CN105264115A - 带有绝缘被膜的电磁钢板 - Google Patents

带有绝缘被膜的电磁钢板 Download PDF

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CN105264115A
CN105264115A CN201480029665.3A CN201480029665A CN105264115A CN 105264115 A CN105264115 A CN 105264115A CN 201480029665 A CN201480029665 A CN 201480029665A CN 105264115 A CN105264115 A CN 105264115A
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insulation tunicle
steel plate
electro
magnetic steel
tunicle
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CN105264115B (zh
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佐志一道
村松直树
藤林亘江
洼田隆广
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JFE Steel Corp
JFE Engineering Corp
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NKK Corp
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Abstract

本发明提供一种耐腐蚀性、粘附性优良的带有绝缘被膜的电磁钢板。一种带有绝缘被膜的电磁钢板，其具有电磁钢板和在电磁钢板上形成的绝缘被膜，绝缘被膜含有Zr和Fe，Zr的含量以ZrO2换算为0.05～1.50g/m2，Zr和Fe的含有比例以摩尔比(绝缘被膜中的Fe量(摩尔)/绝缘被膜中的Zr量(摩尔))计为0.10～2.00。优选绝缘被膜还含有Si，并且Zr和Si的含有比例以摩尔比(绝缘被膜中的Si量(摩尔)/绝缘被膜中的Zr量(摩尔))计为2.00以下。

Description

带有绝缘被膜的电磁钢板
技术领域
本发明涉及耐腐蚀性、粘附性(密着性)优良的带有绝缘被膜的电磁钢板。
背景技术
对于在电动机、变压器等中使用的电磁钢板上所形成的绝缘被膜，不仅要求层间电阻，还要求加工成型时的便利性以及保管、使用时的稳定性等各种特性。并且，对于在电磁钢板上形成的绝缘被膜所要求的特性，随着用途而不同，因此根据用途进行了各种绝缘被膜的开发。
通常，在使用电磁钢板制造制品时，对电磁钢板实施冲裁加工、剪切加工、弯曲加工等。在对电磁钢板实施这些加工时，磁特性有时会因残余应变而劣化。为了消除该磁特性的劣化，大多情况下在700～800℃左右的温度下进行去应力退火。在进行去应力退火时，要求绝缘被膜具有耐去应力退火时的热的程度的耐热性。
此外，在电磁钢板上所形成的绝缘被膜可以分为以下3种。
(1)重视焊接性、耐热性，耐去应力退火的无机被膜。
(2)以兼顾冲裁性和焊接性为目标，耐去应力退火的含有树脂的无机被膜(即，半有机被膜)。
(3)具有特殊用途、不可去应力退火的有机被膜。
