CN107923046B - 绝缘被膜处理液和带有绝缘被膜的金属的制造方法 - Google Patents

绝缘被膜处理液和带有绝缘被膜的金属的制造方法 Download PDF

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CN107923046B
CN107923046B CN201680050204.3A CN201680050204A CN107923046B CN 107923046 B CN107923046 B CN 107923046B CN 201680050204 A CN201680050204 A CN 201680050204A CN 107923046 B CN107923046 B CN 107923046B
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steel sheet
mass
insulating coating
metal
average particle
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CN107923046A (zh
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寺岛敬
末广龙一
渡边诚
高宫俊人
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JFE Steel Corp
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    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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Abstract

本发明提供一种可得到显示良好物性的绝缘被膜的绝缘被膜处理液。上述绝缘被膜处理液含有选自Mg、Ca、Ba、Sr、Zn、Al和Mn中的至少1种的磷酸盐以及平均粒径不同的2种以上的胶体二氧化硅，上述胶体二氧化硅的合计含量相对于上述磷酸盐的固体成分100质量份以SiO2固体成分换算计为50～120质量份，将上述胶体二氧化硅的平均粒径从小的一方起依次设为r1、…、rn时，由ri+1/ri表示的平均粒径比为1.5以上，将上述胶体二氧化硅的SiO2固体成分换算的质量从平均粒径小的一方起依次设为w1、…、wn时，由wi+1/(wi+1+wi)表示的质量比为0.30～0.90。其中，n表示2以上的整数，i表示1～n的整数。

Description

绝缘被膜处理液和带有绝缘被膜的金属的制造方法
技术领域
本发明涉及绝缘被膜处理液和带有绝缘被膜的金属的制造方法。
背景技术
一般来说，方向性电磁钢板(以下，也简称为“钢板”)中，为了赋予绝缘性、加工性以及防锈性等，在表面设置被膜。该表面被膜由以最终退火时形成的镁橄榄石为主体的基底被膜(镁橄榄石被膜)和其上形成的磷酸盐系的上涂层被膜构成。
应予说明，以下，在设于方向性电磁钢板的表面的被膜中，仅将后者的上涂层被膜称为“绝缘被膜”。
这些被膜在高温下形成，并且具有低的热膨胀率，因此由于降低到室温时的钢板与被膜的热膨胀率之差而对钢板赋予张力，具有降低钢板的铁损的效果。因此，要求被膜对钢板赋予尽可能高的张力。
例如，专利文献1～2中公开了一种由含有磷酸盐和1种胶体二氧化硅或粒径不同的2种以上的胶体二氧化硅的处理液形成的绝缘被膜。应予说明，以下，有时将带有绝缘被膜的方向性电磁钢板也简称为“方向性电磁钢板”或“钢板”。
现有技术文献
专利文献
专利文献1：日本特开平3－39484号公报
专利文献2：日本特开平8－277475号公报
发明内容
本发明人等在完成最终退火的方向性电磁钢板(即，形成有镁橄榄石被膜的方向性电磁钢板)的表面上形成专利文献1～2中记载的绝缘被膜，结果发现有降低铁损的效果不充分的情况。
另外，绝缘被膜也可以应用于形成有镁橄榄石被膜的方向性电磁钢板以外的金属(例如，未形成镁橄榄石被膜的方向性电磁钢板、无方向性电磁钢板等)，这时，可期待例如绝缘性、密合性等基本物性的发挥，但本发明人等发现专利文献1～2中记载的绝缘被膜中这些基本物性也有不充分的情况。
本发明是鉴于以上问题而完成的，其目的在于提供一种可得到显示良好的物性的绝缘被膜的绝缘被膜处理液、以及使用上述绝缘被膜处理液的带有绝缘被膜的金属的制造方法。
应予说明，这里，“物性”是指在形成有镁橄榄石被膜的方向性电磁钢板的表面上形成绝缘被膜的情况下，降低铁损的性能，在其以外的金属的表面上形成时，表示绝缘性和密合性。
本发明人等为了实现上述目的而进行了深入研究，其结果发现，通过以特定的组成配合平均粒径不同的2种以上的胶体二氧化硅，可得到优异的物性，从而完成了本发明。
