CN101600559A - 制造具有牢固粘附的塑料护套的金属管线的方法 - Google Patents
制造具有牢固粘附的塑料护套的金属管线的方法 Download PDFInfo
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Abstract
本发明涉及一种制造具有牢固粘附的塑料护套的金属管线的方法,其中,通过等离子体处理或通过气焊枪火焰产生活化的金属管表面,其中在表面上的作用时间小于3秒,将塑料护套涂装在裸露的活化金属管表面上,和在涂装护套时,金属管表面的温度低于80℃。
Description
技术领域
根据权利要求1的前述部分,本发明涉及一种制造具有牢固粘附的塑料护套的金属管线的方法。
背景技术
这种分离的管线通常是指由材料彼此匹配地连接的金属成分和塑料成分制成的管。例如由德国公开文本1 675 338公开了一种用于液体和气体的管线,所述管线由带有由热塑性聚合物制的牢固粘附的护套的薄壁铜管构成。所述护套可以通过挤出或通过卷绕塑料带而制得。通过使用热塑材料作为外壳直接粘合或者通过胶带而形成塑料和金属之间的粘合。该文中,由共聚单体形成并含有丙烯酸酯作为官能团的改性的聚乙烯起到良好粘合的作用。
WO 2006/005297 A1还公开了一种对带有牢固粘附的塑料护套的薄壁铜管或钢管的改进。为了改善金属和塑料之间的粘合,用作为增粘剂的试剂处理金属表面,该试剂的基础可以是苯并三唑。该文还建议,通过给外表面镀锡来改善粘合性。
另外,例如专利文本EP 0 794 376 B1还公开一种复合管,该复合管由位于内部的带有增粘剂层的铜箔以及内侧和外侧聚合物覆盖层组成。该文中,位于内部的铜箔在内侧和外侧设置有应防止离子形成或离子迁移的无机敷层。该敷层通过浸渍或通过电镀沉积而涂布,并优选由镍形成。
其它文献还常常讨论的金属和塑料之间的粘合以及对其施加影响的措施。还描述了通过使表面粗糙或者有目的地引入刻痕来改善塑料和金属之间的力学耦合。还通过用非氧化性的酸进行预处理,通过将粘附较差的氧化物层除去来改善金属表面上的粘合性。同时产生洼地状微粗糙性。在使用氧化性酸情况下,还可以额外涂布特定厚度的良好粘附的氧化物层。但由于金属晶格的物理结构和不同原子间化学键的本性,该氧化物层具有强极性。因此,非极性的聚合物,例如聚乙烯,很差地粘附在金属上。在非极性的聚合物骨架中含有极性官能团,例如离聚物的增粘剂被用作中间层。但对于增粘剂和极性金属表面之间键合机理的化学过程还没有完全弄清楚。猜想是这样的键,其键能介于有机分子的共价键和盐的离子键之间。与这两种极限情况哪个更准确描述了化学真实性无关,无可置疑的是,金属表面必须至少部分被氧化,从而改善粘合性。基于该考虑,例如金属表面在喷漆工艺中形成有机涂层之前对金属表面进行铬酸盐处理。
因此,由该设计方案出发需要一种工艺,通过这种工艺要使金属管的表面形成牢固粘附的聚合物涂层。
发明内容
因此本发明的目的在于,提供一种改善金属管线上塑料护套粘合性的方法。
通过权利要求1的特征来描述本发明。其它引用的权利要求涉及本发明有利的实施方案何改进方案。
本发明包括一种制造带有牢固粘附的塑料护套的金属管线的方法,其中:
-通过等离子体处理或通过气焊枪火焰产生活化的金属管表面,在此情况下,在表面上的作用时间小于3秒,
-将塑料护套涂装在裸露的活化金属管表面上,以及
-在涂装护套时,金属管表面的温度低于80℃。
本发明还从以下考虑出发,制造带有塑料护套的管线的方法可以脱离开前面对管进行预处理的方法步骤。对管进行预处理通常包括将卷绕的管放开,或者从管笼或之前制造步骤中将其输送出来,退火处理以及冷却,任选用下述的冷成形进行。通过本发明的方法,金属管表面在涂装护套之前直接被活化,并且为了良好的粘合能力而被预处理。
具体实施方式
气焊枪火焰以小于3秒的处理时间作用在表面上是以温度闪变(flash)来完成的。由于接触时间短,所以避免了造成对表面加热,在此情况下,在管相应向前进刀时,温度升高可以低于30℃。甚至在低于半秒的处理时间后就可以达到足够活化的表面。
通过等离子体预处理可以可靠地提供金属裸露的并活化的表面,并很大程度上与生产速度无关地实现。因此,较大带宽的管初加工材料卷在管笼中,或者可以直的长度使用,只要原材料满足对表面品质提出的某些最低要求。经调节的金属裸露的并活化的表面在操作上可对测量方法和其灵敏度进行定量化。作为测量表面性能的标准,在此可以考虑表面张力作为清洁性的尺度。另外,在表面上不应存在可被膜测试察觉的碳膜。在过程中可以简便地通过用白色材料的擦布进行刮擦测试来检验颗粒污染情况。满足预定要求的管表面适合作为初加工材料用在采用牢固粘附的塑料护套进行护套方面,并且可以直接进一步加工。提供金属裸露的活化表面也是脱离开所述工艺次序的重要前提。
不需要对表面进行氧化处理以形成氧化物层。不过,通过气焊枪,尤其是带有环形喷嘴的气焊枪,对表面进行活化,在应用中证实是有效的。通过活化提高了表面的反应性,因此与护套的塑料材料的反应在将其涂装后马上开始,并且在较短的反应时间后就在金属和塑料之间形成了良好的粘合连接。可以用气焊枪进行热活化,所述气焊枪用过量氧气或过量空气运行。从而可以达到500℃以上的很高温度,不过仅短时间对表面附近以作用。用上述等离子体处理的物理方法进行处理也相应观察到类似的活化作用。有利于观察的效果可能与对表面进行微腐蚀有关。
