JPH11151774A - Transparent gas barrier film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To impart not only excellent transparency, gas barrier properties or the like but also excellent post-processing aptitude such as printing, lamination, bag making or the like by providing a coating film based on a silicon oxide film heat-treated under a constant temp. and constant humidity temp. by a polysilazane-containing coating soln. on the surface of a vapor deposition film of inorg. oxide. SOLUTION: A vapor deposition film 3 of inorg. oxide is provided on the surface of a base material film 2 and a coating film 4 based on a silicon oxide film is provided on the surface of this vapor deposition film 3. That is, aluminum is used as a vapor deposition source and a vapor deposition film of aluminum with a thickness of 200 Å is formed on the single surface of a biaxially stretched polyethylene terephthalate film with a thickness of 12 μm by a vacuum vapor deposition method by an electron beam heating system while supplying oxygen gas. Further, a soln. containing 20 wt.% polysilazane is applied to the surface of the vapor deposition film by a bar coater and the coated film is heated at 120 deg.C for 1 hr by a dryer to form a coating film based on silicon oxide with a thickness of 1.2 μm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a transparent gas barrier.
More specifically, the transparent film is excellent in transparency, gas barrier properties against oxygen gas or water vapor, etc., and is also excellent in laminating suitability, for example, food and drink, pharmaceuticals, cosmetics, chemicals, electronic components, The present invention relates to a transparent gas barrier film useful as a packaging material for various articles such as miscellaneous goods and others.

[0002]

2. Description of the Related Art Conventionally, various packing materials have been developed and proposed for filling and packaging various articles such as food and drink, pharmaceuticals, cosmetics, and others. Among them, in recent years,
Various materials have been developed and proposed as a gas barrier material against oxygen gas or water vapor. For example, a polyvinylidene chloride resin, polyvinyl alcohol, or ethylene-vinyl alcohol copolymer is coated on the surface of a plastic film. A material provided with a coating film by coalescence or the like is known. As a gas barrier material, a metal such as aluminum, or an inorganic oxide such as silicon oxide, aluminum oxide, magnesium oxide, or the like is used on the surface of a plastic substrate, and is subjected to vacuum deposition, sputtering, ion plating, or the like. A gas barrier film formed by forming a vapor-deposited film of a metal or an inorganic oxide by using a physical vapor deposition method (PVD method) such as a plating method is also known. Furthermore, recently, a vapor-deposited silicon oxide film is formed using a chemical vapor deposition (CVD) method such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, or a photochemical vapor deposition method. Gas barrier films have also been reported.

[0003]

However, among the gas barrier materials as described above, for example, a material in which a coating film made of a polyvinylidene chloride resin is provided on the surface of a plastic film has an oxygen permeability of 1 cc / m.
It is not suitable for packaging materials requiring a high barrier property such as ² / day or less.
Since it contains chlorine atoms, there is a problem that harmful gas is generated at the time of incineration when disposing after use, and there is also a problem that it is not suitable for recycling. In the gas barrier material described above, a material in which a coating film made of polyvinyl alcohol or an ethylene-vinyl alcohol copolymer is provided on the surface of a plastic film is not limited in terms of gas barrier properties. And the gas barrier property is significantly deteriorated particularly at high temperature or high humidity. Further, in the above gas barrier material, the gas barrier film obtained by forming a vapor deposited film of a metal such as aluminum on the surface of a plastic substrate is opaque, so that the contents cannot be confirmed, In addition, there is a problem that heating by a microwave oven cannot be performed, and further, it is not suitable for recyclability. Furthermore, in the gas barrier material described above, a gas barrier film formed by forming a deposited film of an inorganic oxide such as silicon oxide, aluminum oxide, magnesium oxide, or the like on the surface of a plastic substrate is kneaded or bent. Printing, laminating,
The post-processing of packaging materials such as bag making has the problem that cracks and the like are generated in the deposited film and the gas barrier property is significantly deteriorated. However, there is also a problem that it is technically extremely difficult to obtain a high barrier property of 1 cc and 1 g or less. Further, the gas barrier film obtained by forming a vapor-deposited film of silicon oxide on the surface of the plastic substrate has a problem that the color of the film is slightly brownish and the transparency is insufficient. is there. Further, a gas barrier film formed by forming a vapor-deposited film of an inorganic oxide on the surface of a plastic substrate cannot be used for boiling and retorting because the vapor-deposited film of an inorganic oxide has poor heat resistance. There are also problems. Therefore, the present invention is excellent in transparency, gas barrier properties against oxygen gas or water vapor and the like, and is also excellent in post-processing suitability such as printing, laminating, bag making, and the like, for example, food and drink, pharmaceuticals, cosmetics, An object of the present invention is to provide a transparent gas barrier film which is useful as a packaging material for various articles such as chemicals, electronic parts, miscellaneous goods and others.

