Classifications

• • 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
  • B01D—SEPARATION
  • B01D53/00—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
  • B01D53/02—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 adsorption, e.g. preparative gas chromatography
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—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
  • 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
• • 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
• • 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
  • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
  • B01J20/046—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing halogens, e.g. halides
• • 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
  • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
  • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
  • B01J20/28004—Sorbent size or size distribution, e.g. particle size
• • 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
  • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
  • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
  • B01J20/28016—Particle form
• • 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
  • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
  • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
  • B01J20/28016—Particle form
  • B01J20/28019—Spherical, ellipsoidal or cylindrical
• • 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
  • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
  • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
  • B01J20/2805—Sorbents inside a permeable or porous casing, e.g. inside a container, bag or membrane
• • 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
  • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
  • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J20/28057—Surface area, e.g. B.E.T specific surface area
• • 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
  • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
  • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J20/28057—Surface area, e.g. B.E.T specific surface area
  • B01J20/28059—Surface area, e.g. B.E.T specific surface area being less than 100 m2/g
• • 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
  • B01J20/30—Processes for preparing, regenerating, or reactivating
• • 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
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/3092—Packing of a container, e.g. packing a cartridge or column
• • 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
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
  • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
  • B01J20/3204—Inorganic carriers, supports or substrates
• • 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
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
  • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
  • B01J20/3234—Inorganic material layers
  • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
• • 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
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
  • B01J20/3291—Characterised by the shape of the carrier, the coating or the obtained coated product
  • B01J20/3293—Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
  • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
  • 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
  • B65D81/268—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 the absorber being enclosed in a small pack, e.g. bag, included in the package
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
  • A23B2/00—Preservation of foods or foodstuffs, in general
  • A23B2/70—Preservation of foods or foodstuffs, in general by treatment with chemicals
  • A23B2/704—Preservation of foods or foodstuffs, in general by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor
  • A23B2/708—Preservation of foods or foodstuffs, in general 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
  • A23B2/712—Preservation of foods or foodstuffs, in general 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
  • A23B2/717—Oxygen absorbent
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
  • B01D2253/10—Inorganic adsorbents
  • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
  • B01D2253/1122—Metals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2255/00—Catalysts
  • B01D2255/20—Metals or compounds thereof
  • B01D2255/207—Transition metals
  • B01D2255/20738—Iron
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/10—Single element gases other than halogens
  • B01D2257/104—Oxygen

Definitions

• the present invention relates to an oxygen absorber composition, an oxygen absorber package, and a method for producing an oxygen absorber package.
• a method using an oxygen absorber is known as a preservation technique for foods, medicines, etc.
• the article to be stored and an oxygen absorber are sealed in a sealed container with gas barrier properties, and the oxygen in the container is absorbed by the oxygen absorber, thereby substantially eliminating the atmosphere inside the container.
• an oxygen scavenger In order to function as an oxygen scavenger, it is required to be small and absorb a large amount of oxygen. In other words, there is a need for an oxygen scavenger composition that has a high oxygen absorption per unit volume.
• Typical oxygen scavengers include iron-based oxygen scavengers whose main ingredient is iron (iron powder), and non-ferrous oxygen scavengers whose main ingredient is ascorbic acid, glycerin, or the like.
• the oxygen scavenger is appropriately selected depending on the application, but iron-based oxygen scavengers are widely used from the viewpoint of oxygen absorption performance. Under these circumstances, attempts have been made to downsize iron-based oxygen scavengers and improve their oxygen absorption.
• Patent Document 1 discloses an oxygen scavenger composition that includes an oxygen absorbing substance, water, and a swelling agent, and is solidified by pressure molding to eliminate gaps between particles, thereby reducing the volume and making it more compact. things are disclosed.
• Patent Document 2 discloses, for the purpose of providing an oxygen scavenger composition with an excellent oxygen absorption amount, an ⁇ layer containing a water retention agent, a swelling agent, a metal salt, and water, a ⁇ layer containing iron, a ⁇ layer containing a porous carrier, and the granular material has a layered structure in the order of the ⁇ layer, the ⁇ layer, and the ⁇ layer from the inside to the outside of the granular material.
• An oxygen scavenger composition is disclosed.
• an object of the present invention is to provide an oxygen absorber composition, an oxygen absorber package, and a method for producing an oxygen absorber package that has a high oxygen absorption rate at the initial stage of the reaction and can exhibit high oxygen absorption performance.
• the gist of the present invention is as follows.
• [1] Contains iron, metal salts and water, Content of water present on the surface of iron per unit surface area of iron [content of water present on the surface of iron (g)/ ⁇ content of iron (g) x specific surface area of iron (m 2 /g) ) ⁇ is 0.60 g/m 2 or more and 2.00 g/m 2 or less.
• [2] The oxygen scavenger composition according to [1] above, wherein at least a portion of the metal salt is present on the surface of the iron.
• [3] The oxygen scavenger composition according to [2] above, wherein the metal salt present on the surface of the iron coats the surface of the iron.
• the metal salt present on the surface of the iron is one or more selected from the group consisting of calcium chloride, sodium chloride, calcium bromide, and sodium bromide, as described in [2] or [3] above.
