JPS6136942B2 - - Google Patents
Info
- Publication number
- JPS6136942B2 JPS6136942B2 JP53018746A JP1874678A JPS6136942B2 JP S6136942 B2 JPS6136942 B2 JP S6136942B2 JP 53018746 A JP53018746 A JP 53018746A JP 1874678 A JP1874678 A JP 1874678A JP S6136942 B2 JPS6136942 B2 JP S6136942B2
- Authority
- JP
- Japan
- Prior art keywords
- packaging bag
- blood
- protective sheet
- bag
- liquid nitrogen
- 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
Landscapes
- Medical Preparation Storing Or Oral Administration Devices (AREA)
- Packages (AREA)
Description
本発明は液体窒素温度−196℃という低温にお
いて使用するプラスチツクフイルム製容器の保護
方法に関し、特に−170℃〜−196℃の低温度で血
液あるいは血液中の一成分を保存するために使用
する血液保存用又は輸送用プラスチツクフイルム
容器の保護方法に関する。
近年、血液の保存に関して、液体窒素中(−
196℃)での急速凍結法が注目され、従来からの
冷蔵保存(4〜6℃、ガラス瓶、軟質塩化ビニル
製容器、ポリプロピレン製容器)や、緩速冷凍法
(−80〜−90℃、軟質塩化ビニル製容器)に対
し、血液凍結時間の短縮(緩速法5時間に対して
急速法2〜3分間)、赤血球の回収率や、回収さ
れる赤血球の質が良く、保存期間も大幅に伸びる
等の利点があり、実際の輸血使用量も増大してき
ており、この急速深冷保存用血液容器への要求も
高まつている。
しかしながら、前記の塩化ビニル製容器は−
196℃の低温では耐性を有せず、ほんの僅かな衝
撃によつても亀裂を生じ使用に耐えない。又この
冷凍血液用容器としてステンレス・スチール製の
ものが試験的に用いられてきたが封緘の困難、液
体窒素が容器中に流入し、赤血球を破壊する、透
明性がなく保存血液の状態がわからない、さらに
加工がむずかしく高価である等の欠点を有してい
る。このようなことから近年高度に2軸延伸した
ポリオレフイン系材料からなる袋や、内層に低温
耐性、血液適性のあるフツ素系樹脂を使用した袋
が提案されてきたが、ポリオレフイン系材料では
低温下での衝撃に弱い為にアルミ製のホルダーや
金網でサンドイツチして凍結する等の操作が必要
となり、また低温耐性の良好と言われるフツ素系
樹脂を使用した場合でも注意深い操作が必要で、
保存用の液体窒素を充填したストツカーに投入す
るに際して袋体下部の熱融着部に亀裂が生じた
り、シール時の温度・圧力の不均一によつて低温
下でのちよつとした衝撃で破袋が発生するといつ
た問題がある。
本発明は以上のような事情に鑑みてなされたも
ので、貴重な血液が保存操作段階での容器の破損
によつて失なわれることなく、また急速冷凍の通
常の操作に支障がなく、安定して作業ができるよ
う追求する中で得られたものである。
さらに本発明は−196℃という低温下において
も柔軟性あるいは強度を失なわない材料を追求す
る中で、布や網状の形態をもつたもの、さらには
それらが高度に延伸された繊維形態を取つている
ものが、同じ材料のフイルムや板等の連続体に見
られない低温下での強度を有し、屈曲や衝撃に対
して破壊しないという事実を発見し、本発明を得
るにいたつたのである。
すなわち本発明は低温耐性を有する熱可塑性合
成樹脂から成る包装袋に物質を入れて液体窒素中
で保存するに際して、この包装袋を化学繊維、天
然繊維、一軸延伸プラスチツクテープ又はコー
ド、あるいは割繊維から成る布状又は網状の保護
シートによつて保護することを特長とする低温凍
結用包装袋の保護方法である。
まず、保護すべき熱可塑性合成樹脂製包装袋は
例えば内層としてエチレン−四フツ化エチレンコ
ーポリマー、四フツ化エチレン−六フツ化プロピ
レンコーポリマー、塩化三フツ化エチレン樹脂又
はエチレン−塩化三フツ化エチレンコーポリマー
のうちの一種を有する単層又は多層の一定の低温
耐性を有するフイルム製包装袋等である。これは
目的とする血液あるいは血液中の一成分を凍結保
存するところから、衛生性、血液適合性を有し、
かつ熱融着によつて完全なシールが可能であり、
かつ−196℃という液体窒素中においても一定の
柔軟性、強度の保持が要求され上記樹脂はこれら
の要求を満足するものである。包装袋は単層でも
良いが、通常熱伝導の点でできるだけ薄いことが
求められ、強度面での考慮が必要なこと、さらに
熱シール加工の安定性等から他の強度のある耐熱
性合成樹脂フイルムと積層して使用される。袋体
は第1図に示すように上記樹脂を内側にして注
入、注出用口部材をとりつけて熱シールされ血液
