JP2006290430A - Packaging product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a packaging product capable of protecting the quality of contents by exhibiting the oxygen collecting function. <P>SOLUTION: The packaging product consists of a laminated body successively laminating a substrate film, a barrier property base film, an oxygen absorbing resin layer formed of a resin composition comprising an oxidizing resin and a transition metal catalyst, and a heat-sealable resin layer. The laminated body is overlapped with the face of the heat sealable resin layer opposing each other, and end parts around the outer periphery are heat-sealed to form a packaging bag. In addition, contents are filled in from an opening part into the packaging bag, and packaged. Before, after or simultaneously with the filling and packaging, the inner surface of the packaging bag is irradiated with ultraviolet rays having the ultraviolet wavelength zone of 200-280 nm in a range of the ultraviolet ray irradiation of 200-1,000 mJ/cm<SP>2</SP>. The inner surface of the laminated body to constitute the packaging bag is sterilized thereby, the oxygen absorbing performance is realized, and the opening part is heat-sealed to form and seal a seal part. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a packaged product, and more specifically, sterilizes the inner surface of a laminate constituting a packaging bag, fills and packs the contents, captures oxygen present or generated in the package, and It relates to packaging products that protect quality.

Conventionally, materials such as plastic films, paper base materials, metal foils or vapor-deposited films thereof, etc. are used, and these are arbitrarily combined and laminated to produce packaging materials having various layer configurations. Use and bag making to manufacture packaging bags of various forms, and then in the packaging bags, for example, various foods and drinks, chemical products such as liquid detergents, cosmetics, pharmaceuticals, miscellaneous goods Products, industrial members, and other various articles are filled and packaged, and plastic packaging products having various forms have been developed and proposed.
Thus, the packaging materials constituting the plastic packaging products described above have excellent heat sealability and sufficient sealing properties due to demands for protecting the quality of contents, extending the storage period, etc. In addition to being able to satisfy the above requirements, it is required to have an easy-opening property that allows the packaging bag to be easily opened at the time of consumption.
In addition, the packaging material constituting the plastic packaging product described above has a gas barrier property that prevents permeation of oxygen gas, water vapor, etc., depending on the contents to be filled and packaged, or the odor of the contents. It is also required to have a fragrance retaining property that protects the like.
Furthermore, the packaging material constituting the plastic packaging product is also required to have a light shielding property or a light shielding property for preventing transmission of sunlight, fluorescent light, and the like.
Further, the packaging material constituting the plastic packaging product described above may be required to be sterilized or sterilized by sterilization treatment or the like when filling and packaging the contents.
Therefore, in recent years, various materials, materials, and the like have been used to develop packaging materials having various layer structures, and accordingly, packaging bags and packaging products having various forms have been proposed.
Thus, in recent years, one of them, for example, a container that prevents oxidation of the contents of the container by removing oxygen from the container and preventing oxygen from entering the container from outside the container. A product article comprising: an oxygen scavenging composition comprising a polymer main chain, a cyclic olefin pendant group, a linking group binding the olefin pendant group to the main chain, and a transition metal catalyst; A multilayer film, a container, a manufacturing method, and others have been proposed (for example, refer to Patent Document 1).
Special table 2003-521552 gazette.

However, when the packaging film, packaging material, etc. according to the above-mentioned Patent Document 1 are used, a packaging container is produced therefrom, and then a packaging product using the packaging container is produced. As an example, when using a biaxially stretched polyester resin film, the biaxially stretched polyester resin film absorbs light from around 350 nm, which is near ultraviolet light. For example, the oxygen scavenging function of attacking radicals into the unsaturated bond part of the cyclohexene ring as an oxygen-absorbing resin through the metal catalyst, and binding and absorbing oxygen from the chain reaction should be sufficiently performed. There is a problem that it is difficult.
In general, in a packaged product, the base film forming the packaging bag is composed of, for example, characters, figures, patterns, symbols, etc., for displaying, explaining, etc. the contents to be filled and packaged. A print pattern layer is provided. Thus, when such a print pattern layer or the like is provided, a solid base print layer composed of one color of black or white is formed as the base layer of the print pattern layer. is there.
By the way, when the underprint layer as described above is formed, similarly to the above, the packaged product is irradiated with ultraviolet light, through the transition metal catalyst, for example, to the unsaturated bond portion of the cyclohexene ring as the oxygen-absorbing resin. It has been found that the oxygen scavenging function of attacking radicals, binding oxygen from the chain reaction, and absorption is not sufficiently performed.
Furthermore, it was found that when a biaxially stretched polyester resin film is used as a base film and a desired printed pattern layer, base printed layer, etc. are provided on this, an oxygen scavenging function cannot be expected at all. Is.
Therefore, the present invention sterilizes the inner surface of the laminate constituting the packaging bag, fills and packs the contents, sufficiently captures oxygen present or generated in the package, and exhibits its oxygen collecting function. To provide packaging products that protect the quality of the contents.

As a result of various studies to solve the above problems, the present inventor firstly made a base film, a barrier base film, an oxygen-absorbing resin by a resin composition containing an oxidizing resin and a transition metal catalyst. And a laminate in which the heat-seal resin layer is sequentially laminated, and then the laminate is overlaid with the surfaces of the heat-seal resin layers facing each other. After that, when a packaging bag is manufactured by heat sealing the periphery of the outer periphery, and then the contents are filled and packaged from the opening in the packaging bag, or before the packaging After filling or packaging, or simultaneously with filling packaging, the inner surface of the packaging bag is irradiated with ultraviolet rays having an ultraviolet wavelength region of 200 to 280 nm in the range of 200 to 1000 mJ / cm ² from the inner surface side. Then fill the contents and open When a packaged product was manufactured by heat sealing the part to form a seal part and sealing it, the inner surface of the laminate constituting the packaging bag was sterilized and its oxygen absorption performance was expressed. Even if the packaged product is stored and stored for a long time and displayed for sale, no change in the color, taste, smell, etc. of the content is observed, and the quality of the content is protected very well The present invention has been completed by finding a packaged product that can be made.

That is, the present invention sequentially forms a base film, a barrier base film, an oxygen-absorbing resin layer comprising a resin composition containing an oxidizing resin and a transition metal catalyst, and a heat-sealable resin layer. A packaging bag comprising a laminated body, and further laminating the laminated body with the surfaces of the heat-sealable resin layers facing each other, and further heat-sealing the end portion around the outer periphery. Further, the contents are filled and packaged from the opening in the packaging bag and before the filling packaging, or after the filling packaging, or simultaneously with the filling packaging, on the inner surface of the packaging bag. Irradiates ultraviolet rays having an ultraviolet wavelength region of 200 to 280 nm in the range of 200 to 1000 mJ / cm < ² >, and sterilizes the inner surface of the laminate constituting the packaging bag and expresses its oxygen absorption performance And the above Opening heat - tosylate - Le to be - relates packaged product characterized by sealing by forming a pole tip.

In the packaged product according to the present invention, by irradiating the inner surface of the laminate constituting the packaging bag with ultraviolet rays having an ultraviolet wavelength region of 200 to 280 nm in an ultraviolet irradiation amount range of 200 to 1000 mJ / cm ² , The inner surface of the laminate constituting the packaging bag can be sterilized or sterilized, whereby a sterilized or aseptically packaged packaged product can be manufactured.
Further, in the packaged product according to the present invention, the contents are filled and packaged, and the inner surface of the packaging bag is irradiated with ultraviolet light from the inner surface side, and then the opening is heat sealed. The ultraviolet light easily reaches the oxygen-absorbing resin layer, and the transition metal catalyst constituting the oxygen-absorbing resin layer acts on the oxidizing resin. The oxidizing resin binds and absorbs oxygen present in the head space or the like in the packaging bag, oxygen contained in the contents, or generated oxygen, and develops an oxygen collecting function. It is something that can be done.
Thus, in the packaged product according to the present invention, as a result, it becomes possible to simultaneously perform sterilization or sterilization of the inner surface of the laminate constituting the packaging bag and expression of the oxygen collecting function, The oxygen permeated from outside the packaged product is coupled with the function of blocking the permeation by the barrier substrate film, and the quality, freshness, etc. of the contents are almost the same as when packed and packaged. Maintaining the product as it is or more, and even when the packaged product is stored, stored, or displayed for a long period of time, almost no change in the quality of the content, such as color, taste, smell, etc. is observed. Quality, freshness, etc. can be protected very well.
In addition, the packaged product according to the present invention does not impair its appearance, is excellent in its cosmetics, etc., is compatible with the above-mentioned content protection performance, and can extend the product life of the content. It is a thing.

Hereinafter, the packaged product according to the present invention will be described in more detail with reference to the drawings.
First, a description will be given of a laminated body forming a packaging bag constituting a packaged product according to the present invention with reference to the drawings by exemplifying a few examples of the layer structure. FIG. 1, FIG. 2 and FIG. FIG. 4 is a schematic cross-sectional view showing a layer configuration of a few examples of a laminated body forming a packaging bag constituting the packaging product according to FIG. 4, and FIG. 4 uses the laminated body according to the present invention shown in FIG. FIG. 5 and FIG. 6 are schematic perspective views showing an example of the configuration of the packaging bag according to the present invention manufactured by bag-making this, and FIG. 5 and FIG. 6 are inside the packaging bag according to the present invention shown in FIG. It is a schematic perspective view which shows an example of the structure about the packaging product which filled and packaged the contents in the.

  First, as shown in FIG. 1, a laminate A forming a packaging bag constituting a packaged product according to the present invention includes a substrate film 1, a barrier substrate film 2, an oxidizing resin, a transition metal catalyst, The basic structure is composed of a structure in which an oxygen-absorbing resin layer 3 and a heat-sealable resin layer 4 are sequentially laminated.

Thus, with regard to the laminated body forming the packaging bag constituting the packaged product according to the present invention, as shown in FIG. 2, first, the base film 1 having the desired printed pattern 5 and The barrier substrate film 2 is overlapped with the surface of the printed pattern 5 facing each other, and then both are laminated via an adhesive layer 6 for laminating, while the oxidizing resin and the transition metal are laminated. A resin composition containing a catalyst and a resin composition containing a resin as a main component of a vehicle are used, and these are formed into a two-layer coextrusion film using a T-die co-extruder or an inflation co-extruder. And an oxygen-absorbing resin layer 3a made of a resin composition containing the oxidizing resin and the transition metal catalyst, and a transparent or translucent heat seal made of a resin composition containing the resin as a main component of the vehicle. Co-extrusion consisting of 2 types and 2 layers with conductive resin layer 4a The layer laminated film 7 is manufactured, and then the surface of the barrier base film 2 laminated above is overlapped with the surface of the oxygen-absorbing resin layer 3a of the coextruded multilayer laminated film 7 produced above. , Thereafter, the both lamination - can be exemplified a laminate a ₁ to form a packaging bag that constitutes the packaging product according to the present invention was laminated via preparative adhesive layer 6a.