• oxygen scavenger composition [5] Any of [2] to [4] above, wherein the content of the metal salt present on the surface of the iron is 0.1 parts by mass or more and 5.0 parts by mass or less based on 100 parts by mass of iron.
• Step (III-1) Storing the oxygen scavenger composition (a) in the air-permeable packaging container (b1)
• Step (II-1) Place the oxygen scavenger composition (a) in the air-permeable packaging container (b1).
• step (IV-1) How the body is manufactured.
• Step (IV-1) Step [12] of further accommodating the air-permeable packaging container (b1) containing the oxygen scavenger composition (A) in a gas barrier container (b2) [12] Following the step (I) , the method for producing an oxygen absorber package according to [9] above, which comprises the following steps (III-2), (IV-2), and (II-2) in this order.
• Step (III-2) A step of storing the oxygen scavenger composition (a) and the moisture donor in the air permeable packaging container (b1)
• Step (IV-2) The oxygen scavenger composition (a) and Step (II-2) of further accommodating the breathable packaging container (b1) containing the moisture donor in a gas barrier container (b2): From the moisture donor to the oxygen scavenger composition (a). Supplying water to obtain the oxygen scavenger composition (A)
• an oxygen scavenger composition an oxygen scavenger package, and a method for producing an oxygen scavenger package that has a high oxygen absorption rate in the initial stage of the reaction and can exhibit high oxygen absorption performance.
• Embodiments of the oxygen absorber composition, the oxygen absorber package, and the method for manufacturing the oxygen absorber package according to the present invention will be described in detail below.
• the term "A to B” regarding the description of numerical values means “A or more and B or less” (in the case of A ⁇ B) or "A or less and B or more” (in the case of A>B).
• combinations of preferred embodiments are more preferred embodiments.
• the oxygen scavenger composition of the present invention contains iron, a metal salt, and water, and the content of water present on the surface of iron per unit surface area of iron [content of water present on the surface of iron (g)] / ⁇ Iron content (g) ⁇ Specific surface area of iron (m 2 /g) ⁇ ] is 0.60 g/m 2 or more and 2.00 g/m 2 or less.
• the content of water present on the surface of iron per unit surface area of iron is an index of "thickness of the water film formed on the surface of iron" If the content of water present on the surface per unit surface area of iron is within the above-mentioned predetermined range, it means that a water film having a predetermined thickness is formed on the iron surface.
• the oxygen scavenger composition of the present invention can increase the oxygen absorption rate at the initial stage of the reaction and exhibit high oxygen absorption performance.
• the reason why the oxygen scavenger composition of the present invention achieves the above effects is not clear, it is speculated as follows.
• iron-based oxygen scavengers iron reacts with water and oxygen, resulting in a rapid oxygen scavenging reaction.
• water vapor in a deoxidized environment moisture evaporated from an object to be preserved, etc.
• a water-containing carrier moisture donor, etc.
• the reaction rate of the deoxygenation reaction when the water film is thin, the amount of oxygen absorbed is small due to the lack of water on the iron surface, and it is thought that when the water is consumed and becomes extremely small, the reaction rate becomes slow. On the other hand, if the water film is too thick, the rate of deoxygenation reaction is considered to be slow due to diffusion-limiting, which lowers the dissolved oxygen concentration in the water film.
• the oxygen scavenger composition of the present invention by forming a water film with a predetermined thickness on the surface of iron in advance, the iron surface can be coated with appropriate moisture and oxygen (dissolved oxygen) from the initial stage of the oxygen scavenging reaction. ), it is thought that the reaction rate of the deoxygenation reaction and the amount of oxygen absorption can be increased, and high oxygen absorption performance can be exhibited.
• iron The form of iron contained in the oxygen scavenger composition of the present invention is not particularly limited, but from the viewpoints of oxygen absorption performance, availability, and ease of handling, iron powder is preferable.
• the iron powder is preferably one with an exposed surface of iron (zero-valent metal iron), but it may also have an extremely thin oxide film like a normal metal surface as long as it does not impede the effects of the present invention. good.
• reduced iron powder, electrolytic iron powder, atomized iron powder, etc. can be suitably used.
• crushed or cut products such as cast iron can also be used.
• One type of iron powder can be used alone, or two or more types can be used in combination as necessary. Moreover, these iron powders can be easily obtained and used as commercially available products.
• the average particle diameter (D50) of the iron powder is preferably 3000 ⁇ m or less, more preferably 1000 ⁇ m or less, even more preferably 300 ⁇ m or less, from the viewpoint of improving contact with oxygen, and from the viewpoint of suppressing dust generation. , preferably 1 ⁇ m or more, more preferably 10 ⁇ m or more, and even more preferably 20 ⁇ m or more. More specifically, the average particle diameter (D50) of the iron powder is preferably 1 ⁇ m or more and 3000 ⁇ m or less, more preferably 1 ⁇ m or more and 1000 ⁇ m or less, even more preferably 10 ⁇ m or more and 1000 ⁇ m or less, even more preferably 20 ⁇ m or more and 300 ⁇ m or less. It is.
