WO2015152300A1 - Method for producing gas barrier film, and gas barrier film produced using said production method - Google Patents

Abstract

The present invention provides a gas barrier film having excellent optical characteristics and low water vapor permeability, and a method for producing said gas barrier film. Provided is a method for producing a gas barrier film, said method having a step of forming a gas barrier layer on one surface of a TAC film substrate using a vacuum deposition method, wherein the step of forming the gas barrier layer is carried out with a heat-resistant laminate film, which has a laminate substrate and an adhesive layer, disposed via the adhesive layer on the surface opposite to a surface on which the gas barrier layer of the TAC film substrate is formed, and the ratio (A/B) of the thickness (A) of the TAC film substrate during said step to the thickness (B) of the laminate substrate is at most 2.2.

Description

Gas barrier film production method and gas barrier film produced by the production method

The present invention relates to a method for producing a gas barrier film and a gas barrier film produced by the production method.

Conventionally, in the fields of food, packaging materials, pharmaceuticals, etc., in order to prevent the permeation of gases such as water vapor and oxygen, it is relatively simple to provide an inorganic film such as a metal or metal oxide vapor deposition film on the surface of a resin substrate. Gas barrier films having a structure have been used.

In addition to packaging applications, it has been requested to develop into flexible electronic devices such as flexible solar cell elements, organic electroluminescence (EL) elements, liquid crystal display elements, etc., and many studies have been made.

Especially in optical applications such as organic EL, high barrier properties and transparency are required for the gas barrier film. For this reason, for example, as disclosed in Patent Document 1, a protective film is formed on the gas barrier film for the purpose of suppressing damage to the gas barrier layer during manufacturing and transport of the gas barrier film using a conventional resin substrate such as polyethylene terephthalate. A film was sometimes provided.

Further, as in Patent Document 2, when forming a gas barrier layer, when using a roll-to-roll method in which a roll-shaped substrate is continuously fed to a vacuum film forming apparatus and wound up again after forming the gas barrier layer, For the purpose of suppressing deterioration of the gas barrier layer due to winding tightening or air entrainment during lamination, a laminate film has been bonded to the gas barrier layer.

Thus, in the resin material used for the conventional base material, damage to the gas barrier layer generated after the gas barrier layer is formed has been suppressed by the laminate film.

In recent years, there is an increasing demand for transparency in gas barrier films used for optical film applications, and it is required to change the resin material used for the base material to a material with higher transparency. As such a material, triacetyl cellulose (TAC) is expected to be applied to a gas barrier film because of its high transparency.

Japanese Patent No. 5239240 JP 2010-234340 A

However, when a TAC film is used as the base resin, only a gas barrier film with insufficient barrier properties can be obtained even when the conventional laminate film as described above is applied.

Therefore, the present invention has been made in view of the above circumstances, and an object thereof is to provide a method for producing a gas barrier film having excellent optical characteristics and low water vapor permeability.

As a result of intensive studies to solve the above problems, the inventors of the present invention have a ratio of the thickness to the TAC film substrate in a certain range when forming a gas barrier layer by a vacuum film forming method. The present inventors have found that the above problem can be solved by forming a gas barrier layer in a state in which a heat-resistant laminate film having a laminate substrate is provided on the surface opposite to the gas barrier layer of the TAC film substrate. The invention has been completed.

That is, the above-mentioned subject of the present invention is a method for producing a gas barrier film having a step of forming a gas barrier layer on one surface of a TAC film substrate by a vacuum film forming method, wherein the laminate substrate and the adhesive layer are formed. A step of forming the gas barrier layer in a state in which the heat-resistant laminate film is disposed on the surface opposite to the surface of the TAC film substrate on which the gas barrier layer is formed via the adhesive layer, This is achieved by a method for producing a gas barrier film, wherein the ratio A / B of the thickness (A) of the film substrate and the thickness (B) of the laminate substrate is 2.2 or less.

According to the present invention, it is possible to provide a gas barrier film that suppresses the occurrence of defects in the gas barrier layer, has excellent optical properties, and has excellent barrier properties.

It is a schematic sectional drawing which shows the layer structure of the gas barrier film obtained by the manufacturing method of the gas barrier film which concerns on one Embodiment of this invention. It is a schematic diagram which shows an example of the vacuum plasma CVD apparatus used for formation of a 1st inorganic layer in the manufacturing method of the gas barrier film which concerns on one Embodiment of this invention. It is a schematic diagram which shows an example of the other manufacturing apparatus used for formation of a 1st inorganic layer in the manufacturing method of the gas barrier film which concerns on one Embodiment of this invention. Gas barrier film No. 1 is a silicon distribution curve, an oxygen distribution curve, and a carbon distribution curve.

The present invention relates to a method for producing a gas barrier film having a step of forming a gas barrier layer on one surface of a TAC film substrate by a vacuum film formation method, and the heat resistant laminate film having a laminate substrate and an adhesive layer Is formed on the surface of the TAC film substrate opposite to the surface on which the gas barrier layer is formed via the adhesive layer, and the step of forming the gas barrier layer is performed, and the thickness of the TAC film substrate A method for producing a gas barrier film, characterized in that the ratio A / B between (A) and the thickness (B) of the laminate substrate is 2.2 or less.

The method for producing a gas barrier film according to the present invention is a surface on which a heat-resistant laminate film having a laminate substrate having a thickness ratio with a TAC film substrate in a specific range is formed on the gas barrier layer of the TAC film substrate. And a step of forming a gas barrier layer by a vacuum film-forming method in a state where the gas barrier layer is disposed on the opposite surface.

According to such a method for producing a gas barrier film, by suppressing the thermal expansion of the TAC film substrate in the gas barrier layer forming step, it is possible to suppress the occurrence of defects in the gas barrier layer, and to achieve good water vapor barrier properties and A gas barrier film having optical properties can be obtained. Here, the mechanism for exerting the above-described effects by the configuration of the present invention is presumed as follows. The present invention is not limited to the following.

That is, the gas barrier layer on the base material of the gas barrier film is often formed by a vacuum film formation method such as a chemical vapor deposition method (chemical vapor deposition method). Alternatively, there is a method in which a coating liquid containing polysilazane is applied by a known wet coating method, dried, and reformed at a high temperature.

However, since such a method places a great thermal load on the TAC film substrate, when a material having a large thermal deformation such as TAC is used, the TAC film is formed during the formation of the gas barrier layer. Substrate deformation occurs. This makes it difficult to form a uniform formed gas barrier layer, and defects such as cracks and dangling bonds occur in the gas barrier layer. For this reason, the gas barrier layer thus formed has been deteriorated starting from the above-described defects under high humidity conditions.

As a result, a gas barrier film using a TAC film base material produced under a great thermal load has a problem in barrier performance that the water vapor permeability is high under high humidity conditions.

On the other hand, as in the method for producing a gas barrier film according to the present invention, the heat-resistant laminate film having a laminate substrate having a thickness ratio with the TAC film substrate is in a specific range, through the adhesive layer, By having the step of forming the gas barrier layer in a state of being disposed on the surface opposite to the surface on which the gas barrier layer of the TAC film substrate is formed, for example, during vacuum film formation (a large thermal load is applied). Thus, the TAC film substrate (prepared in this way) can be prevented from being thermally deformed, and the composition of the gas barrier layer can be prevented from becoming nonuniform and cracks can be effectively suppressed.

Also, it becomes possible to use a TAC film having excellent optical characteristics as a base material for a gas barrier film, and a gas barrier film having excellent barrier performance and optical characteristics can be obtained.

Therefore, the gas barrier film obtained by the production method according to the present invention has a low water vapor transmission rate and excellent optical characteristics.

Hereinafter, embodiments of the present invention will be described. In addition, this invention is not limited only to the following embodiment.

Unless otherwise specified, measurements such as operation and physical properties are performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.

The structure of the gas barrier film layer obtained by one embodiment of the production method according to the present invention will be described with reference to FIG.

