JPH10314581A - Oxygen absorbent and culture method for anaerobic bacteria using the same - Google Patents
Oxygen absorbent and culture method for anaerobic bacteria using the sameInfo
- Publication number
- JPH10314581A JPH10314581A JP3891898A JP3891898A JPH10314581A JP H10314581 A JPH10314581 A JP H10314581A JP 3891898 A JP3891898 A JP 3891898A JP 3891898 A JP3891898 A JP 3891898A JP H10314581 A JPH10314581 A JP H10314581A
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- JP
- Japan
- Prior art keywords
- oxygen
- oxygen absorbent
- thermoplastic resin
- absorbent
- anaerobic bacteria
- 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.)
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- Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、大気中での自然発
火や使用中の過熱発火の危険性がないアスコルビン酸類
を主剤とする酸素吸収剤に関する。さらに詳しくは、ア
スコルビン酸類主剤の酸素吸収組成物に熱可塑性樹脂の
粒状体を混合してなる酸素吸収剤、並びにこの酸素吸収
剤を用いた嫌気性菌の培養方法に関する。[0001] The present invention relates to an oxygen absorbent containing ascorbic acids as a main component, which has no danger of spontaneous ignition in the atmosphere or overheating during use. More specifically, the present invention relates to an oxygen absorbent obtained by mixing a granular material of a thermoplastic resin with an oxygen absorbing composition of an ascorbic acid-based agent, and a method for culturing anaerobic bacteria using the oxygen absorbent.
【０００２】[0002]
【従来の技術】アスコルビン酸類を主剤とする酸素吸収
剤は、食品の包装内に封入し、食品のカビ防止、酸化防
止等に用いられる脱酸素剤の原料として知られている。
脱酸素剤に用いられる酸素吸収剤としては、アスコルビ
ン酸類を主剤とするものの他に、鉄粉を主剤とするもの
が良く知られているが、食品メーカーでは針等の金属異
物混入防止のため金属探知器を使用することがあり、鉄
粉主剤の脱酸素剤は金属探知器に感応するためそのよう
な用途には用いることができず、アスコルビン酸類を主
剤とした脱酸素剤が用いられる。また、アスコルビン酸
類を主剤とした脱酸素剤は、吸収した酸素とほぼ同量の
炭酸ガスを発生するため、包装内の容積変化が無く酸素
を吸収して包装内のガス量が減少することによる外見上
の変化等を嫌う食品等に使用されてきている。更に医療
機関・食品メーカーなどでは、病原菌，食中毒原因菌，
食品汚染菌の検査の目的で嫌気性菌の培養検査を行って
いるが、嫌気性菌を培養するためには、培養環境から短
時間で酸素を排除し、かつ炭酸ガスが存在する雰囲気に
する必要があり、アスコルビン酸類を主剤とする酸素吸
収剤は、通気性に優れた包材に充填して嫌気性菌培養用
のガス濃度調節剤として使用されている。2. Description of the Related Art An oxygen absorber containing ascorbic acid as a main component is known as a raw material of a deoxidizer used to prevent mold and oxidation of food by being enclosed in food packaging.
As the oxygen absorber used for the oxygen scavenger, in addition to those containing ascorbic acid as a main component, those containing iron powder as a main component are well known. In some cases, a detector is used, and the oxygen absorber of the iron powder base material cannot be used for such applications because it is sensitive to the metal detector, and an oxygen absorber based on ascorbic acids is used. In addition, the oxygen scavenger containing ascorbic acids as the main component generates carbon dioxide gas in almost the same amount as the absorbed oxygen, so there is no volume change in the package and the oxygen is absorbed and the amount of gas in the package decreases. It has been used for foods and the like that dislike appearance changes. Furthermore, in medical institutions and food manufacturers, pathogens, food poisoning bacteria,
We conduct anaerobic culture tests for the purpose of testing for food contaminants, but in order to culture anaerobic bacteria, remove oxygen from the culture environment in a short time and create an atmosphere containing carbon dioxide gas. It is necessary to use an oxygen absorbent containing ascorbic acid as a main component, which is used as a gas concentration regulator for anaerobic bacterium cultivation by filling in a highly air-permeable packaging material.
【０００３】アスコルビン酸類を用いた酸素吸収剤は、
特開昭５１−１３６８４５、特開昭５２−１０８８４、
特開昭５４−９８３４８、特開昭５４−１３２２４６、
特開昭５５−６１９１４等に知られるように、アスコル
ビン酸類とアルカリ粉末、金属塩及び水に活性炭を混合
して得られる。また、特開昭５４−１０５２８８、特開
昭５８−５１８９０には、アスコルビン酸類を用いた酸
素吸収剤の炭酸ガス発生性能を利用した嫌気性菌の培養
方法が知られている。[0003] Oxygen absorbents using ascorbic acids are
JP-A-51-136845, JP-A-52-10884,
JP-A-54-98348, JP-A-54-132246,
As known from JP-A-55-61914 and the like, it can be obtained by mixing activated carbon with ascorbic acid, an alkali powder, a metal salt and water. Japanese Patent Application Laid-Open Nos. 54-105288 and 58-51890 disclose methods for cultivating anaerobic bacteria utilizing the carbon dioxide generation performance of an oxygen absorbent using ascorbic acids.
【０００４】アスコルビン酸類主剤の酸素吸収剤は、ア
スコルビン酸類の酸化反応により酸素吸収を行うので、
反応の際に発熱を伴い、この発熱により更に反応が進行
することにより、短時間での酸素吸収を可能としてい
る。ところが、主剤として使用されるアスコルビン酸類
は有機化合物であるため可燃物であり、また、アスコル
ビン酸類と混合添加される活性炭も消防法（石炭，木炭
類）における指定可燃物である。したがって、大量の酸
素吸収剤が、あるいは、酸素吸収剤を通気性包装袋に充
填したガス濃度調節剤を大量に集積されたものが酸素吸
収したり、酸素吸収剤が少量でも高い雰囲気温度で酸素
吸収すると、反応熱による発熱が大きくなり、その結
果、酸素吸収剤組成中の可燃物が自然発火をする恐れが
あった。このため、この種の酸素吸収剤は、保管、使
用、廃棄等の際の自然発火の危険を考慮して、その取扱
いに十分注意する必要があった。[0004] The oxygen absorber of the ascorbic acid-based agent absorbs oxygen by the oxidation reaction of ascorbic acid.
