JPH02229840A - Oxygen absorbing sheet - Google Patents
Oxygen absorbing sheetInfo
- Publication number
- JPH02229840A JPH02229840A JP1306204A JP30620489A JPH02229840A JP H02229840 A JPH02229840 A JP H02229840A JP 1306204 A JP1306204 A JP 1306204A JP 30620489 A JP30620489 A JP 30620489A JP H02229840 A JPH02229840 A JP H02229840A
- Authority
- JP
- Japan
- Prior art keywords
- oxygen
- sheet
- weight
- iron powder
- ethylene
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000001301 oxygen Substances 0.000 title claims abstract description 81
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 81
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002250 absorbent Substances 0.000 claims abstract description 23
- 230000002745 absorbent Effects 0.000 claims abstract description 23
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 19
- 239000005977 Ethylene Substances 0.000 claims abstract description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 229920001577 copolymer Polymers 0.000 claims abstract description 11
- 238000012545 processing Methods 0.000 claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- 239000011342 resin composition Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 6
- 239000004711 α-olefin Substances 0.000 claims abstract description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000008096 xylene Substances 0.000 claims abstract description 3
- 239000006096 absorbing agent Substances 0.000 claims description 19
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- -1 propylene, propylene Chemical group 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- 229920001400 block copolymer Polymers 0.000 claims description 3
- 239000002184 metal Chemical class 0.000 claims description 3
- 229910052751 metal Chemical class 0.000 claims description 3
- 229920005604 random copolymer Polymers 0.000 claims description 3
- 229920001684 low density polyethylene Polymers 0.000 claims description 2
- 239000004702 low-density polyethylene Substances 0.000 claims description 2
- 229920001384 propylene homopolymer Polymers 0.000 claims description 2
- 229920001903 high density polyethylene Polymers 0.000 claims 1
- 239000004700 high-density polyethylene Substances 0.000 claims 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 abstract description 2
- 239000001110 calcium chloride Substances 0.000 abstract description 2
- 229910001628 calcium chloride Inorganic materials 0.000 abstract description 2
- 239000011780 sodium chloride Substances 0.000 abstract description 2
- 235000011148 calcium chloride Nutrition 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 7
- 238000004806 packaging method and process Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 208000032484 Accidental exposure to product Diseases 0.000 description 2
- 229940123973 Oxygen scavenger Drugs 0.000 description 2
- 239000004708 Very-low-density polyethylene Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000021485 packed food Nutrition 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 2
- 229920001866 very low density polyethylene Polymers 0.000 description 2
- 244000025272 Persea americana Species 0.000 description 1
- 235000008673 Persea americana Nutrition 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 241000208422 Rhododendron Species 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910001567 cementite Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000021067 refined food Nutrition 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Packages (AREA)
- Wrappers (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、酸素吸収シートに関する．さらに詳しくは、
取扱いが容易であり、酸素吸収能力を制御した酸素吸収
シートに関する．
く従来の技術〉
脱酸素荊は食品をはじめ、種々の製品の保存に際して酸
素が好まれないような場合に、酸素の除去を目的として
多方面において使用されている．例えば酸素吸収剤とし
ては特開昭６２ − ２３４５４４号公報に示されるよ
うな鉄粉などが好んで用いられているが、粉体の酸素吸
収剤、特に微粉のものは、空気中で酸素を吸収し易く、
特に鉄系の酸素吸収剤の場合は自然発火性でさえあるた
め取扱いが難しい．
特公昭６２ − ５４７０４号公報に示される粉体の酸
素吸収荊を通気度のある素材で包装する方法は、粉体の
密封が完全でないと、粉体が外部に漏れるという問題が
ある．また、酸素吸収剤は通気性の包装素材面から酸素
吸収を行うために粉体の酸素吸収剤表面部で反応・硬化
する．このため、内部までの吸収反応が期待できず、結
果的に吸収剤の充填量に比例した酸素吸収特性が発揮さ
れないため、酸素吸収速度が充分に制御できないという
問題があった．
酸素吸収剤の包装方法としては特開昭５５−１１６４３
６号公報に示されるような方法等が提案されているが、
少量の酸素吸収剤を正確にかつ高速で充填することは極
めて難しい上に高価な自動充填包装機が必要である．ま
た、このように酸素吸収剤を包装したものは通常食品と
一緒に包装されていることが多く、誤って酸素吸収剤を
食べてしまうケースもあり得る．
また、シートタイプのものとしては、特開昭５５− ４
４３４４号公報に示されるように活性酸化鉄からなる酸
素吸収剤をポリエチレン等の熱可塑性樹脂とブレンドレ
シート杖にしたものがあるが、酸素吸収能が必ずしも十
分とはいえない．特開昭５５−１０９４２８号公報に示
されるようにシートまたはフィルム状の有孔基材の孔内
に酸素吸収剤を充填したものは、取扱いによって酸素吸