In FIG. 1, a gas barrier film (with a heat resistant laminate film) 201 according to the production method of the present invention includes a TAC film substrate 52, a clear hard coat layer 51 formed on both surfaces of the TAC film substrate 52, An adhesive layer is formed on the gas barrier layer 50 (also referred to as “first inorganic layer” in the present specification) 50 formed on the clear hard coat layer, and on the clear hard coat layer 51 on which the gas barrier layer is not formed. And a heat-resistant laminate base material 54 (heat-resistant laminate film 203) bonded through 53.

The gas barrier film obtained by the production method according to the present invention is, for example, between the TAC film substrate and the gas barrier layer, on the gas barrier layer, or on the other surface of the TAC film substrate on which the gas barrier layer is not formed. In addition, other members may be included. Here, the other members are not particularly limited, and members used for conventional gas barrier films can be used in the same manner or appropriately modified. Specific examples include the above-described clear hard coat layer, protective film, smooth layer, anchor coat layer, easy adhesion layer, bleed-out prevention layer, and functionalized layers such as a protective layer, a moisture absorption layer and an antistatic layer. .

According to the method for producing a gas barrier film according to the present invention, when forming a gas barrier layer produced by applying a great thermal load (for example, produced by a vacuum film forming method), the TAC film substrate is Since it is possible to prevent expansion and defects in the gas barrier layer, the water vapor transmission rate can be kept low.

Even at the initial stage of film formation or after continuous production, the water vapor permeability is preferably as low as possible.

The water vapor transmission rate (initial film formation) in a state where the heat-resistant laminate film is peeled off from the gas barrier film obtained by the production method according to the present invention is preferably 1 × 10 ⁻² g / m ² / day or less. More preferably, it is 8 × 10 ⁻³ g / m ² / day or less, and further preferably 5 × 10 ⁻³ g / m ² / day or less.

The water vapor transmission rate (after continuous production) is preferably 1 × 10 ⁻² g / m ² / day or less, more preferably 8 × 10 ⁻³ g / m ² / day or less, and still more preferably Is 5 × 10 ⁻³ g / m ² / day or less. The water vapor transmission rate (initial film formation) and the water vapor transmission rate (after continuous production) can be measured by the methods described in the following examples.

The ratio of the water vapor transmission rate (after continuous production) to the water vapor transmission rate (initial film formation) is preferably 1, and more preferably 1 to 1.5.

Further, the gas barrier film obtained by the production method according to the present invention is excellent in optical characteristics because it uses a TAC film substrate. The higher the total light transmittance is, the more preferable, but in the state where the heat resistant laminate film is peeled off from the gas barrier film obtained by the present invention, the total light transmittance is preferably 90% or more, and higher than 90%. Preferably, it is 92% or more, more preferably 94% or more. The total light transmittance can be measured by the method described in the following examples.

[TAC film substrate]
The base material used in the method for producing a gas barrier film according to the present invention is a TAC film. On the TAC film base, other members (for example, intermediate layers) may be appropriately formed as described above. Examples of the intermediate layer include an anchor coat layer, a smooth layer, a transparent conductive layer, a functional layer such as a primer layer, a bleed-out prevention layer, and a clear hard coat layer. Of these, it is preferable to form a clear hard coat layer on the substrate. In particular, it is preferable to have a clear hard coat layer on both surfaces of the substrate.

The thickness of the TAC film substrate used in the method for producing a gas barrier film according to the present invention is not particularly limited because it is appropriately selected depending on the application, but is typically 1 to 800 μm, preferably from the viewpoint of handling. The thickness is 10 to 200 μm, more preferably 20 to 120 μm. These TAC film base materials may have functional layers such as a transparent conductive layer and a primer layer as described above. As the functional layer, those described in paragraph numbers “0036” to “0038” of JP-A-2006-289627 can be preferably used.

[Middle layer]
(Clear hard coat layer (CHC layer))
The clear hard coat layer improves adhesion between the TAC film substrate and the gas barrier layer, relaxes internal stress resulting from the expansion / contraction difference between the TAC film substrate and the gas barrier layer under high temperature and high humidity, and a lower layer on which the gas barrier layer is provided. It has functions such as flattening and prevention of bleed out of low molecular weight components such as monomers and oligomers from the TAC film substrate.

The clear hard coat layer can be formed by applying a photosensitive resin composition on a TAC film substrate and then curing it.

The photosensitive resin composition usually contains a photosensitive resin, a photopolymerization initiator, and a solvent.

The photosensitive resin is not particularly limited as long as it is a photosensitive resin containing a reactive monomer having at least one photopolymerizable unsaturated bond in the molecule, but an acrylate compound having a radical reactive unsaturated bond. Resin containing acrylate compound and mercapto compound having thiol group, resin containing polyfunctional acrylate monomer such as epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, polyethylene glycol acrylate, glycerol methacrylate, etc. Can be mentioned. These resins can be used alone or in admixture of two or more. Specifically, it is possible to use a UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) series (compound formed by bonding an organic compound having a polymerizable unsaturated group to silica fine particles) manufactured by JSR Corporation. it can. Further, any mixture of the above-described compositions can be used, and any photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule can be used. There is no particular limitation.

The photopolymerization initiator is not particularly limited, but acetophenone, benzophenone, Michler ketone, benzoin, benzylmethyl ketal, benzoin benzoate, hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2- (4-morpholinyl) -1-propane, α-acyloxime ester, thioxanthones and the like. These photopolymerization initiators may be used alone or in combination of two or more.

The solvent is not particularly limited, but alcohols such as methanol, ethanol, propanol, isopropyl alcohol, ethylene glycol, propylene glycol; terpenes such as α- or β-terpineol; acetone, methyl ethyl ketone, cyclohexanone, N-methyl- Ketones such as 2-pyrrolidone, diethyl ketone, 2-heptanone and 4-heptanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methylcarbitol, ethyl Carbitol, butyl carbitol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, propylene glycol monomethyl Ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl Glycol ethers such as ether; ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-Methoxye Esters such as diacetate, cyclohexyl acetate, 2-ethoxyethyl acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate and methyl benzoate; amides such as N, N-dimethylacetamide and N, N-dimethylformamide Is mentioned. These solvents may be used alone or in combination of two or more.

The method for applying the photosensitive resin composition to the substrate is not particularly limited, but is a wet coating method such as spin coating method, spray method, blade coating method, gravure method, bar coating method, die coating method, dip method, Alternatively, a dry coating method such as a vapor deposition method may be used.

A clear hard coat layer can be formed by irradiating the coating film obtained by coating with ionizing radiation and curing it. The ionizing radiation may be 100 to 400 nm, preferably 200 to 400 nm of vacuum ultraviolet light emitted from an ultrahigh pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, carbon arc, metal halide lamp or the like, or scanning or curtain type electrons. An electron beam having a wavelength region of 100 nm or less emitted from a line accelerator can be used.

The thickness of the clear hard coat layer is preferably 1 to 10 μm, more preferably 2 to 7 μm. It is preferable that the thickness of the clear hard coat layer is 1 μm or more because the heat resistance of the gas barrier film can be improved. On the other hand, when the thickness of the clear hard coat layer is 10 μm or less, the optical properties of the gas barrier film are preferably adjusted, and curling of the gas barrier film can be suppressed.

(Smooth layer (underlayer, primer layer))
In the method for producing a gas barrier film according to the present invention, as described above, a smooth layer (underlying layer, primer layer) is provided between the surface of the base material having the gas barrier layer, preferably between the base material and the gas barrier layer. Also good.

The smooth layer is provided in order to flatten the rough surface of the substrate on which the protrusions and the like exist, or to fill the unevenness and pinholes generated in the gas barrier layer with the protrusions existing on the substrate. Such a smooth layer may be formed of any material, but preferably includes a carbon-containing polymer, and more preferably includes a carbon-containing polymer. That is, in the method for producing a gas barrier film according to the present invention, a smooth layer containing a carbon-containing polymer may be further provided between the base material and the gas barrier layer.

