JP2010013692A - Insulating film treatment agent, grain-oriented electrical steel sheet coated with the film treatment agent and insulating film treatment method therefor - Google Patents
Insulating film treatment agent, grain-oriented electrical steel sheet coated with the film treatment agent and insulating film treatment method therefor Download PDFInfo
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本発明は、クロムを含有せずに張力絶縁被膜を有する方向性電磁鋼板と、該鋼板に塗布する絶縁被膜処理剤及びその処理方法に関するものである。 The present invention relates to a grain-oriented electrical steel sheet that does not contain chromium and has a tensile insulating film, an insulating film treating agent applied to the steel sheet, and a treatment method thereof.
方向性電磁鋼板では、スラブを熱延して熱延板とした後、場合によっては焼鈍して冷間圧延し、さらに脱炭焼鈍を経て高温仕上げ焼鈍した際に形成されるフォルステライト層と、仕上げ焼鈍の後にフラットニングと同時にりん酸塩などを主成分とする処理液を塗布し焼き付け形成されるりん酸塩被膜層の２層の絶縁被膜がある。 In a grain-oriented electrical steel sheet, after hot-rolling a slab into a hot-rolled sheet, in some cases, it is annealed and cold-rolled, and further, a forsterite layer formed when high-temperature finish annealing is performed through decarburization annealing, There is a two-layered insulating coating, which is a phosphate coating layer that is formed by applying a treatment liquid mainly composed of phosphate at the same time as flattening after finish annealing and baking it.
フォルステライト層は１次被膜とも称され、鋼板とりん酸塩被膜の密着性向上に重要な役割を果たしている。りん酸塩被膜は２次被膜とも称され、電磁鋼板に絶縁性を付与して渦電流損を低減して鉄損を改善し電気機器の効率を向上させるが、絶縁性以外にも耐蝕性、耐熱性、すべり性、加工性といった種々の被膜特性が要求されている。 The forsterite layer is also called a primary coating and plays an important role in improving the adhesion between the steel plate and the phosphate coating. Phosphate coating is also called secondary coating, which provides electrical insulation to electrical steel sheets to reduce eddy current loss and improve iron loss to improve the efficiency of electrical equipment. Various film properties such as heat resistance, slipperiness and workability are required.
つまり、電磁鋼板を加工してトランスなどの鉄芯を製造するためには種々の工程を経る必要があるが、この鉄芯製造の際に加工性、耐熱性、すべり性が劣っていると歪み取り焼鈍時に被膜が剥離したりして絶縁性が低下したり、鋼板を積層するのに時間がかかったりして作業性や組み立て効率が悪化する。 In other words, in order to manufacture an iron core such as a transformer by processing an electromagnetic steel sheet, it is necessary to go through various processes. However, when this iron core is manufactured, distortion is caused when workability, heat resistance, and slipperiness are inferior. Workability and assembly efficiency are deteriorated because the coating is peeled off during annealing and the insulation is lowered, and it takes time to laminate the steel plates.
更に方向性電磁鋼板の絶縁被膜には、電磁鋼板に表面張力を付与し方向性電磁鋼板の磁気特性を向上させるという特性がある。これは張力を付与された電磁鋼板は容易に磁壁移動が可能であり、その結果、鉄損が改善するもので、方向性電磁鋼板を鉄芯に用いて製造されたトランスでは、騒音の主原因のひとつである磁気ひずみの低減にも効果がある。 Furthermore, the insulating coating of the grain-oriented electrical steel sheet has a characteristic of imparting surface tension to the magnetic steel sheet and improving the magnetic properties of the grain-oriented electrical steel sheet. This is because the magnetic steel sheet to which tension is applied can easily move the domain wall, and as a result, the iron loss is improved. In the transformer manufactured using the directional magnetic steel sheet as the iron core, the main cause of noise is It is also effective in reducing magnetostriction, which is one of the above.
特許文献１には、仕上げ焼鈍後に鋼板表面に形成されたフォルステライト被膜の上に特定組成のりん酸塩、クロム酸塩、コロイド状シリカを主成分とする絶縁被膜処理液を塗布焼き付けることにより、高い張力を有する絶縁被膜を鋼板表面に形成し、方向性電磁鋼板の鉄損と磁気ひずみを低減する方法が開示されている。
また特許文献２には、粒径が８ｍμｍ以下の超微粒子コロイド状シリカと第一りん酸塩、クロム酸塩を特定割合含有する処理液を塗布焼き付けることにより、絶縁被膜の高張力を保持し、さらに被膜の潤滑性を向上する方法が開示されている。
さらに特許文献３において、りん酸塩とクロム酸塩とガラス転移点が９５０〜１２００℃のコロイド状シリカを主成分とする絶縁被膜を特定付着量とする高張力絶縁被膜を有する方向性電磁鋼板に関する技術が開示されている。
In Patent Document 1, by applying and baking an insulating coating treatment liquid mainly composed of phosphate, chromate, colloidal silica of a specific composition on a forsterite coating formed on the surface of a steel plate after finish annealing, A method of reducing the iron loss and magnetostriction of a grain-oriented electrical steel sheet by forming an insulating coating having high tension on the steel sheet surface is disclosed.
