JPH01168005A - Forming method for insulating film with excellent heat resistance of electromagnetic steel plate - Google Patents
Forming method for insulating film with excellent heat resistance of electromagnetic steel plateInfo
- Publication number
- JPH01168005A JPH01168005A JP32589587A JP32589587A JPH01168005A JP H01168005 A JPH01168005 A JP H01168005A JP 32589587 A JP32589587 A JP 32589587A JP 32589587 A JP32589587 A JP 32589587A JP H01168005 A JPH01168005 A JP H01168005A
- Authority
- JP
- Japan
- Prior art keywords
- insulating film
- heat resistance
- calcium chromate
- excellent heat
- steel sheet
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims description 13
- 229910000831 Steel Inorganic materials 0.000 title abstract description 30
- 239000010959 steel Substances 0.000 title abstract description 30
- BCFSVSISUGYRMF-UHFFFAOYSA-N calcium;dioxido(dioxo)chromium;dihydrate Chemical compound O.O.[Ca+2].[O-][Cr]([O-])(=O)=O BCFSVSISUGYRMF-UHFFFAOYSA-N 0.000 claims abstract description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 10
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 24
- 229910000976 Electrical steel Inorganic materials 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 13
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 9
- 239000008119 colloidal silica Substances 0.000 abstract description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract 3
- -1 acetic acid ions Chemical class 0.000 abstract 2
- 238000000137 annealing Methods 0.000 description 15
- 238000000576 coating method Methods 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229960004793 sucrose Drugs 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- WMYWOWFOOVUPFY-UHFFFAOYSA-L dihydroxy(dioxo)chromium;phosphoric acid Chemical compound OP(O)(O)=O.O[Cr](O)(=O)=O WMYWOWFOOVUPFY-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 1
- KHADWTWCQJVOQO-UHFFFAOYSA-N zinc;oxido-(oxido(dioxo)chromio)oxy-dioxochromium Chemical compound [Zn+2].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KHADWTWCQJVOQO-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Soft Magnetic Materials (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、電磁鋼板の耐熱性に優れた絶縁皮膜の形成
方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for forming an insulating film with excellent heat resistance on an electrical steel sheet.
従来、電磁鋼板の絶縁皮膜としては、リン酸塩、クロム
酸塩系の無機質皮膜と、フェノール樹脂、アクリル樹脂
を含有した有機−無機混合皮膜とに大別されている。Conventionally, insulating coatings for electrical steel sheets have been broadly classified into phosphate- and chromate-based inorganic coatings and organic-inorganic mixed coatings containing phenolic resins and acrylic resins.
一般に電磁鋼板の絶縁皮膜に要求される性能としては、
層間絶縁性、溶接性、占積率、耐熱性に重点が置かれて
いたが、最近、打抜き性についても高い要求がなされて
いる。それらの性能を満足する絶縁皮膜として、本出願
人は、有機樹脂を含有する有機−無機混合皮膜を以前提
案した（特開昭４９−１２０１９７号）。Generally, the performance required for the insulation coating of electrical steel sheets is as follows:
Although emphasis has been placed on interlayer insulation, weldability, space factor, and heat resistance, high demands have recently been placed on punchability as well. As an insulating film that satisfies these performances, the present applicant previously proposed an organic-inorganic mixed film containing an organic resin (Japanese Unexamined Patent Publication No. 120197/1983).
この絶縁皮膜は、有機成分としてフェノール樹脂、スチ
レン−ブタジェン共重合体、エポキシ樹脂のいずれか１
種または２種を含み、無機成分として重クロム酸亜鉛お
よび硝酸アルミニウムを含む処理液を、電磁鋼板の表面
に塗布し、焼き付けてなるものである、しかしながら、
この絶縁皮膜は有機樹脂を含有するため耐熱性に欠け、
皮膜形成後の歪み取り焼鈍で有機樹脂の変質により劣化
する。This insulating film contains any one of phenol resin, styrene-butadiene copolymer, and epoxy resin as an organic component.
However, a treatment solution containing zinc dichromate and aluminum nitrate as inorganic components is applied to the surface of an electrical steel sheet and baked.
This insulating film lacks heat resistance because it contains organic resin,
Deterioration occurs due to deterioration of the organic resin during strain relief annealing after film formation.
