JP7263989B2 - Oxygen absorber, oxygen absorber package and food package - Google Patents

Description

The present invention relates to oxygen scavengers. The present invention also relates to oxygen absorber packages and food packages containing oxygen absorbers.

For long-term preservation of food, there is a method of enclosing an oxygen scavenger in a food packaging container. In this method, an article to be stored and an oxygen scavenger are enclosed in a gas-barrier sealed bag or sealed container, the oxygen in the sealed system is absorbed by the oxygen scavenger, and the storage atmosphere is maintained in a substantially oxygen-free state. This is a method that suppresses quality deterioration due to oxidation and the growth of bacteria and microorganisms.

There are two main types of oxygen absorbers in common use today: inorganic oxygen absorbers based on iron and organic oxygen absorbers based on ascorbic acid-based oxygen-absorbing substances. . Each is used according to the purpose and target food, but in recent years, the need to put products through metal detectors has increased, so the demand for organic oxygen absorbers that can be put through metal detectors has increased. there is

However, organic oxygen scavengers have the disadvantage that their oxygen absorption speed is slower than that of iron-based oxygen scavengers. In addition, since oxygen scavengers are packed in small bags, they are required to have powder characteristics such as high bulk density and high flowability without causing dusting at the time of filling. In view of the circumstances described above, a method of granulating a finely powdered oxygen absorber composition to prevent powder scattering may be adopted. However, when granulated, the fine powder is compressed and the reaction surface area is reduced, so there is a problem that the oxygen absorption rate is very slow compared to the powder state.

When used as an oxygen absorber to improve the shelf life of food, the oxygen concentration must be reduced to less than 0.1% within 24 hours in order to suppress the growth of mold, which grows in 24 to 48 hours at the earliest. It is desirable to let Therefore, how to increase the oxygen absorption rate has been one of the problems in organic oxygen scavengers. In addition, from the point of view of accidental ingestion of oxygen scavengers and the risk of transfer of ingredients to foods, oxygen scavengers are also required to be composed of highly safe ingredients.

Therefore, in order to increase the oxygen absorption rate of organic oxygen scavengers, various efforts have been made, such as adding a reaction catalyst that accelerates the oxidation reaction of the oxygen-absorbing substance, or adding an alkaline compound to achieve the optimum pH. As one of them, composite particles having hydrophilic inorganic fine particles on the surface of granules of an oxygen-absorbing composition carried on a porous carrier have been proposed (Patent Document 1).

Japanese Patent No. 6020757

However, the inventors have found that using the oxygen absorber having the configuration described in Patent Document 1, the oxygen absorption rate in a 25 ° C. environment and a refrigeration environment (10 ° C. or lower by JAS method, 5 ° C. or lower by Food Sanitation Law) When evaluated, sufficient oxygen absorption performance could not be obtained.

The present invention has been made in view of the above points, and an object of the present invention is to provide an oxygen scavenger with improved oxygen absorption performance.

The oxygen absorber according to the present invention comprises a porous support and a powder containing an oxygen-absorbing composition supported on the support. compounds, transition metal compounds and alkali salts of 1,4-dihydro-9,10-dihydroxyanthracene.

According to one aspect of the present invention, it is possible to obtain an oxygen absorber with improved oxygen absorption performance compared to conventional ones.

Several embodiments of the invention are described in detail below. However, the present invention is not limited to the following embodiments.

The oxygen scavenger according to one embodiment includes a porous support and a powder or granule containing an oxygen-absorbing composition supported on the support, or a granule thereof, and a hydrophilic material adhered to the surface of the granule. a plurality of composite particles mainly composed of organic fine inorganic particles. Here, granules and granules are composed of a large number of fine particles and mean an aggregate that maintains fluidity as a whole, and the fine particles adhere to each other as a whole to form a single solid tablet. not included. The number of composite particles contained in the oxygen absorber according to the present embodiment may be, for example, 10 or more and 10000 or less per 1 g of the oxygen absorber.

The mass of the individual composite particles constituting the granules of the oxygen absorber may be 0.3 mg or more, or 0.5 mg or more, and may be 10.0 mg or less, or 7.0 mg or less per composite particle. may be Such finer composite particles tend to provide higher oxygen absorption capacity.

