JP4264362B2 - Insulating coating agent for grain-oriented electrical steel sheet not containing chromium and grain-oriented electrical steel sheet having an insulating film not containing chromium - Google Patents
Insulating coating agent for grain-oriented electrical steel sheet not containing chromium and grain-oriented electrical steel sheet having an insulating film not containing chromium Download PDFInfo
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- 239000011248 coating agent Substances 0.000 title claims description 35
- 229910001224 Grain-oriented electrical steel Inorganic materials 0.000 title claims description 18
- 239000011651 chromium Substances 0.000 title claims description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims description 10
- 229910052804 chromium Inorganic materials 0.000 title claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 title 1
- 229910019142 PO4 Inorganic materials 0.000 claims description 41
- 235000021317 phosphate Nutrition 0.000 claims description 41
- 239000010452 phosphate Substances 0.000 claims description 38
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 35
- 238000000576 coating method Methods 0.000 claims description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- 239000008119 colloidal silica Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 229910010272 inorganic material Inorganic materials 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 150000002484 inorganic compounds Chemical class 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 4
- 229910000976 Electrical steel Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 35
- 238000000137 annealing Methods 0.000 description 33
- 230000000694 effects Effects 0.000 description 27
- 238000000034 method Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 15
- 150000001845 chromium compounds Chemical class 0.000 description 13
- 229910000831 Steel Inorganic materials 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- 230000006872 improvement Effects 0.000 description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- -1 organic acid salt Chemical class 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000011049 filling Methods 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000004804 winding Methods 0.000 description 6
- 230000009471 action Effects 0.000 description 4
- 229960004887 ferric hydroxide Drugs 0.000 description 4
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 230000005381 magnetic domain Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- QVLTXCYWHPZMCA-UHFFFAOYSA-N po4-po4 Chemical compound OP(O)(O)=O.OP(O)(O)=O QVLTXCYWHPZMCA-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Description
本発明は方向性電磁鋼板用の絶縁皮膜形成技術に関わり、特に、クロムを含有しない処理液を提供すると共に、それを用いて、耐焼鈍性、被膜張力、絶縁性、密着性、耐食性等の優れた絶縁皮膜特性を有する製品と絶縁皮膜形成方法に関する。 The present invention relates to an insulating film forming technique for grain-oriented electrical steel sheets, and in particular, provides a treatment liquid that does not contain chromium, and uses it, such as annealing resistance, film tension, insulation, adhesion, and corrosion resistance. The present invention relates to a product having excellent insulating film characteristics and an insulating film forming method.
方向性電磁鋼板は、Ｓｉを例えば２〜４％含有する珪素鋼スラブを熱延し、焼鈍した後、１回或いは中間焼鈍を挟む２回以上の冷延を施して最終板厚とし、次いで脱炭焼鈍した後ＭｇＯを主成分とする焼鈍分離剤を塗布し、仕上げ焼鈍を行ってゴス方位を持つ二次再結晶を発達させ、さらにＳ，Ｎ等の不純物を除去すると共にグラス被膜を形成し、次いで絶縁皮膜剤を塗布し、焼き付けとヒートフラットニング処理を施して最終製品とされる。 For a grain-oriented electrical steel sheet, a silicon steel slab containing, for example, 2 to 4% of Si is hot-rolled and annealed, and then subjected to cold rolling twice or more sandwiching intermediate annealing to obtain a final sheet thickness, and then removing the steel sheet. After carbon annealing, an annealing separator containing MgO as the main component is applied, finish annealing is performed to develop secondary recrystallization with goth orientation, and impurities such as S and N are removed and a glass film is formed. Then, an insulating film agent is applied and subjected to baking and heat flattening to obtain a final product.
このようにして得られる方向性電磁鋼板は、主として、電気機器、トランス等の鉄心材料として使用され、磁束密度が高く、鉄損が優れるものが要求される。方向性電磁鋼板がトランス鉄心として用いられる際には方向性電磁鋼板コイルはスリットされ、連続的に解きほどかれながら所定長さに切断され、鉄心加工機によって積み重ね或いは巻き加工されて積み鉄心や巻き鉄心とされる。巻き鉄心の場合には圧縮成型、歪み取り焼鈍を経てレーシングと呼ばれる巻き線作業を行ってトランスとされる。このトランス製造工程においては切断、巻き加工、成形作業が容易に行えることが重要である。特に、巻きコア製造においては切断や巻き成型時に絶縁皮膜の密着性が優れて発粉等の作業環境を損なわないことや巻き加工性、耐焼鈍性が優れて被膜性能、磁気特性及び作業性を損なわないためにも重要である。 The grain-oriented electrical steel sheet obtained in this manner is mainly used as an iron core material for electrical equipment, transformers, etc., and is required to have a high magnetic flux density and excellent iron loss. When a directional electromagnetic steel sheet is used as a transformer iron core, the directional electromagnetic steel sheet coil is slit, cut to a predetermined length while being continuously unwound, and stacked or wound by an iron core processing machine to be a stacked iron core or winding. It is said to be an iron core. In the case of a wound iron core, it is made into a transformer by performing a winding operation called racing after compression molding and strain relief annealing. In this transformer manufacturing process, it is important that cutting, winding, and molding can be easily performed. In particular, in the manufacture of wound cores, the adhesion of the insulating film is excellent during cutting and winding molding, and it does not impair the working environment such as powdering, and it has excellent winding workability and annealing resistance, and has coating performance, magnetic properties and workability. It is important not to damage.
