JP4589128B2 - Gas barrier film that prevents bending - Google Patents

Description

  The present invention relates to a gas barrier film, and more particularly to a gas barrier film having scratch resistance, heat resistance, and gas barrier properties, and capable of preventing a base film film from being curved.

In the present specification, “ratio”, “part”, “%” and the like indicating the blending are based on mass unless otherwise specified, and the “/” mark indicates that they are integrally laminated.
“HC layer” is “hard coat layer”, “IP” is “ion plating”, “CVD” is “chemical vapor deposition”, “PET” is “polyethylene terephthalate”, “PC” is “polycarbonate” ”,“ PEN ”are“ polyethylene naphthalate ”and“ EL ”are abbreviations, functional expressions, common names, or industry terms for“ electroluminescence ”.

(Background Art) Gas barrier films are mainly used as (b) packaging materials for foods and pharmaceuticals to prevent the influence of oxygen and water vapor, etc., which cause the quality of the contents to change. In order to avoid that elements formed on a panel, an EL display panel, and the like are exposed to water vapor and deteriorate in performance, they are used for electrode plates, panel substrates, and the like as packaging materials for electronic devices and the like. As gas barrier films, there are conventionally known those in which a film having a gas barrier property is bonded, and those in which a film having a gas barrier property is formed into a wet film or a dry film. Preferably, it is composed of a base film and an inorganic thin film layer having an excellent gas barrier property provided on the base film, and the inorganic thin film is formed by vacuum deposition, sputtering, CVD (chemical vapor deposition). ) Method, and generally uses a roll coater type apparatus.
When the inorganic thin film is formed, if the base film is scratched, the gas barrier property is remarkably lowered, so that excellent scratch resistance is required, and the packaging material and the image display device are required to be visible. Therefore, it is necessary to prevent the base film from being damaged. Moreover, since the packaging material and the base film for an image display device are subjected to a high temperature process, heat resistance is required, and chemical resistance is required for using various solvents. Furthermore, in the permeation of water vapor, adsorption to the outermost surface of the base film is the first process, and it has been found that the reduction of the surface area by flattening the surface is effective for the reduction of the water vapor transmission rate. .
Therefore, the gas barrier film provides excellent gas barrier properties by forming an inorganic thin film layer on a base film having a flat surface and improved scratch resistance, chemical resistance and heat resistance. In order to maintain a stable process in continuous operation, good flatness to the product to be used, and excellent dimensional accuracy, a material having a small curvature (also referred to as warpage or curl) is required.

(Prior art) Conventionally, a functional film (corresponding to the gas barrier film of the present invention) has been exposed to air at the intermediate vacuum processing surface, and the active species on the surface are deactivated, or the surface is oxidized. There is known a multiple vacuum processing method that can obtain a laminate (corresponding to the inorganic thin film layer of the present invention) having a constant quality without being affected by the interface between the layers (for example, see Patent Document 1). .) However, there is no description or suggestion about the curvature and heat resistance of the obtained functional film.
Conventionally, as a method for producing a gas barrier film, a method of forming a gas barrier film by plasma CVD in the presence of at least an organic silicon compound vapor and a gas having oxygen or oxidizing power is known (for example, Patent Documents 2 to 2). 3). However, it relates to hydrophobicity and water repellency, and prevents surface curvature, scratch resistance, chemical resistance and heat resistance, as well as curving as much as possible to maintain good flatness and excellent dimensional accuracy for the products used. Is not described or suggested.
Further, conventionally, a transparent film substrate (corresponding to the gas barrier film of the present invention) having a gas barrier layer and a solvent-resistant protective layer made of a curable resin on at least one surface of a polymer film is known. (For example, refer to Patent Document 4). However, the refractive index of the polymer film and the solvent-resistant protective layer is limited to reduce interference spots. As in the present invention, the base film / hard coat layer (surface property, scratch resistance, It has no chemical / heat-resistant) / gas barrier layer configuration, nor is it described or suggested to prevent bending.
Furthermore, the present applicant has disclosed a decorative sheet for building materials in which the ease of curling has been eliminated (see, for example, Patent Document 5). However, it is limited to a decorative sheet using an electron beam (EB) curable resin, does not consider the change in curl strength due to heat load, there is no reference to a fragile substrate such as a heat resistant substrate, There is no description or suggestion of preventing surface curvature, scratch resistance, chemical resistance, and heat resistance, as well as curving as much as possible to maintain good flatness and excellent dimensional accuracy to the product used.
Furthermore, the present applicant has disclosed a gas barrier film having bending resistance and impact resistance (see, for example, Patent Document 6). However, it is very limited to the specific component ratio of silicon oxide, and it is very difficult to impart surface properties, scratch resistance, chemical resistance and heat resistance, and good flatness to the product used and excellent There is no description or suggestion of preventing bending as much as possible to maintain dimensional accuracy.

Japanese Patent Laid-Open No. 08-176326 Japanese Patent Laid-Open No. 11-309815 JP 2000-6301 A JP 2003-291274 A JP 2001-96707 A JP 2002-361774 A

  Accordingly, the present invention has been made to solve such problems. Its purpose is to provide an excellent gas barrier property by forming an inorganic thin film layer on a base film having a flat surface and improved scratch resistance, chemical resistance and heat resistance. It is to provide a gas barrier film that prevents bending as much as possible in order to maintain stable progress in continuous work, good flatness to a product to be used, and excellent dimensional accuracy.

In order to solve the above-mentioned problems, the gas barrier film according to the invention of claim 1 is a gas barrier film in which at least a hard coat layer and an inorganic thin film layer are provided on a base film directly or through another layer. The surface roughness centerline average roughness (Ra) measured by JIS-B-0601 of the base film is 300 nm or less, the total light transmittance measured by JIS-K7105 is 80% or more, and the hard coat The layer is made of an ionizing radiation resin , the pencil hardness measured by JIS-K-5400 is H or higher, the moisture permeability measured by JIS-K-7129 of the gas barrier film is 13 g / m ² · day or less, and The curvature κ satisfies the formula 0 ≦ κ ≦ 5 (κ = 1 / R) (where κ is the curvature, R is the radius of curvature, and the unit is m), and the cardopoly is formed on the inorganic thin film layer. Have a planarizing layer containing over, the ionizing radiation resin is mainly (meth) acrylates and melamine acrylates, wherein the melamine acrylate, to those having 1 or more methylol groups, is obtained by.
The gas barrier film according to the invention of claim 2 is characterized in that the inorganic thin film layer is a metal, an inorganic oxide layer, an inorganic nitride layer or an inorganic oxynitride layer, and further contains an inorganic oxide carbide layer or an inorganic nitride carbide layer containing carbon. Inorganic oxynitride carbide, the inorganic thin film layer having a thickness of 5 to 500 nm.
The gas barrier film according to the invention of claim 3 has a stress relaxation layer formed on at least one surface of the base film.
The gas barrier film according to the invention of claim 4 is such that the stress relaxation layer is formed on the surface of the base film opposite to the surface on which the hard coat layer and the inorganic thin film layer are formed. It is a thing.
The gas barrier film according to the invention of claim 5 is formed by providing an inorganic thin film layer and / or an organic substance layer on at least one surface of the gas barrier film according to any one of claims 1 to 4. .
The packaging material, color filter, or transparent electrode according to the invention of claim 6 is formed by using the gas barrier film according to any one of claims 1 to 5 .
A liquid crystal display device or an organic EL display device according to the invention of claim 7 is formed by using the gas barrier film according to any one of claims 1 to 5 .

According to the first aspect of the present invention, a hard coat layer having a prescribed pencil hardness is provided on a substrate film having a prescribed surface roughness and total light transmittance, and an inorganic thin film layer is formed on the hard coat layer surface. Further, it is possible to provide a gas barrier film which imparts surface properties, scratch resistance, chemical resistance, heat resistance and gas barrier properties, and has little curvature.
According to the second aspect of the present invention, by limiting the material and thickness of the inorganic thin film layer, excellent gas barrier properties and stable production by continuous operation can be achieved. In order to maintain excellent dimensional accuracy, a gas barrier film with less curvature is provided.
According to the fifth aspect of the present invention, there is further provided a gas barrier film that can be applied to various members by providing an inorganic thin film layer and / or an organic material layer.
According to the present invention of claim 6, a packaging material, a color filter, or a transparent electrode, which is excellent in surface properties, scratch resistance, chemical resistance, heat resistance and gas barrier properties, and can be processed efficiently since it is less curved. Is provided.
According to the seventh aspect of the present invention, there is provided a liquid crystal display device or an organic EL display device which is excellent in surface property, scratch resistance, chemical resistance, heat resistance and gas barrier property, and which can be efficiently assembled because of less bending. Provided.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a cross-sectional view of a gas barrier film showing one embodiment of the present invention.
FIG. 2 is a cross-sectional view of a gas barrier film showing one embodiment of the present invention.
FIG. 3 is a cross-sectional view of a gas barrier film showing one embodiment of the present invention.

(Invention of Product) The gas barrier film 10 of the present invention is provided with at least a hard coat layer (also referred to as HC layer) 15 and an inorganic thin film layer 13 on a base film 11, and the hard coat layer 15 and the inorganic thin film layer 13 are directly provided. Although in contact, other layers may optionally be provided on other layers or surfaces. The surface roughness center line average roughness (Ra) measured by JIS-B-0601 of the said base film 11 shall be 300 nm or less, the total light transmittance measured by JIS-K7105 shall be 80% or more, The said hard-coat layer 15 consists of ionizing radiation or a thermosetting resin, and the pencil hardness measured by JIS-K-5400 is set to H or more. By doing in this way, the water vapor transmission rate measured by JIS-K-7129 of the said gas barrier film can be made into 13 g / m < ² > * day or less, and curvature (kappa) can be made into the range of 0 <= k = 5.
In addition, another layer may be laminated or formed on the gas barrier film 10 of the present invention as necessary to form a packaging material, a color filter, or a transparent electrode, or an image display device using the color filter or the transparent electrode. It is preferable to do.

  (Base film) The base film 11 used in the present invention has a surface roughness measured according to JIS-B-0601, a center line average roughness (Ra) of 300 nm or less, and all measured according to JIS-K7105. Any natural or synthetic plastic film having a light transmittance of 80% or more and bending resistance may be used. When the total light transmittance is 80% or more, the transparency required for a display device can be obtained, and the surface roughness center line average roughness (Ra) is 300 nm or less. Thus, by forming the hard coat layer 15 and the inorganic thin film layer 13 on the surface, excellent gas barrier properties can be obtained, and both transparency and gas barrier properties can be achieved.

  Examples of the base film 11 include polyolefin (PO) resins such as homopolymers or copolymers or copolymers such as ethylene, polypropylene and butene, amorphous polyolefin resins (APO) such as cyclic polyolefins, and polyethylene terephthalate. Polyester resins such as (PET), polyethylene 2,6-naphthalate (PEN), polyamide (PA) resins such as nylon 6, nylon 12, copolymer nylon, polyvinyl alcohol (PVA) resin, ethylene-vinyl alcohol copolymer Polyvinyl alcohol resins such as coalescence (EVOH), polyimide (PI) resin, polyetherimide (PEI) resin, polysulfone (PS) resin, polyethersulfone (PES) resin, polyetheretherketone (PEEK) resin, polycarbonate PC) resin, polyvinyl butyrate (PVB) resin, polyarylate (PAR) resin, ethylene-tetrafluoroethylene copolymer (ETFE), ethylene trifluoride chloride (PFA), tetrafluoroethylene-perfluoroalkyl vinyl ether It is possible to use a fluororesin such as a copolymer (FEP), vinylidene fluoride (PVDF), vinyl fluoride (PVF), perfluoroethylene-perfluoropropylene-perfluorovinyl ether-copolymer (EPA), and the like. it can. Preferably, a polycarbonate resin suitable for display applications with a deflection temperature under load of 150 ° C. or higher and a small optical anisotropy, and a polyethylene naphthalate resin suitable for display applications for high definition with a deflection temperature under load of 150 ° C. or more and a low linear expansion coefficient Or a transparent polyimide resin having a deflection temperature under load of 230 ° C. or higher, and may be appropriately selected depending on the application. It is also possible to use a material in which various thermoplastic resins are infused into a glass fiber as disclosed in JP-A-2003-84264. The linear expansion coefficient at 25 to 150 ° C. is about 1 to 100 ppm / K or less, preferably 1 to 80 ppm / K or less, more preferably 1 to 60 ppm / K or less, and most preferably 1 to 30 ppm / K or less. For example, when a high-definition pattern is formed, necessary and sufficient dimensional stability accuracy can be obtained, and high performance by heating in the barrier film forming process and the transparent conductive film forming process can be formed.

In addition to the resins listed above, a resin composition comprising an acrylate compound having a radical-reactive unsaturated compound, a resin composition comprising a mercapto compound having an acrylate compound and a thiol group, epoxy acrylate, urethane acrylate It is also possible to use a photocurable resin such as a resin composition in which an oligomer such as polyester acrylate or polyether acrylate is dissolved in a polyfunctional acrylate monomer, and a mixture thereof. Furthermore, it is also possible to use what laminated | stacked 1 or 2 or more types of these resin by means, such as a lamination and a coating, as a base film.
The base film of the present invention using the above-described resins and the like may be an unstretched film or a stretched film. The flexible substrate film preferably has a thickness of 5 to 500 μm, more preferably 8 to 200 μm.

