JP4878788B2 - Insulating coating agent for electrical steel sheet containing no chromium - Google Patents
Insulating coating agent for electrical steel sheet containing no chromium Download PDFInfo
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- JP4878788B2 JP4878788B2 JP2005206215A JP2005206215A JP4878788B2 JP 4878788 B2 JP4878788 B2 JP 4878788B2 JP 2005206215 A JP2005206215 A JP 2005206215A JP 2005206215 A JP2005206215 A JP 2005206215A JP 4878788 B2 JP4878788 B2 JP 4878788B2
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- colloidal
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- electrical steel
- insulating coating
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- 239000011248 coating agent Substances 0.000 title claims description 82
- 229910000976 Electrical steel Inorganic materials 0.000 title claims description 25
- 239000011651 chromium Substances 0.000 title claims description 23
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims description 19
- 229910052804 chromium Inorganic materials 0.000 title claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 105
- 229910019142 PO4 Inorganic materials 0.000 claims description 56
- 235000021317 phosphate Nutrition 0.000 claims description 56
- 239000010452 phosphate Substances 0.000 claims description 51
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 50
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 46
- 229910052751 metal Inorganic materials 0.000 claims description 44
- 239000002184 metal Substances 0.000 claims description 39
- 239000002245 particle Substances 0.000 claims description 34
- 239000006185 dispersion Substances 0.000 claims description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 29
- 239000008119 colloidal silica Substances 0.000 claims description 28
- -1 oxide Chemical compound 0.000 claims description 25
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 21
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 11
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 150000001450 anions Chemical group 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 150000001768 cations Chemical class 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 6
- 150000003819 basic metal compounds Chemical class 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002891 organic anions Chemical class 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- YCAGGFXSFQFVQL-UHFFFAOYSA-N Endothion Chemical group COC1=COC(CSP(=O)(OC)OC)=CC1=O YCAGGFXSFQFVQL-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 70
- 238000000576 coating method Methods 0.000 description 50
- 238000000137 annealing Methods 0.000 description 36
- 230000000694 effects Effects 0.000 description 33
- 239000000243 solution Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 17
- 229910001224 Grain-oriented electrical steel Inorganic materials 0.000 description 14
- 239000002585 base Substances 0.000 description 14
- 230000007797 corrosion Effects 0.000 description 13
- 238000005260 corrosion Methods 0.000 description 13
- 150000001845 chromium compounds Chemical class 0.000 description 11
- 229910000831 Steel Inorganic materials 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- 239000011521 glass Substances 0.000 description 8
- 230000006872 improvement Effects 0.000 description 8
- 238000009413 insulation Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 238000004804 winding Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 238000005554 pickling Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 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
- 239000002131 composite material Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 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
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000084 colloidal system Substances 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
- 238000000227 grinding Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011882 ultra-fine particle Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910018084 Al-Fe Inorganic materials 0.000 description 1
- 229910018192 Al—Fe Inorganic materials 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-L L-tartrate(2-) Chemical compound [O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O FEWJPZIEWOKRBE-JCYAYHJZSA-L 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910011212 Ti—Fe Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000000573 anti-seizure effect Effects 0.000 description 1
- 150000007514 bases Chemical class 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
- 239000011575 calcium Substances 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
- 238000005097 cold rolling Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 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
- 238000009826 distribution Methods 0.000 description 1
- 238000002296 dynamic light scattering 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
- 239000010419 fine particle Substances 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- 230000005381 magnetic domain Effects 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011701 zinc Substances 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
- C23C22/73—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
-
- 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
- C23C22/05—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
- C23C22/60—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 alkaline aqueous solutions with pH greater than 8
- C23C22/62—Treatment of iron or alloys based thereon
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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)
- Silicon Compounds (AREA)
- Chemical Treatment Of Metals (AREA)
- Manufacturing Of Steel Electrode Plates (AREA)
- Soft Magnetic Materials (AREA)
Description
本発明は方向性電磁鋼板用の絶縁被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被膜特性を有する製品と絶縁被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 not containing chromium, and using 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、次いで絶縁被膜剤を塗布し、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。 The grain-oriented electrical steel sheet is obtained by hot-rolling and annealing a silicon steel slab containing 2 to 4% of Si, and then subjecting it to a final sheet thickness by subjecting it to cold rolling twice or more sandwiching intermediate annealing. After annealing, an annealing separator containing MgO as a main component is applied, finish annealing is performed to develop secondary recrystallization with Goth orientation, and further, impurities such as S and N are removed and a glass film is formed, Next, an insulating coating agent is applied, and baking and heat flattening are performed 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。 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 winding work called racing after compression molding and strain relief annealing.
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被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。 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 insulation coating has excellent adhesion during cutting and winding, and does not impair the working environment such as powdering, and has excellent winding workability and annealing resistance, providing 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被膜とからなる。この絶縁被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、絶縁被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 coating of a 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 and industrialized a tensile 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. Furthermore, in Patent Document 3, uniform mixing is performed on the surface of the insulating coating 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. 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.
これらの絶縁被膜は、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 mixed with a chromium compound in consideration of hygroscopicity after film baking treatment with phosphate, film seizure property during strain relief annealing, and the like.
絶縁被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や分解性のある遊離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この場合、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。 The role of the chromium compound in the insulating coating is to reduce the effects of filling the porous coating structure in the phosphate or phosphate and colloidal silica coatings and the hygroscopic and decomposable free phosphoric acid remaining in the coating components after baking the insulating coating. The effect of fixing and forming a stable phosphate-chromium compound brings about the effect of improving the stickiness of the coating, the seizure during annealing, the coating tension, and the like. In this case, chromic anhydride, chromate or dichromate is used as the treatment liquid and hexavalent chromium is contained. In this case, there are problems in the working environment during the application 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.
この対策として、クロム化合物を含有しない絶縁被膜剤の研究もなされてきた。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被膜形成法が提案されている。 As a countermeasure, an insulating coating agent containing no 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. There has been proposed an insulating film forming method in which a treatment liquid containing 4 to 40 parts by mass in total of any one or two selected from among them 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被膜剤に比較すると、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 coating agent, it cannot be said that the coating performance has been improved sufficiently, and further improvement has been desired.
本発明は、クロム化合物を含有しない絶縁被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被膜を有する方向性電磁鋼板と絶縁被膜剤を提供する。 The present invention solves environmental problems by having an insulating coating agent composition that does not contain a chromium compound, and also provides chromium in insulation based on phosphate, such as conventional phosphate or phosphate-colloidal silica-based coatings. Provided are a grain-oriented electrical steel sheet and an insulating coating agent having an insulating coating excellent in coating performance that solves the problems of moisture absorption resistance, annealing resistance, denseness, and poor coating tension when no compound is contained.
本発明はクロム化合物を含有しない絶縁被膜を有する方向性電磁鋼板と絶縁被膜剤組成として以下の構成を要旨とする。
（１）次のＩ）、II）およびIII ）を含有することを特徴とするクロムを含まない電磁鋼板用絶縁被膜剤。
The gist of the present invention is as follows: a grain-oriented electrical steel sheet having an insulating coating containing no chromium compound and an insulating coating agent composition.
