JP5430739B2 - 膜、特にガス貯蔵用膜 - Google Patents

膜、特にガス貯蔵用膜 Download PDF

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JP5430739B2
JP5430739B2 JP2012502520A JP2012502520A JP5430739B2 JP 5430739 B2 JP5430739 B2 JP 5430739B2 JP 2012502520 A JP2012502520 A JP 2012502520A JP 2012502520 A JP2012502520 A JP 2012502520A JP 5430739 B2 JP5430739 B2 JP 5430739B2
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membrane
layer
rubber
separate
webs
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JP2012521906A (ja
Inventor
シュトレ・イェンス
ブロマイアー・カール−ハインツ
パパディミトリオウ・アレクサンダー
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コンテイテヒ・エラストマー−ベシヒトウンゲン・ゲゼルシヤフト・ミト・ベシユレンクテル・ハフツング
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    • B32B25/04Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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    • B29C66/7375General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined uncured, partially cured or fully cured
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    • B29C66/9141Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature
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    • B29C66/919Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges
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Description

本発明は膜、特にガス貯蔵用膜に関する。
膜は、同種または異種の2流体を可撓な様式で分離するか、または互いに封止する場合に使用される。特に、ガス状流体の分離または封止に用いる膜は、それぞれの流体に適するように調整されたさまざまな特性を有する必要がある。例えば、圧縮ガスを可撓な様式で液体から分離する必要がある場合、その圧力をガス中に保持することが重要である。従って、この種の膜はガスに対して最大限不透過性である必要である。
ガスの拡散によるガス室からの散逸を防ぐために、ガス、特に窒素に対して最大限の不透過性を有する膜を設計できることが知られている。一例としては、独国特許出願公開第4243652A1号明細書、独国特許発明第4117411C2号明細書、および独国特許出願公開第3638828A1号明細書に、エラストマー層でできた膜がバリア層とも呼ばれるガスバリア層を有することが開示されている。ここで使用可能なガスバリア層の例としては、ポリアミド、ポリビニルアルコールまたはエチレン−ビニルアルコールコポリマーでできた層である。このガスバリア層を有する膜の寿命は比較的短く、即ち、通常ガスバリア層には周囲の弾性サブレイヤーがもつ弾性挙動がないため、その膨張は恒常的になり、しばしば長期使用後は恒常的な膨張を示す。
独国特許出願公開第4446304A1号明細書には、PTFEで構成された寿命が延長したダイアフラムポンプまたはダイアフラムバルブ用の膜が開示されている。ここではPTFE層は布層にホットプレス法により直接連結している。しかし、独国特許出願公開第4446304A1号明細書の寿命はガスに対する不透過性とは関連せず、むしろダイアフラムポンプまたはダイアフラムバルブに必要な負荷サイクルおよび折り曲げサイクルに関連する。