The support may be porous particles capable of supporting the oxygen-absorbing composition. Usually, the oxygen-absorbing substance is supported on the carrier by impregnating the carrier with the oxygen-absorbing composition. As the carrier, for example, one or more selected from activated carbon, zeolite particles, bentonite particles, activated alumina particles, activated clay, calcium silicate particles, and diatomaceous earth can be used.

The oxygen-absorbing composition contains a liquid agent containing an oxygen-absorbing substance, an alkaline compound, a transition metal compound, and an alkali salt of 1,4-dihydro-9,10-dihydroxyanthracene. By using such an oxygen-absorbing composition, a sufficient oxygen-absorbing rate can be obtained in a wide temperature range. This point will be described in detail below.

The liquid agent containing an oxygen-absorbing substance may be an oxygen-absorbing substance that is liquid at room temperature (5 to 35° C.), or may be a solution containing a liquid or solid oxygen-absorbing substance. The oxygen-absorbing substance is the main ingredient of the oxygen-absorbing composition and is a substance that absorbs oxygen. An organic oxygen-absorbing substance is generally a compound that consumes and absorbs oxygen by oxidizing itself.

In this embodiment, an oxygen-absorbing substance that is liquid at room temperature or dissolved in a solvent can be used. Such oxygen-absorbing substances are, for example, one or more compounds selected from the group consisting of glycerin, 1,2-glycol, and sugar alcohols. Specific examples of 1,2-glycols 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, examples of solvents in which the oxygen-absorbing substance dissolves include water; methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, secondary butanol, the third
Lower aliphatic alcohols such as lower butanol and tertiary amyl alcohol; glycols such as ethylene glycol, propylene glycol and trimethylene glycol. As the oxygen-absorbing substance, the compounds described above can be used singly or in combination.

Moreover, even if the oxygen-absorbing substance itself is liquid at room temperature, water can be added to the liquid agent 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, per 100 parts by mass of the oxygen-absorbing substance. The amount of water is usually 0 to 90 parts by weight, and may be 20 to 70 parts by weight, with respect to 100 parts by weight of the carrier.

The amount of the oxygen-absorbing substance is usually 80 to 200 parts by weight, and may be 100 to 180 parts by weight, per 100 parts by weight 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.

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 hydroxyl group is ionized by the alkaline compound, thereby activating the oxygen absorption reaction. In the state of the oxygen-absorbing composition, 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 hydrogen carbonate, sodium hydrogen carbonate, lithium hydrogen carbonate, tribasic sodium phosphate, tribasic potassium phosphate, dibasic sodium phosphate, and dibasic potassium phosphate It may be one or more compounds that are

The amount of the alkaline compound is usually 90 to 300 parts by weight, and may be 150 to 250 parts by weight, per 100 parts by weight of the carrier. When the amount of the alkaline compound is within these ranges, it tends to be easy to obtain an oxygen scavenger having a suitable oxygen absorption capacity.

A 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. 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 transition metal elements include iron, cobalt, nickel, copper, zinc, and manganese. The transition metal compound can 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 include copper(I) chloride, copper(II) chloride, copper(II) sulfate, copper(II) hydroxide, copper(I) oxide, copper(II) oxide, manganese chloride, manganese nitrate, manganese carbonate , and 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, per 100 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 a suitable oxygen absorption capacity.

In this embodiment, it is essential to contain an alkali salt of 1,4-dihydro-9,10-dihydroxyanthracene. Since the oxygen scavenger utilizes the oxidation reaction of an oxygen-absorbing substance, its mechanism is considered to be an ionic reaction (oxidation-reduction reaction) or a radical chain reaction. Therefore, in order to improve the oxygen absorption performance, it is necessary to promote ionization or improve the efficiency of the chain initiation reaction or free radical chain reaction.

In addition, due to the reaction mechanism, the kinetic energy of the molecules decreases in a refrigerated environment, resulting in a decrease in the reaction rate. Therefore, in order to improve the oxygen absorption performance in a refrigerated environment, it is necessary to lower the activation energy of the reaction or use a material that is more easily oxidized than the oxygen-absorbing substance in the refrigerated environment as an oxidation reaction initiator.

