JP4983334B2 - Insulating coating solution for grain-oriented electrical steel sheet and method for producing grain-oriented electrical steel sheet - Google Patents
Insulating coating solution for grain-oriented electrical steel sheet and method for producing grain-oriented electrical steel sheet Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims description 61
- 239000011248 coating agent Substances 0.000 title claims description 59
- 229910001224 Grain-oriented electrical steel Inorganic materials 0.000 title claims description 48
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 238000000137 annealing Methods 0.000 claims description 47
- 239000007788 liquid Substances 0.000 claims description 36
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 29
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 26
- 238000001953 recrystallisation Methods 0.000 claims description 23
- 229910019142 PO4 Inorganic materials 0.000 claims description 22
- 235000021317 phosphate Nutrition 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000008119 colloidal silica Substances 0.000 claims description 19
- 229910000831 Steel Inorganic materials 0.000 claims description 18
- 239000010959 steel Substances 0.000 claims description 18
- 229910052748 manganese Inorganic materials 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 15
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 229910001919 chlorite Inorganic materials 0.000 claims description 14
- 229910052619 chlorite group Inorganic materials 0.000 claims description 14
- 229910052725 zinc Inorganic materials 0.000 claims description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 13
- 229910052749 magnesium Inorganic materials 0.000 claims description 13
- 229910052791 calcium Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 12
- 239000010452 phosphate Substances 0.000 claims description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 10
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 10
- 238000005097 cold rolling Methods 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- 229910052788 barium Inorganic materials 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 description 25
- 239000011777 magnesium Substances 0.000 description 23
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 18
- 239000011575 calcium Substances 0.000 description 13
- 230000002265 prevention Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical compound [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 description 9
- 229910020366 ClO 4 Inorganic materials 0.000 description 7
- 229910052839 forsterite Inorganic materials 0.000 description 7
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 5
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 5
- 238000005098 hot rolling Methods 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005261 decarburization Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Chemical class O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 239000004137 magnesium phosphate Substances 0.000 description 2
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 2
- 229960002261 magnesium phosphate Drugs 0.000 description 2
- 235000010994 magnesium phosphates Nutrition 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- WHQOKFZWSDOTQP-UHFFFAOYSA-N 2,3-dihydroxypropyl 4-aminobenzoate Chemical compound NC1=CC=C(C(=O)OCC(O)CO)C=C1 WHQOKFZWSDOTQP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910000976 Electrical steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 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
- 238000006243 chemical reaction Methods 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- QQFLQYOOQVLGTQ-UHFFFAOYSA-L magnesium;dihydrogen phosphate Chemical compound [Mg+2].OP(O)([O-])=O.OP(O)([O-])=O QQFLQYOOQVLGTQ-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 sulfate Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
- C23C22/74—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process for obtaining burned-in conversion coatings
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Manufacturing Of Steel Electrode Plates (AREA)
Description
本発明は、被膜張力、耐吸湿性、防錆性および占積率が共に優れる方向性電磁鋼板の製造に用いられる絶縁被膜処理液と、その処理液を用いた方向性電磁鋼板の製造方法に関するものである。 The present invention relates to an insulating coating treatment liquid used for the production of a grain-oriented electrical steel sheet having excellent coating tension, moisture absorption resistance, rust resistance and space factor, and a method for producing a grain-oriented electrical steel sheet using the treatment liquid. Is.
近年、電力用変圧器から発生する騒音が新たな公害として問題となっている。電力用変圧器の騒音は、変圧器の鉄心に用いられている方向性電磁鋼板の磁歪に起因するものであることが知られている。したがって、変圧器の騒音を減らすためには、方向性電磁鋼板の磁歪を小さくする必要がある。方向性電磁鋼板の磁歪を低減する工業的に有効な手段としては、低熱膨張性の上塗絶縁被膜を形成し、鋼板に引張応力を付与する方法がある。 In recent years, noise generated from power transformers has become a problem as new pollution. It is known that the noise of a power transformer is caused by magnetostriction of a grain-oriented electrical steel sheet used for the iron core of the transformer. Therefore, in order to reduce the noise of the transformer, it is necessary to reduce the magnetostriction of the grain-oriented electrical steel sheet. As an industrially effective means for reducing the magnetostriction of a grain-oriented electrical steel sheet, there is a method of forming a low thermal expansion top coat insulating film and imparting a tensile stress to the steel sheet.
方向性電磁鋼板の表面に形成される被膜は、通常、二次再結晶焼鈍時に形成された結晶質のフォルステライト被膜と、その上に形成されたリン酸塩系の絶縁被膜とから構成されている。この絶縁被膜を形成する従来技術としては、特許文献１あるいは特許文献２に開示されているような、コロイド状シリカとリン酸塩、さらに無水クロム酸、クロム酸塩、重クロム酸塩のうちから選ばれる１種または２種以上を含有する絶縁被膜処理液を塗布し焼き付ける方法がある。
The film formed on the surface of grain-oriented electrical steel sheets is usually composed of a crystalline forsterite film formed during secondary recrystallization annealing and a phosphate-based insulating film formed thereon. Yes. Conventional techniques for forming this insulating film include colloidal silica and phosphate, as well as chromic anhydride, chromate, and dichromate as disclosed in
この方法によって形成される絶縁被膜は、方向性電磁鋼板に引張応力を付与し、磁歪特性を改善する効果を有する。しかし、この絶縁被膜形成に用いられる処理液には、絶縁被膜の耐吸湿性を改善するために、無水クロム酸やクロム酸塩、重クロム酸塩が添加されており、これに由来する６価クロムを含有している。この処理液中に含まれる６価クロムは、塗布後の焼付けにより３価クロムに還元されて無害化されるとはいえ、廃液処理作業において、取り扱いが難しいなどの問題がある。 The insulating film formed by this method has the effect of imparting tensile stress to the grain-oriented electrical steel sheet and improving the magnetostriction characteristics. However, in order to improve the moisture absorption resistance of the insulating coating, chromic anhydride, chromate, and dichromate are added to the treatment liquid used for forming the insulating coating, and the hexavalent derived therefrom. Contains chromium. Although hexavalent chromium contained in the treatment liquid is reduced to trivalent chromium by baking after coating and rendered harmless, there is a problem that handling is difficult in waste liquid treatment work.
