JP4867906B2 - Transparent barrier film - Google Patents

Description

  The present invention relates to a transparent barrier film, and more specifically, is excellent in transparency, oxygen gas barrier property, water vapor barrier property, etc. The present invention relates to a transparent barrier film useful as a packaging material suitable for packaging.

Conventionally, as barrier materials useful as packaging materials suitable for filling and packaging articles such as foods and drinks, various types of barrier materials have been developed and proposed. Recently, plastic films have been proposed. A vapor-deposited thin film of inorganic oxide such as silicon oxide or aluminum oxide is applied to at least one surface of the substrate using physical vapor deposition (PVD) such as vacuum deposition, sputtering, or ion plating. A transparent barrier film formed or a transparent barrier film formed by forming a vapor-deposited thin film of silicon oxide using a chemical vapor deposition method (CVD method) has attracted attention.
Thus, in the transparent barrier film as described above, as a technique for improving its oxygen gas barrier property, for example, a corona discharge treatment, a glow discharge treatment, etc., in advance on the surface of a plastic film as a base film. By roughening the surface by applying or coating a urethane anchor coating agent, etc., to improve the adhesion between the plastic film as the base film and the deposited thin film, Alternatively, a method of improving the barrier property by coating hydrogen peroxide on the surface of the silicon oxide vapor deposition film has been proposed (see, for example, Patent Document 1).
Furthermore, in the above transparent barrier film, as a measure for preventing deterioration of oxygen gas barrier property due to mechanical stress, etc., even after a post-processing step such as printing or laminating, aluminum oxide There has also been proposed a method of forming a protective film layer by coating a primer composition containing a polymer material as a main component after forming a vapor-deposited thin film.
In addition, in a transparent gas barrier film formed by forming a vapor deposition film of an inorganic oxide such as aluminum oxide, moisture is adsorbed offline after vapor deposition of aluminum oxide, and then moisture is adsorbed at a temperature higher than the temperature. There has been proposed a method for producing a transparent gas barrier film with improved transparency, gas barrier properties, etc. by heat treatment (see, for example, Patent Document 2).
JP-A-8-197675 Japanese Patent No. 26389797

However, in the transparent barrier film as described above, for example, when forming a vapor-deposited thin film of aluminum oxide, the raw material aluminum is heated and evaporated using an electron beam or the like, and oxygen gas is generated in the generated aluminum vapor. It is extremely difficult to find conditions for producing a transparent barrier film having transparency and excellent oxygen gas barrier properties, etc. .
For example, if the degree of oxidation of aluminum during vapor deposition is increased in order to improve transparency, the transparency is improved, but there is a problem that oxygen gas barrier properties, particularly water vapor barrier properties are deteriorated.
In addition, the transparent barrier film having an aluminum oxide vapor-deposited thin film is weak in elongation, and has a problem that cracks occur in the aluminum oxide vapor-deposited thin film at an elongation of about 2% or more. It has the problem of being inferior in processability.
Further, in the case of forming a vapor-deposited thin film of aluminum oxide after previously coating a urethane-based organic anchor coating agent on the surface of a plastic film as a base film, the anchor coating agent is used. Due to the residual solvent contained in the coating film, the degree of vacuum during the deposition is reduced or the coating film by the anchor coating agent itself is soft. The deposited aluminum oxide thin film does not grow well on the surface of the film, and it is extremely difficult to form a desirable deposited aluminum oxide thin film. As a result, the deposited aluminum oxide has excellent oxygen gas barrier properties, water vapor barrier properties, etc. There is a problem that it is difficult to produce a transparent barrier film having a thin film.
Furthermore, a method for forming a protective film layer by coating a primer composition containing a polymer material as a main component on the aluminum oxide vapor-deposited thin film surface involves a manufacturing process in the coating itself. As a result, the cost increases. In addition, a method for improving the barrier property by coating hydrogen peroxide on the surface of the deposited silicon oxide film has been proposed, but the effect can be expected as such, but it is still sufficient. In fact, it is difficult to produce a transparent gas barrier film having a high barrier property that can satisfy the above, and in addition, since such an operation itself increases the production process, There is a problem of increasing the manufacturing cost.
Furthermore, the method of adsorbing moisture and the like on the surface of the deposited film after forming a vapor deposition film as described above, and then subjecting it to a high temperature heat treatment has a problem in terms of production cost because the number of production steps increases as described above. There is something.
Therefore, the present invention is excellent in transparency, oxygen gas barrier property, water vapor barrier property, etc., and can be produced at low cost. For example, various articles such as food and drink, pharmaceuticals, electronic parts, cosmetics, detergents, etc. It is to provide a transparent barrier film useful as a packaging material suitable for filling and packaging.

  As a result of various studies to solve the above-mentioned problems, the present inventor used an electron beam type physical vapor deposition method on at least one side of a transparent polymer film to form aluminum oxide. When the vapor deposition thin film is provided, the aluminum oxide vapor deposition thin film faces the surface of the film thickness, and the aluminum element: oxygen element content ratio (aluminum element content / oxygen element content) constituting the vapor deposition film. That is, when a transparent barrier film was produced by forming an aluminum oxide vapor deposited thin film in which the aluminum element content in the aluminum oxide vapor deposited thin film was increased toward the surface of the film thickness, The strength against the elongation of the deposited thin film of aluminum oxide increases, and the impact resistance and wettability of the deposited thin film surface are improved. For example, printing processing, laminating It is excellent in post-processing suitability such as processing, bag-making processing, etc., and prevents cracks etc. from occurring in the aluminum oxide vapor-deposited thin film at the time of processing, thereby excellent in oxygen gas barrier property, water vapor barrier property, etc. In addition, it is excellent in transparency and can be manufactured at low cost. For example, it is transparent as a packaging material suitable for filling and packaging various articles such as foods and drinks, pharmaceuticals, electronic parts, cosmetics, detergents, etc. The present invention has been completed by finding that a barrier film can be produced.