作为通用品，耐去应力退火的热的绝缘被膜是上述(1)、(2)所示的绝缘被膜。作为这些绝缘被膜中含有的无机成分，大多使用铬化合物。使用了铬化合物的(2)类型的绝缘被膜的一个例子是铬酸盐系绝缘被膜。
(2)类型的铬酸盐系绝缘被膜，是通过一涂一烘的制造而形成的。并且，(2)类型的铬酸盐系绝缘被膜与(1)类型的无机被膜相比，可以显著提高带有绝缘被膜的电磁钢板的冲裁性，因此被广泛使用。
例如，专利文献1中记载了一种具有电绝缘被膜的电工铁板，其是通过下述方法得到的：在含有至少1种2价金属的重铬酸盐系水溶液中，相对于该水溶液中的CrO3：100重量份，配合以树脂固体成分计为5～120重量份比例的作为有机树脂的树脂乳液和10～60重量份比例的有机还原剂，其中所述树脂乳液的乙酸乙烯酯/VeoVA比为90/10～40/60的比例，得到处理液，将该处理液涂布到基底铁板的表面，通过常规方法实施烘烤。
然而，近来环境意识提高，在电磁钢板领域中也要求具有不含铬化合物的绝缘被膜的电磁钢板。
因此，开发了带有不含铬化合物的绝缘被膜的电磁钢板。例如，专利文献2中公开了一种不含铬化合物，并且可以改善上述冲裁性等的绝缘被膜。专利文献2所记载的绝缘被膜含有树脂和胶体二氧化硅(含氧化铝的二氧化硅)。此外，专利文献3中公开了一种由胶体状二氧化硅、氧化铝溶胶、氧化锆溶胶中的1种或2种以上所形成的、含有水溶性或乳液树脂的绝缘被膜。此外，专利文献4中公开了一种不含铬化合物、以磷酸盐作为主体的含有树脂的绝缘被膜。
然而，带有不含铬化合物的绝缘被膜的电磁钢板，与含有铬化合物的绝缘被膜相比，有时耐腐蚀性、粘附性(绝缘被膜与电磁钢板的粘附性)会变差。专利文献2～4各技术也试图进行耐腐蚀性、粘附性的改善，但还要求更适合的改善方法。
对此，例如，专利文献5中公开了一种通过将由多价金属磷酸盐构成的被膜中的Fe量抑制为0≤Fe/P≤0.10，从而改善耐腐蚀性、粘附性的方法。而且，虽然专利文献6中未记载具体的数值，但其公开了一种通过抑制Fe溶出而改善绝缘被膜特性的方法。也就是说，专利文献6提出了一种绝缘被膜，其除了含有树脂、Al化合物和Si化合物以外，还含有离子化倾向比Fe高并且在水系介质中可以成为2价以上离子的Al以外的1种或2种以上易离子性元素(Cr除外)。作为所述易离子性元素，可以列举Mg、Zn、Zr、Ca、Sr、Mn和Ba。
如上所述，通常可以认为由于Fe向绝缘被膜中的溶出，而存在有绝缘被膜的特性变差的倾向。并且，在将不含具有钝化效果的铬化合物的涂料在电磁钢板表面直接涂装并烘烤而形成的被膜的情况下，很难控制Fe的上述溶出。结果，难以充分提高绝缘被膜的性能。
现有技术文献
专利文献
专利文献1：日本特公昭60－36476号公报
专利文献2：日本特开平10－130858号公报
专利文献3：日本特开平10－46350号公报
专利文献4：日本专利第2944849号公报
专利文献5：日本专利第3718638号公报
专利文献6：日本特开2005－240131号公报
发明内容
发明所要解决的问题
本发明是为了解决上述问题而进行的，其目的在于提供一种耐腐蚀性、粘附性优良的带有绝缘被膜的电磁钢板。
用于解决问题的方法
本发明人们为了解决上述问题而进行了深入研究。结果，本发明人们意外地发现，在含有Zr的绝缘被膜中，含有特定量Fe的绝缘被膜的被膜特性(绝缘被膜的耐腐蚀性、粘附性)提高，从而完成了本发明。更具体而言，本发明提供以下内容。
(1)一种带有绝缘被膜的电磁钢板，其特征在于，具有电磁钢板和在所述电磁钢板上形成的绝缘被膜，所述绝缘被膜含有Zr和Fe，所述Zr的含量以ZrO2换算为0.05～1.50g/m2，所述Zr和所述Fe的含有比例以摩尔比(绝缘被膜中的Fe量(摩尔)/绝缘被膜中的Zr量(摩尔))计为0.10～2.00。
