JP2006224399A - Oxygen absorbent multilayered laminated film, laminate using it, packaging bag and packaged product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a packaging material used for performing the filling packaging of content, developing an oxygen collecting function for sufficiently capturing oxygen present or produced in a package and useful for protecting the quality of the content, a packaging bag and a packaged product. <P>SOLUTION: This oxygen absorbent multilayered laminated film comprises a film composed of at least three layers and formed by a coextrusion film forming method. The first layer, which constitutes the surface layer of the film formed by the coextrusion film forming method, comprises a white resin layer formed from a resin composition containing a thermoplastic resin and a white colorant and the second layer, which constitutes the intermediate layer of the film formed by the coextrusion film forming method, comprises an oxygen absorbent resin layer formed from a resin composition containing an oxidizable resin and a transition metal catalyst. Further, the third layer, which constitutes the back layer of the film, comprises a transparent or translucent resin layer formed from a resin composition containing a thermoplastic resin. A laminate using it, the packaging bag and the packaged product are also disclosed. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an oxygen-absorbing multilayer laminated film and a laminate using the same, a packaging bag, and a packaged product. More specifically, the contents are filled and packaged, and oxygen present or generated in the package is captured. The present invention relates to an oxygen-absorbing multilayer laminated film useful for producing a packaged product that protects the quality of contents, a laminate using the same, a packaging bag, and a packaged product.

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 it to make bags, manufacture packaging bags of various forms, and then in the packaging bags, for example, various foods and beverages, chemical products such as liquid detergents, cosmetics, pharmaceuticals, miscellaneous goods In addition, plastic packaging products having various forms filled and packed with industrial articles and other various articles have been developed and proposed.
Thus, the above plastic packaging products are excellent in heat sealability and can sufficiently satisfy the sealing performance from the demands of protecting the quality of the contents, extending the storage period, etc. In addition, it is required to have an easy-open property that allows the packaging bag to be easily opened at the time of consumption.
In addition, depending on the contents to be filled and packaged, for example, it is required to have a gas barrier property that prevents permeation of oxygen gas, water vapor, or the like, or to have an aroma retaining property that protects the odor and the like of the content. It is what.
Furthermore, it is also required to have a light blocking property or a light blocking property that blocks transmission of sunlight, fluorescent light, and the like.
Therefore, in recent years, various materials, materials, etc. have been used to develop packaging materials having various layer configurations, and accordingly, packaging bags, packaging products, etc. having various forms have been developed and proposed. Yes.
Thus, in recent years, as one of them, for example, an iron powder-based oxygen absorbent 30 to 30 in which a thermoplastic resin 15 to 70% by weight and a powder having a primary particle diameter of 0.01 to 20 μm are aggregated to 5 to 200 μm. In an oxygen absorbing sheet that has been subjected to sheet processing of a thermoplastic resin composition comprising 85% by weight to a thickness of 10 μm to 5 mm, and then stretched at a magnification of 1.5 to 8.0 times in at least a uniaxial direction, There has been proposed an oxygen-absorbing multilayer sheet characterized in that a resin composition comprising a filler and a resin component is disposed as a porous layer on one or both sides of an oxygen-absorbing sheet (for example, a patent Reference 1).
Also, as another one, for example, a manufactured article suitable as 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 packaging article comprising an oxygen scavenging composition comprising a polymer backbone, a cyclic olefin pendant group, a linking group binding the olefin pendant group to the backbone and a transition metal catalyst, a multilayer film, a container, Manufacturing methods and others have also been proposed (see, for example, Patent Document 2).
Japanese Patent No. 3081976. Special table 2003-521552 gazette.

However, the oxygen-absorbing multilayer sheet according to Patent Document 1 has excellent controllability of oxygen-absorbing ability and oxygen-absorbing speed, and in particular, liquid (water, aqueous solution, etc.) or a substance containing liquid (solid matter, It has excellent resistance to elution contamination of oxygen absorbers when it comes in contact with paste-like materials, etc., especially for packaging materials such as highly water-containing foods, such as trays, lid materials, crown liners, mounts, etc. Although it is described that it can be used widely, in practice, for example, iron powder as an oxygen scavenger dissolves and exudes to the surface due to the influence of iron powder as an oxygen scavenger. In addition, there is a problem that it is difficult to perform visual inspection or inspection with a metal detector, and it is not suitable for cooking in a microwave oven.
Moreover, when using the packaging film, packaging material, etc. according to the above-mentioned Patent Document 2, and further producing a packaging container and then producing a packaging product using the packaging container, for example, a substrate film 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 a radical to an unsaturated bond part of a cyclohexene ring as an oxygen-absorbing resin through a metal catalyst, and binding and absorbing oxygen from a 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 is filled and packaged with the contents, sufficiently captures oxygen present or generated in the package, exhibits its oxygen collecting function, and is useful for protecting the quality of the contents, It is to provide packaging bags and packaging products.

  As a result of various studies to solve the above-mentioned problems, the present inventor first comprises at least three layers of a co-extrusion film-forming film, and further constitutes a surface layer of the above-mentioned co-extrusion film-forming film. The first layer comprises a white resin layer made of a resin composition containing a thermoplastic resin and a white colorant, and the second layer constituting the intermediate layer of the coextruded film-forming film is oxidizable. A third layer that comprises an oxygen-absorbing resin layer made of a resin composition containing a resin and a transition metal catalyst, and that constitutes the back layer of the coextruded film-forming film is made of a resin composition containing a thermoplastic resin. An oxygen-absorbing multilayer laminated film comprising a transparent or translucent resin layer is produced, and then the above oxygen-absorbing multilayer laminated film is used to form a base film, a barrier base film, and the above-described oxygen-absorbing property Multi-layer laminated film in order Further, the laminate is used, and the laminate is overlapped with the surfaces of the oxygen-absorbing multilayer laminate film facing each other, and then the peripheral edge of the outer periphery. Heat-sealed to make a packaging bag, and then the packaging bag is filled with the contents from the opening and before the filling packaging, after the filling packaging, or Simultaneously with filling and packaging, the inner surface of the packaging bag was irradiated with ultraviolet rays, and then the above-mentioned opening was heat sealed to form a seal portion and sealed to produce a packaged product. After filling and wrapping the contents with a conductive base film, oxygen-absorbing multilayer laminated film, etc., it blocks or prevents the permeation of oxygen gas and the like from the outside into the package, and is present or generated in the package Capture oxygen and store the packaged product for a long time, Even in tubes and exhibits, no change in the color, taste, odor, etc. of the contents is observed, and the quality of the contents can be protected very well, improving quality and extending shelf life. In addition, the white resin layer is excellent in light-shielding properties and cosmetics, etc., causing consumer's willingness to purchase without impairing the appearance, and is compatible with cosmetics and content protection. Useful oxygen-absorbing multilayer laminated film that has excellent rigidity, strength, etc., has excellent shape retention and self-supporting properties, and can achieve significant weight reduction and volume reduction of packaging materials, and can greatly contribute to reducing environmental impact. The present invention has been completed by finding bodies, packaging bags, packaging products, and the like.

  That is, the present invention comprises at least three layers of a co-extrusion film-forming film, and further, the first layer constituting the surface layer of the co-extrusion film-forming film comprises a thermoplastic resin and a white colorant. An oxygen-absorbing resin comprising a resin composition comprising a white resin layer comprising a resin composition, and wherein the second layer constituting the intermediate layer of the coextruded film-forming film comprises an oxidizing resin and a transition metal catalyst And the third layer constituting the back layer of the coextruded film-forming film comprises a transparent or translucent resin layer made of a resin composition containing a thermoplastic resin. The present invention relates to a conductive multilayer laminated film and a laminate using the same, a packaging bag, and a packaged product.

In the packaged product according to the present invention, first, the contents are filled and packaged, 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, or oxygen contained in the contents or generated oxygen, and absorbs oxygen. As a result, 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, for example, the state when filled and packaged Almost as it is or more In addition, even when the packaged product is stored, stored and displayed for a long period of time, almost no change in the quality of the contents such as color, taste, smell etc. is observed, and the quality, freshness, etc. of the contents are not observed. It can be protected very well, improving its quality and extending shelf life.
Further, in the packaged product according to the present invention, the base film or the transparent or translucent resin layer is excellent in heat sealability at the time of bag making and can sufficiently satisfy the sealing property. In addition, it has an easy-opening property that allows easy opening of packaging bags, is excellent in rigidity, strength, etc., has high shape retention and self-supporting properties, and further reduces the weight and volume of packaging materials. Achieved and can greatly contribute to reducing environmental impact.
Furthermore, in the packaged product according to the present invention, the white resin layer or the like does not impair the appearance, is excellent in its cosmetics, etc. Etc. can be extended.