  That is, the present invention comprises a vapor deposition film in which an aluminum oxide vapor deposition thin film by an electron beam type physical vapor deposition method is provided on at least one side of a polymer film having transparency. The present invention relates to a transparent barrier film characterized in that the thin film is formed by increasing the content ratio of aluminum element: oxygen element constituting the deposited film toward the surface of the film thickness.

  The present invention provides an aluminum oxide vapor-deposited thin film on at least one surface of a transparent polymer film using an electron beam physical vapor deposition method. Increasing the aluminum element: oxygen element content ratio (aluminum element content / oxygen element content) constituting the vapor deposition film toward the surface of the film thickness, that is, the aluminum element in the vapor deposition thin film of aluminum oxide A transparent barrier film is produced by forming an aluminum oxide vapor deposition thin film having a higher content rate toward the surface of the film thickness, and the strength against the elongation of the aluminum oxide vapor deposition thin film itself is increased. The impact resistance, wettability, etc. of the deposited thin film surface are improved. For example, they are excellent in post-processing suitability such as printing, laminating, bag making, etc. It is possible to prevent the occurrence of cracks and the like in the deposited thin film of aluminum oxide, thereby being excellent in oxygen gas barrier property, water vapor barrier property and the like, and in its transparency, and can be produced at low cost. For example, it is possible to produce a transparent barrier film useful as a packaging material suitable for filling and packaging various articles such as foods and drinks, pharmaceuticals, electronic parts, cosmetics, detergents, and others.

The above-described present invention will be described in more detail below.
First, the method for producing the transparent barrier film according to the present invention will be described. As the production method, basically, a method capable of forming an aluminum oxide vapor-deposited thin film may be used. For example, an aluminum metal or the like is used. While vaporizing this, oxygen gas is supplied, and aluminum oxide is deposited by physical vapor deposition methods (physical vapor deposition method, physical vapor deposition method, PVD method) such as vacuum deposition method, sputtering method, ion plating method, etc. Any method may be used as long as it can form a thin film.
In the above, for example, an electron beam (EB) method, a high-frequency induction heating method, a resistance heating method, or the like is used as a heating method for the vapor deposition material.

Thus, in the present invention, the method for producing the transparent barrier film according to the present invention will be specifically described with reference to a most preferred example. FIG. 1 shows a winding for producing an aluminum oxide deposited thin film by an electron beam method. It is a schematic block diagram which shows the outline | summary of a structure of a take-off type vacuum evaporation system.
As shown in FIG. 1, in a vacuum chamber 2 of a take-up vacuum deposition apparatus 1, a polymer film 4 having transparency is fed from an unwinding roll 3 to a coating drum via a guide roll 5. 6 through the deposition chamber-7.
Thus, in the above-described vapor deposition chamber 7, the aluminum 9 as the vapor deposition source is put in the crucible 8, and the surface 10 of the aluminum 9 is generated by the electron gun 11. Shooting with a pre-programmed deflection at 12 causes the aluminum 9 to evaporate from the surface 10 of the aluminum 9 to generate vapor of the aluminum 9.
Next, the aluminum vapor generated above is reacted in advance with the aluminum vapor and oxygen gas while supplying oxygen gas or the like from the oxygen gas cylinder 13 through the gas pipe 14 and the oxygen gas supply port 15 to the aluminum oxide vapor generated above. And depositing the produced aluminum oxide on the polymer film 4 having transparency passing through the coating zone 16 on the cooled coating drum 6 through masks 17 and 17. Then, an aluminum oxide vapor-deposited thin film is formed.
Next, the transparent polymer film 4 on which the aluminum oxide vapor-deposited thin film is formed as described above is fed into the vacuum chamber-2 and wound on the winding roll 18 through the guide roll 5 ', thereby making the present invention. A transparent barrier film can be produced.
In the above, the degree of vacuum in the deposition chamber is about 1 × 10 ⁻⁵ to 1 × 10 ⁻² Torr, and the amount of oxygen gas introduced from the gas pipe is adjusted according to the amount of evaporation of aluminum. Is done.
The above illustration is an example, and the present invention is not limited thereto.

By the way, in the present invention, when the reactive vapor deposition method of aluminum vapor and oxygen gas is used as described above, the irradiation position of the electron beam when the electron beam shoots the surface of the aluminum nitride, which is the evaporation material, This is a major factor in determining the film structure of the aluminum oxide vapor-deposited thin film to be formed, that is, the film physical properties such as oxygen gas barrier property, water vapor barrier property, and post-processing suitability of the resulting aluminum oxide vapor-deposited thin film.
In the present invention, the relationship between the electron beam irradiation position and the film physical properties of the resulting aluminum oxide vapor-deposited thin film will be described with reference to FIGS.
FIG. 2 shows a case where the irradiation position of the electron beam is directly below the oxygen gas supply port in the take-up vacuum deposition apparatus for producing the aluminum oxide deposited thin film by the electron beam method shown in FIG. FIG. 3 is a schematic configuration diagram showing an outline of the configuration, and FIG. 3 shows the irradiation position of the electron beam in the take-up vacuum deposition apparatus for producing the aluminum oxide deposited thin film by the electron beam method shown in FIG. FIG. 4 is a schematic configuration diagram showing an outline of the configuration when the oxygen gun is located on the electron gun side from the oxygen gas supply port, and FIG. 4 is a winding for manufacturing an aluminum oxide vapor deposition thin film by the electron beam system shown in FIG. FIG. 5 is a schematic configuration diagram showing an outline of a configuration in a case where the irradiation position of an electron beam is on the back side with respect to an electron gun from an oxygen gas supply port in a take-type vacuum deposition apparatus.