In Patent Document 2, the high tension of the insulating coating is maintained by applying and baking a treatment liquid containing a specific proportion of ultrafine colloidal silica having a particle size of 8 mμm or less, primary phosphate, and chromate, Furthermore, a method for improving the lubricity of the coating is disclosed.
Furthermore, in patent document 3, it is related with the grain-oriented electrical steel sheet which has a high tension | tensile_strength insulating film which makes the specific amount of the insulating film which has a phosphoric acid, chromate, and a glass transition point 950-1200 degreeC colloidal silica as a main component. Technology is disclosed.
上記公報に開示された技術により、各種被膜特性が格段に優れ、被膜張力も従来より向上したものの、いずれもクロム化合物であるクロム酸塩が配合されているが、近年では環境問題がクローズアップされており、鉛、クロム、カドミウムといった化合物の使用を禁止・制限することが求められている。 The technology disclosed in the above publication has various coating properties that are much better and the coating tension has been improved compared to the conventional ones, but they all contain a chromate that is a chromium compound, but in recent years environmental issues have been highlighted. The use of compounds such as lead, chromium and cadmium is prohibited and restricted.
上記クロム化合物を含有しない技術として、特許文献４にはコロイド状シリカをＳｉＯ２で２０重量部、りん酸アルミを１０〜１２０重量部、ほう酸２〜１０重量部とＭｇ、Ａｌ、Ｆｅ、Ｃｏ、Ｎｉ、Ｚｎのそれぞれの硫酸塩の内から選ばれる１種または２種の合計を４〜４０重量部とを含有する処理液を３００℃以上で焼付処理する絶縁被膜処理方法が開示されている。
さらに特許文献５には、Ｃａ、Ｍｎ、Ｆｅ、Ｚｎ、Ｃｏ、Ｎｉ、Ｃｕ、Ｂ及びＡｌから選ばれる有機酸塩として、蟻酸塩、酢酸塩、蓚酸塩、酒石酸塩、乳酸塩、クエン酸塩、コハク酸塩およびサリチル酸塩から選ばれる有機酸塩の１種または２種以上を添加することを特徴とする方向性電磁鋼板用表面処理剤に関する技術が開示されている。
As a technique which does not contain the chromium compound, 20 parts by weight of colloidal silica SiO 2 in Patent Document 4, 10 to 120 parts by weight of phosphoric acid aluminum borate 2-10 parts by weight of Mg, Al, Fe, Co, An insulating film treatment method is disclosed in which a treatment liquid containing 4 to 40 parts by weight of one or two kinds selected from the sulfates of Ni and Zn is baked at 300 ° C. or higher.
Furthermore, in Patent Document 5, as an organic acid salt selected from Ca, Mn, Fe, Zn, Co, Ni, Cu, B and Al, formate, acetate, oxalate, tartrate, lactate, citrate A technique relating to a surface treatment agent for grain-oriented electrical steel sheets, characterized by adding one or more organic acid salts selected from succinates and salicylates, is disclosed.
しかしながら、上記特許文献４では、硫酸塩中の硫酸イオンによる耐蝕性低下の問題があり、特許文献５では、有機酸塩中の有機酸による変色および液安定性に問題が有り、更なる改善が必要であった。 However, in Patent Document 4, there is a problem of deterioration in corrosion resistance due to sulfate ions in the sulfate, and in Patent Document 5, there are problems in discoloration and liquid stability due to organic acid in the organic acid salt, and further improvements are made. It was necessary.
なお特許文献６には、段落〔００３３〕に、「第一層中のりん酸水素塩から遊離したりん酸を補助するものとして、第一層中に遊離のりん酸を添加することも可能である。また、遊離のりん酸を過剰に添加すると第一層中のりん酸分が余剰となるので、酸化クロムを併用することで耐蝕性が向上するだけでなく、余剰りん酸による歪み取り焼鈍時の焼き付き、いわゆるスティッキングを防止することが可能である。」との技術が開示されているが、上記公報の技術にはホウ酸アルミニウムを主成分とする第二層が必須であって、遊離のりん酸と第二層との化学的親和性に着目した技術であり、従って第一層と第二層という複数層状構造が不可欠で工業的にコスト高になるという問題点があった。 In Patent Document 6, paragraph [0033] states that “free phosphoric acid can be added to the first layer as an aid to the phosphoric acid liberated from the hydrogen phosphate in the first layer. In addition, excessive addition of free phosphoric acid results in an excess of phosphoric acid in the first layer, so the combined use of chromium oxide not only improves the corrosion resistance, but also removes strain by annealing with excess phosphoric acid. It is possible to prevent seizure of time and so-called sticking. "However, the technique disclosed in the above publication requires a second layer mainly composed of aluminum borate and is free. This technique focuses on the chemical affinity between the phosphoric acid and the second layer. Therefore, the multi-layer structure of the first layer and the second layer is indispensable, and there is a problem that the cost is increased industrially.
