JPWO2015029859A1 - Gas barrier film and method for producing gas barrier film - Google Patents

Abstract

An object of the present invention is to provide a gas barrier film having good gas barrier performance, color stability and high transparency, and having excellent durability under a high temperature and high humidity environment, and a method for producing the same. The gas barrier film of the present invention has a gas barrier layer on a resin substrate, and contains a color tone adjusting agent and a compound having a metal-oxygen bond capable of holding the color adjusting agent on the gas barrier layer. It has the above-mentioned color tone adjustment layer.

Description

  The present invention relates to a gas barrier film and a method for producing the gas barrier film. More specifically, the present invention relates to a gas barrier film having good gas barrier performance and color stability, high transparency, and excellent durability under a high temperature and high humidity environment, and a method for producing the same.

  Conventionally, various studies have been made on a film having a property of blocking permeation of water vapor and oxygen, that is, a so-called gas barrier property (hereinafter referred to as “gas barrier film”). A gas barrier film is generally a gas barrier layer (hereinafter simply referred to as “a thin film containing a metal oxide such as aluminum oxide, magnesium oxide, silicon oxide, etc.) on the surface of a resin substrate or resin film composed of a thermoplastic resin or the like. Also referred to as a “barrier layer”).

  Such a gas barrier film has a function of suppressing permeation of various gases such as water vapor and oxygen, and is widely used for packaging an article that requires blocking of various gases. In addition to the above packaging applications, it is also used for sealing member applications for sealing electronic devices such as solar cells, liquid crystal display elements, and organic EL elements in order to prevent deterioration due to various gases. A gas barrier film using a resin film as a base material has superior flexibility compared to the case of using a glass substrate, and is suitable for production in a roll-to-roll system, and it is lightweight and easy to handle electronic devices. This is also advantageous.

  In the production of such a gas barrier film, as a film forming method used for forming a gas barrier layer, mainly a vapor deposition method, a plasma CVD method (chemical vapor deposition method), a sputtering method are used. For example, a method of forming a gas barrier layer on a substrate such as a film is known.

Among these methods, a plasma CVD method is used to form a silicon oxide film (SiO _x ) on a film substrate, a SiO _x N _y film having a nitrogen atom N or a carbon atom C in the silicon oxide film composition, or SiO _x C. A technique for producing a gas barrier film having gas barrier properties by a gas barrier film made of a _z film is known.

However, the method for producing a gas barrier film by the roll-to-roll method is based on contact between the film-forming surface of the gas barrier layer and the surface of a conveying member such as a conveying roller, or contact between the film-forming surface and the back surface of the film during winding The SiO _x N _y film and the SiO _x C _z film as described above have a relatively small advantage over the SiO ₂ film in that the gas barrier property is deteriorated due to damage or the like. However, when the gas barrier layer is formed on the resin film substrate, for example, in the formation method using the plasma CVD method, the manufactured gas barrier film is easily colored, and it is possible to achieve both gas barrier properties and transparency. It was difficult.

  With respect to the problem that the resin film substrate is colored when the gas barrier layer is formed as described above, for the purpose of adjusting the color tone, a technique for containing a fluorescent brightener or ultraviolet absorption in the resin film substrate is disclosed ( For example, see Patent Document 1.) In the method described in Patent Document 1, the initial color tone of the resin film constituting the gas barrier film before the formation of the gas barrier layer can be adjusted. However, color deterioration due to heat during CVD film formation, UV absorbers and fluorescent whitening. There is a problem of bleed-out, which is a phenomenon that the agent oozes out on the surface of the resin film substrate.

  As a technique for adjusting the color tone of the gas barrier film without causing problems due to the low heat resistance of the resin film substrate as described above, a silicon oxide vapor deposition layer is provided as a gas barrier layer, and an organosilicon compound and a surface thereof are provided. A gas barrier in which one or more silicon-containing hydrocarbon layers are provided by plasma enhanced chemical vapor deposition using chain hydrocarbons as a monomer gas for vapor deposition, thereby doping carbon atoms in the silicon oxide vapor deposition layer The technique which improves the transparency of a gas barrier film with the manufacturing method of a film is proposed (for example, refer patent document 2).

  However, in the method proposed in Patent Document 2, a plasma chemical vapor deposition method is used for color adjustment, so that a CVD multilayer film forming process is required, and it is difficult to achieve both productivity.

In addition, instead of the plasma chemical vapor deposition method, a technique is known in which a protective film in which an adhesive layer containing a fluorescent brightening agent is laminated on a base material is bonded onto a gas barrier layer by a simple wet coating method. (For example, refer to Patent Document 3)
In this case, since the adhesive layer containing the optical brightener is disposed outside the gas barrier layer against the outside air, it is not completely protected from water vapor, oxygen, etc. -After being exposed for a long time in a high-humidity environment, the color tone changed and the quality deteriorated.

JP 2008-195829 A JP2013-121686A Special table 2011-521813 gazette

  The present invention has been made in view of the above problems, and a solution to the problem is a gas having good gas barrier performance, color stability and high transparency, and excellent durability in a high temperature and high humidity environment. It is providing a barrier film and its manufacturing method.

  As a result of intensive studies in view of the above problems, the present inventor has a gas barrier layer on a resin base material, and a metal capable of holding the color tone adjusting agent and the color tone adjusting agent on the gas barrier layer. -It has been found that the above-mentioned problems can be solved by a gas barrier film characterized in that a color tone adjusting layer containing a compound having an oxygen bond is laminated in this order, and the present invention has been completed.

  That is, the above problems are solved by the following means.

  1. Having a gas barrier layer on the resin substrate, and having a color tone adjusting layer containing a compound having a metal-oxygen bond capable of holding the color tone adjusting agent and the color tone adjusting agent on the gas barrier layer. Characteristic gas barrier film.

  2. 2. The gas barrier film according to item 1, wherein the gas barrier layer comprises a vapor deposition film.

  3. 2. The gas barrier film according to item 1, wherein the gas barrier layer comprises a coating film.

  4). 4. The gas barrier film according to item 3, wherein the gas barrier layer is composed of a coating film containing at least polysilazane or a modified product thereof.

  5. 5. The gas barrier film according to any one of items 1 to 4, wherein the color tone adjusting layer is laminated on the gas barrier layer as a coating film.

  6). The gas barrier film according to any one of claims 1 to 5, wherein the color tone adjusting agent contained in the color tone adjusting layer is a fluorescent material.

  7). 7. The gas barrier film according to item 6, wherein the fluorescent substance is an organic fluorescent agent or an inorganic fluorescent agent.

  8). Item 8. The gas barrier film according to Item 6 or 7, wherein the fluorescent material is a blue fluorescent material having a maximum emission wavelength of 500 nm or less.

  9. The compound having a metal-oxygen bond capable of holding the color tone adjusting agent contained in the color tone adjusting layer is a polysilazane or a compound having a polysiloxane structure, and the color tone adjusting layer is the polysilazane or polysiloxane. The gas barrier film according to any one of items 1 to 8, which comprises a coating film containing a compound having a structure.

  10. The pencil hardness (JIS K 5600-5-4) of the surface of the color tone adjusting layer is in the range of HB to 4H, and the gas according to any one of items 1 to 9 Barrier film.

  11. After forming a gas barrier layer on a resin substrate by plasma CVD, a color tone adjustment layer is laminated on the gas barrier layer by a wet coating method using a color tone adjustment layer forming coating solution containing a color tone adjusting agent. And manufacturing a gas barrier film.

  12 A gas barrier layer-forming coating solution containing polysilazane is applied and dried on a resin substrate by a wet coating method to form a thin film containing polysilazane, and the thin film is subjected to a modification treatment to form a gas barrier layer. After forming, a gas barrier film is produced by laminating a color tone adjusting layer by a wet coating method using a coating solution for forming a color tone adjusting layer containing a color tone adjusting agent on the gas barrier layer. A method for producing a barrier film.

  By the above means of the present invention, it is possible to provide a gas barrier film having good gas barrier performance and color tone stability, high transparency, and excellent durability under a high temperature and high humidity environment, and a method for producing the same. .

  It is presumed that the above problem can be solved by the configuration defined in the present invention for the following reason.

  A gas barrier film in which a gas barrier layer is formed on a transparent resin base material is colored yellowish in the resin film as the base material as the barrier becomes higher, and the transparency (visible light transmittance) is increased. descend. By adding a blue (complementary) colorant to cancel the yellow coloration to any of the layers that make up the gas barrier film, the coloration that occurs in the resin film is offset and neutral (neutral) The color tone of the resin film can be maintained, but the gray coloration by yellow + blue is relatively increased, and the transmittance of the resin film is lowered. Deposition of gas barrier film due to heat during deposition, thermal energy application by vacuum ultraviolet light during polysilazane excimer modification treatment, or oxygen or water when stored in a high-temperature or high-humidity environment after device sealing As a result, a decrease in transparency occurs.

  In order to solve such a problem, in the present invention, after forming a gas barrier layer on a resin base material, a color tone fluctuation due to thermal energy received at the time of forming the gas barrier layer is formed by laminating a color tone adjusting layer for adjusting the color tone. Without being damaged, etc., and after device sealing, it is shielded from the outside air by the gas barrier layer, so there is little deterioration under high temperature and high humidity environment. Furthermore, by applying a fluorescent material that absorbs ultraviolet light and generates blue light as a color tone adjusting agent, it is possible to compensate for yellowness generated in the gas barrier film without reducing visible light transmittance. it can.

  In particular, in the gas barrier film of the present invention, the compound having a metal-oxygen bond used in the color tone adjusting layer according to the present invention can uniformly disperse or dissolve the color tone adjusting agent therein, and Better transparency and color development can be obtained as compared with the case of a single body. In addition, by using a compound having a metal-oxygen bond, high durability can be realized by suppressing damage caused by heat of the color adjusting agent and movement and diffusion of the color adjusting agent to the contacting layer interface. it can.

Schematic sectional view showing an example of the configuration of the gas barrier film of the present invention Schematic sectional view showing an example of another configuration of the gas barrier film of the present invention Schematic which shows an example of the manufacturing method of the gas barrier film using the roller CVD method by the discharge plasma CVD apparatus between the rollers which applied the magnetic field.

  The gas barrier film of the present invention has a gas barrier layer on a resin substrate, and contains a color tone adjusting agent and a compound having a metal-oxygen bond capable of holding the color adjusting agent on the gas barrier layer. It is possible to realize a gas barrier film with excellent gas barrier performance, high transparency, and excellent productivity by using a thin resin substrate having flexibility, and having a color tone adjusting layer. . This feature is a technical feature common to the inventions according to claims 1 to 12.

  As an embodiment of the present invention, from the viewpoint that the effects intended by the present invention can be further manifested, it is possible to obtain a high-quality gas barrier layer whose composition is precisely controlled by the gas barrier layer being a deposited film It is preferable from the viewpoint that can be achieved.

  In addition, the gas barrier layer comprises a coating film, and further comprises a coating film containing at least polysilazane or a modified product thereof, which has good gas barrier performance and high transparency, and is easy to manufacture. It is preferable from the viewpoint that it can be formed by an apparatus and excellent productivity can be obtained.

  In addition, it is preferable that the color tone adjusting layer is laminated on the gas barrier layer as a coating film from the viewpoint of being able to be formed with a simple manufacturing apparatus and obtaining excellent productivity.

  Further, the color tone adjusting agent contained in the color tone adjusting layer is a fluorescent substance, and further, the fluorescent substance is an organic fluorescent agent or an inorganic fluorescent agent, or the fluorescent substance has a maximum emission wavelength of 500 nm or less. When the resin base material is yellow-colored due to heat damage or the like, it is possible to efficiently compensate for variations in color tone and to achieve good color tone and high transparency. preferable.

  Further, the compound having a metal-oxygen bond that can hold the color tone adjusting agent contained in the color tone adjusting layer is a polysilazane or a compound having a polysiloxane structure, and the color tone adjusting layer is the polysilazane, or A coating film containing a compound having a polysiloxane structure is preferable from the viewpoint of forming a color tone adjusting layer having excellent surface hardness.

  The pencil hardness (JIS K 5600-5-4) of the surface of the color tone adjustment layer formed in this way is within the range of HB to 4H, even when subjected to external pressure, such as scratches on the surface. Generation | occurrence | production can be prevented effectively and it is preferable.

  In the method for producing a gas barrier film of the present invention, after a gas barrier layer is formed on a resin substrate by a plasma CVD method, a color tone adjusting layer containing a color tone adjusting agent is formed on the gas barrier layer. A coating layer is used to produce a gas barrier film by laminating a color tone adjustment layer by a wet coating method, or a coating solution for forming a gas barrier layer containing polysilazane is applied on a resin substrate by a wet coating method. And drying to form a thin film containing polysilazane, reforming the thin film to form a gas barrier layer, and then applying a color tone adjusting layer forming coating solution on the gas barrier layer And a gas barrier film is produced by laminating a color tone adjusting layer by a wet coating method.

