JPH0687969B2 - Oxygen absorber composition - Google Patents
Oxygen absorber compositionInfo
- Publication number
- JPH0687969B2 JPH0687969B2 JP10315386A JP10315386A JPH0687969B2 JP H0687969 B2 JPH0687969 B2 JP H0687969B2 JP 10315386 A JP10315386 A JP 10315386A JP 10315386 A JP10315386 A JP 10315386A JP H0687969 B2 JPH0687969 B2 JP H0687969B2
- Authority
- JP
- Japan
- Prior art keywords
- oxygen
- polyallylamine
- composition
- water
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は食品、農水産物、毛皮、天然繊維、紙、又は、
これらの加工製品を微生物、昆虫及び、酸素の害から保
護するための赤褐色の鉄錆の発生及び水素の副生を抑制
した脱酸素剤組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to food, agricultural and marine products, fur, natural fiber, paper, or
The present invention relates to an oxygen scavenger composition which suppresses the generation of reddish brown iron rust and the by-product of hydrogen for protecting these processed products from the damage of microorganisms, insects and oxygen.
金属粉末が酸化促進剤の共存下で空気中の酸素と速やか
に反応して酸化物となることは、よく知られ、金属粉末
として鉄粉又はその造粒物を、又、酸化促進剤としてア
ルカリ又は、アルカリ土類金属のハロゲン化物と水分を
利用した組成物が、酸素除去剤として広く用いられてい
る。It is well known that a metal powder rapidly reacts with oxygen in the air to form an oxide in the presence of an oxidation promoter, and an iron powder or a granulated product thereof is used as the metal powder, and an alkali is used as the oxidation promoter. Alternatively, a composition using a halide of an alkaline earth metal and water is widely used as an oxygen scavenger.
さらに、かかる組成物をガス透過性の容器に包装し、食
品、農水産物、毛皮、天然繊維、紙、及びこれらの加工
製品（以下これらを総称して物品等という）と共にガス
バリヤー性の容器に封入して、カビなどの微生物や象虫
などの昆虫の被害、酸素の被害から物品を保護する保存
剤として広く実用化されている。Further, such a composition is packaged in a gas permeable container, and a gas barrier container is provided together with food, agricultural and marine products, fur, natural fiber, paper, and processed products thereof (hereinafter collectively referred to as articles, etc.). Encapsulated and widely used as a preservative to protect articles from damages of microorganisms such as molds and insects such as elephants, and damages of oxygen.
他方、金属表面が水と反応して金属酸化物を生成すると
同時に水素を発生するという難点があり、また、金属と
して鉄を使用した場合には、この鉄が空気中の酸素や水
と反応し酸化物となつたとき発錆して赤褐色を呈し、こ
の酸化物の微粉が容器中にもれるおそれもあり、物品の
保存剤として難点があつた。これを解決するための方法
として、特公昭56−33980、特開昭56−148272、特開昭5
6−150433等、種々提案されているが、これらの方法
は、いずれも繁雑で実施に困難を伴い実用化されていな
い。On the other hand, there is a problem that the metal surface reacts with water to generate a metal oxide and at the same time hydrogen is generated.When iron is used as a metal, the iron reacts with oxygen in the air and water. When it becomes an oxide, it rusts and exhibits a reddish brown color, and fine powder of this oxide may be contained in the container, which is a problem as a preservative for articles. As a method for solving this, Japanese Patent Publication No. 56-33980, Japanese Patent Publication No. 56-148272, Japanese Patent Publication No.
Various proposals such as 6-150433 have been made, but none of these methods have been put to practical use because they are complicated and difficult to carry out.
本発明は、これらの欠点を克服した安全で清潔な物品保
存用の脱酸素剤組成物を提供することにある。The present invention provides a safe and clean oxygen absorber composition for storing articles, which overcomes these drawbacks.
本発明組成物は、鉄粉又はその造粒物及びその酸化促進
剤並びにポリアリルアミンを有効成分とする脱酸素剤組
成物であつて、該組成物をガス通過性の容器に充填し物
品の保存剤として利用するものである。The composition of the present invention is an oxygen scavenger composition containing iron powder or a granulated product thereof, an oxidation promoter thereof, and polyallylamine as an active ingredient, and the composition is filled in a gas permeable container to store articles. It is used as an agent.
