JP2009235530A - Magnetic steel sheet having insulating film - Google Patents
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Abstract
Description
本発明は、Ｃｒを含有しない絶縁被膜を有する電磁鋼板に関するものであり、前記被膜中及び被膜形成の塗布液中にも６価クロムのような有害物質を含まない環境を考慮した絶縁被膜を有する電磁鋼板に関するものである。 The present invention relates to an electrical steel sheet having an insulating coating that does not contain Cr, and has an insulating coating that takes into account an environment that does not contain harmful substances such as hexavalent chromium in the coating and the coating liquid for coating formation. It relates to electrical steel sheets.
モータや変圧器等に使用される電磁鋼板の絶縁被膜は、層間抵抗だけでなく種々の特性が要求される。例えば、加工成形時の利便性、保管、使用時の安定性などである。さらに、電磁鋼板は多様な用途に使用されるため、その用途に応じて種々の絶縁被膜の開発が行われている。
例えば、電磁鋼板に打抜加工、せん断加工、曲げ加工などを施すと残留歪みにより磁気特性が劣化する。そこで、劣化した磁気特性を回復させるため７５０〜８５０℃程度で歪取り焼鈍を行う場合が多い。この場合には絶縁被膜が歪取り焼鈍に耐えるものでなければならない。
Insulating coatings on electrical steel sheets used for motors, transformers and the like are required to have not only interlayer resistance but also various characteristics. For example, convenience during processing, storage, stability during use, and the like. Furthermore, since electromagnetic steel sheets are used for various applications, various insulating coatings have been developed according to the applications.
For example, when a magnetic steel sheet is subjected to punching, shearing, bending, etc., the magnetic properties are deteriorated due to residual strain. Therefore, in order to recover the deteriorated magnetic properties, strain relief annealing is often performed at about 750 to 850 ° C. In this case, the insulating coating must withstand strain relief annealing.
絶縁被膜は、（１）溶接性、耐熱性を重視し、歪取り焼鈍に耐える無機質被膜（原則として有機樹脂を含まない）、（２）打抜性、溶接性の両立を目指し、歪取り焼鈍に耐える、無機質をベースとして有機樹脂を含有する半有機質被膜、（３）特殊用途で歪取り焼鈍を施すことができない有機被膜、の３種に大別される。この中で、汎用品として歪取り焼鈍に耐えるのは（１）、（２）の無機質を含む被膜であり、両者とも被膜中にクロム化合物を含む。特に、（２）のタイプで有機樹脂を含有したクロム酸塩系絶縁被膜は、無機系絶縁被膜に比べて打抜性を格段に向上させることができるので広く利用されている。 Insulating coatings are (1) inorganic coating (in principle not including organic resin) that can withstand strain relief annealing with emphasis on weldability and heat resistance, and (2) strain relief annealing with the aim of achieving both punchability and weldability. It is roughly classified into three types: a semi-organic film containing an organic resin based on an inorganic material, and (3) an organic film that cannot be subjected to strain relief annealing for special applications. Among these, as a general-purpose product, it is a film containing the inorganic substances (1) and (2) that can withstand strain relief annealing, and both contain a chromium compound in the film. In particular, the chromate-based insulating coating containing the organic resin in the type (2) is widely used because punchability can be remarkably improved as compared with the inorganic insulating coating.
例えば、特許文献１には、少なくとも１種の２価金属を含む重クロム酸塩系水溶液に、水溶液中のＣｒＯ３：１００重量部に対し、酢酸ビニル／ベオバ(登録商標)比が９０／１０〜４０／６０の比率である樹脂エマルジョンを樹脂固形分で５〜１２０重量部、および有機還元剤を１０〜６０重量部の割合で配合して処理液（coating liquid）とし、その処理液を基地鉄板（steel sheet）の表面に塗布し、常法による焼付け工程を経て形成した、電気絶縁被膜を有する電磁鋼板が記載されている。
このような電磁鋼板用のクロム酸塩系被膜は、鋼板製品としては三価クロムとなっていることがほとんどのため、有害性の問題はない。しかし、塗布液の段階では有害な六価クロムを使用しなければならないため、良好な作業環境の確保のためには、設備の充実はもちろんのこと、厳しい取り扱い基準の遵守が要求される。
このような現状を受けて、さらには昨今の環境意識の高まりを受けて、電磁鋼板の分野においてもＣｒを含有しない絶縁被膜を有する製品が需要家等から望まれてきている。
For example, Patent Document 1 discloses that a dichromate-based aqueous solution containing at least one divalent metal has a vinyl acetate / veova (registered trademark) ratio of 90/10 with respect to 100 parts by weight of CrO 3 in an aqueous solution. A resin emulsion having a ratio of ˜40 / 60 is blended in a ratio of 5 to 120 parts by weight of resin solids and an organic reducing agent in a proportion of 10 to 60 parts by weight to form a coating liquid. There is described an electrical steel sheet having an electrical insulating coating that is applied to the surface of a steel sheet and formed through a conventional baking process.
Since such chromate-based coatings for electrical steel sheets are mostly trivalent chromium as steel sheet products, there is no problem of toxicity. However, since harmful hexavalent chromium must be used at the coating solution stage, in order to ensure a good working environment, it is required to comply with strict handling standards as well as to improve facilities.
In response to such a current situation, and in response to the recent increase in environmental awareness, in the field of electromagnetic steel sheets, products having an insulating coating containing no Cr have been desired by customers and the like.
