KR101677222B1 - Aluminum coating material for condenser case - Google Patents
Aluminum coating material for condenser case Download PDFInfo
- Publication number
- KR101677222B1 KR101677222B1 KR1020147033587A KR20147033587A KR101677222B1 KR 101677222 B1 KR101677222 B1 KR 101677222B1 KR 1020147033587 A KR1020147033587 A KR 1020147033587A KR 20147033587 A KR20147033587 A KR 20147033587A KR 101677222 B1 KR101677222 B1 KR 101677222B1
- Authority
- KR
- South Korea
- Prior art keywords
- coating film
- coating
- aluminum
- diisocyanate
- resistance
- Prior art date
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- 238000000576 coating method Methods 0.000 title claims abstract description 113
- 239000011248 coating agent Substances 0.000 title claims abstract description 112
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 44
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000000463 material Substances 0.000 title claims abstract description 37
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims abstract description 35
- 239000000126 substance Substances 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 230000008961 swelling Effects 0.000 claims abstract description 13
- 238000007739 conversion coating Methods 0.000 claims abstract description 10
- 125000005442 diisocyanate group Chemical group 0.000 claims description 36
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 27
- 229920000570 polyether Polymers 0.000 claims description 27
- 229920001228 polyisocyanate Polymers 0.000 claims description 24
- 239000005056 polyisocyanate Substances 0.000 claims description 24
- 125000002947 alkylene group Chemical group 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical group OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 4
- 230000007704 transition Effects 0.000 claims 1
- 238000007639 printing Methods 0.000 abstract description 25
- 230000007797 corrosion Effects 0.000 abstract description 23
- 238000005260 corrosion Methods 0.000 abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 20
- 238000009413 insulation Methods 0.000 abstract description 17
- 230000000903 blocking effect Effects 0.000 abstract description 16
- 239000003990 capacitor Substances 0.000 abstract description 16
- 238000000465 moulding Methods 0.000 abstract description 16
- 230000009477 glass transition Effects 0.000 abstract description 15
- 239000011342 resin composition Substances 0.000 abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 19
- 239000008199 coating composition Substances 0.000 description 19
- 229920005989 resin Polymers 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- -1 nitrogen-containing compound Chemical class 0.000 description 18
- 239000007788 liquid Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- 229910000838 Al alloy Inorganic materials 0.000 description 11
- 238000004140 cleaning Methods 0.000 description 11
- 238000002845 discoloration Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000001993 wax Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexyloxide Natural products O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000004645 polyester resin Substances 0.000 description 5
- 229920001225 polyester resin Polymers 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000008021 deposition Effects 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003822 epoxy resin 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
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000004925 denaturation Methods 0.000 description 2
- 230000036425 denaturation Effects 0.000 description 2
- 239000012769 display material Substances 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
- 239000003112 inhibitor Substances 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
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 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 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004593 Epoxy 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
- 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
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent 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
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000010407 anodic oxide Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- KHEMNHQQEMAABL-UHFFFAOYSA-J dihydroxy(dioxo)chromium Chemical compound O[Cr](O)(=O)=O.O[Cr](O)(=O)=O KHEMNHQQEMAABL-UHFFFAOYSA-J 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 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
- 239000004210 ether based solvent Substances 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
- 150000002334 glycols Chemical class 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
- 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
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000011259 mixed solution Substances 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
- 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
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000001648 tannin Substances 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Paints Or Removers (AREA)
- Laminated Bodies (AREA)
Abstract
콘덴서 케이스에 성형할 수 있는 양호한 성형성, 및 콘덴서 케이스로서 성형한 후의 절연성, 내 고온수성, 2차 밀착성, 내 세정액성, 내식성, 내 블로킹성, 인쇄성이 뛰어나며, 그리고 비용면이나 안전성, 환경면에도 우수한 콘덴서 케이스용 알루미늄 도장재를 제공한다.
콘덴서 케이스용 알루미늄 도장재는, 알루미늄 기재와, 상기 알루미늄 기재의 적어도 일측 표면에 형성되는 화성(化成) 피막과, 상기 화성 피막 상에 형성된 도막(塗膜)을 포함하는 알루미늄 도장재에 있어서, 상기 도막은, 비스페놀 A 에폭시 수지(bisphenol A epoxy resin)를 주성분으로 하고, 메틸에틸케톤(methyl ethyl ketone)에 의한 팽윤도가 1.5 미만, 표면 자유 에너지가 36 mN/m~50mN/m 이고, 유리 전이 온도가 50℃~100℃이다.Excellent moldability that can be molded into a capacitor case, insulation after molding as a capacitor case, high temperature water resistance, secondary adhesion, lye resistance, corrosion resistance, blocking resistance, printing property, Provides an aluminum coating material for a condenser case which is also excellent on the surface.
An aluminum coating material for a condenser case is an aluminum coating material comprising an aluminum substrate, a chemical conversion coating formed on at least one surface of the aluminum base, and a coating film formed on the chemical conversion coating, A resin composition comprising bisphenol A epoxy resin as a main component, a degree of swelling by methyl ethyl ketone of less than 1.5, a surface free energy of 36 mN / m to 50 mN / m, a glass transition temperature of 50 ° C Lt; 0 > C.
Description
본 발명은, 양호한 딥드로잉 성형성, 피막 밀착성, 및, 절연성, 내 고온수성, 2차 밀착성, 내 세정액성, 내식성, 내 블로킹성, 인쇄성이 우수하고, 더불어 비용면이나 안전성, 환경면에도 우수한 콘덴서 케이스용 알루미늄 도장재에 관한 것이다.An object of the present invention is to provide a resin composition which is excellent in deep draw forming formability, film adhesion property, insulation property, high temperature water resistance, secondary adhesion property, lye resistance, corrosion resistance, blocking resistance and printing property, And an aluminum coating material for an excellent capacitor case.
최근, 성형후의 절연용 수지 피막이 불필요한 수지 피복 알루미늄 합금재가, 콘덴서 케이스 재로서 사용되고 있다. 이러한 콘덴서 케이스는 원통형이며, 다양한 높이/직경비를 가진다. 판재를 원통형으로 형성하기 위하여, 딥드로잉 성형이나, 아이어닝 성형(ironing forming)을 조합한 가혹한 조건에서의 성형이 실시된다. 따라서, 건재 등에 이용되는 일반적인 수지 피복 알루미늄 합금 판재를 적용하면, 수지층의 균열이나 박리 등이 발생하여 충분한 절연성을 얻을 수 없다. 특히, 높이/직경비가 큰 케이스의 성형에 있어서, 이러한 경향이 현저하다.Recently, a resin-coated aluminum alloy material which does not require a molded resin for insulation after molding has been used as a capacitor case material. Such a capacitor case is cylindrical and has various height / diameter ratios. In order to form the plate material into a cylindrical shape, molding in a severe condition in which deep drawing forming and ironing forming are combined is carried out. Therefore, when a general resin-coated aluminum alloy sheet material used for construction materials or the like is applied, cracking or peeling of the resin layer occurs and sufficient insulating property can not be obtained. Particularly, in the case of molding a case having a large height / diameter ratio, such a tendency is remarkable.
특허문헌 1에는, 콘덴서 케이스 등에 이용되고, 성형성이 우수하며, 내 열변색성 및 고온고습 내구성을 가지는 수지 피복 알루미늄 재료가 개시되어 있다. 이러한 수지 피복 알루미늄 재료는, 순수 알루미늄 또는 알루미늄 합금 표면에 유공율 5% 이하의 무공질 양극 산화 피막을 형성하고, 그 층 위에 수평균 분자량(number-average molecular weight, Mn)이 2,000~100,000인 에폭시계 수지를 실란 커플링제(silane coipling agent)를 통하여 피복한 구조를 가진다. 또한, 상기 무공질 양극 산화 피막의 막 두께가 30~200nm, 상기 실란 커플링제의 무공질 양극 산화 피막 상에 대한 도포량이 0.5~10mg/㎡, 및 상기 에폭시계 수지의 수평균 분자량이 5,000~80,000에서 그 피복 두께가 2~20㎛인 것이 바람직하다는 것이 개시되어 있다.Patent Document 1 discloses a resin-coated aluminum material which is used for a capacitor case and the like, has excellent moldability, thermal discoloration resistance and high temperature and high humidity durability. Such a resin-coated aluminum material is formed by forming an anodic anodic oxide film having a porosity of 5% or less on the surface of pure aluminum or aluminum alloy and forming an epoxy resin film having a number-average molecular weight (Mn) of 2,000 to 100,000 Based resin is coated through a silane co-coupling agent. The coating amount of the silane coupling agent on the nonporous anodized film is 0.5 to 10 mg / m 2, and the number average molecular weight of the epoxy resin is 5,000 to 80,000 It is preferable that the coating thickness is 2 to 20 mu m.
