JP5092814B2 - Oxygen-absorbing resin composition - Google Patents

Description

  The present invention relates to an oxygen-absorbing resin composition. The oxygen-absorbing resin composition of the present invention can be used for all or part of an oxygen scavenger or an oxygen-absorbing container.

  In this specification, “deoxygenation” means that the oxygen concentration in a sealed environment is 0.1 vol% or less, and “deoxygenation agent” is for the purpose of realizing a deoxygenation state. It means things such as drugs and materials used. Further, “deoxygenating” is synonymous with “having a function as an oxygen scavenger”. Furthermore, “oxygen absorption” means that drugs, materials, and the like take up oxygen in the environment regardless of the reached oxygen concentration.

  These are stored for the purpose of preventing oxygen oxidation of various items that are easily altered or deteriorated by the influence of oxygen, such as food, beverages, pharmaceuticals, medical products, cosmetics, metal products, and electronic products, for the purpose of long-term storage. An oxygen scavenger is used to remove oxygen in the packaging container and the packaging bag. The form that was initially developed as the oxygen scavenger and is still widely used is one in which an oxygen scavenger composed of powdered or granular iron powder or ascorbic acid is packed in a breathable sachet.

  In recent years, film-like oxygen scavengers that are easier to handle, have a wide application range, and have a very low possibility of accidental eating have come to be used. Many proposals have been made on the oxygen-absorbing composition and film structure of the film-like oxygen absorber. An oxygen scavenger such as iron powder or ascorbic acid is blended into the resin and formed into a film or sheet, and a separator layer having heat-fusibility is laminated on one side and a gas barrier layer is laminated on the other side. A basic deoxidizing multilayer body is known (Patent Document 1). Moreover, the packaging film containing the layer which consists of the organic component or resin component which can be oxidized, and a transition metal catalyst is also known (patent documents 2, 3). Furthermore, in order to suppress the odor generated by oxidation of an oxygen scavenger made of organic matter, an oxygen absorbing composition containing an adsorbent such as zeolite or a layer containing a layer containing an adsorbent is laminated. It has been proposed to form a film or a deoxygenating multilayer film in which a layer containing a base as a neutralizing agent is laminated (Patent Documents 4 to 6).

  In addition, aldehyde gas removers that cause off-flavors are known to have amine compounds, hydrazide compounds, and hydrazine derivatives supported on inorganic substances, mainly for the purpose of deodorizing tobacco odors and preventing sick house syndrome. (Patent Documents 7 and 8).

  As described above, the deoxygenating multilayer film including the oxygen-absorbing layer composed of an oxidizable organic component or resin component and a metal catalyst generates an odorous organic component by oxidation of the organic component or resin component during the deoxygenation process. Have a problem to do. In particular, when a deoxygenating multilayer film is used for food packaging, even if a slight odor is generated, the scent of the food deteriorates and a serious problem occurs that the value of the food is lowered.

  As a solution to this problem, when a layer containing an odor absorber is laminated between the oxygen absorption layer and the isolation layer, the migration of odorous organic components generated from the oxygen absorption layer into the packaging container is suppressed. However, since the layer containing the odor absorbent provides resistance to oxygen permeation, the rate of removing oxygen in the packaging container is reduced. In addition, when a layer containing an odor absorber is laminated between the oxygen absorption layer and the gas barrier layer, the rate of removing oxygen in the packaging container is not affected, but the odorous organic matter generated from the oxygen absorption layer is not affected. It is not possible to sufficiently prevent the components from diffusing into the packaging container through the isolation layer. Furthermore, when an oxygen-absorbing resin composition contains an inorganic base or amino compound as an odor absorbent, the rate of removing oxygen is significantly reduced. Thus, a deoxygenating film having both a practically sufficient odor absorbing function and oxygen absorbing ability has not been found so far, and the compatibility has been a major issue.

