostructure. A nanowire dispersion made of carbon is preferable because a transparent and highly conductive counter electrode can be produced by a coating method.

Moreover, when making the counter electrode side light-transmitting, for example, after forming a thin conductive material suitable for the counter electrode such as aluminum and aluminum alloy, silver and silver compound with a film thickness of about 1 to 20 nm, By providing a film of the conductive light transmissive material mentioned in the description of the transparent electrode, a light transmissive counter electrode can be obtained.

(Intermediate electrode)
Moreover, as a material of the intermediate electrode required in the case of the tandem configuration as in (v) of the layer configuration of the organic photoelectric conversion element, a layer using a compound having both transparency and conductivity is preferable. Transparent metal oxides such as ITO, AZO, FTO, and titanium oxide used in the transparent electrode, very thin metal layers such as Ag, Al, Au, or layers containing nanoparticles / nanowires, PEDOT: PSS, polyaniline, etc. The conductive polymer material or the like can be used.

In addition, some of the hole transport layer and the electron transport layer described above function as a charge recombination layer by stacking them in an appropriate combination, and when the intermediate electrode has such a configuration, a step of further manufacturing is omitted. Can be preferable.

(Metal nanowires)
As the conductive fibers, organic fibers and inorganic fibers coated with metal, conductive metal oxide fibers, metal nanowires, carbon fibers, carbon nanotubes, etc. can be used.
Metal nanowires are preferred.

In general, the metal nanowire refers to a linear structure having a metal element as a main component. In particular, the metal nanowire in the present invention means a linear structure having a diameter of nm size.

The metal nanowires preferably have an average length of 3 μm or more in order to produce a long conductive path with one metal nanowire and to exhibit appropriate light scattering properties, and more preferably 3 μm to 3 μm 500 μm is preferable, and 3 μm to 300 μm is particularly preferable. In addition, the relative standard deviation of the length is preferably 40% or less.

Moreover, it is preferable that an average diameter is small from a transparency viewpoint, On the other hand, the larger one is preferable from an electroconductive viewpoint. In the present invention, the average diameter of the metal nanowire is 10
nm to 300 nm is preferable, and 30 nm to 200 nm is more preferable. In addition, the relative standard deviation of the diameter is preferably 20% or less.

There is no restriction | limiting in particular as a metal composition of metal nanowire, Although it can comprise from the 1 type or several metal of a noble metal element and a base metal element, it is gold, platinum, silver, palladium, rhodium, iridium, ruthenium, osmium, iron In addition, it preferably contains at least one metal selected from the group consisting of cobalt, copper and tin, and more preferably contains at least silver from the viewpoint of conductivity.

Moreover, in order to make electroconductivity and stability, such as sulfidation of metal nanowire, oxidation resistance, and migration resistance, it is also preferable that silver and a noble metal except silver are included. When the metal nanowire contains two or more kinds of metal elements, for example, the metal composition may be different between the surface and the inside of the metal nanowire, or the entire metal nanowire has the same metal composition. May be.

There is no restriction | limiting in particular in the manufacturing method of metal nanowire, For example, well-known manufacturing methods, such as a liquid phase method and a gaseous-phase method, can be used.

For example, as a manufacturing method of Ag nanowire, Adv. Mater. , 2002, 1
4, 833-837; Chem. Mater. , 2002, 14, 4736-4745, etc., as a method for producing Au nanowires, such as JP 2006-233252A, etc., as a method for producing Cu nanowires, JP 2002-266007 A, etc. For example, Japanese Patent Application Laid-Open No. 2004-149871 can be referred to. In particular, Adv. Mater. And Chem. Mater. The method for producing Ag nanowires reported in 1) can be easily produced in an aqueous system, and the electrical conductivity of silver is the highest among metals, so it is preferably applied as a method for producing silver nanowires. can do.

Metal nanowires come into contact with each other to create a three-dimensional conductive network, exhibiting high conductivity, and allowing light to pass through the conductive network window where no metal nanowire exists, Due to the scattering effect of the metal nanowires, it is possible to efficiently generate power from the organic power generation layer. If a metal nanowire is installed in the 1st electrode at the side close | similar to an organic electric power generation layer part, since this scattering effect can be utilized more effectively, it is more preferable embodiment.

(Optical function layer)
The organic photoelectric conversion element may have various optical functional layers for the purpose of more efficient light reception of sunlight. As the optical functional layer, for example, a light condensing layer such as an antireflection layer or a microlens array, or a light diffusion layer that can scatter light reflected by the cathode and enter the power generation layer again may be provided. .

Various known antireflection layers can be provided as the antireflection layer. For example, when the transparent resin film is a biaxially stretched polyethylene terephthalate film, the refractive index of the easy adhesion layer adjacent to the film is 1.57. It is more preferable to set it to ˜1.63 because the interface reflection between the film substrate and the easy adhesion layer can be reduced and the transmittance can be improved. The method for adjusting the refractive index can be carried out by appropriately adjusting the ratio of the oxide sol having a relatively high refractive index such as tin oxide sol or cerium oxide sol and the binder resin. The easy-adhesion layer may be a single layer, but may be composed of two or more layers in order to improve adhesion.

