JP2001172441A - Heat resistant sheet and infusion bag by using the same - Google Patents
Heat resistant sheet and infusion bag by using the sameInfo
- Publication number
- JP2001172441A JP2001172441A JP2000187338A JP2000187338A JP2001172441A JP 2001172441 A JP2001172441 A JP 2001172441A JP 2000187338 A JP2000187338 A JP 2000187338A JP 2000187338 A JP2000187338 A JP 2000187338A JP 2001172441 A JP2001172441 A JP 2001172441A
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- Japan
- Prior art keywords
- density
- polyethylene
- infusion bag
- transparency
- weight
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は耐熱性シートに関す
る。またこの耐熱性シートを用いて形成した、透明性、
柔軟性に優れ、不溶性微粒子の発生の少ない輸液バッグ
に関する。The present invention relates to a heat-resistant sheet. Transparency, formed using this heat-resistant sheet,
The present invention relates to an infusion bag which has excellent flexibility and generates little insoluble fine particles.
【０００２】[0002]
【従来の技術】輸液バッグや血液バッグ等プラスチック
製医療用容器には、柔軟性や透明性が要求される一方、
高圧蒸気滅菌に耐えうる耐熱性も要求される。医療用容
器の形成材料としては、従来、ポリエチレンやポリプロ
ピレンなどのオレフィン系樹脂、ポリ塩化ビニル、エチ
レン−酢酸ビニルコポリマー等が使用されており、中で
もオレフィン系樹脂、特にポリエチレンは耐薬品性に優
れていることから輸液バッグの形成材料として多用され
ている。2. Description of the Related Art While plastic medical containers such as infusion bags and blood bags are required to have flexibility and transparency,
Heat resistance that can withstand high-pressure steam sterilization is also required. As a material for forming a medical container, conventionally, olefin resins such as polyethylene and polypropylene, polyvinyl chloride, ethylene-vinyl acetate copolymer, and the like have been used. Among them, olefin resins, particularly polyethylene, have excellent chemical resistance. Therefore, it is widely used as a material for forming an infusion bag.
【０００３】しかしながら、ポリエチレンは低密度では
比較的柔軟性、透明性に優れているが、軟化点が低いた
め耐熱性に乏しく、そのため高圧蒸気滅菌に絶えられ
ず、変形、白化、ブロッキング等を生じる。そこで、こ
のようなポリエチレンの欠点を補うものとして、容器の
形成材料を多層シートにして柔軟性、透明性、耐熱性の
バランスをとろうとする提案が種々なされている（特許
第２５５０２５６号公報、特開昭５８−１６５８６６号
公報、特開平６−２０９９８１号公報など）。特許第２
５５０２５６号公報のバッグは、内外層に高密度ポリエ
チレンを主成分とする樹脂層、中間層に直鎖状低密度ポ
リエチレンの層を配した多層シートを使用しており、特
開昭５８−１６５８６６号公報の容器は、エチレン−酢
酸ビニル共重合体、エラストマー等のポリマーを中間層
とする多層シートを使用している。また、特開平６−２
０９９８１号公報の容器は、直鎖状低密度ポリエチレン
の第一層と、高密度ポリエチレンと低密度ポリエチレン
の重合体組成物の第二層を有する多層シートを使用して
いる。[0003] However, polyethylene is relatively excellent in flexibility and transparency at low density, but has poor heat resistance due to its low softening point, so that it cannot be continuously sterilized by high-pressure steam and causes deformation, whitening, blocking, and the like. . In order to compensate for such disadvantages of polyethylene, various proposals have been made to balance the flexibility, transparency, and heat resistance by using a multi-layer sheet of a container forming material (Japanese Patent No. 255502256, JP-A-58-165866, JP-A-6-209981 and the like. Patent No. 2
Japanese Patent Application Laid-Open No. 58-165866 discloses a bag disclosed in Japanese Patent Application Laid-Open No. 58-165866, in which a bag having a resin layer mainly composed of high-density polyethylene as an inner layer and an intermediate layer having a layer of linear low-density polyethylene is used. The container in the publication uses a multilayer sheet having a polymer such as an ethylene-vinyl acetate copolymer or an elastomer as an intermediate layer. Also, JP-A-6-2
No. 09981 uses a multilayer sheet having a first layer of linear low density polyethylene and a second layer of a polymer composition of high density polyethylene and low density polyethylene.
