EP4357488A1 - Additive for composite plating solutions - Google Patents
Additive for composite plating solutions Download PDFInfo
- Publication number
- EP4357488A1 EP4357488A1 EP22824733.4A EP22824733A EP4357488A1 EP 4357488 A1 EP4357488 A1 EP 4357488A1 EP 22824733 A EP22824733 A EP 22824733A EP 4357488 A1 EP4357488 A1 EP 4357488A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- additive
- nickel
- plating solution
- fine particles
- occurred
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000000654 additive Substances 0.000 title claims abstract description 131
- 230000000996 additive effect Effects 0.000 title claims abstract description 128
- 238000007747 plating Methods 0.000 title claims abstract description 84
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 239000010419 fine particle Substances 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 23
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims abstract description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 33
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 32
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 32
- 229910052782 aluminium Inorganic materials 0.000 claims description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 24
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 23
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 23
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 15
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000007711 solidification Methods 0.000 claims description 7
- 230000008023 solidification Effects 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000004767 nitrides Chemical class 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 150000003568 thioethers Chemical class 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000004677 hydrates Chemical class 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 30
- 239000007788 liquid Substances 0.000 abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 54
- 239000000243 solution Substances 0.000 description 49
- 239000000843 powder Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 29
- 238000002156 mixing Methods 0.000 description 28
- 238000003756 stirring Methods 0.000 description 28
- 229940053662 nickel sulfate Drugs 0.000 description 26
- 239000000377 silicon dioxide Substances 0.000 description 26
- 235000012239 silicon dioxide Nutrition 0.000 description 25
- 238000012360 testing method Methods 0.000 description 25
- 239000007864 aqueous solution Substances 0.000 description 21
- 150000002815 nickel Chemical class 0.000 description 20
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 15
- 238000001556 precipitation Methods 0.000 description 15
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 239000004327 boric acid Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- -1 aluminum ions Chemical class 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229910000365 copper sulfate Inorganic materials 0.000 description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 2
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- NRNCYVBFPDDJNE-UHFFFAOYSA-N pemoline Chemical compound O1C(N)=NC(=O)C1C1=CC=CC=C1 NRNCYVBFPDDJNE-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910006147 SO3NH2 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical compound [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 description 1
- 229960001950 benzethonium chloride Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910052927 chalcanthite Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- PSHRANCNVXNITH-UHFFFAOYSA-N dimethylamino acetate Chemical compound CN(C)OC(C)=O PSHRANCNVXNITH-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 229940094506 lauryl betaine Drugs 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- UPHWVVKYDQHTCF-UHFFFAOYSA-N octadecylazanium;acetate Chemical compound CC(O)=O.CCCCCCCCCCCCCCCCCCN UPHWVVKYDQHTCF-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/52—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
- C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
- C25D21/14—Controlled addition of electrolyte components
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/16—Regeneration of process solutions
- C25D21/18—Regeneration of process solutions of electrolytes
Definitions
- the present invention relates to a technique for causing an additive containing non-conductive fine particles used in a composite plating solution to become a liquid.
- Plating that has a non-shiny uniform semi-bright or almost matte appearance is called satin nickel.
- a method for obtaining a satin-like appearance includes composite plating in which non-conductive fine particles are suspended in a liquid and codeposited with nickel (NPL 1).
- plating utilizing similar non-conductive fine particles includes microporous plating used for a base for chrome plating used as decorative plating for an automobile part, a faucet fitting, or the like.
- microporous plating film With this microporous plating film, a large number of invisible tiny pores can be formed in the surface layer of chrome plating, and corrosion resistance can be improved by dispersing a corrosion current (PTL 1).
- This microporous plating is also a type of composite plating.
- the fine particles used to form a satin-like appearance or micropores have a very small particle diameter, and therefore scatter into the atmosphere when added to the plating solution, are exposed to a worker or adhere to the surroundings in working, and a liquid additive form has long been desired.
- NPL 1 Electroplating & Chemical Plating Guide Book, 1987 Edition, Tokyo Plating Material Cooperative Association, P. 151
- an object of the invention is to provide an additive for a composite plating solution, which is a liquid containing non-conductive fine particles, does not require preparation of special fine particles, and has high stability.
- the present inventors conducted intensive studies to solve the above problems, and as a result, they found that the above problems can be solved by incorporating nickel ions for dispersing non-conductive fine particles in a liquid, and thus completed the invention.
- the invention is directed to an additive for a composite plating solution characterized by containing non-conductive fine particles, nickel ions, and water.
- the invention is directed to a method for preventing solidification of a precipitate of non-conductive fine particles in an additive for a composite plating solution, characterized by incorporating nickel ions in an additive for a composite plating solution containing non-conductive fine particles and water.
- the additive for a composite plating solution of the invention can prevent sedimentation of non-conductive fine particles (separation between a suspension layer of non-conductive fine particles and a supernatant is delayed: a time until formation of a precipitate is slow), and prevent solidification of a precipitate (non-conductive fine particles do not re-disperse even if shaking is performed), and can maintain a stable state as a liquid additive.
- the additive for a composite plating solution of the invention can be used stably without scattering into the atmosphere when added to the plating solution, or exposure to a worker or adhesion to the surroundings in working.
- the additive for a composite plating solution of the invention contains non-conductive fine particles, nickel ions, and water.
- the non-conductive fine particles used in the additive of the invention are not particularly limited, and examples thereof include oxides, nitrides, sulfides, and inorganic salts of metals such as silicon, barium, zirconium, aluminum and titanium.
- oxides, nitrides, sulfides, and inorganic salts of silicon, barium, zirconium, and aluminum are preferred in terms of effect, and oxides such as silica (silicon dioxide) and zirconia (zirconium dioxide), and inorganic salts such as barium sulfate are particularly preferred.
- these non-conductive fine particles one type or two or more types can be used.
- non-conductive fine particles for example, commercially available products such as MP POWDER 308 and MP POWDER 309A of JCU CORPORATION can also be used.
- the average particle diameter of these non-conductive fine particles is not particularly limited, but is, for example, 0.1 to 10 um, and preferably 1.0 to 3.0 um.
- the average particle diameter is a value measured by a zeta potential/particle diameter/molecular weight measurement system ELSZ-2000 manufactured by Otsuka Electronics Co., Ltd.