First, in the present invention, as shown in FIG. 2, electron beams shown in Figure 1 above - the take-up type vacuum vapor deposition apparatus 1 for producing an aluminum oxide deposited film by beam method, as shown by the dotted line L _1, the electronic When the irradiation position P _{1 of the} beam 12 is directly below the position P ₂ of the oxygen gas supply port 15, the resulting aluminum oxide vapor-deposited thin film has an aluminum element in the thickness direction (depth direction): The content ratio with the oxygen element is about 0.7 to 0.9 in the vicinity of the interface of the polymer film having transparency as the base film and the outermost surface of the deposited thin film, and in the intermediate layer portion, it is 0.2 to It is about 0.3 (see FIG. 5).
Thus, the aluminum oxide vapor-deposited thin film having the above-described film structure has sufficient transparency, but has insufficient water vapor barrier properties, and is inferior to conventional products in terms of post-processing suitability. Is.

Then, in the present invention, as shown in FIG. 3, electron beam shown in Figure 1 above - the take-up type vacuum vapor deposition apparatus 1 for producing an aluminum oxide deposited film by beam method, as shown by the dotted line L _2, When the irradiation position P ₁ of the electron beam 12 is closer to the electron gun 11 than the position P ₂ of the oxygen gas supply port 15, the resulting aluminum oxide vapor-deposited thin film is in the thickness direction (depth direction). The content ratio of aluminum element: oxygen element decreases from the vicinity of the interface of the polymer film having transparency as the base film toward the outermost surface of the deposited thin film (see FIG. 6).
This means that the oxygen content increases as it approaches the outermost surface, and the transparency of the transparent barrier film obtained thereby is excellent. However, on the other hand, the film structure of the aluminum oxide vapor-deposited thin film has a porous structure because a large amount of excess oxygen is taken into the film, and therefore has poor oxygen gas barrier properties, water vapor barrier properties, etc. Also, in the post-processing suitability, the outermost surface of the aluminum oxide vapor-deposited thin film has the highest degree of oxidation, so that the film becomes hard, and the vapor-deposited thin film is easily cracked due to mechanical stress. In addition, deterioration such as water vapor barrier property is likely to occur.

Further, in the present invention, as shown in FIG. 4, electron beams shown in Figure 1 above - the take-up type vacuum vapor deposition apparatus 1 for producing an aluminum oxide deposited film by beam method, as shown by the dotted line L _3, the electronic When the irradiation position P _{1 of the} beam 12 is on the back side with respect to the electron gun 11 from the position P ₂ of the oxygen gas supply port 15, the resulting aluminum oxide vapor-deposited thin film has a thickness direction (depth). Direction), the content ratio of aluminum element: oxygen element increases from the vicinity of the interface of the polymer film having transparency as the base film toward the outermost surface of the deposited thin film (see FIG. 7).
This is opposite to the case shown in FIG. 3 above, and means that the oxygen content decreases as the outermost surface of the vapor-deposited thin film is approached. However, it is slightly inferior, but on the contrary, it has excellent oxygen gas barrier properties, water vapor barrier properties, etc., and the impact resistance of the outermost surface of the vapor-deposited thin film is improved, and it is most excellent in post-processing suitability. Is.

In addition, in this invention, about the transparent barrier film obtained using the vacuum evaporation system shown in said FIG. 2-4, the content rate of the aluminum element and oxygen element in an aluminum oxide vapor deposition thin film was measured by X-ray electron spectroscopy. Measurement was performed using an apparatus [Esca, ESCA, UK, manufactured by KRATOS, model name, AXIS-HS type].
In the above, the measurement conditions were Al-Kα1 (monochrome) as a light source, and the output was 1486.6 eV. The results are shown in FIGS.
Thus, FIG. 5 is a graph showing the results of measurement of the transparent barrier film obtained using the vacuum vapor deposition apparatus shown in FIG. 2, and FIG. 6 is the vacuum vapor deposition apparatus shown in FIG. FIG. 7 is a graph showing the results of measurement performed on the transparent barrier film obtained using the vacuum vapor deposition apparatus shown in FIG. 4 above. It is.
The measurement results are as described above.
That is, as shown in FIG. 5, the aluminum oxide vapor-deposited thin film obtained using the vacuum vapor deposition apparatus shown in FIG. 2 has a content ratio of aluminum element: oxygen element in the thickness direction (depth direction), In the vicinity of the interface of the polymer film having transparency as the base film and the outermost surface of the deposited thin film, it is about 0.7 to 0.9, and in the intermediate layer portion is about 0.2 to 0.3 (see FIG. 5).
Moreover, as shown in FIG. 6, the aluminum oxide vapor-deposited thin film obtained using the vacuum vapor deposition apparatus shown in FIG. 3 has a content ratio of aluminum element: oxygen element in the thickness direction (depth direction): It decreases from the vicinity of the interface of the polymer film having transparency as the base film toward the outermost surface of the deposited thin film (see FIG. 6).
Furthermore, as shown in FIG. 7, the aluminum oxide vapor-deposited thin film obtained using the vacuum vapor deposition apparatus shown in FIG. 4 has a content ratio of aluminum element: oxygen element in the thickness direction (depth direction): It increases from the vicinity of the interface of the polymer film having transparency as the base film toward the outermost surface of the deposited thin film (see FIG. 7).

