200946716 六、發明說明： 【發明所屬之技術領域】 發明領域 5 ❿ 10 15 ❹ 本發明係有關適用於電動機器之鐵怎等具有導熱性優 異之絕緣被膜的電磁鋼板及其製造方法。 發明背景 近年來，從保護地球環境之觀點，及世界的電力及節 能之觀點言’極力地要求電動機^之高效率化及小型化。 為電動機器之高效率化及小型化，已有種種之技術被開 發。在用於馬達及小型變壓器等鐵芯之電磁鋼板中，被要 求提高磁氣特性及提高加工性等。 為相關電動機器之高效率化及小型化，有效於抑制馬 達的發熱（焦耳熱）。過去，因而提高鐵芯及捲線效率、使用 散熱板等以提高去熱性。特別為隨著馬達之高效率化及小 型化以提高散熱性，故從積層鐵芯去熱顯示其重要性。 關於去熱’在傳統的電動機器中，馬達所發生之熱從 積層鐵芯之端部傳導於機殼，從機殼表面如有散熱板時從 散熱板’藉由對流或幅射擴散於周圍。 關於積層鐵芯之形成，係將電磁鋼板鑿成鐵芯之形狀 後積層。但是，此類用於電動機器之鐵芯的電磁鋼板表面 上’設有絕緣被膜。該絕緣被膜除具有絕緣性外，需有耐 姓性、熔接性、密著性及耐熱性等特性。 關於電磁鋼板之絕緣被膜技術，已有如專利文獻1所揭 20 200946716 示之使用重鉻酸鹽及乙酸乙稀、丁一稀-本乙稀共聚合物、 丙烯酸樹脂等有機樹脂乳劑為主成分之處理液，以形成絕 緣被膜之方法。又’如專利文獻2所揭示’將鉻酸水溶液、 乳劑型樹脂及有機還原劑混合’使用易溶性銘化合物、2價 5 金屬之氧化物等及硼酸、更於鉻酸溶液中之Me2 + /Al3 +之摩 耳比為0.7〜7.0，且（Al3++Me2 + )/Cr03之摩耳比為〇·2〜 0.5，H3B03/Cr03之摩耳比為〇.1〜1.5之範圍的處理液，以 形成絕緣被膜之方法。 專利文獻3中記載’以含有鉻酸、易溶性之2價及/或3 10價鹼性金屬化合物、水性乳劑樹脂、硼酸及有機還原劑之 處理液塗布及烘烤、應變退火後，以X光電子分光法测定， 存在於被膜的外面側最表層之鉻，係由6價鉻形成之電磁鋼 板0 不過，氧化物系之絕緣被膜的熱傳導率低於金屬很 15多。因此熱向鐵芯之積層方向的傳導不易，故該方向之散 熱以馬達全體之散熱而言，未曾寄與厚望。 近年來，己有種種形狀之馬達被開發。因此，特別 從扁平狀馬達等之積層鐵芯的端面去熱不太完全的馬達而 2〇 ^提高積層鐵芯之馬達轴方向的熱傳導性之要求，日益 ^ …巧介馬達之直徑，積層鐵芯之厚 散熱效果不佳時,及從散熱 不充二==;使熱傳導較有效果時，則散熱 、、、’電礤鋼板中，絕緣被膜不具充分 200946716 熱傳導性。 再者，雖有熱傳導性較愚之绝緣被膜，對於普通電磁 鋼板所要求之密著性、耐蝕性、作業性，絕緣性等特性無 法獲得。又，降低佔積率。 5 【專利文獻1】特公昭5〇-15〇13號公報 【專利文獻2】特開平3-36284號公報 【專利文獻3】特開平6-10149鱿公報 【發明内容】 發明揭示 10 本發明之目的在於提供可維持高度的絕緣被膜之密著 性等’同時可提高熱傳導率的具有熱傳導性優異之絕緣被 膜的電磁鋼板及其製造方法。 本發明相關之具有熱傳導性優異之電磁鋼板係具有電 磁鋼板及形成於前述電磁鋼板表面之絕緣被膜，且前述絕 15緣被膜係以絡酸金屬鹽與相對於該前述路酸金屬越（換算 為三氧化鉻(Cr〇3))l重量份為0.01〜0.5重量份且結晶化率 為10〜50%苯乙烯樹脂、丙烯酸樹脂、環氧樹脂及聚醯亞胺 樹脂中之1種或2種以上的混合物或共聚合物作為主成分； 又’該絕緣被膜含有作為鉻酸化合物之氫氧化鉻化合物， 20其相對於已換算為三氧化二絡（Cr2〇s)之鉻酸化合物 100%，以換算成三氧化鉻(Cr2〇3)計係30。/。以上。 本發明相關之具有熱傳導性優異之絕緣被膜的電磁鋼 板製造方法係具有在電磁鋼板表面塗布預定的塗布液之步 驟及乾燥前述預定之塗布液所形成的絕緣被膜之步驟；且 5 200946716 作為剛述預定的塗布液’係使用主成分為鉻酸金屬鹽與苯 乙烯樹脂乳劑、丙烯酸樹脂乳劑、環氧樹脂乳劑、聚醯亞 胺樹脂分散液中之i種或2種以上的混合物或共聚合物且添 加有鉻酸當量之12〜3 6倍之聚醇化合物作為鉻酸還原劑 5者，且前述笨乙烯樹脂乳劑、丙烯酸樹脂乳劑、環氧樹脂 乳劑、聚醯亞胺樹脂分散液相對於前述鉻酸金屬鹽(換算為 二氧化鉻(CrO3))1重量份，換算為樹脂固形物係0.01〜0.5 重ϊ份，且結晶化率為1〇〜5〇% :且，前述形成絕緣被膜之 步驟具有將前述預定之塗布液於501〜200。(：之溫度範圍 10下，以10 C/秒鐘〜35°C/秒鐘之速度進行加熱之步驟。 【實施方式】 用以實施發明之最佳形態 關於本發明之實施態樣詳細說明如下。 本發明之實施態樣相關的電磁鋼板，以含有矽：0.1重 15量％以上、鋁：0·05重量％以上為佳。隨著矽含量增加，電 阻增大雖提高電磁特性，脆性卻增加。因此 ，矽含量以小 於4.0重量％為佳。隨著鋁含量增加，雖提高電磁特性壓 延性卻降低。因此，鋁含量以小於3.0重量％為佳。 石夕及铭以外，亦可含有錳等。錳含量以0.01重量％〜1.0 20重量/°為佳。又’路及鎳等轉移原素(transit element)之含 量’以小於0.1重量％為佳，而以小於0.01重量％較佳。又， 硫氮及碳專之典型原素(typical element)之含量，以小於 lOOppm為佳，較佳為小於2〇ppm。 有關本發明之實施態樣相關之電磁鋼板製造方法， 200946716 例如，將具有前述成分之平板熱軋’捲成線圈狀，因應 需要退火，冷軋至厚度約為0.15公厘〜〇5公厘，再予以 退火。 再者，本發明之實施態樣相關的電磁鋼板之表面粗 5度，以較小為佳。其為獲得南度密著性有關。因此，在壓 延方向及與壓延方向垂直的方向之中心線平均粗度尺3，以 0.8微米以下為佳，而以〇·5微米〜〇1微米較佳。平均粗度 Ra大於0.8微米時，無法獲得充分之彎曲密著性。 在本發明之實施態樣相關的電磁鋼板表面上，形成含 10有鉻&金屬鹽及有機樹脂之絕緣被膜。鉻酸金屬鹽，係將 主成分為重鉻酸及金屬離子的水溶液乾燥時之固形物。相 對於視為2價陰離子之重鉻酸，金屬種以摩耳比含有〇5〜 I.3為佳。又，金屬種2價時，金屬種以摩耳比為ι 〇5〜ι ι5 較佳；金屬種3價時，金屬種以摩耳比為〇7〜〇 77較佳。 15 再者，金屬離子减、銘、鎂，、錄及鈦等輕金屬 離子為佳，而以鎂等鹼土類金屬離子特佳。在使金屬離子 溶解於重鉻酸溶液時，亦可用金屬離子之氧化物、碳酸鹽 或風氧化合物。特別是溶解链等驗金屬離子及鎮等驗土類 金屬離子時，由於使金屬本身溶解時引起激烈反應，故以 20使用氧化物或氫氧化合物為佳。 當製造傳統之電磁鋼板時，將重鉻酸鹽溶液於2〇〇它以 上加熱乾燥所形成之絕緣被膜中，使塗布的重絡酸之絡由6 價還原成3價，鉻之大部分成為三氧化二絡(Cr2〇3)，絡之 10%〜20%成為氫氧化鉻(Cr(〇H)3)。 200946716 相對於此，本發明人等發現重鉻酸鹽溶液，雖於20(rc 以上加熱乾燥時，隨著條件將氫氧化鉻(Cr(OH)3)之比例， 比傳統者大幅增加。即，本發明人等發現氫氧化鉻(Cr(〇H)3) 之生成量，依存於聚醇化合物之添加量及昇溫至200〇c之速 5度。因此，了解可藉由控制氫氧化鉻(Cr(OH)3)之生成量， 可改善絕緣被膜之熱傳導性。 氫氧化鉻(Cr(OH)3)被推定於被膜中形成某種之聚合狀 態，當氫氧化鉻(Cr(OH)3)之比例提高，則熱傳導性提高。 因此，該效果顯著地顯示於絕緣被膜中之氫氧化鉻 1〇 (Cr(0H)3)換算為三氧化二鉻(ChO3)存在30。/。以上時《又， 存在45%以上時，更顯著地顯示效果；存在6〇%以上時，更 上一層顯著地顯示效果。 為還原重鉻酸，可使用有機還原劑。有機還原劑大幅 度地影響到氫氧化鉻(Cr(OH)3)之生成，在本發明之實施態 15樣中，可將聚醇化合物作為有機還原劑使用。又，可控制 氫氧化鉻(Cr(〇H)3)生成之聚醇化合物的添加量，其範圍極 為狹窄。具體可言，作為聚醇化合物，可使用乙二醇、甘 油及嚴糖，其添加比例係視為3價氧化劑之重絡酸鹽當量的 1.2倍〜3.6倍。由於小於h2倍則氫氧化鉻(Cr(〇H)3)之生成 2〇不充分，且難於獲得充分之熱傳導性；大於3.6倍則烘烤範 圍變狹窄，難於獲得充分之作業性。故以使成為重鉻酸^ 量之1.5〜2.4倍為佳。 田 過去，有關對於無方向性電磁鋼板之絕緣被祺的形 成，有關絕緣被膜之塗布作業線、乾燥作業線及冷郤作業 200946716 線，係連續地設在該等之前步驟的橫型退火作業線之下 部。因此，為塗布起至乾燥之步驟的合計設備長，係基於 烘烤爐之爐長作決定。又，由於冷卻係實施空氣冷卻之關 係，故冷卻爐較長，該結果，昇溫爐較短，從有關昇溫爐 5 之設備條件言，以昇溫速度作決定。 對於此，本發明人等對有關前述樣之設備條件所決定 之昇溫速度，從氫氧化鉻(Cr(OH)3)之生成觀點，更進一步 進行檢討。其結果，本發明人等發現於50°C〜200°C之温度 範圍的昇溫速度，藉由使l〇°C/秒鐘〜35°C/秒鐘之昇溫速度 10比傳統者遲缓，可使氫氧化鉻(Cr(OH)3)之比例成為30。/〇以 上。50C〜200°C之溫度範圍的昇溫速度，不論小於1〇。〇/ 秒鐘、大於35°C/秒鐘’皆難於生成充分量之氫氧化絡 (Cr(OH)3)。因此，50°C〜200°C之溫度範圍的昇溫速度，以 io°c/秒鐘〜35°c(oh)3)/秒鐘為佳，而以1(rc/秒鐘〜2(rc/ 15 秒鐘較佳。 昇溫速度不在於前述的範圍時，難於生成充分之氫氧 化鉻(Cr(OH)3)之詳細理由不明。小於10〇c/秒鐘時，被推定 是由於在熱力學上穩定的三氧化二鉻(ChOj之生成量相對 地增大。又，大於35<t/秒鐘時，被推定是由於聚醇之蒸發 20迅速，鉻酸之還原反應所寄託之聚醇的比例降低，因而受 到藉由加熱還原重鉻酸鹽之還原反應所支配。 在200C以上的溫度領域之昇溫速度，並未特予限，故 亦可大於35。(：/秒鐘。在2〇(rc以上，使殘存的還原劑及有 機樹脂中之界面活性劑等分子量較小的有機化合物揮發之 200946716 同時，生成之氫氧化鉻(Cr(OH)3)由於加熱還原少量逐漸地 被重鉻酸鹽氧化之反應，及從氫氧化鉻(Cr(OH)3)生成三氧 化二鉻(Cr203)之反應同時進行，且相被抵消。因此，在2〇〇 。(：以上的溫度領域之昇溫速度雖大於35°C/秒鐘，不會發生 5 特別的問題。 再者，加熱溫度以加到400°C為佳，加熱大於4〇〇°c則 有機樹脂之分解易起動。加熱溫度以加到350°C較佳。 