WO2015037322A1 - Coated aluminum material for capacitor case - Google Patents
Coated aluminum material for capacitor case Download PDFInfo
- Publication number
- WO2015037322A1 WO2015037322A1 PCT/JP2014/068602 JP2014068602W WO2015037322A1 WO 2015037322 A1 WO2015037322 A1 WO 2015037322A1 JP 2014068602 W JP2014068602 W JP 2014068602W WO 2015037322 A1 WO2015037322 A1 WO 2015037322A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- coating film
- resistance
- coating
- diisocyanate
- aluminum
- Prior art date
Links
- 239000000463 material Substances 0.000 title claims abstract description 51
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 47
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000003990 capacitor Substances 0.000 title claims abstract description 38
- 238000000576 coating method Methods 0.000 claims abstract description 124
- 239000011248 coating agent Substances 0.000 claims abstract description 121
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims abstract description 34
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 230000009477 glass transition Effects 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 16
- 230000008961 swelling Effects 0.000 claims abstract description 12
- 125000005442 diisocyanate group Chemical group 0.000 claims description 36
- 229920000570 polyether Polymers 0.000 claims description 26
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 25
- 229920001228 polyisocyanate Polymers 0.000 claims description 23
- 239000005056 polyisocyanate Substances 0.000 claims description 23
- 239000008199 coating composition Substances 0.000 claims description 19
- 125000002947 alkylene group Chemical group 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 6
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical group OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 24
- 230000007797 corrosion Effects 0.000 abstract description 23
- 238000005260 corrosion Methods 0.000 abstract description 23
- 230000000903 blocking effect Effects 0.000 abstract description 18
- -1 secondary adhesion Substances 0.000 abstract description 15
- 239000003599 detergent Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 23
- 229920005989 resin Polymers 0.000 description 22
- 239000011347 resin Substances 0.000 description 22
- 238000004140 cleaning Methods 0.000 description 21
- 238000009413 insulation Methods 0.000 description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 238000000465 moulding Methods 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 12
- 229910000838 Al alloy Inorganic materials 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 238000002845 discoloration Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000001993 wax Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 229920001225 polyester resin Polymers 0.000 description 5
- 239000004645 polyester resin Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- WMYWOWFOOVUPFY-UHFFFAOYSA-L dihydroxy(dioxo)chromium;phosphoric acid Chemical compound OP(O)(O)=O.O[Cr](O)(=O)=O WMYWOWFOOVUPFY-UHFFFAOYSA-L 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 239000010407 anodic oxide Substances 0.000 description 3
- 239000002981 blocking agent Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000004210 ether based solvent Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000010409 ironing Methods 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007610 electrostatic coating method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/08—Housing; Encapsulation
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4028—Isocyanates; Thioisocyanates
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
Definitions
- the present invention has excellent deep drawability, film adhesion, insulation, high temperature water resistance, secondary adhesion, cleaning solution resistance, corrosion resistance, blocking resistance, printability, and further cost and safety. ⁇ It relates to aluminum coating materials for capacitor cases that are excellent in terms of environment.
- the capacitor case is cylindrical and has various height / diameter ratios.
- molding is performed under severe conditions in combination with deep drawing and ironing. Therefore, when a general resin-coated aluminum alloy plate material used for building materials or the like is applied, the resin layer is cracked or peeled off, and sufficient insulation cannot be obtained. In particular, this tendency is remarkable in molding of a case having a large height / diameter ratio.
- Patent Document 1 discloses a resin-coated aluminum material that is used for a capacitor case or the like and has excellent moldability, heat discoloration resistance, and high temperature and high humidity durability.
- This resin-coated aluminum material forms a nonporous anodic oxide film having a porosity of 5% or less on the surface of pure aluminum or aluminum alloy, and an epoxy resin having a number average molecular weight of 2000 to 100,000 is formed on the upper layer thereof as a silane coupling agent It has a structure coated via.
- the nonporous anodic oxide film has a thickness of 30 to 200 nm, the silane coupling agent is applied on the nonporous anodic oxide film in an amount of 0.5 to 10 mg / m 2 , and the epoxy resin.
- the number average molecular weight is preferably 5,000 to 80,000 and the coating thickness is preferably 2 to 20 ⁇ m.
- Patent Document 2 (A) a film-forming resin composition containing a hydroxyl group-containing resin and a blocked isocyanate curing agent, (B) an inorganic compound surface-treated with a nitrogen-containing compound having an aldehyde compound adsorption ability, and (C) The titanium phosphate compound is contained in a proportion of 0.1 to 10 parts by weight of component (B) and 0.1 to 10 parts by weight of component (C) with respect to 100 parts by weight of component (A).
- a thermosetting coating composition for pre-coating and a pre-coating metal plate obtained by coating it on a metal plate are disclosed.
- the hydroxyl group-containing resin contained in the component (A) a hydroxyl group-containing polyester resin having a hydroxyl value of 5 to 200 mgKOH / g and a number average molecular weight of 1,000 to 20,000 is disclosed.
- Patent Document 3 includes polyethylene wax and / or carnauba wax, the resin layer thickness is 2 ⁇ m or more and 22 ⁇ m or less, and the sum of the lengths of wax particles that can be cut by one straight line having a length of 100 ⁇ m on the surface of the resin layer is 10 ⁇ m. There are 3 or more and 50 or less wax particles having a long-diameter portion that is 80% or less of the resin layer thickness and 0.1 ⁇ m or more, and the resin layer thickness is 80 or less.
- a resin-coated aluminum alloy sheet for an aluminum electrolytic capacitor case is disclosed in which the number of wax particles having a major axis portion of more than% is less than ten.
