JP6171419B2 - Method for producing gas barrier film - Google Patents

Description

  The present invention relates to a film excellent in gas barrier properties and transparency.

  Gas barrier films are widely used in precision electronic parts such as hard disks and semiconductor modules, back sheets for solar cells, packaging fields for foods and pharmaceuticals, etc., and parts that need to block oxygen and water vapor in non-packaging fields. It is used.

  That is, in precision electronic parts, in order to prevent corrosion of metal parts, insulation failure, etc., there is a packaging body having a gas barrier property that blocks oxygen and water vapor that permeate the packaging material and other gases that alter the contents. It has been demanded.

  In particular, in food packaging, it is necessary to maintain the taste and freshness by suppressing the oxidation and alteration of proteins and fats and oils. In addition, in pharmaceuticals that require handling under aseptic conditions, it is necessary to suppress the alteration of the active ingredient and maintain its efficacy.

  Therefore, metal foils such as aluminum that have not been affected by temperature and humidity, aluminum deposited films, polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), polyvinylidene chloride (PVDC), polyacrylonitrile ( PAN) and the like, and plastic films laminated or coated with these resins have been used favorably.

  However, a gas barrier resin film or a film coated with a gas barrier resin is highly temperature dependent and cannot maintain high gas barrier properties. Furthermore, PVDC, PAN, and the like are discarded after use and may cause harmful substances when incinerated.

  A packaging material using a metal foil such as aluminum or an aluminum vapor-deposited film is excellent in gas barrier properties, but has no retort resistance and is opaque, so that it is difficult to identify the contents through the packaging material. Not only that, it has the disadvantages that it must be treated as an incombustible material upon disposal after use, and that it cannot perform foreign matter inspection with a metal detector or heat treatment in a microwave oven.

  Further, as a packaging material that overcomes these drawbacks, a gas barrier film in which an inorganic oxide such as silicon oxide, aluminum oxide, magnesium oxide, or calcium oxide is deposited on a transparent base film has recently been promoted. . These gas barrier vapor-deposited films are known to have transparency and gas barrier properties such as oxygen and water vapor, although not as much as metal vapor-deposited films.

JP 2009-23114 A

  The present invention is intended to solve the above-described problems of the prior art, and an object thereof is to provide a gas barrier film capable of obtaining high gas barrier properties and transparency.

Method for producing a gas barrier film of the present invention has been made in view of the problems relating to at least one side of the substrate, and an organic film, an inorganic oxide film, a metal thin film, and an inorganic oxide film , together with you laminated in this order,
The organic film is selected from one or a plurality of polyester resins, isocyanate resins, urethane resins, acrylic resins, vinyl alcohol resins, ethylene vinyl alcohol resins, vinyl modified resins, and epoxy resins,
The metal thin film refers to aluminum (Al),
The inorganic oxide film refers to silicon oxide (SiO _X ), where X = 1.5 to 1.8.
The inorganic oxide film comprises, as an evaporation material, a metal silicon having a diameter of 50 μm or less of 95% or more of metal silicon and a powder having a crystal structure of 95% and a diameter of 50 μm or less of 95% or more of silicon dioxide. Using a mixture having an Si ratio of 1.5, an electron beam heating type vacuum evaporation apparatus was used to form a film by a heating evaporation method in which an electron beam emitted from an electron gun was irradiated to the evaporation material and evaporated. It is characterized by that.
The present invention, the thickness of the pre-Symbol organic layer may be a 0.01 to 3 [mu] m.
The inorganic oxide film of the present invention may have a total film thickness of 10 nm to 150 nm.
In the metal thin film of the present invention, the metal thin film refers to aluminum (Al), and may have a thickness of 1 nm to 4 nm.
The present invention, transmittance that put the wavelength 350nm can Rukoto is 40% or more.
In the present invention , an inorganic oxide film, a metal thin film, and an inorganic oxide film can be laminated in this order on at least one surface of a substrate.

The present invention, before further provided organic film between the Kimotozai and an inorganic oxide film, the organic material film, polyester resins, isocyanate resins, urethane resins, acrylic resins, polyvinyl alcohol resins, ethylene vinyl alcohol resins, vinyl One or a plurality of modified resins and epoxy resins can be selected.

The present invention, before Symbol inorganic oxide film refers to a silicon oxide (SiO _X), can be at x = 1.5 to 1.8.

The present invention, before Symbol inorganic oxide film can be total thickness is 10nm or more 150nm or less.

The present invention, before Symbol metal thin film can be a film thickness of 1nm or more 4nm or less.

The present invention transparently ratio can be 40% or more.