Moreover, if another specific example is given about the laminated body which forms the packaging bag which comprises the packaging product which concerns on this invention, as shown in FIG. 3, it has the desired printed pattern 5 first as shown above. The base film 1 and the barrier base film 2 are overlapped with the surface of the printed pattern 5 facing each other, and then both of them are laminated via a laminating adhesive layer 6, and the other is oxidized. A resin composition containing a functional resin and a transition metal catalyst, and a resin composition containing the resin as a main component of the vehicle, and using a T-die co-extruder or an inflation co-extruder, etc. A resin composition comprising a transparent or translucent heat-sealable resin layer 4a made of a resin composition comprising the above resin as a main component of a vehicle, and a co-extruded film, and an oxidizing resin and a transition metal catalyst. Oxygen-absorbing resin layer 3a made of material and the above tree A coextruded multi-layer laminated film 7a composed of two types and three layers with a transparent or translucent heat-sealable resin layer 4b made of a resin composition containing as a main component of the vehicle, and then laminated as described above The surface of the conductive substrate film 2 and the surface of the transparent or translucent heat-seal resin layer 4a of the coextruded multilayer laminated film 7a produced above are opposed to each other, and then both are laminated. A laminate A ₂ that forms a packaging bag constituting the packaged product according to the present invention laminated through the laminating adhesive layer 6a can be exemplified.
The above exemplification shows a few examples of the laminated body for producing the packaging bag constituting the packaged product according to the present invention, and the present invention is not limited to this. In the present invention, although not shown in the drawings, according to the purpose of use, application, etc., other substrates are optionally laminated to form a laminate constituting the packaging bag according to the present invention having various forms. It can be designed and manufactured.

  Next, in the present invention, an example of the packaging bag according to the present invention produced by using the laminate according to the present invention as described above will be described and the configuration thereof will be described. As the bag, for example, the packaging bag according to the present invention produced by using the laminate A according to the present invention shown in FIG. 1 will be described. As shown in FIG. Two laminates A and A according to the present invention are prepared, and the heat seal resin layers 4 and 4 located in the innermost layer are overlapped with each other facing each other. The three-side seal type packaging bag B according to the present invention can be manufactured by heat-sealing these three sides to form the seal portions 11, 11, 11 and the opening 12. it can.

Thus, in the present invention, as shown in FIG. 5, the packaging bag B according to the present invention manufactured as described above is used, and, for example, the ultraviolet irradiation device 13 is indicated by an arrow P from the opening 12 thereof. The inner surface of the packaging bag B is irradiated with ultraviolet light 14, and then, as shown in FIG. 6, in the packaging bag B according to the present invention irradiated with ultraviolet light 14, From the opening 12, for example, various contents 15 composed of food and drink, miscellaneous goods, and other articles are filled, and then the opening 12 is heat sealed to form the upper seal 16. Forming can produce the packaged product C according to the present invention.
Thus, in the present invention, when ultraviolet light is irradiated using the above-described ultraviolet irradiation device or the like, ultraviolet light having an ultraviolet wavelength region of 200 to 280 nm from the inner surface side is irradiated on the inner surface of the packaging bag with an ultraviolet irradiation amount of 200. Irradiation in the range of up to 1000 mJ / cm ² , thereby sterilizing or sterilizing the inner surface of the laminate constituting the packaging bag, and expressing its oxygen absorption performance, this sterilization or sterilization and oxygen absorption Both performance and performance are performed simultaneously.
In particular, in the present invention, when ultraviolet light is irradiated using an ultraviolet irradiation device or the like, an ultraviolet wavelength region in the range of 250 nm to 265 nm having the highest wavelength of sterilization or sterilization from the inner surface to the inner surface of the packaging bag. Is irradiated in the range of 200 to 1000 mJ / cm ² of ultraviolet irradiation amount, thereby sterilizing or sterilizing the inner surface of the laminate constituting the packaging bag and expressing its oxygen absorption performance, This sterilization or sterilization and the development of oxygen absorption performance are performed simultaneously.

In the present invention, although not shown in the drawings, for example, a vertical or horizontal pillow-type packaging bag filling and packaging machine or the like is used. First, the packaging product according to the present invention as described above from the winding roll. The laminated body forming the packaging bag constituting the film is supplied in the form of a raw film, and then ultraviolet light is applied to the surface of the heat-sealable resin layer constituting the laminated body in the state of the raw film. , Followed by steps such as back sealing, end sealing, filling the contents, bag making such as a top seal, filling and packaging the contents, etc. Can be manufactured.
In the present invention, although not shown, the packaging bag can be provided with an opening notch such as an I notch or a V notch.
The above illustration is an example of the laminated body, packaging bag, or packaged product according to the present invention, and the present invention is not limited thereto. For example, the packaging according to the present invention Although not shown in the figure, the bag for packaging can be manufactured in various forms such as a pillow packaging form, a gusset packaging form, a standing (self-supporting) pouch packaging form, and the like.
In the present invention, although not shown, the laminate according to the present invention shown in FIG. 2 and FIG. 3 is used, and in the same manner as described above, according to the present invention having various forms as described above. It can manufacture packaging bags, packaging products, and the like.
Furthermore, in the present invention, for the irradiation with ultraviolet light, for example, the state of the raw film before bag making, the packaging bag before filling the contents, the packaging bag after filling, or packaging at the same time as filling A bag can be irradiated with ultraviolet light.

Next, in the present invention, materials, manufacturing methods, etc. constituting the laminate, packaging bag, packaged product, etc. according to the present invention will be described. First, the laminate, packaging bag, packaged product according to the present invention. As a base film that constitutes, etc., since this becomes a basic material constituting a laminate, packaging bag, packaging product, etc., it has excellent strength in mechanical, physical, chemical, etc. Furthermore, it is possible to use a resin film or sheet that is excellent in puncture resistance and the like, in addition, excellent in heat resistance, moisture resistance, transparency, etc., and in particular, a resin film or sheet having printability is used. It is preferable to do.
Specifically, in the present invention, as the base film, for example, polyethylene resin, polypropylene resin, cyclic polyolefin resin, fluorine resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile Ru-butadiene-styrene copolymer (ABS resin), polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin, polyethylene terephthalate, polyethylene naphthalate Polyester resins such as various polyamide resins such as nylon, polyimide resins, polyamideimide resins, polyaryl phthalate resins, silicone resins, polysulfone resins, polyphenylene sulfide resins, polyether sulfones Resin, polyurethane resin, AS - Le resins, cellulose - scan resin, various resins other such film or sheet - may be used and.
In the above, as the resin film or sheet, any of an unstretched film or a stretched film stretched in a uniaxial direction or a biaxial direction can be used.
In the present invention, the thickness of the resin film or sheet may be a thickness that can be kept to the minimum necessary for strength, puncture resistance, etc., and if it is too thick, the cost increases. On the other hand, if it is too thin, the strength, puncture resistance, etc. will be undesirably reduced.
In the present invention, for the reasons described above, about 3 μm to 100 μm, preferably about 5 μm to 50 μm is most desirable.
Thus, in the present invention, it is desirable to use a biaxially stretched polyethylene terephthalate film having a thickness of 5 to 12 μm from the viewpoints of strength and others as the base film.

  In the present invention, the above-mentioned base film can be provided with a desired printed pattern, and as such printed pattern, for example, one or more kinds of normal ink vehicles are used as a main component. If necessary, one kind of additives such as plasticizers, stabilizers, antioxidants, light stabilizers, UV absorbers, curing agents, crosslinking agents, lubricants, antistatic agents, fillers, etc. Furthermore, two or more kinds are optionally added, and further, a coloring agent such as a dye or pigment is added, and the ink composition is prepared by sufficiently kneading with a solvent, an imperial agent, etc., and then the ink composition is used. Using, for example, gravure printing, offset printing, letterpress printing, screen printing, transfer printing, flexographic printing, etc., on the surface and / or back surface of the aforementioned plastic substrate, for example, letters, graphics, etc. , Symbols, patterns, etc. It can be formed by printing a desired printed pattern.

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

Next, in the present invention, the barrier substrate film constituting the laminate, the packaging bag, the packaged product, etc. according to the present invention will be described. As such a barrier substrate film, mainly oxygen gas, water vapor, etc. In particular, it is possible to use a material / material that prevents oxygen gas from permeating into the packaging bag from the outside through the laminated body constituting the packaging bag.
Specifically, for example, a resin film that prevents permeation of oxygen gas, water vapor, or the like, a resin film having a metal foil or a deposited film of the metal, or a resin film having a deposited film of an inorganic oxide, Others can be used.
For example, as the resin film for preventing permeation of oxygen gas, water vapor and the like, for example, polyvinylidene chloride resin, polyvinyl alcohol resin, saponified ethylene-vinyl acetate copolymer, nylon MXD6 and the like alone Or a resin film or sheet such as co-extrusion or a coating film thereof can be used.
The film thickness of the resin film or sheet or the coating film thereof is, for example, several μm to several tens μm, specifically 3 to 50 μm, preferably about 5 to 30 μm. Things can be used.
Moreover, as said metal foil, aluminum foil, copper foil, tin foil, various alloy foils, etc. can be used, for example, Generally, it is preferable to use aluminum foil.
The film thickness of the metal foil is about 6 to 20 μm, preferably about 7 to 10 μm.

