JP2016087951A - Gas barrier film, production method for gas barrier film, and electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a gas barrier film that has a very high gas barrier property which makes it possible to be used as a substrate for an electronic device such as an organic EL element, and that generates, when used as a substrate for an organic EL device, less dark spots, and that produces a uniform light emission; a production method for gas barrier film; and also an electronic device that has a uniform light emission characteristic.SOLUTION: Provided is a gas barrier film including a resin substrate, and one or more layer of gas barrier layer provided on one surface of the resin substrate, and in which, characterized, at least one layer of the gas barrier layer is a layer formed by applying an energy to a polysilazane-containing layer, as well as in which the surface specific resistance of the other surface of the resin substrate is in a range of 1×10to 5×10Ω/sq..SELECTED DRAWING: Figure 1

Description

  The present invention relates to a gas barrier film, a method for producing a gas barrier film, and an electronic device, and particularly relates to a gas barrier film having one or more gas barrier layers on one surface of a resin substrate.

  Conventionally, a gas barrier film in which a metal oxide thin film such as aluminum oxide, magnesium oxide or silicon oxide is formed on the surface of a plastic substrate or film is used to wrap articles and foods that require blocking of various gases such as water vapor and oxygen. It is widely used for packaging and the like to prevent alteration of industrial products and pharmaceuticals. In addition to packaging applications, they are used in liquid crystal display elements, solar cells, organic electroluminescence (hereinafter abbreviated as organic EL) elements, and the like. In particular, liquid crystal display elements, organic EL elements, and the like are required to have high gas barrier properties (gas barrier properties) because internal penetration of water vapor or air causes deterioration in quality.

  The demand for such a high gas barrier property such as water vapor and air has become more severe in recent years, and a gas barrier film used for a substrate of an organic EL device is required to have a very high gas barrier property. Yes. In particular, it is required to reduce as much as possible a so-called barrier defect region having a low local gas barrier property that causes dark spots.

In recent years, as a new gas barrier film forming method capable of reducing barrier defects, silicon oxide such as polysilazane is applied on a substrate, and the applied polysilazane coating film is irradiated with vacuum ultraviolet light to thereby form silicon oxide. A method for producing a film has been proposed (see, for example, Patent Documents 1 to 5).
This method uses light energy in the range of 100 to 200 nm called vacuum ultraviolet light (hereinafter also referred to as “VUV” or “VUV light”), which is larger than the interatomic bonding force in the silazane compound. Thus, the silicon oxide film can be produced at a relatively low temperature by causing the oxidation reaction with active oxygen or ozone to proceed while directly cutting the atomic bond by the action of only photons called a photon process.
Studies are underway to reduce dark spots by using the gas barrier film thus produced as a substrate for organic EL devices.
However, on the other hand, it has been found that the organic EL device using the gas barrier film has a new problem that uneven light emission occurs.

Special table 2009-503157 JP 2009-255040 A JP 2012-148416 A JP2013-255910A International Publication No. 2013/002026

  The present invention has been made in view of the above-described problems and circumstances, and a solution to the problem is that it has a very high gas barrier property that can be used as a substrate of an electronic device such as an organic EL element, and an organic EL. When used as a substrate of a device, it is to provide a gas barrier film and a gas barrier film manufacturing method capable of obtaining uniform light emission with less generation of dark spots. Moreover, it is providing the electronic device which has a uniform light emission characteristic.

The inventor infers the cause of the occurrence of uneven light emission of the electronic device as follows.
For example, as in Patent Document 4 above, a polysilazane compound is applied to a sheet-like film sample on which a coating film is formed, placed on a sample stage in an apparatus chamber, and irradiated with an excimer lamp of a VUV light source. In the method of converting a compound into a silicon oxide film, a metal plate such as SUS is used for the sample stage in the apparatus chamber. Therefore, when the sample is removed from the sample stage after the conversion process, the sample may be stuck due to charging. As a result, uneven distribution of static electricity is formed in the obtained gas barrier film.
On the other hand, as described in Patent Document 5, a method for producing a so-called roll-to-roll process, which is said to be capable of industrial continuous production of a gas barrier film, is performed by applying a polysilazane compound to a roll-shaped substrate fed from a roller. After coating and forming a coating film, the substrate and coating film are conveyed by a roller to dry the coating film, and then irradiated with an excimer lamp of a VUV light source while being conveyed, the polysilazane compound is converted into a silicon oxide film. It is a method to convert into. In this case, in order to maintain a constant distance between the excimer lamp tube surface and the roll-shaped substrate film surface, a support roller is disposed immediately below each excimer lamp. And since the holding angle between the roll-shaped substrate film on which the coating film is formed and the support roller is very small, the rotation of the support roller due to the contact with the roll-shaped substrate film being conveyed is not sufficient, and not a little Rubbing occurs, and uneven distribution of static electricity is formed in the gas barrier film obtained thereby.
When an electronic device is manufactured by using the gas barrier film with the uneven distribution of static electricity as a substrate in this way, when the constituent layers of the electronic device are formed by vapor deposition under vacuum, the traveling path of the vapor deposition vapor is unified by static electricity. The portion is bent to form uneven coating of the layer. And it is guessed that the unevenness of the amount of this layer appears as unevenness of light emission.

As described above, in order to solve the above problems, the present inventor, in the process of examining the cause of the above problems, the surface specific resistance of the surface of the resin substrate opposite to the gas barrier layer is within a specific range. By defining, it was found that uneven distribution of static electricity can be suppressed, and as a result, it has high gas barrier properties, little dark spots are generated, and uniform light emission can be obtained, and the present invention has been achieved.
That is, the said subject which concerns on this invention is solved by the following means.
1. A gas barrier film having one or more gas barrier layers on one surface of a resin substrate,
At least one of the gas barrier layers is a layer formed by applying energy to a layer containing polysilazane, and
A gas barrier film characterized in that the surface specific resistance of the other surface of the resin substrate is in the range of 1 × 10 ^{7 to} 5 × 10 ¹² Ω / □.

  2. The surface roughness Ra of the other surface of the resin base material is in the range of 1.0 to 3.0 nm, and the surface roughness Rz is in the range of 10 to 30 nm. The gas barrier film according to item 1.

3. A method for producing a gas barrier film according to item 1 or 2, wherein the gas barrier film is produced.
The method for producing a gas barrier film, wherein the application of energy is application of light energy by irradiation with vacuum ultraviolet rays.

  4). 4. The method for producing a gas barrier film according to item 3, wherein the irradiation with the vacuum ultraviolet rays is performed in a nitrogen atmosphere.

  5. An electronic device comprising the gas barrier film according to item 1 or 2.

  6). 6. The electronic device according to item 5, wherein at least one of the layers constituting the electronic device is a layer formed by a vapor deposition method in a vacuum.

By the above-mentioned means of the present invention, it has a very high gas barrier property that can be used as a substrate of an electronic device such as an organic EL element, and when used as a substrate of an organic EL device, the occurrence of dark spots is small. And the manufacturing method of the gas barrier film which can obtain uniform light emission, and a gas barrier film can be provided. In addition, an electronic device having uniform light emission characteristics can be provided.
The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.
The uneven distribution of static electricity in the gas barrier film, which is considered to be a cause of uneven emission of electronic devices, is the surface on the side where the gas barrier layer of the resin substrate is not formed when energy is applied to the polysilazane-containing layer of the gas barrier film. However, it is considered that the gas barrier film is charged and formed by contacting / separating with a member forming the reformer.
Therefore, in the present invention, as described above, the surface specific resistance of the other surface of the resin base material on which the gas barrier layer is not formed is in the range of 1 × 10 ^{7 to} 5 × 10 ¹² Ω / □. Thus, it is presumed that the uneven distribution of static electricity of the gas barrier film generated when applying energy to the polysilazane-containing layer is suppressed, and the uneven light emission of the electronic device can be improved.

Schematic which shows one Embodiment of the vacuum ultraviolet irradiation apparatus for manufacturing the gas barrier film of this invention Schematic which shows one Embodiment of the manufacturing apparatus for manufacturing the gas barrier film of this invention. Schematic which shows one Embodiment of the film-forming apparatus for manufacturing the gas barrier film of this invention Schematic which shows one Embodiment of the film-forming apparatus for manufacturing the gas barrier film of this invention

The gas barrier film of the present invention is a gas barrier film having one or more gas barrier layers on one surface of a resin base material, wherein at least one of the gas barrier layers has energy in a layer containing polysilazane. The surface specific resistance of the other surface of the resin base material is in the range of 1 × 10 ^{7 to} 5 × 10 ¹² Ω / □. . This feature is a technical feature common to the inventions according to claims 1 to 6.
As an embodiment of the present invention, from the viewpoint of manifesting the effect of the present invention, the surface roughness Ra of the other surface of the resin substrate is in the range of 1.0 to 3.0 m, and the surface roughness When Rz is in the range of 10 to 30 nm, the uneven distribution of static electricity of the gas barrier film can be further reduced, and as a result, the uneven light emission of the electronic device can be further improved.

The method for producing a gas barrier film according to the present invention is characterized in that the application of energy is application of light energy by irradiation with vacuum ultraviolet rays. Thereby, a gas barrier film with reduced barrier defects can be obtained.
Further, when the irradiation with the vacuum ultraviolet ray is performed in a nitrogen atmosphere, it is possible to obtain a gas barrier film that is difficult to be charged and in which uneven distribution of static electricity is further reduced.

The gas barrier film according to the present invention is suitably used for electronic devices.
Moreover, it is preferable that at least one layer constituting the electronic device is a layer formed by a vapor deposition method in a vacuum. When forming by vacuum deposition in a vacuum, if there is uneven distribution of static electricity in the gas barrier film, the effect of uneven light emission is likely to occur, so it is effective to use the gas barrier film according to the present invention.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

[Gas barrier film]
The gas barrier film according to the present invention is a gas barrier film having one or more gas barrier layers on one surface of a resin substrate, wherein at least one of the gas barrier layers is a layer containing polysilazane. It is a layer formed by applying energy, and the surface specific resistance of the other surface of the resin base material is in the range of 1 × 10 ^{7 to} 5 × 10 ¹² Ω / □. To do.
Although there is no restriction | limiting in particular in the method of making surface specific resistance in the said range, It is preferable to provide one or more electroconductive layers as a structural layer of a gas barrier film.
By setting the surface specific resistance to 5 × 10 ¹² Ω / □ or less, unevenness in light emission can be improved to a level that cannot be detected with the naked eye. In addition, by setting the surface resistivity to 1 × 10 ⁷ or more, the physical properties of the conductive layer provided for adjusting the surface specific resistance can be maintained in an appropriate range, and scratches may occur due to rubbing during transportation, or peeling may be lost. There is no concern.

  The surface specific resistance can be measured according to the standard of JIS K 7194 using Hiresta UP manufactured by Mitsubishi Chemical Analytech. A standard ring probe (URS) is used for the measurement, the measurement voltage is 1000 V, the measurement position is changed, five points are measured, and the average value is the surface specific resistance value.

Further, the gas barrier film according to the present invention has a surface roughness Ra of the surface opposite to the gas barrier layer of the resin substrate (the other surface) within a range of 1.0 to 3.0 nm, and The surface roughness Rz is preferably in the range of 10 to 30 nm.
That is, when a conductive layer is provided on the other surface of the resin base material, the surface roughness Ra and Rz of the conductive layer is preferably within the above range. By setting the surface roughness Ra and the surface roughness Rz within the above ranges, charging unevenness is further improved, leading to improvement in light emission unevenness of the electronic device.
The surface roughness Ra and Rz can be measured by a general method. For example, it can be performed using a non-contact three-dimensional surface shape roughness meter: Wyko NT9300 manufactured by Veeco.

The “gas barrier film” as used in the present invention is a water vapor permeability (abbreviation: WVTR, temperature: 38 ° C., relative humidity (RH): 100%) measured by a method based on JIS K 7129-1992. It means that the film is 1 (g / m ² · 24 h) or less.
The water vapor transmission rate can be measured, for example, with a water vapor transmission rate measuring device (trade name: manufactured by Permatran Mocon) in an atmosphere of 38 ° C. and 100% RH.

Hereinafter, each component of the gas barrier film will be described.
<Conductive layer>
The conductive layer may be provided on either the one surface (surface on the gas barrier layer side) or the other surface (surface opposite to the surface on the gas barrier layer side) of the resin base material. When provided on the surface on the barrier layer side, the outermost layer is preferably provided as a gas barrier layer. More preferably, it is preferably provided on the surface opposite to the surface on the gas barrier layer side, and in this case, it is further preferable that the outermost layer be a conductive layer.