一方、無機質皮膜としてリン酸塩系の絶縁皮膜が知られ
ているが、この皮膜は絶縁性を高くするためには厚塗り
する必要がある上、厚塗りのため歪み取り焼鈍により皮
膜の剥離を生じ易い欠点もある。On the other hand, a phosphate-based insulating film is known as an inorganic film, but this film needs to be coated thickly in order to have high insulation properties, and due to the thick coating, it is difficult to peel off the film by annealing to remove distortion. There are also some drawbacks that can easily occur.
ところで、特公昭４９−６７４２号は、上記□の歪み取
り焼鈍によっても皮膜の劣化がなく、絶縁性に優れた絶
縁皮膜として、リン酸塩、クロム酸塩の１種または２種
に耐熱性成分としてアルミナゾルとコロイド状シリカと
を添加することにより、耐熱性を持たせた皮膜を提案し
ている。By the way, Japanese Patent Publication No. 49-6742 discloses that the film does not deteriorate even after the strain relief annealing described in □ above, and that a heat-resistant component is added to one or both of phosphates and chromates to create an insulating film with excellent insulation properties. By adding alumina sol and colloidal silica, we are proposing a film with heat resistance.
しかしながら、上記特公昭４９−６７４２号の技術では
、絶縁皮膜に耐熱性を持たせるためにアルミナゾルとコ
ロイド状シリカとを併用しなければならないという難点
があるだけでなく、その耐熱性も未だ充分でない欠点も
ある。However, the technique disclosed in Japanese Patent Publication No. 49-6742 has the disadvantage that alumina sol and colloidal silica must be used together in order to impart heat resistance to the insulating film, and the heat resistance is still insufficient. There are also drawbacks.
この発明の目的は、上述の現状に鑑み、皮膜形成後の歪
み取り焼鈍によっても劣化することのない、耐熱性に優
れた絶縁皮膜を、アルミナゾルにコロイド状シリカを併
用することなく形成できる、電磁鋼板の耐熱性にイ憂れ
た絶縁皮膜の形成方法を提供することにある。In view of the above-mentioned current situation, it is an object of the present invention to provide an electromagnetic film that can form an insulating film with excellent heat resistance that does not deteriorate even when subjected to strain relief annealing after film formation, without using colloidal silica in combination with alumina sol. An object of the present invention is to provide a method for forming an insulating film that is concerned about the heat resistance of a steel plate.
本発明者等は、電磁鋼板の耐熱性に優れた絶縁皮膜を耐
熱性成分としてアルミナゾルにコロイド状シリカを併用
することなく形成できる方法を得べく鋭意研究を重ねた
結果、単にクロム酸塩でなく特定のクロム酸カルシウム
を用い、アルミナゾルとして酢酸イオンで安定化させた
アルミナゾルを用いて、これらを組み合せれば、アルミ
ナゾルに更にコロイド状シリカを併用しなくても、耐熱
性に優れた絶縁皮膜を得ることができることを見い出し
た。The inventors of the present invention have conducted intensive research to find a method for forming an insulating film with excellent heat resistance on electrical steel sheets using a heat-resistant component without using colloidal silica in alumina sol. By using a specific calcium chromate, using an alumina sol stabilized with acetate ions, and combining these, an insulating film with excellent heat resistance can be obtained without using colloidal silica in addition to the alumina sol. I found out that it is possible.
この発明の絶縁皮膜の形成方法は上記知見に基づいてな
されたもので、
クロム酸カルシウムをＣｒＣｈ ｍ算で１０〜７０ｇ／
２含有し、酢酸イオンで安定化させたアルミナゾルを固
型分量で前記クロム酸カルシウムのＣｒＪ換算の含有量
の２５〜７５％含有し、還元性の有機化合物を前記クロ
ム酸カルシウムのＣｒＯ３換算の含有量の１０〜４０％
含有する処理液を、電磁鋼板の表面に乾燥重量で０．５
〜４ｇ／＋ｔｆ塗布し、前記処理液を２００〜４００℃
の温度で前記電磁鋼板の表面に焼き付けることに特徴を
有するものである。The method for forming an insulating film of the present invention was made based on the above knowledge, and consists of using calcium chromate of 10 to 70 g/m calculated as CrCh.
2 and stabilized with acetate ions in a solid amount of 25 to 75% of the content in terms of CrJ of the calcium chromate, and the content of a reducing organic compound in terms of CrO3 of the calcium chromate. 10-40% of the amount
The treatment liquid contained in the electromagnetic steel sheet is applied to the surface of the electrical steel sheet in a dry weight of 0.5
~4g/+tf was applied, and the treatment liquid was heated at 200~400°C.