특허문헌 2에는, (A) 수산기 함유 수지와 블락 이소시아네이트(blocked isocyanate) 경화제를 함유하는 피막 형성 수지 조성물, (B) 알데히드 화합물 흡착능을 가진 질소 함유 화합물로 표면 처리된 무기 화합물, 및, (C) 인산 티타늄계 화합물(titanium phosphate solution)을, (A) 성분 100 중량부에 대하여 (B) 성분 0.1~10 중량부 및 (C) 성분 0.1~10 중량부의 비율로 함유하는 것을 특징으로 하는 프리코트(pre-coat)용 열 경화형 도료 조성물과, 그것을 금속판에 도장하여 얻어지는 프리코트 금속판이 개시되어 있다. 또한, (A) 성분에 포함된 수산기 함유 수지로서, 수산기 값 5~200mgKOH/g, 수평균 분자량이 1,000~20,000인 수산기 함유 폴리에스테르 수지(polyester resin)가 개시되어 있다.Patent Document 2 discloses a film forming resin composition comprising (A) a resin composition containing a hydroxyl group and a blocked isocyanate curing agent, (B) an inorganic compound surface-treated with a nitrogen-containing compound capable of adsorbing an aldehyde compound, and (C) Characterized by containing a titanium phosphate solution in an amount of 0.1 to 10 parts by weight of the component (B) and 0.1 to 10 parts by weight of the component (C) based on 100 parts by weight of the component (A) pre-coat type, and a pre-coated metal plate obtained by coating a metal plate. Further, a hydroxyl group-containing polyester resin having a hydroxyl value of 5 to 200 mg KOH / g and a number average molecular weight of 1,000 to 20,000 is disclosed as the hydroxyl group-containing resin contained in the component (A).
특허문헌 3에는, 폴리에틸렌왁스(polyethylene wax) 및/또는 카나우바 왁스(carnauba wax)를 포함하고, 수지층 두께가 2㎛ 이상 22㎛ 이하이며, 수지층 표면에 있어서 길이 100㎛인 하나의 직선이 절단하는 왁스 입자 길이의 합이 10㎛ 이상이고, 수지층 두께의 80% 이하에 있어서, 0.1㎛ 이상인 긴 직경 부분을 구비한 단면 형상의 왁스 입자가, 3개 이상 50개 이하 존재하며, 수지층 두께의 80%를 넘는 길이의 긴 직경 부분을 구비한 왁스 입자가 10개 미만인 알루미늄 전해 콘덴서 케이스용 수지 피복 알루미늄 합금재가 개시되어 있다.Patent Literature 3 discloses that a single straight line including a polyethylene wax and / or a carnauba wax and having a resin layer thickness of 2 탆 or more and 22 탆 or less and a length of 100 탆 on the surface of the resin layer The wax particles having a cross-sectional shape having a long diameter portion of 0.1 占 퐉 or more are present in an amount of not less than 3 but not more than 50, and the sum of the lengths of the wax particles to be cut is not less than 10 占 퐉 and not more than 80% A resin-coated aluminum alloy material for an aluminum electrolytic capacitor case having less than 10 wax particles having a long diameter portion having a length exceeding 80% of the thickness is disclosed.
그러나, 특허문헌 1 및 특허문헌 2의 수지 피복 알루미늄재는, 에폭시계 수지나 폴리에스테르계 수지가 최표면에 형성되어 있기 때문에, 성형성은 뛰어날지라도, 가공후의 프레스 성형에서 사용한 프레스유를 떨어뜨리기 위한 세정액에 의하여 도막의 변성이나 용해가 일어나는 경우가 있다. 또한, 조립한 콘덴서를 가혹한 환경에 노출하면, 2차 밀착성이 떨어지기 때문에 수지 피막의 박리나 변색이 일어나는 일이 있다. 그 결과, 절연 불량이 되고, 콘덴서 자체로서 신뢰성을 잃는 문제가 있다.However, since the resin-coated aluminum material of Patent Document 1 and Patent Document 2 is formed on the outermost surface of the epoxy resin or polyester resin, even if the moldability is excellent, a cleaning liquid for dropping the press oil used in the post- May cause denaturation or dissolution of the coating film. Further, if the assembled capacitor is exposed to a harsh environment, the secondary adhesion may deteriorate, so that peeling or discoloration of the resin coating may occur. As a result, there is a problem that the insulation becomes defective and the reliability of the capacitor itself is lost.
또한, 특허문헌 3의 수지 피막 알루미늄 합금 판재에서는, 윤활성을 부여하여 성형성을 향상시키기 위하여, 표면에 왁스를 함유시키고 있으나, 표면에 왁스가 존재함으로써, 인쇄시 잉크가 튀어버려, 생산성이 저하되고 마는 문제가 있다.In the resin-coated aluminum alloy sheet of Patent Document 3, wax is contained on the surface in order to impart lubricity to improve moldability. However, since wax is present on the surface, the ink splashes at the time of printing, There is a problem.
본 발명의 목적은, 콘덴서 케이스에 성형할 수 있는 양호한 성형성, 및 콘덴서 케이스로서 성형한 후의 절연성, 내 고온수성, 2차 밀착성, 내 세정액성, 내식성, 내 블로킹성, 인쇄성이 뛰어나며, 그리고 비용면이나 안전성, 환경면에도 우수한 콘덴서 케이스용 알루미늄 도장재를 제공하는 것이다.It is an object of the present invention to provide a resin composition which is excellent in moldability that can be molded into a capacitor case and has excellent insulation properties after molding as a capacitor case, high temperature water resistance, secondary adhesion, lye resistance, corrosion resistance, blocking resistance, An aluminum coating material for a condenser case which is excellent in terms of cost, safety, and environment.
본 발명에 따른 콘덴서 케이스용 알루미늄 도장재는, 알루미늄 기재와, 상기 알루미늄 기재의 적어도 일측 표면에 형성되는 화성(化成) 피막과, 상기 화성 피막 상에 형성된 도막(塗膜)을 포함하는 알루미늄 도장재에 있어서, 상기 도막은, 비스페놀 A 에폭시 수지(bisphenol A epoxy resin)를 주성분으로 하고, 메틸에틸케톤(methyl ethyl ketone)에 의한 팽윤도가 1.5 미만, 표면 자유 에너지가 36 mN/m~50mN/m 이고, 유리 전이 온도가 50℃~100℃인 것을 특징으로 한다.An aluminum coating material for a condenser case according to the present invention is an aluminum coating material comprising an aluminum base material, a chemical conversion coating formed on at least one surface of the aluminum base, and a coating film formed on the chemical conversion coating, The coating film comprises bisphenol A epoxy resin as a main component, swelling degree by methyl ethyl ketone of less than 1.5, surface free energy of 36 mN / m to 50 mN / m, glass transition And the temperature is 50 ° C to 100 ° C.
본 발명에 따른 콘덴서 케이스용 알루미늄 도장재에 있어서, 상기 도막은, 비스페놀 A 에폭시 수지 및 폴리이소시아네이트(polyisocyanate)를 포함하는 도료 조성물의 경화물에 있어서, 상기 비스페놀 A 에폭시 수지와 상기 폴리이소시아네이트의 중량 비율은, 50/50~90/10인 것이 바람직하다.In the aluminum coating material for a condenser case according to the present invention, the coating film is a cured product of a coating composition comprising a bisphenol A epoxy resin and a polyisocyanate, wherein the weight ratio of the bisphenol A epoxy resin to the polyisocyanate is, 50/50 to 90/10.
본 발명에 따른 콘덴서 케이스용 알루미늄 도장재에 있어서, 상기 폴리이소시아네이트는, 폴리에테르(polyether) 골격을 가지는 디이소시아네이트(diisocyanate)인 것이 바람직하다.In the aluminum coating material for a condenser case according to the present invention, the polyisocyanate is preferably a diisocyanate having a polyether skeleton.
본 발명에 따른 콘덴서 케이스용 알루미늄 도장재에 있어서, 상기 폴리이소시아네이트는, 폴리에테르 골격을 가지는 디이소시아네이트 및 알킬렌(alkylene) 사슬을 가지는 디이소시아네이트이며, 상기 폴리에테르 골격을 가지는 디이소시아네이트와 상기 알킬렌 사슬을 가진 디이소시아네이트의 중량 비율은, 50/50~95/5인 것이 바람직하다.In the aluminum coating material for a condenser case according to the present invention, the polyisocyanate is a diisocyanate having a polyether skeleton and a diisocyanate having an alkylene chain, the diisocyanate having the polyether skeleton and the alkylene chain The weight ratio of diisocyanate to be used is preferably 50/50 to 95/5.
본 발명에 따른 콘덴서 케이스용 알루미늄 도장재에 있어서, 상기 폴리에테르 골격은, 네오펜틸글리콜(neopentyl glycol) 골격인 것이 바람직하다.In the aluminum coating material for a condenser case according to the present invention, the polyether skeleton is preferably a neopentyl glycol skeleton.
본 발명에 따른 콘덴서 케이스용 알루미늄 도장재는, 콘덴서 케이스에 요구되는 높은 성형성과, 가공후의 절연성, 가혹한 환경에도 견딜 수 있는 내 고온수성, 2차 밀착성을 가지며, 그리고 세정액에 노출되어도 변성되지 않은 우수한 내 세정액성을 가지며, 그리고 내식성, 내 블로킹성, 인쇄성이 우수하다.An aluminum coating material for a condenser case according to the present invention is characterized by having a high moldability required for a capacitor case, an insulation property after processing, resistance to internal hot water and secondary adhesion capable of enduring harsh environments, and an excellent scrubbing liquid And is excellent in corrosion resistance, blocking resistance and printing property.