Hereinafter, the oxygen-absorbing multilayer laminated film according to the present invention and a laminate using the same, a packaging bag, a packaged product, and the like will be described in more detail with reference to the drawings.
First, the oxygen-absorbing multilayer laminated film, laminate, packaging bag, packaged product and the like according to the present invention will be described with reference to the drawings. FIG. 1 and FIG. 2 show the oxygen-absorbing multilayer laminated film according to the present invention. FIG. 3 is a schematic cross-sectional view showing the layer configuration of the example, and FIG. 3 is a schematic diagram showing the layer configuration of the example of the laminate using the oxygen-absorbing multilayer laminated film according to the present invention shown in FIG. FIG. 4 is a schematic cross-sectional view, and FIG. 4 is a packaging bag according to the present invention produced by using a laminate using the oxygen-absorbing multilayer laminated film 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 product according to the present invention in which the contents are packed in the packaging bag according to the present invention shown in FIG. It is a schematic perspective view which shows an example.

  First, as the oxygen-absorbing multilayer laminated film A according to the present invention, as shown in FIG. The first layer 2 constituting the layer is composed of a white resin layer 2a made of a resin composition containing a thermoplastic resin and a white colorant, and the first layer 2 constituting the intermediate layer of the co-extrusion film-forming film 1 described above. The second layer 3 is composed of an oxygen-absorbing resin layer 3a made of a resin composition containing an oxidizing resin and a transition metal catalyst, and the third layer 4 constituting the back layer of the coextruded film-forming film 1 is The basic laminated structure consists of a transparent or translucent resin layer 4a made of a resin composition containing a thermoplastic resin.

Next, in the present invention, as another example of the oxygen-absorbing multilayer laminated film according to the present invention, as shown in FIG. 2, in the oxygen-absorbing multilayer laminated film A according to the present invention shown in FIG. The oxygen-absorbing multilayer laminated film A ₁ having a structure in which a transparent or translucent resin layer 5a made of a resin composition containing a thermoplastic resin is further provided as the fourth layer 5 on the white resin layer 2a. Can be illustrated.
In FIG. 2, symbols such as 1, 2, 2a, 3, 3a, 4, 4a and the like represent the same meaning as those in FIG.

Next, in the present invention, an example of the laminate using the oxygen-absorbing multilayer laminate film according to the present invention will be described as an example. As the laminate B according to the present invention, for example, FIG. The laminated body according to the present invention using the oxygen-absorbing multilayer laminated film A according to the present invention will be described as an example. As shown in FIG. 3, the oxygen-absorbing multilayer laminated structure according to the present invention shown in FIG. Using the film A, a basic laminated structure is obtained by sequentially laminating the base film 11, the barrier base film 12, and the oxygen-absorbing multilayer laminated film A according to the present invention shown in FIG. Is.
In the above, the base film 11 can be provided with a desired printed pattern layer 13 (FIG. 3) and the like.
In the present invention, it is preferable that the oxygen-absorbing multilayer laminated film according to the present invention is laminated in such a manner that the surface of the white resin layer faces the surface of the barrier substrate film.
In FIG. 3, reference numerals 1, 2, 2a, 3, 3a, 4, 4a and the like represent the same meaning as those in FIG.
In the present invention, the oxygen-absorbing multilayer laminated film according to the present invention shown in FIG. 2 is used and laminated with a base film, a barrier base film and the like in the same manner as above, The laminate according to the present invention can be manufactured. In this case, it is preferable that the surface of the transparent or translucent resin layer is laminated so as to face the surface of the barrier substrate film. Is.

  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 as an example. The packaging bag C according to the present invention will be described. As an example, the packaging bag according to the present invention produced by using the laminate B according to the present invention shown in FIG. 3 will be described. As shown in FIG. 2 are prepared, and the oxygen-absorbing multilayer laminated films A and A located in the innermost layer are overlapped with each other facing each other. -Sealing to form the sealing portions 21, 21, 21 and the opening 22 to produce the three-sided sealing type packaging bag C according to the present invention.

  Thus, in the present invention, as shown in FIG. 5, the packaging bag C according to the present invention manufactured as described above is used, and from the opening 22, for example, using an ultraviolet irradiation device 23, It is moved up and down as indicated by an arrow P, and the inner surface of the packaging bag C is irradiated with ultraviolet light 24, and then irradiated with ultraviolet light 24 as shown in FIG. The bag C is filled with various contents 25 made of, for example, food and drink, miscellaneous goods, and other articles from the opening 22, and then the opening 22 is heat sealed and the upper sheet is placed. -The package part D which concerns on this invention can be manufactured by forming the lug part 26. FIG.

The above exemplification is an example of the oxygen-absorbing multilayer laminated film, laminate, packaging bag, or packaging product according to the present invention, and the present invention is not limited thereby. Needless to say.
For example, although not shown in the present invention, for example, a vertical or horizontal pillow-type packaging bag filling and packaging machine or the like is used. The laminate that forms the packaging bag constituting the film is supplied in the form of an original film, and then the surface of the oxygen-absorbing multilayer laminated film that constitutes the laminate in the state of the original film is irradiated with ultraviolet light. Then, through the steps of back seal, end seal (bottom seal), filling the contents, normal bag making such as top seal, filling and packaging the contents, etc. The packaged product according to the present invention 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.

Of course, using the oxygen-absorbing multilayer laminated film according to the present invention shown in FIG. 2, the laminate, packaging bag, or packaged product according to the present invention can be produced in the same manner as described above. It is something that can be done.
Further, in the present invention, although not shown in the drawings, it is possible to design and manufacture laminates having various layers by arbitrarily laminating other base materials depending on the purpose of use, application, and the like. .
Further, for example, as a form of the packaging bag according to the present invention, although not shown, for example, for packaging comprising various forms such as a pillow packaging form, a gusset packaging form, a standing (self-supporting) pouch packaging form, etc. A bag can be manufactured.
Further, in the present invention, although not shown in the drawings, for the irradiation of ultraviolet light, for example, the state of the raw film before bag making, the packaging bag before filling the contents, or the packaging bag after filling, or Simultaneously with filling, the packaging bag or the like can be irradiated with ultraviolet light.
In the above, although not shown, as a laminating method for laminating a base film, a barrier base film, an oxygen-absorbing multi-layer laminated film, etc., for example, the lamination is performed through a laminating adhesive layer. Lamination can be performed by a dry lamination method, a melt extrusion method in which layers are laminated via an anchor coating agent layer, a melt-extruded resin layer, or the like.

Next, in the present invention, the oxygen-absorbing multilayer laminated film, the laminate, the packaging bag, the packaging product and the like constituting the above-described present invention will be described. First, the oxygen absorption according to the present invention will be described. As the multi-layer laminated film, mainly has heat seal performance, cosmetics, oxygen absorption performance, etc., for example, the laminate according to the present invention is used to make a bag for packaging. When a bag is manufactured or when a packaged product or the like is manufactured, a seal part is formed by a heat seal, and the function of making or manufacturing a bag for packaging or a packaged product is achieved. In addition, it has an oxygen collecting function of binding and absorbing oxygen present in the head space of the packaging bag, packaged product, etc., or oxygen contained in the contents or generated oxygen. In addition, packaging bags and packaging products When producing, without compromising the beautification of it is intended to arouse consumer confidence like.
Of course, the oxygen-absorbing multilayer laminated film according to the present invention is excellent in rigidity, strength, etc., and has high shape retention and self-supporting properties, and further achieves weight reduction and volume reduction of packaging materials, and reduces environmental impact. It can greatly contribute to.
Thus, in the present invention, the oxygen-absorbing multilayer laminated film according to the present invention comprises at least three layers of a co-extrusion film-forming film, and further comprises a surface layer of the above-mentioned co-extrusion film-forming film. One layer is composed of a white resin layer made of a resin composition containing a thermoplastic resin as a main component of a vehicle and a white colorant, and constitutes an intermediate layer of the coextruded film-forming film. The two layers consist of an oxygen-absorbing resin layer made of a resin composition containing an oxidizing resin and a transition metal catalyst, and the third layer constituting the back layer of the coextruded film-forming film is a thermoplastic resin. The basic layer structure is composed of a transparent or translucent resin layer made of a resin composition containing as a main component of the vehicle.
Furthermore, in the present invention, as the oxygen-absorbing multilayer laminated film according to the present invention, on the white resin layer in the oxygen-absorbing multilayer laminated film according to the present invention, as a fourth layer, A transparent or translucent resin layer made of a resin composition containing a thermoplastic resin as a main component of a vehicle can be provided.