Here, 1,4-dihydro-9,10-dihydroxyanthracene is known to perform a reversible oxidation-reduction reaction and acts as a catalyst, that is, it lowers the activation energy of the reaction, making the initiation reaction easier to occur. It is expected. However, when 1,4-dihydro-9,10-dihydroxyanthracene is used in the form of powder, its effect is not exhibited, and its effect is exhibited only when it is used in the form of an alkali salt. This is because 1,4-dihydro-9,10-dihydroxyanthracene has poor solubility in oxygen-absorbing substances. It is believed that this is because it becomes easier to diffuse and permeate into the oxygen-absorbing substance and easily contribute to the reaction. Therefore, an alkali salt solution of 1,4-dihydro-9,10-dihydroxyanthracene is more preferable in terms of acting as a reaction accelerator and increasing the oxygen absorption rate.

The ratio of the alkali salt of 1,4-dihydro-9,10-dihydroxyanthracene is preferably 0.6 to 2.4% by mass of the total amount of the oxygen-absorbing composition. If it is less than 0.6% by mass, it is difficult to obtain sufficient oxygen absorption performance, and if it is 2.4% by mass or more, from the viewpoint of solubility, the alkali salt solution of 1,4-dihydro-9,10-dihydroxyanthracene Since it becomes difficult to use, it may be difficult to obtain an oxygen absorption rate proportional to the amount added.

The alkali salt of 1,4-dihydro-9,10-dihydroxyanthracene is not particularly limited, but specifically, SAQ (1 ,4-dihydro-9,10-dihydroxyanthracene disodium salt 23% aqueous solution, manufactured by Kawasaki Kasei Co., Ltd.).

In the present embodiment, the powder containing the oxygen-absorbing composition supported on the carrier may be granulated and used as a granulated material. Granulation increases the fluidity, so when the oxygen absorber is filled in a small bag, it is possible to prevent the scattering of powder and granules, adhesion to the outside of the small bag, and poor sealing of the small bag due to powder biting. The suitability for filling into sachets is enhanced. In addition, since the fluidity is higher than that of granules, the handling properties such as the stability of transportation and weighing are improved.

The oxygen absorbing composition may further contain a binder so that granules can be easily formed. Specific examples of binders include gum arabic, polyvinyl alcohol, sodium alginate, gelatin and cellulose. The amount of the binder is usually 0 to 30 parts by weight, and may be 10 to 20 parts by weight, per 100 parts by weight of the carrier.

The particle diameter (maximum width) of the granules before adhesion of the inorganic fine particles is not particularly limited, but in order to prevent the work of filling small bags and the occurrence of defects, for example, 0.3 to 8.0 mm, or 0.3 mm More than or equal to less than 5 mm is preferable.

A granulated product composed of the carrier and the oxygen-absorbing composition can be obtained by granulating a mixture containing the carrier and components constituting the oxygen-absorbing composition. Each component constituting the oxygen-absorbing composition may be mixed together or separately. The mixer for mixing is not particularly limited, and may be, for example, a container rotating mixer such as a cylindrical or V-shaped mixer, or a ribbon type, horizontal screw type, paddle type, or planetary motion type. It may be a container fixed type mixer such as. Granulation can be carried out, for example, by an extrusion granulation method using a screen having predetermined apertures.

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 the hydrophilic inorganic substance based on the total mass. Hydrophilic inorganic materials include, for example, hydrophilic silicon dioxide, calcium silicate hydrate, magnesium oxide, and aluminum silicate.

The average particle diameter of the hydrophilic inorganic fine particles is not particularly limited, and may be 0.1 to 100 μm or less, which is the general definition of fine particles. Fine irregularities are usually formed on the surface of the granules, and inorganic fine particles having a small particle size easily enter the recesses on the surface of the granules. As a result, the surface area of the granules is greatly increased, which is considered to contribute to the improvement of the oxygen absorption capacity.

The hydrophilic inorganic fine particles having the average particle diameters exemplified above can be produced by a normal method, and can be obtained by appropriately selecting from commercially available products.

The amount (attachment amount) of the hydrophilic inorganic fine particles adhering to the surface of the granules is preferably 1 part by mass or more with respect to 100 parts by mass of the granules. When the amount of the hydrophilic inorganic fine particles is within these ranges, the appropriate oxygen absorption capacity of the oxygen scavenger is likely to be obtained. The upper limit of the amount of the hydrophilic inorganic fine particles adhering to the surface of the granules is not particularly limited, but is preferably 15 parts by mass or less from the viewpoints of adherence to the surface and cost. It is possible that the single hydrophilic inorganic fine particles not adhering to the granules are mixed with the particles of the oxygen scavenger, but the amount of the single hydrophilic inorganic fine particles is not included in the amount of adhesion. .