본 발명에 따른 콘덴서 케이스용 알루미늄 도장재는, 알루미늄 또는 알루미늄 합금의 기재와, 상기 기재의 적어도 일측 표면에 형성된 화성(化成) 피막과, 상기 화성 피막 상에 형성된 도막을 구비한다.An aluminum coating material for a condenser case according to the present invention comprises a substrate made of aluminum or an aluminum alloy, a chemical conversion coating formed on at least one surface of the substrate, and a coating film formed on the chemical conversion coating.
본 발명에서 이용되는 기재는, 알루미늄 또는 알루미늄 합금으로 이루어진 기재이다. 이하에 있어서, 알루미늄 또는 알루미늄 합금으로 이루어진 기재를, 단순히 '알루미늄 기재'로 쓴다. 그리고, 알루미늄 이외의 금속을 기재로 이용하는 것도 가능하다.The substrate used in the present invention is a substrate made of aluminum or an aluminum alloy. Hereinafter, a substrate made of aluminum or an aluminum alloy is simply referred to as an " aluminum substrate ". It is also possible to use a metal other than aluminum as a substrate.
본 발명에서 이용되는 화성 피막은, 도포형이든 반응형이든 좋으나, 알루미늄 기재 및 도막에 대한 밀착성의 관점으로부터, 반응형이 바람직하다. 구체적으로는, 인산크로메이트(phosphoric acid chromate), 크롬산크로메이트(chromic acid chromate), 인산지르코늄(zirconium phosphate), 인산티타늄(titanium phosphate) 등의 처리액으로 형성되는 피막이다. 내식성, 2차 밀착성, 경제성의 관점으로부터, 인산크로메이트가 더욱 바람직하다. 인산크로메이트 피막의 부착량은 금속 Cr 원소 환산으로 2mg/㎡~50mg/㎡인 것이 바람직하다. 부착량이 Cr 원소 환산으로 2mg/㎡ 미만에서는, 충분한 내식성을 얻을 수 없으며, 게다가 도막에 대한 2차 밀착성을 얻을 수 없다. 또한, 부착량이 Cr 원소 환산으로 50mg/㎡을 넘어도, 내식성이나 도막의 2차 밀착성의 효과가 포화하여 경제성이 결여된다. 바람직한 부착량은 Cr 원소 환산으로 5mg/㎡~40mg/㎡이다.The chemical conversion film used in the present invention may be either a coating type or a reactive type, but a reaction type is preferable from the viewpoint of adhesion to an aluminum base and a coating film. Specifically, it is a film formed of a treatment liquid such as phosphoric acid chromate, chromic acid chromate, zirconium phosphate, or titanium phosphate. From the viewpoints of corrosion resistance, secondary adhesion, and economy, phosphoric acid chromate is more preferable. The deposition amount of the phosphoric acid chromate film is preferably 2 mg / m 2 to 50 mg / m 2 in terms of the metal Cr element. When the deposition amount is less than 2 mg / m < 2 > in terms of Cr element, sufficient corrosion resistance can not be obtained and secondary adhesion to the coating film can not be obtained. Further, even if the amount of deposition exceeds 50 mg / m < 2 > in terms of Cr element, the effect of corrosion resistance and secondary adhesion of the coating film is saturated, and economic efficiency is lacking. The preferable deposition amount is 5 mg / m 2 to 40 mg / m 2 in terms of Cr element.
본 발명에서 이용되는 도막은, 비스페놀 A 에폭시 수지(bisphenol A epoxy resin)를 주성분으로 하고, 메틸에틸케톤(methyl ethyl ketone, 이하 MEK로 쓴다)에 의한 팽윤도가 1.5 미만, 표면 자유 에너지가 36 mN/m~50mN/m 이고, 유리 전이 온도가 50℃~100℃이다.The coating film used in the present invention is a coating film composed mainly of bisphenol A epoxy resin and having a swelling degree of less than 1.5 by methyl ethyl ketone (MEK) and a surface free energy of 36 mN / m to 50 mN / m, and a glass transition temperature of 50 ° C to 100 ° C.
알루미늄 기재에, 비스페놀 A 에폭시 수지를 도장함으로써, 내습성, 밀착성, 내 고온수성, 내식성 등에 있어서 우수한 도막이 얻어진다. 그러나, 화성 피막이 강하고 견고하므로, 도막이 변형하면 도막 중에 왜곡이 잔존하기 쉽고, 2차 밀착성이 낮아지는 경향이 있다.By coating a bisphenol A epoxy resin on an aluminum substrate, a coating film excellent in moisture resistance, adhesion, high temperature water resistance, corrosion resistance, and the like can be obtained. However, since the chemical conversion coating is strong and rigid, if the coating is deformed, the distortion tends to remain in the coating film and the secondary adhesion tends to be lowered.
여기서, 본 발명에서는, 도막의 주성분을 비스페놀 A 에폭시 수지로 하고, 도막의 유리 전이 온도를 50℃~100℃로 함으로써, 2차 밀착성의 저하를 억제하는 것이 가능하게 되었다. 도막의 유리 전이 온도가 50℃ 미만이면, 도장후에 알루미늄 기재를 겹쳐 쌓은 경우, 재료가 달라붙어 버리는 현상을 블로킹이라 말하며, 도막이 눌러붙여진 상태가 장시간 지속되어도 달라붙지 않는 성질을 내 블로킹성이라 말한다. 한편, 도막의 유리 전이 온도가 100℃를 넘으면, 성형 가공시의 왜곡이 잔존하여, 2차 밀착성의 저하가 현저하게 된다.Here, in the present invention, it becomes possible to suppress deterioration of the secondary adhesion property by setting the glass transition temperature of the coating film to 50 to 100 占 폚 with the main component of the coating film being bisphenol A epoxy resin. When the glass transition temperature of the coating film is less than 50 ° C, the phenomenon that the materials adhere to each other when the aluminum base material is stacked after coating is referred to as blocking, and the property that the coating film does not stick even when the pressing state is maintained for a long time is referred to as blocking resistance. On the other hand, when the glass transition temperature of the coating film exceeds 100 캜, the distortion during molding processing remains, and the secondary adhesion property is remarkably deteriorated.
또한, 본 발명에서는 도막의 표면 자유 에너지를 36mN/m~50mN/m로 함으로써, 인쇄성을 충분히 확보할 수 있다. 그리고, 성형성을 양호하게 하는 방법 중 하나로서, 왁스 등의 윤활제를 첨가하는 것을 들 수 있으나, 첨가한 왁스가 표면에 노출되어, 표면 자유 에너지가 36mN/m 미만으로 낮아져버리는 일이 있다. 도막의 표면 자유 에너지가 36mN/m 미만이면, 인쇄시에 잉크가 튕기거나, 인쇄된 부분이 박리되어버리는 일이 있다. 또한, 도막의 표면 자유 에너지가 50mN/m를 넘으면, 잉크가 있는 표면 장력과 화성 피막의 표면 자유 에너지와의 차이가 커지게 되며, 잉크가 튕겨 인쇄하기 힘들게 된다. 그리고, 도막의 표면 자유 에너지는, 표면 자유 에너지가 기존에 알려진 액체에서 측정한 접촉각을 기반으로 확장 Fowkes의 식에 의하여 산출할 수 있다.Further, in the present invention, the surface free energy of the coating film is set to 36 mN / m to 50 mN / m, whereby the printing property can be sufficiently secured. One of the methods for improving the moldability is to add a lubricant such as wax. However, the added wax is exposed to the surface, and the surface free energy may be lowered to less than 36 mN / m. If the surface free energy of the coating film is less than 36 mN / m, ink may be repelled during printing or the printed portion may peel off. Further, when the surface free energy of the coating film exceeds 50 mN / m, the difference between the surface tension of the ink and the surface free energy of the chemical conversion film becomes large, and the ink repels and becomes difficult to print. And, the surface free energy of the coating can be calculated by the expansion Fowkes' equation based on the contact angle measured in the previously known liquid.
또한, 본 발명에서는, 도막의 MEK에 의한 팽윤도를 1.5 미만으로 함으로써, 성형시의 성형유나 성형후의 세정액 등에 의한 도막의 용해를 억제할 수 있으며, 내 세정액성을 부여할 수 있다. MEK에 의한 팽윤도는, 1.2 이하인 것이 더욱 바람직하다. MEK에 의한 팽윤도가 1.5 이상이면, 성형시의 성형유나 성형후의 세정액에 의하여, 도막의 팽윤, 용해 및 변색 등이 일어나 절연성이 떨어진다. 또한, 고온에 노출되었을 때, 도막의 변색이나 용해 등이 생기며, 내식성이 나빠진다.Further, in the present invention, the swelling degree of the coating film by MEK is less than 1.5, the dissolution of the coating film due to the molding oil or the cleaning liquid after molding can be suppressed, and the cleaning liquid can be imparted. The degree of swelling by MEK is more preferably 1.2 or less. If the degree of swelling by MEK is 1.5 or more, swelling, dissolution and discoloration of the coating film occur due to the molding oil or the cleaning liquid after molding at the time of molding, resulting in poor insulation. Further, when exposed to a high temperature, discoloration or dissolution of the coating film occurs and the corrosion resistance is deteriorated.
