TW201504455A - 帶絕緣覆膜的電磁鋼板 - Google Patents

帶絕緣覆膜的電磁鋼板 Download PDF

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TW201504455A
TW201504455A TW103117702A TW103117702A TW201504455A TW 201504455 A TW201504455 A TW 201504455A TW 103117702 A TW103117702 A TW 103117702A TW 103117702 A TW103117702 A TW 103117702A TW 201504455 A TW201504455 A TW 201504455A
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insulating film
steel sheet
electromagnetic steel
amount
ratio
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TW103117702A
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TWI504755B (zh
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Kazumichi Sashi
Naoki Muramatsu
Nobue Fujibayashi
Takahiro Kubota
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Jfe Steel Corp
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    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
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Abstract

本發明提供一種耐腐蝕性、密接性優異的帶絕緣覆膜的電磁鋼板。本發明的帶絕緣覆膜的電磁鋼板包括電磁鋼板、以及形成於電磁鋼板上的絕緣覆膜，且絕緣覆膜含有Zr及Fe，Zr的含量以ZrO2換算為0.05g/m2~1.50g/m2，Zr及Fe的含有比例以莫耳比(絕緣覆膜中的Fe量(莫耳)/絕緣覆膜中的Zr量(莫耳))計為0.10~2.00。絕緣覆膜進而含有Si，且Zr及Si的含有比例以莫耳比(絕緣覆膜中的Si的量(莫耳)/絕緣覆膜中的Zr的量(莫耳))計較佳為2.00以下。

Description

帶絕緣覆膜的電磁鋼板
本發明是有關於一種耐腐蝕性、密接性優異的帶絕緣覆膜的電磁鋼板。
對於形成於馬達或變壓器等中所使用的電磁鋼板上的絕緣覆膜而言，不僅要求層間電阻特性，且要求加工成形時的便利性及保管、使用時的穩定性等各種特性。而且，對形成於電磁鋼板上的絕緣覆膜所要求的特性，根據用途而相異，因而根據用途而開發出各種絕緣覆膜。
