JPH0941153A - Separation agent at annealing, excellent in reactivity, and production of grain oriented silicon steel sheet using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a uniform, good-quality and high tensile strength glass film and to provide a steel sheet having excellent magnetic properties by using a separation agent at annealing, prepared by mixing MgO and a specific amount of a specific solid solution type combined hydroxide, at the final finish annealing for a grain oriented silicon steel sheet. SOLUTION: A separation agent at annealing, in which a solid solution type combined hydroxide represented by the general formula M<2> 1-x M<3> x (OH)2+x-ny yA<n-> .mH2 O is mixed at a rate of 0.5-15 pts.wt. based on 100 pts.wt. of MgO, is used. In the formula, M<2+> is one or more divalent metals selected from Be, Mg, Ca, Ba, Sr, Sn, Mn, Fe, Co, Ni, Cu, and Zn, M<3+> is one or more elements selected from Al, Fe, Cr, Co, In, B, Ga, and Ti, A<n-> is an n-valent anion, such as OH<-> , F<-> , Cl<-> , Br<-> , CO3 <2-> , SO4 <2-> , SiO3 <2-> , HPO4 <2-> , CH3 COO<-> , Fe(CN)6 <3-> and HBO3 <2-> , (x) and (y) stand for 01-and 0-2, respectively, and (m) is the number of molecules of interlamellar water.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】本発明は方向性電磁鋼板の製
造に際し、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反応性の優れる焼鈍分離剤及びそれ
を用いた方向性電磁鋼板の製造方法に関する。TECHNICAL FIELD The present invention relates to forming a glass coating having a uniform and excellent coating performance in the final finishing annealing step in the production of grain-oriented electrical steel sheet, and at the same time, to improve the reactivity for obtaining excellent magnetic properties. The present invention relates to an excellent annealing separator and a method for manufacturing a grain-oriented electrical steel sheet using the same.

【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 Usually, grain-oriented electrical steel sheets have Si: 2.5-
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 as a slurry 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 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, Inhibitor A in steel is used.
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 surface of the steel sheet formed by the decarburization annealing, the annealing separator, the heat cycle in the final finishing annealing, and the atmospheric gas conditions.

【０００４】これらの中でとりわけ焼鈍分離剤に用いる
グラス被膜形成剤のＭｇＯの反応性は、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。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。Among these, the reactivity of MgO as a glass film forming agent used as an annealing separator has a great influence on the behavior of the inhibitor through the formation of the glass film. 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.

【０００５】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。[0005] The glass film forming reaction in the finish annealing is performed by using MgO as an annealing separator and SiO 2 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.

【０００６】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ず、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不純物の調整、粒
径、粒子形状、表面状態、活性度等を制御して仕上げ焼
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
ための重要なカギとなる。In the formation of this glass film, the reaction between MgO and SiO ₂ does not occur in a pure system unless the temperature is close to 1600 ° C., and the properties of the oxide film (components, formation state) and finish annealing conditions are controlled ( Heat cycle, atmosphere gas) and how to control impurities such as particle size, particle shape, surface condition and activity as properties of annealing separator, how to make uniform glass film formation from low temperature in finish annealing process. It is an important key to obtaining a good glass coating and good magnetic properties.

【０００７】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焼鈍分
離剤ＭｇＯの影響が大きいことから、焼鈍分離剤の改善
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ＭｇＣ
ｌ₂ 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。Since the influence of the annealing separating agent MgO on the glass coating and the magnetic properties which are important in determining the commercial value of the grain-oriented electrical steel sheet as described above, the improvement of the annealing separator is to improve the grain strength of the grain-oriented electrical steel sheet. It is becoming an important technical issue. MgO used for the annealing separator is generally MgC.
The l _2, or seawater as a raw material, first, Ca (OH) ₂
The Mg (OH) ₂ crystal is adjusted by the reaction with and is made into MgO once by compression washing or the like for the purpose of adjusting the purity and the like, or MgO is obtained by firing twice or more between washing and crystal adjustment, and crushed as necessary, The product is made by adjusting the particle size by classification.

【０００８】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るが、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
らの条件を最適にすることが重要である。Among the properties of MgO, the factors that influence the formation of a glass film and the stability of the inhibitor and the magnetic properties in relation to this are mainly the purity of MgO, the particle size, the activity, and the adhesion to a steel sheet. However, when applied to a steel sheet, there are a degree of progress of hydration, a dispersed state of particles in an aqueous slurry, an applied amount, and the like. Therefore, it is important to optimize these conditions in order to obtain a grain-oriented electrical steel sheet having an excellent glass coating and magnetic properties.

【０００９】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。この際、Ｍ
ｇＯ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。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。As mentioned above, MgO is usually applied to a steel sheet in the form of a slurry by suspending it in water together with a small amount of an additive to be added as a reaction accelerator, if necessary. At this time, M
Depending on the production conditions of gO, for example, in the case of high activity, depending on the mixing and stirring conditions with water, MgO → MgO (OH) ₂
As a result, a water hydration reaction occurs and the moisture is brought into the coil (between the plates), and as a result, there is a problem that the dew point between the plates is increased and the atmosphere state becomes nonuniform in the coil longitudinal direction and the width direction. For this reason, in the final annealing temperature rising process, it causes non-uniform and excessive additional oxidation, causing serious film defects such as scales, gas marks, pinholes, and discoloration.

【００１０】ところが、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５
５−７３８２３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。However, as a means for solving the problem caused by the high hydration, a method by high temperature firing is generally adopted. As this method, for example, Japanese Patent Laid-Open No.
There is a publication of 5-73823. As described above, the low activity MgO obtained by increasing the firing temperature has a drawback that the activity (reactivity) and the adhesion are reduced although the hydration property is reduced. Further, JP-A-62-156226 proposes a method of 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.

【００１１】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ＭｇＯ１００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。Further, as a technique for improving the glass coating and the magnetism by the additive in the annealing separator, Japanese Patent Publication No. 2820/1985
In the publication, one or more kinds of chlorides of Sb, Sr, Ti and Zr are added in an amount of 0.02 to 1.
A method of adding 5 parts by weight has been proposed. This allows
The additive compound brings about the enrichment and densification of the oxide layer component on the surface of the steel sheet with SiO ₂ and suppresses the additional oxidation and the effect of accelerating the reaction in the finish annealing, whereby the excellent iron loss characteristics and the glass coating film are obtained.

【００１２】又、特開平３−１２０３７６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，Ｎ
ａ，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、メタほう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, Japanese Patent Laid-Open No. 3-120376 discloses a technique for improving the chloride addition technique described above by using Mg, N.
It has been shown that by adding a metal chloride selected from a, K and Ca to MgO, the effect of improving magnetic properties can be obtained without the combined use of antimony sulfate and sodium metaborate.