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

<Composition of gas barrier film>
The gas barrier film of the present invention includes a gas barrier layer on a resin base material surface, and a color tone adjusting layer containing a compound having a metal-oxygen bond capable of holding the color tone adjusting agent and the color tone adjusting agent thereon. It is the structure which has.

  Hereinafter, a typical configuration of the gas barrier film of the present invention will be described. However, an example of the embodiment is shown below, and is not limited only to the configuration exemplified here.

  FIG. 1 is a schematic cross-sectional view showing an example of the configuration of the gas barrier film of the present invention.

  FIG. 2 is a schematic cross-sectional view illustrating an example of another configuration in which the applied resin base material further includes an anchor coat layer and a bleed-out prevention layer as a functional layer.

  As shown in FIG. 1, the basic structure of the gas barrier film 1 of the present invention includes a gas barrier layer 3 on a transparent resin substrate 2, and a color tone adjusting agent on the gas barrier layer 3. And a color tone adjusting layer 4 containing a compound having a metal-oxygen bond capable of holding the color tone adjusting agent as a surface layer.

  Further, as an example of a developmental configuration, as shown in FIG. 2, an anchor coat layer 5 is provided between the transparent resin substrate 2 and the gas barrier layer 3, and the gas of the transparent resin substrate 2 is obtained. The structure which has the bleed-out prevention layer 6 in the surface on the opposite side to the surface which forms the barrier layer 3 can be mentioned.

<< Configuration of Gas Barrier Film and Method for Producing Gas Barrier Film >>
Subsequently, the structure of the gas barrier film of this invention and the outline | summary of the manufacturing method of a gas barrier film are demonstrated.

  As a method for producing a gas barrier film of the present invention, using a resin base material, at least a step of forming a gas barrier layer on the surface of the resin base material, and a step of laminating a color tone adjustment layer on the gas barrier layer It is characterized by having.

  Hereafter, the detail of the specific manufacturing apparatus and manufacturing method applied to each component of the gas barrier film of this invention and the manufacturing method of the gas barrier film of this invention is demonstrated.

[Resin substrate]
As a resin base material which comprises the gas barrier film which concerns on this invention, it is preferable to be comprised with the material which contains a thermoplastic resin as a main component and has flexibility. More preferably, a resin substrate made of a thermoplastic resin is used, and as such a resin substrate, a plastic film or a plastic sheet is generally used, and a film or sheet made of a colorless and transparent resin is preferably used.

  The plastic film applicable as the resin substrate according to the present invention is not particularly limited in material and thickness as long as it can hold a gas barrier layer, a bleed-out prevention layer, an anchor coat layer, etc. It can be selected as appropriate according to the conditions.

  In the present invention, as a plastic film applicable as a resin substrate, specifically, polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, Polyamide resin, polyamideimide resin, polyetherimide resin, cellulose acylate resin, polyurethane resin, polyetheretherketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, cycloolefin Transparent film composed of thermoplastic resin such as copolymer, fluorene ring modified polycarbonate resin, alicyclic modified polycarbonate resin, fluorene ring modified polyester resin, acryloyl compound, etc. , A heat-resistant transparent film (product name: Silplus, manufactured by Nippon Steel Chemical Co., Ltd.) having silsesquioxane having an organic-inorganic hybrid structure as a basic skeleton, and a composite resin formed by laminating two or more layers of the above films A film etc. are mentioned.

  More preferable specific examples of the thermoplastic resin that can be used as the resin base material according to the present invention include, for example, polyethylene terephthalate (abbreviation: PET), polyethylene naphthalate (abbreviation: PEN) in terms of cost and availability. ), Polycarbonate (abbreviation: PC), polyester (for example, Cosmo Shine (registered trademark) A4300 manufactured by Toyobo Co., Ltd.), alicyclic polyolefin (abbreviation: COP, for example, ZEONOR (registered trademark) 1600 manufactured by Nippon Zeon Co., Ltd.) ), Polyarylate (abbreviation: PAr), polyethersulfone (abbreviation: PES), polysulfone (abbreviation: PSF), cycloolefin copolymer (abbreviation: COC, compound described in JP-A-2001-150584), polyimide (abbreviation) : PI, for example, manufactured by Mitsubishi Gas Chemical Co., Ltd. Neoprim (registered trademark)), fluorene ring-modified polycarbonate (abbreviation: BCF-PC, compound described in JP 2000-227603 A), alicyclic modified polycarbonate (abbreviation: IP-PC, JP 2000-227603 A) And acryloyl compounds (compounds described in JP-A No. 2002-80616).

  When the gas barrier film produced according to the present invention is applied to an electronic device such as an organic EL element, the plastic film is preferably transparent.

  The term “transparent” as used in the present invention means that the average light transmittance in the visible light region is usually 80% or more, preferably 85% or more, and more preferably 90% or more.

  The light transmittance can be measured by the method described in JIS K7105 1981. Specifically, the total light transmittance and the amount of scattered light are measured using an integrating sphere light transmittance measuring device, and the total light transmittance is measured. It can be calculated by subtracting the diffuse transmittance from the rate.

  The thickness of the resin substrate constituting the gas barrier film of the present invention is not particularly limited because it is appropriately selected depending on the application, but is generally within the range of 2 to 200 μm, preferably within the range of 12 to 125 μm. . If the thickness of the resin substrate is 2 μm or more, the handling property, transportability, and heat resistance can be maintained in the form of the resin substrate applied to the gas barrier film of the present invention. Moreover, if it is 200 micrometers or less, the flexibility as a resin base material is fully securable.

  Moreover, as a resin base material using the resin etc. which were mentioned above, an unstretched film may be sufficient and a stretched film may be sufficient.

  The resin base material applicable to the present invention can be produced by a conventionally known general method. For example, a melt casting method for producing an unstretched resin base material that is substantially amorphous and not oriented by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and rapidly cooling it. Can be applied. Alternatively, a solution casting method in which a resin as a material is dissolved in an organic solvent or the like to prepare a dope, and the dope is cast into a metal endless belt shape to form a film can be applied. In addition, the unstretched resin base material is transported in the direction of the resin base material (vertical direction) by a known method such as uniaxial stretching, tenter sequential biaxial stretching, tenter simultaneous biaxial stretching, tubular simultaneous biaxial stretching , MD direction) and a stretched resin base material can be produced by stretching in a direction perpendicular to the transport direction of the resin base material (also referred to as a horizontal axis direction or a TD direction). The draw ratio in this case can be appropriately selected according to the resin used as the raw material of the resin base material. However, the draw ratio is 2 to 10 times in the vertical axis direction (MD direction) and the horizontal axis direction (TD direction), respectively. It is preferable to stretch within the range.

  The surface of the resin base material may be subjected to a known surface treatment method, for example, corona discharge treatment, flame treatment, oxidation treatment, plasma treatment, etc., from the viewpoint of improving adhesion with the constituent layer laminated thereon. Good.

[Functional layer that can be applied to resin base material]
The resin substrate according to the present invention may be provided with various functional layers as necessary to constitute a resin substrate laminate. Examples of applicable functional layers include an anchor coat layer 5 provided between the resin base 2 and the gas barrier layer 3 as illustrated in FIG. 2 and a bleed-out prevention layer provided on the back side of the resin base 2. 6 etc. can be mentioned.

(Anchor coat layer)
As shown in FIG. 2, the anchor coat layer 5 is provided on the surface of the resin base 2 on the side in contact with the gas barrier layer 3, and the adhesion (adhesion) between the gas barrier layer 3 and the resin base 2. And a layer formed for the purpose of improving smoothness.

  Examples of the anchor coating agent used for forming the anchor coat layer 5 include polyester resins, isocyanate resins, urethane resins, acrylic resins, ethylene vinyl alcohol resins, vinyl modified resins, epoxy resins, modified styrene resins, modified silicone resins, and alkyl resins. One or more titanates can be used in combination. A commercially available product may be used as the anchor coating agent.

Conventionally known additives such as a solvent can be added to these anchor coating agents. The anchor coating agent is coated on a resin substrate using a known wet coating method such as roller coating, gravure coating, knife coating, dip coating, or spray coating, and the solvent, diluent, and the like are removed by drying. Can be formed. The application amount of the anchor coating agent is preferably in the range of 0.1 to 5 g / m ² as the solid content. In addition, you may apply the commercially available resin base material with an easily bonding layer.

(Bleed-out prevention layer)
The bleed-out prevention layer applicable to the resin base material according to the present invention includes a plasticizer present inside a resin base material composed of a thermoplastic resin, a monomer or an oligomer that is a raw material of the resin base material, and the like. It is a layer provided on the surface of the resin base material for the purpose of suppressing the phenomenon of low molecular components diffusing to the surface of the resin base material and contaminating the contacting surface, so-called bleed out.

  In the bleed-out prevention layer, it is preferable to use a carbon-containing polymer, preferably a curable resin, as a hard coat agent.

  In the present invention, the curable resin applicable to the formation of the bleed-out layer is not particularly limited, and examples thereof include a thermosetting resin and a photocurable resin (for example, an active energy ray curable resin). The formation method using an active energy ray-curable resin is preferable because it can be easily formed as a bleed-out prevention layer. Such curable resins may be used alone or in combination of two or more. The curable resin may be a commercially available product or a synthetic product.

  Examples of the active energy ray-curable resin composition include a composition containing an acrylate compound, a composition containing an acrylate compound and a mercapto compound containing a thiol group, epoxy acrylate, urethane acrylate, polyester acrylate, and polyether acrylate. And radically polymerizable compounds or cationically polymerizable compounds such as compositions containing polyfunctional acrylate monomers such as polyethylene glycol acrylate and glycerol methacrylate.

  Specifically, NK ester A-DCP (tricyclodecane dimethanol diacrylate), which is a curable difunctional acrylate of Shin-Nakamura Chemical Co., Ltd., a UV curable organic / inorganic hybrid hard coat material manufactured by JSR Corporation A certain OPSTAR (registered trademark) series (compound obtained by bonding an organic compound having a polymerizable unsaturated group to silica fine particles) or the like can be used.

  It is also possible to use any mixture of the above-mentioned compositions, and an active energy ray-curable material containing a reactive monomer having at least one photopolymerizable unsaturated bond in the molecule. If there is no restriction in particular.

  Examples of the active energy ray-curable resin used to form the bleed-out prevention layer include resins that can be cured by irradiating active energy rays such as ultraviolet rays and electron beams, among these, An ultraviolet curable resin that is cured by ultraviolet irradiation is preferred.

  A matting agent may be contained as another additive of the bleed-out prevention layer. As the matting agent, inorganic particles having an average particle diameter of about 0.1 to 5 μm are preferable.

  As such inorganic particles, for example, silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide and the like are used alone or in combination of two or more. be able to.

  Here, the matting agent composed of inorganic particles is 2 parts by mass or more, preferably 4 parts by mass or more, more preferably in the range of 6 to 20 parts by mass with respect to 100 parts by mass of the solid content of the active energy ray-curable resin. Is within.

  The bleed-out prevention layer may contain, for example, a thermoplastic resin, a thermosetting resin, a photopolymerization initiator, etc. as other components of the active energy ray-curable resin and the matting agent.

  The above bleed-out prevention layer is prepared by blending an active energy ray-curable resin and other components as required, and preparing a coating solution for forming a bleed-out prevention layer with a diluting solvent used as necessary. The coating solution can be formed by applying the coating solution to the surface of the resin substrate by a conventionally known wet coating method and then curing it by irradiating with ionizing radiation, for example, ultraviolet rays.

  As a method of irradiating with ionizing radiation, ultraviolet rays having a wavelength region 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, etc. are irradiated. Alternatively, the irradiation can be performed by irradiating an electron beam having a wavelength region of 100 nm or less emitted from a curtain type electron beam accelerator.

  The layer thickness of the bleed-out prevention layer 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 film of the present invention is characterized by having a gas barrier layer having gas barrier properties on the surface of the produced resin base material or resin base material laminate.

The “gas barrier property” as used in the present invention is a water vapor permeability (water vapor permeability) (38 ± 0.5 ° C., relative humidity (90 ± 2)) measured by a method according to JIS K 7129-1992. % RH) is 1.0 g / (m ² · 24 h) or less, and in the present invention, it is defined as having gas barrier properties if it has such characteristics.

  The gas barrier layer forming method according to the present invention includes a vapor deposition method in which a metal or metal oxide is evaporated to form a gas barrier layer, or a wet coating method using a gas barrier layer forming coating solution containing polysilazane. It is preferable to apply the method of forming by.

  Hereinafter, typical examples of the vapor deposition method and the wet coating method that can be used for forming the gas barrier layer according to the present invention will be described.

