JP2006116704A - Barrier film and laminated material using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a barrier film excellent in transparency, having high gas barrier properties and excellent high temperature hot water sterilization treatment optitude against boiling or retorting and enhanced in practicality having boiling resistance and retorting resistance not causing the deterioration of barrier properties, interlaminar peeling (delamination) or the like, and a laminated material using it. <P>SOLUTION: An anchor coating agent layer comprising a resin composition, which contains a polyacrylic or polymethacrylic resin having at least two hydroxy groups in its structure and a curing agent, is provided on one side of a base material film while a vapor deposition layer comprising an inorganic oxide is further provided on the anchor coating agent layer and a gas barrier coating film comprising a gas barrier composition is furthermore provided on the vapor deposition layer comprising the inorganic oxide to constitute the barrier 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.
For example, the thickness of a silicon compound having a composition of the general formula Si _x O _y (x = 1, 2, y = 0, 1, 2, 3) is 100 to 3000 mm on at least one surface of a flexible plastic film having a thickness of 5 to 300 μm. A transparent flexible plastic film having a high degree of air resistance and moisture resistance provided with a transparent thin film layer has been proposed (for example, see Patent Document 1).
Moreover, it has a barrier property comprising a plastic substrate and a transparent thin film layer of silicon oxide having a silicon atom to oxygen atom ratio of 1: 0.3 to 2 provided on one surface of the plastic substrate. A packaging material such as a transparent retort food has also been proposed (see, for example, Patent Document 2). Furthermore, it is a laminated material including a barrier film in which a thin film layer of an inorganic substance is formed and a sealant layer, and the shrinkage rate when the sealant layer is heated at 120 ° C. for 20 minutes has a longitudinal direction and a transverse direction A packaging material for transparent retort sterilization, which is characterized by being unstretched polypropylene each containing 0.5% or less and containing no rubber component, has also been proposed (for example, see Patent Document 3).
Japanese Examined Patent Publication No. 53-12953 (Claims) JP-A-1-202436 (Claims etc.) Japanese Patent No. 2827772 (Claims etc.)

However, for the barrier substrate proposed in Patent Documents 1 to 3 above, for example, a laminated material is produced using this, and further, a bag is produced from this to produce a packaging bag, After that, the contents were filled and packaged in the packaging bag, and an attempt was made to produce a packaged product having various forms. In the packaged product, the base film constituting the barrier base material and There is a problem in the adhesive strength between the vapor-deposited layer made of an inorganic oxide, often causing delamination, and it is extremely difficult to produce a fully satisfactory packaged product.
In particular, the packaging bag is filled and packaged with the contents to produce a packaging semi-finished product, and then the packaging semi-finished product is boiled or sterilized with hot water by retorting to produce the packaging product. In this case, the above-mentioned barrier base material is particularly inferior in water vapor barrier property, gas barrier property is remarkably deteriorated during processing, adhesive strength and the like are lowered, delamination and the like are remarkably generated, The actual condition is that the mechanical strength is deteriorated and is not suitable for the sterilization method as described above.
Therefore, the present invention is excellent in transparency, has a high gas barrier property, is excellent in high-temperature hot water sterilization treatment such as boil and retort, and has no boil resistance without causing deterioration of barrier properties, delamination, etc. An object of the present invention is to provide a highly practical barrier film having retort resistance and a laminate using the same.

  As a result of various studies to solve the above problems, the present inventor paid attention to providing an anchor coating agent layer for improving the tight adhesion on one surface of the base film. And using an anchor coating agent comprising a resin composition containing a polyacrylic or polymethacrylic resin having two or more hydroxyl groups in its structure and a curing agent, on one side of the base film An anchor coating agent layer made of a resin composition containing a polyacrylic or polymethacrylic resin having two or more hydroxyl groups in its structure and a curing agent is provided, and then the anchor coating is provided. A vapor-deposited layer made of an inorganic oxide is provided on the agent layer, and further, an alkoxysilane, a silane coupling agent and a water-soluble resin are contained on the vapor-deposited layer made of the inorganic oxide; Degenerate by sol-gel method A gas barrier coating film by the gas barrier composition obtained as described above is provided to produce a barrier film, and then the barrier film is used, for example, at least on the surface of the gas barrier coating film. Laminated resin layers are laminated to produce a laminated material, and then the laminated material is used, and this is made into a bag to produce a packaging bag, and then the packaging bag is filled with contents. As a result, when we manufactured packaging products with various forms, it was extremely excellent in close adhesion between the base film and the vapor-deposited layer made of inorganic oxide, and there was no reduction in delamination between the layers. In addition, it has excellent transparency, high gas barrier properties and excellent suitability for high-temperature hot water sterilization treatment such as boil and retort, and resistance to boil that does not cause deterioration of barrier properties, delamination, etc. Leto And it completed the present invention have found that it is possible to manufacture the laminated material using highly practical barrier film and it has bets resistance.

  That is, the present invention provides an anchor coating agent comprising a resin composition comprising a polyacrylic or polymethacrylic resin having two or more hydroxyl groups in its structure on one surface of a base film and a curing agent. A vapor deposition layer made of an inorganic oxide on the anchor coating agent layer, and an alkoxysilane and a silane coupling agent on the vapor deposition layer made of the inorganic oxide. In addition, the present invention relates to a barrier film comprising a water-soluble resin and further provided with a gas barrier coating film made of a gas barrier composition obtained by polycondensation by a sol-gel method, and a laminate using the barrier film.

By using an anchor coating agent comprising a resin composition containing a polyacrylic or polymethacrylic resin having two or more hydroxyl groups in its structure and a curing agent, the present invention The adhesion strength between the deposited layers of inorganic oxides can be remarkably improved, and the close adhesion between the two is extremely excellent, and there is no decrease in delamination between the layers. is there.
Thereby, in this invention, it is excellent in transparency, and has high gas barrier property, and is excellent in high temperature hot water sterilization treatment such as boil and retort, and does not cause deterioration of barrier properties, delamination, etc. It has an advantage that a highly practical barrier film having boil resistance and retort resistance and a laminate using the same can be produced.
Further, in the present invention, a gas barrier property that prevents permeation of oxygen gas, water vapor, etc., in particular, water vapor, is obtained by laminating a vapor deposition layer made of an inorganic oxide and a gas barrier coating film in multiple layers to form a composite gas barrier layer. Excellent barrier properties, and excellent post-processing suitability such as laminating, bag making, etc. Furthermore, water resistance in heat sterilization treatment such as retort treatment and boil treatment can be markedly improved. It is extremely excellent in moisture resistance and the like.
Furthermore, in the present invention, when the vapor-deposited layer made of inorganic oxide and the gas barrier coating film are laminated in multiple layers, the surface of the vapor-deposited layer made of inorganic oxide is laminated by providing a plasma-treated surface with oxygen gas or the like. By doing so, the adhesion between the layers is extremely strong, the adhesion between the two is remarkably improved, and phenomena such as delamination between the layers are not recognized at all, The lamination strength can be remarkably improved, and with the remarkable improvement in the adhesion strength between the above-mentioned base film and the vapor deposition layer made of inorganic oxide, the advantage that it is extremely excellent in water resistance strength, etc. It is what you have.

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.
FIG. 1 is a schematic cross-sectional view showing an example of the layer structure of the barrier film according to the present invention, and FIGS. 2, 3 and 4 show the laminated material using the barrier film according to the present invention. It is a schematic sectional drawing which shows a few examples of a layer structure, FIG. 5 and FIG. 6 shows an example of the structure about the packaging bag made using the laminated material using the barrier film based on this invention. It is a schematic perspective view.

  First, as shown in FIG. 1, the barrier film A according to the present invention is cured with a polyacrylic or polymethacrylic resin having two or more hydroxyl groups in its structure on one surface of a base film 1. An anchor coating agent layer 2 made of a resin composition containing an agent is provided, and a vapor deposition layer 3 made of an inorganic oxide is further provided on the anchor coating agent layer 2, and the inorganic coating agent is further provided. A configuration in which a gas barrier coating film 4 made of a gas barrier composition containing an alkoxysilane, a silane coupling agent and a water-soluble resin and obtained by polycondensation by a sol-gel method is provided on the vapor deposition layer 3 made of an oxide. The basic structure consists of

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. 2, in the present invention, the heat seal resin layer 11 is laminated on the surface of the gas barrier coating film 4 constituting the barrier film A according to the present invention shown in FIG. On the surface of the gas barrier coating film 4 constituting the barrier film A according to the present invention shown in FIG. 1 as shown in FIG. A laminate B ₁ using a barrier film according to the present invention having a structure in which a heat-seal resin layer 11 is laminated, and further, as shown in FIG. 4, the book shown in FIG. The barrier film A according to the invention is constructed. A plastic substrate 13 is further laminated on the other surface of the substrate film 1 to be heated, and a heat seal resin is formed on the surface of the gas barrier coating film 4 constituting the barrier film A according to the present invention. Examples thereof include a laminate B ₂ using the barrier film according to the present invention having a configuration in which the layers 11 are laminated.
2, 3, and 4, reference numerals 1, 2, 3, 4, and the like have the same meanings as reference numerals 1, 2, 3, 4, and the like shown in FIG.