【００１３】[0013]

【発明が解決しようとする課題】このように、これらの
ＭｇＯ性状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言え
ず、更なる技術改善が望まれているところである。As described above, by improving these MgO properties, the glass film forming reaction is improved and the effect is obtained. However, the coating properties and magnetic properties may become unstable depending on the steel composition, decarburization annealing conditions, and final finish annealing conditions, and this is not a sufficient technique yet, and further technical improvements are desired. .

【００１４】[0014]

【課題を解決するための手段】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研究を重ね
た。その結果、低水和ＭｇＯの反応性向上策として、低
水和ＭｇＯに固溶型複合水酸化物を配合し、更に必要に
応じて酸化物、塩化物、硫酸塩、ほう酸塩、珪酸塩等を
添加した焼鈍分離剤を適用することにより、グラス被膜
形成における反応性が良好で、均一、高張力のグラス被
膜が得られ、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。[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies in order to achieve an annealing separator having low hydration and high reactivity. As a result, as a measure for improving the reactivity of low hydrated MgO, a solid solution type composite hydroxide is blended with low hydrated MgO, and if necessary, oxides, chlorides, sulfates, borates, silicates, etc. By applying an annealing separator with added, it is possible to obtain a grain coating with excellent reactivity in forming a glass coating, a uniform and high tensile strength glass coating, and extremely good coating characteristics and magnetic characteristics. I found it.

【００１５】本発明は焼鈍分離剤で使用するＭｇＯ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。 （１）ＭｇＯ１００重量部に対し、Ｍ²⁺ _1-x Ｍ³⁺ _x （Ｏ
Ｈ）_2+x-nyｙＡ^n-・ｍＨ₂ Ｏの一般式で表される固溶型
複合水酸化物を０．５〜１５重量部の割合で配合した反
応性の優れる方向性電磁鋼板用焼鈍分離剤。但し、 Ｍ²⁺；Ｂｅ，Ｍｇ，Ｃａ，Ｂａ，Ｓｒ，Ｓｎ，Ｍｎ，Ｆ
ｅ，Ｃｏ，Ｎｉ，Ｃｕ，Ｚｎの中から選ばれる２価金属
の１種又は２種以上 Ｍ³⁺；Ａｌ，Ｆｅ，Ｃｒ，Ｃｏ，Ｉｎ，Ｂ，Ｇａ，Ｔｉ
の中から選ばれる３価金属の１種又は２種以上 Ａ^n-；ＯＨ^- ，Ｆ^- ，Ｃｌ^- ，Ｂｒ^- ，ＣＯ₃ ^2-，ＳＯ
₄ ^2-，ＳｉＯ₃ ^2-，ＨＰＯ₄ ^2-，ＣＨ₃ ＣＯＯ^- ，Ｆｅ
（ＣＮ）₆ ^3-，ＨＢＯ₃ ^2-等のｎ価のアニオン ０≦ｘ≦１．０， ０≦ｙ＜２．０， ｍ；層間水の分
子数The present invention has the following features as a solution in the prior art of MgO used as an annealing separator. (1) M ²⁺ _1-x M ³⁺ _x (O
_{H) 2 + x-ny yA} n- · mH 2 O for grain-oriented electrical steel sheet having excellent reactivity solute type complex hydroxide represented by the general formula was added in an amount of 0.5 to 15 parts by weight of Annealing agent. However, M ²⁺ ; Be, Mg, Ca, Ba, Sr, Sn, Mn, F
One or more divalent metal selected from e, Co, Ni, Cu and Zn M ³⁺ ; Al, Fe, Cr, Co, In, B, Ga, Ti
One trivalent metal selected from among two or more ^{A n-; OH -, F -} , Cl -, Br -, CO 3 2-, SO
₄ ²⁻ , SiO ₃ ²⁻ , HPO ₄ ²⁻ , CH ₃ COO ⁻ , Fe
(CN) ₆ ³⁻ , HBO ₃ ^{2−, and} other n-valent anions 0 ≦ x ≦ 1.0, 0 ≦ y <2.0, m; number of molecules of interlayer water

【００１６】（２）ＭｇＯ１００重量部に対し、Ｍ²⁺
_1-x Ｍ³⁺ _x （ＯＨ）_2+x-nyｙＡ^n-・ｍＨ₂ Ｏの一般式で
表される固溶型複合水酸化物を０．５〜１５重量部と添
加剤として、酸化物、塩化物、硫酸塩、ほう酸塩、珪酸
塩の中から選ばれる１種又は２種以上を０．０５〜１０
重量部の割合で配合した反応性の優れる方向性電磁鋼板
用焼鈍分離剤。(2) M ²⁺ based on 100 parts by weight of MgO
_1-x M ³⁺ _x (OH) _{2 + x-ny} yA ^n- · mH ₂ O 0.5 to 15 parts by weight of a solid solution type composite hydroxide represented by the general formula and oxidation are performed as an additive. One or two or more selected from compounds, chlorides, sulphates, borates, and silicates in an amount of 0.05 to 10
An annealing separator for grain-oriented electrical steel sheets with excellent reactivity, which is blended in a ratio of parts by weight.

【００１７】（３）Ｓｉ：２．５〜４．０％を含有する
方向性電磁鋼板素材を公知の方法で処理し、最終板厚の
冷延板とし、脱炭焼鈍してＳｉＯ₂ 主成分の酸化被膜を
形成し、焼鈍分離剤を塗布し、最終仕上げ焼鈍を行った
後、絶縁被膜剤を塗布してヒートフラットニングを行う
ことからなる方向性電磁鋼板の製造方法において、前記
焼鈍分離剤の塗布工程で、ＭｇＯ１００重量部に対し、
Ｍ²⁺ _1-x Ｍ³⁺ _x （ＯＨ）_2+x-nyｙＡ^n-・ｍＨ₂ Ｏの一般
式で表される固溶型複合水酸化物を０．５〜１５重量部
の割合で添加したスラリーを鋼板に塗布するグラス被膜
形成反応の優れる方向性電磁鋼板の製造方法。(3) A grain-oriented electrical steel sheet material containing Si: 2.5 to 4.0% is treated by a known method to obtain a cold-rolled sheet having a final thickness, decarburization-annealed, and a SiO ₂ main component. In the method for producing a grain-oriented electrical steel sheet, which comprises forming an oxide film, applying an annealing separator, performing final finishing annealing, and then performing heat flattening by applying an insulating film agent, the annealing separator. In the coating process of 100 parts by weight of MgO,
At a ratio of ^{_{M 2+ 1-x M 3+ x}} (OH) 2 + x-ny yA n- · mH 0.5~15 parts by weight of solid solution type complex hydroxide represented by the general formula ₂ O A method for producing a grain-oriented electrical steel sheet having an excellent glass film forming reaction, which comprises applying the added slurry to a steel sheet.

