JP4407394B2 - Laminated materials and laminated packaging bags with reduced pinholes - Google Patents
Laminated materials and laminated packaging bags with reduced pinholes Download PDFInfo
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Description
本発明は、医療、医薬品や、食品などの分野において、酸素により品質が容易に劣化するような、厚みと重みを有する易酸化性内容物を包装・梱包して輸送する目的に使用される酸素バリア性を有するピンホールの発生を抑制した積層材料および積層包装袋に関する。特に、５００ｍｌ〜１５００ｍｌと大容量の注射剤を柔軟なプラスチック容器に充填してなる、輸液バックの２次外装材料などとして好適に使用される。 The present invention relates to oxygen used for the purpose of packaging, packing and transporting easily oxidizable contents having thickness and weight, such that the quality is easily deteriorated by oxygen in the fields of medicine, pharmaceuticals, foods, etc. The present invention relates to a laminated material and a laminated packaging bag in which generation of pinholes having a barrier property is suppressed. In particular, it is suitably used as a secondary exterior material for an infusion bag, in which a flexible plastic container is filled with a large volume of 500 ml to 1500 ml of injection.
比較的大容量（５００ｍｌ〜１５００ｍｌ）の注射剤が充填される輸液バックは、近年、ハンドリング（取り扱い）性の良さや、輸液バックの軽量化、ゴミの減容化などの観点から、ガラス瓶、プラスチック成形容器から柔軟なプラスチック包装袋に充填されたものが増えている。 Infusion bags filled with relatively large volumes (500 ml to 1500 ml) of injections have recently been used in glass bottles and plastics from the viewpoints of ease of handling (handling), weight reduction of infusion bags, volume reduction of garbage, etc. An increasing number of plastic containers are filled from molded containers.
輸液バックに充填されるアミノ酸液や糖・電解質液などの薬液は、酸素によって著しく変質しやすく、更には直接体内に薬液を注入する事からも、薬液が直接接触する輸液バックは無添加のポリオレフィン材料を用いる事が多く、酸素バリア性はほとんど無いに等しい。そのため、輸液バックを大気中に放置しておくと、大気中の酸素が輸液バックを透過し経時的に薬液を変質させてしまい、沈殿物の生成や、薬液の黄変、臭いの発生などの現象が起こり、実際に使用する事ができなくなる。そこで、近年は薬液の充填された輸液バックを酸素バリア性の高い透明包装材料で２次包装することが行われている。 Chemical solutions such as amino acid solution and sugar / electrolyte solution filled in the infusion bag are remarkably easily altered by oxygen. In addition, the infusion bag that is in direct contact with the drug solution is an additive-free polyolefin because it is directly injected into the body. Many materials are used, and there is almost no oxygen barrier property. Therefore, if the infusion bag is left in the atmosphere, oxygen in the atmosphere permeates the infusion bag and changes the chemical solution over time, resulting in the formation of precipitates, yellowing of the chemical solution, generation of odor, etc. A phenomenon occurs and it cannot be used in practice. Therefore, in recent years, infusion bags filled with a chemical solution are secondarily packaged with a transparent packaging material having a high oxygen barrier property.
この輸液バック外装材には上記しているように酸素バリア性が高く要求されるため、Ｐポリ塩化ビニリデン（ＶＤＣ）コートを施したプラスチックフィルムや、エチレン‐ビニルアルコール共重合体（ＥＶＯＨ）フィルム、ポリビニルアルコール（ＰＶＡ）フィルム、酸化アルミニウムや酸化珪素などを蒸着したポリエステルテレフタレート（ＰＥＴ）フィルムなどがバリア層に用いられた積層包装材料が使用されている。 Since the infusion bag exterior material is required to have high oxygen barrier properties as described above, a plastic film coated with P polyvinylidene chloride (VDC), an ethylene-vinyl alcohol copolymer (EVOH) film, A laminated packaging material in which a polyvinyl alcohol (PVA) film, a polyester terephthalate (PET) film on which aluminum oxide, silicon oxide or the like is deposited is used as a barrier layer is used.