The conductive layer is preferably formed by applying a coating liquid dispersed in a binder resin that cures conductive fine particles, followed by drying and curing.
(Conductive fine particles)
The conductive fine particles are not particularly limited as long as they are conductive metal oxide fine particles. For example, tin oxide-based fine particles such as tin oxide, antimony-doped tin oxide, phosphorus-doped tin oxide, and fluorine-doped tin oxide; Titanium oxide fine particles such as titanium, cerium oxide fine particles such as cerium oxide, zirconium oxide fine particles such as zirconium oxide, aluminum oxide fine particles such as aluminum oxide, silicon oxide fine particles such as silicon oxide, indium oxide, tin-doped indium oxide Indium oxide-based fine particles such as antimony oxide, antimony oxide-based fine particles such as antimony oxide, and zinc oxide-based fine particles such as zinc antimonate, zinc oxide, aluminum-doped zinc oxide, and gallium-doped zinc oxide.
Among these, tin oxide-based fine particles, indium oxide-based fine particles, zinc oxide-based fine particles, and antimony oxide-based fine particles are preferable. In terms of obtaining high conductivity and high transparency, in particular, tin oxide, antimony-doped tin oxide (ATO), phosphorus-doped tin oxide (PTO), fluorine-doped tin oxide, tin-doped indium oxide (ITO), aluminum-doped zinc oxide, Gallium-doped zinc oxide, zinc antimonate and antimony oxide are preferred.

  The average particle diameter of the conductive fine particles is preferably in the range of 10 to 120 nm as the average primary particle diameter. Moreover, it is preferable to use in the state disperse | distributed to the solvent. By setting the average primary particle size to 10 nm or more, dispersion can be performed without causing excessive aggregation, and a stable dispersion can be obtained. Further, by setting the average primary particle diameter to 120 nm or less, light scattering is not caused and transparency can be improved.

  As a commercial item of conductive fine particles, manufactured by Nissan Chemical Industries: San Epoque EFR-6N, San Epoque EFR-6NP (antimony pentoxide), manufactured by Ishihara Sangyo: SN-100P (ATO), FS-10P (ATO), SN-102P (ATO), FS-12P (ATO), ET-300W (ATO-coated titanium oxide), manufactured by Mitsubishi Materials: T-1 (ITO), S-1200, S-2000 (tin oxide), EPT-1 -5L (ATO), EPSP-2 (PTO), Mitsui Metals: Pastoran (ITO, ATO), CI Kasei: Nanotech ITO, Nanotech SnO2, Catalytic Chemical Industries: TL-20 (ATO), TL-30 (ATO), TL-30S (PTO), TL-120 (ITO), TL-130 (ITO), manufactured by Hakusui Tech: PazetCK (A Miniumudopu zinc oxide), PazetGK (gallium-doped zinc oxide), manufactured by Sakai Chemical Industry Co.: SC-18 (aluminum-doped zinc oxide) and the like. These can be appropriately dispersed and used by a conventional method.

  Commercially available solvent dispersions of conductive inorganic fine particles include: Nissan Chemical Co., Ltd .: Celnax CX-Z610M-F2, CX-Z603M-F2, CX-Z410K (Zinc Antimonate), Cellnax CX- S204IP, CX-S501M, CX-S505M (above PTO), JGC Catalysts & Chemicals: ELECOM series (ATO), and the like.

(Binder resin)
As the binder resin, a thermosetting resin material or a photosensitive resin material used for a smooth layer described later can be preferably used.
In addition, a (meth) acrylic resin polymer having conductivity described in JP2011-99056A can be used.
Moreover, in formation of an electroconductive layer, additives, such as antioxidant, a ultraviolet absorber, a plasticizer, can be added to the above-mentioned photosensitive resin material as needed. In addition, an appropriate resin or additive may be used for improving the film formability and preventing the film from generating pinholes.

In order to adjust the surface specific resistance within the range of the present invention, the ratio of the conductive fine particles to the binder resin, the thickness of the conductive layer, and the like can be controlled. For example, when the ratio of the conductive fine particles is increased, the surface specific resistance is decreased, and when the thickness is increased, the surface specific resistance is decreased.
In the present invention, the mass ratio of the conductive fine particles / binder resin is preferably in the range of 20/80 to 80/20, more preferably in the range of 30/70 to 70/30. More preferably, it is within the range of / 60 to 60/40.
By setting the ratio of the conductive fine particles / binder resin within the range of 20/80 to 80/20, the ratio of the conductive fine particles to the binder resin does not become too high, and the conductive layer becomes brittle. There is no concern that scratches may occur due to rubbing or the like during conveyance, or peeling may be lost.
The thickness of the conductive layer is preferably in the range of 0.1 to 5.0 μm, and more preferably in the range of 0.2 to 3.0 μm.

<Resin substrate>
As a resin base material used for the gas barrier film of the present invention, for example, a plastic film is used.
The plastic film used is not particularly limited in material, thickness and the like as long as it can hold a gas barrier layer, a conductive layer and the like, and can be appropriately selected according to the purpose of use.
Specific examples of the plastic film include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, and polyetherimide. Resin, Cellulose acylate resin, Polyurethane resin, Polyether ether ketone resin, Polycarbonate resin, Alicyclic polyolefin resin, Polyarylate resin, Polyether sulfone resin, Polysulfone resin, Cycloolefin copolymer, Fluorene ring modified polycarbonate resin, Alicyclic Examples thereof include thermoplastic resins such as modified polycarbonate resins, fluorene ring-modified polyester resins, and acryloyl compounds.

When the gas barrier film according to the present invention is used as a substrate for an electronic device such as an organic EL element, the resin base material is preferably made of a heat-resistant material.
Specifically, a resin base material having a linear expansion coefficient in the range of 15 to 100 ppm / K and a glass transition temperature (Tg) in the range of 100 to 300 ° C. is used.
The resin base material satisfies the necessary conditions as a laminated film for electronic parts and displays. That is, when the gas barrier film of the present invention is used for these applications, the gas barrier film may be exposed to a process at 150 ° C. or higher. In this case, if the linear expansion coefficient of the resin base material in the gas barrier film is in the range of 15 to 100 ppm / K, the substrate dimensions are stabilized when the gas barrier film is passed through the temperature process as described above, and the thermal expansion is performed. In addition, with the shrinkage, inconvenience that the blocking performance is deteriorated or a problem that it cannot withstand the heat process is less likely to occur. Further, it is possible to prevent the film from being broken like glass and the flexibility is deteriorated.

The Tg and linear expansion coefficient of the resin base material can be adjusted by an additive or the like.
More preferable specific examples of the thermoplastic resin that can be used as the resin substrate include, for example, polyethylene terephthalate (PET: 70 ° C.), polyethylene naphthalate (PEN: 120 ° C.), polycarbonate (PC: 140 ° C.), and alicyclic ring. Polyolefin (for example, ZEONOR (registered trademark) 1600: 160 ° C) manufactured by Nippon Zeon Co., Ltd., polyarylate (PAr: 210 ° C), polyethersulfone (PES: 220 ° C), polysulfone (PSF: 190 ° C), cycloolefin Copolymer (COC: Compound described in JP-A No. 2001-150584: 162 ° C.), polyimide (for example, Neoprim (registered trademark): 260 ° C. manufactured by Mitsubishi Gas Chemical Co., Ltd.), fluorene ring-modified polycarbonate (BCF-PC: special Kai 2000-227603 Compound described in JP: 225 ° C.), alicyclic modified polycarbonate (IP-PC: compound described in JP-A No. 2000-227603: 205 ° C.), acryloyl compound (compound described in JP-A No. 2002-80616): 300 (In the parentheses indicate Tg).

  Since the gas barrier film according to the present invention is used as an electronic device such as an organic EL element, the plastic film is preferably transparent. That is, the light transmittance is usually 80% or more, preferably 85% or more, and more preferably 90% or more.

The light transmittance is calculated by measuring the total light transmittance and the amount of scattered light using the method described in JIS K7105: 1981, that is, using an integrating sphere light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance. can do.
However, even when the gas barrier film according to the present invention is used for display, transparency is not necessarily required when it is not installed on the observation side. Therefore, in such a case, an opaque material can be used as the plastic film. Examples of the opaque material include polyimide, polyacrylonitrile, and known liquid crystal polymers.

The thickness of the plastic film used for the gas barrier film according to the present invention is appropriately selected depending on the application and is not particularly limited, but is typically in the range of 1 to 800 μm, preferably in the range of 10 to 200 μm. Is within. These plastic films may have functional layers such as a transparent conductive layer and a primer layer. As the functional layer, in addition to those described above, those described in paragraph numbers “0036” to “0038” of JP-A-2006-289627 can be preferably employed.
Moreover, the unstretched film may be sufficient as the resin base material quoted above, and a stretched film may be sufficient as it.

  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, the unstretched base material is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, etc. A stretched substrate can be produced by stretching in the direction perpendicular to the flow direction of the substrate (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the base material, but is preferably 2 to 10 times in each of the vertical axis direction and the horizontal axis direction.

  It is preferable to perform various known treatments for improving adhesion, such as corona discharge treatment, flame treatment, oxidation treatment, or plasma treatment, on at least the side of the substrate on which the gas barrier layer according to the present invention is provided, It is more preferable to combine the above treatments as necessary.

<Layers with various functions>
In the gas barrier film of the present invention, layers having various functions can be provided.
(Anchor coat layer)
An anchor coat layer may be formed on the surface of the base material on the side on which the gas barrier layer according to the present invention is formed for the purpose of improving the adhesion with the gas barrier layer.

  As anchor coating agents used in the anchor coat layer, polyester resins, isocyanate resins, urethane resins, acrylic resins, ethylene vinyl alcohol resins, vinyl modified resins, epoxy resins, modified styrene resins, modified silicone resins, alkyl titanates, etc. are used alone. Or in combination of two or more.

Conventionally known additives can be added to these anchor coating agents. The above-mentioned anchor coating agent is coated on the support by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, etc., and anchor coating is performed by drying and removing the solvent, diluent, etc. be able to. The application amount of the anchor coating agent is preferably about 0.1 to 5.0 g / m ² (dry state).

The anchor coat 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. Alternatively, by forming an anchor coat layer as described in JP 2004-314626 A, when an inorganic thin film is formed thereon by a vapor phase method, the gas generated from the substrate side is blocked to some extent. Thus, an anchor coat layer can be formed for the purpose of controlling the composition of the inorganic thin film.
The thickness of the anchor coat layer is not particularly limited, but is preferably about 0.5 to 10 μm.

(Smooth layer)
In the gas barrier film of this invention, you may have a smooth layer between a resin base material and a gas barrier layer. Moreover, you may provide a smooth layer also in the back surface (surface on the opposite side to a gas barrier layer) of a resin base material. In this case, it is preferable to provide a smooth layer between the resin substrate and the conductive layer. The smooth layer used in the present invention flattens the rough surface of the resin base material on which protrusions and the like are present, or fills in the unevenness and pinholes generated in the gas barrier layer by the protrusions existing on the resin base material. Is provided. 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, Examples thereof include a resin composition in which a polyfunctional acrylate monomer such as polyester acrylate, polyether acrylate, polyethylene glycol acrylate, or 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.

  Specific examples of thermosetting materials include TutProm Series (Organic Polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Co., Ltd., Nanohybrid Silicone manufactured by Adeka, and Unidic manufactured by DIC. (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 manufactured by Nittobo Co., Ltd. Examples include coats, thermosetting urethane resins composed of acrylic polyols and isocyanate prepolymers, phenol resins, urea melamine resins, epoxy resins, unsaturated polyester resins, and silicon resins. 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 spin coating method, a spray method, a blade coating method, or a dip method, or a dry coating method such as an evaporation 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 in order to improve the film formability and prevent the generation of pinholes in the film.

The thickness of the smooth layer is preferably in the range of 1 to 10 μm, more preferably in the range of 2 to 7 μm, from the viewpoint of improving the heat resistance of the film and facilitating balance adjustment of the optical properties of the film. It is preferable to do.
The smoothness of the smooth layer is a value expressed by the surface roughness defined by JIS B 0601: 2001, and the ten-point average roughness Rz is preferably in the range of 10 to 30 nm. If it is this range, even if it is a case where a barrier layer is apply | coated by the application type, even if it is a case where a coating means contacts the smooth layer surface by application methods, such as a wire bar and a wireless bar, applicability | paintability will be impaired. In addition, it is easy to smooth the unevenness after coating.

