JP3336547B2 - Method for manufacturing grain-oriented electrical steel sheet with extremely excellent glass coating and magnetic properties - Google Patents
Method for manufacturing grain-oriented electrical steel sheet with extremely excellent glass coating and magnetic propertiesInfo
- Publication number
- JP3336547B2 JP3336547B2 JP28229394A JP28229394A JP3336547B2 JP 3336547 B2 JP3336547 B2 JP 3336547B2 JP 28229394 A JP28229394 A JP 28229394A JP 28229394 A JP28229394 A JP 28229394A JP 3336547 B2 JP3336547 B2 JP 3336547B2
- Authority
- JP
- Japan
- Prior art keywords
- annealing
- steel sheet
- weight
- mgo
- oriented electrical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
- H01F1/147—Alloys characterised by their composition
- H01F1/14766—Fe-Si based alloys
- H01F1/14775—Fe-Si based alloys in the form of sheets
- H01F1/14783—Fe-Si based alloys in the form of sheets with insulating coating
Description
【０００１】[0001]
【産業上の利用分野】本発明は方向性電磁鋼板の製造に
際し、最終仕上げ焼鈍工程において、均一で優れた被膜
性能をもつグラス被膜を形成すると共に、優れた磁気特
性を得るための方向性電磁鋼板の製造方法に関する。BACKGROUND OF THE INVENTION The present invention relates to a directional electromagnetic steel sheet for producing a directional magnetic steel sheet in a final finish annealing step to form a glass film having a uniform and excellent coating performance and to obtain excellent magnetic properties. The present invention relates to a method for manufacturing a steel sheet.
【０００２】[0002]
【従来の技術】通常、方向性電磁鋼板はＳｉ：２．５〜
４．０％を含有する素材スラブを熱延し、焼鈍と１回又
は中間焼鈍を挟む２回以上の冷延により最終板厚とされ
る。次いで、連続焼鈍炉においてＨ2 或いはＮ2 ＋Ｈ2
雰囲気中でＰ H2 O ／Ｐ H2 を制御して脱炭焼鈍を行
い、脱炭、一次再結晶及びＳｉＯ2 を主成分とする酸化
層形成処理を行う。その後、ＭｇＯを主成分とする焼鈍
分離剤をスラリー状としてコーティングロール等により
鋼板に塗布し、乾燥後、コイルに巻き取り最終仕上げ焼
鈍を行い、通常は絶縁被膜剤処理とヒートフラットニン
グを行って最終製品とされる。2. Description of the Related Art Grain-oriented electrical steel sheets are usually made of Si: 2.5 to
A material slab containing 4.0% is hot-rolled, and the final thickness is made by annealing and one or two or more cold-rolling sandwiching intermediate annealing. Then, in a continuous annealing furnace, H 2 or N 2 + H 2
Decarburization annealing is performed in an atmosphere while controlling P H 2 O / P H 2, and decarburization, primary recrystallization, and an oxide layer forming process mainly containing SiO 2 are performed. After that, an annealing separator containing MgO as a main component is applied in a slurry state to a steel plate by a coating roll or the like, dried, wound up in a coil, and then subjected to final finish annealing, and is usually subjected to an insulating coating agent treatment and heat flattening. It is considered a final product.
【０００３】この方向性電磁鋼板は〈００１〉軸をもつ
（１１０）〈００１〉結晶が高温の二次再結晶で優先的
に成長し、鋼中にインヒビターとして分散しているＡｌ
Ｎ，ＭｎＳ等によって、その成長を抑えられている他の
結晶を侵食するために（１１０）〈００１〉結晶が優先
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、鋼中インヒビターＡ
ｌＮ，ＭｎＳ等の分散状態とこれらの分解までの制御が
重要である。特に、最終仕上げ焼鈍においてインヒビタ
ーは脱炭焼鈍で形成した鋼板表面の酸化膜、焼鈍分離剤
及び最終仕上げ焼鈍での熱サイクルや雰囲気ガス条件に
より影響を受ける。[0003] In this grain-oriented electrical steel sheet, (110) <001> crystal having <001> axis grows preferentially by secondary recrystallization at high temperature, and Al is dispersed as an inhibitor in the steel.
It is considered that the (110) <001> crystal grows preferentially because it erodes other crystals whose growth is suppressed by N, MnS and the like. Therefore, in order to produce an excellent grain-oriented electrical steel sheet, it is necessary to use the inhibitor A in steel.
It is important to control the dispersion state of 1N, MnS, and the like, and to control their decomposition. In particular, in the final finish annealing, the inhibitor is affected by the oxide film on the steel sheet surface formed by the decarburizing annealing, the annealing separator, the heat cycle in the final finish annealing, and the atmospheric gas conditions.
【０００４】これ等の中で、とりわけ脱炭焼鈍時に鋼板
表面に形成する酸化膜の質及び量と焼鈍分離剤に用いる
グラス被膜形成剤のＭｇＯと添加剤は、グラス被膜形成
を介してのインヒビターの挙動に影響が大きいため、結
晶の方向性を左右する。[0004] Among them, the quality and quantity of the oxide film formed on the steel sheet surface during the decarburization annealing, and the MgO and the additive of the glass film forming agent used as the annealing separator are, among others, an inhibitor through the formation of the glass film. Has a large influence on the behavior of the crystal, and thus determines the directionality of the crystal.
【０００５】又、グラス被膜の張力効果による鉄損改善
効果にも大きい影響を与える。これは、ＭｇＯの粒子の
純度、活性度、粒度等の物性値が最終焼鈍での昇温過程
における脱炭酸化膜の変化やグラス被膜の形成反応開始
温度、成長速度、コイル板間の雰囲気酸化度等に多大な
影響をもたらして、グラス被膜の形成状態等によって鋼
中インヒビターの安定性に影響を与えるからである。[0005] In addition, the effect of improving the iron loss due to the tension effect of the glass coating is greatly affected. This is because physical properties such as purity, activity, and particle size of the MgO particles change in the decarboxylation film during the temperature rise process in the final annealing, the glass film formation reaction initiation temperature, the growth rate, and the atmospheric oxidation between coil plates. This is because it has a great influence on the degree and the like, and the stability of the inhibitor in steel is affected by the state of formation of the glass film.
【０００６】仕上げ焼鈍におけるグラス被膜形成反応
は、焼鈍分離剤のＭｇＯと脱炭焼鈍で形成されたＳｉＯ
2 主体の酸化膜と反応して通常グラス被膜と呼ぶフォル
ステライト被膜を形成する（２ＭｇＯ＋ＳｉＯ2 →Ｍｇ
2 ＳｉＯ4 ）。又、この際、鋼中インヒビターとしてＡ
ｌＮを用いる場合にはフォルステライト被膜直下付近に
Ａｌ2 Ｏ3 とＭｇＯ，ＳｉＯ2 等によるスピネル構造の
化合物を形成する。[0006] The reaction of forming a glass film in the finish annealing is performed by using MgO as an annealing separator and SiO formed by decarburizing annealing.
It reacts with the oxide film mainly composed of 2 to form a forsterite film usually called a glass film (2MgO + SiO 2 → Mg)
2 SiO 4 ). At this time, A as an inhibitor in steel
When 1N is used, a compound having a spinel structure of Al 2 O 3 , MgO, SiO 2 or the like is formed immediately below the forsterite film.
