JP2019150780A - Organic deoxidation material with suppressed coloration - Google Patents
Organic deoxidation material with suppressed coloration Download PDFInfo
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本発明は、脱酸素材に関し、より詳しくは易酸化性有機物を含有する組成物及び包装材を有する脱酸素材に関する。 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.
脱酸素材としては、鉄などの易酸化性無機物を主剤とするものや、アスコルビン酸化合物、多価フェノール化合物、不飽和炭化水素化合物などの易酸化性有機物を主剤とするものが知られている（特許文献１）。
脱酸素材への金属性異物の混入を検査するために金属探知器を使用する場合は、金属探知器に不感な有機物を主剤とする有機系脱酸素材が用いられている。
易酸化性有機物は通常、化合物として無色であるが、酸化やラジカル分解により黄色や褐色の着色が起こる。黄色や褐色は無色からの色調変化が大きいため、実質的に酸化性能がほとんど変化しない程度の微量の酸化であっても色調変化が目立つという問題がある。
酸素吸収材の包装材として、有孔ポリエチレンフィルムでラミネートした和紙を用いること（特許文献１）が知られているように、脱酸素材用の包装材としては、酸素吸収性能を妨げないような、空気や水蒸気透過性の良い、薄い材料が用いられる。そのため、易酸化性有機物が微量の酸化等によって着色すると着色が目立ってしまい、使用前であっても性能劣化が疑われる問題がある。
包装材の色を、内容物の黄色が目立たないよう濃い黄や褐色系統等にする方法もあるが、選択できる色が限定されてしまう。
Known deoxidizing materials include those based on oxidizable inorganic materials such as iron, and those based on oxidizable organic materials such as ascorbic acid compounds, polyhydric phenol compounds, and unsaturated hydrocarbon compounds. (Patent Document 1).
When a metal detector is used to inspect the mixing of metallic foreign matter into the deoxidizing material, an organic deoxidizing material mainly composed of an organic substance that is insensitive to the metal detector is used.
The easily oxidizable organic substance is usually colorless as a compound, 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 noticeable even with a very small amount of oxidation that does not substantially change the oxidation performance.
As it is known to use Japanese paper laminated with a perforated polyethylene film as a packaging material for an oxygen absorbing material (Patent Document 1), as a packaging material for a deoxidizing material, oxygen absorbing performance is not hindered. A thin material with good air and water vapor permeability is used. Therefore, when an 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 a method of making the color of the packaging material dark yellow or brown so that the yellow of the contents does not stand out, but the colors that can be selected are limited.
本発明の課題は、易酸化性有機物を主剤とする脱酸素材において、高い酸素吸収性能を維持しつつ、長期保管や酸化による包装材外観の変色を抑制可能な脱酸素材を提供することである。 An object of the present invention is to provide a deoxidizing material that can suppress discoloration of the appearance of a packaging material due to long-term storage or oxidation while maintaining high oxygen absorption performance in a deoxidizing material mainly composed of an easily oxidizable organic substance. is there.
本発明者らは鋭意研究を重ねた結果、以下の発明により本課題を解決できることを見出した。
本発明は以下の通りである。
As a result of intensive studies, the present inventors have found that the present invention can be solved by the following invention.
The present invention is as follows.
［１］ 易酸化性有機物（ａ１）を含有する組成物（Ａ）と多孔質体、繊維及びフィルム包装材からなる群より選ばれる包装材（Ｂ）を有し、前記包装材（Ｂ）に還元性物質（Ｃ）を含浸させたものである脱酸素材。
［２］ 包装材（Ｂ）が紙、不織布及びプラスチックフィルムからなる群より選択される１以上を含有する[1]に記載の脱酸素材。
［３］ 前記易酸化性有機物（ａ１）が、アスコルビン酸、アスコルビン酸塩、エリソルビン酸及びエリソルビン酸塩からなる群より選ばれる１以上の化合物を含む[１]又は[２]に記載の脱酸素材。
［４］ 前記還元性物質（Ｃ）がブリリアントブルーＦＣＦである[１]〜[３]のいずれかに記載の脱酸素材。
[1] It 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) A deoxidizing material impregnated with a reducing substance (C).