• the iron powder having an average particle diameter within the above range can be obtained by appropriately selecting commercially available iron powder. It can also be obtained by classifying, for example, using a sieve according to the desired average particle diameter.
• the average particle size is measured as the average particle size (D50) at a cumulative frequency of 50% in the volume-based particle size distribution using, for example, a commercially available laser diffraction/scattering particle size distribution analyzer (LA-960 manufactured by Horiba, Ltd.). can do.
• the specific surface area of the iron powder is preferably 0.03 m 2 /g or more, more preferably 0.05 m 2 /g or more from the viewpoint of oxygen absorption performance, and from the viewpoint of suppressing dust generation, Preferably it is 0.20 m 2 /g or less, more preferably 0.10 m 2 /g or less, still more preferably 0.09 m 2 /g or less. More specifically, the specific surface area of the iron powder is preferably 0.03 m 2 /g or more and 0.20 m 2 /g or less, more preferably 0.03 m 2 / g or more and 0.10 m 2 /g or less, More preferably, it is 0.05 m 2 /g or more and 0.09 m 2 /g or less. Note that the specific surface area of the iron powder can be measured by the BET multipoint method. Specifically, it can be measured by the method described in Examples.
• the oxygen scavenger composition of the present invention contains iron as a main ingredient.
• the content of iron in the oxygen scavenger composition is not particularly limited, but is preferably 40% by mass or more and 98% by mass or less, more preferably 60% by mass or more and 98% by mass or less, even more preferably 80% by mass or more and 98% by mass.
• the content is more preferably 85% by mass or more and 96% by mass or less, even more preferably 85% by mass or more and 94% by mass or less.
• the metal salt contained in the oxygen scavenger composition of the present invention is a substance that acts catalytically on the oxidation reaction of iron and improves the activity of iron.
• the metal salt also plays a role in preventing water contained in the oxygen scavenger composition from being evaporated and lost from the oxygen scavenger composition.
• the oxygen scavenger composition of the present invention needs to form a water film of a predetermined thickness on the surface of iron in advance, but in order to attract moisture to the surface of iron, the deliquescence of the metal salt is necessary. used. Therefore, it is preferable that the metal salt is present at least partially, more preferably mainly, on the surface of the iron.
• the oxygen scavenger composition of the present invention may contain a water donor, as described below, and the water donor may contain a metal salt, and the metal salt is not supported on the carrier of the water donor. It is distinguished from the metal salts that exist on the surface of iron. Therefore, when the oxygen scavenger composition contains a moisture donor, a portion of the metal salt only needs to be present on the surface of the iron, and the rest may be supported on the carrier of the moisture donor.
• the metal salt is mainly present on the surface of iron
• the metal salt includes, for example, a case where a component containing a metal salt such as a moisture donor is not added to the oxygen scavenger composition, and the metal salt is substantially present on the surface of the iron. This means that all of the above is present on the iron surface.
• the metal salt present on the surface of iron coats the surface of iron.
• the method for coating the surface of iron with the metal salt is not particularly limited, but for example, as described below, after mixing iron powder and an aqueous solution containing the metal salt, drying to remove moisture, forming the iron powder This can be done by attaching a metal salt to the surface of the
• the metal salt is not particularly limited, but a metal salt having deliquescent properties is preferable.
• metal halides are preferred.
• the metal in the metal halide is not particularly limited, but includes, for example, one or more selected from the group consisting of alkali metals, alkaline earth metals, copper, zinc, aluminum, tin, iron, cobalt, and nickel. Among these, one or more selected from the group consisting of lithium, potassium, sodium, magnesium, calcium, barium, and iron is more preferable, and one or more selected from the group consisting of sodium and calcium is even more preferable.
• the halide in the metal halide is not particularly limited, but examples thereof include chloride, bromide, and iodide, and preferably one or more selected from the group consisting of chloride and bromide.
• the metal halide may be one or more selected from the group consisting of calcium chloride, sodium chloride, calcium bromide, sodium bromide, calcium iodide, and sodium iodide from the viewpoint of ease of handling and safety.
• it is one or more selected from the group consisting of calcium chloride, sodium chloride, calcium bromide, and sodium bromide.
• the metal salt present on the surface of iron is preferably one or more selected from the group consisting of calcium chloride, sodium chloride, calcium bromide, and sodium bromide.
• One type of metal salt can be used alone, or two or more types can be used in combination as necessary. Moreover, these metal salts can be easily obtained and used as commercial products.
• the content of the metal salt is not particularly limited, but is preferably 0.09% by mass or more and 10% by mass or less, more preferably 0.09% by mass or more and 5.0% by mass or less, even more preferably It is 0.10% by mass or more and 2.0% by mass or less. Further, the content of the metal salt is preferably 0.09% by mass or more and 5.0% by mass or less, more preferably 0.10% by mass or more and 2.0% by mass in the oxygen scavenger composition excluding the moisture donor. The content is more preferably 0.10% by mass or more and 1.0% by mass or less.
• the content of the metal salt is preferably 0.1 parts by mass or more and 5.0 parts by mass or less, more preferably 0.1 parts by mass or more and 2.0 parts by mass or less, and even more preferably is 0.1 parts by mass or more and 1.0 parts by mass or less, and even more preferably 0.2 parts by mass or more and 1.0 parts by mass or less.
