CN103732794A - 具有绝缘被膜的电磁钢板 - Google Patents
具有绝缘被膜的电磁钢板 Download PDFInfo
- Publication number
- CN103732794A CN103732794A CN201280039457.2A CN201280039457A CN103732794A CN 103732794 A CN103732794 A CN 103732794A CN 201280039457 A CN201280039457 A CN 201280039457A CN 103732794 A CN103732794 A CN 103732794A
- Authority
- CN
- China
- Prior art keywords
- steel plate
- surface treatment
- electro
- treatment agent
- magnetic steel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 79
- 239000010959 steel Substances 0.000 title claims abstract description 79
- 239000011248 coating agent Substances 0.000 title abstract description 14
- 238000000576 coating method Methods 0.000 title abstract description 14
- 239000012756 surface treatment agent Substances 0.000 claims abstract description 50
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 27
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 57
- 238000009413 insulation Methods 0.000 claims description 44
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 34
- 239000000377 silicon dioxide Substances 0.000 claims description 28
- 235000012239 silicon dioxide Nutrition 0.000 claims description 26
- 229960001866 silicon dioxide Drugs 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 16
- 229910000077 silane Inorganic materials 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 11
- 239000000314 lubricant Substances 0.000 claims description 9
- 238000003892 spreading Methods 0.000 claims description 2
- 238000000137 annealing Methods 0.000 abstract description 27
- -1 chrome compound Chemical class 0.000 abstract description 14
- 125000001424 substituent group Chemical group 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 29
- 230000006978 adaptation Effects 0.000 description 19
