JP2006327202A - Barrier film and its manufacturing process - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a barrier film which has a higher barrier capability preventing the permeation of an oxygen gas, a water vapor and the like and is useful for manufacturing various kinds of packaging containers. <P>SOLUTION: The barrier film comprises a base film having a vapor deposited film of an inorganic oxide. The base film is annealed so as to exhibit a water-vapor permeation in the range of 2.0 g/m<SP>2</SP>day-0.000001 g/m<SP>2</SP>day and an oxygen permeation in the range of 2.0 cc/m<SP>2</SP>day-0.000001 cc/m<SP>2</SP>day. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a barrier film and a method for producing the same, and more specifically, has a higher barrier property that prevents permeation of oxygen gas, water vapor, and the like, and is useful for manufacturing various packaging containers. And its manufacturing method.

  Conventionally, packaging containers of various forms have been developed and proposed for filling and packaging foods and drinks, pharmaceuticals, chemicals, etc. In such packaging containers, the contents are usually In order to prevent the quality of the product from being deteriorated and to further improve its storage stability, storage property, and the like, a barrier material made of various forms is used as a material constituting the packaging container together with a plastic film or the like. Thus, in recent years, as one of the barrier materials, an inorganic oxide such as silicon oxide or aluminum oxide is formed on one surface of a base film such as a biaxially stretched polyethylene terephthalate film or a biaxially stretched nylon film. A transparent barrier film provided with a vapor deposition film of a product has been attracting attention, and packaging containers having various forms using the film have been developed and proposed. This is a barrier material made of a plastic film such as a conventional polyvinylidene chloride resin or polyvinyl alcohol resin, or a barrier made of a metal layer such as an aluminum foil or a resin film provided with a deposited film thereof. Compared to functional materials, etc., it has a barrier function that blocks the permeation of oxygen gas, water vapor, etc., and has a barrier function equivalent to or higher than that, and is particularly suitable for disposal as containers and packaging waste. For example, even if it is disposed of by incineration as it is, it is excellent in environmental measures so that it does not cause environmental destruction, and its use, demand, etc. are highly expected as a barrier material constituting packaging containers etc. It is what.

However, as a barrier material, a vapor-deposited film of an inorganic oxide such as silicon oxide or aluminum oxide is formed on one surface of a base film such as the above-described biaxially stretched polyethylene terephthalate film or biaxially stretched nylon film. In the provided transparent barrier film, for example, vapor deposition comprising the type of substrate film, vapor deposition speed, vapor deposition gas composition, vapor deposition pressure, vapor deposition gas flow rate, degree of vacuum, vapor deposition output, vapor deposition temperature, etc. It is extremely difficult to adjust the conditions, and simply forming a vapor-deposited film of an inorganic oxide such as silicon oxide or aluminum oxide makes it possible to prevent the transmission of oxygen gas, water vapor, etc. It is not something that can produce a material. For example, as a barrier material, the most important function is barrier property to prevent permeation of oxygen gas, water vapor, etc. It is extremely difficult to prepare conditions and the like, and there is often a problem that a lot of defective products are produced due to variations in each product number. Also, a transparent barrier property in which a vapor-deposited film of an inorganic oxide such as silicon oxide or aluminum oxide is provided on one surface of a base film such as the above biaxially stretched polyethylene terephthalate film or biaxially stretched nylon film The film generally has a barrier property of water vapor permeability of 10.0 g / m ² · day, and an oxygen permeability of around 10.0 cc / m ² · day · atm. It is very difficult to produce a transparent barrier film having a degree of 5.0 g / m ² · day or less and an oxygen permeability of 5.0 cc / m ² · day · atm or less. It is. Further, in the above transparent barrier film, a transparent biaxially stretched polyethylene terephthalate film or a biaxially stretched nylon film is used as a base film, and an inorganic oxide vapor deposition film such as silicon oxide is used for this. In the case of a barrier film provided with a barrier film, the reason is not clear, but it becomes a barrier film having a yellowish or tan color, which is, for example, transparent or decorated with a printed pattern, etc. There is also a problem of hindering the production of a packaging material, a packaging container, etc. that can be sufficiently satisfied. Therefore, the present invention is to provide a barrier film having a higher barrier property that prevents permeation of oxygen gas, water vapor, etc., and useful for producing various packaging containers, and a method for producing the same.

The present inventor has made various studies on the transparent barrier film, and the silicon oxide is formed on one surface of a base film such as the biaxially stretched polyethylene terephthalate film or the biaxially stretched nylon film. Alternatively, a transparent barrier film provided with a vapor deposition film of an inorganic oxide such as aluminum oxide is subjected to an annealing treatment comprising a heat treatment, whereby the base film is thermally contracted and the vapor deposition film of the inorganic oxide. Focusing on the phenomenon of yellowish or yellowish brown color change, first, silicon oxide or a biaxially stretched polyethylene terephthalate film, or a base film such as a biaxially stretched nylon film, A transparent barrier film is produced by forming a vapor-deposited film of an inorganic oxide such as aluminum oxide, and then the transparent barrier film. For example, when the annealing treatment is performed by setting the heat treatment temperature at room temperature or higher and performing the heat treatment that is left in the oven overnight, the base film constituting the transparent barrier film shrinks. In addition, the vapor deposition film of the inorganic oxide becomes closer, and further, the yellowish or yellowish brown color tone at the time of forming the vapor deposited inorganic oxide film changes. Formula MO _X that increases the degree of yellowing and increases its transparency, and constitutes an inorganic oxide vapor-deposited film (where M represents a metal element, and the value of X is a metal element The amount of change in the X value of an inorganic oxide such as silicon oxide or aluminum oxide, which is represented by the formula (1) is slightly increased, and the surface roughness of the deposited film of the inorganic oxide is also changed. As a barrier material that composes the container , The oxygen gas barrier property for blocking transmission is significantly improved, such as water vapor, and completed the present invention have found that it is possible to produce useful barrier film in the production of various packaging containers.

That is, the present invention comprises a base film provided with an inorganic oxide vapor-deposited film, and is further subjected to an annealing treatment to give a water vapor permeability of 2.0 g / m ² · day to 0.000001 g. / m ² · day range also, oxygen permeability, the barrier film and characterized by being configured in the range of ^{2.0cc / m 2 · day · atm~0.000001cc} / m 2 · day · atm It relates to the manufacturing method.

The present invention provides a transparent barrier property in which a deposited film of an inorganic oxide such as silicon oxide or aluminum oxide is provided on one surface of a base film such as a biaxially stretched polyethylene terephthalate film or a biaxially stretched nylon film. Paying attention to the phenomenon that the film undergoes annealing treatment consisting of heat treatment, the base film heat shrinks and the yellowish or tan color tone of the inorganic oxide deposition film changes. A transparent barrier is formed by forming a vapor-deposited film of an inorganic oxide such as silicon oxide or aluminum oxide on one surface of a base film such as a biaxially stretched polyethylene terephthalate film or a biaxially stretched nylon film. Then, for example, the heat treatment temperature is set to room temperature or higher, and the transparent barrier film is kept open all day and night. When the annealing treatment consisting of the heat treatment to be left was performed, the base film constituting the transparent barrier film contracted and the vapor deposition film of the inorganic oxide became tight. Further, the vapor deposition film of the inorganic oxide The yellowish or yellowish brown color tone at the time of film formation changes, the yellowness or yellowish brown color tone at the time of film formation improves its yellowing degree and increases its transparency, and the inorganic oxide Inorganic oxide such as silicon oxide or aluminum oxide represented by the formula MO _X constituting the deposited film (wherein M represents a metal element, and the value of X varies depending on the metal element) The amount of change in the X value is slightly increased, and the surface roughness of the deposited film of the inorganic oxide is also changed, and as a barrier material constituting the packaging container, a barrier that prevents permeation of oxygen gas, water vapor, etc. Improved significantly, It is that it can be produce useful barrier film in the production of packaging containers of the species.

  Hereinafter, the present invention will be described in more detail with reference to the drawings. First, an example of the layer structure of the barrier film according to the present invention will be described with reference to the drawings. FIGS. 1 and 2 show two examples of the layer structure of the barrier film according to the present invention. It is a schematic sectional drawing.

First, in the present invention, as the barrier film A according to the present invention, as shown in FIG. 1, a vapor deposition film 2 of an inorganic oxide such as silicon oxide or aluminum oxide is provided on one surface of a base film 1. Furthermore, the base film 1 provided with the vapor-deposited film 2 of the inorganic oxide is subjected to an annealing treatment including a heat treatment at a heat treatment temperature of room temperature or more and a heat treatment time of 30 minutes or more. As shown by the arrow P, the vapor deposition film 2 of the above inorganic oxide has its water vapor permeability, oxygen permeability, yellowing of color tone, and the formula MO _X constituting the vapor deposition film of the inorganic oxide (however, the formula M represents a metal element, and the value of X varies depending on the metal element.) The amount of change in the X value of the inorganic oxide, the surface roughness of the deposited inorganic oxide film, Improved properties such as shrinkage and other properties of material film And in which a basic structure to form a deposited film 3 of an inorganic oxide.

Specifically, as shown in FIG. 2, as a barrier film according to the present invention, a deposited film 2 of an inorganic oxide such as silicon oxide or aluminum oxide is provided on one surface of a base film 1, The base film 1 provided with the vapor-deposited film 2 of the inorganic oxide is subjected to an annealing treatment including a heat treatment in which the heat treatment temperature is set to room temperature or higher and the heat treatment time is set to 30 minutes or more. for vapor deposited film 2 of silicon oxide, as indicated by the arrow P _1, the water vapor ^{permeability, 2.0g / m 2 · day~0.000001g /} m 2 · day range, also the oxygen permeability, 2 It is mentioned barrier film a ₁ having the configuration that was modified in the deposited film 3a of an inorganic oxide having a ^{.0cc / m 2 · day · atm~0.000001cc} / m 2 · day · atm configuration characteristics to a range of Can

Furthermore, as another example of the barrier film according to the present invention, as shown in FIG. 3, a vapor deposition film 2 of an inorganic oxide such as silicon oxide or aluminum oxide is formed on one surface of the base film 1. Furthermore, the base film 1 provided with the inorganic oxide vapor-deposited film 2 is subjected to an annealing treatment comprising a heat treatment at a heat treatment temperature of room temperature or higher and a heat treatment time of 30 minutes or longer. Then, with respect to the above-described silicon oxide vapor deposition film 2, as shown by an arrow P ₂ , the water vapor permeability is improved in a range of 1/100 to 99/100 as compared with that before the annealing treatment. In addition, a barrier film A ₂ having a structure in which the oxygen permeability improvement rate is improved to an inorganic oxide vapor-deposited film 3b having a characteristic of improving to a range of 1/100 to 99/100 is given. be able to. In the above, the improvement rate of water vapor transmission rate means [enhancement rate = (water vapor transmission rate after annealing treatment / water vapor transmission rate before annealing treatment)], and improvement of oxygen transmission rate. The rate means [improvement rate = (oxygen permeability after annealing treatment / oxygen permeability before annealing treatment)].

Moreover, as another example of the barrier film according to the present invention, as shown in FIG. 4, a vapor deposited film of an inorganic oxide such as silicon oxide or aluminum oxide is formed on one surface of the base film 1 as shown in FIG. 2 and the base film 1 provided with the inorganic oxide vapor-deposited film 2 is subjected to an annealing treatment comprising a heat treatment in which the heat treatment temperature is at least room temperature and the heat treatment time is at least 30 minutes. As shown by the arrow P ₃ , the amount of decrease in the water vapor permeability of the silicon oxide vapor-deposited film 2 is −0.1 to −30 g / m as compared with that before the annealing treatment. range of ² · day, also modify the amount of reduction in the oxygen permeability, the vapor deposition film 3c of inorganic oxides having properties improved in a range of ^{-0.1~-10cc / m 2 · day} · atm like the barrier film a ₃ consisting of the structure It is possible.

Furthermore, as another example of the barrier film according to the present invention, as shown in FIG. 5, a vapor deposition film 2 of an inorganic oxide such as silicon oxide or aluminum oxide is formed on one surface of the base film 1. Furthermore, the base film 1 provided with the vapor-deposited film 2 of the inorganic oxide is subjected to an annealing treatment comprising a heat treatment at a heat treatment temperature of room temperature or higher and a heat treatment time of 30 minutes or longer. Then, as shown in the arrow P ₄ , the deposition of the inorganic oxide having the characteristics in which the yellowing degree of the silicon oxide deposition film 2 is improved in the range of −0.3 to −2.0. An example of the barrier film A ₄ is a modified film 3d.

Further, as another example of the barrier film according to the present invention, as shown in FIG. 6, a vapor-deposited film of an inorganic oxide such as silicon oxide or aluminum oxide is formed on one surface of the base film 1 as shown in FIG. 2 and further, an annealing treatment comprising a heat treatment in which the heat treatment temperature is set to room temperature or higher and the heat treatment time is set to 30 minutes or more on the base film 1 provided with the inorganic oxide vapor deposition film 2. As shown by the arrow P ₅ , the formula MO _X (wherein M represents a metal element, X The range of the X value of the inorganic oxide represented by the following formula is +0. An example of the barrier film A ₅ is a structure modified to an inorganic oxide vapor-deposited film 3e having characteristics increased in a range of 01 to +0.50.

Next, as another example of the barrier film according to the present invention, as shown in FIG. 7, an inorganic oxide such as silicon oxide or aluminum oxide is formed on one surface of the base film 1 as shown in FIG. The base film 1 provided with the vapor deposition film 2 and further provided with the inorganic oxide vapor deposition film 2 is heated to a temperature of room temperature or higher and a heat treatment time of 30 minutes or longer. Inorganic having a characteristic that the surface roughness of the vapor deposition film of the inorganic oxide is changed within the range of 3 to 30 nm as shown by an arrow P ₆ with respect to the vapor deposition film 2 of the above silicon oxide after the ring treatment. An example of the barrier film A ₆ is a modified structure of the oxide vapor deposition film 3f.

Next, as another example of the barrier film according to the present invention, an inorganic oxide such as silicon oxide or aluminum oxide is formed on one surface of the base film 1 as shown in FIG. The base film 1 provided with the vapor deposition film 2 and further provided with the inorganic oxide vapor deposition film 2 is heated to a temperature of room temperature or higher and a heat treatment time of 30 minutes or longer. subjected to ring process, the deposited film 2 of the silicon oxide, as indicated by an arrow P _7, as the surface roughness of the deposited film of the inorganic oxide, the standard deviation of the surface irregularities, the Rms value, 1. An example of the barrier film A ₇ is a structure modified to an inorganic oxide vapor-deposited film 3g having characteristics improved by 01 to 100 times. In the above description, the standard deviation value and Rms value of the surface irregularities are as described later.

Next, as another example of the barrier film according to the present invention, as shown in FIG. 9, an inorganic oxide such as silicon oxide or aluminum oxide is formed on one surface of the base film 1 as shown in FIG. The base film 1 provided with the vapor deposition film 2 and further provided with the inorganic oxide vapor deposition film 2 is heated to a temperature of room temperature or higher and a heat treatment time of 30 minutes or longer. subjected to ring process, the deposited film 2 of the silicon oxide, as indicated by an arrow P _8, the flow direction at the time of the shrinkage film formation of the base film, and one of at least one of the width direction In the direction, the film is shrunk in the range of -0.001 to -1.0% and the vapor deposition film of the inorganic oxide is made to be tight, and the film thickness of the vapor deposition film of the inorganic oxide is 50 to 1000 mm (5 to 100 nm) Specially constructed in the range of Mention may be made of a barrier film A ₈ having the configuration in which modified the deposited film 3h of an inorganic oxide having a. In the above, the film thickness of the vapor-deposited film of the inorganic oxide is 0.01% to 10%, and further 0.01% to 5% thinner than the film thickness before the annealing treatment. To do.

