JP2006082319A - Barrier film and laminated material using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a barrier film using a base material film excellent in dimensional stability, stably keeping high gas barrier properties and having good transparency, moistureproofness, impact resistance, hot water resistance, close adhesiveness and the like, and a laminated material using it. <P>SOLUTION: In the barrier film wherein a composite gas barrier layer composed of a vapor deposition layer comprising an inorganic oxide and a gas barrier composite polymer layer is laminated on one side of the base material film, a biaxially stretched polyester resin film, of which the dimensional change ratios in its longitudinal and lateral directions are respectively -5.0 to -2.0% and -1.0 to +1.0% when a load of 0.05-0.15 N/mm is applied to the base material film and a temperature is raised to 25-200°C at a temperature rising speed is 5°C/min, is used as the above base material film. The laminated material using it is also disclosed. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a barrier film and a laminated material using the same.

Conventionally, as packaging materials for filling and packaging foods, beverages, chemicals, miscellaneous goods, etc., the permeation of oxygen gas, water vapor, etc. is blocked in order to prevent deterioration, discoloration, etc. of the contents to be filled and packaged. Barrier substrates having various forms have been developed and proposed.
For example, an aluminum foil or a vapor-deposited film thereof has been proposed as the most typical one, but this one exhibits an extremely stable gas barrier property. There is a problem that it is inferior to incineration, and disposal processing after use is not easy, and there is also a problem that transparency is lacking.

In order to cope with this, for example, it is attempted to use a barrier resin film that blocks or prevents permeation of oxygen gas, water vapor, and the like made of polyvinylidene chloride resin, ethylene-vinyl alcohol copolymer, etc. It has been.
However, since the polyvinylidene chloride resin contains chlorine atoms in its structure, when it is incinerated as waste after use, harmful chlorine gas is generated, which is unfavorable for environmental hygiene.
On the other hand, the ethylene-vinyl alcohol copolymer has the advantages that the oxygen permeability is low and the adsorptivity of the flavor component is low, but there is a problem that the gas barrier property is remarkably lowered when it comes into contact with water vapor. .
For this reason, in order to block the ethylene-vinyl alcohol copolymer as a barrier base material from water vapor, it is necessary to make it a complicated laminated structure, and the fact is that the manufacturing cost is increasing.

Therefore, in recent years, a barrier layer made of a thin film of an inorganic oxide such as silicon oxide or aluminum oxide has been provided as a barrier material that exhibits high gas barrier properties and fragrance stability stably and has transparency. Barrier substrates have been developed and proposed.
Thus, the above-mentioned barrier base material is made of, for example, silicon oxide, aluminum oxide or the like on one surface of a base film made of a resin film such as a polyester resin, a polyamide resin, or a polypropylene resin. It is manufactured by depositing an inorganic oxide by vacuum deposition and providing a thin film of the inorganic oxide.
This product has excellent gas barrier properties that prevent the permeation of oxygen gas, water vapor, etc., and has excellent transparency. Also, after use, it is suitable for disposal without generating harmful substances during incineration disposal. It is excellent in environmental suitability and the like, and its use is developed in various fields, and the demand is expanding.
However, the barrier layer made of a thin film of an inorganic oxide such as silicon oxide or aluminum oxide is simply obtained by heating and vaporizing the inorganic oxide to deposit and deposit the particles on the base film. Therefore, there is a gap called a grain boundary between the inorganic oxide particles, and although it has excellent gas barrier properties, it cannot be said to have sufficiently satisfactory gas barrier properties. The fact is that there is.
For this reason, for example, an improvement proposal such as increasing the film thickness (500 to 1000 mm) or decreasing the oxygen atom ratio in the inorganic oxide thin film to improve the gas barrier property is proposed. However, on the other hand, for example, when the film thickness is increased, the transparency is lowered, and by increasing the film thickness, the thin film of the inorganic oxide is inferior in stretchability, spreadability, etc., and cracks etc. There are various problems such as being easy to occur and poor adhesion between the base film and the particles constituting the inorganic oxide thin film.

Therefore, in order to solve the problems of the barrier base material having a barrier layer made of a thin film of an inorganic oxide such as silicon oxide and aluminum oxide as described above, and improve its gas barrier performance, for example, a plastic substrate A barrier substrate comprising a multilayer laminate in which an olefin-vinyl acetate copolymer saponified resin layer having a thickness of at least 1 μm is laminated on a metal or metal oxide thin film formed on the surface of the material. It has been proposed (see, for example, Patent Document 1).
Also, a barrier substrate made of a multilayer laminate in which a polyvinyl alcohol-based resin layer having a thickness of at least 3 μm is laminated on a metal or metal oxide thin film formed on the surface of a plastic substrate. It has been proposed (see, for example, Patent Document 2).
Further, a barrier made of a gas barrier film in which at least one surface of the base film layer (1) is coated with a barrier resin coating layer (3) via an inorganic substance (2) having transparency. Also proposed is a conductive substrate (see, for example, Patent Document 3).
JP-A-6-246868 (Claims etc.) JP-A-6-316025 (Claims etc.) Japanese Patent Laid-Open No. 7-80986 (claims, etc.)

Further, for example, a vapor deposition layer made of an inorganic compound is used as a first layer on a base material made of a polymer resin composition, and a water-soluble polymer and (a) one or more alkoxides and / or a hydrolyzate thereof or (B) Applying a coating agent mainly composed of an aqueous solution containing at least one of tin chlorides or a water / alcohol mixed solution, followed by heating and drying, and laminating a gas barrier film as a second layer. There has also been proposed a gas barrier laminate film characterized in that it is formed (see, for example, Patent Document 4).
Further, in the transparent gas barrier laminate film having a metal oxide layer on at least one surface of the transparent polymer film, the portion of the alkoxysilane represented by the following general formula (1) is in contact with the metal oxide (part) A transparent gas barrier laminate film comprising a cured film containing a polyvinyl alcohol crosslinked with a hydrolyzate, a (partial) condensate thereof, or a mixture thereof.
R ¹ _n —Si (OR ² ) _4-n (1)
(Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms; vinyl group; or an organic group having one or more groups selected from the group consisting of a methacryloxy group, an epoxy group, and a mercapto group, and R ² is a carbon number. 1 to 4 alkyl groups and n is an integer of 0 to 2) has also been proposed (see, for example, Patent Document 5).
Japanese Patent No. 2790054 (Claims etc.) Japanese Patent No. 3403880 (claims, etc.)

However, in the barrier base material proposed in the above Patent Documents 1 to 3, for example, the hydroxyl group in the olefin-vinyl acetate copolymer saponified resin layer or the polyvinyl alcohol-based resin layer A polar group such as an amide group easily binds to water molecules, and therefore, there is a problem in that its gas barrier property decreases as the environmental humidity increases.
That is, as the contents to be filled and packaged, for example, when filling and packaging a liquid containing moisture, or a food or drink containing moisture, the gas barrier property is reduced due to the moisture vapor etc. of the contents, and during storage There is a problem that the quality of the contents deteriorates and changes.
In addition, depending on the food and drink to be filled and packaged, the packaged product may be manufactured by sterilizing with hot water by boil treatment or retort treatment after filling and packaging. The substrate has a problem that the gas barrier property is remarkably deteriorated during the treatment, and further, the adhesive strength and the like are lowered, the mechanical strength is deteriorated, and is not suitable for the sterilization treatment method as described above. .
Moreover, in the barrier base material proposed in the above Patent Documents 4 to 5, a high gas barrier property can be obtained, and the oxygen barrier property has sufficient performance. For example, in the same manner as described above, when a packaged product is manufactured by filling and packaging food and drink, followed by boil treatment or retort treatment with hot water to produce a packaged product, The material is inferior in water vapor barrier property, the gas barrier property is remarkably deteriorated during processing, the adhesive strength is also lowered, delamination is caused, and the mechanical strength is also deteriorated. The fact is that it is not suitable for such a sterilization treatment method.
Furthermore, in the barrier substrate proposed in the above Patent Documents 1 to 5, when forming a barrier layer made of a thin film of an inorganic oxide such as silicon oxide or aluminum oxide, As a thin film of an inorganic oxide such as silicon oxide and aluminum oxide, an olefin-vinyl acetate copolymer saponified resin layer, a polyvinyl alcohol-based resin layer, a barrier resin coating layer, and a second layer When forming a barrier coating film made of a gas barrier coating or a cured coating containing polyvinyl alcohol, a base film made of a plastic substrate, a polymer film, etc. There is a problem that a considerable thermal load is applied when a thin film is formed or when a barrier coating film is dried.
Thus, the substrate film is subjected to a considerable thermal load as described above, and accordingly, if a thermal dimensional change occurs in the vertical, horizontal, etc., it corresponds to the thermal dimensional change of the base film. It is extremely difficult for a barrier layer made of an inorganic oxide thin film such as silicon oxide or aluminum oxide to follow, and as a result, for example, a barrier layer made of an inorganic oxide thin film such as silicon oxide or aluminum oxide. Cracks and the like are generated, and the gas barrier performance for blocking and preventing permeation of oxygen gas, water vapor and the like is remarkably deteriorated and has a fatal problem that it is no longer necessary.
Therefore, the present invention uses a base film having excellent dimensional stability, stably maintains a high gas barrier property, particularly improves the water vapor barrier property, and has good transparency and moisture resistance. An object of the present invention is to provide a barrier film having impact resistance, hot water resistance, tight adhesion, and the like, and a laminate using the same.

  As a result of various studies to solve the above problems, the present inventor has focused on the thermal dimensional stability of the biaxially stretched polyester resin film. In a barrier film in which a composite gas barrier layer composed of a vapor-deposited layer and a gas barrier composite polymer layer is laminated, a load of 0.05 to 0.15 N / mm is applied to the base film as the base film. When the temperature is raised to 25 to 200 ° C. at a rate of temperature rise of 5 ° C./min, the dimensional change rate in the vertical and horizontal directions is −5.0 to −2.0%, −1.0%, respectively. A barrier film is produced using a biaxially stretched polyester resin film in a range of ˜ + 1.0%, and further, a heat seal property is formed on the surface of the composite gas barrier layer constituting the barrier film. Laminating resin layers, etc. A layer material is manufactured, and further, the laminated material is used, the heat-sealable resin layers face to face each other, and the outer peripheral edge is heat-sealed to make a packaging bag. Thus, when a packaging product is manufactured by filling and packaging various contents in the packaging bag, a gas barrier due to a thermal dimensional change by the biaxially stretched polyester resin film as the base film is produced. In addition to maintaining stable high gas barrier properties in the width direction and flow direction, improving water vapor barrier properties and improving transparency, moisture resistance, impact resistance, heat resistance, etc. The present invention has been completed by finding that a barrier film having water-based properties, tight adhesion, and the like and a laminate using the same can be produced.

  That is, the present invention is a barrier film in which a composite gas barrier layer composed of a vapor deposited layer composed of an inorganic oxide and a gas barrier composite polymer layer is laminated on one surface of the base film, When a load of 0.05 to 0.15 N / mm is applied to the base film and the temperature is raised to 25 to 200 ° C. at a rate of temperature increase of 5 ° C./min, the dimensional change rate in the vertical and horizontal directions is Use a biaxially stretched polyester resin film in the range of -5.0 to -2.0% and -1.0 to + 1.0%, respectively, and the use thereof It relates to the laminated material.

In the barrier film according to the present invention and the laminate material using the same, oxygen gas, water vapor, etc. are formed by laminating a vapor deposition layer made of an inorganic oxide and a gas barrier composite polymer layer as a composite gas barrier layer. Excellent gas barrier properties, especially water vapor barrier properties, and excellent post-processing suitability such as laminating processing, bag making processing, etc., and further, for example, heat sterilization processing by retort processing, boil processing, etc. The water-resistant strength in can also be markedly improved, and is extremely excellent in moisture proofing and the like.
Further, in the barrier film according to the present invention and the laminate using the same, the gas barrier composite polymer layer constituting the composite gas barrier layer is composed of a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer and one kind. The above alkoxide chemically reacts with each other to form a very strong three-dimensional network composite polymer layer, and also has high tight adhesion with a vapor deposition layer made of an inorganic oxide. The two synergistically maintain an extremely high gas barrier property, and can produce a barrier film having good transparency, impact resistance, hot water resistance, and the like.
In particular, in the present invention, when a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer are used in combination, the polyvinyl alcohol-based resin and at least one alkoxide, the ethylene / vinyl alcohol copolymer, and at least one or more types are used. An alkoxide, a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer, and one or more alkoxides are combined to form a very complex hybrid three-dimensional network composite polymer layer. In addition, the tight adhesion to the vapor deposition layer made of an inorganic oxide is also strong, thereby synergizing both of them, and maintaining a very high gas barrier property stably. Gas barrier product with improved transparency, good transparency, impact resistance, hot water resistance, etc. Film is one that can be manufactured.
Further, the barrier film according to the present invention and the laminate using the same are laminated on the respective surfaces when the vapor-deposited layer made of inorganic oxide and the gas barrier composite polymer layer are laminated in multiple layers, for example, inert. By providing and stacking a plasma-treated surface with gas or a plasma-treated surface with oxygen gas, the adhesion between each layer is extremely strong, and the adhesion between the two is remarkably improved. Phenomena such as delamination (delamination) are not recognized at all, and the lamination strength can be remarkably improved, and accordingly, it has the advantage of extremely excellent water resistance strength.

The barrier film according to the present invention and a laminate using the same will be described in more detail below with reference to the drawings.
1 and 2 are schematic cross-sectional views showing one example of the layer structure of the barrier film according to the present invention, and FIGS. 3, 4 and 5 use the barrier film according to the present invention. Fig. 6 and Fig. 7 are schematic cross-sectional views showing a few examples of the layer structure of the laminated material, and Figs. It is a schematic perspective view which shows an example of a structure.

First, as shown in FIG. 1, the barrier film A according to the present invention is provided with a vapor deposition layer 2 made of an inorganic oxide on one surface of a biaxially stretched polyester resin film 1 as a base film. In addition, on the vapor deposition layer 2 made of the inorganic oxide, a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M) and at least one alkoxide represented by A gas barrier composite polymer layer 3 comprising a gas barrier composition containing a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and obtained by polycondensation by a sol-gel method, And the vapor deposition layer 2 made of the inorganic oxide and the gas The basic structure is that the composite gas barrier layer 4 including the barrier composite polymer layer 3 is provided.

Thus, as a specific example of the barrier film according to the present invention, as shown in FIG. 2, on one surface of the biaxially stretched polyester resin film 1 of the base film, if necessary, an inert gas. The vapor-deposited layer 2 made of an inorganic oxide by chemical vapor deposition or physical vapor deposition is provided through the plasma-treated surface 5 by the following method. For example, the general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, and M represents A metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M. Alcohol-based resin and / or ethylene / vinyl alcohol copolymer And a gas barrier composite polymer layer 3 made of a gas barrier composition obtained by polycondensation by a sol-gel method. - it can be exemplified barrier film a ₁ having the configuration providing the composite gas barrier layer 4 having a layer 3.