大容量容器、例えば、バイオガスシステムに必要な容器の封止用の膜は、一例として、独国実用新案第202007007060U1号明細書および欧州特許出願公開第1746336A1号明細書により周知である。独国実用新案第202007007060U1号明細書は、この種のガス貯蔵用膜の寿命を維持するために、即ち、その損傷を低減または回避するために、超高圧または超低圧により生ずる危険に対抗するよう封止可能な外部連通孔の取り付けを示している。欧州特許出願公開第1746336A1号明細書は、例えば、屋外部のガス貯蔵用ホイルの引き裂きを回避するために追加的な網の取り付けを記載している。両者共に実質的には、化学的寿命または化学的安定性の維持よりはむしろ機械的寿命の維持のための対策に関係する。
従って、本発明の目的は、良好な化学的安定性と、費用対効果の向上した長寿命という特徴をもつ可撓性膜、特に可撓性ガス貯蔵用膜を提供することである。
本発明は、少なくとも1つの継ぎ目構造により互いに連結された少なくとも2つの別個の膜ウェブから構成された膜であって、別個の膜ウェブが少なくとも1つのエラストマー層と少なくとも1つのPTFEベースの外層とを含むことを特徴とする膜により前記目的を達成する。
本発明の目的に適する“PTFEベース”とは、ポリテトラフルオロエチレン(PTFE)、変成ポリテトラフルオロエチレン(TFM)、フルオロエチレンポリマー(FEP)、パーフッ素化アルキルビニルエーテル−テトラエチレンコポリマー(PFA)またはエチレン−テトラフルオロエチレンコポリマー(ETFE)を意味する。本明細書ではPTFEまたはTFMの関与が好ましい。
驚くべきことに、この種の膜、特にこの種のガス貯蔵用膜は、ガス類に対する良好な不透過性および、特に寿命の延長による対費用効果の向上という特徴をもつことが分かった。
本発明の膜は、好ましくはコークス化プラント用ガスとも言われるコークス炉ガスの封止に使用し、好ましくはウイギンス(Wiggins)型ガス貯蔵システムで使用する。
更なる利点は、環境汚染が大きく削減されるため汚染シールオイルの処分の必要がなく、従って、シールオイルの連続循環用ポンプユニットの必要もない。更にこの種の膜は、ガス容量およびガス圧の変化に対しても機械的、化学的障害なしに柔軟に対応できる良好な復元力を有する弾性システムに相当する。
コークス炉ガスは、実質的には水素、メタン、窒素、一酸化炭素、二酸化炭素、硫化水素、アンモニア、低級炭化水素類、および高級炭化水素類を含む。このガスは石炭の熱分解により生成される。出発原料の石炭は天然産物であり、成分が変動するため、コークス炉ガスの構成は常に異なるが、その吸入または皮膚接触は、多くの場合有機体、人間または他の動物の命にかかわるほどに常に攻撃的である。
またコークス炉ガスの中には、エラストマー層だけでできた膜、ある場合にはレイドスクリム層、織物層または編み物層だけでできた膜を通して拡散でき、また前記層を破壊できるものもあることから、この攻撃的な特性は明らかである。
単なるPTFEベースのホイルである封止膜を用いた場合には、先ず極端なコスト高と全体強度が低いことと共に引っ張り強度の欠如となり、次いでガス貯蔵システムのプランジャーが、例えば、ねじれに対して安定化しない結果になる。
従って、本発明の膜は、少なくとも1つの継ぎ目構造により互いに連結された少なくとも2つの別個の膜ウェブから構成され、別個の膜ウェブは少なくとも1つのエラストマー層と少なくとも1つのPTFEベースの外層とを含む。
別個の膜ウェブ内の層数は好ましくは2〜6であり、特に好ましい1つの実施形態では別個の膜ウェブは4層を有する。
別個の膜ウェブは少なくとも1つのエラストマー層と少なくとも1つのPTFEベースの外層、ならびに少なくとも1つのレイドスクリム層または織物層または編み物層を含み、レイドスクリム層または織物層または編み物層が少なくとも片面でエラストマー層と連結していることが有利なことが証明された。
エラストマー層は、好ましくはクロロプレンゴムおよび/またはエチレン−プロピレンゴムおよび/またはエチレンープロピレンージエンゴムおよび/またはニトリルゴムおよび/またはハロニトリルゴムおよび/またはフッ素ゴムおよび/またはシリコーンゴムおよび/または塩素化ポリエチレンおよび/またはクロロスルホン化ポリエチレンベースのゴム混合物である。上述のゴムの定量的比率は50〜100phrが有利である。
本明細書では50〜100phrのクロロプレンゴムを含むことが好ましい。
