WO2020241378A1 - 脱酸素剤組成物及びその製造方法 - Google Patents

脱酸素剤組成物及びその製造方法 Download PDF

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Publication number
WO2020241378A1
WO2020241378A1 PCT/JP2020/019772 JP2020019772W WO2020241378A1 WO 2020241378 A1 WO2020241378 A1 WO 2020241378A1 JP 2020019772 W JP2020019772 W JP 2020019772W WO 2020241378 A1 WO2020241378 A1 WO 2020241378A1
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WIPO (PCT)
Prior art keywords
oxygen scavenger
scavenger composition
iron
oxygen
layer
Prior art date
Application number
PCT/JP2020/019772
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English (en)
French (fr)
Inventor
大揮 佐藤
井上　敦
Original Assignee
三菱瓦斯化学株式会社
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Filing date
Publication date
Application filed by 三菱瓦斯化学株式会社 filed Critical 三菱瓦斯化学株式会社
Priority to CN202080035355.8A priority Critical patent/CN113811195A/zh
Priority to US17/609,921 priority patent/US20220226799A1/en
Priority to EP20815025.0A priority patent/EP3977864A4/en
Priority to KR1020217036697A priority patent/KR20220012235A/ko
Publication of WO2020241378A1 publication Critical patent/WO2020241378A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
    • B01J20/0229—Compounds of Fe
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3409—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor
    • A23L3/3418—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere, e.g. partial vacuum, comprising only CO2, N2, O2 or H2O
    • A23L3/3427—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere, e.g. partial vacuum, comprising only CO2, N2, O2 or H2O in which an absorbent is placed or used
    • A23L3/3436—Oxygen absorbent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
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    • B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
    • B65D81/26—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators
    • B65D81/266—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators for absorbing gases, e.g. oxygen absorbers or desiccants
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Definitions

  • the present invention relates to an oxygen scavenger composition and a method for producing the same, and more particularly to an iron-based oxygen scavenger composition and a method for producing the same.
  • a method using an oxygen scavenger is known as a storage technology for foods and pharmaceuticals.
  • the stored article and the oxygen scavenger are sealed in a gas barrier sealed container to absorb oxygen in the sealed container by the oxygen scavenger, and the atmosphere in the sealed container is substantially changed. It can be kept anoxic.
  • the oxygen scavenger As a function of the oxygen scavenger, it is required to be small and absorb a large amount of oxygen. In other words, an oxygen scavenger composition having a high oxygen absorption amount per unit volume is required.
  • Typical oxygen scavengers include iron-based oxygen scavengers containing iron (iron powder) as the main component and non-iron-based oxygen scavengers containing ascorbic acid, glycerin, etc. as the main components.
  • the oxygen scavenger is appropriately selected according to the application, but an iron-based oxygen scavenger is widely used from the viewpoint of oxygen absorption performance.
  • Iron powder requires water to absorb oxygen.
  • the iron powder and the water-retaining agent holding water for supplying water are contained as different powders and granules that can be separated from each other. Therefore, a gap is formed between the powder and the granules of the iron powder and the water retention agent, and the gap contributes to a decrease in the amount of oxygen absorbed per unit volume of the oxygen scavenger composition. Further, the iron powder and the water-retaining agent are likely to be aggregated and combined with each other or the water-retaining agent to form a lump.
  • the surface area of the iron powder that can be oxidized decreases, so that there is a problem that the amount of oxygen absorbed decreases as compared with the case where the iron powder and the water retention agent are uniformly dispersed and mixed.
  • Patent Document 1 contains an oxygen absorbing substance, water, and a swelling agent, and solidifies by pressure molding to eliminate gaps between powders and granules to reduce the volume and make the oxygen scavenger composition compact. The thing is disclosed.
  • the oxygen scavenger composition as described in Patent Document 1 requires a new pressure molding step as compared with the oxygen scavenger composition that can be produced only by mixing, so that the production cost increases. To do.
  • iron powder inside the powder or granular material is less likely to oxidize, there is room for improvement in the amount of oxygen absorbed per unit volume.
  • Patent Document 2 describes, for the purpose of solving the problems in the oxygen scavenger composition of Patent Document 1 and providing an oxygen scavenger composition having an excellent oxygen absorption amount per unit volume, a water retention agent, a swelling agent, and the like. It contains a powder or granular material having an ⁇ layer containing a metal salt and water, a ⁇ layer containing iron, and a ⁇ layer containing a porous carrier, and the powder or granular material is directed from the inside to the outside of the powder or granular material.
  • the oxygen scavenger composition which forms a layer structure in the order of the ⁇ layer, the ⁇ layer, and the ⁇ layer is disclosed.
  • the oxygen scavenger of Patent Document 2 is prepared by adding an aqueous solution of a metal halide metal salt while mixing a water retention agent and a swelling agent to prepare a powder or granular material which is a raw material of the ⁇ layer, and then iron is added to the powder or granular material. It is necessary to go through the manufacturing process of adding powder and adhering iron powder to the outside of the ⁇ layer ( ⁇ layer / ⁇ layer) to prepare powder or granular material, and there is a method for more efficiently producing an oxygen scavenger. It has been demanded.
  • an object to be solved by the present invention is to provide an oxygen scavenger composition having a high oxygen absorption rate at the initial stage of the iron oxidation reaction.
  • Another problem to be solved by the present invention is to provide a method for efficiently producing an oxygen scavenger composition having a high oxygen absorption rate at the initial stage of the iron oxidation reaction.
  • the present invention relates to the following oxygen scavenger composition and a method for producing the same.
  • An oxygen scavenger composition containing a mixed granule of a composition containing a water retention agent, a swelling agent, a metal salt, water and iron.
  • ⁇ 4> The oxygen scavenger composition according to any one of ⁇ 1> to ⁇ 3> above, wherein the water retention agent contains at least one selected from the group consisting of diatomaceous earth, silica and activated carbon.
  • the swelling agent contains at least one selected from the group consisting of calcium carboxymethyl cellulose, sodium carboxymethyl cellulose, calcium bentonite and sodium bentonite.
  • Oxygen scavenger composition ⁇ 6> The oxygen scavenger composition according to any one of ⁇ 1> to ⁇ 5> above, wherein the mixed granulated product is not a pressure molded product.
  • ⁇ 7> The oxygen scavenger composition according to any one of ⁇ 1> to ⁇ 6> above, wherein iron is dispersed throughout the mixed granulated product.
  • ⁇ 8> The method for producing the oxygen scavenger composition according to any one of ⁇ 1> to ⁇ 7> above, wherein a water retention agent, a swelling agent, a metal salt, water and iron are mixed at once.
  • a method for producing an oxygen scavenger composition which comprises a step of granulating.
  • An oxygen scavenger package comprising the oxygen scavenger composition according to any one of ⁇ 1> to ⁇ 7> and a breathable packaging material containing the oxygen scavenger composition.
  • the oxygen scavenger composition of the present invention has a high oxygen absorption rate at the initial stage of the iron oxidation reaction, and can absorb oxygen in a closed container in a short time. Further, according to the production method of the present invention, it is possible to efficiently produce an oxygen scavenger composition that has a high oxygen absorption rate at the initial stage of the iron oxidation reaction and absorbs oxygen in a closed container in a short time. it can.
  • the oxygen scavenger composition of the present invention includes a mixed granule of a composition containing a water retention agent, a swelling agent, a metal salt, water and iron. In the mixed granulated product of the present invention, it is preferable that iron is dispersed throughout the mixed granulated product.
  • the oxygen scavenger composition of the present invention may consist only of the mixed granules, or may have a layer containing a porous carrier on the outside of the mixed granules.
  • the present inventors have obtained mixed granulation of a composition containing a water retention agent, a swelling agent, a metal salt, water and iron, which is obtained by collectively mixing and granulating a water retention agent, a swelling agent, a metal salt, water and iron. It has been found that the oxygen scavenger composition containing a substance has a high oxygen absorption rate at the initial stage of the iron oxidation reaction and can absorb oxygen in a closed container in a short time.
  • Patent Document 2 an aqueous solution of a metal halide salt is added while mixing a water retention agent and a swelling agent to prepare a powder or granular material as a raw material for the ⁇ layer, and then iron powder is added to the powder or granular material.
  • Iron powder is attached to the outside of the ⁇ layer ( ⁇ layer / ⁇ layer) to prepare powder or granular material, and hydrophobic silica is further added to the ( ⁇ layer / ⁇ layer) powder or granular material to the outside of the ⁇ layer.
  • Granular materials are prepared by attaching hydrophobic silica ( ⁇ layer / ⁇ layer / ⁇ layer).
  • the oxygen scavenger composition described in Patent Document 2 has a practically sufficient oxygen absorption rate at the initial stage of reaction, but the oxygen scavenger composition of the present invention has a faster oxygen absorption rate at the initial stage of reaction and a short time. Can absorb oxygen in a closed container.