通常はアミノ酸などの高カロリー輸液が充填された輸液バックが上記した輸液外装袋に入れられ、更にダンボールに積載梱包され輸送される。しかし、輸送工程中の振動・衝撃により、輸液外装袋にピンホールが生じる問題があり（１００万袋に１袋のｐｐｍオーダー）、そのため内容物の品質を保持する酸素バリア性が得られなくなる。 Usually, an infusion bag filled with a high-calorie infusion solution such as amino acid is put in the above-mentioned infusion bag, and further packed and transported in cardboard. However, there is a problem that pinholes are generated in the infusion outer packaging bag due to vibration and impact during the transportation process (ppm order of one bag per million bag), and therefore, an oxygen barrier property that maintains the quality of the contents cannot be obtained.
一般的にピンホールは３つの要素が加味して発生する事が多く、（１）屈曲疲労による屈曲ピンホール、（２）包装材料同士が摩耗する、及び内容物容器と２次包装材が摩耗する、あるいは２次包装材とダンボールが摩耗する事による摩耗ピンホール、（３）包装材料の突起部が突き刺すことによる突き刺しピンホールに大別される。上記、輸送工程におけるピンホールはこれらの３つの要素が複合して発生すると考えられる。 In general, pinholes often occur due to three factors: (1) bent pinholes due to bending fatigue, (2) the packaging materials wear, and the contents container and secondary packaging material wear Or a wear pinhole due to wear of the secondary packaging material and cardboard, and (3) a piercing pinhole due to the piercing of the projection of the packaging material. The above-mentioned pinhole in the transportation process is considered to be generated by combining these three elements.
本発明は、従来、包装袋の輸送工程上での問題点を解決するためになされたものであり、医療、医薬品や、食品などの分野において、酸素により品質が容易に劣化するような、例えば、５００ｍｌ〜１５００ｍｌと大容量の注射剤などのような厚みと重みを有する易酸化性内容物を包装・梱包して輸送する目的に使用される酸素バリア性を有するピンホールの発生を抑制した積層材料および積層包装袋を提供することを目的とする。 The present invention has heretofore been made to solve the problems in the packaging bag transport process, and in the fields of medicine, pharmaceuticals, foods, etc., the quality is easily deteriorated by oxygen, for example, Lamination that suppresses the generation of pinholes having oxygen barrier properties that are used for packaging and packing and transporting easily oxidizable contents having a thickness and weight, such as large-capacity injections of 500 ml to 1500 ml The object is to provide materials and laminated packaging bags.
上記課題を解決するために、
請求項１に係るの発明は、少なくとも、２軸延伸ポリプロピレン（ＯＰＰ）フィルム層、酸素バリア層、熱融着（シーラント）層とがこの順序で積層された酸素バリア性を有するピンホールの発生を抑制した積層材料であって、
前記２軸延伸ポリプロピレンフィルム層と酸素バリア層とは押し出しラミネーション法によって積層され、前記酸素バリア層と熱融着層とはドライラミネーション法によって積層されており、かつ、押し出しラミネーション樹脂にメタロセン触媒によって重合された直鎖状低密度ポリエチレン（ｍ−ＬＬＤＰＥ）を用いることを特徴とするピンホールの発生を抑制した積層材料である。
To solve the above problem,
The invention according to claim 1 is the generation of a pinhole having an oxygen barrier property in which at least a biaxially stretched polypropylene (OPP) film layer, an oxygen barrier layer, and a heat sealing (sealant) layer are laminated in this order. A suppressed laminate material,
The biaxially stretched polypropylene film layer and the oxygen barrier layer are laminated by an extrusion lamination method, the oxygen barrier layer and the heat fusion layer are laminated by a dry lamination method, and are polymerized on the extrusion lamination resin by a metallocene catalyst. It is a laminated material that suppresses the generation of pinholes, characterized by using a linear low-density polyethylene (m-LLDPE).
請求項２に係るの発明は、前記メタロセン触媒によって重合された直鎖状低密度ポリエチレンは、ＪＩＳ Ｋ７１１２に準拠する密度が０．９２０ｇ／ｃｍ3以下であり、ＪＩＳ Ｋ７２１０に準拠する溶融フロー速度（ＭＦＲ）が４〜１５ｇ／１０ｍｉｎ．であることを特徴とする請求項１記載のピンホールの発生を抑制した積層材料である。 The invention according to claim 2 is that the linear low density polyethylene polymerized by the metallocene catalyst has a density of 0.920 g / cm 3 or less in accordance with JIS K7112, and a melt flow rate in accordance with JIS K7210 ( MFR) is 4 to 15 g / 10 min. The laminate material according to claim 1, wherein generation of pinholes is suppressed.