特别有利的是,通过用等离子体处理或用气焊枪火焰处理,金属表面被活化,从而在紧接下来的工艺中,可以使涂装的护套具有特别良好的粘合性。
在本发明优选的方案中,在使用气焊枪火焰时,作为燃烧气体,可以使用含有过量空气的甲烷、丙烷或丁烷。有利地,在使用气焊枪火焰时,燃烧气体可以含有20-30倍过量空气。
在本发明有利的方案中,涂装护套那刻,金属管表面的温度可以从室温到最高50℃。特别良好的粘合结果总是在具有所定义的且比较低的表面温度的活化管进入挤出机时达到。
在本发明优选的实施方式中,在涂装护套前,可以向金属管表面上抹增粘剂。为了使增粘剂和护套材料在工作步骤中涂装在管上,可以对方法步骤进行不同组合,这些方法步骤基本上不同于在进入挤出机前直接对管进行的预处理。增粘剂可以以薄膜涂布在表面上。加工温度视增粘剂的种类和组成而定,在此情况下,聚合物基底的热稳定性以及熔点扮演重要角色。增粘剂可以以膜形式涂布在表面上,此时最佳地使表面润湿,从而使实际的表面最大地用于官能团和金属之间的化学反应。
有利地,可以使用聚合物作为增粘剂,所述聚合物的基底例如通过马来酸酐或离聚体进行官能化。还可以向增粘剂中掺入其它起活化作用的物质作为组成部分。适合于此的尤其是基于有机或无机基础的过氧化物。
对于增粘剂和护套材料适当的组合而言,这样热涂装护套材料,使得其起到加热增粘剂的作用并引发过氧化物分解。这样就使表面发生氧化。通过过氧化物的浓度可以控制表面氧化的程度。必须准确地计量加入过氧化物,从而保证定量反应。同时该浓度不能太高,以至于对聚合物基底造成氧化性伤害。因此有利的是,向增粘剂中掺入与过氧化物量等量的抗氧化剂。因此,增粘剂的氧化作用限于金属/聚合物接触面,同时尽可能抑制对聚合物的氧化性伤害。
在本发明优选的实施方式中,增粘剂可以被涂布成薄膜。增粘剂的涂装和护套的涂装有利地可以在两个时间和地点上独立的工艺中进行。从而使各工艺步骤彼此脱离开。
在涂敷铜表面时表明,在40mN/m以上的值时就调节到可靠的粘合性。在另一优选的实施方式中,活化的金属管表面可以具有45至75mN/m的表面张力,特别优选为55至75mN/m。金属和聚合物的表面能可以通过根据DIN 53364的测试墨测得。
Claims (10)
1、一种制造带有牢固粘附的塑料护套的金属管线的方法,其特征在于:
-通过等离子体处理或通过气焊枪火焰产生活化的金属管表面,在此情况下,在表面上的作用时间小于3秒,
-将塑料护套涂装在活化的金属管表面上,以及
-在涂装护套时,金属管表面的温度低于80℃。
2、根据权利要求1所述的方法,其特征在于,在使用气焊枪火焰时,作为燃烧气体,使用含有过量空气的甲烷、丙烷或丁烷。
3、根据权利要求2所述的方法,其特征在于,燃烧气体含有20-30倍过量空气。
4、根据权利要求1-3中任意一项所述的方法,其特征在于,涂装护套那刻,金属管表面的温度为从室温到最高50℃。
5、根据权利要求1-4中任意一项所述的方法,其特征在于,在涂装护套前,向金属管表面上抹增粘剂。
6、根据权利要求5所述的方法,其特征在于,使用通过马来酸酐或离聚体官能化的聚合物作为增粘剂。
7、根据权利要求5或6所述的方法,其特征在于,增粘剂被涂布成薄膜。
8、根据权利要求5、6或7所述的方法,其特征在于,增粘剂的涂装和护套的涂装在两个时间和地点上独立的工艺中进行。
9、根据权利要求1-3中任意一项所述的方法,其特征在于,活化的金属管表面具有45至75mN/m的表面张力。
10、根据权利要求9所述的方法,其特征在于,活化的金属管表面具有55至75mN/m的表面张力。
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DE102006057884A DE102006057884B4 (de) | 2006-12-08 | 2006-12-08 | Verfahren zur Herstellung eines metallischen Leitungsrohrs mit fest anhaftender Kunststoffummantelung |
DE102006057884.8 | 2006-12-08 | ||
PCT/EP2007/010454 WO2008067963A1 (de) | 2006-12-08 | 2007-12-01 | Verfahren zur herstellung eines metallischen leitungsrohrs mit fest anhaftender kunststoffummantelung |
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EP (1) | EP2121283B1 (zh) |
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AT (1) | ATE488352T1 (zh) |
DE (2) | DE102006057884B4 (zh) |