[0004]

As a result of various studies to solve the above problems, the present inventor focused on a silicon oxide film formed by a coating solution containing polysilazane, A deposited film of an inorganic oxide is provided, and a coating film mainly composed of a silicon oxide film that is heat-treated at a constant temperature and constant humidity with a coating solution containing polysilazane is provided on the surface of the deposited film of the inorganic oxide to be transparent. When a gas-barrier film was produced, the transparent gas-barrier film was excellent in transparency, gas barrier properties against oxygen gas or water vapor, etc., and was suitable for post-processing suitability such as printing, laminating, and bag making. The present invention has been completed by finding that it is a gas barrier material useful as a packaging material for various articles such as food and drink, pharmaceuticals, cosmetics, chemicals, electronic parts, miscellaneous goods, etc. It is intended.

That is, according to the present invention, an inorganic oxide vapor-deposited film is provided on the surface of a substrate film, and the surface of the inorganic oxide vapor-deposited film is heated under a constant temperature and humidity with a coating solution containing polysilazane. The present invention relates to a transparent gas barrier film having a coating film mainly composed of a treated silicon oxide film.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. First, an example of the structure of the transparent gas barrier film according to the present invention will be described with reference to the accompanying drawings. FIG. 1 is a schematic diagram showing a layer structure of an example of the transparent gas barrier film according to the present invention. FIG.

First, in the transparent gas barrier film 1 according to the present invention, as shown in FIG. 1, an inorganic oxide vapor deposition film 3 is provided on the surface of a base film 2, and the inorganic oxide vapor deposition film 3 is further deposited. The film 3 has a structure in which a coating film 4 mainly composed of a silicon oxide film subjected to heat treatment under a constant temperature and humidity condition with a coating solution containing polysilazane is provided on the surface of the film 3. The above examples are examples of the transparent gas barrier film according to the present invention, and the present invention
Needless to say, this is not a limitation.

Next, in the present invention, the transparent gas barrier film according to the present invention as described above will be described in terms of the materials used, its production method, etc. First, in the present invention, the transparent gas barrier film according to the present invention will be described. −
As the base film constituting the functional film, films or sheets of various colorless and transparent resins can be used. Specifically, for example, polyolefin resins such as polyethylene or polypropylene, polyethylene terephthalate Polyester resin such as polyethylene or naphthalate, polyamide resin, polycarbonate
Film or sheet of various resins such as
Can be used. The resin film or sheet may be a single layer, a film formed by a co-extrusion method of two or more layers, or a film stretched biaxially, and the like. The thickness is preferably about 10 to 100 μm, and more preferably about 20 to 50 μm, from the viewpoint of the stability during the production of the transparent gas barrier film. If necessary, the surface of the resin film or sheet may be optionally subjected to a surface activation treatment such as a corona treatment, a plasma treatment, a frame treatment or the like. Further, in the present invention, in order to achieve a strong adhesion strength with the deposited film, for example, a first thin film is coated with an anchor coating agent such as a polyester-based, urethane-based, epoxy-based, amine-based, or the like. In the vapor deposition step for forming, it can be formed in-line or off-line. Furthermore, in the present invention, depending on the application, for example, an antistatic agent, an ultraviolet absorber, a plasticizer,
Desired additives such as lubricants, fillers, etc. may be arbitrarily added within a range that does not affect the transparency, and a film or sheet of a resin containing them may be used.

