JP4187643B2 - 固形物品のための多層酸素検出システム - Google Patents
固形物品のための多層酸素検出システム Download PDFInfo
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- JP4187643B2 JP4187643B2 JP2003502485A JP2003502485A JP4187643B2 JP 4187643 B2 JP4187643 B2 JP 4187643B2 JP 2003502485 A JP2003502485 A JP 2003502485A JP 2003502485 A JP2003502485 A JP 2003502485A JP 4187643 B2 JP4187643 B2 JP 4187643B2
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- Prior art keywords
- oxygen
- indicator
- layer
- film
- patch
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/02—Food
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
- G01N31/223—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators for investigating presence of specific gases or aerosols
- G01N31/225—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators for investigating presence of specific gases or aerosols for oxygen, e.g. including dissolved oxygen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1324—Flexible food casing [e.g., sausage type, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
- Y10T428/1341—Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1355—Elemental metal containing [e.g., substrate, foil, film, coating, etc.]
- Y10T428/1359—Three or more layers [continuous layer]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1379—Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1379—Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
- Y10T428/1383—Vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit is sandwiched between layers [continuous layer]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24851—Intermediate layer is discontinuous or differential
Description
オレフィンポリマーまたはコポリマー/接合剤/EVOH/接合剤/オレフィンポリマーまたはコポリマーである。
Tanθ=2πfτ
によって寿命と関連付けられる。
τ0/τ=1+ksvp02
に用いられる。
一般に、標準スクリーニングのために3つのポリマー材料を用いた。これらは酢酸セルロースブチラート(CAB)、ポリスチレン(PS)、およびポリメチル−メタクリラート(PMMA)である。これらのポリマーはそれぞれ、非常に良好、良好、および低い酸素感受性を示し、ポリマー母材による応答の微調整の可能性を示すために選択した。
Perkin Elmar LS50B走査発光分光計を用いてリン光のスペクトルが得られた。投射光ビームに正しく位置合わせするために、プラスチックフィルムを支持するガラス板を、プラスチックまたは石英発光セルの中心にPTFEの支持体を用いて載せた。セルには、ガスの流れを可能にする入り口と出口のラインを有する気密ストッパーを装備した。セルは23℃に制御し、励起および放射波長を100%窒素雰囲気中で求めた。
フィルムの酸素に対する感度は、強度減衰測定および寿命遅延測定の両方によって求めた。前者は、Perkin Elmar LS50B走査発光分光計で行われ、後者はApplied Photophysics Laser Kinetic spectrometerを備えるNd/YAG Spectron Laserを用いて記録した。レーザー励起の軌跡はGould OS4072デジタル記憶オッシロスコープで記録し、反応速度の解析のためにコンピュータに送った。窒素/酸素ガスのブレンドをSignal Instrumentsガス混合機を用いて発生させた。
式中、I0およびIは酸素の不在および存在時の放射強度であり、KsvはStern−Volmer定数であり、%O2は存在する酸素のパーセントである。I0/I対%O2のプロットはStern−Volmer定数Ksvをもたらす。酸素センサーの他の有用な感度測定は、1/Ksvを与える。これはリン光強度IをI0/2の値に低下させるのに必要な%O2を表す。
多くの薄膜センサーで、ポリマー母材のガス透過性を高めるために使用される。本明細書に報告された大部分の測定は可塑化しないフィルムで行われたが、可塑化したフィルムも報告されている。
または、200:ITHF中の1mgのPtOEP
