JP2006168003A - Heat-sealable multilayered laminated film, laminate using it, packaging bag and packaged product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a packaging material, a packaging bag, a packaged product and the like used for filling and packaging the content, developing an oxygen capturing function for sufficiently capturing oxygen present or generated in a package and useful for protecting the quality of the content. <P>SOLUTION: This heat-sealable multilayered laminated film is constituted of a coextruded film composed of at least five layers and characterized in that the first layer, which constitutes the surface layer of the film, and the fifth layer, which constitutes the back layer thereof, comprise low density polyethylenic resin layers, the second and fourth layers of the film comprise a polypropylene resin layer and the third layer which constitutes the core layer of the film comprises an oxygen absorbent resin layer based on a resin composition containing an oxidizable resin and a transition metal catalyst. A laminate using it, the packaging bag and the packaged product using the film are also disclosed. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  TECHNICAL FIELD The present invention relates to a heat-sealable multilayer laminated film and a laminate, a packaging bag, and a packaged product using the same, and more specifically, the contents are filled and packaged, and oxygen present or generated in the package is reduced. The present invention relates to a heat-sealable multilayer laminated film useful for producing a packaged product that captures and protects the quality of contents, and a laminate, a packaging bag, and a packaged product using the same.

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 problems, the present inventor first comprises a coextrusion film-forming film comprising at least 5 layers, and further comprises a first layer constituting the surface layer of the film, The fifth layer constituting the back layer is composed of a low density polyethylene resin layer, the second layer and the fourth layer constituting the intermediate layer of the film are composed of a polypropylene resin layer, A third layer constituting the core layer of the above film is a heat-sealable multilayer laminated film comprising an oxygen-absorbing resin layer made of a resin composition containing an oxidizing resin and a transition metal catalyst, Using the above-mentioned heat-sealable multilayer laminated film, a base film, a barrier-type base film, and the above-mentioned heat-sealable multilayer laminated film are sequentially laminated to produce a laminate. Furthermore, using the above laminate, The laminated body is overlapped with the surfaces of the heat-sealable multilayer laminated film facing each other, and then, the end of the outer periphery is heat-sealed to form a packaging bag, and thereafter The packaging bag is filled with the contents from the opening, and the inner surface of the packaging bag is irradiated with ultraviolet rays before, after, or simultaneously with the filling and packaging. Then, the above-mentioned opening was heat sealed to form a seal portion and sealed to produce a packaged product. After filling and packaging the contents, oxygen gas into the package from the outside Even if the packaged product is stored, stored, or displayed for a long period of time, the content color, taste, smell, etc. No change is observed and the quality of the contents can be protected very well. Improves quality and extends shelf life. Of course, it excels in rigidity, strength, etc., and has excellent shape retention and independence. Further, it achieves weight reduction and volume reduction of packaging materials, reducing environmental impact. The present invention has been completed by finding useful heat-sealable multilayer laminated films, laminates, packaging bags, packaging products and the like that can greatly contribute to the above.

  That is, the present invention comprises a coextruded film-forming film comprising at least 5 layers, and further, the first layer constituting the surface layer of the film and the fifth layer constituting the back layer are low density polyethylene-based resins. The second layer and the fourth layer constituting the intermediate layer of the film are made of a polypropylene resin layer, and the third layer constituting the core layer of the film is oxidized. A heat-sealable multilayer laminated film comprising a resin composition containing a conductive resin and a transition metal catalyst, a laminate using the same, a packaging bag, and a packaging product It is.

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 first layer constituting the surface layer and the fifth layer constituting the back surface layer are constituted by a low density polyethylene resin layer, and the second layer and the fourth layer. Is made of a polypropylene-based resin layer, which has excellent heat sealability at the time of bag making and can sufficiently satisfy its sealing property, and can easily open the packaging bag. Easily openable, excellent in rigidity and strength, excellent in shape retention and self-supporting, and can achieve a significant reduction in environmental impact by reducing the volume and volume of packaging materials. It is.
Furthermore, in the packaged product according to the present invention, its appearance is not impaired, its cosmetics and the like are excellent, it is compatible with the above-mentioned content protection performance, and further the product life of the content can be extended. It is a thing.

Hereinafter, the heat-sealable 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, a heat-sealable multilayer laminated film, a laminate, a packaging bag, a packaged product and the like according to the present invention will be described with reference to the drawings. FIG. 1 and FIG. FIG. 3 is a schematic cross-sectional view showing a layer configuration of one or two examples of a multilayer multilayer film, and FIG. 3 is a laminate using the heat-seal multilayer multilayer film according to the present invention shown in FIG. FIG. 4 is a schematic cross-sectional view showing an example of the layer structure of FIG. 4, and FIG. 4 is a cross-sectional view of the laminate using the heat-sealable multilayer laminated film according to the present invention shown in FIG. It is a schematic perspective view which shows an example of the structure about the packaging bag which concerns on this invention manufactured by bagging, FIG.5 and FIG.6 is filled with the contents in the packaging bag which concerns on this invention shown in FIG. A schematic oblique view showing an example of the configuration of a packaged product according to the present invention. It is a diagram.

  First, as the heat-sealable multilayer laminated film A according to the present invention, as shown in FIG. 1, it comprises a coextruded film-forming film 1 composed of at least 5 layers, and further the surface layer of the film 1 is The first layer 2 constituting the back layer and the fifth layer 3 constituting the back layer are composed of low-density polyethylene resin layers 4 and 4a, and the second layer 5 and the fourth layer constituting the intermediate layer of the film 1 described above. The layer 6 comprises polypropylene resin layers 7 and 7a, and the third layer 8 constituting the core layer of the film 1 further absorbs oxygen by a resin composition containing an oxidizing resin and a transition metal catalyst. The basic structure is composed of the conductive resin layer 9.

