JP3524058B2 - Method for manufacturing oriented silicon steel sheet with insulating film having excellent space factor and seizure resistance - Google Patents
Method for manufacturing oriented silicon steel sheet with insulating film having excellent space factor and seizure resistanceInfo
- Publication number
- JP3524058B2 JP3524058B2 JP2000403125A JP2000403125A JP3524058B2 JP 3524058 B2 JP3524058 B2 JP 3524058B2 JP 2000403125 A JP2000403125 A JP 2000403125A JP 2000403125 A JP2000403125 A JP 2000403125A JP 3524058 B2 JP3524058 B2 JP 3524058B2
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- particle size
- space factor
- silicon steel
- oriented silicon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
- H01F1/147—Alloys characterised by their composition
- H01F1/14766—Fe-Si based alloys
- H01F1/14775—Fe-Si based alloys in the form of sheets
- H01F1/14783—Fe-Si based alloys in the form of sheets with insulating coating
Landscapes
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Soft Magnetic Materials (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Chemical Treatment Of Metals (AREA)
- Manufacturing Of Steel Electrode Plates (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、方向性珪素鋼板を
所定の形状に成形した後、成形時に導入される加工歪を
除去するために焼鈍を施す、いわゆる巻き鉄心用方向性
珪素鋼板の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the production of a so-called grain oriented silicon steel sheet for wound iron core, which is produced by forming a grain-oriented silicon steel sheet into a predetermined shape and then annealing it to remove work strain introduced during the forming. It is about the method.
【０００２】[0002]
【従来の技術】方向性珪素鋼板は主に変圧器の鉄心材料
として用いられる。変圧器用鉄心製作法には大きく分け
て２種類の方法がある。その一つは所定の形状と寸法に
調製した方向性珪素鋼板を積層して鉄心を製作する積み
鉄心法であり、他の一つは所定の形状と寸法に調製した
方向性珪素鋼板を円筒状に巻き取り、鉄心とする巻き鉄
心法である。2. Description of the Related Art Grain-oriented silicon steel sheets are mainly used as core materials for transformers. There are roughly two types of manufacturing methods for iron cores for transformers. One of them is a laminated iron core method in which a grain-oriented silicon steel sheet prepared in a predetermined shape and size is laminated to manufacture an iron core, and the other one is a grain-oriented silicon steel sheet prepared in a predetermined shape and size in a cylindrical shape. It is a winding iron core method in which the iron core is wound around.
【０００３】このうち後者の巻き鉄心法は次に述べるよ
うな工程を経る。まず、方向性珪素鋼板を所定の幅に剪
断後、円筒形に巻き取り、次いで、この円筒状に巻き取
ったもの（以後、コアと呼ぶ）に曲げ加工を施し、所定
の形態に成形する。この時、曲げ加工に伴い、鋼板に機
械的歪みが導入されるために導入された歪により鉄心特
性が劣化してしまう。そのため、歪みを取り除くために
コアに対し焼鈍が施される。焼鈍されたコアは一旦、展
開される。展開された焼鈍済み鋼板は銅線等の間に挿入
され変圧器となる。このコア展開と銅線への巻き込みか
らなる一連の作業はレーシング作業と呼ばれる。Of these, the latter wound iron core method goes through the following steps. First, a grain-oriented silicon steel sheet is sheared to a predetermined width and then rolled up into a cylindrical shape, and then this rolled up cylindrical shape (hereinafter referred to as a core) is subjected to bending processing to be formed into a predetermined shape. At this time, mechanical stress is introduced into the steel sheet with the bending work, and thus the introduced strain deteriorates the iron core characteristics. Therefore, the core is annealed to remove the strain. The annealed core is once expanded. The expanded annealed steel sheet is inserted between copper wires or the like to form a transformer. A series of work consisting of core unwinding and winding on a copper wire is called lacing work.
【０００４】レーシング作業は変圧器製造工程において
生産性を左右する重要な工程である。この作業の際、コ
ア展開に時間を要すると生産性が低下してしまう。その
ため、焼鈍されたコアは展開し易いことが望まれてい
る。ところが、時として焼鈍済みコアにおいて鋼板同士
が焼き付きと呼ぶ一種の焼き付き現象を起こすことがあ
る。鋼板同士が焼き付きを起こすとコア展開に多大の労
力と時間が必要となり、生産性を低下させてしまう。そ
こで、このような焼き付き現象を誘起させない技術とし
て以下に示す技術が開示されている。The lacing operation is an important process that affects productivity in the transformer manufacturing process. In this work, if it takes time to develop the core, the productivity will be reduced. Therefore, it is desired that the annealed core be easily developed. However, in some cases, in the annealed core, a kind of seizure phenomenon occurs in which steel sheets are referred to as seizure. If the steel sheets stick to each other, a great deal of labor and time are required to develop the core, which lowers the productivity. Therefore, the following technology is disclosed as a technology that does not induce such a burn-in phenomenon.
【０００５】例えば、塗布液中に粉末を添加する技術と
して次のようなものがある。まず、特開昭５２−２５２
９６号公報においては、コロイド状シリカ、第１リン酸
塩、クロム酸を主体とする水分散液に一次粒子径７０〜
５００Å（７〜５０nm）、見掛け比重１００ｇ／リット
ル以下のＳｉＯ2 ，Ａｌ2 Ｏ3 ，ＴｉＯ2 粒子の１種ま
たは２種以上を添加する技術が提案されている。次に、
特開昭５３−６３３８号公報においては、リチウムシリ
ケート水溶液中にアルミナ、シリカ、チタニア、マイカ
の粉末の１種を添加する技術が提案されている。また、
特開昭５４−１４３７３７号公報においては、コロイド
状シリカ、リン酸アルミニウム、ホウ酸、硫酸塩を主体
とする水分散液に、一次粒子径１０００Å（１００nm）
以下の超微粒のＳｉＯ2 ，Ａｌ2 Ｏ3 ，ＴｉＯ2 粒子１
種または２種以上を添加する技術が提案されている。さ
らには、特開平４−１６５０８２号公報において、リン
酸塩、クロム酸、粒子径５０nm以下のコロイド状シリカ
を主体とする塗布液に、粒子径が５〜２０００nmの非コ
ロイド状の固形物を添加する技術が提案されている。上
述の塗布液中への粉末添加技術とは別に、比較的小さな
粒径と比較的大きな粒径をもつコロイド状シリカを使用
する技術として特開平３−３９４８４号公報において、
リン酸塩、クロム酸を主体とする水分散液に、粒子径２
０nm以下のコロイド状シリカと粒子径８０〜２０００ｍ
μｍ（８０nm〜２０００nm）のコロイド状シリカを添加
する技術も提案されている。For example, there are the following techniques for adding powder to the coating liquid. First, JP-A-52-252
In Japanese Patent Laid-Open No. 96-96, a primary particle diameter of 70 to 70 is added to an aqueous dispersion mainly containing colloidal silica, primary phosphate and chromic acid.
