WO2018122935A1 - めっきされたアルミニウム又はアルミニウム合金製のスライドファスナー又はボタンの部材 - Google Patents
めっきされたアルミニウム又はアルミニウム合金製のスライドファスナー又はボタンの部材 Download PDFInfo
- Publication number
- WO2018122935A1 WO2018122935A1 PCT/JP2016/088769 JP2016088769W WO2018122935A1 WO 2018122935 A1 WO2018122935 A1 WO 2018122935A1 JP 2016088769 W JP2016088769 W JP 2016088769W WO 2018122935 A1 WO2018122935 A1 WO 2018122935A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- plating layer
- plating
- slide fastener
- button member
- copper
- Prior art date
Links
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 22
- 238000007747 plating Methods 0.000 claims abstract description 312
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 claims abstract description 54
- 239000000463 material Substances 0.000 claims abstract description 48
- 239000011701 zinc Substances 0.000 claims abstract description 47
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 45
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 45
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 45
- 238000009792 diffusion process Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims description 32
- 229910045601 alloy Inorganic materials 0.000 claims description 29
- 239000000956 alloy Substances 0.000 claims description 29
- 229910052802 copper Inorganic materials 0.000 claims description 22
- 239000010949 copper Substances 0.000 claims description 22
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 238000005336 cracking Methods 0.000 abstract description 8
- 239000002585 base Substances 0.000 description 34
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 235000019646 color tone Nutrition 0.000 description 13
- 230000007797 corrosion Effects 0.000 description 13
- 238000005260 corrosion Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910020994 Sn-Zn Inorganic materials 0.000 description 8
- 229910009069 Sn—Zn Inorganic materials 0.000 description 8
- 238000005238 degreasing Methods 0.000 description 7
- 238000013507 mapping Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 230000003746 surface roughness Effects 0.000 description 6
- 238000002788 crimping Methods 0.000 description 5
- 238000009713 electroplating Methods 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000004080 punching Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910017755 Cu-Sn Inorganic materials 0.000 description 4
- 229910017927 Cu—Sn Inorganic materials 0.000 description 4
- 206010020751 Hypersensitivity Diseases 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 230000007815 allergy Effects 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 4
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
- 230000002708 enhancing effect Effects 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910018134 Al-Mg Inorganic materials 0.000 description 3
- 229910018467 Al—Mg Inorganic materials 0.000 description 3
- 229910001369 Brass Inorganic materials 0.000 description 3
- 239000010951 brass Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 229910021365 Al-Mg-Si alloy Inorganic materials 0.000 description 2
- 229910018131 Al-Mn Inorganic materials 0.000 description 2
- 229910018461 Al—Mn Inorganic materials 0.000 description 2
- 229910017518 Cu Zn Inorganic materials 0.000 description 2
- 229910017752 Cu-Zn Inorganic materials 0.000 description 2
- 229910017943 Cu—Zn Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- -1 organic acid salts Chemical class 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 229910021364 Al-Si alloy Inorganic materials 0.000 description 1
- 229910018182 Al—Cu Inorganic materials 0.000 description 1
- 229910018571 Al—Zn—Mg Inorganic materials 0.000 description 1
- 229910018569 Al—Zn—Mg—Cu Inorganic materials 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 1
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910020810 Sn-Co Inorganic materials 0.000 description 1
- 229910020938 Sn-Ni Inorganic materials 0.000 description 1
- 229910018757 Sn—Co Inorganic materials 0.000 description 1
- 229910008937 Sn—Ni Inorganic materials 0.000 description 1
- 229910008996 Sn—Ni—Cu Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 229910007568 Zn—Ag Inorganic materials 0.000 description 1
- 229910007610 Zn—Sn Inorganic materials 0.000 description 1
- JAVUICMNNLXTRS-UHFFFAOYSA-L [O-]P([O-])(=O)OP(=O)(O)O.P(=O)(O)(O)O.[Cu+2] Chemical compound [O-]P([O-])(=O)OP(=O)(O)O.P(=O)(O)(O)O.[Cu+2] JAVUICMNNLXTRS-UHFFFAOYSA-L 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001447 alkali salts Chemical group 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229940050410 gluconate Drugs 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229940074439 potassium sodium tartrate Drugs 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
-
- A—HUMAN NECESSITIES
- A44—HABERDASHERY; JEWELLERY
- A44B—BUTTONS, PINS, BUCKLES, SLIDE FASTENERS, OR THE LIKE
- A44B1/00—Buttons
- A44B1/02—Buttons characterised by their material
-
- A—HUMAN NECESSITIES
- A44—HABERDASHERY; JEWELLERY
- A44B—BUTTONS, PINS, BUCKLES, SLIDE FASTENERS, OR THE LIKE
- A44B1/00—Buttons
- A44B1/04—Ornamental buttons
-
- A—HUMAN NECESSITIES
- A44—HABERDASHERY; JEWELLERY
- A44B—BUTTONS, PINS, BUCKLES, SLIDE FASTENERS, OR THE LIKE
- A44B1/00—Buttons
- A44B1/08—Constructional characteristics
-
- A—HUMAN NECESSITIES
- A44—HABERDASHERY; JEWELLERY
- A44B—BUTTONS, PINS, BUCKLES, SLIDE FASTENERS, OR THE LIKE
- A44B19/00—Slide fasteners
-
- A—HUMAN NECESSITIES
- A44—HABERDASHERY; JEWELLERY
- A44B—BUTTONS, PINS, BUCKLES, SLIDE FASTENERS, OR THE LIKE
- A44B19/00—Slide fasteners
- A44B19/24—Details
-
- A—HUMAN NECESSITIES
- A44—HABERDASHERY; JEWELLERY
- A44B—BUTTONS, PINS, BUCKLES, SLIDE FASTENERS, OR THE LIKE
- A44B19/00—Slide fasteners
- A44B19/42—Making by processes not fully provided for in one other class, e.g. B21D53/50, B21F45/18, B22D17/16, B29D5/00
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/42—Pretreatment of metallic surfaces to be electroplated of light metals
- C25D5/44—Aluminium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/02—Slide fasteners
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
Definitions
- the present invention relates to a slide fastener or button member made of plated aluminum or aluminum alloy.