(First gas barrier layer forming method: forming a gas barrier layer by vapor deposition)
As a vapor deposition method applicable to the formation of the gas barrier layer according to the present invention, a physical vapor deposition method (abbreviation: PVD method) in which a metal or a metal oxide is evaporated to form a film on a resin substrate, A source gas containing a desired thin film component (for example, an organosilicon compound typified by tetraethoxysilane (abbreviation: TEOS)) is supplied, and the film is deposited by a chemical reaction on the surface of the resin substrate or in the gas phase. Examples include a chemical vapor deposition method (abbreviation: CVD method) for forming a gas barrier layer, a sputtering method in which metal Si is evaporated and deposited on a substrate in the presence of oxygen, using a semiconductor laser or the like. In the present invention, the chemical vapor deposition method (CVD method) or the physical vapor deposition method (PVD method) is preferable, and more preferably, the plasma chemical vapor deposition method (abbreviation: plasma) in which plasma discharge is performed. Particularly preferably a discharge plasma chemical vapor deposition method (hereinafter referred to as “roller CVD method”) having a discharge space between rollers to which a magnetic field is applied using a source gas containing an organosilicon compound. .).

  The gas barrier layer according to the present invention preferably contains at least a carbon atom as a constituent element of the gas barrier layer. By including a carbon atom, it is preferable from the viewpoint that a gas barrier film excellent in flexibility (flexibility) and adhesion can be obtained.

  In the present invention, the content ratio of carbon atoms and other atoms in the gas barrier layer can be determined by a measurement method using X-ray photoelectron spectroscopy (XPS) under the following conditions.

Etching ion species: Argon (Ar ⁺ )
Etching rate (SiO ₂ thermal oxide equivalent value): 0.05 nm / sec
Etching interval (SiO ₂ equivalent value): 10 nm
X-ray photoelectron spectrometer: Model “VG Theta Probe”, manufactured by Thermo Fisher Scientific
Irradiation X-ray: Single crystal spectroscopy AlKα
X-ray spot and size: 800 × 400 μm oval.

  The thickness of the gas barrier layer according to the present invention is preferably in the range of 5 to 3000 nm, more preferably in the range of 10 to 2000 nm, and more preferably in the range of 100 to 1000 nm. When the thickness of the gas barrier layer is within the above range, the gas barrier property against oxygen and water vapor is excellent, and the gas barrier property is not deteriorated by bending.

  As described in detail below, the gas barrier layer constituting the gas barrier film of the present invention is preferably formed on the surface of the resin substrate by a roll-to-roll method from the viewpoint of productivity. In addition, a forming apparatus that can be used when producing a gas barrier layer by a plasma CVD method is not particularly limited, and includes a film forming roller to which at least a pair of magnetic fields are applied, a plasma power source, and a pair of It is preferable that the apparatus has a configuration capable of discharging between film forming rollers to which a magnetic field is applied. Specifically, when a thin film forming manufacturing apparatus as shown in FIG. It becomes possible to manufacture by a roll-to-roll method using the CVD method.

<Plasma CVD production equipment>
FIG. 3 is a schematic diagram showing an example of a manufacturing flow of a gas barrier layer by a roller CVD method using a plasma CVD manufacturing apparatus to which a magnetic field applicable to the present invention is applied.

  The plasma CVD manufacturing apparatus S1 shown in FIG. 3 is a process for forming a gas barrier film by laminating the gas barrier layer 3 on the surface of the resin base material 2, for example.

  As the plasma CVD manufacturing apparatus S1, mainly as shown in FIG. 3, a roll-shaped feeding roller 11A in which the resin base material 2 is laminated, and transport rollers 22 and 23 for transporting the resin base material 2, A pair of film forming rollers 31 and 32, a film forming gas supply pipe 41, a plasma generating power source 51, and a winding roller 11B are provided. In addition, magnetic field generators 61 and 62 that are fixed so as not to rotate even when the film forming roller rotates are provided inside the film forming rollers 31 and 32, respectively.

  In the plasma CVD manufacturing apparatus S1, the components such as the film forming rollers 31 and 32 are disposed in the vacuum chamber 16 as shown in FIG. Further, a vacuum pump 17 which is a vacuum exhaust means is connected to the vacuum chamber 16 via an exhaust port 18, and the pressure in the vacuum chamber 16 is appropriately adjusted by the vacuum pump 17 and the film forming gas supply pipe 41. It is possible. The vacuum pump 17 can evacuate the inside of the vacuum chamber 16 to a vacuum state or a low pressure state according to vacuum.

  Next, a method for forming a gas barrier layer using a plasma CVD manufacturing apparatus will be described.

  When forming the gas barrier layer, as shown in FIG. 3, the resin base material 2 is arranged around each of the pair of film forming rollers 31 and 32, and a voltage is applied between the pair of film forming rollers 31 and 32. This is applied to generate plasma to form a plasma discharge space.

  Next, a gas barrier film is formed by forming a gas barrier layer 3 on the surface of the resin substrate 2 that is continuously conveyed while supplying a film forming gas for forming a gas barrier layer from the film forming gas supply pipe 41 to the discharge space. Then, it is wound up into a roll by the winding roller 11B.

  In the present invention, it is preferable that the surface temperatures of the film forming rollers 31 and 32 at the time of forming the gas barrier layer are controlled within a certain range. As a specific temperature range of the surface temperature of each film forming roller, an appropriate range varies depending on the type of resin base material constituting the resin base material 2 and Tg (crown transition temperature), but generally 0 to 150 ° C. More preferably, it is in a temperature range of 15 to 80 ° C, and more preferably in a temperature range of 20 to 60 ° C.

  A specific method for controlling the surface temperature of the film forming roller to the above temperature will be described in detail below.

  As the configuration of the film forming rollers 31 and 32 applicable to the plasma CVD manufacturing apparatus S1 according to the present invention, for example, the surface of the film forming roller is coated with titanium, stainless steel, chrome plating, cemented carbide, or the like. The thing which equips the inside with the mechanism which can distribute | circulate a refrigerant | coolant or a heat carrier is mentioned. And it is preferable to control so that the surface temperature of the film-forming rollers 31 and 32 may become the said range by distribute | circulating a refrigerant | coolant or a heat medium in the inside. Moreover, a well-known thing can be used as a mechanism which distribute | circulates a refrigerant | coolant or a heat medium.

  The conveyance speed (line speed) of the resin base material 2 can be appropriately adjusted according to the type of film forming gas, the pressure in the vacuum chamber, and the like, but should be in the range of 0.25 to 100 m / min. Is preferable, and it is more preferable to set it within the range of 0.3 to 30 m / min. If the conveyance speed is 0.25 m / min or more, generation of wrinkles due to heat of the resin base material 2, illegal peeling between the resin base materials, and the like can be effectively suppressed. On the other hand, if it is 100 m / min or less, the adhesiveness at the peelable interface between the resin base materials can be maintained without impairing the productivity, and a sufficient layer thickness as a gas barrier layer should be secured. Can do.

  Next, a specific method for forming a gas barrier layer will be described.

  As described above, in the plasma CVD manufacturing apparatus S1 having a pair of film formation rollers (the film formation roller 31 and the film formation roller 32), the pair of film formation rollers 31 and 32 can function as a pair of counter electrodes. Each film-forming roller 31 and 32 is connected to a plasma generation power source 51 so that

  Therefore, in such a plasma CVD manufacturing apparatus S1, it is possible to discharge into the space between the film forming roller 31 and the film forming roller 32 by supplying electric power from the power source 51 for plasma generation. Plasma is generated in a discharge space between the film forming roller 31 and the film forming roller 32. In addition, when using the film-forming roller 31 and the film-forming roller 32 as electrodes in this way, the material and design may be changed as appropriate so that they can also be used as electrodes.

  In the plasma CVD manufacturing apparatus S1 shown in FIG. 3, it is preferable that the pair of film forming rollers (film forming rollers 31 and 32) be arranged so that their central axes are substantially parallel on the same plane. As described above, by arranging the pair of film forming rollers (film forming rollers 31 and 32) horizontally, the film forming rate can be doubled. According to such a plasma CVD manufacturing apparatus, the gas barrier layer can be formed on the surface of one resin substrate of the resin substrate unit 2 by the CVD method at the position of the film forming roller 31. Also in the film roller 32 region, since the gas barrier layer 3 component can be deposited on the surface of one resin base material F1 of the resin base material unit 2, the gas barrier layer 3 is formed on the surface of the resin base material 2. It can be formed efficiently.

  Inside the film forming roller 31 and the film forming roller 32, as described above, the magnetic field generators 61 and 62 are provided so as to be fixed so as not to rotate even if the film forming roller rotates. ing.

  The magnetic field generators 61 and 62 provided in each of the film forming roller 31 and the film forming roller 32 include a magnetic field generating device 61 provided in one film forming roller 31 and a magnetic field provided in the other film forming roller 32. It is preferable to arrange the magnetic poles so that the magnetic field lines do not cross between the generators 62 and the magnetic field generators 61 and 62 form a substantially closed magnetic circuit. By providing such magnetic field generators 61 and 62, it is possible to promote the formation of a magnetic field in which the magnetic lines of force swell in the vicinity of the surface on the opposite surface side of each of the film forming rollers 31 and 32. Therefore, it is excellent in that the film formation efficiency of the gas barrier layer can be improved.

  Further, the magnetic field generators 61 and 62 provided in the film forming roller 31 and the film forming roller 32 respectively have racetrack-shaped magnetic poles that are long in the roller axis direction of the film forming roller. It is preferable to arrange the magnetic poles so that the magnetic poles facing the other magnetic field generator 62 have the same polarity. By providing such magnetic field generators 61 and 62, the opposing space along the length direction of the roller shaft without straddling the magnetic field generator on the roller side where the lines of magnetic force of each of the magnetic field generators 61 and 62 are opposed. Resin base material wound along the roller width direction because a racetrack-like magnetic field can be easily formed in the vicinity of the roller surface facing (discharge space), and the plasma can be focused on the magnetic field. 2 is excellent in that the gas barrier layer 3 which is a vapor deposition film can be efficiently formed on the substrate 2.

  Furthermore, as the film formation roller 31 and the film formation roller 32, known rollers can be used as appropriate. As the film forming rollers 31 and 32, those having the same diameter are preferably used from the viewpoint of forming a thin film more efficiently. In addition, the diameters of the film forming rollers 31 and 32 are preferably in the range of 300 to 1000 mmφ, particularly in the range of 300 to 700 mmφ, from the viewpoint of discharge conditions, chamber space, and the like. If the diameter is 300 mmφ or more, it is preferable that the plasma discharge space is not reduced, the productivity is not deteriorated, the total amount of heat of the plasma discharge can be prevented from being applied to the film in a short time, and the residual stress is hardly increased. On the other hand, a diameter of 1000 mmφ or less is preferable because practicality can be maintained in terms of device design including uniformity of the plasma discharge space.

  Further, as the feed roller 11A and the transport rollers 22 and 23 used in such a plasma CVD manufacturing apparatus S1, known rollers can be appropriately selected and used. Further, the winding roller 11B is not particularly limited as long as it can wind the resin base material 2 having the gas barrier layer 3 formed on one surface side, and a known roller is appropriately used. Can do.

  Further, as the film forming gas supply pipe 41 and the vacuum pump 17, those capable of supplying or discharging the source gas at a predetermined speed can be used as appropriate.

  Further, the film formation gas supply pipe 41 as the film formation gas supply means is preferably provided on one side of the facing space (discharge space) between the film formation roller 31 and the film formation roller 32, and is a vacuum exhaust means. The vacuum pump 17 is preferably provided on the other side of the facing space. Thus, by disposing the film forming gas supply pipe 41 as the film forming gas supply means and the vacuum pump 17 as the vacuum exhaust means, the facing space (discharge space) between the film forming roller 31 and the film forming roller 32 is arranged. It is excellent in that the film forming gas can be efficiently supplied to the substrate and the film forming efficiency can be improved.

  Furthermore, as the plasma generating power source 51, a known power source for a plasma generating apparatus can be used as appropriate. Such a power source 51 for generating plasma supplies power to the film forming roller 31 and the film forming roller 32 connected to the power source 51 and makes it possible to use them as a counter electrode for discharging. As such a plasma generation power source 51, an AC power source capable of alternately reversing the polarities of the pair of film forming rollers is used because plasma CVD can be performed more efficiently. Is preferred. In addition, since such a plasma generating power source 51 can perform the plasma CVD process more efficiently, the applied power can be in the range of 100 W to 10 kW, and the AC frequency can be More preferably, it can be within the range of 50 Hz to 500 kHz. As the magnetic field generators 61 and 62, known magnetic field generators can be used as appropriate.

  Using such a plasma CVD manufacturing apparatus S1 as shown in FIG. 3, for example, the type of source gas, the power of the electrode drum of the plasma generator, the pressure in the vacuum chamber, the diameter of the film forming roller, and the film (resin A gas barrier layer having desired characteristics can be formed by appropriately adjusting the conveyance speed of the substrate.

