CN1571809A - 由热塑性材料制成的不可渗透性的空心体及其生产方法 - Google Patents
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Abstract
适合作为燃料箱的不可渗透性空心体,由热塑性材料制成,所述热塑性材料包含至少一种聚烯烃并用聚乙烯醇膜层被覆,所述聚乙烯醇膜层由于其分子由化学试剂交联和/或由于环氧树脂保护层的存在而使其对水不可渗透和在水中不可溶解。本发明还涉及使由包含至少一种聚烯烃的热塑性材料制成的空心体不可渗透的两步法。在第一步中,首先用聚乙烯醇膜层涂覆空心体的表面,并在第二步中,通过用化学试剂交联所述聚乙烯醇分子和/或在所述膜层上沉积环氧树脂层使所述聚乙烯醇膜层不可溶解并且不可渗透。
Description
本发明涉及一种由热塑性材料制成的不可渗透性的空心体。
由热塑性材料制成的不可渗透性空心体已为人所知很长时间了。尤其是,由对气态烃和液态烃具有非常低的渗透性的热塑性材料制成的燃料箱是已知的。基本上可将这些已知的燃料箱分为独立的两类,即:其内表面已用活性气体(例如F2或SO3)处理过的箱,所述活性气体改善所用塑料的性能并且使所处理的箱的表面成为不可渗透性的;和由含有由阻挡材料制成的内层的多层结构构成的箱,所述内层通常是薄的,并且从机械的观点看不非常坚固,所述阻挡材料防止烃的渗透。
此外,已知专利GB-1 006 622描述了通过用由环氧树脂涂层保护的聚乙烯醇涂层涂覆用于包装的聚丙烯薄膜以改善这些膜的粘附性能的方法(“Treatment4”,第9页,第18行)。
然而,观察到的结果是,用这种已知的方法聚乙烯醇层本身对聚丙烯基质的粘附不良。特别是,当壁厚充分地大于包装薄膜的厚度时,例如在可以用作如燃料箱的空心体中所遇到的壁,粘着力不足以长期保证聚乙烯醇层的机械完整性。
本发明的目的是提供一种由热塑性材料制成的空心体,所述热塑性材料对烃是不能渗透的并且不需利用诸如氟或三氧化硫这样的高活性气体进行处理,也不必使用在结构内部含有阻挡层的多层结构的复合体。
为了达到这个目的,本发明涉及由热塑性材料制成的空心体,它包含至少一种聚烯烃并且在至少其一个面(face)上和在至少其表面(surface)的一部分上被覆聚乙烯醇膜,其中所述聚乙烯醇膜由于利用选自酯化和缩醛化剂的化学试剂引起的其分子交联状态以及/或通过在其与大气的界面上存在覆盖它的保护层而具有大大减小的水渗透性和水溶解性。
术语“空心体”表示在其表面(surface)上具有至少一个空的或凹的部分的任何结构。优选地,空心体在此应理解为是指用于容纳液体和/或气体的密闭结构。尤其优选的是容器和箱。本发明的空心体尤其适合用作燃料箱,特别是出现在汽车上或适用于装在汽车上的燃料箱。从扩大的范围来讲,它们也指各种与这些空心体相关联的附件,也指用于将这些附件连接到空心体上的界面。这样的附件例如是抽取流体的组件和泵、罐、阀和与空心体相关联的导管系统,它们安装在空心体上或只是简单地连接到空心体上。
本发明的空心体是对液体或气体燃料,特别是对烃和对含有少于10个碳原子的醇以及它们的混合物的渗透性非常低的空心体。本发明的空心体可以将在总共24小时内的累积渗流限制在少于2g烃和/或醇。
术语“热塑性材料”是指包含至少一种通过至少一种热处理可以非永久性成形的聚合物的任何材料。术语“聚合物”是指均聚物和共聚物(特别是二元或三元共聚物)。这样的共聚物的例子是,但不限于,无规共聚物、线性嵌段共聚物、其他嵌段共聚物和接枝共聚物。
热塑性聚合物还包括热塑性弹性体和它们的共混物。
其熔点低于分解温度的任何类型的热塑性聚合物或共聚物都是适宜的。具有延续至少10℃的熔融范围的合成热塑性材料是特别好的。这样的材料的例子是那些其分子量呈多分散性的材料。
特别是,聚烯烃、接枝聚烯烃、热塑性聚酯、聚酮、聚酰胺和它们的共聚物可以用于所述空心体。
经常使用的共聚物是乙烯-乙烯醇(EVOH)共聚物。也可以使用聚合物或共聚物的混合物,同样可以使用聚合物材料与无机、有机和/或天然填料,例如但不限于碳、盐和其他无机衍生物以及天然纤维或聚合纤维的混合物。
本发明空心体的热塑性材料包括至少一种聚烯烃。优选地,这种聚烯烃是聚乙烯。高密度聚乙烯(HDPE)已给出优良的结果。
根据本发明,至少在热塑性材料的一个面上和至少在其表面的一部分上涂覆一层聚乙烯醇膜。可以在空心体的一个面的全部或两个面的全部上形成涂层。所述涂层也可以只位于其表面的一部分上,在需要更高程度的不可渗透性的地方。
聚乙烯醇更通常地通过水解聚乙酸乙烯酯来生产。然而,聚乙烯醇也可能含有一定比例的、在其生产过程中尚未水解的乙酸酯基团。取决于其水解度,在本发明的空心体的热塑性材料中存在的聚乙烯醇的量可以在一定范围内变化。例如,对应于至少80%、并优选至少95%的被水解乙酸酯基团总数的水解度,对于覆盖本发明空心体的热塑性材料的膜来说是非常适宜的。
覆盖本发明的空心体的热塑性材料的聚乙烯醇膜具有大大降低的对水的渗透性和在水中的溶解度的优点。这些特有性能直接来源于聚乙烯醇膜的独特状态,所述聚乙烯醇膜通过化学试剂交联,或者,二者择一地,其与外界大气的界面上被涂覆了一层保护层,将聚乙烯醇膜与大气中的水蒸气隔离,也将聚乙烯醇膜与空心体内可能含有的水隔离。也可以同时联合运用由化学试剂引起的交联状态和覆盖聚乙烯醇膜的保护层。
本发明的空心体的一种令人感兴趣的变体(variant)是其中热塑性材料包含粘合促进剂的变体。这种促进剂可以在空心体的壁的本体内分布,或者与此相反,它也可以仅存在于与空心体的聚乙烯醇膜相邻接的表面部分。
