JP2008173636A - Oxygen scavenger and method for manufacturing oxygen scavenger - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oxygen scavenger and a method for manufacturing an oxygen scavenger. <P>SOLUTION: The oxygen scavenger is an oxygen scavenger that absorbs oxygen away in an atmosphere, and is configured by adding an addition element: yttrium (Y), calcium (Ca), or praseodymium (Pr) that increases the amount of oxygen absorbed by an inorganic oxide to the inorganic oxide (cerium oxide, titanium oxide, zinc oxide or the like) that has oxygen defect, and the oxygen absorbed amount is increased by the addition of each addition element. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an oxygen scavenger that absorbs and removes oxygen in an atmosphere and a method for producing the oxygen scavenger.

In recent years, in response to strong demands for food safety and quality maintenance, it has been carried out to suppress oxidative degradation of food by making the inside of a food packaging body for packaging food anaerobic.
Specifically, an oxygen scavenger that absorbs and removes oxygen in the atmosphere is placed inside the food packaging body together with the food, and residual oxygen inside the food packaging body is removed to eliminate the inside of the food packaging body. An oxygen state is performed. In addition, in an inert gas not containing oxygen, the food is packaged together with the oxygen scavenger in a food packaging body so as not to allow oxygen to enter the food packaging body, and the food packaging body includes A slight amount of oxygen that permeates and penetrates into the inside is also removed by an enclosed oxygen scavenger.

  As described above, oxygen scavengers that remove oxygen in the atmosphere include organic materials and inorganic materials. From the viewpoint of cost, iron-based oxygen scavengers are inorganic materials. Agents are mainly used. As shown in the following chemical formula (1), this iron-based oxygen scavenger removes oxygen from the atmosphere by reacting iron with oxygen in the atmosphere together with slight moisture in the atmosphere. Yes.

Fe + 1 / 2H ₂ O + 3 / 4O ₂ → FeOOH (1)

However, when the conventional iron-based oxygen scavenger as described above is used, there are the following problems.
(1) Since a little water is required for the reaction with oxygen, the performance of conventional oxygen scavengers when storing foods that dislike water such as dried foods, electronic parts, solder powder, etc. There is a problem that cannot be fully demonstrated.
(2) When checking whether foreign materials such as metals are mixed in the food packaged with a conventional oxygen scavenger along with an inert gas in the package, a metal detector is added to the iron-based oxygen scavenger. Reacts, and there is a problem that a simple examination cannot be performed.
(3) There is a problem that it is rapidly heated by a microwave such as a microwave oven and ignites.

  For this reason, oxygen absorbers using inorganic oxides such as titanium oxide instead of iron-based oxygen absorbers have been proposed (Patent Documents 1 to 5).

JP 2005-104064 A JP 2005-105194 A JP 2005-105195 A JP 2005-105199 A JP 2005-105200 A

  However, there is a problem that the oxygen absorbing ability using only an inorganic oxide such as titanium oxide is not sufficient for oxygen absorption.

  This invention makes it a subject to provide the manufacturing method of the oxygen absorber and oxygen absorber which oxygen absorption ability improved in view of the said problem.

  A first invention of the present invention for solving the above-described problem is an oxygen scavenger that absorbs and removes oxygen in an atmosphere, and an oxygen absorption amount of the inorganic oxide is reduced in an inorganic oxide having oxygen defects. An oxygen scavenger is characterized in that an increasing additive element is added.

  According to a second invention, in the first invention, the inorganic oxide is cerium oxide, and the additive element is one or more of yttrium (Y), calcium (Ca), and praseodymium (Pr). The oxygen absorber is characterized by being dissolved.

  A third invention is the oxygen scavenger according to the second invention, wherein the additive element is added in an amount of 1 to 20 mol%.

  4th invention is a manufacturing method of the oxygen scavenger of 1st invention, Comprising: The composite inorganic oxide formed by adding the additional element which increases an oxygen absorption amount to the said inorganic oxide is 1000 degreeC or more. There is a method for producing an oxygen scavenger characterized by calcining at a temperature followed by reduction calcining.

  According to a fifth aspect of the present invention, there is provided the method for producing an oxygen scavenger according to the fourth aspect of the present invention, wherein the molded body is formed by pressure molding before firing at 1000 ° C. or higher.