  More specifically, a pair of film forming rollers (film forming rollers 31 and 32) is supplied while supplying a film forming gas (such as a raw material gas) into the vacuum chamber 16 using a plasma CVD manufacturing apparatus S1 as shown in FIG. By generating a discharge in the meantime, the film forming gas (raw material gas or the like) is decomposed by plasma, and the gas barrier layer 3 is plasma on the film forming roller 31 and the surface of the resin substrate 2 on the film forming roller 32. It is formed by the CVD method. In such film formation, the resin base material 2 is conveyed by the feed roller 11A, the film formation rollers 31 and 32, the conveyance rollers 22 and 23, etc., respectively, so that the roll-to-roll type continuous formation is performed. The gas barrier layer 3 is continuously formed on one surface of the resin base material 2 by the film process.

<Film forming gas for gas barrier layer formation>
In the method for forming the gas barrier layer 3 according to the present invention, as the film forming gas supplied from the film forming gas supply pipe 41 to the facing space (discharge space), source gas, reaction gas, carrier gas, discharge gas, etc. It can be used alone or in combination of two or more.

  The source gas in the film forming gas used for forming the gas barrier layer 3 can be appropriately selected and used according to the material of the gas barrier layer 3 to be formed. As such a source gas, for example, an organic silicon compound containing silicon or an organic compound gas containing carbon can be used. In the gas barrier layer according to the present invention, a metal oxide containing at least a carbon atom is used. The raw material which can form a physical layer is preferable.

  Examples of the organosilicon compound applicable to the present invention include hexamethyldisiloxane (abbreviation: HMSO), hexamethyldisilane (abbreviation: HMDS), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, Methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (abbreviation: TMOS), tetraethoxysilane (abbreviation: TEOS), phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane and the like. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of handling properties of the compound and gas barrier properties of the resulting gas barrier layer. These organosilicon compounds can be used alone or in combination of two or more. Examples of the organic compound gas containing carbon include methane, ethane, ethylene, and acetylene. As these organosilicon compound gas and organic compound gas, an appropriate source gas is selected according to the type of the gas barrier layer.

  In addition to the source gas, a reactive gas may be used as the film forming gas. As such a reactive gas, a gas that reacts with the raw material gas to become an inorganic compound such as an oxide or a nitride can be appropriately selected and used. As a reaction gas for forming an oxide, for example, oxygen or ozone can be used. Moreover, as a reactive gas for forming nitride, nitrogen and ammonia can be used, for example. These reaction gases can be used singly or in combination of two or more. For example, when forming an oxynitride, a reaction gas for forming an oxide and a nitride are formed. The reaction gas can be used in combination.

  Further, as a film forming gas, a carrier gas may be used as necessary in order to supply the source gas into the vacuum chamber. Further, as a film forming gas, a discharge gas may be used as necessary in order to generate plasma discharge. As such carrier gas and discharge gas, known ones can be used as appropriate, and for example, a rare gas such as helium, argon, neon, xenon, or hydrogen gas can be used.

  When such a film forming gas contains a raw material gas and a reforming reaction gas (hereinafter also simply referred to as “reactive gas”), the ratio of the raw material gas to the reactive gas is as follows. It is preferable that the ratio of the reaction gas is not excessively larger than the ratio of the amount of the reaction gas that is theoretically necessary for completely reacting the reaction gas. By not excessively increasing the ratio of the reaction gas, the gas barrier layer formed is excellent in that excellent gas barrier properties and bending resistance can be obtained. In addition, when the film forming gas contains the organosilicon compound and oxygen, it may be less than or equal to the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film forming gas. preferable.

Hereinafter, as the composition of the film forming gas, hexamethyldisiloxane (organosilicon compound, HMDSO, (CH ₃ ) ₆ Si ₂ O) is used as a source gas, and oxygen (O ₂ ) as a reaction gas is contained. Using a silicon-oxygen-based gas barrier layer as an example, a suitable ratio of the raw material gas to the reactive gas in the film forming gas will be described in more detail.

A film-forming gas containing hexamethyldisiloxane (HMDSO, (CH ₃ ) ₆ Si ₂ O) as a source gas and oxygen (O ₂ ) as a reaction gas is reacted by plasma CVD to produce silicon- When an oxygen-based gas barrier layer is formed, a reaction represented by the following reaction formula (1) occurs by the film forming gas, and silicon dioxide is generated.

Equation _{(1) :( CH 3) 6} Si 2 O + 12O 2 → 6CO 2 + 9H 2 O + 2SiO 2
In the above reaction formula, the amount of oxygen required to completely oxidize 1 mol of hexamethyldisiloxane is 12 mol. Therefore, when the film forming gas contains 12 moles or more of oxygen with respect to 1 mole of hexamethyldisiloxane and is completely reacted, a uniform silicon dioxide film is formed. However, in the present invention, in order to improve the gas barrier property of the gas barrier layer to be formed, oxygen of one mole of hexamethyldisiloxane is prevented so that the reaction of the reaction formula (1) does not proceed completely. It is preferred that the amount be less than the stoichiometric ratio of 12 moles. In the actual reaction in the plasma CVD chamber, the raw material hexamethyldisiloxane and the reaction gas oxygen are supplied from the film formation gas supply unit 41 to the film formation region to form a film. Even if the molar amount (flow rate) of the catalyst is 12 times the molar amount (flow rate) of the raw material hexamethyldisiloxane, the reaction cannot actually proceed completely. It is considered that the reaction is completed only when the content is supplied in a large excess compared to the stoichiometric ratio. For example, in order to obtain silicon oxide by complete oxidation by CVD, the molar amount (flow rate) of oxygen may be about 20 times or more the molar amount (flow rate) of hexamethyldisiloxane as a raw material. Therefore, the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of hexamethyldisiloxane as a raw material is preferably 12 times the stoichiometric ratio or less, more preferably 10 times or less. is there. By containing hexamethyldisiloxane and oxygen in such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane that have not been completely oxidized are incorporated into the layer when the gas barrier layer is formed, and carbon obtained In a gas barrier film containing atoms, it is possible to exhibit excellent gas barrier properties and bending resistance.

  From the viewpoint of use as a flexible substrate for devices that require transparency, such as organic EL elements and solar cells, the molar amount of oxygen relative to the molar amount (flow rate) of hexamethyldisiloxane in the deposition gas The lower limit of (flow rate) is preferably greater than 0.1 times the molar amount (flow rate) of hexamethyldisiloxane, more preferably greater than 0.5 times.

  Moreover, although the pressure (degree of vacuum) in the vacuum chamber 16 can be suitably adjusted according to the kind etc. of source gas, it is preferable to set it as the range of 0.5-50 Pa.

  Further, in such a plasma CVD method, an electrode drum (not shown, in the configuration shown in FIG. 3) connected to the plasma generation power source 51 in order to discharge between the film formation roller 31 and the film formation roller 32. The applied power applied to the film forming rollers 31 and 32 can be appropriately adjusted according to the type of the source gas, the pressure in the vacuum chamber, etc., and cannot be generally described. The range of 0.1 to 10 kW is preferable. If such an applied power is 0.1 kW or more, the generation of particles can be sufficiently suppressed. On the other hand, if the applied power is 10 kW or less, the amount of heat generated during film formation can be suppressed. It can suppress that the temperature of the substrate surface rises. Therefore, the substrate is excellent in that wrinkles can be prevented during film formation without being deformed by heat.

(Second gas barrier layer forming method: forming a gas barrier layer by a wet coating method)
In the gas barrier film of the present invention, as a second method of forming the gas barrier layer, a method of forming by a wet coating method, specifically, a gas barrier layer forming coating solution containing polysilazane is applied on the resin substrate. A method of forming a gas barrier layer by coating and drying is preferably applied, and more preferably, a coating solution for forming a gas barrier layer containing polysilazane is applied and dried by a wet coating method, and the formed coating film has a wavelength of 200 nm or less. It is possible to apply a method of forming a gas barrier layer by irradiating the vacuum ultraviolet light (VUV light, excimer light) and modifying the formed coating film to form a gas barrier layer by the above-described vapor deposition method. This method is one of the preferable methods because a gas barrier layer can be easily formed without using large-scale equipment such as a vacuum apparatus.

  The thickness of the gas barrier layer formed by the wet coating method is preferably in the range of 1 to 500 nm, more preferably in the range of 10 to 300 nm. If the thickness of the gas barrier layer is 1 nm or more, the desired gas barrier performance can be exhibited, and if it is 500 nm or less, film quality deterioration such as generation of cracks in a dense silicon oxynitride film can be prevented. Can do.

<Polysilazane>
The polysilazane used for forming the gas barrier layer according to the present invention is a polymer having a silicon-nitrogen bond in the molecular structure and a precursor of silicon oxynitride, and the polysilazane to be applied is not particularly limited. Is preferably a compound having a structure represented by the following general formula (1).

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

In the present invention, from the viewpoint of denseness as a gas barrier layer to be obtained, perhydropolysilazane (abbreviation: PHPS) in which all of R ¹ , R ² and R ³ are composed of hydrogen atoms is particularly preferable.

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

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

  The second gas barrier layer may be formed by applying and drying a coating liquid containing polysilazane on a gas barrier layer formed by an inter-roller discharge plasma CVD method to which a magnetic field is applied, and then irradiating with vacuum ultraviolet rays. it can.

  As an organic solvent for preparing a coating liquid containing polysilazane, it is preferable to avoid using an alcohol or water-containing one that easily reacts with polysilazane. Examples of applicable organic solvents include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, ethers such as halogenated hydrocarbon solvents, aliphatic ethers, and alicyclic ethers. Specific examples include hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, and ethers such as dibutyl ether, dioxane and tetrahydrofuran. These organic solvents may be selected according to purposes such as the solubility of polysilazane and the evaporation rate of the organic solvent, and a plurality of organic solvents may be mixed.

  The concentration of polysilazane in the gas barrier layer-forming coating solution containing polysilazane varies depending on the thickness of the gas barrier layer to be formed and the pot life of the coating solution, but is preferably in the range of 0.2 to 35% by mass. is there.

  In order to promote modification to silicon oxynitride, an amine catalyst, a Pt compound such as Pt acetylacetonate, a Pd compound such as propionic acid Pd, an Rh compound such as Rh acetylacetonate, etc. It is also possible to add a metal catalyst. In the present invention, it is particularly preferable to use an amine catalyst. Specific amine catalysts include N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, N ′, N′-tetramethyl-1 , 3-diaminopropane, N, N, N ′, N′-tetramethyl-1,6-diaminohexane and the like.

  The amount of the catalyst added relative to the polysilazane is preferably in the range of 0.1 to 10% by mass, and in the range of 0.2 to 5.0% by mass with respect to the total mass of the coating liquid for forming the gas barrier layer. More preferably, it is more preferably in the range of 0.5 to 2.0% by mass. By setting the addition amount of the catalyst within the range specified above, excessive silanol formation due to rapid progress of the reaction, reduction in film density, increase in film defects, and the like can be avoided.

  As a method of applying the gas barrier layer forming coating solution containing polysilazane, any appropriate wet coating method can be appropriately selected and employed. Specific examples include a roller coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method.

  The layer thickness of the gas barrier layer formed from polysilazane is as described above, preferably in the range of 1 to 500 nm, and more preferably in the range of 10 to 300 nm.

<Excimer light treatment>
In the gas barrier layer formed by the wet coating method according to the present invention, at least a part of the polysilazane is converted into silicon oxynitride by irradiating the coating film formed of the coating liquid containing polysilazane with vacuum ultraviolet rays (VUV). And modified.

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

Perhydropolysilazane can be represented by a composition of “— (SiH ₂ —NH) _n —”, and in order to satisfy x> 0 in the composition of the gas barrier layer represented by SiO _x N _y , an external oxygen source However, as this oxygen source,
(I) oxygen and moisture contained in the polysilazane coating solution,
(Ii) oxygen and moisture taken into the coating film from the atmosphere of the coating and drying process,
(Iii) oxygen, moisture, ozone, singlet oxygen taken into the coating film from the atmosphere in the vacuum ultraviolet irradiation process,
(Iv) Oxygen and moisture moving into the coating film as outgas from the substrate side by heat applied in the vacuum ultraviolet irradiation process,
(V) When the vacuum ultraviolet ray irradiation step is performed in a non-oxidizing atmosphere, when moving from the non-oxidizing atmosphere to the oxidizing atmosphere, oxygen and moisture taken into the coating film from the atmosphere,
Etc.