Next, in the present invention, the laminated material using the barrier film according to the present invention will be described by exemplifying the case of the laminated material using the barrier film A according to the present invention shown in FIG. As shown in FIG. 3, a heat-sealable resin layer 11 is laminated on the surface of the gas barrier composite polymer layer 3 of the composite gas barrier layer 4 constituting the barrier film A according to the present invention shown in FIG. Laminated material B using the barrier film according to the present invention having the structure described above, or the gas barrier of the composite gas barrier layer 4 constituting the barrier film A according to the present invention shown in FIG. 1 as shown in FIG. A laminated material B ₁ using a barrier film according to the present invention having a structure in which a heat-sealable resin layer 11 is laminated on the surface of the conductive composite polymer layer 3 via an intermediate substrate 12; Shown in Figure 5 In addition, a plastic substrate 13 is further laminated on the other surface of the biaxially stretched polyester resin film 1 as a substrate film constituting the barrier film A according to the present invention shown in FIG. A barrier film according to the present invention comprising a structure in which a heat-sealable resin layer 11 is laminated on the surface of the gas barrier composite polymer layer 3 of the composite gas barrier layer 4 constituting the barrier film A according to the present invention. it can be exemplified laminate B ₂ or the like used.
In FIG. 4, FIG. 5, and FIG. 6, reference numerals 1, 2, 3, 4 and the like have the same meaning as reference numerals 1, 2, 3, 4, and the like shown in FIG.
Of course, in the present invention, although not shown, the barrier film according to the present invention shown in FIG. 2 is used, and in the same manner as described above, the laminate using the barrier film according to the present invention is used in the same manner as described above. The material can be manufactured.

  Furthermore, in this invention, if the example is given about the packaging bag which made a bag using the barrier film which concerns on this invention, and the laminated material using it, as this packaging bag concerning this invention, for example, When illustrating and explaining a packaging bag made using the laminated material B shown in FIG. 3, two laminated materials B and B are prepared as shown in FIG. The heat-sealable resin layers 11 and 11 that are positioned are overlapped with each other facing each other, and thereafter, heat-seal parts 15 and 15 are formed by heat-sealing the three ends of the outer periphery. , 15 and an opening 16 thereabove to form a bag using the barrier film according to the present invention and a laminate using the barrier film, and the three-sided seal type packaging according to the present invention Bag C can be manufactured.

Thus, in the present invention, as shown in FIG. 7, the three-sided seal type according to the present invention produced by using the barrier film according to the present invention produced above and the laminated material using the same is produced. The packaging bag C is filled with the contents 17 such as food and drink from the opening 16, and then the upper opening 16 is heat sealed and the upper sealing part 18 is filled. Etc. can be formed to produce a packaged product D having various forms.
In the present invention, although not shown in the drawings, the barrier film according to the present invention produced above and the three-sided seal type packaging bag according to the present invention produced using the laminated material using the same are used. From the opening, for example, desired food and drink such as curry, stew, soup, meat sauce, hamburger, meatball, sushi, oden, etc. Fill the contents, then heat seal the upper opening to form an upper seal or the like to produce a packaged semi-finished product, after which the packaged semi-finished product, for example, temperature , 110 ° C to 130 ° C, pressure, 1 to 3 kgf / cm 2 · Retort treatment such as pressure heat sterilization for about 20 to 60 minutes at G position to produce retort packaging products of various forms It is something that can be done.
In addition, in this invention, it replaces with the above retort processes, for example, it can boil for about 30 minutes at about 90 degreeC, and can also heat-sterilize, etc., and can also manufacture a bactericidal treatment packaging product. .
Further, in the present invention, although not shown, the barrier film according to the present invention shown in FIGS. 4 and 5 and the laminate material using the same are used, and the same as above, It is possible to manufacture a packaging bag, a packaged product, and the like that are made using the barrier film according to the invention and a laminate using the barrier film.
In the present invention, it is needless to say that the packaging bag, packaged product and the like according to the present invention are not limited to the shape of the illustrated packaging bag illustrated above, and its purpose, use, etc. Thus, packaging bags having various forms such as a four-side seal type, a self-supporting type, a gusset type, a square bottom type, a pillow type, and the like can be manufactured.

The above examples illustrate one or two examples of the barrier film according to the present invention, a laminated material using the barrier film, a packaging bag made using the laminated material, a packaged product, and the like. However, the present invention is not limited to these.
For example, in the present invention, although not shown in the drawings, other materials and the like are arbitrarily used depending on the purpose of use, application, etc., barrier films having various forms, laminates using the same, and lamination It is possible to design and manufacture packaging bags, packaging products and the like that are made using materials.
Further, for example, although not shown in the drawings, in the present invention, the vapor deposition layer made of an inorganic oxide is not limited to a single layer film made of one of the vapor deposition layers made of an inorganic oxide, but also a vapor deposition layer made of an inorganic oxide. It can also be composed of a multilayer film composed of more than one layer.
Further, for example, although not shown, in the present invention, the gas barrier composite polymer layer can be provided not only in one layer but also in two or more layers.
In the present invention, as a method of laminating a laminate using the barrier film according to the present invention as described above, although not shown, for example, an anchor coat agent layer by an anchor coat agent, Lamination is performed via a melt extrusion laminating method in which a polyolefin resin or the like is laminated through a melt extruded resin layer or the like, or laminating adhesive layer by a laminating adhesive, for example. Lamination can be performed by a dry lamination method or the like.

Next, in the present invention, the material constituting the barrier film, the laminated material, the packaging bag, the packaged product, etc. according to the present invention, the production method, etc. will be described. First, the base constituting the barrier film according to the present invention. When the biaxially stretched polyester resin film as the material film is described, the biaxially stretched polyester resin film as the base film constitutes the barrier film, the laminate, the packaging bag, etc. according to the present invention. Since it is a base material, and further, a vapor deposition film layer made of inorganic oxide, or a base material that holds a gas barrier composite polymer layer, etc., first, it is excellent in thermal dimensional change, their formation, Be able to withstand conditions such as processing and maintain them well without impairing their characteristics, and, in addition, workability during bag making of packaging bags Heat resistance, slip properties, resistance to pinhole - Le resistance, excellent physical properties of the other or the like, can be used the biaxially oriented polyester resin film capable of satisfying the other conditions such as.
In the present invention, as the above-mentioned biaxially stretched polyester resin film, a load of 0.05 to 0.15 N / mm is applied to the film, and the temperature is increased to 25 to 200 ° C. at a temperature increase rate of 5 ° C./min. When using a biaxially stretched polyester resin film, the dimensional change rate in the vertical and horizontal directions is in the range of -5.0 to -2.0% and -1.0 to + 1.0%, respectively. Specifically, for example, a biaxially stretched polyethylene terephthalate film, a biaxially stretched polybutylene terephthalate film, a biaxially stretched polyethylene naphthalate film, or the like can be used. .
In the present invention, among the above-described resin films or sheets, it is particularly preferable to use a biaxially stretched polyethylene terephthalate film.

In the present invention, the numerical limitation of the biaxially stretched polyester resin film as described above is limited to the biaxial stretching in the vapor deposition process for forming a vapor deposition layer made of an inorganic oxide and the coating process for forming a gas barrier composite polymer layer. Focusing on the dimensional change of the biaxially stretched polyester resin film in an environment where the polyester resin film is exposed, that is, in an environment where a tension is applied and running in a high temperature region, the dimensional change is limited. It is.
Thus, in the present invention, the limitation of the load of 0.05 to 0.15 N / mm means the tension actually applied to the biaxially stretched polyester resin film in each step.
In the present invention, the limitation of 25 to 200 ° C. at a heating rate of 5 ° C./min means the temperature range in the drying hood of the coater in the vapor deposition chamber.
Furthermore, in the present invention, the dimensional change rates in the vertical direction and the horizontal direction are limited to -5.0 to -2.0% and -1.0 to + 1.0%, respectively. The range in which microcracks do not enter the vapor-deposited layer made of an inorganic oxide is quantified and limited due to dimensional changes.

In the present invention, as the biaxially stretched polyester resin film as described above, for example, one or more of the above-mentioned various polyester resins are used, extrusion method, cast molding method, T-die method, cutting method. , A method of forming the above-mentioned various resins independently using a film-forming method such as an inflation method or the like, or a multilayer co-extrusion film-forming using two or more types of various resins In addition, two or more types of resins are used, and various resin films or sheets are manufactured by a method of mixing and forming a film before forming a film. Various biaxially stretched polyester resin films formed by stretching in a biaxial direction using a method or a tuber method can be used.
In the present invention, the film thickness of various resin films or sheets is preferably about 6 to 200 μm, more preferably about 9 to 100 μm.

In addition, when using 1 type or more of the above-mentioned various polyester resins and forming the film, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, Various plastic compounding agents and additives can be added for the purpose of improving and modifying slipperiness, releasability, flame retardancy, antifungal properties, electrical properties, strength, etc. The amount can be arbitrarily added from a very small amount to several tens of percent depending on the purpose.
In the above, as a general additive, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment, and the like can be used. Furthermore, a modifying resin or the like can be used.

By the way, in the barrier film according to the present invention, the biaxially stretched polyester resin film as described above has a close adhesiveness with a vapor deposition layer made of an inorganic oxide by a chemical vapor deposition method or a physical vapor deposition method which will be described later. In order to improve and ultimately bring the two into close contact with each other and prevent the occurrence of delamination or the like, the one surface of the above-mentioned biaxially stretched polyester resin film is, for example, It is preferable to provide a plasma-treated surface with an active gas.
Thus, in the present invention, the plasma processing surface by the inert gas will be described. As the plasma processing surface, the plasma is subjected to surface modification using plasma gas generated by ionizing the gas by arc discharge. A plasma treatment surface can be formed by using a surface treatment method or the like.
That is, in the present invention, a plasma treatment surface is formed by an inert gas by performing a plasma treatment by a plasma surface treatment method using an inert gas such as nitrogen gas, argon gas, helium gas, etc. as a plasma gas. Can do.
In the present invention, as the plasma gas, a mixed gas obtained by further adding oxygen gas to the above inert gas can also be used.
In the present invention, when a plasma-treated surface with an inert gas is formed, a vapor deposition layer made of an inorganic oxide by a chemical vapor deposition method or a physical vapor deposition method is formed on one surface of a biaxially stretched polyester resin film. Immediately before forming the film, in-line plasma treatment removes moisture, dust, etc. from the surface of the biaxially stretched polyester resin film and enables surface treatment such as smoothing, activating, etc. This is desirable.
Further, in the present invention, it is preferable to perform the plasma discharge treatment in consideration of conditions such as plasma output, plasma gas type, plasma gas supply amount, treatment time, and the like.
In the present invention, as a method for generating plasma, for example, a direct current glow discharge, a high frequency discharge, a microwave discharge, or the like can be used.
Of course, in the present invention, the plasma processing surface can be formed also by the atmospheric pressure plasma processing method.

  Next, in the present invention, a description will be given of a vapor deposition layer made of an inorganic oxide provided on one surface of the biaxially stretched polyester resin film constituting the barrier film according to the present invention. Is, for example, a chemical vapor deposition method, a physical vapor deposition method, or a combination of both, and a single layer film consisting of one layer of an inorganic oxide vapor deposition layer or a multilayer film consisting of two or more layers Alternatively, it can be manufactured by forming a composite film.

In the present invention, the vapor deposition layer made of the inorganic oxide by the chemical vapor deposition method will be described in more detail. As the vapor deposition layer made of the inorganic oxide by the chemical vapor deposition method, for example, a plasma chemical vapor deposition method can be used. A vapor deposition layer made of an inorganic oxide can be formed using a chemical vapor deposition method (Chemical Vapor Deposition method, CVD method) such as a thermal chemical vapor deposition method or a photochemical vapor deposition method.
In the present invention, specifically, on one surface of the biaxially stretched polyester resin film, a vapor deposition monomer gas such as an organosilicon compound is used as a raw material, and a carrier gas such as argon gas or helium gas is not used. A vapor deposition layer made of an inorganic oxide such as silicon oxide is used by using a low temperature plasma chemical vapor deposition method using an active gas, further using an oxygen gas as an oxygen supply gas, and utilizing a low temperature plasma generator or the like. Can be formed.
In the above, for example, high-frequency plasma, pulse wave plasma, microwave plasma, or the like can be used as the low-temperature plasma generator. Thus, in the present invention, highly active and stable plasma is obtained. Therefore, it is desirable to use a high-frequency plasma generator.

Specifically, an example of the method for forming a vapor deposition layer made of an inorganic oxide by the low temperature plasma chemical vapor deposition method will be described. FIG. 8 shows an inorganic oxide by the plasma chemical vapor deposition method described above. 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 the vapor deposition layer which consists of.
In the present invention, as shown in FIG. 8, the biaxially stretched polyester-based resin film 1 is fed out from an unwinding roll 23 disposed in a vacuum chamber 22 of a plasma chemical vapor deposition apparatus 21, and further, The biaxially stretched polyester resin film 1 is conveyed onto the circumferential surface of the cooling / electrode drum 25 at a predetermined speed via the auxiliary roll 24.
Thus, 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 26 and 27 and the raw material volatilization supply device 28, and the like. The vapor deposition mixed gas composition was introduced into the vacuum chamber 22 through the raw material supply nozzle 29 without adjusting the vapor deposition mixed gas composition, and was conveyed onto the cooling / electrode drum 25 peripheral surface. The plasma is generated on one surface of the biaxially stretched polyester resin film 1 by the glow discharge plasma 30 and irradiated to form a deposited layer made of an inorganic oxide such as silicon oxide.
In the present invention, at that time, the cooling / electrode drum 25 is applied with a predetermined power from the power source 31 disposed outside the vacuum chamber 22, and the cooling / electrode drum 25 is disposed in the vicinity of the cooling / electrode drum 25. The generation of plasma is promoted by arranging the magnet 32.
Subsequently, after forming the vapor deposition layer which consists of inorganic oxides, such as a silicon oxide, on the one side of the biaxial stretching polyester-type resin film 1 above, the biaxial stretching polyester-type resin film 1 consists of inorganic oxides. In a state where the vapor deposition layer is held, it is wound around the take-up roll 34 via the auxiliary roll 33 to form the vapor deposition layer made of the inorganic oxide by the plasma chemical vapor deposition method according to the present invention. It can be done.
In the figure, 35 represents a vacuum pump.
The above exemplification is an example, and it goes without saying that the present invention is not limited thereby.
Although not shown, in the present invention, the vapor deposition layer made of an inorganic oxide may be not only one vapor deposition layer made of an inorganic oxide but also a multilayer film in which two or more layers are laminated, The material to be used can also be used by 1 type, or 2 or more types of mixtures, and can also comprise the vapor deposition layer which consists of an inorganic oxide mixed with a different kind of material.

