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JP2001037457A - Deoxidizer - Google Patents

Deoxidizer

Info

Publication number
JP2001037457A
JP2001037457A JP11212749A JP21274999A JP2001037457A JP 2001037457 A JP2001037457 A JP 2001037457A JP 11212749 A JP11212749 A JP 11212749A JP 21274999 A JP21274999 A JP 21274999A JP 2001037457 A JP2001037457 A JP 2001037457A
Authority
JP
Japan
Prior art keywords
carrier
oxygen
magnesium
water
oxygen scavenger
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.)
Pending
Application number
JP11212749A
Other languages
Japanese (ja)
Inventor
Hidechika Wakabayashi
英親 若林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Gas Chemical Co Inc
Original Assignee
Mitsubishi Gas Chemical Co Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mitsubishi Gas Chemical Co Inc filed Critical Mitsubishi Gas Chemical Co Inc
Priority to JP11212749A priority Critical patent/JP2001037457A/en
Publication of JP2001037457A publication Critical patent/JP2001037457A/en
Pending legal-status Critical Current

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  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain a deoxidizer having practical oxygen absorption ability even in an atmosphere of low humidity wherein conventional deoxidizers are not functionable, generating no nasty smell and undetectable with a metal detector by including a carrier and activated magnesium supported on the carrier. SOLUTION: This deoxidizer is obtained by comprising (A) a carrier such as diatomite, zeolite or acid clay and (B) activated magnesium supported on the carrier wherein the activated magnesium is obtained by supporting a magnesium compound on the carrier and reducing or decomposing the compound (the supporting ratio is preferably 5-90 wt.%). The deoxidizer comprises the activated magnesium as principal ingredient and a water donor such as a water- absorbing resin as an auxiliary and is substantially free from magnetic material.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明は、担体に担持された
活性化マグネシウム金属を主剤とする脱酸素剤に関す
る。詳しくは、金属探知機に検知されない脱酸素剤又は
低湿度雰囲気下でも酸素吸収活性を有する脱酸素剤に関
する。
[0001] The present invention relates to a deoxidizer containing activated magnesium metal supported on a carrier as a main component. More specifically, the present invention relates to a deoxidizer that is not detected by a metal detector or a deoxidizer that has oxygen absorption activity even in a low humidity atmosphere.

【0002】[0002]

【従来の技術】最近、密閉包装体中で物品を保存する方
法として、種々の脱酸素剤を用いる保存方法が開発さ
れ、安価で確実な保存方法として注目されている。そし
て、これまでに種々の有機系及び無機系主剤の脱酸素剤
が知られている。例えば、無機系主剤として鉄粉などの
金属粉、亜硫酸塩、亜硫酸水素塩、亜二チオン酸塩、チ
オ硫酸塩などを用いたもの、有機系主剤としてL−アス
コルビン酸、エルソルビン酸及びそれらの塩、グルコー
スなどの還元性糖類、カテコール、ピロガロールなどの
還元性多価フェノール類、エチレングリコール、グリセ
リンなどの多価アルコール類を用いたものがあげられ
る。
2. Description of the Related Art Recently, a storage method using various oxygen absorbers has been developed as a method for storing articles in a sealed package, and has attracted attention as an inexpensive and reliable storage method. Various organic and inorganic base oxygen scavengers have been known. For example, inorganic powders such as metal powders such as iron powder, sulfites, bisulfites, dithionites, thiosulfates, etc., and L-ascorbic acid, ersorbic acid and salts thereof as organic bases. And reducing sugars such as glucose, catechol and pyrogallol, and polyhydric alcohols such as ethylene glycol and glycerin.

【0003】しかし、これら従来の脱酸素剤は、無機
系、有機系問わず、いずれも機能発現に水もしくは水分
が共存することが必須であるために乾燥食品、医薬品、
金属製品などの極めて共存水分の低い低湿度雰囲気で保
存する必要がある物品には適用できなかった。
[0003] However, these conventional oxygen scavengers, whether inorganic or organic, require the coexistence of water or water for their function to be exhibited, so that dry foods, pharmaceuticals,
It cannot be applied to articles that need to be stored in a low humidity atmosphere with extremely low coexisting moisture, such as metal products.

【0004】更に、代表的な無機系主剤の鉄粉系脱酸素
剤では、金属探知機に感応するため、食品などの物品と
同封した状態で金属検査が出来ない。無機系主剤の内、
亜硫酸塩などの含硫黄化合物系脱酸素剤では、硫黄臭が
発生し開封時に不快感を感じ、食品の風味を損なうなど
の悪影響が懸念される問題があった。また、有機系主剤
の脱酸素剤は、多くの場合、主剤原料が高価である。
Further, a typical inorganic base iron powder-based oxygen scavenger is sensitive to a metal detector, so that a metal inspection cannot be performed in a state of being enclosed with an article such as food. Of the inorganic base agents,
Sulfur-containing compound-based oxygen scavengers such as sulfites have a problem in that a sulfur odor is generated and unpleasant sensation is felt at the time of opening, which may adversely affect the flavor of food. In addition, in many cases, the base material of the oxygen-based oxygen scavenger is expensive.

