CN100386830C - 压敏电阻器的制备方法及压敏电阻器 - Google Patents

压敏电阻器的制备方法及压敏电阻器 Download PDF

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CN100386830C
CN100386830C CNB038011247A CN03801124A CN100386830C CN 100386830 C CN100386830 C CN 100386830C CN B038011247 A CNB038011247 A CN B038011247A CN 03801124 A CN03801124 A CN 03801124A CN 100386830 C CN100386830 C CN 100386830C
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potassium
varistor
compound
prepare
dispersant
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CN1557003A (zh
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寺浦亮
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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Abstract

当通过向用于ZnO-Pr体系的压敏电阻器材料中添加Co或K来制备陶瓷材料粉末时，碱金属K是以KClO4、KHC4H4O6、K2(PtCl6)或K2[Co(NO2)6]的形式加入的。在该陶瓷材料粉末的湿磨期间，向其中加入了0.1至5.0重量%的多羧酸盐分散剂。因此，可以制备出具有高可靠性、高质量、良好而且几乎不变的压敏电阻器特征例如压敏电阻器电压V1mA和绝缘电阻IR的压敏电阻器。

Description

压敏电阻器的制备方法及压敏电阻器
技术领域
本发明涉及压敏电阻器的制备方法及压敏电阻器。具体而言，本发明涉及一种压敏电阻器的制备方法，该方法包括混合作为主要组分的氧化锌(ZnO)和作为微量组分的含有钾(K)的化合物，和通过湿法来粉碎该混合物的步骤制备，并且本发明还涉及通过这种方法所制备的压敏电阻器。
背景技术
众所周知的压敏电阻器组合物的主要组分包括SiC、SrTiO3和ZnO如ZnO-Bi和ZnO-Pr。在它们中间，ZnO-Bi基和ZnO-Pr基压敏电阻器作为冲击保护器正变得普遍。具有比SiC基和SrTiO3基压敏电阻器更优异的电压非直线性和冲击电流容量的ZnO-Bi基和ZnO-Pr基压敏电阻器，提供了防止电子设备遭受冲击电流的高性能。
在这两类ZnO基压敏电阻器之间，ZnO-Pr基压敏电阻器比ZnO-Bi基压敏电阻器表现优异的电压非直线性，但产生较大的泄漏电流。
为解决这个缺点，例如日本已审查专利申请63-30763提出了一种ZnO-Pr基压敏电阻器，其包含微量组分如镨(Pr)；钴(Co)；钾(K)、铷(Rb)和铯(Cs)中的至少两种；铬(Cr)；及镁(Mg)和钙(Ca)中的至少一种。
特别地，为了减小泄漏电流，该压敏电阻器包含0.1至5atm％的镨；0.5至5atm％的钴；总和为0.05至0.5atm％的钾、铷和铯；0.05至0.5atm％的铬；和0.01至2atm％的镁和/或钙。