In the above, the inside of the vacuum chamber is depressurized by a vacuum pump and adjusted to a vacuum degree of 1 × 10 ⁻¹ to 1 × 10 ⁻⁸ Torr, preferably a vacuum degree of 1 × 10 ⁻³ to 1 × 10 ⁻⁷ Torr It is desirable to do.
In the raw material volatilization supply device, the organic silicon compound as the raw material is volatilized and mixed with oxygen gas, inert gas, etc. supplied from the gas supply device, and this mixed gas is supplied to the vacuum chamber through the raw material supply nozzle. It is introduced in the inside.
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 from the power source, glow discharge plasma is generated in the vicinity of the opening of the raw material supply nozzle in the vacuum chamber and the cooling / electrode drum. The glow discharge plasma is derived from one or more gas components in the mixed gas. In this state, the biaxially stretched polyester resin film is transported at a constant speed, and is cooled by a glow discharge plasma. A vapor deposition layer made of an inorganic oxide such as silicon oxide can be formed on the surface of the biaxially stretched polyester resin film on the electrode drum peripheral surface.
At this time, the degree of vacuum in the vacuum chamber should be adjusted to 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to 1 × 10 ⁻² Torr. In addition, it is desirable that the biaxially stretched polyester resin film transport speed is adjusted to about 10 to 300 m / min, preferably about 50 to 150 m / min.

In addition, in the plasma chemical vapor deposition apparatus described above, the formation of a vapor deposition layer made of an inorganic oxide such as silicon oxide is performed by oxidizing a plasma source gas with oxygen gas on one surface of a biaxially stretched polyester resin film. However, since it is formed as a thin film in the form of SiO _x , the formed vapor-deposited film of inorganic oxide such as silicon oxide is a continuous layer that is dense, has few gaps, and is highly flexible. Therefore, the barrier property of the vapor deposition layer made of an inorganic oxide such as silicon oxide is much higher than that of a vapor deposition layer made of an inorganic oxide such as silicon oxide formed by a conventional vacuum vapor deposition method or the like, A sufficient gas barrier property can be obtained with a thin film thickness.
Further, in the present invention, the surface of the biaxially stretched polyester resin film is cleaned by SiO _x plasma, and polar groups, free radicals, etc. are generated on the surface of the biaxially stretched polyester resin film. It has the advantage that the tight adhesion between the deposited layer made of an inorganic oxide such as silicon oxide and the surface of the biaxially stretched polyester resin film is high.
Furthermore, the degree of vacuum when forming a continuous film made of an inorganic oxide such as silicon oxide as described above is about 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to 1 ×. Since the pressure is adjusted to 10 ⁻² Torr, the degree of vacuum is 1 × 10 ⁻⁴ to 1 × 10 ⁻⁵ Torr when a vapor deposition layer made of an inorganic oxide such as silicon oxide is formed by a conventional vacuum vapor deposition method. Compared to the low degree of vacuum, the biaxially stretched polyester resin film can be shortened in the vacuum setting time when the raw material is replaced, the degree of vacuum is easily stabilized, and the film forming process is stabilized. is there.

In the present invention, a vapor deposition layer made of silicon oxide formed by using a vapor deposition monomer gas such as an organosilicon compound chemically reacts with a vapor deposition monomer gas such as an organic silicon compound and oxygen gas, etc. The product is closely bonded to one surface of the biaxially stretched polyester resin film to form a dense, flexible thin film, and is generally represented by the general formula SiO _x (where X is 0 to 2). Is a continuous thin film mainly composed of silicon oxide.
Thus, the vapor deposition layer made of silicon oxide is represented by the general formula SiO _x (where X represents a number of 1.3 to 1.9) in terms of transparency, barrier properties, and the like. A thin film mainly composed of a deposited layer made of silicon oxide 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.

The vapor deposition layer made of silicon oxide is mainly composed of silicon oxide, and further contains at least one kind of compound of carbon, hydrogen, silicon or oxygen, or two or more elements thereof. It consists of a vapor-deposited film contained by chemical bonding or the like.
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 layer made of silicon oxide become insufficient, and scratches, cracks, etc. occur due to bending. It is easy to maintain a high barrier property stably, and if it exceeds 50%, the barrier property is lowered, which is not preferable.
Furthermore, in the present invention, in the vapor deposition layer made of silicon oxide, the content of the above compound is preferably decreased in the depth direction from the surface of the vapor deposition layer made of silicon oxide. On the surface of the deposited layer, the impact resistance and the like can be enhanced by the above compound and the like. On the other hand, the content of the above compound is small at the interface with the surface of the biaxially stretched polyester resin film. This has the advantage that the tight adhesion between the axially stretched polyester resin film and the vapor deposition layer made of silicon oxide is strong.

Thus, in the present invention, the above-described vapor deposition layer made of silicon oxide, for example, the surface of an X-ray photoelectron spectrometer (Xray Photoelectron Spectroscopy, XPS), a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy, SIMS) or the like. The physical properties as described above can be confirmed by performing an elemental analysis of the vapor deposition layer made of silicon oxide using an analysis apparatus and a method of analyzing by ion etching in the depth direction.
In the present invention, the thickness of the vapor deposition layer made of silicon oxide is preferably about 50 mm to 4000 mm, and specifically, the film thickness is preferably about 100 to 1000 mm, Therefore, in the above, if it is thicker than 1000 mm, and more than 4000 mm, it is not preferable because cracks and the like are likely to occur in the film, and if it is less than 100 mm, further less than 50 mm, there is a barrier effect. This is undesirable because it becomes difficult.
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. Moreover, in the above, as means for changing the film thickness of the vapor deposition layer made of silicon oxide, a method of increasing the volume velocity of the vapor deposition layer, that is, a method of increasing the amount of monomer gas and oxygen gas, or the vapor deposition rate. This can be done by a method of slowing down.

Next, as a monomer gas for vapor deposition of an organic silicon compound or the like for forming a vapor deposition layer made of an inorganic oxide such as silicon oxide in the above, for example, 1.1.3.3-tetramethyldisiloxane, hexamethyl Disiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, Phenyltrimethoxysilane, methyltriethoxysilane, 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 vapor deposition layer made of the inorganic oxide by the physical vapor deposition method will be described in more detail. As the vapor deposition layer made of the inorganic oxide by the physical vapor deposition method, for example, a vacuum vapor deposition method is used. A vapor deposition layer made of an inorganic oxide can be formed using a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as sputtering, ion plating, or ion cluster beam method.
In the present invention, specifically, using a metal or metal oxide as a raw material, this is heated and vaporized, and this is vapor-deposited on one surface of a biaxially stretched polyester resin film, or Using a metal or metal oxide as a raw material, introducing oxygen to oxidize and depositing it on one side of a biaxially stretched polyester resin film, and further plasma assisting to assist the oxidation reaction with plasma The vapor deposition layer can be formed using an oxidation reaction vapor deposition method of the formula.
In the above, as a heating method for 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.

In the present invention, a specific example of a method for forming a thin film layer made of an inorganic oxide by physical vapor deposition will be described. FIG. 9 is a schematic configuration diagram showing an example of a take-up vacuum deposition apparatus. .
As shown in FIG. 9, the biaxially stretched polyester resin film 1 fed out from the unwinding roll 43 in the vacuum chamber 42 of the wind-up type vacuum vapor deposition apparatus 41 passes through the guide rolls 44 and 45. Then, it is guided to the cooled coating drum 46.
Thus, a vapor deposition source 48 heated by a crucible 47 on one surface of the biaxially stretched polyester resin film 1 guided on the cooled coating drum 46, for example, metallic aluminum, or Aluminum oxide is evaporated, and if necessary, oxygen gas or the like is ejected from an oxygen gas outlet 49 and supplied from the inorganic oxide such as aluminum oxide through the masks 50 and 50 while supplying this. Then, in the above, for example, the biaxially stretched polyester resin film 1 on which the vapor deposition layer made of an inorganic oxide such as aluminum oxide is formed is sent out through the guide rolls 51 and 52. By winding on the winding roll 53, a vapor deposition layer made of an inorganic oxide can be formed by the physical vapor deposition method according to the present invention.
In the present invention, first, a vapor deposition layer composed of the inorganic oxide of the first layer is formed using the above-described winding type vacuum vapor deposition apparatus, and then, similarly, the vapor deposition layer is composed of the inorganic oxide. A vapor deposition layer made of an inorganic oxide is further formed on the vapor deposition layer, or these are connected in series using a take-up vacuum vapor deposition apparatus as described above, and are continuously oxidized by inorganic oxidation. By forming a vapor deposition layer made of a material, a vapor deposition layer made of an inorganic oxide consisting of two or more multilayer films can be formed.

In the above, as the vapor deposition layer made of an inorganic oxide, basically, any thin film on which a metal oxide is vapor-deposited can be used. For example, silicon (Si), aluminum (Al), magnesium (Mg) Of metals such as calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y) It is possible to use a deposited film of a product.
Thus, preferable examples include vapor-deposited films of metal oxides such as silicon (Si) and aluminum (Al).
The metal oxide vapor deposition film can be referred to as a metal oxide such as silicon oxide, aluminum oxide, magnesium oxide, etc., and the notation thereof is, for example, SiO _x , AlO _x , MgO. MO _X (in the formula, M represents a metal element, the value of X is in the range respectively of a metal element different.) as _X, etc. represented by.
As the range of the value of X, 0 to 2 for silicon (Si), 0 to 1.5 for aluminum (Al), 0 to 1 for magnesium (Mg), 0 to 1 for calcium (Ca). 1, 0 to 0.5 for potassium (K), 0 to 2 for tin (Sn), 0 to 0.5 for sodium (Na), 0 to 1, 5 for boron (B), titanium ( Ti) can be 0 to 2, lead (Pb) is 0 to 1, zirconium (Zr) is 0 to 2, and yttrium (Y) is 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 vapor-deposited layer composed of the inorganic oxide as described above varies depending on the metal used or the kind of the metal oxide, but is, for example, about 50 to 2000 mm, preferably 100 to It is desirable to select and form arbitrarily within the range of about 1000 mm.
Moreover, in this invention, as a vapor deposition layer which consists of inorganic oxides, as a metal to be used or a metal oxide, it is used by 1 type, or 2 or more types of mixtures, and from the inorganic oxide mixed by the dissimilar material. It is also possible to constitute a deposited layer.

  Thus, in the present invention, in the thin film layer made of an inorganic oxide by the physical vapor deposition method described above, as the vapor deposition layer made of aluminum oxide, if the degree of oxidation is too high, the formed film quality becomes hard. Since cracks are easily generated and transparency is lowered when the degree of oxidation is too low, the transmittance of ultraviolet rays (wavelength 366 nm) during or immediately after deposition is in the range of 85 to 96%, more preferably 87. It is preferable to use an aluminum oxide vapor-deposited film having a thickness in the range of ~ 94% and a film thickness in the range of 150 to 600 mm in consideration of post-processing suitability. The vapor deposition layer made of silicon oxide is formed by a physical vapor deposition method using a mixture of silicon monoxide and silicon as a raw material and a film thickness in the range of 50 to 300 mm in consideration of post-processing suitability. Those it is preferable to use a deposited film of silicon.

By the way, in the barrier film according to the present invention, the vapor-deposited layer made of the inorganic oxide is formed on the surface of the vapor-deposited layer made of the inorganic oxide provided on one surface of the biaxially stretched polyester resin film as described above. In order to improve the tight adhesion and the like with the gas barrier composite polymer layer provided on the top, in the end, in order to firmly adhere both of them and prevent the occurrence of delamination, etc., oxygen gas It is preferable to form a plasma-treated surface.
Thus, in the present invention, the plasma-treated surface with oxygen gas can be formed in the same manner as the plasma-treated surface with the aforementioned inert gas.
That is, in the present invention, the oxygen-treated plasma treatment surface is a plasma surface treatment method in which surface modification is performed using a plasma gas generated by ionizing a gas by arc discharge. It is possible to form a plasma-treated surface.
Thus, in the present invention, the plasma gas is a plasma surface treatment method using oxygen gas or a mixed gas of oxygen gas and inert gas such as nitrogen gas, argon gas, helium gas, or the like. By performing the treatment, a plasma treatment surface with oxygen gas can be formed.
In the present invention, when forming a plasma-treated surface with oxygen gas, after forming a vapor deposition layer made of inorganic oxide, immediately after that, a plasma discharge with oxygen gas is performed inline on the vapor deposition layer made of inorganic oxide. By performing the treatment, a plasma treatment surface by oxygen gas can be formed.
Further, in the present invention, it is preferable to perform the plasma discharge treatment in consideration of conditions such as plasma output, plasma gas type, plasma gas supply amount, treatment time, and the like.
In the present invention, as a method for generating plasma, for example, a direct current glow discharge, a high frequency discharge, a microwave discharge, or the like can be used.
Of course, in the present invention, the plasma processing surface can be formed also by the atmospheric pressure plasma processing method.

Next, in the present invention, the gas barrier composite polymer layer constituting the barrier film according to the present invention will be described. As the gas barrier composite polymer layer, for example, a general formula R ¹ _n M (OR ² ) _m (In the formula, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, and m represents an integer of 1 or more. N + m represents the valence of M.) and contains a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and a sol-gel. A process for preparing a gas barrier composition that is polycondensed by a sol-gel method in the presence of a process catalyst, acid, water, and an organic solvent, comprising an inorganic oxide provided on one surface of a biaxially stretched polyester resin film Vapor deposition A step of applying a gas barrier composition that is polycondensed by the sol-gel method on the layer to provide a coating film, a biaxial stretching in which a coating film is provided on the vapor deposition layer made of the inorganic oxide The polyester-based resin film is heated at 20 ° C. to 180 ° C. and at a temperature equal to or lower than the melting point of the biaxially stretched polyester resin film for 10 seconds to 10 minutes. It can be manufactured by a manufacturing process including a process of forming a gas barrier composite polymer layer with the above gas barrier composition on a vapor deposition layer made of an inorganic oxide provided on one surface.

In the present invention, the gas barrier composite polymer layer constituting the barrier film according to the present invention has a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² are carbon The organic group of the number 1-8 is represented, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents the valence of M. Containing at least one or more alkoxides represented, a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer, and further in the presence of a sol-gel catalyst, an acid, water, and an organic solvent. In addition, a step of preparing a gas barrier composition that is polycondensed by a sol-gel method, polycondensation by the above-mentioned sol-gel method on a vapor deposition layer made of an inorganic oxide provided on one surface of a biaxially stretched polyester resin film Gas barrier composition A biaxially stretched polyester-based resin film provided with a coating film in which two or more layers are laminated on the vapor-deposited layer made of the above inorganic oxide; Inorganic provided on one surface of the above-mentioned biaxially stretched polyester resin film by heat treatment for 10 seconds to 10 minutes at a temperature not lower than the melting point of the above biaxially stretched polyester resin film. On the vapor deposition layer which consists of oxides, it can manufacture by the manufacturing process including the process of forming the composite polymer layer which laminated | stacked two or more gas barrier composite polymer layers by said gas barrier composition.

