JP2012035436A - Laminated film and package - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated film superior in oxygen absorbency.SOLUTION: The laminated film 100 includes an oxygen absorbing layer 150 and a barrier layer 130. The oxygen absorbing layer 150 contains an oxygen absorbent and an oxygen absorbing reaction catalyst, and the barrier layer 130 has gas barrier properties. The oxygen absorbing reaction catalyst is contained in the oxygen absorbing layer 150 at a weight ratio of 100-5,000 ppm. Further, the oxygen absorbing layer 150 contains an oxidation inhibitor at a weight ratio of 0-170 ppm with respect to the oxygen absorbing layer 150.

Description

  The present invention relates to a laminated film and a package.

  Conventionally, a plastic container is used as a packaging container for storing food and beverages. When foods and beverages are wrapped in this plastic container, oxygen may remain in the plastic container. In addition, plastic containers are inferior in oxygen barrier properties compared to metal containers and glass containers. For this reason, oxygen tends to enter the inside of the plastic container from the outside. Oxygen inside the plastic container oxidizes and alters the contents of food and beverage.

  In order to solve the problem caused by oxygen in the plastic container, for example, Patent Document 1 includes an oxygen absorbing layer that contains an oxygen absorbing resin and does not contain an oxygen absorbing reaction catalyst, and is a layer adjacent to the oxygen absorbing layer. Discloses an oxygen-absorbing multilayer body selected from the group consisting of an oxygen barrier layer, a thermoplastic resin layer, and an adhesive layer.

JP 2009-12443 A

  The plastic container provided with the oxygen-absorbing multilayer body described in Patent Document 1 can absorb oxygen inside the plastic container by the oxygen absorption layer. However, there is a demand for an oxygen-absorbing multilayer body that is superior in oxygen absorption.

  An object of the present invention is to provide a laminated film having excellent oxygen absorbability.

(1)
The laminated film according to one aspect of the present invention includes an oxygen absorption layer and a barrier layer. The oxygen absorption layer includes an oxygen absorbent and an oxygen absorption reaction catalyst. The barrier layer has gas barrier properties. The oxygen absorption reaction catalyst is contained in a weight ratio of 100 ppm to 5000 ppm with respect to the oxygen absorption layer. Furthermore, the oxygen absorbing layer includes an antioxidant contained in a weight ratio of 0 ppm to 170 ppm with respect to the oxygen absorbing layer. That is, the oxygen absorbing layer may not contain an antioxidant.

  As a result of intensive studies by the inventors of the present application, in the above configuration, the oxygen absorption reaction catalyst is contained in the oxygen absorption layer in a weight ratio of 100 ppm to 5000 ppm with respect to the oxygen absorption layer, and the antioxidant is in a weight ratio with respect to the oxygen absorption layer. Thus, it was clarified that when the oxygen absorption layer contains 0 ppm or more and 170 ppm or less, the oxygen absorption amount of the laminated film is increased and the deterioration of the appearance of the laminated film is suppressed. For this reason, a laminated film is excellent in oxygen absorptivity. Furthermore, it has been clarified that when the oxygen absorbing layer contains an antioxidant, it is possible to effectively prevent the laminated film from being oxidized and deteriorated by the antioxidant while maintaining the above effects.

(2)
In the laminated film described in (1) above, the barrier layer has an oxygen permeability of 200 ml / (m ² · 24 h · atm) or less.

As a result of intensive studies by the inventor of the present application, it is clear that when the barrier layer having an oxygen permeability of 200 ml / (m ² · 24 h · atm) or less is used in the laminated film according to the present invention, the above-mentioned effect is easily exhibited. It became.

(3)
In the laminated film of the above (1) or (2), the oxygen absorption reaction catalyst is contained in a weight ratio of 500 ppm to 5000 ppm with respect to the oxygen absorption layer. The antioxidant is contained in a weight ratio of 0 ppm to 120 ppm with respect to the oxygen absorbing layer.

  As a result of intensive studies by the inventors of the present application, in the above configuration, the oxygen absorption reaction catalyst is contained in the oxygen absorption layer in a weight ratio of 500 ppm to 5000 ppm with respect to the oxygen absorption layer, and the antioxidant is in a weight ratio with respect to the oxygen absorption layer. In the oxygen absorption layer, the oxygen absorption amount of the laminated film in the initial stage (on the first day after being stored in the sealed state) is increased, and the deterioration of the appearance of the laminated film is suppressed. It became clear. Further, it has been clarified that when the oxygen absorbing layer contains an antioxidant, it is possible to effectively prevent the laminated film from being oxidized and deteriorated by the antioxidant while maintaining the above effect.

(4)
In the laminated film of (3) above, the antioxidant is contained in a weight ratio of 5 ppm to 60 ppm with respect to the oxygen absorbing layer.

  As a result of intensive studies by the inventor of the present application, in the above configuration, the antioxidant is contained in the oxygen absorption layer in a weight ratio of 5 ppm to 60 ppm by weight with respect to the oxygen absorption layer, so that storage is started in a sealed state for 3 days. It became clear that the oxygen absorption amount of the laminated film on the eyes and the seventh day increased, and the deterioration of the appearance of the laminated film and the deterioration due to oxidation were suppressed.

(5)
In the laminated film of the above (4), the oxygen absorption reaction catalyst is contained in a weight ratio of 3000 ppm to 5000 ppm with respect to the oxygen absorption layer.

  As a result of intensive studies by the inventor of the present application, in the above configuration, the oxygen absorption reaction catalyst is contained in the oxygen absorption layer in a weight ratio of 3000 ppm to 5000 ppm by weight with respect to the oxygen absorption layer, and storage is started in a sealed state. It became clear that the oxygen absorption amount of the laminated film on the day and the seventh day was increased, and the deterioration of the appearance of the laminated film and the deterioration due to oxidation were suppressed.

(6)
In the laminated film according to any one of the above (1) to (5), the oxygen absorbent is made of an oxygen-absorbing resin.

  The oxygen absorbent is made of an oxygen-absorbing resin. Unlike oxygen absorbers such as iron powder, the oxygen-absorbing resin does not color the oxygen-absorbing layer in a unique hue. For this reason, oxygen absorption resin can provide transparency to an oxygen absorption layer.

(7)
The package which concerns on 1 aspect of this invention is equipped with the laminated | multilayer film in any one of the above-mentioned (1)-(6).

  This package includes the above laminated film. For this reason, while the oxygen absorption amount of a package increases, the fall of the external appearance of a package is suppressed. Moreover, in this package, when the oxygen absorption layer of a laminated film contains antioxidant, it can prevent effectively that a laminated | multilayer film oxidizes and deteriorates with antioxidant, maintaining said effect.

