JP4852822B2 - Barrier film and laminated material using the same - Google Patents

Description

  The present invention relates to a barrier film and a laminate 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 packed Barrier substrates of 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 in incineration and is easy to dispose after use, 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, water vapor, and the like made of polyvinylidene chloride resin, ethylene-vinyl alcohol copolymer, and the like. ing.
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 uses are developed in various fields, and the demand is expanding.
However, the barrier layer made of a thin film of an inorganic oxide such as silicon oxide or aluminum oxide is simply obtained by heating and vaporizing the inorganic oxide to deposit and deposit the particles on the base film. Therefore, there is a gap called a grain boundary between the inorganic oxide particles, and although it has excellent gas barrier properties, it cannot be said to have sufficiently satisfactory gas barrier properties. The fact is that there is.
For this reason, for example, an improvement proposal such as increasing the film thickness (500 to 1000 mm) or decreasing the oxygen atom ratio in the inorganic oxide thin film to improve the gas barrier property is proposed. However, on the other hand, for example, when the film thickness is increased, the transparency is lowered, and by increasing the film thickness, the thin film of the inorganic oxide is inferior in stretchability, spreadability, etc., and cracks etc. There are various problems such as being easy to occur and poor adhesion between the substrate film and the particles constituting the inorganic oxide thin film.

In order to solve the problems of the barrier substrate having a barrier layer made of an inorganic oxide thin film such as silicon oxide and aluminum oxide, and to improve the gas barrier performance, the above silicon oxide and aluminum oxide are used. Arco on the thin film of the inorganic oxide etc., for example, an alkoxysilane having R ₁ -Si group represented by the general formula II, and alkoxysilane having no R ₁ -Si group of the general formula III A hydrolysis product obtained by dissolving in an organic solvent and hydrolyzing with an acid catalyst (see, for example, Patent Document 1), a hydrolyzate of an Si alkoxide represented by Formula I, and Formula II And / or a mixture of hydrolysates of one or more metal alkoxides selected from Ti, Zr, and Al represented by the general formula III (see, for example, Patent Document 2), alkoxysilanes , A composition containing a silane coupling agent and boric acid (see, for example, Patent Document 3), a composition containing alkoxysilane, a silane coupling agent, and a polyvinyl alcohol (see, for example, Patent Document 4). Or a composition containing an alkoxysilane, a silane coupling agent and an ethylene-vinyl alcohol copolymer (see, for example, Patent Document 5) and drying to form a coating film thereof, Attempts have been made to produce various barrier substrates.
Specifically, for example, a vapor deposition layer made of an inorganic compound is used as a first layer on a base material made of a polymer resin composition, and a water-soluble polymer and (a) one or more alkoxides and / or water thereof are added. The second layer is a gas barrier coating formed by applying an aqueous solution containing at least one of decomposition products or (b) tin chloride, or a coating agent mainly composed of a water / alcohol mixed solution, followed by drying by heating. A gas barrier laminate film characterized by being laminated as described above has been proposed (see, for example, Patent Document 6).
In addition, a metal or metal oxide vapor-deposited layer is laminated on at least one surface of the resin molded body, and further, an organic compound having a primary and / or secondary amino group in the molecule and containing no Si (OR ¹ ) group. For surface treatment containing compound (A), compound (B) having a functional group capable of reacting with the amino group in the molecule, organometallic compound (C) and / or hydrolysis condensate thereof and solvent (D) A surface-treated resin molded body in which treatment films of the composition are laminated has been proposed (for example, see Patent Document 7).
JP-A-8-302043 (Claims etc.) Japanese Patent Laid-Open No. 10-244613 (claims, etc.) Japanese Patent No. 2971105 (claims, etc.) Japanese Patent No. 2556940 (Claims etc.) Japanese Patent No. 2880654 (Claims etc.) Japanese Patent No. 2790054 (claims, etc.) JP-A-8-295848 (claims)

However, in the barrier base material in which the coating film is formed by the composition according to Patent Documents 1 to 5, the gas barrier property against oxygen gas can be improved, but the barrier property against water vapor is insufficient. There is a problem that it is.
Also in the specific examples shown in the above Patent Documents 6 and 7, there is a tendency that the barrier property against water vapor is insufficient, and it cannot be said that it is sufficiently satisfactory.
Usually, a thin film of an inorganic oxide such as silicon oxide or aluminum oxide is provided on one surface of a base film made of a resin film such as a polyester resin, a polyamide resin, or a polypropylene resin by vacuum deposition or the like. Further, in the laminated material in which the heat-sealable resin layer is laminated on the surface of the inorganic oxide thin film via an adhesive layer or an anchor coating agent layer, the inorganic oxide thin film Is known to show a water vapor barrier property higher than the theoretical calculated value of the water vapor barrier property by the heat-sealable resin layer and the water vapor barrier property by the heat seal resin layer. The reason for the problem is not clear and is difficult to explain.
Therefore, in view of the circumstances as described above, the present invention improves the barrier property against water vapor as well as the gas barrier property against oxygen gas, and stably maintains the high gas barrier property against oxygen gas, water vapor, etc. An object of the present invention is to provide a barrier film having good transparency, impact resistance, hot water resistance, and the like, and a laminate using the same.

As a result of various studies to solve the above problems, the present inventor firstly has a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² have 1 to 8 carbon atoms). M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents the valence of M. It contains at least one alkoxide, a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer, and in the presence of a sol-gel catalyst, an acid, water, and an organic solvent, A gas barrier composition that undergoes polycondensation is prepared, and then an inorganic oxide vapor-deposited film is provided on one side of the base film or on one side of the base film, and then the inorganic oxidation is performed. Gas that is polycondensed by the sol-gel method on the surface of the deposited film The barrier composition is applied to provide a coating film, and then the base film provided with the coating film is at a temperature of 20 ° C. to 180 ° C. and below the melting point of the base film. The gas barrier composition is heated on the surface of the base film for 10 seconds to 10 minutes, or on the inorganic oxide vapor deposition film provided on the one side of the base film. 1 or more gas barrier coating films are formed on the surface of the gas barrier coating film formed of the gas barrier composition formed above, and a plasma gas composed of an inorganic gas containing oxygen gas in a vacuum. To form a plasma-treated surface, and a heat-sealable resin layer is laminated on the plasma-treated surface via an adhesive layer or an anchor coat agent layer, etc. And produced various laminated materials Not only the gas barrier property against oxygen gas but also the barrier property against water vapor is improved, and relatively high gas barrier property against oxygen gas, water vapor, etc. is stably maintained, and good transparency and impact resistance, The present invention has been completed by finding that a barrier film having hot water resistance and the like and a laminate using the film can be produced.

That is, the present invention provides a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M) and at least one alkoxide represented by , A polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer, and further provided with a gas barrier coating film by a gas barrier composition obtained by polycondensation by a sol-gel method. A barrier film characterized in that a plasma-treated surface by plasma treatment is provided on the surface of the conductive coating film, or an inorganic oxide vapor-deposited film is provided on one surface of the base film, and the inorganic oxide On the surface of the deposited film of general formula R ¹ _n M (OR ² ) _m (wherein, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M.), and a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer. A gas barrier coating film made of a gas barrier composition obtained by polycondensation by a sol-gel method, and a plasma treatment surface by plasma treatment is further provided on the surface of the gas barrier coating film. The present invention relates to a barrier film and a laminated material using them.

In the present invention described above, first, a plasma treatment surface is formed on the surface of the gas barrier coating film made of the gas barrier composition by using a plasma gas composed of an inorganic gas containing oxygen gas in a vacuum. Thus, Si—C bonds and the like existing in the gas barrier coating film by the gas barrier composition are converted into SiO ₂ , and thereby the crosslink density of the gas barrier coating film by the gas barrier composition and the like are reduced. To improve the humidity dependency, etc., gas barrier properties against oxygen gas as well as water vapor barrier properties, and relatively stably maintain high gas barrier properties against oxygen gas, water vapor, etc. It is possible.
In the present invention, the surface of the gas barrier coating film made of the gas barrier composition is subjected to plasma treatment using a plasma gas composed of an inorganic gas containing oxygen gas in a vacuum to form a plasma treatment surface. Thus, when a substrate such as a printed pattern layer, an adhesive layer, an anchor coating agent layer, a heat seal resin layer, or the like is laminated on the surface of the plasma treatment surface, It is possible to improve honey adhesion and the like and to remarkably increase the lamination strength and the like.
Furthermore, in the present invention, the gas barrier coating film itself of the gas barrier composition is extremely strong because the polyvinyl alcohol resin or ethylene / vinyl alcohol copolymer and one or more alkoxides chemically react with each other. A three-dimensional network composite polymer layer, which is synergistic with the vapor deposited film of inorganic oxide, stably maintaining extremely high gas barrier properties, and having good transparency and impact resistance A barrier film having hot water resistance can be produced.
In particular, in the present invention, when a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer are used in combination, the polyvinyl alcohol-based resin and at least one alkoxide, the ethylene / vinyl alcohol copolymer, and at least one or more types are used. An alkoxide, a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer, and one or more alkoxides are combined to form an extremely complex, hybrid, strong three-dimensional network composite polymer layer. Thus, they are synergistic with the inorganic oxide vapor deposition film to stably maintain an extremely high gas barrier property, as well as a barrier having good transparency, impact resistance, hot water resistance, and the like. It is possible to produce a conductive film.
Further, in the present invention, when two or more gas barrier coating films are stacked, in the same manner as described above, an inorganic oxide vapor deposition film and a composite polymer layer comprising two or more gas barrier coating films are used. Synergistically, stably maintaining extremely high gas barrier properties, and capable of producing a barrier film having good transparency, impact resistance, hot water resistance, and the like.

