JP2000050850A - Deoxidizer composition and preservation using the same - Google Patents
Deoxidizer composition and preservation using the sameInfo
- Publication number
- JP2000050850A JP2000050850A JP14973099A JP14973099A JP2000050850A JP 2000050850 A JP2000050850 A JP 2000050850A JP 14973099 A JP14973099 A JP 14973099A JP 14973099 A JP14973099 A JP 14973099A JP 2000050850 A JP2000050850 A JP 2000050850A
- Authority
- JP
- Japan
- Prior art keywords
- oxygen
- absorbing
- weight
- iodine
- metal iodide
- 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
- Food Preservation Except Freezing, Refrigeration, And Drying (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、低湿度雰囲気下で
脱酸素能を有する脱酸素剤組成物、及びこの脱酸素剤組
成物と熱可塑性樹脂とを含む脱酸素樹脂組成物に関す
る。詳しくは、鉄粉及びヨウ素からなる脱酸素剤組成
物、あるいは、鉄粉、ヨウ素及び金属ヨウ化物からなる
脱酸素剤組成物、及びこの脱酸素剤組成物と熱可塑性樹
脂とを含む脱酸素樹脂組成物に関する。また、本発明
は、前記脱酸素剤組成物あるいは脱酸素樹脂組成物を用
いた物品の保存方法、殊に乾燥状態にあって吸湿の嫌わ
れる医薬品や食品等の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 an oxygen scavenger composition having oxygen scavenging ability under a low humidity atmosphere, and an oxygen scavenger resin composition containing the oxygen scavenger composition and a thermoplastic resin. Specifically, an oxygen scavenger composition comprising iron powder and iodine, or an oxygen scavenger composition comprising iron powder, iodine and metal iodide, and an oxygen scavenging resin comprising the oxygen scavenger composition and a thermoplastic resin Composition. The present invention also relates to a method for preserving articles using the above-described oxygen-absorbing composition or oxygen-absorbing resin composition, and particularly to a method for preserving articles such as medicines and foods that are in a dry state and do not absorb moisture.
【０００２】[0002]
【従来の技術】還元性金属の酸化反応を利用した脱酸素
剤は、従来から広く知られている。この脱酸素剤は、還
元性金属の他、還元性金属の酸化反応を促進する触媒と
して、ハロゲン化金属を備えている。この種の脱酸素剤
は、主として食品の鮮度等を保持するために、食品等の
被保存物とともに容器内に投入するか、あるいは、容器
内に貼り付けるなどして、食品等を保存することが行わ
れている。このような脱酸素剤としては、例えば、特公
昭５６−３３９８０号公報に記載されたものがある。こ
の脱酸素剤は、鉄粉等の金属粉とハロゲン化金属からな
り、具体的には、金属粉をハロゲン化金属で被覆した構
造を備えている。このタイプの脱酸素剤は、酸素を吸収
する際に、雰囲気中から水分を補給する必要があるた
め、「水分依存型脱酸素剤」と呼ばれている。この脱酸
素剤は、非保存物からの蒸散水分を利用できる高（多）
含水分食品に利用されている。2. Description of the Related Art An oxygen scavenger utilizing an oxidation reaction of a reducing metal has been widely known. The oxygen scavenger includes a reducing metal and a metal halide as a catalyst for accelerating the oxidation reaction of the reducing metal. This type of oxygen absorber is mainly used for preserving food, etc., in order to maintain the freshness of the food, etc., by putting it in a container together with the preservation object such as food, or attaching it to the container. Has been done. Examples of such oxygen absorbers include those described in Japanese Patent Publication No. 56-33980. This oxygen absorber comprises a metal powder such as iron powder and a metal halide, and has a structure in which the metal powder is coated with a metal halide. This type of oxygen absorber is called a “moisture-dependent oxygen absorber” because it is necessary to supply water from the atmosphere when absorbing oxygen. This oxygen scavenger has a high (many) capacity to use the water evaporated from non-preserved materials.
Used for moisture-containing foods.
【０００３】一方、水分の含有量が少ない（言い換える
と水分活性が低い）乾燥食品等の保存には、脱酸素剤中
に、水分供与体を存在させて、酸素吸収反応に必要な水
分を補うようにしていた。この種の脱酸素剤は、被包装
物からの水分に頼らず酸素吸収を行えるので、「自力反
応型脱酸素剤」として知られている。このような脱酸素
剤としては、特公昭５７−３１４４９号公報に記載され
たものがある。また、特開平２−７２８５１号公報、特
開平７−１３７７６１号公報、特開平７−２１９４３０
号公報などには、脱酸素樹脂シートを通気性包材で包装
した脱酸素樹脂包装体が、ラベル型、カード型、パッキ
ン型等の脱酸素剤として食品等の物品の脱酸素保存に利
用されることが記載されている。[0003] On the other hand, for preservation of dried food or the like having a low water content (in other words, low water activity), a water donor is present in an oxygen scavenger to supplement the water required for the oxygen absorption reaction. Was like that. This type of oxygen absorber is known as a "self-reactive oxygen absorber" because it can absorb oxygen without relying on moisture from the package. As such a deoxidizer, there is one described in JP-B-57-31449. Also, JP-A-2-72851, JP-A-7-137761, JP-A-7-219430
In the publication, oxygen-absorbing resin packages in which oxygen-absorbing resin sheets are wrapped with a breathable packaging material are used as oxygen absorbers for labels, cards, packing, etc. for oxygen storage of foods and other articles. Is described.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、水分を
保有する自力反応型脱酸素剤は、樹脂に練り込もうとし
た場合、混練してシート化する際の加熱により、保水成
分中の水分が蒸発する虞がある。そして、この蒸発した
水分によって樹脂シート内に気泡が発生し、シートの押
し出し時にムラなどが発生する原因となり、シート化が
困難である。また、自力反応型脱酸素剤は、雰囲気中の
相対湿度に関係なく脱酸素を行うことができるが、脱酸
素中に脱酸素剤に含有されている水分が蒸散して、被保
存物に移行することが避けられない。したがって、乾燥
状態にあって吸湿の嫌われる医薬品や食品などの被保存
物には使用できないという問題がある。However, when the self-reactive oxygen scavenger having water content is to be kneaded into the resin, the water in the water retention component evaporates due to heating during kneading to form a sheet. There is a risk of doing so. The vaporized water generates bubbles in the resin sheet, which causes unevenness when the sheet is extruded, and it is difficult to form the sheet. In addition, the self-reactive oxygen absorber can perform oxygen removal regardless of the relative humidity in the atmosphere, but during the oxygen removal, the water contained in the oxygen absorber evaporates and migrates to the storage object. It is inevitable to do. Therefore, there is a problem that it cannot be used for preservation items such as medicines and foods that are in a dry state and do not like to absorb moisture.
【０００５】また、水分を保有しない水分依存応型脱酸
素剤は、樹脂に混練してシート材を得た後に、水分をこ
の脱酸素剤に保有させることも考えられるが、この様な
処理は脱酸素組成物製造工程とは別工程となり、工業的
な生産には不利である。また、この様な処理を行った脱
酸素剤は、乾燥物品に使用した場合、脱酸素剤に保持さ
れている水分が蒸散して被保存物に移行することはさけ
られない。また、被保存物によっては、この水分移行に
より、食味低下（湿気）、性状変化（粉体の塊状化）、
化学変化（加水分解）等の問題を起こすことが考えられ
る。さらにまた、長期間の保存中には、脱酸素剤から水
分が蒸散してしまって脱酸素性能が低下し、容器外から
進入する酸素を吸収することができず、結果的に系内の
酸素濃度が上昇して、品質劣化を来すという問題があ
る。また、脱酸素樹脂組成物を中間層とし、外層にバリ
ア層、内層にシール層を配した脱酸素性多層体に至って
は、中間層である脱酸素剤層に水分を保持させることは
非常に困難である。したがって、従来の脱酸素樹脂組成
物は、実質上、多くの水分を含んだ食品にしか適用でき
ず、含有水分の低い被保存物に適用することが困難であ
った。It is conceivable to use a water-dependent oxygen absorbing agent that does not retain moisture, after kneading the resin to obtain a sheet material, and then retaining the moisture in the oxygen absorbing agent. This is a separate step from the oxygen composition production step, which is disadvantageous for industrial production. Further, when the oxygen scavenger subjected to such treatment is used for a dry article, it is inevitable that the moisture retained in the oxygen scavenger evaporates and migrates to the object to be preserved. In addition, depending on the object to be preserved, this moisture migration causes a decrease in taste (moisture), a change in properties (agglomeration of powder),
Problems such as chemical change (hydrolysis) may occur. Furthermore, during long-term storage, water evaporates from the oxygen scavenger and the oxygen scavenging performance decreases, and oxygen entering from outside the container cannot be absorbed, resulting in oxygen in the system. There is a problem that the concentration is increased and the quality is deteriorated. Further, in the case of an oxygen-absorbing multilayer body in which the oxygen-absorbing resin composition is used as an intermediate layer, and a barrier layer is provided as an outer layer and a seal layer is provided as an inner layer, it is extremely difficult to retain moisture in the oxygen-absorbing agent layer as the intermediate layer. Have difficulty. Therefore, the conventional oxygen-absorbing resin composition can be practically applied only to foods containing a large amount of moisture, and it has been difficult to apply the composition to preservation materials having a low moisture content.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、鉄粉／ヨ
ウ素系あるいは、鉄粉／ヨウ素／金属ヨウ化物系の新規
な脱酸素剤が、水分供与体を存在させなくとも低湿度雰
囲気下でも迅速に脱酸素することを見いだした。この新
規な脱酸素剤は、被保存物が吸湿する虞がないため、乾
燥状態にある被保存物の脱酸素保存に最適である。この
ヨウ素、あるいはヨウ素／金属ヨウ化物は、鉄による酸
素吸収反応の促進剤として機能する。また、特に、ヨウ
素及びヨウ化金属塩を被覆した鉄粉は、樹脂に良好に練
り込み、シート化、延伸することが可能であり、この脱
酸素樹脂組成物も、低湿度雰囲気下で脱酸素能力を発揮
することを見いだした。Means for Solving the Problems The present inventors have developed a novel oxygen scavenger based on iron powder / iodine or iron powder / iodine / metal iodide in a low-humidity atmosphere without the presence of a moisture donor. We found that it quickly deoxygenated below. This novel oxygen absorber is optimal for deoxidizing and preserving a dried object, since the object to be preserved does not absorb moisture. This iodine or iodine / metal iodide functions as an accelerator for the oxygen absorption reaction by iron. In particular, iron powder coated with iodine and a metal iodide salt can be kneaded well with a resin, formed into a sheet, and stretched. This deoxidized resin composition can also be deoxygenated in a low-humidity atmosphere. We found that we showed ability.
【０００７】本発明によれば、水分供与体を必要としな
い脱酸素剤として一層広い範囲の水分活性の被保存物の
保存が可能であり、特に、吸湿が嫌われ保存に低湿度の
乾燥雰囲気を必要とする水分活性が０．１〜０．７の被
保存物、例えば乾燥状態にある健康食品あるいは粉末や
顆粒等の医薬品を長期間脱酸素状態で保存し、吸湿する
ことなく酸素に起因する劣化を防止して、品質を良好に
保持することができる。すなわち、本発明は、低湿度雰
囲気下においても十分な脱酸素性能を発揮する新規な脱
酸素剤組成物及びこれを用いた脱酸素剤樹脂組成物を提
供するものである。また、前記脱酸素剤組成物及びこれ
を用いた脱酸素剤樹脂組成物を用いた被保存物の保存方
法を提供するものである。According to the present invention, it is possible to store an object to be preserved having a wider range of water activity as an oxygen scavenger which does not require a water donor. Preserved substances having a water activity of 0.1 to 0.7 requiring, for example, health foods in the dry state or pharmaceuticals such as powders and granules are stored in a deoxygenated state for a long period of time and caused by oxygen without absorbing moisture It is possible to prevent deterioration and to maintain good quality. That is, the present invention provides a novel oxygen-absorbing composition exhibiting sufficient oxygen-absorbing performance even in a low-humidity atmosphere, and an oxygen-absorbing resin composition using the same. Another object of the present invention is to provide a method for preserving an object to be preserved using the oxygen scavenger composition and the oxygen scavenger resin composition using the same.
【０００８】具体的には、本発明は、鉄粉とヨウ素を備
えた脱酸素剤組成物を提供するものである。また、鉄
粉、ヨウ素及び金属ヨウ化物を備えた脱酸素剤組成物を
提供するものである。前記金属ヨウ化物は、アルカリ金
属のヨウ化物またはアルカリ土類金属のヨウ化物とする
ことができる。また、前記金属ヨウ化物は、ヨウ化ナト
リウム、ヨウ化カリウムまたはヨウ化カルシュウムとす
ることが好ましい。そしてまた、前記ヨウ素と金属ヨウ
化物の重量の和は、鉄粉１００重量部当たり０．０１〜
２０重量部であり、かつヨウ素に対する金属ヨウ化物の
重量比は、０．１〜５の範囲にすることができる。ま
た、前記脱酸素剤組成物中の水分含有量は、１重量％以
下にすることができる。[0008] Specifically, the present invention provides an oxygen scavenger composition comprising iron powder and iodine. Another object of the present invention is to provide an oxygen scavenger composition comprising iron powder, iodine and metal iodide. The metal iodide can be an alkali metal iodide or an alkaline earth metal iodide. Preferably, the metal iodide is sodium iodide, potassium iodide, or calcium iodide. Further, the sum of the weights of the iodine and the metal iodide is 0.01 to 100 parts by weight of iron powder.
