JP2003082472A - Separation agent for annealing, and method for producing grain oriented magnetic steel sheet having excellent glass film and magnetic property - Google Patents
Separation agent for annealing, and method for producing grain oriented magnetic steel sheet having excellent glass film and magnetic propertyInfo
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- JP2003082472A JP2003082472A JP2001275076A JP2001275076A JP2003082472A JP 2003082472 A JP2003082472 A JP 2003082472A JP 2001275076 A JP2001275076 A JP 2001275076A JP 2001275076 A JP2001275076 A JP 2001275076A JP 2003082472 A JP2003082472 A JP 2003082472A
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は主として方向性電磁
鋼板の製造に用いら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ものである。特に、優れ
た反応性を有する焼鈍分離剤を用いることにより、極め
て均一なグラス被膜と優れた磁気特性を有する方向性電
磁鋼板の製造を可能にする。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an annealing separator used mainly for producing grain-oriented electrical steel sheets and a method for producing grain-oriented electrical steel sheets using the same. In particular, by using an annealing separator having excellent reactivity, it becomes possible to manufacture a grain-oriented electrical steel sheet having an extremely uniform glass film and excellent magnetic properties.
【０００２】[0002]
【従来の技術】通常、方向性電磁鋼板の製造方法として
は、質量％で、Ｃ：０．０３０〜０．１００％、Ｓｉ：
２．５０〜４．５０％含有する素材スラブを熱延し、焼
鈍と１回または中間焼鈍を挟む２回以上の冷延により最
終板厚とされる。次いで、Ｈ2或いはＮ２＋Ｈ２雰囲気
中で酸化度を制御して脱炭焼鈍し、脱炭、一次再結晶及
びＳｉＯ２主体の酸化膜形成を行う。また特開昭５９−
５６５２２号公報のようにＭｎ：０．０８〜０．４５
％、Ｓ：０．００７％以下にすることにより低温スラブ
加熱化を可能にした技術においては、脱炭焼鈍の後に窒
化処理が行われる。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鋼板に塗布し、乾燥後、コイ
ルに巻き取り仕上げ焼鈍を行う。この後、絶縁被膜剤を
塗布し、乾燥し、焼付け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 Usually, as a method for producing a grain-oriented electrical steel sheet, C: 0.030 to 0.100% and Si:
A raw material slab containing 2.50 to 4.50% is hot-rolled and annealed and cold-rolled once or twice or more with intermediate annealing to obtain a final plate thickness. Next, decarburization annealing is performed by controlling the degree of oxidation in an H 2 or N 2 + H 2 atmosphere, decarburization, primary recrystallization, and SiO 2 -based oxide film formation are performed. In addition, JP-A-59-
Mn: 0.08 to 0.45 as in Japanese Patent No. 56522.
%, S: 0.007% or less, in the technique that enables low-temperature slab heating, nitriding treatment is performed after decarburization annealing. After that, an annealing separator containing MgO as a main component is applied to the steel sheet in the form of slurry, dried, and then coiled to finish annealing. After that, an insulating coating agent is applied, dried, baked and heat flattened to obtain a final product.
【０００３】この方向性電磁鋼板の製造過程におけるグ
ラス被膜形成反応は、脱炭焼鈍で生成する酸化膜の性状
（成分、量、形成状態等）、焼鈍分離剤主成分であるＭ
ｇＯの性状（粒度、不純物、活性度、表面状態等）、反
応促進剤としての添加剤（種類、分散状態、量等）及び
仕上げ焼鈍条件（ヒートサイクル、雰囲気等）のバラン
スが重要である。これらを適切に制御すれば、グラス被
膜形成時期まで脱炭焼鈍酸化膜が安定に保たれ、より低
温から均一なグラス被膜の形成反応を行わせることが出
来る。この結果、二次再結晶開始に適切な高温域までイ
ンヒービターの安定化が保たれ、優れた磁気特性が得ら
れる。The glass film forming reaction in the manufacturing process of this grain-oriented electrical steel sheet is characterized by the properties (component, amount, formation state, etc.) of the oxide film formed by decarburization annealing, and the main component of the annealing separator M.
It is important to balance the properties of gO (particle size, impurities, activity, surface state, etc.), additives as reaction accelerators (type, dispersion state, amount, etc.) and finish annealing conditions (heat cycle, atmosphere, etc.). If these are properly controlled, the decarburizing annealing oxide film can be kept stable until the glass film forming time, and a uniform glass film forming reaction can be carried out from a lower temperature. As a result, the stabilization of the in-heater is maintained up to a high temperature range suitable for the initiation of secondary recrystallization, and excellent magnetic characteristics are obtained.
【０００４】グラス被膜形成においては、とりわけ焼鈍
分離剤の役割が大きい。焼鈍分離剤が鋼板に塗布される
場合には、主成分ＭｇＯ粒子のスラリー中の分散状態、
水和進行状態、乾燥後の鋼板への密着状態等が重要であ
る。通常、このＭｇＯスラリーに適切な反応促進剤を添
加すると、ＭｇＯと脱炭酸化膜ＳｉＯ2の反応によるグ
ラス被膜形成時に融点低下効果をもたらし、反応が促進
される。特に、Ｓｂ、Ｂｉ、Ｃｌ等の化合物の反応促進
効果は優れており、本発明者等によって数々の提案がな
されてきた。In forming the glass film, the role of the annealing separator is particularly large. When the annealing separator is applied to the steel sheet, the dispersion state of the main component MgO particles in the slurry,
The progress of hydration and the state of adhesion to the steel sheet after drying are important. Usually, when a suitable reaction accelerator is added to this MgO slurry, a melting point lowering effect is brought about when the glass film is formed by the reaction between MgO and the decarboxylated film SiO 2 , and the reaction is accelerated. In particular, the compounds such as Sb, Bi and Cl are excellent in the reaction accelerating effect, and various proposals have been made by the present inventors.
【０００５】このような焼鈍分離剤中への添加剤の改善
技術としては、例えば、特公昭６３−３０２２号公報に
はＭｇＯ：１００質量部に対し、硫酸アンチモン０．０
５〜２．０質量部と該硫酸アンチモン中にＳｂ，Ｓｒ，
Ｔｉ，Ｚｒの塩化物の１種又は２種以上を塩素として質
量で５〜２０％添加した焼鈍分離剤を用いることによ
り、磁気特性、被膜特性共に優れる方向性電磁鋼板を得
られることが開示されている。又、特開平１１−３６０
１８号公報には脱炭焼鈍後の鋼板上にＭｇＯ：１００質
量部に対し、平均粒子径３μ以下のＣａ，Ｍｇ，Ｂａ，
Ａｌから選ばれる水酸化物の１種又は２種以上を０．１
〜５．０質量部とＳｂ及び／又はＢｉの硫酸塩、塩化
物、オキシ塩化物、酸化物の１種又は２種以上を０．０
５〜０．５０質量部添加することを特徴とするもので、
これによってグラス被膜形成における低融点化効果によ
り優れたグラス被膜と磁気特性が得られることが述べら
れている。As a technique for improving the additives in the annealing separator, for example, JP-B-63-3022 discloses that MgO: 100 parts by mass, antimony sulfate 0.0:
5 to 2.0 parts by mass and Sb, Sr,
It is disclosed that a grain-oriented electrical steel sheet excellent in both magnetic properties and coating properties can be obtained by using an annealing separator in which 5 to 20% by mass of one or more chlorides of Ti and Zr are added as chlorine. ing. In addition, JP-A-11-360
No. 18, gazette on the steel sheet after decarburization annealing, Ca, Mg, Ba having an average particle diameter of 3 μm or less with respect to 100 parts by mass of MgO.
0.1 or more of one or more hydroxides selected from Al
To 5.0 parts by mass of Sb and / or Bi sulfate, chloride, oxychloride, oxide and 0.0
It is characterized by adding 5 to 0.50 parts by mass,
It is stated that this makes it possible to obtain excellent glass coating and magnetic properties due to the effect of lowering the melting point in forming the glass coating.