The smooth layer also contains a carbon-containing polymer, preferably a curable resin. The curable resin is not particularly limited, and the active energy ray curable resin or the thermosetting material obtained by irradiating the active energy ray curable material or the like with an active energy ray such as an ultraviolet ray to be cured is heated. And thermosetting resins obtained by curing. These curable resins may be used alone or in combination of two or more.

Examples of the active energy ray-curable material used for forming the smooth layer 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, and polyester. Examples thereof include compositions containing polyfunctional acrylate monomers such as acrylate, polyether acrylate, polyethylene glycol acrylate, and glycerol methacrylate. Specifically, it is possible to use a UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) series (compound formed by bonding an organic compound having a polymerizable unsaturated group to silica fine particles) manufactured by JSR Corporation. it can.

The method for forming the smooth layer is not particularly limited, but a coating solution containing a curable material is applied to a dry coating method such as a spin coating method, a spray method, a blade coating method, a dipping method, a gravure printing method, or a vapor deposition method. After applying the coating method to form a coating film, irradiation with active energy rays such as visible light, infrared rays, ultraviolet rays, X-rays, α rays, β rays, γ rays, electron beams, and / or heating, the coating films are formed. A method of forming by curing is preferred. As a method of irradiating active energy rays, for example, an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a metal halide lamp or the like is preferably used to irradiate ultraviolet rays in a wavelength region of 100 to 400 nm, more preferably 200 to 400 nm. Alternatively, a method of irradiating an electron beam having a wavelength region of 100 nm or less emitted from a scanning or curtain type electron beam accelerator can be used.

Specific examples of thermosetting materials include TutProm Series (Organic Polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Coat, Nanohybrid Silicone manufactured by Adeka, Unicom manufactured by DIC, Inc. Dick (registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (ultra-high heat resistant epoxy resin), silicon resin X-12-2400 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., Nittobo Co., Ltd. Inorganic / organic nanocomposite material SSG coating, thermosetting urethane resin consisting of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicone resin, polyamidoamine-epichlorohydrin Butter, and the like can be mentioned.

The smoothness of the smooth layer is a value expressed by the surface roughness specified in JIS B 0601: 2001, and the maximum cross-sectional height Rt (p) is preferably 10 nm or more and 30 nm or less.

The surface roughness is calculated from an uneven cross-sectional curve continuously measured by an AFM (Atomic Force Microscope) with a detector having a stylus having a minimum tip radius, and the measurement direction is several tens by the stylus having a minimum tip radius. It is the roughness related to the amplitude of fine irregularities measured in a section of μm many times.

The thickness of the smooth layer is not particularly limited, but is preferably in the range of 0.1 to 10 μm.

(Anchor coat layer)
As described above, an anchor coat layer may be formed on the surface of the substrate according to the present invention as an easy-adhesion layer for the purpose of improving adhesiveness (adhesion). Examples of the anchor coating agent used in this anchor coat layer include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, and alkyl titanate. One type or two or more types can be used in combination. A commercially available product may be used as the anchor coating agent. Specifically, a siloxane-based UV curable polymer solution (manufactured by Shin-Etsu Chemical Co., Ltd., “X-12-2400” 3% isopropyl alcohol solution) can be used.

The thickness of the anchor coat layer is not particularly limited, but is preferably about 0.5 to 10.0 μm.

(Bleed-out prevention layer)
As described above, the substrate having a smooth layer may be contaminated on the surface of the substrate due to migration of unreacted oligomers and the like from the substrate to the surface during heating. The bleed-out prevention layer has a function of suppressing contamination of the substrate surface. The bleed-out prevention layer is usually provided on the surface opposite to the smooth layer of the substrate having the smooth layer.

The bleed-out prevention layer may have the same configuration as the smooth layer as long as it has the above function. That is, the bleed-out prevention layer can be formed by applying a photosensitive resin composition on a TAC film substrate and then curing it.

When at least one intermediate layer selected from the group consisting of the above-mentioned anchor coat layer, smooth layer, and clear hard coat layer is formed on the TAC film substrate, the total film thickness of the substrate and the intermediate layer is: The thickness is preferably 5 to 500 μm, more preferably 25 to 250 μm.

[Heat-resistant laminate film]
In the method for producing a gas barrier film according to the present invention, the TAC film substrate has a heat resistant laminate film on the surface opposite to the surface on which the gas barrier layer is formed. The heat resistant laminate film has a laminate base material and an adhesive layer. By providing the heat resistant laminate film, it is possible to suppress the occurrence of defects in the gas barrier layer when the first gas barrier layer is formed by a vacuum film forming method.

Hereinafter, preferred modes of the laminate base material and the adhesive layer of the heat resistant laminate film will be described.

(Laminated substrate)
The heat resistant laminate film according to the present invention can suppress deformation of the gas barrier film caused by the TAC film trying to expand due to heat. Therefore, the laminate base material is not easily expanded and contracted by heat, and has a waist strength sufficient to suppress deformation.

The laminate base material used for the heat resistant laminate film is preferably a thermoplastic resin, and examples thereof include plastic films such as polyvinyl chloride, polyester, polyethylene and stretched polypropylene. Among these, a polyethylene terephthalate film is preferably used from the viewpoints of heat resistance and availability.

The heat-resistant laminate film preferably has a thermal expansion coefficient at 25 to 80 ° C. of 50 ppm / ° C. or less, more preferably 40 ppm / ° C. or less, still more preferably 30 ppm / ° C. or less, and still more preferably 20 ppm / ° C. It is as follows. If the coefficient of thermal expansion at 25 to 80 ° C. is 50 ppm / ° C. or less, it is possible to suppress the occurrence of defects in the barrier layer due to dimensional changes and characteristic changes due to temperature during the formation of the first inorganic layer, and ensure sufficient barrier properties. be able to. The lower limit of the thermal expansion coefficient at 25 to 80 ° C. is not particularly limited, but is usually 1 or 2 ppm / ° C. or higher.

The waist strength of the laminate substrate of the heat resistant laminate film can be adjusted by the Young's modulus (material of the laminate substrate) and the thickness of the laminate substrate when the area of the heat resistant laminate film is constant. When the TAC film substrate to which the heat-resistant laminate film is bonded is expanded by heat during vacuum film formation, a bending moment is generated in the heat-resistant laminate film, leading to distortion of the film. When the laminate substrate has a sufficient thickness with respect to the TAC film substrate, the bending stress applied to the gas barrier film is reduced, and the center of the bending moment of the entire film moves to the heat resistant laminate film side, so that the gas barrier film is It becomes difficult to distort.

The ratio of the thickness (A) of the TAC film substrate and the thickness (B) of the laminate substrate of the heat-resistant laminate film, that is, A / B is 2.2 or less, which is a feature of the present invention. . By setting it as such a value, the defect to a gas barrier layer can be suppressed.

Preferably, the lower limit of A / B is 0.3 or more. Preferably it is 0.5 or more, More preferably, it is 0.8 or more, More preferably, it is 1.0 or more. If A / B is less than 0.3, it is not preferable from the viewpoint of ease of handling.

The upper limit of A / B is 2.2 or less. It is preferable that it is 2.2 or less because defects in the gas barrier layer can be further suppressed.

According to a preferred embodiment of the present invention, the water vapor transmission rate is low, and from the viewpoint of optical properties, it is preferably 0.3 to 2.0, more preferably 0.3 to 1.6.

If A / B is greater than 2.2, it is difficult to suppress distortion due to thermal expansion of the TAC film, and defects in the gas barrier layer cannot be suppressed.

The thickness of the laminate base material of the heat resistant laminate film is preferably 10 μm or more, more preferably 15 μm or more from the viewpoint of handleability. In addition, it is 300 μm or less from the viewpoint of productivity (that is, from the viewpoint that if the thickness is too thick, there is a possibility that one roll may be shortened or become heavy), and in terms of transportability and adhesion to a roll. Is more preferable, 150 μm or less is more preferable, and 120 μm or less is more preferable.