Next, as another example of the barrier film according to the present invention, as shown in FIG. 10, an inorganic oxide such as silicon oxide or aluminum oxide is formed on one surface of the base film 1 as shown in FIG. The base film 1 provided with the vapor deposition film 2 and further provided with the inorganic oxide vapor deposition film 2 is heated to a temperature of room temperature or higher and a heat treatment time of 30 minutes or longer. The silicon oxide vapor-deposited film 2 is subjected to a ring treatment, and the surface roughness of the vapor-deposited film of the inorganic oxide is compared with that before the annealing treatment, as shown by an arrow P _9. deviation value, the Rms value, increase in 1.01 to 100 times, more, its water vapor ^{permeability, 2.0g / m 2 · day~0.000001g /} m 2 · day range, also oxygen permeability the, 2.0cc / m ² · day mention may be made of a barrier film A ₉ having the configuration that was modified in the deposited film 3i of an inorganic oxide having the properties configured in the range of ^{atm~0.000001cc / m 2 · day · atm} . In the above, the standard deviation value and Rms value of the surface irregularities are the same as described above.

Next, as another example of the barrier film according to the present invention, as shown in FIG. 11, an inorganic oxide such as silicon oxide or aluminum oxide is formed on one surface of the base film 1 as shown in FIG. The base film 1 provided with the vapor deposition film 2 and further provided with the inorganic oxide vapor deposition film 2 is heated to a temperature of room temperature or higher and a heat treatment time of 30 minutes or longer. As shown by the arrow P ₁₀ , the shrinkage rate of the base film of the silicon oxide vapor-deposited film 2 is changed in the flow direction during film formation, , Shrinking to a range of -0.001 to -1.0% with respect to at least one of the width directions, and making the vapor-deposited film of the inorganic oxide closer, the water vapor permeability is 2.0 g / m ² · day~0.00 Range of 001g / m ² · day, also deposition of the oxygen permeability, an inorganic oxide having a structure characteristics in the range of ^{2.0cc / m 2 · day · atm~0.000001cc} / m 2 · day · atm An example of the barrier film A ₁₀ is a modified film 3j.

Furthermore, as another example of the barrier film according to the present invention, as shown in FIG. 12, vapor deposition of an inorganic oxide such as silicon oxide or aluminum oxide on one surface of the base film 1 is performed. An annealing consisting of a heat treatment in which a film 2 is provided and a heat treatment temperature is set to room temperature or higher and a heat treatment time is set to 30 minutes or more on the base film 1 provided with the inorganic oxide vapor deposition film 2. subjected to a treatment, for deposited film 2 of the silicon oxide, as indicated by an arrow P _11, the water vapor ^{permeability, 2.0g / m 2 · day~0.000001g /} m 2 · day range, also the oxygen permeability, constitutes in the range of ^{2.0cc / m 2 · day · atm~0.000001cc} / m 2 · day · atm, further, the yellowing factor, -0.3 2.0 And improve the range of inorganic acids Wherein MO _X (In the formula, M represents a metal element, the value of X is in the range respectively by the metal element is different.) Constituting the deposited film of an object X of the deposited film of an inorganic oxide represented by The amount of change in the value is increased to the range of +0.01 to +0.50, and the surface roughness of the inorganic oxide vapor-deposited film is varied within the range of 3 to 30 nm. An example of the barrier film A ₁₁ is a modified film 3k. The above illustrations illustrate several examples of the barrier film according to the present invention, and the present invention is not limited thereby. In the present invention, a vapor deposition film of an inorganic oxide such as silicon oxide or aluminum oxide is provided on one surface of the base film, and the base film provided with the vapor deposition film of the inorganic oxide is further subjected to a heat treatment temperature. Basically, the deposited film of an inorganic oxide such as silicon oxide or aluminum oxide is modified by performing an annealing treatment including a heat treatment at a room temperature or higher and a heat treatment time of 30 minutes or longer. The present invention relates to a barrier film having a structure.

  Next, in the present invention, materials, production methods and the like constituting the barrier film according to the present invention will be described. First, as a base film constituting the barrier film according to the present invention, silicon oxide is used as the base film. Or, since it provides a vapor-deposited film of inorganic oxide such as aluminum oxide, it has excellent properties in mechanical, physical, chemical, etc., especially it has strength and toughness, and heat resistance A resin film or sheet having the following can be used. Specifically, in the present invention, as the base film, for example, polyethylene resin, polypropylene resin, cyclic polyolefin resin, fluorine resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile Ru-butadiene-styrene copolymer (ABS resin), polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin, polyethylene terephthalate, polyethylene naphthalate Polyester resins such as various polyamide resins such as various nylons, polyimide resins, polyamideimide resins, polyaryl phthalate resins, silicone resins, polysulfone resins, polyphenylene sulfide resins, polyethersulfones Resin, polyurethane resin, AS - Le resins, cellulose - scan resin, various resins other such film or sheet - may be used and. In the present invention, it is particularly preferable to use a film or sheet of polypropylene resin, polyester resin, or polyamide resin.

  In the present invention, as the above-mentioned various resin films or sheets, for example, one or more of the above-mentioned various resins are used, and an extrusion method, a cast molding method, a T-die method, a cutting method, an inflation method are used. -A method of forming the above-mentioned various resins independently using a film-forming method such as an ionization method or the like, or a method of forming a multilayer co-extrusion film using two or more types of various resins Furthermore, films or sheets of various resins are produced by a method of using two or more kinds of resins and mixing them to form a film before forming the film. Next, regarding the various resin films or sheets produced above, the mechanical and physical properties such as heat resistance, strength, toughness, tensile strength, impact resistance, wear resistance, breakability, etc. In order to improve strength such as mechanical, chemical, etc., for example, a uniaxial stretching method that stretches in one direction or a biaxial stretching method that stretches in two directions using a tenter method, a tuber method, or the like Etc. are used to produce various resin films or sheets that are stretched uniaxially or biaxially. In the above stretching process, as the uniaxial stretching method, for example, a film extruded from a T die is stretched in the transverse direction by a longitudinal uniaxial stretching method in which the film is stretched in a longitudinal direction by a roll or a tenter called a tenter. The horizontal uniaxial stretching method can be used. In addition, as the above biaxial stretching method, for example, a tube-like film extruded from a ring-shaped die is further blown into air to be expanded, and at the same time, pulled in the vertical direction in the vertical and horizontal directions. A tube method that stretches at the same time, or a film extruded from a T-die is solidified by a cooling roll, heated to a stretching temperature (80 to 140 ° C.), and then heated at both ends with a clip of a tenter. Simultaneously biaxial stretching method that holds and extends the clip interval at a constant pitch and simultaneously stretches in the longitudinal direction at the same time as stretching in the transverse direction, or the longitudinal and lateral type method that stretches in the longitudinal direction and then stretches in the transverse direction Alternatively, the stretching process can be performed by using a sequential biaxial stretching method such as a transverse-longitudinal method in which stretching is performed in the transverse direction and then in the longitudinal direction.

  Furthermore, the various resin films or sheets stretched as described above are used to improve their physical properties such as dimensional stability, temperature expansion coefficient, humidity expansion coefficient, smoothness, and the like. Depending on the type of the material, for example, heat treatment such as heat treatment of heating at about 70 to 150 ° C. for about 1 to 76 hours is performed, so that the length is 2.5 to 6 times and the width is about 2.5 to 10 times. Various resins that are stretched and have residual stress or residual strain, and thus the residual stress or residual strain is 1% or less, specifically 0.1 to 1%. Thus, in the present invention, the above-described various resin films or sheets are used as the base film. In the present invention, the film thickness of the above-mentioned various resin films or sheets is preferably about 6 to 100 μm, more preferably about 9 to 50 μm. Regarding the residual stress or residual strain of the above-mentioned various resin films or sheets, for example, a device such as Oyama Optical Co., Ltd., model name, glass scale DL-301 is used, and JIS: C2318 Electric It can be measured by a method such as a polyester film.

  Thus, in the present invention, an inorganic oxide vapor-deposited film is provided on one surface of the base film as described above, and the base film provided with the inorganic oxide vapor-deposited film is further subjected to heat treatment. Alternatively, by performing an annealing treatment or the like comprising heat treatment, the shrinkage rate of the base film is −0.001 to at least one of the flow direction and the width direction during film formation. It shrinks in the range of -1.0% and closes the deposited film of inorganic oxide. More specifically, in the present invention, as described later, an inorganic oxide vapor deposition film is provided on one surface of the base film as described above, and the inorganic oxide vapor deposition film is further provided. By subjecting the material film to heat treatment or annealing treatment comprising heat treatment, the residual stress or residual strain within the range of 1% or less, specifically 0.1 to 1% of the base film. Etc. is corrected to a range of about 0.01 to 0.999%, so that the base film is in a range of −0.001 to −1.0% in at least one direction of one direction or two directions. As the substrate film shrinks, the inorganic oxide vapor-deposited film also shrinks, and the inorganic oxide particles themselves constituting the inorganic oxide vapor-deposited film are closely packed, whereby the oxygen permeability or Water vapor permeability, etc. The barrier is intended to significantly improve.

  It should be noted that one or more of the above-mentioned various resins are used, and in forming the film, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness Various plastic compounding agents and additives can be added for the purpose of improving and modifying mold release properties, flame retardancy, antifungal properties, electrical properties, strength, etc. Can be optionally added from a very small amount to several tens of percent depending on the purpose. In the above, general additives include, for example, colorants such as lubricants, crosslinking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, antistatic agents, lubricants, antiblocking agents, dyes, pigments and the like. Others can be used, and a modifying resin can also be used.

  In addition, in the present invention, the surface of the above-described various resin films or sheets may have a desired shape in advance in order to improve close adhesion with a silicon oxide vapor deposition film to be described later. A surface treatment layer can be provided. In the present invention, as the surface treatment layer, for example, corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, etc., For example, a corona treatment layer, an ozone treatment layer, a plasma treatment layer, an oxidation treatment layer, or the like can be formed and provided by optionally performing other pretreatments. The surface pretreatment is carried out as a method for improving the close adhesion between various resin films or sheets and a silicon oxide vapor deposition film described later. As other methods for improvement, for example, on the surface of various resin films or sheets, a primer coat agent layer, an undercoat agent layer, an anchor coat agent layer, an adhesive, in advance. A surface treatment layer can also be formed by arbitrarily forming a layer or a deposition anchor coating agent layer. Examples of the pretreatment coating agent layer include polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, melamine resins, (meth) acrylic resins, and polyacetic acid. A resin composition containing a vinyl resin, a polyolefin resin such as polyethylene or polypropylene, or a copolymer or modified resin thereof, a cellulose resin, or the like as a main component of the vehicle can be used.

  Next, in the present invention, the vapor deposition film of an inorganic oxide such as silicon oxide or aluminum oxide constituting the barrier layer according to the present invention will be described. As the vapor deposition film of an inorganic oxide such as silicon oxide or aluminum oxide, For example, a single-layer film or a two-layer film composed of one layer of a vapor-deposited film of an inorganic oxide such as silicon oxide or aluminum oxide by using, for example, chemical vapor deposition or physical vapor deposition, or a combination of both. It can be manufactured by forming a multilayer film or a composite film comprising the above.

  In the present invention, the silicon oxide vapor-deposited film by the chemical vapor deposition method will be further described. Examples of the silicon oxide vapor-deposited film by the chemical vapor deposition method include plasma chemical vapor deposition and thermal chemical vapor deposition. A vapor-deposited film of silicon oxide can be formed by using a chemical vapor deposition method (chemical vapor deposition method, CVD method) such as a growth method or a photochemical vapor deposition method. In the present invention, specifically, a vapor deposition monomer gas such as an organosilicon compound is used as a raw material on one surface of a base film, and an inert gas such as argon gas or helium gas is used as a carrier gas. In addition, a vapor deposition film of silicon oxide can be formed by using a low temperature plasma chemical vapor deposition method using an oxygen gas or the like as an oxygen supply gas and using a low temperature plasma generator or the like. In the above, as the low-temperature plasma generator, for example, a generator such as high-frequency plasma, pulse wave plasma, or microwave plasma can be used. Thus, in the present invention, highly active and stable plasma is obtained. For this purpose, it is desirable to use a high-frequency plasma generator.

  Specifically, an example of the method for forming the silicon oxide vapor deposition film by the low temperature plasma chemical vapor deposition method will be described. FIG. 13 shows the silicon oxide vapor deposition film by the plasma chemical vapor deposition method. It is a schematic block diagram of the low-temperature plasma chemical vapor deposition apparatus which shows the outline | summary about the formation method of this. As shown in FIG. 13 above, in the present invention, the base film 1 is fed out from the unwinding roll 13 arranged in the vacuum chamber 12 of the plasma chemical vapor deposition apparatus 11, and the base material is further fed. The film 1 is conveyed onto the circumferential surface of the cooling / electrode drum 15 through the auxiliary roll 14 at a predetermined speed. Therefore, in the present invention, oxygen gas, inert gas, a monomer gas for vapor deposition such as an organosilicon compound, and the like are supplied from the gas supply devices 16 and 17 and the raw material volatilization supply device 18 and the like. The vapor deposition mixed gas composition was introduced into the vacuum chamber 12 through the raw material supply nozzle 19 without adjusting the vapor deposition mixed gas composition, and was conveyed onto the cooling / electrode drum 15 peripheral surface. On the base film 1, plasma is generated by glow discharge plasma 20, and this is irradiated to form a silicon oxide vapor deposition film. In the present invention, at that time, the cooling / electrode drum 15 is applied with a predetermined power from the power source 21 disposed outside the vacuum chamber 12, and the cooling / electrode drum 15 is in the vicinity of the cooling / electrode drum 15. The generation of plasma is promoted by arranging the magnet 22. Next, the base film 1 on which the silicon oxide vapor-deposited film is formed is wound on the winding roll 24 via the auxiliary roll 23, and silicon oxide by the plasma chemical vapor deposition method according to the present invention is used. The deposited film can be formed. In the figure, 25 represents a vacuum pump. The above exemplification is an example, and it is needless to say that the present invention is not limited thereby. Although not shown, in the present invention, the inorganic oxide vapor deposition film may be not only one layer of the inorganic oxide vapor deposition film but also a multilayer film in which two or more layers are laminated, and is used. The material may be used alone or as a mixture of two or more, and an inorganic oxide vapor deposition film mixed with different materials may be formed.

