JP6834282B2 - Oxygen scavenger, method of manufacturing oxygen scavenger, oxygen scavenger package and food package - Google Patents

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 containing an oxygen scavenger and a food package.

Oxygen scavengers may be encapsulated in food packaging for long-term storage of food. Oxygen scavengers absorb and remove oxygen as a means of suppressing quality deterioration due to oxidation and the growth of bacteria and microorganisms. In addition to the oxygen absorption capacity, the oxygen scavenger is required to have excellent safety, low cost, and ease of handling. Iron powder has been used as an excellent material that can satisfy these characteristics. However, since metal detectors have been introduced especially in the food packaging process, iron powder may not be used in some cases. Therefore, oxygen scavengers made of organic materials that are not detected by metal detectors have come to be used. In order to approach the excellent oxygen absorption of iron powder, various oxygen scavengers in the form of a combination of an organic material and a granular material made of a porous material have been proposed.

For example, Patent Document 1 discloses an oxygen scavenger containing glycerin as a main component and phenols, in which t-butylhydroquinone is used as the phenols, in order to solve the above problems. As a result, the oxygen absorption performance can be significantly improved, and an oxygen scavenger that is inexpensive, safe in terms of food hygiene, and has excellent practicality and is not detected even by a metal detector is provided.

Further, in Patent Document 2, when an oxygen scavenger whose main agent is an organic substance, which has a large pore volume of calcium silicate impregnated with a deoxidizing solution and a large specific surface area, the amount of oxygen absorbed is comparable to that of iron. It was found that the amount can be increased ^{, and calcium silicate having a specific surface area of 10 m 2} / g or more and a pore volume of 3.0 cc / g or more is impregnated with an oxygen-absorbing liquid. As a result, the oxygen absorption performance is greatly improved.

Further, in Patent Document 3, an oxygen scavenger composition containing a swelling agent that swells with water and water is pressure-molded to obtain a solid oxygen scavenger composition, and the granules are sized to obtain a granular product. Disclosed is a method for producing an oxygen scavenger composition having improved fluidity by mixing a hydrophobic lubricant with, and the lubricant may be hydrophobic silica, magnesium stearate or calcium stearate. It is disclosed.

However, the oxygen absorption capacity of the organic material-based oxygen scavenger obtained by these techniques is not always sufficient, and further improvement in performance is required.

Japanese Patent No. 3541859 Japanese Unexamined Patent Publication No. 2003-144112 Japanese Patent No. 4821692

In view of the above circumstances, an object of the present invention is to further improve the oxygen absorption capacity of a granular oxygen scavenger using an organic oxygen absorption composition.

One aspect of the present invention is a granule containing a carrier made of an alkaline compound and an oxygen absorbing composition supported on the support, and a hydrophilic inorganic particulate matter adhering to the surface of the granule. To provide an oxygen scavenger which is a powder containing a plurality of composite particles comprising.

Another aspect of the present invention is a support made of an alkaline compound, a granulated powder made of a plurality of granules containing an oxygen absorbing composition supported on the support, and a hydrophilic inorganic particulate matter. The present invention comprises a step of adhering the hydrophilic inorganic particulate matter to the surface of the granulated product by mixing to obtain an oxygen scavenger which is a powder containing the granulated product and the hydrophilic inorganic particulate matter. , Regarding the method of producing an oxygen scavenger.

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

By adhering a hydrophilic inorganic particulate substance 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 produced. can get.

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 including the oxygen scavenger package and a food packaging container in which the oxygen scavenger package is enclosed.

Therefore, as a means for solving the above-mentioned problems, the invention according to claim 1 of the present invention comprises a granulated product containing an oxygen absorbing composition supported on a carrier made of an alkaline compound, and a surface of the granulated product. A deoxidizer that is a powder containing composite particles containing a hydrophilic inorganic particulate substance adhering to the oxygen absorbing composition, wherein the oxygen absorbing composition contains a liquid agent containing the oxygen absorbing substance and a transition metal compound . The hydrophilic inorganic particulate substance is a deoxidizing agent characterized by being hydrophilic silicon dioxide particles.

The invention according to claim 2 is the oxygen scavenger according to claim 1, wherein the hydrophilic inorganic particulate matter has an average particle size of 150 μm or less.