  The laminated film and package according to the present invention are excellent in oxygen absorption.

It is sectional drawing of the laminated film which concerns on one Embodiment of this invention. It is sectional drawing of a package provided with a laminated film. It is an enlarged view of A part of the package shown in FIG. It is sectional drawing which showed the state which is measuring the oxygen absorption amount inside a package with the trace amount oxygen analyzer for foodstuffs.

  As shown in FIG. 1, the laminated film 100 according to this embodiment mainly includes an outer layer 110, a first adhesive layer 120, a barrier layer 130, a second adhesive layer 140, an oxygen absorption layer 150, and a seal layer 160. It is formed by laminating in this order. As shown in FIGS. 2 and 3, the laminated film 100 is used for the bottom material 300 of the package 200. Hereinafter, each configuration of the laminated film 100 will be described in detail.

<Outer layer>
The material of the outer layer 110 may be any material as long as it can be used as the bottom material 300. For example, a polyester resin is used. The outer layer 110 made of polyester resin has high rigidity. In addition, the laminated film 100 including the outer layer 110 made of a polyester resin has good transparency and surface gloss. For this reason, the package 200 is excellent in appearance and texture.

  As the polyester resin used for the outer layer 110, a saturated polyester resin is used. The saturated polyester resin has a divalent acid such as terephthalic acid as an acid component or a derivative thereof having an ester forming ability, a glycol having 2 to 10 carbon atoms as a glycol component, and other divalent alcohol or ester forming ability. And their derivatives. Specifically, examples of the polyester-based resin include polyethylene terephthalate resin, polybutylene terephthalate resin, polytrimethylene terephthalate resin, polyalkylene terephthalate resin such as polyhexamethylene terephthalate resin, and copolyester resin.

<First adhesive layer>
As a material of the first adhesive layer 120, a known adhesive resin is used, and for example, an adhesive polyolefin resin or the like is used. Specifically, as the material of the first adhesive layer 120, for example, an ethylene-methacrylate-glycidyl acrylate terpolymer, or various polyolefins, monobasic unsaturated fatty acids such as acrylic acid and methacrylic acid, maleic acid, etc. , Dibasic unsaturated fatty acids such as fumaric acid and itaconic acid or those grafted with these anhydrides (maleic acid grafted EVA, maleic acid grafted ethylene-α-olefin copolymer, etc.) are used.

<Barrier layer>
The barrier layer 130 limits the permeation of oxygen entering from the outside of the package 200. As the material of the barrier layer 130, a known material having oxygen barrier properties is used. For example, polyvinyl alcohol resin, saponified ethylene vinyl acetate copolymer (hereinafter referred to as “EVOH resin”), vinylidene chloride resin, or A polyamide resin having an aromatic ring in the diamine component is used. The barrier layer 130 preferably has an oxygen permeability of 200 ml / (m ² · 24 h · atm) or less, more preferably an oxygen permeability of 10 ml / (m ² · 24 h · atm) or less, The rate is more preferably 1 ml / (m ² · 24 h · atm) or less.

<Second adhesive layer>
As the material of the second adhesive layer 140, a known adhesive resin is used, and for example, an adhesive polyolefin resin or the like is used. Specifically, as the material of the second adhesive layer 140, for example, ethylene-methacrylate-glycidyl acrylate terpolymer or various polyolefins, monobasic unsaturated fatty acids such as acrylic acid and methacrylic acid, maleic acid , Dibasic unsaturated fatty acids such as fumaric acid and itaconic acid or those grafted with these anhydrides (maleic acid grafted EVA, maleic acid grafted ethylene-α-olefin copolymer, etc.) are used.

  The second adhesive layer 140 may contain an antioxidant or may not contain an antioxidant. When the second adhesive layer 140 contains an antioxidant, a known antioxidant is used as the antioxidant. For example, a hindered phenol-based antioxidant, a phosphorus-based antioxidant, a thioether-based antioxidant is used. Etc. are used alone or in combination of two or more.

<Oxygen absorption layer>
The oxygen absorbing layer 150 includes an oxygen absorbing resin that is an oxygen absorbent and an oxygen absorbing reaction catalyst. As the oxygen absorbing resin, an unsaturated polyolefin oxygen absorbing resin or the like is used. Specifically, examples of the oxygen-absorbing resin include an ethylenically unsaturated hydrocarbon polymer, a main chain ethylenically unsaturated hydrocarbon polymer, a polyether unit polymer, a copolymer of ethylene and a distorted cyclic alkylene, a polyamide resin, and an acid-modified resin. Polybutadiene, hydroxyaldehyde polymer or the like is used alone or mixed with a base resin that does not affect the transparency other than the oxygen-absorbing resin.

  As the oxygen absorption reaction catalyst, a transition metal catalyst such as zinc stearate, cobalt stearate, cobalt naphthenate, zinc naphthenate, acetylacetonate zinc, acetylacetonate cobalt or acetylacetonate copper is used. The content of the oxygen absorption reaction catalyst is 100 ppm to 5000 ppm by weight with respect to the oxygen absorption layer 150. In particular, the content of the oxygen absorption reaction catalyst is preferably 500 ppm to 5000 ppm by weight with respect to the oxygen absorption layer 150, and more preferably 1000 ppm to 5000 ppm by weight with respect to the oxygen absorption layer 150. Preferably, the weight ratio with respect to the oxygen absorption layer 150 is 3000 ppm or more and 5000 ppm or less, and the weight ratio with respect to the oxygen absorption layer 150 is more preferably 3500 ppm or more and 5000 ppm or less.

  The oxygen absorption layer 150 may contain an antioxidant or may not contain an antioxidant. When the oxygen absorption layer 150 contains an antioxidant, a known antioxidant is used as the antioxidant. For example, a hindered phenol-based antioxidant, a phosphorus-based antioxidant, a thioether-based antioxidant, etc. Are used alone or in admixture of two or more. The content of the antioxidant in the oxygen absorption layer 150 is 0 ppm or more and 170 ppm or less by weight with respect to the oxygen absorption layer 150. In particular, the content of the antioxidant in the oxygen absorption layer 150 is preferably 0 ppm or more and 120 ppm or less by weight with respect to the oxygen absorption layer 150, and is 5 ppm or more and 120 ppm or less by weight with respect to the oxygen absorption layer 150. More preferably, it is more preferably 5 ppm or more and 60 ppm or less by weight with respect to the oxygen absorption layer 150.