- the invention relates to a fastener element made of plated aluminum or aluminum alloy.
- Japanese Patent Application Laid-Open No. 2014-19953 discloses a step 1 in which shape processing is performed using aluminum or an aluminum alloy as a raw material, and a semi-finished product of a button or a slide fastener member, and an electric strike plating of copper in a barrel.
- Step 2 of forming the first copper plating layer directly on the whole, and then the second copper plating thicker than the first copper plating layer directly on the first copper plating layer by electroplating copper with a barrel
- a method of manufacturing a copper-plated button or fastener member comprising the step 3 of forming a layer is described.
- JP 2012-143798 A an aluminum alloy having a predetermined composition is cast to obtain a casting, the surface of the casting is electropolished and then subjected to a zincate treatment, and an electrolytic copper plating layer is formed thereon, Furthermore, a method for producing a plated aluminum alloy casting on which an electric nickel plating layer is formed is described.
- the gazette describes that the adhesion of a plating layer formed thereon can be improved by forming a zincate (zinc substitution) treatment layer as a base layer on the casting surface. It is also described that it is preferable to perform the zincate treatment a plurality of times from the viewpoint of the properties and the glitter.
- JP-A-2-240290 discloses a copper pyrophosphate plating bath containing phosphoric acid and / or phosphate after pretreatment such as alkali degreasing, washing with a surfactant, pickling and washing with water.
- a method is described in which copper is plated directly onto aluminum by plating and then heat treating the aluminum.
- Example 1 of the publication describes that a copper plating layer having a thickness of about 10 ⁇ m was formed on an aluminum plate by the above method. According to this method, a uniform copper plating layer can be formed, the adhesion between the aluminum substrate and the copper plating layer is extremely good, and the appearance is also beautiful.
- plating is performed on the deformed line and the round line before being processed into an element, so that when the element shape is processed after plating, the cross section where the plating film is not formed is exposed and the aesthetic appearance is impaired.
- nickel plating provides high gloss, the coating film is hard and easily cracked, and there is a risk of allergies, so there is much room for improvement.
- the method described in Japanese Patent Application Laid-Open No. 2014-19953 is a technique for forming a copper plating film on the entire surface by performing barrel plating after performing shape processing on a fastener element or the like.
- a fastener element is required to have high resistance to cracking because frictional force and bending stress are applied to the plating film when crimped to a fastener tape.
- JP 2012-143798 A a zincate treatment using a substitution reaction between zinc and aluminum is performed as a pretreatment to improve the adhesion between the plating film and the material aluminum.
- this method employs nickel plating, and it cannot be said that the crack resistance is sufficient, and the problem of allergy remains.
- the present invention was created in view of the above circumstances, and an object of the present invention is to provide a plated fastener or button member made of plated aluminum or aluminum alloy that has both crack resistance and gloss. Another object of the present invention is to provide a method for producing such a slide fastener or button member.
- the present inventor conducted extensive research to solve the above problems, and after performing zincate treatment on a material made of aluminum or an aluminum alloy, the plating adhesion and cracking resistance were formed by forming a copper pyrophosphate plating layer. It has been found that high gloss can be ensured by forming a copper sulfate plating layer thereon. Furthermore, it has been found that by forming a hard finish plating layer on the copper sulfate plating layer, appearances of various colors are given, wear resistance is improved, and corrosion of the slide fastener or button member is prevented. The present inventor has completed the present invention based on such knowledge.
- the present invention includes a base material made of aluminum or an aluminum alloy, a zinc diffusion layer in which zinc is diffused on the inner surface of the base material, and a plurality of plating layers covering the zinc diffusion layer.
- the layer is a slide fastener or button member having a copper pyrophosphate plating layer and a copper sulfate plating layer in order from the inside.
- the average thickness of the copper pyrophosphate plating layer is 20 ⁇ m or less.
- the copper pyrophosphate plating layer has an average thickness of 5 to 20 ⁇ m.
- the copper pyrophosphate plating layer has a copper pyrophosphate strike plating layer having an average thickness of 0.1 to 5 ⁇ m as a base.
- the average thickness of the copper sulfate plating layer is 7 ⁇ m or less.
- the average thickness of the copper sulfate plating layer is 1 to 7 ⁇ m.
- the ratio of the average thickness of the copper sulfate plating layer to the average thickness of the copper pyrophosphate plating layer is 0.1 to 0.5.
- the plurality of plating layers further include a finish plating layer harder than the copper sulfate plating layer outside the copper sulfate plating layer.
- the finish plating layer is an alloy plating layer containing Cu and Sn.
- the average thickness of the finish plating layer is 0.5 to 5 ⁇ m.
- the arithmetic average roughness of the outermost surface is 0.3 ⁇ m or less.
- the plurality of plating layers further include a plating layer having a color tone different from that of the finish plating layer on the outside of the finish plating layer.
- the entire surface of the base material is covered with the plurality of plating layers.
- the present invention is an article provided with a slide fastener or button member according to the present invention.
- FIG. 1 Another aspect of the present invention is a fastener stringer in which a member of the slide fastener according to the present invention is a fastener element, and a plurality of the fastener elements are fixed by caulking along one side edge of the fastener tape.
- Preparing an aluminum or aluminum alloy base material processed into the shape of a slide fastener or button member A step of sequentially performing zincate treatment, copper pyrophosphate plating, and copper sulfate plating on at least a part of the surface of the base material; The manufacturing method of the member of a slide fastener or a button containing this.
- a slide fastener or button member made of plated aluminum or aluminum alloy having both crack resistance and gloss.
- a fastener element having both crack resistance and glossiness and low sliding resistance.
- the plating structure concerning one embodiment of the member of the slide fastener or button of the present invention is shown.
- the plating structure which concerns on another one Embodiment of the member of the slide fastener or button of this invention is shown.
- the plating structure concerning another one embodiment of the member of the slide fastener or button of the present invention is shown.
- FIG. 1 shows a plating structure according to an embodiment of a slide fastener or button member according to the present invention.