保存用袋体となる。
次にこのようにして得られた包装袋を化学繊維
天然繊維又は一軸方向に延伸強化された合成樹脂
テープ、コード(細線)、割繊維からなる、液体
窒素が自由に通過可能な布状及び網状のシートに
よつて、包装袋端部の融着部分の下部全面を含む
包装袋の全体または一部を該シートが袋体の端部
よりも外側に出る形で被覆する。ここでいう布状
又は網状シートを構成する化学繊維にはレーヨン
等の再生繊維、アセテート等の半合成繊維、ナイ
ロン、ビニロン、アクリル等の合成繊維、ガラス
繊維等の無機繊維が含まれ、天然繊維には綿、麻
等の植物繊維、羊毛、絹等の動物繊維、石綿−鉱
物繊維が含まれる。また布状又は網状シートはポ
リエチレン、ポリプロピレン等の熱可塑性樹脂を
一軸延伸してなるテープや割繊維、さらにコード
によつて構成されても良い。これら布状及び網状
シートは液体窒素の通過が自由で血液の凍結速度
を遅らせない様、また低温下で包装袋に加わる衝
撃を吸収できる様に適当な開口性をもつことが求
められる。
血液の凍結は2〜3分という短時間で均一に行
うことが必要で包装袋は偏平で、かつ血液中に含
まれるガス分による熱伝導の低下を防ぐ為に垂直
な状態で液体窒素中に投入され、包装袋の下部に
応力・衝撃が集中する。この為、本発明で言う保
護用シートは少なく共包装袋端部の融着部分の下
部全面を含む包装袋の全体または一部を保護シー
トが包装袋の端部よりも外側に出る形にして被覆
することによつて凍結時及び保存時に包装袋が凍
結槽や保存槽の器壁に直接触れるのをさけるよう
にする。このことによつて、本来包装体が保持し
ていた耐低温耐性と相まつて、衝撃による亀裂・
破損がなく、血液凍結作用が容易に行なえるよう
になるのである。
さらに保護シートによる包装袋の被覆方法とし
ては、使用時にあらかじめ縫製してある保護シー
トの袋中へ包装袋を入れて、包装袋の外部で保合
シート同しを結合するか、又は使用時に包装袋を
第2図に示すような保護シートでサンドイツチ
し、包装袋の周縁部にポイント的に固定される様
にして被覆し、保護シートが包装袋面に密着はし
ても全く固定されていないか周縁部の一部に部分
的に固定されている様にする。これは加わつた衝
撃をできるだけ保護シートが受けるようにするこ
とと、固定される事によつて繊維又は延伸プラス
チツクスの柔軟性、弾力性が失なわれないように
するものである。また血液保存用包装袋は使用前
に121℃−20分のオートクレープ滅菌、又は200℃
−30分の乾熱滅菌等が行なわれる為、一部の繊
維、延伸プラスチツクは溶融したり、弾性・強度
を失ない、低温耐性がなくなる。この為保護シー
トによる包装袋の被覆は、包装袋の滅菌後通常使
用の直前に行なわれる必要がある。
以上述べて来た様に本発明による保護方法はほ
とんどすべての繊維から成る布や延伸ポリオレフ
イン等の網がつかえ、かつ袋体を布または網で被
覆するだけである為操作も容易であり、しかも低
温下での包装袋の破損を大幅に減少させるなど大
いなる利点を有する。また布・網も粗い目である
為内袋の透視が可能であり必要ならば窓をつける
ことも可能である。
以下実施例を述べる。
実施例 1
片面をコロナ放電処理し、更にポリエステルイ
ソシアネート系接着剤3g/m2を塗布した厚さ
0.05mmのエチレン−四フツ化エチレンコーポリマ
ーフイルムと厚さ0.05mmの架橋ポリエチレン樹脂
フイルムを貼り合わせ2層のフイルムとなし、こ
れに注入及び注出用口部材をつけてエチレン−四
フツ化エチレンコーポリマーフイルムを内面に合
わせて熱シールし血液保存用袋(400c.c.入り)を
得た。これを延伸強化した高密度ポリエチレンフ
イルムの割繊維から成る網状不織布で2つ折りに
した部分をミシン縫いしたものでもつて下部から
被覆し、上部をポリエチレン製の留め具によつて
結合し、密着複合させた。(第3図)
この複合袋に水:グリセリン=1:1液を充填
し口部を熱封緘して通常の血液凍結保存操作に従
つて液体窒素槽に垂直に入れ、3分間で凍結を行
なつた後直ちにひき出し液体窒素の充填してある
ストツカーに投入した。本発明によつて保護した
もの及び包装袋のみで共に同一の操作を行つた
が、本発明による保護をしないものは約2割の袋
で下部シール部に亀裂が生じたり、4%の袋に破
袋が生じて解凍すると内容物が流出したが本発明
では2%の袋のシール部に亀裂の発生はあつたが
内容物の流出という現象は発生しなかつた。また
保護シートには何の損傷も発生しなかつた。
実施例 2
片面をコロナ放電処理し、更にポリエステルイ
ソシアネート系接着剤3g/m2を塗布した厚さ
0.05mmの塩化三フツ化エチレン樹脂フイルムと厚
さ0.025mmの2軸延伸ポリエチレンテレフタレー
トフイルムを貼り合せて2層のフイルムとなし、
これに注入及び注出用口部材をつけて、塩化三フ
ツ化エチレンフイルムを内面に合わせて熱シール
し血液保存用袋(400c.c.)を得た。
次にスフ(レーヨン)70g/m2 ガラスク
ロス(ポリテトラフツ化エチレンで表面コート)
押出延伸PEネツト40g/m2 木綿布80g/
m2 ナイロン製ネツト35g/m2
をミシンで耳を出す形で三方縫合して保護シート
