JP2023034210A - Deoxidizer package and existence confirmation method of the same, and deoxidizer composition - Google Patents

Abstract

The present invention provides an oxygen absorber package, a method for confirming the existence thereof, and an oxygen absorber composition that are detectable by an X-ray foreign matter detector but not detected by a metal detector. [Solution] A non-ferrous oxygen-absorbing substance and at least one inorganic compound (A) selected from the group consisting of copper compounds, zinc compounds, strontium compounds, zirconium compounds, barium compounds, tungsten compounds and bismuth compounds. Oxygen absorber package containing. [Selection figure] None

Description

TECHNICAL FIELD The present invention relates to an oxygen absorber package, a method for confirming the existence thereof, and an oxygen absorber composition.

A method using an oxygen scavenger has been conventionally used as a technique for preserving pharmaceuticals, foods, and the like. In this method, an article to be stored and an oxygen scavenger are sealed in a gas-barrier sealed container, so that the oxygen in the sealed container is absorbed by the oxygen scavenger, and the atmosphere in the sealed container is substantially reduced. Can be kept oxygen-free.

A metal detector or an X-ray foreign matter detector is generally used as a method for checking for foreign matter when an article to be stored and an oxygen scavenger are sealed and packaged. Metal detectors can detect metal foreign matter such as iron and stainless steel, and X-ray foreign matter detectors can also detect foreign matter such as glass and plastic.

On the other hand, as a method for confirming the existence of the oxygen scavenger in the sealed container, it is common to inspect visually or with a metal detector.
However, only iron-based oxygen absorbers can be tested using a metal detector. Inspection using a detector is not applicable. Therefore, there is a problem that the inspection of oxygen scavengers based on non-ferrous oxygen-absorbing substances must rely on visual inspection.

Visual inspection requires a great deal of labor, inevitably fails to be inspected, and there are problems such as impossibility of inspection when opaque packaging materials are used. As a method for solving such problems, Patent Document 1 proposes an oxygen absorbent in which an oxygen absorbent composition containing a reducing organic compound as a main ingredient and stainless steel powder are filled in an air-permeable bag. Since stainless steel powder is used in the oxygen scavenger of Patent Document 1, it is possible to confirm the presence of the oxygen scavenger with a metal detector.

JP-A-2008-212838

However, in the case of the oxygen absorbent of Patent Document 1, since the oxygen absorbent is detected by a metal detector, metal foreign substances such as iron and stainless steel widely used in the production process of food and pharmaceuticals are stored in sealed containers. There is a problem that these foreign substances cannot be detected by the metal detector when they are mixed in the inside.

Therefore, the present invention provides an application in which a metal detector is used to inspect metal foreign matter such as iron and stainless steel, and when an oxygen absorber containing a non-ferrous oxygen-absorbing substance as a main component is used, an article to be stored and the oxygen absorber An oxygen absorber package and its existence confirmation that enable confirmation of the presence of the oxygen absorber when enclosing and sealing packaging with an X-ray foreign matter detector, and can also be used in combination with foreign matter confirmation with a metal detector. It is an object to provide a method, as well as an oxygen scavenger composition.

As a result of intensive studies, the present inventors have focused on inspection by an X-ray foreign matter detector as a new inspection method that does not rely on visual inspection or a metal detector, regarding a method for confirming the presence of an oxygen absorber package. The present inventors have found that the above problems can be solved by obtaining an oxygen absorber package which is not detected by a machine but can be detected by an X-ray foreign matter detector, and have completed the present invention.

That is, the gist and configuration of the present invention are as follows.
[1] Contains a nonferrous oxygen-absorbing substance and at least one inorganic compound (A) selected from the group consisting of copper compounds, zinc compounds, strontium compounds, zirconium compounds, barium compounds, tungsten compounds and bismuth compounds , an oxygen absorber package.
[2] The oxygen absorber package, wherein the oxygen absorber package according to the above [1] is inspected to confirm that the oxygen absorber package is enclosed using an X-ray foreign matter detector. How to confirm the existence of a body.
[3] Contains a non-ferrous oxygen-absorbing substance and at least one inorganic compound (A) selected from the group consisting of copper compounds, zinc compounds, strontium compounds, zirconium compounds, barium compounds, tungsten compounds and bismuth compounds The oxygen scavenger composition.

According to the present invention, it is possible to provide an oxygen absorber package, a method for confirming the presence thereof, and an oxygen absorber composition that are detectable by an X-ray foreign matter detector but not detectable by a metal detector. According to the oxygen absorber package of the present invention, when the article to be stored and the oxygen absorber package are sealed and packaged, the presence of the oxygen absorber package in the sealed container is confirmed by X. It is possible to use a wire foreign matter detector, and simultaneously check for foreign matter by a metal detector as an inspection for metallic foreign matter contamination in the sealed container.

FIG. 1 is an X-ray photograph when the packaging bag containing the oxygen absorber package of Example 10 and the polished rice is passed through an X-ray foreign matter detector.

[Oxygen absorber package]
The oxygen absorber package of the present invention comprises a nonferrous oxygen-absorbing substance and at least one inorganic compound selected from the group consisting of a copper compound, a zinc compound, a strontium compound, a zirconium compound, a barium compound, a tungsten compound and a bismuth compound. and the compound (A).

Since the oxygen absorber package of the present invention has the above structure, it can be detected by an X-ray foreign matter detector without being detected by a metal detector.
The reason why the oxygen absorber package of the present invention exhibits the above effects is considered as follows.
Both the nonferrous oxygen-absorbing substance contained in the oxygen absorber package of the present invention and the predetermined inorganic compound (A) are substances that cannot be detected by a metal detector. On the other hand, the predetermined inorganic compound (A) is a substance with high detection sensitivity to an X-ray foreign object detector. Although it is not detected by the machine, it is considered that it can be detected by the X-ray foreign object detector.