  According to a sixth invention, in the fourth or fifth invention, the inorganic oxide is cerium oxide, and the additive element is one or two of yttrium (Y), calcium (Ca), and praseodymium (Pr). The present invention is a method for producing an oxygen scavenger characterized by solid solution.

  A seventh aspect of the present invention is a deoxygenated package characterized in that any one of the first to third deoxygenating agents is included in a gas permeable package.

  According to an eighth aspect of the present invention, there is provided a deoxygenating functional film comprising a deoxygenating layer comprising any one of the first to third deoxidizing agents.

  According to a ninth invention, in the eighth invention, a gas barrier layer having a gas barrier property provided on the outer layer side of the deoxidation layer, and further an outer layer for protecting the gas barrier layer on the outer layer side, and the deoxygenation layer The deoxidation functional film is characterized by comprising a gas permeable layer having gas permeable properties provided on the inner layer side.

  A tenth aspect of the invention is the deoxidation functional film according to the eighth or ninth aspect of the invention, wherein an advanced gas barrier layer is provided between the gas barrier layer and the outer layer.

  An eleventh aspect of the invention is the deoxygenation functional film according to the ninth or tenth aspect of the invention, wherein a buffer layer is provided between the deoxygenation layer and the gas barrier layer.

  A twelfth aspect of the invention is a deoxygenated resin composition comprising any one of the first to third oxygen scavengers dispersed or kneaded in a resin having oxygen permeability.

  According to the present invention, since an additive element that increases the amount of oxygen absorption is added, the oxygen absorption effect is higher than that of the oxygen scavenger using only the inorganic oxide.

  Hereinafter, the present invention will be described in detail with reference to the drawings. The present invention is not limited to the embodiments and examples. In addition, constituent elements in the following embodiments and examples include those that can be easily assumed by those skilled in the art or those that are substantially the same.

The oxygen absorber according to the present embodiment is an oxygen absorber that absorbs and removes oxygen in the atmosphere, and an additive element that increases the oxygen absorption amount of the inorganic oxide is added to the inorganic oxide having oxygen defects. It has been made.
Here, the inorganic oxide in the present invention is any one of cerium oxide, titanium oxide, zinc oxide, or a mixture thereof.
In particular, it is preferable to use cerium oxide as an inorganic oxide, which has a large oxygen absorption ability alone. As an additive element added to the inorganic oxide, an element in the vicinity of the ionic radius of the inorganic oxide is preferably added, but is limited to this as long as the oxygen absorption amount is increased by the addition. is not.

Here, in this embodiment, the case where cerium oxide is used as the inorganic oxide will be described below.
The high-temperature reduction-treated cerium oxide (CeOx: where x is a positive number less than 2) having oxygen defects is oxygen deficient due to oxygen being extracted from the crystal lattice by the reduction treatment, and oxygen in the atmosphere. And the following chemical formula (2), the reaction as an oxygen scavenger is exhibited.
CeOx + ((2-X) / 2) O ₂ → CeO ₂ (2)

Furthermore, in the present invention, when adjusting the oxide with respect to cerium oxide having oxygen defects, a specific additive element is added to form a solid solution by substitution, thereby increasing the amount of oxygen absorbed significantly. I try to let them.
As this specific additive element, for example, any one of yttrium (Y), calcium (Ca) and praseodymium (Pr) or a mixture thereof is desirable.
These additive elements are added during the production of cerium oxide powder to form a composite oxide together with cerium oxide.

  Here, since oxygen scavengers are generally used in food packages, there are demands for food safety, such as titanium, zirconium, magnesium, yttrium, calcium, praseodymium, lanthanum, or strontium. Of these, when adding yttrium, calcium and praseodymium having an ionic radius slightly smaller than 1.143Å of cerium (trivalent), as shown in the examples described later Thus, the effect of enhancing the oxygen absorption amount is expressed.

  Here, the relationship between the metal element and the ion radius is shown in Table 1 and FIG.

The addition of this specific additive element increases the oxygen absorption amount as follows.
First, cerium oxide is usually 4+, but its valence changes to 3+ when it is reduced at a high temperature. With this change in valence, the ionic radius of cerium oxide expands and the crystal lattice itself expands. However, the yttrium, calcium, and praseodymium have an ionic radius smaller than that of the expanded 3+ cerium ion. By adding, expansion of the lattice can be suppressed. As a result, more oxygen defects can be retained.

