JP4414748B2 - Gas barrier film, laminate material using the same, and image display medium - Google Patents

Description

  The present invention relates to a packaging material such as food and medical products, a packaging material such as an electronic device, a gas barrier film having a very high barrier property used as a substrate material, a laminated material using the gas barrier film, and an image display medium.

  The gas barrier film is mainly used as a packaging material for foods and pharmaceuticals to prevent the influence of oxygen and water vapor, which cause the quality of the contents to change, and is used for liquid crystal display panels and EL (electroluminescence) display panels. In order to avoid deterioration of performance due to contact with oxygen or water vapor, elements formed in the above are used as packaging materials for electronic devices and the like. In recent years, a gas barrier film is sometimes used for the purpose of providing flexibility and impact resistance to a portion where glass has been conventionally used.

The gas barrier film as described above generally has a configuration in which a plastic film is used as a base material and a gas barrier layer is provided on one side or both sides thereof. Such a gas barrier film is formed by forming a silicon oxide film (silica film) or an aluminum oxide film (alumina film) by using a dry film forming method such as a CVD method, a PVD method, a sputtering method, or a plasma CVD method. It is manufactured (Patent Documents 1 to 3). In particular, the plasma CVD method has an advantage that a silicon oxide film or an aluminum oxide film having excellent gas barrier properties and flexibility can be formed without causing thermal damage to the plastic film substrate.
JP-A-8-176326 Japanese Patent Laid-Open No. 11-309815 JP 2000-6301 A

However, even if any method is used, the conventional gas barrier film has an oxygen transmission rate (OTR) of about 1.0 cc / m ² / day · atm, or about 1.0 g / m ² / day. However, when it is used as a packaging material for an electronic device or the like that requires a higher gas barrier property, the gas barrier property is still insufficient.
Recently, a flexible display panel in which a liquid crystal display panel or an organic EL display panel is formed on a flexible base material such as a plastic film has been developed. The surface of the flexible base material used is very smooth. Is strictly demanded. When the surface smoothness cannot be obtained, for example, there is a problem in that short-circuiting of the electrodes occurs and causes black spots (dark spots). In addition, in order to realize such a flexible display panel, a higher gas barrier property is required than a packaging gas barrier film, and the performance of liquid crystal display materials, organic EL display materials and elements deteriorates when exposed to oxygen or water vapor. In order to prevent this, a gas barrier property equivalent to that of a glass substrate (for example, an oxygen permeability of 0.1 cc / m ² / day · atm or less and a water vapor permeability of 0.1 g / m ² / day or less) is a flexible substrate. Required for the material.

In addition, the flexible base material used for the flexible display panel is required to be capable of electrode patterning of the conductive layer, but the flexible base material made of the conventional gas barrier film has a gas barrier property due to the etching process of electrode patterning. There was also the problem of a drop.
The present invention has been made in view of such circumstances, and has a gas barrier film having high gas barrier properties, high surface smoothness, and capable of electrode patterning of a conductive layer, and the gas barrier film. An object is to provide a laminated material and an image display medium.

In order to achieve such an object, the gas barrier film of the present invention includes a base film, a barrier vapor deposition layer having a smooth surface provided on at least one surface of the base film, and the barrier vapor deposition layer. And an acid-resistant protective layer having a smooth surface laminated on the substrate, having an oxygen transmission rate of 0.1 cc / m ² / day · atm or less and a water vapor transmission rate of 0.1 g / m ² / day or less. The barrier vapor deposition layer is made of indium zinc oxide, and the atomic ratio of indium (In) to zinc (Zn) in the indium zinc oxide is in the range of In / (In + Zn) of 0.5 to 0.8. The acid resistance of the protective layer is such that the etching rate with an indium tin oxide etchant having a volume mixing ratio of hydrochloric acid: nitric acid: water of 1: 0.08: 1 is 0.01 μm / min or less. Ruyo It was Do configuration.
As another aspect of the present invention, the laminate of the barrier vapor deposited layer and the protective layer is repeatedly formed twice or more.
As another aspect of the present invention, the smooth surface of the barrier vapor-deposited layer is configured such that the surface roughness Ra is 6 nm or less and the maximum height difference PV is 60 nm or less.

As another aspect of the present invention, the smooth surface of the protective layer is configured such that the surface roughness Ra is 6 nm or less and the maximum height difference PV is 60 nm or less.
As another embodiment of the present invention, the barrier vapor-deposited layer is doped with one or more of tin, aluminum, antimony, gallium and germanium in a range of 20 atomic% or less with respect to the total amount of indium and zinc. The configuration was
As another aspect of the present invention, the protective layer is a layer formed by a vapor deposition method and has a thickness in the range of 50 nm to 1 μm, and the protective layer includes a silicon oxide film, a silicon nitride film, and a carbonized film. Silicon film, silicon oxycarbide film, silicon oxynitride film, silicon oxynitride carbide film, hydrocarbon film, fluorocarbon film, polyimide film, polyamide film, acrylate film, methacrylate film, urethane acrylate film, epoxy film, epoxy acrylate film The layer is composed of one or more films selected from acrylic films and olefin films.

  As another aspect of the present invention, the protective layer is a layer formed by a wet film forming method, and the thickness is in the range of 50 nm to 10 μm. The protective layer is an acrylate resin, an acrylic resin, or a urethane. It was set as the structure which is a layer which consists of 1 or more types of resin selected from resin, urethane acrylate resin, an epoxy resin, an epoxy acrylate resin, an olefin resin, a cardo resin, and a methacryl resin.

The laminate of the present invention was configured such that a heat-sealable resin layer was provided on at least one surface of any of the gas barrier films described above.
The laminate of the present invention was configured such that a conductive layer was provided on at least one surface of any of the gas barrier films described above.
The image display medium of the present invention is configured to use the above-mentioned laminated material as a base material and to have an image display layer on the conductive layer.

According to the present invention, at least one surface of a base film is provided with a barrier vapor deposition layer having a smooth surface and an acid-resistant protective layer having a smooth surface laminated on the barrier vapor deposition layer. Since the surfaces of the barrier vapor-deposited layer and the protective layer are smooth, the adsorption property of oxygen and moisture is low, which gives a high gas barrier property to the entire gas barrier film, and also on the surface of the gas barrier film. Since a protective layer with acid resistance is located, even if etching processing such as electrode patterning is performed on this protective layer, the barrier vapor-deposited layer is not etched, thereby maintaining conductivity while maintaining a high gas barrier property. Layer electrode patterning is possible. Such a gas barrier film of the present invention can be used for applications requiring high gas barrier properties, and the laminated material of the present invention is excellent as a packaging material for foods, pharmaceuticals, etc., and a packaging material for electronic devices, for example. The image display medium of the present invention exhibits gas barrier properties, and has an effect of enabling a display in which short-circuiting of electrodes and performance deterioration of elements and the like are prevented.
The protective layer serves to protect the barrier vapor deposition layer from an acidic liquid such as an etching liquid.