- the content of the non-conductive fine particles in the additive of the invention is not particularly limited, but is, for example, 0.01 to 20 wt% (hereinafter simply referred to as "%"), and preferably 0.05 to 10%.
- the content of the non-conductive fine particles in the additive of the invention can also be set to a concentration higher than when the non-conductive fine particles are used in an ordinary composite plating solution. In this case, the content is, for example, 5 to 50%, and preferably 10 to 40%.
- the content of nickel ions in the additive of the invention is not particularly limited, but is, for example, 0.01 to 12%, and preferably 0.05 to 10%.
- the nickel ion supply source of the nickel ions is not particularly limited as long as nickel ions are generated when it is dissolved in water.
- Examples thereof include nickel sulfate, nickel chloride, nickel sulfamate, and nickel acetate. These can be used in the form of a hydrate or an anhydride. Among these, nickel sulfate hexahydrate is preferred in terms of cost and containing no halogens.
- nickel ion supply sources one type or two or more types can be used.
- the mass ratio of the non-conductive fine particles and the nickel ions in the additive of the invention may be appropriately set according to the type of non-conductive fine particles, but for example, when silicon dioxide is used as the non-conductive fine particles, the mass ratio is 1:0.001 to 1:3, and preferably 1:0.003 to 1:2.
- the water used in the additive of the invention is not particularly limited, and for example, distilled water, ion-exchanged water, ultrapure water, city water, or the like may be used.
- the pH of the additive of the invention is not particularly limited, but is preferably neutral or acidic, and in particular, since a hydroxide of nickel is generated at pH 6 or higher, it is more preferably pH 6 or lower.
- an inorganic acid such as sulfuric acid, hydrochloric acid, or nitric acid
- an organic acid such as acetic acid, sulfamic acid, or the like may be used.
- the additive of the invention can prevent sedimentation of the non-conductive fine particles and solidification of a precipitate thereof in the additive for composite plating solution containing water and the non-conductive fine particles by the action of nickel ions described above, and can maintain a stable state as a liquid additive, but may further contain one type or two or more types selected from a charge imparting agent, a surfactant, and a brightener.
- Examples of the charge imparting agent include aluminum ions.
- the supply source of the aluminum ions is not particularly limited, but when it is added to a composite plating solution containing a Watts bath in which nickel sulfate or nickel chloride is used as a base, use of polyaluminum chloride or aluminum sulfate has little effect on sulfate ions or chlorine ions.
- polyaluminum chloride in the form of a powder may be added, or for example, a commercially available product in the form of an aqueous solution of about 10% in terms of aluminum oxide such as PAC of Nankai Chemical Industry Co., Ltd. or TAIPAC series of Taimei Chemicals Co., Ltd. may be added.
- Such polyaluminum chloride may be added as it is or after being appropriately diluted or the like.
- the content of polyaluminum chloride in the additive of the invention is not particularly limited, but is, for example, 0.01 to 50.0%, and preferably 0.1 to 30% in terms of aluminum oxide (for example, 0.002 to 15%, and preferably 0.02 to 7% in terms of aluminum).
- aluminum sulfate in the form of a powder may be added, or aluminum sulfate in the form of a liquid may be added.
- a commercially available product such as an aluminum sulfate solution for tap water or an aluminum sulfate solution for general use of Taimei Chemical Co., Ltd. may be added.
- the surfactant is not particularly limited, but examples thereof include nonionic surfactants such as polyethylene glycol, anionic surfactants such as sodium polyoxyethylene alkyl ether sulfates, cationic surfactants such as benzethonium chloride, stearylamine acetate, and dodecyltrimethylammonium chloride, and amphoteric surfactants such as lauryl betaine, lauryl dimethylamino acetate betaine, amidopropyl dimethylamino acetate betaine laurate, and lauryl dimethylamine oxide.
- nonionic surfactants such as polyethylene glycol
- anionic surfactants such as sodium polyoxyethylene alkyl ether sulfates
- cationic surfactants such as benzethonium chloride, stearylamine acetate, and dodecyltrimethylammonium chloride
- amphoteric surfactants such as lauryl betaine, lauryl dimethylamino acetate betaine
- a cationic surfactant that is positively charged or an amphoteric surfactant that exhibits cationic in a pH range where it is used is preferred. With the use of such a surfactant, the dispersibility is further maintained.
- the content of the surfactant in the additive of the invention is not particularly limited, but is, for example, 0.001 to 5%, and preferably 0.001 to 2%.
- the brightener is not particularly limited, and examples thereof include a primary brightener and a secondary brightener that are used in an ordinary composite plating solution.
- the primary brightener include sulfonamides, sulfonimides, benzenesulfonic acid, and alkylsulfonic acids.
- MP333 manufactured by JCU CORPORATION
- the secondary brightener include 1,4-butynediol and coumarin.
- #810 manufactured by JCU CORPORATION
- These primary brighteners and secondary brighteners may be used alone or a plurality thereof may be used in combination.
- the content of the brightener in the additive of the invention is not particularly limited, but for example, the primary brightener is preferably added in an amount of 0.1 to 900 mL/L, and the secondary brightener is preferably added in an amount of about 0.1 to 900 mL/L.
- the additive of the invention contains non-conductive fine particles, nickel ions, and water, and therefore, an electrolytic nickel solution that is used for a composite plating solution such as a Watts bath or a sulfamate bath may be utilized as one containing nickel ions and water.
- the composition of the Watts bath includes the following composition. This Watts bath may be diluted as appropriate.
- the additive of the invention becomes one containing non-conductive fine particles and the Watts bath.
- composition of the sulfamate bath includes the following composition. This sulfamate bath may be diluted as appropriate.
- the additive of the invention becomes one containing non-conductive fine particles and the sulfamate bath.
- Examples of the additive of the invention include those containing non-conductive fine particles, nickel ions, and water as described above, but the following ones may also be used.
- the additive of the invention described above can be prepared by stirring and mixing the above-mentioned components until homogeneity.
- a composite plating solution such as a satin nickel plating solution or a microporous nickel plating solution by adding the additive of the invention to a composite plating solution base.
- a microporous nickel plating solution base it is possible to perform microporous plating with a good number of micropores as in a conventional case.