  The base film of the present invention can be produced by a conventionally known general method. For example, an unstretched substrate film that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching. Further, the unstretched base film is uniaxially stretched, tenter-type sequential biaxial stretch, tenter-type simultaneous biaxial stretch, tubular-type simultaneous biaxial stretch, and other known methods such as the base film flow (vertical axis) direction. Alternatively, a stretched substrate film can be produced by stretching in the direction perpendicular to the flow direction of the substrate film (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the base film, but is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction, respectively.

  Also, for the purpose of improving the adhesion of the deposited film, at least one surface of the base film is treated with a known silane coupling agent or primer (polyester, polyurethane, acrylic, silicon, etc.), corona discharge. Surface treatment such as treatment or low-temperature plasma treatment may be performed, or a uniaxially stretched plastic film may be used as the base film. Furthermore, the substrate film may be heated during or after vapor deposition in order to stabilize the vapor deposition film composition and improve adhesion. In particular, when a commonly used primer layer is provided, adhesion with the base film 11 and the inorganic thin film layer 13 is remarkably improved, and flexibility and chemical resistance are also improved.

  (Hard Coat Layer) As the hard coat layer 15 of the present invention, an ionizing radiation curable resin obtained by irradiating an ionizing radiation curable resin composition with an ionizing radiation and cured, or a thermosetting resin can be applied. Examples of the ionizing radiation curable resin composition before curing include (meth) acrylates of polyfunctional compounds such as polyhydric alcohols (hereinafter, acrylate and methacrylate are described as (meth) acrylates in this specification), and the like. The well-known thing which consists of an oligomer or prepolymer of this, a reactive diluent, a photoinitiator, a photosensitizer, etc. is applicable. An ultraviolet absorber is dissolved or dispersed in the ionizing radiation curable resin composition as necessary, applied to the base film 11, and cured by irradiation with ionizing radiation to obtain an ionizing radiation curable resin. Examples of photopolymerization initiators include acetophenones, benzophenones, Michler benzoylbenzoate, α-amyloxime esters, thioxanthones, and photosensitizers include n-butylamine, triethylamine, tri-n-butylphosphine, Use by mixing. The hard coat layer preferably has a small linear expansion coefficient like the substrate, and is 1 to 80 ppm / K or less, preferably 1 to 60 ppm / K or less, more preferably 1 to 30 ppm / K at 25 to 150 ° C. If it is below, it is possible to suppress the peeling phenomenon due to the difference from the linear expansion coefficient of the base material, and particularly when forming a high-definition pattern, a necessary and sufficient dimensional stability accuracy can be obtained. High performance by heating in the transparent conductive film forming step enables film formation.

Examples of the ionizing radiation curable resin composition include those having an acrylate functional group, for example, relatively low molecular weight polyester, polyether, acrylic resin, epoxy resin, polyurethane, alkyd resin, spiroacetal resin, polybutadiene, polythiol. Polyethylenic resins, oligomers or prepolymers such as (meth) acrylates (hereinafter referred to as (meth) acrylates) of polyfunctional compounds such as polyhydric alcohols, and ethyl which is a reactive diluent Monofunctional monomers such as (meth) acrylate, ethylhexyl (meth) acrylate, styrene, vinyltoluene, N-vinylpyrrolidone, and polyfunctional monomers such as trimethylolpropane tri (meth) acrylate, hexanediol (meth) acrylic , Tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl Those containing a relatively large amount of glycol di (meth) acrylate and the like are used. Preferably, monofunctional monomers such as ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, N-vinylpyrrolidone, and polyfunctional monomers such as tripropylene glycol diacrylate, trimethylolpropane tri (meth) acrylate, diethylene glycol Examples include di (meth) acrylate, pentaerythritol tri (meth) acrylate, neopentyl glycol di (meth) acrylate, and the like. More preferably, a thermal or ionizing radiation curable resin such as an epoxy acrylate prepolymer having a melting point of 50 ° C. or higher or a urethane acrylate prepolymer having a melting point of 50 ° C. or higher can be used, and satisfies the characteristics as a display medium such as liquid crystal. If possible, a thermally more stable thermosetting type may be used.
Examples of the thermosetting resin include epoxy resins such as phenol novolac, which is a reaction product of phenol and formaldehyde, and polyfunctional epoxy resins formed by reaction with epichlorohydrin, and acrylic resins.

  The ionizing radiation curable resin includes a reactive organosilicon compound represented by the general formula RmSi (OR ') n (wherein R and R' represent an alkyl group having 1 to 10 carbon atoms, m + n = 4 And m and n are each integers). Examples of such silicon compounds include tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert- Butoxysilane, tetrapentaethoxysilane, tetrapenta-iso-propoxysilane, tetrapenta-n-propoxysilane, tetrapenta-n-butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-tert-butoxysilane, methyltrimethoxysilane, methyltrimethoxysilane Ethoxysilane, methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, di Chill propoxysilane, dimethyl-butoxy silane, methyl dimethoxy silane, methyl diethoxy silane, hexyl trimethoxy silane, and the like to.

  Polyfunctional acrylate crosslinkers include ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate , Trimethylolpropane triacrylate, pentaerythritol tetraacrylate, or dipentaerythritol hexaacrylate.

  The materials used for the hard coat layer 13 are mainly (meth) acrylate and melamine acrylate. In order to obtain melamine acrylate, first, the methylol group of methylolmelamine obtained by reacting the amino group of melamine with formaldehyde is reacted with an alcohol (for example, an aliphatic alcohol having about 1 to 4 carbon atoms such as methanol) to obtain alkoxy. Methyl melamine is produced and subsequently reacted with 2-hydroxyethyl acrylate or the like to produce an acryloyl group at the alkoxymethyl group. In order to cure by irradiation with ionizing radiation such as electron beam or ultraviolet ray, the number of acrylate groups in melamine acrylate is preferably 2 or more, more preferably 3 or more. The crosslinking density can be adjusted by using a melamine acrylate together with a crosslinking agent which is a polyfunctional acrylate.

  Polyfunctional acrylate crosslinkers include ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate , Trimethylolpropane triacrylate, pentaerythritol tetraacrylate, or dipentaerythritol hexaacrylate.

  By the way, since the number of amino groups of melamine is 3, and the total number of hydrogens attached to the amino groups is 6, the maximum number of alkoxymethyl groups is 6. The number of introduced alkoxymethyl groups is reduced, or, once six alkoxymethyl groups are introduced, a part thereof is returned to the methylol group form to reduce the number of hydroxyl groups in the methylol group to 0-6. Can be controlled within the range. Therefore, when the melamine is crosslinked using a crosslinking agent, the crosslinking density of the melamine acrylate can be controlled by changing the number of hydroxyl groups. When the crosslink density of melamine is changed and the crosslink density is improved in this way, the stain resistance is improved. The number of hydroxyl groups introduced in the sense of improving stain resistance is preferably 1 or more, and if it is 3 or more, it is not contaminated by most substances. In the above example, an acrylate group is introduced into melamine, but other vinyl groups may be introduced instead of the acrylate base.

  The crosslinking agent for crosslinking melamine is preferably one having two or more functional groups in the molecule that can react with the hydroxyl group of melamine introduced with the above hydroxyl group. For example, tolylene diisocyanate (TDI) ), Or an isocyanate compound having two or more isocyanate groups such as xylylene diisocyanate (XDI) can be used, and very excellent stain resistance is obtained, and the curling of the decorative sheet is moderate and easy to handle. However, in this invention, since the effect by using melamine acrylate is large, even if it uses the above-mentioned polyfunctional acrylate as a crosslinking agent, it is excellent in stain resistance, and it is hard to curl also in the case of a decorative sheet. In addition, the use of a polyfunctional acrylate has an advantage that the reaction is completed quickly.

  The melamine acrylate and the crosslinking agent as described above are mixed with an additive such as a filler, a solvent, or a diluent as necessary to obtain a predetermined blending ratio, and then a coating composition is applied. It coat | covers with a suitable application | coating means on the base film which gave the object makeup | decoration, and forms a coating film. As the coating method, those mentioned as the method for forming the colored layer can be used. The thickness of the coating film is about 2 μm to 50 μm. After application, the thermosetting component in the coating film is reacted by heating. If it is an example of the melamine acrylate which has a hydroxyl group, and the said isocyanate compound, reaction of the hydroxyl group in a melamine acrylate and isocyanate will advance. As an example of the reaction condition, it is about 1 minute at 120 ° C., and this time is substantially equal to the time required to pass through the drying zone in a general coater, although it depends on the coating speed.

  Subsequently, the coating film is cured by irradiating the coating film with ionizing radiation. As an electron beam source, various electron beam accelerators such as a cockcroft Walton type, a bandegraph type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type are used. Preferably, the one that irradiates electrons having energy of 100 to 300 KeV is used. As the ultraviolet light source, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light, a metal halide lamp can be used, and technically easy ultraviolet curing is preferable.

  The film thickness of the hard coat layer as described above is usually in the range of 1 to 30 μm, and the formation method is not particularly limited, and a normal coating method can be used. If the thickness of the hard coat layer is too thin, it will not be possible to maintain the hardness of each layer formed on it, and if it is too thick, the flexibility of the entire transparent laminated film will be reduced, and it will take time to cure, etc. Lead to a decline. Thus, the pencil hardness measured by JIS-K-5400 can be made into H or more by using ionizing radiation or a thermosetting resin for the hard coat layer 15. Since the hard coat layer 15 has excellent scratch resistance, even when the inorganic thin film layer 13 is formed with a roll-running continuous device, the inorganic thin film layer 13 with very few scratches can be formed. The gas barrier property can be maintained.

  (Inorganic thin film layer) The inorganic thin film layer 13 used in the present invention is not particularly limited as long as it has gas barrier properties, and the materials thereof are aluminum, nickel, chromium, iron, cobalt, zinc, gold, silver, copper. Metals such as silicon, germanium, carbon, etc .; oxides such as aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, hafnium oxide, barium oxide; aluminum nitride, boron nitride, Examples thereof include nitrides such as magnesium nitride; sulfides; carbides and the like. Preferable inorganic thin film layer 13 is a metal, an inorganic oxide layer, an inorganic nitride layer or an inorganic oxynitride layer, an inorganic oxide carbide layer containing carbon, an inorganic nitride carbide layer, or an inorganic oxynitride carbide. More preferably, it is an oxide such as aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, zirconium oxide, titanium oxide or the like, or a metal or semiconductor added or substituted therefor, or a mixture thereof. The inorganic thin film layer 13 is preferable from the viewpoint of reducing water vapor transmission rate while maintaining transparency.

  The inorganic thin film layer 13 is composed of an inorganic oxide layer, an inorganic nitride layer, or an inorganic oxynitride layer, and is preferably silicon oxide, aluminum oxide, titanium oxide, silicon nitride, aluminum nitride, titanium nitride, oxynitride Either silicon, aluminum oxynitride, or titanium oxynitride. In addition, a film layer of an inorganic oxide layer, an inorganic nitride layer, or an inorganic oxynitride layer containing carbon is also suitable, and is referred to as an inorganic oxide carbide layer, an inorganic nitride carbide layer, or an inorganic oxynitride carbide layer herein To do. That is, as the inorganic thin film, inorganic oxide (MOx), inorganic nitride (MNy), inorganic oxide carbide (MOxCz), inorganic nitride carbide (MNyCz), inorganic oxynitride (MOxNy), inorganic oxynitride carbide (MOxNyCz) And preferable M is Si, Al, Ti. In this specification, the notation of inorganic oxide, inorganic nitride, inorganic oxide carbide, inorganic nitride carbide, inorganic oxynitride, and inorganic oxynitride carbide indicates that x, y, and z have predetermined chemical equivalents. Includes less than.

(Formation of inorganic thin film layer) Next, the inorganic thin film layer 13 will be described. As a method for forming the inorganic thin film layer 13, for example, a vacuum deposition method, a chemical vapor deposition method, a physical vapor deposition method, or a sol-gel method is used. In the present invention, a vacuum film-forming method such as a vacuum deposition method, a sputtering method, an ion plating method, a chemical vapor deposition (CVD) method, or a physical vapor deposition (PVD) method is applied. The ion plating method and the plasma CVD method are particularly preferable. According to the vacuum film-forming method, it is possible to form a continuous layer that is dense and has few gaps, and thus has low moisture permeability and / or oxygen permeability and excellent flame retardancy that suppresses the generation of flammable gases. In addition, continuous production is highly productive and low cost.
The inorganic thin film layer 13 in the present invention may be a single layer film composed of one layer of the inorganic thin film layer 13, or a multilayer film or a composite film composed of two or more layers, alone or in combination. Moreover, when providing the inorganic thin film layer 13 on both surfaces, after forming in one surface, what is necessary is just to form in the other surface similarly.