As the condensing layer, for example, it is processed so as to provide a structure on the microlens array on the sunlight receiving side of the support substrate, or the amount of light received from a specific direction is increased by combining with a so-called condensing sheet. Conversely, the incident angle dependency of sunlight can be reduced.

As an example of the microlens array, quadrangular pyramids having a side of 30 μm and an apex angle of 90 degrees are two-dimensionally arranged on the light extraction side of the substrate. One side is preferably 10 to 100 μm.
If it is smaller than this, the effect of diffraction is generated and colored, and if it is too large, the thickness becomes thick, which is not preferable.

Examples of the light diffusion layer include various antiglare layers, layers in which nanoparticles or nanowires such as metals or various inorganic oxides are dispersed in a colorless and transparent polymer, and the like.

(Film formation method / surface treatment method)
Examples of a method for producing a bulk heterojunction layer in which an electron acceptor and an electron donor are mixed, and a transport layer / electrode include a coating method such as an evaporation method, a cast method, and a spin coating method.

Among these, the coating method is preferable in order to increase the area of the interface where charge and electron separation are performed, and to produce a device having high photoelectric conversion efficiency. Also, the coating method is excellent in production speed.

Although there is no restriction | limiting in the coating method used in this case, For example, a spin coat method, the cast method from a solution, a dip coat method, a blade coat method, a wire bar coat method, a gravure coat method, a spray coat method etc. are mentioned. Furthermore, inkjet method, screen printing method,
Patterning can also be performed by a printing method such as a relief printing method, an intaglio printing method, an offset printing method, or a flexographic printing method.

After coating, heating is preferably performed in order to cause removal of residual solvent, moisture and gas, and increase mobility and absorption longwave by crystallization of the semiconductor material. When heat treatment is performed at a predetermined temperature during the manufacturing process, a part of the particles is microscopically aggregated or crystallized, and the bulk heterojunction layer can have an appropriate phase separation structure. As a result, the carrier mobility of the bulk heterojunction layer is improved and high efficiency can be obtained.

The bulk heterojunction layer may be composed of a single layer in which an electron acceptor and an electron donor are uniformly mixed, or may be composed of a plurality of layers in which the mixing ratio of the electron acceptor and the electron donor is changed. Good. In this case, it can be manufactured by using a material that can be insolubilized after coating as described above.

(Patterning)
There is no particular limitation on the method and process for patterning the electrode, the power generation layer, the hole transport layer, the electron transport layer, and the like, and known methods can be applied as appropriate.

If it is a soluble material such as a bulk heterojunction layer and a transport layer, only unnecessary portions may be wiped after the entire surface application such as die coating and dip coating, or directly at the time of application using a method such as ink jet method or screen printing. Patterning may be performed.

In the case of an insoluble material such as an electrode material, mask evaporation can be performed during vacuum deposition of the electrode, or patterning can be performed by a known method such as etching or lift-off. Alternatively, the pattern may be produced by transferring a pattern produced on another substrate.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the indication of “%” is used in the examples, “% by mass” unless otherwise specified.
".
<< Evaluation 1: Gas barrier film provided with a single gas barrier layer >>
[Example 1-1]
[Preparation of base material (a)]
As a thermoplastic resin substrate (support), a 125 μm-thick polyester film (KDL86W, manufactured by Teijin DuPont Films Ltd.) that was easily bonded on both surfaces was used as the substrate as it was. The surface roughness measured according to the method defined in JIS B 0601 (2001) of the substrate (a) was 4 nm for Ra and 320 nm for Rz.

The surface roughness is AFM (Atomic Force Microscope) SPI3800N DFM manufactured by SII.
It measured using. The measurement range at one time is 80 μm × 80 μm, the measurement location is changed and the measurement is performed three times, and the Ra value obtained by each measurement and the average of the 10-point average roughness Rz are measured. Value.

[Formation of anchor coat layer (AC1)]
Snow Techx (registered trademark; hereinafter omitted for the same description) N (particle diameter: 10 to 20 nm) as a metal compound particle, N (particle diameter: 10 to 20 nm), soap-free acrylic emulsion AE986B manufactured by Etec as an emulsion containing a hydrophobic material ( Particle size 60nm, T
g2 ° C.). As a surfactant, Surfynol (registered trademark; hereinafter, the same description is omitted) 465 manufactured by Air Products Co., Ltd. was used. Metal compound particles / hydrophobic material / surfactant as a solid content are mixed at a mass ratio of 80.0 / 19.8 / 0.2, and further diluted with pure water to obtain a coating liquid having a solid content of 10% by mass. did.

This coating solution was applied onto the substrate so as to give a dry weight of 0.5 g / m ^2, and then 120
The anchor coat layer (AC1) was formed by drying at 2 ° C. for 2 minutes.

[Formation of gas barrier layer]
(Formation of polysilazane layer)
On the anchor coat layer formed as described above, a coating solution containing polysilazane prepared as described below was applied using a spin coater under the condition that the film thickness after drying was 250 nm. The drying conditions were 100 ° C. and 2 minutes.