- the composite plating solution base refers to a base containing some or all of the components other than the non-conductive fine particles in the composite plating solution, and becoming the composite plating solution by adding the additive of the invention thereto.
- the screw tube bottles were sealed in a state where the additives of Examples 1 to 21 and Comparative Examples 1 to 6 were placed therein, and shaking was performed until homogeneity, and then, the state of each additive was investigated after 24 hours passed. When precipitation occurred, shaking was performed again and redispersibility of the non-conductive fine particles was investigated. In the shaking, the screw tube bottle was shaken up and down 30 times. After shaking, it was visually evaluated whether precipitation occurred in the additive after 24 hours passed, and further redispersibility after shaking was performed again was evaluated according to the following criteria. The results are shown in Table 1.
- the screw tube bottles were sealed in a state where the additives of Examples 1 to 21 and Comparative Examples 1 to 6 were placed therein, and shaking was performed until homogeneity, and then, the state of each additive was investigated after 168 hours passed. When precipitation occurred, shaking was performed again and redispersibility of the non-conductive fine particles was investigated. In the shaking, the screw tube bottle was shaken up and down 30 times. After shaking, it was visually evaluated whether precipitation occurred in the additive after 168 hours passed, and redispersibility after shaking was performed again was evaluated according to the same criteria as in Test Example 1. The results are shown in Table 2.
- Example 1 occurred A Example 15 occurred A Example 2 occurred A Example 16 occurred A Example 3 occurred A Example 17 occurred A Example 4 occurred A Example 18 occurred A Example 5 occurred A Example 19 occurred A Example 6 occurred A Example 20 occurred A Example 7 occurred A Example 21 occurred A Example 8 occurred A Example 9 occurred A Comparative Example 1 occurred B Example 10 occurred A Comparative Example 2 occurred A Example 11 occurred A Comparative Example 3 occurred B Example 12 occurred A Comparative Example 4 occurred B Example 13 occurred A Comparative Example 5 occurred A Example 14 occurred A Comparative Example 6 occurred B
- Example 1 The additive prepared in Example 1 was added in an amount of 0.5 mL/L to a plating bath having the following composition, thereby preparing a microporous plating solution.
- a microporous plated product was produced as a test piece according to the following steps using a bent cathode test piece (brass: manufactured by Yamamoto-MS Co., Ltd.) having a shape shown in FIG. 7 .
- test piece was treated with SK-144 (manufactured by JCU CORPORATION) for 5 minutes for degreasing, and then treated with V-345 (manufactured by JCU CORPORATION) for 30 seconds for acid activation.
- test piece subjected to the degreasing and acid activation treatments above were plated in the following nickel plating solution at 4 A/dm 2 for 3 minutes.
- test piece subjected to bright plating was plated in the microporous plating solution prepared above at 3 A/dm 2 for 3 minutes.
- test piece subjected to microporous nickel plating above was plated in a hexavalent chromium plating solution having the following composition at 10 A/dm 2 for 3 minutes.
- test piece after chrome plating was immersed in a copper sulfate plating solution having the following composition for 3 minutes, and then plated in the copper sulfate plating solution at 0.5 A/dm 2 for 3 minutes.
- the expected number of micropores could be obtained even when a microporous nickel plating solution was prepared by adding non-conductive fine particles in a liquid state.
- the additive of the invention can be utilized for preparing a composite plating solution.
Abstract
An additive for a composite plating solution characterized by containing non-conductive fine particles, nickel ions, and water is a liquid containing the non-conductive fine particles, does not require preparation of special fine particles, and has high stability.
Description
- The present invention relates to a technique for causing an additive containing non-conductive fine particles used in a composite plating solution to become a liquid.
- Plating that has a non-shiny uniform semi-bright or almost matte appearance is called satin nickel. A method for obtaining a satin-like appearance includes composite plating in which non-conductive fine particles are suspended in a liquid and codeposited with nickel (NPL 1).
- In addition, plating utilizing similar non-conductive fine particles includes microporous plating used for a base for chrome plating used as decorative plating for an automobile part, a faucet fitting, or the like. With this microporous plating film, a large number of invisible tiny pores can be formed in the surface layer of chrome plating, and corrosion resistance can be improved by dispersing a corrosion current (PTL 1). This microporous plating is also a type of composite plating.
- The fine particles used to form a satin-like appearance or micropores have a very small particle diameter, and therefore scatter into the atmosphere when added to the plating solution, are exposed to a worker or adhere to the surroundings in working, and a liquid additive form has long been desired.
- However, as for an additive in which water is used as a solvent, when non-conductive fine particles such as silica particles were added thereto, a phenomenon in which the non-conductive fine particles sediment, precipitate, and then solidify after several hours was observed, and it was unsuitable as a stable fine particle liquid additive.
- Incidentally, as a technique for forming micropores during plating, it is known to perform electroplating using a plating solution containing non-conductive particles such as silica particles that are positively charged using aluminum hydroxide (PTL 2) .
- However, if positively charged non-conductive fine particles are prepared in advance as an additive by such a conventional technique, the particles will solidify, so that it is necessary to add the particles separately each time when used, which made it unsuitable as a stable fine particle liquid additive.
-
- PTL 1:
JPH03-291395A - PTL 2:
JPH04-371597A - NPL 1: Electroplating & Chemical Plating Guide Book, 1987 Edition, Tokyo Plating Material Cooperative Association, P. 151
- Therefore, an object of the invention is to provide an additive for a composite plating solution, which is a liquid containing non-conductive fine particles, does not require preparation of special fine particles, and has high stability.
- The present inventors conducted intensive studies to solve the above problems, and as a result, they found that the above problems can be solved by incorporating nickel ions for dispersing non-conductive fine particles in a liquid, and thus completed the invention.
- That is, the invention is directed to an additive for a composite plating solution characterized by containing non-conductive fine particles, nickel ions, and water.
- In addition, the invention is directed to a method for preventing solidification of a precipitate of non-conductive fine particles in an additive for a composite plating solution, characterized by incorporating nickel ions in an additive for a composite plating solution containing non-conductive fine particles and water.
- The additive for a composite plating solution of the invention can prevent sedimentation of non-conductive fine particles (separation between a suspension layer of non-conductive fine particles and a supernatant is delayed: a time until formation of a precipitate is slow), and prevent solidification of a precipitate (non-conductive fine particles do not re-disperse even if shaking is performed), and can maintain a stable state as a liquid additive.
