JP5519212B2 - 吸収物質を有する一体型生成物 - Google Patents
吸収物質を有する一体型生成物 Download PDFInfo
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- JP5519212B2 JP5519212B2 JP2009188070A JP2009188070A JP5519212B2 JP 5519212 B2 JP5519212 B2 JP 5519212B2 JP 2009188070 A JP2009188070 A JP 2009188070A JP 2009188070 A JP2009188070 A JP 2009188070A JP 5519212 B2 JP5519212 B2 JP 5519212B2
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Description
本出願は1998年5月29日に出願された米国特許出願No.09/087,830の一部継続出願であり、この出願は1997年3月5日に出願された米国特許出願No.08/812,315の一部継続出願であり、この出願は1996年3月5日に出願された米国特許出願No.08/611,298の一部継続出願であり,この出願は1995年4月に出願された米国特許出願No.08/424,996の一部継続出願である。
本発明は一般に、水不溶性ポリマー、親水性物質および吸収物質を含むモノリシック組成物(以下、一体型組成物と記す)に関する。一実施態様において、本発明は、一以上の吸収物質と混合して吸収物質含有ポリマーを形成する改質ポリマーに関する。本発明は、更に、ポリマー構造中に位置する吸収物質をポリマー体の外部の条件に曝す手段を有する含有ポリマーに関する。一実施態様において、本発明の含有ポリマーは、制御された環境を要求する物品の容器および包装体の製造に有用である。
定められているように、本発明の詳細な実施態様をここに開示する。しかしながら、開示される実施態様は色々な形で例示できる本発明の単なる代表例であることを理解すべきである。図は必ずしも定率縮尺ではなく、特定の成分の詳細を示すために若干の特徴は誇張されている。従って、ここに開示される具体的な構造および機能の詳細は制限的と解釈されるべきでなく、単なるクレームの基礎および当業者が本発明を様々に用いるように当業者を教示するための典型的基礎と解釈されるべきである。
ある別の実施態様では、本発明の親水性物質の一部又は全部を疎水性物質で置き換えることができる。
以下の実施例の目的は、本発明の組成物が以下の物質を膨潤および重量損失分析に付すことによって内部連絡溝を有することを証明することにある。
[A.サンプルの調製]
[フィルム#1]
約93質量%のポリプロピレン(Exxon Chemincals,商標Escorene(登録商標)ポリプロピレン3505G)および約7質量%のポリ(エチレングリコール)(Dow Chemical,商標E−4500)の配合物を十分混合して均一な配合物を得る。次ぎにこの配合物を約145℃から約165℃の範囲の16ゾーンの温度、供給速度約40lbs/時、スクリュー速度約460rpm、押出型6インチでLeistritz二軸スクリュー式押出機へ送った。次ぎに押出した組成物を約85℃から約92℃の範囲の温度で三本ロール式ホットプレスへ送って約4ミリのフィルムを形成した。
約68質量%のポリプロピレン(Exxon Chemincals,商標Escorene(登録商標)ポリプロピレン3505G)、約12質量%のポリ(エチレングリコール)(Dow Chemical,商標E−4500)および約20質量%のモレキュラーシーブ乾燥剤(Elf Atochem,商標Siliporite(登録商標)モレキュラーシーブ,4オングストローム)の配合物を十分混合して均一な配合物を得る。次ぎにこの配合物を約145℃から約165℃の範囲の16ゾーンの温度、供給速度約40lbs/時、スクリュー速度約460rpm、押出型6インチでLeistritz二軸スクリュー式押出機へ送った。次ぎに押出した組成物を約85℃から約92℃の範囲の温度で三本ロール式ホットプレスへ送って約4ミリのフィルムを形成した。
約34.88質量%のポリプロピレン(Exxon Chemincals,商標Escorene(登録商標)ポリプロピレン3505G)、約11.96質量%のポリ(エチレングリコール)(Dow Chemical,商標E−4500)、約52.82質量%のモレキュラーシーブ乾燥剤(Elf Atochem,商標Siliporite(登録商標)モレキュラーシーブ,4オングストローム)および約0.34質量%のグレー色素の配合物を十分混合して均一な配合物を得る。次ぎにこの配合物を約145℃から約165℃の範囲の16ゾーンの温度、供給速度約50lbs/時、スクリュー速度約460rpm、押出型6インチでLeistritz二軸スクリュー式押出機へ送った。次ぎに押出した組成物を約85℃から約92℃の範囲の温度で三本ロール式ホットプレスへ送って約4ミリのフィルムを形成した。