<Preparation of polysilazane-containing coating solution>
A dibutyl ether solution containing 20% by mass of non-catalytic perhydropolysilazane (manufactured by AZ Electronic Materials Co., Ltd., NN120-20) and N, N, N as an amine catalyst
', N'-tetramethyl-1,6-diaminohexane and perhydropolysilazane 19
Dibutyl ether solution containing mass% (NAX manufactured by AZ Electronic Materials Co., Ltd.)
120-20) at a mass ratio of 4: 1, and 1% by mass relative to the solid content of the coating solution.
Adjusted. Further, a coating solution was prepared by appropriately diluting with dibutyl ether according to the set film thickness.

(Vacuum ultraviolet irradiation treatment)
After forming the polysilazane layer coating film as described above, vacuum gas irradiation treatment was performed according to the following method to form a gas barrier layer. Details of the processing conditions are shown in Table 1.

<Measurement of vacuum ultraviolet irradiation conditions and irradiation energy>
The vacuum ultraviolet irradiation was performed using the apparatus shown in the schematic sectional view of FIG.

In FIG. 2, reference numeral 11 denotes an apparatus chamber, which supplies appropriate amounts of nitrogen and oxygen from a gas supply port (not shown) to the inside and exhausts gas from a gas discharge port (not shown), thereby substantially removing water vapor from the inside of the chamber. The oxygen concentration can be maintained at a predetermined concentration. 12 is 172n
An Xe excimer lamp 13 having a double tube structure for irradiating vacuum ultraviolet rays of m, 13 is an excimer lamp holder that also serves as an external electrode. Reference numeral 14 denotes a sample stage. The sample stage 14 can be reciprocated horizontally at a predetermined speed in the apparatus chamber 11 by a moving means (not shown). The sample stage 14 can be maintained at a predetermined temperature by a heating means (not shown). Reference numeral 15 denotes a sample on which a polysilazane coating layer is formed. Sample stage 14
As the sample moves horizontally, the height of the sample stage 14 is adjusted so that the shortest distance between the surface of the coating layer of the sample and the excimer lamp tube surface is 3 mm. Reference numeral 16 denotes a light shielding plate, which prevents the vacuum ultraviolet light from being applied to the coating layer of the sample during the aging of the Xe excimer lamp 12.

The energy applied to the surface of the sample coating layer in the vacuum ultraviolet irradiation step is an ultraviolet integrated light meter manufactured by Hamamatsu Photonics: C8026 / H8025 UV POWER METER.
Measurements were made using a 172 nm sensor head. In the measurement, the sensor head is installed in the center of the sample stage 4 so that the shortest distance between the Xe excimer lamp tube surface and the measurement surface of the sensor head is 3 mm, and the atmosphere in the apparatus chamber 11 is irradiated with vacuum ultraviolet rays. Nitrogen and oxygen were supplied so that the oxygen concentration was the same as in the process, and the sample stage 4 was moved at a speed of 0.5 m / min for measurement. Prior to the measurement, in order to stabilize the illuminance of the Xe excimer lamp 2, an aging time of 10 minutes was provided after the Xe excimer lamp 12 was turned on, and then the sample stage was moved to start the measurement.

Based on the irradiation energy obtained by this measurement, the irradiation energy shown in Table 1 was adjusted by adjusting the moving speed of the sample stage 14. The vacuum ultraviolet irradiation was performed after aging for 10 minutes as in the case of irradiation energy measurement.

  As described above, a gas barrier film was produced.

[Example 1-2]
The above examples except that the type of metal compound particles contained in the anchor coat layer was changed to form an anchor coat layer (AC2) as a Snowtex PS-M (particle diameter 80-120 nm) of Nissan Chemical Industries, Ltd. A gas barrier film was produced in the same manner as in 1-1.

[Example 1-3]
Except for changing the mass ratio of metal compound particles / hydrophobic material / surfactant contained in the anchor coat layer to form an anchor coat layer (AC3) of 70.0 / 29.8 / 0.2, A gas barrier film was produced in the same manner as in Example 1-2.

[Example 1-4]
Except that each component included in the anchor coat layer, and the mass ratio of each component was changed,
A gas barrier film was produced in the same manner as in Example 1-1. Anchor coat layer (A
The components and component ratios contained in C4) are as follows.

IPA-S from Nissan Chemical Industries, which is hydrophilic metal compound particles as metal compound particles
T (isopropanol dispersion, particle size 10 to 20 nm) was used, and the compound represented by the chemical formula S1 was used as hydrophobic metal compound particles. Hydrophilic metal compound particles / hydrophobic metal compound particles were mixed as a solid content at a mass ratio of 80.0 / 20.0, and further diluted with isopropanol to obtain a coating solution having a solid content of 10% by mass.

[Example 1-5]
A gas barrier film was produced in the same manner as in Example 1-1 except that each component contained in the anchor coat layer, the mass ratio of each component, and the method for forming the anchor coat layer were changed. The components contained in the anchor coat layer (AC5) and the method for forming the anchor coat layer (AC5) are as follows.

IPA-S from Nissan Chemical Industries, which is hydrophilic metal compound particles as metal compound particles
T (isopropanol dispersion, particle diameter 10 to 20 nm) was used, and the compound represented by the chemical formula S2 was used as hydrophobic metal compound particles.