The oxygen-absorbing multilayer laminated film according to the present invention will be described in more detail. First, in the present invention, one or more thermoplastic resins are used as the main component of the vehicle, and one of the white colorants is added thereto. In addition, two or more kinds are added, and if necessary, when forming the film, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold release, etc. 1 to 2 or more kinds of various plastic compounding agents and additives are optionally added for the purpose of improving and modifying the property, flame retardancy, antifungal property, electrical characteristics, strength, etc. If necessary, a first resin composition containing at least a thermoplastic resin and a white colorant constituting the white resin layer is prepared by adding a solvent, a diluent and the like and kneading sufficiently.
Further, in the present invention, as described above, it contains an oxidizing resin and a transition metal catalyst, and if necessary, a thermoplastic resin as a binder, a radical generator or a photosensitizer, and the like. Additives, such as film processing, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slip properties, mold release properties, flame retardancy, antifungal properties, For the purpose of improving and modifying electrical characteristics, strength, etc., one or more of various plastic compounding agents and additives are arbitrarily added, and if necessary, solvents, diluents, etc. Is added and kneaded sufficiently to prepare a second resin composition for forming the oxygen-absorbing resin layer according to the present invention.
Furthermore, in the present invention, one or more thermoplastic resins are used as the main component of the vehicle, and, if necessary, when forming the film, for example, the processability, heat resistance, and weather resistance of the film. Various plastics blended for the purpose of improving and modifying properties, mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold release properties, flame retardancy, antifungal properties, electrical properties, strength, etc. At least one or two or more of additives, additives, etc. are optionally added, and if necessary, a solvent, a diluent, etc. are added and kneaded sufficiently to constitute at least a transparent or translucent resin layer. A third resin composition containing a thermoplastic resin is prepared.
In the present invention, as the plastic compounding agent and additive, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a flame retardant, Flame retardants, foaming agents, antifungal agents, pigments, dyes, dispersants, surfactants, antiblocking agents, etc. can be used, and further, modifying resins can be used, 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, the first, second, and third resin compositions are prepared as described above, and then the first, second, and third resin compositions are used. The oxygen-absorbing multilayer laminated film according to the present invention comprising at least three layers of a co-extrusion film-formed film can be produced by co-extrusion molding using a co-extruder, an inflation co-extruder or the like.
Thus, in the present invention, a specific method for producing a coextruded film-formed film of at least three layers using each of the first, second, and third resin compositions described above will be described. First, the first, second, and third resin compositions prepared above are used, and then these are coextruded to form a film using, for example, a T-die coextrusion machine, an inflation coextrusion machine, etc. The first layer constituting the layer is a white resin layer made of the first resin composition, and the second layer constituting the intermediate layer is an oxygen-absorbing resin layer made of the second resin composition. And the third layer constituting the back surface layer is a three-layer / three-layer coextrusion film-forming film comprising a transparent or translucent resin layer. be able to.

  Moreover, in this invention, when another example is illustrated about the oxygen absorptive multilayer laminated film which concerns on this invention, it uses the 1st, 2nd, 3rd resin composition prepared above, Then, these are used, for example, A first layer constituting a surface layer formed by coextrusion film formation using a T-die coextrusion machine, an inflation coextrusion machine, or the like is composed of a transparent or translucent resin layer made of the above third resin composition. Further, the second layer constituting the first intermediate layer is made of a white resin layer made of the first resin composition, and the third layer constituting the second intermediate layer is made of the second resin layer. In addition, the fourth layer constituting the back surface layer is composed of three types and four layers of transparent or translucent resin layers made of the above-mentioned third resin composition. Oxygen-absorbing multilayer laminate film according to the present invention comprising an extruded film It is possible to manufacture the Lum.

The above exemplifications illustrate one or two examples of the oxygen-absorbing 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, in addition to the above first, second, and third resin compositions, other resin compositions and the like are further prepared, arbitrarily selected, and combined to form a coextrusion film. The oxygen-absorbing multilayer laminated film according to the present invention having various layer configurations can be produced.
Further, in the present invention, when producing the oxygen-absorbing multilayer laminated film according to the present invention, other materials are used depending on the purpose of use, applications, etc., and these are optionally coextruded and laminated. Thus, the oxygen-absorbing multilayer laminated film according to the present invention having the layer structure can be designed and manufactured.
Thus, in the present invention, as the oxygen-absorbing multilayer laminated film according to the present invention, basically, the white resin layer and the oxygen-absorbing resin layer are adjacent to each other, and one or both surfaces thereof are transparent or translucent. A layer structure laminated with a resin layer is preferable.

Next, in the present invention, as the film thickness of the oxygen-absorbing multilayer laminated film according to the present invention, first, the film thickness of each layer constituting the oxygen-absorbing multilayer laminated film will be described. The film thickness is preferably in the range of about 5 μm to 50 μm, preferably about 10 μm to 30 μm.
Next, the film thickness of the white resin layer and the transparent or translucent resin layer is desirably in the range of about 5 μm to 100 μm, preferably about 10 μm to 50 μm.
Thus, in the present invention, the film thickness of the oxygen-absorbing multilayer laminated film according to the present invention is about 15 μm to 250 μm, preferably about 30 μm to 130 μm when the film has a three-layer structure. In the case of a four-layer structure, a total thickness of about 20 μm to 350 μm, preferably about 40 μm to 180 μm is desirable.

In the above, if the film thickness of the oxygen-absorbing resin layer is 5 μm, more preferably less than 10 μm, it is not preferable because the required oxygen-absorbing physical properties are not sufficiently exhibited, and 50 μm Further, if it exceeds 30 μm, it is not preferable because of an increase in cost and a layer whose strength is deteriorated by oxygen absorption affects the physical properties of the whole film.
Furthermore, in the above, when the film thickness of the white resin layer and the transparent or translucent resin layer is 5 μm, and further less than 10 μm, the function as the seal layer is lowered, and the heat seal strength is reduced. It is not preferable because it may be insufficient and cosmetic properties are impaired, and if it exceeds 100 μm, more than 50 μm, there is no problem in seal strength, cosmetic properties, etc., but the cost This is not preferable for reasons such as an increase in the temperature and environmental problems.

Next, in the present invention, the thermoplastic resin constituting the white resin layer and the transparent or translucent resin layer is, for example, melted by heat and can be extruded from an extrusion die such as an extruder. A mixture of one type or two or more types of thermoplastic resins that can be thermally fused to each other can be used.
Specifically, for example, using low density polyethylene (LDPE), linear (linear) low density polyethylene (polymer polymerized using multi-site catalyst, LLDPE), metallocene catalyst (single site catalyst) Polymerized 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 -Polyolefin resins such as ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyethylene or polypropylene. Acrylic acid, methacrylic acid, malein , Acid-modified polyolefin resins modified with unsaturated carboxylic acids such as maleic anhydride, fumaric acid, itaconic acid, polyvinyl acetate resins, poly (meth) acrylic resins, polyvinyl chloride resins, thermoplastic polyester resins One type or two or more types of thermoplastic resins such as resins, thermoplastic polyamide resins, and the like can be used.

Thus, in the present invention, the white resin layer and the oxygen-absorbing resin layer constituting the oxygen-absorbing multilayer laminated film according to the present invention using one or more of the above thermoplastic resins. And, by forming a transparent or translucent resin layer, etc., each layer has an affinity, etc., and at the time of co-extrusion molding, each layer is firmly and tightly bonded, excellent in strength, etc. The oxygen-absorbing multilayer laminated film according to the present invention, which is excellent in various physical properties such as heat resistance, heat resistance, water resistance and others, can be constituted.
In the present invention, one or more of the above thermoplastic resins are used to form a transparent or translucent resin layer or the like constituting the oxygen-absorbing multilayer laminated film according to the present invention. Since it is made of a thermoplastic resin that can be heat-sealed with each other, it acts as a heat-sealable resin layer that forms a seal portion or the like when making a bag such as a packaging bag, An extremely good seal portion or the like can be formed.

