JPH1045177A - Method for storing article - Google Patents
Method for storing articleInfo
- Publication number
- JPH1045177A JPH1045177A JP10163697A JP10163697A JPH1045177A JP H1045177 A JPH1045177 A JP H1045177A JP 10163697 A JP10163697 A JP 10163697A JP 10163697 A JP10163697 A JP 10163697A JP H1045177 A JPH1045177 A JP H1045177A
- Authority
- JP
- Japan
- Prior art keywords
- oxygen
- container
- carbon dioxide
- article
- packaging
- 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.)
- Granted
Links
Landscapes
- Packages (AREA)
- Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
- Storage Of Fruits Or Vegetables (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は酸素吸収樹脂層を備
えた包装容器に物品を密封保存する物品の保存方法に関
する。本発明は、詳しくは、熱可塑性樹脂に鉄系脱酸素
剤を混練し分散してなる酸素吸収樹脂層を少なくとも容
器の一部に備え、酸素を吸収するようにしてなる包装容
器内に物品を収納して容器を密封することにより、炭酸
ガスの存在下に酸素を吸収して実質的に無酸素状態に物
品を保持することを特徴とする物品の保存方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preserving articles in a packaging container provided with an oxygen-absorbing resin layer. The present invention specifically provides an oxygen-absorbing resin layer obtained by kneading and dispersing an iron-based oxygen absorber in a thermoplastic resin, at least in a part of the container, and placing the article in a packaging container configured to absorb oxygen. The present invention relates to a method for preserving an article, wherein the article is stored and hermetically sealed, thereby absorbing oxygen in the presence of carbon dioxide gas and keeping the article in a substantially oxygen-free state.
【０００２】[0002]
【従来の技術】近年、物品の包装技術の一つとして脱酸
素剤を用いる包装技術、すなわち脱酸素剤包装技術が確
立され、食品、医薬品の他様々な物品の保存に適用され
るようになって、色々な分野で利用されている。この脱
酸素剤包装技術は、保存すべき物品を被包した包装容器
内を脱酸素剤を用いて嫌気状態に保つことにより、酸素
の存在に起因する物品の品質劣化を防止する技術をい
う。この技術によれば、例えば、食品にあっては、食品
の酸化劣化、油脂分の酸化防止、変褪色防止、風味保
持、虫害防止、細菌やカビの繁殖防止等を図ることがで
き、また、医薬品にあっては、酸化や変色の防止を図る
ことができる。このように脱酸素剤包装によれば、品質
を良好に保持しながら物品を長期に保存することが可能
となる。2. Description of the Related Art In recent years, a packaging technique using an oxygen scavenger, that is, an oxygen scavenger packaging technique, has been established as one of article packaging techniques, and has been applied to preservation of various articles such as foods and pharmaceuticals. It is used in various fields. The oxygen absorbing agent packaging technology refers to a technology for preventing the quality deterioration of an article caused by the presence of oxygen by keeping the inside of a packaging container enclosing articles to be preserved in an anaerobic state using an oxygen absorbing agent. According to this technology, for example, in the case of food, it is possible to prevent oxidative deterioration of the food, prevention of oxidation of fats and oils, prevention of discoloration and discoloration, retention of flavor, prevention of insect damage, prevention of growth of bacteria and mold, and the like. For pharmaceuticals, oxidation and discoloration can be prevented. As described above, according to the oxygen scavenger packaging, it is possible to store articles for a long period of time while maintaining good quality.
【０００３】脱酸素剤包装に用いられる脱酸素剤は、酸
素吸収能を有する還元性物質を主剤とする脱酸素剤組成
物からなり、通常、脱酸素剤組成物の粉粒体を通気性小
袋に充填した脱酸素剤包装体として用いられる。脱酸素
剤としては、従来から種々の脱酸素剤組成物が提案され
ているが、今日では鉄粉を主剤とする鉄粉系脱酸素剤
が、安全性、酸素吸収効率、コスト等の点から最も汎用
的に使用されている。しかしながら、このように優れた
鉄粉系脱酸素剤にしても、次に説明するように、炭酸ガ
スの存在する雰囲気下における酸素吸収性能は必ずしも
満足すべきものではない。[0003] The oxygen scavenger used for the oxygen scavenger packaging is composed of an oxygen scavenger composition mainly composed of a reducing substance having an oxygen absorbing ability. It is used as a package of oxygen scavenger filled with water. Various oxygen absorber compositions have been conventionally proposed as oxygen absorbers, but today iron powder-based oxygen absorbers containing iron powder as a main component have been proposed in view of safety, oxygen absorption efficiency, cost, etc. Most commonly used. However, even with such an excellent iron-powder-based oxygen scavenger, the oxygen absorption performance in an atmosphere containing carbon dioxide gas is not always satisfactory, as described below.
【０００４】包装技術の一つに炭酸ガス置換包装があ
る。例えば、食肉類の赤味保持、カステラ、蒸しケーキ
等の風味保持、医薬品の保存等に炭酸ガス置換は有効で
あり、食品、医薬品等の品質保持を目的として広く行わ
れている。炭酸ガス置換包装は単に炭酸ガスによる品質
保持効果を狙うだけでなく、ガス置換による包装容器内
の酸素除去を目的とする。このため、炭酸ガス置換包装
に脱酸素剤を併用することは、極めて効果的な方法とな
ると考えられる。しかしながら、この場合、鉄粉系脱酸
素剤は、炭酸ガスの影響により酸素吸収性能が著しく阻
害され、酸素吸収速度が低下して残余の酸素除去に長時
間を要したり、また酸素吸収が途中で停止したりするこ
とがある。[0004] One of the packaging techniques is carbon dioxide replacement packaging. For example, carbon dioxide replacement is effective for maintaining the redness of meat, maintaining the flavor of castella, steamed cake, etc., and preserving pharmaceuticals, and is widely performed for the purpose of maintaining the quality of foods, pharmaceuticals, and the like. Carbon dioxide replacement packaging is not only aimed at the effect of maintaining the quality of carbon dioxide gas, but also for removing oxygen in the packaging container by gas replacement. For this reason, it is considered that the combined use of a deoxidizer in the carbon dioxide gas replacement packaging is an extremely effective method. However, in this case, the oxygen absorption performance of the iron-powder-based oxygen scavenger is significantly impaired due to the influence of carbon dioxide gas, and the oxygen absorption rate decreases, so that it takes a long time to remove the remaining oxygen, or the oxygen absorption is not complete. And may stop.
【０００５】またチーズ・ヨーグルト等の発酵食品、豆
類・穀物類等の農産物等は、包装容器内に保存中に炭酸
ガスが発生することがあり、また、レトルト処理等の加
熱処理により炭酸ガスを発生する食品も多い。このよう
に炭酸ガスを発生するものに鉄粉系脱酸素剤を用いて脱
酸素剤包装する場合にも、鉄粉系脱酸素剤はやはり発生
する炭酸ガスの影響を受ける。炭酸ガス発生が著しい場
合には、当然前述のように、鉄粉系脱酸素剤は酸素吸収
性能が著しく阻害され、脱酸素剤包装の目的を達成する
ことはできない。また包装直後には炭酸ガスの発生が僅
かで無酸素状態が達成できた場合でも、その後炭酸ガス
濃度が上がると、外部から侵入する酸素を十分吸収する
ことができず実質的に無酸素状態を保つことができず、
長期的にはやはり脱酸素剤包装の目的が達成できないよ
うなことが起こる。[0005] Fermented foods such as cheese and yogurt, and agricultural products such as beans and grains may generate carbon dioxide gas during storage in a packaging container, and carbon dioxide gas may be generated by heat treatment such as retort treatment. Many foods are generated. As described above, when packaging the oxygen-absorbing agent using an iron-powder-based oxygen absorber for the one that generates carbon dioxide, the iron-powder-based oxygen absorber is also affected by the generated carbon dioxide. When the generation of carbon dioxide gas is remarkable, the oxygen absorption performance of the iron-powder-based oxygen scavenger is significantly impaired as described above, and the purpose of the oxygen scavenger packaging cannot be achieved. Immediately after packaging, even if the generation of carbon dioxide is slight and an oxygen-free state can be achieved, if the concentration of carbon dioxide subsequently increases, oxygen that intrudes from the outside cannot be absorbed sufficiently, and the oxygen-free state can be substantially reduced. I ca n’t keep it,
In the long term, it will still be impossible to achieve the purpose of oxygen scavenger packaging.