また、表面処理鋼板の分野でも同様にクロムを含有しないコーティングの開発が進められており、特許文献７には、水ガラスと少なくともチオカルボニル基含有化合物およびバナジウム酸化合物のうち少なくとも１種を含む皮膜層を持つ非クロム型耐熱処理鋼板に関する技術が開示されている。
さらに、特許文献８には、ジルコニウム化合物として、１０〜３０質量％、バナジル化合物をバナジウムとして５〜２０質量％含有している皮膜を少なくとも片面に付着量として２００〜１２００ｍｇ／ｍ２ 形成する技術が開示されている。
Similarly, in the field of surface-treated steel sheets, the development of a coating that does not contain chromium is also proceeding. Patent Document 7 discloses a film containing water glass and at least one of a thiocarbonyl group-containing compound and a vanadate compound. A technique related to a non-chromium heat-resistant steel sheet having a layer is disclosed.
Furthermore, Patent Document 8 discloses a technique for forming a coating containing 10 to 30% by mass as a zirconium compound and 5 to 20% by mass of a vanadyl compound as vanadium and having an adhesion amount of 200 to 1200 mg / m 2 on at least one surface. It is disclosed.
しかしながら、これら表面処理鋼板用のコーティングでは、鋼板に張力を付与する被膜張力も無くまた張力付与に関する技術的言及は無く、さらに電磁鋼板では必要とされる歪み取り焼鈍に耐える耐熱性も無く、電磁鋼板用としては使用に耐えるものではなかった。 However, in these coatings for surface-treated steel sheets, there is no coating tension that imparts tension to the steel sheet, there is no technical reference relating to the application of tension, and there is no heat resistance that can withstand strain relief annealing, which is required for electrical steel sheets. It was not durable for use as a steel sheet.
一方、特許文献９には、酸化アルミニウムあるいは酸化アルミニウム−酸化ホウ素を主成分とし、さらに添加剤としてバンジウム化合物、ビスマス化合物、鉛化合物の中より選ばれる１種または２種以上を含み、被膜形成反応を促進する技術が開示されている。
また特許文献１０には、αアルミナ、ムライト、コーディエライト、ＺｒＯ２ 、Ｍｇ２Ａｌ２Ｏ４ 、Ｍｇ２ＳｉＯ４ 、窒化ケイ素、あるいは炭化ケイ素などのセラミック微結晶と、酸化アルミニウム、あるいは酸化アルミニウム−酸化ホウ素、さらに必要に応じバナジウム化合物、ビスマス化合物、鉛化合物の３種の中より選ばれる１種または２種以上の添加物を含む絶縁被膜に関する技術が開示されている。
On the other hand, Patent Document 9 includes aluminum oxide or aluminum oxide-boron oxide as a main component, and further includes one or more selected from a vandium compound, a bismuth compound, and a lead compound as an additive, and a film forming reaction. A technique for promoting the above is disclosed.
Patent Document 10 discloses ceramic fine crystals such as α-alumina, mullite, cordierite, ZrO 2 , Mg 2 Al 2 O 4 , Mg 2 SiO 4 , silicon nitride, or silicon carbide, and aluminum oxide or aluminum oxide. -A technique relating to an insulating coating containing boron oxide, and optionally one or more additives selected from three kinds of vanadium compounds, bismuth compounds, and lead compounds is disclosed.
しかし、これらの技術では酸化アルミニウムあるいは酸化アルミニウム−酸化ホウ素を含有するため、焼付け温度が低くできず、被膜形成が困難で生産性が低いといった主に生産上の問題点が解決できず、一般化には至っていない。 However, since these technologies contain aluminum oxide or aluminum oxide-boron oxide, the baking temperature cannot be lowered, the film formation is difficult and the productivity is low, and the production problems cannot be solved. It has not reached.
本発明は、方向性電磁鋼板製造の最終工程で鋼板に塗布し焼き付けることにより表面に形成される絶縁被膜の性状を改善することにより、クロム化合物を含有しないにもかかわらず、密着性などの各種被膜特性が良好で生産性も良好であり、かつ従来よりも格段に優れた高張力被膜を有する方向性電磁鋼板を得ることを目的とする。 The present invention improves the properties of the insulating film formed on the surface by applying and baking to the steel sheet in the final step of the production of grain-oriented electrical steel sheet, so that it does not contain a chromium compound, but various such as adhesion It is an object of the present invention to obtain a grain-oriented electrical steel sheet having good coating properties and good productivity, and having a high-tensile coating that is much better than before.
上記目的を達成するため、本発明は以下の構成を要旨とする。
（１）りん酸塩とコロイド状シリカを主成分とし、りん酸塩１００重量部に対しコロイド状シリカ３０〜７０重量部と、りん酸塩中の金属成分が、２価の金属元素を２０〜８０重量％、３価金属が１０〜７０重量％、４価以上の価数を持つ金属元素が３〜２０重量％であることを特徴とする方向性電磁鋼板の絶縁被膜用処理剤。
（２）表面に、りん酸塩とコロイド状シリカ中のシリカ分を主成分とし、りん酸塩とシリカ分の比率がりん酸塩に対しシリカ分が２３〜４１重量％でかつ、りん酸塩の全金属元素中の２価の金属元素の比率が２０〜８０重量％、３価の金属元素の比率が１０〜７０重量％、４価以上の金属元素の比率が３〜２０重量％であることを特徴とする絶縁被膜を有する方向性電磁鋼板。
(３) 前記（１）又は（２）に記載のりん酸塩中の金属成分が、２価の金属元素としてＭｇ、Ｃａ、Ｓｒ、Ｎｉ、Ｃｏ、Ｍｎ、Ｚｎの群、３価の金属元素としてＦｅ、Ａｌ、Ｍｎの群、４価以上の金属元素としてＭｏ、Ｖ、Ｚｒの群からなり、これらそれぞれの群の中から少なくとも１種を選択してなることを特徴とするクロムを含有しない絶縁被膜を有する方向性電磁鋼板。
In order to achieve the above object, the gist of the present invention is as follows.
(1) Mainly composed of phosphate and colloidal silica, 30 to 70 parts by weight of colloidal silica with respect to 100 parts by weight of phosphate, and the metal component in the phosphate contains 20 to 20 divalent metal elements. A treating agent for insulating coatings on grain-oriented electrical steel sheets, wherein 80% by weight, trivalent metal is 10 to 70% by weight, and metal element having a valence of 4 or more is 3 to 20% by weight.
(2) The surface is mainly composed of phosphate and silica in colloidal silica, and the ratio of phosphate to silica is 23 to 41% by weight of silica with respect to phosphate, and phosphate. The ratio of divalent metal elements in all metal elements of 20 to 80% by weight, the ratio of trivalent metal elements to 10 to 70% by weight, and the ratio of tetravalent or higher metal elements to 3 to 20% by weight. A grain-oriented electrical steel sheet having an insulating coating.
(3) The metal component in the phosphate described in (1) or (2) above is a group of Mg, Ca, Sr, Ni, Co, Mn, Zn as a divalent metal element, and a trivalent metal element As a group consisting of Fe, Al, Mn and Mo, V, Zr as tetravalent or higher metal elements, and containing at least one selected from these groups, and does not contain chromium A grain-oriented electrical steel sheet having an insulating coating.
(４) 方向性電磁鋼板にりん酸塩とコロイド状シリカを主成分とする処理剤を塗布して張力被膜を形成する際に、りん酸塩中の２価の金属元素としてＭｇ、Ｃａ、Ｓｒ、Ｎｉ、Ｃｏ、Ｍｎ、Ｚｎの群、３価の金属元素としてＦｅ、Ａｌ、Ｍｎの群、４価以上の金属元素としてＭｏ、Ｖ、Ｚｒの群からなり、これらそれぞれの群の中から少なくとも１種の金属元素を選択してなるりん酸塩混合物１００重量部に対し、コロイド状シリカ４０〜６７重量部とりん酸を２〜５０重量部含有し、ｐＨが１〜４で固形分濃度が１５〜３５％の処理剤を塗布乾燥して焼き付け処理することを特徴とするクロムを有しない方向性電磁鋼板の絶縁被膜処理方法。 (4) When a tensile coating is formed by applying a treatment mainly composed of phosphate and colloidal silica to grain-oriented electrical steel sheets, Mg, Ca, Sr are used as divalent metal elements in the phosphate. , Ni, Co, Mn, Zn group, trivalent metal element Fe, Al, Mn group, tetravalent or higher metal element group Mo, V, Zr, and at least one of these groups. It contains 40 to 67 parts by weight of colloidal silica and 2 to 50 parts by weight of phosphoric acid with respect to 100 parts by weight of a phosphate mixture obtained by selecting one metal element, and has a pH of 1 to 4 and a solid content concentration of 1 to 4 parts. A method for treating an insulating coating on a grain-oriented electrical steel sheet having no chromium, characterized by applying and drying 15 to 35% of a treating agent and baking.
本発明によれば、鋼板の表面に付与される被膜張力が大きく、密着性、耐蝕性が良好で、磁気特性も良好な方向性電磁鋼板を得ることができる。 According to the present invention, it is possible to obtain a grain-oriented electrical steel sheet having a large coating tension applied to the surface of the steel sheet, good adhesion and corrosion resistance, and good magnetic properties.