含於絕緣被膜之有機樹脂，係苯乙稀樹脂、丙婦酸樹 脂、環氧樹脂、聚醯亞胺樹脂之1種或2種以上之混合物或 ® 10共聚合物，其結晶化率為1〇°/◦〜50%。作為有機樹脂，特別 以苯乙烯樹脂及丙烯酸之共聚合物為佳，結晶化率之控制 簡便且可成為種種範圍之結晶化率。使結晶化率成為1〇% 〜5〇°/〇，係由於小於1〇。/。時，熱傳導性有降低之傾向，而大 於50%則有起霜(blooming)之傾向。 15 再者，有機樹脂含量，係相對於重鉻酸鹽1重量份，以 0.01重量份〜〇.5重量份為佳。理由是小於〇 〇1重量份則有機 樹脂之添加效果少，難於獲得充分之塗布性，而大於〇5重 © 量份則難於獲得充分之耐熱性。更以適宜範圍為〇1重量份 〜〇.4重量份，對於有機樹脂之分散，亦是在特別優異之範 20圍=。至於與1〇%〜50%之結晶化率的相乘效果，認為亦有 提高佔積率之效果。 藉由共聚合條件及其後之加熱等處理，雖亦可控制結 晶化率，由於添加各種核化劑，亦可簡便地控制結晶化率°。 作為核化劑，雖可使用任何物質，以氧化石夕、氧化鎮及滑 10 200946716 石等氧化物系核化劑具有效果’特別是對於丙稀酸樹脂、 環氧樹脂，以滑石具有效果。 有機樹脂之塗布量雖未特別限定，以05g/m2〜4.0g/m2 為佳。理由是塗布量小於〇.5g/m2，則結晶化易於進行而 5難於控制結晶化率，大於4.Og/m2則密著性降低之傾向顯 著。 氫氧化鉻(Cr(OH)3)之比例的測定方法，未特予限定。 ©例如’藉由化學分析用電子能谱術(electron spectroscopy for chemical analysis、ESCA)之鉻-氧結合與絡_氫氧結合之強 10 度比，從數個深度分析(depth profile)算出亦可。特別是從 鉻(III)所算出氧-鉻-氫氧結合尖峯之量扣除的方法，由於方 ' 法簡便故佳。 ' 當絕緣被膜形成時，以處理液塗布電磁鋼板表面時， 塗布方法未特予限定，以輕塗機塗布亦可，亦可用喷霧器 15 塗布，藉由浸潰塗布亦可。 〇 再者，加熱方法亦未特予限定，藉由一般之幅射爐加 熱亦可，以感應加熱等電力加熱亦可。但是，從加熱速度 之控制精度言，以感應加熱為佳。 根據本發明之實施態樣，不論熱傳導率之提高及外觀 20之提高均顯著。外觀良好當然可提高商品價值，對於凹洞 及突起等電磁鋼板之瑕疵，可期待於機械性檢查時提高精 度。通常被膜為微細結晶質時，雖顯呈無光澤、白濁之傾 向，但平滑且具有高度均勻性。又被膜為非結晶質時，雖 顯呈發出光澤之傾向，因場所而有降低均勻性之傾向。在 11 200946716 本發明中，由於結晶化率控制適宜，可取得光澤、平滑性 及均勻性之平衡，故可得良好之外觀。 諸如此類，含有特定的有機樹脂及特定的還原劑之重 鉻酸鹽溶液，藉由特定的昇溫速度的加熱，控制鉻酸鹽之 形態，可控制氫氧化鉻之生成比例。該結果，可提高無方 向性電磁鋼板之絕緣被膜的熱傳導性，可得散熱性良好之 無方向性電磁鋼板。 (實施例） 在含有矽：2.5%、鋁：〇·5%、錳：0.05%，且厚度0.3 10公厘之無方向性電磁鋼板表面上，將顯示於第丨表之塗布 液，根據第2表所顯示之條件塗布。作為重鉻酸鹽係混合加 熱鉻薄片及氫氧化鎂(Mg(〇H)2)、氫氧化鋁(Al(〇H)3)、氧化 鈣(CaO)、碳酸鳃(SrC〇3)等之金屬氫氧化物、氧化物或碳 酸鹽以調製金屬重鉻酸鹽，使用50%水溶液。 15 關於有機樹脂，將苯乙烯樹脂、丙稀酸樹脂、環氧樹 脂分別作成30°/。乳劑溶液使用，而聚醯亞胺樹脂作成3〇%分 散溶液使用。更將還原劑加入預定量，調整第丨表之組成的 塗布液。又，第1表中之「有機樹脂：重量份」欄之右側的 數值’係表示相對於重鉻酸1重量份之有機樹脂的重量，左 20 側之（）内的數值’係表示有機樹脂之結晶化率。結晶化率 0%係非晶質狀態之意。 第！表中’試驗版卜版3及No.5(實施例)之有機樹脂， 係作為核化劑之滑石（超微粉髮），使用相對於樹脂固形物1 重量份添加0.03重量份者。塗布液以輥塗機塗布，以觀壓 12 200946716 下量調整使塗布量為2g/m2。 乾燥係以熱風爐進行，為獲得預定之昇溫速度以設定 爐溫進行調整。到達溫度雖依試樣之不同而異，以調整使 成為於225°C〜400°C之範圍。所得試樣之評價結果顯示於 5 第2表。表中之氫氧化鉻量以光電子分光分析法(ESCA)從氧 及鉻之尖峯決定氫氧化鉻(Cr(OH)3)量。200946716 VI. Description of the Invention: [Technical Field of the Invention] Field of the Invention 5 ❿ 10 15 ❹ The present invention relates to an electromagnetic steel sheet which is suitable for an electric insulating machine and has an insulating film excellent in thermal conductivity, and a method for producing the same. Background of the Invention In recent years, from the viewpoint of protecting the global environment and the world's power and energy saving, it has been demanded to increase the efficiency and miniaturization of electric motors. Various technologies have been developed for the efficiency and miniaturization of electric machines. In an electromagnetic steel sheet for a core such as a motor or a small transformer, it is required to improve magnetic characteristics and improve workability. In order to increase the efficiency and miniaturization of the related electric machine, it is effective in suppressing heat generation (joule heat) of the motor. In the past, the core and winding efficiency were improved, and heat sinks and the like were used to improve heat removal. In particular, as the efficiency and miniaturization of the motor are increased to improve heat dissipation, the importance of heat removal from the laminated core is revealed. Regarding heat removal, in a conventional electric machine, heat generated by the motor is conducted from the end of the laminated core to the casing, and from the surface of the casing, if there is a heat sink, the convection or radiation is diffused from the heat sink. . Regarding the formation of the laminated iron core, the electromagnetic steel sheet is chiseled into the shape of an iron core and then laminated. However, such an electromagnetic steel sheet for an iron core of an electric machine is provided with an insulating film. In addition to insulating properties, the insulating film needs to have properties such as resistance to the surname, weldability, adhesion, and heat resistance. Regarding the insulating film technology of the electromagnetic steel sheet, an organic resin emulsion such as dichromate and vinyl acetate, butan-diethyl-diethylide copolymer or acrylic resin is mainly used as disclosed in Patent Document 1 No. 20 200946716. A method of treating a liquid to form an insulating film. Further, as disclosed in Patent Document 2, 'mixing a chromic acid aqueous solution, an emulsion type resin, and an organic reducing agent' uses a readily soluble compound, a divalent 5 metal oxide, and the like, and boric acid, and Me2 + in a chromic acid solution. The molar ratio of Al3 + is 0.7 to 7.0, and