または、200:ITHF中の1mgのPdOEP
ジクロロメタン中の20重量/容量%ポリスチレン(MW=180,000)を5cm3
カンファーキノン(CQ)は、2つの光学異性体で存在するα−ジケトンである。R−形状の構造は以下に示されているが、本明細書で使用したサンプルは2つの異性体のブレンドである。
ジクロロメタン中の20重量/容量%ポリスチレン(mwt180,000)を10cm3
指示剤はポリマー溶液に固体として直接加え、完全に攪拌した。他のポリマーフィルムでは、酢酸セルロースブチラート(CAB)(アセトン中20重量/容量%)およびポリメチルメタクリラート(PMMA)(ジクロロメタン中30重量/容量%)を用いて同じ手順に従った。カンファーキノンのスペクトルおよび感度データは以下の表4に示されている。
エリスロシンBは2つの形状で入手可能な四ヨウ素置換キサンテン染料であり、その構造は以下に示されている。1つは特に「アルコール可溶性(spirit−soluble)」と呼ばれるが、どちらも水には特に非溶性である。
本研究には2つの処方を用いた。酸素センサーとしてのその容量は、エリスロシンBは予め樹脂ベースのビーズ上に不動化し、次いでそれはカラム中に充填し、またはシリコンフィルム中に分散した。これらのビーズは極めて低い酸素濃度(0.0005%)に対して感度のあることが報告されている。本研究ではこの仕事を再現し、また、感度をわれわれの目的により適うレベルに調節するため、染料を直接プラスチックフィルムの中に分散する試みを行った。2つの処方は以下の通りである
Amberlite XAD−2非イオン性ポリマー吸着剤を0.1g
90%エタノール中1×10−5MのエリスロシンB/0.1M酢酸10%/酢酸ナトリウムpH6の緩衝剤を4cm3
樹脂は最初にエタノール、次いで水で洗い、次いでオーブンで80ECで乾燥した。0.1gの樹脂を4cm3の染料溶液に浸漬し、ときどき攪拌しながら24時間放置した。得られた輝くピンクのビーズを濾過し、2重蒸留水で完全に洗い、40ECで12時間乾燥し、使用するまで乾燥して貯蔵した。これらのビーズはガラススライド上に鋳造した粘性のあるポリマーフィルム(例えばポリスチレン)の上に散布した。
150μlのアセトン中のエリスロシンを0.6mg
ジコロロメタン中の20重量/容量%ポリスチレンを5cm3
指示剤溶液をポリマー溶液に加え、完全に攪拌した。次いで通常の方法でフィルムを鋳造した。エリスロシンBは約550nmの励起波長を有し、放射波長は約625〜700nmである。フィルムは100%窒素中の発光スペクトルを示し、5%の酸素で完全に停止した。
酸素検知発光染料を含む2つの除去剤フィルムを、共押し出し成形および接着剤積層によって調製した。一般化した構造は以下の通りである。
この実施例は発光酸素検知指示剤(PdTPP)をパッチの形で使用することを示す。パッチは、9μm(0.36ミル)のPE表面上に2000ppmのPdTPP、および感圧接着剤を有する金属化PETラベル材を含む、押し出し成形多層フィルムから作った。パッチの酸素検知部の寸法は1.27×1.27cm(0.5×0.5インチ)であり、パッチ全体の寸法は3.8×3.8cm(1.5×1.5インチ)であった。上述のようにして起動した、市場で入手可能な酸素除去フィルム(OS1000(登録商標)、Cryovac Inc.)にパッチを貼付した。機械の速度および光の段数を変えることによって、表6に示すような種々のUV線量を達成した。Cryovac Inc.から入手可能な、酸素非除去の、標準的な市販の酸素バリア頂部ウェブT6230Bを使用して、比較試験用梱包も調製した。
封止材/接合剤/ナイロン/EVOH/ナイロン/接合剤/封止材
を有しており、
封止材は本明細書に開示されたいかなるものも含み、接合剤層は無水の修飾ポリマー性オレフィンまたはアミドの接着剤であり、ナイロン層はいかなるポリアミドまたはコポリアミドをも含み、EVOH(エチレン/ビニルアルコールコポリマー)層は酸素バリア層として機能する。酸素除去剤は上記フィルム構造内の層として適切に含むことができ、酸素指示剤層は同様に構造自体の中に、または本明細書に開示された隣接するパッチ内に、好ましくはパッチ内の個々の酸素バリア層を伴って含むことができる。
Claims (3)
- a)i)25℃、0%RH、1気圧で100cc/m2/24時間以下(ASTM D 3985)の酸素透過速度を有する酸素バリア層と、および
ii)酸素除去剤を含む層と
を含むフィルムと、ならびに
b)i)25℃、0%RH、1気圧で100cc/m2/24時間以下(ASTM D 3985)の酸素透過速度を有する酸素バリア層と、および
ii)発光化合物を含む酸素指示剤と
を含むパッチと
を含み、
前記パッチが、前記フィルムに接着され、
前記酸素指示剤が、パッチの酸素バリアとフィルムの酸素バリアの間に配置された固形物品。 - a)i)25℃、0%RH、1気圧で100cc/m2/24時間以下(ASTM D 3985)の酸素透過速度を有する酸素バリアを含む、トレーに接着された内張りと、および
ii)トレーフランジと
を含むトレーと、
b)トレー内張り上に配置された酸素感受性製品と、ならびに
c)i)25℃、0%RH、1気圧で100cc/m2/24時間以下(ASTM D 3985)の酸素透過速度を有する酸素バリアを含む層と、
ii)酸素除去剤を含む層と、および
iii)発光化合物を含んだ酸素指示剤を含む層と
を含む、酸素感受性製品の上に配置され、トレーフランジの領域内のトレー内張りに接着されたフィルムとを含み、
前記酸素指示剤が、トレー内張りの酸素バリアとフィルムの酸素バリアの間に配置された梱包。 - a)i)ポリエチレンテレフタレートを含んだポリマーを含む第1の層と、
ii)酸素除去剤を含む第2の層と、および
iii)ポリエチレンテレフタレートを含んだポリマーを含む第3の層と
を含む瓶壁と、ならびに
b)i)25℃、0%RH、1気圧で100cc/m2/24時間以下(ASTM D 3985)の酸素透過速度を有する酸素バリアと、および
ii)発光化合物を含む酸素指示剤と
を含む、瓶壁に接着されたパッチとを含み、