  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 laminate B shown in FIG. 2, two laminates 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. 6, 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 laminate 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 to 135 ° C, pressure, 1 to 3 kgf / cm 2 · Retort treatment such as pressure heat sterilization for about 20 to 60 minutes at the 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, boil | boil at about 90 to 95 degreeC for about 30 to 60 minutes, give a heat sterilization process etc., and manufacture a sterilization treatment packaging product. It is also possible.
Further, in the present invention, although not shown in the drawings, a laminated material using the barrier film according to the present invention shown in FIG. 3 and FIG. 4 is used. It is possible to manufacture packaging bags, packaging products, and the like that are made using the laminated material 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 coating film 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. The material film will be described. As such a base film, this is a basic material constituting the barrier film, laminated material, packaging bag and the like according to the present invention, and further, an anchor coating agent layer, inorganic Because it is a base material that holds a vapor-deposited layer made of oxide or a gas barrier coating film, etc., first, withstand the conditions of their formation, processing, etc., and improve them without impairing their properties In addition, it is excellent in various work properties such as workability, heat resistance, slipperiness, pinhole resistance, etc., and other conditions are satisfied. Gain Resin film or sheet - may be used and. In the present invention, specific examples of the resin film or sheet include polyolefin resins such as polyethylene resins and polypropylene resins, cyclic polyolefin resins, polystyrene resins, and acrylonitrile-styrene copolymer. Polyester such as coalescence (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), poly (meth) acrylic resin, polycarbonate resin, polyethylene terephthalate, polyethylene naphthalate Films or sheets of various resins such as polyamide resins, polyamide resins such as various nylon resins, polyurethane resins, acetal resins, cellulose resins, and the like can be used.
In the present invention, it is particularly preferable to use a polyester resin, a polyolefin resin, or a polyamide resin film or sheet among the resin films or sheets.

In the present invention, as the above-mentioned various resin films or sheets, for example, one or more of the above-mentioned various resins are used, and an extrusion method, a cast molding method, a T-die method, a cutting method, an inflation method are used. -A method of forming the above-mentioned various resins independently using a film-forming method such as an ionization method or the like, or a method of forming a multilayer co-extrusion film using two or more types of various resins In addition, by using two or more kinds of resins, various film or sheet of resin is manufactured by a method of mixing and forming before forming a film, and if necessary, for example, Various resin films or sheets formed by stretching in a uniaxial or biaxial direction using a tenter system, a tuber system, or the like 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.

  It should be noted that one or more of the above-mentioned various resins are used, and in forming the film, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness Various plastic compounding agents and additives can be added for the purpose of improving and modifying mold release properties, flame retardancy, antifungal properties, electrical properties, strength, etc. Can be optionally added from a very small amount to several tens of percent depending on the purpose. In the above, 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.

Next, the anchor coat agent layer constituting the barrier film according to the present invention will be described. The anchor coat agent layer is a close adhesive property between a base film and a vapor deposition layer made of an inorganic oxide. In order to prevent the occurrence of delamination between the two layers.
Thus, in the present invention, the polyacrylic or polymethacrylic resin having two or more hydroxyl groups in the structure forming the resin composition constituting the anchor coating agent layer includes a polyacrylic or polyacrylic resin. A polyacrylic polymer or polymethacrylic resin having a polymethacrylic polymer as a basic skeleton and having two or more hydroxyl groups at its main chain, side chain, terminal, etc. and capable of reacting with a curing agent described later is used. be able to.
Specific examples of the polyacrylic or polymethacrylic resin include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 3-chloro-2-hydroxypropyl acrylate, di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl-monobutyl fumarate or polyethylene glycol monoacrylate, 2-hydroxyethyl methacrylate, 2- Hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl Α, β-ethylenically unsaturated carboxylic acids such as tacrylate, 3-chloro-2-hydroxypropyl methacrylate, di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl-monobutyl fumarate or polyethylene glycol monomethacrylate A homopolymer of a hydroxyalkyl ester monomer or a copolymer with another monomer can be used.
Alternatively, in the present invention, as the polyacrylic or polymethacrylic resin having two or more hydroxyl groups in the structure, for example, a polyacrylic resin or a polymethacrylic resin is modified with, for example, a polyester resin or the like. A modified polyacrylic resin or polymethacrylic resin having two or more hydroxyl groups in the structure can also be used.

In the above, other monomers include, for example, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, unsaturated mono- or dicarboxylic acids such as itaconic acid or citraconic acid, methyl acrylate, ethyl acrylate, n -Propyl acrylate, i-propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, pentyl acrylate, heptyl acrylate, octyl acrylate, benzyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl meta Acrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, pentyl methacrylate, (Meth) acrylate alkyl esters such as butyl methacrylate, octyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, glycidyl acrylate, glycidyl methacrylate, (β-methyl) glycidyl acrylate, (β-methyl) glycidyl methacrylate, allyl glycidyl ether, methacryl glycidyl ether Monomers having epoxy groups such as, monomers containing amide groups such as acrylamide, methacrylamide, dimethylacrylamide, dimethylmethacrylamide, styrene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl fluoride Alternatively, monomers such as vinylidene fluoride, ethylene, propylene, and the like can be used.
Moreover, in the above, as a polyester-type resin, the various polyester-type resin obtained by making a dicarboxylic acid component and a glycol component react can be used, for example.

Next, in the present invention, the curing agent for forming the resin composition constituting the anchor coating agent layer is a polyacrylic or polymethacrylic resin having two or more hydroxyl groups in the structure. It is added in order to improve the close adhesion between the base film and the vapor deposition layer made of an inorganic oxide by a urethane bond formed by reaction, and mainly acts as a crosslinking agent or a curing agent.
Thus, specific examples of the curing agent include aromatic tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), methylene bis (p-phenylene diisocyanate), 1 -Chlorophenyl-2,4-diisocyanate, 1,5-naphthylene diisocyanate, ethylbenzene-2,4-diisocyanate, 2,4-tolylene diisocyanate duplex, 4, 4 ', 4 "triphenylmethane triisocyanate, tris (4-phenylisocyanate) thiophosphate, xylene diisocyanate (XDI), aliphatic hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), hexa Adduct of methylene diisocyanate hexane triol, thiodipropyldi It is possible to use an isocyanate compound such as isocyanate, or one or more of these initial condensates or derivatives.

In the present invention, the mixing ratio of the polyacrylic or polymethacrylic resin having two or more hydroxyl groups in the structure and the isocyanate compound as the curing agent is not particularly limited, but the isocyanate compound is too small. If the amount is too large, blocking or the like occurs and there is a problem in processing.
In the present invention, the compounding ratio of the polyacrylic or polymethacrylic resin having two or more hydroxyl groups in the structure and the isocyanate compound as the curing agent is an NCO group derived from an isocyanate compound having 2 in the structure. It is preferably 50 times or less of the OH group derived from the above polyacrylic or polymethacrylic resin having a hydroxyl group, and particularly preferred is the case where the NCO group and the OH group are mixed in an equivalent amount. .

  In the present invention, in addition to a polyacrylic or polymethacrylic resin having two or more hydroxyl groups in the structure as described above and an isocyanate compound as a curing agent, for example, a vinyl resin or an epoxy resin One or more resins, urethane resins, or polyester resins can be added to reinforce the strength of the coating.

In the present invention, a polyacrylic or polymethacrylic resin having two or more hydroxyl groups in the structure and other necessary additives are added, and further, a solvent and a diluent are added and mixed well, and an arbitrary After diluting to a concentration, the resin composition constituting the anchor coat agent layer is prepared by mixing with an isocyanate compound as a curing agent.
In the present invention, various additives such as curing accelerators such as tertiary amines, imidazole derivatives, carboxylic acid metal salt compounds, quaternary ammonium salts, and quaternary phosphonium salts, phenols, sulfurs, phosphines, and the like. An antioxidant such as a phyto-based agent, a leveling agent, a flow regulator, a catalyst, a crosslinking reaction accelerator, a filler and the like can be added.
Thus, in the present invention, the resin composition prepared as described above is used, and this is applied to a printing method such as offset printing, gravure printing, silk screen printing, roll coating, knife edge coating, gravure, etc. Using a coating method such as coating, kiss coating, spin coating, etc., printing, coating or coating on the base film, and then drying the printed film or coating film to remove the solvent and curing. Thus, the anchor coating agent layer according to the present invention can be formed.
As a film thickness of said anchor coating agent layer, 0.05-10 g / m < ² > (dry state) rank is preferable.