- the resin-coated aluminum materials of Patent Document 1 and Patent Document 2 are excellent in moldability because an epoxy resin or a polyester resin is formed on the outermost surface.
- the coating liquid may be modified or dissolved by the cleaning liquid for removing the used press oil.
- the secondary adhesion is inferior, and the resin film may be peeled off or discolored. As a result, there is a problem that insulation failure occurs and reliability of the capacitor itself is impaired.
- the object of the present invention is good moldability that can be molded into a capacitor case, as well as insulation after molding as a capacitor case, high-temperature water resistance, secondary adhesion, cleaning liquid resistance, corrosion resistance, blocking resistance,
- the object is to provide an aluminum coating material for capacitor cases that is excellent in printability, cost, safety, and environment.
- An aluminum coating material for a capacitor case according to the present invention includes an aluminum base material, a chemical conversion film formed on at least one surface of the aluminum base material, and a coating film formed on the chemical conversion film.
- the coating film is mainly composed of bisphenol A epoxy resin, has a degree of swelling with methyl ethyl ketone of less than 1.5, a surface free energy of 36 mN / m to 50 mN / m, and a glass transition temperature of 50 ° C. to 100 ° C. It is characterized by being at ° C.
- the coating film is a cured product of a coating composition containing bisphenol A epoxy resin and polyisocyanate, and the weight ratio of the bisphenol A epoxy resin to the polyisocyanate is 50/50 to 90/10.
- the polyisocyanate is preferably a diisocyanate having a polyether skeleton.
- the polyisocyanate is a diisocyanate having a polyether skeleton and a diisocyanate having an alkylene chain, and the weight ratio of the diisocyanate having the polyether skeleton and the diisocyanate having the alkylene chain is 50/50 to 95/5 is preferable.
- the polyether skeleton is preferably a neopentyl glycol skeleton.
- the aluminum coating material for a capacitor case according to the present invention has high formability required for the capacitor case, insulation after processing, high-temperature water resistance that can withstand harsh environments, and secondary adhesion. Furthermore, it has excellent cleaning solution resistance that does not denature even when exposed to a cleaning solution, and further has excellent corrosion resistance, blocking resistance, and printability.
- the aluminum coating material for a capacitor case according to the present invention includes an aluminum or aluminum alloy base material, a chemical conversion film formed on at least one surface of the base material, and a coating film formed on the chemical conversion film.
- the base material used in the present invention is a base material made of aluminum or an aluminum alloy.
- a base material made of aluminum and an aluminum alloy is simply referred to as an “aluminum base material”.
- metals other than aluminum can also be used for a base material.
- the chemical conversion film used in the present invention may be a coating type or a reactive type, but a reactive type is preferable from the viewpoint of adhesion to an aluminum substrate and a coating film. Specifically, it is a film formed with a treatment liquid such as phosphate chromate, chromate chromate, zirconium phosphate, or titanium phosphate. From the viewpoint of corrosion resistance, secondary adhesion, and economical efficiency, phosphoric acid chromate is more preferable.
- the adhesion amount of the phosphate chromate film is preferably 2 mg / m 2 to 50 mg / m 2 in terms of metallic Cr element.
- the adhesion amount is less than 2 mg / m 2 in terms of Cr element, sufficient corrosion resistance cannot be obtained, and further, secondary adhesion with the coating film cannot be obtained. Moreover, even if the adhesion amount exceeds 50 mg / m 2 in terms of Cr element, the effect of corrosion resistance and secondary adhesion with the coating film is saturated and lacks economic efficiency.
- Preferred coating weight is 5mg / m 2 ⁇ 40mg / m 2 of Cr in terms of element.
- the coating film used in the present invention is composed mainly of bisphenol A epoxy resin, has a degree of swelling of less than 1.5 by methyl ethyl ketone (hereinafter referred to as MEK), a surface free energy of 36 mN / m to 50 mN / m, and a glass transition temperature. 50 ° C to 100 ° C.
- MEK methyl ethyl ketone
- the main component of the coating film is bisphenol A epoxy resin, and the glass transition temperature of the coating film is set to 50 ° C. to 100 ° C., thereby making it possible to suppress a decrease in secondary adhesion. .
- the glass transition temperature of the coating film is less than 50 ° C., when the aluminum base material is stacked after coating, the material sticks and the productivity is significantly reduced. The phenomenon in which these materials stick together is called blocking, and the property of not sticking even if the state where the coating film is pressed continues for a long time is called blocking resistance.
- the glass transition temperature of a coating film exceeds 100 degreeC, the distortion at the time of a shaping
- the printability can be sufficiently ensured by setting the surface free energy of the coating film to 36 mN / m to 50 mN / m.
- one method for improving moldability is to add a lubricant such as wax, but the added wax is exposed to the surface, and the surface free energy is reduced to less than 36 mN / m. There is. When the surface free energy of the coating film is less than 36 mN / m, the ink may be repelled or the printed part may be peeled off during printing.
- the surface free energy of the coating film can be calculated from the extended Fowkes equation based on the contact angle measured with a liquid having a known surface free energy.
- the degree of swelling of the coating film by MEK by setting the degree of swelling of the coating film by MEK to less than 1.5, dissolution of the coating film by molding oil at the time of molding or cleaning liquid after molding can be suppressed, and the resistance to cleaning liquid is increased. Can be granted.
- the degree of swelling by MEK is more preferably 1.2 or less.
- the coating oil swells, dissolves, discolors, and the like due to the molding oil at the time of molding and the cleaning liquid after molding, resulting in poor insulation.
- discoloration or dissolution of the coating film occurs, resulting in poor corrosion resistance.
