JP2001192738A - Method for producing grain oriented silicon steel sheet excellent in glass film characteristic and magnetic property - Google Patents
Method for producing grain oriented silicon steel sheet excellent in glass film characteristic and magnetic propertyInfo
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- JP2001192738A JP2001192738A JP2000002864A JP2000002864A JP2001192738A JP 2001192738 A JP2001192738 A JP 2001192738A JP 2000002864 A JP2000002864 A JP 2000002864A JP 2000002864 A JP2000002864 A JP 2000002864A JP 2001192738 A JP2001192738 A JP 2001192738A
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- steel sheet
- annealing
- tio
- mgo
- grain
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、脱炭焼鈍後に、低
水和で微粒のＭｇＯに対し、微粒子ＴｉＯ2 を添加・配
合して使用する際に、水スラリー中にＴｉＯ2 を均一に
微細分散させることにより、反応性の極めて優れる焼鈍
分離剤を得て、グラス被膜特性と磁気特性を向上させる
方向性電磁鋼板の製造方法に関する。BACKGROUND OF THE INVENTION The present invention is, after the decarburization annealing, to a low hydration of fine MgO, when used by admixing of particulate TiO 2, a TiO 2 uniformly in a water slurry fine The present invention relates to a method for producing a grain-oriented electrical steel sheet that obtains an annealing separator having extremely excellent reactivity by dispersing the same, thereby improving glass coating properties and magnetic properties.
【０００２】[0002]
【従来の技術】方向性電磁鋼板は、Ｓｉをたとえば２〜
４％含有する珪素鋼スラブを熱延し、焼鈍した後、１回
又は中間焼鈍を挟む２回以上の冷延を施して最終板厚と
し、次いで、脱炭焼鈍をした後、ＭｇＯを主成分とする
焼鈍分離剤を塗布し、仕上げ焼鈍を行ってゴス方位を持
つ二次再結晶を発達させ、更に、Ｓ、Ｎ等の不純物を除
去すると共にグラス被膜を形成し、次いで絶縁皮膜剤を
塗布し、焼き付けとヒートフラットニング処理を施して
最終製品とされる。2. Description of the Related Art Grain-oriented electrical steel sheets are formed by adding Si,
A 4% silicon steel slab is hot-rolled and annealed, and then cold-rolled once or twice or more with intermediate annealing to a final thickness, and then decarburized annealing, followed by MgO as a main component. Applying an annealing separating agent, and performing final annealing to develop secondary recrystallization having a Goss orientation, further removing impurities such as S and N, forming a glass coating, and then applying an insulating coating agent After baking and heat flattening, it is finished.
【０００３】このようして得られる方向性電磁鋼板は、
主として電気機器、トランス等の鉄心材料として使用さ
れるが、これらの材料として、磁束密度が高く、鉄損が
優れるものが要求される。良好な磁気特性を得るために
は、磁化容易軸である＜００１＞軸を、圧延方向に高度
にそろえることが重要である。結晶の方向性について
は、ＡｌＮを主インヒビターとして高圧下最終冷延を行
う方法により大幅に向上し、磁束密度がほぼ理論値に近
いものまで得られるようになってきた。更に、近年は、
薄手化や高Ｓｉ化技術が進歩し、鉄損レベルも大幅に改
善されてきている。[0003] The grain-oriented electrical steel sheet thus obtained is
It is mainly used as an iron core material for electrical equipment and transformers, and these materials are required to have a high magnetic flux density and an excellent iron loss. In order to obtain good magnetic properties, it is important that the <001> axis, which is the axis of easy magnetization, be highly aligned in the rolling direction. The directionality of the crystal has been greatly improved by a method of performing final cold rolling under high pressure using AlN as a main inhibitor, and magnetic flux density can be obtained up to a value close to a theoretical value. Furthermore, in recent years,
Advances in thinning and high Si technologies have led to significant improvements in iron loss levels.
【０００４】この磁気特性と共に、需要家における鉄心
加工時に重要なのは、仕上げ焼鈍中に形成されるグラス
被膜とヒートフラットニングで形成される絶縁コーティ
ングからなる絶縁皮膜特性である。これは、グラス被膜
特性が電磁鋼板を使用したトランス鉄心において、磁気
特性や絶縁性のみならず、ビルディングファクター、磁
歪、歪み敏感度、鉄心加工作業性等に多大な影響を与え
るからである。[0004] Along with the magnetic properties, what is important in the processing of the iron core in the consumer is the properties of the insulating film composed of the glass film formed during the finish annealing and the insulating coating formed by the heat flattening. This is because the properties of the glass coating greatly affect not only the magnetic properties and insulation properties but also the building factor, magnetostriction, strain sensitivity, core workability, and the like in the transformer core using the electromagnetic steel sheet.
【０００５】この方向性電磁鋼板のグラス被膜は、その
形成過程においても鋼中インヒビター制御の面で重要
で、又、形成されたグラス被膜の磁区細分化効果機能の
面でも重要な役割を有している。それ故、高磁束密度で
低鉄損の製品を得るためには、製造過程でのグラス被膜
形成速度、質、量、均一性等に優れることが重要であ
る。[0005] The glass film of the grain-oriented electrical steel sheet is important in controlling the inhibitor in the steel also in the forming process, and also plays an important role in the magnetic domain refining effect function of the formed glass film. ing. Therefore, in order to obtain a product having a high magnetic flux density and a low iron loss, it is important that the glass film formation rate, quality, quantity, uniformity, etc., be excellent in the manufacturing process.
【０００６】即ち、本発明のように、脱炭焼鈍後の鋼板
にＭｇＯを主成分とする焼鈍分離剤を塗布しグラス被膜
形成を行う工程においては、グラス被膜の形成時期、形
成速度、形成状態、量等が、鋼板界面における雰囲気ガ
スからの窒化や鋼中インヒビターの分解挙動に影響を与
え、更に、グラス被膜は追加酸化や還元の影響を受け易
いという問題を抱えている。したがって、グラス被膜形
成速度の向上や被膜形成過程の質改善によるシール性向
上は、グラス被膜特性と磁気特性の両方が優れた製品を
得る上で重要である。That is, as in the present invention, in the step of applying an annealing separator containing MgO as a main component to a steel sheet after decarburizing annealing to form a glass film, the time, speed and formation state of the glass film are formed. , The amount and the like affect the nitriding from the atmospheric gas at the steel plate interface and the decomposition behavior of the inhibitor in the steel, and further, the glass coating has a problem that it is easily affected by additional oxidation and reduction. Therefore, the improvement of the glass film forming speed and the improvement of the sealing property by improving the quality of the film forming process are important for obtaining a product having both excellent glass film characteristics and magnetic characteristics.