JP 55-90535 A Japanese Patent No. 2991437 Japanese Patent No. 3183704 Japanese Patent Laid-Open No. 05-247276 Japanese Patent Laid-Open No. 06-100042 Japanese Patent No. 3306071 Japanese Patent No. 2837057 Japanese Patent Laid-Open No. 2007-204892

  An object of the present invention is to provide an oxygen-absorbing resin composition capable of suppressing the generation of odorous components generated with oxidation and capable of absorbing oxygen at a practically sufficient rate.

  As a result of advancing research on the oxygen-absorbing resin composition, the present inventors have dispersed odor-inhibiting agents containing a hydrazine derivative in the oxygen-absorbing resin composition, thereby producing an odorous organic component generated along with oxidation. The inventors have found that a resin composition capable of suppressing generation and absorbing oxygen at a practically sufficient rate can be obtained, and the present invention has been completed.

  That is, the present invention relates to an oxygen-absorbing resin composition comprising an easily oxidizable thermoplastic resin, a transition metal catalyst, and an odor absorbent, wherein the odor absorbent contains a hydrazine derivative. It is a thing.

  As the hydrazine derivative used in the present invention, an aminoguanidine derivative or a hydrazine double salt is preferable.

  The oxygen-absorbing resin composition of the present invention can further contain a photosensitizer.

  The present invention also provides a deoxygenating sheet or film comprising the above oxygen-absorbing resin composition.

  The present invention solves the problem of odor generated in the process of deoxygenation in a resin composition containing an easily oxidizable thermoplastic resin and a transition metal catalyst.

  The easily oxidizable thermoplastic resin used in the oxygen-absorbing resin composition of the present invention includes an organic polymer compound having a portion in which carbon and carbon are bonded by a double bond, and a hydrogen atom bonded to a tertiary carbon atom. An organic polymer compound having a benzyl group can be used. The carbon-carbon double bond in the organic polymer compound having a portion in which carbon and carbon are bonded by a double bond may be in the polymer main chain or in the side chain. Representative examples include 1,4-polybutadiene, 1,2-polybutadiene, 1,4-polyisoprene, 3,4-polyisoprene, styrene butadiene rubber, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer. And polymers, ethylene / methyl acrylate / cyclohexenylmethyl acrylate copolymer, and the like. Examples of the organic polymer compound having a hydrogen atom bonded to a tertiary carbon atom include polypropylene and polymethylpentene. Examples of the organic polymer compound having a benzyl group include hydrogenated styrene butadiene rubber and hydrogenated styrene isoprene rubber. Among these, an organic polymer compound having a portion in which carbon and carbon are bonded by a double bond is preferable, and 1,2-polybutadiene is more preferable.

  The transition metal catalyst is a metal compound such as a salt or oxide of a transition element metal. Manganese, iron, cobalt, nickel, and copper are suitable, and manganese, iron, and cobalt are particularly suitable because they exhibit excellent catalytic action. Examples of the metal salt of the transition element metal include a mineral salt and a fatty acid salt of the transition element metal, such as a hydrochloride, sulfate, nitrate, acetate, or higher fatty acid salt of the transition element metal. Representative examples include cobalt octylate, manganese octylate, manganese naphthenate, iron naphthenate, cobalt stearate and the like.

  A transition metal catalyst preferable from the viewpoint of ease of handling is a supported catalyst in which a salt of a transition element metal is supported on a support. Although the kind of support | carrier is not specifically limited, A zeolite, diatomaceous earth, calcium silicates, etc. can be used. In particular, an agglomerate having a size of 0.1 to 200 μm at the time of catalyst preparation and after the catalyst preparation is preferable because of easy handling. In particular, a carrier having a thickness of 10 to 100 nm when dispersed in a resin is preferable because it gives a transparent resin composition when blended in the resin. An example of such a carrier is synthetic calcium silicate. The blending ratio of the transition metal catalyst is preferably from 0.001 to 10 wt%, particularly preferably from 0.01 to 1 wt%, as the weight of metal atoms in the oxygen-absorbing resin composition, from the viewpoint of oxygen absorption performance, physical strength, and economy.