[2] The deoxidizing material according to [1], wherein the packaging material (B) contains one or more selected from the group consisting of paper, nonwoven fabric and plastic film.
[3] The deoxidation according to [1] or [2], wherein the oxidizable organic substance (a1) contains one or more compounds selected from the group consisting of ascorbic acid, ascorbate, erythorbic acid and erythorbate. Material.
[4] The deoxidizing material according to any one of [1] to [3], wherein the reducing substance (C) is brilliant blue FCF.
本発明により、高い酸素吸収性能を維持しつつ、長期保管や酸化による包装材外観の変色の抑制が可能な有機系脱酸素材を提供することができる。 According to the present invention, 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 can be provided.
本発明の脱酸素材は易酸化性有機物（ａ１）を含有する組成物（Ａ）と多孔質体、繊維及びフィルム包装材からなる群より選ばれる包装材（Ｂ）を有し、前記包装材（Ｂ）に還元性物質（Ｃ）を含浸させたものである。
以下、これらについて詳細に説明する。
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. (B) is impregnated with a reducing substance (C).
Hereinafter, these will be described in detail.
［易酸化性有機物（ａ１）を含有する組成物（Ａ）］
本願の組成物（Ａ）は易酸化性有機物（ａ１）、水（ａ２）、多孔性担体（ａ３）及び、必要に応じて、その他の成分を含有する。
[Composition (A) containing 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 other components as required.
＜易酸化性有機物（ａ１）＞
易酸化性有機物（ａ１）とは、空気中に含まれる酸素により容易に酸化される有機物であり、空気雰囲気下で酸化される有機物であれば特に限定されない。酸素吸収性が高いことから好ましい具体例としては、アスコルビン酸、アスコルビン酸塩、エリソルビン酸及びエリソルビン酸塩が挙げられる。特にアスコルビン酸及びその塩がより好ましい。
<Easily oxidizable organic substance (a1)>
The easily oxidizable 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. Preferable specific examples because of high oxygen absorption include ascorbic acid, ascorbate, erythorbic acid and erythorbate. In particular, ascorbic acid and its salt are more preferable.
＜水（ａ２）＞
水（ａ２）は易酸化性有機物（ａ１）の酸化反応の進行を促進するために用いられる。
組成物（Ａ）に配合する水の配合量は、易酸化性有機物（ａ１）１００質量部に対して、１００〜２００質量部が好ましく、１１０〜１８０質量部がより好ましく、１２０〜１８０質量部がさらに好ましい。この範囲にあることで酸素吸収速度が速くなる。
<Water (a2)>
Water (a2) is used for promoting the progress of the oxidation reaction of the easily oxidizable organic substance (a1).
The amount of water 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 oxidizable organic substance (a1). Is more preferable. By being in this range, the oxygen absorption rate is increased.