3種類の各サンプルから円形ディスク(OD 1.1cm)を切り取った。各サンプルの最初の乾燥質量を記録した。次ぎにサンプルを蒸留水2.0ml中でインキュベートし、室温で振盪放置した。定期的に1、2、3および34日目にディスクを取り出し、表面を吸い取り乾燥し、サンプルを秤量して膨潤程度を測定した。各時点で蒸留水を置換して浸漬条件とした。実験の終了時にサンプルを凍結乾燥して水分を除去し、サンプルを秤量して質量損失を測定した。図9は分析結果のグラフである。膨潤率(%)はある時点(t)の湿潤質量を最初の質量(0)で割って100をかけたものとして定義される。「乾燥」は34日間インキュベーションした後、最終的に凍結乾燥させたサンプル重を表す。
以下の実施例の目的は本発明の組成物が水不溶性ポリマーと親水性物質からなる2つの分離相を有することを証明することである。
[A.サンプルの調製]
[フィルム#4]
100%ポリプロピレン(Exxon Chemincals,商標Escorene(登録商標)3505G)を約145℃から約165℃の範囲の16ゾーンの温度、供給速度約40lbs/時、スクリュー速度約460rpm、押出型6インチでLeistritz二軸スクリュー式押出機へ送った。次ぎに押出した組成物を約85℃から約92℃の範囲の温度で三本ロール式ホットプレスへ送って約4ミリのフィルムを形成した。
約88質量%のポリプロピレン(Exxon Chemincals,商標Escorene(登録商標)ポリプロピレン3505G)、約12質量%のポリ(エチレングリコール)(Dow Chemical,商標E−4500)の配合物を十分混合して均一な配合物を得る。次ぎにこの配合物を約145℃から約165℃の範囲の16ゾーンの温度、供給速度約40lbs/時、スクリュー速度約460rpm、押出型6インチでLeistritz二軸スクリュー式押出機へ送った。次ぎに押出した組成物を約85℃から約92℃の範囲の温度で三本ロール式ホットプレスへ送って約4ミリのフィルムを形成した。
約68質量%のポリプロピレン(Exxon Chemincals,商標Escorene(登録商標)ポリプロピレン3505G)、約12質量%のポリ(エチレングリコール)(Dow Chemical,商標E−4500)および約20質量%のモレキュラーシーブ乾燥剤(Elf Atochem,商標Siliporite(登録商標)モレキュラーシーブ,4オングストローム)の配合物を十分混合して均一な配合物を得る。次ぎにこの配合物を約145℃から約165℃の範囲の16ゾーンの温度、供給速度約12lbs/時、スクリュー速度約460rpm、押出型6インチでLeistritz二軸スクリュー式押出機へ送った。次ぎに押出した組成物を約105℃の温度で三本ロール式ホットプレスへ送って約4ミリのフィルムを形成した。
処理したフィルムサンプルをTAC 7DX熱制御装置を備えたPerkin Elmer DSC7を用いて分析した。データはPerkin Elmer Pyrisソフトウエア(バージョン2.01)を用いて解析した。サンプルを−50から250℃まで10または15℃/分の速度で加熱した後、同じ速度で冷却し、その後同じ速度で250℃まで再び加熱した。以下の表はDSCから収集したデータである。融点のデータは融点ピーク(℃)と、第1の加熱ランプ(1°)および第2の加熱ランプ(2°)でのエンタルピー(ΔH、ジュール/gm)で示されている。図10から18について記載した縦列は表からのデータに対応するDSCからグラフ上アウトプットしたものである。サンプルは250℃までしか加熱していないので、フィルムサンプル#2、#3および#7中のモレキュラーシーブは融解せず、従って融点は記録できなかった。
ピーク℃ ピーク℃
100%ポリ(エチ 図10 1°63.808 190.362 なし なし
レングリコー
ル)
フィルム#4 図11 1°なし なし 162.700 78.462
2°なし なし 157.200 96.123
フィルム#5 図12 1°57.700 22.253 161.700 80.524
2°58.033 20.361 157.366 79.721
フィルム#6 図13 1°なし なし 159.366 42.385
2°なし なし 160.033 42.876
図14 1°56.366 19.460 162.200 70.073
フィルム#7
2°57.200 17.094 156.866 58.038
フィルム#2 図15 1°58.554 20.845 163.062 60.577
[インキュベー 2°58.779 16.037 157.783 53.706
ション前]
フィルム#2 図16 1°55.804 0.379 163.062 86.215
[インキュベー 2°57.529 0.464 158.533 67.949
ション後]
フィルム#3 図17 1°59.308 18.849 162.562 40.291
[インキュベー 2°56.529 10.122 158.283 24.980
ション前]
フィルム#3 図18 1°55.554 0.138 160.562 46.931
[インキュベー 2°なし なし 156.033 26.081
ション後]
以下の実施例の目的は、本発明の組成物が内部連絡溝を有し、かつ、親水性物質内に内分混合した吸水材を有することを証明することにある。
[A.走査電子顕微鏡(「SEM」)法]