【０００６】このように鉄粉系脱酸素剤は、炭酸ガスの
影響を受けて酸素吸収性能が阻害されるために、炭酸ガ
スを含む雰囲気下では十分機能しないという問題があ
る。このため、炭酸ガスを含む系の脱酸素剤包装技術の
開発が望まれていた。[0006] As described above, the iron powder-based oxygen scavenger has a problem that it does not function sufficiently in an atmosphere containing carbon dioxide gas because the oxygen absorption performance is impaired by the influence of carbon dioxide gas. For this reason, the development of a packaging technology for oxygen scavengers containing carbon dioxide has been desired.
【０００７】[0007]
【発明が解決しようとする課題】本発明の目的は、炭酸
ガスを含む雰囲気下では鉄粉系脱酸素剤が十分機能しな
いという前記従来技術の問題を解決して、炭酸ガスを含
む雰囲気下で酸素を吸収して実質的に無酸素状態とする
ことができ、炭酸ガス置換しての脱酸素剤包装や炭酸ガ
スを発生する物品の脱酸素剤包装を可能とする物品の保
存方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problem of the prior art that the iron powder-based oxygen scavenger does not function sufficiently in an atmosphere containing carbon dioxide. Provided is a method for preserving an article, which is capable of absorbing oxygen to form a substantially oxygen-free state and allowing oxygen-absorbing packaging for carbon dioxide-substituted articles and oxygen-absorbing packaging for articles generating carbon dioxide. It is in.
【０００８】[0008]
【発明が解決しようとする手段】本発明者らは、上記従
来の脱酸素剤包装技術の問題点を解決するべく鋭意研究
を行った結果、熱可塑性樹脂に鉄粉系脱酸素剤を混練し
分散させた酸素吸収樹脂組成物が炭酸ガスを含む雰囲気
下で十分に酸素吸収性能を発揮することを見出し本発明
を完成するに至った。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems of the conventional oxygen absorber packaging technology, and as a result, kneaded an iron powder-based oxygen absorber into a thermoplastic resin. The inventors have found that the dispersed oxygen-absorbing resin composition exhibits sufficient oxygen-absorbing performance under an atmosphere containing carbon dioxide gas, and have completed the present invention.
【０００９】すなわち、本発明は、熱可塑性樹脂に鉄系
脱酸素剤を混練し分散してなる酸素吸収樹脂層を少なく
とも容器の一部に備え、酸素を吸収するようにしてなる
包装容器内に物品を収納して容器を密封することによ
り、炭酸ガスの存在下に酸素を吸収して実質的に無酸素
状態に物品を保持することを特徴とする物品の保存方法
を提供するものである。That is, the present invention provides an oxygen-absorbing resin layer obtained by kneading and dispersing an iron-based oxygen-absorbing agent in a thermoplastic resin at least in a part of a container, so that the oxygen-absorbing resin layer is contained in a packaging container capable of absorbing oxygen. It is an object of the present invention to provide a method for preserving an article, wherein the article is stored and hermetically sealed, whereby oxygen is absorbed in the presence of carbon dioxide gas and the article is kept substantially in an oxygen-free state.
【００１０】[0010]
【発明の実施の形態】本発明の包装容器は、少なくとも
その一部に酸素吸収樹脂層を備え容器内の酸素を吸収す
るようにしてなる容器であり、そして酸素吸収樹脂層は
熱可塑性樹脂に鉄系脱酸素剤を混練し分散してなる樹脂
組成物の層である。酸素吸収樹脂層は、被収納物品と直
接接触することのないように、通常は表面（容器内面）
に保護層を配した積層体として用いられる。ここでは、
熱可塑性樹脂に鉄系脱酸素剤を混練し分散してなる酸素
吸収樹脂層を単に酸素吸収樹脂層ということがある。BEST MODE FOR CARRYING OUT THE INVENTION The packaging container of the present invention is a container provided with an oxygen-absorbing resin layer at least in a part thereof so as to absorb oxygen in the container, and the oxygen-absorbing resin layer is made of a thermoplastic resin. This is a layer of a resin composition obtained by kneading and dispersing an iron-based oxygen scavenger. The oxygen-absorbing resin layer is usually on the surface (inside of the container) so that it does not come into direct contact with the articles to be stored.
Used as a laminate in which a protective layer is disposed. here,
An oxygen-absorbing resin layer obtained by kneading and dispersing an iron-based oxygen scavenger in a thermoplastic resin is sometimes simply referred to as an oxygen-absorbing resin layer.
【００１１】本発明においては、包装容器は、その一部
または全部が酸素吸収樹脂層を含む積層体からなる容器
であってもよく、また容器内に酸素吸収樹脂層を含む積
層体を備えた容器であってもよい。さらに、包装容器は
酸素吸収樹脂層を含む多層フィルムからなる包装袋であ
ってもよい。In the present invention, the packaging container may be a container composed of a laminate including an oxygen-absorbing resin layer partially or entirely, or provided with a laminate including an oxygen-absorbing resin layer in the container. It may be a container. Further, the packaging container may be a packaging bag made of a multilayer film including an oxygen absorbing resin layer.
【００１２】本発明に係る酸素吸収樹脂層は、炭酸ガス
を含む雰囲気下でも酸素を吸収することができる。した
がって、本発明の方法によれば、包装容器内に物品を収
納し容器内を炭酸ガスで置換したのち容器を密封するこ
とにより、容器内の酸素を吸収して実質的に酸素を含む
ことなくかつ炭酸ガスを含む雰囲気下に物品を保持する
ことができる。本発明のより好ましい態様として、物品
を収納後、炭酸ガスで置換した容器を密封した後、低温
で保存する方法を挙げることができる。ここで保存温度
は１５℃以下が好ましく、より好ましくは１０℃以下で
あり、特に５℃以下が好適である。The oxygen absorbing resin layer according to the present invention can absorb oxygen even in an atmosphere containing carbon dioxide gas. Therefore, according to the method of the present invention, by storing an article in a packaging container, replacing the inside of the container with carbon dioxide gas, and then sealing the container, it absorbs oxygen in the container and contains substantially no oxygen. In addition, the article can be held under an atmosphere containing carbon dioxide gas. As a more preferred embodiment of the present invention, there can be mentioned a method of storing the article, storing the article at a low temperature after sealing the container replaced with carbon dioxide gas. Here, the storage temperature is preferably 15 ° C. or lower, more preferably 10 ° C. or lower, and particularly preferably 5 ° C. or lower.
【００１３】本発明によれば、物品、特に食品の保存に
おいて、炭酸ガスの制菌効果及び色保持効果が期待で
き、窒素置換や真空包装との組み合わせにより、一層優
れた保存性を発揮することができる。また本発明の方法
は、好ましくは、炭酸ガスを発生する物品に適用され
る。また物品は炭酸ガスの発生が加熱によって起こる物
品であってもよく、この場合には、本発明の方法によれ
ば、物品を包装容器内に収納して密封したのち加熱する
か、または加熱した物品を包装容器内に収納して密封す
る。According to the present invention, in the storage of articles, especially foods, a bacteriostatic effect and a color holding effect of carbon dioxide gas can be expected, and more excellent preservability can be exhibited by combining with nitrogen replacement or vacuum packaging. Can be. Further, the method of the present invention is preferably applied to an article generating carbon dioxide gas. Further, the article may be an article in which generation of carbon dioxide gas is caused by heating. In this case, according to the method of the present invention, the article is housed in a packaging container, sealed and then heated, or heated. The article is stored in a packaging container and sealed.