【0005】本発明者は、脱酸素機能の発現に水もしく
は水分の存在が特に必須条件でなく、実用的な脱酸素機
能の発現に促進物質が必要でなく、臭気の発生もない脱
酸素剤として、担体に担持した活性化したマンガン、
鉄、コバルト、ニッケル、銅などの遷移金属を主剤とし
た脱酸素剤を見出し、特開平8−38883、特開平8
−38884に開示した。本発明者は、安全性が高く、
金属探知機に検知されず、低湿度雰囲気にも適用でき
る、安価で実用的な脱酸素能力を有する脱酸素剤につい
て、さらに検討を進めた。
[0005] The present inventor has argued that the presence of water or moisture is not particularly essential for the expression of the deoxygenating function, and that a deoxidizing agent which does not require a promoting substance for the expression of a practical deoxygenating function and which does not generate odor. Activated manganese supported on a carrier,
A deoxidizer containing a transition metal such as iron, cobalt, nickel and copper as a main component has been found.
-38884. The inventor has high security,
Further studies have been conducted on an inexpensive and practical oxygen scavenging agent that is not detected by a metal detector and can be applied to a low-humidity atmosphere.

【0006】[0006]

【発明が解決しようとする課題】本発明の目的は、実用
的な脱酸素能力を有し、金属探知機に検知されず、しか
も低湿度雰囲気にも適用できる、安価で安全性の高い脱
酸素剤を提供することにある。
SUMMARY OF THE INVENTION It is an object of the present invention to provide an inexpensive and highly safe deoxygenator which has a practical deoxidizing ability, is not detected by a metal detector, and can be applied to a low humidity atmosphere. To provide an agent.

【0007】[0007]

【課題を解決するための手段】本発明者は、前記の課題
を解決する方法を検討した結果、担体に担持した活性化
マグネシウムを主剤とする脱酸素剤を見出し、本発明を
完成させるに至った。即ち、本発明は、主剤として安価
なマグネシウム化合物を担体に担持後、還元処理し、活
性化処理することによって実用的な脱酸素機能の発現に
水分の存在が特に必須条件でなく、従来の脱酸素剤が機
能できない低湿度雰囲気下でも酸素吸収活性を示し、実
用的な脱酸素能力を得るのに促進物質も不要で、臭気や
異臭の発生もなく、しかも金属探知機に検知されなく安
価で安全性の高いことを特徴とする脱酸素剤に関する。
Means for Solving the Problems As a result of studying a method for solving the above-mentioned problems, the present inventor has found an oxygen scavenger containing activated magnesium supported on a carrier as a main component and completed the present invention. Was. That is, according to the present invention, the presence of water is not particularly essential for the expression of a practical deoxygenation function by carrying out a reduction treatment and an activation treatment after supporting an inexpensive magnesium compound on a carrier as a main agent. It shows oxygen absorption activity even in low humidity atmosphere where oxygen agent can not function, does not require accelerating substances to obtain practical deoxygenation capacity, does not generate odor or off-odor, and is inexpensive because it is not detected by metal detector It relates to a deoxidizer characterized by high safety.

【0008】[0008]

【発明の実施の形態】本発明において、活性化マグネシ
ウムとは、担体に担持されたマグネシウム化合物を還元
してなるものである。活性化マグネシウムは、担体に担
持されていることが重要である。即ち、主剤原料のマグ
ネシウム化合物を単に活性化したものや金属マグネシウ
ムを単に担体と混合したものでは、実用的な脱酸素能力
を得ることはできない。ここで実用的な脱酸素能力と
は、活性化マグネシウム主剤1g当たり100mlO2
/g以上の酸素吸収を行う能力のことである。
BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, activated magnesium is obtained by reducing a magnesium compound supported on a carrier. It is important that the activated magnesium is supported on a carrier. That is, practical deoxygenation ability cannot be obtained by simply activating the magnesium compound as the base material or simply mixing magnesium metal with the carrier. Here, the practical deoxidizing capacity means 100 ml O 2 per 1 g of activated magnesium base.
/ G or more.

【0009】本発明においては、担体に担持された活性
化マグネシウムを主剤とする。主剤とは、酸素と反応し
てこれを吸収する成分のことである。本発明では、主剤
のみでも酸素吸収を行うが、必要に応じて助剤をこれに
組み合わせる。助剤としては、安全性に問題がなく、金
属探知機に検知されないなど本発明の目的を阻害しない
ものを添加することができる。好ましい助剤としては、
水もしくは水分供与体を挙げることができる。
In the present invention, activated magnesium carried on a carrier is used as a main ingredient. The main agent is a component that reacts with and absorbs oxygen. In the present invention, oxygen absorption is performed with only the main agent, but an auxiliary is combined with this as needed. As the auxiliaries, those which have no problem in safety and which do not inhibit the object of the present invention, such as being not detected by a metal detector, can be added. Preferred auxiliaries include
Water or moisture donors can be mentioned.