即，本发明提供以下的(1)～(6)。
(1)一种绝缘被膜处理液，是在金属的表面上形成绝缘被膜的绝缘被膜处理液，其含有选自Mg、Ca、Ba、Sr、Zn、Al和Mn中的至少1种的磷酸盐以及平均粒径不同的2种以上的胶体二氧化硅，上述胶体二氧化硅的合计含量相对于上述磷酸盐的固体成分100质量份以SiO2固体成分换算计为50～120质量份，将上述胶体二氧化硅的平均粒径从小的一方起依次设为r1、…、rn时，由ri+1/ri表示的平均粒径比为1.5以上，将上述胶体二氧化硅的SiO2固体成分换算的质量从平均粒径小的一方起依次设为w1、…、wn时，由wi+1/(wi+1+wi)表示的质量比为0.30～0.90。其中，n表示2以上的整数，i表示1～n的整数。
(2)根据上述(1)所述的绝缘被膜处理液，其中，将选自Ti、V、Cr、Mn、Fe和Zr中的至少1种设为M时，进一步含有M化合物，上述M化合物的含量相对于上述磷酸盐100质量份以氧化物换算计为5～40质量份。
(3)一种带有绝缘被膜的金属的制造方法，其中，在金属的表面上涂布上述(1)或(2)所述的绝缘被膜处理液后，在800～1000℃实施10～300秒的煅烧，得到带有绝缘被膜的金属。
(4)根据上述(3)所述的带有绝缘被膜的金属的制造方法，其中，上述金属为薄钢板。
(5)根据上述(4)所述的带有绝缘被膜的金属的制造方法，其中，上述薄钢板为电磁钢板。
(6)根据上述(5)所述的带有绝缘被膜的金属的制造方法，其中，上述电磁钢板为完成最终退火的方向性电磁钢板。
根据本发明，能够提供一种可得到显示良好的物性的绝缘被膜的绝缘被膜处理液、以及使用上述绝缘被膜处理液的带有绝缘被膜的金属的制造方法。
附图说明
图1是表示平均粒径不同的胶体二氧化硅的固体成分换算的质量比(w2/(w2+w1))与对钢板的赋予张力的关系的图(r1：8.5nm(AT－300s)，r2：26.1nm(AT－50))。
具体实施方式
[实验结果]
最初对作为本发明的基础的实验结果进行说明。
首先，以下述方式制作试样。
将由公知的方法制造的板厚：0.27mm的完成最终退火的方向性电磁钢板剪切为300mm×100mm的大小，除去未反应的退火分离剂后，实施去应力退火(800℃，2小时)。
用5％磷酸对该钢板进行轻微酸洗后，以干燥后的单位面积重量为两面合计8.0g/m2的方式涂布接下来的绝缘被膜处理液(以下，也简称为“处理液”)。
处理液是按使磷酸二氢镁水溶液以固体成分换算计为100质量份、使平均粒径不同的胶体二氧化硅以固体成分换算计合计为100质量份、使CrO3以固体成分换算计为16.7质量份的比例配合而进行制备。这时，使用平均粒径8.5nm(r1)的胶体二氧化硅(ADEKA公司制的AT－300s，比重：1.21g/mL，SiO2：30.4质量％，Na2O：0.53质量％)和平均粒径26.1nm(r2)的胶体二氧化硅(ADEKA公司制的AT－50，比重：1.38g/mL，SiO2：48.4质量％，Na2O：0.25质量％)(r2/r1＝3.1)，以平均粒径不同的胶体二氧化硅的固体成分换算的质量比(w2/(w2+w1))成为下述表1所记载的数值的方式进行混合。
应予说明，w1表示平均粒径8.5nm(r1)的胶体二氧化硅的质量份，w2表示平均粒径26.1nm(r2)的胶体二氧化硅的质量份，均表示相对于磷酸盐的固体成分100质量份的质量份(固体成分换算)。
接下来，将涂布有处理液的钢板装入干燥炉中(300℃，1分钟)，其后，实施兼具平坦化退火和绝缘被膜的煅烧的热处理(800℃，2分钟，N2：100％)。进而，其后实施去应力退火(800℃，2小时)。
对以这种方式制成的试样评价对钢板的赋予张力、铁损降低效果、以及耐水性。
铁损降低效果根据用SST试验机(单板磁力试验机)测定的磁特性进行评价。磁测定是在即将涂布处理液之前、刚煅烧绝缘被膜之后和刚进行去应力退火之后对各试样进行(后述的[实施例]中也同样)。
耐水性通过磷的溶出试验进行评价。该试验是通过从刚煅烧绝缘被膜之后的钢板切下3张50mm×50mm的试验片，将切下的试验片在100℃的蒸馏水中沸腾5分钟，从而使磷从绝缘被膜的表面溶出，根据其溶出量[μg/150cm2]判断绝缘被膜在水中的溶解的容易性。磷的溶出量越少，可以评价为耐水性越优异(后述的[实施例]中也同样)。
下述表1中示出对钢板的赋予张力、磁特性以及磷溶出量的测定结果等。另外，将平均粒径不同的胶体二氧化硅的固体成分换算的质量比(w2/(w2+w1))与对钢板的赋予张力的关系示于图1。
应予说明，下述表1中的各项目如下。
·赋予张力：设为轧制方向的张力，使用碱、酸等剥离单面的绝缘被膜后的钢板的翘曲量使用下述式(1)计算。
对钢板的赋予张力[MPa]＝钢板杨氏模量[GPa]×板厚[mm]×翘曲量[mm]÷(翘曲测定长度[mm])2×103···式(1)
其中，钢板杨氏模量为132GPa。
·B8(R)：涂布处理液前的磁通密度[T]