Thus, when another example of the heat-sealable multilayer laminated film according to the present invention is illustrated, as shown in FIG. 2, it comprises a coextrusion film-forming film 11 consisting of at least 7 layers, The first layer 12 constituting the surface layer of the film 11 and the seventh layer 13 constituting the back layer are composed of low density polyethylene resin layers 14 and 14a, and the first intermediate layer of the film 11 is The second layer 15 and the sixth layer 16 are composed of mixed resin layers 17 and 17a of a polypropylene resin and a polyethylene resin, and the third layer is the second intermediate layer of the film 11 described above. 18 and the 5th layer 19 consist of the polypropylene-type resin layers 20 and 20a, and also the 4th layer 21 which comprises the core layer of said film 11 contains the oxidation resin and a transition metal catalyst, and the resin composition Oxygen absorption by objects Heat according to the present invention comprising a resin layer 22 - tosylate - can be exemplified Le multilayer laminated film A _1.

Next, in the present invention, an example of the laminated body using the heat-sealable multilayer laminated film according to the present invention will be described and its configuration will be described. As the laminated body B according to the present invention, for example, The laminate according to the present invention using the heat-sealable multilayer laminated film A according to the present invention shown in FIG. 1 will be described as an example. As shown in FIG. 3, the laminate shown in FIG. Using the heat-sealable multilayer laminate film A according to the present invention, the base film 25, the barrier base film 26, and the heat-seal multilayer laminate film A shown in FIG. It is assumed that the laminated structure is a basic laminated structure.
In the above, the base film 21 can be provided with a desired printed pattern layer 27 (FIG. 2) and the like.
In FIG. 2, reference numerals 1, 2, 3, 4, 4a, 5, 6, 7, 7a, 8, and 9 have the same meanings as those in FIG.

  Next, in the present invention, an example of the packaging bag according to the present invention produced by using the laminate according to the present invention as described above will be described and the configuration thereof will be described. As the bag C, for 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. Two laminates B and B according to the present invention are prepared, and the heat-sealable multilayer laminated films A and A located in the innermost layer are opposed to each other and overlap each other. The three sides of the end are heat-sealed to form the seal portions 31, 31, 31 and the opening 32 is formed to manufacture the three-side seal-type packaging bag C according to the present invention. be able to.

  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 32, for example, using an ultraviolet irradiation device 33. It is moved up and down as indicated by an arrow P, irradiated with ultraviolet light 34 on the inner surface of the packaging bag C, and then irradiated with ultraviolet light 34 as shown in FIG. The bag C is filled with various contents 35 including, for example, food and drink, miscellaneous goods, and other articles from the opening 32, and then the opening 32 is heat sealed and the upper sheet is placed. -The package part D which concerns on this invention can be manufactured by forming the thread part 36. FIG.

In the present invention, although not shown in the drawings, for example, a vertical or horizontal pillow-type packaging bag filling and packaging machine or the like is used. First, the packaging product according to the present invention as described above from the winding roll. The laminated body forming the packaging bag constituting the film is supplied in the form of a raw film, and then the surface of the heat-sealable multilayer laminated film constituting the laminated body in the state of the raw film is irradiated with ultraviolet rays. After irradiating light, then through each process such as back seal, end seal (bottom seal), filling the contents, normal bag making such as top seal, filling packing of the contents, etc. Similarly, 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.
In addition, using the heat-sealable multilayer laminated film according to the present invention shown in FIG. 2 above, the laminate, packaging bag, packaged product, etc. according to the present invention are produced in the same manner as described above. It goes without saying that it can be done.

The above examples are examples of the heat-sealable multilayer laminated film, laminate, packaging bag, or packaged product according to the present invention, and the present invention is limited thereby. It goes without saying that it is not.
For example, in the present invention, although not shown in the drawings, according to the purpose of use, application, etc., other base materials can be arbitrarily laminated, and a laminate having various layers can be designed and manufactured. .
In addition, for example, as a form of the packaging bag according to the present invention, although not shown, for example, for packaging made of 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 lamination method for laminating a base film, a barrier base film, a heat-sealable multilayer laminated film, etc., for example, through a laminating adhesive layer The layers can be laminated by a dry laminate lamination method of laminating and a melt extrusion laminating method of laminating via an anchor coating agent layer, a melt extrusion resin layer, or the like.

Next, in the present invention, the materials constituting the heat-sealable multilayer laminated film, the laminate, the packaging bag, the packaged product and the like according to the present invention will be described. The heat-sealable multilayer laminated film will be described. The heat-sealable multilayer laminated film according to the present invention mainly has heatseal performance and oxygen absorption performance. When the laminate according to the invention is used to make a bag and produce a packaging bag, or when producing a packaged product or the like, a seal part is formed with a heat seal, and the product is used for packaging. Oxygen present in the head space of the packaging bag, packaged product, etc., or oxygen contained in the contents, or is generated. Oxygen that binds and absorbs oxygen, etc. And it has a collection function.
Of course, the heat-sealable multilayer laminated film according to the present invention is excellent in rigidity, strength, etc., and is excellent in high shape retention and self-supporting properties, and further achieves weight reduction and volume reduction of packaging materials, It can greatly contribute to reducing environmental impact.
Thus, in the present invention, the heat-sealable multilayer laminated film according to the present invention comprises a low-density polyethylene resin layer and a polypropylene resin made of a resin composition comprising a low-density polyethylene resin as a main component of a vehicle. It can be configured as a co-extrusion film-forming film comprising a polypropylene resin layer made of a resin composition comprising a vehicle as a main component and an oxygen-absorbing resin layer made of a resin composition containing an oxidizing resin and a transition metal catalyst. It can be done.
Furthermore, in the present invention, the heat-sealable multilayer laminated film according to the present invention includes a low-density polyethylene resin layer, a polypropylene resin and a polyethylene-based resin composition comprising a low-density polyethylene resin as a main component of a vehicle. A mixed resin layer made of a mixed resin composition containing a resin as a main component of a vehicle, a polypropylene resin layer made of a resin composition containing a polypropylene resin as a main component of a vehicle, and a resin containing an oxidizing resin and a transition metal catalyst It can be configured as a coextrusion film-forming film comprising an oxygen-absorbing resin layer made of the composition.