【０００６】[0006]
【発明が解決しようとする課題】以上のように、ＭｇＯ
の性状やグラス被膜形成における反応促進剤としての添
加剤を改善することでグラス被膜形成反応が改善されて
きた。しかしながら、従来の方法でＳｂ或いはＢｉ化合
物による低融点化効果を得ようとする場合には、Ｓｂ、
Ｂｉ化合物の溶解性に大きな問題があった。即ち、Ｓ
ｂ、Ｂｉの硫酸塩、塩化物、炭酸塩、ケイ酸塩、酸化
物、水酸化物等においては殆ど水溶性を持たないため、
未溶解の化合物による反応の不均一性や粒状偏析物質に
よるピンホール状被膜欠陥の発生が生じやすくなるとい
う問題である。特に硫酸塩、塩化物においては、水に入
れるとオキシ化合物状の不溶性化合物を再析出し、鋼板
上に凝集物が偏在する。この結果、Ｓｂ，Ｂｉ化合物特
有の低融点化効果が十分に得られないばかりか、未溶解
粒子や凝集物の鋼板面上の付着部分において被膜形成時
に溶融したり、過酸化状の反応を生じ、被膜欠陥を生じ
やすい。本発明は特にこのような問題を解決し、Ｓｂ，
Ｂｉ化合物の添加効果を十分に発揮させることを目的と
する。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention As described above, MgO
The glass film formation reaction has been improved by improving the properties of the above and additives as a reaction accelerator in the glass film formation. However, in order to obtain the effect of lowering the melting point of Sb or Bi compound by the conventional method, Sb,
There was a big problem in the solubility of the Bi compound. That is, S
b, Bi has almost no water solubility in sulfates, chlorides, carbonates, silicates, oxides, hydroxides, etc.
This is a problem that nonuniform reaction due to undissolved compounds and pinhole-like film defects due to granular segregated substances are likely to occur. Particularly in the case of sulfates and chlorides, when placed in water, insoluble compounds in the form of oxy compounds are re-precipitated, and agglomerates are unevenly distributed on the steel sheet. As a result, not only the melting point lowering effect peculiar to Sb and Bi compounds cannot be sufficiently obtained, but also undissolved particles and agglomerates are melted at the time of film formation in the adhered portion on the steel plate surface, or a reaction such as a peroxidation occurs. , Coating defects are likely to occur. The present invention particularly solves such a problem, and
The purpose is to fully exert the effect of adding the Bi compound.
【０００７】[0007]
【課題を解決するための手段】本発明者等は、前述の如
く、従来のグラス被膜形成反応促進剤としてのＳｂ，Ｂ
ｉ化合物が水溶性を殆ど持たない問題を解決するため、
水溶性化合物を得るための方策を検討した。その結果、
予め、Ｓｂ，Ｂｉの硫化物、硫酸塩、塩化物、硝酸塩、
酢酸塩等の化合物を、オキシカルボン酸系化合物、オキ
シスルホン酸系化合物、アミノカルボン酸系化合物、ア
ミン系化合物、カルボン酸系化合物を用いて溶解処理
し、有機金属化合物もしくは錯体化合物とすることで、
水溶液において安定した溶解性が得られることを見出し
た。As described above, the inventors of the present invention have used Sb and B as conventional glass film formation reaction accelerators.
In order to solve the problem that the i compound has almost no water solubility,
A method for obtaining a water-soluble compound was investigated. as a result,
In advance, Sb, Bi sulfide, sulfate, chloride, nitrate,
By dissolving a compound such as an acetate salt with an oxycarboxylic acid-based compound, an oxysulfonic acid-based compound, an aminocarboxylic acid-based compound, an amine-based compound, or a carboxylic acid-based compound to form an organometallic compound or a complex compound ,
It has been found that stable solubility can be obtained in an aqueous solution.
【０００８】この有機金属水溶性化合物と粉末状化合物
を用いて焼鈍分離剤主成分ＭｇＯへの添加条件、作用効
果についての研究を重ねた結果、Ｓｂ，Ｂｉの有機化合
物及び／又は錯体化合物の水溶液を添加剤として微量添
加することにより、従来の粉末状Ｓｂ，Ｂｉ化合物添加
において問題であった凝集物による反応の不均一性や斑
点の発生がなく、コイル全面に渡り均一な低融点化効果
を得て、安定したグラス被膜反応を得ることを発見し
た。これにより、コイル内での不均一な追加酸化を抑制
し、コイル全面に渡って均一なグラス被膜を得ると共
に、二次再結晶開始時期までインヒービターを安定に保
つことを可能にし、優れた磁気特性を同時に得ることに
成功した。As a result of repeated studies on the addition conditions and action effects to the main component MgO of the annealing separator by using this organic metal water-soluble compound and powdery compound, an aqueous solution of an organic compound and / or complex compound of Sb and Bi. By adding a small amount of as an additive, there is no unevenness of reaction or spots due to agglomerates, which was a problem in the conventional addition of powdery Sb and Bi compounds, and a uniform low melting point effect can be obtained over the entire surface of the coil. It was then discovered that a stable glass coating reaction was obtained. As a result, it is possible to suppress uneven additional oxidation in the coil, obtain a uniform glass coating over the entire surface of the coil, and keep the in-heater stable until the secondary recrystallization start time. Succeeded in getting at the same time.
【０００９】又、Ｓｂ，Ｂｉの水溶性添加剤と共に水溶
性のＢ，Ｃｌ化合物を併用することにより、更に優れた
反応性向上効果が得られることを見出した。更に、グラ
ス被膜形成と二次再結晶を行う仕上げ焼鈍における昇温
時の雰囲気ガスとその酸化度の適正化により、優れたグ
ラス被膜と磁気特性の改善効果を得ることに成功した。It has also been found that a more excellent reactivity improving effect can be obtained by using a water-soluble B or Cl compound together with a water-soluble additive of Sb or Bi. Furthermore, we succeeded in obtaining an excellent glass coating and the effect of improving the magnetic properties by optimizing the atmospheric gas and the degree of oxidation at the time of temperature rise in the final annealing that performs glass coating formation and secondary recrystallization.
【００１０】本発明は反応性の極めて均一で優れる焼鈍
分離剤と、これを用い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として、以下の構成を
要旨とする。
（１）ＭｇＯ：１００質量部に対し、Ｓｂ，Ｂｉからな
る水溶性化合物の１種又は２種以上を固形分換算で０．
００５〜０．５００質量部添加したことを特徴とする焼
鈍分離剤。
（２）Ｓｂ，Ｂｉ水溶性化合物が有機金属化合物及び／
又は錯体化合物であることを特徴とする（１）の焼鈍分
離剤。
（３）有機金属化合物又は錯体化合物が、オキシカルボ
ン酸系化合物、オキシスルホン酸系化合物、アミノカル
ボン酸系化合物、アミン系化合物、カルボン酸系化合物
から選ばれる１種又は２種以上であることを特徴とする
（２）の焼鈍分離剤。
（４）Ｓｂ，Ｂｉ水溶性化合物が、Ｓｂ，Ｂｉの硫化
物、硫酸塩、塩化物、硝酸塩、酢酸塩から選ばれる１種
又は２種以上と、オキシカルボン酸系化合物、オキシス
ルホン酸系化合物、アミノカルボン酸系化合物、アミン
系化合物、カルボン酸系化合物から選ばれる１種又は２
種以上を混合して得たものであることを特徴とする
（２）または（３）の焼鈍分離剤。
（５）オキシカルボン酸系化合物、オキシスルホン酸系
化合物、アミノカルボン酸系化合物、アミン系化合物、
カルボン酸系化合物から選ばれる１種又は２種以上の配
合量の合計と、Ｓｂ，Ｂｉの硫化物、硫酸塩、塩化物、
硝酸塩、酢酸塩から選ばれる１種又は２種以上の配合量
の合計が、モル比で１〜５であることを特徴とする
（４）の焼鈍分離剤。
（６）さらに水溶性のＢ，Ｃｌ化合物の１種又は２種以
上を、ＭｇＯ：１００質量部に対しＢ及び／又はＣｌと
して０．００５〜０．５００質量部添加したことを特徴
とする（１）〜（５）のいずれかの焼鈍分離剤。
（７）物性値として粒度分布が粒子径１μｍ以下のもの
が１５％以上で、且つ、水和水分２．０％以下のＭｇＯ
を用いることを特徴とする（１）〜（６）のいずれかの
焼鈍分離剤。
（粒度分布：水を溶媒としてレーザー回折法により測
定）
（８）質量％で、Ｃ：０．０３０〜０．１００％、Ｓ
ｉ：２．５０〜４．５０％含有するスラブを加熱し、熱
延し、熱延鋼板を焼鈍しもしくは焼鈍せず、１回又は焼
鈍を挟む２回の冷延により最終板厚とし、脱炭焼鈍し、
窒化焼鈍を行いもしくは行わず、焼鈍分離剤を塗布し、
仕上げ焼鈍し、絶縁被膜剤塗布と焼付けを含むヒートフ
ラットニング処理を行うことからなる方向性電磁鋼板の
製造方法において、焼鈍分離剤として（１）〜（７）の
いずれかの焼鈍分離剤を用いることを特徴とするグラス
被膜と磁気特性の優れる方向性電磁鋼板の製造方法。
（９）仕上げ焼鈍の昇温過程、炉温８５０℃以上におけ
る雰囲気ガス組成をＮ2；５０ｖｏｌ％以下、雰囲気ガ
ス酸化度ＰH2O／ＰH2を０．０２以下とすることを特徴
とする（８）のグラス被膜と磁気特性の優れる方向性電
磁鋼板の製造方法。The present invention has the following features as an annealing separator having extremely uniform reactivity and excellent properties, and a method for producing a glass coating using the same and a grain-oriented electrical steel sheet having extremely excellent magnetic properties. (1) MgO: With respect to 100 parts by mass, one or more water-soluble compounds composed of Sb and Bi are added in an amount of 0.
