JP2000355070A - Barrier film and laminated material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a barrier film having high transparency, excellent in oxygen gas barrier properties, steam barrier properties or the like, especially reduced in the change of oxygen barrier properties even if environmental temp. changes and comprising a vapor deposition film of aluminum oxide withstanding temp. dependence sufficiently. SOLUTION: A barrier film A is obtained by forming a vapor deposition film 22 of aluminum oxide of which the transmissivity of ultraviolet rays with a wavelength of 366 nm is adjusted on the single surface of a substrate film 4 by adjusting a gaseous phase reaction system wherein aluminum vapor and oxygen are reacted in-line. Next, the vapor deposition film comprising the substrate film 4 having the vapor deposition film of aluminum oxide formed thereon is allowed to stand in environment with a relative humidity of 50% RH at the normal temp. of 25 deg.C for one week or more for constant temperature/ constant humidity processing to be adjusted to 95% or more in its transmissivity of ultraviolet rays with a wavelength of 366 nm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a barrier film and a laminated material using the same, and more particularly to a barrier film having high transparency, excellent oxygen gas barrier properties, excellent water vapor barrier properties, and the like. The present invention relates to a barrier film having an aluminum oxide vapor-deposited film that has a small change in oxygen gas barrier properties even when the temperature changes and sufficiently withstands temperature dependency, and a laminate using the same.

[0002]

2. Description of the Related Art Conventionally, various films having excellent barrier properties such as oxygen gas barrier property and water vapor barrier property have been developed and proposed.
2. Description of the Related Art A vapor-deposited film in which a vapor-deposited film of an inorganic oxide such as silicon oxide or aluminum oxide is provided on a surface of a plastic film using a physical vapor deposition method such as a vacuum vapor deposition method is known. Thus, the above-mentioned vapor-deposited film has transparency, and is excellent in oxygen gas barrier properties, water vapor barrier properties, and the like, and is attracting attention as a barrier material suitable for environmental protection. Laminated with base materials, etc., to constitute laminated materials of various forms, food and beverage,
BACKGROUND ART As a packaging material for filling and packing articles such as chemicals and others, its development and demand are expected.

[0003]

By the way, in the case of a vapor-deposited film obtained by forming the above-mentioned vapor-deposited film of aluminum oxide, in order to produce a vapor-deposited film having high transparency, for example, aluminum oxide is used as an evaporation source. Although there is a case where vapor deposition is performed, in this case, there is an advantage that a product having excellent transparency can be manufactured.However, since the evaporation temperature of aluminum oxide is high, and its thermal efficiency is remarkably inferior, at the time of vapor deposition, There is a problem that the thermal effect on the base film is large, and there is a problem that the cost is high. For this reason, a method is known in which a vapor-deposited film of aluminum oxide is formed on a base film while reacting the vapor of aluminum oxide and oxygen gas in a gas phase. When the amount is large, it is possible to produce a vapor-deposited film having high transparency, but there is a problem that oxygen gas barrier properties and the like are inferior.Also, when the supply amount of oxygen gas is small, the oxygen gas barrier properties and the like are improved, It is inferior in transparency, and further attempts have been made to leave it in the air to completely oxidize it in order to enhance the transparency, but in this case, a long processing time is required and cost is a problem. There is a point. In addition, oxygen plasma is irradiated on the aluminum oxide deposited film surface in the deposition in-line,
A method is also known in which highly reactive oxygen is introduced on the surface of the deposited film to form a composite film composed of aluminum oxide and aluminum hydroxide, but in this case, the composite film becomes more amorphous. For example, there is a problem that the oxygen gas barrier property greatly changes due to a temperature change, resulting in a composite film having high temperature dependency and poor usability. Furthermore, a method of forming a composite film composed of aluminum oxide and aluminum hydroxide by treating an aluminum oxide vapor-deposited film surface in a vapor deposition off-line is also known as described above. As described above, there is a problem that the temperature dependence is increased and a composite film having a deteriorated oxygen gas barrier property at a high temperature is obtained. In any case, a deposited film formed by forming a deposited film of aluminum oxide, the deposited film of aluminum oxide,
Although it has the advantage of having high transparency, it is inferior to a vapor-deposited film formed by forming a silicon oxide vapor-deposited film in terms of oxygen gas barrier properties and the like. It is inferior to a deposited film formed into a film. In addition, in a deposited film formed by forming a deposited film of aluminum oxide, in order to increase its oxygen gas barrier properties, water vapor gas barrier properties, and the like, it has been attempted to increase the thickness of the deposited film of aluminum oxide, In this case, the film hardness of the deposited film of aluminum oxide is high. For example, a printing process for providing a desired print pattern layer, a lamination process for laminating another plastic film, or the like, and a laminating material is used. In post-processing such as bag making,
There is a problem that cracks and the like occur in the aluminum oxide vapor-deposited film, which is not necessary. Further, an undercoating agent for vapor deposition or the like is coated on the surface of the base film in advance to improve the adhesion strength to an aluminum oxide vapor deposition film or a silicon oxide vapor deposition film, etc. Attempts have also been made to improve gas barrier properties, water vapor gas barrier properties, etc., but in the case of a deposited film of aluminum oxide,
The effect is not recognized. Therefore, the present invention
Highly transparent, excellent in oxygen gas barrier properties, water vapor barrier properties, etc., and in particular, a deposited film of aluminum oxide that sufficiently withstands temperature dependence with little change in oxygen gas barrier properties even when environmental temperature changes. An object of the present invention is to provide a barrier film formed into a film and a laminated material using the barrier film.