The heat-sealable multilayer film according to the present invention will be described in more detail. First, in the present invention, one or more kinds of low-density polyethylene resins are used as the main component of the vehicle, and this is further necessary. Then, when forming the film, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold release properties, flame retardancy, antifungal properties, electricity In order to improve and improve the mechanical properties, strength, etc., one or more kinds of various plastic compounding agents and additives are arbitrarily added, and if necessary, a solvent, a diluent, etc. The first resin composition that is added and sufficiently kneaded to form the heat-sealable multilayer laminated film according to the present invention is prepared.
Further, in the present invention, as described above, one or more of polypropylene-based resins are used as the main component of the vehicle, and, if necessary, when forming the film, for example, processability of the film, For the purpose of improving and modifying heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold release properties, flame retardancy, antifungal properties, electrical properties, strength, etc. One or more kinds of various plastic compounding agents and additives are arbitrarily added, and if necessary, a solvent, a diluent and the like are added and kneaded sufficiently to obtain the heat stain according to the present invention. -Adjust the 2nd resin composition which forms a multilayer multilayer laminated film.
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, or a radical generator or a photosensitizer, etc. 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 third resin composition for forming the oxygen-absorbing resin layer according to the present invention.
In the present invention, as described above, a mixed resin of one or more types of polypropylene resins and one or more types of polyethylene resins is used as the main component of the vehicle. For example, at the time of film formation, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold release properties, flame retardancy, antifungal properties, electrical properties For the purpose of improving and modifying properties, strength, etc., one or more of various plastic compounding agents and additives are arbitrarily added, and if necessary, solvents, diluents, etc. are added. Then, it is sufficiently kneaded to prepare a fourth mixed resin composition that forms the heat-sealable multilayer laminated film according to the present invention.
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. A heat-sealable multilayer laminated film according to the present invention comprising a coextruded film-formed film can be produced by coextrusion molding using a coextrusion machine, an inflation coextrusion machine or the like.
Thus, in the present invention, a specific method for producing a coextruded film-formed film using each of the first, second, and third resin compositions will be described. In the present invention, first, The prepared first, second, and third resin compositions are used, and then these are coextruded to form a surface layer using, for example, a T-die coextrusion machine, an inflation coextrusion machine, or the like to form a surface layer. The first layer and the fifth layer constituting the back layer are composed of a low-density polyethylene-based resin layer made of the first resin composition, and the second layer and the fourth layer constituting the intermediate layer are: An oxygen-absorbing resin comprising a third resin composition comprising a polypropylene resin layer comprising the second resin composition, wherein the third layer constituting the core layer comprises an oxidizing resin and a transition metal catalyst. The present invention comprising a three-layer, five-layer coextrusion film-forming film comprising layers According heat - tosylate - can be produced Le multilayer laminate film.

  Alternatively, in the present invention, first, the first, second, third, and fourth resin compositions are prepared as described above, and then the first, second, third, and fourth resin compositions are used. For example, the first layer constituting the surface layer and the seventh layer constituting the back surface layer are formed by coextrusion film formation using a T-die coextrusion machine, an inflation coextrusion machine, or the like. A low-density polyethylene-based resin layer made of a resin composition, and a second layer and a sixth layer constituting the first intermediate layer are made of a polypropylene-based resin and a polyethylene-based resin made of the above-mentioned fourth mixed resin composition And a third layer and a fifth layer constituting the second intermediate layer are made of a polypropylene-based resin layer made of the second resin composition, and further, an intermediate core layer The fourth layer constituting the first layer contains the above-mentioned oxidizing resin and a transition metal catalyst. Arsenide according to the present invention comprising co-extruded manufactured form a film film four 7-layer comprising an oxygen absorbing resin layer of a resin composition - tosylate - can be produced Le multilayer laminate film.

The above exemplification illustrates one or two examples of the heat-sealable 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 first, second, third, and fourth resin compositions described above, other resin compositions and the like are further prepared, arbitrarily selected, and combined to form a coextrusion film. Thus, a heat-sealable multilayer laminated film according to the present invention having various layer structures can be produced.
Further, in the present invention, when manufacturing the heat-sealable multilayer laminated film according to the present invention, other materials are further used depending on the purpose of use, application, etc., and this is optionally coextruded and laminated. Thus, the heat-sealable multilayer laminated film according to the present invention having various layer structures can be designed and manufactured.

Next, in the present invention, the thickness of the heat-sealable multilayer laminated film according to the present invention is as follows. Taking the case of a conductive multilayer laminated film as an example, the total thickness is about 45 μm to 450 μm, preferably about 70 μm to 270 μm.
In the present invention, in the case of the heat-sealable multilayer laminated film according to the present invention consisting of the above-described three types and five layers of coextruded film-forming films, the film thickness thereof is more than the above film thickness. Slightly thicker.
Thus, in the heat-sealable multilayer laminate film according to the present invention described above, the thickness of each layer constituting the heat-sealable multilayer laminate film is, first, the oxygen constituting the core layer. The thickness of the absorbent resin layer is desirably about 5 μm to 50 μm, preferably about 10 μm to 30 μm.
Next, the film thickness of the low-density polyethylene-based resin layer constituting the first layer and the fifth layer is desirably about 10 μm to 100 μm, preferably about 15 μm to 60 μm.
Further, the film thickness of the polypropylene resin layer constituting the second layer and the fourth layer is desirably about 10 μm to 100 μm, preferably about 15 μm to 60 μm.
In addition, also in the case of the polypropylene-type resin layer which comprises the 3rd layer and 5th layer which are 2nd intermediate | middle layers, it is preferable that it is the same as that of said film thickness.
Furthermore, in the present invention, the film thickness of the mixed resin layer of the polypropylene resin and the polyethylene resin constituting the second layer and the sixth layer as the first intermediate layer is about 10 μm to 100 μm, preferably It is desirable to be in the range of about 15 μm to 60 μm.