- Therefore, the additive for a composite plating solution of the invention can be used stably without scattering into the atmosphere when added to the plating solution, or exposure to a worker or adhesion to the surroundings in working.
-
- [
FIG. 1] FIG. 1 is a view showing a state of an additive of Comparative Example 1 after being left for 168 hours in Test Example 2 (the left and right views are the same, and the right view has an explanation added to the left view). - [
FIG. 2] FIG. 2 is a view showing a state of an additive of Example 1 after being left for 168 hours in Test Example 2 (the left and right views are the same, and the right view has an explanation added to the left view). - [
FIG. 3] FIG. 3 is a view showing a state of an additive of Example 2 after being left for 168 hours in Test Example 2 (the left and right views are the same, and the right view has an explanation added to the left view). - [
FIG. 4] FIG. 4 is a view showing a state of an additive of Comparative Example 1 after being left for 168 hours and then being shaken in Test Example 2 (the left and right views are the same, and the right view has an explanation added to the left view). - [
FIG. 5] FIG. 5 is a view showing a state of an additive of Example 1 after being left for 168 hours and then being shaken in Test Example 2 (the left and right views are the same, and the right view has an explanation added to the left view). - [
FIG. 6] FIG. 6 is a view showing a state of an additive of Example 2 after being left for 168 hours and then being shaken in Test Example 2 (the left and right views are the same, and the right view has an explanation added to the left view). - [
FIG. 7] FIG. 7 is a view showing an appearance of a test piece used in Test Example 3. - The additive for a composite plating solution of the invention (hereinafter referred to as "the additive of the invention") contains non-conductive fine particles, nickel ions, and water.
- The non-conductive fine particles used in the additive of the invention are not particularly limited, and examples thereof include oxides, nitrides, sulfides, and inorganic salts of metals such as silicon, barium, zirconium, aluminum and titanium. Among these, oxides, nitrides, sulfides, and inorganic salts of silicon, barium, zirconium, and aluminum are preferred in terms of effect, and oxides such as silica (silicon dioxide) and zirconia (zirconium dioxide), and inorganic salts such as barium sulfate are particularly preferred. Among these non-conductive fine particles, one type or two or more types can be used.
- In addition, as the non-conductive fine particles, for example, commercially available products such as MP POWDER 308 and MP POWDER 309A of JCU CORPORATION can also be used.
- The average particle diameter of these non-conductive fine particles is not particularly limited, but is, for example, 0.1 to 10 um, and preferably 1.0 to 3.0 um. The average particle diameter is a value measured by a zeta potential/particle diameter/molecular weight measurement system ELSZ-2000 manufactured by Otsuka Electronics Co., Ltd.
- The content of the non-conductive fine particles in the additive of the invention is not particularly limited, but is, for example, 0.01 to 20 wt% (hereinafter simply referred to as "%"), and preferably 0.05 to 10%. In addition, the content of the non-conductive fine particles in the additive of the invention can also be set to a concentration higher than when the non-conductive fine particles are used in an ordinary composite plating solution. In this case, the content is, for example, 5 to 50%, and preferably 10 to 40%.
- The content of nickel ions in the additive of the invention is not particularly limited, but is, for example, 0.01 to 12%, and preferably 0.05 to 10%.
- The nickel ion supply source of the nickel ions is not particularly limited as long as nickel ions are generated when it is dissolved in water. Examples thereof include nickel sulfate, nickel chloride, nickel sulfamate, and nickel acetate. These can be used in the form of a hydrate or an anhydride. Among these, nickel sulfate hexahydrate is preferred in terms of cost and containing no halogens. Among these nickel ion supply sources, one type or two or more types can be used.
- The mass ratio of the non-conductive fine particles and the nickel ions in the additive of the invention may be appropriately set according to the type of non-conductive fine particles, but for example, when silicon dioxide is used as the non-conductive fine particles, the mass ratio is 1:0.001 to 1:3, and preferably 1:0.003 to 1:2.
- The water used in the additive of the invention is not particularly limited, and for example, distilled water, ion-exchanged water, ultrapure water, city water, or the like may be used.
- The pH of the additive of the invention is not particularly limited, but is preferably neutral or acidic, and in particular, since a hydroxide of nickel is generated at pH 6 or higher, it is more preferably pH 6 or lower. In order to adjust the pH, for example, an inorganic acid such as sulfuric acid, hydrochloric acid, or nitric acid, an organic acid such as acetic acid, sulfamic acid, or the like may be used.
- The additive of the invention can prevent sedimentation of the non-conductive fine particles and solidification of a precipitate thereof in the additive for composite plating solution containing water and the non-conductive fine particles by the action of nickel ions described above, and can maintain a stable state as a liquid additive, but may further contain one type or two or more types selected from a charge imparting agent, a surfactant, and a brightener.
- Examples of the charge imparting agent include aluminum ions. The supply source of the aluminum ions is not particularly limited, but when it is added to a composite plating solution containing a Watts bath in which nickel sulfate or nickel chloride is used as a base, use of polyaluminum chloride or aluminum sulfate has little effect on sulfate ions or chlorine ions.
- When polyaluminum chloride is incorporated in the additive of the invention, polyaluminum chloride in the form of a powder may be added, or for example, a commercially available product in the form of an aqueous solution of about 10% in terms of aluminum oxide such as PAC of Nankai Chemical Industry Co., Ltd. or TAIPAC series of Taimei Chemicals Co., Ltd. may be added. Such polyaluminum chloride may be added as it is or after being appropriately diluted or the like.
- The content of polyaluminum chloride in the additive of the invention is not particularly limited, but is, for example, 0.01 to 50.0%, and preferably 0.1 to 30% in terms of aluminum oxide (for example, 0.002 to 15%, and preferably 0.02 to 7% in terms of aluminum).
- Further, when aluminum sulfate is incorporated in the additive of the invention, aluminum sulfate in the form of a powder may be added, or aluminum sulfate in the form of a liquid may be added. To aluminum sulfate in the form of a liquid, a commercially available product such as an aluminum sulfate solution for tap water or an aluminum sulfate solution for general use of Taimei Chemical Co., Ltd. may be added.