  Next, in the present invention, a description will be given of a vapor deposition layer made of an inorganic oxide provided on an anchor coating agent layer provided on one surface of a base film constituting the barrier film according to the present invention. As a vapor deposition layer made of an inorganic oxide, for example, a chemical vapor deposition method, a physical vapor deposition method, or a combination of both, a single layer film consisting of one of the vapor deposition layers made of an inorganic oxide Alternatively, it can be produced by forming a multilayer film or a composite film composed of two or more layers.

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, a monomer gas for vapor deposition such as an organosilicon compound is used as a raw material on one surface of a base film, and an inert gas such as argon gas or helium gas is used as a carrier gas. Furthermore, an oxygen gas or the like is used as an oxygen supply gas, and a vapor deposition layer made of an inorganic oxide such as silicon oxide can be formed using a low temperature plasma chemical vapor deposition method using a low temperature plasma generator or the like. it can.
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 deposited layer made of an inorganic oxide by the low temperature plasma chemical vapor deposition method will be described. FIG. 7 shows an inorganic oxide by the plasma chemical vapor deposition method. It is a schematic block diagram of the low-temperature plasma chemical vapor deposition apparatus which shows the outline | summary about the formation method of the vapor deposition layer which consists of.
In the present invention, as shown in FIG. 7, the base film 1 is fed out from the unwinding roll 23 arranged in the vacuum chamber 22 of the plasma chemical vapor deposition apparatus 21, and further, the base film 1 Is conveyed onto the circumferential surface of the cooling / electrode drum 25 through the auxiliary roll 24 at a predetermined speed.
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. Then, plasma is generated on one surface of the base film 1 by the glow discharge plasma 30, and this is 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 surface of the base film 1 in the above, the base film 1 is the state holding the vapor deposition layer which consists of inorganic oxides, A vapor deposition layer made of an inorganic oxide by the plasma chemical vapor deposition method according to the present invention can be formed by being wound around a winding roll 34 via an auxiliary roll 33.
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 base film is transported at a constant speed, and the glow discharge plasma is used to cool the electrode drum peripheral surface. A vapor deposition layer made of an inorganic oxide such as silicon oxide can be formed on the surface of the upper biaxially stretched polyester resin film.
At this time, the degree of vacuum in the vacuum chamber should be adjusted to 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably to 1 × 10 ⁻¹ to 1 × 10 ⁻² Torr. In addition, it is desirable that the conveying speed of the base film 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 vapor deposition layer made of an inorganic oxide such as silicon oxide is formed on one surface of the base film by oxidizing the plasma source gas with oxygen gas while oxidizing the SiO _x Therefore, the formed vapor-deposited film of inorganic oxide such as silicon oxide is a continuous layer having high density, few gaps, and high flexibility. The barrier property of a vapor deposition layer made of an inorganic oxide such as silicon 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. A sufficient gas barrier property can be obtained.
In the present invention, the surface of the base film is cleaned by SiO _x plasma, and polar groups and free radicals are generated on the surface of the base film. It has the advantage that the tight adhesion between the vapor-deposited layer made of the product and the surface of the substrate 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 preparation of the 10 ^-2 Torr level, the degree of vacuum when forming a deposition layer of an inorganic oxide such as silicon oxide by a conventional vacuum deposition method, a ^{1 × 10 -4 ~1 × 10 -5} Torr position Since the degree of vacuum is lower than that of the base film, it is possible to shorten the time for setting the vacuum state at the time of replacing the base film, to easily stabilize the degree of vacuum, and to stabilize the film forming process.

In the present invention, a vapor deposition layer made of silicon oxide formed 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. The object is closely bonded to one surface of the base film to form a dense, flexible thin film, and is generally represented by the general formula SiO _x (where X represents a number from 0 to 2). It 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-mentioned compound, etc. This has the advantage that the tight adhesion to the vapor deposition layer made of silicon 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, a metal or a metal oxide is used as a raw material, this is heated and vaporized, and this is vapor-deposited on one surface of a base film, or a raw material is a metal or metal An oxidation reaction deposition method that uses metal oxide, oxidizes by introducing oxygen and deposits on one side of the base film, and further plasma-assisted oxidation reaction deposition method that assists the oxidation reaction with plasma. Can be used to form a deposited layer.
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. 8 is a schematic configuration diagram showing an example of a take-up vacuum deposition apparatus. .
As shown in FIG. 8, the base film 1 fed out from the unwinding roll 43 in the vacuum chamber 42 of the wind-up type vacuum deposition apparatus 41 is cooled through the guide rolls 44 and 45. Guided to the coating drum 46.
Thus, the vapor deposition source 48 heated by the crucible 47 such as metal aluminum or aluminum oxide is applied to one surface of the base film 1 guided on the cooled coating drum 46. Further, if necessary, a vapor deposition layer made of an inorganic oxide such as aluminum oxide is provided through the masks 50 and 50 while supplying oxygen gas or the like from the oxygen gas outlet 49 and supplying it. Then, the base film 1 on which a vapor deposition layer made of an inorganic oxide such as aluminum oxide is formed is sent out through the guide rollers 51 and 52 and wound around the winding roller 53. By taking it, the vapor deposition layer which consists of an inorganic oxide by the physical vapor deposition method concerning this invention can be formed.
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, on the surface of the vapor deposition layer made of an inorganic oxide provided on the anchor coating agent layer provided on one surface of the base film as described above, Improving tight adhesion with gas barrier coating film provided on vapor-deposited layer made of inorganic oxide. Ultimately, both of them are firmly adhered to prevent the occurrence of delamination. Therefore, it is preferable to form a plasma treatment surface with oxygen gas.
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 coating film constituting the barrier film according to the present invention will be described. The gas barrier coating film is provided on a vapor deposition layer made of an inorganic oxide, and is transparent and flexible. In addition, it forms a film with excellent gas barrier properties that prevents permeation of oxygen gas, water vapor, etc., and is firmly adhered to the vapor-deposited layer made of the above-mentioned inorganic oxide, and its inorganic A composite barrier layer consisting of two layers of an oxide vapor deposition layer and a gas barrier coating film is constructed, and due to the synergistic effect of both, it has an extremely excellent gas barrier property that prevents and blocks the transmission of oxygen gas, water vapor, etc. There is an effect.
Thus, in the present invention, the gas barrier coating film includes, for example, first an alkoxysilane, a silane coupling agent, and a water-soluble resin, and further includes a sol-gel method catalyst, an acid, water, and an organic solvent. A step of preparing a gas barrier composition that is polycondensed by a sol-gel method in the presence of a gas barrier; A step of applying a coating composition to provide a coating film, a base film provided with a coating film on a vapor-deposited layer made of the above inorganic oxide, at a temperature of 20 ° C. to 180 ° C. and the above group A gas barrier property by the above gas barrier property composition on a vapor deposition layer made of an inorganic oxide provided on one surface of the above base film by heat treatment at a temperature below the melting point of the material film for 10 seconds to 10 minutes. Painting It can be produced by including a manufacturing process step or the like for forming a film.

In the present invention, the gas barrier coating film constituting the barrier film according to the present invention is formed by applying a sol-gel method on a vapor deposition layer made of an inorganic oxide provided on one surface of the base film. When forming a coating film by applying a gas barrier composition to be condensed, a step of stacking two or more gas barrier compositions to be polycondensed by the sol-gel method, on the vapor deposition layer comprising the above inorganic oxide A base film provided with a coating film having two or more layers is heated at 20 ° C. to 180 ° C. and at a temperature not higher than the melting point of the base film for 10 seconds to 10 minutes. It is manufactured by a manufacturing process including a process of forming two or more gas barrier coating films of the above gas barrier composition on a vapor deposition layer made of an inorganic oxide provided on one surface of a material film. Can Kill.
In the present invention, the gas barrier composition preferably further contains at least one metal alkoxide according to a preferred embodiment.

Next, in the above description, the alkoxysilane used in the present invention 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.
Specific examples of the above alkoxysilane include, 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 ], and the like.

Furthermore, in the present invention, the alkoxysilane is represented by the general formula Rb _n Si (ORc) _4-m (wherein n represents an integer of 0 or more, and m represents 1, 2, 3). An alkylalkoxysilane represented by an integer, wherein Rb and Rc represent a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and the like) can be used.
Specific examples of the above 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.

In the present invention, a metal alkoxide such as zirconium alkoxide or titanium alkoxide can be used together with the above alkoxysilane, if necessary.
In the above, examples of the zirconium alkoxide include, for example, tetramethoxyzirconium [Zr (OCH ₃ ) ₄ ], tetraethoxyzirconium [Zr (OC ₂ H ₅ ) ₄ ], tetraipropoxyzirconium [Zr (is0-0C ₃ H ₇ ). ₄ ], tetra-n-butoxyzirconium [Zr (OC ₄ H ₉ ) ₄ ], and the like can be used.
In the present invention, toughness and heat resistance of the obtained barrier film can be improved by using zirconium alkoxide.
In the above, the amount used is in the range of 10 parts by weight or less, preferably about 5 parts by weight, based on 100 parts by weight of the alkoxysilane.
In the above, if it exceeds 10 parts by weight, the formed gas barrier coating film is likely to be gelled, the brittleness thereof becomes large, and further, the gas barrier coating film is easily peeled when coated on the base film. Tend to be.