【００１８】（４）Ｓｉ：２．５〜４．０％を含有する
方向性電磁鋼板素材を公知の方法で処理し、最終板厚の
冷延板とし、脱炭焼鈍してＳｉＯ₂ 主成分の酸化被膜を
形成し、焼鈍分離剤を塗布し、最終仕上げ焼鈍を行った
後、絶縁被膜剤を塗布してヒートフラットニングを行う
ことからなる、方向性電磁鋼板の製造方法において、前
記焼鈍分離剤の塗布工程において、ＭｇＯ１００重量部
に対し、Ｍ²⁺ _1-x Ｍ³⁺ _x （ＯＨ）_2+x-nyｙＡ^n-・ｍＨ₂
Ｏの一般式で表される固溶型複合水酸化物を０．５〜１
５重量部と添加剤として酸化物、塩化物、硫酸塩、ほう
酸塩、珪酸塩の中から選ばれる１種又は２種以上を０．
０５〜１０重量部の割合で配合したスラリーを鋼板に塗
布するグラス被膜形成反応の優れる方向性電磁鋼板の製
造方法。(4) A grain-oriented electrical steel sheet material containing Si: 2.5 to 4.0% is treated by a known method to obtain a cold-rolled sheet having a final thickness, and decarburized and annealed to obtain a SiO ₂ main component. In the method for producing a grain-oriented electrical steel sheet, which comprises forming an oxide film, applying an annealing separator, performing final finishing annealing, then applying an insulating film agent and performing heat flattening, the annealing separation in the coating step of the agent, relative MgO100 ^{_{parts, M 2+ 1-x M 3+}} x (OH) 2 + x-ny yA n- · mH 2
The solid solution type composite hydroxide represented by the general formula of O is 0.5 to 1
5 parts by weight and one or more kinds selected from oxides, chlorides, sulfates, borates, and silicates as an additive are added.
A method for producing a grain-oriented electrical steel sheet excellent in a glass film forming reaction, which comprises applying a slurry compounded in a proportion of 05 to 10 parts by weight to a steel sheet.

【００１９】（５）焼鈍分離剤の主成分に使用するＭｇ
Ｏの水和水分が３％以下である（３）〜（４）のいずれ
かに記載のグラス被膜形成反応の優れる方向性電磁鋼板
の製造方法。 （６）最終仕上げ焼鈍における昇温速度が昇温時７００
〜１１５０℃の間を平均１５℃／Hr以下とする（３）〜
（４）のいずれかに記載のグラス皮膜形成反応の優れる
方向性電磁鋼板の製造方法。(5) Mg used as the main component of the annealing separator
The method for producing a grain-oriented electrical steel sheet according to any one of (3) to (4), wherein the hydrated water content of O is 3% or less. (6) The temperature rising rate in the final finish annealing is 700 during heating.
-1150 ° C is set to an average of 15 ° C / Hr or less (3)-
The method for producing a grain-oriented electrical steel sheet having an excellent glass film forming reaction according to any one of (4).

【００２０】これにより、従来技術では実現できなかっ
たＭｇＯ表面水和層による反応性向上や、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、広範囲の
仕上げ焼鈍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を
得ることに成功した。As a result, we have succeeded in improving the reactivity due to the MgO surface hydrated layer, which could not be realized by the prior art, and in the development of a technology that surpasses the conventional chloride addition technology. In other words, we succeeded in obtaining a grain-oriented electrical steel sheet in which the glass coating is uniform under a wide range of finish annealing conditions and the magnetic characteristics are good over the entire surface and the entire length of the coil.

【００２１】本発明の適用にあたっては、出発材として
はＳｉ：２．５〜４．０％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表面にＳｉ
Ｏ₂ を主成分とする酸化膜を形成したいわゆる脱炭焼鈍
板が用いられる。この鋼板に、前記のように、ＭｇＯに
固溶型の複合水酸化物を配合した焼鈍分離剤スラリーを
均一に微細分散した後、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。In applying the present invention, as a starting material, a silicon steel slab containing Si: 2.5 to 4.0% is hot-rolled by a known method and cold-rolled once or twice or more with annealing interposed. To the final thickness and then decarburization annealing to remove Si on the surface.
A so-called decarburized annealed plate having an oxide film containing O ₂ as a main component is used. As described above, an annealing separator slurry in which MgO is mixed with a solid solution type composite hydroxide is uniformly finely dispersed in this steel sheet, and then applied to the steel sheet surface with a coating roll or the like in a continuous line to obtain 150 to 400 It is dried at a temperature of about ℃ (plate temperature) and wound on a coil.

【００２２】この際、焼鈍分離剤には、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、酸化物、塩化物、硫酸塩、ほう酸、珪酸
塩等が鋼成分や処理条件に応じて添加配合される。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 is a steel component such as an oxide, chloride, sulfate, boric acid, or silicate as a reaction accelerating aid for forming a glass film, a plate dew point adjusting agent, and an inhibitor strengthening assisting agent. And added according to the treatment conditions. The coil thus treated is subjected to final finishing annealing in a batch type or continuous type furnace at 1150 to 1200 ° C.
The treatment is performed at a high temperature of × 20 Hr for a long time, and the glass film formation, the secondary recrystallization and the purification are simultaneously performed.

【００２３】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 grain-oriented electrical steel sheet, the formation timing, the formation amount, the formation state, etc. of the glass coating at this time affect the decomposition rate of the inhibitors AlN, MnS, etc., and the quality, tension or purification reaction of the glass coating. As a result of
It affects the glass coating properties and magnetic properties of the product.

【００２４】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、歪取り焼鈍をかねてヒートフ
ラットニングが行われ、最終製品とされる。この際、方
向性電磁鋼板は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は張力付与型のものが適用
される。The coil thus treated with the glass coating film is washed with water to remove the excess annealing separator in a continuous line, lightly pickled, and then coated with an insulating coating agent.
The final product is subjected to heat flattening while also performing the baking, shape correction, and strain relief annealing. At this time, grain-oriented electrical steel sheets have a large effect of improving iron loss due to coating tension, magnetostriction, etc., especially in high magnetic flux density materials, so in order to further reinforce the tension effect of the glass coating formed by finish annealing, insulating coating component A tensioning type is applied as the above.

【００２５】この張力被膜剤としては、例えば、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。この後、更に鉄損を改善しようとする場合には絶縁
被膜剤処理前後において、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。Examples of the tension coating agent include Al, Mg, and 100 parts by weight of solid colloidal silica.
130 to 200 parts by weight of one or more phosphates such as Ca and 12 to 40 parts by weight of one or more of chromic acid, chromate and dichromate as CrO ₃ are blended. It is suitable to economically obtain a high-strength coating. After this, when further improving the iron loss, before and after the treatment with the insulating coating agent, the intervals and depths should be linear or dotted in the direction substantially perpendicular to the rolling direction by laser, tooth roll, etching, local plating, etc. Control, distortion, flaws,
A magnetic layer subdivision process is performed by treating the plated layer and the like.