且說，通常在使用電磁鋼板來製造製品時，對電磁鋼板實施衝壓加工、剪切加工、彎曲加工等。若對電磁鋼板實施該些加工，則有時會因殘留應力而導致磁特性劣化。為了消除該磁特性的劣化，多數情況下以700℃~800℃左右的溫度進行去應力退火。在進行去應力退火時，要求絕緣覆膜具有可經受得住去應力退火時的熱的程度的耐熱性。
而且，形成於電磁鋼板上的絕緣覆膜可分為以下3種。
(1)重視焊接性、耐熱性且經受得住去應力退火的無 機覆膜。
(2)目的在於同時實現衝壓性、焊接性且經受得住去應力退火的含有樹脂的無機覆膜(亦即，半有機覆膜)。
(3)特殊用途下無法進行去應力退火的有機覆膜。
作為通用品，經受得住去應力退火的熱的絕緣覆膜為所述(1)、(2)所示的絕緣覆膜。作為該些絕緣覆膜中所含有的無機成分，多使用鉻化合物。使用了鉻化合物的(2)類型的絕緣覆膜的一例為鉻酸鹽系絕緣覆膜。
(2)類型的鉻酸鹽系絕緣覆膜是利用一塗一烤(one coat one bake)的製造而形成。而且，(2)類型的鉻酸鹽系絕緣覆膜比起(1)類型的無機覆膜，因可格外提高帶絕緣覆膜的電磁鋼板的衝壓性而得到廣泛利用。
例如，專利文獻1中記載了具有電絕緣覆膜的電鐵板，該電絕緣覆膜是將處理液塗佈於基底鐵板的表面並實施利用了普通方法的燒附而獲得，所述處理液是相對於至少含有1種2價金屬的重鉻酸鹽系水溶液，將樹脂乳液以樹脂固體成分為5重量份~120重量份且將有機還原劑以10重量份~60重量份的比例加以調配所得，其中所述樹脂乳液中的作為有機樹脂的醋酸乙烯酯/第三碳酸乙烯酯(VeoVa)比相對於所述水溶液中的CrO3：100重量份為90/10~40/60的比例。
然而，現如今環境意識提高，即便在電磁鋼板的領域亦要求具有不含有鉻化合物的絕緣覆膜的電磁鋼板。
因此，開發出帶不含有鉻化合物的絕緣覆膜的電磁鋼板。例如，專利文獻2中揭示了一種絕緣覆膜，該絕緣覆膜不含有鉻化合物且可改善所述衝壓性等。專利文獻2中所記載的絕緣覆膜中含有樹脂及矽酸膠(colloidal silica)(含氧化鋁的氧化矽)。而且，專利文獻3中揭示了一種絕緣覆膜，該絕緣覆膜包含膠體狀氧化矽、氧化鋁溶膠、氧化鋯溶膠中的1種或2種以上，且含有水溶性或乳液樹脂。而且，專利文獻4中揭示了一種絕緣覆膜，該絕緣覆膜不含有鉻化合物，以磷酸鹽為主體且含有樹脂。
然而，若將帶不含有鉻化合物的絕緣覆膜的電磁鋼板與含有鉻化合物的絕緣覆膜相比，則存在耐腐蝕性、密接性(絕緣覆膜與電磁鋼板的密接性)劣化的情況。專利文獻2~專利文獻4的各技術中雖實現了耐腐蝕性或密接性的改善，但尋求更佳的改善方法。
與此相對，例如，專利文獻5中揭示了如下方法：藉由將包含多價金屬磷酸鹽的覆膜中的Fe量控制為0≦Fe/P≦0.10而改善耐腐蝕性、密接性。進而，專利文獻6中雖未記載具體數值，但揭示了藉由控制Fe溶析而改善絕緣覆膜的特性的方法。亦即專利文獻6中提出一種絕緣覆膜，該絕緣覆膜除樹脂、Al化合物及Si化合物之外，亦含有離子化傾向比Fe高且水系媒體中可能成為2價以上的離子的Al以外的1種或2種以上的易離子性元素(除Cr外)。作為所述易離子性元素，可列舉Mg、Zn、Zr、Ca、Sr、Mn及Ba。
如此，一般來說，認為因Fe向絕緣覆膜中的溶析，而存在絕緣覆膜的特性劣化的傾向。而且，在為將不含有具有鈍化效果的鉻化合物的塗料直接塗裝燒附於電磁鋼板表面而成的覆膜的情況下，難以控制Fe的所述溶析。結果，難以充分提高絕緣覆膜的性能。