20 parts by weight, and the weight ratio of metal iodide to iodine can be in the range of 0.1-5. Further, the water content in the oxygen scavenger composition can be 1% by weight or less.
【０００９】前記鉄粉の表面には、前記ヨウ素と金属ヨ
ウ化物の混合物を被覆することができる。また、本発明
の脱酸素樹脂組成物は、熱可塑性樹脂の中に低湿度雰囲
気下で酸素吸収可能なヨウ素及びヨウ化金属塩と鉄粉よ
りなる脱酸素剤組成物を均一に分散させ得られた脱酸素
樹脂組成物であり、単層もしくは多層にてフィルムまた
はシートとして加工する、またはこのシートを延伸する
ことにより脱酸素性能の改良された多孔性の脱酸素性シ
ートが得られる。また本発明の他の目的は、前記脱酸素
樹脂組成物を通気性包材を用いて包装して小袋型脱酸素
剤とし、または通気性もしくは非通気性のカバーシート
及び貼着用の粘着剤が積層されてなるラベル型脱酸素剤
とし、バリアーフィルムよりなる袋に低水分含有被保存
物と共に保存し、低酸素濃度雰囲気下に保持することが
できる低水分含有被保存物の保存方法を提供することに
ある。[0009] The surface of the iron powder may be coated with a mixture of the iodine and the metal iodide. Further, the oxygen-absorbing resin composition of the present invention can be obtained by uniformly dispersing an oxygen-absorbing composition composed of iron powder and iodine and metal iodide capable of absorbing oxygen under a low humidity atmosphere in a thermoplastic resin. The resulting oxygen-absorbing resin composition is processed into a single-layer or multilayer film or sheet, or is stretched to obtain a porous oxygen-absorbing sheet having improved oxygen-absorbing performance. Another object of the present invention is to provide a small bag-type oxygen absorber by packaging the oxygen-absorbing resin composition using a gas-permeable packaging material, or a gas-permeable or non-gas-permeable cover sheet and a pressure-sensitive adhesive. Provided is a method for preserving a low moisture-containing preservation material that can be stored as a label type oxygen absorbing agent that is laminated and stored in a bag made of a barrier film together with a low moisture content preservation material, and can be maintained under a low oxygen concentration atmosphere. It is in.
【００１０】さらに低湿度の保存条件を必要とする低水
分含有被保存物を低酸素濃度雰囲気下に保存する包装体
を提供することもしくは、少なくとも一部が脱酸素性多
層体からなる容器に密閉して低酸素濃度雰囲気下に保存
する包装体を提供することにある。具体的には、鉄粉及
びヨウ素を備えた脱酸素剤組成物と、熱可塑性樹脂から
なる脱酸素性樹脂組成物を提供するものである。[0010] Further, the present invention provides a package for storing a low-moisture content preservation object requiring a low-humidity storage condition in a low-oxygen-concentration atmosphere, or hermetically sealed in a container at least partially composed of a deoxidizing multilayer body. To provide a package that is stored under a low oxygen concentration atmosphere. Specifically, the present invention provides an oxygen-absorbing composition comprising iron powder and iodine, and an oxygen-absorbing resin composition comprising a thermoplastic resin.
【００１１】また、前記脱酸素剤組成物は、金属ヨウ化
物をさらに加えることができる。この脱酸素剤組成物
は、鉄粉１００重量部、金属ヨウ化物０．０１〜２０重
量部、及びヨウ素０．０１〜２０重量部から構成するこ
とができる。また、前記脱酸素剤組成物は、前記ヨウ素
及び金属ヨウ化物により被覆された鉄粉から構成するこ
ともできる。前記金属ヨウ化物は、アルカリ金属のヨウ
化物またはアルカリ土類金属のヨウ化物とすることがで
きる。そしてまた、前記脱酸素剤組成物重量当りの、金
属ヨウ化物のヨウ素イオン（Ｉ-）の重量は、ヨウ素
（Ｉ2）の重量の１／２より大きくすることができる。
また、前記脱酸素剤組成物の水分含有量は、１重量％以
下にすることができる。The oxygen scavenger composition may further include a metal iodide. The oxygen scavenger composition can be composed of 100 parts by weight of iron powder, 0.01 to 20 parts by weight of metal iodide, and 0.01 to 20 parts by weight of iodine. Further, the oxygen scavenger composition may be composed of iron powder coated with the iodine and the metal iodide. The metal iodide can be an alkali metal iodide or an alkaline earth metal iodide. Further, the weight of the iodine ion (I − ) of the metal iodide per weight of the oxygen scavenger composition can be larger than 重量 of the weight of the iodine (I 2 ).
The water content of the oxygen scavenger composition can be 1% by weight or less.
【００１２】さらにまた、本発明は、前述した脱酸素剤
組成物を、通気性包装材料からなる小袋に充填してなる
脱酸素剤包装体を提供するものである。そしてまた、本
発明は、前述した脱酸素性樹脂組成物からなる厚さ２０
μｍ〜５ｍｍの脱酸素性シートを提供するものである。
また、本発明は、前記脱酸素性シートを、少なくとも１
軸方向に、１．５〜１２倍の範囲で延伸し、多孔性脱酸
素性シートを提供することもできる。さらにまた、本発
明は、前記脱酸素性シートを通気性包装材料により包装
してなる小袋型脱酸素剤を提供するものである。また、
本発明は、通気性又は非通気性のカバーシート、前述し
た脱酸素性シート、及び貼着用の粘着剤が積層されてな
るラベル型脱酸素剤を提供するものである。また、本発
明は、酸素透過性熱可塑性樹脂からなる酸素透過層、前
述した脱酸素性シートからなる脱酸素層、及びガスバリ
アー性材料からなるガスバリアー層が積層されてなる脱
酸素性多層体を提供するものである。Further, the present invention provides an oxygen-absorbing agent package obtained by filling the above-described oxygen-absorbing agent composition into a small bag made of a breathable packaging material. In addition, the present invention relates to the above-described oxygen-absorbing resin composition having a thickness of 20%.
The purpose of the present invention is to provide an oxygen-absorbing sheet of μm to 5 mm.
Further, the present invention provides the oxygen-absorbing sheet,
It can be stretched in the axial direction in a range of 1.5 to 12 times to provide a porous oxygen-absorbing sheet. Furthermore, the present invention provides a small bag-type oxygen absorber obtained by packaging the oxygen-absorbing sheet with a breathable packaging material. Also,
The present invention provides a label-type oxygen absorber formed by laminating a gas-permeable or air-impermeable cover sheet, the above-described oxygen-absorbing sheet, and an adhesive for application. Further, the present invention provides an oxygen-permeable multilayer body formed by laminating an oxygen-permeable layer made of an oxygen-permeable thermoplastic resin, an oxygen-absorbing layer made of the above-described oxygen-absorbing sheet, and a gas barrier layer made of a gas-barrier material. Is provided.
【００１３】そしてまた、本発明は、水分活性が０．１
〜０．７である被保存物を、前述した脱酸素剤包装体と
共にガスバリヤー性容器に収納し密閉する低水分含有物
品の保存方法を提供するものである。また、本発明は、
水分活性が０．１〜０．７の被保存物を、前述した脱酸
組成シートと共に、ガスバリヤー性容器に密閉する低水
分物品の保存方法を提供するものである。そしてまた、
本発明は、水分活性が０．１〜０．７の被保存物を、少
なくとも一部が前述した脱酸素性多層体からなる容器に
密閉する低水分物品の保存方法を提供するものである。
前記被保存物の水分活性は、０．２〜０．５であること
がより好ましい。Further, the present invention provides a water activity of 0.1
An object of the present invention is to provide a method for storing low moisture content articles, in which a preservation object having a size of 0.7 is stored in a gas barrier container together with the above-described oxygen absorber package and sealed. Also, the present invention
An object of the present invention is to provide a method for preserving a low moisture article in which a preservation object having a water activity of 0.1 to 0.7 is hermetically sealed in a gas barrier container together with the deoxidizing composition sheet described above. and again,
The present invention provides a method for preserving a low-moisture article in which an object to be preserved having a water activity of 0.1 to 0.7 is sealed at least partially in a container made of the above-described deoxidizing multilayer body.
The water activity of the object to be preserved is more preferably 0.2 to 0.5.
【００１４】また、本発明は、被保存物を、前述した脱
酸組成シートと共に、ガスバリヤー性容器に密閉してな
る包装品を提供するものである。そしてまた、本発明
は、被保存物を、少なくとも一部が前述した脱酸素性多
層体からなる容器に密閉してなる包装品を提供するもの
である。本発明に係る脱酸素剤組成物は、鉄粉／ヨウ素
の２成分系あるいは鉄粉／ヨウ素／金属ヨウ化物の３成
分系からなる。この脱酸素剤組成物は、公知の鉄粉／金
属ハロゲン化物の２成分系と比較して、低湿度の乾燥雰
囲気下において極めて優れた脱酸素性能を発揮する。The present invention also provides a package in which a preservation object is hermetically sealed in a gas barrier container together with the above-mentioned deoxidizing composition sheet. Further, the present invention provides a packaged product in which a preservation object is sealed at least partially in a container made of the above-described deoxidizing multilayer body. The oxygen scavenger composition according to the present invention comprises a two-component system of iron powder / iodine or a three-component system of iron powder / iodine / metal iodide. This oxygen scavenger composition exhibits extremely excellent oxygen scavenging performance in a low humidity dry atmosphere as compared with the known iron powder / metal halide two-component system.
【００１５】鉄粉は、脱酸素剤組成物の主剤であり、雰
囲気中の酸素と反応して脱酸素する役割を果たす。ヨウ
素あるいはヨウ素と金属ヨウ化物は、この酸化反応を促
進する触媒の役割を果たしている。なお、本発明の鉄粉
／ヨウ素の２成分系脱酸素剤組成物に、他の成分、例え
ば、金属ハロゲン化物を添加してもよい。金属ハロゲン
化物のなかでは、金属ヨウ化物が最も触媒作用の促進効
果があり、本発明の３成分系脱酸素剤組成物になってい
る。本発明で使用する鉄粉としては、脱酸素反応を起こ
しうるものであれば純度等に特に制限することなく使用
でき、表面の一部が酸化されているものでもよいし、他
の金属を含有するものでもよい。例えば、還元鉄粉、電
解鉄粉、噴霧鉄粉等が好適に用いられる。その他、鋳鉄
等の粉砕物または、研削品等が用いられる。Iron powder is a main component of the oxygen scavenger composition, and plays a role of deoxidizing by reacting with oxygen in the atmosphere. Iodine or iodine and metal iodide play a role of a catalyst for promoting this oxidation reaction. In addition, other components, for example, a metal halide may be added to the iron powder / iodine two-component oxygen scavenger composition of the present invention. Among the metal halides, metal iodides have the most catalyzing effect, and constitute the three-component oxygen scavenger composition of the present invention. The iron powder used in the present invention can be used without any particular limitation on the purity and the like as long as it can cause a deoxygenation reaction, and may have a partially oxidized surface or may contain other metals. You may do it. For example, reduced iron powder, electrolytic iron powder, spray iron powder and the like are suitably used. In addition, a crushed product such as cast iron or a ground product is used.
【００１６】鉄粉の粒度は、酸素との接触を良好にする
ためには細かい方がよく、通常最大粒径１０メッシュ
（約１．７ｍｍ）以下、特に５０メッシュ（約０．３ｍ
ｍ）以下が好ましい。あまりに小さい粒径の鉄粉は取り
扱い上、発火等の問題があり、また高価であることか
ら、平均粒径としては、１０〜５００μｍのものが好ま
しく使用される。鉄粉の比表面積は、５００cm2/g以上
が好ましい。本発明の鉄粉／ヨウ素の２成分系脱酸素剤
組成物は、例えば、鉄粉とヨウ素の粉体混合物であり、
この脱酸素剤組成物を通気性包装材料からなる小袋に充
填した脱酸素剤包装体として脱酸素保存用途に使用す
る。The particle size of the iron powder is preferably fine in order to make good contact with oxygen, and usually the maximum particle size is 10 mesh (about 1.7 mm) or less, especially 50 mesh (about 0.3 m).
m) The following is preferred. Iron powder having an extremely small particle size has problems in handling, such as ignition, and is expensive, so that an average particle size of 10 to 500 μm is preferably used. The specific surface area of the iron powder is preferably 500 cm 2 / g or more. The iron powder / iodine two-component oxygen scavenger composition of the present invention is, for example, a powder mixture of iron powder and iodine,
This oxygen-absorbing composition is used for oxygen-absorbing preservation as an oxygen-absorbing package packed in a small bag made of a breathable packaging material.