以金属氧化物或者例如通过焙烧形成的氧化物的碳酸盐、氢氧化物或氟化物的形式使用这些添加剂。
ZnO基压敏电阻器在陶瓷烧结块体中积极地利用晶粒间界。两个晶粒和它们的晶粒间界提供了最小单位的压敏电阻器。因此，这种压敏电阻器显示了优异的电压非直线性。另外，可以通过例如改变所使用的添加剂的类型来控制电压非直线性。
但是，电压非直线性由于有缺陷的晶粒间界而降低，而这种有缺陷的晶粒间界由于例如所添加元素的不均匀沉积，和由加入元素所产生的化合物而增加。特别地，压敏电阻器特征如绝缘电阻很大程度上取决于在晶粒间界上沉积的碱金属。对于含有少量晶粒间界的低电压压敏电阻器，通过所加入元素的不均匀沉积和组成变化所产生的有缺陷的晶粒间界削弱了静电放电(以下称之为ESD)特征。对此ESD特征这种的削弱损害导致压敏电阻器电压V1mA和绝缘电阻IR的下降和改变。
对于上面提出的这种压敏电阻器，在湿法粉碎期间，可以在包含于第一浆液的水中溶解钾，其是碱金属并且是以可溶性的钾化合物如氧化钾、碳酸钾、氢氧化钾和氟化钾形式而加入的。然后，在脱水期间将钾与水一同除去，导致产物材料组成的变化，即组成变化。组成变化难以提供具有优异及稳定压敏电阻器特征的高质量压敏电阻器。
另外，钾化合物在水中的溶解引起第一浆液pH的变化。这样的变化可以增加第一浆液的粘度，以至于降低第一浆液的溶混性、可轧性和分散性。在为固体和液体混合物的第一浆液中，每一元素是通过由元素的ζ电势所产生的静电推斥而分散的。ζ电势取决于第一浆液的氢离子指数，即pH。如果由于钾化合物的水合使该浆液的pH变化至ζ电势为0(0)，那么第一浆液中的颗粒不再彼此推斥。那么，该浆液不能保持其分散体系。结果是，颗粒聚集以至增加该浆液的粘度，导致该浆液的溶混性、可轧性和分散性降低。
此外，在脱水后的干燥期间，钾通过重结晶快速地聚集并且不均匀沉积，以至降低其分散性。这可以导致压敏电阻器特征的进一步削弱。
本发明是基于上面所述的问题。因此，本发明的一个目的是提供一种制备可靠、高质量压敏电阻器的方法，所述的压敏电阻器具有优异的压敏电阻器特征如变电阻电压V1mA和绝缘电阻IR并且可以防止这些特征变化，并且也提供该压敏电阻器。
发明内容
本发明提供一种用于制备压敏电阻器的方法。该方法包括混合和通过湿法来粉碎作为主要组分的氧化锌和作为微量组分的含有钾的化合物的步骤。在此方法中，包含钾的化合物是溶解性差的钾化合物。
根据本发明，以溶解性差的钾化合物形式而加入的钾，在混合和粉碎步骤中不溶解于以含有的水作为溶剂的第一浆液中，不引起组成变化。另外，这样的不溶解于第一浆液中的化合物，不改变第一浆液的pH，防止浆液粘度的增加和溶混性、可轧性和分散性的降低。此外，这样的化合物可以防止在干燥期间钾通过重结晶的聚集和不均匀沉积。因此，本发明可以提供一种制备可靠的可以在低电压下操作的压敏电阻器的方法。
在此方法中，优选使用含有镨的化合物和含有钴的化合物作为附加的微量组分。这些化合物用于减小压敏电阻器的泄漏电流。
为提高上述的效果，优选在所使用的溶解性差的钾化合物中包含的钾的溶解度于25℃100克水溶液中为3克或更低。所使用的溶解性差的钾化合物的优选实例包括：选自高氯酸钾、酒石酸氢钾、六氯铂酸钾和六硝基钴酸钾中的至少一种材料。
因此，在本发明的压敏电阻器制备方法中，优选所使用的溶解性差的钾化合物中包含的钾的溶解度于25℃100克水溶液中为3克或更低。优选溶解性差的钾化合物包括：选自高氯酸钾、酒石酸氢钾、六氯铂酸钾和六硝基钴酸钾中的至少一种材料。
