JPH0413147B2 - - Google Patents
Info
- Publication number
- JPH0413147B2 JPH0413147B2 JP25316687A JP25316687A JPH0413147B2 JP H0413147 B2 JPH0413147 B2 JP H0413147B2 JP 25316687 A JP25316687 A JP 25316687A JP 25316687 A JP25316687 A JP 25316687A JP H0413147 B2 JPH0413147 B2 JP H0413147B2
- Authority
- JP
- Japan
- Prior art keywords
- oxygen
- layer
- film
- iron powder
- sodium chloride
- 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.)
- Expired
Links
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 45
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 31
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 31
- 229910052760 oxygen Inorganic materials 0.000 claims description 31
- 239000001301 oxygen Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000011780 sodium chloride Substances 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 14
- 239000002023 wood Substances 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 9
- 229920005992 thermoplastic resin Polymers 0.000 claims description 9
- 239000012256 powdered iron Substances 0.000 claims description 6
- 230000002265 prevention Effects 0.000 claims description 6
- 230000035699 permeability Effects 0.000 claims description 5
- 230000004888 barrier function Effects 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- 235000013312 flour Nutrition 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009820 dry lamination Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Description
（産業上の利用分野）
本発明は、改良された酸素吸収性の複合フイル
ム又はシートに関する。更に詳しくは保存する内
容物、環境条件に左右されず、常に一定の酸素吸
収性を有する複合フイルムまたはシートに関する
ものである。
上記の複合フイルムまたはシートを包装材料と
して利用するならば、食品の長期保存、衣類の防
虫、医薬品、化粧品の酸化防止及び電子部品、精
密機器の防錆等に顕著な効果を示す。
（従来の技術）
脱酸素機能を有する組成物として特公昭54−
438では鉄粉、もしくは銅粉等と塩化ナトリウム
に水分を含ませることが開示されている。また特
公昭61−32348ではポリエチレン樹脂に鉄粉及び
塩化ナトリウムを配合して溶融成形して得られた
フイルムまたはシートが脱酸素包材として利用さ
れうることが示されている。
さらに特公昭62−1824では樹脂に鉄粉及び塩化
ナトリウム等を配合して溶融成形し、得られた脱
酸素用フイルムを酸素不透過性フイルムを外側に
酸素透過性フイルムを内側に積層する使用方法が
あげられている。鉄粉が酸化されるのは塩化ナト
リウムが水分に僅かに溶けた条件（溶けてイオン
化し、このイオンの存在）下で鉄粉と酸素が結合
するという機構が考えられる。即ち鉄粉−塩化ナ
トリウム−水という三成分共存が必須要件とな
る。
しかるにこれらの脱酸素用フイルムはいずれも
溶融成形して得られたフイルムの為、酸素吸収に
必要な水分が完全に除去された状態、即ち鉄粉−
塩化ナトリウムの共存下であり、もし水分を得る
としたら周囲からの供給を受けて徐々に酸素吸収
が進行することになる。しかしこの方法は周囲の
条件で左右され、場合によつては鉄粉の理論的酸
素吸収量に達しないまま吸収が進まないことが判
明した。よつて従来の技術では、配合する鉄粉が
充分利用されていないことが明らかである。
