CN107251253A - 压电振动部件和涂布方法 - Google Patents

压电振动部件和涂布方法 Download PDF

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CN107251253A
CN107251253A CN201580076402.2A CN201580076402A CN107251253A CN 107251253 A CN107251253 A CN 107251253A CN 201580076402 A CN201580076402 A CN 201580076402A CN 107251253 A CN107251253 A CN 107251253A
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molecular weight
conductive adhesive
average molecular
insulating properties
piezo
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CN107251253B (zh
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永原恒治
大代宗幸
齐藤政浩
杉政淳
北山裕树
矢后滋久
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Murata Manufacturing Co Ltd
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Abstract

压电振动部件(40)具备压电振子(20)、基板(10)和将压电振子(20)与基板(10)接合的导电性粘接剂(12)。导电性粘接剂(12)含有有机硅系基础树脂(121)、交联剂(121)、导电性填料(122)和绝缘性填料(123)。有机硅系基础树脂(121)的重均分子量为20000～102000。交联剂(121)的数均分子量为1950～4620。导电性填料(122)和绝缘性填料(123)的粒径为10μm以下。

Description

压电振动部件和涂布方法
技术领域
本发明涉及压电振动部件和涂布方法。
背景技术
作为用于将电子部件安装于基板的粘接剂，一直使用使导电性填料分散于粘合剂树脂而成的导电性粘接剂。若使导电性粘接剂介于电子部件的端子与形成于基板上的配线之间而进行压接，则端子与配线之间夹入的导电性填料彼此接触而相连并形成导通路径。作为这种导电性粘接剂，例如已知在专利文献1～3中提出的那样，除了导电性填料以外还使绝缘性填料分散而成的导电性粘接剂以及其粘合剂树脂配合有基础树脂和用于促进基础树脂的交联而高分子量化的交联剂而成的导电性粘接剂等。根据专利文献1，报道了为提高与其它配合物的混合性，基础树脂的重均分子量优选为10000以上且小于1000000。根据专利文献2，提出了作为环氧树脂的交联剂，使用分子量2000以上且小于5000的聚氧丙烯二胺或分子量2000以上且小于4000的Jeffamine(注册商标)。根据专利文献3，作为导电性填料的平均粒径例示了4μm，作为绝缘性填料的平均粒径例示了3μm。
现有技术文献
专利文献
专利文献1：日本特开2011－179006号公报
专利文献2：日本特开平11－343397号公报
专利文献3：日本专利4816827号
发明内容
然而，伴随着电子部件的微间距化，为了将导电性粘接剂高精度地涂布于粘接位置，使用喷射点胶(Jet dispensing)方法。作为点胶方法的方式，已知利用空气压力在喷嘴前端喷出规定量的粘接剂的一般的空气脉冲方式；以及，利用电磁空气阀的开闭从喷嘴前端喷射粘接剂，以非接触方式涂布粘接剂的喷射点胶方法。喷射点胶方法中，为了确保导电性粘接剂的喷出稳定性且以使喷出的导电性粘接剂着落于被粘接面时其涂布直径不扩散，导电性粘接剂优选兼具适度的粘性和防滴落性(液切れ性)。若减小基础树脂的分子量则粘性变低，因此防滴落性变好，但固化后的弹性模量变高，柔软性受损，对机械冲击的耐性、导通可靠性下降。另一方面，若增大基础树脂的分子量，则粘性变高，因此可以抑制着落后的涂布直径的扩散，但防滴落性劣化，来自喷射点胶器的导电性粘接剂的喷出变难。此外，导电性粘接剂的固化后的弹性模量不仅依赖于基础树脂的分子量，而且也依赖于交联剂的分子量，因此优选将交联剂的分子量也进行了考虑而调整导电性粘接剂的组成。而且，在通过喷射点胶方法涂布导电性粘接剂时，优选以导电性填料、绝缘性填料容易通过喷嘴孔的方式调整导电性填料、绝缘性填料的粒径。上述专利文献1～3中，并未考虑为了平衡良好地满足导电性粘接剂所需的防滴落性、涂布直径、耐冲击性、导通可靠性而综合地考虑基础树脂的平均分子量、交联剂的分子量、导电性填料的粒径、绝缘性填料的粒径，进而调整导电性粘接剂的组成。
本发明是鉴于这种情况而完成的，其课题是能够将固化前的导电性粘接剂高精度地涂布于粘接位置的同时提高固化后的导电性粘接剂的可靠性。
本发明的一个方式所涉及的压电振动部件具有压电振子、基板和接合压电振子与基板的导电性粘接剂。导电性粘接剂含有有机硅系基础树脂、交联剂、导电性填料和绝缘性填料，有机硅系基础树脂的重均分子量为20000～102000，交联剂的数均分子量为1950～4620，导电性填料和绝缘性填料的粒径为10μm以下。
根据本发明，能够将固化前的导电性粘接剂高精度地涂布于粘接位置且能够提高固化后的导电性粘接剂的可靠性。
附图说明
图1是本发明的实施方式所涉及的压电振动部件的分解立体图。
图2是以本发明的实施方式所涉及的压电振子与基板之间的连接位置为中心的局部截面图。
图3是表示本实施例所涉及的有机硅系基础树脂的重均分子量与涂布直径的关系的图。
图4是表示本实施例所涉及的交联剂的数均分子量与导通可靠性故障率的关系的图。
图5是表示本实施例所涉及的交联剂的数均分子量与耐落下性试验故障率的关系的图。
图6是表示本实施例所涉及的导电性填料的粒径的分布的图。
图7是表示本实施例所涉及的绝缘性填料的粒径的分布的图。
具体实施方式
以下，一边参照图1～图2一边对本发明的实施方式进行说明。这里，相同符号表示相同的构件，省略其重复的说明。
图1是本发明的实施方式所涉及的压电振动部件40的分解立体图。如图1所示，压电振动部件40主要具备：压电振子20、具有安装压电振子20的主面11的基板10以及用于密封压电振子20来防止外部空气的盖30。压电振子20具备：具有在厚度方向对置的二个面的平板状的压电板21、形成于压电板21的一面的激励电极22、以及形成于压电板21的另一面的激励电极23。若对激励电极22、23施加交流电压，则压电板21以厚度切变模式振动。压电板21由显示压电特性的压电材质(例如，水晶板、压电陶瓷等)构成。激励电极22、23例如由金、铬、镍、铝、钛等的导电性薄膜构成。
基板10为具有在其厚度方向对置的二个面的平板状，将二个面中安装压电振子20的面称为主面11。主面11上形成有介由导电性粘接剂12与激励电极23导通的配线13和介由导电性粘接剂15与激励电极22导通的配线16。作为在各个配线13、16上涂布导电性粘接剂12、15的方式，例如，使用点胶方法，特别优选为喷射点胶方法。在点胶方法中，喷射点胶方法在量产性方面优异。基板10由具有适度的机械强度和电绝缘性的材质(例如，氧化铝等绝缘陶瓷、以绝缘层被覆合成树脂、金属板的表面而成的复合材料等)构成。另外，基板10具有以将拐角部分(角部分)的一部分切下而成为圆筒曲面状的方式形成的缺口部14、17，配线13、16可分别从缺口部14、17延伸至主面11的背面而与外部电路连接。盖30是用于密封压电振子20来防止外部空气的有底盖构件，由金属材质、绝缘材质或复合材料(例如，以金属薄膜被覆绝缘构件的表面而成的复合材料等)构成。