- the coating film is preferably a cured product of a coating composition containing a bisphenol A epoxy resin.
- the bisphenol A epoxy resin is preferably used from the viewpoints of industrial versatility and good corrosion resistance.
- the weight average molecular weight of the bisphenol A epoxy resin is not particularly limited, but is, for example, 20,000 to 100,000.
- the epoxy equivalent is not particularly limited, but is, for example, 100 to 1000.
- One type of bisphenol A epoxy resin may be used, or two or more types of different types of bisphenol A epoxy resins may be used.
- the present inventors further include a polyisocyanate in the coating composition, and form a coating film in which the bisphenol A epoxy resin is cross-linked by a urethane bond, thereby providing moldability, insulation, secondary adhesion, and anti-washing liquid. It has been found that the property, corrosion resistance and blocking resistance can be improved.
- the weight ratio of bisphenol A epoxy resin and polyisocyanate is preferably 50/50 to 90/10.
- the content of the bisphenol A epoxy resin is 50 to 90 mass% with respect to the total amount of the bisphenol A epoxy resin and the polyisocyanate, the secondary adhesion and the cleaning liquid resistance can be satisfied. If the content of the bisphenol A epoxy resin is less than 50 mass%, the cleaning liquid resistance cannot be satisfied. Moreover, when content of bisphenol A epoxy resin exceeds 90 mass%, the glass transition temperature of a coating film will be high, a coating film will become strong and secondary adhesiveness cannot be satisfied.
- the polyisocyanate is preferably a diisocyanate having a polyether skeleton.
- the diisocyanate having a polyether skeleton is a compound in which a diisocyanate is derived from a polyether compound.
- Polyether compounds include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyneopentyl glycol and other glycols, compounds obtained by reacting these glycols, acrylic polyols, polyester polyethers And acrylic polyether.
- a neopentyl glycol skeleton is particularly preferable.
- a diisocyanate having a neopentyl glycol skeleton is contained, secondary adhesion and blocking resistance are excellent.
- polyisocyanate trifunctional or higher functional polyisocyanates such as a burette body, an adduct body and an isocyanurate body can be used.
- the block type polyisocyanate which masked the isocyanate group with the blocking agent.
- the blocking agent is, for example, active methylene such as phenol, alcohol, dimethyl malonate, and ethyl acetoacetate.
- the block type polyisocyanate is easy to handle and store because crosslinking starts when the blocking agent is dissociated by heating.
- the content of the diisocyanate having a polyether skeleton is 10 to 50 mass% with respect to the total amount of the bisphenol A epoxy resin and the diisocyanate having a polyether skeleton.
- the cleaning liquid resistance can be satisfied.
- the content of the diisocyanate having a polyether skeleton is less than 10 mass%, the glass transition temperature of the coating film is high, the coating film becomes strong, and the secondary adhesion tends to be inferior. Moreover, surface free energy becomes low and printability tends to be inferior.
- the content of the diisocyanate having a polyether skeleton exceeds 50 mass%, the degree of swelling and surface free energy due to MEK of the coating film increases, and the cleaning liquid resistance and printability tend to be inferior.
- the aluminum coating material of the present invention is used for a case for housing a capacitor mounted on an automobile, home appliance or the like. Such a capacitor must maintain the function of the capacitor in a severe environment such as high temperature and high humidity, and the capacitor case requires high-temperature water resistance.
- the present inventors have found that high-temperature water resistance can be improved by incorporating a diisocyanate having a polyether skeleton and a diisocyanate having an alkylene chain as a polyisocyanate in the coating composition.
- the weight ratio of the diisocyanate having a polyether skeleton and the diisocyanate having an alkylene chain is preferably 50/50 to 95/5.
- content of the diisocyanate having an alkylene chain is 5 to 50 mass% with respect to the total amount of the diisocyanate having a polyether skeleton and the diisocyanate having an alkylene chain, good moldability, insulation, secondary adhesion, The high temperature water resistance can be improved while maintaining the cleaning liquid property, the corrosion resistance, the blocking resistance and the printability.
- the content of diisocyanate having an alkylene chain is less than 5 mass%, good moldability, insulation, secondary adhesion, cleaning solution resistance, corrosion resistance, blocking resistance, and printability can be maintained, but in severe environments Discoloration or modification of the coating film occurs, and sufficient effects of high temperature and water resistance cannot be exhibited.
- the content of the diisocyanate having an alkylene chain exceeds 50 mass%, the degree of crosslinking of the urethane bond increases, and the high temperature water resistance can be satisfied, but the secondary adhesion cannot be satisfied.
- the diisocyanate having an alkylene chain has, for example, a structure in which isocyanate groups are added to both ends of the alkylene chain.
- the number of carbon atoms in the alkylene chain is preferably 1-10.
- the alkylene chain is preferably a hexamethylene chain.
- a coating composition containing a bisphenol A epoxy resin, a diisocyanate having a polyether skeleton, and a diisocyanate having an alkylene chain is applied on an aluminum substrate and baked, whereby a diisocyanate having a bisphenol A epoxy resin and a polyether skeleton. Are crosslinked to form a urethane bond, and the bisphenol A epoxy resin and the diisocyanate having an alkylene chain are crosslinked to form a urethane bond.
- the coating composition for forming a coating film in the present invention may contain a rust inhibitor, a leveling agent, a surfactant and the like, if necessary. Moreover, you may contain a coloring agent in the range which does not impair compatibility.
- the rust preventive include tannic acid, gallic acid, phytic acid, phosphinic acid and the like.
- the leveling agent include polyalcohol alkyl esters.
- the surfactant include alkyl sulfate ester salts, silicone oils, and fatty acids.
