JP2011140327A - Exterior bag for transfusion - Google Patents
Exterior bag for transfusion Download PDFInfo
- Publication number
- JP2011140327A JP2011140327A JP2010001817A JP2010001817A JP2011140327A JP 2011140327 A JP2011140327 A JP 2011140327A JP 2010001817 A JP2010001817 A JP 2010001817A JP 2010001817 A JP2010001817 A JP 2010001817A JP 2011140327 A JP2011140327 A JP 2011140327A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- oxygen
- infusion
- bag
- film
- 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
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- 239000001301 oxygen Substances 0.000 claims abstract description 100
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 100
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- 238000004806 packaging method and process Methods 0.000 claims abstract description 19
- 238000007789 sealing Methods 0.000 claims abstract description 8
- 238000001802 infusion Methods 0.000 claims description 47
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 28
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- 239000011347 resin Substances 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 16
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- 235000013343 vitamin Nutrition 0.000 claims description 9
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 150000001413 amino acids Chemical class 0.000 claims description 7
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- 229960000907 methylthioninium chloride Drugs 0.000 claims description 5
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- 238000006479 redox reaction Methods 0.000 claims description 3
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- 230000007246 mechanism Effects 0.000 claims description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims 1
- 230000035515 penetration Effects 0.000 abstract 1
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- 239000004707 linear low-density polyethylene Substances 0.000 description 22
- 229920000098 polyolefin Polymers 0.000 description 12
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- 239000000203 mixture Substances 0.000 description 7
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- 229920000642 polymer Polymers 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 239000012790 adhesive layer Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 239000012793 heat-sealing layer Substances 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 4
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- 235000010323 ascorbic acid Nutrition 0.000 description 3
- 239000011668 ascorbic acid Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
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- 229920002799 BoPET Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
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- RUKISNQKOIKZGT-UHFFFAOYSA-N 2-nitrodiphenylamine Chemical compound [O-][N+](=O)C1=CC=CC=C1NC1=CC=CC=C1 RUKISNQKOIKZGT-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-DCSYEGIMSA-N Beta-Lactose Chemical compound OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-DCSYEGIMSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- YTBSYETUWUMLBZ-UHFFFAOYSA-N D-Erythrose Natural products OCC(O)C(O)C=O YTBSYETUWUMLBZ-UHFFFAOYSA-N 0.000 description 1
- RFSUNEUAIZKAJO-VRPWFDPXSA-N D-Fructose Natural products OC[C@H]1OC(O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-VRPWFDPXSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-araboascorbic acid Natural products OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 1
- YTBSYETUWUMLBZ-IUYQGCFVSA-N D-erythrose Chemical compound OC[C@@H](O)[C@@H](O)C=O YTBSYETUWUMLBZ-IUYQGCFVSA-N 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 101000576320 Homo sapiens Max-binding protein MNT Proteins 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QQOPAWAPLFHEEP-UHFFFAOYSA-M [7-(dimethylamino)-2-methylphenoxazin-3-ylidene]-diethylazanium;chloride Chemical compound [Cl-].O1C2=CC(N(C)C)=CC=C2N=C2C1=CC(=[N+](CC)CC)C(C)=C2 QQOPAWAPLFHEEP-UHFFFAOYSA-M 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229940072107 ascorbate Drugs 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
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- SQHOAFZGYFNDQX-UHFFFAOYSA-N ethyl-[7-(ethylamino)-2,8-dimethylphenothiazin-3-ylidene]azanium;chloride Chemical compound [Cl-].S1C2=CC(=[NH+]CC)C(C)=CC2=NC2=C1C=C(NCC)C(C)=C2 SQHOAFZGYFNDQX-UHFFFAOYSA-N 0.000 description 1
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- CIWXFRVOSDNDJZ-UHFFFAOYSA-L ferroin Chemical compound [Fe+2].[O-]S([O-])(=O)=O.C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 CIWXFRVOSDNDJZ-UHFFFAOYSA-L 0.000 description 1
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- 239000011888 foil Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
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- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- KHLVKKOJDHCJMG-QDBORUFSSA-L indigo carmine Chemical compound [Na+].[Na+].N/1C2=CC=C(S([O-])(=O)=O)C=C2C(=O)C\1=C1/NC2=CC=C(S(=O)(=O)[O-])C=C2C1=O KHLVKKOJDHCJMG-QDBORUFSSA-L 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
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Images
Landscapes
- Packages (AREA)
- Wrappers (AREA)
Abstract
Description
本発明は、医療・医薬品や食品などの分野において、酸素や光の進入により品質を劣化させるような内容物が充填された遮光積層包装袋に関し、特に酸素が進入していることを色の変化により外から識別可能な輸液外装袋に関するものである。 The present invention relates to a light-shielding laminated packaging bag filled with contents that degrade the quality due to the ingress of oxygen or light in the fields of medical / pharmaceuticals, foods, etc., and in particular, the color change that oxygen has entered. It is related with the infusion exterior bag identifiable from the outside.