＜多孔性担体（ａ３）＞
多孔性担体（ａ３）は、水を含浸させる担体としての機能を有する。多孔性担体の具体例としては、活性炭、珪藻土、シリカゲル、ゼオライト、パーライト、珪酸カルシウム、軽石、セルロース、活性白土、アルミナ、ヒドロキシアパタイト、多孔質樹脂及び多孔質ガラスが挙げられ、活性炭が好ましく、特に流動性が良好であるという理由から粒子径が０．１ｍｍ〜２ｍｍ、好ましくは０．５〜１ｍｍの粒状活性炭が好ましい。
多孔性担体の配合量は、易酸化性有機物（ａ１）１００質量部に対して５０〜４００質量部が好ましく、７５〜３００質量部がより好ましい。この範囲にあることで、組成物（Ａ）の流動性が向上し、組成物（Ａ）を包装材（Ｂ）に充填する際の充填性を高めることが出来る。
＜その他の成分＞
組成物（Ａ）に含まれても良いその他の成分としては、例えば遷移金属触媒、金属水酸化物、炭酸塩、リン酸塩、金属塩及び熱可塑性樹脂が挙げられる。
遷移金属触媒は酸化反応の進行を促進させることができる。遷移金属触媒としては、鉄、マンガン、亜鉛、銅、コバルト及び、これらのハロゲン化物及び鉱酸塩が挙げられる。
金属水酸化物、炭酸塩、リン酸塩および金属塩は、水溶液のｐＨ調製や活量調製に用いられる。金属水酸化物としては、アルカリ金属水酸化物及びアルカリ土類金属水酸化物が挙げられる。炭酸塩としては炭酸ナトリウム及び炭酸水素ナトリウムが挙げられる。リン酸塩としてはリン酸ナトリウム及びポリリン酸ナトリウムが挙げられる。
熱可塑性樹脂は、酸化による組成物（Ａ）の異常な発熱を抑制することができる。熱可塑性樹脂としては軟化点が９０〜１２５℃の熱可塑性樹脂が好ましく、ポリエチレン、ポリプロピレン、エチレン−酢酸ビニル共重合体、エラストマー及びこれらの混合物が挙げられる。
<Porous carrier (a3)>
The porous carrier (a3) has a function as a carrier to be impregnated with water. Specific examples of the porous carrier include activated carbon, diatomaceous earth, silica gel, zeolite, pearlite, calcium silicate, pumice, cellulose, activated clay, alumina, hydroxyapatite, porous resin and porous glass, and activated carbon is particularly preferable. Granular activated carbon having a particle diameter of 0.1 mm to 2 mm, preferably 0.5 to 1 mm is preferable because of good fluidity.
50-400 mass parts is preferable with respect to 100 mass parts of oxidizable organic substances (a1), and the compounding quantity of a porous support | carrier is more preferable 75-300 mass parts. By being in this range, the fluidity | liquidity of a composition (A) improves and the fillability at the time of filling a packaging material (B) with a composition (A) can be improved.
<Other ingredients>
Examples of other components that may be included in the composition (A) include transition metal catalysts, metal hydroxides, carbonates, phosphates, metal salts, and thermoplastic resins.
The transition metal catalyst can promote the progress of the oxidation reaction. Transition metal catalysts include iron, manganese, zinc, copper, cobalt and their halides and mineral salts.
Metal hydroxides, carbonates, phosphates and metal salts are used for pH adjustment and activity adjustment of aqueous solutions. Examples of the metal hydroxide include alkali metal hydroxide and 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 abnormal heat generation of the composition (A) due to oxidation. The thermoplastic resin is preferably a thermoplastic resin having a softening point of 90 to 125 ° C., and examples thereof include polyethylene, polypropylene, ethylene-vinyl acetate copolymer, elastomer, and mixtures thereof.
＜組成物（Ａ）の調製方法＞
組成物（Ａ）の調製方法としては、例えば易酸化性有機物（ａ１）及び水（ａ２）を通常の方法で均一になるまで攪拌して水溶液（又はスラリー）とし多孔性担体（ａ３）に含浸することで調製できる。この際組成物（Ａ）は、不活性ガス中で調製することが好ましい。
易酸化性有機物（ａ１）にアスコルビン酸塩又はエリソルビン酸塩を用いる場合は、アルカリ水溶液で中和した水溶液を用いても良い。また、その他の成分は適宜添加することができる。
<Method for Preparing Composition (A)>
As a preparation method of the composition (A), for example, an easily oxidizable organic substance (a1) and water (a2) are stirred until they become uniform by a usual method to form an aqueous solution (or slurry) and impregnated into the porous carrier (a3). Can be prepared. At this time, the composition (A) is preferably prepared in an inert gas.
When using ascorbate or erythorbate as the oxidizable organic substance (a1), an aqueous solution neutralized with an alkaline aqueous solution may be used. Other components can be added as appropriate.