- 1 includes a base material (101) made of aluminum or an aluminum alloy, a zinc diffusion layer (102) in which zinc diffuses inside the base material surface, and a zinc diffusion layer ( 102), and the plurality of plating layers have a copper pyrophosphate plating layer (103) and a copper sulfate plating layer (104) in that order from the inside.
- the base material (101) is preferably coated with the plurality of plating layers in order to enhance the aesthetic appearance and the corrosion resistance.
- FIG. 2 shows a plating structure according to another embodiment of a slide fastener or button member according to the present invention.
- the finish plating layer (105) is harder than the copper sulfate plating layer (104) on the outer side of the copper sulfate plating layer (104). It differs from the embodiment of FIG. Also in the present embodiment, it is preferable for the base material (101) that the entire surface is covered with the plurality of plating layers in terms of enhancing the aesthetics and enhancing the corrosion resistance.
- FIG. 3 shows a plating structure according to still another embodiment of a slide fastener or button member according to the present invention.
- the plurality of plating layers further have a plating layer (106) having a color tone different from that of the finish plating layer (105) outside the finish plating layer (105). This is different from the embodiment of FIG. Also in the present embodiment, it is preferable for the base material (101) that the entire surface is covered with the plurality of plating layers in terms of enhancing the aesthetics and enhancing the corrosion resistance.
- the member of the slide fastener or button according to the present invention uses aluminum or an aluminum alloy as a base material (101).
- aluminum alloys include, but are not limited to, Al—Cu alloys, Al—Mn alloys, Al—Si alloys, Al—Mg alloys, Al—Mg—Si alloys, Al—Zn—Mg alloys. And Al—Zn—Mg—Cu based alloys.
- Al—Mg alloy, an Al—Mn alloy, and an Al—Mg—Si alloy are preferable, and an Al—Mg alloy is more preferable because of strength and workability.
- the base material is preferably processed into the shape of a slide fastener or a button before various plating layers are formed.
- the fastener element can be processed into individual element shapes by punching a flat wire made of aluminum or aluminum alloy. Accordingly, it is not necessary to perform a cutting process after forming the plating layer on the base material, so that it is possible to prevent an exposed surface where the plating layer is not formed. Further, since the base material is processed into the shape of a slide fastener or a button member, the size of the base material is reduced, so that barrel plating can be performed in each plating step described below.
- Barrel plating eliminates the need to set the material to be plated on the jig, enables mass production compared to stationary plating, and leaves no contact marks when the material to be plated is set on the jig. No worries about corrosion from contact marks. Barrel plating can plate the entire surface of the product, while static plating does not plate the parts covered by the jig.
- the slide fastener or button member according to the present invention has a zinc diffusion layer (102) in which zinc is diffused on the inner surface of the base material.
- the zinc diffusion layer preferably has an average thickness of 50 nm or more from the viewpoint of improving plating adhesion, more preferably has an average thickness of 100 nm or more, still more preferably has an average thickness of 200 nm or more, and 250 nm or more.
- the average thickness of a zinc diffused layer is defined as a value obtained by measuring as follows.
- a slice sample for cross-sectional observation is produced from a slide fastener or button member by CP method (Cross-section Polisher) and focused ion beam (FIB).
- FIB focused ion beam
- a section of the zinc diffusion layer is observed with a TEM using the obtained flake sample, and elemental analysis is performed by energy dispersive X-ray spectroscopy (EDX).
- EDX energy dispersive X-ray spectroscopy
- the island having the farthest distance from the base material surface is the boundary line length of 500 nm on the base material surface.
- “Distance from the surface of the base metal” refers to the distance from the base material surface to the far end of the island when the normal line is drawn from the base material surface toward the island (the farthest distance from the base material surface in the island) Is defined as the distance.
- the average value when the said distance about the island with the longest distance from a base material surface is measured in 10 or more observation visual fields is made into the average thickness of a zinc diffusion layer.
- the length of the boundary line on the surface of the base material is about 500 nm, and among the “islands” in which the diameter of the smallest circle that can surround one island is 10 nm or more, The island that is the farthest from the base metal surface when the normal is drawn from the surface is circled in the figure.
- the distance from the base material surface of the island is about 210 nm.
- the zinc diffusion layer can be formed by performing a zincate treatment.
- FIG. 5 exemplarily shows a preferred execution procedure for the zincate treatment and its pretreatment.
- the method of the zincate treatment is known per se and need not be explained in particular, but illustratively, there is a method in which the surface of a slide fastener or button made of aluminum or aluminum alloy is cleaned and then immersed in a zinc replacement treatment solution. Can be mentioned.
- a zinc replacement treatment liquid a mixed solution containing sodium hydroxide and zinc oxide is generally used. Zinc sulfate may be used instead of zinc oxide or in combination with zinc oxide.
- Rochelle salt potassium sodium tartrate
- other complexing organic acid salts such as gluconate and salicylate
- other additives such as sodium nitrate, copper, iron or nickel salts
- the bath temperature can be 10 to 40 ° C.
- the treatment time can be 10 to 60 minutes.
- a typical example of a method for carrying out the zincate treatment a plurality of times is a double zincate treatment.
- the double zincate treatment after the article to be treated is once immersed in the zinc replacement treatment solution, the slide fastener or button member is immersed in nitric acid or the like to separate the deposited zinc, and the treatment subject article is again made into the zinc replacement treatment solution. It is a method including soaking. A water washing treatment may be appropriately sandwiched between the steps.
- pretreatment such as degreasing, pickling, washing with a surfactant, washing with water, and ultrasonic washing may be mentioned.
- a method of performing degreasing, chemical polishing (etching) and desmutting in this order is exemplified as a suitable method.
- a water washing treatment may be appropriately sandwiched between the steps.
- the degreasing liquid include an alkaline degreasing liquid containing an appropriate amount of a surfactant and further containing at least one alkali salt such as sodium hydroxide, sodium carbonate, sodium phosphate, sodium metasilicate, sodium sulfate, sodium borate and the like.
- Degreasing can be performed by immersing the slide fastener or button member in a degreasing solution at 70 to 80 ° C. for 1 to 3 minutes.
- etching solution used for chemical polishing examples include an alkaline etching solution containing sodium hydroxide and an acidic etching solution containing at least one of sulfuric acid and phosphoric acid.