（発明が解決しようとする問題点）
従来の技術では熱可塑性樹脂に鉄粉及び塩化ナ
トリウムを配合し、フイルム成形する為、得られ
たフイルムは水分が完全に除去されたものであ
る。このような状態において前述の酸素遮断性の
フイルムを外側に酸素透過性、透湿防止性フイル
ムを内側にして積層した場合には、酸素吸収フイ
ルムの表面は鉄粉−塩化ナトリウムの二成分の状
態であり、塩化ナトリウムがイオン化する程の水
分が供給できず、その為鉄粉の酸素吸収能に自ら
限界を生じたものと考えられる。
（問題点を解決するための手段）
以上の考察から酸素吸収性フイルムに水分をい
かに供給すべきか、その適切な供給量はどれ程
か、長期安定化させるにはどういう形態で補うべ
きかが課題となつた。
本願発明者は酸素遮断性を有する層Ａ、熱可塑
性樹脂に微粉末鉄粉、塩化ナトリウムを充填した
層Ｂ、水分を含有する無機粉末、活性炭、木粉ま
たは高分子水溶液の中から選ばれた１つまたは２
つ以上の成分を散布または塗布した層Ｃ、及び酸
素透過性が大きく、透湿防止性を有する層Ｄをこ
の順に積層する方式により上記の課題を一挙に解
決した。即ち上記の水分の供給手段である水分を
含有する無機粉末、活性炭、木粉または高分子水
溶液の層Ｃを、熱可塑性樹脂に微粉末鉄粉、塩化
ナトリウムを充填した層Ｂと酸素透過性が大き
く、透湿防止性を有する層Ｄな間に挿入すること
にある。
本発明が適用される無機粉末とは、ゼオライ
ト、セリサイト、モンモリナイト、カオリンクレ
ー、タルク、珪酸カルシウム、天然珪酸、合成珪
酸、炭酸カルシウム、硫酸カリシウムなどを指
す。更に高分子水溶液としてはポリ酢酸ビニル、
エチレン−酢酸ビニル共重合体、ポリスチレン
系、ポリアクリル酸エステル及びゴム系のラテツ
クスが考えられる。
また上記の水分を含有する無機粉末、活性炭、
木粉または高分子水溶液の散布または塗布量は、
酸素吸収フイルムの酸素吸収速度、能力に大きく
左右される。即ち鉄粉が酸化されるのは、鉄粉−
塩化ナトリウム−水分の三成分共存が必須条件で
ある。このうち鉄粉−塩化ナトリウムはフイルム
層Ｂ中に存在しており一定である。水分量は遊離
水であり、一定の範囲内で多い程酸素の吸収速
度、能力が向上する。
なお、水分を含有する無機粉末、活性炭、木粉
は均一に散布し、高分子水溶液は全面に塗布する
方法が好ましい。
本発明に適用される熱可塑性樹脂は、低密度ポ
リエチレン、高密度ポリエチレン、線状低密度ポ
リエチレン、ポリプロピレン、ポリ塩化ビニル、
エチレン−プロピレン共重合体の如き熱可塑性エ
ラストマー等である。
なお熱可塑性樹脂に微粉末鉄粉、塩化ナトリウ
ムを配合してなる樹脂組成物としては特公昭61−
32348に準じ、熱可塑性樹脂100部に対して微粉末
鉄粉50〜400部、粉末の塩化ナトリウムは鉄粉に
対して２〜20％重量部配合したものである。
本発明に適用される外層用樹脂としてはナイロ
ン、ポリエステル、ポリ塩化ビニリデン、エチレ
ン酢酸ビニル共重合体ケン合物等が好んで用いら
れる。
また内層用樹脂としては、酸素透過性、透湿防
止性良好な低密度ポリエチレン、中密度ポリエチ
レン、エチレン−プロピレン共重合体、エチレン
−酢酸ビニル共重合体、エチレン−アクリル酸エ
ステル共重合体をはじめとするエチレン含量の高
いポリエチレン系樹脂及びプロピレンがあげられ
る。なおＡ，Ｂ，Ｃ，Ｄの各層の積層方法として
は、Ａ層とＢ層の場合両者同時に溶融押出する共
押出法、または片方の層の上にもう一方の層を溶
融押出される押出コーテイング法、接着剤使用に
よるドライラミネート法、溶液分散コーテイング
法、加熱圧着法などが考えられる。またＢ層、Ｃ
層及びＤ層の場合、点加熱圧着法、熱着テープ貼
布法、及びドライラミネート法、溶液分散コーテ
イング法が考えられる。
本発明によれば水分を含有する無機粉末、活性
炭、木粉または高分子水溶液を散布または塗布し
た酸素吸収性フイルムまたはシートは常に一定の
水分が供給される。
従来のように環境条件、内容物の水分に影響さ
れない。他方、塩化ナトリウムはその水分の影響
を受けてイオンに解離し、解離したイオンの存在
下で鉄粉を酸化し、つまり酸素の吸収が促進され
るわけである。鉄粉−塩化ナトリウム−水という
三成分の共存が当該酸素吸収性フイルム又はシー
ト内で安定化し、充分な効力が発揮される。なお
酸素吸収速度、及び酸素吸収能力は鉄粉、塩化ナ
トリウムが一定であるとすると、用途により、水
分を含有する無機粉末、活性炭、木粉または高分
子水溶液の水分量をコントロールすることで更に
向上させることができるという特徴も具備してい
る。
（実施例）
次に本発明の効果を説明するための実施例を示
す。
実施例 １
Ａ 調整した樹脂の配合比
熱可塑性樹脂〔宇部興産製ポリエチレン
HF19〕 100重量部
鉄粉 200メツシユ以上 200
塩化ナトリウム 200メツシユ以上 10
添加剤 ステアリング酸カルシウム 0.3
まずこれらの配合物を所定の重量比で配合、
ヘンシエルミキサーで昇温しながら混合する。
150℃付近で凝集性粒状物を生成後、冷却して
粒状組成物を得る。
Ｂ インフレーシヨン法によるフイルム成形
シリンダー、ダイス内温度は180〜200℃、引
