JP2021167217A - Oxygen scavenger package and food package - Google Patents

Abstract

To provide an oxygen scavenger package that does not easily deteriorate in performance due to air exposure.SOLUTION: In an oxygen scavenger package 1 composed of an oxygen scavenger 20 and a breathable packaging material 10 for storing the oxygen scavenger, the oxygen scavenger is a composite particle containing a porous carrier, a granulated product containing an oxygen absorbing composition supported on the carrier, and a hydrophilic inorganic fine particle adhering to the surface of the granulated product. The oxygen absorbing composition comprises a liquid containing an oxygen absorbing substance, an alkaline compound, and a transition metal compound. The packaging material has an air permeability of 5000 to 10000 seconds measured according to JIS P 8117: 2009.SELECTED DRAWING: Figure 1

Description

The present invention relates to an oxygen scavenger package and a food package having the oxygen scavenger package.

As one of the methods for long-term storage of food, there is a method of enclosing an oxygen scavenger in a food packaging container. In this method, food and oxygen scavenger are enclosed in a gas barrier sealed bag or container, oxygen in the sealed container is absorbed by the oxygen scavenger, and the atmosphere in the sealed container is kept substantially oxygen-free. As a result, quality deterioration due to oxidation and growth of bacteria and microorganisms are suppressed.

There are two main types of oxygen scavengers that are commonly used today. An inorganic oxygen scavenger containing iron as a main component and an organic oxygen scavenger containing an ascorbic acid-based oxygen absorbing substance as a main component. These are used properly according to the application and target food, but in recent years there has been an increasing need to apply products to metal detectors, so the demand for organic oxygen scavengers that can be applied to metal detectors has increased. It's coming.

The organic oxygen scavenger has a drawback that the oxygen absorption rate is slower than that of the iron oxygen scavenger. In the use of oxygen scavengers for the purpose of improving food preservation, the oxygen concentration is reduced to less than 0.1% within 24 hours from the viewpoint of suppressing the growth of mold that grows in 24 to 48 hours at the earliest. However, it is not easy to satisfy this condition with an organic oxygen scavenger.
Therefore, in order to increase the oxygen absorption rate in the organic oxygen scavenger, it has been proposed to add a reaction catalyst or reaction accelerator that promotes the oxidation reaction of the oxygen absorbing substance, or to add an alkaline compound to obtain the optimum pH ( For example, see Patent Document 1.).

Japanese Patent No. 3541859

When the oxygen absorption rate of the oxygen scavenger increases, it absorbs oxygen more and more just by leaving it in the air, so it is necessary to quickly enclose the oxygen scavenger in the packaging container and seal it. The inventor evaluated the relationship between the air exposure time and the oxygen absorption rate in an environment of 25 ° C. using the oxygen scavenger package having the configuration described in Patent Document 1, and found that the relationship between the air exposure time and the oxygen absorption rate was 1 hour. Oxygen absorption performance was significantly reduced. It is considered that this is because oxygen was absorbed to the limit in one hour, and it was considered that the expected performance could not be obtained even if this oxygen scavenger package was sealed in the packaging container.
The above-mentioned oxygen scavenger packaging is difficult to handle at the site of food packaging because care must be taken such as keeping it out of contact with the atmosphere until just before encapsulation.

Based on the above circumstances, it is an object of the present invention to provide an oxygen scavenger package in which performance deterioration due to atmospheric exposure is unlikely to occur.

The first aspect of the present invention is an oxygen scavenger package composed of an oxygen scavenger and a breathable packaging material for storing the oxygen scavenger.
The oxygen scavenger is a composite particle containing a porous carrier, a granulated product containing an oxygen absorbing composition supported on the carrier, and hydrophilic inorganic fine particles adhering to the surface of the granulated product.
The oxygen absorbing composition comprises a liquid containing an oxygen absorbing substance, an alkaline compound, and a transition metal compound.
The packaging material has an air permeability of 5000 to 10000 seconds measured according to JIS P 8117: 2009.

The second aspect of the present invention is a food package including the oxygen scavenger package according to the first aspect, the oxygen scavenger package, and a packaging container in which food is enclosed.