方向性電磁鋼板の表面被膜は、通常、最終仕上げ焼鈍中に形成された通常グラス被膜と呼ばれるフォルステライト被膜とその上に処理される絶縁皮膜とからなる。この絶縁皮膜の形成技術としては、特許文献１に本発明者らによってコロイダルシリカと燐酸塩及びクロム化合物からなる張力被膜が発明され開示され工業化された。また、特許文献２で示される様に第一燐酸塩に粒子径８ｎｍ以下の微粒子コロイダルシリカとクロム化合物からなる処理剤が開示された。更に特許文献３では、Ａｌ，Ｍｇ，Ｃａ，Ｚｎの第一燐酸塩とクロム化合物に対し粒径２０ｎｍ以下のコロイダルシリカと粒径８０〜２０００ｎｍのコロイダルシリカを混合することにより、絶縁皮膜表面に均一な突起効果を得て巻き鉄心加工工程における巻き加工性（滑り性）、耐焼鈍性、被膜張力の向上を実現する技術が示されている。これらにより張力効果と鉄心加工性向上効果が得られ、磁気特性や磁歪特性が優れる方向性電磁鋼板が得られるようになった。 The surface film of the grain-oriented electrical steel sheet is usually composed of a forsterite film, usually called a glass film, formed during the final finish annealing, and an insulating film processed thereon. As a technique for forming this insulating film, Patent Document 1 invented, disclosed and industrialized a tension film made of colloidal silica, a phosphate, and a chromium compound by the present inventors. Further, as disclosed in Patent Document 2, a treatment agent comprising fine colloidal silica having a particle diameter of 8 nm or less and a chromium compound is disclosed in primary phosphate. Further, in Patent Document 3, by mixing colloidal silica having a particle size of 20 nm or less and colloidal silica having a particle size of 80 to 2000 nm with a primary phosphate of Al, Mg, Ca, Zn and a chromium compound, the surface of the insulating film is uniform. Techniques have been shown for obtaining a good protrusion effect and improving winding workability (sliding property), annealing resistance, and film tension in the wound iron core machining process. As a result, a tensile effect and an effect of improving iron core workability are obtained, and a grain-oriented electrical steel sheet having excellent magnetic properties and magnetostrictive properties can be obtained.
これらの絶縁皮膜は、燐酸塩による被膜焼き付け処理後における吸湿性や歪み取り焼鈍時の被膜焼き付き性等を考慮して、何れもクロム化合物が添加配合されてきた。 These insulating films have been added and mixed with a chromium compound in consideration of the hygroscopicity after the film baking treatment with phosphate, the film seizure property during strain relief annealing, and the like.
絶縁皮膜中におけるクロム化合物の役割は、燐酸塩或いは燐酸塩とコロイダルシリカ系被膜におけるポーラスな被膜構造を充填する効果と絶縁被膜焼付け後の被膜成分に残留する吸湿性屋分解性のあるフリー燐酸を固定して安定な燐酸−クロム化合物を形成する効果とが相俟って被膜のベタツキや焼鈍時の焼き付性及び被膜張力等を改善する効果をもたらす。処理液に無水クロム酸、クロム酸塩或いは重クロム酸塩を用い６価クロムを含有する場合、塗布作業時の作業環境や廃液処理作業の問題がある。更に、焼き付け処理後の被膜においては、Ｃｒはほぼ、３価クロムに還元されており有害性は少ないもの、鉄心加工工程における発粉が生じる場合には作業環境を汚染する恐れもある。この対策として、クロム化合物を含有しない絶縁皮膜剤の研究もなされてきた。また特許文献４には、コロイド状シリカをＳｉＯ2で２０質量部、燐酸Ａｌ １０〜１２０質量部、硼酸２〜１０質量部とＭｇ，Ａｌ，Ｆｅ，Ｃｏ，Ｎｉ及びＺｎの、それぞれの硫酸塩のうちから選ばれる何れか１種または２種合計で４〜４０質量部とを含有する処理液を３００℃以上で焼き付け処理する絶縁皮膜形成法が提案されている。 The role of the chromium compound in the insulating film is the effect of filling the porous coating structure in the phosphate or phosphate and colloidal silica-based coating, and the hygroscopic decomposable free phosphoric acid remaining in the coating components after baking the insulating coating. Combined with the effect of fixing and forming a stable phosphate-chromium compound, the effect of improving the stickiness of the coating, the seizure during annealing, the coating tension and the like is brought about. When the treatment liquid contains hexavalent chromium using chromic anhydride, chromate or dichromate, there are problems in the working environment during the coating work and the waste liquid treatment work. Furthermore, in the coating after the baking treatment, Cr is almost reduced to trivalent chromium and has little harmfulness. If powdering occurs in the iron core processing step, the working environment may be contaminated. As a countermeasure, an insulating film agent not containing a chromium compound has been studied. In Patent Document 4, colloidal silica is composed of 20 parts by mass of SiO 2 , 10 to 120 parts by mass of Al phosphate, 2 to 10 parts by mass of boric acid, and Mg, Al, Fe, Co, Ni and Zn sulfates. An insulating film forming method is proposed in which a treatment liquid containing 4 to 40 parts by mass in total of any one or two selected from among these is baked at 300 ° C. or higher.