Next, in the present invention, as the white colorant constituting the white resin layer, for example, without sacrificing the cosmetics of the packaging bag or the packaged product, further, the sun or the fluorescent lamp or the like. Reflecting or diffusing fluorescence, etc., blocking or blocking its transmission, and preventing the degradation or alteration of the contents filled and packaged in the packaging bag, or light deterioration such as discoloration, etc. For example, it is desirable to use one kind or a mixture of two or more kinds of colorants such as various white type inorganic or organic dyes and pigments.
In the present invention, as the above-mentioned various white type inorganic or organic dyes, pigments and other colorants, for example, basic lead carbonate, basic lead sulfate, basic lead silicate, zinc white, sulfide One or more of white pigments such as zinc, lithopone, antimony trioxide, anatase-type titanium oxide, rutile-type titanium oxide, calcium carbonate, zinc oxide, barium sulfate, etc. can be used.
The amount used is about 0.1 wt% to 30 wt%, preferably about 0.5 wt% to 20 wt% added to the thermoplastic resin constituting the resin composition constituting the white resin layer. It is desirable to use.

  In the present invention, examples of the plastic compounding agent and additive that constitute the white resin layer, the oxygen-absorbing resin layer, and the transparent or translucent resin layer include a lubricant, a crosslinking agent, and an antioxidant. UV absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, flame retardants, flame retardants, foaming agents, fungicides, pigments, dyes, dispersants, surfactants, antiblocking agents, etc. Further, a modifying resin or the like can also be used, and the addition amount is arbitrarily added from a very small amount to several tens of weight% depending on the purpose. Can do.

Furthermore, in the above, as the compounding agent or additive, specifically, a lubricant having its own lubricity and little migration in the resin can be used. For example, liquid paraffin, white Vaseline, petroleum wax, microcrystalline wax, montan wax, polyethylene wax and the like, higher fatty acids having 8 to 22 carbon atoms, or higher fatty acid aluminum, higher fatty acid calcium, higher fatty acid magnesium higher fatty acid zinc, higher fatty acid lithium Higher fatty acids or metal salts thereof, linear aliphatic monohydric alcohols having 8 to 18 carbon atoms, glycerin, sorbitol, propylene glycol, pentaerythritol, triethylene glycol, etc. Aliphatic alcohols, higher fatty acids having 4 to 22 carbon atoms and straight chain aliphatics having 8 to 18 carbon atoms Esters with polyhydric alcohols, butyl acetyl citrate, di-2-ethyl-hexyl adipate, azelaic acid-n-hexyl, ethanediol montanate, poly (1.3-butanediol adipate) ester, acetylricino Methyl ester, poly (1.3-butylene glycol, 1.4-butylene glycol, octyl alcohol adipic acid) ester, ester of sugar sugar sugar and fatty acid, hydrogenated Edible oils and fats, castor oil, spam acetyl wax, glycerides of acetylated monoglyceride sugar, ethylene bis-fatty acid amide represented by, for example, ethylene bisoleyl amide having 16 to 18 carbon atoms, higher fatty acid amide having 8 to 22 carbon atoms , Stearyl erucamide, erucic acid amide, oleyl palmitoamide, etc. 1 to 2 of fatty acid amides, silicone oil such as methylhydrodiene polysiloxane, dimethylpolysiloxane, methylphenylpolysiloxane, polyoxyalkylene / dimethylpolysiloxane, glycerin ester of rosin and maleic acid modified rosin More than seeds can be used.
In the present invention, among the lubricants as described above, in particular, erucic acid amide, ethylene bis oleyl amide, stearic acid amide, oleic acid amide, methylene bis stearic acid amide, etc. themselves have lubricity, It is a very effective material.
As the addition amount of the above-mentioned lubricant, it is preferable to add at a ratio of about 0.08 wt% to 10.0 wt% with respect to 100 parts by weight of the thermoplastic resin.

In the present invention, other oxides such as aluminum oxide, magnesium oxide, silica, calcium oxide, titanium oxide, and zinc oxide; hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide; Carbonates such as magnesium and calcium carbonate, sulfates such as calcium sulfate and barium sulfate, silicates such as magnesium silicate, aluminum silicate, calcium silicate and aluminosilicate, and others, kaolin, talc, diatomaceous earth, etc. Anti-blocking agent based on inorganic compounds, or high-density polyethylene, ultra-high molecular weight polyethylene having a molecular weight of 300000 or more, polypropylene, polycarbonate, polyamide, polyester, melamine resin, diallyl phthalate resin, acrylic resin, etc. Organic consisting of fine powder It one free of compounds based antiblocking agents can be added two or more.
The addition amount is preferably about 0.01 to 3% by weight with respect to 100 parts by weight of the thermoplastic resin.

Next, in the present invention, as the oxidizing resin for forming the oxygen-absorbing resin layer constituting the oxygen-absorbing multilayer laminated film 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 Japanese Patent Application Publication No. 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, the above-mentioned low density polyethylene (LDPE), linear (linear) low density polyethylene (polymer polymerized using a multisite catalyst, LLDPE), metallocene catalyst (single site catalyst) is used. Polymerized 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-acrylic Polyolefin resins such as ethyl acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyethylene or polypropylene, acrylic acid, methacrylic acid, Malay Acid-modified polyolefin resins modified with unsaturated carboxylic acids such as acid, maleic anhydride, fumaric acid, itaconic acid, polyvinyl acetate resins, poly (meth) acrylic resins, polyvinyl chloride resins, thermoplastic polyester resins One, two or more thermoplastic resins such as thermoplastic 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, which are generally known as photoinitiators, are used.
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.
Therefore, 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.

Thus, in the oxygen-absorbing multi-layer laminated film according to the present invention produced as described above, the white resin layer can be further removed from the sun or a fluorescent lamp without impairing the cosmetics of the packaging bag or packaged product. Reflects or diffuses sunlight, fluorescence, etc., and blocks or blocks the transmission of light, providing light-shielding performance. Decomposition or alteration of the contents filled in the packaging bag, or light deterioration such as discoloration, etc. In addition, the oxygen-absorbing resin layer and the like are concealed and have a close adhesiveness with a base film, a barrier base film and the like described below, and then a transparent or translucent resin layer Mainly exhibits heat seal performance, especially heat seal performance that can heat seal at low temperatures and express stable seal strength. This allows for packaging In addition, the oxygen-absorbing resin layer mainly fills and packs the contents in a packaging bag, and then, for example, the head space in the packaged product. Absorbs and captures oxygen that is present in food, etc., oxygen that is contained in the contents, oxygen generated from the contents, and other oxygen that is present or contained in the packaged product such as others It is.
In the oxygen-absorbing multilayer laminated film according to the present invention, the white resin layer, the oxygen-absorbing resin layer, the transparent or translucent resin layer, etc. are firmly and tightly bonded, have rigidity, strength, etc. It exhibits physical properties such as impact, independence, and shape retention.
The oxygen-absorbing resin layer includes an oxidizing resin and a transition metal catalyst as described above. Further, if necessary, a thermoplastic resin as a binder, a radical generator or a photosensitizer, and the like. It can comprise from the resin film by the resin composition which contains additives, such as these arbitrarily.
Thus, in the oxygen-absorbing multilayer laminated film according to the present invention produced as described above, the oxygen-absorbing performance of the oxygen-absorbing resin layer is about 1000 mJ / cm ² when the oxygen-absorbing resin layer is about 10 μm or more. It exhibits oxygen absorption performance of 300 cc / m ² · 5 day · atm or more, preferably 500 cc / m ² · 5 day · atm or more after UV irradiation, and is extremely useful as an oxygen-absorbing material. .

  As is clear from the above description, the oxygen-absorbing multilayer laminated film according to the present invention mainly has heat seal performance, cosmetics, oxygen absorption performance, and the like. A material film, a barrier substrate film, and the above oxygen-absorbing multilayer laminated film are sequentially laminated to produce a laminate having various layer configurations, and then the laminate is used to produce the laminate. A bag can be made into various forms of packaging bags, and then the desired contents can be filled and packaged in the packaging bags to produce various types of packaging products. It is.