【０００４】しかしながら、多層シートは、多層にする
ことにより製膜条件が複雑になり、製造コストの増加に
つながるという欠点を有している。そこで、最近、柔軟
性と透明性に優れたバッグ形成材料としてメタロセン触
媒系低密度ポリエチレン（以下Ｍ−ＬＬＤＰＥという）
が注目されるようになってきており、このような樹脂を
用いた医療用容器、または医療容器に好適なフィルムの
提案がなされている（特開平６−３２９８４８号公報、
特開平９−９９０３５号公報、特開平１１−１９１８３
号公報等）。特開平６−３２９８４８号公報に示される
組成物は、特定の物性を有し、密度およびＭＦＲが共に
異なるエチレン・α−オレフィン共重合体［Ａ］および
［Ｂ］からなるエチレン・α−オレフィン共重合体組成
物と、特定の物性を有する高圧ラジカル法低密度ポリエ
チレンとをブレンドして得られるものであり、この組成
物から製造されたフィルムは、優れた透明性および熱安
定性を有している。また、特開平９−９９０３５号公報
に示される医療用容器は、密度０．９２８ｇ／ｃｍ3以
下のＭ−ＬＬＤＰＥからなる層が内層または中間層を構
成している多層シートより形成されており、透明性と柔
軟性が改良されている。一方、特開平１１−１９１８３
号公報に示される医療用容器は、容器本体壁が、密度
０．９２１〜０．９２５ｇ／ｃｍ3の範囲にあるＭ−Ｌ
ＬＤＰＥ層（Ｍ−ＬＬＤＰＥは、層中に６０％以上含
有、または厚み６０％以上の主層を構成）からなるもの
で、透明性、柔軟性と共に熱寸法安定性も改良されてい
る。[0004] However, the multilayer sheet has the drawback that the film formation conditions become complicated by multi-layering, which leads to an increase in manufacturing cost. Therefore, recently, a metallocene-catalyzed low-density polyethylene (hereinafter, referred to as M-LLDPE) has been used as a bag-forming material having excellent flexibility and transparency.
Has been attracting attention, and a medical container using such a resin, or a film suitable for a medical container, has been proposed (Japanese Patent Application Laid-Open No. 6-329848,
JP-A-9-99035, JP-A-11-19183
No.). The composition disclosed in JP-A-6-329848 has specific physical properties, and ethylene / α-olefin copolymers comprising ethylene / α-olefin copolymers [A] and [B] having different densities and MFRs. It is obtained by blending a polymer composition and a high-pressure radical method low-density polyethylene having specific physical properties, and a film produced from this composition has excellent transparency and heat stability. I have. Further, the medical container disclosed in JP-A-9-99035 is formed from a multilayer sheet in which a layer made of M-LLDPE having a density of 0.928 g / cm 3 or less constitutes an inner layer or an intermediate layer, Transparency and flexibility have been improved. On the other hand, JP-A-11-19183
In the medical container disclosed in Japanese Patent Application Laid-Open Publication No. H10-209, the container body wall has an M-L having a density of 0.921 to 0.925 g / cm 3.