そこで、無水クロム酸やクロム酸塩、重クロム酸塩を含まない絶縁被膜処理液の開発が行われている。例えば、特許文献３には、コロイド状シリカとリン酸アルミニウムと硼酸とＭｇ，Ａｌ，Ｆｅ，Ｃｏ，Ｎｉ，Ｚｎの硫酸塩から選ばれる１種または２種以上を含有する絶縁被膜処理液が開示され、また、特許文献４には、コロイド状シリカとリン酸マグネシウムおよびＭｇ，Ａｌ，Ｍｎ，Ｚｎの硫酸塩から選ばれる１種または２種以上を含有するクロム酸化物を含まない絶縁被膜の形成方法が開示されている。
ところで、方向性電磁鋼板の表面に形成される絶縁被膜に必要とされる特性としては、被膜張力が大きいことの他に、耐吸湿性や防錆性に優れ、占積率が高いことが挙げられる。しかし、特許文献３や特許文献４に記載された、無水クロム酸やクロム酸塩、重クロム酸塩等のクロム酸類を含有しない絶縁被膜は、近年における被膜特性に対する高い要求に対しては、必ずしも十分な被膜張力や耐吸湿性を有するものではない。
By the way, as a characteristic required for the insulating coating formed on the surface of the grain-oriented electrical steel sheet, in addition to the high coating tension, it is excellent in moisture absorption resistance and rust prevention and has a high space factor. It is done. However, the insulating coatings described in
そこで、本発明の目的は、クロムを含有しない、被膜張力、耐吸湿性、防錆性および占積率が共に優れた方向性電磁鋼板用絶縁被膜処理液と、その処理液を用いた方向性電磁鋼板の製造方法を提案することにある。 Accordingly, an object of the present invention is to provide an insulating coating treatment solution for grain-oriented electrical steel sheets that does not contain chromium and has excellent coating tension, moisture absorption resistance, rust prevention, and space factor, and directionality using the treatment solution. The purpose is to propose a method of manufacturing an electrical steel sheet.
発明者らは、従来技術のクロムフリー絶縁被膜が抱える上記問題点を解決するために、各種リン酸塩とコロイド状シリカを配合し、さらにこれに、種々の水溶性金属塩を添加した絶縁被膜処理液を二次再結晶焼鈍後の方向性電磁鋼板に塗布し、焼き付けて、被膜特性を評価した。その結果、ある特定金属の次亜塩素酸塩、亜塩素酸塩、塩素酸塩、過塩素酸塩を添加することにより、所期した特性を有する絶縁被膜が得られることを見出した。そしてさらに、種々のリン酸塩、金属の次亜塩素酸塩、亜塩素酸塩、塩素酸塩、過塩素酸塩を用いて、絶縁被膜処理液の最適組成を検討するとともに、その処理液を用いて方向性電磁鋼板を製造する方法を検討し、本発明を完成させた。 In order to solve the above-mentioned problems of the prior art chromium-free insulating coating, the inventors have blended various phosphates and colloidal silica, and further added various water-soluble metal salts thereto. The treatment liquid was applied to the grain-oriented electrical steel sheet after the secondary recrystallization annealing and baked to evaluate the film properties. As a result, it has been found that by adding hypochlorite, chlorite, chlorate, and perchlorate of a specific metal, an insulating film having the desired characteristics can be obtained. In addition, using various phosphates, metal hypochlorites, chlorites, chlorates, and perchlorates, we examined the optimal composition of the insulating coating treatment liquid, and treated the treatment liquid. The present invention was completed by studying a method for producing a grain-oriented electrical steel sheet.
すなわち、本発明は、Ｍｇ，Ｃａ，Ｂａ，Ｓｒ，Ｚｎ，ＡｌおよびＭｎのリン酸塩から選ばれるいずれか１種または２種以上に対して、そのリン酸塩のリン酸（ＰＯ４）１ｍｏｌに対し、コロイド状シリカをＳｉＯ２にして０．５〜１０ｍｏｌ、Ｃａ，Ｍｎ，Ｆｅ，Ｍｇ，Ｚｎ，Ｃｏ，Ｎｉ，ＣｕおよびＡｌの次亜塩素酸塩、亜塩素酸塩、塩素酸塩、過塩素酸塩から選ばれるいずれか１種または２種以上を金属元素のモル数にして合計０．０５〜３．０ｍｏｌ含有する方向性電磁鋼板用絶縁被膜処理液である。 That is, in the present invention, 1 mol or more of phosphoric acid (PO 4 ) of the phosphate with respect to any one or two or more selected from phosphates of Mg, Ca, Ba, Sr, Zn, Al and Mn. to, 0.5 to 10 mol and the colloidal silica SiO 2, Ca, Mn, Fe , Mg, Zn, Co, hypochlorite Ni, Cu and Al, chlorite, chlorate, It is an insulating film treatment liquid for grain-oriented electrical steel sheets containing any one or more selected from perchlorates in a total number of 0.05 to 3.0 mol in terms of the number of moles of metal element.
また、本発明は、方向性電磁鋼板用鋼スラブを熱間圧延し、熱延板焼鈍したのちあるいは熱延板焼鈍することなく、１回の冷間圧延または中間焼鈍を挟む２回以上の冷間圧延により最終板厚とし、一次再結晶焼鈍および二次再結晶焼鈍し、その後、絶縁被膜を形成する方向性電磁鋼板の製造方法において、上記の絶縁被膜処理液を塗布し、３５０℃以上の温度で焼付処理して絶縁被膜を形成することを特徴とする方向性電磁鋼板の製造方法を提案する。 In addition, the present invention provides a steel slab for grain-oriented electrical steel sheets that is hot-rolled and subjected to two or more cold sandwiches between one cold rolling or intermediate annealing without hot-rolled sheet annealing or hot-rolled sheet annealing. In the manufacturing method of the grain-oriented electrical steel sheet that forms the final sheet thickness by hot rolling, primary recrystallization annealing and secondary recrystallization annealing, and then forms an insulating film, the above-mentioned insulating film treatment liquid is applied, and 350 ° C or higher A method of manufacturing a grain-oriented electrical steel sheet characterized by forming an insulating coating by baking at a temperature is proposed.
本発明によれば、方向性電磁鋼板の表面に、被膜張力、耐吸湿性、防錆性および占積率が共に優れた絶縁被膜を形成することができるので、方向性電磁鋼板の磁歪の低減、ひいては騒音公害の低減に寄与することができる。また、本発明の処理液は、クロムを含まないため、廃液処理が容易となり、環境保護の面からも好ましい。 According to the present invention, since an insulating coating having excellent coating tension, moisture absorption resistance, rust resistance, and space factor can be formed on the surface of a grain-oriented electrical steel sheet, the magnetostriction of the grain-oriented electrical steel sheet is reduced. As a result, it can contribute to the reduction of noise pollution. Further, since the treatment liquid of the present invention does not contain chromium, the waste liquid treatment becomes easy, which is preferable from the viewpoint of environmental protection.
本発明を開発する契機となった実験について説明する。
リン酸マグネシウムＭｇ（Ｈ２ＰＯ４）２の３４ｍａｓｓ％水溶液４５０ｍｌ（リン酸（ＰＯ４）に換算して１ｍｏｌに相当）に、ＳｉＯ２分を３０ｍａｓｓ％含むコロイド状シリカ４５０ｍｌ（ＳｉＯ２に換算して２ｍｏｌに相当）を添加し、さらに、過塩素酸マグネシウムＭｇ（ＣｌＯ４）２の添加量をＭｇに換算して０．０１〜３ｍｏｌの範囲で変化させて添加して絶縁被膜処理液を調整した。次いで、この絶縁被膜処理液を、板厚０．２２ｍｍでフォルステライト被膜を有する二次再結晶焼鈍後の方向性電磁鋼板に塗布し、８００℃×６０秒の焼付処理を施し、厚さが片面当たり２μｍの絶縁被膜を形成させた。この絶縁被膜焼付処理後の方向性電磁鋼板について、被膜張力、耐吸湿性、防錆性および占積率を下記の方法で評価した。
An experiment that triggered the development of the present invention will be described.