【０００７】ＴｉＯ2 を添加した焼鈍分離剤は数多く提
案されている。特公昭４９−２９４０９号公報には、嵩
比重０．１８〜０．３０ｇ／ccの重質で低活性のＭｇＯ
の微粒マグネシア１００重量部に対し、２〜２０重量部
のアナターゼ型のＴｉＯ2 と水とを混合して液温１５℃
以下に保って３０分以上攪拌し、水和水分１〜４％のス
ラリーとし、このスラリーを均一に塗布すると、方向性
電磁鋼板の表面に均一なガラス状絶縁皮膜が得られるこ
とが開示されている。[0007] Many annealing separators to which TiO 2 has been added have been proposed. JP-B-49-29409 discloses heavy and low-activity MgO having a bulk specific gravity of 0.18 to 0.30 g / cc.
2 to 20 parts by weight of anatase type TiO 2 and water are mixed with 100 parts by weight of fine magnesia of
It is disclosed that a slurry having a hydration moisture of 1 to 4% is obtained by stirring for 30 minutes or more while maintaining the following conditions, and when this slurry is uniformly applied, a uniform glassy insulating film is obtained on the surface of the grain-oriented electrical steel sheet. I have.
【０００８】又、特公昭５６−１５４６６号公報には、
前記技術の改善技術として、脱炭焼鈍し、ＳｉＯ2 を形
成後マグネシアを主成分とする焼鈍分離剤を鋼板に塗布
する際、３２５メッシュ（４４μｍ）のタイラー標準篩
を９８wt％以上通過し、且つ、２０μｍ以下の粒子を８
０wt％以上含有する微細なＴｉＯ2 を１〜２０重量部含
有する焼鈍分離剤を用いることにより、粗粒子ＴｉＯ2
がもたらす黒点状付着物の発生を阻止する技術が提案さ
れている。そして、これらの従来技術により、方向性電
磁鋼板におけるグラス被膜の形成技術は、飛躍的な発展
を遂げてきた。[0008] Japanese Patent Publication No. 56-15466 discloses that
As an improvement technique of the above technique, when applying an annealing separator mainly composed of magnesia to a steel sheet after decarburizing annealing and forming SiO 2 , the steel sheet passes through a 325 mesh (44 μm) Tyler standard sieve at 98 wt% or more, and , Particles of 20 μm or less
By using an annealing separator containing 1 to 20 parts by weight of fine TiO 2 containing 0 wt% or more, coarse TiO 2
There has been proposed a technique for preventing the generation of black spot-like deposits caused by the above. And, with these conventional techniques, the technique of forming a glass coating on a grain-oriented electrical steel sheet has made remarkable progress.
【０００９】しかしながら、グラス被膜の安定形成は、
素材の成分や工程条件の違いからもたらされる表面酸化
膜の違いや、ＭｇＯの性質によっては未だ十分なものと
は言い難く、鋼板板厚の薄手化と共に、グラス被膜形成
の安定向上や、これに関連するインヒビターの安定化は
より重要な課題であり、更なる技術改善が望まれてい
る。However, the stable formation of the glass film is
Depending on the difference in the surface oxide film caused by the difference in the composition of the material and the process conditions, and the properties of MgO, it is still difficult to say that it is sufficient. Stabilization of related inhibitors is a more important issue, and further technical improvements are desired.
【００１０】[0010]
【発明が解決しようとする課題】焼鈍分離剤の添加剤と
して用いるＴｉＯ2 は、ＭｇＯと混合してスラリー調整
を行う場合、ＴｉＯ2 粒子の凝集が生じ粗大化するとい
う問題を有している。更には、素材の成分や工程条件の
違いからもたらされる表面酸化膜の違いや、Ｍｇの性質
によっては、グラス被膜形成の安定性は未だ十分なもの
とは言い難く、鋼板板厚の薄手化と共に、グラス被膜形
成の安定向上や磁気特性の向上は重要な課題である。TiO 2 used as an additive of an annealing separator has a problem that when mixed with MgO and adjusted for slurry, TiO 2 particles are aggregated and coarsened. Furthermore, depending on the difference in the surface oxide film resulting from the difference in the composition of the material and the process conditions, and the nature of Mg, the stability of the glass film formation is still not sufficiently satisfactory. However, it is important to improve the stability of glass film formation and the magnetic properties.
【００１１】[0011]
【課題を解決するための手段】本発明は、極めて反応性
に優れ、グラス被膜特性と磁気特性を向上するためのＴ
ｉＯ2 を含有し、且つ、分散性に優れる焼鈍分離剤を用
い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）脱炭焼鈍後の鋼板の表面に焼鈍分離剤を塗布し、
仕上げ焼鈍の後、絶縁皮膜処理を行う方向性電磁鋼板の
製造方法において、ＭｇＯ１００重量部に対し、ＴｉＯ
2 を０．３〜１０重量部、及び、ヘキサメタ燐酸ナトリ
ューム、コロイダルシリカ、珪酸ナトリュームの１種又
は２種以上を０．００２５〜１．０重量部添加した水ス
ラリーを、攪拌後、前記脱炭焼鈍後の鋼板の表面に塗布
し、その後、仕上げ焼鈍をすることを特徴とするグラス
被膜特性及び磁気特性の優れる方向性電磁鋼板の製造方
法。 （２）前記０．００２５〜１．０重量部のヘキサメタ燐
酸ナトリューム、コロイダルシリカ、珪酸ナトリューム
の１種又は２種以上を水に分散させ、次いで、攪拌しな
がら、前記０．３〜１０重量部のＴｉＯ2 を分散させ、
その後、前記１００重量部のＭｇＯを分散させ水スラリ
ーとすることを特徴とする前記（１）記載のグラス被膜
特性及び磁気特性の優れる方向性電磁鋼板の製造方法。 （３）前記ＴｉＯ2 の比表面積が１５ｍ2 ／ｇ以上であ
ることを特徴とする前記（１）又は（２）記載のグラス
被膜特性及び磁気特性の優れる方向性電磁鋼板の製造方
法。なお、比表面積はＢＥＴ法による測定値である。 （４）前記ＴｉＯ2 の平均粒子径が０．１５μｍ以下で
あることを特徴とする前記（１）、（２）又は（３）記
載のグラス被膜特性及び磁気特性の優れる方向性電磁鋼
板の製造方法。なお、ＴｉＯ2 粒子径は電子顕微鏡によ
る単一粒子測定値である。 （５）前記焼鈍分離剤主成分として粒度１μｍ以下１０
％以上で、且つ、水和水分１〜３％のＭｇＯを用いるこ
とを特徴とする前記（１）、（２）、（３）又はは
（４）記載のグラス被膜特性及び磁気特性の優れる方向
性電磁鋼板の製造方法。なお、ＭｉＯ粒子径はレーザー
回折・散乱式粒度分布測定法による測定値である。DISCLOSURE OF THE INVENTION The present invention has an extremely high reactivity, and a T film for improving glass coating characteristics and magnetic characteristics.