本発明に用いる酸化促進剤としては、アルカリ又はアル
カリ土類金属の水酸化物、又は塩化物、又はこれをゼオ
ライト、活性炭等の多孔質粉粒体に担持させたものなど
が用いられる。アルカリ又はアルカリ土類金属の塩化物
が最も好ましい。本発明組成物は水を含有せしめておく
のが好ましいが水を含ませる場合、水を予め混合前の成
分に含有させておいてもよく、又、混合した後に添加し
てもよい。水を他の吸着体に吸着させたものを混合して
もよく、又、アルカリ又はアルカリ土類金属の塩化物を
水溶液として吸着体に担持させたものをそのまゝ用いて
もよく、或いは、該担持した吸着体を一旦乾燥して貯蔵
しておいた場合には金属粉末と混合する前に又は混合し
た後に水を添加してもよい。As the oxidation accelerator used in the present invention, a hydroxide or chloride of an alkali or alkaline earth metal, or a substance obtained by supporting this on a porous powder or granular material such as zeolite or activated carbon can be used. Most preferred are alkali or alkaline earth metal chlorides. The composition of the present invention preferably contains water, but in the case of containing water, water may be contained in the components before mixing in advance, or may be added after mixing. Water adsorbed on another adsorbent may be mixed, or the adsorbent may be used as it is, on which chloride of an alkali or alkaline earth metal is carried as an aqueous solution. When the supported adsorbent is once dried and stored, water may be added before or after mixing with the metal powder.
又、水分を多量に含有している食品等にあつては、本組
成物中に水を加えなくても、この食品等に含有させる水
分に由来する水蒸気によつて目的が達成される。即ち、
本発明の組成物が酸素と結合し系内から酸素を除去する
効果を発揮する際に水分が共存していればよいので、か
ならずしも本発明の組成物中に水が存在しなくてもよ
い。Further, in the case of foods containing a large amount of water, the object can be achieved by the water vapor derived from the water contained in the foods without adding water to the composition. That is,
It is not always necessary that water be present in the composition of the present invention, as long as water is present when the composition of the present invention binds to oxygen and exerts the effect of removing oxygen from the system.
本発明に用いるポリアリルアミンは重合度に関わりなく
有効である。ポリアリルアミンの鉄粉に対する反応のメ
カニズムは、明確でないので一概には言えないが、赤褐
色のサビの生成を抑制し水素の発生を極度に減少せしめ
ている点から、鉄の水酸化物の生成を抑制していると考
えられる。しかもその作用は、脱酸素剤組成物の酸素除
去能力には、全く影響を与えないという利点がある。The polyallylamine used in the present invention is effective regardless of the degree of polymerization. The mechanism of the reaction of polyallylamine with iron powder is unclear, so it cannot be generally stated.However, since the generation of reddish brown rust is suppressed and the generation of hydrogen is extremely reduced, the formation of iron hydroxide is suppressed. It is considered to be suppressed. Moreover, its action has an advantage that it does not affect the oxygen removing ability of the oxygen absorber composition at all.
ポリアリルアミンは、そのもの自身で加えてもよく、ま
た、それを溶液とした後、他の多孔質吸着体に吸着させ
た形で加えてもよい。最も好ましくは、本発明者等が先
に発明し、特許出願した方法、すなわち、ポリアリルア
ミン溶液を多孔質吸着体に吸着させた後、加熱乾燥する
ことにより未重合モノマーや揮発性のオリゴマーを除去
し、無臭のものにしたものを他の成分と混合するのがよ
い。これは、未重合モノマーや揮発性オリゴマーが著し
く悪臭を有し、特に食品等の保存用に使用した場合に好
ましくないからである。The polyallylamine may be added by itself, or may be added in the form of being adsorbed to another porous adsorbent after it is made into a solution. Most preferably, the method that the present inventors previously invented and applied for a patent, that is, after adsorbing the polyallylamine solution on the porous adsorbent and then heating and drying, the unpolymerized monomer and the volatile oligomer are removed. However, it is better to mix the odorless one with other ingredients. This is because unpolymerized monomers and volatile oligomers have a marked odor and are not preferable especially when used for storage of foods and the like.
ポリアリルアミンは、また、架橋してアニオン交換樹脂
としたものも好適に利用しうる。As the polyallylamine, those obtained by crosslinking to form an anion exchange resin can be preferably used.
本発明の組成物は鉄の赤褐色の錆の発生及び水素の副生
を抑制する以外に、その系内にアルコールが存在する場
合、それが別の悪臭源となることをポリアリルアミンの
共存により防止する利点をも有する。その作用は理論的
には明らかでないがアルコール類が金属粉の酸化物の存
在下に酸素によつて酸化されてアルデヒド類を生成する
反応を抑制するためか或いは、アルデヒド類と反応して
全く他の無臭の物質に変えるためのいずれかと考えられ
る。この特性は食品等の保存に用いる際に、それがアル
コールを含んでいるか、或いは、同じ保存の目的でアル
コールを併用する場合に悪臭を生じないという大きな利
点となる。The composition of the present invention, in addition to suppressing the generation of reddish brown rust of iron and the by-product of hydrogen, when alcohol is present in the system, it prevents another malodor source by the coexistence of polyallylamine. It also has the advantage of Although its action is not theoretically clear, it may be due to suppressing the reaction in which alcohols are oxidized by oxygen in the presence of metal powder oxides to form aldehydes, or by reacting with aldehydes to completely eliminate other reactions. It is thought to be either for the conversion to odorless substances. This characteristic is a great advantage that when it is used for preservation of foods, it does not produce a bad odor when it contains alcohol or when alcohol is used together for the same preservation purpose.