(Bleed-out prevention layer)
The gas barrier film of the present invention may have a bleed-out preventing layer on the base material surface opposite to the surface on which the smooth layer is provided.
The bleed-out prevention layer is for the purpose of suppressing the phenomenon that, when a film having a smooth layer is heated, unreacted oligomers etc. migrate from the film having the smooth layer to the surface and contaminate the contact surface. , Provided on the opposite surface of the substrate having a smooth layer. 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. Or the monounsaturated organic compound etc. which have one polymerizable unsaturated group in a molecule | numerator can be mentioned.

  As other additives, a matting agent may be contained. As the matting agent, inorganic particles having an average particle diameter of about 0.1 to 5 μm are preferable. 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 parts by mass or more, preferably 4 parts by mass or more, more preferably 6 parts by mass or more and 20 parts by mass or less, preferably 18 parts per 100 parts by mass of the solid content of the hard coat agent. It is desirable that they are mixed in a proportion of not more than part by mass, more preferably not more than 16 parts by mass.

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 mixed with a hard coat agent, a matting agent, and other components as necessary, and is prepared as a coating solution by using a diluent solvent as necessary, and supports the coating solution. It can form by apply | coating to a body film surface by a conventionally well-known coating method, and then irradiating with ionizing radiation and making it harden | cure.

  In addition, as a method of irradiating ionizing radiation, ultraviolet rays having a wavelength range of 100 to 400 nm, preferably 200 to 400 nm, emitted from an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide lamp or the like. Or an electron beam in a wavelength region of 100 nm or less emitted from a scanning or curtain type electron beam accelerator.

  The thickness of the bleed-out prevention layer improves the heat resistance of the film, facilitates the balance adjustment of the optical properties of the film, and prevents curling when a bleed-out prevention layer is provided only on one side of the gas barrier film. From the viewpoint of achieving this, it is preferably in the range of 1 to 10 μm, and more preferably in the range of 2 to 7 μm.

<Gas barrier layer>
The gas barrier layer according to the present invention is a layer formed on one surface of the resin base material. The gas barrier layer may be a single layer or a laminated structure of two or more layers, but at least one of the gas barrier layers is a layer formed by applying energy to a layer containing polysilazane.
The gas barrier layer is formed by applying energy to at least one gas barrier layer obtained by applying and drying a coating liquid containing polysilazane (hereinafter simply referred to as a coating film). The formation method of the other gas barrier layer is not particularly limited, but vacuum film formation methods such as physical vapor deposition (PVD) and chemical vapor deposition (CVD) And a coating film forming method.

When the gas barrier layer has a laminated structure of two or more layers, the gas barrier layers may have the same composition or different compositions.
The thickness of the gas barrier layer (the total thickness in the case of a laminated structure of two or more layers) is preferably about 10 to 1000 nm, and more preferably in the range of 50 to 500 nm. Within this range, the balance between gas barrier properties and crack resistance at the time of bending is good, which is preferable. That is, the gas barrier property is good and cracks are hardly generated during bending.
Hereinafter, the coating film forming method and the vacuum film forming method will be described.

(Coating film formation method)
At least one of the gas barrier layers according to the present invention is formed by a method (coating film forming method) in which energy is further applied to a coating film formed by applying a coating liquid containing polysilazane. . By applying this energy, the gas barrier layer exhibits gas barrier properties.
Polysilazane is a polymer having a silicon-nitrogen bond, and ceramics such as SiO ₂ , Si ₃ N ₄ , and both intermediate solid solutions SiO _x N _y having bonds such as Si—N, Si—H, and N—H. It is a precursor inorganic polymer.

上記一般式（Ｉ）において、Ｒ_１、Ｒ_２及びＲ_３は、それぞれ独立して、水素原子、置換又は非置換の、アルキル基、アリール基、ビニル基又は（トリアルコキシシリル）アルキル基である。この際、Ｒ_１、Ｒ_２及びＲ_３は、それぞれ、同じであっても又は異なるものであってもよい。
ここで、アルキル基としては、炭素原子数１〜８の直鎖、分岐鎖又は環状のアルキル基が挙げられる。より具体的には、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、ネオペンチル基、ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基、２−エチルヘキシル基、シクロプロピル基、シクロペンチル基、シクロヘキシル基などがある。
また、アリール基としては、炭素原子数６〜３０のアリール基が挙げられる。より具体的には、フェニル基、ビフェニル基、ターフェニル基などの非縮合炭化水素基；ペンタレニル基、インデニル基、ナフチル基、アズレニル基、ヘプタレニル基、ビフェニレニル基、フルオレニル基、アセナフチレニル基、プレイアデニル基、アセナフテニル基、フェナレニル基、フェナントリル基、アントリル基、フルオランテニル基、アセフェナントリレニル基、アセアントリレニル基、トリフェニレニル基、ピレニル基、クリセニル基、ナフタセニル基などの縮合多環炭化水素基が挙げられる。
（トリアルコキシシリル）アルキル基としては、炭素原子数１〜８のアルコキシ基で置換されたシリル基を有する炭素原子数１〜８のアルキル基が挙げられる。より具体的には、３−（トリエトキシシリル）プロピル基、３−（トリメトキシシリル）プロピル基などが挙げられる。 Specifically, the polysilazane preferably has the following structure.

In the general formula (I), R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group. . At this time, R ₁ , R ₂ and R ₃ may be the same or different.
Here, as an alkyl group, a C1-C8 linear, branched or cyclic alkyl group is mentioned. More specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n -Hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like.
Moreover, as an aryl group, a C6-C30 aryl group is mentioned. More specifically, non-condensed hydrocarbon groups such as phenyl group, biphenyl group, terphenyl group; pentarenyl group, indenyl group, naphthyl group, azulenyl group, heptaenyl group, biphenylenyl group, fluorenyl group, acenaphthylenyl group, preadenenyl group A condensed polycyclic hydrocarbon group such as an Can be mentioned.
Examples of the (trialkoxysilyl) alkyl group include an alkyl group having 1 to 8 carbon atoms having a silyl group substituted with an alkoxy group having 1 to 8 carbon atoms. More specifically, 3- (triethoxysilyl) propyl group, 3- (trimethoxysilyl) propyl group and the like can be mentioned.

The substituent optionally present in R _{1 to} R ₃ is not particularly limited. For example, an alkyl group, a halogen atom, a hydroxy group (—OH), a mercapto group (—SH), a cyano group (—CN), There are a sulfo group (—SO ₃ H), a carboxy group (—COOH), a nitro group (—NO ₂ ), and the like. Incidentally, the optional substituents may not be the same as R ₁ to R ₃ to be replaced. For example, when R _{1 to} R ₃ are alkyl groups, they are not further substituted with an alkyl group.
Of these, R ₁ , R ₂ and R ₃ are preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a phenyl group, a vinyl group, 3 -(Triethoxysilyl) propyl group or 3- (trimethoxysilylpropyl) group.

In the general formula (I), n is an integer, and the polysilazane having the structure represented by the general formula (I) is determined to have a number average molecular weight of 150 to 150,000 g / mol. preferable.
In the compound having the structure represented by the general formula (I), one of preferable embodiments is perhydropolysilazane (also referred to as PHPS) in which all of R ₁ , R _2, and R ₃ are hydrogen atoms.
Alternatively, polysilazane has a structure represented by the following general formula (II).

上記一般式（II）において、Ｒ_１′、Ｒ_２′、Ｒ_３′、Ｒ_４′、Ｒ_５′及びＲ_６′は、それぞれ独立して、水素原子、置換又は非置換の、アルキル基、アリール基、ビニル基又は（トリアルコキシシリル）アルキル基である。この際、Ｒ_１′、Ｒ_２′、Ｒ_３′、Ｒ_４′、Ｒ_５′及びＲ_６′は、それぞれ、同じであっても又は異なるものであってもよい。上記における、置換又は非置換の、アルキル基、アリール基、ビニル基又は（トリアルコキシシリル）アルキル基は、上記一般式（Ｉ）の定義と同様であるため、説明を省略する。

In the above general formula (II), R _{1 ′} , R _{2 ′} , R _{3 ′} , R _{4 ′} , R _{5 ′} and R _{6 ′} each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, An aryl group, a vinyl group or a (trialkoxysilyl) alkyl group. In this case, R _{1 ′} , R _{2 ′} , R _{3 ′} , R _{4 ′} , R _{5 ′} and R _{6 ′} may be the same or different. The substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the above is the same as the definition of the general formula (I), and thus the description is omitted.

  In the general formula (II), n ′ and p are integers, and the polysilazane having the structure represented by the general formula (II) is determined to have a number average molecular weight of 150 to 150,000 g / mol. Is preferred. Note that n ′ and p may be the same or different.

Among the polysilazanes of the general formula (II), R _{1 ′} , R _{3 ′} and R _{6 ′} each represent a hydrogen atom, and R _{2 ′} , R _{4 ′} and R _{5 ′} each represent a methyl group; R _{1 ′} , R _{3 ′} and R _{6 ′} each represent a hydrogen atom, R _{2 ′} and R _{4 ′} each represent a methyl group, and R _{5 ′} represents a vinyl group; R _{1 ′} , R _{3 ′} and R ₄ Preferred are compounds in which _' and R _6' each represent a hydrogen atom, and R _{2 '} and R _5' each represent a methyl group.
Alternatively, polysilazane has a structure represented by the following general formula (III).

上記一般式（III）において、Ｒ_１″、Ｒ_２″、Ｒ_３″、Ｒ_４″、Ｒ_５″、Ｒ_６″、Ｒ_７″、Ｒ_８″及びＲ_９″は、それぞれ独立して、水素原子、置換又は非置換の、アルキル基、アリール基、ビニル基又は（トリアルコキシシリル）アルキル基である。この際、Ｒ_１″、Ｒ_２″、Ｒ_３″、Ｒ_４″、Ｒ_５″、Ｒ_６″、Ｒ_７″、Ｒ_８″及びＲ_９″は、それぞれ、同じであっても又は異なるものであってもよい。上記における、置換又は非置換の、アルキル基、アリール基、ビニル基又は（トリアルコキシシリル）アルキル基は、上記一般式（Ｉ）の定義と同様であるため、説明を省略する。

In the general formula (III), R _{1 ″} , R _{2 ″} , R _{3 ″} , R _{4 ″} , R _{5 ″} , R _{6 ″} , R _{7 ″} , R _{8 ″} and R _{9 ″} are each independently A hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group. In this case, R _{1 ″} , R _{2 ″} , R _{3 ″} , R _{4 ″} , R _{5 ″.} , R _{6 ″} , R _{7 ″} , R _{8 ″} and R _{9 ″} may be the same or different. The substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the above is the same as the definition of the general formula (I), and thus the description is omitted.

In the general formula (III), n ″, p ″ and q are integers, and the polysilazane having the structure represented by the general formula (III) has a number average molecular weight of 150 to 150,000 g / mol. Preferably, it is defined. Note that n _″ , p _″ and q may be the same or different.

Among the polysilazanes of the general formula (III), R _{1 ″} , R _{3 ″} and R _{6 ″} each represent a hydrogen atom, and R _{2 ″} , R _{4 ″} , R _{5 ″} and R _{8 ″} each represent a methyl group. , R _{9 ″} represents a (triethoxysilyl) propyl group, and R _{7 ″} represents an alkyl group or a hydrogen atom.

  On the other hand, the organopolysilazane in which a part of the hydrogen atom portion bonded to Si is substituted with an alkyl group or the like has improved adhesion to the base material as a base by having an alkyl group such as a methyl group and is hard. The ceramic film made of brittle polysilazane can be toughened, and there is an advantage that the occurrence of cracks can be suppressed even when the (average) film thickness is increased. For this reason, perhydropolysilazane and organopolysilazane may be selected as appropriate according to the application, and may be used in combination.

  Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings. Its molecular weight is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), and there is a liquid or solid substance, and its state varies depending on the molecular weight.

Polysilazane is commercially available in the form of a solution dissolved in an organic solvent, and the commercially available product can be used as it is as a coating solution for forming a gas barrier layer.
Examples of commercially available polysilazane solutions include NN120-10, NN120-20, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL120-20, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials Co., Ltd. Is mentioned.