特許文献５には、Ｍ2+ 1-xＭ3+ x(ＯＨ)- 2+x-nyＡn- y・ｍＨ2Ｏの一般式で表される平均粒子径１μｍ以下の固溶型複合水酸化物組成である処理剤が開示されている。また特許文献６には、Ｃａ，Ｍｎ，Ｆｅ，Ｍｇ，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、コハク酸塩及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が提案されている。 Patent Document 5, M 2+ 1-x M 3+ x (OH) - 2 + x-ny A ny · mH 2 O Formula average particle size 1μm or less of the solid solution type composite represented by the A treatment agent having a hydroxide composition is disclosed. In Patent Document 6, as an organic acid salt selected from Ca, Mn, Fe, Mg, Zn, Co, Ni, Cu, B and Al, formate, acetate, oxalate, tartrate, lactate, citric acid, A surface treatment agent for grain-oriented electrical steel sheets characterized by adding one or more organic acid salts selected from acid salts, succinates and salicylates has been proposed.
これらは、何れも被膜張力効果を発揮できる技術であり、それなりに効果を発揮している。しかしながら、特許文献４の場合、添加する硫酸塩の硫酸イオンによる焼鈍時の変色や絶縁性、耐蝕性等の問題がある。また、特許文献６は、金属元素を溶解するための有機物による色調の問題や溶液安定性の問題が考えられる。このように、従来のクロム含有絶縁皮膜剤に比較すると、総合的には十分に被膜性能が改善されているものとは言い難く、更なる改善が望まれていた。 These are all technologies that can exert the effect of the film tension, and are effective as they are. However, in the case of Patent Document 4, there are problems such as discoloration, insulation, and corrosion resistance during annealing with sulfate ions of the added sulfate. Further, Patent Document 6 may have a problem of color tone due to an organic substance for dissolving a metal element and a problem of solution stability. Thus, compared with the conventional chromium-containing insulating film agent, it cannot be said that the film performance has been improved sufficiently comprehensively, and further improvement has been desired.
本発明は、クロム化合物を含有しない絶縁皮膜剤組成を有することで環境問題を解決すると共に、従来の燐酸塩或いは燐酸塩−コロイダルシリカ系被膜のように、燐酸塩をベースとする絶縁における、クロム化合物を含有しない場合の耐吸湿性、耐焼鈍性、緻密性、被膜張力不良問題を解決する被膜性能の優れた絶縁皮膜を有する方向性電磁鋼板と絶縁皮膜剤を提供する。 The present invention solves environmental problems by having an insulating film agent composition that does not contain a chromium compound, and provides chromium in insulation based on phosphate, such as conventional phosphate or phosphate-colloidal silica-based coatings. There are provided a grain-oriented electrical steel sheet and an insulating film agent having an insulating film with excellent film performance that solves problems of moisture absorption resistance, annealing resistance, denseness, and film tension failure when no compound is contained.
本発明は、クロム化合物を含有しない方向性電磁鋼板用絶縁皮膜剤とクロム化合物を含有しない絶縁皮膜を有する方向性電磁鋼板として以下の構成を要旨とする。
（１）Ａｌ，Ｍｇ，Ｃａの中から選ばれる第一燐酸塩の１種または２種以上の合計で１モルに対し、Ｆｅ，Ｎｉの無機化合物の中から選ばれる１種又は２種を金属元素として０．０６〜２．１０モル含有し、前記第一燐酸塩１００質量部に対し、さらにコロイダルシリカを固形分相当として３５〜１００質量部含有し、前記Ｆｅ，Ｎｉの無機化合物が、水酸化物であり、前記Ｆｅ，Ｎｉの水酸化物が、水溶液として安定なコロイダル物質であり、前記コロイダル物質の形態が、単独化合物コロイド、ＳｉＯ２或いはＡｌ２ Ｏ ３ との複合コロイド、あるいはこれらの混合物であり、前記コロイダル物質の粒子径が５０ｎｍ以下であることを特徴とするクロムを含まない方向性電磁鋼板用絶縁皮膜剤。
（２）絶縁皮膜が、上記（１）に記載の絶縁皮膜剤を焼き付け処理して形成されたものであることを特徴とするクロムを含まない絶縁皮膜を有する方向性電磁鋼板。
The gist of the present invention is the following structure as a grain- oriented electrical steel sheet having an insulating film agent for grain- oriented electrical steel sheets not containing a chromium compound and an insulation film containing no chromium compound .
( 1 ) One or two kinds selected from inorganic compounds of Fe and Ni with respect to 1 mol in total of one kind or two or more kinds of primary phosphates selected from Al, Mg and Ca It contains 0.06 to 2.10 mol as an element, and further contains 35 to 100 parts by mass of colloidal silica as solid content with respect to 100 parts by mass of the first phosphate, and the inorganic compound of Fe and Ni is water. An oxide, the hydroxide of Fe, Ni is a colloidal material that is stable as an aqueous solution, and the form of the colloidal material is a single compound colloid, a composite colloid with SiO 2 or Al 2 O 3 , or these An insulating coating agent for grain-oriented electrical steel sheets, which is a mixture and does not contain chromium, wherein the colloidal substance has a particle size of 50 nm or less.
