TWI823024B - 無方向性電磁鋼板及無方向性電磁鋼板用表面處理劑 - Google Patents
無方向性電磁鋼板及無方向性電磁鋼板用表面處理劑 Download PDFInfo
- Publication number
- TWI823024B TWI823024B TW109132414A TW109132414A TWI823024B TW I823024 B TWI823024 B TW I823024B TW 109132414 A TW109132414 A TW 109132414A TW 109132414 A TW109132414 A TW 109132414A TW I823024 B TWI823024 B TW I823024B
- Authority
- TW
- Taiwan
- Prior art keywords
- steel plate
- phosphate
- insulating film
- zinc
- mass
- Prior art date
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 85
- 239000010959 steel Substances 0.000 title claims abstract description 85
- 239000012756 surface treatment agent Substances 0.000 title claims description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 82
- 239000002184 metal Substances 0.000 claims abstract description 72
- 150000003839 salts Chemical class 0.000 claims abstract description 66
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 54
- 239000010452 phosphate Substances 0.000 claims abstract description 54
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 53
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 51
- 239000011701 zinc Substances 0.000 claims abstract description 49
- 239000011347 resin Substances 0.000 claims abstract description 31
- 229920005989 resin Polymers 0.000 claims abstract description 31
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 25
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000010953 base metal Substances 0.000 claims abstract description 8
- 238000001420 photoelectron spectroscopy Methods 0.000 claims abstract description 3
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 21
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 21
- 229910000565 Non-oriented electrical steel Inorganic materials 0.000 claims description 17
- 229910001463 metal phosphate Inorganic materials 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 13
- 239000004925 Acrylic resin Substances 0.000 claims description 12
- 229920000178 Acrylic resin Polymers 0.000 claims description 12
- 229910052748 manganese Inorganic materials 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000009413 insulation Methods 0.000 abstract description 19
- 235000021317 phosphate Nutrition 0.000 description 48
- 239000000463 material Substances 0.000 description 27
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 20
- 238000000576 coating method Methods 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 18
- 230000007797 corrosion Effects 0.000 description 17
- 238000005260 corrosion Methods 0.000 description 17
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000011572 manganese Substances 0.000 description 10
- 239000000523 sample Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- -1 chromic acid compound Chemical class 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Chemical class O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 235000011007 phosphoric acid Nutrition 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000003595 spectral effect Effects 0.000 description 5