According to the present invention, it is possible to provide an oxygen scavenger package that is unlikely to deteriorate in performance due to atmospheric exposure.

It is a figure which shows the oxygen scavenger package which concerns on one Embodiment of this invention. It is a schematic cross-sectional view which shows the layer structure of the packaging material which concerns on the oxygen scavenger packaging body.

Hereinafter, an embodiment of the present invention will be described with reference to FIGS. 1 and 2.
FIG. 1 is a diagram showing an oxygen scavenger package 1 according to the present embodiment. The oxygen scavenger package 1 includes a breathable packaging material 10 and an oxygen scavenger 20 housed in the packaging material 10.

The oxygen scavenger 20 includes a porous support, a powder or granular material containing an oxygen absorbing composition supported on the support, or a granulated product thereof, and hydrophilic inorganic fine particles adhering to the surface of the granulated product. Contains a plurality of composite particles mainly composed of. Here, the powder or granular material is composed of a large number of fine particles and means an aggregate that maintains fluidity as a whole, and the fine particles are fixed to each other to form a single solid tablet as a whole. It does not include what you have done. The number of composite particles contained in the oxygen scavenger 20 may be, for example, 10 or more and 10,000 or less in 1 g of the oxygen scavenger 20.

The mass of the individual composite particles constituting the granulated product of the oxygen scavenger 20 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. It may be. Such fine particles of composite particles tend to provide higher oxygen absorption capacity.

The carrier may be any 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 kinds 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, and a transition metal compound. A sufficient oxygen absorption rate can be obtained by using such an oxygen absorption composition.

The liquid preparation containing an oxygen-absorbing substance is the main agent of the oxygen-absorbing composition and is a substance that absorbs oxygen. An organic oxygen absorber is generally a compound that consumes oxygen by oxidizing itself and absorbs oxygen. For example, one or more compounds selected from the group consisting of glycerin, 1,2-glycol and sugar alcohols. Specific examples of 1,2-glycol include ethylene glycol and propylene glycol.

As the liquid agent, it is preferable to use glycerin which is liquid at room temperature. By using the liquid oxygen absorbing substance, not only the dispersibility with the carrier and the alkaline compound is improved, but also the oxygen absorbing substance is easily transferred to the hydrophilic inorganic fine particles adhering to the surface of the granulated product. As a result, the contact area between the oxygen absorbing substance and the air increases, and the oxygen absorbing performance can be easily obtained.
Water may be added to the liquid preparation containing glycerin for the purpose of improving the dispersibility and transferability to the hydrophilic inorganic fine particles. The amount of water added 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.

The amount of the oxygen absorbing substance is usually 80 to 200 parts by mass and may be 100 to 180 parts by mass with respect to 100 parts by 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.

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 a liquid agent containing an oxygen absorbing substance. The alkaline compound can be an alkali metal or alkaline earth metal hydroxide, carbonate, bicarbonate, tertiary phosphate, secondary phosphate or the like. Specific 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, etc. Consists of sodium carbonate, 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. One or more compounds selected from the group can be exemplified. Of these, calcium hydroxide is particularly preferred. This is because calcium hydroxide forms a soluble complex with glycerin, and the oxidation reaction is easily promoted.

The amount of the alkaline compound is usually 90 to 300 parts by mass and may be 150 to 250 parts by mass with respect to 100 parts by mass 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 an appropriate oxygen absorbing capacity.

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 10 to 70 parts by mass and may be 30 to 50 parts by mass with respect to 100 parts by mass of the carrier. 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.

Generally, when a powder or granular material containing an oxygen absorbing composition supported on a carrier is granulated, the reaction surface area is reduced due to the compression of the powder or granular material, so that the oxygen absorption rate is higher than that before granulation. Will be very slow. In this case, the oxygen absorption performance is less likely to deteriorate due to atmospheric exposure, but when sealed in the package, the required performance of oxygen concentration of 0.1% or less within 24 hours cannot be satisfied.