(2) an insulating coating, oriented electrical steel sheet having an insulating film not containing chromium characterized by der Rukoto those formed by processing baking an insulating coating agent according to (1).
本発明によれば、燐酸塩−コロイダルシリカをベースとするクロム化合物を含有しない張力被膜において、Ｆｅ，Ｎｉの水酸化物を添加することにより、焼付け後被膜の耐蝕性が向上し、歪み取り焼鈍時における耐焼き付き性の顕著な改善効果が得られる。特に、Ｆｅの超微粒子コロイダル物質の添加において極めて優れた効果を発揮する。 According to the present invention, phosphate - in tension coating containing no chromium compound based on colloidal silica, Fe, by adding a hydroxide of N i, improves the corrosion resistance of the baking after coating, straightening A significant improvement in seizure resistance during annealing can be obtained. In particular, an extremely excellent effect is exhibited in the addition of an ultrafine colloidal substance of Fe.
本発明者等は燐酸塩単体及び燐酸塩とコロイダルシリカ及びクロム化合物を主成分とする従来の張力付与型絶縁皮膜における無クロム組成化に取り組んだ。即ち、従来組成で、無クロム化を行った燐酸塩と燐酸塩とコロイダルシリカ主成分組成の場合の欠点であった被膜焼き付け処理後の吸湿性（ベタツキや錆発生）と歪み取り焼鈍における焼き付き性及び被膜ポーラス化による被膜張力減少を改善するための被膜組成の開発に取り組んだ。その結果、燐酸塩及び燐酸塩とコロイダルシリカを主成分とする張力付与型被膜成分において、Ｆｅ，Ｎｉの無機化合物を燐酸塩燐酸塩１モルに対し、それぞれの金属元素として０．０６〜２．１０モル％含有するよう添加することにより、従来の無クロム化における問題を解決し耐蝕性、耐焼鈍性、密着性、滑り性、絶縁性等が優れ、磁気特性と磁歪特性が優れる絶縁皮膜剤とその処理方法の完成に成功した。以下、詳細に説明する。 The inventors of the present invention have made efforts to make a chromium-free composition in a conventional tension-imparting insulating film mainly composed of phosphate alone, phosphate, colloidal silica, and a chromium compound. That is, moisture absorption (stickiness and rust generation) after film baking treatment and seizure resistance in strain relief annealing, which were the disadvantages of the conventional composition, chromium-free phosphate, phosphate and colloidal silica main component composition And developed a coating composition to improve coating tension reduction due to coating porosity. As a result, in the tension-imparting film component mainly composed of phosphate and phosphate and colloidal silica, an inorganic compound of Fe and Ni is used as each metal element in an amount of 0.06 to 2 with respect to 1 mol of phosphate phosphate. .Insulating film with excellent corrosion resistance, annealing resistance, adhesion, slipperiness, insulation, etc., and excellent magnetic and magnetostrictive properties by adding 10 mol% to solve conventional problems of chromium-free The agent and its treatment method were successfully completed. Details will be described below.
本発明剤の適用に当たっては、出発材としては、最終仕上げ焼鈍された方向性電磁鋼板を用い、連続処理焼き付けラインにおいて余剰焼鈍分離剤を除去し、軽酸洗の後、絶縁被膜液を鋼板表面に塗布し、焼き付け処理が行われる。 In application of the agent of the present invention, as a starting material, a final-finish annealed grain-oriented electrical steel sheet is used, the excess annealing separator is removed in a continuous processing baking line, and after light pickling, the insulating coating liquid is applied to the steel sheet surface. Then, a baking process is performed.
本発明においては、まず、その被膜組成に特徴がある。ここでは、燐酸塩とコロイダルシリカを主成分とする絶縁被膜の形成法について述べる。即ち、燐酸塩とコロイダルシリカを主成分被膜においては、その被膜張力発現のために、一般に、固形分質量でＡｌ，Ｍｇ，Ｃａの第一燐酸塩１００質量部とコロイダルシリカ３５〜１００質量部からなるベース液が採用される。この第一燐酸塩としては、Ａｌ，Ｍｇ，Ｃａの第一燐酸塩が用いられる。本発明では、この第一燐酸塩１モルに対し、Ｆｅ，Ｎｉの無機化合物を燐酸塩に対し、０．０６〜２．１０モルの範囲で添加される。 In the present invention, first, the film composition is characterized. Here, a method for forming an insulating film mainly composed of phosphate and colloidal silica will be described. That is, in the main component coating of phosphate and colloidal silica, generally from 100 parts by mass of the primary phosphate of Al, Mg, Ca and 35 to 100 parts by mass of colloidal silica in terms of solid content in order to express the film tension. A base solution is employed. As the primary phosphate, primary phosphates of Al, Mg, and Ca are used. In the present invention, with respect to the first phosphate salt 1 mole, Fe, relative to the phosphate inorganic compounds N i, is added in the range of 0.06 to 2.10 mol.