Phosphate magnesium Mg (
（１）被膜張力
本発明における被膜張力とは、絶縁被膜によって鋼板に付与される張力のことである。この被膜張力は、上記焼付処理後の方向性電磁鋼板から、長さ方向を圧延方向として、幅３０ｍｍ×長さ２８０ｍｍの試験片を剪断により採取し、片面の絶縁被膜を除去してから、鋼板の長さ方向端部３０ｍｍを固定して、長さ方向を水平方向、幅方向を鉛直方向とし、この時の試験片端部の反りの大きさを測定し、下記式；
σ（ＭＰａ）＝１．２１５２×１０６（ＭＰａ）×板厚（ｍｍ）×反り（ｍｍ）／２５０（ｍｍ）／２５０（ｍｍ）
から算出した。
（２）耐吸湿性
耐吸湿性は、上記焼付処理後の方向性電磁鋼板から、５０ｍｍ×５０ｍｍの試験片を３枚採取し、これらを１００℃の蒸留水に浸漬して５分間煮沸し、被膜表面からのＰ溶出量を定量分析することにより評価した。
（３）防錆性
防錆性は、温度５０％、露点５０℃の空気中に５０時間保持した後、鋼板表面を目視観察し、錆びの発生の有無により評価した。
（４）占積率
占積率は、ＪＩＳ Ｃ２５５０に規定された方法により評価した。
(1) Film tension The film tension in the present invention is the tension applied to the steel sheet by the insulating film. This coating tension is obtained by shearing a test piece having a width of 30 mm and a length of 280 mm from the grain-oriented electrical steel sheet after the baking treatment, with the length direction being the rolling direction, and removing the insulating coating on one side, The length direction end 30 mm is fixed, the length direction is the horizontal direction, the width direction is the vertical direction, and the amount of warping of the test piece end at this time is measured.
σ (MPa) = 1.152 × 10 6 (MPa) × plate thickness (mm) × warp (mm) / 250 (mm) / 250 (mm)
Calculated from
(2) Hygroscopic resistance The hygroscopic resistance is obtained by collecting three 50 mm × 50 mm test pieces from the grain-oriented electrical steel sheet after the baking treatment, immersing them in distilled water at 100 ° C. and boiling for 5 minutes. The amount of P elution from the coating surface was evaluated by quantitative analysis.
(3) Rust prevention property The rust prevention property was evaluated by visually observing the surface of the steel sheet after being held in air at a temperature of 50% and a dew point of 50 ° C. for 50 hours.
(4) Space factor The space factor was evaluated by the method defined in JIS C2550.
図１は、Ｐ溶出量、即ち、耐吸湿性に及ぼす過塩素酸マグネシウムの添加量の影響を示したものである。図１から、リン酸塩とコロイド状シリカからなる絶縁被膜処理液に、過塩素酸マグネシウムを添加することにより耐吸湿性は改善され、リン酸（ＰＯ４）１ｍｏｌに対し、過塩素酸マグネシウムを０．０５ｍｏｌ以上添加することにより、良好な耐吸湿性が得られることがわかる。 FIG. 1 shows the influence of the amount of magnesium perchlorate added on the P elution amount, that is, the moisture absorption resistance. From FIG. 1, the moisture absorption resistance is improved by adding magnesium perchlorate to an insulating coating treatment liquid composed of phosphate and colloidal silica, and magnesium perchlorate is added to 1 mol of phosphoric acid (PO 4 ). It can be seen that good moisture absorption resistance can be obtained by adding 0.05 mol or more.
また、図２は、被膜張力に及ぼす過塩素酸マグネシウムの添加量の影響を示したものである。図２から、リン酸塩とコロイド状シリカからなる絶縁被膜処理液に対して、リン酸（ＰＯ４）１ｍｏｌに対し、過塩素酸マグネシウムを３．０ｍｏｌ超添加すると、被膜張力は、低下する傾向にあることがわかる。なお、他の特性（防錆性、占積率）については、過塩素酸マグネシウムの添加量に因らず良好であった。
本発明は、上記新規な知見に基き開発したものである。
FIG. 2 shows the influence of the amount of magnesium perchlorate added on the film tension. From FIG. 2, the coating tension tends to decrease when magnesium perchlorate exceeds 3.0 mol with respect to 1 mol of phosphoric acid (PO 4 ) with respect to the insulating coating treatment liquid composed of phosphate and colloidal silica. You can see that In addition, about other characteristics (rust prevention property, space factor), it was favorable irrespective of the addition amount of magnesium perchlorate.
The present invention has been developed based on the above novel findings.
次に、本発明に係る絶縁被膜処理液について説明する。
本発明の絶縁被膜処理液は、Ｍｇ，Ｃａ，Ｂａ，Ｓｒ，Ｚｎ，ＡｌおよびＭｎのリン酸塩から選ばれるいずれか１種または２種以上と、コロイド状シリカと、Ｃａ，Ｍｎ，Ｆｅ，Ｍｇ，Ｚｎ，Ｃｏ，Ｎｉ，ＣｕおよびＡｌの次亜塩素酸塩、亜塩素酸塩、塩素酸塩、過塩素酸塩から選ばれるいずれか１種または２種以上とから構成されるものである。
Next, the insulating coating solution according to the present invention will be described.
The insulating coating treatment liquid of the present invention includes any one or more selected from phosphates of Mg, Ca, Ba, Sr, Zn, Al and Mn, colloidal silica, Ca, Mn, Fe, Mg, Zn, Co, Ni, Cu and Al hypochlorite, chlorite, chlorate and perchlorate are selected from one or more kinds .
まず、本発明の絶縁被膜処理液は、Ｍｇ，Ｃａ，Ｂａ，Ｓｒ，Ｚｎ，Ａｌ，Ｍｎのリン酸塩から選ばれる１種または２種以上を含有するものであることが必要である。各種リン酸塩の中で、これら金属元素のリン酸塩に限定する理由は、クロム酸類を添加しない場合には、これら以外の金属元素のリン酸塩では、耐吸湿性に優れる被膜が得られないからである。特に、Ｍｇ，Ｃａ，Ｂａ，Ｓｒ，Ｚｎ，Ａｌ，Ｍｎの第一リン酸塩であるＭｇ（Ｈ２ＰＯ４）２、Ｃａ（Ｈ２ＰＯ４）２、Ｂａ（Ｈ２ＰＯ４）２、Ｓｒ（Ｈ２ＰＯ４）２、Ｚｎ（Ｈ２ＰＯ４）２、Ａｌ（Ｈ２ＰＯ４）３、Ｍｎ（Ｈ２ＰＯ４）２およびこれらの水和物は、水に容易に溶解するため、本発明に好適に用いることができる。 First, the insulating coating solution of the present invention needs to contain one or more selected from the phosphates of Mg, Ca, Ba, Sr, Zn, Al, and Mn. Among various phosphates, the reason for limiting to phosphates of these metal elements is that when chromic acids are not added, phosphates of metal elements other than these can provide a coating with excellent moisture absorption resistance. Because there is no. In particular, Mg (H 2 PO 4 ) 2 , Ca (H 2 PO 4 ) 2 , Ba (H 2 PO 4 ) 2 , which are primary phosphates of Mg, Ca, Ba, Sr, Zn, Al, and Mn, Sr (H 2 PO 4 ) 2 , Zn (H 2 PO 4 ) 2 , Al (H 2 PO 4 ) 3 , Mn (H 2 PO 4 ) 2 and their hydrates are easily dissolved in water. Can be suitably used in the present invention.