First, a solution containing only hydrophilic metal compound particles was applied on a base material so that the dry weight was 0.5 g / m ^2, and then dried at 120 ° C. for 2 minutes.

Next, for the purpose of imparting hydrophobicity to the anchor coat layer, a solution obtained by diluting methyl hydrogen silicone oil KF-9901 manufactured by Shin-Etsu Silicone Co., Ltd. with methyl ethyl ketone is added to the layer of only the metal compound particles in an amount of 0. Apply to 03 g / m ² , then 1
An anchor coat layer (AC5) was formed by drying at 20 ° C. for 2 minutes. That is, the anchor coat layer (AC5) was formed so that the mass ratio of hydrophilic metal compound particles / hydrophobic metal compound particles was 94.3 / 5.7 as a solid content.

[Example 1-6]
A gas barrier film was produced in the same manner as in Example 1-1 except that only the hydrophobic metal compound particles were used as the metal compound particles contained in the anchor coat layer and no hydrophobic material was added. . The components contained in the anchor coat layer (AC6) and the method for forming the anchor coat layer (AC6) are as follows.

SP-1120 (MEK) manufactured by Konishi Chemical Co., Ltd. (particle diameter 20) as hydrophobic metal compound particles
nm). This was diluted with methyl isobutyl ketone to a solid content of 5% by mass to obtain a coating solution. This coating solution was applied onto the substrate so as to give a dry weight of 0.2 g / m ^2.
The anchor coat layer (AC6) was formed by drying at 0 degree for 2 minutes. That is, the anchor coat layer was formed so that the hydrophobic metal compound particles were 100% by mass as the solid content.

[Example 1-7]
As the hydrophobic metal compound particles contained in the anchor coat layer, the compound represented by the chemical formula S19 (particle diameter: 1 to 3 nm) was used. When forming the anchor coat layer (AC7), methyl ethyl ketone / methyl isobutyl ketone = 50 / A gas barrier film was produced in the same manner as in Example 1-6 above, except that a coating solution prepared by dissolving so as to have a solid content of 5% by mass with 50 mixed solvents was used.

[Example 1-8]
A gas barrier film was produced in the same manner as the gas barrier film of Example 1-6 except that the base material was changed to the base material (A) shown below.

[Production of substrate (I)]
As a thermoplastic resin substrate (support), a 125 μm thick polyester film (manufactured by Teijin DuPont Films Co., Ltd., extremely low heat yield PET Q83) that is easily bonded on both sides is used.
As shown below, a substrate (I) was prepared by forming a bleed-out preventing layer on one side and a smooth layer on the opposite side.

<Formation of bleed-out prevention layer>
On one side of the thermoplastic resin substrate, UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark; hereinafter, the same description is omitted) manufactured by JSR Corporation
After applying Z7535 under the condition that the film thickness after drying is 4.0 μm, the curing condition is an irradiation energy of 1.0 J / cm ² , using a high-pressure mercury lamp in an air atmosphere, and a drying condition of 80 ° C. Then, a curing process for 3 minutes was performed to form a bleed-out prevention layer.

<Formation of smooth layer>
Next, a UV curable organic / inorganic hybrid hard coat material OPSTA manufactured by JSR Corporation is formed on the surface of the thermoplastic resin substrate opposite to the surface on which the bleed-out prevention layer is formed.
RZ7501 was applied under the condition that the film thickness after drying was 4.0 μm, and then dried at 80 ° C. for 3 minutes. Then, using a high pressure mercury lamp in an air atmosphere, the curing condition was as follows: Irradiated and cured at 0.0 J / cm ² to form a smooth layer.

As a result of measuring according to the method prescribed | regulated by JISB0601 (2001) of the obtained smooth layer, surface roughness Ra was about 1 nm. Rz was 20 nm. In addition, the measurement of surface roughness was performed by the method similar to having used for preparation of the said base material (a). The coated surface of the anchor coat layer was a smooth layer surface.

[Example 1-9]
A gas barrier film was produced in the same manner as the gas barrier film of Example 1-4, except that the substrate was changed to the substrate (c) shown below.

[Production of substrate (c)]
As a heat-resistant substrate, a 200 μm thick transparent polyimide film (manufactured by Mitsubishi Gas Chemical Co., Ltd., Neoprim L) with easy-adhesion processing on both sides is used. As shown below, a smooth layer is formed on both sides of the substrate. What was formed was made into the base material (c).

(Formation of smooth layer)
<Preparation of smooth layer coating solution>
Trimethylolpropane triglycidyl ether (Epolite (registered trademark) 100MF)
8.0 g of Kyoeisha Chemical Co., Ltd.), 5.0 g of ethylene glycol diglycidyl ether (Epolite (registered trademark) 40E Kyoeisha Chemical Co., Ltd.), silsesquioxane having an oxetanyl group: OX-SQ-H (Toagosei Co., Ltd.) 12.0 g, 3-glycidoxypropyltrimethoxysilane 32.5 g, Al (III) acetylacetonate 2.2 g, methanol silica sol (manufactured by Nissan Chemical Co., Ltd., solid content concentration 30 mass%) 134 .0g, BYK33
3 (manufactured by Big Chemie Japan Co., Ltd., silicon surfactant), 125.0 g of butyl cellosolve, and 15.0 g of 0.1 mol / L hydrochloric acid aqueous solution were mixed and sufficiently stirred.
This was further left standing and deaerated at room temperature to obtain a smooth layer coating solution.