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

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

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

(1) Dehydrogenation and associated Si—N bond formation Si—H bonds and N—H bonds in perhydropolysilazane are relatively easily cleaved by excitation by vacuum ultraviolet irradiation, etc., and in an inert atmosphere, Si— It is considered that they are recombined as N (a dangling bond of Si may be formed). That is, the cured as SiN _y composition without oxidizing. In this case, the polymer main chain is not broken. The breaking of Si—H bonds and N—H bonds is promoted by the presence of a catalyst and heating. The cut H is released out of the membrane as H ₂ .

(2) Formation of Si—O—Si bond by hydrolysis and dehydration condensation The Si—N bond in perhydropolysilazane is hydrolyzed by water, and the polymer main chain is cleaved to form Si—OH. Two Si—OHs are dehydrated and condensed to form Si—O—Si bonds and harden. This is a reaction that occurs even in the atmosphere, but during vacuum ultraviolet irradiation in an inert atmosphere, it is considered that water vapor generated as outgas from the resin base material by the heat of irradiation becomes the main moisture source. When the water becomes excessive, Si—OH that cannot be dehydrated and condensed remains, and a cured film having a low gas barrier property represented by a composition of SiO _2.1 to SiO _2.3 is obtained.

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

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

  Adjustment of the composition of silicon oxynitride in a layer obtained by subjecting a layer containing polysilazane to vacuum ultraviolet irradiation can be performed by appropriately combining the oxidation mechanisms (1) to (4) described above to control the oxidation state. .

In vacuum ultraviolet irradiation step in the present invention, the illuminance of the VUV in the coated surface for receiving the polysilazane coating film is preferably in the range of 30~200mW / cm ^2, within the range of 50~160mW / cm ² More preferably. If the illuminance is 30 mW / cm ² or more, there is no concern about the reduction in the reforming efficiency, and if it is 200 mW / cm ² or less, the coating film is not ablated, and the substrate is not damaged. Ablation as used in the present invention refers to a phenomenon in which bonds between molecules are broken by irradiation with vacuum ultraviolet rays and the film is scattered by evaporation or thermal destruction of the coating film.

Irradiation energy amount of the VUV in the polysilazane coating film surface is preferably in the range of 200~10000mJ / cm ^2, and more preferably in a range of 500~5000mJ / cm ^2. If the irradiation energy amount is 200 mJ / cm ² or more, desired modification can be performed, and if it is 10000 mJ / cm ² or less, over-reformation does not occur, and cracking and thermal deformation of the resin base material occur. Can be prevented.

  As a vacuum ultraviolet light source required for this, a rare gas excimer lamp is preferably used.

  In addition, although there is no restriction | limiting in particular as a detailed content and specific conditions of a vacuum ultraviolet irradiation process (excimer irradiation process), For example, paragraph number [0079]-same [0091] of Unexamined-Japanese-Patent No. 2011-031610 The contents described therein or the contents described in paragraph numbers [0086] to [0098] of JP 2012-016854 A can be referred to.

《Color tone adjustment layer》
In the gas barrier film of this invention, after forming the said gas barrier layer on a resin base material, it has a metal-oxygen bond which can hold | maintain a color tone regulator and the said color tone regulator on the said gas barrier layer. It is characterized by being formed by laminating a color tone adjusting layer containing a compound.

  In the gas barrier film of the present invention, the compound having a metal-oxygen bond capable of holding the color tone adjusting agent contained in the color tone adjusting layer is, for example, a compound having a polysilazane or polysiloxane structure, and the color tone For example, the adjustment layer is preferably formed by applying and drying a coating solution for forming a color tone adjustment layer containing a compound having a polysilazane or a polysiloxane structure on the gas barrier layer by a wet application method. .

[Color tone adjuster]
First, the color tone adjusting agent applied to the color tone adjusting layer according to the present invention will be described.

  The color tone adjusting agent applied to the color tone adjusting layer according to the present invention is not particularly limited, and examples thereof include a blue dye and a fluorescent material. Among them, a fluorescent material is preferable, and the fluorescent material is an organic fluorescent agent or an inorganic fluorescent material. It is more preferable that the fluorescent material is a blue light-emitting fluorescent material having an emission wavelength of 500 nm or less, which compensates for yellowing of the resin base material and does not reduce the transmittance. It is preferable from the viewpoint that the color tone can be obtained.

  An example of a blue dye applicable to the present invention is an anthraquinone dye. The anthraquinone dye may have an arbitrary substituent at an arbitrary position from the 1st position to the 8th position of the anthraquinone. Preferred substituents include an anilino group, hydroxyl group, amino group, nitro group, or hydrogen atom. In particular, the blue dyes described in paragraphs (0034) to (0037) of JP-A No. 2001-154017, particularly anthraquinone dyes, can be mentioned.

  In the color tone adjusting layer according to the present invention, it is particularly preferable to apply a fluorescent material as the color tone adjusting agent. Further, as described above, specifically, an organic fluorescent agent or an inorganic fluorescent agent is used as the fluorescent material. It is preferable.

  In the color tone adjustment layer according to the present invention, the addition amount of the color tone adjusting agent is not particularly limited, but from the viewpoint of exhibiting a color tone compensation effect against the coloring of the resin substrate, particularly yellowing, the color tone adjustment. It is preferably in the range of 1 to 10% by mass, more preferably in the range of 2 to 6% by mass with respect to the total mass of the layer. If the addition amount is 1% by mass or more, a sufficient color tone compensation effect can be obtained, and if it is 10% by mass or less, the color tone fluctuation caused by excessive blue shift of the gas barrier film due to the influence of the color tone adjusting agent itself. Can be suppressed.

<Organic fluorescent agent>
The organic fluorescent agent applicable to the present invention is preferably an organic fluorescent agent that is excited by light having a wavelength of 400 to 450 nm and emits light having a wavelength of 500 to 600 nm. This means that the excitation wavelength of the organic fluorescent agent in the present invention is in the band of 400 to 450 nm and the emission wavelength is in the range of 500 to 600 nm. If the excitation wavelength or emission wavelength is outside the range defined above, the color compensation effect is weak, and it becomes difficult to obtain a neutral color gas barrier film.

  When the excitation wavelength is not in the region of 400 to 450 nm and is in the region of less than 400 nm, it is not possible to obtain a compensation effect for the coloring of the resin substrate, while the excitation wavelength is only in the region of more than 450 nm. Is colored by absorption of visible light, and a transparent and nearly colorless gas barrier film cannot be obtained. When the emission wavelength is not in the region of 500 to 600 nm, but in the region of less than 500 nm or more than 600 nm, the effect of improving the reflectivity cannot be obtained when used as the reflector of the surface crystal display device, and the effect of improving the luminance is obtained. Can't get. For the above reasons, the organic fluorescent agent applied to the present invention is preferably a compound that is excited by light having a wavelength of 400 to 450 nm and emits light having a wavelength of 500 to 600 nm.

  Examples of the organic fluorescent agent satisfying the requirements for the excitation wavelength and emission wavelength include, for example, stilbene fluorescent agents, distilbene fluorescent agents, benzoxazole fluorescent agents, styryl / oxazole fluorescent agents, and pyrene / oxazole fluorescent agents. , A coumarin fluorescent agent, an imidazole fluorescent agent, a benzimidazole fluorescent agent, a pyrazoline fluorescent agent, an aminocoumarin fluorescent agent, a distyryl-biphenyl fluorescent agent, and a naphthalimide fluorescent agent. Among these, benzoxazole-based fluorescent agents, styryl-oxazole-based fluorescent agents, and naphthalimide-based fluorescent agents are preferred because of their high durability and high effect of improving reflectance. Specifically, yeast bright OB- 1 (benzoxazole-based fluorescent agent manufactured by Eastman Chemical Japan), Uvitex-OB (styryl / oxazole-based fluorescent agent manufactured by BASF Japan), and Lumogen Green 850 (naphthalimide-based fluorescent agent manufactured by BASF Japan) are used. preferable.

<Inorganic fluorescent agent>
Inorganic fluorescent agents applicable to the present invention include zinc oxide (ZnO), zinc sulfide (ZnS), zinc selenide (ZnSe), cadmium sulfide (CdS); Er ³⁺ , Yb ³⁺ , Tm ³⁺ , Ho ³⁺ , Pr ³⁺ Inorganic fluorescent agents such as rare earth-containing YAG (yttrium, aluminum, garnet) containing rare earth elements such as Eu ³⁺ .

The inorganic fluorescent agent according to the present invention converts a part of incident color light into light having a longer wavelength range. For example, color conversion (energy conversion) is performed using blue light as excitation light, green light, It includes at least one fluorescent material that generates red light or yellow light. Specifically, examples of the yellow conversion fluorescent material include (Y, Gd) ₃ (Al, Ga) ₅ O ₁₂ : Ce ³⁺ (common name: YAG: Ce ³⁺ ), α-SiAlON: Eu ^{2+, and the} like. Examples of yellow or green conversion fluorescent material include (Ca, Sr, Ba) ₂ SiO ₄ : Eu ²⁺ . Examples of the green conversion fluorescent material include SrGa ₂ S ₄ : Eu ²⁺ , β-SiAlON: Eu ²⁺ , Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce ^{3+, and the} like. Examples of fluorescent materials for red conversion include (Ca, Sr, Ba) S: Eu ²⁺ , (Ca, Sr, Ba) ₂ Si ₅ N ₈ : Eu ²⁺ , and CaAlSiN ₃ : Eu ²⁺ .

[Compound having a metal-oxygen bond capable of holding a color tone regulator]
The color tone adjusting layer according to the present invention contains a compound having a metal-oxygen bond (hereinafter referred to as “metal oxide binder”) that can hold the above-described color tone adjusting agent and acts as a binder. It is preferable.

  The metal oxide binder applicable to the color tone adjusting layer according to the present invention is not particularly limited as long as it is a compound having a metal-oxygen bond in its structure. For example, the following exemplified compounds are used alone or in combination. It may be a composition mixed with an organic compound or an inorganic compound.

  Examples of the metal oxide binder that can be used for forming the color tone adjusting layer include tetrachlorosilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, methyltrimethoxysilane, dimethyldimethoxysilane, and phenyltrimethoxysilane. , Tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, decyl Trimethoxysilane, trifluoropropyltrimethoxysilane, hexamethyldisilazane, perhydropolysilazane, methylpolysilazane, vinyl trime Xysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldi Ethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3- Methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropi Trimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3 -Ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, tetra Examples thereof include compounds composed of silicon oxide formed by hydrolysis and dehydration condensation of silane compounds such as isocyanate silane and methyl triisocyanate silane.

  In addition, a titanium alkoxide represented by the following general formula (2), a titanium acylate represented by the following general formula (3), and an organic titanium represented by a titanium chelate (complex) represented by the following general formula (4) Compound etc. are mentioned. In addition, R as described in the general formulas (2) to (4) represents an alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a dodecyl group, a tridecyl group, a tetradecyl group, and a pentadecyl group. .

  In addition, titanium tetra-2-ethylhexoxide, titanium diisopropoxybis (acetylacetonate), titanium tetraacetylacetonate, titanium dioctyloxybis (octylene glycolate), titanium diisopropoxybis (ethylacetoacetate) ), Titanium diisopropoxybis (triethanolaminate), titanium lactate ammonium salt, titanium lactate, titanium lactate, polyhydroxy titanium stearate and the like.

  Alternatively, a zirconium alkoxide represented by the following general formula (5), a zirconium acylate represented by the following general formula (6), and an organic zirconium represented by a zirconium chelate (complex) represented by the following general formula (7) Compound etc. are mentioned. Note that R described in the general formulas (5) to (7) each represents an alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a dodecyl group, a tridecyl group, a tetradecyl group, and a pentadecyl group. .

  Further, zirconium tetranormal propoxide, zirconium tetranormal butoxide, zirconium tetraacetylacetonate, zirconium tributoxymonoacetylacetonate, zirconium monobutoxyacetylacetonate bis (ethylacetoacetate), zirconium dibutoxybis (ethylacetoacetate), Organic zirconium compounds such as zirconium tetraacetylacetonate, zirconium tributoxy monostearate and the like can be mentioned.

(Other additives used to form the color tone adjustment layer)
An organic compound or an inorganic compound that is solid at room temperature can be added to the color tone adjusting layer. Examples of these compounds include known thermoplastic resins, heat or photocurable resins, and inorganic fine particle compounds. Moreover, when a compound is a liquid at normal temperature, what the additive can hold | maintain stably in a color tone adjustment layer can be used.

(Method for forming color tone adjustment layer)
The method for producing the gas barrier film of the present invention comprises:
(1) For forming a color tone adjusting layer containing a color tone adjusting agent on the gas barrier layer after forming the gas barrier layer on the resin base material by the plasma CVD method which is the first gas barrier layer forming method. A method for producing a gas barrier film by laminating a color tone adjusting layer by a wet coating method using a coating solution, or (2) a gas containing polysilazane which is a method for forming a second gas barrier layer on a resin substrate The barrier layer-forming coating solution is applied and dried by a wet coating method to form a thin film containing polysilazane, and after the thin film is subjected to a modification treatment to form a gas barrier layer, on the gas barrier layer, A method for producing a gas barrier film by laminating a color tone adjusting layer by a wet coating method using a coating solution for forming a color tone adjusting layer containing a color tone adjusting agent,
It is characterized by being.