A technique has been proposed in which one or more particles of SiO 2 , Al 2 O 3 , and TiO 2 particles having an apparent specific gravity of 500 g (7 to 50 nm) and an apparent specific gravity of 100 g / liter or less are added. next,
Japanese Patent Application Laid-Open No. 53-6338 proposes a technique of adding one kind of powder of alumina, silica, titania, and mica to an aqueous solution of lithium silicate. Also,
In Japanese Unexamined Patent Publication (Kokai) No. 54-143737, an aqueous dispersion mainly containing colloidal silica, aluminum phosphate, boric acid and sulfate has a primary particle diameter of 1000Å (100 nm).
The following ultrafine SiO 2 , Al 2 O 3 , and TiO 2 particles 1
Techniques for adding one species or two or more species have been proposed. Further, in JP-A-4-165082, a non-colloidal solid substance having a particle diameter of 5 to 2000 nm is added to a coating liquid mainly composed of phosphate, chromic acid and colloidal silica having a particle diameter of 50 nm or less. The technology to do is proposed. In addition to the above-mentioned technique of adding powder to the coating liquid, JP-A-3-39484 discloses a technique of using colloidal silica having a relatively small particle size and a relatively large particle size.
Aqueous dispersion mainly composed of phosphate and chromic acid, with particle size 2
Colloidal silica of 0 nm or less and particle size 80 to 2000 m
A technique for adding colloidal silica of μm (80 nm to 2000 nm) has also been proposed.
【０００６】一方、本発明が対象にしている一方向性珪
素鋼板においては、歪み取り焼鈍焼き付き性の他に、占
積率と呼ばれる製品指標も重要視される。占積率とは、
方向性珪素鋼板を積層し、鉄心を製作した際、鉄心厚さ
全体に占める鉄の割合を示すものである。鋼板表面の絶
縁皮膜が厚過ぎたり、皮膜あるいは鋼板自体の凹凸が激
しすぎるとこの割合が低下してしまう。占積率が低いと
いうことは、同一鉄心厚さで比較した場合、鉄の占める
部分が少ないことを意味する。鉄の占める部分が少ない
と、変圧器内部で鉄心が電磁誘導の法則に従い、電圧変
換ユニットとして作動する時、磁束が通りにくくなる。
そうなると、電圧変換の際、熱エネルギー損失が増大し
てしまう。そのため、占積率は高い方が望ましい。On the other hand, in the unidirectional silicon steel sheet targeted by the present invention, in addition to the strain relief annealing seizure property, a product index called a space factor is also considered important. What is the space factor?
When an iron core is manufactured by laminating grain-oriented silicon steel sheets, the ratio of iron to the entire iron core thickness is shown. If the insulating coating on the surface of the steel sheet is too thick, or if the coating or the unevenness of the steel sheet itself is too severe, this ratio will decrease. The low space factor means that the iron occupies a small portion when compared with the same iron core thickness. When the portion occupied by iron is small, the magnetic flux becomes difficult to pass through when the iron core operates as a voltage conversion unit according to the law of electromagnetic induction inside the transformer.
Then, the heat energy loss increases during voltage conversion. Therefore, a higher space factor is desirable.
【０００７】こうした耐焼き付き性に優れ、かつ占積率
にも優れる方向性珪素鋼板用の絶縁皮膜として、本発明
らは特開２０００−２６９７９号公報において平均粒径
２μｍ超２０μｍ以下の無機鉱物質粒子を塗布液中固形
分比率で０．０２質量％以上２０質量％以下含有させる
方法を提案した。As an insulating film for grain-oriented silicon steel sheet which is excellent in seizure resistance and space factor, the present inventors disclosed in JP-A-2000-26979 an inorganic mineral substance having an average particle size of more than 2 μm and 20 μm or less. A method has been proposed in which the particles are contained in the coating liquid in a solid content ratio of 0.02% by mass or more and 20% by mass or less.
【０００８】[0008]
【発明が解決しようとする課題】本発明らは、上述の技
術を適用し実用化に向けての検討を進める中で、無機鉱
物質粒子の平均粒径を制御すれば耐焼き付き性は良好で
あるものの、時として占積率が悪いという現象に遭遇
し、この占積率低下を引き起こさない技術の開発に取り
組んだ。The present invention, while applying the above-mentioned technology and proceeding with the examination for practical use, has good seizure resistance if the average particle size of the inorganic mineral particles is controlled. However, I sometimes encountered a phenomenon that the space factor was poor, and I worked on developing a technology that does not cause this decrease in the space factor.
【０００９】[0009]
【課題を解決するための手段】本発明は、上記課題を解
決するためになされたもので、その要旨は以下の要件よ
りなる。
（１）仕上げ焼鈍済みの方向性珪素鋼板に対し、無機鉱
物質粒子を含有する塗布液を塗布し焼き付けることによ
り鋼板上に絶縁皮膜を形成する方向性珪素鋼板の製造方
法において、前記無機鉱物質粒子として、レーザー散乱
・回折式粒度分布測定法により測定された５０％中心粒
径が２μｍ超２０μｍ以下で、かつ９０％積算粒径と５
０％中心粒径の比率が１０以下である無機鉱物質粒子を
使用することを特徴とする占積率と耐焼き付き性に優れ
る絶縁皮膜付き方向性珪素鋼板の製造方法。
（２）絶縁皮膜と地鉄金属との間にフォルステライト、
スピネルのいずれか一方または両方を主体とする皮膜を
有することを特徴とする（１）の占積率と耐焼き付き性
に優れる方向性珪素鋼板の製造方法。
（３）絶縁皮膜と地鉄金属との間にフォルステライト、
スピネルのいずれか一方または両方を主体とする皮膜を
有しないことを特徴とする（１）の占積率と耐焼き付き
性に優れる方向性珪素鋼板の製造方法。
（４）皮膜と地鉄金属との界面凹凸がＲａで０．２μｍ
以下であることを特徴とする（３）の占積率と耐焼き付
き性に優れる方向性珪素鋼板の製造方法。The present invention has been made to solve the above problems, and the gist thereof is as follows. (1) In the method for producing a grain-oriented silicon steel sheet, wherein a finish-annealed grain-oriented silicon steel sheet is coated with an application liquid containing inorganic mineral particles and baked to form an insulating film on the steel sheet. As the particles, the 50% central particle size measured by a laser scattering / diffraction type particle size distribution measuring method is more than 2 μm and 20 μm or less, and 90% integrated particle size and 5
A method for producing a grain-oriented silicon steel sheet with an insulating film having excellent space factor and seizure resistance, characterized by using inorganic mineral particles having a 0% center particle diameter ratio of 10 or less. (2) Forsterite between the insulating film and the base metal,
A method for producing a grain-oriented silicon steel sheet having an excellent space factor and seizure resistance as set forth in (1), characterized in that the spinel has a film mainly containing either one or both of them. (3) Forsterite between the insulating film and the base metal,
The method for producing a grain-oriented silicon steel sheet having excellent space factor and seizure resistance of (1), which is characterized by not having a film mainly containing one or both of spinel. (4) Ra of the unevenness of the interface between the film and the base metal is 0.2 μm
(3) A method for producing a grain-oriented silicon steel sheet having excellent space factor and seizure resistance, characterized in that:
【００１０】[0010]
【発明の実施の形態】発明者らは占積率低下を最小化す
る技術開発に取り組む中、絶縁皮膜形成用の塗布液中に
添加する無機鉱物質粒子の粒径分布、特に、粒径の大き
な部分の比率が占積率に大きく影響していることを突き
止めた。以下、その取り組みについて述べる。BEST MODE FOR CARRYING OUT THE INVENTION While the inventors are working on the development of technology for minimizing the decrease in space factor, the particle size distribution of inorganic mineral particles added to a coating solution for forming an insulating film, We have found that the proportion of a large part has a great influence on the space factor. Below, we will describe our efforts.