Sectional drawing of the gas barrier film based on one Embodiment in this invention.

Embodiments of the present invention will be described below.
FIG. 1 is a cross-sectional view illustrating a gas barrier film of the present invention.
The gas barrier film is formed by laminating an organic film 2, an inorganic oxide film 3, a metal thin film 4 and an inorganic oxide film 5 on a polymer film substrate 1.

  The polymer film substrate 1 is not particularly limited, and a known one can be used. For example, polyolefin (polyethylene, polypropylene, etc.), polyester (polyethylene naphthalate, polyethylene terephthalate, etc.), polyamide (nylon-6, nylon-66, etc.), polystyrene, ethylene vinyl alcohol, polyvinyl chloride, polyimide, polyvinyl alcohol , Polymer film bases such as polycarbonate, polyethersulfone, acrylic, and cellulose (triacetylcellulose, diacetylcellulose, etc.), but not particularly limited.

  It is preferable to use a transparent film as the polymer film substrate 1 because it is suitable for mass production. In addition, the thickness is not particularly limited, and practically in the range of 12 μm or more and 188 μm or less is preferable in consideration of workability such as vapor deposition for forming a gas barrier film.

An inorganic oxide film 3 is formed on the polymer film substrate 1, and an organic film 2 is formed on the polymer film substrate 1 in order to improve the adhesion between the inorganic oxide film 3 and the polymer film substrate 1. It is preferable to provide an anchor coat layer.
The anchor coating agent is selected from one or a plurality of solvent-soluble or water-soluble polyester resins, isocyanate resins, urethane resins, acrylic resins, vinyl alcohol resins, ethylene vinyl alcohol resins, vinyl modified resins, and epoxy resins.

The thickness of the organic film 2 is usually 0.01 to 3 μm, preferably 0.05 to 1 μm. When the film thickness exceeds 3 μm, it becomes easy to peel from the base film or sheet due to the internal stress of the film. If it is less than 0.05 μm, the film thickness may not be uniform.
Moreover, in order to improve the adhesiveness of the coating film to a film, you may perform a chemical process, an electrical discharge process, etc. on the surface of a base film before application | coating. Examples of the coating method include, but are not limited to, bar coater, knife coat, die coat, and gravure coat.

  As a film forming means for the inorganic oxide films 3 and 5 and the metal thin film 4, a heat evaporation method using an electron beam, a laser beam, or the like is preferably used among vacuum evaporation methods. In particular, the electron beam heating vapor deposition method is effective in that the film formation rate and the temperature rise / fall to the inorganic oxide vapor deposition material can be performed in a short time.

  The metal used for the inorganic oxide film or the metal thin film is selected from one or more of the group consisting of silicon, aluminum, titanium, tin, zinc, indium, and magnesium.

  In general, the thickness of the inorganic oxide film 3 and the inorganic oxide film 5 formed on the surface of the organic film 2 by the evaporated material for vapor deposition is desirably in the range of 5 nm to 300 nm. More preferably, it is 10 nm or more and 150 nm or less, and the value is appropriately selected.

  However, if the thickness of the inorganic oxide film 3 and the inorganic oxide film 5 is less than 5 nm, a uniform film may not be obtained or sufficient barrier performance may not be exhibited. In addition, when the film thickness exceeds 300 nm, the film cannot retain flexibility, and there is a possibility that the film may crack due to external factors such as bending and tension after the film formation.

  The thickness of the metal thin film 4 formed on the surface of the inorganic oxide film 3 by the vapor deposition material made of evaporated metal aluminum is generally preferably in the range of 1 nm to 4 nm, and the value is appropriately selected. .

  However, if the thickness of the metal thin film 4 is less than 1 nm, a uniform film may not be obtained or sufficient barrier performance may not be exhibited. Moreover, when a film thickness exceeds 4 nm, there exists a possibility that the transmittance | permeability of a gas barrier vapor deposition film may become low.

Examples of the present invention will be specifically described below.
<Example 1>
A urethane resin film was obtained by coating a urethane resin on 16 μm polyethylene terephthalate (PET) with a bar coater. Metallic silicon and silicon dioxide were used as the inorganic oxide for the vapor deposition material and mixed so that the O / Si ratio was 1.5.

  The metal silicon used was 95% or more of powder having a diameter of 50 μm or less, and silicon dioxide containing 95% of crystal structure and 95% or more of powder having a diameter of 50 μm or less was used. Aluminum (ALE03GB manufactured by High Purity Chemical Co., Ltd.) was used as a vapor deposition material for forming a metal thin film.

