JP5475794B2 - 多層可撓性管 - Google Patents
多層可撓性管 Download PDFInfo
- Publication number
- JP5475794B2 JP5475794B2 JP2011534816A JP2011534816A JP5475794B2 JP 5475794 B2 JP5475794 B2 JP 5475794B2 JP 2011534816 A JP2011534816 A JP 2011534816A JP 2011534816 A JP2011534816 A JP 2011534816A JP 5475794 B2 JP5475794 B2 JP 5475794B2
- Authority
- JP
- Japan
- Prior art keywords
- block copolymer
- styrene block
- styrene
- blend
- flexible tube
- 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 - Fee Related
Links
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Images
Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
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- B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29K2023/10—Polymers of propylene
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29L2023/00—Tubular articles
- B29L2023/22—Tubes or pipes, i.e. rigid
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- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
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- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/402—Coloured
- B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
- B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
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- 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]
- Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
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- 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]
- Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
- Y10T428/1393—Multilayer [continuous layer]
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Description
ポリマーブレンドの試料は、プロピレンポリマーおよびスチレンブロックコポリマーから調製する。プロピレンポリマーは、ランダムプロピレンコポリマーまたはシンジオタクチックポリプロピレンから選択する。プロピレンランダムコポリマーは、25dg/分のメルトフローインデックスおよび900MPaの曲げ弾性率を有する。プロピレンランダムコポリマーは、Huntsmanから入手できる。Total Petrochemicalから入手できるシンジオタクチックポリプロピレンは、12dg/分のメルトフローインデックスおよび377MPaの曲げ弾性率を有する。スチレンブロックコポリマーは、Kraton Polymer(Houston、USA)から入手できるSEBSコポリマーであり、18dg/分のメルトフローインデックス、50ショアAの硬度、および1.5MPaの100%モジュラスを有する。
ポリマーブレンドの試料は、プロピレンポリマーおよびスチレンブロックコポリマーから調製する。プロピレンポリマーは、ランダムプロピレンコポリマーまたはシンジオタクチックポリプロピレンから選択する。Huntsmanから入手できるプロピレンランダムコポリマーは、25dg/分のメルトフローインデックスおよび900MPaの曲げ弾性率を有する。Total Petrochemicalから入手できるシンジオタクチックポリプロピレンは、12dg/分のメルトフローインデックスおよび377MPaの曲げ弾性率を有する。スチレンブロックコポリマーは、Hybrarの商品名で株式会社クラレ(倉敷、日本)から入手できるSEPSコポリマーであり、4dg/分のメルトフローインデックス、64ショアAの硬度、および1.7MPaの100%モジュラスを有する。
ポリマーブレンドの試料は、プロピレンポリマーおよびスチレンブロックコポリマーから調製する。プロピレンポリマーは、ランダムプロピレンコポリマーまたはシンジオタクチックポリプロピレンから選択する。Huntsmanから入手できるプロピレンランダムコポリマーは、25dg/分のメルトフローインデックスおよび900MPaの曲げ弾性率を有する。Total Petrochemicalから入手できるシンジオタクチックポリプロピレンは、12dg/分のメルトフローインデックスおよび377MPaの曲げ弾性率を有する。スチレンブロックコポリマーは、Hybrarの商品名で株式会社クラレ(倉敷、日本)から入手できるSEEPSコポリマーであり、2dg/分のメルトフローインデックス、41ショアAの硬度、および0.6MPaの100%モジュラスを有する。