  (Chemical Vapor Deposition CVD) Vacuum deposition methods such as vacuum deposition, sputtering, or PVD are well known to those skilled in the art, and are preferred inorganic thin films formed by the preferred chemical vapor deposition method and ion plating method of the present invention. The layer 13 will be further described. Examples of the inorganic thin film formed by the chemical vapor deposition method include chemical vapor deposition such as plasma chemical vapor deposition, thermal chemical vapor deposition, photochemical vapor deposition, and catalytic chemical vapor deposition (Cat-CVD). A phase growth method (Chemical Vapor Deposition method, CVD method) or the like can be applied. Specifically, on one surface of the base film 11, an evaporation gas such as an organosilicon compound is used as a raw material, an inert gas such as argon gas or helium gas is used as a carrier gas, and oxygen is supplied. As the gas, an oxygen gas or the like is used, and an inorganic oxide such as silicon oxide, aluminum oxide, titanium oxide, silicon nitride, aluminum nitride, titanium nitride, silicon oxynitride, aluminum oxynitride, or titanium oxynitride, inorganic nitride, or An inorganic oxynitride film which can form an inorganic oxynitride film and further contains carbon in the above-mentioned inorganic thin film layer by using a low temperature plasma chemical vapor deposition method utilizing a low temperature plasma generator or the like. Alternatively, an inorganic oxynitride carbide film can be formed. The inorganic thin film not containing carbon can be produced by an ion plating method. The carbon-free inorganic thin film produced by this production method can have sufficient flexibility and adhesion as well as the CVD method, and can be suitably used. As the low-temperature plasma generator, for example, a generator such as a high-frequency plasma, a pulse wave plasma, or a microwave plasma can be used. It is preferable to do.

FIG. 8 is an explanatory diagram of a CVD apparatus that can be suitably used in the present invention.
An example of the method for forming the inorganic thin film 13 by the low-temperature plasma chemical vapor deposition method (referred to as plasma CVD) can be suitably used. The plasma CVD apparatus 200 includes a vacuum container 210, a gas supply unit, a vacuum pump, a power source, and a control device (not shown). The vacuum container 210 includes a paper feeding unit 211, a film forming unit 213, and a winding unit 215. ing. The film forming unit 213 includes a plurality of rooms such as a chamber 221, b chamber 223, and c chamber 213 according to the inorganic oxide to be formed. The base film 11 is fed out from the unwinding roll disposed in the paper supply unit 211 in the vacuum vessel 210, cooled at a predetermined speed through the guide roll, and conveyed onto the circumferential surface of the electrode drum 231. The gas supply unit supplies oxygen gas, inert gas, monomer gas such as an organosilicon compound, etc. from a gas supply device and a raw material volatilization supply device, etc., and does not adjust their single or mixed gas composition. It introduces into the vacuum vessel 210.

  FIG. 8 shows an example using three kinds of gases, and the gas composition is introduced into the vacuum vessel 210 through the raw material supply nozzles 251, 253, and 255. The substrate film 11 transported on the peripheral surface of the cooling and electrode drum 221 is irradiated with plasma generated by glow discharge plasma, and an inorganic oxide such as silicon oxide, an inorganic nitride, or an inorganic oxynitride film Is formed (formed). At that time, predetermined power is applied to the cooling, electrode drum 221, a chamber electrode 251, b chamber electrode 253, and c chamber electrode 255 from a power source arranged outside the vacuum vessel 210, Further, a magnet or the like may be disposed in the vicinity of the cooling and electrode drum 221 to promote the generation of plasma. Next, the base film 11 on which the inorganic oxide, inorganic nitride, or inorganic oxynitride film is formed as described above is wound up through a guide roll, and the inorganic oxide, inorganic nitride, or inorganic oxide is formed by a plasma CVD method. A nitride film can be formed. The inorganic oxide, inorganic nitride, or inorganic oxynitride film is not only a single layer of inorganic oxide, inorganic nitride, or inorganic oxynitride film, but also a multilayer film in which two or more layers are stacked. But you can.

  Moreover, the material to be used can also be used by 1 type, or 2 or more types of mixtures, and can also comprise the inorganic thin film film mixed with the dissimilar material. By selecting a material to be used, an inorganic thin film layer 13 such as an inorganic oxide layer, an inorganic nitride layer, an inorganic oxynitride layer, an inorganic oxycarbide layer, an inorganic oxycarbide layer, or an inorganic oxynitride carbide layer is formed. Can do.

  In addition, about composition of the inorganic thin film layer 13, surface analyzers, such as a photoelectron spectrophotometer, an X-ray photoelectron spectrometer (Xray Photoelectron Spectroscopy, XPS), a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy, SIMS), are used, for example. By using elemental analysis of the silicon oxide film using a method such as ion etching in the depth direction for analysis, the above-described composition ratio and physical properties can be confirmed.

  (Inorganic oxide) As the inorganic oxide film, basically any thin film on which a metal oxide is deposited can be used. For example, silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y) and other metal oxides An inorganic oxide film can be used, and an oxide of a metal such as silicon (Si), aluminum (Al), titanium (Ti), or the like is preferable. The inorganic oxide film can be referred to as a metal oxide such as silicon oxide, aluminum oxide, magnesium oxide, etc., and its notation is, for example, MOx (provided that the formula is SiOx, AlOx, MgOx, etc.) M represents a metal element, and the value of X varies depending on the metal element.) Moreover, as a range of said x value, silicon (Si) is 0.1-2, aluminum (Al) is 0.1-1.5, magnesium (Mg) is 0.1-1, Calcium (Ca) is 0.1 to 1, potassium (K) is 0.1 to 0.5, tin (Sn) is 0.1 to 2, and sodium (Na) is 0.1 to 0. 5, Boron (B) is 0.1 to 1, 5, Titanium (Ti) is 0.1 to 2, Lead (Pb) is 0.1 to 1, Zirconium (Zr) is 0.1 to 2 Yttrium (Y) can take a value in the range of 0.1 to 1.5. In the above formula, when x = 0, it is a complete metal and is not transparent and cannot be used. The upper limit of the range of x is a completely oxidized value. Preferred metal oxides of the present invention are silicon (Si), aluminum (Al), and titanium (Ti) oxides. The value of x is, for example, silicon (Si) 1.0-2. If 0 is aluminum (Al), 0.5 to 1.5 can be used, and if titanium (Ti), 1.3 to 2.0 can be used.

  In the present invention, the film thickness of the inorganic thin film varies depending on the type of metal or metal oxide used, for example, about 1 to 1000 nm, preferably 5 It is about -500 nm, More preferably, it exists in the range of 10-200 nm. Above this range, cracks and the like are likely to occur in the film, and below this range, it becomes difficult to achieve gas barrier properties. The film thickness of the inorganic oxide film such as silicon oxide is increased by increasing the deposition rate of the inorganic oxide film, that is, by increasing the amount of monomer gas and oxygen gas or by decreasing the running speed of the base film. It can be performed and may be selected as appropriate. The film thickness can be measured by, for example, a fundamental parameter method, an ellipsometer UVISEL ™ (trade name) manufactured by JOBIN YVON, using a fluorescent X-ray analyzer (model name, RIX2000 type) manufactured by Rigaku Corporation. .

  (Aluminum oxide) An aluminum oxide inorganic oxide film is formed by forming (forming or chemically reacting) aluminum oxide or metal aluminum in oxygen gas, and the reaction product is formed on one surface of the base film. The aluminum oxide represented by the general formula AlOx (where x represents a number of 0.5 to 1.5) is usually formed. It is a continuous thin film mainly composed of

  (Titanium oxide) The formation of an inorganic oxide film of titanium oxide is performed by forming titanium oxide or metal titanium in oxygen gas (formation or chemical reaction), and the reaction product is formed on one side of the base film. Titanium oxide represented by the general formula TiOx (where x represents a number from 1.3 to 2.0) is usually formed. It is a continuous thin film mainly.

  (Inorganic nitride) As the inorganic nitride film, basically any thin film on which a metal nitride is deposited can be used. For example, silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y) and other metal nitrides An inorganic nitride film can be used, and a nitride of a metal such as silicon (Si), aluminum (Al), titanium (Ti), or the like is preferable. The inorganic nitride film can be referred to as a metal nitride such as silicon nitride, aluminum nitride, titanium nitride, and the like, and the notation thereof is, for example, MNy (wherein the formula M represents a metal element, and the value of y is represented by a range depending on the metal element). In addition, the range of the y value is y = 0.1 to 1.3 for silicon (Si), y = 0.1 to 1.1 for aluminum (Al), and y = 0 for titanium (Ti). 0.1 to 1.3 and tin (Sn) can take values in the range of y = 0.1 to 1.3. In the above formula, when y = 0, it is a complete metal and is not transparent and cannot be used. The upper limit of the range of y = is a completely nitrided value. The preferred metal nitride of the present invention is preferably an oxide of silicon (Si), aluminum (Al), or titanium (Ti). The value of y = is, for example, silicon (Si), y = 0.5. -1.3, if aluminum (Al), y = 0.3-1.0, if titanium (Ti), y = 0.5-1.3, if tin (Sn), y = 0. The thing of the range of 5-1.3 can be used. However, even a colored film may be used because it can maintain transparency if it is 3 to 15 nm.

  (Inorganic oxynitride film) As the inorganic oxynitride film, a thin film in which a metal oxynitride is basically deposited can be used. For example, silicon (Si), aluminum (Al), magnesium ( Metals such as Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y) An inorganic oxynitride film of oxynitride can be used, and a metal oxynitride such as silicon (Si), aluminum (Al), titanium (Ti), or the like is preferable. The inorganic oxynitride film can be called as a metal oxynitride such as silicon oxynitride, aluminum oxynitride, titanium oxynitride, etc., and its notation is, for example, SiOxNy, AlOxNy, TiOxNy, etc. MOxNy (where, M represents a metal element, and the values of X and y are different depending on the metal element). Moreover, as a range of said value of x and y, silicon (Si) is x = 1.0-2.0, y = 0.1-1.3, aluminum (Al) is x = 0.5- 1.0, y = 0.1-1.0, magnesium (Mg) is x = 0.1-1.0, y = 0.1-0.6, calcium (Ca) is x = 0.1 1.0, y = 0.1-0.5, potassium (K) is x = 0.1-0.5, y = 0.1-0.2, tin (Sn) is x = 0.1 2.0, y = 0.1 to 1.3, sodium (Na) x = 0.1 to 0.5, y = 0.1 to 0.2, boron (B) x = 0.1 1.0, y = 0.1-0.5, titanium (Ti) x = 0.1-2.0, y = 0.1-1.3, lead (Pb) x = 0.1 1.0, y = 0.1 to 0.5, zirconium (Zr) is x = 0.1 to 2.0, y = 0.1 .0, yttrium (Y) may have a value in the range of x = 0.1~1.5, y = 0.1~1.0. In the above formula, when x = 0, it is a complete metal and is not transparent and cannot be used. Preferred metal nitrides of the present invention include silicon (Si), aluminum (Al), titanium (Ti ) And tin (Sn) oxides are preferable, and the values of x and y are, for example, silicon (Si) x = 1.0 to 2.0, y = 0.1 to 1.3, aluminum ( Al) for x = 0.5 to 1.0, y = 0.1 to 1.0, and titanium (Ti) for x = 1.0 to 2.0, y = 0.1 to 1. Those in the range of 3 can be used. However, even a colored film may be used because it can maintain transparency if it is 3 to 50 nm.

  (Inorganic oxide carbide film) As the inorganic oxide carbide film, any inorganic oxide carbide film can be used as long as it is basically a thin film in which a metal oxide carbide is deposited. For example, silicon (Si), aluminum ( Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium ( An inorganic oxide carbide film of a metal oxycarbide such as Y) can be used, and a metal oxycarbide such as silicon (Si), aluminum (Al), titanium (Ti), or the like is preferable. The inorganic oxide carbide film can be referred to as a metal oxide carbide such as silicon oxide carbide, aluminum oxide carbide, magnesium oxide carbide, etc., and its notation is, for example, MOxCz (wherein the formula is SiOxCz, AlOxCz, TiOxCz, etc.). M represents a metal element, and the values of x and z have different ranges depending on the metal element. Moreover, as a range of said x and z value, silicon (Si) is x = 0.1-1.95, z = 0.1-2.0, aluminum (Al) is x = 0.1-0.1. 1.5, z = 0.1-2.0, magnesium (Mg) x = 0.1-1.0, z = 0.1-1.5, calcium (Ca) x = 0.1 1.0, z = 0.1 to 1.5, potassium (K) x = 0.1 to 0.5, z = 0.1 to 1.0, tin (Sn) x = 0.1 2.0, z = 0.1-2.0, sodium (Na) x = 0.1-0.5, z = 0.1-1.0, boron (B) x = 0.1 1.0, z = 0.1-1.5, titanium (Ti) x = 0.1-2.0, z = 0.1-2.0, lead (Pb) x = 0.1 1.0, z = 0.1 to 2.0, zirconium (Zr) is x = 0.1 to 2.0, z = 0.1 2.0, yttrium (Y) may have a value in the range of x = 0.1~1.5, z = 0.1~2.0. In the above formula, when x = 0 and z = 0, the metal oxide is a complete metal and is not transparent and cannot be used. Preferred metal oxide carbides of the present invention include silicon (Si) and aluminum (Al). Titanium (Ti) oxide carbide is preferable, and the values of x and z are, for example, silicon (Si) x = 1.0 to 1.95, z = 0.1 to 2.0, aluminum (Al ) X = 1.0 to 1.5, z = 0.1 to 2.0, and titanium (Ti) x = 1.0 to 2.0, z = 0.1 to 2.0. The ones in the range can be used.

