CN105682894A - 使用熔接促进剂来熔接塑料的方法 - Google Patents

使用熔接促进剂来熔接塑料的方法 Download PDF

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Publication number
CN105682894A
CN105682894A CN201480047741.3A CN201480047741A CN105682894A CN 105682894 A CN105682894 A CN 105682894A CN 201480047741 A CN201480047741 A CN 201480047741A CN 105682894 A CN105682894 A CN 105682894A
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Prior art keywords
welding
polymer
polymer surfaces
granule
metal
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CN201480047741.3A
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Inventor
P·沃尔特
M·伦克尔
C·霍尔特格雷韦
T·巴雄
R·舍恩菲尔德
K·黑尔梅特格
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of CN105682894A publication Critical patent/CN105682894A/zh
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    • B29C65/04—Dielectric heating, e.g. high-frequency welding, i.e. radio frequency welding of plastic materials having dielectric properties, e.g. PVC
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Abstract

本发明涉及一种在聚合物表面之间形成熔接结合的方法，其包括(i)将熔接促进剂组合物施加至一个或两个聚合物表面的将要熔接区域，其中所述熔接促进剂组合物包含颗粒尺寸范围为0.1至1000μm的颗粒，所述颗粒由对与第一和/或第二聚合物表面的化学反应呈惰性的材料制成；(ii)将能量施加至第一聚合物表面、第二聚合物表面或者二者的将要熔接的区域，所述能量足以熔融聚合物表面的将要熔接区域中的至少一部分聚合物，并使所述聚合物表面的将要熔接的区域相互接触；和(iii)使将要熔接的区域中的熔融聚合物固化，从而在所述聚合物表面之间形成熔接结合。本发明还涉及由此制得的制品，以及所描述的组合物作为熔接促进剂的用途。

Description

使用熔接促进剂来熔接塑料的方法
技术领域
本发明涉及一种使用熔接促进剂来熔接塑料的方法。本发明还涉及由此制得的制品，以及在本文中描述的组合物作为熔接促进剂的用途。
背景技术
使用螺钉、粘合剂或熔接技术来连接不同的材料在本领域中是广为人知的。例如，对于组装制品的生产来说，通常需要将两个部件——特别是两个由聚合物制成的部件——熔接在一起。尽管合适的熔接技术(例如，热气熔接、热板熔接、高频熔接、超声熔接、摩擦熔接和激光熔接)为已知的，但是可熔接复杂部件的界面设计仍然是具有挑战性的。这是由于这样的事实：所有如上所述的技术均具有这样的共同点，它们会在将要连接的两个部件之间诱发大量的能量或热量。为了将能量导向至界面并避免所述部件的未定界(undefined)熔融，对将要连接的部件或者更特别地它们的界面的特别设计就是必须的。通常使用的特殊的界面设计形状被称为“能量导向器(energydirector)”。例如，粗糙表面或者具有小的凸起的表面对于熔接来说是极其有利的，因为更小的接触面积促使熔接能量聚焦于目标区域。然而，对于这种特殊的表面设计的需求造成高度复杂的部件设计和生产。