The reaction generates heat during the reaction, and the reaction further proceeds by the heat generation, thereby enabling oxygen absorption in a short time. However, ascorbic acids used as a main ingredient are organic compounds and therefore are combustibles, and activated carbon mixed and added with ascorbic acids is also a designated combustible in the Fire Service Law (coal and charcoal). Therefore, a large amount of oxygen absorbent or a large amount of a gas concentration regulator filled with oxygen absorbent in a breathable packaging bag absorbs oxygen. When absorbed, the heat generated by the reaction heat increases, and as a result, the combustibles in the oxygen absorbent composition may ignite spontaneously. For this reason, it is necessary to pay close attention to the handling of this type of oxygen absorbent in consideration of the danger of spontaneous ignition during storage, use, disposal, and the like.
【０００５】また、酸素吸収剤の加熱を抑制する方法も
知られている。例えば、特開平５−２６９３７６には、
無機フィラーを担体とし自然発火危険性を抑制する方法
が開示されているが、ここで無機フィラーを担体として
使用する場合、無機フィラーによる熱の吸収が大きいた
め、充分な発熱が起こらず、酸素吸収反応の進行が遅れ
る。そのため、短時間に酸素吸収を完了するには、酸素
吸収剤が大量に必要となるという欠点があった。また、
特開平３−１８８２８８に、不飽和脂肪酸を主剤とする
防錆剤に加熱融解性の添加剤を加えて加熱を抑制する方
法が開示されているが、ここで防錆剤は炭酸ガスを発生
しないことおよび臭気などの点で、嫌気性菌培養用のガ
ス濃度調節剤、食品等用の脱酸素剤に用いる酸素吸収剤
としては使用できないものであった。[0005] Also, a method of suppressing heating of the oxygen absorbent is known. For example, in Japanese Patent Application Laid-Open No. 5-269376,
A method is disclosed in which the inorganic filler is used as a carrier to suppress the risk of spontaneous ignition.However, when the inorganic filler is used as a carrier, sufficient heat is not generated due to large heat absorption by the inorganic filler, and oxygen absorption is not performed. The progress of the reaction is delayed. Therefore, there is a disadvantage that a large amount of an oxygen absorbent is required to complete the oxygen absorption in a short time. Also,
JP-A-3-188288 discloses a method of suppressing heating by adding a heat-meltable additive to a rust preventive agent containing an unsaturated fatty acid as a main component, wherein the rust preventive agent does not generate carbon dioxide gas. In terms of the odor and the odor, they could not be used as a gas concentration regulator for anaerobic bacteria culture or an oxygen absorber used as a deoxidizer for foods and the like.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、上記
従来の酸素吸収剤を改良し、アスコルビン酸類を主剤と
して含み、活性炭を含む酸素吸収剤の優れた酸素吸収性
能を保持しつつ、過熱を抑制して自然発火を防止した酸
素吸収剤を得ることにある。SUMMARY OF THE INVENTION An object of the present invention is to improve the above-mentioned conventional oxygen absorbent, which contains ascorbic acid as a main component, and maintains the excellent oxygen absorption performance of the oxygen absorbent containing activated carbon while maintaining the oxygen absorption performance. To obtain an oxygen absorbent in which spontaneous combustion is prevented by suppressing the occurrence of spontaneous combustion.
【０００７】[0007]
【課題を解決するための手段】すなわち、本発明は、上
記課題を解決するための手段として、アスコルビン酸
類、水および活性炭を含む酸素吸収組成物に、軟化点が
９０〜１２５℃で粒子径が１〜５００μｍの粒状熱可塑
性樹脂を、酸素吸収組成物１００重量部当たり、１０〜
６０重量部混合してなることを特徴とする酸素吸収剤に
関する。That is, according to the present invention, as a means for solving the above-mentioned problems, an oxygen-absorbing composition containing ascorbic acids, water and activated carbon has a softening point of 90 to 125 ° C. and a particle size of 90%. A granular thermoplastic resin having a particle size of 1 to 500 μm is added in an amount of 10 to 10 parts by weight per 100 parts by weight of the oxygen absorbing composition.
An oxygen absorbent characterized by being mixed with 60 parts by weight.
【０００８】本発明の上記酸素吸収剤において、熱可塑
性樹脂の粒状体の粒子径は、通常は１〜５００μｍであ
るが、１０〜３００μｍであることがより好ましく、ま
た、熱可塑性樹脂の種類は、特に制限はなく各種のもの
を用いることができるが、ポリエチレン，ポリプロピレ
ン又はこれらの混合物であることが好ましい。[0008] In the oxygen absorbent of the present invention, the particle size of the thermoplastic resin particles is usually 1 to 500 µm, more preferably 10 to 300 µm. There is no particular limitation, and various types can be used, but polyethylene, polypropylene or a mixture thereof is preferable.
【０００９】本発明の酸素吸収剤は、上記の構成をとる
ことによって、過熱による発火が防止される。すなわ
ち、アスコルビン酸類，水および活性炭からなる酸素吸
収剤は、一般に、通気性包材に被包して酸素吸収剤包装
体として使用されるが、酸素吸収剤包装体を大量に集積
して大気に触れたり、使用時の雰囲気温度が異常に高く
なったりした際、過度の酸化反応により急激な発熱をす
る場合がある。酸素吸収剤が酸素と反応して温度上昇す
るとき或る程度急激に上昇しても、通常は、酸素吸収剤
に含まれる水分が蒸発するために、９０〜１２５℃付近
で温度上昇は一旦緩やかになる。しかし、過度の発熱や
加熱があると水分の蒸発が追いつかず、酸素吸収剤の温
度は前記温度の範囲を越えて急激に上昇し、可燃物であ
る活性炭が発火に至る危険性がある（図１参照）。The oxygen absorbent of the present invention has the above-described configuration, thereby preventing ignition due to overheating. That is, an oxygen absorbent composed of ascorbic acids, water and activated carbon is generally used as an oxygen absorbent package by being wrapped in a gas permeable packaging material. When touching or when the ambient temperature during use becomes abnormally high, rapid heat generation may occur due to excessive oxidation reaction. Even when the oxygen absorbent reacts with oxygen and rises in temperature, even if the temperature rises to a certain degree, usually the temperature rise is once moderate around 90 to 125 ° C. because the water contained in the oxygen absorbent evaporates. become. However, if there is excessive heat generation or heating, the evaporation of water cannot catch up, and the temperature of the oxygen absorbent rises rapidly beyond the above temperature range, and there is a risk that activated carbon, which is a combustible substance, may ignite (see FIG. 1).