An annealing separator, characterized by being added in an amount of 005 to 0.500 parts by mass. (2) Sb, Bi water-soluble compound is an organometallic compound and /
Alternatively, the annealing separating agent of (1), which is a complex compound. (3) The organometallic compound or complex compound is one or more selected from oxycarboxylic acid compounds, oxysulfonic acid compounds, aminocarboxylic acid compounds, amine compounds, and carboxylic acid compounds. An annealing separator characterized by (2). (4) Sb, Bi water-soluble compound is one or more selected from Sb, Bi sulfides, sulfates, chlorides, nitrates, acetates, oxycarboxylic acid compounds, oxysulfonic acid compounds 1 or 2 selected from the group consisting of an aminocarboxylic acid compound, an amine compound and a carboxylic acid compound
The annealing separator according to (2) or (3), which is obtained by mixing at least one kind. (5) Oxycarboxylic acid compound, oxysulfonic acid compound, aminocarboxylic acid compound, amine compound,
Sb, Bi sulfides, sulfates, chlorides, and a total of one or two or more selected from carboxylic acid compounds
The annealing separator according to (4), wherein the total amount of one or more selected from nitrates and acetates is 1 to 5 in terms of molar ratio. (6) One or more water-soluble B and Cl compounds are added in an amount of 0.005 to 0.500 parts by mass as B and / or Cl with respect to 100 parts by mass of MgO ( An annealing separator according to any one of 1) to (5). (7) As a physical property value, MgO having a particle size distribution of 15 μm or more with a particle size of 1 μm or less and a hydration water content of 2.0% or less
The annealing separator according to any one of (1) to (6), characterized in that (Particle size distribution: measured by laser diffraction method using water as a solvent) (8)% by mass, C: 0.030 to 0.100%, S
i: A slab containing 2.50 to 4.50% is heated and hot-rolled, and the hot-rolled steel sheet is annealed or not annealed to obtain the final plate thickness by one or two cold-rolling with annealing sandwiched between Charcoal annealed,
With or without nitriding annealing, apply an annealing separator,
In the method for producing a grain-oriented electrical steel sheet, which comprises finish annealing, heat flattening treatment including insulating film coating and baking, the annealing separator of any one of (1) to (7) is used. A method of manufacturing a grain coating and a grain-oriented electrical steel sheet having excellent magnetic properties. (9) It is characterized in that the atmospheric gas composition at the temperature rising process of finish annealing and the furnace temperature of 850 ° C. or higher is N 2 ; 50 vol% or less, and the atmospheric gas oxidation degree PH 2 O / PH 2 is 0.02 or less ( 8) A method for producing a grain coating and a grain-oriented electrical steel sheet having excellent magnetic properties.
【００１１】これにより、従来のＳｂ，Ｂｉ化合物添加
技術では実現できなかった、焼鈍分離剤中でのＳｂ，Ｂ
ｉ化合物の均一溶解を可能にし、被膜形成反応の均一
性、反応温度の低温化を実現した。この結果、従来のＳ
ｂ，Ｂｉ粉体状化合物添加法において粒状粒子や凝集体
物質によるグラス被膜形成の不均一性や、局部的な被膜
溶融問題を防止して、広範囲の仕上げ焼鈍条件でグラス
被膜と磁気特性が優れる方向性電磁鋼板が得られる。As a result, Sb and B in the annealing separator cannot be realized by the conventional Sb and Bi compound addition technology.
The i-compound was uniformly dissolved, and the film-forming reaction was made uniform and the reaction temperature was lowered. As a result, the conventional S
b, Bi In the powdery compound addition method, non-uniformity of glass film formation due to granular particles and agglomerate substances and local film melting problems are prevented, and the glass film and magnetic properties are excellent under a wide range of finish annealing conditions. A grain-oriented electrical steel sheet is obtained.
【００１２】[0012]
【発明の実施の形態】以下に本発明を詳細に説明する。BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
【００１３】先ず、本発明の焼鈍分離剤としては、Ｍｇ
Ｏ：１００質量部に対し、Ｓｂ，Ｂｉからなる水溶性化
合物の１種又は２種以上を固形分換算で０．０５〜０．
５０質量部添加することが重要である。Ｓｂ，Ｂｉの水
溶性化合物としては、Ｓｂ，Ｂｉ化合物をオキシカルボ
ン酸系化合物、オキシスルホン酸系化合物、アミノカル
ボン酸系化合物、アミン系化合物、カルボン酸系化合物
を用いて、水溶液として完全溶解された有機金属化合物
及び／又は錯体化合物が用いられる。このような溶液状
の有機金属化合物及び／又は錯体化合物は、ＭｇＯスラ
リーに溶解して鋼板酸化膜に均一に塗布され、従来の粉
末状化合物添加技術に比較して極めて安定して均一な低
融点化効果を発揮する。この結果、仕上げ焼鈍におい
て、グラス被膜がより低温の段階から均一に形成され、
従来の粉末状化合物の場合に見られる斑点状欠陥を生じ
ることがない。又、均一グラス被膜形成効果により、仕
上げ焼鈍昇温過程における表面の追加酸化をより安定し
て抑制したり、雰囲気ガスからの不必要な窒化を抑制
し、結果として二次再結晶開始時点の高温域迄インヒビ
ターが安定化され、良好な磁気特性が得られる。First, as the annealing separator of the present invention, Mg
O: With respect to 100 parts by mass, one or more water-soluble compounds composed of Sb and Bi are added in an amount of 0.05 to 0.
It is important to add 50 parts by mass. As the water-soluble compounds of Sb and Bi, the Sb and Bi compounds are completely dissolved as an aqueous solution using an oxycarboxylic acid compound, an oxysulfonic acid compound, an aminocarboxylic acid compound, an amine compound and a carboxylic acid compound. Other organometallic compounds and / or complex compounds are used. Such a solution-type organometallic compound and / or complex compound is dissolved in a MgO slurry and uniformly applied to a steel plate oxide film, which is extremely stable and has a low melting point as compared with the conventional powdery compound addition technology. Exerts the effect of chemical conversion. As a result, in finish annealing, the glass film is formed uniformly from the lower temperature stage,
It does not cause the speckled defects found in conventional powdery compounds. Also, due to the effect of forming a uniform glass film, it is possible to more stably suppress the additional oxidation of the surface during the finishing annealing temperature rise process and to suppress unnecessary nitriding from the atmospheric gas, resulting in the high temperature at the start of secondary recrystallization. The inhibitor is stabilized up to the range and good magnetic properties are obtained.
【００１４】Ｓｂ，Ｂｉ水溶性化合物の添加量について
は、ＭｇＯ：１００質量部に対し固形分で０．０５質量
部未満の添加の場合、低融点化効果が十分でなく、工程
条件によってはグラス被膜がやや薄くなり、磁気特性も
やや悪化傾向が見られるため制限される。一方０．５０
質量部超では低融点化効果が過剰になりすぎて、過酸化
現象と見られる厚ぼったく、黒っぽいグラス被膜とな
り、局部的に金属斑点状の被膜欠陥が発生する場合があ
る。又、磁気特性についても、特に、磁束密度の低下が
生じることから制限される。Regarding the amount of Sb, Bi water-soluble compound added, when the solid content is less than 0.05 parts by mass relative to 100 parts by mass of MgO, the effect of lowering the melting point is not sufficient, and depending on the process conditions, the glass may be added. This is limited because the coating becomes slightly thinner and the magnetic properties tend to deteriorate slightly. On the other hand, 0.50
If the amount exceeds the mass part, the effect of lowering the melting point becomes excessive, resulting in a thick, dark glass film which is considered to be a peroxide phenomenon, and metal spot-like film defects may locally occur. Further, the magnetic characteristics are also limited because the magnetic flux density is lowered.