Since the oxygen absorber package of the present invention can be detected by an X-ray foreign matter detector, the presence or absence of the oxygen absorber can be easily and accurately confirmed by non-destructive inspection using the X-ray foreign matter detector. it becomes possible to As a result, it is possible to prevent forgetting to insert the oxygen absorber package, which is useful for reducing defective products, and the inspection process can be labor-saving because manual visual confirmation can be automated.
Further, according to the oxygen absorber package of the present invention, foreign matter confirmation using a metal detector can be used in combination with the inspection for metal foreign matter contamination in the product. That is, since the oxygen absorber package of the present invention is not detected by a metal detector, it does not hinder the inspection of foreign matter contamination using a metal detector, and only foreign matter such as iron and stainless steel can be accurately detected. It is thought that foreign matter detection accuracy will improve.

In this specification, the oxygen absorber package is selected from the group consisting of nonferrous oxygen-absorbing substances, copper compounds, zinc compounds, strontium compounds, zirconium compounds, barium compounds, tungsten compounds and bismuth compounds. It means that at least one inorganic compound (A) is packaged with a packaging material.
Each component and the like will be described below.

<Non-ferrous oxygen-absorbing substance>
The nonferrous oxygen-absorbing substance used in the present invention is a nonferrous substance that absorbs oxygen and is not limited as long as it is a substance that is not detected by a metal detector. isoascorbic acid), ascorbic acids such as erythorbate; polyhydric alcohols such as glycerin, ethylene glycol, propylene glycol and glyceric acid; polyhydric phenols such as gallic acid and catechol; a compound having an unsaturated double bond; These may be used individually by 1 type, and may use 2 or more types together.

Among them, the nonferrous oxygen-absorbing substance is preferably at least one selected from the group consisting of ascorbic acid, ascorbate, erythorbic acid, erythorbate, glycerin, glyceric acid, gallic acid and catechol. In particular, ascorbic acids generate carbon dioxide as they absorb oxygen, so the volume of gas in the closed container is kept constant, so it is possible to suppress the deformation of the closed container and maintain the shape of the object to be stored. is more preferable in that

The content of the nonferrous oxygen-absorbing substance per oxygen absorber package is preferably 0.1 g or more, more preferably 1 g or more, from the viewpoint of obtaining a sufficient oxygen absorption effect, and is economical. From the viewpoint, it is preferably 100 g or less, more preferably 50 g or less. The content of the non-ferrous oxygen-absorbing substance per oxygen absorber package is preferably 0.1 g or more and 100 g or less, more preferably 0.1 g or more and 50 g or less, and still more preferably 1 g or more. 50 g or less. In addition, the content of the non-ferrous oxygen-absorbing substance is preferably 1% by mass or more and 70% by mass or less in the contents of the oxygen absorber package (the portion excluding the packaging material) from the viewpoint of oxygen absorption performance, It is more preferably 10% by mass or more and 50% by mass or less, and still more preferably 20% by mass or more and 50% by mass or less.

<Inorganic compound (A)>
The inorganic compound (A) used in the present invention is at least one selected from the group consisting of copper compounds, zinc compounds, strontium compounds, zirconium compounds, barium compounds, tungsten compounds and bismuth compounds. Such an inorganic compound (A) is a substance that cannot be detected by a metal detector but can be detected by an X-ray foreign matter detector. In some cases, it plays the role of a detectable marker. The inorganic compound (A) is preferably at least one compound selected from the group consisting of zinc compounds, strontium compounds, zirconium compounds, barium compounds and bismuth compounds from the viewpoints of enhancing the X-ray shielding effect and easy availability. be.

The inorganic compound (A) is not particularly limited as long as it is not detected by a metal detector and can be detected by an X-ray foreign object detector. Oxides, chlorides, and the like can be used. In addition, from the viewpoint of enhancing the X-ray shielding effect and from the viewpoint of easy availability, copper oxide (CuO), copper hydroxide (Cu(OH) ₂ ), zinc oxide (ZnO), strontium carbonate (SrCO ₃ ), strontium oxide (SrO), zirconium oxide (ZrO ₂ ), barium sulfate (BaSO ₄ ), tungsten boride (WB), bismuth oxide (Bi ₂ O ₃ ), and the like can be preferably used. Among them, barium sulfate and zinc oxide are more preferable.

The content of the inorganic compound (A) per oxygen absorber package is preferably 0.01 g or more, more preferably 0.01 g or more, from the viewpoint of enhancing the X-ray shielding effect and improving the detection accuracy of X-ray foreign matter detection. is 0.02 g or more, more preferably 0.05 g or more, still more preferably 0.10 g or more, still more preferably 0.30 g or more, and from the viewpoint of economy, preferably 5.0 g or less , more preferably 3.0 g or less, and still more preferably 1.0 g or less. The content of the inorganic compound (A) per oxygen absorber package is preferably 0.01 g or more and 5.0 g or less, more preferably 0.02 g or more and 5.0 g or less, and still more preferably. is 0.02 g or more and 3.0 g or less, more preferably 0.05 g or more and 3.0 g or less, still more preferably 0.10 g or more and 3.0 g or less, still more preferably 0.30 g or more and 1.0 g or less. 0 g or less. In addition, the content of the inorganic compound (A) is preferably 0.001% by mass or more and 50% by mass or less, more preferably 0.001% by mass or more and 40% by mass or less, still more preferably 0.001% by mass or more and 20% by mass or less, and even more preferably 0 01% by mass or more and 10% by mass or less, more preferably 0.4% by mass or more and 10% by mass or less.

