JP6163776B2 - Gas barrier vapor deposition film and method for producing the vapor deposition film - Google Patents

Description

The present invention relates to a method for producing a moth gas barrier property deposited films and the deposition film.

  Gas barrier vapor-deposited films are widely used for materials in the packaging field such as back sheets of solar cells, electronic parts, foods and pharmaceuticals, or members outside the packaging field where oxygen and water vapor need to be blocked.

  It is necessary to protect the contents of precision electronic parts such as hard disks and semiconductor modules, or packaging materials used for packaging foods and pharmaceuticals. In particular, packaging materials used in foods must maintain the taste and freshness by suppressing the oxidation and alteration of proteins and fats and oils.

  In addition, pharmaceuticals that require handling under aseptic conditions need to suppress the alteration of active ingredients and maintain their efficacy. Furthermore, for precision electronic components, in order to prevent corrosion of metal parts, insulation failure, etc., packaging materials having gas barrier properties that block oxygen and water vapor that permeate the packaging material and other gases that alter the contents are required. It has been.

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

  However, packaging materials using metal foils such as aluminum and aluminum vapor deposition films have excellent gas barrier properties, but they are opaque, so it is not only difficult to identify the contents through the packaging material, but also to use There are drawbacks in that it must be treated as an incombustible material at the time of subsequent disposal, and cannot be inspected for foreign matter by a metal detector or heat-treated in a microwave oven.

  Moreover, a gas barrier resin film or a film coated with a gas barrier resin has a large temperature dependency, and it is difficult to maintain a high gas barrier property. Furthermore, polyvinylidene chloride (PVDC), polyacrylonitrile (PAN), and the like have problems such as the possibility of causing harmful substances during disposal and incineration after use as packaging materials.

  Therefore, a gas barrier film in which inorganic oxides such as magnesium oxide, calcium oxide, aluminum oxide, and silicon oxide are vapor-deposited on a transparent base film has recently been proposed as a packaging material to overcome the above disadvantages. (For example, see Patent Documents 1 and 2).

  These gas barrier vapor-deposited films are known to have transparency and gas barrier properties such as oxygen and water vapor, and as packaging materials having both functions of transparency and gas barrier properties that cannot be obtained with metal foil or the like. Particularly, a film on which silicon oxide SiOx is deposited is used as a food packaging film. In addition, when silicon oxide SiOx is deposited by a heating method as a deposition material, the film formation rate is very fast, and the productivity efficiency can be increased.

  However, silicon oxide SiOx (0 <x <2), which is a vapor deposition material used here, is manufactured by vacuum vapor deposition using metal silicon and silicon dioxide as raw materials. Have.

  Since silicon oxide SiOx (0 <x <2), which is a material for vapor deposition produced by vacuum vapor deposition, is not a production method suitable for mass productivity, there is a problem that the material cost is high and the production cost is high.

  Further, silicon oxide SiOx (0 <x <2) as a deposition material has a density close to the true density and has a very dense structure. Therefore, when a barrier film is manufactured by evaporating the deposition material, the unvaporized deposition material scatters as high-temperature particles due to the thermal shock caused by heating during vapor deposition or the pressure of the gas generated from the inside. There is a problem that the phenomenon of splash occurs.

  In addition, when high-temperature particles reach the polymer film, pinholes and foreign matters are generated, resulting in reduced barrier properties and poor appearance. Further, as the heating method described above, particularly when heating using an electron gun is performed, the occurrence of splash and foreign matter appears more remarkably when the deposition material is subjected to a larger thermal shock.

  On the other hand, the mixed vapor deposition material of metal silicon and silicon dioxide is relatively inexpensive, but it is difficult to evaporate because it has a higher vapor pressure than silicon monoxide during heating, and is a fusion type vapor deposition material. For this reason, a larger thermal shock is required, and the vapor deposition material easily scatters accordingly, so that splash is likely to occur. Further, the generation of oxygen gas due to the decomposition of silicon dioxide increases the pressure in the film formation chamber, thereby lowering the deposition rate and thus reducing the productivity. In addition, there is a problem in that the barrier property of the deposited film is lowered due to the lowered deposited film density.