(1) An insulating coating agent for an electrical steel sheet that does not contain chromium, comprising the following I), II), and III):
Ｉ） 燐酸塩 １００質量部
II） コロイダルシリカをＳｉＯ2固形分に換算して３５〜１００質量部
III ） Ｆｅの金属元素を含有するコロイド状化合物の分散液を、該金属元素に換算して０．１〜２０質量部、かつ、前記コロイド状化合物の平均粒子径が５〜８０ｎｍであって、次のａ）またはｂ）から選ばれるもの
ａ）Ｆｅを含有する化合物（但し、該化合物は水酸化物、酸化物、硫酸塩，燐酸塩，炭酸塩または珪酸塩から選ばれる）によりＳｉＯ 2 ，ＺｒＯ 2 またはＴｉＯ 2 から選ばれる１種または２種以上の酸化物からなるコロイド物質を改質して得られるコロイド状化合物
ｂ）Ｆｅの金属元素を含有する化合物（但し、該化合物は水酸化物、酸化物、硫酸塩、燐酸塩、炭酸塩または珪酸塩から選ばれる）を含んでなるコロイド状化合物
I) Phosphate 100 parts by mass
II) 35 to 100 parts by mass of colloidal silica in terms of SiO 2 solid content
III) A dispersion of a colloidal compound containing a metal element of Fe is 0.1 to 20 parts by mass in terms of the metal element , and the average particle size of the colloidal compound is 5 to 80 nm, Selected from the following a) or b)
compounds containing a) Fe (with the proviso that the compound is a hydroxide, oxide, sulfate, phosphate, selected from carbonate or silicate) by one selected from SiO 2, ZrO 2 or TiO 2 or Colloidal compounds obtained by modifying colloidal materials composed of two or more oxides
b) a colloidal compound comprising a compound containing a metal element of Fe (wherein the compound is selected from hydroxide, oxide, sulfate, phosphate, carbonate or silicate)
（２） 前記III）のコロイド状化合物の分散液が、更にＳｉＯ2，Ａｌ2Ｏ3，ＺｒＯ2またはＴｉＯ2から選ばれる１種または２種以上の酸化物からなるコロイド物質を含むものである（１）に記載のクロムを含有しない電磁鋼板用絶縁被膜剤。
（３） 前記III）のコロイド状化合物が、シロキサン結合を有するシリカ系粒子の表面に下記化学式（１）で表される塩基性金属化合物が反応してなる改質シリカ系ゾルを含むことを特徴とする（１）または（２）のいずれかに記載のクロムを含有しない電磁鋼板用絶縁被膜剤。
(2) The dispersion of the colloidal compound of III) further contains a colloidal substance composed of one or more oxides selected from SiO 2 , Al 2 O 3 , ZrO 2 or TiO 2 ( 1 insulation coating agent for electrical steel sheet not containing chromium described).
(3) The colloidal compound of III) includes a modified silica-based sol formed by a reaction of a basic metal compound represented by the following chemical formula (1) on the surface of silica-based particles having a siloxane bond. The insulating coating agent for electrical steel sheets that does not contain chromium according to any one of (1) and (2) .
｛Ｍ2（ＯＨ）nＸ(2a-n)/b｝m −（１）
｛式中、Ｍはそれぞれ独立に、Ｆｅ，Ａｌ，Ｇａ，ＴｉまたはＺｒから選ばれる一種または二種の３価及び／または４価の金属カチオン、Ｘはアニオンであり、ａはＭの金属カチオンの価数、ｂは該アニオンの価数を示し、１≦ｎ≦７，ｎ＜２ａであり、１≦ｍ≦２０である。｝
（４） 前記化学式（１）におけるアニオンＸが、ハロゲンイオン、硫酸イオン、硝酸イオン、有機アニオンの１種または２種以上からなることを特徴とする（３）記載のクロムを含有しない電磁鋼板用絶縁被膜剤。
（５） 前記III）のコロイド状化合物の分散液のｐＨが０．５〜３の範囲にあり、該金属の酸化物換算で１〜２５質量％の金属元素を含有し、該コロイド状化合物の平均粒子径が５〜８０ｎｍの範囲にあることを特徴とする（１）〜（４）のいずれかに記載のクロムを含有しない電磁鋼板用絶縁被膜剤。
（６） 前記III）のコロイド状化合物の分散液が、更に、Ｍｎ，Ｎｉ，Ｃｏ，ＣｕまたはＳｒから選ばれる一種または二種以上の金属元素を含有する化合物を含むものであることを特徴とする（１）〜（５）のいずれかに記載のクロムを含有しない電磁鋼板用絶縁被膜剤。
（７） 前記Ｉ）の燐酸塩が、燐酸塩の水溶液であり、該燐酸塩がＡｌまたはＭｇの第一燐酸塩の１種又は２種を複合した組成であって、該燐酸塩の水溶液中に含まれる遊離燐酸の含有量が該燐酸塩の１５質量％未満であることを特徴とする（１）〜（６）のいずれかに記載のクロムを含有しない電磁鋼板用絶縁被膜剤。
{M 2 (OH) n X (2a-n) / b} m - (1)
{Wherein M is independently one or two trivalent and / or tetravalent metal cations selected from Fe, Al, Ga, Ti or Zr, X is an anion, and a is a metal cation of M And b represents the valence of the anion, 1 ≦ n ≦ 7, n <2a, and 1 ≦ m ≦ 20. }
(4) The electromagnetic steel sheet not containing chromium according to ( 3 ), wherein the anion X in the chemical formula (1) is composed of one or more of halogen ions, sulfate ions, nitrate ions, and organic anions. Insulating coating agent.
(5) The pH of the dispersion of the colloidal compound of III) is in the range of 0.5 to 3, and contains 1 to 25% by mass of the metal element in terms of oxide of the metal, The insulating coating agent for electrical steel sheets containing no chromium according to any one of (1) to ( 4) , wherein the average particle diameter is in the range of 5 to 80 nm.
(6) The dispersion of the colloidal compound of III) further contains a compound containing one or more metal elements selected from Mn, Ni, Co, Cu or Sr ( The insulating coating agent for electrical steel sheets which does not contain chromium according to any one of 1) to ( 5 ).
(7) The phosphate of I) is an aqueous solution of phosphate, and the phosphate has a composition in which one or two kinds of primary phosphates of Al or Mg are combined, and the aqueous solution of the phosphate is The insulating coating agent for electrical steel sheets not containing chromium according to any one of (1) to ( 6 ), wherein the content of free phosphoric acid contained in is less than 15% by mass of the phosphate.
