CN103025917B - 电磁钢板及其制造方法 - Google Patents

电磁钢板及其制造方法 Download PDF

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CN103025917B
CN103025917B CN201180036048.2A CN201180036048A CN103025917B CN 103025917 B CN103025917 B CN 103025917B CN 201180036048 A CN201180036048 A CN 201180036048A CN 103025917 B CN103025917 B CN 103025917B
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mass parts
resin
composition
electro
treatment solution
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CN103025917A (zh
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竹田和年
小菅健司
高濑达弥
栋田孝司
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Nippon Steel Corp
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Nippon Steel Corp
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    • Y10T428/31699Ester, halide or nitrile of addition polymer

Abstract

本发明的电磁钢板(10)中,设置有基底铁(1)和形成在基底铁(1)的表面上的绝缘被膜(2)。绝缘被膜(2)包含100质量份的第1成分和0.5质量份~10质量份的第2成分,所述第1成分包含100质量份的磷酸金属盐和1质量份~50质量份的平均粒径为0.05μm~0.50μm的选自由丙烯酸树脂、环氧树脂和聚酯树脂组成的组中的1种或2种以上的混合物或者共聚物,所述第2成分由平均粒径为0.05μm~0.35μm的氟树脂的分散液或粉末形成。

Description

电磁钢板及其制造方法
技术领域
本发明涉及适用于电气设备的铁芯材料等的电磁钢板及其制造方法。 
背景技术
在使用电磁钢板制造发动机、变压器时,在将箍状的电磁钢板以规定形状打孔加工后,将多个电磁钢板层叠固定来制作层叠铁芯。然后,在层叠铁芯的齿等上缠绕铜线。接着,有时根据用途,会以提高耐久性和耐候性等为目的进行树脂模塑。 
此处,模塑树脂与层叠铁芯密合是重要的。这是因为与层叠铁芯不密合时,无法达成耐久性和耐候性的提高等目的。另外,在使用了磁铁的发动机中,磁铁使用模塑树脂固定于发动机,在密合性低的情况下,磁铁的固定变得不充分。 
在另一方面,发现模塑树脂与层叠铁芯的密合性过高时,在发动机等的制造过程中会产生各种问题。例如,在汽车所使用的发动机等中,从模塑树脂对层叠铁芯作用压缩应力,有时会增加铁损。即,在对层叠铁芯安装线圈等通电部后进行了树脂模塑的情况下,模塑树脂与层叠铁芯的露出部粘接时,来自模塑树脂的压缩应力作用于层叠铁芯,有时铁损变差而发动机的性能降低。另外,在使用模塑树脂将磁铁固定于发动机的情况下,模塑树脂与层叠铁芯的密合性过高时,难以除去附着在不必要的位置的模塑树脂。 
现有技术文献 
专利文献 
专利文献1:日本特公昭50-15013号公报 
专利文献2:日本特开平03-36284号公报 
专利文献3:日本特公昭49-19078号公报 
专利文献4:日本特开平06-330338号公报 
专利文献5:日本特开平09-323066号公报 
专利文献6:日本特开2002-309379号公报 
专利文献7:日本特开2002-164207号公报 
发明内容
发明所要解决的问题 
本发明的目的在于提供能够提高模塑树脂的剥离性的电磁钢板及其制造方法。 
