CN113248902A - 用于可热成形电路的导热电介质 - Google Patents
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Abstract
本发明涉及聚合物厚膜导热的可热成形电介质组合物，其包含聚氨酯树脂、热塑性苯氧基树脂、双丙酮醇和导热粉末。由所述组合物制成的电介质可用于多种电应用中以保护电元件，并且尤其用于电容式开关应用中以隔离和保护的导电性可热成形银和聚碳酸酯基板二者。随后可对热成形电路进行注塑加工。
Description
本发明专利申请是国际申请号为PCT/US2014/048766，国际申请日为2014年7月30日，进入中国国家阶段的申请号为201480035694.0，名称为“用于可热成形电路的导热电介质”的发明专利申请的分案申请。
技术领域
本发明涉及具有导热性的聚合物厚膜可热成形电介质组合物。由组合物制成的电介质可用于多种电应用中以保护电元件，并且尤其用于在电容式开关中提供导热性。
背景技术
长久以来，电介质已被用于保护电元件。它们也已被用作隔离层。虽然它们已在这些类型的应用中使用多年，但在热成形程序期间将电介质用作热导体并不常见。这在使用高导电性银并且必须防止热在电路中积聚的可热成形电容电路中尤其重要。热可对电路的性能具有有害影响，常常导致不希望的电阻变化。本发明的目的之一是减轻该问题并制备其中可控制产生的热的可热成形电容构造。
发明内容
本发明涉及聚合物厚膜导热的可热成形电介质组合物，其包含：
(a)10-35重量％的第一有机介质，所述第一有机介质包含溶解于50-90重量％的第一有机溶剂中的10-50重量％的聚氨酯树脂，其中所述聚氨酯树脂和所述第一有机溶剂的重量百分比是基于所述第一有机介质的总重量计的；
(b)10-35重量％的第二有机介质，所述第二有机介质包含溶解于50-90重量％的第二
(c)有机溶剂中的10-50重量％的热塑性苯氧基树脂，其中所述热塑性苯氧基树脂和所述第二有机溶剂的重量百分比是基于所述第二有机介质的总重量计的；
(d)2-20重量％的双丙酮醇，其中所述重量百分比是基于所述组合物的总重量计的；以及
(e)1-70重量％的导热粉末；
其中所述第一有机介质、所述第二有机介质、所述双丙酮醇和所述导热粉末的重量百分比是基于所述组合物的总重量计的。
本发明还涉及使用导热的可热成形电介质以在可热成形电容电路中形成保护层和/或绝缘层。
具体实施方式
本发明涉及用于热成形电路中的聚合物厚膜导热的可热成形电介质组合物。
常用于聚合物厚膜可热成形电容电路中的基板是聚碳酸酯(PC)。PC通常为优选的，因为其可容易地热成形。然而，PC对沉积在其上的层中使用的溶剂非常敏感。不适当的溶剂能够并且将造成PC基板中的裂缝或裂纹。
聚合物厚膜(PTF)导热的可热成形电介质组合物由下列物质构成：(i)包含两种溶解于相同或不同有机溶剂中的聚合物树脂的两种有机介质，(ii)双丙酮醇有机溶剂和(iii)导热粉末。另外，可将粉末和印刷助剂添加到组合物。
在一个实施例中，聚合物厚膜导热的可热成形电介质组合物还可被描述为包含聚氨酯树脂、热塑性苯氧基树脂、双丙酮醇和导热粉末，所述导热粉末选自氮化硼、氮化铝和氧化铝。
有机介质
第一有机介质由溶解于第一有机溶剂中的聚氨酯树脂构成。聚氨酯树脂必须实现对电元件(例如沉积在其上的银层)以及聚氨酯树脂在其上沉积的下面的基板两者的良好粘附性。聚氨酯树脂还必须提供用于热成形的弹性。其必须与电元件的性能相容并且不会不利地影响电元件的性能。
在一个实施例中，聚氨酯树脂占所述第一有机介质总重量的10-50重量％并且第一有机溶剂占所述第一有机介质总重量的50-90重量％。在另一个实施例中，聚氨酯树脂占所述第一有机介质总重量的25-45重量％并且第一有机溶剂占所述第一有机介质总重量的55-75重量％。在另一个实施例中，聚氨酯树脂占所述第一有机介质总重量的15-25重量％并且第一有机溶剂占所述第一有机介质总重量的75-85重量％。在一个实施例中，聚氨酯树脂为聚氨酯弹性体。在另一个实施例中，聚氨酯树脂为基于聚酯的共聚物。
第二有机介质由溶解于第二有机溶剂中的苯氧基树脂构成，所述第二有机溶剂可与第一有机溶剂相同。也可以使用不同的溶剂。苯氧基树脂增加组合物的耐高温能力，这有助于该电介质用作焊接掩膜(如果需要的话)，并且还改善透湿性。也就是说，其帮助阻止水分穿过组合物的过程。在一个实施例中，苯氧基树脂占所述第二有机介质总重量的10-50重量％并且第二有机溶剂占所述第二有机介质总重量的50-90重量％。在另一个实施例中，苯氧基树脂占所述第二有机介质总重量的20-35重量％并且第二有机溶剂占所述第二有机介质总重量的65-80重量％。
在一个实施例中，每种介质基于所述组合物的总重量计为10-35重量％。在另一个实施例中，每种介质基于所述组合物的总重量计为15-30重量％。
虽然制备两种单独的有机介质是优选的，但如果对两种介质使用相同的溶剂，则可以使用等价于上述两种有机介质的单一有机介质。
通常通过机械混合向有机溶剂加入聚合物树脂以形成所述介质。适用于聚合物厚膜组合物的有机介质中的溶剂是本领域技术人员已知的，并且包括乙酸酯和萜烯，诸如卡必醇乙酸酯和α-萜品醇或β-萜品醇，或它们与其它溶剂的混合物，所述其它溶剂诸如煤油、邻苯二甲酸二丁酯、丁基卡必醇、丁基卡必醇乙酸酯、己二醇和高沸点醇以及醇酯。此外，可以包含挥发性液体，以促进在施用于基板上之后快速硬化。在本发明的许多实施例中，可以使用溶剂诸如乙二醇醚、酮、酯和相似沸点(在180℃至250℃的范围内)的其它溶剂、以及它们的混合物。配制这些溶剂和其他溶剂的各种组合，以达到所需的粘度和挥发性要求。所用溶剂必须使树脂溶解。
双丙酮醇有机溶剂
聚合物厚膜导热的可热成形电介质组合物还包含有机溶剂双丙酮醇。这种特定溶剂已显示与PC相容并且不会造成基板的任何可感知的裂纹。在一个实施例中，双丙酮醇基于所述组合物的总重量计为2-20重量％。在另一个实施例中，双丙酮醇基于所述组合物的总重量计，占所述总重量的3-10重量％，并且在另一个实施例中，双丙酮醇基于所述组合物的总重量计为4-6重量％。
导热粉末
导热粉末包括此类粉末。在一个实施例中，导热粉末的量占整体组合物总重量的1-70％。在另一个实施例中，导热粉末占整体组合物总重量的20-60重量％，并且在另一个实施例中，导热粉末占整体组合物总重量的40-55重量％。优选将导热粉末的粒度保持在1-10微米的范围内以便避免任何裂纹问题。
附加粉末
可将各种粉末添加到PTF防潮层电介质组合物以改善粘附性、改变流变特性并增加低剪切粘度从而改善印刷适性。一种此类粉末是热解法二氧化硅，已发现其显著改善抗透湿性。
PTF导热的可热成形电介质组合物的施用
通常将也称为“浆料”的PTF导热的可热成形电介质组合物沉积在一定程度上对气体和水分不可渗透的基板上，诸如聚碳酸酯。基板也可为由塑性片材与沉积在其上的任选的金属或电介质层的组合构成的复合材料片材。在其它构造中，导热的可热成形电介质可沉积在现有的银/电介质构造之上。
通常通过丝网印刷进行PTF导热的可热成形电介质组合物的沉积，但也可使用其它沉积技术，诸如孔版印刷、注射式滴涂或涂覆技术。在使用丝网印刷的情况下，筛网的目尺寸控制沉积的厚膜厚度。
一般来讲，厚膜组合物包含向组合物赋予适当电功能性质的功能相。功能相包含分散于有机介质中的电功能粉末，所述有机介质充当功能相的载体。一般来讲，焙烧组合物以烧尽有机介质的聚合物和溶剂二者并赋予电功能性质。然而，就聚合物厚膜而言，有机介质的聚合物部分在干燥后作为组合物的整体部分保留。
可在除去所有溶剂所必需的时间和温度下加工PTF导热的可热成形电介质组合物。例如，通常通过暴露于130℃的热下10-15分钟来干燥沉积的厚膜。
电容电路构造
所用的底部基板通常为10密耳厚的聚碳酸酯。按照上述条件印刷并干燥防潮层电介质，例如如US 8,785,799中所述。可印刷并干燥多个层。然后在用于阻隔层的相同条件下印刷并干燥可热成形的导电银组合物，诸如DuPont 5043。然后也可将防潮层印刷在银导体之上，从而形成保护夹层。然后沉积导热的可热成形电介质。可包括热成形整个单元的后续步骤在3D电路的生产中是典型的。如果不使用防潮层电介质，银组合物将经受水分渗透穿过聚碳酸酯基板并且功能电路将受到损害，这常常导致寿命减少。
在制备三维电容电路的过程中，在热成形步骤之后，最终步骤将常常是模塑步骤，其中使用树脂诸如聚碳酸酯通过注塑形成成品电路。该过程被称为模内成形并且涉及较高的温度。取决于所选择的树脂，这些温度可通常超过250℃并持续10-30秒。因此，用于PTF组合物中的树脂的选择是至关重要的。已经示出用于即用PTF组合物中的树脂的组合耐受模内成形过程并且产生全功能电路，然而通常用于PTF组合物中的大多数树脂将不耐受。
