JPH1053818A - Production of separation agent at annealing, excellent in film forming capacity, and grain oriented silicon steel sheet using same - Google Patents
Production of separation agent at annealing, excellent in film forming capacity, and grain oriented silicon steel sheet using sameInfo
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- JPH1053818A JPH1053818A JP8211506A JP21150696A JPH1053818A JP H1053818 A JPH1053818 A JP H1053818A JP 8211506 A JP8211506 A JP 8211506A JP 21150696 A JP21150696 A JP 21150696A JP H1053818 A JPH1053818 A JP H1053818A
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- annealing
- steel sheet
- mgo
- film
- grain
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は方向性電磁鋼板の製
造に際し、グラス皮膜形成能に優れ、均一で極めて優れ
たグラス被膜を有すると同時に塗布作業性の優れる焼鈍
分離剤とそれを用いた方向性電磁鋼板の製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an annealing separator having excellent glass film forming ability, a uniform and extremely excellent glass coating, and excellent coating workability at the time of producing a grain-oriented electrical steel sheet. The present invention relates to a method for manufacturing a conductive electrical steel sheet.
【０００２】[0002]
【従来の技術】通常、方向性電磁鋼板は４％以下のＳｉ
を含有する素材を熱延し、焼鈍と１回叉は焼鈍を挟む２
回以上の冷間圧延により最終板厚にされる。次いでＮ2
＋Ｈ2又はＨ2 等の雰囲気ガス中でＰＨ2 Ｏ／ＰＨ2 を
制御して脱炭焼鈍を行い、一次再結晶、脱炭及びＳｉＯ
2 を主成分とする酸化膜の形成処理を行う。2. Description of the Related Art Grain-oriented electrical steel sheets usually contain less than 4% of Si.
Hot rolled material containing and contains annealing and one or two annealing
The final thickness is obtained by cold rolling more than once. Then N 2
+ H 2 or H 2 or other atmosphere gas to control PH 2 O / PH 2 for decarburization annealing, primary recrystallization, decarburization and SiO 2
An oxide film mainly composed of 2 is formed.
【０００３】その後、ＭｇＯを主成分とする焼鈍分離剤
をスラリー状にしてコーティングロール等で塗布し、最
終焼鈍を行い、二次再結晶、純化、グラス被膜形成を行
った後、通常は張力付与型の絶縁被膜剤を塗布し、連続
ライン中で焼き付け処理を行い製品とされる。更に、高
磁束密度方向性電磁鋼板の場合、特に板厚０．２７mm以
下の様な薄手材に於いては、レーザー、プレスロール、
歯型ロール、ケガキ等によって線状疵を付与する磁区細
分化処理を行って鉄損改善が施される。[0003] Thereafter, an annealing separator containing MgO as a main component is made into a slurry and applied by a coating roll or the like, and then subjected to final annealing to perform secondary recrystallization, purification, and formation of a glass film. A mold insulating coating agent is applied and baked in a continuous line to obtain a product. Further, in the case of a high magnetic flux density oriented magnetic steel sheet, especially in a thin material having a thickness of 0.27 mm or less, a laser, a press roll,
Iron loss is improved by performing a magnetic domain refining treatment for providing linear flaws by using a tooth-shaped roll, marking, or the like.
【０００４】この方向性電磁鋼板は＜００１＞軸をもつ
（１１０）＜００１＞結晶が高温の仕上げ焼鈍（二次再
結晶焼鈍）で優先的に成長する現象を利用している。こ
の二次再結晶過程で低表面エネルギーをもつ（１１０）
面結晶が優先的に成長し、鋼中のインヒビターとして微
細に分散しているＡｌＮ，ＭｎＳ等により成長を抑えら
れている他の結晶を浸食するために優先的に成長するも
のと考えられている。従って、優れた方向性電磁鋼板を
製造するためには、鋼中のＡｌＮ，ＭｎＳ等の分散制御
とこれらの分解までの制御が重要である。This grain-oriented electrical steel sheet utilizes a phenomenon in which (110) <001> crystals having a <001> axis grow preferentially by high-temperature finish annealing (secondary recrystallization annealing). It has low surface energy during this secondary recrystallization process (110)
It is thought that the plane crystal grows preferentially and grows preferentially to erode other crystals whose growth is suppressed by AlN, MnS, etc. which are finely dispersed as an inhibitor in the steel. . Therefore, in order to manufacture an excellent grain-oriented electrical steel sheet, it is important to control the dispersion of AlN, MnS, and the like in the steel and control the decomposition thereof.
【０００５】最終焼鈍に於けるインヒビターの変化は、
脱炭焼鈍で形成する酸化膜、焼鈍分離剤及び最終仕上げ
焼鈍の熱サイクルや雰囲気条件により影響を受けること
は知られている。これらの中でとりわけ焼鈍分離剤のＭ
ｇＯの性状や添加剤はグラス被膜形成開始時期、形成速
度、被膜の質、量等に大きい影響力をもつためインヒビ
ターへの影響が大きい。[0005] The change in the inhibitor during the final annealing is as follows:
It is known that it is affected by an oxide film formed by decarburizing annealing, an annealing separator, a thermal cycle of final finishing annealing, and atmospheric conditions. Among these, M of the annealing separator
The properties and additives of gO have a great influence on the glass film formation start time, formation rate, film quality, quantity, etc., and therefore have a great influence on the inhibitor.
【０００６】焼鈍分離剤ＭｇＯは、脱炭焼鈍で形成され
るＳｉＯ2 主体の酸化膜と反応して、通常、グラス被膜
と呼ばれるフォルステライト主体の被膜を形成する（２
ＭｇＯ＋ＳｉＯ2 →Ｍｇ2 ＳｉＯ4 ）。このグラス被膜
形成に於いては、従来のＭｇＯパウダーを使用する場
合、グラス被膜形成に於ける反応性制御の問題から、Ｍ
ｇＯの性状として特に粒度、純度、活性度の他、鋼板へ
の塗布時における水への分散性、水和量、塗布量、塗布
膜の均一性、鋼板面への密着性等の影響が大きい。更
に、前記グラス被膜形成の反応促進剤として添加される
添加剤の種類、添加量及びＭｇＯ表面と鋼板表面への分
散状態が被膜形成の形成開始温度、形成速度、形成量等
に影響を及ぼす。これらの、焼鈍分離剤における種々の
ＭｇＯ特性の違いが最終製品の被膜特性のみならず磁気
特性を左右する結果をもたらすのである。The annealing separator MgO reacts with the SiO 2 -based oxide film formed by the decarburizing annealing to form a forsterite-based coating usually called a glass coating (2).
MgO + SiO 2 → Mg 2 SiO 4 ). When a conventional MgO powder is used in the formation of the glass film, it is difficult to control the reactivity in the formation of the glass film.
In addition to the particle size, purity, and activity, the properties of gO are greatly affected by dispersibility in water, the amount of hydration, the amount of coating, the uniformity of the coating film, the adhesion to the steel sheet surface, and the like during application to steel sheets. . Further, the type and amount of the additive added as a reaction accelerator for the formation of the glass film and the state of dispersion on the MgO surface and the steel sheet surface affect the film formation start temperature, the formation speed, the formation amount, and the like. These differences in the various MgO properties of the annealing separator result in determining not only the coating properties but also the magnetic properties of the final product.