以下に本発明の内容を詳細に説明する。
まず、本発明を適用する電磁鋼板について、その製造方法としては特に限定するものではなく、従来開示されている方法により製造された仕上げ焼鈍後の方向性電磁鋼板で、通常のフォルステライト被膜を有する鋼板を用いるのが好適である。仕上げ焼鈍後は、余剰の焼鈍分離剤を水洗除去し、硫酸浴などによる酸洗処理、水洗処理を行い表面洗浄と表面の活性化を行った後、本発明の処理液を塗布・乾燥し焼き付けるものである。
The contents of the present invention will be described in detail below.
First, the electrical steel sheet to which the present invention is applied is not particularly limited as a manufacturing method thereof, and is a grain-oriented electrical steel sheet after finish annealing manufactured by a conventionally disclosed method, and has a normal forsterite coating. It is preferable to use a steel plate. After the final annealing, the excess annealing separator is removed by washing with water, pickling with a sulfuric acid bath, washing with water, activating the surface, applying, drying and baking the treatment liquid of the present invention. Is.
具体的にはＳｉを２．０〜４．０ｗｔ％含有し、ＡｌＮ、ＭｎＳ、ＣｕＳなどの化合物をインヒビターとして含有するスラブを熱延してから、場合によっては焼鈍後に冷延して、最終的に０．２〜０．５ｍｍ程度の板厚としたものを脱炭焼鈍し、ＭｇＯを主成分とする焼鈍分離剤を塗布してから、１１００℃前後までゆっくり加熱してバッチ炉で高温焼鈍を行い、いわゆる２次再結晶させると共に表面にフォルステライト被膜を形成した後、余剰のＭｇＯを水洗したものを用いる。 Specifically, after hot-rolling a slab containing 2.0 to 4.0 wt% of Si and containing a compound such as AlN, MnS, or CuS as an inhibitor, in some cases, it is cold-rolled after annealing, and finally Then, decarburizing and annealing with a plate thickness of about 0.2 to 0.5 mm, applying an annealing separator mainly composed of MgO, and slowly heating to around 1100 ° C., followed by high-temperature annealing in a batch furnace. After performing a so-called secondary recrystallization and forming a forsterite film on the surface, an excess of MgO washed with water is used.
次に、本発明で使用する絶縁被膜処理剤は、添加するりん酸塩に特徴がある。
すなわち、りん酸塩には様々な種類があるが、本発明では２価のりん酸金属塩と３価のりん酸金属塩と４価以上のりん酸金属塩を混合し、さらに好適には特定割合で混合することである。
Next, the insulating film treating agent used in the present invention is characterized by the added phosphate.
That is, although there are various types of phosphates, in the present invention, a divalent phosphate metal salt, a trivalent phosphate metal salt, and a tetravalent or higher phosphate metal salt are mixed, and more preferably specified. Mixing in proportion.
具体的には、２価のりん酸金属塩としてりん酸マグネシウム、りん酸カルシウム、りん酸ストロンチウム、りん酸ニッケル、りん酸マンガン、りん酸コバルト、りん酸亜鉛などが適当で、３価のりん酸金属塩としてはりん酸アルミニウム、りん酸鉄、りん酸マンガンが、４価以上のりん酸金属塩として、りん酸モリブデン、りん酸バナジウム、りん酸ジルコニウムが適当である。 Specifically, magnesium phosphate, calcium phosphate, strontium phosphate, nickel phosphate, manganese phosphate, cobalt phosphate, zinc phosphate, etc. are suitable as the divalent metal phosphate, and trivalent phosphate. As the metal salt, aluminum phosphate, iron phosphate, and manganese phosphate are suitable, and as the tetravalent or higher phosphate metal salt, molybdenum phosphate, vanadium phosphate, and zirconium phosphate are suitable.
さらには、２価ではりん酸マグネシウム、りん酸マンガン、りん酸ニッケル、りん酸亜鉛を、３価ではりん酸アルミニウムを、４価以上ではりん酸バナジウムを、それぞれ少なくとも１種以上含有させることが好ましい。 Furthermore, it is preferable to contain at least one of magnesium phosphate, manganese phosphate, nickel phosphate and zinc phosphate for divalent, aluminum phosphate for trivalent, and vanadium phosphate for tetravalent or higher. .
りん酸マンガンは特異な性質を持ち、２価としても３価としても安定なりん酸塩を形成可能であるが、比較的２価のりん酸金属塩として安定であるため、２価として好適である。同様に複数の価数が存在する場合でも、処理液のｐＨや配合する配位子によって、特定価数のりん酸金属塩として安定する場合には使用することが可能である。
これらりん酸塩は、水溶性である場合には水溶液として使用するが、難溶性の場合にはゾル状やコロイド状の分散液を用いても良い。
Manganese phosphate has unique properties and can form stable phosphates as both divalent and trivalent. However, since it is relatively stable as a divalent metal phosphate, it is suitable as divalent. is there. Similarly, even when a plurality of valences are present, they can be used if they are stabilized as a phosphate metal salt having a specific valence depending on the pH of the treatment liquid and the ligand to be blended.