用于解决问题的手段 
本发明的发明者们对使模塑树脂的剥离性降低的主要原因进行了研究,结果发现设置在电磁钢板的表面上的绝缘被膜与模塑树脂的密合性变得过高。绝缘被膜主要是为了确保层叠的电磁钢板彼此的绝缘性而设置的。另外,对于绝缘被膜除了绝缘性之外,还要求耐蚀性、焊接性、密合性、耐热性等各种特性。在绝缘被膜的形成中,通常涂布有以铬酸盐和磷酸盐等无机酸盐和有机树脂为主要成分的混合物。关于电磁钢板的绝缘被膜已知各种技术。并且,近年来,由于对环境问题的意识增强,因此正在进行不使用含有6价铬的铬酸水溶液的绝缘被膜的开发。 
然而,在现有的绝缘被膜中,即使是绝缘性等特性充分的绝缘被膜,也未注意到模塑树脂的剥离性,如上所述,伴随着模塑树脂的剥离性低存在各种问题点。本发明者们为了解决这样的问题点而进行了深入研究,结果想到了下述的各种方案。 
(1)一种电磁钢板,其特征在于,具有: 
基底铁(Jigane:body ofiron blade)、和 
形成在所述基底铁的表面上的绝缘被膜, 
所述绝缘被膜包含: 
100质量份的第1成分,所述第1成分包含:100质量份的磷酸金属盐、和1质量份~50质量份的平均粒径为0.05μm~0.50μm的选自由丙烯酸树脂、环氧树脂和聚酯树脂组成的组中的1种或2种以上的混合物或者共聚物;和 
0.5质量份~10质量份的由平均粒径为0.05μm~0.35μm的氟树脂的分 散液或粉末形成的第2成分。 
(2)一种电磁钢板,其特征在于,具有: 
基底铁、和 
形成在所述基底铁的表面上的绝缘被膜, 
所述绝缘被膜包含: 
100质量份的第1成分,所述第1成分包含:100质量份的胶体二氧化硅、和40质量份~400质量份的平均粒径为0.05μm~0.50μm的选自由丙烯酸树脂、环氧树脂和聚酯树脂组成的组中的1种或2种以上的混合物或者共聚物;和 
0.5质量份~10质量份的由平均粒径为0.05μm~0.35μm的氟树脂的分散液或粉末形成的第2成分。 
(3)根据(1)或(2)所述的电磁钢板,其特征在于,所述第1成分和所述第2成分占所述绝缘被膜的90%以上。 
(4)一种电磁钢板的制造方法,其特征在于,具有: 
在基底铁的表面涂布处理液的工序、和 
对所述处理液进行烘烤干燥的工序, 
作为所述处理液,使用包含下述成分的处理液: 
按固体成分计为100质量份的第1成分,所述第1成分包含:100质量份的磷酸金属盐、和按树脂固体成分计为1质量份~50质量份的平均粒径为0.05μm~0.50μm的选自由丙烯酸树脂、环氧树脂和聚酯树脂组成的组中的1种或2种以上的混合物或者共聚物的乳液;和 
按树脂固体成分计为0.5质量份~10质量份的由平均粒径为0.05μm~0.35μm的氟树脂的分散液或粉末形成的第2成分。 
(5)一种电磁钢板的制造方法,其特征在于,具有: 
在基底铁的表面涂布处理液的工序、和 
对所述处理液进行烘烤干燥的工序, 
作为所述处理液,使用包含下述成分的处理液: 
按固体成分计为100质量份的第1成分,所述第1成分包含:100质量份的胶体二氧化硅、和按树脂固体成分计为40质量份~400质量份的平均粒径为0.05μm~0.50μm的选自由丙烯酸树脂、环氧树脂和聚酯树脂组成的 组中的1种或2种以上的混合物或者共聚物的乳液;和 
按树脂固体成分计为0.5质量份~10质量份的由平均粒径为0.05μm~0.35μm的氟树脂的分散液或粉末形成的第2成分。 
(6)根据(4)或(5)所述的电磁钢板的制造方法,其特征在于,将所述烘烤干燥的达到温度设为150℃~350℃,将时间设为5秒钟~60秒钟。 
(7)根据(4)或(5)所述的电磁钢板的制造方法,其特征在于,所述第1成分和所述第2成分按固体成分换算计占所述处理液的90%以上。 
发明效果 
根据本发明,由于设置有适当的绝缘被膜,因此能够在维持较高绝缘性等的同时获得高的模塑树脂的剥离性。 
附图说明
图1是表示本发明的实施方式的电磁钢板的制造方法的流程图。 
图2是表示本发明的实施方式的电磁钢板的结构的剖视图。 
具体实施方式
以下,对于本发明的实施方式,参照所附的附图进行说明。图1是表示本发明的实施方式的电磁钢板的制造方法的流程图,图2是表示本发明的实施方式的电磁钢板的结构的剖视图。 