この重要な役割を有するＦｅ，Ｎｉ化合物としては、水酸化物を添加する。これらの物質は、微粒分散液であり、コロイダルシリカのようなシロキサン構造状の溶液として調整し、添加するのが、溶液安定性や前記、化合物燐酸塩の安定化、被膜充填作用等の効果を高めるのによりすぐれた効果を得られる。更に、より好ましい条件としては、コロイダル物質の水分散液で、それらの粒子径が５００ｎｍ以下の場合のものが用いられる。このようなコロイダル物質としては、水酸化物の単体コロイダル物質や、ＳｉＯ２，Ａｌ２Ｏ３との複合コロイダル物質として添加する等の方法の何れでも良い。 Fe with this important role, as the N i of compound, the addition of hydroxide thereof. These substances are fine particle dispersions, which are prepared and added as a siloxane-structured solution such as colloidal silica, and have effects such as solution stability, stabilization of the compound phosphate, and film filling action. A better effect can be obtained by increasing the value. Furthermore, as a more preferable condition, an aqueous dispersion of a colloidal substance having a particle diameter of 500 nm or less is used. Such colloidal materials, and simple colloidal substances hydroxide product may be either a method such as adding the composite colloidal material with SiO 2, Al 2 O 3.
この様にして調整された処理剤は、連続ラインでコーテイングロール等を用いて塗布量を制御して、塗布後３５０℃以上で焼き付け処理が行われる。塗布量としては、適用される鋼板厚みや製品の使用目的により決められる。本発明の被膜剤の場合には、２〜１０ｇ／ｍ2であれば被膜性能、外観は勿論のこと磁気特性、磁歪特性の優れた方向性電磁鋼板が得られる。 The treatment agent thus adjusted is subjected to a baking process at 350 ° C. or higher after coating by controlling the coating amount using a coating roll or the like in a continuous line. The coating amount is determined depending on the thickness of the applied steel sheet and the intended use of the product. In the case of the coating agent of the present invention, a grain-oriented electrical steel sheet having excellent magnetic properties and magnetostrictive properties as well as coating performance and appearance can be obtained at 2 to 10 g / m 2 .
本発明剤の適用に際しては、仕上げ焼鈍でグラス被膜を形成した材料の他、焼鈍分離剤にグラス被膜形成阻止剤を用いてグラス形成を阻止した鋼板や酸洗によりグラス被膜を除去した、いわゆるグラスレス材に適用してもよい。 In applying the agent of the present invention, in addition to the material in which the glass film is formed by finish annealing, the glass film is removed by pickling with a steel plate that has been prevented from forming glass by using a glass film formation inhibitor as an annealing separator, or so-called glass. It may be applied to loess materials.
ベース液が燐酸塩単独成分を主成分とする場合においても、同様にして燐酸塩に応じて本発明のＦｅ，Ｎｉの化合物が添加される。 When the base liquid is mainly composed of phosphate alone components also, Fe of the present invention in accordance with the phosphate, the compound of N i is added in the same manner.
次に、本発明の限定理由について述べる。 Next, the reason for limitation of the present invention will be described.
本発明の絶縁皮膜においては、まず、製品の絶縁皮膜の成分に特徴がある。 The insulating film of the present invention is first characterized by the component of the insulating film of the product.
まず、主成分が燐酸塩のみからなる場合、燐酸塩とコロイダルシリカを主成分とする場合、何れの場合にも、本発明が適用される。特に、後者の燐酸塩とコロイダルシリカを主成分とする場合には、クロムレス組成においては、焼き付けあと被膜の構造が、ポーラスで、吸湿性や焼鈍時の焼き付性が増し、被膜張力の低下減少が見られるため、極めて大きい改善効果がもたらされる。 First, the present invention is applied to any case where the main component is composed only of a phosphate, and when the main component is a phosphate and colloidal silica. In particular, when the latter phosphate and colloidal silica are the main components, in the chromeless composition, the structure of the coating after baking is porous, the hygroscopicity and seizure during annealing are increased, and the decrease in coating tension is reduced. As a result, an extremely large improvement effect is brought about.
方向性電磁鋼板製品の絶縁皮膜は、燐酸塩１モルに対し、Ｆｅ，Ｎｉ化合物の１種又は２種以上をそれぞれの金属元素として０．０６〜２．１０モルを含有する絶縁皮膜剤を用いて形成したことに特徴がある。本発明者らは、Ｃｒ代替作用を発揮する化合物について膨大な研究と実験を行った結果、Ｆｅ，Ｎｉ化合物は、燐酸塩のポーラスな構造を充填するのに有効であり、また、フリー燐酸分と容易に結合して、燐酸分の安定化効果をもたらし、特に、Ｆｅ化合物は極めて優れた効果を発揮することを発見した。 An insulating film of grain-oriented electrical steel sheet products, with respect to phosphate 1 mol, Fe, 1 or two or more as each metal element you containing 0.06 to 2.10 molar insulation film agent of the Ni compound It is characterized by being formed using . The present inventors have conducted extensive research and experiments on compounds that exhibit a Cr-substituting action, and as a result, the Fe and Ni compounds are effective in filling the porous structure of phosphate, and the free phosphoric acid content. It was found that the Fe compound exhibits a very excellent effect, in particular, by bringing about a phosphoric acid stabilizing effect.