JP-A-8-296036 JP-A-6-016848

  The present invention has been made in order to solve the above-described problems of the prior art, and is a vapor deposition material capable of suppressing the occurrence of a splash phenomenon and maintaining a high gas barrier property, and a gas barrier deposited with the vapor deposition material. It is an object to provide a vapor-deposited film and a method for producing the vapor-deposited film.

In order to solve the above problems, the gas barrier vapor deposition film of the present invention is
A polymer film substrate;
A gas barrier vapor deposition film having a vapor deposition film deposited as a SiOx / SnOy film on one side or both sides of the polymer film substrate,
Before the total number of atoms of tin (Sn) and silicon Ki蒸-deposit (Si), atomic ratio of oxygen (O) (O / (Si + Sn)) is 1.0 to 2.0, tin The ratio of the number of atoms of (Sn) and silicon (Si) (Sn / Si) is 0.03 to 0.15,
During pre Ki蒸-deposit, there is a metal Sn peak represents a metal bond,
Said metal Sn peak area, the ratio of the Sn peak area present in the deposited film (metal Sn / Sn) is characterized in that 0.1 to 1.0.
The method for producing a gas barrier vapor deposition film of the present invention is a method for producing the above gas barrier vapor deposition film,
A material for vapor deposition by a heating method containing both metallic silicon and silicon dioxide powder and metallic tin powder, wherein the total number of atoms of silicon (Si) and tin (Sn) and oxygen (O) The ratio of the number of atoms (O / (Si + Sn)) is 0.3 to 1.8, and the ratio of the number of atoms of tin (Sn) and silicon (Si) (Sn / Si) is 0.03 to 0.00. the deposition material is 15, and evaporated by vacuum evaporation apparatus of the electron beam heating method, it is possible that deposited the deposited film on one or both surfaces of the polymer film substrate.
In the present invention, the bulk density of the vapor deposition material may be in the range of 0.9 to 1.5 g / cm ³ .
In the present invention, the silicon dioxide powder may contain at least 20% of a crystal structure.
In the present invention, the metal silicon has a powder having a diameter of 50 μm or less of 95% or more, the silicon dioxide contains a crystal structure of 95%, and the powder having a diameter of 50 μm or less is 95% or more. The metal tin may have a powder having a diameter of 50 μm or less of 95% or more.
The present invention is a material for vapor deposition by a heating method containing a powder of either or both of metal silicon and silicon dioxide, and a powder of either or both of metal tin and tin oxide, and silicon (Si) And the ratio of the total number of atoms of tin (Sn) and the number of atoms of oxygen (O) (O / (Si + Sn)) is 0.3 to 1.8, and tin (Sn) and silicon (Si) The ratio of the number of atoms (Sn / Si) can be an evaporation material having a ratio of 0.03 to 0.15.

The present invention, in the vapor deposition material, the bulk density by molding of the deposition material can be in the range of 0.9~1.5g / cm ^3.

The present invention, in the vapor deposition material, the powder of the silicon dioxide can contain a crystal structure at least 20% or more.

The present invention is a gas barrier vapor deposition film having a polymer film substrate and a deposited film deposited on one or both surfaces of the polymer film substrate,
The ratio (O / (Si + Sn)) of the total number of atoms of silicon (Si) and tin (Sn) to the number of atoms of oxygen (O) (O / (Si + Sn)) in the deposited film deposited on the polymer film substrate is 1.0-2. a .0 atomic ratio of tin (Sn) and silicon (Si) (Sn / Si) can be 0.03 to 0.15 der Ruga gas barrier property deposited film.

In the gas barrier vapor deposition film according to the present invention, a metal Sn peak representing a metal bond by XPS can be present in the vapor deposition film constituting the gas barrier vapor deposition film.

In the gas barrier vapor deposition film according to the present invention, a ratio (metal Sn / Sn) between the metal Sn peak area and the Sn peak area present in the vapor deposition film may be 0.1 to 1.0. .

Further, the present invention provides a vapor deposition material having a configuration described in the invention corresponding to any one of the above , by evaporating the vapor deposition material using an electron beam heating type vacuum vapor deposition apparatus, on one or both surfaces of the polymer film substrate. it can be a method for producing a film to Ruga gas barrier property deposited film as deposited film.