収剤が脱落したり、また脱落防止用の通気性フィルム層
を設けたものは高価になるという欠点がある．特開昭６
０−１８３３７３号公報に示されるように連続気泡構造
を有する発泡ポリウレタンシ一トの気泡内に脱酸素剤粉
末が埋入されたものは、連続気泡を工業的に安定して得
ることが難しい上に材料自体が高価であり実用的でない
．
〈発明が解決しようとする課題〉
本発明の目的は取扱いが容易で酸素吸収剤の外部への漏
れがなく、酸素唆収能力を任意に制御でき、充填包装と
いう技術的に難しい工程を必要とせず、かつ、誤食防止
効果の大きい酸素吸収剤を提供することである．
〈課題を解決するための手段〉
本発明者らは上記ｉＪ題に鑑み、取扱いが容易で酸素吸
収剤の外部への漏れがな《、酸素吸収能力を任意に制御
できる脱酸素剤について鋭意研究を続けてきた．その結
果、熱可塑性樹脂と酸素吸収剤とを混合し溶融成形して
得られたフィルムを特定条件で延伸加工することにより
目的とする酸素吸収シートが得られることを見出し本発
明を完成するに至った．
すなわち、本発明は、熱可塑性樹脂１５〜７０重量％と
酸素吸収剤３０〜８５重量％からなる樹脂組成物を厚さ
１０μｍ〜５閣にシート加工した後、少なくとも一軸方
向に１．５〜８．０倍の倍率で延伸されたことを特徴と
する酸素吸収シートである．
本発明の酸素吸収シートは熱可塑性樹脂の中に酸素吸収
剤を溶融混練により均一に分散させ得られたフィルムま
たはシートを特定条件下で延伸することにより熱可塑性
樹脂フィルムまたはシートに小さな空隙（ミクロポイド
）を多数発生させて多孔質化したものであって、該フィ
ルムまたはシート中に均一に分散された酸素吸収剤はミ
クロポイドを通じて大気と接触しており大気中の酸素を
効果的に吸収することができる特徴を有している．本発
明で使用される酸素吸収剤としては鉄粉または鉄粉と電
解質からなるものが好ましいが、鉄粉と電解質からのな
るものがより好ましい．鉄粉には鉄系副成分として炭化
鉄や鉄の酸化物などを表面等に含み、該副成分の含有量
は、通常０．１〜２０重量％である．鉄粉の粒径は通常
０．１〜１００μｍくらいのものが好ましく、より好ま
しくは１〜５０μｍである。粒径が大きすぎると比表面
積が小さくなるため酸素吸収能が低く、また、薄物シー
トの製膜が出来ないという制限もある．一方、小さすぎ
ると熱可塑性樹脂中での分散性が悪化するという問題の
他に工業的に安定して小粒径鉄粉を入手することが難し
いという問題がある．また、鉄粉は比表面積が１０００
ｃＪ／ ｇ以上で通常は１０００ｃｍ２／ ｇ以上が好
まし＜ 、５０００ｃｍ２／ ｇ以上がさらに好ましい
．従って鉄粉の形状としては多孔賞またはそれに近いも
のが最適である．１！１解質は鉄粉の酸素吸収速度を促
進するものであり、例えばハロゲン化物、炭酸塩、硫酸
塩または水酸化物等である．これらの塩類の中で好まし
いのはハロゲン化物であり、さらに好ましくはＣａＣ１
ｘ， ＮａＣ１，１１ｇｃ ｌ．等である．電解質は前
記鉄粉の表面に付着またはコーティングして使用するの
が好ましいが、鉄粉との単なるブレンドで使用してもよ
い． また、電解質の添加量は０．１〜１０ｗｔ％が好
ましいが、鉄粉の表面に付着またはコーティングしたタ
イプの場合は、０．１〜５重量％の添加量が最も実用的
である。添加Ｗが１０重量％を越すと水分を吸湿しすぎ
てシート全体が水で濡れ商品価値が失われる．
本発明で使用される酸素吸収剤は湿度が低い場合には殆
ど酸素を吸収せず水分の充分な存在下（例えば、相対湿
度５０％以上の大気中）で初めて酸素を吸収するため取
扱いが容易であるという特徴を有する．
本発明の酸素吸収シートにおいて酸素吸収剖の含有量が
３０重量％未満の場合はミクロボイドの発生が少ないた
め大気と連帯するミクロボイドも少なくなり、その結果
大気中の酸素を吸収する能力が極めて低く実用に供し得
ない．一方、８５重量％を超す場合は得られる酸素吸収
シートが著しく跪くなって実用に供し得ない．
本発明で使用される熱可塑性樹脂としては、高圧法で得
られる分岐低密度ポリエチレン、エチレンと炭素数４〜
１２のα−オレフィンとの共重合体、高密度ボリエ千レ
ン、エチレンおよび／またはブテン−１とプロピレンと
のランダムおよびブロック共重合体、プロピレン単独重
合体、酢酸ビニルおよび／または（メタ）アクリル酸エ
ステルとエチレンとの共重合体、エチレンとアクリル酸
との共重合体の金属塩から選ばれる１種または２種以上
の混合物があるが、エチレンと炭素数４〜ｌ２のα−オ
レフィンとの共重合体、エチレンおよび／またはブテン
−１とプロピレンとのランダムおよびブロック共重合体
、酢酸ビニルおよび／または（メタ）アクリル酸エステ
ルとエチレンとの共重合体、エチレンとアクリル酸との
共重合体の金属塩が好ましい．さらに好ましくはエチレ
ンと炭素数４〜１２のα−オレフィンとの共重合体であ
って、密度が０．８７０＝ ０．９１５ ｇ ／ ｃ４
、２５℃におけるキシレン抽出成分（以下、ｒｃｘｓ成
分Ｊという）の重量平均分子鎖長が１０００〜９０００
人で該抽出成分を１８〜４５重量％含むもの（以下、「
超低密度ポリエチレン」という）および超低密度ポリエ
チレンを少なくとも１０重量％以上含む熱可塑性樹脂が
挙げられる．
本発明において使用する熱可塑性樹脂として超低密度ポ
リエチレンを１０重量％以上含むものは、酸素吸収剤の
溶融混練時の分散性が良好で、得られるシートの延伸性
が優れ高倍率の延伸が可能である．
また、超低密度ポリエチレンは例えば特開昭５６− ９
９２０９号公報、特開昭５９ − ２８００１ １号公
報等公知の技術によって製造することができる．熱可塑
性樹脂と酸素吸収剤からなる延伸前の樹脂組成物のシー
ト厚さは用途目的により様々であるが、ＩＯμｍ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
酸素吸収シートを使用しなければならないケースもあり
包装される食品本体より大きく目立ってしまうという問
題が生じる。一方、５ｍを超す場合は、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無理な場合もある，
また、得られたシートの延伸倍率について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酸素吸
収剤が大気と充分に接触できないため実用に充分な酸素
吸収能力を得ることができない．また、８．０倍を越え
ると得られる酸素吸収シートは引裂などのフィルム強度
が著しく低下し、わずかな外力で破損するため実用に供
し得ない。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to an oxygen absorbing sheet. For more details,
This article relates to an oxygen-absorbing sheet that is easy to handle and has a controlled oxygen-absorbing capacity. Prior Art> Oxygen-absorbing rhododendrons are used in a wide range of applications for the purpose of removing oxygen when preserving food and other products where oxygen is not preferred. For example, iron powder as shown in JP-A No. 62-234544 is preferably used as an oxygen absorbent, but powder oxygen absorbers, especially fine powders, do not absorb oxygen in the air. easy to do,
In particular, iron-based oxygen absorbers are difficult to handle because they are even spontaneously flammable. The method disclosed in Japanese Patent Publication No. 62-54704, in which oxygen-absorbing powder is packaged with a breathable material, has the problem that if the powder is not completely sealed, the powder may leak outside. In addition, the oxygen absorber reacts and hardens on the surface of the powder oxygen absorber in order to absorb oxygen from the air-permeable packaging material surface. For this reason, an absorption reaction that reaches the interior cannot be expected, and as a result, oxygen absorption characteristics proportional to the amount of absorbent filled cannot be exhibited, resulting in the problem that the oxygen absorption rate cannot be sufficiently controlled. A method for packaging oxygen absorbers is disclosed in Japanese Patent Application Laid-Open No. 55-11643.
Although methods such as those shown in Publication No. 6 have been proposed,