【００１０】しかしながら、本発明によれば、上述のア
スコルビン酸類，水および活性炭からなる酸素吸収剤
（酸素吸収組成物）に、熱可塑性樹脂の粒状体を添加、
混合したものにすることにより、得られる酸素吸収剤
は、その温度が前述したような９０〜１２５℃付近に達
すると、添加した熱可塑性樹脂が軟化し、酸素吸収剤表
面を覆って酸素吸収剤の過度の酸化反応を抑制し、水分
が減少した酸素吸収剤の異常な発熱を抑制することがで
きる。また本発明の酸素吸収剤は、熱可塑性樹脂の粒状
体が添加されていても正常な酸素吸収反応は阻害され
ず、食品の保存用の脱酸素剤、嫌気性菌の培養用のガス
濃度調節剤等に好適に用いることができる。However, according to the present invention, a granular thermoplastic resin is added to the above-mentioned oxygen absorbent (oxygen absorbing composition) comprising ascorbic acids, water and activated carbon.
By making the mixture, when the temperature reaches about 90 to 125 ° C. as described above, the added thermoplastic resin softens and covers the oxygen absorbent surface to cover the oxygen absorbent. Excessive oxidation reaction of the oxygen absorber can be suppressed, and abnormal heat generation of the oxygen absorbent having reduced water content can be suppressed. In addition, the oxygen absorber of the present invention does not inhibit the normal oxygen absorption reaction even if the thermoplastic resin granules are added, the oxygen absorber for preserving food, and the gas concentration control for culturing anaerobic bacteria. It can be suitably used as an agent.
【００１１】[0011]
【発明の実施の形態】以下、本発明をさらに詳細に説明
する。本発明においては、アスコルビン酸類としては、
Ｌ−アスコルビン酸、Ｌ−アスコルビン酸ナトリウム、
Ｌ−アスコルビン酸カルシウム、Ｄ−ｉｓｏ−アスコル
ビン酸ナトリウムの単独もしくはこれらの混合物が用い
られる。これらアスコルビン酸類は、水溶液として活性
炭に含浸させて用いるのが好ましい。アスコルビン酸類
水溶液は濃度の濃い方が活性炭の使用量を少なくするこ
とができ、アスコルビン酸類の濃度は、できるだけ飽和
溶解度に近い濃度にすることが好ましく、また、必要な
水分量はアスコルビン酸類の水溶液を用いることによっ
て、十分確保される。このため、アスコルビン酸類は溶
解度の高い塩が好ましく、具体的には、Ｌ−アスコルビ
ン酸ナトリウムが好ましい。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. In the present invention, ascorbic acids include
L-ascorbic acid, sodium L-ascorbate,
Either calcium L-ascorbate or sodium D-iso-ascorbate or a mixture thereof is used. These ascorbic acids are preferably used by impregnating activated carbon as an aqueous solution. A higher concentration of the aqueous solution of ascorbic acid can reduce the amount of activated carbon used. By using it, it is ensured sufficiently. For this reason, ascorbic acids are preferably salts having high solubility, and specifically, sodium L-ascorbate is preferred.
【００１２】活性炭としては、おが粉、石炭、椰子殻等
を原料として水蒸気賦活、薬品賦活、炭酸ガス賦活等の
各種製法で製造された活性炭を用いることができる。ま
た活性炭は、アスコルビン酸類等を水溶液として活性炭
に担持させ顆粒状で小袋に充填して用いられるために、
粒状活性炭が好ましい。粒状活性炭の粒子径は、好まし
くは０．１ｍｍ〜２ｍｍ、より好ましくは０．５〜１ｍ
ｍである。粒状活性炭の粒子径は上記範囲より細かくな
ると、酸素吸収剤の流動性が悪くなり自動充填が困難と
なる。また、粒子径が大きすぎると酸素吸収性能が低下
したり、酸素吸収剤の包装体を突き破り、内容物がこぼ
れ出すという問題が生じる。As the activated carbon, there can be used activated carbon produced from sawdust, coal, coconut shell and the like by various methods such as steam activation, chemical activation and carbon dioxide activation. Activated carbon is used as an aqueous solution of ascorbic acids or the like, which is supported on activated carbon and filled into small bags in granular form.
Granular activated carbon is preferred. The particle size of the granular activated carbon is preferably 0.1 mm to 2 mm, more preferably 0.5 to 1 m.
m. When the particle size of the granular activated carbon is smaller than the above range, the fluidity of the oxygen absorbent deteriorates and automatic filling becomes difficult. Further, if the particle size is too large, there arises a problem that the oxygen absorbing performance is reduced, the package of the oxygen absorbent is broken through, and the contents spill out.