  ADVANTAGE OF THE INVENTION According to this invention, generation | occurrence | production of the splash phenomenon can be suppressed, the vapor deposition material which can maintain high gas barrier property, the gas barrier vapor deposition film vapor-deposited using this vapor deposition material, and the manufacturing method of vapor deposition film can be provided. Furthermore, even when a high-power electron beam heating vapor deposition method is used to improve productivity, the splash phenomenon can be suppressed, and a vapor deposition film having a high gas barrier property can be obtained.

Sectional drawing which shows one Embodiment of the gas barrier vapor deposition film which concerns on this invention. The figure explaining the measurement result of the various characteristics in the comparative example for comparing with the Example of the gas barrier vapor deposition film using the manufacturing method of the gas barrier vapor deposition film which concerns on this invention.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
FIG. 1 is a cross-sectional view showing an embodiment of a gas barrier vapor deposition film according to the present invention.

  The gas barrier vapor deposition film 10 includes a polymer film substrate 11, a powder of either or both of metal silicon and silicon dioxide, and a powder of any one or both of metal tin and tin oxide. Is vapor-deposited by a vacuum evaporation method of a heating method, and includes an inorganic oxide film 12 formed by vapor deposition on one surface (upper surface) side of the polymer film substrate 11.

  By setting it as such a structure, as mentioned later in detail, the preferable gas barrier property vapor deposition film which can ensure gas barrier performance and the uniformity of film-forming can be obtained.

  The polymer film substrate 11 is not particularly limited by materials, and a known material 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.

  The use of a transparent film as the polymer film substrate 11 is preferable because it is suitable for mass production and can be realized at low cost. The thickness of the film base 11 is not particularly limited, and is practically preferably in the range of 12 to 188 μm in consideration of workability such as vapor deposition processing for forming the gas barrier vapor deposition film 10.

  In addition, although the inorganic oxide film 12 is formed on one side of the polymer film substrate 11, it may be formed on both surfaces of the polymer film substrate 11, or may be in the form of a multilayer structure. Or what formed the inorganic oxide film 12 of a different composition on both surfaces of the polymer film base material 11 may be used.

  As the film forming means for the inorganic oxide film 12, it is preferable to use a heating vapor deposition method using an electron beam, a laser beam, or the like, among the heating vacuum deposition methods described above. In addition to being able to control the temperature rise and fall of the inorganic oxide vapor deposition material in a short time, it is also suitable when silicon dioxide is used as the powder material for vapor deposition.

  The reason for this is that since silicon dioxide contains 20% or more of the crystal structure, oxygen gas is generated from silicon dioxide by electron beam heating, and this oxygen gas reacts with metal powder or metal tin, which is another powder material. It is because it can be made.

  In general, the thickness of the inorganic oxide film 12 is desirably in the range of 5 to 300 nm, and the value is appropriately selected. However, if the thickness of the inorganic oxide film 12 is less than 5 nm, it may be difficult to obtain a uniform film, the film thickness may not be sufficient, and sufficient barrier performance may not be exhibited. Further, when the thickness of the inorganic oxide film 12 exceeds 300 nm, it becomes difficult to maintain the flexibility of the inorganic oxide film 12, and when external factors such as bending and tension are applied after the film formation, The physical film 12 may be cracked, and it becomes difficult to maintain the barrier property.

  Next, the action (various characteristics) of the heating oxide vapor deposition material containing a plurality of powders and the vapor deposition film formed by evaporating the vapor deposition material using the heating vacuum deposition method. ) Or the utility will be described in detail.

  The “evaporation material” used in the heating method containing either or both of the metal silicon and silicon dioxide powders and the metal tin and tin oxide powders in this embodiment is silicon ( Ratio of the total number of atoms of Si) and tin (Sn) and the number of atoms of oxygen (O) (O / (Si + Sn)), ratio of the number of atoms of tin (Sn) and silicon (Si) (Sn / Si) In addition, it is possible to form the inorganic oxide film 12 that is not easily destroyed by the thermal shock caused by the electron beam by controlling the bulk density appropriately. Therefore, the thermal shock resistance of the inorganic oxide film 12 is improved and the splash phenomenon is suppressed.

  That is, during vapor deposition by electron beam heating, the bulk density is suitably controlled to reduce the thermal conductivity so as not to become a dense structure, and silicon dioxide or tin oxide having a low thermal conductivity is mixed. As a result, it is possible to suppress the occurrence of bumping due to a rapid temperature rise due to electron beam heating, and to reduce the splash phenomenon.