In the above, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m forming the gas barrier composite polymer layer constituting the barrier film according to the present invention, a partial hydrolyzate of alkoxide, alkoxide At least one kind of hydrolysis condensate can be used, and the partial alkoxide hydrolysis product described above does not require that all alkoxy groups are hydrolyzed, and one or more of them are hydrolyzed. In addition, the hydrolysis condensate may be a dimer or more of a partially hydrolyzed alkoxide, specifically a 2 to 6 mer. The

In the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m , silicon, zirconium, titanium, aluminum, and the like can be used as the metal atom represented by M.
Thus, in the present invention, examples of a preferable metal include silicon.
In the present invention, the alkoxide can be used alone or in combination of two or more different metal atom alkoxides in the same solution.

In the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , specific examples of the organic group represented by R ¹ include, for example, a methyl group, an ethyl group, an n-propyl group, i Examples thereof include alkyl groups such as -propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-octyl group and others.
In the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , specific examples of the organic group represented by R ² include, for example, a methyl group, an ethyl group, an n-propyl group, i -Propyl group, n-butyl group, sec-butyl group, and the like.
In the present invention, these alkyl groups may be the same or different in the same molecule.

Thus, in the present invention, as the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m , for example, it is preferable to use an alkoxysilane in which M is Si.
The alkoxysilane is represented by the general formula Si (ORa) ₄ (wherein Ra represents a lower alkyl group).
In the above, Ra includes a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and the like.
As specific examples of the above alkoxysilane, for example, tetramethoxysilane Si (OCH ₃ ) ₄ , tetraethoxysilane Si (OC ₂ H ₅ ) ₄ , tetrapropoxysilane Si (0C ₃ H ₇ ) ₄ , tetrabutoxysilane Si (OC ₄ H ₉ ) ₄ , etc. can be used.

In the present invention, examples of the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m include, for example, the general formula Rb _n Si (ORc) _4-m (where n is 0 The above-mentioned integer is represented, m represents an integer of 1, 2, and 3, and Rb and Rc represent a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and the like. Alkoxysilanes can be used.
Specific examples of the above-mentioned alkylalkoxysilane include, for example, methyltrimethoxysilane CH ₃ Si (OCH ₃ ) ₃ , methyltriethoxysilane CH ₃ Si (OC ₂ H ₅ ) ₃ , dimethyldimethoxysilane (CH ₃ ) ₂ Si (OCH ₃ ) ₂ , dimethyldiethoxysilane (CH ₃ ) ₂ Si (OC ₂ H ₅ ) ₂ , etc. can be used.
Said alkoxysilane, alkylalkoxysilane, etc. can be used individually or in mixture of 2 or more types.
In the present invention, a polycondensation product of the above alkoxysilane can also be used, and specifically, for example, polytetramethoxysilane, polytetraemethoxysilane, and the like can be used.

Next, in the present invention, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , for example, a zirconium alkoxide in which M is Zr can be used.
Specific examples of the zirconium alkoxide include, for example, tetramethoxyzirconium Zr (OCH ₃ ) ₄ , tetraethoxyzirconium Zr (OC ₂ H ₅ ) ₄ , tetra ipropoxyzirconium Zr (is0-0C ₃ H ₇ ) ₄ , tetra nButoxyzirconium Zr (OC ₄ H ₉ ) ₄ , etc. can be used.

In the present invention, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , for example, a titanium alkoxide in which M is Ti can be used.
Specific examples of the titanium alkoxide include, for example, tetramethoxytitanium Ti (OCH ₃ ) ₄ , tetraethoxytitanium Ti (OC ₂ H ₅ ) ₄ , tetraisopropoxytitanium Ti (is0-0C ₃ H ₇ ) ₄ , tetra n-butoxy titanium Ti (OC ₄ H ₉ ) ₄ , etc. can be used.

Furthermore, in the present invention, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , for example, an aluminum alkoxide in which M is Al can be used.
Specific examples of the aluminum alkoxide include, for example, tetramethoxyaluminum Al (OCH ₃ ) ₄ , tetraethoxyaluminum Al (OC ₂ H ₅ ) ₄ , tetraisopropoxyaluminum Al (is0-0C ₃ H ₇ ) ₄ , tetra nButoxyaluminum Al (OC ₄ H ₉ ) ₄ , etc. can be used.

In the present invention, the above alkoxides may be used by mixing two or more of them.
Thus, in the present invention, in particular, by using a mixture of alkoxysilane and zirconium alkoxide, it is possible to improve the toughness, heat resistance, etc. of the resulting barrier film according to the present invention, and at the time of stretching. A decrease in the retort resistance of the film is avoided.
The amount of the zirconium alkoxide used is in the range of 10 parts by weight or less with respect to 100 parts by weight of the alkoxysilane, preferably about 5 parts by weight. In the above, if it exceeds 10 parts by weight, the formed gas barrier composite polymer layer is easily gelled, the brittleness of the film is increased, and the gas barrier property is obtained when the biaxially stretched polyester resin film is coated. This is not preferable because the composite polymer layer tends to peel easily.

In the present invention, in particular, by using a mixture of alkoxysilane and titanium alkoxide, the thermal conductivity of the resulting gas barrier composite polymer layer is lowered, and the heat resistance of the barrier film according to the present invention is remarkably improved. There is an advantage of doing.
In the above, the amount of titanium alkoxide used is in the range of 5 parts by weight or less with respect to 100 parts by weight of the alkoxysilane, and preferably about 3 parts by weight.
In the above, if it exceeds 5 parts by weight, the brittleness of the gas barrier composite polymer layer to be formed increases, and the gas barrier composite polymer layer tends to peel off when the biaxially stretched polyester resin film is coated. Therefore, it is not preferable.

Next, as the polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer forming the gas barrier composite polymer layer constituting the barrier film according to the present invention, a polyvinyl alcohol resin, or , An ethylene / vinyl alcohol copolymer can be used alone, or a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer can be used in combination. In the present invention, by using a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, the physical properties such as gas barrier properties, water resistance, weather resistance, and the like of the gas barrier composite polymer layer are remarkably improved. It can be made to.
In particular, in the present invention, by using a combination of a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer, in addition to the above physical properties such as gas barrier properties, water resistance, and weather resistance, hot water resistance and hot water A gas barrier composite polymer layer remarkably excellent in gas barrier properties after the treatment can be formed.

  In the present invention, when a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer are used in combination, the blending ratio of each is polyvinyl alcohol resin: ethylene / vinyl alcohol by weight ratio. The copolymer is preferably in the 10: 0.05 to 10: 6 position, and more preferably in a blending ratio of about 10: 1.

In the present invention, the content of the polyvinyl alcohol-based resin and / or the ethylene / vinyl alcohol copolymer is in the range of 5 to 500 parts by weight with respect to 100 parts by weight of the total amount of the alkoxide, It is preferable to prepare the gas barrier composition at a blending ratio of about 20 to 200 parts by weight.
In the above, if it exceeds 500 parts by weight, the brittleness of the gas barrier composite polymer layer is increased, and the water resistance and weather resistance of the resulting barrier film tend to be lowered, which is not preferable. If it is less than 1, the gas barrier property is lowered, which is not preferable.

In the present invention, as the polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer, first, as the polyvinyl alcohol resin, generally obtained by saponifying polyvinyl acetate is used. be able to.
As the above-mentioned polyvinyl alcohol-based resin, a partially saponified polyvinyl alcohol-based resin in which several tens percent of acetic acid groups remain, or a completely saponified polyvinyl alcohol in which no acetic acid groups remain, or OH groups have been modified. A modified polyvinyl alcohol resin may be used and is not particularly limited.
Specific examples of the polyvinyl alcohol-based resin include RS-110 (saponification degree = 99%, polymerization degree = 1,000) manufactured by Kuraray Co., Ltd., and Kuraray Poval LM-20SO (saponification degree) manufactured by Kuraray Co., Ltd. Degree = 40%, degree of polymerization = 2,000), Gohsenol NM-14 (degree of saponification = 99%, degree of polymerization = 1,400) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. can be used.

In the present invention, as the ethylene-vinyl alcohol copolymer, a saponified product of a copolymer of ethylene and vinyl acetate, that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer should be used. Can do.
Specific examples include partial saponification products in which several tens mol% of acetic acid groups remain to complete saponification products in which acetic acid groups remain only a few mol% or no acetic acid groups remain. However, it is desirable to use a saponification degree that is preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more from the viewpoint of gas barrier properties. The content of repeating units derived from ethylene in the ethylene / vinyl alcohol copolymer (hereinafter also referred to as “ethylene content”) is usually 0 to 50 mol%, preferably 20 to 45 mol%. Is preferably used.
Specific examples of the ethylene / vinyl alcohol copolymer include Kuraray Co., Ltd., Eval EP-F101 (ethylene content: 32 mol%), Nippon Synthetic Chemical Industry Co., Ltd., Soarnol D2908 (ethylene content: 29 mol%). ) Etc. can be used.

Next, in the present invention, the gas barrier composition for forming the gas barrier composite polymer layer constituting the barrier film according to the present invention will be described. As the gas barrier composition, the general formula R ¹ as described above is used. _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m Represents an integer of 1 or more, and n + m represents the valence of M.) and at least one alkoxide represented by the above, a polyvinyl alcohol resin and / or an ethylene vinyl alcohol as described above. A gas barrier composition containing a copolymer and further polycondensed by a sol-gel method in the presence of a sol-gel method catalyst, an acid, water, and an organic solvent is prepared.

In preparing the gas barrier composition, for example, a silane coupling agent or the like can be added.
Thus, as the silane coupling agent, known organic reactive group-containing organoalkoxysilanes can be used.
In the present invention, an organoalkoxysilane having an epoxy group is particularly suitable. For example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, or β- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane or the like can be used.
The above silane coupling agents may be used alone or in combination of two or more. In this invention, the usage-amount of the above silane coupling agents can be used within the range of 1-20 weight part with respect to 100 weight part of said alkoxysilane.
In the above, when 20 parts by weight or more is used, the rigidity and brittleness of the gas barrier composite polymer layer to be formed increase, and the insulation and workability of the gas barrier composite polymer layer tend to decrease. Is not preferable.

Next, as a sol-gel method catalyst, mainly a polycondensation catalyst, used in the gas barrier composition, a tertiary amine that is substantially insoluble in water and soluble in an organic solvent is used.
Specifically, for example, N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine, and the like can be used.
In the present invention, N, N-dimethylbenzylamine is particularly preferred.
The amount used is 0.01 to 1.0 part by weight, preferably about 0.03 parts by weight per 100 parts by weight of the total amount of alkoxide and silane coupling agent.
The acid used in the gas barrier composition is used as a catalyst for the sol-gel method, mainly as a catalyst for hydrolysis of an alkoxide, a silane coupling agent, or the like.
Examples of the acid include mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid, organic acids such as acetic acid and tartaric acid, and the like.
The amount of the acid used is about 0.001 to 0.05 mol, preferably about 0.01 mol, relative to the total molar amount of the alkoxide and the alkoxide content of the silane coupling agent (for example, silicate moiety). Is preferred.

Furthermore, in the gas barrier composition, water can be used in a proportion of 0.1 to 100 mol, preferably 0.8 to 2 mol, relative to 1 mol of the total molar amount of the alkoxide.
When the amount of water exceeds 2 mol, the polymer obtained from the alkoxysilane and the metal alkoxide becomes spherical particles, and the spherical particles are three-dimensionally cross-linked, resulting in low density and porosity. Therefore, such a porous polymer is not preferable because the gas barrier property of the barrier film cannot be improved.
Moreover, when the amount of the water is less than 0.8 mol, it is not preferable because the hydrolysis reaction tends to hardly proceed.

Furthermore, as the organic solvent used in the gas barrier composition, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol, and the like can be used.
Furthermore, in the gas barrier composition, the polyvinyl alcohol-based resin and / or the ethylene / vinyl alcohol copolymer is in a state of being dissolved in a coating solution containing the alkoxide or the silane coupling agent. Therefore, the type of the organic solvent is appropriately selected.
In the case of using a combination of a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer, it is preferable to use n-butanol.
In the present invention, as the ethylene / vinyl alcohol copolymer solubilized in a solvent, for example, those commercially available as Soarnol (trade name) can be used.
The amount of the organic solvent used is usually 30 per 100 parts by weight of the total amount of the alkoxide, silane coupling agent, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer, acid and sol-gel catalyst. ~ 500 parts by weight.

Next, in the present invention, the gas barrier composite polymer layer according to the present invention is specifically produced as follows, for example.
First, an alkoxide such as alkoxysilane, a silane coupling agent, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, a sol-gel catalyst, an acid, water, an organic solvent, and, if necessary, A metal alkoxide or the like is mixed to prepare a gas barrier composition (coating liquid).
Next, a polycondensation reaction gradually proceeds in the gas barrier composition (coating liquid).
Next, on the vapor-deposited layer made of an inorganic oxide formed on one surface of the biaxially stretched polyester resin film, the above gas barrier composition (coating liquid) is applied by a usual method by a conventional method, dry.
Thus, by the above drying, polycondensation of the alkoxide such as alkoxysilane, metal alkoxide, silane coupling agent, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer proceeds, and the coating film Is formed.
Further, preferably, the above coating operation is repeated to laminate a plurality of coating films composed of two or more layers.
Finally, the biaxially stretched polyester resin film coated with the above coating solution is at a temperature of about 20 ° C. to 180 ° C. and below the melting point of the biaxially stretched polyester resin film, preferably about 50 ° C. to 160 ° C. On the vapor deposition layer which consists of the inorganic oxide formed in one side of the biaxially stretched polyester-type resin film by heat-processing for 10 second-10 minutes at the temperature of the range of about degree C, said gas barrier composition ( The gas barrier composite polymer layer according to the present invention can be produced by forming one or more gas barrier composite polymer layers by the coating liquid.
The gas barrier composite polymer layer according to the present invention thus obtained is excellent in gas barrier properties.

  In the present invention, in place of the polyvinyl alcohol resin, an ethylene / vinyl alcohol copolymer, or both a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer are used in the same manner as described above. The gas barrier composite polymer layer according to the present invention produced by performing drying and heat treatment has the advantage that the gas barrier properties after hot water treatment such as boil treatment and retort treatment are further improved.

  Furthermore, in the present invention, as described above, when ethylene vinyl alcohol copolymer or polyvinyl alcohol resin and ethylene vinyl alcohol copolymer are not used in combination, that is, only polyvinyl alcohol resin is used. Then, when producing the gas barrier composite polymer layer according to the present invention, in order to improve the gas barrier property after the hot water treatment, for example, a gas barrier composition using a polyvinyl alcohol-based resin in advance is used. A first coating layer is formed by coating, and then a gas barrier composition containing an ethylene / vinyl alcohol copolymer is coated on the coating layer to form a second coating layer. It is possible to improve the gas barrier property of the gas barrier composite polymer layer according to the present invention by forming the composite layer. It is intended to.