比較的大容量の液剤が充填される輸液バックは、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、柔軟なプラスチック一次容器に充填されたものが増えている。輸液バックに充填されるアミノ酸液や糖・電解質液などの薬剤は、酸素によって著しく変質しやすく、更には直接体内に薬剤を注入する事からも、一次容器は無添加のプラスチック容器を用いられることが多く、酸素バリア性はほとんど無いに等しい。そのため、充填された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剤を変質させてしまう。そこで、近年は輸液バックを酸素バリア性の高い包装材料で二次包装することが行われている。更に、使用直前にビタミンの混注忘れ防止のために、ビタミンの部屋を設けた3室構造(1室:アミノ酸、2室:糖・電解液、3室:ビタミン)も増えてきており、この場合、ビタミンがバック内に充填されている為、酸素バリア性以外に遮光性が必要となる。ビタミンが光に弱いことから遮光性が必要となる。 An infusion bag filled with a relatively large volume of liquid is filled in a flexible plastic primary container from the viewpoints of ease of handling (handling), weight reduction of the infusion bag, and volume reduction of garbage. is increasing. Drugs such as amino acid solution and sugar / electrolyte solution that are filled in the infusion bag are remarkably easily altered by oxygen, and because the drug is directly injected into the body, the primary container should be an additive-free plastic container. There are many oxygen barrier properties. Therefore, if the filled infusion bag is left in the atmosphere, oxygen in the atmosphere permeates the infusion bag and deteriorates the drug over time. Therefore, in recent years, secondary packaging of an infusion bag with a packaging material having a high oxygen barrier property has been performed. Furthermore, in order to prevent forgetting to mix vitamins just before use, a three-room structure (1 room: amino acids, 2 rooms: sugar / electrolyte, 3 rooms: vitamins) has been increasing. Since vitamins are filled in the bag, light shielding properties are required in addition to oxygen barrier properties. Since vitamins are sensitive to light, light shielding is necessary.
従来、酸素バリア性を満たす為に、PVDC(ポリ塩化ビニリデン)コートを施したOPP(延伸ポリプロピレン)、ONY(延伸ナイロン)、PET(ポリエチレンテレフタレート)などのKコートフィルム、EVOP(エチレン‐ビニルアルコール共重合体)フィルム、PVA(ポリビニルアルコール)フィルム、酸化アルミニウムや酸化珪素などを蒸着したPETフィルム、酸化アルミウムや酸化珪素などを蒸着した延伸ナイロンフィルム、EVOH層を中間層に有する多層フィルムや、MXD6ナイロン層を中間層に有するバリアナイロンなどが用いられた積層包装材料が広く用いられている。更に、遮光性を満たす為には、アルミ箔や、アルミ蒸着をしたPETフィルム、あるいはアルミ蒸着をした延伸ナイロンフィルムが用いられる。 Conventionally, in order to satisfy oxygen barrier properties, PPP (polyvinylidene chloride) coated OPP (stretched polypropylene), ONY (stretched nylon), PET (polyethylene terephthalate) and other K-coated films, EVOP (ethylene-vinyl alcohol) Polymer) film, PVA (polyvinyl alcohol) film, PET film deposited with aluminum oxide or silicon oxide, stretched nylon film deposited with aluminum oxide or silicon oxide, multilayer film having EVOH layer as intermediate layer, MXD6 nylon Laminated packaging materials using barrier nylon or the like having a layer as an intermediate layer are widely used. Furthermore, in order to satisfy the light shielding property, an aluminum foil, a PET film with aluminum vapor deposition, or a stretched nylon film with aluminum vapor deposition is used.
通常は、アミノ酸や、糖、電解液からなる高カロリー輸液が充填された一次容器が上記したフィルム材料を用い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。輸送工程中の振動により、輸液外装袋にピンホールが生じることがあり、発生したピンホールの検知と内容物を品質の保証をするために、酸素の有無で色の変色が起こる錠剤型、あるいはペーパー型の酸素インジケーターが用いられていた。しかし、ビタミンがあらかじめ充填された3室バックタイプの外装袋では遮光性が必要な為、外から色の変色を確認することができず、輸液外装袋を開封して確認しなければならなかった。 Usually, a primary container filled with a high-calorie infusion solution consisting of amino acids, sugars, and electrolytes is put in an infusion bag using the above-mentioned film material, and further packed and transported in cardboard. Tablet holes that may cause pinholes in the infusion bag due to vibration during the transportation process, and in order to detect the generated pinholes and guarantee the quality of the contents A paper-type oxygen indicator was used. However, since the three-chamber back-type exterior bag pre-filled with vitamins needs to be light-shielded, the color change cannot be confirmed from the outside, and the infusion exterior bag must be opened and confirmed. .
特許文献1では、酸素インジケーターをラベルとして機能付与したもので、ラベルを包装袋に貼着したものである。一体型となっている本発明とは異なる。 In Patent Document 1, an oxygen indicator is provided with a function as a label, and the label is attached to a packaging bag. It is different from the present invention which is an integrated type.
特許文献2では、酸素バリア性の必要性からアルミ蒸着を利用し、部分的にアルミ蒸着を抜き、窓部を作ることで、外装袋の外から酸素インジケーターを目視確認することを可能にする提案であるが、本発明とは異なる。 Patent Document 2 proposes that it is possible to visually check the oxygen indicator from the outside of the outer bag by using aluminum vapor deposition from the necessity of oxygen barrier property, partially extracting aluminum vapor, and making a window part. However, it is different from the present invention.
本発明は、従来技術の問題を解決するために成されたものであり、酸素バリア性と遮光性を付与した外装袋において、ピンホールの有無やシール不良によって中に酸素が進入したことを検知できる酸素インジケーターが外装袋の外から確認可能であり、更には、従来のような脱酸素剤を同封することなく、充填後の溶存酸素を吸収すること可能とすることを特徴とし、輸液外装袋の提供を課題としている。 The present invention has been made to solve the problems of the prior art, and in an exterior bag with oxygen barrier properties and light shielding properties, it is detected that oxygen has entered due to the presence or absence of pinholes or poor sealing. The oxygen indicator can be confirmed from the outside of the outer bag, and further, it is possible to absorb the dissolved oxygen after filling without enclosing a conventional oxygen scavenger. Is a challenge.