  Further, when silicon dioxide or tin oxide is heated, oxygen gas is desorbed and generated. As a result, the heated metal silicon reacts without bumping because it has oxygen gas generated from silicon dioxide or tin oxide nearby, and becomes SiOx vapor. In the heated metal tin, oxygen gas generated from silicon dioxide or tin oxide is present in the vicinity, so that it reacts without bumping and becomes SnOy vapor. Further, the tin oxide evaporates into SnOy vapor, whereby a SiOx / SnOy film is formed on the polymer base film 11. And since melted silicon dioxide remains in the surface layer of vapor deposition material, it is thought that a splash is suppressed and the vapor deposition film provided with high barrier property can be formed.

  Vapor deposition material containing either or both of metal silicon and silicon dioxide powders and metal tin and / or tin oxide powders in this embodiment is evaporated by a heating vacuum deposition method. The ratio of the total number of atoms of silicon (Si) and tin (Sn) and the number of atoms of oxygen (O) (O / (Si + Sn) for the “deposited film” deposited on the polymer film substrate 11 ) Is preferably 1.0 to 2.0. When the atomic ratio O / (Si + Sn) is less than 1.0, the oxide component contained in the deposited film is small, so that the transparency of the film is lowered, and the atomic ratio O / (Si + Sn) is 2. It is theoretically impossible to exceed 0.

  A vapor deposition material containing either or both of powders of metal silicon and silicon dioxide and powders of either or both of metal tin and tin oxide in the present embodiment is applied by a vacuum vapor deposition method among heating methods. Regarding the “deposition film” evaporated and evaporated on the polymer film substrate 11, the ratio of the number of atoms of Sn (Sn) and silicon (Si) (Sn / Si) is preferably 0.03 to 0.15. The reason is that when Sn / Si in the ratio of the number of atoms is less than 0.03, the effect of improving the barrier property due to the inclusion of the tin component cannot be obtained, and when Sn / Si exceeds 0.15, the deposited film Since the amount of tin (Sn) contained in the film increases, the water resistance of the film decreases.

  A vapor deposition material containing either or both of powders of metal silicon and silicon dioxide and powders of either or both of metal tin and tin oxide in the present embodiment is applied by a vacuum vapor deposition method among heating methods. Regarding the “deposited film” evaporated and deposited on the polymer film substrate 11, the metal-bonded metal Sn peak obtained from the spectrum analysis by XPS (X-ray Photoelectron Spectroscopy) is included in the deposited film. The ratio of the metal Sn peak area to the Sn peak area present in the deposited film (metal Sn / Sn) is preferably 0.1 to 1.0. Theoretically, if the metal Sn / Sn that is the peak area ratio is less than 0.1, the effect of improving the barrier property due to the inclusion of the metal Sn component cannot be obtained, and the metal Sn / Sn exceeds 1.0. I don't get it.

  On the other hand, regarding the “evaporation material” used in the heating system containing either or both of the metal silicon and silicon dioxide powders in this embodiment and the powder of either or both of metal tin and tin oxide, The ratio of the total number of atoms of silicon (Si) and tin (Sn) to the number of atoms of oxygen (O) (O / (Si + Sn)) is preferably 0.3 to 1.8.

  When the atomic ratio O / (Si + Sn) is less than 0.3, the amount of oxide contained in the material is small, so that the melted portion of the material surface layer is small, splash is likely to occur, and O / (Si + Sn) is 1. If it exceeds 8, the generation of oxygen gas increases, so that the pressure in the film formation chamber rises, the deposition rate is lowered, and the productivity is lowered, and the barrier property of the deposited film is lowered due to the lowered deposited film density. To do.

  In addition, regarding the “evaporation material” used in the heating method containing either or both of the metal silicon and silicon dioxide powders and the metal tin and tin oxide powders in the present embodiment, The ratio (Sn / Si) of the number of atoms of tin (Sn) and silicon (Si) is preferably 0.03 to 0.15. When the ratio of the number of atoms of tin (Sn) and silicon (Si) (Sn / Si) is less than 0.03, the effect of improving the barrier property by adding the tin component cannot be obtained, and Sn / Si is 0.15. If it exceeds 1, the amount of tin (Sn) contained in the deposited film increases, so that the water resistance of the film decreases.