The barrier film according to the present invention and a laminate using the same will be described in more detail below with reference to the drawings.
1 and 2 are schematic cross-sectional views showing one example of the layer structure of the barrier film according to the present invention, and FIG. 3 is a book using the barrier film according to the present invention shown in FIG. FIG. 4 is a schematic cross-sectional view showing an example of the layer structure of the laminated material according to the invention, and FIG. 4 shows an example of the layer structure of the laminated material according to the present invention using the barrier film according to the present invention shown in FIG. It is a schematic sectional drawing which shows.

First, as shown in FIG. 1, the barrier film A according to the present invention has a general formula R ¹ _n M (OR ² ) _m (where R ¹ , R ² represents an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents the valence of M. Gas barrier properties obtained by polycondensation by a sol-gel method, containing at least one alkoxide represented by the formula (1)), a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. A gas barrier coating film 2 made of a composition is provided, and a structure in which a plasma treatment surface 3 by plasma treatment is further provided on the surface of the gas barrier coating film 2 is a basic structure.

Moreover, when another example is illustrated about the barrier film which concerns on this invention, as shown in FIG. 2, the vapor deposition film | membrane 4 of the inorganic oxide was provided in one surface of the base film 1, and also this inorganic oxide On the surface of the deposited film 4 of the general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, and M represents a metal atom) N represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M.), a polyvinyl alcohol resin, and at least one alkoxide represented by And / or an ethylene / vinyl alcohol copolymer, and further provided with a gas barrier coating film 2 made of a gas barrier composition obtained by polycondensation by a sol-gel method. Based on the configuration provided with plasma processing surface 3 by processing This structure is used.
The above exemplification illustrates one or two examples of the layer structure of the barrier film according to the present invention, and it goes without saying that the present invention is not limited thereto.
For example, although not shown, in the above-described barrier film according to the present invention, the inorganic oxide vapor-deposited film is of the same type or different type, and further is a composite film composed of an inorganic oxide vapor-deposited film having two or more layers. Can be configured as

Next, in the present invention, when the laminated material according to the present invention using the barrier film according to the present invention as described above is exemplified, the barrier film A according to the present invention shown in FIG. 1 is used. to illustrate, as shown in FIG. 3, on one surface of a substrate film 1, the general formula _{^{R 1 n M (OR 2)}} m ( where in the formula, R ^1, R ² is from 1 to 8 carbon atoms Represents an organic group, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents an atomic valence of M). A gas barrier coating film 2 comprising a gas barrier composition containing at least one kind of alkoxide, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and further obtained by polycondensation by a sol-gel method. Further, the gas barrier coating film 2 is provided. A printed pattern layer 5, a laminating adhesive layer 6, and a heat seal are formed on the surface of the plasma-treated surface 3 of the barrier film A having a structure in which a plasma-treated surface 3 by plasma treatment is provided on the surface. It is possible to manufacture the laminate B according to the present invention using the barrier film A according to the present invention by sequentially laminating the functional resin layer 7 and the like.

Alternatively, in the present invention, will be described an example of using the barrier film A ₁ according to the present invention shown in FIG. 2 described above, as shown in FIG. 4, on one side of a substrate film 1, the inorganic oxide A vapor deposition film 4 is provided, and on the surface of the inorganic oxide vapor deposition film 4, a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² have 1 to 8 carbon atoms) M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents the valence of M. A gas barrier coating film 2 comprising a gas barrier composition containing one or more alkoxides, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and obtained by polycondensation by a sol-gel method is further provided. The plasma treatment is applied to the surface of the gas barrier coating film 2. The surface of the plasma treated surface 3 of the barrier film A ₁ having the configuration in which a plasma treated surface 3 by the same manner as described above, the printed pattern layer 5, laminating - DOO adhesive layer 6 and, heat - city - It is possible to manufacture the laminate B _{1 according} to the present invention using the barrier film A _{1 according} to the present invention by sequentially laminating the rusty resin layer 7 and the like.
The above examples illustrate one or two examples of the layer structure of the laminated material according to the present invention using the barrier film according to the present invention, and the present invention is not limited thereby. Needless to say.
For example, although not shown, various substrates can be laminated on the surface of the plasma-treated surface of the barrier film according to the present invention. For example, as described above, a printed pattern layer, an adhesive layer for laminating An arbitrary base material such as an anchor coating agent layer, a melt-extruded resin layer, a primer agent layer, various plastic film layers, and the like can be laminated to produce laminated materials having various forms. .

Thus, in the present invention, the laminate material according to the present invention as described above can be used to produce a bag for packaging in various forms, for example, although not illustrated, Prepare the laminated material according to the present invention shown in FIG. 3, FIG. 4 and the like, and put the heat-seal resin layers located on the innermost layer facing each other, overlap each other, and then around the outer periphery. A two- or three-way seal type using the laminated material according to the present invention, in which a heat seal portion is formed by heat sealing two or three ends of the end portion and an opening is formed in the upper portion thereof. The packaging bag can be manufactured.
Thus, in the present invention, the packaging bag produced as described above is used, and the contents such as food and drink are filled from the opening at the top, and then the opening is heated to the heat sink. -A package product using a packaging bag manufactured by using the laminated material according to the present invention can be manufactured by forming an upper heat seal part.
The above illustrations are examples of packaging bags and packaging products using the laminated material according to the present invention, and the present invention is not limited thereto, for example, the form of packaging bags Although not shown, for example, it is possible to manufacture packaging bags having various forms suitable for contents such as a pillow packaging form, a gusset packaging form, a standing (self-supporting) pouch packaging form, and the like. .

Next, in the present invention, the barrier film according to the present invention and the laminated material using the same will be described with respect to the material constituting the barrier film, the laminated material, etc., the production method thereof, etc. Since the base film constituting the barrier film according to the invention is provided with a gas barrier coating film, an inorganic oxide deposition film, etc., it has excellent properties in mechanical, physical, chemical, etc. In particular, it has strength and toughness, has heat resistance, withstands the conditions for forming an inorganic oxide vapor-deposited film, and does not deteriorate the properties of the inorganic oxide vapor-deposited film A resin film or sheet that can be held can be used. Specifically, in the present invention, as the base film, for example, polyethylene resin, polypropylene resin, cyclic polyolefin resin, fluorine resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile Ru-butadiene-styrene copolymer (ABS resin), polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin, polyethylene terephthalate, polyethylene naphthalate Polyester resins such as nylon, various polyamide resins such as nylon, polyimide resins, polyamideimide resins, polyaryl phthalate resins, silicone resins, polysulfone resins, polyphenylene sulfide resins, polyethersulfones Resin, polyurethane resin, AS - Le resins, cellulose - scan resin, various resins other such film or sheet - may be used and.
In the present invention, it is particularly preferable to use a film or sheet of polypropylene resin, polyester resin, or polyamide resin.

In the present invention, as the above-mentioned various resin films or sheets, for example, one or more of the above-mentioned various resins are used, and an extrusion method, a cast molding method, a T-die method, a cutting method, an inflation method are used. -A method of forming the above-mentioned various resins independently using a film-forming method such as an ionization method or the like, or a method of forming a multilayer co-extrusion film using two or more types of various resins In addition, by using two or more kinds of resins, a film or sheet of various resins 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 tubular 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 100 μm, more preferably about 9 to 50 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, general additives include, for example, colorants such as lubricants, crosslinking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, antistatic agents, lubricants, antiblocking agents, dyes, pigments and the like. Others can be arbitrarily used, and further, a modifying resin or the like can be used.

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

Next, in the present invention, the gas barrier coating film constituting the barrier film according to the present invention will be described. As the gas barrier coating film, the general formula R ¹ _n M (OR ² ) _m (wherein, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents M At least one alkoxide represented by the formula (1)), a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer, and a sol-gel catalyst, acid, water And a step of preparing a gas barrier composition that is polycondensed by a sol-gel method in the presence of an organic solvent, provided on one side of the base film, or provided on one side of the base film On the inorganic oxide deposition film The step of applying a gas barrier composition that undergoes polycondensation by the sol-gel method to provide a coating film, the base film provided with the coating film at 20 ° C. to 180 ° C. and the above An inorganic oxide vapor deposition film provided on one surface of the above base film or on one surface of the above base film by heat treatment for 10 seconds to 10 minutes at a temperature below the melting point of the base film. Further, it can be manufactured by a manufacturing process including a process of forming a gas barrier coating film with the above gas barrier composition.