  • iron is dispersed throughout the granulated product by collectively mixing and granulating a water retention agent, a swelling agent, a metal salt, water and iron. Since iron and water are close to each other, the reaction amount at the initial stage of the iron oxidation reaction is large, and as a result, the oxygen absorption rate at the initial stage of the reaction is high, and oxygen in the closed container can be absorbed in a short time. It is estimated that it can be done.
  • the water-retaining agent contained in the oxygen scavenger composition of the present invention is a substance that can be impregnated with water and retained without exuding water.
  • the water-retaining agent is not particularly limited as long as it can retain water, but a generally available porous substance or superabsorbent polymer can be used.
  • the porous substance include diatomaceous earth, zeolite, sepiolite, cristobalite, porous glass, silica, activated clay, acid clay, activated carbon, vermiculite and wood powder.
  • the highly water-absorbent resin examples include polyacrylate-based resins, polysulfonate-based resins, polyacrylamide-based resins, polyvinyl alcohol-based resins, starch-based resins, cellulose-based resins, and polyarginic acid-based resins.
  • the water retention agent preferably contains at least one selected from the group consisting of diatomaceous earth, silica and activated carbon. As the above-mentioned water retention agent, one type can be used alone, or two or more types can be used in combination as required. In addition, commercially available products of these water retention agents can be easily obtained.
  • activated carbon is particularly preferable because it has a function of promoting the oxidation reaction of iron in addition to the water retention function.
  • the type of activated carbon is not particularly limited, and may be any of wood, coconut shell, coal and the like.
  • the properties of the water retention agent are not particularly limited, but from the viewpoint of handleability during production of the oxygen scavenger, a powdery material having high fluidity is preferably used, and a material having a shape close to a sphere is more preferable.
  • the average particle size of the water retention agent is preferably 10 ⁇ m or more and 1000 ⁇ m or less, and more preferably 100 ⁇ m or more and 500 ⁇ m or less, from the viewpoint of handleability during production of the oxygen scavenger.
  • the particles of the water retention agent can be used regardless of whether they are primary particles, aggregated particles, or granulated products, as long as they have a particle size in the above range.
  • the water retention agent having a particle size in the above range can be used alone, or a plurality of types having different particle sizes can be mixed and used at an arbitrary ratio.
  • the content of the water retention agent in the oxygen scavenger composition is not particularly limited, but in 100% by mass of the oxygen scavenger composition, it is preferably 10% by mass or more and 40% by mass or less, and more preferably 15% by mass or more and 30% by mass or less. Is. Further, it is preferably 20 parts by mass or more and 300 parts by mass or less, and more preferably 50 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of water. When the content of the water retention agent is within the above range, the oxygen scavenger composition can sufficiently retain water, and the amount of oxygen absorbed per unit volume of the oxygen scavenger composition can be increased.
  • the swelling agent contained in the oxygen scavenger composition of the present invention is a substance that swells with water and has a caking function for maintaining the shape of the granulated product.
  • the swelling agent is preferably used in a substantially dry state, or in a semi-swelled or swelled state in which a small amount to a required amount of water is absorbed.
  • the swelling agent is not particularly limited as long as it is a generally known swelling agent, and known swelling agents, binders, adhesives, and binders used in foods and the like can be used.
  • the inorganic swelling agent include clay minerals such as sodium bentonite, calcium bentonite, and sodium montmorillonite.
  • Organic swelling agents include organic bentonite; natural products such as defatted frozen tofu, agar, starch, dextrin, gum arabic, gelatin, casein; crystalline cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, carboxymethyl cellulose calcium, hydroxyethyl cellulose, lignin sulfonic acid, Semi-synthetic products such as hydroxyethylated starch; synthetic products such as water-insoluble polyvinyl alcohol and polyvinyl methyl ether can be mentioned.
  • One of the above-mentioned swelling agents can be used alone, and two or more of them can be used in combination if necessary. In addition, commercially available products of these swelling agents can be easily obtained.
  • Clay minerals are preferable because they are inexpensive and have excellent performance. Clay minerals are also known as inorganic soaps and have a function as a lubricant. Further, it is known that a viscous mineral swollen by water exhibits high thixotropy and also exhibits cohesiveness, which is preferable. Further, the cellulosic semi-synthetic product is preferable because it exhibits excellent swelling property. Among these, bentonites such as calcium bentonite and sodium bentonite, carboxymethyl cellulose, sodium carboxymethyl cellulose, calcium carboxymethyl cellulose and the like are preferable because they are inexpensive and have strong cohesive strength.
  • the swelling agent preferably contains at least one selected from the group consisting of calcium carboxymethyl cellulose, sodium carboxymethyl cellulose, calcium bentonite and sodium bentonite.
  • the average particle size of the swelling agent is preferably 0.001 ⁇ m or more and 10 ⁇ m or less, and more preferably 0.01 ⁇ m or more and 1.0 ⁇ m or less, from the viewpoint of suppressing the generation of dust and the caking function.
  • the content of the swelling agent in the oxygen scavenger composition is not particularly limited, but in 100% by mass of the oxygen scavenger composition, it is preferably 0.1% by mass or more and 20% by mass or less, and more preferably 1% by mass or more and 15% by mass. % Or less. Further, it is preferably 1 part by mass or more and 15 parts by mass or less, and more preferably 3 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of iron.
  • the content of the swelling agent is within the above range, it becomes easy to maintain the shape of the oxygen scavenger composition, the ratio of the water retention agent does not become too small, the amount of water supplied to iron does not decrease, and oxygen absorption occurs. The amount tends to be higher.
  • the metal salt contained in the oxygen scavenger composition of the present invention is a substance that catalyzes the oxidation reaction of iron and improves the activity of iron. Further, the metal salt plays a role of preventing water contained in the oxygen scavenger composition from evaporating and being lost from the oxygen scavenger composition.
  • the metal salt is not particularly limited, but a metal halide is preferable.
  • the metal halide any generally known metal halide can be used without particular limitation.
  • the metal in the halogenated metal is not particularly limited, and examples thereof include at least one selected from the group consisting of alkali metals, alkaline earth metals, copper, zinc, aluminum, tin, iron, cobalt and nickel. Among them, at least one selected from the group consisting of lithium, potassium, sodium, magnesium, calcium, barium and iron is more preferable.
  • the halide in the metal halide is not particularly limited, and examples thereof include chlorides, bromides, and iodides.
  • metal halide calcium chloride, sodium chloride, calcium bromide, sodium bromide, calcium iodide, and sodium iodide are preferable, and calcium chloride and sodium chloride are more preferable, from the viewpoint of handleability, safety, and the like.
  • One type of metal salt can be used alone, and two or more types can be used in combination if necessary. In addition, commercially available products of these metal salts can be easily obtained.
  • the concentration of the salt is preferably 5% by mass or more and 30% by mass or less, and more preferably 10% by mass or more and 20% by mass or less.
  • the salt concentration is 5% by mass or more, the action of catalyzing iron oxidation is suppressed from becoming small, and when the salt concentration is 30% by mass or less, the vapor pressure of water is lowered. Can be suppressed. It is possible to prevent the amount of oxygen absorption from being reduced due to insufficient supply of water to iron.
  • the content of the metal salt in the oxygen scavenger composition is not particularly limited, but in 100% by mass of the oxygen scavenger composition, it is preferably 0.5% by mass or more and 15% by mass or less, and more preferably 1% by mass or more and 10% by mass. % Or less. Further, it is preferably 0.5 parts by mass or more and 20 parts by mass or less, and more preferably 2 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of iron.
  • the oxygen scavenger composition of the present invention contains water.
  • the content of water in the oxygen scavenger composition is not particularly limited, but is preferably 10% by mass or more and 40% by mass or less, more preferably 15% by mass or more and 30% by mass or less in 100% by mass of the oxygen scavenger composition. is there. Further, from the viewpoint of oxygen absorption performance, it is preferably 20 parts by mass or more and 50 parts by mass or less, and more preferably 25 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of iron.
  • iron The shape of iron contained in the oxygen scavenger composition of the present invention is not particularly limited, but iron powder is preferable from the viewpoint of oxygen absorption performance, availability, and handling.
  • the iron powder is not particularly limited as long as the surface of iron is exposed, and reduced iron powder, electrolytic iron powder, sprayed iron powder and the like can be preferably used. Further, a crushed product such as cast iron or a cut product can also be used.
  • One type of iron powder can be used alone, and two or more types can be used in combination if necessary. In addition, commercially available products of these iron powders can be easily obtained.
  • iron powder whose surface is coated with a metal halide can also be used.
  • the iron powder coated with the metal halide can be prepared by mixing the iron powder and the aqueous solution of the metal halide and then drying to remove water.
  • the metal halide coated on the iron powder may be coated with the above-mentioned metal salt.
  • the average particle size of the iron powder is preferably 1 mm or less, more preferably 500 ⁇ m or less, still more preferably 200 ⁇ m or less from the viewpoint of improving contact with oxygen, and preferably from the viewpoint of suppressing the generation of dust. Is 1 ⁇ m or more, more preferably 10 ⁇ m or more, still more preferably 20 ⁇ m or more.