クロム酸以外を主剤とする技術として、シリカ等の無機コロイドを主剤とする半有機質絶縁被膜が、数多く開示されている。これらによると、有害な六価クロム液の取り扱いを行う必要がないため、環境上非常に有利に適用が可能である。例えば、特許文献２には、無機コロイド系の耐食性を向上させる方法として、樹脂/シリカ被膜中のCl、S量を規定量以下にする方法が開示されている。この方法によると、製品板の耐食性は湿潤試験環境では向上する。しかしながら、塩水噴霧等のような過酷な条件下での耐食性は、Ｃｒ含有絶縁被膜を用いた場合の耐食性には及ばない。また、シリカを配合した場合、打抜性に関しても、耐食性と同様に、Ｃｒ含有絶縁被膜を用いた場合の良好な打抜性には及ばない。 A number of semi-organic insulating coatings based on inorganic colloids such as silica have been disclosed as technologies based on materials other than chromic acid. According to these, since it is not necessary to handle harmful hexavalent chromium liquid, it can be applied very advantageously in the environment. For example, Patent Document 2 discloses a method for reducing the amount of Cl and S in a resin / silica coating to a specified amount or less as a method for improving the corrosion resistance of an inorganic colloidal system. According to this method, the corrosion resistance of the product plate is improved in a wet test environment. However, the corrosion resistance under severe conditions such as salt spray does not reach the corrosion resistance when the Cr-containing insulating coating is used. In addition, when silica is blended, the punchability is not as good as the punching property when the Cr-containing insulating coating is used, similarly to the corrosion resistance.
すなわち、電磁鋼板では、常温環境下での湿潤耐食性、塩水噴霧耐食性、および７００℃
以上の高温処理後（歪取焼鈍後）の耐食性を併せ持つ必要がある。腐食環境下での犠牲防
食のため亜鉛や錫などのめっきを施している表面処理鋼板と異なり電磁鋼板は鉄部が表面
に露出している。このような場合には、被膜特性として、高度なバリヤ性を有すること
で、腐食因子となる水、酸素、塩素などを遮蔽し、その結果カソード型腐食を抑制するこ
とが重要となる。このような高バリヤ特性を持たせるためには無機被膜のような連続的か
つ緻密な構造を有することが望ましい。
一方、打抜き加工性を良好にすること、すなわち、打抜き加工で弊害となる連続打抜き後
の金型磨耗を抑制させるためには、被膜中に潤滑成分を含有させることが有効である。し
かしながら、耐食性と加工性を両立させるため、無機系と有機樹脂系の混合被膜とする
と、被膜の連続性が損なわれ耐食性が劣化する。
That is, in the electromagnetic steel sheet, wet corrosion resistance under normal temperature environment, salt spray corrosion resistance, and 700 ° C.
It is necessary to have corrosion resistance after the above high-temperature treatment (after strain relief annealing). Unlike surface-treated steel sheets that are plated with zinc or tin for sacrificial corrosion protection in corrosive environments, the steel part of the electromagnetic steel sheet is exposed on the surface. In such a case, it is important to have a high barrier property as a film characteristic, thereby shielding water, oxygen, chlorine, and the like, which are corrosion factors, and consequently suppressing cathodic corrosion. In order to have such high barrier properties, it is desirable to have a continuous and dense structure such as an inorganic coating.
On the other hand, in order to improve punching workability, that is, to suppress die wear after continuous punching, which is harmful in punching, it is effective to include a lubricating component in the coating. However, in order to achieve both corrosion resistance and workability, if a mixed coating of inorganic and organic resin is used, the continuity of the coating is impaired and the corrosion resistance deteriorates.
本発明者らは、特許文献３および特許文献４にて上記問題点を克服し、耐食性と打ち抜き加工性とを両立するクロムを含有しない絶縁被膜を有する電磁鋼板を開発した。
しかし、特許文献３および４の高いバリヤを有する被膜であっても、焼鈍雰囲気が酸化性である場合、耐スティッキング性（焼鈍時に鋼板どうしが密着（スティッキング）すると電気的短絡が生じて鉄損が増加する現象）がクロム系皮膜と比較すると低位でありさらなる被膜の改良が必要であった。
However, even in the coating film having a high barrier of Patent Documents 3 and 4, when the annealing atmosphere is oxidizing, sticking resistance (when the steel sheets are in close contact (sticking) during annealing, an electrical short circuit occurs and iron loss occurs. Increasing phenomenon) was lower than that of the chromium-based film, and further improvement of the film was necessary.
本発明は、上記の事情に鑑み、例えば、酸化性を有する雰囲気下であっても耐スティッキング性がＣｒ含有絶縁被膜と同等の性能を有する絶縁被膜を有する電磁鋼板を提供することを目的とする。 In view of the above circumstances, an object of the present invention is to provide an electrical steel sheet having an insulating coating having a performance equivalent to that of a Cr-containing insulating coating even in an oxidizing atmosphere, for example. .
本発明者らは、上記の課題を解決するために鋭意研究を行った。その結果、以下の知見を得た。
歪取焼鈍時の雰囲気ガスに酸素が含有した場合、従来のクロムフリー被膜は、被膜の酸素遮蔽性が低いため被膜直下に内部酸化層を形成する。同時に鋼中の鉄は表面に濃化し、皮膜欠陥が存在した場合、導通点が生じ鉄損が発生する。
皮膜中に無機物やほう酸の含有量を増加させると耐スティッキング除去性が向上する。
無機物の配合として、酸化ゾルとほう酸にシランカップリング剤を添加した場合、シランカップリング剤を添加しない状態より緻密な無機化合物になり、酸素バリヤ性が向上し、その結果、鉄の拡散を抑制し耐スティッキング除去性が向上する。
酸化物ゾルとして、シリカゾル、アルミナゾル、チタニアゾル、アンチモンゾル、タングステンゾル、モリブデンゾルが、除去性に効果がある。
The inventors of the present invention have intensively studied to solve the above problems. As a result, the following knowledge was obtained.