The method for attaching the hydrophilic inorganic fine particles to the surface of the granules is not particularly limited. can be obtained by mixing For example, by mixing granules and hydrophilic inorganic fine particles and shaking the resulting mixture, the hydrophilic inorganic fine particles can be adhered to the granules.

The hydrophilic inorganic fine particles adhered to the granules by the method of mixing powders as described above form a relatively thin layer. It generally differs from a tablet with an outer shell obtained by tableting. Specifically, the hydrophilic inorganic fine particles adhering to the surface of the granules can form a layer with a thickness of 1 mm or less, or 0.7 mm or less. When the surface of the composite particles is subjected to elemental analysis by energy dispersive X-ray analysis (EDX analysis), the fact that the layer of hydrophilic inorganic fine particles is thin indicates that the material (oxygen-absorbing substance, alkaline compound or transition metal) constituting the granules It can also be confirmed because the elements contained in the compound) are detected. In general, in the case of the oxygen absorber according to the present embodiment, at least one element contained in the material constituting the granules is detected at a concentration of 0.05 atomic % or more, or 0.1 atomic % or more. It is often done. On the other hand, when a certain thickness of the shell enclosing the granules is formed by tableting, the elements of the material constituting the granules are not substantially detected by EDX analysis.

An oxygen scavenging package according to one embodiment can be mainly composed of the oxygen scavenging agent according to the above embodiment and an air-permeable packaging material containing this oxygen scavenging agent. The air-permeable wrapping material can be appropriately selected from those commonly used in the technical field. Specific examples of air-permeable packaging materials include bags made of a substrate made of perforated plastic film, nonwoven fabric, microporous film, paper, or a combination thereof. This oxygen absorber package can be housed in, for example, various food packaging containers and used for the purpose of maintaining the freshness of food.

A food package according to one embodiment includes the above oxygen absorber package and a food packaging container in which the oxygen absorber package is enclosed. The food packaging container can be appropriately selected from those commonly used in the field of food packaging, and a sealable container is suitable. Food packaging containers include bags, deep drawn packages, tray packages, stretch packages and the like.

(Effect)
(1) The oxygen absorber according to the present embodiment is a porous support and a powder containing an oxygen-absorbing composition supported on the support, wherein the oxygen-absorbing composition contains an oxygen-absorbing substance. The oxygen scavenger containing a liquid agent, an alkaline compound, a transition metal compound and an alkali salt of 1,4-dihydro-9,10-dihydroxyanthracene. Therefore, an oxygen scavenger having an improved oxygen absorption rate compared to the conventional one can be obtained.
(2) In addition, in the oxygen scavenger according to the present embodiment, the alkali salt of 1,4-dihydro-9,10-dihydroxyanthracene is 1,4-dihydro-9,10-dihydroxyanthracene disodium salt. Therefore, the oxygen absorption rate can be increased more effectively. Moreover, it is possible to prevent the material cost of the deoxidizer from increasing.
(3) In addition, in the oxygen absorber according to the present embodiment, the proportion of the alkali salt of 1,4-dihydro-9,10-dihydroxyanthracene is 0.5 to 2.0 mass% of the total amount of the oxygen-absorbing composition. . Therefore, the oxygen absorption rate can be increased more effectively. Moreover, it is possible to prevent the material cost of the deoxidizer from increasing.
(4) The oxygen scavenger according to the present embodiment includes granules containing a porous carrier and an oxygen-absorbing composition carried on the carrier, and hydrophilic a liquid agent containing an oxygen-absorbing substance, an alkaline compound, a transition metal compound, and an alkali salt of 1,4-dihydro-9,10-dihydroxyanthracene. let me Therefore, it is possible to obtain an oxygen absorber granule that has an improved oxygen absorption rate and is highly suitable for filling into small bags.
(5) In addition, in the oxygen absorber according to the present embodiment, the amount of the hydrophilic inorganic fine particles is 1.0 to 10 parts by mass with respect to 100 parts by mass of the granules. Therefore, the oxygen absorption rate can be increased more effectively. Moreover, it is possible to prevent the material cost of the deoxidizer from increasing.
(6) In addition, in the oxygen absorber according to the present embodiment, the mass of each composite particle is in the range of 0.3 to 10.0 mg. Therefore, the oxygen absorption rate can be increased more effectively.