- The surfactant is not particularly limited, but examples thereof include nonionic surfactants such as polyethylene glycol, anionic surfactants such as sodium polyoxyethylene alkyl ether sulfates, cationic surfactants such as benzethonium chloride, stearylamine acetate, and dodecyltrimethylammonium chloride, and amphoteric surfactants such as lauryl betaine, lauryl dimethylamino acetate betaine, amidopropyl dimethylamino acetate betaine laurate, and lauryl dimethylamine oxide. Among these surfactants, one type or two or more types can be used. Among these surfactants, a cationic surfactant that is positively charged or an amphoteric surfactant that exhibits cationic in a pH range where it is used is preferred. With the use of such a surfactant, the dispersibility is further maintained.
- The content of the surfactant in the additive of the invention is not particularly limited, but is, for example, 0.001 to 5%, and preferably 0.001 to 2%.
- The brightener is not particularly limited, and examples thereof include a primary brightener and a secondary brightener that are used in an ordinary composite plating solution. Examples of the primary brightener include sulfonamides, sulfonimides, benzenesulfonic acid, and alkylsulfonic acids. As the primary brightener, for example, MP333 (manufactured by JCU CORPORATION) or the like is commercially available and therefore may be used. Examples of the secondary brightener include 1,4-butynediol and coumarin. The secondary brightener is an organic compound having a functional group as follows (C=O, C=C, C=C, C=N, C=N, N-C=S, N=N, -CH2-CH-O). As the secondary brightener, for example, #810 (manufactured by JCU CORPORATION) is commercially available and therefore may be used. These primary brighteners and secondary brighteners may be used alone or a plurality thereof may be used in combination.
- The content of the brightener in the additive of the invention is not particularly limited, but for example, the primary brightener is preferably added in an amount of 0.1 to 900 mL/L, and the secondary brightener is preferably added in an amount of about 0.1 to 900 mL/L.
- It is only necessary that the additive of the invention contains non-conductive fine particles, nickel ions, and water, and therefore, an electrolytic nickel solution that is used for a composite plating solution such as a Watts bath or a sulfamate bath may be utilized as one containing nickel ions and water.
- The composition of the Watts bath includes the following composition. This Watts bath may be diluted as appropriate.
- Nickel sulfate (NiSO4·6H2O): 1 to 450 g/L
- Nickel chloride (NiCl2·6H2O): 0.1 to 45 g/L
- Boric acid (H3BO3) : 0.1 to 45 g/L
- Water: balance
- When the Watts bath is utilized in this manner, the additive of the invention becomes one containing non-conductive fine particles and the Watts bath.
- The composition of the sulfamate bath includes the following composition. This sulfamate bath may be diluted as appropriate.
- Nickel sulfamate (Ni(SO3NH2)2·4H2O): 1 to 600 g/L
- Nickel chloride (NiCl2·6H2O): 0 to 15 g/L
- Boric acid (H3BO3) : 0.1 to 40 g/L
- Water: balance
- When the sulfamate bath is utilized in this manner, the additive of the invention becomes one containing non-conductive fine particles and the sulfamate bath.
- Examples of the additive of the invention include those containing non-conductive fine particles, nickel ions, and water as described above, but the following ones may also be used.
- (1) An additive for a composite plating solution characterized by containing non-conductive fine particles, nickel ions, and water.
- (2) The additive for a composite plating solution according to (1), wherein the composite plating solution is a satin nickel plating solution or a microporous nickel plating solution.
- (3) The additive for a composite plating solution according to (1) or (2), wherein the non-conductive fine particles are one or more types selected from oxides, nitrides, sulfides, and inorganic salts of silicon, barium, zirconium, aluminum, and titanium.
- (4) The additive for a composite plating solution according to any one of (1) to (3), wherein the supply source of nickel ions is one type or two or more types selected from nickel sulfate hexahydrate, nickel chloride, and nickel sulfamate.
- (5) An additive for a composite plating solution characterized by containing:
- non-conductive fine particles;
- nickel ions; and
- one or more types selected from a charge imparting agent, a surfactant, and a brightener.
- (6) An additive for a composite plating solution characterized by containing:
- non-conductive fine particles; and
- a Watts bath or a sulfamate bath.
- (7) An additive for a composite plating solution characterized by containing:
- non-conductive fine particles;
- a Watts bath or a sulfamate bath; and
- one or more types selected from a charge imparting agent, a surfactant, and a brightener.
- (8) A method for preventing solidification of a precipitate of non-conductive fine particles in an additive for a composite plating solution, characterized by incorporating nickel ions in an additive for a composite plating solution containing non-conductive fine particles and water.
- The additive of the invention described above can be prepared by stirring and mixing the above-mentioned components until homogeneity.
- Then, it is possible to prevent sedimentation of the non-conductive fine particles of the invention or solidification of a precipitate thereof, and maintain a stable state as a liquid additive.
- It is possible to prepare a composite plating solution such as a satin nickel plating solution or a microporous nickel plating solution by adding the additive of the invention to a composite plating solution base. In particular, by adding the additive of the invention to a microporous nickel plating solution base to prepare a microporous nickel plating solution, it is possible to perform microporous plating with a good number of micropores as in a conventional case. The composite plating solution base refers to a base containing some or all of the components other than the non-conductive fine particles in the composite plating solution, and becoming the composite plating solution by adding the additive of the invention thereto.
- Hereinafter, the invention will be described in detail with reference to Examples, but the invention is by no means limited to these Examples or the like. In the preparation of additives in Examples and Comparative Examples, a 110 mL glass screw tube bottle (9-852-10, manufactured by AS ONE Co., Ltd.) (hereinafter referred to as a screw tube bottle) was used.
- In a screw tube bottle, 100 mL of a 500 g/L aqueous solution of nickel sulfate and 6 g of a powder of silicon dioxide were placed, followed by stirring and mixing until homogeneity, thereby obtaining an additive (pH 5.31).
- In a screw tube bottle, 100 mL of a Watts bath prepared with the following composition and 6 g of a powder of silicon dioxide (average particle diameter: 1.5 um) were placed, followed by stirring and mixing until homogeneity, thereby obtaining an additive (pH 3.69).