【0010】本発明で用いられる活性化マグネシウム
は、マグネシウムの無機塩、有機塩等のマグネシウム化
合物を担体に担持後、加熱還元または分解還元などの還
元処理をしたものである。この一連の操作によって、酸
素吸収反応に対して活性化したマグネシウムが得られ
る。マグネシウムの無機塩化合物としては、例えば、マ
グネシウムの硫酸塩、硝酸塩、塩酸塩、炭酸塩などが用
いられる。また、マグネシウムの有機塩化合物として
は、例えば、その蟻酸塩、酢酸塩、蓚酸塩などが用いら
れる。
The activated magnesium used in the present invention is obtained by carrying a magnesium compound such as an inorganic salt or an organic salt of magnesium on a carrier and then subjecting the carrier to a reduction treatment such as heat reduction or decomposition reduction. Through this series of operations, magnesium activated for the oxygen absorption reaction is obtained. As the inorganic salt compound of magnesium, for example, magnesium sulfate, nitrate, hydrochloride, carbonate and the like are used. Further, as the organic salt compound of magnesium, for example, its formate, acetate, oxalate and the like are used.

【0011】本発明において用いられる担体には、天然
物もしくは合成物に特に限定されなく、例えば、活性
炭、珪藻土、粘土、ゼオライト、セライト、酸性白土、
アルミナ、シリカ、チタニア及びその他の金属酸化物を
使用できる。好ましくは、珪藻土、ゼオライト、酸性白
土である。これらの担体に、上記マグネシウム化合物を
常法の含侵法、共沈法などの公知の方法によって担持さ
せる。
The carrier used in the present invention is not particularly limited to a natural product or a synthetic product. For example, activated carbon, diatomaceous earth, clay, zeolite, celite, acid clay,
Alumina, silica, titania and other metal oxides can be used. Preferably, diatomaceous earth, zeolite, and acid clay are used. The above-mentioned magnesium compound is supported on these carriers by a known method such as a conventional impregnation method and a coprecipitation method.

【0012】特に、本発明の脱酸素剤組成物は、磁性体
を実質的に含まない場合に、金属探知機に検知されない
脱酸素剤組成物になるので、好ましい。そのために、磁
性体を実質的に含まない担体を使用することが好まし
い。
In particular, the oxygen scavenger composition of the present invention is preferable when it does not substantially contain a magnetic substance, because the oxygen scavenger composition is not detected by a metal detector. Therefore, it is preferable to use a carrier substantially free of a magnetic substance.

【0013】担体に担持させるマグネシウム化合物の量
は、活性化マグネシウムの担持率が5〜90重量%であ
るようにする。活性化に要する時間、活性効率から30
〜80重量%が好ましい。活性化マグネシウムの担持率
は、マグネシウム量(マグネシウム元素換算値)と担体
量(乾燥状態換算値)の合計に対するマグネシウム量の
重量%で表される。
The amount of the magnesium compound to be carried on the carrier is such that the activated magnesium carrying ratio is 5 to 90% by weight. Activation time, 30% from activation efficiency
~ 80% by weight is preferred. The loading ratio of activated magnesium is represented by the weight% of the amount of magnesium with respect to the total of the amount of magnesium (converted to a magnesium element) and the amount of carrier (converted to a dry state).

【0014】本発明におけるマグネシウムの活性化処理
方法としては、ホルマリン、蟻酸などの還元性化合物に
よる化学還元法や一酸化炭素、水素などの還元性ガスに
よる接触還元法等の還元方法があげられる。また、蟻酸
マグネシウム等の分解性マグネシウム化合物を、不活性
ガス中、又は、一酸化炭素、水素などの還元性ガス中で
加熱分解する分解方法も用いられる。
Examples of the method for activating magnesium in the present invention include reduction methods such as a chemical reduction method using a reducing compound such as formalin and formic acid, and a catalytic reduction method using a reducing gas such as carbon monoxide and hydrogen. Further, a decomposition method in which a decomposable magnesium compound such as magnesium formate is thermally decomposed in an inert gas or a reducing gas such as carbon monoxide or hydrogen is also used.

【0015】本発明におけるマグネシウムの活性化処理
条件については、担持されるマグネシウム化合物の還元
性もしくは分解性、またその担持量、処理方法などによ
り異なり一義的には決められないが、接触還元方法では
通常、還元雰囲気温度100℃〜800℃で10分〜1
0時間、特に200℃〜600℃で30分〜6時間の条
件が好適に用いられる。
The conditions for the activation treatment of magnesium in the present invention vary depending on the reducibility or decomposability of the supported magnesium compound, the amount of the supported magnesium compound, the treatment method, and the like, and cannot be uniquely determined. Usually, at a reducing atmosphere temperature of 100 ° C to 800 ° C for 10 minutes to 1
A condition of 0 hour, particularly 200 ° C. to 600 ° C. for 30 minutes to 6 hours is suitably used.

【0016】活性化する際のマグネシウム化合物の担持
された担体の形態としては、粒状または粉末のいずれの
形態で活性化しても良いし、また、加圧成型、押し出し
成型などの通常の成型法によって成型してから活性化し
ても良い。
As the form of the carrier carrying the magnesium compound upon activation, it may be activated in either granular or powder form, or by a usual molding method such as pressure molding or extrusion molding. It may be activated after molding.