In addition, from the viewpoint of sufficiently suppressing the thermal expansion of the TAC substrate film, the laminate substrate of the heat-resistant laminate film has the same width as that of the TAC film substrate or a width that is at least within 1 mm after lamination. Is preferred. That is, it is preferable that the TAC base material end and the laminate base material end are aligned, or the laminating base material protrudes within 1 mm. The base material end portions are four sides when vacuum film formation is performed on a single sheet, and the end portions in the transport direction when vacuum film formation is performed by roll-to-roll.

By increasing the Young's modulus of the laminate base material, the radius of curvature of the TAC film base material when a certain bending moment is applied is reduced, so that the distortion can be suppressed to a low level. The lower limit of the Young's modulus is preferably 0.4 GPa or more, more preferably 1.0 GPa or more, still more preferably 1.5 GPa or more, and even more preferably 2.0 GPa or more. It is preferable for the Young's modulus to be 0.4 GPa or more because expansion and distortion of the TAC film substrate can be sufficiently suppressed. The upper limit of the Young's modulus is preferably 5.0 GPa or less, and more preferably 4.0 or less. A Young's modulus of 5.0 GPa or less is preferable from the viewpoint of handling the heat-resistant laminate film.

Thus, according to a preferred embodiment of the present invention, the Young's modulus of the laminate base material is 0.4 to 4.0.

The heat resistant laminate film may be wound into a roll before being bonded to the TAC film substrate of the gas barrier film. Moreover, you may have a release layer on the film surface by the side of the adhesion layer, and you may wind in the roll shape in the state which bonded the release layer.

(Adhesive layer)
Due to the difference in thermal expansion coefficient between the heat-resistant laminate film and the TAC film substrate, thermal stress is applied to the bonding surface. Therefore, the heat resistant laminate film and the TAC film substrate require a sufficient adhesive force. The heat-resistant laminate film that can be used in the method for producing a gas barrier film according to the present invention has a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive on the surface of the heat-resistant laminate film in order to ensure adhesion with the TAC film substrate.

The pressure-sensitive adhesive is not particularly limited, but an acrylic pressure-sensitive adhesive is preferable from the viewpoints of durability, transparency, and ease of adjustment of adhesive properties. The acrylic pressure-sensitive adhesive uses an acrylic polymer that is mainly composed of alkyl acrylate and copolymerized with a polar monomer component. The alkyl acrylate ester is an alkyl ester of acrylic acid or methacrylic acid and is not particularly limited. For example, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, (meth ) Pentyl acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, and the like. Specifically, Toyo Ink BPS5978 can be used.

The adhesive strength between the TAC film substrate and the heat resistant laminate film (that is, the adhesive strength of the adhesive layer) is preferably 0.08 to 0.2 N / inch. When the adhesive strength of the adhesive layer is 0.08 N / inch or more, sufficient adhesive strength between the heat resistant laminate film and the TAC film substrate can be ensured.

If the adhesive strength is 0.20 N / inch or less, it is not necessary to apply an excessive force to the gas barrier film when the heat resistant laminate film is peeled off, and damage to the gas barrier layer can be prevented. According to a preferred embodiment of the present invention, it is more preferably 0.08 to 0.14 N / inch, and further preferably 0.08 to 0.1 N / inch.

The adhesive force between the TAC film substrate and the heat-resistant laminate film can be adjusted by changing the type and degree of curing of the pressure-sensitive adhesive and the curing agent. Moreover, it can adjust by changing the lamination temperature at the time of lamination.

The adhesive strength of the pressure-sensitive adhesive can be determined by measuring 20 minutes after using a Corning 1737 as a test plate and pressing the heat-resistant laminate film on the test plate in accordance with a measurement method based on JIS Z 0237 2000. In the examples, such measurement is performed.

Further, the thickness of the adhesive layer is preferably 10 to 50 μm, more preferably 15 to 30 μm from the viewpoint of handling. Within such a range, sufficient adhesion between the resin material (that is, the laminate base material) and the gas barrier film can be obtained, and when the heat-resistant laminate film is peeled off, it is excessive for the gas barrier film. It is not necessary to apply a force, and damage to the gas barrier layer can be prevented.

The method of applying the adhesive to the heat-resistant laminate film is not particularly limited. For example, the blade coater method, die coater method, screen method, air knife coat method, spray coater method, gravure method, gravure roll coater method, mesh method A dip coating method, a transfer method, a bar coating method, etc. can be applied. These can be used alone or in combination. Moreover, the heat resistant laminate film using a commercially available PET base material can be used. Alternatively, coating can be performed using a dispersed coating solution, and a known material can be used as the solvent.

(Method for forming adhesive layer)
The adhesive layer may be formed directly on the heat-resistant laminate film using the previous coating method, or once coated on the release film and dried, then the heat-resistant laminate film is bonded. The adhesive may be transferred.

The drying temperature is preferably such that the residual solvent is as small as possible. For this purpose, the drying temperature and time are not specified, but it is preferable to provide a drying time of 10 seconds to 5 minutes at a temperature of 50 to 150 ° C.

[Lamination of heat-resistant laminate film to TAC film substrate]
The bonding of the heat-resistant laminate film to the TAC film substrate is not particularly limited, but can be performed by bonding the heat-resistant laminate film to the TAC film substrate with an adhesive layer.

In the present invention, the gas barrier film substrate and the heat-resistant laminate film can be bonded using, for example, a roll laminator. Further, in a preferred embodiment, even if it is an on-line system in which the first inorganic layer is formed continuously with the heat-resistant laminate film, or after the heat-resistant laminate film is bonded, An off-line method may be used in which the first inorganic layer is formed in a separate step after winding the TAC film on which the heat-resistant laminate film is bonded with the take-off shaft.

After forming the first inorganic layer, the gas barrier film is wound around the roll, but at this time, the bleeding out component from the TAC film substrate is prevented from being transferred to the roll or attached to the gas barrier layer. It is preferable to wind up the gas barrier film which bonded the heat resistant laminate film in roll shape from a viewpoint which can do.

Thus, according to a preferred embodiment of the present invention, after forming a gas barrier layer on the TAC film substrate having the heat resistant laminate film, the gas barrier film bonded with the heat resistant laminate film is wound into a roll shape. It is preferable to further include the step of taking.

Generally, the resin base material of the gas barrier film is manufactured as an elongated body, but it is not desirable to perform a long manufacturing process in one line from the viewpoint of space and conveyance. At the same time, if a defect occurs in a part of the line, it is preferable to divide into a plurality of lines from the viewpoint of availability and yield. For example, it is necessary to stop the entire line. In that case, it is convenient to wind up the resin base material which is a long body around a roll once, and to convey or store.

Furthermore, to prevent the gas barrier layer surface from being attached to the surface of the gas barrier layer when it is wound into a roll or from being damaged by scratching with the heat-resistant laminate film, the surface of the gas barrier layer is protected as described above. A film or the like may be bonded.

As described above, the heat-resistant laminate film is mainly composed of a laminate base material and an adhesive layer containing an adhesive on the laminate base material, and further has a release layer containing a release agent thereon. Good. The heat resistant laminate film is preferably prepared in a state of being wound in a roll shape with the release layer inside. Next, the heat-resistant laminate film is unwound from the roll, the release layer is separated to expose the adhesive layer, and the separated release layer is taken up by a take-up roll.

On the other hand, the TAC film substrate is also fed out from the roll, and a heat-resistant laminate film adhesive layer is bonded to the surface. The TAC film substrate to which the heat-resistant laminate film is bonded is conveyed to the gas barrier layer forming step located downstream, and the first inorganic layer is formed on the TAC film substrate by a vacuum film formation method. An inorganic layer is formed.

After the gas barrier layer is formed, the gas barrier film is wound into a roll around a winding core attached to a winding shaft. At this time, since the heat-resistant laminate film is located between the TAC film substrate and the gas barrier layer, it is possible to prevent the bleed-out component from the TAC film substrate from adhering to the gas barrier layer when it is rolled up.