<Sealing layer>
The sealing layer 160 has a sealing function for sealing the lid member 400 to the bottom member 300 (heat sealing, ultrasonic sealing, high frequency sealing, impulse sealing, etc.), and the contents stored in the package 200 It does not have an adverse effect. The material of the seal layer 160 includes low density polyethylene (LDPE) resin, linear low density polyethylene (LLDPE) resin, medium density polyethylene (MDPE) resin, high density polyethylene (HDPE) resin, polypropylene (PP) resin, ethylene -Vinyl acetate copolymer (EVA) resin, ethylene-methyl methacrylate copolymer (EMMA) resin, ethylene-ethyl acrylate copolymer (EEA) resin, ethylene-methyl acrylate copolymer (EMA) resin, ethylene-ethyl Acrylate-maleic anhydride copolymer (E-EA-MAH) resin, ethylene-acrylate copolymer (EAA) resin, ethylene-methacrylic acid copolymer (EMAA) resin, ionomer (ION) resin, etc. Or two or more types are used in combination.

  The seal layer 160 may contain an antioxidant or may not contain an antioxidant. When the seal layer 160 contains an antioxidant, a known antioxidant is used as the antioxidant, and examples thereof include hindered phenol-based antioxidants, phosphorus-based antioxidants, and thioether-based antioxidants. , Used alone or in combination of two or more.

<Packaging body>
As shown in FIGS. 2 and 3, the package 200 includes a bottom member 300 and a lid member 400. The bottom material 300 is made of the laminated film 100 in which the pockets 310 are formed such that the outer layer 110 is on the outside and the seal layer 160 is on the inside (see FIG. 3).

  Examples of the material of the lid member 400 include a biaxially stretched polypropylene film (OPP film), a biaxially stretched polyethylene terephthalate film (VM-PET film) on which a metal oxide is deposited, or a film in which a polyethylene resin is laminated. It is done. Contents (not shown) such as food, beverages or industrial parts are accommodated in the pocket 310 of the bottom member 300 from which the air inside has been removed. After the contents are stored in the pocket 310, the lid member 400 is sealed to the bottom member 300, and the pocket 310 of the bottom member 300 is sealed.

  Next, Examples 1 to 26 and Comparative Examples 1 to 10 according to the package 200 including the laminated film 100 of the present invention will be described. In addition, this invention is not limited at all by these Examples.

Example 1
<Production of bottom material>
A copolymer polyester resin (manufactured by Eastman Chemical Japan Co., Ltd., product number: GN071) was prepared as a resin constituting the outer layer 110. An adhesive polyolefin-based resin (manufactured by Mitsui Chemicals, product number: SF740) was prepared as a resin constituting the first adhesive layer 120. As a resin constituting the barrier layer 130, an EVOH resin (manufactured by Kuraray Co., Ltd., product number: J171B) was prepared. An adhesive polyolefin resin (manufactured by Mitsui Chemicals, product number: LF308) was prepared as a resin constituting the second adhesive layer 140. As the resin constituting the oxygen absorbing layer 150, a mixture of 80% by weight of the base resin and 20% by weight of the unsaturated polyolefin oxygen absorbing resin was prepared. An LDPE resin (manufactured by Ube Maruzen Polyethylene Co., Ltd., product number: F522N) was prepared as a resin constituting the seal layer 160.

  Cobalt stearate that is an oxygen absorption reaction catalyst is added to the mixture of the base resin of the oxygen absorption layer 150 and the unsaturated polyolefin-based oxygen absorption resin so that the content is 100 ppm by weight with respect to the oxygen absorption layer 150. did. In addition, the antioxidant was not added to the oxygen absorption layer 150, the second adhesive layer 140, and the seal layer 160.

  The LDPE resin of the seal layer 160, the base resin of the oxygen absorption layer 150 and a mixture of the unsaturated polyolefin oxygen absorption resin, the adhesive polyolefin resin of the second adhesive layer 140, the EVOH resin of the barrier layer 130, the first The adhesive polyolefin resin of the adhesive layer 120 and the copolyester resin of the outer layer 110 were coextruded in this order, and the laminated film 100 was produced. In the obtained laminated film 100, the thickness of the seal layer 160 is 10 μm, the thickness of the oxygen absorption layer 150 is 30 μm, the thickness of the second adhesive layer 140 is 20 μm, the thickness of the barrier layer 130 is 40 μm, and the first adhesion The thickness of the layer 120 was 20 μm, and the thickness of the outer layer 110 was 90 μm.

Using a deep drawing type fully automatic vacuum packaging machine (manufactured by MULTIVAC, model number: R-530), the pocket 310 (long side 160 mm × short side 105 mm) is formed on the laminated film 100 under conditions of a molding temperature of 95 ° C. and a molding time of 3 seconds. X depth 1.5 mm, surface area 240 cm ² inside the pocket) was molded to prepare the bottom material 300.

<Production of lid material>
An LLDPE resin (manufactured by Prime Polymer Co., Ltd., product number: ULT ZEXX 2022L) was formed into a film by a T-die extrusion method to obtain an LLDPE film having a thickness of 30 μm. This LLDPE film, a biaxially stretched polypropylene film (OPP film) with a thickness of 30 μm, and a biaxially stretched polyethylene terephthalate film (VM-PET film) with a thickness of 12 μm subjected to aluminum deposition were bonded together by a dry laminating method, A lid member 400 which is a multilayer film was produced.

<Production of packaging>
The bottom member 300 and the lid member 400 were sealed by heat sealing under conditions of 135 ° C. and 1.5 seconds without removing the air inside the pocket 310, thereby producing a package 200. The volume of the package 200 was 250 cm ³ .

<Measurement of oxygen absorption>
As shown in FIG. 4, when the bottom material 300 and the lid material 400 are heat-sealed using a food trace oxygen analyzer 500 (manufactured by Iijima Electronics Co., Ltd., model number: IS-300), that is, in a sealed state. The oxygen absorption amount inside the package 200 on the first day, the third day, and the seventh day after the storage of the package 200 was measured. Specifically, the oxygen absorption of the package 200 is performed under the conditions of a storage temperature of 5 ° C. and a sampling time of 7 seconds with the needle 510 of the trace oxygen analyzer for food 500 stuck into the lid member 400 through the adhesive rubber 520. The amount was measured. The oxygen absorption amount on the third day is the total amount of oxygen absorbed by the package 200 from the first to the third day, and the oxygen absorption amount on the seventh day is the packaging from the first to the seventh day. This is the total amount of oxygen absorbed by the body 200.

As a result, the oxygen absorption amount on the first day was 0.008 cc / cm ² , the oxygen absorption amount on the third day was 0.016 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.029 cc / cm ² . (See Table 1 below).