【0017】活性化処理して得られたマグネシウム金属
からなる脱酸素剤主剤は、空気中では非常に酸化されや
すいので、保管する際には、酸素バリヤー性の高い容器
に収納される。本発明の脱酸素剤主剤のみ又は脱酸素剤
主剤と助剤からなる脱酸素剤組成物は、保存する対象物
品に応じて、例えば、適度の通気性を有する小袋に充填
して小袋入り脱酸素剤包装体として用いられる。この小
袋入り脱酸素剤包装体を保存物品と共に酸素・湿分バリ
ヤー性の高い材料、例えば、KOP/ポリエチレン、K
ON/ポリエチレン、Al/ポリエチレン、PET/A
l/ポリエチレンなどのガスバリヤー性包装袋に密封し
て用いられる。本発明の脱酸素剤主剤は、水分を共存さ
せた条件で速やかに多量の酸素吸収を行うが、共存させ
ない条件でも、実用的な酸素吸収を行うことができる。
[0017] The oxygen scavenger base obtained from the magnesium metal obtained by the activation treatment is very easily oxidized in the air, and is stored in a container having a high oxygen barrier property when stored. The oxygen scavenger composition comprising the oxygen scavenger main agent alone or the oxygen scavenger main agent and the auxiliary agent according to the target article to be preserved, for example, is filled in a small bag having a suitable air permeability and is filled in a small bag. It is used as an agent package. The package containing the oxygen-absorbing agent in the small bag is stored together with the preserved article in a material having a high oxygen / moisture barrier property, such as KOP / polyethylene,
ON / polyethylene, Al / polyethylene, PET / A
1 / Used sealed in a gas barrier packaging bag such as polyethylene. The oxygen scavenger main agent of the present invention quickly absorbs a large amount of oxygen under the condition of coexisting moisture, but can perform practical oxygen absorption even under the condition of no coexistence.

【0018】本発明の脱酸素剤主剤のみ又は脱酸素剤主
剤と助剤からなる脱酸素剤組成物を充填・包装した小袋
入り脱酸素剤と水または水分を共存させる場合、保存す
る物品の水分活性、保存量の条件によっていくつかの方
法がある。その一つは、保存する物品の水分活性値が
0.6以上で保存する物品量が脱酸素剤に対して過剰量
にある場合には、この乾燥状態にある小袋入り脱酸素剤
が物品の性状に悪影響を及ぼす恐れが事実上ないのでこ
の小袋入り脱酸素剤をそのまま用いることができる。し
かし、水分活性値が0.6未満の乾燥した物品を保存す
る場合には、本発明の小袋入り脱酸素剤が脱酸素機能以
外に除湿機能をも有するため物品から水分を奪い品性を
変化させる場合がある。このような場合には、活性化マ
グネシウムが担持されている担体に直接、適量の水もし
くは調湿液を添加するか、又は、この担体とは別に水分
供給体として、適量の水もしくは調湿液を含侵させた含
水性の多孔質体を用いて、物品の保存条件に対応した条
件で水分または湿気を共存させる。
When water or moisture coexists with the oxygen absorber in the sachet filled and packed with the oxygen absorber alone or the oxygen absorber composition comprising the oxygen absorber and the auxiliary agent according to the present invention, the water content of the preserved article is There are several methods depending on the conditions of activity and storage amount. One of them is that when the water activity value of the stored product is 0.6 or more and the amount of the stored product is excessive relative to the oxygen scavenger, the oxygen scavenger in the dry pouch is considered to be Since there is practically no possibility of adversely affecting the properties, the oxygen absorber contained in the small bag can be used as it is. However, when storing a dried product having a water activity value of less than 0.6, the oxygen absorber contained in the sachet of the present invention has a dehumidifying function in addition to the deoxidizing function, so that it deprives the product of moisture and changes its properties. May be caused. In such a case, an appropriate amount of water or a humidifying solution is directly added to the carrier on which the activated magnesium is supported, or an appropriate amount of water or a humidifying solution is separately provided from the carrier as a water supplier. Using a water-containing porous body impregnated with water, moisture or moisture is allowed to coexist under conditions corresponding to the storage conditions of the article.

【0019】また、特に水分活性値が0.4未満の物品
で40%RH未満の乾燥条件で保存する場合には、乾燥
条件に応じて低湿度用の調湿液を用いたりするが、より
乾燥条件が好ましい場合には、調湿液、水分を特に共存
させることなく乾燥状態にある小袋状の脱酸素剤をその
まま用いることができる。その一例として、例えば、3
0%RH以下の特に低い湿度雰囲気で保存する必要があ
る乾燥食品、医薬品、金属製品などの乾燥系物品では、
水分や調湿液を用いずに物品と上記の小袋入り脱酸素剤
をそのまま、Al/ポリエチレン積層包装袋に密封して
用いられる。特に、低水分物品を保存する場合又は乾燥
した雰囲気で保存する場合、吸水性の固体を担体として
使用することが好ましい。吸水性の固体は、乾燥状態に
ある前記した多孔質固体を使用することができる。
In particular, when an article having a water activity value of less than 0.4 is stored under drying conditions of less than 40% RH, a humidity control liquid for low humidity may be used depending on the drying conditions. When the drying conditions are preferable, a small bag-shaped oxygen absorber in a dry state can be used as it is without coexisting a humidity control solution and moisture. As an example, for example, 3
In the case of dry products such as dry foods, pharmaceuticals, and metal products that need to be stored in a particularly low humidity atmosphere of 0% RH or less,
The article and the oxygen-absorbing agent in the above-mentioned small bag are used as they are, without using moisture or a humidity control liquid, sealed in an Al / polyethylene laminated packaging bag. In particular, when storing low-moisture articles or when storing in a dry atmosphere, it is preferable to use a water-absorbing solid as a carrier. As the water-absorbing solid, the above-mentioned porous solid in a dry state can be used.