- Chemical polishing treatment is possible by immersing the button member for 0.5 to 3 minutes. The oxide film on the surface of the member can be removed by chemical polishing.
- Desmut includes a method in which a slide fastener or button member is immersed for 1 to 60 seconds in a processing solution at 20 to 50 ° C. containing a strong acid such as nitric acid, sulfuric acid and hydrofluoric acid.
- the average thickness of each plating layer refers to an average value when the plating layer is analyzed with an electron microscope or an optical microscope, and each plating thickness of 10 or more points is measured.
- a copper pyrophosphate plating layer (103) is formed on the zinc diffusion layer (102).
- the copper pyrophosphate plating layer is excellent in that the effect of suppressing cracking is high.
- a fastener tape is disposed between a pair of legs of the fastener element, It is attached to the fastener tape by caulking the leg of the inner side.
- FIG. 6 illustrates a state before the fastener element 108 is crimped (a) and after the fastener element 108 is crimped to the fastener tape 109 (b).
- the opening angle ⁇ of the pair of legs is typically 30 to 50 ° before caulking, and the pair of legs is typically parallel after caulking. Therefore, when the fastener element is caulked, the plating layer formed on the surface is extended and cracking is likely to occur.
- a copper pyrophosphate plating layer (103) with a small amount of deformation because it is close to the base material inside, a copper sulfate plating layer (explained later) formed on the outside of the copper pyrophosphate plating layer (103) 104) and a hard finish plating layer (105) can be formed thinly, and a crack can be suppressed.
- the copper pyrophosphate plating solution is weakly alkaline, and is excellent in that the plating around the zincate treatment is good.
- the copper pyrophosphate plating layer is a plating layer obtained by using a plating solution containing copper pyrophosphate, and Cu and P are contained in the plating layer.
- the average thickness of the copper pyrophosphate plating layer (103) is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less in order to shorten the processing time (cost reduction) or to reduce the sliding resistance. More preferably, it is 11 ⁇ m or less.
- the average thickness of the copper pyrophosphate plating layer (103) is preferably 5 ⁇ m or more, more preferably 6 ⁇ m or more, and even more preferably 8 ⁇ m or more for reasons of corrosion resistance.
- the copper pyrophosphate plating layer (103) is formed by forming a copper pyrophosphate phosphate plating layer (103b) thick after forming a copper pyrophosphate strike plating layer (103a) as a base for the purpose of preventing replacement of the zinc diffusion layer. It is preferable from the viewpoint of improving plating adhesion and improving leveling properties.
- the average thickness of the copper pyrophosphate strike plating layer (103a) is preferably 5 ⁇ m or less in order to shorten the processing time (cost reduction) or to reduce the sliding resistance, and more preferably 3 ⁇ m or less. Preferably, it is still more preferable that it is 2 micrometers or less.
- the average thickness of the copper pyrophosphate strike plating layer (103a) is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, and more preferably 0.8 ⁇ m or more for reasons of corrosion resistance. Is more preferable.
- the thickness of the copper pyrophosphate plating layer refers to the total thickness of the copper pyrophosphate strike plating layer and the copper pyrophosphate copper plating layer.
- Copper pyrophosphate strike plating can be performed by electroplating at a current density of 2 to 15 A / dm 2 for about 0.5 to 30 minutes in a weak alkaline plating bath containing copper pyrophosphate at 40 to 70 ° C. .
- Copper pyrophosphate main plating can be performed by electroplating in a weak alkaline plating bath containing copper pyrophosphate at 40 to 70 ° C. at a current density of 1 to 10 A / dm 2 for about 1 to 120 minutes.
- Zn in the zinc diffusion layer is an amphoteric metal, it is easy to dissolve in acidic and alkaline solutions, but copper pyrophosphate plating can be performed with a plating solution close to neutrality, so damage to the zinc diffusion layer is not possible. There is an advantage of less.
- a copper sulfate plating layer (104) is formed on the copper pyrophosphate plating layer (103).
- the copper sulfate plating layer is excellent in that high gloss is obtained. For this reason, laminating the copper pyrophosphate plating layer (103) and the copper sulfate plating layer (104) in this order is important for achieving both plating adhesion and gloss.
- the copper sulfate plating layer is a plating layer obtained by using a plating solution containing copper sulfate, and Cu and S are contained in the plating layer.
- the average thickness of the copper sulfate plating layer (104) is preferably 7 ⁇ m or less in order to shorten the processing time (cost reduction), to prevent cracking or to reduce the sliding resistance, and is 5 ⁇ m or less. More preferably, it is 4 ⁇ m or less. Further, the average thickness of the copper sulfate plating layer (104) is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, and even more preferably 3 ⁇ m or more in order to obtain high gloss.
- the thickness ratio between the copper pyrophosphate plating layer (103) and the copper sulfate plating layer (104) affects the balance between plating adhesion and gloss. Therefore, from the viewpoint of achieving both excellent plating adhesion and high gloss, the ratio of the average thickness of the copper sulfate plating layer (104) to the average thickness of the copper pyrophosphate plating layer (103) is 0.1 to 0. 0.5 is preferable, and 0.3 to 0.4 is more preferable.
- Copper sulfate plating can be carried out by electroplating for about 1 to 120 minutes at a current density of 0.5 to 10 A / dm 2 in an acidic plating bath containing copper sulfate at 10 to 40 ° C.
- a brightener may be appropriately added to the plating bath.
- a finish plating layer (105) harder than the copper sulfate plating layer (104) is formed on the copper sulfate plating layer (104).
- the finish plating layer (105) also has the purpose of giving the appearance of a desired color tone, but by forming the hard finish plating layer (105) thin, a sliding resistance reduction function, a corrosion prevention function, and a crack prevention function Can be effectively expressed.
- the fact that the finish plating layer (105) is harder than the copper sulfate plating layer (104) means that the finish plating is formed on the surface of the member formed up to the copper sulfate plating layer (104) rather than the Vickers hardness. It means that the Vickers hardness of the member surface on which the layer (105) is formed is larger.
- the Vickers hardness Hv of the member surface formed up to the copper sulfate plating layer (104) is about 100 (load 50 g).