• the content of the metal salt present on the surface of iron is preferably 0.1 parts by mass or more and 5.0 parts by mass or less, more preferably 0.1 parts by mass or more and 2.0 parts by mass or less, per 100 parts by mass of iron.
• the amount is not more than 0.1 part by mass and not more than 1.0 part by mass, even more preferably not less than 0.1 part by mass and not more than 0.5 part by mass.
• Water contained in the oxygen scavenger composition of the present invention is a necessary component for advancing the oxygen scavenging reaction.
• the oxygen scavenger composition of the present invention requires that a water film of a predetermined thickness be formed on the surface of iron in advance. It is thought to be incorporated into the metal salts present. Therefore, water is preferably present at least partially, more preferably primarily, on the surface of the iron together with the metal salt.
• “at least a portion of water is present on the surface of iron” means that a portion or all of the water contained in the oxygen scavenger composition is present on the surface of iron.
• the oxygen scavenger composition of the present invention may contain a moisture donor, as described later, and the moisture donor contains water, but since the water is supported on the carrier of the moisture donor, iron It is distinguished from water that exists on the surface of Therefore, when the oxygen scavenger composition contains a water donor, part of the water may be present on the surface of the iron, and the rest may be supported on the carrier of the water donor.
• water mainly exists on the surface of iron includes, for example, a case where a water-containing component such as a moisture donor is not added to the oxygen scavenger composition, and substantially all of the water is present on the surface of the iron. This means that it exists on the surface of iron. Further, it is more preferable that the water present on the surface of the iron coats the surface of the iron together with a metal salt.
• the oxygen absorption rate at the initial stage of the reaction can be increased and high oxygen absorption performance can be achieved.
• the thickness of the water film can be determined by the content of water present on the surface of iron per unit surface area of iron. Content of water present on the surface of iron per unit surface area of iron [content of water present on the surface of iron (g)/ ⁇ content of iron (g) x specific surface area of iron (m 2 /g) ) ⁇ ] is 0.60 g/m 2 or more and 2.00 g/m 2 or less.
• the content of water present on the iron surface per unit surface area of iron is preferably 0.70 g/m 2 or more and 2.00 g/m 2 or less, more preferably 1.10 g/m 2 or more and 2.00 g/m 2 or less. m 2 or less, more preferably 1.10 g/m 2 or more and 1.98 g/m 2 or less, even more preferably 1.50 g/m 2 or more and 1.90 g/m 2 or less.
• Content of water present on the surface of iron per unit surface area of iron is not particularly limited, but for example, (1) the method of supplying water to the iron surface and its conditions (atmospheric humidity and humidity of the moisture donor) may be appropriately selected. (2) The desired thickness can be controlled by appropriately selecting and adjusting the type and content of the metal salt present on the surface of the iron. In particular, when drawing moisture to the surface of iron, the deliquescence phenomenon of metal salts is used. For example, when controlling by humidity conditions, the higher the humidity, the greater the amount of water present on the surface of iron.
• the per-unit content [water content (g) present on the surface of iron/ ⁇ iron content (g) ⁇ specific surface area of iron (m 2 /g) ⁇ ] can be increased.
• the more the content of metal salts present on the iron surface is increased, the more the content of water present on the iron surface per unit surface area of iron [ It is considered that the existing water content (g)/ ⁇ iron content (g) x specific surface area of iron (m 2 /g) ⁇ ] can be increased.
• humidity conditions cannot often be adjusted arbitrarily, so it is more preferable to control them by the method (2) above.
• the content of water in the oxygen scavenger composition is not particularly limited, but is preferably 2.0% by mass or more and 30% by mass or less, more preferably 3.0% by mass or more and 20% by mass or less, and even more preferably The content is 4.0% by mass or more and 15% by mass or less, and even more preferably 7.0% by mass or more and 14% by mass or less.
• the content of water in the oxygen scavenger composition excluding the moisture donor is preferably 3.0% by mass or more and 20% by mass or less, more preferably 4.0% by mass or more and 15% by mass or less, and even more preferably It is 7.0% by mass or more and 14% by mass or less.
• the water content is preferably 2.0 parts by mass or more and 30 parts by mass or less, more preferably 3.0 parts by mass or more and 20 parts by mass or less, based on 100 parts by mass of iron. More preferably, it is 4.0 parts by mass or more and 19 parts by mass or less, even more preferably 7.0 parts by mass or more and 17 parts by mass or less.
• the content of water present on the surface of the iron is preferably 3.0 parts by mass or more and 20 parts by mass or less, more preferably 4.0 parts by mass or more and 19 parts by mass or less, and more preferably 4.0 parts by mass or more and 19 parts by mass or less, based on 100 parts by mass of iron.
• it is 7.0 parts by mass or more and 17 parts by mass or less, and even more preferably 8.0 parts by mass or more and 16 parts by mass or less.
• the oxygen scavenger composition of the present invention can further contain a moisture donor.
• the moisture donor is a carrier impregnated with moisture (water-containing carrier), and supplies water to iron.
• the moisture donor includes a carrier, a metal salt, and water.