  Other examples of polysilazanes that can be used in the present invention include, but are not limited to, for example, silicon alkoxide-added polysilazanes obtained by reacting silicon alkoxides with the above polysilazanes (Japanese Patent Laid-Open No. 5-23827), Glycidol-added polysilazane (Japanese Patent Laid-Open No. 6-122852) obtained by reaction, alcohol-added polysilazane obtained by reacting alcohol (Japanese Patent Laid-Open No. 6-240208), metal carboxylate obtained by reacting metal carboxylate Addition polysilazane (JP-A-6-299118), acetylacetonate complex-added polysilazane (JP-A-6-306329) obtained by reacting a metal-containing acetylacetonate complex, metal obtained by adding metal fine particles Fine particle added polysila Emissions, such as (JP-A-7-196986), and a polysilazane ceramic at low temperatures.

When polysilazane is used, the content of polysilazane in the gas barrier layer before energy application can be 100% by mass when the total mass of the gas barrier layer is 100% by mass.
Further, when the gas barrier layer contains a material other than polysilazane, the content of polysilazane in the layer is preferably in the range of 10 to 99% by mass, and in the range of 40 to 95% by mass. Is more preferable, and particularly preferably in the range of 70 to 95% by mass.

<< Gas barrier layer forming coating liquid >>
The solvent for preparing the coating liquid for forming the gas barrier layer is not particularly limited as long as it can dissolve the silicon compound, but water and reactive groups (for example, hydroxy group, easily reacting with the silicon compound). Or an amine group and the like, and an inert organic solvent with respect to the silicon compound is preferable, and an aprotic organic solvent is more preferable.
Specifically, the solvent includes an aprotic solvent; for example, carbon such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso, and turben. Hydrogen solvents; Halogen hydrocarbon solvents such as methylene chloride and trichloroethane; Esters such as ethyl acetate and butyl acetate; Ketones such as acetone and methyl ethyl ketone; Aliphatic ethers such as dibutyl ether, dioxane and tetrahydrofuran; Alicyclic ethers and the like Ethers: Examples include tetrahydrofuran, dibutyl ether, mono- and polyalkylene glycol dialkyl ethers (diglymes), and the like.
The solvent is selected according to purposes such as the solubility of the silicon compound and the evaporation rate of the solvent, and may be used alone or in the form of a mixture of two or more.

  The concentration of the silicon compound in the gas barrier layer forming coating solution is not particularly limited, and varies depending on the film thickness of the layer and the pot life of the coating solution, but is preferably in the range of 1 to 80% by mass, more preferably 5 to 5%. It is in the range of 50% by mass, more preferably in the range of 10-40% by mass.

The gas barrier layer forming coating solution preferably contains a catalyst in order to promote reforming. As the catalyst applicable to the present invention, a basic catalyst is preferable, and in particular, N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, Amine catalysts such as N ', N'-tetramethyl-1,3-diaminopropane, N, N, N', N'-tetramethyl-1,6-diaminohexane, Pt compounds such as Pt acetylacetonate, propion Examples thereof include metal catalysts such as Pd compounds such as acid Pd, Rh compounds such as Rh acetylacetonate, and N-heterocyclic compounds. Of these, it is preferable to use an amine catalyst.
The concentration of the catalyst added at this time is preferably in the range of 0.1 to 10% by mass, more preferably in the range of 0.5 to 7% by mass, based on the silicon compound. By setting the catalyst addition amount within this range, it is possible to avoid excessive silanol formation due to rapid progress of the reaction, reduction in film density, increase in film defects, and the like.

  The following additives can be used in the gas barrier layer forming coating solution as necessary. For example, cellulose ethers, cellulose esters; for example, ethyl cellulose, nitrocellulose, cellulose acetate, cellulose acetobutyrate, etc., natural resins; for example, rubber, rosin resin, etc., synthetic resins; Aminoplasts, especially urea resins, melamine formaldehyde resins, alkyd resins, acrylic resins, polyesters or modified polyesters, epoxides, polyisocyanates or blocked polyisocyanates, polysiloxanes, and the like.

<Method of applying gas barrier layer forming coating solution>
As a method of applying the gas barrier layer forming coating solution, a conventionally known appropriate wet coating method may be employed. Specific examples include spin coating method, roll coating method, flow coating method, ink jet method, spray coating method, printing method, dip coating method, casting film forming method, bar coating method, die coating method, gravure printing method and the like. It is done.
The coating thickness can be appropriately set according to the preferred thickness and purpose.

  After applying the coating solution, it is preferable to dry the coating film. By drying the coating film, the organic solvent contained in the coating film can be removed. At this time, all of the organic solvent contained in the coating film may be dried or may be partially left. Even when a part of the organic solvent is left, a suitable gas barrier layer can be obtained. The remaining solvent can be removed later.

Although the drying temperature of a coating film changes also with the base material to apply, it is preferable to exist in the range of 50-200 degreeC.
For example, when a polyethylene terephthalate substrate having a glass transition temperature (Tg) of 70 ° C. is used as the substrate, the drying temperature is preferably set to 150 ° C. or less in consideration of deformation of the substrate due to heat.
The temperature can be set by using a hot plate, oven, furnace or the like.
The drying time is preferably set to a short time. For example, when the drying temperature is 150 ° C., the drying time is preferably set within 30 minutes.
The drying atmosphere may be any condition such as an air atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum atmosphere, or a reduced pressure atmosphere with a controlled oxygen concentration.

The coating film obtained by applying the gas barrier layer forming coating solution may include a step of removing moisture before application of energy or during application of energy. As a method for removing moisture, a form of dehumidification while maintaining a low humidity environment is preferable. Since humidity in a low-humidity environment varies depending on temperature, a preferable form is shown for the relationship between temperature and humidity by defining the dew point temperature. A preferable dew point temperature is 4 ° C. or lower (temperature 25 ° C./humidity 25%), a more preferable dew point temperature is −5 ° C. (temperature 25 ° C./humidity 10%) or lower, and the maintained time is the film thickness of the gas barrier layer. It is preferable to set appropriately.
Under the condition that the film thickness of the gas barrier layer is 1.0 μm or less, it is preferable that the dew point temperature is −5 ° C. or less and the maintaining time is 1 minute or more. The lower limit of the dew point temperature is not particularly limited, but is usually −50 ° C. or higher and preferably −40 ° C. or higher. This is a preferred form from the viewpoint of promoting the dehydration reaction of the gas barrier layer converted to silanol by removing water before or during the reforming treatment.

(Energy application)
Subsequently, energy is applied to the coating film formed as described above, and a conversion reaction of the silicon compound to silicon oxide or silicon oxynitride is performed, so that the gas barrier layer can exhibit gas barrier properties. Modification to inorganic thin film.
The conversion reaction of the silicon compound to silicon oxide or silicon oxynitride can be applied by appropriately selecting a known method.
Specific examples of the modification treatment include plasma treatment, ultraviolet irradiation treatment, and heat treatment. However, in the case of modification by heat treatment, formation of a silicon oxide film or a silicon oxynitride layer by a substitution reaction of a silicon compound requires a high temperature of 450 ° C. or higher, so it is difficult to adapt to a flexible substrate such as plastic. . For this reason, it is preferable to perform the heat treatment in combination with other reforming treatments.
Therefore, as the modification treatment, from the viewpoint of adapting to a plastic substrate, a plasma treatment capable of a conversion reaction at a lower temperature or a conversion reaction by ultraviolet irradiation treatment is preferable. Hereinafter, plasma treatment and ultraviolet irradiation treatment, which are preferable modification treatment methods, will be described.

《Plasma treatment》
In the present invention, a known method can be used as the plasma treatment that can be used as the modification treatment, and an atmospheric pressure plasma treatment or the like can be preferably used.
The atmospheric pressure plasma CVD method, which performs plasma CVD processing near atmospheric pressure, does not need to be reduced in pressure and is more productive than the plasma CVD method under vacuum. The film speed is high, and further, under a high pressure condition under atmospheric pressure as compared with the conditions of a normal CVD method, the gas mean free process is very short, so that a very homogeneous film can be obtained.
In the case of atmospheric pressure plasma treatment, as the discharge gas, nitrogen gas or a gas containing Group 18 atoms in the long-period periodic table, specifically helium, neon, argon, krypton, xenon, radon, or the like is used. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.

<Ultraviolet irradiation treatment>
As one of the modification treatment methods, treatment by ultraviolet irradiation is preferable. Ozone and active oxygen atoms generated by ultraviolet rays (synonymous with ultraviolet light) have high oxidation ability, and can form silicon oxide films or silicon oxynitride films with high density and insulation at low temperatures. It is.
By this ultraviolet irradiation, the base material is heated, and O ₂ and H ₂ O contributing to ceramicization (silica conversion), an ultraviolet absorber, and polysilazane itself are excited and activated. Ceramics are promoted and the resulting gas barrier layer becomes denser. Irradiation with ultraviolet rays is effective at any time after the formation of the coating film.

In the ultraviolet irradiation treatment, any commonly used ultraviolet ray generator can be used.
The ultraviolet ray referred to in the present invention generally refers to an electromagnetic wave having a wavelength of 10 to 400 nm, but in the case of an ultraviolet irradiation treatment other than the vacuum ultraviolet ray (10 to 200 nm) treatment described later, it is preferably 210 to 375 nm. Use ultraviolet light.
In the irradiation with ultraviolet rays, it is preferable to set the irradiation intensity and the irradiation time as long as the substrate carrying the irradiated gas barrier layer is not damaged.

Taking a case where a plastic film is used as a base material, for example, a 2 kW (80 W / cm × 25 cm) lamp is used, and the strength of the base material surface is within a range of ²⁰ to 300 mW / cm ² , preferably 50 to The distance between the substrate and the ultraviolet irradiation lamp can be set so as to be within the range of 200 mW / cm ² , and irradiation can be performed for 0.1 seconds to 10 minutes.

  In general, when the substrate temperature during ultraviolet irradiation treatment is 150 ° C. or more, in the case of a plastic film or the like, the properties of the substrate are impaired, such as deformation of the substrate or deterioration of its strength. Become. However, in the case of a film having high heat resistance such as polyimide, a modification treatment at a higher temperature is possible. Accordingly, there is no general upper limit for the substrate temperature at the time of ultraviolet irradiation, and it can be appropriately set by those skilled in the art depending on the type of substrate. Moreover, there is no restriction | limiting in particular in ultraviolet irradiation atmosphere, What is necessary is just to implement in air.

  Examples of such ultraviolet ray generating means include metal halide lamps, high pressure mercury lamps, low pressure mercury lamps, xenon arc lamps, carbon arc lamps, and excimer lamps (single wavelengths of 172 nm, 222 nm, and 308 nm, for example, USHIO INC. Manufactured by M.D. Com Co., Ltd.), UV light laser, and the like, but are not particularly limited. In addition, when irradiating the generated ultraviolet ray to the gas barrier layer, it is preferable to apply the ultraviolet ray from the generation source to the gas barrier layer after reflecting the ultraviolet ray from the generation source with a reflector from the viewpoint of achieving efficiency improvement and uniform irradiation. .

The ultraviolet irradiation can be adapted to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate to be used. For example, in the case of batch processing, a laminate having a gas barrier layer on the surface can be processed in an ultraviolet baking furnace equipped with an ultraviolet source as described above.
The ultraviolet baking furnace itself is generally known. For example, an ultraviolet baking furnace manufactured by I-Graphics Co., Ltd. can be used. When the laminate having the gas barrier layer on the surface is a long film, the ceramic is obtained by continuously irradiating ultraviolet rays in the drying zone having the ultraviolet ray generation source as described above while transporting the laminate. Can be
The time required for ultraviolet irradiation is generally within the range of 0.1 second to 10 minutes, preferably within the range of 0.5 second to 3 minutes, although it depends on the composition and concentration of the substrate and gas barrier layer used. It is.

<< Vacuum UV irradiation treatment: Excimer irradiation treatment >>
In the present invention, the most preferable modification treatment method is treatment by vacuum ultraviolet irradiation (excimer irradiation treatment).
The treatment by vacuum ultraviolet irradiation uses light energy of 100 to 200 nm, preferably light energy with a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound, and bonds the atoms with only photons called photon processes. This is a method of forming a silicon oxide film at a relatively low temperature (about 200 ° C. or lower) by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by action.
In addition, when performing an excimer irradiation process, it is preferable to use heat processing together as mentioned above, and the detail of the heat processing conditions in that case is as having mentioned above.