  Furthermore, the coating layer formed by the gas barrier composition containing the above-mentioned ethylene / vinyl alcohol copolymer, or the gas barrier composition containing a combination of a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer. Forming a plurality of coating layers formed of an object by stacking a plurality of layers is also an effective means for improving the gas barrier properties of the gas barrier composite polymer layer according to the present invention.

Next, with regard to the method for producing a gas barrier composite polymer layer according to the present invention, as an alkoxide, the action of an alkoxysilane will be described as an example. Hydrolyzed.
At that time, the acid serves as a catalyst for hydrolysis.
Next, protons are taken from the generated hydroxyl groups by the action of the sol-gel method catalyst, and hydrolyzed products undergo dehydration polycondensation.
At this time, the silane coupling agent is simultaneously hydrolyzed by the acid catalyst, and the alkoxy group becomes a hydroxyl group.
In addition, due to the action of the base catalyst, ring opening of the epoxy group also occurs and a hydroxyl group is generated.
A polycondensation reaction between the hydrolyzed silane coupling agent and the hydrolyzed alkoxide also proceeds.
Furthermore, since the reaction system contains a polyvinyl alcohol resin, an ethylene / vinyl alcohol copolymer, or a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer, the polyvinyl alcohol resin and the ethylene / vinyl alcohol Reaction with the hydroxyl group of the copolymer also occurs.
The resulting polycondensate contains, for example, an inorganic part composed of bonds such as Si—O—Si, Si—O—Zr, Si—O—Ti, and the like, and an organic part derived from the silane coupling agent. In the above reaction constituting the composite polymer, for example, a linear polymer having a partial structural formula represented by the following formula (III) and further having a portion derived from a silane coupling agent is first formed. .
This polymer has an OR group (an alkoxy group such as an ethoxy group) branched from a linear polymer.
This OR group is hydrolyzed to become an OH group using an existing acid as a catalyst, and the OH group is first deprotonated by the action of a sol-gel method catalyst (base catalyst), and then polycondensation proceeds.
That is, this OH group undergoes a polycondensation reaction with a polyvinyl alcohol-based resin represented by the following formula (I) or an ethylene / vinyl alcohol copolymer represented by the following formula (II) to form Si—O—Si. It is considered that a composite polymer having a bond, for example, represented by the following formula (IV), or a copolymerized composite polymer represented by the following formulas (V) and (VI) is generated.

The above reaction proceeds at room temperature, and the viscosity of the gas barrier composition (coating liquid) increases during preparation.
This gas barrier composition (coating solution) is applied onto a vapor-deposited layer made of an inorganic oxide provided on a biaxially stretched polyester resin film, heated to produce a solvent and an alcohol produced by a polycondensation reaction. When removed, the polycondensation reaction is completed, and a transparent coating layer is formed on the vapor-deposited layer made of an inorganic oxide provided on one surface of the biaxially stretched polyester resin film.
In the case of laminating a plurality of the above-mentioned coating layers, the composite polymers in the coating layers between the layers are also condensed, and the layers are firmly bonded to each other.
Furthermore, the organic reactive group of the silane coupling agent and the hydroxyl group generated by hydrolysis are bonded to the hydroxyl group on the surface of the vapor deposition layer made of an inorganic oxide provided on one surface of the biaxially stretched polyester resin film. The adhesion between the surface of the vapor deposition layer made of an inorganic oxide provided on one surface of the biaxially stretched polyester resin film and the coating layer, the adhesiveness, and the like are also good.

In the method of the present invention, the amount of water added is adjusted to 0.8 to 2 mol, preferably 1.5 mol, relative to 1 mol of the alkoxide, so that the linear polymer described above is used. Is formed.
Such a linear polymer has crystallinity and has a structure in which a large number of minute crystals are embedded in an amorphous part.
Such a crystal structure is the same as that of a crystalline organic polymer (for example, vinylidene chloride or polyvinyl alcohol), and a polar group (0H group) is partially present in the molecule, resulting in a high molecular aggregation energy and a molecular chain. Excellent gas barrier properties due to high rigidity.

The barrier film according to the present invention is provided with a vapor-deposited layer made of an inorganic oxide and a gas barrier composite polymer layer on one surface of a biaxially stretched polyester resin film as described above, and thus the inorganic film A composite gas barrier layer is formed from an oxide-deposited layer and a gas barrier composite polymer layer, thereby having the above-described excellent characteristics, and is useful as a packaging material. In particular, the gas barrier property (O ₂ , N ₂ , H ₂ O, CO ₂ , etc., which is excellent in blocking and preventing permeation), it is preferably used as a barrier substrate constituting a food packaging film.
In particular, when used in so-called gas-filled packaging filled with N ₂ or CO ₂ gas, the excellent gas barrier property is extremely effective for holding the filled gas.
Furthermore, the barrier film according to the present invention is excellent in hot water treatment, particularly high-pressure hot water treatment (retort treatment), and exhibits extremely excellent gas barrier properties.

In the present invention, the vapor deposition layer made of an inorganic oxide and the gas barrier composite polymer layer form, for example, a chemical bond, a hydrogen bond, or a coordinate bond by hydrolysis / co-condensation reaction, and the inorganic oxide. Adhesion between the vapor-deposited layer and the gas barrier composite polymer layer is improved, and a synergistic effect of the two layers forms a composite gas barrier layer composed of the vapor-deposited layer made of inorganic oxide and the gas barrier composite polymer layer. Thus, a better gas barrier property can be exhibited.
As a method for applying the gas barrier composition of the present invention, for example, a roll coating such as a gravure roll coater, a spray coating, a spin coating, a date coating, a brush, a barcode, an applicator, etc. Alternatively, a coating film having a dry film thickness of 0.01 to 30 μm, preferably about 0.1 to 10 μm, can be formed by applying a plurality of times, and further, under a normal environment, 50 to 300 ° C., Preferably, condensation is performed by heating and drying at a temperature of 70 to 200 ° C. for 0.005 to 60 minutes, preferably 0.01 to 10 minutes, and the gas barrier composite polymer layer of the present invention. Can be formed.
If necessary, when applying the gas barrier composition of the present invention, a primer agent or the like can be applied on the vapor-deposited film made of an inorganic oxide in advance, or corona discharge treatment or plasma treatment. Further, pre-processing such as other can be arbitrarily performed.

As described above, the barrier film according to the present invention is provided on one surface of the biaxially stretched polyester resin film, if necessary, a plasma-treated surface with an inert gas, a chemical vapor deposition method or a physical vapor phase. A vapor deposition layer made of an inorganic oxide by a growth method, if necessary, a plasma-treated surface with oxygen gas, and a gas barrier composite polymer layer are sequentially laminated, and the vapor deposition layer made of the inorganic oxide and the gas barrier composite polymer layer The present invention relates to a barrier film characterized by providing a composite gas barrier layer comprising:
Thus, the barrier film according to the present invention has a good gas tight adhesion between the biaxially stretched polyester resin film, the vapor-deposited layer made of inorganic oxide, and the gas barrier composite polymer layer, and further has a high gas barrier. It is extremely useful as a gas barrier material constituting a packaging bag, etc., having stable transparency and good transparency, heat resistance, impact resistance, etc. Heat seal resin layer, intermediate base material, plastic base material, etc. are arbitrarily laminated to produce a laminated material as a packaging material composed of various layer configurations, and then used. By making a bag, it is possible to manufacture packaging bags and packaging products of various forms.

Next, in the present invention, the heat-seal resin layer constituting the laminated material according to the present invention will be described. The heat-seal resin layer can be melted by heat and fused to each other. For example, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate Polyolefin resin such as copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene or polypropylene, acrylic acid, methacrylic acid, maleic anhydride Acid-modified polyolefin resin modified with unsaturated carboxylic acid such as fumaric acid, etc. , One or a film of a resin or sheet consisting of more resins other like - can be used bets or a coating film.
The resin film or sheet can be used in a single layer or multiple layers, and the thickness of the resin film or sheet is about 5 μm to 300 μm, preferably 10 μm to 110 μm. The position is desirable.
Furthermore, in the present invention, the thickness of the resin film or sheet is from the inorganic oxide that constitutes the barrier film at the time of making a packaging bag, using the laminated material according to the present invention. In order to prevent generation of scratches or cracks in the deposited layer, it is preferable to relatively increase the film thickness, specifically, about 40 μm to 110 μm, preferably 50 μm. It is preferable that it is about ~ 100 μm.
Thus, in the present invention, among the resin films or sheets as described above, it is particularly preferable to use an unstretched polypropylene film or sheet having a thickness of about 50 μm to 100 μm.

Next, in the present invention, as an intermediate base material constituting the laminated material according to the present invention, as with the biaxially stretched polyester resin film described above, the basic or auxiliary material constituting the packaging bag according to the present invention. Because it is a material, it has excellent properties in mechanical, physical, chemical, etc., has excellent strength, heat resistance, moisture resistance, pinhole resistance, puncture resistance, transparency In addition, an excellent resin film or sheet can be used.
Specifically, for example, a film of tough resin such as polyester resin, polyamide resin, polyaramid resin, polypropylene resin, polycarbonate resin, polyacetal resin, fluorine resin, or the like. A sheet can be used.
Thus, as the resin film or sheet, any of an unstretched film and a stretched film stretched in a uniaxial direction or a biaxial direction can be used.
In the present invention, the thickness of the resin film or sheet may be a thickness that can be kept to the minimum necessary for strength, puncture resistance, rigidity, and the like. On the other hand, if it is too thin, the strength, puncture resistance, rigidity, etc. are lowered, which is not preferable.
In the present invention, for the reasons described above, about 10 μm to 100 μm, preferably about 12 μm to 50 μm is most desirable.
Thus, in the present invention, among the resin films or sheets as described above, it is particularly preferable to use a biaxially stretched polyamide resin film having a thickness of about 15 μm to 30 μm.

Next, in the present invention, the plastic substrate constituting the laminated material according to the present invention will be described. As such a plastic substrate, this is the basic material or auxiliary material constituting the packaging bag according to the present invention. Excellent mechanical, physical, chemical, etc. In addition, it has excellent puncture resistance, etc., as well as excellent heat resistance, moisture resistance, pinhole resistance, transparency, etc. Resin films or sheets can be used.
Specifically, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins such as various nylon resins, polyaramid resins, polypropylene resins, polyethylene resins, polycarbonate resins, polyacetal resins, fluorine resins Further, a tough resin film or sheet such as other can be used.
In the above, any film such as an unstretched film, a stretched film stretched in a uniaxial direction or a biaxial direction can be used as the resin film or sheet. In the present invention, the thickness of the resin film or sheet may be a thickness that can be kept to the minimum necessary for strength, puncture resistance, and the like. If it is too thick, the cost increases. On the other hand, if it is too thin, the strength, puncture resistance, and the like are undesirably lowered.
In the present invention, about 9 μm to 100 μm, preferably about 12 μm to 50 μm is the most desirable for the reasons described above.
In the present invention, a desired printed pattern layer or the like can be provided on the front surface and / or back surface of the plastic substrate.

By the way, since packaging bags are usually subjected to severe physical and chemical conditions, the laminated materials constituting the packaging bags are required to have strict packaging suitability, deformation prevention strength, drop impact. Various conditions such as strength, pinhole resistance, heat resistance, sealability, quality maintenance, workability, hygiene, etc. are required. For this reason, in the present invention, in addition to the above materials, In addition, other materials that satisfy the above-mentioned conditions can be arbitrarily used. Specifically, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, Ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid or methacrylic acid copolymer, Ten 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. Can be used.
In addition, for example, 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.

In particular, in the present invention, the other base material includes, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene having a barrier property that prevents permeation of water vapor, water, and the like. -Films or sheets of resin such as propylene copolymer, and various colored resin films having light-shielding properties formed by adding a colorant such as a pigment to the resin and kneading the resin with a desired additive. Or a sheet or the like can be used.
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, on one side or both sides of the above-mentioned base material constituting the barrier film, laminated material or the like according to the present invention, for example, it consists of characters, figures, symbols, patterns, etc. A desired printed pattern can be printed to form a printed pattern layer.
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 absorber, a curing agent. One or more additives such as additives, crosslinking agents, lubricants, antistatic agents, fillers, etc. are optionally added, and colorants such as dyes and pigments are added, and solvents, diluents, etc. Kneaded sufficiently to prepare an ink composition, and then the ink composition is used. For example, gravure printing, offset printing, letterpress printing, screen printing, transfer printing, flexographic printing, etc. Can be used to form a printed pattern layer according to the present invention by printing a desired printed pattern consisting of characters, figures, symbols, patterns, etc. on one side of the substrate film. .

  In the above, as the ink vehicle, known ones such as sesame oil, drill oil, soybean oil, hydrocarbon oil, rosin, rosin ester, rosin modified resin, shellac, alkyd resin, phenolic resin, maleic acid Resin, natural resin, hydrocarbon resin, polyvinyl chloride resin, polyvinyl acetate resin, polystyrene resin, polyvinyl butyral resin, acrylic or methacrylic resin, polyamide resin, polyester resin, polyurethane resin, One or more of epoxy resins, urea resins, melamine resins, aminoalkyd resins, nitrocellulose, ethyl cellulose, chlorinated rubber, cyclized rubber, etc. can be used.

In the present invention, examples of the laminating adhesive constituting the laminating adhesive layer forming the laminate according to the present invention include, for example, polyvinyl acetate adhesive, ethyl acrylate, butyl, 2-ethylhexyl ester Homopolymers such as these, or polyacrylic acid ester adhesives, cyanoacrylate adhesives, ethylene and vinyl acetate, ethyl acrylate, acrylic acid, and the like, and their copolymers with methyl methacrylate, acrylonitrile, styrene, etc. , Ethylene copolymer adhesives composed of copolymers with monomers such as methacrylic acid, cellulose adhesives, polyester adhesives, polyamide adhesives, polyimide adhesives, amino acids composed of urea resins or melamine resins, etc. Resin adhesive, phenol resin adhesive, epoxy adhesive, Urethane adhesive, reactive (meth) acrylic adhesive, chloroprene rubber, nitrile rubber, rubber adhesive made of styrene-butadiene rubber, silicone adhesive, alkali metal silicate, low melting point glass, etc. Adhesives such as system adhesives and others can be used.
The composition system of the above-mentioned adhesive may be any composition form such as an aqueous type, a solution type, an emulsion type, and a dispersion type, and the property is any of film / sheet form, powder form, solid form, etc. Further, the bonding mechanism may be any of a chemical reaction type, a solvent volatilization type, a heat melting type, a hot pressure type, and the like.
Thus, in the present invention, the above laminating adhesive is applied to one side of both of the laminated layers, for example, a coating method such as a roll coating method, a gravure roll coating method, a kiss coating method, or the like, or a printing method. Then, the solvent or the like is dried to form an adhesive layer for laminating, and the coating or printing amount is preferably about 0.1 to 10 g / m ² (dry state).