【００１４】本発明の方法によって畜肉食品類や発酵食
品のように品質劣化の早い食品を保存する場合は、炭酸
ガス置換や窒素ガス置換等のガス置換を併用すれば、初
期酸素濃度を低減させることができる。その場合、容器
内部を早く無酸素状態にするためには、初期酸素濃度が
低いほど好ましい。この初期酸素濃度は、状況により異
なるが、通常は５％以下が好ましく、１％以下が特に好
ましい。本発明においては、ガス置換中でも炭酸ガス置
換を併用することが好ましい。本発明に係る容器を用
い、炭酸ガス置換を併用することによって、畜肉食品類
の色保持や制菌、カステラ等の菓子類の風味保持、医薬
品の品質劣化防止等に効果をあげることができる。When preserving foods having a rapid deterioration in quality, such as meat or fermented foods, according to the method of the present invention, the initial oxygen concentration can be reduced by using gas replacement such as carbon dioxide replacement or nitrogen gas replacement. be able to. In that case, in order to quickly bring the interior of the container to an oxygen-free state, the lower the initial oxygen concentration, the better. The initial oxygen concentration varies depending on the situation, but is usually preferably 5% or less, particularly preferably 1% or less. In the present invention, it is preferable to use carbon dioxide gas replacement during gas replacement. By using the container according to the present invention and replacing the carbon dioxide gas, it is possible to improve the effects of keeping the color of livestock meat foods, controlling bacteria, maintaining the flavor of confectionery such as castella, and preventing quality deterioration of pharmaceuticals.
【００１５】本発明の係る容器は、容器内の炭酸ガスの
存在の有無に関わらず、性能を発揮することができるた
め、炭酸ガス置換による容器内の炭酸ガス濃度は特に制
限はないが、１％以上が好ましく、５％以上がより好ま
しい。また、容器内の初期酸素濃度を低減させるため
に、高濃度の炭酸ガス置換により、容器内の炭酸ガス濃
度を３０％以上とすることもできる。本発明の方法は、
炭酸ガスを発生する物品や炭酸ガス雰囲気下の保存が適
する物品の脱酸素剤包装に適し、食品、例えば畜肉加工
品，野菜類，果物類，魚介類，発酵食品（チーズ，ヨー
グルトなど），菓子類（カステラ，蒸しケーキなど）や
豆類・穀物類、化粧品、石鹸、医薬品などの物品の保存
に適用される。The container according to the present invention can exhibit its performance regardless of the presence or absence of carbon dioxide in the container. Therefore, the concentration of carbon dioxide in the container by carbon dioxide substitution is not particularly limited, % Or more is preferable, and 5% or more is more preferable. Further, in order to reduce the initial oxygen concentration in the container, the concentration of carbon dioxide in the container can be increased to 30% or more by replacing the carbon dioxide with a high concentration. The method of the present invention comprises:
Suitable for packaging oxygen absorbers for products that generate carbon dioxide or for products that are suitable for storage in a carbon dioxide atmosphere. Food, such as processed meat, vegetables, fruits, seafood, fermented foods (cheese, yogurt, etc.), confectionery It is applied to the preservation of articles such as foods (castella, steamed cake, etc.), beans and cereals, cosmetics, soaps, and pharmaceuticals.
【００１６】本発明の包装容器に配される酸素吸収樹脂
層は、熱可塑性樹脂に鉄系脱酸素剤を混練し分散してな
る樹脂組成物からなる。熱可塑性樹脂としては、鉄粉系
脱酸素剤と混練して酸素を吸収することができる樹脂で
あればよく、例えば、低密度ポリエチレン，中密度ポリ
エチレン，高密度ポリエチレン，ポリプロピレン，プロ
ピレン−エチレン共重合体，エチレン−酢酸ビニル共重
合体、これらのブレンド物などのオレフィン系樹脂、ポ
リスチレン，スチレン−ブタジエン共重合体，スチレン
−イソプレン共重合体などのスチレン系樹脂などが挙げ
られる。これらの樹脂は単独でもまたはブレンド物とし
ても使用できる。The oxygen-absorbing resin layer provided in the packaging container of the present invention comprises a resin composition obtained by kneading and dispersing an iron-based oxygen scavenger in a thermoplastic resin. The thermoplastic resin may be any resin that can absorb oxygen by being kneaded with an iron powder-based oxygen absorber, and examples thereof include low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene, and propylene-ethylene copolymer. Olefinic resins such as coalescables, ethylene-vinyl acetate copolymers, and blends thereof; and styrene-based resins such as polystyrene, styrene-butadiene copolymers, and styrene-isoprene copolymers. These resins can be used alone or as a blend.
【００１７】熱可塑性樹脂に配合される鉄粉系脱酸素剤
は、鉄粉およびハロゲン化金属からなる公知の脱酸素剤
が使用できる。鉄粉としては、還元鉄粉、噴霧鉄粉など
の各種製法で得られる鉄粉が使用でき、鉄粉の粒径は１
０〜５０μｍが好ましく、その最大粒子径は酸素吸収樹
脂層の加工を考慮して制限を受ける。ハロゲン化金属と
しては、塩化ナトリウム、臭化ナトリウム、ヨウ化ナト
リウム、塩化カリウム、ヨウ化カリウム、臭化カリウ
ム、塩化カルシウム、塩化マグネシウムまたは塩化バリ
ウム等で例示されるアルカリ金属又はアルカリ土類金属
のハロゲン化物の１種もしくは２種以上が好ましく用い
られる。As the iron powder-based oxygen scavenger mixed with the thermoplastic resin, a known oxygen scavenger composed of iron powder and a metal halide can be used. As the iron powder, iron powder obtained by various methods such as reduced iron powder and spray iron powder can be used.
It is preferably 0 to 50 μm, and the maximum particle size is limited in consideration of the processing of the oxygen-absorbing resin layer. Examples of the metal halide include alkali metal and alkaline earth metal halogens exemplified by sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium iodide, potassium bromide, calcium chloride, magnesium chloride and barium chloride. One or more compounds are preferably used.
【００１８】ハロゲン化金属の鉄粉に対する配合量は、
鉄粉１００重量部に対して好ましくは０．０５〜５０重
量部であり、より好ましくは０．１〜２０重量部であ
る。ハロゲン化金属の配合量が０．０５部未満の場合に
は酸素吸収性能が発揮されず、また５０重量部を越える
と、酸素吸収反応に過剰すぎるため、過剰に水分を吸収
して酸素吸収が停止することがあり、いずれにしても上
記範囲を越えることは好ましくない。The compounding amount of the metal halide to the iron powder is as follows:
It is preferably 0.05 to 50 parts by weight, more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of iron powder. If the amount of the metal halide is less than 0.05 part, the oxygen absorption performance is not exhibited. If the amount exceeds 50 parts by weight, the oxygen absorption reaction is excessive, so that excessive moisture is absorbed and oxygen absorption is reduced. It may stop, and in any case, it is not preferable to exceed the above range.
【００１９】鉄粉とハロゲン化金属とからなる酸素吸収
剤は、鉄粉とハロゲン化金属の粉末を単に混合したも
の、あるいは鉄粉の表面に各種の手段でハロゲン化金属
を被覆したものであってもよい。また鉄粉とハロゲン化
金属粉末を酸素吸収樹脂と直接混合する方法も可能であ
る。The oxygen absorbent consisting of iron powder and metal halide is obtained by simply mixing iron powder and metal halide powder or by coating the surface of iron powder with metal halide by various means. You may. Further, a method of directly mixing iron powder and metal halide powder with the oxygen absorbing resin is also possible.
【００２０】酸素吸収剤の熱可塑性樹脂に対する配合比
は、好ましくは熱可塑性樹脂の８０重量％以下、より好
ましくは２０〜５０重量％である。酸素吸収剤の配合比
が少なすぎると酸素吸収性能が得られず、また多すぎる
と、得られたシートやフィルムの成形性、強度が低下し
て好適なシートやフィルムが得ることができない。この
ため、酸素吸収剤の配合比は、酸素吸収性能や酸素吸収
樹脂層の加工方法に応じて上記範囲内に適宜選ばれる。
酸素吸収樹脂層には酸素吸収剤以外にも保存性や加工性
の向上のためのアルカリ土類金属酸化物、臭気成分対策
のためのガス吸着剤、着色剤、フィラーなどを配合、分
散させることができる。The mixing ratio of the oxygen absorbent to the thermoplastic resin is preferably 80% by weight or less, more preferably 20 to 50% by weight of the thermoplastic resin. If the compounding ratio of the oxygen absorbent is too small, the oxygen absorbing performance cannot be obtained, and if it is too large, the moldability and strength of the obtained sheet or film are reduced, and a suitable sheet or film cannot be obtained. For this reason, the compounding ratio of the oxygen absorbent is appropriately selected from the above range according to the oxygen absorbing performance and the processing method of the oxygen absorbing resin layer.
