JP7020192B2 - Organic deoxidizing material that suppresses coloring - Google Patents

Description

The present invention relates to a deoxidizing material, and more particularly to a deoxidizing material having a composition containing an easily oxidizable organic substance and a packaging material.

As the deoxidizing material, those having an easily oxidizable inorganic substance such as iron as a main component and those having an easily oxidizable organic substance such as an ascorbic acid compound, a polyhydric phenol compound and an unsaturated hydrocarbon compound as a main component are known. (Patent Document 1).
When a metal detector is used to inspect the mixing of metallic foreign substances into the deoxidizing material, an organic deoxidizing material whose main component is an organic substance that is insensitive to the metal detector is used.
Easy-to-oxidize organic substances are usually colorless as compounds, but yellow or brown coloring occurs due to oxidation or radical decomposition. Since yellow and brown have a large change in color tone from colorless, there is a problem that the change in color tone is conspicuous even with a small amount of oxidation to the extent that the oxidation performance hardly changes.
As is known to use Japanese paper laminated with a perforated polyethylene film as a packaging material for an oxygen absorbing material (Patent Document 1), the packaging material for a deoxidizing material does not interfere with oxygen absorption performance. , A thin material with good air and steam permeability is used. Therefore, if the easily oxidizable organic substance is colored by a small amount of oxidation or the like, the coloring becomes conspicuous, and there is a problem that performance deterioration is suspected even before use.
There is also a method of changing the color of the packaging material to dark yellow or brown so that the yellow color of the contents is not noticeable, but the colors that can be selected are limited.

Japanese Unexamined Patent Publication No. 10-314581

An object of the present invention is to provide a deoxidizing material containing an easily oxidizable organic substance as a main component, which can suppress discoloration of the appearance of the packaging material due to long-term storage or oxidation while maintaining high oxygen absorption performance. be.

As a result of diligent research, the present inventors have found that the present invention can be solved by the following inventions.
The present invention is as follows.

[1] A packaging material (B) selected from the group consisting of a composition (A) containing an easily oxidizable organic substance (a1) and a porous body, a fiber and a film packaging material is provided, and the packaging material (B) has a packaging material (B). A deoxidizing material impregnated with a reducing substance (C).
[2] The deoxidizing material according to [1], wherein the packaging material (B) contains 1 or more selected from the group consisting of paper, non-woven fabric and plastic film.
[3] The deoxidation according to [1] or [2], wherein the easily oxidizing organic substance (a1) contains one or more compounds selected from the group consisting of ascorbic acid, ascorbic acid salt, erythorbic acid and erythorbic acid salt. material.
[4] The deoxidizing material according to any one of [1] to [3], wherein the reducing substance (C) is brilliant blue FCF.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an organic deoxidizing material capable of suppressing discoloration of the appearance of a packaging material due to long-term storage or oxidation while maintaining high oxygen absorption performance.

The deoxidizing material of the present invention has a composition (A) containing an easily oxidizable organic substance (a1) and a packaging material (B) selected from the group consisting of a porous body, a fiber and a film packaging material, and the packaging material. (B) is impregnated with the reducing substance (C).
Hereinafter, these will be described in detail.

[Composition (A) containing an easily oxidizable organic substance (a1)]
The composition (A) of the present application contains an easily oxidizable organic substance (a1), water (a2), a porous carrier (a3), and if necessary, other components.

<Easy-oxidizing organic matter (a1)>
The easily oxidizing organic substance (a1) is an organic substance that is easily oxidized by oxygen contained in the air, and is not particularly limited as long as it is an organic substance that is oxidized in an air atmosphere. Preferred specific examples thereof because of their high oxygen absorption are ascorbic acid, ascorbic acid salt, erythorbic acid and erythorbic acid salt. In particular, ascorbic acid and salts thereof are more preferable.

<Water (a2)>
Water (a2) is used to promote the progress of the oxidation reaction of the easily oxidizable organic substance (a1).
The amount of water to be blended in the composition (A) is preferably 100 to 200 parts by mass, more preferably 110 to 180 parts by mass, and 120 to 180 parts by mass with respect to 100 parts by mass of the easily oxidizing organic substance (a1). Is even more preferable. Being in this range increases the oxygen absorption rate.