Thus, in the present invention, as the base film constituting the laminate, packaging bag, packaged product, etc. according to the present invention, this is the basic material constituting the laminate, packaging bag, packaged product, etc. Therefore, the resin has excellent strength in mechanical, physical, chemical, etc., and also has excellent puncture resistance, etc., and other excellent heat resistance, moisture resistance, transparency, etc. A film or sheet can be used, and it is particularly preferable to use a resin film or sheet having printability.
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 reduced, which is not preferable.
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, packaging bag, packaged product and the like according to the present invention will be described. As such a barrier substrate film, mainly oxygen gas, It is possible to use a material / material that prevents water vapor or the like, in particular, oxygen gas from permeating through the laminated body constituting the packaging bag from the outside into 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, etc., for example, polyvinylidene chloride resin, polyvinyl alcohol resin, saponified ethylene-vinyl acetate copolymer, nylon MXD6, etc. 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.
Thus, 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, more 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. A transparent or translucent film or sheet of various resins such as polyamide resins such as nylon 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 of the vapor deposition material, for example, a resistance heating method, a high frequency induction heating method, an electron beam heating method (EB), or the like can be used.
In the present invention, 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, a high-frequency plasma, a pulse wave plasma, a microwave plasma, or the like can be used as the low-temperature plasma generator. Thus, in the present invention, a highly active and stable plasma is obtained. 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 50 to 2000 mm, preferably 100 to 1000 mm.
Moreover, in the above, the resin film or sheet which comprises the above-mentioned base film can be used similarly as a resin film.
Specifically, polyethylene resins, polypropylene resins, polystyrene resins, polyvinyl chloride resins, polycarbonate resins, polyethylene terephthalates, polyester resins such as polyethylene naphthalates, and the like. A transparent or translucent film or sheet of various resins such as polyamide resins such as nylon 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, as the laminate forming the packaging bag constituting the packaged product according to the present invention, the above-mentioned substrate film, barrier substrate film, oxygen-absorbing multilayer laminate film, etc. For example, a dry lamination lamination method in which lamination is performed via an adhesive layer for lamination, or a melt extrusion lamination lamination method in which various resins are laminated while being extruded through an anchor coating agent layer, etc. By sequentially laminating using a laminating method, it is possible to produce a laminate according to the present invention having various layer configurations.

In the above, as the laminating adhesive constituting the laminating adhesive layer, for example, polyvinyl acetate adhesive, homopolymers 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 composed of coalescence, cellulose adhesives, polyester adhesives, polyamide adhesives, polyimide adhesives, amino resin adhesives composed of urea resins or melamine resins, phenol resin adhesives , Epoxy adhesives, polyurethane adhesives, reactive (meth) a Uses adhesives such as rubber adhesives made of ril adhesives, chloroprene rubber, nitrile rubber, styrene-butadiene rubber, silicone adhesives, alkali metal silicates, low melting point 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, the anchor coating agent constituting the anchor coating agent layer includes, for example, various aqueous or oil-based 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 lamination 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 laminate according to the present invention, the oxygen-absorbing multilayer laminate film of the inner layer is opposed to each other, and the two layers are folded, or two of them are overlapped, and the peripheral edge portion is further heated to the sheet. It is possible to manufacture a packaging bag having various forms by providing a seal part.
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 heat seals such as seal type, pleated seal type, flat bottom seal type, square bottom seal type, etc. 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, one-piece type, two-piece type, other spouts, opening / closing zippers, etc. are 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 ultraviolet light is transparent or translucent of the oxygen-absorbing multilayer laminated film constituting the packaging bag. And the ultraviolet light acts on the transition metal catalyst, which is activated, thereby causing, for example, a cyclohexene ring as an oxidizing resin. It is possible to exhibit an oxygen scavenging function in which radicals are attacked to the unsaturated bond portion of this to bind and absorb oxygen from the chain reaction.
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. It can be, as its irradiation conditions, for example, as the intensity of ultraviolet rays, as the integrated quantity of ^{light, 500mJ / cm 2 ~2000mJ / cm} 2 -position, ^{preferably, 500mJ / cm 2 ~1000mJ / cm} 2 -position, the ultraviolet As the irradiation time, it is possible to irradiate with a time satisfying the above integrated light quantity by correlation with the lamp light quantity, for example, about 10 seconds to 80 seconds.
In the above, if less than 500 mJ / cm ² , the ultraviolet light energy is insufficient and the oxidation reaction tends to be insufficient, and if it exceeds 2000 mJ / cm ² , the influence on the film is large. It is not preferable because it may be difficult to use.
Of course, in the present invention, as described above, the ultraviolet irradiation method is replaced with a method of irradiating the inner surface of the packaging bag from the inner surface side, for example, before, after, or simultaneously with the contents. Thus, the outer surface of the packaging bag can be irradiated from the outer surface side, for example, before, after, or simultaneously with the filling of the contents.
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 (d) were prepared.
(I). Single-site linear low-density polyethylene [made by Mitsui Chemicals, trade name, Evolu-SP2020, density, 0.916 g / m ³ , melt flowlet (MFR), 1.5 g / 10 minutes] The first layer was sufficiently kneaded with 100.0 parts by weight, 0.5 parts by weight of synthetic silica, 0.05 parts by weight of erucic acid amide, and 0.05 parts by weight of ethylene bisoleic acid amide. The resin composition which forms was prepared.
(B). Single-site linear low-density polyethylene [Mitsui Chemicals, trade name, Evolu-SP2020, density, 0.916 g / m ³ , melt, the same as the first layer, in the first intermediate layer (second layer) Flowlet (MFR), 1.5 g / 10 min], 80.0 parts by weight, 20.0 parts by weight of titanium oxide as a white pigment, 0.5 parts by weight of synthetic silica, and 0.05 parts by weight of erucamide Then, 0.05 part by weight of ethylenebisoleic acid amide was sufficiently kneaded to prepare a resin composition for forming the second layer.
(C). In the second intermediate layer (third layer), 100.0 parts by weight of [ethylene / methyl acrylate / methyl cyclohexene methyl acrylate copolymer] as an oxidizing resin, and [cobalt 2- Ethylhexanoate] 0.01 parts by weight and [1-hydroxy-cyclohexyl-phenyl-ketone] 0.001 part by weight as a radical photopolymerization initiator are sufficiently kneaded to form the third layer. A resin composition was prepared.
(D). Single-site linear low-density polyethylene [Mitsui Chemicals, trade name, Evolu-SP2020, density, 0.916 g / m ³ , melt flow ( MFR), 1.5 g / 10 minutes] 100.0 parts by weight, 0.5 parts by weight of synthetic silica, 0.05 parts by weight of erucic acid amide, and 0.05 parts by weight of ethylenebisoleic acid amide A resin composition for forming the fourth layer was prepared by kneading.
Next, by using the resin compositions of (a) to (d) prepared above, and using these three types and four layers of top blown air-cooled inflation coextrusion film forming machine, the resin composition of (a) The first layer is 5 μm, the second layer made of the resin composition (b) is 20 μm, the third layer made of the resin composition (c) is 10 μm, and the fourth layer made of the resin composition (d) is 15 μm. Extruded to produce a co-extruded multilayer laminated film according to the present invention having a total thickness of 50 μm consisting of three types and four layers.
The coextruded multilayer laminated film produced above was milky white and excellent in aesthetics.
Further, the light blocking property was sufficient, and it was very good because it hardly transmitted ultraviolet rays due to oxidation of fats and oils.
The coextruded multi-layer laminated film manufactured above is used from the fourth layer side by using an ultraviolet irradiation device [manufactured by Eye Graphics Co., Ltd., model name, ECS-401GX]. When irradiated with / cm ² , oxygen began to be sucked.
A film sample of 100 mm x 100 mm was put into an aluminum pouch, and 100 ml of air was injected and sealed. As a result, the oxygen concentration dropped to about half (10%) in 5 days. "About 1000 cc / m ² · 5 day · atm).
(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 a two-component curable urethane-based adhesive (main agent: Polyester polyol, curing agent: aliphatic isocyanate) is coated to a thickness of 4.0 g / m ² (dry state) using a gravure roll coat method to form an adhesive layer for laminating Then, a 12 μm-thick biaxially stretched polyethylene terephthalate film having a 200-nm-thick silicon oxide vapor-deposited film is placed on the surface of the laminating adhesive layer so that the silicon-oxide vapor-deposited film faces the surface. Overlapping, and then laminating both layers together, and further having a 200 μm thick silicon oxide vapor-deposited film laminated in the above-described dry lamination manner, a biaxially stretched polycrystal having a thickness of 12 μm. 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 the two-component curable urethane-based adhesive (main component: polyester polyol, (Hardening agent: aliphatic socyanate), and this is coated to a thickness of 4.0 g / m ² (dry state) using a gravure roll coating method to form an adhesive layer for laminating. Then, a 12 μm thick biaxially stretched polyethylene terephthalate film having a desired printed pattern layer is laminated on the surface of the laminating adhesive layer with the corona-treated surface and the printed pattern layer facing each other. Thereafter, 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, the surfaces of the fourth layer of the coextruded multilayer laminate film according to the present invention constituting the laminate are overlapped with 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, the inner surface of the packaging bag produced as described above is irradiated with ultraviolet light 1000 mJ / cm ² using an ultraviolet irradiation device [made by Eye Graphics Co., Ltd., model surface, ECS-401GX]. The pasta was filled and then the opening was heat sealed to form an upper seal to produce a packaged product.
In the packaged product produced above, the raw pasta, which is deteriorated by oxygen, was not observed to be discolored or deteriorated in odor even in a retention test for one month.

