JP2003326633A - Laminated material and packaging bag using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a barrier laminated material which is useful as a packing material and can decrease amounts of solid wastes of a container and packing by realizing excellent adhesion of the laminated material and reducing thickness of an extruded resin layer functioning as an adhesive layer for the laminated material to improve the barrier property, and to provide a packaging bag using the same. <P>SOLUTION: A barrier layer provided with a vapor deposition film of an inorganic oxide and a gas barrier coating film on one side surface of at least a substrate film or a substrate film for vapor deposition, and a heat sealing resin layer are successively laminated to provide the laminated material, and the packaging bag using the same is provided. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated material and a packaging bag using the laminated material, and more specifically to an extruded resin layer which is excellent in tight adhesion as a laminated material and serves as an adhesive layer for the laminated material. The present invention relates to a barrier laminated material which is useful as a packaging material capable of improving the barrier property by further reducing the thickness of the container and further reducing the amount of containers and packaging waste, and a packaging bag using the same. is there.

[0002]

2. Description of the Related Art Conventionally, as a laminated material as a packaging material for filling and packaging foods, etc., protection of flavor of foods,
Due to the extension of the storage period, it is often attempted to use a barrier film having a barrier property against oxygen and water vapor, such as a polyvinylidene chloride resin, an ethylene-vinyl alcohol copolymer, nylon 6MXD, etc. ing. Furthermore, in recent years, transparent vapor deposition barrier films have been widely used so that the contents can be confirmed. As a laminated material using the transparent vapor deposition barrier film, for example, a vapor deposition film of an inorganic oxide is provided on a biaxially stretched polyester resin film having a thickness of 12 μm, and the inorganic oxidation film is further formed. A printed pattern layer, an anchor-coating agent layer, a melt-extruded resin layer having a thickness of 15 μm using low-density polyethylene, etc., and a thickness of 30 on the vapor deposition film of the object.
A laminated material in which low-density polyethylene films or unstretched polypropylene films having a thickness of μm to 60 μm are sequentially laminated is known. Thus, in the above laminated material as a packaging material, a biaxially stretched polyester resin film having a thickness of 12 μm is a basic material constituting a laminated material or a packaging container. , Has a predetermined thickness, and has a predetermined strength in terms of mechanical, chemical or physical strength, for example, heat resistance, water resistance, light resistance, weather resistance, chemical resistance, etc. It is desirable that it is excellent in various fastness properties such as, and protects the contents and the like filled and packed. Further, in the above-mentioned laminated material as a packaging material, a vapor deposition film of an inorganic oxide provided on a biaxially stretched polyester resin film having a thickness of 12 μm has a barrier property of preventing permeation of oxygen, water vapor and the like ( It has a barrier property), is excellent in moisture-proof property, waterproof property, air-proof property, aroma retaining property, and the like, and has an action of protecting the contents and the like filled and packaged. Furthermore, in the laminated material as the packaging material as described above, the low-density polyethylene film or the unstretched polypropylene film having a thickness of 30 μm to 60 μm is mainly used when making a packaging container or the like.
It acts as a heat-sealable layer or the like to form a packaging container or the like. In addition, the print pattern layer is used for decoration, display,
The other functions are fulfilled, and the anchor coating agent layer, the melt-extruded resin layer and the like serve as an adhesive layer and the like when the laminated material is manufactured.

[0003]

However, in the barrier film as described above, for example, a laminated material using a barrier film made of polyvinylidene chloride resin has a gas barrier for preventing permeation of oxygen gas, water vapor and the like. However, when the flexible packaging bag is used as a packaging container and then disposed of as waste, for example, when it is disposed of by incineration, it contains chlorine atoms. Therefore, when incinerated, it may cause toxic gases such as dioxins, which may affect the human body.Therefore, it lacks suitability for disposal and causes environmental damage. Then
There is a problem that it lacks environmental suitability. Further, for example, a barrier film made of an ethylene-vinyl alcohol copolymer, a barrier film made of nylon 6MXD, and a multilayer coextrusion laminated film using them (for example, nylon / nylon 6MXD /
Nylon co-extruded film, nylon / ethylene vinyl alcohol copolymer / nylon co-extruded film, etc.)
Regarding the gas barrier property that prevents the permeation of water vapor, etc., it has the intended effect, but in the wet state, the gas barrier property that blocks the permeation of oxygen gas, water vapor, etc.
There is a problem that it is significantly lowered and can no longer be used. As a solution to the above-mentioned problems, a transparent vapor deposition barrier film provided with a vapor deposition film of an inorganic oxide is used, and it has excellent barrier properties to prevent the permeation of oxygen gas, water vapor, etc., and further, it is incinerated and disposed of after use. There is provided a laminated material which is excellent in waste disposal suitability, environmental suitability and the like without generating harmful substances and the like. However, when a laminated material is produced using the above transparent vapor deposition barrier film, the vapor deposition film of an inorganic oxide is an inorganic film, is a glassy film, is inactive, and is an extremely thin film. In addition, in the manufacturing process, there is a possibility that it will be damaged a little and the original barrier property cannot be exhibited. In particular, in a laminating method using a melt extruded resin layer widely used in the production of laminated materials as an adhesive layer, when the melt extruded resin layer is formed by melt extrusion at a high temperature of 300 ° C. or higher, Received the heat damage,
Further, when melt-extruded with a film thickness of 15 μm or more, there is a problem that the film is also subjected to thermal damage due to the film thickness, the barrier property thereof is deteriorated, and the dense adhesion property is lacking. For example, in a melt extruded resin layer using low density polyethylene, in order to obtain the flow characteristics of the melt extruded resin, it is necessary to melt extrude at about 320 ° C., at least 300 ° C. or more, and In order to obtain a molten extruded resin layer, it is extremely difficult to reduce the film thickness to 15 μm or less as described above. The thermal damage to the transparent vapor deposition barrier film is due to the synergistic effect of the melting temperature and the film thickness, and the problem is to reduce the film thickness and lower the temperature. Further, when another substrate is laminated on the surface of the vapor-deposited film of the transparent vapor-deposited barrier film, there is a problem in that it lacks in dense adhesion, laminar strength, etc. and causes delamination. In recent years, the amount of garbage in containers and packaging has increased, and it is said that this is a cause of environmental damage, and it is necessary to deal with it. As a priority order for the response, reduction is the highest priority, and reduction of the amount of materials for containers and packaging is an issue. Therefore, the present invention has an object to solve the above-mentioned problems, and is excellent in dense adhesion as a laminated material and thinned the extruded resin layer serving as an adhesive layer for the laminated material, thereby forming a barrier layer. To improve
Further, the present invention provides a barrier laminate which is useful as a packaging material capable of reducing the amount of containers and packaging waste, and a packaging bag using the same.

[0004]

As a result of various studies to solve the above-mentioned problems, the present inventor has made the melt-extruded resin layer into a thin film and lowers the melting temperature to thereby form a barrier of a transparent vapor deposition barrier film. The present invention has been completed without deteriorating the property and enabling the reduction of container / packaging waste. That is, the present invention focuses on the ethylene-methacrylic acid copolymer as the melt-extruded resin layer,
Further, this is melt extruded at about 290 ° C. to obtain a thickness of 2 to 10
A melt extruded resin layer of about μm can be formed, and
Through this, on the surface of the vapor-deposited film of the transparent vapor-deposited barrier film, for example, it is possible to laminate a heat-sealable resin layer such as low-density polyethylene or unstretched polypropylene, and at least the substrate A film, a barrier layer in which a vapor deposition film of an inorganic oxide and a gas barrier coating film are provided on one surface of a substrate film for vapor deposition, and a heat sealable resin layer are, for example, the above-mentioned substrate film. And a barrier layer in which a vapor deposition film of an inorganic oxide and a gas barrier coating film are provided on one surface of a substrate film for vapor deposition has a gas barrier property that constitutes the one surface of the substrate film and the barrier layer. Face the surface of the coating film, the interlayer, through the extruded resin layer,
Alternatively, the barrier layer in which a vapor deposition film of an inorganic oxide and a gas barrier coating film are provided on one surface of the above vapor deposition base material film, and the heat sealable resin layer are the barrier layers. The surface of the gas barrier coating film and the surface of the heat-sealable resin layer that constitute the layer are opposed to each other, and the layers are sequentially laminated via the extruded resin layer to produce a laminated material, and thus, Using the laminated material, this is made into a bag to produce a packaging bag, and further,
In the packaging bag, for example, when a packed product is manufactured by filling and packaging articles such as confectionery, snack foods, and the like,
The above laminated material has excellent barrier performance against oxygen and water vapor,
Further, it has excellent laminating strength and the like, delamination and the like are not observed, and further, heat sealing performance and the like are excellent. A packaging bag manufactured using this is mechanical, chemical, or It has a predetermined physical strength and the like, for example, heat resistance, water resistance, light resistance, weather resistance, chemical resistance, puncture resistance, and other various fastnesses, and further moisture resistance,
It is excellent in waterproof, air-proof, aroma-retaining, heat-insulating, etc., fully protects the contents packed and packed, and has excellent storage, storage stability, suitability for packing and packaging, and a packaging bag. A laminated material as a very useful packaging material that can reduce the thickness of each material constituting the laminated material to be formed and reduce the amount of the container / packaging waste, and a packaging bag using the same That is, the present invention has been completed.

That is, according to the present invention, at least a substrate film, a barrier layer in which a vapor deposition film of an inorganic oxide and a gas barrier coating film are provided on one surface of a vapor deposition substrate film, and a heat sheet. TECHNICAL FIELD The present invention relates to a laminated material characterized by sequentially laminating a flexible resin layer and a packaging bag using the laminated material.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The laminated material according to the present invention and the packaging bag using the same will be described below in more detail with reference to the drawings. 1, 2, and 3 are schematic cross-sectional views showing a few examples of the layer structure of the laminated material according to the present invention, and FIG. 4 uses the laminated material according to the present invention shown in FIG. Is a schematic perspective view showing an example of a packaging bag made of flexible packaging bag or the like formed by
FIG. 5 is a schematic perspective view showing an example of a packaged product obtained by filling and packaging the contents in a packaging bag such as the flexible packaging bag shown in FIG.

First of all, as shown in FIG. 1, the laminated material A according to the present invention has a vapor deposition film 3 of inorganic oxide and a gas barrier coating film 4 on one surface of the substrate film 1 and the vapor deposition substrate film 2. The basic structure is a structure in which the barrier layer 5 provided with and the heat-seal resin layer 6 are sequentially laminated. As a specific example of the laminated material according to the present invention, as shown in FIG.
The printed pattern layer 7 is provided on the back surface of the substrate, and the substrate film 1 provided with the printed pattern layer 7 and the vapor deposition film 3 of inorganic oxide and the gas barrier coating film 4 on one surface of the vapor deposition substrate film 2. And the barrier layer 5 provided with are arranged such that one surface including the print pattern layer 7 provided on the base film 1 and the surface of the gas barrier coating film 4 constituting the barrier layer 5 are opposed to each other, and As shown in FIG. 1 above, a vapor deposition film 3 of inorganic oxide and a gas barrier coating film 4 are provided on one surface of the base film 1 and the vapor deposition base film 2 via the extruded resin layer 8. It is possible to exemplify the laminated material A ₁ according to the present invention, which has a structure in which the barrier layer 5 and the heat-sealable resin layer 6 are sequentially laminated.

Furthermore, regarding another specific example of the laminated material according to the present invention, as shown in FIG. 3, first, a printed pattern layer 7 is provided on the back surface of the base material film 1, and further, a vapor deposition base material. The barrier layer 5 in which the vapor deposition film 3 of the inorganic oxide and the gas barrier coating film 4 are provided on one surface of the film 2 and the heat-sealing resin layer 6 constitute the barrier layer 5. The surface of the gas barrier coating film 4 and the surface of the heat-sealable resin layer 6 are opposed to each other, and the interlayer is interposed via the extruded resin layer 8 as shown in FIG. A structure in which a barrier layer 5 in which a vapor deposition film 3 of an inorganic oxide and a gas barrier coating film 4 are provided on one surface of a vapor deposition base material film 2 and a heat sealable resin layer 6 are sequentially laminated. The laminated material A _{2 according} to the present invention can be exemplified. The above exemplifications exemplify a few examples of the laminated material according to the present invention, and the present invention is not limited thereto. For example, although not shown, in the above-mentioned laminated material according to the present invention, if necessary, another substrate such as a plastic film can be optionally laminated. Further, although not shown, in the above-mentioned laminated material according to the present invention, the vapor deposition film of an inorganic oxide can be formed by stacking vapor deposition films of two or more inorganic oxides of the same kind or different kinds. Is. Further, although not shown, in the laminated material shown in FIG. 2, when a heat-sealable resin layer is laminated on the surface of the vapor deposition substrate film forming the barrier layer, or in the case of FIG. In the case of laminating the base material film on the surface of the vapor deposition base material film forming the barrier layer in the laminated material shown in (1), of course, it can be laminated via the extruded resin layer as described above. Needless to say, in addition, for example, a melt extrusion laminating method of laminating via an anchor coating agent layer, a melt extruded resin layer or the like, or laminating via a laminate adhesive layer or the like. It can also be laminated using a dry lamination method or the like.

Next, in the present invention, a case of using the laminated material A according to the present invention shown in FIG. Exemplifying and explaining, as shown in FIG. 4, first, for example, the laminated material A according to the present invention shown in FIG.
Of the heat-sealable resin layers 6 and 6 are opposed to each other, and the end portions around the outer periphery of the heat-sealable resin layers 6 and 6 are heat-sealed. , 9 and 9 and an opening 10 formed at the upper end thereof, and made into a bag by using the laminated material A according to the present invention, which is a three-way seal type soft packaging bag 11. A packaging bag B including the packaging bag 11 and the like is manufactured. Next, in the present invention, as shown in FIG. 5, a bag-making process using the laminated material A according to the present invention, which comprises the above-described bag-making bag 11 of the three-way seal type shown in FIG. For example, the contents 12 such as confectionery, snack foods, etc. are filled from the opening 10 of the packaging bag B, and then the opening 10 is heat-sealed to seal the upper sheet.
To produce a packaged product C using a packaging bag B formed of a flexible packaging bag 11 and the like formed by using the laminated material A according to the present invention. Is what you can do. It goes without saying that the above-mentioned exemplification is one example of the packaging bag using the laminated material according to the present invention, and the present invention is not limited thereto. For example, in the present invention, although not shown, the laminated material according to the present invention shown in FIGS. 2 to 3 is used, and the laminated material according to the present invention is used in the same manner as above. It is possible to manufacture a packaging bag that has been made into a bag. Further, in the present invention, although not shown, as the form of the packaging bag made of the above soft packaging bag, instead of the packaging bag made of the three-way seal type soft packaging bag as described above, For example, two-way
It is possible to make and use a packaging bag made of a flexible packaging bag having a shape such as a leu-type, a gusset seal type, a self-supporting type, a horizontal or vertical pillow-wrapping type, and the like. .