实例和比较实验
实例1
按以下方式制备PTF导热的可热成形电介质组合物。通过将20.0重量％的Desmocoll 540聚氨酯(Bayer MaterialScience LLC(Pittsburgh,PA))与作为有机溶剂的80.0重量％二元酸酯(DuPont Co.(wilmington，DE))混合来制备第一有机介质。树脂的分子量为大约40,000。将该混合物在90℃下加热1-2小时以溶解所有树脂。通过将27.0重量％的PKHH(苯氧基)树脂(InChem Inc.)加入73.0重量％的二元酸酯来制备第二有机介质，并如上加热。上述重量百分比分别是基于各介质的总重量计的。所有以下重量百分比均是基于所述PTF导热的可热成形电介质组合物的总重量计的。然后，添加48.5重量％氮化硼粉末(Saint-Gobain Corp)。加入5重量％双丙酮醇(购自Eastman Chemical(Kingsport，TN))并将整个组合物混合。然后将组合物在三辊磨上以150psi研磨两个循环。
基于所述组合物的总重量计，组成为：
23.50重量％的第一有机介质
23.00重量％的第二有机介质
5.00重量％的双丙酮醇溶剂
48.50重量％的氮化硼粉末
然后如下制造电路：在10密耳厚聚碳酸酯基板上，用200不锈钢筛网印刷US 8,785,799中所述的防潮层电介质组合物的胶印物并在120℃下干燥10分钟。然后印刷并干燥相同组合物的第二印刷物。使用280目的不锈钢筛网用DuPont银浆5043(DuPont Co.(Wilmington,DE))印刷银线图案。在加压气流箱式炉中，将图案化的线在120℃下干燥15分钟。用280SS筛网印刷如上所述制备的导热的可热成形电介质组合物并在130℃下干燥10分钟。检查所述部件并且没有发现下面基板的裂纹或变形的证据。然后使电路经受热成形条件(160℃持续10秒)。然后测量并记录电阻。然后使该部件经受加电状态的85℃/85％相对湿度(R.H.)100小时以模拟加速老化条件，并测量电阻。将模拟老化导致的电阻变化记录为ΔR并示于表1中。
比较实验A
严格地如实例1中所述制备电路。唯一的差别是未使用导热的可热成形电介质组合物。将模拟老化导致的电阻变化记录为ΔR并示于表1中。
比较实验B
严格地如实例1中所述制备电路。差别在于在5043银导体下方和上方均印刷防潮层电介质组合物，并且未使用导热的可热成形电介质组合物。将模拟老化导致的电阻变化记录为ΔR并示于表1中。
从表1中所示结果看，由导热的可热成形电介质引起的性能改善是显而易见的。
表1：
Claims (6)
1.一种聚合物厚膜导热的可热成形电介质组合物，其包含：
(a)15-35重量％的第一有机介质，所述第一有机介质包含溶解于75-85重量％的第一有机溶剂中的15-25重量％的聚氨酯树脂，其中所述聚氨酯树脂和所述第一有机溶剂的重量百分比是基于所述第一有机介质的总重量计的，所述聚氨酯树脂是聚氨酯弹性体或基于聚酯的共聚物；
(b)15-35重量％的第二有机介质，所述第二有机介质包含溶解于65-80重量％的第二有机溶剂中的20-35重量％的热塑性苯氧基树脂，其中所述热塑性苯氧基树脂和所述第二有机溶剂的重量百分比是基于所述第二有机介质的总重量计的；
(c)3-10重量％的双丙酮醇；以及
(d)20-60重量％的导热粉末，所述导热粉末选自氮化硼、氮化铝、氧化铝、以及它们的混合物；
其中所述第一有机介质、所述第二有机介质、所述双丙酮醇和所述导热粉末的重量百分比是基于所述组合物的总重量计的。
2.一种电容式开关电路，其包括由根据权利要求1所述的聚合物厚膜导热的可热成形电介质组合物形成的导热的可热成形电介质。
3.根据权利要求2所述的电容式开关电路，其还包括聚碳酸酯基板。
4.根据权利要求2所述的电容式开关电路，其中所述电路为热成形的。
5.根据权利要求3所述的电容式开关电路，其中所述电路为热成形的。
6.根据权利要求4所述的电容式开关电路，其中随后对所述电容式开关电路进行注塑加工。
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