フィルムの構造特性をHitachi S−2700顕微鏡を用い、照射ダメージを最小にするため8kV加速圧で操作して画像形成した。各フィルムの3種の遠近法で視認化した:1)フィルム表面;2)破壊フィルムの横断面(0°)および3)配向#2(90°)に対して90°の破壊フィルムの横断面。Polaron Instruments Sputter Coater E5100を用い、金パラジウムの5から10nm層でインキュベーション前のフィルムサンプルをスパッター被覆した。インキュベーション後のサンプルを70重量%エタノール10ml中で振盪しながら室温で24時間インキュベーションした。エタノールを除去し、サンプルを一晩風乾した。次ぎにサンプルを凍結させ、一晩凍結乾燥して残留した水分を除去した後スパッター被覆した。
フィルムサンプル#4、すなわち100%ポリプロピレンの走査電子顕微鏡写真は、水不溶性ポリマーが典型的には実質的に孔のない稠密で均質な形態であることを示している。外表面は、外表面が稠密で実質的に孔のないことを示している。倍率200倍における横断面図は、フィルムの脆性破壊の際に明らかとなった重合体の平板様領域を示している。倍率1000倍におけるもう1つの横断面図は、稠密な繊維質形態を示している。
以下の実施例の目的は本発明の組成物の吸水特性を証明することにある。フィルム#1と同様の処理条件を持つフィルムサンプルは、約50質量%のモレキュラーシーブ[4オングストローム]、約12質量%のポリ(エチレングリコール)および約38質量%のポリプロピレンを有しており、これらを以下の試験法を用いてその総質量についての吸水に関して評価した:(a)一方の環境チャンバーを予め72°F、相対湿度(「Rh」)10%に設定し、もう一方のチャンバーを予め72°F、20%Rhに設定する;(b)皿を秤量して質量を記録する;(c)天秤皿の風袋を測って天秤から皿の質量を除く;(d)次ぎにフィルムを載せて皿を秤量する;(e)次ぎに材料を秤量してその質量を記録する;(g)サンプルを所望の時間チャンバー内に置く;(h)所望の時間に達したらサンプルの載った皿を取り出して再び秤量し、その質量を記録する;さらに(i)、モレキュラーシーブ1グラム当たり増加した水分率(%)を、(サンプルの総質量増)/(サンプル中のモレキュラーシーブの質量)×100で算出する。結果は図19A[10%Rh]と19B[20%Rh]に示されている。4オングストロームのモレキュラーシーブの質量当たり増加した最大理論水分率(%)は約24ないし25%である。図19Aおよび19Bは本発明の高い伝導速度(例えば、吸水速度)を証明している。
本発明は、以下の特徴と有している。
(1)(a)水不溶性ポリマー、
(b)処理中にその融点を超えて加熱される親水性物質、および
(c)吸収物質
を含んでなる成分を配合することによって形成された一体型組成物。
(2)(a)水不溶性ポリマー、
(b)処理中にその融点を超えて加熱される親水性物質、および
(c)吸収物質
を含んでなる一体型組成物。
(3)(a)水不溶性ポリマー、
(b)処理中にその融点を超えて加熱される親水性物質、および
(c)吸収物質
を含んでなる成分を配合することによって形成された一体型組成物であって、混合後の成分の組合せが少なくとも3相からなる組成物を形成する、一体型組成物。
(4)(a)水不溶性ポリマー、
(b)処理中にその融点を超えて加熱される親水性物質、および
(c)吸収物質
を含んでなる一体型組成物であって、混合後の成分の組合せが少なくとも3相からなる組成物を形成する、一体型組成物。
(5)(a)水不溶性ポリマー、
(b)有機親水性物質、および
(c)吸収物質
を含んでなる成分を配合することによって形成された一体型組成物であって、混合後の成分の組合せが少なくとも3相からなる組成物を形成する、一体型組成物。
(6)(a)水不溶性ポリマーと親水性物質(該ポリマーと該物質は相互に可溶でない)を配合し;
(b)該ポリマーと該物質を混合し;
(c)該ポリマーと該物質の混合物をその物質の融点を超えて加熱し;
(d)吸収物質を加え;
(e)工程(d)の成分を混合し;
(f)その組成物を冷却する
ことを含んでなる工程によって形成された一体型組成物。
(7)水不溶性ポリマーがポリオレフィン、ポリカーボネートおよびポリアミドからなる群より選択される、(1)に記載の方法。
(8)水不溶性ポリマーがポリオレフィン、ポリカーボネートおよびポリアミドからなる群より選択される、(4)に記載の方法。
(9)親水性物質がポリグリコール、ポリ(エチレンビニルアルコール)、グリセリンおよびポリビニルアルコールからなる群より選択される、(1)に記載の方法。
(10)親水性物質がポリグリコール、ポリ(エチレンビニルアルコール)、グリセリンおよびポリビニルアルコールからなる群より選択される、(4)に記載の方法。
(11)成型品がシート、フィルム、ペレットおよびビーズからなる群より選択される、(1)に記載の方法。
(12)成型品がシート、フィルム、ペレットおよびビーズからなる群より選択される、(4)に記載の方法。
Claims (2)
- (a)25℃及び大気圧下で0.1%未満の水に対する溶解度を有する水不溶性ポリマー、該水不溶性ポリマーは、ポリオレフィン、ポリカーボネートおよびポリアミドからなる群より選択される;
(b)架橋されておらず且つ25℃及び大気圧下で1%以上の水に対する溶解度を有する有機親水性物質、該親水性物質は、ポリグリコール、ポリ(エチレンビニルアルコール)、グリセリンおよびポリビニルアルコールからなる群より選択される;及び
