CN106103802B - It is surface-treated substrate - Google Patents
It is surface-treated substrate Download PDFInfo
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- CN106103802B CN106103802B CN201580014157.2A CN201580014157A CN106103802B CN 106103802 B CN106103802 B CN 106103802B CN 201580014157 A CN201580014157 A CN 201580014157A CN 106103802 B CN106103802 B CN 106103802B
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- 239000000758 substrate Substances 0.000 title claims abstract description 140
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 149
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 124
- 210000000981 epithelium Anatomy 0.000 claims abstract description 66
- 238000012545 processing Methods 0.000 claims abstract description 60
- 238000004381 surface treatment Methods 0.000 claims abstract description 55
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 41
- 125000001165 hydrophobic group Chemical group 0.000 claims abstract description 28
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims description 22
- 238000005259 measurement Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000001514 detection method Methods 0.000 claims description 10
- -1 phosphate ester salt Chemical class 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 1
- 230000002209 hydrophobic effect Effects 0.000 claims 1
- 239000010410 layer Substances 0.000 description 113
- 238000007747 plating Methods 0.000 description 113
- 229910052717 sulfur Inorganic materials 0.000 description 96
- 239000011593 sulfur Substances 0.000 description 95
- 229910000679 solder Inorganic materials 0.000 description 46
- 239000011701 zinc Substances 0.000 description 31
- 238000000034 method Methods 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
- 238000004321 preservation Methods 0.000 description 14
- 230000007774 longterm Effects 0.000 description 13
- 150000002894 organic compounds Chemical class 0.000 description 13
- 238000011282 treatment Methods 0.000 description 13
- 230000001174 ascending effect Effects 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 125000001424 substituent group Chemical group 0.000 description 8
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910001026 inconel Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- 150000003456 sulfonamides Chemical class 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- FTLYMKDSHNWQKD-UHFFFAOYSA-N (2,4,5-trichlorophenyl)boronic acid Chemical compound OB(O)C1=CC(Cl)=C(Cl)C=C1Cl FTLYMKDSHNWQKD-UHFFFAOYSA-N 0.000 description 1
- WSGYTJNNHPZFKR-UHFFFAOYSA-N 3-hydroxypropanenitrile Chemical compound OCCC#N WSGYTJNNHPZFKR-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PQMOXTJVIYEOQL-UHFFFAOYSA-N Cumarin Natural products CC(C)=CCC1=C(O)C(C(=O)C(C)CC)=C(O)C2=C1OC(=O)C=C2CCC PQMOXTJVIYEOQL-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- FSOGIJPGPZWNGO-UHFFFAOYSA-N Meomammein Natural products CCC(C)C(=O)C1=C(O)C(CC=C(C)C)=C(O)C2=C1OC(=O)C=C2CCC FSOGIJPGPZWNGO-UHFFFAOYSA-N 0.000 description 1
- 229910000792 Monel Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000003287 bathing Methods 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
- DMFGNRRURHSENX-UHFFFAOYSA-N beryllium copper Chemical compound [Be].[Cu] DMFGNRRURHSENX-UHFFFAOYSA-N 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000833 kovar Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 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
- XTEGVFVZDVNBPF-UHFFFAOYSA-L naphthalene-1,5-disulfonate(2-) Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1S([O-])(=O)=O XTEGVFVZDVNBPF-UHFFFAOYSA-L 0.000 description 1
- HEWDOWUUTBCVJP-UHFFFAOYSA-L naphthalene-1,6-disulfonate(2-) Chemical compound [O-]S(=O)(=O)C1=CC=CC2=CC(S(=O)(=O)[O-])=CC=C21 HEWDOWUUTBCVJP-UHFFFAOYSA-L 0.000 description 1
- HEWDOWUUTBCVJP-UHFFFAOYSA-N naphthalene-1,6-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 HEWDOWUUTBCVJP-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 229940085605 saccharin sodium Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
-
- 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
- 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
- C25D5/48—After-treatment of electroplated surfaces
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Electrochemistry (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- Electroplating Methods And Accessories (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Laminated Bodies (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Abstract
The present invention provides a kind of surface treatment substrate (100), it is characterized in that, the processing epithelium (30) for successively including the nickel coating (20) for containing sulphur atom with 0.01~0.13 weight % from substrate (10) side on the surface of substrate (10) and being formed by the inorganic agent with hydrophobic group and hydrophilic group.The thickness that the present invention is surface-treated the aforementioned processing epithelium (30) of substrate (100) is preferably 1~100nm.In addition, the aforementioned processing agent that the present invention is surface-treated substrate (100) preferably has compound of the fluorocarbon chain as hydrophobic group.