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の組成において、更に、Ｆｅの金属元素を含有するコロイド状化合物、具体的には、燐酸塩とコロイダルシリカからなるベース液に、Ｆｅを含有する化合物（但し、該化合物は水酸化物、酸化物、硫酸塩、燐酸塩、炭酸塩または珪酸塩から選ばれる）によりＳｉＯ2 ，ＺｒＯ 2 またはＴｉＯ2から選ばれる１種または２種以上の酸化物からなるコロイド物質を改質して得られるコロイド状化合物の分散液、または前記Ｆｅの金属元素を含有する化合物（但し、該化合物は水酸化物、酸化物、硫酸塩、燐酸塩、炭酸塩または珪酸塩から選ばれる）を含んでなるコロイド状化合物の分散液を添加することにより、焼付け後の被膜の耐蝕性が向上し、歪取り焼鈍時における耐焼き付き性の顕著な改善効果を得ることができる。 According to the present invention, in the composition of a tension coating containing no chromium compound based on phosphate-colloidal silica, a colloidal compound containing a metal element of Fe , specifically, phosphate and colloidal silica The base solution is selected from SiO 2 , ZrO 2, or TiO 2 with a compound containing Fe (provided that the compound is selected from hydroxide, oxide, sulfate, phosphate, carbonate or silicate) A dispersion of a colloidal compound obtained by modifying a colloidal substance composed of one or more oxides, or a compound containing the metal element of Fe (provided that the compound is a hydroxide, an oxide, The addition of a colloidal compound dispersion comprising a sulfate, phosphate, carbonate or silicate) improves the corrosion resistance of the coating after baking, Ri can be obtained a remarkable effect of improving galling resistance at the time of annealing.
このうち、特に、Ｆｅおよび／またはＡｌから選ばれる金属元素の水酸化物、酸化物、硫酸塩，燐酸塩，炭酸塩または珪酸塩から選ばれる化合物により、ＳｉＯ 2 ，ＺｒＯ 2 またはＴｉＯ2から選ばれる１種または２種以上の酸化物からなるコロイド物質を改質して得られるコロイド状化合物の分散液を前記ベース液に添加することにより、極めて優れた効果が発揮される。 Among these, a metal element selected from Fe and / or Al is selected from SiO 2 , ZrO 2 or TiO 2 depending on a compound selected from hydroxide, oxide, sulfate, phosphate, carbonate or silicate. By adding a colloidal compound dispersion obtained by modifying a colloidal material composed of one or more oxides to the base solution, an extremely excellent effect is exhibited.
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被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。 The inventors of the present invention have made efforts to make a chromium-free composition in a conventional tension-imparting insulating coating mainly composed of a phosphate simple substance and a phosphate, colloidal silica, and a chromium compound. In other words, it was a defect in the case of phosphate-free phosphate and phosphate and colloidal silica main component composition with the conventional composition, and the moisture absorption (stickiness and rust generation) after film baking treatment and seizure in strain relief annealing. The development of coating compositions to improve the coating properties and the reduction of coating tension due to coating porosity.
その結果、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の金属元素を含有するコロイド状化合物を、燐酸塩１００質量部に対し金属元素として０．１〜２０質量部添加することにより、従来の無クロム化組成が検討された張力付与型の電磁鋼板用絶縁被膜剤における諸問題を解決し、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被膜剤を提供し、またとその処理方法の完成に成功した。以下、詳細に説明する。 As a result, in a tension-imparting film component mainly composed of phosphate and colloidal silica, 0.1 to 20 parts by mass of a colloidal compound containing a metal element of Fe is added as a metal element to 100 parts by mass of phosphate. By solving the problems in the conventional insulating coating agent for tension-applied electrical steel sheet, for which the chromium-free composition has been studied, the corrosion resistance, annealing resistance, adhesion, slipperiness, insulation, etc. are excellent. We have provided an insulating coating agent with excellent magnetic and magnetostrictive properties, and have successfully completed the treatment method. 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.
本発明の絶縁被膜の最も特徴とするところは、燐酸塩１００質量部とコロイダルシリカ３５〜１００質量部に対し、Ｆｅの金属元素を含有するコロイド状化合物を、金属元素として０．１〜２０質量部を添加するところにある。 The most characteristic feature of the insulating coating of the present invention is that a colloidal compound containing a metal element of Fe is used in an amount of 0.1 to 20 mass as a metal element with respect to 100 mass parts of phosphate and 35 to 100 mass parts of colloidal silica. Part is to be added.
本発明者らは、絶縁被膜に対して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の金属元素を含有するコロイド状化合物が、被膜のポーラスな構造を充填するのに有効であり、また、遊離燐酸分と容易に結合して、燐酸分の安定化効果をもたらすことを発見した。特にＦｅ化合物は、極めて優れた効果を発揮する。 The present inventors have conducted extensive research and experiments on compounds that exhibit a Cr-substituting effect on insulating coatings. As a result, colloidal compounds containing a metallic element of Fe fill the porous structure of the coating. It has been found that it is effective in binding to free phosphoric acid, and has a stabilizing effect on phosphoric acid. In particular, the Fe compound exhibits an extremely excellent effect.
本発明で焼き付け処理後の吸湿性や歪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の酸化物、水酸化物，硫酸塩，炭酸塩、珪酸塩化合物が、溶液調製〜焼付け過程において分解し、コロイダルシリカ成分のみを添加した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生成することで、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、反応サイトの増加と濃度の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. Porous nest formed when Fe oxide, hydroxide, sulfate, carbonate, silicate compound uniformly dispersed in solution decomposes during solution preparation and baking process and only colloidal silica component is added The defective portion is filled. Moreover, it seems that producing a strong and stable phosphoric acid compound brings an effect of densifying the film, preventing hygroscopicity and improving the film tension. In particular, it is considered that the colloidal shape of ultrafine particles has a large improvement effect due to an increase in reaction sites and a uniform concentration.
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.
本発明においては、まず、その被膜組成に特徴がある。本発明においてはベース液として、燐酸塩１００質量部に対し、コロイダルシリカを３５〜１００質量部が用いられる。この燐酸塩としては、ＡｌまたはＭｇの第一燐酸塩が好ましい。リン酸塩に対するコロイダルシリカの割合は，被膜の緻密性や張力効果の発現に重要である。コロイダルシリカが３５質量部未満では張力効果が小さくなり、耐食性、絶縁性、密着性等の特性の他、焼鈍時の耐焼き付き性が低下する。一方、１００質量部超では被膜にクラックが発生して、耐食性悪化やベタツキ性が生じ、極端な場合、被膜張力の低下が生じる。 In the present invention, first, the film composition is characterized. In this invention, 35-100 mass parts of colloidal silica is used with respect to 100 mass parts of phosphates as a base liquid. As this phosphate, Al or Mg primary phosphate is preferable. The ratio of colloidal silica to phosphate is important for the denseness of the coating and the manifestation of the tension effect. If the colloidal silica is less than 35 parts by mass, the tension effect is reduced, and the seizure resistance during annealing is deteriorated in addition to the properties such as corrosion resistance, insulation and adhesion. On the other hand, if it exceeds 100 parts by mass, cracks occur in the coating, resulting in deterioration of corrosion resistance and stickiness, and in extreme cases, a decrease in coating tension occurs.
本発明の特徴は、上記ベース液に対し、Ｆｅの金属元素を含有するコロイド状化合物の分散液が金属元素として０．１〜２０質量部を添加されることにある。このコロイド状化合物は、それぞれの金属元素として、０．１質量部未満では、燐酸塩被膜中のポーラス構造を形成し易く、吸湿性や焼鈍時の焼き付性を抑える効果が十分でない。一方２０質量部超の場合、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、被膜の色調がやや不透明化する等の問題から制限される。 A feature of the present invention is that 0.1 to 20 parts by mass of a dispersion of a colloidal compound containing a metal element of Fe is added as a metal element to the base liquid. If the colloidal compound is less than 0.1 part by mass as each metal element, it is easy to form a porous structure in the phosphate coating, and the effect of suppressing hygroscopicity or seizure during annealing is not sufficient. On the other hand, in the case of more than 20 parts by mass, these improvement effects reach saturation and are limited by problems such as no further improvement, a slight decrease in film tension, and a slight color tone of the film.
この重要な役割を有するコロイド状化合物としては、平均粒子径が５〜８０ｎｍであって、次のａ）またはｂ）から選ばれるものが使用される。 As the colloidal compound having this important role, those having an average particle diameter of 5 to 80 nm and selected from the following a) or b) are used.
ａ） Ｆｅを含有する化合物（但し、該化合物は水酸化物、酸化物、硫酸塩、燐酸塩、炭酸塩または珪酸塩から選ばれる）によりＳｉＯ 2 ，ＺｒＯ 2 またはＴｉＯ2から選ばれる１種または２種以上の酸化物からなるコロイド物質を改質して得られるコロイド状化合物、
ｂ） または前記Ｆｅの金属元素を含有する化合物（但し、該化合物は水酸化物、酸化物、硫酸塩、燐酸塩、炭酸塩または珪酸塩から選ばれる）を含んでなるコロイド状化合物
上記ａ）またはｂ）のコロイド状化合物は、該コロイド状化合物の分散液として前記ベース液に添加される。該コロイド状化合物の分散液について、例えば、コロイダルシリカの様なポリシロキサン構造を有する微粒子の溶液として調製され、前記燐酸塩およびコロイドシリカに添加されることにより、電磁鋼板用絶縁被膜剤の溶液安定性や前記燐酸塩の安定化、被膜の緻密性を高めることができる。
a) a compound containing Fe (provided that the compound is selected from hydroxide, oxide, sulfate, phosphate, carbonate or silicate) and one or more selected from SiO 2 , ZrO 2 or TiO 2 A colloidal compound obtained by modifying a colloidal substance composed of two or more oxides,
b) or a compound containing a metal element of Fe (wherein the compound is selected from hydroxide, oxide, sulfate, phosphate, carbonate or silicate) a) Alternatively, the colloidal compound of b) is added to the base solution as a dispersion of the colloidal compound. About the dispersion of the colloidal compound, for example, it is prepared as a solution of fine particles having a polysiloxane structure such as colloidal silica, and is added to the phosphate and colloidal silica to thereby stabilize the solution of the insulating coating agent for electrical steel sheets. Property, stabilization of the phosphate, and denseness of the coating can be improved.
コロイド状化合物の平均粒子径としては、粒子径が８０ｎｍ以下であることが重要で，好ましくは１５ｎｍ以下の超微粒子のものが良い。これは、反応面積が増加して，ベース液成分のみの場合に被膜に生じるポーラスな被膜構造への充填作用、および遊離燐酸の安定化に対して優れた効果が得られ、格段に優れた改善効果が得られる。粒径の下限は必ずしも限定されるものではないが、５ｎｍ未満でコロイド状とすることは困難なため制限される。 As the average particle size of the colloidal compound, it is important that the particle size is 80 nm or less, preferably ultrafine particles of 15 nm or less. This increases the reaction area, and has an excellent effect on filling the porous film structure that occurs in the film when only the base liquid component is present, and the stabilization of free phosphoric acid. An effect is obtained. The lower limit of the particle size is not necessarily limited, but it is limited because it is difficult to form a colloidal shape below 5 nm.
Ｆｅの金属元素を含有するコロイド状化合物については、実質的にシロキサン構造を有するゾル溶液を用いることにより、分散性、安定性に優れた溶液が得られる。これらのコロイド状化合物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、均一な被膜構造が得られ，焼付け処理時に、前記、充填作用や遊離燐酸の安定化作用に対し、極めて優れた効果を発揮する。 About the colloidal compound containing the metallic element of Fe, the solution excellent in the dispersibility and stability is obtained by using the sol solution which has a siloxane structure substantially. When these colloidal compounds are blended into the base solution, a very uniform dispersion is produced, so that a uniform coating structure is obtained. During the baking process, the above-mentioned filling action and free phosphoric acid stabilization action are extremely difficult. Exhibits excellent effects.
コロイド状化合物としては、ａ） Ｆｅを含有する化合物（但し、該化合物は水酸化物、酸化物、硫酸塩、燐酸塩、炭酸塩または珪酸塩から選ばれる）によりＳｉＯ 2 ，ＺｒＯ 2 またはＴｉＯ2から選ばれる１種または２種以上の酸化物からなるコロイド物質を改質して得られるコロイド状化合物、または、ｂ） 前記Ｆｅの金属元素を含有する化合物（但し、該化合物は水酸化物、酸化物、硫酸塩、燐酸塩、炭酸塩または珪酸塩から選ばれる）を含んでなるコロイド状化合物があり、どちらにおいても良好な作用効果が得られる。 Colloidal compounds include: a) Fe- containing compounds (wherein the compounds are selected from hydroxides, oxides, sulfates, phosphates, carbonates or silicates), SiO 2 , ZrO 2 or TiO 2 A colloidal compound obtained by modifying a colloidal substance composed of one or more oxides selected from the above, or b) a compound containing a metal element of Fe (provided that the compound is a hydroxide, There are colloidal compounds comprising oxides, sulfates, phosphates, carbonates or silicates, both of which have good effects.
より好適には、コロイド状化合物として、Ｆｅを含有する化合物（但し、該化合物は水酸化物、酸化物、硫酸塩、燐酸塩、炭酸塩または珪酸塩から選ばれる）によりＳｉＯ 2 ，ＺｒＯ 2 またはＴｉＯ2から選ばれる１種または２種以上の酸化物からなるコロイド物質を改質して得られるコロイド状化合物を使用することが好ましい。これらのコロイド状化合物を添加した場合、被膜性能を損なうことなく、絶縁被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、被膜の緻密化や遊離燐酸の固定効果をもたらすことができる。 More preferably, as the colloidal compound, a compound containing Fe (provided that the compound is selected from hydroxide, oxide, sulfate, phosphate, carbonate or silicate) is used as SiO 2 , ZrO 2 or It is preferable to use a colloidal compound obtained by modifying a colloidal substance composed of one or more oxides selected from TiO 2 . When these colloidal compounds are added, the filling performance is brought about in the insulating film baking process without impairing the film performance, and the film is densified and free phosphoric acid is fixed in the baking process and the strain relief annealing process. Can do.
実験の結果では、上記コロイド状化合物の中で、ＳｉＯ2ゾル，Ａｌ2Ｏ3ゾル等を前記金属元素（Ｆｅ）を含有する化合物で改質してなるコロイド状化合物を添加した場合が、液の安定性、作業性等が優れ、また被膜特性の向上効果が大きいことがわかった。これは、この様な金属元素を含有するコロイド状化合物が遊離燐酸との反応性に優れ、また被膜中に容易に充填され、被膜表面を緻密化するためと推定される。 As a result of the experiment, a case where a colloidal compound obtained by modifying SiO 2 sol, Al 2 O 3 sol, etc. with a compound containing the metal element ( Fe) among the above colloidal compounds is added. It was found that the stability and workability of the film were excellent, and the effect of improving the film properties was great. This is presumed to be because the colloidal compound containing such a metal element is excellent in reactivity with free phosphoric acid, and is easily filled in the coating, thereby densifying the coating surface.