【０００７】一般的に、焼鈍分離剤として用いるＭｇＯ
は水酸化マグネシウム、炭酸マグネシウム、塩基性炭酸
マグネシウム等の原料を平均粒径数百〜数千オングスト
ローム程度のサイズの微粒子結晶に調整し、７００〜１
２００℃程度の高温で焼成して０．２〜５μｍ程度のＭ
ｇＯの微細な結晶粒子を得て用いられる。この際、Ｍｇ
Ｏや添加剤は製造段階での焼結や焼成から使用段階まで
の保存時の吸湿による経時変化による粒子の凝集や水に
懸濁させる段階での粒子同士の強い凝集反応により、鋼
板面に塗布される段階では、数ミクロン〜数十ミクロン
の粗大粒子となり反応性低下を引き起こす。特に従来の
ＭｇＯでは、低水和ＭｇＯを得ようとすると、高温焼成
での製造が必須であり、この様な場合にはＭｇＯの焼
結、凝集等の反応が一段と強まる。このため、塗布乾燥
後の鋼板表面では、ＭｇＯ粒子の接触面積が低下、塗布
膜密度の低下、鋼板面に対する密着性の低下、塗膜の均
一性の低下等が生じる。Generally, MgO used as an annealing separator
Adjusts raw materials such as magnesium hydroxide, magnesium carbonate, basic magnesium carbonate and the like into fine-particle crystals having an average particle size of several hundreds to several thousand Angstroms;
M is fired at a high temperature of about 200 ° C and has a M of about 0.2 to 5 µm.
It is used by obtaining fine crystal particles of gO. At this time, Mg
O and additives are applied to the steel plate surface by agglomeration of particles due to temporal change due to moisture absorption during storage from sintering and baking in the manufacturing stage to use stage, and strong agglutination reaction between particles in the stage of suspension in water. At this stage, the particles become coarse particles of several microns to several tens microns, causing a decrease in reactivity. In particular, in the case of conventional MgO, in order to obtain low hydrated MgO, production at high temperature sintering is indispensable, and in such a case, reactions such as sintering and agglomeration of MgO are further strengthened. For this reason, on the steel sheet surface after coating and drying, the contact area of the MgO particles is reduced, the coating film density is reduced, the adhesion to the steel sheet surface is reduced, and the uniformity of the coating film is reduced.
【０００８】また、ＭｇＯにグラス被膜の反応促進剤と
して添加剤を配合して使用する場合にも、添加剤自体も
製造時の焼結やスラリー中の凝集が生じ、粗大粒子のま
まで塗布膜中あるいは鋼板酸化膜上に存在する。特に、
凝集性の強いＭｇＯに添加する場合には、更にこの現象
が顕著になる。その結果、反応促進効果が弱まったり、
不均一反応を生じることになり、均一で、良好なグラス
被膜が得られ難く、これによる磁気特性の劣化を引き起
こす。したがって、分散性が良く、微粒子で反応性の良
い焼鈍分離剤の開発は重要な課題である。反面、高活性
で反応性の良いＭｇＯを得ようとすると水和水分が増加
する傾向があり、同時にスラリーの粘性が増加して高速
ラインでの塗布作業において均一な塗布性が得られなく
なる問題がある。Further, when an additive is added to MgO as a reaction accelerator for a glass film, the additive itself also undergoes sintering during production and agglomeration in a slurry, resulting in a coating film with coarse particles. Present inside or on steel oxide film. Especially,
This phenomenon becomes more remarkable when it is added to MgO having strong cohesiveness. As a result, the reaction promoting effect weakens,
Heterogeneous reaction occurs, and it is difficult to obtain a uniform and good glass coating, thereby deteriorating magnetic properties. Therefore, development of an annealing separator having good dispersibility and good reactivity with fine particles is an important issue. On the other hand, when trying to obtain highly active and reactive MgO, the hydration moisture tends to increase, and at the same time, the viscosity of the slurry increases, and there is a problem that uniform application properties cannot be obtained in the coating operation in a high-speed line. is there.
【０００９】反応性の優れる焼鈍分離剤ＭｇＯの製造技
術として、特開平０２−２６７２７８号公報では、焼成
したＭｇＯを１００℃以上の水蒸気含有雰囲気中を通過
させ、ＭｇＯ表面にＯＨ化学吸着層をＨ2 Ｏ換算でＭｇ
Ｏ量にもとずいて０．８〜２．５％形成したＭｇＯを含
む焼鈍分離剤を脱炭焼鈍後の鋼板に塗布し、仕上げ焼鈍
する技術が提案されている。これにより、均一なグラス
被膜を有し、磁気特性の優れる方向性電磁鋼板が得られ
ることが述べられている。As a production technique of an annealing separator MgO having excellent reactivity, Japanese Patent Application Laid-Open No. 02-267278 discloses a technique in which baked MgO is passed through a steam-containing atmosphere at 100 ° C. or higher to form an OH chemically adsorbed layer on the MgO surface. Mg in 2 O conversion
There has been proposed a technique in which an annealing separator containing 0.8 to 2.5% of MgO based on the amount of O is applied to a steel plate after decarburizing annealing and finish annealing is performed. It is described that a grain-oriented electrical steel sheet having a uniform glass coating and having excellent magnetic properties is thereby obtained.
【００１０】また、特開平７−３１０１８８には、本発
明者らによって〔Ｍｇｌ-XＭ3+ X 〕Ｏ，〔Ｍｇｌ-XＭ2+
X 〕Ｏ，〔Ｍｇｌ-XＭ2+ X1Ｍ3+ X2〕Ｏの一般式で表され
る複合金属酸化物が提案されている（Ｍ2+；Ｂｅ，Ｃ
ａ，Ｂａ，Ｓｒ，Ｓｎ，Ｍｎ，Ｆｅ，Ｃｏ，Ｎｉ，Ｃ
ｕ，Ｚｎ，Ｍ3+；Ａｌ，Ｆｅ，Ｃｒ，Ｃｏ，Ｂ，Ｔｉ，
Ｓｂ ０．０１≦ｘ≦０．４０，ｘ＝ｘ１＋ｘ２）。こ
の発明ではＭｇの一部を前記２価、３価或いは両者によ
って置換固溶し、複合金属酸化物により低融点化し、均
一で高張力のグラス皮膜が得られるものである。この技
術は、いずれも焼鈍分離剤の塗布時におけるＭｇＯ粒子
の凝集の解決法として、焼鈍後のＭｇＯ表面を高温での
特殊な表面処理を行って改質したり、ＭｇＯの複合化
（固溶体）によって融点を低下させたりするものであ
る。また、微粒子のＭｇＯを得てグラス皮膜形成反応を
向上させるものであり、かなりの改善効果が得られてい
る。Japanese Patent Application Laid-Open No. Hei 7-310188 discloses that [Mg -X M 3+ X ] O, [Mg -X M 2+
X] O, [Mgl -X M 2+ X1 M 3+ X2] composite metal oxide represented by the general formula of O has been proposed (M 2+; Be, C
a, Ba, Sr, Sn, Mn, Fe, Co, Ni, C
u, Zn, M 3+ ; Al, Fe, Cr, Co, B, Ti,
Sb 0.01 ≦ x ≦ 0.40, x = x1 + x2). In the present invention, a part of Mg is substituted and solid-dissolved by the above-mentioned divalent or trivalent, and the melting point is lowered by the composite metal oxide, whereby a uniform and high-tensile glass film can be obtained. In this technique, as a solution to coagulation of MgO particles at the time of applying an annealing separating agent, the MgO surface after annealing is modified by performing a special surface treatment at a high temperature, or MgO is combined (solid solution). Or lowering the melting point. Further, it is to obtain MgO of fine particles to improve the glass film forming reaction, and a considerable improvement effect is obtained.