［包装材（Ｂ）］
包装材（Ｂ）は、組成物（Ａ）を包む外側の部材であり多孔質体、繊維及びフィルム包装材からなる群より選択される。包装材としては、酸素を透過する前記の包装材であれば限定されないが、ガーレ式試験機法による透気抵抗度が６００秒以下、より好ましくは９０秒以下のものが好適に用いられる。透気抵抗度は、ＪＩＳ Ｐ８１１７−１９９８に記載の手法により測定される値である。
包装材（Ｂ）の具体例としては、紙、不織布及びプラスチックフィルムに通気性を付与したものが挙げられる。
プラスチックフィルムとしては例えば、ポリエチレンテレフタレート、ポリアミド、ポリプロピレン、ポリカーボネート等のフィルムと、シール層としてポリエチレン、アイオノマー、ポリブタジエン、エチレンアクリル酸コポリマー、エチレンメタクリル酸コポリマーまたはエチレン酢酸ビニルコポリマー等のフィルムとを積層接着した積層フィルムなどが使用できる。
通気性を付与する方法は限定されないが、例えば冷針、熱針による穿孔加工が挙げられる。
還元性物質（Ｃ）の含浸性が高くなることから包装材（Ｂ）としては紙や不織布を含むことが好ましく、更に水溶液バリア性や頑丈さが高くなることから、紙又は不織布にプラスチックフィルムを積層した包装材がより好ましい。
包装材（Ｂ）の厚さは、５０〜３００μｍであることが好ましく、６０〜２５０μｍであることが特に好ましい。この範囲にあることで強度、ヒートシール性や包装適性に優れる。
包装材（Ｂ）は例えば、長方形に成形し、中央で折り曲げてから折り曲げ部を除く２辺を接着剤やヒートシールで接着する等、通常の手法で袋状にして使用できる。
[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-described packaging material that allows oxygen to pass therethrough, but those having an air resistance of 600 seconds or less, more preferably 90 seconds or less, by the Gurley tester method are suitably used. The air 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 air permeability to paper, nonwoven fabric and plastic film.
As a plastic film, for example, a film of polyethylene terephthalate, polyamide, polypropylene, polycarbonate or the like and a film of polyethylene, ionomer, polybutadiene, ethylene acrylic acid copolymer, ethylene methacrylic acid copolymer or ethylene vinyl acetate copolymer as a sealing layer are laminated and adhered. A laminated film or the like can be used.
The method for imparting air permeability is not limited, and examples thereof include drilling with a cold needle and a hot needle.
Since the impregnating property of the reducing substance (C) is high, the packaging material (B) preferably contains paper or non-woven fabric. Further, since the aqueous solution barrier property and robustness are high, a plastic film is applied to the paper or non-woven fabric. A laminated packaging material is more preferable.
The thickness of the packaging material (B) is preferably 50 to 300 μm, and particularly preferably 60 to 250 μm. By being in this range, it is excellent in strength, heat sealability and packaging suitability.
The packaging material (B) can be used, for example, by forming it into a rectangular shape, folding it at the center, and then bonding the two sides excluding the bent part with an adhesive or heat seal.