It is characterized in that the surface of the electromagnetic steel sheet is baked at a temperature of .
以下、この発明の方法について詳述する。The method of this invention will be explained in detail below.
この発明で使用する処理液では、主剤としてクロム酸カ
ルシウム（ＣａＣｒ０ａ ）を用いる。これは、第１図
にクロム酸含有溶液の薬液相溶性を示すように、クロム
酸カルシウム以外のクロム酸塩またはクロム酸を用いた
クロム酸含有溶液では、クロム酸カルシウムを用いたク
ロム酸含有溶液よりも薬液の相溶性が劣り、品質特性的
に満足できないからである。The treatment liquid used in this invention uses calcium chromate (CaCr0a) as the main ingredient. As shown in Figure 1, which shows the chemical compatibility of chromic acid-containing solutions, in chromic acid-containing solutions using chromate or chromic acid other than calcium chromate, chromic acid-containing solutions using calcium chromate This is because the compatibility of the chemical liquid is inferior to that of the solution, and the quality characteristics cannot be satisfied.
処理液のクロム酸カルシウムの含有量はＣｒＪ換算で１
０〜７０ｇ／ｌとする。これは、クロム酸カルシウムの
含有量がＣｒＯ３換算で１０ ｇ／ＩＶ、未満であると
絶縁皮膜に充分な耐食性が得られないからであり、また
７ ０ ｇ ／ ｊ！を超えると膜厚が厚くなり、絶縁
皮膜を形成した電磁鋼板に占める鋼板部分の占積率が小
さくなり過ぎるからである。The content of calcium chromate in the treatment liquid is 1 in terms of CrJ.
0 to 70 g/l. This is because if the content of calcium chromate is less than 10 g/IV in terms of CrO3, sufficient corrosion resistance cannot be obtained in the insulating film; This is because if it exceeds , the film thickness becomes thick and the space factor of the steel sheet portion of the electrical steel sheet on which the insulating film is formed becomes too small.
処理液にはクロム酸カルシウムの還元剤として、還元性
の有機化合物を含有させる。還元性の有機化合物として
は、ショ糖、エチレングリコールなどの有機アルコール
が適している。その含有量は、クロム酸カルシウムのＣ
ｒＯ３換算の含有量の１０〜４０％の範囲とすることが
好ましい。これは、還元性の有機化合物の含有量がクロ
ム酸カルシウムのＣ「０３換算の含有量の１０％未満で
あると、クロム酸カルシウムに対して不充分過ぎて、ク
ロム酸カルシウム中のＣｒ’°のＣｒ”への還元が充分
に行なわれず、絶縁皮膜にヘタ付きが生じるからであり
、また４０％を超えると、クロム酸カルシウムに対して
過剰になり過ぎ、還元性の有機化合物が絶縁皮膜中に残
存して、皮膜形成後の歪み取り焼鈍で劣化し、耐熱性に
劣る絶縁皮膜になるからである。The treatment liquid contains a reducing organic compound as a reducing agent for calcium chromate. Suitable reducing organic compounds include organic alcohols such as sucrose and ethylene glycol. Its content is C of calcium chromate
The content is preferably in the range of 10 to 40% in terms of rO3. This is because if the content of reducing organic compounds is less than 10% of the C'03 content of calcium chromate, it is too insufficient for calcium chromate, and the Cr'° content in calcium chromate is too low. This is because the reduction of Cr to Cr is not carried out sufficiently, causing the insulating film to sag.If it exceeds 40%, the amount is too much compared to calcium chromate, and reducing organic compounds are deposited in the insulating film. This is because the insulating film remains in the film and deteriorates during strain relief annealing after film formation, resulting in an insulating film with poor heat resistance.
処理液には絶縁皮膜の耐熱性成分として、酢酸イオンで
安定化させたアルミナゾルを含有させる。The treatment solution contains alumina sol stabilized with acetate ions as a heat-resistant component of the insulating film.
これは、酢酸イオンで安定化させたアルミナゾルが、絶
縁皮膜に耐熱性を持たせるのに最も効果があり、皮膜形
成後の歪み取り焼鈍によっても劣化のない絶縁皮膜が得
られるからである。This is because alumina sol stabilized with acetate ions is most effective in imparting heat resistance to the insulating film, and an insulating film that does not deteriorate even when subjected to strain relief annealing after film formation can be obtained.