- the colorant include phthalocyanine compounds.
- a coating film can be formed by applying (coating) a liquid coating composition for a coating to the surface of the aluminum substrate of the present invention and baking it.
- the coating composition for forming a coating film in the present invention contains a solvent.
- Each component is prepared by dissolving and dispersing in a solvent.
- the solvent is not particularly limited as long as it can dissolve or disperse each component, for example, an aqueous solvent such as water, a ketone solvent such as acetone, ethyl ethyl ketone, cyclokexanone, an alcohol solvent such as ethanol, Examples include ethylene glycol alkyl ether solvents such as ethylene glycol monoethyl ether, propylene glycol alkyl ether solvents, and ester compounds of a series of glycol alkyl ether solvents.
- the total content of bisphenol A epoxy resin and polyisocyanate in the coating composition is preferably 5 to 50 mass%.
- the total content is less than 5 mass%, foaming or the like occurs during baking, and a coating film cannot be formed uniformly.
- the total content exceeds 50 mass%, the viscosity of the coating composition becomes high, handling is difficult, and it is difficult to apply the coating composition uniformly.
- a coating method of the coating composition methods such as a roll coater method, a spray method, and an electrostatic coating method are used, and a roll coater method having excellent coating film uniformity and good productivity is preferable.
- a roll coater method a gravure roll method with easy coating amount management, a natural coating method suitable for thick coating, a reverse coating method suitable for imparting an aesthetic appearance to the coated surface, and the like can be employed.
- a general heating method, a dielectric heating method, etc. are used for drying of a coating film.
- Baking at the time of forming the coating film is preferably performed at a baking temperature (reaching plate surface temperature) of 150 ° C. to 320 ° C.
- a baking temperature reaching plate surface temperature
- the coating film is not sufficiently formed and the adhesion with the chemical conversion film is lowered.
- the baking temperature exceeds 320 ° C., the coating film is denatured, the strength and elongation of the coating film are remarkably lowered, and the moldability is lowered.
- the baking time is preferably 1 to 120 seconds.
- the thickness of the coating film needs to be 1 ⁇ m to 20 ⁇ m, preferably 5 ⁇ m to 15 ⁇ m. If the thickness of the coating film is less than 1 ⁇ m, desired corrosion resistance and insulation cannot be obtained. On the other hand, if the thickness of the coating film is thicker than 20 ⁇ m, the corrosion resistance and insulation effects are saturated, which is uneconomical.
- the aluminum coated plate produced in this way is a capacitor case with a desired cylindrical shape by applying press processing oil for press forming to the surface and then performing forming processing such as slit processing and deep drawing processing. Is produced.
- a capacitor case is suitably used as an electrolytic capacitor, for example, but requires high workability, insulation, high-temperature water resistance, secondary adhesion, cleaning liquid resistance, corrosion resistance, blocking resistance, and printability. If it is possible, it can be used and is not particularly limited.
- coating compositions containing each component shown in Tables 1 to 3 were prepared.
- a solvent for the coating composition a mixed liquid of cyclohexanone and xylene (cyclohexanone 20 mass%) was used.
- a coating film was formed on the aluminum material surface as follows.
- An aluminum alloy plate (1100-H24 material, 0.30 mm thickness) was degreased with a weak alkaline degreasing solution, washed with water, and dried.
- the surface of the aluminum alloy plate treated in this manner was subjected to chemical conversion treatment using a commercially available phosphoric acid chromate treatment solution. In Comparative Example 11, no chemical conversion treatment was performed.
- Each coating composition was applied to this aluminum alloy plate with a roll coater.
- a final plate surface temperature (PMT) was 270 ° C., and the baking time was 42 seconds to obtain a specimen of an aluminum coating material.
- the film thickness was measured with an eddy current film thickness meter.
- Bisphenol A epoxy resin (A1): Bisphenol A epoxy resin having a weight average molecular weight of 28,000 Bisphenol A epoxy resin (A2): Bisphenol A epoxy resin having a weight average molecular weight of 50000 Bisphenol A epoxy resin (A3): Bisphenol A epoxy having a weight average molecular weight of 25,000
- Resin polyisocyanate (B1): Polyethylene glycol diisocyanate polyisocyanate (B2): Polypropylene glycol diisocyanate polyisocyanate (B3): Polyneopentyl glycol diisocyanate polyisocyanate (C1): Hexamethylene diisocyanate
- the diiodomethane dispersion component, dipole component, and hydrogen bond component are each 46.8 mN / m, 4 mN / m, and 0 mN / m, and the ethylene glycol dispersion component, dipole component, and hydrogen bond component were 30.1 mN / m, 0 mN / m, and 17.6 mN / m, respectively.
- Glass-transition temperature The glass transition temperature was evaluated by measuring dynamic viscoelasticity under the conditions of a frequency of 10 Hz, a temperature increase rate of 5.0 ° C./min, a sample length of 5 cm, and an amplitude of 0.01 mm. Tan ⁇ was calculated and the peak was taken as the glass transition temperature.
- Formability is evaluated by forming a capacitor case with a drawing ratio of 2.0, with the coated surface formed on the outer surface, and visually observing the formed coating film with a five-stage squeezing and ironing method. did.
- a volatile press oil having a kinematic viscosity of 1.6 mm 2 / s was used. Evaluation was performed based on the following evaluation criteria.
- X The surface is rough and further streaks are observed, and the cracks of the coating film can be confirmed visually. ⁇ , ⁇ , or ⁇ was accepted.
- the test material was printed with silk screen ink.
- the adhesion with the ink after UV curing was evaluated by the non-peeling rate of the grid by strip tape peeling.