【００１５】Ｓｂ，Ｂｉ水溶性化合物としては、オキシ
カルボン酸系化合物、オキシスルホン酸系化合物，アミ
ノカルボン酸系化合物、アミン系化合物、カルボン酸系
化合物を用いる。これらの有機化合物は、Ｓｂ，Ｂｉ化
合物と酸性からアルカリ性にわたる広いｐＨ範囲で結合
して、有機金属化合物や錯体を生成しやすく、最小限の
有機物配合量で効果を発揮するからである。これらの中
で、特に、オキシカルボン酸系有機化合物とアミノカル
ボン酸系有機化合物が優れており、さらにオキシカルボ
ン酸は、高い溶解性に加え低価格であり、工業的に用い
るのに有利である。As the Sb and Bi water-soluble compounds, oxycarboxylic acid compounds, oxysulfonic acid compounds, aminocarboxylic acid compounds, amine compounds and carboxylic acid compounds are used. This is because these organic compounds are likely to combine with Sb and Bi compounds in a wide pH range from acidic to alkaline to form organometallic compounds and complexes, and exhibit effects with a minimum amount of organic compound. Among these, in particular, oxycarboxylic acid-based organic compounds and aminocarboxylic acid-based organic compounds are excellent. Further, oxycarboxylic acid is advantageous in industrial use because it has high solubility and low cost. .
【００１６】オキシカルボン酸系化合物としてはグリコ
ール酸、乳酸、グリセリン酸、りんご酸、酒石酸、クエ
ン酸等が用いられる。この中で酒石酸、クエン酸は使用
の容易性、コスト面を考慮すると有利で本発明の使用に
最も適している。As the oxycarboxylic acid compound, glycolic acid, lactic acid, glyceric acid, malic acid, tartaric acid, citric acid and the like are used. Among these, tartaric acid and citric acid are advantageous in terms of easiness of use and cost, and are most suitable for use in the present invention.
【００１７】また、オキシスルホン酸系有機化合物とし
ては、スルホサリチル酸、ＢＡＬ、ＨＱＳ等が用いられ
る。アミノカルボン酸系化合物としてはグルタミン酸、
ピコリン酸、ＥＤＴＡ、ＤＣＴＡ、ＮＴＡ、ＤＴＰＡ、
ＥＧＴＡ、ＨＥＤＴＡ等が用いられる。アミン系化合物
としては、例えばエチレンジアミン、Ｄｅｎ、Ｔｒｉｅ
ｎ、Ｔｅｔｒｅｎ、Ｔｒｅｎ、ＴＥＡ、ＤＤＳ等が用い
られる。しかしながらこれらの化合物に限定されるもの
ではなく、オキシカルボン酸系化合物、オキシスルホン
酸系化合物、アミノカルボン酸系化合物、アミン系化合
物、カルボン酸系化合物であれば、他の化合物を用いて
も良い。As the oxysulfonic acid type organic compound, sulfosalicylic acid, BAL, HQS and the like are used. Glutamic acid as the aminocarboxylic acid compound,
Picolinic acid, EDTA, DCTA, NTA, DTPA,
EGTA, HEDTA, etc. are used. Examples of amine compounds include ethylenediamine, Den, Trie
n, Tetren, Tren, TEA, DDS, etc. are used. However, the compounds are not limited to these compounds, and other compounds may be used as long as they are oxycarboxylic acid compounds, oxysulfonic acid compounds, aminocarboxylic acid compounds, amine compounds, and carboxylic acid compounds. .
【００１８】Ｓｂ，Ｂｉ水溶性化合物の構成物質として
は、Ｓｂ，Ｂｉの硫化物、硫酸塩、塩化物、硝酸塩、酢
酸塩の１種又は２種以上が用いられる。これらの化合物
は前記、オキシカルボン酸系化合物、オキシスルホン酸
系化合物、アミノカルボン酸系化合物、アミン系化合
物、カルボン酸系化合物との相溶性に優れており、本発
明の有機金属化合物溶液の生成に有利である。特に、硫
化物、硫酸塩、塩化物を用いることにより、優れた被膜
形成促進効果と磁性改善効果を発揮する。As the constituent substance of the Sb, Bi water-soluble compound, one or more of Sb, Bi sulfides, sulfates, chlorides, nitrates and acetates are used. These compounds are excellent in compatibility with the above-mentioned oxycarboxylic acid type compound, oxysulfonic acid type compound, aminocarboxylic acid type compound, amine type compound, carboxylic acid type compound, and form the organometallic compound solution of the present invention. Is advantageous to. In particular, the use of sulfides, sulfates, and chlorides exerts an excellent effect of promoting film formation and an effect of improving magnetism.
【００１９】Ｓｂ，Ｂｉ化合物から有機金属化合物、錯
体の調整調整を行う場合には、先ず、水にオキシカルボ
ン酸系化合物、オキシスルホン酸系化合物、アミノカル
ボン酸系化合物、アミン系化合物、カルボン酸系化合物
を溶解し、次いで、Ｓｂ，Ｂｉ化合物を徐々に添加して
溶解し、水で希釈するのが好ましい。このとき、Ｓｂ，
Ｂｉ化合物を急速に配合すると、加水分解により水酸化
物が生成し、安定した有機化合物或いは錯体が生じな
い。溶液の濃度はできるだけ低濃度にするのが溶液の安
定化を得るのに有利である。When the organometallic compound or complex is prepared and adjusted from the Sb or Bi compound, first, oxycarboxylic acid compound, oxysulfonic acid compound, aminocarboxylic acid compound, amine compound, carboxylic acid is added to water. It is preferable to dissolve the system compound, then gradually add and dissolve the Sb and Bi compounds, and dilute with water. At this time, Sb,
When the Bi compound is blended rapidly, a hydroxide is generated by hydrolysis and a stable organic compound or complex is not formed. It is advantageous to obtain the stabilization of the solution that the concentration of the solution is as low as possible.
【００２０】溶液調整における有機物の添加量はＳｂ，
Ｂｉの無機物と等モル比以上であれば良い。Ｓｂ，Ｂｉ
化合物と反応した有機物は乾燥工程や仕上げ焼鈍昇温過
程で分解するが、有機物量が多くなりすぎると乾燥や焼
鈍条件によっては残留し、鋼板への浸炭等の懸念が生じ
るため、有機物／無機物のモル比は１〜５程度に抑える
のが良く、好ましくは２以下に抑えるのが良い。このよ
うな範囲であれば、本発明のようなＳｂ，Ｂｉ等の有機
金属化合物及び／又は錯体を微量添加する技術において
は有機物による害は生じない。The amount of organic matter added in the solution preparation is Sb,
It suffices if it is at least an equimolar ratio to the inorganic substance of Bi. Sb, Bi
The organic matter that has reacted with the compound decomposes in the drying process and the temperature increase in the final annealing, but if the amount of organic matter becomes too large, it may remain depending on the drying and annealing conditions, and there is a risk of carburizing the steel sheet. The molar ratio is preferably controlled to about 1 to 5, preferably 2 or less. Within such a range, no harm is caused by organic substances in the technique of adding a small amount of an organometallic compound and / or complex such as Sb and Bi as in the present invention.
【００２１】この様に調整された水溶液は、ＭｇＯスラ
リー中におけるｐＨ：８〜１０程度の弱アルカリ性の条
件下においても安定で、再析出したり、凝集する問題が
なく安定的に鋼板面に塗布焼付けされる。The thus prepared aqueous solution is stable even under weak alkaline conditions of pH: about 8 to 10 in MgO slurry, and is stably applied to the steel sheet surface without the problem of reprecipitation or aggregation. Baked.