Alternatively, in the present invention, the gas barrier coating film constituting the barrier film according to the present invention may be represented by the general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² have 1 carbon atom) -8 represents an organic group, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M. In the presence of a sol-gel catalyst, an acid, water, and an organic solvent. The step of preparing a gas barrier composition that undergoes polycondensation by the sol-gel method, on one side of the base film, or on an inorganic oxide vapor deposition film provided on one side of the base film, Gas condensed by the above sol-gel method The step of coating the barrier film composition to form two or more layers of the coating film, and the base film provided with the coating film having the above two or more layers laminated thereon are at 20 ° C. to 180 ° C. and the above group Heat treatment at a temperature not higher than the melting point of the material film for 10 seconds to 10 minutes, and the inorganic oxide vapor deposition film provided on one side of the base film or on one side of the base film. Further, it can be manufactured by a manufacturing process including a process of forming a composite polymer layer in which two or more gas barrier coating films of the above gas barrier composition are stacked.

In the above, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m for forming the gas barrier coating film constituting the barrier film according to the present invention, a partial hydrolyzate of alkoxide, hydrolysis of alkoxide At least one kind of condensate can be used, and as the partial hydrolyzate of the above alkoxide, it is not necessary that all alkoxy groups are hydrolyzed, and at least one is hydrolyzed. In addition, the hydrolysis condensate may be a dimer or more of a partially hydrolyzed alkoxide, specifically, a 2 to 6 mer.

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

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

Thus, in the present invention, as the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m , for example, it is preferable to use an alkoxysilane in which M is Si.
The alkoxysilane is represented by the general formula Si (ORa) ₄ (wherein Ra represents a lower alkyl group).
In the above, Ra includes a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and the like.
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 , etc. can be used.

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

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

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

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

In the present invention, the above alkoxides may be used as a mixture of two or more thereof.
Thus, in the present invention, in particular, by using a mixture of alkoxysilane and zirconium alkoxide, it is possible to improve the toughness, heat resistance, etc. of the resulting gas barrier laminate film, and to improve the resistance of the film during stretching. A decrease in retort property is avoided.
The amount of the zirconium alkoxide used is in the range of 10 parts by weight or less with respect to 100 parts by weight of the alkoxysilane, preferably about 5 parts by weight. In the above, when the amount exceeds 10 parts by weight, the formed gas barrier coating film is easily gelled, and the brittleness of the film is increased, so that the gas barrier coating film is easily peeled off when the base film is coated. This is not preferable.

In the present invention, in particular, by using a mixture of alkoxysilane and titanium alkoxide, the thermal conductivity of the resulting gas barrier coating film is lowered, and the heat resistance of the barrier film according to the present invention is significantly improved. There are advantages.
In the above, the amount of titanium alkoxide used is in the range of 5 parts by weight or less with respect to 100 parts by weight of the alkoxysilane, and preferably about 3 parts by weight.
In the above, if it exceeds 5 parts by weight, the gas barrier coating film to be formed becomes more brittle, and when the base film is coated, the gas barrier coating film tends to peel off, which is not preferable. is there.

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

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

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

In the present invention, as the polyvinyl alcohol-based resin and / or ethylene / vinyl alcohol copolymer, first, as the polyvinyl alcohol-based resin, generally obtained by saponifying polyvinyl acetate is used. be able to.
As the above-mentioned polyvinyl alcohol-based resin, partially saponified polyvinyl alcohol resin in which several tens of percent of acetic acid groups remain, or completely saponified polyvinyl alcohol in which acetic acid groups do not remain, or OH groups have been modified. A modified polyvinyl alcohol resin may be used and is not particularly limited.
Specific examples of the polyvinyl alcohol resin include RS-110 (saponification degree = 99%, polymerization degree = 1,000), an RS polymer manufactured by Kuraray Co., Ltd., and Kuraray Poval LM-20SO (saponification) manufactured by the same company. Degree = 40%, degree of polymerization = 2,000), Gohsenol NM-14 (degree of saponification = 99%, degree of polymerization = 1,400) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. can be used.

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

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

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

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

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

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

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

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

  Furthermore, in the present invention, as described above, when ethylene vinyl alcohol copolymer or polyvinyl alcohol resin and ethylene vinyl alcohol copolymer are not used in combination, that is, only polyvinyl alcohol resin is used. And when manufacturing the barrier film which concerns on this invention, in order to improve the gas barrier property after a hot-water process, for example, the gas barrier composition which used the polyvinyl alcohol-type resin beforehand is applied. Forming a first coating layer, and then coating a gas barrier composition containing an ethylene / vinyl alcohol copolymer on the coating layer to form a second coating layer, By forming these composite layers, the gas barrier property of the barrier film according to the present invention can be improved.

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

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

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

In the method of the present invention, the amount of water added is 0.8 to 2 mol, preferably 1. Since it is adjusted to 5 moles, the above linear polymer is formed.
Such a linear polymer has crystallinity and has a structure in which a large number of minute crystals are embedded in an amorphous part.
Such a crystal structure is the same as that of a crystalline organic polymer (for example, vinylidene chloride or polyvinyl alcohol), and a polar group (OH group) is partially present in the molecule, and the molecular aggregation energy is high. Excellent gas barrier properties due to high rigidity.

Since the barrier film according to the present invention has the above-described excellent characteristics, it is useful as a packaging material. In particular, the barrier film (permeation of gas barrier properties (O ₂ , N ₂ , H ₂ O, CO ₂ , etc.) Therefore, it is preferably used as a barrier substrate constituting a food packaging film.
In particular, when used in so-called gas-filled packaging filled with N ₂ or CO ₂ gas, the excellent gas barrier property is extremely effective for holding the filled gas.
Furthermore, the barrier film according to the present invention is excellent in hot water treatment, particularly high-pressure hot water treatment (retort treatment), and exhibits extremely excellent gas barrier properties.

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

    As described above, the present invention is, for example, a base film such as a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, an inorganic oxide vapor-deposited film on the base film, and an inorganic oxide vapor-deposited film. A gas barrier laminate in which an alkoxysilane, a polyvinyl alcohol and / or an ethylene vinyl alcohol copolymer, and a gas barrier coating film by a gas barrier composition comprising a silane coupling agent as required are sequentially provided. It relates to materials.

Next, in the present invention, the plasma processing surface constituting the barrier film according to the present invention will be described. First, as the plasma processing for forming the plasma processing surface, gas is ionized by arc discharge. Plasma treatment can be performed using a plasma surface treatment method that performs surface modification using plasma gas.
That is, in the present invention, the plasma treatment can be performed by a method using an inorganic gas such as oxygen gas, nitrogen gas, argon gas, helium gas as the plasma gas.
Thus, in the present invention, when the plasma treatment is performed on the surface of the gas barrier coating film, oxygen plasma or a mixed gas of oxygen gas and argon gas is used during the plasma discharge treatment. It is preferable to perform plasma treatment using an inorganic gas containing a gas as a plasma gas.
In the present invention, it is possible to perform plasma treatment at a lower voltage by the plasma treatment as described above, and thereby, there is no discoloration of the surface of the gas barrier coating film and the gas barrier coating. For example, OH groups or the like can be introduced into the surface of the film by a chemical reaction or the like, and Si—C bonds and the like existing in the gas barrier coating film can be converted to SiO ₂ .
Thus, in the present invention, the plasma treatment surface by the plasma treatment as described above increases the crosslinking density of the gas barrier coating film by the gas barrier composition, improves its humidity dependency, etc., and provides a gas barrier against oxygen gas. As a matter of course, the barrier property against water vapor is improved, and relatively high gas barrier property against oxygen gas, water vapor, etc. can be stably maintained. The surface is subjected to plasma treatment using a plasma gas composed of an inorganic gas containing oxygen gas in a vacuum, thereby forming a plasma treatment surface. When laminating base materials such as adhesive layers, anchor coating layers, heat-sealable resin layers, etc., the bee adhesion is improved and the lamination strength is remarkably increased. And it makes it possible to be Mel.

By the way, in the present invention, plasma processing conditions are extremely important for the above-described plasma processing, and the effects obtained by the conditions are variously different.
Thus, in the present invention, factors that influence a chemical reaction or the like by plasma treatment include plasma output, gas type, gas supply amount, treatment time, and the like.
In the present invention, as the plasma treatment, specifically, it is desirable to use a mixed gas of oxygen gas and argon gas, and the gas pressure of the mixed gas of oxygen gas and argon gas is 1 ×. 10 ⁻¹ to 10 ⁻¹⁰ Torr position, more preferably 1 × 10 ⁻² to 1 × 10 ⁻⁸ Torr position is desirable, and the ratio of oxygen gas to argon gas is oxygen gas: argon by partial pressure ratio Gas = 100: 0 to 30:70, more preferably 90:10 to 70:30, and the plasma output is preferably about 100 to 2500 W, more preferably about 500 to 1500 W. Furthermore, the processing speed is preferably about 100 to 600 m / min, more preferably about 200 to 500 m / min. When the partial pressure ratio between the oxygen gas and the argon gas is increased, if the argon gas partial pressure is increased, oxygen molecules activated by the plasma are reduced, the argon gas acts as a reducing gas, and the introduction of hydroxyl groups is inhibited. Is not preferable.
In addition, when the plasma output is less than 100 W, more preferably less than 500 W, the activation of oxygen gas is lowered, and it is difficult to produce highly active oxygen atoms. Furthermore, if it exceeds 2500 W, the plasma output is too high, which is not preferable because it causes a problem that the physical properties of the coating itself deteriorate due to the deterioration of the gas barrier coating film or the like.
Further, when the above processing speed is less than 100 m / min, further less than 250 m / min, the amount of oxygen plasma is small, and when it exceeds 600 m / min, and further exceeds 500 m / min, a gas barrier is obtained. Oxidation of the conductive coating film proceeds rapidly and the transparency becomes high, but the barrier property is lowered, which is not preferable.