  • the particle size referred to here is the weight fraction according to the size of the mesh after vibrating for 5 minutes using a standard sieve conforming to ISO 3310-1: 2000 (equivalent to JIS Z8801-1: 2006). Indicates the particle size to be measured.
  • the specific surface area of the iron powder from the viewpoint of the oxygen-absorbing ability is preferably 0.05 m 2 / g or more, more preferably 0.1 m 2 / g or more.
  • the specific surface area of iron powder can be measured by the BET multipoint method.
  • the oxygen scavenger composition of the present invention contains iron as a main agent.
  • the content of iron in the oxygen scavenger composition is preferably 40% by mass or more and 90% by mass or less, more preferably 45% by mass or more and 80% by mass or less, and 50% by mass or more and 70% by mass with respect to the oxygen scavenger composition. % Or less is more preferable, and 50% by mass or more and 60% by mass or less is further preferable.
  • the oxygen scavenger composition of the present invention includes a mixed granule of a composition containing a water retention agent, a swelling agent, a metal salt, water and iron.
  • “granulation” means reducing the abundance ratio of fine powder as compared with the state of the raw material powder by mixing the raw material powder composed of a single or multiple components with a binder or the like. , Refers to the operation of processing into granules larger than the raw material powder.
  • a "granular material” is a powder or granular material obtained by a granulation operation, in which the abundance ratio of fine powder is reduced as compared with the state of the raw material powder, and the powder or granular material is processed into particles larger than the raw material powder.
  • the mixed granulated product in the present invention is not a pressure molded product. That is, the granulated product contained in the oxygen scavenger composition of the present invention can be easily produced at low cost simply by mixing without performing pressure molding.
  • iron is dispersed throughout the mixed granulated product.
  • an aqueous solution of a metal halide is added while mixing a water retention agent and a swelling agent to prepare a powder or granular material as a raw material for the ⁇ layer, and then iron powder is added to the powder or granular material. Since iron powder is attached to the outside of the ⁇ layer ( ⁇ layer / ⁇ layer) to prepare a powder or granular material, the iron powder is localized near the outside of the powder or granular material.
  • the method for producing the oxygen scavenger composition of the present invention is a method including a step of collectively mixing and granulating a water retention agent, a swelling agent, a metal salt, water and iron.
  • iron is dispersed throughout the granulated product.
  • the content of the mixed granulated product in the oxygen scavenger composition of the present invention is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 98% by mass or more, still more preferably substantially. It is 100% by mass.
  • the oxygen scavenger composition of the present invention may consist only of the mixed granules, or may have a layer containing a porous carrier on the outside of the mixed granules.
  • the porous carrier that can be used in the present invention is not particularly limited as long as it has a porous shape.
  • the term “porous” refers to a state in which a large number of pores that can be confirmed with an electron microscope are provided on the surface and inside.
  • the porous carrier the porous substance used for the above-mentioned water retention agent can be appropriately used, but silicas are preferable. Silicas mean those containing silicon dioxide (SiO 2 ) as a main component. By using silicas, the bulk density of the obtained powder or granular material is increased, and the amount of oxygen absorbed is increased.
  • Silicas are not particularly limited, and examples thereof include hydrophobic silica (surface treated silica), wet silica, dry silica, silica gel, diatomaceous earth, acid clay, activated clay, pearlite, kaolin, talc and bentonite.
  • hydrophobic silica surface treated silica
  • wet silica wet silica
  • dry silica silica gel
  • diatomaceous earth diatomaceous earth
  • acid clay activated clay
  • pearlite pearlite
  • kaolin kaolin
  • talc talc
  • bentonite a porous carrier
  • one type can be used alone, or two or more types can be used in combination as required.
  • these porous carriers can be easily obtained as commercial products.
  • the content of the porous carrier in the layer containing the porous carrier is preferably 30% by mass or more, more preferably 50% by mass or more. More preferably, it is 80% by mass or more.
  • the content of the porous carrier in the oxygen scavenger composition is preferably 0.1% by mass or more and 5% by mass or less, more preferably. It is 0.5% by mass or more and 3% by mass or less.
  • the content of the porous carrier is in such a range, the bulk density of the oxygen scavenger composition tends to increase, the oxygen absorption amount tends to be higher, and the fluidity of the oxygen scavenger composition is improved. Therefore, the handleability of the oxygen scavenger package at the time of manufacturing can be improved.
  • the shape of the oxygen scavenger composition of the present invention is not particularly limited, and examples thereof include a spherical shape, an elliptical shape, and a cylindrical shape, and a spherical shape is preferable because it is superior in filling property and tends to have a higher bulk density. ..
  • the average particle size of the oxygen scavenger composition of the present invention is preferably 0.3 mm or more and 5.0 mm or less, and more preferably 0.5 mm or more and 2.0 mm or less.
  • the average particle size is 0.3 mm or more, it is possible to prevent the powder or granular material contact portion of the packaging machine from adhering due to static electricity or the like during filling and packaging, and the average particle size is 5.0 mm or less. As a result, the gaps between the powders and particles become too large, and there is a tendency to suppress a decrease in the amount of oxygen absorbed per unit volume.
  • sieving may be performed using a sieve having a mesh size of 0.3 mm and 2 mm.
  • the average particle size can be measured by, for example, a commercially available laser diffraction / scattering type particle size distribution measuring device (“LA-960” manufactured by Horiba Seisakusho Co., Ltd.) or the like.
  • the bulk density of the oxygen scavenger composition of the present invention is not particularly limited, but is preferably 1.0 g / mL or more, more preferably 1.3 g / mL or more, still more preferably 1.5 g / mL or more. Is. When the bulk density is 1.0 g / mL or more, the amount of oxygen absorbed per unit volume tends to be superior. In order to obtain an oxygen scavenger composition having a bulk density in the above range, for example, a specific gravity classifier (such as "High Speed Aspirator" manufactured by Tokyo Flour Milling Machinery Co., Ltd.) is used to select the desired bulk density. Just do it.
  • the bulk density can be measured according to JIS Z8901.
  • the method for producing the oxygen scavenger composition of the present invention is not particularly limited, but a method including a step of batch mixing and granulating a water retention agent, a swelling agent, a metal salt, water and iron (the production method of the present invention) preferable.
  • a mixed granule is prepared by mixing a water retention agent, a swelling agent, a metal salt, water and iron until they are uniformly dispersed, and an oxygen scavenger composition is efficiently prepared. be able to.
  • Patent Document 2 an aqueous solution of a metal halide salt is added while mixing a water retention agent and a swelling agent to prepare a powder or granular material as a raw material for the ⁇ layer, and then iron powder is added to the powder or granular material.
  • Iron powder is attached to the outside of the ⁇ layer ( ⁇ layer / ⁇ layer) to prepare powder or granular material, and hydrophobic silica is further added to the ( ⁇ layer / ⁇ layer) powder or granular material to the outside of the ⁇ layer.
  • Hydrophobic silica is attached ( ⁇ layer / ⁇ layer / ⁇ layer) to prepare powder or granular material.
  • the oxygen scavenger composition can be produced in a one-step step of batch mixing and granulating a water retention agent, a swelling agent, a metal salt, water and iron.
  • the oxygen scavenger composition can be produced more efficiently than the method of Patent Document 2.
  • the mixed granulated product contained in the oxygen scavenger composition of the present invention can be easily produced at low cost simply by mixing without performing pressure molding.
  • the mixing device is not particularly limited, but specific examples thereof include a Nauter mixer (manufactured by Hosokawa Micron Co., Ltd.), a conical mixer (manufactured by Ohno Chemical Machinery Co., Ltd.), a vertical granulator (manufactured by Paulek Co., Ltd.), and a high-speed mixer (EarthTechnica Co., Ltd.). ) And a granulator (manufactured by Akira Kiko Co., Ltd.) can be used.
  • a Nauter mixer manufactured by Hosokawa Micron Co., Ltd.
  • a conical mixer manufactured by Ohno Chemical Machinery Co., Ltd.
  • a vertical granulator manufactured by Paulek Co., Ltd.
  • a high-speed mixer EarthTechnica Co., Ltd.
  • a granulator manufactured by Akira Kiko Co., Ltd.
  • an oxygen scavenger composition having a layer containing a porous carrier
  • surface-treated silica hydrophobic silica
  • An oxygen scavenger composition can be prepared by forming a layer containing a porous carrier in silica.
  • Iron which is the main agent of oxygen scavenger, reacts with oxygen, so the reaction with oxygen gradually proceeds even in the absence of water or metal salts. Therefore, it is preferable that the mixing is performed in an inert atmosphere (in the case of a substantially closed system, the inside of the system is usually made into a reducing atmosphere without oxygen), and heat removal measures are appropriately taken.
  • the oxygen scavenger package of the present invention includes the above-mentioned oxygen scavenger composition and a breathable packaging material containing the oxygen scavenger composition.