The shape of the inorganic compound (A) is not particularly limited, but examples thereof include powder, granules, granules, and the like. Among them, from the viewpoint of easy availability, it is preferably at least one selected from the group consisting of powder and granules, and more preferably granules from the viewpoint of enhancing the X-ray shielding effect and handling properties. .

The average particle diameter (D50) of the inorganic compound (A) is preferably 1 μm or more, more preferably 50 μm or more, from the viewpoint of enhancing the X-ray shielding effect and improving the detection accuracy of X-ray foreign matter detection. It is preferably 100 µm or more, more preferably 300 µm or more, still more preferably 500 µm or more, still more preferably 1000 µm or more, and from the viewpoint of handling and filling properties, preferably 5000 µm or less, more preferably is 4000 μm or less, more preferably 3000 μm or less, still more preferably 2500 μm or less. The average particle diameter (D50) of the inorganic compound (A) is preferably 1 μm or more and 5000 μm or less, preferably 1 μm or more and 4000 μm or less, more preferably 100 μm or more and 3000 μm or less, and still more preferably 300 μm or more and 2500 μm. It is below.
The average particle size (D50) of the inorganic compound (A) can be measured by the method described in Examples.

The loose bulk density of the inorganic compound (A) is preferably 0.5 g/mL or more, more preferably 1.0 g/mL, from the viewpoint of enhancing the X-ray shielding effect and improving the detection accuracy of X-ray foreign matter detection. or more, more preferably 1.2 g/mL or more, and from the viewpoint of availability, preferably 10.0 g/mL or less, more preferably 5.0 g/mL or less, and still more preferably 3 .5 g/mL or less. The loose bulk density of the inorganic compound (A) is preferably 0.5 g/mL or more and 10.0 g/mL or less, more preferably 1.0 g/mL or more and 5.0 g/mL or less, and still more preferably 1 .2 g/mL or more and 3.5 g/mL or less.
The loose bulk density of the inorganic compound (A) can be measured by the method described in Examples.

The form of existence of the inorganic compound (A) is not limited as long as it is contained in the oxygen absorber package. Specifically, the inorganic compound (A) may be contained in the oxygen absorber composition described later, or may be present inside the packaging material by coating, printing, or the like. From the viewpoint of production cost, the inorganic compound (A) is preferably contained in the oxygen absorber composition.

<Other ingredients>
In the oxygen absorber package of the present invention, in addition to the nonferrous oxygen-absorbing substance and the inorganic compound (A) described above, other may contain ingredients. Specific examples include alkaline substances, catalysts, carriers, swelling agents, exothermic inhibitors, water, and odor adsorbents. In particular, it preferably contains at least one selected from the group consisting of an alkaline substance, a catalyst, a carrier, a swelling agent, an exothermic suppressant and water, and more preferably contains an alkaline substance, a catalyst and a carrier.

(alkaline substance)
Alkaline substances are used for the purpose of rapidly advancing the oxidation reaction of non-ferrous oxygen-absorbing substances and controlling the reaction field in the alkaline region. , a salt composed of a weak acid and a strong base, and the like. Among them, the alkaline substance is preferably at least one selected from the group consisting of alkali metal carbonates, alkali metal hydroxides and alkaline earth metal hydroxides. Further, the alkaline substance is selected from the group consisting of alkali metal carbonates and alkali metal hydroxides from the viewpoint of water solubility when salted with a non-ferrous oxygen-absorbing substance such as ascorbic acid. is more preferable.

As the alkali metal carbonate, water-soluble alkali metal carbonates such as sodium carbonate, sodium hydrogencarbonate and sodium carbonate hydrate are suitably used, with sodium carbonate being particularly preferred.
Examples of alkali metal hydroxides include potassium hydroxide and sodium hydroxide, with sodium hydroxide being preferred.
Alkaline earth metal hydroxides include calcium hydroxide and magnesium hydroxide.

From the viewpoint of neutralizing the hydrolysis product, the content of the alkaline substance in one oxygen absorber package is preferably an equimolar amount with respect to the molar amount of the non-ferrous oxygen-absorbing substance. In addition, the content of the alkaline substance is preferably 1% by mass or more and 15% by mass or less, more preferably 5% by mass or more and 10% by mass or less in the contents of the oxygen absorber package (the portion excluding the packaging material). more preferably 8% by mass or more and 10% by mass or less.

(catalyst)
The catalyst has a role of improving the oxygen absorption amount and the oxygen absorption rate, and examples thereof include transition metal catalysts.
The transition metal catalyst is preferably a transition metal salt.
The transition metal salt is preferably at least one transition metal salt selected from the group consisting of Cu, Fe, Co, Ni, Cr and Mn, and more preferably Mn and Fe in consideration of oxygen absorption performance and safety. is at least one transition metal salt selected from the group consisting of, more preferably Fe.
As transition metal salts, for example, inorganic salts such as sulfates, chloride salts and nitrates, organic salts such as fatty acid salts and acetylacetone metal salts, and the like can be suitably used, and sulfates are more preferable.

The content of the catalyst is preferably 0.5% by mass or more and 5% by mass or less, more preferably 1% by mass or more and 5% by mass or less, in the contents of the oxygen absorber package (the portion excluding the packaging material). more preferably 2% by mass or more and 4% by mass or less. Within the above range, a sufficient catalytic effect is obtained and the metal detector does not detect the content.

(Carrier)
The carrier supports the non-ferrous oxygen-absorbing substance and the catalyst, and has a role of improving the oxygen absorption amount and oxygen absorption speed. silicate; zeolite and the like. Among them, activated carbon is preferred.
Activated carbon not only serves as a carrier, but also has a function of suppressing the generation of odor, and may be any of wood, coconut shell, coal, and the like.