また、本発明におけるコロイド状化合物として、最も顕著な効果を示したのは、酸化物、または水酸化物を含有する場合であり、特に、Ｆｅの酸化物、またはＦｅの水酸化物によりＳｉＯ 2 ，ＺｒＯ 2 またはＴｉＯ2から選ばれる１種または２種以上の酸化物からなるコロイド物質を改質して得られるコロイド状化合物により優れた被膜性能が得られた。 In addition, the colloidal compound in the present invention has the most remarkable effect when it contains an oxide or hydroxide. In particular, it is SiO 2 due to the oxide of Fe or the hydroxide of Fe. Excellent coating performance was obtained with a colloidal compound obtained by modifying a colloidal material composed of one or more oxides selected from ZrO 2 and TiO 2 .
前記コロイド状化合物が、シロキサン結合を有するシリカ系粒子の表面に塩基性金属化合物が反応してなる改質シリカ系ゾルを含む場合、該塩基性金属化合物としては、下記式（１）で表される塩基性金属化合物が用いられる。 When the colloidal compound includes a modified silica-based sol obtained by reacting a basic metal compound on the surface of silica-based particles having a siloxane bond, the basic metal compound is represented by the following formula (1). Basic metal compounds are used.
｛Ｍ2（ＯＨ）nＸ(2a-n)/b｝m −（１）
式中、Ｍはそれぞれ独立に、Ｆｅ，Ａｌ，Ｇａ，ＴｉまたはＺｒから選ばれる一種または二種の３価及び／または４価の金属カチオン、Ｘはアニオンであり、ａはＭの金属カチオンの価数、ｂは該アニオンの価数を示し、１≦ｎ≦７、ｎ＜２ａであり、１≦ｍ≦２０である。上記のとおりこの塩基性化合物は同一化合物においてＭが１種または２種の元素の金属カチオンを含んでいてもよい。なかでもＦｅ3+を含む化合物は、好適に用いることが出来る。Ｆｅ3+を含む２種以上の金属カチオンからなる場合の組み合わせとしては、Ａｌ−Ｆｅ，Ｔｉ−Ｆｅ，Ｚｒ−Ｆｅ等があげられる。
{M 2 (OH) n X (2a-n) / b} m - (1)
In the formula, each M is independently one or two trivalent and / or tetravalent metal cations selected from Fe, Al, Ga, Ti, or Zr, X is an anion, and a is an M metal cation. The valence, b, represents the valence of the anion, 1 ≦ n ≦ 7, n <2a, and 1 ≦ m ≦ 20. As described above, this basic compound may contain a metal cation of one or two elements of M in the same compound. Among these, a compound containing Fe 3+ can be preferably used. Examples of the combination of two or more metal cations containing Fe 3+ include Al—Fe, Ti—Fe, and Zr—Fe.
Ｘはアニオンであり、例えば、ハロゲンイオン、硫酸イオン、硝酸イオン、有機アニオン等があげられる。具体的には、｛Ａｌ2（ＯＨ）1（ＳＯ4）2.5｝4，｛Ｆｅ2（ＯＨ）1（ＳＯ4）2.5｝4，Ｚｒ2（ＯＨ）1（ＳＯ4）3.5｝4，Ａｌ2（ＯＨ）2（ＳＯ4）2｝4，｛Ｆｅ2（ＯＨ）2（ＳＯ4）2｝4，｛Ｆｅ2（ＯＨ）1（ＳＯ4）2.5｝6，｛Ｆｅ2-XＡｌx（ＯＨ）1（ＳＯ4）2.5｝4 （０＜ｘ＜２）等の他、前記（ＳＯ4）を他の前記アニオンに置換した化合物などがあげられる。 X is an anion, and examples thereof include a halogen ion, a sulfate ion, a nitrate ion, and an organic anion. Specifically, {Al 2 (OH) 1 (SO 4 ) 2.5 } 4 , {Fe 2 (OH) 1 (SO 4 ) 2.5 } 4 , Zr 2 (OH) 1 (SO 4 ) 3.5 } 4 , Al 2 (OH) 2 (SO 4 ) 2 } 4 , {Fe 2 (OH) 2 (SO 4 ) 2 } 4 , {Fe 2 (OH) 1 (SO 4 ) 2.5 } 6 , {Fe 2 -X Al x In addition to (OH) 1 (SO 4 ) 2.5 } 4 (0 <x <2), etc., compounds in which (SO 4 ) is substituted with other anions are exemplified.
また、式中、ｍは１≦ｍ≦２０、好ましくは２≦ｍ≦１０の範囲にある。ｍが２０を超えるとシリカ系粒子表面への結合が起こりにくくなり、また、表面電荷が付与できないために得られる改質シリカ系ゾルが不安定であったり、凝集することがある。 In the formula, m is in the range of 1 ≦ m ≦ 20, preferably 2 ≦ m ≦ 10. When m exceeds 20, bonding to the surface of the silica-based particles becomes difficult to occur, and the modified silica-based sol obtained because the surface charge cannot be imparted may be unstable or aggregate.
Ｆｅを含有する化合物（但し、該化合物は水酸化物、酸化物、硫酸塩、燐酸塩、炭酸塩または珪酸塩から選ばれる）によりＳｉＯ 2 ，ＺｒＯ 2 またはＴｉＯ2から選ばれる１種または２種以上の酸化物からなるコロイド物質を改質して得られるコロイド状化合物の調製方法としては、酸性金属塩の水溶液、例えば、ポリ硫酸鉄水溶液の中に、粒径５〜８０ｎｍのコロイダルシリカを徐々に攪拌しながら添加することにより、Ｆｅを含有するコロイド状化合物を調製する方法を挙げることができる。 One or two selected from SiO 2 , ZrO 2 or TiO 2 by a compound containing Fe (provided that the compound is selected from hydroxide, oxide, sulfate, phosphate, carbonate or silicate) As a method for preparing a colloidal compound obtained by modifying a colloidal substance composed of the above oxide, colloidal silica having a particle diameter of 5 to 80 nm is gradually added to an aqueous solution of an acidic metal salt, for example, an aqueous solution of polyiron sulfate. A method of preparing a colloidal compound containing Fe can be mentioned by adding to the mixture while stirring.
前記コロイド物質とＦｅを含有する化合物の混合比は、コロイド物質の固形分１．０質量部に対し、これらの金属を含有する化合物を金属酸化物に換算して０．０１〜７．０質量部の範囲が良く、特に、１．０〜４．０質量部の範囲が好ましい。 The mixing ratio of the colloidal substance and the compound containing Fe is 0.01 to 7.0 masses when the compound containing these metals is converted into a metal oxide with respect to 1.0 mass part of the solid content of the colloidal substance. The range of parts is good, and the range of 1.0 to 4.0 parts by mass is particularly preferable.