- 230000003628 erosive effect Effects 0.000 description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 229910052742 iron Inorganic materials 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 7
- 239000011651 chromium Substances 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 238000004381 surface treatment Methods 0.000 description 6
- 239000001993 wax Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 238000003466 welding Methods 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 239000002775 capsule Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 230000004520 agglutination Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000007761 roller coating Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000003352 sequestering agent Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 150000003755 zirconium compounds Chemical class 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101100134922 Gallus gallus COR5 gene Proteins 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MKYLOMHWHWEFCT-UHFFFAOYSA-N Manthidine Natural products C1C2=CC=3OCOC=3C=C2C2C3=CC(OC)C(O)CC3N1C2 MKYLOMHWHWEFCT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- SNFRINMTRPQQLE-JQWAAABSSA-N Montanin Chemical compound O[C@H]([C@@]1(CO)O[C@H]1[C@H]1[C@H]2O3)[C@]4(O)C(=O)C(C)=C[C@H]4[C@]11OC3(CCCCCCCCCCC)O[C@@]2(C(C)=C)C[C@H]1C SNFRINMTRPQQLE-JQWAAABSSA-N 0.000 description 1
- SNFRINMTRPQQLE-OFGNMXNXSA-N Montanin Natural products O=C1[C@@]2(O)[C@@H](O)[C@@]3(CO)O[C@H]3[C@@H]3[C@H]4[C@@]5(C(=C)C)O[C@](CCCCCCCCCCC)(O4)O[C@@]3([C@H](C)C5)[C@@H]2C=C1C SNFRINMTRPQQLE-OFGNMXNXSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QTZPBQMTXNEKRX-UHFFFAOYSA-N Voacristine pseudoindoxyl Natural products N1C2=CC=C(OC)C=C2C(=O)C21CCN(C1)C3C(C(C)O)CC1CC32C(=O)OC QTZPBQMTXNEKRX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
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- 239000013530 defoamer Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