Next, embodiments of the present invention will be described with reference to the drawings.
Gas Barrier Film FIG. 1 is a schematic sectional view showing an embodiment of the gas barrier film of the present invention. In FIG. 1, a gas barrier film 1 is provided on one surface of a base film 2 by laminating a barrier vapor deposition layer 3 having a smooth surface and a protective layer 4 having a smooth surface in this order. In addition, the gas barrier film 1 of this invention may be provided with the barriering vapor deposition layer 3 and the protective layer 4 laminated on both surfaces of the base film 2.

  FIG. 2 is a schematic cross-sectional view showing another embodiment of the gas barrier film of the present invention. In FIG. 2, a gas barrier film 1 ′ is formed by laminating a barrier vapor-deposited layer 3 having a smooth surface and a protective layer 4 having a smooth surface on one surface of the base film 2 repeatedly in this order twice or more (see FIG. 2). In the example shown, it is provided four times). Note that the gas barrier film 1 ′ may also be provided by repeatedly laminating the barrier vapor deposition layer 3 and the protective layer 4 on both surfaces of the base film 2. Thus, gas barrier property can be improved further by laminating | stacking the barrier property vapor deposition layer 3 and the protective layer 4 in multiple numbers. The number of repetitions of the lamination of the barrier vapor-deposited layer 3 and the protective layer 4 can be set in consideration of the obtained gas barrier property, production efficiency, and the like. For example, the range is 2 to 20 times, preferably 2 to 10 times. Can be set.

Next, each component of the above-described gas barrier film of the present invention will be described.
(Barrier vapor deposition layer)
The barrier vapor deposition layer which comprises the gas barrier film of this invention will not be specifically limited if the surface is a vapor deposition film with the smoothness. The smooth surface of the barrier vapor-deposition layer has a surface average roughness Ra of 6 nm or less, preferably 3 nm or less, and a maximum height difference PV of 60 nm or less, preferably 30 nm or less. In the present invention, an atomic force microscope (Nanopics 1000; manufactured by Seiko Instruments Inc.) is used to measure the clean surface in a non-contact mode, and the surface average roughness Ra (scan area = 4 μm square) and the maximum height difference PV (Scan area = 100 μm square) is measured. Such a smooth barrier vapor-deposited layer has a low oxygen and moisture adsorptivity and an excellent gas barrier property. Further, the protective layer on the barrier vapor deposition layer also has a smooth surface.

The barrier vapor deposition layer as described above is preferably a film containing oxygen and at least one element selected from aluminum, zinc, indium, silicon and tin. These elements can form the film formation surface smoothly in the process of forming a vapor deposition film, and at the same time, the oxygen element imparts transparency to the film, and uses for which transparency is required, for example, transparent packaging The range of use of the gas barrier film of the present invention can be expanded in materials and image display media.
Among the barrier vapor-deposited layers described above, the barrier vapor-deposited layer containing indium, zinc and oxygen as constituent elements is particularly preferable because of its high gas barrier property and transparency, and a smooth surface. The atomic ratio of indium (In) and zinc (Zn) in such a barrier vapor deposition layer is such that In / (In + Zn) is in the range of 0.3 to 0.9, preferably 0.5 to 0.8. It is. When the atomic ratio is within the above range, the formed deposited film becomes a hexagonal layered compound, and the film stability and transparency are increased. In the present invention, the above atomic ratio is measured by a photoelectron spectroscopy (ESCA) method.

  Further, in the barrier vapor-deposition layer containing indium, zinc and oxygen as constituent elements, one or more of tin, aluminum, antimony, gallium and germanium is in a range of 20 atomic% or less with respect to the total amount of indium and zinc. You may dope with. Such a barrier vapor-deposition layer is preferable because atoms doped in defects in the vapor-deposited film are incorporated, and a more stable film is obtained without distorting the film structure, and strength, hardness, and light transmittance are improved. . If the doping range exceeds 20 atomic%, the formed deposited film does not become a hexagonal layered compound and becomes a film having an unstable structure, which is not preferable because the film stability and transparency are lowered.

Such a barrier vapor deposition layer can be formed using a dry film forming method such as a CVD method, a PVD method, a sputtering method, or a plasma CVD method. The thickness of the barrier vapor deposition layer (in the example shown in FIG. 2, the thickness per layer) can be appropriately set in the range of 5 to 300 nm, preferably 30 to 180 nm. When the thickness of the barrier vapor-deposition layer is less than 5 nm, high gas barrier properties (oxygen permeability is 0.1 cc / m ² / day · atm or less and water vapor permeability is about 0.1 g / m ² / day or less. Cannot be expressed). In addition, when the thickness of the barrier vapor deposition layer exceeds 300 nm, a large stress is applied, and when the base film is flexible, the barrier vapor deposition layer is liable to crack and the gas barrier property is lowered, and the time required for film formation is long. It is not preferable. Further, the thickness of the barrier vapor deposition layer can be selected to be optimal so as to cause optical interference and suppress optical reflection.

  The gas barrier film of the present invention can be arbitrarily laminated with a layer having poor transparency as a base film, a protective layer, or other laminated material according to various uses, and is required as a final product. The degree of transparency and the degree thereof vary depending on the application. For example, when the gas barrier film of the present invention is used as a packaging material, it may be light-shielded by printing with colored ink or the like in order to protect the contents from light rays. Further, a layer in which an additive such as an antistatic agent or a filler, which causes a decrease in the transparency of the entire gas barrier film, is laminated, or a metal foil having no transparency may be laminated. However, when used for applications such as a gas barrier film for a film liquid crystal display panel, a gas barrier film for a film organic EL display panel, or a gas barrier film for a film solar cell, transparency of the entire gas barrier film is required. Therefore, the effect of the transparency of the barrier vapor deposition layer containing indium, zinc and oxygen as constituent elements is significant.

(Protective layer)
The protective layer constituting the gas barrier film of the present invention is not particularly limited as long as it is formed on the barrier vapor-deposited layer and has a smooth surface and acid resistance. As described above, the protective layer is laminated on the barrier vapor-deposited layer having a smooth surface, thereby increasing the smooth interface and increasing the thickness, thereby improving the gas barrier property. The protective layer simultaneously acts as an acid protective film for the barrier vapor deposition layer, and after forming a transparent electrode such as an indium tin oxide film (ITO film) on the gas barrier film, an etching process using an acid is performed. Even when the patterning is performed, the barrier vapor-deposited layer is prevented from being etched, and the gas barrier property of the entire gas barrier film is not deteriorated, and a good gas barrier property can be maintained.