- the silk screen ink used was RIG (trade name, manufactured by Seiko Advance Co., Ltd., UV curable metal ink).
- ⁇ No peeling 100/100
- ⁇ Partially peeled 1/100 to 99/100
- X Full surface peeling 0/100, or ink was smeared after printing and could not be used. ⁇ was accepted.
- Examples 1 to 21 have good moldability, film adhesion, insulation, high temperature water resistance, secondary adhesion, cleaning solution, corrosion resistance, blocking resistance and printability. there were.
- Examples 7 to 9 and 20 to 21 are remarkably excellent in moldability, cleaning liquid resistance, corrosion resistance, blocking resistance, and printability.
- Comparative Example 1 since a polyester resin was used as the base resin, high-temperature water resistance could not be satisfied.
- Comparative Example 2 since a polyester resin and polyacrylic acid were used as the base resin, the high temperature water resistance could not be satisfied.
- Comparative Example 3 since polypropylene was used as the base resin, the blocking resistance and printability could not be satisfied.
- Comparative Example 4 only the bisphenol A epoxy resin was used and no polyisocyanate was used. Therefore, the glass transition temperature was too high to satisfy the secondary adhesion. In Comparative Example 5, since a polyester resin was used as the base resin, high-temperature water resistance could not be satisfied.
- Comparative Example 6 since the glass transition temperature of the coating film was too low, the blocking resistance could not be satisfied. In Comparative Example 7, since the glass transition temperature of the coating film was too high, the secondary adhesion could not be satisfied. In Comparative Example 8, since the surface free energy of the coating film was too high, bleeding occurred during printing. In Comparative Example 9, since the degree of swelling of the coating film by MEK was too high, the washing resistance could not be satisfied. In Comparative Example 10, since the polyethylene wax was contained in the coating film, the surface free energy of the coating film was low, and the printability could not be satisfied. Since the comparative example 11 was not subjected to chemical conversion treatment, it could not satisfy the corrosion resistance and the secondary adhesion.
- the present invention is excellent in moldability, film adhesion, insulation, high temperature water resistance, secondary adhesion, cleaning liquid resistance, corrosion resistance, blocking resistance and printability, and also in cost, safety and environmental aspects.
- An aluminum coating material for a capacitor case having a coating film exhibiting performance on the surface was obtained.
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Abstract
Description
本発明における塗膜を形成する塗料組成物には、必要に応じて、防錆剤、レベリング剤、界面活性剤等を含有させてもよい。また、相溶性を損なわない範囲で着色剤を含有させてもよい。防錆剤としては、例えば、タンニン酸、没食子酸、フイチン酸、ホスフィン酸等が挙げられる。レベリング剤としては、例えば、ポリアルコールのアルキルエステル類等が挙げられる。界面活性剤としては、例えば、アルキル硫酸エステル塩、シリコーンオイル系、脂肪酸等が挙げられる。着色剤としては、例えば、フタロシアニン化合物等が挙げられる。 (Other additives)
The coating composition for forming a coating film in the present invention may contain a rust inhibitor, a leveling agent, a surfactant and the like, if necessary. Moreover, you may contain a coloring agent in the range which does not impair compatibility. Examples of the rust preventive include tannic acid, gallic acid, phytic acid, phosphinic acid and the like. Examples of the leveling agent include polyalcohol alkyl esters. Examples of the surfactant include alkyl sulfate ester salts, silicone oils, and fatty acids. Examples of the colorant include phthalocyanine compounds.
本発明のアルミニウム基材表面に塗膜用の液状の塗料組成物を塗装(塗布)し、それを焼付けることにより、塗膜を形成しうる。 (Formation of coating film)
A coating film can be formed by applying (coating) a liquid coating composition for a coating to the surface of the aluminum substrate of the present invention and baking it.
ビスフェノールAエポキシ樹脂(A1):重量平均分子量28000のビスフェノールAエポキシ樹脂
ビスフェノールAエポキシ樹脂(A2):重量平均分子量50000のビスフェノールAエポキシ樹脂
ビスフェノールAエポキシ樹脂(A3):重量平均分子量25000のビスフェノールAエポキシ樹脂
ポリイソシアネート(B1):ポリエチレングリコールジイソシアネート
ポリイソシアネート(B2):ポリプロピレングリコールジイソシアネート
ポリイソシアネート(B3):ポリネオペンチルグリコールジイソシアネート
ポリイソシアネート(C1):ヘキサメチレンジイソシアネート (Each component in the coating composition)
Bisphenol A epoxy resin (A1): Bisphenol A epoxy resin having a weight average molecular weight of 28,000 Bisphenol A epoxy resin (A2): Bisphenol A epoxy resin having a weight average molecular weight of 50000 Bisphenol A epoxy resin (A3): Bisphenol A epoxy having a weight average molecular weight of 25,000 Resin polyisocyanate (B1): Polyethylene glycol diisocyanate polyisocyanate (B2): Polypropylene glycol diisocyanate polyisocyanate (B3): Polyneopentyl glycol diisocyanate polyisocyanate (C1): Hexamethylene diisocyanate
供試材をMEKに24時間浸漬し、表面に付着しているMEKを拭き取り、重量を測定した。その後供試材を十分乾燥し、塗膜中のMEKを蒸発させ、脱膜し、塗膜量を測定した。
膨潤度=(MEKにて膨潤した塗膜量)/(乾燥した塗膜量) (Swelling degree by MEK)
The test material was immersed in MEK for 24 hours, MEK adhering to the surface was wiped off, and the weight was measured. Thereafter, the test material was sufficiently dried, MEK in the coating film was evaporated, the film was removed, and the coating amount was measured.