Filling small amounts of oxygen absorbers accurately and at high speed is extremely difficult and requires expensive automatic filling and packaging machines. In addition, oxygen absorbers packaged in this way are often packaged together with food, and there are cases where oxygen absorbers are accidentally eaten. In addition, as a sheet type, JP-A-55-4
As shown in Japanese Patent No. 4344, there is a receipt cane made by blending an oxygen absorbent made of activated iron oxide with a thermoplastic resin such as polyethylene, but it cannot be said that the oxygen absorption capacity is necessarily sufficient. As shown in Japanese Patent Application Laid-Open No. 55-109428, a sheet or film-like perforated base material in which the pores are filled with an oxygen absorbent may cause the oxygen absorbent to fall off due to handling, or may require air permeability to prevent it from falling off. The disadvantage of those with a film layer is that they are expensive. Tokukai Showa 6
As shown in Publication No. 0-183373, a foamed polyurethane sheet having an open cell structure in which oxygen scavenger powder is embedded in the cells is difficult to stably obtain open cells industrially. However, the material itself is expensive and impractical. <Problems to be Solved by the Invention> The objects of the present invention are to provide an oxygen absorbent that is easy to handle, does not leak to the outside, can arbitrarily control the oxygen absorption capacity, and does not require the technically difficult process of filling and packaging. It is an object of the present invention to provide an oxygen absorbent that is highly effective in preventing accidental ingestion. <Means for Solving the Problems> In view of the above-mentioned iJ problem, the present inventors have conducted intensive research into an oxygen scavenger that is easy to handle, does not leak to the outside, and can arbitrarily control its oxygen absorption capacity. I have continued to do so. As a result, they discovered that the desired oxygen-absorbing sheet could be obtained by stretching a film obtained by mixing and melt-molding a thermoplastic resin and an oxygen absorber under specific conditions, leading to the completion of the present invention. Ta. That is, in the present invention, after processing a resin composition consisting of 15 to 70% by weight of a thermoplastic resin and 30 to 85% by weight of an oxygen absorber into a sheet with a thickness of 10 to 5 μm, the sheet has a thickness of 1.5 to 8 μm in at least one axis direction. This is an oxygen-absorbing sheet characterized by being stretched at a magnification of 0.0 times. The oxygen absorbing sheet of the present invention is produced by uniformly dispersing an oxygen absorbent in a thermoplastic resin by melt-kneading and then stretching the obtained film or sheet under specific conditions. ), and the oxygen absorbent uniformly dispersed in the film or sheet is in contact with the atmosphere through micropoid and can effectively absorb oxygen in the atmosphere. It has the characteristics of being able to The oxygen absorbent used in the present invention is preferably one made of iron powder or iron powder and an electrolyte, and more preferably one made of iron powder and an electrolyte. Iron powder contains iron carbide, iron oxide, etc. as iron-based subcomponents on its surface, and the content of these subcomponents is usually 0.1 to 20% by weight. The particle size of the iron powder is usually preferably about 0.1 to 100 μm, more preferably 1 to 50 μm. If the particle size is too large, the specific surface area will be small, resulting in low oxygen absorption capacity, and there is also the limitation that thin sheets cannot be formed. On the other hand, if the particle size is too small, there is the problem that the dispersibility in the thermoplastic resin deteriorates, as well as the problem that it is difficult to obtain small-sized iron powder in an industrially stable manner. In addition, iron powder has a specific surface area of 1000
cJ/g or more, preferably 1000cm2/g or more, and more preferably 5000cm2/g or more. Therefore, the best shape of iron powder is porous or similar. 1!1 Solutes promote the oxygen absorption rate of iron powder, such as halides, carbonates, sulfates, or hydroxides. Among these salts, halides are preferred, and CaC1 is more preferred.