本発明の請求項1に係る発明は、一次容器を密封包装する輸液外装袋において、前記一次容器を密封している側から、少なくとも熱溶着層、酸素インジケーター層、酸素バリアフィルム層の順で積層されており、前記熱溶着層は、少なくとも遮光層と酸素吸収層が積層されていることを特徴とする輸液外装袋である。
本発明の請求項2に係る発明は、 前記熱溶着層は、少なくとも2層以上の多層構成によって形成されており、遮光層はポリエチレン中に遮光物質を分散させ、酸素吸収性層はポリエチレン中に鉄系酸素吸収物質を分散させることによって成され、遮光層による遮光性は全光線透過率において0.5%未満、酸素吸収層による酸素吸収性は0.1ml/cm2以上あることを特徴とする請求項1記載の輸液外装袋である。
The invention according to claim 1 of the present invention is an infusion package for sealing and packaging a primary container, and is laminated in the order of at least a thermal welding layer, an oxygen indicator layer, and an oxygen barrier film layer from the side sealing the primary container. The heat-welded layer is an infusion outer packaging bag in which at least a light shielding layer and an oxygen absorbing layer are laminated.
The invention according to claim 2 of the present invention is such that the thermal welding layer is formed of a multilayer structure of at least two layers, the light shielding layer disperses a light shielding material in polyethylene, and the oxygen absorbing layer in polyethylene. It is formed by dispersing an iron-based oxygen-absorbing substance, characterized in that the light-shielding property by the light-shielding layer is less than 0.5% in total light transmittance, and the oxygen-absorbing property by the oxygen absorbing layer is 0.1 ml / cm 2 or more. The infusion outer packaging bag according to claim 1.
本発明の請求項3に係る発明は、前記酸素インジケーター層は、メチレンブルーの酸化還元反応による変色機構を用いたことを特徴とする請求項1または2項記載の輸液外装袋である。 The invention according to claim 3 of the present invention is the infusion bag according to claim 1 or 2, wherein the oxygen indicator layer uses a discoloration mechanism by a redox reaction of methylene blue.
本発明の請求項4に係る発明は、前記熱溶着層は、前記一次容器を密封している側の最内層には遮光物質、酸素吸収物質が含まれていないことを特徴とする請求項1〜3の何れか1項に記載の輸液外装袋である。 The invention according to claim 4 of the present invention is characterized in that, in the heat welding layer, the innermost layer on the side where the primary container is sealed does not contain a light-shielding substance or an oxygen-absorbing substance. It is an infusion outer packaging bag given in any 1 paragraph of ~ 3.
本発明の請求項5に係る発明は、前記酸素バリアフィルム層は、アルミナや酸化珪素が蒸着された透明蒸着フィルム、又は、ナイロン樹脂層とエチレン−ビニルアルコール共重合樹脂層とナイロン樹脂層からなる共押し出しフィルム、エチレン‐ビニルアルコール共重合フィルム、ポリビニルアルコールフィルムのいずれかであることを特徴とする請求項1〜4の何れかに1項に記載の輸液外装袋である。 In the invention according to claim 5 of the present invention, the oxygen barrier film layer comprises a transparent vapor-deposited film in which alumina or silicon oxide is vapor-deposited, or a nylon resin layer, an ethylene-vinyl alcohol copolymer resin layer, and a nylon resin layer. The infusion exterior bag according to any one of claims 1 to 4, which is any one of a co-extruded film, an ethylene-vinyl alcohol copolymer film, and a polyvinyl alcohol film.
本発明の請求項6に係る発明は、前記一次容器は、アミノ酸、糖・電解液、ビタミンが分けられて充填されている輸液バックであることを特徴とする請求項1〜5の何れか1項に記載の輸液外装袋である。 The invention according to claim 6 of the present invention is characterized in that the primary container is an infusion bag filled with amino acids, sugar / electrolyte, and vitamins separately. The infusion outer packaging bag according to item.
熱溶着層が、酸素吸収層を持つことによって、従来のような脱酸素剤、酸素検知剤を同封することなく、輸液外装袋の外から酸素有無を検知可能な酸素バリア層、遮光層を持った輸液包装袋が可能となった。 The heat welding layer has an oxygen absorption layer, so it has an oxygen barrier layer and a light shielding layer that can detect the presence or absence of oxygen from outside the infusion outer packaging bag without enclosing a conventional oxygen scavenger and oxygen detector. Infusion packaging bags are now possible.
本発明の輸液外装袋は、酸素吸収層、遮光層、酸素バリアフィルム層を持つことによって、アミノ酸、糖・電解液、ビタミンを含む輸液バックの内容物を劣化させることなく保存することができる。酸素吸収性層は、輸液パック充填後の袋内の溶存酸素、輸液外装袋内の残存酸素を吸収する。遮光層は、光線から光劣化物質を遮光し保護する。酸素バリアフィルム層は、大気中の酸素が輸液バックを透過して内容物を経時的に変質させないために使用する。即ち、酸素吸収物質、酸素バリアフィルム層を備えることで、易酸化性物質
であるアミノ酸や糖・電解液などの薬剤の劣化を防ぎ、また遮光性を具えることで、光劣化物質であるビタミンの劣化を防ぐことができる。
The infusion bag of the present invention has an oxygen absorbing layer, a light-shielding layer, and an oxygen barrier film layer, so that it can be stored without deteriorating the contents of the infusion bag containing amino acids, sugar / electrolyte, and vitamins. The oxygen-absorbing layer absorbs dissolved oxygen in the bag after filling the infusion pack and residual oxygen in the infusion outer packaging bag. The light shielding layer shields and protects the photodegradable material from light rays. The oxygen barrier film layer is used so that oxygen in the atmosphere does not permeate the infusion bag and change the contents over time. That is, by providing an oxygen-absorbing substance and an oxygen barrier film layer, it is possible to prevent degradation of chemicals such as amino acids and sugars / electrolytes that are easily oxidizable substances, and to provide light-shielding properties, vitamins that are photo-degrading substances. Can be prevented.