In the present invention, as a method of generating plasma in plasma processing, for example, three types of devices such as direct current glow discharge, radio frequency (AF) discharge, and microwave discharge are used. It can be carried out.
Thus, in the present invention, it can be performed using a 3.56 MHz high frequency (AF) discharge device.

  Next, in the present invention, the inorganic oxide vapor deposition film constituting the barrier film according to the present invention will be described. As the inorganic oxide vapor deposition film, for example, chemical vapor deposition or physical vapor deposition may be used. A growth method, or a combination of both, can be produced by forming a single layer film consisting of one layer of an inorganic oxide vapor-deposited film, a multilayer film consisting of two or more layers, or a composite film.

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

Specifically, an example of the formation method of the deposited film of the inorganic oxide by the low temperature plasma chemical vapor deposition method will be described as an example. FIG. 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 a vapor deposition film.
In the present invention, as shown in FIG. 5, the base film 1 is fed out from the unwinding roll 23 disposed in the vacuum chamber 22 of the plasma chemical vapor deposition apparatus 21. 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. Plasma is generated by the glow discharge plasma 30 on the base film 1 and irradiated to form a deposited film 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.
Next, the base film 1 on which the vapor-deposited film of inorganic oxide such as silicon oxide is formed is wound on the winding roll 34 via the auxiliary roll 33, and the plasma chemical vapor phase according to the present invention is applied. A vapor-deposited film of an inorganic oxide can be formed by a growth method.
In the figure, 35 represents a vacuum pump.
The above exemplification is an example, and it is needless to say that the present invention is not limited thereby.
Although not shown, in the present invention, the inorganic oxide vapor deposition film may be not only one layer of the inorganic oxide vapor deposition film but also a multilayer film in which two or more layers are laminated, and is used. The material may be used alone or as a mixture of two or more, and an inorganic oxide vapor deposition film mixed with different materials may be formed.

In the above, the inside of the vacuum chamber 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 substrate film is conveyed at a constant speed, and the glow discharge plasma is used to cool the electrode drum peripheral surface. A vapor deposition film of an inorganic oxide such as silicon oxide can be formed on the upper base 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.

Further, in the plasma chemical vapor deposition apparatus, the formation of deposited film of an inorganic oxide of such as silicon oxide, on a substrate film, a plasma raw material gas in the form of SiO _X while oxidized with oxygen gas Since it is formed in a thin film, the formed deposited film of inorganic oxide such as silicon oxide is a dense, flexible, continuous layer with few gaps. The barrier property of the inorganic oxide vapor deposition film is much higher than that of the inorganic oxide vapor deposition film such as silicon oxide formed by the conventional vacuum vapor deposition method. It 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. This has the advantage that the tight adhesion between the deposited film of the product and the substrate film is high.
Furthermore, as described above, the degree of vacuum when forming a continuous film of an inorganic oxide such as silicon oxide is about 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to 1 × 10. ^{-2 Since} it is prepared at the Torr position, the degree of vacuum when forming a deposited film of an inorganic oxide such as silicon oxide by the conventional vacuum evaporation method is compared with the 1 × 10 ⁻⁴ to 1 × 10 ⁻⁵ Torr position. Since the degree of vacuum is low, it is possible to shorten the time for setting the vacuum state at the time of exchanging the base film, to easily stabilize the degree of vacuum, and to stabilize the film forming process.

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

In addition, the silicon oxide vapor-deposited film is mainly composed of silicon oxide, and further, at least one kind of compound composed of one kind of carbon, hydrogen, silicon, or oxygen, or two or more kinds thereof is chemically used. It consists of a vapor deposition film contained by 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 silicon oxide film become insufficient, and scratches, cracks, etc. are likely to occur due to bending. It is difficult to stably maintain a high barrier property, and if it exceeds 50%, the barrier property is lowered, which is not preferable.
Furthermore, in the present invention, in the silicon oxide vapor deposition film, the content of the above-mentioned compound is preferably decreased from the surface of the silicon oxide vapor deposition film in the depth direction. On the surface, the impact resistance and the like can be enhanced by the above compound and the like. On the other hand, at the interface with the base film, the content of the above compound is small. This has the advantage that the tight adhesion of the material becomes strong.

Thus, in the present invention, the above-described deposited film of silicon oxide is subjected to surface analysis such as, for example, an X-ray photoelectron spectrometer (Xray), secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy, SIMS), or the like. The physical properties as described above can be confirmed by conducting an elemental analysis of the deposited film of silicon oxide using a method of analyzing by ion etching in the depth direction using an apparatus.
In the present invention, the film thickness of the above-described silicon oxide vapor deposition film is preferably about 50 to 4000 mm, and specifically, the film thickness is preferably about 100 to 1000 mm. In the above, if it is thicker than 1000 mm, and more preferably 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 an effect of barrier properties. Is not preferable 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. In the above, as means for changing the film thickness of the silicon oxide vapor deposition film, the volume velocity of the vapor deposition film is increased, that is, the method of increasing the amount of monomer gas and oxygen gas and the vapor deposition rate. This can be done by a method of slowing down.

Next, in the above, as a vapor deposition monomer gas such as an organic silicon compound for forming a vapor deposition film of an inorganic oxide such as silicon oxide, for example, 1.1.3.3-tetramethyldisiloxane, hexamethyldisiloxane Siloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyl Trimethoxysilane, 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 inorganic oxide vapor-deposited film by the physical vapor deposition method will be described in more detail. Examples of the inorganic oxide vapor-deposited film by the physical vapor deposition method include, for example, vacuum vapor deposition and sputtering. A vapor deposition film of an inorganic oxide can be formed using a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a method, an ion plating method, or an ion cluster beam method.
In the present invention, specifically, a metal or metal oxide is used as a raw material, this is heated and vaporized, and this is vapor-deposited on one of the substrate films, or a raw material is metal or metal. Using an oxidation reaction vapor deposition method in which oxygen is introduced and oxidized to be deposited on one side of the base film, and further, a plasma assisted oxidation reaction vapor deposition method in which the oxidation reaction is supported by plasma is used. A vapor deposition film can be formed.
In the above, as a heating method of the vapor deposition material, for example, a resistance heating method, a high frequency induction heating method, an electron beam heating method (EB), or the like can be used.

In the present invention, specific examples of a method for forming a thin film of an inorganic oxide by physical vapor deposition are given. FIG. 6 is a schematic configuration diagram showing an example of a take-up vacuum deposition apparatus.
As shown in FIG. 6, 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 dating drum 46;
Thus, the evaporation source 48 heated by the crucible 47, for example, metal aluminum or aluminum oxide is evaporated on the base film 1 guided on the cooled coating drum 46, Further, if necessary, an oxygen gas or the like is ejected from the oxygen gas outlet 49 and an inorganic oxide vapor deposition film such as aluminum oxide is formed through the masks 50 and 50 while supplying the oxygen gas. Next, in the above, for example, the base film 1 on which a vapor-deposited film of an inorganic oxide such as aluminum oxide is formed is sent out through the guide rolls 51 and 52 and wound up on the take-up roll 53. An inorganic oxide vapor-deposited film can be formed by physical vapor deposition according to the invention.
In the present invention, the first-layer inorganic oxide vapor deposition film is first formed using the above-described take-up vacuum vapor deposition apparatus, and then the inorganic oxide vapor deposition film is formed in the same manner. Further, an inorganic oxide vapor deposition film is formed on the substrate, or by using the above-described take-up vacuum vapor deposition apparatus, these are connected in series, and the inorganic oxide vapor deposition is continuously performed. By forming the film, it is possible to form an inorganic oxide vapor-deposited film composed of two or more multilayer films.

In the above, as the deposited film of metal or inorganic oxide, basically, any thin film on which a metal oxide is deposited can be used. For example, silicon (Si), aluminum (Al), magnesium (Mg ), Calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y), etc. Oxide deposited films can be used.
Thus, preferable examples include vapor-deposited films of metal oxides such as silicon (Si) and aluminum (Al).
Thus, the metal oxide vapor-deposited film can be referred to as a metal oxide such as silicon oxide, aluminum oxide, magnesium oxide, and the like, for example, SiO _x , AlO _x , MgO _{x, and} the like, represented by MO _X (wherein M represents a metal element, and the value of X varies depending on the metal element).
Moreover, as a range of said X value, silicon (Si) is 0-2, aluminum (Al) is 0-1.5, magnesium (Mg) is 0-1, calcium (Ca) is 0 to 1, potassium (K) is 0 to 0.5, tin (Sn) is 0 to 2, sodium (Na) is 0 to 0.5, boron (B) is 0 to 1, 5, Titanium (Ti) can take values in the range of 0 to 2, lead (Pb) in the range of 0 to 1, zirconium (Zr) in the range of 0 to 2, and yttrium (Y) in the range of 0 to 1.5.
In the above, when X = 0, it is a complete metal and is not transparent and cannot be used at all. The upper limit of the range of X is a completely oxidized value.
In the present invention, generally, examples other than silicon (Si) and aluminum (Al) are scarcely used. Silicon (Si) is 1.0 to 2.0, and aluminum (Al) is 0.5. Those with values in the range of -1.5 can be used.
In the present invention, the film thickness of the inorganic oxide vapor-deposited film as described above varies depending on the metal used or the type of metal oxide, but is, for example, about 50 to 2000 mm, preferably 100 to 1000 mm. It is desirable to select and form arbitrarily within the range.
Moreover, in this invention, as a vapor deposition film of an inorganic oxide, as a metal or metal oxide to be used, it is used by 1 type, or 2 or more types of mixtures, and vapor deposition of the inorganic oxide mixed by the dissimilar material A membrane can also be constructed.