(2)根据(1)所述的带有绝缘被膜的电磁钢板，其特征在于，所述绝缘被膜进一步含有Si，所述Zr和所述Si的含有比例以摩尔比(绝缘被膜中的Si量(摩尔)/绝缘被膜中的Zr量(摩尔))计为2.00以下。
(3)根据(1)或(2)所述的带有绝缘被膜的电磁钢板，其特征在于，所述绝缘被膜进一步含有P，所述Zr和所述P的含有比例以摩尔比(绝缘被膜中的P量(摩尔)/绝缘被膜中的Zr量(摩尔))计为1.50以下。
(4)根据(1)～(3)中任一项所述的带有绝缘被膜的电磁钢板，其特征在于，所述绝缘被膜进一步含有有机树脂，所述Zr和所述有机树脂的含有比例以固体成分比率(绝缘被膜中的有机树脂的固体成分量(g)/Zr的含量(g)(ZrO2换算质量))计为0.50以下。
发明效果
本发明的带有绝缘被膜的电磁钢板，具有优良的耐腐蚀性、粘附性(绝缘被膜与电磁钢板之间的粘附性)。
此外，根据本发明，即使绝缘被膜不含Cr，带有绝缘被膜的电磁钢板也具有优良的耐腐蚀性和上述粘附性。
附图说明
图1是表示使用了俄歇电子能谱仪的深度分析结果的一个例子的图。
图2是表示绝缘被膜与电磁钢板的粘附性与摩尔比(Fe/Zr)的关系的图。
具体实施方式
以下，具体说明本发明的实施方式。需要说明的是，本发明并不限定于以下的实施方式。
本发明的带有绝缘被膜的电磁钢板，具有电磁钢板和在该电磁钢板上形成的绝缘被膜。
电磁钢板
本发明中使用的电磁钢板，并不限定于特定的电磁钢板。例如，构成电磁钢板的成分，只要是在通常的电磁钢板中能够含有的成分即可。作为电磁钢板含有的成分，除了Si以外，还可以列举用于提高磁特性或其他性能的Mn、P、Al、S、N、V等。此外，电磁钢板的余量由Fe和不可避免的杂质构成。
电磁钢板的种类没有特别限定。磁通密度高的所谓软铁板(电工铁板)、SPCC等通常的冷轧钢板、含有用于提高比电阻的Si、Al的无取向性电磁钢板等均可以优选适用于本发明。
作为具体的电磁钢板的特性，适合的是铁损W15/50为16.0W/kg以下，优选为13.0W/kg以下，和/或磁通密度B50为1.5T以上，优选为1.6T以上。作为电磁钢板，合计含有0.1～10.0质量％左右的Si和/或Al的电磁钢板是代表性的材料。
绝缘被膜
绝缘被膜是在上述电磁钢板上所形成的绝缘被膜。在此，绝缘被膜的层间电阻一般为1Ω·cm2/片以上。上述绝缘被膜含有Zr和Fe。此外，上述绝缘被膜可以优选含有选自Si、P和有机树脂中的至少一种。
通过在绝缘被膜中含有Zr，绝缘被膜成为强韧的被膜。该强韧的被膜可以认为是通过Zr彼此或Zr与其他无机化合物形成网络而形成的。之所以能够形成上述网络，其原因在于Zr具有3个以上的原子键，并且Zr与氧的键合力强，可以与Fe表面的氧化物、氢氧化物等牢固地键合。为了获得上述使用Zr的效果，同时对带有绝缘被膜的电磁钢板赋予耐腐蚀性，需要将Zr化合物的附着量调整至以ZrO2换算为0.05g/m2以上。认为当Zr化合物的附着量以ZrO2换算小于0.05g/m2时，由于被覆不充分，因此上述耐腐蚀性下降。此外，认为当Zr化合物的附着量超过1.50g/m2时，由于被膜变得容易产生破裂，因此认为绝缘被膜与电磁钢板之间的粘附性，以及带有绝缘被膜的电磁钢板的耐腐蚀性变差。因此，需要将Zr化合物的附着量调整为1.50g/m2以下。从被膜性能的观点考虑，更优选的下限为0.20g/m2，更优选的上限为1.00g/m2。
之所以将绝缘被膜中的Zr量以ZrO2进行换算，其原因在于推定每1个Zr原子最多可以存在4个的Zr－O(－Zr)键构成了被膜结构的基础。