In addition, as the resin film having the above-described metal vapor-deposited film, for example, a metal is applied to one surface of the resin film, for example, a vacuum vapor deposition method, a sputtering method, an ion plating method, an ion cluster beam method. The metal vapor deposition resin film etc. which formed the vapor deposition film | membrane of the metal using physical vapor deposition methods etc. can be used.
In the above, as a metal which comprises a vapor deposition film, metals, such as aluminum, nickel, tin, bismuth, indium, cadmium, lead, others, can be used, for example.
Therefore, in the present invention, it is preferable to use aluminum as the metal in consideration of versatility, economy, etc.
In the above, the thickness of the metal deposition film is preferably about 200 to 1000 mm, preferably about 300 to 800 mm.
Next, in the above, as the resin film, the resin film or sheet constituting the base film can be used in the same manner.
Specifically, polyethylene resins, polypropylene resins, polystyrene resins, polyvinyl chloride resins, polycarbonate resins, polyethylene terephthalates, polyester resins such as polyethylene naphthalates, and the like. Transparent or translucent films or sheets of various resins such as polyamide resins such as nylon and others can be used.
The film thickness is most desirably about 3 μm to 50 μm, preferably about 5 μm to 30 μm.

Next, as a resin film having an inorganic oxide vapor deposition film, for example, a vacuum vapor deposition method, a sputtering method, an ion plating method, an ion cluster beam method, etc. on one surface of the resin film. Using a physical vapor deposition method (Physical Vapor Deposition method, PVD method), for example, a resin film in which a deposited film of an inorganic oxide such as aluminum oxide or silicon oxide is formed can be used.
In the present invention, specifically, a metal or a metal oxide is used as a raw material, this is heated and vaporized, and this is vapor-deposited on one surface of the resin film, or a metal or metal as a raw material. Inorganic oxidation using an oxidation reaction deposition method that uses an oxide, oxidizes by introducing oxygen and deposits on one side of the resin film, and a plasma-assisted oxidation reaction deposition method that promotes the oxidation reaction with plasma. A resin film on which a vapor deposition film of an object is formed can be used.
In the above, as a heating method for the vapor deposition material, for example, a resistance heating method, a high frequency induction heating method, an electron beam heating method (EB), or the like can be used.
In the present invention, for example, on one surface of the resin film, a chemical vapor deposition method (chemical vapor deposition method, CVD, etc.) such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, or a photochemical vapor deposition method is used. For example, a resin film in which a vapor-deposited film of an inorganic oxide such as silicon oxide is used can be used.
In the present invention, specifically, on one surface of the resin film, a monomer gas for vapor deposition such as an organosilicon compound is used as a raw material, and an inert gas such as argon gas or helium gas is used as a carrier gas, In addition, oxygen gas is used as the oxygen supply gas, and a resin film in which an inorganic oxide vapor deposition film such as silicon oxide is formed using a low temperature plasma chemical vapor deposition method using a low temperature plasma generator or the like is used. can do.
In the above, for example, high-frequency plasma, pulse wave plasma, microwave plasma, or the like can be used as the low-temperature plasma generator. Thus, in the present invention, highly active and stable plasma is obtained. Therefore, it is desirable to use a high-frequency plasma generator.

In the present invention, the film thickness of the inorganic oxide vapor-deposited film as described above is, for example, desirably selected and formed within a range of about 50 to 2000 mm, preferably about 100 to 1000 mm.
In the above, as the resin film, a resin film or sheet constituting the above-mentioned base film can be used in the same manner.
Specifically, polyethylene resins, polypropylene resins, polystyrene resins, polyvinyl chloride resins, polycarbonate resins, polyethylene terephthalates, polyester resins such as polyethylene naphthalates, and the like. Transparent or translucent films or sheets of various resins such as polyamide resins such as nylon and others can be used.
The film thickness is most desirably about 3 μm to 50 μm, preferably about 5 μm to 30 μm.

  Next, in the present invention, an oxygen-absorbing resin layer made of a resin composition containing an oxidizing resin and a transition metal catalyst constituting the laminate, packaging bag, packaged product, etc. according to the present invention will be described. As the functional resin layer, the contents are mainly filled and packaged in a packaging bag, and thus, oxygen present in the packaged product, for example, in the head space or the like, is inherent in the contents. It absorbs and captures oxygen contained in the packaged product, such as oxygen generated from the contents, other oxygen, etc., and more specifically, oxidizing resin and transition metal catalyst And, if necessary, a thermoplastic resin as a binder, or a resin film made of a resin composition optionally containing additives such as a radical generator, a photosensitizer, and the like. .

Next, in the present invention, the heat-sealable resin layer constituting the laminate, packaging bag, packaged product and the like according to the present invention will be described. As the heat-sealable resin layer, mainly, When the laminated body according to the present invention described later is used to form a bag and to produce a packaging bag, it has a function of forming a seal portion with a heat seal and the above-mentioned It is provided for protection, concealment, etc. of the oxygen-absorbing resin layer.
Thus, in the present invention, the heat-sealable resin layer can be composed of a resin film made of a resin composition containing a thermoplastic resin as a main component of the vehicle.

Thus, in the present invention, the oxygen-absorbing resin layer, the heat-sealable resin layer, and the like constituting the laminate, the packaging bag, the packaged product and the like according to the present invention are specifically the above-mentioned The oxygen-absorbing resin layer and the heat-sealable resin layer can be configured as a coextruded multilayer laminated film.
The coextruded multilayer laminated film including the oxygen-absorbing resin layer and the heat-sealable resin layer according to the present invention will be described. First, it includes an oxidizing resin and a transition metal catalyst, and further if necessary. , Thermoplastic resins as binders, or additives such as radical generators or photosensitizers, etc., for example, when forming the film, film processability, heat resistance, weather resistance, mechanical properties, dimensions Various plastic compounding agents and additives, etc., for the purpose of improving and modifying stability, antioxidant properties, slipperiness, mold release properties, flame retardancy, antifungal properties, electrical properties, strength, etc. A resin composition that forms the oxygen-absorbing resin layer according to the present invention is prepared by optionally adding seeds or two or more kinds, and if necessary, adding a solvent, a diluent, etc., and kneading sufficiently. .
On the other hand, in the same manner as described above, for example, one or more thermoplastic resins are used as the main component of the vehicle, and if necessary, for example, when forming the film, for example, film processability, heat resistance, Various plastics for the purpose of improving and modifying weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold release properties, plowing properties, mold resistance, electrical properties, strength, etc. One or two or more of compounding agents, additives and the like are arbitrarily added, and if necessary, a solvent, a diluent, etc. are added and kneaded sufficiently to make the heat seal property according to the present invention. The resin composition for forming the resin layer is adjusted. In the present invention, examples of the plastic compounding agent and additive include, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, a band dragon inhibitor, and a flame retardant. , Flame retardants, foaming agents, anti-fungal agents, pigments, dyes, dispersants, surfactants, anti-blocking agents, etc. can be used, and further, modifying resins can be used, Furthermore, the addition amount can be arbitrarily added from a very small amount to several tens of weight% according to the purpose.

Next, in the present invention, first, after preparing the respective resin compositions as described above, the resin compositions are used, and they are combined, for example, a T-die co-extruder, an inflation co-extruder, etc. Can be coextruded to produce coextruded multilayer laminated films having various layer configurations.
Thus, in the present invention, a specific method for producing a coextruded multilayer laminated film using each resin composition as described above will be described. In the present invention, first, for example, the present invention prepared above is used. The resin composition for forming the oxygen-absorbing resin layer according to the present invention and the resin composition for forming the heat-sealable resin layer according to the present invention are used. Two-layer coextrusion molding using an inflation co-extrusion machine, etc., the first layer is an oxygen-absorbing resin layer, the second layer is a heat-sealable resin layer in this order, and two-layer coextrusion lamination A coextruded multilayer laminated film comprising two types and two layers according to the present invention having the above-described structure can be produced.

  Alternatively, in the present invention, first, for example, the resin composition for forming the oxygen-absorbing resin layer according to the present invention prepared above and the resin composition for forming the heat-sealable resin layer according to the present invention. These are then co-extruded in three layers using, for example, a T-die co-extruder, an inflation co-extruder, etc., so that the first layer is a heat-sealable resin layer, Coextruded multilayer laminated film comprising two types and three layers according to the present invention, wherein two layers are constituted by coextruding three layers in the order of an oxygen-absorbing resin layer and a third layer being a heat-sealable resin layer. Can be manufactured.

The above exemplifications illustrate one or two examples of the coextruded multilayer laminated film and the production method thereof according to the present invention, and the present invention is not limited thereto.
In the present invention, a method for producing a coextruded multilayer laminated film having an arbitrary layer structure is prepared by preparing each resin composition, and further, other resin compositions, etc., arbitrarily selecting them, and combining them. To get.
In the present invention, when producing the co-extruded multilayer laminated film according to the present invention, other materials are further used depending on the purpose of use, applications, etc., and these are optionally co-extruded and laminated. A coextruded multilayer laminated film having a shape can be designed and manufactured.

Next, in the present invention, the thickness of the coextruded multilayer laminated film according to the present invention is desirably about 20 μm to 250 μm in total thickness, preferably about 30 μm to 190 μm.
Thus, in the above-mentioned coextruded multilayer laminated film, as the film thickness of each layer constituting the coextruded multilayer laminated film, first, the film thickness of the oxygen-absorbing resin layer is preferably about 5 μm to 50 μm. Is preferably in the range of about 10 μm to 30 μm.
Further, the thickness of the heat-sealable resin layer is desirably in the range of about 5 μm to 100 μm, preferably about 10 μm to 80 μm.
In the above, if the film thickness of the co-extruded multilayer laminated film according to the present invention is 20 μm, more preferably less than 30 μm, it becomes difficult to form the film itself, and the strength decreases, blurring, scratches, etc. This is not preferable because it is likely to cause defects, and if it exceeds 250 μm, and more than 190 μm, there is no problem in the strength of the film, but it is not preferable in terms of the environment and cost.
In addition, in the above, if the film thickness of the oxygen-absorbing resin layer according to the present invention is 5 μm, more preferably less than 10 μm, there is a high possibility that the required oxygen-absorbing physical properties are not sufficiently exhibited. Further, it is not preferable, and if it exceeds 50 μm, and more than 30 μm, it is not preferable for reasons such as an increase in cost and a layer whose strength has deteriorated due to oxygen absorption affects the physical properties of the entire film.
Furthermore, in the above, when the film thickness of the heat-sealable resin layer according to the present invention is 5 μm, and further less than 10 μm, the function as the seal layer is lowered, and the heat seal strength is reduced. Is unpreferable for reasons such as the possibility that it may become insufficient, and if it exceeds 100 μm, and more than 80 μm, there is no problem as seal strength, but it is preferable for reasons such as an increase in cost and environmental problems. There is nothing.