In the above, the inside of the vacuum chamber 12 is depressurized by the vacuum pump 25, and the degree of vacuum is 1 × 10 ⁻¹ to 1 × 10 ⁻⁸ Torr, preferably the degree of vacuum is 1 × 10 ⁻³ to 1 × 10 ⁻⁷ Torr. It is desirable to prepare it. In the raw material volatilization supply device 18, the organic silicon compound as the raw material is volatilized and mixed with oxygen gas, inert gas, etc. supplied from the gas supply devices 16, 17, and this mixed gas is supplied to the raw material supply nozzle 19. And introduced into the vacuum chamber-12. In this case, the content of the organosilicon compound in the mixed gas is about 1 to 40%, the content of oxygen gas is about 10 to 70%, and the content of inert gas is about 10 to 60%. For example, the mixing ratio of the organosilicon compound, oxygen gas, and inert gas can be about 1: 6: 5 to 1:17:14. On the other hand, since a predetermined voltage is applied to the cooling / electrode drum 15 from the power source 21, the glow discharge plasma is generated in the vicinity of the opening of the raw material supply nozzle 19 in the vacuum chamber 12 and the cooling / electrode drum 15. 20 is generated, and the glow discharge plasma 20 is derived from one or more gas components in the mixed gas. In this state, the base film 1 is transported at a constant speed, and the glow discharge plasma 20 20, a deposited film of silicon oxide can be formed on the base film 1 on the circumferential surface of the cooling / electrode drum 15. At this time, the degree of vacuum in the vacuum chamber should be adjusted to 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably to 1 × 10 ⁻¹ to 1 × 10 ⁻² Torr. Further, it is desirable that the conveying speed of the base film 1 is adjusted to about 10 to 300 m / min, preferably about 50 to 150 m / min.

Further, in a plasma chemical vapor deposition apparatus 11 described above, formation of the deposited film of silicon oxide, on the substrate film 1, a thin film in the form of a formula SiO _X while the plasma raw material gas is oxidized with oxygen gas Therefore, the formed silicon oxide vapor-deposited film is a continuous layer that is dense, has few gaps, and is highly flexible. Therefore, the barrier property of the silicon oxide vapor-deposited film is conventionally This is much higher than the silicon oxide vapor deposition film formed by the vacuum vapor deposition method, and a sufficient barrier property can be obtained with a thin film thickness. In the present invention, the surface of the base film 1 is cleaned by plasma, and polar groups, free radicals, etc. are generated on the surface of the base film 1. This has the advantage that the close adhesion with the base film 1 is high. Further, as described above, the degree of vacuum at the time of forming the silicon oxide vapor deposition film is about 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably about 1 × 10 ⁻¹ to 1 × 10 ⁻² Torr. Since the degree of vacuum is lower than that of the 1 × 10 ⁻⁴ to 1 × 10 ⁻⁵ Torr position when forming a deposited film of silicon oxide by a conventional vacuum deposition method, The vacuum state setting time when the material film 1 is replaced can be shortened, the degree of vacuum is easily stabilized, and the film forming process is stabilized.

In the present invention, a deposited film of silicon oxide formed using a vapor-deposited monomer gas such as an organosilicon compound chemically reacts with a vapor-deposited monomer gas such as an organosilicon compound and oxygen gas. Is closely bonded to one surface of the base film to form a dense, flexible thin film, and is generally represented by the general formula SiO _x (where X represents a number from 0 to 2). Is a continuous thin film mainly composed of silicon oxide. Thus, the silicon oxide vapor-deposited film is represented by the general formula SiO _x (where X represents a number from 1.3 to 1.9) from the viewpoint of transparency and barrier properties. A thin film mainly composed of a deposited silicon oxide film is preferable. In the above, the value of X varies depending on the molar ratio of the vapor-deposited monomer gas and oxygen gas, the energy of the plasma, etc. Generally, the gas permeability decreases as the value of X decreases, but the film itself Becomes yellowish and the transparency is poor.

In addition, the silicon oxide vapor-deposited film is mainly composed of silicon oxide, and further, at least one kind of compound composed of one kind of carbon, hydrogen, silicon, or oxygen, or two or more kinds thereof is chemically used. It consists of the vapor deposition film | membrane contained by a coupling | bonding etc., It is characterized by the above-mentioned. For example, when a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit is in the form of graphite, diamond, fullerene, etc. A derivative may be contained by a chemical bond or the like. Specific examples include hydrocarbons having a CH ₃ site, hydrosilica such as SiH ₃ silyl, SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol. In addition to the above, the type, amount, etc., of the compound contained in the deposited film of silicon oxide can be changed by changing the conditions of the vapor deposition process. Thus, the content of the above compound in the deposited film of silicon oxide is about 0.1 to 50%, preferably about 5 to 20%. In the above, if the content is less than 0.1%, the impact resistance, spreadability, flexibility, etc. of the deposited silicon oxide film become insufficient, and scratches, cracks, etc. are likely to occur due to bending. It is difficult to stably maintain a high barrier property, and if it exceeds 50%, the barrier property is lowered, which is not preferable. Further, in the present invention, in the silicon oxide vapor-deposited film, the content of the above-mentioned compound is preferably decreased in the depth direction from the surface of the silicon oxide vapor-deposited film. On the surface, the impact resistance and the like can be enhanced by the above compound and the like. On the other hand, since the content of the above compound is small at the interface with the resin film, the base film and the deposited silicon oxide film This has the advantage that the tight adhesion becomes strong.

  Thus, in the present invention, the above silicon oxide vapor deposition film is subjected to surface analysis such as an X-ray photoelectron spectrometer (Xray Photoelectron Spectroscopy, XPS), a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy, SIMS), etc. The physical properties as described above can be confirmed by conducting an elemental analysis of the deposited film of silicon oxide using a method of analyzing by ion etching in the depth direction using an apparatus. In the present invention, the film thickness of the above-described silicon oxide vapor deposition film is preferably about 50 to 4000 mm, and specifically, the film thickness is preferably about 50 to 1000 mm. In the above, if it is thicker than 1000 mm, more preferably 4000 mm, it is not preferable because cracks and the like are likely to be generated in the film, and if it is less than 50 mm, it is difficult to achieve a barrier effect. Is not preferable. In the above, the film thickness can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name, RIX2000 type) manufactured by Rigaku Corporation. In the above, as means for changing the film thickness of the silicon oxide vapor deposition film, the volume velocity of the vapor deposition film is increased, that is, the method of increasing the amount of monomer gas and oxygen gas and the vapor deposition rate. This can be done by a method of slowing down.

  Next, in the above, as a monomer gas for vapor deposition of an organic silicon compound or the like that forms a vapor deposition film of silicon oxide, for example, 1.1.3.3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane , Methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyl Triethoxysilane, octamethylcyclotetrasiloxane, etc. can be used. In the present invention, among the organic silicon compounds as described above, use of 1.1.3.3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material is easy to handle and formed continuous film. In view of the above characteristics and the like, it is a particularly preferable raw material. Moreover, in the above, as an inert gas, argon gas, helium gas, etc. can be used, for example.

  Next, in the present invention, the deposited film of an inorganic oxide such as silicon oxide or aluminum oxide by the physical vapor deposition method will be described in more detail. Inorganic oxidation such as silicon oxide or aluminum oxide by the physical vapor deposition method will be described. As a vapor deposition film of an object, for example, vapor deposition of silicon oxide using a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum vapor deposition method, a sputtering method, an ion plating method, an ion cluster beam method, or the like. A film can be formed. In the present invention, specifically, a metal oxide is used as a raw material, and this is heated and vapor-deposited on a base film, or a metal or metal oxide is used as a raw material, and oxygen is added. An amorphous thin film of inorganic oxide is formed using an oxidation reaction vapor deposition method in which it is introduced and oxidized to deposit on a base film, and further a plasma-assisted oxidation reaction vapor deposition method in which the oxidation reaction is supported by plasma. be able to. In the above, as a heating method of the vapor deposition material, for example, a resistance heating method, a high frequency induction heating method, an electron beam heating method (EB), or the like can be used.

Therefore, in the present invention, as the inorganic oxide vapor-deposited film, basically, any thin film on which a metal oxide is vapor-deposited can be used. For example, silicon (Si), aluminum (Al), Magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y), etc. It is possible to use a metal oxide vapor-deposited film. Thus, preferable examples include vapor-deposited films of metal oxides such as silicon (Si) and aluminum (Al). Thus, the metal oxide vapor-deposited film can be referred to as a metal oxide such as silicon oxide, aluminum oxide, magnesium oxide, and the like, for example, SiO _x , AlO _x , MO _X (in the formula, M represents a metal element, the value of X is in the range respectively by the metal element is different.) as such MgO _X represented by. Moreover, as a range of said X value, silicon (Si) is 0-2, aluminum (Al) is 0-1.5, magnesium (Mg) is 0-1, calcium (Ca) is 0 to 1, potassium (K) is 0 to 0.5, tin (Sn) is 0 to 2, sodium (Na) is 0 to 0.5, boron (B) is 0 to 1, 5, Titanium (Ti) can take values in the range of 0 to 2, lead (Pb) in the range of 0 to 1, zirconium (Zr) in the range of 0 to 2, and yttrium (Y) in the range of 0 to 1.5. In the above, when X = 0, it is a complete metal and is not transparent and cannot be used at all. The upper limit of the range of X is a completely oxidized value. In the present invention, generally, examples other than silicon (Si) and aluminum (Al) are scarce, silicon (Si) is 1.0 to 2.0, and aluminum (Al) is 0.5. A value in the range of -1.5 can be used. In the present invention, the film thickness of the inorganic oxide vapor-deposited film as described above varies depending on the type of metal or metal oxide used, but is, for example, about 50 to 4000 mm, preferably 50 to 1000 mm. It is desirable to select and form arbitrarily within the range. In the present invention, the inorganic oxide vapor-deposited film is a metal to be used, or the metal oxide is one or a mixture of two or more, and mixed with different materials. It is also possible to constitute a vapor deposition film.

  Next, when the specific example is given about the method of forming the said inorganic oxide vapor deposition film in this invention, FIG. 14 is a schematic block diagram which shows an example of a winding-type vacuum vapor deposition apparatus. As shown in FIG. 14, the base film 1 fed out from the unwinding roll 33 in the vacuum chamber 32 of the wind-up type vacuum vapor deposition apparatus 31 is cooled through the guide rolls 34 and 35. -Guided to the dating drum 36; Thus, the evaporation source 39 heated by the crucible 37, for example, metal aluminum, aluminum oxide or the like is evaporated on the base film 1 guided on the cooled coating drum 36, Furthermore, if necessary, an oxygen gas or the like is ejected from the oxygen gas outlet 39 and an inorganic oxide vapor deposition film such as aluminum oxide is formed through the masks 40 and 40 while supplying it. Is. Next, in the present invention, in the above, for example, the base film 1 on which a vapor-deposited film of an inorganic oxide such as aluminum oxide is formed is wound on the winding roll 43 or the like via the guide rolls 41 and 42 or the like. Thus, the resin film 1 having an inorganic oxide vapor deposition film according to the present invention can be produced. The above exemplification is an example, and it is needless to say that the present invention is not limited thereby. In the present invention, the first-layer inorganic oxide vapor deposition film is first formed using the above-described take-up vacuum vapor deposition apparatus, and then the inorganic oxide vapor deposition film is formed in the same manner. Further, an inorganic oxide vapor deposition film is formed on the substrate, or by using the above-described take-up vacuum vapor deposition apparatus, these are connected in series, and the inorganic oxide vapor deposition is continuously performed. By forming the film, it is possible to form an inorganic oxide vapor-deposited film composed of two or more multilayer films.

  Next, in the present invention, the heat treatment temperature applied to the base film provided with the inorganic oxide vapor deposition film such as silicon oxide or aluminum oxide is set to room temperature or more, and the heat treatment time is set to 30 minutes or more. The heat treatment process will be described. First, as the heat treatment method, for example, a temperature-adjustable room is prepared, and in the room, the heat treatment temperature is adjusted to a predetermined temperature equal to or higher than room temperature, and silicon oxide or A substrate film provided with a vapor deposition film of inorganic oxide such as aluminum oxide is left in a state where it is stacked in a single sheet or wound around a roll, or the temperature is adjusted. In order to efficiently control the temperature of a possible drying cabinet, a substrate film provided with a vapor deposition film of an inorganic oxide such as silicon oxide or aluminum oxide in a thermostatic chamber having an air circulation device such as a rotary fan. Arm of the state stacked in two leaflets each one or, b - a method of performing left to heat treatment in a state where wound Le etc., it can be subjected to heat treatment other like methods.

  In the above, the heat treatment temperature will be further described. In the present invention, the heat treatment temperature depends on the heat treatment time and the like, but is, for example, in the range of room temperature to 200 ° C, more preferably 55 ° C to 150 ° C. It is desirable that the temperature is in the range of about ° C. Further, in the above, the heat treatment time will be further described. In the present invention, the heat treatment time depends on the heat treatment temperature and the like, but for example, is in the range of about 30 minutes to about 5 days, more preferably 12 hours. It is desirable to be in the range of about 3 days or more. Thus, in the present invention, specifically, the heat treatment temperature and the heat treatment time are such that the heat treatment temperature is in the range of about 55 ° C. to 150 ° C., and the heat treatment time is 12 hours to 36 hours. Heat treatment is preferably performed in the time range. In the present invention, more specifically, as the heat treatment, the heat treatment temperature is set to about 55 ° C., and the heat treatment time is set to about 24 hours. Further, the heat treatment temperature is set to 70 ° C. The heat treatment time is set to about 24 hours, or the heat treatment temperature is set to about 90 ° C., and the heat treatment time is set to about 24 hours. You can also. In the above heat treatment, conditions such as pressure, humidity, and others were not particularly required to be prepared.

  Thus, in the present invention, the heat treatment as described above corresponds to an annealing treatment of the base film in which the base film is raised to a certain temperature, left at that temperature for a while and then cooled to room temperature. is there. That is, in the present invention, if schematically illustrated, as shown in FIG. 15, the base film 1 provided with a vapor deposition film of an inorganic oxide such as silicon oxide or aluminum oxide is uniaxial or biaxial as described above. It is subjected to axial stretching and further subjected to heat stabilization treatment such as heat treatment, and has residual stress or residual strain. Further, the residual stress or residual strain is 1% or less, specifically 0.1% to Various resin films or sheets 1a within the range of 1% are used as the base film. Thus, in the present invention, for example, on one side of the base film 1 (1a), for example, silicon oxide, metal aluminum, aluminum oxide or the like is used as a deposition source, and this is heated and evaporated to be necessary. Then, while supplying oxygen gas or the like, inorganic oxide particles 4 such as silicon oxide or aluminum oxide are deposited, and the deposited inorganic oxide vapor deposition film 2 is formed.

Next, in the present invention, as shown in FIG. 16, the base film 1 (in which the inorganic oxide particles 4 such as silicon oxide or aluminum oxide are deposited and the deposited inorganic oxide vapor deposition film 2 is formed as described above. By performing heat treatment or annealing treatment consisting of heat treatment on 1a), first, as shown by arrow X, the base film 1 (1a) itself or its surface layer undergoes thermal shrinkage, and the base film The shrinkage rate of the film is reduced to a range of -0.001 to -1.0% with respect to at least one of the flow direction and the width direction during film formation, and the deposited inorganic oxide film is closely It is to make it. More specifically, in the present invention, an inorganic oxide vapor-deposited film is provided on one surface of the base film as described above, and the base film provided with the inorganic oxide vapor-deposited film is heated. 1% or less, specifically, residual stress or residual strain within the range of 0.1 to 1% of the base film 1 (1a) by performing annealing treatment or heat treatment. The residual stress or the residual strain is corrected to a range of about 0.01% to 0.99%, and the base film is −0.001−− in one direction or at least one of the two directions. The base film 1b is formed by shrinking to a range of 1.0% to give its dimensional stability, eliminating defects, and improving physical properties, and accompanying this, silicon oxide provided thereon Or aluminum oxide As a result, the deposited inorganic oxide vapor deposition film 2 contracts and the like, and as shown by the arrow Y, the silicon oxide or the silicon oxide constituting the inorganic oxide vapor deposition film 2 is deposited. Inorganic oxide particles 4 such as aluminum oxide are in close contact with each other in some form, sealing the gaps, etc., and closing them to form a dense, continuous thin film of inorganic oxide. By forming the vapor-deposited film 2a, the water vapor permeability, oxygen permeability, yellowing of the color tone, and the formula MO _X constituting the vapor-deposited film of the inorganic oxide (wherein M represents a metal element, The range of X values varies depending on the metal element.) Inorganic oxides with modified properties such as the amount of change in the X value of inorganic oxides, the surface roughness of the deposited inorganic oxide film, etc. Vapor deposition film (steamed inorganic oxide shown in 3 to 3k in the above-mentioned illustration) It is capable of forming a film). In the above, 1% or less of the base film, specifically, the residual stress or residual strain within the range of 0.1 to 1% is removed, and the residual stress or residual strain is 0.01% to Correction to the range of about 0.99% means that the residual stress or residual strain within the range of 1% or less, specifically 0.1-1% of the base film is 0.01-95. This corresponds to correcting the residual stress or residual strain of the base film at a rate of about%.