·涂布后△B＝B8(C)－B8(R)
(其中，B8(C)：绝缘被膜的煅烧后的磁通密度[T])
·去应力退火后△B＝B8(A)－B8(R)
(其中，B8(A)：去应力退火后的磁通密度[T])
·W17/50(R)：涂布处理液前的铁损[W/kg]
·涂布后△W＝W17/50(C)－W17/50(R)
(其中，W17/50(C)：绝缘被膜的煅烧后的铁损[W/kg])
·去应力退火后△W＝W17/50(A)－W17/50(R)
(其中，W17/50(A)：去应力退火后的铁损[W/kg])
·磷溶出量：在绝缘被膜的煅烧后测定
Figure BDA0001584526380000051
由上述表1所示的结果可明确，混合使用平均粒径不同的胶体二氧化硅时(试样No.2～10)，任意质量比中，对钢板的赋予张力都大于未混合时(试样No.1和11)的单纯平均。
特别是在质量比为0.30～0.90的范围(试样No.4～10)，磁特性和耐水性良好，在质量比为0.50～0.80的范围(试样No.6～9)，这些特性更加良好。
本发明人等以下述方式考察上述试验结果。
以往，认为磷酸盐和胶体二氧化硅在煅烧时发生反应而一体化。在这种情况下，认为胶体二氧化硅的粒径、混合比对一体化不造成影响，但上述试验结果显示并非如此。假定不是胶体二氧化硅完全反应而一体化的模型，而是胶体二氧化硅在保持为某种程度形状的状态下分散在磷酸盐中的模型。认为如果假定这样的模型，则与组合大石和小石而建造坚固的石墙同样，胶体二氧化硅的平均粒径比和混合比影响胶体二氧化硅的填充率，进而，产生使绝缘被膜的物性发生改变的结果。
接下来，对本发明的绝缘被膜处理液进行了说明后，接着，对本发明的带有绝缘被膜的金属的制造方法进行说明。
[绝缘被膜处理液]
本发明的绝缘被膜处理液(以下，也简称为“本发明的处理液”)是在金属的表面上形成绝缘被膜的绝缘被膜处理液，概略地说，是含有选自Mg、Ca、Ba、Sr、Zn、Al和Mn中的至少1种的磷酸盐以及平均粒径不同的2种以上的胶体二氧化硅的绝缘被膜处理液。
而且，本发明的处理液中，通过使胶体二氧化硅采用后述的特定的组成，胶体二氧化硅的填充率提高，得到的绝缘被膜的物性优异。
具体而言，在应用于形成有镁橄榄石被膜的方向性电磁钢板时，对钢板的赋予张力提高，降低铁损的效果优异，在应用于其以外的金属时，绝缘性和密合性等物性优异。
以下，对本发明的处理液含有的各成分等的详细内容进行说明。
<磷酸盐〉
作为本发明的处理液中含有的磷酸盐的金属种，只要是选自Mg、Ca、Ba、Sr、Zn、Al以及Mn中的至少1种，就没有特别限定。应予说明，碱金属(Li、Na等)的磷酸盐因得到的绝缘被膜的耐水性明显差而不适合。
磷酸盐可以单独使用1种，也可以并用2种以上。通过并用2种以上，能够精确地控制得到的绝缘被膜的物性值。
作为这样的磷酸盐，从获得容易性的观点考虑，优选举出磷酸二氢盐(磷酸氢盐)。
<胶体二氧化硅〉
本发明的处理液中，混合地含有平均粒径不同的2种以上的胶体二氧化硅。应予说明，混合前的胶体二氧化硅在控制混合比的方面优选为单分散。另外，胶体二氧化硅的粒子形状为针状，板状，立方体等形状时，不易得到本发明的效果，因此优选为接近球状的形状，更优选为球状。
另外，胶体二氧化硅的液体中的Na浓度高时，由于绝缘被膜的玻璃化转变温度的降低、热膨胀系数的增大，有时在钢板上形成绝缘被膜时的赋予张力降低。因此，相对于胶体二氧化硅的总质量的Na浓度以Na2O换算计优选为1.0质量％以下。
(含量)
本发明的处理液中，胶体二氧化硅含量相对于磷酸盐的固体成分100质量份，以SiO2固体成分换算计为50～120质量份，优选为50～100质量份，更优选为60～100质量份。
如果胶体二氧化硅的含量过少，则有时绝缘被膜的热膨胀系数降低的效果变小，而对钢板赋予的张力降低。另一方面，如果胶体二氧化硅的含量过多，则在后述的煅烧时绝缘被膜的结晶化变得容易进行，仍然有时对钢板赋予的张力降低，并且有时耐水性也差。
然而，如果胶体二氧化硅的含量在上述范围内，则由绝缘被膜对钢板赋予适度的张力，铁损的改善效果优异。另外，绝缘被膜的耐水性也优异。
(粒径比)
本发明的处理液中，将胶体二氧化硅的平均粒径从小的一方起依次设为r1、…、rn时，由ri+1/ri表示的平均粒径比(以下，也简称为“粒径比”)为1.5以上(其中，n表示2以上的整数，i表示1～n的整数)。应予说明，n优选为10以下的整数，更优选为5以下的整数。
通过使粒径比为1.5以上，胶体二氧化硅的填充率提高，绝缘被膜的物性优异。从该效果更优异的理由出发，粒径比优选为1.9以上。
应予说明，粒径比的上限没有特别限定，如果胶体二氧化硅的粒径极小或者极大，则一般而言制造成本变高，进而，绝缘被膜的成本变高，因此从成本的观点考虑，粒径比优选为50以下，更优选为25以下。
(质量比)