<Formation of smooth layer 1>
After applying a corona discharge treatment to one surface side of the heat-resistant substrate by a conventional method, the smooth layer coating solution is applied under the condition that the film thickness after drying is 4.0 μm, and then 3 ° C. at 80 ° C. Dried for minutes.
Furthermore, the heat processing for 10 minutes were performed at 120 degreeC, and the smooth layer 1 was formed.

<Formation of smooth layer 2>
A smooth layer 2 was formed on the surface of the heat resistant substrate opposite to the surface on which the smooth layer 1 was formed in the same manner as the method for forming the smooth layer 1.

The surface roughness of the formed smooth layer 1 and smooth layer 2 is measured according to JIS B 0601 (2001).
As a result of measurement in accordance with the method defined in (2), Ra was 2 nm and Rz was 25 nm. In addition, the measurement of surface roughness was performed by the method similar to having used for preparation of the said base material (a). The coated surface of the anchor coat layer was the surface of the smooth layer 1.

[Example 1-10]
A gas barrier film was produced in the same manner as the gas barrier film of Example 1-6 except that the base material was changed to the base material (D) shown below.

[Production of substrate (d)]
In the production of the base material (c), easy-adhesion processing was performed on both surfaces which are heat-resistant base materials 200
Instead of a transparent polyimide film having a thickness of μm (manufactured by Mitsubishi Gas Chemical Co., Ltd., Neoprim L), a film having a basic skeleton of silsesquioxane having an organic-inorganic hybrid structure as a heat-resistant substrate, having a thickness of 100 μm Silplus (registered trademark) H1 manufactured by Nippon Steel Chemical Co., Ltd.
A substrate (D) was prepared in the same manner except that 00 was used. In addition, as a result of measuring the surface roughness of the smooth layer 1 and the smooth layer 2 of the base material (d) in accordance with a method defined in JIS B 0601 (2001), Ra was 1 nm and Rz was 20 nm. It was. In addition, the measurement of surface roughness was performed by the method similar to having used for preparation of the said base material (a). The coated surface of the anchor coat layer was the surface of the smooth layer 1.

[Comparative Example 1-1]
A gas barrier film was produced in the same manner as the gas barrier film of Example 1-8 except that the anchor coat layer was not formed.

[Comparative Example 1-2]
A gas barrier film was produced in the same manner as the gas barrier film of Example 1-1 except that the anchor coat layer was not formed.

[Comparative Example 1-3]
The gas barrier film was formed in the same manner as the gas barrier film of Example 1-1, except that the anchor coat layer was not formed and the integrated irradiation energy was changed to 4500 mJ / cm ² as the VUV light irradiation condition of the gas barrier layer. Was made.

[Comparative Example 1-4]
A gas barrier film was produced by forming an anchor coat layer (AC8) in the same manner as in Example 1-5 except that the anchor coat layer did not contain the exemplified compound S2 as a hydrophobic material.

[Comparative Example 1-5]
A gas barrier film was produced in the same manner as in Example 1-1 except that each component contained in the anchor coat layer, the mass ratio of each component, and the method for forming the anchor coat layer were changed. The components contained in the anchor coat layer (AC9) and the method for forming the anchor coat layer (AC9) are as follows.

Snowtex O (particle diameter 10-20 nm) of Nissan Chemical Industries as metal compound particles
As a water-soluble binder, Poval (registered trademark) R-1130 manufactured by Kuraray Co., Ltd. was used. As a surfactant, Surfynol 465 manufactured by Air Products was used. Metal compound particles / water-soluble binder / surfactant as a solid content is mixed at a mass ratio of 60.0 / 39.8 / 0.2, and further diluted with pure water to obtain a coating liquid having a solid content of 10% by mass. did.

This coating solution was applied onto the substrate so as to give a dry weight of 0.5 g / m ^2, and then 120
The anchor coat layer (AC9) was formed by drying at 2 ° C. for 2 minutes.

[Comparative Example 1-6]
A gas barrier film was produced in the same manner as in Example 1-1 except that the metal compound particles contained in the anchor coat layer and the mass ratio of each component were changed. The components and component ratios contained in the anchor coat layer (AC10) are as follows.

As the metal compound particles, Snowtex NXS (particle diameter: 5 nm) of Nissan Chemical Industries, which is a hydrophilic metal compound particle, is used. Further, hydrophilic metal compound particles / hydrophobic material /
The surfactant was mixed as a solid content at a mass ratio of 50.0 / 49.8 / 0.2, and further diluted with pure water to obtain a coating solution having a solid content of 10% by mass.

This coating solution was applied onto the substrate so as to give a dry weight of 0.5 g / m ^2, and then 120
The anchor coat layer (AC10) was formed by drying at 2 ° C. for 2 minutes.

[Comparative Example 1-7]
Except that the mass ratio of hydrophilic metal compound particles / hydrophobic metal compound particles contained in the anchor coat layer was changed to form 99.95 / 0.05 anchor coat layer (AC11). A gas barrier film was produced in the same manner as in Example 1-4.