【００１７】本発明の鉄粉／ヨウ素／金属ヨウ化物の３
成分系脱酸素剤組成物は、例えば鉄粉、ヨウ素及び金属
ヨウ化物の粉体混合物であり、好ましくは、ヨウ素と金
属ヨウ化物の触媒効果を効率よく発揮させるために、鉄
粉の表面にヨウ素と金属ヨウ化物の混合物が付着してい
る被覆鉄粉である。鉄粉の表面にヨウ素と金属ヨウ化物
の混合物が被覆されている３成分系脱酸素剤組成物は、
ヨウ素の気散が防止され、優れた脱酸素性能を有してい
る。なお、２成分系、３成分系とは、脱酸素反応に直接
関与する構成要素をいい、その他の成分を添加しても差
し支えない。The iron powder / iodine / metal iodide 3 of the present invention
The component-based oxygen scavenger composition is, for example, a powder mixture of iron powder, iodine and metal iodide.Iodine is preferably added to the surface of the iron powder in order to efficiently exhibit the catalytic effect of iodine and metal iodide. And a coated iron powder to which a mixture of and metal iodide is adhered. A three-component oxygen scavenger composition in which a mixture of iodine and metal iodide is coated on the surface of iron powder,
The diffusion of iodine is prevented, and it has excellent deoxygenation performance. The two-component system and the three-component system refer to components directly involved in the deoxygenation reaction, and other components may be added.
【００１８】本発明における鉄の酸素吸収反応触媒は、
ヨウ素及びヨウ化物からなる。金属ヨウ化物としては、
電解性金属ヨウ化物が使用でき、具体的には、アルカリ
金属ヨウ化物、アルカリ土類金属ヨウ化物、あるいは、
銅、亜鉛、アルミニウム、錫、鉄、コバルト、ニッケ
ル、カドミウム等の遷移金属ヨウ化物が使用できる。金
属ヨウ化物としては、各種金属のヨウ化物が挙げられる
が、安全面や触媒性能面からはアルカリ金属またはアル
カリ土類金属のヨウ化物が好ましく、ヨウ化ナトリウ
ム、ヨウ化カリウムまたはヨウ化カルシウムが特に好ま
しい。なお、２種以上の金属ヨウ化物を混合して用いて
もよい。The catalyst for oxygen absorption reaction of iron according to the present invention comprises:
Consists of iodine and iodide. As metal iodides,
Electrolytic metal iodides can be used, specifically, alkali metal iodides, alkaline earth metal iodides, or
Transition metal iodides such as copper, zinc, aluminum, tin, iron, cobalt, nickel, cadmium and the like can be used. Examples of the metal iodide include iodides of various metals.From the viewpoint of safety and catalytic performance, an iodide of an alkali metal or an alkaline earth metal is preferable, and sodium iodide, potassium iodide or calcium iodide is particularly preferable. preferable. Note that two or more metal iodides may be used as a mixture.
【００１９】鉄粉１００重量部当たりのヨウ素の重量
は、０．０１〜２０重量部が好ましく、０．１〜１０重
量部がより好ましい。またヨウ素の粒度は、最大粒径１
０メッシュ以下が好ましく、特に５０メッシュ以下が好
ましい。本発明の脱酸素剤組成物に係る触媒は、低水分
下において、脱酸素反応を達成することを妨げない範囲
で、他のハロゲン化物の介在を妨げるものではない。好
ましい実施の形態では、触媒中のヨウ素とヨウ化物を合
わせた含有量は、９０重量％以上である。好ましくは９
５重量％以上である。本発明の反応促進剤は、鉄粉と混
合されても良いが、好ましくは、鉄粉に被覆される。鉄
粉１００重量部当たりのヨウ素と金属ヨウ化物の重量の
和は、０．０１〜２０重量部が好ましく、０．１〜１０
重量部がより好ましく、０．５〜６重量部が更に好まし
い。ヨウ素と金属ヨウ化物の重量の和が上記範囲より小
さいと脱酸素性能が低下し、大きいと脱酸素剤が過剰に
吸湿して浸みだしの原因となることがあり、問題を生じ
る。The weight of iodine per 100 parts by weight of iron powder is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight. The particle size of iodine is 1
It is preferably 0 mesh or less, and particularly preferably 50 mesh or less. The catalyst according to the oxygen scavenger composition of the present invention does not prevent the interposition of other halides in a range that does not prevent achievement of the oxygen scavenging reaction under low moisture. In a preferred embodiment, the combined content of iodine and iodide in the catalyst is 90% by weight or more. Preferably 9
5% by weight or more. The reaction accelerator of the present invention may be mixed with iron powder, but is preferably coated on iron powder. The sum of the weights of iodine and metal iodide per 100 parts by weight of iron powder is preferably 0.01 to 20 parts by weight, and 0.1 to 10 parts by weight.
A part by weight is more preferable, and 0.5 to 6 parts by weight is further preferable. If the sum of the weights of iodine and metal iodide is smaller than the above range, the oxygen scavenging performance decreases, and if the sum is large, the oxygen scavenger absorbs moisture excessively and may cause leaching, causing a problem.
【００２０】また、ヨウ素に対する金属ヨウ化物の重量
比は、脱酸素剤重量当りの、金属ヨウ化物のヨウ素イオ
ン（Ｉ-）の重量がヨウ素（Ｉ2）の重量の１／２より大
きい量である。重量比が１／２より大きいと、ヨウ素は
金属ヨウ化物と錯塩を形成し、これが脱酸素の触媒作用
を向上させると共に、ヨウ素の気散防止に寄与するの
で、好ましい。反応活性成分が鉄紛の表面に付着し、脱
酸素剤樹脂に配合された際に鉄紛とヨウ素及びヨウ化物
が、分離せず、その触媒反応が十分期待できる場合に
は、ヨウ素及びヨウ化物の重量の和が０．１〜１０重量
部でもよく、より好ましくは０．５〜６重量部である。
また、ヨウ素に対するヨウ化金属塩の重量比が１：０．
６５〜１０である場合により好適な脱酸素樹脂組成物が
得られる。The weight ratio of the metal iodide to the iodine is such that the weight of the metal iodide iodide ion (I − ) per weight of the oxygen scavenger is greater than の of the weight of the iodine (I 2 ). is there. When the weight ratio is more than 1/2, the iodine forms a complex salt with the metal iodide, which improves the catalytic action of deoxygenation and contributes to the prevention of iodine gas diffusion. If the reaction active component adheres to the surface of the iron powder and is mixed with the oxygen scavenger resin, the iron powder and iodine and iodide do not separate, and if the catalytic reaction can be sufficiently expected, iodine and iodide May be 0.1 to 10 parts by weight, more preferably 0.5 to 6 parts by weight.
The weight ratio of the metal iodide salt to iodine is 1: 0.
When it is 65 to 10, a more suitable deoxygenated resin composition is obtained.
【００２１】３成分系脱酸素剤組成物の調製方法の一例
を挙げる。先ず金属ヨウ化物の濃厚な水溶液にヨウ素を
溶解してヨウ素と金属ヨウ化物の水溶液とし、次に鉄粉
を攪拌しながらこの水溶液を噴霧・混合し、乾燥して水
分を除去することにより、鉄粉の表面にヨウ素と金属ヨ
ウ化物の混合物が被覆された流動性がよくハンドリング
し易い粒状の脱酸素剤組成物が得られる。ヨウ素と金属
ヨウ化物とは錯塩を形成し、これが脱酸素の触媒作用を
向上させると共に、ヨウ素の気散防止に寄与している。
２成分系ないし３成分系の脱酸素剤組成物中の水分含有
量は、１重量％以下が好ましく、０．２重量％以下がよ
り好ましい。水分含有量が上記範囲より大きいと、脱酸
素剤組成物の粉体としての流動性が悪化して剤の調製が
困難になる上に、剤から保存物品への水分移行が起こり
問題が生ずる。なお、脱酸素剤組成物には、臭気防止、
粉塵抑制、錆防止等のため必要に応じて、シリカ粉末、
パーライト、珪藻土、水酸化アルミニウム、アルミナ、
活性炭、吸水性高分子等の添加剤を加えることができ
る。An example of a method for preparing a three-component oxygen scavenger composition will be described. First, iodine is dissolved in a concentrated aqueous solution of a metal iodide to form an aqueous solution of iodine and a metal iodide, and then the aqueous solution is sprayed and mixed while stirring iron powder, and dried to remove water. A powdery oxygen scavenger composition having good flowability and easy handling, in which a mixture of iodine and metal iodide is coated on the surface of the powder, can be obtained. Iodine and metal iodides form complex salts, which improve the catalytic action of deoxygenation and contribute to the prevention of iodine gas diffusion.
The water content in the two-component or three-component oxygen scavenger composition is preferably 1% by weight or less, more preferably 0.2% by weight or less. If the water content is larger than the above range, the fluidity of the oxygen scavenger composition as a powder is deteriorated, making the preparation of the agent difficult, and the transfer of water from the agent to the storage article causes a problem. In addition, the oxygen scavenger composition includes odor prevention,
Silica powder, if necessary for dust suppression, rust prevention, etc.
Perlite, diatomaceous earth, aluminum hydroxide, alumina,
Additives such as activated carbon and water-absorbing polymers can be added.
【００２２】２成分系ないし３成分系の脱酸素剤組成物
を通気性包装材料の小袋に充填して脱酸素剤包装体と
し、この形態で物品保存の用途に利用する。通気性包装
材料としては、酸素透過度が１００ｃｃ／ｍ2・atm・da
y（25℃、50%RH）以上の包装材料、例えば、プラスチッ
クフィルム、不織布、紙等、またはこれらを素材とする
多層体フィルムが用いられる。なお、脱酸素剤組成物を
樹脂に練り込みフィルム状脱酸素剤の形態にして、被保
存物の用途に利用することもできる。樹脂に練り込む場
合、脱酸素剤組成物（以下、脱酸素剤ともいう）及び／
又は樹脂中には、アルカリ土類金属酸化物や、珪藻土、
アルミナ、パルプ、吸水性高分子等の吸水剤、臭気吸着
剤（活性炭、モレキュラーシーブ等）、着色用顔料（酸
化チタン、酸化鉄、カーボンブラック等）等を添加する
ことが可能である。A two-component or three-component oxygen scavenger composition is filled in a small bag of a breathable packaging material to form an oxygen scavenger package, which is used for preserving articles in this form. As a breathable packaging material, the oxygen permeability is 100 cc / m 2 · atm · da
A packaging material of y (25 ° C., 50% RH) or more, for example, a plastic film, nonwoven fabric, paper, or the like, or a multilayer film made of these materials is used. The oxygen scavenger composition may be kneaded into a resin to form a film-shaped oxygen scavenger and used for the purpose of preservation. When kneaded into a resin, an oxygen scavenger composition (hereinafter also referred to as an oxygen scavenger) and / or
Or in the resin, alkaline earth metal oxides, diatomaceous earth,
It is possible to add a water absorbing agent such as alumina, pulp, or a water-absorbing polymer, an odor adsorbent (eg, activated carbon, molecular sieve), a coloring pigment (eg, titanium oxide, iron oxide, and carbon black).
【００２３】脱酸素剤が配合される熱可塑性樹脂は、特
に限定されることはないが、好ましくは、ポリエチレ
ン、ポリプロピレン、各種エチレン共重合体、変性ポリ
オレフィン、エラストマー類等の単独またはブレンド品
である。本発明の脱酸素性樹脂組成物は、前記脱酸素剤
と熱可塑性樹脂を溶融混練して製造される。また、加熱
軟化した熱可塑性樹脂間に前記脱酸素剤を挟みこむこと
によっても製造される。両者の配合比は、熱可塑性樹脂
１５〜７５重量部に対し前記脱酸素剤を２５〜８５重量
部の割合が好ましく、熱可塑性樹脂３０〜７０重量部に
対し前記脱酸素剤を３０〜７０重量部の割合がより好ま
しい。The thermoplastic resin in which the oxygen scavenger is blended is not particularly limited, but is preferably a single or a blend of polyethylene, polypropylene, various ethylene copolymers, modified polyolefins, elastomers and the like. . The oxygen-absorbing resin composition of the present invention is produced by melt-kneading the oxygen-absorbing agent and the thermoplastic resin. Further, it is also produced by sandwiching the oxygen scavenger between the heat-softened thermoplastic resins. The mixing ratio of the two is preferably 25 to 85 parts by weight of the oxygen scavenger with respect to 15 to 75 parts by weight of the thermoplastic resin, and 30 to 70 parts by weight of the oxygen scavenger with respect to 30 to 70 parts by weight of the thermoplastic resin. The ratio of parts is more preferred.