图2是以压电振子20的激励电极23与基板10的配线13之间的连接位置为中心的局部截面图。导电性粘接剂12是使导电性填料122和绝缘性填料123分散于作为基材的粘接剂组合物121而成的。粘接剂组合物121含有基础树脂和用于促进该基础树脂的交联而高分子量化的交联剂(固化剂)。应予说明，导电性粘接剂15的组成与导电性粘接剂12的组成相同。
作为基础树脂，优选使用具有热固性成分的树脂，例如，优选为有机硅树脂。有机硅树脂具有以无机质的硅氧烷键(-Si-O-Si-)为主链且在支链上键合有有机基团的结构，有加成固化型和湿气固化型(缩合固化型)。加成固化型是分成作为基础树脂的聚硅氧烷和交联剂的双液型，通过使用铂催化剂进行加热而固化。湿气固化型在室温下与空气中的水分进行化学反应而固化。若有机硅系基础树脂的重均分子量变小，则其结果为固化后的导电性粘接剂12的弹性模量(橡胶弹性)变大，存在对机械冲击的耐性、导通可靠性下降的趋势。此外，若有机硅系基础树脂的重均分子量变小，则低分子硅氧烷的含量变多，低分子硅氧烷有可能从固化后的导电性粘接剂12渗出而发散，从而产生接点不良等不良影响。此外，在通过喷射点胶方法涂布时也会产生导电性粘接剂12的涂布直径不必要地扩大的问题。因此，有机硅系基础树脂的重均分子量的下限实质上为20000～30000左右。另一方面，若有机硅系基础树脂的重均分子量变大，则通过喷射点胶方法涂布导电性粘接剂12时的防滴落性劣化。具体而言，若有机硅系基础树脂的重均分子量大于80000，则防滴落性开始显现劣化，产生取得喷嘴与被粘接面的距离的需要，或喷出结束时间变长，因此可稳定地涂布的有机硅系基础树脂的重均分子量的上限实质上为100000左右。考虑到这种情况，为了将通过喷射点胶方法而涂布的导电性粘接剂的涂布直径调整为155μm以下，有机硅系基础树脂的重均分子量优选为20000～100000，更优选为30000～80000，特别优选为43000～70000。
另外，伴随着制品小型化，要求通过喷射点胶方法而涂布的导电性粘接剂的涂布直径变小。如图1所示那样将压电振子20以短边上的2点保持的情况下，若在压电振子20的宽度尺寸(短边的尺寸)为600μm～650μm时上述涂布直径为130μm～155μm则可以将压电振子高精度且稳定地保持在基板上。在这种情况下，制品可以是长边为1.2mm，短边为1.0mm。
若交联剂的数均分子量变大，则存在固化物的交联密度变小、凝聚力下降、并且粘接强度变弱、导通可靠性故障率变高的趋势，另一方面，若交联剂的数均分子量变小，则固化物的交联密度变大，柔软性下降，因此存在无法吸收冲击而耐落下性试验故障率变高的趋势。考虑到这种情况，交联剂的数均分子量优选为1950～4620。
导电性填料122只要具有可得到电连接的导电性即可。作为导电性填料122，例如，可举出Au、Ag、Ni、Cu和焊料等金属粒子或碳粒子等。此外，导电性填料122可以是以1层或2层以上的层被覆成为核的粒子，其最外层具有导电性的填料。在这种情况下，从得到更优异的有效期的观点出发，就最外层而言，与Ni、Cu等过渡金属相比，优选以Au、Ag和/或铂族金属等贵金属为主成分，更优选由这些贵金属的1种以上构成。这些贵金属中，最优选为Au。例如，为了将通过喷射点胶方法而涂布的导电性粘接剂12的涂布直径调整为155μm以下，导电性填料122的粒径优选为10μm以下。应予说明，导电性填料122的形状可以是球状、鳞片状等任何形状，此外，也可以混合多个种类的形状。