The invention according to claim 3 is the oxygen scavenger according to claim 1 or 2, wherein the hydrophilic inorganic particulate matter has a pore volume of 0.5 mL / g or more. ..

The invention according to claim 4 is characterized in that the amount of the hydrophilic inorganic particulate matter 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 3.

The invention according to claim 5 is the desorption according to any one of claims 1 to 4, wherein the mass of the composite particles is 0.3 to 10.0 mg per composite particle. It is an oxygen agent.

The invention according to claim 6 is characterized in that the hydrophilic inorganic particulate matter adhering to the surface of the granulated product forms a layer having a thickness of 1 mm or less. The deoxidizer according to any one of 5.

Further, in the invention according to claim 7, when the hydrophilic inorganic particulate substance is elementally analyzed on the surface of the composite particle by energy dispersive X-ray analysis, the carrier, the oxygen absorbing substance or the transition metal. The deoxidizer according to any one of claims 1 to 6, which is attached to the surface of the granulated product so that an element contained in the compound can be detected.

The invention according to claim 8 is a step of obtaining a granulated product powder composed of a plurality of granules containing an oxygen absorbing composition supported on an oxygen absorbing substance carrier made of an alkaline compound, and the granulation. By mixing the product powder and a plurality of hydrophilic inorganic particulate matter , the hydrophilic inorganic particulate matter is adhered to the surface of the granulated product, and the granulated product and the hydrophilic inorganic particulate matter are attached. The oxygen absorbing composition comprises a liquid agent containing an oxygen absorbing substance and a transition metal compound, and the hydrophilic inorganic particulate matter is hydrophilic silicon dioxide particles. It is a method for producing a deoxidizer.

The invention according to claim 9 is the method for producing an oxygen scavenger according to claim 8, wherein the hydrophilic inorganic particulate matter has an average particle size of 150 μm or less.

The invention according to claim 10 is the production of the oxygen scavenger according to claim 8 or 9, wherein the hydrophilic inorganic particulate matter has a pore volume of 0.5 mL / g or more. The method.

Further, in the invention according to claim 11, the amount of the hydrophilic inorganic particulate matter adhering to the granulated product is 0.1 to 30 parts by mass with respect to 100 parts by mass by mass of the granulated product. The method for producing an oxygen scavenger according to any one of claims 8 to 10.

The invention according to claim 12 is characterized by comprising the oxygen scavenger according to any one of claims 1 to 7 and a breathable packaging material containing the oxygen scavenger. It is an agent package.

The invention according to claim 13 is characterized by comprising the oxygen scavenger package according to claim 12 and a food packaging container in which the oxygen scavenger package is enclosed. Is.

The present invention can provide a powdered 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.

The oxygen scavenger of the present invention will be described.
The oxygen scavenger of the present invention comprises a granulated product containing an oxygen absorbing composition supported on a carrier made of an alkaline compound, and a hydrophilic inorganic particulate matter adhering to the surface of the granulated product. It is an oxygen scavenger that is a powder containing composite particles.
The oxygen scavenger of the present invention is a powder characterized in that the oxygen absorbing composition contains a liquid agent containing an oxygen absorbing substance and a transition metal compound.
Here, "powder" means an aggregate that is composed of a large number of particulate matter and maintains fluidity as a whole. As a whole, the powder itself does not contain the particulate matter formed by sticking to each other to form a single solid tablet. The number of composite particles contained in the oxygen scavenger according to the present embodiment may be, for example, 10 or more and 10000 or less per 1 g of the oxygen scavenger.

The mass of each composite particle constituting the powder of the oxygen scavenger may be 0.3 mg or more, 0.5 mg or more, or 10.0 mg or less, or 7.0 mg or less per composite particle. You may. Such fine particles of composite particles tend to provide higher oxygen absorption capacity.

The carrier may be particles made of an alkaline compound capable of supporting the oxygen absorbing composition. Usually, the oxygen absorbing composition is supported on the carrier by impregnating the carrier with the oxygen absorbing composition. 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. The alkaline compound may be a hydroxide, carbonate, bicarbonate, tertiary phosphate, or secondary phosphate of an alkali metal or alkaline earth metal. 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 hydrogen carbonate, sodium hydrogen carbonate, lithium hydrogen carbonate, sodium tertiary phosphate, potassium tertiary phosphate, sodium secondary phosphate, and potassium secondary phosphate. It may be one or more compounds.