Here, by adhering the hydrophilic inorganic fine particles to the surface of the granulated product, the oxygen absorbing composition contained in the granulated product is partially transferred to the hydrophilic inorganic fine particles. As a result, the reaction surface area increases and the oxygen absorption rate increases. In addition, since the oxygen absorption composition exists both on the surface layer of the granulated product and inside the granulated product, the oxidation reaction of the surface layer of the granulated product proceeds by exposure to the atmosphere, but the oxygen absorbing composition inside the granulated product is exposed to the atmosphere. It is in a state of being hard to be exposed, and the influence of the oxidation reaction can be reduced.
Therefore, the oxygen scavenger 20 of the present embodiment can suppress the deterioration of the oxygen absorption performance due to atmospheric exposure while maintaining the oxygen absorption rate. Since the amount of the oxygen absorbing composition in the surface layer of the granulated product and the inside of the granulated product changes depending on the particle size of the granulated product, the control of the allowable air exposure time can also be controlled by the particle size of the granulated product.
If the powder is used as it is without granulation, the oxygen absorption performance is greatly reduced even if it is exposed to the atmosphere for a short time due to its high reactivity.

The oxygen absorbing composition may further contain a binder so that the 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 carrier.

The particle size (maximum width) of the granulated product before the inorganic fine particles adhere to it is not particularly limited, but it should be 0.3 mm or more and less than 5.0 mm in order to prevent performance deterioration due to atmospheric exposure and to achieve both oxygen absorption performance. Preferably, it is 0.3 mm or more and 2.0 mm. When the particle size of the granulated product is 5.0 mm or more, the performance deterioration due to atmospheric exposure can be prevented, but the oxygen absorption performance may not satisfy the requirement, which makes control difficult.

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. The means for granulation is not limited as long as the particle size is uniform to some extent, but as a method that can be easily performed, for example, an extrusion granulation method using a screen having a predetermined opening can be performed.

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 hydrophilic inorganic substances based on the total mass thereof. Examples of hydrophilic inorganic substances include hydrophilic silicon dioxide, calcium silicate hydrate, magnesium oxide, and aluminum silicate.

The average particle size of the hydrophilic inorganic fine particles is not particularly limited, and may be 0.1 to 100 μm or less, which is a general definition of fine particles. Fine irregularities are usually formed on the surface of the granulated product, and inorganic fine particles having a small particle size easily enter 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.

The hydrophilic inorganic fine particles having the above-exemplified average particle size can be produced by a usual method, and can also be appropriately selected and obtained from commercially available products.

The amount (adhesion amount) of the hydrophilic inorganic fine particles adhering to the surface of the granulated product is preferably 1 part by mass or more with respect to 100 parts by mass of the mass of the granulated product. When the amount of the hydrophilic inorganic fine particles 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 fine particles adhering to the surface of the granulated product is not particularly limited, but is preferably 15 parts by mass or less from the viewpoint of adhesion to the surface and cost. The single hydrophilic inorganic fine particles that are not attached to the granulated product may be mixed with the particles of the oxygen scavenger, but the amount of the single hydrophilic inorganic fine particles is not included in the above-mentioned adhesion amount. ..

The method of adhering the hydrophilic inorganic fine particles to the surface of the granulated product is not particularly limited, but the granulated powder containing a plurality of granulated products including the carrier and the oxygen absorbing composition and the plurality of hydrophilic inorganic fine particles Can be exemplified as a method of mixing. 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 obtained mixture.

The hydrophilic inorganic fine particles adhering to the granulated product by the method of mixing the powders as described above form a relatively thin layer on the surface of the granulated product. In this respect, the form of the oxygen scavenger 20 of the present embodiment is different from, for example, a tablet having an outer shell obtained by tablet molding. 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. The thin layer of hydrophilic inorganic fine particles means that when the surface of the composite particles is elementally analyzed by energy dispersive X-ray analysis (EDX analysis), the materials (oxygen absorbers, alkaline compounds or transition metals) that make up the granules Since the element contained in the compound) is detected, it can be confirmed. Generally, in the case of the oxygen scavenger 20 according to the present embodiment, in the surface EDX analysis, at least one element contained in the material constituting the granulated product is 0.05 atomic number% (at%) or more, or It is often detected at a concentration of 0.1 at% or higher. 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 rarely detected in the EDX analysis of the surface.