含有Zr的绝缘被膜通过含有特定量的Fe，绝缘被膜的被膜特性提高。如上所述，可以认为绝缘被膜中的Fe导致绝缘被膜的被膜特性变差。然而，如实施例中所示，在含有Zr的绝缘被膜中，通过使绝缘被膜含有特定量的Fe，绝缘被膜的被膜特性提高。虽然这种被膜特性提高的原因尚未明确，但可以认为是由于绝缘被膜中的Zr与Fe之间的某种相互作用导致的。
为了获得含有Zr的绝缘被膜含有Fe而带来的上述效果，需要考虑绝缘被膜中的Fe含量和绝缘被膜中的Zr含量来确定。具体而言，需要确定Fe的含量，以使摩尔比(绝缘被膜中的Fe量(摩尔)/绝缘被膜中的Zr量(摩尔)，在本说明书中，有时称为摩尔比(Fe/Zr))为0.10～2.00。当摩尔比(Fe/Zr)小于0.10时，粘附性变得不充分。其原因可以认为是，在绝缘被膜与电磁钢板的界面处，Zr与Fe的相互作用变得不充分。此外，当摩尔比(Fe/Zr)超过2.00时，可以认为在Zr的4个原子键以上含有Fe，上述粘附性、上述耐腐蚀性变差。摩尔比(Fe/Zr)的优选范围是0.2～1.5。
绝缘被膜中的摩尔比(Fe/Zr)是指通过俄歇电子能谱分析得到的摩尔比。在一边溅射一边在深度方向上进行分析的俄歇电子能谱分析中，可以通过求出直至Zr强度减半处的Fe、Zr各自的平均值，测定摩尔比(Fe/Zr)。将这时的分析点数设定为10点以上，将其平均值作为摩尔比(Fe/Zr)。需要说明的是，直至Zr强度减半处为止为绝缘被膜。不言而喻，比上述Zr强度减半位置更深的部分为电磁钢板。
需要说明的是，通过将后述的Fe化合物用于绝缘被膜的形成，能够在电磁钢板上形成含有Fe的绝缘被膜，但也可以在不使用Fe化合物的情况下使电磁钢板中的Fe包含于绝缘被膜中。
绝缘被膜优选含有Si。通过在绝缘被膜中含有Si，可以提高绝缘被膜的绝缘性。此外，如果含有特定量Zr和特定量Fe的绝缘被膜进一步含有Si，则绝缘被膜和电磁钢板之间的粘附性进一步提高。为了获得这些效果，绝缘被膜优选以摩尔比(绝缘被膜中的Si量(摩尔)/绝缘被膜中的Zr量(摩尔)，在本说明书中，有时称为摩尔比(Si/Zr))满足0.30以上的方式含有Si。
此外，优选调整Si的量，以使摩尔比(Si/Zr)满足2.00以下。通过使摩尔比(Si/Zr)为2.00以下，能够充分抑制由于相对于Zr含有较多的Si而导致的粘附性的劣化。在含有Si时，可以认为在被膜结构中附加了Si－O键。
绝缘被膜优选含有P。通过使含有特定量Zr和特定量Fe的绝缘被膜进一步含有Si，带有绝缘被膜的电磁钢板的耐腐蚀性提高。为了获得耐腐蚀性提高的效果，绝缘被膜优选以摩尔比(绝缘被膜中的P量(摩尔)/绝缘被膜中的Zr量(摩尔)，在说明书中，有时称为摩尔比(P/Zr))满足0.20以上的方式含有P。更优选为0.50以上。
此外，优选进行调整以使摩尔比(P/Zr)满足1.50以下。即使以摩尔比(P/Zr)超过1.50的条件含有P，上述耐腐蚀性的效果也不会提高，有时还会下降。
绝缘被膜优选含有有机树脂。通过使绝缘被膜含有有机树脂，带有绝缘被膜的电磁钢板具有优良的耐腐蚀性、耐擦伤性和冲裁性。从获得这些效果的观点考虑，优选将干燥被膜中的有机树脂含量调整至5质量％以上。需要说明的是，所谓干燥被膜中的含量，是指形成于钢板表面上的绝缘被膜中的有机树脂的比例。干燥被膜量还可以由将用于在钢板上形成绝缘被膜的处理液在180℃下干燥30分钟后的干燥后残留成分(固体成分)求出。
此外，通过使含有特定量Zr和特定量Fe的绝缘被膜进一步含有有机树脂，带有绝缘被膜的电磁钢板的被膜特性(耐腐蚀性)显著提高。从该被膜特性提高的观点考虑，优选调整绝缘被膜中的有机树脂的含量，以使固体成分比率((有机树脂的含量)/Zr的含量(ZrO2换算质量))满足0.50以下。