輸液外装袋の外から酸素有無を検知可能な輸液外装袋であるためには、熱溶着層の構成は、輸液パックを密封している側から、遮光物質及び酸素吸収物質を含まない最内層、酸素吸収層、遮光層の順で積層されることが好ましい。 In order to be an infusion outer bag that can detect the presence or absence of oxygen from the outside of the infusion outer bag, the configuration of the heat-welded layer is the innermost layer that does not contain a light shielding substance and an oxygen absorbing substance from the side where the infusion pack is sealed, The oxygen absorbing layer and the light shielding layer are preferably laminated in this order.
輸液外装袋の構成としては、輸液パックを密封している側から、遮光物質及び酸素吸収物質を含まない最内層、酸素吸収層、遮光層、酸素インジケーター層、酸素バリアフィルム層の順で積層される。特に酸素インジケーター層は、ピンホールなど要因で、熱溶着層や、酸素バリアフィルム層から透過した酸素があれば、遮光層の外側面に位置しているため、輸液外装袋の外から酸素有無検知することができる。即ち熱溶着層と透明性を有する酸素バリアフィルム層との間に設けることで可能となる。 As the structure of the infusion bag, the innermost layer not containing the light-shielding substance and the oxygen-absorbing substance, the oxygen-absorbing layer, the light-shielding layer, the oxygen indicator layer, and the oxygen barrier film layer are laminated in this order from the side where the infusion pack is sealed. The In particular, the oxygen indicator layer is located on the outer surface of the light shielding layer if there is oxygen transmitted from the heat-welded layer or oxygen barrier film layer due to factors such as pinholes. can do. That is, it is possible to provide it between the heat welding layer and the transparent oxygen barrier film layer.
熱溶着層の最内層に遮光物質及び酸素吸収物質を含まないことで、シール強度を低下させることなく、耐内容物の安定性、保護性を維持した輸液外装袋である。とりわけ、500ml〜2000mlの大容量輸液バックの外装袋として有用である。 The inner bag of the heat-welded layer is an infusion outer bag that does not contain a light-shielding substance and an oxygen-absorbing substance, and maintains the stability and protective properties of the contents without reducing the sealing strength. In particular, it is useful as an outer bag of a large volume infusion bag of 500 ml to 2000 ml.
以下に、本発明を実施するための形態について具体的に説明する。 Below, the form for implementing this invention is demonstrated concretely.
図1は本発明の輸液外装袋の一例を示す断面図である。その構成は、印刷基材層(A)、接着層(B)、酸素バリアフィルム層(C)、熱溶着層(D)、酸素インジケーター層(E)からなる。熱溶着層(D)は、遮光層(F)、酸素吸収層(G)、最内層(H)からなる。 FIG. 1 is a cross-sectional view showing an example of the infusion outer packaging bag of the present invention. The structure consists of a printing base material layer (A), an adhesive layer (B), an oxygen barrier film layer (C), a heat welding layer (D), and an oxygen indicator layer (E). The heat welding layer (D) includes a light shielding layer (F), an oxygen absorption layer (G), and an innermost layer (H).
図2は輸液外装袋の一例を示す正面図であり、輸液外装袋(I)である。 FIG. 2 is a front view showing an example of an infusion exterior bag, which is an infusion exterior bag (I).
印刷基材層(A)は、印刷可能なプラスチックフィルムであれば制限はなく、ポリエチレンテレフタレート(PET)フィルム、延伸ナイロンフィルム、延伸ポリプロピレンフィルムなどがあり、厚みは12μ〜40μ程度が望ましい。耐ピンホール性を考慮しなければ、印刷基材層はなくても構わない。 The printing substrate layer (A) is not limited as long as it is a printable plastic film, and includes a polyethylene terephthalate (PET) film, a stretched nylon film, a stretched polypropylene film, and the like, and the thickness is desirably about 12 to 40 μm. If the pinhole resistance is not taken into consideration, the printing base material layer may be omitted.
接着層(B)は、1液あるいは2液硬化型ウレタン系接着剤なら制限はなく、固形分は40%以下、乾燥塗布量は1〜3g/m2程度が望ましい。グラビア塗布にてコーテイングされる。 The adhesive layer (B) is not limited as long as it is a one-component or two-component curable urethane adhesive, and the solid content is preferably 40% or less and the dry coating amount is preferably about 1 to 3 g / m 2 . Coated with gravure coating.