- Examples of the finish plating layer (105) that is harder than the copper sulfate plating layer (104) include a Cu—Sn alloy plating layer, a Cu—Zn alloy plating layer, a Sn—Co alloy plating layer, and a Sn—Ni alloy plating layer.
- Cu-Sn-Zn alloy plating layer Cu-Zn-Sn alloy plating layer, Cu-Zn-Sn alloy plating layer, Cu-Ag-Zn alloy plating layer, Cu-Zn-Ag alloy plating layer, Sn-Ni-Cu alloy plating layer, Co plating layer, Examples thereof include a Cr plating layer and a Cr—Mo alloy plating layer, and among these, an alloy plating layer containing Cu and Sn such as a Cu—Sn alloy plating layer and a Cu—Sn—Zn alloy plating layer is preferable.
- Ni may cause allergies, but by using a Cu-Sn-Zn alloy plating layer, it is possible to express the same color as Ni plating, and by changing the plating composition, silver white, brass color, gold color, etc. This is because various color tones can be expressed.
- the finish plating layer can be formed by employing known plating conditions depending on the type.
- the surface Vickers hardness Hv of the slide fastener or button member is preferably 300 or more, more preferably 400 or more, and even more preferably 500 or more.
- the Vickers hardness can be set to Hv 300 to 800.
- the Vickers hardness of the surface of the member after forming the silver finish plating layer (copper 50 to 55 mass%, tin 30 to 35 mass%, zinc 13 to 17 mass%) is about 600 Hv (load 50 g).
- the Vickers hardness of the member surface after forming the gold finish plating layer (copper 76 to 86% by mass, tin 2 to 6% by mass, zinc 12 to 17% by mass) is about It can be set to 400 Hv (load 100 g).
- the Vickers hardness Hv is measured according to JIS Z2244: 2009.
- the average thickness of the finish plating layer is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, and even more preferably 2 ⁇ m or less.
- the average thickness is preferably 0.5 ⁇ m or more, more preferably 0.7 ⁇ m or more. More preferably, the thickness is 0.8 ⁇ m or more.
- the average thickness of the finish plating layer (105) is preferably about 5 to 15% with respect to the total average thickness of the copper pyrophosphate plating layer (103) and the copper sulfate plating layer (104) thereunder. .
- a plating layer (106) having a color tone different from that of the finish plating layer (105) (hereinafter referred to as “color tone adjusting plating layer”) may be formed.
- the color tone adjusting plating layer is not particularly limited, and examples thereof include a Cu—Sn—Zn alloy plating layer, a Cu—Sn alloy plating layer, and a Cu—Zn alloy plating layer (brass plating layer).
- the average thickness of the color tone adjusting plating layer is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 2 ⁇ m or less in order to reduce sliding resistance.
- a Cu—Sn—Zn alloy plating layer may be used for the color tone adjustment plating layer.
- the color tone adjusting plating layer can be formed by adopting known plating conditions depending on the type.
- the total thickness of all the plating layers of the copper pyrophosphate plating layer, the copper sulfate plating layer, the finish plating layer when present, and the color adjustment plating layer when present is preferably 50 ⁇ m or less on average, more preferably Is 30 ⁇ m or less on average, and even more preferably 20 ⁇ m or less on average.
- the arithmetic average roughness (Ra) of the outermost surface can be 0.3 ⁇ m or less, preferably 0.15 ⁇ m or less.
- the thickness can be preferably 0.1 ⁇ m or less, more preferably 0.08 ⁇ m or less, for example, 0.02 to 0.15 ⁇ m.
- the arithmetic average roughness (Ra) is measured by a non-contact type surface roughness measuring device in accordance with JIS B0601: 2001.
- slide fastener or button member can be assembled by any known means using the obtained slide fastener or button member.
- the member of the button include a rivet and a button main body attached to the fabric by the rivet.
- the slide fastener member include a slider (body and / or puller), a fastener element, an upper stopper, and a lower stopper.
- a fastener stringer can be produced by crimping and fixing a plurality of fastener elements along one side edge of the fastener tape, and a fastener chain in which a pair of fastener stringers are connected via a row of fastener elements is produced.
- slide fastener in which an upper stop and a lower stop are attached to the fastener chain as needed in addition to the slider.
- the slide fastener can be attached to the opening / closing part of various articles including daily necessities such as clothing, bags, shoes and sundries.
- Comparative Example 2 Under the same conditions as in Comparative Example 1, pretreatment and zincate treatment were performed on a large number of slide fastener elements manufactured by punching a flat aluminum wire with a press. Next, a copper cyanide plating layer (strike plating layer ⁇ main plating layer) and a copper sulfate plating layer having an average thickness shown in Table 1 were sequentially formed by electric barrel plating. Finally, a finish plating layer (Cu—Sn—Zn alloy plating layer) having an average thickness shown in Table 1 was formed by electric barrel plating.
- Examples 1 to 5 Under the same conditions as in Comparative Example 1, pretreatment and zincate treatment were performed on a large number of slide fastener elements manufactured by punching a flat aluminum wire with a press. Next, a copper pyrophosphate plating layer (strike plating layer ⁇ main plating layer) and a copper sulfate plating layer having an average thickness shown in Table 1 were formed in order by electric barrel plating. Thereafter, in Examples 2 to 4, a finish plating layer (Cu—Sn—Zn alloy plating layer) having an average thickness described in Table 1 was formed by electric barrel plating. For Example 5, a Cu—Sn black plating layer (color tone adjustment plating layer) having the average thickness shown in Table 1 was formed on the finish plating layer by electric barrel plating. For Example 1, no finish plating layer was formed.
- Average thickness of zinc diffusion layer and each plating layer > (1) Zinc diffusion layer About each element with a plating of the Example and comparative example obtained on said conditions, from a cross-section sample produced by CP method, using FIB (SIOS DualBeam made from FEI), electric current and processing time An ultrathin section sample (thickness of 200 nm or less) for cross-sectional observation was prepared while adjusting. Next, the section of the zinc diffusion layer was observed by STEM using Hitachi HD-2300A using the obtained slice sample, and elemental analysis was performed by EDX to obtain an element mapping image (acceleration voltage 200 kV).