the molar ratio of (Al3++Me2 + )/Cr03 is 〇·2 to 0.5, and the molar ratio of H3B03/Cr03 is 〇.1 to 1.5. To form an insulating film. Patent Document 3 describes "coating, baking, and strain annealing a treatment liquid containing chromic acid, a readily soluble divalent and/or 3 10 valent basic metal compound, an aqueous emulsion resin, boric acid, and an organic reducing agent, and X. The chromium which is the outermost layer of the outer surface of the film is measured by photoelectron spectroscopy, and is an electromagnetic steel sheet formed of hexavalent chromium. However, the thermal conductivity of the oxide-based insulating film is much higher than that of the metal. Therefore, the conduction of heat to the lamination direction of the iron core is not easy, so the heat dissipation in this direction has not been expected to be high in terms of heat dissipation of the entire motor. In recent years, motors of various shapes have been developed. Therefore, in particular, from the end face of the laminated iron core of a flat motor or the like, the heat is not completely completed, and the heat conductivity of the motor core direction of the laminated iron core is increased, and the diameter of the motor is increasingly increased. When the heat dissipation effect of the core is not good, and the heat dissipation is not charged twice ==; when the heat conduction is more effective, the heat dissipation, and the 'electrical steel plate, the insulating film does not have sufficient thermal conductivity of 200946716. Further, although there is an insulating film which is less thermally conductive, the properties such as adhesion, corrosion resistance, workability, and insulation which are required for ordinary electromagnetic steel sheets cannot be obtained. Also, reduce the occupancy rate. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. It is an object of the invention to provide an electromagnetic steel sheet having an insulating film having excellent thermal conductivity and capable of improving the thermal conductivity of a high-temperature insulating film, and a method for producing the same. An electromagnetic steel sheet having excellent thermal conductivity according to the present invention includes an electromagnetic steel sheet and an insulating coating formed on a surface of the electromagnetic steel sheet, and the absolute 15 edge film is made of a metal acid salt and a metal acid relative to the acid metal. Chromium trioxide (Cr 〇 3)) 1 part by weight or less of 1 to 2 parts by weight and a crystallization ratio of 10 to 50% of styrene resin, acrylic resin, epoxy resin and polyimide resin The above mixture or copolymer is used as a main component; and the insulating film contains a chromium hydroxide compound as a chromic acid compound, 20 which is 100% relative to a chromic acid compound which has been converted into a trioxide complex (Cr 2 〇s), Calculated by conversion to chromium trioxide (Cr2〇3) system 30. /. the above. The method for producing an electromagnetic steel sheet having an insulating film having excellent thermal conductivity according to the present invention includes a step of applying a predetermined coating liquid on the surface of the electromagnetic steel sheet and a step of drying the insulating coating formed by the predetermined coating liquid; and 5 200946716 The predetermined coating liquid is a mixture or copolymer of a metal chromic acid metal salt and a styrene resin emulsion, an acrylic resin emulsion, an epoxy resin emulsion, or a polyimide resin dispersion. And a polyhydric alcohol compound having a chromic acid equivalent of 12 to 36 times as a chromic acid reducing agent 5, and the above-mentioned stupid vinyl resin emulsion, acrylic resin emulsion, epoxy resin emulsion, polyimine resin dispersion liquid phase for the aforementioned 1 part by weight of a metal chromate salt (calculated as chromium dioxide (CrO3)), converted into a resin solid content of 0.01 to 0.5 parts by weight, and a crystallization ratio of 1 〇 to 5 〇%: and the above-mentioned insulating film is formed. The step has a predetermined coating liquid of 501 to 200. (The temperature range is 10, and the step of heating at a rate of 10 C/sec to 35 ° C/sec.) BEST MODE FOR CARRYING OUT THE INVENTION The embodiments of the present invention will be described in detail below. The electromagnetic steel sheet according to the embodiment of the present invention