In the above, if the film thickness of the heat-sealable multilayer laminated film according to the present invention is 45 μm, and further less than 70 μm, it becomes difficult to form the film itself, and the strength is reduced, It is not preferable for reasons such as inconveniences such as blurring and scratches, and if it exceeds 450 μm, and more than 270 μm, there is no problem in the strength of the film, but it is not preferable in terms of environment, cost, etc. is there.
Further, in the above, if the film thickness of the oxygen-absorbing resin layer constituting the core layer according to the present invention is 5 μm, and further less than 10 μm, the required oxygen-absorbing physical properties may not be sufficiently exhibited. It is not preferable for reasons such as high, and if it exceeds 50 μm, and more than 30 μm, it is preferable for reasons such as an increase in cost, and a layer whose strength has deteriorated due to oxygen absorption affects the physical properties of the entire film. There is nothing.
Furthermore, in the above, when the film thickness of the low density polyethylene resin layer constituting the first layer and the fifth layer according to the present invention is 10 μm, and further less than 15 μm, the function as a seal layer is lowered. However, it is not preferable because the heat seal strength may be insufficient, and if it exceeds 100 μm, more than 60 μm, there is no problem as the seal strength, but the cost increases, the environment It is not preferable for reasons such as surface problems.
In the above, when the film thickness of the polypropylene resin layer constituting the second layer and the fourth layer according to the present invention is 10 μm, and further less than 15 μm, the function as the seal layer is reduced, It is not preferable because the heat seal strength may be insufficient. If the thickness exceeds 100 μm or even 60 μm, there is no problem as the seal strength, but the cost increases and the environmental It is not preferable for reasons such as problems.
The same applies to the polypropylene resin layers constituting the third and fifth layers, which are the second intermediate layer.
In the present invention, the film thickness of the mixed resin layer of the polypropylene resin and the polyethylene resin constituting the second layer and the sixth layer as the first intermediate layer is 10 μm, and more preferably less than 15 μm. , The function as a seal layer is lowered, and there is a possibility that the heat seal strength may be insufficient. Also, if it exceeds 100 μm, and more than 60 μm, the seal strength is However, it is not preferable for reasons such as cost increase and environmental problems.

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

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

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

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

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

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

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

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

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

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

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

Next, in the present invention, examples of the low density polyethylene resin constituting the first and fifth low density polyethylene resin layers according to the present invention include, for example, an extrusion die such as an extruder that is melted by heat. It is possible to use one or more low-density polyethylene resins that can be extruded from the above, and that are heat-fused to each other.
Specifically, for example, low-density polyethylene (LDPE) by a high-pressure polymerization method, linear (linear) low-density polyethylene (LLDPE) polymerized using a multi-site Ziegler-Natta catalyst, single-site metallocene catalyst It is possible to use an ethylene-α / olefin copolymer polymerized using
Thus, as the above-mentioned low density polyethylene resin, ethylene or a homo- or copolymer of ethylene and α-olefin can be used, and a density of about 0.930 or less is used. It is preferable to do.

Next, in the present invention, the polypropylene resin constituting the second layer and the fourth layer polypropylene resin layer according to the present invention is basically a propylene homopolymer or an α such as propylene and ethylene. -A copolymer (copolymer) with an olefin or the like can be used. Further, as the copolymer (copolymer), a block copolymer (copolymer) or a random copolymer (copolymer) is used. In particular, it is preferable to use a random copolymer (copolymer).
Therefore, in the present invention, as the polypropylene resin, it is preferable to use a polypropylene resin that is excellent in melt tension, stretchability and the like and has an inflation molding suitability. It is preferable to use those in which long chain branching is introduced into the chain to increase the tension in the molten state.
In the present invention, specifically, as a polypropylene resin excellent in melt tension and stretchability, a polypropylene resin composed of a block or random copolymer of propylene and ethylene or propylene and 1-octene is used. Is preferred.

Thus, in the polypropylene resin composed of a block or random copolymer of propylene and ethylene or propylene and 1-octene, the density is about 0.9 [g / cm ³ ]. The rate (MFR) is in the range of about 0.1 to 2.0 [g / 10 min], and the melt tension is in the range of 100 [mN] or more (10 [cN] or more). Can be used.
Thus, in the above, when the melt flow rate (MFR) is less than 0.1 [g / 10 min], the resin pressure rises during resin extrusion, and a large load is applied to the film forming machine. If it exceeds 2.0 [g / 10 minutes], it is not suitable for the top blowing inflation film forming method and is not preferred because it does not blow upward. Furthermore, in the above, when the melt tension is less than 100 [mN] (less than 10 [cN]), it is not preferable because it is not suitable for the top blown inflation film forming method.
In addition, as a polypropylene resin which comprises the polypropylene resin layer which comprises the 3rd layer and 5th layer which are the 2nd intermediate | middle layer, the polypropylene resin similar to the above can be used similarly.

  Furthermore, in the present invention, the above polypropylene resin is also used as the polypropylene resin constituting the mixed resin layer of the polypropylene resin and the polyethylene resin of the second layer and the sixth layer as the first intermediate layer. Can be used.

  Further, in the present invention, the polyethylene resin constituting the mixed resin layer of the polypropylene resin and the polyethylene resin of the second layer and the sixth layer as the first intermediate layer is specifically, for example, the above-mentioned Low-density polyethylene (LDPE) by high pressure polymerization method, linear (linear) low-density polyethylene (LLDPE) polymerized using multi-site Ziegler-Natta catalyst, polymerized using single-site metallocene catalyst Ethylene-α / olefin copolymer, medium density polyethylene, high density polyethylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer Polymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene- Lopylene copolymer, methylpentene polymer, polybutene polymer, polyethylene resin modified with unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, etc. Can be used.

  In the present invention, in the resin composition forming the first layer, the fifth layer, the second layer, and the fourth layer constituting the heat-sealable multilayer laminated film according to the present invention, In order to modify the film quality etc., for example, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid Polyolefin resins such as methyl copolymers, ethylene-propylene copolymers, methylpentene polymers, polybutene polymers, polyethylene or polypropylene are used as unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid. Modified acid-modified polyolefin resin, polyvinyl acetate resin, poly (meth) acrylic resin Can be used by adding polyvinyl chloride resin, thermoplastic polyester resin, a thermoplastic polyamide resin, to one free thermoplastic resin other such two or more.