在本实施方式中,首先制作基底铁1(步骤S1)。在基底铁1的制作中,例如首先将规定组成的板坯在1050℃~1250℃左右加热,进行热轧来制作热轧板,将热轧板卷绕成线圈状。接着,边将热轧板开卷边进行冷轧来制作厚度为0.15mm~0.5mm左右的冷轧板,将冷轧板卷绕成线圈状。然后,在750℃~1100℃下退火(最终退火)。这样操作得到基底铁1。此外,在冷轧前,也可以根据需要在800℃~1050℃的范围内退火。 
基底铁1的组成例如为适于无方向性电磁钢板的组成。即,基底铁1例如包含:Si:0.1质量%以上、Al:0.05质量%以上,剩余部分含有Fe及不可避免的杂质。此外,除了Si及Al以外,也可以含有Mn:0.01质量%以上且1.0质量%以下。另外,可以含有Sn:0.01质量%以上且1.0质量%以下。另外,S、N及C等典型元素的含量优选小于100ppm,更优选小于 20ppm。含有Si越多,电阻就越大,从而磁特性就越高。但是,Si的含量超过4.0质量%时,有时脆性变得明显。因此,Si含量优选为4.0质量%以下。另外,含有Al越多,磁特性就越高。但是,Al的含量超过3.0质量%时,有时制作基底铁1时的冷轧会变得困难。因此,优选Al含量为3.0质量%以下。 
此外,基底铁1的组成也可以是适于方向性电磁钢板的组成。 
另外,基底铁1的表面粗糙度越低,层叠铁芯中的电磁钢板彼此的密合性就越高。因此,基底铁1的轧制方向及与轧制方向垂直的方向(板宽方向)的中心线平均粗糙度(Ra)优选为1.0μm以下,更优选为0.5μm以下。中心线平均粗糙度(Ra)超过1.0μm时,电磁钢板彼此的密合性低,难以得到层叠方向的高导热性。此外,为了使中心线平均粗糙度(Ra)小于0.1μm,需要严格地对冷轧进行控制,成本容易增高。因此,中心线平均粗糙度(Ra)优选为0.1μm以上。 
接着,如图2所示,在基底铁1的表面上形成绝缘被膜2(步骤S2)。在绝缘被膜2的形成中,将规定的处理液涂布在基底铁1的表面上(步骤S2a),然后通过加热使处理液干燥(步骤S2b)。其结果是,处理液中的成分被烘烤粘附到基底铁1的表面上。涂布处理液的方法没有特别限定,例如可以使用辊涂机或喷雾机涂布处理液,也可以将基底铁1浸渍在处理液中。另外,使处理液干燥的方法也没有特别限定,例如可以使用常规的辐射炉或热风炉使处理液干燥,也可以通过感应加热、高频加热等使用了电能的加热使处理液干燥。另外,关于处理液的干燥及烘烤(步骤S2b)的条件,该处理的温度(烘烤温度)优选设为150℃~300℃。特别是如后所述那样在处理液中包含磷酸金属盐时,烘烤温度优选设为230℃~300℃。另外,在处理液中包含磷酸金属盐时,该处理的时间优选设为5秒钟~60秒钟,在包含胶体二氧化硅时,优选设为3秒钟~60秒钟。 
此外,在涂布处理液前,可以在基底铁1的表面实施前处理。作为前处理,例如可以列举出:使用了碱性药剂等的脱脂处理、及使用了盐酸、硫酸或磷酸等的酸洗处理等。 
这里,对用于形成绝缘被膜2的处理液进行说明。作为该处理液,能够使用大致分类为以下两种类((a)、(b))的处理液。 
(a)一种处理液,其包含: 
按固体成分计为100质量份的第1成分,所述第1成分包含:100质量份的的磷酸金属盐、和按树脂固体成分计为1质量份~50质量份的平均粒径为0.05μm~0.50μm的选自由丙烯酸树脂、环氧树脂和聚酯树脂组成的组中的1种或2种以上的混合物或者共聚物的乳液;和 
按树脂固体成分计为0.5质量份~10质量份的由平均粒径为0.05μm~0.35μm的氟树脂的分散液或粉末形成的第2成分。 
(b)一种处理液,其包含: 
按固体成分计为100质量份的第1成分,所述第1成分包含:100质量份的胶体二氧化硅、和按树脂固体成分计为40质量份~400质量份的平均粒径为0.05μm~0.50μm的选自由丙烯酸树脂、环氧树脂和聚酯树脂组成的组中的1种或2种以上的混合物或者共聚物的乳液;和 
按树脂固体成分计为0.5质量份~10质量份的由平均粒径为0.05μm~0.35μm的氟树脂的分散液或粉末形成的第2成分。 
此外,第1成分及第2成分的总量优选以固体成分换算计为处理液整体的90%以上。这是为了确保绝缘被膜的良好的绝缘性、导热性、耐热性等。 