  In addition, as a method of forming a color tone adjustment layer by the wet coating method, a coating solution for forming a color tone adjustment layer is applied and dried on a gas barrier layer to form a coating film, and then necessary for the formed coating film. The color tone adjustment layer is formed by performing a suitable modification process (for example, an ultraviolet irradiation process for irradiating vacuum ultraviolet light similar to that used for forming the second gas barrier layer or a heating process for irradiating heat rays). A method may be applied.

  As a method for forming a color tone adjusting layer according to the present invention, when an inorganic compound reactive with moisture is used, a coating solution obtained by dissolving and dispersing the compound in a solvent having a low moisture content is used in a low humidity environment. It is preferable to form by applying and drying. Here, since the humidity in a low humidity environment changes with temperature, the relationship between temperature and humidity shows a preferable form by the regulation of dew point temperature. A preferable dew point temperature is 4 ° C. or less (temperature 25 ° C./humidity 25%), a more preferable dew point temperature is −8 ° C. (temperature 25 ° C./humidity 10%) or less, and a more preferable dew point temperature is −31 ° C. (temperature 25 ° C./temperature). Humidity 1%) or less.

  Moreover, the layer thickness of the color tone adjusting layer according to the present invention is usually in the range of 1 to 1000 nm, and preferably in the range of 10 to 500 nm. When the layer thickness of the color tone adjusting layer according to the present invention is within the range specified above, it is easy to ensure the uniformity of the coating film and to easily adjust the color tone of the gas barrier layer.

  In the present invention, the layer thickness of the color tone adjusting layer is such that the layer thickness of the gas barrier layer falls within the range of 0.2 to 10 times the layer thickness of the color tone adjusting layer when compared with the layer thickness of the gas barrier layer. It is preferable to form.

(About color adjustment by the color adjustment layer)
In the gas barrier film of the present invention, a preferable color tone range of the transmission color (L ^* , a ^* , b ^* ) of the gas barrier film is a distance ΔE (a ^* from the Z origin according to the description of JIS Z 8722) ^. -b ^*) = ^{[((a *) 2 + (} b *) 2) 1/2 ] value of a generally less than 4.0, preferably less than 2.0. L ^* here is an index representing the brightness of the color, L ^* = 0 is black, and L ^* = 100 is white. Further, a ^* and b ^* are called chromatic index, a ^* is a coordinate relating to red / magenta and green, b ^* is a coordinate relating to yellow and blue, and ΔE (a ^* − b ^* ) represents the color difference from the Z origin.

In particular, when the gas barrier layer according to the present invention is laminated on a resin base material, the value of L ^* decreases and the value of b ^* tends to increase. In this case, when a blue color tone adjusting agent is contained in any of the constituent layers of the gas barrier film so that b ^* is negative, the adjustment is performed so as to approach the b ^* value of the initial resin base material. Although it is possible, the value of L ^* may further decrease at the same time. In this case, there is no problem if L ^* after color tone adjustment can be kept within a preferable range, but when a color tone adjusting agent (fluorescent substance) that emits fluorescence preferably used according to the present invention is added, it is included in the observation light. Since it is converted to a wavelength that cancels yellowishness by absorbing short-wavelength light, the b ^* value is adjusted in the preferred direction without resulting in a decrease in L ^* value, that is, a decrease in brightness. can do.

(Pencil hardness of color tone adjustment layer)
As the surface hardness of the color tone adjusting layer according to the present invention, the pencil hardness is preferably in the range of HB to 4H.

  The pencil hardness defined in the present invention is a value measured by “scratch hardness (pencil method)” in accordance with JIS K 5600-5-4: 1999 (ISO / DIS 15184: 1996) Part 5—Section 5. is there.

  As means for adjusting the pencil hardness (JIS K 5600-5-4) on the surface of the color tone adjusting layer within the range of HB to 4H, the binder type constituting the color tone adjusting layer, its ratio, or curing conditions are appropriately controlled. As a result, the gas barrier properties and transparency after storage in a high temperature and high humidity environment can be maintained better.

<Application field of gas barrier film>
Applications of the gas barrier film of the present invention include application to the following electronic devices and optical members.

(Electronic device)
The gas barrier film of the present invention can be preferably used for an electronic device that is easily affected by performance deterioration due to chemical components in the air (for example, oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.). .

  Examples of the electronic device include an 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 effects of the present invention can be obtained more efficiently, it is preferably used for an organic EL element or a solar cell, and particularly preferably applied to an organic EL element.

  As a method for applying the gas barrier film of the present invention to the electronic device, it can be used as a substrate for an electronic device or a film for sealing by a solid sealing method. The solid sealing method is a method in which a protective layer is formed on an electronic device, and then 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.

<Organic EL device>
The specific structure of the organic EL element using the gas barrier film of the present invention is described in detail in JP-A No. 2007-30387.

<Liquid crystal display element>
The reflective liquid crystal display device has a configuration including a lower substrate, a reflective electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, a transparent electrode, an upper substrate, a λ / 4 plate, and a polarizing film in order from the bottom. The gas barrier film of the present invention can be used as a substrate for the transparent electrode and an upper substrate. In the case of color display, it is preferable to further provide a color filter layer between the reflective electrode and the lower alignment film, or between the upper alignment film and the transparent electrode.

  The transmissive liquid crystal display device includes a backlight, a polarizing plate, a λ / 4 plate, a lower transparent electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, an upper transparent electrode, an upper substrate, a λ / 4 plate, and a polarization in order from the bottom. It has a structure consisting of a film. In the case of color display, it is preferable to further provide a color filter layer between the lower transparent electrode and the lower alignment film, or between the upper alignment film and the transparent electrode.

The type of the liquid crystal cell is not particularly limited, but more preferably, a TN type (Twisted Nematic), an STN type (Super Twisted Nematic), a HAN type (Hybrid Aligned Nematic), a VA type (Vertical Alignment), an EC type, a Bt type. , OCB type (Optically Compensated)
Bend), IPS type (In-Plane Switching), and CPA type (Continuous Pinwheel Alignment) are preferable.

<Other electronic devices>
Examples of other applications of the gas barrier film of the present invention include, for example, the thin film transistors described in JP-T-10-512104, JP-A-5-127822, JP-A-2002-48913, and the like. Examples thereof include a touch panel and electronic paper described in JP-A No. 2000-98326.

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

<Circularly polarizing plate>
A circularly polarizing plate can be prepared by using the gas barrier film of the present invention as a substrate and laminating a λ / 4 plate and a polarizing plate. In this case, the lamination is performed so that the angle formed by the slow axis of the λ / 4 plate and the absorption axis of the polarizing plate is 45 °. As such a polarizing plate, one that is stretched in a direction of 45 ° with respect to the longitudinal direction (MD) is preferably used. For example, those described in JP-A-2002-865554 can be suitably used. . By sealing these electronic devices using the gas barrier film according to the present invention, a lighter and more flexible product can be obtained.

  The effects of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples. Moreover, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented. In the following operations, unless otherwise specified, measure operation and physical property values. It is performed in an environment of 25 ° C. and a relative humidity of 50%. In addition, the number described in parentheses after each constituent element represents the code number described in each figure.

<Production of gas barrier film>
[Preparation of gas barrier film 1]
(1. Production of resin base material laminate)
<1-1. Preparation of resin base material (2)>
As the resin base material (2), a 100 μm thick polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., Cosmo Shine A4300, abbreviated as PET in Table 1), which is a thermoplastic resin base material and is easily bonded to both surfaces. The resin substrate was used and conditioned for 96 hours in an environment of a temperature of 25 ° C. and a relative humidity of 55%.

<1-2. Formation of Bleed-Out Prevention Layer (6)>
On one side of the resin base material (2), a UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) Z7535 manufactured by JSR Co., Ltd. is used so that the film thickness after drying becomes 3 μm. After coating at 80 ° C. for 3 minutes, the coating was cured at 1.0 J / cm ² as a curing condition using a high-pressure mercury lamp in an air atmosphere to form a bleed-out prevention layer (6). This was designated as resin base material 1S.

<Formation of Anchor Coat Layer 1 (5)>
Next, on the other surface side of the resin substrate (2), OPSTA Z7501 which is a UV curable organic / inorganic hybrid hard coat material manufactured by JSR Corporation is used under the condition that the film thickness after coating and drying is 4 μm. After applying using a wire bar, drying was performed at 80 ° C. for 3 minutes, and then curing was performed under a curing condition of 1.0 J / cm ² using a high-pressure mercury lamp in an air atmosphere. (5) was formed.

(2. Formation of gas barrier layer (3))
Next, using the plasma CVD manufacturing apparatus (S1) that is provided with a gas barrier layer forming station and applies a magnetic field by the online method shown in FIG. 3, the following plasma CVD method ("CVD method" is shown in Table 1). The gas barrier layer (3) was formed on the anchor coat layer 1 (5) of the resin base material (2) produced above.

  In the plasma CVD manufacturing apparatus (S1) according to the present invention, the resin base material (2) laminated in a roll shape was mounted on the feeding roller (11A). Subsequently, the resin base material (2) fed out from the feeding roller (11A) is formed into a film forming roller (31), a conveying roller (22), a conveying roller (23), and a film forming roller (32) at a station for forming a gas barrier layer. ) In this order, and then a conveyance line was formed in a configuration in which the film was wound around the winding roller (11B).

  The gas barrier layer (3) is formed on the anchor coat layer 1 (5) of the resin base material (2) fed from the feed roller (11A) by the plasma CVD manufacturing apparatus (S1), and the film forming roller (31) and the composition roller. A gas barrier layer (3) was formed in a discharge space (film formation station) configured between the film rollers (32).

  In the formation of the gas barrier layer (3) in the discharge space (film formation station), a magnetic field is applied using a magnetic field generator (61 and 62) between a pair of film formation rollers (31 and 32) having a diameter of 180 mm. At the same time, power is supplied from the plasma generation power source (51) to the film forming rollers (31 and 32) to generate a plasma between the film forming rollers to form a discharge space. A film-forming gas composed of hexamethyldisiloxane (HMDSO) as a reactive gas and oxygen gas as a reaction gas is supplied from a film-forming gas supply pipe (41), and the film-forming conditions (plasma CVD conditions) shown below are satisfied. Then, a thin film was formed by a plasma CVD method, and a gas rear layer (3) was formed on one surface of the resin base material (2).

<Gas barrier layer deposition conditions>
Source gas: Hexamethyldisiloxane (HMDSO) Supply amount: 50 sccm (Standard Cubic Centimeter per Minute, 0 ° C., 1 atm standard)
Reaction gas: Oxygen gas (O ₂ ) Supply amount: 500 sccm (0 ° C., 1 atm standard)
Degree of vacuum in the vacuum chamber: 1.5 Pa
Applied power from the power source for plasma generation: 0.9 kW
Frequency of power source for plasma generation: 70 kHz
Transport speed of resin base unit: 1.0 m / min
The layer thickness of the gas barrier layer (3) formed as described above was 250 nm.

(3. Formation of color tone adjustment layer (4))
<3.1: Preparation of color tone adjusting agent solution 1>
The following organic fluorescent agent 1 was dissolved using anhydrous toluene as a solvent to prepare a color tone adjusting agent solution 1.

Organic fluorescent agent 1: Blue organic fluorescent material Lumogen Blue 650 (BASF Japan)
5% by mass
Organic solvent: anhydrous toluene 95% by mass
<3.2: Preparation of metal oxide binder liquid B1>
The following additives were mixed and dissolved to prepare a metal oxide binder liquid B1.

Silicone organic-inorganic hybrid material (silsesquioxane): SQ series OX-SQ SI-20 (polysiloxane, manufactured by Toagosei Co., Ltd.)
97% by mass
Epoxy monomer: Celoxide 2021P (manufactured by Daicel Corporation)
1.5% by mass
Photopolymerization initiator: RHODORSIL (R) PHOTOINITIATOR 2074 (manufactured by Rhodia Japan) 1.5% by mass
<3.3: Preparation of coating liquid for forming color tone adjusting layer>
The prepared color tone adjusting agent solution 1 and the metal oxide binder liquid B1 were mixed at the following ratio to prepare a color tone adjusting layer forming coating solution.

Color adjusting agent solution 1 30 parts by mass Metal oxide binder liquid B1 100 parts by mass <3.4: Application of coating solution for forming color adjusting layer>
After applying the prepared coating solution for forming the color tone adjusting layer on the gas barrier layer (3) of the resin base material in a nitrogen atmosphere, drying at 70 ° C. for 3 minutes and then curing under the following photocuring conditions. Thus, a color tone adjusting layer having a thickness of 100 nm after drying was formed.