  The oxygen-absorbing resin composition of the present invention can activate oxygen absorption by adding a photosensitizer if desired. A photosensitizer is a substance that causes an oxygen absorption reaction upon photosensitization. In the present invention, photosensitizer molecules excited by light irradiation extract hydrogen from the resin to form active radicals and initiate an oxidation reaction. Representative examples of the photosensitizer include benzophenone and derivatives thereof, thiazine dyes, metal porphyrin derivatives, anthraquinone derivatives, and the like. Preferably, it is a benzophenone derivative containing a benzophenone skeleton structure. The blending ratio of the photosensitizer is preferably 0.001 to 10 wt%, particularly preferably 0.01 to 1 wt% in the oxygen-absorbing resin composition.

The odor absorbent is a compound that chemically or physically fixes an odorous component generated from an easily oxidizable thermoplastic resin. The odor absorbent used in the present invention contains a hydrazine derivative as an essential component, and is preferably used with a hydrazine derivative supported on a carrier. Although the kind of support | carrier is not specifically limited, A zeolite, diatomaceous earth, calcium silicates, etc. can be used. The amount of the hydrazine derivative supported on the carrier is preferably 0.001 to 30 mmol / g-carrier, particularly preferably 0.01 to 10 mmol / g-carrier.
The blending ratio of the odor absorbent is preferably 0.01 to 50 wt%, particularly preferably 0.1 to 10 wt% with respect to the easily oxidizable thermoplastic resin.

The hydrazine derivative is an organic substance having an N—NH ₂ group such as hydrazine or phenylhydrazine and derivatives thereof, semicarbazide, hydrazide and derivatives thereof, and the like. Specifically, hydrazine, hydrazine sulfate, hydrazine hydrochloride, aluminum hydrazine sulfate double salt, carbazic acid, formohydrazide, 1,5-diphenylcarbonohydrazide, isopropylhydrazine sulfate, tert-butylhydrazine hydrochloride, 1-aminopyrrolidine Aminoguanidine sulfate, aminoguanidine hydrochloride, aminoguanidine bicarbonate, diaminoguanidine hydrochloride, triaminoguanidine nitrate, guanidine, urea, thiourea, ethylene urea, melamine, acetohydrazide, benzohydrazide, pentanohydrazide, cyclohexanecarbohydrazide, Benzenesulfonohydrazide, thiobenzohydrazide, pentaneimide hydrazide, benzohydrazonohydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecandi Hydrazide, isophthalic acid hydrazide, propionic acid hydrazide, salicylic acid hydrazide, 3-hydroxy-2-naphthoic acid hydrazide, benzophenone hydrazone, aminopolyacrylamide, 4,4-dimethyl-1-phenyl semicarbazide, 4-amino-1,2,4 -Triazole is mentioned as a preferable example, and among these, aluminum sulfate hydrazine double salt, aminoguanidine sulfate, and aminoguanidine hydrochloride are particularly preferable.

  The aminoguanidine derivative is a hydrazine derivative represented by the following structural formula (1) having a guanidine structure or a salt thereof, and examples thereof include aminoguanidine sulfate and aminoguanidine hydrochloride.

なお、式中のＲ^１乃至Ｒ^４は任意の元素を意味する。

Incidentally, R ¹ to R ⁴ in the formula refers to any element.

  The hydrazine double salt of the present invention is a compound in which an acidic metal salt and hydrazine are chemically bonded to form a double salt. Examples of the metal of the acidic metal salt include magnesium, aluminum, and chromium, and examples of the salt include any one of sulfate, hydrochloride, and phosphate, or a mixture thereof. For example, when aluminum sulfate and hydrazine are mixed in water, a hydrazine double salt is prepared, which is called aluminum sulfate hydrazine double salt.

Hydrazine (N ₂ H ₄ ) as a compound has an odor absorbing ability, but has a boiling point as low as 113 ° C. and easily decomposes, so that it can be kneaded with a resin to obtain the oxygen-absorbing resin composition of the present invention. It's not easy. However, by preparing a hydrazine double salt, it is possible to overcome these drawbacks while maintaining the odor absorbing ability inherent in hydrazine, and therefore, it is possible to produce an odor absorbent containing a hydrazine double salt. Is a preferred embodiment.