【００１１】しかしながら、ＭｇＯの製造条件からもた
らされる焼結、ＯＨ化学吸着層の安定性、ＭｇＯ製造か
ら使用までの経時変化による凝集、水和水分、塗布作業
工程における粘性制御の問題からもたらされる不均一塗
布等の問題は完全に解決されたわけではなく、脱炭焼鈍
において形成される酸化膜の品質によっては被膜や磁気
特性のトラブル等回避出来ない問題が残った。このた
め、更に低水和で且つ高反応性且つ現場塗布工程におけ
る塗布作業性の優れるＭｇＯの開発が望まれた。However, the sintering caused by the MgO production conditions, the stability of the OH chemically adsorbed layer, the agglomeration due to the aging change from the MgO production to the use, the hydration moisture, and the viscosity control in the coating process cause problems. The problems of uniform coating and the like were not completely solved, and there were problems that could not be avoided such as troubles in the coating and magnetic properties depending on the quality of the oxide film formed in the decarburization annealing. For this reason, there has been a demand for the development of MgO which has a lower hydration, a higher reactivity, and an excellent coating workability in a coating process on site.
【００１２】本発明では、上述した従来技術における問
題解決策として、焼鈍分離剤の塗布性とグラス皮膜形成
反応の問題を解決することを主眼としてなされた。In the present invention, as a solution to the above-mentioned problems in the prior art, it has been made to solve the problems of the applicability of the annealing separator and the reaction of forming a glass film.
【００１３】[0013]
【発明が解決しようとする課題】本発明では、方向性電
磁鋼板製造時に於ける焼鈍分離剤の塗布に際し、従来の
ＭｇＯに於けるグラス被膜形成に於ける反応性向上と低
融点化の限界の問題及び焼鈍分離剤スラリーの水和性、
粘性の問題がもたらす高速ラインにおける不均一塗布の
問題を新規な焼鈍分離剤を適用することにより解決を図
る。これにより、均一なグラス皮膜形成と良好な磁気特
性を得る方向性電磁鋼板の製造方法を提供することを目
的としてなされる。SUMMARY OF THE INVENTION According to the present invention, when applying an annealing separator in the production of grain-oriented electrical steel sheets, there is a limit on the improvement of reactivity and the lowering of the melting point in the conventional glass film formation of MgO. Problems and hydration properties of the annealing separator slurry,
The problem of uneven coating in high-speed lines caused by the problem of viscosity is solved by applying a new annealing separator. Accordingly, an object of the present invention is to provide a method for manufacturing a grain-oriented electrical steel sheet that can form a uniform glass film and obtain good magnetic properties.
【００１４】[0014]
【課題を解決するための手段】本発明者等は方向性電磁
鋼板の脱炭焼鈍〜最終仕上げ焼鈍過程までのグラス被膜
形成工程において、均一なグラス被膜を有し、磁気特性
の優れる製品の製造方法について検討した。この研究に
おいては、特に焼鈍分離剤として使用するＭｇＯの反応
性向上と塗布作業時におけるスラリー性状に着目して研
究を行った。Means for Solving the Problems In the glass coating forming process from the decarburizing annealing to the final finishing annealing of the grain-oriented electrical steel sheet, the present inventors manufactured a product having a uniform glass coating and excellent magnetic properties. The method was discussed. In this study, the research was conducted focusing on the improvement of the reactivity of MgO used as an annealing separator and the properties of the slurry during the coating operation.
【００１５】焼鈍分離剤として、通常は、ＭｇＯと反応
促進剤としてＴｉ化合物等の添加剤が用いられる。この
ような従来技術においては、ＭｇＯの性状がグラス被膜
形成、主として反応性や被膜の安定性に対して影響し、
被膜のみならず、磁気特性に多大な影響を及ぼすため、
添加剤による補助効果の方がむしろ重要なためである。As an annealing separator, MgO and an additive such as a Ti compound are usually used as a reaction accelerator. In such prior art, the properties of MgO affect glass film formation, mainly the reactivity and stability of the film,
Because it has a great effect on not only the coating but also the magnetic properties,
This is because the auxiliary effect of the additive is rather important.
【００１６】本発明者らは新規な高反応性焼鈍分離剤と
して、複合酸化物ＭｇＯについて膨大な研究と実験を行
って検討した。その結果、前記問題を解決する新規な焼
鈍分離剤として、ＭｇＯの一部にＡｌ，Ｃａ，Ｔｉ，
Ｖ，Ｃｒ，Ｍｎ，Ｆｅ，Ｓｒ，Ｃｏ，Ｚｒ，Ｓｂの１種
又は２種以上を一定量を含有し、且つ、Ａｌとのモル比
を一定範囲とすることにより、焼鈍分離剤の水和水分や
粘性が改善された微粒子の高反応性酸化物が得られる。
その結果、現場高速通板の塗布作業が容易で、更に広範
囲の他の工程条件においてグラス皮膜の安定化が得ら
れ、磁性改善効果が得られる技術の開発に至ったもので
ある。The present inventors have conducted extensive research and experiments on a composite oxide MgO as a novel highly reactive annealing separator. As a result, Al, Ca, Ti,
The hydration of the annealing separator can be achieved by containing a certain amount of one or more of V, Cr, Mn, Fe, Sr, Co, Zr, and Sb and keeping the molar ratio with Al within a certain range. A highly reactive oxide of fine particles having improved moisture and viscosity can be obtained.
As a result, the application of the high-speed sheet passing on-site is easy, the glass film is stabilized under a wide range of other process conditions, and the technology for improving the magnetism has been developed.
【００１７】本発明は、方向性電磁鋼板の製造において
脱炭焼鈍後の鋼板表面に焼鈍分離剤を塗布するに際し、
適用される新規な焼鈍分離剤とそれを用いた方向性電磁
鋼板に関するものである。その要旨は以下のとおりであ
る。 （１）モル比でＭｇ；１００に対し、Ａｌ，Ｃａ，Ｔ
ｉ，Ｖ，Ｃｒ，Ｍｎ，Ｆｅ，Ｓｒ，Ｃｏ，Ｚｒ，Ｓｂの
中から選ばれる１種又は２種以上を合計で０．０５〜１
０を含有する酸化物で、且つ、（Ａｌ以外の元素のモル
比のトータル数）／（Ａｌのモル数）比率が０．５〜１
０であり、ＢＥＴ比表面積が１０〜１００ｍ 2 ／ｇ、水
和水分が０．５〜６．０％である皮膜形成能に優れる焼
鈍分離剤。 （２）焼鈍分離剤中のＡｌ，Ｃａ，Ｔｉ，Ｖ，Ｃｒ，Ｍ
ｎ，Ｆｅ，Ｓｒ，Ｃｏ，Ｚｒ，Ｓｂの中から選ばれる１
種又は２種以上の合計の２０％以上がＭｇＯ結晶の中で
置換固溶されている上記（１）の皮膜形成能に優れる方
向性電磁鋼板用焼鈍分離剤。 （３）最終板厚に冷間圧延した方向性電磁鋼板コイルを
脱炭焼鈍し、焼鈍分離剤を塗布乾燥後、仕上げ焼鈍し、
絶縁皮膜剤を塗布焼き付けすることからなる工程におい
て、脱炭焼鈍後の鋼板表面に特許請求項（１）または
（２）の焼鈍分離剤を塗布乾燥後仕上げ焼鈍を行うに際
し、昇温時の雰囲気ガスをＮ2 １０〜９０％、残部をＨ
2 とし、ＰＨ2 Ｏ／ＰＨ2 を０．０１〜０．４として焼
鈍するグラス皮膜の優れる方向性電磁鋼板の製造方法。The present invention relates to a method for manufacturing a grain-oriented electrical steel sheet.