The oxygen-absorbing resin layer should contain and disperse, besides the oxygen-absorbing agent, alkaline earth metal oxides for improving storability and processability, gas adsorbents for preventing odor components, coloring agents, fillers, etc. Can be.
【００２１】本発明の酸素吸収樹脂層は、熱可塑性樹脂
に鉄系脱酸素剤を混練し分散して樹脂層を形成し、被包
装物品と直接接触することのないように、少なくとも一
面に酸素透過性の保護層を配した積層体とされ、この積
層体は、多層のシートまたはフィルムとして、容器や袋
などの包装容器に加工して用いられる。酸素吸収樹脂層
の厚みは、特に制限はないが０．１〜３ｍｍの範囲が好
ましい。The oxygen-absorbing resin layer of the present invention is formed by kneading and dispersing an iron-based oxygen-absorbing agent in a thermoplastic resin to form a resin layer. The laminate is provided with a transparent protective layer, and the laminate is used as a multilayer sheet or film processed into a packaging container such as a container or a bag. The thickness of the oxygen absorbing resin layer is not particularly limited, but is preferably in the range of 0.1 to 3 mm.
【００２２】酸素吸収樹脂層は、Ｔダイ法、リングダイ
法等の方法により、単層のフィルムまたはシートとな
し、必要に応じて、一面に熱可塑性樹脂の保護層（容器
の内層を構成）、他面にバリア性樹脂，金属箔などのバ
リア層（容器の外層を構成）を積層し、多層シートまた
は多層フィルムとすることができる。つまり、この多層
シートまたは多層フィルムは、保護層（酸素透過性）、
酸素吸収樹脂層、及びバリア層（酸素バリア性）をこの
順に積層してなるもの、あるいはこれらの層にさらに適
宜所望により中間層を配したものが好ましい。積層方法
としては、ウェットラミネーション、ドライラミネーシ
ョン、押出ラミネーションなどの公知の方法をとること
ができる。また共押出法により前記各層の樹脂を同時に
押し出し、多層シートまたは多層フィルムを形成するこ
ともできる。なお、上記酸素吸収樹脂層は、上述のよう
にして形成されるが、無延伸フィルムまたはシートとす
べきであり、延伸処理したものは表面にボイド等が発生
しやすく、本発明の所期の目的を達成することが困難と
なる。また、多層シートまたは多層フィルム全体も無延
伸のものを用いることが好ましい。The oxygen-absorbing resin layer is formed into a single-layer film or sheet by a method such as a T-die method or a ring-die method. If necessary, a protective layer of a thermoplastic resin may be formed on one side (constituting the inner layer of the container). Alternatively, a barrier layer (constituting the outer layer of the container) such as a barrier resin or a metal foil may be laminated on the other surface to form a multilayer sheet or a multilayer film. In other words, this multilayer sheet or multilayer film has a protective layer (oxygen permeability),
A layer obtained by laminating an oxygen-absorbing resin layer and a barrier layer (oxygen barrier property) in this order, or a layer in which an intermediate layer is further appropriately disposed as required, is preferable. As a lamination method, a known method such as wet lamination, dry lamination, or extrusion lamination can be used. The resin of each layer can be simultaneously extruded by coextrusion to form a multilayer sheet or multilayer film. The oxygen-absorbing resin layer is formed as described above, but it should be a non-stretched film or sheet. It is difficult to achieve the purpose. It is also preferable to use a non-stretched multilayer sheet or multilayer film as a whole.
【００２３】酸素吸収樹脂層に配する保護層としては、
酸素吸収樹脂層に用いられる熱可塑性樹脂が用いられ
が、この層にシール性、ピール性を付与するために、ポ
リビニルアルコール、ポリスチレン、アイオノマー等の
樹脂を添加したり、多層化したりすることもできる。As the protective layer disposed on the oxygen absorbing resin layer,
The thermoplastic resin used for the oxygen-absorbing resin layer is used, but in order to impart sealing properties and peeling properties to this layer, resins such as polyvinyl alcohol, polystyrene, and ionomers may be added, or the layers may be multilayered. .
【００２４】またバリア層としては、エチレン−ビニル
アルコール共重合体、ナイロン、ポリ塩化ビニリデン等
のガスバリア性樹脂、アルミ箔等の金属箔、金属または
金属酸化物蒸着膜等が用いられる。As the barrier layer, a gas-barrier resin such as ethylene-vinyl alcohol copolymer, nylon or polyvinylidene chloride, a metal foil such as an aluminum foil, a metal or metal oxide vapor-deposited film, or the like is used.
【００２５】本発明の方法が適用される物品としては、
酸素吸収樹脂層に分散した鉄系脱酸素剤が水分を得て酸
素吸収性能を発揮するために、水分を含有し、酸素吸収
樹脂層に水分を供給することができる物品が好ましい。Articles to which the method of the present invention is applied include:
In order for the iron-based oxygen scavenger dispersed in the oxygen-absorbing resin layer to obtain moisture and exhibit oxygen-absorbing performance, an article containing water and capable of supplying moisture to the oxygen-absorbing resin layer is preferable.
【００２６】本発明の保存方法に適する物品としては、
上述したとおりであるが、更に具体的には、包装容器内
を炭酸ガス置換することにより、より効果的な保存効果
が得られる物品として、例えば、穀物類、生肉、ソーセ
ージ、ハム、ケーキ等の食品、輸液バッグ等の医薬品が
挙げられる。また、そのもの自体から炭酸ガスを発生す
る物品としては、例えば、農産物である豆や穀物等の穀
物類やチーズ、ヨーグルト、納豆、キムチ等の発酵食品
が挙げられる。さらに、加熱処理した際に油分の分解や
膨張剤の影響で食品自身から炭酸ガスを発生する食品と
して、例えば、ハンバーグ、油揚げ、焼き鳥、饅頭、コ
ロッケ、アメリカンドッグ、餃子、シュウマイ、カステ
ラ、蒸しケーキ等の食品が挙げられる。Articles suitable for the storage method of the present invention include:
As described above, more specifically, by replacing the inside of the packaging container with carbon dioxide gas, as an article that can obtain a more effective storage effect, for example, cereals, raw meat, sausage, ham, cake, etc. Pharmaceutical products such as foods and infusion bags. Examples of the article that generates carbon dioxide from itself include, for example, cereals such as beans and cereals, and fermented foods such as cheese, yogurt, natto, and kimchi, which are agricultural products. Furthermore, as foods that generate carbon dioxide from the food itself under the influence of oil components and swelling agents when subjected to heat treatment, for example, hamburger, fried, yakitori, bun, croquette, American dog, gyoza, Shumai, castella, steamed cake And the like.
【００２７】本発明の方法が適用される物品は、必ずし
も上記の食品、穀物類、医薬品等に限定されるものでな
く、本発明の方法を適用して所期の目的の達成すること
のできる物品であればよい。The articles to which the method of the present invention is applied are not necessarily limited to the above-mentioned foods, cereals, pharmaceuticals and the like, and the intended objects can be achieved by applying the method of the present invention. Any article may be used.
【００２８】[0028]
【実施例】以下、実施例によって本発明を説明するが、
本発明はこれらの実施例に限定されるものではない。 実施例１ 脱酸素性容器の製造：スクリュー（５０ｍｍ径）２本を
内蔵する２軸押出機／ストランドダイ／ブロワー冷却機
／カッターで構成されるペレタイザーを用いて、ポリプ
ロピレン（ＰＰ；メルトインデックス（ＭＩ）０．５ｇ
／１０分、２３０℃）と、鉄粉（平均粒径３０μｍ）に
塩化カルシウム１重量％をコーティングしてなる脱酸素
剤とを６０：４０（重量比）の割合で混練しペレット化
した。Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited to these examples. Example 1 Production of a deoxygenating container: polypropylene (PP; melt index (MI) was measured using a pelletizer composed of a twin screw extruder / strand die / blower cooler / cutter containing two screws (50 mm in diameter). ) 0.5g
/ 10 min, 230 ° C.) and an oxygen scavenger obtained by coating iron powder (average particle size: 30 μm) with 1% by weight of calcium chloride at a ratio of 60:40 (weight ratio) and pelletized.