In the above, 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-butoxytitanium [Ti (OC ₄ H ₉ ) ₄ ], etc. can be used.
The use of titanium alkoxide has the advantage that the thermal conductivity of the formed gas barrier coating film is lowered and the heat resistance of the base film is remarkably improved.
The amount used is in the range of 5 parts by weight or less, preferably about 3 parts by weight, based on 100 parts by weight of the alkoxysilane.
In the above, when the amount exceeds 5 parts by weight, the brittleness of the formed gas barrier coating film is increased, and when the base film is coated, the gas barrier coating film tends to be easily peeled off.

Furthermore, in the present invention, for example, aluminum alkoxide 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-n-butoxyaluminum [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.

Next, as the silane coupling agent used together with the above alkoxysilane, a known organic reactive group-containing organoalkoxysilane is used.
In particular, an organoalkoxysilane having an epoxy group is suitable.
Specifically, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, or β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane may be used. it can.
Two or more silane coupling agents as described above may be mixed and used.
The usage-amount of such a silane coupling agent exists in 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 coating film formed are increased, and the insulation and workability of the gas barrier coating film tend to be lowered.

Next, in the present invention, examples of the water-soluble resin constituting the gas barrier composition include, for example, polyvinyl alcohol resins, polyvinyl pyrrolidone resins, starch, methyl cellulose, carboxymethyl cellulose, sodium alginate, and the like. Further, in the present invention, an ethylene-vinyl alcohol copolymer can also be used.
Therefore, in the present invention, it is most preferable to use a polyvinyl alcohol-based resin as the water-soluble resin, and by using this, the gas barrier property can be remarkably improved.
Furthermore, in the present invention, from the viewpoint of improving gas barrier properties, it is also preferable to use a polyvinyl alcohol resin and an ethylene-vinyl alcohol copolymer in combination.

In the present invention, when a polyvinyl alcohol-based resin is used as a water-soluble resin as an example, the content of the polyvinyl alcohol-based resin is 100 parts by weight in total of the above alkoxysilane and metal alkoxide. The range is 50 to 200 parts by weight, preferably about 100 parts by weight.
In the above, if it exceeds 200 parts by weight, the brittleness of the gas barrier coating film becomes large, and the water resistance of the resulting barrier film is also unfavorable.
Further, if it is less than 50% by weight, the gas barrier property is lowered, which is not preferable.

Next, in the present invention, the sol-gel method catalyst constituting the gas barrier composition, that is, mainly the polycondensation catalyst, is a tertiary amine that is substantially insoluble in water and soluble in an organic solvent. Is used.
Specific examples include N, N-dimethylbenzylamine, tripropylamine, tributylamine, and tripentylamine, and N, N-dimethylbenzylamine is particularly preferable.
The amount used is 0.01 to 1 part by weight, preferably about 0.03 parts by weight per 100 parts by weight of the total amount of alkoxysilane, metal alkoxide, and silane coupling agent.

In the present invention, the acid constituting the gas barrier composition is used not only as a catalyst for the sol-gel method but also as an acetalization catalyst (mainly a hydrolysis catalyst) described later.
Specifically, sulfuric acid, hydrochloric acid, nitric acid or the like is used as the acid, and the amount of the acid used is 0. 001-0.05 mol, preferably about 0.01 mol.

Next, in the present invention, in the gas barrier composition according to the present invention, 0.8 to 2 mol of water is used with respect to 1 mol of the total molar amount of the above alkoxysilane and metal alkoxide.
In the above, when the amount of water exceeds 2 mol, the gas barrier coating film obtained from the alkoxysilane and the metal alkoxide becomes spherical particles, and the spherical particles are three-dimensionally cross-linked to have a low density. , Which is not preferable because it tends to be a porous polymer.
The porous polymer is not preferable because the gas barrier property of the base film cannot be improved.
In the above, if the amount of water is less than 0.8 mol, the hydrolysis reaction is difficult to proceed, which is not preferable.

Next, as the organic solvent used in the gas barrier composition according to the present invention, ethyl alcohol, isopropyl alcohol, butyl alcohol, or the like is used.
The amount of the solvent used is usually 30 to 100 parts by weight per 100 parts by weight of the total amount of the alkoxysilane, metal alkoxide, silane coupling agent, polyvinyl alcohol resin, acid and sol-gel method catalyst. is there.

According to the present invention, the gas barrier coating film of the present invention is formed, for example, as follows.
First, a coating solution is prepared by mixing the above alkoxysilane, silane coupling agent, polyvinyl alcohol resin, sol-gel method catalyst, acid, water, organic solvent, and, if necessary, metal alkoxide. To do.
In this coating solution, the polycondensation reaction gradually proceeds.
Next, the above-mentioned coating liquid is applied by a conventional method on the vapor-deposited layer made of an inorganic oxide provided on the above-mentioned base film and dried.
By the above drying, the polycondensation of the above alkoxysilane, metal alkoxide, silane coupling agent and polyvinyl alcohol resin further proceeds, and a gas barrier coating film is formed.
In the present invention, preferably, the above operation is repeated to laminate a plurality of gas barrier coating films.
Finally, the substrate film obtained by applying the coating liquid on the vapor deposition layer made of an inorganic oxide is at a temperature of about 120 ° C. or higher and below the melting point of the substrate film, preferably 150 to 200 ° C. When heated for 30 seconds to 10 minutes at a temperature within the range, the gas barrier coating film of the present invention is obtained. The gas barrier coating film of the present invention thus obtained is excellent in gas barrier properties for preventing and blocking the permeation of oxygen gas, water vapor and the like.
Thus, the barrier film in which the one or several gas barrier coating film was formed is acetalized as needed.
For example, specifically, when this barrier film is immersed in an aldehyde solution containing an acid, an acetalization treatment using formaldehyde, acetaldehyde, butyraldehyde or the like as the aldehyde is performed, so that a trace amount in the gas barrier coating film. The unreacted hydroxyl group resulting from the existing polyvinyl alcohol resin reacts with the aldehyde to be acetalized, thereby further improving the water resistance (moisture resistance) of the gas barrier coating film.

In the method of the present invention, the alkoxysilane and the metal alkoxide are hydrolyzed by the added water, and then protons are taken from the generated hydroxyl groups by the action of the sol-gel method catalyst, and the hydrolysis products are dehydrated. At the same time, the silane coupling agent is hydrolyzed and the alkoxy group becomes a hydroxyl group. Further, the opening of the epoxy group also occurs due to the action of the catalyst, resulting in a hydroxyl group, and thus hydrolyzed. A polycondensation reaction between the silane coupling agent and the hydrolyzed alkoxide also proceeds.
Furthermore, since a polyvinyl alcohol resin is present in the reaction system, a reaction with the hydroxyl group of the polyvinyl alcohol resin also occurs, and the resulting polycondensates are Si—O—Si, Si—O—Zr. A gas barrier coating film made of a composite polymer containing an inorganic part composed of a bond such as Si—O—Ti and an organic part derived from a silane coupling agent can be formed.
In the above reaction, for example, a linear polymer having a partial structural formula represented by the following formula (II) and further having a portion derived from a silane coupling agent is first produced. The OR group (alkoxy group such as ethoxy group) is branched from a linear polymer.
This OR group is hydrolyzed to become an OH group using an existing acid as a catalyst, and this undergoes a polycondensation reaction with a polyvinyl alcohol resin represented by the following formula (I) to form a Si—O—Si bond. It is considered that a composite polymer represented by the following formula (III) is produced.
In the above polycondensation reaction, it is considered that the OH group is first deprotonated and then polycondensation proceeds by the action of the sol-gel method catalyst (base catalyst).

The above reaction proceeds at room temperature, the viscosity of the coating solution increases during preparation, and this coating solution is applied onto a vapor deposition layer made of an inorganic oxide provided on a base film and heated. When the solvent and the alcohol produced by the polycondensation reaction are removed, the polycondensation reaction is completed, and a transparent gas barrier coating film is formed on the vapor deposition layer made of an inorganic oxide provided on the base film. .
When a plurality of gas barrier coating films are laminated, the gas barrier coating films between the layers are condensed with each other, the layers are firmly bonded, and the organic reactive groups of the silane coupling agent and In addition, since the hydroxyl group generated by hydrolysis binds to the hydroxyl group of the vapor deposition layer made of inorganic oxide provided on the base film, the adhesion between the vapor deposition layer made of inorganic oxide and the gas barrier coating film is also good. .