Further, the “bulk density” of the vapor deposition material used in the heating method containing the powder of either or both of metal silicon and silicon dioxide and the powder of either or both of metal tin and tin oxide in the present embodiment. Is preferably in the range of 0.9 to 1.5 g / cm ³ . The reason is that if the bulk density of the vapor deposition material is less than 0.9 g / cm ³ , the vapor deposition material is likely to be cracked or scattered, and if the bulk density exceeds 1.5 g / cm ³ , it is necessary for evaporation of the material. This is because more energy is required, the evaporation rate is lowered, the deposition rate is lowered, and the productivity is lowered.

  Furthermore, as the “silicon oxide” used in each of the above embodiments, it is desirable to use silicon dioxide having at least 20% X-ray crystal structure. This is because if the silicon dioxide having a crystallinity of less than 20%, that is, a crystal structure of less than 20% is used, the evaporation rate of the deposition material and the barrier property of the deposited film are lowered. In the measurement of the crystal part and the non-crystal part of silicon dioxide, each peak is separated using an X-ray diffractometer (XRD), and the degree of crystallinity is obtained from the ratio of integrated intensities.

  Therefore, as a deposition material used in this embodiment, the ratio of the total number of atoms of silicon (Si) and tin (Sn) to the number of atoms of oxygen (O) (O / (Si + Sn)), tin (Sn) In addition to the ratio of the number of atoms of silicon (Si) (Sn / Si), the bulk density is suitably controlled, and the crystallinity of silicon dioxide is further controlled, so that the splash is higher than that of conventional deposition materials. The gas barrier vapor deposition film 10 having a high barrier property can be obtained without causing the phenomenon.

  Hereinafter, the Example of the manufacturing method of the gas barrier vapor deposition film which concerns on this invention is described concretely.

<Example 1>
For metal silicon, a powder having a diameter of 50 μm or less is 95% or more, and for silicon dioxide, a crystal structure is 95% and a powder having a diameter of 50 μm or less is 95% or more. As the metal tin, 95% or more of powder having a diameter of 50 μm or less was used. The ratio of the total number of atoms of silicon (Si) and tin (Sn) to the number of atoms of oxygen (O) (O / (Si + Sn)) is set to 1.7, so that tin (Sn) and silicon (Si) A deposition material made of metal silicon, silicon dioxide, and metal tin mixed so that the atomic ratio (Sn / Si) is 0.07 is prepared, and then the bulk density is 1.0 g / cm ³ by press working. It was press-molded so that

  Further, using an electron beam heating type vacuum deposition apparatus, the mixed deposition material is evaporated by emitting and irradiating an electron beam from an electron gun to form a film on the polymer film substrate 11. did.

<Example 2>
Similar to the vapor deposition material produced in Example 1, metal silicon having a powder having a diameter of 50 μm or less having a diameter of 95% or more is used, and silicon dioxide contains a crystal structure of 95% and has a diameter of 50 μm or less. The powder having 95% or more was used, and the metal tin having a diameter of 50 μm or less was 95% or more. The ratio of the total number of atoms of silicon (Si) and tin (Sn) to the number of atoms of oxygen (O) (O / (Si + Sn)) is set to 1.3, so that tin (Sn) and silicon (Si) After producing a deposition material composed of metallic silicon, silicon dioxide, and metallic tin mixed so that the atomic ratio (Sn / Si) is 0.06, the bulk density is 1.0 g / s as in Example 1. It was press-molded so as to cm ^3.

<Example 3>
Moreover, after preparing the vapor deposition material which mixed the powder material similar to Example 1 mentioned above, it press-molded so that a bulk density might be 0.8 g / cm < ³ >.

<Example 4>
Furthermore, after preparing the vapor deposition material which mixed the powder material similar to Example 1 mentioned above, it press-molded so that bulk density might be 1.7 g / cm < ³ >.

  Next, a comparative example for comparison with the above-described embodiment will be described.

<Comparative Example 1>
The metal silicon used was a powder having a diameter of 50 μm or less of 95% or more, and the silicon dioxide containing a crystal structure containing 95% and a powder having a diameter of 50 μm or less was 95% or more. At this time, a deposition material made of metal silicon and silicon dioxide mixed so that the ratio of the number of atoms of silicon (Si) to the number of atoms of oxygen (O) (O / Si) was 1.7 was prepared. Press molding was performed so that the density was 1.0 g / cm ³ .