Thus, in the heat-sealable multilayer laminated film according to the present invention produced as described above, the low-density polyethylene resin layer constituting the first layer and the fifth layer is mainly composed of heat -Exhibit seal performance, in particular, exhibit heat seal performance that can be heat sealed at low temperatures and exhibit stable seal strength. The polypropylene resin layer constituting the layer has heat seal performance in the same manner as the low density polyethylene resin layer constituting the first layer and the fifth layer, and the first layer and the fifth layer are The heat-seal performance of the low-density polyethylene-based resin layer to be constructed is supported, and it has rigidity, strength, etc., and exhibits physical properties such as impact resistance, self-supporting property, and shape retention. The oxygen-absorbing resin layer constituting the core layer is mainly filled with the contents in a packaging bag and then packed. Oxygen present in the packaged product, for example, oxygen present in the head space, etc., oxygen present in the contents, oxygen generated from the contents, etc. It absorbs and captures oxygen.
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 heat-sealable 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 when the oxygen-absorbing resin layer is about 10 μm or more. It exhibits an oxygen absorption performance of 300 cc / m ² · 5 days · atm or more, preferably 500 cc / m ² · 5 days · atm or more after irradiation with ultraviolet rays of / cm ² , and is extremely useful as an oxygen-absorbing material. Is.
In the present invention, the mixed resin layer of the polypropylene resin and the polyethylene resin constituting the second layer and the sixth layer as the first intermediate layer is a low density polyethylene constituting the first layer and the fifth layer. Is located between the resin layer and the polypropylene resin layer constituting the second layer and the fourth layer, and mainly functions as an intervening layer by virtue of its presence, making both stronger It has an effect of preventing the occurrence of delamination (migration) and the like by closely adhering to each other.

  As is clear from the above description, the heat-sealable multilayer laminate film according to the present invention has heat-seal performance and oxygen absorption performance, and uses this, and at least a substrate film. , A barrier substrate film, and the above-mentioned heat-sealable multilayer laminate film are sequentially laminated to produce laminates having various layer structures, and then the laminate is used. Bag making is performed to form packaging bags of various forms, and then the packaging bags are filled with desired contents and irradiated with ultraviolet rays to produce packaging products of various forms. It can be manufactured.

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 undesirably reduced.
In the present invention, for the reasons described above, about 3 μm to 100 μm, preferably about 5 μm to 50 μm is most desirable.
Thus, in the present invention, it is desirable to use a biaxially stretched polyethylene terephthalate film having a thickness of 5 to 12 μm from the viewpoints of strength and others as the base film.

In the present invention, the above-mentioned base film can be provided with a desired printed pattern, and as such printed pattern, for example, one or more kinds of normal ink vehicles are used as a main component. If necessary, one kind of additives such as plasticizers, stabilizers, antioxidants, light stabilizers, UV absorbers, curing agents, crosslinking agents, lubricants, antistatic agents, fillers, etc. Furthermore, two or more kinds are optionally added, and further, a colorant 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 is possible to print and form a desired printed pattern.
Of course, in the present invention, an underlayer or the like for the printed pattern can be provided.

  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 and the like, for example, polyvinylidene chloride resin, polyvinyl alcohol resin, saponified ethylene-vinyl acetate copolymer, nylon MXD6 and the like alone Or a resin film or sheet such as co-extrusion or a coating film thereof can be used.
The film thickness of the resin film or sheet or the coating film thereof is, for example, several μm to several tens μm, specifically 3 to 50 μm, preferably about 5 to 30 μm. Things can be used.
Moreover, as said metal foil, aluminum foil, copper foil, tin foil, various alloy foils, etc. can be used, for example, Generally, it is preferable to use aluminum foil.
The film thickness of the metal foil is about 6 to 20 μm, preferably about 7 to 10 μm.

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

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

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

  Next, in this invention, as a laminated body which forms the packaging bag which comprises the packaging product which concerns on this invention, as above-mentioned base film, barriering base film, and heat-sealable multilayer Laminate film or the like, for example, a dry laminate lamination method for laminating via a laminating adhesive layer or the like, or a melt extrusion lamination laminating method for laminating various resins or the like via an anchor coating agent layer or the like, By sequentially laminating using other laminating methods, 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, homopolymer such as ethyl acrylate, butyl, 2-ethylhexyl ester, etc. Copolymerization of polyacrylic acid ester adhesive, cyanoacrylate adhesive, ethylene and vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, and other monomers consisting of copolymers with methyl acid, acrylonitrile, styrene, etc. Ethylene copolymer adhesives made of coalescence, cellulose adhesives, polyester adhesives, polyamide adhesives, polyimide adhesives, amino resin adhesives made of urea resin or melamine resin, phenolic resin adhesives , Epoxy adhesives, polyurethane adhesives, reactive (meth) a Uses adhesives such as ril adhesives, chloroprene rubber, nitrile rubber, rubber adhesives made of styrene-butadiene rubber, silicone adhesives, alkali metal silicates, inorganic adhesives made of low-melting glass, etc. You can do it.
The composition system of the above-mentioned adhesive may be any composition form such as an aqueous type, a solution type, an emulsion type, and a dispersion type, and the property is any of film / sheet form, powder form, solid form, etc. Further, the bonding mechanism may be any of a chemical reaction type, a solvent volatilization type, a heat melting type, a hot pressure type, and the like.
Thus, the adhesive can be applied by, for example, a roll coating method, a gravure roll coating method, a kiss coating method, a coating method such as others, a printing method, or the like. ˜10.0 g / m ² (dry explosion state) is desirable.