또한, 본 발명에 있어서, 도막은, 비스페놀 A 에폭시 수지를 함유하는 도료 조성물의 경화물인 것이 바람직하다. 비스페놀 A 에폭시 수지는, 공업적 범용성 및 양호한 내식성 등의 점으로부터 바람직하게 이용된다. 비스페놀 A 에폭시계 수지의 수평균 분자량은 특히 제한되지 않으나, 예를 들면, 20,000~100,000이다. 또한, 에폭시 당량은 특히 제한되지 않으나, 예를 들면, 100~1,000이다. 비스페놀 A 에폭시계 수지를 1종류 이용하여도 좋고, 또는 다른 종류의 비스페놀 A 에폭시계 수지를 2종 이상 이용하여도 좋다.Further, in the present invention, 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 number 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 1,000. One type of bisphenol A epoxy resin may be used, or two or more different kinds of bisphenol A epoxy resins may be used.
본 발명자들은, 도료 조성물에 폴리이소시아네이트(polyisocyanate)를 더 함유시켜, 비스페놀 A 에폭시 수지가 우레탄 결합에 의하여 가교되고 있는 도막을 형성함으로써, 성형성, 절연성, 2차 밀착성, 내 세정액성, 내식성, 내 브로킹성을 향상시킬 수 있는 것을 발견하였다. The present inventors have found that when a coating composition in which a bisphenol A epoxy resin is crosslinked by a urethane bond is formed by further containing a polyisocyanate in a coating composition, the formability, insulation, secondary adhesion, lye resistance, corrosion resistance, And the broke property can be improved.
비스페놀 A 에폭시 수지와 폴리이소시아네이트의 중량 비율은, 50/50~90/10인 것이 바람직하다. 비스페놀 A 에폭시 수지와 폴리이소시아네이트의 총량에 대하여, 비스페놀 A 에폭시 수지의 함유량이 50~90mass%인 것에 의하여, 2차 밀착성, 내 세정액성을 만족할 수 있다. 비스페놀 A 에폭시 수지의 함유량이 50mass% 미만에서는, 내 세정액성을 만족할 수 없다. 또한, 비스페놀 A 에폭시 수지의 함유량이 90mass%를 넘으면, 도막의 유리 전이 온도가 높고, 도막이 강하고 견고해져, 2차 밀착성을 만족할 수 없다.The weight ratio of the bisphenol A epoxy resin to the polyisocyanate is preferably 50/50 to 90/10. The content of the bisphenol A epoxy resin is 50 to 90 mass% based on the total amount of the bisphenol A epoxy resin and the polyisocyanate, so that the secondary adhesion property and the liquid cleaning property can be satisfied. When the content of the bisphenol A epoxy resin is less than 50% by mass, the cleaning liquid resistance can not be satisfied. When the content of the bisphenol A epoxy resin exceeds 90 mass%, the glass transition temperature of the coating film becomes high, and the coating film becomes strong and firm, and the secondary adhesion property can not be satisfied.
폴리이소시아네이트로서는, 폴리에테르(polyether) 골격을 가지는 디이소시아네이트(diisocyanate)가 바람직하다. 폴리에테르 골격을 가진 디이소시아네이트로서는, 폴리에테르 화합물에 디이소시아네이트를 유도한 화합물이다. 폴리에테르 화합물로서는, 폴리에틸렌글리콜(polyethylene glycol), 폴리프로필렌글리콜(polypropylene glycol), 폴리테트라메틸렌글리콜(polytetramethylene glycol), 폴리헥사메틸렌글리콜(polyhexamethylene glycol), 폴리네오펜틸글리콜(polyneopentyl glycol) 등의 글리콜(glycol)류, 이들의 글리콜류 끼리를 반응시켜 얻어진 화합물, 아크릴폴리올(acrylic polyol), 폴리에스테르폴리에테르(polyester polyether), 아크릴폴리에테르(acrylic polyether) 등을 들 수 있다.The polyisocyanate is preferably a diisocyanate having a polyether skeleton. As the diisocyanate having a polyether skeleton, a diisocyanate is derived from a polyether compound. Examples of the polyether compound include glycol such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyneopentyl glycol, etc. glycol, a compound obtained by reacting these glycols with each other, an acrylic polyol, a polyester polyether, and an acrylic polyether.
폴리에테르 골격으로서는, 특히 네오펜틸글리콜(neopentyl glycol) 골격이 바람직하다. 네오펜틸글리콜 골격을 가지는 디이소시아네이트를 함유시키면, 2차 밀착성 및 내 블로킹성이 우수해진다.As the polyether skeleton, a neopentyl glycol skeleton is particularly preferable. When a diisocyanate having a neopentyl glycol skeleton is contained, secondary adhesion and blocking resistance are improved.
폴리이소시아네이트는, 뷰렛 화합물(buret compound), 첨가 화합물(adduct compound), 이소시아누레이트 화합물(isocyanurate compound) 등의 3 관능 이상의 폴리이소시아네이트를 사용하는 것도 가능하다. 또한, 이소시아네이트 기의 반응성을 억제하기 위하여, 이소시아네이트 기를 블록제(blocking agent)에 의하여 마스크한 블록형 폴리이소시아네이트(blocked polyisocyanate)를 사용하는 것이 바람직하다. 블록제는, 예를 들면, 페놀(phenol), 알콜(alcohol), 말론산디메틸(dimethyl malonate), 아세트초산에틸(acetoacetic acid ethyl) 등의 활성 메틸렌(active methylene)이다. 블록형 폴리이소시아네이트는, 가열에 의하여 블록제가 해리함으로써 가교가 개시되므로, 취급이나 보관이 용이하다.As the polyisocyanate, it is also possible to use a trifunctional or higher polyisocyanate such as a buret compound, an adduct compound and an isocyanurate compound. In addition, in order to suppress the reactivity of the isocyanate group, it is preferable to use a blocked polyisocyanate in which an isocyanate group is masked by a blocking agent. The blocking agent is, for example, active methylene such as phenol, alcohol, dimethyl malonate, acetoacetic acid ethyl, and the like. In the block-type polyisocyanate, since crosslinking is initiated by dissociation of the block agent by heating, it is easy to handle and store.
비스페놀 A 에폭시 수지와 폴리에테르 골격을 가진 디이소시아네이트를 함유하는 도료 조성물을 알루미늄 기재 상에 도포하고, 인화를 실시함으로써, 비스페놀 A 에폭시 수지와 폴리에테르 골격을 가지는 디이소시아네이트가 가교되고, 우레탄 결합이 형성된다.A coating composition containing a bisphenol A epoxy resin and a diisocyanate having a polyether skeleton is applied on an aluminum substrate and then subjected to a printing to crosslink the bisphenol A epoxy resin and the diisocyanate having a polyether skeleton to form a urethane bond do.
비스페놀 A 에폭시 수지와 폴리에테르 골격을 가진 디이소시아네이트의 총량에 대하여, 폴리에테르 골격을 가진 디이소시아네이트의 함유량이 10~50 mass%인 것에 의하여, 도막의 유연성이 증가하고, 2차 밀착성, 내 세정액성을 만족할 수 있다. 폴리에테르 골격을 가진 디이소시아네이트의 함유량이 10 mass% 미만에서는, 도막의 유리 전이 온도가 높고, 도막이 강하고 견고하게 되어, 2차 밀착성이 나빠지는 경향이 있다. 또한, 표면 자유 에너지가 낮아지게 되고, 인쇄성이 나빠지는 경향이 있다. 한편, 폴리에테르 골격을 가진 디이소시아네이트의 함유량이 50 mass%를 넘으며, 도막의 MEK에 의한 팽윤도나 표면 자유 에너지가 높아지고, 내 세정액성이나 인쇄성이 나빠지는 경향이 있다.When the content of the diisocyanate having a polyether skeleton is in the range of 10 to 50 mass% based on the total amount of the bisphenol A epoxy resin and the polyether skeleton-containing diisocyanate, the flexibility of the coating film is increased and the secondary adhesion, Can be satisfied. When 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 is strong and firm, and the secondary adhesion property tends to deteriorate. Further, the surface free energy is lowered, and the printability tends to deteriorate. On the other hand, the content of the diisocyanate having a polyether skeleton exceeds 50 mass%, the degree of swelling and the surface free energy of the coating film due to MEK increase, and the cleaning liquid and printing property tend to deteriorate.
본 발명의 알루미늄 도장재는, 자동차나 가전 기기 등에 탑재되는 콘덴서를 수용하는 케이스에 사용된다. 이와 같은 콘덴서는, 고온 다습 등의 가혹한 환경하에서 콘덴서의 기능을 유지해야만 하며, 콘덴서 케이스에 있어서는, 내 고온수성이 필요하게 된다. 본 발명자들은, 도료 조성물에, 폴리이소시아네이트로서, 폴리에테르 골격을 가진 디이소시아네이트와 알킬렌(alkylene) 사슬을 가진 디이소시아네이트를 함유시킴으로써, 내 고온수성을 향상시킬 수 있음을 발견하였다.The aluminum coating material of the present invention is used in a case for accommodating a capacitor mounted on an automobile or a household electric appliance. Such a condenser must maintain the function of the condenser under harsh environments such as high temperature and humidity, and in the condenser case, high temperature water resistance is required. The present inventors have found that by containing a diisocyanate having a polyether skeleton and a diisocyanate having an alkylene chain as a polyisocyanate in the coating composition, it is possible to improve the high temperature water resistance.