In the oxygen scavenger 20 of the present embodiment, when the oxygen absorbing composition transferred to the hydrophilic inorganic fine particles reacts with the atmosphere, the oxygen absorbing composition contained inside the granulated product is sequentially transferred to the surface layer of the granulated product (sustained release). Therefore, it shows the same oxygen absorption performance as when it is used as a powder. As a result, high oxygen absorption performance is maintained for a long time.

Although the oxygen scavenger 20 has the above-mentioned advantages, it is the same as the conventional one in that it starts absorbing oxygen as soon as it is exposed to the atmosphere. Therefore, if the exposure time until the food is sealed in the packaging container is long, the expected oxygen absorption performance cannot be exhibited.
Considering the actual handling of the oxygen scavenger package in the line for sealing and packaging food, if the expected oxygen absorption performance can be exhibited even after exposure for about 5 hours, the handleability as an oxygen scavenger is very excellent. It can be said that. In consideration of this point, in the present embodiment, the above characteristics are realized by setting the air permeability of the packaging material 10 within a predetermined range.

FIG. 2 is a schematic cross-sectional view showing the layer structure of the packaging material 10. The packaging material 10 includes a fiber layer 11 in which a large number of fibers are entangled, a first resin layer 12 covering the first surface 11a of the fiber layer 11, and a second resin layer 13 covering the second surface 11b of the fiber layer 11. It includes a protective layer 15 attached to the second resin layer 13.

The fiber layer 11 has a structure in which a large number of fibers are entangled, and air can permeate through the first surface 11a and the second surface 11b. Examples of the material of the fiber layer 11 include natural fibers such as pulp and synthetic resins. Specific examples of the fiber layer 11 include various types of paper, non-woven fabric, and the like.
The first resin layer 12 and the second resin layer 13 have a plurality of ventilation holes penetrating in the thickness direction. The mode of the ventilation hole is not particularly limited, and various modes such as a hole shape having a resin-free region and a linear cut (slit) penetrating in the thickness direction can be selected. In FIG. 2, the first resin layer 12 has a hole-shaped ventilation hole 12a, and the second resin layer 13 has a slit-shaped ventilation hole 13a, but this is an example, and both may be reversed. , Both may be hole-shaped or slit-shaped.
The first resin layer 12 and the second resin layer 13 are joined so as to cover the first surface 11a and the second surface 11b, respectively, but the joining mode is not particularly limited. Examples of the joining mode include joining using an adhesive, joining by heat fusion, and the like. The entire surface of the first resin layer 12 and the second resin layer 13 may be bonded, or may have a non-bonded region such as bonding only the peripheral edge portion.
The materials of the first resin layer 12 and the second resin layer 13 are not particularly limited, and various resins can be used.

The protective layer 15 has a function of forming the outer surface of the bag-shaped packaging material 10 and protecting the oxygen scavenger package 1. A plurality of ventilation holes 15a are also formed in the protective layer 15. The mode of the ventilation holes 15a can be appropriately set, and may be the same as or different from the first resin layer 12 and the second resin layer 13.
The material of the protective layer 15 is not particularly limited, and various resins can be used, and polyethylene terephthalate (PET) can be mentioned as a preferable example.
A resin film having a two-layer structure can also be used as the second resin layer 13 and the protective layer 15. By forming the ventilation holes penetrating the resin film, the ventilation holes 13a and the ventilation holes 15a can be produced in the same process. In this case, the ventilation holes 13a and the ventilation holes 15a have substantially the same aspects.
Various known microporous films can also be used as the resin layers 12, 13 and 15.

The packaging material 10 configured as described above has air permeability as the total packaging material 10 by appropriately setting the structure and thickness of the fiber layer 11, the mode of the ventilation holes of the resin layers 12, 13 and 15, and the like. The degree can be in the desired range.
As a result of the inventor's examination, when the Oken type air permeability of the packaging material 10 is 5000 to 10000 seconds, the oxygen scavenger 20 housed and sealed in the packaging material 10 is resistant to long-term atmospheric exposure. It was found that both good oxygen absorption performance after exposure can be achieved.
In the present invention, the "Oken-type air permeability" means the air permeability measured according to JIS P 8117: 2009, and measurable devices are sold by various companies.