  • Packaging material As the packaging material, two sheets of breathable packaging material are bonded to form a bag, or one breathable packaging material and one non-breathable packaging material are bonded to form a bag.
  • An example is one in which one piece of breathable packaging material is bent and the edges excluding the bent portion are sealed to form a bag.
  • the packaging material may be a bag-shaped packaging material obtained by superimposing two breathable packaging materials and heat-sealing the four sides. 1. One piece of breathable wrapping material and one piece of non-breathable wrapping material are overlapped and four sides are heat-sealed to form a bag. One piece of breathable wrapping material is bent and the bent part is excluded. Examples include those in which the sides are heat-sealed to form a bag. Further, the packaging material may be a bag-shaped packaging material in which the breathable packaging material is formed into a tubular shape and both ends and the body of the tubular body are heat-sealed.
  • the breathable packaging material As the breathable packaging material, a packaging material that allows oxygen and carbon dioxide to permeate is selected. Among them, those having an air permeation resistance of 600 seconds or less, more preferably 90 seconds or less by the Gale type testing machine method are preferably used.
  • the air permeation resistance refers to a value measured by the method of JIS P8117 (1998). More specifically, it refers to the time required for 100 mL of air to permeate the breathable packaging material using a Gale type denso meter (manufactured by Toyo Seiki Seisakusho Co., Ltd.).
  • a plastic film having breathability is used.
  • a film such as polyethylene terephthalate, polyamide, polypropylene, or polycarbonate and a film such as polyethylene, ionomer, polybutadiene, ethylene acrylic acid copolymer, ethylene methacrylic acid copolymer, or ethylene vinyl acetate copolymer as a sealing layer are laminated and bonded.
  • Laminated film or the like can be used.
  • these laminates can also be used as a breathable packaging material.
  • breathability As a method of imparting breathability, various methods can be adopted in addition to drilling with cold needles and hot needles. When breathability is imparted by drilling, the breathability can be freely adjusted depending on the diameter, number, material, etc. of the holes to be drilled.
  • the thickness of the laminated film is preferably 50 to 300 ⁇ m, and particularly preferably 60 to 250 ⁇ m.
  • the packaging material can maintain strength and have excellent heat-sealing properties and packaging suitability as compared with the case where the thickness is out of the above range.
  • the average particle size of the oxygen scavenger composition was measured by a laser diffraction / scattering type particle size distribution measuring device (“LA-960” manufactured by Horiba Seisakusho Co., Ltd.).
  • the bulk density (unit: g / mL) of the oxygen scavenger composition was measured according to JIS Z8901.
  • Oxygen absorption amount of oxygen scavenger composition 1 g of the oxygen scavenger composition was placed in a gas barrier bag (dimensions 250 mm ⁇ 400 mm) made of nylon / polyethylene laminated film together with 3000 mL of air and sealed. After holding this gas barrier bag at 25 ° C. for 4 hours and 72 hours, the oxygen concentration in the gas barrier bag was measured, and the oxygen absorption amount (unit: mL) was calculated. The obtained oxygen absorption amount was divided by the volume (unit: mL) of the oxygen scavenger composition to calculate the oxygen absorption amount per unit volume (unit: mL / mL).
  • Example 1 1240 parts of diatomaceous soil (“CG-2U” manufactured by Isolite Industry Co., Ltd.), 1120 parts of activated charcoal (“SW50” manufactured by Futamura Chemical Co., Ltd.), 225 parts of calcium bentonite (“Neo Kunibond” manufactured by Kunimine Industry Co., Ltd.), sodium carboxylmethylcellulose (“F350HC-4" manufactured by Nippon Paper Chemicals Co., Ltd.) 20 parts, 6000 parts of sodium chloride aqueous solution and iron powder (average particle size 100 ⁇ m) in which 407 parts of sodium chloride are dissolved in 2008 parts of water, high speed mixer (Earth Co., Ltd.) It was put into "SPG20L” manufactured by Technica Co., Ltd. and mixed at 240 rpm for 3 minutes to obtain a mixed granule.
  • the composition was obtained.
  • the average particle size of the obtained oxygen scavenger composition was 0.9 mm.
  • Example 2 In Example 1, the mixed granules before the surface-treated silica was added were collected and used as the oxygen scavenger composition of Example 2.
  • Comparative Example 1 1240 parts of diatomaceous soil (“CG-2U” manufactured by Isolite Industry Co., Ltd.), 1120 parts of activated charcoal (“SW50” manufactured by Futamura Chemical Co., Ltd.), 225 parts of calcium bentonite (“Neo Kunibond” manufactured by Kunimine Industry Co., Ltd.) and sodium carboxylmethylcellulose (“F350HC-4" manufactured by Nippon Paper Chemicals Co., Ltd.) 20 parts were put into a high speed mixer (“SPG20L” manufactured by EarthTechnica Co., Ltd.) and mixed at 240 rpm for 30 seconds.
  • CG-2U diatomaceous soil
  • SW50 activated charcoal
  • F350HC-4" sodium carboxylmethylcellulose
  • an aqueous sodium chloride solution prepared by dissolving 407 parts of sodium chloride in 2008 parts of water was added over 30 seconds while mixing at 240 rpm, and further mixed for 60 seconds to obtain powder or granular material as a raw material for the ⁇ layer.
  • Comparative Example 2 In Comparative Example 1, the powder or granular material ( ⁇ layer / ⁇ layer) before the surface-treated silica was added was collected and used as the oxygen scavenger composition of Comparative Example 2.
  • Table 1 shows the bulk density of the obtained oxygen scavenger composition and the amount of oxygen absorbed per unit volume.
  • method of adding raw materials indicates a method of adding raw materials other than surface-treated silica
  • batch mixing indicates that raw materials other than surface-treated silica were mixed in a batch
  • ⁇ layer / ⁇ layer Indicates that after the surface-treated silica and the raw materials other than the iron powder were mixed to form the powder or granular material which is the raw material of the ⁇ layer, the iron powder was added to form the ⁇ layer on the outside of the ⁇ layer.
  • Example 1 and Comparative Example 1 the raw materials were compared with the oxygen scavenger compositions of Comparative Examples 1 and 2 in which the ⁇ layer was formed on the outside of the ⁇ layer. It can be seen that the oxygen scavenger compositions of Examples 1 and 2 that were mixed together had a significantly larger amount of oxygen absorbed after 4 hours, and the oxygen absorption rate at the initial stage of the oxidation reaction of iron powder was faster. That is, it can be seen that the oxygen scavenger compositions of Examples 1 and 2 can absorb oxygen in the closed container in a shorter time.
  • Example 1 and Comparative Example 1 after forming the powder or granular material which is the raw material of the ⁇ layer, iron powder is added to the outside of the ⁇ layer.
  • the bulk density and the unit volume after 72 hours were compared with the production method of the comparative example which required the two-step process of forming the ⁇ layer. It can be seen that the oxygen scavenger composition having substantially the same amount of oxygen absorption can be efficiently produced in one step.