  (General formula SiOxCz) A preferable silicon oxide film containing carbon is mainly composed of silicon oxide and further contains a carbon element. In the general formula SiOxCz, when the amount of carbon is small (z value is small), the adhesion to the base film is lacking, and when the amount of carbon is large (z value is large), the moisture permeability and oxygen permeability are large. Since flame retardancy is lowered, in the general formula SiOxCz, x = 0.1 to 1.95 and z = 0.1 to 2.0 are preferable.

Next, as a vapor deposition monomer gas such as an organic silicon compound that forms an inorganic thin film that does not contain carbon such as silicon oxide, if it contains carbon, it will remain in the thin film. For example, monosilane, The use of Si, H, O, and N as a raw material that does not contain carbon, such as disilane, is a particularly preferable raw material because of its handleability and the characteristics of the formed continuous film. Moreover, in the above, as an inert gas, argon gas, helium gas, etc. can be used, for example.
Next, as a vapor deposition monomer gas such as an organic silicon compound for forming an inorganic thin film containing carbon such as silicon oxide carbide, for example, 1.1.3.3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethyl. Methoxysilane, vinyltrimethylsilane, tetramethoxysilane (TMOS), methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, tetraethoxysilane (TEOS), dimethyldiethoxysilane, methyldimethoxysilane, methyldiethoxysilane, hexamethyl In addition to preferably using disilazane, trimethoxysilane, etc., it is possible to use one or more known materials such as tetramethyldisiloxane, normal methyltrimethoxysilane as a raw material. Formed From characteristics of the continuous film, in particular, it is a preferred material. Moreover, in the above, as an inert gas, argon gas, helium gas, etc. can be used, for example.

  (Silicon oxide) In the present invention, an inorganic oxide film of silicon oxide formed by a vacuum film formation method using a vapor deposition monomer gas such as an organic silicon compound is a vapor deposition monomer gas such as an organic silicon compound and an oxygen gas or the like. And the reaction product closely adheres to one surface of the base film to form a dense, flexible thin film. Usually, the general formula SiOx (where x is A continuous thin film mainly composed of silicon oxide represented by the formula (1). As the inorganic oxide film of silicon oxide, silicon oxide represented by the general formula SiOx (where x represents a number of 1.3 to 2) from the viewpoint of transparency, gas barrier properties, flame retardancy, and the like. A thin film mainly composed of an inorganic oxide film is preferred. The value of x varies depending on the molar ratio of vapor deposition monomer gas to oxygen gas, plasma energy, etc. Generally, as the value of x decreases, the film itself becomes dense and the oxygen permeability decreases. It becomes yellowish and its transparency is poor.

In addition, the silicon oxide film is mainly composed of silicon oxide, and further contains at least one compound composed of one or more of carbon, hydrogen, silicon, or oxygen, or two or more of these elements by chemical bonding or the like. May be. For example, when a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit is in the form of graphite, diamond, fullerene, or the like, the raw material organosilicon compound or a derivative thereof is further added. It may be contained by a chemical bond or the like. Specific examples include hydrocarbons having a CH ₃ site, hydrosilica such as SiH ₃ silyl, SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol. In addition to the above, the type, amount, etc. of the compound contained in the inorganic oxide film of silicon oxide can be changed by changing the conditions of the vapor deposition process.

  The content of the above-mentioned compound in the silicon oxide film is about 0.1 to 50%, preferably about 5 to 20%. In the above, if the content is less than 0.1%, the impact resistance, spreadability, flexibility, etc. of the inorganic oxide film of silicon oxide become insufficient, and scratches, cracks, etc. occur due to bending etc. It is easy and it becomes difficult to stably maintain the gas barrier property, and if it exceeds 50%, the gas barrier property is lowered, which is not preferable. Furthermore, in the present invention, in the silicon oxide film, the content of the above compound is preferably decreased from the surface of the silicon oxide inorganic oxide film in the depth direction. On the surface of the material film, impact resistance and the like can be enhanced by the above compound and the like. On the other hand, since the content of the above compound is small at the interface with the base film, the base film and the silicon oxide film It has the advantage that the tight adhesion of the material becomes strong.

  (Inorganic nitride carbide film) As the inorganic nitride carbide film, any inorganic nitride carbide film can be used as long as it is basically a thin film obtained by vapor deposition of metal nitride carbide. For example, silicon (Si), aluminum ( Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium ( An inorganic nitride carbide film of a metal nitride carbide such as Y) can be used, and preferably a metal nitride carbide such as silicon (Si), aluminum (Al), titanium (Ti) or the like. The inorganic nitride carbide film can be referred to as a metal nitride carbide such as silicon nitride carbide, aluminum nitride carbide, titanium nitride carbide, and the like. M represents a metal element, and the values of y and z vary depending on the metal element.) Moreover, as a range of said y and z value, silicon (Si) is y = 0.1-1.3, z = 0.1-2.0, and aluminum (Al) is y = 0.1-0.1. 1.0, z = 0.1-1.5, magnesium (Mg) is y = 0.1-1.0, z = 0.1-1.5, calcium (Ca) is y = 0.1 1.0, z = 0.1 to 1.5, potassium (K) is y = 0.1 to 0.3, z = 0.1 to 1.0, tin (Sn) is y = 0.1 1.3, z = 0.1-2.0, sodium (Na) is y = 0.1-0.3, z = 0.1-1.5, boron (B) is y = 0.1 1.0, z = 0.1-1.5, titanium (Ti) is y = 0.1-1.3, z = 0.1-2.5, lead (Pb) is y = 0.1 1.0, z = 0.1 to 1.5, zirconium (Zr) is y = 0.1 to 1.3, z = 0.1 .0, yttrium (Y) may have a value in the range of y = 0.1~1.0, z = 0.1~2.0. In the above formula, when x = 0, it is a complete metal and is not transparent and cannot be used. Preferred metal nitride carbides of the present invention include silicon (Si), aluminum (Al), titanium (Ti ) Nitrided carbide is preferred, and the values of y and z are, for example, silicon (Si), y = 1.0 to 1.4, z = 0.1 to 2.0, and aluminum (Al). If y = 0.5 to 1.0, z = 0.1 to 2.0, and titanium (Ti), y = 1.0 to 1.3 and z = 0.1 to 2.0. Things can be used. However, even a colored film may be used because it can maintain transparency if it is 3 to 30 nm.

  (Inorganic oxynitride carbide film) A preferred inorganic oxynitride (inorganic oxynitride carbide) containing carbon is mainly composed of silicon oxynitride or titanium oxynitride and further contains a carbon element. In the general formula MOxNyCz, when the amount of carbon is small (z value is small), the adhesion to the base film is lacking, and when the amount of carbon is large (z value is large), the moisture permeability and oxygen permeability are large. Examples of the M element include silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), and titanium (Ti). ), Lead (Pb), zirconium (Zr), yttrium (Y), and the like can be used, and Si, Al, and Ti are preferable. However, even a colored film may be used because it can maintain transparency if it is 3 to 50 nm.

  As a preferable inorganic oxynitride carbide, for example, in the general formula SiOxNyCz, x = 0.1 to 1.95, y = 0.1 to 1.2, and z = 0.1 to 2.0 are preferable.

  In addition, in the general formula AlOxNyCz, the aluminum oxynitride thin film is formed by setting the composition in the range of x = 0.1 to 1.4, y = 0.1 to 0.9, and z = 0.1 to 2.0. A thin film with a low ratio of the residual carbon component of the titanium oxynitride thin film can suppress performance deterioration due to oxidation, and has high transparency and excellent adhesion to a CVD material (base film). .

  Further, in the general formula TiOxNyCz, the titanium oxynitride thin film can be obtained by setting the composition in the range of x = 1.0 to 1.8, y = 0.5 to 1.0, z = 0.3 to 1.5. A thin film with a low ratio of the residual carbon component of the titanium oxynitride film can be prevented from degrading performance due to oxidation, and a high transparency and excellent adhesion to the CVD material (base film) can be obtained. . As the material constituting the thin film layer, an organic titanium compound such as titanium tetrachloride or tetraisopropoxide is suitable. If the x value is less than this range, the Ti—O bond decreases and the film stress increases, peeling from the base film or chipping occurs in the thin film, and the barrier property decreases. Since it progresses and many functional groups are formed, it lacks heat resistance and moisture resistance. If the y value is less than this range, the film density is small and a dense film cannot be formed. Therefore, the barrier property is lowered. The barrier property is likely to be lowered by external force, and the flame retardancy is deteriorated. If the z value is less than this range, the carbon-containing component at the interface with the base film decreases, and the adhesion to the base film decreases. If the z-value exceeds this range, the carbon-containing component increases, resulting in film absorption. Coloring occurs.

  (Thickness) A preferable thickness in the general formula TiOxNyCz is 5 to 500 nm. Below this range, the barrier properties are almost the same as when the TiOxNyCz layer is not present, and the barrier properties are not improved, and beyond this range, the film stress increases and cracks occur in the thin film. Does not improve.

  In the present invention, the film thickness of the inorganic thin film layer 13 such as the inorganic oxide layer, inorganic nitride layer, inorganic oxynitride layer, inorganic oxide carbide layer, inorganic nitride carbide layer or inorganic oxynitride carbide layer as described above Depending on the type of metal or metal oxide used, etc., for example, it may be formed by arbitrarily selecting within the range of about 1 to 1000 nm, preferably about 5 to 500 nm, more preferably 10 to 200 nm. desirable. In the present invention, the inorganic oxide, the inorganic nitride, or the inorganic oxynitride film is a metal to be used, or the metal oxide is used as one kind or a mixture of two or more kinds of different materials. An inorganic oxide layer, an inorganic nitride layer, an inorganic oxynitride layer, an inorganic oxycarbide layer, an inorganic oxycarbide layer, or an inorganic oxynitride carbide layer film mixed in (1) can be formed.

  (Formation of inorganic thin film layer) Next, the inorganic thin film layer 13 will be described. As a method for forming the inorganic thin film layer 13, for example, a vacuum deposition method, a chemical vapor deposition method, a physical vapor deposition method, or a sol-gel method is used. In the present invention, it is preferable to apply a vacuum film forming method such as a vacuum deposition method, a sputtering method, a chemical vapor deposition (CVD) method, or a physical vapor deposition (PVD) method, Of these, an ion plating method and a plasma CVD method are preferable. According to the vacuum film-forming method, it is possible to make a continuous layer that is dense and has few gaps, and therefore has low moisture permeability and / or oxygen permeability and excellent flame retardancy that suppresses the generation of flammable gases. In addition, continuous production has high productivity and low cost. The inorganic thin film layer 13 in the present invention may be a single layer film composed of one layer of the inorganic thin film layer 13, or a multilayer film or a composite film composed of two or more layers, alone or in combination. Moreover, when providing the inorganic thin film layer 13 on both surfaces, after forming in one surface, what is necessary is just to form in the other surface similarly.

  For example, the vacuum evaporation method is a method of obtaining an inorganic thin film by heating and evaporating the material contained in the crucible by resistance heating, high-frequency induction heating, beam heating such as electron beam or ion beam, and so on. is there. At this time, the heating temperature and the heating method differ depending on the material, purpose, etc., and a reactive vapor deposition method that causes an oxidation reaction or the like can also be used. The sputtering method is a method in which a discharge gas (such as argon) is introduced into a vacuum chamber, a high frequency voltage or a direct current voltage is applied between the target and the base film to make the discharge gas into plasma and collide with the target. In this method, the target material is skipped and adhered to the substrate to obtain an inorganic thin film. Also, a reactive sputtering method in which a reaction gas such as oxygen is introduced to cause an oxidation reaction may be used.

  (Chemical Vapor Deposition CVD) Vacuum deposition methods such as vacuum deposition, sputtering, or PVD are well known to those skilled in the art, and are preferred inorganic thin films formed by the preferred chemical vapor deposition method and ion plating method of the present invention. The layer 13 will be further described. Examples of the inorganic thin film formed by the chemical vapor deposition method include chemical vapor deposition such as plasma chemical vapor deposition, thermal chemical vapor deposition, photochemical vapor deposition, and catalytic chemical vapor deposition (Cat-CVD). A phase growth method (Chemical Vapor Deposition method, CVD method) or the like can be applied. Specifically, on one surface of the base film 11, an evaporation gas such as an organosilicon compound is used as a raw material, an inert gas such as argon gas or helium gas is used as a carrier gas, and oxygen is supplied. As the gas, an oxygen gas or the like is used, and an inorganic oxide such as silicon oxide, aluminum oxide, titanium oxide, silicon nitride, aluminum nitride, titanium nitride, silicon oxynitride, aluminum oxynitride, or titanium oxynitride, inorganic nitride, or An inorganic oxynitride film which can form an inorganic oxynitride film and further contains carbon in the above-mentioned inorganic thin film layer by using a low temperature plasma chemical vapor deposition method utilizing a low temperature plasma generator or the like. Alternatively, an inorganic oxynitride carbide film can be formed. The inorganic thin film not containing carbon can be produced by an ion plating method. The carbon-free inorganic thin film produced by this production method can have sufficient flexibility and adhesion as well as the CVD method, and can be suitably used. As the low-temperature plasma generator, for example, a generator such as a high-frequency plasma, a pulse wave plasma, or a microwave plasma can be used. It is preferable to do.