폴리에테르 골격을 가지는 디이소시아네이트와 알킬렌 사슬을 가진 디이소시아네이트의 중량 비율은, 50/50~95/5인 것이 바람직하다. 폴리에테르 골격을 가지는 디이소시아네이트와 알킬렌 사슬을 가진 디이소시아네이트의 총량에 대하여, 알킬렌 사슬을 가진 디이소시아네이트의 함유량이 5~50 mass%인 것에 의하여, 양호한 성형성, 절연성, 2차 밀착성, 내 세정액성, 내식성, 내 블로킹성, 인쇄성을 유지하고, 내 고온수성을 향상시킬 수 있다. 알킬렌 사슬을 가진 디이소시아네이트의 함유량이 5 mass% 미만이면, 양호한 성형성, 절연성, 2차 밀착성, 내 세정액성, 내식성, 내 블로킹성, 인쇄성을 유지할 수 있지만, 가혹한 환경하에서 도막의 변색이나 변성이 일어나고, 내 고온수성의 충분한 효과를 발휘할 수 없다. 한편, 알킬렌 사슬을 가진 디이소시아네이트의 함유량이 50 mass%를 넘으면, 우레탄 결합의 가교도가 높아지고, 내 고온수성을 만족시킬 수 있지만, 2차 밀착성을 만족할 수 없다.The weight ratio of the diisocyanate having a polyether skeleton to the diisocyanate having an alkylene chain is preferably 50/50 to 95/5. When the content of the diisocyanate having an alkylene chain is from 5 to 50 mass% based on the total amount of the diisocyanate having a polyether skeleton and the diisocyanate having an alkylene chain, good moldability, insulation, secondary adhesion, It is possible to maintain the cleaning liquid property, the corrosion resistance, the blocking resistance and the printing property, and to improve the high temperature water resistance. If the content of the diisocyanate having an alkylene chain is less than 5 mass%, it is possible to maintain good moldability, insulation, secondary adhesion, lye resistance, corrosion resistance, blocking resistance and printing property, but under the harsh environment, Denaturation occurs, and sufficient effect of the high temperature aqueous solution can not be exhibited. On the other hand, when the content of the diisocyanate having an alkylene chain is more than 50 mass%, the degree of crosslinking of the urethane bond increases and the high temperature aqueous solution can be satisfied, but the secondary adhesion property can not be satisfied.
알킬렌 사슬을 가진 디이소시아네이트는, 예를 들면, 알킬렌 사슬의 양 말단에 이소시아네이트 기가 부가된 구조를 가진다. 알킬렌 사슬의 탄소수는 1~10인 것이 바람직하다. 특히, 알킬렌 사슬은, 헥사메틸렌(hexamethylene) 사슬인 것이 바람직하다.The diisocyanate having an alkylene chain has, for example, a structure in which an isocyanate group is added to both terminals of the alkylene chain. The alkylene chain preferably has 1 to 10 carbon atoms. In particular, the alkylene chain is preferably a hexamethylene chain.
비스페놀 A 에폭시 수지, 폴리에테르 골격을 가지는 디이소시아네이트, 알킬렌 사슬을 가진 디이소시아네이트를 함유하는 도료 조성물을 알루미늄 기재 상에 도포하고, 인화를 실시함으로써, 비스페놀 A 에폭시 수지와 폴리에테르 골격을 가지는 디이소시아네이트가 가교하여, 우레탄 결합이 형성되며, 비스페놀 A 에폭시 수지와 알킬렌 사슬을 가진 디이소시아네이트가 가교하여, 우레탄 결합이 형성된다.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 subjected to a printing process to obtain a bisphenol A epoxy resin and a diisocyanate having a polyether skeleton Is crosslinked to form a urethane bond, and a bisphenol A epoxy resin and a diisocyanate having an alkylene chain are crosslinked to form a urethane bond.
(기타 첨가제)(Other additives)
본 발명에 있어서 도막을 형성하는 도료 조성물에는, 필요에 따라, 방청제, 레벨링제(표면 조정제), 계면 활성제 등을 함유시켜도 좋다. 또한, 상용성(相溶性)을 잃지않는 범위에서 착색제를 함유시켜도 좋다. 방청제로서는, 예를 들면, 탄닌산(tannin), 몰식자산(gallic acid), 피트산(phytic acid), 포스핀산(phosphinic acid) 등을 들 수 있다. 레벨링제로서는, 예를 들면, 폴리알콜(polyalcohol)의 알킬에스테르류(alkyl esters) 등을 들 수 있다. 계면 활성제로서는, 예를 들면, 알킬 황산 에스테르 염(alkyl sulfuric ester salt), 실리콘 오일계, 지방산 등을 들 수 있다. 착색제로서는, 예를 들면, 프탈로시아닌 화합물(phthalocyanine compound) 등을 들 수 있다.In the present invention, a coating composition for forming a coating film may contain a rust inhibitor, a leveling agent (surface conditioner), a surfactant, and the like, if necessary. In addition, the coloring agent may be contained in such a range that the compatibility is not lost. Examples of the rust inhibitor include tannin, gallic acid, phytic acid, phosphinic acid, and the like. Examples of the leveling agent include alkyl esters of polyalcohol and the like. Examples of the surfactant include alkyl sulfuric ester salts, silicone oils, fatty acids, and the like. As the coloring agent, for example, a phthalocyanine compound and the like can be mentioned.
(도막의 형성)(Formation of Coating Film)
본 발명의 알루미늄 기재 표면에 도막용의 액상 도료 조성물을 도장(도포)하고, 그것을 인화함으로써, 도막을 형성하고자 한다.A liquid coating composition for a coating film is applied to the surface of the aluminum substrate of the present invention, and the coating composition is printed to form a coating film.
본 발명에 있어서 도막을 형성하는 도료 조성물은, 용매를 함유한다. 각 성분은, 용매에 용해, 분산시켜 제조된다. 용매는, 각 성분을 용해 또는 분산할 수 있는 것이면 특히 한정되는 것은 없으며, 예를 들면, 물 등의 수성 용매, 아세톤(acetone), 에틸에틸케톤 , 시클로헥사논(cyclohexanone) 등의 케톤계 용제(ketone solvent), 에탄올 등의 알콜계 용제, 에틸렌글리콜모노에틸에테르(ethylene glycol monoethyl ether) 등의 에틸렌글리콜알킬에테르계 용제(ethylene glycol alkyl ether solvent), 프로필렌글리콜알킬에테르계 용제(propylene glycol alkyl ether solvent), 및 일련의 글리콜알킬에테르계 용제(glycol alkyl ether solvent)의 에스테르 화합물 등을 들 수 있다. 도료 조성물에 있어서 비스페놀 A 에폭시 수지, 및 폴리이소시아네이트의 총 함유량은, 5~50 mass%인 것이 바람직하다. 총 함유량이 5 mass% 미만이면, 인화시 발포 등이 생기며, 도막이 균일하게 형성될 수 없다. 한편, 총 함유량이 50 mass%를 넘으면, 도료 조성물의 점도가 높아지고, 취급이 어려우며, 도료 조성물을 균일하게 도포하기 힘들다.In the present invention, the coating composition for forming a coating film 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 the respective components, and examples thereof include an aqueous solvent such as water, a ketone solvent such as acetone, ethyl ethyl ketone and cyclohexanone ketone solvent and ethanol; an ethylene glycol alkyl ether solvent such as ethylene glycol monoethyl ether; a propylene glycol alkyl ether solvent; ), And ester compounds of a series of glycol alkyl ether solvents. The total content of the bisphenol A epoxy resin and the polyisocyanate in the coating composition is preferably 5 to 50 mass%. When the total content is less than 5 mass%, foaming or the like occurs upon printing, and the coating film can not be uniformly formed. On the other hand, if the total content exceeds 50 mass%, the viscosity of the coating composition becomes high, which makes handling difficult, and it is difficult to uniformly coat the coating composition.
도료 조성물의 도포 방법으로서는, 롤 코터법(roll coater method), 스프레이 법, 정전 도장법 등의 방법이 이용되지만, 도막의 균일성이 우수하고, 생산성이 양호한 롤 코터법이 바람직하다. 롤 코터법으로서는, 도포량 관리가 용이한 그라비아 롤(gravure roll) 방식이나, 두껍게 바르는 데 적합한 내추럴 코트(natural coat) 방식이나, 도포면에 미적 외관을 부여하는 것에 적합한 리버스 코트(reverse coat) 방식 등을 채용할 수 있다. 또한, 도막의 건조에는 일반적인 가열법, 유도 가열법 등이 이용된다.As a coating method of the coating composition, a roll coater method, a spraying method, an electrostatic coating method, or the like is used, but a roll coater method which is excellent in uniformity of a coating film and has good productivity is preferable. Examples of the roll coater method include a gravure roll method in which the coating amount is easy to manage and a reverse coat method in which a natural coat method suitable for thick application or an aesthetic appearance is applied to a coated surface Can be adopted. For drying the coating film, a general heating method, an induction heating method, or the like is used.