次に実施例を挙げて説明する。Next, examples will be described.
遊離ポリアリルアミン担持体の調製 ポリアリルアミン塩酸塩水溶液（PAA−HCl−10L、濃度5
0％、日東紡績製）1.0重量部に対し、10％NaOH水溶液2.
2重量部を加え撹拌し、遊離のポリアリルアミン水溶液
としたものと、粉末状二酸化ケイ素（フロイント産業
アドソリダー101）5.0重量部を均一に撹拌混合し、105
℃で５時間通風乾燥し、粉末状遊離ポリアリルアミン担
持体を得た。（以下これを「Ｐ」と省略する。） 実施例１−６、比較例１−３ 鉄粉及び酸化促進剤として各種塩化物にＰを表−１に示
す処方で混合して酸素除去用組成物を得た。これを保存
剤として使用するためにレーヨン和紙に有孔ポリエチレ
ンをラミネートしたフイルムで作成した小袋内に入れヒ
ートシールし、市販の切り餅６枚（270g）と共に容積1.
2のポリ塩化ビニリデンでコートしたナイロン／ポリ
エチレンの積層フイルムで作つた袋に入れ密閉した。こ
れらを室温にて保存し、保存効果、酸素除去能力、赤サ
ビの発生状態、及び水素濃度を測定した。又、比較例と
して、鉄粉と酸化促進剤のみのものを用いて同様に実験
を行つた。その結果を表−１に示す。Preparation of free polyallylamine carrier Polyallylamine hydrochloride aqueous solution (PAA-HCl-10L, concentration 5
0%, made by Nitto Boseki) 1.0 part by weight, 10% NaOH aqueous solution 2.
Add 2 parts by weight and stir to make a free polyallylamine aqueous solution and powdered silicon dioxide (Freund Industrial
Ad Solider 101) 5.0 parts by weight are uniformly mixed by stirring, and 105
It was air-dried at 5 ° C. for 5 hours to obtain a powdery free polyallylamine carrier. (Hereinafter, this is abbreviated as "P".) Example 1-6, Comparative Example 1-3 Iron powder and various chlorides as oxidation promoters were mixed with P in the formulation shown in Table 1 to remove oxygen. I got a thing. To use this as a preservative, heat-seal it in a small bag made of rayon Japanese paper laminated with perforated polyethylene, and heat-seal it.
It was put in a bag made of a laminated film of nylon / polyethylene coated with polyvinylidene chloride of 2 and sealed. These were stored at room temperature, and the storage effect, oxygen removal capacity, generation state of red rust, and hydrogen concentration were measured. As a comparative example, the same experiment was conducted using only iron powder and an oxidation promoter. The results are shown in Table-1.
実施例−７、８ 実施例１で調製した酸素除去用組成物を使用した保存剤
をアルコールを含む菓子類と共に容積1.0のポリ塩化
ビニリデンコートしたナイロン／ポリエチレンの積層フ
イルムで作つた袋に入れ密封した。これらを室温で保存
したときの保存効果、赤錆の発生状態、水素発生、及
び、異臭に関する官能試験を行つた。又、比較例５及び
７として比較例１の保存剤を用いて、また、比較例６及
び７として脱酸素剤を使用しないものについて同様に実
施した。結果を表−２及び表−３に示す。 Examples -7 and 8 The preservative using the oxygen scavenging composition prepared in Example 1 was placed in a bag made of a polyvinylidene chloride-coated nylon / polyethylene laminated film having a volume of 1.0 together with confectionery containing alcohol and sealed. did. A sensory test was conducted on the storage effect when these were stored at room temperature, the generation state of red rust, hydrogen generation, and offensive odor. Further, the same procedure was performed for Comparative Examples 5 and 7 using the preservative of Comparative Example 1, and for Comparative Examples 6 and 7 not using the oxygen scavenger. The results are shown in Table-2 and Table-3.