In the above, as the oxidizing resin constituting the oxygen-absorbing resin layer according to the present invention, for example, the following materials can be used.
(1). Ethylenically unsaturated hydrocarbon polymer: ethylenically unsaturated hydrocarbon polymer having a molecular weight of at least 1,000, atactic-1,2-polybutadiene, EPDM rubber, polyoctenamer, 1,4-polybutadiene, syndiotactic- 1,2-polybutadiene, partially polymerized unsaturated fatty acids and esters, block or graft copolymers, hydrosite-like materials can be used.
The oxygen-absorbing anion is an ascorbate anion, a thiolate anion, a phenolate anion, or a mixture thereof, bisulfite, dithionic acid or a mixture thereof.
These carriers are polyethylene, polyolefin, ethylene / vinyl acetate copolymer, butyl rubber, styrene / butadiene rubber, styrene / butadiene / styrene block copolymer, styrene / ethylene / butylene / styrene block copolymer, vinyl chloride homopolymer, chloride. A thermoplastic resin selected from the group consisting of vinyl polymers and blends thereof.

(2). Main chain ethylenically unsaturated hydrocarbon polymer: Number average molecular weight is in the range of 1,000 to 500,000.
R _{1 is} an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkyl aryl group, or an alkoxy group, and R ₂ and R are each a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, A substituted aryl group, an unsubstituted aryl group, —COOR ₄ , —OCOR ₅ , a cyano group, or a halogen atom, and R ₄ and R ₅ are each independently an alkyl group having 1 to 10 carbon atoms, An aryl group, an alkyl aryl group or an alkoxy group.
A thermoplastic resin containing carbon-carbon double bonds at a rate of 0.0001 eq / g or more.
Structural formula —CH ₂ —CH—
｜
C-R ₁
‖
R ₂ —C—R ₃
A resin composition in which R ₁ , R ₂ and R ₃ are a methyl group and a hydrogen atom, respectively.

(3). Polyether unit polymer: A polymer containing 0.001 to 10 parts by weight of an oxidation catalyst with respect to 100 parts by weight of a polymer having a polyether unit.
A multi-block copolymer in which a polyether unit has a polyalkylene glycol ether segment as a soft segment and at least one selected from the group consisting of polyester, polyamide, and polyurethane segments as a hard segment.
A polymer containing polyether units.
As a polymer containing a polyether unit, if it is a polymer containing an aromatic polyether unit, a polyalkylene ether unit (aliphatic polyether unit) or other generally known polyether unit as a polyether unit, It may be a single polymer or a copolymer.
Examples of the polymer containing an aromatic polyether unit include poly (2,6-dimethyl-1,4-phenylene ether), poly (2,6-diethyl-1,4-phenylene ether) and the like. And polyphenylene ethers or copolymers containing these. Polymers containing polyalkylene ether units include polymethylene glycol, polyethylene glycol, poly (1,2-propylene glycol), poly (1,3-propylene glycol), poly In addition to linear and branched aliphatic ethers such as tetramethylene glycol, poly (1,2-butylene glycol) and polyhexamethylene glycol, cyclohexanediol condensates and cyclohexanedi Examples thereof include a single polymer or copolymer of an alicyclic ether such as a condensation product of methanol.
In addition, random copolymers in these ether units are also included in the gist of the present invention.
A polymer containing a polyalkylene ether unit is particularly preferably used, and among them, a multiblock copolymer having a polyalkylene ether unit can be preferably used.
As these multi-block copolymers, polyester ether block copolymers (polyester thermoplastic elastomer) using aromatic polyester and polyalkylene ether, aliphatic polyester and polyalkylene ether are used. Polyurethane block having a hard segment composed of a polymer of a multi-block copolymer, a polymer of a short-chain glycol and a diisocyanate, and a soft segment composed of a polymer of a diisocyanate and a polyalkylene ether Examples thereof include a plastic elastic body, and a polyamide polyether copolymer (block copolyetheramide, block copolyetheresteramide, block copolyetheresteramide, etc.) using polyamide and polyalkylene ether.
When the segment copolymerized with the polyalkylene ether has crystallinity, these copolymers generally become elastic bodies.
The polyalkylene ether units contained in these copolymers include polyalkylene ethers having a number average molecular weight of 400 to 6,000 (for example, polyethylene glycol, poly (1,2- and 1,3 -Propylene glycol), polytetramethylene glycol, polyhexamethylene glycol, etc.) can be suitably used.
Particularly preferred is polytetramethylene glycol.
As the polyalkylene ether unit, those having a number average molecular weight of 400 to 6,000 are usually used, but those having 600 to 4,000 are preferable, and those having 1,000 to 3,000 are particularly preferable. is there.
When the number average molecular weight is less than 400, sufficient oxygen absorption performance cannot be exhibited.
On the other hand, those exceeding 6,000 tend to cause phase separation in the system and tend to lower the physical properties of the polymer obtained by copolymerization or the like (see JP-A-2003-64250).

(4). Copolymers of ethylene and strained cyclic alkylene: Cyclic alkylene includes cyclopentene, cyclobutene, cycloptene, cyclooctene, cyclononene, cyclohexene.
And a photosensitizer (see JP-T-2003-504042).

(5). Polyamide resin: poly-m-xylylene-adipamide, nylon 6-6, poly-m-xylylene adipamide, poly-m-xylylene sebacamide and poly-m-xylylene speramide as examples of homopolymers, Examples of copolymers include m-xylylene / p-xylylene adipamide copolymer, m-xylylene / p-xylylene piperamide copolymer, m-xylylene / p-xylylene azelamide copolymer.
Examples of aliphatic diamines include hexamethylene diamine, examples of cyclic diamines, piperazine, examples of aromatic diamines, p-bis (2-aminoethyl) benzene, examples of aromatic dicarboxylic acids include terephthalic acid. .
In addition, benzylamine, 3-methylbenzylamine, metaxylylenediamine, paraxylylenediamine, N, N′-dimethylmetaxylylenediamine, N, N, N ′, N′-tetramethylmetaxylylenediamine, N , N′-dimethylparaxylylenediamine, N, N, N ′, N′-tetramethyl parameter xylylenediamine, N, N′-diethylmetaxylylenediamine, N, N, N ′, N′-tetraethylmeta Xylylenediamine, N, N′-diethylparaxylylenediamine, N, N, N ′, N′-tetraethylparaxylylenediamine, 1,3,5-tris (aminomethyl) benzene, metaxylylenediamine or para Xylylenediamine and organic carboxylic acids, such as monocarboxylic acids such as stearic acid, oleic acid, lauric acid, tall oil fatty acid It is obtained by reacting salts and amides with dicarboxylic acids such as adipic acid, sebacic acid and dimer acid, and metaxylylenediamine or paraxylylenediamine, which is widely used as an epoxy resin curing agent, with formaldehyde and phenol. Mannich base, metaxylylenediamine or paraxylylenediamine and adducts of vinyl compounds such as acrylonitrile and methyl methacrylate, metaxylylenediamine or paraxylylenediamine and epoxy compounds such as bisphenol A epoxy resins, bisphenol Adducts with F-based epoxy resin, butyl glycidyl ether, etc., and cured epoxy resins cured with these curing agents, amino group-containing epoxy compounds represented by tetraglycidyl metaxylylenediamine , Metaxylylene diisocyanate, isocyanate compounds represented by paraxylylene diisocyanate and polyurethanes derived from each of them can be exemplified, but a plurality of these compounds are used in combination. You can also

  (6). Acid-modified polybutadiene: Polybutadiene, polyisoprene, styrene-butadiene block copolymer, acrylate or polyterpene produced by transesterification of poly (ethylene-methyl acrylate) (see JP 2002-505575 A).

(7). Hydroxyaldehyde polymer: Glycolaldehyde, Glyceraldehyde-As aliphatic aldehyde, aliphatic unsaturated aldehyde such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, aliphatic unsaturated such as acrylic aldehyde, fumaraldehyde Hydroxy aldehydes such as aldehyde, glycol aldehyde and glyceraldehyde, alkoxy aldehydes such as 2-methoxyethanol, oxo aldehydes such as 2-oxopropanal, amino aldehydes such as 2-amino ethanol, 2-chloroethanol Halogen-substituted aldehydes such as ruthenium, alicyclic aldehydes such as cyclohexanecarbaldehyde, and aldehydes substituted with aromatic rings such as 2-phenylethanol.
It is possible to use two or more kinds of polymers.
Thus, in the present invention, the oxidizing resin as described above mainly has an unsaturated double bond unit in the main chain and in the skeleton or in the side chain, and the unsaturated double bond. The portion exhibits a function such as oxygen absorption by being saturated by interaction with oxygen, for example, by a chain reaction with radicals.
In the present invention, specific examples of the oxidizing resin include ethylene / methyl acrylate / cyclohexenyl methyl acrylate polymer, cyclohexenyl methyl acrylate / ethylene copolymer, and cyclohexenyl. Preference is given to using a methyl acrylate / styrene copolymer, a cyclohexenyl methyl acrylate homopolymer or a methyl acrylate / cyclohexenyl methyl acrylate copolymer.

In the above, the transition metal catalyst constituting the oxygen-absorbing resin layer according to the present invention is selected from, for example, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Sn, Cu or a mixture thereof. Transition metals can be used.
Compositions in which the transition metal is selected from Co, Cu, Fe or mixtures thereof, and Group VIII metal components of the periodic table are preferred, but Group I metals: Group IV metals such as tin, titanium, zirconium, etc. Group V such as vanadium, Group VI such as chromium, and Group VII such as manganese.
Used in the form of low-valent inorganic acid salts, organic acid salts or complex salts of the above transition metals.
Examples of inorganic acid salts include halides such as chlorides, sulfur oxyacid salts such as sulfates, nitrogen oxyacid salts such as nitrates, phosphorus oxyacid salts such as phosphates, and silicates.
Examples of the organic acid salt include carboxylate, sulfonate, phosphonate and the like.
Carboxylate is considered optimal.
Specific examples include acetic acid, propionate, isopropionic acid, butanoic acid, isobutanoic acid, pentanoic acid, isopentanoic acid, hexanoic acid, heptanoic acid, isoheptanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, 3, 5,5-trimethylhexanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, lindelic acid, tuzuic acid, petroceric acid, oleic acid, Examples include transition metal salts such as linoleic acid, linolenic acid, arachidonic acid, formic acid, oxalic acid, sulfamic acid, and naphthenic acid.
Thus, in the present invention, the transition metal catalyst as described above mainly promotes radical decomposition reaction by applying energy such as ultraviolet light (UV), and the oxidation resin shown above is used. It functions to start and develop oxygen absorption.
In the present invention, as the above transition metal catalyst, specifically, cobalt neodecanoate, cobalt 2-ethylhexanoate, cobalt oleate and cobalt stearate are preferably used. Is.