【0020】本発明で用いられる水分供与体としては、
含水機能を有する物質であれば特に制限はなく、マグネ
シウム化合物を担持した担体そのものを利用しても良い
し、別に無機性の多孔質担体や各種の吸水性樹脂、親水
性樹脂、不織布、紙、綿などの有機性の含水性物質を助
剤として用いても良い。
The water donor used in the present invention includes:
There is no particular limitation as long as the substance has a water-containing function, and the carrier itself carrying the magnesium compound may be used, or an inorganic porous carrier or various water-absorbing resins, hydrophilic resins, nonwoven fabric, paper, An organic water-containing substance such as cotton may be used as an auxiliary.

【0021】[0021]

【実施例】以下、本発明を実施例によって説明する。The present invention will be described below with reference to examples.

【0022】実施例1 硫酸マグネシウム・7水和物114.09gを60℃の
水550mlに溶解し、これにゼオライト20gを入れ
攪拌混合する。次に、無水炭酸ナトリウム53.96g
を水200mlに溶解した水溶液を滴下し、そのまま1
時間30分攪拌した。終了後、不溶物を濾取し、濾液が
中性になるまで水で洗浄してから110℃で乾燥し、乾
燥粉末を得た。この乾燥粉末3.9gを採取し、磁器製
ボートに入れて窒素気流中で200℃、30分間予備加
熱後、水素気流中で450℃、3時間還元し、還元終了
後、窒素を通じて室温に冷却して脱酸素剤主剤を得た。
得られた脱酸素剤主剤には、マグネシウムが36重量%
含まれており、マグネシウム以外の成分はほとんどがゼ
オライトであった。
Example 1 Magnesium sulfate heptahydrate (114.09 g) was dissolved in 550 ml of water at 60 ° C., and 20 g of zeolite was added and mixed with stirring. Next, 53.96 g of anhydrous sodium carbonate
Was dissolved in 200 ml of water and added dropwise.
The mixture was stirred for 30 minutes. After completion, insolubles were collected by filtration, washed with water until the filtrate became neutral, and dried at 110 ° C. to obtain a dry powder. 3.9 g of the dried powder was collected, placed in a porcelain boat, preheated at 200 ° C. for 30 minutes in a nitrogen stream, reduced at 450 ° C. for 3 hours in a hydrogen stream, and cooled to room temperature through nitrogen after the reduction was completed. Thus, an oxygen scavenger base was obtained.
36% by weight of magnesium was contained in the obtained oxygen absorber.
Most of the components other than magnesium were zeolite.

【0023】窒素雰囲気のグローブボックス中で前記主
剤2.0gを有孔ポリエチレンでラミネートした紙小袋
に充填・包装して脱酸素剤包装体を得た。この脱酸素剤
包装体1個をグローブボックスより外に取り出し、水分
供与体として珪藻土1gを300kg/m2、3分の条
件で成型した直径12mmの圧密成型体に飽和食塩水を
1gずつ含浸させた錠剤2個及び湿度75%RHの空気
1500mlと共に、ポリ塩化ビニリデンコートナイロ
ン/ポリエチレン積層フィルムからなる包装袋に密封
し、これを25℃で保存し、10時間、30時間、50
時間後の袋内空間の酸素濃度及び湿度を分析した。その
結果を表1に示した。
In a glove box in a nitrogen atmosphere, 2.0 g of the main ingredient was filled and packed in a paper bag laminated with perforated polyethylene to obtain a package of an oxygen scavenger. One package of the oxygen absorber was taken out of the glove box, and 1 g of saturated saline was impregnated into a 12 mm-diameter compacted body formed by molding 1 g of diatomaceous earth as a moisture donor at 300 kg / m 2 for 3 minutes. Together with two tablets and 1500 ml of air at a humidity of 75% RH in a packaging bag made of a polyvinylidene chloride-coated nylon / polyethylene laminated film, and stored at 25 ° C. for 50 hours for 30 hours.
After a period of time, the oxygen concentration and the humidity of the space in the bag were analyzed. The results are shown in Table 1.

【0024】実施例2 実施例1で得られた脱酸素剤主剤2.0gに助剤として
水2.0gを含浸させ、これを有孔ポリエチレンでラミ
ネートした紙小袋に充填・包装して脱酸素剤包装体を得
た。この脱酸素剤包装体を湿度75%RHの空気150
0mlと共に、ナイロン/ポリ塩化ビニリデン/ポリエ
チレン積層フィルムからなる包装袋に密封した以外は実
施例1と全く同じ操作を行った。その結果を表1に示し
た。
Example 2 2.0 g of the oxygen scavenger base material obtained in Example 1 was impregnated with 2.0 g of water as an auxiliary agent, and this was filled and packaged in a paper bag laminated with perforated polyethylene to remove oxygen. An agent package was obtained. This oxygen-absorbing agent package is immersed in 150% air of 75% RH.
The same operation as in Example 1 was performed except that the container was sealed in a packaging bag composed of a nylon / polyvinylidene chloride / polyethylene laminated film together with 0 ml. The results are shown in Table 1.