〔発明の効果〕 前記実施例及び比較例の対比から明らかなように本発明
は従来の鉄粉又はその造粒物及び酸化促進剤からなる脱
酸素剤にポリアリルアミンを配合することにより、これ
を食品その他の物品の保存剤として使用した場合、長期
間有効であり、異臭、赤錆、水素等の発生を抑制すると
いう利点がある。 [Effect of the invention] As is clear from the comparison of the above-mentioned Examples and Comparative Examples, the present invention provides a conventional iron powder or a granulated product thereof and an oxygen scavenger by adding a polyallylamine to the deoxidant. When used as a preservative for foods and other articles, it is effective for a long period of time and has the advantage of suppressing the generation of offensive odor, red rust, hydrogen and the like.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 池間 龍二 東京都新宿区高田馬場２丁目14番２号 フ ロイント産業株式会社内 (72)発明者 猪鼻 伸二 東京都新宿区高田馬場２丁目14番２号 フ ロイント産業株式会社内 (72)発明者 星野 正子 東京都新宿区高田馬場２丁目14番２号 フ ロイント産業株式会社内 (56)参考文献 特開 昭62−186941（ＪＰ，Ａ) 特開 昭62−186942（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Ryuji Ikema 2-14-2 Takadanobaba, Shinjuku-ku, Tokyo Inside Freund Sangyo Co., Ltd. (72) Shinji Inohana 2-14-2 Takadanobaba, Shinjuku-ku, Tokyo No. Freonto Sangyo Co., Ltd. (72) Inventor Masako Hoshino 2-14-2 Takadanobaba, Shinjuku-ku, Tokyo No. 2 Freonto Sangyo Co., Ltd. (56) Reference JP-A-62-186941 (JP, A) JP 62-186942 (JP, A)
Claims (2)
びにポリアリルアミンを有効成分とする脱酸素剤組成
物。1. An oxygen scavenger composition containing iron powder or a granulated product thereof, an oxidation promoter thereof, and polyallylamine as an active ingredient.
れたものである特許請求の範囲第１項記載の脱酸素剤組
成物。2. The oxygen absorber composition according to claim 1, wherein the polyallylamine is supported on a porous adsorbent.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10315386A JPH0687969B2 (en) | 1986-05-07 | 1986-05-07 | Oxygen absorber composition |
| US06/945,364 US4820442A (en) | 1985-12-26 | 1986-12-22 | Preservative composition |
| DE8686117959T DE3675752D1 (en) | 1985-12-26 | 1986-12-23 | PRESERVATIVE COMPOSITION. |
| EP86117959A EP0229380B1 (en) | 1985-12-26 | 1986-12-23 | Preservative composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10315386A JPH0687969B2 (en) | 1986-05-07 | 1986-05-07 | Oxygen absorber composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62262744A JPS62262744A (en) | 1987-11-14 |
| JPH0687969B2 true JPH0687969B2 (en) | 1994-11-09 |
Family
ID=14346557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10315386A Expired - Lifetime JPH0687969B2 (en) | 1985-12-26 | 1986-05-07 | Oxygen absorber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0687969B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3669414B2 (en) * | 1999-07-01 | 2005-07-06 | 味の素株式会社 | Iron-based oxygen-absorbing resin composition and packaging material and container using the same |
| JP6088940B2 (en) * | 2013-08-26 | 2017-03-01 | フロイント産業株式会社 | Deoxidizer for alcohol-containing foods |
-
1986
- 1986-05-07 JP JP10315386A patent/JPH0687969B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62262744A (en) | 1987-11-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4384972A (en) | Foodstuff freshness keeping agents | |
| JP2701999B2 (en) | Oxygen absorber | |
| US4820442A (en) | Preservative composition | |
| KR0130460B1 (en) | Oxygen absorber and method for producing same | |
| JPH04293474A (en) | Food preservative and preservation of food using the same | |
| CA2385738C (en) | Rapid oxygen absorption by using activators | |
| JPH0687969B2 (en) | Oxygen absorber composition | |
| JP3541859B2 (en) | Oxygen absorber and its package | |
| JP2923978B2 (en) | Oxygen scavenger | |
| JPS5939243A (en) | Freshness-keeping agent | |
| JP2001321141A (en) | Food preservative | |
| JP2800178B2 (en) | Food preservation composition | |
| JPH11207177A (en) | Deoxidizer | |
| JP2822440B2 (en) | Oxygen scavenger | |
| JPH0436086B2 (en) | ||
| JP2668888B2 (en) | Oxygen absorber | |
| JPH0570420B2 (en) | ||
| JPH08140643A (en) | Food preserving agent and preservation of food | |
| JP2943156B2 (en) | Oxygen scavenger | |
| JP2943155B2 (en) | Oxygen scavenger | |
| JPH04244229A (en) | Oxygen absorbent | |
| JPS63233769A (en) | Freshness-keeping agent | |
| JP3431043B2 (en) | Oxygen scavenger | |
| JPH0437710B2 (en) | ||
| JP2993085B2 (en) | Oxygen scavenger |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |