CN104884670A - 在非导电性的基底材料上制造导电结构的方法以及用于此的特定添加物和基底材料 - Google Patents

在非导电性的基底材料上制造导电结构的方法以及用于此的特定添加物和基底材料 Download PDF

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CN104884670A
CN104884670A CN201380069097.5A CN201380069097A CN104884670A CN 104884670 A CN104884670 A CN 104884670A CN 201380069097 A CN201380069097 A CN 201380069097A CN 104884670 A CN104884670 A CN 104884670A
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additive
area
base material
metallic compound
substrate material
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R.A.克鲁格
B.罗斯纳
W.约翰
A.施努尔
R.奥斯特霍尔特
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LPKF Laser and Electronics AG
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Abstract

本发明涉及在非导电性的基底材料上制造导电结构，特别是印刷电路的方法，所述基底材料包括具有至少一种金属化合物的添加物(1)。为此，使用激光来照射所述基底材料以选择性活化添加物(1)中所含的例如无机金属化合物。随后，金属化通过活化所形成的金属种晶以提供基底材料上的导电结构。由于在将添加物(1)引入基底材料之前该添加物具有全包围涂层，从而通过激光活化使添加物(1)被还原并所述涂层被氧化，因此借由涂层为与该添加物(1)进行所需的化学反应提供了必要的反应物。当与所述基底材料的相互作用因此被显著减少时，也同时解除了对特定塑料或塑料组的限制。

Description

在非导电性的基底材料上制造导电结构的方法以及用于此的特定添加物和基底材料
本发明涉及在非导电性的基底材料上制造导电结构，特别是印刷电路(Leiterbahn)的方法，所述基底材料包括具有至少一种金属化合物的添加物(Additiv)，其中使所述基底材料部分经受激光照射并且添加物中所含的金属化合物被活化，以便在这样的激光活化的区域形成催化活性的种晶(Keime)，随后将其在无外电流的(auβenstromlose)金属化浴中金属化，并由此在非导电性的基底材料上创建导电结构。
在实践中，名为MID(Molded Interconnect Devices)(模内互连装置)的立体注塑电路板已为人所知并被广泛应用。所述MID技术在一个部件中结合了电气和机械功能。在这种情况下，将导电结构集成进壳体并由此取代传统的电路板，从而减少了重量、安装空间和安装成本。
在这种情况下，所谓的激光直接结构化(LDS)特别受到重视。在LDS工艺中，基底材料作为模制件在单组元注塑成型(Einkomponenten-Spritzguss)中以专门添加的塑料颗粒注塑。借助于激光可使添加物在物理化学反应中选择定位性地(ortsselektiv)转化成催化活性的种晶，其中在随后的化学金属化浴(Metallisierungsbad)中金属有针对性地沉积于如此处理过的位点处。
除了活化，激光还具有以下目的，即产生微粗糙的表面以确保金属层在塑料基板上的足够的附着力。
由于通过计算机软件控制经受激光照射的区域，因而在LDS工艺中可以在尽可能短的时间内并在不修改工具的情况下调整或改变电路布局。这种情况以及各种可用于LDS的塑料的商业供应最终导致，对于MID的制造来说LDS工艺是领先技术。
在DE 101 32 092 A1中描述了非导电性基底材料上的印刷电路结构，其包括金属种晶和随后施加在其上的金属化，其中通过使用电磁辐射击碎基底材料中所含的精细粒度分布的非导电性无机金属化合物来形成金属种晶。
DE 10 2004 021 747 A1也描述了这样的印刷电路结构，其中通过使用电磁辐射击碎基底材料中所含的精细粒度分布的纳米级的金属化合物来形成金属种晶。为了保持基底材料的透明度(其使光导(Lichtleitung)成为可能并由此使得印刷电路结构和光导的基底材料的组合能够用于光电方面的应用)，而使用纳米级的非导电性的金属化合物，其颗粒具有特征尺寸低于200nm的纳米尺寸。由此基底材料的透明度和非导电性金属化合物的功能得以保持。
此外，WO 2012/056385 A1描述了一种LDS材料的经改进的无电流的电镀性能(stromlosen Plattierungsleistung)的方法。
由于技术方面的限制，现如今借助于LDS工艺能够可靠地制造最小间距为150μm的电路板电路。为了进一步推动所需的MID的小型化，当务之急是将所述限制进一步向后推。为此作出了很大的努力，使激光照射聚焦程度更高并将其更精确地在模件的表面引导。其次是减小添加物的尺寸，以确保更好的激光结构化的边缘锐度。然而，必须注意的是这种方式受到限制，因为在混炼或注塑成型的过程中在颗粒尺寸减小的情况下一般会使添加物聚集在一起的可能性增加。
在此，以下三个方面尤为重要：
1)基础聚合物以及由其制造出的工件的物理特性，例如耐冲击性和断裂强度，受到添加物的数量、大小、形状和类型的影响。
2)添加物的类型在本质上决定所使用的激光射线可具有什么样的波长并且其是如何有效地被吸收的。
3)使用不同的材料来不同程度地促进添加物向催化活性的种晶的化学物理的转化并且在某些材料中可以不发生所述转化。
本发明的目的在于，以适当的方式来实施添加物，使得相比于添加物的独立作用，添加物-包覆-混合对基础聚合物的物理性能的不利影响较小并且通过激光照射更有效地转化成催化活性的种晶。
根据本发明，上述目的通过根据权利要求1的特征的方法得以实现。本发明进一步的实施方式由从属权利要求来限定。
本发明还提供一种方法，其中添加物包括除由例如无机金属化合物形成的第一区域以外的至少一个第二区域，所述第二区域具有不同的化学组成，并且通过激光活化来降低所述添加物中的金属的氧化态。当所述添加物具有第二区域作为含不同化学组成的物质时，为该添加物创建了反应性的微环境，并且基本减少或完全避免了与基底材料的化学反应。由于通过这样的方法可有效地进行添加物至催化活性的种晶的转化，因而还降低了所需的添加物的剂量，并由此降低了基底材料中所需的比重。根据本发明降低的添加物的最小量由此直接导致较小的对基底材料的性能的影响。由于添加物-包覆-混合为所需的化学物理反应提供了所有必要的物质，因而还同时解除了对特定塑料或塑料组的限制。当基底材料混合了具备第二区域的添加物时，例如具有相当大比例的PTFE的基底材料适用于实施本发明的方法。当然，本发明不排除在添加物中还额外混合作为第二区域的物质。
已表明，这样的第二区域(例如在某些情况下作为涂层)不仅可以显著地压制聚集，而且还有利地影响到随后的化学金属化。更准确的检查表明，一些包覆物质(Hüllsubstanzen)能够比它们周围的基底材料的塑料基质更好地促进添加物至催化活性种晶的化学物理的转化。
本发明的一个显著的优势主要来自以下事实，可将添加物供给任何基底材料并因而无需考虑基底材料的特定属性而实现可靠的所需的激光活化。因此，特别地，可省去先前为适应基底材料的不同属性而要求的辅助手段。因此，也可以仅在成型(formgebend)过程中才提供或混入添加物，从而添加物并不一定要在处理之前就存在于基底材料中。
然而，当第二区域基本上包含有机化合物时，该区域也基本会导致明显改善的机械性能。在此，在第二区域和基底材料之间的界面处有机成分基本上总是彼此重叠在一起。通过第二区域，在作为添加物的基底材料的塑料的结构中出现小得多的干扰。特别地，通过包围金属化合物的第二区域可将所存在的颗粒边缘整平，从而减少或者甚至避免了在现有技术中不能可靠排除的基底材料中添加物的缺口效应(Kerbwirkung)。
可将第二区域作为涂层优选全包围地涂覆于添加物，以实现添加物相对于基底材料的分离。这种情况下，这样来选择涂层厚度，以使涂层在添加物上具有足够的附着强度，并因此特别是在将设置有涂层的添加物混入基底材料时不会使涂层与该添加物分离或损坏该涂层。特别优选的是，以相应于涂层中所含的至少一种活性成分与添加物的化学计量比的量将所述涂层涂覆于添加物上，以在涂层中提供还原添加物所需的物质的量。其结果是，添加物与基底材料的相互作用或化学反应被大大抑制。在实践中，根据本发明涂覆5nm～2μm的涂层厚度。