本发明的处理液中，将胶体二氧化硅的SiO2固体成分换算的质量从平均粒径小的一方起依次设为w1、…、wn时，由wi+1/(wi+1+wi)表示的质量比(以下，也简称为“质量比”)为0.30～0.90(其中，n表示2以上的整数，i表示1～n的整数)。应予说明，n优选为10以下的整数，更优选为5以下的整数。
质量比为0.30～0.90的范围外的情况下，粒径小或者大的胶体二氧化硅的量过多，胶体二氧化硅的填充率的提高不充分，但如果质量比为0.30～0.90的范围内，则胶体二氧化硅的填充率提高，绝缘被膜的物性优异。从该效果更优异的理由出发，质量比优选为0.50～0.80。
(平均粒径)
应予说明，胶体二氧化硅的平均粒径是指中值径(50％直径)，例如使用激光衍射法、动态光散射法等测定。
胶体二氧化硅的平均粒径只要满足上述粒径比，就没有特别限定，从抑制成本的观点考虑，胶体二氧化硅均优选为1.0～150nm，更优选为4.0～100nm。
另外，从造膜性等的观点考虑，最小的粒径(r1)优选为1.0～60nm，进一步优选为1.0～30nm。
<M化合物〉
将选自Ti、V、Cr、Mn、Fe以及Zr中的至少1种设为“M”时，从得到的绝缘被膜的耐水性(防止因吸湿所致的发粘)的观点考虑，本发明的处理液也可以进一步含有M化合物。
此时，M化合物的含量相对于磷酸盐100质量份以氧化物换算计优选为5～40质量份，更优选为10～30质量份。如果M化合物的含量在该范围，则除了绝缘被膜的耐水性优异以外，绝缘被膜赋予到钢板的张力提高而铁损的改善效果也优异。
应予说明，M化合物的含量中的“氧化物换算”具体按每个M的金属种列举时，如下所示。
Ti：TiO2换算，V：V2O5换算，Cr：CrO3换算，Mn：MnO换算，Fe：FeO换算，Zr：ZrO2换算
作为在本发明的处理液中添加时的M化合物的形态，没有特别限定，从处理液的稳定性的观点考虑，优选以水溶性的化合物(金属盐)或氧化物溶胶的形态含有。
作为Ti化合物，例如，可举出TiO2溶胶、Ti螯合物、磷酸Ti溶胶等。
作为V化合物，例如，可举出NH4VO3、VOSO4等。
作为Cr化合物，例如，可举出铬酸化合物，作为其具体例，可举出三氧化铬(CrO3)、铬酸盐、重铬酸盐等。
作为Mn化合物，例如，可举出MnCO3、MnSO4、Mn(OH)2等。
作为Fe化合物，例如，可举出FeO(OH)溶胶等。
作为Zr化合物，例如，可举出ZrO2溶胶等。
作为这样的M化合物，可以单独使用1种，也可以并用2种以上。
<无机矿物粒子〉
从使得到的绝缘被膜的抗粘性良好的观点考虑，本发明的处理液可以进一步含有例如二氧化硅、氧化铝等无机矿物粒子。
但是，为了不使占积率降低，无机矿物粒子的含量相对于胶体二氧化硅20质量份优选为1质量份以下。
<处理液的制造等〉
本发明的处理液的制造可以利用公知的条件和方法进行。例如，本发明的处理液通过将上述的各成分混合而制造。
将本发明的处理液涂布在薄钢板等金属的表面上，实施干燥、煅烧等，从而在金属的表面上形成绝缘被膜。
应用本发明的处理液而形成绝缘被膜的金属(被绝缘处理材料)主要是完成最终退火的方向性电磁钢板(形成有镁橄榄石被膜的方向性电磁钢板)，也可以应用于其以外的金属，例如，形成有镁橄榄石被膜的方向性电磁钢板、无方向性电磁钢板、冷轧钢板、其他的一般的薄钢板等。
[带有绝缘被膜的金属的制造方法]
本发明的带有绝缘被膜的金属的制造方法是在金属的表面上涂布本发明的处理液后，在800～1000℃实施10～300秒的煅烧，得到带有绝缘被膜的金属的带有绝缘被膜的金属的制造方法。
<金属〉
如上所述，涂布有本发明的处理液的金属(被绝缘处理材料)例如为薄钢板，作为其具体例，可举出完成最终退火的方向性电磁钢板(形成有镁橄榄石被膜的方向性电磁钢板)；未形成镁橄榄石被膜的方向性电磁钢板；无方向性电磁钢板；冷轧钢板等，其中，优选为电磁钢板，更优选为方向性电磁钢板。
作为方向性电磁钢板，没有特别限定，可以使用以往公知的方向性电磁钢板。通常，方向性电磁钢板通过如下方式制造：将含硅钢坯用公知的方法进行热轧，通过1次或者隔着中间退火的多次的冷轧精加工成最终板厚后，实施一次再结晶退火，接着，涂布退火分离剂后进行最终退火。以这种方式得到形成有镁橄榄石被膜的方向性电磁钢板。
应予说明，最终退火后，通过酸洗等将镁橄榄石被膜除去，从而能够得到没有镁橄榄石被膜的方向性电磁钢板。
<处理液的涂布〉
作为本发明的处理液的涂布方法，没有特别限定，可以使用以往公知的方法。
涂布有本发明的处理液的金属为板状时，本发明的处理液优选涂布在该金属的两面，更优选以煅烧后(进行后述的干燥的情况下，干燥和煅烧后)的单位面积重量以两面合计为4～15g/m2的方式进行涂布。这是因为如果该量过少，则有时层间阻力降低，过多时，有时占积率的降低变大。
<干燥〉
接下来，优选进行涂布有本发明的处理液的金属的干燥。具体而言，干燥例如可举出将涂布有处理液的金属装入干燥炉中，在150～450℃进行0.25～2分钟的干燥，但不限于此。
<煅烧〉
接下来，对涂布本发明的处理液且任意干燥的金属实施煅烧，由此，形成绝缘被膜。