<Porosity carrier (a3)>
The porous carrier (a3) has a function as a carrier for impregnating water. Specific examples of the porous carrier include activated carbon, diatomaceous earth, silica gel, zeolite, pearlite, calcium silicate, pumice stone, cellulose, activated white clay, alumina, hydroxyapatite, porous resin and porous glass, and activated carbon is particularly preferable. Granular activated carbon having a particle size of 0.1 mm to 2 mm, preferably 0.5 to 1 mm is preferable because of its good fluidity.
The blending amount of the porous carrier is preferably 50 to 400 parts by mass, more preferably 75 to 300 parts by mass with respect to 100 parts by mass of the easily oxidizable organic substance (a1). Within this range, the fluidity of the composition (A) can be improved, and the filling property when the composition (A) is filled in the packaging material (B) can be improved.
<Other ingredients>
Other components that may be included in the composition (A) include, for example, transition metal catalysts, metal hydroxides, carbonates, phosphates, metal salts and thermoplastic resins.
Transition metal catalysts can accelerate the progress of the oxidation reaction. Examples of transition metal catalysts include iron, manganese, zinc, copper, cobalt, and halides and mineral salts thereof.
Metal hydroxides, carbonates, phosphates and metal salts are used to adjust the pH and activity of aqueous solutions. Examples of the metal hydroxide include an alkali metal hydroxide and an alkaline earth metal hydroxide. Examples of the carbonate include sodium carbonate and sodium hydrogen carbonate. Examples of the phosphate include sodium phosphate and sodium polyphosphate.
The thermoplastic resin can suppress the abnormal heat generation of the composition (A) due to oxidation. The thermoplastic resin preferably has a softening point of 90 to 125 ° C., and examples thereof include polyethylene, polypropylene, an ethylene-vinyl acetate copolymer, an elastomer, and a mixture thereof.

<Preparation method of composition (A)>
As a method for preparing the composition (A), for example, the easily oxidizable organic substance (a1) and water (a2) are stirred by a usual method until they become uniform to form an aqueous solution (or slurry), which is impregnated into the porous carrier (a3). Can be prepared by At this time, the composition (A) is preferably prepared in an inert gas.
When ascorbic acid salt or erythorbic acid salt is used as the easily oxidizable organic substance (a1), an aqueous solution neutralized with an alkaline aqueous solution may be used. In addition, other components can be added as appropriate.

[Packaging material (B)]
The packaging material (B) is an outer member that wraps the composition (A) and is selected from the group consisting of a porous body, a fiber, and a film packaging material. The packaging material is not limited as long as it is the above-mentioned packaging material that allows oxygen to permeate, but a material having an air permeation resistance of 600 seconds or less, more preferably 90 seconds or less by the Gale type testing machine method is preferably used. The air permeation resistance is a value measured by the method described in JIS P8117-1998.
Specific examples of the packaging material (B) include those obtained by imparting breathability to paper, non-woven fabric and plastic film.
As the plastic film, for example, a film such as polyethylene terephthalate, polyamide, polypropylene, polycarbonate or the like and a film such as polyethylene, ionomer, polybutadiene, ethylene acrylic acid copolymer, ethylene methacrylic acid copolymer or ethylene vinyl acetate copolymer as a sealing layer are laminated and bonded. Laminated film etc. can be used.
The method for imparting breathability is not limited, and examples thereof include drilling with a cold needle and a hot needle.
Since the impregnation property of the reducing substance (C) is high, it is preferable to include paper or non-woven fabric as the packaging material (B), and since the aqueous solution barrier property and toughness are further improved, a plastic film is applied to the paper or non-woven fabric. Laminated packaging materials are more preferred.
The thickness of the packaging material (B) is preferably 50 to 300 μm, and particularly preferably 60 to 250 μm. Within this range, it is excellent in strength, heat sealability and packaging suitability.
The packaging material (B) can be used in a bag shape by a usual method, for example, by forming it into a rectangular shape, bending it at the center, and then adhering the two sides excluding the bent portion with an adhesive or a heat seal.

[Reducing substance (C)]
The reducing substance (C) is not particularly limited as long as it is a compound that is oxidized by oxygen or radicals. The easily oxidizable organic substance (a1) is generally colorless, but it is colored yellow or brown by a denatured substance generated by a slight amount of oxidation or radical reaction. Therefore, by contacting with the reducing substance (C), oxidative denaturation of the easily oxidizable organic substance (a1) can be prevented, and yellow or brown coloring can be prevented.
The reducing substance (C) of the present application includes inorganic reducing substances such as sodium sulfite, sodium pyrosulfite, sodium thiosulfate, and sodium nitrite; oxidation-reducing dyes such as methylene blue, methyl orange, phenolphthalein, and bromotimol blue; Organic reducing substances such as acetaldehyde, benzaldehyde, formic acid and hydroquinones; easily decomposable dyes such as Brilliant Blue FCF, Floxin B and Sunset Yellow can be mentioned. Among them, Brilliant Blue FCF is preferable from the viewpoint of safety, stability and impregnation confirmation.
When an easily decomposable dye is used, yellow or brown coloring can be prevented, but discoloration of the dye itself may occur. Therefore, the easily decomposable dye and the persistently decomposable dye can be mixed or applied twice to leave the color of the persistently decomposable dye. For example, a packaging material impregnated with the easily decomposable dye Brilliant Blue after coloring with the persistent dye phthalocyanine blue can prevent the color change.
The amount of the reducing substance (C) used is not particularly limited, and even a small amount of the reducing substance (C) is effective. Further, although there is no particular effect even if it is used excessively, the impregnation amount may be any as long as it does not affect the properties such as the air permeability of the packaging material. The mass ratio to the packaging material (B) is preferably in the range of 0.01% to 10%.
The method of impregnating the packaging material (B) with the reducing substance (C) is not limited, but for example, a method such as dipping or spraying a reducing solution can be used. The impregnation of the reducing substance (C) may be performed on the entire packaging material (C) or may be partially impregnated. For example, when the packaging material (C) has a laminated film, one layer of the laminated film may be used.
As a more specific example, the non-woven fabric may be impregnated with a reducing substance and then laminated with a plastic film to form a packaging material (B). The packaging material (B) after impregnation is preferably used as a deoxidizing material after undergoing drying steps such as natural drying, heat drying, and vacuum drying to fix the reducing substance (C).