取速度11ｍ／分
析径42cm、フイルム厚さはおよそ130μｍ
Ｃ フイルムの積層
(1) 上記130μｍのフイルムの一方の面に酸素
遮断性のバリアフイルムとしてナイロン70μ
ｍのフイルムを貼付した。
(2) 水分含有木粉の散布
水分35wt％／木粉（150メツシユ）65wt％
上記積層フイルムの130μｍのフイルム面に
水分として10-4ｇ／cm2を単位として、
５，10，50，100及び0.01，0.1倍の濃度で塗
布する。
Ｄ 複合フイルムの作製
上記Ｃ工程終了後酸素透過性、透湿防止性フ
イルムである低密度ポリエチレンフイルム（宇
部興産製F019使用、厚み30μｍ）を重ね、点熱
融着した。その後、縦、横15cm×20cmの大きさ
にして、バリアフイルムを外側にし袋（空気量
200c.c.封入）を作製した。
Ｅ 袋内の酸素の追跡
袋内にシリカゲルを通して乾燥した空気で置
換した後、密封し以後常温で袋内の酸素濃度を
ガスクロマトグラフを用いて経時的に追跡す
る。
なお対照として水分含有木粉を使用しない場
合及び使用しても散布量が少ない場合もつけ加
えた。
(Industrial Field of Application) The present invention relates to an improved oxygen-absorbing composite film or sheet. More specifically, it relates to a composite film or sheet that always has a constant oxygen absorbency regardless of the contents to be stored or environmental conditions. When the above-mentioned composite film or sheet is used as a packaging material, it exhibits remarkable effects in long-term preservation of foods, insect protection for clothing, oxidation prevention for pharmaceuticals and cosmetics, and rust prevention for electronic parts and precision equipment. (Prior art) As a composition having an oxygen scavenging function,
438 discloses adding water to iron powder, copper powder, etc. and sodium chloride. Furthermore, Japanese Patent Publication No. 61-32348 discloses that a film or sheet obtained by melt-molding a mixture of iron powder and sodium chloride in polyethylene resin can be used as an oxygen-absorbing packaging material. Furthermore, in Japanese Patent Publication No. 62-1824, iron powder, sodium chloride, etc. are mixed with resin, melt-molded, and the resulting deoxidizing film is laminated with an oxygen-impermeable film on the outside and an oxygen-permeable film on the inside. is listed. The possible mechanism by which iron powder is oxidized is that iron powder and oxygen combine under conditions where sodium chloride is slightly dissolved in water (dissolved and ionized, and the presence of these ions). That is, the coexistence of the three components iron powder, sodium chloride, and water is an essential requirement. However, since all of these deoxidizing films are obtained by melt molding, they are in a state where the water necessary for oxygen absorption has been completely removed, that is, iron powder.