  The odor absorbent of the present invention has a particularly remarkable effect with respect to absorption of aldehydes.

  The oxygen-absorbing resin composition of the present invention comprises an easily oxidizable thermoplastic resin containing a resin composition containing an easily oxidizable thermoplastic resin, a resin composition containing a transition metal catalyst, and an odor absorbent containing a hydrazine derivative. Can be produced by mixing in a molten state. Or it can manufacture by mixing the resin composition containing an oxidizable thermoplastic resin and a transition metal catalyst, and the oxidizable thermoplastic resin which mix | blended the odor absorbent containing a hydrazine derivative in a molten state.

  The oxygen-absorbing resin composition of the present invention can be made into a pellet-like, film-like or sheet-like oxygen absorbent by melt-kneading using an extruder for resin or the like. Moreover, it can also be set as the resin composition which the oxygen-absorbing resin composition disperse | distributed in the other thermoplastic resin by adding another thermoplastic resin and melt-kneading.

  The oxygen-absorbing resin composition of the present invention is used as an oxygen scavenger processed into pellets, films or other small pieces, or an oxygen scavenger package in a form in which it is placed in a breathable sachet. be able to. Moreover, the said small piece can be shape | molded in forms, such as a label, a card | curd, and packing, and can be used as a deoxidation body.

  Furthermore, the oxygen-absorbing resin composition of the present invention can be used as a deoxidizing packaging material in part or all of a packaging bag or packaging container as it is or by laminating with an appropriate packaging material. For example, the oxygen-absorbing resin composition of the present invention is used as a deoxygenating layer, and a thermoplastic resin having high oxygen permeability and heat fusion on one side is used as an isolation layer from the contents to be packaged. It is possible to form a film-like or sheet-like deoxygenating multilayer body by laminating and laminating a resin, metal or metal oxide having low oxygen permeability on the other side as a gas barrier layer. The thickness of the deoxidation layer contained in the deoxidation multilayer is preferably 300 μm or less, and more preferably 10 to 200 μm.

  The oxygen-absorbing resin composition of the present invention can be made transparent. Therefore, it is suitable as a packaging material having transparency. In particular, a deoxygenating multilayer body having a basic structure of polyolefin layer / oxygen-absorbing resin composition layer of the present invention / transparent gas barrier resin layer can be used as a transparent deoxygenating packaging material. Examples of the transparent gas barrier resin layer include a layer made of polyester or polyamide on which silica or alumina is vapor-deposited, nylon MXD6, ethylene-vinyl alcohol copolymer, and vinylidene chloride.

  In addition, the above oxygen-absorbing composition is mixed with at least one selected from a desiccant, an adsorbent, an antibacterial agent, and a colorant to form a composition having both an oxygen absorption function and a drying function. be able to. Moreover, it can also be set as the multilayer body containing the layer of an oxygen absorptive composition, and the layer containing 1 or more types chosen from a desiccant, an adsorbent, an antibacterial agent, and a coloring agent.

  The use of the oxygen-absorbing resin composition of the present invention is not limited, and exhibits highly practical deoxygenation performance in the field of preservation and quality maintenance of foods, beverages, pharmaceuticals, medical products, cosmetics, metal products, electronic products, etc. To do.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1
Cobalt octylate (trade name “Nikka Octix Cobalt”, manufactured by Nippon Chemical Industry Co., Ltd., cobalt content 8% by weight) is impregnated into synthetic calcium silicate (trade name “Microcell E”, manufactured by Celite Co., Ltd.) Then, the transition metal catalyst obtained by drying under reduced pressure and the photosensitizer 4-phenylbenzophenone are mixed, and these are melt-kneaded at 160 ° C. using low-density polyethylene and a biaxial kneader / extruder to obtain cobalt. A catalyst master batch comprising a resin composition having an atomic content of 1.2 wt%, a synthetic calcium silicate (average particle diameter of 2 μm) of 7.5 wt%, and a phenylbenzophenone content of 2.1 wt% was prepared.