- 238000000859 sublimation Methods 0.000 description 5
- 230000008022 sublimation Effects 0.000 description 5
- 238000000137 annealing Methods 0.000 description 4
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 4
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 4
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 4
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 4
- 239000004137 magnesium phosphate Substances 0.000 description 4
- 229960002261 magnesium phosphate Drugs 0.000 description 4
- 235000010994 magnesium phosphates Nutrition 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 229920000858 Cyclodextrin Polymers 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000013626 chemical specie Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910000159 nickel phosphate Inorganic materials 0.000 description 2
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- 150000008163 sugars Chemical class 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-M 2-ethylacrylate Chemical compound CCC(=C)C([O-])=O WROUWQQRXUBECT-UHFFFAOYSA-M 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- 229910018516 Al—O Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229910007541 Zn O Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- MSJMDZAOKORVFC-UAIGNFCESA-L disodium maleate Chemical compound [Na+].[Na+].[O-]C(=O)\C=C/C([O-])=O MSJMDZAOKORVFC-UAIGNFCESA-L 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000001530 fumaric acid Substances 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
- 239000007789 gas Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- MDYPDLBFDATSCF-UHFFFAOYSA-N nonyl prop-2-enoate Chemical compound CCCCCCCCCOC(=O)C=C MDYPDLBFDATSCF-UHFFFAOYSA-N 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
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
- 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
- C23C22/20—Orthophosphates containing aluminium cations
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- 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
- C23C22/12—Orthophosphates containing zinc cations
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/008—Heat treatment of ferrous alloys containing Si
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
- C21D8/1277—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties involving a particular surface treatment
- C21D8/1283—Application of a separating or insulating coating
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
- H01F1/16—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of sheets
- H01F1/18—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of sheets with insulating coating
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- 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