【００１３】本発明の酸素吸収剤においては、必要に応
じ、炭酸塩や金属化合物等の添加剤がアスコルビン酸類
に加えられる。炭酸塩としては、炭酸ナトリウム、炭酸
水素ナトリウム、炭酸ナトリウムの水和物等の水溶性の
炭酸塩が好ましい。炭酸塩のの配合量は、アスコルビン
酸類１００重量部に対し、炭酸塩１０〜３０重量部が好
ましい。金属化合物としては、塩化第１鉄、塩化第２
鉄、硫酸第２鉄、硫酸第１鉄、塩化マンガン、硫酸亜
鉛、硫酸銅、塩化銅の無水塩又は含水塩が好ましい。金
属化合物の配合量は、アスコルビン酸類１００重量部に
対し、金属化合物５〜２０重量部が好ましい。In the oxygen absorbent of the present invention, an additive such as a carbonate or a metal compound is added to the ascorbic acids as required. As the carbonate, a water-soluble carbonate such as sodium carbonate, sodium hydrogen carbonate, or a hydrate of sodium carbonate is preferable. The amount of the carbonate is preferably 10 to 30 parts by weight based on 100 parts by weight of ascorbic acids. Metal compounds include ferrous chloride, ferric chloride
Iron, ferric sulfate, ferrous sulfate, manganese chloride, zinc sulfate, copper sulfate, and anhydrous or hydrated salts of copper chloride are preferred. The amount of the metal compound is preferably 5 to 20 parts by weight based on 100 parts by weight of ascorbic acids.
【００１４】本発明の酸素吸収剤の製造方法は、特に制
限はないが、上記の各成分により酸素吸収組成物を調製
し、これに下記の熱可塑性樹脂の粒状体を混合する方法
が好ましい。酸素吸収組成物の調製方法としては、例え
ば、アスコルビン酸類の水溶液に炭酸塩、金属化合物等
を溶解し、この溶液を活性炭に混合、含浸させる方法、
或いは、アスコルビン酸類の水溶液に金属化合物を溶解
させた溶液を、炭酸塩と活性炭の混合物と混合する方法
が挙げられる。The method for producing the oxygen absorbent of the present invention is not particularly limited, but a method is preferred in which an oxygen absorbing composition is prepared from the above-mentioned components, and the following thermoplastic resin particles are mixed with the composition. As a method for preparing the oxygen-absorbing composition, for example, a method of dissolving a carbonate, a metal compound, or the like in an aqueous solution of ascorbic acids, mixing the solution with activated carbon, and impregnating the solution,
Alternatively, a method in which a solution in which a metal compound is dissolved in an aqueous solution of ascorbic acids is mixed with a mixture of carbonate and activated carbon may be used.
【００１５】本発明に用いられる熱可塑性樹脂は、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、又はこれらの混合物等の熱可塑性樹
脂が例示される。特に分子量１００００以下の低分子量
のポリエチレン、ポリプロピレン等のポリオレフィン類
が好ましい。また、酸素吸収組成物に添加した際の臭気
の影響が少ない点でも、ポリエチレンまたはポリプロピ
レンまたはこれらの混合物が特に好ましく用いられる。
添加する熱可塑性樹脂は、軟化点が低すぎると、通常の
酸素吸収反応を阻害することになる。また、樹脂の軟化
点が高すぎると、酸素吸収剤の温度が前記９０〜１２５
℃を越えても樹脂が軟化せず、酸素吸収剤の過度の発熱
反応を抑制することができない。[0015] The thermoplastic resin used in the present invention is preferably a thermoplastic resin having a softening point of 90 to 125 ° C, such as a thermoplastic resin such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, elastomer, or a mixture thereof. Is exemplified. In particular, low molecular weight polyolefins such as polyethylene and polypropylene having a molecular weight of 10,000 or less are preferable. In addition, polyethylene or polypropylene or a mixture thereof is particularly preferably used in that the effect of odor when added to the oxygen absorbing composition is small.
If the softening point of the thermoplastic resin to be added is too low, a normal oxygen absorption reaction is inhibited. On the other hand, if the softening point of the resin is too high, the temperature of the oxygen absorbent may be in the range of 90 to 125.
Even if the temperature exceeds ℃, the resin does not soften and the excessive exothermic reaction of the oxygen absorbent cannot be suppressed.
【００１６】熱可塑性樹脂は、酸素吸収組成物と混合す
る時に、主剤溶液を含浸した活性炭表面を効率よく覆う
必要があるため、粒径１〜５００μｍであることが必要
であり、より好ましくは、１０〜３００μｍのものが用
いられる。粒径が小さすぎると、酸素吸収剤の流動性を
悪くし機械充填を困難にする。一方、粒径が大きすぎる
と、温度が上昇して熱可塑性樹脂が軟化したときに、効
率よく酸素吸収剤表面を覆うことができないため、自然
発火の危険性を抑制することができない。When the thermoplastic resin is mixed with the oxygen-absorbing composition, it is necessary to efficiently cover the surface of the activated carbon impregnated with the base solution, so that the thermoplastic resin must have a particle size of 1 to 500 μm, and more preferably, Those having a thickness of 10 to 300 μm are used. If the particle size is too small, the fluidity of the oxygen absorbent deteriorates and mechanical filling becomes difficult. On the other hand, if the particle size is too large, when the temperature rises and the thermoplastic resin is softened, the surface of the oxygen absorbent cannot be efficiently covered, so that the risk of spontaneous ignition cannot be suppressed.
【００１７】熱可塑性樹脂の配合量は、酸素吸収組成物
１００重量部当たり１０〜６０重量部であり、特に１５
〜４０重量部が好ましい。配合量が前記の範囲より少な
くなると目的の発熱抑制効果が低く、また配合量が多す
ぎると、樹脂によって奪われる熱量が多くなり反応の進
行が遅れたり、酸素吸収剤容積が嵩張るという問題があ
る。熱可塑性樹脂の添加にあたっては、組成、性状、用
途等に応じて、樹脂の種類、粒状体の粒子径、配合量を
適宜勘案して決めればよい。The amount of the thermoplastic resin is from 10 to 60 parts by weight, preferably from 15 to 100 parts by weight, per 100 parts by weight of the oxygen absorbing composition.
~ 40 parts by weight are preferred. If the compounding amount is less than the above range, the intended heat generation suppressing effect is low, and if the compounding amount is too large, there is a problem that the amount of heat taken by the resin increases, the progress of the reaction is delayed, and the oxygen absorbent volume is bulky. . The addition of the thermoplastic resin may be determined by appropriately considering the type of the resin, the particle diameter of the granular material, and the amount of the resin according to the composition, properties, application, and the like.