此时，从兼具平坦化退火的观点考虑，优选在800～1000℃实施10～300秒的煅烧。如果煅烧温度过低或者煅烧时间过短，则有时平坦化不充分，形状不良，成品率降低，另一方面，煅烧温度过高时，有时平坦化退火的效果过强而蠕变变形，磁特性容易劣化，只要是上述条件，则平坦化退火的效果变得充分且适度。
实施例
以下，举出实施例对本发明进行具体说明。但是，本发明不限于这些。
[实验例1]
准备板厚：0.27mm的完成最终退火的方向性电磁钢板(磁通密度B8：1.912T)，将该方向性电磁钢板切成100mm×300mm的大小，用5质量％磷酸进行酸洗。其后，将按下述表2所示的组成配合的绝缘被膜处理液以干燥和煅烧后的单位面积重量为两面合计10g/m2的方式进行涂布后，装入干燥炉中，在300℃实施1分钟的干燥，其后，在850℃、30秒、N2100％气氛的条件下实施煅烧，其后，在800℃、2小时、N2100％气氛的条件下实施去应力退火，制造带有绝缘被膜的方向性电磁钢板。
应予说明，均使用磷酸二氢盐水溶液作为磷酸盐，下述表2中记载了经固体成分换算的量。
另外，作为胶体二氧化硅，使用以下市售品。
·AT－300s(平均粒径：8.5nm，ADEKA公司制)
·AT－30(平均粒径：14.1nm，ADEKA公司制)
·AT－50(平均粒径：26.1nm，ADEKA公司制)
·SNOWTEX XS(平均粒径：4.0nm，日产化学工业公司制)
·SNOWTEX 50(平均粒径：22.5nm，日产化学工业公司制)
·SNOWTEX 30L(平均粒径：47.4nm，日产化学工业公司制)
·SNOWTEX ZL(平均粒径：100nm，日产化学工业公司制)
·MP－1040(平均粒径：130nm，日产化学工业公司制)
·MP－4540M(平均粒径：410nm，日产化学工业公司制)
Figure BDA0001584526380000121
对以这种方式得到的带有绝缘被膜的方向性电磁钢板的各特性进行评价。将结果示于下述表3。应予说明，各特性的评价以下述方式进行。
·赋予张力：设为轧制方向的张力，由使用碱、酸等将单面的绝缘被膜剥离后的钢板的翘曲量，使用下述式(1)算出。
对钢板的赋予张力[MPa]＝钢板杨氏模量[GPa]×板厚[mm]×翘曲量[mm]÷(翘曲测定长度[mm])2×103···式(1)
其中，钢板杨氏模量为132GPa。
·W17/50(R)：涂布处理液前的铁损[W/kg]
·涂布后△W＝W17/50(C)－W17/50(R)
(其中，W17/50(C)：绝缘被膜的煅烧后的铁损[W/kg])
·去应力退火后△W＝W17/50(A)－W17/50(R)
(其中，W17/50(A)：去应力退火后的铁损[W/kg])
·磷溶出量：在绝缘被膜的煅烧后测定
表3
Figure BDA0001584526380000131
由上述表2和表3所示的结果可明确，胶体二氧化硅的含量相对于磷酸盐100质量份以SiO2固体成分换算计为50～120质量份的范围内、粒径比均为1.5、并且质量比均为0.30～0.90的范围内的发明例与偏离上述条件中的至少一个的比较例相比，对钢板的赋予张力高，铁损的降低效果良好。另外，耐水性也良好。
[实验例2]
准备板厚：0.23mm的完成最终退火的方向性电磁钢板(磁通密度B8：1.912T)，将该方向性电磁钢板切成100mm×300mm的大小，用5质量％磷酸进行酸洗。其后，将按下述表4所示的组成配合的绝缘被膜处理液以干燥和煅烧后的单位面积重量为两面合计15g/m2的方式进行涂布后，装入干燥炉中，在300℃实施1分钟的干燥，其后，在950℃、10秒、N2100％气氛的条件下实施煅烧，其后，在800℃、2小时、N2100％气氛的条件下实施去应力退火，制造带有绝缘被膜的方向性电磁钢板。
下述表4所示的No.1～No.13的绝缘被膜处理液是以上述[实验例1]的表2中示出的No.13作为基本组成，进一步添加了M化合物。
同样地，下述表4所示的No.14～No.20的绝缘被膜处理液是以上述[实验例1]的表2示出的No.14作为基本组成，进一步添加了M化合物。
M化合物使用作为Ti化合物的TiO2溶胶、作为V化合物的NH4VO3、作为Cr化合物的CrO3、作为Mn化合物的MnCO3、作为Fe化合物的FeO(OH)溶胶、作为Zr化合物的ZrO2溶胶。
Figure BDA0001584526380000151
对以这种方式得到的带有绝缘被膜的方向性电磁钢板的各特性进行评价。将结果示于下述表5。应予说明，各特性的评价如下进行。
·赋予张力：设为轧制方向的张力，由使用碱、酸等将单面的绝缘被膜剥离后的钢板的翘曲量使用下述式(1)算出。
对钢板的赋予张力[MPa]＝钢板杨氏模量[GPa]×板厚[mm]×翘曲量[mm]÷(翘曲测定长度[mm])2×103···式(1)
其中，钢板杨氏模量为132GPa。
·W17/50(R)：涂布处理液前的铁损[W/kg]