- C23C22/12—Orthophosphates containing zinc cations
- C23C22/17—Orthophosphates containing zinc cations containing also organic acids
-
- 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
- C23C22/82—After-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Electromagnetism (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Power Engineering (AREA)
- Chemical Treatment Of Metals (AREA)
- Soft Magnetic Materials (AREA)
Abstract
一種無方向性電磁鋼板,具備母材鋼板及形成於前述母材鋼板表面之絕緣被膜,絕緣被膜係以磷酸金屬鹽、有機樹脂及水溶性有機化合物為主體,水溶性有機化合物之SP值在10.0~20.0(cal/cm3
)1/2
之範圍內,磷酸金屬鹽包含鋁及鋅作為金屬元素,當從絕緣被膜表面沿無方向電磁鋼板之厚度方向藉由光電子能譜分析法進行測定時,鋅之2p波峰強度達最大之深度存在於較鋁之2p波峰強度達最大之深度更靠前述表面側,並且鋅之2p波峰強度之最大值係在前述鋅之2p波峰強度達最大之深度中之鋁之2p波峰強度的1~20倍。
Description
本發明係關於無方向性電磁鋼板及無方向性電磁鋼板用表面處理劑。
無方向性電磁鋼板之表面一般係形成有絕緣被膜。對於絕緣被膜,不僅要求絕緣性,還要求如耐蝕性、密著性、耐受退火所需之耐熱性、作為被膜之穩定性等的各種被膜特性。以往,絕緣被膜中摻混有鉻酸化合物,而以極高等級實現了如上述之被膜的各種特性。然而,近年來,在對環境問題之意識高漲之中,針對不含鉻酸化合物之絕緣被膜正持續進行開發。
例如,專利文獻1中揭示有一種具有絕緣被膜之無方向性電磁鋼板,該絕緣被膜係以選自特定金屬元素中之1種磷酸金屬鹽、與有機樹脂作為主成分。
先前技術文獻
專利文獻
專利文獻1:日本專利特開平11-80971號公報
發明欲解決之課題
然而,在如專利文獻1所揭示之使用了不含鉻酸化合物之絕緣被膜的情況下,雖顯示出優異絕緣性且沖裁性(亦即加工性)提升,但在實現更兼具密著性、耐蝕性及耐熱性的絕緣被膜之際,仍有改善餘地。
本發明係有鑑於上述問題而作成者,其目的在於提供一種具有絕緣被膜之無方向性電磁鋼板及用以形成該絕緣被膜之無方向性電磁鋼板用表面處理劑,該絕緣被膜不含鉻酸化合物而具優異絕緣性、加工性、密著性、耐蝕性及耐熱性。
用以解決課題之手段
本發明係為了解決上述課題而作成者,其主旨在於下述無方向性電磁鋼板及無方向性電磁鋼板用表面處理劑。
(1)一種無方向性電磁鋼板,具備母材鋼板及形成於前述母材鋼板表面之絕緣被膜;
前述絕緣被膜中相對於前述絕緣被膜之總質量,含有合計50質量%以上之磷酸金屬鹽、有機樹脂及水溶性有機化合物;
前述水溶性有機化合物之SP值在10.0~20.0(cal/cm3
)1/2
之範圍內;
前述磷酸金屬鹽包含鋁及鋅作為金屬元素;
當從前述絕緣被膜表面沿前述無方向電磁鋼板之厚度方向藉由光電子能譜分析法進行測定時,
鋅之2p波峰強度達最大之深度存在於較鋁之2p波峰強度達最大之深度更靠前述表面側,並且
鋅之2p波峰強度之最大值係在前述鋅之2p波峰強度達最大之深度中之鋁之2p波峰強度的1~20倍。
(2)如上述(1)之無方向性電磁鋼板,其中前述絕緣被膜含有相對於前述磷酸金屬鹽100質量份為3~50質量份之丙烯酸樹脂作為前述有機樹脂。
(3)如上述(1)或(2)之無方向性電磁鋼板,其中前述磷酸金屬鹽更包含選自於由Co、Mg、Mn及Ni所構成群組中之1種以上作為金屬元素。
(4)一種無方向性電磁鋼板用表面處理劑,係用以於無方向性電磁鋼板表面形成絕緣被膜者;
該表面處理劑中相對於含鋁及鋅之磷酸金屬鹽100質量份,包含有機樹脂3~50質量份及水溶性有機化合物5~50質量份;
前述水溶性有機化合物之SP值在10.0~20.0(cal/cm3
)1/2
之範圍內;並且
前述磷酸金屬鹽中之鋁元素與鋅元素之莫耳比(Al:Zn)在10:90~75:25之範圍內。
(5)如上述(4)之無方向性電磁鋼板用表面處理劑,其中前述有機樹脂為丙烯酸樹脂。
(6)如上述(4)或(5)之無方向性電磁鋼板用表面處理劑,其更包含磷酸金屬鹽,該磷酸金屬鹽具有選自於由Co、Mg、Mn及Ni所構成群組中之1種以上元素。
發明效果
根據本發明,可獲得一種具有絕緣被膜之無方向性電磁鋼板,該絕緣被膜不含鉻酸化合物而具優異絕緣性、加工性、密著性、耐蝕性及耐熱性。
用以實施發明之形態
本發明人等針對實現兼具絕緣性、加工性、密著性、耐蝕性及耐熱性之絕緣被膜的方法致力進行了研討,結果終至獲得以下知識見解。
(a)為了發揮涵蓋絕緣性、加工性、密著性、耐蝕性及耐熱性之多種類的所有特性,必須活用包含複數種金屬元素之磷酸金屬鹽。
(b)本發明人等進行研討的結果發現,使耐蝕性佳的鋅之磷酸金屬鹽在絕緣被膜表面側濃化,並且使密著性及耐熱性佳的鋁之磷酸金屬鹽在母材鋼板側濃化,藉此除了絕緣性及加工性之外,還可兼顧密著性、耐蝕性及耐熱性。
(c)然而,僅調整添加在表面處理劑中作為磷酸金屬鹽之鋁及鋅的含量,無法實現鋅之磷酸金屬鹽在絕緣被膜表面側濃化且鋁之磷酸金屬鹽在母材鋼板側濃化的被膜構成。
(d)以各種條件形成絕緣被膜並解析被膜之構成,結果藉由控制在表面處理劑中與磷酸金屬鹽一同添加之水溶性有機化合物的組成、及塗佈表面處理劑後的加熱條件,可實現上述被膜構成。
(e)鋅之磷酸金屬鹽在絕緣被膜表面側濃化且鋁之磷酸金屬鹽在母材鋼板側濃化的機制尚不明確,但推測係磷酸金屬鹽之金屬離子的穩定性造成的影響。
(f)磷酸金屬鹽因在水溶液中大多不穩定,而有在早期析出的傾向。因此,磷酸金屬鹽在鋼板側濃化的情況較多。但,藉由使表面處理劑中之水溶性有機化合物的組成及添加量變得適當,可使金屬元素的穩定性產生差異,尤其可提升鋅之磷酸金屬鹽的穩定性。其結果,穩定性高的鋅之磷酸金屬鹽變得比穩定性相對較低的鋁之磷酸金屬鹽更慢析出,而在絕緣被膜表面側濃化。
(g)除此之外,為了使鋅及鋁的濃化位置產生差異,必須在母材鋼板表面塗佈表面處理劑後至凝固為止之間,確保表面處理劑中之各元素充分擴散的時間。由該觀點來看,塗佈表面處理劑後放置預定時間,且將加熱速度及加熱溫度皆控制得較低。
(h)藉由使以上條件變得適當,便可形成鋅之磷酸金屬鹽在絕緣被膜表面側濃化且鋁之磷酸金屬鹽在母材鋼板側濃化的被膜。
本發明係根據上述知識見解而作成者。以下,說明本發明之各要件。
1.關於無方向性電磁鋼板之整體構成