x, NaCl, 11gc l. etc. The electrolyte is preferably used by being attached or coated on the surface of the iron powder, but it may also be used simply as a blend with the iron powder. Further, the amount of electrolyte added is preferably 0.1 to 10 wt%, but in the case of a type that is attached or coated on the surface of iron powder, the amount of addition of 0.1 to 5 wt% is most practical. If the added W exceeds 10% by weight, too much moisture will be absorbed, the entire sheet will become wet and its commercial value will be lost. The oxygen absorbent used in the present invention absorbs almost no oxygen when the humidity is low, and only absorbs oxygen in the presence of sufficient moisture (for example, in the atmosphere with a relative humidity of 50% or more), so it is easy to handle. It has the characteristic that When the content of oxygen absorbing material in the oxygen absorbing sheet of the present invention is less than 30% by weight, the generation of microvoids is small, so the number of microvoids that connect with the atmosphere is also small, and as a result, the ability to absorb atmospheric oxygen is extremely low for practical use. It cannot be provided to On the other hand, if the content exceeds 85% by weight, the resulting oxygen-absorbing sheet will become extremely weak and cannot be put to practical use. The thermoplastic resin used in the present invention includes branched low-density polyethylene obtained by a high-pressure method, ethylene and carbon atoms having 4 to 4 carbon atoms.
copolymers with α-olefins of 12, dense polyethylene, random and block copolymers of propylene with ethylene and/or butene-1, propylene homopolymers, vinyl acetate and/or (meth)acrylic acid There are one or more mixtures selected from copolymers of ester and ethylene and metal salts of copolymers of ethylene and acrylic acid. polymers, random and block copolymers of ethylene and/or butene-1 and propylene, copolymers of vinyl acetate and/or (meth)acrylic acid esters with ethylene, copolymers of ethylene and acrylic acid. Metal salts are preferred. More preferably, it is a copolymer of ethylene and an α-olefin having 4 to 12 carbon atoms, and has a density of 0.870=0.915 g/c4
, the weight average molecular chain length of the xylene extracted component (hereinafter referred to as rcxs component J) at 25°C is 1000 to 9000.
Those containing 18 to 45% by weight of the extract component for humans (hereinafter referred to as "
Examples include "very low density polyethylene") and thermoplastic resins containing at least 10% by weight of very low density polyethylene. The thermoplastic resin used in the present invention containing 10% by weight or more of ultra-low density polyethylene has good dispersibility of the oxygen absorber during melt-kneading, and the resulting sheet has excellent stretchability and can be stretched at high ratios. It is. Furthermore, ultra-low density polyethylene is disclosed in Japanese Patent Application Laid-open No. 56-9, for example.
It can be manufactured using known techniques such as No. 9209 and Japanese Unexamined Patent Publication No. 59-280011. The sheet thickness of a resin composition made of a thermoplastic resin and an oxygen absorber before stretching varies depending on the purpose of use, but if it is less than IO μm, an oxygen absorbing sheet with a very large area is required to obtain the desired oxygen absorption capacity. In some cases, it may be necessary to use a packaged food product, which causes the problem that it is larger and more conspicuous than the packaged food itself. On the other hand, if the length exceeds 5 m, it may be difficult to bring the sheet to a uniform stretching temperature during stretching after sheet processing, and uniform stretching may not be possible, or the stretching stress may be so large that it may not be possible with normal equipment. Furthermore, if the stretching ratio of the obtained sheet is less than 1.5 times, the generation of microvoids is small and the uniformly dispersed oxygen absorbent cannot sufficiently contact the atmosphere, making it impossible to obtain a sufficient oxygen absorption capacity for practical use. Further, if the ratio exceeds 8.0 times, the resulting oxygen-absorbing sheet will have a marked decrease in film strength such as tearing, and will be damaged by a slight external force, so it cannot be put to practical use.