此外，通过本发明人深入细致的研究发现，在混合和粉碎步骤中添加的分散剂可以均匀地分散与溶解性差的钾化合物结合的组分，以防止有缺陷的晶粒间界。本研究还发现，考虑到所使用的焙烧炉的环境和耐久性，优选所加入入的分散剂是多羧酸盐分散剂。
因此，在本发明的压敏电阻器制备方法中，优选混合和粉碎的步骤是进一步包括多羧酸盐分散剂的加入。
研究还发现，考虑到保持满意的分散性，优选所加入的多羧酸盐分散剂的量是主要和微量组分总重量的0.1至5.0重量％。
因此，在本发明的压敏电阻器制备方法中，优选所加入的多羧酸盐分散剂的量是主要和微量组分总重量的0.1至5.0重量％。
本发明进一步提供了根据上述的制备方法所制备的压敏电阻器。
在制备方法中，钾不溶解或不被除去，提供了优异的分散性。因此，本发明可以提供一种可靠的压敏电阻器，其可以在低电压下操作并且具有优异的压敏电阻器特征。
附图说明
图1所示为根据本发明的实施方案的压敏电阻器制备方法所制备的多层压敏电阻器的剖视图。
图2所示为根据本发明的压敏电阻器制备方法的主要步骤。
图3所示为在ESD敏感度的测量中所使用的ESD脉冲波形曲线图。
图4所示为冲击电流容量的测量中所使用的冲击电流波形曲线图。
实施本发明的最佳方式
现在将详细描述本发明的实施方案。
图1所示为根据本发明实施方案的多层压敏电阻器的纵向剖视图。
该多层压敏电阻器包括陶瓷烧结块体1，内电极2至5，及外电极6和7。内电极2至5是由导电材料如铂和银所组成的，并包埋于陶瓷烧结块体1中。外电极6和7是由导电材料如铂和银所组成的，并安置于陶瓷烧结块体1的两端。内电极2和4与外电极6电连接，并且内电极3和5与外电极7电连接。
现在将详细描述用于制备上述压敏电阻器的方法。
首先，称量预定量的是主要组分的ZnO，和是微量组分的Pr6O11、Co3O4、CaCO3、Al2O3及溶解性差的钾化合物，以便提供预定的组成。
和其它添加剂对比，该钾化合物溶解性差是由于下列原因：
对于可溶性的钾化合物如K2O和K2CO3，在湿法粉碎后的干燥期间，钾与水一起被除去，以至引起产物压敏电阻器的组成变化，这将在以后描述。另外，可溶性的钾化合物溶解于第一浆液所含的溶剂中，因此第一浆液的pH变化。结果是第一浆液的粘度增加，以至降低了每种组分的分散性。此外，在干燥期间，钾通过重结晶聚集并且不均匀地沉积，以至产生有缺陷的晶粒间界，导致压敏电阻器特征的削弱。
压敏电阻器特征，如绝缘电阻IR很大程度上取决于沉积在晶粒间界的钾。因此，钾的组成变化和由例如钾的重结晶所引起的浆液分散性的降低，发展成初始绝缘电阻IR的变化。
因此，在此实施方案中，钾是以溶解性差的钾化合物形式而加入的。
特别地，优选所使用的溶解性差的钾化合物的溶解度于25℃100克水溶液中为3克或更低。如果溶解度超过3克，钾溶解在水中，干燥中与水一起被除去，并且在干燥期间通过重结晶而不均匀沉积，以至削弱压敏电阻器特征。在这些条件下，最低可能的溶解度是所需要的。
这种溶解性差的钾化合物的实例包括高氯酸钾(KClO4)、酒石酸氢钾(KHC4H4O6)、六氯铂酸钾(K2(PtCl6))和六硝基钴酸钾(K2[Co(NO2)6])。
接着，在包含研磨介质如氧化锆的球磨机中混合称量过的原料与离子交换水及多羧酸盐分散剂，其量为原料的0.1至5.0重量％，，以形成第一浆液。在第一浆液中，这些组分由湿法粉碎并且均匀地分散。
由于下列原因，将多羧酸盐分散剂加入到原料中：