請求項３に係るの発明は、請求項１または２記載のピンホールの発生を抑制した積層材料を用いてなることを特徴とする積層包装袋である。 The invention according to claim 3 is a laminated packaging bag characterized by using the laminated material in which generation of pinholes according to claim 1 or 2 is suppressed.
本発明により、医療、医薬品や、食品などの分野において、酸素により品質が容易に劣化するような、厚みと重みを有する易酸化性内容物を包装・梱包して輸送する目的に使用される酸素バリア性を有するピンホールの発生を抑制した積層材料および積層包装袋を提供することができる。 According to the present invention, oxygen used for the purpose of packaging, packing and transporting easily oxidizable contents having thickness and weight such that quality is easily deteriorated by oxygen in the fields of medicine, pharmaceuticals, foods, etc. It is possible to provide a laminated material and a laminated packaging bag in which generation of pinholes having a barrier property is suppressed.
本発明のピンホールの発生を抑制した積層材料および積層包装袋は、例えば、５００ｍｌ〜１５００ｍｌと大容量の注射剤を柔軟なプラスチック容器に充填してなる輸液バックの２次外装材料などととして好適に用いられる。 The laminated material and laminated packaging bag in which the occurrence of pinholes according to the present invention is suppressed are suitable as, for example, a secondary exterior material for an infusion bag formed by filling a flexible plastic container with a large-capacity injection of 500 ml to 1500 ml. Used for.
以下、本発明の一実施例としての実施の形態について具体的に説明する。図１は、本発明のピンホールの発生を抑制した積層材料の一例を示す断面図である。図に示すように、本発明のピンホールの発生を抑制した積層材料の構成は、２軸延伸ポリプロピレン（ＯＰＰ）フィルム層（ａ）、接着樹脂層（ｂ）、酸素バリア層（ｃ）、接着剤層（ｄ）、熱融着層（ｅ）からなる。 Hereinafter, an embodiment as an example of the present invention will be described in detail. FIG. 1 is a cross-sectional view showing an example of a laminated material in which the generation of pinholes of the present invention is suppressed. As shown in the figure, the structure of the laminated material in which the occurrence of pinholes of the present invention is suppressed is as follows: biaxially oriented polypropylene (OPP) film layer (a), adhesive resin layer (b), oxygen barrier layer (c), adhesive It consists of an agent layer (d) and a heat sealing layer (e).
本発明における２軸延伸ポリプロピレン（ＯＰＰ）フィルム層（ａ）は、各社ポリプロピレンフィルムメーカーから上市されてい２軸延伸ポリプロピレンフィルムなら特に制限はなく、厚みは３０μｍ以下が望ましい。厚みが、３０μｍを超えると積層材料の剛性が増大することで耐屈曲性が減少し、耐ピンホール性が低下する。 The biaxially stretched polypropylene (OPP) film layer (a) in the present invention is not particularly limited as long as it is a biaxially stretched polypropylene film marketed by a polypropylene film manufacturer of each company, and the thickness is desirably 30 μm or less. If the thickness exceeds 30 μm, the rigidity of the laminated material increases, so that the bending resistance decreases and the pinhole resistance decreases.