The content of the carrier is preferably 1% by mass or more and 20% by mass or less, more preferably 4.5% by mass or more and 10% by mass or less, in the contents of the oxygen absorber package (the portion excluding the packaging material). and more preferably 6% by mass or more and 10% by mass or less.

(swelling agent)
The swelling agent is a substance that swells with water and has a caking function to retain the shape of the granules. The swelling agent is preferably used in a substantially dry state or in a semi-swollen or swollen state after absorbing a small amount or necessary amount of water.

The swelling agent is not particularly limited as long as it is a generally known swelling agent, and known swelling agents, binders, adhesives, and binders used in foods and the like can be used.
Inorganic swelling agents include clay minerals such as sodium bentonite, calcium bentonite and sodium montmorillonite. Organic swelling agents include organic bentonite; natural products such as defatted frozen tofu, agar, starch, dextrin, gum arabic, gelatin, and casein; semi-synthetic products such as hydroxyethylated starch; and synthetic products such as water-insoluble polyvinyl alcohol and polyvinyl methyl ether. One of the swelling agents described above can be used alone, or two or more of them can be used in combination, if necessary. Moreover, you may use a commercial item as these swelling agents.

Among them, the swelling agent is preferably at least one selected from the group consisting of clay minerals and cellulosic semi-synthetic products.
Clay minerals are preferable because they are inexpensive and excellent in performance. Clay minerals, also known as inorganic soaps, function as lubricants. Clay minerals swollen with water are also known to exhibit high thixotropy and are preferred because they also exhibit caking properties.
Cellulosic semi-synthetic products are also preferred because they exhibit excellent swelling properties.
Among such clay minerals and cellulose-based semisynthetic products, bentonites such as calcium bentonite and sodium bentonite, and cellulose-based products such as carboxymethyl cellulose, sodium carboxymethyl cellulose, and calcium carboxymethyl cellulose are used because they are inexpensive and have strong caking power. Semi-synthetics are preferred.
From the above viewpoint, the swelling agent more preferably contains at least one selected from the group consisting of carboxymethylcellulose calcium, carboxymethylcellulose sodium, calcium bentonite and sodium bentonite.

The average particle size of the swelling agent is preferably 0.001 μm or more and 10 μm or less, more preferably 0.01 μm or more and 1.0 μm or less, from the viewpoint of suppressing the generation of dust and the viewpoint of the caking function.

The content of the swelling agent is not particularly limited. % by mass or less, more preferably 2.0% by mass or more and 10% by mass or less, and even more preferably 2.5% by mass or more and 5% by mass or less. Moreover, it is preferably 1 part by mass or more and 20 parts by mass or less, more preferably 5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the non-ferrous oxygen-absorbing substance. If the content of the swelling agent is within this range, the shape of the contents of the oxygen absorber package (the oxygen absorber composition) can be easily maintained, and the ratio of the water retention agent does not become too small. The moisture supply to the absorbent material does not decrease, and the oxygen absorption tends to be higher.

(Exothermic suppressant)
The exothermic inhibitor plays a role in suppressing heat generation when the nonferrous oxygen-absorbing material absorbs oxygen, and is preferably crystalline thermoplastic resin particles.
Normally, non-ferrous oxygen-absorbing substances generate heat as they absorb oxygen, and the temperature rises. Also, problems such as swelling and deformation of packaging materials may occur. In addition, there is a possibility of local heating due to heat accumulation during mass disposal.
Since the crystalline thermoplastic resin particles have a crystalline portion and a melting point, when added to the oxygen absorber, the heat of fusion is locally taken away during melting, thereby suppressing the heat generation.

The heat of fusion per unit mass of the thermoplastic resin forming the crystalline thermoplastic resin particles is preferably 190 mJ/mg or more. Moreover, the melting point of the thermoplastic resin is preferably 80° C. or higher and 150° C. or lower.
The degree of crystallinity of the thermoplastic resin forming the crystalline thermoplastic resin particles is preferably 50% or higher, more preferably 60% or higher, and still more preferably 65% or higher.
The degree of crystallinity of a thermoplastic resin is a value calculated by a density method.

The crystalline thermoplastic resin particles include polyolefin particles, polyester particles, polyamide particles and the like, preferably polyolefin particles and polyester particles, and more preferably polyolefin particles.
Polyolefin particles are preferably polyethylene particles or polypropylene particles, more preferably polyethylene particles.

The crystallinity of polyethylene constituting the polyethylene particles is preferably 50% or more, more preferably 60% or more, and still more preferably 65% or more.
The degree of crystallinity of polyethylene is a value calculated by the density method [JIS K6922-1: 2018, and Polyethylene Resin, Plastic Material Course, Nikkan Kogyo Shimbun, 22 (1969)].
Polyethylene is a crystalline polymer, and the crystalline portion is structurally more stable than the amorphous portion. Therefore, the higher the degree of crystallinity, the higher the density, which is preferable. Also, the polyethylene used in the present invention may be copolymerized with other monomers such as propylene, 1-butene and the like.
The heat of fusion per unit mass of polyethylene is preferably 190 mJ/mg or more, and the melting point is preferably 80° C. or higher and 150° C. or lower.

The content of the crystalline thermoplastic resin particles is not particularly limited, but is preferably 1% by mass or more and 20% by mass or less, more preferably 2% by mass, in the contents of the oxygen absorber package (the portion excluding the packaging material). .5% by mass or more and 10% by mass or less, more preferably 3% by mass or more and 6% by mass or less.

The oxygen absorber package of the present invention may contain an iron-based oxygen-absorbing substance such as iron powder within a range that does not interfere with the detection of foreign substances such as iron and stainless steel, that is, within a range that cannot be detected by a metal detector. . The content of the iron-based oxygen-absorbing substance in one oxygen absorber package is preferably 0 g or more and 0.05 g or less, more preferably 0 g or more and 0.001 g or less, and still more preferably 0 g. That is, it is preferable that the oxygen absorber package of the present invention does not substantially contain an iron-based oxygen-absorbing substance.