优选向原料中加入分散剂是因为它可以分散与溶解性差的钾化合物结合的第一浆液中的组分。
在几类分散剂中，优选将多羧酸盐分散剂用作原料的添加剂。如果向原料中加入例如磺酸盐分散剂，在焙烧期间它产生硫氧化物，这以后将作描述。这种硫氧化物可以毁坏所使用的焙烧炉并削弱其耐久性。
另外，按照0.1至5.0重量％的量加入多羧酸盐分散剂是由于下列原因：
如果所加入的多羧酸盐分散剂的量小于0.1重量％，组分的颗粒将令人不满意地吸附该分散剂。结果是第一浆液的粘度增加，导致在湿法粉碎期间不充分的可轧性和分散性。另一方面，如果所加入的多羧酸盐分散剂的量过大，即大于5.0重量％，在一颗颗粒上所吸附的分散剂组分接触到另一颗颗粒上所吸附的分散剂组分。这样的分散剂组分可以缠绕以至再聚集。因此，优选所加入的多羧酸盐分散剂的量是主要组分和微量组分总量的0.1至5.0重量％，更优选是主要组分和微量组分总量的0.5至3.5重量％。所加入的多羧酸盐分散剂的实例包括多羧酸铵和多羧酸钠。
在湿法粉碎后，将第一浆液脱水并干燥以制备颗粒。将这些颗粒在预定的条件下煅烧并充分地粉碎，以制备煅烧过的粉末。
将该煅烧过的粉末与有机粘合剂、有机溶剂和有机增塑剂混合以制备用于压片的第二浆液。
如图2中所示，用刮刀将该第二浆液成型，以制备具有预定厚度的陶瓷生片8至13。
然后，通过丝网印刷在该陶瓷生片9至12的顶面用主要含有铂的导电糊料(下文称之为铂糊料)形成内电极的导体图案14至17。该导体图案14至17是以条状形式形成的并且从端面9a延伸至14a。导体图案14至17的另一末端位于陶瓷生片9至12上。层压在上面印刷了导体图案的陶瓷生片9至12，并夹入作为保护层的陶瓷生片8和13之间，并且压紧以形成未焙烧的层压材料。
将此层压材料切割到预定的尺寸，装入氧化铝箱，去掉粘合并焙烧以制备陶瓷烧结块体1，即焙烧过的层压材料。该长方体的陶瓷烧结块体1包括内电极2至5。
随后，向陶瓷烧结块体1的两端涂覆另一种主要含有银的导电糊料(下文称之为银糊料)，并焙烧以形成外电极6和7。结果是完成了多层压敏电阻器。
根据此实施方案，在混合和粉碎步骤中，向ZnO中加入的是溶解性差的化合物形式的钾，例如KClO4和KHC4H4O6(即溶解度于25℃100克水溶液中为3克或更小的钾化合物)。如果使用了这种化合物，钾不溶解于水中，或在脱水期间不与水一起被除去。因此，所述的第一浆液可以具有优异的分散性，并且避免在干燥期间通过重结晶钾的聚集和不均匀沉积。由此，该实施方案可以提供可靠的多层压敏电阻器，其具有稳定的压敏电阻器特征。
另外，在混合和粉碎步骤中，向原料中加入0.1至5.0重量％的多羧酸盐分散剂。这种分散剂可以均匀地分散与溶解性差的钾化合物结合的组分，以防止在焙烧后钾沉积到晶粒间界上时有缺陷的晶粒间界的产生。因此，这个实施方案可以提供一种可靠的多层压敏电阻器，其具有满意的压敏电阻器特征，并且可以容易低成本地制备。
现在，将根据实施例来描述本发明。
具体实施方式
<第一组实施例>
制备包含ZnO和可溶性的或溶解性差的钾化合物的压敏电阻器，并且评价其多种压敏电阻器特征。
(实施例1)
首先，以作为主要组分的ZnO粉末作为参考，各自称量Pr6O11、Co3O4、CaCO3、Al2O3和KClO4粉末，以使镨占0.3atm％、钴占2.0atm％、钙占0.2atm％、铝占1.0×10-4atm％和钾占0.5atm％。Pr6O11、Co3O4、CaCO3、Al2O3粉末的溶解度优良，而KClO4粉末的溶解度差，即于25℃100克水溶液中的溶解度为3克或更小。
在包含部分稳定的氧化锆(PSZ)研磨介质的球磨机中，将这些原料与离子交换水混合并粉碎，以制备以含有的纯水作为溶剂的第一浆液。离子交换水的重量是这些原料总重量的3倍，以使第一浆液的粘度(浆液粘度)达到最小。随后，将第一浆液脱水并干燥以制备颗粒。然后于800℃将这些颗粒在空气中煅烧2小时，再充分粉碎以制备煅烧过的粉末。
将此煅烧过的粉末与预定量的作为有机粘合剂的聚乙烯醇缩丁醛、作为有机增塑剂的邻苯二甲酸二丁酯和作为有机溶剂的甲苯及乙醇混合。将该混合物通过湿法粉碎以制备用于形成陶瓷生片的第二浆液。
用刮刀将此第二浆液涂覆到聚对苯二甲酸乙二醇酯(PET)薄膜上，以形成厚度为大致为30μm的薄片。切割得到的薄片以制备许多具有预定尺寸的陶瓷生片。
然后，通过丝网印刷将铂糊料涂覆到陶瓷生片的顶面以形成条形电极图案。这些电极图案从陶瓷生片的端面延伸。电极图案的另一末端位于陶瓷生片上面。
层压在其上面形成有电极图案的陶瓷生片，夹入到作为保护层的没有电极图案的附加的陶瓷生片之间，并且压紧以形成层压材料。
将该层压材料修剪成1.6mm长0.8mm宽，装入氧化铝箱，在空气中于500℃去掉粘合，并在空气中于1200℃焙烧2小时以制备陶瓷烧结块体。
随后，将银糊料涂覆到陶瓷烧结块两个端面上，并于800℃焙烧以形成外电极。结果是，完成了实施例1的多层压敏电阻器。
(实施例2至4)
制备含有KHC4H4O6(实施例2)、K2(PtCl6)(实施例3)或K2[Co(NO2)6](实施例4)形式的钾，以代替KClO4的多层压敏电阻器。
(比较例1至12)
按照与实施例1相同的方法，制备多层压敏电阻器，其各自含有的钾不是以溶解性差的钾化合物的形式，而是以下列可溶性钾化合物中的任何一种的形式：氟化钾(KF)(比较例1)、碳酸钾(K2CO3)(比较例2)、氧化钾(K2O)(比较例3)、氢氧化钾(KOH)(比较例4)、氯化钾(KCl)(比较例5)、溴化钾(KBr)(比较例6)、磷酸钾(K3PO4)(比较例7)、高锰酸钾(KHMnO4)(比较例8)、硫酸钾(K2SO4)(比较例9)、硫化钾(K2S)(比较例10)、硝酸钾(KNO3)(比较例11)和碘化钾(KI)(比较例12)。这些化合物于25℃100克水溶液中的溶解度为10克或更大。
为实施例1至4及比较例1至12的每一个制备总数为100件的试验样品。对这些试验样品测量压敏电阻器电压V1mA、压敏电阻器电压V1mA的变化、电压非直线性系数α、初始绝缘电阻IR、初始绝缘电阻IR的变化和表示ESD特征的ESD敏感度。
压敏电阻器电压V1mA是当施加1mA的直流电穿过试验样品时，通过测量每件试验样品两端的电压而确定的。
电压非直线性系数α是基于方程式(1)，用压敏电阻器电压V1mA和施加0.1mA直流电穿过试验样品时每件试验样品两端的电压来计算的：
&alpha; = log ( I lmA / I 0.1 mA ) log ( V 1 mA / V 0.1 mA ) &CenterDot; &CenterDot; &CenterDot; &CenterDot; &CenterDot; &CenterDot; ( 1 )
对每件试验样品施加为压敏电阻器电压V1mA60％量的直流电压0.1秒，用超高电阻微安培计(由ADVANTEST公司生产的“R8340A”)测量初始绝缘电阻IR。
压敏电阻器电压V1mA的变化和初始绝缘电阻IR的变化，是通过测量压敏电阻器电压V1mA及初始绝缘电阻IR的最小值和最大值之间的变化百分率而确定的。将压敏电阻器电压V1mA的变化为15％或更小的并且绝缘电阻IR的变化为30％或更小的压敏电阻器判定为合格品。
另外，ESD敏感度是按下列程序计算的。
首先，如图3中所示，向每件试验样品两端施加根据Internationa]Electrotechnical Commission(国际电工委会)(IEC)801.2的10个ESD脉冲。压敏电阻器电压的变化百分率ΔV1mA/V1mA是根据该施加前与后的压敏电阻器电压差值ΔV1mA，与施加前的压敏电阻器电压V1mA而计算的。然后，计算该施加前与后绝缘电阻的差值ΔlogIR。压敏电阻器电压的变化百分率ΔV1mA/V1mA在±10％以内，和绝缘电阻的差值ΔlogIR是1/2时所施加的最大电压，被计算作为所述的ESD敏感度。在图3中，tr表示的是上升边的时间，P表示100％的峰值电流，1AT 30ns表示在30ns时的振幅，而1 AT60ns表示在60ns时的振幅。
Figure C0380112400121
如在表1中清楚地表明，比较例1至12的压敏电阻器含有可溶性钾化合物，其展示了超过20％的压敏电阻器电压V1mA的变化，和超过200％的初始绝缘电阻IR的变化。
相反地，实施例1至4的压敏电阻器含有溶解性差的钾化合物，其可以抑制压敏电阻器电压V1mA的变化至15％或更小，并且初始绝缘电阻IR的变化至30％或更小。这些结果表明，这些压敏电阻器显示了被抑制的压敏电阻器特征的变化和改善的ESD特征。
然后，通过感应耦合等离子体(ICP)发射光谱学来分析实施例和比较例压敏电阻器的钾的组成。从处理前(原料的钾含量)的钾含量和处理后(焙烧后压敏电阻器的钾含量)的钾含量计算每种压敏电阻器钾含量的变化量。随后，将此变化量除以处理前的钾含量以确定其变化百分率。
下表2显示了钾的组成的分析。
表2
Figure C0380112400131
如在表2中清楚地表明，比较例1至12的压敏电阻器的钾含量在处理后下降了0.17至0.39atm％，并且它们的变化为34％至78％。这是因为对于这些压敏电阻器，钾溶解在水中，或在制备过程中与水一起被除去。这些结果表明发生了组成变化。另外，如由表1中的结果所示，由于钾在水中良好的溶解性，通过例如重结晶钾的分散性降低，导致电压非直线性系数α、初始绝缘电阻IR和ESD敏感度的降低。
另一方面，实施例1至4的压敏电阻器的钾含量在处理后最多下降了0.05atm％，并且它们的变化是10％或更小。这些结果表明没有发生钾的组成变化。因此，如表1中所示，这些压敏电阻器可以避免初始绝缘电阻IR的降低，并且抑制压敏电阻器电压V1mA和初始绝缘电阻IR的变化。
<第二组实施例>
使用不同分散剂来制备压敏电阻器，并且评价其多种压敏电阻器特征。
所使用的溶解性差的钾化合物是KHC4H4O6。分别称量作为主要组分的ZnO，和作为微量组分的Pr6O11、Co3O4、CaCO3、Al2O3和KHC4H4O6。在将离子交换水和分散剂加入它们的时候，混合并通过湿法粉碎这些已称量过的原料。随后，按照与第一组实施例相同的方法和程序来制备多层压敏电阻器，并且评价其多种压敏电阻器特征。
具体而言，实施例21中所使用的分散剂是多羧酸铵，实施例22中使用的是多羧酸钠，比较例21中使用的是多磺酸铵，比较例22中使用的是多磺酸钠。
在第二组实施例中，所加入的离子交换水的量等同于原料的总重量，以检验分散剂的效果。所加入的分散剂的量是原料的1.0重量％。