(c)前記ポリマーに対して10重量%〜60重量%の量で存在する、吸収物質、該吸収物質はモレキュラーシーブである;
を含んでなる成分を配合することによって形成されたモノリシック組成物であって、
少なくとも3つの相を有し、そして前記親水性物質で構成され且つ前記ポリマーを通して前記ガスを透過連絡させる通路として働く相互連結したチャンネルを有するモノリシック組成物、
から構成された容器であって、該容器が制御された環境を要求する物品を更に含み、該物品が食物又は医薬品である、容器。 - (a)25℃及び大気圧下で0.1%未満の水に対する溶解度を有する水不溶性ポリマー、該水不溶性ポリマーは、ポリオレフィン、ポリカーボネートおよびポリアミドからなる群より選択される;
(b)架橋されておらず且つ25℃及び大気圧下で1%以上の水に対する溶解度を有する有機親水性物質、該親水性物質は、ポリグリコール、ポリ(エチレンビニルアルコール)、グリセリンおよびポリビニルアルコールからなる群より選択される;及び
(c)前記ポリマーに対して10重量%〜60重量%の量で存在する、吸収物質、該吸収物質はモレキュラーシーブである;
を含んでなる成分を配合することによって形成されたモノリシック組成物であって、
少なくとも3つの相を有し、そして前記親水性物質で構成され且つ前記ポリマーを通して前記ガスを透過連絡させる通路として働く相互連結したチャンネルを有するモノリシック組成物、
から構成された包装体であって、該包装体が制御された環境を要求する物品を更に含み、該物品が食物又は医薬品である、包装体。
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-
1998
- 1998-09-18 US US09/156,937 patent/US6194079B1/en not_active Expired - Lifetime
-
1999
- 1999-09-17 ES ES99969423T patent/ES2344037T3/es not_active Expired - Lifetime
- 1999-09-17 EP EP99969423A patent/EP1187874B1/en not_active Expired - Lifetime
- 1999-09-17 DE DE69940931T patent/DE69940931D1/de not_active Expired - Lifetime
- 1999-09-17 BR BR9913886-7A patent/BR9913886A/pt not_active IP Right Cessation
- 1999-09-17 AU AU60460/99A patent/AU6046099A/en not_active Abandoned
- 1999-09-17 CN CN99812673A patent/CN1332770A/zh active Pending
- 1999-09-17 AT AT99969423T patent/ATE432319T1/de not_active IP Right Cessation
- 1999-09-17 WO PCT/US1999/021423 patent/WO2000017258A1/en active Application Filing
- 1999-09-17 JP JP2000574164A patent/JP2002526580A/ja not_active Withdrawn
- 1999-09-17 CA CA2344189A patent/CA2344189C/en not_active Expired - Lifetime
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2009
- 2009-08-14 JP JP2009188070A patent/JP5519212B2/ja not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
WO2000017258A1 (en) | 2000-03-30 |
CN1332770A (zh) | 2002-01-23 |
AU6046099A (en) | 2000-04-10 |
ATE432319T1 (de) | 2009-06-15 |
ES2344037T3 (es) | 2010-08-16 |
US6194079B1 (en) | 2001-02-27 |
JP2002526580A (ja) | 2002-08-20 |
CA2344189C (en) | 2012-05-29 |
CA2344189A1 (en) | 2000-03-30 |
EP1187874B1 (en) | 2009-05-27 |
EP1187874A1 (en) | 2002-03-20 |
JP2010018808A (ja) | 2010-01-28 |
EP1187874A4 (en) | 2002-04-17 |
BR9913886A (pt) | 2002-01-22 |
DE69940931D1 (de) | 2009-07-09 |
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