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- 239000011229 interlayer Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- 201000009240 nasopharyngitis Diseases 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
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- 229920001155 polypropylene Polymers 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
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- 239000011164 primary particle Substances 0.000 description 1
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000011347 resin Substances 0.000 description 1
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- 239000004170 rice bran wax Substances 0.000 description 1
- 235000019384 rice bran wax Nutrition 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 125000005624 silicic acid group Chemical group 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4476—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications comprising polymerisation in situ
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/122—Inorganic polymers, e.g. silanes, polysilazanes, polysiloxanes
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1229—Composition of the substrate
- C23C18/1241—Metallic substrates
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
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Abstract
本发明提供一种即使绝缘被膜中不含铬化合物,其冲裁性、被膜密合性和退火后的被膜特性也优良的具有绝缘被膜的电磁钢板。本发明的具有绝缘被膜的电磁钢板的特征在于,其具有在电磁钢板的至少单面涂布表面处理剂并使其干燥而形成的绝缘被膜,所述表面处理剂以质量比(A/B):0.05~1.0含有三烷氧基硅烷和/或二烷氧基硅烷(A)和硅烷偶联剂(B),所述三烷氧基硅烷和/或二烷氧基硅烷(A)仅包含选自氢、烷基和苯基中的至少一种非反应性取代基。
Description
技术领域
本发明涉及一种具有绝缘被膜的电磁钢板。本发明特别涉及一种即使绝缘被膜中不含铬化合物,其冲裁性、被膜密合性和退火后的被膜特性也优良的具有绝缘被膜的电磁钢板。
背景技术
对于用于电动机、变压器等的电磁钢板的绝缘被膜,不仅要求层间电阻,还要求被膜密合性、冲裁性、焊接性等各种特性。由于电磁钢板被用于多种用途,因此根据其用途进行了各种绝缘被膜的开发。此外,在对电磁钢板实施冲裁加工、剪切加工、弯曲加工等时,残余应变会导致磁特性变差,因此,为了解决该问题,大多情况下在700~800℃左右的温度下进行去应力退火。因此,在该情况下,绝缘被膜必须能够承受去应力退火。
电磁钢板的绝缘被膜,大致分为以下3种:
(1)重视焊接性、耐热性且能够承受去应力退火的无机被膜、
(2)以兼顾冲裁性和焊接性作为目标,并且能够承受去应力退火的含有树脂的无机被膜(即半有机被膜)、
(3)为特殊用途而无法进行去应力退火的有机被膜,
其中,作为通用品而能够承受去应力退火的是上述(1)、(2)所示的含有无机成分的被膜,这两者通常均含有铬化合物。
例如,作为上述(2)的技术,专利文献1中记载了一种在电磁钢板的表面上形成有由硅酸盐被膜和含铬酸的上层被膜这两层所构成的绝缘被膜的电磁钢板。通过使这两层绝缘被膜的至少一者含有硅烷偶联剂,提高了与电磁钢板的被膜密合性等性能。
然而,近来环境意识有所提高,在电磁钢板领域,消费者等也期待具有不含铬化合物的绝缘被膜的无铬酸盐的产品。
在此,专利文献2中记载了一种对于镀锌钢板形成不含铬化合物的表面处理被膜的以下技术。即,专利文献2记载了一种耐腐蚀性和被膜密合性等各种性能优良的镀锌钢板,其具有将表面处理剂涂布在钢板表面上并使其干燥而得到的表面处理被膜,所述表面处理剂以规定比率包含水溶性锆化合物、四烷氧基硅烷、具有环氧基的化合物、螯合剂、钒酸化合物以及含有选自由钛、铝和锌组成的组中的至少一种以上的金属的金属化合物。
现有技术文献
专利文献
专利文献1:日本特开平2-38582号公报
专利文献2:日本特开2010-255105号公报
发明内容
发明所要解决的问题
对于电磁钢板表面上所形成的绝缘被膜来说,和镀锌钢板表面上的表面处理被膜的情况一样,也希望具有高耐腐蚀性和被膜密合性。因此,本发明人将可作为镀锌钢板上形成的表面处理被膜而发挥高被膜密合性的专利文献2中所述的pH8~10的表面处理剂涂布到电磁钢板表面上,并且进行干燥,形成绝缘被膜,所述表面处理剂含有锆化合物、四烷氧基硅烷、具有环氧基的化合物、螯合剂、钒酸化合物以及含有选自由Ti、Al和Zn构成的组中的至少一种以上的金属的金属化合物。于是可知,该表面处理剂意外地无法对电磁钢板赋予充分的耐腐蚀性和被膜密合性。因此,本发明人进行了各种研究,发现通过使用在水中混合四烷氧基硅烷和硅烷偶联剂所得的表面处理剂,在电磁钢板上可以获得耐腐蚀性。然而明确可知,即使在该情况下,被膜密合性依然不充分,冲裁性也不充分,并且还无法充分获得作为电磁钢板特有性能的退火后的被膜特性(具体来说是低铁损)。
因此,本发明鉴于上述问题,其目的在于提供一种即使绝缘被膜中不含铬化合物,其冲裁性、被膜密合性和退火后的被膜特性也优良的具有绝缘被膜的电磁钢板。
用于解决问题的方法
本发明人为了实现上述目的而作了进一步的研究,结果发现,作为用于在电磁钢板上形成绝缘被膜的表面处理剂成分,不使用四烷氧基硅烷而使用三烷氧基硅烷和/或二烷氧基硅烷,将其与硅烷偶联剂并用且以硅烷偶联剂作为主成分,由此可以实现上述目的,从而完成了本发明。
本发明基于这种见解而完成,其主要构成如下所述。
(1)一种具有绝缘被膜的电磁钢板,其特征在于,具有在电磁钢板的至少单面涂布表面处理剂并使其干燥而形成的绝缘被膜,所述表面处理剂以质量比(A/B):0.05~1.0含有三烷氧基硅烷和/或二烷氧基硅烷(A)和硅烷偶联剂(B),所述三烷氧基硅烷和/或二烷氧基硅烷(A)仅含有选自氢、烷基和苯基中的至少一种非反应性取代基。
(2)如上述(1)所述的具有绝缘被膜的电磁钢板,其中,所述表面处理剂含有相对于所述表面处理剂的总固体成分为2~30质量%的平均粒径为0.08~0.9μm并且长径比为10~100的板状二氧化硅(C)。
(3)如上述(2)所述的具有绝缘被膜的电磁钢板,其中,所述板状二氧化硅(C)的平均粒径为0.1~0.3μm并且长径比为10~50。
(4)如上述(1)~(3)中任一项所述的具有绝缘被膜的电磁钢板,其中,所述表面处理剂含有相对于所述表面处理剂的总固体成分为0.5~30质量%的润滑剂(D)。
发明效果
根据本发明,作为应用于电磁钢板的表面处理剂的成分,使用三烷氧基硅烷和/或二烷氧基硅烷,将其与硅烷偶联剂并用且以硅烷偶联剂作为主成分,由此可以提供一种即使绝缘被膜中不含铬化合物,其冲裁性、被膜密合性和作为电磁钢板特有性能的退火后的被膜特性也优良的具有绝缘被膜的电磁钢板。
具体实施方式
以下,对本发明进行具体说明。
<电磁钢板>
在本发明中,作为原材料的电磁钢板没有特别限制,以往公知的电磁钢板均适合。也就是说,磁通密度较高的所谓软铁板(电铁板)、SPCC等通常的冷轧钢板,以及为了提高比电阻而含有Si、Al的无方向性电磁钢板等均有利地适用。