【００１１】一般に２相界面の焼き付き性はその接触面
積に依存する。そのため、２相を接触させ、高温に保持
した場合、接触面積が大きいと焼き付きを起こし易く、
接触面積が小さいと焼き付きを起こし難い。焼き付き防
止のため、接触面積を低減させる方法の１つとして、表
面に凹凸を付与する方法がある。特開２０００−２６９
７９号公報はこの技術思想に基づき、塗布液中に無機鉱
物質粒子を添加する方法である。一方、占積率の観点か
らは表面凹凸はできるだけ少ない方が好ましい。つま
り、占積率の観点からは絶縁皮膜表面は平坦な方が望ま
しい。Generally, the seizure property of the two-phase interface depends on the contact area. Therefore, when the two phases are brought into contact with each other and kept at a high temperature, a large contact area easily causes seizure,
If the contact area is small, it is difficult to cause seizure. As one of the methods for reducing the contact area to prevent seizure, there is a method of giving unevenness to the surface. JP-A-2000-269
Japanese Patent Publication No. 79 is a method of adding inorganic mineral particles to a coating liquid based on this technical idea. On the other hand, from the viewpoint of space factor, it is preferable that the surface unevenness is as small as possible. That is, it is desirable that the surface of the insulating film is flat from the viewpoint of the space factor.
【００１２】こうした相反する技術的要請を解決する技
術的切り口として、塗布液中に添加する無機鉱物質粒子
の粒度分布に着目した。発明者らは占積率を支配してい
るのは無機鉱物質粒子の平均粒径に加え、その粒子母集
団が含む、粒径の大きな粒子ではないかと推測した。絶
縁皮膜表面の大部分の表面凹凸形成状況は添加した無機
鉱物質粒子集団の平均粒径と対応する。しかしながら、
そのうち、添加した粒子母集団の中に平均粒径と比較
し、著しく大きな粒子径をもつ粒子が存在すると、その
粒子により形成される皮膜表面凹凸は極めて大きなもの
となる。そうした大きな凹凸は皮膜同士の接触面積を低
減させる効果は大きいので、耐焼き付き性を向上させ
る。しかしながら、占積率の観点からみるとこうした、
言うなれば粗大突起が皮膜表面に散在すると、鋼板同士
の間隔が広がるため、板間に大きな空間が生じ占積率は
著しく低下してしまう。As a technical approach for solving these conflicting technical requirements, attention was paid to the particle size distribution of the inorganic mineral particles added to the coating solution. The inventors have speculated that the space factor is governed by particles having a large particle size included in the particle population in addition to the average particle size of the inorganic mineral particles. Most of the surface irregularity formation conditions on the surface of the insulating film correspond to the average particle size of the added inorganic mineral particle population. However,
Among them, when particles having a remarkably large particle size are present in the added particle population as compared with the average particle size, the unevenness of the coating surface formed by the particles becomes extremely large. Such large unevenness has a great effect of reducing the contact area between the coatings, and therefore improves the seizure resistance. However, from the viewpoint of space factor,
In other words, if the coarse projections are scattered on the surface of the coating film, the gap between the steel plates widens, resulting in a large space between the plates, resulting in a significant decrease in the space factor.
【００１３】発明者らはこのような考え方の下に、耐焼
き付き性を確保しつつ、占積率の低下を最小化しうる無
機鉱物質粒子の粒度分布を実験的に求める試みを次のよ
うな手順で行なった。仕上げ焼鈍を施し二次再結晶済み
の一次皮膜（フォルステライトとスピネル主体の無機鉱
物質で構成された皮膜）付きの鋼板を多数用意した。こ
の鋼板にクロム酸とリン酸アルミニウムを合計で５０質
量％含有する水溶液５０mlと、濃度２０質量％のコロイ
ド状シリカ水分散液１００mlを主体とし、これに平均粒
子径３．５μｍのシリカ粒子を０．５ｇ配合した液を塗
布し乾燥させた。Based on such an idea, the inventors have made the following attempt to experimentally obtain a particle size distribution of inorganic mineral particles capable of minimizing seizure resistance and minimizing the decrease in space factor. The procedure was done. A large number of steel plates with a primary film (a film composed of forsterite and an inorganic mineral mainly composed of spinel) that had been subjected to finish annealing and had been subjected to secondary recrystallization were prepared. This steel sheet was mainly composed of 50 ml of an aqueous solution containing 50% by mass of chromic acid and aluminum phosphate and 100 ml of an aqueous dispersion of colloidal silica having a concentration of 20% by mass, to which silica particles having an average particle diameter of 3.5 μm were added. A liquid containing 0.5 g was applied and dried.
【００１４】この時、平均粒子径、即ち、レーザー散乱
・回折式粒度分布測定法において、累積積算率でいう５
０％中心粒径はどれも同じ３．５μｍであるが、粒度分
布の広がりが異なり、粒径の大きな粒子の含有割合が異
なる粒度分布をもつもの５種類を用意し、それぞれ塗布
液に添加した。ここで、粒径の大きな粒子の割合は累積
積算率９０％の粒径で評価した。累積積算率５０％もし
くは９０％とは、体積換算の粒度分布ヒストグラムにお
いて、粒径の小さい集団からその存在割合に応じ、粒子
体積を積算していき、母集団全体の合計体積のちょうど
５０％もしくは９０％の体積に達した時の粒径を示す。
したがって、９０％粒径が大きいということは、この粒
径以上の粗大な粒径をもつ粒子が全体の１０％存在する
ことを意味する。そのため、５０％中心粒径が同じであ
っても９０％粒径が大きな粒子群の場合、粗大な粒子に
起因する大きな表面凹凸が絶縁皮膜に形成されるものと
考えた。At this time, the average particle diameter, that is, the cumulative integration rate of 5 in the laser scattering / diffraction type particle size distribution measuring method.
The 0% central particle diameters are all the same 3.5 μm, but five kinds having different particle size distributions with different broadening of particle size distribution and different content ratios of particles having a large particle diameter were added to the coating liquid. . Here, the ratio of particles having a large particle size was evaluated by a particle size having a cumulative integration rate of 90%. The cumulative integration rate of 50% or 90% means that in a volume-converted particle size distribution histogram, the particle volume is integrated according to the existence ratio of a group having a small particle size, and is exactly 50% of the total volume of the entire population or The particle size when 90% volume is reached is shown.