When oxygen is contained in the atmosphere gas during strain relief annealing, the conventional chromium-free coating film forms an internal oxide layer directly under the coating film because of its low oxygen shielding property. At the same time, the iron in the steel is concentrated on the surface, and when there is a film defect, a conduction point occurs and iron loss occurs.
When the content of inorganic substance or boric acid is increased in the film, the sticking removal resistance is improved.
When a silane coupling agent is added to the sol and boric acid as an inorganic compound, it becomes a denser inorganic compound than when no silane coupling agent is added, resulting in improved oxygen barrier properties and, consequently, suppression of iron diffusion. In addition, the sticking removal resistance is improved.
As the oxide sol, silica sol, alumina sol, titania sol, antimony sol, tungsten sol, and molybdenum sol are effective for removal.
本発明は、以上の知見に基づきなされたもので、その要旨は以下のとおりである。
［１］絶縁被膜を有する電磁鋼板であって、該絶縁被膜中には、シリカゾル、アルミナゾル、チタニアゾル、アンチモンゾル、タングステンゾル、モリブデンゾルの１種又は２種以上からなる酸化物ゾルと、ほう酸と、シランカップリング剤を含有し、固形分率で３０質量％超９０質量％未満である無機化合物と、アクリル樹脂、スチレン樹脂、シリコン樹脂、ポリエステル樹脂、ウレタン樹脂、ポリエチレン樹脂、ポリアミド樹脂、フェノール樹脂およびエポキシ樹脂の１種又は２種以上含有する有機樹脂とを含み、前記酸化物ゾル固形分１００質量部に対し、ほう酸は２質量部超４０質量部未満、シランカップリング剤は１質量部以上１５質量部未満であることを特徴とする絶縁被膜を有する電磁鋼板。
［２］前記［１］において、前記絶縁被膜は、前記無機化合物と前記有機樹脂を含む塗液を電磁鋼板に塗布、焼付けしてなる被膜であることを特徴とする絶縁被膜を有する電磁鋼板。
［３］前記［１］または［２］において、前記有機樹脂中に、架橋剤として、メラミン、イソシアネート、シランカップリング剤（前記無機化合物中への添加とは別に有機樹脂中に添加）、オキサドリンから選ばれる１種又は２種以上を被膜全固形分に対して３０質量％以下含有することを特徴とする絶縁被膜を有する電磁鋼板。
The present invention has been made based on the above findings, and the gist thereof is as follows.
[1] An electrical steel sheet having an insulating coating, wherein the insulating coating includes an oxide sol composed of one or more of silica sol, alumina sol, titania sol, antimony sol, tungsten sol, molybdenum sol, boric acid, , An inorganic compound containing a silane coupling agent and having a solid content of more than 30% by mass and less than 90% by mass, acrylic resin, styrene resin, silicon resin, polyester resin, urethane resin, polyethylene resin, polyamide resin, phenol resin And an organic resin containing one or more of epoxy resins, with respect to 100 parts by mass of the oxide sol solid content, boric acid is more than 2 parts by mass and less than 40 parts by mass, and the silane coupling agent is 1 part by mass or more. An electrical steel sheet having an insulating coating characterized by being less than 15 parts by mass.
[2] The electromagnetic steel sheet having an insulating film according to [1], wherein the insulating film is a film formed by applying and baking a coating liquid containing the inorganic compound and the organic resin on an electromagnetic steel sheet.
[3] In the above [1] or [2], in the organic resin, melamine, isocyanate, a silane coupling agent (added to the organic resin separately from the addition to the inorganic compound) as a crosslinking agent, oxadrine An electrical steel sheet having an insulating coating, comprising one or more selected from the group consisting of 30% by mass or less based on the total solid content of the coating.
本発明の絶縁被膜を有する電磁鋼板は、Ｃｒを含有しない無機物を主成分とする絶縁被膜であってもＣｒ含有絶縁被膜と同等以上の性能を有し、さらには、歪取焼鈍時の雰囲気ガスに酸素が混入しているような劣悪な条件で歪取り焼鈍を行ったとしても優れた耐スティッキングを有する。そのため、製造における適用範囲がひろがり、コストダウンがはかれる。また、最終製品だけでなく製造工程においても環境に優しく、モータ、トランス等の用途をはじめ広く利用するなど産業上有益な発明と言える。 The electrical steel sheet having the insulating coating of the present invention has performance equivalent to or better than that of the Cr-containing insulating coating, even if it is an insulating coating containing an inorganic material not containing Cr, and further, atmospheric gas during strain relief annealing. Even if the strain relief annealing is performed under such an inferior condition that oxygen is mixed in, it has excellent anti-sticking property. Therefore, the range of application in manufacturing is expanded, and cost reduction is achieved. In addition to the final product, it is environmentally friendly not only in the manufacturing process, but can be said to be an industrially useful invention that is widely used including motors and transformers.
以下に本発明を詳細に説明する。
本発明の電磁鋼板は、絶縁被膜を有する鋼板であり、前記絶縁被膜は、シリカゾル、アルミナゾル、チタニアゾル、アンチモンゾル、タングステンゾル、モリブデンゾルの１種又は２種以上からなる酸化物ゾルと、ほう酸と、シランカップリング剤を含有し、固形分率で３０質量％超９０質量％未満である無機化合物と、アクリル樹脂、スチレン樹脂、シリコン樹脂、ポリエステル樹脂、ウレタン樹脂、ポリエチレン樹脂、ポリアミド樹脂、フェノール樹脂およびエポキシ樹脂の１種又は２種以上含有する有機樹脂とを含み、前記酸化物ゾル固形分１００質量部に対し、ほう酸は２質量部超４０質量部未満、シランカップリング剤は１質量部以上１５質量部未満である。これは本発明において、最も重要な要件である。そして、このような絶縁被膜を有することにより、酸化性雰囲気の歪取り焼鈍であっても、Ｃｒ含有絶縁被膜を有する電磁鋼板と同等以上の優れた耐スティッキング性を有することになる。
The present invention is described in detail below.