These phosphates are used as aqueous solutions when water-soluble, but sol-like or colloidal dispersions may be used when they are sparingly soluble.
次に、本発明で使用するりん酸塩の形態は特に限定するものでは無く、従って処理液に使用するりん酸としては、オルトりん酸やメタりん酸、ポリりん酸が使用できる。また、ホスホン酸を用いても良い。 Next, the form of the phosphate used in the present invention is not particularly limited. Accordingly, orthophosphoric acid, metaphosphoric acid, and polyphosphoric acid can be used as the phosphoric acid used in the treatment liquid. Further, phosphonic acid may be used.
処理液中の価数と、絶縁被膜中の価数が異なっていても問題無い。すなわち、焼付けにより価数が変化することは十分考えられ、本発明の場合には大気中で８００℃から１０００℃で加熱することからオルトりん酸塩が安定であり、処理液中の状態とは異なり化学的に安定なオルトりん酸塩状態を取り易いと考えられる。 There is no problem even if the valence in the treatment liquid and the valence in the insulating coating are different. That is, it is considered that the valence changes due to baking, and in the case of the present invention, orthophosphate is stable because it is heated at 800 to 1000 ° C. in the atmosphere. Unlikely, it is considered that it is easy to take a chemically stable orthophosphate state.
絶縁被膜中のりん酸金属塩の金属原子の価数が不明な場合にはＸ線構造解析を行い、りん酸金属塩の構造を決定して価数を決めることも可能である。この場合、りん酸鉄は非晶質になり易く、Ｘ線構造解析が困難な場合もあるが、オルトりん酸鉄が安定であることから、鉄元素は３価になっていると考えて問題ない。 When the valence of the metal atom of the metal phosphate in the insulating coating is unknown, the valence can be determined by performing X-ray structural analysis and determining the structure of the metal phosphate. In this case, iron phosphate is likely to be amorphous, and X-ray structural analysis may be difficult, but since iron orthophosphate is stable, it is considered that the iron element is trivalent. Absent.
それぞれの価数の金属元素の配合割合は、２価の金属元素が２０〜８０ｗｔ％、３価の金属元素が１０〜７０ｗｔ％、４価以上の金属元素が３〜２０ｗｔ％に限定される。その理由は、２価金属元素が２０ｗｔ％未満、３価金属元素が１０ｗｔ％未満、４価以上の金属元素が３ｗｔ％未満では、本発明の効果が不完全で、被膜の密着性や耐蝕性、あるいは被膜張力が劣化する恐れがあり、２価の金属元素が８０ｗｔ％超では被膜が白色化して密着性が低下する恐れがあり、３価金属元素が７０ｗｔ％超では被膜張力が劣化する傾向があり、４価以上の金属元素が２０ｗｔ％超では処理液の安定性が劣るためである。
さらに好適な範囲は２価金属元素が４０〜６０ｗｔ％、３価の金属元素が３０〜５０ｗｔ％、４価以上の金属元素が５〜１５ｗｔ％である。
The mixing ratio of each valence metal element is limited to 20 to 80 wt% for divalent metal elements, 10 to 70 wt% for trivalent metal elements, and 3 to 20 wt% for tetravalent or higher metal elements. The reason is that if the divalent metal element is less than 20 wt%, the trivalent metal element is less than 10 wt%, and the tetravalent or higher metal element is less than 3 wt%, the effect of the present invention is incomplete, and the adhesion and corrosion resistance of the coating are incomplete. Otherwise, the film tension may be deteriorated. If the divalent metal element exceeds 80 wt%, the film may be whitened and the adhesion may be lowered. If the trivalent metal element exceeds 70 wt%, the film tension tends to deteriorate. This is because the stability of the treatment liquid is inferior when the tetravalent or higher-valent metal element exceeds 20 wt%.
A more preferable range is 40 to 60 wt% for divalent metal elements, 30 to 50 wt% for trivalent metal elements, and 5 to 15 wt% for tetravalent or higher metal elements.
また、本発明で使用する絶縁被膜処理剤はｐＨ１〜４の範囲とするのがよい。ｐＨが１未満では鋼板を腐食し易く、耐蝕性が劣化する恐れがあり、４超では処理液が不安定になり、沈殿等が発生してコーティングが困難になるためである。さらに好適にはｐＨ２〜３の範囲である。
ｐＨの調整には、各種ｐＨ調整剤やジオキサン、エタノール、クエン酸、アジピン酸、りんご酸などの有機物を用いても良い。
Moreover, it is good for the insulating-film processing agent used by this invention to be the range of pH 1-4. If the pH is less than 1, the steel sheet is easily corroded and the corrosion resistance may be deteriorated, and if it exceeds 4, the treatment liquid becomes unstable, precipitation occurs, and coating becomes difficult. More preferably, the pH is in the range of 2 to 3.