Therefore, the fact that the 90% particle size is large means that 10% of all particles having a coarse particle size equal to or larger than this particle size exist. Therefore, it was considered that in the case of a particle group having a large 90% particle diameter even if the 50% central particle diameter is the same, large surface irregularities due to coarse particles are formed in the insulating film.
【００１５】次に、塗布乾燥済みの鋼板を８３５℃で３
０秒間、窒素雰囲気中で焼鈍し、鋼板表面に絶縁皮膜を
形成した。このようにして調製した試料について、以下
のような方法で焼き付き性と占積率を評価した。焼き付
き性の評価は次のような方法で行った。まず、絶縁皮膜
を形成した一方向性珪素鋼板から短辺３cm、長辺４cmの
試料を多数切り出した。次に、これらの試料の短辺と長
辺とが互い違いになるように積層した。このように積層
すると試料同士が丁度３cm角で接触することになる。従
って接触面積は９cm2 となる。この積層したものに６０
kg／cm2 の荷重をかけボルトで固定した。ついで、これ
に温度８００℃、均熱時間２時間の焼鈍を施した。室温
まで冷却し、荷重とボルトを外した後、吸盤付きのバネ
秤で積層した鋼板を鋼板の法線方向に引っ張って、１枚
ずつ引き剥がし、剥がれた時のバネ秤の値を読み取り、
剥離力を求めた。試料は１５枚用意し、それらの剥離力
の平均値を求めた。このような試験法で求めた剥離力は
実際のコア展開における展開しやすさを反映しているも
のと考えられる。Next, the coated and dried steel sheet is heated at 835 ° C. for 3 hours.
Annealing was performed for 0 seconds in a nitrogen atmosphere to form an insulating film on the surface of the steel sheet. The seizure property and space factor of the sample thus prepared were evaluated by the following methods. The image sticking property was evaluated by the following method. First, a large number of samples each having a short side of 3 cm and a long side of 4 cm were cut out from an unidirectional silicon steel sheet on which an insulating film was formed. Next, these samples were laminated so that the short side and the long side were staggered. When laminated in this way, the samples will contact each other at exactly 3 cm square. Therefore, the contact area is 9 cm 2 . 60 for this stack
A load of kg / cm 2 was applied and fixed with bolts. Then, this was annealed at a temperature of 800 ° C. for a soaking time of 2 hours. After cooling to room temperature, removing the load and bolts, pull the laminated steel plates with a spring balance with a suction cup in the normal direction of the steel plate, peel off one by one, read the value of the spring balance when peeled off,
The peel strength was determined. Fifteen samples were prepared, and the average value of their peeling forces was determined. It is considered that the peeling force obtained by such a test method reflects the ease of deployment in actual core deployment.
【００１６】また、占積率の評価は次のような方法で行
った。まず、焼き付き性評価用試料と同じように絶縁皮
膜を形成した一方向性珪素鋼板から短辺３cm、長辺１５
cmの試料を多数切り出した。これらの試料を積層し、一
定の荷重を印加した後、その時の厚さを測定した。次
に、この厚さ分すべてが鉄で構成されていると仮定し、
質量を算出した。（算出質量）。このとき密度は７．６
５ｇ／ｍ2 として計算した。一方でこの試料の実質量も
測定し、算出質量に対する実質量の比率を％で表したも
のを占積率とした。このような試験法で求めた占積率は
実際の鉄心における占積率を反映しているものと考えら
れる。The space factor was evaluated by the following method. First, the short side 3 cm, the long side 15 from the unidirectional silicon steel plate on which the insulating film was formed in the same manner as the seizure evaluation sample.
A large number of cm samples were cut out. After laminating these samples and applying a constant load, the thickness at that time was measured. Next, assuming that all this thickness is composed of iron,
The mass was calculated. (Calculated mass). At this time, the density is 7.6.
Calculated as 5 g / m 2 . On the other hand, the real amount of this sample was also measured, and the space factor was defined as the ratio of the real amount to the calculated mass in%. The space factor obtained by such a test method is considered to reflect the space factor in the actual iron core.
【００１７】以上のようにして評価した結果を表１に示
す。Table 1 shows the results of evaluations performed as described above.
【００１８】[0018]
【表１】 [Table 1]
【００１９】表１から次のことがわかる。まず、歪み取
り焼鈍時の耐焼き付き性を表している剥離力をみると、
いずれの粒度分布をもつシリカ粒子でも０．２１mPa
（１９ｇ）以下と小さく、良好である。次に、占積率を
みると実験番号１），２），３），４）の９０％積算粒
径が６．４μｍ、８．６μｍ、１２．５μｍ、３４．３
μｍの条件、即ち、９０％積算粒径と５０％中心粒径の
比率（９０％粒径／５０％粒径）がそれぞれ、１．８、
２．５、３．６、９．８の場合は占積率９７．３％から
９７．８％と良好である。The following can be seen from Table 1. First, looking at the peeling force, which represents the seizure resistance during strain relief annealing,
0.21 mPa for silica particles with any particle size distribution
(19 g) or less, which is small and good. Next, looking at the space factor, the 90% cumulative particle diameters of Experiment Nos. 1), 2), 3) and 4) were 6.4 μm, 8.6 μm, 12.5 μm and 34.3.
The condition of μm, that is, the ratio of 90% integrated particle size to 50% central particle size (90% particle size / 50% particle size) is 1.8,
In the cases of 2.5, 3.6, and 9.8, the space factor is good, from 97.3% to 97.8%.
【００２０】一方、実験条件５），６）の９０％積算粒
径が５１．０μｍ、８０．５μｍの条件、即ち、５０％
中心粒径と９０％積算粒径の比率が１４．６、２３．０
と１０以上の比率をもつ場合は占積率が９４．４％、９
４．１％と悪い。以上の結果から、剥離力が小さく、歪
み取り焼鈍時の耐焼き付き性に優れることと占積率が高
いこととを両立できるのは５０％中心粒径と９０％積算
粒径の比率が１０以下であることがわかった。On the other hand, in the experimental conditions 5) and 6), the 90% cumulative particle size is 51.0 μm and 80.5 μm, that is, 50%.
The ratio of the central particle size to the 90% cumulative particle size is 14.6, 23.0
And the ratio is 10 or more, the space factor is 94.4%, 9
It is as bad as 4.1%. From the above results, it is possible to achieve both a small peeling force, an excellent seizure resistance during strain relief annealing and a high space factor in which the ratio of the 50% central particle size to the 90% integrated particle size is 10 or less. I found out.
【００２１】発明者らは、更に良好な占積率をもつ方向
性珪素鋼板製品を実現すべく検討した。その結果、フォ
ルステライトやスピネルを主体とする一次皮膜のない方
が占積率が良好で、更には一次皮膜のない金属面を化学
研磨等の手法で平滑化すれば、より一層、占積率を高め
ることができるのではないかと推測し、次に述べる手順
で検証した。The inventors have conducted studies to realize a grain-oriented silicon steel sheet product having a better space factor. As a result, the space factor is better without the primary film mainly composed of forsterite or spinel, and further, if the metal surface without the primary film is smoothed by a method such as chemical polishing, the space factor is further increased. We speculated that it could be improved, and verified it by the procedure described below.