  In addition, as addition amount, it is preferable to set it as 1-20 mol%. This is because if the amount is less than 1 mol%, the amount of the effect of addition is small.

  In general, when an element having no or little change in valence is added to cerium oxide, the effect of increasing the amount of oxygen absorbed is not exhibited, but the additive element (Y, Ca, Pr) having a specific ionic radius is not exhibited. This is because if the addition amount is up to about 20 mol%, the expansion suppressing function of the cerium oxide fluorite lattice is sufficiently exhibited, and as a result, the amount of oxygen absorbed can be increased.

  Here, with reference to FIG. 2, it will be described that a specific additive element forms a composite oxide by solid solution with an inorganic oxide. FIG. 2 is a graph showing the relationship between the addition amount of the additive element and the lattice constant. As shown in FIG. 1, when the amount of the additive element added increases, the additive element in the oxide forms a solid solution to form a composite oxide, but the lattice constant follows a Vegard law and is monotonically linear until the solid solution limit. Increase (may decrease). And after exceeding a predetermined inflection point, it exceeds a solid solution limit and produces | generates as a single oxide.

3 to 5 show the relationship between the additive amount and the lattice constant for each additive element.
FIG. 3 shows calcium (Ca), FIG. 4 shows praseodymium (Pr), and FIG. 5 shows yttrium (Y).
As shown in these drawings, an inflection point exists when calcium (Ca) is added in an amount of about 20 mol%, praseodymium (Pr) is about 50 mol%, and yttrium (Y) has a solid solubility limit around 60 mol%. It was confirmed. The results are shown in Table 2. Therefore, it was confirmed that if the addition amount is about 1 to 20 mol%, any element is surely in a solid solution state.

Here, the oxygen absorption performance was confirmed using calcium (Ca), praseodymium (Pr), and yttrium (Y) as additive elements. The results are shown in FIG. 6, FIG. 8 and FIG. 10 as a relationship diagram between the oxygen absorption elapsed time and the oxygen absorption amount.
As shown in FIGS. 6, 8 and 10, the relationship between the elapsed time and the amount of oxygen absorbed is assumed to be 1 mol%, 5 mol%, 10 mol%, 20 mol%, 30 mol%, 40 mol%, 50 mol%, 60 mol%. Asked.
The case of no addition is indicated by ▲.

As shown in FIGS. 6, 8, and 10, as each added amount increases to 1 mol%, 5 mol%, 10 mol%, and 20 mol%, the oxygen absorption amount gradually increases as compared to the case of no addition. It was confirmed.
On the other hand, even when added in an amount of 20 mol% or more, the function of increasing oxygen absorption was not exhibited.

Moreover, the relationship between the addition amount and the oxygen absorption amount after 96 hours is shown in FIG. 7, FIG. 9, and FIG.
As shown in FIG. 7 and FIG. 11, in the case of calcium and yttrium, it was found that the addition amount was 20 mol% and became an inflection point, and addition beyond this did not contribute to oxygen absorption. In addition, as shown in FIG. 9, in the case of praseodymium, it was found that the addition amount was 15 mol% and became an inflection point, and addition beyond this did not contribute to oxygen absorption.
In the case of calcium, it is considered that as a result of the increase in the amount of a single oxide other than the complex oxide in the solid solution state, the oxygen absorption function is inhibited. In the case of yttrium and praseodymium, it is well within the solubility limit, but it is considered that the lattice is too small beyond the effect of suppressing the expansion of the lattice.

  Such oxygen scavengers, in the case of powders, are fired at a temperature of 1400 ° C. or higher (about 1 hour) and then reduced to, for example, hydrogen or the like. It can be easily produced by reducing and firing at 1000 ° C. for 1 hour in a reactive gas stream.

On the other hand, in the case of compacts such as tablets and flakes, a compact is obtained by pressing a composite oxide powder with cerium oxide to which an additive element is added at a predetermined pressure (for example, 0.5 t / cm ² or more). After being manufactured and sintered at a temperature of 1000 ° C. or higher, for example, it can be easily manufactured by reducing and sintering at 1000 ° C. for 1 hour in a reducing gas stream such as hydrogen.