The electromagnetic steel sheet of the present invention is a steel sheet having an insulating coating, and the insulating coating comprises an oxide sol composed of one or more of silica sol, alumina sol, titania sol, antimony sol, tungsten sol, molybdenum sol, boric acid, , An inorganic compound containing a silane coupling agent and having a solid content of more than 30% by mass and less than 90% by mass, acrylic resin, styrene resin, silicon resin, polyester resin, urethane resin, polyethylene resin, polyamide resin, phenol resin And an organic resin containing one or more of epoxy resins, with respect to 100 parts by mass of the oxide sol solid content, boric acid is more than 2 parts by mass and less than 40 parts by mass, and the silane coupling agent is 1 part by mass or more. Less than 15 parts by mass. This is the most important requirement in the present invention. And by having such an insulating film, even if it is the stress relief annealing of an oxidizing atmosphere, it will have the outstanding sticking resistance equivalent to or more than the electromagnetic steel sheet which has a Cr containing insulating film.
まず、本発明で用いる電磁鋼板について説明する。
本発明で用いることができる被膜を形成する前の電磁鋼板（電気鉄板ともいう）は、比抵抗を変化させて所望の磁気特性を得るために調整された鋼板（鉄板）であればどのような組成の鋼板でもよく、特に制限されない。特に、Si単独あるいはSi＋Alが０．１〜１０．０質量％程度含有された、Ｗ15/50≦５．０W/Kg程度の中〜高級電磁鋼板は好適に使用される。
また、絶縁被膜が形成される電磁鋼板の表面は、アルカリなどによる脱脂処理、塩酸、硫酸、リン酸などによる酸洗処理など、任意の前処理を施してもよいし、製造されたままの未処理の表面であってもよい。
さらに、絶縁被膜と地鉄表面との間に第３の層を形成させることは必ずしも要さないが、必要に応じて形成させてもよい。例えば、通常の製法では地鉄金属の酸化被膜が絶縁被膜と地鉄表面との間に形成されることがあるが、これを除去する手間は省いてもよい。また、製法によってはフォルステライト被膜が生成するが、これを除去する手間も省いてよい。
First, the electrical steel sheet used in the present invention will be described.
The electromagnetic steel plate (also referred to as an electric iron plate) before forming a coating that can be used in the present invention is any steel plate (iron plate) adjusted to obtain a desired magnetic property by changing the specific resistance. A steel plate having a composition may be used and is not particularly limited. In particular, medium to high-grade electrical steel sheets containing about W 15/50 ≦ 5.0 W / Kg, containing Si alone or about 0.1 to 10.0% by mass of Si + Al, are preferably used.
Further, the surface of the electrical steel sheet on which the insulating coating is formed may be subjected to any pretreatment such as degreasing treatment with alkali, pickling treatment with hydrochloric acid, sulfuric acid, phosphoric acid, etc. It may be the surface of the treatment.
Furthermore, although it is not always necessary to form the third layer between the insulating coating and the surface of the ground iron, it may be formed as necessary. For example, in a normal manufacturing method, a metal oxide metal oxide film may be formed between the insulating film and the metal iron surface, but it may be possible to omit the trouble of removing this. Moreover, although a forsterite film is produced depending on the production method, the trouble of removing this film may be omitted.
次に、上記鋼板の表面に塗布される本発明の絶縁被膜について説明する。
本発明の絶縁被膜は、以下に述べる必須成分である無機化合物と有機樹脂とを含有する塗布液を、電磁鋼板表面に塗布し、その後焼付け乾燥することで得られる。
Next, the insulating coating of the present invention applied to the surface of the steel plate will be described.
The insulating coating of the present invention is obtained by applying a coating solution containing an inorganic compound and an organic resin, which are essential components described below, to the surface of the magnetic steel sheet, and then baking and drying.
無機化合物
本発明の無機化合物は、酸化物ゾルと、ほう酸と、シランカップリング剤を含有する。そして、その割合は、酸化物ゾル固形分１００質量部に対し、ほう酸は２質量部超４０質量部未満、シランカップリング剤は１質量部以上１５質量部未満である。また、無機化合物は、固形分率で３０質量％超９０質量％未満である。
酸化物ゾルは、シリカゾル、アルミナゾル、チタニアゾル、アンチモンゾル、タングステンゾル、モリブデンゾルから選択でき、１種又は２種以上を用いることができる。
酸化物ゾル固形分１００質量部に対し、ほう酸は２質量部超４０質量部未満、シランカップリング剤は１質量部以上１５質量部未満の範囲は耐スティッキング性を向上させる良好範囲であって、このような範囲内に酸化物ゾル・ほう酸・シランカップリングを添加してなる３元無機化合物を絶縁被膜中に含有することで、酸化性を有する雰囲気下であっても耐スティッキング性が優れることになる。
ほう酸が２質量部以下では耐スティッキング性、焼鈍後密着性が劣化する。一方、４０質量部以上では、湿潤耐食性が劣化する。
シランカップリング剤が１質量部未満では、酸化ゾル間の結合が弱く緻密な無機化合物が得られないことから、焼鈍後性能の低下がみられ、特に耐スティッキング性、焼鈍後密着性、焼鈍後耐食性が劣化する。一方、１５質量部以上では、未反応のシランカップリング剤が皮膜中に残存することになり、湿潤耐食性、皮膜密着性が低下する。
上記無機化合物（酸化物ゾル・ほう酸・シランの３元無機化合物）は、皮膜全固形分換算で３０質量％超９０質量％未満皮膜中固形分に含有させる。３０質量％未満では、耐スティッキング性が劣化し、９０質量％超では湿潤耐食性が低下する。
Inorganic Compound The inorganic compound of the present invention contains an oxide sol, boric acid, and a silane coupling agent. And the ratio is more than 2 mass parts and less than 40 mass parts, and a silane coupling agent is 1 mass part or more and less than 15 mass parts with respect to 100 mass parts of oxide sol solid content. Moreover, an inorganic compound is more than 30 mass% and less than 90 mass% by solid content rate.