【００２２】仕上げ焼鈍を施し二次再結晶済みの一次皮
膜（フォルステライトとスピネル主体の無機鉱物質で構
成された皮膜）付きの鋼板を多数用意した。この鋼板を
弗化アンモニウムと硫酸の混酸に浸漬することにより、
鋼板表面に一次皮膜のない二次再結晶済みの方向性珪素
鋼板を作製した。ついで、一部の試料については弗化水
素と過酸化水素を主体とする水溶液を用いて化学研磨
し、最終的に、金属表面の表面粗さ：Ｒａを０．２５μ
ｍ（化学研磨なし）、０．２０μｍ、０．１２μｍ、
０．０５μｍに調製した。この表面粗さ（Ｒａ）は、二
次元粗度計を用いて評価した。こうして調製した鋼板
に、クロム酸入とリン酸マグネシウムを合計で５０質量
％含有する水溶液５０mlと、濃度２０質量％のコロイド
状シリカ水分散液１００mlを主体とする液を塗布し、乾
燥した。この時、５０％中心粒子径は４．５μｍで同一
で、粒度分布が異なり、９０％積算粒径／５０％中心粒
径の比率がそれぞれ５．５、９．８、１３．５のアルミ
ナ粒子を０．４ｇ添加した。次に、これらを８３５℃で
３０秒間、窒素雰囲気中で焼鈍し、鋼板表面に絶縁皮膜
を形成した。このようにして調製した試料について、前
述の方法で耐焼き付き性と占積率を評価した。A large number of steel plates with a primary film (a film composed of forsterite and an inorganic mineral mainly composed of spinel) which had been subjected to finish annealing and which had been subjected to secondary recrystallization were prepared. By immersing this steel sheet in a mixed acid of ammonium fluoride and sulfuric acid,
A secondary recrystallized grain-oriented silicon steel sheet having no primary coating on the surface of the steel sheet was produced. Then, some of the samples were chemically polished using an aqueous solution mainly containing hydrogen fluoride and hydrogen peroxide, and finally the surface roughness of the metal surface: Ra was 0.25 μm.
m (without chemical polishing), 0.20 μm, 0.12 μm,
The thickness was adjusted to 0.05 μm. The surface roughness (Ra) was evaluated using a two-dimensional roughness meter. On the thus-prepared steel sheet, 50 ml of an aqueous solution containing 50 mass% of chromic acid and magnesium phosphate in total, and 100 ml of an aqueous dispersion of colloidal silica having a concentration of 20 mass% were applied and dried. At this time, the 50% central particle diameter was 4.5 μm, the particle diameter distribution was different, and the 90% cumulative particle diameter / 50% central particle diameter ratios were 5.5, 9.8, and 13.5, respectively. 0.4g was added. Next, these were annealed at 835 ° C. for 30 seconds in a nitrogen atmosphere to form an insulating film on the surface of the steel sheet. The seizure resistance and the space factor of the sample thus prepared were evaluated by the methods described above.
【００２３】評価結果を表２に示す。The evaluation results are shown in Table 2.
【００２４】[0024]
【表２】 [Table 2]
【００２５】表２から次のことがわかる。まず、歪み取
り焼鈍時の耐焼き付き性を表している剥離力をみると、
いずれの条件においても剥離力は０．２１mPa （１９
ｇ）以下と小さく、アルミナ粒子を添加したこれらすべ
ての条件において耐焼き付き性は非常に良好である。次
に占積率について、それぞれ素材別に述べる。The following can be seen from Table 2. First, looking at the peeling force, which represents the seizure resistance during strain relief annealing,
The peeling force is 0.21 mPa (19
It is as small as g) or less, and the seizure resistance is very good under all of these conditions in which alumina particles are added. Next, the space factor is described for each material.
【００２６】一次皮膜付き試料群（実験番号１），
２），３））において、９０％積算粒径／５０％中心粒
径比率が５．５（実験番号１））と９．８（実験番号
２））の条件では、占積率はそれぞれ、９７．８％、９
７．７％と高く、良好である。一方、９０％積算粒径／
５０％中心粒径比率が１３．５の条件では、占積率は９
４．９％と著しく低い。Sample group with primary coating (Experiment No. 1),
2), 3)), the 90% cumulative particle size / 50% central particle size ratio is 5.5 (Experiment No. 1)) and 9.8 (Experiment No. 2)), the space factor is 97.8%, 9
It is as good as 7.7%. On the other hand, 90% cumulative particle size /
When the 50% center particle size ratio is 13.5, the space factor is 9
Remarkably low at 4.9%.
【００２７】こうした傾向は酸洗によって一次皮膜を除
去した試料群（実験番号４），５），６））においても
同様で、９０％積算粒径／５０％中心粒径比率が５．５
（実験番号４））と同比率が９．８（実験番号５））で
は、占積率が９８．２％、９８．１％と非常に高く、良
好であるのに対し、９０％積算粒径／５０％中心粒径比
率が１３．５（実験番号６））の条件では、占積率は９
４．８％と低く、良好でない。This tendency is the same in the sample groups (Experiment No. 4), 5), 6)) in which the primary film is removed by pickling, and the 90% cumulative particle diameter / 50% central particle diameter ratio is 5.5.
(Experiment No. 4)), which has the same ratio as 9.8 (Experiment No. 5)), has a very high space factor of 98.2% and 98.1%, which is good, while 90% integrated particles Under the condition of (diameter / 50% center particle size ratio 13.5 (Experiment No. 6)), the space factor is 9
It is as low as 4.8%, which is not good.
【００２８】一次皮膜付き試料を酸洗した後、さらに化
学研磨によって鋼板表面を平坦にした試料群（実験番号
７）から実験番号１５））についても、こうした傾向は
見られた。即ち、９０％積算粒径／５０％中心粒径比率
が５．５（実験番号７），１０），１３））と９．８
（実験番号８），１１），１４））では占積率は９８．
３％以上と良好であるが、同比率が１３．５（実験番号
９），１２），１５））では占積率は９４．９％と非常
に低く、良好でない。This tendency was also observed in the sample group (Experiment No. 7) to Experiment No. 15)) in which the steel sheet surface was flattened by chemical polishing after pickling the sample with the primary coating. That is, the ratio of 90% cumulative particle diameter / 50% central particle diameter is 5.5 (Experiment No. 7), 10), 13)) and 9.8.
In (Experiment No. 8), 11), 14)), the space factor is 98.
It is good at 3% or more, but when the ratio is 13.5 (Experiment No. 9), 12), 15)), the space factor is very low at 94.9%, which is not good.
【００２９】以上の結果から、歪み取り焼鈍時の優れた
耐焼き付き性に維持したまま、より高い占積率をもつ絶
縁皮膜付き方向性珪素鋼板を製造するには、絶縁皮膜形
成用の塗布液の中に添加する無機鉱物質粒子の粒度分布
がレーザー散乱・回折式粒度分布測定法において、９０
％積算粒径と５０％中心粒径の比率が１０以下であるこ
とがわかった。From the above results, in order to produce a grain-oriented silicon steel sheet with an insulating film having a higher space factor while maintaining excellent seizure resistance during strain relief annealing, a coating solution for forming an insulating film is required. The particle size distribution of the inorganic mineral particles added to the powder is 90 in the laser scattering / diffraction type particle size distribution measurement method.