【００１８】得られた酸素吸収剤は、酸素吸収能力に優
れ、金属探知器にかからず、また、吸収した酸素量とほ
ぼ同量の炭酸ガスを発生するため、従来のアスコルビン
酸系の脱酸素剤が用いられていた食品等の用途にそのま
ま適用でき、また、通気性に優れた包材に充填したり、
大量に使った場合でも自然発火の危険性がないため、医
療機関等で用いられている嫌気性菌培養用のガス濃度調
節剤として好適に使用される。The obtained oxygen absorbent is excellent in oxygen absorption capacity, does not affect metal detectors, and generates carbon dioxide gas in the same amount as the amount of oxygen absorbed. It can be applied as it is to applications such as food where an oxygen agent was used, and it can be filled into a highly breathable packaging material,
Since there is no danger of spontaneous ignition even when used in large quantities, it is suitably used as a gas concentration regulator for anaerobic bacteria culture used in medical institutions and the like.
【００１９】[0019]
【実施例】次に本発明を実施例により更に具体的に説明
する。 実施例１及び比較例１ Ｌ−アスコルビン酸ナトリウム水溶液（濃度４５重量
％）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、該溶液全量を顆粒
状活性炭（平均粒径0.６ｍｍ）６０ｇに含浸させて酸素
吸収剤Ａ（比較例１）を得た。酸素吸収剤Ａ１００ｇ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）２５
ｇを添加し、混合して酸素吸収剤Ｂ（実施例１）を得
た。この酸素吸収剤Ａ及びＢについて自然発火危険性試
験を行った。試験方法は、運輸省海上技術安全局により
定められている「未知物質の危険性評価の試験方法及び
判定基準」に準じて行い、３階段の容器等級に分類され
る容器等級IIに準ずる試験を行った。すなわち、槽内温
度を１４０℃に設定した熱風循環式恒温槽の中心に１辺
2.５ｃｍの試料容器（１００メッシュの金網使用）を
置き、この試料容器に充填した試料が、２４時間以内に
発火又は温度が２００℃を超えるかどうかを試験するも
のである。この試験によれば、酸素吸収剤Ａ（比較例
１）は約３０分で発火に至ったが、酸素吸収剤Ｂ（実施
例１）は２４時間経過しても恒温槽内温度である１４０
℃を超えることなく、発火には至らなかった。これは、
酸素吸収剤Ｂ（実施例１）は、温度が上昇しても発火に
至る前に添加した熱可塑性樹脂が軟化して効率よく酸素
吸収剤表面を覆い、適度に酸素を遮断することにより発
熱が抑制され、発火点まで温度が上昇しなかったことに
よると考えられる。Next, the present invention will be described more specifically with reference to examples. Example 1 and Comparative Example 1 6 g of ferrous sulfate · 7 hydrate and 10 g of sodium carbonate · 10 hydrate were dissolved in 100 g of an aqueous solution of sodium L-ascorbate (concentration: 45% by weight). (Average particle size: 0.6 mm) 60 g was impregnated to obtain an oxygen absorbent A (Comparative Example 1). Low molecular weight polyethylene having an average particle size of 200 μm and an average molecular weight of 2,000 (softening point 105 ° C .: JIS K2531) 25 per 100 g of oxygen absorbent A
g was added and mixed to obtain an oxygen absorbent B (Example 1). A spontaneous ignition risk test was performed on the oxygen absorbers A and B. The test method shall be in accordance with “Test Methods and Judgment Criteria for Hazard Assessment of Unknown Substances” established by the Maritime Technical Safety Bureau of the Ministry of Transport. went. That is, one side is located at the center of the hot air circulation type
A 2.5-cm sample container (using a 100-mesh wire net) is placed, and it is tested whether the sample filled in the sample container ignites or the temperature exceeds 200 ° C. within 24 hours. According to this test, the oxygen absorbent A (Comparative Example 1) ignited in about 30 minutes, but the oxygen absorbent B (Example 1) had the same temperature in the thermostat even after 24 hours.
No ignition occurred without exceeding ℃. this is,
Even if the temperature rises, the added oxygen resin of the oxygen absorbent B (Example 1) softens before it ignites, efficiently covers the surface of the oxygen absorbent, and appropriately cuts off oxygen to generate heat. It is considered that the temperature was suppressed and the temperature did not rise to the ignition point.
【００２０】酸素吸収剤Ｂ（実施例１）１ｃｃ、酸素吸
収剤Ａ（比較例１）１ｃｃを、それぞれ、有孔ポリエチ
レンフィルムでラミネートした和紙の通気性小袋に充填
して酸素吸収包装体とし、それぞれ、ポリ塩化ビニリデ
ン被覆ナイロン／ポリエチレンの積層フィルムのガスバ
リア袋に空気量１５０ｃｃとともに密封し、２５℃に保
持し、袋内の酸素濃度及び炭酸ガス濃度の経時変化を調
査した。結果を表１に示すが、酸素吸収剤Ｂは、熱可塑
性樹脂を添加していない酸素吸収剤Ａと同等の酸素吸収
性能を示すことがわかる。また、それぞれの酸素吸収剤
の見掛け密度（軽装カサ比重；ＪＩＳＫ６７２１）を測
定したところ、酸素吸収剤Ａは0.５３ｇ／ｃｃ、酸素吸
収剤Ｂは0.５２ｇ／ｃｃとほとんど変わりなく、ともに
流動性は良好であった。1 cc of the oxygen absorbent B (Example 1) and 1 cc of the oxygen absorbent A (Comparative Example 1) were each filled in a gas-permeable small bag of Japanese paper laminated with a perforated polyethylene film to form an oxygen-absorbing package. Each was sealed in a gas barrier bag of a laminated film of polyvinylidene chloride-coated nylon / polyethylene with an air volume of 150 cc, kept at 25 ° C., and examined over time for changes in oxygen concentration and carbon dioxide concentration in the bag. The results are shown in Table 1. It can be seen that the oxygen absorbent B exhibits the same oxygen absorption performance as the oxygen absorbent A to which no thermoplastic resin is added. When the apparent densities of the respective oxygen absorbents were measured (specific gravity of lightly-fitted bulk material; JIS K6721), oxygen absorbent A was 0.53 g / cc, oxygen absorbent B was 0.52 g / cc, which was almost the same. The properties were good.