【００２９】次にポリプロピレン（ＭＩ０．５ｇ／１０
分、２３０℃）、上記ペレット化した鉄系脱酸素剤を含
む樹脂組成物、エチレンビニルアルコール共重合体（エ
チレン含有量３５％、ケン化度９９．６％）および無水
マレイン酸変成ポリプロピレン（ＭＩ０．５ｇ／１０
分、２３０℃）を４種６層共押出機より押し出し、ポリ
プロピレン（ＰＰ層）を内外層とし、鉄系酸素吸収剤を
含む酸素吸収樹脂層を第一の中間層、エチレンビニルア
ルコール共重合体（ＥＶＯＨ層）を第二の中間層とし、
無水マレイン酸変成ポリプロピレンを第二の中間層の接
着層とする４種６層の多層シートを製造した。多層シー
トの層構成（合計厚み８００μｍ）；ＰＰ層（１００）
／第一中間層（２００）／接着層（３０）／第二中間層
（４０）／接着層（３０）／ＰＰ層（４００）Next, polypropylene (MI 0.5 g / 10
, 230 ° C), a resin composition containing the pelletized iron-based oxygen scavenger, an ethylene-vinyl alcohol copolymer (ethylene content 35%, saponification degree 99.6%), and maleic anhydride-modified polypropylene (MI0 0.5g / 10
Extruded from a four-type, six-layer co-extruder, a polypropylene (PP layer) as an inner and outer layer, an oxygen-absorbing resin layer containing an iron-based oxygen absorbent as a first intermediate layer, an ethylene-vinyl alcohol copolymer. (EVOH layer) as the second intermediate layer,
Four types and six layers of multi-layer sheets were prepared in which maleic anhydride-modified polypropylene was used as an adhesive layer for the second intermediate layer. Layer configuration of multilayer sheet (total thickness 800 μm); PP layer (100)
/ First intermediate layer (200) / adhesive layer (30) / second intermediate layer (40) / adhesive layer (30) / PP layer (400)
【００３０】上記多層シートを、真空成型機を用いて温
度約１９０℃で、第二中間層に対して第一中間層が内側
に位置する長方形トレイ状容器（長軸１３０ｍｍ×短軸
１００ｍｍ、深さ２５ｍｍ）に成形加工した。Using a vacuum forming machine, the above-mentioned multilayer sheet is placed in a rectangular tray-shaped container (long axis 130 mm × short axis 100 mm, deep (25 mm).
【００３１】食品（生ハム）の保存試験：上記のトレイ
状容器に生ハム（水分活性０. ９８）１５０ｇを入れ、
ガス不透過性のアルミニウム箔積層材からなる蓋をトレ
イ開口部にヒートシールして密封した。なおトレイ状容
器の密封に際し、容器内を炭酸ガス：窒素ガス＝７：３
の混合ガスで置換して酸素濃度を約１％、炭酸ガス濃度
が約６５％となるようにした。生ハムを収納し炭酸ガス
置換して密封したトレイ状容器を温度１０℃で保存し
て、容器内の酸素濃度を経日的に測定した。この密封ト
レイ状容器を７日目に開封して、容器内の生ハムの色調
および香りを調べた。結果を表１に示す。Preservation test of food (cured ham): 150 g of ham (water activity: 0.98) was placed in the above tray-like container,
A lid made of a gas-impermeable aluminum foil laminate was heat-sealed to the tray opening and sealed. When sealing the tray-shaped container, the inside of the container was carbon dioxide gas: nitrogen gas = 7: 3.
Was replaced by a mixed gas of about 1% and about 65% carbon dioxide. The tray-shaped container containing the raw ham and replacing with carbon dioxide and sealing was stored at a temperature of 10 ° C., and the oxygen concentration in the container was measured daily. The sealed tray-shaped container was opened on the seventh day, and the color tone and aroma of the raw ham in the container were examined. Table 1 shows the results.
【００３２】比較例１ 実施例１で製造したトレイ状容器に、実施例１と同様
に、生ハム（水分活性０. ９８）１５０ｇを入れアルミ
ニウム箔積層材の蓋をヒートシールして密封した。なお
この場合には、容器の密封に際し容器内を窒素ガスでガ
ス置換して酸素濃度が約１％となるようにした。Comparative Example 1 As in Example 1, 150 g of raw ham (water activity: 0.98) was placed in the tray-shaped container manufactured in Example 1, and the lid of the aluminum foil laminated material was sealed by heat sealing. In this case, when the container was sealed, the inside of the container was replaced with nitrogen gas so that the oxygen concentration became about 1%.
【００３３】比較例２ ガス不透過性のアルミニウム箔積層フィルムの袋（サイ
ズ；１３０ｍｍ×１００ｍｍ）に、生ハム（水分活性
０. ９８）１５０ｇと共に、鉄粉（平均粒径３０μｍ）
に塩化カルシウム１重量％をコーティングしてなる脱酸
素剤１ｇを耐水・耐油性和紙（坪量５０ｇ／ｍ2 ）の小
袋（サイズ；４０ｍｍ×４０ｍｍ）に充填した脱酸素剤
包装体を収納し、袋内部のガスを炭酸ガス：窒素ガス＝
７：３の混合ガスで置換して酸素濃度を約１％、炭酸ガ
ス濃度が約６５％となるようにした後、袋をヒートシー
ルして密封した。（以下、脱酸素剤包装体を単に脱酸素
剤という。）Comparative Example 2 150 g of raw ham (water activity: 0.98) and iron powder (average particle size: 30 μm) in a bag (size: 130 mm × 100 mm) of a gas-impermeable aluminum foil laminated film.
The oxygen absorber packaged with 1 g of oxygen absorber coated with 1% by weight of calcium chloride in a small bag (size: 40 mm × 40 mm) of water-resistant and oil-resistant Japanese paper (basis weight 50 g / m 2 ) is stored. Carbon dioxide gas inside the bag: Nitrogen gas =
After replacing with a mixed gas of 7: 3 so that the oxygen concentration was about 1% and the carbon dioxide concentration was about 65%, the bag was heat-sealed and sealed. (Hereinafter, the oxygen scavenger package is simply referred to as an oxygen scavenger.)
【００３４】比較例３ 比較例２と同様に、アルミニウム箔積層フィルムの袋に
生ハム（水分活性０.９８）１５０ｇと脱酸素剤とを入
れ、この場合には袋内部を窒素ガスで置換して酸素濃度
が約１％となるようにした後、袋をヒートシールして密
封した。Comparative Example 3 As in Comparative Example 2, 150 g of raw ham (water activity: 0.98) and an oxygen scavenger were placed in a bag of an aluminum foil laminated film, and in this case, the inside of the bag was replaced with nitrogen gas. After adjusting the oxygen concentration to about 1%, the bag was sealed by heat sealing.
【００３５】それぞれ、生ハムを収納した比較例１、比
較例２および比較例３の密封容器または袋は、実施例１
の場合と同様に、温度１０℃で保存して容器内の酸素濃
度を経日的に測定すると共に、７日目に容器を開封して
保存した生ハムの色調および香りを調べた。結果を表１
に併記する。なお、密封容器内のガス置換に窒素ガスを
用いた比較例１および比較例３では、保存期間中の容器
内のガスにはどの場合も、炭酸ガスは検出されなかっ
た。The sealed containers or bags of Comparative Example 1, Comparative Example 2, and Comparative Example 3 each containing prosciutto ham were prepared in Example 1.
As in the case of the above, while storing at a temperature of 10 ° C., the oxygen concentration in the container was measured daily, and on the 7th day, the container was opened and the color tone and aroma of the stored ham were examined. Table 1 shows the results
It is described together. In Comparative Examples 1 and 3 in which nitrogen gas was used for gas replacement in the sealed container, carbon dioxide gas was not detected in any case of the gas in the container during the storage period.