The following configuration is a gist of a method for manufacturing a grain-oriented electrical steel sheet using an annealing separator containing iO 2 and having excellent dispersibility. (1) An annealing separator is applied to the surface of the steel sheet after decarburizing annealing,
In the method for producing a grain-oriented electrical steel sheet which is subjected to an insulating film treatment after the finish annealing, the TiO is mixed with 100 parts by weight of MgO.
2 to 0.3 to 10 parts by weight, and a water slurry to which 0.0025 to 1.0 part by weight of one or more of sodium hexametaphosphate, colloidal silica, and sodium silicate are added, and then the decarburization is performed. A method for producing a grain-oriented electrical steel sheet having excellent glass coating properties and magnetic properties, which is applied to the surface of a steel sheet after annealing and then subjected to finish annealing. (2) One or more of 0.0025 to 1.0 parts by weight of sodium hexametaphosphate, colloidal silica and sodium silicate are dispersed in water, and then, with stirring, the above 0.3 to 10 parts by weight is dispersed. Of TiO 2
Thereafter, 100 parts by weight of MgO is dispersed into a water slurry to produce a grain-oriented electrical steel sheet having excellent glass coating properties and magnetic properties according to (1). (3) The method for producing a grain-oriented electrical steel sheet according to (1) or (2), wherein the specific surface area of the TiO 2 is 15 m 2 / g or more. The specific surface area is a value measured by the BET method. (4) The production of a grain-oriented electrical steel sheet having excellent glass coating properties and magnetic properties according to (1), (2) or (3), wherein the average particle diameter of the TiO 2 is 0.15 μm or less. Method. The TiO 2 particle diameter is a single particle measured value by an electron microscope. (5) A particle size of 1 μm or less as a main component of the annealing separator 10
% Or more, and MgO having a hydration moisture of 1 to 3% is used, wherein the glass coating characteristics and the magnetic characteristics are excellent in the above (1), (2), (3) or (4). Manufacturing method of conductive electrical steel sheet. The MiO particle diameter is a value measured by a laser diffraction / scattering particle size distribution measuring method.
【００１２】[0012]
【発明の実施の形態】本発明者等は、方向性電磁鋼板の
製造において、脱炭焼鈍後の鋼板の表面にＴｉＯ2 含有
の焼鈍分離剤を塗布し、仕上げ焼鈍を行う際のグラス被
膜の安定化とインヒビター安定化技術の開発に取り組ん
だ。その結果、スラリー中におけるＴｉＯ2 粒子の分散
性を向上させ、超微粒子のＴｉＯ2 を焼鈍分離剤中に均
一に分散させ、脱炭焼鈍板の表面に塗布することによ
り、従来技術と比較して、最終仕上げ焼鈍におけるグラ
ス被膜形成反応を極めて改善できることを見い出した。BEST MODE FOR CARRYING OUT THE INVENTION In the production of grain-oriented electrical steel sheets, the present inventors applied a TiO 2 -containing annealing separating agent to the surface of a steel sheet after decarburization annealing, and formed a glass coating for finish annealing. We worked on stabilization and development of inhibitor stabilization technology. As a result, the dispersibility of the TiO 2 particles in the slurry is improved, and the ultrafine TiO 2 is uniformly dispersed in the annealing separator, and is applied to the surface of the decarburized annealed plate. It has been found that the glass film forming reaction in the final annealing can be significantly improved.
【００１３】又、この改善により、仕上げ焼鈍における
雰囲気変動の影響を弱め、酸化や窒化がグラス被膜特性
や磁気特性に及ぼす問題を解決し、グラス被膜特性と磁
気特性を安定的に向上できる技術の開発に成功した。以
下詳細に説明する。本発明においては、出発材として、
通常の工程で処理された脱炭焼鈍板を用いる。グラス被
膜特性と磁気特性の安定的な向上を目的とする本発明に
おいては、焼鈍分離剤の添加剤として用いるＴｉＯ2 の
分散方法に大きな特徴がある。[0013] Further, this improvement reduces the influence of the atmosphere change in the finish annealing, solves the problem of oxidation and nitridation on the glass film characteristics and magnetic characteristics, and stably improves the glass film characteristics and magnetic characteristics. Successful development. This will be described in detail below. In the present invention, as a starting material,
A decarburized annealed plate treated in a normal process is used. In the present invention, which aims at stably improving the properties of the glass coating and the magnetic properties, there is a great feature in the method of dispersing TiO 2 used as an additive of the annealing separator.
【００１４】即ち、本発明者等は、焼鈍分離剤として用
いるＴｉＯ2 について検討した結果、ＴｉＯ2 の一次粒
子として微粒子のものを用いても、ＭｇＯスラリー中に
おいて凝集が生じ、鋼板の表面に塗布される際には、実
質的な粒子のサイズが大きくなっていて、グラス被膜形
成の際の反応性向上効果が損なわれるという問題がある
ことを突き止めた。That is, the present inventors have studied TiO 2 used as an annealing separating agent. As a result, even if fine particles of TiO 2 are used as primary particles, agglomeration occurs in the MgO slurry and the TiO 2 is coated on the surface of the steel sheet. In this case, it was found that there was a problem that the size of the particles was substantially increased and the effect of improving the reactivity in forming the glass film was impaired.
【００１５】本発明においては、このＴｉＯ2 の凝集発
生問題を解決するためのスラリー中における新規なＴｉ
Ｏ2 の分散技術を提供するものである。本発明は、Ｍｇ
Ｏ１００重量部に対し、ＴｉＯ2 を０．３〜１０重量部
添加・配合し水にスラリー状に分散させて用いる際、特
定の分散剤を一定量添加・配合することにより、ＴｉＯ
2 微粒子のスラリー中での均一分散性を高め、鋼板に塗
布される際のＭｇＯ中における均一分散効果を得るもの
である。In the present invention, a novel Ti in slurry is used to solve the problem of TiO 2 aggregation.