本発明者等は、絶縁皮膜に耐熱性を持たせることに関し
種々の耐熱性成分を試した結果、第１表に示すように、
酢酸イオンで安定化させたアルミナゾルが、コロイド状
シリカや塩素イオン等で安定化させたアルミナゾルなど
よりも効果があり、耐熱性に優れた絶縁皮膜が得られる
ことを初めて見い出したものである。The present inventors tested various heat-resistant components in order to impart heat resistance to the insulating film, and as a result, as shown in Table 1,
This is the first discovery that alumina sol stabilized with acetate ions is more effective than alumina sol stabilized with colloidal silica or chloride ions, and can produce an insulating film with excellent heat resistance.
この発明で用いるｌ５１１：酸イオンで安定化させたア
ルミナゾルは、他の塩素イオン、６１１酸イオンで安定
化させたアルミナゾルと同様、粒径約１００ｍμ×１０
ｍμの羽毛状粒子になっている。酢酸イオンで安定化さ
せたアルミナゾルとしては、例えば日照化学製アルミナ
ゾル−２００や触媒化学型ＭＳ−１等が市販品として入
手することができる。The alumina sol stabilized with l511 acid ions used in this invention has a particle size of approximately 100 mμ x 10
It is a feather-like particle of mμ. As alumina sol stabilized with acetate ions, for example, alumina sol-200 manufactured by Nissho Chemical Co., Ltd. and Catalyst Chemical Type MS-1 can be obtained as commercial products.
酢酸、イオンで安定化させたアルミナゾルを耐熱性成分
とすると、絶縁皮膜の耐熱性が優れる理由は、その形状
が異形の羽毛状粒子であるために、球状のシルカ粒子な
どと違って、絶縁皮膜中で互いにからみあうことにより
緻密な状態で存在するからであると考えられる。When alumina sol stabilized with acetic acid and ions is used as a heat-resistant component, the reason why the insulating film has excellent heat resistance is that the insulating film has an irregularly shaped feather-like particle shape, unlike spherical silica particles. This is thought to be because they exist in a dense state by intertwining with each other inside.
酢酸イオンで安定化させたアルミナゾルの含有量が固型
分量で、クロム酸カルシウムのＣｒ０ｉ換算の含有量の
２５％未満であると、絶縁皮膜の歪み取り焼鈍後の湿潤
試験（ＨＣＴ ）の結果を示す第２図から明らかなよう
に、絶縁皮膜の耐熱性に劣るようになり、歪み取り焼鈍
で絶縁皮膜が劣化する。一方、前記含有量が同じく７５
％を超えると、処理液の粘度が急激に増加し、作業性が
悪化する。If the solid content of the alumina sol stabilized with acetate ions is less than 25% of the Cr0i equivalent content of calcium chromate, the results of the wet test (HCT) after strain relief annealing of the insulation film As is clear from FIG. 2, the heat resistance of the insulating film becomes inferior, and the insulating film deteriorates during strain relief annealing. On the other hand, the content is also 75
%, the viscosity of the treatment liquid will increase rapidly and workability will deteriorate.
以上から、酢酸イオンで安定化させたアルミナゾルの含
有量は固型分量で、クロム酸カルシウムのＣｒＯ＋換算
の含有量の２５〜７５％が良く、好ましくは３０〜６０
％が良い。From the above, the solid content of the alumina sol stabilized with acetate ions is preferably 25 to 75% of the CrO+ content of calcium chromate, preferably 30 to 60%.
% is good.
以上の処理液を調製し、これを電磁鋼板の表面に塗布し
、焼き付けて、電磁鋼板の表面に絶縁皮膜を形成する。The above treatment liquid is prepared, applied to the surface of the electrical steel sheet, and baked to form an insulating film on the surface of the electrical steel sheet.
処理液の電磁鋼板表面への塗布量は乾燥重量で４ ｇ／
ｒｄを超えると、絶縁皮膜の電磁鋼板表面への密着性が
低下する原因となり、一方０．５ｇ／％未満であると、
絶縁皮膜に充分な耐熱性を得ることができない、従って
、処理液の塗布量は乾燥重量で０．５〜４ ｇ／ｍの範
囲が良く、好ましくは１．０〜２．５ｇ／ｒｒｒの範囲
が良い。The amount of treatment liquid applied to the surface of the electrical steel sheet is 4 g/dry weight.