(1). First, a co-extruded multilayer laminated film was produced by the following method.
First, the following resin compositions (a) to (d) were prepared.
(I). Ethylene-α-olefin copolymer polymerized using a single-site catalyst (metallocene catalyst) on the surface layer (first 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 erucic acid amide, 0.05 parts by weight of ethylenebisoleic acid amide The resin composition for forming the first layer was prepared by sufficiently kneading the part.
(B). Single-site linear low-density polyethylene [Mitsui Chemicals, trade name, Evolu-SP2020, density, 0.916 g / m ³ , melt, the same as the first layer, in the first intermediate layer (second layer) Flowlet (MFR), 1.5 g / 10 min], 80.0 parts by weight, 20.0 parts by weight of titanium oxide as a white pigment, 0.5 parts by weight of synthetic silica, and 0.05 parts by weight of erucamide Then, 0.05 part by weight of ethylenebisoleic acid amide was sufficiently kneaded to prepare a resin composition for forming the second layer.
(C). 100.0 parts by weight of [styrene / butadiene copolymer] as an oxidizing resin in the second intermediate layer (third layer) and 0.01 parts by weight of [cobalt 2-ethylhexanoate] as a transition metal catalyst Part and 0.001 part by weight of [1-hydroxy-cyclohexyl-enyl-ketone] as a radical photopolymerization initiator were sufficiently kneaded to prepare a resin composition forming the third layer.
(D). Single-site linear low-density polyethylene [Mitsui Chemicals, trade name, Evolu-SP2020, density, 0.916 g / m ³ , melt flow ( MFR), 1.5 g / 10 minutes], 100.0 parts by weight, 0.5 parts by weight of synthetic silica, 0.05 parts by weight of erucic acid amide, and 0.05 parts by weight of ethylenebisoleic acid amide A resin composition for forming the fourth layer was prepared by kneading.
Next, by using the resin compositions of (a) to (d) prepared above, and using these three types and four layers of top blown air-cooled inflation coextrusion film forming machine, the resin composition of (a) The first layer is 5 μm, the second layer made of the resin composition (b) is 20 μm, the third layer made of the resin composition (c) is 10 μm, and the fourth layer made of the resin composition (d) is 15 μm. Extruded to produce a co-extruded multilayer laminated film according to the present invention having a total thickness of 50 μm and comprising three types and four layers.
The coextruded multilayer laminated film produced above was milky white and excellent in aesthetics.
Furthermore, the light blocking property was sufficient, and the ultraviolet ray resulting from the oxidation of fats and oils was hardly transmitted, and was very good.
Next, UV light of 250 nm to 320 nm is integrated into the coextruded multilayer laminated film produced above from the fourth layer side using an ultraviolet irradiation device [model name, ECS-401GX, manufactured by Eye Graphics Co., Ltd.] When 1000 mJ / cm ^{2 was} irradiated with the light amount, oxygen began to be sucked.
As a result of putting a 100 mm × 100 mm film sample into an aluminum pouch and injecting and sealing 100 ml of air, the oxygen concentration dropped to about half (10%) in 5 days, “about 1000 cc / m ² .5 day. atm).
(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 a two-component curable urethane-based adhesive (main agent: Polyester polyol, curing agent: aliphatic isocyanate) is coated to a thickness of 4.0 g / m ² (dry state) using a gravure roll coat method to form an adhesive layer for laminating Then, a 15 μm-thick biaxially stretched nylon 6 film having an aluminum oxide vapor deposition film having a thickness of 200 mm is laminated on the surface of the laminating adhesive layer with the aluminum oxide vapor deposition film facing the surface. After that, both of them were dry laminated, and further, a dry-laminated laminated aluminum oxide vapor-deposited film having a thickness of 200 mm and a biaxial thickness of 15 μm. The surface of the biaxially stretched nylon 6 film of the stretched nylon 6 film is subjected to corona discharge treatment in the same manner as described above, and the two-component curable urethane adhesive (main agent: polyester polyol, curing agent: Aliphatic socyanate) is coated using a gravure roll coat method to a thickness of 4.0 g / m ² (dry state) to form an adhesive layer for laminating, A 12 μm thick biaxially stretched polyethylene terephthalate film having a desired printed pattern layer is laminated on the surface of the laminating adhesive layer with the corona-treated surface and the printed pattern layer facing each other, and thereafter Both were laminated by dry lamination to produce a laminate according to the present invention.
(3). Next, two laminates produced as described above are prepared, the surfaces of the fifth layer of the coextruded multilayer laminate film according to the present invention constituting the laminate are overlapped with each other, and then the periphery of the outer periphery is prepared. 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, the inner surface of the packaging bag produced as described above is irradiated with ultraviolet light 1000 mJ / cm ² using an ultraviolet irradiation device [made by Eye Graphics Co., Ltd., model surface, ECS-401GX]. The pasta was filled, and then the opening was heat sealed to form an upper seal to produce a packaged product.
In the packaged product produced above, the raw pasta, which is deteriorated by oxygen, was not observed to be discolored or deteriorated in odor even in the retention test for one month.