現有技術文獻 專利文獻
專利文獻1：日本專利特公昭60-36476號公報
專利文獻2：日本專利特開平10-130858號公報
專利文獻3：日本專利特開平10-46350號公報
專利文獻4：日本專利第2944849號公報
專利文獻5：日本專利第3718638號公報
專利文獻6：日本專利特開2005-240131號公報
本發明為了解決所述課題而完成，其目的在於提供一種耐腐蝕性、密接性優異的帶絕緣覆膜的電磁鋼板。
發明者等人為了解決所述課題而反覆進行了積極研究。結果本發明者等人在含有Zr的絕緣覆膜中，意外地發現含有特定量Fe的絕緣覆膜的覆膜特性(絕緣覆膜的耐腐蝕性、密接性)提高，從而完成了本發明。更具體而言，本發明提供以下的帶絕 緣覆膜的電磁鋼板。
(1)一種帶絕緣覆膜的電磁鋼板，其特徵在於包括：電磁鋼板；以及絕緣覆膜，形成於所述電磁鋼板上，所述絕緣覆膜含有鋯(Zr)及鐵(Fe)，所述Zr的含量以二氧化鋯(ZrO2)換算為0.05g/m2~1.50g/m2，所述Zr及所述Fe的含有比例以莫耳比(絕緣覆膜中的Fe量(莫耳)/絕緣覆膜中的Zr量(莫耳))計為0.10~2.00。
(2)如(1)所述的帶絕緣覆膜的電磁鋼板，其特徵在於：所述絕緣覆膜進而含有矽(Si)，所述Zr及所述Si的含有比例以莫耳比(絕緣覆膜中的Si的量(莫耳)/絕緣覆膜中的Zr的量(莫耳))計為2.00以下。
(3)如(1)或(2)所述的帶絕緣覆膜的電磁鋼板，其特徵在於：所述絕緣覆膜進而含有磷(P)，所述Zr及所述P的含有比例以莫耳比(絕緣覆膜中的P的量(莫耳)/絕緣覆膜中的Zr的量(莫耳))計為1.50以下。
(4)如(1)至(3)中任一項所述的帶絕緣覆膜的電磁鋼板，其特徵在於：所述絕緣覆膜進而含有有機樹脂，所述Zr及所述有機樹脂的含有比例以固體成分比率(絕緣覆膜中的有機樹脂的固體成分量(g)/Zr的含量(g)(ZrO2換算質量))計為0.50以下。
本發明的帶絕緣覆膜的電磁鋼板具有優異的耐腐蝕性、密接性(絕緣覆膜與電磁鋼板之間的密接性)。
而且，根據本發明，即便絕緣覆膜不含有鉻(Cr)，帶絕緣覆膜的電磁鋼板亦具有優異的耐腐蝕性、所述密接性。
圖1是表示使用了奧傑電子(Auger electron)分光分析計的深度分析的結果的一例的圖。
圖2是表示絕緣覆膜與電磁鋼板的密接性和莫耳比(Fe/Zr)的關係的圖。
以下，對本發明的實施形態進行具體說明。另外，本發明不限定於以下的實施形態。
本發明的帶絕緣覆膜的電磁鋼板包括電磁鋼板、及形成於該電磁鋼板上的絕緣覆膜。
電磁鋼板
本發明中使用的電磁鋼板不限定為特定的電磁鋼板。例如，構成電磁鋼板的成分只要為普通的電磁鋼板中可含有的成分即可。關於電磁鋼板所含有的成分，除Si外，可列舉為了提高磁特性或其他性能而使用的錳(Mn)、磷(P)、鋁(Al)、硫(S)、氮(N)、釩(V)等。而且，電磁鋼板的剩餘部分包含鐵(Fe)及不可避免的雜質。
電磁鋼板的種類不作特別限定。磁通密度高的所謂的軟鐵板(電鐵板)、SPCC等普通冷軋鋼板、為了提高電阻率而含有Si或Al的無方向性電磁鋼板等均可較佳地適用於本發明中。
關於具體的電磁鋼板的特性，鐵損(iron loss)W15/50為16.0W/kg以下，較佳為13.0W/kg以下，及/或磁通密度B50為1.5 T以上，較佳為1.6 T以上者較佳。合計含有0.1質量%~10.0質量%左右的Si及/或Al者則作為電磁鋼板的代表。