[Method of forming gas barrier layer]
In the method for producing a gas barrier film according to the present invention, in a preferred embodiment, a chemical vapor deposition method (CVD) is formed on a TAC film base or a TAC film base (if another member such as an intermediate layer is provided). The gas barrier layer (second inorganic layer) may be formed by forming at least one gas barrier layer by a vacuum film forming method such as a physical vapor deposition method (PVD method) or by applying a solution containing a silicon compound. .

Further, in the present invention, in addition to the vacuum film forming method, the wet coating method described above may be used. Even when the thermal load is applied, the production method of the present invention can provide a gas barrier film having excellent optical characteristics and low water vapor permeability.

(Method for forming a gas barrier layer (first inorganic layer) by vacuum film formation)
Hereinafter, as a preferred embodiment, a method for forming a gas barrier layer (first inorganic layer) by a vacuum film forming method will be described.

The method for producing a gas barrier film according to the present invention includes a step of forming a gas barrier layer on the surface of the TAC film substrate opposite to the surface having the heat resistant laminate film, for example, by a vacuum film forming method.

The gas barrier layer formed by the vacuum film forming method contains an inorganic compound. Although it does not specifically limit as an inorganic compound contained in a 1st inorganic layer, For example, at least 1 sort (s) of oxide, nitride, oxynitride, or oxycarbide selected from the group which consists of silicon, aluminum, and titanium, for example Including species. Specific examples of the at least one oxide, nitride, oxynitride, or oxycarbide selected from the group consisting of silicon, aluminum, and titanium include silicon oxide (SiO ₂ ), silicon nitride, silicon oxynitride ( These composites include SiON), silicon oxycarbide (SiOC), silicon carbide, aluminum oxide, titanium oxide, and aluminum silicate. Of these, silicon oxynitride (SiON), silicon nitride (SiN), silicon oxycarbide (SiOC), silicon oxide (SiO ₂ ), aluminum silicate (SiAlO), and silicon oxynitride carbide (SiONC) are preferable. These may contain other elements as secondary components.

The thickness of the first inorganic layer is preferably 5 to 200 nm, more preferably 10 to 150 nm, and still more preferably 20 to 100 nm.

The first inorganic layer has the above compound and thus has a gas barrier property.

The physical vapor deposition method (PVD method) is a method of depositing a target material, for example, a thin film such as a carbon film, on the surface of the material in a gas phase by a physical method. For example, a sputtering method (DC sputtering, RF Sputtering, ion beam sputtering, magnetron sputtering, etc.), vacuum deposition, ion plating, and the like.

As a raw material compound, a silicon compound, a titanium compound, and an aluminum compound are used. Conventionally known compounds can be used for these, and hexamethyldisiloxane (HMDSO) is preferable.

In addition, as a decomposition gas for decomposing a raw material gas containing metal to obtain an inorganic compound, hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, nitrous oxide gas, Nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor and the like can be mentioned. Further, the decomposition gas may be mixed with an inert gas such as argon gas or helium gas.

Hereinafter, the plasma CVD method which is a preferable form among the CVD methods will be described in detail.

FIG. 2 is a schematic view showing an example of a vacuum plasma CVD apparatus used for forming the first inorganic layer according to the present invention.

In FIG. 2, the vacuum plasma CVD apparatus 101 has a vacuum chamber 102, and a susceptor 105 is disposed on the bottom surface inside the vacuum chamber 102. Further, a cathode electrode 103 is disposed on the ceiling side inside the vacuum chamber 102 at a position facing the susceptor 105. A heat medium circulation system 106, a vacuum exhaust system 107, a gas introduction system 108, and a high-frequency power source 109 are disposed outside the vacuum chamber 102. A heat medium is disposed in the heat medium circulation system 106. The heat medium circulation system 106 stores a pump for moving the heat medium, a heating device for heating the heat medium, a cooling device for cooling, a temperature sensor for measuring the temperature of the heat medium, and a set temperature of the heat medium. A heating / cooling device 160 having a storage device is provided. For details of the vacuum plasma CVD apparatus described in FIG. 2, reference can be made to International Publication No. WO12 / 014653.

(Other suitable forms of the first inorganic layer)
As another preferred embodiment of the first inorganic layer of the present invention, there is a layer containing carbon, silicon, and oxygen as constituent elements. A more preferred form is the first inorganic layer that satisfies the following requirements (i) to (ii).

(I) The distance (L) from the surface of the first inorganic layer in the film thickness direction of the first inorganic layer and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (silicon atomic ratio) A distribution curve showing the relationship between L and the oxygen distribution curve showing the relationship between the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atomic ratio of oxygen); In the carbon distribution curve showing the relationship between the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (the atomic ratio of carbon), the carbon distribution curve has at least two extreme values,
(Ii) The absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 3 at% or more.

Having such a composition is preferable from the viewpoint of achieving both high gas barrier properties and flexibility.

Furthermore, in the region of 90% or more of the total thickness of the first inorganic layer, the average atomic ratio of each atom to the total amount (100 at%) of silicon atoms, oxygen atoms and carbon atoms is expressed by the following formula (A) or (B It is preferable to have an order of magnitude relationship represented by

Formula (A)
(Carbon average atomic ratio) <(silicon average atomic ratio) <(oxygen average atomic ratio)
Formula (B)
(Oxygen average atomic ratio) <(silicon average atomic ratio) <(carbon average atomic ratio)
If so, the bending resistance is further improved, which is more preferable.

Hereinafter, the preferred embodiment will be described.

(I) The distance (L) from the surface of the first inorganic layer in the film thickness direction of the first inorganic layer and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (silicon atoms Ratio), a silicon distribution curve showing the relationship between the L and the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (atomic ratio of oxygen), and In the carbon distribution curve showing the relationship between L and the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (the atomic ratio of carbon), the carbon distribution curve has at least two extreme values. preferable. The first inorganic layer preferably has at least three extreme values in the carbon distribution curve, more preferably at least four extreme values, but may have five or more extreme values. When the carbon distribution curve has at least two extreme values, the carbon atom ratio continuously changes with a concentration gradient, and the gas barrier performance during bending is enhanced. The upper limit of the extreme value of the carbon distribution curve is not particularly limited, but is preferably 30 or less, more preferably 25 or less, for example. Since the number of extreme values is also caused by the film thickness of the gas barrier layer, it cannot be defined unconditionally.

Here, in the case of having at least three extreme values, one extreme value of the carbon distribution curve and the first inorganic layer in the film thickness direction of the first inorganic layer at the extreme value adjacent to the extreme value. The absolute value of the difference in distance (L) from the surface (hereinafter also simply referred to as “distance between extreme values”) is preferably 200 nm or less, more preferably 100 nm or less, and 75 nm or less. It is particularly preferred. If it is such a distance between extreme values, since there are portions having a large carbon atom ratio (maximum value) in the first inorganic layer at an appropriate period, the first inorganic layer is imparted with an appropriate flexibility, Generation of cracks during bending of the gas barrier film can be more effectively suppressed / prevented. In this specification, the extreme value means the maximum value or the minimum value of the atomic ratio of the element to the distance (L) from the surface of the first inorganic layer in the film thickness direction of the first inorganic layer. Further, in this specification, the maximum value is a point where the value of the atomic ratio of the element (oxygen, silicon or carbon) changes from increase to decrease when the distance from the surface of the first inorganic layer is changed, Further, the atom of the element at a position where the distance from the surface of the first inorganic layer in the film thickness direction of the first inorganic layer from the point is further changed within the range of 4 to 20 nm, rather than the value of the atomic ratio of the element at that point. This is the point at which the ratio value decreases by 3 at% or more. That is, it is sufficient that the atomic ratio value of the element is reduced by 3 at% or more in any range when changing in the range of 4 to 20 nm. This varies depending on the film thickness of the first inorganic layer. For example, when the first inorganic layer is 300 nm, the value of the atomic ratio of the element at the position where the distance from the surface of the first inorganic layer in the film thickness direction of the first inorganic layer is changed by 20 nm decreases by 3 at% or more. A point is preferable. Furthermore, the minimum value in the present specification is a point where the value of the atomic ratio of the element (oxygen, silicon or carbon) changes from decrease to increase when the distance from the surface of the first inorganic layer is changed, and The atomic ratio of the element at the position where the distance from the surface of the first inorganic layer in the film thickness direction of the first inorganic layer is further changed within the range of 4 to 20 nm from the value of the atomic ratio of the element at that point This means that the value increases by 3 at% or more. That is, when changing in the range of 4 to 20 nm, the atomic ratio value of the element only needs to increase by 3 at% or more in any range. Here, the lower limit of the distance between the extreme values in the case of having at least three extreme values is particularly high because the smaller the distance between the extreme values, the higher the effect of suppressing / preventing crack generation when the gas barrier film is bent. Not limited.