By the way, in the present invention, as the inorganic oxide vapor deposition film according to the present invention, for example, two or more layers of different inorganic oxide vapor deposition films using both physical vapor deposition and chemical vapor deposition are combined. It is also possible to form and use a composite film.
Thus, as a composite film composed of two or more layers of the above-mentioned different types of inorganic oxide vapor-deposited films, first, on the base film, it is dense and flexible by chemical vapor deposition. An inorganic oxide vapor deposition film capable of preventing the occurrence of cracks is provided, and then an inorganic oxide vapor deposition film formed by physical vapor deposition is provided on the inorganic oxide vapor deposition film to form two or more layers. It is desirable to constitute an inorganic oxide vapor-deposited film made of a composite film made of
Of course, in the present invention, contrary to the above, an inorganic oxide vapor-deposited film is first provided on the base film by physical vapor deposition, and then dense by chemical vapor deposition. It is also possible to provide an inorganic oxide vapor deposition film composed of a composite film composed of two or more layers by providing an inorganic oxide vapor deposition film that is highly flexible and can relatively prevent the occurrence of cracks. is there.

Next, in the present invention, the barrier film according to the present invention produced as described above uses this as a barrier substrate, and other plastic film, paper substrate, cellophane, woven fabric or nonwoven fabric, A laminated material having various forms is produced by arbitrarily laminating one or more of various substrates such as a glass plate, etc., and thus the laminated material is used as a packaging material, an optical member, Protective sheet for solar cell module, protective film for organic EL display, protective film for film liquid crystal display, packaging material for polymer battery, aluminum packaging material, etc. It is.
As an example of the method for producing the laminated material, for example, a laminating adhesive layer is formed, for example, on the surface of the plasma processing surface constituting the barrier film according to the present invention, and then, By laminating a desired base material such as a plastic film constituting a heat-sealable resin layer or the like through a laminating adhesive layer or the like using a dry lamination method, various The laminated material which consists of these forms can be manufactured.
Alternatively, in the present invention, for example, an anchor coating agent layer is formed on the surface of the plasma processing surface constituting the barrier film according to the present invention, and then the anchor coating agent layer, etc. For example, various resins are melt-extruded and, for example, a desired base material such as a plastic film forming a heat-sealable resin layer is laminated using a melt-extrusion laminating method. Thus, laminated materials having various forms can be manufactured.
In addition, in this invention, it is the same as the above also on the surface of the base film which comprises the barrier film which concerns on this invention, Laminated material which laminates | stacks another desired base material arbitrarily and consists of various forms Further, in the present invention, it is possible to manufacture a laminated material having various forms by arbitrarily laminating a desired base material between the respective layers, and thus the present invention. In various types of laminated materials, various types of laminated materials can be designed and manufactured by arbitrarily laminating other base materials depending on the purpose of use, usage pattern, application, etc.

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

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

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

Examples of the melt-extruded resin layer in the melt-extrusion laminating method include polyethylene resin, polypropylene resin, acid-modified polyethylene resin, acid-modified polypropylene resin, ethylene-acrylic acid or methacrylic acid copolymer. Thermoplastics such as coalesced resin, sarin resin, ethylene-vinyl acetate copolymer, polyvinyl acetate resin, ethylene-acrylic acid ester or methacrylic acid ester copolymer, polystyrene resin, polyvinyl chloride resin, etc. One type or two or more types of resins can be used.
In the melt extrusion lamination method described above, in order to obtain stronger adhesive strength, for example, lamination may be performed via an anchor coating agent layer such as the above anchor coating agent. it can.

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

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

Next, in the present invention, as the base material constituting the laminated material, for example, various paper base materials constituting the paper layer can be used. Specifically, in the present invention, Materials include formability, bending resistance, rigidity, etc., for example, strong sized bleached or unbleached paper base, or pure white roll paper, kraft paper, paperboard, processed paper Paper base materials such as, etc., etc. can be used.
In the above, as the paper substrate constituting the paper layer, it is desirable to use a material having a basis weight of about 80 to 600 g / m ² , preferably a basis weight of about 100 to 450 g / m ² .
Of course, in the present invention, the paper base material constituting the paper layer and various resin films or sheets as the base film mentioned above can be used in combination.

Furthermore, in the present invention, examples of the material constituting the laminated material include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, and ethylene having barrier properties such as water vapor and water. -Resin film or sheet such as propylene copolymer, or resin film such as polyvinyl alcohol, saponified ethylene-vinyl acetate copolymer, nylon MXD6 resin having barrier properties against oxygen, water vapor, etc. It is also possible to use various colored resin films or sheets having light-shielding properties obtained by adding a colorant such as a pigment to a sheet or a resin and adding a desired additive and kneading to form a film. it can.
These materials can be used alone or in combination. The thickness of the film or sheet is arbitrary, but is usually about 5 μm to 300 μm, more preferably about 10 μm to 100 μm.

In the present invention, usually, when the above laminated material is applied to various applications, it is subjected to severe conditions both physically and chemically. Various requirements such as deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealing performance, quality maintenance, workability, hygiene, etc. are required. Can be used by arbitrarily selecting a material that satisfies the above-mentioned conditions. Specifically, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene , Ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid or methacrylic acid copolymer, methyl Pentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (meth) acrylic resin, polyacrylonitrile resin, polystyrene Resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate resin, polyvinyl alcohol Resin, saponified ethylene-vinyl acetate copolymer, fluorine resin, diene resin, polyacetal resin, polyurethane resin, nitrocellulose, etc. You can select and use.
In addition, for example, a film such as cellophane, a synthetic paper, or the like can be used. In the present invention, the above-described film or sheet may be any of unstretched, uniaxially or biaxially stretched.
The thickness is arbitrary, but can be selected from a range of several μm to 300 μm.
Furthermore, in the present invention, the film or sheet may be a film having any property such as extrusion film formation, inflation film formation, and coating film.

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

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

Next, in the present invention, a description will be given of a bag making or box making method for manufacturing a packaging container using the above-described laminated material. For example, when the packaging container is a flexible packaging bag made of a plastic film or the like Using the laminated material manufactured by the method as described above, facing the heat-sealable film of the inner layer facing each other, folding them up or stacking the two sheets, The bag body can be configured by heat sealing the portion to provide a seal portion.
Thus, as a bag-making method, the above-mentioned laminated material is folded with the inner layer faces facing each other, or the two sheets are overlapped, and the peripheral edge of the outer periphery is, for example, a side sheet. Seal type, two-sided seal type, three-sided seal type, four-sided seal type, envelope-sealed seal type, jointed seal type (pillar seal type), pleated seal type The various types of packaging containers according to the present invention can be manufactured by heat sealing in the form of a heat sealing such as a flat bottom sealing type, a square bottom sealing type, or the like.
In addition, for example, a self-supporting packaging bag (standing pouch) or the like can be manufactured, and in the present invention, a tube container or the like can also be manufactured using the above-described laminated material.
In the above, as the heat seal method, for example, a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal and the like are known. It can be done by the method.
In the present invention, a spout such as a one-piece type, a two-piece type, or the like, or a zipper for opening and closing can be arbitrarily attached to the packaging container as described above.

Next, in the case of a liquid-filled paper container including a paper base material as a packaging container, for example, as a laminated material, a laminated material in which a paper base material is laminated is manufactured, and a blank plate for manufacturing a desired paper container is prepared from this. After that, the body, bottom, head, etc. can be boxed by using the blank plate, and for example, a brick type, flat type or gable top type liquid paper container can be manufactured. .
Further, the shape can be any of a rectangular container, a cylindrical paper can such as a round shape, and the like.

In the present invention, the packaging container produced as described above is used for filling and packaging various foods, chemicals such as adhesives and adhesives, cosmetics, pharmaceuticals, miscellaneous goods such as chemical warmers, and other items. It is what is used.
Thus, in the present invention, in particular, for example, a liquid sachet filled with soy sauce, sauce, soup, etc., a sachet filled with candy, a soft packaging bag filled with fresh confectionery, or the like, or It is useful as a packaging container for filling and packaging foods and beverages such as soft packaging bags for filling and packaging boiled or retort foods.