絕緣覆膜
絕緣覆膜為形成於所述電磁鋼板上的絕緣覆膜。此處，絕緣覆膜的層間電阻一般為1Ω．cm2/片以上。所述絕緣覆膜含有Zr及Fe。而且，所述絕緣覆膜可較佳地含有選自Si、P及有機樹脂中的至少一種。
藉由絕緣覆膜中含有Zr，而絕緣覆膜為強韌的覆膜。認為該強韌的覆膜是藉由Zr彼此或Zr與其他無機化合物形成網狀結構而形成。之所以可形成所述網狀結構，是因為Zr具有3個以上的結合鍵，而且，Zr與氧的鍵結力強，可與Fe表面的氧化物、氫氧化物等牢固鍵結。為了獲得使用所述Zr的效果且對帶絕緣覆膜的電磁鋼板賦予耐腐蝕性，而需要將Zr化合物的附著量調整為以ZrO2換算為0.05g/m2以上。認為當Zr化合物的附著量以ZrO2換算小於0.05g/m2時，基於被覆不充分的原因，所述耐腐蝕性下降。而且，認為若Zr化合物的附著量超過1.50g/m2，則基於容易產生覆膜的裂紋的原因，絕緣覆膜與電磁鋼板間的密接性及帶絕 緣覆膜的電磁鋼板的耐腐蝕性劣化。因此，需要將Zr化合物的附著量調整為1.50g/m2以下。從覆膜的性能的觀點來說，更佳的下限為0.20g/m2，更佳的上限為1.00g/m2。
將絕緣覆膜中的Zr量以ZrO2進行換算是因為推測每一個Zr原子最多可存在4個的Zr-O(-Zr)鍵成為覆膜結構的基本。
含有Zr的絕緣覆膜藉由含有特定的量的Fe，而絕緣覆膜的覆膜特性提高。如所述般，認為絕緣覆膜中的Fe會使絕緣覆膜的覆膜特性劣化。然而，亦如實施例中所示，對於含有Zr的絕緣覆膜而言，藉由絕緣覆膜含有特定量的Fe，而絕緣覆膜的覆膜特性提高。雖然如所述般覆膜特性提高的原因不明，但認為是絕緣覆膜中的Zr與Fe間的某種相互作用所造成。
為了獲得藉由含有Zr的緣覆膜含有Fe而達成的所述效果，需要考慮絕緣覆膜中的Fe的含量與絕緣覆膜中的Zr的含量來決定。具體來說，需要以莫耳比(絕緣覆膜中的Fe量(莫耳)/絕緣覆膜中的Zr量(莫耳)，本說明書中有時稱作莫耳比(Fe/Zr))為0.10~2.00的方式，來規定Fe的含量。當莫耳比(Fe/Zr)小於0.10時，密接性不充分。認為其原因在於，在絕緣覆膜與電磁鋼板的界面，Zr與Fe的相互作用不充分。而且，認為當莫耳比(Fe/Zr)超過2.00時，在Zr的4個結合鍵以上中含有Fe，所述密接性、所述耐腐蝕性劣化。莫耳比(Fe/Zr)的較佳的範圍為0.2~1.5。
絕緣覆膜中的莫耳比(Fe/Zr)是指利用奧傑電子分光分析所獲得的莫耳比。在為一面進行濺鍍一面向深度方向進行分析 的奧傑電子分光分析的情況下，可藉由測定直至Zr的強度減半為止的Fe、Zr各自的平均值來測定莫耳比(Fe/Zr)。此時的分析點數設為10點以上，將其平均值作為莫耳比(Fe/Zr)。另外，將直至Zr的強度減半為止之處作為絕緣覆膜。當然，比所述Zr的強度減半的位置深的部分為電磁鋼板。
另外，藉由將後述的Fe化合物用於絕緣覆膜的形成中，而可將含有Fe的絕緣覆膜形成於電磁鋼板上，亦可不使用Fe化合物，而使電磁鋼板中的Fe包含於絕緣覆膜中。
絕緣覆膜較佳為含有Si。藉由絕緣覆膜含有Si，而提高絕緣覆膜的絕緣性。而且，若含有特定量的Zr及特定量的Fe的絕緣覆膜進而含有Si，則絕緣覆膜與電磁鋼板間的密接性進一步提高。為了獲得該些效果，較佳為絕緣覆膜以莫耳比(絕緣覆膜中的Si的量(莫耳)/絕緣覆膜中的Zr的量(莫耳)，本說明書中有時稱作莫耳比(Si/Zr))滿足0.30以上的方式含有Si。