【００２６】次に本発明の限定理由を述べる。本発明の
焼鈍分離剤の組成としては、ＭｇＯ１００重量部に対
し、Ｍ²⁺ _1-x Ｍ³⁺ _x （ＯＨ）_2+x-nyｙＡ^n-・ｍＨ₂ Ｏの
一般式で表される２元素以上で構成される固溶型複合水
酸化物を０．５〜１５重量部の割合で配合した焼鈍分離
剤である。Next, the reasons for limitation of the present invention will be described. 2 The composition of annealing separator of the present invention, with respect to MgO100 parts, represented by the general formula _{^{M 2+ 1-x M 3+ x}} (OH) 2 + x-ny yA n- · mH 2 O It is an annealing separator containing 0.5 to 15 parts by weight of a solid solution composite hydroxide composed of elements or more.

【００２７】このような物質としては、：３価の水酸
化物に２価の水酸化物を固溶したものの、：２価の水
酸化物に３価の水酸化物を固溶したもの、：２価の水
酸化物に２価の水酸化物を固溶したもの、：或いはこ
れらの２種以上が用いられる。Examples of such substances include: a solution of divalent hydroxide in solid solution in trivalent hydroxide, but a solution of trivalent hydroxide in divalent hydroxide in solid solution, : Divalent hydroxide in solid solution with divalent hydroxide, or: Two or more kinds of these are used.

【００２８】これらの複合水酸化物の配合により、焼鈍
分離剤主成分ＭｇＯと鋼板表面はこれら複合水酸化物の
微粒子により覆われ、固溶型複合水酸化物はそれ自体が
低融点であること、更に、ＭｇＯ粒子の鋼板への接触面
積と接着力を高める。これらにより、グラス被膜の結晶
化温度の低下と結晶化反応促進をもたらし、優れたグラ
ス被膜形成反応を生じる。By mixing these composite hydroxides, the annealing separator main component MgO and the surface of the steel sheet are covered with fine particles of these composite hydroxides, and the solid solution type composite hydroxide itself has a low melting point. Further, the contact area of the MgO particles with the steel sheet and the adhesive force are increased. Due to these, the crystallization temperature of the glass film is lowered and the crystallization reaction is promoted, and an excellent glass film forming reaction occurs.

【００２９】ベースＭｇＯは特に限定するものではない
が、水酸化物、炭酸塩、塩基性炭酸塩等のＭｇＯ原料を
出発剤として、７００〜１２００℃程度の温度で焼成し
て得られるものが、均一な被膜形成反応を得る上で好ま
しい。配合される固溶型複合酸化物としては、ベースＭ
ｇＯ１００重量部に対し、０．５〜１５重量部の範囲で
鋼成分、脱炭焼鈍、仕上げ焼鈍条件等に応じて適量配合
される。固溶型複合水酸化物添加量は０．５重量部未満
ではグラス被膜の形成反応の改善効果が弱く、被膜性能
向上と被膜張力の向上効果が得られない。このため、磁
気特性の改善効果も得られない。The base MgO is not particularly limited, but those obtained by firing MgO starting materials such as hydroxides, carbonates and basic carbonates at a temperature of about 700 to 1200 ° C. It is preferable for obtaining a uniform film-forming reaction. As a solid solution type composite oxide to be blended, base M
An appropriate amount is blended within a range of 0.5 to 15 parts by weight with respect to 100 parts by weight of gO according to the steel composition, decarburization annealing, finish annealing conditions and the like. If the amount of the solid solution type composite hydroxide added is less than 0.5 part by weight, the effect of improving the reaction of forming the glass film is weak, and the effect of improving the film performance and the film tension cannot be obtained. Therefore, the effect of improving the magnetic characteristics cannot be obtained.

【００３０】一方、１５重量部超では、シモフリと呼ば
れる金属斑点状やスケール等の酸化過度時に見られる欠
陥が生じるため制限される。０．５〜１０重量部の範囲
では固溶型複合水酸化物によるＭｇＯ表面の被覆、鋼板
面への密着力向上や複合水酸化物の複合固溶化による単
体酸化物や単体水酸化物物質では得られなかったような
低融点化効果が得られる。On the other hand, if the amount exceeds 15 parts by weight, defects such as metal spots called scales and scales that are seen during excessive oxidation occur, so that the amount is limited. In the range of 0.5 to 10 parts by weight, in the case of a single oxide or a single hydroxide substance by coating the MgO surface with a solid solution type composite hydroxide, improving the adhesion to the steel plate surface, or forming a complex solution of the composite hydroxide. The effect of lowering the melting point, which has not been obtained, is obtained.

【００３１】固溶型複合水酸化物の形態はＭ²⁺ _1-x Ｍ³⁺
_x （ＯＨ）_2+x-nyｙＡ^n-・ｍＨ₂ Ｏの一般式で表される
２元素以上で構成された固溶型複合体であれば特に限定
するものではない。この場合、：３価水酸化物への２
価水酸化物の固溶体、：２価水酸化物への２価水酸化
物の固溶体、：３価水酸化物への３価水酸化物を固溶
体の１種又は２種以上が用いられる。これら３つのケー
スではいずれも良好なグラス被膜の改善と磁気特性の向
上効果が得られる。The form of the solid solution type composite hydroxide is M ²⁺ _1-x M ³⁺
_{x (OH) 2 + x-} ny yA n- · mH is not particularly limited as long as it is a solid solution-type complexes composed of two or more elements represented by the general formula ₂ O. In this case: 2 to trivalent hydroxide
One or more solid solutions of divalent hydroxides: solid solutions of divalent hydroxides in divalent hydroxides: solid solutions of trivalent hydroxides in trivalent hydroxides are used. In all of these three cases, good improvement of the glass coating and improvement of the magnetic properties can be obtained.

【００３２】Ａ^n-で表わされるアニオン基はＯＨ^- ，Ｆ
^- ，Ｃｌ^- ，Ｂｒ^- ，ＣＯ₃ ^2-，ＳＯ₄ ^2-，Ｓｉ
Ｏ₃ ^2-，ＨＰＯ₄ ^2-，ＣｒＯ₄ ^2-，ＣＨ₃ ＣＯＯ^- ，Ｆ
ｅ（ＣＮ）₆ ^3-，ＨＢＯ₃ ^2-等のものが選ばれる。これ
らは、前記固溶型複合水酸化物による固溶複合による低
融点化効果を補助する形で、ＭｇＯ粒子間の充填作用に
よる反応表面積増加、ＭｇＯの密着性向上により、グラ
ス被膜形成反応を向上させる働きをもたらす。The anion group represented by A ^n- is OH ^-, F
^{-, Cl -, Br -,} CO 3 2-, SO 4 2-, Si
O ₃ ²⁻ , HPO ₄ ²⁻ , CrO ₄ ²⁻ , CH ₃ COO ⁻ , F
e (CN) ₆ ³⁻ , HBO ₃ ^2−, etc. are selected. These improve the glass surface forming reaction by increasing the reaction surface area due to the filling action between MgO particles and improving the adhesion of MgO in a form that assists the effect of lowering the melting point by the solid solution complexing with the solid solution type complex hydroxide. Bring the work to be done.