Furthermore, in the above, as the thermoplastic resin as a binder to be used, if necessary, constituting the oxygen-absorbing resin layer according to the present invention, it can be melted by heat and extruded from an extrusion die such as an extruder. Furthermore, it is possible to use a mixture of one type or two or more types of thermoplastic resins which are thermally fused to each other.
Specifically, for example, low density polyethylene (LDPE), linear (linear) low density polyethylene (polymer polymerized using a multisite catalyst, LLDPE), polymerization using a metallocene catalyst (single site catalyst) Ethylene-α / olefin copolymer, medium density polyethylene (MDPE), high density polyethylene (HDPE), polypropylene resin, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate Copolymers, ethylene-methacrylic acid copolymers, ethylene-methyl methacrylate copolymers, ethylene-propylene copolymers, methylpentene polymers, polybutepolymers, polyolefin resins such as polyethylene or polypropylene, acrylic acid, methacrylic acid, maleic acid , Acid-modified polyolefin resin modified with unsaturated carboxylic acid such as hydromaleic acid, fumaric acid, itaconic acid, polyvinyl acetate resin, poly (meth) acrylic resin, polyvinyl chloride resin, thermoplastic polyester resin, heat One type or two or more types of thermoplastic resins such as plastic polyamide resins and others can be used.
Therefore, in the present invention, as the thermoplastic resin, it is preferable to use an ethylene-α-olefin copolymer polymerized using a metallocene catalyst (single site catalyst) as a main component of the vehicle. .
Thus, in the present invention, the thermoplastic resin as described above mainly has a certain degree of affinity for the oxidizing resin, is thermoplastic, and exhibits functions such as heat seal suitability. It is.

Furthermore, in the above, examples of the radical generator or photosensitizer that constitutes the oxygen-absorbing resin layer according to the present invention, if necessary, include benzoin, acenaphthenequinone, benzoin methyl ether, benzoin ethyl. Benzoin such as ether and benzoin isopropyl ether and alkyl ethers thereof; acetophenone, methyl ethyl ketone, valerophenone, hexaphenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloro Acetophenone such as acetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one Anthraquinones such as 2-methylanthraquinone and 2-amylanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; acetophenone dimethylketer In general, ketones such as benzyl dimethyl ketal; benzophenones such as benzophenone or xanthones are generally known as photoinitiators.
These photoradical initiators can be used in combination with one or more known and commonly used photopolymerization accelerators such as benzoic acid type or tertiary amine type.
In addition, at least one selected from ketocarbonyl compounds, amine compounds, transition metals and their compounds, and halogen compounds can be used.
Examples of the α-ketocarbonyl compound include α-diketone, α-ketoaldehyde, α-ketocarboxylic acid, α-ketocarboxylic acid ester, specifically, diacetyl, 2,3-pentanedione, 2,3-hexanedione, Α- such as benzyl, 4,4-dimethoxybenzyl, 4,4-oxybenzyl, 4,4-dichlorobenzyl, 4-nitrobenzyl, α-naphthyl, β-naphthyl, camphorquinone, 1,2-cyclohexanedione, etc. Α-Ketoaldehydes such as diketones, methylglyoxal, phenylglyoxal, pyruvic acid, benzoylformic acid, phenylpyruvic acid, methyl pyruvate, ethyl benzoylformate, methyl phenylpyruvate, butyl phenylpyruvate have been used.
Acetyltetralone, Linderic acid, Margaric acid, Stearic acid, Adipic acid, Diacetylbenzoin, Distearoylmethane, methane, and dibivaloylmethane can be used.
Thus, in the present invention, the radical generator or photosensitizer as described above mainly serves as an auxiliary function of the transition metal catalyst used as a catalyst, and performs the oxidation reaction of the oxidizing resin. It plays a function of making it progress dramatically and forcibly.
In the present invention, as the radical generator or photosensitizer, specifically, benzophenone, benzoin methyl ether, or the like is preferably used.

Next, in the present invention, in the resin composition containing the oxidizing resin constituting the oxygen-absorbing resin layer and the transition metal catalyst, the blending ratio of the oxidizing resin and the transition metal catalyst is the oxidizing resin 100. It is preferable to prepare the resin composition at a blending ratio of 0.001 to 10 parts by weight of transition metal catalyst with respect to parts by weight.
In the above, if the transition metal catalyst is less than 0.001, it is not preferable because the catalytic action is low and the oxidation reaction does not proceed, and if it exceeds 10 parts by weight, the catalyst amount is too large. Although the oxidation reaction proceeds, it is not preferable because other side reactions or the like occur or the cost increases.
In the present invention, when a radical generator or a photosensitizer is added, it is preferably added at a blending ratio of 0.001 to 10 parts by weight with respect to 100 parts by weight of the oxidizing resin. .
Furthermore, in the present invention, when adding a thermoplastic resin, it is also preferable to add it at a blending ratio of 50 to 100 parts by weight with respect to 100 parts by weight of the oxidizing resin.

Next, in the present invention, the thermoplastic resin constituting the heat-sealable resin layer according to the present invention is, for example, melted by heat and can be extruded from an extrusion die such as an extruder, It is possible to use a mixture of one or two or more thermoplastic resins that are thermally fused to each other. Specifically, for example, low density polyethylene (LDPE), linear (linear) low density polyethylene (polymer polymerized using a multisite catalyst, LLDPE), polymerization using a metallocene catalyst (single site catalyst) Ethylene-α / olefin copolymer, medium density polyethylene (MDPE), high density polyethylene (HDPE), polypropylene resin, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate Copolymers, ethylene-methacrylic acid copolymers, ethylene-methyl methacrylate copolymers, ethylene-propylene copolymers, methylpentene polymers, polybutepolymers, polyolefin resins such as polyethylene or polypropylene, acrylic acid, methacrylic acid, maleic acid , Acid-modified polyolefin resin modified with unsaturated carboxylic acid such as hydromaleic acid, fumaric acid, itaconic acid, polyvinyl acetate resin, poly (meth) acrylic resin, polyvinyl chloride resin, thermoplastic polyester resin, heat One type or two or more types of thermoplastic resins such as plastic polyamide resins and others can be used.
Therefore, in the present invention, as the thermoplastic resin, it is preferable to use an ethylene-α-olefin copolymer polymerized using a metallocene catalyst (single site catalyst) as a main component of the vehicle. .

And Thus, it coextruded multilayer laminate film according to the to the present invention produced as described above, after UV irradiation of ^{1000mJ / cm 2, 300cc / m} 2 · 5day · atm or more, preferably, 500 cc / m ² · It exhibits an oxygen absorption performance of 5 days · atm or more, and is extremely useful as an oxygen-absorbing material.

  Next, in this invention, the laminated body which forms the packaging bag which comprises the packaging product which concerns on this invention is the above base film, barrier base film, oxygen-absorbing resin layer, and heat Examples of the laminate in which the tosyl resin layers and the like are sequentially laminated include, for example, various types of resins such as a dry laminate lamination method in which lamination is performed through an adhesive layer for lamination, or anchor coat agent layers. Laminates according to the present invention having various forms can be produced using a melt extrusion laminate lamination method in which layers are laminated while being melt extruded, and other lamination methods.

In the above, as the laminating adhesive constituting the laminating adhesive layer, for example, polyvinyl acetate adhesive, homopolymer such as ethyl acrylate, butyl, 2-ethylhexyl ester, etc. Copolymerization of polyacrylic acid ester adhesive, cyanoacrylate adhesive, ethylene and vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, and other monomers consisting of copolymers with methyl acid, acrylonitrile, styrene, etc. Ethylene copolymer adhesives made of coalescence, cellulose adhesives, polyester adhesives, polyamide adhesives, polyimide adhesives, amino resin adhesives made of urea resin or melamine resin, phenolic resin adhesives , Epoxy adhesives, polyurethane adhesives, reactive (meth) a Uses adhesives such as ril adhesives, chloroprene rubber, nitrile rubber, rubber adhesives made of styrene-butadiene rubber, silicone adhesives, alkali metal silicates, inorganic adhesives made of low-melting glass, etc. You can do it.
The composition system of the above-mentioned adhesive may be any composition form such as an aqueous type, a solution type, an emulsion type, and a dispersion type, and the property is any of film / sheet form, powder form, solid form, etc. Further, the bonding mechanism may be any of a chemical reaction type, a solvent volatilization type, a heat melting type, a hot pressure type, and the like.
Thus, the adhesive can be applied by, for example, a roll coating method, a gravure roll coating method, a kiss coating method, a coating method such as others, a printing method, or the like. ˜10.0 g / m ² (dry explosion state) is desirable.

In the above, examples of the anchor coating agent constituting the anchor coating agent layer include various aqueous or oily anchor coating agents such as organic titanium-based, isocyanate-based, polyethyleneimine-based, polyptadiene-based, etc. such as alkyl titanate. Can be used.
The anchor coating agent can be coated by using a coating method such as roll coating, gravure roll coating, kiss coating, etc., and the coating amount is 0.1 to 5.0 g / m ² (dry). Explosive state is desirable.

Examples of the melt-extruded resin layer in the melt-extrusion laminate lamination method include, for example, polyethylene resins, polypropylene resins, acid-modified polyethylene resins, acid-modified polypropylene resins, ethylene-acrylic acid or methacrylic acid copolymers, One type of thermoplastic resin such as Surlyn resin, ethylene-vinyl acetate copolymer, polyvinyl acetate resin, ethylene-acrylic acid ester or methacrylic acid ester copolymer, polystyrene resin, polyvinyl chloride resin, etc. Two or more types can be used.
In the melt extrusion lamination laminating method, in order to obtain stronger adhesive strength, for example, lamination can be performed via an anchor coating agent layer such as the anchor coating agent.
In the present invention, when performing the above-described lamination, for example, on the surface of each substrate to be laminated, for example, corona discharge treatment, ozone treatment, flame treatment, plasma treatment, etc. A pretreatment can be optionally applied.