Next, in the present invention, a description will be given of the above-mentioned laminated material according to the present invention, the material constituting the packaging bag and the like, the manufacturing method thereof and the like. First, the laminated material according to the present invention, the packaging bag and the like will be described. The base material film to be constituted has excellent strength, rigidity, etc. in mechanical, physical, chemical, etc. because it is a basic material constituting the laminated material, packaging bag, etc. according to the present invention. However, for example, a resin film or sheet having excellent heat resistance, water resistance, light resistance, weather resistance, chemical resistance, pinhole resistance, puncture resistance, transparency, etc. Can be used. Specifically, for example, a film of a tough resin such as polyester resin, polyamide resin, polyaramid resin, polypropylene resin, polycarbonate resin, polyacetal resin, fluorine resin, etc. Sheets can be used. As the resin film or sheet, either an unstretched film or a stretched film uniaxially or biaxially stretched can be used. Further, in the present invention, as the thickness of the resin film or sheet,
It is only necessary to have the minimum necessary thickness that can maintain the above-mentioned various solidities, and if it is too thick, it will be difficult to achieve the objectives of thinning, weight reduction, etc., and further, the cost will increase. On the contrary, if it is too thin, it is not preferable because the various fastnesses mentioned above and the like are deteriorated. In the present invention, for the reasons described above, the thickness of the base film is most preferably within the range of about 6 μm to 20 μm. Thus, in the present invention, as the substrate film, specifically, a biaxially oriented polypropylene film having a thickness of 15 μm, a biaxially oriented polyethylene terephthalate film having a thickness of 12 μm, or a biaxially oriented film having a thickness of 15 μm is used. It is preferable to use a stretched nylon film or the like.

Thus, in the present invention, a desired printed pattern consisting of, for example, characters, figures, symbols, patterns, etc. is printed on one surface of either the front surface or the back surface of the substrate film. Thus, the printed pattern layer can be formed. The above-mentioned printed pattern layer contains, as a main component, one or more ordinary ink vehicles, and if necessary, a plasticizer, a stabilizer, an antioxidant, a light stabilizer, an ultraviolet absorber, a curing agent. One or more kinds of additives such as agents, cross-linking agents, lubricants, antistatic agents, fillers, etc. are optionally added, and further colorants such as dyes and pigments are added,
A solvent, a diluent, etc. are sufficiently kneaded to prepare an ink composition, and then the ink composition is used, for example, gravure printing, offset printing, letterpress printing, screen printing,
Using printing methods such as transfer printing, flexographic printing, etc., characters, figures, symbols, on one side of the above base film,
It is possible to form a printed pattern layer according to the present invention by printing a desired printed pattern including a pattern and the like.

In the above, as the ink vehicle,
Known substances such as linseed oil, cutting oil, soybean oil, hydrocarbon oil, rosin, rosin ester, rosin modified resin, shellac, alkyd resin, phenol resin, maleic acid resin, natural resin, hydrocarbon resin , Polyvinyl chloride resin, polyvinyl acetate resin, polystyrene resin, polyvinyl butyral resin, acrylic or methacrylic resin, polyamide resin, polyester resin, polyurethane resin, epoxy resin, urea resin, melamine One or more of resins, aminoalkyd resins, nitrocellulose, ethylcellulose, chlorinated rubber, cyclized rubber, and the like can be used.

Next, in the present invention, as the vapor deposition base material film constituting the laminated material, the packaging bag, etc. according to the present invention, a vapor deposition film of an inorganic oxide is provided on the vapor deposition base material film. It is possible to use a resin film or sheet which has excellent properties in terms of chemical properties and the like, and particularly has strength and toughness and heat resistance. Specifically, in the present invention, as the vapor deposition substrate film, for example, polyethylene resin, polypropylene resin, cyclic polyolefin resin, fluorine resin,
Polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-
Styrene copolymer (ABS resin), polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin, polyethylene terephthalate, polyethylene naphthalate, and other polyester resins. Resin, polyamide resin such as various nylon, polyimide resin,
Polyamideimide-based resin, polyarylphthalate-based resin, silicone-based resin, polysulfone-based resin, polyphenylene sulfide-based resin, polyethersulfone-based resin, polyurethane-based resin, acetal-based resin, cellulose
Films or sheets of various resins such as glass-based resins and others
Can be used. In the present invention,
In particular, it is preferable to use a polypropylene resin, polyester resin, or polyamide resin film or sheet.

In the present invention, as the film or sheet of the above-mentioned various resins, for example, one or more of the above-mentioned various resins is used, and an extrusion method, a cast molding method, a T-die method, a cutting method is used. Method, film formation method such as inflation method, etc., to form a film of each of the above resins alone, or multilayer coextrusion film formation using two or more kinds of resins. Film or sheet of various resins is produced by a method of forming a resin, and a method of forming a film by mixing two or more kinds of resins and mixing them before forming a film. For example, various resin films or sheets obtained by uniaxially or biaxially stretching using a tenter system or a tuber system can be used. In the present invention, the film thickness of various resin films or sheets is 6 to 100 μm.
Position, more preferably about 9 to 50 μm.

It should be noted that, when one or more of the above various resins are used, and when forming a film, for example, the processability of the film, heat resistance, weather resistance, mechanical properties, dimensional stability,
Various plastic compounding agents and additives may be added for the purpose of improving and modifying antioxidative properties, slipperiness, releasability, flame retardancy, antifungal properties, electrical properties, strength, etc. You can
The addition amount thereof can be arbitrarily added from a very small amount to several tens of% depending on the purpose. In the above, as a general additive, for example, a lubricant, a crosslinking agent,
Antioxidants, ultraviolet absorbers, light stabilizers, fillers, antistatic agents, lubricants, anti-blocking agents, coloring agents such as dyes and pigments, and the like can be used, and further, modifying resins and the like. Can also be used.

Further, in the present invention, the surface of the film or sheet of the above various resins is, if necessary, in order to improve the close adhesion to a vapor deposition film of an inorganic oxide described later, etc. 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, Pretreatments such as others can be optionally performed to form, for example, a corona treatment layer, an ozone treatment layer, a plasma treatment layer, an oxidation treatment layer, and the like. The above-mentioned surface pretreatment is carried out as a method for improving the close adhesion property between various resin films or sheets and the inorganic oxide vapor deposition film described later. As a method of improving the above, other methods, for example, various resin films or sheets
In advance, a primer-coating agent layer, an under-coating agent layer, an anchor-coating agent layer, an adhesive layer, or
A vapor-deposited anchor coating agent layer or the like may be optionally formed to form the surface-treated layer. Examples of the pretreatment coating agent layer include polyester resin, polyamide resin, polyurethane resin, epoxy resin, phenol resin, (meth) acrylic resin, polyvinyl acetate resin, A resin composition containing a polyolefin resin such as polyethylene or polypropylene, a copolymer or modified resin thereof, a cellulose resin, or the like as a main component of the vehicle can be used.

Next, in the present invention, the vapor deposition film of the inorganic oxide which constitutes the laminated material, the packaging bag and the like according to the present invention will be explained. Examples of the vapor deposition film of the inorganic oxide include chemical vapor deposition. Method, or physical vapor deposition method, or a combination of both methods, to form a monolayer film composed of one layer of a vapor deposition film of an inorganic oxide or a multilayer film or composite film composed of two or more layers to produce the film. Is something that can be done.

In the present invention, the deposition film of the inorganic oxide by the chemical vapor deposition method will be described in more detail. Examples of the deposition film of the inorganic oxide by the chemical vapor deposition method include plasma chemical vapor deposition. Chemical vapor deposition (Che, chemical vapor deposition, photochemical vapor deposition, etc.)
medical vapor deposition method, C
A vapor deposition film of an inorganic oxide can be formed by using the VD method) or the like. In the present invention, specifically, on one surface of the substrate film for vapor deposition, a monomer gas for vapor deposition such as an organic silicon compound is used as a raw material, and an inert gas such as argon gas or helium gas is used as a carrier gas. And further using oxygen gas or the like as an oxygen supply gas, and forming a deposited film of an inorganic oxide such as silicon oxide by low temperature plasma chemical vapor deposition using a low temperature plasma generator or the like. You can In the above, as the low temperature plasma generator, for example, a generator such as a high frequency plasma, a pulse wave plasma or a microwave plasma may be used, and therefore, in the present invention, a highly active and stable plasma is obtained. For this purpose, it is desirable to use a high frequency plasma type generator.

A specific example of the method for forming a deposited film of an inorganic oxide by the above-mentioned low temperature plasma-enhanced chemical vapor deposition method will be described by way of example. FIG. 1 is a schematic configuration diagram of a low temperature plasma chemical vapor deposition apparatus showing an outline of a method for forming an oxide vapor deposition film. As shown in FIG. 6 above, in the present invention, the vacuum chamber of the plasma enhanced chemical vapor deposition apparatus 21--
The substrate film 2 for vapor deposition is unwound from the unwinding roll 23 disposed inside the substrate 22, and the substrate film 2 for vapor deposition is further provided.
Is conveyed onto the peripheral surface of the cooling / electrode drum 25 at a predetermined speed via the auxiliary roll 24. In the present invention, therefore, oxygen gas, an inert gas, a monomer gas for vapor deposition of an organic silicon compound, and the like are supplied from the gas supply devices 26 and 27, the raw material volatilization supply device 28, and the like, and from them. The mixed gas composition for vapor deposition is adjusted, and then the mixed gas composition for vapor deposition is introduced into the vacuum chamber 22 through the raw material supply nozzle 29, and the cooling / electrode drum 25 is used.
Plasma is generated by glow discharge plasma 30 on the substrate film 2 for vapor deposition conveyed on the peripheral surface, and this is irradiated to form a vapor deposition film of an inorganic oxide such as silicon oxide. In the present invention, at this time, the cooling / electrode drum 25 is applied with a predetermined electric power from the power source 31 arranged outside the vacuum chamber-22, and the cooling / electrode drum 25 is provided near the cooling / electrode drum 25. The magnet 32 is arranged to promote the generation of plasma. Next, the vapor deposition base material film 2 on which the vapor deposition film of the inorganic oxide such as silicon oxide is formed is wound on the winding roll 34 via the auxiliary roll 33, and the plasma chemistry according to the present invention. It is possible to form a vapor deposition film of an inorganic oxide by a vapor phase growth method. In the figure, 35 represents a vacuum pump. It is needless to say that the above-mentioned exemplification is one example, and the present invention is not limited thereby. Although not shown, in the present invention, the vapor deposition film of the inorganic oxide may be not only one layer of the vapor deposition film of the inorganic oxide but also a multi-layered film in which two or more layers are laminated and used. The materials may be used singly or in a mixture of two or more kinds, and it is also possible to form a vapor deposition film of an inorganic oxide in which different materials are mixed.

In the above, the inside of the vacuum chamber is vacuumed.
The pressure is reduced by a pump and the degree of vacuum is 1 × 10. ^-1~ 1 x 10^-8To
rr position, preferably vacuum degree 1 × 10^-3~ 1 x 10^-7T
It is desirable to prepare it at the orr position. Also,
In the raw material volatilization supply device, the raw material organosilicon compound
Oxygen gas that volatilizes things and is supplied from the gas supply device,
It is mixed with an inert gas, etc.
It is introduced into the vacuum chamber via a cable.
In this case, the content of the organosilicon compound in the mixed gas is 1
-40%, oxygen gas content is 10-70%,
The content of active gas should be in the range of 10-60%
For example, an organic silicon compound, oxygen gas and an inert gas
The mixing ratio with the soot is about 1: 6: 5 to 1:17:14.
be able to. On the other hand, from the power supply to the cooling and electrode drum
Since a predetermined voltage is applied, the inside of the vacuum chamber
In the vicinity of the opening of the raw material supply nozzle and the cooling / electrode drum
A glow discharge plasma is generated, and this glow discharge plasma is generated.
Ma is derived from one or more gas components in a gas mixture
In this state, the vapor deposition base material film is
It is transported at a constant speed and cooled by a glow discharge plasma
On the base film on the outer surface of the electrode drum, silicon oxide
Which can form a vapor-deposited film of inorganic oxides such as
is there. The degree of vacuum in the vacuum chamber at this time is
1 x 10^-1~ 1 x 10^-FourTorr position, preferably vacuum
1 × 10^-1~ 1 x 10^-2Can be adjusted to Torr position
Desirably, the transport speed of the vapor deposition substrate film is 1
0 to 300 m / minute, preferably 50 to 150 m / minute
It is desirable to adjust the position.

Further, in the above-described plasma enhanced chemical vapor deposition apparatus, the formation of a vapor deposition film of an inorganic oxide such as silicon oxide is performed by oxidizing a plasma-processed source gas with oxygen gas on a vapor deposition substrate film. Since it is formed into a thin film in the form of SiO _x , the formed vapor-deposited film of an inorganic oxide such as silicon oxide is a dense, small gap, and flexible continuous layer. The barrier property of a vapor deposited film of an inorganic oxide such as silicon oxide is much higher than that of a vapor deposited film of an inorganic oxide such as silicon oxide formed by a conventional vacuum vapor deposition method, etc. It is possible to obtain a sufficient barrier property. Further, in the present invention, SiO
The surface of the vapor deposition substrate film is cleaned by _X plasma, and polar groups and frees are formed on the surface of the vapor deposition substrate film.
Since radicals and the like are generated, there is an advantage that dense adhesion between the formed vapor deposition film of an inorganic oxide such as silicon oxide and the vapor deposition base material film is high. Furthermore,
As described above, the degree of vacuum at the time of forming a continuous film of an inorganic oxide such as silicon oxide is 1 × 10 ^-1 to 1 × 10 ^-4 Torr, preferably 1 × 10 ^-1 to 1 × 10 ^-2. The degree of vacuum is 1 × 10 ⁻⁴ to 1 × when a vapor deposition film of an inorganic oxide such as silicon oxide is formed by a conventional vacuum vapor deposition method, since it is adjusted to the Torr position.
Since the degree of vacuum is lower than that of 10 ⁻⁵ Torr,
This has the advantage that the vacuum state setting time at the time of exchanging the substrate film for vapor deposition can be shortened, the degree of vacuum can be easily stabilized, and the film forming process can be stabilized.