【０００７】このグラス被膜形成においては、ＭｇＯと
ＳｉＯ2 の反応は純粋系においては１６００℃近い高温
でなければ反応が生じないため、酸化膜の性状（成分、
形成状態）、仕上げ焼鈍条件の制御（ヒートサイクル、
雰囲気ガス）と共に焼鈍分離剤の性状として、主成分の
ＭｇＯの不純物の調整、粒径、粒子形状、表面状態、活
性度等の他、反応促進剤の添加剤を利用して、仕上げ焼
鈍工程においていかに低温から均一なグラス被膜形成を
行わせるかが優れたグラス被膜と良好な磁気特性を得る
ための重要な鍵となる。In the formation of the glass film, the reaction between MgO and SiO 2 does not occur in a pure system unless the temperature is as high as about 1600 ° C., so that the properties (components,
Control of finish annealing conditions (heat cycle,
Atmosphere gas) together with the properties of the annealing separator, such as adjustment of impurities of the main component MgO, particle size, particle shape, surface state, activity, etc. How to form a uniform glass film from a low temperature is an important key for obtaining an excellent glass film and good magnetic properties.
【０００８】このように、方向性電磁鋼板の商品価値を
決定する上で重要なグラス被膜と磁気特性に対して、脱
炭酸化膜と焼鈍分離剤ＭｇＯの添加剤の影響が大きいこ
とから、酸化膜の成分や量にマッチした新しい添加剤物
質の開発と改善は方向性電磁鋼板製造技術上重要な課題
となってきている。焼鈍分離剤に使用するＭｇＯは、一
般的にはＭｇＣｌ2 或いは海水等を原料として、先ず、
Ｃａ（ＯＨ）2 との反応によりＭｇ（ＯＨ）2 結晶を調
整し、純度等の調整の目的で圧縮洗浄等によって１回又
は洗浄と結晶調整を挟む２回以上の焼成によってＭｇＯ
とされ、必要に応じて粉砕、分級等による粒度調整を行
って製品とされる。[0008] As described above, the additive of the decarbonated film and the annealing separator MgO has a large effect on the glass coating and the magnetic properties which are important in determining the commercial value of the grain-oriented electrical steel sheet. The development and improvement of new additive materials that match the composition and amount of the film has become an important issue in the production technology of grain-oriented electrical steel sheets. MgO used for the annealing separator is generally made of MgCl 2 or seawater as a raw material.
The Mg (OH) 2 crystal is adjusted by the reaction with Ca (OH) 2, and the MgO is crystallized once by compression washing or the like or by firing two or more times between washing and crystal adjustment for the purpose of adjusting the purity and the like.
The product is subjected to particle size adjustment by pulverization, classification, and the like, if necessary, to obtain a product.
【０００９】ＭｇＯの性状の中でグラス被膜形成とこれ
に関連して、インヒビターの安定性ひいては磁気特性に
影響する因子としては、ＭｇＯの純度、粒度、活性度、
鋼板への密着性等が主なものであり、このＭｇＯが鋼板
に塗布される際には、水和の進行度合い、粒子の水スラ
リー中の分散状態、塗布量等がある。このため、優れた
グラス被膜と磁気特性を有する方向性電磁鋼板を得るた
めには、これ等の条件を最適にすることが重要である。Among the properties of MgO, glass film formation and related factors that affect the stability of the inhibitor and thus the magnetic properties include the purity, particle size, activity of MgO, and the like.
The main property is adhesion to a steel sheet and the like. When this MgO is applied to a steel sheet, there are a progress degree of hydration, a dispersion state of particles in a water slurry, an application amount, and the like. Therefore, in order to obtain a grain-oriented electrical steel sheet having excellent glass coating and magnetic properties, it is important to optimize these conditions.
【００１０】前述のように、通常、ＭｇＯは必要に応じ
て反応促進剤として配合する少量の添加剤と共に水に懸
濁させて、スラリー状として鋼板に塗布される。この添
加剤は通常、酸化物、Ｓ化合物、Ｂ化合物等がフォルス
テライト被膜形成の反応促進剤として利用されてきた。
この際、ＭｇＯの製造条件によっては、例えば高活性の
場合、水との混合撹拌条件によってはＭｇＯ→ＭｇＯ
（ＯＨ）2 となる水和反応が生じ、コイル内（板間）に
水分を持ち込む結果、板間露点を高め且つコイル長手方
向及び幅方向において雰囲気状態を不均一にする問題が
ある。As described above, usually, MgO is suspended in water together with a small amount of an additive to be added as a reaction accelerator if necessary, and is applied to a steel sheet as a slurry. As the additives, oxides, S compounds, B compounds, and the like have been generally used as a reaction accelerator for forming a forsterite film.
At this time, depending on the production conditions of MgO, for example, in the case of high activity, depending on the mixing and stirring conditions with water, MgO → MgO
A hydration reaction to form (OH) 2 occurs, bringing moisture into the coil (between the plates). As a result, there is a problem that the dew point between the plates is increased and the atmosphere state is made non-uniform in the longitudinal and width directions of the coil.
【００１１】又、添加剤の種類や量によっては、余剰の
酸素や反応促進効果の違いによって、グラス被膜の質、
量に大きい影響を与える。このため、仕上げ焼鈍昇温過
程で不均一で、過剰な追加酸化を生じさせ、スケール、
ガスマーク、ピンホール、変色等の重度の被膜欠陥を引
き起こす。Further, depending on the type and amount of the additive, the quality of the glass film may be affected by the difference between the excess oxygen and the reaction promoting effect.
Has a great effect on quantity. For this reason, the non-uniform, excessive additional oxidation occurs during the temperature rise process of the finish annealing, and the scale,
Causes severe film defects such as gas marks, pinholes and discoloration.
【００１２】この高水和による問題点を解決するための
手段としては、一般的には、高温焼成による方法が採用
される。この方法として、例えば特開昭５５−７３８２
３号公報がある。このように焼成温度を上げることで得
られた低活性ＭｇＯでは、水和性の低下は得られるが、
活性（反応性）や付着性が低下する欠点がある。又、特
開昭６２−１５６２２６号公報には、ＭｇＯ粒子の最表
面層を活性化処理する方法が提案されている。この方法
では、高温焼成したＭｇＯの最表面層のみを気相中で処
理して水和層を形成するものである。これによりグラス
被膜と磁気特性のかなりの向上が見られている。As a means for solving the problem caused by the high hydration, a method of firing at high temperature is generally adopted. As this method, for example, JP-A-55-7382 is used.
There is No. 3 publication. In the case of the low-activity MgO obtained by increasing the firing temperature in this way, although a decrease in hydration is obtained,
There is a disadvantage that the activity (reactivity) and the adhesiveness are reduced. Japanese Patent Application Laid-Open No. Sho 62-156226 proposes a method for activating the outermost surface layer of MgO particles. In this method, only the outermost surface layer of MgO fired at a high temperature is treated in a gas phase to form a hydrated layer. This shows a considerable improvement in glass coating and magnetic properties.
【００１３】更に、焼鈍分離剤中への添加剤によるグラ
ス被膜及び磁性の改善技術として、特公平２−５８２０
号公報には、Ｓｂ，Ｓｒ，Ｔｉ，Ｚｒの塩化物の１種又
は２種以上をＭｇＯ：１００重量部に対して０．０２〜
１．５重量部添加する方法が提案されている。これによ
り、添加剤化合物が鋼板表面の酸化層成分のＳｉＯ2リ
ッチ化と緻密化をもたらし、仕上げ焼鈍において追加酸
化の抑制と反応促進効果をもたらして、優れた鉄損特性
とグラス被膜が得られるものである。又、特開平３−１
２０３７６号公報には前記のような塩化物の添加技術の
改善技術として、Ｍｇ，Ｎａ，Ｋ及びＣａから選択され
た金属塩化物をＭｇＯへ添加すれば硫酸アンチモン、メ
タ珪酸ナトリウムの併用なしに磁気特性の改善効果が得
られることが示されている。Further, as a technique for improving the glass coating and magnetism by using an additive in an annealing separator, Japanese Patent Publication No. 2-5820
The publication discloses that one or more of chlorides of Sb, Sr, Ti and Zr are used in an amount of 0.02 to 100 parts by weight of MgO.