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

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

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

In the present invention, the packaging bag according to the present invention manufactured as described above includes, for example, various foods and drinks, chemicals such as adhesives and adhesives, cosmetics, detergents, pharmaceuticals, miscellaneous goods such as chemical warmers, Various products such as other can be filled and packaged to produce packaged products having various forms.
Thus, in the present invention, in the packaged product according to the present invention manufactured as described above, when filling and packaging the contents from the opening in the packaging bag constituting the packaged product, the filling Before, after filling, or simultaneously with filling, the inner surface of the packaging bag is irradiated with ultraviolet light from the inner surface side, and then the opening of the packaging bag is heat sealed. -A package product according to the present invention is manufactured by forming a sealing portion and sealing it.
In the present invention, by irradiating the inner surface of the packaging bag with ultraviolet light from the inner surface side as described above, the ultraviolet light is reduced to a low density polyethylene resin layer, medium density to high It passes through a heat-sealable resin layer such as a density polyethylene-based resin layer, reaches the oxygen-absorbing resin layer very well, and ultraviolet light acts on the transition metal catalyst, which is activated, Thereby, for example, it is possible to perform an oxygen scavenging function in which a radical is attacked to an unsaturated bond part of a cyclohexene ring as an oxidizing resin, and oxygen is bonded and absorbed from a 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 (c) were prepared.
(I). Single-site linear low-density polyethylene [made by Mitsui Chemicals, trade name, Evolu-SP2020, density, 0.917 g / m ³ , melt flow rate (MFR), 2.0 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). Polypropylene random copolymer using a metallocene catalyst in the intermediate layer (second layer) [manufactured by Nippon Polypro Co., Ltd., trade name, Wintech WFX4TA, density, 0.900 g / m ³ , melt flow (MFR), 7 0.0 g / 10 min] 100.0 parts by weight and 0.5 parts by weight of synthetic silica were sufficiently kneaded to prepare a resin composition for forming the second layer.
(C). As the oxidizing resin in the middle core layer (third layer), 100.0 parts by weight of [ethylene / methyl acrylate / methyl cyclohexene methyl acrylate copolymer] and as the transition metal catalyst, [cobalt 2-ethylhexa Noeto] 0.01 parts by weight, [1-hydroxy-cyclohexyl-phenyl-ketone] 0.001 part by weight as a radical photopolymerization initiator is sufficiently kneaded to form a third layer. A product was prepared.
(D). Polypropylene random copolymer using the same metallocene catalyst as the second layer in the intermediate layer (fourth layer) [manufactured by Nippon Polypro Co., Ltd., trade name, Wintech WFX4TA, density, 0.900 g / m ³ , melt Flowlet (MFR), 7.0 g / 10 min] 100.0 parts by weight and 0.5 parts by weight of synthetic silica were sufficiently kneaded to prepare a resin composition for forming the second layer.
(E). The same single-site linear low density polyethylene as the above first layer (Mitsui Chemicals, trade name, Evolu-SP2020, density, 0.917 g / m ³ , melt flow ( MFR), 2.0 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 fifth layer was prepared by kneading.
Next, by using the resin compositions of (a) to (e) prepared above, and using these three types and five layers of top-blown air-cooled inflation coextrusion film forming machine, the resin composition of (a) The first layer is 20 μm, the second layer made of the resin composition (b) is 25 μm, the third layer made of the resin composition (c) is 10 μm, the fourth layer made of the resin composition (d) is 25 μm, ) Was co-extruded to a thickness of 20 μm to produce a co-extruded multilayer laminated film according to the present invention having a total thickness of 100 μm consisting of three types and five layers.
When the coextruded multilayer laminated film produced above is irradiated with 1000 mJ / cm ² of UV light of 250 nm to 320 nm using an ultraviolet irradiation device [manufactured by Eye Graphics Co., Ltd., model name, ECS-401GX] with an integrated light quantity. Began to breathe oxygen.
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 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.