In the present invention, a vapor deposition film of silicon oxide formed by using a vapor deposition monomer gas such as an organic silicon compound causes a chemical reaction between a vapor deposition monomer gas such as an organic silicon compound and oxygen gas, and the like. The reaction product is closely adhered to one surface of the substrate film for vapor deposition to form a dense thin film having a high flexibility, and is generally represented by the general formula SiO _x (where X is 0 to 2). Is a continuous thin film mainly composed of silicon oxide. And Thus, the deposited film of the silicon oxide, transparency, from the viewpoint of the barrier property and the like, the general formula SiO _X (provided that, X represents represents. A number of 1.3 to 1.9) are represented by It is preferable that the thin film mainly comprises a vapor-deposited film of silicon oxide. In the above, the value of X changes depending on the molar ratio of vapor deposition monomer gas and oxygen gas, the energy of plasma, etc. Generally, the smaller the value of X, the smaller the gas permeability, but the film itself. Becomes yellowish and the transparency becomes poor.

The silicon oxide vapor-deposited film is mainly composed of silicon oxide, and further contains at least one compound of carbon, hydrogen, silicon or oxygen, or a compound consisting of two or more of these elements. It is characterized in that it is composed of a vapor-deposited film containing types by chemical bonding or the like. For example,
When the compound having a C—H bond, the compound having a Si—H bond, or the carbon unit is in a graphite form, a diamond form, a fullerene form, or the like, a raw material organosilicon compound or a derivative thereof It may be contained by a chemical bond or the like. To give a specific example, CH
Hydrocarbon with ₃ sites, SiH ₃ silyl, Si
Examples thereof include hydrosilica such as H ₂ silylene and hydroxyl group derivatives such as SiH ₂ OH silanol. In addition to the above, the type, amount, etc. of the compound contained in the vapor deposition film of silicon oxide can be changed by changing the conditions in the vapor deposition process. The content of the above compound in the vapor deposited film of silicon oxide is 0.1 to 5
About 0%, preferably about 5 to 20% is desirable. In the above, if the content rate is less than 0.1%,
The impact resistance, spreadability, flexibility, etc. of the vapor-deposited film of silicon oxide are insufficient, and when it is bent, scratches, cracks, etc. easily occur, and it becomes difficult to stably maintain high barrier properties, On the other hand, if it exceeds 50%, the barrier property is deteriorated, which is not preferable. Further, in the present invention, it is preferable that the content of the above compound in the vapor-deposited film of silicon oxide be decreased in the depth direction from the surface of the vapor-deposited film of silicon oxide. On the surface of, the impact resistance and the like can be enhanced by the above compounds and the like, while on the other hand, at the interface with the substrate film for vapor deposition, since the content of the above compound is small, the substrate film for vapor deposition and silicon oxide can be This has the advantage that the tight adhesion with the vapor-deposited film becomes strong.

Therefore, in the present invention, the above-mentioned vapor-deposited film of silicon oxide is, for example, an X-ray photoelectron spectrometer (Xr
ay Photoelectron Spectros
copy, XPS), secondary ion mass spectrometer (Sec)
onary Ion Mass Spectrosc
The above physical properties are confirmed by performing elemental analysis of the vapor-deposited film of silicon oxide by using a method of analyzing by ion etching in the depth direction using a surface analyzer such as can do. Further, in the present invention, the film thickness of the vapor deposition film of silicon oxide is preferably 50 Å to 4000 Å, specifically, the film thickness is preferably 100 to 1000 Å. Then, in the above, 1000Å, and further 40
If it is thicker than 00Å, cracks and the like are likely to occur in the film, which is not preferable.
When it is less than 0Å, it is difficult to exert the effect of barrier property, which is not preferable. In the above, the film thickness can be measured by the fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name, RIX2000 type) manufactured by Rigaku Co., Ltd. Further, in the above, as a means for changing the film thickness of the above-mentioned vapor-deposited film of silicon oxide, increasing the volumetric velocity of the vapor-deposited film, that is, a method of increasing the amount of monomer gas and oxygen gas or a vapor deposition rate is used. It can be done by a method such as slowing down.

Next, in the above, as the vapor deposition monomer gas of the organic silicon compound or the like for forming the vapor deposition film of the inorganic oxide such as silicon oxide, for example, 1.1.3.3-tetramethyldisiloxane, Hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxy Silane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, etc. can be used. In the present invention, among the above-mentioned organic silicon compounds, it is preferable to use 1.1.3.3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material for its handleability and formed continuous film. It is a particularly preferable raw material in view of the characteristics and the like. Further, in the above, as the inert gas, for example, argon gas, helium gas or the like can be used.

Next, in the present invention, the inorganic oxide vapor deposition film by the above physical vapor deposition method will be described in more detail. Examples of the inorganic oxide vapor deposition film by the physical vapor deposition method include vacuum vapor deposition. Method, sputtering method,
Physical vapor deposition methods such as an ion plating method and an ion cluster beam method (Physical Vapor Deposition)
A deposition film of an inorganic oxide can be formed by using a position method or a PVD method). In the present invention, specifically, a metal oxide is used as a raw material, a vapor deposition method in which this is heated and vaporized, and this is vapor-deposited on one of the substrate films for vapor deposition, or a metal or a metal as a raw material. The oxidation reaction vapor deposition method in which oxygen is introduced to oxidize and deposit on one side of the vapor deposition substrate film, and the plasma-assisted oxidation reaction vapor deposition method in which the oxidation reaction is plasma-assisted are used. It can be used to form a vapor deposited film. 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, a specific example of the method for forming a thin film of an inorganic oxide by physical vapor deposition is given. FIG. 7 is a schematic configuration diagram showing an example of a winding type vacuum vapor deposition apparatus. Is. As shown in FIG. 7, in the vacuum chamber-42 of the take-up type vacuum vapor deposition device 41, the vapor deposition substrate film 2 fed from the unwind roll 43 is
It is guided to the cooled coating drum 46 via the guide rollers 44 and 45. Then, the vapor deposition source 48 heated by the crucible 47, for example, metal aluminum or aluminum oxide is evaporated on the vapor deposition substrate film 2 guided on the cooled coating drum 46. Further, if necessary, oxygen gas or the like is ejected from the oxygen gas outlet 49, and while supplying this, the mask 5
0, 50, for example, a vapor deposition film of an inorganic oxide such as aluminum oxide is formed, and then, in the above, for example, a vapor deposition base film 2 on which a vapor deposition film of an inorganic oxide such as aluminum oxide is formed. The guide rolls 51, 52
It is possible to form a vapor deposition film of an inorganic oxide by the physical vapor deposition method according to the present invention by sending it out through a winding roll 53 and winding it up. In addition, in the present invention, first, a vapor deposition film of the inorganic oxide of the first layer is formed by using the above-described winding type vacuum vapor deposition device, and then, the vapor deposition film of the inorganic oxide is similarly formed. On top of
By forming a vapor-deposited film of an inorganic oxide, or by using the above-described roll-up type vacuum vapor-deposition apparatus and connecting them in series, a vapor-deposited film of an inorganic oxide is continuously formed. It is possible to form a vapor deposition film of an inorganic oxide, which is a multilayer film having two or more layers.

In the above, as the vapor deposition film of the inorganic oxide, basically any thin film obtained by vapor deposition of a metal oxide can be used. For example, silicon (Si), aluminum (Al), magnesium (Mg). , Calcium (C
a), potassium (K), tin (Sn), sodium (N
It is possible to use a vapor deposition film of an oxide of a metal such as a), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), or yttrium (Y). Thus, preferred are silicon (Si), aluminum (A
Examples thereof include vapor deposited films of metal oxides such as l).
Thus, the above-mentioned vapor-deposited film of metal oxide can be referred to as a metal oxide such as silicon oxide, aluminum oxide, and magnesium oxide, and the notation is, for example, SiO _x , AlO _x. , MO such as MgO _x
X (However, in the formula, M represents a metal element, and the value of X is
Each metal element has a different range. ). Further, the range of the value of X is silicon (S
i) is 0 to 2, aluminum (Al) is 0 to 1.
5, magnesium (Mg) is 0 to 1, calcium (C
a) is 0 to 1, potassium (K) is 0 to 0.5, tin (Sn) is 0 to 2, and sodium (Na) is 0 to 0.
5, boron (B) is 0 to 1, 5, titanium (Ti) is
0-2, lead (Pb) is 0-1, zirconium (Zr)
Can range from 0 to 2 and yttrium (Y) can range from 0 to 1.5. In the above, when X = 0,
It is a perfect metal and is not transparent and cannot be used at all, and the upper limit of the range of X is a completely oxidized value. In the present invention, generally, other than silicon (Si) and aluminum (Al), there are few examples used, and silicon (Si) is 1.0 to 2.0 and aluminum (A).
As l), those having a value in the range of 0.5 to 1.5 can be used. In the present invention, the film thickness of the vapor deposition film of the inorganic oxide as described above varies depending on the metal used, the type of the metal oxide, and the like, but is, for example, 50 to 20.
It is desirable to form it by arbitrarily selecting it in the range of 00Å, preferably in the range of 100 to 1000Å. Further, in the present invention, the metal used as the vapor deposition film of the inorganic oxide, or the metal oxide to be used, is used in one kind or in a mixture of two or more kinds. It is also possible to configure a vapor deposition film.

By the way, in the present invention, for example, both the physical vapor deposition method and the chemical vapor deposition method are used in combination as the vapor deposition film of the inorganic oxide constituting the laminated material, the packaging bag and the like according to the present invention. It is also possible to form and use a composite film composed of two or more vapor deposition films of different kinds of inorganic oxides.
Thus, the composite film composed of two or more layers of the above-mentioned vapor-deposited films of different kinds of inorganic oxides is first formed on the substrate film for vapor deposition by the chemical vapor deposition method and is dense and highly flexible. A vapor-deposited film of an inorganic oxide capable of relatively preventing the occurrence of cracks is provided, and then a vapor-deposited film of an inorganic oxide formed by physical vapor deposition is provided on the vapor-deposited film of the inorganic oxide. It is desirable to form a vapor-deposited film of an inorganic oxide composed of a composite film composed of multiple layers. Of course, in the present invention,
Contrary to the above, on the substrate film for vapor deposition, first, the vapor deposition film of the inorganic oxide is provided by the physical vapor deposition method, and then by the chemical vapor deposition method, it becomes dense and flexible. It is also possible to provide a vapor-deposited film of an inorganic oxide which is rich and relatively capable of preventing the generation of cracks, thereby forming a vapor-deposited film of an inorganic oxide composed of a composite film composed of two or more layers.

Next, in the present invention, the product according to the present invention
About the gas barrier coating film that composes layer materials, packaging bags, etc.
In other words, such a gas barrier coating film is less
Even without polyvinyl alcohol resin [below (A)
Minutes. ] And the general formula R¹ _mM (OR²)_n...
(1) (wherein M represents a metal atom, R¹Are the same
R represents an organic group having 1 to 8 carbon atoms, R²Is the same
One or different, an alkyl group having 1 to 5 carbon atoms or carbon
Represents an acyl group or a phenyl group of the formulas 1 to 6, and m and
And n each represent an integer of 0 or more, and m + n is M
Represents valence. ) A metal alcoholate represented by
Hydrolyzate of alcoholate, condensation of the metal alcoholate
, A chelate compound of the metal alcoholate, the chelate
Selected from the group of compound hydrolysates and metal acylates
At least one kind [hereinafter referred to as (B) component. ] And
A coating film having a gas barrier property by using the gas barrier composition having
Can be used. In the above, gas barrier properties
It is preferable that the product contains a nitrogen-containing organic solvent.
In addition, inorganic fine particles [hereinafter referred to as (C) component. ]
It is also preferable to have. Also, the smell above
As the component (B), the component (B) is water or a parent with water.
After hydrolysis in a mixed solvent containing an aqueous organic solvent,
A gas barrier composition can be prepared by mixing with the component (A).
It is capable of

In the above gas barrier composition,
As the polyvinyl alcohol-based resin that constitutes the component (A), at least one selected from the group consisting of polyvinyl alcohol and ethylene / vinyl alcohol-based copolymers can be used. Of the above component (A), polyvinyl alcohol is generally obtained by saponifying polyvinyl acetate. The polyvinyl alcohol may be a partially saponified polyvinyl alcohol having an acetic acid group remaining of several tens of percent, a fully saponified polyvinyl alcohol having no acetic acid group remaining, or a modified polyvinyl alcohol having an OH group modified. It is not particularly limited. Specific examples of the polyvinyl alcohol include RS-110 (saponification degree = 99%, polymerization degree = 1,00), which is an RS polymer manufactured by Kuraray Co., Ltd.
0), Kuraray Poval LM-20SO manufactured by the same company (saponification degree = 40%, polymerization degree = 2,000), and Gohsenol NM-14 (saponification degree = 99) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
%, Degree of polymerization = 1,400) and the like can be used.
Further, among the component (A), the ethylene / vinyl alcohol copolymer is obtained by saponifying a copolymer of ethylene and vinyl acetate, that is, an ethylene-vinyl acetate random copolymer. The partial saponified product in which the acetic acid group remains several tens mol%, to the complete saponified product in which the acetic acid group remains only several mol% or the acetic acid group does not remain, is not particularly limited. From the viewpoint of gas barrier properties, the preferable saponification degree is 80 mol% or more,
More preferably, it is 90 mol% or more, and further preferably 9
It is 5 mol% or more. 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%. Specific examples of the ethylene / vinyl alcohol copolymer include Eval EP-F101 manufactured by Kuraray Co., Ltd. (ethylene content;
32 mol%), manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Soarnol D2908 (ethylene content; 29 mol%) and the like can be used.

The melt flow index of the polyvinyl alcohol resin constituting the above component (A) is 210
1 to 20 g / 10 under a condition of ℃ and load of 21.168N
Min, preferably 1-18 g / 10 min. These polyvinyl alcohol resins constituting (A) may be used alone or in combination of two or more. Further, the polyvinyl alcohol-based resin constituting the component (A) itself has a gas barrier property,
Excellent weather resistance, organic solvent resistance, transparency, gas barrier property after heat treatment, etc. In addition, in the polyvinyl alcohol-based resin constituting the component (A), when the coating film obtained from the gas barrier composition of the present invention is cured, the hydroxyl group present in the repeating unit derived from polyvinyl alcohol will be described later ( By co-condensing with the component B) and / or the component (C), excellent coating performance can be brought about. The ratio of the component (A) in the gas barrier composition of the present invention is
10 to 10,000 with respect to 100 parts by weight of the component (B) described later.
0 parts by weight, preferably 20 to 5,000 parts by weight, and more preferably 100 to 1,000 parts by weight. 10
If it is less than 1 part by weight, the resulting coating film tends to be cracked and the gas barrier property is deteriorated, whereas if it exceeds 10,000 parts by weight, the gas coating property is deteriorated under high humidity, which is not preferable. Is.