  In the present invention, when the heat treatment temperature is not more than room temperature, the deposition of an inorganic oxide such as silicon oxide or aluminum oxide is performed on a base film provided with a vapor deposition film of an inorganic oxide such as silicon oxide or aluminum oxide. There is no change in the film quality of the film, and it is not preferable to create its effect, and when it is 200 ° C. or higher, more preferably 150 ° C. or higher, the base film is melted and its shape It is preferable because it cannot be retained, and it is not preferable because the productivity is also inferior. In the present invention, when the heat treatment time is not longer than 30 minutes, in the base film provided with a vapor-deposited film of an inorganic oxide such as silicon oxide or aluminum oxide, as described above, silicon oxide or oxidation There is no change in the film quality of the vapor-deposited film of inorganic oxide such as aluminum, and it is not preferable to create its effect, and it is not preferable, and if it is 5 days or more, further 3 days or more, its productivity It is not preferable because it is inferior to the above.

As apparent from the above description, in the present invention, a vapor deposition film of an inorganic oxide such as silicon oxide or aluminum oxide is provided on one surface of the base film, and further, an inorganic film such as silicon oxide or aluminum oxide is provided. The base film provided with the oxide film is subjected to an annealing treatment including a heat treatment at a heat treatment temperature of room temperature or higher and a heat treatment time of 30 minutes or more. to be reformed deposited film of silicon oxide or the inorganic oxide such as aluminum oxide reforming provided, its water vapor permeability, oxygen permeability, color of yellowing, silicon oxide represented by the formula SiO _X constituting the deposited film Inorganic oxides such as silicon oxide or aluminum oxide whose characteristics such as X value change amount, deposited film surface roughness, base film shrinkage, inorganic oxide deposited film thickness, etc. have changed It is capable of forming a deposited film.

Thus, in the present invention, as the barrier material constituting the packaging container or the like, a vapor deposition film of an inorganic oxide such as silicon oxide or aluminum oxide is provided on one surface of the base film, and the oxidation A base film provided with a vapor deposition film of an inorganic oxide such as silicon or aluminum oxide is heat-treated at a temperature of room temperature or higher and a heat treatment time of 30 minutes or longer to be provided on the base film. and the film quality of the deposited film of an inorganic oxide such as silicon oxide or aluminum oxide, the water vapor ^{permeability, 2.0g / m 2 · day~0.000001g /} m 2 · day range, also the oxygen permeability constitutes in the range of ^{2.0cc / m 2 · day · atm~0.000001cc} / m 2 · day · atm, further, the degree of yellowing, enhance the range of -0.3 to 2.0, And, Machine formula MO _X constituting the deposited film of oxide (wherein, M represents a metal element, the value of X is in the range respectively by the metal element is different.) X inorganic oxide represented by The amount of change in the value is increased to the range of +0.01 to +0.50, and the surface roughness of the inorganic oxide vapor-deposited film is adjusted to the range of 3 to 30. It is preferable to produce a barrier film having a modified structure.

Further, in the present invention, a vapor deposition film of an inorganic oxide such as silicon oxide or aluminum oxide is provided on one surface of the base film, and a vapor deposition film of an inorganic oxide such as silicon oxide or aluminum oxide is further provided. The substrate film is subjected to an annealing treatment comprising a heat treatment in which the heat treatment temperature is set to room temperature or higher and the heat treatment time is set to 30 minutes or more. The shrinkage rate is contracted within a range of -0.001 to -1.0% with respect to at least one of the flow direction and the width direction during film formation, and is inorganic. The oxide deposited film has a thickness in the range of 50 to 1000 mm (5 to 100 nm). In the present invention, after the annealing treatment as described above, the base film provided with a vapor deposition film of an inorganic oxide such as silicon oxide or aluminum oxide has its water vapor permeation as compared with that before the annealing treatment. The improvement rate of the rate [improvement rate = (after treatment / before treatment)] is in the range of 1/100 to 99/100, and the improvement rate of the oxygen permeability [improvement rate = (treatment After ÷ before treatment)] is in the range of 1/100 to 99/100, and the water vapor transmission rate decreases in the range of −0.1 to −30 g / m ² · day. And the amount of decrease in oxygen permeability is in the range of −0.1 to −10 cc / m ² · day · atm. Furthermore, in the present invention, after the annealing treatment as described above, the base film provided with a vapor deposition film of an inorganic oxide such as silicon oxide or aluminum oxide has a surface roughness of the vapor deposition film of the inorganic oxide, The standard deviation value and Rms value of the surface irregularities are improved 1.01 to 100 times as compared with those before the annealing treatment. The standard deviation value and Rms value of the surface irregularities are as described later.

Next, in the present invention, an inorganic oxide vapor deposition film such as silicon oxide or aluminum oxide is provided on one surface of the base film, and the inorganic oxide vapor deposition film is further provided on the base film. The annealing process comprising the heat treatment at a heat treatment temperature of room temperature or higher and a heat treatment time of 30 minutes or more is performed, and the silicon oxide vapor-deposited film is compared with that before the annealing treatment. The surface roughness of the deposited film of the inorganic oxide is improved, and the standard deviation value and the Rms value of the surface unevenness are improved by 1.01 to 100 times. Further, the water vapor permeability is set to 2.0 g / m ² · day. range ~0.000001g / m ² · day, also inorganic oxide having an oxygen permeability, was constructed in the range of ^{2.0cc / m 2 · day · atm~0.000001cc} / m 2 · day · atm characteristics Vapor deposition film It is capable of producing a barrier film consisting of modified configuration.

Next, in the present invention, a vapor deposition film of an inorganic oxide such as silicon oxide or aluminum oxide is provided on one surface of the base film, and further, the base film provided with the vapor deposition film of the inorganic oxide is provided. The annealing process comprising the heat treatment at a heat treatment temperature of room temperature or higher and a heat treatment time of 30 minutes or more is performed, and the silicon oxide vapor-deposited film is compared with that before the annealing treatment. The shrinkage rate of the base film is shrunk in a range of −0.001 to −1.0% with respect to at least one of the flow direction and the width direction during film formation, the water vapor ^{permeability, 2.0g / m 2 · day~0.000001g /} m 2 · day range, also the oxygen ^{permeability, 2.0cc / m 2 · day ·} atm~0.000001cc / m 2 · range of day and atm It is capable of producing a barrier film consisting of modified the configuration deposited film of an inorganic oxide having characteristics configuration.

  In the present invention, the film quality of the deposited film of inorganic oxide such as silicon oxide or aluminum oxide provided on the base film is changed and modified by heat treatment or annealing treatment comprising heat treatment. The reason for this is not clear, but as described above, the vapor-deposited film of inorganic oxide such as silicon oxide or aluminum oxide provided on one surface of the base film by vapor deposition or the like is vaporized such as silicon oxide or aluminum oxide. Is deposited, and an inorganic oxide vapor deposition film made of silicon oxide or aluminum oxide with the accumulated particles is formed. A large number of micropores are formed, and the gaps constituting the micropores are caused by heat treatment or annealing treatment comprising heat treatment. In addition, the base film itself or its surface layer shrinks and the inorganic oxide vapor deposition film made of silicon oxide or aluminum oxide also cooperates, and the particles such as silicon oxide or aluminum oxide constituting the vapor deposition film of the inorganic oxide However, it is understood that this is due to the formation of a dense, continuous thin film by closing the gap or the like and closing the gap.

  Next, in the present invention, the barrier film according to the present invention produced as described above uses this as a barrier material, and other plastic film, paper base material, metal foil or metal plate, cellophane, One or more kinds of various base materials such as woven or non-woven fabrics, glass plates, and the like are arbitrarily laminated to produce laminated materials having various forms, and thus the laminated materials are used for packaging. Various applications such as materials, optical members, protective sheets for solar cell modules, protective films for organic EL displays, protective films for film liquid crystal displays, packaging materials for polymer batteries, aluminum packaging materials, etc. It can be applied to. As an example of the method for producing the laminated material, for example, a primer agent layer is first formed on the surface of the vapor-deposited film of an inorganic oxide such as silicon oxide or aluminum oxide of the barrier film according to the present invention. Then, a laminating adhesive layer is formed on the surface of the primer layer, and then a substrate such as a plastic film is interposed through the primer layer and the laminating adhesive layer. By laminating the materials using the dry lamination method, laminated materials having various forms can be produced. Alternatively, in the present invention, for example, first, a primer agent layer is formed on the surface of an inorganic oxide vapor deposition film such as silicon oxide or aluminum oxide of the barrier film according to the present invention, and then the primer agent layer. An anchor coat agent layer is formed on the surface, and then various resins are melt-extruded through the primer agent layer and the anchor coat agent layer to laminate a desired base material. Laminating materials having various forms can be produced by laminating using the extrusion laminating method. In addition, in this invention, it is the same as the above on the surface of the base film which comprises the barrier film concerning this invention. In the present invention, other base materials can be arbitrarily laminated depending on the purpose of use, use form, application, etc., and various forms of laminated materials can be designed and produced. It can be done.

  Next, in the present invention, the above-described laminated material will be described as an example of use, and a packaging container will be described as an example. In the present invention, as the packaging container, for example, two sheets of the above-mentioned laminated material are prepared. Then, the surfaces of the heat-sealable resin layer located in the innermost layer are made to face each other, and thereafter, the seal part is formed by heat-sealing the three ends of the outer periphery. In addition, a three-sided seal type soft packaging container can be manufactured by providing an opening on the upper side. Thus, in the present invention, although not shown, from the opening of the three-sided seal type soft packaging container manufactured above, for example, the contents such as food and drink, etc. are filled, and then the upper Heat seal the opening to form an upper seal, etc., and, if necessary, for example, boil treatment, retort treatment, etc., to produce packaged products of various forms It is something that can be done. In the present invention, it goes without saying that the present invention is not limited to the illustrated packaging containers shown above, and depending on the purpose, use, etc., a flexible packaging bag, a liquid paper container, a paper can, It goes without saying that various types of packaging containers such as others can be manufactured.

Next, in the present invention, the primer agent layer constituting the laminate material will be described. First, as the primer agent layer, a polyurethane resin or a polyester resin is used as a main component of the vehicle, and the polyurethane agent layer The silane coupling agent is about 0.05 to 10% by weight, preferably about 0.1 to 5% by weight, and the filler is 0.1 to 20% by weight with respect to 1 to 30% by weight of the resin or polyester resin. , Preferably in a proportion of about 1 to 10% by weight, and if necessary, additives such as stabilizers, curing agents, crosslinking agents, lubricants, ultraviolet absorbers, etc. are optionally added to the solvent. Then, a diluent or the like is added and mixed well to prepare a polyurethane-based or polyester-based resin composition, and thus the polyurethane-based or polyester-based resin composition is used. For example, by using a roll coat, a gravure coat, a knife coat, a dip coat, a spray coat, or other coating methods, an inorganic oxide vapor deposited film such as silicon oxide or aluminum oxide is used. Then, the coating film is dried to remove the solvent, diluent, etc., and if necessary, an aging treatment or the like is performed to obtain the primer layer according to the present invention. Can be formed. In the present invention, the film thickness of the primer layer is preferably, for example, about 0.1 g / m ^{2 to} 1.0 g / m ² (dry state). Therefore, in the present invention, the primer layer as described above improves the tight adhesion between the deposited film of inorganic oxide such as silicon oxide or aluminum oxide and the heat seal resin layer. In addition, the degree of elongation of the primer agent layer is improved, for example, laminating processing or improving post-processing suitability such as bag making processing, and a deposited film of an inorganic oxide such as silicon oxide or aluminum oxide at the time of post-processing This prevents the occurrence of cracks and the like.

  In the above, as the polyurethane resin constituting the polyurethane resin composition, for example, a polyurethane resin obtained by a reaction between a polyfunctional isocyanate and a hydroxyl group-containing compound can be used. Specifically, for example, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, hexamethylene diisocyanate, xylylene diisocyanate One obtained by reacting a polyfunctional isocyanate such as an aliphatic polyisocyanate such as a salt with a hydroxyl group-containing compound such as a polyether polyol, a polyester polyol, a polyacrylate polyol, or the like. A liquid or two-component curable polyurethane resin can be used. Thus, in the present invention, by using the polyurethane-based resin as described above, the close adhesion between the deposited silicon oxide film and the heat-sealable resin layer is improved and the primer agent layer is improved. The degree of elongation is improved and, for example, the suitability for post-processing such as laminating or bag making is improved, and the occurrence of cracks or the like in the deposited film of silicon oxide during post-processing is prevented.

  In the above, the polyester resin constituting the polyester resin composition includes, for example, one or more aromatic saturated dicarboxylic acids having a benzene nucleus such as terephthalic acid as a basic skeleton, A thermoplastic polyester resin produced by polycondensation with one or more valent alcohols can be used. In the above, examples of the aromatic saturated dicarboxylic acid having a benzene nucleus as a basic skeleton include terephthalic acid, isophthalic acid, phthalic acid, diphenyl ether-4, 4-dicarboxylic acid, and the like. In the above, saturated divalent alcohols include ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, Polytetramethylene glycol, hexamethylene glycol, dodecamethylene glycol, aliphatic glycols such as neopentyl glycol, alicyclic glycols such as cyclohexanedimethanol, 2.2- Bis (4'-β-hydroxyethoxyphenyl) propane, naphthalene diol, other aromatic geo- and the like can be used.

  In the present invention, specific examples of the polyester resin include thermoplastic polyethylene terephthalate resin produced by polycondensation of terephthalic acid and ethylene glycol, terephthalic acid and tetramethylene glycol. Polybutylene terephthalate resin produced by polycondensation with styrene, thermoplastic polycyclohexanedimethylene terephthalate resin produced by polycondensation of terephthalic acid and 1,4-cyclohexanedimethanol, terephthalic acid Polyethylene terephthalate resin produced by copolycondensation of phthalic acid, isophthalic acid and ethylene glycol, produced by copolycondensation of terephthalic acid, ethylene glycol and 1,4-cyclohexanedimethanol Thermoplastic polyethylene terephthalate resin, terephthalic acid and isophthalic acid And ethylene glycol - le and propylene glycol - thermoplastic polyethylene terephthalate produced by co-polycondensation of Le - DOO resins, polyester polyol - can be used Le resin, other like. In the present invention, the saturated aromatic dicarboxylic acid having a benzene nucleus as a basic skeleton as described above, for example, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, One or more aliphatic saturated dicarboxylic acids such as sebacic acid and dodecanoic acid can be added and copolycondensed, and the amount used is an aromatic saturated dicarboxylic acid having a benzene nucleus as a basic skeleton, It is preferable to add 1 to 10% by weight. Thus, in the present invention, by using the polyester resin as described above, the tight adhesion and the like are improved and the elongation of the primer layer is improved, for example, laminating or It improves post-processing suitability such as bag-making processing and prevents the occurrence of cracks and the like in the deposited film of inorganic oxide during post-processing.