Various pH adjusting agents and organic substances such as dioxane, ethanol, citric acid, adipic acid and malic acid may be used for adjusting the pH.
本発明で使用するコロイド状シリカは、特に粒径を限定するものではないが、５〜５０ｎｍのものがよく、さらには粒径６〜１５ｎｍのものが好適である。また、処理剤がｐＨ２〜６の酸性領域であることから、添加するコロイド状シリカは酸性タイプのものが好適で、表面にＡｌ処理を施したものは特に良好である。 The colloidal silica used in the present invention is not particularly limited in particle size, but is preferably 5 to 50 nm, more preferably 6 to 15 nm. In addition, since the treatment agent is in the acidic region of pH 2 to 6, the colloidal silica to be added is preferably of the acidic type, and the surface treated with Al is particularly good.
絶縁被膜の形成量は２〜７ｇ／ｍ２ が好適である。２ｇ／ｍ２未満では高張力を得るのが困難であり、また絶縁性、耐蝕性等も低下し、７ｇ／ｍ２を超えると占積率が低下するためである。 The formation amount of the insulating coating is preferably 2 to 7 g / m 2 . If it is less than 2 g / m 2, it is difficult to obtain a high tension, and insulation and corrosion resistance also decrease. If it exceeds 7 g / m 2 , the space factor decreases.
次に、本発明で使用する処理剤のコロイド状シリカとりん酸塩との配合割合は固形分換算で、りん酸塩１００重量部に対し、コロイド状シリカが３０〜７０重量部に限定される。３０重量部未満ではコロイド状シリカの割合が少な過ぎて張力効果が劣り、７０重量部超ではコーティングに割れや剥離などの欠陥が発生しやすくなるためである。 Next, the blending ratio of the colloidal silica and phosphate of the treating agent used in the present invention is limited to 30 to 70 parts by weight of colloidal silica with respect to 100 parts by weight of phosphate in terms of solid content. . If the amount is less than 30 parts by weight, the proportion of colloidal silica is too small and the tension effect is inferior. If it exceeds 70 parts by weight, defects such as cracking and peeling are likely to occur in the coating.
本発明の効果が発現するメカニズムは詳細には明らかではないが、一般にりん酸金属塩は重合し易く、緻密な被膜を形成するものであるが、本発明のような電磁鋼板用途では比較的大量のコロイド状シリカが混合されており、結合強度の高い被膜を得ることは困難であった。
そこで本発明者らはりん酸金属塩の重合を助長する組成を鋭意検討した結果、りん酸金属塩の金属元素の価数を複数導入し、かつ２価と３価と４価以上の金属元素の構成割合を特定することにより、りん酸金属塩がより重合し、緻密な被膜を形成することを知見した。特に４価以上の金属元素を特定量導入することで飛躍的に緻密な被膜が形成されることを見出したものである。
Although the mechanism by which the effects of the present invention are manifested is not clear in detail, metal phosphates are generally easy to polymerize and form a dense film. It was difficult to obtain a coating film having a high bond strength.
Accordingly, the present inventors have intensively studied the composition that promotes the polymerization of metal phosphates, and as a result, introduced a plurality of metal element valences of metal phosphates, and metal elements that are divalent, trivalent, and tetravalent or higher. It was found that the metal phosphate was more polymerized and a dense film was formed by specifying the constituent ratio of. In particular, it has been found that by introducing a specific amount of a tetravalent or higher-valent metal element, a remarkably dense film can be formed.
次に本発明の実施例について述べる。
Ｓｉを３．３ｗｔ％、Ａｌを０．０２７ｗｔ％、Ｎを０．００８ｗｔ％、Ｃを０．０８ｗｔ％含有する溶鋼を鋳造し、スラブ加熱後熱間圧延を行い、１１００℃で５分間熱延板を焼鈍してから冷却し、冷間圧延を行い０．２３ｍｍ厚にした。その後８５０℃で３分間脱炭焼鈍を行い、ＭｇＯを主成分とする焼鈍分離剤を塗布した後、１２００℃で２０時間最終仕上げ焼鈍を行った。このコイルから幅７ｃｍ×長さ３０ｃｍの試料を切り出し、表面に残存している焼鈍分離剤を水洗と軽酸洗で除去し、グラス被膜を残した後に歪取り焼鈍を行った。
Next, examples of the present invention will be described.
A molten steel containing 3.3 wt% Si, 0.027 wt% Al, 0.008 wt% N and 0.08 wt% C is cast, hot-rolled after slab heating, and hot rolled at 1100 ° C. for 5 minutes. The plate was annealed and then cooled and cold rolled to a thickness of 0.23 mm. Thereafter, decarburization annealing was performed at 850 ° C. for 3 minutes, and after applying an annealing separator mainly composed of MgO, final finishing annealing was performed at 1200 ° C. for 20 hours. A sample having a width of 7 cm and a length of 30 cm was cut out from this coil, the annealing separator remaining on the surface was removed by washing with water and light pickling, and after removing the glass film, strain relief annealing was performed.