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Abstract

保水剤、膨潤剤、金属塩、水及び鉄を含む組成物の混合造粒物を含む脱酸素剤組成物、並びに保水剤、膨潤剤、金属塩、水及び鉄を一括混合して造粒する工程を含む、脱酸素剤組成物の製造方法。

Description

脱酸素剤組成物及びその製造方法
　本発明は、脱酸素剤組成物及びその製造方法に関し、詳しくは鉄系脱酸素剤組成物及びその製造方法に関する。
　食品や医薬品等の保存技術として、脱酸素剤を用いる方法が知られている。この方法では、ガスバリア性の密封容器内に被保存物品と脱酸素剤とを封入して密封することで、密封容器内の酸素を脱酸素剤に吸収させ、密封容器内の雰囲気を実質的に無酸素状態に保つことができる。脱酸素剤の機能として、小型であり、かつ、多くの酸素を吸収することが必要とされる。言い換えれば、単位体積当たりの酸素吸収量が高い脱酸素剤組成物が必要とされる。
　代表的な脱酸素剤としては、鉄（鉄粉）を主剤とする鉄系脱酸素剤、アスコルビン酸やグリセリン等を主剤とする非鉄系脱酸素剤が挙げられる。脱酸素剤は用途に応じて適宜選択されるが、酸素吸収性能の観点からは鉄系脱酸素剤が広く使用されている。
　鉄粉は、酸素を吸収するために水分を必要とする。鉄粉と水とを含む従来の脱酸素剤では、鉄粉と、水分を供給する水を保持した保水剤とが、それぞれ分離できる異なる粉粒体として含まれる。そのため、鉄粉と保水剤との粉粒体間には隙間が生じ、その隙間が脱酸素剤組成物の単位体積当たりの酸素吸収量を低下させる一因となる。また、鉄粉と保水剤とは、鉄粉同士、あるいは、保水剤同士でそれぞれ集合し、結合して、塊になり易い。鉄粉が塊になると、酸化できる鉄粉の表面積が減少するため、鉄粉と保水剤とが均一に分散して混じり合っている場合に比べて、酸素吸収量が低下する問題がある。
　例えば特許文献１には、酸素吸収物質、水及び膨潤剤を含み、加圧成形により固形化することで粉粒体間の隙間を消失させ、体積を縮小しコンパクト化を図った脱酸素剤組成物が開示されている。しかしながら、特許文献１に記載するような脱酸素剤組成物は、混合するだけで製造できる脱酸素剤組成物に比べて、加圧成形する工程が新たに必要となるために、製造コストが増大する。また、粉粒体の内部にある鉄粉ほど酸化し難いため、単位体積当たりの酸素吸収量について改善の余地がある。
　特許文献２には、特許文献１の脱酸素剤組成物における課題を解決して単位体積当たりの酸素吸収量が優れた脱酸素剤組成物を提供することを目的として、保水剤、膨潤剤、金属塩及び水を含むα層と、鉄を含むβ層と、多孔性担体を含むγ層と、を有する粉粒体を含み、前記粉粒体は、該粉粒体の内側から外側に向かって、前記α層、前記β層、前記γ層の順に層構造を形成している脱酸素剤組成物が開示されている。
国際公開第２００７／０４６４４９号 国際公開第２０１７／１６９０１５号
　密封容器内の被保存物品の酸化を防ぐ観点からは、できるだけ短時間で密封容器内の酸素を吸収する脱酸素剤が求められている。また、特許文献２の脱酸素剤は、保水剤及び膨潤剤を混合しながらハロゲン化金属塩の水溶液を投入してα層の原料である粉粒体を調製した後に、この粉粒体に鉄粉を投入してα層の外側に鉄粉を付着させて（α層／β層）粉粒体を調製するという製造工程を経る必要があり、より効率的に脱酸素剤を製造する方法が求められている。
　したがって、本発明が解決しようとする課題は、鉄の酸化反応の反応初期の酸素吸収速度が速い脱酸素剤組成物を提供することである。また、本発明が解決しようとする別の課題は、鉄の酸化反応の反応初期の酸素吸収速度が速い脱酸素剤組成物を効率的に製造する方法を提供することである。
　本発明は、以下の脱酸素剤組成物及びその製造方法に関する。
＜１＞　保水剤、膨潤剤、金属塩、水及び鉄を含む組成物の混合造粒物を含む脱酸素剤組成物。
＜２＞　平均粒子径が０．３ｍｍ以上５．０ｍｍ以下である、上記＜１＞に記載の脱酸素剤組成物。
＜３＞　前記混合造粒物の外側に多孔性担体を含む層を有する、上記＜１＞又は＜２＞に記載の脱酸素剤組成物。
＜４＞　前記保水剤が、珪藻土、シリカ及び活性炭からなる群より選択される少なくとも１種を含有する、上記＜１＞～＜３＞のいずれか１つに記載の脱酸素剤組成物。
＜５＞　前記膨潤剤が、カルボキシメチルセルロースカルシウム、カルボキシメチルセルロースナトリウム、カルシウムベントナイト及びナトリウムベントナイトからなる群より選択される少なくとも１種を含有する、上記＜１＞～＜４＞のいずれか１つに記載の脱酸素剤組成物。
＜６＞　前記混合造粒物が加圧成形物ではない、上記＜１＞～＜５＞のいずれか１つに記載の脱酸素剤組成物。
＜７＞　前記混合造粒物中の全体に鉄が分散している、上記＜１＞～＜６＞のいずれか１つに記載の脱酸素剤組成物。
＜８＞　上記＜１＞～＜７＞のいずれか１つに記載の脱酸素剤組成物を製造する方法であって、保水剤、膨潤剤、金属塩、水及び鉄を一括混合して造粒する工程を含む、脱酸素剤組成物の製造方法。
＜９＞　上記＜１＞～＜７＞のいずれか１つに記載の脱酸素剤組成物と、該脱酸素剤組成物を収容した通気性包装材とを備える、脱酸素剤包装体。
　本発明の脱酸素剤組成物は、鉄の酸化反応の反応初期の酸素吸収速度が速く、短時間で密閉容器内の酸素を吸収することができる。また、本発明の製造方法によれば、鉄の酸化反応の反応初期の酸素吸収速度が速く、短時間で密閉容器内の酸素を吸収する脱酸素剤組成物を、効率的に製造することができる。
　以下、本発明の一実施形態について説明する。本発明の内容は以下に説明する実施形態に限定されるものではない。
　なお、本明細書において、数値の記載に関する「Ａ～Ｂ」という用語は、「Ａ以上Ｂ以下」（Ａ＜Ｂの場合）又は「Ａ以下Ｂ以上」（Ａ＞Ｂの場合）を意味する。また、本発明において、好ましい態様の組み合わせは、より好ましい態様である。
〔脱酸素剤組成物〕
　本発明の脱酸素剤組成物は、保水剤、膨潤剤、金属塩、水及び鉄を含む組成物の混合造粒物を含む。本発明における混合造粒物は、混合造粒物中の全体に鉄が分散していることが好ましい。本発明の脱酸素剤組成物は、前記混合造粒物のみからなるものでもよく、前記混合造粒物の外側に多孔性担体を含む層を有するものであってもよい。
　本発明者らは、保水剤、膨潤剤、金属塩、水及び鉄を一括混合して造粒して得られる、保水剤、膨潤剤、金属塩、水及び鉄を含む組成物の混合造粒物を含む脱酸素剤組成物が、鉄の酸化反応の反応初期の酸素吸収速度が速く、短時間で密閉容器内の酸素を吸収することができることを見出した。
　上記特許文献２では、保水剤及び膨潤剤を混合しながらハロゲン化金属塩の水溶液を投入してα層の原料である粉粒体を調製した後に、この粉粒体に鉄粉を投入してα層の外側に鉄粉を付着させて（α層／β層）粉粒体を調製し、更にこの（α層／β層）粉粒体に疎水性シリカを投入してβ層の外側に疎水性シリカを付着させて（α層／β層／γ層）粉粒体を調製している。特許文献２に記載の脱酸素剤組成物は実用的には十分な反応初期の酸素吸収速度を有するが、本発明の脱酸素剤組成物は、更に反応初期の酸素吸収速度が速く、短時間で密閉容器内の酸素を吸収することができる。
　本発明の効果が得られる詳細な機構は不明であるが、保水剤、膨潤剤、金属塩、水及び鉄を一括混合して造粒することで造粒物中の全体に鉄が分散し、鉄と水とが近接して存在するため、鉄の酸化反応の反応初期の反応量が大きく、その結果として反応初期の酸素吸収速度が速く、短時間で密閉容器内の酸素を吸収することができると推定される。
（保水剤）
　本発明の脱酸素剤組成物に含まれる保水剤は、その内部に水を含浸し、水を染み出さずに保持できる物質である。
　保水剤としては、水を保持できるものであれば特に限定されないが、一般的に入手できる多孔性物質や高吸水性樹脂を使用できる。多孔性物質としては、例えば、珪藻土、ゼオライト、セピオライト、クリストバライト、多孔質ガラス、シリカ、活性白土、酸性白土、活性炭、バーミキュライト及び木粉が挙げられる。高吸水性樹脂としては、例えば、ポリアクリル酸塩系樹脂、ポリスルホン酸塩系樹脂、ポリアクリルアミド系樹脂、ポリビニルアルコール系樹脂、澱粉系樹脂、セルロース系樹脂、及びポリアルギン酸系樹脂が挙げられる。保水剤は、珪藻土、シリカ及び活性炭からなる群より選択される少なくとも１種を含有することが好ましい。上述した保水剤は、１種を単独で用いることができ、又は必要に応じて２種以上を併用して用いることもできる。また、これらの保水剤は、市販品を容易に入手することもできる。