  Next, in the above, as the silane coupling agent constituting the polyurethane-based or polyester-based resin composition, organic functional silane monomers having binary reactivity can be used, for example, γ-chloropropyl Trimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- Glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyl Dimethoxysilane, γ One or more of ureidopropyltriethoxysilane, bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, an aqueous solution of γ-aminopropylsilicone, and the like can be used.

  In the silane coupling agent as described above, a functional group at one end of the molecule, usually, chloro, alkoxy, or acetoxy group is hydrolyzed to form a silanol group (SiOH), which is a silicon oxide. Alternatively, a metal constituting an inorganic oxide vapor deposition film such as aluminum oxide, or an active group on the surface of an inorganic oxide vapor deposition film such as silicon oxide or aluminum oxide, for example, a functional group such as a hydroxyl group and some action, for example, Then, a reaction such as a dehydration condensation reaction is caused, and a silane coupling agent is modified with a covalent bond or the like on the surface of the deposited film of an inorganic oxide such as silicon oxide or aluminum oxide. Further, the silicon oxide of the silanol group itself or A strong bond is formed on the surface of the deposited film of an inorganic oxide such as aluminum oxide by adsorption or hydrogen bonding. On the other hand, an organic functional group such as vinyl, methacryloxy, amino, epoxy, or mercapto at the other end of the silane coupling agent is formed on the thin film of the silane coupling agent. -Reacts with substances constituting the adhesive layer, anchor coating layer, other layers, etc. to form a strong bond, and further, the above-mentioned printed pattern layer, laminating adhesive layer, The heat-sealable resin layer is firmly and tightly bonded through the anchor coating agent layer and the like to increase the laminating strength. Thus, in the present invention, the laminating strength is increased. It is possible to form a high-strength laminated structure. In the present invention, the inorganic property and organic property of the silane coupling agent are utilized, and the heat treatment is carried out through a silicon oxide vapor-deposited film and a printed pattern layer, an adhesive layer or an anchor coating agent layer. -Improving the tight adhesion with the rusty resin layer, thereby increasing the laminating strength and the like.

  Next, in the present invention, examples of the filler constituting the polyurethane-based or polyester-based resin composition include calcium carbonate, barium sulfate, alumina white, silica, talc, glass frit, resin powder, and the like. Can be used. Thus, the above-mentioned filler adjusts the viscosity of the polyurethane-based or polyester-based resin composition liquid, improves its coating suitability, and is a silane coupling with a polyurethane-based or polyester-based resin as a binder resin. It binds via an agent to improve the cohesive strength of the coating film.

Next, in the present invention, the laminating adhesive layer constituting the laminated material will be described. Examples of the laminating adhesive layer constituting the laminating adhesive layer include a polyvinyl acetate adhesive and acrylic acid. Homopolymers such as ethyl, butyl, 2-ethylhexyl ester, etc., or polyacrylate adhesives comprising these and copolymers of methyl methacrylate, acrylonitrile, styrene, etc., cyanoacrylate adhesives, ethylene Ethylene copolymer adhesives, cellulose adhesives, polyester adhesives, polyamide adhesives, polyimides, and the like, and copolymers of monomers such as vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, etc. -Based adhesives, amino resin-based adhesives made of urea resin or melamine resin, and phenolic resin-based adhesives Epoxy adhesives, polyurethane adhesives, reactive (meth) acrylic adhesives, rubber adhesives such as chloroprene rubber, nitrile rubber, styrene-butadiene rubber, silicone adhesives, alkali metal silicates Inorganic adhesives made of low-melting glass or the like, and other adhesives can be used. The composition system of the above adhesive may be any composition form such as an aqueous type, a solution type, an emulsion type, and a dispersion type, and the properties thereof are film / sheet type, powder type, solid type, etc. Any form may be used, and the bonding mechanism may be any form such as a chemical reaction type, a solvent volatilization type, a heat melting type, and a hot pressure type. Thus, the above adhesive can be applied by, for example, a roll coating method, a gravure roll coating method, a kiss coating method, a coating method, etc., or a printing method. The coating amount is preferably about 0.1 to 10 g / m ² (dry state).

Next, in the present invention, the anchor coat agent layer constituting the laminated material will be described. As the anchor coat agent constituting the anchor coat agent layer, for example, alkyl titanate or the like is used. Various aqueous or oil-based anchor coating agents such as organic titanium, isocyanate, polyethyleneimine, polyptadiene, etc. can be used. The above-mentioned anchor coating agent can be coated using a coating method such as a roll coat, a gravure roll coat, a kiss coat, and the like. The amount is preferably 0.1 to 5 g / m ² (dry state).

  Examples of the melt-extruded resin layer in the melt-extrusion laminating method include, for example, polyethylene resins, polypropylene resins, acid-modified polyethylene resins, acid-modified polypropylene resins, ethylene-acrylic acid or methacrylic acid copolymers, saps. 1 of thermoplastic resins such as phosphorus resin, ethylene-vinyl acetate copolymer, polyvinyl acetate resin, ethylene-acrylic acid ester or methacrylic acid ester copolymer, polystyrene resin, polyvinyl chloride resin, etc. Species or two or more can be used. In the melt extrusion lamination method, in order to obtain stronger adhesive strength, for example, lamination can be performed through an anchor coating agent layer such as the above-described anchor coating agent.

  Next, in the present invention, as the base material such as a plastic film forming the innermost layer or the outermost layer of the laminated material, for example, a heat-seal resin film that can be melted by heat and fused to each other Specifically, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, ethylene polymerized using a metallocene catalyst -Α-olefin copolymer, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid Acid methyl copolymer, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyethylene Polyolefin resins such as polyethylene or polypropylene modified with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, polyvinyl acetate resins, poly A film or sheet of a resin such as (meth) acrylic resin, polyvinyl chloride resin, or the like can be used. Thus, the above film or sheet can be used in the state of a coating film made of a composition containing the resin. The thickness of the film or film or sheet is preferably about 5 μm to 300 μm, more preferably about 10 μm to 100 μm.

  Furthermore, in the present invention, as a base material such as a plastic film constituting the above laminated material, for example, as a basic material of the laminated material, excellent properties in mechanical, physical, chemical, etc. In particular, a resin film or sheet having strength, toughness, and heat resistance can be used. Specifically, for example, polyester resin, polyamide resin, polyaramid Films, sheets, etc. of tough resins such as resin, polyolefin resin, polycarbonate resin, polystyrene resin, polyacetal resin, fluorine resin, etc. can be used. . Thus, as the resin film or sheet, any of an unstretched film or a stretched film stretched in a uniaxial direction or a biaxial direction can be used. The thickness of the film is about 5 μm to 100 μm, preferably about 10 μm to 50 μm. In the present invention, the base film as described above is subjected to surface printing or back printing by a normal printing method with a desired printing pattern such as letters, figures, symbols, patterns, patterns, etc., for example. May be.

Next, in the present invention, as the base material constituting the laminated material, for example, various paper base materials constituting the paper layer can be used. Specifically, in the present invention, Materials include formability, bending resistance, rigidity, etc., for example, strong sized bleached or unbleached paper base, or pure white roll paper, kraft paper, paperboard, processed paper Paper base materials such as, etc., etc. can be used. 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 . Of course, in the present invention, the paper base material constituting the paper layer and various resin films or sheets as the base film mentioned above can be used in combination.

  Furthermore, in the present invention, examples of the material constituting the laminated material include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, and ethylene having barrier properties such as water vapor and water. -Resin film or sheet such as propylene copolymer, or resin film such as polyvinylidene chloride, polyvinyl alcohol, saponified ethylene-vinyl acetate copolymer having barrier properties against oxygen, water vapor, etc. It is also possible to use various colored resin films or sheets having light-shielding properties obtained by adding a colorant such as a pigment to a sheet or a resin and adding a desired additive and kneading to form a film. it can. These materials can be used alone or in combination. The thickness of the film or sheet is arbitrary, but is usually about 5 μm to 300 μm, more preferably about 10 μm to 100 μm.

  In the present invention, usually, when the above laminated material is applied to various applications, it is subjected to severe conditions both physically and chemically. Various requirements such as deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealing performance, quality maintenance, workability, hygiene, etc. are required. Can be used by arbitrarily selecting a material that satisfies the above-mentioned conditions. 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, methyl Pentene 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 (ABS resin), polyester resin, polyamide resin, polycarbonate resin, polyvinyl alcohol Resin, saponified ethylene-vinyl acetate copolymer, fluorine resin, diene resin, polyacetal resin, polyurethane resin, nitrocellulose, etc. You can select and use. In addition, for example, a film such as cellophane, a synthetic paper, or the like can be 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.

  Thus, in the present invention, when performing the above-mentioned lamination, if necessary, pretreatment such as corona treatment and ozone treatment can be applied to the film, and for example, isocyanate (urethane) Type), polyethyleneimine type, polybutadiene type, organic titanium type anchor coating agent, or polyurethane type, polyacrylic type, polyester type, epoxy type, polyvinyl acetate type, cellulose type, etc. -Known pretreatments such as adhesives for coating, anchor coating agents, adhesives, and the like can be used.

  In the present invention, a desired printed pattern layer can be formed between any of the layers constituting the laminated material. Thus, the printed pattern layer is mainly composed of one or more ordinary ink vehicles, and if necessary, a plasticizer, a stabilizer, an antioxidant, a light stabilizer, an ultraviolet ray, and the like. One or more additives such as an absorbent, a curing agent, a crosslinking agent, a lubricant, an antistatic agent, a filler, and the like are arbitrarily added, and a colorant such as a dye / pigment is added, and a solvent is added. The ink composition is prepared by sufficiently kneading with a diluent, and then the ink composition is used. For example, gravure printing, offset printing, letterpress printing, screen printing, transfer printing, flexographic printing, etc. The printing pattern layer according to the present invention can be formed by printing a desired printing pattern composed of characters, figures, symbols, patterns, etc. on the above-described coating thin film using a printing method such as .

In the present invention, as the primer agent layer provided on the surface of the vapor-deposited film of the inorganic oxide such as silicon oxide or aluminum oxide, a primer agent layer made of the polyurethane-based or polyester-based resin composition described above is used. Furthermore, for example, a polyamide resin, an epoxy resin, a phenol resin, a (meth) acrylic resin, a polyvinyl acetate resin, a polyolefin resin such as polyethylene aly polypropylene, or a copolymer or modified resin thereof. The primer agent layer can be formed using a resin composition containing cellulose-based resin, etc. as the main component of the vehicle. In the present invention, for example, a primer coating layer is formed by coating using a coating method such as a roll coat, a gravure roll coat, a kiss coat, or the like. Therefore, the coating amount is preferably about 0.1 to 10 g / m ² (dry state).

  Next, in the present invention, a description will be given of a bag making or box making method for manufacturing a packaging container using the above-described laminated material. For example, when the packaging container is a flexible packaging bag made of a plastic film or the like Using the laminated material manufactured by the method as described above, facing the heat-sealable film of the inner layer facing each other, folding them up or stacking the two sheets, The bag body can be configured by heat sealing the portion to provide a seal portion. Thus, as a bag-making method, the above-mentioned laminated material is folded with the inner layer faces facing each other, or the two sheets 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, and in the present invention, a tube container or the like can also be manufactured using the above-described laminated material. 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 laminated material in which a paper base material is laminated is manufactured, and a blank plate for manufacturing a desired paper container is prepared 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 used for filling and packaging various foods, chemicals such as adhesives and adhesives, cosmetics, pharmaceuticals, miscellaneous goods such as chemical warmers, and other items. It is what is used. Thus, in the present invention, in particular, for example, a liquid sachet for filling and packaging soy sauce, sauce, soup, etc., a soft packaging bag for filling and packaging fresh confectionery, etc., or boiled or retort food, etc. It is useful as a packaging container for filling and packaging liquid foods and drinks such as soft packaging bags to be filled and packaged, and other foods and drinks containing moisture.

Hereinafter, the present invention will be described in more detail with reference to examples. In the examples below, water vapor permeability, oxygen permeability, degree of yellowing, the variation of X values of silicon oxide represented by the formula SiO _X constituting the deposited film, and, for deposited film surface roughness Measured by the following measurement method.
(1). Measurement of water vapor permeability This is a barrier film measured at a temperature of 40 ° C. and a humidity of 90% RH with a measuring instrument manufactured by MOCON, USA (model name: PERMATRAN). did.
(2). Measurement of oxygen permeability This was measured for a barrier film under the conditions of a temperature of 23 ° C. and a humidity of 90% RH with a measuring instrument (model name: OXTRAN) manufactured by MOCON, USA.
(3). This is a measurement of the yellowing degree (YI ₀ ) of a barrier film based on the provisions of JIS-K7103, the yellowness (YI ₀ ) is measured before heating, and the yellowness (YI) is measured again after heating. Thus, the difference between before and after was defined as the degree of yellowing (ΔYI).
(4). Measurement of the amount of change in the X value of the silicon oxide of the formula SiO _X constituting the deposited film which, for a barrier film, X-ray photoelectron spectrometer (Xray Photoelectron Spectroscopy: XPS) using a vapor deposition of silicon oxide Elemental analysis of the film surface is performed, the ratio of silicon and oxygen on the surface detected at that time is obtained, the ratio of oxygen to silicon 1 is taken as X value, and before and after heating under the conditions described in the examples The amount of change in value was calculated and measured.

(5). Measurement of surface roughness of deposited film First, in the present invention, the surface roughness of the deposited film was measured using an atomic force microscope (AFM). This uses an atomic force microscope (US, Digital Instruments, model name, NanoScope IIIa) for the barrier film, and the probe is a single crystal silicon [US Manufactured by Nanosensors, product name, NCH-10T]. In the measurement area 5 × 5 μm area, the number of data points measured at 256 × 256 points is “N”, the height of each data is “Zi”, and the average value is “Z avg”. In this case, in order to obtain the size of the surface unevenness, the standard deviation value of the Z value of all data, “Rms value”, was obtained and measured. As the reason for obtaining the standard deviation, only the unevenness when the singular point exists can be measured only by obtaining the Max-Min difference in the measurement area, and therefore the standard deviation value was measured. The calculation formula is as shown in the following formula 1.

With respect to the Rms value obtained with an atomic force microscope, the surface roughness was measured using a material whose surface step was previously calibrated with a known sample. Further, in the present invention, the surface roughness of the deposited film was separately measured using an electron microscope (Scanning Electron Microscope, SEM). This is because, with respect to the barrier film, first, in order to protect the deposited film, a cyanoacrylate-based adhesive is applied to the surface of the deposited film, and then dried. The substrate film provided with was cut, and the cut surface was photographed at a magnification of 50,000 times or more, and the state of the undulation (waved state) of the deposited film was confirmed. Further, for a base film provided with an inorganic oxide vapor deposition film, first, another resin film is laminated on the inorganic oxide vapor deposition film to form a laminate (product state), and then the lamination In the same manner as above, the material was cut with a diamond knife, and the cut surface was photographed at a magnification of 50,000 times or more. ) Can also be confirmed. Next, the height of each concavo-convex was measured with a caliper from a photograph taken of the surface waviness (waved state, concavo-convex). Moreover, the actual value of the height of each unevenness | corrugation was computed from the scale calibrated previously shown on the electron micrograph. Regarding the unevenness determined from the above electron microscope, the measurement area is small compared to the atomic force microscope, and the atomic force microscope calculates the unevenness of the surface from the entire surface, whereas in the electron microscope, Since only information on the cross section can be obtained and a large number of measurements cannot be obtained, the result of the electron microscope (SEM) is a Range value that is the MAX-MIN difference of the unevenness. The calculation method is as follows.
Range value = MAX-MIN As a result, the MAX-MIN difference of the electron microscope is almost the same as the MAX-MIN difference obtained from the atomic force microscope, and the surface unevenness due to the heat treatment or the annealing treatment comprising the heat treatment. It was also possible to confirm the effect on From this point, it was found that almost the same results were obtained regardless of the atomic force microscope or electron microscope.