の袋とした。
上記血液保存用包装袋中に水:グリセリン=
1:1液を充填し、口部を熱封緘し、下部側から
保護シートの袋に入れ、保護シートの上部をナイ
ロン糸でポイント縫合して通常の血液凍結保存操
作に従つて実施例1と同様の操作を行なつた。以
下にその結果を示す。
The present invention relates to a method for protecting plastic film containers used at liquid nitrogen temperatures as low as -196°C, and particularly for blood used to preserve blood or one of its components at low temperatures of -170°C to -196°C. This invention relates to a method for protecting plastic film containers for storage or transportation. In recent years, blood preservation in liquid nitrogen (-
Rapid freezing at 196℃ (196℃) has attracted attention, while traditional refrigerated storage (4 to 6℃, glass bottles, soft vinyl chloride containers, polypropylene containers) and slow freezing (-80 to -90℃, soft Compared to vinyl chloride containers), the blood freezing time is shorter (5 hours for the slow method vs. 2 to 3 minutes for the rapid method), the recovery rate of red blood cells is better, the quality of the collected red blood cells is better, and the storage period is significantly longer. Due to its advantages such as stretchability, the amount of blood transfusions actually used is increasing, and the demand for blood containers for rapid cryogenic storage is also increasing. However, the vinyl chloride container mentioned above is-
It is not resistant to temperatures as low as 196°C, and cracks occur even with the slightest impact, making it unusable. Stainless steel containers have been used experimentally for frozen blood, but they are difficult to seal, liquid nitrogen flows into the container and destroys red blood cells, and the container is not transparent, making it difficult to determine the condition of the stored blood. Furthermore, it has disadvantages such as being difficult and expensive to process. For this reason, bags made of highly biaxially oriented polyolefin materials and bags made of fluorine-based resins with low temperature resistance and blood suitability for the inner layer have been proposed in recent years. Because it is vulnerable to shock, it is necessary to freeze it by sandwiching it with an aluminum holder or wire mesh, and even when using fluorine resin, which is said to have good low temperature resistance, careful operation is required.