preferably contains yttrium: 0.1 by weight of 15% by volume or more, and aluminum: 0.02% by weight or more. As the cerium content increases, the electrical resistance increases while improving electromagnetic properties, brittleness Therefore, the content of niobium is preferably less than 4.0% by weight. As the aluminum content increases, the ductility of the electromagnetic properties is lowered. Therefore, the aluminum content is preferably less than 3.0% by weight. Manganese, etc. The manganese content is preferably from 0.01% by weight to 1.020% by weight. Further, the content of the transfer element such as 'road and nickel' is preferably less than 0.1% by weight, and more preferably less than 0.01% by weight. Further, the content of the typical element of the sulfur nitrogen and the carbon is preferably less than 100 ppm, preferably less than 2 Torr. The method for producing an electromagnetic steel sheet according to an embodiment of the present invention, 200946716 For example, Will have the foregoing The flat hot rolled sheet is rolled into a coil shape, which is annealed in accordance with the need, and cold rolled to a thickness of about 0.15 mm to about 5 mm, and then annealed. Further, the surface of the electromagnetic steel sheet according to the embodiment of the present invention is rough. 5 degrees, preferably smaller. It is related to the south degree of adhesion. Therefore, the center line of the calendering direction and the direction perpendicular to the rolling direction has an average thickness of 3, preferably 0.8 microns or less. 5 μm to 〇 1 μm is preferable. When the average roughness Ra is more than 0.8 μm, sufficient bending adhesion cannot be obtained. On the surface of the electromagnetic steel sheet related to the embodiment of the present invention, 10 chrome & metal is formed. An insulating film of a salt and an organic resin. The metal chromate is a solid substance obtained by drying an aqueous solution containing a dichromic acid and a metal ion as a main component. The metal species is contained in a molar ratio with respect to dichromic acid which is regarded as a divalent anion. 〇5~ I.3 is better. Also, when the metal species is 2, the metal species is preferably ι 〇5~ι ι5; when the metal species is 3 valence, the metal species is 摩7~〇 77 is better. 15 Furthermore, metal ion reduction, Ming, magnesium, recording and titanium Light metal ions are preferred, and alkaline earth metal ions such as magnesium are particularly preferred. When metal ions are dissolved in dichromic acid solution, metal ion oxides, carbonates or wind oxides can also be used. When the metal ions such as ions and towns are used to cause a violent reaction when the metal itself is dissolved, it is preferable to use an oxide or a hydroxide as 20. When manufacturing a conventional electromagnetic steel sheet, the dichromate solution is used in 2 〇〇 It is heated and dried to form an insulating film, so that the coated heavy acid complex is reduced from 6 to 3, and most of the chromium is trioxide (Cr2〇3), 10%~20 % becomes chromium hydroxide (Cr(〇H)3). In contrast, the present inventors have found that the dichromate solution has a large increase in the ratio of chromium hydroxide (Cr(OH) 3 ) as compared with the conventional ones when heated at 20 (rc or more). The present inventors have found that the amount of chromium hydroxide (Cr(〇H)3) formed depends on the amount of the polyphenol compound added and the temperature rise to 5 度c at a rate of 200 〇c. Therefore, it is understood that the chromium hydroxide can be controlled. The amount of (Cr(OH)3) produced can improve the thermal conductivity of the insulating film. Chromium hydroxide (Cr(OH)3) is presumed to form a certain polymerization state in the film, when chromium hydroxide (Cr(OH)) When the ratio of 3) is increased, the thermal conductivity is improved. Therefore, the effect is remarkably shown in the insulating film. The chromium hydroxide (Cr(0H)3) is converted to chromium oxide (ChO3) in an amount of 30% or more. At the time of "more than 45%, the effect is more prominently displayed; when there is more than 6%, the upper layer is significantly more effective. For the reduction of dichromic acid, an organic reducing agent can be used. The organic reducing agent greatly affects To the formation of chromium hydroxide (Cr(OH)3), in the embodiment 15 of the present invention, the polyalcohol compound can be used as