  Moreover, the material to be used can also be used by 1 type, or 2 or more types of mixture, and can also comprise the inorganic thin film mixed by the different material. By selecting a material to be used, an inorganic thin film layer 13 such as an inorganic oxide layer, an inorganic nitride layer, an inorganic oxynitride layer, an inorganic oxycarbide layer, an inorganic oxycarbide layer, or an inorganic oxynitride carbide layer is formed. Can do.

  An example of the method of forming the inorganic thin film layer 13 by the low temperature plasma chemical vapor deposition method (referred to as plasma CVD) that can be suitably used will be described. Although FIG. 8 illustrates an example in which film formation is performed in three chambers, the number of chambers may be arbitrary depending on the inorganic thin film layer even in one or two or more chambers. The plasma CVD apparatus 200 includes a vacuum container 210, a gas supply unit, a vacuum pump, a power source, and a control device (not shown). The vacuum container 210 includes a paper feeding unit 211, a film forming unit 213, and a winding unit 215. ing. The film forming unit 213 includes a plurality of rooms such as an a chamber 221, a b chamber 223, and a c chamber 225 depending on the inorganic oxide to be formed. The base film 11 is fed out from the unwinding roll disposed in the paper feed unit 211 in the vacuum vessel 210, cooled at a predetermined speed through the guide roll, and conveyed onto the circumferential surface of the electrode drum 231. The gas supply unit supplies oxygen gas, inert gas, monomer gas such as an organosilicon compound, etc. from a gas supply device and a raw material volatilization supply device, etc., and does not adjust their single or mixed gas composition It introduces into the vacuum vessel 210.

  FIG. 8 shows an example using three kinds of gases, and the gas composition is introduced into the vacuum vessel 210 through the raw material supply nozzles 251, 253, and 255. The substrate film 11 transported on the peripheral surface of the cooling and electrode drum 221 is irradiated with plasma generated by glow discharge plasma, and an inorganic oxide such as silicon oxide, an inorganic nitride, or an inorganic oxynitride film Is formed (formed). At that time, predetermined power is applied to the cooling, electrode drum 221, a chamber electrode 251, b chamber electrode 253, and c chamber electrode 255 from a power source arranged outside the vacuum vessel 210, Further, a magnet or the like may be disposed in the vicinity of the cooling and electrode drum 221 to promote the generation of plasma. Next, the base film 11 on which the inorganic oxide, inorganic nitride, or inorganic oxynitride film is formed as described above is wound up through a guide roll, and the inorganic oxide, inorganic nitride, or inorganic oxide is formed by a plasma CVD method. A nitride film can be formed.

  The inorganic oxide, inorganic nitride, or inorganic oxynitride film is not only a single layer of inorganic oxide, inorganic nitride, or inorganic oxynitride film, but also a multilayer film in which two or more layers are stacked. But you can. Moreover, the material to be used can also be used by 1 type, or 2 or more types of mixtures, and can also comprise the inorganic thin film film mixed with the dissimilar material. By selecting a material to be used, an inorganic thin film layer 13 such as an inorganic oxide layer, an inorganic nitride layer, an inorganic oxynitride layer, an inorganic oxycarbide layer, an inorganic oxycarbide layer, or an inorganic oxynitride carbide layer is formed. Can do.

  In addition, about composition of the inorganic thin film layer 13, surface analyzers, such as a photoelectron spectrophotometer, an X-ray photoelectron spectrometer (Xray Photoelectron Spectroscopy, XPS), a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy, SIMS), are used, for example. By using elemental analysis of the silicon oxide film using a method such as ion etching in the depth direction for analysis, the above-described composition ratio and physical properties can be confirmed.

  (Film formation monitor) In the method of forming the inorganic thin film layer 13 of the gas barrier film 10 of the present invention, the atoms forming the inorganic thin film 13 are excited and released from the excited state to the continuously running base film 11. It is preferable to form the inorganic thin film 13 while monitoring the film thickness by measuring the characteristic X-ray intensity of at least one of the characteristic X-rays of the element. By measuring the characteristic X-ray intensity of at least one element among the characteristic X-rays of the elements emitted from the excited state, with the atoms forming the inorganic thin film being in an excited state on the continuously running substrate film 11 The film is formed while monitoring the film thickness of the inorganic thin film. In this way, by forming the inorganic thin film layer 13 while monitoring the film thickness, it can be formed with a stable element structure, a dense film quality, and a uniform film thickness, so there are few scratches in the thin film forming process. Synergistically, it has excellent gas barrier properties and can prevent bending.

  The thickness of the inorganic thin film layer varies depending on the metal to be used or the kind of the inorganic thin film, but is, for example, about 1 to 1000 nm, preferably about 5 to 500 nm, and more preferably 10 to 200 nm. Further, if transparency is ensured, the color may not be particularly colorless. Above this range, cracks and the like are likely to occur in the film, and below this range, the gas barrier property against water vapor, oxygen, etc. is poor, and the preservation of the content is poor.

(Water vapor transmission rate) Thus, the water vapor transmission rate measured by JIS-K-7129 of the gas barrier film 10 can be 13 g / m < ² > * day or less. In the packaging material described later, the moisture permeability may be 13 g / m ² · day or less, but in the case of a color filter and a transparent electrode, it is about 1.0 g / m ² · day or less, preferably 0.5 g / m ² · day or less. Yes, the material and / or thickness of the inorganic thin film layer may be appropriately selected.
The (oxygen permeability) The oxygen permeability, as long as the packaging material 10cc / m ² · atm · day degree or less, the color filter and the transparent electrode 1.0cc / m ² · atm · day degree or less, preferably 0. It is 5 cc / m ² · atm · day or less, and the material, thickness and / or layer configuration of the HC layer / inorganic thin film layer may be appropriately selected.

  The permeation of water vapor, oxygen, etc. is the first process of adsorption of water vapor on the surface that is in contact with gas such as water vapor, oxygen, etc., for example, the surface of a substrate film or a laminate including a substrate film, and then dissolved and diffused. Therefore, reducing the surface area of the adsorption surface by flattening the surface is effective for reducing the water vapor transmission rate. Therefore, a layer (planarization layer) having a planarization function such as a hard coat layer and preferably a scratch prevention function is formed and planarized. The planarizing layer may be the same material and coating method as the hard coat layer described above, or may be a solution obtained by dehydrating and condensing a solution obtained by hydrolyzing a metal alkoxide. The order of lamination is not particularly limited as long as the surface area of the inorganic thin film layer 13 is reduced.

However, even if the surface roughness of the base material is extremely rough, the flatness of the surface of the base film becomes insufficient due to the influence of the protrusions. And about 300 nm or less, preferably 200 nm or less, more preferably 100 nm or less. If it exceeds this range, the surface area of the substrate film having the same area will be remarkably increased, and there is a risk of defects due to protrusions, so that the water vapor transmission rate cannot be lowered sufficiently. Ra is larger than 0, but is naturally omitted. The surface roughness of the base film is the surface roughness of the surface to be formed when the hard coat layer 15 is formed, and when the treatment is performed in advance for easy adhesion to the base film, The surface roughness after the treatment is also included.
Naturally, the surface roughness of the hard coat layer 15 and / or the inorganic thin film layer 13 in the state of the gas barrier film 10 is also flat in terms of preventing defects such as a laminated transparent conductive film and improving the film quality. Therefore, the center line average roughness Ra is about 100 nm or less, preferably 10 nm or less, more preferably 5 nm or less. Rmax (maximum roughness) is also about 150 nm or less, preferably 80 nm or less. In this way, for example, even when used as a support substrate for a flat display or the like, the electrode film due to the minute projections is less likely to be defective or disconnected, and the display element is slightly remaining or contained in the outside or the element. Even when the moisture and / or organic components are low, it is difficult to be adversely affected, and it is possible to reduce the decrease in emission intensity and emission lifetime and the cause of dark spots.

  Further, when the curvature κ of the gas barrier film 10 composed of at least the base film 11 / hard coat layer 15 / inorganic thin film layer 13 is set to a range of 0 ≦ κ ≦ 5, the display substrate or By relieving the film stress of the transparent conductive film or heat seal material that is required as a packaging material and further laminated, the entire gas barrier film 10 is also prevented from being bent. In the case of a display substrate, for example, when it is heated to 180 ° C., it is greatly curved. This is because the inorganic thin film layer 13 curls with a large film stress remaining despite the extremely thin film thickness of about several hundred nm. However, once the hard coat layer 15 is provided and the inorganic thin film layer 13 is provided on the surface of the hard coat layer 15, surprisingly, the film stress is relieved and the chemical resistance is improved.

  (Other Layers) In the gas barrier film 10 of the present invention, one or a plurality of other layers may be laminated or formed on at least one surface or interlayer of the gas barrier film 10. For example, base film / HC layer / inorganic thin film layer / organic layer (primer) / organic layer (thermal adhesive layer), organic layer (second base film layer) / organic layer (adhesive layer) / base film / HC Layer / inorganic thin film layer / organic layer (primer) / organic layer (adhesive layer), organic layer (thermal adhesive layer) / organic layer (second base film layer) / organic layer (adhesive layer) / base film / HC Layer / inorganic thin film layer / organic layer (primer) / organic layer (thermal adhesive layer), organic layer (thermal adhesive layer) / organic layer (paper layer) / organic layer (adhesive layer) / substrate film / HC layer / inorganic A thin film layer / organic layer (primer) / organic layer (thermoadhesive layer) can be used as a packaging or packaging material. Also, base film / HC layer / inorganic thin film layer / inorganic thin film layer (conductive layer), inorganic layer (antifouling layer) / HC layer / base film / HC layer / inorganic thin film layer / inorganic thin film layer (conductive layer) For example, the electrode plate or the touch panel member can be used. In short, the base film 11 and the inorganic thin film layer 13 and the hard coat layer 15 are laminated in this order on at least one surface of the base film 11, and the base film 11 / the inorganic thin film layer 13 / the hard coat. As shown in FIG. 1B, the inorganic thin film layer 13 and the hard coat layer 15 are laminated in this order, and the hard coat layer 15 and the inorganic thin film layer are formed on the base film 11. It is sufficient that 13A has a set of adjacent layer structures.

  Further, as shown in FIG. 2A, an inorganic thin film layer may be further provided on the hard coat layer surface, or as shown in FIG. 2B, a hard coat layer may be provided on the inorganic thin film layer surface. , Base film 11 / inorganic thin film layer 13A / hard coat layer 15A / inorganic thin film layer 13B, or base film 11 / hard coat layer 15A / inorganic thin film layer 13A / hard coat layer 15B. In addition, an inorganic thin film layer or a hard coat layer may be further provided in the configuration, and a plurality of sets may be repeatedly laminated so that the inorganic thin film layer and the hard coat layer become one set. By repeating in this way, the gas barrier property can be remarkably improved.

  Furthermore, it is preferable to form a stress relaxation layer on at least one surface of the base film so as to cancel out the stress. That is, the stress relaxation layer 31 (an example of the inorganic thin film layer 13C) shown in FIG. 3A (an example of the inorganic thin film layer 13C) and the stress relaxation layer 31 (the inorganic thin film layer 13C / hard coat layer) shown in FIG. 15C), an (asymmetric) stress relaxation layer 31 (an example of the inorganic thin film layer 13C) shown in FIG. 3C, and at least one layer of the base film 11 is provided on at least one surface. What is necessary is just to have the stress relaxation layer 31. FIG.

(Planarization) The other layer provided on the gas barrier film 10 of the present invention is preferably a layer having a planarization function. By providing a planarizing layer on the gas barrier film 10 of the present invention, the planarization can be remarkably improved. As the degree of flattening, for example, in a transparent electrode for use in an image display device, the center line average roughness Ra on the outermost surface is about 50 nm or less, preferably 20 nm or less. Then, the center line average roughness Ra on the outermost layer surface is required to be 10 m or less, and Rmax (maximum roughness) is required to be 100 nm or less.
If the surface is uneven, the gas barrier property is poor, and the protrusions have an adverse effect on the electrode layer, for example, the electrode layer.In other words, overcurrent is generated in the protrusion due to electric field concentration, causing a short circuit and darkness. Spots are generated. If flattened, the gas barrier property is further improved, the environment resistance is excellent, the light emitting element of the display is not adversely affected, the light emitting life is reduced, the occurrence and growth of dark spots are small, and the electrode is not easily broken. It is suitable for transparent electrodes, color filters, and flexible displays that have high reliability, are easy to manufacture and are low cost, and enable high-definition multicolor display.