Cracks may occur in the heat-sealed part at the bottom of the bag when it is placed in a stocker filled with liquid nitrogen for storage, or the bag may break due to a strong impact at low temperatures due to uneven temperature and pressure during sealing. There is a problem when this happens. The present invention has been made in view of the above circumstances, and it is possible to prevent valuable blood from being lost due to damage to the container during the preservation operation, and to ensure stability without interfering with normal rapid freezing operations. This is what I gained in my pursuit of being able to do the work. Furthermore, in the pursuit of materials that do not lose their flexibility or strength even at temperatures as low as -196°C, the present invention has developed fabrics that have a cloth or net shape, as well as highly stretched fibers. The inventors have discovered that the present invention has a strength at low temperatures that is not found in continuous bodies such as films and plates made of the same material, and does not break when subjected to bending or impact. be. That is, the present invention provides a method for storing a substance in a packaging bag made of a thermoplastic synthetic resin having low-temperature resistance in liquid nitrogen. This is a method for protecting a packaging bag for low temperature freezing, which is characterized by protecting it with a cloth-like or net-like protective sheet. First, the thermoplastic synthetic resin packaging bag to be protected may have an inner layer of, for example, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, chlorinated trifluoroethylene resin, or ethylene-tetrafluoroethylene trifluoride copolymer. These include single-layer or multi-layer film packaging bags having a certain low temperature resistance and having one kind of ethylene copolymer. Since this method freezes and preserves the target blood or a component of the blood, it is hygienic and compatible with blood.
And complete sealing is possible by heat fusion,
It is also required to maintain a certain level of flexibility and strength even in liquid nitrogen at -196°C, and the above resin satisfies these requirements. The packaging bag may be a single layer, but it is usually required to be as thin as possible in terms of heat conduction, and consideration must be given to strength, and in addition, other strong heat-resistant synthetic resins are used to ensure stability of heat sealing. Used by laminating with film. As shown in FIG. 1, the bag is heat-sealed with the above-mentioned resin inside, and a spout member for injection and dispensing is attached to form a blood storage bag. Next, the packaging bags obtained in this way are made of chemical fibers, natural fibers, synthetic resin tapes stretched and strengthened in a uniaxial direction, cords (thin wires), split fibers, and are made of cloth or net-like materials through which liquid nitrogen can freely pass. The sheet covers the entire or part of the packaging bag, including the entire lower part of the fused portion at the end of the packaging bag, in such a way that the sheet protrudes outside the end of the bag body. The chemical fibers constituting the cloth-like or net-like sheet mentioned here include recycled fibers such as rayon, semi-synthetic fibers such as acetate, synthetic fibers such as nylon, vinylon, acrylic, inorganic fibers such as glass fiber, and natural fibers. These include vegetable fibers such as cotton and hemp, animal fibers such as wool and silk, and asbestos-mineral fibers. Further, the cloth-like or net-like sheet may be composed of a tape or split fibers formed by uniaxially stretching a thermoplastic resin such as polyethylene or polypropylene, or a cord. These cloth-like and net-like sheets are required to have appropriate opening properties so that liquid nitrogen can pass through freely and the rate of freezing of blood is not delayed, and so that they can absorb shocks applied to the packaging bag at low temperatures. Blood needs to be frozen evenly in a short time of 2 to 3 minutes, and the packaging bag is flat and placed vertically in liquid nitrogen to prevent heat conduction from decreasing due to the gases contained in the blood. The stress and impact are concentrated at the bottom of the packaging bag. For this reason, the protective sheet referred to in the present invention is rarely used, and the entire or part of the packaging bag, including the entire lower part of the fused portion at the end of the co-packaging bag, is formed so that the protective sheet protrudes outside the end of the packaging bag. The coating prevents the packaging bag from directly touching the walls of the freezing tank or storage tank during freezing and storage. This, combined with the low-temperature resistance that the packaging originally had, makes it less susceptible to cracks and cracks caused by impact.
