JP6020757B1 - Oxygen scavenger and method for producing the same - Google Patents

Abstract

To improve the oxygen absorption capacity of a granular oxygen scavenger. A plurality of composites comprising a porous support and a granulated product comprising an oxygen absorbing composition supported on the support and hydrophilic inorganic fine particles attached to the surface of the granulated product. An oxygen scavenger that is a powder containing particles is disclosed. The oxygen absorbing composition contains a liquid agent containing an oxygen absorbing substance, an alkaline compound, and a transition metal compound. [Selection figure] None

Description

  The present invention relates to an oxygen scavenger and a method for producing the same. The present invention also relates to an oxygen scavenger package and a food package containing an oxygen scavenger.

  An oxygen scavenger may be enclosed in a food packaging container for long-term storage of food. A conventional general oxygen scavenger is a granular material obtained by granulating a liquid oxygen absorbing material together with a carrier (for example, Patent Documents 1 to 3).

Japanese Patent No. 4821692 JP 2003-144112 A Japanese Patent No. 3541859

  The main object of the present invention is to further improve the oxygen absorption capacity of the granular oxygen scavenger.

  One aspect of the present invention is a granulated product comprising a porous carrier and an oxygen absorbing composition supported on the carrier, and hydrophilic inorganic fine particles attached to the surface of the granulated product. An oxygen scavenger that is a powder including a plurality of composite particles is provided.

  Another aspect of the present invention is to mix a porous support and a granulated powder composed of a plurality of granules containing an oxygen-absorbing composition supported on the support and hydrophilic inorganic fine particles. To produce an oxygen scavenger comprising the step of attaching the hydrophilic inorganic fine particles to the surface of the granulated material to obtain an oxygen scavenger that is a powder containing the granulated material and the hydrophilic inorganic fine particles. Regarding the method.

  The oxygen absorbing composition contains a liquid agent containing an oxygen absorbing substance, an alkaline compound, and a transition metal compound.

  By attaching hydrophilic inorganic fine particles to the surface of the granulated product containing the oxygen-absorbing composition, the oxygen-absorbing property inherent in the oxygen-absorbing substance is exhibited, and an oxygen scavenger having an improved oxygen-absorbing ability is obtained. .

  The present invention also provides an oxygen scavenger package comprising the oxygen scavenger and a breathable packaging material containing the oxygen scavenger. The present invention further provides a food package comprising the oxygen absorber package and a food packaging container in which the oxygen absorber package is enclosed.

  The present invention can provide a powdery oxygen scavenger having an improved oxygen absorption capacity.

  Hereinafter, some embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

  An oxygen scavenger according to one embodiment includes a porous carrier and an oxygen-absorbing composition carried on the carrier, and a granulated product and hydrophilic inorganic fine particles attached to the surface of the granulated product. A powder containing a plurality of composite particles mainly composed of Here, the “powder” means an aggregate composed of a large number of fine particles and maintaining fluidity as a whole. As a whole, the fine particles fixed to each other to form a single solid tablet are not included in the powder. The number of composite particles contained in the oxygen scavenger according to the present embodiment may be, for example, 10 or more and 10,000 or less per 1 g of oxygen scavenger.

  The mass of the individual composite particles constituting the oxygen scavenger powder may be 0.3 mg or more, or 0.5 mg or more per composite particle, and may be 10.0 mg or less, or 7.0 mg or less. May be. When the composite particles are so small, higher oxygen absorption ability tends to be obtained.

  The carrier may be any porous particle that can carry the oxygen-absorbing composition. Usually, the oxygen absorbing material is supported on the support by impregnating the support with the oxygen absorbing composition. The carrier is selected from, for example, activated carbon, zeolite particles, bentonite particles, activated alumina particles, activated clay, calcium silicate particles, and diatomaceous earth.

  The oxygen absorbing composition contains a liquid agent containing an oxygen absorbing substance, an alkaline compound, and a transition metal compound.