In the present invention, as is apparent from FIGS. 5 to 7 described above, when the reactive vapor deposition method of aluminum vapor and oxygen gas is used as described above, the surface of the aluminum nitride whose electron beam is an evaporation material is used. The electron beam irradiation position at the time of shooting determines the film structure of the resulting aluminum oxide vapor deposited thin film, that is, the film physical properties such as the oxygen gas barrier property, water vapor barrier property, post-processing suitability, etc. of the resulting aluminum oxide vapor deposited thin film It is a big factor.
And Thus, in the present invention, as shown in FIG. 4 above, electron beam shown in Figure 1 above - the take-up type vacuum vapor deposition apparatus 1 for producing an aluminum oxide deposited film by beam method, a dotted line L ₃ As shown, the irradiation position P ₁ of the electron beam 12 is located on the back side with respect to the electron gun 11 from the position P ₂ of the oxygen blowing port 15. At this position, as shown in FIG. The surface 10 of the aluminum 9 in the crucible 8 is shot with an electron beam 12 generated by using an electron gun 11, and vapor of aluminum 9 is generated from the surface 10, and then the aluminum 9 generated above is generated. While supplying oxygen gas or the like from the oxygen gas cylinder 13 through the gas pipe 14 and the oxygen gas supply port 15 in advance to the steam, the aluminum vapor and the oxygen gas are reacted to produce aluminum oxide. An aluminum oxide vapor deposition thin film is formed by depositing and laminating on the transparent polymer film 4 passing through the coating zone 16 on the coating drum 6 on which the cooled aluminum oxide is cooled, through masks 17 and 17. It is desirable to produce a transparent barrier film by forming a film.

In the present invention, the transparent barrier film according to the present invention produced as described above has an aluminum oxide vapor-deposited thin film directed toward the surface of the film thickness as shown in FIG. It is characterized in that the content ratio of aluminum element: oxygen element constituting is increased.
Specifically, the aluminum oxide vapor-deposited thin film comprises an aluminum oxide vapor-deposited film represented by the formula AlOx (where X represents a number of 1 to 1.5), and further, an aluminum oxide vapor-deposited thin film A transparent barrier film can be produced, wherein the content ratio of aluminum element: oxygen element is in the range of 0.1 to 9.0 in the outermost surface layer portion of the deposited film. It can be done.
In the transparent barrier film according to the present invention, the content ratio of aluminum element: oxygen element constituting the aluminum oxide vapor-deposited thin film is desirably in the range of 0.1 to 9.0 as described above. Further, the content ratio of aluminum element: oxygen element constituting the aluminum oxide vapor-deposited thin film is in the range of 0.3 to 6.0 at the outermost surface layer portion of the vapor-deposited film, and also the oxidation It is desirable that there is a transparent barrier film in which the aluminum element: oxygen element content ratio constituting the aluminum deposited thin film is in the range of 0.6 to 4.0 at the outermost surface layer portion of the deposited film thickness. Is.
In the above, when it is 0.1 or less, oxygen gas barrier property, water vapor barrier property, post-processing suitability, etc. are all insufficient, and when it is 9.0 or more, the transparency of the transparent barrier film is impaired. Is.

In the production method as described above, as the polymer film having transparency, a colorless and transparent polymer film used as an ordinary packaging material can be used.
For example, polyolefin resin films such as polyethylene and polypropylene, polyester resin films such as polyethylene terephthalate and polyethylene naphthalate, polyamide resin films such as various nylon films, polystyrene resin films, polycarbonate It is possible to use various resin films or sheets such as a resin-based resin film, an acetal-based resin film, a saponified film of an ethylene-vinyl acetate copolymer, and the like.
The resin film or sheet as described above may be, for example, a biaxially stretched film or sheet stretched in a biaxial direction by a tenter method or a tuber method, The thickness is preferably about 3 to 200 μm, more preferably about 5 to 100 μm.
In addition, the resin film or sheet as described above is used for corona discharge treatment, plasma discharge treatment, or anchoring, which are known surface modification methods, in order to improve adhesion to the aluminum oxide vapor-deposited thin film. Anchor coating with a coating agent can also be performed.

The transparent barrier film A according to the present invention produced by the production method as described above has an electronic film on at least one side of a transparent polymer film 4 as shown in the schematic cross-sectional view of FIG. A vapor deposition film provided with an aluminum oxide vapor-deposited thin film 21 by a mud physical vapor deposition method, and the aluminum oxide vapor-deposited thin film 21 is directed toward the surface of the film thickness (in the depth direction). It is characterized in that the content ratio of aluminum element: oxygen element constituting is increased.
In the transparent barrier film according to the present invention, the film thickness of the aluminum oxide vapor-deposited thin film is preferably about 50 to 2000 mm, more preferably about 100 to 1000 mm. In the above, if the film thickness of the aluminum oxide vapor-deposited thin film is less than 50 mm, film unevenness occurs, and it is difficult to produce an aluminum oxide vapor-deposited thin film having sufficient oxygen gas barrier properties, water vapor barrier properties, etc. When the film is formed at 2000 mm or more, after forming the aluminum oxide vapor-deposited thin film, microcracks and the like are likely to occur in the vapor-deposited thin film at the stage of winding up the transparent barrier film, and the like, as described above, sufficient oxygen gas barrier property, water vapor barrier property, etc. It becomes difficult to produce an aluminum oxide vapor-deposited thin film having the following.