【００２２】次に、Ｓｂ，Ｂｉの水溶性添加剤と共に水
溶性のＢ或いはＣｌ化合物を添加すると、他の工程条件
によっては更に優れた反応性向上効果が得られる場合が
あり併用添加するのがより好ましい。Ｂ，Ｃｌ化合物に
ついては、本発明者等により、過去数々の提案がなされ
ている。これらは単独使用において効果が認められ、実
用化されてきた。これらの化合物の中で、特に、水溶性
の化合物の場合、本発明のＳｂ，Ｂｉの水溶液化合物と
併用すると相乗的な向上効果が得られる。添加物として
は、硼酸、硼酸塩、塩酸、塩化物等が用いられる。添加
量としてはＢ及び／又はＣｌ量としてＭｇＯ１００質量
部あたり０．０５〜０．５０質量部が添加される。０．
０５質量部未満では相乗的改善効果が殆ど見られない。
一方、０．５０％超になると、低融点化作用が過剰にな
ったり、過酸化状現象が見られ、グラス被膜がポーラス
になったり、ガスマーク状ムラを生じるため好ましくな
い。又、磁気特性の低下を生じる場合があることから制
限される。Next, when a water-soluble B or Cl compound is added together with the water-soluble additives of Sb and Bi, a more excellent reactivity improving effect may be obtained depending on other process conditions, so that they should be added together. More preferable. Regarding the B and Cl compounds, the present inventors have made numerous proposals in the past. These are effective when used alone, and have been put into practical use. Among these compounds, particularly in the case of a water-soluble compound, a synergistic improvement effect can be obtained when used in combination with the aqueous solution compound of Sb and Bi of the present invention. As the additive, boric acid, borate, hydrochloric acid, chloride or the like is used. The amount of B and / or Cl added is 0.05 to 0.50 parts by mass per 100 parts by mass of MgO. 0.
When the amount is less than 05 parts by mass, the synergistic improvement effect is hardly seen.
On the other hand, if it exceeds 0.50%, the effect of lowering the melting point becomes excessive, a phenomenon of peroxidation is observed, the glass film becomes porous, and gas mark-like unevenness occurs, which is not preferable. In addition, there is a possibility that the magnetic characteristics may be deteriorated, so that it is limited.
【００２３】次に、本発明に使用されるＭｇＯとして
は、粒度分布が粒子径１μｍ以下のものが１５％以上
で、且つ、水和水分２．０％未満のＭｇＯを用いるのが
より好ましい条件である。ここで粒度分布は、水を溶媒
とするレーザー回折法を用いて測定した値を用いてい
る。本発明のようにＳｂ、Ｂｉの水溶性化合物を使用す
る場合には、それによる低融点化効果が顕著であり、Ｍ
ｇＯの物性値としては低水和のものを使用するのがより
好ましい。粒子径１μｍ以下が１５％未満の場合には、
本発明のＳｂ、Ｂｉ化合物を用いてもグラス被膜形成反
応がやや低下傾向が見られ、コイル外周部の被膜の均一
性がやや不安定になる場合がある。又、水和水分が２％
超の場合には、仕上げ焼鈍の昇温時に分解水分により鋼
板間がやや高酸化性になる結果、コイルエッジ、外周部
のグラス被膜の厚み、色調が黒っぽくなる傾向が見られ
る場合があるため制限される。Next, as MgO used in the present invention, it is more preferable to use MgO having a particle size distribution of 15 μm or more with a particle size of 1 μm or less and having a hydration water content of less than 2.0%. Is. Here, the particle size distribution uses a value measured by a laser diffraction method using water as a solvent. When a water-soluble compound of Sb or Bi is used as in the present invention, the effect of lowering the melting point is remarkable, and M
It is more preferable to use a low hydration property as the physical property value of gO. When the particle size of 1 μm or less is less than 15%,
Even if the Sb and Bi compounds of the present invention are used, the glass film forming reaction tends to be slightly decreased, and the uniformity of the film on the outer peripheral portion of the coil may be slightly unstable. Also, the hydrated water content is 2%
If it is over, there is a possibility that the coil edge, the thickness of the glass coating on the outer circumference, and the color tone may tend to be dark as a result of the slightly oxidized nature between the steel sheets due to the decomposed moisture during the temperature rise during finish annealing. To be done.
【００２４】本発明の焼鈍分離剤を用いる方向性電磁鋼
板の製造にあたっては、出発材として、質量％で、Ｃ：
０．０３０〜０．１００％、Ｓｉ：２．５０〜４．５０
％を含有する方向性電磁鋼板スラブを加熱し、熱延し、
熱延鋼板を焼鈍しもしくは焼鈍せず、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、次いで、８００
〜９００℃で、Ｈ２又はＮ２＋Ｈ２雰囲気ガスで酸化度
を調節して脱炭、一次再結晶及び酸化膜形成を行う。必
要に応じて同一ライン中或いは別ラインで窒化処理をイ
ンヒビターを形成・強化しても良い。In the production of the grain-oriented electrical steel sheet using the annealing separator of the present invention, C:
0.030-0.100%, Si: 2.50-4.50
% Of grain-oriented electrical steel sheet slab is heated and hot rolled,
The hot-rolled steel sheet is annealed or not annealed to obtain the final sheet thickness by cold rolling once or two or more times with annealing sandwiched, and then 800
Decarburization, primary recrystallization, and oxide film formation are performed by adjusting the degree of oxidation with H 2 or N 2 + H 2 atmosphere gas at ˜900 ° C. If necessary, an inhibitor may be formed and strengthened in the nitriding treatment in the same line or in another line.
【００２５】この鋼板上に、ＭｇＯ：１００質量部に対
し、本発明のＳｂ，Ｂｉ水溶性化合物の１種又は２種以
上を固形分換算で０．００５〜０．５００質量部と、も
しくはさらに水溶性のＢ，Ｃｌ化合物をＢ，Ｃｌとして
０．００５〜０．２００質量部を添加した焼鈍分離剤ス
ラリーをコーティングロール等で鋼板に塗布し、乾燥後
コイルに巻き取る。この際、焼鈍分離剤スラリーには、
グラス被膜生成反応促進、板間雰囲気調整、インヒビタ
ー強化の目的で、前記反応促進補助剤に加えて、硫黄化
合物、窒素化合物、酸化物等を鋼成分、処理条件に応じ
て併用しても良い。On this steel sheet, 0.005 to 0.500 parts by mass of solid content of one or more of Sb and Bi water-soluble compounds of the present invention is added to 100 parts by mass of MgO, or further. The steel sheet is coated with an annealing separator slurry containing 0.005 to 0.200 parts by mass of a water-soluble B and Cl compound as B and Cl, and dried and wound on a coil. At this time, the annealing separator slurry,
For the purpose of accelerating the reaction for forming a glass film, adjusting the atmosphere between plates, and strengthening the inhibitor, a sulfur compound, a nitrogen compound, an oxide, etc. may be used in combination according to the steel composition and the processing conditions, in addition to the reaction accelerating aid.
【００２６】以上のように本発明の焼鈍分離剤を塗布さ
れたコイルは、最終仕上げ焼鈍としてバッチ式或いは連
続焼鈍式炉内において１１００〜１２５０℃で２０Ｈｒ
程度の長時間焼鈍が行われ、二次再結晶、純化及びグラ
ス被膜形成が行われる。このとき、本発明の仕上げ焼鈍
条件として好ましくは、昇温過程、８５０℃以上の雰囲
気ガスとして、Ｎ２＋Ｈ２でＮ２５０ｖｏｌ％以下、且
つ雰囲気酸化度ＰH2O／ＰH2を０．０２以下として行わ
れる。Ｎ2が５０ｖｏｌ％を超えると、８５０℃以上で
の酸化度を０．０２以下とするのが困難になる他、鋼板
を窒化してインヒビター挙動に影響し、磁気特性が劣化
する場合がある。As described above, the coil coated with the annealing separating agent of the present invention is subjected to final finish annealing in a batch type or continuous annealing type furnace at 1100 to 1250 ° C. for 20 hours.
Annealing is performed for about a long time, and secondary recrystallization, purification, and glass film formation are performed. At this time, as the finish annealing conditions of the present invention, it is preferable that N 2 + H 2 is N 2 50 vol% or less and the atmospheric oxidation degree PH 2 O / PH 2 is 0.02 as a temperature rising process and an atmospheric gas of 850 ° C. or higher. It is done as follows. When N 2 exceeds 50 vol%, it becomes difficult to set the degree of oxidation at 850 ° C. or higher to 0.02 or less, and the steel sheet is nitrided to affect the inhibitor behavior, which may deteriorate the magnetic properties.