In the present invention, examples of the anchor coating agent constituting the anchor coating agent layer forming the laminated material according to the present invention include isocyanate (urethane), polyethyleneimine, and polybutadiene. Anchor coating agents such as those based on organic, organic titanium, etc. can be used.
Furthermore, in the present invention, as the melt-extruded resin in the melt-extrusion laminating method, for example, a low density polyethylene, a medium density polyethylene, a high density polyethylene, a linear (linear) low density polyethylene, or a metallocene catalyst is used. Polymerized ethylene-α-olefin copolymer, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene- Acid-modified polyolefin resins such as propylene copolymer, methylpentene polymer, polyethylene, polypropylene, etc. modified with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, etc., etc. Can be used.
In the present invention, when performing the above lamination, if necessary, for example, pretreatment such as corona treatment, ozone treatment, frame treatment, etc. can be optionally applied to the surface of the substrate to be laminated. .

By the way, in the present invention, as the anchor coat agent for forming the anchor coat layer as described above and the adhesive for laminate forming the laminate adhesive layer, for example, Aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, or aliphatics such as hexamethylene diisocyanate, xylylene diisocyanate A polyether polyurethane resin obtained by reacting a polyfunctional isocyanate such as a polyisocyanate with a hydroxyl group-containing compound such as a polyether polyol, a polyester polyol or a polyacrylate polyol, Mainly polyester-based polyurethane resin or polyacrylate polyurethane-based resin Lanka - co - DOO agents, or laminating - those it is desirable to use the preparative adhesive.
Thus, the anchor coat agent layer or the laminate adhesive layer formed by using the anchor coat agent or the laminating adhesive as described above, A thin film that is soft, flexible, and flexible can be formed, improves its tensile elongation, and acts as a film having flexibility, flexibility, etc. on the vapor deposition layer made of inorganic oxide. , For example, improving the post-processing suitability of the vapor deposition layer composed of inorganic oxide at the time of post-processing such as laminating, printing, or bag making, and applying the vapor deposition layer composed of inorganic oxide at the time of post-processing It prevents the occurrence of cracks and the like.
Incidentally, in the present invention, the anchor coat layer by the anchor coat agent and / or the laminate adhesive layer by the laminate adhesive as described above are based on JIS standard K7113. It has a tensile elongation of 100 to 300%.
Thus, in the present invention, the tensile elongation of the anchor coating layer by the anchor coating agent and / or the laminating adhesive layer by the laminating adhesive as described above, etc. Improves the tight adhesion between the barrier film and the heat-seal resin layer, thereby preventing the occurrence of cracks in the vapor deposition layer made of inorganic oxide, and the laminating strength, etc. Is to increase.
In the above, it is not preferable that the tensile elongation is less than 100%, because the flexibility as a laminated material is lost, and cracks and the like in the deposited film of the inorganic oxide are likely to occur, and the tensile elongation is not preferable. If it exceeds 300%, the adhesive strength as an anchor coating agent or a laminating adhesive is not sufficient, and the required laminating strength becomes difficult to be expressed. Is.

Next, in the present invention described above, the method for producing the laminated material according to the present invention will be described in more detail. As such a method, for example, a lamination method used when producing a normal packaging material, for example, wet lamination. , Dry lamination method, solvent-free lamination method, extrusion lamination method, coextrusion lamination method, inflation method, and other methods.
Thus, in the present invention, when performing the above-described lamination, if necessary, for example, pretreatment such as corona treatment, ozone treatment, or frame treatment is optionally applied to the surface of the substrate to be laminated. be able to.
In the above, when extrusion lamination is performed, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin. , A polyolefin resin such as ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene or polypropylene with acrylic acid, Acid-modified polyolefin resins modified with unsaturated carboxylic acids such as methacrylic acid, maleic anhydride, fumaric acid, etc. can be used as the resin for melt extrusion lamination.
At that time, as an adhesion assistant, for example, an anchor coating agent such as isocyanate, polyethyleneimine, or the like can be arbitrarily used.
In the present invention, when dry lamination is performed, for example, a solvent type, an aqueous type, an emulsion type having a vehicle as a main component such as vinyl, acrylic, polyurethane, polyamide, polyester, epoxy, etc. Other adhesives for laminating, etc. can be used.

Next, in the present invention, the packaging bag according to the present invention manufactured using the above laminated material will be described. The packaging bag uses the above laminated material, and its heat seal. The surfaces of the conductive resin layers are overlapped with each other, and then the peripheral end portion is heat sealed to form a seal portion, and a packaging bag having an opening at the upper end portion is formed. be able to.
Thus, as the bag making method, the above-mentioned laminated material is folded or overlapped so that the inner layer faces each other, and the peripheral edge thereof is, for example, a side seal type, two-layer type. Square seal type, three-way seal type, four-side seal type, envelope-attached seal type, jointed seal type (pill seal type), pleated seal type, flat bottom seal Heat-sealing in the form of a heat seal such as a shell type, square bottom seal type, gusset type, etc., and manufacturing packaging bags having various forms having an opening at the upper end. Can do.
In addition, as the packaging bag, for example, a self-supporting packaging bag (standing pouch) can be used.
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.

Next, in the present invention, various contents according to the present invention are filled by filling the contents from the opening of the packaging bag produced above, and then sealing the opening at the upper end with a heat seal or the like. A packaged product having the form of can be produced.
In the present invention, the contents are filled from the opening of the packaging bag produced above, and then the opening is sealed with a heat seal or the like at the upper end of the bag for retort according to the present invention. A semifinished packaging product using a pouch is manufactured, and then the semifinished packaging product is subjected to a heat treatment such as a retort treatment or a boil treatment, thereby producing a retort packaged food using the retort pouch according to the present invention. It is something that can be done.
In the above, as a method for retorting or boiling, for example, a normal retort kettle is used, and the temperature is about 110 to 130 ° C., preferably about 120 ° C., pressure, 1 to 3 kgf / cm ² · G, Preferably, a method of heating and pressurizing at about 2.1 kgf / cm ² · G, about 20 to 60 minutes, preferably about 30 minutes, or temperature, 90 to 100 ° C., preferably 90 ° C. It can be carried out by a method of performing a boil treatment in about front and rear, time, about 5 to 20 minutes, preferably about 10 minutes.
Thus, in the present invention, the contents can be subjected to heat sterilization, heat sterilization cooking, or the like by retort processing or boil processing as described above.

Next, in the present invention, the contents to be filled and packaged in the packaging bag according to the present invention include, for example, cooked food, marine product, frozen food, boiled food, simmered food, liquid soup, seasoning, drinking water, Other foods and drinks, such as curry, stew, soup, meat sauce, hamburger, meatball, sweet potato, oden, rice cake etc. Various foods and beverages such as foods, jelly-like foods, seasonings, water, etc. can be mentioned.
Thus, in the present invention, the packaging bag according to the present invention has heat resistance, pressure resistance, water resistance, heat seal resistance, pin hole resistance, puncture resistance, tight adhesion, etc. Excellent physical properties, especially barrier properties that prevent permeation of oxygen gas, water vapor, etc., transparency, withstands heat treatment associated with retort processing, etc., and further reduces weight and weight of containers and packaging waste In addition, the manufacturing cost can be reduced by shortening the manufacturing process, and the contents can be packed and packaged and the quality is excellent.

Specifically, in the present invention, for example, when a polyester-based resin film is used as the base film, particularly for packaging excellent in physical properties such as thermal dimensional stability, heat resistance, and bending resistance. A bag can be manufactured, and when a polyamide-based resin (nylon) film is used as an intermediate substrate, for example, a packaging bag excellent in pinhole resistance can be manufactured. It can be done.
In the present invention, the vapor-deposited layer made of an inorganic oxide and the gas barrier composite polymer layer each have transparency and barrier properties that prevent permeation of oxygen gas, water vapor, and the like. With these, the effects such as barrier properties that block the permeation of oxygen gas, water vapor, etc. are exhibited. Ultimately, the synergistic effects thereof exert the effects such as barrier properties, and aluminum Unlike metal foil such as aluminum foil, it exhibits excellent effects such as barrier properties that are almost equivalent to metal foil such as foil, and is excellent in transparency, etc. This enables a metal detection test using a metal detector or the like.
Further, in the present invention, the vapor deposition layer or the like made of an inorganic oxide has a film thickness of several tens to several thousand mm, and the gas barrier composite polymer layer also has a film thickness of 0.1 g. / M ^{2 to} 2.0 g / m ² (dry state), for example, the film thickness is significantly reduced compared to metal foils such as aluminum foil having a film thickness of about 5 to 20 μm. Thus, the weight can be reduced and the weight can be remarkably reduced to reduce the weight and weight of the container / packaging waste.
Furthermore, in the present invention, an organic silicon compound is used as a vapor deposition monomer gas, and a vapor deposition layer made of silicon oxide formed into a film by plasma chemical vapor deposition is used as an inorganic material constituting the barrier layer. When used as a vapor deposition layer made of an oxide, the vapor deposition layer made of silicon oxide is flexible and has bending resistance. It has the advantage that there is nothing to do.
Next, the present invention will be described more specifically with reference to examples.

(1). First, as a base material film, a load of 0.07 N / mm is applied to the film, and when the temperature is raised to 25 to 200 ° C. at 5 ° C./min, the longitudinal dimensional change rate is −4.0%, and the transverse dimension. Using a biaxially stretched polyethylene terephthalate film with a change rate of + 0.1% and a thickness of 12 μm, this is mounted on a feed roll of a wind-up type vacuum evaporation apparatus, and then fed out and biaxially stretched The polyethylene terephthalate film is subjected to ultraviolet (366 nm) transmission under the following deposition conditions by vacuum deposition using an electron beam (EB) heating method while supplying oxygen gas to the corona-treated surface of aluminum terephthalate film. An aluminum oxide vapor deposition film having a rate of 94% and a film thickness of 20 nm was formed.
(Deposition conditions)
・ Vapor deposition method: Physical vapor deposition (PVD)
・ Vacuum degree in the evaporation chamber; 2 × 10 ^-4 mbar
・ Vacuum degree in the take-up chamber; 2 × 10 ^-2 mbar
・ Electron beam power: 25kW
-Cooling drum temperature: -15 ° C
-Film conveyance speed: 540 m / min-Vapor deposition surface: Corona-treated surface Next, immediately after forming a 20 nm thick aluminum oxide vapor deposition film, a glow discharge plasma generator is formed on the aluminum oxide vapor deposition film surface. , Power 9 kw, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2.5 (unit: Slm) mixed gas, mixed gas pressure 6.0 × 10 ⁻² Oxygen / argon mixed gas plasma treatment was performed at mbar and a treatment speed of 200 m / min to form a plasma treatment surface in which the surface tension of the aluminum oxide vapor deposition film surface was improved by 54 dyne / cm or more.
(2). On the other hand, according to the composition shown in Table 1 below, the composition a. Composition prepared in advance in EVOH solution in which EVOH (ethylene copolymerization ratio 29%) was dissolved in a mixed solvent of isopropyl alcohol and ion-exchanged water b. A hydrolyzed solution composed of ethyl silicate 40, isopropyl alcohol, acetylacetone aluminum, and ion-exchanged water, and stirred, and further prepared in advance c. A mixed solution composed of an aqueous polyvinyl alcohol solution, a silane coupling agent (epoxysilica SH6040), acetic acid, isopropyl alcohol and ion-exchanged water was added and stirred to obtain a colorless and transparent barrier coating solution.
(Table 1)
a EVOH (ethylene copolymerization rate 29%) 0.610 (wt%)
Isopropyl alcohol 3.294
H ₂ O 2.196
b Ethyl silicate 40 11.460
Isopropyl alcohol 17.662
Aluminum acetylacetone 0.020
H ₂ O 13.752
c Polyvinyl alcohol 1.520
Silane coupling agent 0.050
Isopropyl alcohol 13.844
H ₂ O 35.462
Acetic acid 0.130
Total 100.000 (wt%)
Next, the gas barrier composition produced above is used for the plasma-treated surface with oxygen gas formed in (1) above, and this is coated by the gravure roll coating method, and then at 130 ° C. for 1 minute. Heat treatment was performed to form a gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state) to produce a barrier film according to the present invention.
(3). Next, after forming a desired printing pattern on the surface of the gas barrier coating film of the barrier film produced in the above (2), a two-component curable polyurethane laminating film is formed on the entire surface including the printing pattern. The adhesive for coating is coated to a thickness of 4.0 g / m ² (in a dry state) using a gravure roll coating method to form an adhesive layer for laminating, and then the adhesive for laminating A biaxially stretched nylon 6 film having a thickness of 15 μm was laminated on the surface of the agent layer with the corona-treated surfaces facing each other, and then both were laminated by dry lamination.
Next, after applying the corona discharge treatment to the surface of the biaxially stretched nylon 6 film laminated as described above, a laminating adhesive layer is formed on the corona treatment surface in the same manner as described above, and thereafter The laminate material according to the present invention was manufactured by dry laminating and laminating an unstretched polypropylene film having a thickness of 60 μm on the laminating adhesive layer surface.
(4). Next, two sheets of the laminated material produced above are prepared, the non-stretched polypropylene film faces are overlapped with each other, and then the outer peripheral edge is sealed in a three-way heat seal. A three-sided seal-type flexible packaging bag having an opening portion and an opening on the upper side was manufactured. 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 packaged food according to the present invention was produced.
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. .