The smooth surface of the protective layer has a surface average roughness Ra of 6 nm or less, preferably 3 nm or less, and a maximum height difference PV of 60 nm or less, preferably 30 nm or less. Thus, the protective layer having a smooth surface can prevent deterioration of gas barrier properties due to adsorption of oxygen, moisture, etc. on the surface, and a transparent electrode such as an ITO film formed on the protective layer. Also have a smooth surface.
The acid resistance of the protective layer is such that the etching rate in the thickness direction with an indium tin oxide etching solution (liquid temperature 23 ° C.) having a volume mixing ratio of hydrochloric acid: nitric acid: water of 1: 0.08: 1 is 0.01 μm / It is desirable that it is not more than minutes, preferably not more than 0.005 μm / minute.

  Such a protective layer is not particularly limited as long as it has a smooth surface as described above and has acid resistance. For example, it may be a layer formed by a vapor deposition method, or may be a wet film-forming method, that is, a layer formed by applying a coating liquid for forming a protective layer. In addition, when the material used in the coating liquid is a thermosetting resin, an ultraviolet curable resin, or an electron beam curable resin, it is irradiated with electromagnetic waves such as heat, ultraviolet rays, electron beams, and plasma after coating. Thus, the protective layer can be formed by applying energy to the coating and curing it. Further, a protective layer may be formed by using a thermoplastic resin and melting and applying the resin. Further, the protective layer may be formed by bonding a protective film formed in a film shape.

  Considering that the above-mentioned barrier vapor-deposited layer is formed by the vapor deposition method, the barrier vapor-deposited layer and the protective layer can be formed continuously in the same vacuum film forming apparatus. It is preferable to form a layer. As the formation method when the protective layer is formed by the vapor deposition method, the following plasma polymerization method, plasma CVD method, vapor deposition method, and sputtering method can be cited because a smooth surface film can be formed and the film formation speed is high. Can do.

(1) Plasma polymerization method At least one or more organic metal compounds are used. In some cases, one or more inert gases for stable film formation are added simultaneously, and these are plasma-discharged under reduced pressure. The film is formed by introducing it into the film. Examples of organometallic compounds include hexamethyldisiloxane (HMDSO), tetramethyldisiloxane (TMDSO), tetramethylsilane (TMS), trimethoxysilane, hexamethyldisilane, tetramethoxysilane, (TMOS), methyltrimethoxysilane, Any compound such as dimethyldimethoxysilane, tetraethoxysilane (TEOS), hexamethyldisilazane, trimethylaluminum (TMA), and tetraisopropylalkoxide (TTIP) can be used. Among these materials, organosilicon compounds can be preferably used because they are easy to handle and inexpensive. Since the material for the protective layer is usually a liquid at atmospheric pressure and room temperature, it is heated in advance and introduced into the film forming section as a vaporized gas. As the inert gas species, argon, helium, nitrogen, or the like can be used.

  As a power source for film formation, a power source of any frequency such as VHF, microwave (2.54 GHz), RF (13.56 MHz) high frequency power source, low frequency power source (10 Hz to 500 kHz) can be used. is there. In addition, the discharge electrode may have any shape such as a parallel plate, ICP, a holocathode gun, and surface wave plasma. Further, in order to efficiently form a film on the substrate, a plasma can be confined by installing a magnet in the vicinity of the substrate.

  The film thus formed depends on the type of organometallic compound used, but a polymerization reaction is caused by plasma to form a polymerized film. Therefore, the film to be formed is usually composed of element species contained in the raw material. For example, when hexamethyldisiloxane is used as a raw material, a polymer film made of Si, O, C, and H is formed. When hexamethyldisilazane is used, it is made of Si, N, C, and H. When a film is formed and there is a large amount of residual moisture in the film formation chamber, O is taken into the film in addition to Si, N, C, and H. For these films, for example, the degree of polymerization can be increased by optimally selecting film formation conditions such as film formation pressure, and a film having a protective film function can be formed.

(2) Plasma CVD method The plasma CVD method uses the same apparatus as the plasma polymerization method, and forms a film by adding a reactive gas in addition to the above-mentioned organometallic compound. It is also possible to add an inert gas. As the reactive gas, an oxygen-containing gas such as O ₂ , CO ₂ , or N ₂ O, a nitrogen-containing gas such as NH ₃ , a halogen-containing gas such as Cl or F, or the like can be used.
The film formed in this manner depends on the organometallic compound species and the reactive gas used, but as with the plasma polymerization method, a film composed of the element species contained in the raw materials and the reactive gas can be formed. It is also possible to remove some elements by increasing the reactivity. For example, when tetramethoxysilane is used as the organosilicon compound gas and oxygen is used as the reactive gas, it is possible to efficiently remove carbon and form a SiO ₂ film containing only Si and O. As described above, the film formed by the plasma CVD method is generally a dense film with fewer defects in the film than the plasma polymerized film. For this reason, it acts as an effective protective film against acid, alkali, moisture and the like.

(3) Vapor deposition method As the vapor deposition method, a resistance heating method, an induction heating method, an electron beam vapor deposition method, a vapor deposition polymerization method, a flash vapor deposition method, or the like, and an ion plating method using a holocathode electrode can be used. The film can be formed using any material. In the case of a transparent film, an inorganic oxide film, an inorganic oxynitride film, an inorganic nitride film (inorganic: silicon, aluminum, titanium, niobium, tin, etc.), Examples of the organic film include a carbonized film such as polyethylene, a carbonized oxide film, a carbonitride / nitride film, a carbonized oxynitride film, a carbonized fluoride film and the like, or a polymer film. Moreover, when the vapor deposition polymerization method which forms into a film using 2 or more types of materials is used, a polyimide film, a polyamide film, etc. can be formed. Further, when the flash vapor deposition method is used, a polymer film such as a polyacrylate film can be formed in addition to the above film. A metal film can be formed as the opaque film.

(4) Sputtering method As the sputtering method, DC sputtering, pulse DC sputtering, RF sputtering, dual magnetron sputtering, or the like can be used. The film can be formed using any material. In the case of a transparent film, an inorganic oxide film, an inorganic oxynitride film, an inorganic nitride film (inorganic: silicon, aluminum, titanium, niobium, tin, etc.), Examples thereof include a carbonized film, a carbonized oxide film, a carbonitride film, a carbonized oxynitride film, and a carbonized fluoride film. A metal film can be formed as the opaque film.
On the other hand, it is relatively difficult to form a film with a high molecular weight by a vapor deposition method. When various protective layer materials not applied to such a vapor deposition method are used, a protective layer is formed by a wet film formation method. It is also preferable.