【００３６】[0036]
【表１】 注１）風味： ３；良好 ２；ややすえ臭あり １；すえ臭大 注２）色調： ３；赤味 ２；やや褐変 １；褐変[Table 1] Note 1) Flavor: 3; Good 2: Slight odor 1: Large odor Note 2) Color: 3; Reddish 2: Slightly browning 1: Browning
【００３７】実施例１の場合、炭酸ガス置換による大量
の炭酸ガスの存在にもかかわらず、本発明の脱酸素性容
器は十分に酸素を吸収して容器内は実質的に無酸素状態
が保たれ、かつ炭酸ガス雰囲気下に保持されたことによ
って、生ハムは風味が損なわれることなく、色調も鮮や
かで変化することもなく、品質は良好に保持されてい
た。これに対して比較例２の場合、ガスバリヤ袋に生ハ
ムと鉄粉系脱酸素剤を封入して炭酸ガス置換を行ったた
めに、従来型の脱酸素剤は炭酸ガスの影響を受けて十分
に酸素吸収できず、生ハムは品質劣化を来していた。ま
た、脱酸素性容器を用いた比較例１およびガスバリヤ袋
に脱酸素剤を用いた比較例３の場合、両者は窒素ガス置
換のために炭酸ガスの影響を受けることなく脱酸素能は
十分に発揮されたが、炭酸ガス雰囲気下の保存でなかっ
ために、色調変化が起こった。In the case of Example 1, despite the presence of a large amount of carbon dioxide due to carbon dioxide replacement, the oxygen-absorbing container of the present invention sufficiently absorbs oxygen and maintains a substantially oxygen-free state in the container. By being dripped and kept in a carbon dioxide atmosphere, the quality of the raw ham was well maintained without any loss of flavor, without vivid color change. On the other hand, in the case of Comparative Example 2, since the raw oxygen and the iron powder-based oxygen absorber were sealed in the gas barrier bag and the carbon dioxide gas was replaced, the conventional oxygen absorber was sufficiently affected by the carbon dioxide gas. Due to the inability to absorb oxygen, the raw ham had degraded in quality. In the case of Comparative Example 1 using a deoxidizing container and Comparative Example 3 using a deoxidizing agent in a gas barrier bag, both of them have sufficient deoxygenating capacity without being affected by carbon dioxide gas due to nitrogen gas replacement. Although it was exhibited, the color tone changed because it was not stored under a carbon dioxide atmosphere.
【００３８】実施例２ 実施例１で製造したトレイ状容器にチーズ２００ｇを入
れアルミニウム箔積層材の蓋をヒートシールして容器を
密封した。なお、トレイ状容器の密封に際して、容器内
は窒素ガスでガス置換して容器内の酸素濃度が約１％と
なるようにした。Example 2 200 g of cheese was placed in the tray-shaped container produced in Example 1, and the lid of the aluminum foil laminate was heat-sealed to seal the container. When the tray-shaped container was sealed, the inside of the container was replaced with nitrogen gas so that the oxygen concentration in the container became about 1%.
【００３９】比較例４ 比較例２と同じアルミニウム箔積層フィルムの袋にチー
ズ２００ｇと脱酸素剤１個を入れ、袋内部を窒素ガスで
置換して酸素濃度約１％としたのち袋をヒートシールし
て密封した。Comparative Example 4 200 g of cheese and one oxygen scavenger were placed in the same aluminum foil laminated film bag as in Comparative Example 2, the inside of the bag was replaced with nitrogen gas to make the oxygen concentration about 1%, and the bag was heat-sealed. And sealed.
【００４０】それぞれ、実施例２および比較例４のチー
ズを収納した密封容器を温度１０℃で保存して容器内の
酸素濃度を経日的に測定すると共に、７日目に容器を開
封して保存したチーズの風味を調べた。結果を表２に示
す。Each of the sealed containers containing the cheeses of Example 2 and Comparative Example 4 was stored at a temperature of 10 ° C. to measure the oxygen concentration in the containers daily, and the containers were opened on the seventh day. The flavor of the preserved cheese was examined. Table 2 shows the results.
【００４１】[0041]
【表２】 [Table 2]
【００４２】表２の結果に明らかなように、保存中にチ
ーズから炭酸ガスの発生が認められたが、実施例２の場
合、炭酸ガスの発生があっても、容器内の酸素は良好に
吸収されて保存系内は実質的に無酸素状態に保たれ、チ
ーズの風味は変化することなく品質が良好に保持されて
いた。これに対して比較例４の場合には、炭酸ガスの影
響を受けて容器内の酸素が十分に吸収されず、チーズは
異臭大にして品質劣化が起こっていた。As is evident from the results in Table 2, generation of carbon dioxide from the cheese was observed during storage, but in the case of Example 2, even if carbon dioxide was generated, the oxygen in the container was satisfactorily increased. The cheese was absorbed and the storage system was kept substantially in an oxygen-free state, and the quality of the cheese was well maintained without changing the flavor. On the other hand, in the case of Comparative Example 4, the oxygen in the container was not sufficiently absorbed due to the influence of the carbon dioxide gas, and the cheese had an unpleasant smell and the quality was deteriorated.
【００４３】実施例３ 脱酸素性フィルム袋の製造：実施例１と同じくペレタイ
ザーを用いて、ポリプロピレン（Ｍ９．０ｇ／１０分、
２３０℃）と、鉄粉（平均粒径３０μｍ）に塩化カルシ
ウム１重量％をコーティングしてなる酸素吸収剤とを６
０：４０（重量比）の割合で混練しペレット化した。Example 3 Production of a deoxygenated film bag: Polypropylene (M 9.0 g / 10 min, using a pelletizer in the same manner as in Example 1)
230 ° C.) and an oxygen absorber obtained by coating iron powder (average particle size: 30 μm) with 1% by weight of calcium chloride.
The mixture was kneaded at a ratio of 0:40 (weight ratio) and pelletized.
【００４４】まず上記ペレット化した鉄系酸素吸収剤を
含む樹脂組成物を押出機を用いてフィルム化したフィル
ム（厚さ６０μｍ）の両面にポリプロピレンフィルム
（厚さ３０μｍ）をラミネートした。このフィルムに、
アルミ箔（厚さ１０μｍ）、さらにポリエステルフィル
ム（ポリエチレンテレフタレート（ＰＥＴ）；厚さ１０
μｍ）をドライラミネートし、酸素吸収性フィルムを製
造した。酸素吸収性フィルムの層構成（合計厚み１４０
μｍ）；ＰＰ（３０）／酸素吸収樹脂層（６０）／ＰＰ
（３０）／アルミ箔（１０）／ＰＥＴ（１０）First, a polypropylene film (thickness: 30 μm) was laminated on both surfaces of a film (thickness: 60 μm) obtained by using an extruder to form a film of the resin composition containing the pelletized iron-based oxygen absorber. In this film,
Aluminum foil (thickness 10 μm), and polyester film (polyethylene terephthalate (PET); thickness 10
μm) was dry-laminated to produce an oxygen-absorbing film. Layer structure of oxygen-absorbing film (total thickness 140
μm); PP (30) / oxygen absorbing resin layer (60) / PP
(30) / Aluminum foil (10) / PET (10)
【００４５】上記の酸素吸収性フィルムの酸素吸収樹脂
層側を内側として、このフィルムにポリ塩化ビニリデン
コートナイロン（ＫＯＮ；厚さ１５μｍ）／ポリエチレ
ン（ＰＥ；厚さ７０μｍ）フィルムのＰＥ側を重ね合わ
せて三方をヒートシールした脱酸素性袋（サイズ；１５
０ｍｍ×２００ｍｍ）を作成した。The PE side of a polyvinylidene chloride-coated nylon (KON; thickness 15 μm) / polyethylene (PE; thickness 70 μm) film is superposed on the oxygen-absorbing film, with the oxygen-absorbing resin layer side of the above film as the inner side. Deoxygenated bag heat-sealed on all sides (size: 15
0 mm x 200 mm).