本明細書におけるphr(ゴム100重量部当たりの重量部)データは、ゴム業界で慣習的な処方混合用の定量データである。本明細書では各物質の添加される重量部は、ゴム混合物中に存在する全てのゴム類の全組成の100重量部に常に基づく。エラストマー層の厚さは0.2〜1.3mm、好ましくは0.4〜1.0mmである。2つ以上のエラストマー層を使用する場合、その層の厚さは同一でも異なってもよい。同様に2つ以上のエラストマー層が存在する場合、別個のエラストマー層の定性的および/または定量的構成は同一でも異なってもよい。
レイドスクリム層または織物層または編み物層は、好ましくはポリアミド糸および/またはポリエステル糸および/またはアラミド糸および/または綿糸および/またはガラス繊維および/または金属糸から構成され、本明細書で特に好ましいのはポリアミド糸である。レイドスクリム層または織物層または編み物層の厚さは好ましくは0.1〜0.5mm、特に好ましくは0.2〜0.4mmであるが、PTFEベースの外層の厚さは好ましくは0.05〜0.5mm、特に好ましくは0.1〜0.3mmである。
2つ以上のレイドスクリム層または織物層または編み物層を用いた場合には、これら層の厚さは同一でも異なってもよい。同様に2つ以上のレイドスクリム層、織物層または編み物層が存在する場合には、これら層は上述の同一材料または異なる材料からなってもよい。
更にPTFEベースの外層はその両面がエッチングされているのが有利である。外層の両面をエッチングすることで化学結合が良好になり、その結果安定な継ぎ目構造と非常に薄い層厚さが得られる。層厚さが薄いことにより外層を含む層は可逆的な膨張が可能になり、膨張時にも外層とエラストマー層または外層とレイドスクリム層または織物層または縫い物層との分離を防ぐことができる。両面をエッチングした外層により得られる優れた遮閉性は、特に攻撃的なコークス炉ガスに対しても影響を受けない。本明細書ではこの外層の両面エッチングにおいて当業者に周知の任意のエッチングプロセスを使用できる。
非常に重要な他の要素は、特にガス貯蔵システムに使用される膜の継ぎ目構造である。通常重なり継ぎ目として設計され、低温で溶接および/または接着剤により接着される継ぎ目は、膜のかなり弱い場所の1つであることは当業者が承知している。本発明の膜は特定の継ぎ目構造を備える有利な特色を有する。この継ぎ目構造は、相互に当接するように配置された少なくとも2つの別個の膜ウェブから構成され、別個の膜ウェブの同種の層が、相互に当接するようにそれぞれ配置され、別個の膜ウェブのエラストマー層が相互に当接するようにそれぞれ配置された膜の外面において、別個の膜ウェブが重ね合わせシートと第1ゴムマトリックスとにより互いに連結され、かつ、別個の膜ウェブの外層が相互に当接するようにそれぞれ配置された膜の他方の面において、別個の膜ウェブがPTFEベースの重ね合わせ層と第2ゴムマトリックスとにより互いに連結されている。
別個の膜ウェブの全体の層厚さは、それらが当接して配置されているため、同じはずである。
それぞれの重ね合わせシートの幅と重ね合わせ層の幅は、最も幅が狭い膜ウェブを起点とすると別個の膜ウェブの幅より小さいことは自明である。
重ね合わせシートの幅および/または重ね合わせ層の幅は、本明細書ではそれぞれ2〜20cm、好ましくは5〜15cmであることが有利であることが明らかになった。
1つの好ましい実施形態では、この重ね合わせシートは加硫シートまたは未加硫シートである。しかし未加硫シートが有利である。
重ね合わせシートの構成と構造は、少なくとも1つの膜ウェブ構成および/または構造に一致することが更に有利である。重ね合わせシートの厚さは、外層を除いた別個の膜ウェブの全厚さと同一であっても、異なってもよい。
1つの特定の実施形態では、重ね合わせ層はポリテトラフルオロエチレン(PTFE)または変成ポリテトラフルオロエチレン(TFM)から構成される。重ね合わせ層の材料および/または厚さは、外層の材料および/または厚さと同一でもあっても、異なってもよい。少なくとも重ね合わせ層の材料が外層の材料と同一であることが有利である。
この重ね合わせ層は両面がエッチングされていることがまた有利である。
重ね合わせ層の両面がエッチングされていることで化学結合が良好になり、その結果安定な継ぎ目構造と非常に薄い層厚さが得られる。層厚さが薄いことにより重ね合わせ層は可逆的な膨張が可能になり、膨張時でも重ね合わせ層と第2ゴムマトリックスおよび/または外層との分離を防ぐことができる。両面エッチングされた重ね合わせ層により得られる優れた遮閉性は、特に攻撃的なコークス炉ガスに対しても影響をうけない。本明細書では重ね合わせ層の両面エッチングにおいて当業者に周知の任意のエッチングプロセスが使用できる。