- FIB SIOS DualBeam made from FEI
- the island having the furthest distance from the base material surface is selected as the parent.
- An average value was calculated by specifying the distance of the boundary line on the surface of the material having a length of 500 nm and measuring the distance of the island having the longest distance from the surface of the base material in 10 or more observation fields. The results are shown in Table 1.
- Corrosion test The plated elements of Examples and Comparative Examples obtained under the above conditions were subjected to salt spray 24h and visually examined for corrosion. The results were determined according to the following criteria. The results are shown in Table 2. ⁇ : Corrosion was not observed on the plating surface. X: Corrosion was observed on the plating surface.
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Abstract
Description
スライドファスナー又はボタンの部材の形状に加工されたアルミニウム又はアルミニウム合金製の母材を準備する工程と、
該母材表面の少なくとも一部に対してジンケート処理、ピロリン酸銅めっき、及び硫酸銅めっきを順に実施する工程と、
を含むスライドファスナー又はボタンの部材の製造方法である。
本発明に係るスライドファスナー又はボタンの部材は、アルミニウム又はアルミニウム合金を母材(101)としている。アルミニウム合金としては、限定的ではないが、Al-Cu系合金、Al-Mn系合金、Al-Si系合金、Al-Mg系合金、Al-Mg-Si系合金、Al-Zn-Mg系合金、Al-Zn-Mg-Cu系合金などが挙げられる。これらの中でも、強度、加工性の理由により、Al-Mg系合金、Al-Mn系合金及びAl-Mg-Si系合金が好ましく、Al-Mg系合金がより好ましい。
本発明に係るスライドファスナー又はボタンの部材においては、母材表面内側に亜鉛が拡散した亜鉛拡散層(102)を有する。亜鉛拡散層を設けることでめっきの密着性を向上させることが可能となる。亜鉛拡散層はめっき密着性を高めるという観点から50nm以上の平均厚みを有することが好ましく、100nm以上の平均厚みを有することがより好ましく、200nm以上の平均厚みを有することが更により好ましく、250nm以上の平均厚みを有することが更により好ましい。また、亜鉛拡散層費用対効果の観点から500nm以下の平均厚みを有することが好ましく、400nm以下の平均厚みを有することがより好ましく、350nm以下の平均厚みを有することが更により好ましい。
亜鉛拡散層(102)の上にはピロリン酸銅めっき層(103)が形成される。ピロリン酸銅めっき層はひび割れの抑制効果が高い点で優れている。例えば、ファスナーエレメントは、アルミニウム合金製の平角線材を打ち抜くことにより形成された個々のファスナーエレメントの表面にめっき層を形成した後、ファスナーエレメントの一対の脚部の間にファスナーテープを配置し、一対の脚部を内側に向けて加締めることによってファスナーテープに取り付けられる。図6には、ファスナーエレメント108を加締める前(a)及びファスナーエレメント108をファスナーテープ109に加締めた後(b)の様子が例示してある。加締め前には一対の脚部の開き角度θは30~50°であるのが典型的であり、加締め後に一対の脚部は平行になるのが典型的である。そのため、ファスナーエレメントを加締める際に、表面に形成されためっき層が延ばされひび割れが生じやすい。母材に近く内側にあるために変形量の少ないピロリン酸銅めっき層(103)を厚く形成することで、後述する、ピロリン酸銅めっき層(103)の外側に形成される硫酸銅めっき層(104)や硬質な仕上げめっき層(105)を薄く形成することができ、ひび割れを抑制することができる。また、ピロリン酸銅めっき液は弱アルカリ性であり、ジンケート処理後のめっきの付き回りが良いという点でも優れている。ピロリン酸銅めっき層というのはピロリン酸銅を含有するめっき液を使用することにより得られためっき層であり、めっき層中にCu及びPが含まれる。
ピロリン酸銅めっき層(103)の上には硫酸銅めっき層(104)が形成される。硫酸銅めっき層は高い光沢が得られる点で優れている。このため、ピロリン酸銅めっき層(103)と硫酸銅めっき層(104)をこの順に積層することは、めっき密着性及び光沢性を両立を図る上で重要である。硫酸銅めっき層は硫酸銅を含有するめっき液を使用することにより得られためっき層であり、めっき層中にCu及びSが含まれる。
硫酸銅めっき層(104)の上には硫酸銅めっき層(104)よりも硬質の仕上げめっき層(105)が形成される。仕上げめっき層(105)は所望の色調の外観を付与するという目的もあるが、硬質の仕上げめっき層(105)を薄く形成することで、摺動抵抗低減機能、腐食防止機能、及びひび割れ防止機能を効果的に発現可能となる。ここで、硫酸銅めっき層(104)よりも仕上げめっき層(105)が硬質であるというのは、硫酸銅めっき層(104)まで形成された部材表面のビッカース硬さよりも、その上に仕上げめっき層(105)が形成された部材表面のビッカース硬さのほうが大きいことを指す。典型的には、硫酸銅めっき層(104)まで形成された部材表面のビッカース硬さHvは100程度(荷重50g)である。
仕上げめっき層(105)の上には更に、仕上げめっき層(105)とは色調の異なるめっき層(106)(以下、「色調調整めっき層」という。)を形成してもよい。これによりカラーバリエーションを充実させることができる。色調調整めっき層としては特に制限はないが、Cu-Sn-Zn合金めっき層、Cu-Sn合金めっき層、Cu-Zn合金めっき層(真鍮めっき層)が挙げられる。また、色調調整めっき層の平均厚みは、摺動抵抗を小さくするため、10μm以下とするのが好ましく、5μm以下とするのがより好ましく、2μm以下とするのが更により好ましい。また、アレルギーを起こすおそれのあるNiの代わりに、Cu-Sn-Zn合金めっき層を色調調整めっき層に用いることもできる。色調調整めっき層はその種類に応じて公知のめっき条件を採用することにより形成可能である。