  The liquid agent containing the oxygen-absorbing substance may be an oxygen-absorbing substance that is liquid at normal temperature (for example, 5 to 35 ° C.), or may be a solution containing a liquid or solid oxygen-absorbing substance. The oxygen-absorbing substance is a main component of the oxygen-absorbing composition and is a substance that absorbs oxygen. The oxygen absorbing material may be, for example, a compound that consumes oxygen by oxidizing itself and absorbs oxygen. In this embodiment, an oxygen-absorbing substance that is liquid at room temperature or dissolved in a solvent can be used. Such an oxygen-absorbing substance is, for example, one or more compounds selected from the group consisting of glycerin, 1,2-glycol, and sugar alcohol. Specific examples of 1,2-glycol include ethylene glycol and propylene glycol. Specific examples of sugar alcohols include erythritol, arabitol, xylitol, adonitol, mannitol, and sorbitol. When the liquid agent is a solution of oxygen-absorbing substance, examples of the solvent in which the oxygen-absorbing substance dissolves include water; methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, secondary butanol, Lower aliphatic alcohols such as tertiary butanol and tertiary amyl alcohol; glycols such as ethylene glycol, propylene glycol and trimethylene glycol; and phenol. These oxygen-absorbing substances can be used alone or in combination.

  The amount of the oxygen-absorbing substance is usually 80 to 200 parts by mass with respect to 100 parts by mass of the support, and may be 100 to 180 parts by mass. When the amount of the oxygen-absorbing substance is within these ranges, an oxygen scavenger having an appropriate oxygen-absorbing ability tends to be obtained.

  Oxygen absorbing materials may require water for reactions that absorb oxygen. For this reason, even if the oxygen absorbing substance itself is liquid at room temperature, water can be added to the liquid as necessary. The amount of water added as necessary is usually 0 to 80 parts by mass and may be 20 to 60 parts by mass with respect to 100 parts by mass of the oxygen-absorbing substance. The amount of water is usually 0 to 90 parts by mass and may be 20 to 70 parts by mass with respect to 100 parts by mass of the carrier.

  An alkaline compound is a compound that forms an alkaline aqueous solution when dissolved in water. When the oxygen absorbing substance has a hydroxyl group, the oxygen absorption reaction is activated by ionizing the hydroxyl group with an alkaline compound. In the state of the oxygen-absorbing composition, a part of the alkaline compound is often dissolved in the liquid agent containing the oxygen-absorbing substance. The alkaline compound may be an alkali metal or alkaline earth metal hydroxide, carbonate, bicarbonate, tertiary phosphate, or secondary phosphate. Alkaline compounds include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, radium hydroxide, lithium carbonate, sodium carbonate, Selected from the group consisting of calcium carbonate, magnesium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate, lithium bicarbonate, tribasic sodium phosphate, tribasic potassium phosphate, dibasic sodium phosphate, and dibasic potassium phosphate One or more compounds may be used.

  The amount of the alkaline compound is usually 100 to 300 parts by mass and may be 150 to 250 parts by mass with respect to 100 parts by mass of the support. When the amount of the oxygen-absorbing substance is within these ranges, an oxygen scavenger having an appropriate oxygen-absorbing ability tends to be obtained.

  The transition metal compound is a compound containing a transition metal element, and is added to promote the oxygen absorption reaction of the oxygen absorbing material. The transition metal compound is often dissolved in a liquid agent containing an oxygen-absorbing substance in the state of the oxygen-absorbing composition. Specific examples of the transition metal element include iron, cobalt, nickel, copper, zinc, and manganese. The transition metal compound may be, for example, a transition metal halide, sulfate, nitrate, phosphate, carbonate, organic acid salt, oxide, hydroxide, or chelate compound. The transition metal compound may be a double salt containing a transition metal element. Transition metal compounds are copper chloride (I), copper chloride (II), copper sulfate (II), copper hydroxide (II), copper oxide (I), copper oxide (II), manganese chloride, manganese nitrate, manganese carbonate And one or more compounds selected from the group consisting of nickel chloride.

  The amount of the transition metal compound is usually 10 to 70 parts by mass and may be 30 to 50 parts by mass with respect to 100 parts by mass of the support. When the amount of the transition metal compound is within these ranges, an oxygen scavenger having an appropriate oxygen absorption capacity tends to be obtained.

  The oxygen absorbing composition may further contain a binder so that a granulated product can be easily formed. Specific examples of the binder include gum arabic, polyvinyl alcohol, sodium alginate, gelatin and cellulose. The amount of the binder is usually 0 to 30 parts by mass and may be 10 to 20 parts by mass with respect to 100 parts by mass of the support.