  The oxygen scavenger produced in this way is used by being sealed by a treatment such as laminating with a known oxygen scavenging package such as a porous film that can permeate oxygen sufficiently and sufficiently.

  In the oxygen scavenger according to the present embodiment, oxygen can be significantly absorbed and removed from the atmosphere by reacting with oxygen in the atmosphere as shown in the chemical formula (2).

  For this reason, in the oxygen scavenger comprising the composite oxide mainly composed of cerium oxide according to the present embodiment, (1) since it can react with oxygen without requiring any water, for example, dry food, It can be used for storage in the case of things that dislike moisture such as electronic parts and solder powder. Further, (2) since cerium oxide to which an additive is added is non-metallic, it is not detected by a metal detector, and foreign substances in food can be found using the metal detector. In addition, (3) since the microwave resistance is excellent, the oxygen scavenger composed of cerium oxide to which an additive element that increases the amount of oxygen absorption is added can prevent heating in microwave cooking. Further, (4) the addition of an additive to cerium oxide increases the oxygen absorption amount, so that the oxygen absorption amount per unit weight can be significantly increased as compared with the case of cerium oxide alone.

  Therefore, according to the present embodiment, it is possible to provide an oxygen scavenger in which the oxygen absorption amount is increased as compared with the case of cerium oxide alone which is an inorganic oxide.

Thus, according to the present embodiment, it is possible to provide a deoxidizing agent that exhibits a deoxidizing function using cerium oxide, which is an inorganic oxide, and a deoxidizing method in a sealed atmosphere.
Therefore, for example, pharmaceuticals, supplements, chemicals (for example, dyes, fragrances, lipids, enzymes, vitamins, fatty acids) or food materials that are easily oxidized, foods, precision machinery and parts thereof, semiconductor substrates, and the like can be stably stored. It becomes possible.

Moreover, as shown in FIG. 12, it is good also as a deoxidation functional film 20A. As shown in FIG. 12, the deoxygenating functional film 20A is provided with a deoxygenating layer 21 made of a deoxidizing agent in which an additive element is dissolved in the cerium oxide, and on the outer layer side of the deoxygenating layer 21, and a gas barrier. The gas barrier layer 22 having the property and the gas easily permeable layer 23 provided on the inner layer side of the deoxidized layer 21 and having the gas permeable property are provided to provide a deoxidized functional film. May be. Here, in FIG. 12, reference numeral 25 represents oxygen.
In FIG. 12, an outer layer 24 is provided outside the gas barrier layer 22 to protect the gas barrier layer 22.

  Here, as the deoxygenation layer 21, polypropylene, polybutadiene, polymethylpentene, elastomer, polyethylene terephthalate, silicon resin ethylene-vinyl acetate copolymer containing an oxygen scavenger in which an additive element is dissolved in the cerium oxide. , Polybutadiene, polyisoprene, low density polyethylene, medium density polyethylene, propylene-ethylene copolymer, propylene-ethylene random polymer, and ethylene-α olefin copolymer, etc. However, the present invention is not limited to these.

  Here, as the gas barrier layer 22, aluminum foil polyethylene terephthalate (PET) polyethylene (PE), stretched polypropylene (PP), polyvinyl alcohol, polyethylene, polyvinylidene chloride coated stretched nylon (trade name), terephthalic acid-trimethylhexamethylene Diamine condensation polymer, 2,2-bis (P-aminocyclohexyl) propane-adipic acid copolymer, ethylene-vinyl alcohol copolymer, polyvinyl chloride, nylon MXD (trade name), nylon 6 (trade name), Although what consists of single layers or multilayers, such as nylon 6,6 (brand name), can be illustrated, this invention is not limited to these.

Examples of the gas permeable layer 23 include nonwoven fabric, polyethylene terephthalate (PET), polyethylene (PE), stretched polypropylene (PP), polyvinyl alcohol, polyethylene, polyvinylidene chloride-coated stretched nylon (trade name), and low density polyethylene. Examples of such a low-density polyethylene, polypropylene, ethylene-propylene copolymer, polyethylene terephthalate, ethylene-propylene rubber, ethylene-ethyl acrylate copolymer, and the like can be exemplified by the present invention. For example, a layer made of fibers such as paper and non-woven fabric can also be used.
In addition, the gas permeable layer 23 may use the function of a sealant layer (for example, a polyolefin such as PP or PE) in combination.