【0025】実施例3 実施例1で得られた脱酸素剤主剤0.51gを、穿孔し
たPET/ポリエチレン積層フィルムを用い、充填・包
装して脱酸素剤包装体を得た。水分供与体を用いない
で、湿度40%RHの空気250mlと共に、PET/
アルミ箔/ポリエチレン積層フィルムからなる包装袋に
密封した以外は実施例1と全く同じ操作を行った。その
結果を表1に示した。
Example 3 0.51 g of the oxygen-absorbing agent base material obtained in Example 1 was filled and packaged using a perforated PET / polyethylene laminated film to obtain an oxygen-absorbing agent package. Without using a water donor, PET /
The same operation as in Example 1 was performed except that the package was sealed in a packaging bag made of aluminum foil / polyethylene laminated film. The results are shown in Table 1.

【0026】比較例1 実施例1においてゼオライト担体を用いなかった以外は
全く同じく反応、後処理を行い、乾燥粉末を得た。この
乾燥粉末とゼオライト20gをポリエチレンの袋の中で
均一に混合し、実施例1と全く同じく加熱還元した後、
有孔ポリエチレンでラミネートした紙小袋に充填・包装
して脱酸素剤包装体を得、包装袋に密封し、経時的に酸
素濃度・湿度分析を行った。その結果を表1に示した。
Comparative Example 1 The same reaction and post-treatment were carried out as in Example 1 except that no zeolite carrier was used, to obtain a dry powder. This dry powder and 20 g of zeolite were uniformly mixed in a polyethylene bag, and heated and reduced exactly in the same manner as in Example 1.
It was filled and packed in a paper pouch laminated with perforated polyethylene to obtain an oxygen absorber package, which was sealed in the packaging bag and analyzed for oxygen concentration and humidity over time. The results are shown in Table 1.

【0027】[0027]

【表1】 [Table 1]

【0028】表1から、本発明の活性化マグネシウム担
持担体からなる脱酸素剤主剤は、水分の存在下及び不存
在下において、実用的な酸素吸収活性を有し、担体に担
持させないで還元処理したマグネシウムよりも高活性な
脱酸素剤であることが分かる。
From Table 1, it can be seen that the oxygen-absorbing base material comprising the activated magnesium-supported carrier of the present invention has a practical oxygen absorption activity in the presence and absence of water, and has a reduction treatment without being supported on the carrier. It is clear that the oxygen absorber is more active than magnesium.

【0029】実施例4〜6 脱酸素剤主剤の担体としてゼオライトの代わりに、珪藻
土、チタニア又は活性炭を用いた以外は、実施例1と全
く同じく脱酸素剤主剤を調製し、その1g及び水分供与
体として水2.0gを含浸させた粒状ゼオライト2.0
gを有孔ポリエチレンでラミネートした紙小袋に充填・
包装して脱酸素剤包装体を得た。この脱酸素剤包装体1
個を蒸し饅頭10個及び92%RHの空気500mlと共
に、ポリ塩化ビニリデンコートナイロン/ポリエチレン
積層フィルムからなる包装袋に密封した以外は実施例1
と全く同じ操作を行った。50時間後の結果を表2に示
した。
Examples 4 to 6 Except for using diatomaceous earth, titania or activated carbon instead of zeolite as a carrier for the oxygen scavenger main agent, the oxygen scavenger main agent was prepared in exactly the same manner as in Example 1, and 1 g of the oxygen scavenger main agent and water donation were prepared. 2.0 g of granular zeolite impregnated with 2.0 g of water
g into a paper pouch laminated with perforated polyethylene.
Packaging was performed to obtain an oxygen scavenger package. This oxygen absorber package 1
Example 1 except that the pieces were sealed in a packaging bag made of polyvinylidene chloride-coated nylon / polyethylene laminated film together with 10 steamed buns and 500 ml of 92% RH air.
Performed exactly the same operation as. The results after 50 hours are shown in Table 2.

【0030】[0030]

【表2】 [Table 2]

【0031】実施例7〜9 脱酸素剤主剤の担体として、ゼオライト、珪藻土又は酸
性白土活性を用い、水分供与体を用いた以外は、実施例
1と全く同じく脱酸素剤主剤を調製し、その2.0gを
有孔ポリエチレンでラミネートした紙小袋に充填・包装
して脱酸素剤包装体を得た。この脱酸素剤包装体1個を
ピーナツ100g及び40%RHの空気500mlと共
に、ナイロン/Six蒸着PET/ポリエチレン積層フ
ィルムからなる包装袋に密封した以外は実施例1と全く
同じ操作を行った。50時間後の結果を表3に示した。
Examples 7 to 9 Except that zeolite, diatomaceous earth or acidic clay was used as a carrier for the oxygen scavenger, and a water donor was used, the oxygen scavenger was prepared in exactly the same manner as in Example 1. 2.0 g was filled and packed in a paper pouch laminated with perforated polyethylene to obtain a package of oxygen scavenger. The oxygen absorber packet 1 together with peanut 100g and 40% RH of the air 500 ml, subjected to exactly the same operation except for sealed packaging bag made of nylon / S i O x deposition PET / polyethylene laminated film Example 1 Was. The results after 50 hours are shown in Table 3.