  The oxygen-absorbing composition may further contain other substances as necessary. Examples of other substances include catechol compounds. The amount of the other substance is usually about 30 parts by mass or less with respect to 100 parts by mass of the support.

  The particle size (maximum width) of the granulated product before the inorganic fine particles adhere is not particularly limited, but may be, for example, 0.3 to 8.0 mm, or 0.3 mm or more and less than 5 mm.

  The granulated product composed of the carrier and the oxygen absorbing composition can be obtained by granulating a mixture containing the carrier and the components constituting the oxygen absorbing composition. Each component which comprises an oxygen absorption composition may be mixed collectively, and may be mixed separately. The mixing machine for mixing is not particularly limited, and may be, for example, a cylindrical type, a V type container rotating type mixer, a ribbon type, a horizontal screw type, a paddle type, a planetary motion type, or the like. A container-fixing type mixer such as the above may be used. Granulation can be performed, for example, by an extrusion granulation method using a screen having a predetermined opening.

  The hydrophilic inorganic fine particles are water-insoluble particles containing a hydrophilic inorganic substance as a main component. The hydrophilic inorganic fine particles usually contain 50% by mass or more of a hydrophilic inorganic substance based on the total mass thereof. Examples of the hydrophilic inorganic substance include hydrophilic silicon dioxide, calcium silicate hydrate, magnesium oxide, and aluminum silicate.

  The average particle diameter of the hydrophilic inorganic fine particles may be 150 μm or less. When the average particle size of the hydrophilic inorganic fine particles is 150 μm or less, the oxygen absorbing ability of the oxygen scavenger can be improved. Usually, fine irregularities are formed on the surface of the granulated product, and the inorganic fine particles having a small particle diameter tend to enter the recesses on the surface of the granulated product. As a result, the surface area of the granulated product is greatly increased, which is considered to contribute to an improvement in oxygen absorption capacity. From the same viewpoint, the average particle size of the hydrophilic inorganic fine particles may be 100 μm or less, or 50 μm or less. The lower limit of the average particle diameter is not particularly limited, but for nano-sized microparticles, for example, it is 0.1 μm or more because the price increases and handling becomes difficult because it is taken into the human body from the skin surface. Also good. Here, the average particle diameter is a value of secondary particle diameter measured by a laser diffraction method.

  The pore volume of the hydrophilic inorganic fine particles may be 0.5 mL / g or more. When the pore volume of the hydrophilic inorganic fine particles is 0.5 mL / g, the oxygen absorbing ability of the oxygen scavenger can be improved. The hydrophilic inorganic fine particles having a large pore volume are considered to easily absorb the oxygen-absorbing composition in the vicinity of the granulated surface. If the oxygen-absorbing composition (especially oxygen-absorbing substance) is absorbed by the hydrophilic inorganic fine particles, the area where the oxygen-absorbing substance comes into contact with the oxygen in the environment increases, and as a result, it is assumed that the oxygen-absorbing ability is improved. A combination of an average particle diameter of 150 μm or less and a pore volume of 0.5 mL / g or more is particularly effective for improving the oxygen absorption capacity. From the same viewpoint, the pore volume of the hydrophilic inorganic fine particles may be 0.8 mL / g or more, or 1.2 mL / g or more. The upper limit of the pore volume is not particularly limited, but may be, for example, 10 mL / g or less. The pore volume here is a value measured by a nitrogen adsorption method or a mercury intrusion method. The pore volume measured by at least one of the nitrogen adsorption method and the mercury intrusion method may be within the above numerical range.

The specific surface area of the hydrophilic inorganic fine particles may be 50 to 1000 m ² / g, or 100 to 400 m ² / g. When the specific surface area of the hydrophilic inorganic fine particles is within these numerical ranges, the oxygen absorbing ability of the oxygen scavenger tends to be further improved. The specific surface area here is a value measured by a nitrogen adsorption method or a water source press-fitting method. The specific surface area measured by at least one of the nitrogen adsorption method and the water source press-in method may be within the above numerical range.