  Next, the electron beam emitted from the electron gun is irradiated onto the deposition material by an electron beam heating type vacuum deposition apparatus to evaporate it, and a 15 nm thick silicon oxide film, a 2 nm thick metal aluminum film, and a thickness are formed on the anchor coat layer. A 15 nm silicon oxide film was formed in this order to obtain a gas barrier film.

<Example 2>
A gas barrier film was obtained in the same manner as in Example 1 except that the metal aluminum film had a thickness of 3.5 nm.

Hereinafter, comparative examples of the present invention will be described.
<Comparative Example 1>
A gas barrier film was obtained in the same manner as in Example 1 except that the metal aluminum film had a thickness of 5 nm.

<Comparative example 2>
As a polymer film substrate, silicon oxide having a thickness of 15 nm was laminated twice on 16 μm PET, and a metal aluminum film having a thickness of 2 nm was formed in this order to obtain a gas barrier film.

<Comparative Example 3>
A 15 nm thick silicon oxide film was formed twice on 16 μm PET as a polymer film substrate to obtain a gas barrier film.

  The gas barrier films of Examples 1 and 2 and Comparative Examples 1 to 3 were measured and evaluated for transmittance and water vapor permeability by the following methods.

<About transmittance>
The gas barrier vapor deposition films of Examples 1 and 2 and Comparative Examples 1 to 3 were cut into an area of 20 mm wide × 30 mm long, and these gas barrier films were measured at a wavelength of 350 nm using a spectrophotometer (SHIMADZU UV-2450). The transmittance was measured. A film having a transmittance of 40% or more was marked with ◯, and a film with a transmittance of less than 40%.

<About water vapor barrier properties>
The water vapor barrier properties of the gas barrier vapor-deposited films of Examples 1 and 2 and Comparative Examples 1 to 3 were measured in an atmosphere of 40 ° C. and 90% RH using a water vapor permeability measuring device (MOCON PERMATRAN 3/21) manufactured by Modern Control. It was measured.

Table 1 below shows the measurement results.

<Evaluation>
As shown in Table 1, the transmittance, retort resistance, and water vapor permeability of Examples 1 and 2 were superior to the transmittance, retort resistance, and water vapor permeability of Comparative Examples 1 and 2. Although the water vapor permeability of Comparative Example 3 was superior to that of Examples 1 and 2, the transmittance was superior to that of Comparative Example 3 in Examples 1 and 2.

  The present invention has a high gas barrier property against oxygen, water vapor, and the like, and can be widely applied to the field of materials such as foods, daily necessities, medical products, etc. that need to block oxygen and water vapor outside the packaging field.

  DESCRIPTION OF SYMBOLS 1 ... Polymer film base material, 2 ... Organic substance film, 3 ... Inorganic oxide film, 4 ... Metal thin film, 5 ... Inorganic oxide film.

Claims (5)

On at least one side of the substrate, and an organic film, an inorganic oxide film, a metal thin film, and an inorganic oxide film, together with you laminated in this order,
The organic film is selected from one or a plurality of polyester resins, isocyanate resins, urethane resins, acrylic resins, vinyl alcohol resins, ethylene vinyl alcohol resins, vinyl modified resins, and epoxy resins,
The metal thin film refers to aluminum (Al),
The inorganic oxide film refers to silicon oxide (SiO _X ), where X = 1.5 to 1.8.
The inorganic oxide film comprises, as an evaporation material, a metal silicon having a diameter of 50 μm or less of 95% or more of metal silicon and a powder having a crystal structure of 95% and a diameter of 50 μm or less of 95% or more of silicon dioxide. Using a mixture having an Si ratio of 1.5, an electron beam heating type vacuum evaporation apparatus was used to form a film by a heating evaporation method in which an electron beam emitted from an electron gun was irradiated to the evaporation material and evaporated. A method for producing a gas barrier film , comprising: The manufacturing method of claim 1 of the gas barrier film, the thickness of the pre-Symbol organic film, method for producing a gas barrier film, which is a 0.01 to 3 [mu] m. The method of manufacturing a gas barrier film of claim 1, wherein the inorganic oxide film, a manufacturing method of the gas barrier film, wherein the total thickness is 10nm or more 150nm or less. The method of manufacturing a gas barrier film of claim 1, wherein the metal thin film, the metal thin film refers to aluminum (Al), method for producing gas barrier film, wherein a film thickness of 1nm or more 4nm or less. The method of manufacturing a gas barrier film of claim 1, method for producing a gas barrier film transmittance that put the wavelength 350nm is characterized Rukoto is 40% or more.

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