In the coexistence of sodium chloride, if water were to be obtained, oxygen absorption would gradually proceed as a result of the supply from the surroundings. However, this method is affected by the surrounding conditions, and in some cases it has been found that absorption does not proceed until the theoretical amount of oxygen absorbed by the iron powder is not reached. Therefore, it is clear that in the conventional technology, the iron powder to be mixed is not sufficiently utilized. (Problems to be Solved by the Invention) In the conventional technology, iron powder and sodium chloride are blended into a thermoplastic resin and film is formed, so the obtained film has completely removed moisture. In such a situation, if the above-mentioned oxygen-blocking film is laminated with the oxygen-permeable and moisture-permeable film on the inside, the surface of the oxygen-absorbing film will be in a two-component state of iron powder and sodium chloride. Therefore, it is thought that sufficient moisture could not be supplied to ionize the sodium chloride, and as a result, the oxygen absorption ability of the iron powder reached its own limit. (Means for solving the problem) Based on the above considerations, the issues are how to supply moisture to the oxygen-absorbing film, what is the appropriate supply amount, and in what form should it be supplemented for long-term stability? It became. The inventor of the present application selected layer A having oxygen barrier properties, layer B comprising a thermoplastic resin filled with finely powdered iron powder and sodium chloride, an inorganic powder containing water, activated carbon, wood powder, or an aqueous polymer solution. one or two
The above problems were solved at once by laminating in this order Layer C, in which three or more components were dispersed or coated, and Layer D, which had high oxygen permeability and moisture permeation prevention properties. That is, layer C of water-containing inorganic powder, activated carbon, wood flour, or polymer aqueous solution, which is the means for supplying water, is replaced with layer B, which is a thermoplastic resin filled with finely powdered iron powder and sodium chloride, and layer B, which has a high oxygen permeability. The purpose is to insert the layer D between the large and moisture permeable layer D. The inorganic powder to which the present invention is applied refers to zeolite, sericite, montmorinite, kaolin clay, talc, calcium silicate, natural silicic acid, synthetic silicic acid, calcium carbonate, potassium sulfate, and the like. Furthermore, as polymer aqueous solutions, polyvinyl acetate,
Possible latexes include ethylene-vinyl acetate copolymers, polystyrene-based, polyacrylic acid ester, and rubber-based latexes. In addition, the above water-containing inorganic powder, activated carbon,
The amount of wood powder or polymer aqueous solution to be sprayed or applied is
It greatly depends on the oxygen absorption rate and ability of the oxygen absorption film. In other words, iron powder is oxidized because iron powder -
The coexistence of the three components sodium chloride and water is an essential condition. Among these, iron powder-sodium chloride exists in film layer B and is constant. The water content is free water, and within a certain range, the higher the water content, the better the oxygen absorption rate and ability. Note that it is preferable to uniformly sprinkle the inorganic powder, activated carbon, and wood flour containing water, and apply the polymer aqueous solution to the entire surface. Thermoplastic resins applicable to the present invention include low density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, polyvinyl chloride,
These include thermoplastic elastomers such as ethylene-propylene copolymers. Note that a resin composition made by blending finely powdered iron powder and sodium chloride with a thermoplastic resin is
32348, 50 to 400 parts of finely powdered iron powder is blended to 100 parts of thermoplastic resin, and powdered sodium chloride is blended in an amount of 2 to 20% by weight based on the iron powder. As the resin for the outer layer applied to the present invention, nylon, polyester, polyvinylidene chloride, ethylene-vinyl acetate copolymer, etc. are preferably used. In addition, resins for the inner layer include low-density polyethylene, medium-density polyethylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, and ethylene-acrylic acid ester copolymer, which have good oxygen permeability and moisture permeation prevention properties. Examples include polyethylene resins with high ethylene content and propylene. The lamination method for each layer of A, B, C, and D is a co-extrusion method in which layers A and B are both melt-extruded at the same time, or an extrusion coating method in which one layer is melt-extruded on top of the other layer. Possible methods include a dry lamination method using an adhesive, a solution dispersion coating method, and a heat pressure bonding method. Also, B layer, C
In the case of the layer and the D layer, possible methods include a point heat compression bonding method, a heat-adhesive tape application method, a dry lamination method, and a solution dispersion coating method. According to the present invention, a constant amount of moisture is always supplied to an oxygen-absorbing film or sheet on which moisture-containing inorganic powder, activated carbon, wood flour, or aqueous polymer solution is sprinkled or coated. Unlike conventional products, it is not affected by environmental conditions or moisture content. On the other hand, sodium chloride dissociates into ions under the influence of its moisture, and in the presence of the dissociated ions, iron powder is oxidized, which promotes oxygen absorption. The coexistence of the three components iron powder, sodium chloride, and water is stabilized within the oxygen-absorbing film or sheet, and sufficient efficacy is exhibited. Assuming that the oxygen absorption rate and oxygen absorption capacity are constant for iron powder and sodium chloride, they can be further improved by controlling the water content of water-containing inorganic powder, activated carbon, wood flour, or polymer aqueous solution depending on the application. It also has the feature of being able to (Example) Next, an example for explaining the effects of the present invention will be shown. Example 1 A Compounding ratio of adjusted resin Thermoplastic resin [polyethylene manufactured by Ube Industries, Ltd.