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

The liquid agent containing the oxygen absorbing substance may be a liquid oxygen absorbing substance at room 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 the main agent of the oxygen absorbing composition and is a substance that absorbs oxygen. The oxygen absorbing substance may be, for example, a compound that consumes oxygen by oxidizing itself and absorbs oxygen. In the present 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 an oxygen absorbing substance, the solvent in which the oxygen absorbing substance is dissolved includes, for example, water; methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, secondary butanol, and the like. Lower aliphatic alcohols such as tertiary butanol and tertiary amyl alcohol; glycols such as ethylene glycol, propylene glycol and trimethylene glycol; and phenol. The oxygen absorbing substance can be used alone or in combination of two or more.

The amount of the oxygen absorbing substance is usually 20.0 to 55.0 parts by mass and may be 25.0 to 50.0 parts by mass with respect to 100.0 parts by mass of the mass of the carrier. When the amount of the oxygen absorbing substance is within these ranges, it tends to be easy to obtain an oxygen scavenger having an appropriate oxygen absorbing capacity.

Oxygen scavengers may require water for the reaction to absorb oxygen. Therefore, even if the oxygen absorbing substance itself is a liquid at room temperature, water can be added to the liquid agent as needed. The amount of water added as needed is usually 0.0 to 80.0 parts by mass with respect to 100.0 parts by mass of the oxygen absorbing substance, even if it is 20.0 to 60.0 parts by mass. Good. The amount of water is usually 0.0 to 25.0 parts by mass and may be 5.0 to 20.0 parts by mass with respect to 100.0 parts by mass of the carrier.

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

The amount of the transition metal compound is usually 2.5 to 20.0 parts by mass and may be 7.5 to 15.0 parts by mass with respect to 100.0 parts by mass of the support. When the amount of the transition metal compound is within these ranges, it tends to be easy to obtain an oxygen scavenger having an appropriate oxygen absorbing capacity.

The oxygen absorbing composition may further contain a binder so that the granules 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 0.0 to 8.0 parts by mass and may be 2.5 to 5.5 parts by mass with respect to 100 parts by mass of the carrier.

The oxygen absorption composition may further contain other substances if necessary. Examples of other substances include catechol compounds. The amount of other substances is usually about 8.0 parts by mass or less with respect to 100.0 parts by mass of the mass of the carrier.

The particle size (maximum width) of the granulated product before the inorganic particulate matter adheres is not particularly limited, but may be, for example, 0.3 to 8.0 mm, or 0.3 mm or more and less than 5.0 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. The components constituting the oxygen absorption composition may be mixed together or separately. The mixer for mixing is not particularly limited, and may be, for example, a container rotary type mixer such as a cylindrical type or a V type, a ribbon type, a horizontal screw type, a paddle type, or a planetary motion type. It may be a container fixed type mixer such as. Granulation can be performed, for example, by an extrusion granulation method using a screen having predetermined openings.

The hydrophilic inorganic particulate matter is a water-insoluble particle containing a hydrophilic inorganic substance as a main component. The hydrophilic inorganic particulate matter usually contains 50% by mass or more of the hydrophilic inorganic substance based on the total mass thereof. Hydrophilic inorganic substances include, for example, hydrophilic silicon dioxide, calcium silicate hydrate, magnesium oxide, and aluminum silicate.

The average particle size of the hydrophilic inorganic particulate matter may be 150 μm or less. When the average particle size of the hydrophilic inorganic particulate matter is 150 μm or less, the oxygen absorption capacity of the oxygen scavenger can be improved. Fine irregularities are usually formed on the surface of the granulated product, and an inorganic particulate matter having a small particle size easily enters the recesses on the surface of the granulated product. As a result, the surface area of the granulated product is significantly increased, which is considered to contribute to the improvement of oxygen absorption capacity. From the same viewpoint, the average particle size of the hydrophilic inorganic particulate matter may be 100 μm or less, or 50 μm or less. The lower limit of the average particle size is not particularly limited, but nano-sized particulate matter increases the price and is difficult to handle because it is taken into the human body from the skin surface. Therefore, for example, it is 0.1 μm or more. There may be. The average particle size here is a value of the volume average diameter of the secondary particles measured by the laser diffraction method.