关于第1成分,磷酸金属盐为使以磷酸及金属离子作为主要成分的水溶液干燥时成为固体成分的物质。构成磷酸金属盐的磷酸的种类没有特别限定,例如能够使用正磷酸、偏磷酸、多磷酸等。另外,构成磷酸金属盐的金属离子的种类也没有特别限定,但优选Li、Al、Mg、Ca、Sr、Ti、Ni、Mn及Co等,特别优选Al、Ca、Mn及Ni。另外,磷酸金属盐溶液例如优选通过在正磷酸中混合金属离子的氧化物、碳酸盐和/或氢氧化物来制备。 
作为磷酸金属盐,可以仅使用1种,也可以混合使用2种以上。第1成分可以仅由磷酸金属盐构成,在第1成分中,也可以包含膦酸和/或硼酸等添加剂。 
同样,关于第1成分,作为胶体二氧化硅,例如优选使用平均粒径为5nm~40nm、且Na含量为0.5质量%以下的胶体二氧化硅。另外,胶体二氧化硅的Na含量更优选为0.01质量%~0.3质量%。 
在本实施方式中,优选在第1成分中包含丙烯酸树脂、环氧树脂和/或 聚酯树脂的乳液。作为丙烯酸树脂、环氧树脂和/或聚酯树脂的乳液,可以使用市售的树脂乳液。丙烯酸树脂、环氧树脂和/或聚酯树脂的熔点虽然没有特别限定,但优选为50℃以下。这是由于它们的熔点超过50℃时,容易发生粉化。另外,考虑成本时,它们的熔点优选为0℃以上。 
作为丙烯酸树脂,优选作为常规的单体的丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸正辛酯、丙烯酸异辛酯、丙烯酸2-乙基己酯、丙烯酸正壬酯、丙烯酸正癸酯及丙烯酸正十二酯等。另外,作为丙烯酸树脂,也优选使作为具有官能团的单体的丙烯酸、甲基丙烯酸、马来酸、马来酸酐、富马酸、巴豆酸及衣康酸以及作为具有羟基的单体的(甲基)丙烯酸2-羟乙酯、(甲基)丙烯酸2-羟丙酯、(甲基)丙烯酸3-羟丁酯及2-羟乙基(甲基)烯丙醚等共聚而成的树脂。 
作为环氧树脂,例如可以列举出:使羧酸酐与胺改性环氧树脂反应而成的树脂。具体而言,可以列举出:双酚A-二缩水甘油醚、双酚A-二缩水甘油醚的己内酯开环加成物、双酚F-二缩水甘油醚、双酚S-二缩水甘油醚、酚醛清漆缩水甘油醚、二聚酸缩水甘油醚等。作为改性的胺,可以列举出:异丙醇胺、单丙醇胺、单丁醇胺、单乙醇胺、二亚乙基三胺、乙二胺、丁胺、丙胺、异佛尔酮二胺、四氢糠胺、二甲苯二胺、己胺、壬胺、三亚乙基四胺、四亚甲基五胺、二氨基二苯砜等。作为羧酸酐,优选使琥珀酸酐、衣康酸酐、马来酸酐、柠康酸酐、邻苯二甲酸酐、偏苯三酸酐等反应而成的产物。 
作为聚酯树脂,例如优选使二羧酸与二醇反应而得到的树脂。作为二羧酸,可以列举出:对苯二甲酸、间苯二甲酸、邻苯二甲酸、萘二甲酸、联苯二甲酸、琥珀酸、己二酸、癸二酸、富马酸、马来酸、马来酸酐、衣康酸及柠康酸等。作为二醇,可以列举出:乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、新戊二醇、1,6-己二醇、三乙二醇、二丙二醇及聚乙二醇等。另外,也可以使用使丙烯酸、甲基丙烯酸、马来酸、富马酸、衣康酸、柠康酸或甲基丙烯酸酐等与这些聚酯树脂接枝聚合而得到的产物。 
另外,作为丙烯酸树脂、环氧树脂及聚酯树脂,可以仅使用1种,也可以混合使用2种以上。此外,作为这些有机树脂,使用平均粒径为 0.05μm~0.50μm的有机树脂。平均粒径小于0.05μm时,容易在处理液中凝聚,从而存在绝缘被膜2的均匀性降低的可能性。另一方面,平均粒径超过0.50μm时,存在处理液的稳定性降低的可能性。处理液的稳定性降低时,存在在处理液中产生凝聚物而堵塞管道和/或泵、或者凝聚物进入绝缘被膜2中而在绝缘被膜2中产生缺陷的可能性。另外,这些有机树脂的平均粒径优选为0.1μm以上,且优选为0.3μm以下。此外,作为平均粒径,例如能够使用由粒径为1μm以下的粒子求出的数均粒径。 
关于磷酸金属盐与丙烯酸树脂、环氧树脂及聚酯树脂的混合比率,相对于磷酸金属盐100质量份的丙烯酸树脂、环氧树脂及聚酯树脂的总量为1质量份~50质量份。丙烯酸树脂、环氧树脂及聚酯树脂的总量小于1质量份时,丙烯酸树脂、环氧树脂及聚酯树脂容易发生凝聚,绝缘被膜2的均匀性容易降低。另一方面,丙烯酸树脂、环氧树脂及聚酯树脂的总量超过50质量份时,耐热性降低。 