Next, in the present invention, a method for producing a bag for packaging according to the present invention by making a bag using the laminate according to the present invention as described above will be described. Using the laminated body according to the present invention, the inner heat-seal resin layer face is faced and folded, or two of them are overlapped, and the peripheral end is further heated. The bag for packaging which consists of various forms can be manufactured by providing a seal part by tossing.
Thus, as the bag making method, the laminated body constituting the packaging bag according to the present invention as described above is folded with the inner layers facing each other, or the two sheets are overlapped, and further, For example, the peripheral edge of the outer periphery may be, for example, a side seal type, a two-sided seal type, a three-sided seal type, a four-sided seal type, an envelope-attached seal type, a joint-attached seal type (pillar Various types of heat seals according to the present invention, such as a seal type), a pleated seal type, a flat bottom seal type, a square bottom seal type, and the like. The packaging bag which consists of a form can be manufactured.
In addition, for example, a self-supporting packaging bag (standing pouch) or the like can be manufactured.
In the above, as the heat seal method, for example, a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal and the like are known. It can be done by the method.
In the present invention, for example, a one-piece type, a two-piece type, or other spout, or a zipper for opening and closing is arbitrarily attached to the packaging bag according to the present invention as described above. Can do.

In the present invention, the packaging bag according to the present invention manufactured as described above includes, for example, various foods and drinks, chemicals such as adhesives and adhesives, cosmetics, detergents, pharmaceuticals, miscellaneous goods such as chemical warmers, Various products such as other can be filled and packaged to produce packaged products having various forms.
Thus, in the present invention, in the packaged product according to the present invention manufactured as described above, when filling and packaging the contents from the opening in the packaging bag constituting the packaged product, the filling Before, after filling, or simultaneously with filling, the inner surface of the packaging bag is irradiated with ultraviolet light from the inner surface side, and then the opening of the packaging bag is heat sealed. -A package product according to the present invention is manufactured by forming a sealing portion and sealing it.
In the present invention, by irradiating the inner surface of the packaging bag with ultraviolet light from the inner surface side as described above, the surface of the laminated body constituting the packaging bag is sterilized or sterilized and subjected to sterilization treatment. Ultraviolet light passes through the heat-sealable resin layer constituting the packaging bag and reaches the oxygen-absorbing resin layer very well, and the ultraviolet light acts on the transition metal catalyst, Activated, thereby enabling, for example, an oxygen scavenging function of attacking a radical to an unsaturated bond part of a cyclohexene ring as an oxygen resin, and binding and absorbing oxygen from a chain reaction. is there.
In addition, in this invention, an ultraviolet light is irradiated to the laminated body which is the state of the original fabric film before bag making, and then bag making, filling packing of contents, etc. can also be performed.

In the above, as an ultraviolet irradiation device that irradiates ultraviolet light, an irradiation method, irradiation conditions, etc., for example, as an ultraviolet irradiation device, for example, an ultraviolet (UV) irradiation device using a high-pressure mercury lamp (for example, Eye Graphics Corporation) Company name, model name, ECS-401GX, etc. can be used.
Thus, in the present invention, as described above, as the ultraviolet irradiation method, the inner surface of the packaging bag is irradiated from the inner surface side, for example, before, after, or simultaneously with the contents. As the irradiation conditions, for example, as the intensity of ultraviolet rays, ultraviolet rays having an ultraviolet wavelength region of an ultraviolet wavelength of 200 to 280 nm, particularly an ultraviolet wavelength in the range of 250 nm to 265 nm having the highest sterilization or sterilization action with ultraviolet having a region, as the integrated quantity of ^{light, 200mJ / cm 2 ~2000mJ / cm} 2 -position, preferably at 200mJ / cm ² ~1000mJ / cm ^2-position, as an irradiation time of the ultraviolet light, the correlation between the lamp light intensity In this case, the irradiation can be performed for a time satisfying the above integrated light quantity, for example, about 10 seconds to 80 seconds.
In the above, if the ultraviolet wavelength is less than 200 nm, it is not preferable because it is difficult to generate ultraviolet rays, and if it exceeds 280 nm, it is not preferable because there is a possibility of generating odor due to ultraviolet irradiation. It is.
In addition, in the above, if the integrated light amount is less than 200 mJ / cm ² , the ultraviolet light energy is insufficient and the oxidation reaction tends to be insufficient, and if the integrated light amount exceeds 2000 mJ / cm ² , This is unfavorable because it has a large influence and may be difficult to use as a film.
Next, the present invention will be described more specifically with reference to examples.

(1). First, a co-extruded multilayer laminated film was produced by the following method.
First, the following resin compositions (a) to (c) were prepared.
(I). 100.0 parts by weight of high-pressure low-density polyethylene [HPLDPE, density, 0.923 g / m ³ , melt flow rate (MFR), 3.5 g / 10 min] and 0.5% by weight of synthetic silica Part, 0.05 part by weight of erucic acid amide, and 0.05 part by weight of ethylenebisoleic acid amide were sufficiently kneaded to prepare a resin composition for forming the first layer.
(B). As the oxidizing resin (second layer), 100.0 parts by weight of [ethylene / methyl acrylate / methyl cyclohexene methyl acrylate copolymer] and as the transition metal catalyst [cobalt 2-ethylhexanoate A resin composition for forming the second layer by sufficiently kneading 0.01 part by weight and 0.001 part by weight of [1-hydroxy-cyclohexyl-enyl-ketone] as a radical photopolymerization initiator Prepared.
(C). High pressure method low density polyethylene (HPLDPE, density, 0.923 g / m ³ , melt flow rate (MFR), 3.5 g / 10 min) 100.0 parts by weight and 0.5% by weight of synthetic silica The resin composition for forming the third layer was prepared by sufficiently kneading the part.
Next, using the resin compositions (a) to (c) prepared above, the first layer of the resin composition (a) was formed using a top-blown air-cooled inflation coextrusion film forming machine. Co-extruded multilayer according to the present invention having a total thickness of 50 μm consisting of three layers by coextrusion of 20 μm, (b) the second layer of the resin composition to 10 μm, and (c) the third layer of the resin composition to 20 μm A laminated film was produced.
(2). Next, the surface of the first layer of the coextruded multilayer laminated film according to the present invention produced above is subjected to a corona discharge treatment, and then the two-component curable urethane adhesive (main agent: Polyester polyol, curing agent: aliphatic isocyanate) is used, and this is coated with a gravure roll coat method to a thickness of 4.0 g / m ² (dry state) to form an adhesive layer for laminating. Thereafter, a biaxially stretched polyethylene terephthalate film having a thickness of 200 μm and having a vapor deposition film of silicon oxide having a thickness of 200 mm is laminated on the surface of the adhesive layer for laminating with the surface of the vapor deposition film of silicon oxide facing each other. In addition, after that, both of them were dry laminated, and further, the above-mentioned dry laminated laminate of 200 μm thick silicon oxide deposited film having a thickness of 12 μm was formed. The biaxially stretched polyethylene terephthalate film surface of the ethylene terephthalate film is subjected to corona discharge treatment in the same manner as described above, and a two-component curable urethane-based adhesive (main component: polyester polyol, (Hardening agent: aliphatic isocyanate) is used, and this is coated to a thickness of 4.0 g / m ² (in a dry state) using a gravure roll coat method to form an adhesive layer for laminating. The biaxially oriented polypropylene film having a thickness of 20 μm having a desired printed pattern layer is superimposed on the surface of the adhesive layer for laminating, with the corona-treated surface and the printed pattern layer facing each other, and then, Both of them were dry laminated to produce a laminate according to the present invention. (3). Next, two laminates according to the present invention produced as described above are prepared, the surfaces of the third layer of the co-extruded multilayer laminate film according to the present invention are opposed to each other, and then, the edges around the outer periphery thereof. The part was heat-sealed to form a seal part, and a packaging bag composed of a three-way seal type soft packaging bag having an opening at the top was formed.
Next, on the inner surface of the packaging bag produced as described above, an ultraviolet irradiation device [manufactured by Eye Graphics Co., Ltd., model surface, ECS-401GX] is used, and ultraviolet light having an ultraviolet wavelength of 254 nm is used as an integrated light quantity of 1000 mJ / The packaged product was manufactured by irradiating cm ² and then filling with fresh pasta and then heat sealing the opening to form an upper seal.
In the packaged product produced above, the raw pasta that enables sterilization packaging and deteriorates due to oxygen was not observed to be discolored or deteriorated in odor even in a 1-month holding test.