[0004]

Means for Solving the Problems The present inventor has conducted various studies to solve the above-mentioned problems, and as a result, while allowing aluminum vapor and oxygen to react on one surface of the base film in the gas phase, The reaction system was adjusted in-line to 366n
m, an aluminum oxide vapor-deposited film having an ultraviolet transmittance adjusted to a range of 88 to 92% was formed. At room temperature and a relative humidity of 50
% RH for 1 week or more to produce a barrier film by constant temperature and humidity treatment, the UV transmittance at 366 nm can be adjusted to 95% or more, and it has extremely high transparency. Furthermore, a barrier film that is excellent in oxygen gas barrier properties, water vapor barrier properties, etc., and in particular, has found a barrier film that sufficiently withstands temperature dependency with little change in oxygen gas barrier properties even when the environmental temperature changes, and furthermore, in the above barrier film, Then, a laminated material is manufactured by laminating another plastic film or the like, and then the laminated material is used, and a bag is manufactured from the laminated material to manufacture a packaging container. Products and other products, especially powdered foods and beverages such as flour, bread crumbs, curry flour, rice cereal flour, etc., have sufficient filling and packaging suitability and sufficient distribution and storage routes. It has a storage suitability, and completed the present invention have found that it is possible to produce a very good packaging products.

That is, according to the present invention, while reacting aluminum vapor and oxygen in a gas phase on one surface of a base film, the reaction system is adjusted in-line to increase the ultraviolet transmittance at 366 nm from 88 to 92%. Then, a deposited film of a base film obtained by forming a deposited film of the aluminum oxide into a film having a relative humidity of 50% R at a normal temperature of 25 ° C.
The present invention relates to a barrier film characterized in that ultraviolet transmittance at 366 nm is adjusted to 95% or more by leaving it in an environment of H for at least one week and subjecting it to a constant temperature and humidity treatment, and a laminated material using the same. .

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. First, the barrier film according to the present invention will be described with reference to an example of a method for producing the barrier film.The barrier film according to the present invention first uses a vacuum evaporation apparatus or the like, and on one side of the base film, aluminum vapor is applied. The reaction system was adjusted in-line while reacting oxygen with the gas phase, and the ultraviolet transmittance at 366 nm was 88%.
A deposited film of a base film obtained by forming a deposited film of aluminum oxide adjusted to ~ 92%, and then forming the deposited film of the aluminum oxide, for example, with the deposited film surface of the aluminum oxide inward. After that, the aluminum oxide film is further rewound so that the vapor-deposited film surface is on the outside, and the rewound film is left in an environment of a temperature of 25 ° C. and a relative humidity of 50% RH for at least one week to be kept at a constant temperature. By performing the constant humidity treatment, the ultraviolet transmittance at 366 nm is adjusted to 95% or more, and the barrier film according to the present invention can be manufactured.

The above-mentioned method for producing a barrier film according to the present invention will be described more specifically by taking a roll-up vacuum vapor deposition machine as an example. As shown in FIG. In the vacuum chamber 2 of the apparatus 1, the base film 4 is unwound from the unwinding roll 3,
Next, the base film 4 is guided to a cooled coating drum 7 via guide rolls 5 and 6. On the other hand, in the vacuum chamber-2, the aluminum (metal) heated as the evaporation source 9 in the crucible 8 is evaporated, and at that time, oxygen gas or the like is supplied from the oxygen blowing port 10,
While reacting the aluminum vapor and the oxygen gas, a vapor-deposited film of aluminum oxide is formed on the surface of the base film 4 guided on the cooled coating drum 7 through the masks 11 and 11. Then, a deposited film composed of the base film 4 obtained by forming the deposited film of aluminum oxide into a film is wound through guide rolls 5 'and 6' with the deposited film of aluminum oxide inside. The film is wound up on a take-up roll 12, and a vapor deposition film is formed by forming a vapor deposition film of aluminum oxide on the base film 4. Thus, in the present invention, when supplying oxygen gas or the like from the oxygen blow-out port 10 in the above-described vapor deposition film manufacturing process, the ultraviolet ray transmittance at 366 nm is adjusted to 88 while adjusting the supply amount of the oxygen gas. ~ 92
% Of the deposited aluminum oxide film. Incidentally, the deposited film of aluminum oxide formed as described above has a low degree of oxidation of aluminum and has a black or dark brown color. Then
In the present invention, the vapor-deposited film produced as described above, since the vapor-deposited film of aluminum oxide is not completely transparent as described above, by performing the transparency offline, the barrier film according to the present invention is produced Is what you do. That is, in the present invention, although not shown, after the above-prepared vapor-deposited film is taken out of the vacuum chamber, it is rewound using, for example, a rewinder so that the aluminum oxide vapor-deposited film surface is on the outside. Thereafter, the rolled-up deposited film is allowed to stand at a temperature of 25 ° C. and a relative humidity of 50% for one week or more under constant conditions and subjected to a constant-temperature and constant-humidity treatment to form an aluminum oxide deposited film. The barrier film according to the present invention is produced by adjusting the UV transmittance at 366 nm to 95% or more by increasing the degree of oxidation to achieve transparency. In the present invention,
In the state of the vapor-deposited film, the aluminum oxide that forms the vapor-deposited film of aluminum oxide is incomplete aluminum oxide, which is not completely aluminum oxide, such as Al ₂ O ₃ , and this is the state of oxygen in the air. It is presumed that by absorbing the oxygen and reacting with the oxygen to change to a complete aluminum oxide state of Al ₂ O ₃ , transparency can be improved while maintaining performance such as gas barrier properties. is there.