而且，較佳為以莫耳比(Si/Zr)滿足2.00以下的方式來調整Si的量。藉由將莫耳比(Si/Zr)設為2.00以下，而可充分抑制因相對於Zr而含有大量Si所導致的密接性的劣化。在含有Si的情況下，考慮對覆膜結構附加Si-O鍵。
絕緣覆膜較佳為含有P。藉由含有特定量的Zr及特定量的Fe的絕緣覆膜進而含有P，而帶絕緣覆膜的電磁鋼板的耐腐蝕性提高。為了獲得提高耐腐蝕性的效果，較佳為絕緣覆膜以莫耳比(絕緣覆膜中的P的量(莫耳)/絕緣覆膜中的Zr的量(莫耳)， 本說明書中有時稱作莫耳比(P/Zr))滿足0.20以上的方式含有P。更佳為0.50以上。
而且，較佳為以莫耳比(P/Zr)滿足1.50以下的方式進行調整。即便在莫耳比(P/Zr)超過1.50的條件下含有P，所述耐腐蝕性的效果亦未得到提高或存在降低的情況。
絕緣覆膜較佳為含有有機樹脂。絕緣覆膜藉由含有有機樹脂，而帶絕緣覆膜的電磁鋼板具有優異的耐腐蝕性、耐劃傷性及衝壓性。從獲得該些效果的觀點而言，較佳為將乾燥覆膜中的有機樹脂的含量調整為5質量%以上。另外，乾燥覆膜中的含量為已形成於鋼板的表面的絕緣覆膜中的有機樹脂的比例。亦可根據將用以在鋼板上形成絕緣覆膜的處理液在180℃下乾燥30分鐘後的乾燥後殘存成分(固體成分)來求出乾燥覆膜量。
而且，藉由含有特定量的Zr及特定量的Fe的絕緣覆膜進一步含有有機樹脂，而帶絕緣覆膜的電磁鋼板的覆膜特性(耐腐蝕性)顯著提高。從提高該覆膜特性的觀點考慮，較佳為以固體成分比率((有機樹脂的含量)/Zr的含量(ZrO2換算質量))滿足0.50以下的方式，來調整絕緣覆膜中的有機樹脂的含量。
絕緣覆膜除所述成分外，亦可含有界面活性劑、防鏽劑、潤滑劑、抗氧化劑等通常使用的添加劑，或其他無機化合物或有機化合物等。作為有機化合物，例如可列舉作為無機成分與有機樹脂的接觸抑制劑而使用的有機酸。作為有機酸，例示含有羧酸的聚合物或共聚物等。而且，作為無機化合物，可列舉硼、 顏料等。該些其他成分(本說明書中有時稱作「添加物」)可在不破壞本發明的效果的範圍內含有於絕緣覆膜中。本發明中，較佳為在質量比((添加物的固體成分合計質量)/Zr的含量(ZrO2換算質量))為1.00以下的範圍內含有所述添加物。更佳為，在質量比((添加物的固體成分合計質量)/Zr的含量(ZrO2換算質量))為0.50以下的範圍內含有所述添加物。
而且，本發明的特徵在於：即便絕緣覆膜不含有Cr化合物，亦可提高帶絕緣覆膜的電磁鋼板的耐腐蝕性、絕緣覆膜與電磁鋼板的密接性。此處，所謂不含有Cr化合物，從Cr化合物不會對耐腐蝕性等造成影響的觀點來說，是指Cr的含量在乾燥覆膜中以Cr換算為0.1質量%以下，若考慮Cr化合物對環境的影響，是指Cr的含量在乾燥覆膜中以Cr換算為0.01質量%以下。
另外，絕緣覆膜中有時混入Hf、HfO2、TiO2等作為雜質。該些雜質的總量例如相對於Zr的含量(ZrO2換算質量)為5質量%以下即可。絕緣覆膜中的Zr量較佳為以ZrO2換算質量相對於固體成分整體的比率計為15質量%以上，更佳為以該比率計為20質量%以上。
其次，對帶絕緣覆膜的電磁鋼板的製造方法進行說明。