Next, as the component (B) used in the present invention, a metal alcoholate, a hydrolyzate of the metal alcoholate, and a condensate of the metal alcoholate represented by the above-mentioned general formula (1). A chelate compound of the metal alcoholate,
At least one selected from the group of hydrolysates of the chelate compounds and metal acylates can be used,
As the component (B), only one kind thereof may be used, or a mixture of any two or more kinds may be used. In addition, as the hydrolyzate of the metal alcoholate, it is not necessary that all OR ² contained in the metal alcoholate be hydrolyzed, and for example, only one of them is hydrolyzed, or two or more of them are hydrolyzed. May be hydrolyzed, or a mixture thereof. Further, the above-mentioned metal alcoholate condensate is one in which M-OH groups of the hydrolyzate of metal alcoholate are condensed to form an M-O-M bond, but in the present invention, the M-OH group is used. Does not need to be all condensed, and is a concept including a mixture of a small part of M-OH groups, a mixture of those having different degrees of condensation, and the like. Further, the above-mentioned metal alcoholate chelate compounds include metal alcoholates, β-diketones, β-ketoesters, hydroxycarboxylic acids, hydroxycarboxylic acid salts, hydroxycarboxylic acid esters,
It is obtained by a reaction with at least one compound selected from keto alcohol and amino alcohol. Among these compounds, it is preferable to use β-diketones or β-ketoesters, and specific examples thereof include:
Acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate-sec-
Butyl, acetoacetic acid-t-butyl, 2,4-hexane-
Dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane-dione, 5-methyl-hexane-dione and the like can be mentioned. Further, the hydrolyzate of the above chelate compound, like the hydrolyzate of the above metal alcoholate,
It is not necessary for all the OR ² groups contained in the chelate compound to be hydrolyzed, and for example, only one of them is hydrolyzed, or two or more are hydrolyzed.
Alternatively, it may be a mixture thereof. In the present invention, the component (B) is considered to function to form a cocondensate with the component (A).

As the metal atom represented by M in the above general formula (1), zirconium, titanium and aluminum can be mentioned as preferable ones, and titanium is particularly preferable. The monovalent organic group having 1 to 8 carbon atoms of R ¹ differs depending on whether the compound represented by the general formula (1) is a metal alcoholate or a metal acylate. In the case of metal alcoholate, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-
Alkyl groups such as butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group; acetyl group, propionyl group, butyryl group Acyl groups such as valeryl group, benzoyl group and trioyl group; vinyl group, allyl group, cyclohexyl group, phenyl group, glycidyl group,
In addition to (meth) acryloxy group, ureido group, amide group, fluoroacetamide group, isocyanate group, etc.,
Substituted derivatives of these groups and the like can be mentioned. R
The substituent in the substituted derivative of ¹ , for example, a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group, 3,
4-epoxycyclohexyl group, (meth) acryloxy group, ureido group, ammonium base and the like can be mentioned. However, the carbon number of R ¹ including these substituted derivatives is 8 or less including the carbon atoms in the substituent.
When the metal acylate is used, R ¹ has 1 carbon atom.
Examples of the monovalent organic group of to 8 include acyloxyl groups such as an acetoxyl group, a propionyloxyl group, a butyryloxyl group, a valeryloxyl group, a benzoyloxyl group and a trioyloxyl group. When two R ^{1 s} are present in the general formula (1), they may be the same or different.

The alkyl group having 1 to 5 carbon atoms for R ² is, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group. Group, n-pentyl group and the like, and examples of the acyl group having 1 to 6 carbon atoms include acetyl group, propionyl group, butyryl group, valeryl group and caproyl group. A plurality of R ^{2 s} in the general formula (1) may be the same or different from each other.

Among these components (B), specific examples of metal alcoholates and chelate compounds of metal alcoholates include (a). Tetra-n-butoxyzirconium, tri-n
-Butoxy ethyl acetoacetate zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium, n-butoxy tris (ethyl acetoacetate) zirconium, tetrakis (n-propyl acetoacetate) zirconium, tetrakis (acetylacetoacetate) Zirconium compounds such as zirconium and tetrakis (ethylacetoacetate) zirconium;

(B). Tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetra-t-butoxytitanium, di-i-propoxy bis (ethylacetoacetate) titanium, di-i-propoxy.
Bis (acetylacetate) titanium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (triethanolaminato) titanium, dihydroxybislactatertotitanium, dihydroxytitanium lactate, tetrakis (2 −
Titanium compounds such as ethylhexyloxy) titanium;

(C). Tri-i-propoxy aluminum, di-i-propoxy ethyl acetoacetate aluminum, di-i-propoxy acetyl acetonate aluminum, i-propoxy bis (ethyl acetoacetate) aluminum, i-propoxy bis (acetyl acetonate) ) Aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, aluminum compounds such as monoacetylacetonatobis (ethylacetoacetate) aluminum; and the like. Among these metal alcoholates and chelate compounds of metal alcoholates, preferred are tri-n-butoxyethyl acetoacetate zirconium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy. Bis (triethanolaminato) titanium, dihydroxy bislactetatotitanium, di-i-propoxy ethylacetoacetate aluminum and tris (ethylacetoacetate) aluminum can be mentioned, and particularly preferred compounds are di-i-propoxy. Titanium compounds such as bis (acetylacetonato) titanium, di-n-butoxy bis (triethanolaminato) titanium, and dihydroxy bislactate titanium.

Specific examples of the metal acylate include:
Dihydroxy titanium dibutyrate, di-i-propoxy titanium diacetate, di-i-propoxy titanium dipropionate, di-i-propoxy titanium dimaloniate, di-i-propoxy titanium dibenzoylate, di -N-butoxy zirconium diacetate, di-i-propylaluminum monomaloniate and the like can be mentioned, and a particularly preferred compound is dihydroxy.
Titanium compounds such as titanium dibutyrate and di-i-propoxy titanium diacetate. These (B) components may be used alone or in combination of two or more.

As the component (B), the viscosity of the coating liquid does not change with time and is easy to handle. It is preferable to use a decomposed product. In this case, the amount of water used is R ¹ _m M (OR
² ) 0.1 to 1 mol of the compound represented by _n (1)
It is 1000 mol, preferably 0.5 to 500 mol. In the case of a mixed solvent, the mixing ratio of water and the hydrophilic organic solvent is water / hydrophilic organic solvent = 10 to 90/90 to 10.
(Weight ratio), preferably 30 to 70/70 to 30, and more preferably 40 to 60/60 to 40.

Next, the gas barrier composition of the present invention preferably contains the inorganic fine particles as the component (C). The above-mentioned inorganic fine particles are particulate inorganic substances having an average particle diameter of 0.2 μm or less and substantially not containing carbon atoms, and examples thereof include metals or silicon oxides, metals or silicon nitrides, and metal borides. The method for producing the inorganic fine particles includes, for example, a gas phase method for obtaining silicon oxide by hydrolysis of silicon tetrachloride in a flame of oxygen and hydrogen, a liquid phase method for obtaining ion exchange of sodium silicate, and a silica gel mill. Examples of the production method include a solid-phase method obtained by pulverization by, for example, but are not limited to these methods.

Specific examples of compounds include SiO ₂ and A
l ₂ O ₃ , TiO ₂ , WO ₃ , Fe ₂ O ₃ , ZnO, NiO,
RuO ₂ , CdO, SnO ₂ , Bi ₂ O ₃ , 3Al ₂ O ₃・ 2
_{SiO 2, Sn-In 2 O} 3, Sb-In 2 O 3, CoFe
Ox and other oxides, Si ₃ N ₄ , Fe ₄ N, AlN, Ti
N, ZrN, TaN and other nitrides, Ti ₂ B, ZrB ₂ ,
Examples thereof include borides such as TaB ₂ and W ₂ B. The form of the inorganic fine particles may be powder, colloid or sol dispersed in water or an organic solvent, but is not limited thereto. Among these, the (A) component and /
Alternatively, in order to obtain excellent coating performance by co-condensing with the component (B), colloidal silica, colloidal alumina, alumina sol, tin sol, zirconium sol, antimony pentoxide sol, cerium oxide sol, zinc oxide sol, and oxidation are preferable. A colloidal oxide having a hydroxyl group on the surface of particles such as titanium sol is used. The average particle size of the inorganic fine particles is 0.2 μm or less, preferably 0.1 μm or less, and if the average particle size exceeds 0.2 μm, the gas barrier property may be poor from the viewpoint of the denseness of the film.

The ratio of the component (C) in the composition of the present invention is
The total amount of the components (A) and (B) is 100 parts by weight, preferably 10 to 900 parts by weight, particularly preferably 20 to 400 parts by weight. In the above, 900
When it exceeds the weight part, the gas barrier property of the obtained coating film may be deteriorated.

Next, in the present invention, the purpose of curing the gas barrier coating film of the gas barrier composition of the present invention faster is to facilitate the formation of a cocondensate of the components (A) and (B). The (D) curing accelerator may be used for the purpose, and it is more effective to use the (D) curing accelerator together in order to cure at a relatively low temperature and obtain a more dense coating film. .

Examples of the (D) curing accelerator include inorganic acids such as hydrochloric acid; alkali metal salts such as naphthenic acid, octylic acid, nitrous acid, sulfurous acid, aluminic acid and carbonic acid; sodium hydroxide, potassium hydroxide and the like. Alkaline compounds; Alkyl titanic acid, phosphoric acid, methanesulfonic acid, p-toluenesulfonic acid, phthalic acid and other acidic compounds; ethylenediamine, hexanediamine, diethylenetriamine,
Triethylenetetramine, tetraethylenepentamine,
Piperidine, piperazine, metaphenylenediamine, ethanolamine, triethylamine, various modified amines used as curing agents for epoxy resins, γ-aminopropyltriethoxysilane, γ- (2-aminoethyl)-
Aminopropyltrimethoxysilane, γ- (2-aminoethyl) -aminopropylmethyldimethoxysilane, γ
An amine compound such as anilinopropyltrimethoxysilane, (C ₄ H ₉ ) ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ (C ₄ H ₉ ) ₂ Sn (OCOCH = CHCOOCH ₃ ) ₂ ,
(C ₄ H ₉ ) ₂ Sn (OCOCH = CHCOOC
₄ H ₉ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ , (C
₈ H ₁₇ ) ₂ Sn (OCOCH = CHCOOCH ₃ ) ₂ , (C
_{8 H 17) 2 Sn (OCOCH} = CHCOOC 4 H 9) 2,
(C ₈ H ₁₇ ) ₂ Sn (OCOCH = CHCOOC
Carboxylic acid type organic tin compounds such as ₈ H ₁₇ ) ₂ and Sn (OCOCC ₈ H ₁₇ ) ₂ ; (C ₄ H ₉ ) ₂ Sn (SCH ₂ COOC
₈ H ₁₇ ) ₂ , (C ₄ H ₉ ) ₂ Sn (SCH ₂ COOC
₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOC
₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ CH ₂ COOC ₈
H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOC
₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOC
₁₂ H ₂₅ ) ₂ , Sulfide type organotin compounds such as;

(C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ Sn
O, or a reaction product of an organic tin oxide such as (C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ SnO and an ester compound such as ethyl silicate, dimethyl maleate, diethyl maleate and dioctyl phthalate. Organotin compounds and the like are used. The proportion of these (D) curing accelerators in the gas barrier composition is usually 0. 0 with respect to 100 parts by weight of the solid content of the gas barrier composition of the present invention.
5 to 50 parts by weight, preferably 0.5 to 30 parts by weight are used.

Further, the above-mentioned β-diketones and / or β-ketoesters can be added to the gas barrier composition of the present invention as a stability improver. That is, the action of controlling the condensation reaction between the component (A) and the component (B) by coordinating with the metal atom in the metal alcoholate present in the gas barrier composition as the component (B). Therefore, it is considered that the gas barrier composition obtained has the function of improving the storage stability. The amount of β-diketones and / or β-ketoesters used is preferably 2 mol or more, and more preferably 3 to 20 mol, per 1 mol of the metal atom in the component (B).

The gas barrier composition of the present invention is usually obtained by dissolving and dispersing the components (A) to (D) and optionally the optional components in water and / or a hydrophilic organic solvent. Here, specific examples of the hydrophilic organic solvent include methanol, ethanol, n-propanol, i-propanol, n-butyl alcohol, and se.
c-butyl alcohol, tert-butyl alcohol,
Carbon number 1 such as diacetone alcohol, ethylene glycol, diethylene glycol, triethylene glycol
~ 8 saturated aliphatic monohydric alcohol or dihydric alcohol; 1 to 8 carbon atoms such as ethylene glycol monobutyl ether and ethylene glycol monoethyl ether acetate
Saturated aliphatic ether compounds; C1-8 saturated aliphatic dihydric alcohol ester compounds such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate; N, N-dimethyl Acetamide, N, N-dimethylformamide, γ-
Nitrogen-containing compounds (nitrogen-containing organic solvents) such as butyrolactone, N-methylpyrrolidone, pyridine; sulfur-containing compounds such as dimethyl sulfoxide; hydroxycarboxylic acids or hydroxycarboxylic acid esters such as lactic acid, methyl lactate, ethyl lactate, salicylic acid, and methyl salicylate. And so on. Of these, preferred are methanol, ethanol, n-propanol, i-
Saturated aliphatic monohydric alcohol having 1 to 8 carbon atoms such as propanol, n-butyl alcohol, sec-butyl alcohol and tert-butyl alcohol; N, N-dimethylacetamide, N, N-dimethylformamide, γ-
Examples thereof include nitrogen-containing compounds (nitrogen-containing organic solvents) such as butyrolactone, N-methylpyrrolidone and pyridine.

These water and / or hydrophilic organic solvent are more preferably used as a mixture of water and a hydrophilic organic solvent. The preferred composition of the solvent is water / saturated aliphatic monohydric alcohol having 1 to 8 carbon atoms and water / nitrogen-containing compound (nitrogen-containing organic solvent). More preferably, it is water / saturated aliphatic monohydric alcohol having 1 to 8 carbon atoms / nitrogen-containing compound (nitrogen-containing organic solvent). By mixing the nitrogen-containing organic solvent, it is possible to obtain a good coating film having a transparent appearance in thin film coating.