本発明における接着樹脂層（ｂ）は、押し出しラミネーション用接着樹脂としてメタロセン触媒によって重合された直鎖状低密度ポリエチレン（ｍ−ＬＬＤＰＥ）を用いていることを特徴とし、一般的には、低密度ポリエチレン（ＬＤＰＥ）やチーグラー・ナッタ触媒によって重合された直鎖状低密度ポリエチレン（ＬＬＤＰＥ）よりは組成分布が均一であり、分子量分布が狭いために強い膜物性を持つことが知られている。メタロセン触媒によって重合された直鎖状低密度ポリエチレンでフィルム膜強度を向上させ、密度を０．９２０ｇ／ｃｍ3以下とすることで包装材の腰（スティフネス）は柔らかくし、屈曲ピンホールを抑制している。また、溶融フロー速度は加工適性を考慮して、４〜１５ｇ／１０ｍｉｎ．が望ましい押し出し樹脂の厚みは３０μｍ以下でありことが望ましい。特に、密度を０．９１０ｇ／ｃｍ3以下にすることで、２軸延伸ポリプロピレンの処理面（処理度：
４０ダイン）にアンカーコート無しで接着することが可能である。そして、押し出しラミネーションで使用可能なｍ−ＬＬＤＰＥ樹脂としては、各社から上市されているものを使用することができる。
The adhesive resin layer (b) in the present invention is characterized by using linear low density polyethylene (m-LLDPE) polymerized by a metallocene catalyst as an adhesive resin for extrusion lamination, and generally has a low density. It is known that the composition distribution is more uniform than polyethylene (LDPE) and linear low density polyethylene (LLDPE) polymerized by Ziegler-Natta catalyst, and the molecular weight distribution is narrow, so that it has strong film properties. A linear low-density polyethylene polymerized with a metallocene catalyst improves the film membrane strength, and by making the density 0.920 g / cm 3 or less, the stiffness of the packaging material is softened and bent pinholes are suppressed. ing. The melt flow rate is 4 to 15 g / 10 min. Desirably, the thickness of the extruded resin is desirably 30 μm or less. In particular, by setting the density to 0.910 g / cm 3 or less, the treated surface of biaxially oriented polypropylene (treatment degree:
40 dynes) without an anchor coat. And as m-LLDPE resin which can be used by extrusion lamination, what is marketed by each company can be used.
本発明における酸素バリア層（ｃ）は、酸化アルミニウムや、酸化珪素を蒸着したガスバリア性フィルムやエチレン−ビニルアルコール共重合（ＥＶＯＨ）フィルム、ポリビニルアルコール（ＰＶＡ）フィルムなどが使用でき、厚みは１５μｍ前後が望ましい。 As the oxygen barrier layer (c) in the present invention, aluminum oxide, a gas barrier film on which silicon oxide is deposited, an ethylene-vinyl alcohol copolymer (EVOH) film, a polyvinyl alcohol (PVA) film, and the like can be used, and the thickness is about 15 μm. Is desirable.
本発明における接着剤層（ｄ）は、ドライラミネーションに用いられる２液硬化型ウレタン系接着剤ならどれも使用可能であり、乾燥時の塗布量は１．５〜３．５ｇ／ｍ2程度であれば接着強度の観点からも望ましい。 As the adhesive layer (d) in the present invention, any two-component curable urethane adhesive used for dry lamination can be used, and the coating amount when dried is about 1.5 to 3.5 g / m 2 . If present, it is also desirable from the viewpoint of adhesive strength.
本発明における熱融着層（ｅ）は、ｍ−ＬＬＤＰＥ樹脂が使用できる。各社フィルムメーカから上市されているｍ−ＬＬＤＰＥであれば特に制限はなく、更には、インフレーション法、キャスト法によって製膜された密度勾配を持った２層以上の多層構成からなり、密度０．９２ｇ／ｃｍ3以下の低密度層と密度０．９２〜０．９５ｇ／ｃｍ3の中密度層の少なくとも２層以上から構成され、低密度層が熱融着層の６０％以上を占め、かつ、酸素バリア層側にあることが望ましい。 M-LLDPE resin can be used for the heat sealing | fusion layer (e) in this invention. If m-LLDPE is marketed by a film maker of each company, there is no particular limitation. Furthermore, it consists of a multilayer structure of two or more layers having a density gradient formed by an inflation method or a cast method, and has a density of 0.92 g. At least two layers of a low density layer of / cm 3 or less and a medium density layer of density 0.92 to 0.95 g / cm 3 , the low density layer occupies 60% or more of the heat fusion layer, and It is desirable to be on the oxygen barrier layer side.
本発明のピンホールの発生を抑制した積層材料を用いて、様々の包装形態の積層袋に成形して用いることができる。特に、５００ｍｌ〜１５００ｍｌと大容量の注射剤を柔軟なプラスチック容器に充填してなる、輸液バックの２次外装材料などとして好適に使用される。 Using the laminated material in which the generation of pinholes of the present invention is suppressed, it can be used by forming into laminated bags of various packaging forms. In particular, it is suitably used as a secondary exterior material for an infusion bag, which is formed by filling a flexible plastic container with a large volume of 500 ml to 1500 ml of injection.
以下、本発明の実施例を具体的に説明する。 Examples of the present invention will be specifically described below.