Further, the amount of the polyalcohol compound formed by chromium hydroxide (Cr(〇H)3) can be controlled, and the range thereof is extremely narrow. Specifically, as the polyalcohol compound, ethylene glycol, glycerin, and the like can be used. Yan sugar, the addition ratio is regarded as 1.2 times to 3.6 times the weight equivalent of the trivalent oxidizing agent. Since less than h2 times, the formation of chromium hydroxide (Cr(〇H)3) is insufficient, and it is difficult A sufficient thermal conductivity is obtained; when the ratio is more than 3.6 times, the baking range becomes narrow, and it is difficult to obtain sufficient workability, so that it is preferably 1.5 to 2.4 times that of dichromic acid. In the past, related to non-directional electrical steel sheets. The formation of the insulating bedding, the coating line for the insulating film, the drying line, and the cooling operation 200946716 line are continuously provided below the horizontal annealing line of the previous step. Therefore, from coating to drying The total length of the steps is determined based on the length of the oven. Moreover, since the cooling system is air-cooled, the cooling furnace is long. As a result, the furnace is shorter, from the equipment of the heating furnace 5 Condition, The temperature rise rate determined by the inventors of the present invention is further reviewed from the viewpoint of the generation of chromium hydroxide (Cr(OH)3) from the viewpoint of the temperature rise rate determined by the above-mentioned equipment conditions. As a result, the present invention People found that the temperature rise rate in the temperature range of 50 ° C ~ 200 ° C, by l ° ° C / sec ~ 35 ° C / sec temperature increase speed 10 than the traditional slow, can make chromium hydroxide The ratio of (Cr(OH)3) is 30./〇 or more. The temperature rise rate in the temperature range of 50C to 200 °C is less than 1 〇. 〇 / sec, more than 35 ° C / sec. Amount of hydroxide (Cr(OH)3). Therefore, the temperature rise rate in the temperature range of 50 ° C to 200 ° C is preferably io ° c / sec to 35 ° c (oh) 3) / sec, and 1 (rc / sec ~ 2 (rc / 15 seconds is preferable. When the temperature increase rate is not within the above range, the detailed reason why it is difficult to form sufficient chromium hydroxide (Cr(OH) 3 ) is unknown. When it is less than 10 〇 c / sec, it is presumed to be due to thermodynamics. Stable chromium oxide (the amount of ChOj produced is relatively increased. Further, when it is greater than 35 < t / sec, it is presumed that the evaporation of the polyol is rapid, and the reduction of the chromic acid is based on the polyhydric alcohol The ratio is lowered, and thus it is dominated by the reduction reaction by heating and reducing the dichromate. The temperature rise rate in the temperature range of 200 C or more is not particularly limited, so it may be greater than 35. (: / sec. at 2 〇 (rc or more, volatilization of the residual reducing agent and the organic compound having a small molecular weight such as a surfactant in the organic resin, 200946716, and the generated chromium hydroxide (Cr(OH)3) is gradually densified by a small amount of heat reduction. The oxidation reaction of the acid salt and the reaction of generating chromium oxide (Cr203) from chromium hydroxide (Cr(OH)3) are simultaneously carried out, The phase is offset. Therefore, at 2 〇〇. (: The temperature rise rate in the above temperature range is greater than 35 ° C / sec, no special problems will occur. Moreover, the heating temperature is preferably added to 400 ° C. When the heating is more than 4 〇〇 °c, the decomposition of the organic resin is easy to start. The heating temperature is preferably added to 350 ° C. The organic resin contained in the insulating film is styrene resin, propylene glycol resin, epoxy resin, One or a mixture of two or more kinds of polyimine resins or a copolymer of 10 and a crystallization ratio of 1 〇 ° / ◦ 50%. As an organic resin, especially a copolymer of styrene resin and acrylic acid Preferably, the control of the crystallization ratio is simple and can be a crystallization ratio in various ranges. When the crystallization ratio is 1% to 5 〇 ° / 〇, the thermal conductivity is lowered when it is less than 1 〇. And more than 50% has a tendency to bloom. 