【００３３】しかし、これらのアニオン基が多すぎる場
合には、仕上げ焼鈍における酸化膜や形成過程のグラス
被膜の腐食や酸化反応を生じ、グラス被膜の質を低下し
たり、被膜厚みを極端に厚くする。その結果、磁気特性
を劣化させる場合があるので、その適量制御は重要であ
る。好ましくは、０＜ｙ＜０．５の場合が安定して良好
なグラス被膜特性が得られる。However, when the amount of these anionic groups is too large, the oxide film in the finish annealing or the glass film in the forming process is corroded or oxidized to deteriorate the quality of the glass film or increase the film thickness extremely. To do. As a result, the magnetic properties may be deteriorated, so that the appropriate amount control is important. Preferably, when 0 <y <0.5, stable and good glass film characteristics can be obtained.

【００３４】本発明の固溶型複合水酸化物の適用におい
ては、好ましい条件としてベースＭｇＯの水和水分が制
限される。水和水分の好ましい範囲は３％未満である。
３％超では、複合水酸化物から仕上げ焼鈍昇温過程で放
出される水分の影響で鋼板間が酸化性になり、コイルエ
ッジにシモフリ、スケール等の被膜欠陥が生じたり、素
材成分によっては磁気特性を劣化させる場合がある。In the application of the solid solution type composite hydroxide of the present invention, the hydrated water content of the base MgO is limited as a preferable condition. The preferred range of hydration water content is less than 3%.
If the content exceeds 3%, the moisture released from the composite hydroxide during the final annealing temperature rise will cause oxidation between the steel sheets, resulting in film defects such as shimofuri and scale at the coil edge, and depending on the material composition, it may be magnetic. It may deteriorate the characteristics.

【００３５】焼鈍分離剤中にグラス被膜形成反応促進補
助剤として添加される酸化物、塩化物、硫酸塩、ほう酸
塩、珪酸塩等はＭｇＯ１００重量部に対し０．０５〜１
０重量部である。これらの添加剤は、前記、固溶型複合
水酸化物中のアニオン物質と類似の反応性向上効果を生
じる。０．０５重量部未満では十分な反応性向上効果が
得られない。一方、１０重量部以上の添加では、アニオ
ン物質が多い場合と同様に酸化過度状の被膜欠陥が生
じ、磁気特性をも劣化させる場合があるので制限され
る。Oxides, chlorides, sulfates, borates, silicates and the like added to the annealing separator as a glass film forming reaction accelerating aid are contained in an amount of 0.05 to 1 with respect to 100 parts by weight of MgO.
0 parts by weight. These additives produce a reactivity improving effect similar to the anionic substance in the solid solution type composite hydroxide. If it is less than 0.05 part by weight, a sufficient effect of improving reactivity cannot be obtained. On the other hand, the addition of 10 parts by weight or more is limited because excessive oxidative coating defects may occur and magnetic properties may be deteriorated as in the case where the amount of anionic substances is large.

【００３６】次に、本発明の焼鈍分離剤適用における仕
上げ焼鈍雰囲気としては、昇温時７００〜１１５０℃の
温度域を平均昇温速度１５℃／Hr未満として焼鈍するの
が好ましい。本発明の焼鈍分離剤のＭｇＯと複合水酸化
物は構造水として、吸着水、水和水、層間水等を有す
る。これらは、鋼板酸化膜上に塗布されると単純に水和
水分の分解温度とされる４００℃前後の温度では分解放
出が終了せず、仕上げ焼鈍昇温時に１００〜９００℃の
温度範囲でこれらを徐々に分散放出する。特に、鋼板酸
化の生じる７００℃以上の水分量の制御が重要であり、
７００〜１１５０℃のグラス被膜形成の行われる温度域
を徐々に加熱することによって前述の焼鈍分離剤から放
出される水分による鋼板の過酸化を抑える。Next, as the finish annealing atmosphere in the application of the annealing separating agent of the present invention, it is preferable to anneal in a temperature range of 700 to 1150 ° C. at the time of heating at an average heating rate of less than 15 ° C./hr. MgO and the composite hydroxide of the annealing separator of the present invention have adsorbed water, hydration water, interlayer water, etc. as structural water. When these are applied on the steel sheet oxide film, decomposition and release do not end at a temperature around 400 ° C., which is simply the decomposition temperature of hydrated water, and these are not exceeded in the temperature range of 100 to 900 ° C. during finish annealing temperature rise. Is gradually dispersed and released. In particular, it is important to control the amount of water above 700 ° C at which steel sheet oxidation occurs.
By gradually heating the temperature range where the glass film is formed at 700 to 1150 ° C., the peroxidation of the steel sheet due to the water released from the annealing separator is suppressed.

【００３７】加熱速度は１５℃／Hr未満であれば鋼板間
のドライ化が進み、複合水酸化物の効果と相俟って均一
で、高張力のグラス被膜が形成できる。１５℃／Hr超の
昇温では、複合水酸化物による効果でグラス被膜、磁気
特性の向上効果が得られるものの、前記、徐加熱方式と
比較してやや被膜欠陥が発生しやすい傾向が見られる。When the heating rate is less than 15 ° C./Hr, the steel sheet is dried more, and combined with the effect of the composite hydroxide, a uniform and high-strength glass film can be formed. When the temperature is raised above 15 ° C./Hr, the effect of the composite hydroxide improves the glass coating and magnetic properties, but the coating defects tend to occur more easily than the slow heating method.

【００３８】本発明は、焼鈍分離剤として、ＭｇＯに固
溶型複合水酸化物を添加することにより、固溶複合水酸
化物自体の低融点化効果と焼鈍分離剤の鋼板への接触・
密着性を高め、仕上げ焼鈍におけるグラス被膜形成反応
を安定して、均一に形成させる。これにより鋼板表面被
膜の追加酸化や還元が抑制され、インヒビターの安定化
効果が得られる。この結果、グラス被膜特性と磁気特性
の改善効果が得られるものと考えられる。In the present invention, by adding a solid solution type composite hydroxide to MgO as an annealing separator, the melting point lowering effect of the solid solution composite hydroxide itself and the contact of the annealing separator with the steel sheet
Improves adhesion and stabilizes and uniformly forms the glass film formation reaction during finish annealing. As a result, additional oxidation and reduction of the steel sheet surface coating are suppressed, and the inhibitor stabilizing effect is obtained. As a result, it is considered that the effect of improving the glass coating characteristics and the magnetic characteristics can be obtained.