<Appearance evaluation>
The appearance of the laminated film 100 was visually observed and evaluated for the presence or absence of color. In the evaluation, “◯” indicates that no color is attached, and “X” indicates that the color is attached. The appearance of the laminated film 100 was evaluated as “Good” without any color (see Table 1 below).

(Example 2)
A hindered phenolic antioxidant (manufactured by BASF Corp., product number) was added to the mixture of the base resin of the oxygen absorbing layer 150 and the unsaturated polyolefin oxygen absorbing resin so that the content ratio was 35 ppm by weight with respect to the oxygen absorbing layer 150. : IRGANOX 1010) except that the package 200 was prepared in the same manner as in Example 1, and the oxygen absorption amounts on the first, third, and seventh days of the package 200 were measured in the same manner as in Example 1, Furthermore, the appearance was evaluated.

As a result, the oxygen absorption amount on the first day was 0.004 cc / cm ² , the oxygen absorption amount on the third day was 0.023 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.042 cc / cm ² . . The appearance of the laminated film 100 was evaluated as “Good” without any color (see Table 1 below).

(Example 3)
Except for adding a hindered phenol-based antioxidant to the mixture of the base resin of the oxygen-absorbing layer 150 and the unsaturated polyolefin-based oxygen-absorbing resin so that the content ratio is 170 ppm by weight with respect to the oxygen-absorbing layer 150, A package 200 was produced in the same manner as in Example 1, and each oxygen absorption amount on days 1, 3, and 7 of the package 200 was measured in the same manner as in Example 1, and the appearance was further evaluated.

As a result, the oxygen absorption amount on the first day was 0.003 cc / cm ² , the oxygen absorption amount on the third day was 0.015 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.032 cc / cm ² . . The appearance of the laminated film 100 was evaluated as “Good” without any color (see Table 1 below).

Example 4
Example 1 except that cobalt stearate was added to the mixture of the base resin of the oxygen absorption layer 150 and the unsaturated polyolefin-based oxygen absorption resin so that the content ratio was 500 ppm by weight with respect to the oxygen absorption layer 150. In the same manner, a package 200 was produced, and the oxygen absorption amounts on the first, third, and seventh days of the package 200 were measured in the same manner as in Example 1, and the appearance was further evaluated.

As a result, the oxygen absorption amount on the first day was 0.018 cc / cm ² , the oxygen absorption amount on the third day was 0.025 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.039 cc / cm ² . . The appearance of the laminated film 100 was evaluated as “Good” without any color (see Table 1 below).

(Example 5)
Except for adding a hindered phenol-based antioxidant to the mixture of the base resin of the oxygen-absorbing layer 150 and the unsaturated polyolefin-based oxygen-absorbing resin so that the content is 35 ppm by weight with respect to the oxygen-absorbing layer 150, The package 200 was produced in the same manner as in Example 4, and the oxygen absorption amounts on the first, third, and seventh days of the package 200 were measured in the same manner as in Example 1, and the appearance was further evaluated.

As a result, the oxygen absorption amount on the first day was 0.020 cc / cm ² , the oxygen absorption amount on the third day was 0.054 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.071 cc / cm ² . . The appearance of the laminated film 100 was evaluated as “Good” without any color (see Table 1 below).

(Example 6)
Except for adding a hindered phenol-based antioxidant to the mixture of the base resin of the oxygen-absorbing layer 150 and the unsaturated polyolefin-based oxygen-absorbing resin so that the content ratio is 170 ppm by weight with respect to the oxygen-absorbing layer 150, The package 200 was produced in the same manner as in Example 4, and the oxygen absorption amounts on the first, third, and seventh days of the package 200 were measured in the same manner as in Example 1, and the appearance was further evaluated.

As a result, the oxygen absorption amount on the first day was 0.003 cc / cm ² , the oxygen absorption amount on the third day was 0.019 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.035 cc / cm ² . . The appearance of the laminated film 100 was evaluated as “Good” without any color (see Table 1 below).

(Example 7)
Example 1 except that cobalt stearate was added to the mixture of the base resin of the oxygen absorption layer 150 and the unsaturated polyolefin-based oxygen absorption resin so that the content ratio was 1000 ppm by weight with respect to the oxygen absorption layer 150. In the same manner, a package 200 was produced, and the oxygen absorption amounts on the first, third, and seventh days of the package 200 were measured in the same manner as in Example 1, and the appearance was further evaluated.

As a result, the oxygen absorption amount on the first day was 0.018 cc / cm ² , the oxygen absorption amount on the third day was 0.028 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.040 cc / cm ² . . The appearance of the laminated film 100 was evaluated as “Good” without any color (see Table 1 below).

(Example 8)
Except for adding a hindered phenol-based antioxidant to the mixture of the base resin of the oxygen-absorbing layer 150 and the unsaturated polyolefin-based oxygen-absorbing resin so that the content is 5 ppm by weight with respect to the oxygen-absorbing layer 150, The package 200 was produced in the same manner as in Example 7, the oxygen absorption amounts on the first, third, and seventh days of the package 200 were measured in the same manner as in Example 1, and the appearance was further evaluated.

As a result, the oxygen absorption amount on the first day was 0.020 cc / cm ² , the oxygen absorption amount on the third day was 0.047 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.076 cc / cm ² . . The appearance of the laminated film 100 was evaluated as “Good” without any color (see Table 1 below).

Example 9
Except for adding a hindered phenol-based antioxidant to the mixture of the base resin of the oxygen-absorbing layer 150 and the unsaturated polyolefin-based oxygen-absorbing resin so that the content is 35 ppm by weight with respect to the oxygen-absorbing layer 150, The package 200 was produced in the same manner as in Example 7, the oxygen absorption amounts on the first, third, and seventh days of the package 200 were measured in the same manner as in Example 1, and the appearance was further evaluated.

As a result, the oxygen absorption amount on the first day was 0.030 cc / cm ² , the oxygen absorption amount on the third day was 0.053 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.078 cc / cm ² . . The appearance of the laminated film 100 was evaluated as “Good” without any color (see Table 1 below).

(Example 10)
The package 200 was prepared in the same manner as in Example 9, and the oxygen absorption amounts on the first, third, and seventh days of the package 200 were measured in the same manner as in Example 1 except that the storage temperature was 23 ° C. Further, the appearance was evaluated.

As a result, the oxygen absorption amount on the first day was 0.051 cc / cm ² , the oxygen absorption amount on the third day was 0.113 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.133 cc / cm ² . . The appearance of the laminated film 100 was evaluated as “Good” without any color (see Table 1 below).