圖1係用以說明本實施形態之無方向性電磁鋼板之構造的示意圖。無方向性電磁鋼板1具備母材鋼板11及形成於母材鋼板11表面之絕緣被膜13。又,圖1中係於母材鋼板11之厚度方向上之兩側表面設有絕緣被膜13,但絕緣被膜13亦可僅設於母材鋼板11之單側表面。
2.關於母材鋼板
用於無方向性電磁鋼板1之母材鋼板11的鋼種並無特別限定。例如,可適宜使用具有以下化學組成之無方向性電磁鋼板:以質量%計,含有Si:0.1%以上與Al:0.05%以上,且剩餘部分為Fe及不純物。
Si係藉由含量達0.1質量%以上而會使電阻增加,使磁特性提升之元素。雖然隨著Si含量增加,磁特性也會提升,但在電阻增加的同時,脆性會有增加的傾向。脆性增加之情形在Si含量大於4.0質量%時十分明顯,故Si含量宜為4.0質量%以下。
與Si同樣地,Al亦為藉由含量在0.05質量%以上而會使電阻增加,使磁特性提升之元素。雖然隨著Al含量增加,磁特性也會提升,但在電阻增加的同時,軋延性會有降低的傾向。軋延性降低之情形在Al含量大於3.0質量%時十分明顯,故Al含量宜為3.0質量%以下。
只要為具有如上述之Si含量及Al含量之無方向性電磁鋼板,則無特別限定,可使用周知之各種無方向性電磁鋼板作為母材鋼板11。
另外,母材鋼板11除上述Si及Al以外,亦可取代剩餘部分之Fe的一部分,而以0.01~3.0質量%之範圍含有Mn。此外,在本實施形態之母材鋼板中,其他之S、N、C之類的元素含量合計宜小於100ppm,小於30ppm更佳。
在本實施形態中,宜使用以下之物作為母材鋼板11:藉由熱軋延將具有上述化學組成之鋼塊(譬如扁胚)作成熱軋板並捲取成卷狀,且視需求在熱軋板之狀態下於800~1050℃之溫度範圍下退火,然後冷軋延成0.15~0.50mm之厚度,再進一步進行退火而得之物。母材鋼板11的板厚在0.25mm以下較佳。又,要進行冷軋延後之退火時,其退火溫度宜為750~1000℃之範圍。
此外,在母材鋼板11中表面粗度較小者,磁特性較佳故較理想。具體而言,軋延方向及相對於軋延方向為直角方向的算術平均粗度(Ra)分別宜為1.0µm以下,更宜為0.1~0.5µm。其原因在於Ra大於1.0µm時會觀察到磁特性劣化之傾向。
3.關於絕緣被膜
絕緣被膜13係形成於母材鋼板11之至少單側的表面上。絕緣被膜係以如以下詳述之磷酸金屬鹽、有機樹脂及水溶性有機化合物為主成分且不含鉻的絕緣被膜。具體而言,其中相對於絕緣被膜之總質量,含有合計50質量%以上之磷酸金屬鹽、有機樹脂及水溶性有機化合物。以下,詳細說明各成分。
3-1.磷酸金屬鹽
絕緣被膜所含之磷酸金屬鹽,係在使以磷酸與金屬離子為主成分之溶液(譬如水溶液等)乾燥時會成為固體成分者,且係在絕緣被膜中作為黏結劑發揮功用者。磷酸之種類並無特別限定,可使用周知的各種磷酸,譬如宜使用正磷酸、偏磷酸、多磷酸等。又,磷酸金屬鹽之溶液可藉由對各種磷酸混合金屬離子之氧化物、碳酸鹽及氫氧化物中至少任一者來調製。
磷酸金屬鹽包含鋁(Al)及鋅(Zn)作為金屬元素。亦即,絕緣被膜中包含Al之磷酸金屬鹽(亦即磷酸鋁)與Zn之磷酸金屬鹽(亦即磷酸鋅)。
另,本實施形態之絕緣被膜除了Al及Zn之磷酸金屬鹽之外,亦可更包含其他2價金屬元素M之磷酸鹽金屬。所述2價金屬元素M可舉例如選自於由Co、Mg、Mn及Ni所構成群組中之1種以上元素。藉由除磷酸鋁及磷酸鋅以外,還包含具有如上述之金屬元素M的磷酸金屬鹽作為磷酸金屬鹽,可使絕緣被膜變得更加細密,而進一步提升絕緣被膜之各種特性。
又,在本發明中,如上所述係透過使磷酸鋅在絕緣被膜表面側濃化,並且使磷酸鋁在母材鋼板側濃化,來實現兼具絕緣性、加工性、密著性、耐蝕性及耐熱性的絕緣被膜。
更具體而言,在本發明之無方向性電磁鋼板中,從絕緣被膜表面沿厚度方向藉由光電子能譜分析法(X-ray Photoelectron Spectroscopy:XPS)進行測定時,Zn之2p波峰強度達最大之深度存在於較Al之2p波峰強度達最大之深度更靠表面側(在以下說明中亦稱為「條件(a)」)。
又,當存在複數個Zn之2p波峰強度達最大之深度時,設為採用其中最靠近絕緣被膜表面之深度。關於Al之2p波峰強度達最大之深度亦相同。
如上所述,磷酸金屬鹽在水溶液中通常不穩定,因此會在早期析出而有於母材鋼板側濃化的傾向。圖2~圖4係用以說明無方向性電磁鋼板之絕緣被膜中之XPS光譜行為的圖表。圖2中顯示針對分別使用磷酸鎂、磷酸鈷、磷酸錳及磷酸鋁之4種形成有絕緣被膜的試樣進行XPS光譜測定的結果。亦即,其係有關各絕緣被膜之Mg、Co、Mn及Al之2p波峰的解析結果。另,關於上述4種試樣,所使用之母材鋼板及絕緣被膜中除磷酸金屬鹽以外的成分為共通,測定條件亦設為互相相同。
如圖2所示,當使用1種金屬元素之磷酸金屬鹽形成絕緣被膜時,不論在哪一種金屬元素中皆呈2p波峰強度越靠表面側就變得越低的結果。從該結果亦可知磷酸金屬鹽在水溶液中不穩定,而易於母材鋼板側濃化。
接著,針對分別形成有使用磷酸鋁及磷酸鋅之絕緣被膜、使用磷酸鋁及磷酸鎂之絕緣被膜、使用磷酸鋁及磷酸鈷之絕緣被膜、以及使用磷酸鋁及磷酸錳之絕緣被膜之4種試樣亦進行了相同解析。將其結果顯示於圖3及圖4。
圖3係有關各絕緣被膜之Zn、Mg、Co及Mn各自之2p波峰的解析結果,圖4係有關各絕緣被膜之Al之2p波峰之解析結果。
如圖3所示,Mg、Co及Mn之2p波峰強度係呈越靠表面側就變得越低的結果。另一方面,Zn之2p波峰可知係在如以虛線包圍之區域,在絕緣被膜表面附近達極大後便逐漸減少。
又,如圖4所示,關於各絕緣被膜之Al之2p波峰強度,在與Mg、Co、Mn之組合中係在絕緣被膜表面附近達極大,相對於此,在與Zn之組合中係在如以虛線包圍之區域,在深度150nm左右達極大。比較圖3及圖4即可明瞭只有在組合磷酸鋁與磷酸鋅時,係呈Zn之2p波峰強度達最大之深度存在於較Al之2p波峰強度達最大之深度更靠表面側的結果。
另,針對除了磷酸鋁及磷酸鋅之外還含有磷酸鎂、磷酸鈷、磷酸錳及磷酸鎳中之至少任一者的情況,以與上述同樣方式進行了確認,結果磷酸鋁與磷酸鋅之位置關係會重現。
並且,本發明之無方向性電磁鋼板中,在藉由XPS進行測定時,Zn之2p波峰強度之最大值係在Zn之2p波峰強度達最大之深度(以下亦稱為「最大Zn深度」)中之Al之2p波峰強度的1~20倍(以下說明中亦稱「條件(b)」)。亦即,在最大Zn深度中,Zn之2p波峰強度係Al之2p波峰強度的1~20倍。
在最大Zn深度中,Zn之2p波峰強度小於Al之2p波峰強度的1倍時,不會有足夠的量的磷酸鋅在絕緣被膜表面附近濃化,而無法獲得優異耐蝕性。另一方面,當Zn之2p波峰強度大於Al之2p波峰強度的20倍時,磷酸鋁的量變得過少,而無法實現優異的密著性及耐熱性。在最大Zn深度中,Zn之2p波峰強度相對於Al之2p波峰強度宜為1.2倍以上,更宜為1.5倍以上。並且,Zn之2p波峰強度相對於Al之2p波峰強度宜為10倍以下,更宜為5倍以下。