スライドファスナーの分野においては、スライダーを操作するときの摺動抵抗を抑制することが重要な課題の一つである。ピロリン酸銅めっき層から色調の異なるめっき層までの各種めっき層の合計の厚みが大きくなると、摺動抵抗が増加する傾向にあることから、低減させておくことが望ましい。そこで、ピロリン酸銅めっき層、硫酸銅めっき層、存在する場合の仕上げめっき層、及び存在する場合の色調調整めっき層のすべてのめっき層の合計厚みは好ましくは平均で50μm以下であり、より好ましくは平均で30μm以下であり、更により好ましくは平均で20μm以下である。
光沢の程度は、面粗度で比較することができる。面粗度が小さいほど表面の凹凸が少なく、光沢が出る。本発明に係るスライドファスナー又はボタンの部材は一実施形態において、最表面の算術平均粗さ(Ra)は0.3μm以下とすることができ、好ましくは0.15μm以下とすることができ、より好ましくは0.1μm以下とすることができ、更に好ましくは0.08μm以下とすることができ、例えば0.02~0.15μmとすることができる。本発明において、算術平均粗さ(Ra)はJIS B0601:2001に準拠して非接触式表面粗さ測定装置により測定する。
このようにして、素材表面へのめっきが完了した後、得られたスライドファスナー又はボタンの部材を用いて、公知の任意の手段によってスライドファスナー又はボタンを組み立てることができる。限定的ではないが、ボタンの部材としては、リベットや、リベットにより生地に取り付けられるボタン本体が挙げられる。スライドファスナーの部材としてはスライダー(胴体及び/又は引手)、ファスナーエレメント、上止、下止が挙げられる。ファスナーエレメントはファスナーテープの一側縁に沿って複数加締め固定することによってファスナーストリンガーを作製することができ、また、一対のファスナーストリンガーをファスナーエレメントの列を介して連結させたファスナーチェーンを作製することができ、更には、ファスナーチェーンにスライダーの他、必要に応じて上止や下止を取り付けたスライドファスナーを作製することができる。スライドファスナーは衣料品、鞄類、靴類及び雑貨品といった日用品含む各種物品の開閉部に取り付けることができる。
(比較例1)
アルミニウム製の平角線材をプレスにより打ち抜いて製造された多数のスライドファスナー用エレメントを用意し、これに対して図5に記載の手順で前処理及びジンケート処理を行った。次いで、表1に記載の平均厚みを有するピロリン酸銅めっき層(ストライクめっき層→本めっき層)を電気バレルめっきにより形成した。最後に、表1に記載の平均厚みを有する仕上げめっき層(Cu-Sn-Zn合金めっき層)を電気バレルめっきにより形成した。各めっき層の平均厚みの測定法については後述する。
比較例1と同様の条件で、アルミニウム製の平角線材をプレスにより打ち抜いて製造された多数のスライドファスナー用エレメントに対して前処理及びジンケート処理を行った。次いで、表1に記載の平均厚みを有する青化銅めっき層(ストライクめっき層→本めっき層)及び硫酸銅めっき層を電気バレルめっきにより順に形成した。最後に、表1に記載の平均厚みを有する仕上げめっき層(Cu-Sn-Zn合金めっき層)を電気バレルめっきにより形成した。
比較例1と同様の条件で、アルミニウム製の平角線材をプレスにより打ち抜いて製造された多数のスライドファスナー用エレメントに対して前処理及びジンケート処理を行った。次いで、表1に記載の平均厚みを有するピロリン酸銅めっき層(ストライクめっき層→本めっき層)及び硫酸銅めっき層を順に電気バレルめっきにより形成した。その後、実施例2~4については表1に記載の平均厚みを有する仕上げめっき層(Cu-Sn-Zn合金めっき層)を電気バレルめっきにより形成した。実施例5については表1に記載の平均厚みを有するCu-Sn黒色めっき層(色調調整めっき層)を仕上げめっき層の上に電気バレルめっきにより形成した。実施例1については仕上げめっき層を形成しなかった。
(1)亜鉛拡散層
上記の条件で得られた実施例及び比較例の各めっき付きエレメントについて、CP法によって作製した断面試料から、FIB(FEI社製Scios DualBeam)を用いて電流と処理時間を調節しながら断面観察用の超薄切片サンプル(厚さ200nm以下)を作製した。次いで、得られた切片サンプルを用いて亜鉛拡散層の断面を日立製HD-2300AによりSTEM観察し、EDXにより元素分析を行って元素マッピング像を得た(加速電圧200kV)。
上記の条件で得られた実施例及び比較例の各めっき付きエレメントを樹脂に埋め込み、表面を研磨して断面観察用サンプルを作製した。各めっき層を金属顕微鏡(オリンパス社製型式GX51)で分析し、10点以上のめっき厚みを測定して平均値を算出した。結果を表1に示す。
上記の条件で得られた実施例及び比較例の各めっき付きエレメントについて、表面観察(実体顕微鏡オリンパス製SZ60)によりめっき層の密着性を確認した。結果は以下の基準により判定した。結果を表2に示す。
○:めっき層の剥離箇所が観察されなかった。
×:めっき層の剥離箇所が観察された。
上記の条件で得られた実施例及び比較例の各めっき付きエレメントを一対のファスナーテープの側縁に複数加締め固定してエレメント列を形成し、一対のエレメント列を噛合することによりファスナーチェーンを作製した。引張試験機(JIS-B-7721準拠)を用いて、ファスナーチェーンをスライダーを介して開閉し、JIS-S-3015:2007に準拠して摺動抵抗を測定した。摺動抵抗は積分平均値を採用した。結果を表2に示す。摺動抵抗が4.9N以下であれば実用上問題ないと判断される。なお、比較例2は、密着性が悪く、表面が部分的に膨れたようなめっき付きエレメントとなったため、表面に膨れの無い他の例と比較できる摺動抵抗のデータが得られなかった。
上記の条件で得られた実施例及び比較例の各めっき付きエレメントについて、最表面の算術平均粗さ(Ra)をJIS B0601:2001に準拠して非接触三次元表面形状測定装置(米国ザイゴ社製、Zygo NewView 6300)により測定した。結果を表2に示す。なお、比較例2は、密着性が悪く、表面が部分的に膨れたようなめっき品となったため、表面に膨れの無い他の例と比較できる表面粗さのデータが得られなかった。
上記の条件で得られた実施例及び比較例の各めっき付きエレメントについて、ビッカース硬度計(JIS-Z-2244:2009準拠)により、硬さを測定した。荷重は50gとした。測定は3回行い、その平均値を測定値とした。結果を表2に示す。