因此，在本领域中存在着对于克服现有技术中如上所述的缺陷并允许使部件在相对于这种连接技术来说无需调整它们的形状或界面的情况下进行熔接的方法的需求。这将具有如下的优点：用于在可熔接界面方面的部件设计以及注射成型方法的时间可被显著地缩短。
尽管在本领域中已知的是，在界面处使用用以活化或清洁将要连接的表面的底层涂料(primer)或者粘合剂以在将要连接的两个部件之间形成更好的连接，但是这样的应用并未克服部件设计问题，因为它们仅支持连接两个已被设计用于熔接的部件。
发明内容
本发明满足了对于熔接方法的如上所述的需求，即：对于这种连接技术来说，通过提供使用熔接促进剂组合物来熔接未经特别调整的两个聚合物表面的方法，所述方法允许在无需调整它们的形状或界面的情况下熔接部件，所述熔接促进剂为对与表面聚合物的化学反应呈惰性的，并且不会增强两个将要连接的表面之间的粘附性。更特别地，本发明的发明人令人惊讶地发现，使用粉末、凝胶或分散体形式的化学惰性颗粒作为熔接促进剂能够消除对起能量导向器作用的表面结构的需求，因为所述颗粒可以接替这种功能，并将熔接能量导向至将要熔接的表面的特定(concrete)区域。
在第一方面中，本发明由此涉及一种用于在第一和第二聚合物表面之间形成熔接结合的方法，其包括：
(i)将熔接促进剂组合物施加至所述第一聚合物表面、所述第二聚合物表面或者二者的将要熔接的区域，其中所述熔接促进剂组合物包含颗粒尺寸范围为0.1至1000μm的颗粒，所述颗粒为对与所述第一和/或第二聚合物表面的化学反应呈惰性的材料；
(ii)将能量施加至所述第一聚合物表面、所述第二聚合物表面或者二者的将要熔接的区域，所述能量足以熔融所述第一聚合物表面、所述第二聚合物表面或者二者的将要熔接区域中的至少一部分聚合物，并使所述第一和第二聚合物表面的将要熔接的区域接触在一起，其中所述施加能量的步骤可以在使所述第一和第二聚合物表面的将要熔接的区域相互接触之前和/或期间执行；和
(iii)使所述第一聚合物表面、所述第二聚合物表面或者二者的将要熔接的区域中的熔融聚合物固化，从而在所述第一和第二聚合物表面之间形成熔接结合。
本发明的另一个方面涉及包含熔接结合的制品，所述熔接结合可以根据如上所述的方法获得。
在又一个方面中，本发明还包括包含颗粒的组合物作为熔接促进剂用以在两个聚合物表面之间形成熔接结合的用途，所述颗粒为对与聚合物表面的化学反应呈惰性的材料，并且不会增强第一和第二聚合物表面之间的粘附性，其中所述颗粒的颗粒尺寸范围为0.1至1000μm。
具体实施方式
在下文中，更加详细地描述本发明。然而，可以理解的是，本发明并不限于如下的实施方案，而是可以容易地经调整以使用其它的聚合物和颗粒材料。这样的替代实施方案同样包括在本发明的范围内。
在用于形成熔接结合的方法的第一步中，将熔接促进剂组合物施加至第一聚合物表面、第二聚合物表面或者二者的将要熔接的区域。其中所使用的术语“聚合物表面”是指构成将要连接的部件的表面的聚合物材料。优选地，部件由这种聚合物材料构成，即，聚合物表面为聚合物主体或部件(例如树脂主体)的表面。如在本文中所使用的，“聚合材料”或者“聚合物材料”涉及除了聚合物之外还可以包含其它组分(例如填料、添加剂等)的聚合物组合物。将要连接的两个表面的两种聚合物——或者在更特别的实施方案中，将要连接的两个主体或部件的材料——可以是相同的或不同的。如果它们为不同的，那么所述不同的材料可能具有不等的熔融温度范围，这会使现有的熔接方法变得复杂，但是当采用在本文中所描述的方法时就是不成问题的。如在本文中所使用的，“不等的熔融温度范围”是指两种聚合材料的熔融温度范围可检测为不同的。
构成将要连接的表面或部件的聚合物优选为热塑性聚合物。尽管优选的是，两个表面的聚合物均为热塑性的，但是在某些实施方案中，两个聚合物表面中的任意一个可以由热塑性材料构成，而另一个则由不同的聚合物材料(例如热固性聚合物)构成。