In the above-mentioned production method, as the base film, various colorless and transparent resin films or sheets can be used. Specifically, for example, polyolefin resins such as polyethylene or polypropylene;
Polyester resin such as polyethylene terephthalate or polyethylene naphthalate, polyamide resin,
Films or sheets of various resins such as polycarbonate resins and others can be used. The resin film or sheet may be a single layer, a film formed by co-extrusion of two or more layers, or a sequential biaxial stretching method by a flat method, a simultaneous biaxial stretching method, a tube, or the like.
What has been biaxially stretched using a simultaneous biaxial stretching method or the like can be used. Further, the thickness of the film may be, for example, the stability at the time of production of a film or sheet. From about 7 to 100 μm, preferably 9 to 30 μm
Position is desirable. Further, a film or sheet of the above resin is used.
If necessary, the surface can be arbitrarily subjected to a surface activation treatment such as a corona discharge treatment, a plasma treatment, a frame treatment or the like, if necessary. 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, a lubricant, a filler, and other additives as desired, within a range that does not affect the transparency thereof. In addition, a film or sheet of a resin containing them can also be used.

In the present invention, among the above-mentioned resin films or sheets, polyethylene terephthalate obtained by the condensation reaction of terephthalic acid and ethylene glycol is used as the base film. It is desirable to use a polyester resin film or sheet that is a dehydration condensate of an acid component of dicarboxylic acid and an alcohol component of diol such as a film. As the above-mentioned polyester resin, for example, an acid component or an alcohol component may be used as another component, or a multi-component may be used as a copolymer, depending on the purpose. Can also. Further, as the above-mentioned polyester resin film or sheet, in addition to ordinary general types, any of transparent type, easily adhesive type, retort type, and other special types can be used. be able to. Further, in the present invention, as the content to be filled and packed, particularly when filling and packaging powdered food or drink such as wheat flour, bread crumbs, curry flour, rice flour, etc., it is rich in toughness and piercing resistance. It is desirable to use a polyamide resin film or sheet such as nylon 6, nylon 66, nylon 7, nylon 12, etc., which is excellent in chemical resistance, chemical resistance, etc.

Next, in the present invention, as a deposited film of aluminum oxide constituting the barrier film according to the present invention, a deposited film of amorphous aluminum oxide having excellent transparency is preferable. Formula AlO _X (However,
In the formula, X represents a number of 1 to 1.5. ) Is preferable. Further, in the present invention, the thickness of the deposited film of aluminum oxide is about 50 to 500 °, more preferably about 150 °.
About 300 ° is desirable, and in the above, 30
When the thickness is 0 ° or more than 500 °, the flexibility of the film is reduced and cracks or the like easily occur in the film, which is not preferable. When the thickness is less than 50 ° or less than 150 °, the barrier property is poor. It is not preferable because it is difficult to achieve the effects such as above. Thus, in the present invention, the above-mentioned deposited film of aluminum oxide is, specifically, for example, using aluminum as a deposition material, evaporating the aluminum with an electron beam gun or the like, and forming the aluminum vapor phase. By supplying oxygen gas or the like, aluminum is oxidized, and a vapor-deposited film of aluminum oxide is favorably formed on the base film at low cost. In the above, in order to efficiently perform the oxidation reaction, a method of performing deposition while irradiating a microwave wave can also be used. In the present invention, examples of the vapor deposition method include a physical vapor deposition method (physical vapor deposition method, physical vapor deposition method) such as a vacuum vapor deposition method, a sputtering method, and an ion plating method.
An aluminum oxide deposited film can be formed by an ion method or a PVD method and used. Further, in the above, as a heating method of the deposition material, for example, an electron beam (EB) method, a high-frequency induction heating method,
A resistance heating method or the like can be used, and in the present invention, an electron beam type vacuum deposition method which has good thermal efficiency and can be deposited at a high speed is more preferable.