绝缘性填料123只要在与导电性填料122接触时可阻止与导电性填料122的电导通即可。作为绝缘性填料123，优选为含有绝缘性的树脂作为主成分的粒子。作为绝缘性的树脂，例如，可举出聚乙烯树脂、聚苯乙烯树脂、聚酰胺树脂、聚氨酯树脂、(甲基)丙烯酸树脂、苯乙烯－(甲基)丙烯酸酯共聚物、乙烯－(甲基)丙烯酸酯共聚物等(甲基)丙烯酸酯共聚物、乙烯－(甲基)丙烯酸共聚物等(甲基)丙烯酸共聚物、苯乙烯－二乙烯基苯共聚物、苯乙烯－丁二烯共聚物、二乙烯基苯树脂、苯乙烯－异丁烯共聚物、乙烯－丙烯共聚物、苯氧基树脂、固态环氧树脂和有机硅树脂。这些之中，从柔软性更加优异的观点出发，优选为有机硅树脂。通过使用有机硅树脂作为绝缘性填料123，可减小固化后的导电性粘接剂12的弹性模量，提高对机械冲击的耐性、导通可靠性。它们可以单独使用1种或组合使用2种以上。绝缘性填料123可以是由以绝缘性的树脂为主成分的绝缘性材料构成的粒子，也可以是以1层或2层以上的绝缘层或导电层被覆成为绝缘性或导电性的核的粒子，其最外层具有绝缘性的粒子。例如，为了将通过喷射点胶方法而涂布的导电性粘接剂12的涂布直径调整为155μm以下，绝缘性填料123的粒径优选为10μm以下。应予说明，绝缘性填料123的形状可以是球状、鳞片状等任何形状，此外，也可以混合多个种类的形状。
如图2所示，在导电性填料122的形状为鳞片形状，绝缘性填料123的形状为球状，且导电性填料122小于绝缘性填料123时，与绝缘性填料123的形状为鳞片形状的情况相比，可以增大绝缘性填料123彼此之间的空间。此外，由于导电性填料122的形状为鳞片形状，且导电性填料122小于绝缘性填料123，因此导电性填料122彼此没有间隙地密集，在绝缘性填料123彼此之间的空间高密度地填充有导电性填料122。由此，可提高导电性粘接剂12的电接合可靠性。从这种观点出发，导电性填料122的中值径优选小于绝缘性填料123的中值径。例如，也可以将导电性填料122的中值径设为2.1μm，将绝缘性填料123的中值径设为4.0μm。
另外，导电性粘接剂12不限定于用于接合压电振子20和基板10的用途，可用于所有电子部件的制造。尤其是可以很好地用于通过喷射点胶方法将导电性粘接剂12涂布于被粘接面而制造电子部件的工序。
[实施例1]
将有机硅系基础树脂的重均分子量调整为43000、72000、102000、131000、160000，测量通过喷射点胶方法而涂布的导电性粘接剂12的涂布直径的结果，如图3所示，对于各个重均分子量，可得到152.6μm、149μm、150μm、186.9μm、199μm的涂布直径。由该实验结果可知，为了将通过喷射点胶方法而涂布的导电性粘接剂12的涂布直径调整为155μm以下，有机硅系基础树脂的重均分子量优选为102000以下。应予说明，有机硅系基础树脂的重均分子量是通过高效液相色谱法测定，作为聚苯乙烯换算的相对分子量算出的。
[实施例2]
将交联剂的数均分子量调整为1200、2900、4620、6100，测量导电性粘接剂12的导通可靠性故障率的结果，如图4所示，对于各个数均分子量，可得到0％、0％、0％、17％的导通可靠性故障率。由该实验结果可知，为了提高导电性粘接剂12的导通可靠性，交联剂的数均分子量优选为4620以下。另外，导通可靠性故障率的测量中，对在基板表面将电极(镍合金基底电极(膜厚0.1μm)、金基底电极(膜厚0.4μm))成膜而成的陶瓷基板的槽(宽度30μm和深度30μm)涂布导电性粘接剂12，在大气中200℃的温度环境下用60分钟使导电性粘接剂12固化。然后，将在施加压力的过程中导电性粘接剂12的电阻值大于初期值的5倍的情况判定为“故障”。电阻值的测定是使用毫欧表通过4端子法而进行的。应予说明，导通可靠性故障率的测量中使用的试样数为6。
[实施例3]
将交联剂的数均分子量调整为1200、1950、2900、4620，测量导电性粘接剂12的耐落下性试验故障率，其结果，如图5所示，对于各个数均分子量，可得到50％、0％、0％、0％的耐落下性试验故障率。由该实验结果可知，为了提高导电性粘接剂12的耐冲击性，交联剂的数均分子量优选为1950以上。另外，在耐落下性试验故障率的测量中，使用导电性粘接剂12将压电振子20安装于基板10而制作压电振动部件40，将其安装于试验用基板，将试验用基板旋拧到模仿手机外壳的试验用具的内部。然后，从1.5m的高度分别将试验用具的6个面朝向下方地使其落下到混凝土上各1次合计6次，将上述工序作为1个循环，将在100次循环数以内压电振子20与基板10之间不能出现电特性的样品判定为“故障”。应予说明，耐落下性试验故障率的测量中使用的试样数为6。