Hereinafter, the present invention will be described in more detail with reference to examples.
(1). First, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used as a base film, and the gas barrier composition shown in Table 1 below is used on the corona-treated surface of the biaxially stretched polyethylene terephthalate film. This was coated by a gravure roll coating method, and then heat-treated at 100 ° C. for 30 seconds to form a gas barrier coating film having a thickness of 3 μm (in a dry operation state).
According to the composition shown in Table 1 below, the composition a. Composition prepared in advance in an EVOH solution prepared by dissolving an ethylene-vinyl alcohol copolymer (EVOH, ethylene copolymerization ratio 29%) in a mixed solvent of isopropyl alcohol and ion-exchanged water b. A hydrolyzate composed of ethyl silicate 40, isopropyl alcohol, acetylacetone aluminum, and ion-exchanged water, followed by stirring, and a composition prepared in advance c. A mixed liquid composed of an aqueous polyvinyl alcohol resin solution, a silane coupling agent (epoxysilica SH6040), acetic acid, isopropyl alcohol and ion-exchanged water was added and stirred to obtain a colorless and transparent gas barrier composition.
(Table 1)
Composition a: EVOH (ethylene copolymerization ratio 29%) 0.610 (wt%)
Isopropyl alcohol 3.294
H ₂ O 2.196
Composition b: Ethyl silicate 40 11.460
Isopropyl alcohol 17.662
Aluminum acetylacetone 0.020
H ₂ O 13.752
Composition c: Polyvinyl alcohol resin 1.520
Silane coupling agent 0.050
Isopropyl alcohol 13.844
H ₂ O 35.462
Acetic acid 0.130
Total 100.000 (wt%)
(2). Next, on the surface of the gas barrier coating film of the biaxially stretched polyethylene terephthalate film formed with the gas barrier coating film formed in the above (1), a plasma output of 15 kW and an oxygen gas (at a vacuum degree of 10 ⁻³ Toor) O ₂ ): Argon gas (Ar) = 3.0: 1.0 (unit: Slm), a mixed gas pressure of 6.0 × 10 ⁻⁵ Torr, a processing speed of 300 m / min, oxygen / Argon mixed gas plasma treatment was performed to form a plasma treated surface, and a barrier film according to the present invention was produced.
(3). Next, using the normal gravure ink composition on the surface of the plasma-treated surface of the barrier film produced above, a predetermined printing pattern consisting of letters, figures, symbols, patterns, etc. is printed by the gravure printing method. Thus, a printed pattern layer was formed.
Next, on the entire surface including the printed pattern layer formed above, a two-component curable polyurethane laminating adhesive was coated by the gravure roll coating method in the same manner as described above to obtain a thickness of 4.0 g / An adhesive layer for laminating m ² (dry operation state) was formed.
Next, on the surface of the laminating adhesive layer, a low-density polyethylene film having a thickness of 30 μm is overlapped with the corona-treated surface facing each other, and then both are laminated by dry lamination. A laminate according to the present invention was produced.
(4). Next, two laminated materials manufactured as described above are prepared, and the surfaces of the low-density polyethylene film as the heat-seal resin layer located in the innermost layer are opposed to each other, and then the periphery of the periphery A three-side seal type liquid-filled packaging bag is manufactured by heat-sealing the three sides of the end, and then, for example, water is filled from the opening, and then the opening is heated. -Tossed to produce a packaged product according to the present invention.

(1). First, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used as a base film. First, the biaxially stretched polyethylene terephthalate film is mounted on a delivery roll of a plasma chemical vapor deposition apparatus, and then this is attached. A silicon oxide vapor deposition film having a thickness of 100 mm was formed on the corona-treated surface of the biaxially stretched polyethylene terephthalate film under the following vapor deposition conditions.
(Deposition conditions)
Reaction gas mixing ratio: Hexamethyldisiloxane: Oxygen gas: Helium = 1.2: 5.0: 2.5 (Unit: Slm)
Ultimate pressure: 5.0 × 10 ^-5 mbar
Film forming pressure: 7.0 × 10 ⁻² mbar
Line speed: 150 m / min
Power; 35kw
Next, immediately after forming a silicon oxide vapor-deposited film having a thickness of 100 mm as described above, a glow discharge plasma generator is used on the surface of the silicon oxide vapor-deposited film, and the power is 9 kw, oxygen gas (O ₂ ): argon Oxygen / argon mixed gas plasma treatment using a mixed gas consisting of gas (Ar) = 7.0: 2.5 (unit: Slm) at a mixed gas pressure of 6.0 × 10 ⁻² mba and a processing speed of 150 m / min. Was performed to form a plasma-treated surface in which the surface tension of the deposited silicon oxide film surface was improved by 54 dyne / cm or more.
(2). On the other hand, according to the composition shown in Table 2 below, composition a. Composition prepared in advance in an EVOH solution prepared by dissolving an ethylene-vinyl alcohol copolymer (EVOH, ethylene copolymerization ratio 29%) in a mixed solvent of isopropyl alcohol and ion-exchanged water b. A hydrolyzate composed of ethyl silicate 40, isopropyl alcohol, acetylacetone aluminum, and ion-exchanged water, followed by stirring, and a composition prepared in advance c. A mixed liquid composed of an aqueous polyvinyl alcohol resin solution, a silane coupling agent (epoxysilica SH6040), acetic acid, isopropyl alcohol and ion-exchanged water was added and stirred to obtain a colorless and transparent gas barrier composition.
(Table 2)
Composition a: EVOH (ethylene copolymerization ratio 29%) 0.610 (wt%)
Isopropyl alcohol 3.294
H ₂ O 2.196
Composition b: Ethyl silicate 40 11.460
Isopropyl alcohol 17.662
Aluminum acetylacetone 0.020
H ₂ O 13.752
Composition c: Polyvinyl alcohol resin 1.520
Silane coupling agent 0.050
Isopropyl alcohol 13.844
H ₂ O 35.462
Acetic acid 0.130
Total 100.000 (wt%)
Next, the gas barrier composition produced above is used on the plasma-treated surface formed in the above (1), and this is coated by a gravure roll coating method, and then heated at 100 ° C. for 10 seconds. The gas barrier coating film having a thickness of 0.3 μm (in the dry operation state) was formed by processing.
(3). Next, on the surface of the gas barrier coating film of the biaxially stretched polyethylene terephthalate film formed with the vapor deposited silicon oxide film and the gas barrier coating film formed in the above (1) and (2), the degree of vacuum is 10 ^{−. 3} Toor, plasma output 15 kw, oxygen gas (O ₂ ): Argon gas (Ar) = 3.0: 1.0 (unit: Slm) mixed gas, mixed gas pressure 6.0 × 10 ^{− An} oxygen / argon mixed gas plasma treatment was performed at ⁵ Torr and a treatment speed of 300 m / min to form a plasma treated surface, thereby producing a barrier film according to the present invention.
(4). Next, using the normal gravure ink composition on the surface of the plasma-treated surface of the barrier film produced above, a predetermined printing pattern consisting of letters, figures, symbols, patterns, etc. is printed by the gravure printing method. Thus, a printed pattern layer was formed.
Next, on the entire surface including the printed pattern layer formed above, a two-component curable polyurethane laminating adhesive was coated by the gravure roll coating method in the same manner as described above to obtain a thickness of 4.0 g / An adhesive layer for laminating m ² (dry operation state) was formed.
Next, on the surface of the laminating adhesive layer, a low-density polyethylene film having a thickness of 30 μm is overlapped with the corona-treated surface facing each other, and then both are laminated by dry lamination. A laminate according to the present invention was produced.
(5). Next, two laminated materials manufactured as described above are prepared, and the surfaces of the low-density polyethylene film as the heat-seal resin layer located in the innermost layer are opposed to each other, and then the periphery of the periphery A three-side seal type liquid-filled packaging bag is manufactured by heat-sealing the three sides of the end, and then, for example, water is filled from the opening, and then the opening is heated. -Tossed to produce a packaged product according to the present invention.