また、前記コロイダル物質と前記Ｆｅを含有する化合物を混合し、反応させた得られたコロイド状化合物については、固形分濃度（酸化物換算）は、１〜２５質量％の範囲の分散液であることが望ましく、特に２〜２０質量％の範囲の分散液であることが好ましい。このようなコロイド状化合物の分散液のｐＨは０．５〜３の範囲とするのが好ましく、この範囲外では母液の安定性を損ね、ゲル化が生じる場合があり、また焼付け後の被膜の外観に影響する。 Moreover, about the colloidal compound obtained by mixing the said colloidal substance and the said compound containing Fe and making it react, solid content concentration (oxide conversion) is a dispersion liquid of the range of 1-25 mass%. It is desirable that the dispersion be in the range of 2 to 20% by mass. The pH of such a colloidal compound dispersion is preferably in the range of 0.5 to 3. Outside this range, the stability of the mother liquor may be impaired, and gelation may occur. Affects appearance.
また、Ｆｅの金属元素を含有するコロイド状化合物の分散液にさらにＭｎ，Ｎｉ，Ｃｏ，Ｃｕ，またはＳｒから選ばれる一種または二種以上の金属元素を含有する化合物を配合しても構わない。これらを添加することで、耐食性や歪取り焼鈍時の耐焼き付き性が向上する。 In addition, a compound containing one or more metal elements selected from Mn, Ni, Co, Cu, or Sr may be added to the dispersion of the colloidal compound containing the Fe metal element. By adding these, corrosion resistance and seizure resistance during strain relief annealing are improved.
ベ−ス液に使用する燐酸塩中の遊離燐酸は固形分割合で１５％未満であることが重要である。ここで遊離燐酸とは、Ａｌ2Ｏ3，ＭｇＯ，Ａｌ（ＯＨ）3，Ｍｇ（ＯＨ）2等を燐酸と混合してＡｌ（Ｈ2ＰＯ4）3，Ｍｇ（Ｈ2ＰＯ4）2を生成した後の燐酸塩溶液中の未反応Ｈ3ＰＯ4である。遊離燐酸量が１５％超になると，コロイダルシリカや他のコロイダルシリカを混合した溶液の安定性が低下し、また焼き付け後の被膜表面平滑度の減退や被膜透明度を減退させるため制限される。好ましくは１０％未満とすることで、上記のような問題が生じにくく、優れた被膜特性と作業性が得られる。 It is important that the free phosphoric acid in the phosphate used in the base solution is less than 15% by solids. Here, free phosphoric acid refers to Al (H 2 PO 4 ) 3 , Mg (H 2 PO 4 ) 2 by mixing Al 2 O 3 , MgO, Al (OH) 3 , Mg (OH) 2, etc. with phosphoric acid. Unreacted H 3 PO 4 in the phosphate solution after formation. When the amount of free phosphoric acid exceeds 15%, the stability of the solution mixed with colloidal silica or other colloidal silica is lowered, and the surface smoothness after baking and the coating transparency are reduced. When the content is preferably less than 10%, the above-described problems hardly occur, and excellent film characteristics and workability can be obtained.
本発明の電磁鋼板用絶縁被膜剤は、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、鋼板へ塗布後、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 insulating coating agent for electrical steel sheets according to the present invention is subjected to baking treatment at 350 ° C. or higher after being applied to the steel sheet 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 .
絶縁被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，Ａｌ，Ｇａ，ＴｉまたはＺｒの酸化物，水酸化物、硫酸塩，炭酸塩、珪酸塩化合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。 The application baking condition of the insulating coating 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. When the baking temperature is lower than 350 ° C., the reaction with the oxide, hydroxide, sulfate, carbonate or silicate compound of Fe, Al, Ga, Ti or Zr added with the primary phosphate is sufficient. This is because the stickiness is reduced.
磁気特性の改善のため、製品にレーザー等の磁区細分化処理を行った後に被膜形成する場合には、焼き付け温度は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。 In order to improve the magnetic properties, when the film is formed after the magnetic domain fragmentation treatment such as laser is applied to the product, the baking temperature is preferably 350 to 450 ° C. 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.
この際の焼付け処理時の雰囲気としては、Ｎ2或いはＨ2＋Ｎ2雰囲気、好ましくはＨ2＝１％以上で露点が３５℃以下の雰囲気とすると、表面外観の優れた絶縁被膜が形成される。これは添加剤のＦｅ，Ａｌ等の酸化物、水酸化物、硫酸塩、炭酸塩、珪酸塩化合物の溶液中成分が安定な燐酸化合物を形成できることの他に、酸化反応が生じると化合物の形態が変化し、安定な燐酸塩形成反応を阻害するので、これを抑制するような低酸化性雰囲気が好ましいものと考えられる。 In this case, the atmosphere during the baking treatment is an N 2 or H 2 + N 2 atmosphere, preferably an atmosphere with H 2 = 1% or more and a dew point of 35 ° C. or less, whereby an insulating film having an excellent surface appearance is formed. . In addition to being able to form stable phosphoric acid compounds in solution of oxides such as Fe and Al, hydroxides, sulfates, carbonates, and silicate compounds as additives, the form of compounds when oxidation reactions occur Changes and inhibits a stable phosphate formation reaction, so a low oxidizing atmosphere that suppresses this is considered preferable.
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.
最終仕上げ焼鈍を行った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℃×４Ｈｒの歪取り焼鈍を行った。その後、２％−Ｈ2ＳＯ4水溶液中で８５℃、１５秒間の軽酸洗を行って試験用サンプルを調製した。この鋼板表面に、表１に示すように、燐酸塩として固形分５０％の第一燐酸アルミニウム水溶液（〔表１〕、〔表３〕、〔表５〕においては「５０％第一燐酸Ａｌ」と表記する。）、およびコロイダルシリカとして商品名「カタロイド−ＳＮ」（触媒化成工業株式会社製、酸性ゾル、粒子径１１ｎｍ、シリカ濃度２０％）からなるベース液に、更に金属元素を含有するコロイド状化合物の分散液（添加剤）として、３０℃のポリ硫酸鉄水溶液（Ｆｅ2Ｏ3に換算した固形分濃度１５％）の中に商品名「カタロイド−ＳＮ」を、Ｆｅ2Ｏ3／ＳｉＯ2質量比が１．８となるように３０分かけて添加し、３０℃×６０分で反応させて得られた、Ｆｅを含有するコロイド状化合物の分散液（Ｆｅ2Ｏ3／ＳｉＯ2質量比：１．８）を、表１に示す添加量にて配合し、電磁鋼板用絶縁被膜剤を調製した。なお、平均粒子径の測定は、動的光散乱法による粒子径分布測定装置（Ｐａｒｔｉｃｌｅ Ｓｉｚｉｎｇ Ｓｙｓｔｅｍｓ社製：ＮＩＣＯＭＰ ＭＯＤＥＬ３８０）を使用した。 A sample was cut out from a 0.23 mm thick high magnetic flux density grain-oriented electrical steel sheet coil having a glass coating subjected to final finish annealing, and after rinsing with water, 850 ° C. × 4 Hr strain relief annealing was performed. Thereafter, a light pickling was performed in a 2% -H 2 SO 4 aqueous solution at 85 ° C. for 15 seconds to prepare a test sample. As shown in Table 1, a primary aluminum phosphate aqueous solution having a solid content of 50% (refer to “50% primary phosphate Al” in [Table 1], [Table 3], and [Table 5]) is formed on the surface of the steel sheet. And a colloidal silica containing a trade name “Cataloid-SN” (catalyst chemical industry Co., Ltd., acidic sol, particle size 11 nm, silica concentration 20%) and a colloid further containing a metal element. The product name “Cataroid-SN” was added to a 30 ° C. polyiron sulfate aqueous solution (solid content concentration of 15% converted to Fe 2 O 3 ) as Fe 2 O 3 / SiO. A dispersion of Fe-containing colloidal compound (Fe 2 O 3 / SiO 2 mass) obtained by adding over 30 minutes so that the 2 mass ratio becomes 1.8 and reacting at 30 ° C. × 60 minutes. Ratio: 1.8) as shown in Table 1 Blended with, to prepare a electromagnetic steel sheet insulating coating agent. In addition, the average particle diameter was measured using a particle size distribution measuring apparatus (manufactured by Particle Sizing Systems: NICOMP MODEL380) by a dynamic light scattering method.