(Planarizing layer) The planarizing layer may be provided on the surface of the inorganic thin film layer 13 of the gas barrier film 10 constituted of the base film 11 / HC layer 15 / inorganic thin film layer 13. If an inorganic thin film layer is further provided on the flattened layer surface, gas barrier properties and prevention of disconnection of the electrode can be further obtained. Of course, the HC layer 15 also has a flattening effect. As the material of the planarizing layer, ionizing radiation or thermosetting resin used in the HC layer, part or all of the material is aminoalkyl dialkoxysilane, aminoalkyltrialkoxysilane, and a composite mainly composed of these compounds. A reaction product obtained by a chemical reaction (so-called sol-gel method) in which part or all of the body is mainly hydrolyzed, a material mainly composed of a modified polyvinyl alcohol resin, and the like can be applied.
The planarization layer can be formed by a known method such as a spin coating method, a roll coating method, or a casting method.

  (Sol-gel method) As a material for the planarization layer, a sol-gel material using a sol-gel method capable of forming a coating film of the same material type is preferable in order to obtain adhesion with the inorganic thin film layer (gas barrier layer). It is. The sol-gel method is a coating composition comprising at least a silane coupling agent having an organic functional group and a hydrolyzable group and a crosslinkable compound having an organic functional group that reacts with the organic functional group of the silane coupling agent. It is a method of coating an object and a coating film. Examples of the silane coupling agent having an organic functional group and a hydrolyzable group (hereinafter sometimes simply referred to as a silane coupling agent) include, for example, the following general formula (a) disclosed in JP-A-2001-207130. It is aminoalkyl dialkoxysilane represented by these, or aminoalkyltrialkoxysilane.

（但し、Ａ¹はアルキレン基を表す。Ｒ⁴は水素原子、低級アルキル基、または、下記一般式（ｂ）で表される。）

(Wherein, A ¹ represents an alkylene group .R ⁴ is a hydrogen atom, a lower alkyl group, or represented by the following general formula (b).)

（ただし、Ａ²は直接結合またはアルキレン基を表し、Ｒ⁸、Ｒ⁹は水素原子または低級アルキル基を表す）で表される基を表す。Ｒ⁵は水素原子または低級アルキル基を表す。Ｒ⁶は炭素数１〜４のアルキル基、アリール基または不飽和脂肪族残基を表す。分子中にＲ⁶が複数存在する場合、それらは互いに同一であっても異なっていてもよい。Ｒ⁷は水素原子、炭素数１〜４のアルキル基またはアシル基を表し、水素原子、炭素数１〜３のアルキル基またはアシル基であることが好ましい。分子中にＲ⁷が複数存在する場合、それらは互いに同一であっても異なっていてもよい。ただし、Ｒ⁴、Ｒ⁵、Ｒ⁸、Ｒ⁹のうちの少なくとも一つが水素原子である。ｗは０、１、２のいずれかであり、ｚは１〜３の整数であり、かつｗ＋ｚ＝３である。）

(Wherein A ² represents a direct bond or an alkylene group, and R ⁸ and R ⁹ represent a hydrogen atom or a lower alkyl group). R ⁵ represents a hydrogen atom or a lower alkyl group. R ⁶ represents an alkyl group having 1 to 4 carbon atoms, an aryl group, or an unsaturated aliphatic residue. When a plurality of R ⁶ are present in the molecule, they may be the same as or different from each other. R ⁷ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acyl group, and is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an acyl group. When a plurality of R ⁷ are present in the molecule, they may be the same as or different from each other. However, at least one of R ⁴ , R ⁵ , R ⁸ and R ⁹ is a hydrogen atom. w is 0, 1, or 2, z is an integer of 1 to 3, and w + z = 3. )

  Specific examples of the aminoalkyl dialkoxysilane or aminoalkyltrialkoxysilane represented by the general formula (a) include N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltriisopropoxysilane, N-β (aminoethyl) γ-aminopropyltributoxysilane, N-β (aminoethyl) γ- Aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiisopropoxysilane, N-β (aminoethyl) γ-aminopropyl Methyldibutoxysilane, N-β (aminoethyl) γ-aminopropylethyl Methoxysilane, N-β (aminoethyl) γ-aminopropylethyldiethoxysilane, N-β (aminoethyl) γ-aminopropylethyldiisopropoxysilane, N-β (aminoethyl) γ-aminopropylethyldibutoxy Silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltributoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxy Silane, γ-aminopropylmethyldiisopropoxysilane, γ-aminopropylmethyldibutoxysilane, γ-aminopropylethyldimethoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropylethyldiisopropoxysilane .gamma.-aminopropyl ethyl dibutoxy silane, .gamma.-aminopropyl triacetoxysilane, and the like, may be used alone or two or more thereof.

  The crosslinkable compound having an organic functional group that reacts with the organic functional group of the silane coupling agent (sometimes simply referred to as a crosslinkable compound) is a glycidyl group that is a functional group capable of reacting with an amino group. , Carboxyl group, isocyanate group, or oxazoline group, and specific examples thereof include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, and nonaethylene glycol diester. Glycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neope Diglycidyl ethers such as til glycol diglycidyl ether, adipic acid diglycidyl ether, o-phthalic acid diglycidyl ether, glycerol diglycidyl ether; glycerol triglycidyl ether, diglycerol triglycidyl ether, triglycidyl tris (2-hydroxyethyl) ) Triglycidyl ethers such as isocyanurate and trimethylolpropane triglycidyl ether; tetraglycidyl ethers such as pentaerythritol tetraglycidyl ether; other polyglycidyl ethers or polymers having a glycidyl group as a functional group; tartaric acid and adipic acid Dicarboxylic acids such as; carboxyl-containing polymers such as polyacrylic acid; hexamethylene diisocyanate, xylylene diisocyanate Isocyanates such as: oxazoline-containing polymers; alicyclic epoxy compounds, etc., and one or more of these can be used, but in terms of reactivity, they have two or more glycidyl groups. Are preferably used.

  The amount of the crosslinkable compound used is preferably 0.1 to 300% (mass basis, the same applies hereinafter) with respect to the silane coupling agent, and more preferably 1 to 200%. When the crosslinkable compound is less than 0.1%, the flexibility of the coating film becomes insufficient, and when it exceeds 300%, the gas barrier property may be lowered. The silane coupling agent and the crosslinkable compound are stirred while heating as necessary to obtain a coating composition. By coating and drying the coating composition using the silane coupling agent and the crosslinkable compound as raw materials on the thin film layer 4, hydrolysis and condensation of the silane coupling agent and crosslinking with the crosslinkable compound proceed. Thus, a polysiloxane coating film having a crosslinked structure is obtained.

  The above composition may further contain a silane compound having a hydrolyzable group and not having an organic functional group such as an amino group. Specifically, tetramethoxysilane, tetraethoxysilane, tetraisopropoxy Silane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, dimethyldimethoxy Silane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldiisopropoxysilane, diethyldibutoxysilane, vinyltrimethoxy Silane, vinyltriethoxysilane, γ-glycidpropyltrimethoxysilane, γ-glycidpropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, etc. 1 type, or 2 or more types of these can be used.

  When containing a silane compound having the above-mentioned hydrolyzable group and not having an organic functional group such as an amino group, co-hydrolysis of an organic functional group such as an amino group and a silane coupling agent having a hydrolyzable group Condensation and crosslinking with a crosslinkable compound proceed to obtain a polysiloxane coating film having a crosslinked structure. The coating composition further comprises a (co) hydrolysis of a silane coupling agent having an organic functional group such as an amino group and a hydrolyzing group and / or a hydrolyzing group and not having an organic functional group such as an amino group. A decomposition condensate may be contained. In addition to these, various inorganic and organic additives such as silane compounds, solvents, curing catalysts, wettability improvers, plasticizers, antifoaming agents, thickeners, etc. are added to the coating composition as necessary. can do.

  (Cardopolymer) As a material for the planarizing layer, it is preferable to contain a cardo polymer. The cardo polymer is a polymer having the following cardo structure, which is synthesized from a monomer having a cardo structure and another polymerizable monomer, and can be applied to a cardo polyester polymer, a cardo acrylic polymer, a cardo epoxy polymer, etc. Is a cardo epoxy polymer. The planarization layer should just contain the cardo polymer as a main component. Also, for the planarizing layer containing cardo polymer, if necessary, additives such as plasticizers, fillers, antistatic agents, lubricants, antiblocking agents, antioxidants, ultraviolet absorbers, light stabilizers, May be added with a modifying resin or the like.

  The cardo polymer has a unique structure called a cardo structure in the main chain skeleton of the polymer, and the cardo structure has a large number of aromatic rings. Due to its steric hindrance, the fluorene skeleton part and the main chain The direction is twisted, so the central carbon atom part can change the bond angle relatively freely, so it is strong and strong, but it is not brittle even at low temperatures, and it has high hardness and scratch resistance. It is estimated that

  Moreover, since the layer containing a cardo polymer has a good leveling property, it fills and covers a defect, and the surface after drying becomes smoother. Moreover, since it has good affinity and wettability with the inorganic compound (inorganic thin film layer 13 of the present invention), it fills, covers, and closes defects such as holes, recesses, and cracks. The leveling property and synergistic effect exert a super flattening function, and flattening, that is, Ra and Rmax on the surface can be significantly reduced. In this way, by increasing the surface smoothness, the gas permeation proceeds to adsorb gas to the surface of the material, dissolve in the material, diffuse in the material, and dissipate to the opposite surface. By reducing the adsorption site (surface area), the adsorption on the surface of the first stage can be greatly reduced, so that the gas barrier property can be remarkably improved.

  (Repetition of layer) Further, by repeating the constitution of the HC layer 15 (or planarization layer) / inorganic thin film layer 13 1 to n times, the flatness is further increased and the gas barrier property is further improved. Even if there is a local defect in the underlying film (layer), the film grows discontinuously through the HC layer, so the defect continuity is lost. Therefore, the deterioration of barrier properties and the presence of abnormal protrusions can be suppressed. Even if there is a defect, the probability that the defect overlaps at the same location can be extremely low. On the layer of the inorganic thin film layer 13, the planarization layer (HC layer 15) / inorganic thin film layer 13 is laminated in the order of 1 to 5 times in order to provide high water vapor barrier properties and oxygen barrier properties. Is desirable. Repeating more than this is not preferable from the viewpoint of reaching the limit of improvement in gas barrier properties by planarization and reducing productivity. Further, by controlling the coating conditions so as to cancel the stress, it is possible to prevent distortion and warpage.

(Symmetrical layer structure) When the resin base film 11 is used as the support material, it is preferable to have the same or similar layer structure so that the stresses on the front and back surfaces are symmetrical. As shown in FIG. 3, by forming a layer (stress relaxation function) such as an HC layer or an inorganic thin film layer on the opposite side, the stress generated when the film is formed only on one side is offset or relaxed. Further, since distortion, warpage (also referred to as bending or curling) in post-processing steps including heating can be prevented, right-angle accuracy, dimensional accuracy, and dimensional accuracy at a partial location can be improved. Further, for example, the problem of alignment required at the time of patterning is eliminated in a subsequent process such as electrode formation. Furthermore, there is no bias in flexibility and there are no problems in use.
Furthermore, at the same time, since degassing generated from the opposite surface of the base film can be prevented, a high-quality gas barrier film having a dense and uniform thickness can be stably formed. When forming the inorganic thin film layer on the opposite side, it is more preferable to consider the thickness of the layer to be formed, the inorganic material to be used, the layer structure, and the like for stress cancellation or relaxation. Another layer for relaxing stress relaxation may be formed on the opposite side. The stress relaxation layer is not particularly limited, but materials such as an inorganic thin film layer and an HC layer can be preferably used.

  (Use) The gas barrier film 10 of the present invention is a packaging material, a color filter, or a transparent electrode by laminating or forming one or more other layers on at least one surface or layer of the gas barrier film 10, It becomes possible to make an image display device using a color filter or a transparent electrode, or to develop the gas barrier film 10 for various uses. The other layers laminated here can be variously used depending on the application to be used, and are not particularly limited. However, the laminated material can effectively utilize the above-described characteristics of the gas barrier film. As below, the aspect which laminated | stacked the heat seal layer, and the aspect which laminated | stacked the electroconductive layer are demonstrated below.

FIG. 4 is a schematic sectional view showing an embodiment of the packaging application of the present invention.
FIG. 5 is a schematic cross-sectional view showing another example of the laminated material in the present embodiment.
FIG. 6 is a schematic cross-sectional view showing another example of the laminated material of this embodiment.

(First embodiment, soft packaging material) The packaging material according to the first embodiment of the present invention will be described. The packaging material in FIG. 4 includes a heat seal layer 27 formed on one surface of the base film 11 of the gas barrier film 10 via the primer layer 23, and is referred to as a soft packaging material in this specification.
(Paper Base Material Packaging Material) The packaging material in FIG. 5 includes a heat seal layer 27 formed on one surface of the base film 11 of the gas barrier film 10 via the primer layer 23, and the other surface has Two base material layers 11A are provided, and are referred to as a paper base material packaging material in this specification.
(Double-sided heat seal packaging material) The packaging material in FIG. 6 includes a heat seal layer 27 formed on one surface of the base film 11 of the gas barrier film 10 via the primer layer 23, and is necessary on the other surface. Accordingly, the adhesive layer, the second base material layer 11A, and the heat seal layer 29 are provided, and are referred to as a double-sided heat seal packaging material in this specification. In the present specification, the packaging material is referred to as a packaging material including a soft packaging material, a paper base packaging material, and a double-sided heat-sealing packaging material. However, the packaging material is not limited to this, and the gas barrier film 10 of the present invention is used. Includes what was.