Further, in the first inorganic layer, (ii) the absolute value of the difference between the maximum value and the minimum value of the carbon atomic ratio in the carbon distribution curve is preferably 3 at% or more, and more preferably 5 at% or more. Preferably, it is 7 at% or more. When the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 3 at% or more, the gas barrier performance during bending is enhanced. In the present specification, the “maximum value” is the atomic ratio of each element that is maximum in the distribution curve of each element, and is the highest value among the maximum values. Similarly, in this specification, the “minimum value” is the atomic ratio of each element that is the minimum in the distribution curve of each element, and is the lowest value among the minimum values.

Also, in the region of 90% or more (upper limit: 100%) of the film thickness of the first inorganic layer, (atomic ratio of oxygen), (atomic ratio of silicon), and (atomic ratio of carbon) increase in order (atomic ratio) Is preferably O> Si> C). By satisfying such conditions, the resulting gas barrier film has sufficient gas barrier properties and flexibility. Here, in the carbon distribution curve, the relationship between the above (atomic ratio of oxygen), (atomic ratio of silicon) and (atomic ratio of carbon) is at least 90% or more (upper limit: 100%) of the film thickness of the gas barrier layer. ) And more preferably at least 93% or more (upper limit: 100%). Here, the term “at least 90% or more of the film thickness of the gas barrier layer” does not need to be continuous in the gas barrier layer.

The silicon distribution curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon distribution curve are obtained by using X-ray photoelectron spectroscopy (XPS) measurement and rare gas ion sputtering such as argon in combination. Thus, it can be created by so-called XPS depth profile measurement in which surface composition analysis is sequentially performed while exposing the inside of the sample. A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time). In this way, in the element distribution curve with the horizontal axis as the etching time, the etching time is the distance (L) from the surface of the first inorganic layer in the film thickness direction of the first inorganic layer in the film thickness direction. Since there is a general correlation, the “distance from the surface of the first inorganic layer in the film thickness direction of the first inorganic layer” is calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement. The distance from the surface of one inorganic layer can be employed. In the present invention, the silicon distribution curve, oxygen distribution curve, carbon distribution curve, and oxygen carbon distribution curve were prepared under the following measurement conditions.

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

From the viewpoint of forming a first inorganic layer that is uniform over the entire film surface and has excellent gas barrier properties, the first inorganic layer is substantially uniform in the film surface direction (direction parallel to the surface of the first inorganic layer). It is preferable that Here, the fact that the first inorganic layer is substantially uniform in the film surface direction means that the oxygen distribution curve and the carbon distribution curve are measured at any two measurement points on the film surface of the first inorganic layer by XPS depth profile measurement. When the oxygen carbon distribution curve is created, the number of extreme values of the carbon distribution curve obtained at any two measurement locations is the same, and the maximum value of the atomic ratio of carbon in each carbon distribution curve And the absolute value of the difference between the minimum values is the same as each other or within 5 at%.

Furthermore, it is preferable that the carbon distribution curve is substantially continuous. Here, the carbon distribution curve is substantially continuous means that the carbon distribution curve does not include a portion where the atomic ratio of carbon changes discontinuously. Specifically, the carbon distribution curve is calculated from the etching rate and the etching time. The distance (x, unit: nm) from the surface of the first inorganic layer in the film thickness direction of at least one of the first inorganic layers to be formed, and the atomic ratio of carbon (C, unit: at%) In the relationship, the condition expressed by the following formula (1) is satisfied.

When the first inorganic layer has a sublayer, a plurality of sublayers that satisfy all of the above conditions (i) to (ii) may be stacked to form the first inorganic layer. When two or more sublayers are provided, the materials of the plurality of sublayers may be the same or different.

The layer satisfying the requirements of (i) to (ii), which is a preferred form of the first inorganic layer, is preferably a layer formed by a plasma CVD (PECVD) method, and a substrate is formed as a pair of films. More preferably, it is formed on a roller and formed by a plasma CVD method in which plasma is generated by discharging between the pair of film forming rollers. The plasma CVD method may be a Penning discharge plasma type plasma CVD method.

When generating plasma in the plasma CVD method, it is preferable to generate plasma discharge in a space between a plurality of film forming rollers. A pair of film forming rollers is used, and each of the pair of film forming rollers has the above-mentioned base. More preferably, a material is disposed and discharged between a pair of film forming rollers to generate plasma. In this way, by using a pair of film forming rollers, placing a base material on the pair of film forming rollers, and discharging between the pair of film forming rollers, one film forming roller It is possible not only to produce a thin film efficiently because it is possible to form a film on the surface part of the base material existing in the film while simultaneously forming a film on the surface part of the base material present on the other film forming roller. Compared with the plasma CVD method using no roller, the film formation rate can be doubled, and a film having substantially the same structure can be formed, so that the extreme value in the carbon distribution curve can be at least doubled, and it is efficient. It is possible to form a layer that satisfies all of the above conditions (i) to (ii).

Further, when discharging between the pair of film forming rollers in this way, it is preferable to reverse the polarities of the pair of film forming rollers alternately. Further, the film forming gas used in such a plasma CVD method preferably contains an organic silicon compound and oxygen, and the content of oxygen in the film forming gas is determined by the organosilicon compound in the film forming gas. It is preferable that the amount of oxygen be less than the theoretical oxygen amount necessary for complete oxidation. In the gas barrier film of the present invention, the gas barrier layer is preferably a layer formed by a continuous film forming process.

Also, from the viewpoint of productivity, it is preferable to form the first inorganic layer on the surface of the substrate by a roll-to-roll method. Further, an apparatus that can be used when producing the first inorganic layer by such a plasma CVD method is not particularly limited, and includes at least a pair of film forming rollers and a plasma power source, and the pair of pairs. It is preferable that the apparatus has a configuration capable of discharging between the film forming rollers. For example, when the manufacturing apparatus shown in FIG. 3 is used, a roll-to-roll system is used while using a plasma CVD method. It can also be manufactured.

Hereinafter, the method for forming the first inorganic layer will be described in more detail with reference to FIG. FIG. 3 is a schematic diagram showing an example of a manufacturing apparatus that can be suitably used for manufacturing the first inorganic layer. In the following description and drawings, the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted.

3 includes a delivery roller 32, transport rollers 33, 34, 35, and 36, film formation rollers 39 and 40, a gas supply pipe 41, a plasma generation power source 42, and a film formation roller 39. And magnetic field generators 43 and 44 installed inside 40 and a winding roller 45. In such a manufacturing apparatus, at least the film forming rollers 39 and 40, the gas supply pipe 41, the plasma generating power source 42, and the magnetic field generating apparatuses 43 and 44 are arranged in a vacuum chamber (not shown). ing. Further, in such a manufacturing apparatus 31, the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by the vacuum pump. Details relating to the apparatus can be referred to conventionally known documents, for example, Japanese Patent Application Laid-Open No. 2011-73430.

As described above, as a more preferable aspect of the present embodiment, the first inorganic layer is formed by a plasma CVD method using a plasma CVD apparatus (roll-to-roll method) having a counter roll electrode shown in FIG. This is excellent in flexibility (flexibility) and mechanical strength, especially when transported by roll-to-roll, when mass-produced using a plasma CVD apparatus (roll-to-roll method) having a counter roll electrode. This is because it is possible to efficiently produce the first inorganic layer having both the barrier performance and the barrier performance. Such a manufacturing apparatus is also excellent in that it can inexpensively and easily mass-produce gas barrier films that are required for durability against temperature changes used in solar cells and electronic components.