The oxide sol can be selected from silica sol, alumina sol, titania sol, antimony sol, tungsten sol, and molybdenum sol, and one or more of them can be used.
With respect to 100 parts by mass of the oxide sol solid content, boric acid is in the range of more than 2 parts by mass and less than 40 parts by mass, and the silane coupling agent in the range of 1 part by mass to less than 15 parts by mass is a good range for improving the sticking resistance. By including a ternary inorganic compound in which oxide sol, boric acid, and silane coupling are added in such a range in the insulating coating, the sticking resistance is excellent even in an oxidizing atmosphere. become.
When boric acid is 2 parts by mass or less, the sticking resistance and the adhesion after annealing deteriorate. On the other hand, if it is 40 parts by mass or more, the wet corrosion resistance deteriorates.
When the silane coupling agent is less than 1 part by mass, the bonding between the oxide sols is weak and a dense inorganic compound cannot be obtained, so that the post-annealing performance is deteriorated, especially sticking resistance, post-annealing adhesion, post-annealing Corrosion resistance deteriorates. On the other hand, when the amount is 15 parts by mass or more, unreacted silane coupling agent remains in the film, and wet corrosion resistance and film adhesion deteriorate.
The inorganic compound (a ternary inorganic compound of oxide sol, boric acid, and silane) is contained in the solid content in the film of more than 30% by mass and less than 90% by mass in terms of the total solid content of the film. If it is less than 30% by mass, the sticking resistance deteriorates, and if it exceeds 90% by mass, the wet corrosion resistance decreases.
有機樹脂
有機樹脂としては、アクリル樹脂、スチレン樹脂、シリコン樹脂、ポリエステル樹脂、ウレタン樹脂、ポリエチレン樹脂、ポリアミド樹脂、フェノール樹脂およびエポキシ樹脂があげられ、これらから選ばれる１種または２種以上を選択し、有機樹脂として用いる。
Organic resin Examples of the organic resin include acrylic resin, styrene resin, silicon resin, polyester resin, urethane resin, polyethylene resin, polyamide resin, phenol resin, and epoxy resin, and one or more selected from these are selected. Used as an organic resin.
架橋剤として、メラミン、イソシアネート、シランカップリング剤、オキサドリンから選ばれる１種又は２種以上含有（好適条件）
本発明では、さらに、架橋剤としてメラミン、イソシアネート、シランカップリング剤およびオキサドリンの１種又は２種以上を有機樹脂中に含有させることができる。上記架橋剤の添加によって、湿潤耐食性、耐傷つき性の向上が発現される。なお、架橋剤として、シランカップリングを含有させる場合は、無機化合物中に含有するシランカップリング剤とは別に改めて添加するものとする。
これら架橋剤の含有量は被膜全固形分に対して３０質量％以下とすることが好ましい。
As a cross-linking agent, one or more selected from melamine, isocyanate, silane coupling agent, and oxadrine (preferred conditions)
In the present invention, one or more of melamine, isocyanate, silane coupling agent and oxadrine can be further contained in the organic resin as a crosslinking agent. Addition of the cross-linking agent can improve wet corrosion resistance and scratch resistance. In addition, when a silane coupling is contained as a crosslinking agent, it shall be newly added separately from the silane coupling agent contained in an inorganic compound.
The content of these crosslinking agents is preferably 30% by mass or less with respect to the total solid content of the film.
以上より、本発明は目的とする特性が得られるが、上記の含有物に加えて、本発明の作用効果を害さない範囲で、以下に示す目的で添加剤を含有することができる。
添加剤
添加剤としては、公知の界面活性剤、消泡剤、防錆剤、潤滑剤などが添加可能である。添加量は被膜全固形分に対して３０質量％以下程度が好ましい。
As described above, the present invention can provide the desired properties, but in addition to the above-mentioned inclusions, additives can be contained for the following purposes within a range not impairing the effects of the present invention.
As additive additives, known surfactants, antifoaming agents, rust preventives, lubricants and the like can be added. The addition amount is preferably about 30% by mass or less with respect to the total solid content of the film.
なお、本発明はクロム化合物を添加せずに良好な被膜特性を得ることを目的としている。したがって、本発明の絶縁被膜は製造工程および製品からの環境汚染を防止する観点から、Ｃｒを実質的に含まないことが好ましい。不純物として許容されるクロム量としては、絶縁被膜の全固形分質量（全被膜量）に対してＣｒＯ３換算した量で０．１質量％以下とすることが好ましい。 It is to be noted that an object of the present invention is to obtain good film characteristics without adding a chromium compound. Therefore, it is preferable that the insulating coating of the present invention does not substantially contain Cr from the viewpoint of preventing environmental contamination from the manufacturing process and products. The amount of chromium allowed as an impurity is preferably 0.1% by mass or less in terms of CrO 3 with respect to the total solid mass (total coating amount) of the insulating coating.