  Examples of the outer layer 24 include polyethylene, polypropylene, polyethylene terephthalate (PET), and nylon (trade name), but the present invention is not limited thereto.

Moreover, as shown in the deoxidation functional film 20B of FIG. 13, a buffer layer 27 may be provided between the deoxygenation layer 21 and the gas barrier layer 22 to impart adhesiveness and buffering properties to the film. .
Further, an advanced gas barrier layer 28 may be provided between the gas barrier layer 22 and the outer layer 24 to improve the certainty of preventing the invasion of gas from the outside.

  Here, examples of the buffer layer 27 include resins having a buffering action and an adhesive action such as polyethylene and polypropylene, but the present invention is not limited thereto.

  Examples of the advanced gas barrier layer 28 include various metal foils including aluminum foil, aluminum vapor deposition films, various oxide (silica, titania, zirconia, alumina) vapor deposition films and the like. It is not limited to these.

  By using the deoxygenation functional film 20B having a six-layer structure as shown in FIG. 13, the buffering action is improved and the invasion of gas from the outside is strengthened, so that a film with higher added value can be provided.

  Further, as shown in FIG. 14, the oxygen scavenger 30 in which the additive element is dissolved in the cerium oxide, and the packaging body 31 that packages the oxygen scavenger 30 and has gas permeability. The oxygen scavenging package 32 may be configured.

  Further, as shown in FIG. 15, a deoxidizing resin composition 42 may be configured by dispersing or kneading a deoxidizing agent 40 in which an additive element is dissolved in cerium oxide in a resin layer 41.

  The material constituting the resin layer 41 may be any material that can permeate oxygen, such as low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, propylene-ethylene copolymer, ethylene-vinyl acetate. Examples thereof include olefin resins such as copolymers, blends thereof, and styrene resins such as polystyrene, styrene-butadiene copolymers, and styrene-isoprene copolymers. These resins can be used alone or as a blend.

  Hereinafter, although one Example for confirming the effect of this invention is described, this invention is not limited to this Example.

<Adjustment of raw materials>
While stirring an aqueous solution in which ammonium hydrogen carbonate, ammonia, ammonium carbonate and oxalic acid are dissolved in water, a cerium nitrate aqueous solution is added dropwise to carry out reverse neutralization, and the resulting precipitate is washed with ion-exchanged water (in this example, 2 Filtered). Thereafter, the filtrate was dried (at 300 ° C. for 2 hours) to obtain cerium oxide (CeO ₂ ) powder (average particle size: about 0.5 μm) (adjustment in the case of cerium oxide alone).

<Type of additive element>
In the process of dropping the aqueous cerium nitrate solution for producing the powder of the cerium oxide alone, titanium (Ti), iron (Fe), zirconium (Zr), magnesium (Mg), yttrium (Y), calcium (Ca) are added as additive elements. ), Praseodymium (Pr), lanthanum (La), and yttrium (Y), and each was added to a concentration of 10 mol% nitrate.

In this example, a molded body having a diameter of 20 mm was used. As the molding conditions, the composite oxide powder was used and pressed into a tablet shape under 1 t / cm ² press conditions. The compact was sintered at 1100 ° C. for 1 hour. Further, the reduction conditions were 1000 ° C. for 1 hour and 100% hydrogen gas at 400 SCCM flow. The package used was an inner bag (many pinholes) manufactured by Wonder Keep.

FIG. 16 shows the oxygen absorption ability when various elements described above are added.
As shown in FIG. 16, when yttrium (Y), calcium (Ca), and praseodymium (Pr) were added as additives, a significant increase in oxygen absorption was observed as compared to the case of cerium oxide alone. .

Moreover, the oxygen absorption amount at the time of adding 1 mol%, 5 mol%, 10 mol%, and 20 mol% about yttrium (Y), calcium (Ca), and praseodymium (Pr) as an additive element was measured.
The results are shown in FIGS.

As shown in FIGS. 17 and 19, for yttrium (Y) and praseodymium (Pr), an increase in oxygen absorption was confirmed at any addition amount compared to the case where no addition was made.
Moreover, as shown in FIG. 18, about calcium (Ca), except 1 mol%, the increase in oxygen absorption amount was confirmed compared with the case of no addition.