为实施例21和22及比较例21和22的每一个制备总数为100件的试验样品。如第一组实施例中一样，测量这些试验样品的压敏电阻器电压V1mA、压敏电阻器电压V1mA的变化、电压非直线性系数α、初始绝缘电阻IR、初始绝缘电阻IR的变化，和另外测量冲击电流容量。
冲击电流容量是按照下列程序计算的。
参考图4，以5分钟的时间间隔，在每个试验样品的两端施加波前周期为8μs和波尾周期为20μs的8×20μs的两个三角形电流波。压敏电阻器电压的变化百分率ΔV1mA/V1mA是根据施加前与后之间压敏电阻器电压的差值ΔV1mA，与施加前的压敏电阻器电压V1mA计算的。然后，计算该施加前与后绝缘电阻的差值ΔlogIR。当压敏电阻器电压的变化百分率ΔV1mA/V1mA在±10％以内，和绝缘电阻的差值ΔlogIR是1/2时的波峰值，被计算作为冲击电流容量。冲击电流容量为30A/mm2或更多的的压敏电阻器被判定为合格品。在图4中，CF表示波峰值，P表示波峰，并且Q表示半波峰。
下表3显示了每个实施例和比较例的测量结果。
Figure C0380112400161
如在表3中清楚地表明，实施例21和22及比较例21和22的压敏电阻器的任何一种，与表1中实施例1至4的不含分散剂的压敏电阻器相比，显示了优异的冲击电流容量和小的压敏电阻器电压V1mA及绝缘电阻IR的变化。这些结果显示分散剂可以均匀地分散与溶解性差的钾化合物结合的组分，以防止有缺陷的晶粒间界。
比较例21与22的压敏电阻器具有优异的压敏电阻器特征，但包含多磺酸盐分散剂，其在焙烧期间产生硫氧化物。这样的硫氧化物可以毁坏焙烧炉并削弱其耐久性。
因此，考虑到所使用的焙烧加热炉的环境和耐久性，多羧酸盐分散剂是更满意的。上面的结果显示，多羧酸盐分散剂允许对压敏电阻器电压V1mA和绝缘电阻IR变化的抑制。
<第三组实施例>
制备含有不同量分散剂的压敏电阻器，并且评价其多种压敏电阻器特征。
所使用的溶解性差的钾化合物是KHC4H4O6，所使用的分散剂是多羧酸铵，所使用的溶剂是离子交换水。制备含有不同量分散剂的多层压敏电阻器，并且测量浆液粘度、初始绝缘电阻IR及初始绝缘电阻IR的变化。
具体而言，制备含有0.1至5.0重量％分散剂的多层压敏电阻器(实施例31至42)，和分别含有0.05重量％、5.5重量％和6.00重量％分散剂的多层压敏电阻器(比较例31至33)。用简单粘度计测量浆液粘度。按照与第一组实施例相同的方法计算初始绝缘电阻IR和它的变化。与在第二组实施例中一样，在第三组实施例中所加入的离子交换水的重量等同于原料的总重量，以计算对应于所加入分散剂量的浆液粘度、初始绝缘电阻IR和初始绝缘电阻IR的变化。
下表4显示了结果。
表4
Figure C0380112400181
如在表4中清楚地表明，含有少量分散剂(即0.05重量％)的比较例31的压敏电阻器显示在原料颗粒上面差的分散剂吸附性，导致1.500Pa·s的浆液粘度。因此，在比较例31中分散性的降低导致初始绝缘电阻IR320％的大变化。
含有分散剂为5.5重量％或更多的比较例32和33的压敏电阻器显示0.550Pa·s或更大的浆液粘度。这些结果显示分散剂缠绕于并再聚集原料的颗粒，以至发展成初始绝缘电阻IR的下降和变化。
在另一方面，实施例31至42的压敏电阻器显示了0.500Pa·s或更小的浆液粘度。在它们中间，含有0.3至4.5重量％分散剂的压敏电阻器显示了大大降低的浆液粘度，即，0.100Pa·s或更小。这样的粘度可以促进浆液的混合和粉碎，提供原料的优异分散性，导致初始绝缘电阻IR的增加。上面的结果显示实施例31至42的压敏电阻器可以抑制30％或更少的初始绝缘电阻IR的变化。