シートの延伸温度については熱可塑性樹脂の融点より５
゜Ｃ程度以下の温度を設定すればよいが、例えば、ポリ
オレフィン系樹脂の場合、通常室温から７０℃程度の温
度がよく用いられる．なお、本発明の酸素吸収シートを
得るための組成物の中には、本発明の効果を実質的に損
なわない範囲で酸化防止剤、分散剤、帯電防止剤、消臭
剤、殺菌剤等を配合させることができる．本発明の酸素
吸収シートを製造する方法は例えば次の通りである．
まず、熱可塑性樹脂と酸素吸収剤とを、ロール型または
バンバリー型の混練機あるいは一軸または二軸押出機な
どを用いる通常の方法で混合あるいは混練して組成物を
得る．次いでこの組成物からインフレーション加工、カ
レンダー加工、Ｔダイ加工等の通常の成形方法によって
フィルムあるいはシートを製造し、得られたフィルムあ
るいはシートを延伸するが、延伸は一軸または二輪で行
う．一軸延伸の場合は通常ロール延伸が好ましいが、チ
ューブラー延伸で行ってもよい．また、延伸は一段でも
二段以上でも可能であり、二軸延伸の場合は同時二輪で
の延伸でもよいし、縦方向の延伸を行った後に横方向を
延伸する逐次二軸延伸でもよい．
このように酸素吸収シートの製造は熟可塑性樹脂と酸素
吸収剤からなる樹脂組成物の製造フィルムあるいはシー
トの成形および延伸という工程によりなるが、これら工
程を連続で行ってもよいし個別に行ってもよい．
〈実施例〉
以下、実施例によって詳細に説明するが、本発明はこれ
によって限定されるものではない．なお、実施例および
比較例に示した物性の測定法は以下の通りである．
酸素吸収速度：酸素吸収速度は空気１ｉに対し、酸素吸
収シートを３．７ｇの割合で密閉容器に存在させ、初期
の４時間で吸収した量から吸収速度の平均を求めたもの
である．
密閉容器とは、目盛付きのガラス製の円筒容器を水面に
立てたもので酸素が吸収されると減少した容量が水によ
って占有される仕組みとなっている．
重量平均分子鎖長：ＣＸＳ成分の重量平均分子鎖長は、
東洋曹達■製のゲル浸透クロマトグラフィー（ＧＰＣ）
８１１型にカラムとしてＧ？ｌＨ６ − ＨＤを２本取
り付け、１３０゜Ｃの条件下でポリスチレンを基準とし
て測定した．
密 度 ：樹脂の密度はＪＩＳ Ｋ６７６０−１９
８１に準拠して密度勾配管法により２３゜Ｃで測定した
．メルトフローレート： ＪＩＳ Ｋ６７６０−１９８
１に準拠して測定した．
比表面積：試料約０．３ｇを吸着試料管に入れ、窒素３
０ｖｏｌ％、ヘリウム７０νｏｌ％の混合ガスのフロー
（３０ＩＩｉＺ分）下、２００℃で２０分間加熱処理を
行ない放冷後、約−１９６゜Ｃの液体窒素の中に吸着試
料管を入れＮ，ガスの吸着量を２２゜Ｃ１気圧の吸着量
（Ｖ）として測定した．ＢＥＴ式より近似して求めた次
式に吸着Ｍ （Ｖ）を全表面積をサンプル重量（Ｗ）で
割ることにより比表面積Ｓを算出した．
Ｓ＝Ｓｔ／Ｗ（ポ／ｇ）
注） Ｂ．Ｅ．Ｔ．式
Ｘ （Ｐｏ／Ｐ−１）
ここで
Ｐ
ＰＯ：
Ｘ ：
Ｘ一 ：
Ｃ
Ｘ一・Ｃ ｘ鵬・Ｃ
吸着ガスの蒸気圧
冷却温度での吸着ガスの飽和蒸気圧
相関圧力Ｐ／ＰＧにおいて試料表面に吸着されたガス量
（重！）
単分子層に吸着したガス量帽１）
吸着エネルギーに関する定数
ここで
（１）弐で 一〇と仮定すると次式が得られ
る．
Ｘｍ ＝ Ｘ （ １ −Ｐ／Ｐｏ）ガスの理想状態
方程式から
ＲＴ
ここで
Ｐ： 大気圧
■： 吸着又は脱着したガス量（体積）Ｍ： １モルの
吸着ガス量（重量）
Ｒ： 気体定数
Ｔ： 大気温度
Ｘを（２）に代入すると
Ｒ−Ｔ
そしてサンプルの全表面積は次式により求められる．
Ｓｔ：単分子層を形成した全表面積
即ち、サンプルの全表面積
Ｎ ： アボガド口数
Ｍ ： １モルの吸着ガス量
ＡｃＳ ： 吸着ガスの断面積
Ｒ−Ｔ
吸着ガスとして窒素を用い、２２℃１気圧のもとで上式
は次のように表される．
Ｓｔ − Ｖ （ １ −Ｐ／Ｐａ） Ｘ ４．０３
（６）ＰＯは大気圧より平均して１５＋ｗｍＨｇ
高いと仮定すると（６）式は次のように表される．（Ｐ
／Ｐｏ＝７６０／７７５）Ｓｔ−２．８４ｘｖ Ｃｒ
ｄ）
実施例！
線状密度ポリエチレンＡとして重量平均分子鎖長が３７
００人であるＣｘＳ成分２１重量％を含み、密度が０．
９００ｇ／ｃｍ２であり、メルトフローレートが１．８
ｇ／１０分であるエチレンーブテン−１共重合体（以下
、この線状低密度ポリエチレンを第２表の通りｒＡ−
Ｉ Ｊと記す）２５重量％、酸素吸収剤として鉄粉（平
均粒径４０μｍ、電解πとして塩化カルシウムをｌ＠ｔ
％含み、鉄成分としてはＦｅ ８５ｍｔ％， Ｆｅ．Ｃ
９ｗｔ％およびＦｅＯ ６ｗｔ％からなる。比表面積
９００００ｃｊ／ ｇ ） ７５重量％と分散剤として
ステアリン酸亜鉛を樹脂組成物１００重量部に対し１．
０重量部とを森田精機■製のタンブラーミキサーＭＴ５
０型によって予め混合した後、得られた混合物を神戸製
ｍｏ！Ｉ製のＢＲ型バンバリーによって１２０〜１５０
℃で５分間さらに混練して組成物を得た。The stretching temperature of the sheet is 5° below the melting point of the thermoplastic resin.