燐酸塩に対し、Ｆｅ，Ｎｉ化合物は、それぞれの金属元素として、０．０６未満では、燐酸塩被膜中のポーラス構造充填や、吸湿性や焼鈍時の焼き付性を抑える効果が十分でない。２．１０モル％超の場合、これらの向上効果が飽和に達し、それ以上、改善されないこと、被膜張力の若干の低下が生じることから制限される。 To phosphate, Fe, N i of Gobutsu as respective metal elements is less than 0.06, porous structure filled and the phosphate in the coating, the effect of suppressing the baked with resistance during moisture absorption and annealing sufficient Not. When the content exceeds 2.10 mol%, these improving effects reach saturation and are not further improved, and are limited because a slight decrease in film tension occurs.
Ｆｅ，Ｎｉ化合物としては、水酸化物として添加される。水酸化物により添加した場合、被膜性能を損なうことなく、絶縁皮膜焼き付け処理過程で充填作用をもたらし、焼付け時や歪取り焼鈍過程において、フリー燐酸固定効果をもたらす。実験の結果では、これらの中で水酸化物の場合が最も優れた結果が得られる傾向が認められることがわかった。これは、水酸化物が焼付けや歪取り焼鈍過程で容易に分解して、被膜中に充填され、フリーな燐酸成分と反応して安定化させるためと推定される。 F e, as the Ni compound are added as a hydroxide. When added by a hydroxide, it provides a filling action in the insulating film baking treatment process without impairing the film performance, and provides a free phosphoric acid fixing effect during baking or in a strain relief annealing process. From the experimental results, it was found that the most excellent results were obtained with hydroxides. This is presumed to be because the hydroxide is easily decomposed during the baking and strain relief annealing, filled in the coating, and reacted with the free phosphoric acid component to stabilize it.
次に、Ｆｅ，Ｎｉの水酸化物の水溶液としては、コロイドダル物質とした場合、極めて優れた改善効果が得られる。コロイダル溶液の場合、コリダルシリカの場合のシロキサン構造状の溶液が得られ、微細な粒子で分散性、安定性の優れた溶液が得られる。これらのコロイダル物質をベース液に配合すると、非常に均一な分散液を生成するため、焼付け処理時に、前記、充填作用やフリー燐酸の安定化作用に対し、極めて優れた効果を発揮する。 Next, Fe, as the aqueous solution of the hydroxide of N i, when the colloidal dull material, excellent improvement effect is obtained. In the case of colloidal solution, a solution having a siloxane structure in the case of colloidal silica is obtained, and a solution having excellent dispersibility and stability is obtained with fine particles. When these colloidal substances are blended into the base solution, a very uniform dispersion is produced, and therefore, an extremely excellent effect is exhibited with respect to the filling action and the stabilizing action of free phosphoric acid during the baking process.
コロイダル物質としては、前記、それぞれの単体コロイダル物質の溶液か、ＳｉＯ2やＡｌ2Ｏ3の表層部のみ被覆した複合コロイダル物質の溶液として添加する等の方法があり、どちらにおいても良好な作用効果が得られる。本発明のコロイダル物質としては、最も顕著な効果を示したのは水酸化物の場合で、特に、Ｆｅ水酸化物のコロイドであった。 As the colloidal material, there is a method of adding each of the above-mentioned individual colloidal materials as a solution or a composite colloidal material solution in which only the surface layer part of SiO 2 or Al 2 O 3 is coated. Is obtained. As the colloidal material of the present invention, the most remarkable effect was in the case of hydroxide, and in particular, the colloid of Fe hydroxide.
コロイダル物質としては、粒子径が５００ｎｍ以下の場合、被膜充填作用、フリー燐酸の安定化のすぐれた効果が得られ、特に、５０ｎｍ以下の場合は、通常の湿式反応で調整した結晶質の化合物に比し、格段に優れた改善効果が得られる。 As colloidal materials, when the particle diameter is 500 nm or less, excellent effects of film filling and stabilization of free phosphoric acid are obtained. In particular, when the particle size is 50 nm or less, a crystalline compound prepared by a normal wet reaction is used. compared, improvement with excellent rating stage is obtained.
絶縁皮膜剤の塗布焼付け条件は、特に限定するものではないが、コーテイングロール等を用いて塗布後の焼付けに際しては、３５０℃以上の温度で焼き付けが行われる。これは、焼き付け温度が３５０℃未満では、第一燐酸塩と添加する、Ｆｅ，Ｎｉの水酸化物との反応が十分に進まないため、ベタツキ等の減少が生じることによる。製品にレーザー等の磁区細分化処理を行い磁気特性の改善効果を得るような場合には３５０〜４５０℃の温度域が好ましい。しかし、通常の方向性電磁鋼板のように焼き付け処理時に熱膨張差を利用して十分な張力効果と耐蝕性、耐焼鈍性を得るためには、７５０℃〜９００℃での焼き付け処理が必要である。 The application baking condition of the insulating film agent is not particularly limited, but baking is performed at a temperature of 350 ° C. or higher when baking is performed using a coating roll or the like. This is less than the baking temperature of 350 ° C., it is added to the first phosphoric acid salt, for Fe, reaction with hydroxide of N i does not proceed sufficiently, due to the reduction of such stickiness occurs. A temperature range of 350 to 450 ° C. is preferred when the product is subjected to magnetic domain subdivision treatment such as laser to obtain an effect of improving magnetic properties. However, in order to obtain a sufficient tension effect, corrosion resistance, and annealing resistance by using the thermal expansion difference at the time of baking processing as in a normal grain-oriented electrical steel sheet, baking processing at 750 ° C. to 900 ° C. is necessary. is there.