A method of adding 1.5 parts by weight has been proposed. As a result, the additive compound brings about the SiO 2 enrichment and densification of the oxide layer component on the steel sheet surface, suppresses the additional oxidation in the finish annealing, and has the effect of accelerating the reaction, so that excellent iron loss characteristics and glass coating can be obtained. Things. Also, Japanese Patent Laid-Open No. 3-1
Japanese Patent No. 20376 discloses a technique for improving the above-mentioned chloride addition technique, in which a metal chloride selected from Mg, Na, K and Ca is added to MgO without using antimony sulfate and sodium metasilicate together. It is shown that an effect of improving characteristics can be obtained.
【００１４】[0014]
【発明が解決しようとする課題】このように、これ等の
ＭｇＯの性状や反応促進剤の添加剤を改善することでグ
ラス被膜形成反応が改善され、効果が得られている。し
かし、鋼成分、脱炭焼鈍条件や最終仕上げ焼鈍条件によ
ってはグラス被膜特性や磁気特性が不安定になる場合が
あり、未だ十分な技術とはいえず、更なる技術改善が望
まれているところである。このように、低水和で高反応
性の焼鈍分離剤の開発は方向性電磁鋼板の製造に関わる
技術者の長年の目標となっている。As described above, by improving the properties of MgO and the additives of the reaction accelerator, the glass film forming reaction is improved and the effect is obtained. However, depending on the steel composition, decarburizing annealing conditions and final finishing annealing conditions, the glass coating properties and magnetic properties may be unstable, and this is not yet a sufficient technology, and further technical improvements are desired. is there. Thus, the development of a low hydration, highly reactive annealing separator has been a long-standing goal of engineers involved in the production of grain-oriented electrical steel sheets.
【００１５】本発明者等は低水和で且つ高反応性の焼鈍
分離剤の実現に到達すべく、グラス被膜の反応性向上策
について膨大な研究と実験を行って検討した。その結
果、脱炭酸化膜成分の（Ｆｅ，Ｍｎ）−Ｏ量の一定条件
下において、ＭｇＯの反応性向上促進剤として、一定域
の融点を有する塩素化合物とアルカリ金属化合物及び／
又はアルカリ土類金属化合物を複合添加することで、グ
ラス被膜の形成反応性が優れ、被膜特性と磁気特性の極
めて良好な方向性電磁鋼板が得られることを見いだし
た。The present inventors have conducted a great deal of research and experiments to improve the reactivity of glass coatings in order to achieve an annealing separator having low hydration and high reactivity. As a result, under a certain condition of the amount of (Fe, Mn) -O of the decarboxylation film component, a chlorine compound having a certain range of melting point, an alkali metal compound and / or
Alternatively, it has been found that by adding an alkaline earth metal compound in combination, a grain-oriented electrical steel sheet having excellent glass film formation reactivity and extremely good film properties and magnetic properties can be obtained.
【００１６】[0016]
【課題を解決するための手段】本発明は、グラス被膜形
成における脱炭焼鈍酸化膜成分と焼鈍分離剤ＭｇＯへの
添加剤の従来技術における解決策として、以下の構成を
要旨とする。Ｃ：０．０３０〜０．１００wt％、Ｓｉ：
２．５〜４．０wt％及び硫化物、窒化物の少なくともど
ちらか一方をインヒビターとして含有する熱延板を、必
要に応じて焼鈍し、１回又は焼鈍を挟む２回以上の冷延
により最終板厚とした後、脱炭焼鈍し、表面に酸化膜を
形成し、焼鈍分離剤を塗布後仕上げ焼鈍し、絶縁被膜処
理することからなる方向性電磁鋼板の製造方法におい
て、前記脱炭焼鈍における酸化膜の（Ｆｅ，Ｍｎ）−Ｏ
(*1)を０．０１５〜０．３０ｇ／ｍ2 の範囲で焼鈍され
た鋼板上に、ＭｇＯ：１００重量部に対し、その融点が
１０００℃以下の塩素化合物の１種又は２種以上を塩素
として０．０１５〜０．１２重量部とアルカリ金属化合
物及び／又はアルカリ土類金属化合物の１種又は２種以
上を０．０１〜０．５０重量部含有する焼鈍分離剤を用
いることを特徴とするグラス被膜性能と磁気特性の極め
て優れる方向性電磁鋼板の製造方法。Means for Solving the Problems The present invention has the following constitution as a solution in the prior art of a decarburized annealing oxide film component in forming a glass film and an additive to an annealing separator MgO. C: 0.030 to 0.100 wt%, Si:
A hot-rolled sheet containing 2.5 to 4.0% by weight and at least one of sulfide and nitride as an inhibitor is annealed as necessary, and is finally rolled once or twice or more with the annealing interposed therebetween. After the sheet thickness, decarburizing annealing, forming an oxide film on the surface, finish annealing after applying an annealing separating agent, in the method of manufacturing a grain-oriented electrical steel sheet comprising insulating coating treatment, in the decarburizing annealing (Fe, Mn) -O of oxide film
(* 1) On a steel sheet annealed in a range of 0.015 to 0.30 g / m 2 , one or two or more kinds of chlorine compounds having a melting point of 1000 ° C. or less with respect to 100 parts by weight of MgO. It is characterized in that an annealing separator containing 0.015 to 0.12 parts by weight of chlorine and 0.01 to 0.50 parts by weight of one or more of an alkali metal compound and / or an alkaline earth metal compound is used. A method for producing a grain-oriented electrical steel sheet having extremely excellent glass coating performance and magnetic properties.
【００１７】これにより、従来技術では実現できなかっ
たＭｇＯ添加剤の改善、特に、本発明者等による従来の
塩化物添加技術を凌ぐ技術の開発に成功した。即ち、本
発明によれば、従来のＭｇＯの反応促進用添加剤による
改善技術よりも、低コストで、より確実且つ効果的に広
範囲の条件下においてグラス被膜が均一で、磁気特性が
コイル全面、全長に亘って良好な方向性電磁鋼板が得ら
れる。As a result, the inventors succeeded in improving the MgO additive, which could not be realized by the prior art, and in particular, developing a technique surpassing the conventional chloride addition technique by the present inventors. That is, according to the present invention, the glass coating is uniform under a wide range of conditions at lower cost, more reliably and effectively, and the magnetic characteristics are lower than those of the conventional technology for improving the reaction of MgO by the additive for accelerating MgO. Good grain-oriented electrical steel sheets can be obtained over the entire length.
【００１８】本発明の適用に当たっては、出発材とし
て、Ｓｉ：２．５〜４．０％とＭｎＳ及び／又はＡｌＮ
を含む珪素鋼スラブを公知の方法で熱延し、１回又は焼
鈍を挟む２回以上の冷延を行い、最終板厚とし、次い
で、脱炭焼鈍を行って鋼板表面にＳｉＯ2 を主成分とし
て、（Ｆｅ，Ｍｎ）−Ｏ成分を０．０１５〜０．３０ｇ
／ｍ2 の一定量形成した、いわゆる脱炭焼鈍板が用いら
れる。In the application of the present invention, as starting materials, Si: 2.5 to 4.0%, MnS and / or AlN
The silicon steel slab containing is subjected to hot rolling by a known method, cold rolling is performed once or two or more times by sandwiching annealing to obtain a final sheet thickness, and then decarburizing annealing is performed to make the surface of the steel sheet mainly contain SiO 2 . 0.015 to 0.30 g of the (Fe, Mn) -O component
/ M 2 , a so-called decarburized annealed plate is used.