另外,关于胶体二氧化硅与丙烯酸树脂、环氧树脂及聚酯树脂的混合比率,相对于胶体二氧化硅100质量份的丙烯酸树脂、环氧树脂及聚酯树脂的总量为40质量份~400质量份。丙烯酸树脂、环氧树脂及聚酯树脂的总量小于40质量份时,难以适当形成绝缘被膜2,绝缘被膜2有可能粉化。另一方面,环氧树脂及聚酯树脂的总量超过400质量份时,耐热性降低。 
关于第2成分,作为氟树脂,例如可以使用聚四氟乙烯、四氟乙烯-全氟烷基乙烯基醚共聚物、四氟乙烯-六氟丙烯共聚物、四氟乙烯-乙烯共聚物、聚氯三氟乙烯、聚偏氟乙烯、四氟乙烯-六氟丙烯-全氟烷基乙烯基醚共聚物、氯三氟乙烯-乙烯共聚物及聚氟乙烯等。 
此外,使用赋予了羟基或者进行了环氧改性等的氟树脂时,模塑树脂的剥离性有降低倾向。因此,优选使用除赋予了羟基或者进行了环氧改性等的氟树脂以外的氟树脂。 
作为氟树脂的分散液或粉末,使用平均粒径为0.05μm~0.35μm的物质。氟树脂的分散液或粉末的平均粒径小于0.05μm时,无法获得充分的分散性,容易在处理液中凝聚,绝缘被膜2的均匀性容易降低。其结果是,有时无法获得充分的绝缘性等特性。另外,平均粒径超过0.35μm时,存在处理液的稳定性降低的可能性。另外,氟树脂的分散液或粉末的平均粒径 优选为0.15μm以上,且优选为0.25μm以下。 
此外,氟树脂的分散液或粉末可以单独使用,也可以两种以上混合使用。例如,可以混合使用平均粒径不同的多种分散液或粉末,也可以混合使用分子量不同的多种分散液或粉末。另外,可以将氟树脂的分散液和氟树脂的粉末混合使用。 
无论第1成分的主要成分为磷酸金属盐、胶体二氧化硅中的哪一种,关于第1成分及第2成分的配合比率,相对于第1成分的固体成分100质量份的第2成分的量都设为0.5质量份~10质量份。第2成分的量小于0.5质量份时,存在提高模塑树脂的剥离性的效果不充分的可能性。另一方面,第2成分的量超过10质量份时,存在处理液的稳定性降低的可能性。如上所述,处理液的稳定性降低时,存在在处理液中产生凝聚物而堵塞管道和/或泵、或者凝聚物进入绝缘被膜2中而在绝缘被膜2中产生缺陷的可能性。另外,由于氟树脂与其他有机树脂不同,具有特别是在界面凝聚的倾向,因此第2成分的量超过10质量份时,存在与基底铁1的密合性变得不充分的可能性。 
此外,可以在上述的处理液中加入表面活性剂等添加剂。作为表面活性剂,优选为非离子系表面活性剂,除此之外,也可以添加光泽剂、防腐剂、抗氧化剂等。 
另外,可以在上述的处理液中添加其他成分。例如可以添加碳酸盐、氢氧化物、氧化物、钛酸盐以及钨酸盐等无机化合物,也可以添加多元醇、溶纤剂、羧酸类、醚类以及酯类等有机低分子化合物。进而,还可以添加无机化合物和有机低分子化合物这两者。 
在通过这样的方法制造的电磁钢板10中,在使用了处理液(a)时,绝缘被膜2包含: 
100质量份的第1成分,所述第1成分包含:100质量份的磷酸金属盐、和1质量份~50质量份的平均粒径为0.05μm~0.50μm的选自由丙烯酸树脂、环氧树脂和聚酯树脂组成的组中的1种或2种以上的混合物或者共聚物;和 
0.5质量份~10质量份的由平均粒径为0.05μm~0.35μm的氟树脂的分散液或粉末形成的第2成分。 
另外,在使用了处理液(b)时,绝缘被膜2包含: 
100质量份的第1成分,所述第1成分包含:100质量份的胶体二氧化硅、和40质量份~400质量份的平均粒径为0.05μm~0.50μm的选自由丙烯酸树脂、环氧树脂和聚酯树脂组成的组中的1种或2种以上的混合物或者共聚物;和 
5质量份~40质量份的第2成分,所述第1成分是由平均粒径为2.0μm~15.0μm且熔点为60℃~140℃的选自由聚烯烃蜡、环氧树脂和丙烯酸树脂组成的组中的1种以上的粒子形成的。 
另外,作为绝缘被膜2,可得到在内部分散了氟树脂的绝缘被膜。在氟树脂的分散液或粉末的平均粒径为0.05μm~0.35μm的情况下,由于它们在处理液中的分散性极为良好,因此绝缘被膜2中的氟树脂的分散性也变得极为良好,会适度地降低整个绝缘被膜2的整体的实质的表面张力。其结果是,提高模塑树脂的剥离性。即,对于具备这样的绝缘被膜2的电磁钢板10来说,能够在维持较高的绝缘被膜2与基底铁1的密合性的同时,使得与模塑树脂的密合性为适当的密合性。例如,能够在确保固定磁铁所需的密合性等的同时,实现压缩应力的缓和以及剥离多余的模塑树脂时作业性的提高等。此外,氟树脂的平均粒径不合适时,在绝缘被膜2中氟树脂不均匀地分散,存在在绝缘被膜2的特性中产生不均的可能性。 