It was found that the ratio of the% cumulative particle diameter to the 50% central particle diameter was 10 or less.
【００３０】なお、無機鉱物質の種類は問わないが、Ｓ
ｉＯ2 ，Ａｌ2 Ｏ3 ，ＺｒＯ2 やその複合物など、構造
が熱や溶媒、荷重などに対して安定であることが重要で
ある。また、こうした効果は一次皮膜付きの二次再結晶
済みの電磁鋼板に適用しても得られるのはもちろんであ
るが、一次皮膜を酸洗によって除去した鋼板においては
より高い占積率が得られる。It should be noted that, although the type of the inorganic mineral substance does not matter, S
iO like 2, Al 2 O 3, ZrO 2 or composites thereof, it is important that the structure is stable to heat and solvents, load. Further, although such an effect can be obtained by applying it to a secondary recrystallized electromagnetic steel sheet with a primary coating, a higher space factor can be obtained in a steel sheet with the primary coating removed by pickling. .
【００３１】本発明を適用できる二次再結晶済みの一次
皮膜のない方向性珪素鋼板は一旦、生成した一次皮膜を
酸洗法等により除去しても良いし、あるいは焼鈍分離剤
であるマグネシア中に塩化物等の一次皮膜形成妨害化合
物を添加し、仕上げ焼鈍中に一次皮膜を作らないように
して作製しても良い。さらに本発明の効果は鋼板を酸洗
した後、化学研磨等の手段によって鋼板表面を平坦化す
るとより効果的で、高い占積率を得ることができる。地
鉄金属面の平坦化については化学研磨法や電解研磨法に
よっても良いし、あるいは仕上げ焼鈍純化過程の乾燥水
素雰囲気中、１２００℃、２０時間という条件を活用
し、熱エネルギーを駆動力とする熱的平坦化法を活用し
ても良い。さらには、焼鈍分離剤としてマグネシアでは
なくアルミナなど一次皮膜を形成しない化合物を使用
し、仕上げ焼鈍中に一次皮膜を形成させないようにした
上で熱的平坦化法を重畳し、金属面を平滑にしたもので
もかまわない。The secondary recrystallized grain-oriented silicon steel sheet having no primary coating to which the present invention can be applied may be obtained by temporarily removing the produced primary coating by a pickling method, or in magnesia which is an annealing separator. It may be prepared by adding a primary film formation-inhibiting compound such as chloride to the above so as not to form the primary film during finish annealing. Further, the effect of the present invention is more effective when the surface of the steel sheet is flattened by means such as chemical polishing after pickling the steel sheet, and a high space factor can be obtained. The flattening of the metal surface of the base metal may be performed by a chemical polishing method or an electrolytic polishing method, or by utilizing the condition of 1200 ° C. for 20 hours in a dry hydrogen atmosphere in the final annealing purification process, the thermal energy is used as the driving force. A thermal flattening method may be used. Furthermore, instead of magnesia, a compound that does not form a primary film, such as alumina, is used as an annealing separator, and a thermal flattening method is applied to prevent the formation of a primary film during finish annealing. It doesn't matter what you do.
【００３２】[0032]
【実施例】＜実施例１＞仕上げ焼鈍を施し二次再結晶済
みのフォルステライトとスピネルを主体とする無機鉱物
質皮膜付きの板厚０．２３mmの鋼板に濃度５０質量％の
クロム酸入りリン酸アルミニウム・マグネシウム水溶液
５０ml、濃度２０質量％のコロイド状シリカ水分散液１
００mlを塗布し乾燥させた。Example 1 A 0.23 mm-thick steel sheet with a inorganic reticulation film mainly composed of forsterite and spinel, which has been subjected to finish annealing and secondary recrystallization, and a phosphorus containing chromic acid with a concentration of 50% by mass. Aqueous aluminum / magnesium salt solution 50 ml, 20% by weight concentration of colloidal silica water dispersion 1
00 ml was applied and dried.
【００３３】この時、塗布液中に５０％中心粒子径５．
０μｍで、９０％積算粒径／５０％中心粒径比率が３．
４、４．７、９．６（以上、実施例）と２１．５（比較
例）であるシリカ粒子を０．３ｇ添加した液を用意し、
それぞれに塗布し乾燥させた。次に、これらの試料を８
３５℃で３０秒間、窒素雰囲気中で焼鈍し、鋼板表面に
絶縁皮膜を形成した。このようにして調製した試料を前
述の方法で焼き付き性と占積率を評価した。At this time, a 50% center particle diameter of 5.
At 0 μm, the ratio of 90% cumulative particle size / 50% central particle size is 3.
Prepare a liquid to which 0.3 g of silica particles of 4, 4.7, 9.6 (above, examples) and 21.5 (comparative example) was added,
Each was applied and dried. Next, these samples
Annealing was performed in a nitrogen atmosphere at 35 ° C for 30 seconds to form an insulating film on the surface of the steel sheet. The seizure property and space factor of the sample thus prepared were evaluated by the methods described above.
【００３４】結果を表３に示す。The results are shown in Table 3.
【００３５】[0035]
【表３】 [Table 3]
【００３６】表３から９０％積算粒径／５０％中心粒径
の比率が１０以下の実施例において占積率が９７．５％
以上と高く、良好であるのに対し、同比率が１０以上で
ある比較例においては占積率が９４．７％と低く、良好
でない。
＜実施例２＞仕上げ焼鈍を施し二次再結晶済みのフォル
ステライトとスピネルを主体とする無機鉱物質皮膜付き
の板厚０．３０mmの鋼板に濃度５０質量％のクロム酸入
りリン酸アルミニウム水溶液５０ml、濃度２０質量％の
コロイド状シリカ水分散液１００mlを塗布し乾燥させ
た。From Table 3, the space factor is 97.5% in the examples in which the ratio of 90% cumulative particle size / 50% central particle size is 10 or less.
In the comparative example in which the ratio is 10 or more, the space factor is as low as 94.7%, which is not good. <Example 2> Aluminum phosphide aqueous solution containing chromic acid with a concentration of 50% by mass was applied to a steel plate having a thickness of 0.30 mm with an inorganic mineral film mainly composed of forsterite and spinel that has been subjected to finish annealing and secondary recrystallization. 100 ml of an aqueous dispersion of colloidal silica having a concentration of 20% by mass was applied and dried.
【００３７】この時、塗布液中に５０％中心粒子径６．
１μｍで、９０％積算粒径／５０％中心粒径比率が２．
７、３．１、７．４（以上、実施例）と１５．５（比較
例）であるホウ酸アルミニウムシリカ粒子を０．２ｇ添
加した液を用意し、それぞれに塗布し乾燥させた。次
に、これらの試料を８３５℃で３０秒間、窒素雰囲気中
で焼鈍し、鋼板表面に絶縁皮膜を形成した。このように
して調製した試料を前述の方法で焼き付き性と占積率を
評価した。At this time, 50% center particle size of 6.