When two packaging materials 10 are prepared or one packaging material 10 is bent so that the first resin layers 12 face each other and the peripheral edges are joined, the packaging material 10 can be formed in a bag shape. There is no particular limitation on the mode of joining. When the first resin layer is made of a heat-sealable material, the peripheral portion can be easily joined by heat sealing.
The oxygen scavenger 20 is charged into the packaging material 10 from the opened peripheral edge, and the opened peripheral edge is joined and sealed to complete the oxygen scavenger package 1 of the present embodiment. When the oxygen scavenger package 1 is sealed in a packaging container containing food and sealed, the food package according to the present embodiment is obtained.

In the oxygen scavenger package 1 of the present embodiment configured as described above, oxygen existing outside the package 1 passes through the ventilation holes 15a of the protective layer 15 and the ventilation holes 13a of the second resin layer 13 to form fibers. Reach layer 11. Further, it enters the inside of the packaging material 10 through the ventilation holes 12a of the first resin layer 12 through the gaps between the fibers in the fiber layer 11, and comes into contact with the oxygen scavenger 20.
Since the Oken-type air permeability of the packaging material 10 is 5000 to 10000 seconds, even if the oxygen scavenger package 1 is exposed to the atmosphere, the oxygen in the atmosphere does not excessively contact the oxygen scavenger 20. For 5 to 6 hours, the deterioration of oxygen absorption performance due to atmospheric exposure is suppressed. Therefore, it is possible to efficiently manufacture a food package having excellent handleability and storage stability at a packaging site where food is enclosed in a packaging container.

Since the Oken-type air permeability of the packaging material 10 is 5000 to 10000 seconds, oxygen absorption by the oxygen scavenger 20 in the packaging container of the food package is not excessively suppressed. As a result, in the packaging container of the food package, oxygen is absorbed by the oxygen scavenger 20 and steadily decreases, and the oxygen concentration becomes 0.1% or less within 24 hours after the production of the food package, such as mold and the like. Proliferation is preferably suppressed.

In the food packaging body according to the present embodiment, there is no particular limitation on the mode of the packaging container as long as it can be sealed, and it can be appropriately selected from those usually used in the field of food packaging. Examples of the packaging container include a bag body, a deeply squeezed package body, a tray package body, and a stretch package body.

As described above, the oxygen scavenger package 1 of the present embodiment has the following advantages.
(1) Since the air permeability of the packaging material 10 in which the oxygen scavenger 20 is enclosed is 5000 to 10000 seconds, both suppression of performance deterioration due to atmospheric exposure and suitable oxygen absorption in the food packaging are achieved. ing.
(2) In the oxygen scavenger 20, when the oxygen-absorbing substance is glycerin, the oxygen absorption rate can be increased more effectively.
(3) In the oxygen scavenger 20, when the alkaline compound is calcium hydroxide, the oxygen absorption rate can be increased more effectively.
(4) In the oxygen scavenger 20, when the amount of hydrophilic inorganic fine particles is 1.0 to 15 parts by mass with respect to 100 parts by mass of the granulated product, the oxygen absorption rate can be increased more effectively. can.
(5) In the oxygen scavenger 20, when the mass of the composite particles is in the range of 0.3 to 10.0 mg per composite particle, the oxygen absorption rate can be increased more effectively.

Further, since the packaging material 10 has a structure in which the fiber layer 11 is sandwiched between the resin layers, fine pieces and powders in which the oxygen scavenger is crushed are compared with the packaging material formed only of the resin film having ventilation holes. Is less likely to leak out of the packaging material 10 and prevents the quality of food and the like in the packaging container from being impaired.

The oxygen scavenger package and the food package according to the present embodiment will be further described with reference to Examples. However, the technical scope of the present invention is not limited by the specific contents of these examples.