Dispersion techniques of O 2 is intended to provide. The present invention relates to Mg
When 0.3 to 10 parts by weight of TiO 2 is added to and blended with 100 parts by weight of O and dispersed in a slurry in water for use, a specific amount of a specific dispersant is added and blended to obtain TiO 2.
(2) It enhances the uniform dispersibility of the fine particles in the slurry and obtains the uniform dispersion effect in MgO when applied to a steel sheet.
【００１６】この際、ＴｉＯ2 均一分散剤として、ヘキ
サメタ燐酸ナトリューム、コロイダルシリカ、珪酸ナト
リュームの１種又は２種以上を、ＭｇＯ１００重量部に
対し０．００２５〜１．０重量部の割合で添加・配合す
る。又、この際に適用される超微粒子ＴｉＯ2 の好まし
い条件は、比表面積１５ｍ 2 ／ｇ以上、又は、平均粒子
径０．１５μｍ以下であり、この超微粒子ＴｉＯ2が、
より大きいグラス被膜反応向上効果を得るために用いら
れる。なお、比表面積はＢＥＴ法による測定値であり、
粒子径は、電子顕微鏡による単一粒子測定値である。At this time, TiOTwoAs a uniform dispersant,
Sodium sodium metaphosphate, colloidal silica, sodium silicate
One or more kinds of rhume are added to 100 parts by weight of MgO
0.0025 to 1.0 parts by weight
You. In addition, the ultrafine TiO applied at this timeTwoPreferred
The condition is specific surface area 15m Two/ G or more, or average particle
The ultrafine TiO particles having a diameter of 0.15 μm or lessTwoBut,
Used to obtain a larger glass coating reaction improvement effect
It is. The specific surface area is a value measured by the BET method,
Particle size is a single particle measurement with an electron microscope.
【００１７】また、本発明のＴｉＯ2 適用においては、
ベースＭｇＯとして、粒度１μｍパス１０％以上で、且
つ、水和水分１〜３％のＭｇＯを用いるのが好ましい。
この条件は、本発明の反応性向上のためのＴｉＯ2 の効
果を発揮するうえにおいて、より優れた条件である。な
お、ＭｇＯ粒子径は、レーザー回折・散乱式粒度分布測
定法による値である。In the application of TiO 2 of the present invention,
As the base MgO, it is preferable to use MgO having a particle size of 1 μm pass of 10% or more and a hydration moisture of 1 to 3%.
These conditions are more excellent conditions for exhibiting the effect of TiO 2 for improving the reactivity of the present invention. The MgO particle diameter is a value obtained by a laser diffraction / scattering type particle size distribution measuring method.
【００１８】更に、この際、必要に応じて、グラス被膜
形成反応促進やインヒビター強化等の目的で、他の酸化
物、Ｂ化合物、Ｓ化合物、Ｃｌ、Ｆ等のハロゲン物質等
が添加される。このように調整された焼鈍分離剤スラリ
ーは、ロールコーター等を用いて、連続ラインで鋼板表
面に塗布され、乾燥後、鋼板はコイル状に巻き取られ
る。次いで、最終仕上げ焼鈍が行われるが、グラス被
膜、二次再結晶、純化等を満足するために、昇温時の雰
囲気は（Ｎ2 ＋Ｈ2 ）ガスを用い、又、均熱中はＨ2 ガ
スを用い、１１５０〜１２００℃で２０Hr程度の焼鈍が
行われる。Further, at this time, if necessary, other oxides, B compounds, S compounds, and halogen substances such as Cl and F are added for the purpose of accelerating the reaction of forming a glass film and strengthening the inhibitor. The annealing separator slurry thus adjusted is applied to the steel sheet surface in a continuous line using a roll coater or the like, and after drying, the steel sheet is wound into a coil. Then, although final annealing is performed, glass film, the secondary recrystallization, in order to satisfy the purification or the like, the atmosphere during heating is used (N 2 + H 2) gas, also equalizing enthusiasm the H 2 gas Is performed at 1150 to 1200 ° C. for about 20 hours.
【００１９】この後、グラス被膜形成後のコイルは、余
剰の焼鈍分離剤が水洗除去された後、連続ラインにおい
て、８００〜９００℃の温度で絶縁皮膜の焼き付けとヒ
ートフラットニング処理が行われる。この際、方向性電
磁鋼板においては、前述の如く、グラス被膜の形成状態
と共に絶縁皮膜が、鉄損及び磁歪特性の向上において重
要であり、このため、特公昭５３−２８３７５号公報に
記載されるような、りん酸塩−コロイダルシリカ系の張
力付与型の絶縁皮膜剤の処理焼き付けが行われる。After that, the coil after the formation of the glass film is subjected to baking of the insulating film and heat flattening at a temperature of 800 to 900 ° C. in a continuous line after the excess annealing separating agent is removed by washing with water. At this time, in the grain-oriented electrical steel sheet, as described above, the insulating film as well as the state of formation of the glass film is important in improving iron loss and magnetostriction characteristics, and is therefore described in JP-B-53-28375. Such a phosphate-colloidal silica-based tension imparting type insulating film agent is baked.
【００２０】次に、本発明の諸条件に係る限定理由につ
いて述べる。本発明の出発材は特に限定されるものでは
なく、本発明は、通常の工程で製造される方向性電磁鋼
板やインヒビターとしてＡｌＮを用いる高磁束密度方向
性電磁鋼板に適用される。本発明における最大の特徴は
ＴｉＯ2 の分散法にある。即ち、ＴｉＯ2 粒子は、それ
自体を単独で水に分散させる場合には極めて分散性が優
れ、ほぼ製造時の粒子サイズを反映した粒子サイズで分
散できる。Next, the reasons for limiting the various conditions of the present invention will be described. The starting material of the present invention is not particularly limited, and the present invention is applied to a grain-oriented electrical steel sheet manufactured by a normal process and a high magnetic flux density grain-oriented electrical steel sheet using AlN as an inhibitor. The greatest feature of the present invention lies in the TiO 2 dispersion method. That is, when TiO 2 particles are themselves dispersed in water, they have extremely excellent dispersibility, and can be dispersed at a particle size substantially reflecting the particle size at the time of production.
【００２１】しかしながら、本発明者等は、ＴｉＯ2 粒
子をＭｇＯのような２価金属の酸化物と同時に分散させ
ようとする際には、ＴｉＯ2 粒子はＭｇ2+やＯＨ基によ
るpHの影響を受けて凝集し、その結果、ＭｇＯ塗布膜中
の粒子粗大化や不均一分散が生じて、グラス被膜形成時
の反応性向上効果が損なわれることを新たに突き止め
た。[0021] However, the present inventors have, when the TiO 2 particles attempting to simultaneously disperse the oxides of divalent metals, such as MgO, the TiO 2 particles influence of pH by Mg 2+ and OH groups Then, they newly aggregated, and as a result, found that the particles were coarsened and unevenly dispersed in the MgO coating film, and the effect of improving the reactivity at the time of forming the glass film was impaired.