(1). First, as a base material film, a load of 0.07 N / mm is applied to the film, and when the temperature is raised to 25 to 200 ° C. at 5 ° C./min, the longitudinal dimensional change rate is −4.0%, and the transverse dimension. Using a biaxially stretched polyethylene terephthalate film with a change rate of -0.1% and a thickness of 12 μm, this film was mounted on a feed roll of a take-up vacuum deposition apparatus, and then fed out. Ultraviolet light (366 nm) is applied to the corona-treated surface of the stretched polyethylene terephthalate film by vacuum deposition using an electron beam (EB) heating method while supplying oxygen gas using aluminum as a vapor deposition source under the following vapor deposition conditions. An evaporated aluminum oxide film having a transmittance of 90% and a film thickness of 15 nm was formed.
(Deposition conditions)
・ Vapor deposition method: Physical vapor deposition (PVD)
・ Vacuum degree in the evaporation chamber; 2 × 10 ^-4 mbar
・ Vacuum degree in the take-up chamber; 2 × 10 ^-2 mbar
・ Electron beam power: 25kW
-Cooling drum temperature: -15 ° C
-Film conveyance speed: 540 m / min-Vapor deposition surface: Corona-treated surface Next, immediately after forming the aluminum oxide vapor deposition film having a thickness of 15 nm as described above, a glow discharge plasma generator is formed on the aluminum oxide vapor deposition film surface. , Power 9 kw, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2.5 (unit: Slm) mixed gas, mixed gas pressure 6.0 × 10 ⁻² Oxygen / argon mixed gas plasma treatment was performed at mbar and treatment speed of 200 m / min to form a plasma treated surface in which the surface tension of the aluminum oxide deposition film surface was improved by 54 dyne / cm or more.
(2). On the other hand, according to the composition shown in Table 2 below, composition a. EVOH (ethylene copolymerization ratio 29%) A composition prepared in advance in an EVOH solution dissolved in a mixed solvent of isopropyl alcohol and ion-exchanged water b. A hydrolyzate composed of ethyl silicate 40, isopropyl alcohol, acetylacetone aluminum, and ion-exchanged water, followed by stirring, and a composition prepared in advance c. A mixed liquid composed of an aqueous polyvinyl alcohol solution, acetic acid, isopropyl alcohol and ion-exchanged water was added and stirred to obtain a colorless and transparent barrier coating liquid.
(Table 2)
a EVOH (ethylene copolymerization ratio 29%) 0.122 (wt%)
Isopropyl alcohol 0.659
H ₂ O 0.439
b Ethylsilicate 40 9.146
Isopropyl alcohol 8.780
Aluminum acetylacetone 0.018
H ₂ O 16.291
c Polyvinyl alcohol 1.220
Isopropyl alcohol 19.893
H ₂ O 43.329
Acetic acid 0.103
Total 100.000 (wt%)
Next, the gas barrier composition produced above is used for the plasma-treated surface with oxygen gas formed in (1) above, and this is coated by the gravure roll coating method, and then at 130 ° C. for 1 minute. Heat treatment was performed to form a gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state) to produce a barrier film according to the present invention.
(3). Next, using the barrier film produced in the above (2), the laminate material and the three-way seal according to the present invention are used in the same manner as in the above-described Example 1 in the same manner as in the above-described Example 1. Molded soft packaging bags, semi-finished packaging products, and retort packaging foods.
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. .

(1). First, as a base film, a load of 0.07 N / mm is applied to the film, and when the temperature is raised to 25 to 200 ° C. at 5 ° C./min, the longitudinal dimensional change rate is −2.5%, and the transverse dimension. A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm and a change rate of + 0.1% was used.
First, 1 part by weight of γ-isocyanatopropyltrimethoxysilane and 10 parts by weight of acrylic polyol are weighed out in a dilute solvent of methyl ethyl ketone (MEK) / ethyl acetate, mixed and stirred, and then isophorone diisocyanate. An anchor was prepared by diluting 3% of a mixed solution in which NCO groups were added in an equivalent amount to the OH groups of acrylyl polyol (IPDI).
Next, the anchoring agent was coated on the corona-treated surface of the biaxially stretched polyethylene terephthalate film by a gravure roll coating method, and then dried to a thickness of 0.2 g / m ² (dry operation State) anchor layer.
Next, the biaxially stretched polyethylene terephthalate film having the anchor agent layer formed thereon was used, and this was mounted on a feed roll of a wind-up type vacuum vapor deposition apparatus. The surface of the anchor layer of the terephthalate film is transmitted with ultraviolet rays (366 nm) under the following vapor deposition conditions by using an electron beam (EB) heating method while supplying oxygen gas using aluminum as a vapor deposition source. An aluminum oxide vapor deposition film having a rate of 94% and a film thickness of 20 nm was formed.
(Deposition conditions)
・ Vapor deposition method: Physical vapor deposition (PVD)
・ Vacuum degree in the evaporation chamber; 2 × 10 ^-4 mbar
・ Vacuum degree in the take-up chamber; 2 × 10 ^-2 mbar
・ Electron beam power: 25kW
-Cooling drum temperature: -15 ° C
-Film conveyance speed: 540 m / min-Vapor deposition surface: Corona-treated surface Next, immediately after forming a 20 nm thick aluminum oxide vapor deposition film, a glow discharge plasma generator is formed on the aluminum oxide vapor deposition film surface. , Power 9 kw, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2.5 (unit: Slm) mixed gas, mixed gas pressure 6.0 × 10 ⁻² Oxygen / argon mixed gas plasma treatment was performed at mbar and a treatment speed of 200 m / min to form a plasma treatment surface in which the surface tension of the aluminum oxide vapor deposition film surface was improved by 54 dyne / cm or more.
(2). On the other hand, according to the composition shown in Table 1 below, the composition a. Composition prepared in advance in EVOH solution in which EVOH (ethylene copolymerization ratio 29%) was dissolved in a mixed solvent of isopropyl alcohol and ion-exchanged water b. A hydrolyzed solution composed of ethyl silicate 40, isopropyl alcohol, acetylacetone aluminum, and ion-exchanged water, and stirred, and further prepared in advance c. A mixed solution composed of an aqueous polyvinyl alcohol solution, a silane coupling agent (epoxysilica SH6040), acetic acid, isopropyl alcohol and ion-exchanged water was added and stirred to obtain a colorless and transparent barrier coating solution.
(Table 1)
a EVOH (ethylene copolymerization rate 29%) 0.610 (wt%)
Isopropyl alcohol 3.294
H ₂ O 2.196
b Ethyl silicate 40 11.460
Isopropyl alcohol 17.662
Aluminum acetylacetone 0.020
H ₂ O 13.752
c Polyvinyl alcohol 1.520
Silane coupling agent 0.050
Isopropyl alcohol 13.844
H ₂ O 35.462
Acetic acid 0.130
Total 100.000 (wt%)
Next, the gas barrier composition produced above is used for the plasma-treated surface with oxygen gas formed in (1) above, and this is coated by the gravure roll coating method, and then at 130 ° C. for 1 minute. Heat treatment was performed to form a gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state) to produce a barrier film according to the present invention.
(3). Next, using the barrier film produced in the above (2), the laminate material and the three-way seal according to the present invention are used in the same manner as in the above-described Example 1 in the same manner as in the above-described Example 1. Molded soft packaging bags, semi-finished packaging products, and retort packaging foods.
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. .

(1). First, as a base film, a load of 0.07 N / mm is applied to the film, and when the temperature is raised to 25 to 200 ° C. at 5 ° C./min, the longitudinal dimensional change rate is −2.5%, and the transverse dimension. Using a biaxially stretched polyethylene terephthalate film with a change rate of + 0.1% and a thickness of 12 μm, this is mounted on the feed roll of a take-up vacuum deposition apparatus, and then fed out and biaxially stretched. Using a mixture of silicon monoxide and silicon as a deposition source on the corona-treated surface of a polyethylene terephthalate film, supplying oxygen gas, and using a vacuum deposition method using an electron beam (EB) heating method, under the following deposition conditions: Then, a deposited film of silicon oxide having a thickness of 30 nm was formed.
(Deposition conditions)
・ Vapor deposition method: Physical vapor deposition (PVD)
・ Vacuum degree in the evaporation chamber; 2 × 10 ^-4 mbar
・ Vacuum degree in the take-up chamber; 2 × 10 ^-2 mbar
・ Electron beam power: 35kW
-Cooling drum temperature: -15 ° C
-Film conveyance speed: 240 m / min-Vapor deposition surface: Corona-treated surface Next, immediately after forming a silicon oxide vapor deposition film having a thickness of 30 nm as described above, a glow discharge plasma generator is formed 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, mixed gas pressure 6.0 × 10 ⁻² Oxygen / argon mixed gas plasma treatment was performed at mbar and a treatment speed of 200 m / min to form a plasma treated surface in which the surface tension of the deposited silicon oxide film surface was improved by 54 dyne / cm or more.
(2). On the other hand, according to the composition shown in Table 1 below, the composition a. Composition prepared in advance in EVOH solution in which EVOH (ethylene copolymerization ratio 29%) was dissolved in a mixed solvent of isopropyl alcohol and ion-exchanged water b. A hydrolyzed solution composed of ethyl silicate 40, isopropyl alcohol, acetylacetone aluminum, and ion-exchanged water, and stirred, and further prepared in advance c. A mixed solution composed of an aqueous polyvinyl alcohol solution, a silane coupling agent (epoxysilica SH6040), acetic acid, isopropyl alcohol and ion-exchanged water was added and stirred to obtain a colorless and transparent barrier coating solution.
(Table 1)
a EVOH (ethylene copolymerization rate 29%) 0.610 (wt%)
Isopropyl alcohol 3.294
H ₂ O 2.196
b Ethyl silicate 40 11.460
Isopropyl alcohol 17.662
Aluminum acetylacetone 0.020
H ₂ O 13.752
c Polyvinyl alcohol 1.520
Silane coupling agent 0.050
Isopropyl alcohol 13.844
H ₂ O 35.462
Acetic acid 0.130
Total 100.000 (wt%)
Next, the gas barrier composition produced above is used for the plasma-treated surface with oxygen gas formed in (1) above, and this is coated by the gravure roll coating method, and then at 130 ° C. for 1 minute. Heat treatment was performed to form a gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state) to produce a barrier film according to the present invention.
(3). Next, using the barrier film produced in the above (2), the laminate material and the three-way seal according to the present invention are used in the same manner as in the above-described Example 1 in the same manner as in the above-described Example 1. Molded soft packaging bags, semi-finished packaging products, and retort packaging foods.
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. .

(1). First, as a base film, a load of 0.07 N / mm is applied to the film, and when the temperature is raised to 25 to 200 ° C. at 5 ° C./min, the longitudinal dimensional change rate is −2.5%, and the transverse dimension. Using a 12 μm thick biaxially stretched polyethylene terephthalate film with a change rate of + 0.1%, this is mounted on a feed roll of a plasma chemical vapor deposition apparatus, and then fed out to provide the biaxially stretched polyethylene terephthalate film. On the corona-treated surface of the film, a silicon oxide vapor deposition film having a thickness of 10 nm was formed under the following vapor deposition conditions.
(Deposition conditions)
・ Vapor deposition method; Plasma chemical vapor deposition (CVD method)
・ Vapor deposition raw materials: hexamethyldisiloxane (HMDSO), oxygen gas (O ₂ ), helium gas (He)
-Raw material composition ratio in the first chamber; HMDSO: O ₂ : He = 1: 0: 1
Raw material composition ratio in second chamber; HMDSO: O ₂ : He = 1: 10: 1
・ Raw material composition ratio in third chamber: None ・ Vacuum degree in chamber: 4.0 × 10 ⁻² Pa
-Film transport speed: 200 m / min
-Vapor deposition surface: Corona-treated surface Next, immediately after forming the silicon oxide vapor deposition film having a thickness of 10 nm as described above, a glow discharge plasma generator was used on the surface of the silicon oxide vapor deposition film, and the power was 9 kw, oxygen Gas (O ₂ ): Argon gas (Ar) = 7.0: 2.5 (unit: Slm) is used, and the mixed gas pressure is 6.0 × 10 ⁻² mbar and the processing speed is 200 m / min. Oxygen / argon mixed gas plasma treatment was performed to form a plasma-treated surface in which the surface tension of the deposited silicon oxide film surface was improved by 54 dyne / cm or more.
(2). On the other hand, according to the composition shown in Table 1 below, the composition a. Composition prepared in advance in EVOH solution in which EVOH (ethylene copolymerization ratio 29%) was dissolved in a mixed solvent of isopropyl alcohol and ion-exchanged water b. A hydrolyzed solution composed of ethyl silicate 40, isopropyl alcohol, acetylacetone aluminum, and ion-exchanged water, and stirred, and further prepared in advance c. A mixed solution composed of an aqueous polyvinyl alcohol solution, a silane coupling agent (epoxysilica SH6040), acetic acid, isopropyl alcohol and ion-exchanged water was added and stirred to obtain a colorless and transparent barrier coating solution.
(Table 1)
a EVOH (ethylene copolymerization rate 29%) 0.610 (wt%)
Isopropyl alcohol 3.294
H ₂ O 2.196
b Ethyl silicate 40 11.460
Isopropyl alcohol 17.662
Aluminum acetylacetone 0.020
H ₂ O 13.752
c Polyvinyl alcohol 1.520
Silane coupling agent 0.050
Isopropyl alcohol 13.844
H ₂ O 35.462
Acetic acid 0.130
Total 100.000 (wt%)
Next, the gas barrier composition produced above is used for the plasma-treated surface with oxygen gas formed in (1) above, and this is coated by the gravure roll coating method, and then at 130 ° C. for 1 minute. Heat treatment was performed to form a gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state) to produce a barrier film according to the present invention.
(3). Next, using the barrier film produced in the above (2), the laminate material and the three-way seal according to the present invention are used in the same manner as in the above-described Example 1 in the same manner as in the above-described Example 1. Molded soft packaging bags, semi-finished packaging products, and retort packaging foods.
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. .

[Comparative Example 1]
(1). First, as a base film, a load ratio of 0.05 to 0.15 N / mm is applied to the film, and the dimensional change rate in the vertical direction when the temperature is raised to 25 to 200 ° C. at 5 ° C./min is −7.0%, A 12 μm thick biaxially stretched polyethylene terephthalate film with a lateral dimensional change rate of −2.0% was used, and this was mounted on a take-up roll of a wind-up type vacuum deposition apparatus, and then fed out. The corona-treated surface of the biaxially stretched polyethylene terephthalate film uses aluminum as a vapor deposition source, supplies oxygen gas, and uses a vacuum vapor deposition method using an electron beam (EB) heating method. A deposited film of aluminum oxide having a thickness of 20 nm was formed.
(Deposition conditions)
・ Vapor deposition method: Physical vapor deposition (PVD)
・ Vacuum degree in the evaporation chamber; 2 × 10 ^-4 mbar
・ Vacuum degree in the take-up chamber; 2 × 10 ^-2 mbar
・ Electron beam power: 25kW
-Cooling drum temperature: -15 ° C
-Film conveyance speed: 540 m / min-Vapor deposition surface: Corona-treated surface Next, immediately after forming a 20 nm thick aluminum oxide vapor deposition film, a glow discharge plasma generator is formed on the aluminum oxide vapor deposition film surface. , Power 9 kw, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2.5 (unit: Slm) mixed gas, mixed gas pressure 6.0 × 10 ⁻² Oxygen / argon mixed gas plasma treatment was performed at mbar and a treatment speed of 200 m / min to form a plasma treatment surface in which the surface tension of the aluminum oxide vapor deposition film surface was improved by 54 dyne / cm or more.
(2). On the other hand, according to the composition shown in Table 1 below, the composition a. Composition prepared in advance in EVOH solution in which EVOH (ethylene copolymerization ratio 29%) was dissolved in a mixed solvent of isopropyl alcohol and ion-exchanged water b. A hydrolyzed solution composed of ethyl silicate 40, isopropyl alcohol, acetylacetone aluminum, and ion-exchanged water, and stirred, and further prepared in advance c. A mixed solution composed of an aqueous polyvinyl alcohol solution, a silane coupling agent (epoxysilica SH6040), acetic acid, isopropyl alcohol and ion-exchanged water was added and stirred to obtain a colorless and transparent barrier coating solution.
(Table 1)
a EVOH (ethylene copolymerization rate 29%) 0.610 (wt%)
Isopropyl alcohol 3.294
H ₂ O 2.196
b Ethyl silicate 40 11.460
Isopropyl alcohol 17.662
Aluminum acetylacetone 0.020
H ₂ O 13.752
c Polyvinyl alcohol 1.520
Silane coupling agent 0.050
Isopropyl alcohol 13.844
H ₂ O 35.462
Acetic acid 0.130
Total 100.000 (wt%)
Next, the gas barrier composition produced above is used for the plasma-treated surface with oxygen gas formed in (1) above, and this is coated by the gravure roll coating method, and then at 130 ° C. for 1 minute. Heat treatment was performed to form a gas barrier coating film having a thickness of 0.4 g / m ² (in the dry operation state) to produce a barrier film.
(3). Next, using the barrier film produced in the above (2), the laminate material and the three-sided seal type soft packaging are used in the same manner as in the above-described Example 1 and in the same manner as in the above-described Example 1. Bags, semi-finished packaging, and retort-packed foods were manufactured.