(1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used as the base film. First, the above-mentioned biaxially stretched polyethylene terephthalate film is mounted on a take-up roll of a take-up vacuum deposition apparatus, and then this is fed out. The film thickness of the biaxially stretched polyethylene terephthalate film is as follows according to the following vapor deposition conditions by using an electron beam (EB) heating method while supplying oxygen gas using aluminum as a vapor deposition source. A 200-mm aluminum oxide vapor deposition film was formed.
(Deposition conditions)
Degree of vacuum in the deposition chamber; 2 × 10 ^-4 mbar
Degree of vacuum in winding chamber; 2 × 10 ^-2 mbar
Electron beam power: 25 kW
Film transport speed: 240 m / min
Vapor deposition surface; Corona treatment surface Next, immediately after forming the 200 nm thick aluminum oxide vapor deposition film, a plasma treatment surface was formed on the aluminum oxide vapor deposition film surface in the same manner as in Example 2 above. did.
(2). On the other hand, according to the composition shown in Table 3 below, composition a. Composition prepared in advance in an EVOH solution prepared by dissolving an ethylene-vinyl alcohol copolymer (EVOH, ethylene copolymerization ratio 29%) in a mixed solvent of isopropyl alcohol and ion-exchanged water b. A hydrolyzate consisting of ethyl silicate 40 (manufactured by Colcoat Co.), isopropyl alcohol, acetylacetone aluminum, and ion-exchanged water and stirred, and further prepared in advance c. A mixed liquid composed of an aqueous polyvinyl alcohol resin solution, a silane coupling agent (epoxysilica SH6040), acetic acid, isopropyl alcohol and ion-exchanged water was added and stirred to obtain a colorless and transparent gas barrier composition.
(Table 3)
Composition a: EVOH (ethylene copolymerization ratio 29%) 0.610 (wt%)
Isopropyl alcohol 3.294
H ₂ O 2.196
Composition b: Ethyl silicate 40 (manufactured by Colcoat Co.) 11.460
Isopropyl alcohol 17.662
Aluminum acetylacetone 0.020
H ₂ O 13.752
Composition c: Polyvinyl alcohol resin 1.520
Silane coupling agent 0.050
Isopropyl alcohol 13.844
H ₂ O 35.462
Acetic acid 0.130
Total 100.000 (wt%)
Next, the gas barrier composition produced above is used on the plasma-treated surface formed in the above (1), and this is coated by a gravure roll coating method, and then heated at 100 ° C. for 10 seconds. The gas barrier coating film having a thickness of 0.3 μm (in the dry operation state) was formed by processing.
(3). Next, on the surface of the gas barrier coating film of the biaxially stretched polyethylene terephthalate film formed with the vapor deposited silicon oxide film and the gas barrier coating film formed in the above (1) and (2), the degree of vacuum is 10 ^{−. 3} Toor, plasma output 15 kw, oxygen gas (O ₂ ): Argon gas (Ar) = 3.0: 1.0 (unit: Slm) mixed gas, mixed gas pressure 6.0 × 10 ^{− An} oxygen / argon mixed gas plasma treatment was performed at ⁵ Torr and a treatment speed of 300 m / min to form a plasma treated surface, thereby producing a barrier film according to the present invention.
(4). Then, the plasma-treated surface of the barrier film produced above was coated with a two-component curable polyurethane laminating adhesive by the gravure roll coating method in the same manner as described above. A laminating adhesive layer of 0 g / m ² (dry operation state) was formed.
Next, on the surface of the laminating adhesive layer, a low-density polyethylene film having a thickness of 30 μm is overlapped with the corona-treated surface facing each other, and then both are laminated by dry lamination. A laminate according to the present invention was produced.
(5). Next, two laminated materials manufactured as described above are prepared, and the surfaces of the low-density polyethylene film as the heat-seal resin layer located in the innermost layer are opposed to each other, and then the periphery of the periphery A three-side seal type liquid-filled packaging bag is manufactured by heat-sealing the three sides of the end, and then, for example, water is filled from the opening, and then the opening is heated. -Tossed to produce a packaged product according to the present invention.

(1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used as the base film. First, the above-mentioned biaxially stretched polyethylene terephthalate film is mounted on a take-up roll of a take-up vacuum deposition apparatus, and then this is fed out. The film thickness of the biaxially stretched polyethylene terephthalate film is as follows according to the following vapor deposition conditions by using an electron beam (EB) heating method while supplying oxygen gas using aluminum as a vapor deposition source. A 200-mm aluminum oxide vapor deposition film was formed.
(Deposition conditions)
Degree of vacuum in the deposition chamber; 2 × 10 ^-4 mbar
Degree of vacuum in winding chamber; 2 × 10 ^-2 mbar
Electron beam power: 25 kW
Film transport speed: 240 m / min
Vapor deposition surface; Corona treatment surface Next, immediately after forming the 200 nm thick aluminum oxide vapor deposition film, a plasma treatment surface was formed on the aluminum oxide vapor deposition film surface in the same manner as in Example 2 above. did.
(2). On the other hand, according to the composition shown in Table 4 below, composition a. Composition prepared in advance in an EVOH solution prepared by dissolving an ethylene-vinyl alcohol copolymer (EVOH, ethylene copolymerization ratio 29%) in a mixed solvent of isopropyl alcohol and ion-exchanged water b. A hydrolyzate composed of ethyl silicate 40, isopropyl alcohol, acetylacetone aluminum, and ion-exchanged water, followed by stirring, and a composition prepared in advance c. A mixed liquid composed of an aqueous polyvinyl alcohol resin solution, a silane coupling agent (epoxysilica SH6040), acetic acid, isopropyl alcohol and ion-exchanged water was added and stirred to obtain a colorless and transparent gas barrier composition.
(Table 4)
Composition a: EVOH (ethylene copolymerization ratio 29%) 0.610 (wt%)
Isopropyl alcohol 3.294
H ₂ O 2.196
Composition b: Ethyl silicate 40 11.460
Isopropyl alcohol 17.662
Aluminum acetylacetone 0.020
H ₂ O 13.752
Composition c: Polyvinyl alcohol resin 1.520
Silane coupling agent 0.050
Isopropyl alcohol 13.844
H ₂ O 35.462
Acetic acid 0.130
Total 100.000 (wt%)
Next, the gas barrier composition produced above is used on the plasma-treated surface formed in the above (1), and this is coated by a gravure roll coating method, and then heated at 100 ° C. for 10 seconds. The gas barrier coating film having a thickness of 0.3 μm (in the dry operation state) was formed by processing.
(3). Next, on the surface of the gas barrier coating film of the biaxially stretched polyethylene terephthalate film formed with the vapor deposited aluminum oxide film and the gas barrier coating film formed in the above (1) and (2), the degree of vacuum is 10 ^{−. 3} Toor, plasma output 15 kw, oxygen gas (O ₂ ): Argon gas (Ar) = 3.0: 1.0 (unit: Slm) mixed gas, mixed gas pressure 6.0 × 10 ^{− An} oxygen / argon mixed gas plasma treatment was performed at ⁵ Torr and a treatment speed of 300 m / min to form a plasma treated surface, thereby producing a barrier film according to the present invention.
(4). Next, an isocyanate anchor coating agent was coated on the surface of the plasma-treated surface of the barrier film produced as described above by the gravure roll coating method in the same manner as described above, and the thickness was 0.5 g / m. ² (dry operation state) anchor coating agent layer was formed.
Next, a low-density polyethylene film having a thickness of 30 μm is passed through a low-density polyethylene resin layer having a thickness of 15 μm while using low-density polyethylene on the surface of the anchor coating agent layer and melt-extruding this. Were laminated with their corona-treated surfaces facing each other, and then both were laminated by melt extrusion lamination to produce a laminate according to the present invention.
(5). Next, two laminated materials manufactured as described above are prepared, and the surfaces of the low-density polyethylene film as the heat-seal resin layer located in the innermost layer are opposed to each other, and then the periphery of the periphery A three-side seal type liquid-filled packaging bag is manufactured by heat-sealing the three sides of the end, and then, for example, water is filled from the opening, and then the opening is heated. -Tossed to produce a packaged product according to the present invention.

(Comparative Example 1)
In Example 1 above, after coating the gas barrier composition to form a gas barrier coating film, instead of forming a plasma-treated surface by plasma treatment on the surface of the gas barrier coating film, After coating the conductive composition, an aging treatment is performed at 55 ° C. for 3 days to form a gas barrier coating film (that is, a plasma-treated surface by plasma processing is not formed on the surface of the gas barrier coating film) Other than that, a barrier film, a laminate, and a packaged product were produced in the same manner as in Example 1 above, in the same manner as in Example 1 above.

(Comparative Example 2)
In Example 2 above, after coating the gas barrier composition to form a gas barrier coating film, instead of forming a plasma-treated surface by plasma treatment on the surface of the gas barrier coating film, After coating the conductive composition, an aging treatment is performed at 55 ° C. for 3 days to form a gas barrier coating film (that is, a plasma-treated surface by plasma processing is not formed on the surface of the gas barrier coating film) Other than that, a barrier film, a laminate, and a packaged product were produced in the same manner as in Example 2 above in the same manner as in Example 2 above.

(Comparative Example 3)
In Example 3 above, after coating the gas barrier composition to form a gas barrier coating film, instead of forming a plasma-treated surface by plasma treatment on the surface of the gas barrier coating film, After coating the conductive composition, an aging treatment is performed at 55 ° C. for 3 days to form a gas barrier coating film (that is, a plasma-treated surface by plasma processing is not formed on the surface of the gas barrier coating film) Other than that, a barrier film, a laminate, and a packaged product were produced in the same manner as in Example 3 above in the same manner as in Example 3 above.

(Comparative Example 4)
In Example 4 above, after coating the gas barrier composition to form a gas barrier coating film, instead of forming a plasma treated surface by plasma treatment on the surface of the gas barrier coating film, After coating the conductive composition, an aging treatment is performed at 55 ° C. for 3 days to form a gas barrier coating film (that is, a plasma-treated surface by plasma processing is not formed on the surface of the gas barrier coating film) In other respects, a barrier film, a laminate, and a packaged product were produced in the same manner as in Example 4 above in the same manner as in Example 4 above.

(Comparative Example 5)
In Example 5 above, after coating the gas barrier composition to form a gas barrier coating film, instead of forming a plasma treated surface by plasma treatment on the surface of the gas barrier coating film, After coating the conductive composition, an aging treatment is performed at 55 ° C. for 3 days to form a gas barrier coating film (that is, a plasma-treated surface by plasma processing is not formed on the surface of the gas barrier coating film) Other than that, a barrier film, a laminate, and a packaged product were produced in the same manner as in Example 5 above in the same manner as in Example 5 above.