第1ゴムマトリックスおよび第2ゴムマトリックスのゴムマトリックスは、好ましくはクロロプレンゴムおよび/またはエチレン−プロピレンゴムおよび/またはエチレンープロピレンージエンゴムおよび/またはニトリルゴムおよび/またはハロニトリルゴムおよび/またはフッ素ゴムおよび/またはシリコーンゴムおよび/または塩素化ポリエチレンおよび/またはクロロスルホン化ポリエチレンで構成する。特に好ましい1つの実施形態では、第2ゴムマトリックスはフッ素ゴム(FKM)で構成する。本明細書では、別個のゴムマトリックスは定性的および/または定量的に同一であっても、異なってもよい。
重ね合わせシートは別個の膜ウェブに面した片面上にPTFEベースの材料を含まないことが更に有利である。
新規な膜の形状は好ましくは中空円柱型、ドーナツ型または円錐型であり、全外周は5〜300m、好ましくは10〜200mである。しかし上述の形状の組み合わせもまた可能である。
この膜の製造は少なくとも以下のステップを含む。
−別個の膜ウェブのPTFEベースの外層が、別個の膜ウェブの加硫中にホイルの形態で適用される、少なくとも2つの別個の膜ウェブの製造;
−別個の膜ウェブの加硫;
−加硫された別個の膜ウェブの同種の層が、相互に当接するようにそれぞれ配置される、加硫された別個の膜ウェブを相互に当接するように配置すること;
−別個の膜ウェブのエラストマー層が、相互に当接するようにそれぞれ配置された膜の外面にシートと第1ゴムマトリックスを適用し、かつ、別個の膜ウェブのPTFEベースの外層が、相互に当接するようそれぞれ配置された他方の外面にPTFEベースの層と第2ゴムマトリックスを適用するような様式で、加硫された別個の膜ウェブを継ぎ目構造により連結すること;
−ホットプレス法による継ぎ目構造の加硫。
本明細書では別個の膜ウェブの加硫および/または継ぎ目構造の加硫は、140〜190Cの温度で実施するのが有利である。
上述のプロセスによって、連結部位で強度ロスが殆どなく、かつ、膜の全領域で膨張が可能になるような様式で、別個の膜ウェブ間の加硫された連結を可能とする継ぎ目構造が得られる。
本発明の膜を特にガス貯蔵膜の形態で使用する場合、コークス炉ガスの封止に関してはガスまたはガス混合物に面する側は、PTFEベースの材料で構成された膜側となる。
次に発明例を用いて、本発明を以下の図面を参考にして図示する。
別個の膜ウェブの断面図が表されている。 継ぎ目構造の断面図が表されている。
以下の番号は前記図に適応する。
1 外層
2、2’ エラストマー層
3 レイドスクリムまたは織物層または編み物層
4、4’ 膜ウェブ
5 重ね合わせシート(帯条片)
6 第1ゴムマトリックス
7 重ね合わせ層
8 第2ゴムマトリックス

Claims (26)

  1. 少なくとも1つの継ぎ目構造を介して互いに連結された少なくとも2つの別個の膜ウェブから構成され、別個の膜ウェブ(4,4’)がそれぞれ少なくとも1つのエラストマー層(2,2’)と少なくとも1つのPTFEベースの外層(1)とを含むことを特徴とするガス貯蔵であって、前記継ぎ目構造が、相互に当接するように配置された少なくとも2つの別個の膜ウェブ(4,4’)から構成され、前記別個の膜ウェブ(4,4’)の同種の層が、相互に当接するようにそれぞれ配置され、別個の膜ウェブ(4,4’)の前記エラストマー層(2,2’)が、相互に当接するようにそれぞれ配置された前記膜の外面において、前記2つの膜ウェブ(4,4’)が重ね合わせシート(5)と第1ゴムマトリックス(6)とにより互いに連結され、かつ、前記別個の膜ウェブ(4,4’)の前記外層(1)が、相互に当接するようにそれぞれ配置された他方の外面において、前記外層(1)がPTFEベースの重ね合わせ層(7)と第2ゴムマトリックス(8)とにより互いに連結されている、ガス貯蔵膜
  2. 前記別個の膜ウェブ(4,4’)内の層数が2〜6であることを特徴とする請求項1に記載の膜。
  3. 前記別個の膜ウェブ(4,4’)内の層数が4であることを特徴とする請求項1または2に記載の膜。
  4. 別個の膜ウェブ(4,4’)がそれぞれ少なくとも1つのレイドスクリム層または織物層または編み物層(3)も含み、前記レイドスクリム層または織物層または編み物層(3)は、少なくとも片面でエラストマー層(2,2’)に連結されていることを特徴とする請求項1〜3のいずれか一項に記載の膜。
  5. 前記エラストマー層(2,2’)が、クロロプレンゴムおよび/またはエチレン−プロピレンゴムおよび/またはエチレンープロピレンージエンゴムおよび/またはニトリルゴムおよび/またはハロニトリルゴムおよび/またはフッ素ゴムおよび/またはシリコーンゴムおよび/または塩素化ポリエチレンおよび/またはクロロスルホン化ポリエチレンをベースとしたゴム混合物であることを特徴とする請求項1〜4のいずれか一項に記載の膜。