In addition, as the protective layer, it is necessary that the formed film is flat and has acid resistance. Therefore, a thermosetting material, an ultraviolet curable material, an electron beam curable material, and a resin material capable of forming a dense film. It is preferable to use a sol-gel material or the like.
Examples of the thermosetting material include polymethyl methacrylate, polyacrylate, polycarbonate, methyl phthalate homopolymer or copolymer, polyethylene terephthalate, polystyrene, diethylene glycol bisallyl carbonate, acrylonitrile / styrene copolymer, poly (-4- Examples thereof include methylpentene-1), phenol resin, epoxy resin, cyanate resin, maleimide resin, polyimide resin, cardo resin, and sol-gel film. In addition, those modified with polyvinyl butyral, acrylonitrile-butadiene rubber, polyfunctional acrylate compound, etc., crosslinked polyethylene resin, crosslinked polyethylene / epoxy resin, crosslinked polyethylene / cyanate resin, polyphenylene ether / epoxy resin, polyphenylene ether / cyanate Examples thereof include a thermosetting resin modified with a thermoplastic resin such as a resin. Moreover, you may use together multiple types of resin quoted above.

  Examples of ultraviolet curable materials and electron beam curable materials include many resin compositions made of acrylate compounds having radical reactive unsaturated compounds, and oligomers such as epoxy acrylate, urethane acrylate, polyester acrylate, and polyether acrylate. Examples thereof include a resin composition or a sol-gel film dissolved in a functional acrylate monomer. It is also possible to use a mixture of the resin compositions as mentioned above.

  The method for forming the resin layer is not particularly limited, and any of a spin coating method, a spray coating method, a blade coating method, a dip method, a roll coating method, and the like may be used. The thermosetting material, the ultraviolet curable material, and the electron beam curable material as described above can be added with additives such as an antioxidant, an ultraviolet absorber, and a plasticizer as necessary. In any material, an appropriate resin or additive may be used in combination for the purpose of improving film formability and preventing pinholes. Furthermore, when forming the protective layer, the resin is dissolved or dispersed in an appropriate diluent solvent such as ethanol, chloroform, tetrahydrofuran, dioxane or the like to form a thin film, but any solvent may be used.

The thickness of the protective layer when formed by the vapor deposition method can be set in the range of 50 nm to 1 μm, preferably 50 to 500 nm. Moreover, the thickness of the protective layer formed by the wet film-forming method can be set in the range of 50 nm to 10 μm, preferably 200 nm to 5 μm. When the thickness of the protective layer is less than the above range, for example, there is a portion where the protective layer is not formed, there is a possibility that the function as the protective layer may not be expressed, especially the protrusion of the barrier vapor deposition layer can not be sufficiently covered, A flat protective layer surface may not be obtained, which is not preferable. Moreover, when the thickness of a protective layer exceeds said range, the further improvement in the function as a protective layer is not acquired, but it will lead to the increase in manufacturing cost, and is unpreferable.
The gas barrier film of the present invention may be required to have transparency depending on the application, and in this case, the protective layer described above is also preferably transparent.

(Base film)
The base film constituting the gas barrier film of the present invention is not particularly limited as long as it is a film that can hold the barrier vapor-deposited layer and the protective layer, and can be appropriately selected from the intended use of the gas barrier film. Specifically, the following can be mentioned as a base film.
-Polyolefin (PO) resins such as homopolymers or copolymers of ethylene, polypropylene, butene, etc.-Amorphous polyolefin (APO) resins such as cyclic polyolefins-Polyethylene terephthalate (PET), polyethylene 2,6-naphthalate Polyester resin such as (PEN), nylon (trade name) 6, nylon (trade name) 12, polyamide (PA) resin such as copolymer nylon (trade name), polyvinyl alcohol (PVA) resin, ethylene-vinyl alcohol Polyvinyl alcohol resin such as copolymer (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 copolymer ( Fluorine resins such as FEP), vinylidene fluoride (PVDF), vinyl fluoride (PVF), perfluoro-perfluoropropylene-perfluorovinyl ether copolymer (EPA)

In addition to the above resins, a resin composition comprising an acrylate compound having a radical reactive unsaturated compound, a resin composition comprising the above acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate, polyester acrylate In addition, a photocurable resin such as a resin composition in which an oligomer such as polyether acrylate or methacrylate is dissolved in a polyfunctional acrylate monomer, and a mixture thereof can also be used. Furthermore, what laminated | stacked 1 type, or 2 or more types of these resin by means, such as a lamination and a coating, can also be used as a base film.
The base film described above may be a stretched (uniaxial or biaxial) film or an unstretched film.

  Such a base film 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 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). Although the draw ratio in this case can be suitably set according to the resin used as the raw material of the substrate, draw ratios of 2 to 10 times are preferable in the vertical axis direction and the horizontal axis direction, respectively. Further, a conventionally known film forming method such as a cast method may be used.

Among the above base films, base films having heat resistance are particularly preferable. When the gas barrier film is used for an image display medium, for example, at least 60 ° C. in the dehydration step, patterning step, and curing step, 100 ° C. for dehydration purposes, and 150 ° C. in the insulating film formation step. It is preferable to use a base film having heat resistance such that at least the glass transition temperature is 60 ° C. or higher, preferably 100 ° C. or higher, more preferably 150 ° C. or higher. Further, when producing a full-color display, it is usually necessary to separately coat the three primary colors (red, blue, and green), and dimensional stability is required for the base film, which is 60 ° C., preferably 100. It is preferable to have dimensional stability such that the linear expansion coefficient is 60 ppm or less at a temperature of ° C, more preferably 150 ° C.
Further, the base film to be used may be subjected to surface treatment such as corona treatment, flame treatment, plasma treatment, glow treatment, roughening treatment, chemical treatment, etc. before forming the barrier vapor deposition layer.

Further, an anchor coat agent layer may be formed on the surface of the base film for the purpose of improving the adhesion with the barrier vapor deposition layer. Examples of the anchor coating agent used in this anchor coating agent layer include polyester resins, isocyanate resins, urethane resins, acrylic resins, ethylene vinyl alcohol resins, vinyl modified resins, epoxy resins, modified styrene resins, modified silicon resins, and alkyl titanates. Etc., and one or two or more of these can be used in combination. Conventionally known additives can be added to these anchor coating agents. For the anchor coating agent layer, the above-mentioned anchor coating agent is coated on a base film by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, etc., and the solvent, diluent, etc. are removed by drying. Can be formed. The application amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state).