次に本発明の絶縁被膜を有する電磁鋼板の製造方法について説明する。
本発明の出発素材として用いる電磁鋼板の前処理は特に規定しない。未処理あるいはアルカリなどの脱脂処理、塩酸、硫酸、リン酸などの酸洗処理が好ましく適用される。
そして、この鋼板上に上述した配合の塗布液を塗布する。その後、前記塗布液を塗布した電磁鋼板に焼き付け処理を施すことにより電磁鋼板上に絶縁被膜を形成させる。
Next, the manufacturing method of the electrical steel sheet which has an insulating film of this invention is demonstrated.
The pretreatment of the electrical steel sheet used as the starting material of the present invention is not particularly defined. Untreated or alkaline degreasing treatment, pickling treatment with hydrochloric acid, sulfuric acid, phosphoric acid or the like is preferably applied.
And the coating liquid of the mixing | blending mentioned above is apply | coated on this steel plate. Then, an insulating film is formed on the magnetic steel sheet by subjecting the magnetic steel sheet coated with the coating solution to a baking process.
塗布する被膜原料は水性または油性の、ペースト状あるいは液状が好ましい。必要以上に被膜厚み（被膜付着量）を増大させない観点からは、水または有機溶剤をベースとした液状とすることが好ましい。なお、本発明において、処理液とはペースト状も含むものとする。 The coating material to be applied is preferably an aqueous or oily paste or liquid. From the viewpoint of not increasing the coating thickness (coating adhesion amount) more than necessary, it is preferable to use a liquid based on water or an organic solvent. In the present invention, the treatment liquid includes a paste.
絶縁被膜の塗布方法としては一般工業的に用いられる、ロールコーター、フローコーター、スプレー、ナイフコーター、バーコーター等種々の設備を用いる方法が適用可能である。
また、焼き付け方法についても通常実施されるような熱風式、赤外線加熱式、誘導加熱式等が可能である。焼き付け温度も通常レベルであればよいが、樹脂の熱分解を避けるため、３５０℃以下とすることが好ましい。より好ましい範囲は１５０℃以上３００℃以下である。
As a method for applying the insulating coating, a method using various facilities such as a roll coater, a flow coater, a spray, a knife coater, and a bar coater, which are generally used industrially, can be applied.
In addition, a hot air method, an infrared heating method, an induction heating method, or the like, which is usually performed, is also possible for the baking method. The baking temperature may be at a normal level, but is preferably 350 ° C. or lower in order to avoid thermal decomposition of the resin. A more preferable range is 150 ° C. or higher and 300 ° C. or lower.
絶縁被膜付着量
絶縁被膜の付着量は特に限定はしない。片面あたり０.０５g/m２以上１０g/m２以下であることが好ましい。より好ましくは、片面あたり合計で０．１ｇ／ｍ２以上１０ｇ／ｍ２以下である。０.０５g/m２未満であると、工業的手段では均一な塗布が困難であり、安定した打抜性や耐食性を確保することが難しい場合がある。一方、１０g/m２超であるとそれ以上の被膜性能向上がなく、不経済となる可能性がある。
なお、付着量の測定は、焼き付け処理後かつ歪み取り焼鈍を施していない鋼板について行うものとし、熱アルカリ等で被膜のみを溶解させて、溶解前後の重量変化から測定する重量法を用いることができる。
歪み取り焼鈍後の付着量としては０.０１g/m２以上９．０g/m２以下程度が好ましい。
Insulating coating amount The insulating coating amount is not particularly limited. Is preferably 0.05 g / m 2 or more per side 10 g / m 2 or less. More preferably, it is 0.1 g / m 2 or more and 10 g / m 2 or less in total per one side. If it is less than 0.05 g / m 2 , uniform application is difficult by industrial means, and it may be difficult to ensure stable punchability and corrosion resistance. On the other hand, if it exceeds 10 g / m 2 , the coating performance is not improved further, which may be uneconomical.
In addition, the amount of adhesion shall be measured on a steel plate that has not been subjected to the strain relief annealing after baking treatment, and a weight method is used in which only the coating is dissolved with hot alkali or the like and measured from the weight change before and after dissolution. it can.
The adhesion amount after strain relief annealing is preferably about 0.01 g / m 2 or more and 9.0 g / m 2 or less.
また、本発明の絶縁被膜は鋼板の両面にあることが好ましいが、目的によっては片面のみでも構わない。すなわち、目的によっては片面のみ施し、他面は他の絶縁被膜としてもよいし、他面に絶縁被覆を施さなくてもよい。 In addition, the insulating coating of the present invention is preferably on both surfaces of the steel sheet, but depending on the purpose, only one surface may be used. That is, depending on the purpose, only one surface may be applied, and the other surface may be another insulating coating, or the other surface may not be provided with an insulating coating.
以上からなる本発明の絶縁被膜を有する電磁鋼板は、被膜の耐熱性を生かす意味で、７５０〜８５０℃程度で歪取り焼鈍を行う用途に用いることが最適である。例えば、電磁鋼板を打ち抜き、歪み取り焼鈍を行った後、積層して積層鉄心を得る用途はとくに好適である。 The electrical steel sheet having the insulating coating of the present invention as described above is optimally used for applications in which strain relief annealing is performed at about 750 to 850 ° C. in order to make use of the heat resistance of the coating. For example, an application in which a laminated iron core is obtained by punching an electromagnetic steel sheet and performing strain relief annealing and then laminating it is particularly suitable.