If it exceeds rd, it will cause the adhesion of the insulating film to the surface of the electrical steel sheet to decrease, while if it is less than 0.5 g/%,
It is not possible to obtain sufficient heat resistance for the insulating film. Therefore, the coating amount of the treatment liquid is preferably in the range of 0.5 to 4 g/m in dry weight, preferably in the range of 1.0 to 2.5 g/rrr. is good.
処理液の電磁鋼板表面への焼き付けによる皮■り形成は
短時間で行なう必要があり、焼付は温度が到達板温で２
００℃未満であると、皮膜形成が不充分で良好な絶縁皮
膜が得られず、一方４００℃を超えても絶縁皮ｊＩりの
性能上の向上は認められない。従って、処理液の焼付は
温度は到達板温で２５０〜４００℃の範囲とすることが
適当である。The formation of a skin by baking the treatment liquid onto the surface of the electrical steel sheet needs to be done in a short time, and the baking is done when the temperature reaches the plate temperature of 2.
If the temperature is less than 00°C, film formation is insufficient and a good insulating film cannot be obtained.On the other hand, if the temperature exceeds 400°C, no improvement in the performance of the insulating film is observed. Therefore, it is appropriate that the baking temperature of the treatment liquid is in the range of 250 to 400°C in terms of the final plate temperature.
以上に述べた条件の処理液およびその塗布、焼付けによ
って、電磁鋼板の表面に耐熱性に優れた無機質系の絶縁
皮膜を得ることができる。By using the treatment liquid under the conditions described above, its application, and baking, an inorganic insulating film with excellent heat resistance can be obtained on the surface of the electrical steel sheet.
この発明の方法に従って電磁鋼板の表面に絶縁皮膜を形
成し、本発明鋼板階１〜３を得た。比較のために、処理
液をこの発明の方法の範囲外とした条件で、電磁鋼板の
表面に絶縁皮膜を形成し、比較鋼板１１ｍ４〜６を得た
。そして、これら本発明鋼板ａ１〜３、比較鋼板阻４〜
６の絶縁皮膜の耐熱性を、７５０’ＣＸ２ｈｒの歪み取
り焼鈍を行なった後の耐食性試験と、歪み取り焼鈍前後
の眉間抵抗の計測とにより評価した。An insulating film was formed on the surface of an electromagnetic steel sheet according to the method of the present invention to obtain steel sheets Grades 1 to 3 of the present invention. For comparison, an insulating film was formed on the surface of an electrical steel sheet under conditions in which the treatment liquid was outside the range of the method of the present invention, and comparative steel sheets 11m4 to 6 were obtained. These steel plates a1 to 3 of the present invention and comparative steel plates a4 to
The heat resistance of the insulating film No. 6 was evaluated by a corrosion resistance test after performing strain relief annealing for 750'CX2 hours and by measuring glabellar resistance before and after strain relief annealing.
主１月１１呈上
０．５１厚の０．２５％Ｓｉの電磁鋼板を、５０℃のア
ルカリ性脱脂剤（オルトケイ酸ソーダ１５ｇ／ｊりで３
０秒間洗浄し、水洗、乾燥した。これに以下の組成の処
理液をロールコータ−により均一に塗布し、次いで焼付
は炉を通して到達板温２８０℃で５０秒間の焼付けを行
ない、電磁鋼板表面に絶縁皮膜を形成した。これを本発
明鋼板隘１とした。A 0.25% Si electrical steel sheet with a thickness of 0.51 was coated with an alkaline degreaser (sodium orthosilicate 15 g/j) at 50°C.
It was washed for 0 seconds, washed with water, and dried. A treatment solution having the following composition was uniformly applied to this using a roll coater, and baking was then carried out through an oven at a final board temperature of 280° C. for 50 seconds to form an insulating film on the surface of the electrical steel sheet. This was designated as steel plate No. 1 of the present invention.
処理液の塗布量は乾燥重量で２．０ｇ／ｍであった。The coating amount of the treatment liquid was 2.0 g/m in terms of dry weight.