所述添加物可存在于富水溶液中，其以液体的形式被施用于基底材料中。然而，本发明的一项特别有希望的实施方式是，其中以可撒布或可流动的形式，特别是粉末的形式来制备具备第二区域的添加物，并将其混入基底材料。其结果是，用于制备所述混合物的制备过程以及另外的系统需求被简化。特别是能够依据质量比以简单的方式来监测所需的混合。
通过根据本发明使添加物与基底材料的相互作用被基本消除，由于在第二区域中包含对所述添加物特定的反应物，因而在选择基底材料时没有那些针对适用于化学反应的塑料材料的限制。由此，这样的反应迟缓或不反应的基底材料也适用于所述方法的实施。
本发明的另一项，同样也特别有希望的实施方式通过以下来实现，在第二区域引入吸收剂，其有利于激光能量用于实现添加物中所含的金属化合物的激光活化的转化。其结果是，以最佳的方式将通过激光照射引入的能量转化成所需的活化能(该活化能对于引发一面包含在第二区域中的反应物与另一面包含在添加物颗粒中的反应物之间的反应是必须的)并且因此效率被提高。因此，在第二区域或添加物对激光射线的波长为透明的情况下，所述充当吸收剂的物质在第二区域甚至以特别有利的方式使所需的活化成为可能。根据本发明还可以使用这种添加物，使用所选择的激光并不能将其活化，而通过使用第二区域中的和由此产生的第二区域所含的物质与添加物的相互作用中的合适的反应物使反应得以实现。因此，以这种方式使添加物基本上脱离激光的选择。这种情况下，吸收剂被调整至激光的波长。例如，此处吸收剂位于红外的波长范围
根据本发明的其它方面，基底材料包括半导体材料、陶瓷和/或玻璃作为主要的材料成分，从而还可以结合这样的基底材料来实施本发明的用于选择性活化和随后的金属化的方法，所述基底材料本身不能对添加物起化学还原的作用。此外，通过添加物与其第二区域的化学反应显著减少了基底材料的化学和物理性能的变化。
实施例1
在真空烘箱中于150℃的温度干燥一份氧化铜(II)粉末(Sigma-Aldrich公司)，并且在双螺杆挤出机(Collin公司)中将其与一份聚对苯二甲酸丁酯(Polybutylenterephthalat)(Lanxess公司)加工成均质的颗粒。首先将所述颗粒在冲击式精磨机(Feinprallmühle)(Hosokawa/Alpine公司)中研磨至0.5mm的粒径，然后在行星式球磨机(Planetenkugelmühle)(Pulverisette 7PremiumLine/1mm氧化锆球/氧化锆研磨罐，Fritsch公司)中研磨成约1μm的最终细度(Endfeinheit)。然后将如此获得的氧化铜(II)-聚对苯二甲酸丁酯-混合以10重量百分比与聚丙烯(Ensinger公司)配混(eincompoundieren)并注塑成工件。可借助于激光选择定位性地活化如此获得的工件以进行无外电流的金属化。相比于仅含有未改性的氧化铜(II)的试样，如此获得的聚丙烯工件相对于金属化具有提高数倍的性能。
实施例2
混合两份氧化铜(I)与一份聚酯树脂(Presto公司)，并将其浇铸成薄板。在所述板完全固化后，先将其机械粉碎。然后在冲击式精磨机(Hosokawa/Alpine公司)中将颗粒研磨至0.5mm的粒径，并随后在行星式球磨机(Planetenkugelmühle)(Pulverisette 7Premium Line/1mm氧化锆球/氧化锆研磨罐，Fritsch公司)中研磨成约1μm的最终细度(Endfeinheit)。然后将如此获得的热固性氧化铜(I)-聚酯-混合以8重量百分比与聚乙烯(LyondellBasell公司)配混并注塑成工件。借助于激光选择定位性地活化如此获得的工件以进行无外电流的金属化。相比于仅含有未改性的氧化铜(I)的试样，如此获得的聚乙烯工件相对于金属化具有提高数倍的性能。
实施例3
于130℃干燥两份氧化铁(III)，并且在双螺杆挤出机(Collin公司)中将其与一份液晶聚合物(Ticona公司)加工成均质的颗粒。然后先在冲击式精磨机(Hosokawa/Alpine公司)中将所述颗粒研磨至0.5mm的粒径，并随后在行星式球磨机(Planetenkugelmühle)(Pulverisette 7Premium Line/1mm氧化锆球/氧化锆研磨罐，Fritsch公司)中研磨成约1μm的最终细度(Endfeinheit)。然后将如此改性的氧化铁(III)以12重量百分比与聚氨酯(SLM Solutions公司)掺混(einarbeiten)并以真空浇铸法模制成工件。借助于激光选择定位性地活化如此获得的工件以进行无外电流的金属化。相比于仅含有未改性的氧化铁(III)的试样，如此获得的聚氨酯工件相对于金属化具有提高数倍的性能。
本发明允许各种实施方式。为了进一步阐明其基本原理，附图示出了其中的一个并在下文中对其进行描述。其分别在界面示意图中显示：
图1示出了具有非均匀分布的第一和第二区域的添加物；
图2示出了具有第二区域的添加物，所述第二区域被设计成形成种晶的第一区域上的涂层；
图3示出了具有种晶所形成的第二区域的添加物。
下面将参照图1至3对本发明的用于在未示出的基底材料上制造导电性结构的添加物进行更详细的描述。此处，添加物1包括至少一种形成第一区域2的金属化合物。通过借助于激光的照射优选选择性活化该金属化合物，由此在这样激光活化的区域形成催化活性的种晶，其随后被金属化。添加物1除金属化合物之外还额外包含第二区域3(其具有一种或多种化学组成不同于所述金属化合物的物质)，从而通过激光活化降低了添加物1中的金属的氧化态。当添加物1具有其它含不同化学组成的与金属化合物相匹配的物质时，创建了针对此的反应性微环境并基本减少或完全避免了与基底材料的化学反应。不依赖于基底材料，金属化合物至催化活性的种晶的转化过程由此更为有效，其中与此同时降低了基底化合物中所需的比重。当添加物1为所需的化学物理反应提供所有必须的物质时，也同时解除了对特定塑料或塑料组的限制。
对于图1所示的添加物1的变化，此处使用了两个区域2、3的非均匀混合物，这特别使得简单的制备(例如甚至在成型过程中)成为可能。
相反，通过图2所示的变化(其中第二区域3作为涂层被全包围地涂覆在金属化合物上)可实现添加剂1相对于基底材料的分离，以阻止基底材料与金属化合的不受期望的化学反应。
此外，在图3所示的变化中，当例如在特定的应用中需要添加物1与基底材料的反应并且第二区域3仅应支持化学反应时，金属化合物可完全包围所述第二区域3。