[Preparation method of deoxidizing material]
As a specific example of the method for preparing the deoxidizing material, for example, the packaging material (B) on which the reducing substance (C) is fixed is processed into a bag shape, the bag is filled with the composition (A), and the remaining one side. There is a method of sealing with an adhesive or a heat seal.
It is desirable to place it in an environment that does not come into contact with oxygen before use as a deoxidizing material, such as in an inert gas during and after preparation.

Hereinafter, the present invention will be specifically described with reference to Examples, but the embodiments can be appropriately modified as long as the effects of the present invention are exhibited.

[Evaluation methods]
<Confirmation of deoxidizing performance>
The deoxidizing material described in Examples and Comparative Examples was sealed in a 100 μm-thick silica-deposited nylon gas barrier bag (IB-ON: Dai Nippon Printing Co., Ltd.) with an air volume of 750 cc, and the oxygen concentration after 4 hours at 25 ° C. Was measured by a gas chromatograph and judged according to the following criteria.
Oxygen concentration less than 0.1%: Pass 0.1% or more: Fail

<Check the color of the packaging material>
The deoxidizing materials described in Examples and Comparative Examples were stored in a nitrogen-substituted aluminum bag 180 mm * 250 mm (AB180250PC: Mitsubishi Gas Chemical Formula Co., Ltd.) at room temperature for 180 days. The color of the surface was confirmed, the yellow colored portion was compared with the color sample of Munsell color system 5Y, and the judgment was made according to the following criteria.
Saturation C2 or less: Pass Saturation C3 or more: Fail

[Example 1]
<Preparation of composition (A) containing easily oxidizing organic substance (a1)>
In 100 g of an aqueous solution of sodium L-ascorbate (concentration 45% by mass), 6 g of ferrous sulfate 7 water salt and 10 g of sodium carbonate 10 water salt were dissolved to prepare an aqueous solution. The entire amount of this aqueous solution was impregnated into 60 g of granular activated carbon (average particle size 0.6 mm) with stirring until a uniform state was obtained. To 100 g of this impregnated product, 25 g of low molecular weight polyethylene (softening point 105 ° C.: JISK2531) having an average particle size of 200 μm and an average molecular weight of 2000 was added and mixed until uniform to prepare the composition (A).
<Preparation of deoxidizing material>
A 60 g / m ² water resistant Japanese paper (Morisa Co., Ltd.) was immersed in a brilliant blue FCF (Wako Pure Chemical Industries, Ltd.) aqueous solution (1 g / l) for 10 minutes and air-dried to color the blue color. This Japanese paper was laminated on a 30 μm-thick high-density polyethylene film (HS-30: Tamapoli Co., Ltd.) with a perforated polyethylene film in which holes were made at intervals of 2.0 mm with a 0.6 mm needle to obtain a packaging material. This was made into a three-way seal bag having a length of 90 mm and a width of 55 mm, filled with 5 g of the composition (A), and heat-sealed to prepare a deoxidizing material.
The evaluation results are shown in Table 1.

[Example 2]
The same experiment as in Example 1 was performed except that Brilliant Blue FCF was changed to Phloxine B (Wako Pure Chemical Industries, Ltd.). The results are shown in Table 1.

[Comparative Example 1]
The same experiment as in Example 1 was performed except that Brilliant Blue FCF was not used. The results are shown in Table 1.

[Comparative Example 2]
The same experiment as in Example 1 was carried out except that the brilliant blue FCF was changed to a non-reducing phthalocyanine blue (persistent dye) paint (Sakura Color Products paint acrylic color phthalocyanine blue ACW-SP # 184). The results are shown in Table 1.

Claims (4)

The composition (A) containing the easily oxidizable organic substance (a1) and
It is an outer member that wraps the composition (A), and has a packaging material (B) selected from the group consisting of a porous body, a fiber, and a film packaging material .
A deoxidizing material obtained by impregnating the packaging material (B) with a reducing substance (C). The deoxidizing material according to claim 1, wherein the packaging material (B) contains one or more selected from the group consisting of paper, non-woven fabric and plastic film. The deoxidizing material according to claim 1 or 2, wherein the easily oxidizing organic substance (a1) contains one or more compounds selected from the group consisting of ascorbic acid, ascorbic acid salt, erythorbic acid and erythorbic acid salt. The deoxidizing material according to any one of claims 1 to 3, wherein the reducing substance (C) is brilliant blue FCF.