<Comparative example 2>
The metal silicon used was 95% or more of powder having a diameter of 50 μm or less, and the metal tin was 95% or more of powder having a diameter of 50 μm or less. Then, the ratio of the total number of atoms of silicon (Si) and tin (Sn) to the number of atoms of oxygen (O) (O / (Si + Sn)) is 1.7, so that tin (Sn) and silicon (Si ) To form a deposition material composed of metallic silicon and metallic tin mixed so that the ratio of the number of atoms (Sn / Si) is 0.18, and press-molded so that the bulk density is 1.0 g / cm ^3. did.

<Comparative Example 3>
In addition, a metal tin having a diameter of 50 μm or less is used for metal tin of 95% or more, and silicon dioxide containing a crystal structure of 95% and a powder having a diameter of 50 μm or less is 95% or more. . The ratio of the total number of atoms of silicon (Si) and tin (Sn) to the number of atoms of oxygen (O) (O / (Si + Sn)) is set to 2.0, and tin (Sn) and silicon (Si ) To produce a vapor deposition material composed of metallic tin and silicon dioxide mixed so that the ratio of the number of atoms (Sn / Si) is 0.08, and press molding so that the bulk density is 1.0 g / cm ^3. did.

  Therefore, for the gas barrier vapor deposition films of Examples 1 to 4 and Comparative Examples 1 to 3 manufactured as described above, the ratio of the number of atoms of the vapor deposition material O / (Si + Sn) and Sn using the following measurement method / Si was measured, and the crystallinity of silicon dioxide was measured.

  In addition, the occurrence of splash during vapor deposition was checked, and the water vapor transmission rate was measured and evaluated. Further, the ratio of the number of atoms of the deposited film evaporated by evaporation, O / (Si + Sn) and Sn / Si, and metal Sn / Sn were measured.

<O / (Si + Sn) and Sn / Si, and metal Sn / Sn of the deposited film>
The O / (Si + Sn) and Sn / Si and metal Sn / Sn of the vapor deposition films in the gas barrier vapor deposition films of Examples 1 to 4 and Comparative Examples 1 to 3 described above were measured using the following method.

  Measurement Method: The polymer film substrate 11 on which the inorganic oxide film 12 was formed was cut into a 10 mm × 10 mm square, and the composition of the film was analyzed using an X-ray photoelectron spectrometer (ESCA). Composition analysis was repeated three or more times in the depth direction of the deposited film with Ar (argon) ions, the average was obtained, and O / (Si + Sn) and Sn / Si, and metal Sn / Sn were obtained.

<O / (Si + Sn) and Sn / Si as vapor deposition materials>
About the material for vapor deposition produced in Examples 1-4 and Comparative Examples 1-3, O / (Si + Sn) and Sn / Si were used for the energy dispersive X-ray-spectral-analysis apparatus (JDE-2300 ... made by JEOL). Asked.

<About the degree of crystallinity of the silicon dioxide vapor deposition material>
About the crystallinity degree of the silicon dioxide of the vapor deposition material produced in Examples 1-4 and Comparative Examples 1-3, it calculated | required using the X-ray-diffraction apparatus (Rigaku RINT-UltimaIV).

<About splash>
The gas barrier vapor deposition films of Examples 1 to 4 and Comparative Examples 1 to 3 were cut into an area of width 500 mm × length 100 m, and about these gas barrier vapor deposition films, whether there are any pinholes and foreign matters due to splash by visual inspection. Examined. At this time, as for the evaluation of the presence or absence of splash, the case where there is no pinhole or foreign matter due to splash is indicated as ◯, the number of pinholes or foreign matter due to splash is 1 to 10 and Δ is 11 or more due to splash. Some were marked with x.

<About water vapor barrier properties>
The water vapor barrier properties of the gas barrier vapor deposition films of Examples 1 to 4 and Comparative Examples 1 to 3 were measured at 40 ° C. and 90% RH using a water vapor permeability measuring device (trade name; MOCON PERMATRAN 3/21) manufactured by Modern Control. Measured in the atmosphere.