此外,在处理液中添加有表面活性剂、无机化合物、有机低分子化合物等时,它们以原样直接含于绝缘被膜2。 
另外,绝缘被膜2的厚度优选为0.3μm~3.0μm左右,更优选为0.5μm以上且1.5μm以下。 
此外,上述的胶体二氧化硅的平均粒径、丙烯酸树脂、环氧树脂和聚酯树脂的平均粒径以及氟树脂的平均粒径为数均粒径。作为胶体二氧化硅的数均粒径,例如使用通过氮吸附法(JIS Z8830)测定的数均粒径。另外,作为丙烯酸树脂、环氧树脂和聚酯树脂的数均粒径以及氟树脂的数均粒径,例如使用通过激光衍射法测定的数均粒径。 
另外,作为处理液,从对环境考虑出发优选使用不含Cr的处理液。 
此外,第1成分及第2成分优选占绝缘被膜2的90%以上。这是为了确保良好的绝缘性、导热性、耐热性等。 
实施例 
接着,对本发明者们进行的试验加以说明。这些试验中的条件等是为了确认本发明的可实施性以及效果而采用的例子,本发明不限定于这些例子。 
制作基底铁,该基底铁具有按质量%计含有Si:2.5%、Al:0.5%、Mn:0.05%的无方向性电磁钢板用的组成。基底铁的厚度设为0.35mm,其中心线平均粗糙度(Ra)设为0.46μm。 
另外,制作各种第1成分用的溶液。该溶液的成分表示在表1中。 
表1 
在包含磷酸金属盐的溶液的制作中,将正磷酸与Mg(OH)2、Al(OH)3等各金属氢氧化物、氧化物、碳酸盐混合搅拌,制备40质量%的水溶液。 
在包含胶体二氧化硅的溶液的制作中,制作包含30质量%的市售的平均粒径为15nm且表面用铝改性了的胶体二氧化硅的溶液。 
表1中的6种有机树脂的详细情况如下所述。 
“丙烯酸树脂1” 
以甲基丙烯酸甲酯为40质量%、甲基丙烯酸2-羟乙酯为10质量%、丙烯酸正丁酯为30质量%以及苯乙烯单体为20质量%进行共聚而得到的丙烯 酸树脂。 
“丙烯酸树脂2” 
以丙烯酸甲酯为40质量%、苯乙烯单体为30质量%、丙烯酸异丁酯为20质量%以及富马酸为10质量%进行共聚而得到的丙烯酸树脂。 
“环氧树脂1” 
在将双酚A用三乙醇胺改性后使琥珀酸酐反应而得到的羧基改性环氧树脂。 
“环氧树脂2” 
在酚醛清漆型环氧树脂中配合乙烯丙烯嵌段共聚物并加成壬基苯基醚环氧乙烷而形成的自乳化型的环氧树脂。 
“聚酯树脂” 
在以对苯二甲酸二甲酯为35质量%及新戊二醇为35质量%进行共聚后以富马酸为15质量%及偏苯三酸酐为15质量%进行接枝聚合而得到的含羧基聚酯树脂。 
“水性聚氨酯” 
用已知的方法由六亚甲基二异氰酸酯及聚乙二醇合成出的水性聚氨酯。 
将这些有机树脂分别制成30%乳液溶液,将它们混合在含有磷酸金属盐或胶体二氧化硅的溶液中。进而,根据需要添加适量粘度调节剂、表面活性剂,制备表1所示的溶液。 
此外,丙烯酸树脂1、2的平均粒径分别为0.25μm、0.64μm、0.6μm。另外,环氧树脂1、2的平均粒径分别为0.33μm、0.76μm。另外,聚酯树脂的平均粒径为0.35μm,水性聚氨酯的平均粒径为0.12μm。在这些平均粒径的测定中,将树脂乳液用蒸馏水稀释后,通过市售的基于激光衍射法的粒径测定装置测定数均粒径,该粒径测定装置以JIS法(JIS Z8826)为基准。此外,表1中的树脂质量份是换算为固体成分的值。 
接着,在表1所示的溶液中,添加规定量的表2所示的氟树脂的分散液或粉末,制作27种处理液。 
表2 
表2中的6种类的氟树脂的详细情况如下所述。 
“氟树脂1” 
聚四氟乙烯(PTFE)类型且平均粒径为0.25μm、浓度为48质量%的氟树脂的分散液。 
“氟树脂2” 
氟化乙烯丙烯(FEP)类型且平均粒径为0.34μm、浓度为50质量%的氟树脂的分散液。 
“氟树脂3” 
通过强制乳化制成水分散类型的平均粒径为0.12μm、浓度为60质量%的氟树脂的分散液。 
“氟树脂4” 
氟橡胶类型且平均粒径为2.5μm的氟树脂的粉末。 
“氟树脂5” 
赋予了羟基的类型且平均粒径为0.06μm、浓度为48质量%的氟树脂的分散液。 
“氟树脂6” 
将平均粒径为0.33μm的PTFE以及平均粒径为0.25μm的偏氟乙烯复合而得到的氟树脂的粉末。 