在此,XPS係指適於區別化學種類的差異並同時觀察化學種類分布的測定方法。藉由使用XPS沿厚度方向濺鍍絕緣被膜並進行觀察,可特定出磷酸金屬鹽的厚度方向分布。
具體而言,上述Al之2p波峰(有關2p電子之波峰)係歸屬於磷酸鋁之Al-O鍵的XPS波峰,可在結合能76eV附近觀察到,上述Zn之2p波峰(有關2p電子之波峰)則係歸屬於磷酸鋅之Zn-O鍵的XPS波峰,可在結合能1023eV附近觀察到。
同樣地,其他金屬元素M(Co、Mg、Mn、Ni)之2p波峰(有關2p電子之波峰)係歸屬於金屬元素M之磷酸金屬鹽之M-O鍵的XPS波峰,例如可在如以下之結合能附近觀測到。
磷酸鈷:780~790eV
磷酸鎂:50~54eV
磷酸錳:642~650eV
磷酸鎳:848~855eV
又,如上述之XPS光譜可使用市售X射線光電子能譜分析裝置來測定。並且,XPS光譜之測定條件設定成以下即可。
測定裝置:ULVAC-PHI, Inc.製之XPS測定裝置PHI5600
X射線源:MgKα
分析面積:800µmφ
濺鍍產率:2nm/分鐘(SiO2
換算)
測定面:最表面、0.1、0.5、1、2、5、10分鐘以後為10分鐘間隔
3-2.有機樹脂
絕緣被膜所含之有機樹脂係以分散在作為黏結劑發揮功用的磷酸金屬鹽中之狀態存在。藉由在磷酸金屬鹽中存在有機樹脂,可抑制磷酸金屬鹽的晶粒大幅成長,而促進磷酸金屬鹽的多晶化,且可形成細密的絕緣被膜。
有機樹脂的種類並無特別限定,可使用丙烯酸樹脂、聚苯乙烯樹脂、乙酸乙烯酯樹脂、環氧樹脂、聚胺甲酸乙酯樹脂、聚醯胺樹脂、酚樹脂、三聚氰胺樹脂、矽樹脂、聚丙烯樹脂、聚乙烯樹脂等周知之各種有機樹脂中之1種或2種以上樹脂。惟,從酸性溶液之液體穩定性之觀點來看,有機樹脂較宜使用丙烯酸樹脂。
若要舉出丙烯酸樹脂之例,則可為1種單體之聚合物,亦可為2種以上單體之共聚物。又,構成上述丙烯酸樹脂之單體並無特別限定,例如可使用丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸異丁酯、丙烯酸正辛酯、丙烯酸異辛酯、丙烯酸2-乙基己酯、丙烯酸正壬酯、丙烯酸正癸酯、丙烯酸正十二酯等。此外,具官能基之單體可使用丙烯酸、甲基丙烯酸、馬來酸、馬來酸酐、延胡索酸、巴豆酸、伊康酸等,具羥基之單體可使用(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸3-羥丁酯、2-羥乙基(甲基)烯丙基醚等。
3-3.水溶性有機化合物
絕緣被膜所含之水溶性有機化合物係醇、酯、酮、醚、羧酸、糖等之水溶性有機化合物,且係可與磷酸金屬鹽等無機組成液相溶者。藉由對包含磷酸金屬鹽及有機樹脂之處理液摻混水溶性有機化合物,在將處理液塗佈於鋼板表面並加以乾燥時,水溶性有機化合物會變成被含在磷酸金屬鹽等無機成分中。另,本實施形態中之水溶性意指可對水無限溶解或部分溶解的特性。
本實施形態之水溶性有機化合物之SP值係在10.0~20.0(cal/cm3
)1/2
的範圍內。在此,SP值係被稱為溶解度參數(Solubility Parameter)者,其表示物質相互的混合性。
SP值為物質的固有特性值,故若為純物質則可使用文獻值。又,從實際測定來獲得SP值之具體數值時,可從蒸發能量的測定值化求算,而若為水溶液,則可從添加了不良溶劑時之濁度變化求算,或可從對已知SP值之溶劑的溶解性求算。
SP值小於10.0(cal/cm3
)1/2
時,無法充分提升磷酸鋅的穩定性,而在絕緣被膜中廣泛分布,變得不會顯示出明顯的波峰。其結果,雖Zn之2p波峰強度之最大值係存在於絕緣被膜表面附近,但並沒有變得較在該深度之Al之2p波峰強度更大,無法充分提升耐蝕性。亦即,變得不滿足條件(b)。另外,在處理溶液中水溶性有機化合物容易分離,而成為塗佈不均及被膜不良的原因。另一方面,當SP值大於20.0(cal/cm3
)1/2
時,與磷酸金屬鹽之交互作用變得極低,無法使磷酸鋅變得穩定,導致磷酸鋁在絕緣被膜表面側濃化。亦即,變得不滿足條件(a)。
具體上,本實施形態之水溶性有機化合物,以醇類而言可舉丁醇、丙醇等直鏈醇類,以多元醇類而言可舉丙二醇、甘油、乙二醇、三乙二醇等,以羧酸類而言可舉甲基乙基酮、二乙基酮等酮類、乙酸、丙酸,以羧酸鹽類而言可舉馬來酸鈉鹽等,以糖類而言可舉蔗糖、果糖等,以賽璐蘇而言可舉甲賽璐蘇、丁賽璐蘇等,以卡必醇類而言可舉二乙二醇單甲基醚、二乙二醇二乙基醚等,以酯類而言可舉四乙二醇二甲基醚、1,4-二㗁烷等之醚類、乙二醇單甲基醚乙酸酯等。該等各種水溶性有機化合物中,可適宜使用SP值為10.0~20.0(cal/cm3
)1/2
之範圍者。
另,水溶性有機化合物有時係使用膦酸。但膦酸不僅SP值不滿足規定範圍,酸性度也較高。因此,當充分確保從將含膦酸之表面處理劑塗佈於母材鋼板表面起到凝固為止的時間時,在母材鋼板表面恐會生鏽。
又,水溶性有機化合物在塗佈燒附後會殘留在被膜中。此時,即便在水溶性有機化合物之沸點或昇華點低於水的沸點的情況下,因水溶性有機化合物與磷酸金屬鹽互相彼此作用,所以水溶性有機化合物會殘留在塗佈燒附後的被膜中。另外,在實際作業時,被膜之乾燥、燒附所需時間為數秒左右,因此水溶性有機化合物會殘留在被膜中。
惟,為了使水溶性有機化合物更確實地殘留在塗佈燒附後之被膜中,當水溶性有機化合物為液體時,以其沸點較水之沸點高為佳,當係固體時則以其昇華點較水之沸點高為佳。更適宜的是本實施形態之水溶性有機化合物之沸點或昇華點在150℃以上為佳,在200℃以上更佳。藉由使用沸點或昇華點為150℃以上的水溶性有機化合物,可抑制被膜中之水溶性有機化合物之殘留率降低,而可更確實地展現水溶性有機化合物的添加效果。另一方面,本實施形態之水溶性有機化合物之沸點或昇華點宜低於300℃。水溶性有機化合物之沸點或昇華點為300℃以上時,可能會成為沾黏及潮解的原因。
4.絕緣被膜之膜厚
絕緣被膜之厚度譬如宜為0.3~5.0µm左右,較佳為0.5µm~2.0µm左右。藉由將絕緣被膜之膜厚設為如上述之範圍,可維持更優異的均一性。
5.關於無方向性電磁鋼板用表面處理劑
接著,針對在製造無方向性電磁鋼板時使用之用以形成絕緣被膜之表面處理劑,於以下詳細說明。
本實施形態之表面處理劑係水溶液系之處理劑,其係用以在作為無方向性電磁鋼板發揮功用之母材鋼板的表面形成如上述之絕緣被膜者。該表面處理劑中相對於含鋁及鋅之磷酸金屬鹽100質量份,包含有機樹脂3~50質量份及水溶性有機化合物5~50質量份。
在此,表面處理劑中之磷酸金屬鹽、有機樹脂及水溶性有機化合物設為使用前述磷酸金屬鹽、有機樹脂及水溶性有機化合物。
又,在本實施形態之表面處理劑所含之磷酸金屬鹽中,使鋁元素與鋅元素之莫耳比(Al:Zn)在10:90~75:25之範圍內。藉由使鋁元素與鋅元素之莫耳比在上述範圍內,使用表面處理劑形成之絕緣被膜便會滿足有關XPS光譜之條件(a)及條件(b)。表面處理劑中磷酸金屬鹽之鋁元素與鋅元素之莫耳比(Al:Zn)宜在30:70~50:50之範圍內。