It is sufficient to set the temperature to about .degree. C. or less, but for example, in the case of polyolefin resins, temperatures from room temperature to about 70.degree. C. are often used. The composition for obtaining the oxygen-absorbing sheet of the present invention may contain antioxidants, dispersants, antistatic agents, deodorants, bactericides, etc. to the extent that the effects of the present invention are not substantially impaired. Can be combined. The method for producing the oxygen absorbing sheet of the present invention is, for example, as follows. First, a composition is obtained by mixing or kneading a thermoplastic resin and an oxygen absorbent by a conventional method using a roll-type or Banbury-type kneader, a single-screw or twin-screw extruder, or the like. Next, a film or sheet is produced from this composition by a conventional forming method such as inflation processing, calendar processing, T-die processing, etc., and the obtained film or sheet is stretched, and the stretching is carried out using a single shaft or two wheels. In the case of uniaxial stretching, roll stretching is usually preferred, but tubular stretching may also be used. Furthermore, stretching can be done in one stage or in two or more stages, and in the case of biaxial stretching, it may be simultaneous two-wheel stretching, or sequential biaxial stretching in which stretching is performed in the longitudinal direction and then in the transverse direction. In this way, the production of oxygen-absorbing sheets involves the steps of producing a resin composition consisting of a mature plastic resin and an oxygen absorbent, forming and stretching a film or sheet, and these steps may be performed continuously or individually. Good too. <Examples> The present invention will be explained in detail below using examples, but the present invention is not limited thereto. The methods for measuring the physical properties shown in Examples and Comparative Examples are as follows. Oxygen absorption rate: The oxygen absorption rate was determined by placing the oxygen absorbing sheet in a closed container at a ratio of 3.7g to 1i of air, and calculating the average absorption rate from the amount absorbed in the initial 4 hours. A closed container is a cylindrical glass container with a scale that is placed above the water surface, and the volume that decreases when oxygen is absorbed is occupied by water. Weight average molecular chain length: The weight average molecular chain length of the CXS component is
Gel permeation chromatography (GPC) manufactured by Toyo Soda
G as a column in 811 type? Two lH6-HDs were attached and measurements were made using polystyrene as a standard at 130°C. Density: Resin density is JIS K6760-19
Measurements were made at 23°C using the density gradient tube method in accordance with 81. Melt flow rate: JIS K6760-198
Measured according to 1. Specific surface area: Place approximately 0.3 g of sample into an adsorption sample tube and add 3
Heat treatment was performed at 200°C for 20 minutes under a mixed gas flow (30IIiZ minutes) of 0vol% helium and 70νol% helium, and after cooling, the adsorption sample tube was placed in liquid nitrogen at approximately -196°C and the gas was The amount of adsorption was measured as the amount of adsorption (V) at 22°C and 1 atm. The specific surface area S was calculated by dividing the adsorption M (V) by the total surface area by the sample weight (W) using the following equation, which was approximated using the BET equation. S=St/W (po/g) Note) B. E. T. Formula X (Po/P-1) where P PO: Amount of gas adsorbed on the surface (heavy!) Amount of gas adsorbed on the monomolecular layer 1) Constant regarding adsorption energy Here, assuming (1) 2 and 10, the following equation is obtained. Xm = : Substituting the atmospheric temperature St: Total surface area on which a monomolecular layer was formed, that is, total surface area of the sample N: Number of avocados M: Amount of adsorbed gas per 1 mole AcS: Cross-sectional area of adsorbed gas R-T Using nitrogen as the adsorbed gas, at 22°C and 1 atm. The above equation can be expressed as follows. St-V (1-P/Pa) X 4.03
(6) PO is on average 15+wmHg above atmospheric pressure
Assuming that it is high, equation (6) can be expressed as follows. (P
/Po=760/775) St-2.84xv Cr
d) Examples! As linear density polyethylene A, the weight average molecular chain length is 37
It contains 21% by weight of CxS components with a density of 0.00 and a density of 0.00.
900g/cm2, melt flow rate is 1.8
g/10 min (hereinafter, this linear low density polyethylene is referred to as rA-
IJ) 25% by weight, iron powder as an oxygen absorber (average particle size 40 μm, calcium chloride as electrolytic π)
%, the iron component is Fe 85mt%, Fe. C
9 wt% and 6 wt% FeO. Specific surface area: 90,000cj/g) 75% by weight and zinc stearate as a dispersant at 1.0% by weight per 100 parts by weight of the resin composition.
0 parts by weight and tumbler mixer MT5 manufactured by Morita Seiki ■
After pre-mixing with Model 0, the resulting mixture was mixed with Kobe MO! 120-150 depending on BR type Banbury made by I
The mixture was further kneaded for 5 minutes at ℃ to obtain a composition.