(Example 11)
The package 200 was prepared in the same manner as in Example 9, and the oxygen absorption amounts on the first, third, and seventh days of the package 200 were measured in the same manner as in Example 1 except that the storage temperature was 50 ° C. Further, the appearance was evaluated.

As a result, the oxygen absorption amount on the first day was 0.165 cc / cm ² , the oxygen absorption amount on the third day was 0.215 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.215 cc / cm ² . . The appearance of the laminated film 100 was evaluated as “Good” without any color (see Table 1 below).

(Example 12)
Except for adding a hindered phenol-based antioxidant to the mixture of the base resin of the oxygen-absorbing layer 150 and the unsaturated polyolefin-based oxygen-absorbing resin so that the content is 60 ppm by weight with respect to the oxygen-absorbing layer 150, The package 200 was produced in the same manner as in Example 7, the oxygen absorption amounts on the first, third, and seventh days of the package 200 were measured in the same manner as in Example 1, and the appearance was further evaluated.

As a result, the oxygen absorption amount on the first day was 0.032 cc / cm ² , the oxygen absorption amount on the third day was 0.046 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.073 cc / cm ² . . The appearance of the laminated film 100 was evaluated as “Good” without any color (see Table 1 below).

(Example 13)
Except for adding a hindered phenol-based antioxidant to the mixture of the base resin of the oxygen-absorbing layer 150 and the unsaturated polyolefin-based oxygen-absorbing resin so that the content is 120 ppm by weight with respect to the oxygen-absorbing layer 150, The package 200 was produced in the same manner as in Example 7, the oxygen absorption amounts on the first, third, and seventh days of the package 200 were measured in the same manner as in Example 1, and the appearance was further evaluated.

As a result, the oxygen absorption amount on the first day was 0.018 cc / cm ² , the oxygen absorption amount on the third day was 0.040 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.065 cc / cm ² . . The appearance of the laminated film 100 was evaluated as “Good” without any color (see Table 1 below).

(Example 14)
Except for adding a hindered phenol-based antioxidant to the mixture of the base resin of the oxygen-absorbing layer 150 and the unsaturated polyolefin-based oxygen-absorbing resin so that the content ratio is 170 ppm by weight with respect to the oxygen-absorbing layer 150, The package 200 was produced in the same manner as in Example 7, the oxygen absorption amounts on the first, third, and seventh days of the package 200 were measured in the same manner as in Example 1, and the appearance was further evaluated.

As a result, the oxygen absorption amount of 1 day 0.005 cc / ^cm 2, the oxygen absorption amount of the third day 0.018cc / ^cm 2, 7 day oxygen absorption amount was 0.043cc / cm ² . The appearance of the laminated film 100 was evaluated as “Good” without any color (see Table 1 below).

(Example 15)
Example 1 except that cobalt stearate was added to the mixture of the base resin of the oxygen absorption layer 150 and the unsaturated polyolefin-based oxygen absorption resin so that the content ratio was 2000 ppm by weight with respect to the oxygen absorption layer 150. In the same manner, a package 200 was produced, and the oxygen absorption amounts on the first, third, and seventh days of the package 200 were measured in the same manner as in Example 1, and the appearance was further evaluated.

As a result, the oxygen absorption amount on the first day was 0.019 cc / cm ² , the oxygen absorption amount on the third day was 0.035 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.043 cc / cm ² . . The appearance of the laminated film 100 was evaluated as “Good” without any color (see Table 1 below).

(Example 16)
Except for adding a hindered phenol-based antioxidant to the mixture of the base resin of the oxygen-absorbing layer 150 and the unsaturated polyolefin-based oxygen-absorbing resin so that the content is 35 ppm by weight with respect to the oxygen-absorbing layer 150, A package 200 was produced in the same manner as in Example 15, and the oxygen absorption amounts on the first, third, and seventh days of the package 200 were measured in the same manner as in Example 1, and the appearance was further evaluated.

As a result, the oxygen absorption amount on the first day was 0.019 cc / cm ² , the oxygen absorption amount on the third day was 0.054 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.070 cc / cm ² . . The appearance of the laminated film 100 was evaluated as “Good” without any color (see Table 1 below).

(Example 17)
Except for adding a hindered phenol-based antioxidant to the mixture of the base resin of the oxygen-absorbing layer 150 and the unsaturated polyolefin-based oxygen-absorbing resin so that the content ratio is 170 ppm by weight with respect to the oxygen-absorbing layer 150, A package 200 was produced in the same manner as in Example 15, and the oxygen absorption amounts on the first, third, and seventh days of the package 200 were measured in the same manner as in Example 1, and the appearance was further evaluated.

As a result, the oxygen absorption amount on the first day was 0.007 cc / cm ² , the oxygen absorption amount on the third day was 0.023 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.048 cc / cm ² . . The appearance of the laminated film 100 was evaluated as “Good” without any color (see Table 1 below).

(Example 18)
Example 1 except that cobalt stearate was added to the mixture of the base resin and unsaturated polyolefin-based oxygen-absorbing resin in the oxygen-absorbing layer 150 so that the content ratio was 3000 ppm by weight with respect to the oxygen-absorbing layer 150. In the same manner, a package 200 was produced, and the oxygen absorption amounts on the first, third, and seventh days of the package 200 were measured in the same manner as in Example 1, and the appearance was further evaluated.

As a result, the oxygen absorption amount on the first day was 0.023 cc / cm ² , the oxygen absorption amount on the third day was 0.037 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.047 cc / cm ² . . The appearance of the laminated film 100 was evaluated as “Good” without any color (see Table 1 below).

(Example 19)
Except for adding a hindered phenol-based antioxidant to the mixture of the base resin of the oxygen-absorbing layer 150 and the unsaturated polyolefin-based oxygen-absorbing resin so that the content is 35 ppm by weight with respect to the oxygen-absorbing layer 150, A package 200 was produced in the same manner as in Example 18, and the oxygen absorption amounts on the first, third, and seventh days of the package 200 were measured in the same manner as in Example 1, and the appearance was further evaluated.

As a result, the oxygen absorption amount on the first day was 0.025 cc / cm ² , the oxygen absorption amount on the third day was 0.076 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.095 cc / cm ² . . The appearance of the laminated film 100 was evaluated as “Good” without any color (see Table 1 below).

(Example 20)
Except for adding a hindered phenol-based antioxidant to the mixture of the base resin of the oxygen-absorbing layer 150 and the unsaturated polyolefin-based oxygen-absorbing resin so that the content ratio is 170 ppm by weight with respect to the oxygen-absorbing layer 150, A package 200 was produced in the same manner as in Example 18, and the oxygen absorption amounts on the first, third, and seventh days of the package 200 were measured in the same manner as in Example 1, and the appearance was further evaluated.