• the carrier may be anything that can supply supported moisture to the iron, and in general, granular materials such as zeolite, calcined diatomaceous earth, silica gel, perlite, vermiculite, activated alumina, activated clay, activated carbon, and bentonite are preferably used. Among them, zeolite, calcined diatomaceous earth, and activated carbon are preferred.
• the metal salt the above-mentioned components can be used, but sodium chloride is preferred.
• the content of the moisture donor is not particularly limited, and may be any amount that can provide the required amount of moisture.
• the content is 15% by mass or more and 60% by mass or less, more preferably 30% by mass or more and 50% by mass or less.
• the content of the moisture donor is preferably 25 parts by mass or more and 100 parts by mass or less, more preferably 40 parts by mass or more and 60 parts by mass or less, based on 100 parts by mass of iron.
• the content of the carrier is preferably 15% by mass or more and 60% by mass or less, more preferably 30% by mass or more and 50% by mass or less in the oxygen absorber composition. % by mass or less.
• the content of the carrier is preferably 20 parts by mass or more and 150 parts by mass or less, more preferably 25 parts by mass or more and 100 parts by mass or less, and even more preferably 40 parts by mass or more and 60 parts by mass or less, per 100 parts by mass of iron. It is.
• the oxygen scavenger composition of the present invention from the viewpoint of ease of controlling the thickness of the water film and from the viewpoint of miniaturization of the oxygen scavenger package, it is preferable that moisture is supplied by external moisture absorption. In that case, the oxygen scavenger composition may be substantially free of moisture donor.
• the oxygen scavenger composition of the present invention may contain other components as necessary.
• Other components include alkaline substances, swelling agents, fluidity improvers, catalysts, odor adsorbents, thermal dispersants, and the like.
• the shape of the oxygen scavenger composition of the present invention is not particularly limited, but examples include spherical, approximately spherical, elliptical, and cylindrical shapes, which tend to have better filling properties and higher bulk density. Spherical and approximately spherical shapes are preferred, and spherical shapes are more preferred.
• the content of water present on the surface of iron per unit surface area of iron [Content of water present on the surface of iron (g)/ ⁇ Content of iron (g) x Specific surface area of iron (m 2 /g) ⁇ ] is 0.60 g/m 2 or more and 2.00 g/m 2 or less.
• Step (i) is a step of obtaining an oxygen scavenger composition (a) containing iron and a metal salt.
• an oxygen scavenger composition (a) containing iron and a metal salt it is as above.
• the metal salt is preferably present on the surface of iron, and more preferably coats the surface of iron.
• the method for obtaining such an oxygen scavenger composition (a) is not particularly limited, but for example, iron powder to which a metal salt is attached may be obtained by mixing an aqueous solution of a metal salt with iron powder and drying the mixture. .
• the concentration of the salt is preferably 1% by mass or more and 20% by mass or less, more preferably 2% by mass or more and 10% by mass or less.
• Step (ii) is to supply water to the oxygen scavenger composition (a), which contains iron, a metal salt, and water, and the content per unit surface area of iron [iron] of water present on the surface of iron.
• the water content (g)/ ⁇ iron content (g) x iron specific surface area (m 2 /g) ⁇ ] is 0.60 g/m 2 or more and 2.00 g/m 2 or less.
• This is a step of obtaining a certain oxygen scavenger composition (A). Through this step, a water film having a desired thickness can be formed on the surface of iron, and an oxygen scavenger composition that has a high oxygen absorption rate at the initial stage of the reaction and can exhibit high oxygen absorption performance can be obtained.
• the method of supplying water to the oxygen scavenger composition (a) is not particularly limited, but examples include the following methods.
• a water-containing body for example, wetted absorbent cotton, etc.
• Another example is (2) a method in which a water-containing carrier (such as a water donor) is further blended into the oxygen scavenger composition (a), and water is supplied from the water-containing carrier to the oxygen scavenger composition (a).
• a water film having a desired thickness can be formed on the surface of iron by adjusting the amount of the water-containing carrier, the water content of the water-containing carrier, and the like.
• the oxygen scavenger composition (A) obtained by this method substantially further contains a carrier in addition to iron, metal salt, and water.
• step (ii) should be performed in an inert atmosphere. It is preferable that the oxygen scavenger composition (A) obtained is stored in an inert atmosphere until it is used as an oxygen scavenger.
• the mixing device for mixing the above components is not particularly limited, but specific examples include a ribbon mixer (manufactured by Ohno Kagaku Kikai Co., Ltd.), a Nauta mixer (manufactured by Hosokawa Micron Co., Ltd.), and a conical mixer (manufactured by Ohno Kagaku Kikai Co., Ltd.) , a vertical granulator (manufactured by Powrec Co., Ltd.), an SP granulator (manufactured by Dalton Co., Ltd.), a high-speed mixer (manufactured by Earth Technica Co., Ltd.), and a granulator (manufactured by Akira Kiko Co., Ltd.) can be used.
• a ribbon mixer manufactured by Ohno Kagaku Kikai Co., Ltd.
• a Nauta mixer manufactured by Hosokawa Micron Co., Ltd.