<表面处理剂>
本发明中使用的表面处理剂含有三烷氧基硅烷和/或二烷氧基硅烷(A)、硅烷偶联剂(B)和水,所述三烷氧基硅烷和/或二烷氧基硅烷(A)的与Si键合的取代基仅包含选自氢、烷基和苯基中的至少一种非反应性取代基。
三烷氧基硅烷的种类没有特别限定,以通式R1Si(OR’)3表示,可以使用它们中的1种以上。R1为选自氢、烷基和苯基中的非反应性取代基。当R1为烷基时,优选碳数为1~6的直链或支链烷基,更优选碳数为1~3的直链或支链烷基。R’为烷基,优选碳数为1~4的直链或支链烷基,更优选碳数为1~2的直链或支链烷基。例如,可以使用甲基三甲氧基硅烷、乙基三甲氧基硅烷、甲基三乙氧基硅烷、乙基三乙氧基硅烷、苯基三乙氧基硅烷、苯基三甲氧基硅烷以及它们的水解物等。其中,从电磁钢板的耐腐蚀性以及冲裁性更优良的观点考虑,优选R1为烷基的三烷氧基硅烷。
二烷氧基硅烷的种类没有特别限定,以通式R2R3Si(OR’’)2表示,可以使用它们中的1种以上。其中,R2和R3为选自氢、烷基和苯基中的非反应性取代基,优选碳数为1~6的直链或支链烷基,更优选碳数为1~3的直链或支链烷基。R’’为烷基,优选碳数为1~4的直链或支链烷基,更优选碳数为1~2的直链或支链烷基。例如,可以使用二甲基二甲氧基硅烷、二甲基二乙氧基硅烷、二苯基二甲氧基硅烷以及它们的水解物等。其中,从电磁钢板的耐腐蚀性以及冲裁性更优良的观点考虑,优选R2和R3为烷基的二烷氧基硅烷。
硅烷偶联剂(B)的种类没有特别限定,以通式XSi(R4)n(OR)3-n(其中,n的范围为0~2)表示,可以同时使用它们中的1种以上。X为选自含活性氢的氨基、环氧基、巯基和甲基丙烯酰氧基中的至少一种反应性官能基。R4为烷基,优选碳数为1~4的直链或支链烷基,更优选碳数为1~2的直链或支链烷基。OR为任意的水解性基团,R例如为烷基,优选碳数为1~4的直链或支链烷基,更优选碳数为1~2的直链或支链烷基。此外,R例如为酰基(-COR5),R5优选碳数为1~4的直链或支链烷基,更优选碳数为1~2的直链或支链烷基。作为硅烷偶联剂(B),例如,可以使用N-(氨乙基)-3-氨丙基三甲氧基硅烷、3-氨丙基三甲氧基硅烷、3-环氧丙氧基丙基三甲氧基硅烷、3-环氧丙氧基丙基甲基二甲氧基硅烷、2-(3,4-环氧基环己基)乙基三乙氧基硅烷、乙烯基三乙氧基硅烷、3-巯基丙基三甲氧基硅烷以及它们的水解物等。其中,从电磁钢板的耐腐蚀性以及冲裁性更优良的观点考虑,优选具有氨基或环氧基的硅烷偶联剂。
本发明中所用的表面处理剂的特征在于,不含四烷氧基硅烷,而含有三烷氧基硅烷和/或二烷氧基硅烷(A)。如上所述,当应用于电磁钢板的表面处理剂含有四烷氧基硅烷时,无法获得充分的被膜密合性,此外,退火后的铁损劣化大,在退火后无法获得充分的被膜特性。然而,在使用含有三烷氧基硅烷和/或二烷氧基硅烷(A)的表面处理剂形成绝缘被膜时,意外地可以获得与电磁钢板表面的充分的被膜密合性,并且还进一步抑制了去应力退火后的铁损劣化。
此外,在使用专利文献2中公开的表面处理剂时,电磁钢板上的耐腐蚀性和被膜密合性不足的原因推测如下。已知在镀锌系钢板上,特别是在锌与被膜的界面处,钒酸化合物富集,推测酸导致锌溶解,在界面处形成反应生成物。另一方面,在电磁钢板的情况下,由于钢板表面上形成Si、Al的氧化膜,因此不与钒酸化合物发生反应,在被膜中残存过量的钒酸化合物,因此无法赋予耐腐蚀性。对于电磁钢板,可以考虑通过使用进一步提高了反应性的试剂除去氧化硅、氧化铝等氧化膜来提高耐腐蚀性的方法,然而由于氧化膜的不均匀除去、氧化膜下的铁的过度溶解,导致了锈的产生等。因此,进行了各种研究,结果发现在残存有表面氧化膜的情况下通过本发明中使用的表面处理剂形成绝缘被膜,由此可以获得良好的耐腐蚀性。
本发明中使用的表面处理剂的另一个特征在于,将三烷氧基硅烷和/或二烷氧基硅烷(A)与硅烷偶联剂(B)的质量比(A/B)设定为0.05~1.0的范围。当质量比超过1.0时,硅烷偶联剂(B)的量不充分,无法充分获得绝缘被膜的强韧性。结果无法获得充分的冲裁性,并且容易产生耐张力垫性(tension pad resistance)的劣化、操作中的损伤、被膜剥离等情况。这样,在本发明中不仅使用三烷氧基硅烷和/或二烷氧基硅烷(A),而且将硅烷偶联剂(B)作为主成分,由此可以显著地提高冲裁性和耐张力垫性。此外,当质量比小于0.05时,TIG焊接性下降。从这种观点出发,将质量比(A/B)设定为0.05~1.0的范围,更优选的质量比为0.1~0.5的范围。