When applying an annealing separator on the steel sheet surface after decarburizing annealing,
Novel annealing separator applied and directional electromagnetics using it
It relates to a steel plate. The summary is as follows:
You. (1) Al, Ca, T with respect to Mg;
i, V, Cr, Mn, Fe, Sr, Co, Zr, Sb
One or more selected from among 0.05 to 1 in total
0, and (moles of elements other than Al
(Total number of ratio) / (mol number of Al) ratio is 0.5 to 1
0 and the BET specific surface area is 10 to 100 m Two/ G, water
Baking with excellent film-forming ability with a total water content of 0.5 to 6.0%
Blunt separating agent. (2) Al, Ca, Ti, V, Cr, M in the annealing separator
1 selected from n, Fe, Sr, Co, Zr, and Sb
More than 20% of the total of the seed or two or more kinds in the MgO crystal
Those who are superior in the film forming ability of the above (1), which are substituted solid solution
Annealing separator for grain-oriented electrical steel sheets. (3) Grain-oriented electrical steel sheet coil cold-rolled to final thickness
After decarburizing annealing, applying an annealing separator and drying, finish annealing,
In the process consisting of applying and baking an insulating film agent
Claim (1) or on the steel sheet surface after decarburization annealing
When performing the final annealing after applying and drying the annealing separator of (2)
And the atmosphere gas at the time of temperature rise is changed to NTwo10-90%, balance H
TwoAnd PHTwoO / PHTwoTo 0.01 to 0.4
A method for producing grain-oriented electrical steel sheets with excellent dull glass coating.
【００１８】[0018]
【発明の実施の形態】本発明では、モル比でＭｇ１００
重量部に対し、Ａｌ，Ｃａ，Ｔｉ，Ｖ，Ｃｒ，Ｍｎ，Ｆ
ｅ，Ｓｒ，Ｃｏ，Ｚｒ，Ｓｂの中から選ばれる１種又は
２種以上を０．０５〜１０からなる酸化物で且つこれら
のＡｌ以外の元素のトータルモル数／Ａｌのモル数が
０．５〜１０であり、更に、酸化物性状としてＢＥＴ比
表面積１０〜１００ｍ2 ／ｇ、水和水分が０．５〜６．
０％であることが特徴であり、これにより、高速ライン
での優れた塗布作業性とグラス皮膜形成効果が得られ
る。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, Mg100 is used as a molar ratio.
Al, Ca, Ti, V, Cr, Mn, F
e, Sr, Co, Zr, and Sb are oxides of one or more selected from 0.05 to 10 and the total mole number of these elements other than Al / the mole number of Al is 0.1. BET specific surface area of 10 to 100 m 2 / g and hydrated water of 0.5 to 6.
It is characterized by being 0%, whereby excellent coating workability and a glass film forming effect in a high-speed line can be obtained.
【００１９】本発明のＭｇ化合物においては、Ａｌを一
定量含有することが必須である。Ａｌは通常のＭｇＯ製
造過程における水酸化物の段階で添加される。このＡｌ
はＭｇＯ主体の水酸化物の結晶の成長を抑制すると同時
に、この水酸化物を焼成して得られる酸化物のシンタリ
ングを極めて効果的に抑制する効果がある。この結果、
非常に微細な酸化物が得られる。Ａｌはモル比でＭｇ１
００に対し、０．０５〜１０の割合で添加される。０．
０５以下の添加では水酸化物の結晶成長抑制やシンタリ
ング抑制の効果が極めて低下する。一方、１０以上にな
ると焼成後のＭｇＯ主体の酸化物が活性過ぎて高水和化
が避けられず、また、スラリーの粘度が高くなりすぎて
高速通板での均一な塗布作業が困難になる。更に、これ
らによりグラス皮膜の不均一性、皮膜欠陥を生じたり、
磁気特性の劣化をもたらすため好ましくない。本発明に
おいて、前記、Ａｌ添加と共に重要なのは同時に添加さ
れるＣａ，Ｔｉ，Ｖ，Ｃｒ，Ｍｎ，Ｆｅ，Ｓｒ，Ｃｏ，
Ｚｒ１種又は２種以上のトータル量とＡｌ量の比であ
る。これらの他の添加元素はＭｇ主体の酸化物の融点を
低下する一方で酸化物を不活性化する働きを有する。こ
の比率がモル比で０．５〜１０の場合、酸化物の微粒子
化効果を保ちつつ低水和の酸化物が得られる。この結
果、通常のＭｇＯに比較して低水和で、極めて高反応性
の酸化物が得られる。また、スラリーの粘性がこの比率
によって自由に制御出来るため、製造ラインの条件に合
った適切な酸化物が得られる。比率が０．５未満では、
この不活性化による低水和化効果が得られない。また、
スラリーの粘性制御効果も得られにくい。一方、比率が
１０以上になるとその作用が強すぎて、微粒化効果を減
少し、グラス皮膜形成反応性の低下を引き起こすため好
ましくない。In the Mg compound of the present invention, it is essential to contain a certain amount of Al. Al is added at the stage of hydroxide in a normal MgO production process. This Al
Has the effect of suppressing the growth of MgO-based hydroxide crystals and at the same time very effectively suppressing the sintering of the oxide obtained by firing this hydroxide. As a result,
Very fine oxides are obtained. Al is Mg1 in a molar ratio.
It is added at a ratio of 0.05 to 10 with respect to 00. 0.
Addition of not more than 05 significantly reduces the effect of suppressing the crystal growth and sintering of the hydroxide. On the other hand, when it is 10 or more, MgO-based oxide after firing is too active to inevitably cause high hydration, and the viscosity of the slurry becomes too high, making it difficult to perform a uniform coating operation with high-speed sheet passing. . In addition, these may cause non-uniformity of the glass film and film defects,
It is not preferable because the magnetic properties are deteriorated. In the present invention, it is important to add Ca, Ti, V, Cr, Mn, Fe, Sr, Co,
It is the ratio of the total amount of one or more Zr to the amount of Al. These other additional elements have a function of lowering the melting point of the oxide mainly composed of Mg while inactivating the oxide. When this ratio is 0.5 to 10 in terms of molar ratio, a low hydration oxide can be obtained while keeping the effect of making the oxide fine. As a result, an oxide having a low hydration and an extremely high reactivity as compared with ordinary MgO is obtained. Further, since the viscosity of the slurry can be freely controlled by this ratio, an oxide suitable for the conditions of the production line can be obtained. If the ratio is less than 0.5,
The dehydration effect by this inactivation cannot be obtained. Also,
It is difficult to obtain the effect of controlling the viscosity of the slurry. On the other hand, if the ratio is 10 or more, the action is too strong, the effect of atomization is reduced, and the reactivity of forming a glass film is lowered.