また、本発明の絶縁被膜処理液は、上記リン酸塩のリン酸（ＰＯ４）１ｍｏｌに対して、コロイド状シリカをＳｉＯ２に換算して０．５〜１０ｍｏｌ含有する必要がある。コロイド状シリカは、上記リン酸塩と共に低熱膨張率のガラスを形成し、被膜張力を発生させるために必須の成分である。コロイド状シリカは、処理液の安定性、相溶性が得られる限り、特に限定されない。たとえば、市販の酸性タイプであるＳＴ−０（日産化学（株）製、ＳｉＯ２含有量２０ｍａｓｓ％）が挙げられるが、アルカリ性タイプのコロイド状シリカでも使用することができる。さらに、被膜の外観品質を向上させるため、加熱によりアルミナとなるゾル、例えば、アルミナゾル１００（日産化学製）を添加してもよい。 In addition, the insulating coating solution of the present invention needs to contain 0.5 to 10 mol of colloidal silica in terms of SiO 2 with respect to 1 mol of phosphoric acid (PO 4 ) of the above phosphate. Colloidal silica is an essential component for forming a glass having a low coefficient of thermal expansion together with the above-mentioned phosphate and generating film tension. Colloidal silica is not particularly limited as long as the stability and compatibility of the treatment liquid can be obtained. For example, ST-0 which is a commercially available acidic type (manufactured by Nissan Chemical Co., Ltd., SiO 2 content 20 mass%) can be mentioned, but alkaline type colloidal silica can also be used. Furthermore, in order to improve the appearance quality of the coating, a sol that becomes alumina by heating, for example, alumina sol 100 (manufactured by Nissan Chemical Industries) may be added.
さらに、本発明の絶縁被膜処理液は、耐吸湿性を高めるために、Ｃａ，Ｍｎ，Ｆｅ，Ｍｇ，Ｚｎ，Ｃｏ，Ｎｉ，Ｃｕ，Ａｌの次亜塩素酸塩、亜塩素酸塩、塩素酸塩、過塩素酸塩から選ばれる１種または２種以上を、金属元素のモル数に換算して合計０．０５〜３．０ｍｏｌの範囲で含有する必要がある。ここで、次亜塩素酸塩、亜塩素酸塩、塩素酸塩、過塩素酸塩とは、それぞれ、（ＣｌＯ）−、（ＣｌＯ２）−、（ＣｌＯ３）−、（ＣｌＯ４）−と金属元素との化合物（金属塩）であり、また、これらの水和物であっても構わない。 Furthermore, the insulating coating treatment liquid of the present invention is provided with hypochlorite, chlorite, and chloric acid of Ca, Mn, Fe, Mg, Zn, Co, Ni, Cu, and Al in order to enhance moisture absorption resistance. It is necessary to contain one or more selected from salts and perchlorates in a range of 0.05 to 3.0 mol in total in terms of the number of moles of the metal element. Here, hypochlorite, chlorite, chlorate, and perchlorate are (ClO) − , (ClO 2 ) − , (ClO 3 ) − , (ClO 4 ) − and It is a compound (metal salt) with a metal element, and these hydrates may also be used.
耐吸湿性を高めるためには、リン酸塩のリン酸（ＰＯ４）１ｍｏｌに対し、次亜塩素酸塩、亜塩素酸塩、塩素酸塩、過塩素酸塩を、金属元素のモル数に換算して０．０５ｍｏｌ以上添加することが必要である。一方、３．０ｍｏｌ以上添加すると、被膜の熱膨張率が増加するため被膜張力が低下するため好ましくない。なお、次亜塩素酸塩、亜塩素酸塩、塩素酸塩、過塩素酸塩を構成する金属元素は、Ｃａ，Ｍｎ，Ｆｅ，Ｍｇ，Ｚｎ，Ｃｏ，Ｎｉ，Ｃｕ，Ａｌであることが必要である。これ以外の金属元素では、例えば、Ｎａでは、被膜張力低下等、被膜特性が劣化するからである。 In order to increase moisture absorption resistance, hypochlorite, chlorite, chlorate, and perchlorate are added to the number of moles of metal element with respect to 1 mol of phosphoric acid (PO 4 ). It is necessary to add 0.05 mol or more in terms of conversion. On the other hand, addition of 3.0 mol or more is not preferable because the thermal expansion coefficient of the coating increases and the coating tension decreases. The metal elements constituting hypochlorite, chlorite, chlorate, and perchlorate must be Ca, Mn, Fe, Mg, Zn, Co, Ni, Cu, and Al. It is. This is because, with other metal elements, for example, Na deteriorates the film characteristics such as a decrease in film tension.
ここで、Ｃａ，Ｍｎ，Ｆｅ，Ｍｇ，Ｚｎ，Ｃｏ，Ｎｉ，Ｃｕ，Ａｌの次亜塩素酸塩、亜塩素酸塩、塩素酸塩、過塩素酸塩の添加により、耐吸湿性が高められる理由は、シリカとリン酸塩はガラスを形成するが、ガラスに取り込まれなかったフリーのリン酸が、次亜塩素酸塩、亜塩素酸塩、塩素酸塩、過塩素酸塩の金属元素（Ｃａ，Ｍｎ，Ｆｅ，Ｍｇ，Ｚｎ，Ｃｏ，Ｎｉ，Ｃｕ，Ａｌ）と結合して不溶化し、耐吸湿性を向上するため推定される。また、次亜塩素酸塩、亜塩素酸塩、塩素酸塩、過塩素酸塩は、硫酸塩など他の水溶性の塩と比較して、被膜中に均一に分散するため、フリーのリン酸と金属元素の結合が容易となり、これが耐吸湿性の向上に有利に働くためと考えられる。 Here, by adding hypochlorite, chlorite, chlorate, and perchlorate of Ca, Mn, Fe, Mg, Zn, Co, Ni, Cu, and Al, moisture absorption resistance is enhanced. The reason is that silica and phosphate form a glass, but free phosphoric acid that was not incorporated into the glass is a hypochlorite, chlorite, chlorate, perchlorate metal element ( Ca, Mn, Fe, Mg, Zn, Co, Ni, Cu, and Al) are combined to insolubilize and are estimated to improve moisture absorption resistance. Hypochlorite, chlorite, chlorate, and perchlorate are evenly dispersed in the film compared to other water-soluble salts such as sulfate, so free phosphoric acid. This is thought to be because the bonding between the metal element and the metal element is facilitated, and this favorably improves the moisture absorption resistance.