クロム酸カルシウム ６．０重置部
シａｔＪＭ １．３重量部（２４，５％
ビ酢酸イオンで安定化させたアルミ
ナゾル（固型分子ｆ）２．６重量部（４９，０％ビ水
９０．１重量部
＊ 箇弧内はクロム酸カルシウムのＣｒＯ３ｍ 算”含
有量に対する割合い。以下同じ。Calcium chromate 6.0 parts sheet JM 1.3 parts by weight (24.5%
2.6 parts by weight of alumina sol (solid molecule f) stabilized with biacetate ions (49.0% biwater)
90.1 parts by weight * The value in parentheses is the ratio to the CrO3m content of calcium chromate. The same applies hereinafter.
主文尻且豊呈１
以下の組成の処理液を使って、本発明鋼板１ｋｌと同様
に処理し、これを本発明鋼板隘２とした。Main Text End of Text 1 Using a treatment solution having the following composition, the steel sheet of the present invention was treated in the same manner as 1kl of the steel sheet of the present invention, and this was designated as the steel sheet of the present invention 2.
処理液の塗布量は乾燥重量で１．８ｇ／ｍ２であった。The coating amount of the treatment liquid was 1.8 g/m2 in terms of dry weight.
クロム酸カルシウム ６．０重量部
シヨ１！ １．３重量部（２４，５％）
酢酸イオンで安定化させたアルミ
ナゾル（固型分量）１．５重量部（２８，０％）水
９１，２重世部才づし朋」［仮］ＬＬ
以下の組成の処理液を使って、本発明鋼板階１と同様に
処理し、これを本発明鋼Ｆｉｌｔ３とした。Calcium chromate 6.0 parts by weight 1! 1.3 parts by weight (24.5%)
Alumina sol stabilized with acetate ions (solid content) 1.5 parts by weight (28.0%) water
91, 2 Yobe Saizushitomo" [Tentative] LL A steel sheet of the present invention was treated in the same manner as the steel plate of the present invention, Filt 3, using a treatment solution having the following composition, and this was designated as the steel of the present invention, Filt3.
処理液の塗布量は乾燥重量で２．０ｇ／ｒｒｒであった
。The coating amount of the treatment liquid was 2.0 g/rrr in terms of dry weight.
クロム酸カルシウム ６．ｏｍｉｓ
シヨ糖 １．３重量部（２４，５％）酢酸
イオンで安定化させたアルミ
ナゾル（固型分量）４，０重量部（７５，０％）水
８８．７重量部
−置体」１贋蕩」−
以下の組成の処理液を使って、本発明鋼板隘１と同様に
処理し、これを比較鋼板階４とした。処理液の塗布量は
乾燥重量で２．０ｇ／ｒ／であった。Calcium chromate 6. omis Cane sugar 1.3 parts by weight (24,5%) Alumina sol stabilized with acetate ions (solid content) 4,0 parts by weight (75,0%) Water
88.7 parts by weight - 1-counterfeit - Using a treatment solution with the following composition, the steel plate of the present invention was treated in the same manner as No. 1, and this was used as comparative steel sheet No. 4. The coating amount of the treatment liquid was 2.0 g/r/dry weight.
クロム酸カルシウム ６．０３１ｔｆｆｉ部ソヨ糖
１．３重世部（２４，５％）酢酸イオンで安
定化させたアルミ
ナゾル（固型分子ｆｔ）０．６重世部（１１，３％）水
９２．１重量部
１木Ｊ１口（ｉ
以下の組成の処理液を使って、本発明鋼板１１１１と同
様に処理し、これを比較鋼板患５とした。処理液の塗布
量は乾燥重量で１゜８ｇ／ｍであった。Calcium chromate 6.031 tffi parts Soyo sugar
1.3 parts by weight (24.5%) Alumina sol stabilized with acetate ions (solid molecules ft) 0.6 parts by weight (11.3%) Water 92.1 parts by weight 1 wood J 1 mouth (i A treatment liquid having the following composition was used to treat steel plate 1111 of the present invention, and this was designated as comparative steel plate No. 5. The amount of treatment liquid applied was 1.8 g/m in terms of dry weight.
クロム酸カルシウム ６．０重量部
シｇ糖 １．３重量部（２４，５％）コロ
イド状シリカ
（固型分量）２．６重量部（４９，０％）水
９０．１重量部
、取木」Ｉえ蕩」−
以下の組成の処理液を使って、本発明鋼板ｌ１ｋ１１と
同様に処理し、これを比較鋼板階６とした。処理液の塗
布量は乾燥重量で１．８８／ｍであった。Calcium chromate 6.0 parts by weight Sig sugar 1.3 parts by weight (24.5%) Colloidal silica (solid content) 2.6 parts by weight (49.0%) Water
90.1 parts by weight, 100.1 parts by weight of wood - Using a treatment solution with the following composition, the steel plate 11k11 of the present invention was treated in the same manner as the steel plate 11k11 of the present invention, and this was used as comparative steel plate 6. The coating amount of the treatment liquid was 1.88/m in terms of dry weight.