【００２０】次に、Ａｌを一定量含有し、Ｃａ，Ｔｉ，
Ｖ，Ｃｒ，Ｍｎ，Ｆｅ，Ｓｒ，Ｃｏ，Ｚｒ，Ｓｂ等の他
の元素をモル比で一定割合で含有する本発明の酸化物に
おいてはそれらの割合で制御される酸化物の比表面積に
特徴がある。本発明の様な工程で製造する酸化物におい
ては、特にＡｌ含有Ｍｇ化合物の場合、前述のような理
由から、極めて微細な酸化物が得られるのが特徴であ
る。通常のＭｇＯの場合、製造工程条件によって異なる
が本発明のＡｌによる微細化効果がないため、高々１０
〜２０ｍ2 ／ｇ程度の比表面積のしか得られない。しか
し、本発明の場合、従来のＭｇＯでは得られないような
著しく比表面積の大きいＭｇ化合物が得られるのが特徴
である。また、従来のＭｇＯと同様な比表面積でも低融
点で高反応性が得られるのが特徴である。これにより、
グラス被膜形成における反応性が向上し、極めて優れる
被膜と磁気特性を有する方向性電磁鋼板が得られる。比
表面積の範囲は１０〜１００ｍ2 ／ｇの範囲であれば本
発明の目的とする低水和、高反応性、スラリー粘度適正
化効果がもたらされる。Next, a certain amount of Al is contained, and Ca, Ti,
The oxide of the present invention containing a constant ratio of other elements such as V, Cr, Mn, Fe, Sr, Co, Zr, and Sb in a molar ratio is characterized by the specific surface area of the oxide controlled by the ratio. There is. An oxide produced by a process like the present invention is characterized in that an extremely fine oxide can be obtained, particularly in the case of an Al-containing Mg compound, for the above-described reason. In the case of ordinary MgO, although it depends on the manufacturing process conditions, there is no miniaturization effect of Al of the present invention, so
Only a specific surface area of about 20 m 2 / g can be obtained. However, the present invention is characterized in that a Mg compound having a remarkably large specific surface area, which cannot be obtained with conventional MgO, is obtained. Further, it is characterized in that high reactivity is obtained at a low melting point even with a specific surface area similar to that of conventional MgO. This allows
The reactivity in forming a glass coating is improved, and a grain-oriented electrical steel sheet having extremely excellent coating and magnetic properties can be obtained. If the specific surface area is in the range of 10 to 100 m 2 / g, the effects of low hydration, high reactivity and slurry viscosity optimization aimed at by the present invention can be obtained.
【００２１】本発明によれば、ＢＥＴ比表面積１０ｍ2
／ｇ未満では、本発明の成分酸化物を以てしてもグラス
形成向上効果が小さくなる為好ましくない。一方、１０
０ｍ 2 ／ｇ以上では、粘性が高くなりすぎ高速ラインで
の塗布が困難になる。また、水和水分の抑制が困難にな
り、脱炭焼鈍や仕上げ焼鈍条件によっては安定したグラ
ス皮膜が得られなくなる。According to the present invention, the BET specific surface area is 10 m.Two
/ G is less than glass even with the component oxide of the present invention.
It is not preferable because the effect of improving the formation becomes small. On the other hand, 10
0m Two/ G or more, the viscosity becomes too high, and
Becomes difficult to apply. In addition, it is difficult to control hydration moisture.
Depending on the conditions of decarburizing annealing and finish annealing.
Film cannot be obtained.
【００２２】次に本発明の酸化物の場合、水和水分は
０．５〜６．０％である。本発明においては、Ｍｇに対
し一定割合で添加されるＡｌと他の金属元素による酸化
物粒子の微粒化や反応性向上による皮膜形成反応向上効
果が得られる。しかしながら、０．５％未満では、仕上
げ焼鈍昇温過程での鋼板間の雰囲気がドライになり過ぎ
て、脱炭酸化膜の変質が生じ、グラス皮膜の厚みが薄く
なったり、密着性の低下、張力の低下が生じる。一方、
６．０％超では、本発明の高反応性焼鈍分離剤をもって
しても、過酸化状の皮膜欠陥として、シモフリ、ガスマ
ーク、スケール等が特に、大型コイルにおいては生じ易
くなるため制限される。Next, in the case of the oxide of the present invention, the water of hydration is 0.5 to 6.0%. In the present invention, the effect of improving the film-forming reaction by atomizing oxide particles and improving reactivity by Al and other metal elements added at a fixed ratio to Mg is obtained. However, if it is less than 0.5%, the atmosphere between the steel sheets in the step of raising the temperature of the finish annealing becomes too dry, and the quality of the decarboxylation film is changed, so that the thickness of the glass film becomes thin or the adhesion decreases. A drop in tension occurs. on the other hand,
When the content exceeds 6.0%, even with the highly reactive annealing separator of the present invention, as a peroxide-like film defect, shimofuri, gas mark, scale, and the like are easily generated particularly in a large coil, so that it is limited. .
【００２３】本発明においては、この様に通常のＭｇＯ
を用いる場合に比較して低水和域から高水和域までグラ
ス皮膜形成が優れるのが一つの特徴である。通常ＭｇＯ
によるグラス皮膜形成反応は、ＭｇＯの水和によって生
じるＭｇ（ＯＨ）2 の仕上げ焼鈍昇温過程に分解し、鋼
板間をウエット化する効果を主に利用にしている。これ
に対し、本発明の場合、前述の如く、Ａｌ等の添加元素
による微粒子化と反応性向上効果により、水分の作用を
それほど必要としない。このため、低水和域で反応性が
良く、且つ低温でグラス皮膜形成が生じるため、高温で
の追加酸化を抑制出来るため、水分の影響を受け難くな
っている為である。In the present invention, ordinary MgO
One of the features is that the glass film formation is excellent from the low hydration region to the high hydration region as compared with the case where is used. Usually MgO
The glass film formation reaction by the method mainly utilizes the effect of decomposing Mg (OH) 2 generated by hydration of MgO during the finish annealing temperature raising process and making the steel plates wet. On the other hand, in the case of the present invention, as described above, the effect of moisture is not so required due to the effect of forming fine particles and improving the reactivity by the additive element such as Al. For this reason, the reactivity is good in the low hydration region and the glass film is formed at a low temperature, so that the additional oxidation at a high temperature can be suppressed, so that it is hardly affected by moisture.
【００２４】次に、本発明におけるＭｇと共に用いられ
る添加元素のＡｌ，Ｃａ，Ｔｉ，Ｖ，Ｃｒ，Ｍｎ，Ｆ
ｅ，Ｓｒ，Ｃｏ，Ｚｒ，Ｓｂから選ばれる１種又は２種
以上の合計のは２０％以上がＭｇＯの結晶に固溶状態で
あることが好ましい。これらの添加元素は水酸化物構造
とされた後、焼成により酸化物とされる。このため、水
酸化物生成条件や焼成条件によっては固溶型の複合酸化
物構造を呈する。固溶量が２０％未満では、グラス皮膜
形成向上効果が弱く、脱炭焼鈍や仕上げ焼鈍条件によっ
ては不安定になるため制限される。Next, the additional elements Al, Ca, Ti, V, Cr, Mn, and F used together with Mg in the present invention.
Preferably, 20% or more of the total of one or more selected from e, Sr, Co, Zr, and Sb is in a solid solution state in the MgO crystal. After these additive elements have a hydroxide structure, they are converted into oxides by firing. For this reason, a solid solution type complex oxide structure is exhibited depending on the hydroxide generation conditions and firing conditions. If the amount of the solid solution is less than 20%, the effect of improving the formation of the glass film is weak, and it becomes unstable depending on the conditions of decarburizing annealing and finish annealing.