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

[Example 1]
An oxygen absorber composition-1 having the following composition was uniformly mixed in a sealed state to obtain an oxygen absorber of Example 1.
The angle of repose of the mixture obtained in Example 1 was measured to be 44.5°.
For the angle of repose, 150 g of the sample was sprinkled over the cylindrical container from a height of 23 cm for about 3 seconds, and the angle of the powder piled up on the cylindrical container was measured with a digital protractor.

(Oxygen absorber composition-1)
・Activated carbon 100.0 parts ・Glycerin 150.8 parts ・Calcium hydroxide 216.7 parts ・Copper (II) sulfate 45.2 parts ・Water 50.4 parts ・Cellulose 16.7 parts ・1,4-dihydro-9 , 12.4 parts of 10-dihydroxyanthracene disodium salt 23% aqueous solution (SAQ manufactured by Kawasaki Chemical Industry Co., Ltd.)

[Example 2]
An oxygen scavenger of Example 2 was obtained in the same manner as in Example 1, except that oxygen scavenger composition-2 having the following composition was used instead of scavenger composition-1.

(Oxygen absorber composition-2)
・Activated carbon 100.0 parts ・Glycerin 150.8 parts ・Calcium hydroxide 216.7 parts ・Copper (II) sulfate 45.2 parts ・Water 20.8 parts ・Cellulose 16.7 parts ・1,4-dihydro-9 , 10-dihydroxyanthracene disodium salt 23% aqueous solution 51.3 parts (SAQ manufactured by Kawasaki Chemical Industry Co., Ltd.)

[Example 3]
An oxygen scavenger of Example 3 was obtained in the same manner as in Example 1 except that oxygen scavenger composition-3 having the following composition was used instead of scavenger composition-1.

(Oxygen absorber composition-3)
・Activated carbon 100.0 parts ・Glycerin 150.8 parts ・Calcium hydroxide 216.7 parts
・Copper (II) sulfate 45.2 parts ・Water 1.1 parts ・Cellulose 16.7 parts ・1,4-dihydro-9,10-dihydroxyanthracene disodium salt 23% aqueous solution 76.9 parts (SAQ Kawasaki Chemical Industry Co., Ltd.)

[Example 4]
The mixture obtained in Example 1 was granulated by an extrusion granulator equipped with a screen having a screen hole diameter of 1.0 mmφ and a porosity of 22.6% to obtain granular granules. 0.9 g of hydrophilic silicon dioxide particles were then placed in an oxygen barrier bag. 30 g of granulated material was put therein and the bag was heat-sealed. The bag was shaken to obtain the oxygen absorber of Example 4 in which the granules were coated with inorganic fine particles. The angle of repose of the resulting mixture was measured to be 26.8°. Silopage 720 (manufactured by Fuji Silysia Chemical) with an average particle size of 3.9 μm was used as the hydrophilic silicon dioxide (SiO ₂ ) particles. The surface of the oxygen scavenger of Example 4 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, a Cu element derived from copper sulfate constituting the granules was detected at a concentration of 1.06 atomic %. From this, it was confirmed that the hydrophilic inorganic fine particles adhered very thinly to the surface of the granules. A tablet having a core and an outer shell made of the same oxygen-absorbing composition was prepared, and the surface was analyzed by EDX analysis, and Cu element was not detected.

[Example 5]
An oxygen scavenger of Example 5 was obtained in the same manner as in Example 4, except that oxygen scavenger composition-2 was used instead of oxygen scavenger composition-1.

[Example 6]
An oxygen scavenger of Example 6 was obtained in the same manner as in Example 4 except that oxygen scavenger composition-3 was used instead of oxygen scavenger composition-1.

[Example 7]
An oxygen scavenger of Example 7 was obtained in the same manner as in Example 5, except that the amount of hydrophilic silicon dioxide particles was changed to 0.3 g.