【００４６】アミノ酸輸液の保存試験：上記に製造した
脱酸素性袋に、アミノ酸輸液をプラスチックバッグに封
入したアミノ酸輸液バッグを収納し、炭酸ガスを用い袋
内部の酸素濃度が約０．５％、炭酸ガス濃度が約９７％
になるようにガス置換したのち、袋をヒートシールして
密封した。アミノ酸輸液バッグを封入した脱酸素性袋を
エアースチーム式高温高圧殺菌装置にて１２０℃で３０
分間加熱処理を行ったのち２５℃で保存した。保存期間
中アミノ酸輸液バッグを封入した脱酸素性袋内の酸素濃
度を経日的に測定すると共に、７日目に袋を開封してア
ミノ酸輸液の色調変化の有無を調べた。結果を表３に記
す。Storage test of amino acid infusion: An amino acid infusion bag in which an amino acid infusion is sealed in a plastic bag is stored in the above-prepared deoxidizing bag, and the oxygen concentration in the bag is about 0.5% using carbon dioxide gas. Carbon dioxide concentration is about 97%
After gas replacement, the bag was heat-sealed and sealed. The deoxygenated bag enclosing the amino acid infusion bag is placed in an air steam type high-temperature and high-pressure sterilizer at 120 ° C. for 30 minutes.
After a heat treatment for 25 minutes, it was stored at 25 ° C. During the storage period, the oxygen concentration in the deoxygenated bag in which the amino acid infusion bag was sealed was measured daily, and on the seventh day, the bag was opened to check for a color change in the amino acid infusion. The results are shown in Table 3.
【００４７】比較例５ 片面をポリ塩化ビニリデンコートナイロン（ＫＯＮ；厚
さ１５μｍ）／ポリエチレン（ＰＥ；厚さ７０μｍ）フ
ィルム、他面をアルミニウム箔積層フィルムとして三方
をヒートシールしたガスバリヤ性袋（サイズ；１５０ｍ
ｍ×２００ｍｍ）に、前記実施例３と同じアミノ酸輸液
バッグと脱酸素剤包装体１個とを入れ、炭酸ガスを用い
袋内部の酸素濃度が約０．５％、炭酸ガス濃度が約９７
％になるようにガス置換したのち、袋をヒートシールし
て密封した。なお、この場合の脱酸素剤包装体は、和紙
／有孔ポリエチレンフィルムの袋の外側にさらにＰＥＴ
フィルム／アルミ箔／ＰＥフィルムの積層材を接着して
被覆しその片面のみに穿孔した袋（サイズ；５０ｍｍ×
５０ｍｍ、包材の透湿度５００ｇ／m2・24HR・atm）
に、比較例２で調製した鉄粉系脱酸素剤２ｇを充填した
ものであった。アミノ酸輸液バッグと脱酸素剤包装体と
を封入したガスバリヤ性袋を、エアースチーム式高温高
圧殺菌装置にて１２０℃で３０分間加熱処理を行った後
２５℃で保存して、実施例３と同様に保存効果を調べ
た。結果を表３に併記する。COMPARATIVE EXAMPLE 5 A gas barrier bag (size; heat sealed on three sides) with one surface made of polyvinylidene chloride-coated nylon (KON; thickness 15 μm) / polyethylene (PE; thickness 70 μm) film and the other surface made of aluminum foil laminated film 150m
mx 200 mm), the same amino acid infusion bag as in Example 3 and one oxygen scavenger package were placed, and the oxygen concentration in the bag was about 0.5% using carbon dioxide gas, and the carbon dioxide concentration was about 97%.
%, And the bag was heat-sealed and sealed. In this case, the oxygen absorber package is further provided with PET on the outside of the bag of Japanese paper / perforated polyethylene film.
A bag (size: 50 mm ×) in which a laminated material of film / aluminum foil / PE film is adhered and covered, and only one side thereof is perforated.
50mm, moisture permeability of 500g / m 2 · 24HR · atm of the packaging material)
Was filled with 2 g of the iron powder-based oxygen absorber prepared in Comparative Example 2. The gas barrier bag enclosing the amino acid infusion bag and the oxygen scavenger package was subjected to a heat treatment at 120 ° C. for 30 minutes in an air steam type high-temperature and high-pressure sterilizer, and then stored at 25 ° C., as in Example 3. The effect of preservation was examined. The results are also shown in Table 3.
【００４８】[0048]
【表３】 [Table 3]
【００４９】表３の結果より明らかなように、本発明の
多層フィルムからなる脱酸素性袋を用いた実施例３の場
合、大量の炭酸ガスの存在にもかかわらず、保存系内の
脱酸素は十分で、アミノ酸輸液の色調には変化なく、ア
ミノ酸輸液バッグが良好に保持されていた。これに対し
て比較例５の場合には、炭酸ガスの影響を受けて容器内
の酸素が十分に吸収されず、アミノ酸輸液は褐色に変化
していた。As is evident from the results in Table 3, in the case of Example 3 using the oxygen-absorbing bag made of the multilayer film of the present invention, the oxygen content in the storage system was maintained despite the presence of a large amount of carbon dioxide. Was sufficient, the color tone of the amino acid infusion did not change, and the amino acid infusion bag was well held. On the other hand, in the case of Comparative Example 5, the oxygen in the container was not sufficiently absorbed due to the influence of the carbon dioxide gas, and the amino acid transfusion turned brown.
【００５０】実施例４ 実施例３に製造した脱酸素性袋に油揚げ、豆等を含む五
目ひじき１５０ｇを入れ、袋をヒートシールして密封し
た。五目ひじきを密封した脱酸素性袋をエアースチーム
式高温高圧殺菌装置にて１２０℃で３０分間加熱処理を
行ったのち２５℃で保存した。保存期間中五目ひじきを
封入した脱酸素性袋内の酸素濃度を経日的に測定すると
共に、７日目に袋を開封して五目ひじきの風味変化の有
無を調べた。結果を表４に記す。Example 4 Into the oxygen-absorbing bag prepared in Example 3, 150 g of gome hijiki containing beans and the like was put, and the bag was heat-sealed and sealed. The deoxygenated bag sealed with Gomehiji was heat-treated at 120 ° C for 30 minutes in an air steam type high-temperature and high-pressure sterilizer, and then stored at 25 ° C. During the preservation period, the oxygen concentration in the deoxygenated bag containing the gojihijiki was measured daily, and on the seventh day, the bag was opened to check for a change in flavor of the gojihijiki. The results are shown in Table 4.
【００５１】比較例６ 油揚げ、豆等を含む五目ひじきと実施例３で調製した脱
酸素剤（包装体）とをアルミニウム箔積層フィルムから
なるガスバリヤ性袋（サイズ；１５０ｍｍ×２００ｍ
ｍ）に入れ、袋をヒートシールして密封した。五目ひじ
きと脱酸素剤と封入したガスバリヤ性袋をエアースチー
ム式高温高圧殺菌装置にて１２０℃で３０分間加熱処理
を行ったのち２５℃で保存し、実施例４と同様にして保
存効果を調べた。結果を表４に記す。COMPARATIVE EXAMPLE 6 A gas barrier bag (size: 150 mm × 200 m) made of an aluminum foil laminated film was prepared by combining a fried seaweed containing fried fish, beans and the like and the oxygen absorber (package) prepared in Example 3.
m) and the bag was heat sealed. The gas barrier bag filled with Gomeji Hijiki and the oxygen scavenger was heat-treated at 120 ° C for 30 minutes in an air steam type high-temperature and high-pressure sterilizer, then stored at 25 ° C, and the storage effect was examined in the same manner as in Example 4. Was. The results are shown in Table 4.
【００５２】[0052]
【表４】 [Table 4]
【００５３】表４の結果に明らかなように、油揚げ、豆
等を含む五目ひじきの保存中に炭酸ガスの発生が認めら
れたが、実施例４の場合、炭酸ガスの発生があっても袋
内の酸素は良好に吸収され、保存系内は実質的に無酸素
状態に保たれ、五目ひじきの風味は変化することなく良
好に保持されていた。これに対して比較例６の場合に
は、炭酸ガスの影響を受けて容器内の酸素は十分に吸収
されず、五目ひじきには異臭があり、品質劣化が起こっ
ていた。As is evident from the results in Table 4, carbon dioxide gas was generated during storage of the deep-fried gojihiji including oil fried, beans and the like. In the case of Example 4, even if carbon dioxide gas was generated, bags were produced. The oxygen inside was well absorbed, the storage system was kept substantially oxygen-free, and the flavor of the gojihijiki was well maintained without change. On the other hand, in the case of Comparative Example 6, the oxygen in the container was not sufficiently absorbed due to the influence of the carbon dioxide gas, and there was an unpleasant odor in the fifth eye-hijiki, resulting in quality deterioration.