-
- Nickel sulfate (NiSO4·6H2O): 250 g/L
- Nickel chloride (NiCl2·6H2O): 40 g/L
- Boric acid (H3BO3) : 40 g/L
- In a screw tube bottle, 100 mL of a 500 g/L aqueous solution of nickel sulfate and 6 g of a powder of silicon dioxide, and further polyaluminum chloride (PAC, Nankai Chemical Co., Ltd.) in an amount of 0.07 g in terms of aluminum were placed, followed by stirring and mixing until homogeneity, thereby obtaining an additive (pH 3.92).
- In a screw tube bottle, 100 mL of a 60 g/L aqueous solution of nickel sulfate and 6 g of a powder of silicon dioxide, and further polyaluminum chloride in an amount of 0.07 g in terms of aluminum were placed, followed by stirring and mixing until homogeneity, thereby obtaining an additive (pH 3.99).
- In a screw tube bottle, 100 mL of a 10 g/L aqueous solution of nickel sulfate and 6 g of a powder of silicon dioxide, and further polyaluminum chloride in an amount of 0.07 g in terms of aluminum were placed, followed by stirring and mixing until homogeneity, thereby obtaining an additive (pH 4.05).
- In a screw tube bottle, 100 mL of a 1 g/L aqueous solution of nickel sulfate and 6 g of a powder of silicon dioxide, and further polyaluminum chloride in an amount of 0.07 g in terms of aluminum were placed, followed by stirring and mixing until homogeneity, thereby obtaining an additive (pH 3.86).
- In a screw tube bottle, 100 mL of an aqueous solution adjusted to 450 g/L of nickel sulfate, 40 g/L of nickel chloride, and 40 g/L of boric acid, and 6 g of a powder of silicon dioxide, and further polyaluminum chloride in an amount of 0.07 g in terms of aluminum were placed, followed by stirring and mixing until homogeneity, thereby obtaining an additive (pH 3.62).
- In a screw tube bottle, 100 mL of an aqueous solution adjusted to 250 g/L of nickel sulfate, 40 g/L of nickel chloride, and 40 g/L of boric acid, and 6 g of a powder of silicon dioxide, and further polyaluminum chloride in an amount of 0.07 g in terms of aluminum were placed, followed by stirring and mixing until homogeneity, thereby obtaining an additive (pH 3.74).
- In a screw tube bottle, 100 mL of an aqueous solution adjusted to 10 g/L of nickel sulfate, 1.6 g/L of nickel chloride, and 1.6 g/L of boric acid, and 6 g of a powder of silicon dioxide, and further polyaluminum chloride in an amount of 0.07 g in terms of aluminum were placed, followed by stirring and mixing until homogeneity, thereby obtaining an additive (pH 3.96).
- In a screw tube bottle, 100 mL of an aqueous solution adjusted to 1 g/L of nickel sulfate, 0.16 g/L of nickel chloride, and 0.16 g/L of boric acid, and 6 g of a powder of silicon dioxide, and further polyaluminum chloride in an amount of 0.07 g in terms of aluminum were placed, followed by stirring and mixing until homogeneity, thereby obtaining an additive (pH 3.85) .
- In a screw tube bottle, 100 mL of a 500 g/L aqueous solution of nickel sulfate and 6 g of a powder of silicon dioxide, and further aluminum sulfate in an amount of 0.07 g in terms of aluminum were placed, followed by stirring and mixing until homogeneity, thereby obtaining an additive (pH 3.31).
- In a screw tube bottle, 100 mL of a 60 g/L aqueous solution of nickel sulfate and 6 g of a powder of silicon dioxide, and further aluminum sulfate in an amount of 0.07 g in terms of aluminum were placed, followed by stirring and mixing until homogeneity, thereby obtaining an additive (pH 3.24).
- In a screw tube bottle, 100 mL of a 10 g/L aqueous solution of nickel sulfate and 6 g of a powder of silicon dioxide, and further aluminum sulfate in an amount of 0.07 g in terms of aluminum were placed, followed by stirring and mixing until homogeneity, thereby obtaining an additive (pH 3.41).
- In a screw tube bottle, 100 mL of a 1 g/L aqueous solution of nickel sulfate and 6 g of a powder of silicon dioxide, and further aluminum sulfate in an amount of 0.07 g in terms of aluminum were placed, followed by stirring and mixing until homogeneity, thereby obtaining an additive (pH 3.31).
- In a screw tube bottle, 100 mL of an aqueous solution adjusted to 450 g/L of nickel sulfate, 40 g/L of nickel chloride, and 40 g/L of boric acid, and 6 g of a powder of silicon dioxide, and further aluminum sulfate in an amount of 0.07 g in terms of aluminum were placed, followed by stirring and mixing until homogeneity, thereby obtaining an additive (pH 3.08).
- In a screw tube bottle, 100 mL of an aqueous solution adjusted to 250 g/L of nickel sulfate, 40 g/L of nickel chloride, and 40 g/L of boric acid, and 6 g of a powder of silicon dioxide, and further aluminum sulfate in an amount of 0.07 g in terms of aluminum were placed, followed by stirring and mixing until homogeneity, thereby obtaining an additive (pH 3.00).
- In a screw tube bottle, 100 mL of an aqueous solution adjusted to 10 g/L of nickel sulfate, 1.6 g/L of nickel chloride, and 1.6 g/L of boric acid, and 6 g of a powder of silicon dioxide, and further aluminum sulfate in an amount of 0.07 g in terms of aluminum were placed, followed by stirring and mixing until homogeneity, thereby obtaining an additive (pH 3.30).
- In a screw tube bottle, 100 mL of an aqueous solution adjusted to 1 g/L of nickel sulfate, 0.16 g/L of nickel chloride, and 0.16 g/L of boric acid, and 6 g of a powder of silicon dioxide, and further aluminum sulfate in an amount of 0.07 g in terms of aluminum were placed, followed by stirring and mixing until homogeneity, thereby obtaining an additive (pH 3.30) .
- In a screw tube bottle, 100 mL of an aqueous solution adjusted to 100 g/L of nickel sulfate and 6 g of a powder of silicon dioxide were placed, followed by stirring and mixing until homogeneity, thereby obtaining an additive (pH 5.63).
- In a screw tube bottle, 100 mL of an aqueous solution adjusted to 100 g/L of nickel sulfate and 6 g of a powder of titanium dioxide (average particle diameter: 0.01 um) were placed, followed by stirring and mixing until homogeneity, thereby obtaining an additive (pH 4.94).