另,上述莫耳比(Al:Zn)之值可使用ICP(Inductively Coupled Plasma:感應耦合電漿)發光分光分析裝置分析所獲得之表面處理劑,將鋁元素及鋅元素之莫耳量定量,再分別從所得莫耳量算出。
表面處理劑所含之有機樹脂含量相對於磷酸金屬鹽100質量份設為3~50質量份。藉由使有機樹脂含量為上述範圍,尤其可提高磷酸鋅的穩定性,而可滿足條件(a)及條件(b)。又,藉由使有機樹脂含量在50質量份以下,可相對提高磷酸金屬鹽之濃度,而可確保耐熱性。
有機樹脂含量相對於磷酸金屬鹽100質量份宜為5質量份以上,較佳為10質量份以上。又,有機樹脂含量相對於磷酸金屬鹽100質量份宜為40質量份以下,較佳為30質量份以下。
本實施形態之表面處理劑藉由含有適當量之具上述範圍之SP值的水溶性有機化合物,可形成磷酸鋅在絕緣被膜表面側濃化且磷酸鋁在母材鋼板側濃化的被膜。因此,表面處理劑所含之水溶性有機化合物含量相對於磷酸金屬鹽100質量份設為5~50質量份。藉由使水溶性有機化合物含量為上述範圍,尤其可提高磷酸鋅的穩定性,而可滿足條件(a)及條件(b)。
此外,藉由使水溶性有機化合物含量在5質量份以上,沖裁性亦會提升。並且,藉由使水溶性有機化合物含量在50質量份以下,可抑制絕緣被膜沾黏或白濁,而可獲得具有光澤的被膜表面。水溶性有機化合物含量相對於磷酸金屬鹽100質量份宜為8質量份以上,較佳為10質量份以上。又,水溶性有機化合物含量相對於磷酸金屬鹽100質量份宜為30質量份以下,較佳為20質量份以下。
此外,本實施形態之表面處理劑除了上述成分以外,亦可含有例如碳酸鹽、氫氧化物、氧化物、鈦酸鹽、鎢酸鹽等無機化合物之類的黏結劑成分。並且,上述處理液中亦可含有其他光澤劑等。
6.關於無方向性電磁鋼板之製造方法
本實施形態之無方向性電磁鋼板之製造方法,係用以製造具備母材鋼板與絕緣被膜之無方向性電磁鋼板之製造方法。本實施形態之製造方法包含以下步驟:將上述表面處理劑塗佈於母材鋼板表面之步驟;及,將塗佈有表面處理劑之母材鋼板予以加熱而形成絕緣被膜之步驟。
在此,將表面處理劑塗佈於母材鋼板表面時的塗佈方法並無特別限定,可使用周知的各種塗佈方式。所述塗佈方式例如可使用輥塗方式,亦可使用噴霧方式、浸漬方式等塗佈方式。
又,如上所述,必須在母材鋼板表面塗佈表面處理劑後至凝固為止之間,確保表面處理劑中之各元素充分擴散的時間。因此,首先,在塗佈表面處理劑後至加熱為止之間放置1.5秒以上。接著,在將塗佈有表面處理劑之母材鋼板予以加熱來形成絕緣被膜時,將加熱溫度設為220℃以上且低於260℃,從開始加熱起至加熱溫度為止的平均加熱速度設為小於25℃/秒。關於開始加熱時之溫度並無特別限制,只要為室溫附近之溫度即可。
並且,加熱方式無特別限定,可使用一般的輻射爐或熱風爐,亦可使用感應加熱方式等使用電之加熱。
以下,利用實施例更具體地說明本發明,惟本發明不限於該等實施例。
實施例
本實施例係使用以下母材鋼板:具有以質量%計含有Si:3.1%、Al:0.6%及Mn:0.2%,且剩餘部分為Fe及不純物之化學成分,板厚為0.30mm且算術平均粗度Ra為0.32µm之母材鋼板。
在母材鋼板表面以塗佈量成為1.0g/m2
之方式塗佈具有表1所示組成之處理液後,以表2所示條件進行燒附處理。又,表1所示水溶性有機化合物之種類符號的意思如表3所示。另外,表2中之加熱速度意指從室溫至加熱溫度為止的平均加熱速度,加熱時間則指在該加熱溫度下維持的時間。
[表1]
[表2]
[表3]
磷酸金屬鹽係將正磷酸與Al(OH)3
、ZnO、Mg(OH)2
等各金屬氫氧化物、氧化物及碳酸鹽混合攪拌,調製出各磷金屬酸鹽處理液,並作成40質量%水溶液。又,所使用之試劑皆為市售品。
表1係以質量份之形式顯示磷酸金屬鹽中之磷酸鋁摻混量、磷酸金屬鹽中之磷酸鋅摻混量及磷酸金屬鹽中之第3元素之磷酸金屬鹽的摻混量。另外,表1中亦列示磷酸金屬鹽中之鋁元素與鋅元素之莫耳比。
水溶性有機化合物亦使用市售品,且各自具有表3所示之SP值。
關於丙烯酸樹脂,係使甲基丙烯酸甲酯30質量%、苯乙烯單體45質量%、甲基丙烯酸2-羥乙酯10質量%、乙二醇甲基丙烯酸酯5質量%與陰離子性反應性乳化劑5質量%、非離子性反應性乳化劑5質量%共聚後,作成30%乳液溶液,使用所得之物作為丙烯酸樹脂。又,丙烯酸樹脂之聚合所用之各試劑皆為市售品。
關於環氧樹脂,係使用以單乙醇胺將雙酚A環氧樹脂加以改質後,接枝聚合琥珀酸酐並使其乳液化者。又,環氧樹脂之聚合所用之各試劑皆為市售品。
表1所示處理液中之磷酸金屬鹽、水溶性有機化合物及有機樹脂的摻混比率會係塗佈、乾燥後之絕緣被膜中之磷酸金屬鹽、水溶性有機化合物及有機樹脂的摻混比率。
針對所得之無方向性電磁鋼板之各試樣,測定XPS光譜且判斷是否滿足上述條件(a)及條件(b)。滿足之條件評為評分「A」,未滿足之條件則評為評分「B」。另,XPS光譜之測定條件如前述。
並且,針對各試樣實施各種評估試驗。以下,詳細說明所製造之試樣的評估方法。
密著性係於具有10mm、20mm、30mm直徑的金屬棒捲附了貼有黏著膠帶的鋼板試樣後,剝除黏著膠帶,從剝落痕跡評估密著性。將即便在10mmφ之彎曲下仍無剝落者評為評分「A」,在20mmφ下無剝落者評為評分「B」,在30mmφ下無剝落者評為評分「C」,有剝落者則評為評分「D」。關於密著性,係以評分A、B者為合格。
絕緣性係根據依據JIS法(JIS C2550-4:2019)測定之層間電阻,將小於5Ω・cm2
/片評為評分「D」,在5Ω・cm2
/片以上且小於10Ω・cm2
/片評為評分「C」,在10Ω・cm2
/片以上且小於50Ω・cm2
/片評為評分「B」,在50Ω・cm2
/片以上則評為評分「A」。關於絕緣性,係以評分A、B者為合格。
耐熱性係以弛力退火後之耐蝕性來評估。在850℃之氮100%氣體環境中進行1小時加熱處理,接著於溫度50℃、濕度90%之恆溫恆濕槽中經過48小時後,與耐蝕性之評估同樣地評估表面生鏽的面積率。評估基準如以下所述,令評分9、10為「A」,評分6、7、8為「B」,評分4、5為「C」,評分1、2、3為「D」,以評分A、B者為合格。
針對加工性,係測定試樣之裁切荷重作為加工性之指標。設置成裁切刀係對加工成3cm×6cm之試樣垂直碰觸,測定裁切試樣時之荷重。以無塗佈絕緣被膜之試樣作比較時的裁切荷重之比小於0.95者評為「A」,在0.95以上且小於1.00者評為「B」,在1.00以上且小於1.05者評為「C」,在1.05以上且小於1.10者評為「D」,在1.10以上者則評為「E」。關於加工性,係以評分A、B者為合格。