可以通过所描述的方法熔接在一起的合适的基础聚合物包括但不限于聚丙烯(PP)、聚乙烯(PE)、聚辛烯、聚(苯乙烯-丁二烯-苯乙烯)(SBS)、聚(苯乙烯-异戊二烯-苯乙烯)(SIS)、聚(苯乙烯-乙烯/丁烯-苯乙烯)(SEBS)、聚(苯乙烯-乙烯/丙烯-苯乙烯)(SEPS)、聚乙烯-醋酸乙烯酯(EVA)、丙烯腈丁二烯苯乙烯共聚物(ABS)、聚(甲基丙烯酸甲酯)(PMMA)、聚甲基丙烯酸酯、聚丙烯酸酯、聚碳酸酯(PC)、聚苯乙烯(PS)、聚酰胺(PA)、聚氯乙烯(PVC)、及它们的共聚物和共混物。合适的共混物包括例如PC/ABS共混物和PA/ABS共混物。在优选的实施方案中，第一表面的聚合物为PP或PA，并且第二表面的聚合物为PA、PP、PC/ABS、ABS、PMMA、PA/ABS或PC。在本文中使用的“基础聚合物”是指其为所给出聚合物组合物的主要聚合成分的聚合物，即在所述组合物中大于所有聚合物50wt％的为基础聚合物。如上提及的共聚物包括其中如上所述的一种单体单元或预聚物与另一种单体单元或预聚物共聚的那些。
将要结合的表面可以是平坦的或平面的，但是还可以是波状外形的(contoured)。
熔接促进剂组合物可以是允许存在所给定规格的离散颗粒的任意形式。合适的形式包括但不限于粉末、凝胶和分散体。因为所述颗粒通常为固体形式，所以在它们以凝胶或分散体形式使用的情况中，它们被分散于合适的基体中。所述基体可以是任意合适的材料，并且还优选为对与第一和/或第二聚合物表面的化学反应呈惰性的。
更特别地，优选的是，熔接促进剂组合物并不包括任何已知的底层涂料或粘合剂，所述底层涂料例如为清洁或活化表面的那些，所述粘合剂例如为与表面聚合物进行化学反应并通常在固化之后于两个表面之间形成化学键的那些。优选的是，颗粒仅起能量导向器的作用，即将熔接能量导向至将要熔接的区域，并导致聚合物表面的至少部分熔融。进一步优选的是，颗粒和熔接组合物并不会增强第一和第二聚合物表面之间的粘附性，即不具有粘合作用。
如在本文中所使用的，“惰性”是指由此指定的材料在方法的任何步骤中，在熔接条件下，不会与将要连接的表面的聚合物发生化学反应。如在本文中所使用的，“发生化学反应”是指在熔接组合物(即特别是颗粒)的材料和聚合物表面之间形成化学键。
取决于熔接促进剂组合物的形式，施加可以通过适合用于这种目的的任意现有的技术来完成。合适的施加技术包括但不限于印刷、喷洒、喷涂、旋涂、浸涂等。
在各种实施方案中，仅将熔接促进剂组合物施加至那些将要熔接的表面区域。在这样的实施方案中，其用于这样的目的，即将所施加的熔接能量导向至这些特定的区域，所述特定的区域当接收到所述能量时表面熔融，从而避免未定界的和不受控制的聚合物表面熔融。
熔接促进剂组合物包含颗粒，所述颗粒为对与第一和/或第二聚合物表面的化学反应呈惰性并且不会增强所述第一和第二聚合物表面之间的粘附性的材料。所述颗粒的比重优选为0.1至20g/cm3，更优选为约1至约4g/cm3。体密度可以是1至10g/cm3。颗粒尺寸为0.1至1000μm，优选为10至500μm。如在这里所使用的，“尺寸”是指沿颗粒最大维度的长度。所述颗粒可以具有任意形状，但是优选为基本上球形的形状或立方体的形状。所述颗粒可以是基本上单分散的或多分散的。颗粒的平均尺寸优选为1至1000μm，优选为10至500μm，更优选为50至400μm。“平均尺寸”是指颗粒的算术平均尺寸。用于确定颗粒尺寸的各种不同的技术为本领域已知的。那些技术包括——仅以举例的方式——筛分技术、动态光散射和激光衍射。优选地，颗粒尺寸通过筛分技术来确定。平均颗粒尺寸优选通过动态光散射来确定。
在各种实施方案中，颗粒的莫氏硬度至少为2.5，优选至少为3，更优选至少为3.5，最优选至少为4。
在各种实施方案中，所述颗粒包含无机材料、基本上由无机材料构成或者由无机材料构成，所述无机材料例如为玻璃、二氧化硅、陶瓷、金属、金属化合物等。所述金属化合物包括金属氧化物、金属盐、和金属与非金属的反应产物(例如磷化物、氮化物等)。优选的无机材料包括但不限于二氧化硅、氧化铝、氧化铁、氧化钛、氧化镁、磷化铁和玻璃(例如钠钙硼硅玻璃)。如上所述的材料的混合物也是可行的。