Next, in the present invention, the inorganic oxide deposited film constituting the transparent gas barrier film of the present invention is basically a thin film obtained by converting an inorganic oxide into an amorphous (amorphous) film. It is possible to use inorganic oxides such as silicon oxide, aluminum oxide, magnesium oxide, calcium oxide, potassium oxide, tin oxide, sodium oxide, boron oxide, titanium oxide, lead oxide, zirconium oxide, and yttrium oxide. An amorphous thin film can be used. In the present invention, specifically, for example, using an inorganic oxide composed of the above-described metal oxide, or a metal, if necessary, while supplying oxygen gas or the like, vacuum evaporation method, sputtering method , Physical vapor deposition method such as ion plating method (physical vapor deposition method, Physical Vap method)
or Deposition method, PVD method)
A deposited film of an inorganic oxide can be formed. 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 method for heating the deposition material. The above-mentioned physical vapor deposition method will be described in more detail by taking an example of a roll-up type vapor deposition machine as an example. As shown in a schematic configuration diagram of FIG. -12, a base film 14 fed from an unwinding roll 13
Passes through a coating drum 15 to a deposition chamber 16
Here, the metal or metal oxide heated as an evaporation source in the crucible 17 is evaporated, and at this time, the cooled coating is performed while ejecting oxygen gas or the like from the oxygen outlet 18. Base film 1 of drum 15
4, a vapor-deposited film of an inorganic oxide is formed through masks 19, 19, and then the base film 1 on which the vapor-deposited film is formed
By feeding the material 4 into the vacuum chamber 12 and winding it up on the take-up roll 12, a deposited film of an inorganic oxide can be formed on the base film 14. In the above, the thickness of the deposited film of the inorganic oxide is 50 to 30.
It is desirably in the range of 00 °, preferably in the range of 100 to 2000 °. When the thickness of the above-mentioned inorganic oxide vapor-deposited film is less than 50 ° or even 100 °, the gas barrier property is insufficient. Is reduced,
It is not preferable because cracks easily occur in the deposited film. In the present invention, as the vapor-deposited film of the inorganic oxide, a vapor-deposited film of amorphous aluminum oxide, which is particularly excellent in transparency, is preferably used.
O _X (where in the formula, X represents the number of 1 to 1.5.)
Is preferable.

Next, in the present invention, a coating film mainly composed of a silicon oxide film which has been heat-treated under a constant temperature and constant humidity with a coating solution containing polysilazane constituting the transparent gas barrier film according to the present invention will be described. First,
The polysilazane described above has a general formula: (SiN
_a H _b ) _n (where a is 1-3, b
Is 0 to 1 and n is a positive integer. A mixture of one or more kinds of perhydropolysilazanes represented by the formula (1) can be used. Thus, the above-mentioned perhydropolysilazane has a structure in which only a hydrogen atom as a side chain is bonded to a structure of -Si-N- which is a main chain. Since the above-mentioned perhydropolysilazane is easily hydrolyzed, the coating solution is usually prepared by dissolving it in an organic solvent which does not dissolve water, such as benzene, xylene and dibutyl ether. Thus, in the present invention, after forming an inorganic oxide vapor-deposited film on the surface of the base film as described above, applying the coating solution prepared above on the surface of the inorganic oxide vapor-deposited film, Next, a heat treatment is performed at a constant temperature and a constant humidity to form a coating film mainly composed of a silicon oxide film.
In the above, as a coating method, for example, gravure river coat, roll coat, die coat, dip coat
Coating can be performed by using a coating method such as spin coating, spin coating, reverse coating, slit coating, or the like. It can be overprinted multiple times. Also, in the above,
As the heat treatment conditions, for example, it is necessary to perform heat treatment at a heating temperature of about 400 to 500 ° C. for about 1 to 2 hours under constant temperature and constant humidity. A heat treatment at a heating temperature of about 100 ° C. for about 5 to 10 minutes under moisture can form a coating film mainly composed of a silicon oxide film. It is possible to form a ceramic coating film mainly composed of a silicon oxide film by performing heat treatment for about 1 to 5 days under moisture. In the above, the condition under constant humidity is desirably 50 to 100%, preferably about 70 to 90%. In the present invention, the thickness of the coating film mainly composed of the silicon oxide film is in the range of about 0.1 to 3 μm, preferably 0.1 to 3 μm.
It can be used in the range of μm to 2 μm. In the above, if it is less than 0.1 μm, the gas barrier property is insufficient, and if it is more than 2 μm, furthermore, if it exceeds 3 μm, the flexibility of the coating film is reduced, and cracks and the like are liable to occur. This is undesirable because