【００２５】次に、本発明の酸化物を焼鈍分離剤に用い
る場合、好ましい仕上げ焼鈍条件は雰囲気ガスがＮ2 １
０〜９０％、残部Ｈ2 とし、ＰＨ2 Ｏ／ＰＨ2 が０．０
１〜０．４である。本発明の焼鈍分離剤では、その高反
応性から比較的ドライ雰囲気でも良好なグラス皮膜が形
成される。雰囲気ガスのＮ2 比率は主に二次再結晶の安
定性の面で制限される。Ｎ2 １０％未満では、昇温時に
脱炭酸化膜の還元が生じ、グラス皮膜形成反応の低下を
もたらす一方、インヒビターとしてＡｌＮを用いる場
合、脱インヒビターが早まり、二次再結晶不安定化をも
たらす。一方、Ｎ 2 ９０％超では、鋼板への窒化が生じ
てＡｌＮの量や形態に影響をもたらす。この場合にも、
磁気特性の低下が生じるため好ましくない。雰囲気ガス
のＰＨ2 Ｏ／ＰＨ2 が０．０１未満の場合には、昇温時
に脱炭酸化膜の還元反応が生じて、グラス皮膜形成反応
を低下する。この場合も脱インヒビターが早まって磁性
の不安定化をもたらす。一方、０．４超の場合には、昇
温中に高温域で不均一な追加酸化が生じ、本発明の焼鈍
分離剤をもってしても均一なグラス皮膜が得られない。
特にコイル外周部やエッジ部に欠陥が生じ易くなる。こ
の場合にも、過剰酸化により脱インヒビターが生じ磁性
の低下が見られる。０．０１〜０．４の範囲ではこの様
な問題がなく、良好なグラス皮膜と磁気特性が得られ
る。Next, the oxide of the present invention is used as an annealing separator.
When the annealing gas is NTwo1
0-90%, balance HTwoAnd PHTwoO / PHTwoIs 0.0
1 to 0.4. In the annealing separator of the present invention,
Good glass film shape even in a relatively dry atmosphere due to its responsiveness
Is done. Atmospheric gas NTwoThe ratio is mainly the cost of secondary recrystallization.
Limited in qualitative terms. NTwoIf it is less than 10%,
Reduction of the decarboxylation film occurs, reducing the glass film formation reaction.
While using AlN as an inhibitor
Inhibition is accelerated, and secondary recrystallization becomes unstable
Sprinkle. On the other hand, N TwoIf it exceeds 90%, nitriding of the steel sheet occurs.
This affects the amount and form of AlN. Again, in this case,
It is not preferable because the magnetic properties are deteriorated. Atmosphere gas
PHTwoO / PHTwoIs less than 0.01,
A reduction reaction of the decarboxylation film occurs in the
Decrease. In this case, too, the inhibitor is prematurely magnetized
Causes instability. On the other hand, if it exceeds 0.4,
Non-uniform additional oxidation occurs in the high temperature range during the temperature, and the annealing of the present invention is performed.
Even with a separating agent, a uniform glass film cannot be obtained.
In particular, defects are likely to occur in the outer peripheral portion and the edge portion of the coil. This
In the case of overheating, deoxidation occurs due to excessive oxidation
Is seen to decrease. In the range of 0.01 to 0.4
Good glass film and good magnetic properties
You.
【００２６】図１に本発明の（Ａ）焼鈍分離剤として、
実施例２−本発明４を使用した場合と（Ｂ）実施例２−
比較例１のＡｌのみ添加した場合、（Ｃ）実施例１の比
較例２の従来のＭｇＯを焼鈍分離剤として使用した場合
のグラス被膜形成反応を仕上げ焼鈍過程で解析した結果
を示す。この実験に於いては適用した方向性電磁鋼板サ
ンプルは、実施例２と同一の素材である。FIG. 1 shows (A) the annealing separator of the present invention.
Example 2-The case where the present invention 4 was used and (B) Example 2-
The results of analyzing the glass film forming reaction in the case of adding only Al of Comparative Example 1 and (C) the case of using the conventional MgO of Comparative Example 2 of Example 1 as an annealing separator in the finish annealing process are shown. In this experiment, the grain-oriented electrical steel sheet sample applied was the same material as in Example 2.
【００２７】図１に示される如く、本発明によるものは
仕上げ焼鈍昇温過程でより低温からグラス被膜が形成さ
れ、最終的な形成量も比較例より多いことが確認され
た。しかし、Ａｌのみを添加した比較例ではやや反応性
が劣るため皮膜形成量が少なく、また、従来のＭｇＯを
用いた場合には極端に皮膜形成量が少ないことが確認さ
れた。As shown in FIG. 1, it was confirmed that the glass according to the present invention formed a glass film from a lower temperature in the course of the finish annealing heating, and the final formation amount was larger than that of the comparative example. However, it was confirmed that in the comparative example to which only Al was added, the film formation amount was small due to slightly inferior reactivity, and when the conventional MgO was used, the film formation amount was extremely small.
【００２８】[0028]
＜実施例１＞重量％でＣ；０．０５４，Ｓｉ；３．０
０，Ｍｎ；０．０６０，Ｓ；０．０２４，Ａｌ；０．０
０７、残部を不可避の不純物とＦｅよりなる方向性電磁
鋼板素材を公知の方法で熱延と焼鈍を挟む２回の冷間圧
延により最終板厚０．３４mmとした。この後、炉温８５
０℃、Ｎ2 ２５％＋Ｈ2 ７５％、露点６６℃の雰囲気ガ
ス中で脱炭焼鈍し、脱炭と表面にＳｉＯ2 主体の酸化層
を形成し、表１に示す組成の焼鈍分離剤を液温度５℃で
プロペラ状の攪拌装置をもうけたタンク内で１５００rp
m ×１２０min.攪拌後、塗布し、乾燥後２０Ｔコイルに
巻取り１２００℃×２０Hrの最終焼鈍を行った。この
後、２０％コロイダルシリカ：１００ml，５０％リン酸
Ａｌ：５０ml，ＣｒＯ3 ：４ｇからなる絶縁被膜剤を乾
燥後の重量で２．５ｇ／ｍ2 の重量になる様に塗布し８
５０℃でヒートフラットニングと焼き付け処理を行っ
た。この試験に於ける仕上げ焼鈍後のグラス被膜の形成
状態、絶縁被膜処理焼き付け後の被膜特性を表２に示
す。<Example 1>C; 0.054, Si; 3.0% by weight.
0, Mn; 0.060, S; 0.024, Al; 0.0
07, the remainder of the grain-oriented electrical steel sheet material consisting of unavoidable impurities and Fe was cold rolled twice with hot rolling and annealing by a known method to a final sheet thickness of 0.34 mm. After this, furnace temperature 85
Decarburizing annealing in an atmosphere gas of 0 ° C., 25% N 2 + 75% H 2 and a dew point of 66 ° C. to form an oxide layer mainly composed of SiO 2 on the surface after decarburizing. 1500 rp in a tank with a propeller-like stirring device at a liquid temperature of 5 ° C
After stirring for mx 120 min., the mixture was applied, dried, wound around a 20T coil, and subjected to final annealing at 1200 ° C for 20 hours. Thereafter, an insulating coating agent composed of 20% colloidal silica: 100 ml, 50% Al phosphate: 50 ml, and CrO 3 : 4 g was applied so that the weight after drying was 2.5 g / m 2.
Heat flattening and baking were performed at 50 ° C. Table 2 shows the state of formation of the glass film after the finish annealing in this test and the film properties after the baking treatment with the insulating film.