(6). Measurement of Heat Shrinkage Ratio of Base Film This measurement was performed on the barrier film based on the measurement of 6.3.5 heat shrinkage ratio in “JIS: C2318 polyester film for electricity”. Five test pieces each having a width of about 20 mm and a length of 150 mm are taken in both the flow direction and the width direction of the base film, and each center is scratched with a knife as a reference point at a distance of about 100 mm. The test piece is hung vertically in a constant temperature box kept at a set temperature of ± 3 ° C., heated for a set time, taken out, left at room temperature for 30 minutes, and then the distance between the gauge points is measured. Calculate with the following formula and find the average value.
Heat shrinkage rate (%) = [(L ₁ −L ₂ ) / L ₁ ] × 100 In the above formula, L ₁ represents the distance between the gauge points before heating (mm), and L ₂ is Represents the distance between the gauge points after heating (mm). The heat shrinkage rate was also calculated for the flow direction and the width direction.

Example 1 (1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used, and this was mounted on a delivery roll of a plasma chemical vapor deposition apparatus. A 200 nm thick silicon oxide vapor deposition film was formed on the corona-treated surface of the film.
(Deposition conditions)
Deposition surface; corona-treated surface introduction gas amount; hexamethyldisiloxane: oxygen gas: helium = 1.0: 3.0: 3.0 (unit: slm)
Degree of vacuum in vacuum chamber; 2-6 × 10 ⁻⁶ mBar Deposition chamber in vacuum; 2-5 × 10 ⁻³ mBar cooling and electrode drum supply power; 10 kW line speed; 100 m / min (2). Next, the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm on which the silicon oxide vapor deposition film having a thickness of 200 mm is formed is wound on a winding roll, and then the winding roll is heated to a heating temperature. Is put in a room (heating oven) where the heat treatment temperature shown in Table 1 below and the annealing treatment consisting of heat treatment according to the heat treatment time are performed, and the characteristics shown in Table 1 below are obtained. A barrier film according to the present invention was produced.

In Table 1 above, the unit of temperature is [° C.], the unit of water vapor permeability is [g / m ² / day · 40 ° C./90% RH], and the unit of oxygen permeability is [cc / M ² / day · 23 ° C. · 90% RH], the unit of surface roughness is [nm], and the unit of thermal shrinkage of the base film is [%].

As is clear from the measurement results shown in Table 1 above, the barrier film according to the present invention has a silicon oxide vapor-deposited film provided on the base film, which has been modified by heat treatment. every time, the color of yellowing, the change amount of the X value of the silicon oxide of the formula SiO _X constituting the deposited film, the deposited film surface roughness, the characteristics of thermal shrinkage or the like of the substrate film was changed, modified It was confirmed that a deposited silicon oxide film can be formed.

Reference Example 1 (1). Next, for the barrier film produced by performing the heat treatment under the conditions of the temperature of 90 ° C. and the time of 24 hours in Example 1 above, a glow discharge plasma generator is used on the silicon oxide vapor deposition film surface, Power: 9 kw, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2.5 (unit: slm) mixed gas pressure: 6 × 10 ⁻⁵ Torr, processing speed: 420 m Oxygen / argon mixed gas plasma treatment was performed at / min to form a plasma treated surface in which the surface tension of the silicon oxide deposition film surface was improved by 54 dyne / cm or more. On the other hand, after applying corona discharge treatment to one side of the paper substrate [basis weight 425 g / m ² ], a low density polyethylene resin was used for the corona discharge treatment surface, and this was extrusion coated. A low-density polyethylene resin layer having a thickness of 30 μm was formed. Next, using a tandem extrusion laminating machine, a polyethyleneimine anchor coating agent layer was formed on the non-coated surface of the paper substrate, and then the anchor coating agent layer was applied to the anchor coating agent layer. The plasma-treated surfaces of the above barrier films are opposed to each other, and an ethylene-methacrylic acid copolymer (manufactured by Mitsui DuPont Polychemical Co., Ltd., trade name, Nucrel N0908C, extrusion temperature: 290 ° C., extrusion film thickness 20 μm) This was extruded and laminated, and the paper base material and the barrier film were bonded to each other, followed by a first extrusion lamination step. Subsequently, in the second extrusion lamination step, a two-component curable anchor coat agent [Takeda Pharmaceutical Co., Ltd.] is applied to the surface of the 12 μm thick biaxially stretched polyethylene terephthalate film constituting the barrier film. Kogyo Co., Ltd., trade name, Takerak A3210 / Takenet A3075, coating amount: 1 g / m ² (dry state)] was applied with a gravure coater, passed through a drying furnace, -On the surface of the coating agent layer, an ethylene-α / olefin copolymer film (Dainippon Resin Co., Ltd., trade name, JME-12N, film thickness 40 μm) polymerized using a metallocene catalyst is opposed. A low-density polyethylene resin (trade name, M16P, extrusion temperature: 320 ° C., extrusion film thickness: 20 μm) manufactured by Mitsui Petrochemical Co., Ltd. is used between the layers, and both are extruded while being extruded. And Nsando, to produce a laminate.
(2). Next, using the laminated material produced above, according to the shape of the Gebel top type liquid paper container, engraved creases in the vertical, horizontal, or slanting and punching processing, the paste margin part After the blank plate is manufactured, and then the end surface of the blank plate manufactured as described above is subjected to a skive hemming treatment to prevent permeation of contents, liquid leakage, etc. Hot-air treatment is performed, and the ethylene-α / olefin copolymer film polymerized using the metallocene catalyst of the adhesive margin is melted, and the other end of the blank plate is overlaid on the melt surface. Both of them were bonded together to form a cylinder-sealed seal portion, and a cylindrical sleeve was manufactured. Next, the inner surface of the bottom of the cylindrical sleeve manufactured above is blown with hot air, and the ethylene-α / olefin copolymer film polymerized using the metallocene catalyst on the inner surface is melted, and the press seal is obtained. To form a bottom seal part, and after filling the juice juice from the other opening, the inner surface of the top was scrubbed with hot air, and the ethylene polymerized using the metallocene catalyst on the inner surface The α-olefin copolymer film was melted and press sealed to form a gel top seal portion, and the sealed liquid paper container according to the present invention filled and packaged with the contents was manufactured. The sealed liquid paper container produced above is free from the occurrence of twisted pinholes, has excellent barrier properties against oxygen gas, water vapor, etc., and has excellent fragrance retention, and alteration of its contents is recognized. Moreover, it was excellent in laminating strength, etc., withstood distribution in the market, and excellent in storage and preservation. In Example 1, the barrier film produced by performing the heat treatment under other conditions was obtained in the same manner as described above, and almost the same results were obtained.

Example 2 (1) A biaxially stretched nylon 6 film having a thickness of 15 μm was used as a substrate, and this was mounted on a feed roll of a plasma chemical vapor deposition apparatus, and a silicon oxide having a thickness of 150 mm under the conditions shown below. Was formed on one surface of the biaxially stretched nylon 6 film.
(Deposition conditions)
Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 11: 10 (unit: slm)
Degree of vacuum in the vacuum chamber: 5.2 × 10 ⁻⁶ mbar Degree of vacuum in the deposition chamber: 5.1 × 10 ⁻² mbar Cooling and electrode drum power supply: 18 kW Film transport speed: 70 m / min Deposition surface: Corona Processing surface (2). Next, the 15 μm-thick biaxially stretched nylon 6 film on which the silicon oxide vapor deposition film having a thickness of 150 mm is formed is wound on a winding roll, and then the heating temperature is adjusted for the winding roll. Barrier property concerning the present invention which has the characteristic shown in the following table 2 by putting into the room (heating oven) which can be done, and performing heat processing at the heat processing temperature shown in the following table 2, and the heat processing time A film was produced.

In Table 2 above, the unit of temperature is [° C.], the unit of water vapor permeability is [g / m ² / day · 40 ° C./90% RH], and the unit of oxygen permeability is [cc / M ² / day · 23 ° C. · 90% RH], the unit of surface roughness is [nm], and the unit of thermal shrinkage of the base film is [%].

As is clear from the measurement results shown in Table 2 above, the barrier film according to the present invention has a silicon oxide vapor-deposited film provided on the base film that has been modified by heat treatment. every time, the color of yellowing, the change amount of the X value of the silicon oxide of the formula SiO _X constituting the deposited film, the deposited film surface roughness, the characteristics of thermal shrinkage or the like of the substrate film was changed, modified It was confirmed that a deposited silicon oxide film can be formed.

Reference Example 2 (1). Next, the barrier film produced by heat treatment in the above Example 2 under the conditions of a temperature of 90 ° C. and a time of 24 hours was used, and on the surface of the deposited silicon oxide film, exactly the same as in the above Example 1 Thus, a plasma-treated surface was formed. Next, an epoxy-based silane coupling agent (8.0% by weight) and an anti-blocking agent (8.0% by weight) are added to the initial condensation product of the polyurethane-based resin on the plasma-treated surface of the deposited silicon oxide film of the barrier film produced above. 1.0% by weight) is added, and a primer composition obtained by sufficiently kneading is used, so that the film thickness becomes 0.4 g / m ² (dry state) by the gravure roll coating method. To form a primer layer. Furthermore, a two-component curable polyurethane laminating adhesive is used on the surface of the primer layer formed as described above, and this is subjected to a film thickness of 4. by the gravure roll coating method as described above. An adhesive layer for laminating was formed by coating so as to be 0 g / m ² (dry state). Next, a linear low density polyethylene film having a thickness of 50 μm is superimposed on the surface of the adhesive layer for laminating formed as described above with the corona-treated surfaces facing each other, and then both are laminated by dry lamination. Thus, a laminated material was manufactured.
(2). Next, two sheets of the laminated material produced above were prepared, the surfaces of the linear low-density polyethylene film were overlapped facing each other, and then the outer peripheral edge was three-sided. A three-sided seal-type flexible packaging pouch having a seal portion and an opening at the top was produced. The soy sauce is filled and packaged from the opening in the three-side seal type sachet produced above, and then the opening is heat sealed to form the upper seal part. A liquid sachet packaging product was produced. The liquid sachet packaged product manufactured above has excellent barrier properties against oxygen gas, water vapor, etc., and has excellent laminating strength, etc., withstands distribution in the market, and is excellent in storage and storage. . . In Example 2, the barrier film produced by performing the heat treatment under other conditions was almost the same as described above.

Example 3 (1). A biaxially stretched polyethylene terephthalate film with a thickness of 12 μm is used, and silicon monoxide (SiO) with a purity of 99.9% is applied to the corona-treated surface by high-frequency dielectric heating under a vacuum of 1 × 10 ⁻⁴ Torr. Evaporation was performed by heating to form a 200Å silicon oxide vapor deposition film.
(2). Next, the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm on which the silicon oxide vapor deposition film having a thickness of 200 mm is formed is wound on a winding roll, and then the winding roll is heated to a heating temperature. Is put in a room (heating oven) in which can be prepared, heat treatment is performed at the heat treatment temperature and heat treatment time shown in Table 3 below, and the present invention having the characteristics shown in Table 3 below is applied. A barrier film was produced.

In Table 3 above, the unit of temperature is [° C.], the unit of water vapor permeability is [g / m ² / day · 40 ° C./90% RH], and the unit of oxygen permeability is [cc / M ² / day · 23 ° C. · 90% RH], the unit of surface roughness is [nm], and the unit of thermal shrinkage of the base film is [%].

As is clear from the measurement results shown in Table 3 above, the barrier film according to the present invention has a silicon oxide vapor-deposited film provided on the base film that has been modified by heat treatment. every time, the color of yellowing, the change amount of the X value of the silicon oxide of the formula SiO _X constituting the deposited film, the deposited film surface roughness, the characteristics of thermal shrinkage or the like of the substrate film was changed, modified It was confirmed that a deposited silicon oxide film can be formed.

Reference Example 3 (1). Next, a barrier film produced by heat treatment in the above Example 3 at a temperature of 90 ° C. for 24 hours was used, and a glow discharge plasma generator was used on the silicon oxide film. , Power 9 kw, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2.5 (unit: slm), mixed gas pressure 6 × 10 ⁻² mbar, processing speed Oxygen / argon mixed gas plasma treatment was performed at 420 m / min to form a plasma treated surface in which the surface tension of the silicon oxide deposition film surface was improved by 54 dyne / cm or more. Next, an epoxy-based silane coupling agent (8.0% by weight) and an anti-blocking agent (8.0% by weight) are added to the initial condensation product of the polyurethane-based resin on the plasma-treated surface of the deposited silicon oxide film of the barrier film produced above. 1.0% by weight) is added, and a primer composition obtained by sufficiently kneading is used, so that the film thickness becomes 0.4 g / m ² (dry state) by the gravure roll coating method. To form a primer layer. Furthermore, a two-component curable polyurethane laminating adhesive is used on the surface of the primer layer formed as described above, and this is subjected to a film thickness of 4. by the gravure roll coating method as described above. An adhesive layer for laminating was formed by coating so as to be 0 g / m ² (dry state). Next, a linear low density polyethylene film having a thickness of 50 μm is superimposed on the surface of the adhesive layer for laminating formed as described above with the corona-treated surfaces facing each other, and then both are laminated by dry lamination. Thus, a laminated material was manufactured.
(2). Next, two sheets of the laminated material produced above were prepared, the surfaces of the linear low-density polyethylene film were overlapped facing each other, and then the outer peripheral edge was three-sided. A three-sided seal-type flexible packaging pouch having a seal portion and an opening at the top was produced. The soy sauce is filled and packaged from the opening in the three-side seal type sachet produced above, and then the opening is heat sealed to form the upper seal part. A liquid sachet packaging product was produced. The liquid sachet packaged product manufactured above has excellent barrier properties against oxygen gas, water vapor, etc., and has excellent laminating strength, etc., withstands distribution in the market, and is excellent in storage and storage. . . In Example 3, the barrier film produced by performing the heat treatment under other conditions was obtained in the same manner as described above, and almost the same results were obtained.

Example 4 (1). Using a biaxially stretched nylon 6 film with a thickness of 15 μm, silicon monoxide (SiO) with a purity of 99.9% is heated and evaporated on the corona-treated surface using a high-frequency dielectric heating method under a vacuum of 1 × 10 ⁻⁴ Torr. To form a 200-nm silicon oxide vapor-deposited film.
(2). Next, the biaxially stretched nylon 6 film having a thickness of 15 μm, on which the silicon oxide vapor deposition film having a thickness of 200 mm is formed as described above, is wound on a winding roll, and then the heating temperature is adjusted for the winding roll. Barrier property concerning the present invention which has the characteristic shown in the following table 4 by putting into the room (heating oven) which can be done, and performing heat processing at the heat processing temperature and heat processing time shown in the following table 4 A film was produced.