As a result, the oxygen absorption amount on the first day was 0.008 cc / cm ² , the oxygen absorption amount on the third day was 0.025 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.050 cc / cm ² . . The appearance of the laminated film 100 was evaluated as “Good” without any color (see Table 1 below).

(Example 21)
Example 1 except that cobalt stearate was added to the mixture of the base resin of the oxygen absorption layer 150 and the unsaturated polyolefin-based oxygen absorption resin so that the content ratio was 3500 ppm by weight with respect to the oxygen absorption layer 150. In the same manner, a package 200 was produced, and the oxygen absorption amounts on the first, third, and seventh days of the package 200 were measured in the same manner as in Example 1, and the appearance was further evaluated.

As a result, the oxygen absorption amount on the first day was 0.022 cc / cm ² , the oxygen absorption amount on the third day was 0.038 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.049 cc / cm ² . . The appearance of the laminated film 100 was evaluated as “Good” without any color (see Table 1 below).

(Example 22)
Except for adding a hindered phenol-based antioxidant to the mixture of the base resin of the oxygen-absorbing layer 150 and the unsaturated polyolefin-based oxygen-absorbing resin so that the content is 35 ppm by weight with respect to the oxygen-absorbing layer 150, A package 200 was produced in the same manner as in Example 21, and the oxygen absorption amounts on the first, third, and seventh days of the package 200 were measured in the same manner as in Example 1, and the appearance was further evaluated.

As a result, the oxygen absorption amount on the first day was 0.027 cc / cm ² , the oxygen absorption amount on the third day was 0.080 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.099 cc / cm ² . . The appearance of the laminated film 100 was evaluated as “Good” without any color (see Table 1 below).

(Example 23)
Except for adding a hindered phenol-based antioxidant to the mixture of the base resin of the oxygen-absorbing layer 150 and the unsaturated polyolefin-based oxygen-absorbing resin so that the content ratio is 170 ppm by weight with respect to the oxygen-absorbing layer 150, A package 200 was produced in the same manner as in Example 21, and the oxygen absorption amounts on the first, third, and seventh days of the package 200 were measured in the same manner as in Example 1, and the appearance was further evaluated.

As a result, the oxygen absorption amount on the first day was 0.009 cc / cm ² , the oxygen absorption amount on the third day was 0.027 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.049 cc / cm ² . . The appearance of the laminated film 100 was evaluated as “Good” without any color (see Table 1 below).

(Example 24)
Example 1 except that cobalt stearate was added to the mixture of the base resin of the oxygen absorption layer 150 and the unsaturated polyolefin-based oxygen absorption resin so that the content ratio was 5000 ppm by weight with respect to the oxygen absorption layer 150. In the same manner, a package 200 was produced, and the oxygen absorption amounts on the first, third, and seventh days of the package 200 were measured in the same manner as in Example 1, and the appearance was further evaluated.

As a result, the oxygen absorption amount on the first day was 0.025 cc / cm ² , the oxygen absorption amount on the third day was 0.040 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.055 cc / cm ² . . The appearance of the laminated film 100 was evaluated as “Good” without any color (see Table 1 below).

(Example 25)
Except for adding a hindered phenol-based antioxidant to the mixture of the base resin of the oxygen-absorbing layer 150 and the unsaturated polyolefin-based oxygen-absorbing resin so that the content is 35 ppm by weight with respect to the oxygen-absorbing layer 150, A package 200 was produced in the same manner as in Example 24, and the oxygen absorption amounts on the first, third, and seventh days of the package 200 were measured in the same manner as in Example 1, and the appearance was further evaluated.

As a result, the oxygen absorption amount on the first day was 0.030 cc / cm ² , the oxygen absorption amount on the third day was 0.085 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.105 cc / cm ² . . The appearance of the laminated film 100 was evaluated as “Good” without any color (see Table 1 below).

(Example 26)
Except for adding a hindered phenol-based antioxidant to the mixture of the base resin of the oxygen-absorbing layer 150 and the unsaturated polyolefin-based oxygen-absorbing resin so that the content ratio is 170 ppm by weight with respect to the oxygen-absorbing layer 150, A package 200 was produced in the same manner as in Example 24, and the oxygen absorption amounts on the first, third, and seventh days of the package 200 were measured in the same manner as in Example 1, and the appearance was further evaluated.

As a result, the oxygen absorption amount on the first day was 0.012 cc / cm ² , the oxygen absorption amount on the third day was 0.035 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.055 cc / cm ² . . The appearance of the laminated film 100 was evaluated as “Good” without any color (see Table 1 below).

(Comparative Example 1)
A package was prepared in the same manner as in Example 1 except that cobalt stearate was not added to the mixture of the base resin and the unsaturated polyolefin-based oxygen absorbing resin of the oxygen absorbing layer 150. The oxygen absorption amount on the first, third, and seventh days of the package was measured, and the appearance was further evaluated.

As a result, the oxygen absorption amount on the first day was 0.000 cc / cm ² , the oxygen absorption amount on the third day was 0.000 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.003 cc / cm ² . . The appearance of the laminated film was evaluated as “Good” without any color (see Table 1 below).

(Comparative Example 2)
Except for adding a hindered phenol-based antioxidant to the mixture of the base resin of the oxygen-absorbing layer 150 and the unsaturated polyolefin-based oxygen-absorbing resin so that the content is 35 ppm by weight with respect to the oxygen-absorbing layer 150, A package was produced in the same manner as in Comparative Example 1, and the oxygen absorption amounts on the first, third, and seventh days of the package were measured in the same manner as in Example 1, and the appearance was further evaluated.

As a result, the oxygen absorption amount on the first day was 0.000 cc / cm ² , the oxygen absorption amount on the third day was 0.000 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.004 cc / cm ² . . The appearance of the laminated film was evaluated as “Good” without any color (see Table 1 below).

(Comparative Example 3)
Except for adding a hindered phenol-based antioxidant to the mixture of the base resin of the oxygen-absorbing layer 150 and the unsaturated polyolefin-based oxygen-absorbing resin so that the content ratio is 170 ppm by weight with respect to the oxygen-absorbing layer 150, A package was produced in the same manner as in Comparative Example 1, and the oxygen absorption amounts on the first, third, and seventh days of the package were measured in the same manner as in Example 1, and the appearance was further evaluated.

As a result, the oxygen absorption amount on the first day was 0.000 cc / cm ² , the oxygen absorption amount on the third day was 0.000 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.001 cc / cm ² . . The appearance of the laminated film was evaluated as “Good” without any color (see Table 1 below).