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DE1675338A1 (de) | 1968-02-24 | 1971-01-21 | Kabel Metallwerke Ghh | Leitungsrohr fuer den Transport von Fluessigkeiten und Gasen |
US3802908A (en) * | 1972-02-28 | 1974-04-09 | D Emmons | Process for forming external multi-layer resinous coating on cylindrical surface at ambient temperature |
US4732632A (en) * | 1984-11-09 | 1988-03-22 | Raychem Corporation | Protecting elongated substrate with multiple-layer polymer covering |
US4702956A (en) * | 1985-12-12 | 1987-10-27 | Ausimont, U.S.A., Inc. | Method of bonding glass fibers or other substrates to various polymers by oxidizing the molten polymer surface, and articles produced thereby |
JPH07290641A (ja) * | 1994-04-21 | 1995-11-07 | Nippon Steel Corp | ポリエチレン被覆鋼材 |
DE4424768C1 (de) * | 1994-07-05 | 1995-11-09 | Kurt Prof Dr Ing Koppe | Verfahren und Vorrichtung zum Beschichten von metallischen Beschichtungsträgern mit einem Beschichtungsmittel auf der Basis von Kunststoff |
AT403087B (de) | 1996-03-05 | 1997-11-25 | Ke Kelit Kunststoffwerk Gmbh | Verbundrohr, dessen mantel eine mittelschicht aus kupfer und je eine haftvermittlerschicht und eine innere und äussere deckschicht aufweist |
EP1060875A3 (de) * | 1999-06-15 | 2001-12-12 | Alcan Technology & Management AG | Sterilisierbare Verbundfolie |
US20010009718A1 (en) * | 2000-01-24 | 2001-07-26 | Sinsel John A. | Polymeric coated metal strip and method for producing same |
DE10019926A1 (de) * | 2000-04-20 | 2001-10-31 | Isimat Gmbh Siebdruckmaschinen | Verfahren zum Modifizieren einer Oberfläche eines kompakten Substrates |
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JP2006527100A (ja) * | 2003-04-03 | 2006-11-30 | アイエスジー・テクノロジーズ・インコーポレイティッド | ポリマー固体薄膜のフラットロール鋼板連続ストリップへのポリマー押し出し溶融薄膜による結合方法 |
DE102005023751A1 (de) | 2004-07-02 | 2006-02-09 | Km Europa Metal Ag | Leitungsrohr zum Transport von Medien |
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DE102006057884A1 (de) | 2008-06-12 |
US20100218893A1 (en) | 2010-09-02 |
EP2121283A1 (de) | 2009-11-25 |
DE502007005713D1 (de) | 2010-12-30 |
ATE488352T1 (de) | 2010-12-15 |
CN101600559B (zh) | 2012-02-15 |
WO2008067963A1 (de) | 2008-06-12 |
DE102006057884B4 (de) | 2010-08-05 |
ES2356578T3 (es) | 2011-04-11 |
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