[Comparative Example 1-8]
The type of metal compound particles contained in the anchor coat layer was changed, and MP-
A gas barrier film was produced in the same manner as in Example 1-1 except that the anchor coat layer (AC12) having a particle size of 4540M (particle diameter 450 nm) was formed.

<Evaluation of water vapor barrier properties>
(Water vapor barrier property evaluation sample preparation device)
Vapor deposition apparatus: Vacuum vapor deposition apparatus JEE-400 manufactured by JEOL
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
(raw materials)
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)
(Preparation of water vapor barrier property evaluation sample)
Examples 1-1 to 1-1 using a vacuum deposition apparatus (vacuum deposition apparatus JEE-400 manufactured by JEOL Ltd.)
Metal calcium was vapor-deposited with a size of 12 mm × 12 mm through a mask on the surface of the gas barrier layer of the gas barrier film produced in −10 and Comparative Examples 1-1 to 1-8.

Thereafter, the mask was removed in a vacuum state, and aluminum was vapor-deposited on the entire surface of one side of the sheet to perform temporary sealing. Next, release the vacuum state, quickly move to a dry nitrogen gas atmosphere,
Thickness 0 on the aluminum deposition surface via UV curable resin for sealing (manufactured by Nagase ChemteX)
. A water vapor barrier property evaluation sample was prepared by pasting together 2 mm quartz glass, irradiating ultraviolet rays to cure and bond the resin, and finally sealing.

(Evaluation method)
The obtained sample was stored at a high temperature and high humidity of 60 ° C. and 90% RH, and the state in which metallic calcium was corroded with respect to the storage time was observed. Observation was performed every 5 hours, and the area where metal calcium corroded relative to the metal calcium vapor deposition area of 12 mm × 12 mm was calculated in%. Table 1 shows the time when the corrosion area of metal calcium exceeds 20% as an index of the time when the progress of corrosion started, that is, when the peeling between the gas barrier layer and the layer immediately below it became significant.

As shown in Table 1, the gas barrier films of the present invention (Examples 1-1 to 1-10)
While the time when the corroded area of metal calcium exceeded 20% was as long as 90 hours or longer, the gas barrier films of Comparative Examples (Comparative Examples 1-1 to 1-8) had a result of being shorter than 35 hours. It was. Therefore, it can be seen that the gas barrier film of the present invention can maintain a very high barrier property for a long time and has good durability.

In particular, in the gas barrier films of Examples 1-6, 1-8, and 1-10, the time until the area where metallic calcium was corroded exceeded 20% was 150 hours. Therefore, at least in the Examples, it was shown that the gas barrier film provided with the anchor coat layer AC6 (anchor coat layer made only of hydrophobic metal compound particles) has particularly good durability.

<< Evaluation of heat resistance of gas barrier film >>
About the gas barrier films of Examples 1-9 and 1-10 produced above, 220 ° C.
For 10 minutes in an air atmosphere. At this time, the member was held so as not to contact the surface of the gas barrier layer of the gas barrier film. After the heat treatment, it was taken out into the air at room temperature and cooled to room temperature as it was. Subsequently, the water vapor barrier property evaluation was performed in the same manner as the evaluation of the water vapor barrier property in Evaluation 1 above. The result was the same as in the case of no heat treatment and was good. Thus, it can be seen that the gas barrier film of the present invention is excellent in heat resistance and maintains a very high barrier property over a long period of time and has good durability.

<< Evaluation 2: Gas barrier film provided with two-layer gas barrier layer >>
<< Production of gas barrier film >>
According to the base material, anchor coat layer, film thickness, and vacuum ultraviolet irradiation treatment conditions shown in Table 2, a laminated gas barrier layer having a two-layer structure was formed. Examples 2-1 to 2-4 and Comparative Example 2 shown below −
A gas barrier film of 1-2-3 was prepared. These gas barrier films were formed in the above Examples 1-2 to 1-4 and 1-6, and Comparative Examples 1-2, 1-4, and 1- 1 except that two gas barrier layers were continuously formed. 5 was produced in the same procedure as the gas barrier film shown in FIG. The numbers (types) of the gas barrier layers described in Table 2 are the numbers described in Table 1 (
The anchor coat layer having the same number and the same number indicates that it was formed by the same configuration and formation method.

<< Production of organic thin film electronic devices >>
Using the gas barrier films of Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-3 as sealing films, organic EL elements (Examples) that are organic thin film electronic devices as shown in FIG. 3-1 to 3-4 and Comparative Examples 3-1 to 3-3) were produced. The gas barrier film used is shown in Table 3.

[Production of organic EL elements]
(Formation of the first electrode layer 22)
On the gas barrier layer 4 of each gas barrier film 21, ITO (indium tin oxide) having a thickness of 150 nm was formed by sputtering, and patterned by photolithography to form the first electrode layer 22. The pattern was such that the light emission area was 50 mm square.

(Formation of hole transport layer 23)
On the first electrode layer 22 of each gas barrier film 21 on which the first electrode layer 22 is formed, the following hole transport layer forming coating solution is extrusion coated in an environment of 25 ° C. and 50% relative humidity. After coating with a machine, drying and heat treatment were performed under the following conditions to form the hole transport layer 23. The coating liquid for forming the hole transport layer was applied so that the thickness after drying was 50 nm.