The thickness of the base film varies depending on the use of the gas barrier film, and thus cannot be defined unconditionally. However, when used as a base material for general packaging materials or package materials, the thickness is preferably about 3 to 188 μm.
The gas barrier film of the present invention as described above has an oxygen permeability of 0.5 cc / m ² / day · atm or less, a water vapor permeability of 0.5 g / m ² / day or less, preferably an oxygen permeability of 0. 0.1 cc / m ² / day · atm or less, and a water vapor permeability of 0.1 g / m ² / day or less is exhibited. Since the gas barrier film of the present invention hardly transmits oxygen and water vapor that cause changes in the quality of the contents, it is used for applications that require high gas barrier properties, such as packaging materials such as food and pharmaceuticals, and electronic devices. It can be preferably used for a packaging material. Moreover, since it has impact resistance as well as its high gas barrier properties, it can be used as a substrate for various displays, for example. Furthermore, it can be used for a cover film of a solar cell. In addition, since a protective layer having acid resistance is located on the surface of the gas barrier film, the barrier vapor deposition layer is not etched even if an etching process such as electrode patterning is performed on the protective layer. Electrode patterning of the conductive layer is possible while maintaining the properties.

  As described above, the gas barrier film of the present invention can be used in various applications alone or in the state of a laminate in which other layers are laminated, and the other layers constituting the laminate are Various materials can be used depending on the application, and in the gas barrier film of the present invention, “other layers” to be further laminated are not limited.

Laminated Material Next, the laminated material of the present invention will be described.
FIG. 3 is a schematic cross-sectional view showing an embodiment of the laminated material of the present invention using the above-described gas barrier film 1 of the present invention. In FIG. 3, a laminated material 11 includes a gas barrier film 1 in which a barrier-type vapor deposition layer 3 having a smooth surface and a protective layer 4 having a smooth surface are laminated in this order on one surface of a base film 2, and the gas barrier. A heat-sealable resin layer 13 formed on the protective layer 4 of the film 1 via an anchor coat agent layer and / or an adhesive layer 12 is provided.
The anchor coating agent layer 12 constituting the laminated material 11 is formed using, for example, an organic titanium anchor coating agent such as an alkyl titanate, an isocyanate anchor coating agent, a polyethyleneimine anchor coating agent, a polybutadiene anchor coating agent, or the like. can do. The anchor coating agent layer 12 is formed by coating the above-described anchor coating agent by a known coating method such as roll coating, gravure coating, knife coating, dip coating, spray coating, etc., and solvent, diluent, etc. It can be carried out after drying. The application amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state).

The adhesive layer 12 constituting the laminated material 11 is, for example, polyurethane-based, polyester-based, polyamide-based, epoxy-based, poly (meth) acrylic-based, polyvinyl acetate-based, polyolefin-based, casein, wax, ethylene- ( It can be formed by using various laminating adhesives such as a solvent type, water-based type, solvent-free type, or hot-melt type mainly composed of a vehicle such as a (meth) acrylic acid copolymer or polybutadiene. . The adhesive layer 12 is formed by coating the above laminating adhesive with, for example, roll coating, gravure coating, knife coating, deb coating, spray coating, or other coating methods, and removing the solvent, diluent, etc. by drying. Can be done. The application amount of the laminating adhesive is preferably about 0.1 to 5 g / m ² (dry state).

  Examples of the heat-sealable resin used for the heat-sealable resin layer 13 constituting the laminated material 11 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, and itaconic acid, a polyvinyl acetate resin, a poly (meth) acrylic resin, and a polyvinyl chloride resin 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.

FIG. 4 is a schematic cross-sectional view showing another embodiment of the laminated material of the present invention using the above-described gas barrier film 1 of the present invention. In FIG. 4, a laminated material 21 includes a gas barrier film 1 in which a barrier-type vapor deposition layer 3 having a smooth surface and a protective layer 4 having a smooth surface are laminated in this order on one surface of a base film 2, and the gas barrier. A heat-sealable resin layer 23 formed on the protective layer 4 of the film 1 via an anchor coat agent layer and / or an adhesive layer 22 and the other surface of the base film 2 of the gas barrier film 1 (barrier vapor deposition layer 3 And a base material layer 24 provided on the non-formation surface.
The anchor coat agent layer, the adhesive layer 22 and the heat sealable resin layer 23 constituting the laminate 21 are the same as the anchor coat agent layer, the adhesive layer 12 and the heat sealable resin layer 13 constituting the laminate 11 described above. The description here is omitted.

  As the base material layer 24 constituting the laminated material 21, for example, when the laminated material 21 constitutes a packaging container, the base material layer 24 becomes a basic material, and therefore, mechanical, physical, chemical, etc. In particular, it is possible to use a resin film or sheet having excellent properties, particularly strong and strong, and having heat resistance. Specifically, stretch of strong resin such as polyester resin, polyamide resin, polyaramid resin, polyolefin resin, polycarbonate resin, polystyrene resin, polyacetal resin, fluorine resin (uniaxial 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.

In the present invention, the base layer 24 may be 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. . Such characters and the like can be seen very well through the gas barrier film 1 because the gas barrier film 1 constituting the laminated material 21 can have excellent transparency as described above. it can.
Furthermore, in this embodiment, the base material layer 24 may be a paper layer using, for example, a paper base material. The paper base material used is a paper base material having formability, flex resistance, rigidity, etc., for example, a strongly sized bleached or unbleached paper base material, or pure white roll paper, kraft paper Paper base materials such as paperboard and processed paper can be used. It is desirable to use such a paper substrate having a basis weight of about 80 to 600 g / m ² , preferably about 100 to 450 g / m ² .
In the present embodiment, as the base material layer 24, the above-described resin film or sheet and the above-mentioned paper base material can be used in combination.

FIG. 5 is a schematic cross-sectional view showing another embodiment of the laminated material of the present invention using the above-described gas barrier film 1 of the present invention. In FIG. 5, a laminated material 31 includes a gas barrier film 1 in which a barrier-type vapor-deposited layer 3 having a smooth surface and a protective layer 4 having a smooth surface are laminated in this order on one surface of the base film 2, and the gas barrier. A heat-sealable resin layer 33 formed on the protective layer 4 of the film 1 via an anchor coat agent layer and / or an adhesive layer 32, and the other surface of the base film 2 of the gas barrier film 1 (barrier vapor deposition layer 3 A base material layer 34 provided on the non-formation surface) and a heat-sealable resin layer 35 formed on the base material layer 34 are provided.
The anchor coat agent layer, the adhesive layer 32 and the heat sealable resin layers 33 and 35 constituting the laminated material 31 are the anchor coat agent layer, the adhesive layer 12 and the heat sealable resin layer 13 constituting the laminated material 11 described above. Since the base material layer 34 constituting the laminated material 31 can be the same as the base material layer 24 constituting the laminated material 21 described above, the description thereof is omitted here. .