The pore volume of the hydrophilic inorganic particulate matter may be 0.5 mL / g or more. When the pore volume of the hydrophilic inorganic particulate matter is 0.5 mL / g, the oxygen absorption capacity of the oxygen scavenger can be improved. It is considered that the hydrophilic inorganic particulate matter having a large pore volume easily absorbs the oxygen absorbing composition near the surface of the granulated product. When the oxygen absorbing composition (particularly the oxygen absorbing substance) is absorbed by the hydrophilic inorganic particulate matter, it is presumed that the area of contact between the oxygen absorbing substance and oxygen in the environment increases, and as a result, the oxygen absorbing capacity is improved. .. A combination of an average particle size 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 particulate matter 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, 10.0 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 particulate matter, 50~1000m ² / g, or 100~400m may be ² / g. When the specific surface area of the hydrophilic inorganic particulate matter is within these numerical ranges, the oxygen absorption capacity 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-fitting method may be within the above numerical range.

The property that the hydrophilic inorganic particulate matter easily absorbs the oxygen absorption composition can contribute to the improvement of the oxygen absorption capacity of the oxygen scavenger. The degree to which the hydrophilic inorganic particulate matter absorbs the oxygen absorbing composition can be evaluated by the amount of liquid absorbed by the hydrophilic inorganic particulate matter. The amount of liquid absorbed is measured by a method of absorbing a test solution composed of a liquid agent containing an oxygen absorbing substance and a transition metal compound constituting the oxygen absorbing composition into a powder of hydrophilic inorganic particulate matter. The test solution for measuring the amount of absorbed liquid contains a liquid agent containing an oxygen absorbing substance and a transition metal compound in the same mass ratio as the mass ratio in the oxygen absorbing composition. When the amount of liquid absorbed (mass of the absorbed test solution per 1 g of hydrophilic inorganic particulate matter) measured by this method is 2.0 g / g or more, high oxygen absorption capacity tends to be obtained. is there. From the same viewpoint, the amount of liquid absorbed may be 2.5 g / g or more, or 3.0 g / g or more. The upper limit of the amount of liquid absorbed is not particularly limited, but may be, for example, 20.0 g / g or less. Details of the method for measuring the amount of liquid absorbed will be described in Examples described later.

The hydrophilic inorganic particulate matter having the average particle size, pore volume, specific surface area and liquid absorption amount exemplified above can be produced by a usual method, and can be appropriately selected and obtained from commercially available products. You can also do it.

The amount (adhesion amount) of the hydrophilic inorganic particulate substance adhering to the surface of the granulated product is 0.1 part by mass or more and 0.5 part by mass with respect to 100.0 parts by mass of the mass of the granulated product. As mentioned above, it may be 1.0 part by mass or more, 2.0 part by mass or more, or 3.0 part by mass or more. When the amount of the hydrophilic inorganic particulate matter is within these ranges, it is easy to obtain an appropriate oxygen absorption capacity of the oxygen scavenger. The upper limit of the amount of hydrophilic inorganic particulate matter 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, 15.0 parts by mass or less, 10.0 It may be less than a part by mass or less than 8.0 parts by mass. A single hydrophilic inorganic particulate matter that is not attached to the granules may be mixed with the particles of the oxygen scavenger, but the amount of the single hydrophilic inorganic particulate matter is included in the above adhesion amount. I can't.

The oxygen scavenger is hydrophilic on the surface of the granules by mixing a granule powder containing a plurality of granules containing a carrier and an oxygen absorbing composition with a plurality of hydrophilic inorganic particulate matter. It can be obtained by a production method including a step of adhering an inorganic particulate matter. By forming a mixed powder in which the granulated product powder and the hydrophilic inorganic particulate matter as a whole are mixed, a plurality of hydrophilic inorganic particulate matter adheres to the surface of each granulated product. For example, the hydrophilic inorganic particulate matter can be attached to the granulated product by mixing the granulated product and the hydrophilic inorganic particulate matter and shaking the obtained mixture.