As is apparent from the above description, the present invention provides:
On the surface of the base film, a deposited film of an inorganic oxide is provided, and further, on the surface of the deposited film of the inorganic oxide, a silicon oxide film subjected to heat treatment under a constant temperature and constant humidity with a coating solution containing polysilazane. The present invention relates to a transparent gas barrier film having a coating film formed thereon. Therefore, the transparent gas barrier film according to the present invention is excellent in transparency, and further, has an oxygen gas or water vapor transmission rate of 1 or more.
cc, or 1 g or less, and it is possible to obtain a gas barrier property that cannot be obtained with a conventional gas barrier film composed of a deposited film of an inorganic oxide. It is useful as a packaging material for producing packaging containers. Further, the transparent gas barrier film according to the present invention is mainly composed of a silicon oxide film heat-treated under a constant temperature and constant humidity with a coating solution containing polysilazane on the surface of an inorganic oxide vapor-deposited film lacking flexibility. Since the coating film is provided, the coating film mainly composed of the silicon oxide film acts as a protective layer of the deposited film of the inorganic oxide, for example, during printing, laminating, and post-processing such as bag making. Cracks and the like do not occur in the deposited film of the inorganic oxide, and are extremely excellent in post-processing suitability. Further, the transparent gas barrier film according to the present invention is a coating film mainly composed of a silicon oxide film that has been heat-treated under a constant temperature and constant humidity with a coating solution containing polysilazane, is excellent in heat resistance, and further has an inorganic oxide. Since it has excellent adhesiveness to a deposited film, for example, a packaging bag or the like that can be used for boiling and retorting can be manufactured. Further, conventionally, as a method for forming a coating film mainly composed of silicon oxide, a so-called sol-gel method utilizing a hydrolysis reaction of an alkoxysilane or the like is known, but this method is not yet fully described. It is difficult to form a dense coating film because the organic compound of the reaction remains in the film, and the film forming efficiency is poor, but the constant temperature and humidity by the coating solution containing the polysilazane according to the present invention described above is used. The method of forming a coating film mainly composed of a silicon oxide film subjected to heat treatment under the following conditions is efficient, and furthermore, since there is no elimination of organic components other than hydrogen atoms, a high-density dense A coating film can be formed.

[0012] The transparent gas barrier film according to the present invention produced as described above is, for example, a resin film, a paper base, a metal material, synthetic paper, cellophane, etc. It is possible to manufacture various laminates by arbitrarily combining them with materials and the like, for example, by laminating by a normal lamination method, and to manufacture a packaging material suitable for filling and packaging various articles. . As the resin film, specifically, 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 Poly (vinylidene chloride) resin, vinyl chloride-vinylidene chloride copolymer, poly (meth) acrylic resin, polyacrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene- Styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate resin, polyvinyl alcohol
Resin, saponified ethylene-vinyl acetate copolymer,
Fluorine resin, diene resin, polyacetal resin,
Any known resin film or sheet such as polyurethane resin, nitrocellulose, etc. can be used. In the present invention, the above-mentioned film or sheet can be used in any of unstretched and uniaxially or biaxially stretched.
The thickness is arbitrary, but is from several μm to 300 μm.
It can be used by selecting from the range of the m-th position. Furthermore,
In the present invention, any film such as an extruded film, an inflation film, or a coating film may be used as the film or sheet. Further, in the above, as the paper substrate, for example, a paper substrate such as a strongly sized bleached or unbleached paper, a paper substrate such as pure white roll paper, kraft paper, paperboard, or processed paper, or the like is used. can do. In the above, the paper base constituting the paper layer has a basis weight of about 80
~ 600 g / m ² , preferably about 100 basis weight
It is desirable to use those of about 450 g / m ² .
In the above description, as the metal material, for example, an aluminum foil, a resin film having an aluminum vapor-deposited film, or the like can be used.

Next, a method of manufacturing a laminate using the above materials in the present invention will be described. As the method, a conventional packaging material is laminated.
For example, a wet lamination method, a dry lamination method, a solventless dry lamination method, an extrusion lamination method, a T-die extrusion molding method, a co-extrusion lamination method, an inflation method, It can be performed by an extrusion inflation method or the like. Thus, in the present invention, when performing the above-mentioned lamination, if necessary, for example, a pre-treatment such as a corona treatment, an ozone treatment, a framing treatment, or the like can be performed on the film. Anchor coating agents such as polyester, isocyanate (urethane), polyethyleneimine, polybutadiene, and organic titanium, or polyurethane, polyacryl, polyester, epoxy, and polyvinyl acetate And known adhesives such as adhesives for laminates such as cellulose, cellulose, etc.
Coating agents, adhesives and the like can be used.