【００２４】熱可塑性樹脂と脱酸素剤とを混練する際、
脱酸素剤の水分含有量は、脱酸素剤に対して１重量％以
下であることが好ましい。脱酸素性能を発揮するために
必ずしもさらに水分を保有させる必要はない。こうする
ことにより、樹脂組成物から樹脂シート（フィルムに相
当する薄いものを含めて総称する）を作る際、シート内
に水分が残存したり、気泡様の性状不良がシートに発生
するのを避けることができる。本発明の脱酸素樹脂組成
物は、水分含有量が低い被保存物の保存に適するように
しているため、シート状等に成形された際にそれ自身が
実質的に保水成分を含まないものが好ましく、水分含有
量が、１重量％以下、好ましくは、０．６重量％以下の
ものが、熱成形加工に際して発泡等の不都合を起こすこ
となく熱成形性が良好であるために、この状態で十分脱
酸素反応を達成することができるので好ましい。When kneading the thermoplastic resin and the oxygen scavenger,
The water content of the oxygen scavenger is preferably 1% by weight or less based on the oxygen scavenger. It is not always necessary to further retain moisture in order to exhibit the deoxidizing performance. In this way, when a resin sheet (collectively including a thin film equivalent to a film) is made from the resin composition, it is possible to prevent moisture from remaining in the sheet and the occurrence of bubble-like property defects on the sheet. be able to. Since the oxygen-absorbing resin composition of the present invention is suitable for preservation of an object to be preserved having a low moisture content, when it is formed into a sheet or the like, it does not substantially contain a water retention component. Preferably, a water content of 1% by weight or less, preferably 0.6% by weight or less has good thermoformability without inconvenience such as foaming during thermoforming. This is preferable since a sufficient deoxygenation reaction can be achieved.
【００２５】本発明の脱酸素性樹脂組成物からなる脱酸
素剤は、その形状によらず、水分活性が０．１以上の物
品の包装体において迅速に脱酸素して長期間の品質保持
を可能にする。脱酸素性シートの厚さは、５０μｍ〜３
ｍｍの範囲が好ましく、必要酸素吸収性能、加工性、装
填性等を考慮して適宜選択される。熱可塑性樹脂と脱酸
素剤からなる樹脂組成物をシート化して利用する場合の
シート厚さは用途、目的により様々であるが、５０μｍ
未満の場合は所望の酸素吸収能力を得るために非常に大
面積の酸素吸収シートをしなければならないケースや鉄
粉を特別細かくする必要が生じるなど問題がある。一
方、５ｍｍを越す場合は、シート加工後の延伸において
シートを均一な延伸温度にすることが難しく均一な延伸
ができなかったり、延伸応力が非常に大きくなり、通常
の装置では困難な場合もある。The oxygen-absorbing agent comprising the oxygen-absorbing resin composition of the present invention, regardless of its shape, quickly deoxygenates a package of an article having a water activity of 0.1 or more to maintain quality for a long time. enable. The thickness of the deoxidizing sheet is 50 μm to 3
The range of mm is preferable, and is appropriately selected in consideration of necessary oxygen absorption performance, workability, loadability, and the like. When a resin composition comprising a thermoplastic resin and an oxygen scavenger is used in the form of a sheet, the sheet thickness varies depending on the use and purpose, but is 50 μm.
If it is less than this, there are problems such as a case where an oxygen absorbing sheet having a very large area must be formed in order to obtain a desired oxygen absorbing capacity, and a need to make iron powder particularly fine. On the other hand, if it exceeds 5 mm, it may be difficult to achieve a uniform stretching temperature of the sheet in stretching after sheet processing, and uniform stretching may not be possible, or stretching stress may be extremely large, which may be difficult with a normal apparatus. .
【００２６】また、該脱酸素樹脂組成物をシート化し、
１軸または２軸延伸することにより、熱可塑性樹脂シー
トに小さな空隙（ミクロボイド）を多数発生させて多孔
質化された脱酸素性シートが得られる。該シート中に均
一に分散されたヨウ素及びヨウ化金属塩と鉄粉よりなる
脱酸素剤は、ミクロボイドを通じて外気と接触してお
り、包装体空間内の酸素を効果的に吸収することができ
る特徴を有している。この場合、延伸倍率は１．５倍か
ら１２倍が好ましく、１．５倍未満ではミクロボイドの
発生が少なく均一分散された脱酸素剤が大気と充分に接
触できないため格別顕著な酸素吸収能力を得ることがで
きない。また、１２倍を越えると得られる脱酸素樹脂組
成物はフィルム強度が延伸方向に対し著しく低下し、僅
かな外力で破損するために実用に供し得ない。シートの
延伸温度については、適宜加工可能な温度を設定すれば
よいが、熱可塑性樹脂の融点より３〜７℃低い温度で延
伸すればミクロボイドが発生しやすく、酸素吸収速度に
優れる脱酸素性シートの作成が可能である。Further, the oxygen-absorbing resin composition is formed into a sheet,
By uniaxially or biaxially stretching, a large number of small voids (microvoids) are generated in the thermoplastic resin sheet to obtain a porous oxygen-absorbing sheet. The oxygen absorber composed of iodine and metal iodide salts and iron powder uniformly dispersed in the sheet is in contact with the outside air through microvoids, and can effectively absorb oxygen in the package space. have. In this case, the stretching ratio is preferably from 1.5 to 12 times, and if it is less than 1.5 times, the microvoids are less generated and the oxygen-dispersing agent uniformly dispersed cannot sufficiently contact the atmosphere, so that a particularly remarkable oxygen absorbing ability is obtained. Can not do. On the other hand, when the ratio exceeds 12 times, the obtained oxygen-absorbing resin composition has an extremely low film strength in the stretching direction and is broken by a small external force, so that it cannot be put to practical use. The stretching temperature of the sheet may be appropriately set at a temperature at which the sheet can be processed. However, if the sheet is stretched at a temperature 3 to 7 ° C. lower than the melting point of the thermoplastic resin, microvoids are easily generated, and the oxygen-absorbing sheet has an excellent oxygen absorption rate. Can be created.
【００２７】[0027]
【発明の実施の形態】被保存物の保存方法としては、水
分活性が０．１以上の物品を上記の脱酸素剤包装体と共
にガスバリヤー性容器に収納し密閉することにより、容
器内が迅速に脱酸素されて長期間の品質保持が可能とな
る。本発明の脱酸素剤包装体の特徴は、低湿度雰囲気下
での優れた脱酸素性能にあり、水分活性が０．１〜０．
６、特に水分活性が０．２〜０．５の低水分含有物品の
保存分野で威力を発揮する。BEST MODE FOR CARRYING OUT THE INVENTION As a method for preserving an object to be preserved, an article having a water activity of 0.1 or more is stored in a gas-barrier container together with the above-described oxygen-absorbing agent package and sealed, so that the inside of the container can be quickly stored. To maintain the quality for a long period of time. The oxygen scavenger package of the present invention is characterized by excellent oxygen scavenging performance under a low humidity atmosphere and a water activity of 0.1 to 0.1.
6, particularly effective in the field of preserving low moisture content articles having a water activity of 0.2 to 0.5.
【００２８】ガスバリヤー性容器（以下、単に容器とい
うことがある）としては、容器の形状、材質は、制限さ
れず、例えば、金属缶、ガラス瓶、プラスチック製の容
器や袋等の内、密封可能で実質的にガスバリヤー性のも
のであればよい。例えば、ポリエチレンテレフタレート
／アルミ蒸着／ポリエチレン、延伸ポリプロピレン／ポ
リビニルアルコール／ポリエチレン、ポリ塩化ビニリデ
ンコート（Ｋコート）延伸ナイロン／ポリエチレン、ア
ルミ箔／ポリエチレン等の積層体、ＭＸＤ６ナイロン系
の共押し出し積層体に例示される、酸素透過度０〜１０
０ｃｃ／ｍ2・atm・day（25℃、50%RH）未満、より好ま
しくは０〜５０ｃｃ／ｍ2・atm・day（25℃、50%RH）未
満の多層シートやフィルムまたはシートからなる容器や
袋が簡便に用いられる。The shape and material of the gas barrier container (hereinafter, sometimes simply referred to as a container) are not limited. For example, a metal can, a glass bottle, a plastic container or bag can be sealed. Any gas barrier properties may be used. Examples are laminates of polyethylene terephthalate / aluminum vapor deposition / polyethylene, stretched polypropylene / polyvinyl alcohol / polyethylene, polyvinylidene chloride coat (K coat) stretched nylon / polyethylene, aluminum foil / polyethylene, and coextruded laminates of MXD6 nylon. Oxygen permeability 0 to 10
Multilayer sheet, film or container of less than 0 cc / m 2 · atm · day (25 ° C., 50% RH), more preferably less than 0-50 cc / m 2 · atm · day (25 ° C., 50% RH) And bags are conveniently used.
【００２９】本発明の脱酸素性シート、好ましくは多孔
性の脱酸素性シートを小片に切り取り、通気性包材に包
装した脱酸素樹脂包装体の形態は、さまざまな形態が考
えられる。例えば、通気性包材を小袋状にしその中に脱
酸酸素樹脂組成物を収納した形態からなる小袋型の脱酸
素剤包装体、片面に通気性包材、他の片面に粘着剤を用
いた、簡便に貼着可能なラベル状形態からなるラベル型
脱酸素剤、バリア性パッキングの片面の中央部に通気性
包材を用いて該脱酸素樹脂組成物を固定し、瓶口と接触
する部分はバリア性パッキングがあたるように配された
パッキング形態からなるパッキン型脱酸素剤、等があげ
られる。ラベル型脱酸素剤を添着した食品包装体は、該
脱酸素剤が十分に酸素吸収して保存効果を発揮するに
は、食品等の保存物品とともにガスバリアー性容器に密
封する。The oxygen-absorbing resin package of the present invention, preferably a porous oxygen-absorbing sheet, is cut into small pieces and wrapped in a gas-permeable packaging material. For example, a small bag-type oxygen-absorbing agent package having a form in which a gas-permeable packaging material is formed into a small bag and a deoxidized oxygen resin composition is stored therein, a gas-permeable packaging material on one surface, and an adhesive on another surface. A label-type oxygen absorber having a label-like form that can be easily stuck, a portion in which the oxygen-absorbing resin composition is fixed to the center of one side of the barrier packing by using a breathable packaging material, and comes into contact with the bottle mouth. And a packing type oxygen scavenger having a packing form arranged so as to be hit by a barrier packing. The food package to which the label-type oxygen absorber has been attached is sealed in a gas barrier container together with food or other stored articles so that the oxygen absorber absorbs oxygen sufficiently and exerts a storage effect.
【００３０】本発明の脱酸素性樹脂組成物からなる脱酸
素性シートまたは多孔性の脱酸素性シートは、酸素透過
性熱可塑性樹脂からなる酸素透過層とガスバリアー性材
料からなるガスバリアー層の間に酸素吸収層として配置
して積層することにより、脱酸素性多層体になる。すな
わち、本発明の一つの態様は、酸素透過性の熱可塑性樹
脂からなる酸素透過層、本発明の脱酸素性樹脂組成物か
らなる脱酸素性シートからなる酸素吸収層、ガスバリア
性材料からなるガスバリア層の少なくとも３層からなる
酸素吸収性多層体である。本発明の脱酸素樹脂組成物を
多層フィルムもしくはシートとする場合には少なくとも
脱酸素剤組成物が含まれる脱酸素樹脂層の片側にはガス
バリア層が配せられているのが必要であり、その反対側
の層には内層が配せられている必要がある。The oxygen-absorbing sheet or porous oxygen-absorbing sheet comprising the oxygen-absorbing resin composition of the present invention comprises an oxygen-permeable layer comprising an oxygen-permeable thermoplastic resin and a gas-barrier layer comprising a gas-barrier material. By arranging and laminating as an oxygen absorbing layer in between, a deoxidized multilayer body is obtained. That is, one embodiment of the present invention is an oxygen-permeable layer made of an oxygen-permeable thermoplastic resin, an oxygen-absorbing layer made of an oxygen-absorbing sheet made of the oxygen-absorbing resin composition of the present invention, and a gas barrier made of a gas-barrier material. An oxygen-absorbing multilayer body comprising at least three layers. When the oxygen-absorbing resin composition of the present invention is to be a multilayer film or sheet, it is necessary that a gas barrier layer be provided on at least one side of the oxygen-absorbing resin layer containing the oxygen-absorbing composition. The opposite layer must have an inner layer.
【００３１】酸素透過層は、包装容器とする場合、保存
される物品と酸素吸収層との直接接触を避けるために設
けられるものであり、主に密閉される場合のシーラント
層としても利用され得るものである。酸素透過層に用い
る樹脂は、酸素吸収層との接着性を考慮して適宜選択さ
れる。酸素透過層の厚みは２０〜１８０μｍの範囲で設
定され、該層の酸素透過度は１００ｃｃ／ｍ2・atm・da
y以上が好ましく、２００ｃｃ／ｍ2・atm・day以上がよ
り好ましい。また、酸素透過層には、顔料、スリップ剤
等を適宜添加してもよい。The oxygen-permeable layer is provided to avoid direct contact between the stored article and the oxygen-absorbing layer when it is used as a packaging container, and can be used mainly as a sealant layer when the container is hermetically closed. Things. The resin used for the oxygen permeable layer is appropriately selected in consideration of the adhesiveness to the oxygen absorption layer. The thickness of the oxygen permeable layer is set in the range of 20 to 180 μm, and the oxygen permeability of the layer is 100 cc / m 2 · atm · da
It is preferably at least y, more preferably at least 200 cc / m 2 · atm · day. Further, a pigment, a slip agent and the like may be appropriately added to the oxygen permeable layer.