［還元性物質（Ｃ）］
還元性物質（Ｃ）は酸素やラジカルで酸化される化合物であれば特に限定されない。易酸化性有機物（ａ１）は一般的に通常無色であるが、微量の酸化やラジカル反応によって生じる変性物質により黄色や褐色に着色してしまう。そこで、還元性物質（Ｃ）と接触することにより、易酸化性有機物（ａ１）の酸化変性を防止し、黄色や褐色の着色を防止することができる。
本願の還元性物質（Ｃ）としては、亜硫酸ナトリウム、ピロ亜硫酸ナトリウム、チオ硫酸ナトリウム、亜硝酸ナトリウムなどの無機還元性物質；メチレンブルー、メチルオレンジ、フェノールフタレイン、ブロモチモールブルーなどの酸化還元色素；アセトアルデヒド、ベンズアルデヒド、ギ酸、ヒドロキノン類などの有機系還元性物質；ブリリアントブルーＦＣＦ、フロキシンＢ、サンセットイエローなどの易分解性色素が挙げられる。なかでもブリリアントブルーＦＣＦは、安全性、安定性、含浸確認性から好ましい。
易分解性色素を用いる場合、黄色や褐色の着色は防ぐことができるが、色素自体の変色が起こる場合がある。そこで、易分解性色素と難分解性色素を混合、または２度塗りして、難分解性色素の色を残すことができる。例えば、難分解性の色素フタロシアニンブルーで着色後に、易分解性の色素ブリリアントブルーを含浸した包材であれば、色の変化を防ぐことができる。
還元性物質（Ｃ）の使用量は特に限定がなく、微量の添加でも効果がある。また、過剰に使用しても特に影響はないが、包装材の通気性などの性状を損なうほどの影響がない含浸量であれば良い。包装材（Ｂ）に対して質量比では０．０１％〜１０％の範囲が好ましい。
還元性物質（Ｃ）を包装材（Ｂ）に含浸させる方法は限定されないが、例えば還元性溶液の浸漬や吹き付けなどの方法をとることができる。還元性物質（Ｃ）の含浸は包装材（Ｃ）の全体に行っても良いし、一部でもよい。例えば包装材（Ｃ）が積層フィルムを有する場合に積層フィルムの一層でも構わない。
より具体的な例として、不織布に還元性物質を含浸後、プラスチックフィルムを積層して包装材（Ｂ）とすることもできる。含浸後の包装材（Ｂ）は、自然乾燥、加熱乾燥、真空乾燥等の乾燥工程を行い、還元性物質（Ｃ）を定着させてから脱酸素材に用いることが好ましい。
[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 modifying substance generated by a small amount of oxidation or radical reaction. Therefore, by contacting with the reducing substance (C), oxidative modification of the easily oxidizable organic substance (a1) can be prevented, and yellow or brown coloring can be prevented.
Examples of the reducing substance (C) of the present application include inorganic reducing substances such as sodium sulfite, sodium pyrosulfite, sodium thiosulfate, and sodium nitrite; redox dyes such as methylene blue, methyl orange, phenolphthalein, and bromothymol blue; Organic reducible substances such as acetaldehyde, benzaldehyde, formic acid, hydroquinones; and readily decomposable dyes such as brilliant blue FCF, phloxine B, and sunset yellow. Among these, brilliant blue FCF is preferable from the viewpoint of safety, stability, and impregnation confirmation.
When an easily decomposable dye is used, yellowing or browning can be prevented, but discoloration of the dye itself may occur. Therefore, the easily decomposable dye and the hardly decomposable dye can be mixed or applied twice to leave the color of the hardly decomposable dye. For example, a color change can be prevented if the packaging material is impregnated with an easily decomposable dye brilliant blue after coloring with the hardly decomposable dye phthalocyanine blue.
The amount of the reducing substance (C) used is not particularly limited, and even if it is added in a small amount, it is effective. Moreover, even if it uses excessively, there will be no influence in particular, However, What is necessary is just the impregnation amount which does not have the influence which damages properties, such as air permeability of a packaging material. A mass ratio of 0.01% to 10% with respect to the packaging material (B) is preferable.
Although the method of impregnating the reducing material (C) in the packaging material (B) is not limited, for example, a method such as immersion or spraying of the reducing solution can be used. The impregnation of the reducing substance (C) may be performed on the entire packaging material (C) or a part thereof. 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, after impregnating a non-woven fabric with a reducing substance, a plastic film may be laminated to obtain a packaging material (B). The impregnated packaging material (B) is preferably used as a deoxidizing material after performing a drying process such as natural drying, heat drying, or vacuum drying to fix the reducing substance (C).
［脱酸素材の調製方法］
脱酸素材の調製方法の具体例としては、例えば還元性物質（Ｃ）を定着させた包装材（Ｂ）を袋状に加工し、この袋に組成物（Ａ）を充填し、残る１辺を接着剤やヒートシールで密封する方法が挙げられる。
調製中及び調製後は不活性ガス中等、脱酸素材として使用前の時点においては酸素に触れない環境下に置くことが望ましい。
[Method for preparing deoxidized material]
As a specific example of the preparation method of the deoxidizing material, for example, a packaging material (B) in which a 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 heat seal.