  The hydrophilic inorganic fine particles having the property of easily absorbing the oxygen-absorbing composition can contribute to the improvement of the oxygen absorbing ability of the oxygen scavenger. The degree to which the hydrophilic inorganic fine particles absorb the oxygen-absorbing composition can be evaluated by the amount of the hydrophilic inorganic fine particles absorbed. This liquid absorption amount is measured by a method in which a test liquid composed of a liquid agent containing an oxygen-absorbing substance constituting the oxygen-absorbing composition and a transition metal compound is absorbed into powder of hydrophilic inorganic fine particles. The test liquid for measuring the liquid absorption contains a liquid agent containing an oxygen absorbing substance and a transition metal compound at the same mass ratio as the mass ratio in the oxygen absorbing composition. When the amount of liquid absorption measured by this method (the mass of the test liquid absorbed per 1 g of hydrophilic inorganic fine particles) is 2.0 g / g or more, high oxygen absorption ability tends to be obtained. From the same viewpoint, the liquid absorption amount may be 2.5 g / g or more, or 3.0 g / g or more. The upper limit of the liquid absorption amount is not particularly limited, but may be, for example, 20 g / g or less. Details of the method for measuring the liquid absorption amount will be described in the examples described later.

  The hydrophilic inorganic fine particles having the average particle diameter, the pore volume, the specific surface area and the liquid absorption amount exemplified above can be produced by a usual method, and can be obtained by appropriately selecting from commercially available products. it can.

  The amount (adhesion amount) of hydrophilic inorganic fine particles adhering to the surface of the granulated product is 0.1 parts by mass or more, 0.5 parts by mass or more, and 1 mass with respect to 100 parts by mass of the granulated product. Part or more, 2 parts by mass or more, or 3 parts by mass or more. When the amount of the hydrophilic inorganic fine particles is within these ranges, it is easy to obtain an appropriate oxygen absorbing capacity of the oxygen scavenger. The upper limit of the amount of the hydrophilic inorganic fine particles adhering to the surface of the granulated product is not particularly limited, but from the viewpoint of granulation property and the like, 30 parts by mass or less, 15 parts by mass or less, 10 parts by mass or less, or 8 parts by mass. Or less. Although the single hydrophilic inorganic fine particles not attached to the granulated material may be mixed with the oxygen scavenger particles, the amount of the single hydrophilic inorganic fine particles is not included in the amount of adhesion.

  The oxygen scavenger is a mixture of a granulated powder containing a plurality of granulated materials containing a carrier and an oxygen absorbing composition and a plurality of hydrophilic inorganic fine particles, whereby hydrophilic inorganic fine particles are formed on the surface of the granulated material. It can be obtained by a method comprising the step of attaching. By forming a mixed powder in which the granulated powder and the hydrophilic inorganic fine particles are mixed together as a whole, a plurality of hydrophilic inorganic fine particles adhere to the surface of each granulated product. For example, the hydrophilic inorganic fine particles can be attached to the granulated product by mixing the granulated product and the hydrophilic inorganic fine particles and shaking the resulting mixture.

  The hydrophilic inorganic fine particles attached to the granulated product by the method of mixing the powders as described above form a relatively thin layer. In this respect, the oxygen scavenger form of the present embodiment is, for example, It is generally different from a tablet having an outer part obtained by tableting. Specifically, the hydrophilic inorganic fine particles adhering to the surface of the granulated product can form a layer having a thickness of 1 mm or less or 0.7 mm or less. The thin layer of hydrophilic inorganic fine particles means that when the surface of the composite particle is subjected to elemental analysis by energy dispersive X-ray analysis (EDX analysis), the material constituting the granulated material (oxygen-absorbing substance, alkaline compound or transition metal) Since the element contained in the compound) is detected, it can also be confirmed. In general, in the case of the oxygen scavenger according to the present embodiment, at least one element contained in the material constituting the granulated material is detected at a concentration of 0.05 atomic% or more, or 0.1 atomic% or more. Often done. On the other hand, when the outer shell having a certain thickness including the granulated material is formed by tableting, the element of the material constituting the granulated material is not substantially detected by EDX analysis.

  The oxygen scavenging package according to one embodiment can be mainly composed of the oxygen scavenger according to the above embodiment and a breathable packaging material containing the oxygen scavenger. The breathable packaging material can be appropriately selected from those normally used in the technical field. Specific examples of the breathable packaging material include a bag formed of a substrate made of a perforated plastic film, a nonwoven fabric, a microporous film, paper, or a combination thereof. This oxygen scavenger package can be used, for example, for the purpose of maintaining the freshness of food by being housed in various food packaging containers.