【００３９】[0039]

【実施例】【Example】

〔実施例１〕重量％でＣ：０．０７５％、Ｓｉ：３．２
５％、Ｍｎ：０．０６５％、Ｓ：０．０２５％、Ａｌ：
０．０２８％、Ｎ：０．００７８％、Ｃｕ：０．０７
％、Ｓｎ：０．０８％、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０．０２２５mmとし
た。その後、Ｎ₂ ２５％＋Ｈ₂ ７５％、露点６７℃のウ
エット雰囲気中で脱炭焼鈍を行った。[Example 1] C: 0.075% by weight, Si: 3.2
5%, Mn: 0.065%, S: 0.025%, Al:
0.028%, N: 0.0078%, Cu: 0.07
%, Sn: 0.08%, the balance being a high magnetic flux density grain-oriented electrical steel sheet material consisting of iron and inevitable impurities, hot rolled, annealed and cold rolled by known methods to give a final sheet thickness of 0.0225 mm. Then, decarburization annealing was performed in a wet atmosphere of N ₂ 25% + H ₂ 75% and a dew point of 67 ° C.

【００４０】次いで、表１に示すように水和水分２．８
％のＭｇＯ１００重量部に固溶型複合水酸化物を配合
し、グラス被膜形成促進剤としてＴｉＯ₂ ５重量部とＮ
ａ₂ Ｂ₄ Ｏ₇ ０．３重量部添加した焼鈍分離剤スラリー
を鋼板に塗布し、乾燥してコイルとして巻き取った。Then, as shown in Table 1, the hydrated water content is 2.8.
% MgO 100 parts by weight with a solid solution type composite hydroxide, and 5 parts by weight of TiO ₂ and N as a glass film formation promoter are added.
The annealing separating agent slurry added with 0.3 part by weight of a ₂ B ₄ O ₇ was applied to a steel sheet, dried and wound into a coil.

【００４１】次いで、１２００℃×２０Hrの仕上げ焼鈍
を行った。この後、絶縁被膜剤として、３０％コロイダ
ルシリカ７０ml、５０％燐酸アルミニウム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／ｍ
² 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。Then, finish annealing at 1200 ° C. × 20 Hr was performed. After that, as an insulating coating agent, a coating agent consisting of 70 ml of 30% colloidal silica and 50 ml of 50% aluminum phosphate was dried and baked at a weight of 5 g / m 2.
^It was applied so as to be ^2, and heat flattened 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.

【００４２】[0042]

【表１】 [Table 1]

【００４３】[0043]

【表２】 [Table 2]

【００４４】この結果、本発明のように焼鈍分離剤に固
溶型複合水酸化物を添加したものは、いずれも均一で光
沢のあるグラス被膜を形成し、被膜張力、密着性のいず
れも良好であった。又、磁気特性も比較例に比し、かな
り良好で、特に複合水酸化物５重量部の場合は磁束密
度、鉄損値とも極めて良好な結果が得られた。As a result, as in the case of the present invention, in which the solid solution type composite hydroxide was added to the annealing separator, all formed a uniform and glossy glass film, and both the film tension and the adhesion were good. Met. The magnetic properties were also considerably better than those of the comparative example, and particularly in the case of 5 parts by weight of the composite hydroxide, extremely good results were obtained in both the magnetic flux density and the iron loss value.

【００４５】〔実施例２〕重量％でＣ：０．０５７％、
Ｓｉ：３．３０％、Ｍｎ：０．１０％、Ａｌ：０．０３
０％、Ｓ：０．００７５％、Ｎ：０．００７８％、Ｓ
ｎ：０．０５％、残留を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０．２３
mmとした。Example 2 C: 0.057% by weight,
Si: 3.30%, Mn: 0.10%, Al: 0.03
0%, S: 0.0075%, N: 0.0078%, S
n: 0.05%, the grain-oriented electrical steel sheet slab consisting of residual Fe and unavoidable impurities is heated at a low temperature of 1150 ° C. by a known method, then hot rolled, and finally sheet thickness 0.23 by annealing and cold rolling.
mm.

【００４６】このコイルを連続焼鈍ラインにおいてＮ₂
２５％＋Ｈ₂ ７５％、露点６５℃のウエット雰囲気中で
８３０℃×１１０秒間の脱炭焼鈍し、引き続き鋼中Ｎ量
が２００ppm となるようにＮ₂ ２５％＋Ｈ₂ ７５％＋Ｎ
Ｈ₃ のドライ雰囲気中で７５０℃×３０秒間の窒化処理
を行った。This coil was subjected to N _{2 in a} continuous annealing line.
25% + H ₂ 75%, decarburization annealing at 830 ° C. × 110 seconds in a wet atmosphere with a dew point of 65 ° C., and then N ₂ 25% + H ₂ 75% + N so that the N content in the steel becomes 200 ppm.
Nitriding treatment was performed at 750 ° C. for 30 seconds in a dry atmosphere of H ₃ .

【００４７】この鋼板に表３に示すように、水和水分
１．５％のＭｇＯに固溶型複合水酸化物と反応促進剤と
してＴｉＯ₂ ５重量部、ＦｅＣｌ₂ ・４Ｈ₂ Ｏ０．１重
量部を配合した焼鈍分離剤を塗布し、乾燥後コイルに巻
き取った。次いで実施例１と同様に仕上げ焼鈍と絶縁被
膜処理を行って最終製品とした。この試験における製品
のグラス被膜と磁気特性の結果を表４に示す。As shown in Table 3 in this steel sheet, 5 parts by weight of TiO ₂ as a solid solution type composite hydroxide in MgO having a hydration water content of 1.5%, a reaction accelerator, and 0.1 parts by weight of FeCl ₂ .4H ₂ O. Then, an annealing separator containing 1 part was applied, dried and wound on a coil. Then, in the same manner as in Example 1, finish annealing and insulation coating treatment were performed to obtain a final product. The results of the glass coating and magnetic properties of the products in this test are shown in Table 4.

【００４８】[0048]

【表３】 [Table 3]

【００４９】[0049]

【表４】 [Table 4]

【００５０】この試験の結果、本発明の固溶型複合水酸
化物を２．５〜７．５重量部添加したものはグラス被膜
が均一で優れ、被膜張力が高く、絶縁被膜処理後の密着
性も良好であった。又、磁気特性も被膜の良好条件では
極めて優れた結果が得られた。一方、比較例の複合水酸
化物の配合量の多い場合には、グラス被膜に酸化過度特
有のスケール、シモフリ状の欠陥が多く、被膜の密着
性、磁気特性等も劣化する傾向が見られた。又、複合水
酸化物を添加しない比較例では、ややグラス被膜が薄
く、光沢が鈍い外観を呈しており、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, 2.5 to 7.5 parts by weight of the solid solution composite hydroxide of the present invention was added, and the glass coating was uniform and excellent, the coating tension was high, and the adhesion after the insulating coating treatment was high. The property was also good. In addition, the magnetic properties were also extremely excellent under the favorable conditions of the coating. On the other hand, when the compounded amount of the composite hydroxide of Comparative Example was large, there were many scales peculiar to excessive oxidation in the glass film, and there were many defects like shimofuri, and the adhesion and magnetic properties of the film tended to deteriorate. . In addition, in the comparative example in which the composite hydroxide was not added, the glass film had a slightly thin appearance and the appearance was dull, and the magnetic properties were considerably inferior to those of the present invention.