首先，帶絕緣覆膜的電磁鋼板的製造中所使用的電磁鋼板為利用普通的方法製造而成，可採用市售的電磁鋼板。
本發明中，未對作為原材料的電磁鋼板的前處理進行特別規定。亦即，即便未進行處理亦可，但有利的是對電磁鋼板實 施鹼性等的脫脂處理，鹽酸、硫酸、磷酸等的酸洗處理。
接下來，製備出用於形成絕緣覆膜的處理液。處理液例如可藉由將以下的化合物等添加至去離子水中而製備。
處理液為了使絕緣覆膜中含有Zr而含有Zr化合物。而且，處理液亦可含有Fe化合物、Si化合物、P化合物及有機樹脂中的至少1種。藉由處理液含有該些成分，而可使絕緣覆膜中含有Fe、Si、P、有機樹脂。另外，本發明中，需要使絕緣覆膜中含有Fe，亦可使絕緣覆膜中含有電磁鋼板中的Fe，因此處理液並非需要含有Fe化合物作為必須成分。
而且，所述化合物、有機樹脂的使用量根據絕緣覆膜中含有的Zr等的量來適當設定即可。即，莫耳比(Si/Zr)、莫耳比(P/Zr)、有機樹脂的固體成分比率在處理液製備階段可調整為所需的值。
作為Zr化合物，例如可列舉醋酸鋯、丙酸鋯、氧氯化鋯、硝酸鋯、碳酸鋯銨、碳酸鋯鉀、羥基氯化鋯、硫酸鋯、磷酸鋯、磷酸鈉鋯、六氟化鋯鉀、四正丙氧基鋯、四正丁氧基鋯、四乙醯丙酮鋯、三丁氧基乙醯丙酮鋯、三丁氧基硬脂酸鋯等。該些化合物當然可單獨添加，亦可複合使用2種以上。
作為Fe化合物，例如可列舉醋酸鐵、檸檬酸鐵、檸檬酸鐵銨等。該些化合物當然可單獨添加，亦可複合使用2種以上。
作為Si化合物，可列舉矽酸膠(粒徑：3nm~300nm)，燻矽(fumed silica)(比表面積：40m2/g~400m2/g)，烷氧基矽 烷及矽氧烷等。該些化合物當然可單獨添加，亦可複合使用2種以上。
作為P化合物，例如可列舉磷酸及磷酸鹽。作為磷酸，可列舉正磷酸、磷酸酐、直鏈狀多磷酸、環狀偏磷酸等。作為磷酸鹽，可列舉磷酸鎂、磷酸鋁、磷酸鈣、磷酸鋅、磷酸銨等。該些化合物當然可單獨添加，亦可複合使用2種以上。
作為有機樹脂，可較佳使用先前以來所使用的公知的有機樹脂。例如可列舉丙烯酸樹脂、醇酸樹脂、聚烯烴樹脂、苯乙烯樹脂、醋酸乙烯酯樹脂、環氧樹脂、酚樹脂、聚酯樹脂、胺基甲酸酯樹脂、三聚氰胺樹脂等的水性樹脂(乳液、分散液、水溶性)。尤佳為丙烯酸樹脂或乙烯丙烯酸樹脂的乳液。另外，該些化合物當然可單獨添加，亦可複合使用2種以上，或者亦可用作共聚物。
另外，處理液若含有界面活性劑、防鏽劑、潤滑劑等添加物，則可使絕緣覆膜中含有該些添加物。
處理液的pH值未作特別限定，但較佳為3以上、12以下。若處理液的pH值為3以上，則基於覆膜中的Fe量不易變得過剩的原因而較佳，若處理液的pH值為12以下，則基於覆膜中的Fe量不易不足的原因而較佳。
其次，將所述處理液塗佈於電磁鋼板的表面並放置固定時間。藉由該固定時間的放置，而電磁鋼板中的Fe溶析，Fe進入至處理液中，因而可使絕緣覆膜中含有Fe。從使絕緣覆膜中含有 特定量的Fe的觀點來說，放置時間較佳設為3秒~220秒的範圍，更佳設為10秒~100秒的範圍。然而，最佳的放置時間因所放置時的環境的溫度(為室溫，例如10℃~30℃的範圍)、處理液的pH值、電磁鋼板的組成而相異。因此，較佳為考慮到所述情況，而在3秒~220秒的範圍、10秒~100秒的範圍中適當選擇最佳的放置時間。