Next, in the present invention, a method of making a bag or a box using the above-mentioned laminate will be described. For example, when the packaging container is a soft packaging bag made of a plastic film or the like, Using the laminated body manufactured by such a method, the heat-sealing resin layer of the inner layer is opposed to the laminated body, and the heat-sealing resin layer is folded, or the two sheets are overlapped, and the peripheral end portion is further folded. A bag can be formed by providing a seal portion by heat sealing. Thus, as a bag making method, the above-mentioned laminate is folded with its inner layer facing the surface, or two of them are overlapped,
Further, the peripheral end portion of the outer periphery is formed, for example, by a side seal type, a two-side seal type, a three-side seal type, a four-side seal type, an envelope-attached seal type, and a gasket-attached seal type ( According to the present invention, a heat seal is formed according to a heat seal form such as a (pyrro-seale type), a pleated seal type, a flat bottom seal type, a square bottom seal type, and the like. Various forms of packaging containers can be manufactured. Others, for example, self-supporting packaging bags (standing pouches)
And the like can be manufactured, and in the present invention, a laminating tube container and the like can also be manufactured using the above-mentioned laminated material. In the above, as a method of heat sealing, for example, a bar seal, a rotating roll seal,
Belt, belt seal, impulse seal, high frequency seal,
It can be performed by a known method such as an ultrasonic seal. In the present invention, the packaging container as described above,
For example, a one-piece type, a two-piece type, or the like, a spout, or a zipper for opening and closing can be arbitrarily attached.

Next, in the case of a liquid-filled paper container containing a paper substrate as the packaging container, for example, a laminated material in which a paper substrate is laminated is produced as a laminated material, and a desired paper container is produced therefrom. A blank plate is manufactured, and thereafter, a body, a bottom, a head and the like are manufactured using the blank plate to manufacture, for example, a liquid paper container of a brick type, a flat type or a gable-top type. be able to. Moreover, the shape can be manufactured by any of a rectangular container, a circular or other cylindrical paper can, 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, etc., impact resistance, etc.
Having post-processing suitability such as printing, bag making or box making,
Further, it prevents peeling of the vapor-deposited thin film as a barrier film, and prevents the occurrence of thermal cracks, prevents its deterioration, and exhibits excellent resistance as a barrier film, for example, It has excellent suitability for filling and packaging, preservation, etc. of various articles such as chemicals and cosmetics such as medicines, detergents, shampoos, oils, toothpastes, adhesives and adhesives, and others.

[0017]

【Example】

Example 1 Vacuum deposition by electron beam (EB) heating method using a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm as a base material and supplying oxygen gas to one surface thereof while using aluminum as an evaporation source. By the method, the film thickness 200
(2) A deposited film of aluminum oxide is formed, and a solution containing 20% by weight of polysilazane is coated on the surface of the deposited film.
It is applied by a coater and then dried at 120 ° C.
By heating for 1 hour, a coating film mainly composed of silicon oxide having a thickness of 1.2 μm was formed, thereby producing a transparent gas barrier film according to the present invention.

Example 2 An electron beam (EB) heating method was used in which a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as a base material, and aluminum was used as a vapor deposition source on one side while supplying oxygen gas. Film thickness of 200 by vacuum evaporation method
(4) A deposited film of aluminum oxide is formed, and a solution containing 10% by weight of polysilazane is coated on the deposited film surface.
It is applied by a coater and then dried at 120 ° C.
By heating for 1 hour, a coating film mainly composed of silicon oxide having a thickness of 0.5 μm was formed, and a transparent gas barrier film according to the present invention was produced.

Example 3 An electron beam (EB) heating method was used in which a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as a base material, and aluminum was used as an evaporation source on one side while supplying oxygen gas. Film thickness of 200 by vacuum evaporation method
(5) An aluminum oxide vapor-deposited film is formed, and a solution containing 5% by weight of polysilazane is applied to the surface of the vapor-deposited film by a bar coater.
By heating for a time, a coating film mainly composed of silicon oxide having a thickness of 0.3 μm was formed, and the transparent gas barrier film according to the present invention was produced.