  The laminated material of the present invention further includes, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer having barrier properties such as water vapor and water. Films or sheets of resins such as, or films or sheets of resins such as polyvinylidene chloride, polyvinyl alcohol, saponified ethylene-vinyl acetate copolymer having a barrier property against oxygen, water vapor, etc., and colorants such as pigments in the resin In addition, films or sheets of various colored resins having light-shielding properties obtained by adding a desired additive and kneading to form a film can be used by laminating. These materials can be used alone or in combination of two or more, and the thickness is arbitrary, but is usually about 5 to 300 μm, preferably about 10 to 200 μm.

  Furthermore, when the laminate of the present invention is used for packaging containers, the packaging containers are usually placed under harsh conditions, both physically and chemically. Required. Specifically, various conditions such as deformation prevention 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 film 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. Polymer, ethylene-acrylic acid or methacrylic acid copolymer, methylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride, vinyl chloride-vinylidene chloride copolymer, poly (meta ) Acrylic resin, polyacrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate Resin Polyvinyl alcohol resin, saponified ethylene-vinyl acetate copolymer, fluorine resin, diene resin, polyacetal resin, polyurethane resin, nitrocellulose and other known resin films or sheets can do. In addition, for example, a film such as cellophane can be used.

As the film or sheet, any of unstretched, uniaxially or biaxially stretched can be used. Moreover, although the thickness is arbitrary, it can select and use from the range of about several micrometers-300 micrometers, and a lamination position does not have a restriction | limiting in particular. In the present invention, the film or sheet may be any film such as extrusion film formation, inflation film formation, and coating film.
The laminated materials of the embodiments such as the above-described laminated materials 11, 21, 31 are a method of laminating a normal packaging material, for example, a wet lamination method, a dry lamination method, a solventless dry lamination method, an extrusion lamination method, T It can be manufactured using a die extrusion molding method, a coextrusion lamination method, an inflation method, a coextrusion inflation method, or the like.

In addition, when performing the above lamination, if necessary, pretreatment such as corona treatment and ozone treatment can be applied to the film. For example, isocyanate (urethane), polyethyleneimine, polybutadiene An organic titanium-based anchor coating agent or a known adhesive such as a polyurethane-based, polyacrylic-based, polyester-based, epoxy-based, polyvinyl acetate-based, or cellulose-based adhesive for lamination can be used. .
In addition, the gas barrier film of the present invention used for the laminated material of the present invention is not limited to the examples shown in the above-mentioned laminated materials 11, 21, 31 and, depending on the purpose of use of the laminated material, for example, FIG. A gas barrier film having a structure as shown in FIG. 2 can be used.

Next, a packaging container using the laminated material of the present invention will be described.
The laminated material of the present invention can provide a packaging container by bag-making or box-making by heat fusion.
Specifically, when the packaging container is a flexible packaging bag, the heat-sealable resin layers of the laminated materials 11, 21 and 31 of the present invention are folded to face each other, or two laminated materials of the present invention are used. For example, 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 Various forms of packaging containers according to the present invention can be manufactured by forming a seal portion by heat-sealing in a heat seal form such as a seal type, a square bottom seal type, or the like.

In the above, the heat fusion can be performed by a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal, and the like.
FIG. 6 is a perspective view showing an embodiment of the packaging container as described above. In FIG. 6, a packaging container 51 is formed by stacking a pair of laminated materials 11 of the present invention so that the heat-sealable resin layer 13 faces each other, and in this state, heat sealing is performed on three sides of the peripheral portion to seal The part 52 is formed. This packaging container 51 can be filled with contents from an opening 53 formed in the remaining one of the peripheral part. Then, after filling the contents, the opening 53 is heat-sealed to form a seal portion, whereby a packaging container filled with the contents can be obtained.

In addition to the above, the packaging container of the present invention can be, for example, a self-supporting packaging bag (standing pouch) or the like, and a tube container or the like can be manufactured using the laminated material of the present invention.
Note that, for example, a one-piece type, a two-piece type, other pouring rods, or an opening / closing zipper can be arbitrarily attached to the packaging container as described above.
Moreover, when the packaging container is a liquid-filled paper container containing a paper base material, a blank plate for producing a desired paper container is produced using the laminated material of the present invention in which the paper base material is laminated, By using this blank plate to form the trunk, bottom, head, etc., for example, a brick type, flat type or gobbel top type liquid container can be manufactured. Moreover, the shape can be manufactured in any shape such as a rectangular container or a cylindrical can such as a round shape.

  FIG. 7 is a perspective view showing an embodiment of a liquid-filled paper container, and FIG. 8 is a plan view of a blank plate used for the packaging container shown in FIG. The blank board 70 uses the laminated material 31 of the present invention shown in FIG. 5, for example, and presses m, m... For bending in container formation and a body part constituting the body part 62 of the container 61. Panels 71, 72, 73, 74, top panels 71a, 72a, 73a, 74a constituting the top 63 of the container 61, bottom panels 71b, 72b, 73b, 74b constituting the bottom 64 of the container 61, and a cylinder It is manufactured by punching so as to include a heat-sealing panel 75 for forming. This blank plate 70 is bent at the pressing lines m, m... And the inner side of the end portion of the body panel 71 and the outer side of the heat-welding panel 75 are heat-sealed to form a cylinder, and then the bottom panel 71b. , 72b, 73b, 74b are bent and heat-sealed by pressing lines m, m... And filled with liquid from the top opening, and then the top panels 71a, 72a, 73a, 74a are pressed by pressing lines m, m,. The packaging container 61 filled and packaged with liquid can be obtained by bending and heat-sealing.

  Packaging containers using the laminated material of the present invention are used for various foods and drinks, chemicals such as adhesives and adhesives, cosmetics, pharmaceuticals, miscellaneous goods such as chemical warmers, and other various articles. It is.

Laminate Next, an embodiment of the laminate of the present invention in which a conductive layer is provided on at least one surface of the gas barrier film will be described with reference to an example using the above-described gas barrier film 1 of the present invention.
FIG. 9 is a schematic cross-sectional view showing an embodiment of a laminated material of the present invention in which a conductive layer is provided on one surface of a gas barrier film. In FIG. 9, a laminated material 41 includes a gas barrier film 1 in which a barrier vapor deposition layer 3 having a smooth surface and a protective layer 4 having a smooth surface are laminated in this order on one surface of the base film 2, and the gas barrier. A conductive layer 42 formed on the protective layer 4 of the film 1 is provided.