There is no damage and blood freezing can be performed easily. Furthermore, the methods of covering the packaging bag with a protective sheet include placing the packaging bag into a bag with a protective sheet that has been sewn before use, and joining the protective sheets together on the outside of the packaging bag, or wrapping the bag during use. Sandwich the bag with a protective sheet as shown in Figure 2 and cover it so that it is fixed at points around the periphery of the packaging bag, and even though the protective sheet is in close contact with the surface of the packaging bag, it is not fixed at all. or partially fixed to a part of the periphery. This is to ensure that the protective sheet receives as much of the applied impact as possible, and to prevent the fibers or stretched plastic from losing their flexibility and elasticity due to being fixed. In addition, blood storage packaging bags must be autoclaved for 20 minutes at 121°C or 200°C before use.
-Due to 30 minutes of dry heat sterilization, some fibers and stretched plastics may melt, lose their elasticity and strength, and lose their low-temperature resistance. For this reason, the packaging bag must be covered with a protective sheet after sterilization and immediately before normal use. As described above, the protection method according to the present invention can be used with cloth made of almost any type of fiber or mesh made of stretched polyolefin, and is easy to operate because the bag body is simply covered with cloth or mesh. It has great advantages such as greatly reducing damage to packaging bags at low temperatures. Also, since the cloth/mesh has coarse mesh, it is possible to see through the inner bag, and a window can be added if necessary. Examples will be described below. Example 1 One side is corona discharge treated and further coated with 3 g/m 2 of polyester isocyanate adhesive.
A 0.05mm ethylene-tetrafluoroethylene copolymer film and a 0.05mm-thick crosslinked polyethylene resin film are bonded together to form a two-layer film, and an injection and pouring spout member is attached to the ethylene-tetrafluoroethylene copolymer film. A copolymer film was placed on the inner surface and heat sealed to obtain a blood storage bag (containing 400 c.c.). This is then folded in half with a net-like non-woven fabric made of split fibers of high-density polyethylene film that has been stretched and reinforced, and then machine-sewn to cover the lower part, and the upper part is joined with a polyethylene fastener to create an adhesive composite. Ta. (Figure 3) Fill this composite bag with water:glycerin = 1:1, heat seal the opening, and place it vertically into a liquid nitrogen bath according to the usual blood cryopreservation procedure, and freeze for 3 minutes. Immediately after it had cooled, it was drawn out and placed in a stocker filled with liquid nitrogen. The same operation was performed on both the bags protected by the present invention and the packaging bags alone, but about 20% of the bags not protected by the present invention had cracks in the lower seal, and 4% of the bags had cracks. When the bags were torn and thawed, the contents leaked out, but in the present invention, cracks occurred in the seals of 2% of the bags, but no leakage of the contents occurred. Further, no damage occurred to the protective sheet. Example 2 One side is corona discharge treated and further coated with 3 g/m 2 of polyester isocyanate adhesive.
A 0.05 mm chloride trifluoride ethylene resin film and a 0.025 mm thick biaxially stretched polyethylene terephthalate film are bonded together to form a two-layer film.
An injection and dispensing opening member was attached to this, and an ethylene chloride trifluoride film was placed on the inner surface and heat sealed to obtain a blood storage bag (400 c.c.). Next, fabric (rayon) 70g/m 2 glass cloth (surface coated with polytetrafluoroethylene)
Extruded stretched PE net 40g/ m2 Cotton cloth 80g/m
A protective sheet bag was made by sewing 35 g/m 2 of m 2 nylon net with the ears exposed using a sewing machine. Water in the above blood storage packaging bag: Glycerin =
Fill with 1:1 liquid, heat seal the mouth, put it into a protective sheet bag from the bottom side, and point suture the top of the protective sheet with nylon thread. A similar operation was performed. The results are shown below.
【表】
以上の様に本発明によつて保護したものは、保
護しないものにくらべて非常に良好な低温耐性を
示した。[Table] As described above, the specimens protected according to the present invention exhibited much better low-temperature resistance than the specimens that were not protected.