Claims (12)

1.在包括具有至少一种金属化合物的添加物(1)的非导电性的基底材料上制造导电结构，特别是印刷电路的方法，其中使用激光照射所述基底材料并由此选择性活化所述添加物(1)中包含的金属化合物，从而在如此激光活化的区域形成催化活性的种晶，随后金属化所述种晶，并由此提供所述非导电性基底材料上的导电结构，其特征在于，所述添加物(1)除通过所述金属化形成的第一区域(2)之外包括至少一具有不同化学组成的第二区域(3)，并通过所述激光活化降低所述添加物(1)中的金属的氧化态。
2.根据权利要求1所述的方法，其特征在于，所述金属化合物形成所述添加物(1)的内核，并且至少部分区段地由所述第二区域(3)，特别是由其作为涂层包围。
3.根据权利要求1所述的方法，其特征在于，所述金属化合物至少部分区段地由所述第二区域(3)渗透。
4.根据权利要求1所述的方法，其特征在于，所述金属化合物至少部分区段地包围所述第二区域(3)。
5.根据前述权利要求中至少一项所述的方法，其特征在于，所述添加物(1)至少一个尺寸小于5μm。
6.根据前述权利要求中至少一项所述的方法，其特征在于，所述第二区域(3)基本上是有机化合物。
7.根据前述权利要求中至少一项所述的方法，其特征在于，所述第二区域(3)基本上是还原的金属化合物。
8.根据权利要求2所述的方法，其特征在于，涂覆厚度在5nm至2μm之间的第二区域(3)。
9.根据前述权利要求中至少一项所述的方法，其特征在于，将吸收剂引入所述第二区域(3)，所述吸收剂促进用于所述添加物(1)中包含的金属化合物的激光活化的激光能转化。
10.根据前述权利要求中至少一项所述的方法，其特征在于，所述添加物(1)中包含的金属化合物是金属氧化物。
11.用于在非导电性的基底材料上制造导电结构的特定的添加物(1)，其包含至少一种金属化合物作为第一区域(2)，其特征在于，所述添加物(1)包括具有不同的化学组成的第二区域(3)，将所述第二区域特别作为所述第一区域(2)的涂层来实施，并且通过激光活化降低所述添加物(1)中的金属的氧化态。
12.用于在根据前述权利要求中至少一项所述的基底材料上制造导电结构，特别是印刷电路的具有添加物(1)的基底材料，其特征在于，所述基底材料包括聚合物、半导体材料、陶瓷、木材和/或玻璃作为主要的材料成分。
CN201380069097.5A 2013-01-02 2013-12-06 在非导电性的基底材料上制造导电结构的方法以及用于此的特定添加物和基底材料 Pending CN104884670A (zh)

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CN114069196A (zh) * 2020-07-30 2022-02-18 Oppo广东移动通信有限公司 壳体组件及其制备方法、天线组件和电子设备

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CN112420300A (zh) * 2020-11-11 2021-02-26 昆山丰景拓电子有限公司 一种新型电阻及其制造方法

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EP2912210A2 (de) 2015-09-02
JP2016507650A (ja) 2016-03-10
KR20150095834A (ko) 2015-08-21

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