·涂布后△W＝W17/50(C)－W17/50(R)
(其中，W17/50(C)：绝缘被膜的煅烧后的铁损[W/kg])
·去应力退火后△W＝W17/50(A)－W17/50(R)
(其中，W17/50(A)：去应力退火后的铁损[W/kg])
·磷溶出量：在绝缘被膜的煅烧后测定
表5
Figure BDA0001584526380000161
由上述表4和表5所示的结果可明确知道，通过在相对于磷酸盐100质量份以氧化物换算计为5～40质量份的范围配合M化合物，耐水性显著提高。
[实验例3]
接下来，为了确认除了带有镁橄榄石被膜的方向性电磁钢板(完成最终退火的方向性电磁钢板)以外，还可以应用由本发明的处理液得到的绝缘被膜，准备下述5种金属A～E作为被绝缘处理材料。
·A：未附有镁橄榄石被膜的方向性电磁钢板
准备板厚：0.23mm的完成最终退火的方向性电磁钢板(磁通密度B8：1.912T)，将在该方向性电磁钢板的表面形成的镁橄榄石被膜使用90℃的HCl－HF混酸除去后，再使用冷却到10℃的H2O2－HF混酸进行化学研磨，将表面精加工成镜面状。
·B：无方向性电磁钢板
在没有绝缘被膜的状态下准备杰富意钢铁公司制的35JNE300。
·C：不锈钢钢板
杰富意钢铁公司制的铁素体系不锈钢JFE430XT 0.5mm厚
·D：冷轧钢板
与SPCC相当的杰富意钢铁公司制的JFE－CC 0.5mm厚
·E：铝
JIS H 4000A5052P 0.5mm厚
将表2所示的No.1、No.3、No.5、No.13、No.14和No.19以及表4所示的No.6和No.20的绝缘被膜处理液以干燥和煅烧后的单位面积重量为两面合计4g/m2的方式涂布在上述5种金属的表面后，装入干燥炉中，在300℃实施1分钟的干燥，其后，在800℃、10秒、N2100％气氛的条件下实施煅烧，其后，在800℃、2小时、N2100％气氛的条件下实施去应力退火，制造在金属表面形成有绝缘被膜的试验材料。
对以这种方式得到的试验材料评价绝缘被膜的绝缘性和绝缘被膜与金属的密合性。将结果示于下述表6。应予说明，各特性的评价如下进行。
·绝缘性：根据JIS C 2550－4所记载的表面电阻的测定方法试验来测定电流值(富兰克林电流值)。如果测定的电流值为0.2A以下，则可以评价为绝缘性优异。
·密合性：用JIS K 5600－5－6的横切法评价密合性。作为粘合胶带，使用Cellotape(注册商标)CT－18(粘合力：4.01N/10mm)。将2mm见方的格子中剥离下来的格子的个数(剥离数)记载于下述表6。如果剥离数为3个以下，则可以评价为密合性优异。
Figure BDA0001584526380000181
由上述表6所示的结果可明确知道，即使将胶体二氧化硅的含量相对于磷酸盐100质量份以SiO2固体成分换算计为50～120质量份的范围内、粒径比均为1.5、并且质量比均为0.30～0.90的范围内的绝缘被膜处理液应用于具有镁橄榄石被膜的方向性电磁钢板以外的金属时，绝缘性、密合性等各特性也优异。

Claims (6)

1.一种绝缘被膜处理液，是在金属的表面上形成绝缘被膜的绝缘被膜处理液，
其含有选自Mg、Ca、Ba、Sr、Zn、Al和Mn中的至少1种的磷酸盐以及平均粒径不同的2种以上的胶体二氧化硅，
所述胶体二氧化硅的合计含量相对于所述磷酸盐的固体成分100质量份以SiO2固体成分换算计为50～120质量份，
将所述胶体二氧化硅的平均粒径从小的一方起依次设为r1、…、rn时，由ri+1/ri表示的平均粒径比为1.9以上，
将所述胶体二氧化硅的SiO2固体成分换算的质量从平均粒径小的一方起依次设为w1、…、wn时，由wi+1/(wi+1+wi)表示的质量比为0.50～0.80，
其中，n表示2以上的整数，i表示1～n的整数。
2.根据权利要求1所述的绝缘被膜处理液，其中，
将选自Ti、V、Cr、Mn、Fe和Zr中的至少1种设为M时，
进一步含有M化合物，
所述M化合物的含量相对于所述磷酸盐100质量份以氧化物换算计为5～40质量份。
3.一种带有绝缘被膜的金属的制造方法，其中，在金属的表面上涂布权利要求1或2所述的绝缘被膜处理液后，在800～1000℃实施10～300秒的煅烧，得到带有绝缘被膜的金属。
4.根据权利要求3所述的带有绝缘被膜的金属的制造方法，其中，所述金属为薄钢板。
5.根据权利要求4所述的带有绝缘被膜的金属的制造方法，其中，所述薄钢板为电磁钢板。
6.根据权利要求5所述的带有绝缘被膜的金属的制造方法，其中，所述电磁钢板为完成最终退火的方向性电磁钢板。