At 1 μm, 90% cumulative particle size / 50% central particle size ratio is 2.
Liquids containing 0.2 g of aluminum borate silica particles of 7, 3.1, 7.4 (above, examples) and 15.5 (comparative example) were prepared, and applied and dried. Next, these samples were annealed at 835 ° C. for 30 seconds in a nitrogen atmosphere to form an insulating film on the surface of the steel sheet. The seizure property and space factor of the sample thus prepared were evaluated by the methods described above.
【００３８】結果を表４に示す。The results are shown in Table 4.
【００３９】[0039]
【表４】 [Table 4]
【００４０】表４から９０％積算粒径／５０％中心粒径
の比率が１０以下の実施例において占積率が９７．６％
以上と高く、良好であるのに対し、同比率が１０以上で
ある比較例においては占積率が９４．８％と低く、良好
でない。
＜実施例３＞仕上げ焼鈍を施し二次再結晶済みのフォル
ステライトとスピネルを主体とする無機鉱物質皮膜付き
の板厚０．３０mmの鋼板を硫酸酸洗し、無機鉱物質皮膜
を除去した後、フッ化水素と過酸化水素を主体とする水
溶液を用いて化学研磨し、金属表面の表面粗さ：Ｒａを
０．１７μｍに調製した。こうして調製した鋼板に濃度
５０質量％のクロム酸入りリン酸アルミニウム・マグネ
シウム水溶液５０ml、濃度２０質量％のコロイド状シリ
カ水分散液１００mlを塗布し乾燥させた。From Table 4, the space factor is 97.6% in the examples in which the ratio of 90% cumulative particle size / 50% central particle size is 10 or less.
The above is high and good, but in the comparative example in which the same ratio is 10 or more, the space factor is as low as 94.8%, which is not good. <Example 3> After finishing annealing, a secondary recrystallized forsterite and a spinel-based inorganic-mineral-material-coated steel sheet having a thickness of 0.30 mm are subjected to sulfuric acid pickling to remove the inorganic mineral coating. The surface roughness Ra of the metal surface was adjusted to 0.17 μm by chemical polishing using an aqueous solution mainly containing hydrogen fluoride and hydrogen peroxide. The thus prepared steel sheet was coated with 50 ml of a 50% by weight aqueous solution of aluminum / magnesium phosphate containing chromic acid and 100 ml of a 20% by weight aqueous colloidal silica dispersion, and dried.
【００４１】この時、塗布液中に５０％中心粒子径２．
４μｍで、９０％積算粒径／５０％中心粒径比率が５．
２、８．１、９．７（以上、実施例）と１８．１（比較
例）であるジルコニア粒子を１．５ｇ添加した液を用意
し、それぞれに塗布し乾燥させた。次に、これらの試料
を８３５℃で３０秒間、窒素雰囲気中で焼鈍し、鋼板表
面に絶縁皮膜を形成した。このようにして調製した試料
を前述の方法で焼き付き性と占積率を評価した。At this time, 50% center particle diameter in the coating solution was 2.
At 4 μm, the ratio of 90% cumulative particle size / 50% central particle size is 5.
Liquids containing 1.5 g of zirconia particles of 2, 8.1, 9.7 (above, examples) and 18.1 (comparative example) were prepared, and applied and dried. Next, these samples were annealed at 835 ° C. for 30 seconds in a nitrogen atmosphere to form an insulating film on the surface of the steel sheet. The seizure property and space factor of the sample thus prepared were evaluated by the methods described above.
【００４２】結果を表５に示す。The results are shown in Table 5.
【００４３】[0043]
【表５】 [Table 5]
【００４４】表５から９０％積算粒径／５０％中心粒径
の比率が１０以下の実施例において占積率が９７．８％
以上と高く、良好であるのに対し、同比率が１０以上で
ある比較例においては占積率が９４．９％と低く、良好
でない。From Table 5, in the examples in which the ratio of 90% cumulative particle size / 50% central particle size is 10 or less, the space factor is 97.8%.
The above is high and good, but in the comparative example in which the ratio is 10 or more, the space factor is as low as 94.9%, which is not good.
【００４５】[0045]
【発明の効果】以上述べたように、５０％中心粒径が２
μｍ超２０μｍ以下で、かつ９０％積算粒径と５０％中
心粒径の比率が１０以下である無機鉱物質粒子を絶縁皮
膜形成用塗布液中に添加し、絶縁皮膜を形成させた方向
性珪素鋼板は、高い占積率を維持したまま、歪み取り焼
鈍時の耐焼き付き性も良好である。As described above, the 50% center particle size is 2
Directional silicon having an insulating film formed by adding inorganic mineral particles having a ratio of 90% cumulative particle size to 50% central particle size of 10 or less to more than 20 μm and less than 20 μm to an insulating film forming coating solution. The steel sheet has good seizure resistance during strain relief annealing while maintaining a high space factor.
───────────────────────────────────────────────────── 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 収 福岡県北九州市戸畑区大字中原46番地の 59 日鐵プラント設計株式会社内 (56)参考文献 特開 昭53−28043（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C23C 22/00 C21D 9/46 501 H01F 1/16 H01F 1/18 B05D 7/14 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shingo Okada 1-1 Tobata-cho, Tobata-ku, Kitakyushu, Fukuoka Prefecture Nippon Steel Co., Ltd. Yawata Works (72) Inventor Tanaka Osamu Nakahara, Tobata-ku, Kitakyushu, Fukuoka 59 Nippon Steel Plant Design Co., Ltd. at address 46 (56) Reference JP-A-53-28043 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) C23C 22/00 C21D 9 / 46 501 H01F 1/16 H01F 1/18 B05D 7/14
Claims (4)
し、無機鉱物質粒子を含有する塗布液を塗布し焼き付け
ることにより鋼板上に絶縁皮膜を形成する方向性珪素鋼
板の製造方法において、前記無機鉱物質粒子として、レ
ーザー散乱・回折式粒度分布測定法により測定された５
０％中心粒径が２μｍ超２０μｍ以下で、かつ９０％積
算粒径と５０％中心粒径の比率が１０以下である無機鉱
物質粒子を使用することを特徴とする占積率と耐焼き付
き性に優れる絶縁皮膜付き方向性珪素鋼板の製造方法。1. A method for producing a grain-oriented silicon steel sheet, which comprises forming an insulating coating on a steel sheet by applying a coating solution containing inorganic mineral particles to a finish-annealed grain-oriented silicon steel sheet and baking the coating solution. As mineral particles, measured by laser scattering / diffraction type particle size distribution measurement method 5
Space factor and seizure resistance characterized by using inorganic mineral particles having a 0% central particle size of more than 2 μm and 20 μm or less and a ratio of 90% integrated particle size to 50% central particle size of 10 or less A method of manufacturing a grain-oriented silicon steel sheet with an insulating film, which is excellent in heat resistance.