도막을 형성할 때의 인화는, 인화 온도(도달판 표면 온도)가 150℃~320℃에서 실시하는 것이 바람직하다. 인화 온도가 150℃ 미만인 경우에는, 도막이 충분히 형성되지 않고 화성 피막과의 밀착성이 낮아진다. 인화 온도가 320℃를 넘는 경우네는, 도막이 변성하고, 도막의 강도, 신장 등을 현저히 낮아지게 하여, 성형성을 저하시키게 된다. 인화 시간은 1~120초의 조건에서 실시하는 것이 바람직하다.The printing at the time of forming the coating film is preferably carried out at a printing temperature (surface temperature of the reaching plate) of 150 ° C to 320 ° C. When the printing temperature is lower than 150 캜, the coating film is not sufficiently formed and adhesion with the chemical conversion film is lowered. When the flame temperature exceeds 320 ° C, the coating film is denatured, and the strength and elongation of the coating film are remarkably lowered, and the formability is lowered. The printing time is preferably 1 to 120 seconds.
도막의 두께는, 예를 들면 콘덴서 케이스용의 알루미늄 도장재에 도막을 형성하는 경우에는, 1㎛~20㎛, 바람직하게는 5㎛~15㎛로 할 필요가 있다. 도막의 두께가 1㎛ 미만이면, 소망하는 내식성, 절연성을 얻을 수 없다. 한편, 도막의 두께가 20㎛보다 두꺼우면, 내식성, 절연성의 효과가 포화하여 경제적이지 못하게 된다.When the coating film is formed on the aluminum coating material for the condenser case, for example, the thickness of the coating film should be 1 mu m to 20 mu m, preferably 5 mu m to 15 mu m. When the thickness of the coating film is less than 1 mu m, desired corrosion resistance and insulation can not be obtained. On the other hand, if the thickness of the coating film is thicker than 20 mu m, the effect of corrosion resistance and insulation becomes saturated and it is not economical.
이와 같이 하여 제작되는 알루미늄 도장판은, 그 표면에 프레스 성형 가공용의 프레스 유를 도포하여 슬릿 가공이나 딥 드로잉 가공 등의 성형 가공을 실시함으로써, 소망하는 원통 형상을 이루는 콘덴서 케이스가 제작된다. 이와 같은 콘덴서 케이스는, 예를 들면 전해 콘덴서로서 자절히 이용되지만, 높은 가공성, 절연성, 내 고온수성, 2차 밀착성, 내 세정액성, 내식성, 내 블로킹성, 인쇄성이 필요로 하는 것이라면 사용 가능하며, 특히 한정되는 것은 없다.An aluminum coated plate manufactured in this way is coated with press oil for press forming on the surface thereof and subjected to molding such as slit processing or deep drawing processing to produce a capacitor case having a desired cylindrical shape. Such a capacitor case is used as an electrolytic capacitor, for example, but it can be used as long as it is required to have high processability, insulation property, high temperature water resistance, secondary adhesion property, lye resistance, corrosion resistance, blocking resistance and printing property , And there is no particular limitation.
[실시예][Example]
이하, 실시예 및 비교예에 기반하여, 본 발명의 적절한 실시 형태를 구체적으로 설명할 것이지만, 본 발명은 이러한 실시예에 한정되는 것은 아니다.Hereinafter, preferred embodiments of the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited to these Examples.
우선, 표 1 내지 표 3에 나타낸 각 성분을 함유하는 도료 조성물을 조제하였다. 도료 조성물의 용매에는, 시클로헥사논과 크실렌(xylene, 시클로헥사논 20 mass%)의 혼합액을 이용하였다.First, a coating composition containing the components shown in Tables 1 to 3 was prepared. As a solvent for the coating composition, a mixed solution of cyclohexanone and xylene (20 mass% of cyclohexanone) was used.
알루미늄 재 표면에는, 도막을 이하와 같이 하여 형성하였다. 알루미늄 합금판(1100-H24재, 두께 0.30mm)을 약 알칼리 탈지액으로 탈지 처리하고, 수세한 후에 건조하였다. 다음으로, 이와 같이 처리한 알루미늄 합금판 표면에, 시판 중인 인산크로메이트 처리액을 이용하여 화성 처리를 실시하였다. 그리고, 비교예 11은, 화성 처리를 실시하지 않는다. 이러한 알루미늄 합금판에, 각각의 도료 조성물을 롤 코터로 도포하였다. 도달판 표면 온도(PMT)는 270℃, 인화 시간은 42초가 되도록 인화하여, 알루미늄 도장재의 공시 재료(供試 材料)를 얻었다. 막 두께는, 와전류식 막 두께 측정계로 측정하였다.On the surface of the aluminum material, a coating film was formed as follows. The aluminum alloy plate (1100-H24 material, thickness: 0.30 mm) was degreased with a weakly alkaline degreasing solution, rinsed with water and dried. Next, the surface of the aluminum alloy plate thus treated was subjected to chemical conversion treatment using a commercially available phosphoric acid chromate treatment solution. In Comparative Example 11, no chemical conversion treatment is performed. To each aluminum alloy plate, each coating composition was applied by a roll coater. Printing plate surface temperature (PMT) was 270 [deg.] C and printing time was 42 seconds to obtain an aluminum coating material (test material). The film thickness was measured with an eddy current type film thickness meter.
(도료 조성물에 있어서 각 성분)(Each component in the coating composition)
비스페놀 A 에폭시 수지(A1): 중량평균 분자량 28,000의 비스페놀 A 에폭시 수지Bisphenol A epoxy resin (A1): bisphenol A epoxy resin having a weight average molecular weight of 28,000
비스페놀 A 에폭시 수지(A2): 중량평균 분자량 50,000의 비스페놀 A 에폭시 수지Bisphenol A epoxy resin (A2): Bisphenol A epoxy resin having a weight average molecular weight of 50,000
비스페놀 A 에폭시 수지(A3): 중량평균 분자량 25,000의 비스페놀 A 에폭시 수지Bisphenol A epoxy resin (A3): bisphenol A epoxy resin having a weight average molecular weight of 25,000
폴리이소시아네이트(B1): 폴리에틸렌글리콜디이소시아네이트(polyethylene glycoldiisocyanate)Polyisocyanate (B1): Polyethylene glycoldiisocyanate
폴리이소시아네이트(B2): 폴리프로필렌글리콜디이소시아네이트(polypropyleneglycoldiisocyanate)Polyisocyanate (B2): Polypropylene glycol diisocyanate
폴리이소시아네이트(B3): 폴리네오펜틸글리콜디이소시아네이트(polyneopentylglycoldiisocyanate)Polyisocyanate (B3): Polyneopentylglycoldiisocyanate
폴리이소시아네이트(C1): 헥사메틸렌디이소시아네이트(hexamethylene diisocyanate)Polyisocyanate (C1): hexamethylene diisocyanate
얻어진 공시 재료에 관하여, MEK에 의한 팽윤도, 표면 자유 에너지, 유리 전이 온도를 측정하였다. 또한, 각각의 공시 재료에 관하여, 성형성, 피막 밀착성, 절연성, 내 고온수성, 2차 밀착성, 내 세정액성, 내식성, 내 블로킹성, 인쇄성을 후술할 방법으로 측정하였다. 결과를, 전부 표 1 내지 표 3에 나타낸다.With respect to the obtained display material, the degree of swelling, surface free energy and glass transition temperature by MEK were measured. The formability, film adhesion, insulation, resistance to hot water, secondary adhesion, lye resistance, corrosion resistance, blocking resistance and printability were measured by the following methods with respect to each of the disclosed materials. The results are shown in all Tables 1 to 3.
(MEK에 의한 팽윤도)(Swelling degree by MEK)
공시 재료를 MEK에 24시간 침지하고, 표면에 부착되어 있는 MEK를 닦아내어, 중량을 측정하였다. 그 후, 공시 재료를 충분히 건조하고, 도막 중의 MEK를 증발시켜, 탈막(脫膜)하고, 도막량을 측정하였다.The test material was immersed in MEK for 24 hours, and the MEK adhering to the surface was wiped off and the weight was measured. Thereafter, the display material was sufficiently dried, the MEK in the coating film was evaporated, the film was separated, and the amount of the coating film was measured.
팽윤도=(MEK에서 팽윤한 도막량)/(건조한 도막량)Swelling degree = (amount of coating film swelled in MEK) / (amount of dried film)
(표면 자유 에너지)(Surface free energy)
표면 자유 에너지의 각 성분이 이미 알려진 액체로서, 증류수, 디요드메탄(diiodomethane) 및 에틸렌글리콜을 각 공시 재료에 떨어뜨렸다. 각 액체의 접촉각을 측정하여 표면 자유 에너지를 산출하였다. 그리고, 물의 분산 성분, 쌍극자 성분, 수소결합 성분은 각각, 29.1 mN/m, 1.3 mN/m, 42.4 mN/m로 하고, 디요드메탄의 분산 성분, 쌍극자 성분, 수소결합 성분은 각각, 46.8 mN/m, 4 mN/m, 0 mN/m로 하며, 에틸렌글리콜의 분산 성분, 쌍극자 성분, 수소결합 성분은 각각, 30.1 mN/m, 0 mN/m, 17.6 mN/m로 하였다.Each component of the surface free energy was a known liquid and distilled water, diiodomethane and ethylene glycol were dropped on each disclosure material. The contact angle of each liquid was measured to calculate the surface free energy. The dispersion component, the dipole component, and the hydrogen bond component of the water were 29.1 mN / m, 1.3 mN / m and 42.4 mN / m, respectively, and the dispersion component, dipole component and hydrogen bond component of the water were 46.8 mN m / m, 4 mN / m, and 0 mN / m, respectively, and the dispersion component, dipole component, and hydrogen bond component of ethylene glycol were 30.1 mN / m, 0 mN / m and 17.6 mN / m, respectively.