　上記の保水剤の中でも活性炭は、保水機能に加えて、鉄の酸化反応を促進する機能を有するため特に好ましい。活性炭の種類は特に限定されず、木質、ヤシ殻、石炭等のいずれであってもよい。
　保水剤の性状は特に限定されないが、脱酸素剤の製造時の取り扱い性の観点から流動性が高い粉体状のものが好適に用いられ、形状は球形に近いものがより好ましい。また、保水剤の平均粒子径は、脱酸素剤の製造時の取り扱い性の観点から、好ましくは１０μｍ以上１０００μｍ以下であり、より好ましくは１００μｍ以上５００μｍ以下である。保水剤の粒子は、上記範囲の粒度を有するものであれば、一次粒子、凝集粒子、造粒物の別を問わず用いることができる。上記範囲の粒度を有する保水剤は一種単独で用いることもでき、異なる粒度を有する複数種を任意の割合で混合して用いることもできる。
　脱酸素剤組成物中の保水剤の含有量は特に限定されないが、脱酸素剤組成物１００質量％において、好ましくは１０質量％以上４０質量％以下、より好ましくは１５質量％以上３０質量％以下である。また、水１００質量部に対して、好ましくは２０質量部以上３００質量部以下、より好ましくは５０質量部以上２００質量部以下である。保水剤の含有量が当該範囲内であれば、脱酸素剤組成物が水を十分に保持することができるとともに、脱酸素剤組成物の単位体積当たりの酸素吸収量を高くすることができる。
（膨潤剤）
　本発明の脱酸素剤組成物に含まれる膨潤剤は、水分により膨潤し、造粒物の形状を保持するための粘結機能を有する物質である。膨潤剤は、実質的に乾燥状態で用いるか又は少量乃至必要量の水を吸収した半膨潤あるいは膨潤した状態で用いることが好ましい。
　膨潤剤としては、一般に知られている膨潤剤であれば特に制限はなく、食品等に用いられている公知の膨潤剤、結着剤、粘着剤、及びバインダーを使用できる。
　無機膨潤剤としては、ナトリウムベントナイト、カルシウムベントナイト、ナトリウムモンモリロナイト等の粘土鉱物が挙げられる。有機膨潤剤としては、有機ベントナイト；脱脂凍豆腐、寒天、澱粉、デキストリン、アラビアゴム、ゼラチン、カゼイン等の天然物；結晶セルロース、カルボキシメチルセルロース、カルボキシメチルセルロースナトリウム、カルボキシメチルセルロースカルシウム、ヒドロキシエチルセルロース、リグニンスルホン酸、ヒドロキシエチル化澱粉等の半合成品；水不溶化したポリビニルアルコール、ポリビニルメチルエーテル等の合成品等が挙げられる。上述した膨潤剤は、１種を単独で用いることができ、必要に応じて２種以上を併用して用いることもできる。また、これらの膨潤剤は、市販品を容易に入手することもできる。
　粘土鉱物は安価で性能的にも優れているので好ましい。粘土鉱物は、無機石鹸としても知られており潤滑剤としての機能を有する。また、水によって膨潤した粘度鉱物は高いチキソトロピー性を示すことが知られており、粘結性も示すので好ましい。また、セルロース系半合成品は優れた膨潤性を示し好ましい。これらの中でも、安価でかつ粘結力が強いことから、カルシウムベントナイト、ナトリウムベントナイト等のベントナイト類及びカルボキシメチルセルロース、カルボキシメチルセルロースナトリウム、カルボキシメチルセルロースカルシウム等が好ましい。膨潤剤は、カルボキシメチルセルロースカルシウム、カルボキシメチルセルロースナトリウム、カルシウムベントナイト及びナトリウムベントナイトからなる群より選択される少なくとも１種を含有することが好ましい。
　膨潤剤の平均粒子径は、粉塵の発生を抑制する観点及び粘結機能の観点から、好ましくは０．００１μｍ以上１０μｍ以下であり、より好ましくは０．０１μｍ以上１．０μｍ以下である。
　脱酸素剤組成物中の膨潤剤の含有量は特に限定されないが、脱酸素剤組成物１００質量％において、好ましくは０．１質量％以上２０質量％以下、より好ましくは１質量％以上１５質量％以下である。また、鉄１００質量部に対して、好ましくは１質量部以上１５質量部以下、より好ましくは３質量部以上１０質量部以下である。膨潤剤の含有量が当該範囲内であれば、脱酸素剤組成物の形状を維持しやすくなるとともに、保水剤の割合が小さくなりすぎず、鉄への水分供給量が低下せず、酸素吸収量がより高くなる傾向にある。
（金属塩）
　本発明の脱酸素剤組成物に含まれる金属塩は、鉄の酸化反応に触媒的に作用し、鉄の活性を向上させる物質である。また、金属塩は、脱酸素剤組成物に含まれる水が蒸散して脱酸素剤組成物から失われるのを防止する役割を果たす。
　金属塩は特に限定されないが、ハロゲン化金属が好ましい。ハロゲン化金属としては、一般に知られているものなら特に制限なく使用することができる。
　ハロゲン化金属における金属としては特に限定されないが、例えば、アルカリ金属、アルカリ土類金属、銅、亜鉛、アルミニウム、スズ、鉄、コバルト及びニッケルからなる群から選ばれる少なくとも１種が挙げられる。中でも、リチウム、カリウム、ナトリウム、マグネシウム、カルシウム、バリウム及び鉄からなる群から選ばれる少なくとも１種がより好ましい。また、ハロゲン化金属におけるハロゲン化物としては特に限定されないが、例えば、塩化物、臭化物、及びヨウ化物が挙げられる。
　ハロゲン化金属としては、取り扱い性、安全性等の点から、塩化カルシウム、塩化ナトリウム、臭化カルシウム、臭化ナトリウム、ヨウ化カルシウム、ヨウ化ナトリウムが好ましく、塩化カルシウム及び塩化ナトリウムがより好ましい。
　金属塩は、１種を単独で用いることができ、必要に応じて２種以上を併用して用いることもできる。また、これらの金属塩は、市販品を容易に入手することもできる。
　金属塩を水溶液として原料とする場合におけるその塩の濃度は、好ましくは５質量％以上３０質量％以下であり、より好ましくは１０質量％以上２０質量％以下である。塩の濃度が５質量％以上であることにより、鉄の酸化を触媒する作用が小さくなることを抑制し、また、塩の濃度が３０質量％以下であることにより、水分の蒸気圧が低下することを抑制できる。鉄に充分な水分が供給されずに酸素吸収量が少なくなることを抑制できる。
　脱酸素剤組成物中の金属塩の含有量は特に限定されないが、脱酸素剤組成物１００質量％において、好ましくは０．５質量％以上１５質量％以下、より好ましくは１質量％以上１０質量％以下である。また、鉄１００質量部に対して、好ましくは０．５質量部以上２０質量部以下、より好ましくは２質量部以上１０質量部以下である。
（水）
　鉄系脱酸素剤が酸素吸収性能を発揮する観点から、本発明の脱酸素剤組成物は水を含む。脱酸素剤組成物中の水の含有量は特に限定されないが、脱酸素剤組成物１００質量％において、好ましくは１０質量％以上４０質量％以下、より好ましくは１５質量％以上３０質量％以下である。また、酸素吸収性能の観点から、鉄１００質量部に対して、好ましくは２０質量部以上５０質量部以下、より好ましくは２５質量部以上４０質量部以下である。
（鉄）
　本発明の脱酸素剤組成物に含まれる鉄の形状は特に限定されないが、酸素吸収性能、入手容易性及び取扱い容易性の観点から、好ましくは鉄粉である。鉄粉は、鉄の表面が露出したものであれば特に限定されるものではなく、還元鉄粉、電解鉄粉、噴霧鉄粉等を好適に用いることができる。また、鋳鉄等の粉砕物、切削品を用いることもできる。
　鉄粉は、１種を単独で用いることができ、必要に応じて２種以上を併用して用いることもできる。また、これらの鉄粉は、市販品を容易に入手することもできる。
　また、金属ハロゲン化物で表面を被覆した鉄粉も使用することができる。金属ハロゲン化物で被覆した鉄粉は、鉄粉と金属ハロゲン化物の水溶液を混合した後、乾燥して水分を除去して調製できる。鉄粉に被覆する金属ハロゲン化物は、前述した金属塩を被覆したものでもよい。
　鉄粉の平均粒子径は、酸素との接触を良好にする観点から、好ましくは１ｍｍ以下、より好ましくは５００μｍ以下、更に好ましくは２００μｍ以下であり、そして、粉塵の発生を抑制する観点から、好ましくは１μｍ以上、より好ましくは１０μｍ以上、更に好ましくは２０μｍ以上である。なお、ここで言う粒子径とは、ＩＳＯ　３３１０－１：２０００（ＪＩＳ　Ｚ８８０１－１：２００６相当）に準拠する標準篩を用いて、５分間振動させた後の篩目のサイズによる重量分率から測定される粒子径を示す。