(1). First, a co-extruded multilayer laminated film was produced by the following method.
First, the following resin compositions (a) to (e) were prepared.
(I). Ethylene-α / olefin copolymer polymerized by using a single-site catalyst (metallocene catalyst) on the surface layer (first layer) [Mitsui Chemicals, trade name, Evolue SP2020, density, 0.917 g / m ³ Melt flowlet (MFR), 2.0 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 The resin composition for forming the first layer was prepared by sufficiently kneading the part.
(B). Single-site linear low-density polyethylene [Mitsui Chemicals, trade name, Evolu-SP2020, density, 0.916 g / m ³ , melt, the same as the first layer, in the first intermediate layer (second layer) Flowlet (MFR), 1.5 g / 10 min], 80.0 parts by weight, 20.0 parts by weight of titanium oxide as a white pigment, 0.5 parts by weight of synthetic silica, and 0.05 parts by weight of erucamide Then, 0.05 part by weight of ethylenebisoleic acid amide was sufficiently kneaded to prepare a resin composition for forming the second layer.
(C). 100.0 parts by weight of [poly-N, N′-dimethylmetaxylylenediamine] as an oxidizing resin in the second intermediate layer (third layer) and [cobalt 2-ethylhexanoate as a transition metal catalyst A resin composition for forming a third layer by sufficiently kneading 0.01 part by weight and 0.001 part by weight of [1-hydroxy-cyclohexyl-phenyl-ketone] as a radical photopolymerization initiator Prepared.
(D). Single-site linear low-density polyethylene [Mitsui Chemicals, trade name, Evolu-SP2020, density, 0.916 g / m ³ , melt flow ( MFR), 1.5 g / 10 minutes] 100.0 parts by weight, 0.5 parts by weight of synthetic silica, 0.05 parts by weight of erucic acid amide, and 0.05 parts by weight of ethylenebisoleic acid amide A resin composition for forming the fourth layer was prepared by kneading.
Next, by using the resin compositions of (a) to (d) prepared above, and using these three types and four layers of top blown air-cooled inflation coextrusion film forming machine, the resin composition of (a) The first layer is 5 μm, the second layer made of the resin composition (b) is 20 μm, the third layer made of the resin composition (c) is 10 μm, and the fourth layer made of the resin composition (d) is 15 μm. Extruded to produce a co-extruded multilayer laminated film according to the present invention having a total thickness of 50 μm consisting of three types and four layers.
The coextruded multilayer laminated film produced above was milky white and excellent in aesthetics.
Further, the light blocking property was sufficient, and it was very good because it hardly transmitted ultraviolet rays due to oxidation of fats and oils.
Next, the coextruded multilayer laminated film manufactured above is used with an ultraviolet irradiation device [manufactured by Eye Graphics Co., Ltd., model name, ECS-401GX], and UV light of 250 nm to 320 nm is 1000 mJ / cm ^{2 in} terms of integrated light quantity. When irradiated, began to breathe oxygen.
A film sample of 100 mm × 100 mm was put into an aluminum pouch, and 100 ml of air was injected and sealed. As a result, the oxygen concentration dropped to about 5% in 5 days, “about 500 cc / m ² · 5 day · atm”.
(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 a two-component curable urethane-based adhesive (main agent: Polyester polyol, curing agent: aliphatic isocyanate) is coated to a thickness of 4.0 g / m ² (dry state) using a gravure roll coat method to form an adhesive layer for laminating Then, a 7 μm thick aluminum foil is laminated on the adhesive layer surface for lamination so as to face each other, and then both are laminated by dry lamination, and further the thickness obtained by laminating the dry lamination as described above. Using a two-component curable urethane adhesive (main agent: polyester polyol, curing agent: aliphatic isocyanate) on the surface of a 7 μm aluminum foil, as above, gravure Using a roll coating method, a laminate adhesive layer is formed by coating to a thickness of 4.0 g / m ² (dry state), and then a desired printed pattern is formed on the surface of the laminate adhesive layer. A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is laminated so that its corona-treated surface and the surface of the printed pattern layer face each other, and then both are laminated by dry lamination. The laminated body which concerns on was manufactured.
(3). Next, two laminates produced as described above are prepared, the surfaces of the fifth layer of the coextruded multilayer laminate film according to the present invention constituting the laminate are overlapped with 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, the inner surface of the packaging bag produced as described above is irradiated with ultraviolet light 1000 mJ / cm ² using an ultraviolet irradiation device [made by Eye Graphics Co., Ltd., model surface, ECS-401GX]. The pasta was filled and then the opening was heat sealed to form an upper seal to produce a packaged product.
In the packaged product produced above, the raw pasta, which is deteriorated by oxygen, was not observed to be discolored or deteriorated in odor even in a retention test for one month.

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 produced as described above, an ultraviolet irradiation device [Model name, ECS-401GX, manufactured by Eye Graphics Co., Ltd.] is used to produce ultraviolet light. Irradiate with 1000 mJ / cm ² , and then supply the raw pasta with filling, seal the top and bottom while filling, and then cut the top and bottom seals to make a pillow bag A packaged product filled with contents was manufactured.
In the packaged product produced above, the raw pasta, which is deteriorated by oxygen, was not observed to be discolored or deteriorated in odor even in a retention test for one month.

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, the inner surface of the self-supporting bag manufactured as described above was irradiated with ultraviolet light 1000 mJ / cm ² using an ultraviolet irradiation device [Model name, ECS-401GX, manufactured by Eye Graphics Co., Ltd.] The pasta was filled and then the opening was heat sealed to form an upper seal to produce a packaged product.
In the packaged product produced above, the raw pasta, which is deteriorated by oxygen, was not observed to be discolored or deteriorated in odor even in a retention test for one month.

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, the inner surface of the gusset-type bag manufactured as described above is irradiated with ultraviolet light 1000 mJ / cm ² using an ultraviolet irradiation device [made by Eye Graphics Co., Ltd., model surface, ECS-401GX]. The pasta was filled and then the opening was heat sealed to form an upper seal to produce a packaged product.
In the packaged product produced above, the raw pasta, which is deteriorated by oxygen, was not observed to be discolored or deteriorated in odor even in a retention test for one month.

(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). Single-site linear low-density polyethylene [made by Mitsui Chemicals, trade name, Evolu-SP2020, density, 0.916 g / m ³ , melt flowlet (MFR), 1.5 g / 10 minutes] 80.0 parts by weight, 20.0 parts by weight of titanium oxide as a white pigment, 0.5 parts by weight of synthetic silica, 0.05 parts by weight of erucic acid amide, 0.05 part by weight of ethylenebisoleic acid amide The resin composition for forming the first layer was prepared by sufficiently kneading the part.
(B). The intermediate layer (second layer) contains 100.0 parts by weight of [ethylene / methyl acrylate / methyl cyclohexene methyl acrylate copolymer] as an oxidizing resin, and [cobalt 2-ethylhexanoe as a transition metal catalyst. -G] 0.01 part by weight, [1-hydroxy-cyclohexyl-phenyl-ketone] as a radical photopolymerization initiator 0.001 part by weight is sufficiently kneaded to form a second layer. Was prepared.
(C). The same single-site linear low-density polyethylene as that of the first layer (trade name, Evolu-SP2020, density, 0.916 g / m ³ , melt flow ( MFR), 1.5 g / 10 minutes] 100.0 parts by weight, 0.5 parts by weight of synthetic silica, 0.05 parts by weight of erucic acid amide, and 0.05 parts by weight of ethylenebisoleic acid amide A resin composition for forming the third layer was prepared by kneading.
Next, the resin compositions of (a) to (c) prepared above were used, and these were used according to the resin composition of (a) using a three-type three-layer top-blown air-cooled inflation coextrusion film-forming machine. The first layer is 25 μm, the second layer of (b) the resin composition is 10 μm, and the third layer of (c) the resin composition is 15 μm. A co-extruded multilayer laminate film according to the invention was produced.
The coextruded multilayer laminated film produced above was milky white and excellent in aesthetics.
Further, the light blocking property was sufficient, and it was very good because it hardly transmitted ultraviolet rays due to oxidation of fats and oils.
The coextruded multi-layer laminated film produced above is used from the third layer side by using an ultraviolet irradiation device [manufactured by Eye Graphics Co., Ltd., model name, ECS-401GX]. When irradiated with / cm ² , oxygen began to be sucked.
A film sample of 100 mm x 100 mm was put into an aluminum pouch, and 100 ml of air was injected and sealed. As a result, the oxygen concentration dropped to about half (10%) in 5 days. "About 1000 cc / m ² · 5 day · atm).
(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 a two-component curable urethane-based adhesive (main agent: Polyester polyol, curing agent: aliphatic isocyanate) is coated to a thickness of 4.0 g / m ² (dry state) using a gravure roll coat method to form an adhesive layer for laminating Then, a 12 μm-thick biaxially stretched polyethylene terephthalate film having a 200-nm-thick silicon oxide vapor-deposited film is placed on the surface of the laminating adhesive layer so that the silicon-oxide vapor-deposited film faces the surface. Overlapping, and then laminating both layers together, and further having a 200 μm thick silicon oxide vapor-deposited film laminated in the above-described dry lamination manner, a biaxially stretched polycrystal having a thickness of 12 μm. 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 the two-component curable urethane-based adhesive (main component: polyester polyol, (Hardening agent: aliphatic socyanate), and this is coated to a thickness of 4.0 g / m ² (dry state) using a gravure roll coating method to form an adhesive layer for laminating. Then, a 12 μm thick biaxially stretched polyethylene terephthalate film having a desired printed pattern layer is laminated on the surface of the laminating adhesive layer with the corona-treated surface and the printed pattern layer facing each other. Thereafter, 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, the surfaces of the fourth layer of the coextruded multilayer laminate film according to the present invention constituting the laminate are overlapped with 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, the inner surface of the packaging bag produced above is irradiated with ultraviolet light 1000 mJ / cm ² using an ultraviolet irradiation device [modeled surface, ECS-401GX, manufactured by Eye Graphics Co., Ltd.] The pasta is filled and then the opening is heat sealed to form the upper seal. In the packaged product manufactured above, the raw pasta that is deteriorated by oxygen is No discoloration or odor deterioration of the product was observed.