By the way, in the barrier film according to the present invention, the transparency of the deposited aluminum oxide film is determined by the supply amount of oxygen gas to be reacted with aluminum. Is good, but the oxygen gas barrier property is poor, and when the supply amount of oxygen gas is small, the oxygen gas barrier property is good, but the transparency is deteriorated. Thus,
In the present invention, as described above, the supply amount of oxygen gas is adjusted in-line with the vapor deposition, the degree of oxidation of aluminum constituting the vapor-deposited film of aluminum oxide is low, and the color tone is black or dark brownish. This is to form a deposited film of aluminum oxide whose ultraviolet transmittance at 366 nm is adjusted to 88 to 92%. Next, in the present invention, the above-mentioned rolled-up film having the aluminum oxide vapor-deposited film formed thereon, the vapor-deposited film composed of the base film formed into the aluminum oxide vapor-deposited film, and the aluminum oxide vapor-deposited film surface wound inward in the vapor deposition in-line, The aluminum oxide deposited film is rewound so that the surface thereof is on the outside, and then the above-mentioned rewound deposited film is left in an environment of a temperature of 25 ° C. and a relative humidity of 50% RH for at least one week to be subjected to a constant temperature and humidity treatment. The barrier film according to the present invention is manufactured by adjusting the ultraviolet transmittance at 366 nm to 95% or more by increasing the degree of oxidation of aluminum constituting the deposited film of aluminum to achieve transparency.

In the present invention, the barrier film A according to the present invention obtained by the above-described manufacturing method is provided with aluminum vapor and oxygen on one side of the base film 4 as shown in the schematic sectional view of FIG. Are reacted in the gas phase, and the reaction system is adjusted in-line to form a film. The aluminum oxide vapor-deposited film 21 having an ultraviolet transmittance at 366 nm in the range of 88 to 92% is formed at a normal temperature of 25 ° C. And left in an environment of relative humidity of 50% RH for at least one week to adjust by constant temperature and constant humidity treatment, and the UV transmittance at 366 nm was 95%.
It has a configuration in which a deposited film 22 of aluminum oxide modified as described above is provided.

Thus, the barrier film according to the present invention produced as described above constitutes a packaging container for a resin film, a paper substrate, a metal material, synthetic paper, cellophane, etc. It is possible to produce a laminated material suitable for filling and packaging various articles by arbitrarily combining with a packaging material and the like. Twelve examples of the above-mentioned laminated material are shown in a specific example. As shown in a schematic cross-sectional view of FIG. 3, the aluminum oxide vapor deposition film 22 (21) of the barrier film A shown in FIG. A laminated material B having a configuration in which at least a heat-sealing resin layer 23 is laminated on the surface can be given. In FIG. 3 above,
In the drawing, reference numeral 4 has the same meaning as described above. Or,
In the present invention, as shown in the schematic sectional view of FIG.
A laminated material C having a configuration in which a substrate film 4a is further laminated on the other surface of the substrate film 4 of the laminated material B shown in FIG. In FIG. 4 described above, reference numerals such as 4, 22, (21), and A have the same meaning as described above. In addition, the above-mentioned example is a thing which illustrated 12 examples about the laminated material using the barrier film concerning this invention, and it cannot be overemphasized that this invention is not limited by these. .

In the present invention, as the heat-sealing resin forming the heat-sealing resin layer, a resin film or sheet which can be melted by heat and fused to each other is used. Specifically, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene- Acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyethylene or Acrylic acid, methacrylic acid, polyolefin resin such as polypropylene,
Acid-modified polyolefin resins modified with unsaturated carboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, polyvinyl acetate resins, poly (meth) acrylic resins, polyvinyl chloride resins, etc. The resin film or sheet can be used. Thus, the above-mentioned film or sheet can be used in a state of a coating film of a composition containing the resin. The thickness of the film or film or sheet is 5μ.
m to 300 μm, more preferably 10 μm
About 150 μm is desirable.