[Example 8]
An oxygen scavenger of Example 8 was obtained in the same manner as in Example 5, except that the amount of hydrophilic silicon dioxide particles was changed to 3.0 g.

[Example 9]
An oxygen scavenger of Example 9 was obtained in the same manner as in Example 5, except that the amount of hydrophilic silicon dioxide particles was changed to 4.5 g.

[Comparative Example 1]
Oxygen absorber Composition-4 having the following composition was uniformly mixed in a sealed state to obtain an oxygen absorber of Comparative Example 1.

(Oxygen absorber composition-4)
・Activated carbon 100.0 parts ・Glycerin 150.8 parts ・Calcium hydroxide 216.7 parts ・Copper (II) sulfate 45.2 parts ・Water 60.3 parts ・Cellulose 16.7 parts

[Comparative Example 2]
The mixture obtained in Comparative Example 1 was granulated by an extrusion granulator equipped with a screen having a screen hole diameter of 1.0 mmφ and a porosity of 22.6% to obtain an oxygen absorber of Comparative Example 2.

[Comparative Example 3]
0.9 g of hydrophilic silicon dioxide particles was placed in an oxygen barrier bag, 30 g of the oxygen scavenger of Comparative Example 2 was placed therein, and the bag was heat-sealed. The bag was shaken to obtain an oxygen absorber of Comparative Example 3 in which the granules were coated with inorganic fine particles.

[Comparative Example 4]
An oxygen scavenger of Comparative Example 4 was obtained in the same manner as in Example 4 except that the oxygen scavenger composition-5 having the following composition was used.

(Oxygen absorber composition-5)
・Activated carbon 100.0 parts ・Glycerin 150.8 parts ・Calcium hydroxide 216.7 parts
· Copper sulfate (II) 45.2 parts · Water 60.3 parts · Cellulose 16.7 parts · 1,4-dihydro-9,10-dihydroxyanthracene 17.7 parts

[Comparative Example 5]
An oxygen scavenger of Comparative Example 5 was obtained in the same manner as in Comparative Example 2 using the above oxygen scavenger composition-2.

[Comparative Example 6]
An oxygen scavenger of Comparative Example 6 was obtained in the same manner as in Example 4, except that the hydrophilic silicon dioxide particles were changed to hydrophobic silicon dioxide particles and the above oxygen scavenger composition-2 was used. Cyrophobic 200 (manufactured by Fuji Silysia Chemical) with an average particle size of 3.9 μm was used as the hydrophobic silicon dioxide particles.

<Oxygen absorption capacity>
2.0 g of the oxygen absorbers of Examples 1 to 9 and Comparative Examples 1 to 6 were placed in a bag (length 60 mm, width 60 mm) formed of a perforated packaging material to prepare an oxygen absorber package. A laminated material composed of polyethylene terephthalate/polyethylene/paper/polyethylene was used as the perforated packaging material. The oxygen absorber package was placed in a gas barrier bag together with absorbent cotton (water activity 0.95) soaked with a 44% sucrose aqueous solution. After sealing the bag and injecting 500 mL of air into it, the bag was left in a refrigerated environment (5°C) and an atmosphere of 25°C. After 12 hours, 24 hours, and 48 hours, the oxygen concentration in the bag was measured. A low oxygen concentration means a high oxygen absorption capacity. Table 1 shows the results. What is generally required is an oxygen concentration of 0.1% or less within 24 hours in a room temperature environment, and an oxygen concentration of 0.1% or less within 48 hours in a refrigeration environment.

As can be seen from the results, the powdery oxygen absorber of the oxygen-absorbing composition containing 1,4-dihydro-9,10-dihydroxyanthracene disodium salt as in Examples 1 to 3 was used only in an environment of 25°C. It was found that the oxygen absorption ability was excellent even in a refrigerated environment (5°C). In Comparative Example 1, which did not contain 1,4-dihydro-9,10-dihydroxyanthracene disodium salt, the oxygen absorption capacity was lowered especially in a refrigeration environment (5°C).
In addition, in Example 1 in which the amount of 1,4-dihydro-9,10-dihydroxyanthracene disodium salt added was 0.6% by mass at 25°C, the oxygen concentration after 12 hours was 2.4% by mass. Compared to Example 2, the oxygen absorption performance tends to decrease, and there is almost no difference in oxygen concentration at the addition amount of 2.4% by mass and 3.6% by mass (Examples 2 and 3). was not seen. For this reason, it was found that the range of the addition amount is most preferably 0.6 parts by mass to 2.4 parts by mass from the viewpoint of performance and prevention of increase in material cost.