<Packaging material>
The oxygen absorber package of the present invention comprises a packaging material containing the non-ferrous oxygen-absorbing substance and the inorganic compound (A) described above.

(packaging material)
The packaging material is not particularly limited as long as it is a packaging material used as an oxygen absorber, but it is preferable to use a highly breathable packaging material from the viewpoint of obtaining sufficient oxygen absorption performance. A bag shape by pasting together, a bag shape by pasting one breathable packaging material and one non-breathable packaging material, one breathable packaging material is folded, and the folding part For example, the edges excluding the edge portions are sealed to form a bag shape.

Here, when the air-permeable packaging material and the non-air-permeable packaging material have a square shape, the packaging material is a bag-shaped material obtained by stacking two air-permeable packaging materials and heat-sealing the four sides of the packaging material. , A sheet of breathable packaging material and a sheet of non-breathable packaging material are superimposed and heat-sealed on four sides to form a bag. A case in which the sides are heat-sealed to form a bag is exemplified. Alternatively, the packaging material may be a bag-like material obtained by forming a tubular air-permeable packaging material into a tubular shape and heat-sealing both ends and a trunk portion of the tubular body.

The shape of the packaging material is preferably one selected from the group consisting of bag-like, three-side-sealed, four-side-sealed, stick-like, cylindrical and box-like, and more preferably stick-like and cylindrical. It is one selected from the group consisting of shape and box shape.
Moreover, when the packaging material is a three-sided seal, the size thereof is, for example, 10 mm or more and 120 mm or less in length and 10 mm or more and 120 mm or less in width.

(Breathable packaging material)
As breathable packaging materials, in particular packaging materials which are permeable to oxygen and carbon dioxide are selected. For example, papers such as Japanese paper, western paper, rayon paper, nonwoven fabrics using various fibers such as fibers from pulp, cellulose, and synthetic resins, plastic films or perforated products thereof, or stretched after adding calcium carbonate. Examples include a microporous film, and a laminate obtained by laminating two or more selected from these films. Examples of plastic films include films such as polyethylene terephthalate, polyamide, polypropylene, and polycarbonate, and films such as polyethylene, ionomer, polybutadiene, ethylene acrylic acid copolymers, ethylene methacrylic acid copolymers, and ethylene vinyl acetate copolymers as sealing layers. A laminated film or the like can be used. As such an air-permeable packaging material, a polyethylene nonwoven fabric or a laminate of a nonwoven fabric and a microporous film is preferable.

Among them, those having an air resistance of 600 seconds or less, more preferably 90 seconds or less, as measured by the Gurley tester method are preferably used. Here, the air resistance means a value measured by the method of JIS P8117 (1998). More specifically, it refers to the time required for 100 mL of air to permeate the air-permeable packaging material using a Gurley densometer (manufactured by Toyo Seiki Seisakusho Co., Ltd.).

As a method for imparting air permeability, various methods such as perforation using cold needles and hot needles can be employed. When air permeability is imparted by perforation, the air permeability can be freely adjusted by the diameter, number, material, etc. of the holes to be perforated.

Moreover, the thickness of the laminated film is preferably 50 μm or more and 300 μm or less, and particularly preferably 60 μm or more and 250 μm or less. In this case, compared with the case where the thickness is outside the above range, the packaging material can be made to have strength, heat-sealing property, and packaging suitability.

(non-breathable packaging material)
Impermeable packaging materials include packaging materials having aluminum foil and the like. For example, when one side of the oxygen absorber package is made of a breathable packaging material and the other side is made of a non-breathable packaging material, oxygen can be absorbed only from one side.

The packaging material contains the non-ferrous oxygen-absorbing substance and the inorganic compound (A) described above and other components added as necessary, but the amount of these contents is not particularly limited. , can be appropriately adjusted according to the method of use of the oxygen absorber package. For example, from the viewpoint of versatility, oxygen absorption performance, and productivity of the oxygen absorber package, the content capacity per oxygen absorber package is preferably 0.1 g or more and 100 g or less, and more preferably. is 0.5 g or more and 50 g or less, more preferably 1 g or more and 20 g or less, still more preferably 3 g or more and 10 g or less.

<Method for manufacturing oxygen absorber package>
The method for producing the oxygen absorber package of the present invention is not particularly limited, and the above-described substances may be collectively mixed by a known method to form an oxygen absorber composition and then enclosed in a packaging material, or the above substances may be mixed together. may be prepared separately and individually enclosed in packaging materials. For example, it can also be produced by weighing and packaging separately using a two-type filling type packaging machine. Alternatively, only the inorganic compound (A) may be present inside the packaging material by coating, printing, or the like, and other substances may be enclosed in the packaging material.

When the shape of the inorganic compound (A) is powder or granules, from the viewpoint of obtaining a high X-ray shielding effect with a small amount added, the inorganic compound (A) is not mixed with other substances, It is preferable to individually enclose them in a packaging material, and it is preferable that the inorganic compound (A) is unevenly distributed in one place in the oxygen absorber package.
Generally, the higher the density of the object, the greater the X-ray shielding effect. Therefore, when the shape of the inorganic compound (A) is powder or granules, the inorganic compound (A) is unevenly distributed in one place in the oxygen absorber package, and is mixed with other materials. As compared with the case where the inorganic compound (A) is uniformly dispersed, a portion having a high existence density of the inorganic compound (A) is locally formed, so that the X-ray shielding effect of this portion is increased, and X-ray detection becomes easier.