(Materials for packaging materials), materials used for the soft packaging materials, paper base packaging materials, double-sided heat-sealing packaging materials, and the forming method will be described.
(Primer layer) The primer layer 23 may be a so-called layer called an anchor coat layer or a primer layer by those skilled in the art. Examples of the anchor coat layer include organic titanium systems such as alkyl titanates, isocyanate systems, polyethyleneimine systems, and polybutadiene systems. Examples of the primer layer include polyurethane systems, polyester systems, polyamide systems, epoxy systems, Solvent type, water-based type, solvent-free type mainly composed of vehicle such as poly (meth) acrylic type, polyvinyl acetate type, polyolefin type, casein, wax, ethylene- (meth) acrylic acid copolymer, polybutadiene type, Alternatively, various laminating adhesives such as a heat melting type can be applied.

The formation of the anchor coat layer and the primer layer 23 is performed by coating the material of the primer layer or the anchor coat layer by a known coating method such as a roll coat, a gravure coat, a knife coat, a dip coat, or a spray coat. It can be carried out by removing the diluent and the like by drying. The application amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state).

  (Heat seal layer) Examples of the heat seal resin used for the heat seal layer 27 include resins that can be melted by heat and fused to each other. Specifically, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene -Methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyolefin resin such as polyethylene or polypropylene, acrylic acid, methacrylic acid, maleic acid, maleic anhydride An acid-modified polyolefin resin modified with an unsaturated carboxylic acid such as acid, fumaric acid or itaconic acid, a polyvinyl acetate resin, a poly (meth) acrylic resin, a polyvinyl chloride resin or the like can be used. The heat-sealable resin layer 13 may be formed by applying the heat-sealable resin as described above, or may be formed by laminating a film or sheet made of the heat-sealable resin as described above. . The thickness of the heat-sealable resin layer 13 can be set within a range of 5 to 300 μm, preferably 10 to 100 μm.

  (Paper base material) As the second base material layer 11A, for example, when forming a packaging container, it becomes a basic material and therefore has excellent properties in mechanical, physical, chemical, etc. In particular, it is possible to use a resin film or sheet having strength and toughness and heat resistance. Specifically, stretching of strong resin such as polyester resin, polyamide resin, polyaramid resin, polyolefin resin, polycarbonate resin, polystyrene resin, polyacetal resin, fluorine resin (axial or biaxial) Or an unstretched film thru | or sheet | seat can be mentioned. The thickness of the base material layer 24 is 5 to 100 μm, preferably about 10 to 50 μm.

  Further, in the present embodiment, the second base material layer 11A is subjected to surface printing or back printing with a desired printing pattern such as characters, figures, symbols, patterns, patterns, etc. by a normal printing method. May be. Such characters and the like can be seen very well through the gas leakage prevention film 1 because the gas leakage prevention film 1 constituting the laminated material 21 has excellent transparency.

  Furthermore, in the present embodiment, for example, various paper base materials constituting the paper layer can be used as the second base material layer 11A. Specifically, it is a paper base material having formability, bending resistance, rigidity, etc., for example, a strong sized bleached or unbleached paper base material, or pure white roll paper, kraft paper, paperboard, processing A paper substrate such as paper can be used. As such a paper base material, one having a basis weight of about 80 to 600 g / m 2, preferably having a basis weight of about 100 to 450 g / m 2 is desirably used.

  The laminated material in this embodiment further includes, for example, low density polyethylene having a barrier property such as water vapor, water, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer. Films or sheets of resin such as coalescence, or films or sheets of resin such as polyvinylidene chloride, polyvinyl alcohol, saponified ethylene-vinyl acetate copolymer having barrier properties against oxygen, water vapor, etc. Other various colored resin films or sheets having light-shielding properties obtained by adding a desired additive and kneading to form a film can be used.

  These materials can be used singly or in combination of two or more, and the thickness is arbitrary, but is usually about 5 to 300 μm, preferably about 10 to 100 μm. Furthermore, when the laminated material of this embodiment is used for packaging containers, the packaging container is usually subjected to severe physical and chemical conditions, so that the packaging material is also severely compliant. Is required. Specifically, various conditions such as anti-deformation strength, drop impact strength, pinhole resistance, heat resistance, sealing performance, quality maintenance, workability, hygiene, etc. are required. For the laminated material, a material satisfying the various conditions as described above can be arbitrarily selected and used as the base material 2, the base material layers 24, 34, or other constituent members. Specifically, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer Copolymer, ethylene-acrylic acid or methacrylic acid copolymer, methylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly ( (Meth) acrylic resins, polyacrylonitrile resins, polystyrene resins, acrylonitrile-styrene copolymers (AS resins), acrylonitrile-butadiene-styrene copolymers (ABS resins), polyester resins, polyamide resins, Polycarbonate A resin, a polyvinyl alcohol resin, a saponified ethylene-vinyl acetate copolymer, a fluorine resin, a diene resin, a polyacetal resin, a polyurethane resin, a film or a sheet of a known resin such as nitrocellulose is arbitrarily selected. Can be used. In addition, for example, a film such as cellophane, a synthetic paper, or the like can be used. The film or sheet may be any of unstretched, uniaxially or biaxially stretched, or the like. Moreover, although the thickness is arbitrary, it can select and use from the range of about several micrometers to 300 micrometers, and a lamination position does not have a restriction | limiting in particular. In the present invention, the film or sheet may be a film having any property such as extrusion film formation, inflation film formation, and coating film.

  The laminated material in the present embodiment such as the above-mentioned packaging material is a method for laminating a normal packaging material, for example, a wet lamination method, a dry lamination method, a solventless dry lamination method, an extrusion lamination method, a T-die extrusion molding method. It can be produced using a coextrusion lamination method, an inflation method, a coextrusion inflation method, or the like. In addition, when performing the above-mentioned lamination, if necessary, for example, pretreatment such as corona treatment and ozone treatment can be applied to the film. For example, isocyanate (urethane), polyethyleneimine, polybutadiene It is possible to use a known adhesive such as an organic titanium-based anchor coating agent or a polyurethane-based, polyacrylic-based, polyester-based, epoxy-based, polyvinyl acetate-based, cellulose-based adhesive for laminating, etc. it can.

(Packaging Container) Next, a packaging container using the packaging material will be described.
The packaging container uses a packaging material such as the above-mentioned soft packaging material, paper base packaging material, double-sided heat-sealing packaging material, for example, bar seal, rotary roll seal, belt seal, impulse seal, frame seal, What is necessary is just to make a bag or make a box by well-known heat-sealing such as a high-frequency seal or an ultrasonic seal.

  As flexible packaging bags, side seal type, two-side seal type, three-side seal type, four-side seal type, envelope-attached seal type, joint-attached seal type (pillow seal type), pleated seal type, flat bottom seal type, square bottom seal There are molds and other heat seal type bags, and they may be self-supporting packaging bags (standing pouches) and tube containers. In addition, by producing a blank plate for manufacturing a desired paper container, and using this blank plate to form a trunk portion, a bottom portion, a head portion, etc., for example, a brick type, a flat type or a gobel top type Liquid paper containers and the like can be manufactured. Further, the shape can be any of a rectangular container, a cylindrical paper can such as a round shape, and the like.

  For example, a one-piece type, a two-piece type, other spouts, or an opening / closing zipper may be arbitrarily attached to the packaging container. The shape, configuration, and manufacturing method of the packaging container are known to those skilled in the art and will not be described. These packaging containers can be liquids, solids, mixtures, etc. Can be used for filling and packaging goods.

  (Color filter) As a color filter, a large number of fine pixels such as RBG three primary colors, black stripes, and a transparent conductive film may be provided on one surface of the base film 11 of the gas barrier film 10 if necessary. . A display device can be obtained by combining the color filter with a display panel such as a known liquid crystal display panel, plasma display (PDP), field emission display (FED), or electroluminescence display (EL).

  In the assembling process of these display devices, work efficiency is good because there are few curves, and when the layers are further laminated, the uniformity is high and the film stress is reduced. Since the display device has high moisture resistance, it has a long lifetime, a good appearance such as curl, and uniform lamination, so that it can have few defects as a display or a packaging material.

FIG. 7 is a schematic cross-sectional view showing another example of the laminated material of the present embodiment.
(Second Embodiment, Transparent Electrode) A second embodiment of the present invention is a laminated material characterized in that a conductive layer is formed on at least one surface. As shown in FIG. 7, the laminated material in this embodiment is obtained by forming a conductive layer 41 on the surface of the inorganic thin film layer 13 of the base film 11 of the gas barrier film 10. Between the base film 11, the inorganic thin film layer 13, and the conductive layer 41, there are one or more other layers such as a primer layer for improving adhesion and / or a protective layer for improving scratch resistance. Multiple layers may be formed.

  For example, an ITO film is used as the conductive layer 41 used in this embodiment, and these are formed by a sputtering method, a PVD method, or an ion plating method. In the present embodiment, an ITO film obtained by a sputtering method or an ion plating method is particularly preferable in order to obtain conductive in-plane uniformity. The film thickness of the conductive layer 41 varies greatly depending on the composition, application, etc., but is usually formed in the range of 50 nm to 200 nm. The conductive layer 41 preferably has characteristics such as a resistance value of 0 to 50Ω / □ and a total light transmittance of 85% or more. Such a conductive layer 41 can be used as a transparent electrode for driving a liquid crystal, a touch panel, etc., for example, in a liquid crystal display device.

  (Image Display Device) An image display medium is obtained by using the laminate material shown in the second embodiment as a base material and having an image display layer formed on the conductive layer. As such an image display device, a non-luminous display such as a liquid crystal display device which performs display with gradation by shuttering the brightness of a backlight, a plasma display (PDP), a field emission display (FED). ), And a self-luminous display that performs display by causing a phosphor to emit light with some energy, such as an electroluminescence display (EL). When the image display medium is a liquid crystal display device, the image display layer indicates a liquid crystal layer, and when the image display medium is a self-luminous display as described above, a phosphor having a phosphor The layer corresponds to the image display layer. In addition, this invention is not limited to the said embodiment.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, it is not limited to this.

(Example 1) As a base film 11, a PET film having a thickness of 100 μm (trade name ester E5000, Ra = 75 nm, manufactured by Toyobo Co., Ltd.) was used, and the following UV curable resin composition was applied and UV cured. After forming the hard coat layer (HC layer), an aluminum oxide film having a thickness of 100 nm was formed by a vacuum vapor deposition method to obtain a gas barrier film having a layer configuration of PET / HC layer / aluminum oxide film. The hard coat layer had a pencil hardness of 2H.
・ <UV curable resin composition>
・ Paracumylphenoxyethylene glycol acrylate: Shin Nakamura Chemical Co., Ltd. 50 parts ・ Photopolymerization initiator (Irgacure 184; Ciba Geigy Co., Ltd.) 5 parts ・ Solvent (Toluene) 50 parts

  (Example 2) A gas barrier film was obtained in the same manner as in Example 1 except that the film thickness was 3 nm.

  (Example 3) A gas barrier film was obtained in the same manner as in Example 1 except that the film thickness was 520 nm.

(Example 4) Using a PET film having a thickness of 100 μm (trade name ester A4100, Ra = 5.0 nm, manufactured by Toyobo Co., Ltd.) as a base film, the following UV curable resin composition was applied and UV cured. After forming a hard coat layer (HC layer), a silicon oxide (SiOx, x = 1.6) film having a thickness of 100 nm is formed by an ion plating method, and a layer structure of PET / HC layer / silicon oxide film is formed. A gas barrier film consisting of
・ <UV curable resin composition>
Pentaerythritol triacrylate: 50 parts manufactured by Nippon Kayaku Co., Ltd. Photopolymerization initiator (Irgacure 184; manufactured by Ciba Geigy) 2 parts Solvent (toluene) 50 parts

(Example 5) As a base film, a PET film having a thickness of 100 μm (trade name ester A4100, Ra = 5.0 nm, manufactured by Toyobo Co., Ltd.) was first subjected to oxygen plasma under conditions of an applied voltage of 3 kW and an oxygen flow rate of 3 slm. Processed. Ra of the base film after a process was 151 nm. The following UV curable resin composition is applied to the treated surface and UV cured to form a hard coat layer, and then a 100 nm thick silicon oxide (SiOx, x = 2.0) film is formed by an ion plating method. Formed to obtain a gas barrier film.
・ <UV curable resin composition>
Pentaerythritol triacrylate: 50 parts manufactured by Nippon Kayaku Co., Ltd. Photopolymerization initiator (Irgacure 184; manufactured by Ciba Geigy) 2 parts Solvent (toluene) 50 parts

  (Example 6) A gas barrier film was obtained in the same manner as in Example 4 except that the film forming method was the sputtering method.