【００１９】この鋼板に、ＭｇＯ：１００重量部に対
し、必要に応じて他の酸化物等の添加物を配合し、更
に、本発明の特徴である融点１０００℃以下の塩素化合
物を塩素として０．０１５〜０．１２重量部とアルカリ
金属及び／又はアルカリ土類金属化合物の１種又は２種
以上０．０１〜０．５０重量部添加した焼鈍分離剤を純
水中で撹拌して均一に微細分散し、スラリー状とした
後、連続ラインにおいてコーティングロール等で鋼板表
面に一定量塗布し、１５０〜４００℃（板温度）程度の
温度で乾燥し、コイルに巻き取られる。If necessary, other additives such as oxides are added to 100 parts by weight of MgO to this steel sheet, and a chlorine compound having a melting point of 1000 ° C. or less, which is a feature of the present invention, is converted to 0% by chlorine. 0.015 to 0.12 parts by weight and one or more of an alkali metal and / or alkaline earth metal compound in an amount of 0.01 to 0.50 parts by weight were added to the annealing separator in pure water to stir uniformly. After finely dispersing and forming a slurry, a predetermined amount is applied to the surface of the steel sheet by a coating roll or the like in a continuous line, dried at a temperature of about 150 to 400 ° C. (plate temperature), and wound around a coil.
【００２０】この際、焼鈍分離剤ＭｇＯには、グラス被
膜形成の反応促進補助剤、板間露点調整剤、インヒビタ
ー強化補助剤として、前記、塩素化合物の他に酸化物、
ほう素化合物、硫黄化合物、窒素化合物等が鋼成分や処
理条件に応じて併用添加される。このように処理された
コイルは、最終仕上げ焼鈍として、バッチ式、或いは連
続式炉内において１１５０〜１２００℃×２０Hrのよう
な高温、長時間処理がなされ、グラス被膜形成と二次再
結晶及び純化が同時に行われる。At this time, the annealing separator MgO is used as a reaction accelerator for glass film formation, a dew point adjuster between plates, and an inhibitor strengthening assistant, in addition to the chlorine compound, an oxide,
Boron compounds, sulfur compounds, nitrogen compounds and the like are added in combination depending on the steel components and processing conditions. The coil treated in this manner is subjected to a high temperature treatment such as 1150-1200 ° C. × 20 hr for a long time in a batch or continuous furnace as a final finish annealing to form a glass film, secondary recrystallization and purification. Are performed simultaneously.
【００２１】このようにして処理されたグラス被膜形成
後のコイルは、連続ラインにおいて余剰の焼鈍分離剤を
水洗により除去し、軽酸洗の後、絶縁被膜剤を塗布し、
その焼き付けと形状矯正、歪取り焼鈍を兼ねてヒートフ
ラットニングが行われ、最終製品とされる。方向性電磁
鋼板においては、この際のグラス被膜の形成時期、形成
量、形成状態等がインヒビターＡｌＮ，ＭｎＳ等の分解
速度に影響を与えたり、グラス被膜の質、張力或いは純
化反応等に影響を及ぼす結果、製品のグラス被膜特性と
磁気特性を左右するものである。In the coil after the formation of the glass film treated in this way, the excess annealing separator is removed by water washing in a continuous line, and after light acid washing, an insulating film agent is applied.
Heat flattening is performed for the baking, shape correction, and strain relief annealing to obtain the final product. In the grain-oriented electrical steel sheet, the timing, amount, and state of formation of the glass coating at this time affect the decomposition rate of the inhibitors AlN, MnS, etc., and affect the quality, tension, purification reaction, etc. of the glass coating. As a result, it affects the glass coating properties and magnetic properties of the product.
【００２２】この際、方向性電磁鋼板、とりわけ高磁束
密度材においては、被膜張力による鉄損、磁歪等の改善
効果が大きいことから、仕上げ焼鈍で形成したグラス被
膜の張力効果を更に補強するために、絶縁被膜成分とし
て張力付与型のものが適用される。この張力付与と絶縁
用被膜剤としては、固形分でコロイダルシリカ１００重
量部に対し、Ａｌ，Ｍｇ，Ｃａ等の燐酸塩の１種又は２
種以上を１３０〜２００重量部とクロム酸、クロム酸
塩、重クロム酸塩の１種又は２種以上をＣｒＯ3 として
１２〜４０重量部配合したものを用いるのが経済的に高
張力被膜を得るのに好適である。At this time, since the grain-oriented electrical steel sheet, particularly a high magnetic flux density material, has a large effect of improving iron loss and magnetostriction due to the coating tension, it is necessary to further reinforce the tensile effect of the glass coating formed by finish annealing. In addition, a tension imparting type is applied as an insulating coating component. As the coating agent for imparting tension and insulating, one or two kinds of phosphates such as Al, Mg, Ca, etc., based on 100 parts by weight of colloidal silica in solid content.
130-200 parts by weight or more species and chromic acid, chromate, to use what one or more of dichromate was blended 12 to 40 parts by weight of CrO 3 is an economically high tensile film It is suitable for obtaining.
【００２３】この後、更に鉄損を改善しようとする場合
には、仕上げ焼鈍の前又は後においてレーザー、歯形ロ
ール、エッチング、局部メッキ等により圧延方向とほぼ
直角方向に線状、点状に間隔と深さをコントロールし
て、歪、疵、メッキ層等を処理して磁区細分化処理が行
われる。After that, when the iron loss is to be further improved, before or after the finish annealing, a linear or dot-like space is formed in a direction substantially perpendicular to the rolling direction by laser, tooth roll, etching, local plating or the like. The magnetic domain refinement process is performed by controlling the strain, the flaw, the plating layer, and the like while controlling the depth and the depth.
【００２４】次に本発明の限定理由を述べる。先ず、本
発明に適用される方向性電磁鋼板の脱炭板の条件として
は、酸化膜成分が（Ｆｅ，Ｍｎ）−Ｏとして０．０１５
〜０．３０ｇ／ｍ2 の範囲である。（Ｆｅ，Ｍｎ）−Ｏ
成分は鋼板表面の表層部に主にＦｅ2 ＳｉＯ4 ，ＦｅＳ
ｉＯ3，Ｍｎ2 ＳｉＯ4 ，ＭｎＳｉＯ3 のような形態で
存在する。この（Ｆｅ，Ｍｎ）−Ｏ系酸化物は、フォル
ステライト被膜形成反応における若干の促進効果をも
ち、又、酸化膜の雰囲気ガス透過性に影響を与える。Next, the reasons for limitation of the present invention will be described. First, the condition of the decarburized sheet of the grain-oriented electrical steel sheet applied to the present invention is as follows: the oxide film component is 0.015 as (Fe, Mn) -O.
０．３0.30 g / m 2 . (Fe, Mn) -O
The components are mainly Fe 2 SiO 4 and FeS in the surface layer of the steel sheet surface.
It exists in the form of iO 3 , Mn 2 SiO 4 , MnSiO 3 . This (Fe, Mn) -O-based oxide has a slight accelerating effect in the forsterite film forming reaction, and also affects the atmospheric gas permeability of the oxide film.
【００２５】これ等は、本発明の塩化物、アルカリ金
属、アルカリ土類金属等と相乗的にＭｇＯとＳｉＯ2 の
間の反応性向上に寄与する。これ等の酸化膜中のトータ
ル量をＦｅ，Ｍｎで定量して得た値（Ｆｅ，Ｍｎ）−Ｏ
量が０．０１５ｇ／ｍ2 未満では、本発明の塩素化合物
とアルカリ及び／又はアルカリ金属化合物の添加技術を
用いてもグラス被膜の安定向上効果が十分に得られな
い。These contribute synergistically to the reactivity between MgO and SiO 2 with the chloride, alkali metal, alkaline earth metal and the like of the present invention. The value obtained by quantifying the total amount of these oxide films with Fe and Mn (Fe, Mn) -O
If the amount is less than 0.015 g / m 2 , the effect of improving the stability of the glass film cannot be sufficiently obtained even by using the technique of the present invention for adding a chlorine compound and an alkali and / or alkali metal compound.