The transparent barrier film according to the present invention comprises a vapor-deposited film in which an aluminum oxide vapor-deposited thin film by an electron beam physical vapor deposition method is provided on at least one side of a polymer film having transparency. The aluminum oxide vapor-deposited thin film is formed by increasing the content ratio of aluminum element: oxygen element constituting the vapor-deposited film toward the surface of the film thickness, that is, the content of aluminum element in the aluminum oxide vapor-deposited thin film By increasing the height toward the film surface, it is possible to increase the strength against the elongation of the vapor deposited thin film itself and improve the crack resistance of the vapor deposited thin film surface, thereby having a conventional transparent barrier film. It can significantly improve post-processing aptitudes such as printing, laminating, bag making, etc. Preventing occurrence such as a rack, oxygen gas barrier properties, in which is excellent in water vapor barrier properties and the like.
Further, the transparent barrier film according to the present invention is such that the aluminum oxide vapor-deposited thin film is formed by increasing the content ratio of aluminum element: oxygen element constituting the vapor-deposited film toward the surface of the film thickness, that is, By increasing the aluminum element content in the aluminum oxide vapor deposited thin film toward the film surface, the impact resistance of the vapor deposited thin film surface is improved, for example, by contacting a guide roll or the like during production, The occurrence of microcracks or the like on the surface of the deposited thin film can be suppressed, thereby preventing deterioration of oxygen gas barrier properties, water vapor barrier properties, and the like.
Furthermore, the transparent barrier film according to the present invention is such that the aluminum oxide vapor-deposited thin film increases the content ratio of aluminum element: oxygen element constituting the vapor-deposited film toward the surface of the film thickness, That is, by reducing the degree of oxidation of aluminum on the surface of the aluminum oxide vapor deposited thin film, and conversely, by increasing the aluminum content toward the surface of the aluminum oxide vapor deposited thin film, the wettability of the vapor deposited thin film is improved. In post-processing, for example, it is excellent in suitability (strength) for printing, laminating, etc., and can prevent deterioration of oxygen gas barrier property, water vapor barrier property and the like.

The transparent barrier film according to the present invention produced as described above is, for example, a packaging material such as a resin film, a paper base material, a metal material, a synthetic paper, a cellophane, etc. In combination, for example, various composite films can be manufactured by laminating, and packaging materials suitable for filling and packaging various articles can be manufactured.
Specifically, as the resin film, for example, 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, ethylene-acrylic acid or methacrylic acid copolymer, acid-modified polyolefin resin, methylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin , Polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (meth) acrylic resin, polyacrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene- Styrene copolymer (AB Resin), polyester resin, polyamide resin, polycarbonate resin, polyvinyl alcohol resin, saponified ethylene-vinyl acetate copolymer, fluorine resin, diene resin, polyacetal resin A resin, polyurethane resin, nitrocellulose, or other known resin film or sheet may be arbitrarily selected and used.
In the present invention, the above-described film or sheet may be any of unstretched, uniaxially or biaxially stretched.
The thickness is arbitrary, but can be selected from a range of several μm to 300 μm.
Furthermore, in the present invention, the film or sheet may be a film having any property such as extrusion film formation, inflation film formation, and coating film.
In addition, in the above, as the paper base, for example, a paper base such as a strong sized bleached or unbleached paper, or a pure white roll paper, kraft paper, paperboard, processed paper, or the like is used. can do.
In the above, as the paper substrate constituting the paper layer, it is desirable to use a material having a basis weight of about 80 to 600 g / m ² , preferably a basis weight of about 100 to 450 g / m ² .
In addition, as the metal material, for example, an aluminum foil or a resin film having an aluminum vapor deposition film can be used.

Next, in the present invention described above, a method for producing a composite film using the above materials will be described. As such a method, an ordinary method for laminating packaging materials, for example, wet lamination, is used. , Dry lamination method, solventless dry lamination method, extrusion lamination method, T-die extrusion molding method, co-extrusion lamination method, inflation method, co-extrusion inflation method, etc. be able to.
Thus, in the present invention, when performing the above lamination, if necessary, pretreatment such as corona treatment, ozone treatment, frame treatment, etc. can be applied to the film. , Polyester-based, isocyanate-based (urethane-based), polyethyleneimine-based, polybutadiene-based, organic titanium-based anchor coating agents, or polyurethane-based, polyacrylic-based, polyester-based, epoxy-based, polyvinyl acetate-based Well-known anchor coating agents, adhesives, etc., such as adhesives for laminating, etc. can be used.

Next, in the present invention, a method for making a bag or box using the composite film as described above will be described. For example, when the packaging container is a soft packaging bag made of a plastic film or the like, the above method is used. Using the composite film manufactured in step 1, the inner heat-seal resin layer faces the opposite side, and the two layers are folded or overlapped, and the peripheral edge of the heat-seal resin layer is overlapped. -A bag body can be constructed by providing a seal portion.
Thus, as a bag-making method, the above-mentioned composite film is folded with its inner layer facing each other, or two of them are overlapped, and the peripheral edge of the outer periphery is, for example, a side sheet. Seal type, two-sided seal type, three-sided seal type, four-sided seal type, envelope-sealed seal type, jointed seal type (pillar seal type), pleated seal type The various types of packaging containers according to the present invention can be manufactured by heat sealing in the form of a heat sealing such as a flat bottom sealing type, a square bottom sealing type, or the like.
In addition, for example, a self-supporting packaging bag (standing pouch) or the like can be manufactured. In the present invention, a tube container or the like can also be manufactured using the composite film.
In the above, as the heat seal method, for example, a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal and the like are known. It can be done by the method.
In the present invention, a spout such as a one-piece type, a two-piece type, or the like, or a zipper for opening and closing can be arbitrarily attached to the packaging container as described above.