本发明中使用的表面处理剂可以含有板状二氧化硅(C)。该板状二氧化硅也被称为叶状二氧化硅或鳞片状二氧化硅,其具有多个SiO2的薄层层叠起来的层状硅酸结构。并且,作为这种板状二氧化硅,优选具有非晶性或微晶性。板状二氧化硅,可以通过制作薄层的一次粒子层叠起来的凝集粒子,并将该凝集粒子粉碎而得到。由于这种板状二氧化硅采用层状的形式,因此与通常的二氧化硅粒子例如胶体二氧化硅等相比,腐蚀物质透过抑制性优良,进而由于羟基较多而密合性优良,并且由于为软质而滑动性优良。此外已知,胶体二氧化硅等无机成分通常会对冲裁性产生不良影响,而板状二氧化硅不易使冲裁性变差。其原因可以推定为,由于板状二氧化硅由薄层SiO2形成,因此冲裁时容易在层间发生滑动而容易变形。而且,由于表面处理剂的无机成分率增加,减少了TIG焊接中发生汽化的成分的比例,并且由于被膜密合性提高,沿着钢板表面的凹凸形成被膜,因此在板与板之间形成间隙,确保了汽化的气体的散逸路径,因而可以提高TIG焊接性。此外,在涂布含有板状二氧化硅的表面处理剂时,即使在涂布量容易变少的钢板表面凸部也会残留表面处理剂,能够沿着钢板表面的凹凸均匀地涂布表面处理剂,因此退火后绝缘被膜的膜厚均匀,并且即使因退火而导致有机系成分分解消失,耐腐蚀性也不会变差,而且不会因电磁钢板间的绝缘不良而导致退火后的铁损劣化。
对于板状二氧化硅(C),优选其平均粒径为0.08~0.9μm并且长径比为10~100的范围,更优选平均粒径为0.1~0.5μm并且长径比为20~90。当板状二氧化硅(C)的粒径为0.08μm以上时并且当长径比为10以上时,对于被膜形态是有效的,并且被膜充分均匀化,粘附性和TIG焊接性不会变差。此外,当平均粒径为0.9μm以下并且长径比为100以下时,三烷氧基硅烷和/或二烷氧基硅烷(A)与硅烷偶联剂(B)充分进入至被膜中,耐张力垫性充分。此处所谓的“耐张力垫性”,是指为了进行卷材的纵剪等而用于按压板的毛毡状张力垫摩擦表面时的被膜的不易剥离程度。
如果板状二氧化硅(C)的平均粒径为0.1~0.3μm并且长径比为10~50,则冲裁性优良,更加优选。如果平均粒径为0.1μm以上,则由冲裁引起的板状二氧化硅粉碎所导致的粉的产生不多,不会污染模具,因此冲裁性优良。此外,虽然存在板状二氧化硅的平均粒径越大,则冲裁时模具损耗越多的倾向,但当平均粒径为0.3μm以下时,模具损耗不成为问题,冲裁性优良。进而,如果长径比为10~50,则如前所述,冲裁时容易变形,冲裁性特别优良。此外,如果长径比为50以下,则能够沿着钢板表面的凹凸而形成均匀的被膜,因此耐腐蚀性和退火后的铁损也优良。
在本说明书中,板状二氧化硅的“平均粒径”,是指用SEM观察时,对于垂直于板状二氧化硅厚度的面上的长径,在视野中的多个粒子间进行平均的长度。
此外,在本说明书中,板状二氧化硅的“长径比”,是指用SEM观察时,对于视野中的10个粒子,将各粒子垂直于板状二氧化硅厚度的面上的长径/最大厚度的比值进行平均的值。
板状二氧化硅(C)的含量相对于表面处理剂的总固体成分优选为2~30质量%的范围,更优选为20质量%以下。如果为2质量%以上,则可以获得粘附性和TIG焊接性优良的电磁钢板,而如果为30质量%以下,则耐腐蚀性和耐张力垫性不会下降。
此外,为了提高冲裁性和耐张力垫性,在本发明中使用的表面处理剂中可以添加润滑剂(D)。作为润滑剂(D),可以列举聚乙烯蜡、氧化聚乙烯蜡、氧化聚丙烯蜡、巴西棕榈蜡、石蜡、褐煤蜡、米糠蜡、特富龙(注册商标)蜡、二硫化碳、石墨等固体润滑剂。此外,作为润滑剂(D),还可以使用非离子性丙烯酸树脂。作为非离子性丙烯酸树脂,例如,可以列举在结构上具有聚环氧乙烷或聚环氧丙烷的非离子系表面活性剂(乳化剂)的存在下,使丙烯酸、甲基丙烯酸、丙烯酸酯、甲基丙烯酸酯、苯乙烯等乙烯系单体在水中乳液聚合所得的水系乳液等通过非离子性乳化剂进行乳化的丙烯酸树脂。可以使用这些固体润滑剂中的1种或2种以上。
本发明中使用的润滑剂(D)的含量,相对于表面处理剂的总固体成分,优选为0.5~30质量%的范围,更优选为2~15质量%。如果为0.5质量%以上,则可以充分获得冲裁性和耐张力垫性的提高,而在30质量%以下时,TIG焊接性不会下降。