  Oxygen guanidine sulfate aqueous solution impregnated with synthetic calcium silicate (trade name “Microcell E” manufactured by Celite Co., Ltd.) and dried to obtain an odor absorbent (aminoguanidine sulfate loading 0.6 mmol / g-carrier) ) And the above catalyst masterbatch with syndiotactic 1,2-polybutadiene (trade name “RB820”, manufactured by JSR Corporation), which is an easily oxidizable thermoplastic resin, and a weight ratio of 6:10:90 (aminoguanidine sulfate 0) 0.03 mmol / g) and melt-kneaded at 140 ° C. using a twin-screw kneading extruder to prepare an oxygen-absorbing resin composition. The produced oxygen-absorbing resin composition was formed into a single-layer film having a thickness of 80 μm by a hot press.

The oxygen absorption performance of the single layer film was evaluated. The single-layer film cut out to a size of 100 × 100 mm was irradiated with ultraviolet light with an illuminance of 6.2 mW / cm ^{2 using} a 1 kW high-pressure mercury lamp as a light source for 90 seconds (irradiation amount: 560 mJ / cm ² ), and then silica-deposited PET The mixture was sealed together with 240 mL of a mixed gas of 5 vol% oxygen and 95 vol% nitrogen and left under conditions of 25 ° C. and 60% RH, and reached an oxygen concentration of 0.1% after 42 hours. . Hereinafter, the time required for the oxygen concentration in the bag to decrease to 0.1% is referred to as deoxygenation time.

  The amount of odorous organic matter released from the single layer film was evaluated. In the above oxygen absorption performance test, the concentration of aldehydes in the bag after deoxygenation was measured with a gas detector tube for acetaldehyde (acetaldehyde 92L (for low concentration), manufactured by Gastec Co., Ltd.). The amount of aldehyde released was determined to be 1.9 μL / g. Moreover, no off-flavor was observed in the bag after deoxygenation.

(Example 2)
Odor absorbent obtained by impregnating an aqueous solution of aminoguanidine hydrochloride with synthetic calcium silicate (trade name “Microcell E” manufactured by Celite Co., Ltd.) and drying (addition amount of aminoguanidine hydrochloride 0.6 mmol / g-carrier) ) And the catalyst masterbatch of Example 1 were mixed with the easily oxidizable thermoplastic resin of Example 1 at a weight ratio of 6:10:90 (aminoguanidine hydrochloride 0.03 mmol / g). A single layer film made of an oxygen-absorbing resin composition was produced. When the oxygen absorption performance and the odorous organic matter release amount of this single layer film were evaluated in the same manner as in Example 1, the deoxygenation time was 47 h, the release amount of aldehydes was 1.6 μL / g, and no off-flavor was observed. .

(Example 3)
Odor absorbent obtained by impregnating synthetic calcium silicate (trade name “Microcell E” manufactured by Celite Co., Ltd.) with 1,3-diaminoguanidine hydrochloride aqueous solution and drying (diaminoguanidine addition amount 0.6 mmol) / G-support) and the catalyst masterbatch of Example 1 were mixed with the oxidizable thermoplastic resin of Example 1 in a weight ratio of 6:10:90 (1,3-diaminoguanidine hydrochloride 0.03 mmol / g). Then, a single layer film made of the oxygen-absorbing resin composition was produced in the same manner as in Example 1. When the oxygen absorption performance and the odorous organic matter release amount of this single layer film were evaluated in the same manner as in Example 1, the deoxygenation time was 43 h, the release amount of aldehydes was 2.1 μL / g, and no off-flavor was observed. .

Example 4
An aqueous solution (molar ratio; hydrazine: aluminum sulfate = 2: 1) in which hydrazine hydrate and aluminum sulfate are dissolved is impregnated with synthetic calcium silicate (trade name “Microcell E”, manufactured by Celite) and dried. The odor absorbent (amount of hydrazine added 3.1 mmol / g-carrier) carrying aluminum sulfate hydrazine double salt and the catalyst masterbatch of Example 1 obtained by the above process are used as the oxidizable thermoplastic resin of Example 1. And a weight ratio of 5 to 10 to 90 (hydrazine 0.15 mmol / g), and a single layer film made of an oxygen-absorbing resin composition was produced in the same manner as in Example 1. When the oxygen absorption performance and the odorous organic substance release amount of this single layer film were evaluated in the same manner as in Example 1, the deoxygenation time was 48 h, the release amount of aldehydes was 2.1 μL / g, and no off-flavor was observed. .