【００２６】一方、０．３０ｇ／ｍ2 超では、酸化膜自
体がポーラスでシール性が弱まる問題がある。又、本発
明の塩素化合物とアルカリ及び／又はアルカリ土類金属
の添加により、過酸化特有のグラス被膜欠陥として、ピ
ンホール状金属光沢斑点、スケール、ガスマーク等が生
じたり、脱インヒビターが過酸化現象によって早まっ
て、磁束密度の低下や鉄損不良が生じるため制限され
る。On the other hand, if it exceeds 0.30 g / m 2 , there is a problem that the oxide film itself is porous and the sealing property is weakened. In addition, the addition of the chlorine compound of the present invention and an alkali and / or alkaline earth metal causes pinhole-shaped metallic luster spots, scales, gas marks, etc. as peroxidation-specific glass coating defects, and the peroxidation of the inhibitor. The phenomenon is restricted early because the magnetic flux density is reduced and iron loss is deteriorated.
【００２７】次に、適用される添加剤としては、Ｍｇ
Ｏ：１００重量部に対し、融点１０００℃以下の塩素化
合物の１種又は２種以上を塩素量に換算して０．０１５
〜０．１２重量部とアルカリ金属及び／又はアルカリ土
類金属の１種又は２種以上を０．０１〜０．５重量部が
併用添加される。先ず、本発明で塩素化合物の融点を１
０００℃と限定したのは、大部分の塩素化合物はＭｇＯ
スラリー中で高水溶性のため溶解し、塗布・乾燥時期に
ＭｇＯや他の添加剤表面或いは鋼板表面に均一に付着す
る。この場合、前述のように金属塩化物、塩酸、水和層
への置換体となってＭｇＯ表面に付着する。塩化物の場
合には、その融点、分解温度等によってグラス被膜形成
の促進効果に差異をもたらすため、適用条件が制限され
る。Next, as an additive to be applied, Mg
O: For 100 parts by weight, one or more chlorine compounds having a melting point of 1000 ° C. or lower are converted to a chlorine amount by 0.015.
0.12 parts by weight and one or more kinds of alkali metals and / or alkaline earth metals are added together in an amount of 0.01 to 0.5 parts by weight. First, in the present invention, the melting point of the chlorine compound is set to 1
The reason for limiting to 000 ° C. is that most chlorine compounds are MgO
It dissolves in the slurry due to its high water solubility, and uniformly adheres to the surface of MgO or other additives or the surface of the steel plate during the application and drying periods. In this case, as described above, it becomes a substitute for the metal chloride, hydrochloric acid, and hydration layer, and adheres to the MgO surface. In the case of chloride, the melting point, decomposition temperature, and the like cause a difference in the effect of promoting the formation of a glass film, so that application conditions are limited.
【００２８】１０００℃超の融点の化合物では、グラス
被膜形成反応に寄与する前に雰囲気ガスや温度により分
解・消失が生じる。このため、反応性向上効果が弱ま
り、グラス被膜の向上が見られないばかりか、シール性
向上によるインヒビターの保護効果が極度に弱まるので
制限される。１０００℃未満の融点を有する塩素化合物
の場合には、脱炭酸化膜上の溶融ガラス層の存在によっ
てＭｇＯとＳｉＯ2 の反応が著しく高められ、ＡｌＮ，
ＭｎＳ等のインヒビターが低温から安定に保たれる結
果、良好な磁束密度と鉄損特性が得られる。Compounds having a melting point of more than 1000 ° C. are decomposed and disappear by the atmospheric gas and temperature before contributing to the glass film forming reaction. For this reason, the effect of improving the reactivity is weakened, and not only the improvement of the glass coating is not observed, but also the effect of protecting the inhibitor by the improvement of the sealing property is extremely weakened, which is limited. In the case of a chlorine compound having a melting point of less than 1000 ° C., the reaction between MgO and SiO 2 is significantly enhanced by the presence of the molten glass layer on the decarbonated film, and AlN,
As a result of keeping an inhibitor such as MnS stable from a low temperature, good magnetic flux density and iron loss characteristics can be obtained.
【００２９】この塩素化合物としては、例えば、ＬｉＣ
ｌ，ＣｕＣｌ，ＣａＣｌ2 ，ＢａＣｌ2 ，ＭｎＣｌ2 ，
ＭｏＣｌ2 ，ＦｅＣｌ2 ，ＣｏＣｌ2 ，ＺｎＣｌ2 ，Ｃ
ｄＣｌ2 ，ＳｎＣｌ2 ，ＢｉＣｌ3 等が効果的で、アル
カリ及び／又はアルカリ土類金属化合物と併用した場合
にその効果が著しく優れる。As the chlorine compound, for example, LiC
1, CuCl, CaCl 2 , BaCl 2 , MnCl 2 ,
MoCl 2 , FeCl 2 , CoCl 2 , ZnCl 2 , C
dCl 2 , SnCl 2 , BiCl 3 and the like are effective, and the effect is remarkably excellent when used in combination with an alkali and / or alkaline earth metal compound.
【００３０】この塩素化合物の添加量は、ＭｇＯ：１０
０重量部に対し塩素に換算して０．０１５〜０．２００
重量部である。０．０１５重量部未満では、アルカリ金
属物質等の併用によっても塩素化合物による低融点化効
果が不足して十分なグラス被膜の厚みと均一度及び被膜
による表面のシール効果が得られない。一方、塩素量と
して０．２重量部超になると低融点化効果によるグラス
被膜の早期形成効果は得られるが過剰塩素分とアルカリ
金属物質による複合作用によって、仕上げ焼鈍高温域で
のグラス被膜のエッチング・分解作用や還元反応が生じ
る。このため、薄膜化やガスマーク状の不均一化が生
じ、密着性不良、絶縁性不良、被膜張力低下を引き起こ
すため制限される。The amount of the chlorine compound added is MgO: 10
0.015 to 0.200 in terms of chlorine based on 0 parts by weight
Parts by weight. If the amount is less than 0.015 parts by weight, the effect of lowering the melting point of the chlorine compound is insufficient even with the combined use of an alkali metal substance or the like, so that a sufficient glass film thickness and uniformity and a surface sealing effect by the film cannot be obtained. On the other hand, when the chlorine content exceeds 0.2 parts by weight, the effect of early formation of the glass film by the effect of lowering the melting point can be obtained, but the etching effect of the glass film in the high temperature region of the finish annealing due to the combined action of the excess chlorine and the alkali metal substance.・ Decomposition and reduction reactions occur. For this reason, thinning and unevenness in the shape of a gas mark occur, resulting in poor adhesion, poor insulation, and a decrease in film tension.
【００３１】次に塩素化合物に併用添加されるアルカリ
金属及び／又はアルカリ土類金属はＭｇＯ：１００重量
部当たり０．０１〜０．５重量部である。本発明では、
アルカリ金属或いはアルカリ土類金属は塩素化合物を添
加時から仕上げ焼鈍のグラス被膜形成の高温時まで安定
に保つのに重要な役割を有する。Next, the alkali metal and / or alkaline earth metal added in combination with the chlorine compound is 0.01 to 0.5 parts by weight per 100 parts by weight of MgO. In the present invention,
The alkali metal or alkaline earth metal plays an important role in keeping the chlorine compound stable from the time of addition of the chlorine compound to the high temperature of forming the glass film in the finish annealing.