【００２１】比較例２ Ｌ−アスコルビン酸ナトリウム水溶液（濃度４５重量
％）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、該溶液６５ｇを顆
粒状珪藻土（平均粒径0.６ｍｍ）６０ｇに含浸させて酸
素吸収剤Ｃ（比較例２）を得た。この場合、顆粒状珪藻
土６０ｇに前記溶液６５ｇを含浸させたところで流動性
が悪くなり、これ以上含浸させることは不可能であっ
た。また、酸素吸収剤Ｃの見掛け密度は0.６５ｇ／ｃｃ
であった。次に、この酸素吸収剤Ｃ１ｃｃを、実施例１
と同様に通気性小袋に充填して酸素吸収包装体とし、こ
れを用いて実施例１と同様に酸素吸収試験を行った。結
果は表１に併記したが、酸素吸収剤Ｃの酸素吸収能力は
他の酸素吸収剤に比べ、著しく劣っていた。Comparative Example 2 6 g of ferrous sulfate · 7 hydrate and 10 g of sodium carbonate · 10 hydrate were dissolved in 100 g of an aqueous solution of sodium L-ascorbate (concentration: 45% by weight), and 65 g of the solution was treated with granular diatomaceous earth ( An oxygen absorbent C (Comparative Example 2) was obtained by impregnation into 60 g of an average particle size (0.6 mm). In this case, when 60 g of granular diatomaceous earth was impregnated with 65 g of the solution, the fluidity deteriorated, and it was impossible to impregnate it further. The apparent density of the oxygen absorbent C is 0.65 g / cc.
Met. Next, this oxygen absorbent C1cc was used in Example 1
The oxygen-absorbing package was filled in the same manner as in Example 1 to obtain an oxygen-absorbing package, and an oxygen-absorbing test was performed in the same manner as in Example 1. The results are also shown in Table 1, but the oxygen absorbing ability of oxygen absorbent C was remarkably inferior to that of other oxygen absorbents.
【００２２】[0022]
【表１】 [Table 1]
【００２３】比較例３ 比較例１と同様に作成した酸素吸収剤Ａ１００ｇ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）５ｇを
添加、混合して、酸素吸収剤Ｄを得た。酸素吸収剤Ｄに
ついて、実施例１と同様に、容器等級IIの試験を実施し
たところ、酸素吸収剤Ｄは約３５分で発火した。Comparative Example 3 To 100 g of the oxygen absorbent A prepared in the same manner as in Comparative Example 1, 5 g of low molecular weight polyethylene (softening point: 105 ° C .; JIS K2531) having an average particle size of 200 μm and an average molecular weight of 2,000 was added and mixed. Agent D was obtained. When the test of container class II was performed on the oxygen absorbent D in the same manner as in Example 1, the oxygen absorbent D ignited in about 35 minutes.
【００２４】比較例４ 比較例１と同様に作成した酸素吸収剤Ａ１００ｇに、平
均粒径１ｍｍ、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、混合して、酸素吸収剤Ｅを得た。酸素吸収剤Ｅにつ
いて、実施例１と同様に、容器等級IIの試験を実施した
ところ、酸素吸収剤Ｅは約３０分で発火した。Comparative Example 4 To 100 g of oxygen absorbent A prepared in the same manner as in Comparative Example 1, 25 g of low molecular weight polyethylene (softening point: 105 ° C .; JIS K2531) having an average particle size of 1 mm and an average molecular weight of 2,000 was added and mixed. Agent E was obtained. When the test of the container class II was performed on the oxygen absorbent E in the same manner as in Example 1, the oxygen absorbent E ignited in about 30 minutes.
【００２５】比較例５ 比較例１と同様に作成した酸素吸収剤Ａ１００ｇに、平
均粒径２００μｍ、平均分子量３０００の低分子量ポリ
プロピレン（軟化点１５２℃；ＪＩＳＫ２５３１）２５
ｇを添加、混合して、酸素吸収剤Ｆを得た。酸素吸収剤
Ｆについて、実施例１と同様に、容器等級IIの試験を実
施したところ、酸素吸収剤Ｆは約４０分で発火した。Comparative Example 5 A low molecular weight polypropylene (softening point: 152 ° C .; JIS K2531) 25 having an average particle size of 200 μm and an average molecular weight of 3000 was added to 100 g of the oxygen absorbent A prepared in the same manner as in Comparative Example 1.
g was added and mixed to obtain an oxygen absorbent F. When the test of the container class II was performed on the oxygen absorbent F in the same manner as in Example 1, the oxygen absorbent F ignited in about 40 minutes.
【００２６】以上の結果から明らかなように、酸素吸収
剤Ｂと同様に熱可塑性樹脂の粒状体を添加しても、同じ
樹脂でも添加量の少ない場合（酸素吸収剤Ｄ）、同じ樹
脂でまた同量でも粒子径の大きい樹脂の場合（酸素吸収
剤Ｅ）、軟化点の高い熱可塑性樹脂を用いた場合（酸素
吸収剤Ｆ）、それぞれ、添加効果が低く、発熱を抑制で
きないために発火した。As is clear from the above results, even when the thermoplastic resin particles are added in the same manner as in the case of the oxygen absorbent B, if the same resin is added in a small amount (oxygen absorbent D), the same resin is used again. Even with the same amount, in the case of a resin having a large particle diameter (oxygen absorbent E) and the case of using a thermoplastic resin having a high softening point (oxygen absorbent F), the addition effect was low, and fire occurred because heat generation could not be suppressed. .