酸素バリアフィルム層(C)は、透明性を有し、酸素バリア性として5.0ml/m2/day/MPa(JIS K7126準拠、温度20℃、湿度65%RH)以下であれば限定されず、例えば2軸延伸ポリエステルフィルムにアルミナや酸化珪素が蒸着された透明蒸着フィルム、又は、ナイロン樹脂層とエチレン−ビニルアルコール共重合樹脂層とナイロン樹脂層からなる共押し出しフィルム、エチレン‐ビニルアルコール共重合フィルム、ポリビニルアルコールフィルムであり、表裏にコロナ処理のような易接着処理があるのが望ましい。上記酸素バリアフィルムは、市販されているものから利用できる。酸素バリア性能を有し、外装袋としての物性を持てば特に限定されない。 The oxygen barrier film layer (C) is not limited as long as it has transparency and has an oxygen barrier property of 5.0 ml / m 2 / day / MPa (conforming to JIS K7126, temperature 20 ° C., humidity 65% RH) or less. For example, a transparent deposited film in which alumina or silicon oxide is deposited on a biaxially stretched polyester film, or a coextruded film comprising a nylon resin layer, an ethylene-vinyl alcohol copolymer resin layer, and a nylon resin layer, ethylene-vinyl alcohol copolymer It is a film and a polyvinyl alcohol film, and it is desirable that the front and back have an easy adhesion treatment such as a corona treatment. The said oxygen barrier film can be utilized from what is marketed. If it has oxygen barrier performance and has the physical property as an exterior bag, it will not be specifically limited.
熱融着層(D)は、熱により溶融することで密封可能な熱可塑性ポリオレフィンであれば制限はなく、例えば低密度ポリエチレン(LDPE)、中密度ポリエチレン(MDPE)、直鎖状低密度ポリエチレン(L―LDPE)、エチレン・酢酸ビニル共重合体樹脂などのエチレン系樹脂や、ホモポリプロピレン樹脂、プロピレン・エチレンランダム共重合体樹脂、プロピレン・エチレンブロック共重合体樹脂、プロピレン・α―オレフィン共重合体樹脂などのプロピレン系樹脂など使用できる。しかし重量物を充填した際の強度を考慮すると、直鎖状低密度ポリエチレン(L―LDPE)が望ましく、厚みは40μ〜150μ程度が好適である。熱融着層(D)は、遮光層/酸素吸収層/最内層の全体の厚みを示している。熱融着層(D)は、それぞれ単層または共押し出し法により作成することができる。共押し出し法を用いて作製する方が、単層をそれぞれ貼り合わせるよりは効率がよく好ましい。 The heat-sealing layer (D) is not limited as long as it is a thermoplastic polyolefin that can be sealed by melting by heat. For example, low-density polyethylene (LDPE), medium-density polyethylene (MDPE), linear low-density polyethylene ( L-LDPE), ethylene resins such as ethylene / vinyl acetate copolymer resins, homopolypropylene resins, propylene / ethylene random copolymer resins, propylene / ethylene block copolymer resins, propylene / α-olefin copolymers Propylene resin such as resin can be used. However, considering the strength when filled with heavy objects, linear low density polyethylene (L-LDPE) is desirable, and the thickness is preferably about 40 μm to 150 μm. The thermal fusion layer (D) indicates the total thickness of the light shielding layer / oxygen absorbing layer / innermost layer. The heat-sealing layer (D) can be formed by a single layer or a coextrusion method, respectively. Manufacturing using the co-extrusion method is more efficient and preferable than laminating each single layer.
酸素インジケーター層(E)は、メチレンブルーの酸化還元反応を利用してインキ化されたものであれば特に制限はなく、グラビア印刷により印刷可能であることが望ましい。酸素インジケーター層Eは、バインダー樹脂に酸化還元色素や還元剤、その他の成分を混合した混合物から成っており、バインダー樹脂は、酸化還元色素や還元剤、その他の成分を基材上に固着させるために用いるものであり、親水基と疎水基を合せ持った樹脂が使用され、例えばポリビニルアセタール樹脂、メチルセルロース、エチルセルロース、親水基を導入したポリエステル樹脂などが好ましく、特にポリビニルアセタール樹脂が好ましい。その他の成分としては、水分を保持する保湿剤、吸収粉末、基材への濡れ性を向上させるためのレベリング剤、消泡剤などが使用される。酸化還元色素としては、メチレンブルー、ニューメチレンブルー、ニュートラルレッド、インジゴカルミン、サフラニンT、フェノサフラニン、カプリブルー、ナイルブルー、ジフェニルアミン、キシレンシアノール、ニトロジフェニルアミン、フェロイン、N−フェニルアントラニル酸ガ使用できる。特にメチレンブルーが好適に利用できる。還元剤としては、アスコルビン酸、エリソルビン酸やその塩、アスコルビン酸塩、D−アルビノース、D−エリスロース、D−グルコース、D−マンノース、D−フラクトース、D−ラクトースなどの還元糖、第一スズ塩、第一鉄塩など金属塩などが使用できる。 The oxygen indicator layer (E) is not particularly limited as long as it is inked using a redox reaction of methylene blue, and is desirably printable by gravure printing. The oxygen indicator layer E is composed of a mixture in which a redox dye, a reducing agent, and other components are mixed with a binder resin, and the binder resin is for fixing the redox dye, the reducing agent, and other components on the base material. A resin having both a hydrophilic group and a hydrophobic group is used. For example, polyvinyl acetal resin, methyl cellulose, ethyl cellulose, a polyester resin having a hydrophilic group introduced therein, and the like are preferable, and a polyvinyl acetal resin is particularly preferable. As other components, a moisturizing agent that retains moisture, an absorbent powder, a leveling agent for improving wettability to a substrate, an antifoaming agent, and the like are used. As the redox dye, methylene blue, new methylene blue, neutral red, indigo carmine, safranin T, phenosafranine, capri blue, nile blue, diphenylamine, xylene cyanol, nitrodiphenylamine, ferroin, and N-phenylanthranilic acid can be used. In particular, methylene blue can be suitably used. Examples of the reducing agent include ascorbic acid, erythorbic acid and salts thereof, ascorbate, D-albinose, D-erythrose, D-glucose, D-mannose, D-fructose, D-lactose, etc. Metal salts such as tin salts and ferrous salts can be used.