In the present invention, the amount of water added is adjusted to 0.8 mol to 2 mol, preferably 1.5 mol, with respect to 1 mol of alkoxides. Is formed.
Thus, such a gas barrier coating film has crystallinity and has a structure in which a large number of minute crystals are embedded in an amorphous part. Similar to polymers (for example, polyvinylidene chloride and polyvinyl alcohol resins), and polar groups (OH groups) are partially present in the molecule, resulting in high molecular cohesive energy and high molecular chain rigidity. It is believed to exhibit good gas barrier properties.
The Si—O—CH bond represented by the above formula (III) is the same as a stable bond formed by acetylation or formalization of a polyvinyl alcohol-based resin.
The barrier film thus obtained is excellent in water resistance, but the water resistance is further improved by further acetalizing treatment as described above.
In the present invention, the film thickness of the gas barrier coating film is preferably in the range of 0.1 to 10 μm (dry state).

As described above, the barrier film according to the present invention includes a polyacrylic or polymethacrylic resin having two or more hydroxyl groups in the structure and a curing agent on one surface of the base film. An anchor coating agent layer made of a resin composition is provided, and then a deposition layer made of an inorganic oxide is provided on the anchor coating agent layer, and further, a deposition layer made of the inorganic oxide is formed. In addition, if necessary, gas barrier properties by a gas barrier composition obtained by polycondensation by a sol-gel method containing an alkoxysilane, a silane coupling agent, and a water-soluble resin through a plasma-treated surface with oxygen gas. The present invention relates to a barrier film characterized by providing a coating film.
Thus, the barrier film according to the present invention has a good tight adhesion between the base film and the vapor-deposited layer made of an inorganic oxide, and further stably maintains a high gas barrier property and has a good transparency. It is extremely useful as a gas barrier material comprising a packaging bag, etc., and has, for example, a heat-sealable resin layer, an intermediate group, and the like. Materials, plastic base materials, etc. are arbitrarily laminated to produce laminated materials as packaging materials consisting of various layers, and then used to form bags and packaging in various forms Bags and packaging products can be manufactured.

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 substrate constituting the laminated material according to the present invention, this is the basic or auxiliary material constituting the packaging bag according to the present invention, as with the aforementioned base film. From mechanical properties, physical properties, chemical properties, etc., excellent strength, excellent strength, heat resistance, moisture resistance, pinhole resistance, puncture resistance, transparency, etc. 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 or 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, for example, 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 A film or sheet of a tough resin such as a resin or the like can be used.
In the above, as the resin film or sheet, any of an unstretched film or a stretched film stretched in a uniaxial direction or a biaxial direction can be used.
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 the 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.
Furthermore, in the present invention, the film or sheet may be a film having any property such as extrusion film formation, inflation film formation, and coating film.

In 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 base 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 adhesives, ethyl butyl acrylate, 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 adhesives, reactive (meth) acrylic adhesives, chloroprene rubber, nitrile rubber, rubber adhesives made of styrene-butadiene rubber, silicone adhesives, alkali metal silicates, inorganics made of low melting 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 coating film each have transparency and barrier properties that prevent permeation of oxygen gas, water vapor, and the like. , Thereby exhibiting operational effects such as barrier properties that prevent the permeation of oxygen gas, water vapor, etc., and ultimately exhibiting operational effects such as barrier properties due to their synergistic effects, such as aluminum foil Unlike metal foil such as aluminum foil, it has excellent transparency and excellent visibility of contents, etc. This makes it possible to perform a metal detection test using a machine.
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). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as the base film.
First, weigh 5 parts by weight of acrylic polyol resin with respect to 1 part by weight of nitrified cotton in a 1: 1 dilution solvent of methyl ethyl ketone (MEK) / ethyl acetate, and add both of them together. The main agent A was obtained by stirring.
Next, as a curing agent, isophorone diisocyanate (IPDI) was added to the OH group of the main agent A so that the NCO group was equivalent to 2%, and the anchor coating agent was diluted by 2%. Obtained.
Next, the above-mentioned anchor coating agent was used, and this was coated on the corona-treated surface of the above biaxially stretched polyethylene terephthalate film having a thickness of 12 μm by using a gravure roll coating method. Then, after aging, an aging treatment was performed at 40 ° C. for 48 hours to form an anchor coating agent layer having a film thickness of 0.3 g / m ² (dry state).
(2). Next, the 12 μm thick biaxially stretched polyethylene terephthalate film in which the anchor coating agent layer is formed in the above (1) is used, and this is mounted on the take-up roll of the take-up type vacuum deposition apparatus. Then, this is fed out, and an electron beam (EB) heating is performed while supplying oxygen gas to the surface of the anchor coating agent layer of the biaxially stretched polyethylene terephthalate film using aluminum as a deposition source. A 20 nm-thick aluminum oxide vapor deposition film was formed by the following vacuum deposition method under the following vapor deposition conditions.
(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.
(3). On the other hand, 25 g of ethyl silicate, 25 g of ethanol, 1.86 g of 2N hydrochloric acid and 1.51 g of water were mixed and stirred at 80 ° C. for 2 hours, and then γ-glycidoxypropyltrimethoxysilane (epoxysilane, east Redou Corning Co., Ltd., trade name, SH6040) 2.5 g was added and stirred, and 17.4 g of an aqueous solution containing 10% polyvinyl alcohol resin (manufactured by Kuraray Co., Ltd., degree of polymerization, 2000) was added thereto, When the mixture became transparent after stirring for 2 hours, 0.1 g of an N, N-dimethylbenzylamine 32 wt% ethanol solution was added and further stirred to prepare a gas barrier composition as a coating solution.
Next, using the gas barrier composition produced above on the plasma treated surface with oxygen gas formed in (2) above, this is coated by the gravure roll coating method, and then at 150 ° C. for 1 minute. Heat treatment was performed to form a gas barrier coating film having a thickness of 0.4 μm (in a dry operation state) to produce a barrier film according to the present invention.
(4). Next, after forming a desired printed pattern on the surface of the gas barrier coating film of the barrier film produced in the above (3), a two-component curable polyurethane laminating film is formed on the entire surface including the printed 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 On the surface of the agent layer, a low-density polyethylene film having a thickness of 60 μm was laminated by dry lamination to produce a laminated material according to the present invention.
Next, two sheets of the laminated material produced as described above are prepared, the surfaces of the low density polyethylene film are opposed to each other, and then, the end portion around the outer periphery 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.
The three-side seal type soft packaging bag manufactured above is filled and packaged with 200 cc of water from the opening, and then the opening is heat sealed to form the upper seal. Then, the packaged semi-finished product was then boiled under the boil treatment conditions consisting of 60 minutes at a temperature of 95 ° C. to produce the boiled packaged food according to the present invention.
The boiled packaged food produced above has excellent heat resistance, pressure resistance, water resistance, barrier properties, heat seal properties, pin hole resistance, piercing properties, transparency, etc. Furthermore, it has excellent barrier properties against oxygen gas, water vapor, etc., no bag breakage or leakage of contents, etc., and functions as a food container, for example, filling and packaging suitability, distribution suitability, storage suitability, etc. It was. (5). Next, after forming a desired printed pattern on the surface of the gas barrier coating film of the barrier film produced in the above (3), a two-component curable polyurethane laminating film is formed on the entire surface including the printed 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 used for the lamination A biaxially stretched nylon 6 film having a thickness of 15 μm was laminated on the surface of the adhesive 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.
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.
The three-side seal type soft packaging bag manufactured above is filled and packaged with 200 cc of water from the opening, and then the opening is heat sealed to form the upper seal. Then, the packaged semi-finished product is manufactured, and then the packaged semi-finished product is put into a retort kettle and subjected to retort treatment under conditions of temperature, 135 ° C., pressure, 2.1 kgf / cm ² · G, time, 60 minutes. The retort packaged food according to the present invention was manufactured.
The retort packaged food manufactured above has excellent heat resistance, pressure resistance, water resistance, barrier properties, heat seal properties, pin hole resistance, piercing properties, transparency, etc. Excellent barrier properties against oxygen gas, water vapor, etc., with no bag breakage or leakage of contents, etc., and functions as a food container, such as content filling and packaging suitability, distribution suitability, storage suitability, etc. .