なお、無水クロム酸やクロム酸塩、重クロム酸塩には、絶縁被膜の耐吸湿性を改善する働きがあるため、本発明の処理液では、リン酸塩のリン酸（ＰＯ４）１ｍｏｌに対し３．０ｍｏｌを上限に添加することができるが、前述したように、有害な６価クロムとして、処理液中に存在し、廃液処理が困難となるので、添加しないか、あるいは添加量を最小限にとどめることが望ましい。 In addition, since chromic anhydride, chromate, and dichromate have a function of improving the moisture absorption resistance of the insulating coating, in the treatment liquid of the present invention, 1 mol of phosphoric acid (PO 4 ) is added. 3.0 mol can be added to the upper limit, but as described above, harmful hexavalent chromium is present in the treatment liquid, making it difficult to treat the waste liquid. It is desirable to limit it to the limit.
ところで、方向性電磁鋼板を用いて巻鉄心型の変圧器を製作する場合、鋼板を鉄心の形に巻いて成形するときに鋼板に導入された歪を除去するために、その後、８００℃×３時間程度の歪取焼鈍が施されるが、その際、隣接する鋼板の被膜同士が融着することがある。この融着は、鉄心の層間絶縁抵抗を低下させ、磁気特性を劣化させる原因にもなるので、絶縁被膜は、耐融着性を有するものであることが望ましい。また、方向性電磁鋼板を用いて積鉄心型の変圧器を製作する場合、積み作業を円滑に行うには、鋼板同士の滑り性が良好であることが望ましい。そこで、耐融着性や滑り性を向上するため、本発明の絶縁被膜処理液には、１次粒径が５０〜２０００ｎｍのＳｉＯ２、Ａｌ２Ｏ３、ＴｉＯ２の内から選ばれる１種または２種以上を含有してもよい。 By the way, when manufacturing a wound core type transformer using a directional electromagnetic steel sheet, in order to remove the distortion introduced into the steel sheet when the steel sheet is wound into a shape of an iron core, 800 ° C. × 3 Although strain relief annealing for about an hour is performed, the coatings of the adjacent steel plates may be fused together. This fusion reduces the interlayer insulation resistance of the iron core and causes the magnetic properties to deteriorate. Therefore, it is desirable that the insulating coating has a fusion resistance. Moreover, when producing a laminated iron core type | mold transformer using a grain-oriented electrical steel sheet, in order to perform a stacking operation smoothly, it is desirable that the slidability of steel plates is favorable. Therefore, in order to improve the anti-fusing property and the slipperiness, the insulating film treatment liquid of the present invention is one kind selected from SiO 2 , Al 2 O 3 and TiO 2 having a primary particle size of 50 to 2000 nm. Or you may contain 2 or more types.
次に、本発明に係る上記絶縁被膜処理液を用いて方向性電磁鋼板を製造する方法について説明する。
本発明の方向性電磁鋼板の製造方法は、所定の成分組成を有する方向性電磁鋼板用鋼スラブを熱間圧延し、熱延板焼鈍しあるいは熱延板焼鈍を施すことなく冷間圧延して最終板厚とし、その後、一次再結晶焼鈍と二次再結晶焼鈍を施した後、上述した本発明の絶縁被膜処理液を鋼板表面に塗布し、３５０℃以上の温度で焼付処理する方法である。
Next, a method for producing a grain-oriented electrical steel sheet using the insulating coating solution according to the present invention will be described.
The method for producing a grain-oriented electrical steel sheet according to the present invention includes hot rolling a steel slab for grain-oriented electrical steel sheet having a predetermined component composition, and cold rolling without hot-rolled sheet annealing or hot-rolled sheet annealing. It is a method of setting the final plate thickness, and subsequently applying the primary recrystallization annealing and the secondary recrystallization annealing, then applying the above-described insulating coating treatment liquid of the present invention to the surface of the steel plate, and baking at a temperature of 350 ° C. or higher. .
上記方向性電磁鋼板用鋼スラブの成分組成は、公知の成分組成あればよく、例えば、Ｓを２００ｍａｓｓｐｐｍ程度添加して、インヒビターとしてＭｎＳを用いる成分系、ｓｏｌ．Ａｌを２００ｐｐｍ程度添加して、インヒビターとしてＡｌＮを用いる成分系、インヒビター成分としてＭｎＳｅとＳｂを用いる成分系、あるいは、インヒビター成分を添加しない成分系など、いずれの成分系でもよい。 The component composition of the steel slab for grain-oriented electrical steel sheet may be a known component composition. For example, a component system in which about 200 mass ppm of S is added and MnS is used as an inhibitor, sol. Any component system such as a component system using AlN as an inhibitor by adding about 200 ppm, a component system using MnSe and Sb as inhibitor components, or a component system without adding inhibitor components may be used.
方向性電磁鋼板用鋼スラブの熱間圧延は、公知の方法を適用できるが、熱間圧延後の板厚は１．５〜３．０ｍｍの範囲とするのが望ましい。熱間圧延後の熱延板は、その後、熱延板焼鈍し、必要に応じて酸洗し、あるいは、熱延板焼鈍を施すことなく、必要に応じて酸洗し、冷間圧延して最終板厚とする。上記冷間圧延は、１回の冷間圧延あるいは中間焼鈍を挟む２回以上の冷間圧延としてもよい。 A known method can be applied to hot rolling of the steel slab for grain-oriented electrical steel sheets, but the thickness after hot rolling is preferably in the range of 1.5 to 3.0 mm. The hot-rolled sheet after hot rolling is then subjected to hot-rolled sheet annealing, pickling as necessary, or pickling as necessary, and cold-rolling without performing hot-rolled sheet annealing. Final thickness. The cold rolling may be one or more cold rollings or two or more cold rollings sandwiching intermediate annealing.
冷間圧延に続く一次再結晶焼鈍は、一次再結晶のために施すが、脱炭を兼ねて行ってもよく、その処理条件は、８００〜９５０℃の温度で１０〜６００秒程度の連続焼鈍で行うのが好ましい。なお、この一次再結晶焼鈍中あるいは一次再結晶焼鈍後に、アンモニアガスなどを用いて窒化処理を施すこともできる。 The primary recrystallization annealing following the cold rolling is performed for the primary recrystallization, but may be performed also for decarburization, and the treatment condition is continuous annealing at a temperature of 800 to 950 ° C. for about 10 to 600 seconds. It is preferable to carry out. Note that nitriding treatment may be performed using ammonia gas or the like during or after the primary recrystallization annealing.
続く二次再結晶焼鈍は、鋼板に二次再結晶を起こさせることによって、磁気特性が優れる結晶方位（いわゆる「ゴス方位」）を圧延方向に高度に集積させた集合組織を得るために施す。また、この二次再結晶焼鈍では、インヒビター成分の純化やフォルステライト被膜の形成を兼ねて行うこともできる。この焼鈍条件としては、８００〜１２５０℃×５〜３００時間程度のバッチ焼鈍とするのが好ましい。 The subsequent secondary recrystallization annealing is performed in order to obtain a texture in which the crystal orientation (so-called “Goth orientation”) having excellent magnetic properties is highly accumulated in the rolling direction by causing secondary recrystallization in the steel sheet. Further, this secondary recrystallization annealing can also be performed to purify the inhibitor component and form a forsterite film. As this annealing condition, it is preferable to perform batch annealing at about 800 to 1250 ° C. for about 5 to 300 hours.