この組成物を南千住製作所製の６５−φ押出機によりＴ
ダイ成形（ダイス幅７００ｍ，ダイリンブ開度０．７ｍ
） Ｌ．、厚さ１閤のシートを得た．なお押出機の温度
はシリンダー１を２５０℃、シリンダー２、シリンダー
３、ヘッド及びダイスを２８０’Ｃとした，
このシートを日本製鋼■製のロール延伸機により６０″
ＣでＭＤに３．２倍に延伸し、第１表に示す通り酸素吸
収速度が１２．０ｃｍ２／Ｈｒであってこのレベルは酸
素吸収剤としての実用に充分なものである．また、この
酸素吸収シートは湿度が低い場合には殆ど酸素を吸収し
ないが、水分の充分な存在の下で初めて酸素を吸収する
ため形態が取扱い易いシートというだけでなく、機能作
用制御の面からも極めて取扱い易いものであった．さら
に、シートからの酸素吸収剤の離脱は認められなかった
．実施例２〜６
第１〜２表に示した成分と配合割合の樹ＴＭ組成物を用
いた以外は実施例１と同様に行ない酸素吸収シートを得
た．これらの酸素吸収シートは第１表に示す通り優れた
性能を有するのみならず取扱いの容易さや酸素吸収剤の
離脱についても実施例ｌと同様優れた結果となった．
比較例１〜４
第１〜２表に示した成分と配合割合の樹脂組成物を用い
た以外は実施例１と同様に行ない酸素吸収シートを得た
．しかし、第１表に示す通り性能の殆ど認められない酸
素吸収シートしか得られなかったり、酸素吸収シートが
全く得られない．〈発明の効果〉
本発明によれば、特許請求の範囲に記載された通り特定
の熱可塑性樹脂と特定の酸素吸収剤とを特定割合で含む
樹脂組成物を特定の延伸倍率下で加工することにより、
取扱いが容易で酸素吸収剤の外部への漏れがなく、酸素
吸収能力を任意に制御でき、充填包装の工程が不要でか
つ誤食防止効果の大きい酸素吸収シートを得ることがで
きた．さらに、特筆すべきは特定の酸素吸収剤を用いる
ことによりシート加工工程および実使用までの取扱いが
酸素吸収の心配もなく通常の大気中で自由に行えること
である．
このような効果は、特定の熱可塑性樹脂と特定の酸素吸
収剤を使用して酸素吸収剤を熱可塑性樹脂の中に均一に
分散させたことおよびこのようにして得られた樹脂組成
物を特定の延伸倍率下で加工し酸素吸収剤と熱可組成樹
脂の間に大気に通じるミクロボイドを多数発生させ結果
的に酸素吸収剤の大気と接触する面積を大きくしたこと
にもとすくものである．
本発明によって得られる酸素吸収シートはその特性を生
かして高含水食品、一般食品等の加工食品包装は勿論、
果物・野菜・花き等の包装、機械部品類の包装、医薬類
の包装等に使用することができる。用途目的に応じて他
の基材と組合せて使用することもできる．
＼This composition was processed using a 65-φ extruder manufactured by Minamisenju Seisakusho.
Die molding (Die width 700m, die limb opening 0.7m
) L. , a sheet with a thickness of 1 loaf was obtained. The temperature of the extruder was 250°C for cylinder 1, and 280°C for cylinders 2, 3, head, and die.
The film was stretched 3.2 times in the MD with C, and as shown in Table 1, the oxygen absorption rate was 12.0 cm2/Hr, which is sufficient for practical use as an oxygen absorbent. In addition, this oxygen-absorbing sheet absorbs almost no oxygen when the humidity is low, but it only absorbs oxygen in the presence of sufficient moisture, so it is not only a sheet that is easy to handle, but also has a good function and action control. It was also extremely easy to handle. Furthermore, no release of the oxygen absorbent from the sheet was observed. Examples 2 to 6 Oxygen-absorbing sheets were obtained in the same manner as in Example 1, except that the tree TM compositions having the components and blending ratios shown in Tables 1 and 2 were used. These oxygen absorbing sheets not only had excellent performance as shown in Table 1, but also showed excellent results in terms of ease of handling and release of the oxygen absorbent, as in Example 1. Comparative Examples 1 to 4 Oxygen-absorbing sheets were obtained in the same manner as in Example 1, except that resin compositions having the components and blending ratios shown in Tables 1 and 2 were used. However, as shown in Table 1, only oxygen absorbing sheets with little or no performance can be obtained, or no oxygen absorbing sheets can be obtained at all. <Effects of the Invention> According to the present invention, as described in the claims, a resin composition containing a specific thermoplastic resin and a specific oxygen absorber in a specific ratio can be processed under a specific stretching ratio. According to
We were able to obtain an oxygen-absorbing sheet that is easy to handle, has no leakage of the oxygen-absorbing agent to the outside, can control its oxygen-absorbing capacity at will, does not require a filling and packaging process, and is highly effective in preventing accidental ingestion. Furthermore, it is worth noting that by using a specific oxygen absorber, the sheet processing process and handling up to actual use can be carried out freely in normal atmosphere without worrying about oxygen absorption. This effect is due to the use of a specific thermoplastic resin and a specific oxygen absorber to uniformly disperse the oxygen absorber in the thermoplastic resin, and the specificity of the resulting resin composition. This is also due to the fact that by processing at a stretching ratio of , many microvoids communicating with the atmosphere are generated between the oxygen absorbent and the thermoplastic resin, and as a result, the area of the oxygen absorbent in contact with the atmosphere is increased. The oxygen absorbing sheet obtained by the present invention can be used not only for packaging processed foods such as high water content foods and general foods by taking advantage of its characteristics.