Swelling degree = (Amount of coating film swollen with MEK) / (Amount of dried coating film)
表面自由エネルギーの各成分が既知の液体として、蒸留水、ジヨードメタン及びエチレングリコールを各供試材に滴下した。各液体の接触角を測定し、表面自由エネルギーを算出した。なお、水の分散成分、双極子成分、水素結合成分はそれぞれ、29.1mN/m、1.3mN/m、42.4mN/mとし、ジヨードメタンの分散成分、双極子成分、水素結合成分はそれぞれ、46.8mN/m、4mN/m、0mN/mとし、エチレングリコールの分散成分、双極子成分、水素結合成分はそれぞれ、30.1mN/m、0mN/m、17.6mN/mとした。 (Surface free energy)
Distilled water, diiodomethane, and ethylene glycol were added dropwise to each specimen as liquids with known components of surface free energy. The contact angle of each liquid was measured, and the surface free energy was calculated. The water dispersion component, dipole component, and hydrogen bond component are 29.1 mN / m, 1.3 mN / m, and 42.4 mN / m, respectively. The diiodomethane dispersion component, dipole component, and hydrogen bond component are each 46.8 mN / m, 4 mN / m, and 0 mN / m, and the ethylene glycol dispersion component, dipole component, and hydrogen bond component were 30.1 mN / m, 0 mN / m, and 17.6 mN / m, respectively.
ガラス転移温度は、周波数10Hz、温度上昇速度5.0℃/min、サンプル長5cm、振幅0.01mmの条件で動的粘弾性を測定することにより評価した。tanδを計算しそのピークをガラス転移温度とした。 (Glass-transition temperature)
The glass transition temperature was evaluated by measuring dynamic viscoelasticity under the conditions of a frequency of 10 Hz, a temperature increase rate of 5.0 ° C./min, a sample length of 5 cm, and an amplitude of 0.01 mm. Tan δ was calculated and the peak was taken as the glass transition temperature.
成形性は、5段の絞りしごき成形方式にて、塗膜が形成されている側を外面にして絞り比2.0のコンデンサケースに成形し、成形後の塗膜を目視観察することにより評価した。成形の際、動粘度1.6mm2/sの揮発性プレス油を使用した。下記評価基準に基づいて評価した。
◎:成形前後において変化がない。
○:表面が若干荒れており、目視では変化ないが、拡大すると塗膜の微小な亀裂が確認される。
△:表面が荒れており、目視でも塗膜の亀裂が確認できる。
×:表面が荒れて更に筋が観察され、目視でも塗膜の亀裂が確認できる。
◎、○、または△を合格とした。 (Formability)
Formability is evaluated by forming a capacitor case with a drawing ratio of 2.0, with the coated surface formed on the outer surface, and visually observing the formed coating film with a five-stage squeezing and ironing method. did. During molding, a volatile press oil having a kinematic viscosity of 1.6 mm 2 / s was used. Evaluation was performed based on the following evaluation criteria.
A: No change before and after molding.
○: The surface is slightly rough and does not change visually, but when enlarged, a minute crack of the coating is confirmed.
(Triangle | delta): The surface is rough and the crack of a coating film can also be confirmed visually.
X: The surface is rough and further streaks are observed, and the cracks of the coating film can be confirmed visually.
◎, ○, or △ was accepted.
成形品の側壁部におけるテープ剥離試験を実施し、塗膜の残存状況目視で観察した。下記評価基準に基づいて評価した。
○:塗膜の剥離が確認されなかった。
×:塗膜が剥離した。
○を合格とした。 (Film adhesion)
A tape peeling test was performed on the side wall of the molded product, and the remaining state of the coating film was visually observed. Evaluation was performed based on the following evaluation criteria.
○: No peeling of the coating film was confirmed.
X: The coating film peeled off.
○ was accepted.
JIS K 6911に準拠した絶縁性試験を実施し、表面抵抗を測定した。下記評価基準に基づいて評価した。
◎:表面抵抗≧1014Ω
○:1014Ω>表面抵抗≧1010Ω
△:1010Ω>表面抵抗≧106Ω
×:106Ω>表面抵抗
◎、○又は△を合格とした。 (Insulation)
An insulation test according to JIS K 6911 was performed, and the surface resistance was measured. Evaluation was performed based on the following evaluation criteria.
A: Surface resistance ≧ 10 14 Ω
○: 10 14 Ω> surface resistance ≧ 10 10 Ω
Δ: 10 10 Ω> surface resistance ≧ 10 6 Ω
×: 10 6 Ω> Surface resistance ◎, ○, or Δ was regarded as acceptable.
上記の成形品を、121℃の水蒸気に5日間暴露した。樹脂塗膜の変色状況を目視で観察した。下記評価基準に基づいて評価した。
◎:塗膜の変色が確認されなかった。
○:塗膜の一部が変色したものの、製品の使用に耐えうる。
×:塗膜全体が変色した。
◎、○を合格とした。 (High temperature water resistance)
The above molded product was exposed to water vapor at 121 ° C. for 5 days. The discoloration state of the resin coating film was visually observed. Evaluation was performed based on the following evaluation criteria.
(Double-circle): Discoloration of the coating film was not confirmed.
○: Although a part of the coating film is discolored, the product can be used.
X: The whole coating film discolored.
◎ and ○ were accepted.
上記の成形品を、121℃の水蒸気に5日間暴露した。成形品の側壁部におけるテープ剥離試験を実施し、塗膜の残存状況にて評価した。下記評価基準に基づいて評価した。
○:塗膜の剥離が確認されなかった。
×:塗膜が剥離した。
○を合格とした。 (Secondary adhesion)
The above molded product was exposed to water vapor at 121 ° C. for 5 days. A tape peeling test was performed on the side wall portion of the molded product, and the remaining state of the coating film was evaluated. Evaluation was performed based on the following evaluation criteria.