(Comparative Example 1)
In Example 1, a single layer film was prepared in the same manner except that the odor absorbent was not used and the catalyst masterbatch and the easily oxidizable thermoplastic resin were mixed at a weight ratio of 10:90. When the oxygen absorption performance and the amount of odorous organic matter released were evaluated in the same manner as in Example 1, the deoxygenation time was 46 h, the amount of aldehyde released was 13 μL / g, and a strong off-flavor was observed. The amount of aldehydes released was determined by measuring the concentration of aldehydes in the bag after deoxygenation using an acetaldehyde gas detector tube (acetaldehyde 92M (for medium concentration), manufactured by Gastec Co., Ltd.). Also in the following comparative examples, the same detector tube was used when determining the release amount of aldehydes.

(Comparative Example 2)
A synthetic calcium silicate (trade name “Microcell E” manufactured by Celite Co., Ltd.) impregnated with an aqueous polyallylamine solution and dried to obtain an odor absorbent (polyallylamine adhering amount 21 wt%) and the catalyst of Example 1 The master batch was mixed with the easily oxidizable thermoplastic resin of Example 1 at a weight ratio of 1.5 to 10:90, and a single layer film made of an oxygen-absorbing resin composition was produced in the same manner as in Example 1. When the oxygen absorption performance of this single layer film was evaluated in the same manner as in Example 1, the oxygen removal time was 340 h, the amount of aldehydes released was 5.5 μL / g, the oxygen absorption performance was significantly reduced, and a strange odor was observed.

(Comparative Example 3)
Impregnation with synthetic aqueous calcium silicate (trade name “Microcell E”, manufactured by Celite Co., Ltd.) and drying with an aqueous solution of urea, followed by drying with an odor absorbent (amount of urea attached: 8.2 mmol / g-carrier) The catalyst masterbatch of Example 1 was mixed with the easily oxidizable thermoplastic resin of Example 1 at a weight ratio of 3 to 10:90 (urea 0.24 mmol / g), and the oxygen-absorbing resin composition was the same as in Example 1. A monolayer film made of a product was prepared. The oxygen absorption performance of this single layer film was evaluated in the same manner as in Example 1. As a result, the deoxygenation time was 110 h, the release amount of aldehydes was 8.0 μL / g, the oxygen absorption performance was significantly reduced, and a strong off-flavor was observed. .

(Comparative Example 4)
An aqueous odor absorbent obtained by impregnating an aqueous 2-aminobenzamide solution with synthetic calcium silicate (trade name “Microcell E” manufactured by Celite Co., Ltd.) and drying (1.7 mmol / attachment amount of 2-aminobenzamide) g-support) and the catalyst masterbatch of Example 1 were mixed with the oxidizable thermoplastic resin of Example 1 in a weight ratio of 6:10:90 (2-aminobenzamide 0.10 mmol / g). In the same manner as described above, a single-layer film made of an oxygen-absorbing resin composition was produced. The oxygen absorption performance of this single layer film was evaluated in the same manner as in Example 1. As a result, the oxygen removal performance was 200 h, the amount of aldehydes released was 11 μL / g, the oxygen absorption performance was significantly reduced, and a strong odor was observed.

(Comparative Example 5)
Odor absorbent obtained by impregnating synthetic silicate aqueous solution (trade name “Microcell E”, manufactured by Celite Co., Ltd.) with nicotinic acid amide aqueous solution and drying (1.7 mmol / g− Carrier) and the catalyst masterbatch of Example 1 were mixed with the oxidizable thermoplastic resin of Example 1 at a weight ratio of 3 to 10:90 (nicotinamide 0.05 mmol / g), and the same as in Example 1 A single layer film made of an oxygen-absorbing resin composition was prepared. When the oxygen absorption performance of this single-layer film was evaluated in the same manner as in Example 1, the oxygen removal performance was 230 h, the amount of aldehydes released was 11 μL / g, the oxygen absorption performance was significantly reduced, and a strong odor was observed.