任何可增强聚乙烯醇膜对包含聚烯烃的基质的粘附性能的组合物都适合作为粘合促进剂。一种已给出良好结果的粘合促进剂是酸的过氧化物或由至少一种极性基团接枝的聚烯烃。特别适宜的极性基团是羧基基团。由酐接枝的、特别是马来酐接枝的聚乙烯已经给出了优良的结果。
用于促进粘合的另一个有益的变体是在热塑性材料的界面上存在酸性位点。当聚乙烯醇膜是由酯交联时,这些酸性位点是特别有利的。
在聚乙烯醇膜是用保护层覆盖的情况下,此保护层可以是包含柔性环氧树脂、聚氨酯清漆或丙烯酸涂料的保护层。
当聚乙烯醇膜由化学试剂交联时,后者是选自酯化剂和缩醛化剂,或选自两种或多种这些试剂的混合物。也可以从属于上述两类中的至少一类的数种试剂的混合物中选择所述的化学试剂。“酯化剂和缩醛化剂”应理解为是指包含至少一种能够至少与聚乙烯醇膜的表面分子发生反应以与这些分子的碳链上的羟基分别生成酯基团或缩醛基团的化合物的任何组合物。
优选地,所述的化学交联剂是一种酯化剂。特别适宜的酯化剂选自乙酸、乙基己基缩水甘油醚、长链有机酸或二酸及其酰氯、异氰酸酯和脲。
“长链有机酸或二酸”应理解为是指含有至少一个具有至少8个碳原子的碳链的脂肪族和/或芳香族羧酸。
术语“异氰酸酯”应理解为是指含有至少一个异氰酸酯基团(-NCO)的化合物。单异氰酸酯和二异氰酸酯是特别适宜的。优选单异氰酸酯。
一种已给出优良结果的酯化剂是乙酸。
本发明还涉及使由包括至少一种聚烯烃的热塑性材料制成的空心体不可渗透的方法,其中,在第一步中,首先用聚乙烯醇膜涂覆空心体的表面,在第二步中,通过用化学试剂交联所述聚乙烯醇分子和/或通过在所述聚乙烯醇膜上沉积环氧树脂涂层使所述聚乙烯醇膜不能溶解和不能渗透。
在该方法中,所述的常见术语与在上文对空心体的描述中所给出的术语具有相同的含义。
实施本发明的方法(过程)的一种特别有利的方法在于活化聚乙烯醇膜的粘附。一种非常适宜的活化方法是局部生热。可以使用任何能在聚乙烯醇膜与空心体中存在的热塑性基质之间的界面上产生热的方法。例如,通过将热空气流定向在聚乙烯醇膜上或通过用适当波长的电磁辐射对覆盖热塑性材料制成的基质的聚乙烯醇膜进行扫描以通过在所述聚合物中的吸收而产生热,可以发生局部生热。
优选地,通过用波长至多等于15000nm的红外辐射或激光辐射扫描覆盖热塑性材料制成的基质的聚乙烯醇膜的表面来发生局部生热。更经常地,用于扫描所述表面的红外辐射或激光辐射具有至少500nm的波长通常也是适宜的。
另一种优选的局部生热的方法是使用与聚乙烯醇膜直接接触的气体气氛中的等离子体。所有类型的等离子体和与用聚乙烯醇膜涂覆空心体表面的操作条件相容的产生它们的方法都是适宜的。
当所涂覆的是封闭空心体的内表面(即凹面)时,优选真空下的等离子体,例如氩等离子体、氮等离子体或氩/氮混合物的等离子体。
当所涂覆的是空心体的外表面(即凸面)时,优选使用常压氮等离子体焰炬。
在这两种情况下,用微波辐射发生器加强等离子体的发生都是有利的。
也可以将作为局部热发生器的等离子体的使用与如上所述的酸性位点的预先产生结合起来。利用等离子体也可以有利地进行酸性位点的产生。优选地,在这种情况下使用CO2等离子体。取决于所涂覆的是封闭空心体的内表面还是其外表面,在此又有可能在真空中或常压(等离子体焰炬)下操作。在产生了酸性位点后,就可以通过使用氩或氮真空等离子体或氮常压等离子体焰炬的局部生热促进聚乙烯醇膜的粘合。
可利用任何可以产生均匀厚度的聚乙烯醇膜涂层的方法或技术来实施用聚乙烯醇膜涂覆空心体的表面的步骤。一种已给出良好结果的技术在于:用水性聚乙烯醇水溶液喷涂待被覆表面,然后对已被覆的空心体进行干燥以蒸发溶剂中的水。利用热空气干燥是非常适宜的。
Claims (10)
1.由热塑性材料制成的空心体,它包含至少一种聚烯烃并且在至少其一个面上和在至少其表面的一部分上被覆聚乙烯醇膜,其特征在于所述聚乙烯醇膜由于利用选自酯化剂和缩醛化剂的化学试剂引起的其分子交联状态以及/或通过在其与大气的界面上存在覆盖它的保护层而具有大大减小的水渗透性和水溶解性。
2.根据前述权利要求所述的空心体,其特征在于所述保护层选自那些包含柔性环氧树脂、聚氨酯清漆和丙烯酸涂料的保护层。
3.根据权利要求1所述的空心体,其特征在于所述化学交联剂是选自至少下列化合物之一的酯化剂:乙酸、乙基己基缩水甘油醚、长链有机酸或二酸及其酰氯、异氰酸酯和脲。
4.根据前述权利要求所述的空心体,其特征在于所述酯化剂是乙酸。
5.使由包含至少一种聚烯烃的热塑性材料制成的空心体不可渗透的方法,其特征在于,在第一步中,首先给所述空心体的至少一个面的至少部分表面涂覆聚乙烯醇膜,在第二步中,通过用化学试剂交联其分子和/或通过在所述膜上沉积环氧树脂涂层使所述膜的水溶性减小。
6.根据前述权利要求所述的方法,其特征在于所述热塑性材料还含有聚乙烯醇膜的粘合促进剂,还在于所述粘合反应是通过局部生热活化的。
7.根据前述权利要求所述的方法,特征在于通过用选自红外辐射和激光辐射的波长为从500至15000nm的电磁辐射扫描所述表面使所述的局部生热发生。
8.根据权利要求6所述的方法,其特征在于通过使用氩或氮的等离子体使所述的局部生热发生。
9.根据权利要求6至8的任一项所述的方法,其特征在于所述的粘合促进剂选自用酐接枝的聚烯烃、酸的过氧化物和由CO2等离子体产生的酸性位点。
10.根据权利要求5至9的任一项所述的方法,其特征在于用聚乙烯醇涂覆所述空心体的表面的步骤是通过用聚乙烯醇的水溶液喷涂所述表面,随后进行干燥以蒸发溶剂中的水而实现的。