下記に示す材料を用いて、図１に示す構成の本発明のピンホールの発生を抑制した積層材料を作成した。
（ａ）ＯＰＰ層：２軸延伸ポリプロピレン（ＯＰＰ）フィルム（東セロ（株）製「Ｕ１」、厚さ２０μｍ）
（ｂ）接着樹脂層：ＵＢＥスーパーポリエチレン「ユメリット」（ｍ−ＬＬＤＰＥ、密度０．９０４ｇ／ｃｍ3、溶融フロー速度８ｇ／１０ｍｉｎ．、２０μｍ）（宇部興産（株）製「０２２ＧＳ」）
（ｃ）酸素バリア層：酸化アルミニウム蒸着２軸延伸ナイロンフィルム（凸版印刷（株）製「ＧＬ−ＡＥＹ」、厚さ１５μｍ）
（ｄ）接着剤層：２液硬化型ウレタン系接着剤（三井武田ケミカル（株）製「Ａ５１５」、乾燥塗布量３ｇ／ｍ2）
（ｅ）熱融着層：メタロセン触媒重合ＬＬＤＰＥ（２層、６０μｍ）
酸素バリア層側←（密度０．９０５ｇ／ｃｍ3、厚み４０μｍ‖密度０．９３１ｇ／ｃｍ3、厚さ２０μｍ）
Using the materials shown below, a laminated material having the configuration shown in FIG.
(A) OPP layer: biaxially oriented polypropylene (OPP) film (“U1” manufactured by Tosero Co., Ltd., thickness 20 μm)
(B) Adhesive resin layer: UBE super polyethylene “Umerit” (m-LLDPE, density 0.904 g / cm 3 , melt flow rate 8 g / 10 min., 20 μm) (“022GS” manufactured by Ube Industries, Ltd.)
(C) Oxygen barrier layer: Aluminum oxide vapor-deposited biaxially stretched nylon film (“GL-AEY” manufactured by Toppan Printing Co., Ltd., thickness 15 μm)
(D) Adhesive layer: two-component curable urethane-based adhesive (“A515” manufactured by Mitsui Takeda Chemical Co., Ltd., dry coating amount 3 g / m 2 )
(E) Thermal fusion layer: metallocene catalyzed polymerization LLDPE (two layers, 60 μm)
Oxygen barrier layer side ← (density 0.905 g / cm 3 , thickness 40 μm ‖ density 0.931 g / cm 3 , thickness 20 μm)
下記に示す材料を用いて、本発明のピンホールの発生を抑制した積層材料と比較するための積層材料を作成した。
（ａ）ＯＰＰ層：２軸延伸ポリプロピレン（ＯＰＰ）フィルム（東セロ（株）製「Ｕ１」、厚さ２０μｍ）
（ｂ）接着樹脂層：高機能性押し出しラミネート樹脂「ジェイレクス」（ＬＤＰＥ、密度０．９１８ｇ／ｃｍ3、溶融フロー速度７ｇ／１０ｍｉｎ．、２０μｍ）（日本ポリオレフィン（株）製「ＪＨ６０７Ｄ」）
（ｃ）酸素バリア層：酸化アルミニウム蒸着２軸延伸ナイロンフィルム（凸版印刷（株）製「ＧＬ−ＡＥＹ」、厚さ１５μｍ）
（ｄ）接着剤層：２液硬化型ウレタン系接着剤（三井武田ケミカル（株）製「Ａ５１５」、乾燥塗布量３ｇ／ｍ2）
（ｅ）熱融着層：メタロセン触媒重合ＬＬＤＰＥ（２層、６０μｍ）
酸素バリア層側←（密度０．９０５ｇ／ｃｍ3、厚み４０μｍ‖密度０．９３１ｇ／ｃｍ3、厚み２０μｍ）
Using the materials shown below, a laminate material was prepared for comparison with the laminate material of the present invention that suppressed the generation of pinholes.
(A) OPP layer: biaxially oriented polypropylene (OPP) film (“U1” manufactured by Tosero Co., Ltd., thickness 20 μm)
(B) Adhesive resin layer: highly functional extruded laminate resin “JEREX” (LDPE, density 0.918 g / cm 3 , melt flow rate 7 g / 10 min., 20 μm) (“JH607D” manufactured by Nippon Polyolefin Co., Ltd.)