表面处理剂可以通过将上述成分在去离子水、蒸馏水等水中混合而得到。表面处理液的固体成分比例适当选择即可。此外,在表面处理剂中,还可以根据需要添加醇、酮、溶纤剂系水溶性溶剂、表面活性剂、消泡剂、流平剂、pH调节剂、防菌防霉剂等。通过添加这些物质,表面处理剂的干燥性、涂布外观、操作性、设计性提高。然而,重要的是以不会损害本发明中所得品质的程度添加这些物质,并且,添加量相对于表面处理剂的总固体成分至多小于5质量%。
如前所述,在本发明中,通过在电磁钢板的表面上涂布表面处理剂并进行加热干燥,从而形成绝缘被膜。作为在电磁钢板上涂布表面处理剂的方法,可以列举辊涂法、棒涂法、浸渍法、喷涂法等,可以根据所处理的电磁钢板的形状等来选择最适当的方法。更具体而言,例如,如果电磁钢板是板状的,则可以选择辊涂法、棒涂法或喷涂法。喷涂法,是向电磁钢板喷射表面处理剂,并通过辊挤压或在高压下吹出气体来调整涂布量的方法。如果在将电磁钢板制成成型品时,可以选择将其浸渍到表面处理液中并提起,并且根据情况用压缩空气吹走多余的表面处理剂而调整涂布量的方法等。
对涂布到电磁钢板表面上的表面处理剂进行加热干燥时的加热温度(最高到达板温),通常为80~350℃,更优选为100~300℃。如果加热温度为80℃以上,则被膜中不会残存作为主溶剂的水分,而如果加热温度为350℃以下,则抑制了被膜的裂纹的产生,因此不会产生电磁钢板的耐腐蚀性下降等问题。此外,对于加热时间,可以根据所使用的电磁钢板的种类等来选择最适当的条件。需要说明的是,从生产性等观点考虑,优选为0.1~60秒钟,更优选为1~30秒钟。
此外,对于具有绝缘被膜的电磁钢板,通过实施去应力退火,可以除去例如冲裁加工所导致的应变。作为优选的去应力退火气氛,可以应用N2气氛、DX气气氛等不易使铁氧化的气氛。此处,通过提高露点,例如设定为Dp:5~60℃左右,使表面和切断端面产生少许氧化,可以进一步提高耐腐蚀性。此外,优选的去应力退火温度为700~900℃,更优选为700~800℃。去应力退火温度的保持时间优选较长,例如为2小时以上。
电磁钢板的被膜附着量没有特别限定,但优选每单面上为0.05~5g/m2左右。附着量,即本发明的绝缘被膜的总固体成分质量,可以由通过碱剥离除去被膜后的重量减少来测定。此外,当附着量较少时,可以通过荧光X射线分析测定使用碱剥离法测定的附着量已知的标准试样,并由所得的校准曲线来测定。如果附着量为0.05g/m2以上,则可以同时满足耐腐蚀性和绝缘性,另一方面,如果为5g/m2以下,则不仅被膜密合性提高,而且在涂装烧结时不会产生膨胀而不会导致涂装性的下降。更优选为0.1~3.0g/m2。优选在钢板的两面上形成绝缘被膜,也可以根据目的仅在单面上形成,而另一面可以为其它绝缘被膜。
以下,使用实施例对本发明进行更详细的说明,但本发明并不受以下实施例的任何限定。
实施例
(1)原材料
使用板厚:0.5mm的电磁钢板[A230(JIS C2552(2000))]作为试验材料。
(2)表面处理剂
以表1中所示的组成(质量比)将各成分在水中混合,得到表面处理剂。
(3)处理方法
在连续退火线中进行用于获得规定材质的退火后,在钢板被冷却后的阶段通过辊涂机涂装添附表面处理剂,并使用烘箱以最高到达板温为140℃的方式进行干燥,在两面上形成被膜附着量为600mg/m2的绝缘被膜。作为辊涂机条件,设定为三辊、全反向方式。需要说明的是,干燥温度表示试验板表面的到达温度。
接着,对表1中使用的化合物进行说明。
<三烷氧基硅烷/二烷氧基硅烷/四烷氧基硅烷>
A1:甲基三甲氧基硅烷
A2:甲基三乙氧基硅烷
A3:二甲基二甲氧基硅烷
A4:苯基三甲氧基硅烷
A5:四甲氧基硅烷(比较例)
A6:四乙氧基硅烷(比较例)
<硅烷偶联剂>
B1:3-环氧丙氧基丙基三甲氧基硅烷
B2:N-(2-氨基乙基)-3-氨基丙基三甲氧基硅烷
B3:3-甲基丙烯酰氧基丙基甲基二甲氧基硅烷
B4:3-巯基丙基三甲氧基硅烷
<板状二氧化硅>
C1:平均粒径为0.2μm,长径比为20
C2:平均粒径为0.1μm,长径比为10
C3:平均粒径为0.5μm,长径比为50
C4:平均粒径为1.0μm,长径比为50
C5:平均粒径为0.08μm,长径比为10
C6:平均粒径为0.1μm,长径比为20
C7:平均粒径为0.15μm,长径比为20
C8:平均粒径为0.3μm,长径比为30
C9:平均粒径为0.3μm,长径比为50
C10:平均粒径为0.3μm,长径比为80
C11:平均粒径为0.5μm,长径比为30
<润滑剂>