(1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as the base film.
First, 1 part by weight of γ-isocyanatopropyltrimethoxysilane and 10 parts by weight of acrylic polyol resin were weighed and added to a dilute solvent of methyl ethyl ketone (MEK) / ethyl acetate 1: 1. The main component A was obtained by mixing and stirring.
Next, as a curing agent, a mixed solution in which isophorone diisocyanate (IPDI) is added so that the NCO group is equivalent to the OH group of the main agent A is diluted by 3%, and the anchor coating agent is added. Obtained.
Next, the above-mentioned anchor coating agent was used, and this was coated on the corona-treated surface of the above biaxially stretched polyethylene terephthalate film having a thickness of 12 μm by using a gravure roll coating method. The film was then dried and then subjected to an aging treatment at 40 ° C. for 48 hours to form an anchor coating agent layer having a film thickness of 0.2 g / m ² (dry state).
(2). Next, the 12 μm thick biaxially stretched polyethylene terephthalate film in which the anchor coating agent layer is formed in the above (1) is used, and this is mounted on the take-up roll of the take-up type vacuum deposition apparatus. Then, this is fed out, and an electron beam (EB) heating is performed while supplying oxygen gas to the surface of the anchor coating agent layer of the biaxially stretched polyethylene terephthalate film using aluminum as a deposition source. A 15 nm-thick aluminum oxide vapor deposition film was formed under the following vapor deposition conditions by the vacuum vapor deposition method.
(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.
(3). On the other hand, 25 g of ethyl silicate, 25 g of ethanol, 1.86 g of 2N hydrochloric acid and 1.51 g of water were mixed and stirred at 80 ° C. for 2 hours, and then γ-glycidoxypropyltrimethoxysilane (epoxysilane, east Redou Corning Co., Ltd., trade name, SH6040) 2.5 g was added and stirred, and 17.4 g of an aqueous solution containing 10% polyvinyl alcohol resin (manufactured by Kuraray Co., Ltd., degree of polymerization, 2000) was added thereto, When the mixture became transparent after stirring for 2 hours, 0.1 g of an N, N-dimethylbenzylamine 32 wt% ethanol solution was added and further stirred to prepare a gas barrier composition as a coating solution.
Next, using the gas barrier composition produced above on the plasma treated surface with oxygen gas formed in (2) above, this is coated by the gravure roll coating method, and then at 150 ° C. for 1 minute. Heat treatment was performed to form a gas barrier coating film having a thickness of 0.4 μm (in a dry operation state) to produce a barrier film according to the present invention.
(4). Next, after forming a desired printed pattern on the surface of the gas barrier coating film of the barrier film produced in the above (3), a two-component curable polyurethane laminating film is formed on the entire surface including the printed 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 On the surface of the agent layer, a low-density polyethylene film having a thickness of 60 μm was laminated by dry lamination to produce a laminated material according to the present invention.
Next, two sheets of the laminated material produced as described above are prepared, the surfaces of the low density polyethylene film are opposed to each other, and then, the end portion around the outer periphery 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.
The three-side seal type soft packaging bag manufactured above is filled and packaged with 200 cc of water from the opening, and then the opening is heat sealed to form the upper seal. Then, the packaged semi-finished product was then boiled under the boil treatment conditions consisting of 60 minutes at a temperature of 95 ° C. to produce the boiled packaged food according to the present invention.
The boiled packaged food produced above has excellent heat resistance, pressure resistance, water resistance, barrier properties, heat seal properties, pin hole resistance, piercing properties, transparency, etc. Furthermore, it has excellent barrier properties against oxygen gas, water vapor, etc., no bag breakage or leakage of contents, etc., and functions as a food container, for example, filling and packaging suitability, distribution suitability, storage suitability, etc. It was. (5). Next, after forming a desired printed pattern on the surface of the gas barrier coating film of the barrier film produced in the above (3), a two-component curable polyurethane laminating film is formed on the entire surface including the printed 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 used for the lamination A biaxially stretched nylon 6 film having a thickness of 15 μm was laminated on the surface of the adhesive 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.
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.
The three-side seal type soft packaging bag manufactured above is filled and packaged with 200 cc of water from the opening, and then the opening is heat sealed to form the upper seal. Then, the packaged semi-finished product is manufactured, and then the packaged semi-finished product is put into a retort kettle and subjected to retort treatment under conditions of temperature, 135 ° C., pressure, 2.1 kgf / cm ² · G, time, 60 minutes. The retort packaged food according to the present invention was manufactured.
The retort packaged food manufactured above has excellent heat resistance, pressure resistance, water resistance, barrier properties, heat seal properties, pin hole resistance, piercing properties, transparency, etc. Excellent barrier properties against oxygen gas, water vapor, etc., with no bag breakage or leakage of contents, etc., and functions as a food container, such as content filling and packaging suitability, distribution suitability, storage suitability, etc. .

(1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as the base film.
First, weigh 5 parts by weight of acrylic polyol resin with respect to 1 part by weight of nitrified cotton in a 1: 1 dilution solvent of methyl ethyl ketone (MEK) / ethyl acetate, and add both of them together. The main agent A was obtained by stirring.
Next, as a curing agent, isophorone diisocyanate (IPDI) was added to the OH group of the main agent A so that the NCO group was equivalent to 2%, and the anchor coating agent was diluted by 2%. Obtained.
Next, the above-mentioned anchor coating agent was used, and this was coated on the corona-treated surface of the above-mentioned biaxially stretched polyethylene terephthalate film having a thickness of 12 μm using a gravure roll coating method. Then, after aging, an aging treatment was carried out at 40 ° C. for 48 hours to form an anchor coating agent layer having a film thickness of 0.3 g / m ² (dry state).
(2). Next, the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm in which the anchor coating agent layer was formed in the above (1) was used, and this was mounted on the delivery roll of the plasma chemical vapor deposition apparatus, This was drawn out, and a 10 nm-thick silicon oxide vapor deposition film was formed on the surface of the anchor coating agent layer of the biaxially stretched polyethylene terephthalate film 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.
(3). On the other hand, 25 g of ethyl silicate, 25 g of ethanol, 1.86 g of 2N hydrochloric acid and 1.51 g of water were mixed and stirred at 80 ° C. for 2 hours, and then γ-glycidoxypropyltrimethoxysilane (epoxysilane, east Redou Corning Co., Ltd., trade name, SH6040) 2.5 g was added and stirred, and 17.4 g of an aqueous solution containing 10% polyvinyl alcohol resin (manufactured by Kuraray Co., Ltd., degree of polymerization, 2000) was added thereto, When the mixture became transparent after stirring for 2 hours, 0.1 g of an N, N-dimethylbenzylamine 32 wt% ethanol solution was added and further stirred to prepare a gas barrier composition as a coating solution.
Next, using the gas barrier composition produced above on the plasma treated surface with oxygen gas formed in (2) above, this is coated by the gravure roll coating method, and then at 150 ° C. for 1 minute. Heat treatment was performed to form a gas barrier coating film having a thickness of 0.4 μm (in a dry operation state) to produce a barrier film according to the present invention.
(4). Next, after forming a desired printed pattern on the surface of the gas barrier coating film of the barrier film produced in the above (3), a two-component curable polyurethane laminating film is formed on the entire surface including the printed 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 On the surface of the agent layer, a low-density polyethylene film having a thickness of 60 μm was laminated by dry lamination to produce a laminated material according to the present invention.
Next, two sheets of the laminated material produced as described above are prepared, the surfaces of the low density polyethylene film are opposed to each other, and then, the end portion around the outer periphery 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.
The three-side seal type soft packaging bag manufactured above is filled and packaged with 200 cc of water from the opening, and then the opening is heat sealed to form the upper seal. Then, the packaged semi-finished product was then boiled under the boil treatment conditions consisting of 60 minutes at a temperature of 95 ° C. to produce the boiled packaged food according to the present invention.
The boiled packaged food produced above has excellent heat resistance, pressure resistance, water resistance, barrier properties, heat seal properties, pin hole resistance, piercing properties, transparency, etc. Furthermore, it has excellent barrier properties against oxygen gas, water vapor, etc., no bag breakage or leakage of contents, etc., and functions as a food container, for example, filling and packaging suitability, distribution suitability, storage suitability, etc. It was. (5). Next, after forming a desired printed pattern on the surface of the gas barrier coating film of the barrier film produced in the above (3), a two-component curable polyurethane laminating film is formed on the entire surface including the printed 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 used for the lamination A biaxially stretched nylon 6 film having a thickness of 15 μm was laminated on the surface of the adhesive 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.
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 manufactured above, 200 cc of water is filled and packaged from the opening, and then the opening is heat sealed to form an upper seal. Then, the packaged semi-finished product is manufactured, and then the packaged semi-finished product is put into a retort kettle and subjected to retort treatment under conditions of temperature, 135 ° C., pressure, 2.1 kgf / cm ² · G, time, 60 minutes. The retort packaged food according to the present invention was manufactured.
The retort packaged food manufactured above has excellent heat resistance, pressure resistance, water resistance, barrier properties, heat seal properties, pin hole resistance, piercing properties, transparency, etc. Excellent barrier properties against oxygen gas, water vapor, etc., with no bag breakage or leakage of contents, etc., and functions as a food container, such as content filling and packaging suitability, distribution suitability, storage suitability, etc. .