前記酸素指示剤が、パッチの酸素バリアと瓶壁の間に配置された瓶。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/875,515 US6689438B2 (en) | 2001-06-06 | 2001-06-06 | Oxygen detection system for a solid article |
PCT/US2002/015384 WO2002099416A1 (en) | 2001-06-06 | 2002-05-15 | Multi-layered oxygen detection system for a solid article |
Publications (3)
Publication Number | Publication Date |
---|---|
JP2004535571A JP2004535571A (ja) | 2004-11-25 |
JP2004535571A5 JP2004535571A5 (ja) | 2005-09-15 |
JP4187643B2 true JP4187643B2 (ja) | 2008-11-26 |
Family
ID=25365942
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2003502485A Expired - Fee Related JP4187643B2 (ja) | 2001-06-06 | 2002-05-15 | 固形物品のための多層酸素検出システム |
Country Status (10)
Country | Link |
---|---|
US (2) | US6689438B2 (ja) |
EP (2) | EP1393064B1 (ja) |
JP (1) | JP4187643B2 (ja) |
AT (1) | ATE473436T1 (ja) |
AU (1) | AU2002345539B2 (ja) |
CA (1) | CA2449786C (ja) |
DE (1) | DE60236930D1 (ja) |
MX (1) | MXPA03011228A (ja) |
NZ (1) | NZ529825A (ja) |
WO (1) | WO2002099416A1 (ja) |
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JP2007514168A (ja) * | 2003-12-12 | 2007-05-31 | クライオバック・インコーポレイテツド | 密閉包装における漏れ検出方法 |
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BRPI0506206A (pt) * | 2005-01-04 | 2007-07-17 | Yuanmei Yang | removedor de oxigênio inteligente com indicação de nìvel de oxigênio |
FR2880619B1 (fr) * | 2005-01-10 | 2010-03-12 | Cebal Sas | Emballages plastiques, en particulier tubes souples, contenant des substances reactives associees a un temoin de presence |
EP1715337A1 (en) * | 2005-04-20 | 2006-10-25 | IEE INTERNATIONAL ELECTRONICS & ENGINEERING S.A. | Leakage detection patch |
US20060289796A1 (en) * | 2005-06-22 | 2006-12-28 | Cryovac, Inc. | UV-C sensitive composition and dosimeter |
EP1966229B1 (en) | 2005-09-12 | 2015-10-21 | Abela Pharmaceuticals, Inc. | Systems for removing dimethyl sulfoxide (dmso) or related compounds, or odors associated with same |
US8435224B2 (en) * | 2005-09-12 | 2013-05-07 | Abela Pharmaceuticals, Inc. | Materials for facilitating administration of dimethyl sulfoxide (DMSO) and related compounds |
US8480797B2 (en) | 2005-09-12 | 2013-07-09 | Abela Pharmaceuticals, Inc. | Activated carbon systems for facilitating use of dimethyl sulfoxide (DMSO) by removal of same, related compounds, or associated odors |
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2001
- 2001-06-06 US US09/875,515 patent/US6689438B2/en not_active Expired - Lifetime
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WO2002099416A8 (en) | 2003-01-23 |
DE60236930D1 (de) | 2010-08-19 |
NZ529825A (en) | 2008-01-31 |
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