[Experimental Example 1]
The oxygen absorption amount of the coextruded multilayer laminated film produced in Examples 1, 2, 3, and 7 was measured.
This is a 130 mm x 170 mm aluminum pouch, into which a film sample consisting of a 100 mm x 100 mm coextruded multilayer laminated film irradiated with 1000 mJ / cm ² is placed, and then 100 ml of air is injected and sealed did.
Then, after 5 days, the oxygen concentration in the pouch was evaluated by measuring the oxygen absorption amount using an oxygen concentration meter [oxygen concentration meter manufactured by Toray Engineering Co., Ltd., model name, LC-750F].
The results are shown in Table 1 below.

(Table 1)
┌────┬─────────┬─────────────────────┐ │ │ Oxygen Absorption Rate [%] │ Oxygen Absorption [Cc / m ² · 5day · atm] │ ├────┼─────────┼─────────────────────┤ Example 1 │ 10 │ 1000 │ ├────┼─────────┼─────────────────────┤ │Example 2 │ 10 │ 1000 │ ├────┼─────────┼─────────────────────┤ │Example 3│ 5 │ 500 │ ├────┼─────────┼─────────────────────┤ │Example 7│ 10 │ 1000 │ └ ────┴─────────┴─────────────────────┘

As shown in Table 1 above, it was found that the coextruded multilayer laminated film according to the present invention exhibits extremely good oxygen absorption performance.

[Experimental example 2]
Next, the total light transmittance was measured for the coextruded multilayer laminated films produced in Examples 1, 2, 3, and 7 above.
This measured the transmittance | permeability in all rays using the haze meter (model name, SM-C) by Suga Test Instruments Co., Ltd.
The results are shown in Table 2 below.

(Table 2)
┌────┬─────────┐ │ │Light transmittance [%] │ ├────┼─────────┤ │Example 1 │ 15.2 │ ├────┼─────────┤ │Example 2│ 15.0 │ ├────┼─────────┤ │Example 3│ 14.6 │ ├────┼─────────┤ │Example 7│ 13.2 │ └────┴─────────┘

As shown in Table 2 above, it has been found that the coextruded multilayer laminated film according to the present invention exhibits extremely good total light transmittance.

  The present invention exerts an oxygen collecting function of binding and absorbing oxygen present in the head space or the like in the packaged product, or oxygen contained in the contents or generated oxygen. Oxygen that permeates from the outside of 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, for example, the state when filled and packaged are almost unchanged. In addition, even when the packaged product is maintained for a long period of time and stored, stored, and displayed for a long period of time, there is almost no change in the quality of the contents such as color, taste, smell, etc. , Freshness, etc. can be protected very well, and further, its appearance is not impaired, its cosmetics are excellent, and it is compatible with the above-mentioned content protection performance. Product life That also be capable of extending, but applicable to packaging products made of various forms.

It is a rough sectional view showing an example of the layer composition about the oxygen absorption multilayer lamination film concerning the present invention. It is a rough sectional view showing an example of the layer composition about the oxygen absorption multilayer lamination film concerning the present invention. FIG. 2 is a schematic cross-sectional view showing an example of the layer structure of the laminate according to the present invention manufactured using the oxygen-absorbing multilayer laminated film according to the present invention shown in FIG. 1. 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 Oxygen-absorbing multilayer laminated film B Laminate C Packaging bag D Packaging product 1 Coextrusion film-forming film 2 First layer 2a White resin layer 3 Second layer 3a Oxygen-absorbing resin layer 4, Third layer 4a Transparent or translucent resin layer 5 Fourth layer 5a Transparent or translucent resin layer 11 Base film 12 Barrier base film 13 Print pattern layer 21 Seal part 22 Opening part 23 Ultraviolet irradiation device 24 Ultraviolet light 25 Contents 26 Upper seal part

Claims (14)

A white layer formed of a resin composition comprising at least three layers of a co-extrusion film-forming film, wherein the first layer constituting the surface layer of the co-extrusion film-forming film comprises a thermoplastic resin and a white colorant The second layer constituting the intermediate layer of the coextruded film-forming film is composed of an oxygen-absorbing resin layer made of a resin composition containing an oxidizing resin and a transition metal catalyst, An oxygen-absorbing multilayer laminated film, wherein the third layer constituting the back layer of the coextruded film-forming film is a transparent or translucent resin layer made of a resin composition containing a thermoplastic resin. The oxygen-absorbing multilayer laminate according to claim 1, wherein a transparent or translucent resin layer made of a resin composition containing a thermoplastic resin is further provided as a fourth layer on the white resin layer. the film. The oxygen according to any one of claims 1 to 2, wherein the resin composition constituting the white resin layer contains 0.1 to 30.0 wt% of a white colorant. Absorbent multilayer laminated film. 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. Oxygen-absorbing multilayer laminated film. 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. Oxygen absorbing multilayer laminated film. 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, The oxygen-absorbing multilayer laminated film described. It consists of at least a base film, a barrier base film, and a co-extrusion film-forming film of at least three layers. Further, the first layer constituting the surface layer of the co-extrusion film-forming film is thermoplastic. It consists of the white resin layer by the resin composition containing resin and a white colorant, and the 2nd layer which comprises the intermediate | middle layer of said coextrusion film-forming film contains oxidizing resin and a transition metal catalyst A third layer comprising an oxygen-absorbing resin layer made of a resin composition and further comprising a back layer of the coextruded film-forming film is made of a transparent or translucent resin layer made of a resin composition containing a thermoplastic resin. The laminated body characterized by laminating | stacking the oxygen absorptive multilayer laminated film which becomes. 8. The laminate according to claim 7, wherein a transparent or translucent resin layer made of a resin composition containing a thermoplastic resin is further provided as a fourth layer on the white resin layer. The laminate according to any one of claims 7 to 8, wherein the base film is composed of a biaxially stretched polyester resin film. The laminate according to any one of claims 7 to 9, wherein the base film has a printed pattern layer on the front surface and / or back surface and an underlayer. It consists of at least a base film, a barrier base film, and a co-extrusion film-forming film of at least three layers. Further, the first layer constituting the surface layer of the co-extrusion film-forming film is thermoplastic. It consists of the white resin layer by the resin composition containing resin and a white colorant, and the 2nd layer which comprises the intermediate | middle layer of said coextrusion film-forming film contains oxidizing resin and a transition metal catalyst A third layer comprising an oxygen-absorbing resin layer made of a resin composition and further comprising a back layer of the coextruded film-forming film is made of a transparent or translucent resin layer made of a resin composition containing a thermoplastic resin. Using a laminate having a structure in which the oxygen-absorbing multilayer laminated film is sequentially laminated, and stacking the laminate with the surfaces of the oxygen-absorbing multilayer laminated film facing each other, and further, an end portion around the outer periphery thereof Heath Packaging bag, which comprises Le. The packaging bag according to claim 11, wherein a transparent or translucent resin layer made of a resin composition containing a thermoplastic resin is further provided as a fourth layer on the white resin layer. It consists of at least a base film, a barrier base film, and a co-extrusion film-forming film of at least three layers. Further, the first layer constituting the surface layer of the co-extrusion film-forming film is thermoplastic. It consists of the white resin layer by the resin composition containing resin and a white colorant, and the 2nd layer which comprises the intermediate | middle layer of said coextrusion film-forming film contains oxidizing resin and a transition metal catalyst A third layer comprising an oxygen-absorbing resin layer made of a resin composition and further comprising a back layer of the coextruded film-forming film is made of a transparent or translucent resin layer made of a resin composition containing a thermoplastic resin. Using a laminate having a structure in which the oxygen-absorbing multilayer laminated film is sequentially laminated, and stacking the laminate with the surfaces of the oxygen-absorbing multilayer laminated film facing each other, and further, an end portion around the outer periphery thereof Heath Next, the contents are filled and packaged from the opening in the packaging bag and before, after, or simultaneously with the filling and packaging. A packaged product characterized by irradiating the inner surface of a bag with ultraviolet rays and further sealing the opening by heat sealing the opening. 14. The packaged product according to claim 13, wherein a transparent or translucent resin layer made of a resin composition containing a thermoplastic resin is further provided as a fourth layer on the white resin layer.

Images