[Gas barrier layer (second inorganic layer) formed by applying a solution containing a silicon compound]
The method for producing a gas barrier film according to the present invention may further have a second inorganic layer on the first inorganic layer. The method for forming the second inorganic layer is not particularly limited. For example, the layer containing a silicon compound is modified by heating, and the layer containing the silicon compound is modified by irradiating active energy rays. Methods and the like.

The layer containing a silicon compound is formed by applying a coating solution containing a silicon compound.

(Silicon compound)
The silicon compound is not particularly limited as long as a coating solution containing the silicon compound can be prepared. Among these, polysilazane such as perhydropolysilazane and organopolysilazane; polysiloxane such as silsesquioxane, etc. are preferable in terms of film formation, fewer defects such as cracks, and less residual organic matter, and high gas barrier performance. Polysilazane is more preferable, and perhydropolysilazane is particularly preferable because the barrier performance is maintained even when bent and under high temperature and high humidity conditions.

The method for forming the gas barrier layer according to the present invention is not particularly limited, and a known method can be applied. However, a gas barrier layer forming coating containing a silicon compound, a compound containing an additive element, and, if necessary, a catalyst in an organic solvent. A method of applying a liquid (hereinafter also simply referred to as “coating liquid”) by a known wet coating method, removing the solvent by evaporation, and then performing a modification treatment is preferable.

As described above, the second gas barrier layer is preferably formed by applying a conventionally known polysilazane compound, and is preferably modified by vacuum ultraviolet rays.

In addition, according to this invention, it is a gas barrier film manufactured by the manufacturing method which has the process of forming a gas barrier layer in one side of a TAC film base material, Comprising: In the said manufacturing method, A step of forming the gas barrier layer in a state where a heat-resistant laminate film having an adhesive layer is disposed on a surface opposite to a surface of the TAC film base material on which the gas barrier layer is formed via the adhesive layer. There is also provided a gas barrier film in which the ratio A / B between the thickness (A) of the TAC film substrate and the thickness (B) of the laminate substrate is 2.2 or less.

Regarding the constituent requirements of the invention, the explanation given by the above-described method for producing a gas barrier film is equally valid, and the explanation is omitted here.

The effect 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. In the following operations, unless otherwise specified, the measurement of the operation and physical properties is performed under the conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.

[Example 1]
<< Production of base material for gas barrier film >>
[Preparation of TAC film substrate 1 for gas barrier film]
A UV curable organic / inorganic hybrid hard coat material (manufactured by JSR Corporation, OPSTAR Z7527) is applied to a 50 μm-thick triacetylcellulose film (manufactured by Konica Minolta, abbreviated as TAC), dried, and then vacuum-ultraviolet. A curing treatment with light was performed, and a triacetyl cellulose film (TAC) substrate 1 for a gas barrier film in which a clear hard coat layer was provided on both surfaces using a die coater was produced. The drying conditions, dry film thickness, and curing conditions are shown below.

Drying conditions: 80 ° C., 3 minutes
Dry film thickness: 2 μm
Curing conditions: high pressure mercury lamp, 1.0 J / cm ² .

[Production of TAC film bases 2 to 4 for gas barrier film]
Except for changing the thickness of the triacetyl cellulose film to 100 μm, 25 μm, and 53 μm, the TAC film substrate 2 for gas barrier film 2 (the thickness of the TAC film substrate) is the same as the preparation of the TAC film substrate 1 for gas barrier film. 100 μm), TAC film substrate 3 for gas barrier film (TAC film substrate thickness is 25 μm) and TAC film substrate 4 for gas barrier film (TAC film substrate thickness is 53 μm).

[Preparation of Comparative PET Base Material 1 for Gas Barrier Film]
Similar to the production of the TAC film substrate 1 for a gas barrier film, except that it was changed to a polyethylene terephthalate film (made by Teijin DuPont Films Ltd., abbreviated as PET) having a thickness of 50 μm instead of the triacetyl cellulose film having a thickness of 100 μm. Thus, a PET base material 1 for a gas barrier film was produced.

<Production of heat-resistant laminate film>
[Preparation of heat-resistant laminate film A]
Acrylic adhesive on one side of a 50 μm thick polyethylene terephthalate film (manufactured by Teijin DuPont Films Ltd., abbreviation: PET) (thermal expansion coefficient at a temperature range of 25 ° C. to 80 ° C .: 15 ppm / ° C. Young's modulus: 4.0) As a curing agent, an adhesive solution in which 5% by mass of Toyo Ink BXX5134 was mixed as a curing agent was applied to a resin of BPS5978 manufactured by Toyo Ink Co., Ltd. using a die coater. After passing through a drying line at 100 ° C. for 1 minute, the film thickness was adjusted to 20 μm. Furthermore, it was allowed to stand for 3 days at 23 ° C. and 50% RH for stabilization.

[Preparation of heat-resistant laminate film B]
A heat resistant laminate film B was prepared in the same manner as the heat resistant laminate film A except that the thickness of the polyethylene terephthalate film was changed to 23 μm.

[Preparation of heat resistant laminate film C]
A heat resistant laminate film C was prepared in the same manner as the heat resistant laminate film A except that the thickness of the polyethylene terephthalate film was changed to 100 μm.

[Preparation of heat-resistant laminate film D]
A heat resistant laminate film D was prepared in the same manner as the heat resistant laminate film A except that BXX5134 manufactured by Toyo Ink Co., Ltd. as a curing agent was changed from 5 mass% to 10 mass%.

[Preparation of heat-resistant laminate film E]
A heat resistant laminate film E was prepared in the same manner as the heat resistant laminate film A except that BXX5134 manufactured by Toyo Ink Co., Ltd. as a curing agent was changed from 5 mass% to 2 mass%.

[Preparation of heat-resistant laminate film F]
A heat resistant laminate film F was prepared in the same manner as the heat resistant laminate film A except that the thickness of the polyethylene terephthalate film was changed to 16 μm.

[Preparation of heat resistant laminate film G]
A heat resistant laminate film G was prepared in the same manner as the heat resistant laminate film A except that the thickness of the polyethylene terephthalate film was changed to 180 μm.

<Bonding of gas barrier film substrate and heat-resistant laminate film>
As shown in Table 1, a gas barrier film substrate and a heat-resistant laminate film were attached at room temperature using a roll laminator. The adhesive force was measured by fixing a gas barrier film substrate using a peel tester (manufactured by SHINPO) and peeling the film at a peel rate of 300 mm / min of a heat resistant laminate film. The results of adhesive strength are shown in Table 1. In addition, after attaching the base material for gas barrier films and the heat-resistant laminate film, before setting to the plasma CVD film forming apparatus, slit to fit the width of the film forming apparatus, The edges of the heat-resistant laminate film were aligned.

<< Production of gas barrier film >>
[Formation of first inorganic layer by plasma CVD method]
The gas barrier film substrate to which the heat-resistant laminate film was bonded was set in a plasma CVD film forming apparatus 31 shown in FIG. 3 and conveyed. Next, a magnetic field is applied between the film forming roller 39 and the film forming roller 40, and electric power is supplied to the film forming roller 39 and the film forming roller 40, respectively. Was discharged to generate plasma. Thereafter, a film-forming gas (mixed gas of hexamethyldisiloxane (HMDSO) as a source gas and oxygen gas (which also functions as a discharge gas) as a reaction gas) is supplied to the formed discharge region, Plasma on the surface of the TAC film substrate opposite to the surface on which the heat-resistant laminate film is bonded (the surface on which the heat-resistant laminate film is not bonded is either surface) under the following conditions: A first inorganic layer having a thickness of 40 nm was formed by the CVD method, and gas barrier films 1 to 13 were prepared.