  Photocuring conditions: A high-pressure mercury lamp (80 W / cm) was used, and light irradiation was performed for 10 minutes in a dry nitrogen atmosphere with a lamp height of 10 cm.

[Preparation of gas barrier film 2]
In the production of the gas barrier film 1, except that the following organic fluorescent agent 2 was used instead of the organic fluorescent agent 1 (blue organic fluorescent material Lumogen Blue 650) used for forming the color tone adjusting layer (4). Thus, a gas barrier film 2 was produced.

Organic fluorescent agent 2: fluorescent whitening agent (Benetex OB, manufactured by Mayzo, following structure)

[Preparation of gas barrier film 3]
In the production of the gas barrier film 1, a gas was produced in the same manner except that the following inorganic fluorescent agent 1 was used instead of the organic fluorescent agent 1 (blue organic fluorescent material Lumogen Blue 650) used for forming the color tone adjusting layer. Barrier film 3 was produced.

Inorganic fluorescent agent 1: 5 mg / ml toluene solution of core-shell type quantum dots (Lumidot CdSe / ZnS 480 average particle diameter: 2.5 nm SIGMA-ALDRICH) [Preparation of gas barrier film 4]
In the production of the gas barrier film 3, the following metal oxide binder liquid B2 is used instead of the metal oxide binder liquid B1 used for forming the color tone adjusting layer, and the inorganic fluorescent agent 1 and the metal oxide binder liquid are used. A gas barrier film 4 was produced in the same manner except that the ratio of B2 was changed as follows.

(1) Metal oxide binder liquid B2: Aquamica NL110A (perhydroxypolysilazane, AZ Electronic Materials Co., Ltd.) 20 mass% xylene solution (2) Mixing ratio; Toluene solution of inorganic fluorescent agent 1 (5 mg / ml) ): Metal oxide binder liquid B2 = 20: 100 (mass ratio)
[Preparation of gas barrier film 5]
In the production of the gas barrier film 1, the formation of the gas barrier layer (3) was performed in the same manner except that it was performed by the following wet coating method (polysilazane / excimer light treatment, polysilazane modification method) instead of the plasma CVD method. Thus, a gas barrier film 5 was produced.

(Formation of gas barrier layer (3) by wet coating method: polysilazane modification method)
10% by weight dibutyl ether solution of perhydropolysilazane (Aquamica NN120-10, manufactured by AZ Electronic Materials Co., Ltd.) and N, N, N ′, N′-tetramethyl-1,6-diaminohexane as an amine catalyst Resin formed as described above under the condition that the (average) layer thickness after drying a gas barrier layer forming coating solution prepared by mixing a 10% by weight dibutyl ether solution at 99: 1 (mass ratio) is 250 nm. It apply | coated on the anchor-coat layer (5) of a base material (2), and it dried for 1 minute with the dry air of temperature 50 degreeC and dew point-5 degreeC. Subsequently, it was treated with dry air at a temperature of 95 ° C. and a dew point of −5 ° C. for 2 minutes to form a polysilazane layer on the anchor coat layer (5) of the resin substrate (2).

(Modification treatment of polysilazane layer)
Next, a polysilazane reforming method (“PS reforming method” is shown in Table 1) in which the formed polysilazane layer surface is irradiated with vacuum ultraviolet light (excimer reforming treatment) under the following reforming treatment apparatus and reforming treatment conditions. The gas barrier layer (3) was formed by modifying the polysilazane layer.

<Modification processing equipment>
Processing apparatus name: Ex D irradiation apparatus MODEL manufactured by MCOM Co., Ltd .: MECL-M-1-200
Wavelength: 172nm
Lamp filled gas: Xe
<Reforming treatment conditions>
Average excimer light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 2mm
Stage heating temperature: 95 ° C
Oxygen concentration in the irradiation apparatus: Maintaining 0.1% by volume or less Stage transport speed during excimer light irradiation: 10 mm / sec Number of stage transport times during excimer light irradiation: Accumulated amount of excimer light exposure on the sample surface is 5000 mj / was adjusted so that the cm ^2.

[Preparation of gas barrier film 6]
In the production of the gas barrier film 4, the formation of the gas barrier layer (3) was carried out in the same manner except that it was carried out by the same polysilazane modification method used for the production of the gas barrier film 5 instead of the plasma CVD method. Thus, a gas barrier film 6 was produced.

[Preparation of gas barrier film 7]
In the production of the gas barrier film 5, instead of the metal oxide binder liquid B1 used for forming the color tone adjusting layer, a binder liquid B3 containing only the polyester urethane resin not containing the following metal oxide is used, and the organic fluorescent agent 1 and The gas barrier film 7 was produced in the same manner except that the mass ratio of the binder liquid B3 was changed as follows and the photocuring treatment with a high-pressure mercury lamp was omitted.

Binder liquid B3: Polyester urethane resin Byron UR-4800 (manufactured by Toyobo Co., Ltd.), 32% by mass of methyl ethyl ketone solution (containing no metal oxide)
5 wt% anhydrous toluene solution of organic fluorescent agent 1: 32 wt% methyl ethyl ketone solution of metal oxide binder B3 = 50: 50 (mass ratio)
[Production of gas barrier film 8]
A gas barrier film 8 was prepared in the same manner as in the preparation of the gas barrier film 5 except that the organic fluorescent agent 1 used for forming the color tone adjusting layer (4) was omitted.

[Preparation of gas barrier film 9]
A gas barrier film 9 was produced in the same manner as in the production of the gas barrier film 1 except that the organic fluorescent agent 1 used for forming the color tone adjusting layer (4) was changed to the following organic fluorescent agent 3.

Organic fluorescent agent 3: Green light emitting organic fluorescent agent Lumogen Green 850 (manufactured by BASF Japan)
[Production of Gas Barrier Film 10]
In the production of the gas barrier film 5, the mixing ratio of the organic fluorescent agent 1 and the metal oxide binder liquid B1 used for forming the color tone adjusting layer was changed to 30 parts by mass: 150 parts by mass, and the surface pencil hardness was changed to B. A gas barrier film 10 was produced in the same manner except that the above was achieved.

[Preparation of gas barrier film 11]
In the production of the gas barrier film 5, the mixing ratio of the organic fluorescent agent 1 and the metal oxide binder liquid B1 used for forming the color tone adjusting layer was changed to 30 parts by mass: 120 parts by mass, and the surface pencil hardness was changed to HB. A gas barrier film 10 was produced in the same manner except that the above was achieved.

[Preparation of gas barrier film 12]
In the production of the gas barrier film 5, the anchor coat layer 1 coating solution formed on the resin substrate 1 (2) is changed to the anchor coat layer coating solution 2 prepared by the following method to produce a resin substrate 2. A gas barrier film 12 was produced in the same manner except that this was used. (Preparation of anchor coat layer coating solution 2)
As the anchor coat layer coating liquid 2, 54 g of an ultraviolet curable resin (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Purple Light UV-1700B) and 6.3 g of a radical polymerization initiator (Ciba Specialty Chemicals, Irgacure 184) are used. The mixture was mixed to prepare an acrylic ultraviolet curable pressure-sensitive adhesive composition solution.

[Production of gas barrier film 13]
In the production of the gas barrier film 12, the configuration of the color tone adjusting layer is changed to the color tone adjusting layer constituting the gas barrier film 6, and vacuum ultraviolet light irradiation (excimer modification is performed with the following reforming processing apparatus and reforming processing conditions. The gas barrier film 13 was produced in the same manner except that the quality treatment was performed.

<Reforming treatment>
Reforming apparatus: excimer irradiation apparatus MODEL manufactured by MCOM Co., Ltd .: MECL-M-1-200
Wavelength: 172nm
Lamp filled gas: Xe
<Reforming treatment conditions>
Average excimer light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 2mm
Stage heating temperature: 95 ° C
Oxygen concentration in the irradiation apparatus: maintained at 0.1% or less Stage transport speed during excimer light irradiation: 10 mm / sec Number of stage transport times during excimer light irradiation: Accumulated amount of excimer light exposure on the sample surface is 5000 mj / cm It adjusted so that it might be set to ² .

[Preparation of gas barrier film 14]
In the production of the gas barrier film 1, a gas barrier film 14 was produced in the same manner except that the color tone adjusting layer was removed.

[Preparation of gas barrier film 15]
In the production of the gas barrier film 14, a gas barrier film 15 was produced in the same manner except that the resin substrate 1 was changed to the resin substrate 4 described below.

(Preparation of resin substrate 2)
The following chip A is used as the raw material for the I layer, and the mixed raw material in which the chips A and B are mixed at a ratio of 90% and 10%, respectively, is used as the raw material for the II layer. After melting at 285 ° C., the I layer is the outer layer (outermost layer) and the II layer is the inner layer (intermediate layer). On the casting drum cooled to 40 ° C., two layers and three layers (I / II / I) Were coextruded and cooled and solidified to obtain a non-oriented film.

  Next, the film was stretched 3.5 times in the temperature range of 85 to 100 ° C. to obtain a longitudinally uniaxially stretched film.

  This film was stretched 4.0 times horizontally in an atmosphere of 85 to 110 ° C., and then heat-treated at 235 ° C. to obtain a resin substrate 3 which is a biaxially stretched polyester film having a thickness of 100 μm.

  Each layer thickness of the resin substrate 3 was 15 μm / 70 μm / 15 μm.

  Manufacture of chip A: Chip A which is a polyester chip having a melt viscosity of 0.66 and containing 0.12 part of amorphous silica having an average particle diameter of 2.5 μm was obtained by a known melt polymerization method.

  Manufacture of chip B: The above chip A was subjected to a twin screw extruder with a vent at an extrusion temperature of 290 ° C., and ADEKA STAB LA-31 (manufactured by ADEKA Corporation) as a benzotriazole-based UV absorber and fluorescence as a color tone adjusting agent A powder obtained by mixing the following compound (A), which is a brightening agent, at a mass ratio of 1: 2 is supplied to a concentration of 10% by mass, melt-kneaded to form a chip, and contains a color tone adjusting agent. A master batch polyester chip (chip B) was manufactured. The intrinsic viscosity of the obtained polyester was 0.60.

[Preparation of gas barrier film 16]
In the production of the gas barrier film 1, the gas barrier film 16 was produced in the same manner except that the positions of the gas barrier layer and the color tone adjusting layer were reversed and the color tone adjusting layer was formed between the resin base material and the gas barrier layer. .

[Production of gas barrier film 17]
A gas barrier film 17 was produced in the same manner as in the production of the gas barrier film 1 except that the color tone adjusting layer was formed on the bleed-out prevention layer on the back surface of the resin base material.

[Preparation of gas barrier film 18]
A silicon-containing hydrocarbon layer (SiC layer) having a thickness of 10 nm is formed on the gas barrier layer of the produced gas barrier film 14 under the following conditions using a winding type plasma CVD apparatus described in JP2013-121686A. The gas barrier film 18 was produced by laminating.

(conditions)
It formed according to (Condition 2) described in Example 1 of JP2013-121686A.

Used film forming chamber; second film forming chamber shown in FIG. 2 of JP2013-121686A supply gas; gas composition of ethylene: HMDSO = 9: 1 (unit: slm) degree of vacuum of film forming chamber; 3.0Pa
Supply power: 22kW
Film transport speed: 50 m / min
[Production of gas barrier film 19]
In the formation of the color tone adjusting layer of the gas barrier film 6, a metal oxide containing the following zirconium compound (abbreviated as Zr in Table 1) as a metal-oxygenated metal oxide instead of the metal oxide binder liquid B1. Using the binder liquid B4, the color tone adjusting layer formed by adjusting the mass ratio of the zirconium compound and the color tone adjusting agent to be the same as the coating liquid for adjusting the color adjusting layer used for forming the color tone adjusting layer of the gas barrier film 6 A gas barrier film 19 was produced in the same manner except that the coating liquid for coating was used.

Zirconium compound: Zirconium tributoxy monoacetylacetonate (trade name: Orgatyx ZC-540, manufactured by Matsumoto Fine Chemical Co., Ltd., component concentration: 45 mass%, zirconium content: 10.2 mass%, solvent composition: toluene, 1-butanol Butyl acetate)
[Preparation of gas barrier film 20]
In the formation of the color tone adjusting layer of the gas barrier film 6, a metal oxide containing the following titanium compound (abbreviated as Ti in Table 1) as a metal-oxygenated metal oxide instead of the metal oxide binder liquid B1. Using the binder liquid B5, the color tone adjusting layer formed by adjusting the mass ratio of the titanium compound and the color tone adjusting agent to be the same as the coating liquid for adjusting the color adjusting layer used for forming the color tone adjusting layer of the gas barrier film 6 A gas barrier film 20 was produced in the same manner except that the coating liquid for coating was used.