- In a screw tube bottle, 100 mL of an aqueous solution adjusted to 100 g/L of nickel sulfate and 6 g of a powder of zirconium silicate (average particle diameter: 1.1 um) were placed, followed by stirring and mixing until homogeneity, thereby obtaining an additive (pH 5.64).
- As Comparative Examples, cases where nickel ions were not contained in the dispersion solvent for the non-conductive fine particles, and water was substantially used as the main solvent will be described below.
- In a screw tube bottle, 100 mL of pure water and 6 g of a powder of silicon dioxide were placed, followed by stirring and mixing until homogeneity, thereby obtaining an additive (pH 7.17) .
- In a screw tube bottle, 100 mL of pure water and 6 g of a powder of titanium dioxide were placed, followed by stirring and mixing until homogeneity, thereby obtaining an additive (pH 7.61) .
- In a screw tube bottle, 100 mL of pure water and 6 g of a powder of zirconium silicate were placed, followed by stirring and mixing until homogeneity, thereby obtaining an additive (pH 6.91) .
- In a screw tube bottle, 100 mL of pure water and 6 g of a powder of silicon dioxide were placed, followed by stirring and mixing until homogeneity, and an additive adjusted to pH 3 or lower with a small amount of sulfuric acid was obtained (pH 2.34) .
- In a screw tube bottle, 100 mL of pure water and 6 g of a powder of silicon dioxide were placed, and further, polyaluminum chloride in an amount of 0.07 g in terms of aluminum was placed, followed by stirring and mixing until homogeneity, thereby obtaining an additive (pH 3.36).
- In a screw tube bottle, 100 mL of pure water and 6 g of a powder of silicon dioxide were placed, and further, aluminum sulfate in an amount of 0.07 g in terms of aluminum was placed, followed by stirring and mixing until homogeneity, thereby obtaining an additive (pH 3.84).
- The screw tube bottles were sealed in a state where the additives of Examples 1 to 21 and Comparative Examples 1 to 6 were placed therein, and shaking was performed until homogeneity, and then, the state of each additive was investigated after 24 hours passed. When precipitation occurred, shaking was performed again and redispersibility of the non-conductive fine particles was investigated. In the shaking, the screw tube bottle was shaken up and down 30 times. After shaking, it was visually evaluated whether precipitation occurred in the additive after 24 hours passed, and further redispersibility after shaking was performed again was evaluated according to the following criteria. The results are shown in Table 1.
-
- A: Homogeneity is achieved when shaking is performed.
- B: Homogeneity is not achieved even when shaking is performed.
- With respect to Examples 1 to 21, although precipitation occurred, when shaking was performed again, the precipitate easily redispersed, and homogeneous dispersibility could be verified.
- On the other hand, with respect to Comparative Examples 1, 3, and 4, precipitation occurred, and even after shaking was performed again, the precipitate solidified and did not redisperse. Further, with respect to Comparative Examples 2, 5, and 6, although precipitation occurred, when shaking was performed again, the precipitate easily redispersed, and homogeneous dispersibility could be verified.
- The screw tube bottles were sealed in a state where the additives of Examples 1 to 21 and Comparative Examples 1 to 6 were placed therein, and shaking was performed until homogeneity, and then, the state of each additive was investigated after 168 hours passed. When precipitation occurred, shaking was performed again and redispersibility of the non-conductive fine particles was investigated. In the shaking, the screw tube bottle was shaken up and down 30 times. After shaking, it was visually evaluated whether precipitation occurred in the additive after 168 hours passed, and redispersibility after shaking was performed again was evaluated according to the same criteria as in Test Example 1. The results are shown in Table 2.
- Further, the results of the additive of Comparative Example 1 are shown in
FIGS. 1 and4 , the results of the additive of Example 1 are shown inFIGS. 2 and5 , and the results of the additive of Example 2 are shown inFIGS. 3 and6 .[Table 2] Precipitation Redispersibility Precipitation Redispersibility Example 1 occurred A Example 15 occurred A Example 2 occurred A Example 16 occurred A Example 3 occurred A Example 17 occurred A Example 4 occurred A Example 18 occurred A Example 5 occurred A Example 19 occurred A Example 6 occurred A Example 20 occurred A Example 7 occurred A Example 21 occurred A Example 8 occurred A Example 9 occurred A Comparative Example 1 occurred B Example 10 occurred A Comparative Example 2 occurred A Example 11 occurred A Comparative Example 3 occurred B Example 12 occurred A Comparative Example 4 occurred B Example 13 occurred A Comparative Example 5 occurred A Example 14 occurred A Comparative Example 6 occurred B - With respect to Examples 1 to 21, although precipitation occurred, when shaking was performed again, the precipitate easily redispersed, and homogeneous dispersibility could be verified.
- On the other hand, with respect to Comparative Examples 1, 3, 4, and 5, precipitation occurred, and even after shaking was performed again, the precipitate solidified and did not redisperse. Further, with respect to Comparative Examples 2 and 5, although precipitation occurred, when shaking was performed again, the precipitate easily redispersed, and homogeneous dispersibility could be verified.
- From the results of Test Examples 1 and 2, it was found that in order to form a liquid state with good dispersibility without causing precipitation of the non-conductive fine particles and solidification of the precipitate thereof, incorporation of nickel ions together with the non-conductive fine particles has an effect on redispersibility.
- The additive prepared in Example 1 was added in an amount of 0.5 mL/L to a plating bath having the following composition, thereby preparing a microporous plating solution.
-
- Nickel sulfate (NiSO4·6H2O): 260 g/L
- Nickel chloride (NiCl2·6H2O): 45 g/L
- Boric acid (H3BO3) : 45 g/L
- Brightener #810*: 3 mL/L
- Brightener MP333*: 10 mL/L
- Polyaluminum chloride: 0.3 mg/L (in terms of aluminum)
- Bath temperature: 55°C
- Specific gravity: 1.205
- *: manufactured by JCU CORPORATION
- Subsequently, a microporous plated product was produced as a test piece according to the following steps using a bent cathode test piece (brass: manufactured by Yamamoto-MS Co., Ltd.) having a shape shown in
FIG. 7 . - The test piece was treated with SK-144 (manufactured by JCU CORPORATION) for 5 minutes for degreasing, and then treated with V-345 (manufactured by JCU CORPORATION) for 30 seconds for acid activation.