<Application of oxygen absorber package>
The oxygen absorber package of the present invention can be suitably used in applications where conventional oxygen absorbers have been used. For example, by enclosing and sealing the article to be stored and the oxygen absorber package in a gas barrier sealed container, the oxygen in the sealed container is absorbed by the oxygen absorber, and the atmosphere in the sealed container is substantially reduced. Can be kept oxygen-free. Examples of articles to be preserved include medicines and foods.

[Method for confirming existence of oxygen absorber package]
The oxygen absorber package of the present invention can be detected by an X-ray foreign matter detector by having the above configuration. For this reason, the product in which the oxygen absorber package is enclosed can be inspected to confirm that the oxygen absorber package has been enclosed using an X-ray foreign matter detector.
According to such a method for confirming the existence of the oxygen absorber package, it is possible to confirm the existence of the oxygen absorber package by non-destructive inspection using an X-ray foreign matter detector. As a result, it is possible to prevent forgetting to insert the oxygen absorber package into the product, which helps to reduce product defects, and also eliminates the need for manual visual confirmation, thereby saving labor in the inspection process.

A specific example of the product enclosing the oxygen absorber package is a package obtained by enclosing the oxygen absorber package and an article to be stored in a packaging container.
The articles to be stored are not particularly limited, but include, for example, medicines and foods. Foods include, for example, sweets, rice such as polished rice and rice cakes, meats, noodles, and fish.
Normally, when confirming the presence of an oxygen absorber in a packaging container, the thicker the article to be stored, the easier it is for the article to block X-rays. X-ray detection becomes difficult. However, since the oxygen-removing package of the present invention itself is easily detectable by X-rays, even if the article to be stored is relatively thick, it can be sufficiently detected by an X-ray foreign matter detector. Therefore, according to this method, it can be suitably used for preserving thick articles for which it has been difficult to detect oxygen scavengers. It is more suitable for the above.
The packaging container is not particularly limited, but from the viewpoint of effectively maintaining the oxygen removing performance of the oxygen absorber package, it is preferably a gas-barrier hermetically sealed container.

The X-ray foreign matter detector used for the confirmation inspection is not particularly limited, and a known inspection device can be used. A specific inspection method can be performed by the method described in Examples.

[Oxygen absorber composition]
The oxygen absorber composition of the present invention comprises a nonferrous oxygen-absorbing substance and at least one inorganic compound selected from the group consisting of a copper compound, a zinc compound, a strontium compound, a zirconium compound, a barium compound, a tungsten compound and a bismuth compound. and the compound (A).
Such an oxygen absorber composition is not detectable by a metal detector, but can be detected by an X-ray foreign matter detector, and thus is suitably used as the content of the oxygen absorber package.

The nonferrous oxygen-absorbing substance, the predetermined inorganic compound (A) and other components are as described above.
In particular, the content of the inorganic compound (A) in the oxygen absorber composition is preferably 0.001% by mass or more and 50% by mass or less from the viewpoint of the balance between the detection sensitivity of the X-ray foreign matter detector and the oxygen absorption performance. , more preferably 0.001% by mass or more and 40% by mass or less, still more preferably 0.001% by mass or more and 20% by mass or less, still more preferably 0.01% by mass or more and 10% by mass or less Yes, more preferably 0.4% by mass or more and 10% by mass or less.

Moreover, the method for producing the oxygen absorber composition is not particularly limited, and is substantially the same as the method for producing the oxygen absorber package described above. That is, the oxygen absorber composition may contain a non-ferrous oxygen-absorbing substance and a predetermined inorganic compound (A), and is produced by collectively mixing the above substances by a known method. Alternatively, the above-mentioned substances may be separately prepared, individually enclosed in a packaging material, and mixed in the packaging material to form the oxygen absorber composition.

Although the embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments, and includes various aspects within the scope of the present invention including the concept of the present invention and the scope of claims. can be modified to

EXAMPLES Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these. In addition, various measurements and evaluations in each Production Example, Example and Reference Example were carried out as follows.

<Average particle size (D50)>
The average particle size (D50) was measured using an image-type particle size distribution analyzer ("Camsizer X2" manufactured by Retsch Technology).
If the average particle size (D50) could not be measured by the image-type particle size distribution measuring device, it was dispersed in water and measured by a laser diffraction/scattering particle size distribution measuring device ("LA" manufactured by Horiba, Ltd.). -960V2 series”) was used to measure the average primary particle size. For the average particle size (D50) measured by this measurement, the values in Table 1 are indicated with ( ).

<Loose bulk density>
The loose bulk density was measured by the following procedure using a powder property evaluation device "Powder Tester PT-X".
(1) Prepare a cylindrical container having an opening, a depth of 4 cm and a volume of 50 cm ³ , and measure the empty weight of the container.
(2) The inorganic compound to be measured is gently sieved into the container and dosed until there is a uniform mound extending upwards from the container over the entire opening of the container.
(3) After the mountain portion of the inorganic compound is worn off, the total weight of the container and the inorganic compound is measured.
(4) Calculate the loose bulk density according to the following formula (I).
Loose bulk density [g/cm ³ ]={(whole weight [g]−empty weight [g])}/container volume [cm ³ ] (I)

<Metal detection test>
The resulting three oxygen absorber packages were passed through a metal detector (“META-HAWK II” manufactured by System Square Co., Ltd.) to conduct a magnetic detection test for iron and stainless steel.
The presence or absence of metal detection was determined according to the following evaluation criteria.
(Evaluation criteria)
None: All three oxygen absorber packages are not detected by the metal detector.
Yes: One or more oxygen absorber packages were detected by the metal detector.