此外,在有机树脂的乳液的平均粒径的测定中,用蒸馏水稀释后,通过市售的基于激光衍射法的粒径测定装置测定数均粒径,该粒径测定装置以JIS法(JIS Z8826)为基准。另外,在氟树脂的粉末的平均粒径的测定中,用超声波清洗机使其在蒸馏水中分散约1分钟,然后通过市售的基于激光衍射法的粒径测定装置测定数均粒径,该粒径测定装置以JIS法(JISZ8826)为基准。此外,对于表面粗糙度,使用以JIS法(JIS B0601)为基准的市售的表面粗度测定装置测定中心线平均粗糙度(Ra)。 
并且,将处理液涂布于基底铁,以表2所示的条件进行烘烤。处理液使用辊涂机涂布。此时,调整辊压下量等,以使绝缘被膜的厚度成为约0.8μm。烘烤(干燥)使用辐射炉进行,调整炉温的设定,以使得可以得到表2所记载的规定的加热条件。以达到板温为160℃~400℃、烘烤时间为5秒钟~55秒钟的方式进行调整。 
并且,对于在烘烤结束后得到的电磁钢板,评价各种特性。即,对模塑树脂的剥离性、绝缘性、密合性、耐蚀性、外观及耐热性进行评价。 
在模塑树脂的剥离性的评价中,将夹持了0.05g的模塑树脂的粉末的2张电磁钢板的样品加热至150℃,在10kgf/cm2的加压下保持1分钟,进行空气冷却,并测定剪切拉伸强度。剪切拉伸强度的测定依据JIS法(JISK6850)进行,将剪切拉伸强度作为模塑树脂粘接力。此外,1kgf/cm2为约9.8N/cm2。剪切拉伸强度为10kgf/cm2以下时,模塑树脂的剥离性可以说是良好的。另一方面,剪切拉伸强度超过10kgf/cm2时,存在由于模塑树脂导致磁性变差的可能性,另外,用于固定磁铁时,存在在除去附着物时等的作业性差的可能性。 
在绝缘性的评价中,基于JIS法(JIS C2550)测定层间电阻。并且,将层间电阻小于5Ω·cm2/张的样品评价为×,将5Ω·cm2/张~10Ω·cm2/张的样品评价为△,将10Ω·cm2/张~50Ω·cm2/张的样品评价为○,将50Ω·cm2/张以上的样品评价为◎。 
在密合性的评价中,将粘合胶带粘贴至电磁钢板的样品,然后将其卷绕成直径为10mm、20mm、30mm的金属棒。接着,撕下粘合胶带,由剥离痕迹评价密合性。将即使卷绕成直径为10mm的金属棒也未剥离的样品评价为10mmφOK,将即使卷绕成直径为20mm的金属棒也未剥离的样品评价为20mmφOK。另外,将即使卷绕成直径为30mm的金属棒也未剥离的样品评价为30mmφOK,将在卷绕成直径为30mm的金属棒时剥离的样品评价为30mmφOUT。 
耐蚀性基于JIS法的盐水喷雾试验(JIS Z2371)进行,使用经过7小时后的样品以10分进行评价。评价基准如下所述。 
10:未生锈 
9:生锈极少量(面积率为0.1%以下) 
8:生锈面积率=超过0.1%且0.25%以下 
7:生锈面积率=超过0.25%且0.50%以下 
6:生锈面积率=超过0.50%且1%以下 
5:生锈面积率=超过1%且2.5%以下 
4:生锈面积率=超过2.5%且5%以下 
3:生锈面积率=超过5%且10%以下 
2:生锈面积率=超过10%且25%以下 
1:生锈面积率=超过25%且50%以下 
在外观的评价中,将有光泽、平滑且均匀的样品评价为5,以下,将有光泽但均匀性略差的样品评价为4,将略有光泽、平滑但均匀性差的样品评价为3,将光泽少、平滑性略差且均匀性差的样品评价为2,将光泽、均匀性、平滑性差的样品评价为1。 
关于耐热性,在钢板表面上以100gf(约0.98N)的负荷摩擦2mm×30mm 的纱布,基于绝缘被膜的剥离状况进行评价。将未剥离的样品评价为5,将略微剥离的样品评价为4,将明显剥离的样品评价为3,将剥离状况严重的样品评价为2,将即使不用纱布摩擦也剥离的样品评价为1。 
这些评价结果表示在表3中。 
表3 
如表3所示,通过该实验可知本发明的效果。即,如表3所示,就属于本发明的实施例的样品而言,模塑树脂的粘接力为10kgf/cm2以下,可以说具有优异的模塑树脂的剥离性。另外,也可知属于本发明的实施例的样品除了模塑树脂的剥离性以外,绝缘性、密合性、耐蚀性、外观及耐热性 也优异。另外,就属于比较例的样品而言,模塑树脂的粘接力成为超过10kgf/cm2的较大的值的样品多,并且,不存在绝缘性、密合性、耐蚀性、外观及耐热性全部优异的样品。 