Before applying the coating solution for forming the hole transport layer, the cleaning surface modification treatment of the barrier film is performed using a low pressure mercury lamp with a wavelength of 184.9 nm, an irradiation intensity of 15 mW / cm ² , and a distance of 10 mm.
It carried out in. The charge removal treatment was performed using a static eliminator with weak X-rays.

<Application conditions>
The application process is in the atmosphere.
<Preparation of hole transport layer forming coating solution>
Polyethylene dioxythiophene / polystyrene sulfonate (PEDOT / PSS,
Bytron P AI 4083 (Bayer) 65% with pure water, 5% methanol
The solution diluted with was prepared as a coating solution for forming a hole transport layer.

<Drying and heat treatment conditions>
After applying the hole transport layer forming coating solution, the height is 100 mm toward the film forming surface, and the discharge air velocity is 1 m / min.
After removing the solvent at s, a wide wind velocity distribution of 5% and a temperature of 100 ° C., a back surface heat transfer system heat treatment was subsequently performed at a temperature of 150 ° C. using a heat treatment apparatus to form the hole transport layer 23.

(Formation of the light emitting layer 24)
On the hole transport layer 23 formed as described above, the following coating solution for forming a white light-emitting layer is applied by an extrusion coater under the following conditions, followed by drying and heat treatment under the following conditions to obtain the light-emitting layer 2
4 was formed. The white light emitting layer forming coating solution was applied so that the thickness after drying was 40 nm.

<White luminescent layer forming coating solution>
As a host material, 1.0 g of a compound represented by the following chemical formula HA, 100 mg of a compound represented by the following chemical formula DA as a dopant material, and 0.1 mg of a compound represented by the following chemical formula DB as a dopant material. 2 mg of a compound represented by the following chemical formula DC as a dopant material was dissolved in 0.2 mg and 100 g of toluene to prepare a white light emitting layer forming coating solution.

<Application conditions>
The coating process is performed in an atmosphere with a nitrogen gas concentration of 99% or more, the coating temperature is 25 ° C., and the coating speed is 1 m.
/ Min.

<Drying and heat treatment conditions>
After applying the white light emitting layer forming coating solution, the height is 100 mm toward the film-forming surface, and the discharge wind speed is 1 m /
After removing the solvent at s, a wide wind velocity distribution of 5% and a temperature of 60 ° C., a heat treatment was subsequently performed at a temperature of 130 ° C. to form the light emitting layer 24.

(Formation of the electron transport layer 25)
On the light emitting layer 24 formed above, the following electron transport layer forming coating solution is applied by an extrusion coater under the following conditions, and then dried and heat-treated under the following conditions to form the electron transport layer 25: did. The coating solution for forming an electron transport layer was applied so that the thickness after drying was 30 nm.

<Application conditions>
The coating process was performed in an atmosphere having a nitrogen gas concentration of 99% or more, the coating temperature of the electron transport layer forming coating solution was 25 ° C., and the coating speed was 1 m / min.

<Coating liquid for electron transport layer formation>
For the electron transport layer, a compound represented by the following chemical formula EA is converted to 2,2,3,3-tetrafluoro-
It melt | dissolved in 1-propanol and it was set as the 0.5 mass% solution, and was set as the coating liquid for electron carrying layer formation.

<Drying and heat treatment conditions>
After applying the electron transport layer forming coating solution, the height is 100 mm toward the film forming surface, and the discharge wind speed is 1 m /
After removing the solvent at s, a wide wind velocity distribution of 5%, and a temperature of 60 ° C., the electron transport layer 25 was formed by subsequently performing heat treatment at a temperature of 200 ° C. in the heat treatment section.

(Formation of electron injection layer 26)
An electron injection layer 26 was formed on the electron transport layer 25 formed as described above. First, the substrate was put into a vacuum chamber and the pressure was reduced to 5 × 10 ⁻⁴ Pa. In advance, cesium fluoride prepared in a tantalum vapor deposition boat was heated in a vacuum chamber to form an electron injection layer having a thickness of 3 nm.

(Formation of the second electrode 27)
Aluminum is used as the second electrode forming material on the electron injection layer 26 formed as described above, except for the portion that becomes the extraction electrode of the first electrode 22 under a vacuum of 5 × 10 ⁻⁴ Pa. Then, a mask pattern was formed by vapor deposition so as to have an extraction electrode so that the light emission area was 50 mm square, and a second electrode 27 having a thickness of 100 nm was laminated.

(Cutting)
As described above, each laminate in which the second electrode 27 is formed is moved again to the nitrogen atmosphere,
The organic EL element was produced by cutting into a specified size using an ultraviolet laser.

(Electrode lead connection)
An anisotropic conductive film DP3232S9 manufactured by Sony Chemical & Information Device Co., Ltd. was used for the produced organic EL element, and a flexible printed circuit board (base film: polyimide 12.5 μm, rolled copper foil 18 μm, coverlay: polyimide 12.5 μm).
m, surface-treated NiAu plating).