  Therefore, when the required characteristic items are measured for the vapor deposition materials and gas barrier vapor deposition films of Examples 1 to 4 and Comparative Examples 1 to 3 manufactured as described above, measurement results as shown in FIG. 2 are obtained. It was.

<Evaluation of measurement results>
As shown in FIG. 2, in the gas barrier vapor deposition films of Examples 3 and 4, it was confirmed that splash was generated to the extent that the water vapor barrier property was not deteriorated, whereas the gas barrier vapor depositions of Example 1 and Example 2 were confirmed. There was no splash on the film. From these results, the occurrence of splash can be suppressed by setting the bulk density of the vapor deposition material within a predetermined setting range.

Furthermore, the gas barrier vapor deposition films of Example 1 and Example 2 manage the crystallinity of silicon dioxide as a vapor deposition material, add metal tin to the vapor deposition material, and add O / (Si + Sn) and Sn / Si in the vapor deposition film. In addition, since the metal Sn / Sn is managed, the water vapor barrier property is remarkably improved. That is, the gas barrier vapor deposition films of Comparative Examples 1 to 3 have a water vapor barrier property worse than 1 g / m ² · day, whereas the gas barrier vapor deposition films of Examples 1 to 4 are crystallized from silicon dioxide as a vapor deposition material. From 1 g / m ² · day, the vapor deposition film made of the vapor deposition material added with metallic tin suitably manages O / (Si + Sn) and Sn / Si of the vapor deposition film, and metal Sn / Sn. A good water vapor barrier property is obtained, and it is considered that the water vapor barrier property is improved.

  The transparent gas barrier film according to the present invention has high productivity, is inexpensive, and has high gas barrier performance. Therefore, a member that needs to block oxygen and water vapor in the packaging field or non-packaging field of food, daily necessities, medical products, etc. Can be widely adapted to.

  In addition, the said embodiment and Example are shown as an example and are not intending limiting the range of invention. Each of the above embodiments and examples can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the spirit of the invention. These embodiments, examples, and modifications thereof are included in the scope and gist of the invention, and are included in the invention described in the claims and the equivalents thereof.

  DESCRIPTION OF SYMBOLS 10 ... Gas barrier vapor deposition film, 11 ... Polymer film base material, 12 ... Inorganic oxide film.

Claims (5)

A polymer film substrate;
A gas barrier vapor deposition film having a vapor deposition film deposited as a SiOx / SnOy film on one side or both sides of the polymer film substrate,
Before the total number of atoms of tin (Sn) and silicon Ki蒸-deposit (Si), atomic ratio of oxygen (O) (O / (Si + Sn)) is 1.0 to 2.0, tin The ratio of the number of atoms of (Sn) and silicon (Si) (Sn / Si) is 0.03 to 0.15,
During pre Ki蒸-deposit, there is a metal Sn peak represents a metal bond,
A gas barrier vapor-deposited film, wherein the ratio of metal Sn peak area to Sn peak area present in the vapor deposition film (metal Sn / Sn) is 0.1 to 1.0. A method for producing a gas barrier vapor-deposited film according to claim 1,
A material for vapor deposition by a heating method containing both metallic silicon and silicon dioxide powder and metallic tin powder, wherein the total number of atoms of silicon (Si) and tin (Sn) and oxygen (O) The ratio of the number of atoms (O / (Si + Sn)) is 0.3 to 1.8, and the ratio of the number of atoms of tin (Sn) and silicon (Si) (Sn / Si) is 0.03 to 0.00. the deposition material is 15, and evaporated by vacuum evaporation apparatus of the electron beam heating method, production of the gas barrier vapor deposition film characterized in that it has deposited the deposited film on one or both surfaces of the polymer film substrate Method. ^3. The method for producing a gas barrier vapor-deposited film according to claim 2, wherein the vapor density of the vapor deposition material is in the range of 0.9 to 1.5 g / cm < ³ >.   3. The method for producing a gas barrier vapor-deposited film according to claim 2, wherein the silicon dioxide powder contains at least 20% of a crystal structure.   The metal silicon powder having a diameter of 50 μm or less is 95% or more, the silicon dioxide contains 95% of a crystal structure, and the powder having a diameter of 50 μm or less is 95% or more, and the metal The method for producing a gas barrier vapor-deposited film according to claim 2, wherein the powder having a diameter of tin of 50 µm or less is 95% or more.

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