(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). Polypropylene random copolymer using a metallocene catalyst in the intermediate layer (second layer) [manufactured by Nippon Polypro Co., Ltd., trade name, Wintech WFX4TA, density, 0.900 g / m ³ , melt flow (MFR), 7 0.0 g / 10 min] 100.0 parts by weight and 0.5 parts by weight of synthetic silica were 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 middle core layer (third layer) and [cobalt 2-ethylhexanoate] as a transition metal catalyst 0.01 parts by weight and 0.001 part by weight of [1-hydroxy-cyclohexyl-phenyl-ketone] as a radical photopolymerization initiator are sufficiently kneaded to prepare a resin composition that forms the third layer. did.
(D). Polypropylene random copolymer using the same metallocene catalyst as the second layer in the intermediate layer (fourth layer) [manufactured by Nippon Polypro Co., Ltd., trade name, Wintech WFX4TA, density, 0.900 g / m ³ , melt Flowlet (MFR), 7.0 g / 10 min] 100.0 parts by weight and 0.5 parts by weight of synthetic silica were sufficiently kneaded to prepare a resin composition for forming the second layer.
(E). Ethylene-α-olefin copolymer polymerized by using the same single-site catalyst (metallocene catalyst) as the first layer on the back layer (fifth layer) [trade name, Evolue SP2020, density, manufactured by Mitsui Chemicals, Inc. 0.917 g / m ³ , melt flow rate (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 erucamide, ethylene bis A resin composition for forming the fifth layer was prepared by sufficiently kneading 0.05 part by weight of oleic acid amide.
Next, by using the resin compositions of (a) to (e) prepared above, and using these three types and five layers of top-blown air-cooled inflation coextrusion film forming machine, the resin composition of (a) The first layer is 20 μm, the second layer made of the resin composition (b) is 25 μm, the third layer made of the resin composition (c) is 10 μm, the fourth layer made of the resin composition (d) is 25 μm, ) Was co-extruded to a thickness of 20 μm to produce a co-extruded multilayer laminated film according to the present invention having a total thickness of 100 μm consisting of three types and five layers.
When the coextruded multilayer laminated film produced above is irradiated with 1000 mJ / cm ² of UV light of 250 nm to 320 nm using an ultraviolet irradiation device [manufactured by Eye Graphics Co., Ltd., model name, ECS-401GX] with an integrated light quantity. Began to breathe oxygen.
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 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 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 (g) 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). Ethylene-α-olefin copolymer polymerized by using a single site catalyst (metallocene catalyst) for the first intermediate layer (second layer) [Mitsui Chemicals Co., Ltd., trade name, Evolue SP2020, density, 0.917 g / M ³ , Melt Flowlet (MFR), 2.0 g / 10 min], 50.0 parts by weight, and a polypropylene random copolymer using a metallocene catalyst [manufactured by Nippon Polypro Co., Ltd., trade name, Wintech WFX4TA, Density, 0.900 g / m ³ , melt flow rate (MFR), 7.0 g / 10 min] 50.0 parts by weight and 0.5 parts by weight of synthetic silica are sufficiently kneaded to form the second layer A resin composition was prepared.
(C). Polypropylene random copolymer using a metallocene catalyst in the second intermediate layer (third layer) [trade name, Wintech WFX4TA, density, 0.900 g / m ³ , melt flowlet (MFR, manufactured by Nippon Polypro Co., Ltd.) 7.0 g / 10 min] 100.0 parts by weight and 0.5 parts by weight of synthetic silica were sufficiently kneaded to prepare a resin composition for forming the third layer.
(D). As the oxidizing resin in the middle core layer (fourth layer), 100.0 parts by weight of [ethylene / methyl acrylate / methyl cyclohexene methyl acrylate copolymer] and as the transition metal catalyst, [cobalt 2-ethylhexa Noeto] 0.01 part by weight, [1-hydroxy-cyclohexyl-phenyl-ketone] 0.001 part by weight as a radical photopolymerization initiator sufficiently kneaded to form a resin layer A product was prepared.
(E). Polypropylene random copolymer using the same metallocene catalyst as the third layer in the second intermediate layer (fifth layer) [manufactured by Nippon Polypro Co., Ltd., trade name, Wintech WFX4TA, density, 0.900 g / m ³ , Melt Flowlet (MFR), 7.0 g / 10 min] 100.0 parts by weight and synthetic silica 0.5 parts by weight were sufficiently kneaded to prepare a resin composition for forming the fifth layer. .
(F). The first intermediate layer (sixth layer) was polymerized using the same single-site catalyst (metallocene catalyst) as in the second layer, an ethylene-α-olefin copolymer [Mitsui Chemicals, trade name, Evolue SP2020, density, 0.917 g / m ³ , melt flowlet (MFR), 2.0 g / 10 min] and 50.0 parts by weight, and a polypropylene random copolymer using a metallocene catalyst [manufactured by Nippon Polypro Co., Ltd., Product name, Wintech WFX4TA, density, 0.900 g / m ³ , melt flow rate (MFR), 7.0 g / 10 min] 50.0 parts by weight and 0.5 parts by weight of synthetic silica were sufficiently kneaded. Thus, a resin composition for forming the sixth layer was prepared.
(G). Ethylene-α-olefin copolymer polymerized by using the same single-site catalyst (metallocene catalyst) as the first layer on the back layer (seventh layer) [trade name, Evolue SP2020, density, manufactured by Mitsui Chemicals, Inc. 0.917 g / m ³ , melt flow rate (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 erucamide, ethylene bis A resin composition for forming the fifth layer was prepared by sufficiently kneading 0.05 part by weight of oleic acid amide.
Next, the resin compositions of (a) to (g) prepared above were used, and these were used according to the resin composition of (a) using a four-kind seven-layer top-blown air-cooled inflation co-extrusion film forming machine. The first layer is 20 μm, the second layer made of the resin composition (b) is 5 μm, the third layer made of the resin composition (c) is 20 μm, the fourth layer made of the resin composition (d) is 10 μm, The fifth layer of the resin composition of () is co-extruded to 20 μm, the sixth layer of the resin composition of (f) is 5 μm, and the seventh layer of the resin composition of (g) is co-extruded to 20 μm. A coextruded multilayer laminate film according to the present invention having a total thickness of 100 μm was produced.
When the coextruded multilayer laminated film produced above is irradiated with 1000 mJ / cm ² of UV light of 250 nm to 320 nm using an ultraviolet irradiation device [manufactured by Eye Graphics Co., Ltd., model name, ECS-401GX] with an integrated light quantity. Began to breathe oxygen.
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 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.

(Experimental example 1)
Each physical property evaluation in the coextruded multilayer laminated film produced in the above Examples 1 to 3 was performed as follows.
(1). Oxygen absorption test A 130 mm x 170 mm aluminum pouch was prepared, and a film sample consisting of a 100 mm x 100 mm coextruded multilayer laminated film irradiated with 1000 mJ / cm ² was placed therein, and then 100 ml of air was injected and sealed. did.
Subsequently, the oxygen concentration in the pouch after the lapse of 5 days was evaluated by measuring the oxygen absorption amount using an oxygen concentration meter [Toray Engineering Co., Ltd., oxygen concentration meter, 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 │ 5 │ 500 │ ├────┼─────────┼─────────────────────┤ │Example 3│ 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 stiffness (koshi) of the coextruded multilayer laminated film produced in Examples 1 to 3 was measured.
(2). Measurement of rigidity (cohesion) This is a coextruded multilayer laminated film produced in Examples 1 to 3 above, and a film sample comprising the coextruded multilayer laminated film of 100 mm x 100 mm is manufactured by SMT Co., Ltd. The stiffness (bending torque) was measured and evaluated from a pure bending tester (model name, JTC-911BT).
The results are shown in Table 2 below.

(Table 2)
┌────┬───────────────┐ │ │ Rigidity [N ・ m] │ ├────┼─────────── ─────┤ │Example 1│ 3.2 × 10 ^-5 │ ├────┼───────────────┤ │Example 2│ 3.3 × 10 ^-5 │ ├────┼───────────────┤ │Example 3│ 3.0 × 10 ^-5 │ └────┴───── ──────────┘

As shown in Table 2 above, it has been found that the co-extruded multilayer laminated film according to the present invention exhibits extremely good rigidity.
In addition, average bending strength was employ | adopted for the measured value of said rigidity (koshi).
Incidentally, in the low density polyethylene film, the rigidity (koshi) is about 1.7 × 10 ⁻⁵ [N · m].