  The food packaging body which concerns on one Embodiment is provided with the said oxygen scavenger packaging body and the food packaging container with which this oxygen scavenger packaging body was enclosed. The food packaging container can be appropriately selected from those normally used in the field of food packaging, and a sealable container is suitable. Examples of food packaging containers include bags, deep drawn packages, tray packages, stretch packages, and the like.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

(Examples 1-5)
1. Granulated product The raw materials shown in Table 1 are uniformly mixed in a sealed state, and a mixture containing activated carbon and an oxygen absorbing composition containing an oxygen scavenger, an alkali compound, a transition metal salt and a binder supported on the activated carbon is prepared. Obtained. The obtained mixture was granulated by an extrusion granulator provided with a screen having a screen hole diameter of 1.0 mmφ and an aperture ratio of 22.6% to obtain a granular granulated product. Table 1 shows the amount of each raw material in parts by mass.

2. Inorganic fine particles The following hydrophilic inorganic fine particles were prepared.
<Hydrophilic silicon dioxide (SiO ₂ ) particles>
・ Silo page 720 (manufactured by Fuji Silysia Chemical)
・ NIPGEL AZ-200 (manufactured by Tosoh Silica)
・ NIPGEL AY-6A3 (Tosoh Silica)
<Amorphous calcium silicate hydrate (CaO.mSiO ₂ .nH ₂ O) particles>
・ Flowlight (Tomita Pharmaceutical)
・ Developed product of amorphous calcium silicate

  Table 2 shows the liquid absorption amount, average particle diameter, average pore diameter, specific surface area, and pore volume of each inorganic fine particle. The average particle diameter is a value measured by a laser diffraction method. The specific surface area and pore volume are measured values by a nitrogen adsorption method for silicon dioxide particles, and measured values by a mercury intrusion method for calcium silicate hydrate particles.

The liquid absorption amount of the inorganic fine particles was measured by the following procedure.
(1) Glycerin, copper (II) sulfate and water are mixed at a mass ratio of 50:15:20 to prepare a test solution.
(2) Knead the inorganic fine particles with a spoon while dripping the test solution little by little into a predetermined amount of the inorganic fine particles. Record the amount (limit amount) of the test solution dripped up to the limit where the powdered inorganic fine particles absorb the test solution and become one lump. When the dropping amount of the test liquid exceeds the limit amount of the inorganic fine particles, the inorganic fine particles cannot absorb the test liquid, and one lump is broken and becomes a slurry.
(3) The amount of liquid absorption is calculated by the following formula.
Liquid absorption [g / g] = limit amount of test liquid [g] / mass of inorganic fine particles [g]

3. Oxygen scavenger 0.9 g of various inorganic fine particles were placed in an oxygen barrier bag. There, 30 g of granulated material was put, and the bag was heat-sealed. The bag was shaken to form an oxygen scavenger in which the granulated material was coated with inorganic fine particles. The bag was opened and heat sealed again to expel the air inside and the oxygen scavenger was stored.

4. Energy dispersive X-ray analysis (EDX analysis)
The surface of the oxygen scavenger of Example 1 was analyzed by EDX analysis under the conditions of an acceleration voltage of 20 kV and an analysis time of 100 seconds (live time). As a result, Cu element derived from copper sulfate constituting the granulated product was detected at a concentration of 1.06 atomic%. From this, it was confirmed that the hydrophilic inorganic fine particles adhered very thinly on the surface of the granulated product. When the tablet which has the center part and outer part which consist of the same oxygen absorption composition was created and the surface was analyzed by EDX analysis, Cu element was not detected.

5. Oxygen absorption capacity 2.0 g of oxygen scavenger was housed in a bag (60 mm long, 60 mm wide) made of a perforated packaging material to produce a deoxidant package. As an effective packaging material, a laminated material composed of polyethylene terephthalate / polyethylene / paper / polyethylene was used. The oxygen scavenger package was placed in a gas barrier bag together with absorbent cotton soaked with a 44% aqueous solution of sucrose (water activity 0.95). The bag was sealed and 500 mL of air was injected therein, and then the bag was left in an atmosphere at 25 ° C. The oxygen concentration in the bag after 24 hours and 48 hours was measured. Low oxygen concentration means high oxygen absorption capacity.

