JP4971348B2 - 多層チューブ - Google Patents
多層チューブ Download PDFInfo
- Publication number
- JP4971348B2 JP4971348B2 JP2008539664A JP2008539664A JP4971348B2 JP 4971348 B2 JP4971348 B2 JP 4971348B2 JP 2008539664 A JP2008539664 A JP 2008539664A JP 2008539664 A JP2008539664 A JP 2008539664A JP 4971348 B2 JP4971348 B2 JP 4971348B2
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- JP
- Japan
- Prior art keywords
- layer
- barrier layer
- multilayer tube
- adhesive resin
- styrene
- 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
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- 239000004840 adhesive resin Substances 0.000 claims description 64
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- 229910052760 oxygen Inorganic materials 0.000 claims description 30
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 29
- 229920001519 homopolymer Polymers 0.000 claims description 27
- -1 styrene-ethylene-propylene-styrene Chemical class 0.000 claims description 23
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 36
- 239000000806 elastomer Substances 0.000 description 36
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- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
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- 230000002708 enhancing effect Effects 0.000 description 1
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 1
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- 230000008020 evaporation Effects 0.000 description 1
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- 229940057995 liquid paraffin Drugs 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
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- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
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- 238000007127 saponification reaction Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
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- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 1
Images
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Landscapes
- Engineering & Computer Science (AREA)
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Description
2 内層
3 外層
4−1 接着樹脂層
4−2 接着樹脂層
4−3 接着樹脂層
5 バリア層
6 液体供給通路
7 酸素遮断層
図1において、1は多層チューブであり、多層チューブ1は、内層2、外層3、バリア層5、接着樹脂層4−1、4−2の5層構造をなしている。6は液体供給通路である。内層2、接着樹脂層4−1、バリア層5、接着層4−2、外層3の各膜厚は、100〜300:5〜50:5〜100:5〜50:200〜600(μm)の範囲が好適である。なお、内層2、外層3、バリア層5、接着樹脂層4−1、4−2の厚さはこれに限定されるものでない。
(1)3層構造:バリア層/接着樹脂層/外層
(2)5層構造:バリア層/接着樹脂層/酸素遮断層/接着樹脂層/外層、または内層/接着樹脂層/バリア層/接着樹脂層/外層
(3)7層構造:内層/接着樹脂層/バリア層/接着樹脂層/酸素遮断層/接着樹脂層/外層
水蒸気バリア性は、1mの多層チューブ内に水を充填して両端を密封し、雰囲気温度40℃にて一週間保管し、重量変化のち水蒸気透過度を求めた。評価は水蒸気透過度(g・mm/m2・day)が0.3以下のものを優、0.5以下のものを良、1.0以下のものを可、1.0より大きいものを不可とした。
耐キンク性は、チューブを屈曲させてキンクが発生した最小半径を測定した。評価は最小半径(mm)が15以下のものを優、20以下のものを良、25以下のものを可、25より大きいものを不可とした。
[実施例1]
以下の層構成を有する5層構造の多層チューブを作成した。
内層2:スチレン系エラストマー(100μm)/接着樹脂層4−1:接着樹脂(25μm)/バリア層5:クロロトリフルオロエチレンのホモポリマー(50μm)/接着樹脂層4−2:接着剤樹脂(25μm)/外層3:スチレン系エラストマー(300μm)である。スチレン系エラストマーはスチレン−エチレン−プロピレン−スチレンブロック共重合体(SEPS)を主成分とする樹脂、クロロトリフルオロエチレンのホモポリマーはMFRが0.5g/10minのものを用い、接着樹脂は無水マレイン酸ポリエチレンにスチレン系エラストマー(SEBSゴム)を10wt%混合したものを用いた。
[実施例2]
以下の層構成を有する5層構造の多層チューブを作成した。
内層2:直鎖状低密度ポリエチレン(100μm)/接着樹脂層4−1:接着樹脂(25μm)/バリア層5:クロロトリフルオロエチレンのホモポリマー(30μm)/接着樹脂層4−2:接着樹脂(25μm)/外層3:スチレン系エラストマー(320μm)である。内層に直鎖状低密度ポリエチレンを用いた以外は実施例1と同様の樹脂とした。
[実施例3]
以下の層構成を有する7層構造の多層チューブを作成した。