The obtained sample (gas barrier film No. 1) was subjected to XPS depth profile measurement under the following conditions to obtain silicon element distribution, oxygen element distribution, and carbon element distribution.

<XPS depth profile measurement>
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 ellipse Based on the data evaluated in this way, the distance from the surface of the barrier is plotted on the horizontal axis and the amount of silicon atoms relative to the total amount of silicon atoms, oxygen atoms and carbon atoms Taking the ratio (silicon atom ratio), oxygen atom ratio (oxygen atom ratio) and carbon atom ratio (carbon atom ratio) on the vertical axis, the silicon distribution curve, oxygen distribution curve and carbon distribution curve of the gas barrier film Is shown in FIG. A is an oxygen distribution curve, B is a silicon distribution curve, and C is a carbon distribution curve. The maximum value of the atomic ratio of carbon in the carbon distribution curve was 14 at%, and the minimum value was 3 at%.

The above is a gas barrier film No. The results of 1 were the same as those of the other examples.

As is clear from this result, it was confirmed that the gas barrier film satisfied the above-mentioned requirements (i) and (ii) in the silicon atom ratio, oxygen atom ratio, and carbon atom ratio.

(Deposition conditions)
Feed rate of raw material gas (hexamethyldisiloxane, abbreviation: HMDSO): 50 sccm (Standard Cubic Centimeter per Minute),
Reaction gas (O ₂ ) supply amount: 500 sccm,
Degree of vacuum in the vacuum chamber: 3 Pa
Applied power from the power source for plasma generation: 0.8 kW,
Frequency of power source for generating plasma: 70 kHz,
Film conveyance speed: 0.8 m / min.

[Evaluation of gas barrier film]
The gas barrier films 1 to 13 produced as described above were evaluated as follows.

<< Evaluation of transparency: Measurement of total light transmittance >>
After the formation of the gas barrier layer by the plasma CVD method, the gas barrier film No. For 1 to 9, 12 and 13, the heat resistant laminate film was peeled off, and the total light transmittance of the gas barrier films 1 to 13 was measured using a haze meter NDH5000 manufactured by Tokyo Denshoku Co., Ltd. The evaluation results are shown in Table 1. Thus, it turned out that the gas barrier film of a TAC film base material is excellent in transparency. When the gas barrier film 8 was peeled off the heat resistant laminate film, it was confirmed that the pressure-sensitive adhesive remained slightly on the back surface of the gas barrier film.

<< Evaluation of water vapor barrier property (water vapor transmission rate WVTR) >>
After the formation of the gas barrier layer by the plasma CVD method, the gas barrier films 1 to 9, 12 and 13 were peeled off the heat resistant laminate film and evaluated for water vapor barrier properties.

The evaluation of the water vapor barrier property was carried out using AQUATRAN manufactured by MOCON, and the water vapor transmission rate WVTR (g / m ² / day) was measured after the numerical value was stabilized at 38 ° C. and 90% RH. The evaluation of the water vapor barrier property was measured by sampling the initial plasma CVD film formation (100 m) and after continuous production (1000 m), respectively. The evaluation results are shown in Table 1.

Thus, it was found that the gas barrier film of the TAC film substrate of the present invention is excellent in water vapor barrier properties. When the gas barrier film 8 was peeled off the heat-resistant laminate film and then observed with an optical microscope, it was found that the inorganic film had some cracks. In addition, 100 m and 1000 m mean that, in the plasma CVD film forming apparatus, a portion where the current and voltage are stable is set to “0 m”, and “100 m” and “1000 m” rolls are sent therefrom.

1 gas barrier film,
2, 52, 110 TAC film substrate,
3, 50 gas barrier layer (first inorganic layer),
31 manufacturing equipment,
32 Feeding roller,
33, 34, 35, 36 transport rollers,
39, 40 Deposition roller,
41 gas supply pipe,
42 Power supply for plasma generation,
43, 44 Magnetic field generator,
45 take-up roller,
101 plasma CVD apparatus,
102 vacuum chamber,
103 cathode electrode,
105 susceptors,
106 heat medium circulation system,
107 vacuum exhaust system,
108 gas introduction system,
109 high frequency power supply,
160 Heating and cooling device.

201 Gas barrier film (with heat resistant laminate film),
202 Gas barrier film (without heat-resistant laminate film),
203 heat resistant laminate film,
51 clear hard coat layer,
53 adhesive layer,
54 Laminated substrate.

Note that this application is based on Japanese Patent Application No. 2014-077315 filed on April 3, 2014, the disclosure of which is incorporated by reference in its entirety.

Claims (13)

A method for producing a gas barrier film having a step of forming a gas barrier layer on one surface of a TAC film substrate by a vacuum film formation method,
The gas barrier layer is manufactured in a state where a heat resistant laminate film having a laminate base material and an adhesive layer is disposed on the surface opposite to the surface on which the gas barrier layer of the TAC film base material is formed through the adhesive layer. Perform the filming process,
A method for producing a gas barrier film, wherein the ratio A / B of the thickness (A) of the TAC film substrate and the thickness (B) of the laminate substrate is 2.2 or less. The method for producing a gas barrier film according to claim 1, wherein the ratio A / B is 0.3 to 2.0. The method for producing a gas barrier film according to claim 1 or 2, wherein the adhesive force between the TAC film substrate and the heat-resistant laminate film is 0.08 to 0.2 N / inch. The method for producing a gas barrier film according to any one of claims 1 to 3, wherein the Young's modulus of the laminate base material is 0.4 to 4.0. The method for producing a heat-resistant laminate film according to any one of claims 1 to 4, wherein a thermal expansion coefficient of the laminate base material at 25 to 80 ° C is 50 ppm / ° C or less. The gas barrier layer has the following conditions (i) to (ii):
(I) The distance (L) from the surface of the first inorganic layer in the film thickness direction of the first inorganic layer and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (silicon atomic ratio) A distribution curve showing the relationship between L and the oxygen distribution curve showing the relationship between the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atomic ratio of oxygen); In the carbon distribution curve showing the relationship between the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (the atomic ratio of carbon), the carbon distribution curve has at least two extreme values,
(Ii) The absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 3 at% or more.
The method for producing a gas barrier film according to any one of claims 1 to 5, which satisfies the following conditions. 7. The method according to claim 1, further comprising a step of winding a gas barrier film bonded with the heat resistant laminate film into a roll after forming a gas barrier layer on the TAC film substrate having the heat resistant laminate film. 2. A method for producing a gas barrier film according to item 1. A gas barrier film produced by a production method having a step of forming a gas barrier layer on one surface of a TAC film substrate,
In the manufacturing method, in a state where a heat-resistant laminate film having a laminate base material and an adhesive layer is disposed on the surface opposite to the surface on which the gas barrier layer of the TAC film base material is formed via the adhesive layer, Performing a process of forming the gas barrier layer;
A gas barrier film in which a ratio A / B between the thickness (A) of the TAC film substrate and the thickness (B) of the laminate substrate is 2.2 or less. The gas barrier film according to claim 8, wherein the ratio A / B is 0.3 to 2.0. The gas barrier film according to claim 8 or 9, wherein an adhesive force between the TAC film substrate and the heat-resistant laminate film is 0.08 to 0.2 N / inch. The gas barrier film according to any one of claims 8 to 10, wherein the Young's modulus of the laminate base material is 0.4 to 4.0. The heat resistant laminate film according to any one of claims 8 to 11, wherein a thermal expansion coefficient of the laminate base material at 25 to 80 ° C is 50 ppm / ° C or less. The gas barrier layer has the following conditions (i) to (ii):
(I) The distance (L) from the surface of the first inorganic layer in the film thickness direction of the first inorganic layer and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (silicon atomic ratio) A distribution curve showing the relationship between L and the oxygen distribution curve showing the relationship between the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atomic ratio of oxygen); In the carbon distribution curve showing the relationship between the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (the atomic ratio of carbon), the carbon distribution curve has at least two extreme values,
(Ii) The absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 3 at% or more.
The gas barrier film according to any one of claims 8 to 12, which satisfies the following conditions.

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