(C) Oxygen barrier layer: Aluminum oxide vapor-deposited biaxially stretched nylon film (“GL-AEY” manufactured by Toppan Printing Co., Ltd., thickness 15 μm)
(D) Adhesive layer: two-component curable urethane-based adhesive (“A515” manufactured by Mitsui Takeda Chemical Co., Ltd., dry coating amount 3 g / m 2 )
(E) Thermal fusion layer: metallocene catalyzed polymerization LLDPE (two layers, 60 μm)
Oxygen barrier layer side ← (density 0.905 g / cm 3 , thickness 40 μm‖density 0.931 g / cm 3 , thickness 20 μm)
本発明のピンホールの発生を抑制した積層材料と比較するために、ＯＰＰ層（厚さ３０μｍ／ＰＶＡ層（厚さ１２μｍ）／ＬＬＤＰＥ（厚さ９０μｍ）の構成からなる市場品を使用した。 In order to compare with the laminated material in which the generation of pinholes of the present invention was suppressed, a commercial product having a configuration of OPP layer (thickness 30 μm / PVA layer (thickness 12 μm) / LLDPE (thickness 90 μm)) was used.
上記実施例１〜３で得られた積層材料を用いて、下記の方法に基づいて耐ピンホール性を評価した。 Using the laminate materials obtained in Examples 1 to 3, pinhole resistance was evaluated based on the following method.
＜ピンホール評価方法＞
上記実施例１〜３で得られた積層材料をヒートシールした後、輸液バックを充填し残りの一方をヒートシールし輸液外装袋を作成した。作成した輸液外装袋を２行×５段でダンボールに梱包積載し、下記条件で振動試験を行い。ダンボール３箱分（３０袋）の輸液外装袋のピンホール数をカウントした。
<Pinhole evaluation method>
After heat-sealing the laminated materials obtained in Examples 1 to 3, the infusion bag was filled and the other one was heat-sealed to prepare an infusion bag. The created infusion outer packaging bag is packed and loaded on cardboard in 2 rows x 5 rows, and a vibration test is performed under the following conditions. The number of pinholes in the infusion outer packaging bag for 3 cardboard boxes (30 bags) was counted.
振動条件：振動加速度±４Ｇ、振動数１１Ｈｚ、垂直方向３０分＋水平方向１５分で２回、計１時間 Vibration conditions: Vibration acceleration ± 4G, vibration frequency 11Hz, vertical direction 30 minutes + horizontal direction 15 minutes twice, total 1 hour
（ａ）：２軸延伸ポリプロピレン（ＯＰＰ）フィルム層
（ｂ）：押し出しラミネーション用接着樹脂層
（ｃ）：酸素バリア層
（ｄ）：ドライラミネーション用接着剤層
（ｅ）：熱融着層
(A): Biaxially oriented polypropylene (OPP) film layer (b): Adhesive resin layer for extrusion lamination (c): Oxygen barrier layer (d): Adhesive layer for dry lamination (e): Thermal fusion layer
Claims (3)
前記２軸延伸ポリプロピレンフィルム層と酸素バリア層とは押し出しラミネーション法によって積層され、前記酸素バリア層と熱融着層とはドライラミネーション法によって積層されており、かつ、押し出しラミネーション樹脂にメタロセン触媒によって重合された直鎖状低密度ポリエチレン（ｍ−ＬＬＤＰＥ）を用いることを特徴とするピンホールの発生を抑制した積層材料。 At least a biaxially stretched polypropylene (OPP) film layer, an oxygen barrier layer, and a heat fusion (sealant) layer are laminated materials that suppress the generation of pinholes having oxygen barrier properties laminated in this order,
The biaxially stretched polypropylene film layer and the oxygen barrier layer are laminated by an extrusion lamination method, the oxygen barrier layer and the heat fusion layer are laminated by a dry lamination method, and are polymerized on the extrusion lamination resin by a metallocene catalyst. A laminated material that suppresses the generation of pinholes, characterized by using a linear low-density polyethylene (m-LLDPE).
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| JP3331243B2 (en) * | 1993-10-29 | 2002-10-07 | 株式会社メイワパックス | Laminated film for packaging and method for producing the same |
| JPH07186337A (en) * | 1993-12-27 | 1995-07-25 | Okura Ind Co Ltd | Gas substituting or oxygen scavenger-containing packaging laminated film |
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