一層チューブ試料は、プロピレンポリマーとスチレンブロックコポリマーとのブレンドから調製する。ブレンドは、プロピレンポリマーおよびスチレンブロックコポリマーを70/30から50/50のPP/スチレンブロックコポリマーの比で含み、約70ショアAの硬度を有する。例えば、プロピレンポリマーは、25dg/分のメルトフローインデックスおよび900MPaの曲げ弾性率を有し、Huntsmanから入手できる。スチレンブロックコポリマーは、18dg/分のメルトフローインデックス、52ショアAの硬度、および1.5MPaの100%モジュラスを有する。スチレンブロックコポリマーは、Krton(Houston、Texas)から入手できる。ブレンドは、共回転する互いにかみ合う二軸押出機を通して混合し、水浴で冷却し、ペレットに切断する。得られたペレットを、管ダイを備えた単軸押出機中に供給する。通常の3ゾーンスクリューを使用する。温度プロファイルは、押出機の3つのセグメントについて、275°F、360°F、および390°Fに設定する。アダプターおよびダイの温度は、それぞれ、380°Fおよび350°Fに設定する。ダイから溶融流出するポリマーは、冷却用の浸漬水槽中に放出し、そこで、押出物は、管形状に凝固する。内部空気圧、スクリュー速度および延伸速度は、組み合わせて、管の寸法および壁厚さを制御する。ID1/4インチおよびOD3/8インチの寸法を有する、透明で、可撓性の管を、上記混合および押出し手順によって得る。
2層管は、2層を共押出しすることによって形成する。1つの層は、プロピレンポリマーとスチレンブロックコポリマーとのブレンドを含み、第2の層はポリオレフィン材料を含む。
実施例4によれば、一層管は、いくつかのブレンドから形成される。実施例5によれば、二層管は、いくつかのブレンドおよびポリオレフィン材料から形成される。これらの試料は、熱可塑性ポリウレタンライナーを有するPVC可撓性管(PVC/TPU)、Tygon 2001、Tygon 2075、Tygoprene XL−60、TPU−2%Blue管(Estane 58070)、SEBS2645(Evoprene G291−75から形成されるチューブ)、およびC−Flex R70−374の試料と比較する。PVC/TPU管、Tygon 2001、Tygon 2075、Tygonprene XL−60およびC−Flex R70−373は、Saint−Gobain Performance Plasticsの市販の管製品である。TPU−2%BlueおよびSEBS 2645のチューブは、市販の樹脂または化合物から製造される。
戸外用途のためのポリマー材料のUV−安定性を試験するために、成形プラークを、UVA−340ランプを備えたQUV試験機に入れ、340nmで1.14w/m2/nmの強化放射照度でのUV線に最大1000時間曝露する。UV曝露前後の材料の機械的特性および黄色指数を試験し、比較する。戸外用途に適した材料について、引張強度、伸び、100%歪みでのモジュラスおよび300%歪みでのモジュラスを含む機械的特性は、25%を超えて変化すべきでなく、一方、材料の黄色指数の変化は、20%を超えるべきでない。
銀系抗菌添加剤を、多層管の流体経路であるポリオレフィン系ライナー層中に、0.5から2重量%の濃度で添加し、管の流体経路を細菌、真菌、カビ、および他の微生物の汚染作用から保護する。例えば、Miliken製1%銀系AlphaSan(登録商標)抗菌剤をポリオレフィン樹脂中に添加する。ASTM E2149により規定された方法に従ってAntimicrobial Test Laboratoriesで行われた試料についての抗菌効果試験は、黄色ブドウ球菌(S.aureus)6538の微生物に対して99.9%を超える殺傷率を示す。
rPP/スチレンブロックコポリマーのブレンドから製造された一層管または多層管も、蠕動ポンプチューブとして使用することができる。Cole Palmerにより提供されるMasterflex(登録商標)回転蠕動ポンプを用いて、ポンプ寿命試験を行う。1/4インチOD3/8インチIDの管試料を、漏出が検出されるまで標準ポンプヘッドを用いて600rpmで試験する。一層管(試料3)および多層管(試料7)のポンプ寿命を、Tygon(登録商標)R3603の商品名でSaint−Gobainより販売される市販のf−PVCポンプ管に対して比較する。以下の表で例証するように、一層管および多層管の両方が、f−PVC管と同様またはより長いポンプ寿命を示す。
Claims (14)
- 150MPa以下の曲げ弾性率を有するポリオレフィン材料を含む第1層;ならびに
前記第1層に直接結合しかつ直接接触している、プロピレンポリマーとスチレンブロックコポリマーとのブレンドを含む第2層を含み、
前記スチレンブロックコポリマーは、水素化スチレン−ブタジエン−スチレンブロックコポリマー、水素化スチレン−イソプレン−スチレンブロックコポリマー、スチレン−エチレン−ブチレン−スチレンブロックコポリマー(SEBS)、スチレン−エチレン−プロピレン−スチレンブロックコポリマー(SEPS)、スチレン−エチレン−エチレン−ブチレン−スチレンブロックコポリマー(SEEBS)、スチレン−エチレン−エチレン−プロピレン−スチレンブロックコポリマー(SEEPS)、またはそれらの任意の組合せからなる群より選択され、
前記第1層が、全体の厚さの5%から20%を形成する可撓性チューブ。 - 前記曲げ弾性率が、120MPa以下である、請求項1に記載の可撓性チューブ。
- 前記ブレンドが、10重量%から80重量%のプロピレンポリマーを含む、請求項1に記載の可撓性チューブ。
- 前記ブレンドが、0.1重量%から1重量%の範囲のUV添加剤をさらに含む、請求項1から3のいずれか一項に記載の可撓性チューブ。
- 前記ブレンドが、少なくとも0.1の25℃での損失タンジェント値(tanδ)を示す、請求項1から3のいずれか一項に記載の可撓性チューブ。
- 前記可撓性チューブが、250mil(0.65mm)以下の平均厚さを有する、請求項1から3のいずれか一項に記載の可撓性チューブ。