(Comparative Example 6)
In Example 6 above, after coating the gas barrier composition to form a gas barrier coating film, instead of forming a plasma-treated surface by plasma treatment on the surface of the gas barrier coating film, After coating the conductive composition, an aging treatment is performed at 55 ° C. for 3 days to form a gas barrier coating film (that is, a plasma-treated surface by plasma processing is not formed on the surface of the gas barrier coating film) In other respects, a barrier film, a laminate, and a packaged product were produced in the same manner as in Example 6 above in the same manner as in Example 6 above.

(Comparative Example 7)
In Example 7 above, after coating the gas barrier composition to form a gas barrier coating film, instead of forming a plasma treated surface by plasma treatment on the surface of the gas barrier coating film, After coating the conductive composition, an aging treatment is performed at 55 ° C. for 3 days to form a gas barrier coating film (that is, a plasma-treated surface by plasma processing is not formed on the surface of the gas barrier coating film) Other than that, a barrier film, a laminate, and a packaged product were produced in the same manner as in Example 7 above in the same manner as in Example 7 above.

(Comparative Example 8)
In Example 8 above, after coating the gas barrier composition to form a gas barrier coating film, instead of forming a plasma treated surface by plasma treatment on the surface of the gas barrier coating film, After coating the conductive composition, an aging treatment is performed at 55 ° C. for 3 days to form a gas barrier coating film (that is, a plasma-treated surface by plasma processing is not formed on the surface of the gas barrier coating film) Other than that, a barrier film, a laminate, and a packaged product were produced in the same manner as in Example 8 above, in the same manner as in Example 8 above.

(Experimental example 1)
About the barrier film manufactured in said Examples 1-8 and Comparative Examples 1-8, and the laminated material using the same, oxygen permeability and water vapor permeability were measured.
(1). Measurement of Oxygen Permeation This is a measuring film manufactured by MOCON, USA (model name, OX-TRAN 2/20) under the conditions of a temperature of 23 ° C. and a humidity of 90% RH for barrier films and laminates. )].
(2). Measurement of water vapor transmission rate This is a measuring instrument manufactured by MOCON Co., USA under the conditions of a barrier film and a laminated material at a temperature of 40 ° C. and a humidity of 90% RH [model name, PERMATRAN 3/31 )].
The measurement results are shown in Table 5 below.

(Table 5)
┌────┬────────────┬────────────┐ │ │ Barrier film │ Laminate │ │ ├ ─────┬─ ─────├─────┬──────┤ │ │ Oxygen permeability │ Water vapor permeability │ Oxygen permeability │ Water vapor permeability │ ├────┼─────┼─ ─────┼─────┼──────┤ │Example 1│ 0.8 │ 3.2 │ 0.6 │ 1.8 │ ├ ────┼──── ─┼──────┼─────┼──────┤ │Example 2│ 0.3 │ 0.9 │ 0.3 │ 0.4 │ ├────┼─ ────┼──────┼─────┼──────┤ │Example 3│ 0.3 │ 0.8 │ 0.3 │ 0.3 │ ├─── ─┼─────┼──────┼─────┼──────┤ │Example 4│ 0.3 │ 0.8 │ 0.3 │ 0. 4 │ ├────┼─────┼──────┼─────┼──────┤ │Example 5│ 0.8 │ 3.8 │ 0.6 │ 2.1 │ ├────┼─────┼──────┼─────┼──────┤ │Example 6│ 0.4 │ 1.2 │ 0.3 │ 0.4 │ ├────┼─────┼──────┼─────┼──────┤ │Example 7│ 0.4 │ 1 .3 │ 0.3 │ 0.4 │ ├────┼─────┼──────┼─────┼──────┤ │Example 8│ 0. 4 │ 1.1 │ 0.3 │ 0.4 │ ├────┼─────┼──────┼─────┼──────┤ │Comparative Example 1 │ 0.8 │ 6.4 │ 0.8 │ 4.8 │ ├────┼─────┼──────┼─────┼──────┤ Comparative Example 2 | 0.3 | 4 │ 0.3 │ 1.2 │ ├────┼─────┼──────┼─────┼──────┤ │Comparative Example 3│ 0. 3 │ 1.5 │ 0.3 │ 1.2 │ ├────┼─────┼──────┼─────┼──────┤ │Comparative Example 4 │ 0.3 │ 1.4 │ 0.3 │ 1.2 │ ├────┼─────┼──────┼─────┼──────┤ │ Comparative Example 5│ 0.8 │ 5.9 │ 0.8 │ 4.6 │ ├────┼─────┼──────┼─────┼────── ─┤ │Comparative Example 6│ 0.4 │ 2.1 │ 0.3 │ 1.8 │ ├────┼─────┼──────┼─────┼── ────┤ │Comparative Example 7│ 0.4 │ 1.8 │ 0.3 │ 1.5 │ ├────┼─────┼──────┼───── ┼──────┤ │ Comparative Example 8│ 0.4 │ 1.8 │ 0.3 │ 1.6 │ └────┴─────┴──────┴─────┴───── In Table 5 above, the unit of oxygen permeability is [cc / m ² / day · 23 ° C./90% RH], and the unit of water vapor permeability is [g / m ² / day · 40 ° C. 90% RH].

  As is clear from the results shown in Table 5 above, the barrier film and laminate according to the present invention were excellent in water vapor permeability as well as oxygen permeability.

  The barrier film according to the present invention stably maintains an extremely high gas barrier property, and has good transparency, impact resistance, hot water resistance, etc., and further, spreadability, flexibility, flexibility, etc. In addition, it is useful as a barrier base material used for packaging materials, etc. without mixing foreign matter, dust, etc. that cause cracks, and other plastic films, A laminate material having various forms is produced by arbitrarily laminating one or more of various substrates such as a paper substrate, cellophane, woven fabric or nonwoven fabric, glass plate, and the like. For example, packaging material, optical member, protective sheet for solar cell module, protective film for organic EL display, protective film for film liquid crystal display, packaging material for polymer battery, or aluminum packaging Material, it is capable of various applications other like.

It is a schematic sectional drawing which shows an example of the layer structure about the barrier film which concerns on this invention. It is a schematic sectional drawing which shows an example of the layer structure about the barrier film which concerns on this invention. It is a schematic sectional drawing which shows an example of the layer structure about the laminated material which uses the barrier film which concerns on this invention shown in FIG. It is a schematic sectional drawing which shows an example of the layer structure about the laminated material which uses the barrier film which concerns on this invention shown in FIG. It is a schematic block diagram which shows an example of a low temperature plasma chemical vapor deposition apparatus. It is a schematic block diagram which shows an example of a winding-type vacuum deposition apparatus.

Explanation of symbols

A, A ₁ barrier film B, B ₁ barrier film 1 substrate film 2 gas barrier coating film 3 inorganic oxide vapor deposition film 4 plasma treated surface

Claims (11)

On one side of the base film, an inorganic oxide vapor deposition film is provided,
Furthermore, on the surface of the vapor-deposited film of the inorganic oxide, a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M Represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M), and at least one alkoxide represented by It contains a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer, and is obtained by polycondensation by the sol-gel method in the presence of a sol-gel method catalyst, acid, water, and an organic solvent. Provide a gas barrier coating film with a gas barrier composition,
Furthermore, a plasma treatment surface by plasma treatment is provided on the surface of the gas barrier coating film,
The barrier film is characterized in that the plasma treatment is performed using an inorganic gas containing oxygen gas as a plasma gas .   The barrier film according to claim 1, wherein the base film is a biaxially stretched polyester resin film, a biaxially stretched polyamide resin film, or a biaxially stretched polyolefin resin film. ^{3. The} barrier film according to claim 1, wherein M in the general formula R ¹ _n M (OR ² ) _m is made of silicon, zirconium, titanium, or aluminum. .   The barrier film according to any one of claims 1 to 3, wherein the alkoxide is composed of alkoxysilane.   The barrier film according to any one of claims 1 to 4, wherein the alkoxide comprises a hydrolyzate of alkoxide or a hydrolyzed condensate of alkoxide.   6. The barrier film according to any one of claims 1 to 5, wherein the gas barrier composition contains a silane coupling agent.   The barrier film according to any one of claims 1 to 6, wherein the gas barrier coating film is composed of a composite polymer layer in which one layer or two or more layers are laminated.   The base film on which the gas barrier coating film is coated with the gas barrier composition and provided with the coating film is 10 to 10 seconds at a temperature of 20 ° C. to 180 ° C. and below the melting point of the base film. The barrier film according to any one of claims 1 to 7, which comprises a cured film that has been heat-treated for a minute. The barrier property according to any one of claims 1 to 8 , wherein the inorganic oxide vapor-deposited film comprises an inorganic oxide vapor-deposited film formed by chemical vapor deposition or physical vapor deposition. the film. 10. The barrier film according to claim 9 , wherein the inorganic oxide vapor-deposited film is a silicon oxide vapor-deposited film formed by chemical vapor deposition. 10. The barrier film according to claim 9 , wherein the inorganic oxide vapor-deposited film comprises an aluminum oxide vapor-deposited film formed by physical vapor deposition.

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