  Next, in the case of a liquid-filled paper container including a paper base material as a packaging container, for example, as a laminated material, a composite film in which a paper base material is laminated is manufactured, and a blank plate for manufacturing a desired paper container is manufactured from this. After that, the body, bottom, head, etc. can be boxed by using the blank plate, and for example, a brick type, flat type or gable top type liquid paper container can be manufactured. . Further, the shape can be any of a rectangular container, a cylindrical paper can such as a round shape, and the like.

In the present invention, the packaging container produced as described above is excellent in transparency, gas barrier properties against oxygen, water vapor and the like, impact resistance, etc., and further, laminating, printing, bag making or box making. It has excellent post-processing suitability, prevents peeling of the deposited thin film as a barrier film, prevents the occurrence of thermal cracks, prevents its deterioration, and has excellent resistance as a barrier film. For example, it is excellent in filling and packaging suitability, storage suitability, etc. for various articles such as foods and drinks, pharmaceuticals, detergents, shampoos, oils, toothpastes, adhesives, adhesives, and other chemicals and cosmetics, etc. Is.
Hereinafter, the present invention will be described in more detail with reference to examples.

A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is mounted on a take-up vacuum deposition apparatus (see FIG. 1 described above). On the other hand, metal aluminum as a deposition material is filled in a ceramic crucible and then coated. The vacuum in the chamber was evacuated to 6 × 10 ⁻⁵ Torr.
Next, an electron beam was generated from the electron gun and irradiated onto the surface of the metal aluminum to heat the surface.
In the above, the irradiation position of the electron beam is a program that is about 5 cm in the direction opposite to the electron gun from the intersection of the perpendicular line drawn from the oxygen gas supply port to the surface of the metal aluminum and the surface of the metal aluminum. Set (see FIG. 4 above).
Next, at the same time as the evaporation of metallic aluminum started, the biaxially stretched polyethylene terephthalate film started to travel. When the traveling speed reached 10 m / s, oxygen gas was supplied from the gas pipe.
The supply amount of the oxygen gas is adjusted while monitoring the degree of vacuum in the chamber and the ultraviolet transmittance monitor of the deposited film, and finally the degree of vacuum is 2 × 10 ⁻⁴ Torr, and the ultraviolet transmittance is 95. % (Biaxially stretched polyethylene terephthalate film was converted to 100%).
As a result, a transparent aluminum oxide vapor-deposited film having a thickness of 220 mm, total light transmittance, and 93% was produced.

A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is mounted on a take-up vacuum deposition apparatus (see FIG. 1 described above). On the other hand, metal aluminum as a deposition material is filled in a ceramic crucible and then coated. The vacuum in the chamber was evacuated to 6 × 10 ⁻⁵ Torr.
Next, an electron beam was generated from the electron gun and irradiated onto the surface of the metal aluminum to heat the surface.
In the above, the irradiation position of the electron beam is a program that is about 8 cm in the direction opposite to the electron gun from the intersection of the perpendicular drawn from the oxygen gas supply port to the surface of the metal aluminum and the surface of the metal aluminum. Set (see FIG. 4 above).
Next, at the same time as the evaporation of metallic aluminum started, the biaxially stretched polyethylene terephthalate film started to travel. When the traveling speed reached 10 m / s, oxygen gas was supplied from the gas pipe.
The supply amount of the oxygen gas is adjusted while monitoring the degree of vacuum in the chamber and the monitor of the ultraviolet transmittance of the deposited film, and finally the degree of vacuum is 2 × 10 ⁻⁴ Torr. % (Biaxially stretched polyethylene terephthalate film was converted to 100%).
As a result, a transparent aluminum oxide vapor-deposited film having a thickness of 220 mm, total light transmittance, and 94% was produced.

(Comparative Example 1)
A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is mounted on a take-up vacuum deposition apparatus (see FIG. 1 described above). On the other hand, metal aluminum as a deposition material is filled in a ceramic crucible and then coated. The vacuum in the chamber was evacuated to 6 × 10 ⁻⁵ Torr.
Next, an electron beam was generated from the electron gun and irradiated onto the surface of the metal aluminum to heat the surface.
In the above, the irradiation position of the electron beam was set by a program so as to be the intersection of the perpendicular drawn from the oxygen gas supply port to the surface of the metal aluminum and the surface of the metal aluminum (see FIG. 2 described above).
Next, at the same time as the evaporation of metallic aluminum started, the biaxially stretched polyethylene terephthalate film started to travel. When the traveling speed reached 10 m / s, oxygen gas was supplied from the gas pipe.
The supply amount of the oxygen gas is adjusted while monitoring the degree of vacuum in the chamber and the ultraviolet transmittance monitor of the deposited film, and finally the degree of vacuum is 2 × 10 ⁻⁴ Torr, and the ultraviolet transmittance is 95. % (Biaxially stretched polyethylene terephthalate film was converted to 100%).
As a result, a transparent aluminum oxide vapor-deposited film having a thickness of 220 mm, total light transmittance, and 93% was produced.