Example 4 An electron beam (EB) heating method was used in which a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as a base material, and aluminum was used as a vapor deposition source on one side while supplying oxygen gas. Film thickness of 200 by vacuum evaporation method
(2) A vapor-deposited film of aluminum oxide is formed, and a solution containing 2.5% by weight of polysilazane is applied to the surface of the vapor-deposited film by a bar coater.
By heating at 1 ° C. for 1 hour, a coating film mainly composed of silicon oxide having a thickness of 0.2 μm was formed to produce a transparent gas barrier film according to the present invention.

Example 5 An electron beam (EB) heating method using a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm as a base material and using aluminum as a vapor deposition source on one surface thereof while supplying oxygen gas. Film thickness of 300 by vacuum evaporation method
(4) A deposited film of aluminum oxide is formed, and a solution containing 10% by weight of polysilazane is coated on the deposited film surface.
It is applied by a coater and then dried at 120 ° C.
By heating for 1 hour, a coating film mainly composed of silicon oxide having a thickness of 0.5 μm was formed, and a transparent gas barrier film according to the present invention was produced.

Example 6 An electron beam (EB) heating method was used in which a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as a base material, and aluminum was used as a vapor deposition source on one side while supplying oxygen gas. Film thickness of 400 by vacuum evaporation method
(4) A deposited film of aluminum oxide is formed, and a solution containing 10% by weight of polysilazane is coated on the deposited film surface.
It is applied by a coater and then dried at 120 ° C.
By heating for 1 hour, a coating film mainly composed of silicon oxide having a thickness of 0.5 μm was formed, and a transparent gas barrier film according to the present invention was produced.

COMPARATIVE EXAMPLE 1 A biaxially oriented polyethylene terephthalate film having a thickness of 12 μm was used as a base material, and an electron beam (EB) heating system was used while supplying oxygen gas to one surface of the substrate using aluminum as an evaporation source. Film thickness of 200 by vacuum evaporation method
A gas barrier film was manufactured by forming an aluminum oxide vapor-deposited film of (1).

Comparative Example 2 A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as a base material, and a solution containing 10% by weight of polysilazane was applied to one surface thereof with a bar coater, and then dried. Heat treatment was performed at 120 ° C. for 1 hour with a machine to form a coating film mainly composed of silicon oxide having a thickness of 0.5 μm, thereby producing a gas barrier film.

Comparative Example 3 A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as a base material, and on one side thereof, an electron beam (EB) heating method was used while using aluminum as an evaporation source and supplying oxygen gas. Film thickness of 200 by vacuum evaporation method
Then, a vapor-deposited film of aluminum oxide is formed, and then tetraethoxysilane [Si (OC ₂ H ₅ )
₄ ) A coating solution consisting of an aqueous solution to which hydrochloric acid is added is coated with a bar coater, and then heat-treated at 120 ° C. for 1 hour in a drier to obtain a silicon oxide film having a thickness of 1 μm. Was formed to produce a gas barrier film.

EXPERIMENTAL EXAMPLE 1 The transparent gas barrier film of the present invention produced in Examples 1 to 6 and the gas barrier film produced in Comparative Examples 1 to 3 were tested for oxygen permeability and water vapor permeability. It was measured. (1). Measurement of Oxygen Permeability The measurement was performed under the conditions of a temperature of 25 ° C. and a humidity of 90% RH using a measuring device (model name, OXTRAN 2/20) manufactured by MOCON, USA. (2). Measurement of Water Vapor Permeability Under the conditions of a temperature of 37.8 ° C. and a humidity of 100% RH, the measurement was carried out using a measuring device (model name, Permatran (PERMATRAN 3/31)) manufactured by MOCON, USA. The results measured above are shown in Table 1 below.

[0027]

[Table 1]

As is clear from the results shown in Table 1 above, the transparent gas barrier film according to the present invention has excellent oxygen permeability and water vapor permeability and is useful as a gas barrier material.