In the present invention, the above-mentioned heat seal
It is particularly preferable to use an ethylene / α-olefin copolymer polymerized using a metallocene catalyst as the heat-sealing resin forming the hydrophilic resin layer. Thus, as the ethylene / α-olefin copolymer polymerized using the above metallocene catalyst, for example, a catalyst obtained by combining a metallocene complex such as a catalyst obtained by combining zirconocene dichloride and methylalumoxane with alumoxane, And an ethylene-α-olefin copolymer obtained by polymerization using a metallocene catalyst. Metallocene catalyst, the current catalyst,
The active sites are heterogeneous and are called multi-site catalysts, whereas the active sites are uniform and are also called single-site catalysts. Specifically, the product name "Kernel" manufactured by Mitsubishi Chemical Corporation, the product name "Evolu" manufactured by Mitsui Petrochemical Industry Co., Ltd., the product name "EXACT" manufactured by EXXON CHEMICAL, USA (EXACT) ", a product name" AFFINITY ", a product name" Engage (E) "manufactured by DOW CHEMICAL, USA.
NGAGE) or the like, and an ethylene / α-olefin copolymer polymerized by using a metallocene catalyst. Thus, in the present invention, as the resin of the ethylene / α-olefin copolymer polymerized by using the above-mentioned metallocene catalyst, a film or sheet or a composition containing the copolymer is used. -It can be used in the form of a coating film or the like, thereby functioning as a heat-sealing resin film or sheet constituting the innermost layer, and thus its low-temperature heat sheet. This makes it possible to prevent the occurrence of cracks or the like occurring in the inorganic oxide thin film or the like during post-processing such as bag making. The thickness of the film or film or sheet is about 3 μm to 300 μm, preferably
5 μm to 100 μm is desirable. In the present invention, the ethylene-α-olefin copolymer obtained by polymerization using the above-mentioned metallocene catalyst is further added to, for example, a partially crosslinked ethylene-propylene rubber (EPDM),
Ethylene-propylene rubber (EPR), styrene-butadiene-styrene block copolymer (SBS), styrene-isobutylene-styrene block copolymer
(SIS), using a heat-sealing resin layer of a resin composition obtained by adding one or more thermoplastic elastomers such as styrene-ethylene-butylene-styrene block copolymer (SEBS). Can also. In the present invention, as the heat-sealing resin layer,
For example, a multilayer low-density polyethylene comprising a co-extruded film obtained by co-extruding a linear low-density polyethylene and an ethylene-α-olefin copolymer obtained by polymerization using a metallocene catalyst is used. It may be a sealable resin layer.

In the present invention, the above-mentioned substrate film can be used in the same manner as the above-mentioned substrate film, for example, polyolefin resins such as polyethylene or polypropylene, polyethylene terephthalate or polyethylene naphthalate. Films or sheets of various resins such as polyester resins, polyamide resins, polycarbonate resins, and others can be used. The above resin film or sheet may be a single layer, a film formed by co-extrusion of two or more layers, or a sequential biaxial stretching method by a flat method, a simultaneous biaxial stretching method, a tube, or the like. What has been biaxially stretched using a simultaneous biaxial stretching method or the like can be used. Further, the thickness of the film may be, for example, the stability at the time of production of a film or sheet. From about 7 to 100 μm
And preferably about 9 to 30 μm.

In the present invention, since the packaging container is usually subjected to severe physical and chemical conditions, strict packaging suitability is required for the packaging material constituting the packaging container. And various conditions such as deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealability, quality maintenance, workability, hygiene, etc. are required. Any material that satisfies the above conditions can be selected and used.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, 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, poly Acrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate resin , Polyvinyl alcohol-based resin, saponified ethylene-vinyl acetate copolymer, fluorine-based resin, diene-based resin, polyacetal-based resin, polyurethane-based resin, nitrocellulose
And any other known resin film or sheet. In the present invention, the above-mentioned film or sheet may be any of unstretched and uniaxially or biaxially stretched. Also, the thickness is arbitrary,
It can be used by selecting from a range of several μm to about 300 μm. Further, in the present invention, the film or sheet may be any film such as an extruded film, an inflation film or a coating film. 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, as the paper base material constituting the paper layer, it is desirable to use a base material having a basis weight of about 80 to 600 g / m ² , preferably a base weight of about 100 to 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.

In the above description, a method of manufacturing the laminated material according to the present invention using the above-mentioned materials will be described. As the method, a method of laminating a normal packaging material, for example, , Wet lamination method, dry lamination method, solvent-free dry lamination
It can be performed by an extrusion method, an extrusion lamination method, a T-die extrusion molding method, a co-extrusion lamination method, an inflation method, a co-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 , Cellulo
Known anchor coating agents, adhesives and the like, such as adhesives for laminating, and other laminating materials, can be used.

In the laminated material according to the present invention,
Any of the layers that make up this, for example, text, graphics,
A desired printed picture layer composed of pictures, symbols, etc. can be formed. As the print pattern layer, for example, on the above-described deposited film of aluminum oxide, or on a substrate such as a substrate film, a normal gravure ink composition, offset ink composition, relief ink composition, Using ink compositions such as a screen ink composition and others, for example, using a printing method such as a gravure printing method, offset printing method, letterpress printing method, silk screen printing method, etc. Shapes, patterns,
It can be constituted by forming a desired printed pattern composed of symbols, others, and the like.