【００５１】〔実施例３〕重量％でＣ：０．０５０％、
Ｓｉ：３．２８％、Ｍｎ：０．１１％、Ａｌ：０．０２
７％、Ｓ：０．００７３％、Ｎ：０．００７８％、Ｓ
ｎ：０．０６％、残部をＦｅと不可避の不純物からなる
方向性電磁鋼スラブを公知の方法で１１５０℃の低温で
加熱し、熱延後、焼鈍と冷延により最終板厚０．２２５
mmとした。このコイルを連続焼鈍ラインにおいてＮ₂ ２
５％＋Ｈ₂ ７５％、露点６５℃で８３０℃×１１０秒間
の脱炭焼鈍し、引き続きＮ₂ ２５％＋Ｈ₂ ７５％＋ＮＨ
₃ のドライ雰囲気中で７５０℃×３０秒間、鋼中Ｎ量が
１８０ppm になるように窒化処理を行った。[Example 3] C: 0.050% by weight,
Si: 3.28%, Mn: 0.11%, Al: 0.02
7%, S: 0.0073%, N: 0.0078%, S
n: 0.06%, the remainder is a grain-oriented electrical steel slab consisting of Fe and unavoidable impurities, which is heated at a low temperature of 1150 ° C. by a known method, hot-rolled, and then annealed and cold-rolled to give a final sheet thickness of 0.225.
mm. This coil was N ₂ 2 in a continuous annealing line.
5% + H ₂ 75%, decarburization annealing at dew point 65 ° C. for 830 ° C. × 110 seconds, then N ₂ 25% + H ₂ 75% + NH
_In the dry atmosphere of No. ₃ , nitriding treatment was performed at 750 ° C. for 30 seconds so that the N content in steel was 180 ppm.

【００５２】この鋼板に表５に示すように水和水分２．
５％のＭｇＯ１００重量部に固溶型複合水酸化物を配合
し、反応補助剤としてＴｉＯ₂ ５重量部とＳｂ₂ （ＳＯ
₄ ）₃ ０．１重量部からなる焼鈍分離剤を塗布し、乾燥
後コイルに巻き取った。次いで、図１（ａ），（ｂ）に
示すような昇温速度を変更した条件で仕上げ焼鈍を行っ
た後、実施例１と同様の絶縁被膜処理を行って最終製品
とした。この試験におけるグラス被膜と磁気特性の結果
を表６に示す。As shown in Table 5, the hydrated water content of 2.
5% by weight of MgO was mixed with 100 parts by weight of solid solution type composite hydroxide, and 5 parts by weight of TiO ₂ and Sb ₂ (SO
₄ ) ₃ 0.1 part by weight of an annealing separator was applied, dried and wound on a coil. Next, after finishing annealing was performed under the condition that the temperature rising rate was changed as shown in FIGS. 1A and 1B, the same insulating film treatment as in Example 1 was performed to obtain a final product. The results of the glass coating and magnetic properties in this test are shown in Table 6.

【００５３】[0053]

【表５】 [Table 5]

【００５４】[0054]

【表６】 [Table 6]

【００５５】この試験の結果、本発明の焼鈍分離剤に固
溶型複合水酸化物を添加し、仕上げ焼鈍の昇温を１０℃
／Hrとしたサイクル（Ｂ）の場合には光沢のあるグラス
被膜が均一に厚く形成し、被膜特性と磁気特性が非常に
良好であった。一方、同一の焼鈍分離剤を用いても仕上
げ焼鈍を昇温速度１５℃／Hrのサイクル（Ａ）によるも
のは被膜特性、磁気特性とも（Ｂ）サイクルにより焼鈍
したものに比し劣る結果となった。又、焼鈍分離剤が通
常のＭｇＯの場合には仕上げ焼鈍条件がいずれの場合に
も、グラス被膜、磁気特性共に本発明材に比しかなり劣
る結果であった。As a result of this test, solid solution type composite hydroxide was added to the annealing separator of the present invention, and the temperature of finish annealing was raised to 10 ° C.
In the case of the cycle (B) in which / Hr was set, a glossy glass film was formed uniformly thick and the film properties and magnetic properties were very good. On the other hand, even if the same annealing separator is used, the finish annealing by the cycle (A) with the temperature rising rate of 15 ° C./Hr is inferior to the one annealed by the cycle (B) in both the coating property and the magnetic property. It was Further, when the annealing separator was ordinary MgO, the glass coating and magnetic properties were considerably inferior to those of the material of the present invention under any of the finish annealing conditions.

【００５６】[0056]

【発明の効果】本発明によれば、従来のＭｇＯを主体に
する焼鈍分離剤を使用する場合に比較して、均一で、良
質の高張力のグラス被膜が形成され、良好な磁気特性が
得られる。According to the present invention, as compared with the case of using a conventional annealing separator mainly composed of MgO, a uniform and high-quality high-tensile-strength glass film is formed and good magnetic characteristics are obtained. To be

【図面の簡単な説明】[Brief description of drawings]

【図１】（ａ），（ｂ）は仕上げ焼鈍の加熱と雰囲気ガ
スを示す図表である。FIG. 1A and FIG. 1B are tables showing heating and atmospheric gas in finish annealing.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 北河 久和 北九州市戸畑区飛幡町１番１号 新日本製 鐵株式会社八幡製鐵所内 (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 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hisawa Kitagawa No. 1 Tobahata-cho, Tobata-ku, Kitakyushu City Shin-Nippon Steel Yawata Works (72) Inventor Tanaka Osamu Nakahara, Tobata-ku, Kitakyushu 46- 59 Nittetsu Plant Design Co., Ltd.

Claims (6)