遮光層(F)は、熱可塑性ポリオレフィン樹脂の中に遮光物質を練り込み、分散させて押出し機で成膜される。遮光層の厚みは、10μm〜30μm程度で、3〜10重量%程度のカーボンブラックをメルトブレンドすることが望ましい。熱融着層の一層を占める。遮光物質としては、炭素系物質として、カーボンブラック、グラファイト、炭素繊維、金属物質として、鉄粉、銅粉、アルミニウム粉、金属酸化物として、シリカ、アルミナ、酸化鉄、酸化亜鉛、酸化マグネシウム、他に水酸化アルミニウム、水酸化マグネシウムなど挙げられる。特に耐熱性があり、不透明化する効果が好ましく、特に耐熱性、耐候性、価格面からカーボンブラックが好ましい。その粒度は細かいものが好ましいが、練り込みにより樹脂層(成膜)形成が可能で、遮光性が発現できれば、粒度範囲はこだわらない。遮光性は、実施例の評価結果から全光線透過率において、0.5%未満であればよい。 The light shielding layer (F) is formed by an extruder by kneading and dispersing a light shielding material in a thermoplastic polyolefin resin. It is desirable that the thickness of the light shielding layer be about 10 μm to 30 μm, and about 3 to 10% by weight of carbon black be melt blended. Occupies one layer of heat-sealing layer. As the light shielding material, carbon-based material, carbon black, graphite, carbon fiber, metal material, iron powder, copper powder, aluminum powder, metal oxide, silica, alumina, iron oxide, zinc oxide, magnesium oxide, etc. Examples thereof include aluminum hydroxide and magnesium hydroxide. In particular, it has heat resistance and the effect of making it opaque is preferable, and carbon black is particularly preferable from the viewpoint of heat resistance, weather resistance, and price. The fine particle size is preferably fine, but if the resin layer (film formation) can be formed by kneading and the light shielding property can be expressed, the particle size range is not particular. The light shielding property may be less than 0.5% in the total light transmittance from the evaluation results of the examples.
酸素吸収層(G)は、熱可塑性ポリオレフィン樹脂の中に酸素吸収物質を練り込み、分散させて押出し機にて成膜される。酸素吸収層の厚みは10μ〜40μ程度で、10〜30重量%程度の金属鉄をメルトブレンドすることが望ましい。熱融着層の一層を占める。酸素吸収物質の金属鉄としては、鉄粉系脱酸素剤に用いられる鉄粉を使用できる。例えば還元鉄粉、電解鉄粉、噴霧鉄粉が用いられる。その粒度は細かいものが好ましいが、練り込みにより樹脂層(成膜)形成が可能で、脱酸素機能が発現できれば、粒度範囲はこだわらない。また、実施例の評価結果から酸素吸収性については、0.1ml/cm2 以上の能力があればよい。 The oxygen absorbing layer (G) is formed into a film by an extruder after kneading and dispersing an oxygen absorbing material in a thermoplastic polyolefin resin. The thickness of the oxygen absorption layer is about 10 to 40 μm, and it is desirable to melt blend about 10 to 30% by weight of metallic iron. Occupies one layer of heat-sealing layer. As metallic iron of the oxygen absorbing substance, iron powder used for iron powder-based oxygen scavengers can be used. For example, reduced iron powder, electrolytic iron powder, or sprayed iron powder is used. The fine particle size is preferably fine, but the particle size range is not particular as long as the resin layer (film formation) can be formed by kneading and the deoxygenation function can be expressed. In addition, from the evaluation results of the examples, the oxygen absorbability is only required to be 0.1 ml / cm 2 or more.
以下に、本発明の具体的実施例について説明する。 Specific examples of the present invention will be described below.
輸液外装袋用として、以下の構成品を作成した。印刷基材層(A)/接着層(B)/酸素バリアフィルム層(C)/酸素インジケーター層(E)/接着層(B)/熱融着層(D)の構成である。
印刷基材層(A):OPP(延伸ポリプロピレン)フィルム、東セロ株式会社、U1、30μm片面処理
接着層(B):ウレタン2液接着剤、三井化学ポリウレタン株式会社、A−525/A−52、固形分30%、乾燥塗布量3g/m2
酸素バリアフィルム層(C):酸素バリア延伸ナイロンフィルム、凸版印刷株式会社、GL−AEYBC、15μm両面コロナ処理
熱溶着層(D):タマポリ株式会社、(遮光層20μm/酸素吸収層20μm/ポリオレフィン層20μm)
遮光層:株式会社プライムポリマー SP2020(L−LDPE)、95重量%、カ
ーボンブラック5重量%
酸素吸収層:SP2020(L−LDPE)、80重量%、金属鉄20重量%
ポリオレフィン層(最内層):SP2020(L−LDPE)、100重量%
酸素インジケーター層(E):東洋インキ株式会社、Y172酸素インジケーターA改、172酸素インジケーターB改、A改/B改=1/1にて使用、版200L、25μm
The following components were created for infusion outer packaging bags. It is the structure of a printing base material layer (A) / adhesion layer (B) / oxygen barrier film layer (C) / oxygen indicator layer (E) / adhesion layer (B) / heat fusion layer (D).