次に、表１に示す配合割合でりん酸塩溶液を調製した後、塗布量が４ｇ／ｍ２ になるよう鋼板にロールコーターで塗布し、８７０℃の加熱炉中で板温が８５０℃になるように６０秒間焼き付けた後、被膜特性と磁気特性を評価した。 Next, after preparing a phosphate solution at a blending ratio shown in Table 1, it was applied to a steel plate with a roll coater so that the coating amount was 4 g / m 2 , and the plate temperature was adjusted to 850 ° C. in a heating furnace at 870 ° C. After baking for 60 seconds, the film properties and magnetic properties were evaluated.
結果を表２に示す。
比較例１では、４価以上の金属元素を配合しないため被膜張力が劣り、比較例２では３価金属元素を配合しないため密着性が劣化し、比較例３では２価金属元素を配合しないため本発明の効果が得られず耐蝕性が劣り、比較例４では２価金属元素の配合量が少なすぎるためまだら模様が発生して耐蝕性が非常に悪くなった。
比較例５では２価金属元素が多過ぎるため本発明の効果が得られず密着性に劣り、比較例６では３価の金属元素が少な過ぎるためやはり本発明の効果が得られず密着性が低い。
比較例７では３価の金属元素が逆に多過ぎて被膜張力が劣化し、比較例８では４価以上の金属元素が少な過ぎて本発明の効果が得られずに被膜張力が低下し、比較例９では４価以上の金属元素が多過ぎて処理液が不安定になり、かろうじて塗布はできたが被膜張力が劣化した。比較例１０では、りん酸塩に対するシリカの割合が多過ぎるため密着性が低い。
The results are shown in Table 2.
In Comparative Example 1, the film tension is inferior because a metal element having a valence of 4 or more is not blended. In Comparative Example 2, the adhesion is deteriorated because a trivalent metal element is not blended. In Comparative Example 3, a divalent metal element is not blended. The effect of the present invention was not obtained, and the corrosion resistance was inferior. In Comparative Example 4, the amount of the divalent metal element was too small, so that mottled patterns were generated and the corrosion resistance was very poor.
In Comparative Example 5, the effect of the present invention cannot be obtained because there are too many divalent metal elements, and the adhesion is inferior. In Comparative Example 6, the effect of the present invention cannot be obtained because there are too few trivalent metal elements. Low.
In Comparative Example 7, the trivalent metal element is too much, and the film tension is deteriorated. In Comparative Example 8, the tetravalent or higher metal element is too small, and the effect of the present invention is not obtained, and the film tension is lowered. In Comparative Example 9, the amount of tetravalent or higher metal element was too much and the treatment solution became unstable, and the coating tension was barely deteriorated, but the film tension was deteriorated. In Comparative Example 10, the adhesiveness is low because the ratio of silica to phosphate is too high.
この試験の結果、りん酸塩１００重量部にコロイド状シリカ３０〜７０重量部、りん酸金属塩中の２価の金属元素が２０〜８０重量％、３価の金属元素が１０〜７０重量％、４価以上の金属元素が３〜２０重量％の処理液を塗布焼付けた絶縁被膜を有する本発明の電磁鋼板は、比較例と比べて高張力で密着性、耐蝕性に優れ、磁気特性の改善効果が顕著であった。
As a result of this test, 100 to 100 parts by weight of phosphate, 30 to 70 parts by weight of colloidal silica, 20 to 80% by weight of divalent metal element in metal phosphate and 10 to 70% by weight of trivalent metal element The electrical steel sheet of the present invention having an insulating coating obtained by applying and baking a treatment liquid containing 3 to 20% by weight of a tetravalent or higher-valent metal element is higher in tension and excellent in adhesion and corrosion resistance than the comparative example, and has magnetic properties. The improvement effect was remarkable.
Claims (4)
When a tensile coating is formed by applying a treatment mainly composed of phosphate and colloidal silica to a grain-oriented electrical steel sheet, Mg, Ca, Sr, Ni, and the like as divalent metal elements in the phosphate are formed. A group of Co, Mn, Zn, a group of Fe, Al, Mn as a trivalent metal element, a group of Mo, V, Zr as a metal element more than tetravalent, and at least one of these groups It contains 40 to 67 parts by weight of colloidal silica and 2 to 50 parts by weight of phosphoric acid with respect to 100 parts by weight of a phosphate mixture formed by selecting a metal element, has a pH of 1 to 4 and a solid content concentration of 15 to 35. % Insulating agent treatment method for grain-oriented electrical steel sheets having no chromium, characterized in that the treatment agent is applied and dried by baking.
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