It is desirable to put it in an environment that does not come into contact with oxygen during preparation and after preparation, such as in an inert gas, before use as a deoxidizing material.
以下、実施例により本発明を具体的に説明するが、本発明の効果を奏する限りにおいて実施形態を適宜変更することができる。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, as long as there exists an effect of this invention, embodiment can be changed suitably.
［評価方法］
＜脱酸素性能の確認＞
実施例及び比較例に記載の脱酸素材を厚さ１００μｍのシリカ蒸着ナイロン製ガスバリア袋（ＩＢ−ＯＮ：大日本印刷株式会社）に空気量７５０ｃｃとともに密封し、２５℃、４時間後の酸素濃度をガスクロマトグラフにより測定し、以下の基準で判断した。
酸素濃度が
０．１％未満：合格
０．１％以上：不合格
[Evaluation method]
<Confirmation of deoxygenation performance>
The deoxidized materials described in Examples and Comparative Examples were sealed in a 100 μm thick silica-deposited nylon gas barrier bag (IB-ON: Dai Nippon Printing Co., Ltd.) together with an air amount 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 is less than 0.1%: Pass 0.1% or more: Fail
＜包装材の色確認＞
実施例及び比較例に記載の脱酸素材を、窒素置換したアルミ袋１８０ｍｍ＊２５０ｍｍ（ＡＢ１８０２５０ＰＣ：三菱ガス化学式会社）に常温で１８０日間保管した。表面の色を確認し、黄色着色部をマンセル表色系５Ｙの色見本と比較し、以下の基準で判断した。
彩度Ｃ２以下：合格
彩度Ｃ３以上：不合格
<Color confirmation of packaging material>
The deoxidized materials described in Examples and Comparative Examples were stored in an aluminum bag 180 mm * 250 mm (AB180250PC: Mitsubishi Gas Chemical Company) substituted with nitrogen for 180 days at room temperature. The color of the surface was confirmed, the yellow colored portion was compared with the color sample of Munsell color system 5Y, and judged according to the following criteria.
Saturation C2 or less: Pass Saturation C3 or more: Fail
［実施例１］
＜易酸化性有機物（ａ１）を含有する組成物（Ａ）の調製＞
Ｌ−アスコルビン酸ナトリウム水溶液（濃度４５質量％）１００ｇに、硫酸第１鉄・７水塩６ｇ及び炭酸ナトリウム・１０水塩１０ｇを溶解させて水溶液にした。この水溶液全量を顆粒状活性炭（平均粒径０．６ｍｍ）６０ｇに均一な状態になるまで攪拌しながら含浸させた。この含浸物１００ｇに平均粒径２００μｍ、平均分子量２０００の低分子量ポリエチレン（軟化点１０５℃：ＪＩＳＫ２５３１）２５ｇを添加し、均一になるまで混合して、組成物（Ａ）を調製した。
＜脱酸素材の調製＞
６０ｇ／ｍ２の耐水性和紙（株式会社モリサ）をブリリアントブルーＦＣＦ（和光純薬工業株式会社）水溶液（１ｇ／ｌ）に１０分間浸漬し、風乾することで青色着色した。この和紙を、厚さ３０μｍの高密度ポリエチレンフィルム（ＨＳ−３０：タマポリ株式会社）に０．６ｍｍの針によって２．０ｍｍ間隔で穴を開けた有孔ポリエチレンフィルムでラミネートし、包装材とした。これを縦９０ｍｍ＊横５５ｍｍの３方シール袋にし、前記組成物（Ａ）を５ｇ充填し、そしてヒートシールして、脱酸素材を調製した。
評価結果を表１に示す。
[Example 1]
<Preparation of composition (A) containing easily oxidizable organic substance (a1)>
In 100 g of sodium L-ascorbate aqueous solution (concentration: 45 mass%), 6 g of ferrous sulfate · 7 hydrate and 10 g of sodium carbonate · 10 hydrate were dissolved to obtain an aqueous solution. The whole amount of this aqueous solution was impregnated with stirring to 60 g of granular activated carbon (average particle size 0.6 mm) until uniform. 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 to 100 g of this impregnated product, and mixed until uniform to prepare a composition (A).