Printing substrate layer (A): OPP (stretched polypropylene) film, Tosero Co., Ltd., U1, 30 μm single-sided treatment adhesive layer (B): Urethane two-part adhesive, Mitsui Chemicals Polyurethanes Co., Ltd., A-525 / A-52, Solid content 30%, dry coating amount 3g / m 2
Oxygen barrier film layer (C): oxygen barrier stretched nylon film, Toppan Printing Co., Ltd., GL-AEYBC, 15 μm double-sided corona-treated heat welding layer (D): Tamapoly Co., Ltd. (light shielding layer 20 μm / oxygen absorbing layer 20 μm / polyolefin layer) 20μm)
Light-shielding layer: Prime Polymer Co., Ltd. SP2020 (L-LDPE), 95% by weight, carbon black 5% by weight
Oxygen absorption layer: SP2020 (L-LDPE), 80% by weight, metallic iron 20% by weight
Polyolefin layer (innermost layer): SP2020 (L-LDPE), 100% by weight
Oxygen indicator layer (E): Toyo Ink Co., Ltd., Y172 oxygen indicator A modified, 172 oxygen indicator B modified, A modified / B modified = 1/1, plate 200L, 25 μm
実施例1の構成の中で熱溶着層(D)を以下の処方にて作成した。
熱溶着層(D):タマポリ株式会社、(遮光層20μm/酸素吸収層20μm/ポリオレフィン層20μm)
遮光層:株式会社プライムポリマー SP2020(L−LDPE)、99重量%、カーボンブラック1重量%
酸素吸収層:SP2020(L−LDPE)、80重量%、金属鉄20重量%
ポリオレフィン層(最内層):SP2020(L−LDPE)、100重量%
In the configuration of Example 1, a heat welding layer (D) was prepared according to the following formulation.
Thermal welding layer (D): Tamapoly Co., Ltd. (light shielding layer 20 μm / oxygen absorbing layer 20 μm / polyolefin layer 20 μm)
Light-shielding layer: Prime Polymer Co., Ltd. SP2020 (L-LDPE), 99% by weight, carbon black 1% by weight
Oxygen absorption layer: SP2020 (L-LDPE), 80% by weight, metallic iron 20% by weight
Polyolefin layer (innermost layer): SP2020 (L-LDPE), 100% by weight
実施例1の構成の中で熱溶着層(D)を以下の処方にて作成した。
熱溶着層(D):タマポリ株式会社、(遮光層20μm/酸素吸収層20μm/ポリオレフィン層20μm)
遮光層:株式会社プライムポリマー SP2020(L−LDPE)、95重量%、カ
ーボンブラック5重量%
酸素吸収層:SP2020(L−LDPE)、95重量%、金属鉄5重量%
ポリオレフィン層(最内層):SP2020(L−LDPE)、100重量%
In the configuration of Example 1, a heat welding layer (D) was prepared according to the following formulation.
Thermal welding layer (D): Tamapoly Co., Ltd. (light shielding layer 20 μm / oxygen absorbing layer 20 μm / polyolefin layer 20 μm)
Light-shielding layer: Prime Polymer Co., Ltd. SP2020 (L-LDPE), 95% by weight, carbon black 5% by weight
Oxygen absorption layer: SP2020 (L-LDPE), 95 wt%, metallic iron 5 wt%
Polyolefin layer (innermost layer): SP2020 (L-LDPE), 100% by weight
実施例1の構成の中で熱溶着層(D)を以下の処方にて作成した。
熱溶着層(D):タマポリ株式会社、(遮光層20μm/酸素吸収層20μm/ポリオレフィン層20μm)
遮光層:株式会社プライムポリマー SP2020(L−LDPE)、98重量%、カーボンブラック2重量%
酸素吸収層:SP2020(L−LDPE)、80重量%、金属鉄20重量%
ポリオレフィン層(最内層):SP2020(L−LDPE)、100重量%
In the configuration of Example 1, a heat welding layer (D) was prepared according to the following formulation.
Thermal welding layer (D): Tamapoly Co., Ltd. (light shielding layer 20 μm / oxygen absorbing layer 20 μm / polyolefin layer 20 μm)
Light-shielding layer: Prime Polymer Co., Ltd. SP2020 (L-LDPE), 98% by weight, carbon black 2% by weight
Oxygen absorption layer: SP2020 (L-LDPE), 80% by weight, metallic iron 20% by weight
Polyolefin layer (innermost layer): SP2020 (L-LDPE), 100% by weight
実施例1の構成の中で熱溶着層(D)を以下の処方にて作成した。
熱溶着層(D):タマポリ株式会社、(遮光層20μm/酸素吸収層20μm/ポリオレ
フィン層20μm)
遮光層:株式会社プライムポリマー SP2020(L−LDPE)、97重量%、カーボンブラック3重量%
酸素吸収層:SP2020(L−LDPE)、80重量%、金属鉄20重量%
ポリオレフィン層(最内層):SP2020(L−LDPE)、100重量%
In the configuration of Example 1, a heat welding layer (D) was prepared according to the following formulation.