The conductive layer 42 constituting the laminated material 41 can be a transparent conductive film such as an indium tin oxide (ITO) film, for example. The ITO film can be formed by a sputtering method, a PVD method, an ion plating method, or the like. In particular, an ITO film formed by a sputtering method is preferably used because of excellent in-plane conductivity uniformity.
The film thickness of the conductive layer 42 can be appropriately set depending on the material, the use of the laminated material 41, and the like, and is usually set within a range of 100 to 200 nm. The conductive layer 42 preferably has a surface resistance value of 0 to 50Ω / □ and a total light transmittance of 85% or more.
For example, in the case of a liquid crystal display panel, such a conductive layer 42 can be used as a transparent electrode for driving a liquid crystal.

  In the laminate of the present embodiment, the gas barrier film is used for the purpose of ensuring the uniformity of the display formed on the conductive layer, improving the adhesion between the protective layer and the conductive layer, and preventing cracks in the conductive layer. An overcoat layer may be interposed between one protective layer 4 and the conductive layer 42. Such an overcoat layer can be formed using, for example, an ultraviolet curable resin such as an epoxy acrylate prepolymer or a urethane acrylate prepolymer having a melting point of 50 ° C. or higher. Further, if the characteristics for use as a display medium such as a liquid crystal can be satisfied, it may be formed using a thermally more stable thermosetting resin. However, it is preferable to use an ultraviolet curable resin from the viewpoint of productivity.

  In such an overcoat layer, it is indispensable that the adhesive strength to the protective layer 4 and the adhesive strength to the conductive layer 42 are sufficiently large, and flexibility and chemical resistance (acid resistance provided in the protective layer described above). Must be excellent. In order to satisfy such requirements, a primer layer may be provided between the overcoat layer and the adjacent layer. The primer layer can be formed using a conventionally known primer material, for example, polyamic acid, polyethylene resin, epoxy resin, melamine resin, polyurethane resin, polyester resin, polyol resin, polyurea resin, polyazomethine resin And commercially available resin materials and sol-gel materials such as polycarbonate resin, polyacrylate resin, polystyrene resin, polyacrylonitrile resin, and polyethylene naphthalate resin.

Image display medium The image display medium of the present invention uses the laminate material of the present invention in which a conductive layer is provided on at least one surface of a gas barrier film, for example, the laminate material 41 described above as a base material, and is formed on the conductive layer 42. An image display layer is provided.
As such an image display medium, 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 such as an electroluminescence display (EL) to emit light with some energy.

When the image display medium of the present invention 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, the phosphor layer having a phosphor has the above image display. Corresponds to the layer.
The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

Next, an Example is shown and this invention is demonstrated further in detail.
[Example 1]
A sheet-like polyethersulfone film (Sumilite FS-1300, thickness 100 μm, manufactured by Sumitomo Bakelite Co., Ltd.) was prepared as a base film, and this base film was magnetron sputtering apparatus (SPF-730H manufactured by Anerva Co., Ltd.). Attached in the chamber.

Next, the inside of the chamber of the magnetron sputtering apparatus was depressurized to an ultimate vacuum of 3.0 × 10 ⁻⁴ Pa with an oil rotary pump and a cryopump. Indium zinc oxide is used as a target, introduced at 30 sccm of argon gas and 1 sccm of oxygen gas, respectively, and applied power of 1.2 kW is applied by a direct current sputtering method, and indium zinc oxide is applied so that the film forming pressure is 25 Pa and the film thickness is 150 nm. A film was formed, and a barrier vapor deposition layer was formed on the base film. Note that sccm is an abbreviation for standard cubic centimeter per minute, and the same applies to the following examples and comparative examples.
Next, a thermosetting resin (V-259-EH manufactured by Nippon Steel Chemical Co., Ltd.) is applied on the above-mentioned barrier vapor-deposition layer by a spin coating method, and then cured at 160 ° C. for 1 hour in an oven. The treatment was performed to form a protective layer having a thickness of 1 μm to obtain a gas barrier film (Example 1).

[Example 2]
First, in the same manner as in Example 1, a barrier vapor deposition layer was formed on a base film.
Next, a silicon oxide carbide film is formed on the barrier vapor-deposited layer by a vapor deposition method (plasma polymerization method) under the following conditions to form a protective layer having a thickness of 500 nm, and a gas barrier film (Example 2) Got.
(Deposition conditions by plasma polymerization method)
・ Film forming apparatus: PED-401 manufactured by Anerva Co., Ltd.
・ Raw material gas: Hexamethyldisiloxane introduction amount 30sccm
・ Additional gas: Argon introduction amount 30 sccm
・ RF power supply: 150W input power
・ Film pressure: 33Pa

[Example 3]
First, in the same manner as in Example 1, a barrier vapor deposition layer was formed on a base film.
Next, a cyclic polyolefin resin (ZEONEX manufactured by Nippon Zeon Co., Ltd.) was dissolved in a cyclohexane solvent at a concentration of 3% by weight to prepare a protective layer coating solution, and this protective layer coating solution was applied to the coating bar. Using this, it was applied onto the above-mentioned barrier vapor-deposited layer and dried at 80 ° C. for 30 minutes to form a protective layer having a thickness of 1 μm to obtain a gas barrier film (Example 3).

[Comparative Example 1]
A gas barrier film (Comparative Example 1) was produced in the same manner as in Example 1 except that the protective layer was not formed.

[Comparative Example 2]
A gas barrier film (Comparative Example 2) was prepared in the same manner as in Example 1 except that the barrier power deposition layer was formed by setting the input power when forming the indium zinc oxide film to 2 kW.

[Comparative Example 3]
A gas barrier film (Comparative Example 3) was prepared in the same manner as in Example 1 except that the surface to be formed of the base film was subjected to oxygen plasma treatment for 30 seconds to be roughened before forming the barrier vapor-deposited layer. ) Was produced.

[Comparative Example 4]
Before forming the barrier vapor deposition layer, the surface of the base film to be formed is subjected to oxygen plasma treatment for 30 seconds to roughen the surface, and the input power for forming the indium zinc oxide film is set to 2 kW for barrier vapor deposition. A gas barrier film (Comparative Example 4) was produced in the same manner as in Example 1 except that the layer was formed.

[Comparative Example 5]
A gas barrier film (Comparative Example 5) was produced in the same manner as in Example 1 except that the curing treatment was not performed in the formation step of the protective layer.
(Surface smoothness measurement)
About the gas barrier film (Examples 1-3, Comparative Examples 1-5) produced as mentioned above, surface smoothness was carried out by the following conditions at the stage of forming a barrier vapor deposition layer and the stage of forming a protective layer, respectively. The surface roughness Ra and the maximum height difference PV were measured and shown in Table 1 below.
Surface smoothness measurement conditions Atomic force microscope (Nanopics 1000; manufactured by Seiko Instruments Inc.)
The clean surface was measured in a non-contact mode, and the surface average roughness Ra (scan area = 4 μm square) and the maximum height difference PV (scan area = 100 μm square) were measured.