<Preparation of deoxidation material>
60 g / m 2 of water-resistant Japanese paper (Morisa Co., Ltd.) was dipped in an aqueous solution (1 g / l) of Brilliant Blue FCF (Wako Pure Chemical Industries, Ltd.) for 10 minutes and air-dried to give a blue color. This Japanese paper was laminated on a high-density polyethylene film (HS-30: Tamapoly Co., Ltd.) having a thickness of 30 μm with a perforated polyethylene film having holes formed at intervals of 2.0 mm with a 0.6 mm needle to obtain a packaging material. This was made into a three-side sealed bag measuring 90 mm in length and 55 mm in width, filled with 5 g of the composition (A), and heat-sealed to prepare a deoxidized material.
The evaluation results are shown in Table 1.
［実施例２］
ブリリアントブルーＦＣＦを、フロキシンＢ（和光純薬工業株式会社）に変更した以外は、実施例１と同様の実験を行った。結果を表１に示す。
[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.
［比較例１］
ブリリアントブルーＦＣＦを使用しなかったこと以外は、実施例１と同様の実験を行った。結果を表１に示す。
[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.
［比較例２］
ブリリアントブルーＦＣＦを、還元性を持たないフタロシアニンブルー（難分解性色素）絵具（サクラクレパス 絵の具 アクリルカラー フタロシアニンブルー ＡＣＷ−ＳＰ＃１８４）に変更した以外は、実施例１と同様の実験を行った。結果を表１に示す。
[Comparative Example 2]
The same experiment as in Example 1 was performed except that the brilliant blue FCF was changed to a phthalocyanine blue (refractory dye) paint having no reducing property (Sakura Crepas paint acrylic color phthalocyanine blue ACW-SP # 184). The results are shown in Table 1.
Claims (4)
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| JPS6214939A (en) * | 1985-07-12 | 1987-01-23 | Kawasaki Kasei Chem Ltd | Oxygen scavenger and its preparation |
| JPS62183834A (en) * | 1986-12-26 | 1987-08-12 | Toppan Printing Co Ltd | Oxygen absorbent package |
| JPH10314581A (en) * | 1997-03-19 | 1998-12-02 | Mitsubishi Gas Chem Co Inc | Oxygen absorbent and culture method for anaerobic bacteria using the same |
| JP2005137215A (en) * | 2003-11-04 | 2005-06-02 | Asahi Kasei Life & Living Corp | Oxygen absorbent |
| JP2012087295A (en) * | 2010-09-21 | 2012-05-10 | Unitika Ltd | Deoxygenation coating agent, coating film containing deoxidation agent and laminate |
| US20130207042A1 (en) * | 2010-08-13 | 2013-08-15 | Ronald Vicente Joven Pineda | Oxygen-absorbing compound encapsulated in a silica matrix and method for the production thereof |
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2018
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6214939A (en) * | 1985-07-12 | 1987-01-23 | Kawasaki Kasei Chem Ltd | Oxygen scavenger and its preparation |
| JPS62183834A (en) * | 1986-12-26 | 1987-08-12 | Toppan Printing Co Ltd | Oxygen absorbent package |
| JPH10314581A (en) * | 1997-03-19 | 1998-12-02 | Mitsubishi Gas Chem Co Inc | Oxygen absorbent and culture method for anaerobic bacteria using the same |
| JP2005137215A (en) * | 2003-11-04 | 2005-06-02 | Asahi Kasei Life & Living Corp | Oxygen absorbent |
| US20130207042A1 (en) * | 2010-08-13 | 2013-08-15 | Ronald Vicente Joven Pineda | Oxygen-absorbing compound encapsulated in a silica matrix and method for the production thereof |
| JP2012087295A (en) * | 2010-09-21 | 2012-05-10 | Unitika Ltd | Deoxygenation coating agent, coating film containing deoxidation agent and laminate |
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