【００２７】実施例２ 実施例１に調製した酸素吸収剤Ｂ２ｇを、有孔ポリエチ
レンフィルムをラミネートした和紙の小袋に充填して酸
素吸収包装体を準備した。次にポリ塩化ビニリデン被覆
ナイロン／ポリエチレンの積層フィルムのガスバリア袋
に、カステラ２００ｇと前記酸素吸収包装体１個を入れ
空気量１５０ｃｃとともに密封して、室温下に２週間保
存した。袋内の酸素濃度は、１日後には０．１％以下に
なったことが確認され、２週間後に開封してカステラの
風味を観察したところ、良好であり、カステラの品質は
保持されていた。Example 2 An oxygen-absorbing package was prepared by filling 2 g of the oxygen-absorbing agent B prepared in Example 1 into a small Japanese paper bag laminated with a perforated polyethylene film. Next, 200 g of Castella and one of the oxygen absorbing packages were put in a gas barrier bag of a laminated film of polyvinylidene chloride-coated nylon / polyethylene, sealed with 150 cc of air, and stored at room temperature for 2 weeks. It was confirmed that the oxygen concentration in the bag became 0.1% or less after one day, and the bag was opened two weeks later and the taste of the castella was observed. As a result, the taste was good, and the quality of the castella was maintained. .
【００２８】実施例３及び比較例６ 実施例１の酸素吸収剤Ｂ及び比較例１の酸素吸収剤Ａ
を、それぞれ、有孔ポリエチレンフィルムでラミネート
した和紙で作成した袋（１００×１４０ｍｍ）に２０ｇ
ずつ充填し、ガス濃度調節剤Ｂ（実施例３）及びガス濃
度調節剤Ａ（比較６）とした。ＧＡＭ寒天培地（日水製
薬）に生育した、Clostridium boturinum （供試菌No１
と記す）の１白金耳を、Ｌ−システィン等を加えて酸化
還元電位を低下させた嫌気性菌用希釈液（以下希釈液と
記す）９ｍｌに懸濁し、更に１０倍ごとの希釈により、
１０7 までの希釈液を調製した。プラスチック製シャー
レに分注固化したＧＡＭ寒天培地に、各希釈液0.１ｍｌ
を２枚ずつ接種し、１枚はガス濃度調節剤Ｂ（実施例
３）とともに、もう１枚はガス濃度調節剤Ａとともに、
ガスバリアー性フィルム（ポリ塩化ビニリデン被覆ナイ
ロン／ポリエチレン）袋に、それぞれ空気量２５００ｍ
ｌとして密封した。Bacteroides fragilis（供試菌No
２）および、Propionibacterium acnes （供試菌No３）
についても、同様に、ガス濃度調節剤Ｂ及びＡととも
に、ガスバリアー性フィルム袋に密封した。上記の、嫌
気性菌を接種した培地およびガス濃度調節剤を密封した
ガスバリア性フィルム袋は、３７℃で３日間保持して培
養を行った後、開封して寒天培地上に出現したコロニー
の数と径の大きさを測定した。結果は、表２に示すよう
に、いずれの菌株においても、実施例３のガス濃度調節
剤Ｂを用いたものは、嫌気性菌は良好な生育を示し、比
較例６のガス濃度調節剤Ａを用いたものと比較して、同
等の嫌気性菌の生育支持能力がみられた。Example 3 and Comparative Example 6 The oxygen absorbent B of Example 1 and the oxygen absorbent A of Comparative Example 1
In a bag (100 × 140 mm) made of Japanese paper laminated with a perforated polyethylene film
Each was filled to obtain a gas concentration regulator B (Example 3) and a gas concentration regulator A (Comparative 6). Clostridium boturinum (test bacteria No. 1) grown on GAM agar medium (Nissui Pharmaceutical)
) Is suspended in 9 ml of a diluent for anaerobic bacteria (hereinafter referred to as diluent) in which the oxidation-reduction potential has been reduced by adding L-cysteine and the like, and further diluted by 10-fold.
Dilutions of up to 10 7 was prepared. 0.1 ml of each diluent was added to a GAM agar medium dispensed and solidified in a plastic petri dish.
Two inoculated with each other, one with gas concentration regulator B (Example 3) and the other with gas concentration regulator A,
Each of the gas barrier films (polyvinylidene chloride-coated nylon / polyethylene) bags have an air volume of 2,500 m.
and sealed. Bacteroides fragilis (test bacteria No
2) and Propionibacterium acnes (test bacteria No. 3)
Was also sealed in a gas barrier film bag together with the gas concentration regulators B and A. The above-described gas-barrier film bag sealed with a medium inoculated with an anaerobic bacterium and a gas concentration regulator was cultured at 37 ° C. for 3 days, and then opened. The number of colonies that appeared on the agar medium was opened. And the size of the diameter were measured. As shown in Table 2, all the strains using the gas concentration regulator B of Example 3 showed good growth of the anaerobic bacteria and the gas concentration regulator A of Comparative Example 6 using any of the strains. As compared with those using, the ability to support the growth of anaerobic bacteria was observed.
【００２９】[0029]
【表２】 [Table 2]
【００３０】[0030]
【発明の効果】本発明の酸素吸収剤は、大量に集積され
たり、雰囲気温度が異常に高くなったりしても、自然発
火の危険性が極めて低く、安全な酸素吸収剤であり、そ
の酸素吸収能や流動性等の性能も、従来のアスコルビン
酸類主剤の酸素吸収剤と変わらず、酸素吸収剤包装体と
してコンパクトに収納でき、実用性に優れた酸素吸収剤
である。特に本発明の酸素吸収剤は、酸素吸収剤包装体
として１袋当たりの酸素吸収剤量が多く、比較的多量に
酸素吸収剤を使用する嫌気性菌培養用のガス濃度調節剤
に好適に使用できる。The oxygen absorbent of the present invention has a very low risk of spontaneous ignition even if it is accumulated in a large amount or the ambient temperature becomes abnormally high, and is a safe oxygen absorbent. The oxygen absorbing agent is excellent in practicality, such as absorption ability and fluidity, which can be stored compactly as an oxygen absorbing agent package and is practically the same as the conventional oxygen absorbing agent of ascorbic acids. In particular, the oxygen absorbent of the present invention has a large amount of oxygen absorbent per bag as an oxygen absorbent package, and is suitably used as a gas concentration regulator for anaerobic bacteria culture using a relatively large amount of oxygen absorbent. it can.