(Comparative Example 2)
A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is mounted on a take-up vacuum deposition apparatus (see FIG. 1 described above). On the other hand, metal aluminum as a deposition material is filled in a ceramic crucible and then coated. The vacuum in the chamber was evacuated to 6 × 10 ⁻⁵ Torr.
Next, an electron beam was generated from the electron gun and irradiated onto the surface of the metal aluminum to heat the surface.
In the above, the irradiation position of the electron beam was set by the program so that it was about 5 cm in the direction of the electron gun from the intersection of the perpendicular drawn from the oxygen gas supply port to the surface of the metal aluminum and the surface of the metal aluminum. (See FIG. 3 above).
Next, at the same time as the evaporation of metallic aluminum started, the biaxially stretched polyethylene terephthalate film started to travel. When the traveling speed reached 10 m / s, oxygen gas was supplied from the gas pipe.
The supply amount of the oxygen gas is adjusted while monitoring the degree of vacuum in the chamber and the monitor of the ultraviolet transmittance of the deposited film, and finally the degree of vacuum is 2 × 10 ⁻⁴ Torr. % (Biaxially stretched polyethylene terephthalate film was converted to 100%).
As a result, a transparent aluminum oxide vapor-deposited film having a thickness of 220 mm, total light transmittance, and 94% was produced.

(Experimental example)
The following data were measured for each of the transparent aluminum oxide deposited films produced in Examples 1-2 and Comparative Examples 1-2.
(1). Gas barrier property evaluation This was evaluated by measuring the oxygen permeability and water vapor permeability of each of the transparent aluminum oxide deposited films produced in Examples 1-2 and Comparative Examples 1-2.
The oxygen permeability was measured with a measuring instrument (model name, OX-TRAN 2/20) manufactured by MOCON, USA under the conditions of a temperature of 25 ° C. and a humidity of 90% RH. Further, the water vapor permeability was measured with a measuring instrument (model name, PERMATRAN 3/31) manufactured by MOCON, USA, under conditions of a temperature of 37.8 ° C. and a humidity of 100% RH. .
(2). Transparency evaluation About this, about each transparent aluminum oxide vapor deposition film manufactured by said Examples 1-2 and Comparative Examples 1-2, a total light transmittance is measured by the method of JIS K-7613, The transparency Sex was evaluated.
(3). Laminate suitability evaluation This is a two-component curable polyurethane adhesive comprising the transparent aluminum oxide vapor-deposited films produced in Examples 1 and 2 and Comparative Examples 1 and 2 and an unstretched polypropylene film having a thickness of 25 μm. And then laminated for 24 hours to produce a composite film, and the composite film thus produced was measured for its oxygen permeability, water vapor permeability, and laminating strength. It was evaluated by doing.
In the above, the dry laminate is formed by applying the above-mentioned adhesive at a coating amount of 4 g / m ^{2 on the} surface of the vapor-deposited thin film of aluminum oxide to form an adhesive layer, and forming an unstretched polypropylene film on the surface of the adhesive layer. Dry lamination was performed.
The oxygen permeability and water vapor permeability are measured in the same manner as described above, and the laminating strength is a tensile tester (manufactured by Orientec Co., Ltd.) cut into a 15 mm wide strip. And then measured by a 180 ° peeling method at a pulling speed of 200 mm / min.
(4). Gelbo suitability evaluation This is about 25 ° C. using a gelbo flex tester according to the MIL-B131H standard for each of the transparent aluminum oxide vapor-deposited films produced in Examples 1-2 and Comparative Examples 1-2. The evaluation was performed by measuring the oxygen permeability and water vapor permeability under the condition of 50% RH. The above-mentioned oxygen permeability and water vapor permeability were measured in the same manner as described above.
The above evaluation results are shown in Table 1 below.

(Table 1)
┌────┬──────────────┬──────────────┐ │ │ Oxygen permeability │ Water vapor permeability │ │ ├── ─────┬──────┼───────┬──────┤ │ │aluminum oxide│composite film│aluminum oxide│composite film│ │ │deposition film│ │ Deposition film │ │ ├────┼───────┼──────┼───────┼──────┤ │Example 1│ 1.5 │ 0 │ 1.3 │ 0.9 │ ├────┼───────┼──────┼───────┼──────┤ │Example 2│ 1.7 │ 1.0 │ 1.8 │ 1.1 │ ├────┼───────┼──────┼───────┼─── ───┤ │Comparative Example 1│ 2.0 │ 1.6 │ 5.3 │ 3.8 │ ├────┼─── ───┼──────┼───────┼──────┤ │Comparative Example 2 │ 2.5 │11.5 │ 6.8 │13.0 │ └── ──┴───────┴──────┴───────┴──────┘
┌────┬──────────┬─────────────────┐ │ │ │ Gas barrier properties after 50 cycles │ │ │Laminé Strength ├───────┬─────────┤ │ │ (gf / 15mm width) │ Oxygen permeability │ Water vapor permeability │ ├────┼────── ────┼───────┼─────────┤ │Example 1│ 430 │ 1.5 │ 1.1 │ ├ ├────┼─────── ────┼───────┼─────────┤ │Example 2│ 410 │ 2.0 │ 1.5 │ ├ ────┼────── ────┼───────┼─────────┤ │Comparative example 1 │ 350 │ 5.9 │ 8.1 │ ├ ────┼─────── ────┼───────┼─────────┤ │Comparative Example 2│ 280 │ 25.0 │ 17 0 │ └────┴──────────┴───────┴─────────┘ In Table 1 above, oxygen permeability is cc / The unit is m ² / day, and the water vapor permeability is a unit of g / m ² / day.