另外，將所述處理液塗佈於電磁鋼板表面的方法不作特別限定，可採用一般工業上使用的輥式塗佈機(roll coater)、流塗機(flow coater)、噴霧、刮刀塗佈機(knife coater)等各種方法。
其次，對塗佈於電磁鋼板上的處理液進行燒附，將經塗佈的處理液製成絕緣覆膜。燒附方法不作特別限定，可採用如通常實施般的熱風加熱式、紅外線加熱式、感應加熱式等的燒附爐。所述燒附時的燒附溫度不作特別限定，以到達鋼板溫度計而為150℃~350℃左右即可。而且，燒附時間(爐內時間)亦不作特別限定，較佳為1秒~600秒。
對本發明的帶絕緣覆膜的電磁鋼板實施去應力退火，例如可將衝壓加工所致的應力去除。作為較佳的去應力退火環境，可列舉N2環境、DX氣體環境等鐵不易氧化的環境等。此處，設定為提高露點、例如Dp：5℃~60℃左右，藉由將表面及切斷端面稍微氧化而可進一步提高耐腐蝕性。而且，較佳的去應力退火溫度為700℃~900℃，更佳為700℃~800℃。去應力退火溫度的保持時間越長越佳，更佳為1小時以上。
絕緣覆膜較佳為位於鋼板的兩面，但可視目的而僅位於單面。而且，亦可視目的而僅在單面形成本發明的絕緣覆膜，另一面設為其他絕緣覆膜。
[實施例]
以乾燥後的絕緣覆膜中的莫耳比(Si/Zr)、莫耳比(P/Zr)、固體成分比率(絕緣覆膜中的有機樹脂/Zr)成為表1(將表1-1與表1-2一併表示為表1)所示的值的方式，將表2所示的Zr化合物、表3所示的Si化合物、表4所示的P化合物、表5所示的有機樹脂化合物添加至去離子水中而製成處理液。此處，各成分相對於去離子水量的合計固體成分濃度設為50g/l。而且，將各處理液的pH值表示於表1中。另外，關於發明例12，若Fe不再從電磁鋼板溶析則以莫耳比(Fe/Zr)為0.40的方式添加醋酸鐵。
將所述各處理液利用輥式塗佈機塗佈於試驗片的表面，該試驗片是自板厚：0.35mm的電磁鋼板[A360(日本工業標準(Japanese Industrial Standards，JIS)C 2552(2000))、W15/50：3.60W/kg以下、B50：1.61 T以上]切出寬：150mm、長：300mm的大小所得。
然後，以表1所示的放置時間來放置塗佈了處理液的鋼板。另外，以Zr含量為表1所示的值的方式調整塗佈量。
所放置的環境的溫度為25℃。藉由該放置，莫耳比(Fe/Zr)為表1所示的值。莫耳比(Fe/Zr)的導出方法將於以後進行敍述。
然後，將所述放置後的鋼板藉由熱風燒附爐而以表1所示的燒附溫度(到達鋼板溫度)及燒附時間(爐內時間)進行燒附。之後，將燒附後的鋼板放冷至常溫為止，從而形成絕緣覆膜。
將對所獲得的帶絕緣覆膜的電磁鋼板(製品板)的覆膜特性進行調查所得的結果表示於表1。覆膜特性的評估方法為以下所述。進而，對帶絕緣覆膜的電磁鋼板，利用相同的方法來調查在氮環境中以750℃進行2小時的去應力退火後的即去應力退火後的帶絕緣覆膜的電磁鋼板(退火板)的覆膜特性。將所獲得的結果表示於表1。
<莫耳比(Fe/Zr)>
使用奧傑電子分光分析計(物理電子(PHISICAL ELECTONICS)(股)製造)，以加速電圧10keV、試樣電流0.2μA進行分析。深度分析中，以濺鍍速率3nm/min(以SiO2計的值)而每2min進行測定，Zr計數器進行測定直至達到雜訊位準為止，並算出至減半值為止的平均值。將深度分析的一例表示於圖1中。根據該分析的結果而導出莫耳比(Fe/Zr)。