It is composed of an LDPE layer (M-LLDPE contains 60% or more in the layer or constitutes a main layer having a thickness of 60% or more) and has improved thermal dimensional stability as well as transparency and flexibility.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、これら
のＭ−ＬＬＤＰＥを用いた医療用容器は、透明性は優れ
ているが、１１５℃で滅菌した場合、しばしば熱による
変形が生じるなど耐熱性については十分とは言えず、問
題であった。また、多層シートを用いた特開平９−９９
０３５号公報の医療用容器は、多層にすることにより製
膜条件が複雑になり、製造コストの増加につながるとい
う欠点も有している。本発明は上記の事情に鑑みてなさ
れたもので、微粒子が少なく、透明性および柔軟性に優
れている上、１１５℃の滅菌でも変形することのない十
分な耐熱性を有する輸液バッグを提供することを目的と
する。However, although medical containers using these M-LLDPEs are excellent in transparency, when sterilized at 115 ° C., they often suffer from deformation due to heat. Not enough, it was a problem. Also, Japanese Patent Application Laid-Open No. 9-99 using a multilayer sheet
The medical container disclosed in Japanese Patent No. 035 also has a drawback that film formation conditions are complicated by multi-layering, which leads to an increase in manufacturing cost. The present invention has been made in view of the above circumstances, and provides an infusion bag having a small amount of fine particles, excellent transparency and flexibility, and having sufficient heat resistance so as not to be deformed even by sterilization at 115 ° C. The purpose is to:
【０００６】[0006]
【課題を解決するための手段】本発明者等は、上記の課
題を解決するために鋭意検討の結果、不溶性微粒子の発
生が少なく耐熱性のよい密度０．９２８ｇ／ｃｍ3以上
のメタロセン触媒系直鎖状ポリエチレンと、溶融時の粘
度が高く透明性のよい高圧法低密度ポリエチレン、柔軟
性・耐衝撃性の優れた密度０．９１ｇ／ｃｍ3以下のメ
タロセン触媒系直鎖状ポリエチレンの、特性の異なる3
つのポリエチレンを適当に組み合わせることにより、耐
熱性が良く、不溶性微粒子が少なく、透明性および耐衝
撃性、柔軟性の優れた輸液バッグ材料が得られることを
見出し、本発明を完成した。すなわち本発明は、密度
０．９２８ｇ／ｃｍ3以上のメタロセン触媒系直鎖状ポ
リエチレン４５〜７５重量％、好ましくは５０〜７０重
量％と、高圧法低密度ポリエチレン５〜３５重量％、好
ましくは１０〜３０重量％と、密度０．９１ｇ／ｃｍ3
以下のメタロセン触媒系直鎖状ポリエチレン１５〜４５
重量％、好ましくは２０〜４０重量％を含む重合体組成
物から形成されてなる耐熱性シートである。また、本発
明は、この耐熱性シートを用いて形成された輸液バッグ
に関する。The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a metallocene catalyst system having a density of 0.928 g / cm 3 or more with less heat generation and less generation of insoluble fine particles. Characteristics of linear polyethylene, high-pressure low-density polyethylene with high viscosity and high transparency when melted, and metallocene-catalyzed linear polyethylene with a density of 0.91 g / cm 3 or less, excellent in flexibility and impact resistance 3 different
It has been found that by appropriately combining two polyethylenes, an infusion bag material having good heat resistance, few insoluble fine particles, and excellent transparency, impact resistance and flexibility can be obtained, and completed the present invention. That is, the present invention relates to a metallocene-catalyzed linear polyethylene having a density of 0.928 g / cm 3 or more of 45 to 75% by weight, preferably 50 to 70% by weight, and a high-pressure low-density polyethylene of 5 to 35% by weight, preferably 10 to 50% by weight. -30% by weight and a density of 0.91 g / cm 3
The following metallocene-catalyzed linear polyethylene 15 to 45
It is a heat-resistant sheet formed from a polymer composition containing 20% by weight, preferably 20 to 40% by weight. The present invention also relates to an infusion bag formed using the heat-resistant sheet.
【０００７】本発明の耐熱性シートをインフレーション
成形する場合、ダイリップのクリアランスは、高速（８
ｍ／min以上）で押し出す場合に、剪断力によりフィル
ムにメルトフラクチャ−が発生しないよう、２．５ｍｍ
以上が望ましい。また、成形温度はダイ温度で１８０〜
２１０℃が望ましい。ダイ温度２１０℃以上で成形を行
うと焼けやフィッシュアイが発生し、また、溶融粘度が
低下して製膜が困難になる。スクリューの圧縮比は３．
０以下が望ましい。圧縮比がそれ以上になると自己発熱
が大きくなり、成形が困難になる。When the heat-resistant sheet of the present invention is subjected to inflation molding, the clearance of the die lip is high (8).
(m / min or more) so as not to cause melt fracture in the film due to shearing force.