本発明で焼き付け処理後の吸湿性や歪み取り焼鈍時の鋼板の焼き付き性が阻止される理由は明確ではないが次のように推定される。溶液中に均一分散されたＦｅ，Ｎｉの水酸化物が、焼付け過程において分解し、燐酸塩や燐酸塩とコロイダルシリカ成分のみの場合に生じるポーラスな巣状の欠陥部に充填される。また、強固で安定した燐酸化合物を精製することで、被膜の緻密化、吸湿性の防止及び被膜張力の向上効果をもたらすものと思われる。特に、超微粒子のコロイダル状のものがこの改善効果が大きいのは、前記、反応サイトの増加と均一化によるものと思われる。 The reason for preventing the hygroscopicity after baking treatment and the seizure property of the steel sheet during strain relief annealing in the present invention is not clear, but is estimated as follows. Fe are uniformly dispersed in the solution, hydroxide of N i is decomposed in the baking process, is filled into the defect portion of the porous focal which occurs when only phosphate or phosphate and colloidal silica component. In addition, it is considered that by refining a strong and stable phosphoric acid compound, it is possible to provide a dense film, prevent hygroscopicity, and improve the film tension. In particular, it is considered that the colloidal shape of ultrafine particles has a large improvement effect due to the increase and uniformization of the reaction sites.
最終仕上げ焼鈍を行った鋼板表面にグラス被膜を有する板厚０．２３ｍｍの高磁束密度方向性電磁鋼板コイルからサンプルを切り出し、水洗後８５０℃Ｘ４Ｈｒの歪み取り焼鈍を行った。その後２％、Ｈ２ＳＯ４水溶液中で８５℃、１５秒間の軽酸洗を行った後、表１に示すようにＦｅ，Ｎｉ化合物の添加条件を変更して添加した処理剤を、コーテイングロールを用いて乾燥、焼き付け後の質量で５ｇ／ｍ２になるよう塗布し、８５０℃×３０秒間の焼き付け処理を行った。この後、この製品板からサンプルを切り出し被膜特性の調査を行った。結果を表２に示す。 A sample was cut out from a high magnetic flux density directional magnetic steel sheet coil having a thickness of 0.23 mm having a glass coating on the surface of the steel sheet subjected to final finish annealing, and subjected to 850 ° C. × 4 Hr strain relief annealing after washing with water. Thereafter 2%, 85 ° C. in H 2 SO 4 aqueous solution, after the light pickling for 15 seconds, Fe as shown in Table 1, the treatment agent added by changing the addition conditions of the N i of compound Then, it was applied using a coating roll so that the mass after drying and baking was 5 g / m 2, and a baking treatment at 850 ° C. for 30 seconds was performed. Thereafter, a sample was cut out from the product plate, and the film characteristics were investigated. The results are shown in Table 2.
この試験の結果、本発明のＦｅ，Ｎｉ化合物添加の場合、添加物を添加しない場合に比較して、焼き付け後被膜の吸湿性、耐焼鈍性が顕著に改善され、従来のクロム化合物を含有する比較例３に比し遜色のない被膜特性が得られた。特に、Ｆｅ化合物添加においては、より優れた改善効果が得られた。しかし、水酸化鉄の添加量が少ない場合には効果が弱く、多過ぎる場合には、液安定性や耐蝕性、被膜張力等の面で劣る結果となった被膜特性の面で劣る結果となった。 The results of this study, Fe of the present invention, when the N i of compound added, as compared with the case without the addition of additives, hygroscopic baking after coating an anneal resistance are significantly improved, conventional chromium compound Film characteristics comparable to those of Comparative Example 3 containing No. 3 were obtained. In particular, when the Fe compound was added, a more excellent improvement effect was obtained. However, when the amount of iron hydroxide added is small, the effect is weak, and when it is too much, the result is inferior in film properties, which are inferior in liquid stability, corrosion resistance, film tension, etc. It was.
実施例１と同様に最終仕上げ焼鈍を行った板厚０．２３ｍｍの高磁束密度方向性電磁鋼板コイルからサンプルを切り出し、水洗後８５０℃×４Ｈｒの歪み取り焼鈍を行った。その後２％、Ｈ2ＳＯ4水溶液中で７５℃×１５秒間の軽酸洗を行った。この鋼板に、表３に示すように添加剤として、Ｆｅ，Ｎｉの水酸化物コロイダル物溶液の粒子径条件を変更した溶液を添加した処理剤をコーテイングロールを用いて乾燥、焼き付け後の質量で５．０ｇ／ｍ2になるよう塗布し、８５０℃×３０秒間の焼き付け処理を行った。この後、この製品板からサンプルを切り出し被膜特性の調査を行った。結果を表４に示す。 A sample was cut out from the 0.23 mm-thick high magnetic flux density grain-oriented electrical steel sheet coil that was subjected to final finish annealing in the same manner as in Example 1, and after rinsing with water, 850 ° C. × 4 Hr strain relief annealing was performed. After that, light pickling at 75 ° C. for 15 seconds was performed in a 2% H 2 SO 4 aqueous solution. As shown in Table 3, this steel sheet is treated with an additive containing a solution in which the particle diameter conditions of the Fe and Ni hydroxide colloidal solution are changed. It apply | coated so that it might become 5.0 g / m < 2 >, and the baking process for 850 degreeC x 30 second was performed. Thereafter, a sample was cut out from the product plate, and the film characteristics were investigated. The results are shown in Table 4.