(Measurement of gas barrier properties)
The gas barrier films (Examples 1 to 3 and Comparative Examples 1 to 5) produced as described above were measured for oxygen transmission rate and water vapor transmission rate under the following conditions, and the results are shown in Table 1 below.
Oxygen permeability measurement conditions Using an oxygen gas permeability measuring device (OX-TRAN 2/20 manufactured by MOCON), the oxygen permeability was measured at a temperature of 23 ° C. and dry (0% RH). The measurement was performed by the measurement method “with independent zero” that removes the background.
Conditions for measuring water vapor transmission rate Water vapor transmission rate measurement device (PERMATRAN-W 3/31 manufactured by MOCON)
Was measured under the conditions of a temperature of 37.8 ° C. and a humidity of 100% RH.

(Acid resistance test)
About the gas barrier film (Examples 1-3, Comparative Examples 1-5) produced as mentioned above, after performing an etching process on the following conditions, oxygen permeability and water vapor permeability were measured on the same conditions as the above. The results are shown in Table 1 below. Further, the thickness of the protective layer after the etching treatment was measured, and the etching rate (μm / min) in the thickness direction was calculated and shown in Table 1 below.
Etching conditions The gas barrier film was immersed in an etching solution having a volume mixing ratio of hydrochloric acid: nitric acid: water of 1: 0.08: 1 for 10 minutes, washed with water and dried.

As shown in Table 1, gas barrier films (Examples 1 to 3) each including a barrier vapor-deposited layer having a smooth surface and an acid-resistant protective layer having a smooth surface laminated on the barrier vapor-deposited layer are as follows. It was confirmed that it has excellent gas barrier properties (oxygen permeability is 0.1 cc / m ² / day · atm or less and water vapor permeability is about 0.1 g / m ² / day or less).
In contrast, the comparative gas barrier films (Comparative Examples 1 to 5) had insufficient gas barrier properties or insufficient acid resistance.

  It can be used as a packaging material such as food and medical products that require barrier properties, a packaging material such as an electronic device, and a substrate material, and can also be used as a laminated material and an image display medium using a gas barrier film.

It is a schematic sectional drawing which shows one Embodiment of the gas barrier film of this invention. It is a schematic sectional drawing which shows other embodiment of the gas barrier film of this invention. It is a schematic sectional drawing which shows one Embodiment of the laminated material using the gas barrier film of this invention. It is a schematic sectional drawing which shows other embodiment of the laminated material using the gas barrier film of this invention. It is a schematic sectional drawing which shows other embodiment of the laminated material using the gas barrier film of this invention. It is a perspective view which shows one Embodiment of the container for packaging using the laminated material of this invention. It is a perspective view which shows other embodiment of the packaging container using the laminated material of this invention. It is a top view of the blank board used for manufacture of the container for packaging shown by FIG. It is a schematic sectional drawing which shows other embodiment of the laminated material using the gas barrier film of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1,1 '... Gas barrier film 2 ... Base film 3 ... Barrier vapor deposition layer 4 ... Protective layer 11, 21, 31, 41 ... Laminate 12, 22, 32 ... Anchor coating agent layer, adhesive layer 13, 23, 33 ... Heat-sealable resin layer 24, 34 ... Base material layer 35 ... Heat-sealable resin layer 42 ... Conductive layer 51, 61 ... Packaging container

Claims (12)

A base film, a barrier vapor deposition layer having a smooth surface provided on at least one surface of the base film, and an acid-resistant protective layer having a smooth surface laminated on the barrier vapor deposition layer. The oxygen transmission rate is 0.1 cc / m ² / day · atm or less, the water vapor transmission rate is 0.1 g / m ² / day or less, and the barrier vapor-deposited layer is made of indium zinc oxide. The atomic ratio of indium (In) to zinc (Zn) in the zinc oxide is such that In / (In + Zn) is in the range of 0.5 to 0.8, and the acid resistance of the protective layer is hydrochloric acid: nitric acid: water volume mixing ratio of 1: 0.08: gas barrier film etch rate, characterized in der Rukoto made a 0.01 [mu] m / min or less by 1 a is indium tin oxide etchant.   The gas barrier film according to claim 1, wherein the laminate of the barrier vapor-deposited layer and the protective layer is repeatedly formed twice or more.   3. The gas barrier film according to claim 1, wherein the smooth surface of the barrier vapor deposition layer has a surface roughness Ra of 6 nm or less and a maximum height difference PV of 60 nm or less.   The gas barrier film according to any one of claims 1 to 3, wherein the smooth surface of the protective layer has a surface roughness Ra of 6 nm or less and a maximum height difference PV of 60 nm or less. 2. The barrier vapor deposition layer, wherein one or more of tin, aluminum, antimony, gallium, and germanium are doped in a range of 20 atomic% or less with respect to a total amount of indium and zinc. The gas barrier film according to claim 4. The gas barrier film according to any one of claims 1 to 5 , wherein the protective layer is a layer formed by a vapor deposition method and has a thickness in a range of 50 nm to 1 µm. The protective layer includes a silicon oxide film, a silicon nitride film, a silicon carbide film, a silicon oxycarbide film, a silicon oxynitride film, a silicon oxynitride carbide film, a hydrocarbon film, a fluorocarbon film, a polyimide film, a polyamide film, and an acrylate film. The gas barrier film according to claim 6 , wherein the gas barrier film is a layer composed of one or more films selected from a methacrylate film, a urethane acrylate film, an epoxy film, an epoxy acrylate film, an acrylic film, and an olefin film. The gas barrier film according to any one of claims 1 to 5 , wherein the protective layer is a layer formed by a wet film forming method and has a thickness in a range of 50 nm to 10 µm. The protective layer is a layer made of one or more resins selected from acrylate resins, acrylic resins, urethane resins, urethane acrylate resins, epoxy resins, epoxy acrylate resins, olefin resins, cardo resins, and methacrylic resins. The gas barrier film according to claim 8 . A laminated material comprising a heat-sealable resin layer provided on at least one surface of the gas barrier film according to any one of claims 1 to 9 . A laminated material comprising a conductive layer provided on at least one surface of the gas barrier film according to any one of claims 1 to 9 . An image display medium comprising the laminate according to claim 11 as a base material, and an image display layer provided on the conductive layer.

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