<耐腐蝕性>
對帶絕緣覆膜的電磁鋼板、去應力退火後的帶絕緣覆膜的電磁鋼板進行濕潤試驗(50℃，相對濕度≧98%)，目視觀察48小時後的赤鏽面積率(發生赤鏽的面積的面積率)。根據赤鏽面積率且按照以下的基準來評估耐腐蝕性。
(判定基準)
◎：赤鏽面積率小於20%
￮：赤鏽面積率20%以上、小於40%
△：赤鏽面積率40%以上、小於60%
×：赤鏽面積率60%以上
<密接性>
將塞璐芬(cellophane)黏著膠帶貼附於帶絕緣覆膜的電磁鋼板、去應力退火後的帶絕緣覆膜的電磁鋼板的表面，φ10mm內彎曲後，將塞璐芬膠帶剝離，目視觀察絕緣覆膜的殘存狀態並進行評估。評估基準為以下所示。
(判定基準)
◎：殘存率90%以上
￮：殘存率60%以上、小於90%
△：殘存率30%以上、小於60%
×：殘存率30%小於
如表1所示，依據本發明所獲得的帶絕緣覆膜的電磁鋼板的耐腐蝕性及密接性均優異。
與此相對，Zr化合物超出適當範圍的比較例的耐腐蝕性、密接性劣化。
而且，圖2是表示去應力退火前的帶絕緣覆膜的電磁鋼板中，絕緣覆膜與電磁鋼板的密接性和莫耳比(Fe/Zr)的關係的圖。根據圖2亦可確認，藉由含有Zr的絕緣覆膜含有規定量的Fe，而覆膜特性顯著提高。

Claims (4)

  1. 一種帶絕緣覆膜的電磁鋼板，其特徵在於包括：電磁鋼板；以及絕緣覆膜，形成於所述電磁鋼板上，所述絕緣覆膜含有Zr及Fe，所述Zr的含量以ZrO2換算為0.05g/m2~1.50g/m2，所述Zr及所述Fe的含有比例以莫耳比(絕緣覆膜中的Fe量(莫耳)/絕緣覆膜中的Zr量(莫耳))計為0.10~2.00。
  2. 如申請專利範圍第1項所述的帶絕緣覆膜的電磁鋼板，其中所述絕緣覆膜進而含有Si，所述Zr及所述Si的含有比例以莫耳比(絕緣覆膜中的Si的量(莫耳)/絕緣覆膜中的Zr的量(莫耳))計為2.00以下。
  3. 如申請專利範圍第1項或第2項所述的帶絕緣覆膜的電磁鋼板，其中所述絕緣覆膜進而含有P，所述Zr及所述P的含有比例以莫耳比(絕緣覆膜中的P的量(莫耳)/絕緣覆膜中的Zr的量(莫耳))計為1.50以下。
  4. 如申請專利範圍第1項至第3項中任一項所述的帶絕緣覆膜的電磁鋼板，其中所述絕緣覆膜進而含有有機樹脂，所述Zr及所述有機樹脂的含有比例以固體成分比率(絕緣覆 膜中的有機樹脂的固體成分量(g)/Zr的含量(g)(ZrO2換算質量))計為0.50以下。
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RU2630723C2 (ru) 2017-09-12
CN105264115A (zh) 2016-01-20
US20160111182A1 (en) 2016-04-21
WO2014188679A1 (ja) 2014-11-27
EP3000915B1 (en) 2017-09-13
EP3000915A1 (en) 2016-03-30
KR20160003164A (ko) 2016-01-08
KR101730434B1 (ko) 2017-04-26
EP3000915A4 (en) 2016-06-22

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