次いで、上記のようにして得た二次再結晶後の方向性電磁鋼板の表面に、本発明の絶縁被膜処理液を、ロールコーター等の公知の方法で塗布し、３５０℃以上の温度で焼付処理し、絶縁被膜を形成する。なお、絶縁被膜の耐吸湿性を向上するためには、３５０℃以上の温度での焼付処理が必要であるが、変圧器の製造工程において歪取焼鈍が行われない場合には、焼付処理温度は７５０℃以上とするのが好ましい。というのは、絶縁被膜による張力は、７５０℃以上の温度に加熱されることにより発生する。歪取焼鈍が行われる場合には、この歪取焼鈍により被膜張力が発生するため、絶縁被膜の焼付処理温度は３５０℃以上であればよいが、歪取焼鈍が行われない場合には、絶縁被膜の焼付処理で被膜張力を発生させる必要があるからである。焼付温度の上限は、１１００℃である。これは、１１００℃を超えると、防錆性が劣化するからである。なお、絶縁被膜処理液を塗布する二次再結晶後の鋼板表面には、フォルステライト被膜が存在してもしていなくても構わない。 Next, the insulating coating treatment liquid of the present invention is applied to the surface of the grain-oriented electrical steel sheet after secondary recrystallization obtained as described above by a known method such as a roll coater, and baked at a temperature of 350 ° C. or higher. Process to form an insulating coating. In addition, in order to improve the moisture absorption resistance of the insulating coating, a baking treatment at a temperature of 350 ° C. or higher is necessary. However, if the strain relief annealing is not performed in the transformer manufacturing process, the baking treatment temperature is Is preferably 750 ° C. or higher. This is because the tension due to the insulating coating is generated by heating to a temperature of 750 ° C. or higher. When strain relief annealing is performed, film tension is generated by this strain relief annealing. Therefore, the baking temperature of the insulating coating may be 350 ° C. or higher. However, when strain relief annealing is not performed, insulation is performed. This is because the film tension needs to be generated by the baking process of the film. The upper limit of the baking temperature is 1100 ° C. This is because if it exceeds 1100 ° C., the rust prevention properties deteriorate. Note that the forsterite film may or may not exist on the surface of the steel sheet after the secondary recrystallization to which the insulating film treatment liquid is applied.
絶縁被膜の厚さは、特に限定しないが、片面当たり１〜５μｍの範囲とするのが好ましい。被膜張力は、被膜の厚さに比例するため、１μｍ未満では、被膜張力が不足する可能性があり、また、５μｍ超では占積率が低下するからである。また、本発明の絶縁被膜処理液には、塗布性を向上するために、水を加えて液比重を調整することもできる。 The thickness of the insulating coating is not particularly limited, but is preferably in the range of 1 to 5 μm per side. This is because the film tension is proportional to the thickness of the film, and if it is less than 1 μm, the film tension may be insufficient, and if it exceeds 5 μm, the space factor decreases. Moreover, in order to improve applicability | paintability, the liquid specific gravity can also be adjusted to the insulating-film processing liquid of this invention by adding water.
Ｃ：０．０５ｍａｓｓ％、Ｓｉ：３ｍａｓｓ％、Ｍｎ：０．０４ｍａｓｓ％、Ｓ：０．０２ｍａｓｓ％、ｓｏｌ．Ａｌ：０．０２ｍａｓｓ％を含有する方向性電磁鋼板用スラブを熱間圧延して板厚２．０ｍｍの熱延板とし、１０００℃×６０秒の熱延板焼鈍を施し、次いで、この熱延板を冷間圧延して板厚１．５ｍｍとし、１１００℃×６０秒の中間焼鈍した後、冷間圧延して最終板厚０．２２ｍｍの冷延板とした。次いで、この冷延板を、脱炭を兼ねた８２０℃×１５０秒の１次再結晶焼鈍し、焼鈍分離剤（ＭｇＯスラリー）を塗布した後、１２００℃×１５時間の二次再結晶焼鈍し、フォルステライト被膜を有する方向性電磁鋼板を得た。 C: 0.05 mass%, Si: 3 mass%, Mn: 0.04 mass%, S: 0.02 mass%, sol. A slab for grain-oriented electrical steel sheet containing Al: 0.02 mass% is hot-rolled to form a hot-rolled sheet having a thickness of 2.0 mm, subjected to hot-rolled sheet annealing at 1000 ° C. for 60 seconds, and then this hot-rolled sheet The plate was cold-rolled to a thickness of 1.5 mm, subjected to intermediate annealing at 1100 ° C. for 60 seconds, and then cold-rolled to obtain a cold-rolled plate having a final thickness of 0.22 mm. Next, this cold-rolled sheet is subjected to primary recrystallization annealing at 820 ° C. × 150 seconds, which also serves as decarburization, and after applying an annealing separator (MgO slurry), it is subjected to secondary recrystallization annealing at 1200 ° C. for 15 hours. A grain-oriented electrical steel sheet having a forsterite film was obtained.
次に、リン酸マグネシウムＭｇ（Ｈ２ＰＯ４）２をリン酸（ＰＯ４）換算で１ｍｏｌ含有する水溶液５００ｍｌと、ＳｉＯ２を３ｍｏｌ含有するコロイド状シリカ７００ｍｌとを混合し、これに、表１に示す次亜塩素酸塩、亜塩素酸塩、塩素酸塩、過塩素酸塩を添加して絶縁被膜処理液を調整し、この処理液を、上記のようにして得た方向性電磁鋼板の表面に塗布し、７５０℃×１分の焼付処理を施した。被膜厚さはいずれも片面当たり２μｍとした。このようにして得た絶縁被膜付き方向性電磁鋼板について、被膜張力、耐吸湿性、防錆性および占積率を下記の方法で評価した。 Next, 500 ml of an aqueous solution containing 1 mol of magnesium phosphate Mg (H 2 PO 4 ) 2 in terms of phosphoric acid (PO 4 ) and 700 ml of colloidal silica containing 3 mol of SiO 2 were mixed. Hypochlorite, chlorite, chlorate, and perchlorate shown in Fig. 2 were added to adjust the insulating coating treatment liquid, and this treatment liquid was prepared as described above for the grain-oriented electrical steel sheet. It was applied to the surface and baked at 750 ° C. for 1 minute. The film thickness was 2 μm per side. The thus-obtained grain-oriented electrical steel sheet with an insulating coating was evaluated for coating tension, moisture absorption resistance, rust resistance, and space factor by the following methods.