The above is desirable. The molding temperature is 180 to
210 ° C. is desirable. If the molding is performed at a die temperature of 210 ° C. or higher, burning and fish eyes are generated, and the melt viscosity is lowered to make film formation difficult. The compression ratio of the screw is 3.
0 or less is desirable. When the compression ratio is higher than that, self-heating becomes large, and molding becomes difficult.
【０００８】[0008]
【発明の実施の形態】次に本発明の実施例について具体
的に説明する。 〔実施例１〜７〕密度０．９２８ｇ／ｃｍ3以上のメタ
ロセン触媒系直鎖状ポリエチレン（M−PE−１）、高圧
法低密度ポリエチレン（LDPE）、密度０．９１ｇ／ｃｍ
3以下のメタロセン触媒系直鎖状ポリエチレン（M−PE−
２）を、ブレンダーを使用して表１に示すような割合で
混合し、インフレーション機を用いて、リップクリアラ
ンス２．５ｍｍ、引き出し速度８ｍ／min、ダイス温度
１９０℃の成形条件で、折り形１００ｍｍ、肉厚２５０
μｍのチューブシートを作成した。次に、チューブシー
トを１５０ｍｍの長さにカットし、両端をシールして容
器を各１０個作成し、各容器についてそれぞれ耐熱性、
透明性、微粒子の有無、柔軟性（耐衝撃性、落下強度）
の評価を行った。その結果を表２に示す。但し、評価方
法は次の要領に従った。 耐熱性評価：各容器に生理食塩水１００mlを入れて密封
し、高圧蒸気滅菌機を用いて１１５℃、内圧０．２MPa
で３０分間滅菌処理を行い、処理後、トレー穴形状のバ
ッグへの転写の有無を確認し、転写の無いものを良好と
する。 透明性評価：波長４５０ｎｍにおける水中光透過率を分
光光度計で測定する。 微粒子評価：液中微粒子カウンタークライメットで測定
する。 耐衝撃性評価：（株）東洋精機の振り子式衝撃試験機
（ＤＧ−ＴＢ）を用いて、ＪＩＳ Ｋ ７１６０に従っ
て行った。 落下強度評価：室温で、１５０ｃｍの高さから落下さ
せ、落下時の破袋の有無を確認する。Next, embodiments of the present invention will be specifically described. [Examples 1 to 7] Metallocene catalyst linear polyethylene (M-PE-1) having a density of 0.928 g / cm 3 or more, high-pressure low-density polyethylene (LDPE), density 0.91 g / cm
3 or less metallocene-catalyzed linear polyethylene (M-PE-
2) was mixed at a ratio as shown in Table 1 using a blender, and a lip clearance of 2.5 mm, a drawing speed of 8 m / min, a die temperature of 190 ° C., and a folding shape of 100 mm using an inflation machine. , Wall thickness 250
A μm tube sheet was prepared. Next, the tube sheet was cut to a length of 150 mm, both ends were sealed, and ten containers were prepared.
Transparency, presence or absence of fine particles, flexibility (impact resistance, drop strength)
Was evaluated. Table 2 shows the results. However, the evaluation method followed the following procedure. Heat resistance evaluation: 100 ml of physiological saline was sealed in each container, and sealed at 115 ° C using a high-pressure steam sterilizer at an internal pressure of 0.2 MPa.
For 30 minutes. After the treatment, the presence or absence of transfer to the tray hole-shaped bag is checked, and those without transfer are evaluated as good. Transparency evaluation: The light transmittance in water at a wavelength of 450 nm is measured with a spectrophotometer. Fine particle evaluation: Measured using a submerged fine particle counterclimate. Impact resistance evaluation: It was performed according to JIS K 7160 using a pendulum impact tester (DG-TB) of Toyo Seiki Co., Ltd. Drop strength evaluation: Drop from a height of 150 cm at room temperature, and confirm the presence or absence of bag breakage when dropped.