ライト、スピネルのいずれか一方または両方を主体とす
る皮膜を有することを特徴とする請求項１記載の占積率
と耐焼き付き性に優れる方向性珪素鋼板の製造方法。2. The space factor and the seizure resistance according to claim 1, wherein the insulating film and the base metal have a film containing at least one of forsterite and spinel as a main component. A method for manufacturing an excellent grain-oriented silicon steel sheet.
ライト、スピネルのいずれか一方または両方を主体とす
る皮膜を有しないことを特徴とする請求項１記載の占積
率と耐焼き付き性に優れる方向性珪素鋼板の製造方法。3. The space factor and seizure resistance according to claim 1, wherein the insulating film and the base metal do not have a film mainly containing either or both of forsterite and spinel. Of excellent grain-oriented silicon steel sheet.
０．２μｍ以下であることを特徴とする請求項３記載の
占積率と耐焼き付き性に優れる方向性珪素鋼板の製造方
法。4. The method for producing a grain-oriented silicon steel sheet excellent in space factor and seizure resistance according to claim 3, wherein Ra of the interface between the coating and the base metal is Ra of 0.2 μm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000403125A JP3524058B2 (en) | 2000-12-28 | 2000-12-28 | Method for manufacturing oriented silicon steel sheet with insulating film having excellent space factor and seizure resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000403125A JP3524058B2 (en) | 2000-12-28 | 2000-12-28 | Method for manufacturing oriented silicon steel sheet with insulating film having excellent space factor and seizure resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002206171A JP2002206171A (en) | 2002-07-26 |
| JP3524058B2 true JP3524058B2 (en) | 2004-04-26 |
Family
ID=18867300
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000403125A Expired - Fee Related JP3524058B2 (en) | 2000-12-28 | 2000-12-28 | Method for manufacturing oriented silicon steel sheet with insulating film having excellent space factor and seizure resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3524058B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018117638A1 (en) * | 2016-12-21 | 2018-06-28 | 주식회사 포스코 | Annealing separator composition for oriented electrical steel sheet, oriented electrical steel sheet, and method for manufacturing oriented electrical steel sheet |
| KR20180072487A (en) * | 2016-12-21 | 2018-06-29 | 주식회사 포스코 | Annealing separating agent composition for grain oriented electrical steel sheet, grain oriented electrical steel sheet, and method for manufacturing grain oriented electrical steel sheet |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2006086B1 (en) * | 2006-04-07 | 2019-07-31 | Hitachi Metals, Limited | Process for production of soft magnetic metal strip laminate |
-
2000
- 2000-12-28 JP JP2000403125A patent/JP3524058B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018117638A1 (en) * | 2016-12-21 | 2018-06-28 | 주식회사 포스코 | Annealing separator composition for oriented electrical steel sheet, oriented electrical steel sheet, and method for manufacturing oriented electrical steel sheet |
| KR20180072487A (en) * | 2016-12-21 | 2018-06-29 | 주식회사 포스코 | Annealing separating agent composition for grain oriented electrical steel sheet, grain oriented electrical steel sheet, and method for manufacturing grain oriented electrical steel sheet |
| WO2018117637A3 (en) * | 2016-12-21 | 2018-08-16 | 주식회사 포스코 | Annealing separator composition for oriented electrical steel sheet, oriented electrical steel sheet, and method for manufacturing oriented electrical steel sheet |
| US11168376B2 (en) | 2016-12-21 | 2021-11-09 | Posco | Annealing separator composition for oriented electrical steel sheet, oriented electrical steel sheet, and method for manufacturing oriented electrical steel sheet |
| US11174525B2 (en) | 2016-12-21 | 2021-11-16 | Posco | Annealing separator composition for oriented electrical steel sheet, oriented electrical steel sheet, and method for manufacturing oriented electrical steel sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2002206171A (en) | 2002-07-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6354076B1 (en) | Directional electrical steel sheet with insulating coating, transformer core and transformer, and method for reducing transformer noise | |
| RU2767365C1 (en) | Method for producing a sheet of electrotechnical steel with oriented grain structure | |
| JP2791812B2 (en) | Method for forming insulating film of grain-oriented electrical steel sheet with excellent core workability, heat resistance and tension imparting property, and grain-oriented electrical steel sheet | |
| KR102464102B1 (en) | Grain-oriented electrical steel sheet and method for manufacturing grain-oriented electrical steel sheet | |
| JP2008266743A (en) | Grain oriented electrical steel sheet, and method for producing the same | |
| JP3524058B2 (en) | Method for manufacturing oriented silicon steel sheet with insulating film having excellent space factor and seizure resistance | |
| JP2017061732A (en) | Oriented electromagnetic steel sheet and production method thereof | |
| JP3447697B2 (en) | Oriented silicon steel sheet with insulating film that excels in space factor and seizure resistance | |
| JPS6376819A (en) | Grain-oriented electrical steel sheet having small iron loss and its manufacture | |
| CN114106593B (en) | Paint for oriented silicon steel surface coating, oriented silicon steel plate and manufacturing method thereof | |
| JP3162624B2 (en) | Method for producing low iron loss unidirectional silicon steel sheet | |
| EP3913074A1 (en) | Grain-oriented electromagnetic steel sheet, and steel sheet which can be used as raw material sheet for grain-oriented electromagnetic steel | |
| JPH08333640A (en) | Grain oriented silicon steel sheet extremely excellent in heat resistance and adhesion and formation of insulating film on it | |
| JP3065909B2 (en) | Method for producing low iron loss unidirectional silicon steel sheet | |
| JP2667098B2 (en) | Manufacturing method of low iron loss grain-oriented electrical steel sheet | |
| JPH10306380A (en) | Production of low core loss grain-oriented silicon steel sheet | |
| JP2003293149A (en) | Grain-oriented silicon steel sheet with excellent adhesion to tension-imparting insulation film, and manufacturing method therefor | |
| JP3456893B2 (en) | Low iron loss unidirectional silicon steel sheet | |
| RU2771766C1 (en) | Grain-oriented electrical steel sheet having excellent insulating coating adhesion without forsterite coating | |
| JP3557098B2 (en) | Coating solution for unidirectional silicon steel sheet insulation film with excellent adhesion resistance and space factor and method for forming insulation film | |
| JP4520720B2 (en) | Coating liquid for unidirectional silicon steel sheet with excellent adhesion resistance and space factor, and method for forming insulating film | |
| JP6841296B2 (en) | Processing liquid for forming an insulating film, manufacturing method of an electromagnetic steel sheet with an insulating film, and an electromagnetic steel sheet with an insulating film | |
| HU182582B (en) | Process for preparing electromagnetic steel with texture | |
| JP7311075B1 (en) | Method for manufacturing electrical steel sheet with pretreatment liquid and insulation coating | |
| JP2004346348A (en) | Insulating film excellent in tension-imparting property, grain-oriented magnetic steel sheet with low iron loss and its production method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20040203 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20040210 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 3524058 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080220 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090220 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090220 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100220 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100220 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110220 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110220 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120220 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120220 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130220 Year of fee payment: 9 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130220 Year of fee payment: 9 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130220 Year of fee payment: 9 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140220 Year of fee payment: 10 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| LAPS | Cancellation because of no payment of annual fees |