The amount of water and / or hydrophilic organic solvent used is preferably such that the total solid content of the gas barrier composition is 6%.
It is used so as to be 0% by weight or less. For example, when it is used for the purpose of forming a thin film, it is usually 5 to 40% by weight, preferably 10 to 30% by weight, and when it is used for the purpose of forming a thick film, it is usually 20 to 50% by weight. %, Preferably 30 to 45% by weight. When the total solid content concentration of the gas barrier composition exceeds 60% by weight, the storage stability of the composition tends to decrease. The proportion of the nitrogen-containing organic solvent is usually 1 to 70% by weight, preferably 5 to 50% by weight, based on the total amount of the solvent.

As the organic solvent, water and / or a hydrophilic organic solvent described above are preferable, but in addition to the hydrophilic organic solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, tetrahydrofuran, dioxane, etc. Ethers, ketones such as acetone and methyl ethyl ketone, and esters such as ethyl acetate and butyl acetate can also be used.

Thus, the gas-barrier composition of the present invention is obtained by mixing the above-mentioned components (A) to (B) and optionally the above-mentioned optional components in water and / or a hydrophilic organic solvent, Preferably, it is obtained by hydrolyzing and / or condensing the component (A) and the component (B), and optionally the component (C), in water and / or a hydrophilic organic solvent. At this time, the reaction conditions include a temperature of 20 to 100 ° C., preferably 30 to 80 ° C., and a time of 0.1 to 20 hours, preferably 1 to 10 hours. The weight average molecular weight of the obtained gas barrier composition is a polymethylmethacrylate conversion value by a general GPC method,
Usually, 500 to 1,000,000, preferably 1,000 to 30
In many cases.

The gas barrier composition of the present invention contains
A filler may be added and dispersed separately in order to develop various properties such as coloring of the resulting coating film, thickening of the film, prevention of ultraviolet ray transmission to the base, provision of corrosion resistance, and heat resistance. However, the filler excludes the component (C). Examples of the filler include water-insoluble pigments such as organic pigments and inorganic pigments, or other than pigments, particulate, fibrous or scale-like metals and alloys, and oxides, hydroxides, carbides, and nitrides thereof. , Sulfide and the like. Specific examples of this filler include iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, titanium oxide, aluminum oxide and chromium oxide in the form of particles, fibers or scales. , Manganese oxide, iron oxide, zirconium oxide, cobalt oxide,
Synthetic mullite, aluminum hydroxide, iron hydroxide, silicon carbide, silicon nitride, boron nitride, clay, diatomaceous earth,
Slaked lime, gypsum, talc, barium carbonate, calcium carbonate, magnesium carbonate, barium sulfate, bentonite,
Mica, zinc green, chrome green, cobalt green, viridian, guinea green, cobalt chrome green, schele green, green soil, manganese green, pigment green, ultramarine blue, dark blue, pigment green, rock ultramarine, cobalt blue, cerulean blue, boric acid Copper, molybdenum blue, copper sulfide, cobalt purple, Mars purple,
Manganese purple, pigment violet, lead suboxide, calcium leadate, zinc yellow, lead sulfide, chrome yellow, loess,
Cadmium yellow, strontium yellow, titanium yellow, litharge, pigment yellow, cuprous oxide, cadmium red, selenium red, chrome vermillion, red iron oxide, zinc white, antimony white, basic lead sulfate, titanium white, lithopone, lead silicate, Zircon oxide, tungsten white, lead zinc white, bunchison white, lead phthalate, manganese white, lead sulfate, graphite, bone black, diamond black, thermatomic black, vegetable black, potassium titanate whiskers, molybdenum disulfide, etc. To be

The average particle size or average length of these fillers is usually 50 to 50,000 nm, preferably 100.
~ 5,000 nm. The proportion of the filler in the composition is
With respect to 100 parts by weight of the total solid content of components other than the filler, preferably 0.1 to 300 parts by weight, more preferably 1
~ 200 parts by weight.

The gas barrier composition of the present invention contains
In addition, known dehydrating agents such as methyl orthoformate, methyl orthoacetate, and tetraethoxysilane, various surfactants, silane coupling agents other than the above, titanium coupling agents, dyes, dispersants, thickeners, leveling It is also possible to add additives such as agents.

In preparing the gas barrier composition of the present invention, the above-mentioned components (A) to (B), preferably (A).
~ A composition containing the component (C) may be prepared. Preferably, the component (B) is hydrolyzed in water or a mixed solvent containing water and a hydrophilic organic solvent, and then the component (A) is added. Mix. In this case, the viscosity of the gas barrier composition does not change with time, and a gas barrier composition having excellent handleability can be obtained. Specific examples of the method for preparing the gas barrier composition of the present invention using the component (C) include the following methods. The component (B) used in these preparation methods may be hydrolyzed in advance in water or a mixed solvent containing water and a hydrophilic organic solvent. After adding the component (C) to the component (A) dissolved in water and / or a hydrophilic organic solvent, (B)
How to add ingredients. After adding the component (C) to the component (A) dissolved in water and / or a hydrophilic organic solvent,
A method of adding the component (B) and performing hydrolysis and / or condensation. The component (C) is added to the component (B) dissolved in water and / or a hydrophilic organic solvent to cause hydrolysis and / or
Alternatively, a method in which condensation is carried out and then the component (A) is added. Water and / or hydrophilic organic solvent (A) ~
A method in which the component (C) is added all at once and dissolved / dispersed. Alternatively, a method of performing hydrolysis and / or condensation after that.

Thus, in the present invention, the gas barrier composition prepared above is used, and the composition is applied onto the above-mentioned vapor deposition film of an inorganic oxide to form a gas barrier coating film. be able to. In the present invention, the inorganic oxide vapor deposition film and the gas barrier coating film, for example,
By forming a chemical bond, hydrogen bond, or coordination bond by hydrolysis / cocondensation reaction, the adhesion between the vapor deposition film of the inorganic oxide and the gas barrier coating film is improved. It is possible to exert a better gas barrier effect. Examples of the method of applying the gas barrier composition of the present invention include a roll coating method such as a gravure coater, a spray coating method, a spin coating method, a dipping method, a brush method, a bar code method, and a coating method such as an applicator method. The gas barrier coating film of the present invention having a dry film thickness of 0.01 to 30 μm, preferably 0.1 to 10 μm can be formed by coating once, and under normal environment, it is 50 to 300 ° C., preferably 70-200
At a temperature of 0.005 to 60 minutes, preferably 0.
By heating and drying for 01 to 10 minutes, condensation is performed, and the gas barrier coating film of the present invention can be formed. Further, if necessary, a primer agent or the like can be applied in advance on the vapor-deposited film of the inorganic oxide when applying the gas barrier composition of the present invention. Further, if necessary, when applying the gas barrier composition of the present invention, any pretreatment such as corona discharge treatment, plasma treatment, ozone treatment, and the like is previously performed on the inorganic oxide vapor deposition film. It can also be applied.

Next, in the present invention, the heat-sealable resin layer constituting the above-mentioned laminated material, packaging bag, etc. according to the present invention will be explained. As such a heat-sealable resin layer, Thermoplastic resins that can be melted by heat and fused to each other, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, ethylene-α polymerized using a metallocene catalyst.
-Olefin copolymer, polypropylene, ethylene-vinyl acetate copolymer, ionomer-resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer,
Ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene,
Use one or more types of acid-modified polyolefin resins, such as polypropylene-based polyolefin resins modified with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, etc. A single-layer or multi-layer film or sheet obtained by film-forming the same is used, and this is laminated via the extruded resin layer formed by the above-mentioned melt extrusion to form a heat-sealing resin layer. Can be formed. Thus, in the present invention,
The thickness of the heat-sealable resin layer may be the minimum necessary thickness that can be melted by heat and fused to each other. If it is too thick, the purpose is to reduce the thickness, reduce the weight, and the like. It becomes difficult to achieve the above, and further, there is a drawback that the cost increases, and conversely, if it is too thin, the above-mentioned heat seal performance and the like are deteriorated, which may cause troubles in bag making and the like. Therefore, it is not preferable. In the present invention, for the reasons described above, it is most desirable that the film thickness of the resin film or sheet is within the range of about 10 μm to 110 μm.

In the present invention, among the above-mentioned resin films or sheets, it is particularly preferable to use a resin film or sheet made of linear low density polyethylene. That is, the resin film or sheet made of the linear low-density polyethylene described above has the advantage of having less propagation of breakage and improving impact resistance because it has adhesiveness, and the inner layer is always contained in the contents. Since they are in contact with each other, they are also effective for preventing the deterioration of the environmental stress cracking resistance. In the present invention, the linear low-density polyethylene can be blended with other resins, for example, by blending an ethylene putine copolymer or the like, the heat resistance is slightly inferior and the seal stability is high under a high temperature environment. Although it tends to deteriorate, tearability improves,
There is an advantage that it contributes to easy opening.

Further, in the present invention, among the resin films or sheets constituting the heat-sealable resin layer as described above, further, an ethylene-α / olefin copolymer film or sheet polymerized by using a metallocene catalyst is used. It is preferred to use sheets as well. In the present invention, as described above, as the heat-sealable resin layer, a thermoplastic resin that can be melted by heat and fused to each other, specifically, a polyolefin resin such as low density polyethylene is used. In that case, the seal temperature of the polyolefin resin layer such as low-density polyethylene is
It is about 320 ° C to 350 ° C, which requires an extremely high seal temperature. Therefore, in the present invention,
Focusing on an ethylene-α-olefin copolymer polymerized by using a metallocene catalyst having a low-temperature sealing property, and forming a heat-sealing resin layer by that, 250 ° C. to 30 ° C.
It has the advantages of enabling a low temperature seal of about 0 ° C., preventing the occurrence of pinholes, and avoiding defective seals and liquid leakage. Furthermore, the ethylene-α-olefin copolymer polymerized by using a metallocene catalyst has an advantage that the propagation of breakage is small and the impact resistance is improved because it has adhesiveness, and the innermost layer is always Since it is in contact with the contents, it is also effective for preventing deterioration of the environmental stress cracking resistance. In addition, in the present invention, ethylene-polymerized using a metallocene catalyst
Other resins can be blended with the α / olefin copolymer. For example, by blending an ethylene-butene copolymer or the like, the heat stability is slightly deteriorated and the seal stability is deteriorated in a high temperature environment. Although there is a tendency, there is an advantage that tearability is improved and it contributes to easy opening. In the present invention, in particular, a heat seal comprising an ethylene-α-olefin copolymer layer polymerized using a metallocene catalyst
The use of a resinous resin layer has the advantage that low-temperature heat-sealing is possible.

Examples of the ethylene-α-olefin copolymer polymerized by using the above metallocene catalyst include:
A catalyst obtained by combining a metallocene complex such as a catalyst obtained by combining zirconocene dichloride and methylalumoxane with an alumoxane, that is, an ethylene-α-olefin copolymer obtained by copolymerizing ethylene and α-olefin using a metallocene catalyst. Polymers can be used. The above-mentioned metallocene catalyst is also called a single-site catalyst because the active site is non-uniform and is called a multi-site catalyst, while the active site is uniform (hereinafter referred to as a single-site catalyst). , Metallocene catalysts have the same meaning as single-site catalysts.) Specifically, as an ethylene-α / olefin copolymer polymerized using a metallocene catalyst, Mitsubishi Chemical Co., Ltd., trade name "Kaneru", Mitsui Petrochemical Industry Co., Ltd., trade name "Evolu"-", Exxon Chemical (EXXO, USA
NCHEMICAL's product name "Exact (EX
ACT ", Dow Chemical, USA
Product name “Affinity- (AFFIN
It is possible to use an ethylene-α-olefin copolymer polymerized with a metallocene catalyst such as TY) and a trade name “ENGAGE”. Thus, in the present invention, the film thickness of the heat-sealable resin layer comprising the ethylene-α-olefin copolymer layer polymerized by using the metallocene catalyst as described above is 10 μm to 110 μm.
It is desirable that the thickness is about μm, preferably about 20 to 50 μm.

Next, in the present invention, the extruded resin layer constituting the above-mentioned laminated material, packaging bag, etc. according to the present invention will be explained. Such extruded resin layer can be melted by heat and extruded from a die or the like. Thermoplastic resin, specifically, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, ethylene-α polymerized using a metallocene catalyst
-Olefin copolymer, polypropylene, ethylene-vinyl acetate copolymer, ionomer-resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer,
Ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene,
1 of acid-modified polyolefin resin obtained by modifying polyolefin resin such as polypropylene with unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, etc., and heat sealable resin such as others It can be formed by melt-extruding one kind or two kinds or more and using a T-die extruder or the like to the entire surface including the printed pattern layer provided on the primer agent layer. The film thickness is preferably about 2 to 10 μm in consideration of the damage to the vapor deposition film of the inorganic oxide and the like.

In the present invention, therefore, as the extruded resin layer, it is particularly preferable to use an extruded resin layer made of an ethylene-methacrylic acid copolymer. As the above ethylene-methacrylic acid copolymer, it is preferable to use a copolymer in which the methacrylic acid component is contained in the range of 4 to 12 mol%, preferably 4 to 7 mol%. Is. Further, in the present invention, the ethylene-methacrylic acid copolymer is, for example, a terpolymer containing a component such as an acrylic ester monomer.
Etc. can also be used. Further, in the present invention, as the ethylene-methacrylic acid copolymer, it is preferable to use one having a melt flow rate (MFR) of 4 to 10 positions. Thus, in the present invention, the above-mentioned ethylene-methacrylic acid copolymer is used, and if necessary, desired additives such as a light stabilizer, an ultraviolet absorber, a filler, a lubricant, etc. are added. History of preparing a resin composition by optionally adding an agent, using the resin composition,
The extruded resin layer can be formed by melt-extruding this onto the entire surface including the printed pattern layer using a T-die extruder or the like. In the present invention, by using the above-mentioned ethylene-methacrylic acid copolymer, in the case of low density polyethylene, for example, at a temperature of about 320 ° C., as compared with the conventional extruded resin layer of low density polyethylene. Thus, while the ethylene-methacrylic acid copolymer is extruded at a heating temperature of at least 300 ° C. or higher, the ethylene-methacrylic acid copolymer is extruded at a heating temperature of about 290 ° C., or 270 ° C. at a lower temperature. A resin layer can be formed. As a result, the film thickness of the extruded resin layer made of the ethylene-methacrylic acid copolymer can be reduced, and the film thickness can be 2 to 10 μm.
Furthermore, it is possible to form an extruded resin layer of 3 to 6 μm, more specifically, a film thickness of 5 μm, which is a sufficient film thickness for lamination, into an extruded resin layer, and to form the film. Ethylene-methacrylic acid copolymer, which can be processed at a high speed, and which is capable of stably extruding a predetermined thin film, molding it, and sufficiently functions as an adhesive layer when laminating it with another substrate. An extruded resin layer made of a polymer can be formed. In the present invention, ethylene-
By using a methacrylic acid copolymer and extruding it at a temperature of 290 ° C. or lower and reducing the film thickness of the extruded resin layer, the thermal damage to the vapor deposition film of the inorganic oxide is minimized. Therefore, damage to it can be suppressed.