【００３２】即ち、添加された塩素化合物は、スラリー
中では、殆どが容易に水スラリー中で溶解する。又、一
部はオキシ化合物、塩酸等となってスラリー中に存在す
る。これ等が塗布乾燥時期には新たな塩素化合物を生じ
たり、塩酸、水和層置換物質等になってＭｇＯ表面を均
一に覆い、鋼板面に付着する。この際、コイル塗布・乾
燥時や仕上げ焼鈍の昇温過程早期に消失してはその機能
を失うことになる。That is, most of the added chlorine compound is easily dissolved in the water slurry in the slurry. Further, a part thereof is present as an oxy compound, hydrochloric acid or the like in the slurry. These form a new chlorine compound during the coating and drying period, become a hydrochloric acid, a hydration layer replacement substance, etc., uniformly cover the MgO surface and adhere to the steel plate surface. At this time, if it disappears at the time of coil application / drying or at the early stage of the temperature rise process of finish annealing, the function will be lost.
【００３３】ところが、本発明のように水溶性のアルカ
リ或いはアルカリ土類金属化合物が共存する場合には、
スラリー中でイオン化した不安定な塩素が塗布・乾燥時
に、その水中におけるアルカリ又はアルカリ土類金属の
溶解度に応じて優先的にアルカリ、アルカリ土類金属と
結合して化合物を形成し、塗布乾燥から高温焼鈍のグラ
ス被膜形成時期まで安定して鋼板表面に存在することに
なる。このため、仕上げ焼鈍昇温時早期の反応開始と反
応促進効果をより強力に発揮する。However, when a water-soluble alkali or alkaline earth metal compound coexists as in the present invention,
When the unstable chlorine ionized in the slurry is applied and dried, it preferentially combines with the alkali or alkaline earth metal in accordance with the solubility of the alkali or alkaline earth metal in the water to form a compound, and from application drying. It will be stably present on the steel sheet surface until the high temperature annealing glass film formation time. For this reason, the reaction initiation and the reaction promotion effect at the early stage of the finish annealing are more strongly exerted.
【００３４】このアルカリ金属或いはアルカリ土類金属
化合物としては、水酸化物、ほう酸塩、硫酸塩、硝酸
塩、珪酸塩等の水に可溶の物質が用いられる。添加量が
ＭｇＯ：１００重量部に対し０．０１重量部未満では、
前記塩素の固定による安定化効果が得られない。一方、
０．５重量部超では、過剰のアルカリ金属やアルカリ土
類金属化合物による高温でのエッチングや還元反応が生
じて、前記塩素化合物の添加が多い場合と類似のグラス
被膜欠陥や磁性不良の問題を引き起こすため制限され
る。As the alkali metal or alkaline earth metal compound, water-soluble substances such as hydroxides, borates, sulfates, nitrates and silicates are used. If the added amount is less than 0.01 part by weight with respect to 100 parts by weight of MgO,
No stabilizing effect is obtained by fixing the chlorine. on the other hand,
If the amount exceeds 0.5 parts by weight, etching or reduction reaction at a high temperature due to excessive alkali metal or alkaline earth metal compound occurs, and the problem of glass coating defects and poor magnetic properties similar to the case where the amount of the chlorine compound is added is large. Limited to cause.
【００３５】[0035]
〔実施例１〕重量％でＣ：０．０７８、Ｓｉ：３．３
５、Ｍｎ：０．０６０、Ｓ：０．０２４、Ａｌ：０．０
２５、Ｎ：０．００８０、Ｃｕ：０．０６、Ｓｎ：０．
０１２、残部を鉄と不可避の不純物からなる高磁束密度
方向性電磁鋼板素材を公知の方法で熱延、焼鈍、冷延を
行い、最終板厚０．０２３mmとした。その後、Ｎ2 ２５
％＋Ｈ2 ７５％、露点６７℃のウェット雰囲気中で脱炭
焼鈍を行った。この鋼板の表面酸化膜中の（Ｆｅ，Ｍ
ｎ）−Ｏ量は０．１５ｇ／ｍ2 であった。[Example 1] C: 0.078, Si: 3.3% by weight
5, Mn: 0.060, S: 0.024, Al: 0.0
25, N: 0.0080, Cu: 0.06, Sn: 0.
012, a high magnetic flux density directional magnetic steel sheet material consisting of iron and unavoidable impurities is subjected to hot rolling, annealing, and cold rolling by a known method to a final sheet thickness of 0.023 mm. Then, N 2 25
The decarburizing annealing was performed in a wet atmosphere of 75% of H 2 + 75% and a dew point of 67 ° C. (Fe, M) in the surface oxide film of this steel sheet
n) -O amount was 0.15 g / m 2.
【００３６】次いで、表１に示すように、ＭｇＯ：１０
０重量部とＴｉＯ2 ：５重量部に対し、金属塩化物とア
ルカリ金属及びアルカリ土類金属化合物を複合添加した
焼鈍分離剤スラリーを乾燥後の重量で６ｇ／ｍ2 の割合
で塗布し、乾燥し、コイルに巻き取った。次いで、１２
００℃×２０Hrの最終仕上げ焼鈍を行った後、絶縁被膜
剤として３０％コロイダルシリカ７０ml、５０％りん酸
アルミニウム５０mlからなるコーティング剤を乾燥、焼
き付け後の重量で５ｇ／ｍ2 になるように塗布し、連続
炉中で８５０℃×３０秒間のヒートフラットニング処理
を行い最終製品とした。この試験におけるグラス被膜形
成状況、絶縁被膜特性、磁気特性の結果を表２に示す。Next, as shown in Table 1, MgO: 10
0 weight part and TiO 2 : 5 weight part, an annealing separator slurry in which a metal chloride and an alkali metal and an alkaline earth metal compound are added in combination is applied at a rate of 6 g / m 2 by weight after drying and dried. Then, it was wound around a coil. Then 12
After final annealing at 00 ° C. × 20 hours, a coating agent consisting of 70% of 30% colloidal silica and 50 ml of 50% aluminum phosphate is applied as an insulating coating agent to a dry weight of 5 g / m 2 after baking. Then, heat flattening treatment was performed at 850 ° C. for 30 seconds in a continuous furnace to obtain a final product. Table 2 shows the results of glass film formation, insulating film characteristics, and magnetic characteristics in this test.
【００３７】[0037]
【表１】 [Table 1]
【００３８】[0038]
【表２】 [Table 2]
【００３９】この結果、本発明のように金属塩化物とア
ルカリ或いはアルカリ土類金属化合物を複合添加した場
合には、いずれも均一で光沢のある厚いグラス被膜が均
一に形成され、被膜張力、密着性等の優れたグラス被膜
が形成され、磁気特性も非常に良好な結果が得られた。
一方、比較例の塩素化合物のみでは、グラス被膜が薄く
なる傾向が見られ、本発明に比較してグラス被膜の密着
性が悪く、磁気特性もやや劣る結果であった。又、アル
カリ金属化合物のみの場合には、更に被膜形成状況が不
良で、磁気特性も本発明に比較して、かなり劣る結果と
なった。As a result, when a metal chloride and an alkali or alkaline earth metal compound are added in a complex manner as in the present invention, a uniform, glossy and thick glass film is formed uniformly, and the film tension and the adhesion A glass film excellent in properties and the like was formed, and very good results were obtained in the magnetic properties.
On the other hand, with the chlorine compound of Comparative Example alone, the glass coating tended to be thinner, and the adhesion of the glass coating was poor and the magnetic properties were slightly inferior to those of the present invention. Further, when only the alkali metal compound was used, the film formation was further poor, and the magnetic properties were considerably inferior to those of the present invention.