15 Further, the content of the organic resin is preferably 0.01 parts by weight to 5% by weight based on 1 part by weight of the dichromate. The reason is less than When 1 part by weight is used, the effect of adding an organic resin is small, and it is difficult to obtain sufficient coating properties. Further, it is difficult to obtain sufficient heat resistance, and more than 〇1 parts by weight to 4 parts by weight, and for the dispersion of the organic resin, it is also particularly excellent. As for the effect of multiplying the crystallization ratio of 1% to 50%, it is considered that the effect of increasing the occupation ratio is also improved. The crystallization ratio can also be controlled by the treatment of the copolymerization conditions and the subsequent heating, etc. Various nucleating agents can also easily control the crystallization rate. As a nucleating agent, any substance can be used, and oxide nucleating agents such as oxidized stone oxidized, oxidized and slipped 10 200946716 have an effect, especially For acrylic acid resins and epoxy resins, it has an effect on talc. The coating amount of the organic resin is not particularly limited, and is preferably from 0.5 g/m2 to 4.0 g/m2. The reason is that when the coating amount is less than 〇5 g/m2, crystallization is easy to proceed, and it is difficult to control the crystallization ratio, and when it is more than 4.0 g/m2, the tendency to lower the adhesion is remarkable. The method for measuring the ratio of chromium hydroxide (Cr(OH)3) is not particularly limited. For example, 'by the electron spectroscopy for chemical analysis (ESCA), the ratio of the chromium-oxygen combination to the strong _hydrogen-oxygen combination is calculated from several depth profiles. . In particular, the method of deducting the amount of the oxygen-chromium-hydrogen-oxygen bond peak calculated from chromium (III) is preferable because the method is simple. When the surface of the electromagnetic steel sheet is coated with the treatment liquid when the insulating film is formed, the coating method is not particularly limited, and it may be applied by a light coater, or may be applied by a sprayer 15, and may be applied by dipping. Further, the heating method is not particularly limited, and heating by a general radiation furnace may be performed by electric heating such as induction heating. However, from the control accuracy of the heating rate, induction heating is preferred. According to an embodiment of the present invention, both the improvement in thermal conductivity and the improvement in appearance 20 are remarkable. The appearance is good, of course, the value of the product can be improved, and for the electromagnetic steel sheets such as the pits and the projections, it is expected to improve the accuracy in the mechanical inspection. In general, when the film is finely crystalline, it exhibits a dull, white turbid tendency, but is smooth and highly uniform. When the film is amorphous, the gloss tends to be emitted, and the uniformity tends to be lowered depending on the place. In the present invention, since the crystallization rate is appropriately controlled, a balance of gloss, smoothness, and uniformity can be obtained, so that a good appearance can be obtained. For example, a dichromate solution containing a specific organic resin and a specific reducing agent controls the form of chromate by heating at a specific heating rate to control the ratio of formation of chromium hydroxide. As a result, the thermal conductivity of the insulating coating of the non-oriented electromagnetic steel sheet can be improved, and a non-oriented electrical steel sheet having excellent heat dissipation can be obtained. (Example) On the surface of a non-oriented electrical steel sheet containing ruthenium: 2.5%, aluminum: 〇·5%, manganese: 0.05%, and a thickness of 0.310 mm, the coating liquid shown in the second table is used. 2 The conditions shown in the table are applied. As a dichromate-based mixed heating chromium flake, magnesium hydroxide (Mg (〇H) 2), aluminum hydroxide (Al (〇H) 3), calcium oxide (CaO), strontium carbonate (SrC〇3), etc. A metal hydroxide, oxide or carbonate is used to prepare the metal dichromate using a 50% aqueous solution. 