除了上述成分以外，绝缘被膜还可以含有表面活性剂、防锈剂、润滑剂、抗氧剂等通常使用的添加剂，或其他无机化合物、有机化合物等。作为有机化合物，例如，可以列举作为无机成分与有机树脂的接触抑制剂使用的有机酸。作为有机酸，可以举例含有羧酸的聚合物或共聚物等。此外，作为无机化合物，可以列举硼、颜料等。这些其他成分(在本说明书中，有时称为“添加物”)，可以以不损害本发明效果的范围包含在绝缘被膜中。在本发明中，优选以质量比((添加物的固体成分合计质量)/Zr的含量(ZrO2换算质量))为1.00以下的范围含有上述添加物。更优选以质量比((添加物的固体成分合计质量)/Zr的含量(ZrO2换算质量))为0.50以下的范围含有上述添加物。
此外，本发明的特征在于，即使绝缘被膜不含有Cr化合物，也可以提高带有绝缘被膜的电磁钢板的耐腐蚀性、绝缘被膜与电磁钢板的粘附性。在此，从Cr化合物不对耐腐蚀性等产生影响的观点考虑，所谓不含Cr化合物是指Cr的含量在干燥被膜中以Cr换算为0.1质量％以下，而如果考虑到Cr化合物对环境的影响，则是指Cr的含量在干燥被膜中以Cr换算为0.01质量％以下。
另外，在绝缘被膜中，有时混入了作为杂质的Hf、HfO2、TiO2等。这些杂质的总量，例如，只要相对于Zr的含量(ZrO2换算质量)为5质量％以下即可。绝缘被膜中的Zr量，以ZrO2换算质量相对于固体成分总量的比率计，优选为15质量％以上，该比率进一步优选为20质量％以上。
接着，对带有绝缘被膜的电磁钢板的制造方法进行说明。
首先，用于制造带有绝缘被膜的电磁钢板的电磁钢板，可以采用通过一般方法制造的材料、市售的材料。
在本发明中，对于作为原材料的电磁钢板的预处理没有特别规定。也就是说，可以不进行处理，但是对电磁钢板实施碱等的脱脂处理、盐酸、硫酸、磷酸等的酸洗处理是有利的。
接着，制备用于形成绝缘被膜的处理液。处理液例如可以通过向去离子水中添加以下化合物等来制备。
处理液含有用于使绝缘被膜中含有Zr的Zr化合物。此外，处理液可以含有Fe化合物、Si化合物、P化合物和有机树脂中的至少一种。通过在处理液中含有这些成分，可以使绝缘被膜中含有Fe、Si、P、有机树脂。需要说明的是，在本发明中，虽然在绝缘被膜中必须含有Fe，但由于也可以使绝缘被膜中含有电磁钢板中的Fe，因此处理液中并非必须含有Fe化合物作为必须成分。
此外，上述化合物、有机树脂的使用量，只要根据绝缘被膜中含有的Zr等的量进行适当设定即可。换句话说，摩尔比(Si/Zr)、摩尔比(P/Zr)、有机树脂的固体成分比率，可以在处理液制备阶段调整为所希望的值。
作为Zr化合物，可以列举例如乙酸锆、丙酸锆、氧氯化锆、硝酸锆、碳酸锆铵、碳酸锆钾、羟基氯化锆、硫酸锆、磷酸锆、磷酸锆钠、六氟锆酸钾、四正丙醇锆、四正丁醇锆、四乙酰丙酮合锆、三丁氧基乙酰丙酮合锆、三丁氧基硬脂酸锆等。这些化合物当然可以单独添加，也可以将2种以上复合使用。
作为Fe化合物，可以列举例如乙酸铁、柠檬酸铁、柠檬酸铁铵等。这些化合物当然可以单独添加，也可以将2种以上复合使用。
作为Si化合物，可以列举例如胶体二氧化硅(粒径：3～300nm)、煅制二氧化硅(比表面积：40～400m2/g)、烷氧基硅烷和硅氧烷等。这些化合物当然可以单独添加，也可以将2种以上复合使用。
作为P化合物，可以列举例如磷酸和磷酸盐。作为磷酸，可以列举正磷酸、磷酸酐、直链状多磷酸、环状偏磷酸等。作为磷酸盐，可以列举磷酸镁、磷酸铝、磷酸钙、磷酸锌、磷酸铵等。这些化合物当然可以单独添加，也可以将2种以上复合使用。