以下、本発明の効果を実施例に基づいて具体的に説明するが、本発明はこれら実施例に限定されるものではない。
まず、電磁鋼板として、鋼成分としてSi:０.４５質量％、Mn:０.２５質量％、Al:０.４８質量％を含有し、板厚０.５mm厚の仕上げ焼鈍を施したフルプロセス電磁鋼板を用いた。表１に示す条件にて無機化合物と有機樹脂等を調合した塗液を前記電磁鋼板の表面上に、ロールコーターで塗布し、熱風炉にて焼付け温度：到達板温２３０℃で焼き付けて供試材を得た。
得られた供試材（絶縁被膜を有する電磁鋼板）に対して、沸騰した５０％ＮａＯＨ水溶液中で被膜を溶解させ、前述の重量法で絶縁被膜の付着量を測定した。
また、以上により得られた絶縁被膜を有する電磁鋼板に対して、以下の各被膜特性の測定を行い、評価した。
Hereinafter, although the effect of the present invention is concretely explained based on an example, the present invention is not limited to these examples.
First, as a magnetic steel sheet, the steel component contains Si: 0.45% by mass, Mn: 0.25% by mass, Al: 0.48% by mass, and is subjected to finish annealing with a thickness of 0.5 mm. An electromagnetic steel sheet was used. A coating liquid prepared by mixing an inorganic compound and an organic resin under the conditions shown in Table 1 was applied onto the surface of the magnetic steel sheet with a roll coater, and baked in a hot air oven at a final plate temperature of 230 ° C. I got the material.
The obtained test material (electrical steel sheet having an insulating coating) was dissolved in a boiling 50% NaOH aqueous solution, and the amount of the insulating coating deposited was measured by the weight method described above.
Moreover, with respect to the electrical steel sheet having the insulating coating obtained as described above, the following coating properties were measured and evaluated.
＜耐スティッキング性＞
鋼板を４８ｍｍφに打ち抜いてこれを１１枚積層し、締め付け圧力200ｋｇｆ／ｃｍ2で締め付けた状態で焼鈍（750℃×２時間、窒素90％、酸素10％Ｎ雰囲気中）を行った。焼鈍後、締め付けを解除し、板／板間の全１０箇所でのスティック発生の有無を調べ、スティック発生箇所の数で耐スティッキング性を評価した。その評価基準は以下の通りである。
◎：スティック発生２箇所以下
○：スティック発生３〜４箇所
△：スティック発生５〜７箇所
×：スティック発生８箇所以上
＜耐食性−製品板１＞
供試材に対して湿潤試験（５０℃、＞９８％ＲＨ（相対湿度））を行い、４８ｈ後の赤錆発生率を目視による面積率で評価した。
（判定基準）
◎：赤錆面積率：０%〜２０%未満
○：赤錆面積率：２０%以上〜４０%未満
△：赤錆面積率：４０%以上〜６０%未満
×：赤錆面積率：６０%以上〜１００%
＜歪取焼鈍後耐食性（耐食性−焼鈍板）＞
供試材に対して、窒素90％、酸素10％の雰囲気下、７５０℃×２ｈの条件にて焼鈍を行い、次いで、得られた焼鈍板に対して恒温恒湿試験試験(５０℃、相対湿度８０％)を行い、１４日後の赤錆発生率を目視による面積率で評価した。
（判定基準）
VG：赤錆面積率０%〜５%未満
◎：赤錆面積率５%以上〜２０%未満
○：赤錆面積率２０%以上〜４０%未満
△：赤錆面積率４０%以上〜６０%未満
×：赤錆面積率６０%以上〜１００%
＜製品板密着性＞
供試材を熱処理することなく、２０mmφでの１８０゜曲げ戻し試験を行い、目視による被膜剥離率で評価した。
（判定基準）
◎：剥離なし
○：〜剥離率２０%未満
△：剥離率２０%以上〜４０%未満
×：剥離率４０%以上〜全面剥離
＜焼鈍板密着性＞
供試材に対して、窒素90％、酸素10％の雰囲気下、７５０℃×２hの条件にて焼鈍を行い、得られた焼鈍板に対して、２０mmφでの１８０゜曲げ戻し試験を行い、目視による被膜剥離率で評価した。
（判定基準）
◎：剥離なし
○：〜剥離率２０%未満
△：剥離率２０%以上〜４０%未満
×：剥離率４０%以上〜全面剥離
＜耐傷つき性＞
電磁鋼板をせん断し、ばり高さを２０μｍとし、左記鋼板に５００ｇの分銅をのせ、水平
方向に３回、試験鋼板表面を往復させ、傷つき度を目視評価する。
（判定基準）
◎：変化無し
○：変化ほとんどなし
△：若干変色
×：変化大
以上より得られた結果を実験条件と併せて表1および表2に示す。
<Sticking resistance>
11 sheets of steel plates were punched into 48 mmφ and annealed (750 ° C. × 2 hours, 90% nitrogen, 10% oxygen in N atmosphere) in a state of being clamped at a clamping pressure of 200 kgf / cm 2 . After annealing, the tightening was released, the presence or absence of sticking at all 10 locations between the plates was examined, and the sticking resistance was evaluated by the number of sticking locations. The evaluation criteria are as follows.
◎: Stick generation 2 or less ○: Stick generation 3-4 location Δ: Stick generation 5-7 location ×: Stick generation 8 location or more <Corrosion resistance-Product plate 1>
The test material was subjected to a wet test (50 ° C.,> 98% RH (relative humidity)), and the occurrence rate of red rust after 48 h was evaluated by visual area rate.
(Criteria)
A: Red rust area ratio: 0% to less than 20% B: Red rust area ratio: 20% to less than 40% Δ: Red rust area ratio: 40% to less than 60% X: Red rust area ratio: 60% to 100%
<Corrosion resistance after strain relief annealing (corrosion resistance-annealed plate)>
The specimen was annealed under conditions of 750 ° C. × 2 h in an atmosphere of 90% nitrogen and 10% oxygen, and then the constant temperature and humidity test (50 ° C., relative to the obtained annealed plate) The humidity was 80%), and the occurrence rate of red rust after 14 days was evaluated by visual area ratio.