【００３２】酸素透過層に用いられる樹脂としては、低
密度ポリエチレン、直鎖状低密度ポリエチレン、高密度
ポリエチレン、ポリプロピレン、ポリメチルペンテン等
のポリオレフィン類及びこれらの酸変性ポリオレフィン
類、ポリスチレン等のポリスチレン類及びこれらの変性
物、エチレン−酢酸ビニル共重合体、エチレン−メタク
リル酸メチル共重合体、エチレン−アクリル酸エチル共
重合体、エチレン−アクリル酸共重合体、エチレン−プ
ロピレン共重合体等の各種エチレン共重合体、エラスト
マー類等の熱可塑性樹脂が好ましい。中でも、耐薬品
性、耐熱性及び衛生性が高いので、ポリエチレン、ポリ
プロピレンが好ましく用いられる。これらの樹脂は単独
または適宜ブレンドして用いられる。Examples of the resin used for the oxygen permeable layer include polyolefins such as low-density polyethylene, linear low-density polyethylene, high-density polyethylene, polypropylene and polymethylpentene, and acid-modified polyolefins thereof and polystyrenes such as polystyrene. And various modified ethylene such as ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-propylene copolymer Thermoplastic resins such as copolymers and elastomers are preferred. Among them, polyethylene and polypropylene are preferably used because of high chemical resistance, heat resistance and hygiene. These resins are used singly or in an appropriate blend.
【００３３】酸素吸収層に用いられる脱酸素剤組成物
は、前記の脱酸素剤組成物である。酸素吸収層に用いら
れる熱可塑性樹脂は、前記酸素透過層に用いられる各種
の樹脂が用いられ、酸素吸収層には、前記の脱酸素剤組
成物にアルカリ土類金属酸化物、活性炭、ゼオライト、
酸化チタン等各種添加剤を加えることができる。酸素吸
収層である脱酸素性シートの厚さは、２０〜２００μｍ
の範囲が好ましく、必要酸素吸収性能、加工性、機械物
性等を考慮して適宜選択される。The oxygen scavenger composition used in the oxygen absorbing layer is the above oxygen scavenger composition. As the thermoplastic resin used for the oxygen-absorbing layer, various resins used for the oxygen-permeable layer are used, and for the oxygen-absorbing layer, the oxygen-absorbing composition contains an alkaline earth metal oxide, activated carbon, zeolite,
Various additives such as titanium oxide can be added. The thickness of the oxygen-absorbing sheet as the oxygen-absorbing layer is 20 to 200 μm
Is preferably selected in consideration of necessary oxygen absorption performance, processability, mechanical properties and the like.
【００３４】ガスバリア層としては、バリア層は酸素お
よび水分が透過しにくい層であれば特に特定されない
が、アルミ箔等の金属箔、アルミ、酸化アルミ、酸化珪
素等の金属または金属酸化物を蒸着した樹脂フィルム、
ＭＸＤ６（ポリ（メタキシリレンジアミンアジパミ
ド））、非晶性ポリアミド等のナイロン、エチレン−ビ
ニルアルコール共重合体樹脂、ポリ塩化ビニリデン等の
樹脂、ポリ塩化ビニリデン被覆フィルム等が好適に用い
られ、ガスバリア性が損なわれない限り必要に応じて延
伸したり、他樹脂と積層等により複合化してもよい。ガ
スバリア層の酸素透過度は１００ｃｃ／ｍ2・atm・day
未満が好ましく、５０ｃｃ／ｍ2・atm・day未満がより
好ましい。The gas barrier layer is not particularly limited as long as the barrier layer is a layer through which oxygen and moisture are hardly permeated. However, a metal foil such as an aluminum foil, a metal such as aluminum, aluminum oxide, silicon oxide or a metal oxide is deposited. Resin film,
MXD6 (poly (meta-xylylenediamine adipamide)), nylon such as amorphous polyamide, ethylene-vinyl alcohol copolymer resin, resin such as polyvinylidene chloride, polyvinylidene chloride-coated film and the like are preferably used. As long as the gas barrier property is not impaired, the film may be stretched as necessary, or may be combined with another resin by lamination or the like. The oxygen permeability of the gas barrier layer is 100cc / m 2 · atm · day
Is preferably less than 50 cc / m 2 · atm · day.
【００３５】ガスバリア層の外側には、さらに熱可塑性
樹脂からなる保護層を設けることが好ましい。保護層に
用いる熱可塑性樹脂には、低密度ポリエチレン、直鎖状
低密度ポリエチレン、高密度ポリエチレン等のポリエチ
レン類、各種ポリプロピレン、ナイロン６、ナイロン
６,６及びポリエチレンテレフタレート並びにこれらの
組合せが挙げられる。本発明における酸素吸収性多層体
の積層方法は多層体の層構成、各層の材料や性状に応じ
て、押出ラミネーション、ドライラミネーション、共押
出、ブロー成形等、公知の技術を用いることができる。It is preferable that a protective layer made of a thermoplastic resin is further provided outside the gas barrier layer. Examples of the thermoplastic resin used for the protective layer include polyethylenes such as low-density polyethylene, linear low-density polyethylene, and high-density polyethylene, various polypropylenes, nylon 6, nylon 6,6 and polyethylene terephthalate, and combinations thereof. In the method of laminating the oxygen-absorbing multilayer body in the present invention, known techniques such as extrusion lamination, dry lamination, co-extrusion, and blow molding can be used according to the layer structure of the multilayer body and the material and properties of each layer.
【００３６】本発明では、包装容器壁面の一部または全
部に、酸素吸収性多層体を酸素透過層を容器内面側に配
して使用することにより、容器内に密封した過酸化物含
有物より発生する酸素を吸収除去して、容器内の過酸化
物含有物内の酸素による変質を防止し、且つ包装容器の
内圧上昇による外観変化、破裂、破袋を抑制できる。包
装容器壁面全体に酸素吸収性多層体を使用しても良く、
密封容器壁面の一部に酸素吸収性多層体を使用して他の
壁面部分に酸素吸収性の無いガスバリア材料を使用して
もよい。In the present invention, by using an oxygen-absorbing multilayer body on a part or all of the wall surface of the packaging container with an oxygen-permeable layer disposed on the inner surface side of the container, the peroxide-containing material sealed in the container is reduced. By absorbing and removing the generated oxygen, it is possible to prevent deterioration due to oxygen in the peroxide-containing material in the container, and to suppress changes in appearance, rupture, and bag breakage due to an increase in the internal pressure of the packaging container. An oxygen-absorbing multilayer body may be used on the entire packaging container wall surface,
An oxygen-absorbing multilayer body may be used for a part of the wall surface of the sealed container, and a gas barrier material having no oxygen-absorbing property may be used for the other wall part.
【００３７】本発明の脱酸素性樹脂組成物からなる各種
の脱酸素剤または脱酸素性多層体は、その形状によら
ず、雰囲気の相対湿度（RH）が１０〜７０％、あるいは
２０〜７０％、特に２０〜５０％においても、酸素吸収
性能を発揮する。したがって、水分含有量が低く放散す
る水分が少なく従来の自力反応型脱酸素剤が適用できな
いような物品、具体的には、水分活性が０．１〜０．
７、あるいは０．２〜０．７、特に０．２〜０．５の低
水分含有物品の保存分野で威力を発揮する。すなわち、
水分活性が低く、低湿度の乾燥条件での保存が必要とさ
れる物品に好適に適用される。低水分含有品としては上
記水分活性のものが当てはまるが、特に本発明を適用で
きる低水分含有物品（被包装物）として、水分活性が
０．１以上の吸湿の嫌われる物品、例えば、乾物や油揚
げスナック等の食品、粉体、顆粒、医薬品、健康食品等
の低水分物品の保存に使用できる。その例には、粉末ス
ープ、粉末飲料、粉末菓子、調味料、穀物粉、栄養食
品、健康食品、着色料、着香料、香辛料、散薬類、粉石
鹸、歯磨粉、工業薬品及びこれらのものの成形体（錠剤
型）を例示できる。なお、本発明の樹脂組成物のうち公
知の成分及びその含有量、並びに製造方法としては、公
知の従来例が参考にされる。例えば、本願出願人によっ
て過去に出願された特公昭５６−３３９８０号公報を参
考にすることができる。Various oxygen scavengers or oxygen scavengers comprising the oxygen scavenger resin composition of the present invention have an atmosphere with a relative humidity (RH) of 10 to 70% or 20 to 70, regardless of the shape. %, Particularly 20 to 50%, exhibits oxygen absorption performance. Therefore, an article having a low water content and a small amount of water to be diffused, to which a conventional self-reactive oxygen scavenger cannot be applied, specifically, a water activity of 0.1 to 0.1.
7 or 0.2 to 0.7, especially 0.2 to 0.5. That is,
It is suitably applied to articles which have low water activity and need to be stored under dry conditions of low humidity. The low water-containing products include those having the above-mentioned water activity. In particular, as the low water-containing products (packaged products) to which the present invention can be applied, products having a water activity of 0.1 or more, which are not easily absorbed by moisture, such as dry products and the like. It can be used for preserving foods such as fried snacks, powders, granules, low moisture products such as pharmaceuticals and health foods. Examples include powdered soups, powdered beverages, powdered confectionery, seasonings, cereal flours, nutritional foods, health foods, colorings, flavorings, spices, powdered medicines, powdered soaps, tooth powders, industrial chemicals and the molding of these A body (tablet type) can be exemplified. In addition, as a well-known component in a resin composition of this invention, its content, and a manufacturing method, a well-known conventional example is referred. For example, Japanese Patent Publication No. 56-33980 filed in the past by the present applicant can be referred to.
【００３８】[0038]
【実施例】次に、本発明に係る実施の形態について詳細
に説明する。 （実施例１）最大粒径１５０μｍの鉄粉１００ｇと、乳
鉢ですりつぶしたヨウ素２ｇとをガスバリアー性袋内で
攪拌混合し、水分含有量が０．１重量％以下の脱酸素剤
組成物１を得た。組成比は鉄粉１００重量部当たりヨウ
素２重量部である。この脱酸素剤組成物０．７ｇを通気
性包装材料（ポリスチレン不織布、デュポン社製、商品
名タイペック）からなる小袋（３７mm×４０mm）に充填
して脱酸素剤包装体を多数個得た。次に、Ｋコートナイ
ロン／ポリエチレンよりなるガスバリヤー袋（１５０mm
×２２０mm）に、この脱酸素剤包装体と各種濃度のグリ
セリン水溶液１０mlを含浸させた綿とを入れ、空気250m
l を封入して密封した。この袋を２５℃に保持して袋内
の酸素濃度を経時的に測定し、脱酸素テストを実施し
た。結果を表１に示す。なお、グリセリン水溶液は雰囲
気中の湿度を調節する役目を持ち、グリセリン濃度が７
９重量％の時RH（湿度）は50％、グリセリン濃度が８６
重量％の時RHは40％、グリセリン濃度が９２重量％の時
RHは30％である。Next, embodiments of the present invention will be described in detail. (Example 1) 100 g of iron powder having a maximum particle size of 150 μm and 2 g of iodine ground in a mortar were mixed by stirring in a gas barrier bag, and a deoxidizer composition 1 having a water content of 0.1% by weight or less was obtained. I got The composition ratio is 2 parts by weight of iodine per 100 parts by weight of iron powder. 0.7 g of the oxygen absorber composition was filled into a small bag (37 mm × 40 mm) made of a breathable packaging material (polystyrene nonwoven fabric, manufactured by DuPont, trade name: TYPEC) to obtain a large number of oxygen absorber packaging bodies. Next, a gas barrier bag made of K-coated nylon / polyethylene (150 mm
× 220 mm), the oxygen-absorbing agent package and cotton impregnated with 10 ml of a glycerin aqueous solution of various concentrations were put into the container, and the air was heated to 250 m.
l was sealed and sealed. The bag was kept at 25 ° C., the oxygen concentration in the bag was measured over time, and a deoxygenation test was performed. Table 1 shows the results. The glycerin aqueous solution has a role of adjusting the humidity in the atmosphere, and the glycerin concentration is 7%.
At 9% by weight, the RH (humidity) is 50% and the glycerin concentration is 86.
RH is 40% at weight% and glycerin concentration is 92% by weight
RH is 30%.
【００３９】（実施例２）真空乾燥機に最大粒径１５０
μｍの鉄粉５kgを入れて６０mmHgの真空下に攪拌しなが
ら、水１００mlにヨウ素５０gとヨウ化カリウム５０gを
溶解した水溶液を噴霧し、１２０℃で１時間乾燥して、
水分含有量が０．１重量％以下で粒状の脱酸素剤組成物
２を得た。組成比は鉄粉１００重量部当たりヨウ素１重
量部とヨウ化カリウム１重量部である。脱酸素剤組成物
１の代わりに脱酸素剤組成物２を用いたこと以外は実施
例１と同様にして脱酸素テストを実施した。結果を表１
に示す。(Example 2) The maximum particle size was 150 in a vacuum dryer.