The hydrophilic inorganic particulate matter adhering to the granules by the method of mixing the powders as described above forms a relatively thin layer, and in this respect, the form of the oxygen scavenger of the present embodiment is , For example, it is generally different from a tablet having an outer shell obtained by tableting. Specifically, the hydrophilic inorganic particulate matter adhering to the surface of the granulated product can form a layer having a thickness of 1.0 mm or less or 0.7 mm or less. The thin layer of hydrophilic inorganic particulate matter means that when the surface of the composite particle is elementally analyzed by energy dispersive X-ray analysis (EDX analysis), the material (oxygen absorber, alkaline compound or Since the element contained in the transition metal compound) is detected, it can be confirmed. Generally, in the case of the oxygen scavenger according to the present embodiment, at least one element contained in the material constituting the granulated product is detected at a concentration of 0.05 atomic number% or more or 0.10 atomic number% or more. Often done. On the other hand, when the outer shell portion having a certain thickness containing the granulated product is formed by tableting, the elements of the material constituting the granulated product are not substantially detected by the EDX analysis.

The oxygen scavenger package according to one embodiment may 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 commonly used in the art. Specific examples of the breathable packaging material include a bag formed of a perforated plastic film, a non-woven fabric, a microporous film, paper, or a base material made of a combination thereof. This oxygen scavenger package can be stored in various food packaging containers, for example, and used for the purpose of maintaining the freshness of food.

The food packaging according to the embodiment includes the oxygen scavenger packaging and a food packaging container in which the oxygen scavenger packaging is enclosed. The food packaging container can be appropriately selected from those usually used in the field of food packaging, and a sealable container is preferable. Examples of the food packaging container include a bag body, a deeply squeezed package body, a tray package body, a stretch package body and the like.

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

<Examples 1 to 5 and Comparative Example 1>
-Granulated product First, the granulated product will be explained.
The raw materials shown in Table 1 are uniformly mixed in a sealed state, calcium hydroxide and glycerin are used as the oxygen absorbing substance supported on the calcium hydroxide, and oxygen absorption containing copper sulfate (ll) as the transition metal salt. A mixture was obtained using cellulose as the composition and binder. The obtained mixture was granulated by an extrusion granulator provided with a screen having a screen pore diameter of 1.0 mmφ and an aperture ratio of 22.6% to obtain a granular granule. Table 1 shows the blending amount of each raw material by mass.

-Hydrophilic inorganic particulate matter Next, hydrophilic inorganic particulate matter will be described.
First, the following hydrophilic inorganic particulate matter was prepared. These are the inorganic particulate matter used in Examples 1 to 5, respectively.

<Hydrophilic silicon dioxide (SiO ₂ ) particles>
・ Silo page 720 (manufactured by Fuji Silysia Chemical)
・ NIPGEL AZ-200 (manufactured by Toso Silica)
・ NIPGEL AY-6A3 (manufactured by Tosoh Silica)

<Amorphous calcium silicate hydrate (CaO, mSiO ₂ , nH ₂ O) particles>
・ Fluorite (manufactured by Tomita Pharmaceutical Co., Ltd.)
・ Amorphous calcium silicate development product

Table 2 shows the components of the inorganic particulate matter used in Examples 1 to 5, the product name, the amount of each inorganic particulate matter attached, the amount of liquid absorbed, the average particle size, the specific surface area and the pore volume. The average particle size is a measured value of the volume average diameter by the laser diffraction method. The specific surface area and pore volume are measured values by the nitrogen adsorption method for silicon dioxide particles and measured by the mercury intrusion method for calcium silicate hydrate particles. In addition, Comparative Example 1 in Table 2 is an example in which the granulated product was not coated with the inorganic particulate matter and was used as it was as an oxygen scavenger.

The amount of liquid absorbed by the inorganic particulate matter 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 particulate matter with a spatula while dropping the test solution little by little on a predetermined amount of the inorganic particulate matter. Record the amount (limit amount) of the test solution dropped to the limit where the powdered inorganic particulate matter absorbs the test solution and becomes one mass. When the amount of the test liquid dropped exceeds the limit amount of the inorganic particulate matter, the inorganic particulate matter cannot absorb the test liquid, and one lump collapses into a slurry.
(3) The amount of liquid absorbed is calculated by the following formula.
Liquid absorption [g / g] = limit amount of test solution [g] / mass of inorganic particulate matter [g]

3. 3. Preparation of oxygen scavenger 0.9 g of various inorganic particulate matter was placed in an oxygen barrier bag. 30 g of granulated product was put therein, and the bag was heat-sealed. The bag was shaken to form an oxygen scavenger whose granules were coated with an inorganic particulate matter. 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 number%. From this, it was confirmed that the hydrophilic inorganic particulate matter adhered very thinly to the surface of the granulated product. When a tablet having a central part and an outer part made of the same oxygen absorbing composition was prepared and the surface thereof was analyzed by EDX analysis, no Cu element was detected.