In Table 4 above, the unit of temperature is [° C.], the unit of water vapor permeability is [g / m ² / day · 40 ° C./90% RH], and the unit of oxygen permeability is [cc / M ² / day · 23 ° C. · 90% RH], the unit of surface roughness is [nm], and the unit of thermal shrinkage of the base film is [%].

As is clear from the measurement results shown in Table 4 above, the barrier film according to the present invention has a silicon oxide vapor deposition film provided on the base film that has been modified by heat treatment. every time, the color of yellowing, the change amount of the X value of the silicon oxide of the formula SiO _X constituting the deposited film, the deposited film surface roughness, the characteristics of thermal shrinkage or the like of the substrate film was changed, modified It was confirmed that a deposited silicon oxide film can be formed.

Reference example 4 (1). In the same manner as in Reference Example 3 above, the above-mentioned Reference was applied to the plasma-treated surface of the deposited silicon oxide film of the barrier film produced by heat treatment in Example 4 above at a temperature of 90 ° C. for 24 hours. A primer layer was formed exactly as in Example 3. Next, a two-component curable urethane anchor coat agent is used on the surface of the primer layer formed as described above, and this is coated with a film thickness of 0.1 g / m ² (by gravure roll coat method). The coating layer was dried to form an anchor coating layer. Next, a linear low density polyethylene resin is used on the surface of the anchor coating agent layer formed as described above, and this is melt extruded using an extruder to form a linear low density polyethylene resin having a thickness of 50 μm. The layers were extruded and laminated to produce a laminate.
(2). Next, two sheets of the laminated material produced above were prepared, the surfaces of the linear low-density polyethylene film were overlapped facing each other, and then the outer peripheral edge was three-sided. A three-sided seal-type flexible packaging pouch having a seal portion and an opening at the top was produced. The soy sauce is filled and packaged from the opening in the three-side seal type sachet produced above, and then the opening is heat sealed to form the upper seal part. A liquid sachet packaging product was produced. The liquid sachet packaged product manufactured above has excellent barrier properties against oxygen gas, water vapor, etc., and has excellent laminating strength, etc., withstands distribution in the market, and is excellent in storage and storage. . In Example 4, the barrier film produced by performing the heat treatment under other conditions was almost the same as described above.

Example 5 (1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used as a base film. First, the above-mentioned biaxially stretched polyethylene terephthalate film is mounted on a feed-out roll of a take-up vacuum deposition machine, Next, this is fed out, and an electron beam (EB) heating method is performed while supplying oxygen gas to the corona-treated surface of the biaxially stretched polyethylene terephthalate film using silicon monoxide (SiO) as an evaporation source. A silicon oxide vapor deposition film having a film thickness of 30 nm was formed by the vacuum vapor deposition method under the following vapor deposition conditions.
(Deposition conditions)
Deposition chamber internal vacuum: 1.33 × 10 ⁻² Pa (1 × 10 ⁻⁴ Torr)
Vacuum degree in take-up chamber; 1.33 × 10 ⁻² Pa electron beam power; 25 kw film transport speed; 400 m / min deposition surface; corona treatment surface; Immediately after forming, a glow discharge plasma generator is used on the surface of the deposited silicon oxide film, and further, power is 9 kw, oxygen gas: argon gas = 7.0: 2.5 (unit: slm) A plasma treatment surface was formed by performing a plasma treatment with an oxygen / argon mixed gas at a mixed gas pressure of 6 × 10 ⁻⁵ Torr.
(2). Next, the 12 μm-thick biaxially stretched polyethylene terephthalate film on which the silicon oxide vapor-deposited film having a thickness of 30 nm is formed is wound on the winding roll, and then the winding roll is heated to the heating temperature. Is put into a room (heating oven) in which can be prepared, heat treatment is performed at the heat treatment temperature and the heat treatment time shown in Table 5 below, and the present invention having the characteristics shown in Table 5 below is applied. A barrier film was produced.

In Table 5 above, the unit of temperature is [° C.], the unit of water vapor permeability is [g / m ² / day · 40 ° C./90% RH], and the unit of oxygen permeability is [cc / M ² / day · 23 ° C. · 90% RH], the unit of surface roughness is [nm], and the unit of thermal shrinkage of the base film is [%].

As is clear from the measurement results shown in Table 5 above, the barrier film according to the present invention was modified by the heat treatment to modify the vapor deposition film of silicon oxide provided on the base film, and the water vapor permeability and oxygen permeability. every time, the color of yellowing, the change amount of the X value of the silicon oxide of the formula SiO _X constituting the deposited film, the deposited film surface roughness, the characteristics of thermal shrinkage or the like of the substrate film was changed, modified It was confirmed that a deposited silicon oxide film can be formed.

Reference Example 5 (1). A polyester-based resin (glass transition point: 67 ° C., molecular weight: 18000) on the surface of the vapor-deposited silicon oxide film of the barrier film produced by heat treatment under the conditions of 90 ° C. for 24 hours in Example 5 above. Is used as a main component of the vehicle, and further, a primer agent using ethyl acetate as a diluting solvent is used, and this is coated by the gravure roll coating method, and then heat-treated at 80 ° C. for 1 minute. A transparent resin primer layer having a film thickness of 0.7 to 0.8 g / m ² (dry state) was formed. Next, after forming a desired printed pattern on the surface of the transparent resin primer layer formed above, a two-component curable polyurethane laminating adhesive is used on the entire surface including the printed pattern, This was coated by a gravure roll coating method to a film thickness of 4.0 g / m ² (dry state), and then dried to form a laminating adhesive layer. On the surface of the laminating adhesive layer, a biaxially stretched nylon 6 film having a thickness of 15 μm was laminated with its corona-treated surface facing each other, and then both were laminated by dry lamination. Next, after the corona discharge treatment was applied to the surface of the biaxially stretched nylon 6 film laminated as described above, a two-component curable polyurethane laminating adhesive was used on the corona treatment surface in the same manner as described above. Then, this was coated by a gravure roll coating method to a film thickness of 4.0 g / m ² (in a dry state) to form an adhesive layer for laminating. Next, an unstretched polypropylene film having a thickness of 60 μm was dry-laminated and laminated on the surface of the laminating adhesive layer formed above to produce a laminated material.
(2). Next, two sheets of the laminated material produced above were prepared, the surfaces of the unstretched polypropylene film were opposed to each other, and then the outer peripheral edge was sealed in a three-way heat seal. A three-sided seal-type flexible packaging bag having an opening and an upper opening was produced. In the three-sided seal type soft packaging bag produced above, water is filled and packaged from the opening, and then the opening is heat sealed to form the upper seal. A semi-finished packaging product is manufactured, and then the semi-finished packaging product is placed in a retort kettle and subjected to retort processing under conditions of temperature, 120 ° C., pressure, 2.1 kgf / cm ² · G, time, 30 minutes. Retort packaged food was manufactured. The retort packaged food manufactured above has excellent heat resistance, pressure resistance, water resistance, barrier properties, heat seal properties, pin hole resistance, piercing properties, transparency, etc. Excellent barrier properties against oxygen gas, water vapor, etc., with no bag breakage or leakage of contents, etc., and functions as a food container, such as content filling and packaging suitability, distribution suitability, storage suitability, etc. . Regarding the above barrier properties, before retorting, oxygen permeability, 0.38 cc / m ² / day · 23 ° C./90% RH, water vapor permeability, 0.22 g / m ² / day · 40 ° C./90% RH On the other hand, after retorting, oxygen permeability, 0.56 cc / m ² / day · 23 ° C./90% RH, water vapor permeability, 0.76 g / m ² / day · 40 ° C./90% RH. In Example 5 above, the barrier film produced by performing the heat treatment under other conditions was almost the same as described above, and substantially the same results were obtained.

Example 6 (1). A biaxially stretched nylon 6 film having a thickness of 15 μm is used as a base film. First, the above biaxially stretched nylon 6 film is mounted on a delivery roll of a take-up vacuum deposition apparatus, and then this is attached. Using a vacuum deposition method using an electron beam (EB) heating system while supplying oxygen gas to the corona-treated surface of the biaxially stretched nylon 6 film, while using aluminum as a deposition source, A vapor-deposited film of aluminum oxide having a thickness of 200 mm was formed.
(Deposition conditions)
Degree of vacuum in the deposition chamber: 2 × 10 ⁻⁴ mbar Take-up chamber in vacuum: 2 × 10 ⁻² mbar Electron beam power: 25 kW Film transport speed: 420 m / min Deposition surface: Corona treatment surface (2). Next, the biaxially stretched nylon 6 film having a thickness of 15 μm on which the aluminum oxide vapor-deposited film having a thickness of 200 mm is formed is wound on a winding roll, and then the heating temperature is adjusted for the winding roll. Barrier property concerning the present invention which has the characteristic shown in the following table 6 by putting into the room (heating oven) which can be done, and performing heat processing at the heat processing temperature and the heat processing time shown in the following table 6 A film was produced.

In Table 6, the unit of temperature is [° C.], the unit of water vapor permeability is [g / m ² / day · 40 ° C./90% RH], and the unit of oxygen permeability is [cc / M ² / day · 23 ° C. · 90% RH], the unit of surface roughness is [nm], and the unit of thermal shrinkage of the base film is [%].

As is clear from the measurement results shown in Table 6 above, the barrier film according to the present invention has a silicon oxide vapor-deposited film provided on the base film that has been modified by heat treatment. every time, the color of yellowing, the change amount of the X value of the silicon oxide of the formula SiO _X constituting the deposited film, the deposited film surface roughness, the characteristics of thermal shrinkage or the like of the substrate film was changed, modified It was confirmed that a deposited silicon oxide film can be formed.

Reference Example 6 (1). First, a normal gravure ink composition is used on one side of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, and a predetermined printing pattern composed of letters, figures, symbols, patterns, etc. is formed by a gravure printing method. A printed pattern layer was formed by printing. Next, a two-component curable polyurethane laminating adhesive is used on the entire surface including the printed pattern layer formed as described above, and this is applied to a film thickness of 4.0 g / m by a gravure roll coating method. ² (Dry state) was coated to form an adhesive layer for laminating. Subsequently, the barrier film produced by heat-treating the surface of the adhesive layer for laminating formed in the above in Example 6 under the conditions of a temperature of 90 ° C. and a time of 24 hours was deposited on the aluminum oxide vapor-deposited film. The two surfaces were opposed to each other, and then both were dry laminated. Next, the surface of the biaxially stretched nylon 6 film of the barrier film that has been dry-laminated is subjected to a rolling discharge treatment, and then the corona-treated surface is subjected to a two-component curable polyurethane laminating adhesive. Was coated by a gravure roll coating method so as to have a film thickness of 4.0 g / m ² (in a dry state) to form an adhesive layer for laminating. Next, an unstretched polypropylene film having a thickness of 60 μm was dry-laminated and laminated on the surface of the laminating adhesive layer formed above to produce a laminated material.
(2). Next, two sheets of the laminated material produced above were prepared, the surfaces of the unstretched polypropylene film were opposed to each other, and then the outer peripheral edge was sealed in a three-way heat seal. A three-sided seal-type flexible packaging bag having an opening and an upper opening was produced. In the three-sided seal type soft packaging bag produced above, water is filled and packaged from the opening, and then the opening is heat sealed to form the upper seal. A semi-finished packaging product is manufactured, and then the semi-finished packaging product is placed in a retort kettle and subjected to retort treatment under conditions of temperature, 120 ° C., pressure, 2.1 kgf / cm ² · G, time, 30 minutes. The retort food according to the present invention was manufactured. The retort food produced above has a packaging bag with excellent heat resistance, pressure resistance, water resistance, barrier properties, heat seal properties, pin hole resistance, piercing properties, transparency, etc. It was excellent in barrier properties against oxygen gas, water vapor, etc., and there was no bag breakage or leakage of contents, and it was excellent in functions as a food container, for example, filling / packaging suitability, distribution suitability, storage suitability, etc. Regarding the above barrier properties, before retorting, oxygen permeability, 0.50 cc / m ² / day · 23 ° C./90% RH, water vapor permeability, 0.26 g / m ² / day · 40 ° C./90% RH On the other hand, after retorting, oxygen permeability, 0.56 cc / m ² / day · 23 ° C./90% RH, water vapor permeability, 0.38 g / m ² / day · 40 ° C./90% RH. In Example 6, the barrier film produced by performing the heat treatment under other conditions was obtained in the same manner as described above, and almost the same results were obtained.

Example 7 (1). As a base film, 0.1 to 0.3 g / m of polyester polyol is previously used. ² (Dry state) Using a coated biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, first, the above biaxially stretched polyethylene terephthalate film is mounted on a take-up roll of a take-up type vacuum deposition machine. Next, this is fed out, and an electron beam (EB) heating method is performed while supplying oxygen gas to the coated surface of the biaxially stretched polyethylene terephthalate film using silicon monoxide (SiO) as a deposition source. A silicon oxide vapor deposition film having a thickness of 30 nm was formed by the vacuum vapor deposition method under the following vapor deposition conditions.
(Deposition conditions)
Deposition chamber internal vacuum degree: 1.33 × 10 ^-2 Pa (1 × 10 ^-Four Torr)
Winding chamber internal vacuum degree: 1.33 × 10 ^-2 Pa electron beam power; 25 kw film conveyance speed; 400 m / min deposition surface; corona treatment surface Next, immediately after forming a silicon oxide deposition film with a thickness of 30 nm as described above, the surface of the silicon oxide deposition film is , Using a glow discharge plasma generator, and further using a mixed gas of power 9 kw, oxygen gas: argon gas = 7.0: 2.5 (unit: slm), and mixed gas pressure 6 × 10 ^-Five An oxygen / argon mixed gas plasma treatment was performed at Torr to form a plasma treated surface.
(2). Next, the 12 μm-thick biaxially stretched polyethylene terephthalate film on which the silicon oxide vapor-deposited film having a thickness of 30 nm is formed is wound on the winding roll, and then the winding roll is heated to the heating temperature. Is put in a room (heating oven) where can be prepared, heat treatment is performed at the heat treatment temperature and the heat treatment time shown in Table 7 below, and the present invention having the characteristics shown in Table 7 below is applied. A barrier film was produced.

In Table 5 above, the unit of temperature is [° C.], the unit of water vapor permeability is [g / m ² / day · 40 ° C./90% RH], and the unit of oxygen permeability is [cc / M ² / day · 23 ° C. · 90% RH], the unit of surface roughness is [nm], and the unit of thermal shrinkage of the base film is [%].

As is clear from the measurement results shown in Table 7 above, the barrier film according to the present invention was modified by the heat treatment to modify the vapor deposition film of silicon oxide provided on the base film, and the water vapor permeability, oxygen transmission every time, the color of yellowing, the change amount of the X value of the silicon oxide of the formula SiO _X constituting the deposited film, the deposited film surface roughness, the characteristics of thermal shrinkage or the like of the substrate film was changed, modified It was confirmed that a deposited silicon oxide film can be formed.