(Comparative Example 4)
Example 1 except that cobalt stearate was added to the mixture of the base resin of the oxygen absorbing layer 150 and the unsaturated polyolefin-based oxygen absorbing resin so that the content ratio was 10 ppm by weight with respect to the oxygen absorbing layer 150. A package was produced in the same manner, and the oxygen absorption amount on the first, third, and seventh days of the package was measured in the same manner as in Example 1, and the appearance was further evaluated.

As a result, the oxygen absorption amount on the first day was 0.000 cc / cm ² , the oxygen absorption amount on the third day was 0.000 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.002 cc / cm ² . . The appearance of the laminated film was evaluated as “Good” without any color (see Table 1 below).

(Comparative Example 5)
Except for adding a hindered phenol-based antioxidant to the mixture of the base resin of the oxygen-absorbing layer 150 and the unsaturated polyolefin-based oxygen-absorbing resin so that the content is 35 ppm by weight with respect to the oxygen-absorbing layer 150, A package was produced in the same manner as in Comparative Example 4, and the oxygen absorption amounts on the first, third, and seventh days of the package were measured in the same manner as in Example 1, and the appearance was further evaluated.

As a result, the oxygen absorption amount on the first day was 0.000 cc / cm ² , the oxygen absorption amount on the third day was 0.000 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.002 cc / cm ² . . The appearance of the laminated film was evaluated as “Good” without any color (see Table 1 below).

(Comparative Example 6)
Except for adding a hindered phenol-based antioxidant to the mixture of the base resin of the oxygen-absorbing layer 150 and the unsaturated polyolefin-based oxygen-absorbing resin so that the content ratio is 170 ppm by weight with respect to the oxygen-absorbing layer 150, A package was produced in the same manner as in Comparative Example 4, and the oxygen absorption amounts on the first, third, and seventh days of the package were measured in the same manner as in Example 1, and the appearance was further evaluated.

As a result, the oxygen absorption amount on the first day was 0.000 cc / cm ² , the oxygen absorption amount on the third day was 0.000 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.002 cc / cm ² . . The appearance of the laminated film was evaluated as “Good” without any color (see Table 1 below).

(Comparative Example 7)
Except for adding a hindered phenol-based antioxidant to the mixture of the base resin and unsaturated polyolefin-based oxygen-absorbing resin of the oxygen-absorbing layer 150 so that the content is 200 ppm by weight with respect to the oxygen-absorbing layer 150, A package was produced in the same manner as in Example 7, and the oxygen absorption amount on the first, third, and seventh days of the package was measured in the same manner as in Example 1, and the appearance was further evaluated.

As a result, the oxygen absorption amount on the first day was 0.000 cc / cm ² , the oxygen absorption amount on the third day was 0.000 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.000 cc / cm ² . . The appearance of the laminated film was evaluated as “Good” without any color (see Table 1 below).

(Comparative Example 8)
Example 1 except that cobalt stearate was added to the mixture of the base resin and unsaturated polyolefin-based oxygen-absorbing resin in the oxygen-absorbing layer 150 so that the content ratio was 5500 ppm by weight with respect to the oxygen-absorbing layer 150. A package was produced in the same manner, and the oxygen absorption amount on the first, third, and seventh days of the package was measured in the same manner as in Example 1, and the appearance was further evaluated.

As a result, the oxygen absorption amount on the first day was 0.024 cc / cm ² , the oxygen absorption amount on the third day was 0.040 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.053 cc / cm ² . . The appearance of the laminated film was colored and evaluated as x (see Table 1 below).

(Comparative Example 9)
Except for adding a hindered phenol-based antioxidant to the mixture of the base resin of the oxygen-absorbing layer 150 and the unsaturated polyolefin-based oxygen-absorbing resin so that the content is 35 ppm by weight with respect to the oxygen-absorbing layer 150, A package was produced in the same manner as in Comparative Example 8, and the oxygen absorption amounts on the first, third, and seventh days of the package were measured in the same manner as in Example 1, and the appearance was further evaluated.

As a result, the oxygen absorption amount on the first day was 0.028 cc / cm ² , the oxygen absorption amount on the third day was 0.087 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.103 cc / cm ² . . The appearance of the laminated film was colored and evaluated as x (see Table 1 below).

(Comparative Example 10)
Except for adding a hindered phenol-based antioxidant to the mixture of the base resin of the oxygen-absorbing layer 150 and the unsaturated polyolefin-based oxygen-absorbing resin so that the content ratio is 170 ppm by weight with respect to the oxygen-absorbing layer 150, A package was produced in the same manner as in Comparative Example 8, and the oxygen absorption amounts on the first, third, and seventh days of the package were measured in the same manner as in Example 1, and the appearance was further evaluated.

As a result, the oxygen absorption amount on the first day was 0.013 cc / cm ² , the oxygen absorption amount on the third day was 0.034 cc / cm ² , and the oxygen absorption amount on the seventh day was 0.057 cc / cm ² . . The appearance of the laminated film was colored and evaluated as x (see Table 1 below).

  The packaging body 200 which concerns on Examples 1-26 had many oxygen absorption amount compared with the packaging body which concerns on Comparative Examples 1-10, and had high oxygen absorptivity. Moreover, while the external appearance of the packaging body 200 which concerns on Examples 1-26 was good with no color, the external appearance of the packaging body which concerns on Comparative Examples 8-10 was colored and was unsatisfactory. It was. Further, as is apparent from the oxygen absorption amounts of the packaging bodies 200 according to Examples 9 to 11, excellent oxygen absorption was maintained at any storage temperature of 5 to 50 ° C.

  Examples 4, 5, 7 to 13, 15, 16, 18, 19, 21, 22, 24, 25 in which the oxygen absorption reaction catalyst of the oxygen absorption layer 150 is 500 ppm to 5000 ppm and the antioxidant is 0 ppm to 120 ppm. The package 200 according to the present invention had a larger amount of oxygen absorption on the first day than the package 200 according to the other examples and the packages according to the comparative examples. In addition, the package 200 according to Examples 5, 8-12, 16, 19, 22, and 25, in which the oxygen absorption reaction catalyst of the oxygen absorption layer 150 is 500 ppm to 5000 ppm and the antioxidant is 5 ppm to 60 ppm, Compared with the package 200 according to the example and the package according to the comparative example, the oxygen absorption amount on the third day and the seventh day was larger. Further, the package 200 according to Examples 19, 22, and 25 in which the oxygen absorption reaction catalyst of the oxygen absorption layer 150 is 3000 ppm to 5000 ppm and the antioxidant is 5 ppm to 60 ppm is the same as the package 200 according to the other examples. As compared with the package according to the comparative example, the oxygen absorption amount on the third and seventh days was further increased.