この電磁鋼板用絶縁被膜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。 This insulation coating agent for electrical steel sheets was applied using a coating roll so that the mass after drying and baking was 5 g / m 2, and a baking process was performed at 850 ° C. for 30 seconds. 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、ベース液にＦｅを含有するコロイド状化合物の分散液を添加した場合（実施例１の本発明１〜５）は、同分散液を添加しない場合（実施例１における比較例１）に比較して、焼き付け後被膜の吸湿性がＣｒ化合物添加の場合と同様に顕著に改善され、外観が良く、耐蝕性が顕著に改善された。又、遊離燐酸分によると考えられる、歪取り焼鈍における耐焼付き性も顕著に改善され、被膜張力も従来のクロム化合物を含有する場合（実施例１における比較例４）に比し遜色のない被膜特性が得られた。又、添加量が少ない場合には、ベタツキ性防止、耐焼き付き姓防止効果が弱く、多過ぎる場合には、外観、被膜張力のほか液安定性等の面で劣る結果となった。 As a result of this test, when the dispersion liquid of the colloidal compound containing Fe was added to the base liquid (present inventions 1 to 5 in Example 1), the dispersion liquid was not added (Comparative Example 1 in Example 1). ), The hygroscopicity of the coating after baking was remarkably improved as in the case of adding the Cr compound, the appearance was good, and the corrosion resistance was remarkably improved. In addition, the seizure resistance in strain relief annealing, which is considered to be due to the free phosphoric acid content, is remarkably improved, and the coating tension is comparable to the case where the coating tension contains a conventional chromium compound (Comparative Example 4 in Example 1). Characteristics were obtained. Further, when the addition amount is small, the effect of preventing stickiness and anti-seizure resistance is weak, and when it is too much, the result is inferior in terms of appearance, film tension and liquid stability.
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に示すように複合燐酸塩（第一燐酸アルミニウムと第一燐酸マグネシウムからなる。）と粒子径を変更した各コロイダルシリカからなるベース液に金属元素を含有するコロイド状化合物の分散液（添加剤）として商品名「カタロイド ＳＡ−３００」（触媒化成工業株式会社製、アルカリ性ゾル、粒子径９ｎｍ、シリカ濃度２０％）を脱アルカリしたものを、Ｆｅ2Ｏ3／ＳｉＯ2質量比が２．０となるように、２５℃のポリ硫酸鉄水溶液（Ｆｅ2Ｏ3に換算した固形分濃度７．５％）へ６０分かけて添加した後、５０℃×６０分反応させて得られたＦｅを含有するコロイド状化合物の分散液（Ｆｅ2Ｏ3／ＳｉＯ2質量比：２．０）を表３に示す添加量にて配合し、電磁鋼板用絶縁被膜剤を調製した。 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, washed with water, and subjected to 850 ° C. × 4 Hr strain relief annealing. Thereafter, light pickling at 75 ° C. for 15 seconds was performed in a 2% -H 2 SO 4 aqueous solution. As shown in Table 3, a colloidal compound containing a metal element in a base solution composed of a composite phosphate (comprising primary aluminum phosphate and primary magnesium phosphate) and colloidal silica having a changed particle size is used. Fe 2 O 3 / SiO 2 mass obtained by dealkalizing the product name “Cataloid SA-300” (manufactured by Catalyst Kasei Kogyo Co., Ltd., alkaline sol, particle size 9 nm, silica concentration 20%) as a dispersion (additive) After adding for 60 minutes to 25 ° C polyiron sulfate aqueous solution (solid content concentration of 7.5% converted to Fe 2 O 3 ) so that the ratio becomes 2.0, the mixture is reacted at 50 ° C for 60 minutes. The obtained colloidal compound dispersion containing Fe (Fe 2 O 3 / SiO 2 mass ratio: 2.0) was blended in the addition amount shown in Table 3 to prepare an insulating coating agent for electrical steel sheets.
この溶液を実施例１と同様にコーテイングロールにより、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。 This solution was applied by a coating roll in the same manner as in Example 1 so that the mass after drying and baking was 5.0 g / m 2 and baked at 850 ° C. for 30 seconds. 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における比較例１の場合と同様に、Ｆｅを含有するコロイド状化合物の分散液を含まない電磁鋼板用絶縁被膜剤を用いて実施例１と同様に試験を行なった場合（実施例２における比較例１）、耐蝕性と耐焼鈍性が非常に劣る結果であった。一方、Ｆｅを含有するコロイド状化合物の分散液をベース液に添加してなる電磁鋼板用絶縁被膜剤を使用した場合（実施例２における本発明１〜５）においては、本発明１，２，３のようにベースコロイダルシリカとして粒子径の小さいものを使用した場合、添加効果が非常に大きく、従来のＣｒ化合物添加の場合と同等以上の耐焼付き性、耐蝕性、被膜張力の改善効果が得られた。また、本発明４、５のようにベ−スコロイダルシリカの粒子径が大きいものを使用した場合でも、改善効果は見られるものの、その効果の程度は、粒子径が大きくなるにつれて低下する傾向が見られた。 As a result of this test, the test was conducted in the same manner as in Example 1 using an insulating coating agent for electrical steel sheets that did not contain a dispersion of a colloidal compound containing Fe, as in Comparative Example 1 in Example 1. In the case (Comparative Example 1 in Example 2), the corrosion resistance and the annealing resistance were very poor. On the other hand, in the case of using an insulating coating agent for an electrical steel sheet obtained by adding a dispersion of a colloidal compound containing Fe to a base solution (present inventions 1 to 5 in Example 2), the present invention 1, 2, When the base colloidal silica with a small particle size is used as shown in No. 3, the effect of addition is very large, and the seizure resistance, corrosion resistance, and film tension improvement effects equal to or higher than those of the conventional Cr compound addition are obtained. It was. In addition, even when using particles having a large particle size of bescoloidal silica as in the present inventions 4 and 5, the improvement effect is seen, but the degree of the effect tends to decrease as the particle size increases. It was seen.