The radiation source in the present invention may be any radiation source that generates light having a wavelength of 100 to 180 nm, but preferably an excimer radiator (for example, a Xe excimer lamp) having a maximum emission at about 172 nm and an emission line at about 185 nm. Low pressure mercury vapor lamps, medium and high pressure mercury vapor lamps having a wavelength component of 230 nm or less, and excimer lamps having maximum emission at about 222 nm.
Among these, 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 possessed by the active oxygen, ozone and ultraviolet radiation, the polysilazane coating can be modified in a short time.

  Since the excimer lamp has high light generation efficiency, it can be lit 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 necessary 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 is likely to decrease. It is preferable to carry out in a state where the water vapor concentration is low. That is, the oxygen concentration at the time of irradiation with vacuum ultraviolet rays is preferably in the range of 10 to 20000 volume ppm (0.001 to 2 volume%), and in the range of 50 to 10000 volume ppm (0.005 to 1 volume%). It is more preferable to use the inside. Also, the water vapor concentration during the conversion process is preferably in the range of 1000 to 4000 ppm by volume.

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

In vacuum ultraviolet irradiation step, illuminance of the vacuum ultraviolet rays in the coated surface of the polysilazane coating film is subjected is in the range of 1 to 10 W / cm ² is preferably in the range of 30~200mW / cm ² Is more preferable, and it is more preferable that it is in the range of 50 to 160 mW / cm ² . If it is in the range of 1-10 W / cm < ² >, there will be no fear that a modification | reformation efficiency will fall large, and there will also be no fear that an ablation will be produced in a coating film or a base material may be damaged.

The amount of irradiation energy (irradiation amount) of vacuum ultraviolet rays on the coating surface is preferably in the range of 100 mJ / cm ^{2 to} 50 J / cm ² , and preferably in the range of 200 mJ / cm ^{2 to 20} J / cm ^2. More preferably, it is still more preferably in the range of 500 mJ / cm ^{2 to} 10 J / cm ² . If it is in the range of 100 mJ / cm ^{2 to} 50 J / cm ² , there is no concern that the modification will be insufficient, and there is no concern about the occurrence of cracks due to excessive modification and the thermal deformation of the substrate.

Further, the vacuum ultraviolet light used, CO, may be generated by plasma formed in a gas including at least one CO ₂ and CH _4.
Further, as the gas containing at least one of CO, CO ₂ and CH ₄ (hereinafter also referred to as carbon-containing gas), a carbon-containing gas may be used alone, but a rare gas or H ₂ is used as a main gas. It is preferable to add a small amount of carbon-containing gas. Examples of the plasma generation method include capacitively coupled plasma.

  Similarly to the above-described ultraviolet irradiation, vacuum ultraviolet irradiation can be adapted to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate to be used.

For example, in the case of a sheet-like substrate, for example, a vacuum ultraviolet irradiation device shown in FIG. 1 can be used.
As shown in FIG. 1, the vacuum ultraviolet irradiation apparatus 100 includes an apparatus chamber 1, an Xe excimer lamp 2, a lamp holder 3, a sample stage 4, a light shielding plate 6, and the like.
The apparatus chamber 1 supplies an appropriate amount of nitrogen and oxygen from a gas supply port (not shown) to the inside of the chamber and exhausts it from a gas discharge port (not shown), thereby substantially removing water vapor from the inside of the chamber and adjusting the oxygen concentration to a predetermined value. The concentration can be maintained.
The Xe excimer lamp 2 is, for example, a lamp having a double tube structure that can irradiate vacuum ultraviolet rays of 172 nm.
The lamp holder 3 is a holder for holding the Xe excimer lamp 2 and also serves as an external electrode.
The sample stage 4 can be reciprocated horizontally at a predetermined speed in the apparatus chamber 1 by a moving means (not shown). The sample stage 4 can be maintained at a predetermined temperature by a heating means (not shown). A resin base material 5 on which a coating film containing polysilazane is formed is placed on the upper surface of the sample stage 4 and is irradiated with vacuum ultraviolet rays. When the sample stage 4 moves horizontally, the height of the sample stage 4 is adjusted so that the shortest distance between the coating film surface of the resin substrate 5 and the tube surface of the Xe excimer lamp 2 is 3 mm. .
The light shielding plate 6 prevents the vacuum ultraviolet light from being applied to the coating film of the resin base material 5 during the aging of the Xe excimer lamp 2.

In the case of a roll-shaped substrate, it is preferable to form a gas barrier layer in a roll-to-roll manner by configuring a step of applying and drying a coating liquid containing a polysilazane compound and a vacuum ultraviolet ray irradiation step online. . In this case, for example, the manufacturing apparatus shown in FIG. 2 can be used.
In FIG. 2, the left side is a coating film forming unit 32, and the right side is a coating film modifying unit 33. The resin base material 14 drawn out from the roller 22 is coated with a coating liquid containing polysilazane by a die coater 29 to form a coating film. The die coater 29 is an apparatus for forming a coating film by an extrusion-type coating method. The supplied coating solution is extruded and discharged from a slit-shaped discharge port, and a uniform thickness is formed on a resin substrate having a certain width. Thus, a coating film can be formed.
Subsequently, the resin base material and the coating film 15 are conveyed by the rollers 23 and 24, and the coating film is dried in the dryer 30.
Subsequently, the coating film modifying means 33 irradiates the vacuum ultraviolet light with the vacuum ultraviolet lamps (excimer lamps) L1 to L30 while conveying the base material and the coating film.
In addition to introducing nitrogen into the casing 31 of the coating film reforming means 33, nitrogen or air is supplied to each excimer lamp holder (not shown). A support roller having temperature control devices T1 to T32 is installed on the side of the substrate and the coating film 15 opposite to the excimer lamps L1 to L30.
The temperature of the coating film surface is adjusted by the temperature control devices T1 to T32, and the base material and the coating film 15 irradiated with the vacuum ultraviolet light are wound up by the rollers 26 to 28.
In FIG. 2, thirty excimer lamps are installed, but the necessary number can be selected as appropriate according to the thickness and type of the coating film.

<Vacuum deposition method>
The physical vapor deposition method (PVD method) is a method of depositing a target material, for example, a thin film such as a carbon film, on the surface of the material in a gas phase by a physical method. Examples thereof include a DC sputtering method, an RF sputtering method, an ion beam sputtering method, and a magnetron sputtering method, a vacuum deposition method, and an ion plating method.

Sputtering is a method in which a target is placed in a vacuum chamber, a rare gas element (usually argon) ionized by applying a high voltage is collided with the target, and atoms on the target surface are ejected and adhered to the resin substrate. is there.
At this time, a reactive sputtering method is used in which a gas barrier layer is formed by reacting an element ejected from the target with argon gas and nitrogen or oxygen by flowing nitrogen gas or oxygen gas into the vacuum chamber. Also good.

In the chemical vapor deposition (CVD) method, a raw material gas containing a desired thin film component is supplied onto a resin substrate, and the film is deposited by a chemical reaction on the surface of the resin substrate or in the gas phase. It is a method to do.
In addition, for the purpose of activating the chemical reaction, there is a method of generating plasma or the like. Known CVD such as thermal CVD method, catalytic chemical vapor deposition method, photo CVD method, vacuum plasma CVD method, atmospheric pressure plasma CVD method, etc. The method etc. are mentioned. Although not particularly limited, it is preferable to apply a plasma CVD method such as a vacuum plasma CVD method or an atmospheric pressure plasma CVD method from the viewpoint of a film forming speed and a processing area.

  For example, if a silicon compound is used as a raw material compound and oxygen is used as the decomposition gas, silicon oxide is generated. This is because highly active charged particles and active radicals exist in the plasma space at a high density, so that multistage chemical reactions are accelerated at high speed in the plasma space, and the elements present in the plasma space are thermodynamic. This is because it is converted into an extremely stable compound in a very short time.

In the following, a case where a gas barrier layer is manufactured by using a counter roll type roll-to-roll vacuum film forming apparatus that forms a thin film by a plasma CVD method will be described as an example of the film forming apparatus. .
FIG. 3 is a schematic configuration diagram illustrating an example of a film forming apparatus.
As shown in FIG. 3, the film forming apparatus 400 includes a delivery roller 40, transport rollers 41 to 44, first and second film forming rollers 45 and 46, a take-up roller 47, a gas supply pipe 48, and plasma. The power supply 49 for generation | occurrence | production, the magnetic field generators 50 and 51, the vacuum chamber 60, the vacuum pump 70, and the control part 71 are provided.

The delivery roller 40, the transport rollers 41 to 44, the first and second film forming rollers 45 and 46, and the take-up roller 47 are accommodated in the vacuum chamber 60.
The delivery roller 40 feeds the resin base material 81 a installed in a state of being wound in advance toward the transport roller 41. The delivery roller 40 is a cylindrical roller extending in a direction perpendicular to the paper surface, and is wound around the delivery roller 40 by rotating counterclockwise by a drive motor (not shown) (see the arrow in FIG. 3). The resin base material 81 a thus made is sent out toward the transport roller 41.
As the resin base material 81a, a film or sheet made of a resin or a composite material containing a resin is preferably used.

The transport rollers 41 to 44 are cylindrical rollers configured to be rotatable around a rotation axis substantially parallel to the delivery roller 40.
The transport roller 41 is a roller for transporting the resin base material 81 a from the feed roller 40 to the film forming roller 45 while applying an appropriate tension to the resin base material 81 a.
Further, the transport rollers 42 and 43 are configured to transport the resin base material 81b from the film formation roller 45 to the film formation roller 46 while applying appropriate tension to the resin base material 81b formed by the film formation roller 45. It is a roller.
Further, the transport roller 44 is a roller for transporting the resin base material 81 c from the film formation roller 46 to the take-up roller 47 while applying an appropriate tension to the resin base material 81 c formed by the film formation roller 46. is there.

The first film-forming roller 45 and the second film-forming roller 46 are a pair of film-forming rollers that have a rotation axis substantially parallel to the delivery roller 40 and are opposed to each other by a predetermined distance.
In the example shown in FIG. 3, the separation distance between the first film forming roller 45 and the second film forming roller 46 is a distance connecting the point A and the point B. The first film formation roller 45 and the second film formation roller 46 are discharge electrodes formed of a conductive material and are insulated from each other.
In addition, the material and structure of the 1st film-forming roller 45 and the 2nd film-forming roller 46 can be suitably selected so that a desired function can be achieved as an electrode.
Magnetic field generators 50 and 51 are installed inside the first and second film forming rollers 45 and 46, respectively.
A high frequency voltage for plasma generation is applied to the first film formation roller 45 and the second film formation roller 46 by a plasma generation power source 49. As a result, an electric field is formed in the film forming space S between the first film forming roller 45 and the second film forming roller 46, and discharge plasma of the film forming gas supplied from the gas supply pipe 48 is generated.

The take-up roller 47 has a rotation axis substantially parallel to the feed roller 40, takes up the base material 81c, and stores it in a roll shape. The take-up roller 47 takes up the resin substrate 81c by rotating counterclockwise (see the arrow in FIG. 3) by a drive motor (not shown).
The resin base material 81 a fed from the feed roller 40 is wound around the transport rollers 41 to 44, the first film forming roller 45, and the second film forming roller 46 between the feed roller 40 and the take-up roller 47. Thus, it is conveyed by the rotation of each of these rollers while maintaining an appropriate tension.
In addition, the conveyance direction of resin base material 81a, 81b, 81c is shown by the arrow. The transport speed of the resin base materials 81a, 81b, 81c (for example, the transport speed at the point C in FIG. 3) can be adjusted as appropriate according to the type of source gas, the pressure in the vacuum chamber 60, and the like.
The conveyance speed is preferably in the range of 0.1 to 100 m / min, and more preferably in the range of 0.5 to 20 m / min. The conveyance speed is adjusted by controlling the rotation speeds of the drive motors of the delivery roller 40 and the take-up roller 47 by the control unit 71.