• a conical mixer manufactured by Ohno Kagaku
• the oxygen absorber package of the present invention includes the above-described oxygen absorber composition and an air-permeable packaging container containing the oxygen absorber composition.
• the breathable packaging container is not particularly limited as long as it is a container made of a packaging material used as an oxygen absorber, but from the viewpoint of ensuring that the oxygen absorber package exhibits sufficient oxygen absorption performance, it must contain at least a breathable packaging material.
• a breathable packaging material For example, two pieces of breathable packaging material are pasted together to form a bag, one piece of breathable packaging material and one piece of non-breathable packaging material are pasted together to form a bag shape, and one piece of
• An example is a bag-shaped bag made by folding an air-permeable packaging material and sealing the edges excluding the folded portion.
• Other examples include containers in which an air-permeable packaging material is attached to the opening surface of a non-air-permeable rigid container.
• the breathable packaging container is made into a bag by overlapping two sheets of the breathable packaging material and heat-sealing the four sides.
• one sheet of breathable packaging material and one sheet of non-breathable packaging material are stacked together and heat-sealed on four sides to form a bag, one sheet of breathable packaging material is folded, and the folded part is
• One example is a bag-shaped bag that is heat-sealed on all but three sides.
• the packaging material may also be formed into a bag by making the air-permeable packaging material cylindrical and heat-sealing both ends and the body of the cylindrical body.
• the breathable packaging material As the breathable packaging material, a packaging material that is permeable to oxygen and water vapor is selected. Among these, those having an air permeability resistance measured by the Gurley tester method of 600 seconds or less, more preferably 90 seconds or less, and still more preferably 30 seconds or less are preferably used.
• the air permeability resistance refers to a value measured by the method of JIS P8117:2009. More specifically, it refers to the time required for 100 mL of air to pass through the breathable packaging material using a Gurley densometer (manufactured by Toyo Seiki Seisakusho Co., Ltd.).
• a plastic film made of breathable material can be used.
• a plastic film for example, a film such as polyethylene terephthalate, polyamide, polypropylene, polycarbonate, etc. 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.
• a laminated film etc. can be used.
• these laminates can also be used as breathable packaging materials.
• Various methods can be used to impart breathability, including perforation using cold needles and hot needles.
• the permeability can be freely adjusted by adjusting the diameter, number, material, etc. of the holes to be perforated.
• the thickness of the laminated film is preferably 50 to 300 ⁇ m, particularly preferably 60 to 250 ⁇ m.
• the packaging material can maintain strength and have excellent heat sealability and packaging suitability.
• Non-breathable packaging material packaging materials used as oxygen absorbers can be used, and packaging materials that can block moisture, alcohol, oil, and solid components of the stored items and have sealing properties are suitable.
• examples include laminates with an oxygen permeability of 0.05 to 20 mL/ m2.24 hr.atm (25°C, 50% RH), such as coextruded multilayer sheets and films made of polyethylene terephthalate or nylon. It will be done.
• the oxygen absorber package of the present invention may further include a gas barrier container that houses the air-permeable packaging container containing the oxygen absorber composition described above.
• a gas barrier container that houses the air-permeable packaging container containing the oxygen absorber composition described above.
• the gas barrier container is not particularly limited as long as it can be sealed and has substantially gas barrier properties, but from the viewpoint of blocking external ventilation, it is preferably constructed of the above-mentioned non-breathable material.
• multilayer sheets and films with laminated structures such as polyethylene terephthalate/aluminum vapor deposition/polyethylene, oriented polypropylene/polyvinyl alcohol/polyethylene, polyvinylidene chloride coated oriented nylon/polyethylene, and nylon coextruded multilayer sheets and films.
• a bag or packaging container made of a laminate having an oxygen permeability of 0.05 to 20 mL/m 2 24 hr atm (25° C., 50% RH) can be easily used.
• metal cans, glass bottles, plastic containers, etc. can also be used as gas barrier containers.
• the method for producing the oxygen absorber package is not particularly limited, but preferably includes, for example, the following steps (I) to (III). According to such a method, it is possible to obtain an oxygen scavenger package that has a high oxygen absorption rate at the initial stage of the reaction and can exhibit high oxygen absorption performance. Note that the order of steps (II) and (III) below does not matter.
• Steps (I) and (II) are the same as steps (i) and (ii) in the method for producing the oxygen scavenger composition.
• Step (III) is a step of accommodating at least one of the oxygen absorber composition (a) and the oxygen absorber composition (A) in an air-permeable packaging container (b1).
• the oxygen scavenger composition (a) and the oxygen scavenger composition (A) can be housed in an air-permeable packaging container, and the oxygen absorption rate at the initial stage of the reaction is fast and the oxygen absorption performance is high. It is possible to obtain an oxygen absorber package that can exhibit the following properties.
• the air-permeable packaging container (b1) those described above can be used.
• the air-permeable packaging container (b1) containing at least one of the oxygen absorber composition (a) and the oxygen absorber composition (A) is further transformed into a gas barrier container (b2). It is possible to block the inflow of oxygen and water vapor into the gas barrier container. Therefore, oxidation of iron can be suppressed, and the amount of moisture on the surface of iron can be appropriately controlled.