【００２９】[0029]
【表１】 [Table 1]
【００３０】[0030]
【表２】 この実験の結果、本発明によるものは何れもコイル全長
に渡って、厚く、光沢のあるグラス被膜がコイル全面に
わたって形成され、絶縁被膜処理後の被膜の密着性が良
好であった。一方、比較例の焼鈍分離剤に通常のＭｇＯ
や添加元素のＡｌに対する他の元素の割合が少ない本発
明外の場合には、グラス皮膜が薄かったり、ガスマーク
状のムラが鋼板のエッジ部に生じ、密着性も本発明に比
較してかなり劣る結果となった。又、磁気特性に於いて
も、本発明の焼鈍分離剤の場合、磁気特性が安定して良
好で、特に、鉄損が極めて良好な値を示したのに対し、
比較例は磁束密度、鉄損共かなり劣る結果となった。[Table 2] As a result of this experiment, in any of the devices according to the present invention, a thick and glossy glass film was formed over the entire surface of the coil, and the adhesion of the film after the insulating film treatment was good. On the other hand, ordinary MgO was used for the annealing separator of the comparative example.
In the case where the ratio of other elements to Al and the added element is small outside the present invention, the glass film is thin or gas mark-like unevenness occurs at the edge of the steel sheet, and the adhesion is considerably higher than that of the present invention. Inferior results. Also, in the magnetic properties, in the case of the annealing separator of the present invention, the magnetic properties are stable and good, especially, while the iron loss showed a very good value,
In the comparative example, both the magnetic flux density and the iron loss were inferior.
【００３１】＜実施例２＞重量％でＣ；０．０８０，Ｓ
ｉ；３．３０，Ｍｎ；０．０７５，Ｓ；０．０２５，Ｃ
ｕ；０．０８，Ｓｎ；０．０６，Ａｌ；０．０２８，
Ｎ；０．００７９残部を不可避の不純物とＦｅからなる
高磁束密度方向性電磁鋼板素材スラブを公知の方法で熱
延−焼鈍−酸洗−冷間圧延により最終板厚０．２２５mm
とした。この鋼板をＮ2 ２５％＋Ｈ2 ７５％、露点６８
℃の湿潤雰囲気ガス中で８５０℃×１２０秒間脱炭焼鈍
を行った。次いで、表３に示す組成の酸化物を主成分と
する焼鈍分離剤(*1)を液温１０℃で実施例と同一の攪拌
装置を用いて１０００rpm ×６０分間攪拌した。次い
で、乾燥後の重量で１２ｇ／ｍ2 になる様に塗布し、乾
燥後１２００℃×２０Hrの最終仕上げ焼鈍を行った。そ
の後、絶縁被膜剤として実施例１と同一組成の被膜剤を
乾燥・焼き付け後の重量で５ｇ／ｍ2 になるように塗布
し、炉温８５０℃でヒートフラットニングと焼き付け処
理を行った。このときの被膜特性と磁気特性の結果を表
４に示す。Example 2 C: 0.080, S by weight%
i; 3.30, Mn; 0.075, S; 0.025, C
u; 0.08, Sn; 0.06, Al; 0.028,
N: 0.0079 high magnetic flux density directional magnetic steel sheet material composed of unavoidable impurities and Fe with the balance being 0.0079 by hot rolling, annealing, pickling, and cold rolling by a known method to a final sheet thickness of 0.225 mm.
And The steel plate N 2 25% + H 2 75 %, dew point 68
Decarburization annealing was performed at 850 ° C. for 120 seconds in a humid atmosphere gas at 850 ° C. Next, an annealing separator (* 1) containing an oxide as a main component having the composition shown in Table 3 was stirred at a liquid temperature of 10 ° C. using the same stirring apparatus as in the example at 1,000 rpm × 60 minutes. Next, it was applied so that the weight after drying was 12 g / m 2, and after the drying, final finishing annealing at 1200 ° C. × 20 hours was performed. Thereafter, a coating agent having the same composition as in Example 1 was applied as an insulating coating agent so that the weight after drying and baking was 5 g / m 2 , and heat flattening and baking were performed at a furnace temperature of 850 ° C. Table 4 shows the results of the film properties and magnetic properties at this time.
【００３２】この試験の結果、本発明の酸化物を焼鈍分
離剤として用いたものは、いずれもグラス被膜がコイル
の全長、全面にわたって均一に形成され、グラス被膜の
張力、密着性とも良好であった。又、磁気特性に於いて
も本発明のものは、何れも極めて良好な磁束密度と鉄損
特性が得られた。これに対し、比較例のＡｌ単独添加
や、Ａｌ以外の他の元素の添加の少ない物は水和水分、
スラリー粘度が高く、均一に塗布が出来ず、皮膜磁性、
磁気特性共不良であった。また、Ａｌの添加のない場合
には、焼成時にシンタリングが生じ、グラス皮膜の形成
及び磁気特性がやや劣る結果となった。As a result of this test, in each of the cases where the oxide of the present invention was used as an annealing separator, the glass coating was formed uniformly over the entire length and the entire surface of the coil, and the tension and adhesion of the glass coating were good. Was. Regarding the magnetic characteristics, all of the magnetic recording media of the present invention exhibited extremely good magnetic flux density and iron loss characteristics. On the other hand, in the comparative example, the addition of Al alone or the one in which the addition of other elements other than Al is small indicates hydration
Slurry viscosity is high, coating cannot be performed uniformly, film magnetic,
Both magnetic properties were poor. In addition, when Al was not added, sintering occurred during firing, resulting in the formation of a glass film and the magnetic properties were slightly inferior.
【００３３】[0033]
【表３】 [Table 3]
【００３４】[0034]
【表４】 [Table 4]
【００３５】[0035]
【発明の効果】以上、詳述した様に、本発明は新規な焼
鈍分離剤として、ＭｇＯ製造過程において、モル比でＭ
ｇ１００に対しＡｌを０．０５〜１０とＣａ，Ｔｉ，
Ｖ，Ｃｒ，Ｆｅ，Ｍｎ，Ｃｏ，Ｚｒ，Ｓｂ等をＡｌに対
し０．５〜１０の割合で添加し製造した酸化物を用いる
ことにより、低融点化効果と反応性向上効果が得られ、
更に、塗布工程におけるスラリー調整時に粘性が容易に
制御されて高速ラインにおいても均一な塗布が実現でき
る。この結果、グラス皮膜がコイル全面に渡って均一に
形成され、インヒビターの変質、弱体化を防止して良好
な磁気特性が得られる。As described in detail above, the present invention provides a novel annealing separator as a new annealing separator in a molar ratio of M
g100 with respect to 0.05 to 10 Al and Ca, Ti,
By using an oxide prepared by adding V, Cr, Fe, Mn, Co, Zr, Sb, etc. to Al at a ratio of 0.5 to 10, an effect of lowering the melting point and an effect of improving the reactivity can be obtained.
Further, the viscosity is easily controlled at the time of adjusting the slurry in the coating step, and uniform coating can be realized even in a high-speed line. As a result, the glass film is formed uniformly over the entire surface of the coil, thereby preventing deterioration and weakening of the inhibitor, thereby obtaining good magnetic properties.