An aqueous solution in which 50 g of iodine and 50 g of potassium iodide were dissolved in 100 ml of water was sprayed with 5 kg of iron powder of 5 μm and stirred under a vacuum of 60 mmHg, and dried at 120 ° C. for 1 hour.
A granular oxygen absorber composition 2 having a water content of 0.1% by weight or less was obtained. The composition ratio is 1 part by weight of iodine and 1 part by weight of potassium iodide per 100 parts by weight of iron powder. An oxygen scavenging test was performed in the same manner as in Example 1 except that oxygen scavenger composition 2 was used instead of oxygen scavenger composition 1. Table 1 shows the results
Shown in
【００４０】（実施例３）真空乾燥機に最大粒径１５０
μｍの鉄粉５kgを入れて６０mmHgの真空下に攪拌しなが
ら、水２００mlにヨウ素７０g とヨウ化カリウム３０g
を溶解した水溶液を噴霧し、１２０℃で１時間乾燥し
て、水分含有量が０．１重量％以下で粒状の脱酸素剤組
成物３を得た。組成比は鉄粉１００重量部当たりヨウ素
１．４重量部とヨウ化カリウム０．６重量部である。脱
酸素剤組成物１の代わりに脱酸素剤組成物３を用いたこ
と以外は実施例１と同様にして脱酸素テストを実施し
た。結果を表１に示す。(Example 3) A maximum particle size of 150 was set in a vacuum dryer.
5 g of iron powder of 5 μm was added and stirred under vacuum of 60 mmHg, and 70 g of iodine and 30 g of potassium iodide were added to 200 ml of water.
Was sprayed and dried at 120 ° C. for 1 hour to obtain a granular oxygen absorber composition 3 having a water content of 0.1% by weight or less. The composition ratio is 1.4 parts by weight of iodine and 0.6 parts by weight of potassium iodide per 100 parts by weight of iron powder. A deoxidation test was performed in the same manner as in Example 1 except that the oxygen scavenger composition 3 was used instead of the oxygen scavenger composition 1. Table 1 shows the results.
【００４１】（実施例４）真空乾燥機に最大粒径１５０
μｍの鉄粉５kgを入れて６０mmHgの真空下に攪拌しなが
ら、水１００mlにヨウ素５０gとヨウ化ナトリウム５０g
を溶解した水溶液を噴霧し、１２０℃で１時間乾燥し
て、水分含有量が０．１重量％以下で粒状の脱酸素剤組
成物４を得た。組成比は鉄粉１００重量部当たりヨウ素
１重量部とヨウ化ナトリウム１重量部である。脱酸素剤
組成物１の代わりに脱酸素剤組成物４を用いたこと以外
は実施例１と同様にして脱酸素テストを実施した。結果
を表１に示す。Example 4 A maximum particle size of 150 was set in a vacuum dryer.
Add 5 kg of iron powder of 50 μm and stir under vacuum of 60 mmHg, and add 50 g of iodine and 50 g of sodium iodide to 100 ml of water.
An aqueous solution in which was dissolved was sprayed and dried at 120 ° C. for 1 hour to obtain a granular oxygen absorber composition 4 having a water content of 0.1% by weight or less. The composition ratio is 1 part by weight of iodine and 1 part by weight of sodium iodide per 100 parts by weight of iron powder. An oxygen scavenging test was performed in the same manner as in Example 1 except that oxygen scavenger composition 4 was used instead of oxygen scavenger composition 1. Table 1 shows the results.
【００４２】（実施例５）真空乾燥機に最大粒径１５０
μｍの鉄粉５kgを入れて６０mmHgの真空下に攪拌しなが
ら、水１００mlにヨウ素５０g とヨウ化カルシウム５０
g を溶解した水溶液を噴霧し、１２０℃で１時間乾燥し
て、水分含有量が０．１重量％以下で粒状の脱酸素剤組
成物５を得た。組成比は鉄粉１００重量部当たりヨウ素
１重量部とヨウ化カルシウム１重量部である。脱酸素剤
組成物１の代わりに脱酸素剤組成物５を用いたこと以外
は実施例１と同様にして脱酸素テストを実施した。結果
を表１に示す。(Example 5) The maximum particle size was 150 in a vacuum dryer.
5 g of iron powder having a particle size of 50 μm and stirring under a vacuum of 60 mmHg were added to 50 g of iodine and 50 g of calcium iodide in 100 ml of water.
g was dissolved and sprayed, and dried at 120 ° C. for 1 hour to obtain a granular oxygen absorbing composition 5 having a water content of 0.1% by weight or less. The composition ratio is 1 part by weight of iodine and 1 part by weight of calcium iodide per 100 parts by weight of iron powder. An oxygen scavenging test was performed in the same manner as in Example 1 except that oxygen scavenger composition 5 was used instead of oxygen scavenger composition 1. Table 1 shows the results.
【００４３】（比較例１）真空乾燥機に最大粒径１５０
μｍの鉄粉５kgを入れて６０mmHgの真空下に攪拌しなが
ら、水１００mlに塩化カルシウム１００g を溶解した水
溶液を噴霧し、１２０℃で１時間乾燥して、水分含有量
が０．１重量％以下で粒状の脱酸素剤組成物６を得た。
組成比は鉄粉１００重量部当たり塩化カルシウム２重量
部である。脱酸素剤組成物１の代わりに脱酸素剤組成物
６を用いたこと以外は実施例１と同様にして脱酸素テス
トを実施した。結果を表１に示す。(Comparative Example 1) The maximum particle size was 150 in a vacuum dryer.
An aqueous solution prepared by dissolving 100 g of calcium chloride in 100 ml of water is sprayed while 5 kg of iron powder of 5 μm is added and stirred under a vacuum of 60 mmHg, and dried at 120 ° C. for 1 hour to have a water content of 0.1% by weight or less. Thus, a granular oxygen absorbing composition 6 was obtained.
The composition ratio is 2 parts by weight of calcium chloride per 100 parts by weight of iron powder. An oxygen scavenging test was performed in the same manner as in Example 1 except that oxygen scavenger composition 6 was used instead of oxygen scavenger composition 1. Table 1 shows the results.
【００４４】（比較例２）真空乾燥機に最大粒径１５０
μｍの鉄粉５kgを入れて６０mmHgの真空下に攪拌しなが
ら、水１００mlにヨウ化カリウム１００g を溶解した水
溶液を噴霧し、１２０℃で１時間乾燥して、水分含有量
が０．１重量％以下で粒状の脱酸素剤組成物７を得た。
組成比は鉄粉１００重量部当たりヨウ化カリウム２重量
部である。脱酸素剤組成物１の代わりに脱酸素剤組成物
７を用いたこと以外は実施例１と同様にして脱酸素テス
トを実施した。結果を表１に示す。(Comparative Example 2) The maximum particle size was 150 in a vacuum dryer.
An aqueous solution prepared by dissolving 100 g of potassium iodide in 100 ml of water is sprayed while stirring under a vacuum of 60 mmHg with 5 kg of iron powder of 5 μm, and dried at 120 ° C. for 1 hour to obtain a water content of 0.1% by weight. A granular oxygen absorber composition 7 was obtained below.
The composition ratio is 2 parts by weight of potassium iodide per 100 parts by weight of iron powder. An oxygen scavenging test was performed in the same manner as in Example 1 except that oxygen scavenger composition 7 was used instead of oxygen scavenger composition 1. Table 1 shows the results.
【００４５】[0045]
【表１】 表中の数値は酸素濃度（％）を示す。 RH100% RH50% RH40% RH30% １日目 １日目 １日目 ８日目 実施例１ 0.1以下 0.1以下 0.1以下 0.1以下 実施例２ 0.1以下 0.1以下 0.1以下 0.1以下 実施例３ 0.1以下 0.1以下 0.1以下 0.1以下 実施例４ 0.1以下 0.1以下 0.1以下 2.0 実施例５ 0.1以下 0.1以下 0.1以下 4.2 比較例１ 0.1以下 15.9 16.6 18.7 比較例２ 0.1以下 4.1 6.2 4.8 [Table 1] The numerical values in the table indicate the oxygen concentration (%). RH100% RH50% RH40% RH30% Day 1 Day 1 Day 1 Day 8 Example 1 0.1 or less 0.1 or less 0.1 or less 0.1 or less Example 2 0.1 or less 0.1 or less 0.1 or less 0.1 or less Example 3 0.1 or less 0.1 or less 0.1 0.1 or less 0.1 or less 0.1 or less 0.1 or less Example 4 0.1 or less 0.1 or less 0.1 or less 0.1 or less 4.2 Comparative Example 1 0.1 or less 15.9 16.6 18.7 Comparative Example 2 0.1 or less 4.1 6.2 4.8
【００４６】表１から明らかな様に、鉄粉に塩化カルシ
ウムまたはヨウ化カリウムのみが被覆された脱酸素剤組
成物を用いた比較例１乃至２では、雰囲気中のRH（湿
度）が低いと脱酸素が不十分であるのに対して、本発明
の脱酸素剤組成物を用いた実施例１乃至５では、雰囲気
中のRHが低くても酸素濃度が速やかに低下していて、本
発明の脱酸素剤組成物は低RH下での脱酸素性能が優れて
いることを示している。As is evident from Table 1, in Comparative Examples 1 and 2 using the oxygen scavenger composition in which iron powder was coated only with calcium chloride or potassium iodide, the RH (humidity) in the atmosphere was low. In contrast to the insufficient oxygen removal, in Examples 1 to 5 using the oxygen absorber composition of the present invention, the oxygen concentration was rapidly reduced even when the RH in the atmosphere was low. This shows that the oxygen scavenger composition of Example 1 has excellent oxygen scavenging performance under low RH.
【００４７】（実施例６）Ｋコートナイロン／ポリエチ
レンよりなるガスバリヤー袋（１５０mm×２２０mm）
に、実施例２で得た脱酸素剤包装体と水分活性が０．２
６の市販ラムネ菓子２０ｇとを入れ、空気３５mlを封入
して密封した。この密封袋を２５℃で１ヶ月間保存した
後、袋内の酸素濃度を測定したところ０．１％以下であ
った。保存後のラムネ菓子は風味と食感が良好であっ
た。Example 6 Gas barrier bag made of K-coated nylon / polyethylene (150 mm × 220 mm)
The oxygen scavenger package obtained in Example 2 had a water activity of 0.2
20 g of a commercially available ramune confectionery of No. 6 was put in, sealed with 35 ml of air. After storing this sealed bag at 25 ° C. for one month, the oxygen concentration in the bag was measured and found to be 0.1% or less. The preserved ramune confection had good flavor and texture.
【００４８】（比較例３）実施例２で得た脱酸素剤包装
体の代わりに、比較例１で得た脱酸素剤包装体を用いた
こと以外は、実施例６と同様にして市販ラムネ菓子の保
存テストを実施した。１ヶ月間保存後の袋内の酸素濃度
は１８．０％であり、脱酸素が殆ど進んでいなかった。
また、ラムネ菓子は風味が低下していた。(Comparative Example 3) A commercially available ramune product was prepared in the same manner as in Example 6 except that the oxygen scavenger package obtained in Comparative Example 1 was used instead of the oxygen scavenger package obtained in Example 2. A confectionary storage test was performed. After storage for one month, the oxygen concentration in the bag was 18.0%, and deoxygenation hardly progressed.
In addition, the flavor of the ramune confectionery was reduced.
【００４９】（比較例４）脱酸素剤包装体として市販の
自力反応型脱酸素剤（三菱ガス化学（株）製、商品名エ
ージレスＺ−３０ＰＴ）を用いたこと以外は実施例６と
同様にして市販ラムネ菓子の保存テストを実施した。１
ヶ月保存後の袋内の酸素濃度は０．１％以下であった。
ラムネ菓子は風味に異常がないものの、脱酸素剤からの
水分を吸収して湿り気をおび、ラムネ菓子本来の食感が
損なわれていた。このように、本発明の脱酸素剤組成物
は、自体に水分を保有しない所謂「水分依存型脱酸素
剤」に属するが、従来の「水分依存型脱酸素剤」では対
応が困難な低湿度雰囲気下でも優れた脱酸素性能を発揮
する。本発明によれば、吸湿の恐れなしに低水分物品の
脱酸素保存が可能であり、特に水分活性が０．１〜０．
６の乾燥状態にあって吸湿の嫌われる医薬品や食品の脱
酸素保存に適していて、これら物品を品質を保持したま
ま長期に保存することができる。Comparative Example 4 The procedure of Example 6 was repeated except that a commercially available self-reactive oxygen absorber (Ageless Z-30PT, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used as the oxygen absorber package. A preservation test of a commercially available ramune confection was conducted. 1
After storage for months, the oxygen concentration in the bag was 0.1% or less.