Furthermore, in the oxygen absorber obtained by granulating the powder of the oxygen absorbing composition, as shown in Examples 4 to 9, oxygen containing 1,4-dihydro-9,10-dihydroxyanthracene disodium salt It was found that a granular oxygen absorber in which hydrophilic inorganic fine particles are supported on granules of the absorbent composition exhibits excellent oxygen absorption capacity not only in a 25°C environment but also in a refrigerated environment (5°C). It was also confirmed that granulation reduces the angle of repose and improves the flowability compared to the case of granules. Furthermore, it was confirmed that the fluidity was further improved by carrying hydrophilic inorganic fine particles. Furthermore, when the adhesion amount of the hydrophilic silicon dioxide particles is increased to 15 parts by mass, there is a tendency for the oxygen absorption performance to decrease after 12 hours. have understood.

On the other hand, in Comparative Example 2 (1,4-dihydro-9,10-dihydroxyanthracene disodium salt was not added to the granules) and Comparative Example 3 (Comparative Example 2 carrying hydrophilic inorganic fine particles) , the oxygen absorption performance decreased. In Comparative Example 5, the oxygen absorption capacity was lower than in Example 2 in both the environment of 25 ° C. and refrigeration (5 ° C.), and Comparative Example 6 (when hydrophobic inorganic fine particles were supported on granules). Also, no change in oxygen absorption capacity was observed.
Further, in Comparative Example 4 in which 1,4-dihydro-9,10-dihydroxyanthracene was added, the oxygen absorption performance was not obtained as compared with Example 5, and the highly soluble 1,4-dihydro-9,10- It was found to be better to use dihydroxyanthracene disodium salt.

Particles of an oxygen-absorbing composition containing 1,4-dihydro-9,10-dihydroxyanthracene disodium salt, and an oxygen-absorbing composition containing 1,4-dihydro-9,10-dihydroxyanthracene disodium salt Granules obtained by granulating the powders of No. 1, 1,4-dihydro-9,10-dihydroxyanthracene disodium salt in both oxygen absorbers, not only in a 25 ° C. environment but also in a refrigerated environment ( 5°C), it clearly shows high oxygen absorption performance.

Although the description herein has been made with reference to a limited number of embodiments, the scope of rights is not limited thereto, and modifications of each embodiment based on the above disclosure will be obvious to those skilled in the art. be.

INDUSTRIAL APPLICABILITY The present invention can be applied to an oxygen absorber that improves the storage stability of foods and the like, an oxygen absorber package and a food package using the same.

Claims (8)

It consists of a porous support and a granule containing an oxygen-absorbing composition supported on the support, wherein the oxygen-absorbing composition comprises a liquid agent containing an oxygen-absorbing substance, an alkaline compound, a transition metal compound, and 1,4 - An oxygen scavenger containing an alkali salt of dihydro-9,10-dihydroxyanthracene. 2. The oxygen absorber according to claim 1, wherein the alkali salt of 1,4-dihydro-9,10-dihydroxyanthracene is 1,4-dihydro-9,10-dihydroxyanthracene disodium salt. 3. The oxygen absorber according to claim 1, wherein the proportion of the alkali salt of 1,4-dihydro-9,10-dihydroxyanthracene is 0.6 to 2.4 mass % of the total amount of the oxygen absorbing composition. Consisting of granules of the powdery granular material,
The oxygen absorber according to any one of claims 1 to 3, comprising composite particles having hydrophilic inorganic fine particles on the surface of the granules. 5. The oxygen absorber according to claim 4, wherein the amount of said hydrophilic inorganic fine particles is 1.0 to 10.0 parts by mass with respect to 100 parts by mass of said granules. 6. The oxygen absorber according to claim 4 or 5, wherein each composite particle constituting said granules has a mass of 0.3 to 10.0 mg. An oxygen scavenger package comprising the oxygen scavenger according to any one of claims 1 to 6 and a breathable packaging material containing the oxygen scavenger. A food package comprising: the oxygen absorber package according to claim 7; and a food packaging container enclosing the oxygen absorber package.