　また、鉄粉の比表面積は、酸素吸収能の観点から、好ましくは０．０５ｍ2／ｇ以上、より好ましくは０．１ｍ2／ｇ以上である。鉄粉の比表面積は、ＢＥＴ多点法にて測定することができる。
　本発明の脱酸素剤組成物は、主剤として鉄を含む。脱酸素剤組成物中の鉄の含有量は、脱酸素剤組成物に対して４０質量％以上９０質量％以下が好ましく、４５質量％以上８０質量％以下がより好ましく、５０質量％以上７０質量％以下が更に好ましく、５０質量％以上６０質量％以下が更に好ましい。
＜混合造粒物＞
　本発明の脱酸素剤組成物は、保水剤、膨潤剤、金属塩、水及び鉄を含む組成物の混合造粒物を含む。ここで、本発明において「造粒」とは、単一もしくは多成分からなる原料粉体を、結合剤等を用いて混合することにより、原料粉体の状態と比べて微粉の存在比率を減らし、原料粉体より大きな粒状に加工する操作をいう。「造粒物」とは、造粒操作により得られた粉粒体であって、原料粉体の状態と比べて微粉の存在比率が減少し、原料粉体より大きな粒状に加工された粉粒体をいう。本発明における混合造粒物は、加圧成形物ではない。すなわち、本発明の脱酸素剤組成物に含まれる造粒物は、加圧成形を行うことなく混合するだけで、簡便に低コストで製造することができる。
　また、本発明における混合造粒物は、混合造粒物中の全体に鉄が分散していることが好ましい。上記特許文献２では、保水剤及び膨潤剤を混合しながらハロゲン化金属塩の水溶液を投入してα層の原料である粉粒体を調製した後に、この粉粒体に鉄粉を投入してα層の外側に鉄粉を付着させて（α層／β層）粉粒体を調製するため、鉄粉が粉粒体の外側付近に局在する。これに対して、後述するように、本発明の脱酸素剤組成物の製造方法は、保水剤、膨潤剤、金属塩、水及び鉄を一括混合して造粒する工程を含む方法であり、当該方法によって得られる造粒物では、造粒物中の全体に鉄が分散している。
　本発明の脱酸素剤組成物中の前記混合造粒物の含有量は、好ましくは９０質量％以上、より好ましくは９５質量％以上、更に好ましくは９８質量％以上であり、更に好ましくは実質的に１００質量％である。
（多孔性担体）
　本発明の脱酸素剤組成物は、前記混合造粒物のみからなるものでもよく、前記混合造粒物の外側に多孔性担体を含む層を有するものであってもよい。
　本発明に使用され得る多孔性担体は、多孔質の形状を有している担体であれば特に限定されない。ここで、多孔質とは、電子顕微鏡にて確認できる程度の多数の細孔を表面及び内部に有している状態をいう。多孔性担体は、上述した保水剤に用いる多孔性物質を適宜用いることができるが、シリカ類であることが好ましい。シリカ類とは、二酸化ケイ素（ＳｉＯ2）を主成分とするものを意味する。シリカ類を用いることにより、得られる粉粒体の嵩密度が増大し、酸素吸収量が高くなる。
　シリカ類としては、特に限定されないが、例えば、疎水性シリカ（表面処理シリカ）、湿式シリカ、乾式シリカ、シリカゲル、珪藻土、酸性白土、活性白土、パーライト、カオリン、タルク及びベントナイトが挙げられる。上述した多孔性担体は、１種を単独で、又は、必要に応じて２種以上を併用して用いることができる。また、これらの多孔性担体は、市販品としても容易に入手することができる。
　本発明の脱酸素剤組成物が多孔性担体を含む層を有する場合、多孔性担体を含む層中の多孔性担体の含有量は、好ましくは３０質量％以上、より好ましくは５０質量％以上、更に好ましくは８０質量％以上である。
　本発明の脱酸素剤組成物が多孔性担体を含む層を有する場合、脱酸素剤組成物中の多孔性担体の含有量は、好ましくは０．１質量％以上５質量％以下、より好ましくは０．５質量％以上３質量％以下である。多孔性担体の含有量がこのような範囲にあることにより、脱酸素剤組成物の嵩密度が増大し、酸素吸収量がより高くなる傾向にあるとともに、脱酸素剤組成物の流動性が向上して脱酸素剤包装体の製造時の取扱い性を向上させることができる。
＜脱酸素剤組成物の形状＞
　本発明の脱酸素剤組成物の形状は、特に限定されないが、例えば、球形、楕円形、及び円柱が挙げられ、充填性により優れ、嵩密度がより高くなる傾向にあることから、球形が好ましい。
　本発明の脱酸素剤組成物の平均粒子径は、好ましくは０．３ｍｍ以上５．０ｍｍ以下であり、より好ましくは０．５ｍｍ以上２．０ｍｍ以下である。上記平均粒子径が０．３ｍｍ以上であることにより、充填包装時に包装機の粉粒体接触部に静電気等で付着することを抑制し、また、上記平均粒子径が５．０ｍｍ以下であることにより、粉粒体間の隙間が大きくなりすぎて、単位体積当たりの酸素吸収量が低下することを抑制する傾向にある。平均粒子径が上記範囲にある脱酸素剤組成物を得るためには、例えば、目開き０．３ｍｍ及び２ｍｍの篩を用いて篩分けすればよい。平均粒子径は、例えば市販のレーザ回折・散乱式粒子径分布測定装置（株式会社堀場製作所製「ＬＡ－９６０」）等により測定することができる。
　本発明の脱酸素剤組成物の嵩密度は、特に限定されないが、好ましくは１．０ｇ／ｍＬ以上であり、より好ましくは１．３ｇ／ｍＬ以上であり、更に好ましくは１．５ｇ／ｍＬ以上である。嵩密度が１．０ｇ／ｍＬ以上であることにより、単位体積当たりの酸素吸収量により優れる傾向にある。嵩密度が上記範囲にある脱酸素剤組成物を得るためには、例えば、比重分級機器（株式会社東京製粉機製作所製「ハイスピードアスピレータ」等）により、目的とする嵩密度のものを選別すればよい。嵩密度は、ＪＩＳ　Ｚ８９０１に準拠して測定することができる。
〔脱酸素剤組成物の製造方法〕
　本発明の脱酸素剤組成物を製造する方法は特に限定されないが、保水剤、膨潤剤、金属塩、水及び鉄を一括混合して造粒する工程を含む方法（本発明の製造方法）が好ましい。本発明の製造方法によれば、保水剤、膨潤剤、金属塩、水及び鉄を均一に分散するまで混合することで混合造粒物を調製し、脱酸素剤組成物を効率的に調製することができる。上記特許文献２では、保水剤及び膨潤剤を混合しながらハロゲン化金属塩の水溶液を投入してα層の原料である粉粒体を調製した後に、この粉粒体に鉄粉を投入してα層の外側に鉄粉を付着させて（α層／β層）粉粒体を調製し、更にこの（α層／β層）粉粒体に疎水性シリカを投入してβ層の外側に疎水性シリカを付着させて（α層／β層／γ層）粉粒体を調製している。すなわち、α層の原料である粉粒体を調製した後に、α層の外側に鉄粉を付着させるという二段階の工程を要する。これに対し、本発明の製造方法では、保水剤、膨潤剤、金属塩、水及び鉄を一括混合して造粒するという一段階の工程で脱酸素剤組成物を製造することができるため、特許文献２の方法よりも効率的に脱酸素剤組成物を製造することができる。また、本発明の脱酸素剤組成物に含まれる混合造粒物は、加圧成形を行うことなく混合するだけで、簡便に低コストで製造することができる。
　混合装置は特に限定されないが具体例として、ナウターミキサー（ホソカワミクロン株式会社製）、コニカルミキサー（大野化学機械株式会社製）、バーチカルグラニュレータ（株式会社パウレック製）、ハイスピードミキサ（株式会社アーステクニカ製）及び造粒機（アキラ機工株式会社製）を使用することができる。
　また、多孔性担体を含む層を有する脱酸素剤組成物を製造する方法としては、前記混合造粒物に表面処理シリカ（疎水性シリカ）を投入して混合し、前記混合造粒物の外側に多孔性担体を含む層を形成して脱酸素剤組成物を調製することができる。
　脱酸素剤の主剤である鉄は酸素と反応するので、水や金属塩等がない場合にも酸素との反応は徐々に進行する。そのため、混合は、不活性雰囲気中（実質的に密閉系とする場合には、通常、系内を酸素のない還元性雰囲気にする）で行い、適宜、除熱手段を講じるのが好ましい。
［脱酸素剤包装体］
　本発明の脱酸素剤包装体は、上述した脱酸素剤組成物と、該脱酸素剤組成物を収容した通気性包装材とを備える。
（包装材）
　包装材としては、２枚の通気性包装材を貼り合わせて袋状としたものや、１枚の通気性包装材と１枚の非通気性包装材とを貼り合わせて袋状としたもの、１枚の通気性包装材を折り曲げ、折り曲げ部を除く縁部同士をシールして袋状としたものが挙げられる。
　ここで、通気性包装材及び非通気性包装材が四角形状である場合には、包装材は、２枚の通気性包装材を重ね合わせ、４辺をヒートシールして袋状としたものや、１枚の通気性包装材と１枚の非通気性包装材とを重ね合わせ、４辺をヒートシールして袋状としたもの、１枚の通気性包装材を折り曲げ、折り曲げ部を除く３辺をヒートシールして袋状としたものが挙げられる。また包装材は、通気性包装材を筒状にしてその筒状体の両端部および胴部をヒートシールして袋状としたものであってもよい。