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Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10087529B2 (en) * 2014-01-31 2018-10-02 Jfe Steel Corporation Treatment solution for chromium-free tension coating, method for forming chromium-free tension coating, and grain oriented electrical steel sheet with chromium-free tension coating
PL3358041T3 (pl) * 2015-09-29 2021-09-06 Nippon Steel Corporation Blacha cienka ze stali elektrotechnicznej o ziarnach zorientowanych i sposób wytwarzania blachy cienkiej ze stali elektrotechnicznej o ziarnach zorientowanych
JP6642782B1 (ja) * 2018-08-17 2020-02-12 Ｊｆｅスチール株式会社 絶縁被膜形成用処理液の製造方法および絶縁被膜付き鋼板の製造方法ならびに絶縁被膜形成用処理液の製造装置
KR20220101684A (ko) * 2019-11-21 2022-07-19 닛폰세이테츠 가부시키가이샤 무방향성 전자 강판 및 그 제조 방법
CN115151681A (zh) * 2020-02-28 2022-10-04 杰富意钢铁株式会社 带绝缘被膜的方向性电磁钢板和其制造方法
CN113053651A (zh) * 2021-03-24 2021-06-29 福建尚辉润德新材料科技有限公司 一种软磁复合材料的制备方法及软磁复合材料
WO2024096761A1 (en) * 2022-10-31 2024-05-10 Public Joint-stock Company "Novolipetsk Steel" An electrical insulating coating сomposition providing high commercial properties to grain oriented electrical steel

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1258542A2 (de) * 2001-05-18 2002-11-20 Robert Bosch Gmbh Funktionsbeschichtung und Verfahren zu deren Erzeugug, insbesondere zum Verschleissschutz, Korrosionsschutz oder zur Temperaturisolation
WO2003104160A1 (de) * 2002-06-05 2003-12-18 Van Baerle & Cie Ag Werkstoff umfassend cellulosisches material und silikat
JP2004190068A (ja) * 2002-12-09 2004-07-08 Kobe Steel Ltd 耐食性亜鉛めっき鋼板、その製造方法、及び、そのりん酸塩処理皮膜のシーリング処理組成物
CN101223300A (zh) * 2005-07-14 2008-07-16 新日本制铁株式会社 具有不含铬的绝缘皮膜的取向电磁钢板及其绝缘皮膜剂
CN101591495A (zh) * 2009-07-03 2009-12-02 首钢总公司 一种无取向电工钢无铬绝缘环保涂料及其涂层的制备方法
CN101790599A (zh) * 2007-08-30 2010-07-28 杰富意钢铁株式会社 方向性电磁钢板用绝缘覆膜处理液以及具有绝缘覆膜的方向性电磁钢板的制造方法
CN102115881A (zh) * 2010-12-27 2011-07-06 上海迪升防腐新材料科技有限公司 一种无取向硅钢用环保绝缘涂层溶液及其制备和应用
CN102782185A (zh) * 2010-02-18 2012-11-14 新日本制铁株式会社 无方向性电磁钢板及其制造方法

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6141778A (ja) * 1984-08-02 1986-02-28 Nippon Steel Corp 張力付加性およびスベリ性の優れた方向性電磁鋼板の絶縁皮膜形成方法
JP2709515B2 (ja) 1989-07-05 1998-02-04 新日本製鐵株式会社 鉄心の加工性および耐熱性の優れる方向性電磁鋼板の絶縁皮膜形成方法
CN1039915C (zh) * 1989-07-05 1998-09-23 新日本制铁株式会社 方向性电磁钢板上的绝缘皮膜成型方法