根据上面的详细描述，该实施方案提供了一种压敏电阻器的制备方法，该方法包括混合和湿法来粉碎作为主要组分的氧化锌，和作为微量组分的含有镨的化合物、含有钴的化合物和含有钾的化合物中至少一种的步骤。在此方法中，钾的加入是以溶解性差的钾化合物的形式，其中所包含的钾的溶解度是于25℃100克水溶液中3克或更小，例如以KClO4、KHC4H4O6、K2(PtCl6)或K2[Co(NO2)6]的形式。如果使用了这种化合物，在脱水期间，钾不溶解于水中或不与水一起被除去，不引起组成变化。另外，这样的化合物不改变第一浆液的pH，防止浆液粘度增加及溶混性、可轧性和分散性降低。此外，这种化合物可以防止干燥期间通过重结晶钾的聚集和不均匀沉积。因此，这个实施方案可以提供一种制备可以在低电压下操作的可靠的压敏电阻器的方法。
另外，在混合和粉碎步骤中加入0.1至5.0重量％的多羧酸盐分散剂。这种分散剂可以均匀地分散与溶解性差的钾化合物结合的组分，以防止有缺陷的晶粒间界。考虑到所使用的制备设备的环境和耐久性，这种分散剂也是令人满意的。因此，这个实施方案可以提供一种用于制备具有更小变化的压敏电阻器电压和绝缘电阻的压敏电阻器的简单方法。
因此，由根据本实施方案的方法所制备的压敏电阻器具有小的泄漏电流，可以在低电压下操作，显示了优异的压敏电阻器特征，并且是可靠的。这是因为钾不溶解或者在制备过程中不被除去，并且原料具有良好的分散性。
工业适用性
如上所述，根据本发明的制备压敏电阻器的方法适宜于压敏电阻器的制备，该压敏电阻器提供高性能来防止电子设备遭受冲击电流，并且适于例如用作各种不同电子设备的冲击保护器。

Claims (7)

1.一种用于制备压敏电阻器的方法，该方法包含混合和通过湿法来粉碎作为主要组分的氧化锌和作为微量组分的含有钾的化合物的步骤，其中
所述的含有钾的化合物是溶解性差的钾化合物，并且在该溶解性差的钾化合物中所包含的钾的溶解度于25℃100克水溶液中为3克或更小。
2.根据权利要求1所述的用于制备压敏电阻器的方法，其中含有镨的化合物和含有钴的化合物被使用作为附加的微量组分。
3.根据权利要求1所述的用于制备压敏电阻器的方法，其中所述的溶解性差的钾化合物包含选自高氯酸钾、酒石酸氢钾、六氯铂酸钾和六硝基钴酸钾中的至少一种材料。
4.根据权利要求1所述的用于制备压敏电阻器的方法，其中所述的混合和粉碎步骤进一步包含一种多羧酸盐分散剂的加入。
5.根据权利要求4所述的用于制备压敏电阻器的方法，其中所加入的多羧酸盐分散剂的量是所述的主要组分和微量组分总重量的0.1％至5.0重量％。
6.根据权利要求1所述的用于制备压敏电阻器的方法，其中所述的混合和粉碎步骤是用水进行的。
7.根据权利要求1所述的用于制备压敏电阻器的方法，进一步包含如下步骤：对通过混合和粉碎步骤而提供的材料脱水和干燥以制备颗粒；煅烧所述颗粒以制备煅烧过的粉末；向所述煅烧过的粉末中加入粘合剂和溶剂以制备用于压片的浆液；由所述的浆液形成薄片以制备陶瓷生片；在所述陶瓷生片上面形成内电极的导体图案；层压所述具有导体图案的陶瓷生片以制备层压材料；焙烧所述的层压材料；和在所述焙烧过的层压材料上面形成外电极。
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