【００２２】この対策として、ＴｉＯ2 粒子の凝集を防
ぐ方法を鋭意検討したところ、ヘキサメタ燐酸ナトリュ
ーム、コロイダルシリカや珪酸ナトリュームの１種又は
２種以上を、ＭｇＯ１００重量部に対し０．００２５〜
１．０重量部添加すれば、前述のようなＴｉＯ2 の凝集
は生じず、極めて良好なＴｉＯ2 分散効果によるグラス
被膜向上効果が得られることが判明した。As a countermeasure, a method for preventing the aggregation of TiO 2 particles was intensively studied. One or more of sodium hexametaphosphate, colloidal silica and sodium silicate were added in an amount of 0.0025 to 100 parts by weight of MgO.
It was found that when 1.0 part by weight was added, the above-mentioned aggregation of TiO 2 did not occur, and an extremely good effect of improving the glass film by the TiO 2 dispersion effect was obtained.
【００２３】分散剤添加量が０．００２５重量部未満で
は、ＴｉＯ2 分散向上効果が十分でない。一方、上記添
加量が１．０重量部超では、分散剤が過剰となり、その
結果、脱炭焼鈍条件や仕上げ焼鈍条件によっては、被膜
に欠陥が生じたり、磁性劣化が起きたりする場合がある
ので、１．０重量部以下に制限する。本発明のＴｉＯ2
分散剤の添加に当たっては、ＭｇＯとＴｉＯ2 分散剤を
水中に段階的に投入してスラリー調整を行ってもよい
が、好ましくは、まず水に分散剤を溶解し、その後、Ｔ
ｉＯ2 を投入して攪拌し、分散を十分に行った後ＭｇＯ
を添加すると、より優れた分散が得られ、グラス被膜向
上効果が安定して得られる。If the amount of the dispersant is less than 0.0025 parts by weight, the effect of improving TiO 2 dispersion is not sufficient. On the other hand, when the above-mentioned addition amount exceeds 1.0 part by weight, the dispersant becomes excessive, and as a result, depending on the decarburizing annealing condition and the finish annealing condition, a defect may be generated in the coating or the magnetic deterioration may occur. Therefore, it is limited to 1.0 part by weight or less. TiO 2 of the present invention
When adding the dispersant, the slurry may be adjusted by adding the MgO and TiO 2 dispersants stepwise into water, but preferably, the dispersant is first dissolved in water, and then T
After adding and stirring iO 2 and thoroughly dispersing,
Is added, more excellent dispersion is obtained, and the effect of improving the glass coating is stably obtained.
【００２４】ＴｉＯ2 の比表面積は、粒子形状や表面の
表面処理剤の処理条件等によって異なるが、本発明にお
いてはこれらについて特に限定するものではない。但
し、１５ｍ2 ／ｇ以上のような大きい比表面積を有する
ＴｉＯ2 を用いると、更に優れたグラス被膜形成反応向
上効果が得られる。これは、比表面積が大きいと、Ｍｇ
Ｏや下地酸化膜との接触面積や密着性が向上して、仕上
げ焼鈍昇温過程においてしＴｉＯ2 からの酸素の分解放
出がより均一化されるからである。The specific surface area of TiO 2 varies depending on the particle shape and the treatment conditions of the surface treating agent on the surface, but these are not particularly limited in the present invention. However, when TiO 2 having a large specific surface area such as 15 m 2 / g or more is used, a more excellent effect of improving the glass film forming reaction can be obtained. This is because when the specific surface area is large, Mg
This is because the contact area and adhesion with O and the underlying oxide film are improved, and the decomposition and release of oxygen from TiO 2 are more uniform in the final annealing temperature raising process.
【００２５】また、ＴｉＯ2 の粒子径が０．１５μｍ以
下の場合、超微粒子によるＭｇＯ中のＴｉＯ2 粒子のよ
り良い均一分散効果、鋼板への密着性向上、塗布性向
上、均一化された分解反応等により、優れた反応性向上
効果が更に高まることになる。このようなＴｉＯ2 分散
技術におけるＴｉＯ2 の添加量は、ＭｇＯ１００重量部
に対し０．３〜１０重量部である。この添加量は、素材
の鋼成分（酸化層成分）、脱炭焼鈍条件、ＭｇＯの性
状、他の添加剤条件等の違いによって選択される。添加
量が０．３重量部未満では、本発明の高反応性ＴｉＯ2
をもってしても反応性向上効果が十分でない。一方、１
０重量部超では、高温域で分解放出される酸素が過剰と
なり、酸化過度による被膜欠陥やインヒビターへの悪影
響による磁性劣化が生じ易くなる。それ故、ＴｉＯ2 の
添加量の上限は、１０重量部に制限される。When the particle diameter of TiO 2 is 0.15 μm or less, the effect of dispersing the TiO 2 particles in MgO better by ultrafine particles, improving the adhesion to the steel sheet, improving the coating property, and achieving uniform decomposition Due to the reaction and the like, the excellent reactivity improving effect is further enhanced. The addition amount of TiO 2 in such a TiO 2 dispersion technique is 0.3 to 10 parts by weight based on 100 parts by weight of MgO. The amount of addition is selected depending on differences in the steel component (oxide layer component) of the raw material, decarburizing annealing conditions, properties of MgO, other additive conditions, and the like. If the addition amount is less than 0.3 parts by weight, the highly reactive TiO 2 of the present invention is used.
However, the effect of improving reactivity is not sufficient. Meanwhile, 1
If the amount exceeds 0 parts by weight, oxygen decomposed and released in a high temperature range becomes excessive, so that excessive oxidation tends to cause film defects and magnetic deterioration due to adverse effects on inhibitors. Therefore, the upper limit of the addition amount of TiO 2 is limited to 10 parts by weight.