実施例１、２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５に示すように複合燐酸塩（実施例２で用いたものと同様）に粒子径９ｎｍのコロイダルシリカを添加したベース液に、金属元素を含有するコロイド状化合物の分散液（添加剤）として、実施例２において使用したのと同様に、粒子径を５〜１００ｎｍの範囲で種々変更したアルカリ性コロイド（アルカリ性ゾル：粒子径５〜１００ｎｍ、２０％濃度）を脱アルカリしたものを、Ｆｅ2Ｏ3／ＳｉＯ2質量比が２．０となるように、２５℃のポリ硫酸鉄水溶液（Ｆｅ2Ｏ3に換算した固形分濃度７．５％）へ６０分かけて添加した後、５０℃−６０分反応させて得られたＦｅを含有するコロイド状化合物の分散液を表５に示す添加量にて配合し、電磁鋼板用絶縁被膜剤を調製した。 A sample was cut out from a 0.23 mm thick high magnetic flux density grain-oriented electrical steel sheet coil that had been subjected to final finish annealing in the same manner as in Examples 1 and 2, and after rinsing with water, 850 ° C. × 4 Hr strain relief annealing was performed. Thereafter, light pickling at 75 ° C. for 15 seconds was performed in a 2% -H 2 SO 4 aqueous solution. As shown in Table 5, a dispersion of a colloidal compound containing a metal element in a base solution obtained by adding colloidal silica having a particle diameter of 9 nm to a composite phosphate (similar to that used in Example 2) as shown in Table 5 As the additive), as used in Example 2, an alkali colloid (alkaline sol: particle diameter 5 to 100 nm, 20% concentration) with various changes in the particle diameter in the range of 5 to 100 nm is dealkalized. After adding to an iron polysulfate aqueous solution (solid content concentration of 7.5% converted to Fe 2 O 3 ) at 25 ° C. over 60 minutes so that the Fe 2 O 3 / SiO 2 mass ratio becomes 2.0 A dispersion of a colloidal compound containing Fe obtained by reacting at 50 ° C. for 60 minutes was blended in an addition amount shown in Table 5 to prepare an insulating coating agent for an electrical steel sheet.
この溶液を実施例１と同様にコーテイングロールにより、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６に示す。 This solution was applied by a coating roll in the same manner as in Example 1 so that the mass after drying and baking was 5.0 g / m 2 and baked at 850 ° C. for 30 seconds. Thereafter, a sample was cut out from the product plate, and the film characteristics were investigated. The results are shown in Table 6.
この試験の結果、実施例１における比較例１や実施例２における比較例１の場合と同様に、Ｆｅを含有するコロイド状化合物の分散液を含まない電磁鋼板用絶縁被膜剤を用いて実施例１と同様に試験を行なった場合（実施例３における比較例１）、耐蝕性と耐焼鈍性が非常に劣る結果であった。
一方、Ｆｅを含有するコロイド状化合物の分散液ベース液に添加してなる電磁鋼板用絶縁被膜剤を使用した場合（実施例３における本発明１〜５）においては、本発明１、２、３のようにＦｅを含有するコロイド状化合物として、粒子径の小さいものを使用した場合には添加の効果がより大きく、従来のＣｒ化合物添加の場合と同等以上の耐焼付き性、耐蝕性、被膜張力の改善効果が得られた。また、本発明４，５のようにＦｅを含有するコロイド状化合物の粒子径が大きいものを添加した場合、改善効果はかなり見られるものの、粒子径が小さい場合に比較して、効果の程度は粒子径が大きくなるほど低下する傾向が見られた。
As a result of this test, in the same manner as in Comparative Example 1 in Example 1 and Comparative Example 1 in Example 2, an example using an insulating coating agent for an electrical steel sheet not containing a dispersion of a colloidal compound containing Fe was used. When the test was conducted in the same manner as in Example 1 (Comparative Example 1 in Example 3), the corrosion resistance and the annealing resistance were very poor.
On the other hand, in the case of using an insulating coating agent for an electrical steel sheet added to a dispersion base solution of a colloidal compound containing Fe (present inventions 1 to 5 in Example 3), the present invention 1, 2, 3 When using a colloidal compound containing Fe, such as those with a small particle size, the effect of addition is greater, and seizure resistance, corrosion resistance, and film tension equal to or higher than those of conventional Cr compound addition. The improvement effect was obtained. In addition, when the colloidal compound containing Fe having a large particle size is added as in the present inventions 4 and 5, the improvement effect is considerably seen, but the degree of the effect is less than that when the particle size is small. A tendency to decrease as the particle size increased was observed.
Claims (7)
Ｉ） 燐酸塩 １００質量部
II） コロイダルシリカをＳｉＯ2固形分に換算して３５〜１００質量部
III ） Ｆｅの金属元素を含有するコロイド状化合物の分散液を、該金属元素に換算して０．１〜２０質量部、かつ、前記コロイド状化合物の平均粒子径が５〜８０ｎｍであって、次のａ）またはｂ）から選ばれるもの
ａ）Ｆｅを含有する化合物（但し、該化合物は水酸化物、酸化物、硫酸塩，燐酸塩，炭酸塩または珪酸塩から選ばれる）によりＳｉＯ 2 ，ＺｒＯ 2 またはＴｉＯ 2 から選ばれる１種または２種以上の酸化物からなるコロイド物質を改質して得られるコロイド状化合物
ｂ）Ｆｅの金属元素を含有する化合物（但し、該化合物は水酸化物、酸化物、硫酸塩、燐酸塩、炭酸塩または珪酸塩から選ばれる）を含んでなるコロイド状化合物 An insulating coating agent for electrical steel sheets that does not contain chromium, comprising the following I), II), and III):
I) Phosphate 100 parts by mass
II) 35 to 100 parts by mass of colloidal silica in terms of SiO 2 solid content
III) A dispersion of a colloidal compound containing a metal element of Fe is 0.1 to 20 parts by mass in terms of the metal element , and the average particle size of the colloidal compound is 5 to 80 nm, Selected from the following a) or b)
compounds containing a) Fe (with the proviso that the compound is a hydroxide, oxide, sulfate, phosphate, selected from carbonate or silicate) by one selected from SiO 2, ZrO 2 or TiO 2 or Colloidal compounds obtained by modifying colloidal materials composed of two or more oxides
b) a colloidal compound comprising a compound containing a metal element of Fe (wherein the compound is selected from hydroxide, oxide, sulfate, phosphate, carbonate or silicate)
｛Ｍ2（ＯＨ）nＸ(2a-n)/b｝m −（１）
｛式中、Ｍはそれぞれ独立に、Ｆｅ，Ａｌ，Ｇａ，ＴｉまたはＺｒから選ばれる一種または二種の３価及び／または４価の金属カチオン、Ｘはアニオンであり、ａはＭの金属カチオンの価数、ｂは該アニオンの価数を示し、１≦ｎ≦７，ｎ＜２ａであり、１≦ｍ≦２０である。｝ The colloidal compound of III) includes a modified silica-based sol formed by a reaction of a basic metal compound represented by the following chemical formula (1) on the surface of silica-based particles having a siloxane bond. Item 3. An insulating coating agent for electrical steel sheets that does not contain chromium according to any one of Items 1 and 2 .
{M 2 (OH) n X (2a-n) / b} m - (1)
{Wherein M is independently one or two trivalent and / or tetravalent metal cations selected from Fe, Al, Ga, Ti or Zr, X is an anion, and a is a metal cation of M And b represents the valence of the anion, 1 ≦ n ≦ 7, n <2a, and 1 ≦ m ≦ 20. }
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