(유리 전이 온도)(Glass transition temperature)
유리 전이 온도는, 주파수 10Hz, 온도 상승 속도 5.0℃/min, 샘플 길이 5cm, 진폭 0.01mm의 조건에서 동적 점탄성을 측정함으로써 평가하였다. tanδ를 계산하여 그 피크를 유리 전이 온도로 하였다.The glass transition temperature was evaluated by measuring dynamic viscoelasticity under the conditions of a frequency of 10 Hz, a temperature rise rate of 5.0 DEG C / min, a sample length of 5 cm, and an amplitude of 0.01 mm. and the peak was defined as the glass transition temperature.
(성형성)(Moldability)
성형성은, 5단의 딥 드로잉 아이어닝 성형 방식에서, 도막이 형성되어 있는 쪽을 외면으로 하여 수축비 2.0의 콘덴서 케이스로 성형하고, 성형후의 도막을 육안으로 관찰함으로써 평가하였다. 성형시, 동점도 1.6 ㎟/s의 휘발성 프레스 유를 사용하였다. 하기 평가 기준에 기초하여 평가하였다.The formability was evaluated by forming the outer surface of a condensation case with a contraction ratio of 2.0 in a 5-deep deep drawing ironing molding method and observing the coated film after the molding with naked eyes. A volatile press oil having a kinematic viscosity of 1.6 mm 2 / s was used for molding. And evaluated based on the following evaluation criteria.
◎: 성형 전후에 있어서 변화가 없음◎: No change before and after molding
○: 표면이 약간 거칠어지고, 육안으로 보아서는 변화가 없으나, 확대하면 도막의 미소한 균열이 확인됨○: The surface is slightly rough and does not change when viewed from the naked eye, but when enlarged, a minute crack of the coating film is confirmed
△: 표면이 거칠어지고, 육안으로 보아도 도막의 균열을 확인할 수 있음?: The surface is roughened, and cracks of the coating film can be confirmed even with naked eyes
×: 표면이 거칠고 게다가 줄기가 관찰되며, 육안으로 보아도 도막의 균열을 확인할 수 있음X: The surface is rough and the stem is observed, and the crack of the coating can be confirmed even with the naked eye
◎, ○, 또는 △를 합격으로 하였다.?,?, Or? Was determined as acceptable.
(피막 밀착성)(Film adhesion)
성형품의 측벽부에 있어서 테이프 박리 시험을 실시하여, 도막의 잔존 상황을 육안으로 관찰하였다. 하기 평가 기준에 기초하여 평가하였다.A tape peeling test was performed on the side wall portion of the molded article to visually observe the remaining state of the coated film. And evaluated based on the following evaluation criteria.
○: 도막의 박리가 확인되지 않았다.?: Peeling of the coating film was not confirmed.
×: 도막이 박리되었다.X: The coating film was peeled off.
○를 합격으로 하였다.○ was accepted.
(절연성)(Insulating property)
JIS K 6911을 기준으로 하여 근거로 한 절연성 시험을 실시하고, 표면 저항을 측정하였다. 하기 평가 기준에 기초하여 평가하였다.The insulation resistance test was performed based on JIS K 6911, and the surface resistance was measured. And evaluated based on the following evaluation criteria.
◎: 표면저항≥1014Ω◎: Surface resistance ≥10 14 Ω
○: 1014Ω>표면저항≥1010Ω?: 10 14 ?> Surface resistance? 10 10 ?
△:1010Ω>표면저항≥106Ω?: 10 10 ?> Surface resistance? 10 6 ?
×:106>표면저항×: 10 6 > Surface resistance
◎, ○, 또는 △를 합격으로 하였다.?,?, Or? Was determined as acceptable.
(내 고온수성)(High temperature water resistance)
상기의 성형품을, 121℃의 수증기에 5일간 노출시켰다. 수지 도막의 변색 상황을 육안으로 관찰하였다. 하기 평가 기준에 기초하여 평가하였다.The above molded product was exposed to steam of 121 캜 for 5 days. The discoloration state of the resin coating film was visually observed. And evaluated based on the following evaluation criteria.
◎: 도막의 변색이 확인되지 않았다.?: No discoloration of the coating film was observed.
○: 도막의 일부가 변색되었지만, 제품의 사용에 견딜 수 있다.A: Part of the coating film was discolored, but it can withstand the use of the product.
×: 도막 전체가 변색되었다.X: The entire coating film was discolored.
◎, ○를 합격으로 하였다.◎ and ○ were accepted.
(2차 밀착성)(Secondary adhesion)
상기의 성형품을, 121℃의 수증기에 5일간 노출시켰다. 성형품의 측벽부에 있어서 테이프 박리 시험을 실시하고, 도막의 잔존 상황으로 평가하였다. 하기 평가 기준에 기초하여 평가하였다.The above molded product was exposed to steam of 121 캜 for 5 days. A tape peeling test was performed on the side wall portion of the molded article to evaluate the remaining state of the coated film. And evaluated based on the following evaluation criteria.
○: 도막의 박리가 확인되지 않았다.?: Peeling of the coating film was not confirmed.
×: 도막이 박리되었다.X: The coating film was peeled off.
○를 합격으로 하였다.○ was accepted.
(내 세정액성)(Cleaning liquid resistance)
세정액으로서 사용되는 아쿠아솔벤트G(탄화수소계 세정제: 아쿠아 화학 주식회사 제품, 등록상표)에 침지(상온에서 1시간 침지)하고, 도막의 변색 상황을 육안으로 관찰하였다. 하기 평가 기준에 기초하여 평가하였다.(Immersed at room temperature for 1 hour) in Aqua Solvent G (hydrocarbon-based cleaner: Aqua Chemical Co., Ltd., registered trademark) used as a cleaning liquid, and the discoloration state of the coating film was visually observed. And evaluated based on the following evaluation criteria.
◎: 도막의 용해, 변색이 확인되지 않았다.&Amp; cir &: No dissolution or discoloration of the coating film was observed.
○: 도막의 일부가 변색되었지만, 제품의 사용에 견딜 수 있다.A: Part of the coating film was discolored, but it can withstand the use of the product.
△: 도막은 용해되지 않았지만, 변색이 확인되었다.B: The coating film was not dissolved, but discoloration was confirmed.
×: 도막이 용해되었다.X: The coating film was dissolved.
◎, ○, 또는 △를 합격으로 하였다.?,?, Or? Was determined as acceptable.
(내식성)(Corrosion resistance)
JIS Z2371에 기초하여, 염수 분무 시험을 1,000시간 실시하고, 레이팅 넘버(Rating Number, R.N.)에 의하여 내식성을 측정하였다.Based on JIS Z2371, the salt spray test was carried out for 1,000 hours and the corrosion resistance was measured by a rating number (RN).
R.N. 9.0 이상을 합격으로 하였다.R.N. 9.0 and above were accepted.
(내 블로킹성)(Blocking resistance)
각 재료의 도장면과 화성 피막면을 서로 겹쳐서, 그 위로부터, 2kPa의 하중을 가하고, 50℃에서 1일간 보관하고, 도막의 점착 상태를 육안으로 관찰하였다.The coating surface and the chemical conversion coating surface of each material were overlapped with each other, and a load of 2 kPa was applied thereon. The coating was stored at 50 캜 for one day, and the state of adhesion of the coating film was visually observed.
○: 도막의 변화, 점착이 확인되지 않았다.?: No change in coating film or adhesion was observed.
△: 도막이 변화하였지만, 점착이 확인되지 않았다.C: Coating was changed, but no adhesion was observed.
×: 도막의 점착이 확인되었다.X: Coating adhesion was confirmed.
○, △를 합격으로 하였다.○ and △ were accepted.
(인쇄성)(Printability)
실크스크린 잉크로 공시 재료에 인쇄를 행하였다. UV 경화후의 잉크와의 밀착성을 격자눈이 구비된 테이프의 박리에 의하여 격자눈의 비 박리율로 평가하였다. 실크스크린 잉크는 RIG(상품명, 세이코 어드밴스사 제, UV 경화성 금속용 잉크)를 사용하였다.Printing was performed on the disclosed material with silk screen ink. The adhesiveness to the ink after UV curing was evaluated by the peel ratio of the latticed eyes by the peeling of the tape provided with the latticed eyes. The silk screen ink used was RIG (trade name, a product of Seiko Advance, UV curable metal ink).
○: 박리 없음 100/100○: No peeling 100/100
△: 일부 박리 1/100~99/100?: Partial peeling 1/100 to 99/100
×: 전면 박리 0/100, 또는 인쇄후 잉크가 번져 사용에 견딜 수 없게 되었다.X: Peeling of the entire surface 0/100, or ink bleeds after printing, so that it can not withstand use.
○를 합격으로 하였다.○ was accepted.