【0032】[0032]

【表3】 [Table 3]

【0033】実施例10〜13 硫酸マグネシウム・7水和物12.33gを60℃の水
60mlに溶解し、これに様々な量の酸性白土を入れ攪
拌した。これに無水炭酸ナトリウム10.6gを水50
mlに溶かした水溶液を滴下した。滴下終了後そのまま
2時間攪拌した。攪拌後、不溶物を濾別し濾液が中性に
なるまで洗浄し、110℃で乾燥し、乾燥粉末を得た。
この乾燥粉末を実施例1と同様に加熱還元し、脱酸素剤
主剤を得た。得られた脱酸素剤主剤には、マグネシウム
が5、20、60又は90重量%含まれており、その他
の成分はほとんどがゼオライトであった。以下、実施例
1と同様の操作を行った。50時間後の結果を表4に示
した。
Examples 10-13 12.33 g of magnesium sulfate heptahydrate was dissolved in 60 ml of water at 60 ° C., and various amounts of acid clay were added thereto and stirred. 10.6 g of anhydrous sodium carbonate was added to 50 parts of water.
The aqueous solution dissolved in ml was dropped. After completion of the dropwise addition, the mixture was stirred for 2 hours. After stirring, the insolubles were separated by filtration, washed until the filtrate became neutral, and dried at 110 ° C. to obtain a dry powder.
This dried powder was reduced by heating in the same manner as in Example 1 to obtain a deoxidizer main agent. The obtained oxygen scavenger main agent contained 5, 20, 60 or 90% by weight of magnesium, and most of the other components were zeolites. Hereinafter, the same operation as in Example 1 was performed. The results after 50 hours are shown in Table 4.

【0034】[0034]

【表4】 [Table 4]

【0035】実施例14〜16 酸性白土の量を変えた他は実施例10〜13と同様に加
熱還元し、脱酸素剤主剤を得た。得られた脱酸素剤主剤
には、マグネシウムが36、60又は80重量%含まれ
ており、その他の成分はほとんどがゼオライトであっ
た。以下、実施例1と同様の操作を行った。50時間後
の結果を表5に示した。
Examples 14 to 16 Heat reduction was carried out in the same manner as in Examples 10 to 13 except that the amount of the acid clay was changed to obtain a main oxygen scavenger. The obtained oxygen scavenger main agent contained 36, 60 or 80% by weight of magnesium, and most of the other components were zeolites. Hereinafter, the same operation as in Example 1 was performed. The results after 50 hours are shown in Table 5.

【0036】[0036]

【表5】 [Table 5]

【0037】実施例17 金属探知機に感応しない酸洗処理した珪藻土を用い、実
施例1と同じく還元処理し、還元品2.0gを紙/有孔
ポリエチレン小袋に充填した。この小袋と和菓子ウイロ
ウ100g、湿度95%RHの空気500mlとを延伸
ポリプロピレン/ポリ塩化ビニリデン/ポリエチレン積
層フィルムからなる包装袋に密封し、食品包装体を得
た。この食品包装体を予め鉄球0.8mmφの鉄球のテ
ストピースは検知するが鉄球0.7mmφは検知しない
ように調整した市販の金属探知機(アンリツ(株)製K
D801A)を通過させたが金属検知反応は見られなか
った。検査後は、10℃に保存し、経時的に酸素濃度・
湿度分析を行った。その結果、序々に酸素濃度が減少し
20時間後には、0.1%未満になった。その間、袋内
の湿度は、94〜96%RHで殆ど変化は見られなかっ
た。また、2週間後、開封したところウイロウの色、風
味は良好であった。
Example 17 Using diatomaceous earth which had been pickled and insensitive to a metal detector, a reduction treatment was carried out in the same manner as in Example 1, and 2.0 g of the reduced product was filled in a paper / perforated polyethylene pouch. This small bag, 100 g of Japanese confectionery willow and 500 ml of air at a humidity of 95% RH were sealed in a packaging bag composed of a stretched polypropylene / polyvinylidene chloride / polyethylene laminated film to obtain a food package. A commercially available metal detector (Kr, manufactured by Anritsu Corporation) which has been adjusted so that the food package is detected in advance so as to detect a test piece of an iron ball having a diameter of 0.8 mmφ but not to detect a 0.7 mmφ iron ball.
D801A), but no metal detection reaction was observed. After the inspection, store at 10 ° C,
Humidity analysis was performed. As a result, the oxygen concentration gradually decreased to become less than 0.1% after 20 hours. During that time, the humidity in the bag was hardly changed at 94 to 96% RH. Two weeks later, when opened, the color and flavor of the wax were good.