(Comparative Example 6)
An odor absorbent obtained by impregnating a synthetic calcium silicate (trade name “Microcell E”, manufactured by Celite Co., Ltd.) with an aqueous solution of isonicotinic acid amide (drying amount of isonicotinic acid amide) 1.7 mmol / g-support) and the catalyst masterbatch of Example 1 were mixed with the oxidizable thermoplastic resin of Example 1 in a weight ratio of 3 to 10 to 90 (isonicotinamide 0.05 mmol / g). In the same manner as described above, a single-layer film made of an oxygen-absorbing resin composition was produced. When the oxygen absorption performance of this single layer film was evaluated in the same manner as in Example 1, it was not deoxygenated even after 300 h or more from the start of measurement, and the oxygen absorption performance was significantly reduced.

(Comparative Example 7)
Impregnation with melamine aqueous solution in synthetic calcium silicate (trade name “Microcell E”, manufactured by Celite Co., Ltd.) and drying, followed by odor absorbent (melamine adhesion amount 1.7 mmol / g-carrier) The catalyst masterbatch of Example 1 was mixed with the oxidizable thermoplastic resin of Example 1 at a weight ratio of 3 to 10:90 (melamine 0.05 mmol / g), and the oxygen-absorbing resin composition was the same as in Example 1. A monolayer film made of a product was prepared. The oxygen absorption performance of this single-layer film was evaluated in the same manner as in Example 1. As a result, the oxygen removal performance was 210 h and the release amount of aldehydes was 11 μL / g.

(Comparative Example 8)
Commercially available aldehyde absorbent FC13P Fine (Fukudai Sangyo Co., Ltd.) and the catalyst masterbatch of Example 1 were mixed with the oxidizable thermoplastic resin of Example 1 at a weight ratio of 3 to 10:90, and the same as in Example 1. Thus, a single layer film made of the oxygen-absorbing resin composition was produced. When the oxygen absorption performance of this single-layer film was evaluated in the same manner as in Example 1, the deoxygenation time was 240 h, the amount of aldehydes released was 9.2 μL / g, the oxygen absorption performance was significantly reduced, and a strong off-flavor was observed. .

(Comparative Example 9)
Commercially available amine-based aldehyde absorbent K-FRESH ZA (Taika Co., Ltd.) and the catalyst masterbatch of Example 1 were mixed with the oxidizable thermoplastic resin of Example 1 in a weight ratio of 3 to 10:90. In the same manner as in Example 1, a single layer film made of an oxygen-absorbing resin composition was produced. When the oxygen absorption performance and the odorous organic matter release amount of this single layer film were evaluated in the same manner as in Example 1, the deoxygenation time was 62 h, the release amount of aldehydes was 13 μL / g, and a strong off-flavor was observed.

Claims (6)

Oxidizable thermoplastic resin, an oxygen-absorbing resin composition comprising a transition metal catalyst and odor absorbers, oxygen absorbing said odor absorbing agent is characterized in that it comprises an aminoguanidine derivative and / or a hydrazine double salt Resin composition. The oxygen-absorbing resin composition according to claim 1, wherein the odor absorbent further contains a carrier. The easily oxidizable thermoplastic resin is 1,4-polybutadiene, 1,2-polybutadiene, 1,4-polyisoprene, 3,4-polyisoprene, styrene-butadiene rubber, styrene-butadiene-styrene block copolymer, styrene. The oxygen-absorbing resin composition according to claim 1 or 2, which is an isoprene-styrene block copolymer, an ethylene / methyl acrylate / cyclohexenylmethyl acrylate copolymer, or a mixture thereof. The oxygen-absorbing resin composition according to any one of claims 1 to 3 , wherein the oxygen-absorbing resin composition further contains a photosensitizer. Deoxidizing sheet comprising an oxygen absorbing resin composition according to any one of claims 1-4. Oxygen of a film comprising an oxygen absorbing resin composition according to any one of claims 1-4.