표 1, 2와 같이 실시예 1~21은 모두, 성형성, 피막 밀착성, 절연성, 내 고온수성, 2차 밀착성, 내 세정액성, 내식성, 내 블로킹성 및 인쇄성이 양호하였다. 또한, 실시예 7~9, 20~21은 성형성, 내 세정액성, 내식성, 내 블로킹성, 인쇄성이 뛰어나게 우수하였다.As shown in Tables 1 and 2, in all of Examples 1 to 21, moldability, film adhesion, insulation, high temperature water resistance, secondary adhesion, lye resistance, corrosion resistance, blocking resistance and printability were good. Further, Examples 7 to 9 and 20 to 21 were excellent in moldability, lye resistance, corrosion resistance, blocking resistance and printing property.
이것에 비하여, 표 3과 같이, 비교예 1에서는, 베이스 수지로서 폴리에스테르 수지를 이용하였으므로, 내 고온수성을 만족할 수 없었다. 비교예 2는, 베이스 수지로서 폴리에스테르 수지와 폴리아크릴산을 이용하였으므로, 내 고온수성을 만족할 수 없었다. 비교예 3은, 베이스 수지로서 폴리프로필렌을 이용하였으므로, 내 블로킹성, 인쇄성을 만족할 수 없었다. 비교예 4는, 비스페놀 A 에폭시 수지만 이용하고, 폴리이소시아네이트를 이용하지 않았으므로, 유리 전이 온도가 너무 높아, 2차 밀착성을 만족할 수 없었다. 비교예 5는, 베이스 수지로서 폴리에스테르 수지를 이용하였으므로, 내 고온수성을 만족할 수 없었다. 비교예 6은, 도막의 유리 전이 온도가 너무 낮기 때문에, 내 블로킹성을 만족할 수 없었다. 비교예 7은, 도막의 유리 전이 온도가 너무 높기 때문에, 2차 밀착성을 만족할 수 없었다. 비교예 8은, 도막의 표면 자유 에너지가 너무 높기 때문에, 인쇄시 얼룩이 발생하고 말았다. 비교예 9는, 도막의 MEK에 의한 팽윤도가 너무 높기 때문에, 내 세정액성을 만족할 수 없었다. 비교예 10은, 도막 중에 폴리에틸렌 왁스를 함유시켰기 때문에, 도막의 표면 자유 에너지가 낮아지며, 인쇄성을 만족할 수 없었다. 비교예 11은, 화성 처리를 실시하지 않았기 때문에, 내식성, 2차 밀착성을 만족할 수 없었다.On the other hand, as shown in Table 3, in Comparative Example 1, since the polyester resin was used as the base resin, the high temperature aqueous solution could not be satisfied. In Comparative Example 2, since polyester resin and polyacrylic acid were used as the base resin, the high temperature water resistance could not be satisfied. In Comparative Example 3, polypropylene was used as the base resin, so that blocking resistance and printability were not satisfied. In Comparative Example 4, since only the bisphenol A epoxy resin was used and the polyisocyanate was not used, the glass transition temperature was too high to satisfy the secondary adhesion property. In Comparative Example 5, since the polyester resin was used as the base resin, the high temperature water resistance could not be satisfied. In Comparative Example 6, the anti-blocking property could not be satisfied because the glass transition temperature of the coated film was too low. In Comparative Example 7, since the glass transition temperature of the coated film was too high, the secondary adhesion property could not be satisfied. In Comparative Example 8, since the surface free energy of the coating film was too high, unevenness occurred during printing. In Comparative Example 9, the degree of swelling of the coating film due to MEK was too high, so that the cleaning liquid 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 lowered and the printing property could not be satisfied. In Comparative Example 11, since the chemical conversion treatment was not carried out, the corrosion resistance and the secondary adhesion were not satisfied.
[산업상의 이용 가능성][Industrial Availability]
본 발명에 의하여, 성형성, 피막 밀착성, 절연성, 내 고온수성, 2차 밀착성, 내 세정액성, 내식성, 내 블로킹성 및 인쇄성이 우수하고, 게다가 비용면이나 안전성, 환경면에 있어서 우수한 성능을 발휘하는 도막을 표면에 구비한 콘덴서 케이스용 알루미늄 도장재를 얻을 수 있다.
According to the present invention, it is possible to provide a resin composition which is excellent in moldability, film adhesion, insulation property, high temperature water resistance, secondary adhesion property, lye resistance, corrosion resistance, blocking resistance and printing property, An aluminum coating material for a condenser case having a coating film on its surface can be obtained.
Claims (5)
상기 도막은, 비스페놀 A 에폭시 수지(bisphenol A epoxy resin)를 포함하고, 메틸에틸케톤(methyl ethyl ketone)에 의한 팽윤도가 1.05 이상 1.5 미만, 표면 자유 에너지가 36 mN/m~50mN/m 이고, 유리 전이 온도가 50℃~100℃인 것을 특징으로 하는 콘덴서 케이스용 알루미늄 도장재.An aluminum coating material comprising an aluminum substrate, a chemical conversion coating formed on at least one surface of the aluminum base, and a coating film formed on the chemical conversion coating,
Wherein the coating film comprises bisphenol A epoxy resin and has a degree of swelling by methyl ethyl ketone of 1.05 or more and less than 1.5, a surface free energy of 36 mN / m to 50 mN / m, Wherein the transition temperature is 50 占 폚 to 100 占 폚.
상기 도막은, 비스페놀 A 에폭시 수지 및 폴리이소시아네이트(polyisocyanate)를 함유하고, 상기 비스페놀 A 에폭시 수지와 상기 폴리이소시아네이트의 중량 비율은, 50/50~90/10인 것을 특징으로 하는 콘덴서 케이스용 알루미늄 도장재.The method according to claim 1,
Wherein the coating film contains a bisphenol A epoxy resin and a polyisocyanate and the weight ratio of the bisphenol A epoxy resin to the polyisocyanate is 50/50 to 90/10.
상기 폴리이소시아네이트는, 폴리에테르(polyether) 골격을 가지는 디이소시아네이트(diisocyanate)인 것을 특징으로 하는 콘덴서 케이스용 알루미늄 도장재.The method of claim 2,
Wherein the polyisocyanate is a diisocyanate having a polyether skeleton. 2. The aluminum coating material for a condenser case according to claim 1, wherein the polyisocyanate is a diisocyanate having a polyether skeleton.
상기 폴리이소시아네이트는, 폴리에테르 골격을 가지는 디이소시아네이트 및 알킬렌(alkylene) 사슬을 가지는 디이소시아네이트이며, 상기 폴리에테르 골격을 가지는 디이소시아네이트와 상기 알킬렌 사슬을 가진 디이소시아네이트의 중량 비율은, 50/50~95/5인 것을 특징으로 하는 콘덴서 케이스용 알루미늄 도장재.The method of claim 2,
Wherein the polyisocyanate is a diisocyanate having a polyether skeleton and a diisocyanate having an alkylene chain, the weight ratio of the diisocyanate having the polyether skeleton to the diisocyanate having the alkylene chain is 50/50 To 95/5. ≪ / RTI >
상기 폴리에테르 골격은, 네오펜틸글리콜(neopentyl glycol) 골격인 것을 특징으로 하는 콘덴서 케이스용 알루미늄 도장재.The method according to claim 3 or 4,
Wherein the polyether skeleton is a neopentyl glycol skeleton.
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|---|---|---|---|
| JPJP-P-2013-188381 | 2013-09-11 | ||
| JP2013188381A JP6184266B2 (en) | 2013-09-11 | 2013-09-11 | Aluminum paint for capacitor case |
| PCT/JP2014/068602 WO2015037322A1 (en) | 2013-09-11 | 2014-07-11 | Coated aluminum material for capacitor case |
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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 |
| EP3736841A4 (en) * | 2018-01-25 | 2021-11-24 | Murata Manufacturing Co., Ltd. | Film capacitor, and exterior case for film capacitor |
| 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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| JP2010111111A (en) | 2008-10-10 | 2010-05-20 | Sumitomo Light Metal Ind Ltd | Resin-coated aluminum alloy plate for bottomed cylindrical case for capacitor |
| 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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| JP2886917B2 (en) * | 1989-12-27 | 1999-04-26 | 三井化学株式会社 | Resin composition for paint |
| JP3497818B2 (en) * | 2000-12-13 | 2004-02-16 | 住化バイエルウレタン株式会社 | Paint 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 |
| 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 |
| 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 |
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- 2014-07-11 KR KR1020147033587A patent/KR101677222B1/en active IP Right Grant
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- 2014-07-11 WO PCT/JP2014/068602 patent/WO2015037322A1/en active Application Filing
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010111111A (en) | 2008-10-10 | 2010-05-20 | Sumitomo Light Metal Ind Ltd | Resin-coated aluminum alloy plate for bottomed cylindrical case for capacitor |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2015056488A (en) | 2015-03-23 |
| CN105453202A (en) | 2016-03-30 |
| CN105453202B (en) | 2018-05-11 |
| WO2015037322A1 (en) | 2015-03-19 |
| TW201510119A (en) | 2015-03-16 |
| MY181329A (en) | 2020-12-21 |
| JP6184266B2 (en) | 2017-08-23 |
| KR20150048668A (en) | 2015-05-07 |
| TWI609055B (en) | 2017-12-21 |
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