（通気性包装材）
　通気性包装材としては、酸素と二酸化炭素を透過する包装材が選択される。なかでも、ガーレ式試験機法による透気抵抗度が６００秒以下、より好ましくは９０秒以下のものが好適に用いられる。ここで、透気抵抗度とは、ＪＩＳ　Ｐ８１１７（１９９８）の方法により測定された値を言うものとする。より具体的には、ガーレ式デンソメーター（株式会社東洋精機製作所製）を使用して１００ｍＬの空気が通気性包装材を透過するのに要した時間を言う。
　上記通気性包装材としては、紙や不織布の他、プラスチックフィルムに通気性を付与したものが用いられる。プラスチックフィルムとしては、例えば、ポリエチレンテレフタレート、ポリアミド、ポリプロピレン、ポリカーボネート等のフィルムと、シール層としてポリエチレン、アイオノマー、ポリブタジエン、エチレンアクリル酸コポリマー、エチレンメタクリル酸コポリマーまたはエチレン酢酸ビニルコポリマー等のフィルムとを積層接着した積層フィルム等が使用できる。また、これらの積層物も通気性包装材として使用することができる。
　通気性を付与する方法としては、冷針、熱針による穿孔加工の他、種々の方法が採用可能である。穿孔加工により通気性を付与する場合、通気性は、穿孔する孔の径、数、材質等により自由に調整することができる。
　また、積層フィルムの厚さは、５０～３００μｍであることが好ましく、６０～２５０μｍであることが特に好ましい。この場合、厚さが上記範囲を外れる場合に比べて、強度を保持しヒートシール性や包装適性に優れた包装材とすることができる。
　以下、実施例及び比較例を用いて本実施形態を詳しく説明するが、本実施形態は本発明の作用効果を奏する限りにおいて適宜変更することができる。なお、実施例及び比較例中の「部」は、特に明記しない場合は質量部を意味する。
（脱酸素剤組成物の平均粒子径）
　脱酸素剤組成物の平均粒子径は、レーザ回折・散乱式粒子径分布測定装置（株式会社堀場製作所製「ＬＡ－９６０」）により測定した。
（脱酸素剤組成物の嵩密度）
　脱酸素剤組成物の嵩密度（単位：ｇ／ｍＬ）は、ＪＩＳ　Ｚ８９０１に準拠して測定した。
（脱酸素剤組成物の酸素吸収量）
　脱酸素剤組成物１ｇを、空気３０００ｍＬと共に、ナイロン／ポリエチレンラミネートフィルム製のガスバリア性袋（寸法２５０ｍｍ×４００ｍｍ）に入れ、密封した。このガスバリア袋を、２５℃下で４時間及び７２時間保持した後に、ガスバリア袋内の酸素濃度を測定し、酸素吸収量（単位：ｍＬ）を算出した。得られた酸素吸収量を脱酸素剤組成物の体積（単位：ｍＬ）で除して、単位体積当たりの酸素吸収量（単位：ｍＬ／ｍＬ）を算出した。
実施例１
　珪藻土（イソライト工業株式会社製「ＣＧ－２Ｕ」）１２４０部、活性炭（フタムラ化学株式会社製「Ｓ－Ｗ５０」）１１２０部、カルシウムベントナイト（クニミネ工業株式会社製「ネオクニボンド」）２２５部、カルボキシルメチルセルロースナトリウム（日本製紙ケミカル株式会社製「Ｆ３５０ＨＣ－４」）２０部、水２００８部に塩化ナトリウム４０７部を溶かした塩化ナトリウム水溶液及び鉄粉（平均粒子径１００μｍ）６０００部を、ハイスピードミキサ（株式会社アーステクニカ製「ＳＰＧ２０Ｌ」）に投入し、２４０ｒｐｍで３分間混合して、混合造粒物を得た。
　さらに、表面処理シリカ（東ソー・シリカ株式会社製「ＳＳ－３０Ｐ」）１１０部を投入し、２４０ｒｐｍで３０秒間混合して、混合造粒物の外側に多孔性担体層が形成された脱酸素剤組成物を得た。得られた脱酸素剤組成物の平均粒子径は０．９ｍｍであった。
実施例２
　実施例１において、表面処理シリカを投入する前の混合造粒物を採取し、実施例２の脱酸素剤組成物とした。
比較例１
　珪藻土（イソライト工業株式会社製「ＣＧ－２Ｕ」）１２４０部、活性炭（フタムラ化学株式会社製「Ｓ－Ｗ５０」）１１２０部、カルシウムベントナイト（クニミネ工業株式会社製「ネオクニボンド」）２２５部及びカルボキシルメチルセルロースナトリウム（日本製紙ケミカル株式会社製「Ｆ３５０ＨＣ－４」）２０部を、ハイスピードミキサ（株式会社アーステクニカ製「ＳＰＧ２０Ｌ」）に投入し、２４０ｒｐｍで３０秒間混合した。続いて、水２００８部に塩化ナトリウム４０７部を溶かした塩化ナトリウム水溶液を２４０ｒｐｍで混合しながら３０秒間かけて投入し、更に６０秒間混合して、α層の原料である粉粒体を得た。
　次に、鉄粉（平均粒子径１００μｍ）６０００部を投入し、２４０ｒｐｍで３分間混合して、α層の原料である粉粒体の外側にβ層が形成された粉粒体（α層／β層）を得た。
　さらに、表面処理シリカ（東ソー・シリカ株式会社製「ＳＳ－３０Ｐ」）１１０部を投入し、２４０ｒｐｍで３０秒間混合して、粉粒体（α層／β層）の外側にγ層が形成された粉粒体（α層／β層／γ層）を含む脱酸素剤組成物を得た。得られた脱酸素剤組成物の平均粒子径は０．９ｍｍであった。
　なお、得られた脱酸素剤組成物をカッターで切断した断面についてデジタルマイクロスコープ（株式会社キーエンス製「ＶＨＸ－２０００」）により断面写真を撮影したところ、粉粒体（α層／β層／γ層）が、中心部にα層を有し、その外側にβ層を有し、更にその外側にγ層を有する構造であることを確認した。
比較例２
　比較例１において、表面処理シリカを投入する前の粉粒体（α層／β層）を採取し、比較例２の脱酸素剤組成物とした。
　得られた脱酸素剤組成物の嵩密度及び単位体積当たりの酸素吸収量を表１に示す。表１中、「原料の添加方法」は表面処理シリカ以外の原料の添加方法を示しており、「一括混合」は表面処理シリカ以外の原料を一括混合したことを示し、「α層／β層」は表面処理シリカ及び鉄粉以外の原料を混合してα層の原料である粉粒体を形成した後に、鉄粉を添加して、α層の外側にβ層を形成したことを示す。
Figure JPOXMLDOC01-appb-T000001
 　
　実施例１と比較例１との対比及び実施例２と比較例２との対比から、α層の外側にβ層を形成した比較例１及び２の脱酸素剤組成物に比べて、原料を一括混合した実施例１及び２の脱酸素剤組成物の方が４時間後の酸素吸収量が顕著に多く、鉄粉の酸化反応の反応初期の酸素吸収速度が速いことが分かる。すなわち、実施例１及び２の脱酸素剤組成物の方が短時間で密閉容器内の酸素を吸収できることが分かる。
　また、実施例１と比較例１との対比及び実施例２と比較例２との対比から、α層の原料である粉粒体を形成した後に、鉄粉を添加して、α層の外側にβ層を形成した二段階の工程を要する比較例の製造方法に比べて、表面処理シリカ以外の原料を一括混合した実施例の方法によれば、嵩密度及び７２時間後の単位体積当たりの酸素吸収量がほぼ同等である脱酸素剤組成物を一段階で効率的に製造することができることが分かる。

 

Claims (9)

  1. 　保水剤、膨潤剤、金属塩、水及び鉄を含む組成物の混合造粒物を含む脱酸素剤組成物。
  2. 　平均粒子径が０．３ｍｍ以上５．０ｍｍ以下である、請求項１に記載の脱酸素剤組成物。
  3. 　前記混合造粒物の外側に多孔性担体を含む層を有する、請求項１又は２に記載の脱酸素剤組成物。
  4. 　前記保水剤が、珪藻土、シリカ及び活性炭からなる群より選択される少なくとも１種を含有する、請求項１～３のいずれか１つに記載の脱酸素剤組成物。
  5. 　前記膨潤剤が、カルボキシメチルセルロースカルシウム、カルボキシメチルセルロースナトリウム、カルシウムベントナイト及びナトリウムベントナイトからなる群より選択される少なくとも１種を含有する、請求項１～４のいずれか１つに記載の脱酸素剤組成物。
  6. 　前記混合造粒物が加圧成形物ではない、請求項１～５のいずれか１つに記載の脱酸素剤組成物。
  7. 　前記混合造粒物中の全体に鉄が分散している、請求項１～６のいずれか１つに記載の脱酸素剤組成物。
  8. 　請求項１～７のいずれか１つに記載の脱酸素剤組成物を製造する方法であって、保水剤、膨潤剤、金属塩、水及び鉄を一括混合して造粒する工程を含む、脱酸素剤組成物の製造方法。
  9. 　請求項１～７のいずれか１つに記載の脱酸素剤組成物と、該脱酸素剤組成物を収容した通気性包装材とを備える、脱酸素剤包装体。
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