5. Oxygen absorption capacity 2.0 g of oxygen scavenger was stored in a bag (length 60 mm, width 60 mm) formed of a perforated packaging material to prepare an oxygen scavenger package. As the perforated packaging material, a breathable perforated film in which holes having a diameter of 0.2 mm were formed in a matrix at a pitch of 3 mm was used in a laminated material composed of polyethylene terephthalate / polyethylene / paper / polyethylene. The oxygen scavenger package was placed in a gas barrier bag together with absorbent cotton (water activity 0.95) soaked with a 44% aqueous solution of sucrose. The bag was sealed, 500 mL of air was injected into it, and then the bag was left in an atmosphere of 25 ° C. The oxygen concentration in the bag was measured after 24 hours and 48 hours. A low oxygen concentration means a high oxygen absorption capacity.

5. Results Table 2 shows the evaluation results of the characteristics of the inorganic particulate matter, the combination of the granulated product and the inorganic particulate matter, and the oxygen absorption capacity. A comparative example is an example in which the granulated product is not coated with an inorganic particulate matter and is used as it is as an oxygen scavenger. In the column of oxygen absorption rate, it is described that if the oxygen concentration in the bag reaches 0% within 48 hours, it is effective (◯), and if it does not reach 0%, it is not effective (x). It was confirmed that the oxygen scavengers of Examples 1 to 5 in which the hydrophilic inorganic particulate matter was supported on the porous carrier showed excellent oxygen absorption capacity.

Claims (13)

A powder containing composite particles comprising a granule containing an oxygen absorbing composition supported on a carrier made of an alkaline compound and a hydrophilic inorganic particulate substance adhering to the surface of the granulated product. An oxygen scavenger, wherein the oxygen absorbing composition contains a liquid agent containing an oxygen absorbing substance and a transition metal compound, and the hydrophilic inorganic particulate matter is hydrophilic silicon dioxide particles. .. The oxygen scavenger according to claim 1, wherein the hydrophilic inorganic particulate matter has an average particle size of 150 μm or less. The oxygen scavenger according to claim 1 or 2, wherein the hydrophilic inorganic particulate matter has 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 particulate matter 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 the 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 particulate matter adhering to the surface of the granulated product forms a layer having a thickness of 1 mm or less. When the hydrophilic inorganic particulate substance is elementally analyzed on the surface of the composite particle by energy dispersive X-ray analysis, the element contained in the carrier, the oxygen absorbing substance or the transition metal compound is detected. The deoxidizer according to any one of claims 1 to 6, which is attached to the surface of the granulated product. A step of obtaining a granulated product powder composed of a plurality of granules containing an oxygen absorbing composition supported on an oxygen absorbing substance carrier composed of an alkaline compound, and a step of obtaining the granulated product powder and a plurality of hydrophilic inorganic particulates. By mixing with a substance , the hydrophilic inorganic particulate matter is adhered to the surface of the granulated product to obtain a deoxidizer which is a powder containing the granulated product and the hydrophilic inorganic particulate matter. A method for producing a deoxidizing agent, which comprises a step, wherein the oxygen absorbing composition contains a liquid agent containing an oxygen absorbing substance and a transition metal compound, and the hydrophilic inorganic particulate matter is hydrophilic silicon dioxide particles. The method for producing an oxygen scavenger according to claim 8, wherein the hydrophilic inorganic particulate matter has an average particle size of 150 μm or less. The method for producing an oxygen scavenger according to claim 8 or 9, wherein the hydrophilic inorganic particulate matter has a pore volume of 0.5 mL / g or more. 8. 10 of claims 8-10, wherein the amount of the hydrophilic inorganic particulate matter adhering to the granulated product is 0.1 to 30 parts by mass with respect to 100 parts by mass of the granulated product. The method for producing an oxygen scavenger according to any one. 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 packaging body comprising the oxygen scavenger packaging according to claim 12 and a food packaging container in which the oxygen scavenger packaging is enclosed.