作为有机树脂，可以优选使用一直以来所使用的公知材料。可以列举例如丙烯酸树脂、醇酸树脂、聚烯烃树脂、苯乙烯树脂、乙酸乙烯酯树脂、环氧树脂、酚醛树脂、聚酯树脂、聚氨酯树脂、三聚氰胺树脂等水性树脂(乳液、分散液、水溶性)。特别优选的是丙烯酸树脂、乙烯丙烯酸树脂的乳液。另外，这些材料当然可以单独添加，也可以将2种以上复合使用，或者还可以作为共聚物使用。
另外，如果处理液中含有表面活性剂、防锈剂、润滑剂等添加物，则绝缘被膜中也可以含有这些添加物。
处理液的pH，没有特别限定，优选为3以上且12以下。如果处理液的pH为3以上，则从被膜中的Fe量不易过量的原因考虑是优选的，如果处理液的pH为12以下，则从被膜中的Fe量较难不足的原因考虑是优选的。
接着，将上述处理液涂布到电磁钢板的表面，并放置一定时间。通过该一定时间的放置，电磁钢板中的Fe溶出，Fe进入到处理液中，因此可以使绝缘被膜中含有Fe。从使绝缘被膜中含有特定量Fe的观点考虑，放置时间优选设定为3～220秒的范围，更优选设定为10～100秒的范围。但是，最佳的放置时间根据放置时气氛的温度(室温，例如10～30℃的范围)、处理液的pH、电磁钢板的组成而不同。因此，优选在考虑这些因素的同时，从3～220秒的范围、10～100秒的范围中适当选择最佳的放置时间。
另外，将上述处理液涂布到电磁钢板表面的方法没有特别限定，可以采用在一般工业上使用了辊涂机、流涂机、喷雾、刮刀涂布机等的各种方法。
接着，烘烤涂布到电磁钢板上的处理液，使涂布的处理液成为绝缘被膜。烘烤的方法没有特别限定，可以采用通常实施的热风加热式、红外线加热式、感应加热式等烘烤炉。上述烘烤时的烘烤温度没有特别限定，只要使到达钢板温度为150～350℃左右即可。此外，烘烤时间(在炉时间)也没有特别限定，但优选为1～600秒。
通过对本发明的带有绝缘被膜的电磁钢板实施去应力退火，可以除去例如因冲裁加工而产生的应变。作为优选的去应力退火气氛，可以列举N2气氛、DX气体气氛等铁不易被氧化的气氛等。在此，通过提高露点，例如设定为Dp：5～60℃左右，使表面和切断端面产生少许氧化，可以进一步提高耐腐蚀性。此外，优选的去应力退火温度为700～900℃，更优选为700～800℃。去应力退火温度的保持时间优选较长，更优选为1小时以上。
绝缘被膜优选存在于钢板的两表面，但也可以根据目的仅存在于单面。此外，还可以根据目的仅在单面形成本发明的绝缘被膜，而另一面为其他绝缘被膜。
实施例
向去离子水中添加表2中所示的Zr化合物、表3中所示的Si化合物、表4中所示的P化合物、表5中所示的有机树脂化合物，形成处理液，以使干燥后的绝缘被膜中的摩尔比(Si/Zr)、摩尔比(P/Zr)、固体成分比率(绝缘被膜中的有机树脂/Zr)为表1(将表1－1和表1－2合起来作为表1)所示值。在此，各成分合计相对于去离子水量的固体成分浓度为50g/l。此外，各处理液的pH示于表1。另外，对于发明例12，如果Fe未从电磁钢板中溶出，则添加乙酸铁，以使摩尔比(Fe/Zr)达到0.40。
使用辊涂机将这些处理液涂布于从板厚：0.35mm的电磁钢板[A360(JISC2552(2000))、W15/50：3.60W/kg以下、B50：1.61T以上]切出宽：150mm、长：300mm的大小而成的试验片的表面。
接着，将涂布了处理液的钢板放置表1所示的放置时间。另外，调整涂布量，以使Zr含量达到表1所示的值。
放置的气氛温度为25℃。通过该放置，摩尔比(Fe/Zr)达到表1所示的值。摩尔比(Fe/Zr)的导出方法如后所述。