It can be used for packaging fruits, vegetables, flowers, etc., packaging for mechanical parts, packaging for pharmaceuticals, etc. It can also be used in combination with other base materials depending on the purpose of use. \
Claims (5)
〜８５重量％からなる樹脂組成物を厚さ１０μｍ〜５ｍ
ｍにシート加工した後、少なくとも一軸方向に１．５〜
８．０倍の倍率で延伸されたことを特徴とする酸素吸収
シート。(1) Thermoplastic resin 15-70% by weight and oxygen absorber 30%
A resin composition consisting of ~85% by weight is coated with a thickness of 10 μm ~ 5 m.
After sheet processing to m, at least 1.5 to 1 axial direction
An oxygen-absorbing sheet characterized by being stretched at a magnification of 8.0 times.
を特徴とする特許請求範囲第一項記載の酸素吸収シート
。(2) The oxygen absorbing sheet according to claim 1, wherein the oxygen absorbent is iron powder or iron powder and an electrolyte.
１０００ｃｍ＾２／ｇ以上である鉄粉９５〜９９．９重
量％と電解質０．１〜１０重量％とからなり、鉄粉の表
面に電解質が付着またはコーティングされていることを
特徴とする特許請求範囲第一項記載の酸素吸収シート。(3) The oxygen absorbent consists of 95 to 99.9% by weight of iron powder with a particle size of 0.1 to 100 μm and a specific surface area of 1000 cm^2/g or more and 0.1 to 10% by weight of electrolyte. The oxygen-absorbing sheet according to claim 1, wherein the surface thereof is adhered or coated with an electrolyte.
ンと炭素数４〜１２のα−オレフィンとの共重合体、高
密度ポリエチレン、エチレンおよび／またはブテン−１
とプロピレンとのランダムおよびブロック共重合体、プ
ロピレン単独重合体、酢酸ビニルおよび／または（メタ
）アクリル酸エステルとエチレンとの共重合体、エチレ
ンとアクリル酸との共重合体の金属塩から選ばれる１種
または２種以上の混合物であることを特徴とする特許請
求範囲第一項記載の酸素吸収シート。(4) Thermoplastic resin is branched low-density polyethylene, copolymer of ethylene and α-olefin having 4 to 12 carbon atoms, high-density polyethylene, ethylene and/or butene-1
selected from random and block copolymers of and propylene, propylene homopolymers, copolymers of vinyl acetate and/or (meth)acrylic acid esters with ethylene, and metal salts of copolymers of ethylene and acrylic acid. The oxygen absorbing sheet according to claim 1, which is one type or a mixture of two or more types.
共重合体が、密度０．８７０〜０．９１５ｇ／ｃｍ＾２
であり、２５℃におけるキシレン抽出成分の重量平均分
子鎖長が１０００〜９０００Åで該抽出成分を１８〜４
５重量％含むことを特徴とする特許請求の範囲第四項記
載の酸素吸収シート。(5) A copolymer of ethylene and an α-olefin having 4 to 12 carbon atoms has a density of 0.870 to 0.915 g/cm^2
When the weight average molecular chain length of the xylene extracted component at 25°C is 1000 to 9000 Å, the extracted component is 18 to 4
The oxygen absorbing sheet according to claim 4, characterized in that it contains 5% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1306204A JP2576646B2 (en) | 1988-11-24 | 1989-11-24 | Oxygen absorbing sheet |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29792188 | 1988-11-24 | ||
| JP63-297921 | 1988-11-24 | ||
| JP1306204A JP2576646B2 (en) | 1988-11-24 | 1989-11-24 | Oxygen absorbing sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02229840A true JPH02229840A (en) | 1990-09-12 |
| JP2576646B2 JP2576646B2 (en) | 1997-01-29 |
Family
ID=26561298
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1306204A Expired - Fee Related JP2576646B2 (en) | 1988-11-24 | 1989-11-24 | Oxygen absorbing sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2576646B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05115776A (en) * | 1991-04-02 | 1993-05-14 | W R Grace & Co | Mixture, product and method for scavenging oxygen |
| JP2002080647A (en) * | 2000-09-07 | 2002-03-19 | Mitsubishi Gas Chem Co Inc | Deoxidizing agent resin composition and sheet |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5534164A (en) * | 1978-09-04 | 1980-03-10 | Teijin Ltd | Oxygen capturing composition |
| JPS63139925A (en) * | 1986-07-16 | 1988-06-11 | Sumitomo Chem Co Ltd | Gas-permeable film and its production |
| JPH0272851A (en) * | 1988-09-08 | 1990-03-13 | Mitsubishi Gas Chem Co Inc | Filmy disoxidant |
-
1989
- 1989-11-24 JP JP1306204A patent/JP2576646B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5534164A (en) * | 1978-09-04 | 1980-03-10 | Teijin Ltd | Oxygen capturing composition |
| JPS63139925A (en) * | 1986-07-16 | 1988-06-11 | Sumitomo Chem Co Ltd | Gas-permeable film and its production |
| JPH0272851A (en) * | 1988-09-08 | 1990-03-13 | Mitsubishi Gas Chem Co Inc | Filmy disoxidant |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05115776A (en) * | 1991-04-02 | 1993-05-14 | W R Grace & Co | Mixture, product and method for scavenging oxygen |
| JP2002080647A (en) * | 2000-09-07 | 2002-03-19 | Mitsubishi Gas Chem Co Inc | Deoxidizing agent resin composition and sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2576646B2 (en) | 1997-01-29 |
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