• this step is suitable when the air-permeable packaging container (b1) contains the oxygen scavenger composition (A). Since a water film has already been formed in the oxygen scavenger composition (A), the oxygen scavenging reaction gradually progresses in the presence of oxygen.
• this step is effective from the viewpoint of maintaining good oxygen absorption performance until the time of use as an oxygen scavenger.
• substantially The inside of the gas barrier container (b2) is preferably a closed system, and more preferably the inside of the system is in a reducing atmosphere free of oxygen.
• Method 1 preferably includes the following step (III-1) and step (II-1) in this order after the step (I).
• Step (III-1) Storing the oxygen scavenger composition (a) in the air-permeable packaging container (b1)
• Step (II-1) Place the oxygen scavenger composition (a) in the air-permeable packaging container (b1). Supplying water to composition (a) to obtain the oxygen scavenger composition (A)
• Step (III-1) corresponds to the above step (III) and is a step of accommodating the oxygen absorber composition (a) in an air-permeable packaging container (b1).
• Step (II-1) corresponds to the above step (II), and supplies water to the oxygen scavenger composition (a) through the air-permeable packaging container (b1) to remove the oxygen scavenger composition (a).
• This is the process of obtaining A).
• the method of supplying water to the oxygen scavenger composition (a) through the breathable packaging container (b1) is not particularly limited, but for example, the breathable packaging container containing the oxygen scavenger composition (a)
• a water-containing body for example, wetted absorbent cotton, etc.
• Step (IV-1) A step of further accommodating the air-permeable packaging container (b1) containing the oxygen scavenger composition (A) in a gas barrier container (b2). This is a step of further accommodating the air-permeable packaging container (b1) containing the oxygen agent composition (A) in a gas barrier container (b2). Since the oxygen scavenger composition (A) has excellent oxygen absorption performance, it is preferably stored in a gas barrier container until it is used as an oxygen scavenger.
• Method 2 preferably includes the following steps (III-2), (IV-2), and (II-2) in this order after the above step (I).
• Step (III-2) a step of accommodating the oxygen scavenger composition (a) and the moisture donor in the air-permeable packaging container (b1);
• Step (IV-2) Step (II-2) of further accommodating the breathable packaging container (b1) containing the oxygen scavenger composition (a) and the moisture donor in a gas barrier container (b2) : Supplying water from the moisture donor to the oxygen scavenger composition (a) to obtain the oxygen scavenger composition (A).
• Step (III-2) corresponds to the above step (III), and is a step of housing the oxygen scavenger composition (a) in a breathable packaging container (b1). This is a step of housing the drug composition (a) together with the air-permeable packaging container (b1). Through this step, a self-reactive oxygen scavenger is obtained.
• the above-mentioned ones can be used as the moisture donor.
• Step (IV-2) is a step of further accommodating the breathable packaging container (b1) containing the oxygen scavenger composition (a) and the moisture donor in a gas barrier container (b2).
• a gas barrier container b2
• ventilation with the outside can be blocked.
• water can be effectively supplied from the moisture donor to the oxygen scavenger composition (a) to obtain an oxygen scavenger composition (A) in which a water film having a desired thickness is formed. (corresponds to step (II-2)).
• the average particle diameter was measured by one of the following methods. ⁇ D50 diameter measured with a laser diffraction/scattering particle size distribution measuring device Cumulative measurement in the volume-based particle size distribution using a laser diffraction/scattering particle size distribution measuring device (“LA-960” manufactured by Horiba, Ltd.) The average particle diameter (D50) was measured at a frequency of 50%. ⁇ D50 diameter determined by measuring particle size distribution by classification Weight according to the size of the sieve after 5 minutes of vibration using a standard sieve that complies with ISO 3310-1:2000 (equivalent to JIS Z8801-1:2006) From the fraction, the average particle diameter at a cumulative frequency of 50% (D50) was measured.
• the specific surface area was measured using a constant volume specific surface area measuring device (BELSORP mini II, manufactured by Microtrac Bell Co., Ltd.) under the following conditions, and the specific surface area was calculated by the BET method. . Measurement temperature: -196°C Pretreatment: 300°C, 3 hours, nitrogen flow
• Air permeability resistance The air permeability resistance was measured three times using a digital Oken type air permeability tester (“EG02” manufactured by Asahi Seiko Co., Ltd.). The arithmetic mean value of the obtained results was taken as the measurement result.
• Example 1 (1) Dissolve 0.25 g of sodium chloride (NaCl) in 6 g of water, and add this aqueous solution (NaCl concentration: 4% by mass) to reduced iron powder (manufactured by Höganäs, average particle size 80 ⁇ m (laser diffraction/scattering particle size distribution). D50 diameter measured with a measuring device), specific surface area 0.085 m 2 /g) 100 g), dried, and the surface of the iron powder was coated with sodium chloride by adhering sodium chloride to the surface of the iron powder. (Oxygen scavenger composition (a)) was obtained.
• the oxygen absorber composition (A) containing iron, a metal salt, and water was supplied, and an oxygen absorber package (x2) containing the oxygen absorber composition (A) in an air-permeable packaging container (b1) was obtained.