【００２６】ＴｉＯ2 の添加に当たっては、超微粒子を
単独に添加してもよいし、一般的な比較的小さい粒子径
を有するＴｉＯ2 と超微粒子とを混合して、本発明の比
表面積と粒子径の範囲として添加してもよい。一般に、
超微粒子のＴｉＯ2 を得ようとする場合には、その製造
のコストが高くなる傾向にあるが、このような混合方法
によっても、その問題を回避でき、超微粒子単独使用の
場合と同等の効果が得られる。When adding TiO 2 , ultrafine particles may be added alone, or TiO 2 having a relatively small particle size and ultrafine particles may be mixed, and the specific surface area and the fine particles of the present invention may be mixed. It may be added as a range of the diameter. In general,
When trying to obtain ultrafine TiO 2 , the production cost tends to be high. However, even with such a mixing method, the problem can be avoided, and the same effect as in the case of using ultrafine particles alone can be obtained. Is obtained.
【００２７】ＭｇＯは、仕上げ焼鈍過程においてグラス
被膜形成を行う際、重要な役割を果す。即ち、脱炭焼鈍
板の表面上のＳｉＯ2 層との良好な反応を得るに際し、
反応開始までの鋼板への密着性やグラス被膜形成反応
に、微粒子ＭｇＯが大きな役割を果すからである。主成
分ＭｇＯに係る条件としては、まず、粒子径１μｍパス
値が１０％以上で、且つ、水和水分が１〜３％であるこ
とが好ましい条件である。粒子径１μｍパス以下１０％
未満では、本発明のＴｉＯ2 を有する焼鈍分離剤をもっ
てしても、脱炭焼鈍や仕上げ焼鈍条件によっては、グラ
ス被膜反応向上効果が安定して得られない場合がある。
粒子径が１μｍパス以下１０％以上で、極めて優れた反
応向上効果が発揮される。MgO plays an important role in forming a glass film in the finish annealing process. That is, in obtaining a good reaction with the SiO 2 layer on the surface of the decarburized annealed plate,
This is because the fine particles of MgO play a large role in the adhesion to the steel sheet and the glass film forming reaction until the reaction starts. First, the conditions for the main component MgO are preferably conditions in which a 1 μm particle diameter pass value is 10% or more and hydration moisture is 1 to 3%. Particle size 1% or less 10%
If it is less than 30, the effect of improving the glass film reaction may not be stably obtained depending on the conditions of decarburizing annealing and finish annealing even with the annealing separator having TiO 2 of the present invention.
When the particle diameter is 1% or less and 10% or more, an extremely excellent reaction improving effect is exhibited.
【００２８】また、水和水分としては１〜３％であるこ
とが好ましい。水和水分は、ＭｇＯの鋼板への接着性の
向上や、仕上げ焼鈍昇温過程におけるコイル板間の雰囲
気の適度な酸化度の維持に影響する。水和水分が１％未
満では、密着性やコイル板間の雰囲気の調節が十分に行
われない。特に、後者のコイル板間の雰囲気における適
度な酸化度数の維持は重要で、酸化度が適切でないと脱
炭焼鈍時に生成した酸化膜層の還元による反応性低下を
押さえる効果が不十分となり、本発明のＴｉＯ 2 をもっ
てしても、グラス被膜形成が不均一になる場合がある。
水和水分が３％超では、水分が過剰となり、この水分に
より、鋼板外周やエッジ部に、追加酸化によるグラス被
膜欠陥が生じ、その結果、磁性劣化が生じるので好まし
くない。The hydration water content is 1 to 3%.
Is preferred. Hydration moisture is a property of adhesion of MgO to steel plate.
Atmosphere between coil plates in the process of temperature rise and finish annealing
Affects the maintenance of moderate oxidation degree. Hydration water is less than 1%
In the full state, the adhesion and the atmosphere between the coil plates are sufficiently adjusted.
I can't. In particular, the latter is suitable for the atmosphere between the coil plates.
It is important to maintain a high oxidation degree, and if the oxidation degree is not appropriate,
Reduction of reactivity due to reduction of oxide film layer generated during charcoal annealing
The effect of suppressing is insufficient, and the TiO of the present invention TwoWith
In some cases, the formation of a glass coating may be non-uniform.
If the hydrated water is more than 3%, the water becomes excessive,
The outer periphery and edge of the steel sheet
It is preferable because film defects occur, resulting in magnetic deterioration.
I don't.
【００２９】[0029]
【実施例】（実施例１）質量％で、Ｃ；０．０７８％、
Ｓｉ；３．３０％、Ｍｎ；０．０６８％、酸可溶Ａｌ
０．０２７％、Ｓ；０．０２４％、Ｎ；０．００８０
％、Ｓｎ；０．０６０％、Ｃｕ；０．０８％、残部Ｆｅ
と不可避不純物からなる素材スラブを、１３５０℃で加
熱して熱延し、１１２０℃で２min.の焼鈍を施し、その
後酸洗し、次いで冷延して、０．２２５mm厚の鋼板とし
た。次いで、この鋼板に、８３０℃で１２０sec.、Ｎ2
２５％＋Ｈ2 ７５％、ＤＰ６８℃の雰囲気ガス中で脱炭
焼鈍を施し、これを出発材（鋼板）とした。この鋼板
に、焼鈍分離剤として、１μｍパス１５％で、且つ、水
和水分１．５％のＭｇＯ１００重量部に対し、第１表に
示すように、比表面積と粒子径の異なるＴｉＯ2 と分散
剤を添加したスラリーを塗布し、その後、最終仕上げ焼
鈍を行った。この後、ヒートフラットニングに際し、絶
縁皮膜剤として“３０％コロイダルシリカ７０ml＋５０
％リン酸Ａｌ ５０ml＋ＣｒＯ3 ６．５ｇ”の溶液を焼
き付け、その後、重量で４．５ｇ／ｍ2 になるよう塗布
し、焼き付け処理を行った。グラス被膜特性と磁気特性
の評価・試験結果を第２表に示す。EXAMPLES (Example 1) In mass%, C: 0.078%,
Si: 3.30%, Mn: 0.068%, acid-soluble Al
0.027%, S; 0.024%, N; 0.0080
%, Sn: 0.060%, Cu: 0.08%, balance Fe
The raw material slab consisting of slabs and unavoidable impurities was heated at 1350 ° C., hot-rolled, annealed at 1120 ° C. for 2 minutes, pickled, and then cold-rolled to obtain a 0.225 mm thick steel sheet. Then, the steel sheet, 120 sec at 830 ° C.., N 2
Decarburization annealing was performed in an atmosphere gas of 25% + 75% H 2 and DP 68 ° C., which was used as a starting material (steel plate). As shown in Table 1, this steel sheet was dispersed with TiO 2 having a specific surface area and a particle size different from each other as shown in Table 1 with respect to 100 parts by weight of MgO having a 1 μm pass of 15% and a hydration moisture of 1.5% as an annealing separator. The slurry to which the agent was added was applied, and then a final finish annealing was performed. Thereafter, when heat flattening, “30% colloidal silica 70 ml + 50” was used as an insulating film agent.