【００２７】又、ＰH2Ｏ／ＰH2が０．０２以上では、グ
ラス被膜形成時期の酸化度が高すぎて、鋼板表面の追加
酸化や過酸化現象によるグラス被膜の色調ムラ、ピンホ
ール状被膜欠陥が生じやすくなる。又、このような場合
には、表面酸化により鋼中インヒビターの弱体化が早ま
り、良好な二次再結晶が得られ難くなる。Further, when PH 2 O / PH 2 is 0.02 or more, the degree of oxidation at the time of forming the glass film is too high, and uneven color tone of the glass film due to additional oxidation or peroxidation of the steel plate surface, pinhole-like film Defects are likely to occur. Further, in such a case, weakening of the inhibitor in steel is accelerated due to surface oxidation, and it becomes difficult to obtain good secondary recrystallization.
【００２８】仕上げ焼鈍後のコイルは、連続ラインにお
いて、余剰の焼鈍分離剤の水洗除去、軽酸洗の後、絶縁
被膜剤を塗布し、焼付けと形状矯正及び歪取り焼鈍をか
ねてヒートフラットニングが行われ、最終製品となる。
この際の絶縁被膜剤としては、Ａｌ及び／又はＭｇから
なる５０％燐酸塩：１００ｌに対し、２０％コロイダル
シリカ：１５０〜３００ｌ、Ｃｒ化合物をＣｒＯ3とし
て８〜１８ｋｇ配合したものを用いるのが、張力付与と
被膜性能の面で有利である。The coil after finish annealing is subjected to heat flattening in a continuous line after removing excess annealing separator by washing with water, light pickling, and then applying an insulating film agent, and performing baking, shape correction and strain relief annealing. It is done and it becomes the final product.
In this case, as the insulating coating agent, it is preferable to use 50% phosphate consisting of Al and / or Mg: 100 liters, 20% colloidal silica: 150 to 300 liters, and a compound of 8 to 18 kg of CrO 3 as CrO 3. It is advantageous in terms of applying tension and coating performance.
【００２９】[0029]
【実施例】<実施例１>質量％で、Ｃ：０．０７８％、Ｓ
ｉ：３．３０％、Ｍｎ：０．０６５％、酸可溶Ａｌ：
０．０２６％、Ｓ：０．０２４％、Ｎ：０．００７７
％、Ｓｎ：０．０７５％、Ｃｕ：０．０８０％、残部Ｆ
ｅと不可避の不純物からなる素材スラブを熱延し、熱延
板を１１００℃で２分間焼鈍し、酸洗、冷延して最終板
厚０．２２５ｍｍとした。次いで、８４５℃で１１０秒
間、Ｎ２２５％＋Ｈ２７５％、露点７０℃の雰囲気中で
脱炭焼鈍した。[Examples] <Example 1>% by mass, C: 0.078%, S
i: 3.30%, Mn: 0.065%, acid-soluble Al:
0.026%, S: 0.024%, N: 0.0077
%, Sn: 0.075%, Cu: 0.080%, balance F
A raw material slab consisting of e and inevitable impurities was hot-rolled, and the hot-rolled sheet was annealed at 1100 ° C. for 2 minutes, pickled and cold-rolled to a final sheet thickness of 0.225 mm. Next, decarburization annealing was performed at 845 ° C. for 110 seconds in an atmosphere of N 2 25% + H 2 75% and a dew point of 70 ° C.
【００３０】この鋼板上に表１に示すようにＳｂ，Ｂｉ
化合物を用い、予めオキシカルボン酸系有機物と反応さ
せ、有機金属化合物１０％水溶液とした添加剤、または
比較例として粉末状添加剤を、添加量を変更して添加し
た焼鈍分離剤スラリーを塗布し乾燥してコイル状に巻き
取った。On this steel plate, as shown in Table 1, Sb, Bi
Using a compound, an annealing separation agent slurry was prepared by reacting with an oxycarboxylic acid-based organic material in advance to obtain an organic metal compound 10% aqueous solution additive, or a powdery additive as a comparative example at different addition amounts. It was dried and wound into a coil.
【００３１】このコイルに１２００℃×２０Ｈｒの仕上
げ焼鈍を行い、その後、２０％コロイダルシリカ；１０
０ｌ＋５０％燐酸Ａｌ；５０ｌ＋ＣｒＯ３；５ｋｇから
なる絶縁被膜剤を、乾燥焼き付け後に両面で４．５ｇ／
ｍ２になるよう塗布し、８５０℃でヒートフラットニン
グ処理を行い製品とした。この試験におけるグラス被膜
形成状況、磁気特性の結果を表２に示す。This coil was subjected to finish annealing at 1200 ° C. for 20 hours and then 20% colloidal silica; 10
An insulating film agent consisting of 0 l + 50% Al phosphate; 50 l + CrO 3 ; 5 kg was applied on both sides after drying and baking at 4.5 g /
It was applied so as to be m 2 and subjected to heat flattening treatment at 850 ° C. to obtain a product. Table 2 shows the results of the glass film formation conditions and magnetic properties in this test.
【００３２】[0032]
【表１】 [Table 1]
【００３３】[0033]
【表２】 [Table 2]
【００３４】この試験の結果、本発明の、Ｓｂ，Ｂｉを
有機金属化合物として所定量添加した焼鈍分離剤を用い
た場合には、何れもグラス被膜が均一で光沢があり、良
好なグラス被膜の形成が見られた。又これらは何れも絶
縁被膜の密着性が良好で、磁気特性においても磁束密度
の向上効果が大きく、鉄損特性が優れる結果となった。
しかし、本発明の水溶性化合物を用いても、添加量が多
い比較例１ではグラス被膜がやや厚ぼったく、光沢が低
下し、冷延模様が見えるようなやや過酸化傾向と思われ
るグラス被膜となった。この場合やや磁気特性の低下も
見られた。As a result of this test, when the annealing separating agent of the present invention containing Sb and Bi as an organometallic compound in a predetermined amount was used, the glass coating was uniform and glossy, and a good glass coating was obtained. Formation was seen. In addition, in all of these, the adhesion of the insulating coating was good, the effect of improving the magnetic flux density was great in terms of magnetic characteristics, and the iron loss characteristics were excellent.
However, even when the water-soluble compound of the present invention was used, in Comparative Example 1 in which the amount of addition was large, the glass film was slightly thickened, the gloss was reduced, and a glass film which was considered to be slightly peroxidized so that a cold-rolled pattern was visible was obtained. It was In this case, a slight decrease in magnetic properties was also observed.
【００３５】一方、比較例２〜４のように粉末状のＳ
ｂ、Ｂｉ化合物を添加した場合には、グラス被膜の厚
み、均一性が本発明に比較して劣り、鋼板全面、特にエ
ッジ部周辺には斑点状の斑が多発した。更に、本発明に
比し、絶縁被膜の密着性が劣り、磁気特性についてもか
なり劣る結果となった。
<実施例２>実施例１と同様にして調整した脱炭焼鈍板を
出発材とし、この鋼板上に表３に示すようにＳｂ，Ｂｉ
化合物を用いて、オキシカルボン酸系化合物、アミノカ
ルボン酸系化合物を用いて、予め有機金属化合物５％水
溶液とした添加剤と共に、水溶性Ｂ，Ｃｌ化合物として
硼酸と塩化マンガンを添加量を変更して添加した焼鈍分
離剤スラリーを塗布し乾燥してコイル状に巻き取った。
この際、比較条件には、実施例１と同様に粉末状のＳ
ｂ、Ｂｉ塩化物を添加した。On the other hand, as in Comparative Examples 2 to 4, powdery S
When b and Bi compounds were added, the thickness and uniformity of the glass coating were inferior to those of the present invention, and spot-like spots frequently occurred on the entire surface of the steel sheet, particularly around the edge portion. Furthermore, the adhesion of the insulating coating was poorer than that of the present invention, and the magnetic properties were also considerably poor. <Example 2> A decarburized annealed sheet prepared in the same manner as in Example 1 was used as a starting material, and Sb, Bi as shown in Table 3 on this steel sheet.
The compound was used to change the addition amounts of boric acid and manganese chloride as water-soluble B and Cl compounds, together with an additive that was previously made into a 5% aqueous solution of an organometallic compound using an oxycarboxylic acid compound and an aminocarboxylic acid compound. The added annealing separator slurry was applied, dried and wound into a coil.