(Criteria)
VG: Red rust area ratio 0% to less than 5% ◎: Red rust area ratio 5% to less than 20% ○: Red rust area ratio 20% to less than 40% △: Red rust area ratio 40% to less than 60% ×: Red rust Area ratio 60% to 100%
<Product board adhesion>
Without heat-treating the test material, a 180 ° bending return test at 20 mmφ was performed, and the film peeling rate was visually evaluated.
(Criteria)
◎: No peeling ○: ~ Peeling rate less than 20% △: Peeling rate 20% or more and less than 40% ×: Peeling rate 40% or more to whole face peeling <Annealing plate adhesion>
The specimen was annealed under conditions of 750 ° C. × 2 h in an atmosphere of 90% nitrogen and 10% oxygen, and the obtained annealed plate was subjected to a 180 ° bending return test at 20 mmφ, The film peeling rate was visually evaluated.
(Criteria)
◎: No peeling ○: ~ Peeling rate less than 20% △: Peeling rate 20% or more and less than 40% ×: Peeling rate 40% or more ~ Fully peeled <Scratch resistance>
The magnetic steel plate is sheared, the flash height is 20 μm, a 500 g weight is placed on the left steel plate, the test steel plate surface is reciprocated three times in the horizontal direction, and the degree of damage is visually evaluated.
(Criteria)
◎: No change ○: Almost no change Δ: Slightly discolored ×: Large change The results obtained above are shown in Tables 1 and 2 together with the experimental conditions.
表１および表2から明らかなように、本発明例は耐スティッキング性、耐食性、密着性、耐傷つき性のいずれも優れている。
一方、比較例では、耐スティッキング性、耐食性、密着性、耐傷つき性のいずれか一つ以上が劣っている。
As is apparent from Tables 1 and 2, the examples of the present invention are excellent in all of sticking resistance, corrosion resistance, adhesion, and scratch resistance.
On the other hand, in the comparative example, any one or more of sticking resistance, corrosion resistance, adhesion, and scratch resistance is inferior.
Ｃｒを含有しない無機物を主成分とする絶縁被膜でありながら、例えば耐スティッキング性など、Ｃｒ含有絶縁被膜と同等以上の性能を有し、モータや変圧器等を中心に多様な用途での使用が期待される。 Although it is an insulating film mainly composed of an inorganic substance that does not contain Cr, it has performance equivalent to or better than that of Cr-containing insulating films, such as anti-sticking properties, and can be used in various applications, mainly in motors and transformers. Be expected.
Claims (3)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008085159A JP2009235530A (en) | 2008-03-28 | 2008-03-28 | Magnetic steel sheet having insulating film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008085159A JP2009235530A (en) | 2008-03-28 | 2008-03-28 | Magnetic steel sheet having insulating film |
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| Publication Number | Publication Date |
|---|---|
| JP2009235530A true JP2009235530A (en) | 2009-10-15 |
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| WO2013129282A1 (en) | 2012-02-29 | 2013-09-06 | Ｊｆｅスチール株式会社 | Electromagnetic steel sheet with insulative coating, method for producing same, and coating agent for forming insulative coating |
| WO2015029828A1 (en) | 2013-08-28 | 2015-03-05 | Ｊｆｅスチール株式会社 | Electromagnetic steel sheet with insulating coating film, method for producing same, and coating agent for forming insulating coating film |
| WO2018025846A1 (en) | 2016-08-03 | 2018-02-08 | Ｊｆｅスチール株式会社 | Electromagnetic steel sheet coated with insulating film, process for producing same, and coating material for forming insulating film |
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| JP2013209739A (en) * | 2012-02-29 | 2013-10-10 | Jfe Steel Corp | Electrical steel sheet with insulative coating, method for manufacturing the same, and coating agent for forming insulative coating |
| KR20140119771A (en) | 2012-02-29 | 2014-10-10 | 제이에프이 스틸 가부시키가이샤 | Electrical steel sheet with insulation coating, method of manufacturing same, and coating material for forming insulating coating |
| WO2015029828A1 (en) | 2013-08-28 | 2015-03-05 | Ｊｆｅスチール株式会社 | Electromagnetic steel sheet with insulating coating film, method for producing same, and coating agent for forming insulating coating film |
| KR20160045729A (en) | 2013-08-28 | 2016-04-27 | 제이에프이 스틸 가부시키가이샤 | Electromagnetic steel sheet with insulating coating film, method for producing same, and coating agent for forming insulating coating film |
| CN105556000A (en) * | 2013-08-28 | 2016-05-04 | 杰富意钢铁株式会社 | Electromagnetic steel sheet with insulating coating film, method for producing same, and coating agent for forming insulating coating film |
| JP6030668B2 (en) * | 2013-08-28 | 2016-11-24 | Ｊｆｅスチール株式会社 | Electrical steel sheet with insulating coating, method for producing the same, and coating agent for forming insulating coating |
| WO2018025846A1 (en) | 2016-08-03 | 2018-02-08 | Ｊｆｅスチール株式会社 | Electromagnetic steel sheet coated with insulating film, process for producing same, and coating material for forming insulating film |
| KR20190022846A (en) | 2016-08-03 | 2019-03-06 | 제이에프이 스틸 가부시키가이샤 | An electric steel sheet with an insulating film, a method for producing the same, and an insulating film- |
| JP2021066924A (en) * | 2019-10-21 | 2021-04-30 | Ｊｆｅスチール株式会社 | Magnetic steel sheet with insulation coating |
| JP7040508B2 (en) | 2019-10-21 | 2022-03-23 | Ｊｆｅスチール株式会社 | Electrical steel sheet with insulation coating |
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