HF19〕 100 parts by weight Iron powder 200 mesh or more 200 Sodium chloride 200 mesh or more 10 Additive Calcium steering acid 0.3 First, these compounds are mixed in a predetermined weight ratio,
Mix with a Henschel mixer while increasing the temperature.
After producing cohesive granules at around 150°C, the mixture is cooled to obtain a granular composition. B Film forming by inflation method Temperature inside the cylinder and die is 180-200℃, take-up speed 11m/analysis diameter 42cm, film thickness approximately 130μm C Film lamination (1) On one side of the above 130μm film Nylon 70μ as oxygen barrier film
A film of m was attached. (2) Spreading water-containing wood flour Water 35wt%/wood flour (150 mesh) 65wt% Moisture on the 130μm film surface of the above laminated film in units of 10 -4 g/ cm2 , 5, 10, 50, 100 and apply at a concentration of 0.01 and 0.1 times. D. Preparation of composite film After the completion of the above step C, a low-density polyethylene film (F019 manufactured by Ube Industries, Ltd., thickness 30 μm), which is an oxygen permeable and moisture permeable film, was layered and spot-fused. After that, make it into a bag (air volume
200 c.c. enclosed) was produced. E. Tracking of oxygen inside the bag After passing silica gel into the bag and replacing it with dry air, seal the bag and then monitor the oxygen concentration inside the bag over time using a gas chromatograph at room temperature. As a control, cases were also added in which moisture-containing wood flour was not used, and in which case the amount of spraying was small even when it was used.
【表】
実施例 ２
Ａ 調整した樹脂の配合比
Ｂ インフレーシヨン法によるフイルム成形｝実
施例１と同様
Ｃ フイルムの積層
(1) 実施例１と同様
(2) 高分子水溶液の塗布
アドミツクスMK019（水分35wt％、ポリア
クリル酸エステル65wt％、日産化学工業(株)製）
上記(1)の130μｍのフイルム面に水分として
10-4ｇ／cm2の単位で、５，10，50，100，及び
0.1倍量を塗布する。
Ｄ 複合フイルムの作製
Ｅ 袋内の酸素の追跡｝実施例１と同様な方法[Table] Example 2 A Mixing ratio of adjusted resin B Film molding by inflation method} Same as Example 1 C Lamination of films (1) Same as Example 1 (2) Application of polymer aqueous solution Admix MK019 ( Moisture 35wt%, polyacrylic acid ester 65wt%, manufactured by Nissan Chemical Industries, Ltd.) As moisture on the 130μm film surface of (1) above
10 -4 in units of g/cm 2 , 5, 10, 50, 100, and
Apply 0.1 times the amount. D. Preparation of composite film E. Tracking of oxygen inside the bag} Same method as in Example 1
【表】
（発明の効果）
本発明は酸素遮断性フイルム層Ａ、熱可塑性樹
脂に微粉末鉄粉、塩化ナトリウムを充填した層
Ｂ、水分を含有する無機粉末、活性炭、木粉また
は高分子水溶液の中から選ばれた１つまたは２つ
以上の成分を散布又は塗布した層Ｃ及び酸素透過
性が大きく、透湿防止性フイルムを有する層Ｄを
この順に積層することを特徴としており、複合フ
イルム袋内の酸素吸収を目的としている。この場
合水分を含有する無機粉末、活性炭、木粉または
高分子水溶液が酸素吸収フイルムの吸収能力と速
度をコントロールする。すなわちフイルム表面の
鉄粉、塩化ナトリウムは一定であり、上記Ｃ中の
水分は変更可能であり、常に鉄粉−塩化ナトリウ
ム−水分の三成分共存状態を形成し、鉄の酸化作
用の速度、及び酸素吸収能力を水分量でコントロ
ールすることができる。実験番号１〜５群と６、
及び９〜13群と14を比較して見れば、水分含有木
粉及び高分子水溶液の存在により上記の効果が十
分発揮されていることがわかる。また水分含有木
粉及び高分子水溶液を使用した場合でも実験番号
１〜５群と７，８群、及び９〜13群と15から散布
又は塗布量により酸素吸収速度、及び酸素吸収能
力に違いが生じることがわかる。これから散布ま
たは塗布量は今回の実験内では多い方が酸素吸収
速度、酸素吸収能力が向上する。かくして本願の
酸素吸収性の複合フイルム又はシートは優れた酸
素吸収性を備えており、従来の吸収性複合フイル
ムのように内容物（包装する物）、環境条件に左
右されず常に一定の酸素吸収性を有するのが特徴