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Application Number | Priority Date | Filing Date | Title |
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FR0113627 | 2001-10-19 | ||
FR0113627A FR2831172A1 (fr) | 2001-10-19 | 2001-10-19 | Corps creux impermeable en materiau thermoplastique et procede pour sa fabrication |
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CN1571809A true CN1571809A (zh) | 2005-01-26 |
CN1250617C CN1250617C (zh) | 2006-04-12 |
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US (1) | US20040247809A1 (zh) |
EP (1) | EP1448680B1 (zh) |
JP (1) | JP2005519140A (zh) |
KR (1) | KR20040045835A (zh) |
CN (1) | CN1250617C (zh) |
AT (1) | ATE334163T1 (zh) |
DE (1) | DE60213453D1 (zh) |
FR (1) | FR2831172A1 (zh) |
WO (1) | WO2003035727A1 (zh) |
Cited By (1)
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CN101492552B (zh) * | 2008-01-22 | 2012-11-21 | 包旺科技包材股份有限公司 | 具高渗透阻隔性之改性聚酰胺组成物及该对象之制法 |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
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EP1595913A1 (en) * | 2004-05-14 | 2005-11-16 | Inergy Automotive Systems Research (SA) | Method for preparing a hollow element of a fuel system |
DE602005024653D1 (de) * | 2004-08-27 | 2010-12-23 | Mitsubishi Gas Chemical Co | Verfahren zum Herstellen von Hohlkörpern |
FR2879239A1 (fr) * | 2004-12-15 | 2006-06-16 | Inergy Automotive Systems Res | Systeme de stockage et d'injection d'un additif dans des gaz d'echappement d'un moteur |
WO2006113561A2 (en) * | 2005-04-18 | 2006-10-26 | Advanced Plastics Technologies Luxembourg S.A. | Water-resistant coated articles and methods of making same |
US20070087131A1 (en) * | 2005-10-14 | 2007-04-19 | Hutchinson Gerald A | Methods of forming multilayer articles by surface treatment applications |
KR100744763B1 (ko) * | 2005-11-04 | 2007-08-01 | 김지현 | 불용성 폴리비닐 알콜(pva) 필름이 형성된 이형지의 제조 방법 |
JP4877934B2 (ja) * | 2006-05-10 | 2012-02-15 | 麒麟麦酒株式会社 | ガスバリア性プラスチック容器用のプリフォーム及びガスバリア性プラスチック容器の製造方法 |
FR2925910B1 (fr) * | 2007-12-26 | 2010-02-12 | Centre Nat Rech Scient | Film aux proprietes barrieres a l'eau, aux graisses, au gaz et a la vapeur d'eau |
DE102019102340A1 (de) | 2019-01-30 | 2020-07-30 | Leibniz-Institut Für Polymerforschung Dresden E.V. | Verfahren zur modifizierung von oberflächen |