  As is clear from the above results, it was confirmed that the samples of Examples 1 and 2 had characteristics superior to those of Comparative Example 1/3.

  The present invention provides an aluminum oxide vapor-deposited thin film on at least one surface of a transparent polymer film using an electron beam physical vapor deposition method. Increasing the aluminum element: oxygen element content ratio (aluminum element content / oxygen element content) constituting the vapor deposition film toward the surface of the film thickness, that is, the aluminum element in the vapor deposition thin film of aluminum oxide A transparent barrier film is produced by forming an aluminum oxide vapor deposition thin film having a higher content rate toward the surface of the film thickness, and the strength against the elongation of the aluminum oxide vapor deposition thin film itself is increased. The impact resistance, wettability, etc. of the deposited thin film surface are improved. For example, they are excellent in post-processing suitability such as printing, laminating, bag making, etc. It is possible to prevent the occurrence of cracks and the like in the deposited thin film of aluminum oxide, thereby being excellent in oxygen gas barrier property, water vapor barrier property and the like, and in its transparency, and can be produced at low cost. For example, it is useful as a transparent barrier film constituting a packaging material suitable for filling and packaging various articles such as foods and drinks, pharmaceuticals, electronic parts, cosmetics, detergents, and others.

It is a schematic block diagram which shows the outline | summary of a structure of the winding-type vacuum deposition apparatus which manufactures the aluminum oxide vapor deposition thin film by an electron beam system. In the winding-type vacuum vapor deposition apparatus for producing the aluminum oxide vapor deposition thin film by the electron beam method shown in FIG. 1, the outline of the configuration when the electron beam irradiation position is directly under the oxygen gas supply port is shown below. It is a schematic block diagram shown. In the take-up vacuum deposition apparatus for producing the aluminum oxide vapor deposition thin film by the electron beam system shown in FIG. 1, the configuration in the case where the irradiation position of the electron beam is on the electron gun side from the oxygen gas supply port It is a schematic block diagram which shows an outline | summary. In the take-up vacuum deposition apparatus for manufacturing the aluminum oxide deposition thin film by the electron beam method shown in FIG. 1, the irradiation position of the electron beam is on the back side with respect to the electron gun from the oxygen gas supply port. It is a schematic block diagram which shows the outline | summary of the structure in a case. It is a graph which shows the result measured about the transparent barrier film obtained from said FIG. It is a graph which shows the result measured about the transparent barrier film obtained from said FIG. It is a graph which shows the result measured about the transparent barrier film obtained from said FIG. It is a schematic sectional drawing which shows the layer structure of the transparent barrier film concerning this invention.

Explanation of symbols

1 Rewind-type vacuum evaporation system 2 Vacuum chamber
3 Unwinding roll 4 Transparent polymer film 5 Guide roll 5 'Guide roll 6 Coating drum 7 Deposition chamber
8 Crucible 9 Aluminum 10 Surface of aluminum 9 Electron gun 12 Electron beam 13 Oxygen gas cylinder 14 Gas pipe 15 Oxygen gas supply port 16 Coating zone 17 Mask 18 Winding roll L1, L2, L3 Dotted line P1 Electron beam -Irradiation position of the film 12 P2 Position of the oxygen gas supply port 15 21 Aluminum oxide vapor-deposited thin film A Transparent barrier film

Claims (4)

Reactivity of supplying oxygen gas from an oxygen gas supply port while heating and evaporating aluminum metal as a deposition source on at least one side of a polymer film having transparency by an electron beam irradiation heating method When forming an aluminum oxide vapor-deposited thin film by a vapor deposition method, the irradiation position of the electron beam is set behind the electron gun that shoots the electron beam from the position of the oxygen gas supply port. It is a vapor deposition film produced by depositing an aluminum oxide vapor deposition thin film,
The aluminum oxide vapor-deposited thin film comprises an aluminum oxide vapor-deposited film represented by the formula AlOx (where x represents a number of 1 to 1.5),
And said aluminum oxide vapor deposition thin film is the polymer film which has transparency as a base film in the content ratio of aluminum element: oxygen element in the thickness direction (depth direction) of the aluminum oxide vapor deposition thin film. Increasing the aluminum element deposition thin film from the vicinity of the interface toward the outermost surface of the aluminum oxide vapor deposited thin film, and increasing the aluminum element content in the aluminum oxide vapor deposited thin film toward the surface of the film thickness,
And the aluminum oxide which comprises said aluminum oxide vapor deposition thin film: The content ratio of the oxygen element increases in the range of 0.1-9.0 toward the outermost surface of the film thickness of the vapor deposition thin film A deposited thin film ,
The transparent barrier film, wherein the aluminum oxide vapor-deposited thin film has a thickness of 50 to 2000 mm 2. The transparent barrier film according to claim 1, wherein the polymer film having transparency is a polyamide resin film or a polyester resin film. The content ratio of aluminum element: oxygen element constituting the aluminum oxide vapor-deposited thin film is in the range of 0.3 to 6.0 in the outermost surface layer portion of the film thickness of the vapor-deposited film. The transparent barrier film described in any one of -2. The content ratio of aluminum element: oxygen element constituting the aluminum oxide vapor-deposited thin film is in the range of 0.6 to 4.0 at the outermost surface layer portion of the vapor-deposited film thickness. The transparent barrier film described in any one of -2.

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