D1:聚乙烯蜡(Chemipearl900)
D2:苯乙烯-甲基丙烯酸乙酯-丙烯酸正丁酯-丙烯酸共聚物
(评价方法)
(1)被膜密合性
使用直径为5mm的圆棒,将粘贴有透明胶带的钢板以受试面为压缩侧的方式进行180°弯曲后,剥离透明胶带,并通过荧光X射线测定被膜剥离量。测定180°弯曲前的被膜和剥离的透明胶带的Si的荧光X射线强度,并评价附着在透明胶带上的Si强度相对于180°弯曲前的被膜的Si强度的比例。
(判定基准)
◎:未剥离
○:超过0%,且为10%以下
△:超过10%,且为20%以下
×:超过20%
(2)冲裁性
使用15mmφ的钢模具对试验材料进行冲裁,直至毛刺高度达到50μm,并由该冲裁数进行评价。
(判定基准)
◎:120万次以上
○:100万次以上,且低于120万次
○-:70万次以上,且低于100万次
△:30万次以上,且低于70万次
×:低于30万次
(3)去应力退火后的铁损的测定
层叠5片冲裁为50mm×300mm的试验材料,在通过螺栓紧固并以9.8MPa(100Kgf/cm2)的压力将中央的50mm×50mm部分拧紧的状态下,在N2气氛中在750℃下保持2小时后,冷却至常温。测定这时的铁损以及将5片层叠的钢板拆开并再次层叠时的铁损(W15/50),以其差值(退火后的铁损-拆开后的铁损)进行评价。
(判定基准)
◎:0.5W/Kg以下
○:0.5~1.2W/Kg
△:1.2~2.0W/Kg
×:2.0W/Kg以上
(4)TIG焊接性
以9.8MPa(100kgf/cm2)的压力层叠试验材料,达到30mm的厚度,按照以下条件对其端面部(长度30mm)实施TIG焊接。
·焊接电流:120A
·Ar气体流量:6升/分钟
·焊接速度:10、20、30、40、50、60、70、80、90、100厘米/分钟
(判定基准)
以满足每1个焊珠的气孔数为5个以下的焊接速度的大小来判定优劣。
◎:60厘米/分钟以上
○:40厘米/分钟以上,且小于60厘米/分钟
△:20厘米/分钟以上,且小于40厘米/分钟
×:小于20厘米/分钟
(5)耐腐蚀性
将2片冲裁为50mm×50mm的试验材料重合在一起,载置200g的砝码,在50℃、相对湿度80%的恒温恒湿槽中放置2周。以目视来测定重合的2面上的平均的锈产生面积率。
(判定基准)
◎:0%
○:超过0%~小于2%
△:2%以上~小于5%
×:5%以上
(6)耐张力垫性
使用面积为10mm×10mm的张力垫,并通过太平理化工业(株)制的摩擦试验机施加24.5N(2.5kgf)的载荷,反复摩擦绝缘被膜表面100次。对经摩擦部分及其附近的附着量进行测定,算出反复100次后的绝缘被膜残存率。对于附着量来说,是测定Si的荧光X射线强度,并由根据附着量已知的标准板得到的校准曲线而求出的。
(判定基准)
◎:90%以上
○:80%以上~小于90%
△:60%以上~小于80%
×:小于60%
对于使用实施例和比较例中记载的表面处理剂所得的具有绝缘被膜的电磁钢板,将进行上述评价的结果示于表1。
实施例的结果如表1所示,冲裁性、被膜密合性、退火后的被膜特性(铁损)、TIG焊接性、耐腐蚀性、耐张力垫性全部优良。
产业上的可利用性
根据本发明,可以提供一种即使绝缘被膜中不含铬化合物,其冲裁性、被膜密合性和作为电磁钢板特有性能的退火后的被膜特性也优良的具有绝缘被膜的电磁钢板。
Claims (4)
1.一种具有绝缘被膜的电磁钢板,其特征在于,具有在电磁钢板的至少单面涂布表面处理剂并使其干燥而形成的绝缘被膜,所述表面处理剂以质量比(A/B):0.05~1.0含有三烷氧基硅烷和/或二烷氧基硅烷(A)和硅烷偶联剂(B),所述三烷氧基硅烷和/或二烷氧基硅烷(A)仅包含选自氢、烷基和苯基中的至少一种非反应性取代基。
2.如权利要求1所述的具有绝缘被膜的电磁钢板,其中,所述表面处理剂含有相对于所述表面处理剂的总固体成分为2~30质量%的平均粒径为0.08~0.9μm并且长径比为10~100的板状二氧化硅(C)。
3.如权利要求2所述的具有绝缘被膜的电磁钢板,其中,所述板状二氧化硅(C)的平均粒径为0.1~0.3μm并且长径比为10~50。
4.如权利要求1~3中任一项所述的具有绝缘被膜的电磁钢板,其中,所述表面处理剂含有相对于所述表面处理剂的总固体成分为0.5~30质量%的润滑剂(D)。
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