接着，使用热风烘烤炉，以表1所示的烘烤温度(到达钢板温度)和烘烤时间(在炉时间)对上述放置后的钢板进行烘烤。然后，将烘烤后的钢板自然冷却至常温，形成绝缘被膜。
对得到的带有绝缘被膜的电磁钢板(产品板)的被膜特性进行研究，结果示于表1。被膜特性的评价方法如下所述。进而，对于带有绝缘被膜的电磁钢板，在氮气气氛中进行750℃、2小时的去应力退火，然后通过同样的方法对去应力退火后的带有绝缘被膜的电磁钢板(退火板)的被膜特性进行研究。得到的结果示于表1。
<摩尔比(Fe/Zr)>
使用俄歇电子能谱仪(PHISICALELECTONICS(株)制)，以加速电压10keV、试样电流0.2μA进行分析。对于深度分析，以3nm/分钟的溅射速率(基于SiO2的值)，每2分钟进行测定，一直测定至Zr计数达到噪音级，算出至减半值为止的平均值。深度分析的一例示于图1。基于该分析结果，导出摩尔比(Fe/Zr)。
<耐腐蚀性>
对带有绝缘被膜的电磁钢板、去应力退火后的带有绝缘被膜的电磁钢板进行湿润试验(50℃、相对湿度≥98％)，目测观察48小时后的红锈面积率(产生红锈的面积的面积率)。基于红锈面积率，按照以下基准评价耐腐蚀性。
(判定基准)
◎：红锈面积率小于20％
○：红锈面积率为20％以上、小于40％
△：红锈面积率为40％以上、小于60％
×：红锈面积率为60％以上
<粘附性>
将玻璃纸胶带粘贴到带有绝缘被膜的电磁钢板、去应力退火后的带有绝缘被膜的电磁钢板的表面上，进行φ10mm内弯曲后，剥离玻璃纸胶带，目测观察绝缘被膜的残留状态来进行评价。评价基准如下所述。
(判定基准)
◎：残留率为90％以上
○：残留率为60％以上、小于90％
△：残留率为30％以上、小于60％
×：残留率小于30％
[表2]
[表3]
[表4]
符号 名称 化学式
P1 磷酸 H3PO4
P2 磷酸铵 (NH4)3PO4
[表5]
如表1所示，根据本发明得到的带有绝缘被膜的电磁钢板的耐腐蚀性和粘附性均优良。
与此相对，Zr化合物落在合适范围外的比较例，其耐腐蚀性、粘附性差。
此外，图2是表示在去应力退火前的带有绝缘被膜的电磁钢板中，绝缘被膜和电磁钢板的粘附性与摩尔比(Fe/Zr)的关系的图。由图2也可以确认，通过在含有Zr的绝缘被膜中含有规定量的Fe，被膜特性显著提高。

Claims (4)

1.一种带有绝缘被膜的电磁钢板，其特征在于，
具有电磁钢板和在所述电磁钢板上形成的绝缘被膜，
所述绝缘被膜含有Zr和Fe，
所述Zr的含量以ZrO2换算为0.05～1.50g/m2，
所述Zr和所述Fe的含有比例以摩尔比(绝缘被膜中的Fe量(摩尔)/绝缘被膜中的Zr量(摩尔))计为0.10～2.00。
2.根据权利要求1所述的带有绝缘被膜的电磁钢板，其特征在于，
所述绝缘被膜还含有Si，
所述Zr和所述Si的含有比例以摩尔比(绝缘被膜中的Si量(摩尔)/绝缘被膜中的Zr量(摩尔))计为2.00以下。
3.根据权利要求1或2所述的带有绝缘被膜的电磁钢板，其特征在于，
所述绝缘被膜还含有P，
所述Zr和所述P的含有比例以摩尔比(绝缘被膜中的P量(摩尔)/绝缘被膜中的Zr量(摩尔))计为1.50以下。
4.根据权利要求1～3中任一项所述的带有绝缘被膜的电磁钢板，其特征在于，
所述绝缘被膜还含有有机树脂，
所述Zr和所述有机树脂的含有比例以固体成分比率(绝缘被膜中的有机树脂的固体成分量(g)/Zr的含量(g)(ZrO2换算质量))计为0.50以下。
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