【００４０】〔実施例２〕重量％でＣ：０．０５８、Ｓ
ｉ：３．３０、Ｍｎ：０．１２、Ａｌ：０．０３０、
Ｓ：０．００７５、Ｎ：０．００７８、Ｓｎ：０．０
５、残部をＦｅと不可避の不純物からなる方向性電磁鋼
板スラブを公知の方法で１１５０℃の低温で加熱後、熱
延し、焼鈍と冷延により最終板厚０．２３mmとした。こ
のコイルを連続焼鈍ラインにおいてＮ2 ２５％＋Ｈ2 ７
５％、露点６８℃のウェット雰囲気中で露点を変更して
８３０℃×１１０秒間の脱炭焼鈍し、酸化膜中の（Ｆ
ｅ，Ｍｎ）−Ｏ量の異なる脱炭焼鈍板を得た。引き続き
鋼中Ｎ量が２００ppm となるようにＮ2 ２５％＋Ｈ2 ７
５％＋ＮＨ3 のドライ雰囲気中で７５０℃×３０秒間の
窒化処理を行った。Example 2 C: 0.058 by weight%, S
i: 3.30, Mn: 0.12, Al: 0.030,
S: 0.0075, N: 0.0078, Sn: 0.0
5. A grain-oriented electrical steel sheet slab consisting of Fe and unavoidable impurities was heated at a low temperature of 1150 ° C. by a known method, and then hot-rolled, and then subjected to annealing and cold rolling to a final sheet thickness of 0.23 mm. N 2 25% in the coil continuous annealing line + H 2 7
The dew point was changed in a wet atmosphere having a dew point of 5% and a dew point of 68 ° C., and decarburization annealing was performed at 830 ° C. × 110 seconds to obtain (F) in the oxide film.
e, Mn) Decarburized annealed plates having different amounts of -O were obtained. Continuously, N 2 25% + H 2 7 so that the N content in the steel becomes 200 ppm.
A nitriding treatment was performed at 750 ° C. for 30 seconds in a dry atmosphere of 5% + NH 3 .
【００４１】この鋼板に表３に示すようにＭｇＯ：１０
０重量部に対し、ＴｉＯ2 ：５重量部と金属塩化物とア
ルカリ金属及びアルカリ土類金属化合物を複合添加した
焼鈍分離剤スラリーを乾燥後重量で６ｇ／ｍ2 の割合で
塗布し、乾燥後コイルに巻き取った。次いで、実施例１
と同様に最終焼鈍と絶縁被膜処理を行って最終製品とし
た。この試験における製品のグラス被膜特性と磁気特性
の結果を表４に示す。又、図１に酸化膜中の（Ｆｅ，Ｍ
ｎ）−Ｏ量とＭｇＯ中のＣｌ量とグラス被膜特性の関係
を示す。本発明の範囲で良好なグラス被膜が形成されて
いる。As shown in Table 3, MgO: 10
An annealed separating agent slurry containing 5 parts by weight of TiO 2 and a complex addition of a metal chloride, an alkali metal and an alkaline earth metal compound with respect to 0 parts by weight was applied after drying at a rate of 6 g / m 2 , and then dried. Wound on a coil. Then, Example 1
In the same manner as described above, final annealing and insulation coating treatment were performed to obtain a final product. Table 4 shows the results of the glass coating properties and magnetic properties of the products in this test. FIG. 1 shows (Fe, M) in the oxide film.
n) The relationship between the amount of -O, the amount of Cl in MgO, and the properties of the glass coating is shown. A good glass film is formed within the range of the present invention.
【００４２】[0042]
【表３】 [Table 3]
【００４３】[0043]
【表４】 [Table 4]
【００４４】この試験の結果、本発明のように酸化膜中
の（Ｆｅ，Ｍｎ）−Ｏを一定量とし、塩化物とアルカリ
金属及びアルカリ土類金属化合物を複合添加した場合に
は、いずれもグラス被膜の均一性、張力、密着性が良好
で、磁気特性も極めて優れたものが得られた。一方、比
較例の塩素化合物とアルカリ金属化合物が本発明域で
も、（Ｆｅ，Ｍｎ）−Ｏの多い比較例ではいずれもグラ
ス被膜は不均一で、密着性が劣り、磁気特性も劣る結果
となった。又、脱炭酸化膜の（Ｆｅ，Ｍｎ）−Ｏの本発
明域より多い比較例では、いずれもグラス被膜が過酸化
状の欠陥を呈し、磁気特性も本発明に比し、かなり劣る
結果となった。As a result of this test, when the amount of (Fe, Mn) -O in the oxide film was made constant and chloride and alkali metal and alkaline earth metal compounds were added in combination as in the present invention, all of them were obtained. A glass coating having good uniformity, good tension, good adhesion, and extremely excellent magnetic properties was obtained. On the other hand, even in the case where the chlorine compound and the alkali metal compound of the comparative example are in the range of the present invention, in the comparative examples containing a large amount of (Fe, Mn) -O, the glass coating is nonuniform, the adhesion is inferior, and the magnetic properties are inferior. Was. In the comparative examples in which the content of (Fe, Mn) -O in the decarbonated film was larger than the range of the present invention, the glass film exhibited peroxidation-like defects, and the magnetic properties were considerably inferior to those of the present invention. became.
【００４５】[0045]
【発明の効果】本発明のように、その融点：１０００℃
以下の塩素化合物とアルカリ金属及び／又はアルカリ土
類金属化合物を併用添加することにより、低融点の塩素
化合物が塗布乾燥〜仕上げ焼鈍でのグラス被膜形成時期
まで安定に鋼板上に保たれる。又、微粒子ＭｇＯや微量
の水和物質と塩素とアルカリ金属、アルカリ土類金属の
反応物質や混合物質がＭｇＯや他の添加剤との粒子の間
をバインダー状となって結合し、鋼板との密着力を高
め、更にフォルステライト被膜形成促進に寄与する。こ
の結果、図１に一例を示す如く、塩化物とアルカリ金属
化合物の複合添加により、酸化膜の成分効果をより発揮
して、均一に微粒子結晶のフォルステライト被膜を形成
する。これにより、密着性、被膜張力等の優れたグラス
被膜となる。As in the present invention, its melting point is 1000 ° C.
By adding the following chlorine compounds in combination with the alkali metal and / or alkaline earth metal compounds, the chlorine compounds having a low melting point can be stably maintained on the steel sheet until the time of forming the glass film by coating and drying to finish annealing. In addition, a reactive substance or a mixed substance of fine particles MgO or a trace amount of hydrated substance and chlorine and an alkali metal or an alkaline earth metal forms a binder between the particles of MgO and other additives and binds to the steel sheet. It enhances adhesion and further contributes to the promotion of forsterite film formation. As a result, as shown in an example in FIG. 1, the composite effect of the chloride and the alkali metal compound exerts the effect of the component of the oxide film, and the forsterite film of fine-grain crystals is uniformly formed. This results in a glass coating having excellent adhesion, coating tension, and the like.
【００４６】又、このグラス被膜形成が仕上げ焼鈍昇温
時早期から均一に行われる結果、鋼板雰囲気ガスからの
Ｎガス等の鋼中への侵入を抑える一方、焼鈍中の鋼板へ
の追加酸化を抑制し、均一で、磁性に害を及ぼさない高
張力で良質のグラス被膜を形成する。この際の被膜界面
のシール効果の向上は、インヒビターＡｌＮ，ＭｎＳ等
の分解による脱Ｎ，脱Ｓを抑えたり雰囲気ガスからの窒
素の侵入や酸化を抑えて、高温まで安定化する結果、磁
束密度を向上し、グラス被膜の張力向上効果と相俟って
鉄損を改善するものと考えられる。Further, as a result of the glass film being formed uniformly at an early stage during the temperature rise in the finish annealing, the penetration of N gas and the like from the steel atmosphere gas into the steel is suppressed, while the additional oxidation of the steel sheet during the annealing is suppressed. Suppress, form a uniform, high-strength, high-quality glass coating that does not harm magnetism. In this case, the improvement of the sealing effect at the interface of the coating film is achieved by suppressing the removal of N and S by decomposition of the inhibitor AlN, MnS, etc., and suppressing the invasion and oxidation of nitrogen from the atmosphere gas, and stabilizing to a high temperature. It is considered that the iron loss is improved in combination with the effect of improving the tension of the glass coating.