【特許請求の範囲】[Claims] 【請求項１】 ＭｇＯ１００重量部に対し、Ｍ²⁺ _1-x Ｍ
³⁺ _x （ＯＨ）_2+x-nyｙＡ^n-・ｍＨ₂ Ｏの一般式で表され
る固溶型複合水酸化物を０．５〜１５重量部の割合で配
合した反応性の優れる方向性電磁鋼板用焼鈍分離剤。但
し、 Ｍ²⁺；Ｂｅ，Ｍｇ，Ｃａ，Ｂａ，Ｓｒ，Ｓｎ，Ｍｎ，Ｆ
ｅ，Ｃｏ，Ｎｉ，Ｃｕ，Ｚｎの中から選ばれる２価金属
の１種又は２種以上 Ｍ³⁺；Ａｌ，Ｆｅ，Ｃｒ，Ｃｏ，Ｉｎ，Ｂ，Ｇａ，Ｔｉ
の中から選ばれる３価金属の１種又は２種以上 Ａ^n-；ＯＨ^- ，Ｆ^- ，Ｃｌ^- ，Ｂｒ^- ，ＣＯ₃ ^2-，ＳＯ
₄ ^2-，ＳｉＯ₃ ^2-，ＨＰＯ₄ ^2-，ＣＨ₃ ＣＯＯ^- ，Ｆｅ
（ＣＮ）₆ ^3-，ＨＢＯ₃ ^2-等のｎ価のアニオン ０≦ｘ≦１．０， ０≦ｙ＜２．０， ｍ；層間水の分
子数1. M 2 ⁺ _1-x M based on 100 parts by weight of MgO
_{^{3+ x (OH) 2 + x}} -ny yA n- · mH direction having excellent reactivity blending solid solution type complex hydroxide represented by the general formula ₂ O in a proportion of 0.5 to 15 parts by weight Annealing Separator for Highly Magnetic Electrical Steel Sheets. However, M ²⁺ ; Be, Mg, Ca, Ba, Sr, Sn, Mn, F
One or more divalent metal selected from e, Co, Ni, Cu and Zn M ³⁺ ; Al, Fe, Cr, Co, In, B, Ga, Ti
One trivalent metal selected from among two or more ^{A n-; OH -, F -} , Cl -, Br -, CO 3 2-, SO
₄ ²⁻ , SiO ₃ ²⁻ , HPO ₄ ²⁻ , CH ₃ COO ⁻ , Fe
(CN) ₆ ³⁻ , HBO ₃ ^{2−, and} other n-valent anions 0 ≦ x ≦ 1.0, 0 ≦ y <2.0, m; number of molecules of interlayer water 【請求項２】 ＭｇＯ１００重量部に対し、Ｍ²⁺ _1-x Ｍ
³⁺ _x （ＯＨ）_2+x-nyｙＡ^n-・ｍＨ₂ Ｏの一般式で表され
る固溶型複合水酸化物を０．５〜１５重量部と添加剤と
して、酸化物、塩化物、硫酸塩、ほう酸塩、珪酸塩の中
から選ばれる１種又は２種以上を０．０５〜１０重量部
の割合で配合した反応性の優れる方向性電磁鋼板用焼鈍
分離剤。2. M 2 ⁺ _1-x M based on 100 parts by weight of MgO
³⁺ _x (OH) solid solution type complex hydroxide represented by the ^{_{2 + x-ny yA n- ·}} mH 2 O formula as additive 0.5 to 15 parts by weight, oxides, chlorides , An annealing separator for a grain-oriented electrical steel sheet having excellent reactivity, containing one or more selected from sulfate, borate and silicate in a proportion of 0.05 to 10 parts by weight. 【請求項３】 Ｓｉ：２．５〜４．０％を含有する方向
性電磁鋼板素材を公知の方法で処理し、最終板厚の冷延
板とし、脱炭焼鈍してＳｉＯ₂ 主成分の酸化被膜を形成
し、焼鈍分離剤を塗布し、最終仕上げ焼鈍を行った後、
絶縁被膜剤を塗布してヒートフラットニングを行うこと
からなる方向性電磁鋼板の製造方法において、前記焼鈍
分離剤の塗布工程で、ＭｇＯ１００重量部に対し、Ｍ²⁺
_1-x Ｍ³⁺ _x （ＯＨ）_2+x-nyｙＡ^n-・ｍＨ₂ Ｏの一般式で
表される固溶型複合水酸化物を０．５〜１５重量部の割
合で添加したスラリーを鋼板に塗布するグラス被膜形成
反応の優れる方向性電磁鋼板の製造方法。3. A grain-oriented electrical steel sheet material containing Si: 2.5 to 4.0% is treated by a known method to obtain a cold-rolled sheet having a final thickness, and decarburized and annealed to obtain a SiO ₂ main component. After forming an oxide film, applying an annealing separator, and performing final finishing annealing,
In a method for producing a grain-oriented electrical steel sheet, which comprises applying an insulating coating agent and performing heat flattening, in the step of applying the annealing separator, M ^{2+ is} added to 100 parts by weight of MgO.
_{^{1-x M 3+ x (OH}} ) added slurry solid solution type complex hydroxide represented by the general formula ^{_{2 + x-ny yA n- ·}} mH 2 O in a proportion of 0.5 to 15 parts by weight A method for producing a grain-oriented electrical steel sheet which is excellent in the reaction of forming a glass coating film on a steel sheet. 【請求項４】 Ｓｉ：２．５〜４．０％を含有する方向
性電磁鋼板素材を公知の方法で処理し、最終板厚の冷延
板とし、脱炭焼鈍してＳｉＯ₂ 主成分の酸化被膜を形成
し、焼鈍分離剤を塗布し、最終仕上げ焼鈍を行った後、
絶縁被膜剤を塗布してヒートフラットニングを行うこと
からなる、方向性電磁鋼板の製造方法において、前記焼
鈍分離剤の塗布工程において、ＭｇＯ１００重量部に対
し、Ｍ²⁺ _1-x Ｍ³⁺ _x （ＯＨ）_2+x-nyｙＡ^n-・ｍＨ₂ Ｏの
一般式で表される固溶型複合水酸化物を０．５〜１５重
量部と添加剤として酸化物、塩化物、硫酸塩、ほう酸
塩、珪酸塩の中から選ばれる１種又は２種以上を０．０
５〜１０重量部の割合で配合したスラリーを鋼板に塗布
するグラス被膜形成反応の優れる方向性電磁鋼板の製造
方法。4. A grain-oriented electrical steel sheet material containing Si: 2.5 to 4.0% is treated by a known method to obtain a cold-rolled sheet having a final thickness, decarburized and annealed to obtain a SiO ₂ main component. After forming an oxide film, applying an annealing separator, and performing final finishing annealing,
In a method for producing a grain-oriented electrical steel sheet, which comprises applying an insulating film agent and performing heat flattening, in the step of applying the annealing separator, M ²⁺ _1-x M ³⁺ _x relative to 100 parts by weight of MgO. _{(OH) 2 + x-ny} yA n- · mH oxide solid solution type complex hydroxide represented by the general formula ₂ O as an additive 0.5 to 15 parts by weight, chlorides, sulfates, One or more selected from borate and silicate is 0.0
A method for producing a grain-oriented electrical steel sheet excellent in a glass film forming reaction, which comprises applying a slurry compounded in a proportion of 5 to 10 parts by weight to a steel sheet. 【請求項５】 焼鈍分離剤の主成分に使用するＭｇＯの
水和水分が３％以下である請求項３〜４のいずれかに記
載のグラス被膜形成反応の優れる方向性電磁鋼板の製造
方法。5. The method for producing a grain-oriented electrical steel sheet excellent in a glass film forming reaction according to claim 3, wherein the hydrated water content of MgO used as a main component of the annealing separator is 3% or less. 【請求項６】 最終仕上げ焼鈍における昇温速度が昇温
時７００〜１１５０℃の間を平均１５℃／Hr以下とする
請求項３〜４のいずれかに記載のグラス被膜形成反応の
優れる方向性電磁鋼板の製造方法。6. The excellent directionality of the glass film forming reaction according to claim 3, wherein the temperature rising rate in the final finish annealing is 15 ° C./hr or less on average between 700 and 1150 ° C. when the temperature is raised. Manufacturing method of electrical steel sheet.