[Comparative Example 2]
(1). First, as a base film, a load ratio of 0.05 to 0.15 N / mm is applied to the film, and the dimensional change rate in the vertical direction when the temperature is raised to 25 to 200 ° C. at 5 ° C./min is −7.0%, A biaxially stretched polyethylene terephthalate film having a thickness change rate of −2.0% and a thickness of 12 μm was used, and this was mounted on a feeding roll of a plasma chemical vapor deposition apparatus. On the corona-treated surface of the axially stretched polyethylene terephthalate film, a silicon oxide vapor deposition film having a thickness of 10 nm was formed under the following vapor deposition conditions.
(Deposition conditions)
・ Vapor deposition method; Plasma chemical vapor deposition (CVD method)
・ Vapor deposition raw materials: hexamethyldisiloxane (HMDSO), oxygen gas (O ₂ ), helium gas (He)
-Raw material composition ratio in the first chamber; HMDSO: O ₂ : He = 1: 0: 1
Raw material composition ratio in second chamber; HMDSO: O ₂ : He = 1: 10: 1
・ Raw material composition ratio in third chamber: None ・ Vacuum degree in chamber: 4.0 × 10 ⁻² Pa
-Film transport speed: 200 m / min
-Vapor deposition surface: Corona-treated surface Next, immediately after forming the silicon oxide vapor deposition film having a thickness of 10 nm as described above, a glow discharge plasma generator was used on the surface of the silicon oxide vapor deposition film, and the power was 9 kw, oxygen Gas (O ₂ ): Argon gas (Ar) = 7.0: 2.5 (unit: Slm) is used, and the mixed gas pressure is 6.0 × 10 ⁻² mbar and the processing speed is 200 m / min. Oxygen / argon mixed gas plasma treatment was performed to form a plasma-treated surface in which the surface tension of the deposited silicon oxide film surface was improved by 54 dyne / cm or more.
(2). On the other hand, according to the composition shown in Table 1 below, the composition a. Composition prepared in advance in EVOH solution in which EVOH (ethylene copolymerization ratio 29%) was dissolved in a mixed solvent of isopropyl alcohol and ion-exchanged water b. A hydrolyzed solution composed of ethyl silicate 40, isopropyl alcohol, acetylacetone aluminum, and ion-exchanged water, and stirred, and further prepared in advance c. A mixed solution composed of an aqueous polyvinyl alcohol solution, a silane coupling agent (epoxysilica SH6040), acetic acid, isopropyl alcohol and ion-exchanged water was added and stirred to obtain a colorless and transparent barrier coating solution.
(Table 1)
a EVOH (ethylene copolymerization rate 29%) 0.610 (wt%)
Isopropyl alcohol 3.294
H ₂ O 2.196
b Ethyl silicate 40 11.460
Isopropyl alcohol 17.662
Aluminum acetylacetone 0.020
H ₂ O 13.752
c Polyvinyl alcohol 1.520
Silane coupling agent 0.050
Isopropyl alcohol 13.844
H ₂ O 35.462
Acetic acid 0.130
Total 100.000 (wt%)
Next, the gas barrier composition produced above is used for the plasma-treated surface with oxygen gas formed in (1) above, and this is coated by the gravure roll coating method, and then at 130 ° C. for 1 minute. Heat treatment was performed to form a gas barrier coating film having a thickness of 0.4 g / m ² (in the dry operation state) to produce a barrier film.
(3). Next, using the barrier film produced in the above (2), the laminate material and the three-sided seal type soft packaging are used in the same manner as in the above-described Example 1 and in the same manner as in the above-described Example 1. Bags, semi-finished packaging, and retort-packed foods were manufactured.

[Experimental example]
About the barrier film manufactured in said Examples 1-5 and Comparative Examples 1-2, with respect to the raw film (2m width) used this time, the oxygen permeability in the central part and a total of three places of both ends And the water vapor permeability was measured.
Moreover, about the packaging bag manufactured by bag-making the laminated material manufactured using the barrier film manufactured in Examples 1 to 5 and Comparative Examples 1 and 2, oxygen permeability before and after the retort treatment, The water vapor transmission rate and the laminating strength before and after the retort treatment were measured.
(1). Measurement of Oxygen Permeability This was measured with a measuring instrument (model name, OX-TRAN 2/20) manufactured by MOCON, USA, under conditions of a temperature of 23 ° C. and a humidity of 90% RH.
(2). Measurement of water vapor transmission rate This was measured with a measuring instrument (model name, PERMATRAN 3/31) manufactured by MOCON, USA, under conditions of a temperature of 40 ° C. and a humidity of 100% RH.
(3). Measurement of Laminate Strength Laminate strength was measured using a Tensilon measuring instrument with a test piece of 15 mm and a peeling speed of 50 min.
The measurement results are shown in Table 3 and Table 4 below.

(Table 3)
┌────┬─────────────────────────────┐ │ │ Barrier film │ │ ├─────── ────────┬──────────────┤ │ │ Oxygen permeability │ Water vapor permeability │ │ ├ ─────┬────┬──── │ ────┬────┬────┤ │ │ Left end │ Center │ Right end │ Left end │ Center │ Right end │ ├────┼────┼────┼ ────┼────┼────┼────┤ │Example 1│0.43│0.32│0.40│1.43│1.28│1.40│ ├ ────┼────┼────┼────┼────┼────┼────┤ │Example 2│0.39│0.34│0. 41│1.25│1.18│1.27│ ├────┼────┼────┼────┼────┼─── ３────┤ │Example 3│0.37│0.31│0.40│1.10│1.07│1.09│ ├────┼────┼──── ┼────┼────┼────┼────┤ │Example 4│0.33│0.25│0.26│0.89│0.85│0.91│ ├────┼────┼────┼────┼────┼────┼────┤ │Example 5│0.87│0.30│0 38│1.54│1.45│1.49│ ├────┼────┼────┼────┼────┼────┼───── │ │Comparative Example 1│1.62│0.36│1.86│2.59│1.57│2.88│ ├────┼────┼────┼──── ┼────┼────┼────┤ │Comparative Example 2│1.54│0.34│1.63│2.43│2.11│2.55│ └────┴────┴────┴────┴────┴────┴────┘ In Table 3 above, the unit of oxygen permeability is [ cc / m ² / day / atm · 23 ° C. · 90% RH], and the unit of water vapor permeability is [g / m ² / day · 40 ° C. · 100% RH].

(Table 4)
┌────┬───────────┬───────────┐ │ │ Oxygen permeability │ Water vapor permeability │ │ ├ ─────┬── ───┼─────┬ ─────┤ │ │Before retort │After retort │Before retort │After retort │ ├────┼─────┼─────┼── ───┼─────┤ Example 1│ 0.35│ 0.71│ 1.03│ 1.25│ ├────┼─────┼─────┼─ ────┼─────┤ │Example 2│ 0.37│ 0.74│ 1.11│ 1.30│ ├────┼─────┼─────┼ ─────┼─────┤ │Example 3│ 0.33│ 0.73│ 0.97│ 1.21│ ├────┼─────┼───── ┼─────┼─────┤ │Example 4│ 0.28│ 0.69│ 0.90│ 1.10│ ────┼─────┼─────┼─────┼─────┤ │Example 5│ 0.32│ 0.75│ 1.22│ 1.46│ ├────┼─────┼─────┼─────┼─────┤ │Comparative Example 1│ 0.36│ 1.12│ 1.36│ 1.99 │ ├────┼─────┼─────┼────┼┼─────┤ │Comparative Example 2│ 0.35│ 1.53│ 1.97│ １． 73│ └────┴─────┴─────┴─────┴─────┘
┌────┬───────────────────────┐ │ │ Laminate Strength │ │ ├ ─────────── ┬ ───────────┤ │ │ Before retorting │ After retorting │ ├────┼───────────┼─────────── │ │Example 1│ 280 (FC) │ 240 (FC) │ ├────┼───────────┼───────────┤ │Example 2 │ 310 (FC) │ 300 (FC) │ ├────┼───────────┼───────────┤ │Example 3 │ 460 (FC) │ 440 (FC) │ ├────┼───────────┼───────────┤ │Example 4 │ 350 (FC) │ 330 (FC) │ ├────┼───────────┼───────────┤ │ Example 5 │ 270 (FC) │ 240 (FC) │ ├────┼───────────┼───────────┤ │Comparative Example 1 │ 190 │ 150 │ ├────┼───────────┼───────────┤ │Comparative Example 2 │ 240 (FC) │ 200 (FC) │ └── ──┴───────────┴────────────┘ In Table 4 above, the unit of oxygen permeability is [cc / m ² / day / atm · 23 ° C./90% RH], the unit of water vapor permeability is [g / m ² / day · 40 ° C./100% RH], and the unit of laminating strength is [gf / 15 mm]. The unit of (FC) means that the substrate is cut.

  As is apparent from the measurement results shown in Tables 3 and 4 above, it was confirmed that the samples according to Examples 1 to 5 were sufficiently practical in terms of oxygen permeability and water vapor permeability. In addition, the laminate strength was excellent, the transparency was further improved, and the contents were highly visible.

  The barrier film according to the present invention and the laminated material using the same, and the packaging bag made using the same are excellent in barrier properties for preventing permeation of oxygen gas, water vapor, etc., in particular, in water vapor barrier properties. Furthermore, it has excellent adhesion to the laminated material, for example, withstands heat treatment associated with processing such as retort processing, and further reduces the weight and weight of containers and packaging waste, and shortens the manufacturing process. For example, it is useful for filling and packaging various foods and beverages such as cooked foods, marine products, frozen foods, boiled foods, rice cakes, liquid soups, seasonings, drinking water, etc. It is excellent in filling and packing of contents and quality maintenance.

It is a schematic sectional drawing which shows an example of the layer structure about the barrier film which concerns on this invention. It is a schematic sectional drawing which shows an example of the layer structure about the barrier film which concerns on this invention. It is a schematic sectional drawing which shows an example of the layer structure about the laminated material which uses the barrier film which concerns on this invention shown in FIG. It is a schematic sectional drawing which shows an example of the layer structure about the laminated material which uses the barrier film which concerns on this invention shown in FIG. It is a schematic sectional drawing which shows an example of the layer structure about the laminated material which uses the barrier film which concerns on this invention shown in FIG. It is a schematic perspective view which shows an example of the structure about the packaging bag which uses the laminated material shown in FIG. It is a schematic perspective view which shows an example of the structure about the packaging bag which uses the laminated material shown in FIG. It is a schematic block diagram which shows the outline | summary of the example about a plasma chemical vapor deposition apparatus. It is a schematic block diagram which shows the outline | summary of the example about a winding-type vacuum evaporation system.

Explanation of symbols

A A ₁ barrier film B, B ₁ , B ₂ laminate C packaging bag D packaging product 1 base film 2 vapor-deposited layer made of inorganic oxide 3 gas barrier composite polymer layer 4 composite gas barrier layer 5 plasma treated surface 6 Plasma treatment surface 11 Heat seal resin layer 12 Intermediate substrate 13 Plastic substrate 15 Heat seal portion 16 Opening portion 17 Contents 18 Upper seal portion

Claims (10)

In the barrier film in which a composite gas barrier layer composed of a vapor deposition layer composed of an inorganic oxide and a gas barrier composite polymer layer is laminated on one surface of the base film, a load is applied to the base film as the above base film. When 0.05 to 0.15 N / mm is applied and the temperature is raised to 25 to 200 ° C. at a rate of temperature increase of 5 ° C./min, the dimensional change rate in the vertical and horizontal directions is −5.0, respectively. A barrier film using a biaxially stretched polyester resin film in a range of -2.0% and -1.0- + 1.0%. The biaxially stretched polyester resin film is made of a biaxially stretched polyethylene terephthalate film, a biaxially stretched polybutylene terephthalate film or a biaxially stretched polyethylene naphthalate film. Barrier film. 3. The barrier according to claim 1, wherein the vapor-deposited layer made of an inorganic oxide is a vapor-deposited film of an inorganic oxide by chemical vapor deposition or physical vapor deposition. Sex film. The vapor-deposited layer made of an inorganic oxide is made of a vapor-deposited film of aluminum oxide having an ultraviolet ray (wavelength 366 nm) transmittance of 85 to 96% by physical vapor deposition. 3. The barrier film described in 3. The barrier according to any one of claims 1 to 3, wherein the vapor-deposited layer comprising an inorganic oxide comprises a vapor-deposited film of silicon oxide by physical vapor deposition using a mixture of silicon monoxide and silicon as a raw material. Sex film. The barrier film according to any one of claims 1 to 3, wherein the vapor-deposited layer made of an inorganic oxide is a vapor-deposited film of silicon oxide by a chemical vapor deposition method. The gas barrier composite polymer layer has the general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, and M represents a metal atom) , N represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M), and a polyvinyl alcohol-based resin. And / or an ethylene-vinyl alcohol copolymer, and further comprising a gas barrier coating film made of a gas barrier composition obtained by polycondensation by a sol-gel method. The barrier film described in any one of the above. In the barrier film in which a composite gas barrier layer composed of a vapor deposition layer composed of an inorganic oxide and a gas barrier composite polymer layer is laminated on one surface of the base film, a load is applied to the base film as the above base film. When 0.05 to 0.15 N / mm is applied and the temperature is raised to 25 to 200 ° C. at a rate of temperature increase of 5 ° C./min, the dimensional change rate in the vertical and horizontal directions is −5.0, respectively. Gas barrier properties that constitute a composite gas barrier layer using a barrier film composed of a biaxially stretched polyester resin film in the range of -2.0% and -1.0 to + 1.0% A laminated material comprising a heat sealable resin layer laminated on the surface of a composite polymer layer. The laminated material according to claim 8, wherein a plastic base material is laminated on the other surface of the biaxially stretched polyester resin film. The laminated material according to any one of claims 8 to 9, wherein an intermediate base material is laminated between the barrier film and the heat seal resin layer.

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