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US3294577A (en) * | 1963-08-02 | 1966-12-27 | Union Carbide Corp | Barrier coated thermoplastic olefin high polymer substrates |
BR9007088A (pt) * | 1989-12-01 | 1992-01-28 | Gft Ges Fuer Trenntechnik | Membrana-composita para remocao de agua de fluidos contendo componentes organicos por meio de pervaporacao |
US5508113A (en) * | 1994-11-18 | 1996-04-16 | Mobil Oil Corp. | PVOH-based coating composition coated polymeric film |
JP3040693B2 (ja) * | 1995-05-30 | 2000-05-15 | 住友ベークライト株式会社 | 透明導電積層フイルム |
US5776618A (en) * | 1996-07-25 | 1998-07-07 | Mobil Oil Corporation | Barrier film structures |
FR2776228B1 (fr) * | 1998-03-20 | 2000-05-19 | Solvay | Corps creux multicouche en matiere thermoplastique |
DE60012470T2 (de) * | 2000-02-07 | 2005-09-15 | Ti Automotive Technology Center Gmbh | Mehrschichtkraftstoffbehälter |
US6884482B2 (en) * | 2001-03-27 | 2005-04-26 | Kuraray Co., Ltd. | Fuel container having excellent gasoline barrier properties |
-
2001
- 2001-10-19 FR FR0113627A patent/FR2831172A1/fr active Pending
-
2002
- 2002-10-18 EP EP02774743A patent/EP1448680B1/fr not_active Expired - Lifetime
- 2002-10-18 DE DE60213453T patent/DE60213453D1/de not_active Expired - Lifetime
- 2002-10-18 WO PCT/EP2002/011814 patent/WO2003035727A1/fr active IP Right Grant
- 2002-10-18 JP JP2003538239A patent/JP2005519140A/ja active Pending
- 2002-10-18 AT AT02774743T patent/ATE334163T1/de not_active IP Right Cessation
- 2002-10-18 US US10/491,905 patent/US20040247809A1/en not_active Abandoned
- 2002-10-18 KR KR10-2004-7005573A patent/KR20040045835A/ko not_active Application Discontinuation
- 2002-10-18 CN CNB028206371A patent/CN1250617C/zh not_active Expired - Fee Related
Cited By (1)
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CN101492552B (zh) * | 2008-01-22 | 2012-11-21 | 包旺科技包材股份有限公司 | 具高渗透阻隔性之改性聚酰胺组成物及该对象之制法 |
Also Published As
Publication number | Publication date |
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EP1448680B1 (fr) | 2006-07-26 |
FR2831172A1 (fr) | 2003-04-25 |
CN1250617C (zh) | 2006-04-12 |
JP2005519140A (ja) | 2005-06-30 |
DE60213453D1 (de) | 2006-09-07 |
WO2003035727A1 (fr) | 2003-05-01 |
ATE334163T1 (de) | 2006-08-15 |
KR20040045835A (ko) | 2004-06-02 |
US20040247809A1 (en) | 2004-12-09 |
EP1448680A1 (fr) | 2004-08-25 |
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