JP2698526B2 (ja) * 1992-06-30 1998-01-19 川崎製鉄株式会社 磁気特性と表面性状の優れた方向性電磁鋼板の製造方法
JP3071663B2 (ja) * 1995-04-06 2000-07-31 新日本製鐵株式会社 ぬれ性の優れた一方向性電磁鋼板の絶縁被膜形成方法
JPH09241859A (ja) * 1996-03-11 1997-09-16 Kawasaki Steel Corp 耐クロム溶出性および耐ブリスター性に優れた有機複合被覆鋼板
JPH101779A (ja) * 1996-06-13 1998-01-06 Nippon Steel Corp 高張力絶縁皮膜形成剤及びその形成方法ならびに高張力絶縁皮膜を有する方向性電磁鋼板
JP3379061B2 (ja) * 1997-08-28 2003-02-17 新日本製鐵株式会社 高張力絶縁被膜を有する方向性電磁鋼板とその処理方法
JP4940510B2 (ja) * 2001-06-27 2012-05-30 Ｊｆｅスチール株式会社 耐食性に優れた表面処理鋼板の製造方法
AU2003300475B2 (en) * 2003-01-10 2009-07-16 Henkel Ag & Co. Kgaa A coating composition
JP4461861B2 (ja) * 2004-03-19 2010-05-12 Ｊｆｅスチール株式会社 クロムフリー絶縁被膜付き電磁鋼板
EP2302095B1 (en) * 2008-06-20 2018-04-04 Nippon Steel & Sumitomo Metal Corporation Non-oriented electrical steel sheet and manufacturing method thereof
JP5589639B2 (ja) * 2010-07-22 2014-09-17 Ｊｆｅスチール株式会社 半有機絶縁被膜付き電磁鋼板
JP5846113B2 (ja) * 2011-12-28 2016-01-20 Ｊｆｅスチール株式会社 耐デント性に優れた高強度薄鋼板およびその製造方法
EP2954095B1 (en) * 2013-02-08 2023-05-24 Thyssenkrupp Electrical Steel Gmbh Solution for forming insulation coating and grain-oriented electrical steel sheet
JP6119627B2 (ja) * 2014-02-05 2017-04-26 Ｊｆｅスチール株式会社 比例限の高い高強度冷延薄鋼板およびその製造方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1258542A2 (de) * 2001-05-18 2002-11-20 Robert Bosch Gmbh Funktionsbeschichtung und Verfahren zu deren Erzeugug, insbesondere zum Verschleissschutz, Korrosionsschutz oder zur Temperaturisolation
WO2003104160A1 (de) * 2002-06-05 2003-12-18 Van Baerle & Cie Ag Werkstoff umfassend cellulosisches material und silikat
JP2004190068A (ja) * 2002-12-09 2004-07-08 Kobe Steel Ltd 耐食性亜鉛めっき鋼板、その製造方法、及び、そのりん酸塩処理皮膜のシーリング処理組成物
CN101223300A (zh) * 2005-07-14 2008-07-16 新日本制铁株式会社 具有不含铬的绝缘皮膜的取向电磁钢板及其绝缘皮膜剂
CN101790599A (zh) * 2007-08-30 2010-07-28 杰富意钢铁株式会社 方向性电磁钢板用绝缘覆膜处理液以及具有绝缘覆膜的方向性电磁钢板的制造方法
CN101591495A (zh) * 2009-07-03 2009-12-02 首钢总公司 一种无取向电工钢无铬绝缘环保涂料及其涂层的制备方法
CN102782185A (zh) * 2010-02-18 2012-11-14 新日本制铁株式会社 无方向性电磁钢板及其制造方法
CN102115881A (zh) * 2010-12-27 2011-07-06 上海迪升防腐新材料科技有限公司 一种无取向硅钢用环保绝缘涂层溶液及其制备和应用

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