所述颗粒可以是微球，其可任选地为中空的。“微球”是指直径为μm级(1至1000μm)的球形颗粒。
可以使用的合适的材料包括但不限于玻璃珠(其直径优选为约200μm(Spheriglass，PottersEurope))、Ferrophos2132(OccidentalChemicalCorporation)、CenospheresS500和Cab-o-Sil。对于材料的选择，如果所述材料使得表面之间的摩擦提高，那么其为适用的。
在本文所描述的方法中的下一个步骤中，将能量施加至第一和/或第二聚合物表面的将被熔接的区域。能量的大小足以在将要熔接的区域的表面至少部分地熔融聚合物。熔接促进剂组合物——特别是在其中所包含的颗粒——用于这样的目的：将熔接能量导向至这些特定的区域，并避免未定界的和不受控制的聚合物表面熔融。
为了形成熔接结合，可首先施加能量以在表面熔融聚合物，并在发生熔融之后，可使将要熔接的区域接触在一起。或者，两个步骤可以同时执行，即在施加能量的同时，使两个区域接触在一起。所述接触可以是压制，即两个表面可以通过施加力而被有力地(actively)压制在一起。在接触时，特别是在压制中，所施加的力可以随着时间而变化。施加能量的步骤可以重复一次或多次。例如，可将能量施加至一个或两个表面来诱发熔融，随后使两个表面接触，并在所述接触过程中和/或其后再次施加能量。
所施加的能量可以是热、超声、振动、辐射或摩擦的形式。换句话说，可对将要连接的表面一起进行加热、超声或辐射(特别是红外或激光辐射)、或摩擦。这种处理的目的在于在将要熔接区域的表面至少部分地熔融聚合物。用于将能量引入至系统内并导致聚合物表面熔融的已知技术包括但不限于热气熔接、热板熔接、高频熔接、超声熔接、摩擦熔接和激光熔接以及红外熔接。还优选的是，使用至少两种能量源——特别是两种能量源——的组合。在一种实施方案中，红外熔接与振动熔接或超声熔接联合使用。
在优选的实施方案中，所述能量以超声能量的形式使用。可以使用多个不同的超声能量供给器来向表面提供超声能量。对典型的超声能量供给器进行构建以提供超声能量，并且所述超声能量供给器包括两个或多个能量源(例如电源或发电机)、一个或多个能量处理器(例如转换器、增幅器(booster)或二者)、能量发射器(例如喇叭)。
一旦表面的聚合物已被至少部分地熔融，就可以将两个表面彼此抵靠在一起摩擦，从而将表面的熔融聚合物共混。在两种聚合物为不同的聚合物并且两个表面已被至少部分地熔融的情况中，这是特别适用的。
在所描述方法的最终步骤中，使熔融聚合物再次固化，从而在两个表面之间形成熔融结合。所述固化可以通过停止将能量施加至系统以及由此导致的冷却而发生。
本领域技术人员可以使用如在本文中描述的方法并可以改变将要熔接的主体的聚合物以及用作能量导向器的颗粒的材料、所施加的能量的形式和条件(即熔接促进剂的量和所施加能量的大小、能量施加时间等)，从而得到具有那些预期目标所需要的熔接结合的结合制品。
本发明还涉及通过所描述的方法所获得的或者可以通过所描述的方法获得的熔接制品，即组装制品。
本发明还涵盖包含如上所限定的颗粒的组合物用于在两个聚合物表面之间形成熔接结合的用途。以上所公开的与在本文中描述的方法相关的所有限定均可类似地适用于这些用途。这特别地涉及颗粒和熔接促进剂组合物和将要连接的聚合物主体的定义。
实施例
选择重叠+/-5mm的搭接剪切几何图形的两个聚酰胺(PA6.6；Latamid66H2)聚合物基材。对所述基材通过联合使用KLN超声发生器型号588以及超声波发生器(sonotrode)进行超声熔接而熔接。垂直于熔接区域，施加0.5-1.6N/mm2的恒定压力。熔接时间恒定地保持为1s。
表1示出搭接剪切强度(LSS)试验的结果，其使用不同的颗粒材料作为熔接促进剂来完成，从而显示出熔接的增强。在这个试验中，大于5、优选大于10的LSS值表示良好的熔接结果。一个优点在于将熔接聚集/导向至目标重叠区域，并且另一个优点在于通过引入恰当的熔接区域而提高了LSS值。玻璃珠、Ferrophos2132和CenospheresS500获得特别良好的结果。
表1：LSS试验