Next, in the present invention, a method for producing a bag or a box using the above-described laminated material according to the present invention will be described. In this case, the laminated material manufactured by the above method is used, and the surface of the heat-sealing resin layer of the inner layer is opposed to the laminated material. Heat the peripheral edge
The seal can be provided to form a bag.
Thus, as a bag-making method, the above-mentioned laminated material is bent with its inner layer facing the surface, or two of them are overlapped, and the peripheral end of the outer periphery is further sealed with, for example, a side sheet. Seal type, two-way seal type, three-way seal type, four-way seal type, envelope-attached seal type, gasket-attached seal type (pyro-seals)
Heat seals), heat seals such as pleated seals, flat bottom seals, square bottom seals, and the like. Packaging containers can be manufactured.

In addition, for example, self-standing packaging bags (standing pouches) can be manufactured.
In the present invention, a tube container or the like can be manufactured using the above-described composite film. In the above, as a method of the heat seal, for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal, or the like is used. Can be performed in the following manner. 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 containing a paper substrate as the packaging container, for example, a laminated material obtained by laminating a paper substrate 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 manufactured as described above is excellent in transparency, gas barrier properties against oxygen gas, water vapor, etc., impact resistance, piercing resistance, strength, etc. It is suitable for post-processing such as printing, bag making or box making. It also prevents peeling of the deposited thin film as a barrier film, and prevents the occurrence of thermal cracks and prevents its deterioration. And exhibit excellent resistance as a barrier film, for example, food and drink, chemicals, pharmaceuticals,
Various articles such as others, especially flour, bread crumbs, curry
It has the suitability for filling and packaging of powdered foods and drinks such as flour, rice flour, and others, and has sufficient storage suitability in channels such as distribution and storage, and can produce extremely good packaged products.

[0024]

Next, the present invention will be described more specifically with reference to examples. Example 1 (1). As a base film, a biaxially stretched nylon 6 film having a thickness of 15 μm was used.
(EB) heating system PVD vacuum deposition machine
Vacuum deposition under the following conditions to obtain a film thickness of 20
A deposited film of 0 ° aluminum oxide was formed into a deposited film to produce a deposited film. Deposition material: Aluminum Degree of vacuum in the take-up side chamber: 2.3 × 10 ^-3 mb
ar Degree of vacuum in the coating chamber before introducing oxygen gas:
2.9 × 10 ⁻⁴ mbar Degree of vacuum in the coating chamber after introducing oxygen gas:
4.3 × 10 ⁻⁴ mbar Transfer speed of base film: 500 m / min (Example 1) Vapor deposition surface of base film: Corona treated surface (2). The above-produced vapor-deposited film is wound with its aluminum oxide vapor-deposited film surface inside, and then
The deposited film is taken out of the deposition machine, and the deposited film is rewound with the aluminum oxide deposited film surface outside, and then stored under a constant temperature and humidity condition of 25 ° C./50% RH for 7 days. After the wet treatment, a barrier film according to the present invention was produced. (3). Next, a low-density polyethylene film (LDPE) having a thickness of 50 μm is laminated by a dry lamination method on the aluminum oxide vapor-deposited film surface of the barrier film manufactured as described above, and the present invention has the following layer structure. Was manufactured. In the above, a two-component curable urethane-based adhesive was used as the adhesive, and the amount of the adhesive was 4.5 g / m ² (solid content). 15 μm thick
Biaxially stretched nylon film, aluminum oxide evaporated film / adhesive layer / low-density polyethylene film with a thickness of 50 μm

Embodiment 2 (1). A 12 μm-thick biaxially stretched polyethylene terephthalate film was used as a base film, and was mounted on a delivery roll of an electron beam (EB) heating type PVD vacuum evaporation machine under the following conditions. Vacuum evaporation was performed to form a 200-nm-thick aluminum oxide vapor-deposited film to produce a vapor-deposited film. Deposition material: Aluminum Degree of vacuum in the take-up side chamber: 2.3 × 10 ^-3 mb
ar Degree of vacuum in the coating chamber before introducing oxygen gas:
2.9 × 10 ⁻⁴ mbar Degree of vacuum in the coating chamber after introducing oxygen gas:
4.3 × 10 ⁻⁴ mbar Transfer speed of base film: 500 m / min (Example 1) Vapor deposition surface of base film: Corona treated surface (2). The above-produced vapor-deposited film is wound with its aluminum oxide vapor-deposited film surface inside, and then
The deposited film is taken out of the deposition machine, and the deposited film is rewound with the aluminum oxide deposited film surface outside, and then stored under a constant temperature and humidity condition of 25 ° C./50% RH for 7 days. After the wet treatment, a barrier film according to the present invention was produced. (3). Next, a 60 μm-thick unstretched polypropylene film (CPP) is laminated by a dry lamination method on the aluminum oxide vapor-deposited film surface of the barrier film produced above, and the present invention has the following layer constitution. Was manufactured. In the above, a two-component curable urethane-based adhesive was used as the adhesive, and the amount of the adhesive was 3.5 g / m ² (solid content). 12 μm thick
Biaxially oriented polyethylene terephthalate film / aluminum oxide deposited film / adhesive layer / non-oriented polypropylene film with a thickness of 60 μm