クロム酸カルシウム ６．０重量部
エチレングリコール １，３重量部（２４，５％）硝酸
アルミニウム ２．６重量部（／１９．０％）水
９０．１重量部
これら本発明鋼板階１〜３、比較鋼板磁４〜６の耐食性
試験結果と皮膜層間抵抗の測定値とを、第２表に示す。Calcium chromate 6.0 parts by weight Ethylene glycol 1.3 parts by weight (24.5%) Aluminum nitrate 2.6 parts by weight (/19.0%) Water
90.1 parts by weight Table 2 shows the results of the corrosion resistance test and the measured values of the interlayer resistance of the steel sheets of the present invention Grades 1 to 3 and Comparative steel plates 4 to 6.
第 ２ 表 １）層間１１（抗はＪＩＳ Ｃ２５５０による。Table 2 1) Interlayer 11 (resistance is based on JIS C2550.
２）焼鈍はＮ２９５％、１１２５％の雰囲気中、７５０
℃Ｘ２ｈｒである。2) Annealing was performed at 750° C. in an atmosphere of N295% and 1125%.
℃×2hr.
３）耐食性の試験結果は、上記２）の焼鈍後の湿潤試験
（ＨＣＴ）による３０％赤錆発生時間を示す。3) Corrosion resistance test results indicate the 30% red rust generation time determined by the post-annealing wet test (HCT) in 2) above.
第２表に示されるよう番こ、この発明の方法により絶縁
皮膜を形成した本発明鋼板隘１〜３では、絶縁皮膜が耐
熱性に優れているために、歪み取り焼鈍によっても皮膜
の劣化がなく、このため焼鈍後の耐食性、絶縁性が共に
、比較鋼板隘４〜６に比べて著しく優れている。これは
、本発明鋼板隘１〜３では、既述したように、酢酸イオ
ンで安定化させたアルミナゾルが絶縁皮膜中で互いにか
らみ合って、緻密な状態で存在していることによると考
えられる。As shown in Table 2, in steel sheets Nos. 1 to 3 of the present invention, in which the insulating film was formed by the method of the present invention, the insulating film has excellent heat resistance, so that the film does not deteriorate even after strain relief annealing. Therefore, both the corrosion resistance and insulation properties after annealing are significantly superior to those of comparative steel sheets Nos. 4 to 6. This is considered to be because, in the steel sheets 1 to 3 of the present invention, the alumina sol stabilized with acetate ions is entangled with each other in the insulating film and exists in a dense state, as described above.
以上説明したように、この発明の方法によれば電磁鋼板
の表面に耐熱性に優れた絶縁皮膜を形成することができ
る。As explained above, according to the method of the present invention, an insulating film with excellent heat resistance can be formed on the surface of an electrical steel sheet.
【図面の簡単な説明】
第１図は、クロム酸含有溶液の薬液相溶性を示す説明図
、第２図は、絶縁皮膜の歪み取り焼鈍後の湿潤試験結果
を示すグラフである。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an explanatory diagram showing the chemical liquid compatibility of a chromic acid-containing solution, and FIG. 2 is a graph showing the results of a wetness test after strain relief annealing of an insulating film.
Claims (1)
／ｌ含有し、酢酸イオンで安定化させたアルミナゾルを
固型分量で前記クロム酸カルシウムのＣｒＯ＿３換算の
含有量の２５〜７５％含有し、還元性の有機化合物を前
記クロム酸カルシウムのＣｒＯ＿３換算の含有量の１０
〜４０％含有する処理液を、電磁鋼板の表面に乾燥重量
で０．５〜４ｇ／ｍ＾２塗布し、前記処理液を２００〜
４００℃の温度で前記電磁鋼板の表面に焼き付けること
を特徴とする、電磁鋼板の耐熱性に優れた絶縁皮膜の形
成方法。10-70g of calcium chromate in terms of CrO_3
/l and contains alumina sol stabilized with acetate ions in a solid amount of 25 to 75% of the CrO_3 content of the calcium chromate, and the reducing organic compound is added to the CrO_3 content of the calcium chromate. content of 10
A treatment liquid containing ~40% is applied to the surface of an electrical steel sheet at a dry weight of 0.5~4g/m^2, and the treatment liquid is applied at a dry weight of 0.5~4g/m^2.