<Effect in this embodiment>
As described above, as a result of intensive studies by the inventors of the present application, in the laminated film 100, the oxygen absorption reaction catalyst is contained in the oxygen absorption layer 150 in a weight ratio of 100 ppm or more and 5000 ppm or less with respect to the oxygen absorption layer 150. When oxygen is contained in the oxygen absorption layer 150 in a weight ratio of 0 ppm or more and 170 ppm or less with respect to the oxygen absorption layer 150, the oxygen absorption amount of the laminated film 100 is increased and the deterioration of the appearance of the laminated film 100 is suppressed. Became clear. For this reason, the laminated film 100 is excellent in oxygen absorptivity. Furthermore, it has been clarified that when the oxygen absorbing layer 150 contains an antioxidant, it is possible to effectively prevent the laminated film 100 from being oxidized and deteriorated by the antioxidant while maintaining the above effects.

Moreover, in this embodiment, when the barrier layer whose oxygen permeability is 200 ml / (m < ² > 24h * atm) or less is utilized for the laminated film 100 which concerns on this invention as a result of an inventor's earnest examination, the said effect is obtained. It became clear that became easy to express.

  In the present embodiment, as a result of intensive studies by the inventors of the present application, in the laminated film 100, the oxygen absorption reaction catalyst is contained in the oxygen absorption layer 150 in a weight ratio of 500 ppm to 5000 ppm with respect to the oxygen absorption layer 150, and oxidized. By containing the inhibitor in the oxygen absorption layer 150 in a weight ratio of 0 ppm or more and 120 ppm or less with respect to the oxygen absorption layer 150, the oxygen absorption amount of the laminated film 100 in the initial stage (on the first day after being stored in a sealed state) It became clear that the fall of the external appearance of the laminated | multilayer film 100 was suppressed with increasing. Moreover, when the oxygen absorption layer 150 contains antioxidant, it became clear that it can prevent effectively that the laminated | multilayer film 100 is oxidized and deteriorated with antioxidant, maintaining said effect.

  Further, in the present embodiment, as a result of intensive studies by the inventors of the present application, in the laminated film 100, by containing an antioxidant in the oxygen absorbing layer 150 in a weight ratio of 5 ppm to 60 ppm with respect to the oxygen absorbing layer 150, It becomes clear that the oxygen absorption amount of the laminated film 100 on the third and seventh days after starting storage in the sealed state is increased, and the deterioration of the appearance of the laminated film 100 and the deterioration due to oxidation are suppressed. It was.

  In the present embodiment, as a result of intensive studies by the inventors of the present application, in the laminated film 100, the oxygen absorption reaction catalyst is contained in the oxygen absorption layer 150 in a weight ratio of 3000 ppm to 5000 ppm by weight with respect to the oxygen absorption layer 150. It is clear that the oxygen absorption amount of the laminated film 100 on the third and seventh days after starting storage in a sealed state is increased, and the deterioration of the appearance of the laminated film 100 and the deterioration due to oxidation are suppressed. became.

  In the present embodiment, the oxygen absorbent is made of an oxygen-absorbing resin. Unlike oxygen absorbents such as iron powder, the oxygen-absorbing resin does not color the oxygen-absorbing layer 150 in a unique hue. For this reason, the oxygen-absorbing resin can impart transparency to the oxygen-absorbing layer 150.

  In the present embodiment, the package 200 includes the laminated film 100 described above. For this reason, while the oxygen absorption amount of the package 200 increases, the fall of the external appearance of the package 200 is suppressed. Moreover, in the package 200, when the oxygen absorption layer 150 of the laminated film 100 includes an antioxidant, it is possible to effectively prevent the laminated film 100 from being oxidized and deteriorated by the antioxidant while maintaining the above-described effect. .

<Modification>
(A)
The oxygen absorbent is not an oxygen-absorbing resin, and for example, an iron powder-based oxygen absorbent mainly composed of iron powder may be used. In this case, the iron powder-based oxygen absorbent is added to a known thermoplastic resin, for example, polyolefins such as polyethylene, polypropylene, polybutadiene, and polymethylpentene, elastomers and modified products thereof, or mixed resins thereof. Used.

(B)
The laminated film 100 may include a layer that does not have a sealing function instead of the sealing layer 160. For example, the layer not having a sealing function protects the oxygen absorbing layer 150 from the direct contact between the contents contained in the package 200 and the oxygen absorbing layer 150, and adversely affects the contents. That do not affect In addition, the laminated film 100 may not include at least one of the outer layer 110, the first adhesive layer 120, the second adhesive layer 140, and the seal layer 160.

(C)
The laminated film 100 may be formed on the lid member 400 or may be formed on both the bottom member 300 and the lid member 400. In the package 200 including the lid member 400 made of the laminated film 100, the seal layer 160 of the lid member 400 is disposed so as to face the bottom member 300.

  Since the laminated film according to the present invention is excellent in oxygen absorption, it can be suitably used as a packaging material for foods, beverages, or industrial parts that hate oxidation.

100 Laminated Film 130 Barrier Layer 150 Oxygen Absorbing Layer 200 Package

Claims (7)

An oxygen absorption layer including an oxygen absorbent and an oxygen absorption reaction catalyst;
A barrier layer having gas barrier properties,
The oxygen absorption reaction catalyst is contained in a weight ratio of 100 ppm to 5000 ppm with respect to the oxygen absorption layer,
The oxygen-absorbing layer further includes an antioxidant contained in a weight ratio of 0 ppm to 170 ppm with respect to the oxygen-absorbing layer. The laminated film according to claim 1, wherein the barrier layer has an oxygen permeability of 200 ml / (m ² · 24 h · atm) or less. The oxygen absorption reaction catalyst is contained in a weight ratio of 500 ppm to 5000 ppm with respect to the oxygen absorption layer,
The laminated film according to claim 1 or 2, wherein the antioxidant is contained in a weight ratio of 0 ppm to 120 ppm with respect to the oxygen absorbing layer.   The laminated film according to claim 3, wherein the antioxidant is contained in a weight ratio of 5 ppm to 60 ppm with respect to the oxygen absorption layer.   The laminated film according to claim 4, wherein the oxygen absorption reaction catalyst is contained in a weight ratio of 3000 ppm to 5000 ppm with respect to the oxygen absorption layer.   The laminated film according to any one of claims 1 to 5, wherein the oxygen absorbent is made of an oxygen-absorbing resin.   A package comprising the laminated film according to claim 1.

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