この試験の結果、実施例１と同様に比較例の有機酸塩を添加しない場合には、耐蝕性と耐焼鈍性が非常に劣る結果であった。また、本発明６，９，１０のようにコロイダル物質の粒子径が大きいコロイドを添加した場合、改善効果は見られるものの効果はそれほど大きいものではなかった。また、コロイダル物質として、ＳｉＯ2表面に水酸化第二鉄を複合物質として調整した複合コロイダル物質を添加した場合においても、単独コロイダル物質添加とほぼ同様の結果が得られた。これに対し、本発明のＦｅ，Ｎｉ水酸化物をコロイダル状の溶液として調整した化合物を添加した耐蝕性と耐焼鈍性の極めて大きい改善効果が得られ、従来のクロム化合物を含有する場合に比し、より優れた被膜性能と磁気特性が得られた。 As a result of this test, when the organic acid salt of the comparative example was not added as in Example 1, the corrosion resistance and the annealing resistance were very poor. In addition, when a colloid having a large colloidal substance particle size was added as in the present inventions 6, 9 and 10, although an improvement effect was observed, the effect was not so great. In addition, when a colloidal material prepared by adding ferric hydroxide as a composite material to the SiO2 surface was added as the colloidal material, almost the same result as that obtained when the single colloidal material was added was obtained. On the other hand, an extremely large improvement effect of corrosion resistance and annealing resistance obtained by adding a compound prepared by preparing the Fe, Ni hydroxide of the present invention as a colloidal solution is obtained, compared with the case of containing a conventional chromium compound. As a result, better film performance and magnetic properties were obtained.
実施例２と同一の実験手順で、ベース液として第一燐酸Ａｌ；２５ｍｌ＋第一燐酸Ｍｇ；２５ｍｌ＋２０％コロイダルシリカ（７ｎｍ）；１００ｍｌに対し、コロイド状水酸化鉄第二鉄（１０ｎｍ）溶液の添加量を燐酸塩とのモル比で０〜２．５まで変化させたときの焼付け力（剥離力）を測定した結果を図２に示す。燐酸塩１モル当たり水酸化第二鉄を０．０６モル以上添加することで、剥離力を大きく低減することができた。 Addition of colloidal ferric hydroxide (10 nm) solution to 100 ml of primary aluminum phosphate as base solution; 25 ml + primary Mg phosphate; 25 ml + 20% colloidal silica (7 nm) in the same experimental procedure as in Example 2 FIG. 2 shows the results of measuring the baking force (peeling force) when the amount is changed from 0 to 2.5 in terms of the molar ratio with the phosphate. By adding 0.06 mol or more of ferric hydroxide per mol of phosphate, the peeling force could be greatly reduced.
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| JP5063902B2 (en) * | 2006-02-17 | 2012-10-31 | 新日本製鐵株式会社 | Oriented electrical steel sheet and method for treating insulating film |
| JP4983334B2 (en) * | 2007-03-28 | 2012-07-25 | Ｊｆｅスチール株式会社 | Insulating coating solution for grain-oriented electrical steel sheet and method for producing grain-oriented electrical steel sheet |
| KR101025008B1 (en) * | 2007-12-26 | 2011-03-25 | 주식회사 포스코 | Method for forming insulating film of non-oriented electrical steel sheet and non-oriented electrical steel sheet by using it |
| KR100966819B1 (en) * | 2008-08-08 | 2010-06-29 | 주식회사 포스코 | Cr -free coating solution, manufacturing method and steel sheet, manufacturing method |
| JP5320898B2 (en) * | 2008-08-08 | 2013-10-23 | 新日鐵住金株式会社 | Insulating film coating solution and method for forming insulating film for grain-oriented electrical steel sheet |
| KR101324260B1 (en) * | 2011-12-28 | 2013-11-01 | 주식회사 포스코 | Insulation coating material for non-oriented electrical steel sheet and method for manufacturing the same |
| JP5978009B2 (en) * | 2012-05-30 | 2016-08-24 | 新日鐵住金株式会社 | INSULATION COATING FORMING LIQUID AND METHOD FOR PRODUCING ELECTRIC STEEL STEEL WITH INSULATING COATING |
| RU2698234C1 (en) * | 2016-09-13 | 2019-08-23 | ДжФЕ СТИЛ КОРПОРЕЙШН | Sheet from textured electrical steel having a chromium-free insulating coating creating a tension, and methods of making such a steel sheet |
| KR102174155B1 (en) * | 2018-09-27 | 2020-11-04 | 주식회사 포스코 | Annealing separating agent composition for grain oriented electrical steel sheet, grain oriented electrical steel sheet, and method for manufacturing grain oriented electrical steel sheet |
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