【０００９】〔比較例１〜１０〕表１に示すような割合
で混合した重合体組成物を用いて、実施例と同様の容器
を各１０個作成し、各容器についてそれぞれ耐熱性、透
明性、微粒子の有無、柔軟性の評価を行った。その結果
を表２に示す。[Comparative Examples 1 to 10] Ten containers each of which were the same as those in the examples were prepared using the polymer compositions mixed in the ratios shown in Table 1, and the heat resistance and the transparency of each container were respectively determined. , The presence or absence of fine particles, and the flexibility were evaluated. Table 2 shows the results.
【００１０】表２から分かるように、本発明のシート
は、すべての試験項目において合格であったのに対し
て、M−PE−１の量が４５重量％未満の比較例４、５、
９および１０では、耐熱性が悪く、容器が溶けて変形し
てしまい、透明性、微粒子の有無、柔軟性の評価を行う
ことができなかった。また、M−PE−１の量が７５重量
％を超え、LDPEが５重量％未満の比較例１、３では、透
明性に問題があり、M−PE−２が１５重量％未満の比較
例１、２、６、７では、柔軟性に問題がある。また、実
施例６においてM−PE−２の代わりに、これより密度の
高いメタロセン触媒系直鎖状ポリエチレン（M−PE−
３）を用いた比較例8では、十分な柔軟性が得られてい
ない。[0010] As can be seen from Table 2, the sheets of the present invention passed all of the test items, while the amounts of M-PE-1 were less than 45% by weight.
In Nos. 9 and 10, the heat resistance was poor, the container was melted and deformed, and the transparency, the presence or absence of fine particles, and the flexibility could not be evaluated. In Comparative Examples 1 and 3 in which the amount of M-PE-1 exceeds 75% by weight and LDPE is less than 5% by weight, there is a problem in transparency, and Comparative Examples in which M-PE-2 is less than 15% by weight. In 1, 2, 6, and 7, there is a problem in flexibility. In Example 6, instead of M-PE-2, a metallocene-catalyzed linear polyethylene (M-PE-
In Comparative Example 8 using 3), sufficient flexibility was not obtained.
【００１１】[0011]
【表１】 [Table 1]
【００１２】[0012]
【表２】 （注）滅菌温度は１１５℃であり、微粒子は１〜２μm
のものが１００個／ｍｌ以下、透明性は滅菌後７０％以
上、耐衝撃性は２５０kJ／m2以上であれば合格とした。
また、落下強度は、２３℃の室温で１５０ｃｍの高さか
ら３回落下させたときのリーク数で示す。成形性および
耐熱性については良いものを「○」、悪いものを「×」
にしている。[Table 2] (Note) Sterilization temperature is 115 ° C, and fine particles are 1-2 μm.
Were 100 or less, the transparency was 70% or more after sterilization, and the impact resistance was 250 kJ / m 2 or more.
The drop strength is indicated by the number of leaks when the sample is dropped three times from a height of 150 cm at a room temperature of 23 ° C. Regarding the moldability and heat resistance, “good” is good and “bad” is bad.
I have to.
【００１３】[0013]
【発明の効果】以上説明してきたことから明らかなよう
に、本発明を採用することにより、柔軟性、透明性、耐
熱性が良く、微粒子の少ない輸液バッグを提供すること
ができる。また、単層のフィルムなので、成形が容易で
あり、フィルムのコストも小さいので、輸液バッグを安
価に提供することができる。As is apparent from the above description, by adopting the present invention, it is possible to provide an infusion bag having good flexibility, transparency and heat resistance and containing a small amount of fine particles. Also, since it is a single-layer film, molding is easy and the cost of the film is small, so that an infusion bag can be provided at low cost.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 濱 与志久 大阪市北区本庄西３丁目９番３号 株式会 社ニッショー内 Ｆターム(参考） 4F071 AA15 AA18 AA82 AF30 AF45 AH19 BB09 BC01 4J002 BB031 BB032 BB033 GB01 GG01 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshihisa Hama 3-9-3 Honjo Nishi, Kita-ku, Osaka F-term in Nissha Corporation (reference) 4F071 AA15 AA18 AA82 AF30 AF45 AH19 BB09 BC01 4J002 BB031 BB032 BB033 GB01 GG01
Claims (3)
セン触媒系直鎖状ポリエチレン４５〜７５重量％と、高
圧法低密度ポリエチレン５〜３５重量％と、密度０．９
１ｇ／ｃｍ3以下のメタロセン触媒系直鎖状ポリエチレ
ン１５〜４５重量％を含む重合体組成物から形成されて
なる耐熱性シート。1. A metallocene-catalyzed linear polyethylene having a density of 0.928 g / cm 3 or more, 45 to 75% by weight, a high-pressure low-density polyethylene of 5 to 35% by weight, a density of 0.9%
A heat-resistant sheet formed from a polymer composition containing 15 to 45% by weight of a metallocene-catalyzed linear polyethylene of 1 g / cm 3 or less.