○: No peeling of the coating film was confirmed.
X: The coating film peeled off.
○ was accepted.
洗浄液として使用されるアクアソルベントG(炭化水素系洗浄剤:アクア化学株式会社製、登録商標)に浸漬(常温にて1時間浸漬)し、塗膜の変色状況を目視で観察した。下記評価基準に基づいて評価した。
◎:塗膜の溶解、変色が確認されなかった。
○:塗膜の一部が変色するものの、製品の使用に耐えうる。
△:塗膜は溶解しないものの、変色が確認された。
×:塗膜が溶解した。
◎、○又は△を合格とした。 (Cleaning liquid resistance)
The film was immersed in Aqua Solvent G (hydrocarbon-based cleaning agent: Aqua Chemical Co., Ltd., registered trademark) used as a cleaning solution (immersion for 1 hour at room temperature), and the discoloration of the coating film was visually observed. Evaluation was performed based on the following evaluation criteria.
A: Dissolution or discoloration of the coating film was not confirmed.
○: Although a part of the coating film changes color, it can withstand the use of the product.
(Triangle | delta): Although the coating film did not melt | dissolve, discoloration was confirmed.
X: The coating film dissolved.
◎, ○ or △ was regarded as acceptable.
JIS Z2371に基づき、塩水噴霧試験を1000時間行い、レイティングナンバー(R.N.)により耐食性を測定した。
R.N 9.0以上を合格とした。 (Corrosion resistance)
Based on JIS Z2371, the salt spray test was performed for 1000 hours, and corrosion resistance was measured by rating number (RN).
R. N 9.0 or higher was considered acceptable.
各材料の塗装面と化成皮膜面を重ね合わせ、その上から、2kPaの荷重をかけ、50℃にて1日間保管し、塗膜の貼り付き状態を目視で観察した。
○:塗膜の変化・貼り付きが確認されなかった。
△:塗膜が変化したものの、貼り付きが確認されなかった。
×:塗膜の貼り付きが確認された。
○、△を合格とした。 (Blocking resistance)
The coated surface and the chemical conversion film surface of each material were overlapped, a load of 2 kPa was applied from above, and stored at 50 ° C. for 1 day, and the state of adhesion of the coating film was visually observed.
○: Change or sticking of the coating film was not confirmed.
(Triangle | delta): Although the coating film changed, sticking was not confirmed.
X: Sticking of the coating film was confirmed.
○ and △ were regarded as acceptable.
シルクスクリーンインキで供試材に印刷を行った。UV硬化後のインクとの密着性を碁盤目テープ剥離により碁盤目の非剥離率で評価した。シルクスクリーンインキはRIG(商品名、セイコーアドバンス社製、UV硬化性金属用インキ)を使用した。
○:剥離なし 100/100
△:一部剥離 1/100~99/100
×:全面剥離 0/100、又は印刷後インクが滲んで使用に耐えられなかった。
○を合格とした。 (Printability)
The test material was printed with silk screen ink. The adhesion with the ink after UV curing was evaluated by the non-peeling rate of the grid by strip tape peeling. The silk screen ink used was RIG (trade name, manufactured by Seiko Advance Co., Ltd., UV curable metal ink).
○: No peeling 100/100
Δ: Partially peeled 1/100 to 99/100
X: Full surface peeling 0/100, or ink was smeared after printing and could not be used.
○ was accepted.
Claims (5)
- アルミニウム基材と、当該アルミニウム基材の少なくとも一方の表面に形成された化成皮膜と、当該化成皮膜上に形成された塗膜とを含むアルミニウム塗装材であって、
前記塗膜は、ビスフェノールAエポキシ樹脂を主成分とし、メチルエチルケトンによる膨潤度が1.5未満、表面自由エネルギーが36mN/m~50mN/m、かつ、ガラス転移温度が50℃~100℃であることを特徴とするコンデンサケース用アルミニウム塗装材。 An aluminum coating material comprising an aluminum substrate, a chemical conversion film formed on at least one surface of the aluminum base material, and a coating film formed on the chemical conversion film,
The coating film is composed mainly of bisphenol A epoxy resin, has a degree of swelling with methyl ethyl ketone of less than 1.5, a surface free energy of 36 mN / m to 50 mN / m, and a glass transition temperature of 50 ° C. to 100 ° C. An aluminum coating material for capacitor cases. - 前記塗膜は、ビスフェノールAエポキシ樹脂およびポリイソシアネートを含有する塗料組成物の硬化物であって、前記ビスフェノールAエポキシ樹脂と前記ポリイソシアネートの重量比率は、50/50~90/10であることを特徴とする、請求項1に記載のコンデンサケース用アルミニウム塗装材。 The coating film is a cured product of a coating composition containing bisphenol A epoxy resin and polyisocyanate, and the weight ratio of the bisphenol A epoxy resin and the polyisocyanate is 50/50 to 90/10. The aluminum coating material for a capacitor case according to claim 1, characterized in that it is characterized in that
- 前記ポリイソシアネートは、ポリエーテル骨格を有するジイソシアネートであることを特徴とする、請求項2に記載のコンデンサケース用アルミニウム塗装材。 The aluminum coating material for a capacitor case according to claim 2, wherein the polyisocyanate is a diisocyanate having a polyether skeleton.