(1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as the base film.
First, 1 part by weight of γ-isocyanatopropyltrimethoxysilane and 10 parts by weight of acrylic polyol resin were weighed and added to a dilute solvent of methyl ethyl ketone (MEK) / ethyl acetate 1: 1. The main component A was obtained by mixing and stirring.
Next, as a curing agent, a mixed solution in which isophorone diisocyanate (IPDI) is added so that the NCO group is equivalent to the OH group of the main agent A is diluted by 3%, and the anchor coating agent is added. Obtained.
Next, the above-mentioned anchor coating agent was used, and this was coated on the corona-treated surface of the above biaxially stretched polyethylene terephthalate film having a thickness of 12 μm by using a gravure roll coating method. The film was then dried and then subjected to an aging treatment at 40 ° C. for 48 hours to form an anchor coating agent layer having a film thickness of 0.2 g / m ² (dry state).
(2). Next, the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm in which the anchor coating agent layer was formed in the above (1) was used, and this was mounted on the delivery roll of the plasma chemical vapor deposition apparatus, This was drawn out, and a 10 nm-thick silicon oxide vapor deposition film was formed on the surface of the anchor coating agent layer of the biaxially stretched polyethylene terephthalate film 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.
(3). On the other hand, 25 g of ethyl silicate, 25 g of ethanol, 1.86 g of 2N hydrochloric acid and 1.51 g of water were mixed and stirred at 80 ° C. for 2 hours, and then γ-glycidoxypropyltrimethoxysilane (epoxysilane, east Redou Corning Co., Ltd., trade name, SH6040) 2.5 g was added and stirred, and 17.4 g of an aqueous solution containing 10% polyvinyl alcohol resin (manufactured by Kuraray Co., Ltd., degree of polymerization, 2000) was added thereto, When the mixture became transparent after stirring for 2 hours, 0.1 g of an N, N-dimethylbenzylamine 32 wt% ethanol solution was added and further stirred to prepare a gas barrier composition as a coating solution.
Next, using the gas barrier composition produced above on the plasma treated surface with oxygen gas formed in (2) above, this is coated by the gravure roll coating method, and then at 150 ° C. for 1 minute. Heat treatment was performed to form a gas barrier coating film having a thickness of 0.4 μm (in a dry operation state) to produce a barrier film according to the present invention.
(4). Next, after forming a desired printed pattern on the surface of the gas barrier coating film of the barrier film produced in the above (3), a two-component curable polyurethane laminating film is formed on the entire surface including the printed 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 On the surface of the agent layer, a low-density polyethylene film having a thickness of 60 μm was laminated by dry lamination to produce a laminated material according to the present invention.
Next, two sheets of the laminated material produced as described above are prepared, the surfaces of the low density polyethylene film are opposed to each other, and then, the end portion around the outer periphery 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.
The three-side seal type soft packaging bag manufactured above is filled and packaged with 200 cc of water from the opening, and then the opening is heat sealed to form the upper seal. Then, the packaged semi-finished product was then boiled under the boil treatment conditions consisting of 60 minutes at a temperature of 95 ° C. to produce the boiled packaged food according to the present invention.
The boiled packaged food produced above has excellent heat resistance, pressure resistance, water resistance, barrier properties, heat seal properties, pin hole resistance, piercing properties, transparency, etc. Furthermore, it has excellent barrier properties against oxygen gas, water vapor, etc., no bag breakage or leakage of contents, etc., and functions as a food container, for example, filling and packaging suitability, distribution suitability, storage suitability, etc. It was. (5). Next, after forming a desired printed pattern on the surface of the gas barrier coating film of the barrier film produced in the above (3), a two-component curable polyurethane laminating film is formed on the entire surface including the printed 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 used for the lamination A biaxially stretched nylon 6 film having a thickness of 15 μm was laminated on the surface of the adhesive 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.
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 manufactured above, 200 cc of water is filled and packaged from the opening, and then the opening is heat sealed to form an upper seal. The packaged semi-finished product is then manufactured, and then the packaged semi-finished product is put into a retort kettle and subjected to retort treatment under conditions of retort treatment consisting of temperature, 135 ° C., pressure, 2.1 kgf / cm ² · G, time, 60 minutes. The retort packaged food according to the present invention was manufactured.
The retort packaged food manufactured above has excellent heat resistance, pressure resistance, water resistance, barrier properties, heat seal properties, pin hole resistance, piercing properties, transparency, etc. Excellent barrier properties against oxygen gas, water vapor, etc., with no bag breakage or leakage of contents, etc., and functions as a food container, such as content filling and packaging suitability, distribution suitability, storage suitability, etc. .

[Comparative Example 1]
(1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as a base film, and this was mounted on a feed roll of a wind-up type vacuum evaporation apparatus, and then fed out, and the biaxially stretched polyethylene terephthalate film was fed. An oxidation film having a film thickness of 20 nm is formed on the corona-treated surface of the turret film by a vacuum deposition method using an electron beam (EB) heating method while supplying oxygen gas using aluminum as a deposition source under the following deposition conditions. An aluminum deposited film 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, 25 g of ethyl silicate, 25 g of ethanol, 1.86 g of 2N hydrochloric acid and 1.51 g of water were mixed and stirred at 80 ° C. for 2 hours, and then γ-glycidoxypropyltrimethoxysilane (epoxysilane, east Redou Corning Co., Ltd., trade name, SH6040) 2.5 g was added and stirred, and 17.4 g of an aqueous solution containing 10% polyvinyl alcohol resin (manufactured by Kuraray Co., Ltd., degree of polymerization, 2000) was added thereto, When the mixture became transparent after stirring for 2 hours, 0.1 g of an N, N-dimethylbenzylamine 32 wt% ethanol solution was added and further stirred to prepare a gas barrier composition as a coating solution.
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 150 ° C. for 1 minute. Heat treatment was performed to form a gas barrier coating film having a thickness of 0.4 μm (in a dry operation state) to produce a barrier film.
(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 On the surface of the agent layer, a low-density polyethylene film having a thickness of 60 μm was laminated by dry lamination to produce a laminated material.
Next, two sheets of the laminated material produced as described above are prepared, the surfaces of the low density polyethylene film are opposed to each other, and then, the end portion around the outer periphery 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 manufactured above, 200 cc of water is filled and packaged from the opening, and then the opening is heat sealed to form an upper seal. Then, the packaged semi-finished product was manufactured, and then the packaged semi-finished product was boiled at a temperature of 95 ° C. for 60 minutes under a boil treatment condition to produce a boiled packaged food.
(4). 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 used for the lamination A biaxially stretched nylon 6 film having a thickness of 15 μm was laminated on the surface of the adhesive 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 A laminated material was produced by dry laminating and laminating an unstretched polypropylene film having a thickness of 60 μm on the surface of the adhesive layer for laminating.
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.
The three-side seal type soft packaging bag manufactured above is filled and packaged with 200 cc of water from the opening, and then the opening is heat sealed to form the upper seal. Then, the packaged semi-finished product is manufactured, and then the packaged semi-finished product is put into a retort kettle and subjected to retort treatment under conditions of temperature, 135 ° C., pressure, 2.1 kgf / cm ² · G, time, 60 minutes. To produce a retort packaged food.

[Comparative Example 2]
(1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as a base film, and this was mounted on a delivery roll of a plasma chemical vapor deposition apparatus, and then fed out, and the biaxially stretched polyethylene terephthalate film. A silicon oxide vapor deposition film having a thickness of 10 nm was formed on the surface of the corona-treated surface under the vapor deposition conditions shown below.
(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, 25 g of ethyl silicate, 25 g of ethanol, 1.86 g of 2N hydrochloric acid and 1.51 g of water were mixed and stirred at 80 ° C. for 2 hours, and then γ-glycidoxypropyltrimethoxysilane (epoxysilane, east Redou Corning Co., Ltd., trade name, SH6040) 2.5 g was added and stirred, and 17.4 g of an aqueous solution containing 10% polyvinyl alcohol resin (manufactured by Kuraray Co., Ltd., degree of polymerization, 2000) was added thereto, When the mixture became transparent after stirring for 2 hours, 0.1 g of an N, N-dimethylbenzylamine 32 wt% ethanol solution was added and further stirred to prepare a gas barrier composition as a coating solution.
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 150 ° C. for 1 minute. Heat treatment was performed to form a gas barrier coating film having a thickness of 0.4 μm (in a dry operation state) to produce a barrier film.
(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 On the surface of the agent layer, a low-density polyethylene film having a thickness of 60 μm was laminated by dry lamination to produce a laminated material.
Next, two sheets of the laminated material produced as described above are prepared, the surfaces of the low density polyethylene film are opposed to each other, and then, the end portion around the outer periphery 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 manufactured above, 200 cc of water is filled and packaged from the opening, and then the opening is heat sealed to form an upper seal. Then, the packaged semi-finished product was manufactured, and then the packaged semi-finished product was boiled at a temperature of 95 ° C. for 60 minutes under a boil treatment condition to produce a boiled packaged food.
(4). 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 used for the lamination A biaxially stretched nylon 6 film having a thickness of 15 μm was laminated on the surface of the adhesive 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 A laminated material was produced by dry laminating and laminating an unstretched polypropylene film having a thickness of 60 μm on the surface of the adhesive layer for laminating.
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.
The three-side seal type soft packaging bag manufactured above is filled and packaged with 200 cc of water from the opening, and then the opening is heat sealed to form the upper seal. Then, the packaged semi-finished product is manufactured, and then the packaged semi-finished product is put into a retort kettle and subjected to retort treatment under conditions of temperature, 135 ° C., pressure, 2.1 kgf / cm ² · G, time, 60 minutes. To produce a retort packaged food.