Reference Example 7 (1). A polyester-based resin (glass transition point: 67 ° C., molecular weight: 18000) is formed on the surface of the vapor-deposited silicon oxide film of the barrier film produced by heating at 90 ° C. for 24 hours in Example 7 above. Is used as a main component of the vehicle, and further, a primer agent using ethyl acetate as a diluting solvent is used, and this is coated by the gravure roll coating method, and then heat-treated at 80 ° C. for 1 minute. A transparent resin primer layer having a film thickness of 0.7 to 0.8 g / m ² (dry state) was formed. Next, after forming a desired printed pattern on the surface of the transparent resin primer layer formed above, a two-component curable polyurethane laminating adhesive is used on the entire surface including the printed pattern, This was coated by a gravure roll coating method to a film thickness of 4.0 g / m ² (dry state), and then dried to form a laminating adhesive layer. On the surface of the laminating adhesive layer, a biaxially stretched nylon 6 film having a thickness of 15 μm was laminated with its corona-treated surface facing each other, and then both were laminated by dry lamination. Next, after the corona discharge treatment was applied to the surface of the biaxially stretched nylon 6 film laminated as described above, a two-component curable polyurethane laminating adhesive was used on the corona treatment surface in the same manner as described above. Then, this was coated by a gravure roll coating method to a film thickness of 4.0 g / m ² (in a dry state) to form an adhesive layer for laminating. Next, an unstretched polypropylene film having a thickness of 60 μm was dry-laminated and laminated on the surface of the laminating adhesive layer formed above to produce a laminated material.
(2). Next, two sheets of the laminated material produced above were prepared, the surfaces of the unstretched polypropylene film were opposed to each other, and then the outer peripheral edge was sealed in a three-way heat seal. A three-sided seal-type flexible packaging bag having an opening and an upper opening was produced. In the three-sided seal type soft packaging bag produced above, water is filled and packaged from the opening, and then the opening is heat sealed to form the upper seal. A semi-finished packaging product is manufactured, and then the semi-finished packaging product is placed in a retort kettle and subjected to retort processing under conditions of temperature, 120 ° C., pressure, 2.1 kgf / cm ² · G, time, 30 minutes. Retort packaged food was manufactured. The retort packaged food manufactured above has excellent heat resistance, pressure resistance, water resistance, barrier properties, heat seal properties, pin hole resistance, piercing properties, transparency, etc. Excellent barrier properties against oxygen gas, water vapor, etc., with no bag breakage or leakage of contents, etc., and functions as a food container, such as content filling and packaging suitability, distribution suitability, storage suitability, etc. . Regarding the above barrier properties, before retorting, oxygen permeability, 0.41 cc / m ² / day · 23 ° C./90% RH, water vapor permeability, 0.23 g / m ² / day · 40 ° C./90% RH On the other hand, after retort treatment, oxygen permeability, 0.58 cc / m ² / day · 23 ° C./90% RH, water vapor permeability, 0.65 g / m ² / day · 40 ° C./90% RH. In Example 7, the barrier film produced by performing the heat treatment under other conditions was obtained in the same manner as described above, and almost the same results were obtained.

It is a schematic sectional drawing which shows the layer structure of the example about the barrier film concerning this invention. It is a schematic sectional drawing which shows the layer structure of the example about the barrier film concerning this invention. It is a schematic sectional drawing which shows the layer structure of the example about the barrier film concerning this invention. It is a schematic sectional drawing which shows the layer structure of the example about the barrier film concerning this invention. It is a schematic sectional drawing which shows the layer structure of the example about the barrier film concerning this invention. It is a schematic sectional drawing which shows the layer structure of the example about the barrier film concerning this invention. It is a schematic sectional drawing which shows the layer structure of the example about the barrier film concerning this invention. It is a schematic sectional drawing which shows the layer structure of the example about the barrier film concerning this invention. It is a schematic sectional drawing which shows the layer structure of the example about the barrier film concerning this invention. It is a schematic sectional drawing which shows the layer structure of the example about the barrier film concerning this invention. It is a schematic sectional drawing which shows the layer structure of the example about the barrier film concerning this invention. It is a schematic sectional drawing which shows the layer structure of the example about the barrier film concerning this invention. It is a schematic block diagram which shows the outline | summary about a plasma chemical vapor deposition apparatus. It is a schematic block diagram which shows the outline | summary about a winding-type vacuum deposition apparatus. It is a schematic sectional drawing which shows the layer structure of the example about the barrier film concerning this invention. It is a schematic sectional drawing which shows the layer structure of the example about the barrier film concerning this invention.

Explanation of symbols

A, A _{1 to} A ₁₁ ... barrier film 1 ... base film 2 ... vapor deposition film of inorganic oxide 3, 3a to 3k ... vapor deposition film of modified inorganic oxide

Claims (41)

Made from the substrate film provided with vapor-deposited film of an inorganic oxide, further, it anneal - is subjected to ring process, the water vapor permeability, of ^{2.0g / m 2 · day~0.000001g / m} 2 · day range, the barrier to oxygen permeability, characterized in that it constitutes in the range of ^{2.0cc / m 2 · day · atm~0.000001cc} / m 2 · day · atm film.   It consists of a base film provided with a vapor-deposited film of an inorganic oxide, and further subjected to an annealing treatment, so that the water vapor transmission rate is improved from 1/100 to that before the annealing treatment. A barrier film characterized by improving the range of 99/100 and the improvement rate of oxygen permeability to a range of 1/100 to 99/100. It consists of a base film provided with a vapor-deposited film of an inorganic oxide, and further subjected to an annealing treatment. range -30g / m ² · day, the barrier film characterized in that the amount of decrease in the oxygen permeability, improve the range of ^{-0.1~-10cc / m 2 · day} · atm.   It consists of a base film provided with a vapor-deposited film of inorganic oxide, and further subjected to an annealing treatment to improve the yellowing degree to a range of -0.3 to -2.0. Barrier film. It consists of a base film provided with an inorganic oxide vapor-deposited film, and is further subjected to an annealing treatment to form an inorganic oxide vapor-deposited film. The formula MO _X (where M is a metal element) The range of the value of X varies depending on the metal element.) The amount of change in the X value of the inorganic oxide represented by +0. A barrier film characterized by being increased to a range of 01 to +0.50.   A barrier film comprising a base film provided with an inorganic oxide vapor-deposited film, and further adjusting the surface roughness of the inorganic oxide vapor-deposited film to a range of 3 to 30 nm.   It consists of a base film provided with an inorganic oxide vapor-deposited film, and further subjected to an annealing treatment to adjust the surface roughness of the inorganic oxide vapor-deposited film to a range of 3 to 30 nm. A barrier film.   It is composed of a base film provided with an inorganic oxide vapor deposition film, and further subjected to an annealing treatment, and the surface roughness of the inorganic oxide vapor deposition film as compared with that before the annealing treatment A barrier film characterized in that the standard deviation value of unevenness and the Rms value are improved by 1.01 to 100 times.   It consists of a base film provided with a vapor-deposited film of inorganic oxide, and is further subjected to an annealing treatment, so that the shrinkage rate of the base film is less And at least one of the width direction and the width direction are contracted in the range of -0.001 to -1.0%, and the film thickness of the vapor-deposited film of the inorganic oxide is 50 to 1000 mm (5 to 5%). 100 nm). The barrier film characterized by comprising in the range of 100 nm. It consists of a base film provided with a vapor-deposited film of inorganic oxide, and further subjected to an annealing treatment, and the surface roughness of the vapor-deposited film of the inorganic oxide is compared with that before the annealing treatment. standard deviation of the Rms value, increase in 1.01 to 100 times, more, its water vapor ^{permeability, 2.0g / m 2 · day~0.000001g /} m 2 · day range also, oxygen barrier films of permeability, and wherein the configuring the range of ^{2.0cc / m 2 · day · atm~0.000001cc} / m 2 · day · atm. It consists of a base film provided with a vapor-deposited film of inorganic oxide, which is further subjected to an annealing treatment, so that the shrinkage rate of the base film is less And at least one of the width direction and the width direction are contracted in the range of -0.001 to -1.0%, and the water vapor permeability is set to 2.0 g / m ² · day to 0. .000001g / m ² · day range, the barrier to oxygen permeability, characterized in that it constitutes in the range of ^{2.0cc / m 2 · day · atm~0.000001cc} / m 2 · day · atm the film. Made from the substrate film provided with vapor-deposited film of an inorganic oxide, further, it anneal - is subjected to ring process, the water vapor permeability, of ^{2.0g / m 2 · day~0.000001g / m} 2 · day range and, the oxygen permeability, constitutes in the range of ^{2.0cc / m 2 · day · atm~0.000001cc} / m 2 · day · atm, further, the yellowing factor, -0.3～- Formula MO _X that improves to a range of 2.0 and constitutes a vapor-deposited film of an inorganic oxide (wherein M represents a metal element, and the value of X varies depending on the metal element). ), The amount of change in the X value of the vapor-deposited inorganic oxide film represented by +0. A barrier film characterized by being increased to a range of 01 to +0.50, and adjusting the surface roughness of the inorganic oxide vapor-deposited film to a range of 3 to 30 nm.   The barrier film according to any one of claims 1 to 12, wherein the inorganic oxide vapor-deposited film comprises a silicon oxide vapor-deposited film or an aluminum oxide vapor-deposited film.   14. The barrier film according to claim 1, wherein the base film is made of a polyester resin film, a polyamide resin film, or a polypropylene resin film.   The barrier according to any one of claims 1 to 14, wherein the annealing treatment comprises a heat treatment in which a heat treatment temperature is set to room temperature or higher and a heat treatment time is set to 30 minutes or longer. Sex film.   The barrier film according to any one of claims 1 to 15, wherein the annealing treatment sets the heat treatment temperature to a range of room temperature to 200 ° C.   The barrier film according to any one of claims 1 to 16, wherein the annealing treatment sets the heat treatment temperature in the range of 55C to 150C.   The barrier film according to any one of claims 1 to 17, wherein the annealing treatment has a heat treatment time in a range of 30 minutes to 5 days.   The barrier film according to any one of claims 1 to 18, wherein the annealing treatment has a heat treatment time in the range of 12 hours to 3 days.   The barrier according to any one of claims 1 to 19, wherein the annealing treatment comprises a heat treatment at a heat treatment temperature of 55 ° C and a heat treatment time of 24 hours. Sex film.   The barrier according to any one of claims 1 to 20, wherein the annealing treatment comprises a heat treatment at a heat treatment temperature of 70 ° C and a heat treatment time of 24 hours. Sex film.   The barrier according to any one of claims 1 to 21, wherein the annealing treatment comprises a heat treatment at a heat treatment temperature of 90 ° C and a heat treatment time of 24 hours. Sex film.   A barrier film characterized by providing an inorganic oxide vapor-deposited film on one surface of a base film, and further subjecting the base film provided with the inorganic oxide vapor-deposited film to an annealing treatment. Manufacturing method.   An inorganic oxide vapor-deposited film is provided on one surface of the base film, and an inorganic oxide vapor-deposited film is provided by annealing the base film provided with the inorganic oxide vapor-deposited film. A method for producing a barrier film, characterized in that a base film constituting the base film is thermally shrunk and a deposited film of the inorganic oxide is intimately bonded.   25. The method for producing a barrier film according to any one of claims 23 to 24, wherein the inorganic oxide vapor-deposited film comprises a silicon oxide vapor-deposited film or an aluminum oxide vapor-deposited film.   The barrier according to any one of claims 23 to 25, wherein the annealing treatment comprises a heat treatment in which a heat treatment temperature is set to room temperature or higher and a heat treatment time is set to 30 minutes or longer. Manufacturing method of adhesive film.   The method for producing a barrier film according to any one of claims 23 to 26, wherein the annealing treatment is performed at a heat treatment temperature in the range of room temperature to 200 ° C.   The method for producing a barrier film according to any one of claims 23 to 27, wherein the annealing treatment has a heat treatment temperature in the range of 55C to 150C.   29. The method for producing a barrier film according to any one of claims 23 to 28, wherein the annealing treatment has a heat treatment time of 30 minutes to 5 days.   30. The method for producing a barrier film according to any one of claims 23 to 29, wherein the annealing treatment has a heat treatment time in the range of 12 hours to 3 days.   A silicon oxide vapor deposition film is provided on one surface of the base film, and the heat treatment temperature of the base film provided with the silicon oxide vapor deposition film is 55 ° C. and the heat treatment time is 24 hours. The manufacturing method of the barrier film characterized by performing the annealing process which consists of heat processing.   A silicon oxide vapor deposition film is provided on one surface of the base film, and the base film provided with the silicon oxide vapor deposition film is subjected to a heat treatment temperature of 70 ° C. and a heat treatment time of 24 hours. The manufacturing method of the barrier film characterized by performing the annealing process which consists of heat processing.   A silicon oxide vapor deposition film is provided on one surface of the base film, and the heat treatment temperature of the base film provided with the silicon oxide vapor deposition film is 90 ° C. and the heat treatment time is 24 hours. The manufacturing method of the barrier film characterized by performing the annealing process which consists of heat processing. A silicon oxide vapor deposition film is provided on one surface of the base film, and the base film provided with the silicon oxide vapor deposition film has a heat treatment temperature of room temperature or more and a heat treatment time of 1 hour or more. heat treatment to as, its water vapor ^{permeability, 2.0g / m 2 · day~0.000001g /} m 2 · day range also, the oxygen ^{permeability, 2.0cc / m 2 · day ·} atm~ It is configured in the range of 0.000001 cc / m ² · day · atm, and further, the yellowing degree is improved to the range of −0.3 to −2.0, and the vapor deposition film is composed of the formula SiO _X The amount of change in the X value of the silicon oxide represented is +0. A barrier film characterized by being increased to a range of 01 to +0.50. A silicon oxide vapor deposition film is provided on one surface of the base film, and the base film provided with the silicon oxide vapor deposition film has a heat treatment temperature of room temperature or more and a heat treatment time of 1 hour or more. heat treatment to as, its water vapor ^{permeability, 2.0g / m 2 · day~0.000001g /} m 2 · day range also, the oxygen ^{permeability, 2.0cc / m 2 · day ·} atm~ A barrier film characterized by comprising a range of 0.000001 cc / m ² · day · atm.   A silicon oxide vapor deposition film is provided on one surface of the base film, and the base film provided with the silicon oxide vapor deposition film has a heat treatment temperature of room temperature or more and a heat treatment time of 1 hour or more. As a barrier film, the heat treatment is performed to improve the yellowing degree to a range of -0.3 to -2.0. A silicon oxide vapor deposition film is provided on one surface of the base film, and the base film provided with the silicon oxide vapor deposition film has a heat treatment temperature of room temperature or more and a heat treatment time of 1 hour or more. heat treatment to a barrier film, characterized in that to increase the range of variation of + 0.01 + 0.50 X value of silicon oxide represented by the formula SiO _X constituting the deposited film.   A silicon oxide vapor deposition film is provided on one surface of the base film, and the base film provided with the silicon oxide vapor deposition film has a heat treatment temperature of room temperature or more, and a heat treatment time of 1 hour or more. The manufacturing method of the barrier film characterized by heat-processing to.   A silicon oxide vapor deposition film is provided on one surface of the base film, and the base film provided with the silicon oxide vapor deposition film is heated at a heat treatment temperature of 55 ° C. and a heat treatment time of 24 hours. The manufacturing method of the barrier film characterized by processing.   A silicon oxide vapor deposition film is provided on one surface of the base film, and the base film provided with the silicon oxide vapor deposition film is heated at a heat treatment temperature of 70 ° C. and a heat treatment time of 24 hours. The manufacturing method of the barrier film characterized by processing. A silicon oxide vapor deposition film is provided on one surface of the base film, and the base film provided with the silicon oxide vapor deposition film is heated at a heat treatment temperature of 90 ° C. and a heat treatment time of 24 hours. The manufacturing method of the barrier film characterized by processing.

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