A method for forming an insulating film with excellent heat resistance on an electrical steel sheet, the method comprising baking the surface of the electrical steel sheet at a temperature of 400°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32589587A JP2621267B2 (en) | 1987-12-23 | 1987-12-23 | Method of forming insulating film with excellent heat resistance of electrical steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32589587A JP2621267B2 (en) | 1987-12-23 | 1987-12-23 | Method of forming insulating film with excellent heat resistance of electrical steel sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01168005A true JPH01168005A (en) | 1989-07-03 |
| JP2621267B2 JP2621267B2 (en) | 1997-06-18 |
Family
ID=18181797
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32589587A Expired - Lifetime JP2621267B2 (en) | 1987-12-23 | 1987-12-23 | Method of forming insulating film with excellent heat resistance of electrical steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2621267B2 (en) |
-
1987
- 1987-12-23 JP JP32589587A patent/JP2621267B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2621267B2 (en) | 1997-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6638633B1 (en) | Solvent-resistant electrical steel sheet capable of stress relief annealing and process | |
| WO2007074927A1 (en) | Electromagnetic steel sheet having insulating coating film and method for producing same | |
| JPH1046350A (en) | Method for forming insulating film containing no chromium compound, capable of stress relieving annealing and excellent in corrosion resistance on surface of silicon steel sheet | |
| JP6558325B2 (en) | Treatment liquid for forming chromium-free tension coating, grain-oriented electrical steel sheet with chromium-free tension film, method for producing grain-oriented electrical steel sheet with chromium-free tension film, and core for transformer | |
| JP2001220683A (en) | Silicon steel sheet coated with insulated film | |
| US4295899A (en) | Process for coating iron and steel | |
| JP4635457B2 (en) | A grain-oriented electrical steel sheet having a phosphate insulating coating that does not contain chromium and has excellent moisture absorption resistance, and a method for forming a phosphate insulating coating that does not contain chromium and has excellent moisture absorption resistance. | |
| JPH01168005A (en) | Forming method for insulating film with excellent heat resistance of electromagnetic steel plate | |
| JPH03130376A (en) | Production of unidirectionally oriented silicon steel sheet excellent in magnetic characteristic | |
| JPH09157861A (en) | Coating agent for insulating coating film excellent in bendability of non-oriented silicon steel sheet and heat resistance and formation of coating film | |
| JP2003193251A (en) | Method of producing silicon steel sheet with insulating film having excellent appearance and adhesion | |
| JPH08269573A (en) | Formation of insulated film on grain-oriented silicon steel sheet excellent in adhesion | |
| JP2003193252A (en) | Method of producing silicon steel sheet with insulating film having excellent film appearance | |
| JPH11140665A (en) | Coated steel sheet excellent in edge face corrosion resistance and its production | |
| JP2017101292A (en) | Production method of grain oriented electrical steel sheet | |
| JP2727553B2 (en) | Method of forming a green coating with excellent heat resistance on the surface of electrical steel sheet | |
| JP3299459B2 (en) | Non-oriented electrical steel sheet excellent in punching property and seizure resistance after annealing and method for forming insulating film thereof | |
| JPH07316833A (en) | Coating agent for insulating coating film excellent in heat resistance for nonoriented silicon steel sheet and formation of insulating coating film | |
| JPH01222067A (en) | Formation of insulating coating film having superior heat resistance on surface of electrical steel sheet | |
| JPH04235287A (en) | Method for forming insulating film on magnetic steel sheet | |
| JP3300117B2 (en) | Method of forming insulating coating on grain-oriented silicon steel sheet | |
| JPH0499878A (en) | Formation of insulating coating film for electrical steel sheet | |
| JP3461712B2 (en) | Unidirectional electrical steel sheet and method for forming insulating film on unidirectional electrical steel sheet | |
| JPH01283382A (en) | Production of chromated galvanized steel sheet having superior resistance to blackening, corrosion and removing of fingerprint and high chromium fixing rate after alkali degreasing | |
| JPH06299366A (en) | Production of low iron loss grain oriented silicon steel sheet |