(1). First, a co-extruded multilayer laminated film was produced by the following method.
First, the following resin compositions (a) to (c) were prepared.
(I). Ethylene-α-olefin copolymer polymerized by using a single-site catalyst (metallocene catalyst) for the (first layer) [Mitsui Chemicals, trade name, Eveille SP2020, density, 0.916 g / m ³ , melt Flowlet (MFR), 1.5 g / 10 min] 100.0 parts by weight, 0.5 parts by weight of synthetic silica, 0.05 parts by weight of erucic acid amide, 0.05 parts by weight of ethylenebisoleic acid amide Was sufficiently kneaded to prepare a resin composition for forming the first layer.
(B). As the oxidizing resin (second layer), 100.0 parts by weight of [styrene / butadiene copolymer], as the transition metal catalyst, 0.01 parts by weight of [cobalt 2-ethylhexanoate], a radical system As a photopolymerization initiator, 0.001 part by weight of [1-hydroxy-cyclohexyl-enyl-ketone] was sufficiently kneaded to prepare a resin composition for forming the second layer.
(C). An ethylene-α / olefin copolymer polymerized by using the same single-site catalyst (metallocene catalyst) as the first layer in the (third layer) [Mitsui Chemicals, trade name, Evolue SP2020, density, 0 .916 g / m ³ , Melt Flowlet (MFR), 1.5 g / 10 min] 100.0 parts by weight, 0.5 parts by weight of synthetic silica, 0.05 parts by weight of erucamide, and ethylenebisoleic acid A resin composition for forming the third layer was prepared by sufficiently kneading 0.05 part by weight of the amide.
Next, using the resin compositions (a) to (c) prepared above, the first layer of the resin composition (a) was formed using a top-blown air-cooled inflation coextrusion film forming machine. Co-extruded multilayer according to the present invention having a total thickness of 50 μm consisting of three layers by coextrusion of 20 μm, (b) the second layer of the resin composition to 10 μm, and (c) the third layer of the resin composition to 20 μm A laminated film was produced.
(2). Next, the surface of the first layer of the coextruded multilayer laminated film according to the present invention produced above is subjected to a corona discharge treatment, and then the two-component curable urethane adhesive (main agent: Polyester polyol, curing agent: aliphatic isocyanate) is used, and this is coated with a gravure roll coat method to a thickness of 4.0 g / m ² (dry state) to form an adhesive layer for laminating. Thereafter, a biaxially stretched nylon 6 film having a thickness of 200 μm and having an aluminum oxide vapor deposition film having a thickness of 200 mm is overlapped on the surface of the laminating adhesive layer with the aluminum oxide vapor deposition film face facing each other. Thereafter, both of them are dry laminated, and further, a biaxial layer having a thickness of 15 μm having a vapor deposition film of 200 mm thick aluminum oxide laminated as described above. The surface of the biaxially stretched nylon 6 film of the stretched nylon 6 film is subjected to a corona discharge treatment in the same manner as described above, and the two-component curable urethane adhesive (main agent: polyester polyol, curing agent: Aliphatic isocyanate) is coated using a gravure roll coat method to a thickness of 4.0 g / m ² (in the dry state) to form an adhesive layer for laminating, and then the laminate A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm having a desired printed pattern layer is placed on the surface of the adhesive layer for use so that the corona-treated surface and the printed pattern layer face each other. Both of them were dry laminated to produce a laminate according to the present invention.
(3). Next, two laminated bodies produced as described above are prepared, and the third layer surface of the coextruded multilayer laminated film according to the present invention constituting the laminated body is overlapped facing each other, and then the periphery of the outer periphery is prepared. The end portion was heat sealed to form a seal portion, and a packaging bag composed of a three-sided seal type soft packaging bag having an opening at the top was formed.
Next, on the inner surface of the packaging bag produced as described above, an ultraviolet irradiation device [manufactured by Eye Graphics Co., Ltd., model surface, ECS-401GX] is used, and ultraviolet light having an ultraviolet wavelength of 254 nm is used as an integrated light quantity of 1000 mJ / The packaged product was manufactured by irradiating cm ² and then filling with fresh pasta and then heat sealing the opening to form an upper seal.
In the packaged product produced above, the raw pasta that enables sterilization packaging and deteriorates due to oxygen was not observed to be discolored or deteriorated in odor even in a 1-month holding test.

(1). First, a co-extruded multilayer laminated film was produced by the following method.
First, the following resin compositions (a) to (c) were prepared.
(I). Ethylene-α-olefin copolymer polymerized by using a single-site catalyst (metallocene catalyst) for the (first layer) [Mitsui Chemicals, trade name, Eveille SP2020, density, 0.916 g / m ³ , melt Flowlet (MFR), 1.5 g / 10 min] 100.0 parts by weight, 0.5 parts by weight of synthetic silica, 0.05 parts by weight of erucic acid amide, 0.05 parts by weight of ethylenebisoleic acid amide Was sufficiently kneaded to prepare a resin composition for forming the first layer.
(B). (Poly-m-xylylene-adipamide) 100.0 parts by weight as the oxidizing resin (second layer), 0.01 parts by weight [cobalt 2-ethylhexanoate] as the transition metal catalyst, radical As a photopolymerization initiator, 0.001 part by weight of [1-hydroxy-cyclohexyl-enyl-ketone] was sufficiently kneaded to prepare a resin composition for forming the second layer.
(C). An ethylene-α / olefin copolymer polymerized by using the same single-site catalyst (metallocene catalyst) as the first layer in the (third layer) [Mitsui Chemicals, trade name, Evolue SP2020, density, 0 .916 g / m ³ , Melt Flowlet (MFR), 1.5 g / 10 min] 100.0 parts by weight, 0.5 parts by weight of synthetic silica, 0.05 parts by weight of erucamide, and ethylenebisoleic acid A resin composition for forming the third layer was prepared by sufficiently kneading 0.05 part by weight of the amide.
Next, using the resin compositions (a) to (c) prepared above, the first layer of the resin composition (a) was formed using a top-blown air-cooled inflation coextrusion film forming machine. Co-extruded multilayer according to the present invention having a total thickness of 50 μm consisting of three layers by coextrusion of 20 μm, (b) the second layer of the resin composition to 10 μm, and (c) the third layer of the resin composition to 20 μm A laminated film was produced.
(2). Next, the surface of the first layer of the coextruded multilayer laminated film according to the present invention produced above is subjected to a corona discharge treatment, and then the two-component curable urethane adhesive (main agent: Polyester polyol, curing agent: aliphatic isocyanate) is used, and this is coated with a gravure roll coat method to a thickness of 4.0 g / m ² (dry state) to form an adhesive layer for laminating. Thereafter, a biaxially stretched nylon 6 film having a thickness of 200 μm and having an aluminum oxide vapor deposition film having a thickness of 200 mm is overlapped on the surface of the laminating adhesive layer with the aluminum oxide vapor deposition film face facing each other. Thereafter, both of them are dry laminated, and further, a biaxial layer having a thickness of 15 μm having a vapor deposition film of 200 mm thick aluminum oxide laminated as described above. The surface of the biaxially stretched nylon 6 film of the stretched nylon 6 film is subjected to a corona discharge treatment in the same manner as described above, and the two-component curable urethane adhesive (main agent: polyester polyol, curing agent: Aliphatic isocyanate) is coated using a gravure roll coat method to a thickness of 4.0 g / m ² (in the dry state) to form an adhesive layer for laminating, and then the laminate A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm having a desired printed pattern layer is placed on the surface of the adhesive layer for use so that the corona-treated surface and the printed pattern layer face each other. Both of them were dry laminated to produce a laminate according to the present invention.
(3). Next, two laminates produced as described above are prepared, and the third layer surface of the co-extruded multilayer laminate film according to the present invention that constitutes the laminate is overlapped with each other. The end portion was three-way heat sealed to form a seal portion, and a packaging bag composed of a three-sided seal type soft packaging bag having an opening on the upper side was formed.
Next, on the inner surface of the packaging bag produced as described above, an ultraviolet irradiation device [manufactured by Eye Graphics Co., Ltd., model surface, ECS-401GX] is used, and ultraviolet light having an ultraviolet wavelength of 254 nm is used as an integrated light quantity of 1000 mJ / The packaged product was manufactured by irradiating cm ² and then filling with fresh pasta and then heat sealing the opening to form an upper seal.
In the packaged product produced above, the raw pasta that enables sterilization packaging and deteriorates due to oxygen was not observed to be discolored or deteriorated in odor even in a 1-month holding test.

The laminate manufactured in Example 2 above was used in the same manner, and this was mounted on a vertical pillow filling and packaging machine. Then, while supplying the above laminate, first, the opposite sides were set at the impulse sealer. -Is used to seal the longitudinal direction, and then, on the inner surface of the packaging bag manufactured as described above, an ultraviolet irradiation device [Model name, ECS-401GX, manufactured by Eye Graphics Co., Ltd.] is used to measure the ultraviolet wavelength. Irradiate ultraviolet light of 254 nm as an integrated light amount of 1000 mJ / cm ² , and then supply the raw pasta with filling, and seal the upper and lower sides while filling, and then close the upper and lower sheets. The package portion was cut and the packaged product was produced by filling and packaging the contents in a pillow bag.
In the packaged product produced above, the raw pasta that enables sterilization packaging and deteriorates due to oxygen was not observed to be discolored or deteriorated in odor even in a 1-month holding test.

The laminate manufactured in Example 2 above was used in the same manner. First, from this, two body materials (130 mm × 200 mm) and one bottom material (130 mm × 50 mm) constituting the body portion were prepared. Then, the two body members are faced to each other, and the bottom member is inserted into the inverted V shape between the lower parts, and then the above-mentioned body member is inserted using an impulse sealer. A self-standing bag (stand pouch) was manufactured by heat sealing the left and right ends and the lower end where the body and the bottom overlapped.
Next, an ultraviolet irradiation device [manufactured by Eye Graphics Co., model surface, ECS-401GX] is used on the inner surface of the self-supporting bag manufactured as described above, and ultraviolet light having an ultraviolet wavelength of 254 nm is used as an integrated light amount of 1000 mJ / The packaged product was manufactured by irradiating cm ² and then filling with raw pasta and then heat sealing the opening to form an upper seal.
In the packaged product produced above, the raw pasta that enables sterilization packaging and deteriorates due to oxygen was not observed to be discolored or deteriorated in odor even in a 1-month holding test.

The laminate produced in Example 2 above was used in the same manner. First, one packaging member (280 mm × 170 mm) was prepared from the laminate, and then the opposing 170 mm sides were formed using an impulse sealer. Sealing was performed, and then the upper and lower sides were closed and folded in a V shape so that both ends were heat-sealed to produce a gusset bag.
Next, on the inner surface of the gusset-type bag manufactured as described above, an ultraviolet irradiation device (model surface, ECS-401GX, manufactured by Eye Graphics Co., Ltd.) is used, and ultraviolet light having an ultraviolet wavelength of 254 nm is 1000 mJ / The packaged product was manufactured by irradiating cm ² and then filling with fresh pasta and then heat sealing the opening to form an upper seal.
In the packaged product produced above, the raw pasta that enables sterilization packaging and deteriorates due to oxygen was not observed to be discolored or deteriorated in odor even in a 1-month holding test.

(Experimental example)
Each physical property evaluation in the coextruded multilayer laminated film produced in the above Examples 1 to 3 was performed as follows.
(1). Oxygen absorption test About the coextruded multilayer laminated film manufactured in Examples 1 to 3 above, using an ultraviolet irradiation device [modeled surface, ECS-401GX, manufactured by Eye Graphics Co., Ltd.], distance between lamps 150 mm, lamp output As a result of irradiating an ultraviolet ray having an ultraviolet wavelength of 254 nm with an integrated light quantity of 600 mJ / cm ² at 120 W and a conveyor speed of 3.6 m / min (compare length 125 mm, width 250 mm), the expression of oxygen absorption ability was confirmed.
In order to confirm the expression of oxygen absorption capacity, a test film was cut into 10 cm × 10 cm squares, sealed in an aluminum pouch with 100 ml of air, stored at 3 ° C. and 23 ° C., 1 day, 2 days, 3 days, 7 The residual oxygen concentration in the pouch after the day was measured.
The results are shown in Table 1 below.