Comparative Example 1 (1). As a base film, a biaxially stretched nylon 6 film having a thickness of 15 μm was used.
(EB) heating system PVD vacuum deposition machine
Vacuum deposition under the following conditions to obtain a film thickness of 20
A deposited film of 0 ° aluminum oxide was formed into a deposited film to produce a deposited film. In addition, the supply amount of oxygen gas was adjusted, and the ultraviolet transmittance of the vapor deposition film was adjusted so as to be higher than that of Examples 1 and 2 described above. Deposition material: Aluminum Degree of vacuum in the take-up side chamber: 2.3 × 10 ^-3 mb
ar Degree of vacuum in the coating chamber before introducing oxygen gas:
2.9 × 10 ⁻⁴ mbar Degree of vacuum in the coating chamber after introducing oxygen gas:
4.3 × 10 ⁻⁴ mbar Transfer speed of base film: 500 m / min (Example 1) Vapor deposition surface of base film: Corona treated surface (2). Next, a low-density polyethylene film (LDPE) having a thickness of 50 μm is laminated on the aluminum oxide vapor-deposited film surface of the vapor-deposited film manufactured above using a dry lamination method, and a laminated material having the following layer structure is formed. Manufactured. In the above, a two-component curable urethane-based adhesive was used as the adhesive, and the amount of the adhesive was 4.5 g / m ² (solid content). 15 μm thick biaxially stretched nylon 6 film, aluminum oxide deposited film / adhesive layer / thickness 50
μm low density polyethylene film

Comparative Example 2 (1). As a base film, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used, and this was used as an electron beam (EB) heating type PV.
D The film was mounted on a delivery roll of a vacuum evaporator and vacuum-evaporated under the following conditions to form a 200-mm-thick aluminum oxide vapor-deposited film to produce a vapor-deposited film. In addition, the supply amount of oxygen gas was adjusted, and the ultraviolet transmittance of the vapor deposition film was adjusted so as to be higher than that of Examples 1 and 2 described above. Deposition material: Aluminum Degree of vacuum in the take-up side chamber: 2.3 × 10 ^-3 mb
ar Degree of vacuum in the coating chamber before introducing oxygen gas:
2.9 × 10 ⁻⁴ mbar Degree of vacuum in the coating chamber after introducing oxygen gas:
4.3 × 10 ⁻⁴ mbar Transfer speed of base film: 500 m / min (Example 1) Vapor deposition surface of base film: Corona treated surface (2). Next, an unstretched polypropylene film (CPP) having a thickness of 60 μm was laminated on the aluminum oxide vapor-deposited film surface of the vapor-deposited film produced above by a dry lamination method to produce a laminated material having the following layer constitution. . In the above, a two-component curable urethane-based adhesive was used as the adhesive, and the amount of the adhesive was 3.5 g / m ² (solid content). Biaxially oriented polyethylene terephthalate film with a thickness of 12 μm, aluminum oxide deposited film / adhesive layer / unstretched polypropylene film with a thickness of 60 μm

Experimental Example 1 The film thickness and the ultraviolet transmittance at 366 nm of the vapor-deposited films and barrier films produced in Examples 1 and 2 and the vapor-deposited films produced in Comparative Examples 1 and 2 were measured. The transparency and oxygen permeability of the barrier films manufactured in Examples 1 and 2 and the vapor-deposited films manufactured in Comparative Examples 1 and 2 were measured. The thickness of the above-mentioned deposited film of aluminum oxide was measured by an absolute calibration curve method using a fluorescent X-ray analyzer.
The ultraviolet transmittance was measured using a spectrophotometer (manufactured by Shimadzu Corporation, model name: UV-2200), and the total value of the linear light and the scattered light at 366 nm of the transmitted light as the total light was used. It was measured. Furthermore, the oxygen permeability is
By the MOCON method, an oxygen gas permeability measuring device [model name, OXTRAN 2 / made by MODERN CONTROL, USA]
20]. The results are shown in Table 1 below.

[0029] In Table 1 above, the unit of the ultraviolet transmittance is%, the unit of the film thickness is Δ, and the unit of the oxygen transmittance is c.
c / m ² · day · atm. In Table 1 above, the transparency is a barrier film (Examples 1 and 2).
Judged from the difference in ultraviolet transmittance between the film and the vapor-deposited film (Comparative Examples 1 and 2), ◎ means good, and × means slightly colored.

Experimental Example 2 The laminates manufactured in Examples 1 and 2 and Comparative Examples 1 and 2 were measured for oxygen permeability and the like under the measurement conditions of 23 ° C., 40 ° C./100% RH. The above oxygen permeability is
By the MOCON method, an oxygen gas permeability measuring device [model name, OXTRAN 2 / made by MODERN CONTROL, USA]
20]. The results are shown in Table 2 below.