When this film forming apparatus is used, the direction of conveyance of the resin base materials 81a, 81b, 81c is opposite to the direction indicated by the arrow in FIG. 3 (hereinafter referred to as the forward direction) (hereinafter referred to as the reverse direction). It is also possible to execute the film-forming process of the gas barrier film.
Specifically, in the state where the resin base material 81c is wound up by the take-up roller 47, the control unit 71 sets the rotation direction of the drive motor of the feed roller 40 and the take-up roller 47 in the direction opposite to the above case. Control to rotate. When controlled in this way, the resin base material 81c sent out from the take-up roller 47 is transported between the feed roller 40 and the take-up roller 47, the transport rollers 41 to 44, the first film forming roller 45, and the second forming roller. While being wound around the film roller 46, it is conveyed in the opposite direction by the rotation of each roller while maintaining an appropriate tension.

The gas supply pipe 48 supplies a film forming gas such as a plasma CVD source gas into the vacuum chamber 60.
The gas supply pipe 48 has a tubular shape extending above the film formation space S in the same direction as the rotation axes of the first film formation roller 45 and the second film formation roller 46, and is provided at a plurality of locations. A film forming gas is supplied to the film forming space S from the opened opening.

For the source gas, for example, an organosilicon compound containing silicon can be used. Examples of the organosilicon compound include hexamethyldisiloxane (hereinafter also simply referred to as “HMDSO”), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, Dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, dimethyl Examples include disilazane, trimethyldisilazane, tetramethyldisilazane, pentamethyldisilazane, and hexamethyldisilazane.
Among these organosilicon compounds, it is desirable to use HMDSO from the viewpoint of easy handling of the compound and high gas barrier properties of the resulting gas barrier film. These organosilicon compounds may be used in combination of two or more. The source gas may contain monosilane in addition to the organosilicon compound.

As the film forming gas, a reactive gas may be used in addition to the source gas. As the reaction gas, a gas that reacts with the raw material gas to become an inorganic compound such as oxide or nitride is selected.
As a reactive gas for forming an oxide as a thin film, for example, oxygen gas or ozone gas can be used. These reaction gases may be used in combination of two or more.
As the film forming gas, a carrier gas may be further used to supply the source gas into the vacuum chamber 60. Further, as a film forming gas, a discharge gas may be further used to generate plasma. As the carrier gas and the discharge gas, for example, a rare gas such as argon, hydrogen, or nitrogen is used.

The magnetic field generators 50 and 51 are members that form a magnetic field in the film formation space S between the first film formation roller 45 and the second film formation roller 46. The first film formation roller 45 and the second film formation roller 46 does not follow the rotation of 46 and is stored at a predetermined position.
The vacuum chamber 60 maintains the decompressed state by sealing the delivery roller 40, the transport rollers 41 to 44, the first and second film forming rollers 45 and 46, and the take-up roller 47.
The pressure (vacuum degree) in the vacuum chamber 60 can be appropriately adjusted according to the type of source gas. The pressure in the film formation space S is preferably in the range of 0.1 to 50 Pa. When plasma CVD is used as a low pressure plasma CVD method for the purpose of suppressing a gas phase reaction, it is usually within a range of 0.1 to 100 Pa.

The vacuum pump 70 is communicably connected to the control unit 71 and appropriately adjusts the pressure in the vacuum chamber 60 in accordance with a command from the control unit 71.
The control unit 71 controls each component of the film forming apparatus 400. The controller 71 is connected to the drive motors of the feed roller 40 and the take-up roller 47, and adjusts the conveyance speed of the base material 81a by controlling the rotation speed of these drive motors. Moreover, the conveyance direction of the base material 81a is changed by controlling the rotation direction of the drive motor.
The controller 71 is communicably connected to a film forming gas supply mechanism (not shown), and controls the supply amount of each component gas of the film forming gas.
The control unit 71 is communicably connected to the plasma generating power source 49 and controls the output voltage and output frequency of the plasma generating power source 49.
Further, the control unit 71 is connected to the vacuum pump 70 so as to be communicable, and controls the vacuum pump 70 so as to maintain the inside of the vacuum chamber 60 in a predetermined reduced pressure atmosphere.

The control unit 71 includes a CPU (Central Processing Unit), a HDD (Hard Disk Drive), a RAM (Random Access Memory), and a ROM (Read Only Memory).
The HDD stores a software program describing a procedure for controlling each component of the film forming apparatus 100 to realize a method for producing a gas barrier film. When the power of the film forming apparatus 400 is turned on, the software program is loaded into the RAM and sequentially executed by the CPU. The ROM stores various data and parameters used when the CPU executes the software program.

When forming a gas barrier layer using the film forming apparatus 400 described above, the film forming step of the gas barrier layer is performed by transporting the resin base material 81a in the forward direction and the reverse direction and reciprocating the film forming space S. It is preferable to repeat several times.
As a result, a plurality of gas barrier layers are formed on the resin base material 81a. The gas barrier layer is a film containing silicon, oxygen, and carbon. The carbon distribution curve showing the relationship between the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer and the atomic ratio of carbon to the total amount of silicon atoms, oxygen atoms, and carbon atoms is substantially continuous. And has at least one extreme value. By determining the composition of the gas barrier layer so as to satisfy this condition, a gas barrier layer having sufficient gas barrier properties can be formed.
The details of the relationship between the composition of the gas barrier layer and the gas barrier property obtained by the film forming apparatus and the details of the carbon distribution curve are omitted because they are well known.

[Method for producing gas barrier film]
The method for producing a gas barrier film according to the present invention is a resin base material in which the surface specific resistance of the surface opposite to the surface on which the gas barrier layer is formed is in the range of 1 × 10 ^{7 to} 5 × 10 ¹² Ω / □. The gas barrier layer is formed by applying light energy by vacuum ultraviolet irradiation to a layer containing polysilazane formed by applying a polysilazane compound on one surface of the resin substrate.
The irradiation with the vacuum ultraviolet rays is preferably performed in a nitrogen atmosphere.
Moreover, when providing a conductive layer in a resin base material, after forming a conductive layer in a resin base material beforehand, a gas barrier layer is formed.
In addition, in order to form a gas barrier layer, after apply | coating and drying the coating liquid containing a polysilazane compound on one surface of a resin base material, according to the shape of a base material, the vacuum ultraviolet-ray shown in FIG. The gas barrier layer may be formed by performing irradiation, or by a roll-to-roll method shown in FIG. 2, a step of applying and drying a coating liquid containing a polysilazane compound and a vacuum ultraviolet ray irradiation step are performed. A gas barrier layer may be formed.

[Electronic device]
The gas barrier film according to the present invention can be preferably used for an electronic device whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air. In particular, it is preferably used when at least one of the layers constituting the electronic device is a layer formed by a vapor deposition method in a vacuum.

  Examples of the electronic device include electronic devices such as an organic electroluminescence element (organic EL element), a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, and a solar cell (PV). From the viewpoint that the effect of the present invention can be obtained more efficiently, it is preferably used for an organic EL device or a solar cell, and particularly preferably used for an organic EL device.

The gas barrier film of the present invention can also be used for device membrane sealing. That is, it is a method of providing the gas barrier film of the present invention on the surface of the device itself as a support. The device may be covered with a protective layer before providing the gas barrier film.
The gas barrier film of the present invention can also be used as a device substrate or a film for sealing by a solid sealing method. The solid sealing method is a method in which after a protective layer is formed on a device, an adhesive layer and a gas barrier film are stacked and cured. Although there is no restriction | limiting in particular in an adhesive agent, A thermosetting epoxy resin, a photocurable acrylate resin, etc. are illustrated.

Hereinafter, an organic EL element and an organic EL panel using the same will be described as an example of a specific electronic device.
Although the preferable specific example of the layer structure of an organic EL element is shown below, this invention is not limited to these.
(1) Anode / light emitting layer / cathode (2) Anode / hole transport layer / light emitting layer / cathode (3) Anode / light emitting layer / electron transport layer / cathode (4) Anode / hole transport layer / light emitting layer / electron Transport layer / cathode (5) Anode / anode buffer layer (hole injection layer) / hole transport layer / light emitting layer / electron transport layer / cathode buffer layer (electron injection layer) / cathode

(anode)
As the anode (transparent electrode) in the organic EL element, an electrode material made of a metal, an alloy, an electrically conductive compound or a mixture thereof having a high work function (4 eV or more) is preferably used.
Specific examples of such electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO. Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) capable of forming a transparent conductive film may be used.
For the anode, these electrode materials may be formed as a thin film by a method such as vapor deposition or sputtering, and the thin film may be formed into a desired pattern by photolithography, or when the pattern accuracy is not so necessary ( The pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered.

  When light emission is taken out from the anode, it is desirable that the transmittance be larger than 10%. The sheet resistance as the anode is preferably several hundred Ω / □ or less. Moreover, although the film thickness of an anode is based also on material, it is normally chosen in the range of 10-1000 nm, Preferably it is in the range of 10-200 nm.

(cathode)
As the cathode in the organic EL element, a material having a small work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used.
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 point of durability against electron injection and oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function 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 suitable as the cathode.

The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
The sheet resistance as a cathode is preferably several hundred Ω / □ or less. The thickness of the cathode is usually selected within the range of 10 nm to 5 μm, preferably within the range of 50 to 200 nm. In order to transmit the emitted light, if either the anode or the cathode of the organic EL element is transparent or translucent, the light emission luminance is improved, which is convenient.

  Moreover, after manufacturing the said metal quoted by description of the cathode with a film thickness of 1-20 nm, the transparent transparent or semi-transparent cathode is produced by producing the electroconductive transparent material quoted by description of the anode on it. By applying this, an element in which both the anode and the cathode are transmissive can be manufactured.

(Injection layer: electron injection layer, hole injection layer)
The injection layer includes an electron injection layer and a hole injection layer, and an electron injection layer and a hole injection layer are provided as necessary, between the anode and the light emitting layer or the hole transport layer, and between the cathode and the light emitting layer or the electron. It exists between the transport layers.
An injection layer is a layer provided between an electrode and an organic layer in order to reduce drive voltage and improve light emission luminance. “Organic EL element and its forefront of industrialization (issued by NTT Corporation on November 30, 1998) 2), Chapter 2, “Electrode Materials” (pages 123 to 166) in detail, and includes a hole injection layer (anode buffer layer) and an electron injection layer (cathode buffer layer).

  The details of the anode buffer layer (hole injection layer) are also described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069, and the like. Examples thereof include a phthalocyanine buffer layer typified by phthalocyanine, an oxide buffer layer typified by vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.

  Details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium Metal buffer layer typified by aluminum and aluminum, alkali metal compound buffer layer typified by lithium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, oxide buffer layer typified by aluminum oxide, etc. Is mentioned. The buffer layer (injection layer) is preferably a very thin film, and depending on the material, the film thickness is preferably in the range of 0.1 nm to 5 μm.

(Light emitting layer)
The light emitting layer in the organic EL element is a layer that emits light by recombination of electrons and holes injected from the electrode (cathode, anode) or electron transport layer or hole transport layer, and the light emitting portion is the light emitting layer. It may be in the layer or the interface between the light emitting layer and the adjacent layer.
The light emitting layer of the organic EL device preferably contains the following dopant compound (light emitting dopant) and host compound (light emitting host). Thereby, the luminous efficiency can be further increased.

(Luminescent dopant)
There are two types of luminescent dopants: a fluorescent dopant that emits fluorescence and a phosphorescent dopant that emits phosphorescence.
Representative examples of fluorescent dopants include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes. Stilbene dyes, polythiophene dyes, rare earth complex phosphors, and the like.
As a typical example of the phosphorescent dopant, preferably a complex compound containing a metal of Group 8, Group 9, or Group 10 in the periodic table of elements, more preferably an iridium compound or an osmium compound, Of these, iridium compounds are the most preferred. The light emitting dopant may be used by mixing a plurality of kinds of compounds.

(Light emitting host)
A light-emitting host (also simply referred to as a host) means a compound having the largest mixing ratio (mass) in a light-emitting layer composed of two or more compounds. For other compounds, “dopant compound ( Simply referred to as a dopant). " For example, if the light emitting layer is composed of two types of compound A and compound B and the mixing ratio is A: B = 10: 90, compound A is a dopant compound and compound B is a host compound. Furthermore, if a light emitting layer is comprised from 3 types of compound A, compound B, and compound C, and the mixing ratio is A: B: C = 5: 10: 85, compound A and compound B are dopant compounds, Compound C is a host compound.