耐蝕性係依據JIS法之鹽水噴霧試驗(JIS Z2371:2015)進行評估。具體而言,係將以下製程設為1循環,在重複進行5循環後,以10分之方式評估表面生鏽的面積率,前述製程為在35℃之氣體環境中對試樣噴霧5% NaCl水溶液1小時之製程;在溫度60℃、濕度40%之氣體環境中維持3小時之製程;及,在溫度40℃、濕度95%之氣體環境中維持3小時之製程。評估基準如下。關於耐蝕性,以評分5以上為合格。
10:無生鏽
9:有極少量生鏽(面積率0.10%以下)
8:有生鏽的面積率=大於0.10%且在0.25%以下
7:有生鏽的面積率=大於0.25%且在0.50%以下
6:有生鏽的面積率=大於0.50%且在1.0%以下
5:有生鏽的面積率=大於1.0%且在2.5%以下
4:有生鏽的面積率=大於2.5%且在5.0%以下
3:有生鏽的面積率=大於5.0%且在10%以下
2:有生鏽的面積率=大於10%且在25%以下
1:有生鏽的面積率=大於25%且在50%以下
外觀係將具光澤、平滑且均勻者評為5,以下,具光澤但均勻性稍差者評為4,稍有光澤且平滑但均勻性差者評為3,光澤較少、平滑性稍差且均勻性差者評為2,光澤、均勻性及平滑性差者則評為1。關於外觀,以評分3以上為合格。
並且,針對各試樣,利用電磁式膜厚計測定絕緣被膜之膜厚,從母材鋼板各面之絕緣被膜的測定值及母材鋼板板厚d(300µm)算出占積率(%)。又,本實施例之占積率可使用圖1所示之絕緣被膜之膜厚d1
(µm),以占積率(%)={300µm/(300µm+2×d1
)}×100算出。
將所得結果彙整列示於表4。
[表4]
從表4可明瞭,滿足本發明規定之本發明例的試樣在不含有鉻酸化合物的前提下,在絕緣性、加工性、密著性、耐蝕性及耐熱性方面顯示出更優異的特性。另一方面,落在本發明規定之任一項外之比較例的試樣無法實現兼具絕緣性、加工性、密著性、耐蝕性及耐熱性的特性。
1:無方向性電磁鋼板
11:母材鋼板
13:絕緣被膜
d1
:絕緣被膜之膜厚
d:板厚
圖1係用以說明本發明實施形態之無方向性電磁鋼板之構造的示意圖。
圖2係用以說明無方向性電磁鋼板之絕緣被膜中之XPS光譜行為的圖表。
圖3係用以說明無方向性電磁鋼板之絕緣被膜中之XPS光譜行為的圖表。
圖4係用以說明無方向性電磁鋼板之絕緣被膜中之XPS光譜行為的圖表。
1:無方向性電磁鋼板
11:母材鋼板
13:絕緣被膜
d1:絕緣被膜之膜厚
d:板厚
Claims (6)
- 一種無方向性電磁鋼板,具備母材鋼板及形成於前述母材鋼板表面之絕緣被膜;前述絕緣被膜中相對於前述絕緣被膜之總質量,含有合計50質量%以上之磷酸金屬鹽、有機樹脂及水溶性有機化合物;前述水溶性有機化合物之SP值在10.0~20.0(cal/cm3)1/2之範圍內;前述磷酸金屬鹽包含鋁及鋅作為金屬元素;當從前述絕緣被膜表面沿前述無方向電磁鋼板之厚度方向藉由光電子能譜分析法進行測定時,鋅之2p波峰強度達最大之深度存在於較鋁之2p波峰強度達最大之深度更靠前述表面側,並且鋅之2p波峰強度之最大值係在前述鋅之2p波峰強度達最大之深度中之鋁之2p波峰強度的1~20倍。
- 如請求項1之無方向性電磁鋼板,其中前述絕緣被膜含有相對於前述磷酸金屬鹽100質量份為3~50質量份之丙烯酸樹脂作為前述有機樹脂。
- 如請求項1或請求項2之無方向性電磁鋼板,其中前述磷酸金屬鹽更包含選自於由Co、Mg、Mn及Ni所構成群組中之1種以上作為金屬元素。
- 一種如請求項1至請求項3中任一項之無方向性電磁鋼板的處理方法,其包含使用表面處理劑於前述母材鋼板形成絕緣被膜之步驟;該表面處理劑中相對於含鋁及鋅之磷酸金屬鹽100質量份,包含有機樹脂3~50質量份及水溶性有機化合物5~50質量份;前述水溶性有機化合物之SP值在10.0~20.0(cal/cm3)1/2之範圍內;並且前述磷酸金屬鹽中之鋁元素與鋅元素之莫耳比(Al:Zn)在10:90~75:25之範圍內。
- 如請求項4之無方向性電磁鋼板的處理方法,其中前述有機樹脂為丙烯酸樹脂。
- 如請求項4或請求項5之無方向性電磁鋼板的處理方法,其中前述表面處理劑更包含:具有選自於由Co、Mg、Mn及Ni所構成群組中之1種以上元素之磷酸金屬鹽。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2019-171251 | 2019-09-20 | ||
JP2019171251 | 2019-09-20 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW202120744A TW202120744A (zh) | 2021-06-01 |
TWI823024B true TWI823024B (zh) | 2023-11-21 |
Family
ID=74883560
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW109132414A TWI823024B (zh) | 2019-09-20 | 2020-09-18 | 無方向性電磁鋼板及無方向性電磁鋼板用表面處理劑 |
Country Status (8)
Country | Link |
---|---|
US (1) | US20220341043A1 (zh) |
EP (1) | EP4033005A4 (zh) |
JP (1) | JP7389368B2 (zh) |
KR (1) | KR20220061209A (zh) |
CN (1) | CN114423885A (zh) |
BR (1) | BR112022004260A2 (zh) |
TW (1) | TWI823024B (zh) |
WO (1) | WO2021054450A1 (zh) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117157426A (zh) * | 2021-03-30 | 2023-12-01 | 日本制铁株式会社 | 无取向性电磁钢板及其制造方法 |
JP7215644B1 (ja) * | 2021-03-31 | 2023-01-31 | 日本製鉄株式会社 | 無方向性電磁鋼板及びその製造方法 |
CN116888301A (zh) * | 2021-03-31 | 2023-10-13 | 日本制铁株式会社 | 无取向性电磁钢板及其制造方法 |
CN114525502A (zh) * | 2022-02-16 | 2022-05-24 | 上海岱森化工科技有限公司 | 无方向性电磁钢板用绝缘皮膜处理剂 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3397291B2 (ja) | 1997-09-01 | 2003-04-14 | 新日本製鐵株式会社 | 被膜特性に優れた絶縁被膜を有する無方向性電磁鋼板及びその製造方法並びにその製造に用いる絶縁被膜形成剤 |