【図１】本発明の（Ａ）焼鈍分離剤として、実施例２−
本発明４を使用した場合と（Ｂ）実施例２−比較例１の
Ａｌのみ添加した場合、（Ｃ）実施例１の比較例２の従
来のＭｇＯを焼鈍分離剤として使用した場合のグラス被
膜形成反応を仕上げ焼鈍過程で解析した結果を示す図で
ある。FIG. 1 shows an example of an annealing separator of the present invention (A) of Example 2-
Glass coating in the case of using the present invention 4, (B) in the case of adding only Al of Example 2-Comparative Example 1, and (C) in the case of using the conventional MgO of Comparative Example 2 of Example 1 as an annealing separator. It is a figure which shows the result of having analyzed the formation reaction in the finish annealing process.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山本 紀宏 福岡県北九州市戸畑区飛幡町１−１ 新日 本製鐵株式会社八幡製鐵所内 (72)発明者 田中 収 福岡県北九州市戸畑区大字中原46番地の59 日鐵プラント設計株式会社内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Norihiro Yamamoto 1-1 Niwahata-cho, Tobata-ku, Kitakyushu-shi, Fukuoka Nippon Steel Corporation Yawata Works (72) Inventor Osamu Tanaka Larger section of Tobata-ku, Kitakyushu-shi, Fukuoka Inside Nippon Steel Plant Design Co., Ltd. at 46 Nakahara
Claims (3)
ａ，Ｔｉ，Ｖ，Ｃｒ，Ｍｎ，Ｆｅ，Ｓｒ，Ｃｏ，Ｚｒ，
Ｓｂの中から選ばれる１種又は２種以上を合計で０．０
５〜１０からなる酸化物で、且つ、（Ａｌ以外の元素の
モル比のトータル数）／（Ａｌのモル数）比率が０．５
〜１０であり、ＢＥＴ比表面積が１０〜１００ｍ2 ／
ｇ、水和水分が０．５〜６．０％であることを特徴とす
る皮膜形成能に優れる方向性電磁鋼板用焼鈍分離剤。1. A molar ratio of Mg; 100 to Al, C
a, Ti, V, Cr, Mn, Fe, Sr, Co, Zr,
One or more selected from Sb is used in a total of 0.0
An oxide composed of 5 to 10 and having a ratio of (total number of mole ratios of elements other than Al) / (mol number of Al) of 0.5
And a BET specific surface area of 10 to 100 m 2 /
g, an annealing separator for grain-oriented electrical steel sheets having excellent film-forming ability, having a hydrated water content of 0.5 to 6.0%.
Ｃｒ，Ｍｎ，Ｆｅ，Ｓｒ，Ｃｏ，Ｚｒ，Ｓｂの中から選
ばれる１種又は２種以上の合計の２０％以上がＭｇＯ結
晶の中で置換固溶されていることを特徴とする請求項１
記載の皮膜形成能に優れる方向性電磁鋼板用焼鈍分離
剤。2. The method according to claim 1, wherein Al, Ca, Ti, V,
2. The MgO crystal according to claim 1, wherein at least 20% of a total of one or more selected from Cr, Mn, Fe, Sr, Co, Zr, and Sb is substituted and solid-solved in the MgO crystal.
An annealing separator for grain-oriented electrical steel sheets having excellent film-forming ability as described.
コイルを脱炭焼鈍し、焼鈍分離剤を塗布乾燥後、仕上げ
焼鈍し、絶縁皮膜剤を塗布焼き付けすることからなる工
程において、脱炭焼鈍後の鋼板表面に請求項１または２
記載の焼鈍分離剤を塗布乾燥後仕上げ焼鈍を行うに際
し、昇温時の雰囲気ガスをＮ2 １０〜９０％、残部をＨ
2 とし、ＰＨ2 Ｏ／ＰＨ2 を０．０１〜０．４として焼
鈍することを特徴とするグラス皮膜の優れる方向性電磁
鋼板の製造方法。3. A process comprising the steps of decarburizing and annealing a grain-oriented electrical steel sheet coil cold-rolled to a final thickness, applying and drying an annealing separating agent, finish annealing, and applying and baking an insulating film agent. 3. The steel sheet surface after carbon annealing
When performing the finish annealing after applying and drying the described annealing separator, the atmosphere gas at the time of temperature rise is N 2 10 to 90%, and the remainder is H.
2, and the manufacturing method of the grain-oriented electrical steel sheet having excellent glass coating film, which comprises annealing the PH 2 O / PH 2 as 0.01 to 0.4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21150696A JP3356933B2 (en) | 1996-08-09 | 1996-08-09 | Annealing separator with excellent film-forming ability and method for producing grain-oriented electrical steel sheet using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21150696A JP3356933B2 (en) | 1996-08-09 | 1996-08-09 | Annealing separator with excellent film-forming ability and method for producing grain-oriented electrical steel sheet using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1053818A true JPH1053818A (en) | 1998-02-24 |
| JP3356933B2 JP3356933B2 (en) | 2002-12-16 |
Family
ID=16607067
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21150696A Expired - Lifetime JP3356933B2 (en) | 1996-08-09 | 1996-08-09 | Annealing separator with excellent film-forming ability and method for producing grain-oriented electrical steel sheet using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3356933B2 (en) |
Cited By (6)
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|---|---|---|---|---|
| JPH11302730A (en) * | 1998-04-24 | 1999-11-02 | Kawasaki Steel Corp | Production of grain-oriented silicon steel sheet excellent in coating characteristic and low magnetic field characteristic |
| JP2003082472A (en) * | 2001-09-11 | 2003-03-19 | Nippon Steel Corp | Separation agent for annealing, and method for producing grain oriented magnetic steel sheet having excellent glass film and magnetic property |
| KR20180012335A (en) * | 2016-05-13 | 2018-02-05 | 코노시마카가쿠코우교우 가부시키가이샤 | Magnesium oxide powder and manufacturing method thereof |
| CN109072332A (en) * | 2016-03-30 | 2018-12-21 | 达泰豪化学工业株式会社 | Annealing separation agent magnesia and orientation electrical sheet |
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1996
- 1996-08-09 JP JP21150696A patent/JP3356933B2/en not_active Expired - Lifetime
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|---|---|---|---|---|
| JPH11302730A (en) * | 1998-04-24 | 1999-11-02 | Kawasaki Steel Corp | Production of grain-oriented silicon steel sheet excellent in coating characteristic and low magnetic field characteristic |
| JP2003082472A (en) * | 2001-09-11 | 2003-03-19 | Nippon Steel Corp | Separation agent for annealing, and method for producing grain oriented magnetic steel sheet having excellent glass film and magnetic property |
| CN109072332A (en) * | 2016-03-30 | 2018-12-21 | 达泰豪化学工业株式会社 | Annealing separation agent magnesia and orientation electrical sheet |
| CN109072332B (en) * | 2016-03-30 | 2023-05-30 | 达泰豪化学工业株式会社 | Magnesium oxide for annealing separating agent and oriented electrical steel |
| KR20180012335A (en) * | 2016-05-13 | 2018-02-05 | 코노시마카가쿠코우교우 가부시키가이샤 | Magnesium oxide powder and manufacturing method thereof |
| JP6277334B1 (en) * | 2016-05-13 | 2018-02-07 | 神島化学工業株式会社 | Magnesium oxide powder and method for producing the same |
| KR101878963B1 (en) * | 2016-05-13 | 2018-07-16 | 코노시마카가쿠코우교우 가부시키가이샤 | Magnesium oxide powder and manufacturing method thereof |
| KR20210080084A (en) * | 2019-12-20 | 2021-06-30 | 주식회사 포스코 | Annealing separating agent composition for grain oriented electrical steel sheet, grain oriented electrical steel sheet, and method for manufacturing the same |
| WO2021125863A3 (en) * | 2019-12-20 | 2021-08-05 | 주식회사 포스코 | Annealing separator composition for grain-oriented electrical steel sheet, grain-oriented electrical steel sheet, and manufacturing method therefor |
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