% Of phosphoric acid Al + 6.5 g of CrO 3 6.5 g ”, and then applied at a weight of 4.5 g / m 2 , and baked. The evaluation and test results of the glass coating properties and the magnetic properties are shown in FIG. The results are shown in Table 2.
【００３０】[0030]
【表１】 [Table 1]
【００３１】[0031]
【表２】 [Table 2]
【００３２】この評価・試験結果において、本発明のＴ
ｉＯ2 と共に分散剤を添加した場合には、何れもグラス
被膜改善効果が認められ、特にＢＥＴ値（比表面積）の
大きいＴｉＯ2 の場合には、極めて優れたグラス被膜特
性と磁気特性が得られている。一方、ＴｉＯ2 分散剤を
添加しない場合には、何れもグラス被膜がやや薄かった
り、不均一であった。又、分散剤が少ない比較例におい
ては、グラス被膜形成向上効果が弱く、多すぎる比較例
においては、やや被膜が不均一で、本発明の条件に比
し、グラス被膜特性、磁気特性共に、やや劣る結果とな
った。 （実施例２）実施例１と同様に調整した脱炭焼鈍板に、
焼鈍分離剤として、１μｍパスの微粒子量の異なるＭｇ
Ｏに、第３表に示すように粒度を変更して製造した超微
粒子ＴｉＯ2 を添加量を変更して添加したスラリーを塗
布し、その後、最終仕上げ焼鈍を行った。この際、Ｔｉ
Ｏ2 分散剤としては珪酸ナトリュームを１００重量部当
たり０．０５重量部の割合で水に分散し、攪拌しながら
ＴｉＯ2 を添加し、十分分散処理を行った後、ＭｇＯを
添加してスラリーとした。この後、ヒートフラットニン
グに際し、絶縁皮膜剤として“３０％コロイダルシリカ
７０ml＋５０％リン酸Ａｌ ５０ml＋ＣｒＯ3 ６．５
ｇ”の溶液を焼き付け、その後、重量で４．５ｇ／ｍ2
になるよう塗布し、焼き付け処理を行った。グラス被膜
特性と磁気特性の評価・試験結果を第４表に示す。In the evaluation and test results, the T
When a dispersing agent is added together with iO 2 , the effect of improving the glass coating is recognized, and particularly in the case of TiO 2 having a large BET value (specific surface area), extremely excellent glass coating characteristics and magnetic characteristics are obtained. ing. On the other hand, when no TiO 2 dispersant was added, the glass coating was slightly thin or non-uniform. Further, in the comparative example with a small amount of the dispersant, the effect of improving the glass film formation was weak, and in the comparative example with too much, the film was slightly non-uniform, and compared with the conditions of the present invention, the glass film properties and the magnetic properties were slightly higher. Inferior results. (Example 2) A decarburized annealed plate adjusted in the same manner as in Example 1
Mg with different amount of fine particles in 1μm pass as annealing separator
O was coated with a slurry in which ultrafine TiO 2 produced by changing the particle size as shown in Table 3 was added in a different amount, and then a final finish annealing was performed. At this time, Ti
As an O 2 dispersant, sodium silicate is dispersed in water at a rate of 0.05 part by weight per 100 parts by weight, TiO 2 is added with stirring, and after sufficient dispersion treatment, MgO is added to form a slurry. did. Thereafter, when performing heat flattening, “30% colloidal silica 70 ml + 50% Al phosphate 50 ml + CrO 3 6.5” was used as an insulating film agent.
g "of solution and then 4.5 g / m 2 by weight
And baked. Table 4 shows the evaluation and test results of the glass coating properties and the magnetic properties.
【００３３】[0033]
【表３】 [Table 3]
【００３４】[0034]
【表４】 [Table 4]
【００３５】この評価・試験結果において、本発明のＴ
ｉＯ2 を分散剤で分散処理した場合には、何れも良好な
グラス被膜と磁気特性が得られている。特に、ＭｇＯの
粒子径１μｍ以下が３０％の場合には、極めてグラス被
膜が良好で、この場合にも、粒子径の小さいＴｉＯ2 の
場合には、何れもグラス被膜の均一度、張力、密着性が
優れ、磁気特性も良好であった。これに対し、ＴｉＯ2
として本発明のものを使用しても、添加量が少ない比較
例においては、グラス被膜が薄く、また、添加量が多す
ぎる比較例においては、金属斑点状欠陥や、エッジ部に
は酸化による皮膜外観のムラが多く見られ、これらの比
較例においては、被膜特性が悪いのみならず、何れも磁
気特性が不良であった。The evaluation and test results show that the T
When iO 2 was subjected to dispersion treatment with a dispersant, good glass coating and magnetic properties were obtained in all cases. In particular, when the particle diameter of MgO is 1% or less is 30%, the glass coating is extremely good. In this case, too, in the case of TiO 2 having a small particle diameter, the uniformity, tension and adhesion of the glass coating are all increased. The properties were excellent and the magnetic properties were also good. In contrast, TiO 2
Even when the present invention is used, the glass coating is thin in the comparative example where the addition amount is small, and the metal spot-like defect or the coating film is oxidized in the edge portion in the comparative example where the addition amount is too large. Many irregularities in appearance were observed, and in these comparative examples, not only the coating properties were poor but also the magnetic properties were poor.
【００３６】[0036]
【発明の効果】本発明によれば、方向性電磁鋼板の製造
において、微粒子のＴｉＯ2 を添加した焼鈍分離剤スラ
リーを適用する際、ヘキサメタ燐酸ナトリューム、コロ
イダルシリカ、珪酸ナトリューム等の分散剤を１種又は
２種以上添加することにより、ＴｉＯ2 の均一分散効果
が得られ、仕上げ焼鈍の昇温過程で、極めて良好なグラ
ス被膜形成反応向上効果が得られる。この結果、グラス
被膜特性と磁気特性の優れる方向性電磁鋼板を製造する
ことができる。According to the present invention, a dispersant such as sodium hexametaphosphate, colloidal silica, sodium silicate, etc. is used when applying an annealing separator slurry to which fine particles of TiO 2 are added in the production of grain-oriented electrical steel sheets. By adding one or more species, an effect of uniformly dispersing TiO 2 can be obtained, and a very good effect of improving a glass film forming reaction can be obtained during the temperature rise process of the finish annealing. As a result, a grain-oriented electrical steel sheet having excellent glass coating properties and magnetic properties can be manufactured.