（１）被膜張力
上記焼付処理後の方向性電磁鋼板から、長さ方向を圧延方向として、幅３０ｍｍ×長さ２８０ｍｍの試験片を剪断により採取し、片面の絶縁被膜を除去してから、鋼板の長さ方向端部３０ｍｍを固定して、長さ方向を水平方向、幅方向を鉛直方向とし、この時の試験片端部の反りの大きさを測定し、下記式；
σ（ＭＰａ）＝１．２１５２×１０６（ＭＰａ）×板厚（ｍｍ）×反り（ｍｍ）／２５０（ｍｍ）／２５０（ｍｍ）
により算出した。
（２）耐吸湿性
耐吸湿性は、上記焼付処理後の方向性電磁鋼板から、５０ｍｍ×５０ｍｍの試験片を３枚採取し、これらを１００℃の蒸留水に浸漬して５分間煮沸し、被膜表面から溶出したＰの量を定量分析して評価した。
（３）防錆性
防錆性は、温度５０％、露点５０℃の空気中に５０時間保持した後、鋼板表面を目視で観察し、錆びの発生がないものを防錆性良（○）、若干錆びが発生したものを防錆性やや不良（△）、錆びが激しいものを防錆性劣（×）と評価した。
（４）占積率
占積率は、ＪＩＳ Ｃ２５５０に規定された方法により評価した。
(1) Coating tension After removing the insulating coating on one side, a test piece having a width of 30 mm and a length of 280 mm was collected by shearing from the grain-oriented electrical steel sheet after the baking treatment, with the length direction as the rolling direction, and then the steel sheet was removed. The length direction end 30 mm is fixed, the length direction is the horizontal direction, the width direction is the vertical direction, and the amount of warping of the test piece end at this time is measured.
σ (MPa) = 1.152 × 10 6 (MPa) × plate thickness (mm) × warp (mm) / 250 (mm) / 250 (mm)
Calculated by
(2) Hygroscopic resistance The hygroscopic resistance is obtained by collecting three 50 mm × 50 mm test pieces from the grain-oriented electrical steel sheet after the baking treatment, immersing them in distilled water at 100 ° C. and boiling for 5 minutes. The amount of P eluted from the coating surface was quantitatively analyzed and evaluated.
(3) Rust prevention property Rust prevention property is good for rust prevention (○) when the steel sheet surface is visually observed after being kept in air at a temperature of 50% and a dew point of 50 ° C for 50 hours. The rust-proofing was evaluated as slightly rustproof (△), and the rusting was evaluated as poor (x).
(4) Space factor The space factor was evaluated by the method defined in JIS C2550.
上記評価結果を表１中に併記して示した。表１から、本発明で選定したリン酸塩とコロイド状シリカからなる処理液に対して、次亜塩素酸塩、亜塩素酸塩、塩素酸塩、過塩素酸塩を適量添加することにより、被膜張力、耐吸湿性、防錆性および占積率のいずれの被膜特性にも優れる絶縁被膜を形成できることがわかる。 The evaluation results are shown together in Table 1. From Table 1, by adding an appropriate amount of hypochlorite, chlorite, chlorate, perchlorate to the treatment liquid consisting of phosphate and colloidal silica selected in the present invention, It can be seen that it is possible to form an insulating film excellent in all film properties of film tension, moisture absorption resistance, rust resistance, and space factor.
Ｃ：０．０５ｍａｓｓ％、Ｓｉ：３ｍａｓｓ％、Ｍｎ：０．０４ｍａｓｓ％、Ｓ：０．０１ｍａｓｓ％未満、Ｓｂ：０．０３ｍａｓｓ％、ｓｏｌ．Ａｌ：０．０１ｍａｓｓ％未満を含有する方向性電磁鋼板用スラブを熱間圧延し、板厚２．５ｍｍの熱延板としたのち１０５０℃×６０秒の熱延板焼鈍を施し、冷間圧延して板厚０．３０ｍｍの冷延板とした。次いで、上記冷延板に、９００℃×３０秒の一次再結晶焼鈍を施したのち、焼鈍分離剤（ＭｇＯスラリー）を塗布し、８８０℃×５０時間の二次再結晶焼鈍に続いて１２００℃×１５時間の焼鈍を行うバッチ焼鈍を施して、フォルステライト被膜を有する方向性電磁鋼板を得た。 C: 0.05 mass%, Si: 3 mass%, Mn: 0.04 mass%, S: less than 0.01 mass%, Sb: 0.03 mass%, sol. Al: A slab for grain-oriented electrical steel sheet containing less than 0.01 mass% is hot-rolled to form a hot-rolled sheet having a thickness of 2.5 mm, and then subjected to hot-rolled sheet annealing at 1050 ° C. for 60 seconds, and cold-rolled. Thus, a cold-rolled sheet having a thickness of 0.30 mm was obtained. Next, after subjecting the cold-rolled sheet to primary recrystallization annealing at 900 ° C. for 30 seconds, an annealing separator (MgO slurry) was applied, followed by secondary recrystallization annealing at 880 ° C. for 50 hours to 1200 ° C. The batch-oriented annealing which anneals x15 hours was given, and the grain-oriented electrical steel sheet which has a forsterite film was obtained.
次いで、表２に示したリン酸塩をリン酸（ＰＯ４）に換算して１ｍｏｌを含有する水溶液５００ｍｌに、１００ｍｌ当たり０．５ｍｏｌのＳｉＯ２を含有するコロイド状シリカを表２に示した量添加し、さらに、過塩素酸マグネシウムＭｇ（ＣｌＯ４）２をＭｇ換算で０．５ｍｏｌ、過塩素酸カルシウムＣａ（ＣｌＯ４）２をＣａ換算で１．０ｍｏｌ（合計１．５ｍｏｌ）を添加した絶縁被膜処理液を調整し、この処理液を上記方向性電磁鋼板の表面に塗布し、１０３０℃×６０秒の焼付処理を施した。なお、焼付処理後の被膜厚さは片面当り３μｍであった。この焼付処理後の方向性電磁鋼板について、実施例１と同様にして、被膜張力、耐吸湿性、防錆性および占積率を評価した。 Next, the amount of colloidal silica containing 0.5 mol of SiO 2 per 100 ml in 500 ml of an aqueous solution containing 1 mol of the phosphate shown in Table 2 in terms of phosphoric acid (PO 4 ) Furthermore, 0.5 mol of magnesium perchlorate Mg (ClO 4 ) 2 in terms of Mg and 1.0 mol of calcium perchlorate Ca (ClO 4 ) 2 in terms of Ca (total 1.5 mol) were added. A coating treatment solution was prepared, and this treatment solution was applied to the surface of the grain-oriented electrical steel sheet and subjected to a baking treatment at 1030 ° C. for 60 seconds. The film thickness after baking was 3 μm per side. About the grain-oriented electrical steel sheet after this baking process, it carried out similarly to Example 1, and evaluated the film tension | tensile_strength, moisture absorption resistance, rust prevention property, and a space factor.
上記評価結果を表２に併記して示した。リン酸塩の種類やコロイド状シリカの量が本発明の範囲内で変化しても、次亜塩素酸塩、亜塩素酸塩、塩素酸塩、過塩素酸塩のいずれか１種を適量添加することにより、被膜張力、耐吸湿性、防錆性、占積率のいずれの被膜特性にも優れる絶縁被膜を形成できることがわかる。 The evaluation results are shown together in Table 2. Appropriate addition of any one of hypochlorite, chlorite, chlorate and perchlorate even if the type of phosphate and the amount of colloidal silica change within the scope of the present invention By doing this, it can be seen that an insulating film excellent in all film properties of film tension, moisture absorption resistance, rust resistance, and space factor can be formed.