- 前記ポリイソシアネートは、ポリエーテル骨格を有するジイソシアネートおよびアルキレン鎖を有するジイソシアネートであり、前記ポリエーテル骨格を有するジイソシアネートと前記アルキレン鎖を有するジイソシアネートの重量比率は、50/50~95/5であることを特徴とする、請求項2に記載のコンデンサケース用アルミニウム塗装材。 The polyisocyanate is a diisocyanate having a polyether skeleton and a diisocyanate having an alkylene chain, and the weight ratio of the diisocyanate having the polyether skeleton and the diisocyanate having an alkylene chain is from 50/50 to 95/5. The aluminum coating material for capacitor cases according to claim 2, characterized in that
- 前記ポリエーテル骨格は、ネオペンチルグリコール骨格であることを特徴とする、請求項3又は4にコンデンサケース用アルミニウム塗装材。 5. The aluminum coating material for a capacitor case according to claim 3, wherein the polyether skeleton is a neopentyl glycol skeleton.
Priority Applications (2)
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KR1020147033587A KR101677222B1 (en) | 2013-09-11 | 2014-07-11 | Aluminum coating material for condenser case |
CN201480042218.1A CN105453202B (en) | 2013-09-11 | 2014-07-11 | Capacitor casing aluminium coating material |
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JP2013188381A JP6184266B2 (en) | 2013-09-11 | 2013-09-11 | Aluminum paint for capacitor case |
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JP (1) | JP6184266B2 (en) |
KR (1) | KR101677222B1 (en) |
CN (1) | CN105453202B (en) |
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CN111566768A (en) * | 2018-01-25 | 2020-08-21 | 株式会社村田制作所 | Film capacitor and outer case for film capacitor |
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JP2015174984A (en) * | 2014-03-18 | 2015-10-05 | 株式会社Uacj | Coating composition for coating material for capacitor case and aluminum coating material for capacitor case |
JP6351373B2 (en) * | 2014-05-21 | 2018-07-04 | 株式会社Uacj | Aluminum paint for capacitor case |
CN107418386A (en) * | 2017-09-03 | 2017-12-01 | 安徽天裕汽车零部件制造有限公司 | A kind of process of car floor powder coating |
CN109735226B (en) * | 2018-12-14 | 2020-08-14 | 珠海市润星泰电器有限公司 | Coating material for light alloy pulping and preparation method thereof |
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JPH03199279A (en) * | 1989-12-27 | 1991-08-30 | Mitsui Toatsu Chem Inc | Coating resin composition |
JP2002179998A (en) * | 2000-12-13 | 2002-06-26 | Sumika Bayer Urethane Kk | Coating composition and coated steel sheet using the same |
WO2007004436A1 (en) * | 2005-06-30 | 2007-01-11 | Arakawa Chemical Industries, Ltd. | Aqueous liquid containing vinyl-modified epoxy resin, process for producing the same, and water-based coating material |
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JP2007204579A (en) | 2006-02-01 | 2007-08-16 | Basf Coatings Japan Ltd | Thermosetting coating composition for precoat and precoated metal plate using it |
JP2009032881A (en) | 2007-07-26 | 2009-02-12 | Furukawa Sky Kk | Resin coating aluminum alloy plate material for aluminum electrolytic capacitor case, aluminum electrolytic capacitor case, and aluminum electrolytic capacitor |
JP4616916B2 (en) | 2008-10-10 | 2011-01-19 | 住友軽金属工業株式会社 | Resin-coated aluminum alloy plate for bottomed cylindrical case for capacitors |
JP5252494B2 (en) | 2008-11-28 | 2013-07-31 | 三菱アルミニウム株式会社 | Resin-coated aluminum material and electrolytic capacitor case using the same |
WO2011118027A1 (en) * | 2010-03-26 | 2011-09-29 | 住友軽金属工業株式会社 | Resin-coated aluminum alloy plate for bottomed cylindrical case for capacitor |
JP2012164725A (en) * | 2011-02-04 | 2012-08-30 | Furukawa Sky Kk | Resin-coated aluminum material for aluminum electrolytic capacitor case and method of producing the same |
JP2015174984A (en) | 2014-03-18 | 2015-10-05 | 株式会社Uacj | Coating composition for coating material for capacitor case and aluminum coating material for capacitor case |
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- 2014-07-11 KR KR1020147033587A patent/KR101677222B1/en active IP Right Grant
- 2014-07-11 CN CN201480042218.1A patent/CN105453202B/en not_active Expired - Fee Related
- 2014-07-11 WO PCT/JP2014/068602 patent/WO2015037322A1/en active Application Filing
- 2014-07-11 MY MYPI2016700392A patent/MY181329A/en unknown
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH03199279A (en) * | 1989-12-27 | 1991-08-30 | Mitsui Toatsu Chem Inc | Coating resin composition |
JP2002179998A (en) * | 2000-12-13 | 2002-06-26 | Sumika Bayer Urethane Kk | Coating composition and coated steel sheet using the same |
WO2007004436A1 (en) * | 2005-06-30 | 2007-01-11 | Arakawa Chemical Industries, Ltd. | Aqueous liquid containing vinyl-modified epoxy resin, process for producing the same, and water-based coating material |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN111566768A (en) * | 2018-01-25 | 2020-08-21 | 株式会社村田制作所 | Film capacitor and outer case for film capacitor |
CN111566768B (en) * | 2018-01-25 | 2022-01-21 | 株式会社村田制作所 | Film capacitor and outer case for film capacitor |
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CN105453202A (en) | 2016-03-30 |
CN105453202B (en) | 2018-05-11 |
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MY181329A (en) | 2020-12-21 |
JP6184266B2 (en) | 2017-08-23 |
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KR101677222B1 (en) | 2016-11-17 |
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