Next, in the present invention, a resin film which has strength and is excellent in puncture resistance and the like constituting the laminated material, the packaging bag and the like according to the present invention will be explained.
The film of such a resin has excellent strength in mechanical, physical, chemical, etc., excellent puncture resistance, etc., in addition, heat resistance, moisture resistance, pinhole resistance,
A resin film or sheet excellent in transparency and the like can be used. Specifically, for example, polyester resin, polyamide resin, polyaramid resin, polypropylene resin, polycarbonate resin,
A film or sheet made of a tough resin such as a polyacetal resin, a fluorine resin, or the like can be used. Thus, in the present invention, the above-mentioned resin film or sheet is used, and, for example, the above-mentioned extruded resin is melt-extruded while being melt-extruded through the extruded resin layer. It can be laminated between the extruded resin layer and the heat-sealable resin layer by using an extrusion laminating method for laminating. In the above, as the resin film or sheet, either an unstretched film or a stretched film uniaxially or biaxially stretched can be used.
Further, in the present invention, the resin film or the sheet
As for the thickness of the sheet, strength, puncture resistance, etc. may be any thickness that can be kept to the minimum necessary. The strength, puncture resistance, etc. are unfavorable because they deteriorate. In the present invention, for the reasons described above, about 10 μm to 100 μm, and preferably about 12 μm to 50 μm is most desirable.

By the way, since the packaging bag is usually subjected to harsh conditions both physically and chemically, the laminate material constituting the packaging bag is required to have strict packaging suitability, and the deformation preventing strength is high. , Drop impact strength, pinhole resistance, heat resistance, sealability, quality maintenance, workability, hygiene, etc. are required. Therefore, in the present invention, the above materials are used. In addition to the above, other materials satisfying the above conditions can be arbitrarily used, and specifically,
For example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-pinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene- Acrylic acid or methacrylic acid copolymer, methylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (meth) acrylic resin , Polyacrylonitrile-based resin, polystyrene-based resin, acrylonitrile-styrene copolymer (AS-based resin), acrylonitrile-putagen-styrene copolymer (ABS-based resin), polyester-based resin, polyamide-based resin, polycarbonate-based resin Polyvinyl alcohol resin, saponified ethylene-vinyl acetate copolymer, fluorine resin,
A film or sheet of a known resin such as a gen resin, a polyacetal resin, a polyurethane resin, nitrocellulose, or the like can be arbitrarily selected and used. Besides, for example, synthetic paper or the like can be used. In the present invention, the above film or sheet,
Any one such as unstretched or uniaxially or biaxially stretched can be used. Also, its thickness is
Although it is optional, it can be used by selecting it from the range of several μm to 300 μm. Further, in the present invention, the film or sheet may be any film such as extrusion film formation, inflation film formation, and coating film.

In particular, in the present invention, other substrates include, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene having a barrier property to prevent permeation of water vapor, water, etc. Polypropylene, resin film or sheet such as ethylene-propylene copolymer, oxygen gas, polyvinyl alcohol having a barrier property to prevent permeation of water vapor and the like, resin film or sheet such as saponified ethylene-vinyl acetate copolymer, It is possible to use various colored resin films or sheets having a light-shielding property, which are obtained by adding a colorant such as a pigment to a resin and kneading the desired additives to form a film. These materials can be used alone or in combination of two or more. The thickness of the above-mentioned film or sheet is arbitrary, but is usually about 5 μm to 300 μm, and more preferably 10 μm to 100 μm.
μm is desirable.

Next, in the present invention, the method for producing the laminated material according to the present invention will be specifically described. For example, a dry lamination method of laminating via a laminating adhesive layer with a laminating adhesive, or It can be performed by an extrusion lamination method in which the melt extruded adhesive resin is laminated via a melt extruded resin layer. That is, in the present invention, in addition to laminating via the extruded resin layer as described above, a vapor deposition film of an inorganic oxide and a gas barrier coating film are provided on one surface of the substrate film and the vapor deposition substrate film. A barrier layer and a heat sealable resin layer,
When laminating other layers and the like, for example, an extrusion lamination method or a dry lamination method in which the respective layers are laminated via a melt-extruded resin layer or the respective layers are laminated via an adhesive layer for lamination. , Etc., and the like. In the above, examples of the laminating adhesive include, for example, one-component or two-component curing or non-curing type vinyl-based, (meth) acrylic-based, polyamide-based, polyester-based, polyether-based, polyurethane-based, epoxy-based adhesives. A solvent-based adhesive such as a rubber-based adhesive, a water-based adhesive, or an emulsion adhesive can be used. As a coating method of the above-mentioned laminating adhesive, for example, a direct gravure roll coating method, a gravure roll coating method, a kiss coating method, a reverse roll coating method, a Fonten method, a transfer roll coating method and the like can be applied. The coating amount is preferably 0.
1 to 10 g / m ² (dry state), more preferably 1 to
It is about 5 g / m ² (dry state). In addition, for example, an adhesion promoter such as a silane coupling agent can be optionally added to the laminating adhesive.

In the above, as the melt-extruded adhesive resin, the heat-sealable resin forming the heat-sealable resin layer described above can be used in the same manner.
It is preferable to use low density polyethylene and polypropylene, particularly linear low density polyethylene and acid-modified polyethylene. The film thickness of the melt-extruded resin layer made of the melt-extruded adhesive resin is preferably about 3 to 100 μm, more preferably about 3 to 20 μm. In the present invention, when it is necessary to obtain a stronger adhesive strength when performing the above-mentioned lamination, an adhesion improver such as an anchor coat agent may be coated. Examples of the anchor coating agent include organic titanium-based anchor coating agents such as alkyl titanates, isocyanate-based anchor coating agents, polyethyleneimine-based anchor coating agents, polybutadiene-based anchor coating agents, and other water-based or oil-based anchor coating agents. Can be used.
In the present invention, the anchor coating agent is coated by a roll coating method, a gravure coating method, a knife coating method, a dip coating method, a spray coating method, or another coating method, and a solvent or a diluent is dried to form an anchor coating agent layer. can do. The coating amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state).

Next, in the present invention, a description will be given of a packaging bag made of the above-mentioned laminated material according to the present invention, such as a soft packaging bag. The bag uses the laminated material according to the present invention as described above, and the surfaces of the heat-sealable resin layers are superposed so as to face each other, and then the peripheral end portion is heat-sealed. By forming the seal portion, a packaging bag such as the flexible packaging bag according to the present invention can be manufactured. As a bag-making method, the laminated material according to the present invention as described above is bent or superposed, the surfaces of the inner layers are made to face each other, and the peripheral end portions thereof are, for example, a side surface sheet. Type, two-sided seal type, three-sided seal type, four-sided seal type, envelope-sealed seal type, gassho-sealed seal type (pyro-seal type),
Various types of embodiments according to the present invention can be obtained by heat-sealing with a pleated seal type, a flat-bottomed seal type, a square-bottomed seal type, a gusset type, etc. It is possible to manufacture a packaging bag such as a flexible packaging bag. In addition, for example, a self-supporting packaging bag (standing pouch) or the like is also possible. In the above, as the heat seal method, for example, known are bar seal, rotary roll seal, belt seal, impulse seal, high frequency seal, ultrasonic seal and the like. Can be done by the method.

Next, in the present invention, from the opening of the packaging bag made of the plastic soft packaging bag having various forms according to the present invention produced above, for example, confectionery, snack food, Filling contents such as food and drink, and then heat-sealing the opening to produce a packaged product using a packaging bag produced using the laminated material according to the present invention. Is something that can be done.

The present invention, as explained above,
For example, at least a substrate film provided with a printed pattern layer, an extruded resin layer made of an ethylene-methacrylic acid copolymer having a thickness of 3 to 6 μm, and a vapor deposition film of an inorganic oxide on a vapor deposition substrate film are provided. Furthermore, a barrier layer provided with a gas barrier coating film on the inorganic oxide vapor deposition film, and
For example, a heat-sealable resin layer having a thickness of 10 μm to 40 μm made of a low density polyethylene film and an unstretched polypropylene film is sequentially laminated to produce a laminated material. Thus, the above-mentioned laminated material is excellent in its laminating strength and the like, delamination and the like are not recognized, and further, heat sealing performance and the like are also excellent. Has a predetermined strength in terms of mechanical, chemical or physical strength, for example, heat resistance, water resistance, light resistance, weather resistance, chemical resistance, puncture resistance, etc. It also has excellent barrier properties (blocking properties) that prevent the permeation of oxygen, water vapor, etc.
It has excellent air-proof, aroma-retaining, heat-insulating, and other properties, and fully protects the contents, etc. that have been filled and packaged, and its storage and storage stability,
Excellent in filling and packaging suitability, etc., and further, for each material constituting the laminated material forming the flexible packaging bag, the film thickness thereof is made thin,
It is possible to reduce the amount of the container / packaging waste, and it is possible to reduce the weight and the thickness by about 10% to 30% as compared with the conventional laminated material as the packaging material. It is a thing.

[0072]

EXAMPLES The present invention described above will be described more specifically with reference to the following examples. Example 1 (1). A biaxially stretched nylon 6 film having a thickness of 15 μm was used, and this was mounted on a delivery roll of a plasma enhanced chemical vapor deposition apparatus, and the thickness of the corona-treated surface of the above biaxially stretched nylon 6 film was increased under the following conditions. A 200 Å thick silicon oxide vapor deposition film was formed. (Deposition conditions) Deposition surface; Corona treatment surface Reactive gas mixture ratio; Hexamethyldisiloxane: Oxygen gas: Helium = 1.2: 5.0: 2.5 (unit: sl
m) Ultimate pressure; 5.0 × 10 ⁻⁵ mbar Film forming pressure; 7.0 × 10 ⁻² mbar power; 35 kW Line speed; 300 m / min Next, a silicon oxide vapor-deposited film with a film thickness of 200 Å is formed. Immediately after the formation, a glow discharge plasma generator was used on the surface of the deposited film of silicon oxide, and the power was 9 kw, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2.5 (unit: : Slm) and a mixed gas pressure of 6
Oxygen / argon mixed gas plasma treatment was carried out at × 10 ^-2 mbar, and the surface tension of the vapor-deposited silicon oxide film surface was 54 dy.
A plasma treated surface having an improved ne / cm or more was formed. (2). On the other hand, in a reactor equipped with a reflux condenser and a stirrer,
100 parts of tetra-i-propoxy titanium and 70 parts of acetylacetone were added and stirred at 60 ° C. for 30 minutes to obtain a titanium chelate compound. The purity of this reaction product was 75%. Next, as the component (A), an ethylene / vinyl alcohol copolymer [Nippon Gosei Kagaku KK, trade name,
Soarnol D2935, saponification degree; 98% or more, ethylene content; 29 mol%, melt flow index; 35
g / 10 minutes] and polyvinylpyrrolidone [manufactured by Wako Pure Chemical Industries, Ltd., Mw = 25,000].
% Of water / n-propyl alcohol solution (water / n-propyl alcohol weight ratio = 40/60), and 2 parts of the titanium chelate compound prepared above and n-
Propyl alcohol (16.8 parts) and water (11.2 parts) were mixed and hydrolyzed at 55 ° C. for 4 hours with component (B),
Furthermore, with 12.1 parts of N, N-dimethylformamide,
It mixed at 40 degreeC and stirred for 2 hours, and obtained the gas barrier composition of this invention. Next, the plasma-treated surface formed in the above (1) is coated with the gas barrier composition produced above by the gravure roll coating method, and then heat treated at 120 ° C. for 1 minute. Then, a gas barrier coating film having a thickness of 1.0 g / m ² (dry state) was formed to produce a barrier layer. (3). On the other hand, a biaxially stretched polypropylene film having a thickness of 20 μm is used, and a normal gravure ink composition is used on one side of the film, and a predetermined printed pattern composed of characters, figures, symbols, patterns, etc. by a gravure printing method. Was printed to form a printed pattern layer. Next, ethylene-methacrylic acid copolymer resin (Mitsui Dubon Polychemical Co., Ltd., product side, AN-4228) is used on the entire surface including the printed pattern layer formed above, and melted at about 290 ° C. While being extruded to form a melt-extruded resin layer having a thickness of 5 μm, the surfaces of the gas barrier coating films constituting the barrier layer produced in the above (2) were made to face each other and were overlapped to perform melt extrusion lamination. Further, in the same manner as above, an ethylene-methacrylic acid copolymer resin (Mitsui Dubon Polychemical Co., Ltd.) was formed on the surface of the biaxially stretched nylon 6 film having a thickness of 15 μm constituting the barrier layer melt-extruded and laminated. Made, product side, AN-4228) is used, and this is 290
Melt extruding at a temperature of about ℃ to form a melt-extruded resin layer having a thickness of 5 μm, linear low-density polyethylene films having a thickness of 60 μm are superposed with their corona-treated surfaces facing each other, and melt-extrusion laminated to form the present invention The laminated material according to the present invention was manufactured. (4). Next, two laminated materials produced above are prepared, and the surfaces of the linear low-density polyethylene films are overlapped so as to face each other, and thereafter, the ends around the outer periphery are heat-sealed on three sides to form a sealing portion. A three-way seal type soft packaging bag having an opening at the top was formed to form a packaging bag. Next, from the opening of the packaging bag manufactured above,
A snack confectionery packaging product was manufactured by filling the snack confectionery and then heat sealing the opening to form the upper seal. The packaged product produced as described above was excellent in barrier properties against oxygen gas, water vapor, etc., excellent in laminate strength, etc., endured distribution in the market, and excellent in storage and storage.