5. Results Table 2 shows the evaluation results of the characteristics of the inorganic fine particles, the combination of the granulated product and the inorganic fine particles, and the oxygen absorption capacity. The comparative example is an example in which the granulated material is not coated with inorganic fine particles and used as an oxygen scavenger as it is. It was confirmed that the oxygen scavenger of each Example in which hydrophilic inorganic fine particles were supported on a porous carrier exhibited an excellent oxygen absorbing ability.

(Examples 6 to 15)
An oxygen scavenger was prepared in the same manner as in Example 1 except that the amount of hydrophilic silicon dioxide particles (silopage 720) attached to the granulated product was changed to the amount shown in Table 3. In Example 8, the oxygen scavenger was prepared again with the same adhesion amount as in Example 1. The comparative example is an example in which the granulated material is not coated with inorganic fine particles and used as an oxygen scavenger as it is. 2.74 g of the obtained oxygen scavenger was stored in a bag (length 60 mm, width 60 mm) formed of a perforated packaging material to produce a oxygen scavenger package. As an effective packaging material, a laminated material composed of polyethylene terephthalate / polyethylene / paper / polyethylene was used. The oxygen scavenger package was placed in a gas barrier bag together with absorbent cotton soaked with a 44% aqueous solution of sucrose (water activity 0.95). The bag was sealed and 500 mL of air was injected therein, and then the bag was left in an atmosphere at 25 ° C. The oxygen concentration in the bag after 24 hours was measured. In some examples and comparative examples, the oxygen concentration in the bag after 48 hours was also measured. Table 3 shows the measurement results. It was confirmed that a high deoxygen absorption capacity can be obtained in a wide range of adhesion amount compared with the granulated product before adhesion.

Claims (13)

A granulated product comprising a porous carrier and an oxygen-absorbing composition carried on the carrier;
Hydrophilic inorganic fine particles adhering to the surface of the granulated product,
An oxygen scavenger that is a powder comprising a plurality of composite particles comprising:
The oxygen absorbing composition contains a liquid agent containing an oxygen absorbing substance, an alkaline compound, and a transition metal compound.
Oxygen scavenger.   The oxygen scavenger according to claim 1, wherein the hydrophilic inorganic fine particles have an average particle size of 150 μm or less.   The oxygen scavenger according to claim 1 or 2, wherein the hydrophilic inorganic fine particles have a pore volume of 0.5 mL / g or more.   The oxygen scavenger according to any one of claims 1 to 3, wherein the amount of the hydrophilic inorganic fine particles is 0.1 to 30 parts by mass with respect to 100 parts by mass of the granulated product.   The oxygen scavenger according to any one of claims 1 to 4, wherein a mass of the composite particles is 0.3 to 10.0 mg per composite particle.   The oxygen scavenger according to any one of claims 1 to 5, wherein the hydrophilic inorganic fine particles attached to the surface of the granulated material form a layer having a thickness of 1 mm or less.   The hydrophilic inorganic fine particles so that the elements contained in the oxygen-absorbing substance, the alkaline compound or the transition metal compound are detected when the surface of the composite particle is subjected to elemental analysis by energy dispersive X-ray analysis. The oxygen scavenger according to any one of claims 1 to 6, which is attached to the surface of the granulated product. By mixing a porous support and a granulated powder comprising a plurality of granules containing an oxygen absorbing composition supported on the support and a plurality of hydrophilic inorganic fine particles, the granulated product is mixed. A step of adhering the hydrophilic inorganic fine particles to the surface to obtain an oxygen scavenger that is a powder containing the granulated product and the hydrophilic inorganic fine particles,
The oxygen absorbing composition contains a liquid agent containing an oxygen absorbing substance, an alkaline compound, and a transition metal compound.
A method for producing an oxygen scavenger.   The method according to claim 8, wherein the hydrophilic inorganic fine particles have an average particle diameter of 150 μm or less.   The method according to claim 8 or 9, wherein the hydrophilic inorganic fine particles have a pore volume of 0.5 mL / g or more.   The amount of the hydrophilic inorganic fine particles attached to the granulated product is 0.1 to 30 parts by mass with respect to 100 parts by mass of the granulated product, according to any one of claims 8 to 10. The method described.   An oxygen scavenger package comprising the oxygen scavenger according to any one of claims 1 to 7 and a breathable packaging material containing the oxygen scavenger.   A food package comprising the oxygen scavenger package according to claim 12 and a food packaging container in which the oxygen scavenger package is enclosed.