内層2:スチレン系エラストマー(100μm)/接着樹脂層4−1:接着樹脂(25μm)/バリア層5:クロロトリフルオロエチレンのホモポリマー(50μm)/接着樹脂層4−2:接着樹脂(25μm)/酸素遮断層(30μm)/接着樹脂層4−3:接着樹脂(25μm)/外層3:スチレン系エラストマー(245μm)である。酸素遮断層はエチレン含有量が32モル%のエチレン−酢酸ビニル共重合体けん化物(EVOH)を用いた以外は実施例1と同様の樹脂とした。
[実施例4]
以下の層構成を有する7層構造の多層チューブを作成した。
内層2:直鎖状低密度ポリエチレン(100μm)/接着樹脂層4−1:接着樹脂(25μm)/バリア層5:クロロトリフルオロエチレンのホモポリマー(30μm)/接着樹脂層4−2:接着樹脂(25μm)/酸素遮断層(15μm)/接着樹脂層4−3:接着樹脂(25μm)/外層3:スチレン系エラストマー(280μm)である。内層に直鎖状低密度ポリエチレンを用いた以外は実施例3と同様の樹脂とした。
[実施例5]
最内層にバリア層が配置されるように以下の層構成を有する3層構造の多層チューブを作成した。
バリア層5:クロロトリフルオロエチレンのホモポリマー(20μm)/接着樹脂層4−2:接着剤樹脂(25μm)/外層3:スチレン系エラストマー(455μm)である。内層2および接着樹脂層4−1を設けなかった以外は実施例1と同様の樹脂とした。
[実施例6]
最内層にバリア層が配置されるように以下の層構成を有する5層構造の多層チューブを作成した。
バリア層5:クロロトリフルオロエチレンのホモポリマー(50μm)/接着樹脂層4−2:接着樹脂(10μm)/酸素遮断層(30μm)/接着樹脂層4−3:接着樹脂(10μm)/外層3:スチレン系エラストマー(400μm)である。内層および接着樹脂層4−1をなくした以外は実施例3と同様の樹脂を用いた。
[比較例1]
内層(100μm)/接着樹脂層(25μm)/バリア層(50μm)/接着樹脂層(25μm)/外層(300μm)の5層構造の多層チューブを作成した。
バリア層を構成する樹脂をポリフッ化ビニリデン(PVDF)、外層を直鎖状低密度ポリエチレン(LLDPE)とした以外は実施例2と同様の樹脂を用いた。評価について、水蒸気バリア性、キンク性ともに不可であった。
[比較例2]
内層:スチレン系エラストマー(100μm)/接着樹脂層(25μm)/バリア層(50μm)/接着樹脂層(25μm)/外層:スチレン系エラストマー(300μm)の5層構造の多層チューブを作成した。
内層および外層をスチレン−エチレン−ブチレン−スチレンブロック共重合体からなるスチレン系エラストマーとした以外は実施例1と同様の樹脂を用いた。スチレン系エラストマーの引張弾性率は20MPa、引張降伏点強度は12MPaであった。評価について、水蒸気バリア性は良であったが、キンク性は不可であった。
[比較例3]
内層(100μm)/接着樹脂層(25μm)/バリア層:エチレン−クロロトリフルオロエチレン共重合体(50μm)/接着樹脂層(25μm)/外層(300μm)の多層フィルムを作成した。
バリア層をエチレン−クロロトリフルオロエチレン共重合体とした以外は実施例1と同様の樹脂を用いた。エチレン−クロロトリフルオロエチレン共重合体のMFRは0.05g/10min、引張弾性率は720MPaであった。評価について、水蒸気バリア性は可であった。ただし、共押出し成形により良好な多層チューブが作成できなかったため多層フィルムにて評価した。
[比較例4]
内層:フッ素樹脂(75μm)/接着樹脂層(25)/外層:スチレン系エラストマー(400μm)の積層フィルムを作成して評価した。
フッ素樹脂はポリテトラフルオロエチレン(PTFE)とした以外は実施例1と同様の樹脂を用いた。PTFEの融点は330℃、スチレン系エラストマーの融点は132℃であった。評価について、水蒸気バリア性は可であった。ただし、共押出し成形により良好な多層チューブが作成できなかったため多層フィルムにて評価した。
Claims (2)
- 積層されたフッ素樹脂からなるバリア層を有する多層チューブであって、
前記多層チューブはクロロトリフルオロエチレンのホモポリマーからなるバリア層(A)および引張弾性率が7〜40MPaかつ引張降伏点強度が0.5〜5MPaのスチレン−エチレン−プロピレン−スチレンブロック共重合体からなる外層(B)を少なくとも有しており、
前記バリア層(A)と前記外層(B)とは接着性樹脂を介して共押出し成形することにより一体に積層されてなり、
前記多層チューブの平均厚さに対する前記バリア層(A)の膜厚比率が20%以下であり、バリア層(A)を構成するクロロトリフルオロエチレンのホモポリマーは融点が220℃未満であるとともに230℃におけるメルトフローレイト(MFR)が0.1〜10g/10minで、かつ引張弾性率が750〜1500MPaであることを特徴とする多層チューブ。 - 積層されたフッ素樹脂からなるバリア層を有する多層チューブであって、
前記多層チューブはクロロトリフルオロエチレンのホモポリマーからなるバリア層(A)および引張弾性率が7〜40MPaかつ引張降伏点強度が0.5〜5MPaのスチレン−エチレン−プロピレン−スチレンブロック共重合体からなる外層(B)を少なくとも有しており、
前記バリア層(A)と前記外層(B)の間には樹脂からなる酸素遮断層(C)がそれぞれ接着性樹脂を介して共押出し成形することにより一体に積層されてなり、
前記多層チューブの平均厚さに対する前記バリア層(A)の膜厚比率が20%以下であり、バリア層(A)を構成するクロロトリフルオロエチレンのホモポリマーは融点が220℃未満であるとともに230℃におけるメルトフローレイト(MFR)が0.1〜10g/10minで、かつ引張弾性率が750〜1500MPaであることを特徴とする多層チューブ。
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AU2013237736A1 (en) * | 2012-10-25 | 2014-05-15 | Ge Oil & Gas Uk Limited | Flexible Pipe Body Layers And Method Of Producing Same |
US20140182735A1 (en) * | 2012-12-28 | 2014-07-03 | Thercom Holdings, Llc | Thermoplastic extrusion with vapor barrier and surface sulfonation |
DE102013201302A1 (de) * | 2013-01-28 | 2014-07-31 | Zf Friedrichshafen Ag | Zylinderaggregat mit einer Klebeverbindung |
EP2772354B1 (de) * | 2013-03-01 | 2018-12-05 | TI Automotive (Fuldabrück) GmbH | Mehrschichtige Kraftstoffrohrleitung |
US10406773B2 (en) * | 2014-02-20 | 2019-09-10 | Guill Tool & Engineering Co., Inc. | Method of multi-deflector balancing and strengthening |
CN104061377A (zh) * | 2014-06-30 | 2014-09-24 | 张家港华程机车精密制管有限公司 | 高附着性内衬塑异形钢管 |
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