[Experimental Example 1]
About the packaging bag manufactured by bag-making the laminated material manufactured using the barrier film manufactured in Examples 1 to 4 and Comparative Examples 1 and 2, before and after the boil treatment and before and after the retort treatment Oxygen permeability and laminating strength (peeling strength) were measured and evaluated, and the appearance after the boil treatment and after the retort treatment was 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 Laminate Strength (Peeling Strength) Laminate strength was measured using a Tensilon measuring instrument under the conditions of a test piece 15 mm wide, T-shaped peeling, and a peeling speed of 50 mm / min.
In addition, about the interface at the time of peeling, it estimated from the amount of Al detection obtained by a fluorescent X ray analysis method. (3). Appearance evaluation In Examples 1 and 2 and Comparative Examples 1 and 2 above, instead of filling and packaging 200 cc of water in a pouch, 100 cc of water was packed in the pouch, and then the pouch was ruled. Then, it is bent at 180 ° and fixed with a clip. Then, boil treatment and retort treatment are carried out under the same conditions as above, and then visually confirmed for occurrence of delamination. When the delamination occurred, the appearance was evaluated as x, and when the delamination did not occur, ◎.
The measurement results are shown in Tables 1 and 2 below.

(Table 1) Evaluation results of boil treatment ┌────┬───────────┬───────────┐ │ │ Oxygen permeability │ Laminate strength │ │ ├─────┬─────┼─────┬─────┤ │ │ Before boil │ After boil │ Before boil │ After boil │ ├────┼──── ─┼─────┼─────┼─────┤ │Example 1│0.38 │0.41 │ 390 │ 370 │ ├────┼─────┼── ────┼─────┼ ─────┤ │Example 2│0.45 │0.53 │ 420 │ 415 │ ├────┼─────┼──── ─┼─────┼─────┤ │Example 3│0.43 │0.46 │ 460 │ 440 │ ├────┼─────┼─────┼── ────┼─────┤ │Example 4│0.47 │0.51 │ 48 │ 470 │ ├────┼─────┼─────┼─────┼─────┤ │Comparative Example 1│0.39 │1.69 │ 120 │ 90 │ ├────┼─────┼─────┼─────┼─────┤ │Comparative Example 2│0.44 │1.13 │ 180 │ 120 │ └── ──┴─────┴─────┴─────┴┴─────┘
┌────┬────────┬──┐ │ │ Peeling interface │Appearance│ ├────┼────────┼──┤ │Example 1 │AlO _X Aggregation │ ◎ │ ├────┼────────┼──┤ │Example 2│AlO _X Aggregation │ ◎ │ ├────┼────────┼── │ │Example 3 │SiO _X aggregation │ ◎ │ ├────┼────────┼──┤ │Example 4 │SiO _X aggregation │ ◎ │ ├────┼─── ─────┼──┤ │Comparative Example 1│PET / AlO _X │ × │ ├────┼────────┼──┤ │Comparative Example 2│PET / SiO _X │ × │ └────┴────────┴──┘

(Table 2) Evaluation results of retort treatment ┌────┬───────────┬───────────┐ │ │ Oxygen permeability │ Laminate strength │ │ ├─────┬─────┼─────┬─────┤ │ │Before retort │After retort │Before retort │After retort │ ├────┼──── ─┼─────┼─────┼─────┤ │Example 1│0.30 │0.96 │Out of base material │Out of base material │ ├────┼─── ──┼─────┼─────┼─────┤ │Example 2│0.34 │1.13 │Out of base material │Out of base material │ ├────┼── ───┼─────┼─────┼─────┤ │Example 3│0.32 │0.88 │Out of base material │Out of base material │ ├────┼─ ────┼─────┼─────┼─────┤ │Example 4│0.37 │ 91 │ Out of base material │ Out of base material │ ├────┼─────┼─────┼─────┼─────┤ │Comparative Example 1│0.33 │ 1.56 │ 350 │ 100 │ ├────┼────┼┼─────┼─────┼─────┤ │Comparative Example 2│0.32 │2.13 │ 430 │ 80 │ └────┴─────┴─────┴─────┴─────┘
┌────┬────────┬──┐ │ │ Peeling interface │Appearance│ ├────┼────────┼──┤ │Example 1 │ ◎ │ ├────┼────────┼──┤ │Example 2│ Unmeasurable │ ◎ │ ├────┼────────┼──┤ │ Example 3 │ Measurement impossible │ ◎ │ ├────┼────────┼──┤ │ Example 4 │ Measurement impossible │ ◎ │ ├────┼──────── ─┼──┤ │Comparative Example 1│PET / AlO _X │ × │ ├────┼────────┼──┤ │Comparative Example 2│PET / SiO _X │ × │ └── ──┴────────┴──┘ In Tables 1 and 2 above, the unit of oxygen permeability is [cc / m ² / day / atm, 23 ° C, 90% RH] The unit of laminating strength (peeling strength) is [gf / 15 mm] It is.

  As is clear from the measurement results shown in Tables 1 and 2 above, it was confirmed that the samples according to Examples 1 to 4 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 a laminated material using the same, and a packaging bag made using the same are barrier properties that prevent permeation of oxygen gas, water vapor, and the like, and adhesion of the laminated material For example, it can withstand heat treatments associated with processing such as boil processing and retort processing, and further reduce the manufacturing cost by reducing the weight and weight of containers and packaging waste and shortening the manufacturing process. For example, it is useful for filling and packaging various foods and beverages such as cooked foods, fish paste products, frozen foods, boiled foods, rice cakes, liquid soups, seasonings, drinking water, etc. It has excellent aptitude 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 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 based on this invention which used the laminated material shown in FIG. It is a schematic perspective view which shows an example of the structure about the packaging bag based on this invention which used 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 Barrier film B, B ₁ , B ₂ Laminate C Packaging bag D Packaging product 1 Base film 2 Anchor coat layer 3 Vapor deposition layer made of inorganic oxide 4 Gas barrier coating film 11 Heat sheet Resin layer 12 Intermediate base material 13 Plastic base material 15 Heat seal part 16 Opening part 17 Contents 18 Upper seal part

Claims (12)

On one surface of the base film, an anchor coating agent layer is provided by a resin composition containing a polyacrylic or polymethacrylic resin having two or more hydroxyl groups in its structure and a curing agent, A deposition layer made of an inorganic oxide is provided on the anchor coating agent layer, and further, an alkoxysilane, a silane coupling agent and a water-soluble resin are contained on the deposition layer made of the inorganic oxide. And a gas barrier coating film made of a gas barrier composition obtained by polycondensation by a sol-gel method. 2. The barrier film according to claim 1, wherein the base film comprises a biaxially stretched polyester resin film, a biaxially stretched polyamide resin film, or a biaxially stretched polyolefin resin film. The barrier film according to any one of claims 1 to 2, wherein the curing agent comprises an isocyanate compound. The barrier property according to any one of claims 1 to 3, wherein the resin composition contains one or more of a vinyl resin, an epoxy resin, a urethane resin, or a polyester resin. the film. The barrier layer according to any one of claims 1 to 4, wherein the vapor-deposited layer made of an inorganic oxide is made of a vapor-deposited film of an inorganic oxide by chemical vapor deposition or physical vapor deposition. Sex film. The barrier film according to any one of claims 1 to 5, wherein the vapor deposition layer made of an inorganic oxide comprises a vapor deposition film of aluminum oxide by physical vapor deposition. The vapor deposition layer made of an inorganic oxide is a vapor deposition film of silicon oxide by a physical vapor deposition method using a mixture of silicon monoxide and silicon as a raw material. The barrier film described in the item. The barrier film according to any one of claims 1 to 5, wherein the vapor deposition layer made of an inorganic oxide is a vapor deposition film of silicon oxide by a chemical vapor deposition method. The barrier film according to any one of claims 1 to 8, wherein the vapor-deposited layer made of an inorganic oxide is previously provided with a plasma-treated surface with oxygen gas on the surface thereof. On one surface of the base film, an anchor coating agent layer is provided by a resin composition containing a polyacrylic or polymethacrylic resin having two or more hydroxyl groups in its structure and a curing agent, A deposition layer made of an inorganic oxide is provided on the anchor coating agent layer, and further, an alkoxysilane, a silane coupling agent and a water-soluble resin are contained on the deposition layer made of the inorganic oxide. In addition, a barrier film comprising a gas barrier coating film comprising a gas barrier composition obtained by polycondensation by a sol-gel method is used, and a heat-seal resin is provided on the surface of the gas barrier coating film. A laminated material characterized by laminating layers. The laminated material according to claim 10, wherein a plastic substrate is laminated on the other surface of the substrate film. The laminated material according to any one of claims 10 to 11, wherein an intermediate base material is laminated between the barrier film and the heat-seal resin layer.

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