でありかなり広い分野での適用が可能である。[Table] (Effects of the invention) The present invention consists of an oxygen-blocking film layer A, a layer B in which a thermoplastic resin is filled with finely powdered iron powder and sodium chloride, an inorganic powder containing water, activated carbon, wood powder, or an aqueous polymer solution. The composite film is characterized by laminating in this order a layer C in which one or more components selected from the above are sprayed or coated, and a layer D having a high oxygen permeability and moisture permeation prevention film. The purpose is to absorb oxygen inside the bag. In this case, water-containing inorganic powder, activated carbon, wood flour or aqueous polymer solution controls the absorption capacity and speed of the oxygen-absorbing film. That is, the iron powder and sodium chloride on the film surface are constant, and the water content in C can be changed, so that a three-component coexistence state of iron powder, sodium chloride, and water is always formed, and the rate of iron oxidation and Oxygen absorption capacity can be controlled by water content. Experiment numbers 1 to 5 groups and 6,
Comparing Groups 9 to 13 with Group 14, it can be seen that the above effects are fully exhibited due to the presence of moisture-containing wood flour and aqueous polymer solution. Furthermore, even when water-containing wood flour and aqueous polymer solution were used, there were differences in oxygen absorption rate and oxygen absorption capacity depending on the amount of spraying or application from experiment numbers 1 to 5, groups 7 and 8, and groups 9 to 13 and 15. It can be seen that this occurs. In this experiment, the larger the amount of spraying or application, the better the oxygen absorption speed and ability. Thus, the oxygen-absorbing composite film or sheet of the present application has excellent oxygen-absorbing properties, and unlike conventional absorbent composite films, it always maintains a constant level of oxygen absorption regardless of the contents (wrapping material) or environmental conditions. It is characterized by its unique characteristics and can be applied in a fairly wide range of fields.
Claims (1)
粉末鉄粉及び塩化ナトリウムを充填した層Ｂ、水
分を含有する無機粉末、活性炭、木粉及び高分子
水溶液から選ばれた１つ又は２つ以上の成分を散
布または塗布した層Ｃ、及び酸素透過性の大き
い、透湿防止性を有する層Ｄをこの順に積層する
ことを特徴とする酸素吸収性複合フイルムまたは
シート。1 Layer A having oxygen barrier properties, Layer B in which a thermoplastic resin is filled with finely powdered iron powder and sodium chloride, one or two selected from inorganic powder containing water, activated carbon, wood powder, and an aqueous polymer solution. An oxygen-absorbing composite film or sheet characterized by laminating in this order a layer C in which the above components are dispersed or applied, and a layer D having high oxygen permeability and moisture permeation prevention properties.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25316687A JPH0195044A (en) | 1987-10-07 | 1987-10-07 | Oxygen absorbing composite film or sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25316687A JPH0195044A (en) | 1987-10-07 | 1987-10-07 | Oxygen absorbing composite film or sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0195044A JPH0195044A (en) | 1989-04-13 |
| JPH0413147B2 true JPH0413147B2 (en) | 1992-03-06 |
Family
ID=17247449
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25316687A Granted JPH0195044A (en) | 1987-10-07 | 1987-10-07 | Oxygen absorbing composite film or sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0195044A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05330567A (en) * | 1992-05-22 | 1993-12-14 | Toyo Seikan Kaisha Ltd | Method for hermetically sealing vessel using sealing stopper and sealing stopper |
| CA2165709A1 (en) * | 1994-12-27 | 1996-06-28 | Tadatoshi Ogawa | Oxygen absorber |
| JP5563289B2 (en) * | 2009-12-24 | 2014-07-30 | 株式会社巴川製紙所 | Clay film composite |
-
1987
- 1987-10-07 JP JP25316687A patent/JPH0195044A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0195044A (en) | 1989-04-13 |
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