15 For the organic resin, the styrene resin, the acrylic resin, and the epoxy resin were each made into 30°/. The emulsion solution was used, and the polyimide resin was used as a 3 % dispersion solution. Further, the reducing agent is added to a predetermined amount, and the coating liquid of the composition of the second table is adjusted. In addition, the value 'on the right side of the column of "organic resin: parts by weight" in the first table indicates the weight of the organic resin with respect to 1 part by weight of the dichromic acid, and the value ' in the left 20 side indicates the organic resin. Crystallization rate. The crystallization rate of 0% is intended to be an amorphous state. The first! In the table, the organic resin of the test plate 3 and No. 5 (Example) was used as a nucleating agent talc (ultrafine powder), and 0.03 part by weight was added to 1 part by weight of the resin solid content. The coating liquid was applied by a roll coater, and the amount of coating was adjusted to 2 g/m 2 by the amount of pressure 12 200946716. The drying is carried out in a hot air oven, and the furnace temperature is adjusted in order to obtain a predetermined heating rate. The arrival temperature varies depending on the sample, and is adjusted so as to be in the range of 225 ° C to 400 ° C. The evaluation results of the obtained samples are shown in Table 5 of Table 5. The amount of chromium hydroxide in the table is determined by photoelectron spectroscopy (ESCA) from the peaks of oxygen and chromium to determine the amount of chromium (Cr(OH)3).
13 200946716 昇溫速度(°c/s.) in CN in (N 〇 (N in m 〇 〇 還原劑：重量份 乙二醇：1.5 甘油：0.45 蔗糖：012 ，1 <0 乙二醇：1.5 甘油：0.45 乙二醇：1.5 乙二醇：1.5 甘油：0.9 甘油：0.05 in Ί 〇 乙二醇：1.5 有機樹脂：重量份 丙烯酸樹脂(12%) : 0.3 丙烯酸、苯乙烯(30%) : 0.4 環氧樹脂(20%) : 0.3 聚醯亞胺樹脂(45%) : 0.2 丙烯酸、苯乙稀(20%) : 0.4 丙烯酸、笨乙烯(15%) : 0.4 丙烯酸樹脂(0%) : 0.3 苯乙烯樹脂(75%) : 0.3 丙烯酸、苯乙烯(15%) : 0.4 丙烯酸、苯乙烯(15%) : 0.4 丙烯酸樹脂(12%) : 0.3 環氧樹脂(20%) : 0.3 重鉻酸鹽 MgCr03 MgCr03 MgCr03 Al2(Cr03)2 SrCr03 K2Cr03 MgCr03 MgCr03 MgCr03 Al2(Cr03)2 MgCr03 MgCr03 試驗No. ，呻 (N 寸 卜 00 〇 Τ—Η (N 實施例| 實施例 實施例 實施例 實施例 實施例 比較例 比較例 比較例 比較例 比較例 比較例 Q- 〇 14 200946716 再者，第1表中之「重鉻酸鹽」欄之所記載之組成，係 調整為50重量％溶液時之組成。還原劑之量，係相對於重 鉻酸鹽1重量份之還原劑添加量。「還原劑」欄中之「EG」 表示乙二醇，「GL」表示甘油，「SU」表示蔗糖。氧化還原 5 等量係根據試驗結果，當重鉻酸為3時，乙二醇為4，甘油 為9，蔗糖為12。即，相對於lmol之重鉻酸鹽，等量於乙二 醇1.33mol;等量於甘油3mol:等量於嚴糖4mol。 15 20094671613 200946716 Heating rate (°c/s.) in CN in (N m (N in m 〇〇 reducing agent: parts by weight ethylene glycol: 1.5 glycerol: 0.45 sucrose: 012, 1 < 0 ethylene glycol: 1.5 glycerol : 0.45 ethylene glycol: 1.5 ethylene glycol: 1.5 glycerin: 0.9 glycerin: 0.05 in Ί 〇 ethylene glycol: 1.5 organic resin: parts by weight acrylic resin (12%): 0.3 acrylic acid, styrene (30%): 0.4 ring Oxygen resin (20%) : 0.3 Polyimide resin (45%) : 0.2 Acrylic acid, styrene (20%): 0.4 Acrylic acid, stupid ethylene (15%): 0.4 Acrylic resin (0%): 0.3 Styrene Resin (75%) : 0.3 Acrylic, styrene (15%) : 0.4 Acrylic, styrene (15%) : 0.4 Acrylic resin (12%) : 0.3 Epoxy resin (20%) : 0.3 Dichromate MgCr03 MgCr03 MgCr03 Al2(Cr03)2 SrCr03 K2Cr03 MgCr03 MgCr03 MgCr03 Al2(Cr03)2 MgCr03 MgCr03 Test No., 呻(N 寸 00 〇Τ Η Η (N Example | Example Examples Comparative Examples of Examples EXAMPLES Comparative Example Comparative Example Comparative Example Q- 〇14 200946716 Furthermore, the "dichromate" column in the first table is described. The composition is adjusted to a 50% by weight solution. The amount of the reducing agent is the amount of the reducing agent added to 1 part by weight of the dichromate. The "EG" in the "Reducing Agent" column indicates ethylene glycol. GL" means glycerin, "SU" means sucrose. The redox 5 is based on the test results. When the dichromic acid is 3, the ethylene glycol is 4, the glycerol is 9, and the sucrose is 12. That is, relative to the weight of 1 mol. Chromate, equal to 1.33 mol of ethylene glycol; equal amount of glycerol 3 mol: equal amount of 4 mol of sugar. 15 200946716
Cr(OH)3 »ri in 00 ΓΛ S in (Ν ο iTi iTi (Ν 外觀 in 们 寸 in 寸 寸 们 m 寸 Ο ο ο Ο On 〇\ 卜 卜 Μ Μ Μ Μ ο ο ο Ο ο ο O ο 〇 〇 〇 〇 a B Β Β Β Β B Β B a B a a ε Β Β Β ε B Β B ε B B ο ^Η Ο Ο Ο Ο ί—1 ο τ—Η 宕 〇 〇 件 οο 00 r-； 00 οο α\ 00 〇\ 00 αν Ον 00 00 as od 〇6 ο oo as od od 00 〇\ ιη ρ m Ο Oj p in o ^Ti P CN (Ν ^Τ) (Ν Ά cn (Ν (Ν irl <N o m CN o m 芝 οο c<\ 00 CN 試驗No. ^-Η (Ν m 寸 ι〇 卜 00 Os o i—H CN ¥ 雀 餐 錄 ίΚ Ik ίΚ ΐΚ Aj λ3 -Ο 〇3Cr(OH)3 »ri in 00 ΓΛ S in (Ν ο iTi iTi (Ν in 们 们 们 m m m m m m m in 〇〇〇a B Β Β Β Β B Β B a B aa ε Β Β ε ε B Β B ε BB ο ^Η Ο Ο Ο ί ί 1 τ τ Η 宕〇〇 ο ο 00 r-; 00 οο α\ 00 〇\ 00 αν Ον 00 00 as od 〇6 ο oo as od od 00 〇\ ιη ρ m Ο Oj p in o ^Ti P CN (Ν ^Τ) (Ν rl cn (Ν (Ν irl < N om CN om 芝οοο c<\ 00 CN Test No. ^-Η (Ν m 寸 〇 00 00 Os oi-H CN ¥ 雀 录 Κ Ik Κ ΐΚ Aj λ3 -Ο 〇3