  6. 前記エラストマー層(2,2’)が、クロロプレンゴムおよび/またはエチレン−プロピレンゴムおよび/またはエチレンープロピレンージエンゴムおよび/またはニトリルゴムおよび/またはハロニトリルゴムおよび/またはフッ素ゴムおよび/またはシリコーンゴムおよび/または塩素化ポリエチレンおよび/またはクロロスルホン化ポリエチレンを50〜100phr含むことを特徴とする請求項5に記載の膜。
  7. 前記エラストマー層(2,2’)が50〜100phrのクロロプレンゴムを含むことを特徴とする請求項6に記載の膜。
  8. 前記エラストマー層(2,2’)の厚さが0.2〜1.3mmであることを特徴とする請求項1〜7のいずれか一項に記載の膜。
  9. 前記レイドスクリム層または織物層または編み物層(3)が、ポリアミド糸および/またはポリエステル糸および/またはアラミド糸および/または綿糸および/またはガラス繊維および/または金属糸から構成されることを特徴とする請求項4〜8のいずれか一項に記載の膜。
  10. 前記レイドスクリム層または織物層または編み物層(3)がポリアミド糸から構成されることを特徴とする請求項9に記載の膜。
  11. 前記レイドスクリム層または織物層または編み物層(3)の厚さが0.1〜0.5mmであることを特徴とする請求項9または10に記載の膜。
  12. 前記外層(1)の厚さが0.05〜0.5mmであることを特徴とする請求項1〜11のいずれか一項に記載の膜。
  13. 前記外層(1)の厚さが0.1〜0.3mmであることを特徴とする請求項12に記載の膜。
  14. 前記外層(1)が両面エッチングされていることを特徴とする請求項1〜13のいずれか一項に記載の膜。
  15. 前記重ね合わせシート(5)および/または前記重ね合わせ層(7)の幅がそれぞれ2〜20cmであることを特徴とする請求項1〜14のいずれか一項に記載の膜。
  16. 前記重ね合わせ層(7)が両面エッチングされていることを特徴とする請求項1〜15のいずれか一項に記載の膜。
  17. 前記第2ゴムマトリックス(8)がフッ素ゴムを含むことを特徴とする請求項1〜16のいずれか一項に記載の膜。
  18. 前記重ね合わせシート(5)が、前記別個の膜ウェブ(4,4’)に面した側にPTFEベースの材料を含まないことを特徴とする請求項1〜17のいずれか一項に記載の膜。
  19. 膜の形状が中空円柱型、ドーナッツ型または円錐型であることを特徴とする請求項1〜18のいずれか一項に記載の膜。
  20. 膜の全外周が5〜300mであることを特徴とする請求項1〜19のいずれか一項に記載の膜。
  21. 膜の全外周が10〜200mであることを特徴とする請求項20に記載の膜。
  22. 少なくとも以下のステップ:
    −前記別個の膜ウェブ(4,4’)のPTFEベースの前記外層(1)が、前記別個の膜ウェブ(4,4’)の加硫中にホイルの形態で適用される、少なくとも2つの別個の膜ウェブ(4,4’)の製造;
    −前記別個の膜ウェブ(4,4’)の加硫;
    −加硫された前記別個の膜ウェブ(4,4’)の同種の層が、相互に当接するようにそれぞれ配置される、加硫された前記別個の膜ウェブ(4,4’)を相互に当接するように配置すること;
    −前記別個の膜ウェブ(4,4’)の前記エラストマー層(2,2’)が、相互に当接するようにそれぞれ配置された前記膜の外面にシート(5)と第1ゴムマトリックス(6)を適用し、かつ、前記別個の膜ウェブ(4,4’)の前記PTFEベースの外層(1)が、相互に当接するようそれぞれ配置された他方の外面にPTFEベースの層(7)と第2ゴムマトリックス(8)を適用するような様式で、加硫された前記別個の膜ウェブ(4,4’)を継ぎ目構造により連結すること;
    −ホットプレス法による前記継ぎ目構造の加硫;
    を特徴とする請求項1〜21のいずれか一項に記載の膜の製造方法
  23. 別個の前記膜ウェブ(4,4’)の加硫および/または前記継ぎ目構造の加硫を140〜190Cの温度で実施することを特徴とする請求項22に記載の膜製造方法。
  24. ガス貯蔵用膜としての請求項1〜21のいずれか一項に記載の膜の使用。
  25. コークス炉ガスを含むガス貯蔵システムの封止用のガス貯蔵用膜としての請求項24に記載の膜の使用。
  26. ウイギンス型ガス貯蔵システムにおけるガス貯蔵用膜としての請求項24または25に記載の膜の使用。
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