如以上说明的那样,就本发明的实施方式的电磁钢板而言,例如在层叠铁芯、模具等中,模塑树脂的剥离性良好且层叠铁芯的铁损特性提高,并且电磁钢板的绝缘被膜特性良好。 
以上,对本发明的优选实施方式进行了详细的说明,本发明不限于所述例子。只要是具有本发明所属技术领域的一般知识的人,在权利要求书所记载的技术思想的范畴内,显然可以想到各种的变更例或修改例,关于这些当然也可以理解为属于本发明的技术范围。 
产业上的可利用性 
本发明例如能够在电磁钢板制造产业及电磁钢板利用产业中利用。 

Claims (10)

1.一种用于进行了树脂模塑的层叠铁芯的电磁钢板,其特征在于,具有:基底铁和形成在所述基底铁的表面上的绝缘被膜,
所述绝缘被膜包含:
100质量份的第1成分,所述第1成分包含:100质量份的磷酸金属盐和1质量份~50质量份的平均粒径为0.05μm~0.50μm的选自由丙烯酸树脂、环氧树脂和聚酯树脂组成的组中的1种或2种以上的混合物或者共聚物;和
0.5质量份~10质量份的由平均粒径为0.05μm~0.35μm的氟树脂的分散液或粉末形成的第2成分。
2.一种用于进行了树脂模塑的层叠铁芯的电磁钢板,其特征在于,具有:基底铁和形成在所述基底铁的表面上的绝缘被膜,
所述绝缘被膜包含:
100质量份的第1成分,所述第1成分包含:100质量份的胶体二氧化硅和40质量份~400质量份的平均粒径为0.05μm~0.50μm的选自由丙烯酸树脂、环氧树脂和聚酯树脂组成的组中的1种或2种以上的混合物或者共聚物;和
0.5质量份~10质量份的由平均粒径为0.05μm~0.35μm的氟树脂的分散液或粉末形成的第2成分。
3.根据权利要求1所述的用于进行了树脂模塑的层叠铁芯的电磁钢板,其特征在于,所述第1成分和所述第2成分占所述绝缘被膜的90%以上。
4.根据权利要求2所述的用于进行了树脂模塑的层叠铁芯的电磁钢板,其特征在于,所述第1成分和所述第2成分占所述绝缘被膜的90%以上。
5.一种用于进行了树脂模塑的层叠铁芯的电磁钢板的制造方法,其特征在于,具有:在基底铁的表面涂布处理液的工序和对所述处理液进行烘烤干燥的工序,
作为所述处理液,使用包含下述成分的处理液:
按固体成分计为100质量份的第1成分,所述第1成分包含:100质量份的磷酸金属盐和按树脂固体成分计为1质量份~50质量份的平均粒径为0.05μm~0.50μm的选自由丙烯酸树脂、环氧树脂和聚酯树脂组成的组中的1种或2种以上的混合物或者共聚物的乳液;和
按树脂固体成分计为0.5质量份~10质量份的由平均粒径为0.05μm~0.35μm的氟树脂的分散液或粉末形成的第2成分。
6.一种用于进行了树脂模塑的层叠铁芯的电磁钢板的制造方法,其特征在于,具有:在基底铁的表面涂布处理液的工序和对所述处理液进行烘烤干燥的工序,
作为所述处理液,使用包含下述成分的处理液:
按固体成分计为100质量份的第1成分,所述第1成分包含:100质量份的胶体二氧化硅和按树脂固体成分计为40质量份~400质量份的平均粒径为0.05μm~0.50μm的选自由丙烯酸树脂、环氧树脂和聚酯树脂组成的组中的1种或2种以上的混合物或者共聚物的乳液;和
按树脂固体成分计为0.5质量份~10质量份的由平均粒径为0.05μm~0.35μm的氟树脂的分散液或粉末形成的第2成分。
7.根据权利要求5所述的用于进行了树脂模塑的层叠铁芯的电磁钢板的制造方法,其特征在于,将所述烘烤干燥的达到温度设为150℃~350℃,将时间设为5秒钟~60秒钟。
8.根据权利要求6所述的用于进行了树脂模塑的层叠铁芯的电磁钢板的制造方法,其特征在于,将所述烘烤干燥的达到温度设为150℃~350℃,将时间设为3秒钟~60秒钟。
9.根据权利要求5所述的用于进行了树脂模塑的层叠铁芯的电磁钢板的制造方法,其特征在于,所述第1成分和所述第2成分按固体成分换算计占所述处理液的90%以上。
10.根据权利要求6所述的用于进行了树脂模塑的层叠铁芯的电磁钢板的制造方法,其特征在于,所述第1成分和所述第2成分按固体成分换算计占所述处理液的90%以上。
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