EXPERIMENTAL EXAMPLE 2 Next, the transparent gas barrier film of the present invention produced in Examples 1 to 6 and the gas barrier film produced in Comparative Examples 1 to 3 were used. For such a transparent gas barrier film, the coating film surface mainly composed of silicon oxide, and for the gas barrier film produced in Comparative Examples 1 to 3, its vapor-deposited film surface, or silicon oxide film. A 15 μm-thick biaxially stretched nylon film is laminated on the main coating film surface using a urethane-based adhesive, and a urethane-based adhesive is further used on the nylon film surface in the same manner as described above. Then, an unstretched polypropylene film having a thickness of 30 μm was laminated to produce a laminate. Next, using the above-described laminate, a bag is formed by a usual method to produce a heat-sealed three-sided packing bag, and then the contents are filled through the opening of the packing bag. Then, the opening was heat-sealed to produce a package. Next, the package manufactured above was retorted at 120 ° C. for 30 minutes.
The oxygen permeability of the packaging bags before and after the retort treatment was measured. (1). Measurement of Oxygen Permeability The measurement was performed under the conditions of a temperature of 25 ° C. and a humidity of 90% RH using a measuring device (model name, OXTRAN 2/20) manufactured by MOCON, USA. The results measured above are shown in Table 2 below.

[0030]

[Table 2]

As is clear from the results shown in Table 2 above, the packaging bag made by using the laminate using the transparent gas barrier film according to the present invention has excellent oxygen permeability and gas barrier property. It is useful as an active material.

EXPERIMENTAL EXAMPLE 3 Next, the transparent gas barrier film of the present invention produced in Examples 1 to 6 and the gas barrier film produced in Comparative Examples 1 to 3 were used. For such a transparent gas barrier film, the coating film surface mainly composed of silicon oxide, and for the gas barrier film produced in Comparative Examples 1 to 3, its vapor-deposited film surface, or silicon oxide film. A 30 μm-thick unstretched polypropylene film was bonded to the main coating film surface using a urethane-based adhesive to produce a laminate. In order to evaluate the bending resistance of the laminated body manufactured as described above, the oxygen permeability was measured for the laminated body before and after 50 times of Gerbo. (1). Measurement of Oxygen Permeability The measurement was performed under the conditions of a temperature of 25 ° C. and a humidity of 90% RH using a measuring device (model name, OXTRAN 2/20) manufactured by MOCON, USA. The results measured above are shown in Table 3 below.

[0033]

[Table 3]

As is clear from the results shown in Table 3 above, the laminate using the transparent gas barrier film according to the present invention has excellent flex resistance and is useful as a gas barrier material.

[0035]

As is apparent from the above description, the present invention focuses on a silicon oxide film formed by a coating solution containing polysilazane, and provides a vapor-deposited inorganic oxide film on the surface of a substrate film. On the surface of the inorganic oxide vapor-deposited film, a coating film mainly composed of a silicon oxide film heat-treated under a constant temperature and constant humidity with a coating solution containing polysilazane is provided to produce a transparent gas barrier film. , The transparent gas barrier
Film is excellent in transparency, gas barrier property against oxygen gas or water vapor, etc.
G, excellent post-processing suitability such as bag making, for example, food and drink,
It is a gas barrier material useful as a packaging material for various articles such as pharmaceuticals, cosmetics, chemicals, electronic parts, miscellaneous goods, and the like.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view showing a layer configuration of an example of a transparent gas barrier film according to the present invention.

FIG. 2 is a schematic configuration diagram showing an example of a configuration of a vacuum vapor deposition method for forming a vapor-deposited film of an inorganic oxide on a transparent gas barrier film according to the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 transparent gas barrier film 2 base film 3 inorganic oxide deposited film 4 coating film mainly composed of silicon oxide 11 roll-up vacuum deposition device 12 vacuum chamber 13 unwinding roll 14 base film 15 Coating drum 16 Deposition chamber 17 Crucible 18 Oxygen outlet 19 Mask 20 Winding roll

Claims (2)

[Claims] 1. A silicon oxide obtained by providing a vapor-deposited film of an inorganic oxide on a surface of a substrate film and further heat-treating the surface of the vapor-deposited inorganic oxide film under a constant temperature and constant humidity with a coating solution containing polysilazane. A transparent gas barrier film having a coating film mainly composed of an object film. 2. The transparent gas barrier film according to claim 1, wherein the inorganic oxide deposited film comprises an aluminum oxide deposited film.