  (Embodiment 7) A PET / HC layer / silicon oxynitride film was formed in the same manner as in Embodiment 4 except that a silicon oxynitride film having a thickness of 100 nm was formed by sputtering instead of the silicon oxide film. A gas barrier film was obtained.

  (Example 8) A gas barrier film was obtained in the same manner as in Example 7 except that the film forming method was the ion plating method.

  (Example 9) A gas barrier film having a layer structure of PET / HC layer / silicon oxide carbide film in the same manner as in Example 4 except that a silicon oxide carbide film having a thickness of 100 nm is formed instead of the silicon oxide film. Got.

  (Example 10) A gas barrier film was obtained in the same manner as in Example 9 except that the film forming method was the plasma CVD method.

  (Example 11) As a base film, a PC film having a thickness of 100 μm (trade name AD-5503, manufactured by Teijin Ltd., Ra = 3.4 nm) was coated with UV curable acrylate, UV cured, and hardened. After forming the coat layer, a silicon oxide (SiOx, x = 2.0) film having a thickness of 100 nm was formed by sputtering to obtain a gas barrier film having a layer configuration of PC / HC layer / silicon oxide film.

  Example 12 A gas barrier film was obtained in the same manner as in Example 11 except that the silicon oxide (SiOx, x = 2.0) film was formed by an ion plating method.

  Example 13 A gas barrier film was obtained in the same manner as in Example 11 except that the silicon oxide (SiOx, x = 1.6) film was formed by ion plating.

  (Example 14) Except that the hard coat layer and the silicon oxide (SiOx, x = 2.0) film are formed on both surfaces of the base film, the silicon oxide film / HC layer / PC / A gas barrier film having a layer structure of HC layer / silicon oxide film was obtained.

  (Example 15) Silicon oxide film / HC layer / PC / A gas barrier film having a layer configuration of HC layer / silicon oxide film was obtained.

  (Example 16) Silicon oxide film / HC layer / PC / A gas barrier film having a layer structure of HC layer / silicon oxide film was obtained.

  (Example 17) A UV curable acrylate is further applied to the silicon oxide film surface of the gas barrier film of Example 11 and UV cured to form a planarization layer, and a PC / HC layer / silicon oxide film / planarization layer is formed. A gas barrier film having a layer structure (a cured resin layer and also having an HC layer function) was obtained.

  (Example 18) A UV curable acrylate is further applied to the silicon oxide film surface of the gas barrier film of Example 12 and UV cured to form a planarizing layer, and PC / HC layer / silicon oxide film / planarizing layer is formed. A gas barrier film consisting of the following layer structure was obtained.

  (Example 19) A UV curable acrylate is further applied to the silicon oxide film surface of the gas barrier film of Example 13 and UV cured to form a planarizing layer, and a PC / HC layer / silicon oxide film / planarizing layer is formed. A gas barrier film consisting of the following layer structure was obtained.

  (Example 20) A silicon oxide film having a thickness of 100 nm was further formed on the silicon oxide film surface of the gas barrier film of Example 11 by sputtering, and the layer structure of PC / HC layer / silicon oxide film / silicon oxide film was used. A gas barrier film was obtained.

  (Example 21) A UV-curable acrylate was further applied to the exposed base film surface of the gas barrier film of Example 12 and UV-cured to form a hard coat layer. , X = 2.0) A film was formed by sputtering. The silicon oxide film is further coated with UV curable acrylate and UV cured to form a planarization layer, and the silicon oxide film / HC layer / PC / HC layer / silicon oxide film / planarization layer structure is formed. A gas barrier film was obtained.

  (Example 22) A silicon oxide film having a film thickness of 100 nm was further formed on the silicon oxide film surface of the gas barrier film of Example 13 by sputtering, and the layer structure of PC / HC layer / silicon oxide film / silicon oxide film was used. A gas barrier film was obtained.

  (Example 23) A gas barrier film having a layer structure of PC / HC layer / silicon oxynitride film was obtained in the same manner as in Example 11 except that the silicon oxide film was changed to a silicon oxynitride film.

  (Example 24) A gas barrier film having a layer structure of PC / HC layer / silicon oxynitride film was obtained in the same manner as in Example 12 except that the silicon oxide film was changed to a silicon oxynitride film.

  (Example 25) PC / HC layer / silicon oxynitride film in the same manner as in Example 13 except that the silicon oxide film is a silicon oxynitride (SiOxNy, x = 1.0, y = 0.4) film A gas barrier film consisting of the following layer structure was obtained.

  (Example 26) A gas barrier film comprising a layer structure of silicon oxynitride film / HC layer / PC / HC layer / silicon oxynitride film in the same manner as in Example 14 except that the silicon oxide film is a silicon oxynitride film Got.

  (Example 27) A gas barrier film having a layer structure of silicon oxynitride film / HC layer / PC / HC layer / silicon oxynitride film in the same manner as in Example 15 except that the silicon oxide film is a silicon oxynitride film Got.

  (Embodiment 28) A silicon oxynitride film / HC layer / PC in the same manner as in Embodiment 16 except that the silicon oxide film is a silicon oxynitride (SiOxNy, x = 1.0, y = 0.4) film. A gas barrier film having a layer structure of / HC layer / silicon oxynitride film was obtained.

  Example 29 A gas barrier film having a layer configuration of PC / HC layer / silicon oxynitride film / cured resin layer was obtained in the same manner as in Example 17 except that the silicon oxide film was changed to a silicon oxynitride film.

  (Example 30) A gas barrier film having a layer structure of PC / cured resin layer / silicon oxynitride film / flattening layer was obtained in the same manner as in Example 18 except that the silicon oxide film was changed to a silicon oxynitride film. .

  Example 31 PC / HC layer / silicon oxynitride film in the same manner as in Example 19 except that the silicon oxide film is a silicon oxynitride (SiOxNy, x = 1.0, y = 0.4) film / A gas barrier film having a layer structure of a planarizing layer was obtained.

  (Example 32) A gas barrier film having a layer structure of PC / HC layer / silicon oxynitride film / silicon oxynitride film was obtained in the same manner as in Example 20 except that the silicon oxide film was changed to a silicon oxynitride film. .

  (Example 33) Layer structure of silicon oxynitride film / HC layer / PC / HC layer / silicon oxynitride film / flattening layer in the same manner as in Example 21 except that the silicon oxide film is a silicon oxynitride film A gas barrier film consisting of

  (Example 34) A PC / HC layer / a silicon oxide film / in the same manner as in Example 22 except that the silicon oxide film is a silicon oxynitride (SiOxNy, x = 1.0, y = 0.4) film. A gas barrier film having a layer structure of a silicon oxynitride film was obtained.

  (Example 35) As a base film, polyethylene naphthalate with a thickness of 100 μm (trade name: Teonex Q65A, Ra = 1.5 nm, manufactured by Teijin Ltd.) was applied, UV curable acrylate was applied, UV cured, and hardened. After forming the coat layer, a silicon oxynitride film having a thickness of 100 nm was formed by sputtering to obtain a gas barrier film having a layer structure of PEN / HC layer / silicon oxynitride film.

  (Example 36) A UV curable acrylate is further applied to the silicon oxynitride film surface of the gas barrier film of Example 35 and UV cured to form a planarization layer, and then a PEN / HC layer / silicon oxynitride film / flat A gas barrier film having a layer structure of the chemical layer was obtained.

  (Example 37) A silicon oxynitride film having a thickness of 100 nm was further formed on the planarization layer surface of the gas barrier film of Example 36 by sputtering, and PEN / HC layer / silicon oxynitride film / flattening layer / oxynitriding A gas barrier film composed of a silicon film was obtained.

  (Comparative Example 1) As a base film, an undeposited ester E5000 (Toyobo Co., Ltd., PET film product name, Ra = 75 nm) having no inorganic thin film layer was used as a gas barrier film of Comparative Example 1.

  (Comparative Example 2) Using a 100 μm-thick PET film (trade name ester E5000, Ra = 75 nm, manufactured by Toyobo Co., Ltd.) as a substrate film, a silicon oxide film having a thickness of 100 nm was directly sputtered without providing a hard coat layer. A gas barrier film was obtained by the method.

  (Comparative Example 3) A gas barrier film was obtained in the same manner as in Comparative Example 2, except that a PC film having a thickness of 100 µm (trade name AD-5503, Ra = 3.4 nm) was used as the base film. It was.

  (Comparative Example 4) A gas barrier film was obtained in the same manner as in Comparative Example 2 except that a PEN film having a thickness of 100 µm (trade name: Teonex Q65A, Ra = 1.5 nm) was used as the base film. .

  (Evaluation method) Evaluation was performed by bending, oxygen permeability, moisture permeability, haze, and total light transmittance.

(Measurement method) Oxygen permeability was measured according to JIS-K7126, moisture permeability was measured according to JIS-K7129, haze was measured according to JIS-K7125, and total light transmittance was measured according to JIS-K7125.
The bending was performed in accordance with JIS-C5565, and in detail, by method B in 5.4. The film thickness of the inorganic thin film layer was measured by a fluorescent X-ray method.
Surface roughness Ra is based on JIS-B-0601, using a desktop small probe microscope (Seiko Instruments Inc., trade name Nanopics 1000) capable of measuring in nm, in contact mode, and the reference length during measurement is It is measured as 100 μm. In addition, Ra in a table | surface is a numerical value of the outermost surface as a gas barrier film of an Example and a comparative example. The measurement results are shown in “Tables 1 to 7”.

(Evaluation results) As for the optical characteristics of haze and total light transmittance, all of Examples 1 to 37 and Comparative Examples 1 and 2 passed and were suitable for use.
The curvature κ was 5 or less in Examples 1 to 37, and the curvature was small, so that the efficiency in the assembly process could be improved. However, in Comparative Example 1, the curvature κ was 0.5 and the curvature was good, but the moisture permeability was large and the moisture resistance was low. In Comparative Examples 2 to 4, the moisture resistance was good, but the curvature κ was as large as 5.0 or more, and the efficiency of the assembly process was lowered.

It is sectional drawing of the gas barrier film which shows one Example of this invention. It is sectional drawing of the gas barrier film which shows one Example of this invention. It is sectional drawing of the gas barrier film which shows one Example of this invention. It is a schematic sectional drawing which shows the aspect of the packaging use of this invention. It is a schematic sectional drawing which shows the other example of the laminated material in this embodiment. It is a schematic sectional drawing which shows the other example in the laminated material of this embodiment. It is a schematic sectional drawing which shows the other example in the laminated material of this embodiment. It is explanatory drawing of the CVD apparatus which can be used conveniently by this invention.

Explanation of symbols

10: Gas barrier film 11: Base film 11A: Second base material layer 13, 13A, 13B: Inorganic thin film layer 15, 15A, 15B: Hard coat layer 23: Primer layer 24: Adhesive layer 27, 27A: Heat seal layer 31 : Stress relaxation layer 200: CVD apparatus 210: Vacuum vessel 211: Paper feed unit 213: Film forming unit 215: Winding unit 221: a chamber 223: b chamber 225: c chamber 231: electrode drums 241, 243 and 245: electrodes 251, 253, 255: Gas supply nozzle

Claims (7)

In a gas barrier film in which at least a hard coat layer and an inorganic thin film layer are provided on a base film directly or through another layer, the surface roughness center line measured by JIS-B-0601 of the base film The average roughness (Ra) is 300 nm or less, the total light transmittance measured by JIS-K7105 is 80% or more, the hard coat layer is made of an ionizing radiation resin , and the pencil hardness measured by JIS-K-5400 Is over H,
The gas barrier film has a moisture permeability measured by JIS-K-7129 of 13 g / m ² · day or less, and a curvature κ satisfies the following formula (a):
Have a planarizing layer containing the cardo polymer on the inorganic thin film layer,
The ionizing radiation resin is mainly (meth) acrylate and melamine acrylate,
The gas barrier film , wherein the melamine acrylate has one or more methylol groups .
0 ≦ κ ≦ 5 (κ = 1 / R) (a)
(In the above formula, κ is the curvature, R is the radius of curvature, and the unit is m) The inorganic thin film layer is a metal, an inorganic oxide layer, an inorganic nitride layer or an inorganic oxynitride layer, an inorganic oxide carbide layer containing carbon, an inorganic nitride carbide layer, an inorganic oxynitride carbide, and the inorganic thin film The gas barrier film according to claim 1, wherein the layer has a thickness of 5 to 500 nm. The gas barrier film according to claim 1, further comprising a stress relaxation layer formed on at least one surface of the base film. The gas barrier film according to claim 3 , wherein the stress relaxation layer is formed on a surface of the base film opposite to the surface on which the hard coat layer and the inorganic thin film layer are formed. A gas barrier film comprising an inorganic thin film layer and / or an organic layer provided on at least one surface of the gas barrier film according to claim 1 . A packaging material, a color filter, or a transparent electrode comprising the gas barrier film according to any one of claims 1 to 5 . A liquid crystal display device or an organic EL display device comprising the gas barrier film according to claim 1 .

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