Example 2 (1). In the same manner as in Example 1 above, a biaxially stretched nylon 6 film having a thickness of 15 μm had a thickness of 2 mm on the corona-treated surface.
After forming a vapor-deposited film of silicon oxide of 00Å and forming a plasma-treated surface on the surface of the vapor-deposited film of silicon oxide, a gas barrier was formed on the entire surface of the plasma-treated surface in the same manner as in Example 1 above. To form a barrier coating layer. (2). On the other hand, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used, an ordinary gravure ink composition is used on one side of the film, and a predetermined pattern including characters, figures, symbols, pictures, etc. is obtained by a gravure printing method. The printed pattern was printed to form a printed pattern layer. Next, ethylene-methacrylic acid copolymer resin (manufactured by Mitsui Dubon Polychemical Co., Ltd., AN-4228) was used on the entire surface including the printed pattern layer formed as described above.
While melt-extruding at 0 ° C. to form a melt-extruded resin layer having a thickness of 5 μm, the surfaces of the gas barrier coating films constituting the barrier layer produced in the above (1) are made to face each other and overlap each other to be melt-extruded laminae. -I did. Furthermore, in the same manner as above, an ethylene-methacrylic acid copolymer resin (Mitsui Dubon Polychemical Co., Ltd.) was formed on the surface of the biaxially stretched nylon 6 film having a thickness of 15 μm constituting the barrier layer laminated by melt extrusion. Manufactured by the company, AN-4228), and melt-extruded at about 290 ° C. to form a melt-extruded resin layer having a thickness of 5 μm, and a linear low-density polyethylene film having a thickness of 30 μm was formed on the corona. Laminated materials according to the present invention were manufactured by stacking the treated surfaces facing each other and performing melt extrusion lamination. (3). Furthermore, in the same manner as in Example 1 above, two sheets of the laminated material produced above were prepared, and the surfaces of the linear low-density polyethylene films were laminated so as to face each other. Was heat-sealed on three sides to form a seal portion, and a packaging bag made of a three-way seal type soft packaging bag having an opening portion above was formed. Next, from the opening of the packaging bag produced above, filled with snacks,
Thereafter, the opening was heat-sealed to form an upper seal, and a snack confectionery packaged product was manufactured. The packaged product produced as described above was excellent in barrier properties against oxygen gas, water vapor, etc., excellent in laminate strength, etc., endured distribution in the market, and excellent in storage and storage.

Example 3 (1). As the base film, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used, and this was attached to a delivery roll of a plasma chemical vapor deposition apparatus,
Next, this was fed out, and a vapor-deposited film of silicon oxide having a thickness of 200Å was formed on the corona-treated surface of the biaxially stretched polyethylene terephthalate film under the conditions shown below. (Deposition conditions) Deposition surface; Corona treatment surface Reactive gas mixture ratio; Hexamethyldisiloxane: Oxygen gas: Helium = 1:11:10 (unit: slm) Vacuum degree in vacuum chamber; 5.2 x 10 ^-6 mbar Degree of vacuum in vapor deposition chamber; 5.1 × 10 ^-2 mbar Cooling / power supply to electrode drum; 60 w · min / m ² Film transport speed; 90 m / min Next, the above-mentioned 200 Å thick film of silicon oxide vapor deposition Immediately after the formation of the film, the above-mentioned Example 1 was formed on the surface of the deposited silicon oxide film.
Plasma treatment was performed in the same manner as in 1. to form a plasma-treated surface in which the surface tension of the deposited surface of silicon oxide was improved by 54 dyne / cm or more. (2). On the other hand, in a reactor equipped with a reflux condenser and a stirrer,
100 parts of tetra-i-propoxy titanium and 70 parts of acetylacetone were added and stirred at 60 ° C. for 30 minutes to obtain a titanium chelate compound. The purity of this reaction product was 75%. Next, as the component (A), an ethylene / vinyl alcohol copolymer [Nippon Gosei Kagaku KK, trade name,
Soarnol D2935, saponification degree; 98% or more, ethylene content; 29 mol%, melt flow index; 35
g / 10 minutes] 5% water / n-propyl alcohol solution (water / n-propyl alcohol weight ratio = 40/60) 1
A mixture of 00 parts, 2 parts of the titanium chelate compound prepared above, 16.8 parts of n-propyl alcohol and 11.2 parts of water and hydrolyzed at 55 ° C for 4 hours was added to the component (B) at 40 ° C. And mixed for 2 hours to obtain the gas barrier composition of the present invention. Next, the plasma-treated surface formed in (1) above is coated with the gas barrier composition prepared above by the gravure roll coating method, and then heat-treated at 120 ° C. for 2 minutes. A gas barrier coating film having a thickness of 1.0 g / m ² (dry state) was formed to produce a barrier layer. (3). On the other hand, a biaxially stretched polypropylene film having a thickness of 20 μm is used, and a normal gravure ink composition is used on one side of the film, and a predetermined printed pattern composed of characters, figures, symbols, patterns, etc. by a gravure printing method. Was printed to form a printed pattern layer. Next, ethylene-methacrylic acid copolymer resin (Mitsui Dubon Polychemical Co., Ltd., product side, AN-4228) is used on the entire surface including the printed pattern layer formed above, and melted at about 290 ° C. While being extruded to form a melt-extruded resin layer having a thickness of 5 μm, the surfaces of the gas barrier coating films constituting the barrier layer produced in the above (2) were made to face each other and were overlapped to perform melt extrusion lamination. Further, on the surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm forming the barrier layer melt-extruded and laminated as described above, an ethylene-methacrylic acid copolymer resin (Mitsui Dubon Polychemical A commercial product, AN-4228) manufactured by Co., Ltd. is melt-extruded at about 290 ° C. to form a melt-extruded resin layer having a thickness of 5 μm, and ethylene polymerized using a metallocene catalyst having a thickness of 60 μm. The α-olefin copolymer film was laminated with the corona-treated surfaces facing each other, and melt-extrusion laminated to produce a laminated material according to the present invention. (4). Next, two sheets of the laminated material produced above were prepared, and the surfaces of the ethylene-α / olefin copolymer films polymerized by using the metallocene catalyst were opposed to each other, and were superposed,
Then, the edges around the outer circumference were heat-sealed on three sides to form a seal portion, and a packaging bag made of a three-way seal type soft packaging bag having an opening at the top was formed. Next, from the opening of the packaging bag produced as described above, snack snacks were filled, and then the opening was heat-sealed to form the upper seal portion to produce a snack snack packaged product. . The packaged product produced as described above was excellent in barrier properties against oxygen gas, water vapor, etc., excellent in laminate strength, etc., endured distribution in the market, and excellent in storage and storage.

Example 4 (1). As a base film, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used.
The biaxially stretched polyethylene terephthalate film was mounted on a delivery roll of a roll-up type vacuum vapor deposition device, and then it was fed out, and the corona-treated surface of the biaxially stretched polyethylene terephthalate film was coated with aluminum. Was used as a vapor deposition source while supplying oxygen gas, and a vacuum vapor deposition method by an electron beam (EB) heating system was used to form a vapor deposition film of aluminum oxide having a film thickness of 200 Å under the following vapor deposition conditions. (Deposition conditions) Degree of vacuum in deposition chamber: 2 × 10 ⁻⁴ mbar Degree of vacuum in winding chamber: 2 × 10 ⁻² mbar Electronic beam power: 25 kW Film transfer speed: 240 m / min Deposition surface Next, a plasma-treated surface was formed on the aluminum oxide vapor-deposited film surface in the same manner as in Example 1 immediately after forming the aluminum oxide vapor-deposited film having a thickness of 200Å. (2). On the other hand, in a reactor equipped with a reflux condenser and a stirrer,
100 parts of tetra-i-propoxy titanium and 70 parts of acetylacetone were added and stirred at 60 ° C. for 30 minutes to obtain a titanium chelate compound. The purity of this reaction product was 75%. Next, as the component (A), an ethylene / vinyl alcohol copolymer [Nippon Gosei Kagaku KK, trade name,
Soarnol D2935, saponification degree; 98% or more, ethylene content; 29 mol%, melt flow index; 35
g / 10 minutes] 5% water / n-propyl alcohol solution (water / n-propyl alcohol weight ratio = 40/60) 1
00 parts, 2 parts of the titanium chelate compound prepared above, 16.8 parts of n-propyl alcohol, and 11.2 of water.
The parts were mixed, and the component (B) hydrolyzed at 55 ° C. for 4 hours was mixed at 40 ° C. and stirred for 2 hours to obtain a gas barrier composition of the present invention. Next, the plasma-treated surface formed in (1) above is coated with the gas barrier composition prepared above by the gravure roll coating method, and then heat treated at 120 ° C. for 2 minutes. hand,
A gas barrier coating film having a thickness of 1.0 g / m ² (dry state) was formed to produce a barrier layer. (3). On the other hand, a biaxially stretched polypropylene film having a thickness of 20 μm is used, and a normal gravure ink composition is used on one side of the film, and a predetermined printed pattern composed of characters, figures, symbols, patterns, etc. by a gravure printing method. Was printed to form a printed pattern layer. Next, ethylene-methacrylic acid copolymer resin (Mitsui Dubon Polychemical Co., Ltd., product side, AN-4228) is used on the entire surface including the printed pattern layer formed above, and melted at about 290 ° C. While being extruded to form a melt-extruded resin layer having a thickness of 5 μm, the surfaces of the gas barrier coating films constituting the barrier layer produced in the above (2) were made to face each other and were overlapped to perform melt extrusion lamination. Further, on the surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm forming the barrier layer melt-extruded and laminated as described above, an ethylene-methacrylic acid copolymer resin (Mitsui Dubon Polychemical Manufactured by K.K., product surface, AN-4228), and melt-extruded at about 290 ° C. to form a melt-extruded resin layer having a thickness of 5 μm, and a linear low-density polyethylene film having a thickness of 60 μm, The corona-treated surfaces were made to face each other and overlapped, and melt extrusion lamination was carried out to produce a laminated material according to the present invention. (4). Next, two laminated materials produced above are prepared, and the surfaces of the linear low-density polyethylene films are overlapped so as to face each other, and thereafter, the ends around the outer periphery are heat-sealed on three sides to form a sealing portion. A three-way seal type soft packaging bag having an opening at the top was formed to form a packaging bag. Next, from the opening of the packaging bag manufactured above,
A snack confectionery packaging product was manufactured by filling the snack confectionery and then heat sealing the opening to form the upper seal. The packaged product produced as described above was excellent in barrier properties against oxygen gas, water vapor, etc., excellent in laminate strength, etc., endured distribution in the market, and excellent in storage and storage.

Example 5 (1). As the base film, a biaxially stretched nylon 6 film having a thickness of 15 μm was used. First, the above biaxially stretched nylon 6 film was mounted on a delivery roll of a winding type vacuum vapor deposition device, and then this Out, part 2
Aluminum was used as a vapor deposition source on the corona-treated surface of the axially stretched nylon 6 film, and oxygen gas was supplied, while a vacuum vapor deposition method by an electron beam (EB) heating system was used to obtain a film thickness of 200 Å under the following vapor deposition conditions. A deposited film of aluminum oxide was formed. (Deposition conditions) Degree of vacuum in deposition chamber: 2 × 10 ⁻⁴ mbar Degree of vacuum in winding chamber: 2 × 10 ⁻² mbar Electronic beam power: 25 kW Film transfer speed: 240 m / min Deposition surface Next, a plasma-treated surface was formed on the aluminum oxide vapor-deposited film surface in the same manner as in Example 1 immediately after forming the aluminum oxide vapor-deposited film having a thickness of 200Å. (2). On the other hand, in a reactor equipped with a reflux condenser and a stirrer,
Tetra-n-butoxyzirconium (purity 100%) 1
00 parts and 68 parts of ethyl acetoacetate were added, and the mixture was added at 60 ° C. for 30
After stirring for a minute, a zirconium chelate compound was obtained. The purity of this reaction product was 77%. Next, as the component (A), an ethylene / vinyl alcohol copolymer [manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name, Soarnol D2935, saponification degree: 98% or more, ethylene content: 29 mol%, melt flow index; 35 g / 10 minutes] 5% water / n
100 parts of a propyl alcohol solution (water / n-propyl alcohol weight ratio = 40/60), 2 parts of the zirconium chelate compound prepared above, 16.8 parts of n-propyl alcohol and 11.2 parts of water were mixed. The component (B) hydrolyzed at 55 ° C. for 4 hours was mixed at 40 ° C. and stirred for 2 hours to obtain a gas barrier composition of the present invention. Next, the plasma-treated surface formed in (1) above is coated with the gas barrier composition prepared above by the gravure roll coating method, and then 12
A heat treatment was performed at 0 ° C. for 2 minutes to form a gas barrier coating film having a thickness of 1.0 g / m ² (dry state), and a barrier layer was produced. (3). On the other hand, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used, an ordinary gravure ink composition is used on one side of the film, and a predetermined pattern including characters, figures, symbols, pictures, etc. is obtained by a gravure printing method. The printed pattern was printed to form a printed pattern layer. Next, ethylene-methacrylic acid copolymer resin (manufactured by Mitsui Dubon Polychemical Co., Ltd., AN-4228) was used on the entire surface including the printed pattern layer formed as described above.
While melt-extruding at about 0 ° C. to form a melt-extruded resin layer having a thickness of 5 μm, the surfaces of the gas barrier coating films constituting the barrier layer produced in the above (2) are made to face each other and overlap each other to be melt-extruded laminae. -I did. Furthermore, in the same manner as above, an ethylene-methacrylic acid copolymer resin (Mitsui Dubon Polychemical Co., Ltd.) was formed on the surface of the biaxially stretched nylon 6 film having a thickness of 15 μm constituting the barrier layer laminated by melt extrusion. Manufactured by AN-4228) and melt-extruded at about 290 ° C. to form a melt-extruded resin layer having a thickness of 5 μm, and an unstretched polypropylene film having a thickness of 30 μm was formed on the corona-treated surface. The laminate material according to the present invention was manufactured by stacking them facing each other and performing melt extrusion lamination. (4). Next, two sheets of the laminated material produced above are prepared, and the surfaces of the non-stretched polypropylene films are laminated so as to face each other, and thereafter, the end portions around the outer periphery are heat sealed on three sides to form a seal portion. A packaging bag made of a three-way seal type flexible packaging bag having an opening at the top was formed. Next, the snacks are filled from the opening of the packaging bag produced above, and then the opening is opened in a heat seal.
And the upper seal was formed to produce a snack confectionery packaging product. The packaged product produced as described above was excellent in barrier properties against oxygen gas, water vapor, etc., excellent in laminate strength, etc., endured distribution in the market, and excellent in storage and storage.