At this time, as a comparison condition, powdery S as in Example 1 was used.
b, Bi chloride was added.
【００３６】このコイルに１２００℃×２０Ｈｒの仕上
げ焼鈍を行い、その後、２０％コロイダルシリカ；１０
０ｌ＋５０％燐酸Ａｌ；５０ｌ＋ＣｒＯ３；５ｋｇから
なる絶縁被膜剤を、乾燥焼き付け後に両面で４．５ｇ／
ｍ２になるよう塗布し、８５０℃でヒートフラットニン
グ処理を行い製品とした。この試験におけるグラス被膜
形成状況、磁気特性の結果を表４に示す。This coil was subjected to finish annealing at 1200 ° C. for 20 hours and then 20% colloidal silica; 10
An insulating film agent consisting of 0 l + 50% Al phosphate; 50 l + CrO 3 ; 5 kg was applied on both sides after drying and baking at 4.5 g /
It was applied so as to be m 2 and subjected to heat flattening treatment at 850 ° C. to obtain a product. Table 4 shows the results of the glass film formation conditions and magnetic properties in this test.
【００３７】[0037]
【表３】 [Table 3]
【００３８】[0038]
【表４】 [Table 4]
【００３９】この試験の結果、Ｓｂ，Ｂｉを有機化合物
水溶液として所定量添加した焼鈍分離剤を用いた本発明
例は、何れもグラス被膜が均一で優れており、磁気特性
においても実施例１を上回る良好な結果が得られた。特
に、水溶性Ｂ，Ｃｌ化合物として硼酸、塩化マンガンを
適当量併用添加した場合に極めて良好なグラス被膜と磁
気特性が得られた。しかし併用した水溶性塩化物が多す
ぎる本発明７ではグラス被膜、磁気特性共にやや劣る結
果となった。As a result of this test, in all the examples of the present invention using the annealing separator in which a predetermined amount of Sb and Bi was added as an aqueous solution of an organic compound, the glass coating was uniform and excellent, and the magnetic characteristics of Example 1 were the same. Excellent results were obtained. In particular, when boric acid and manganese chloride were added together in appropriate amounts as the water-soluble B and Cl compounds, extremely good glass coating and magnetic properties were obtained. However, in Invention 7 in which too much water-soluble chloride was used in combination, the glass coating and the magnetic properties were slightly inferior.
【００４０】また、比較例１の様に添加量が多すぎる場
合にはややグラス被膜が薄くなり、磁気特性も低下する
傾向であり、比較例２〜４のように粉末状添加剤を用い
た場合にはグラス被膜の斑の発生が多く見られ、磁気特
性も本発明に比しかなり劣る結果となった。
<実施例３>質量％で、Ｃ：０．０５３％、Ｓｉ：３．３
５％、Ｍｎ：０．１１５％、酸可溶Ａｌ：０．０２９
％、Ｓ：０．００７％、Ｎ：０．００７０％、Ｓｎ：
０．０４５％、残部Ｆｅと不可避不純物からなる素材ス
ラブを熱延し、熱延板を１１２０℃で２分間焼鈍し、酸
洗、冷延して最終板厚０．２２５ｍｍとした。次いで、
８３５℃で１００秒間、Ｎ２２５％＋Ｈ２７５％、露点
６８℃の雰囲気中で脱炭焼鈍し、次いで、同じ連続焼鈍
ラインにおいてＮ２２５％＋Ｈ２７５％＋ＮＨ３雰囲気
中で７５０℃×３０秒間、鋼板窒素量２００ｐｐｍにな
るように窒化焼鈍を行った。Further, when the addition amount is too large as in Comparative Example 1, the glass coating tends to be slightly thinned and the magnetic properties tend to be deteriorated. Therefore, as in Comparative Examples 2 to 4, powdery additives were used. In this case, the occurrence of spots on the glass coating was often observed, and the magnetic properties were considerably inferior to those of the present invention. <Example 3>% by mass, C: 0.053%, Si: 3.3
5%, Mn: 0.115%, acid-soluble Al: 0.029
%, S: 0.007%, N: 0.0070%, Sn:
A raw material slab containing 0.045% of balance Fe and unavoidable impurities was hot-rolled, and the hot-rolled sheet was annealed at 1120 ° C. for 2 minutes, pickled and cold-rolled to a final sheet thickness of 0.225 mm. Then
Decarburization annealing at 835 ° C. for 100 seconds in N 2 25% + H 2 75%, dew point 68 ° C., then 750 ° C. in N 2 25% + H 2 75% + NH 3 atmosphere in the same continuous annealing line. Nitriding annealing was performed for 30 seconds so that the nitrogen content of the steel sheet was 200 ppm.
【００４１】この鋼板上に表５に示すように、水和水
分、微粒子割合の異なるＭｇＯ１００質量部に対し、硼
酸Ｎａを０．３質量部と、Ｓｂ化合物をオキシカルボン
酸系有機物を用いて予め水溶液とした添加剤を添加した
焼鈍分離剤スラリーを塗布乾燥してコイル状に巻き取っ
た。As shown in Table 5 on this steel sheet, 0.3 parts by mass of Na borate and 100 parts by mass of MgO having different hydrated water contents and fine particle ratios were used in advance with an Sb compound as an oxycarboxylic acid organic compound. The annealing separating agent slurry containing the additive as an aqueous solution was applied, dried and wound into a coil.
【００４２】このコイルに１２００℃×２０Ｈｒの仕上
げ焼鈍を行った。このとき、昇温過程における焼鈍雰囲
気条件を表５のようにして焼鈍した。This coil was subjected to finish annealing at 1200 ° C. × 20 Hr. At this time, the annealing atmosphere conditions in the temperature rising process were as shown in Table 5.
【００４３】その後、２０％コロイダルシリカ；１００
ｌ＋５０％燐酸Ａｌ；５０ｌ＋ＣｒＯ３；５ｋｇからな
る絶縁被膜剤を、乾燥焼き付け後に両面で４．５ｇ／ｍ
２になるよう塗布し、８５０℃でヒートフラットニング
処理を行い製品とした。この試験におけるグラス被膜形
成状況、磁気特性の結果を表６に示す。Thereafter, 20% colloidal silica; 100
1 + 50% Al phosphate; 50 l + CrO 3 ; 4.5 g / m on both sides after insulation baking agent consisting of 5 kg
It was applied so as to be 2 and subjected to heat flattening treatment at 850 ° C. to obtain a product. Table 6 shows the results of the glass film formation conditions and magnetic properties in this test.
【００４４】[0044]
【表５】 [Table 5]
【００４５】[0045]
【表６】 [Table 6]
【００４６】この試験の結果、Ｓｂ化合物を所定量添加
した焼鈍分離剤を用いた本発明例は、何れもグラス被膜
が均一で優れており、特に、ＭｇＯとして水和１．８％
で粒子径１μ以下が２５％もしくは４０％の微粒子Ｍｇ
Ｏを用いた場合には、グラス被膜が極めて良好で、磁気
特性においても良好な結果が得られた。また、仕上げ焼
鈍雰囲気として８５０℃以降の雰囲気酸化度ＰH2O／ＰH
2＝０．０１として適用した場合には、更に良好な外観
の緻密なグラス被膜が得られ、被膜張力もＰH2O／ＰH2
＝０．２５の場合と比較して高く、極めて優れた磁気特
性が得られた。As a result of this test, in all of the examples of the present invention using the annealing separator containing the Sb compound added in a predetermined amount, the glass coating was uniform and excellent, and in particular, 1.8% hydration as MgO was obtained.
With a particle size of 1μ or less is 25% or 40%
When O was used, the glass film was extremely good and good results were obtained in terms of magnetic properties. Also, as the finish annealing atmosphere, the atmospheric oxidation degree after 850 ° C. PH 2 O / PH
When applied as 2 = 0.01, a dense glass coating with a better appearance is obtained, and the coating tension is PH 2 O / PH 2
= 0.25, it was higher than that in the case of = 0.25, and extremely excellent magnetic characteristics were obtained.