Although the flavor of the ramune confectionery was not abnormal, the ramune confectionery absorbed moisture from the oxygen scavenger and became moist, impairing the original texture of the ramune confectionery. As described above, the oxygen scavenger composition of the present invention belongs to a so-called “moisture-dependent oxygen scavenger” which does not have moisture in itself, but has a low humidity which is difficult to cope with with the conventional “moisture-dependent oxygen scavenger”. Demonstrates excellent deoxygenation performance even in an atmosphere. ADVANTAGE OF THE INVENTION According to this invention, deoxidation preservation | save of a low-moisture article is possible without fear of moisture absorption.
It is suitable for the deoxygenated preservation of pharmaceuticals and foods that are in a dry state and do not like to absorb moisture, and can store these articles for a long time while maintaining their quality.
【００５０】（実施例７）減圧にできる乾燥機に平均粒
径７０μｍ、最大粒径１５０μｍの鉄粉１００重量部を
入れて６０ｍｍHgの減圧下に攪拌しながら、ヨウ素２重
量部とヨウ化カリウム３重量部を溶解した水溶液を鉄粉
に直接かかるように加え、引き続き６０ｍｍHgの減圧
下、約120℃で１時間混合、乾燥し、粒状の酸素吸収組
成物を得た。次に、２軸押し出し機を用いて、上記酸素
吸収組成物、ポリプロピレン、酸化カルシウムを重量比
６８：３０：２の割合で220℃で混練し、押し出しした
あと、冷却、粉砕して樹脂組成物を得た。この樹脂組成
物を押し出し機に供給し、Ｔダイを通して厚さ１ｍｍの
脱酸素性シートを得た。これを１辺９５ｍｍの正方形に
切り取り、切り取った樹脂組成物を120℃で６倍に１軸
延伸し、多孔性の脱酸素性シートを得た。この脱酸素性
シートの水分量をカールフィッシャー法で測定したとこ
ろ、５００ppm以下であった。次に、Ｋコートナイロン
／ポリエチレンのラミネートフィルムからなるガスバリ
アー性袋２つに、各、前記脱酸素性シート２．２３ｇ
と、袋内を相対湿度100%または30%に調湿するために、
水１０mlまたはグリセリン９２重量％水溶液１０mlを含
ませた綿をそれぞれ入れ、空気２５０mlを封入して密封
し、袋を製造した。この袋を25℃で４日間保存し、ジル
コニア式酸素濃度計（東レエンジニアリング（株）製）
を用いて、袋内の酸素濃度を測定した。袋内相対湿度10
0%または30%で保存後の酸素濃度は、いずれも０．１％
未満に低下していた。Example 7 100 parts by weight of iron powder having an average particle size of 70 μm and a maximum particle size of 150 μm were placed in a dryer capable of reducing pressure, and 2 parts by weight of iodine and 3 parts of potassium iodide 3 were stirred under reduced pressure of 60 mmHg. The aqueous solution in which parts by weight were dissolved was added directly to the iron powder so as to be directly applied thereto, and subsequently mixed and dried at about 120 ° C. for 1 hour under a reduced pressure of 60 mmHg to obtain a granular oxygen absorbing composition. Next, using a twin screw extruder, the oxygen absorbing composition, polypropylene, and calcium oxide were kneaded at a weight ratio of 68: 30: 2 at 220 ° C., extruded, cooled, and pulverized to obtain a resin composition. I got This resin composition was supplied to an extruder, and a 1 mm-thick oxygen-absorbing sheet was obtained through a T-die. This was cut into a square having a side of 95 mm, and the cut resin composition was uniaxially stretched 6 times at 120 ° C. to obtain a porous oxygen-absorbing sheet. The water content of this deoxidized sheet was measured by the Karl Fischer method and found to be 500 ppm or less. Next, 2.23 g of the oxygen-absorbing sheet was placed in each of two gas barrier bags made of a laminated film of K-coated nylon / polyethylene.
To adjust the humidity in the bag to 100% or 30% relative humidity,
A cotton bag containing 10 ml of water or 10 ml of a 92% by weight aqueous glycerin solution was put therein, sealed with 250 ml of air, and a bag was produced. Store this bag at 25 ° C for 4 days, and use a zirconia oxygen analyzer (Toray Engineering Co., Ltd.)
Was used to measure the oxygen concentration in the bag. Relative humidity in bag 10
Oxygen concentration after storage at 0% or 30%, both 0.1%
Had fallen below.
【００５１】（比較例５）ヨウ素２重量部とヨウ化カリ
ウム３重量部を溶解した水溶液の代わりに塩化カリウム
５重量部を溶解した水溶液を使用して脱酸素剤を得たこ
と以外は実施例７と同様にして密封袋を製造し、袋内の
酸素濃度を測定した。袋内相対湿度100％で保存後の酸
素濃度は０．１％未満に低下していたが、袋内相対湿度
30％で保存後の酸素濃度は１８．５％であった。(Comparative Example 5) An oxygen absorbing agent was obtained using an aqueous solution in which 5 parts by weight of potassium chloride was used instead of an aqueous solution in which 2 parts by weight of iodine and 3 parts by weight of potassium iodide were dissolved. A sealed bag was manufactured in the same manner as in Example 7, and the oxygen concentration in the bag was measured. Although the oxygen concentration after storage at 100% relative humidity in the bag had dropped to less than 0.1%, the relative humidity in the bag
The oxygen concentration after storage at 30% was 18.5%.
【００５２】（実施例８）真空乾燥機に平均粒径７０μ
ｍ、最大粒径１５０μｍの鉄粉１００重量部を入れて６
０ｍｍHgの減圧下に攪拌しながら、ヨウ素２重量部とヨ
ウ化カルシウム３重量部を溶解した水溶液を噴霧し、１
２０℃で１時間乾燥して、水分含有量が０．１％以下で
粒状の脱酸素剤を得た。脱酸素剤１００重量部、活性炭
１重量部及び生石灰２重量部とポリプロピレン５０重量
部とを混合後、１９０℃にて溶融混練し、押出機により
脱酸素性樹脂組成物のペレットを得た。実施例７と同様
にして得られた多孔性の脱酸素性シート０．８９ｇを有
孔ポリエステルフィルムからなる通気性包材に入れ脱酸
素樹脂包装体とし、クッキー（水分活性０．４）２０ｇ
とを複合フィルム（Ｋコートナイロン／ポリエチレン）
のバリアー袋に入れ、空気３５mlを封入して密封した。
この密封袋を２５℃で１ヶ月間保存した後、袋内の酸素
濃度を測定したところ０．１％以下であった。クッキー
は、風味は良好であり、食感も良好であった。(Embodiment 8) The average particle size was 70 μm in a vacuum dryer.
m, 100 parts by weight of iron powder having a maximum particle size of 150 μm
While stirring under reduced pressure of 0 mmHg, an aqueous solution in which 2 parts by weight of iodine and 3 parts by weight of calcium iodide were dissolved was sprayed, and 1
After drying at 20 ° C. for 1 hour, a granular oxygen absorber having a water content of 0.1% or less was obtained. After mixing 100 parts by weight of an oxygen scavenger, 1 part by weight of activated carbon, and 2 parts by weight of quicklime with 50 parts by weight of polypropylene, the mixture was melt-kneaded at 190 ° C., and pellets of an oxygen-absorbing resin composition were obtained with an extruder. 0.89 g of the porous oxygen-absorbing sheet obtained in the same manner as in Example 7 was placed in a breathable packaging material made of a perforated polyester film to form an oxygen-absorbing resin package, and 20 g of cookies (water activity: 0.4) were used.
And composite film (K-coated nylon / polyethylene)
, And sealed with 35 ml of air.
After storing this sealed bag at 25 ° C. for one month, the oxygen concentration in the bag was measured and found to be 0.1% or less. The cookies had a good flavor and a good texture.
【００５３】（比較例６）実施例８において、比較例５
で調製した脱酸素性シート０．８９ｇを使用したこと以
外は、実施例８と同様に行った。脱酸素剤包装体とクッ
キーとを封入した密封袋を25℃、１ヶ月保存した後の袋
内の酸素濃度は、１８．０％であった。クッキーの食感
は良好であったものの、風味が低下していた。(Comparative Example 6) In Example 8, Comparative Example 5
Example 8 was carried out in the same manner as in Example 8, except that 0.89 g of the oxygen-absorbing sheet prepared in the above was used. After the sealed bag enclosing the oxygen scavenger package and the cookies was stored at 25 ° C. for one month, the oxygen concentration in the bag was 18.0%. Although the texture of the cookie was good, the flavor was reduced.
【００５４】（比較例７）実施例８において、水分を含
ませた鉄粉系脱酸素剤を通気性包材に入れて充填した脱
酸素剤包装体である市販自力反応型脱酸素剤（商品名；
エージレスＺ−３０ＰＴ、三菱ガス化学（株）製）を使
用したこと以外は、実施例８と同様に行った。脱酸素剤
包装体とクッキーとを封入した密封袋を、25℃、１ヶ月
保存した後の袋内の酸素濃度は０．１％以下であった。
クッキーは風味は良好であったが、若干湿ったために、
本来の食感は損なわれていた。(Comparative Example 7) In Example 8, a commercially available self-reactive oxygen absorber (commercially available) was used as an oxygen absorber package in which an iron powder-based oxygen absorber impregnated with water was placed in a gas-permeable packaging material and filled. Name;
Example 8 was performed except that Ageless Z-30PT, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used. After the sealed bag enclosing the oxygen absorber package and the cookies was stored at 25 ° C. for one month, the oxygen concentration in the bag was 0.1% or less.
The cookies were good in flavor, but slightly wet,
The original texture was impaired.
【００５５】（実施例９）真空乾燥機に平均粒径７０μ
ｍ、最大粒径１５０μｍの鉄粉１００重量部を入れて６
０ｍｍHgの減圧下に攪拌しながら、ヨウ素５重量部とヨ
ウ化ナトリウム５重量部を溶解した水溶液を噴霧し、12
0℃で１時間乾燥して、水分含有量が０．１重量％以下
で粒状の脱酸素剤を得た。 ＜脱酸素性多層体の製造＞直鎖状低密度ポリエチレンか
らなるシートを加熱軟化し、その上に実施例９で得た脱
酸素剤を散布し、さらに溶融した直鎖状低密度ポリエチ
レンを押し出してこの脱酸素剤を挟みこみ、押し出した
樹脂側から鏡面仕上げした冷却ロールを当て、脱酸素剤
１００重量部と直鎖状低密度ポリエチレン４０重量部か
らなる脱酸素性樹脂組成物からなる厚さ２５０μｍの脱
酸素性シートを得た。次いで、単軸押出機２台を備え
た、Ｔダイ、冷却ロールからなる共押出機を用い、酸素
透過層として酸化チタン（平均粒径０．２５μｍ、比重
４ｇ／ｃｃ）を１０重量％配合した直鎖状低密度ポリエ
チレンを冷却ロールを当てた面上に押出し、他面にエチ
レンビニルアルコールフィルム及びポリプロピレンフィ
ルムをラミネートし、直鎖状低密度ポリエチレン層（内
層：７０μｍ）／脱酸素剤層（２５０μｍ）／変性ポリ
オレフリン層（接着剤層：１０μｍ）／エチレンビニル
アルコール層（バリア層：２０μｍ）／変性ポリオレフ
リン層（接着材層：１０μｍ）／ポリプロピレン層
（外：２５０μｍ）の構成からなる脱酸素性多層体を得
た。このシートを12cm（縦）×18cm(横)×1.5cm（深
さ）の形に成形し脱酸素トレーを得た。このトレーに水
分活性０．３のビタミンＣを５０mg含有する錠剤状の健
康食品１５０錠と空気３００ｍｌを入れ、トップフィル
ムに直鎖状低密度ポリエチレン／接着層／アルミ箔／ポ
リプロピレンのフィルムを用いて密封した。該トレーを
30℃、50%RHの環境下に６ヶ月保存した後、系内の酸素
濃度を測定したところ０．０３％であり、内容物である
健康食品のビタミンＣの総量を測定したところ、ビタミ
ンＣの保存率は９２％であった。Example 9 An average particle size of 70 μm was applied to a vacuum dryer.
m, 100 parts by weight of iron powder having a maximum particle size of 150 μm
While stirring under a reduced pressure of 0 mmHg, an aqueous solution in which 5 parts by weight of iodine and 5 parts by weight of sodium iodide were dissolved was sprayed, and 12
After drying at 0 ° C. for 1 hour, a granular oxygen absorber having a water content of 0.1% by weight or less was obtained. <Production of oxygen-depleted multilayer body> A sheet made of linear low-density polyethylene was softened by heating, and the oxygen-absorbing agent obtained in Example 9 was sprayed thereon, and then the molten linear low-density polyethylene was extruded. A chilled roll having a mirror-finished surface applied from the extruded resin side with the lever oxygen scavenger sandwiched therebetween has a thickness of 100% by weight of oxygen scavenger and 40% by weight of linear low-density polyethylene. A 250 μm oxygen-absorbing sheet was obtained. Then, using a co-extruder comprising a T die and a cooling roll equipped with two single-screw extruders, 10% by weight of titanium oxide (average particle size: 0.25 μm, specific gravity: 4 g / cc) was blended as an oxygen permeable layer. A linear low-density polyethylene is extruded on a surface to which a cooling roll is applied, and an ethylene vinyl alcohol film and a polypropylene film are laminated on the other surface, and a linear low-density polyethylene layer (inner layer: 70 μm) / oxygen absorber layer (250 μm) ) / Modified polyolefin layer (adhesive layer: 10 μm) / ethylene vinyl alcohol layer (barrier layer: 20 μm) / modified polyolefin layer (adhesive layer: 10 μm) / polypropylene layer (outside: 250 μm) I got a body. This sheet was formed into a shape of 12 cm (length) × 18 cm (width) × 1.5 cm (depth) to obtain a deoxygenation tray. Put 150 tablets of healthy food containing 50 mg of vitamin C having a water activity of 0.3 and 300 ml of air into the tray, and use a linear low density polyethylene / adhesive layer / aluminum foil / polypropylene film as the top film. Sealed. The tray
After storing in an environment of 30 ° C. and 50% RH for 6 months, the oxygen concentration in the system was measured to be 0.03%, and the total amount of vitamin C in the health food, which was the content, was measured. Was 92%.