  The light emitting host is not particularly limited in terms of structure, but is typically a basic skeleton such as a carbazole derivative, a triarylamine derivative, an aromatic borane derivative, a nitrogen-containing heterocyclic compound, a thiophene derivative, a furan derivative, or an oligoarylene compound. Or a carboline derivative or a diazacarbazole derivative (herein, a diazacarbazole derivative is one in which at least one carbon atom of the hydrocarbon ring constituting the carboline ring of the carboline derivative is substituted with a nitrogen atom) And the like). Of these, carboline derivatives, diazacarbazole derivatives and the like are preferably used.

The light emitting layer can be formed by depositing the above compound by a known thinning method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, or an ink jet method.
The thickness of the light emitting layer is not particularly limited, but is usually selected within the range of 5 nm to 5 μm, preferably within the range of 5 to 200 nm.
The light emitting layer may have a single layer structure in which the dopant compound and the host compound are one type or two or more types, or may have a laminated structure in which a plurality of layers having the same composition or different compositions are formed.

(Hole transport layer)
The hole transport layer is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer. The hole transport layer can be provided as a single layer or a plurality of layers.
The hole transport material has any of hole injection or transport and electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers. The above-mentioned materials can be used as the hole transport material, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound. Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.

  The hole transport layer is formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. Can do. Although there is no restriction | limiting in particular about the film thickness of a positive hole transport layer, Usually, about 5 nm-5 micrometers, Preferably it exists in the range of 5-200 nm. The hole transport layer may have a single layer structure composed of one or more of the above materials.

(Electron transport layer)
The electron transport layer is made of an electron transport material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer. The electron transport layer can be provided as a single layer or a plurality of layers.
The electron transport material only needs to have a function of transmitting electrons injected from the cathode to the light emitting layer, and the material can be selected and used from conventionally known compounds. Examples include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, and the like.
Furthermore, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material.
Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
In addition, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq ₃ ), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) Aluminum, tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), etc., and the central metals of these metal complexes are In, Mg Metal complexes replaced with Cu, Ca, Sn, Ga, or Pb can also be used as electron transport materials. In addition, metal-free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transport material. Similarly to the hole injection layer and the hole transport layer, an inorganic semiconductor such as n-type-Si or n-type-SiC can also be used as the electron transport material.

  The electron transport layer can be formed by thinning the electron transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. . Although there is no restriction | limiting in particular about the film thickness of an electron carrying layer, Usually, about 5 nm-5 micrometers, Preferably it exists in the range of 5-200 nm. The electron transport layer may have a single layer structure composed of one or more of the above materials.

(Method for producing organic EL element)
Here, as an example of the organic EL element, a method for manufacturing an organic EL element including an anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode will be described.
First, a desired electrode material, for example, a thin film made of an anode material is formed on a gas barrier film so as to have a film thickness of 1 μm or less, preferably in the range of 10 to 200 nm, for example, vapor deposition, sputtering, plasma CVD, etc. Thus, an anode is produced.

Next, an organic compound thin film of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, which are organic EL element materials, is formed thereon.
As a method for forming this organic compound thin film, there are a vapor deposition method, a wet process (spin coating method, casting method, ink jet method, printing method), etc., but a homogeneous film is easily obtained and pinholes are not easily generated. From the point of view, the vacuum deposition method, the spin coating method, the ink jet method, and the printing method are particularly preferable. Further, different film formation methods may be applied for each layer.

  In particular, in the present invention, it is preferable to form a film by a vacuum deposition method. If the gas barrier film has uneven distribution of static electricity when it is formed by vacuum deposition in vacuum, the effect of light emission unevenness is likely to occur.However, by using the gas barrier film according to the present invention, it can be formed by vacuum deposition. Even when the film is formed, uneven light emission is good.

When a vapor deposition method is employed for film formation, the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 to 450 ° C., a vacuum degree of 10 ⁻⁶ to 10 ⁻² Pa, and a vapor deposition rate of 0.01 to It is desirable to select appropriately within the range of 50 nm / second, substrate temperature −50 to 300 ° C., film thickness 0.1 nm to 5 μm, preferably 5 to 200 nm.

After these layers are formed, a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably in the range of 50 to 200 nm. A desired organic EL element is obtained by providing.
The organic EL device is preferably manufactured from the anode and the hole injection layer to the cathode consistently by a single evacuation, but may be taken out halfway and subjected to different film forming methods. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere. In addition, it is also possible to reverse the production order and produce the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode in this order.
When a DC voltage is applied to a multicolor display device (organic EL panel) provided with the organic EL element thus obtained, a voltage of about 2 to 40 V is applied with the positive polarity of the anode and the negative polarity of the cathode. Then luminescence can be observed. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

  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 display of "part" or "%" is used in an Example, unless otherwise indicated, "mass part" or "mass%" is represented.

[Resin substrate]
<Preparation of substrate 1>
A 100 μm thick polyethylene terephthalate film (Lumirror (registered trademark) (U48) manufactured by Toray Industries, Inc.) with easy adhesion treatment on both sides is opposite to the surface on which the gas barrier layer is formed. A clear hard coat layer having a block function was formed. That is, a UV curable resin (manufactured by Aika Kogyo Co., Ltd., product number: Z731L) was applied so as to have a dry film thickness of 0.5 μm, and then dried at 80 ° C. Then, using a high-pressure mercury lamp in the air. It was cured under conditions of irradiation energy 0.5 J / cm ^2.
Next, a clear hard coat layer having a thickness of 2 μm was formed on the surface of the base material on the side where the gas barrier layer was to be formed as follows. A UV curable resin OPSTAR (registered trademark) Z7527 manufactured by JSR Corporation was applied to a dry film thickness of 2 μm, dried at 80 ° C., and then irradiated with a high-pressure mercury lamp in air. Curing was performed under the condition of 0.5 J / cm ² . In this way, a substrate 1 was obtained. Moreover, the base material 1 produced the sheet form and the roll-shaped thing, respectively. In addition, the base material 1 is a base material used when there is no electroconductive layer of the following Table 3.

<Preparation of base material 2>
A clear hard coat layer having a thickness of 2 μm was formed on the surface of the substrate on which the gas barrier layer was to be formed as follows. A UV curable resin OPSTAR (registered trademark) Z7527 manufactured by JSR Corporation was applied to a dry film thickness of 2 μm, dried at 80 ° C., and then irradiated with a high-pressure mercury lamp in air. Curing was performed under the condition of 0.5 J / cm ² . In this way, a substrate 2 was obtained. Moreover, the base material 2 also produced the sheet form and the roll-shaped thing, respectively.

[Formation of conductive layer]
<Formation of conductive layer>
On the surface opposite to the surface on which the clear hard coat layer of the substrate 2 is formed, the following conductive layer coating solution is applied so that the dry film thickness is 0.6 μm, and then dried at 80 ° C., and then air Then, curing was performed using a high-pressure mercury lamp under the condition of an irradiation energy amount of 0.5 J / cm ² . In this way, a conductive layer was formed on the substrate.
(Conductive layer coating solution a)
The following materials were sufficiently mixed with stirring and filtered to obtain a coating solution.
Celnax CX-S501M (solid content 50% by mass, methanol dispersion): manufactured by Nissan Chemical Industries, Ltd.
100 parts by mass Silica sol MA-ST-ZL (solid content 30% by mass, methanol dispersion): manufactured by Nissan Chemical Industries, Ltd.
10 parts by mass
KAYARAD DPHA (polyfunctional (meth) acrylate monomer): Nippon Kayaku Co., Ltd.
30 parts by mass
IRGACURE 184: 3 parts by mass, manufactured by BASF Japan
BYK3550: 1 part by mass produced by Big Chemie 291 parts by mass of propylene glycol monomethyl ether

<Formation of conductive layer a>
In the formation of the conductive layer (a), a conductive layer (a) was formed in the same manner as the formation of the conductive layer (a), except that the dry film thickness was 1.0 μm.

<Formation of conductive layer C>
In the formation of the conductive layer (a), the conductive layer (a) was formed in the same manner as the conductive layer (a) except that the conductive layer coating liquid (a) was used instead of the conductive layer coating liquid (a). did.
(Conductive layer coating solution C)
The following materials were sufficiently mixed with stirring and filtered to obtain a coating solution.
Celnax CX-S501M (solid content 50% by mass, methanol dispersion): manufactured by Nissan Chemical Industries, Ltd.
100 parts by mass Silica sol MA-ST-ZL (solid content 30% by mass, methanol dispersion): manufactured by Nissan Chemical Industries, Ltd.
10 parts by mass
KAYARAD DPHA (polyfunctional (meth) acrylate monomer): Nippon Kayaku Co., Ltd.
25 parts by mass
IRGACURE 184: BASF Japan Ltd .: 3 parts by mass
BYK3550: manufactured by Big Chemie: 1 part by mass propylene glycol monomethyl ether 271 parts by mass

<Formation of conductive layer D>
In the formation of the conductive layer (a), a conductive layer (d) was formed in the same manner as the conductive layer (a) except that the conductive layer coating liquid (a) was used instead of the conductive layer coating liquid (a). did.
(Conductive layer coating solution)
The following materials were sufficiently mixed with stirring and filtered to obtain a coating solution.
Celnax CX-S501M (solid content 50% by mass, methanol dispersion): manufactured by Nissan Chemical Industries, Ltd.
100 parts by mass Silica sol MA-ST-ZL (solid content 30% by mass, methanol dispersion): manufactured by Nissan Chemical Industries, Ltd.
15 parts by mass
KAYARAD DPHA (polyfunctional (meth) acrylate monomer): Nippon Kayaku Co., Ltd.
25 parts by mass
IRGACURE 184: 3 parts by mass, manufactured by BASF Japan
BYK3550: manufactured by Big Chemie: 1 part by mass propylene glycol monomethyl ether 273 parts by mass

<Formation of conductive layer E>
In the formation of the conductive layer C, a conductive layer A was formed in the same manner as the formation of the conductive layer C, except that the coating was applied so that the dry film thickness was 1.0 μm.

<Formation of conductive layer>
In the formation of the conductive layer (a), the conductive layer coating liquid (a) was replaced by the following conductive layer coating liquid (a), except that the conductive layer coating liquid was applied so that the dry film thickness was 1.0 μm. A conductive layer was formed in the same manner as the formation of the layer a.
(Conductive layer coating solution)
The following materials were sufficiently mixed with stirring and filtered to obtain a coating solution.
Celnax CX-S501M (solid content 50% by mass, methanol dispersion): manufactured by Nissan Chemical Industries, Ltd.
100 parts by mass
KAYARAD DPHA (polyfunctional (meth) acrylate monomer): Nippon Kayaku Co., Ltd.
15 parts by mass
IRGACURE 184: 2 parts by mass, manufactured by BASF Japan
BYK3550: 1 part by mass produced by Big Chemie, Inc. 222 parts by mass of propylene glycol monomethyl ether

<Formation of conductive layer>
In the formation of the conductive layer (a), the conductive layer coating liquid (a) was replaced with the conductive layer coating liquid described below, and the conductive layer was coated except that the dry film thickness was 1.0 μm. A conductive layer was formed in the same manner as the formation of the layer a.
(Conductive layer coating solution)
The following materials were sufficiently mixed with stirring and filtered to obtain a coating solution.
Celnax CX-S501M (solid content 50% by mass, methanol dispersion): manufactured by Nissan Chemical Industries, Ltd.
100 parts by mass Silica particle dispersion with an average particle size of 200 nm (solid content 30% by mass, methanol dispersion)
15 parts by mass
KAYARAD DPHA (polyfunctional (meth) acrylate monomer): Nippon Kayaku Co., Ltd.
25 parts by mass
IRGACURE 184: 3 parts by mass, manufactured by BASF Japan
BYK3550: manufactured by Big Chemie: 1 part by mass propylene glycol monomethyl ether 273 parts by mass

[Formation of gas barrier layer]
<Formation of gas barrier layers A and B>
On the base material 1 or the clear hard coat layer of the base material 2 obtained above, a gas barrier layer A or B was formed by the following vacuum plasma CVD method.
As shown in FIG. 4, a roll-to-roll type CVD film forming apparatus of the type in which two film forming apparatuses in FIG. 3 are connected (including a first film forming unit 501 and a second film forming unit 502) is used. It was. In the film forming apparatus of FIG. 4, the first film forming unit 501 is the same as the film forming apparatus of FIG. 3, and each component is given the same reference numeral. The second film forming unit 502 has basically the same configuration as the film forming apparatus of FIG. About the same component, "-1 (hyphen-1)" is attached | subjected to the code | symbol similar to the code | symbol of FIG.
That is, in FIG. 4, the base material 81d formed by the first film forming unit 501 is further formed by the film formation roller 45-1 to form the resin base material 81e, and further formed by the film formation roller 46-1. The resin base material 81 c after film formation is wound around the winding roller 47.
Using the film forming apparatus shown in FIG. 4, the effective film forming width is set to 1000 mm, and the film forming conditions are as follows: transfer speed, source gas of each of the first film forming part and the second film forming part (hexamethyldisiloxane (HMDSO ) Supply amount, oxygen gas supply amount, degree of vacuum, applied power, and number of film formations (number of device passes) The second pass is transported in the direction of rewinding the substrate. However, even when the pass directions are different, the first film formation unit 501 is the first film formation unit that passes through, and the second film formation unit 502 is the next film formation unit that passes.
As other conditions, the power frequency was 84 kHz, and the temperature of the film forming roller was all 30 ° C. The film thickness of the gas barrier layer was determined by cross-sectional TEM observation.
The film formation conditions for the gas barrier layer A and the gas barrier layer B are shown in Table 1 below.