Comparative Example 1 (1). A biaxially stretched nylon 6 film having a thickness of 15 μm was used, and this was mounted on a delivery roll of a plasma enhanced chemical vapor deposition apparatus, and the thickness of the corona-treated surface of the above biaxially stretched nylon 6 film was increased under the following conditions. A 200 Å thick silicon oxide vapor deposition film was formed. (Deposition conditions) Deposition surface; Corona treatment surface Reactive gas mixture ratio; Hexamethyldisiloxane: Oxygen gas: Helium = 1.2: 5.0: 2.5 (unit: sl
m) Ultimate pressure; 5.0 × 10 ⁻⁵ mbar Film forming pressure; 7.0 × 10 ⁻² mbar power; 35 kW Line speed; 300 m / min Next, a silicon oxide vapor-deposited film with a film thickness of 200 Å is formed. Immediately after the formation, a glow discharge plasma generator was used on the surface of the deposited film of silicon oxide, and the power was 9 kw, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2.5 (unit: : Slm) and a mixed gas pressure of 6
Oxygen / argon mixed gas plasma treatment was carried out at × 10 ^-2 mbar, and the surface tension of the vapor-deposited silicon oxide film surface was 54 dy.
By forming a plasma-treated surface with an improved ne / cm or more,
A barrier layer was produced. (2). On the other hand, a biaxially stretched polypropylene film having a thickness of 20 μm is used, and a normal gravure ink composition is used on one side of the film, and a predetermined printed pattern composed of characters, figures, symbols, patterns, etc. by a gravure printing method. Was printed to form a printed pattern layer. Next, low density polyethylene was used on the entire surface including the printed pattern layer formed above through a normal anchor coating agent layer, and this was melt extruded at about 320 ° C. and melt extruded with a thickness of 15 μm. While forming the resin layer, the plasma-treated surfaces constituting the barrier layer produced in the above (1) were faced to each other and overlapped, and melt extrusion lamination was performed. Further, on the surface of the biaxially stretched nylon 6 film having a thickness of 15 μm, which constitutes the barrier layer melt-extruded and laminated as described above, in the same manner as described above, a usual anchor coater is used.
Using a low-density polyethylene through a coating agent layer, this is melt-extruded at about 320 ° C. to form a melt-extruded resin layer having a thickness of 15 μm, while a linear low-density polyethylene film having a thickness of 60 μm is The corona-treated surfaces were made to face each other and were overlapped, and melt extrusion lamination was performed to manufacture a laminated material. (3). Next, two laminated materials produced above are prepared, and the surfaces of the linear low-density polyethylene films are overlapped so as to face each other, and thereafter, the ends around the outer periphery are heat-sealed on three sides to form a sealing portion. A three-way seal type soft packaging bag having an opening at the top was formed to form a packaging bag. Next, from the opening of the packaging bag manufactured above,
A snack confectionery packaging product was manufactured by filling the snack confectionery and then heat sealing the opening to form the upper seal.

Comparative Example 2 (1). As a base film, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used.
The biaxially stretched polyethylene terephthalate film was mounted on a delivery roll of a roll-up type vacuum vapor deposition device, and then it was fed out, and the corona-treated surface of the biaxially stretched polyethylene terephthalate film was coated with aluminum. Was used as a vapor deposition source while supplying oxygen gas, and a vacuum vapor deposition method by an electron beam (EB) heating system was used to form a vapor deposition film of aluminum oxide having a film thickness of 200 Å under the following vapor deposition conditions. (Deposition conditions) Degree of vacuum in deposition chamber: 2 × 10 ⁻⁴ mbar Degree of vacuum in winding chamber: 2 × 10 ⁻² mbar Electronic beam power: 25 kW Film transfer speed: 240 m / min Deposition surface Next, a plasma-treated surface was formed on the aluminum oxide vapor-deposited film surface in the same manner as in Example 1 immediately after the aluminum oxide vapor-deposited film having a thickness of 200 Å was formed. , A barrier layer was produced. (2). On the other hand, a biaxially stretched polypropylene film having a thickness of 20 μm is used, and a normal gravure ink composition is used on one side of the film, and a predetermined printed pattern composed of characters, figures, symbols, patterns, etc. by a gravure printing method. Was printed to form a printed pattern layer. Next, low density polyethylene was used on the entire surface including the printed pattern layer formed above through a usual anchor-coating agent layer, and this was melt extruded at about 320 ° C. and melt extruded with a thickness of 15 μm. While forming the resin layer, the plasma-treated surfaces constituting the barrier layer produced in the above (1) were faced to each other and overlapped, and melt extrusion lamination was performed. Further, on the surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, which constitutes the barrier layer melt-extruded and laminated as described above, through a usual anchor coating agent layer in the same manner as above, Use low density polyethylene, melt extrude at about 320 ℃, thickness 15μ
While forming a melt-extruded resin layer of m, a linear low-density polyethylene film having a thickness of 60 μm is superposed with its corona-treated surfaces facing each other, and melt-extrusion laminated,
A laminated material was manufactured. (3). Next, two laminated materials produced above are prepared, and the surfaces of the linear low-density polyethylene films are overlapped so as to face each other, and thereafter, the ends around the outer periphery are heat-sealed on three sides to form a sealing portion. A three-way seal type soft packaging bag having an opening at the top was formed to form a packaging bag. Next, from the opening of the packaging bag manufactured above,
A snack confectionery packaging product was manufactured by filling the snack confectionery and then heat sealing the opening to form the upper seal.

Experimental Example Regarding the laminated materials produced in the above Examples 1 to 5 and Comparative Examples 1 to 2, oxygen permeability, water vapor permeability, and
The heat seal strength was measured. (1). Measurement of Oxygen Permeability This is measured under the conditions of temperature 23 ° C and humidity 90% RH in the United States,
The measurement was performed using a measuring machine [model name, OXTRAN] manufactured by MOCON. (2). Measurement of water vapor permeability This is the temperature of 40 ° C and humidity of 90% RH in the United States,
The measurement was carried out by a measuring machine manufactured by MOCON (model name, Permatran). (3). Measurement of heat seal strength This is a heat seal using a one-sided heating heat sealer, and heat seals at a seal pressure of 0.2 MPa, a seal time of 1 second, and then, 90 degree peeling method, peeling speed, 300
/ Min was measured. The above measurement results are shown in Table 1 below.

[0080] In Table 1 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 ・ 100% R]
H], and the unit of heat seal strength is [150 ° C.,
N / 15 mm].

As is clear from the measurement results shown in Table 1 above, the laminated material according to the present invention is excellent in oxygen barrier property, water vapor barrier property and the like, and is sufficiently used as a packaging material. Was able to withstand.

[0082]

As is apparent from the above description, the present invention makes the melt-extruded resin layer thin and lowers the melting temperature without deteriorating the barrier property of the transparent vapor deposition barrier film, and -It is possible to reduce the amount of packaging waste. Therefore, the present invention focuses on an ethylene-methacrylic acid copolymer as a melt-extruded resin layer, and further melt-extrudes this at 290 ° C to obtain a thickness of 2 A melt-extruded resin layer of about 10 μm can be formed, and a heat seal such as low-density polyethylene or unstretched polypropylene can be formed on the surface of the vapor-deposited film of the transparent vapor-deposited barrier film through the melt-extruded resin layer. Focusing on the ability to laminate a functional resin layer, at least a substrate film, a barrier layer provided with a vapor deposition film of an inorganic oxide and a gas barrier coating film on one surface of the vapor deposition substrate film, And a heat-sealable resin layer, for example, the above-mentioned substrate film, and a barrier layer in which a vapor deposition film of an inorganic oxide and a gas barrier coating film are provided on one surface of the vapor deposition substrate film. Means one surface of the substrate film and the surface of the gas barrier coating film constituting the barrier layer are opposed to each other, and the interlayer is interposed via an extruded resin layer, or one of the above vapor deposition substrate films. The barrier layer having a vapor-deposited film of an inorganic oxide and a gas barrier coating film on its surface and the heat-sealing resin layer are the surface of the gas barrier coating film and the heat-shielding resin layer constituting the barrier layer. The surfaces of the tosyl resin layers are opposed to each other, and the layers are sequentially laminated via the extruded resin layer to produce a laminated material, and the laminated material is used to form a bag. Producing a packaging bag, further, in the packaging bag, for example, confectionery, snack foods, The above-mentioned laminated material is excellent in barrier properties against oxygen and water vapor, is excellent in laminate strength, etc., and is free from delamination etc. Further, the heat-sealing performance is also excellent, and the packaging bag produced by using this has a predetermined strength in mechanical, chemical, or physical strength, for example, heat resistance and water resistance. Excellent in durability, light resistance, weather resistance, chemical resistance, puncture resistance, etc., and also excellent in moisture proof, waterproof, air proof, aroma retention, heat insulation, etc. Sufficiently protects the contents and the like, and is excellent in storage, storage stability, suitability for filling and packaging, etc., and further, for each material constituting the laminated material forming the packaging bag, the film thickness is made thin, An extremely useful packaging material that can reduce the amount of container and packaging waste Be obtained to produce a packaging bag using laminate and its Te is that it is.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing an outline of a layer structure of an example of a laminated material according to the present invention.

FIG. 2 is a schematic cross-sectional view showing an outline of a layer structure of an example of a laminated material according to the present invention.

FIG. 3 is a schematic cross-sectional view showing an outline of a layer structure of an example of a laminated material according to the present invention.

FIG. 4 is a schematic perspective view showing an example of a packaging bag such as a soft packaging bag formed by using the laminated material according to the present invention shown in FIG.

5 is a schematic perspective view showing an example of a packaged product obtained by filling and packaging the contents in a packaging bag such as the flexible packaging bag shown in FIG.

FIG. 6 is a schematic configuration diagram showing an example of a low temperature plasma chemical vapor deposition apparatus.

FIG. 7 is a schematic configuration diagram showing an example of a winding type vacuum vapor deposition device.

[Explanation of symbols]

A Laminated material A ₁ Laminated material A ₂ Laminated material B Packaging bag C Packaging product 1 Base material film 2 Base material film 3 for vapor deposition Inorganic oxide vapor deposition film 4 Gas barrier coating film 5 Barrier layer 6 Heat sealable resin layer 7 Printed pattern layer 8 Extruded resin layer 9 Seal part 10 Opening part 11 Flexible packaging bag 12 Contents 13 Seal part above

Continued front page    F term (reference) 3E064 BA17 BA24 BA36 BA54 BB03                       BC08 BC18                 3E086 AA23 AC07 AC33 AD01 AD08                       BA04 BA15 BA33 BA35 BA40                       BB02 BB05 BB22 BB23 BB51                       BB62 BB85 CA01 DA01                 4F100 AA17C AA19C AA20C AK01A                       AK01B AK01E AK03A AK03B                       AK03E AK07 AK21D AK41A                       AK41B AK46A AK46B AK63                       AK69 AK71E BA05 CC00D                       DA02 EH17E EH23 EH66C                       EJ38A EJ38B GB15 GB16                       HB31A JD02D JK01E JK12E                       JL00 JL11 JL12E

Claims (16)

[Claims] 1. A base film, a barrier layer in which a vapor deposition film of an inorganic oxide and a gas barrier coating film are provided on one surface of a base film for vapor deposition, and a heat seal resin layer. A laminated material characterized by being sequentially laminated. 2. A substrate film, and a barrier layer having a vapor deposition film of an inorganic oxide and a gas barrier coating film provided on one surface of the vapor deposition substrate film, the one surface of the substrate film and the barrier layer. 2. The laminated material according to claim 1, wherein the gas barrier coating film constituting the functional layer is opposed to the surface, and the layers are laminated with an extruded resin layer interposed therebetween. 3. A barrier layer in which a vapor deposition film of an inorganic oxide and a gas barrier coating film are provided on one surface of a substrate film for vapor deposition, and a heat sealable resin layer are the barrier layers. The surface of the gas-barrier coating film and the surface of the heat-sealable resin layer constituting the are opposed to each other, and the layers are interposed via the extruded resin layer,
The laminated material according to claim 1, wherein both are laminated. 4. The base film is a biaxially stretched polyester resin film, a biaxially stretched polyamide resin film,
Alternatively, the laminated material according to any one of claims 1 to 3, which is made of a biaxially stretched polyolefin resin fill. 5. The substrate film for vapor deposition comprises a biaxially stretched polyester resin film, a biaxially stretched polyamide resin film, or a biaxially stretched polyolefin resin paste, as described above. The laminated material as described in any one of 4 above. 6. The vapor deposition film of an inorganic oxide comprises a vapor deposition film of an inorganic oxide formed by a chemical vapor deposition method or a physical vapor deposition method, according to claim 1. The laminated material described in. 7. The laminated material according to claim 1, wherein the vapor-deposited film of an inorganic oxide is a vapor-deposited film of silicon oxide formed by a chemical vapor deposition method. 8. The laminated material according to claim 1, wherein the vapor deposition film of an inorganic oxide is a vapor deposition film of aluminum oxide formed by physical vapor deposition. 9. A gas barrier coating film comprising at least a polyvinyl alcohol resin and a general formula R ¹ _m M (O
R ² ) _n (In the formula, M represents a metal atom, R ¹ is the same or different and represents an organic group having 1 to 8 carbon atoms, and R ² is
Identical or different, each represents an alkyl group having 1 to 5 carbon atoms, an acyl group having 1 to 6 carbon atoms, or a phenyl group, m and n each represent an integer of 0 or more, and m + n represents M.
Represents the valence of. ), A metal alcoholate, a hydrolyzate of the metal alcoholate, a condensate of the metal alcoholate, a chelate compound of the metal alcoholate, and the chelate.
9. A gas barrier coating film comprising a gas barrier composition containing at least one selected from the group consisting of a hydrolyzate of a metal compound and a metal acylate. The laminated material according to item 1. 10. The heat-sealable resin layer has a thickness of 10 to 10.
The laminated material according to any one of claims 1 to 9, which comprises a polyolefin resin layer having a thickness of 110 µm. 11. The extruded resin layer comprises an extruded resin layer having a thickness of 2 to 10 μm.
The laminated material described in any one of 0. 12. The laminate according to claim 1, wherein the extruded resin layer is an extruded resin layer of ethylene-methacrylic acid copolymer having a thickness of 3 to 6 μm. Material. 13. The laminated material according to any one of claims 1 to 12, wherein the extruded resin layer comprises an extruded resin layer of ethylene-methacrylic acid copolymer having a thickness of 5 μm. 14. The laminated material according to any one of claims 1 to 13, wherein the base film has a printed pattern layer. 15. The resin film having strength and excellent puncture resistance is laminated between the barrier layer and the heat-sealing resin layer, and the resin film is laminated. The laminated material according to item 1. 16. A base film, a barrier layer in which a vapor deposition film of an inorganic oxide and a gas barrier coating film are provided on at least one surface of a base film for vapor deposition, and a heat sealable resin layer. Using a laminated material manufactured by sequentially laminating the sheets, the surfaces of the heat-sealable resin layers are made to face each other, and the end portions around the outer periphery thereof are heat-sealed to form a seal. A packaging bag, which is characterized in that a bag layer is formed to form a bag.