上記の条件で得られた実施例及び比較例の各めっき付きエレメントを、ファスナーテープの側縁に治具を用いて加締め固定した後の表面状態を実体顕微鏡(オリンパス社製SZ60)にて観察した。結果は以下の基準により判定した。結果を表2に示す。
○:めっき表面にひび割れが観察されなかった。
×:めっき表面にひび割れが観察された。
上記の条件で得られた実施例及び比較例の各めっき付きエレメントに塩水噴霧24hを行い、腐食の有無を目視により調べた。結果は以下の基準により判定した。結果を表2に示す。
○:めっき表面に腐食が観察されなかった。
×:めっき表面に腐食が観察された。
上記の結果から、実施例1~5に係るめっき付きエレメントは耐ひび割れ性及び光沢性を兼備していたことが分かる。また、仕上げめっきを行うことで、耐食性が向上することが確認された。一方、比較例1は光沢銅めっきを行わなかったために光沢が不十分であった。比較例2はピロリン酸銅めっきに代えて青化銅めっきを行ったことでめっきの密着性が悪く、外観不良となった。
102 亜鉛拡散層
103 ピロリン酸銅めっき層
103a ピロリン酸銅ストライクめっき層
103b ピロリン酸銅本めっき層
104 硫酸銅めっき層
105 仕上げめっき層
106 色調調整めっき層
108 ファスナーエレメント
109 ファスナーテープ
Claims (16)
- アルミニウム又はアルミニウム合金製の母材(101)と、該母材の表面内側に亜鉛が拡散した亜鉛拡散層(102)と、亜鉛拡散層(102)を被覆する複数のめっき層とを備え、該複数のめっき層は内側から順にピロリン酸銅めっき層(103)、及び硫酸銅めっき層(104)を有するスライドファスナー又はボタンの部材。
- ピロリン酸銅めっき層(103)の平均厚みが20μm以下である請求項1に記載のスライドファスナー又はボタンの部材。
- ピロリン酸銅めっき層(103)の平均厚みが5~20μmである請求項1に記載のスライドファスナー又はボタンの部材。
- ピロリン酸銅めっき層(103)は平均厚み0.1~5μmのピロリン酸銅ストライクめっき層(103a)を下地として有する請求項1~3の何れか一項に記載のスライドファスナー又はボタンの部材。
- 硫酸銅めっき層(104)の平均厚みが7μm以下である請求項1~4の何れか一項に記載のスライドファスナー又はボタンの部材。
- 硫酸銅めっき層(104)の平均厚みが1~7μmである請求項1~4の何れか一項に記載のスライドファスナー又はボタンの部材。
- ピロリン酸銅めっき層(103)の平均厚みに対する硫酸銅めっき層(104)の平均厚みの比が0.1~0.5である請求項1~6の何れか一項に記載のスライドファスナー又はボタンの部材。
- 前記複数のめっき層は、硫酸銅めっき層(104)の外側に硫酸銅めっき層(104)よりも硬質の仕上げめっき層(105)を更に有する請求項1~7の何れか一項に記載のスライドファスナー又はボタンの部材。
- 仕上げめっき層(105)がCu及びSnを含有する合金めっき層である請求項8に記載のスライドファスナー又はボタンの部材。
- 仕上げめっき層(105)の平均厚みが0.5~5μmである請求項8又は9に記載のスライドファスナー又はボタンの部材。
- 最表面の算術平均粗さ(Ra)が0.3μm以下である請求項1~10の何れか一項に記載のスライドファスナー又はボタンの部材。
- 前記複数のめっき層は、仕上げめっき層(105)の外側に仕上げめっき層(105)とは色調の異なるめっき層(106)を更に有する請求項8~11の何れか一項に記載のスライドファスナー又はボタンの部材。
- 母材(101)表面全体が前記複数のめっき層に被覆されている請求項1~12の何れか一項に記載のスライドファスナー又はボタンの部材。
- 請求項1~13の何れか一項に記載のスライドファスナー又はボタンの部材を備えた物品。
- 請求項1~13の何れか一項に記載のスライドファスナーの部材がファスナーエレメントであり、当該ファスナーエレメントがファスナーテープの一側縁に沿って複数加締め固定されているファスナーストリンガー。
- スライドファスナー又はボタンの部材の形状に加工されたアルミニウム又はアルミニウム合金製の母材(101)を準備する工程と、
該母材(101)表面の少なくとも一部に対してジンケート処理、ピロリン酸銅めっき、及び硫酸銅めっきを順に実施する工程と、
を含むスライドファスナー又はボタンの部材の製造方法。
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Cited By (5)
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JP2021122517A (ja) * | 2020-02-05 | 2021-08-30 | Ykk株式会社 | スライドファスナー用のAl合金製パーツ及びその製造方法 |
JP7418739B2 (ja) | 2020-02-05 | 2024-01-22 | Ykk株式会社 | スライドファスナー用のAl合金製パーツ及びその製造方法 |
US20220002878A1 (en) * | 2020-07-06 | 2022-01-06 | Ykk Corporation | Aluminum alloy fastening member, fastener chain and method for producing aluminum alloy fastening member |
CN113576116A (zh) * | 2021-08-10 | 2021-11-02 | 浙江伟星实业发展股份有限公司 | 一种真贝纽扣深色处理液及处理工艺和真贝纽扣 |
CN113576116B (zh) * | 2021-08-10 | 2023-11-14 | 浙江伟星实业发展股份有限公司 | 一种真贝纽扣深色处理液及处理工艺和真贝纽扣 |
Also Published As
Publication number | Publication date |
---|---|
EP3560370A1 (en) | 2019-10-30 |
KR102178027B1 (ko) | 2020-11-12 |
CN110072404A (zh) | 2019-07-30 |
JPWO2018122935A1 (ja) | 2019-06-24 |
JP6736690B2 (ja) | 2020-08-05 |
EP3560370A4 (en) | 2020-10-21 |
CN118235922A (zh) | 2024-06-25 |
KR20190060812A (ko) | 2019-06-03 |
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