Titanium compound: Titanium butoxide dimer (trade name: ORGATICS TA-23, manufactured by Matsumoto Fine Chemical Co., Ltd., component concentration: 95% by mass or more, titanium content: 17.4% by mass, solvent composition: 1-butanol)
[Preparation of gas barrier film 21]
In the production of the gas barrier film 6, the gas barrier was similarly obtained except that the following blue dye 1 was used instead of the inorganic fluorescent agent 1 (core-shell type quantum dots) used for forming the color tone adjusting layer (4). Film 21 was produced.

Blue dye 1: 1,4-di (2,4,6-trimethylphenyl) anthraquinone [Preparation of gas barrier film 22]
In the production of the gas barrier film 6, the gas barrier was similarly prepared except that the following blue dye 2 was used instead of the inorganic fluorescent agent 1 (core-shell type quantum dots) used for forming the color tone adjusting layer (4). Film 22 was produced.

Blue dye 2: 1,4-di (2,4,6-triethylphenyl) anthraquinone Table 1 shows the structures of the gas barrier films 1 to 22 produced above.

  The details of each item described in abbreviations in Table 1 are as follows.

<Color tone adjuster>
Organic fluorescent agent 1: Blue organic fluorescent material Lumogen Blue 650 (BASF Japan)
Organic fluorescent agent 2: fluorescent whitening agent (Benetex OB, manufactured by Mayzo)
Organic fluorescent agent 3: Green light emitting organic fluorescent agent Lumogen Green 850 (manufactured by BASF Japan)
Inorganic fluorescent agent 1: core-shell type quantum dot (Lumidot CdSe / ZnS 480)
Average particle diameter: 2.5 nm (SIGMA-ALDRICH)
Blue dye 1: 1,4-di (2,4,6-trimethylphenyl) anthraquinone Blue dye 2: 1,4-di (2,4,6-triethylphenyl) anthraquinone <metal oxide binder>
B1: Silicone organic-inorganic hybrid material (silsesquioxane): SQ series OX-SQ SI-20 (polysiloxane, manufactured by Toagosei Co., Ltd.)
B2: Aquamica NL110A Solid content 20% by mass xylene solution (Perhydroxypolysilazane, manufactured by AZ Electronic Materials Co., Ltd.)
B4: Zirconium tributoxy monoacetylacetonate (trade name: ORGATICS ZC-540, manufactured by Matsumoto Fine Chemical Co., Ltd.)
B5: Titanium butoxide dimer (trade name: Olga Chicks TA-23, manufactured by Matsumoto Fine Chemical Co., Ltd.)
<Binder containing no metal oxide>
B3: Polyester urethane resin Byron UR-4800 (manufactured by Toyobo Co., Ltd.)
<Arrangement position of color tone adjustment layer (addition position of color tone adjustment agent)>
P1: Bleed-out prevention layer / resin substrate / anchor coat layer / gas barrier layer / color tone adjusting layer P2: Bleed-out prevention layer / (resin substrate + color tone adjusting agent) / anchor coat layer / gas barrier layer P3: Bleed out Prevention layer / resin substrate / color tone adjustment layer / anchor coat layer / gas barrier layer P4: Color tone adjustment layer / bleed out prevention layer / resin substrate / anchor coat layer / gas barrier layer << Evaluation of gas barrier film >>
About each produced said gas barrier film, various measurement and evaluation were performed in accordance with the following method.

[Scratch hardness: surface pencil hardness measurement]
The outermost surface of each of the gas barrier films prepared above and the pencil hardness of the resin base material used for the production of each gas barrier film are measured in accordance with the method specified in JIS K 5600-5-4 (ISO / DIN 15184). did. In addition, the pencil hardness of each resin base material was measured about the laminated body of the resin base material (2) and an anchor coat layer (5).

  Using the test equipment specified above, a load of 750 ± 10 g was applied to the tip of the pencil on the surface of the color tone adjustment layer or the anchor coat layer of the resin substrate, and the angle of the pencil was 45 ± 1 °.

  The pencils used were UNI 6B to 6H manufactured by Mitsubishi Pencil Co., Ltd., and the hardness of the hardest pencil with no scars was taken as the pencil hardness.

[Characteristic evaluation in the initial state]
The following evaluation was performed on each gas barrier film immediately after production.

(Evaluation of gas barrier properties)
About each produced said gas barrier film, the water vapor transmission rate in 38 degreeC and 90% RH was measured using MOCON water vapor transmission rate measuring apparatus PERMATRAN-W made from MOCON. Subsequently, gas barrier property was evaluated according to the following evaluation rank.

5: water vapor permeability is less than 0.05g ^/ m 2 · day 4: water vapor permeability, 0.05g ^/ m 2 · day or more and less than 0.10g ^/ m 2 · day 3: water vapor permeability The degree is 0.10 g / m ² · day or more and less than 1.00 g / m ² · day 2: The water vapor permeability is 1.00 g / m ² · day or more and less than 5.00 g / m ² · day 1: Water vapor permeability is 5.00 g / m ² · day or more (evaluation of color tone)
A color difference meter (“SQ2000”, manufactured by Nippon Denshoku Industries Co., Ltd.) is used to measure the transmission color (L ₁ ^* , a ₁ ^* , b ₁ ^* ) of each gas barrier film in accordance with JIS Z8722 and JIS Z8729. Was measured using a C / 2 light source.

For the measurement of the color tone, the distance ΔE ₁ (a ₁ ^* −b ₁ ^* ) from the origin in the plane (a ₁ ^* −b ₁ ^* ) plane was determined according to the lightness L ₁ ^* and the following formula. L ₁ ^* is better as it is closer to 100, and ΔE ₁ (a ₁ ^* −b ₁ ^* ) is better as it is closer to 0.

ΔE ₁ (a ₁ ^* −b ^{1 *} ) = [(a ₁ ^* ) ² + (b ₁ ^* ) ² )] ^1/2
For _L ^{1 *} and Delta] E ₁ was measured _(a ^{1 *} _-b ¹ *) by the above, according to the following criteria were evaluated the color tone immediately after production.

5: L ₁ ^* is 90 or more and ΔE ₁ (a ₁ ^* −b ₁ ^* ) is less than 2.0 4: L ₁ ^* is 88 or more and less than 90, and ΔE ₁ (a ₁ ^* −b ₁ ^* ) is 2.0 or more and less than 3.0 3: L ₁ ^* is 85 or more and less than 88, ΔE ₁ (a ₁ ^* −b ₁ ^* ) is 3.0 or more and 5.0 Is less than 2: L ₁ ^* is 81 or more and less than 85; ΔE ₁ (a ₁ ^* −b ₁ ^* ) is 5.0 or more 1: L ₁ ^* is less than 81 and ΔE ₁ (a ₁ ^* −b ₁ ^* ) is 5.0 or more (evaluation of visible light transmittance)
For each gas barrier film, in accordance with ASTM D 1003, the visible light transmittance is measured with a haze meter (“NDH5000”, manufactured by Nippon Denshoku Industries Co., Ltd.) using a D65 light source. Visible light transmittance was evaluated.

5: Visible light transmittance is 92% or more 4: Visible light transmittance is 90% or more and less than 92% 3: Visible light transmittance is 88% or more and less than 90% 2: Visible Light transmittance is 85% or more and less than 88% 1: Visible light transmittance is less than 85% [Characteristic evaluation after forced deterioration treatment]
Each gas barrier film was subjected to a forced deterioration treatment at 85 ° C. in an environment of 85% RH for 500 hours, and then subjected to the following evaluations.

(Evaluation of gas barrier properties)
About each gas barrier film which performed the said high temperature and high-humidity process, the water vapor permeability in 38 degreeC and 90% RH was measured using MOCON water vapor permeability measuring apparatus PERMATRAN-W made from MOCON. Subsequently, gas barrier property was evaluated according to the following evaluation rank.

5: water vapor permeability is less than 0.05g ^/ m 2 · day 4: water vapor permeability, 0.05g ^/ m 2 · day or more and less than 0.10g ^/ m 2 · day 3: water vapor permeability The degree is 0.10 g / m ² · day or more and less than 1.00 g / m ² · day 2: The water vapor permeability is 1.00 g / m ² · day or more and less than 5.00 g / m ² · day 1: Water vapor permeability is 5.00 g / m ² · day or more (evaluation of color tone stability)
Measure L ₂ ^* , a ₂ ^* , and b ₂ ^* after 500 hours of forced deterioration treatment at 85 ° C. and 85% RH in the same manner as the color tone evaluation in the initial state. did.

Next, ΔE ₂ is measured according to the following equation using L ₂ ^* , a ₂ ^* , b ₂ ^* measured above and L ₁ ^* , a ₁ ^* , b ₁ ^* measured on the sample in the initial state, The color tone stability was evaluated according to the following criteria.

ΔE ₂ = [(L ₂ ^* −L ₁ ^* ) ² + (a ₂ ^* −a ₁ ^* ) ² + (b ₂ ^* −b ₁ ^* ) ² ] ^1/2
5: ΔE ₂ is less than 1.0 4: ΔE ₂ is 1.0 or more and less than 2.0 3: ΔE ₂ is 2.0 or more and less than 4.0 2: ΔE ₂ Is 4.0 or more and less than 7.0 1: ΔE ₂ is 7.0 or more (Evaluation of visible light transmittance)
About the sample after a forced deterioration process, the visible light transmittance | permeability was evaluated with the method and evaluation rank similar to the said initial state.

  The results obtained as described above are shown in Table 1.

  As is clear from the results described in Table 1, the gas barrier film having the color tone adjusting layer having the configuration defined in the present invention has a gas barrier property, a color tone and a visible light transmittance immediately after production with respect to the comparative example. It can be seen that the film has excellent gas barrier properties, color tone stability and visible light transmittance after storage in a high temperature and high humidity environment.

  The gas barrier film of the present invention has excellent gas barrier performance and color tone stability, high transparency, and excellent durability in a high temperature and high humidity environment, and is an electronic device or optical film member. In particular, as an electronic device, it can be suitably used as a sealing member for an organic EL element, a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, a solar cell (PV), or the like.

DESCRIPTION OF SYMBOLS 1 Gas barrier film 2 Resin base material 3 Gas barrier layer 4 Color tone adjustment layer 5 Anchor coat layer 6 Bleed-out prevention layer 11A Feeding roller 11B Winding roller 16 Vacuum chamber 17 Vacuum pump 18 Exhaust port 22, 23 Conveying rollers 31, 32 Composition Film roller 41 Film-forming gas supply pipe 51 Power source for plasma generation 61, 62 Magnetic field generator S1 Plasma CVD manufacturing apparatus

Claims (12)

  Having a gas barrier layer on the resin substrate, and having a color tone adjusting layer containing a compound having a metal-oxygen bond capable of holding the color tone adjusting agent and the color tone adjusting agent on the gas barrier layer. Characteristic gas barrier film.   The gas barrier film according to claim 1, wherein the gas barrier layer is made of a vapor deposition film.   The gas barrier film according to claim 1, wherein the gas barrier layer comprises a coating film.   The gas barrier film according to claim 3, wherein the gas barrier layer comprises a coating film containing at least polysilazane or a modified product thereof.   5. The gas barrier film according to claim 1, wherein the color tone adjusting layer is laminated on the gas barrier layer as a coating film.   The gas barrier film according to any one of claims 1 to 5, wherein the color tone adjusting agent contained in the color tone adjusting layer is a fluorescent substance.   The gas barrier film according to claim 6, wherein the fluorescent substance is an organic fluorescent agent or an inorganic fluorescent agent.   The gas barrier film according to claim 6 or 7, wherein the fluorescent material is a blue fluorescent material having a maximum emission wavelength at 500 nm or less.   The compound having a metal-oxygen bond capable of holding the color tone adjusting agent contained in the color tone adjusting layer is a polysilazane or a compound having a polysiloxane structure, and the color tone adjusting layer is the polysilazane or polysiloxane. It consists of a coating film containing the compound which has a structure, The gas barrier film as described in any one of Claim 1- Claim 8 characterized by the above-mentioned.   10. The gas according to claim 1, wherein a pencil hardness (JIS K 5600-5-4) of the surface of the color tone adjusting layer is in a range of HB to 4H. Barrier film.   After forming a gas barrier layer on a resin substrate by plasma CVD, a color tone adjustment layer is laminated on the gas barrier layer by a wet coating method using a color tone adjustment layer forming coating solution containing a color tone adjusting agent. And manufacturing a gas barrier film.   A gas barrier layer-forming coating solution containing polysilazane is applied and dried on a resin substrate by a wet coating method to form a thin film containing polysilazane, and the thin film is subjected to a modification treatment to form a gas barrier layer. After forming, a gas barrier film is produced by laminating a color tone adjusting layer by a wet coating method using a coating solution for forming a color tone adjusting layer containing a color tone adjusting agent on the gas barrier layer. A method for producing a barrier film.

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