Thermal welding layer (D): Tamapoly Co., Ltd. (light shielding layer 20 μm / oxygen absorbing layer 20 μm / polyolefin layer 20 μm)
Light-shielding layer: Prime Polymer Co., Ltd. SP2020 (L-LDPE), 97% by weight, carbon black 3% by weight
Oxygen absorption layer: SP2020 (L-LDPE), 80% by weight, metallic iron 20% by weight
Polyolefin layer (innermost layer): SP2020 (L-LDPE), 100% by weight
実施例1の構成の中で熱溶着層(D)を以下の処方にて作成した。
熱溶着層(D):タマポリ株式会社、(遮光層20μm/酸素吸収層20μm/ポリオレフィン層20μm)
遮光層:株式会社プライムポリマー SP2020(L−LDPE)、95重量%、カーボンブラック5重量%
酸素吸収層:SP2020(L−LDPE)、90重量%、金属鉄10重量%
ポリオレフィン層(最内層):SP2020(L−LDPE)、100重量%
上記、実施例1〜6で作成したサンプルにて光線透過率、酸素バリア性、応答性評価、光照射試験の測定を行った。
<評価1>光線透過率
測定機:SZ―Σ80(日本電色工業(株))
方法:上記測定機にて全光線透過率を測定した。
<評価2>酸素バリア性(JIS K7126準拠)
測定機:MOCON社(OXTRAN)
測定条件:温度20℃、湿度65%RH
<評価3>応答性評価
方法:上記実施例において、内部を窒素置換した4方製袋品(285mm×340mm)を試作した。3日以内に還元色を示した場合は○、それ以上日数がかかった場合は×とした。最後に還元色を示したパウチを開封し、酸化色に変わるまでの1日以内であれば○、1日以上かかった場合は×とした。
製袋寸法:285mm×340mm
<評価4>光照射試験
方法:上記実施例において、4方製袋品(285mm×340mm)を試作し、高カロリー輸液 ネオパレン2号(1000ml、製造元:(株)大塚製薬工場)を充填し、蛍光灯照射試験(積算光量120万ルクス)後のアスコルビン酸残存量をUV−VIS吸収スペクトルから推定し、残存量50%以上を○、50%未満を×とした。
In the configuration of Example 1, a heat welding layer (D) was prepared according to the following formulation.
Thermal welding layer (D): Tamapoly Co., Ltd. (light shielding layer 20 μm / oxygen absorbing layer 20 μm / polyolefin layer 20 μm)
Light-shielding layer: Prime Polymer Co., Ltd. SP2020 (L-LDPE), 95% by weight, carbon black 5% by weight
Oxygen absorption layer: SP2020 (L-LDPE), 90% by weight, metallic iron 10% by weight
Polyolefin layer (innermost layer): SP2020 (L-LDPE), 100% by weight
The samples prepared in Examples 1 to 6 were measured for light transmittance, oxygen barrier property, responsiveness evaluation, and light irradiation test.
<Evaluation 1> Light transmittance measuring machine: SZ-Σ80 (Nippon Denshoku Industries Co., Ltd.)
Method: The total light transmittance was measured with the measuring instrument.
<Evaluation 2> Oxygen barrier property (conforms to JIS K7126)
Measuring instrument: MOCON (OXTRAN)
Measurement conditions: temperature 20 ° C., humidity 65% RH
<Evaluation 3> Responsiveness evaluation Method: In the above-described example, a four-sided bag-made product (285 mm × 340 mm) in which the inside was replaced with nitrogen was manufactured as a prototype. When the reduction color was shown within 3 days, it was marked with ◯, and when it took more than 3 days, it was marked with ×. Finally, the pouch showing the reduced color was opened, and if it was within 1 day until it changed to the oxidized color, it was marked as ◯, and when it took more than 1 day, it was marked as x.
Bag making dimensions: 285mm x 340mm
<Evaluation 4> Light Irradiation Test Method: In the above examples, a four-sided bag product (285 mm × 340 mm) was prototyped and filled with high-calorie infusion Neoparene No. 2 (1000 ml, manufacturer: Otsuka Pharmaceutical Factory), The residual amount of ascorbic acid after the fluorescent lamp irradiation test (accumulated light amount of 1,200,000 lux) was estimated from the UV-VIS absorption spectrum.
本発明は、酸化劣化、光劣化するような内容物の一次容器の外装袋に適しており、ピンホールやシール不良などにより外から酸素が進入した際に、インキの色の変化により袋内の環境を表示することが可能な酸素インジケーター機能を付与した遮光包材に有用である。 The present invention is suitable for an outer packaging bag of a primary container whose contents deteriorate due to oxidative degradation or photodegradation, and when oxygen enters from the outside due to a pinhole or a seal failure, the inside of the bag is changed due to a change in ink color. It is useful for light-shielding packaging materials that have an oxygen indicator function that can display the environment.
(A):印刷基材層
(B):接着層
(C):酸素バリアフィルム層
(D):熱溶着層
(E):酸素インジケーター層
(F):遮光層
(G):酸素吸収層
(H):最内層
(I):輸液外装袋
(A): Print substrate layer (B): Adhesive layer (C): Oxygen barrier film layer (D): Thermal welding layer (E): Oxygen indicator layer (F): Light shielding layer (G): Oxygen absorbing layer ( H): Innermost layer (I): Infusion outer packaging bag
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Cited By (3)
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JP2015048094A (en) * | 2013-08-30 | 2015-03-16 | 凸版印刷株式会社 | Light blocking packaging bag |
JP2016150191A (en) * | 2015-02-19 | 2016-08-22 | パナソニック株式会社 | Endoscope |
JP2019077505A (en) * | 2019-02-15 | 2019-05-23 | 凸版印刷株式会社 | Packaging bag |
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JP2015048094A (en) * | 2013-08-30 | 2015-03-16 | 凸版印刷株式会社 | Light blocking packaging bag |
JP2016150191A (en) * | 2015-02-19 | 2016-08-22 | パナソニック株式会社 | Endoscope |
JP2019077505A (en) * | 2019-02-15 | 2019-05-23 | 凸版印刷株式会社 | Packaging bag |
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