  From these results, it was confirmed that the oxygen absorption amount was good in the range of 1 to 20 mol%.

  As described above, the oxygen scavenger according to the present invention is obtained by adding a specific additive element to an inorganic oxide such as cerium oxide, so that the amount of oxygen absorbed is greatly increased. Suitable for removal.

It is a figure which shows the ionic radius of an additive element. FIG. 5 is a relationship diagram between the additive element addition amount and the lattice constant. FIG. 6 is a relationship diagram between an additive element (Ca) addition amount and a lattice constant. FIG. 5 is a relationship diagram between an additive element (Pr) addition amount and a lattice constant. FIG. 6 is a relationship diagram between an additive element (Y) addition amount and a lattice constant. It is a relationship figure of the elapsed time of oxygen absorption in the case of an addition element (Ca), and oxygen absorption. FIG. 7 is a relationship diagram between the addition amount and the oxygen absorption amount when 96 hours elapse in FIG. 6. It is a relationship figure of the elapsed time of oxygen absorption in the case of an addition element (Pr) and oxygen absorption amount. FIG. 9 is a relationship diagram between the addition amount and the oxygen absorption amount when 96 hours elapse in FIG. 8. It is a relationship figure of the elapsed time of oxygen absorption in the case of an addition element (Y), and oxygen absorption. FIG. 11 is a relationship diagram between the addition amount and the oxygen absorption amount when 96 hours elapse in FIG. 10. It is a schematic diagram of a deoxidation functional film. It is a schematic diagram of another deoxygenation function film. It is a schematic diagram of a deoxidation package. It is a schematic diagram of a deoxidation resin composition. It is a related figure of the elapsed time and oxygen absorption amount by addition of an additional element. It is a related figure of the elapsed time by the addition element yttrium (Y) addition, and oxygen absorption. It is a related figure of the elapsed time by the addition element calcium (Ca) addition, and oxygen absorption. It is a related figure of the elapsed time by oxygen addition of praseodymium (Pr) and oxygen absorption.

Explanation of symbols

20A, 20B Deoxygenation functional film 32 Deoxygenation package 42 Deoxygenation resin composition

Claims (12)

An oxygen scavenger that absorbs and removes oxygen in the atmosphere,
An oxygen scavenger comprising an inorganic oxide having oxygen defects added with an additive element that increases the amount of oxygen absorbed by the inorganic oxide. In claim 1,
The inorganic oxide is cerium oxide, and the additive element is a solid solution of one or more of yttrium (Y), calcium (Ca), and praseodymium (Pr). Oxygen scavenger. In claim 2,
An oxygen scavenger, wherein the additive element is added in an amount of 1 to 20 mol%. A method for producing an oxygen scavenger according to claim 1,
A method for producing an oxygen scavenger, characterized in that a composite inorganic oxide obtained by adding an additive element that increases the amount of oxygen absorption to the inorganic oxide is fired at a temperature of 1000 ° C. or higher, and then reduced and fired. In claim 4,
A method for producing an oxygen scavenger, wherein the molded body is formed by pressure forming before firing at 1000 ° C. or higher. In claim 4 or 5,
The inorganic oxide is cerium oxide, and the additive element is a solid solution of one or more of yttrium (Y), calcium (Ca), and praseodymium (Pr). A method for producing an oxygen scavenger.   A deoxygenated packaging body comprising the deoxidizing agent according to any one of claims 1 to 3 enclosed in a gas permeable packaging body.   A deoxygenating functional film comprising a deoxygenating layer comprising the deoxidizing agent according to any one of claims 1 to 3. In claim 8,
A gas barrier layer having a gas barrier property provided on the outer layer side of the deoxidation layer and an outer layer for protecting the gas barrier layer on the outer layer side;
A deoxidizing functional film comprising a gas permeable layer having gas permeable properties provided on the inner layer side of the deoxidized layer. In claim 8 or 9,
A deoxygenating functional film, wherein an advanced gas barrier layer is provided between the gas barrier layer and the outer layer. In claim 9 or 10,
A deoxidation functional film, wherein a buffer layer is provided between the deoxygenation layer and the gas barrier layer.   A deoxygenating resin composition comprising the oxygen absorbing agent according to any one of claims 1 to 3 dispersed or kneaded in a resin having oxygen permeability.

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