【図１】実施例２と同一の素材を脱炭焼鈍板の酸化膜の
成分を変更して焼鈍した材料に焼鈍分離剤の添加剤を変
更して塗布し、グラス被膜の形成状況を評価した図表で
ある。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 The same material as in Example 2 was applied by changing the composition of an oxide film of a decarburized annealed plate and changing the additive of an annealing separating agent to a material annealed to evaluate the state of formation of a glass film. It is a chart.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 田中 収 北九州市戸畑区大字中原46−59 日鐵プ ラント設計株式会社内 (56)参考文献 特開 平３−120376（ＪＰ，Ａ) 特公 平２−5820（ＪＰ，Ｂ２) (58)調査した分野(Int.Cl.7，ＤＢ名) C21D 8/12 C21D 9/46 501 C23C 22/00 H01F 1/18 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Osamu Tanaka 46-59 Ohara Nakahara, Tobata-ku, Kitakyushu Nippon Steel Plant Design Co., Ltd. (56) References JP-A-3-120376 (JP, A) 2-5820 (JP, B2) (58) Fields investigated (Int. Cl. 7 , DB name) C21D 8/12 C21D 9/46 501 C23C 22/00 H01F 1/18
Claims (1)
ｉ：２．５〜４．０wt％及び硫化物、窒化物の少なくと
もどちらか一方をインヒビターとして含有する熱延板
を、１回又は焼鈍を挟む２回以上の冷延により最終板厚
とした後、脱炭焼鈍し、表面に酸化膜を形成し、焼鈍分
離剤を塗布後仕上げ焼鈍し、絶縁被膜処理することから
なる方向性電磁鋼板の製造方法において、前記脱炭焼鈍
後における酸化膜の（Ｆｅ，Ｍｎ）−Ｏを０．０１５〜
０．３０ｇ／ｍ2 とすると共に、鋼板に、ＭｇＯ：１０
０重量部に対し、その融点が１０００℃以下の塩素化合
物の１種又は２種以上を、塩素として０．０１５〜０．
１２重量部とアルカリ金属化合物及び／又はアルカリ土
類金属化合物の１種又は２種以上を０．０１〜０．５０
重量部含有する焼鈍分離剤を塗布することを特徴とする
グラス被膜と磁気特性の極めて優れる方向性電磁鋼板の
製造方法。但し（Ｆｅ，Ｍｎ）−Ｏ：鋼板表面の酸化膜
を電解剥離し、Ｆｅ，Ｍｎを定量し、鋼板単位面積当た
りの値として計算した量（ｇ／ｍ2 ）。1. C: 0.030 to 0.100 wt%, S
i: A hot-rolled sheet containing 2.5 to 4.0% by weight and at least one of sulfide and nitride as an inhibitor is subjected to one or two or more cold-rolling steps of annealing to obtain a final sheet thickness. , Decarburizing annealing, forming an oxide film on the surface, applying an annealing separator, finishing annealing, and insulating coating treatment. The method of manufacturing a grain-oriented electrical steel sheet, comprising: Fe, Mn) -O
0.30 g / m 2 and MgO: 10
With respect to 0 parts by weight, one or more chlorine compounds having a melting point of 1000 ° C. or less are used as chlorine in an amount of 0.015 to 0.5.
12 parts by weight and one or more of the alkali metal compound and / or the alkaline earth metal compound in an amount of 0.01 to 0.50
A method for producing a glass coating characterized by applying an annealing separator contained in parts by weight and a grain-oriented electrical steel sheet having extremely excellent magnetic properties. However, (Fe, Mn) -O: the amount (g / m 2 ) of electrolytically peeling off the oxide film on the steel sheet surface, quantifying Fe and Mn, and calculating the value per unit area of the steel sheet.
Priority Applications (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28229394A JP3336547B2 (en) | 1994-11-16 | 1994-11-16 | Method for manufacturing grain-oriented electrical steel sheet with extremely excellent glass coating and magnetic properties |
| KR1019950011676A KR0157539B1 (en) | 1994-05-13 | 1995-05-12 | Annealing separator having excellent reactivity for grain-oriented electrical steel sheet and method of use the same |
| CN95106060A CN1043056C (en) | 1994-05-13 | 1995-05-12 | Anneal isolating objects with good reactivity and used for silica steel sheet |
| US08/440,276 US5685920A (en) | 1994-05-13 | 1995-05-12 | Annealing separator having excellent reactivity for grain-oriented electrical steel sheet and method of use the same |
| CA002149279A CA2149279C (en) | 1994-05-13 | 1995-05-12 | Annealing separator having excellent reactivity for grain-oriented electrical steel sheet and method of use the same |
| EP95107412A EP0699771A1 (en) | 1994-05-13 | 1995-05-15 | Annealing separator having excellent reactivity for grain-oriented electrical steel sheet and method of use the same |
| PCT/JP1995/002346 WO1996015291A1 (en) | 1994-11-16 | 1995-11-16 | Process for producing directional electrical sheet excellent in glass coating and magnetic properties |
| KR1019970703263A KR100245032B1 (en) | 1994-11-16 | 1995-11-16 | Process for producing directional sheet excellent in glass coating and magnetic properties |
| CN951972014A CN1065004C (en) | 1994-11-16 | 1995-11-16 | Process for producing directional electrical sheet excellent in glass coating and magnetic properties |
| EP95938021A EP0789093B2 (en) | 1994-11-16 | 1995-11-16 | Process for producing directional electrical sheet excellent in glass coating and magnetic properties |
| DE69515892T DE69515892T3 (en) | 1994-11-16 | 1995-11-16 | METHOD FOR PRODUCING AN ELECTRIC DIRECTIVE PLATE WITH GOOD GLASS STABILITY AND EXCELLENT MAGNETIC PROPERTIES |
| US08/836,593 US5840131A (en) | 1994-11-16 | 1995-11-16 | Process for producing grain-oriented electrical steel sheet having excellent glass film and magnetic properties |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28229394A JP3336547B2 (en) | 1994-11-16 | 1994-11-16 | Method for manufacturing grain-oriented electrical steel sheet with extremely excellent glass coating and magnetic properties |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08143961A JPH08143961A (en) | 1996-06-04 |
| JP3336547B2 true JP3336547B2 (en) | 2002-10-21 |
Family
ID=17650545
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28229394A Expired - Fee Related JP3336547B2 (en) | 1994-05-13 | 1994-11-16 | Method for manufacturing grain-oriented electrical steel sheet with extremely excellent glass coating and magnetic properties |
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| JP (1) | JP3336547B2 (en) |
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| KR101223108B1 (en) * | 2010-12-23 | 2013-01-17 | 주식회사 포스코 | Grain-oriented electrical steel sheet with extremely low iron loss and Method for manufacturing the same |
| KR101223117B1 (en) * | 2010-12-23 | 2013-01-17 | 주식회사 포스코 | Grain-oriented electrical steel sheet with extremely low iron loss and Method for manufacturing the same |
| KR101223112B1 (en) * | 2010-12-23 | 2013-01-17 | 주식회사 포스코 | Grain-oriented electrical steel sheet with extremely low iron loss and Method for manufacturing the same |
| KR101223115B1 (en) * | 2010-12-23 | 2013-01-17 | 주식회사 포스코 | Grain-oriented electrical steel sheet with extremely low iron loss and method for manufacturing the same |
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1994
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| Publication number | Publication date |
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| JPH08143961A (en) | 1996-06-04 |
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