Crimping conditions: temperature 170 ° C. (ACF temperature 140 ° C. measured using a separate thermocouple), pressure 2
Pressure bonding was performed in MPa for 10 seconds.

(Sealing)
As the sealing member 29, a 30 μm thick aluminum foil (manufactured by Toyo Aluminum Co., Ltd.) and a polyethylene terephthalate (PET) film (12 μm thick) using a dry lamination adhesive (two-component reaction type urethane adhesive) are used. Laminated (adhesive layer thickness 1.5 μm) was prepared.

A thermosetting adhesive was uniformly applied to the aluminum surface of the prepared sealing member 29 with a thickness of 20 μm along the adhesive surface (glossy surface) of the aluminum foil using a dispenser to form an adhesive layer 28.

  At this time, an epoxy adhesive containing the following components was used as the thermosetting adhesive.

Bisphenol A diglycidyl ether (DGEBA), dicyandiamide (DICY)
), Epoxy adduct type curing accelerator.

The sealing member 29 is closely attached and arranged so as to cover the joint between the take-out electrode and the electrode lead, and pressure bonding conditions using a pressure roll, pressure roll temperature 120 ° C., pressure 0.5 MPa, apparatus speed 0.3 m / Sealed tightly with min.

<< Evaluation of organic EL elements >>
The produced organic EL elements (Examples 3-1 to 3-4 and Comparative Examples 3-1 to 3-3)
The durability was evaluated according to the following method.

[Evaluation of durability]
(Accelerated deterioration processing)
Each of the produced organic EL elements was subjected to an accelerated deterioration treatment for 400 hours in an environment of 60 ° C. and 90% RH, and then evaluated for the following black spots together with the organic EL elements not subjected to the accelerated deterioration treatment. .

(Evaluation of sunspots)
A current of 1 mA / cm ² was applied to the organic EL element subjected to the accelerated deterioration treatment and the organic EL element not subjected to the accelerated deterioration treatment to emit light continuously for 24 hours. Moritex MS-804, lens MP-ZE25-20
In 0), a part of the panel was enlarged and photographed. The photographed image was cut out in a 2 mm square, the black spot generation area ratio was determined, the element deterioration resistance rate was calculated according to the following formula, and the durability was evaluated according to the following criteria. If the evaluation rank was ◎ or ◯, it was determined that the characteristic was practically preferable.

Element deterioration tolerance rate = (area of black spots generated in elements not subjected to accelerated deterioration processing / area of black spots generated in elements subjected to accelerated deterioration processing) × 100 (%)
A: The element deterioration resistance rate is 90% or more. B: The element deterioration resistance ratio is 60% or more and less than 90%. Δ: The element deterioration resistance ratio is 20% or more and less than 60%. The deterioration resistance ratio is less than 20%. Table 3 shows the results obtained as described above.

As is apparent from the results shown in Table 3, the elements of Examples 3-1 to 3-4 provided with the gas barrier film of the present invention have an element deterioration resistance ratio of 90% or more, and have good durability. I have. On the other hand, Comparative Examples 3-1 to 3-3 provided with the gas barrier films of Comparative Examples 2-1 to 2-3.
The element had an element deterioration resistance rate of less than 60%.

Therefore, it turns out that the gas-barrier film of Examples 2-1 to 2-4 of this invention has very high gas-barrier property of the grade which can be used as a sealing film of an organic EL element.

1 Base material (support)
2 Anchor coat layer 3 Bleed-out prevention layer 4 Gas barrier layer 11 Apparatus chamber 12 Xe excimer lamp 13 Excimer lamp holder 14 Sample stage 15 Sample 16 with polysilazane coating layer formed Light shielding plate 21 Gas barrier film 22 First electrode layer 23 Positive Hole transport layer 24 Light emitting layer 25 Electron transport layer 26 Electron injection layer 27 Second electrode layer 28 Adhesive layer 29 Sealing member

Claims (11)

A substrate;
A gas barrier layer comprising silicon oxynitride ;
Metal compound particles (A) 65 to 100% by mass, hydrophobic material (B) 0 to 35% by mass (provided between the base material and the gas barrier layer and having a particle diameter of 1 to 200 nm) (A) + (B) = 100% by mass), and an anchor coat layer having hydrophobicity,
A gas barrier film comprising: The gas barrier film according to claim 1, wherein the gas barrier layer is formed by modifying at least part of polysilazane to silicon oxynitride. The gas barrier film according to claim 1, wherein an intermediate layer is further formed between the base material and the anchor coat layer. The gas barrier film according to claim 3, wherein the intermediate layer is a smooth layer. The gas barrier film according to claim 4, wherein the smooth layer has a thickness of 1 to 10 μm. The gas barrier film according to any one of claims 1 to 5 , wherein the metal compound particles are colloidal silica particles. The gas barrier film according to claim 6 , wherein the colloidal silica particles have a chain shape or a bead shape. The gas barrier film according to any one of claims 1 to 5, wherein the metal compound particles are polyorganosiloxane particles or polyorganosilsesquioxane particles. The display material using the gas-barrier film of any one of Claims 1-8. The electronic device using the gas barrier film of any one of Claims 1-8 . The organic electroluminescent element using the gas-barrier film of any one of Claims 1-8.