Ｃ：０．０５ｍａｓｓ％、Ｓｉ：３ｍａｓｓ％、Ｍｎ：０．０４ｍａｓｓ％、Ｓ：０．０２ｍａｓｓ％、ｓｏｌ．Ａｌ：０．０２ｍａｓｓ％、Ｓｎ：０．１０ｍａｓｓ％を含有する方向性電磁鋼板用スラブを熱間圧延して板厚２．０ｍｍの熱延板とし、１０００℃×６０秒の熱延板焼鈍を施し、冷間圧延して１．５ｍｍとし、１１００℃×６０秒の中間焼鈍を施した後、さらに冷間圧延して最終板厚０．２２ｍｍの冷延板とした。次いで、この冷延板に脱炭を兼ねた８２０℃×１５０秒の一次再結晶焼鈍を施し、焼鈍分離剤（Ａｌ２Ｏ３スラリー）を塗布したのち、１２００℃×１５時間の二次再結晶焼鈍を施して、フォルステライト被膜を有しない方向性電磁鋼板を得た。 C: 0.05 mass%, Si: 3 mass%, Mn: 0.04 mass%, S: 0.02 mass%, sol. A slab for grain-oriented electrical steel sheet containing Al: 0.02 mass% and Sn: 0.10 mass% is hot-rolled into a hot-rolled sheet having a thickness of 2.0 mm, and subjected to hot-rolled sheet annealing at 1000 ° C for 60 seconds. And cold-rolled to 1.5 mm, subjected to intermediate annealing at 1100 ° C. for 60 seconds, and further cold-rolled to obtain a cold-rolled sheet having a final thickness of 0.22 mm. Next, this cold-rolled sheet was subjected to primary recrystallization annealing at 820 ° C. for 150 seconds, which also served as decarburization, and after applying an annealing separator (Al 2 O 3 slurry), secondary recrystallization at 1200 ° C. for 15 hours. Annealing was performed to obtain a grain-oriented electrical steel sheet having no forsterite film.
次いで、第一リン酸マグネシウムＭｇ（Ｈ２ＰＯ４）２をリン酸（ＰＯ４）に換算して０．５ｍｏｌ、第一リン酸アルミニウムＡｌ（Ｈ２ＰＯ４）３をリン酸（ＰＯ４）に換算して０．５ｍｏｌ、合計１ｍｏｌ含有する水溶液５００ｍｌと、ＳｉＯ２を３ｍｏｌ含有するコロイド状シリカ７００ｍlとを混合し、これに過塩素酸マグネシウムＭｇ（ＣｌＯ４）２をＭｇ換算で１．５ｍｏｌを添加した絶縁被膜処理液を調整し、この処理液を、上記方向性電磁鋼板の表面にロールコーターで塗布し、８５０℃×１分の焼付処理を施した。被膜厚さは、片面当り３μｍであった。上記焼付処理後の方向性電磁鋼板について、実施例１と同様にして、被膜張力、耐吸湿性、防錆性および占積率を評価した。 Next, 0.5 mol of primary magnesium phosphate Mg (H 2 PO 4 ) 2 is converted to phosphoric acid (PO 4 ), and primary aluminum phosphate Al (H 2 PO 4 ) 3 is phosphoric acid (PO 4 ). 500 ml of an aqueous solution containing 0.5 mol in total, 1 mol in total, and 700 ml of colloidal silica containing 3 mol of SiO 2 were mixed with 1.5 ml of magnesium perchlorate Mg (ClO 4 ) 2 in terms of Mg. Insulating film treatment liquid to which was added was prepared, and this treatment liquid was applied to the surface of the grain-oriented electrical steel sheet with a roll coater, followed by baking at 850 ° C. for 1 minute. The film thickness was 3 μm per side. About the grain-oriented electrical steel sheet after the said baking process, it carried out similarly to Example 1, and evaluated film | membrane tension | tensile_strength, moisture absorption resistance, rust prevention property, and a space factor.
上記評価の結果は、被膜張力が１１．８ＭＰａ、耐吸湿性が５５μｇ／１５０ｃｍ２、防錆性の評価が○、占積率が９７．８％で、いずれの被膜特性にも優れる絶縁被膜を形成することができた。 As a result of the above evaluation, the coating film tension is 11.8 MPa, the moisture absorption resistance is 55 μg / 150 cm 2 , the rust prevention evaluation is ○, and the space factor is 97.8%. Could be formed.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007083325A JP4983334B2 (en) | 2007-03-28 | 2007-03-28 | Insulating coating solution for grain-oriented electrical steel sheet and method for producing grain-oriented electrical steel sheet |
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| JP5862582B2 (en) * | 2013-02-15 | 2016-02-16 | Ｊｆｅスチール株式会社 | Method for producing grain-oriented electrical steel sheet, grain-oriented electrical steel sheet and surface glass coating for grain-oriented electrical steel sheet |
| KR101811249B1 (en) | 2013-11-28 | 2017-12-21 | 제이에프이 스틸 가부시키가이샤 | Electrical steel sheet provided with insulating coating |
| KR20160134781A (en) * | 2014-04-24 | 2016-11-23 | 제이에프이 스틸 가부시키가이샤 | Treatment solution for chromium-free insulating coating for grain-oriented electrical steel sheet and grain-oriented electrical steel sheet coated with chromium-free insulating coating |
| RU2688982C1 (en) * | 2015-09-29 | 2019-05-23 | Ниппон Стил Энд Сумитомо Метал Корпорейшн | Electrotechnical steel sheet with directed crystallization and method for its production |
| 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 |
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| JPS5652117B2 (en) * | 1973-11-17 | 1981-12-10 | ||
| JPS5917521B2 (en) * | 1975-08-22 | 1984-04-21 | 川崎製鉄株式会社 | Method for forming a heat-resistant top insulating film on grain-oriented silicon steel sheets |
| JPS54143737A (en) * | 1978-04-28 | 1979-11-09 | Kawasaki Steel Co | Formation of chromiummfree insulating top coating for directional silicon steel plate |
| JPS5844744B2 (en) * | 1979-11-22 | 1983-10-05 | 川崎製鉄株式会社 | Method for forming a tension-applied top insulating film that does not contain chromium oxide on grain-oriented silicon steel sheets |
| JP3551517B2 (en) * | 1995-01-06 | 2004-08-11 | Ｊｆｅスチール株式会社 | Oriented silicon steel sheet with good magnetic properties and method for producing the same |
| JP2000169972A (en) * | 1998-12-04 | 2000-06-20 | Nippon Steel Corp | Chromium-free surface treating agent for grain oriented silicon steel sheet, and manufacture of grain oriented silicon steel sheet using same |
| JP2000178760A (en) * | 1998-12-08 | 2000-06-27 | Nippon Steel Corp | Surface treating agent containing no chromium and grain oriented magnetic steel sheet using the same |
| JP4305040B2 (en) * | 2003-05-09 | 2009-07-29 | Ｊｆｅスチール株式会社 | Method for forming chromeless coating for grain-oriented electrical steel sheet |
| JP4264362B2 (en) * | 2004-01-15 | 2009-05-13 | 新日本製鐵株式会社 | 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 |
| JP4878788B2 (en) * | 2005-07-14 | 2012-02-15 | 新日本製鐵株式会社 | Insulating coating agent for electrical steel sheet containing no chromium |
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