【図面の簡単な説明】[Brief description of the drawings]
【図１】「未知物質の危険性評価の試験方法及び判定基
準」容器等級IIの試験における酸素吸収剤の温度変化を
示す。FIG. 1 shows the temperature change of an oxygen absorbent in the test of “Danger Evaluation of Unknown Substances and Criteria” for container class II.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｂ０１Ｊ 20/20 Ｂ０１Ｊ 20/20 Ｅ Ｃ１２Ｎ 1/20 Ｃ１２Ｎ 1/20 Ａ ──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. 6 Identification symbol FI B01J 20/20 B01J 20/20 E C12N 1/20 C12N 1/20 A
Claims (4)
む酸素吸収組成物に、軟化点が９０〜１２５℃で粒子径
が１〜５００μｍの粒状熱可塑性樹脂を、酸素吸収組成
物１００重量部当たり、１０〜６０重量部混合してなる
ことを特徴とする酸素吸収剤。1. An oxygen-absorbing composition containing ascorbic acid, water and activated carbon is mixed with a granular thermoplastic resin having a softening point of 90 to 125 ° C. and a particle diameter of 1 to 500 μm, and 10 parts by weight per 100 parts by weight of the oxygen-absorbing composition. An oxygen absorbent, which is obtained by mixing up to 60 parts by weight.
ロピレン又はこれらの混合物である請求項１記載の酸素
吸収剤。2. The oxygen absorbent according to claim 1, wherein the thermoplastic resin is polyethylene, polypropylene or a mixture thereof.
填してなる嫌気性菌培養用ガス濃度調節剤。3. A gas concentration regulator for anaerobic bacteria culture, wherein the oxygen absorbent according to claim 1 is filled in a gas permeable packing material.
気性菌を培養することを特徴とする嫌気性菌の培養方
法。4. A method for cultivating anaerobic bacteria, which comprises culturing anaerobic bacteria in the presence of the gas concentration regulator according to claim 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03891898A JP3741181B2 (en) | 1997-03-19 | 1998-02-20 | Oxygen absorber and method for culturing anaerobic bacteria using the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6641197 | 1997-03-19 | ||
| JP9-66411 | 1997-03-19 | ||
| JP03891898A JP3741181B2 (en) | 1997-03-19 | 1998-02-20 | Oxygen absorber and method for culturing anaerobic bacteria using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10314581A true JPH10314581A (en) | 1998-12-02 |
| JP3741181B2 JP3741181B2 (en) | 2006-02-01 |
Family
ID=26378226
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03891898A Expired - Fee Related JP3741181B2 (en) | 1997-03-19 | 1998-02-20 | Oxygen absorber and method for culturing anaerobic bacteria using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3741181B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1170330A (en) * | 1997-08-29 | 1999-03-16 | Sanyo Electric Co Ltd | Oxygen absorbent and its regenerating method |
| US7022162B2 (en) | 2001-02-15 | 2006-04-04 | Forschungszentrum Karlsruhe Gmbh | Use of a material and a method for retaining polyhalogenated compounds |
| JP2007295826A (en) * | 2006-04-28 | 2007-11-15 | Mitsubishi Gas Chem Co Inc | Method for microscopically observing state of culture |
| JP2009291166A (en) * | 2008-06-09 | 2009-12-17 | Mitsubishi Gas Chem Co Inc | Atmosphere-regulating agent and method for culturing cell by using the same |
| WO2011065363A1 (en) | 2009-11-24 | 2011-06-03 | 三菱瓦斯化学株式会社 | Atmosphere control composition |
| WO2012030618A1 (en) * | 2010-08-30 | 2012-03-08 | Corning Incorporated | Organic antioxidant based filtration apparatus and method |
| JP2013099292A (en) * | 2011-11-09 | 2013-05-23 | Gifu Prefecture | Freshness-keeping sheet for food and manufacturing method therefor |
| JP2019150780A (en) * | 2018-03-05 | 2019-09-12 | 三菱瓦斯化学株式会社 | Organic deoxidation material with suppressed coloration |
-
1998
- 1998-02-20 JP JP03891898A patent/JP3741181B2/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1170330A (en) * | 1997-08-29 | 1999-03-16 | Sanyo Electric Co Ltd | Oxygen absorbent and its regenerating method |
| US7022162B2 (en) | 2001-02-15 | 2006-04-04 | Forschungszentrum Karlsruhe Gmbh | Use of a material and a method for retaining polyhalogenated compounds |
| JP2007295826A (en) * | 2006-04-28 | 2007-11-15 | Mitsubishi Gas Chem Co Inc | Method for microscopically observing state of culture |
| JP4626768B2 (en) * | 2006-04-28 | 2011-02-09 | 三菱瓦斯化学株式会社 | Method for microscopic observation of culture state |
| JP2009291166A (en) * | 2008-06-09 | 2009-12-17 | Mitsubishi Gas Chem Co Inc | Atmosphere-regulating agent and method for culturing cell by using the same |
| WO2011065363A1 (en) | 2009-11-24 | 2011-06-03 | 三菱瓦斯化学株式会社 | Atmosphere control composition |
| US9085752B2 (en) | 2009-11-24 | 2015-07-21 | Mitsubishi Gas Chemical Company, Inc. | Atmosphere control composition |
| WO2012030618A1 (en) * | 2010-08-30 | 2012-03-08 | Corning Incorporated | Organic antioxidant based filtration apparatus and method |
| US8496739B2 (en) | 2010-08-30 | 2013-07-30 | Corning Incorporated | Organic antioxidant based filtration apparatus and method |
| JP2013099292A (en) * | 2011-11-09 | 2013-05-23 | Gifu Prefecture | Freshness-keeping sheet for food and manufacturing method therefor |
| JP2019150780A (en) * | 2018-03-05 | 2019-09-12 | 三菱瓦斯化学株式会社 | Organic deoxidation material with suppressed coloration |
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|---|---|
| JP3741181B2 (en) | 2006-02-01 |
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