(Preparation of oxygen scavenger)
The following oxygen scavenger materials are uniformly mixed in a sealed state, and the obtained mixture is granulated by an extrusion granulator provided with a screen having a screen pore diameter of 1.0 mmφ and a pore size of 22.6% to form granules. Granulated material was obtained. When the particle size of the granulated product is changed, it can be obtained by changing the screen pore size.
Next, 0.9 g of hydrophilic silicon dioxide (SiO ₂ ) particles were placed in an oxygen barrier bag, 30 g of granulated material was placed, and the bag was sealed with a heat seal. The bag was shaken to thoroughly mix the contents to obtain an oxygen scavenger whose granulated material was coated with silicon dioxide particles.
As the hydrophilic silicon dioxide particles, silopage 720 (average particle size 3.9 μm) manufactured by Fuji Silysia Chemical Ltd. was used.
From the above, the oxygen scavengers according to Examples 1 to 8 and Comparative Examples 4 and 5 were obtained. The surface of this oxygen scavenger was analyzed by EDX 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 at%, and it was confirmed that hydrophilic inorganic fine particles were very thinly adhered to the surface of the granulated product. ..
For confirmation, a tablet having a central part made of the same oxygen absorbing composition and an outer part made of a mixture of calcium silicate and silicon dioxide was prepared, and the surface thereof was analyzed by EDX. As a result, no Cu element was detected. rice field.

(Oxygen scavenger material)
・ Activated carbon 100 parts ・ Glycerin 145 parts ・ Calcium hydroxide 216.7 parts ・ Copper sulfate (II) 43.6 parts ・ Water 58.0 parts ・ Cellulose 16.7 parts

(Example 9)
The oxygen scavenger according to Example 9 was obtained in the same procedure as in Example 1 except that the amount of hydrophilic silicon dioxide particles was changed to 0.3 g.
(Example 10)
An oxygen scavenger according to Example 10 was obtained in the same procedure as in Example 1 except that the amount of hydrophilic silicon dioxide particles was changed to 3.0 g.
(Example 11)
The oxygen scavenger according to Example 11 was obtained in the same procedure as in Example 1 except that the amount of hydrophilic silicon dioxide particles was changed to 4.5 g.

(Comparative Example 1)
Hydrophilic silicon dioxide was not added to the granulated product, and the oxygen scavenger according to Comparative Example 1 was used as it was.
(Comparative Example 2)
An oxygen scavenger according to Comparative Example 2 was obtained in the same procedure as in Example 1 except that the hydrophilic silicon dioxide particles were changed to hydrophobic silicon dioxide particles.
As the hydrophobic silicon dioxide particles, Silohobic 200 (average particle size 2.7 μm) manufactured by Fuji Silysia Chemical Ltd. was used.
(Comparative Example 3)
The oxygen scavenger material was uniformly mixed to obtain the oxygen scavenger according to Comparative Example 3 as the powder without granulation.

(Preparation of oxygen scavenger packaging)
Vents in a packaging material in which the fiber layer 11 is made of paper having a basis weight of 50 g / m ³ , the first resin layer 12 and the second resin layer 13 are made of polyethylene having a thickness of 25 μm and 15 μm, respectively, and the protective layer is made of PET having a thickness of 12 μm. By changing the modes of 12a, 13a, and 15a, six types of bag-shaped packaging materials having a Wangken-type air permeability of 1000 seconds, 5000 seconds, 6500 seconds, 8000 seconds, 10000 seconds, and 15000 seconds were prepared. The dimensions of the bag-shaped packaging material were all squares with a side of 60 mm when viewed from the front.
2.5 g of the oxygen scavenger according to each example was put into any of the six types of bag-shaped packaging materials and sealed to prepare an oxygen scavenger package according to each example. The prepared oxygen scavenger package was stored in an oxygen-free environment until the time when the food package was prepared. The air permeability of the packaging material used in each example is shown in Table 1.

(Preparation of food packaging)
Cotton wool soaked with 10 ml of a 44% sucrose aqueous solution was placed in a bag-shaped packaging container having an oxygen barrier property. Further, the oxygen scavenger package according to each example was put into the packaging container and sealed in a substantially vacuum state. Then, 500 ml of air was injected into the packaging container with a syringe and then resealed to obtain a food package according to each example. As a result, the water activity in the packaging container became 0.95. The water activity indicates the ratio of free water to the water in the system, and the water activity of 0.95 simulates a state in which high-moisture foods such as cheese, ham, and sausage are stored.
The oxygen scavenger package was either immediately put into the packaging container in an environment of 25 ° C. (zero air exposure time) or put into the packaging container after being exposed to the atmosphere at 25 ° C. for 5 hours. The air exposure time of each example is shown in Table 1.