- The test piece subjected to the degreasing and acid activation treatments above were plated in the following nickel plating solution at 4 A/dm2 for 3 minutes.
-
- Nickel sulfate (NiSO4·6H2O): 260 g/L
- Nickel chloride (NiCl2·6H2O): 45 g/L
- Boric acid (H3BO3) : 45 g/L
- Brightener #810*: 3 mL/L
- Brightener #83*: 10 mL/L
- *: manufactured by JCU CORPORATION
- The test piece subjected to bright plating was plated in the microporous plating solution prepared above at 3 A/dm2 for 3 minutes.
- The test piece subjected to microporous nickel plating above was plated in a hexavalent chromium plating solution having the following composition at 10 A/dm2 for 3 minutes.
-
- Chromic anhydride (CrO3): 250 g/L
- Sulfuric acid (H2SO4) : 1 g/L
- Additive ECR 300LN*: 10 mL/L
- MISTSHUT NP*: 0.1 mL/L
- *: manufactured by JCU CORPORATION
- The test piece after chrome plating was immersed in a copper sulfate plating solution having the following composition for 3 minutes, and then plated in the copper sulfate plating solution at 0.5 A/dm2 for 3 minutes.
-
- Copper sulfate (CuSO4·5H2O): 220 g /L
- Sulfuric acid (H2SO4): 50 g/L
- Hydrochloric acid (HCl): 0.15 mL/L
- After copper sulfate plating, the test piece was gently washed with water, air-dried, and then, the number of micropores in the plating film was measured. The measurement of the number of micropores was performed for the evaluation surface of the test piece using a microscope VHX-200 manufactured by KEYENCE CORPORATION. The measurement result of the number of micropores is shown in Table 3.
[Table 3] Number of micropores in evaluation surface (micropores/cm2) 30440 - With the use of the additive of the invention, the expected number of micropores could be obtained even when a microporous nickel plating solution was prepared by adding non-conductive fine particles in a liquid state.
- The additive of the invention can be utilized for preparing a composite plating solution.
Precipitation | Redispersibility | Precipitation | Redispersibility | ||
Example 1 | slightly occurred | A | Example 15 | slightly occurred | A |
Example 2 | occurred | A | Example 16 | occurred | A |
Example 3 | occurred | A | Example 17 | occurred | A |
Example 4 | occurred | A | Example 18 | occurred | A |
Example 5 | occurred | A | Example 19 | occurred | A |
Example 6 | occurred | A | Example 20 | occurred | A |
Example 7 | slightly occurred | A | Example 21 | occurred | A |
Example 8 | slightly occurred | A | |||
Example 9 | slightly occurred | A | Comparative Example 1 | occurred | B |
Example 10 | slightly occurred | A | Comparative Example 2 | occurred | A |
Example 11 | slightly occurred | A | Comparative Example 3 | occurred | B |
Example 12 | occurred | A | Comparative Example 4 | occurred | B |
Example 13 | occurred | A | Comparative Example 5 | occurred | A |
Example 14 | occurred | A | Comparative Example 6 | occurred | A |
Claims (6)
- An additive for a composite plating solution, characterized by comprising non-conductive fine particles, nickel ions, and water.
- The additive for a composite plating solution according to claim 1, wherein the composite plating solution is a satin nickel plating solution or a microporous nickel plating solution.
- The additive for a composite plating solution according to claim 1 or 2, wherein the non-conductive fine particles are one type or two or more types of oxides, nitrides, sulfides, or inorganic salts of a metal selected from the group consisting of silicon, barium, zirconium, aluminum, and titanium.
- The additive for a composite plating solution according to any one of claims 1 to 3, which contains one type or two or more types selected from the group consisting of hydrates of nickel sulfate, nickel chloride, nickel sulfamate, and nickel acetate and anhydrides of nickel sulfate, nickel chloride, nickel sulfamate, and nickel acetate.
- The additive for a composite plating solution according to any one of claims 1 to 4, further comprising one type or two or more types selected from a charge imparting agent, a surfactant, and a brightener.
- A method for preventing solidification of a precipitate of non-conductive fine particles in an additive for a composite plating solution, characterized by incorporating nickel ions in an additive for a composite plating solution containing non-conductive fine particles and water.
Applications Claiming Priority (2)
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JP2021100239A JP6945761B1 (en) | 2021-06-16 | 2021-06-16 | Additives for composite plating solutions |
PCT/JP2022/020620 WO2022264739A1 (en) | 2021-06-16 | 2022-05-18 | Additive for composite plating solutions |
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EP4357488A1 true EP4357488A1 (en) | 2024-04-24 |
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Application Number | Title | Priority Date | Filing Date |
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EP22824733.4A Pending EP4357488A1 (en) | 2021-06-16 | 2022-05-18 | Additive for composite plating solutions |
Country Status (4)
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EP (1) | EP4357488A1 (en) |
JP (1) | JP6945761B1 (en) |
CN (1) | CN115478307A (en) |
WO (1) | WO2022264739A1 (en) |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS5727818Y2 (en) * | 1976-07-02 | 1982-06-17 | ||
JP2962598B2 (en) * | 1991-06-20 | 1999-10-12 | 荏原ユージライト株式会社 | Microporous chrome plating method |
BRPI0924283B1 (en) * | 2009-02-13 | 2019-11-12 | Atotech Deutschland Gmbh | chrome part and method of manufacturing it |
JP5435477B2 (en) * | 2010-01-22 | 2014-03-05 | アイテック株式会社 | Composite plating solution in which fine diamond particles are dispersed and method for producing the same |
EP3940119A4 (en) * | 2019-03-12 | 2022-08-10 | JCU Corporation | Microporous plating solution and method of using this plating solution to perform microporous plating on object to be plated |
-
2021
- 2021-06-16 JP JP2021100239A patent/JP6945761B1/en active Active
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2022
- 2022-05-18 EP EP22824733.4A patent/EP4357488A1/en active Pending
- 2022-05-18 WO PCT/JP2022/020620 patent/WO2022264739A1/en active Application Filing
- 2022-06-13 CN CN202210661523.5A patent/CN115478307A/en active Pending
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CN115478307A (en) | 2022-12-16 |
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