<X-ray Foreign Matter Detection Test>
The three obtained oxygen absorber packages were passed through an X-ray foreign matter detector ("X-ray inspection system" manufactured by Anritsu Infivis Co., Ltd.) to conduct an X-ray foreign matter detection test.
The measurement conditions for the X-ray foreign object detector were set at a tube voltage of 60 kV and a tube current of 5.0 mA.
Whether or not X-ray detection was possible was determined based on the lowest value (lowest detection intensity) among the X-ray detection intensities of the three oxygen absorber packages according to the following evaluation criteria. If it is determined that X-ray detection is possible according to the following evaluation criteria, it means that the presence of the oxygen absorber package can be confirmed by an X-ray foreign matter detector.
(Evaluation criteria)
AA: The minimum detection intensity of X-rays is 40 or more, and X-rays can be easily detected.
A: The minimum detection intensity of X-rays is 20 or more and less than 40, and X-ray detection is possible.
B: The minimum detectable intensity of X-rays is more than 0 and less than 20, and X-ray detection is difficult in some cases.
C: The minimum detectable intensity of X-rays is 0, and X-rays cannot be detected.

<Measurement of oxygen concentration (O ₂ ) and carbon dioxide concentration (CO ₂ )>
One obtained oxygen absorber package and 1000 mL of a mixed gas of 75 vol% nitrogen, 20 vol% oxygen and 5 vol% carbon dioxide were placed in a nylon/polyethylene laminated film gas barrier bag and sealed. After storage at 25° C. for 48 hours, the oxygen concentration and carbon dioxide concentration in the gas barrier bag were measured.
Oxygen and carbon dioxide concentrations were measured using a gas analyzer (“Check Mate 3” manufactured by mocon Dansensor). A zirconia oxygen concentration meter of the gas analyzer was used to measure the oxygen concentration, and an infrared absorption type carbon dioxide concentration meter of the gas analyzer was used to measure the carbon dioxide concentration.

(Production Example 1: Preparation of base composition 1)
4.7 kg of sodium erythorbate, 2.1 kg of water, 1.0 kg of sodium carbonate, 1.0 kg of activated carbon ("Taiko S type" manufactured by Futamura Chemical Co., Ltd.), powdered polyethylene ("Sun wax 171P" manufactured by Sanyo Chemical Industries, Ltd.) 0.55 kg, 0.40 kg of ferrous sulfate heptahydrate, 0.30 kg of bentonite (“Neo Kuni Bond” manufactured by Kunimine Industries Co., Ltd.), and 0.19 kg of carboxymethyl cellulose (“JP83” manufactured by Daicel Co., Ltd.) are mixed to form a base. Composition 1 was obtained.

(Production Example 2: Preparation of base composition 2)
1.64 kg of glycerin, 0.3 kg of water, 0.12 kg of manganese chloride tetrahydrate, 0.012 kg of 5-methylresorcinol, and 8.3 kg of calcium hydroxide (granular slaked lime manufactured by Yabashi Industry Co., Ltd.) were mixed to form a base composition. got 2.

(Examples 1 to 16)
First, a three-side seal bag (length 60 mm x width 65 mm) made of a breathable packaging material made of low-density polyethylene nonwoven fabric was prepared.
Next, 5.0 g of the base composition 1 obtained in Production Example 1 and the inorganic compound (A) (marker substance) in the blending amount shown in Table 1 were added to the three-side-sealed bag, and the three-side-sealed bag was was enclosed to form an oxygen absorber package.

(Comparative example 1)
In Comparative Example 1, an oxygen absorber package was obtained in the same manner as in Example 1, except that the inorganic compound (A) was not used.

(Comparative Examples 2 to 6)
In Comparative Examples 2 to 6, oxygen absorber packages were obtained in the same manner as in Example 1, except that the inorganic compound (A) was replaced with the inorganic compound in the amount shown in Table 1.

(Examples 17-20)
In Examples 17 to 20, 7.0 g of the base composition 2 obtained in Production Example 2 was used instead of the base composition 1, and the inorganic compound (A) in the amount shown in Table 1 was used. An oxygen absorber package was obtained in the same manner as in Example 1.

(Comparative Example 7)
In Comparative Example 7, an oxygen absorber package was obtained in the same manner as in Comparative Example 1, except that 7.0 g of Base Composition 2 obtained in Production Example 2 was used instead of Base Composition 1.

Details of the components used in Table 1 are shown below.
* Barium sulfate 1: Nippon Kagaku Kogyo Co., Ltd. "AD barium sulfate", barium sulfate (BaSO ₄ ) powder * Barium sulfate 2: Sakai Chemical Industry Co., Ltd. "BAFELINE", barium sulfate (BaSO ₄ ) granules * Sulfuric acid Barium 3: Granules of barium sulfate (BaSO ₄ ) Barium sulfate 3 is barium sulfate (“AD barium sulfate” manufactured by Nippon Chemical Industry Co., Ltd.) 10 kg, water 1.5 kg, carboxymethyl cellulose (manufactured by Daicel Co., Ltd. “JP83”) 0 0.0075 kg was mixed granulated and dried.
* Zinc oxide 1: Zinc oxide (ZnO) powder manufactured by Sakai Chemical Industry Co., Ltd. * Zinc oxide 2: Zinc oxide (ZnO) granules manufactured by Sakai Chemical Industry Co., Ltd. * Zirconium oxide: Oxidized by Marumi Ceramics Co., Ltd. Fine granules of zirconium (ZrO ₂ )* Bismuth oxide: Powder of bismuth oxide (Bi ₂ O ₃ ), manufactured by Nippon Kagaku Sangyo Co., Ltd.* Calcium hydroxide: Calcium hydroxide (Ca(OH) ₂ ), manufactured by Yabashi Industry Co., Ltd.
* Silicon dioxide: granules of silicon dioxide (SiO ₂ ) manufactured by Mikawa Silica Sand Co., Ltd. * Aluminum oxide: Axens Canada Specialty Aluminas Inc.; manufactured by, aluminum oxide (Al ₂ O ₃ ) fine granules* Titanium oxide: manufactured by Sakai Chemical Industry Co., Ltd., granules of titanium oxide (TiO ₂ )* Iron sand: manufactured by Toto Kosan Co., Ltd., iron oxide (Fe ₃ O ₄ ) granules of