[实施例4]
使用具有293MPa的弹性模量的导电性粘接剂12，试制共振频率37.4MHz的压电振子20。如图6所示，作为导电性填料122，使用中值径为2.1μm、最大直径为10μm的银填料。如图7所示，作为绝缘性填料123，使用中值径为4.0μm、最大直径为10μm的有机硅树脂填料。作为有机硅系基础树脂，使用重均分子量为72000的有机硅系基础树脂。该有机硅系基础树脂由重均分子量为43000的有机硅系基础树脂(75wt％)和重均分子量为160000的有机硅系基础树脂(25wt％)进行调整。作为交联剂，使用数均分子量为3030的交联剂。通过喷射点胶方法涂布导电性粘接剂12，其结果，在连续涂布次数6000次以上能够进行涂布直径130μm以下的微小涂布。由该实验结果可知，通过将有机硅系基础树脂的重均分子量设为80000以下，可以使导电性粘接剂12的防滴落性良好，根据喷射点胶方法可稳定地喷出。此外，通过使用有机硅树脂填料作为绝缘性填料123，导电性粘接剂12的柔软性增加，因此可得到良好的防滴落性，能够进行稳定的连续微小涂布。此外，通过将导电性填料122和绝缘性填料123的最大直径设为10μm，可以从喷射点胶器的微小喷嘴稳定地喷出导电性粘接剂12。对压电振子20的等效串联电阻进行测定的结果，可得到平均值35.6Ω这样的良好的值。对压电振子20的耐落下性试验故障率进行测定，其结果，直至落下次数为100次为止，耐落下性试验故障率为0。由该实验结果可知，通过使用有机硅树脂填料作为绝缘性填料123，并且使用数均分子量为1050以上的交联剂作为交联剂，可以减小导电性粘接剂12的固化后的弹性模量，可提高对机械冲击的耐性。应予说明，耐落下性试验故障率的测量中使用的试样数为6。
另外，以上说明的各实施方式是用于容易地理解本发明的实施方式，但不能解释为限定本发明。本发明能够不脱离其主旨地进行变更/改良，并且本发明中也包含其等价物。即，对于本领域技术人员对各实施方式施加了适当设计变更的方式，只要具备本发明的特征，则也包含于本发明的范围。例如，各实施方式所具备的各因素以及其配置、材料、条件、形状、大小等并不限定于所例示的内容而可以适当地变更。此外，各实施方式所具备的各因素只要在技术上可能则可以进行组合，将它们组合而成的内容只要包含本发明的特征则也包含于本发明的范围。
符号说明
10…基板
11…主面
12…导电性粘接剂
13…配线
14…缺口部
15…导电性粘接剂
16…配线
17…缺口部
20…压电振子
21…压电板
22…激励电极
23…激励电极
30…盖
40…压电振动部件
121…粘接剂组合物
122…导电性填料
123…绝缘性填料

Claims (6)

1.一种压电振动部件，具备：压电振子、基板和将所述压电振子与所述基板接合的导电性粘接剂，
所述导电性粘接剂含有有机硅系基础树脂、交联剂、导电性填料和绝缘性填料，
所述有机硅系基础树脂的重均分子量为20000～102000，
所述交联剂的数均分子量为1950～4620，
所述导电性填料和所述绝缘性填料的粒径为10μm以下。
2.如权利要求1所述的压电振动部件，其中，所述有机硅系基础树脂的重均分子量为43000～72000。
3.如权利要求1或2所述的压电振动部件，其中，所述导电性填料的中值径小于所述绝缘性填料的中值径。
4.如权利要求1～3中任一项所述的压电振动部件，其中，所述导电性填料由银构成。
5.如权利要求1～4中任一项所述的压电振动部件，其中，所述绝缘性填料由球状有机硅树脂构成。
6.一种涂布方法，其中，通过喷射点胶方法将权利要求1～5中任一项所述的导电性粘接剂涂布于所述基板的被粘接面。
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