(Table 1)
┌────┬───────────────┬───────────────┐ │ │ Oxygen absorption rate (3 ℃) │ Oxygen absorption Speed (23 ° C) │ │ ├───┬───┬───┬───┼───┬───┬───┬───┤ │ │1 day later │2 days later │3 days later │ 7 days later │ 1 day later │ 2 days later │ 3 days later │ 7 days later │ ────┼───┼───┼───┼───┼───┼───┼───┼ ───┤ │Example 1│4.2│6.3│6.7│7.5│6.2│7.0│7.2│7.1│ ├────┼─── ┼───┼───┼───┼───┼───┼───┼───┤ │Example 2│3.8│6.0│7.0│7.3│ 5.8│7.2│7.0│7.3│ ├────┼───┼───┼───┼───┼───┼───┼───┼ ───┤ │Example 3│4 .5 | 5.8 | 6.5 | 7.3 | 6.5 | 7.5 | 7.4 | 7.6 | └────┴───┴───┴───┴─ ──┴───┴───┴───┴───┘ In Table 1 above, the unit of oxygen absorption rate is [cc / cm ² ].

As shown in Table 1 above, it was confirmed to show a good oxygen absorption capacity.

(2). Measurement of dissolved oxygen concentration in water For the coextruded multilayer laminated film produced in Examples 1 to 3 above, after irradiating ultraviolet rays of about 600 mJ / cm ² from the side of the heat-sealable resin layer, the inner dimension is 9 cm. Make a pouch of × 10 cm, then make a package sealed with 50 ml of tap water and a package sealed with 50 ml of tap water and 50 ml of air, and then store each at room temperature, one day later, two days later The dissolved oxygen concentration in water after 3 days and 7 days later was measured.
The results are shown in Table 2 below.

(Table 2)
┌────┬────────────────────────┐ │ │ Dissolved oxygen concentration in water (ppm) │ │ ├ ─────── ──────────────────┤ │ │ 50 ml of water │ │ ├────┬────┬────┬────┬──── ┤ │ │ 0 days │ 1 day later │ 2 days later │ 3 days later │ 7 days later │ ├────┼────┼────┼────┼────┼───┤┤ │ Example 1│8.6 │0.9 │0.8 │0.6 │0.7 │ ├────┼───┼────┼────┼────┼ ────┤ │Example 2 │8.6 │1.1 │1.0 │0.8 │0.6 │ ├────┼────┼────┼──── │────┼────┤ │Example 3│8.6 │1.3 │1.5 │1.0 │0.8 │ └────┴────┴─── ─┴─ ──┴────┴────┘
┌────┬────────────────────────┐ │ │ Dissolved oxygen concentration in water (ppm) │ │ ├ ─────── ──────────────────┤ │ │ 50 ml of water + 50 ml of air │ │ ├ ────┬────┬────┬────┬── ──┤ │ │0 days │1 day later │2 days later │3 days later │7 days later │ ├────┼────┼────┼────┼────┼──── ┤ │Example 1 │8.6 │2.2 │3.1 │3.0 │2.4 │ ├────┼───┼────┼────┼─── ─┼────┤ │Example 2 │8.6 │2.0 │2.5 │2.8 │2.7 │ ├────┼────┼────┼── ──┼────┼────┤ │Example 3│8.6 │2.5 │2.4 │2.7 │2.7 │ └ └────┴──── ────┴────┴────┴────┘

As shown in Table 2 above, it was confirmed that good oxygen absorptivity was exhibited.

(3). Measurement of the number of viable bacteria About the coextruded multilayer laminated film produced in the above Examples 1 to 3, A. niger black mold, B.I. Subtilis Bacillus subtilis (spore) is used and the number of viable bacteria of 100 levels is applied on the coextruded multilayer laminated film produced in Examples 1 to 3 above using a sterile cotton swab, and then an ultraviolet wavelength of 254 nm UV lamp (manufactured by Toshiba Corporation, sterilizing lamp GL15 × 2) is used, and the lamp has a film distance of 105 mm, UV illuminance of 2.5 to 2.9 mW / cm ² , and irradiation time of 0, 15 , 30, 45, 60 seconds to sterilize.
After UV irradiation, A. niger include potato dextro-agar medium, B.I. Subtilis was cultured using tryptoiso agar medium.
The culture time was 3 days, and the temperature was A. niger is 30 ° C., B.I. The subtilis was 37 ° C.
The coextruded multilayer laminated film produced in the above Examples 1 to 3 was cultured, and the viable cell count was measured. The results are shown in Table 3 below.

(Table 3)
┌────┬────────────────────────┐ │ │ Viable count (individuals) │ │ ├ ───────── ────────────────┤ │ │ A. niger │ │ ├────┬────┬────┬────┬────┤ │ │0 seconds │15 seconds │30 seconds │45 seconds │60 seconds │ ├─── ─┼────┼────┼────┼────┼────┤ │Example 1│100 │ 9 │ 0 │ 0 │ 0 │ ├────┼── ──┼────┼────┼────┼────┤ │Example 2│100 │ 10 │ 0 │ 0 │ 0 │ ├ ────┼────┼─ ───┼────┼────┼────┤ │Example 3│100 │ 7 │ 0 │ 0 │ 0 │ └────┴────┴────┴ ────┴────┴────┘
┌────┬────────────────────────┐ │ │ Viable count (individuals) │ │ ├ ───────── ────────────────┤ │ │ B. subtilis │ │ ├────┬────┬────┬───┬┬────┤ │ │0 seconds │15 seconds │30 seconds │45 seconds │60 seconds │ ├─── ─┼────┼────┼────┼────┼────┤ │Example 1│100 │ 0 │ 0 │ 0 │ 0 │ ├────┼── ──┼────┼────┼────┼────┤ │Example 2│100 │ 0 │ 0 │ 0 │ 0 │ ├ ────┼────┼─ ───┼────┼────┼────┤ │Example 3│100 │ 0 │ 0 │ 0 │ 0 │ └────┴────┴────┴ ────┴────┴────┘

  As shown in Table 3 above, niger black mold, B.I. About subtilis Bacillus subtilis (spore), it was confirmed that generation | occurrence | production of the living microbe was not recognized.

  The present invention provides a packaging product that sterilizes the inner surface of a laminate constituting a packaging bag, fills and packs the contents, captures oxygen present or generated in the package, and protects the quality of the contents Is something that can be done.

It is a rough sectional view showing an example of the layer composition about the layered product which forms the packaging bag which constitutes the packaging product concerning the present invention. It is a rough sectional view showing an example of the layer composition about the layered product which forms the packaging bag which constitutes the packaging product concerning the present invention. It is a rough sectional view showing an example of the layer composition about the layered product which forms the packaging bag which constitutes the packaging product concerning the present invention. It is a schematic perspective view which shows the structure of the example about the packaging bag which uses the laminated body which concerns on this invention shown in FIG. It is a schematic perspective view which shows the structure of the example about the packaging bag which irradiated the ultraviolet-ray on the inner surface of the packaging bag which concerns on this invention shown in FIG. 4 using the ultraviolet irradiation device. It is a schematic perspective view which shows an example of the structure about the packaging product which filled and packed the contents in the packaging bag based on this invention shown in FIG.

Explanation of symbols

A, A ₁ , A ₂ laminate B Packaging bag C Packaging product 1 Base film 2 Barrier base film 3, 3a Oxygen-absorbing resin layer 4, 4a, 4b Heat seal resin layer 5 Printing pattern 6, 6a Adhesive layer 7, 7b Coextruded multilayer laminated film 11 Seal portion 12 Opening portion 13 Ultraviolet irradiation device 14 Ultraviolet light 15 Contents 16 Upper seal portion

Claims (9)

It consists of a laminate in which a base film, a barrier base film, an oxygen-absorbing resin layer made of a resin composition containing an oxidizing resin and a transition metal catalyst, and a heat-sealable resin layer are sequentially laminated. Further, the laminate is composed of a packaging bag in which the surfaces of the heat-sealable resin layers are opposed to each other, and further, the end of the outer periphery is heat-sealed. An ultraviolet wavelength region of 200 to 280 nm is formed on the inner surface of the packaging bag by filling and packaging the contents from the opening in the packaging bag and before or after the filling packaging or simultaneously with the filling packaging. Is irradiated with ultraviolet rays having a dose of 200 to 1000 mJ / cm ² to sterilize the inner surface of the laminate constituting the packaging bag and to exhibit its oxygen absorption performance. Heat seal Packaging products, characterized in that sealing by forming a pole tip. The packaging product according to claim 1, wherein the base film is made of a biaxially stretched polyester resin film. The packaging product according to any one of claims 1 to 2, wherein the base film has a printed pattern layer on the front surface and / or the back surface and a base layer. The resin composition constituting the oxygen-absorbing resin layer further comprises an oxygen-absorbing resin layer made of a resin composition containing a binder, as described in any one of claims 1 to 3. Packaging products. The resin composition which comprises an oxygen absorptive resin layer consists of an oxygen absorptive resin layer by the resin composition containing a radical generator further, The said any one of Claims 1-4 characterized by the above-mentioned. Packaging products. The resin composition constituting the oxygen-absorbing resin layer further comprises an oxygen-absorbing resin layer made of a resin composition containing a photosensitizer, according to any one of claims 1 to 5, Packaging product to be listed. The oxygen-absorbing resin layer and the heat-sealable resin layer use a resin composition containing an oxidizing resin and a transition metal catalyst, and a resin composition containing a thermoplastic resin as a main component of the vehicle, The oxygen-absorbing resin layer and the heat-sealable resin layer are each composed of a two-layer coextrusion multilayer laminated film, which is sequentially laminated. Packaging products. The oxygen-absorbing resin layer and the heat-sealable resin layer use a resin composition containing an oxidizing resin and a transition metal catalyst, and a resin composition containing a thermoplastic resin as a main component of the vehicle, The heat-sealable resin layer, the oxygen-absorbing resin layer, and the heat-sealable resin layer are composed of a three-layer coextrusion multilayer laminated film sequentially laminated. The packaged product according to any one of 6 above. The packaged product according to any one of claims 1 to 8, wherein the ultraviolet ray is an ultraviolet ray having an ultraviolet wavelength region of a wavelength of 250 nm to 265 nm having the highest bactericidal action.

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