【００５４】[0054]
【発明の効果】以上の実施例から明らかなように、従来
型の鉄粉系脱酸素剤が炭酸ガスの影響を受けて脱酸素性
能が低下するのに対して、脱酸素剤を熱可塑性樹脂に混
練、分散させた酸素吸収樹脂層を配したシートやフィル
ムからなり、脱酸素性能を備えた本発明の容器や袋は、
炭酸ガスが存在しても容易に酸素を吸収することができ
る。このように、本発明の包装容器は、炭酸ガスを含む
雰囲気内においても脱酸素能を発揮することができる特
徴をもつ。As is apparent from the above examples, the conventional iron powder-based oxygen scavenger is affected by the carbon dioxide gas to reduce the oxygen scavenging performance, whereas the oxygen scavenger is replaced by the thermoplastic resin. The container or bag of the present invention comprising a sheet or film having an oxygen-absorbing resin layer kneaded and dispersed therein, and having deoxygenation performance,
Even if carbon dioxide gas is present, oxygen can be easily absorbed. As described above, the packaging container of the present invention has a feature that it can exhibit a deoxidizing ability even in an atmosphere containing carbon dioxide gas.
【００５５】本発明によれば、例えば、穀物類、医薬品
等の物品で、酸素により品質劣化を起こし易い物品で炭
酸ガス置換を行なって保存する物品、また保存中にその
もの自体より炭酸ガスを発生する物品、また加熱等の処
理によって炭酸ガスが発生するような物品等を保存する
場合、保存雰囲気中の酸素を容易に吸収して好適に保存
することができる。According to the present invention, for example, articles such as cereals, pharmaceuticals, etc., whose quality is liable to be degraded by oxygen, are stored by performing carbon dioxide replacement, and carbon dioxide is generated during storage by itself. When preserving an article to be processed or an article or the like in which carbon dioxide gas is generated by a treatment such as heating, oxygen in the preservation atmosphere can be easily absorbed and stored appropriately.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ａ２３Ｂ 4/00 Ｅ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code Agency reference number FI Technical indication A23B 4/00 E
Claims (8)
散してなる酸素吸収樹脂層を少なくとも容器の一部に備
え、酸素を吸収するようにしてなる包装容器内に、物品
を収納して容器を密封することにより、炭酸ガスの存在
下に酸素を吸収して実質的に無酸素状態に物品を保持す
ることを特徴とする物品の保存方法。An oxygen-absorbing resin layer obtained by kneading and dispersing an iron-based oxygen absorber into a thermoplastic resin is provided at least in a part of a container, and the article is stored in a packaging container configured to absorb oxygen. A method for preserving an article, comprising: absorbing oxygen in the presence of carbon dioxide gas and keeping the article substantially oxygen-free by sealing the container.
吸収樹脂層を含む積層体からなる容器または袋である請
求項１に記載の方法。2. The method according to claim 1, wherein the packaging container is a container or a bag formed of a laminate including the oxygen absorbing resin layer in whole or in part.
内を炭酸ガス置換したのち、容器を密封する請求項１に
記載の方法。3. The method according to claim 1, wherein the article is stored in a packaging container, and after the inside of the container is replaced with carbon dioxide, the container is sealed.
請求項１に記載の方法。4. The method according to claim 1, wherein the article is an article that generates carbon dioxide gas.
ち加熱するか、または加熱した物品を包装容器内に収納
して密封する請求項１に記載の方法。5. The method according to claim 1, wherein the article is housed in a packaging container and sealed, followed by heating, or the heated article is housed in a packaging container and sealed.
層、酸素吸収樹脂層からなる中間層、及び酸素バリア性
層からなる外層を有する多層フィルムまたはシートから
形成されたものである請求項１に記載の方法。6. The container according to claim 1, wherein the container is formed of a multilayer film or sheet having an inner layer made of an oxygen-permeable protective layer, an intermediate layer made of an oxygen-absorbing resin layer, and an outer layer made of an oxygen-barrier layer. The method described in.
以上である請求項１に記載の方法。7. The concentration of carbon dioxide in the container after sealing is 1%.
The method of claim 1, wherein:
に記載の方法。8. The method according to claim 1, wherein the storage temperature is 15 ° C. or less.
The method described in.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10163697A JP3808584B2 (en) | 1996-05-28 | 1997-04-18 | How to store goods |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13353796 | 1996-05-28 | ||
| JP8-133537 | 1996-05-28 | ||
| JP10163697A JP3808584B2 (en) | 1996-05-28 | 1997-04-18 | How to store goods |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1045177A true JPH1045177A (en) | 1998-02-17 |
| JP3808584B2 JP3808584B2 (en) | 2006-08-16 |
Family
ID=26442495
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10163697A Expired - Lifetime JP3808584B2 (en) | 1996-05-28 | 1997-04-18 | How to store goods |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3808584B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10338264A (en) * | 1997-06-06 | 1998-12-22 | Ajinomoto Co Inc | Oxygen-absorbing laminate-packaging material |
| JP2001169718A (en) * | 1999-12-17 | 2001-06-26 | Nichimo Co Ltd | Method for packaging fish egg and packaged body |
| JP2003088344A (en) * | 2001-09-17 | 2003-03-25 | Mitsubishi Gas Chem Co Inc | Oxygen and carbon dioxide-adsorbing multilayer body |
| JPWO2004039936A1 (en) * | 2002-10-30 | 2006-03-02 | サントリー株式会社 | Process for producing processed plant products |
| JP2007110937A (en) * | 2005-10-19 | 2007-05-10 | Meiji Milk Prod Co Ltd | Retort fluid food with high concentration and method for producing the same |
| JP2008061591A (en) * | 2006-09-08 | 2008-03-21 | Toyo Seikan Kaisha Ltd | Method for packaging intermediate moisture food |
| WO2008117594A1 (en) * | 2007-03-23 | 2008-10-02 | Kureha Corporation | Tightly packaged food and method of packaging food |
| JP2016524897A (en) * | 2013-08-07 | 2016-08-22 | ネクスト エスアールエルＮｅｃｓｔ Ｓ．Ｒ．Ｌ． | How to store food |
-
1997
- 1997-04-18 JP JP10163697A patent/JP3808584B2/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10338264A (en) * | 1997-06-06 | 1998-12-22 | Ajinomoto Co Inc | Oxygen-absorbing laminate-packaging material |
| JP2001169718A (en) * | 1999-12-17 | 2001-06-26 | Nichimo Co Ltd | Method for packaging fish egg and packaged body |
| JP2003088344A (en) * | 2001-09-17 | 2003-03-25 | Mitsubishi Gas Chem Co Inc | Oxygen and carbon dioxide-adsorbing multilayer body |
| JPWO2004039936A1 (en) * | 2002-10-30 | 2006-03-02 | サントリー株式会社 | Process for producing processed plant products |
| JP2007110937A (en) * | 2005-10-19 | 2007-05-10 | Meiji Milk Prod Co Ltd | Retort fluid food with high concentration and method for producing the same |
| JP2008061591A (en) * | 2006-09-08 | 2008-03-21 | Toyo Seikan Kaisha Ltd | Method for packaging intermediate moisture food |
| WO2008117594A1 (en) * | 2007-03-23 | 2008-10-02 | Kureha Corporation | Tightly packaged food and method of packaging food |
| AU2008230594B2 (en) * | 2007-03-23 | 2011-08-04 | Kureha Corporation | Tightly packaged food and method of packaging food |
| JP2016524897A (en) * | 2013-08-07 | 2016-08-22 | ネクスト エスアールエルＮｅｃｓｔ Ｓ．Ｒ．Ｌ． | How to store food |
| US10426182B2 (en) | 2013-08-07 | 2019-10-01 | Necst S.R.L. | Method for preserving food |
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|---|---|
| JP3808584B2 (en) | 2006-08-16 |
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