(Oxygen concentration measurement)
The food packaging of each example was left in an atmosphere of 25 ° C. After 15 hours and 24 hours, the internal oxygen concentration was measured using a needle-type oxygen densitometer.
The results are shown in Table 1.

As shown in Table 1, in each example in which the air permeability of the packaging material was 5000 to 10000 seconds, good oxygen absorption performance was exhibited even after 5 hours of air exposure, and 24 hours after preparation. Cleared the condition that the oxygen concentration was less than 0.1%.

On the other hand, in Comparative Example 4 using a breathable packaging material having an air permeability of 1000 seconds, a decrease in oxygen absorption performance was confirmed after 5 hours of exposure to the atmosphere.
Further, in Comparative Example 5 using a breathable packaging material having an air permeability of 15,000 seconds, the condition that the oxygen concentration was less than 0.1% could not be cleared after 24 hours. It was considered that this was because the air permeability of the packaging material was too small and the oxygen scavenger could not sufficiently contact oxygen.

Further, in Comparative Example 3 in which the oxygen scavenger in the powder state was used, the oxygen absorption performance was significantly lowered by the air exposure for 5 hours even when the packaging material having an air permeability of 5000 to 10000 seconds was used.
In Comparative Example 1 in which the hydrophilic inorganic fine particles were not attached to the granulated product and Comparative Example 2 in which the hydrophobic inorganic fine particles were attached to the granulated product, sufficient oxygen absorption performance could not be obtained even at zero air exposure time.
In Comparative Examples 3 and 4, it was confirmed that when the air exposure time was 0, the condition that the oxygen concentration was 0.1% or less was cleared after 24 hours. Since these oxygen scavenger packages cannot withstand long-term atmospheric exposure, it is presumed that handling will be complicated in the packaging line and the like.

Although one embodiment of the present invention has been described in detail with reference to the drawings, the specific configuration is not limited to this embodiment, and changes and combinations of configurations within a range that does not deviate from the gist of the present invention are also possible. included.

The present invention can be used for oxygen scavenger packages and food packages that improve the storage stability of foods and the like.

1 Oxygen scavenger Package 10 Packaging material 11 Fiber layer 12 First resin layer 12a Ventilation hole 13 Second resin layer 13a Ventilation hole 20 Oxygen scavenger

Claims (7)

An oxygen scavenger package composed of an oxygen scavenger and a breathable packaging material for storing the oxygen scavenger.
The oxygen scavenger
A granulated product containing a porous carrier and an oxygen absorbing composition supported on the carrier, and
It is a composite particle containing hydrophilic inorganic fine particles adhering to the surface of the granulated product.
The oxygen absorbing composition contains a liquid agent containing an oxygen absorbing substance, an alkaline compound, and a transition metal compound.
The packaging material has an air permeability of 5000 to 10000 seconds measured according to JIS P 8117: 2009.
Oxygen scavenger packaging. The packaging material is
With a fiber layer made of paper or non-woven fabric,
It has a resin layer that sandwiches the fiber layer in the thickness direction.
A plurality of ventilation holes are formed in the resin layer.
The oxygen scavenger package according to claim 1. The oxygen-absorbing substance is glycerin,
The oxygen scavenger package according to claim 1. The alkaline compound is calcium hydroxide,
The oxygen scavenger package according to claim 1. The amount of the hydrophilic inorganic fine particles is 1.0 to 15 parts by mass with respect to 100 parts by mass of the granulated product.
The oxygen scavenger package according to claim 1. The mass of the composite particles is 0.3 to 10.0 mg per particle.
The oxygen scavenger package according to claim 1. The oxygen scavenger package according to claim 1 and
The packaging container in which the oxygen scavenger package and food are enclosed, and
To prepare
Food packaging.

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