【００４７】[0047]
【発明の効果】本発明によれば、水溶性Ｓｂ，Ｂｉ化合
物を焼鈍分離剤に添加することにより、従来の粉末状添
加剤のような不溶解粒子、凝集体による反応性低下、粒
状物によるグラス被膜欠陥問題を解決し、均一で安定し
た反応性向上効果と低融点化効果ガ得られる。この結
果、昇温過程における追加酸化を抑制して均一で優れた
グラス被膜を形成し、同時に優れた磁気特性が得られ
る。According to the present invention, by adding the water-soluble Sb and Bi compounds to the annealing separator, insoluble particles such as the conventional powdery additives, decrease in reactivity due to agglomerates, and particles are caused. It solves the problem of glass coating defects, and provides a uniform and stable reactivity improvement effect and low melting point effect. As a result, additional oxidation in the temperature rising process is suppressed to form a uniform and excellent glass film, and at the same time, excellent magnetic properties are obtained.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 熊野 知二 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 藤井 宣憲 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 岡田 慎吾 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 收 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 (72)発明者 宮田 茂男 福岡県北九州市八幡西区下畑町16番11号 株式会社海水化学研究所内 Ｆターム(参考） 4K026 AA03 AA22 BA08 BB10 CA15 CA18 CA32 CA33 CA34 CA37 DA02 EA17 EB11 4K033 AA02 CA01 CA02 CA09 FA00 FA13 FA14 GA00 HA01 HA03 JA07 LA01 RA04 SA02 SA03 TA02 TA03 5E041 AA02 BC01 CA01 HB11 NN01 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Tomoji Kumano 1-1 Tobata-cho, Tobata-ku, Kitakyushu, Fukuoka Inside the Yawata Works of Hontan Works (72) Inventor Noriyoshi Fujii 1-1 Tobata-cho, Tobata-ku, Kitakyushu, Fukuoka Inside the Yawata Works of Hontan Works (72) Inventor Shingo Okada 1-1 Tobata-cho, Tobata-ku, Kitakyushu, Fukuoka Inside the Yawata Works of Hontan Works (72) Inventor Osamu Tanaka 59, 46 Nakahara, Tobata-ku, Kitakyushu, Fukuoka Nittetsu Plant Design Co., Ltd. (72) Inventor Shigeo Miyata 16-11 Shimohata-cho, Yawatanishi-ku, Kitakyushu City, Fukuoka Prefecture Seawater Chemical Laboratory Co., Ltd. F-term (reference) 4K026 AA03 AA22 BA08 BB10 CA15 CA18 CA32 CA33 CA34 CA37 DA02 EA17 EB11 4K033 AA02 CA01 CA02 CA09 FA00 FA13 FA14 GA00 HA01 HA03 JA07 LA01 RA04 SA02 SA03 TA02 TA03 5E041 AA02 BC01 CA01 HB11 NN01
Claims (9)
ｉからなる水溶性化合物の１種又は２種以上を固形分換
算で０．００５〜０．５００質量部添加したことを特徴
とする焼鈍分離剤。1. Sb and B for 100 parts by mass of MgO:
An annealing separator, characterized in that 0.005 to 0.500 parts by mass of a water-soluble compound of i is added in terms of solid content.
物及び／又は錯体化合物であることを特徴とする請求項
１記載の焼鈍分離剤。2. The annealing separator according to claim 1, wherein the Sb, Bi water-soluble compound is an organometallic compound and / or a complex compound.
シカルボン酸系化合物、オキシスルホン酸系化合物、ア
ミノカルボン酸系化合物、アミン系化合物、カルボン酸
系化合物から選ばれる１種又は２種以上であることを特
徴とする請求項２記載の焼鈍分離剤。3. The organometallic compound or complex compound is one or more selected from oxycarboxylic acid compounds, oxysulfonic acid compounds, aminocarboxylic acid compounds, amine compounds and carboxylic acid compounds. The annealing separator according to claim 2, wherein
の硫化物、硫酸塩、塩化物、硝酸塩、酢酸塩から選ばれ
る１種又は２種以上と、オキシカルボン酸系化合物、オ
キシスルホン酸系化合物、アミノカルボン酸系化合物、
アミン系化合物、カルボン酸系化合物から選ばれる１種
又は２種以上を混合して得たものであることを特徴とす
る請求項２または３記載の焼鈍分離剤。4. The water-soluble compound of Sb, Bi is Sb, Bi
And one or more selected from sulfides, sulfates, chlorides, nitrates and acetates of oxycarboxylic acid compounds, oxysulfonic acid compounds, aminocarboxylic acid compounds,
The annealing separator according to claim 2 or 3, which is obtained by mixing one or more selected from amine compounds and carboxylic acid compounds.
ホン酸系化合物、アミノカルボン酸系化合物、アミン系
化合物、カルボン酸系化合物から選ばれる１種又は２種
以上の配合量の合計と、Ｓｂ，Ｂｉの硫化物、硫酸塩、
塩化物、硝酸塩、酢酸塩から選ばれる１種又は２種以上
の配合量の合計が、モル比で１〜５であることを特徴と
する請求項４記載の焼鈍分離剤。5. A total of one or two or more compounds selected from an oxycarboxylic acid compound, an oxysulfonic acid compound, an aminocarboxylic acid compound, an amine compound and a carboxylic acid compound, and Sb, Bi. Sulfide, sulfate,
The annealing separator according to claim 4, wherein the total amount of one or more selected from chlorides, nitrates and acetates is 1 to 5 in terms of molar ratio.
又は２種以上を、ＭｇＯ：１００質量部に対しＢ及び／
又はＣｌとして０．００５〜０．５００質量部添加した
ことを特徴とする請求項１ないし５のいずれかに記載の
焼鈍分離剤。6. Further, one or more of water-soluble B and Cl compounds are added to B and / or 100 parts by mass of MgO.
Alternatively, 0.005 to 0.500 parts by mass of Cl is added, and the annealing separator according to any one of claims 1 to 5.
下のものが１５％以上で、且つ、水和水分２．０％以下
のＭｇＯを用いることを特徴とする特許項１ないし６の
いずれかに記載の焼鈍分離剤。7. A MgO having a physical property value of 15% or more having a particle size distribution of 1 μm or less and a hydration water content of 2.0% or less is used. An annealing separator as described in.
％、Ｓｉ：２．５０〜４．５０％含有するスラブを加熱
し、熱延し、熱延鋼板を焼鈍しもしくは焼鈍せず、１回
又は焼鈍を挟む２回の冷延により最終板厚とし、脱炭焼
鈍し、窒化焼鈍を行いもしくは行わず、焼鈍分離剤を塗
布し、仕上げ焼鈍し、絶縁被膜剤塗布と焼付けを含むヒ
ートフラットニング処理を行うことからなる方向性電磁
鋼板の製造方法において、焼鈍分離剤として請求項１な
いし７のいずれかに記載の焼鈍分離剤を用いることを特
徴とするグラス被膜と磁気特性の優れる方向性電磁鋼板
の製造方法。8. C: 0.030 to 0.100 in mass%.
%, Si: 2.50 to 4.50% contained slab is heated and hot rolled, and the hot rolled steel sheet is annealed or not annealed to obtain the final plate thickness by cold rolling once or twice with annealing. In the method for producing a grain-oriented electrical steel sheet, which comprises performing decarburization annealing, nitriding annealing or not, applying an annealing separating agent, finishing annealing, and performing a heat flattening process including insulation coating agent application and baking. A method for producing a glass coating and a grain-oriented electrical steel sheet having excellent magnetic properties, characterized by using the annealing separator according to any one of claims 1 to 7 as an annealing separator.
上における雰囲気ガス組成をＮ2：５０ｖｏｌ％以下、
雰囲気ガス酸化度ＰH2O／ＰH2を０．０２以下とするこ
とを特徴とする請求項８記載のグラス被膜と磁気特性の
優れる方向性電磁鋼板の製造方法。9. An atmosphere gas composition at a furnace temperature of 850 ° C. or higher, N 2 : 50 vol% or lower, in the temperature rising process of finish annealing,
The method for producing a grain coating and a grain-oriented electrical steel sheet having excellent magnetic properties according to claim 8, wherein the atmospheric gas oxidation degree PH 2 O / PH 2 is 0.02 or less.
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| EP2940161A4 (en) * | 2012-12-28 | 2016-01-20 | Posco | Grain-oriented electrical steel sheet, and method for manufacturing same |
| JP2021085090A (en) * | 2019-11-29 | 2021-06-03 | Ｊｆｅスチール株式会社 | Annealing separation agent for grain-oriented electromagnetic steel sheet and slurry thereof as well as a method for producing a grain-oriented electromagnetic steel sheet using slurry thereof |
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|---|---|
| JP5000054B2 (en) | 2012-08-15 |
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