【0038】実施例18 実施例1で作製した脱酸素剤主剤2.0gを充填した紙
/有孔ポリエチレン積層系からなる小袋状の脱酸素剤包
装体と玉露抹茶50g、湿度20%RHの空気250m
lをPET/アルミ箔/ポリエチレン包装袋に密封し、
25℃で保存した。保存開始一ヶ月後に開封したとこ
ろ、異臭は無く、保存品の外観に異常は無かった。
Example 18 A pouch-shaped oxygen-absorbing agent package consisting of a paper / perforated polyethylene laminate filled with 2.0 g of the oxygen-absorbing agent base material prepared in Example 1 and 50 g of gyokuro matcha, and air at a humidity of 20% RH 250m
1 in a PET / aluminum foil / polyethylene packaging bag,
Stored at 25 ° C. When opened one month after the start of storage, there was no off-odor and there was no abnormality in the appearance of the stored product.

【0039】比較例2 実施例18で用いた脱酸素剤包装体の代わりに、鉄粉
0.5g、塩化ナトリウム0.5g及び活性炭1.0g
を良く混合し紙/有孔ポリエチレン小袋に充填した脱酸
素剤包装体を用いた以外は、実施例18と同じく行い、
評価した。保存開始一ヶ月後に開封したところ、保存品
の一部に変色が見られ、風味がやや低下した。
Comparative Example 2 In place of the oxygen scavenger package used in Example 18, 0.5 g of iron powder, 0.5 g of sodium chloride and 1.0 g of activated carbon were used.
Was carried out in the same manner as in Example 18, except that the oxygen-absorbing agent package was used which was mixed well and filled in a paper / perforated polyethylene pouch.
evaluated. When opened one month after the start of storage, discoloration was observed in a part of the stored product, and the flavor was slightly reduced.

【0040】以上から明らかなように、本発明の脱酸素
剤は、従来の鉄粉系脱酸素剤が機能できないような低湿
度雰囲気でも実用的な酸素吸収活性を有し、錆臭のよう
な異臭も発生せず、乾燥条件を維持して乾燥物品をも良
好に保存できる。
As is clear from the above, the oxygen scavenger of the present invention has practical oxygen absorption activity even in a low humidity atmosphere where conventional iron powder-based oxygen scavengers cannot function, and has a rust odor. No unpleasant odor is generated, and the drying condition can be maintained and the dried article can be stored well.

【0041】[0041]

【発明の効果】本発明の脱酸素剤は、従来の脱酸素剤が
機能しなかった低湿度雰囲気下でも実用的な酸素吸収能
力を有し、異臭の発生もなく、金属探知機にも検知され
ない安価で実用的な脱酸素剤である。
The oxygen absorber of the present invention has a practical oxygen absorption capacity even in a low-humidity atmosphere where the conventional oxygen absorber did not function, has no odor, and can be detected by a metal detector. It is not a cheap and practical oxygen absorber.

Claims (5)

【特許請求の範囲】[Claims] 【請求項1】担体及び担体に担持された活性化マグネシ
ウムからなる脱酸素剤組成物。
An oxygen scavenger composition comprising a carrier and activated magnesium supported on the carrier.
【請求項2】担体に担持された活性化マグネシウムを主
剤とし、水分供与体を助剤とする脱酸素剤組成物。
2. An oxygen scavenger composition comprising activated magnesium supported on a carrier as a main ingredient and a water donor as an auxiliary.
【請求項3】活性化マグネシウムが、マグネシウム化合
物を担体に担持後、還元又は分解したものであることを
特徴とする請求項1〜2記載の脱酸素剤組成物。
3. The oxygen scavenger composition according to claim 1, wherein the activated magnesium is reduced or decomposed after supporting the magnesium compound on a carrier.
【請求項4】活性化マグネシウムの担持率が、5〜90
重量%であることを特徴とする請求項1〜2記載の脱酸
素剤組成物。
4. The loading ratio of activated magnesium is 5 to 90.
3. The oxygen scavenger composition according to claim 1, wherein the composition is a weight percent.
【請求項5】磁性体を実質的に含まない請求項1〜2記
載の脱酸素剤組成物。
5. The oxygen scavenger composition according to claim 1, which does not substantially contain a magnetic substance.
JP11212749A 1999-07-27 1999-07-27 Deoxidizer Pending JP2001037457A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP11212749A JP2001037457A (en) 1999-07-27 1999-07-27 Deoxidizer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP11212749A JP2001037457A (en) 1999-07-27 1999-07-27 Deoxidizer

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Publication Number Publication Date
JP2001037457A true JP2001037457A (en) 2001-02-13

Family

ID=16627794

Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Status (1)

Country Link
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014080750A1 (en) 2012-11-21 2014-05-30 三井化学株式会社 Polyurethane resin production method
WO2014080749A1 (en) 2012-11-21 2014-05-30 三井化学株式会社 Polymerizable composition for optical material
WO2014157407A1 (en) 2013-03-26 2014-10-02 三井化学株式会社 Polymerizable composition for optical materials, optical material obtained from same, and method for producing optical material

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014080750A1 (en) 2012-11-21 2014-05-30 三井化学株式会社 Polyurethane resin production method
WO2014080749A1 (en) 2012-11-21 2014-05-30 三井化学株式会社 Polymerizable composition for optical material
WO2014157407A1 (en) 2013-03-26 2014-10-02 三井化学株式会社 Polymerizable composition for optical materials, optical material obtained from same, and method for producing optical material

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