(Experimental example 3)
Next, the pouch drop test was done about the laminated body laminated | stacked using the coextruded multilayer laminated film manufactured in said Examples 1-3.
(3). Pouch Drop Test Using each laminate laminated using the co-extruded multilayer laminate film produced in Examples 1 to 3, first, two laminates having a size of 140 mm × 220 mm were cut out and 220 mm facing each other. The two sides were sealed with an impulse sealer.
Subsequently, 140 mm × 70 mm as a bottom material was sealed with an impulse sealer on one side opened portion to produce a self-supporting pouch.
Thereafter, 350 ml of water was put into the self-supporting pouch produced above, and the opening was sealed to produce a water-filled stand pouch.
The stand pouch produced above was subjected to a drop impact test five times from a height of 1.2 m, and the seal strength and practicality were confirmed.
As a result, no bag breakage was observed in all the test laminates.

  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 schematic sectional drawing which shows an example of the layer structure about the heat-sealable multilayer laminated film which concerns on this invention. It is a schematic sectional drawing which shows another example of the layer structure about the heat-sealable multilayer laminated film which concerns on this 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 heat-sealable multilayer laminate 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 packaged the contents in the packaging bag which concerns on this invention shown in FIG.

Explanation of symbols

A, A ₁ Heat-sealable multilayer laminated film B Laminated body C Packaging bag D Packaging product 1 Coextrusion film-forming film 2 First layer 3 Fifth layer 4, 4a Low density polyethylene resin layer 5 Second Layer 6 Fourth layer 7, 7a Polypropylene-based resin layer 8 Third layer 9 Oxygen-absorbing resin layer 11 Coextrusion film-forming film 12 First layer 13 Seventh layer 14, 14a Low-density polyethylene-based resin layer 15 Second layer 16 Sixth layer 17, 17a Mixed resin layer of polypropylene resin and polyethylene resin 18 Third layer 19 Fifth layer 20, 20a Polypropylene resin layer 21 Fourth layer 22 Oxygen-absorbing resin layer 25 Base film 26 Barrier Substrate film 27 printed pattern layer 31 seal part 32 opening 33 ultraviolet irradiation device 34 ultraviolet light 35 contents 36 upper seal part

Claims (11)

It consists of a co-extrusion film-forming film consisting of at least 5 layers, and further, the first layer constituting the surface layer of the film and the fifth layer constituting the back layer consist of a low-density polyethylene resin layer, The second layer and the fourth layer constituting the intermediate layer of the film are made of a polypropylene resin layer, and the third layer constituting the core layer of the film is an oxidizing resin and a transition metal catalyst. A heat-sealable multilayer laminated film comprising an oxygen-absorbing resin layer made of a resin composition comprising: The mixed resin layer of polypropylene resin and polyethylene resin is provided between the first layer and the second layer and between the fifth layer and the fourth layer. Heat seal multi-layer laminate film to be described. The resin composition constituting the oxygen-absorbing resin layer further comprises an oxygen-absorbing resin layer made of a resin composition containing a binder, according to any one of claims 1 and 2, Heat seal multi-layer laminate film. The resin composition constituting the oxygen-absorbing resin layer further comprises an oxygen-absorbing resin layer made of a resin composition containing a radical generator. A heat-sealable 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 4, Heat seal multi-layer laminate film to be described. It consists of at least a base film, a barrier base film, and a coextrusion film-forming film comprising at least five layers, and further, a first layer constituting the surface layer of the film and a fifth layer constituting the back layer Comprising a low density polyethylene-based resin layer, and the second and fourth layers constituting the intermediate layer of the film are composed of a polypropylene-based resin layer. A laminate comprising a heat-sealable multi-layer laminated film composed of an oxygen-absorbing resin layer made of a resin composition containing an oxidizing resin and a transition metal catalyst. A mixed resin layer of a polypropylene resin and a polyethylene resin is provided between the first layer and the second layer and between the fifth layer and the fourth layer. Laminated body to be described. The laminate according to any one of claims 6 to 7, wherein the base film is made of a biaxially stretched polyester resin film. The laminate according to any one of claims 6 to 8, 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 coextrusion film-forming film comprising at least five layers, and further, a first layer constituting the surface layer of the film and a fifth layer constituting the back layer Comprising a low density polyethylene-based resin layer, and the second and fourth layers constituting the intermediate layer of the film are composed of a polypropylene-based resin layer. The third layer to be used is a laminate in which a heat-sealable multilayer laminated film composed of an oxygen-absorbing resin layer made of a resin composition containing an oxidizing resin and a transition metal catalyst is sequentially laminated. A packaging bag, wherein the laminate is superposed with the surfaces of the heat-sealable multi-layer laminate film facing each other, and the end of the outer periphery is heat-sealed. It consists of at least a base film, a barrier base film, and a coextrusion film-forming film comprising at least five layers, and further, a first layer constituting the surface layer of the film and a fifth layer constituting the back layer Comprising a low density polyethylene-based resin layer, and the second and fourth layers constituting the intermediate layer of the film are composed of a polypropylene-based resin layer. The third layer to be used is a laminate in which a heat-sealable multilayer laminated film composed of an oxygen-absorbing resin layer made of a resin composition containing an oxidizing resin and a transition metal catalyst is sequentially laminated. The laminate is composed of a packaging bag in which the surfaces of the heat-sealable multi-layer laminate film are opposed to each other, and the outer peripheral edge is heat-sealed. In the packaging bag, the opening The contents are filled and packaged, and before or after the filling and packaging, or at the same time as the filling and packaging, the inner surface of the packaging bag is irradiated with ultraviolet rays, and the opening is opened to the heatsheet. A packaged product characterized by sealing to form a seal portion and sealing.

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