セン触媒系直鎖状ポリエチレン５０〜７０重量％と、高
圧法低密度ポリエチレン１０〜３０重量％と、密度０．
９１ｇ／ｃｍ3以下のメタロセン触媒系直鎖状ポリエチ
レン２０〜４０重量％を含む重合体組成物から形成され
てなる、請求項１記載の耐熱性シート。Wherein a density of 0.928 g / cm 3 or more metallocene catalyst systems linear polyethylene 50-70% by weight, and 10 to 30 wt% high pressure low density polyethylene, density 0.
91g / cm 3 comprising formed from the metallocene catalyst system linear polyethylene polymer composition comprising 20 to 40 wt%, heat resistance sheet according to claim 1, wherein.
の壁を構成してなる、耐熱性に優れた輸液バッグ。3. An infusion bag having excellent heat resistance, comprising a wall of a main body of the bag using the sheet of claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000187338A JP3799970B2 (en) | 1999-10-08 | 2000-06-22 | Heat resistant sheet and infusion bag using the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11-287855 | 1999-10-08 | ||
| JP28785599 | 1999-10-08 | ||
| JP2000187338A JP3799970B2 (en) | 1999-10-08 | 2000-06-22 | Heat resistant sheet and infusion bag using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001172441A true JP2001172441A (en) | 2001-06-26 |
| JP3799970B2 JP3799970B2 (en) | 2006-07-19 |
Family
ID=26556913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000187338A Expired - Fee Related JP3799970B2 (en) | 1999-10-08 | 2000-06-22 | Heat resistant sheet and infusion bag using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3799970B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005200464A (en) * | 2004-01-13 | 2005-07-28 | Tosoh Corp | Resin composition and container composed thereof |
| JP2006265440A (en) * | 2005-03-25 | 2006-10-05 | Asahi Kasei Chemicals Corp | Polyethylene resin composition for extrusion laminate |
| WO2010098322A1 (en) | 2009-02-26 | 2010-09-02 | 三井化学株式会社 | Multilayer film and bag formed of the film |
| WO2011152387A1 (en) | 2010-05-31 | 2011-12-08 | 三井化学株式会社 | Multilayer film and bag formed from multilayer film |
-
2000
- 2000-06-22 JP JP2000187338A patent/JP3799970B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005200464A (en) * | 2004-01-13 | 2005-07-28 | Tosoh Corp | Resin composition and container composed thereof |
| JP4639590B2 (en) * | 2004-01-13 | 2011-02-23 | 東ソー株式会社 | Resin composition and container comprising the same |
| JP2006265440A (en) * | 2005-03-25 | 2006-10-05 | Asahi Kasei Chemicals Corp | Polyethylene resin composition for extrusion laminate |
| JP4641842B2 (en) * | 2005-03-25 | 2011-03-02 | 旭化成ケミカルズ株式会社 | Polyethylene resin composition for extrusion lamination |
| WO2010098322A1 (en) | 2009-02-26 | 2010-09-02 | 三井化学株式会社 | Multilayer film and bag formed of the film |
| WO2011152387A1 (en) | 2010-05-31 | 2011-12-08 | 三井化学株式会社 | Multilayer film and bag formed from multilayer film |
| US9108391B2 (en) | 2010-05-31 | 2015-08-18 | Otsuka Pharmaceutical Factory, Inc. | Multilayer film and bag formed of multilayer film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3799970B2 (en) | 2006-07-19 |
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