US6159534A (en) * | 1998-11-23 | 2000-12-12 | Nippon Steel Corporation | Method for producing non-oriented electromagnetic steel sheet having insulating film excellent in film properties |
CN100465337C (zh) * | 1998-12-17 | 2009-03-04 | 新日本制铁株式会社 | 非取向型电磁钢板的制备方法及所用的绝缘膜形成剂 |
KR100928798B1 (ko) * | 2007-11-13 | 2009-11-25 | 주식회사 포스코 | 향상된 내알칼리성과 가공성을 갖는 크롬 프리 수지 용액조성물, 이를 이용한 강판의 표면처리 방법 및 표면처리된 강판 |
JP6455526B2 (ja) * | 2014-12-26 | 2019-01-23 | 新日鐵住金株式会社 | 電磁鋼板 |
CN107002244B (zh) * | 2014-12-26 | 2019-06-07 | 新日铁住金株式会社 | 电磁钢板 |
US10706998B2 (en) | 2015-02-26 | 2020-07-07 | Nippon Steel Corporation | Electrical steel sheet and method for producing electrical steel sheet |
JP6682892B2 (ja) * | 2016-02-08 | 2020-04-15 | 日本製鉄株式会社 | 電磁鋼板及び電磁鋼板の製造方法 |
-
2020
- 2020-09-18 TW TW109132414A patent/TWI823024B/zh active
- 2020-09-18 WO PCT/JP2020/035519 patent/WO2021054450A1/ja unknown
- 2020-09-18 EP EP20865681.9A patent/EP4033005A4/en active Pending
- 2020-09-18 BR BR112022004260A patent/BR112022004260A2/pt unknown
- 2020-09-18 CN CN202080065947.4A patent/CN114423885A/zh active Pending
- 2020-09-18 US US17/761,958 patent/US20220341043A1/en active Pending
- 2020-09-18 KR KR1020227011969A patent/KR20220061209A/ko unknown
- 2020-09-18 JP JP2021546985A patent/JP7389368B2/ja active Active
Also Published As
Publication number | Publication date |
---|---|
JP7389368B2 (ja) | 2023-11-30 |
EP4033005A1 (en) | 2022-07-27 |
TW202120744A (zh) | 2021-06-01 |
US20220341043A1 (en) | 2022-10-27 |
EP4033005A4 (en) | 2022-11-09 |
CN114423885A (zh) | 2022-04-29 |
WO2021054450A1 (ja) | 2021-03-25 |
KR20220061209A (ko) | 2022-05-12 |
JPWO2021054450A1 (zh) | 2021-03-25 |
BR112022004260A2 (pt) | 2022-05-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI823024B (zh) | 無方向性電磁鋼板及無方向性電磁鋼板用表面處理劑 | |
KR101774187B1 (ko) | 크롬 프리 장력 피막용 처리액, 크롬 프리 장력 피막의 형성 방법, 및 크롬 프리 장력 피막 형성 방향성 전기 강판 | |
JP6547835B2 (ja) | 方向性電磁鋼板、及び方向性電磁鋼板の製造方法 | |
KR101867257B1 (ko) | 방향성 전기 강판용의 크롬 프리 절연 피막 처리액 및 크롬 프리 절연 피막 형성 방향성 전기 강판 | |
CN108866529B (zh) | 一种耐蚀性和耐高温性优良的环保钝化镀铝硅钢板及生产方法 | |
JP6682892B2 (ja) | 電磁鋼板及び電磁鋼板の製造方法 | |
KR20210151994A (ko) | 전자 강판 | |
CN103025917A (zh) | 电磁钢板及其制造方法 | |
JP6682888B2 (ja) | 方向性電磁鋼板の絶縁被膜用処理剤、方向性電磁鋼板、及び、方向性電磁鋼板の絶縁被膜処理方法 | |
JP6299938B1 (ja) | クロムフリー絶縁張力被膜付き方向性電磁鋼板およびその製造方法 | |
TWI406968B (zh) | An electromagnetic steel sheet having an insulating film excellent in thermal conductivity, and a method of manufacturing the same | |
TWI748654B (zh) | 無方向性電磁鋼板 | |
JP5633402B2 (ja) | クロムレス張力被膜付き方向性電磁鋼板 | |
JP3564079B2 (ja) | 絶縁被膜剤とそれを用いた溶接性の極めて優れる無方向性電磁鋼板の製造方法 | |
JP5633401B2 (ja) | クロムレス張力被膜用処理液およびクロムレス張力被膜の形成方法 | |
JPH0711453A (ja) | 亜鉛含有金属めっき鋼板の表面処理組成物および表面処理方法 | |
JP4112866B2 (ja) | 被膜性能の優れる無方向性電磁鋼板 | |
WO2024048655A1 (ja) | 表面処理鋼板 | |
JP2018090836A (ja) | 無方向性電磁鋼板 | |
JP3555336B2 (ja) | 積層溶接時および溶接後に不快臭の少ない電磁鋼板用絶縁皮膜の形成方法 | |
JPH11158650A (ja) | 金属材料表面処理用水系樹脂クロメート組成物及び金属材料の表面処理方法 |