As shown in Table 1, the oxygen absorber package containing the non-ferrous oxygen-absorbing substance and the predetermined inorganic compound (A) was not detected by the metal detector, but could be detected by the X-ray foreign matter detector. (Examples 1-20).
On the other hand, the oxygen absorber package of Comparative Example 1, which does not contain the inorganic compound (A), and the oxygen absorber package of Comparative Example 2, which contains calcium hydroxide instead of the inorganic compound (A), are not capable of metal detection. It was confirmed that neither the machine nor the X-ray foreign object detector detected it.
Further, the oxygen absorber package of Comparative Example 7 containing no inorganic compound (A), and Comparative Examples 3 to 3 containing any one of silicon dioxide, aluminum oxide and titanium oxide instead of the inorganic compound (A) The oxygen absorber package of No. 5 was not detected by the metal detector, and it was confirmed by the X-ray foreign object detector that it slightly shielded X-rays, but the shielding strength was weak and could not be said to be detectable. rice field.
In addition, the oxygen absorber package of Comparative Example 6 containing iron sand instead of the inorganic compound (A) was detectable by an X-ray foreign object detector, but it was confirmed that it was also detected by a metal detector. was done.

It was also confirmed that all the oxygen absorber packages exhibited sufficient oxygen absorption capacity, and that the addition of the inorganic compound (A) did not affect the oxygen absorption capacity.
In addition, the oxygen absorber package using the base composition 1 containing ascorbic acids also has the ability to generate carbon dioxide. was reduced, and the effect of the addition of calcium hydroxide on the ability to generate carbon dioxide was confirmed. On the other hand, in the deoxidizing packages (Examples 1 to 16) to which the inorganic compound (A) was added, sufficient carbon dioxide was generated, and the effect of the addition of the inorganic compound (A) on the carbon dioxide generation ability. It was confirmed that there is no

As confirmed in the above examples, the oxygen absorber package of the present invention is not detected by a metal detector, but can be detected by an X-ray foreign matter detector. Therefore, even when the article to be stored and the oxygen absorber package are sealed in a sealed container, the presence or absence of the oxygen absorber package in the sealed container can be easily detected using an X-ray foreign matter detector. It is possible to confirm.
For example, in FIG. 1, the oxygen absorber package of Example 10 and 2 kg of polished rice are placed in a 2 L packaging bag (material: polyethylene, thickness 70 mm, length 30 mm x width 20 mm), and X-ray foreign matter detection is performed. An X-ray photograph when passed through the machine is shown. As shown in FIG. 1, the oxygen absorber package of the present invention strongly shields X-rays, so even if the article to be stored is milled rice with a relatively large thickness, it appears as a shadow in an X-ray photograph ( 1). Therefore, by confirming the shadow, the presence of the oxygen absorber package housed in the packaging bag can be easily confirmed.

The oxygen absorber package of the present invention cannot be detected by a metal detector, but can be detected by an X-ray foreign matter detector. Therefore, it can be used together with the inspection of metal foreign substances using a metal detector. It helps reduce product defects and automates visual checks, which saves labor in the inspection process.

Claims (10)

containing a nonferrous oxygen-absorbing substance and at least one inorganic compound (A) selected from the group consisting of copper compounds, zinc compounds, strontium compounds, zirconium compounds, barium compounds, tungsten compounds and bismuth compounds; Oxygen agent package. 2. The non-ferrous oxygen-absorbing substance according to claim 1, which is at least one selected from the group consisting of ascorbic acid, ascorbate, erythorbic acid, erythorbate, glycerin, glyceric acid, gallic acid and catechol. oxygen absorber package. The oxygen absorber package according to claim 1 or 2, wherein the content of the inorganic compound (A) is 0.01 g or more and 5.0 g or less. The oxygen absorber package according to any one of claims 1 to 3, wherein the shape of the inorganic compound (A) is at least one selected from the group consisting of powder and granules. The oxygen absorber package according to any one of claims 1 to 4, wherein the inorganic compound (A) has an average particle size (D50) of 1 µm or more and 5000 µm or less. The deoxidizer according to any one of claims 1 to 5, wherein the inorganic compound (A) is at least one selected from the group consisting of zinc compounds, strontium compounds, zirconium compounds, barium compounds and bismuth compounds. agent package. The oxygen absorber package according to any one of claims 1 to 6, further comprising at least one selected from the group consisting of alkaline substances, catalysts, carriers, swelling agents, exothermic suppressants and water. A packaging material containing the nonferrous oxygen-absorbing substance and the inorganic compound (A),
8. The packaging material according to any one of claims 1 to 7, wherein the shape of the packaging material is one selected from the group consisting of a bag shape, a three-side seal shape, a four-side seal shape, a stick shape, a cylindrical shape and a box shape. oxygen absorber package. For products in which the oxygen absorber package according to any one of claims 1 to 8 is enclosed, an inspection to confirm that the oxygen absorber package is enclosed is performed using an X-ray foreign matter detector. A method for confirming the existence of an oxygen agent package. containing a nonferrous oxygen-absorbing substance and at least one inorganic compound (A) selected from the group consisting of copper compounds, zinc compounds, strontium compounds, zirconium compounds, barium compounds, tungsten compounds and bismuth compounds; Oxygen agent composition.

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