[0031] In Table 2 above, the unit of oxygen permeability is cc / m ²
* Day * atm.

As is clear from the experimental examples 1 and 2,
In the barrier films according to Examples 1 and 2, the UV transmittance at 366 nm was obtained by subjecting the vapor-deposited film at the time of vapor deposition to constant-temperature and constant-humidity treatment at 25 ° C./50% RH for at least one week. , And as a result, the transparency can be significantly improved compared to immediately after the vapor deposition. Further, Examples 1 to
The barrier film according to No. 2 was also superior in oxygen permeability as compared with the vapor deposition films according to Comparative Examples 1 and 2. Further, the laminated material using the barrier film according to Examples 1 and 2 has a low practical use of oxygen permeability even when stored in a laminated film state under a high temperature condition for a long time, and has high practicality. Comparative Example 1
In the samples of No. 2 to 2, the oxygen permeability was significantly deteriorated under high temperature conditions.

[0033]

As is apparent from the above description, according to the present invention, while reacting aluminum vapor and oxygen in the gas phase on one side of the base film, the reaction system is adjusted in-line to 366 nm. UV transmittance of 88-9
A deposited film of aluminum oxide adjusted to a range of 2% was formed into a film, and then a deposited film composed of a base film formed by depositing the deposited aluminum oxide film was subjected to a relative humidity of 50 ° C. at a normal temperature of 25 ° C. % RH for 1 week or more to produce a barrier film by constant temperature and humidity treatment, the UV transmittance at 366 nm can be adjusted to 95% or more, and it has extremely high transparency. Furthermore, a barrier film that is excellent in oxygen gas barrier properties, water vapor barrier properties, etc., and in particular, has found a barrier film that sufficiently withstands temperature dependency with little change in oxygen gas barrier properties even when the environmental temperature changes, and furthermore, in the above barrier film, Then, a laminated material is manufactured by laminating another plastic film or the like, and then the laminated material is used, and a bag is manufactured from the laminated material to manufacture a packaging container. And various other products, especially flour, bread crumbs, curry flour, rice flour, and other powdered foods and drinks. It has storage suitability and can produce very good packaged products.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram showing one example of a roll-up type vacuum evaporation machine.

FIG. 2 is a schematic cross-sectional view showing a layer configuration of an example of a barrier film according to the present invention.

FIG. 3 is a schematic cross-sectional view showing a layer configuration of an example of a laminate using the barrier film according to the present invention.

FIG. 4 is a schematic cross-sectional view showing a layer configuration of an example of a laminate using the barrier film according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Winding type vacuum evaporation apparatus 2 Vacuum chamber 3 Unwinding roll 4 Base film 5 Guide roll 5 'Guide roll 6 Guide roll 6' Guide roll 7 Coating drum 8 Crucible 9 Evaporation source 10 Oxygen outlet 11 Mask 12 Winding roll 22 (21) Evaporated film of aluminum oxide A Barrier film B Laminated material C Laminated material 23 Heat-sealing resin layer 4a Base film

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) BA13 CB02 EH66 EH66B EJ38A GB15 GB23 JA20A JD03 JD04 JD09B JK01 JK10 JL01 JL12C JN01 YY00A YY00B 4K029 AA11 AA25 BA44 BC00 EA01 GA01 GA03

Claims (5)

[Claims] 1. While reacting aluminum vapor and oxygen in a gas phase on one surface of a substrate film, the reaction system is adjusted in-line to adjust the ultraviolet transmittance at 366 nm to a range of 88 to 92%. The deposited film of the aluminum oxide thus formed was formed into a film, and then the deposited film composed of the base film obtained by forming the deposited film of the aluminum oxide was used as a film.
At room temperature of ℃, relative humidity of 50% RH is left for more than one week and subjected to constant temperature and constant humidity treatment to 366 nm
A barrier film, wherein the ultraviolet transmittance of the film is adjusted to 95% or more. 2. The method according to claim 1, wherein the base film is made of a biaxially stretched polyamide resin film.
2. The barrier film described in 1. 3. An aluminum oxide deposited film having a thickness of 15
The barrier film according to any one of claims 1 to 2, wherein the thickness is in the range of 0 to 300 °. 4. The reaction system is adjusted in-line while reacting aluminum vapor and oxygen in a gas phase on one surface of a substrate film to adjust the ultraviolet transmittance at 366 nm to a range of 88 to 92%. The deposited film of the aluminum oxide thus formed was formed into a film, and then the deposited film composed of the base film obtained by forming the deposited film of the aluminum oxide was used as a film.
At room temperature of ℃, relative humidity of 50% RH is left for more than one week and subjected to constant temperature and constant humidity treatment to 366 nm
A laminated material characterized in that at least a heat-sealing resin layer is laminated on a surface of a deposited aluminum oxide film of a barrier film whose ultraviolet transmittance is adjusted to 95% or more. 5. The laminated material according to claim 4, wherein a substrate film is further laminated on the other surface of the substrate film.