【００５６】（比較例８）ヨウ素５重量部とヨウ化ナト
リウム５重量部を溶解した水溶液の代わりに塩化ナトリ
ウム１０重量部を溶解した水溶液を使用して実施例９に
係る脱酸素剤を得たこと以外は実施例７と同様にして、
低水分物品の包装体を製造し、その保存テストを実施し
た。６ヶ月保存した後、系内の酸素濃度を測定したとこ
ろ４．５％であり、内容物である健康食品のビタミンＣ
の総量を測定したところ、ビタミンＣの保存率は６２％
であり、ビタミンＣの減少が認められた。Comparative Example 8 An oxygen absorber according to Example 9 was obtained by using an aqueous solution in which 10 parts by weight of sodium chloride was dissolved instead of an aqueous solution in which 5 parts by weight of iodine and 5 parts by weight of sodium iodide were dissolved. Except that, in the same manner as in Example 7,
A package of low-moisture articles was manufactured and its storage test was performed. After storage for 6 months, the oxygen concentration in the system was measured and found to be 4.5%.
When the total amount of vitamin C was measured, the preservation rate of vitamin C was 62%
And a decrease in vitamin C was observed.
【００５７】[0057]
【発明の効果】本発明によれば、低水分環境下において
も、十分酸素吸収反応を達成することができる脱酸素剤
組成物、及び、これと熱可塑性樹脂からなる脱酸素樹脂
組成物又は脱酸素性シートが提供される。本発明の脱酸
素剤組成物、脱酸素樹脂組成物又は脱酸素性シートを通
気性包装材料により包装してなる脱酸素剤包装体、及
び、この脱酸素樹脂組成物又は脱酸素性シートを使用し
てなるラベル型脱酸素剤、パッキン型脱酸素剤及び脱酸
素性多層体は、高い水分活性を有する物品はもちろん、
粉末食品の如く乾燥された食品等の被保存物を、品質低
下や性状低下を来すことなく、低酸素環境にして確実に
保存せしめることができる。しかも、包装材からの水分
が被保存物に移行することもないために、吸湿の嫌われ
る食品、粉体物質、健康食品及び医薬品等の比較的低い
水分を有する物品にも湿気を与えることなく脱酸素し
て、酸素に起因する劣化を防止して保存することができ
る。本発明の脱酸素剤組成物及び脱酸素樹脂組成物は、
水分保持体の共存を必要としない、低水分物品の脱酸素
保存方法を提供する。According to the present invention, an oxygen scavenger composition capable of sufficiently achieving an oxygen absorption reaction even in a low moisture environment, and an oxygen scavenging resin composition or a scavenging resin composition comprising the same and a thermoplastic resin. An oxygenate sheet is provided. The oxygen absorber composition, the oxygen absorber resin composition or the oxygen absorber sheet obtained by packaging the oxygen absorber resin composition or the oxygen absorber sheet with a breathable packaging material, and the oxygen absorber resin composition or the oxygen absorber sheet are used. Label-type oxygen absorbers, packing-type oxygen absorbers and oxygen-absorbing multilayers are not only articles having high water activity,
Preserved objects such as dried foods such as powdered foods can be reliably stored in a low oxygen environment without lowering the quality or properties. In addition, since moisture from the packaging material does not migrate to the object to be preserved, it does not give moisture to articles having relatively low moisture such as foods, powder substances, health foods, and pharmaceuticals that do not absorb moisture. It can be stored by deoxygenation to prevent deterioration due to oxygen. The oxygen scavenger composition and the oxygen scavenging resin composition of the present invention,
Provided is a method for deoxidizing and preserving low moisture articles, which does not require the coexistence of a moisture retainer.
Claims (25)
記載の脱酸素剤組成物。2. The method according to claim 1, further comprising adding a metal iodide.
The oxygen scavenger composition according to any one of the preceding claims.
化物又はアルカリ土類金属のヨウ化物である請求項２記
載の脱酸素剤組成物。3. The oxygen scavenger composition according to claim 2, wherein said metal iodide is an alkali metal iodide or an alkaline earth metal iodide.
ヨウ化カリウム又はヨウ化カルシウムである請求項２記
載の脱酸素剤組成物。4. The method according to claim 1, wherein the metal iodide is sodium iodide,
The oxygen scavenger composition according to claim 2, which is potassium iodide or calcium iodide.
１００重量部当たり０．０１〜２０重量部であり、かつ
ヨウ素に対する金属ヨウ化物の重量比が、０．１〜５で
ある請求項２記載の脱酸素剤組成物。5. The sum of the weights of iodine and metal iodide is 0.01 to 20 parts by weight per 100 parts by weight of iron powder, and the weight ratio of metal iodide to iodine is 0.1 to 5. The oxygen scavenger composition according to claim 2.
％以下である請求項１又は２記載の脱酸素剤組成物。6. The oxygen scavenger composition according to claim 1, wherein the water content of the oxygen scavenger composition is 1% by weight or less.
化物の混合物が被覆されている請求項２記載の脱酸素剤
組成物。7. The oxygen scavenger composition according to claim 2, wherein the surface of said iron powder is coated with a mixture of said iodine and metal iodide.
樹脂からなる脱酸素性樹脂組成物。8. An oxygen-absorbing resin composition comprising the oxygen-absorbing composition according to claim 1 and a thermoplastic resin.
樹脂からなる脱酸素性樹脂組成物。9. An oxygen-absorbing resin composition comprising the oxygen-absorbing composition according to claim 2 and a thermoplastic resin.
部、金属ヨウ化物０．０１〜２０重量部及びヨウ素０．
０１〜２０重量部からなる請求項９記載の脱酸素性樹脂
組成物。10. The oxygen scavenger composition comprises 100 parts by weight of iron powder, 0.01 to 20 parts by weight of metal iodide and 0.1 part by weight of iodine.
The oxygen-absorbing resin composition according to claim 9, comprising 0.01 to 20 parts by weight.
属ヨウ化物の混合物により被覆された鉄粉からなる請求
項１０記載の脱酸素性樹脂組成物。11. The oxygen-absorbing resin composition according to claim 10, wherein said oxygen-absorbing composition comprises iron powder coated with a mixture of said iodine and metal iodide.
ウ化物又はアルカリ土類金属のヨウ化物である請求項９
記載の脱酸素性樹脂組成物。12. The metal iodide is an alkali metal iodide or an alkaline earth metal iodide.
The deoxidizing resin composition as described in the above.
ウ化物のヨウ素イオン（Ｉ-）の重量が、ヨウ素（Ｉ2）
の重量の１／２より大きい請求項９記載の脱酸素性樹脂
組成物。13. The weight of the iodine ion (I − ) of the metal iodide per weight of the oxygen scavenger composition is iodine (I 2 ).
The oxygen-absorbing resin composition according to claim 9, which is larger than 1/2 of the weight of the resin.
重量％以下である請求項８又は９記載の脱酸素剤樹脂組
成物。14. The water content of the oxygen scavenger composition is 1
The oxygen-absorbing resin composition according to claim 8 or 9, which is not more than 10% by weight.
酸素剤組成物を、通気性包装材料からなる小袋に充填し
てなる脱酸素剤包装体。15. An oxygen-absorbing agent package obtained by filling the oxygen-absorbing agent composition according to any one of claims 1 to 7 into a small bag made of a breathable packaging material.
脱酸素性樹脂組成物からなる厚さ２０μｍ〜５ｍｍの脱
酸素性シート。16. An oxygen-absorbing sheet having a thickness of 20 μm to 5 mm, comprising the oxygen-absorbing resin composition according to any one of claims 8 to 14.
なくとも１軸方向に、１．５〜１２倍の範囲で延伸した
多孔性の脱酸素性シート。17. A porous oxygen-absorbing sheet obtained by stretching the oxygen-absorbing sheet according to claim 16 in at least one axial direction in a range of 1.5 to 12 times.
トを通気性包装材料により包装してなる小袋型の脱酸素
剤包装体。18. A small bag-type oxygen-absorbing agent package obtained by packaging the oxygen-absorbing sheet according to claim 16 with a breathable packaging material.
脱酸素性シート、及び、貼着用の粘着剤が積層されてな
るラベル型脱酸素剤。19. A label-type oxygen absorber obtained by laminating an air-permeable packaging material, the oxygen-absorbing sheet according to claim 16 and an adhesive for sticking.
又は１７記載の脱酸素性シートが固定され、瓶口と接触
する部分にはバリア性パッキングがあたるように配され
たパッキング形態からなるパッキン型脱酸素剤。20. A breathable wrapping material is used in a central portion.
Or a packing type oxygen absorbing agent having a packing form, wherein the oxygen absorbing sheet according to 17 is fixed, and a portion in contact with the bottle mouth is provided with a barrier packing.
過層、請求項１６又は１７記載の脱酸素性シートからな
る脱酸素層、及び、ガスバリアー性材料からなるガスバ
リアー層が積層されてなる脱酸素性多層体。21. An oxygen-permeable layer made of an oxygen-permeable thermoplastic resin, a deoxygenation layer made of the oxygen-desorbing sheet according to claim 16 or 17, and a gas barrier layer made of a gas-barrier material. Deoxidized multilayer body.
物を、請求項１５記載の脱酸素剤包装体と共にガスバリ
ヤー性容器に収納し密閉する低水分含有物品の保存方
法。22. A method for preserving a low moisture content article, comprising storing an object to be preserved having a water activity of 0.1 to 0.7 in a gas barrier container together with the oxygen scavenger package according to claim 15.
を、請求項１６又は１７記載の脱酸組成シートと共に、
ガスバリヤー性容器に密閉する低水分物品の保存方法。23. A preservation object having a water activity of 0.1 to 0.7, together with the deoxidizing composition sheet according to claim 16 or 17,
A method for storing low-moisture articles sealed in a gas barrier container.
を、少なくとも一部が請求項２０記載の脱酸素性多層体
からなる容器に密閉する低水分物品の保存方法。24. A method for preserving a low-moisture article, wherein at least a part of an object to be preserved having a water activity of 0.1 to 0.7 is hermetically sealed in a container comprising the deoxidized multilayer body according to claim 20.
０．５である請求項２２〜２４記載の保存方法。25. The water activity of the object to be preserved is 0.2 to 0.2.
25. The storage method according to claim 22, wherein the value is 0.5.
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|---|---|---|---|
| JP14973099A JP4085218B2 (en) | 1998-06-03 | 1999-05-28 | Oxygen scavenger composition and storage method |
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| JP10-154461 | 1998-06-03 | ||
| JP15446198 | 1998-06-03 | ||
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008539430A (en) * | 2005-04-28 | 2008-11-13 | アキュメトリックス インコーポレイテッド | Method and apparatus for stabilizing arachidonic acid for use in platelet function assays |
| WO2015147305A1 (en) * | 2014-03-28 | 2015-10-01 | テルモ株式会社 | Packaged drug-filled container |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101521023B1 (en) * | 2013-08-08 | 2015-05-20 | 주식회사 티피지 | Deoxidation agent for microwave oven, package for packaging the same and preparing method thereof |
-
1999
- 1999-05-28 JP JP14973099A patent/JP4085218B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008539430A (en) * | 2005-04-28 | 2008-11-13 | アキュメトリックス インコーポレイテッド | Method and apparatus for stabilizing arachidonic acid for use in platelet function assays |
| JP2012181212A (en) * | 2005-04-28 | 2012-09-20 | Accumetrics Inc | Method and system for stabilization of arachidonic acid for use in platelet function assay |
| WO2015147305A1 (en) * | 2014-03-28 | 2015-10-01 | テルモ株式会社 | Packaged drug-filled container |
| JPWO2015147305A1 (en) * | 2014-03-28 | 2017-04-13 | テルモ株式会社 | Packaged drug filling container body |
| US10065784B2 (en) | 2014-03-28 | 2018-09-04 | Terumo Kabushiki Kaisha | Packaged medicine-filled container |
| US10329073B2 (en) | 2014-03-28 | 2019-06-25 | Terumo Kabushiki Kaisha | Packaged medicine-filled container |
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