図面は本発明の実施例を示し、第1図は包装袋
の平面図、第2図は保護シートの斜視図、第3図
は包装袋を保護シートで保護した時の平面図であ
る。
1……包装袋、2……シール部、3……口部、
4……保護シート、5……ミシン目、6……留め
具。
The drawings show embodiments of the present invention; FIG. 1 is a plan view of a packaging bag, FIG. 2 is a perspective view of a protective sheet, and FIG. 3 is a plan view of the packaging bag protected by the protective sheet. 1... Packaging bag, 2... Seal part, 3... Mouth part,
4...protective sheet, 5...perforation, 6...fastener.
Claims (1)
に際して、この包装袋を化学繊維、天燃繊維、一
軸延伸プラスチツクテープ、またはコード、ある
いは割繊維から成る布状又は網状の保護シートに
よつて保護することを特長とする低温凍結用包装
袋の保護方法。 2 少なくとも包装袋の下部全面を保護シートで
被覆することを特長とする前記第1項記載の保護
方法。 3 内層としてエチレン−四フツ化エチレンコー
ポリマー、四フツ化エチレン−六フツ化プロピレ
ンコーポリマー、塩化三フツ化エチレン樹脂又は
エチレン−塩化三フツ化エチレンコーポリマーう
ちの一種の樹脂を有する単層又は多層のプラスチ
ツクフイルム製包装袋を用いることを特長とする
前記第1項又は第2項記載の保護方法。 4 液体窒素中に投下の直前に被覆することを特
長とする前記第1項から第3項のいずれかに記載
の保護方法。[Scope of Claims] 1. When a substance is placed in a packaging bag and stored in liquid nitrogen, the packaging bag is made of synthetic fiber, natural fiber, uniaxially stretched plastic tape, cord, or cloth or net-like material made of split fibers. A method for protecting a packaging bag for low temperature freezing, characterized by protecting it with a protective sheet. 2. The protection method according to item 1 above, characterized in that at least the entire lower part of the packaging bag is covered with a protective sheet. 3. A single layer or a single layer having as an inner layer one of the following resins: ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, chlorotrifluoroethylene resin, or ethylene-chlorotrifluoroethylene copolymer 3. The protection method according to item 1 or 2, characterized in that a multilayer plastic film packaging bag is used. 4. The protection method according to any one of items 1 to 3 above, characterized in that the method is coated immediately before dropping into liquid nitrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1874678A JPS54111998A (en) | 1978-02-21 | 1978-02-21 | Protection method for packaging bag for low-temperature freezing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1874678A JPS54111998A (en) | 1978-02-21 | 1978-02-21 | Protection method for packaging bag for low-temperature freezing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS54111998A JPS54111998A (en) | 1979-09-01 |
| JPS6136942B2 true JPS6136942B2 (en) | 1986-08-21 |
Family
ID=11980210
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1874678A Granted JPS54111998A (en) | 1978-02-21 | 1978-02-21 | Protection method for packaging bag for low-temperature freezing |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS54111998A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5672871A (en) * | 1979-11-20 | 1981-06-17 | Terumo Corp | Blood vessel inside retaining catheter |
| JPS57188263A (en) * | 1981-05-15 | 1982-11-19 | Terumo Corp | Cathetel held in blood vessel |
| JP2002028220A (en) * | 2000-05-09 | 2002-01-29 | Kanto Chem Co Inc | Housing bag for medical liquid agent |
| JP2007055139A (en) * | 2005-08-25 | 2007-03-08 | Sony Corp | Liquid storage container and liquid cartridge |
| US9301520B2 (en) | 2007-12-21 | 2016-04-05 | Sartorius Stedim North America Inc. | Systems and methods for freezing, storing and thawing biopharmaceutical materials |
| US8177123B2 (en) | 2008-09-24 | 2012-05-15 | Sartorius Stedim North America Inc. | Systems and methods for freezing, storing and thawing biopharmaceutical materials |
-
1978
- 1978-02-21 JP JP1874678A patent/JPS54111998A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS54111998A (en) | 1979-09-01 |
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