• an oxygen absorber package (x2) containing the oxygen absorber composition (A) in an air-permeable packaging container (b1) was obtained.
• the absorbent cotton and the oxygen absorber package (x2) are separated in the three-sided aluminum bag, the oxygen absorber package (x2) is cut off along with the three-sided aluminum bag, and the cut end is heated again.
• An oxygen absorber package (y2) in which the oxygen absorber package (x2) was sealed and housed in a three-sided aluminum bag (gas barrier container (b2)) was obtained.
• the following oxygen removal experiment was conducted on the obtained oxygen absorber package (y2) to evaluate its oxygen absorption performance.
• the content of water present on the surface of iron per unit surface area of iron [content of water present on the surface of iron (g)/ ⁇ water present on the surface of iron] Content (g) ⁇ Specific surface area of iron (m 2 /g) ⁇ ] was determined by the following method. First, the weight W 1 of the oxygen absorber package (x1) immediately after production (before water absorption) was measured in advance. Next, the oxygen absorber package (y2) is housed in an aluminum three-sided bag (gas barrier container (b2)) to contain the oxygen absorber package (x2) obtained by supplying water to the oxygen absorber package (x1). ) was measured .
• the amount of water is the amount of water supplied from the absorbent cotton to the surface of the iron in the oxygen absorber composition (a), that is, the content of water present on the surface of the iron in the oxygen absorber composition (A). It can be estimated that the amount.
• Example 2 to 12 and Comparative Examples 1 to 4 oxygen scavenger composition (A) And an oxygen absorber package (y2) was produced.
• the obtained oxygen absorber package (y2) was subjected to the same measurements as in Example 1 and the following evaluation. The results are shown in Table 1.
• an aluminum bag (aluminum foil laminated plastic film bag, manufactured by San-A Kaken Co., Ltd., "700 Aluminum Bag", 700 mm x 800 mm, thickness 0.12 mm), which is a gas barrier bag with higher gas barrier properties, was placed into a size of 350 mm x 400 mm.
• a rubber sheet for sampling (25 mm x 25 mm, 2 mm thick) is glued to the position corresponding to the rubber sheet for sampling of the PTS bag for measurement. I got it.
• the measurement PTS bag contained 3000 mL of air and the oxygen absorber package (y2), and the opening was sealed by heat sealing. Moreover, the oxygen concentration (initial oxygen concentration) in the PTS bag at this time was measured. Next, open the oxygen absorber package (y2) in the PTS bag, take out the oxygen absorber package (x2) from inside, place it together with the PTS bag in the aluminum bag for measurement, and heat seal the opening. and sealed it. At this time, the sampling rubber sheet of the PTS bag and the sampling rubber sheet of the aluminum bag were arranged so as to overlap, and the PTS bag and the aluminum bag were adhered with double-sided tape to prevent the rubber sheets from shifting. The aluminum bag was immediately placed in a constant temperature bath at 25°C and kept there for 7 days. At this time, the oxygen concentration in the PTS bag was measured at each time point of the holding time of 2 hours and 7 days.
• the oxygen concentration was measured using a gas analyzer (“Check Mate 3” manufactured by MOCON). The measurement is performed by inserting the hollow needle at the tip of the sampling silicone tube attached to the gas analyzer into the PTS bag through the sampling rubber sheet attached to the PTS bag and aluminum bag in advance, and measuring the oxygen concentration. This was done by measuring. From the measurement results of the oxygen concentration, the amount of oxygen absorbed per weight of iron powder in the PTS bag (mL/g) was calculated. In this example, when the amount of oxygen absorbed per weight of iron powder after 2 hours is 15 mL/g or more, and when the amount of oxygen absorbed per weight of iron powder after 7 days is 50 mL/g or more, the oxygen absorption It was determined that the performance was good.
• Table 1 The components in Table 1 are shown below.
• - Reduced iron powder manufactured by Höganäs, average particle diameter 80 ⁇ m (D50 diameter measured with a laser diffraction/scattering particle size distribution measuring device), specific surface area 0.085 m 2 /g ⁇ Atomized iron powder 1: Atomized iron powder (manufactured by Kobe Steel, Ltd., average particle diameter 75 ⁇ m (D50 diameter determined by measuring particle size distribution by classification)) passed through a sieve with an opening of 45 ⁇ m, specific surface area 0 .073m 2 /g ⁇ Atomized iron powder 2: Atomized iron powder (same as above) was passed through a sieve with an opening of 180 ⁇ m, and the remaining portion was passed through a sieve with an opening of 150 ⁇ m, specific surface area: 0.035 m 2 /g ⁇ NaCl: Sodium chloride ⁇ NaBr: Sodium bromide ⁇ CaCl 2 : Calcium chloride ⁇
• the content of water present on the surface of iron per unit surface area of iron [content of water present on the surface of iron (g)/ ⁇ content of iron (g) x
• An oxygen scavenger composition having a specific surface area (m 2 /g) ⁇ in the range of 0.60 g/m 2 or more and 2.00 g/m 2 or less has a fast oxygen absorption rate at the initial stage of the reaction and has high oxygen absorption performance. (Examples 1 to 12).

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