16 200946716 由於電磁鋼板表面之熱傳導率難於正確測定，以以下 的方法評價。將形成有絕緣被膜之電磁鋼板加工成30公厘 角，積層80張。周圍以斷熱材料包裹後，在加熱至18〇。〇的 發熱體上，以加壓力2〇kgf/cm2加壓。在60分鐘後顯示溫度 5無變化時’測定發熱體及反方向側（加壓側）之鋼板的溫度， 溫度愈低者判定為熱傳導率良好。 佔積率係根據JIS(日本工業規格）所定之方法（C2550) 測定。 岔著性係在直徑10公厘、20公厘、30公厘之金屬棒， 10以貼有黏膠帶的電磁鋼板之試樣捲繞之後，剝離黏膠帶， 以剝離之痕跡評價。在捲繞於直徑1〇公厘之金屬棒時未被 、 剝離者為WmmcpOK：，在捲繞於直徑20公厘之金屬棒時未被 剝離者為20mm(pOK’在捲繞於直徑30公厘之金屬棒時未被 剝離者為30mm(pOK。未發生剝離的金屬棒之直徑愈小者， 15可說是密著性愈高。 φ 耐蝕性之評價係根據JIS所定之方法(Z2371)，藉由鹽水 噴霧試驗進行。然後，將經過7小時後的生銹狀態分成1〇階 段評價。「10」係表示未生銹。「9」係表示生銹之面積比例 (面積率）大於0%、0.1%以下且很小。「7」係表示生銹之面 20 積率大於0.25%、0.50%以下。「6」係表示生銹之面積率大 於0.50%、1.00%以下。第2表中雖未記載，「1」係表示生銹 之面積率大於25% ' 50°/。以下。 外觀之評價，以具有光澤、平滑且均勻者為5 ;雖有光 澤’均勻性比評價5者略差者為4 ;略有光澤雖是平滑，均 17 200946716 勻性比評價5者差者為3 ;第2表中雖未記載，與評價5者比 較，光澤少，平滑略差而均勻性差者為2 ;光澤、均勻性及 平滑性均差者為1。 如顯示於第2表中，本發明之範圍内之試驗No.l〜6(實 5 施例），與不在於本發明範圍之試驗No.7〜12(比較例）比 較，以熱傳導性之評價所測定之溫度低，佔積率高，密著 性高，对蝕性高，外觀良好。從該結果，根據本發明之效 果顯明。16 200946716 Since the thermal conductivity of the surface of the electromagnetic steel sheet is difficult to measure correctly, it is evaluated by the following method. The electromagnetic steel sheet in which the insulating film was formed was processed to an angle of 30 mm, and 80 sheets were laminated. After being wrapped around a heat-insulating material, it is heated to 18 〇. On the heating element of the crucible, pressurize with a pressure of 2 〇 kgf/cm2. When the temperature 5 was not changed after 60 minutes, the temperature of the steel sheet of the heating element and the opposite side (pressing side) was measured. The lower the temperature, the higher the thermal conductivity. The occupancy rate is measured in accordance with the method (C2550) prescribed by JIS (Japanese Industrial Standards). The squatting is performed on a metal rod having a diameter of 10 mm, 20 mm, and 30 mm, and 10 is wound with a sample of an electromagnetic steel sheet to which an adhesive tape is attached, and the adhesive tape is peeled off, and the peeling marks are evaluated. When it is wound around a metal rod having a diameter of 1 mm, the peel is not WmmcpOK: when it is wound on a metal rod having a diameter of 20 mm, it is 20 mm (pOK' is wound at a diameter of 30 mm) When the metal bar is not peeled, it is 30 mm (pOK. The smaller the diameter of the metal bar that has not been peeled off, the higher the adhesion is. 15) The evaluation of corrosion resistance is based on the method of JIS (Z2371). Then, it was carried out by a salt spray test. Then, the rust state after 7 hours passed was divided into 1 〇 stage evaluation. "10" indicates that there was no rust. "9" indicates that the area ratio (area ratio) of rust was greater than 0. %, 0.1% or less and very small. "7" indicates that the rust surface ratio is greater than 0.25% and 0.50%. "6" indicates that the area ratio of rust is greater than 0.50% and 1.00%. Although it is not described in the middle, "1" indicates that the area ratio of rust is more than 25% '50°/min. The evaluation of the appearance is 5 with gloss, smoothness and uniformity; The slightly worse one is 4; the slightly luster is smooth, both are 17 200946716. The uniformity ratio is 5 in the case of the difference; the second table is not recorded. Compared with the evaluation 5, the gloss is small, the smoothness is slightly poor, and the uniformity is 2; the difference in gloss, uniformity, and smoothness is 1. As shown in the second table, the test No. within the scope of the present invention In the case of Test Nos. 7 to 12 (Comparative Example) which are not in the scope of the present invention, the temperature measured by the evaluation of the thermal conductivity is low, the occupancy rate is high, and the adhesion is high. It has high corrosion resistance and good appearance. From the results, the effects according to the present invention are apparent.
產業上利用之可能性 10 含有特定之有機樹脂及特定之還原劑的重鉻酸鹽溶 液，藉由特定之昇溫速度的加熱，控制鉻酸鹽之形態，而 可控制氫氧化鉻之生成比例。該結果，提高無方向性電磁 鋼板之絕緣被膜的熱傳導性，可得散熱性良好之無方向性 電磁鋼板。 15 【圖式簡單說明】Industrial Applicability 10 A dichromate solution containing a specific organic resin and a specific reducing agent controls the form of chromate by heating at a specific heating rate to control the proportion of chromium hydroxide formed. As a result, the thermal conductivity of the insulating coating of the non-oriented electromagnetic steel sheet can be improved, and a non-oriented electrical steel sheet having excellent heat dissipation can be obtained. 15 [Simple description of the diagram]
(無） 【主要元件符號說明】 (無） 18(none) [Explanation of main component symbols] (none) 18