<Formation of gas barrier layer C>
A gas barrier layer C was formed on the substrate 1 obtained above or on the clear hard coat layer of the substrate 2 by a sputtering method.
Specifically, a batch type magnetron sputtering apparatus was used, and polycrystalline SiO ₂ was used as a target. Argon gas and oxygen gas were introduced to form a SiO ₂ film having a thickness of 300 nm.

<Formation of gas barrier layer D>
A coating liquid containing a polysilazane compound is applied on the base material 1 obtained above or on the clear hard coat layer of the base material 2 or on the first or second gas barrier layer of the base material 1. Then, the gas barrier layer D was formed by applying a modification process by applying energy.
As the reformer, the apparatus shown in FIG. 1 was used when the substrate 1 or 2 was a sheet, and the apparatus shown in FIG. 2 was used when it was a roll.
Specifically, as a coating solution, a dibutyl ether solution containing 20% by mass of perhydropolysilazane (manufactured by AZ Electronic Materials Co., Ltd., NN120-20) and an amine catalyst (N, N, N ′, N′-tetramethyl) -1,6-diaminohexane (TMDAH)) perhydropolysilazane 20 mass% dibutyl ether solution (manufactured by AZ Electronic Materials Co., Ltd., NAX120-20) was mixed at a ratio of 4: 1 (mass ratio) Furthermore, it was diluted with dibutyl ether to adjust the dry film thickness, and the solid content concentration was adjusted to 10% by mass to obtain a coating solution.

(In the case of sheet-like substrate)
On the base material 1 obtained above, or on the clear hard coat layer of the base material 2, or on the first or second gas barrier layer of the base material 1, the above coating solution is applied by spin coating. It apply | coated so that it might become a dry film thickness shown in Table 2, and it dried for 2 minutes at 80 degreeC. Next, the dried coating film is subjected to a vacuum ultraviolet ray irradiation treatment using an Xe excimer lamp having a wavelength of 172 nm under the conditions of an oxygen concentration of 0.1% and an irradiation energy of 3 J / cm ² to form a gas barrier layer D. did.

(In the case of a roll base)
On the base material 1 obtained above or on the clear hard coat layer of the base material 2, or on the first or second gas barrier layer of the base material 1, the coating solution is applied using a die coater. Applied. After drying at 80 ° C., using a Xe excimer lamp with a wavelength of 172 nm, vacuum ultraviolet irradiation treatment was performed under conditions of an oxygen concentration of 0.1% and an irradiation energy of 3 J / cm ² to form a gas barrier layer D.

<Formation of gas barrier layer E>
A gas barrier layer E was formed by applying a coating liquid containing a polysilazane compound on the first gas barrier layer of the base material 2 obtained above and applying energy to the gas barrier layer E. In the case of the sheet-like base material for forming the gas barrier layer D, the gas barrier layer E is the same as the gas barrier layer E except that a vacuum ultraviolet ray irradiation treatment was performed under the condition of irradiation energy of 6 J / cm ^2. Formed.

The film forming method, film forming conditions and film thickness of the gas barrier layers A to E are shown in Table 2.

  As described above, Samples 1 to 14 in which the hard coat layer, the conductive layer, and the gas barrier layer were formed on the substrate were obtained. Table 3 below shows conditions of Samples 1 to 14 for the substrate, the hard coat layer, the conductive layer, and the gas barrier layer.

[Evaluation]
(1) Surface specific resistance on the surface opposite to the gas barrier layer Measured using a Hiresta UP manufactured by Mitsubishi Chemical Analytech. A standard ring probe (URS) was used for the measurement. The measurement voltage was set to 1000 V, and each sample was measured at three points with different measurement positions, and the average value was defined as the surface specific resistance value.

(2) Surface roughness (Ra and Rz) of the surface opposite to the gas barrier layer
A non-contact three-dimensional surface shape roughness meter manufactured by Veeco: Wyko NT9300 was used, and measurement was performed at a PSI mode and a measurement magnification of 40 times. The measurement range in one measurement was 159.2 μm × 119.3 μm, and the measurement point was 640 × 480. Tilt correction was performed on the measurement. Ra and Rz are automatically calculated. The measurement position was changed and five points were measured, and the average values of both Ra and Rz were obtained.

(3) Cross-cut adhesion on the surface opposite to the gas barrier layer Based on JIS-K5600 (cross-cut method), the number of cells not peeled in 100 cells was measured and ranked from the following viewpoints.
5: 96-100
4: 90-95
3: 80-89
2: 70-79
1:69 or less

(4) Resistance to steel wool on the surface opposite to the gas barrier layer While pressing steel wool at a pressure of 100 g / cm ² , a 10 reciprocal sliding test was performed, and the degree of scratches produced was visually observed and Rank by viewpoint.
5: No scratch 4: 1 to 2 scratches 3: 3 to 10 scratches 2: 11 to 50 scratches 1: 51 or more scratches

(5) Gas barrier property The gas barrier property with respect to permeation | transmission of the water vapor | steam of the obtained sample was measured by 38 degreeC and 100% RH atmosphere by the water vapor permeability measuring apparatus (brand name: Aquatran MODEL1 made by Mocon). . In Table 3, the water vapor permeability is abbreviated as WVTR.

(6) Initial Dark Spot of Organic EL Device Four organic EL devices each having a light emitting area of 2.2 inches (diagonal line) size were produced as follows. Then, after storing for 12 hours in an environment of 85 ° C. and 85% RH, the number of generated dark spots / device of 4 devices having a circle-equivalent diameter of 200 μm or more was determined for the generated dark spots, and was ranked from the following viewpoints 5: 0-4
4: 5-10 pieces 3: 11-20 pieces 2: 21-40 pieces 1:41 pieces <Creation of an organic EL device>
Using the gas barrier film obtained in each of the examples and comparative examples, a bottom emission type organic electroluminescence device (organic EL device) having a light emitting region size of 2.2 inches (diagonal line) was formed by the following method. Produced.
(Formation of underlayer and first electrode)
The gas barrier film is fixed to a substrate holder of a commercially available vacuum deposition apparatus, the following compound 118 is placed in a resistance heating boat made of tungsten, and these substrate holder and heating boat are placed in the first vacuum chamber of the vacuum deposition apparatus. Attached. Moreover, silver (Ag) was put into the resistance heating boat made from tungsten, and it attached in the 2nd vacuum chamber of a vacuum evaporation system.
Next, after depressurizing the first vacuum chamber of the vacuum deposition apparatus to 4 × 10 ⁻⁴ Pa, the heating boat containing the compound 118 was energized and heated, and the deposition rate was 0.1 nm / second to 0.2 nm / second. The underlayer of the first electrode was provided with a thickness of 10 nm.
Next, the base material formed up to the underlayer was transferred to the second vacuum chamber while being vacuumed, and the second vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, and then the heating boat containing silver was energized and heated. This formed the 1st electrode which consists of silver with a thickness of 8 nm within the range of vapor deposition rate 0.1-0.2 nm / sec.
(Formation of organic functional layer to second electrode)
Subsequently, the pressure was reduced to a vacuum degree of 1 × 10 ⁻⁴ Pa using a commercially available vacuum vapor deposition apparatus, and then the following compound HT-1 was vapor-deposited at a vapor deposition rate of 0.1 nm / second while moving the base material. A hole transport layer (HTL) was provided.
Next, compound A-3 (blue light emitting dopant), compound A-1 (green light emitting dopant), compound A-2 (red light emitting dopant) and compound H-1 (host compound), compound A-3 having a film thickness The vapor deposition rate is varied depending on the location so that the concentration is linearly 5 to 35% by mass, and the concentration of Compound A-1 and Compound A-2 is 0.2% by mass without depending on the film thickness. The vapor deposition rate is 0.0002 nm / second, and the compound H-1 is co-deposited to a thickness of 70 nm by changing the vapor deposition rate depending on the location so that the compound H-1 is 64.6 to 94.6% by mass to form a light emitting layer. did.
Thereafter, the following compound ET-1 was deposited to a thickness of 30 nm to form an electron transport layer, and potassium fluoride (KF) was further formed to a thickness of 2 nm. Furthermore, aluminum 110nm was vapor-deposited and the 2nd electrode was formed.
In addition, the said compound 118, compound HT-1, compound A-1 to 3, compound H-1, and compound ET-1 are the compounds shown below.

(7) Luminous unevenness of organic EL device The light emitting state after storage for 12 hours in an 85 ° C. and 85% RH environment was visually observed, and the state of the uneven light emission was ranked from the following viewpoints. At this time, light emission was performed under the condition of 0.2 V lower than the reference light emission voltage, and light emission unevenness was emphasized.
5: No light emission unevenness in all 4 sheets 4: Weak light emission unevenness in 1 to 2 out of 4 sheets 3: Weak light emission unevenness in all 4 sheets 2: Strong light emission unevenness in 1 to 2 out of 4 sheets 1: Both in 4 sheets Strong emission unevenness

  From the results shown in Table 3, the sample of the present invention has a very high gas barrier property compared to the sample of the comparative example, and when used as a substrate of an organic EL device, the occurrence of dark spots is small. And it is recognized that uniform light emission is obtained.

DESCRIPTION OF SYMBOLS 1 Apparatus chamber 2 Excimer lamp 3 Lamp holder 4 Sample stage 5 Resin base material 6 Light-shielding plate 100 Vacuum ultraviolet irradiation apparatus 14 Resin base material 15 Resin base material and coating films 22, 23, 24, 26, 27, 28 Roller 29 Die coater 30 Dryer 31 Housing 32 Coating film forming means 33 Coating film modifying means L1 to L30 Excimer lamps T1 to T32 Temperature controller 40 Delivery rollers 41, 42, 43, 44, 42-1, 43-1 Conveying roller 45, 45-1 1st film-forming roller 46, 46-1 2nd film-forming roller 47 Winding roller 48, 48-1 Gas supply pipe 49, 49-1 Power supply 50, 51, 50-1, 51-1 for plasma generation Magnetic field generator 60 Vacuum chamber 70, 70-1 Vacuum pump 71 Controller 81a, 81b, 81c, 81d, 81e Resin base material 400, 50 0 Film forming apparatus 501 First film forming unit 502 Second film forming unit

Claims (6)

A gas barrier film having one or more gas barrier layers on one surface of a resin substrate,
At least one of the gas barrier layers is a layer formed by applying energy to a layer containing polysilazane, and
A gas barrier film characterized in that the surface specific resistance of the other surface of the resin substrate is in the range of 1 × 10 ^{7 to} 5 × 10 ¹² Ω / □.   The surface roughness Ra of the other surface of the resin base material is in the range of 1.0 to 3.0 nm, and the surface roughness Rz is in the range of 10 to 30 nm. Item 6. The gas barrier film according to Item 1. A method for producing a gas barrier film according to claim 1 or 2, wherein the gas barrier film is produced.
The method for producing a gas barrier film, wherein the application of energy is application of light energy by irradiation with vacuum ultraviolet rays.   The method for producing a gas barrier film according to claim 3, wherein the irradiation with the vacuum ultraviolet ray is performed in a nitrogen atmosphere.   An electronic device comprising the gas barrier film according to claim 1.   The electronic device according to claim 5, wherein at least one of the layers constituting the electronic device is a layer formed by a vapor deposition method in a vacuum.

Images