───────────────────────────────────────────────────── フロントページの続き (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 Ｆターム(参考） 4K033 AA02 JA04 LA01 LA02 LA04 MA00 5E041 AA02 BC01 CA02 HB09 HB11 NN05 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Shingo Okada, Inventor 1-1, Tobata-cho, Tobata-ku, Kitakyushu-shi, Fukuoka Prefecture Inside Nippon Steel Corporation Yawata Works (72) Inventor, Osamu Tanaka Ogata, Kitakyushu-shi, Fukuoka 46 Nakahara, 59 Nippon Steel Plant Design Co., Ltd. F term (reference) 4K033 AA02 JA04 LA01 LA02 LA04 MA00 5E041 AA02 BC01 CA02 HB09 HB11 NN05
Claims (5)
塗布し、仕上げ焼鈍の後、絶縁皮膜処理を行う方向性電
磁鋼板の製造方法において、ＭｇＯ１００重量部に対
し、ＴｉＯ2 を０．３〜１０重量部、及び、ヘキサメタ
燐酸ナトリューム、コロイダルシリカ、珪酸ナトリュー
ムの１種又は２種以上を０．００２５〜１．０重量部添
加した水スラリーを、攪拌後、前記脱炭焼鈍後の鋼板の
表面に塗布し、その後、仕上げ焼鈍をすることを特徴と
するグラス被膜特性及び磁気特性の優れる方向性電磁鋼
板の製造方法。1. A coated with the annealing separator to the surface of the steel sheet after decarburization annealing, after the final annealing, in the manufacturing method of a grain-oriented electrical steel sheet to perform insulation coating treatment, to MgO100 parts, the TiO 2 0 0.3 to 10 parts by weight, and a water slurry to which 0.0025 to 1.0 part by weight of one or more of sodium hexametaphosphate, colloidal silica and sodium silicate are added, after stirring, after the decarburizing annealing, A method for producing a grain-oriented electrical steel sheet having excellent glass coating properties and magnetic properties, which is applied to the surface of a steel sheet and then subjected to finish annealing.
サメタ燐酸ナトリューム、コロイダルシリカ、珪酸ナト
リュームの１種又は２種以上を水に分散させ、次いで、
攪拌しながら、前記０．３〜１０重量部のＴｉＯ2 を分
散させ、その後、前記１００重量部のＭｇＯを分散さ
せ、水スラリーとすることを特徴とする請求項１記載の
グラス被膜特性及び磁気特性の優れる方向性電磁鋼板の
製造方法。2. One or two or more of 0.0025 to 1.0 parts by weight of sodium hexametaphosphate, colloidal silica and sodium silicate are dispersed in water,
2. The glass coating properties and magnetic properties according to claim 1, wherein said 0.3 to 10 parts by weight of TiO2 is dispersed with stirring, and then said 100 parts by weight of MgO is dispersed to form a water slurry. A method for producing grain-oriented electrical steel sheets with excellent properties.
以上であることを特徴とする請求項１又は２記載のグラ
ス被膜特性及び磁気特性の優れる方向性電磁鋼板の製造
方法。3. The specific surface area of the TiO 2 is 15 m 2 / g.
3. The method for producing a grain-oriented electrical steel sheet having excellent glass coating properties and magnetic properties according to claim 1 or 2.
ｍ以下であることを特徴とする請求項１、２又は３記載
のグラス被膜特性及び磁気特性の優れる方向性電磁鋼板
の製造方法。4. The TiO 2 has an average particle size of 0.15 μm.
The method for producing a grain-oriented electrical steel sheet having excellent glass coating properties and magnetic properties according to claim 1, 2 or 3.
以下１０％以上で、且つ、水和水分１〜３％のＭｇＯを
用いることを特徴とする請求項１、２、３又は４記載の
グラス被膜特性及び磁気特性の優れる方向性電磁鋼板の
製造方法。5. A particle size of 1 μm as a main component of the annealing separating agent.
The method for producing a grain-oriented electrical steel sheet having excellent glass coating properties and magnetic properties according to claim 1, 2, 3 or 4, wherein MgO having a hydration moisture of 1 to 3% is used. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000002864A JP2001192738A (en) | 2000-01-11 | 2000-01-11 | Method for producing grain oriented silicon steel sheet excellent in glass film characteristic and magnetic property |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000002864A JP2001192738A (en) | 2000-01-11 | 2000-01-11 | Method for producing grain oriented silicon steel sheet excellent in glass film characteristic and magnetic property |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001192738A true JP2001192738A (en) | 2001-07-17 |
Family
ID=18531915
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000002864A Withdrawn JP2001192738A (en) | 2000-01-11 | 2000-01-11 | Method for producing grain oriented silicon steel sheet excellent in glass film characteristic and magnetic property |
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| Country | Link |
|---|---|
| JP (1) | JP2001192738A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009001685A (en) * | 2007-06-21 | 2009-01-08 | Toreede Service:Kk | Aqueous complete inorganic alkali metal silicate composition, aqueous complete inorganic alkali silicate composition aqueous solution, aqueous coating agent, aqueous solution of aqueous coating agent, complete inorganic colored coating, binder for high temperature heat resistant coating, and method for using aqueous complete inorganic alkali metal silicate compound |
| CN112185640A (en) * | 2020-09-23 | 2021-01-05 | 江西艾特磁材有限公司 | Method for coating magnetic powder core with sodium silicate |
-
2000
- 2000-01-11 JP JP2000002864A patent/JP2001192738A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009001685A (en) * | 2007-06-21 | 2009-01-08 | Toreede Service:Kk | Aqueous complete inorganic alkali metal silicate composition, aqueous complete inorganic alkali silicate composition aqueous solution, aqueous coating agent, aqueous solution of aqueous coating agent, complete inorganic colored coating, binder for high temperature heat resistant coating, and method for using aqueous complete inorganic alkali metal silicate compound |
| JP4668954B2 (en) * | 2007-06-21 | 2011-04-13 | 株式会社トレードサービス | Aqueous complete inorganic alkali metal silicate composition, aqueous complete inorganic alkali metal silicate composition aqueous solution, aqueous coating agent, aqueous solution of aqueous coating agent, complete inorganic colored paint, binder for high temperature heat resistant paint, aqueous complete inorganic alkali metal silicate compound How to use |
| CN112185640A (en) * | 2020-09-23 | 2021-01-05 | 江西艾特磁材有限公司 | Method for coating magnetic powder core with sodium silicate |
| CN112185640B (en) * | 2020-09-23 | 2023-01-24 | 江西艾特磁材有限公司 | Method for coating magnetic powder core with sodium silicate |
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