Claims (15)

1.用于在第一和第二聚合物表面之间形成熔接结合的方法，包括：
(i)将熔接促进剂组合物施加至所述第一聚合物表面、所述第二聚合物表面或者二者的将要熔接的区域，其中所述熔接促进剂组合物包含颗粒尺寸范围为0.1至1000μm的颗粒，所述颗粒由对与所述第一和/或第二聚合物表面的化学反应呈惰性的材料制成；
(ii)将能量施加至所述第一聚合物表面、所述第二聚合物表面或者二者的将要熔接的区域，所述能量足以熔融所述第一聚合物表面、所述第二聚合物表面或者二者的将要熔接区域中的至少一部分聚合物，并使所述第一和第二聚合物表面的将要熔接的区域接触在一起，其中所述施加能量的步骤可以在使所述第一和第二聚合物表面的将要熔接的区域接触在一起之前和/或期间执行；
(iii)使所述第一聚合物表面、所述第二聚合物表面或者二者的将要熔接的区域中的熔融聚合物固化，从而在所述第一和第二聚合物表面之间形成熔接结合。
2.权利要求1的方法，其中所述第一聚合物表面和/或所述第二聚合物表面为树脂主体的表面。
3.权利要求1或2的方法，其中所述第一聚合物表面的聚合物和所述第二聚合物表面的聚合物为相同的或不同的。
4.权利要求1至3任一项的方法，其中所述第一聚合物表面的聚合物和/或所述第二聚合物表面的聚合物为热塑性树脂。
5.权利要求1至4任一项的方法，其中所述第一和/或第二表面的基础聚合物独立地选自聚丙烯(PP)、聚乙烯(PE)、聚辛烯、聚(苯乙烯-丁二烯-苯乙烯)(SBS)、聚(苯乙烯-异戊二烯-苯乙烯)(SIS)、聚(苯乙烯-乙烯/丁烯-苯乙烯)(SEBS)、聚(苯乙烯-乙烯/丙烯-苯乙烯)(SEPS)、聚乙烯-醋酸乙烯酯(EVA)、丙烯腈丁二烯苯乙烯共聚物(ABS)、聚(甲基丙烯酸甲酯)(PMMA)、聚(甲基)丙烯酸酯、聚碳酸酯(PC)、聚苯乙烯(PS)、聚酰胺(PA)、聚氯乙烯(PVC)、及它们的共聚物和共混物。
6.权利要求1至5任一项的方法，其中所述熔接促进剂组合物为粉末、凝胶或分散体的形式。
7.权利要求1至6任一项的方法，其中所述颗粒的莫氏硬度至少为2.5，优选至少3，更优选至少4。
8.权利要求1至7任一项的方法，其中所述熔接促进剂组合物的颗粒包含选自玻璃、金属、包括金属氧化物和金属盐的金属化合物、二氧化硅和陶瓷的材料，基本上由选自玻璃、金属、包括金属氧化物和金属盐的金属化合物、二氧化硅和陶瓷的材料构成或者由选自玻璃、金属、包括金属氧化物和金属盐的金属化合物、二氧化硅和陶瓷的材料构成。
9.权利要求1至8任一项的方法，其中所述能量以加热、振动、超声、辐射和/或摩擦的形式施加。
10.权利要求9的方法，其中所述施加能量的步骤包括热气熔接、热板熔接、高频熔接、超声熔接、摩擦熔接、红外熔接和/或激光辐射熔接。
11.权利要求1至10任一项的方法，其中所述方法既不使用底层涂料也不使用粘合剂在所述第一和第二聚合物表面之间形成熔接结合。
12.权利要求11的方法，其中所述熔接促进剂组合物的颗粒起能量导向器的作用以将所施加的能量导向至所述第一和/或第二聚合物表面的将要熔接的区域。
13.制品，包含根据权利要求1至12任一项的方法所获得的熔接结合。
14.包含颗粒的组合物作为熔接促进剂用以在两个聚合物表面之间形成熔接结合的用途，所述颗粒为对与聚合物表面的化学反应呈惰性的材料，其中所述颗粒的颗粒尺寸范围为0.1至1000μm。
15.权利要求14的用途，其中所述组合物的颗粒
(i)具有的莫氏硬度为至少2.5，优选至少3，更优选至少4；
(ii)包含选自玻璃、金属、包括金属氧化物和金属盐的金属化合物、二氧化硅和陶瓷的材料，基本上由选自玻璃、金属、包括金属氧化物和金属盐的金属化合物、二氧化硅和陶瓷的材料构成或者由选自玻璃、金属、包括金属氧化物和金属盐的金属化合物、二氧化硅和陶瓷的材料构成。
CN201480047741.3A 2013-08-30 2014-08-29 使用熔接促进剂来熔接塑料的方法 Pending CN105682894A (zh)

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