- 前記可撓性チューブが、少なくとも20mil(0.508mm)の平均厚さを有する、請求項1から3のいずれか一項に記載の可撓性チューブ。
- 前記ブレンドが、40ショアAから90ショアAの範囲の硬度を有する、請求項1から3のいずれか一項に記載の可撓性チューブ。
- 前記ブレンドが、少なくとも5MPaの90℃でのストレージモジュラスを有する、請求項1から3のいずれか一項に記載の可撓性チューブ。
- 前記可撓性チューブが、少なくとも50時間のポンプ寿命を有する、請求項1から3のいずれか一項に記載の可撓性チューブ。
- ポリオレフィンを含み、150MPa以下の曲げ弾性率を有する第1層を押出しする段階;ならびに
前記第1層と直接接触しかつ直接結合した、プロピレンポリマーとスチレンブロックコポリマーとのブレンドを含む第2層を、前記第1層とともに共押出しする段階を含み、
前記スチレンブロックコポリマーは、水素化スチレン−ブタジエン−スチレンブロックコポリマー、水素化スチレン−イソプレン−スチレンブロックコポリマー、スチレン−エチレン−ブチレン−スチレンブロックコポリマー(SEBS)、スチレン−エチレン−プロピレン−スチレンブロックコポリマー(SEPS)、スチレン−エチレン−エチレン−ブチレン−スチレンブロックコポリマー(SEEBS)、スチレン−エチレン−エチレン−プロピレン−スチレンブロックコポリマー(SEEPS)、またはそれらの任意の組合せからなる群より選択され、
前記第1層が、全体の厚さの5%から20%を形成する可撓性チューブを形成する方法。 - 前記ポリオレフィンが、1から30dg/分のメルトフローインデックスを有する、請求項11に記載の方法。
- 前記プロピレンポリマーが、0.1dg/分から35dg/分の範囲のメルトフローインデックスを有する、請求項11から12のいずれか一項に記載の方法。
- 前記スチレンブロックコポリマーが、少なくとも0.5dg/分のメルトフローインデックスを有する、請求項11から13のいずれか一項に記載の方法。
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TWI385330B (zh) | 2008-10-31 | 2013-02-11 | Saint Gobain Performance Plast | 多層撓性管材 |
DE202010006308U1 (de) * | 2010-04-30 | 2011-09-06 | Rehau Ag + Co. | Flexibler Schlauch |
ES2369809B1 (es) * | 2010-05-10 | 2012-10-15 | Ctl-Th Packaging, S.L. Unipersonal | Tubo de material flexible, procedimiento de fabricación de tubos de material flexible, y formulación utilizada. |
FR2963890B1 (fr) | 2010-08-17 | 2013-03-08 | Sartorius Stedim Biotech Sa | Dispositif biopharmaceutique a usage unique d'elaboration, stockage, transport d'un produit biopharmaceutique et tube multicouche correspondant. |
US9446216B2 (en) | 2010-10-14 | 2016-09-20 | Medtronic, Inc. | Cannular device and method of manufacture |
US8629414B2 (en) * | 2011-04-12 | 2014-01-14 | Xerox Corporation | Clear overcoat compositions and methods for using and detecting the same |
JP5883322B2 (ja) * | 2012-03-26 | 2016-03-15 | 住友理工株式会社 | 樹脂製フューエルチューブ |
US20140037880A1 (en) * | 2012-07-26 | 2014-02-06 | Sridhar Krishnamurthi Siddhamalli | Multilayer flexible tube |
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WO2010051468A3 (en) | 2010-07-08 |
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US8747978B2 (en) | 2014-06-10 |
CN102186669B (zh) | 2015-11-25 |
JP2012506807A (ja) | 2012-03-22 |
US20140234561A1 (en) | 2014-08-21 |
CN102186669A (zh) | 2011-09-14 |
JP5908932B2 (ja) | 2016-04-26 |
TW201022567A (en) | 2010-06-16 |
ES2774917T3 (es) | 2020-07-23 |
TWI385330B (zh) | 2013-02-11 |
US9625061B2 (en) | 2017-04-18 |
EP2349712A4 (en) | 2017-04-26 |
EP2349712B1 (en) | 2019-12-11 |
EP2349712A2 (en) | 2011-08-03 |
CN105196621B (zh) | 2018-05-25 |
JP2014111995A (ja) | 2014-06-19 |
CN105196621A (zh) | 2015-12-30 |
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