Description
Technical field
The present invention relates to surface treatment substrates.
Background technique
In recent years, with the miniaturization of electronic equipment, multifunction, high property is also desirable that for the component for constituting electronic equipment
Energyization, in the component for constituting this electronic equipment, for being made in the connector of electronic equipment, the installation base plate of electronic equipment
For the conductive members such as lead frame, it is desirable that improve the various characteristics such as solder wettability.
For example, Patent Document 1 discloses a kind of conductive member, led used in the connector as electronic equipment etc.
Electric components, by forming 0.1~10nm of thickness containing specific fluorine compounds on the substrate formed by copper foil or copper alloy foil
Film, the solder wettability on surface will not be damaged and can be improved salt water resistance corrosivity.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2012-131051 bulletin
Summary of the invention
Problems to be solved by the invention
However, in conductive member disclosed in above patent document 1, there are the following problems: in the case where long-term preservation,
Outmost surface will form the oxide scale film of copper, due to the oxide scale film influence and reduce solder wettability.
The present invention is completed in view of this actual conditions, it is intended that providing a kind of surface treatment substrate, is led to
The formation for inhibiting oxide scale film is crossed, the reduction of solder wettability when can effectively inhibit long-term preservation.
The solution to the problem
The inventors of the present invention to achieve the goals above, have made intensive studies, as a result, it has been found that: substrate surface formed with
Regulated proportion contains the nickel coating of sulphur atom, and is formed on the nickel coating and formed by the inorganic agent with hydrophobic group and hydrophilic group
Processing epithelium, thus, it is possible to solve the above subject, so as to complete the present invention.
That is, according to the present invention, providing a kind of surface treatment substrate, which is characterized in that on the surface of the substrate from substrate one
Side is successively included with 0.01~0.13 weight % nickel coating for containing sulphur atom and by the processing with hydrophobic group and hydrophilic group
Dosage form at processing epithelium.
In surface treatment substrate of the invention, the thickness of aforementioned processing epithelium is preferably 1~100nm.
In surface treatment substrate of the invention, aforementioned processing agent preferably has compound of the fluorocarbon chain as hydrophobic group.
In addition, aforementioned processing epithelium is preferably in utilization ejected wash water to aforementioned nickel plating in surface treatment substrate of the invention
The surface of layer, which remain on washing and its surface, to be formed in the state of aforementioned ejected wash water.
In turn, being obtained by x-ray photoelectron spectroscopy (ESCA) measurement, aforementioned in surface treatment substrate of the invention
The integrated value at the peak C1s detected by 280~300eV energy range of the most surface part of epithelium is handled relative to aforementioned plating
Nickel layer be not detected the depth (the non-detection layers of O1s) for being present in the peak O1s of 525~540eV of energy range 845~
Ni2p detected by 865eV energy range3/2The ratio of the integrated value at peak is with " integrated value/the Ni2p at the peak C1s3/2The integrated value at peak "
Ratio meter be preferably 4.3 × 10-2~8.01 × 10-2Range.
The effect of invention
According to the present invention it is possible to a kind of surface treatment substrate is provided, it, can be effective by inhibiting the formation of oxide scale film
The reduction of solder wettability when ground inhibition long-term preservation.
Detailed description of the invention
Fig. 1 is the figure for showing the structure of surface treatment substrate of present embodiment.
Fig. 2 is to show to be formed with sulfur-bearing and plate after Ni layer of Al substrate saves under regulation environment, passes through ESCA measurement
The figure of obtained result.
Fig. 3 is to show to be formed with non-sulfur-bearing and plate after Ni layers of Al substrate saves under regulation environment, is carried out by ESCA
The figure of result obtained from measurement.
Fig. 4 be show be measured as surface treatment substrate of the ESCA to present embodiment obtained from result figure.
Specific embodiment
Hereinafter, based on attached drawing, embodiments of the present invention will be described.
Fig. 1 is the figure for showing the structure of surface treatment substrate 100 of present embodiment.As shown in Figure 1, present embodiment
Surface treatment substrate 100 sequentially forms sulfur-bearing plating Ni layer 20 and processing epithelium 30 on the surface of Al substrate 10.
<Al substrate 10>
As constitute Al substrate 10 aluminium sheet, be not particularly limited, can be used pure aluminum plate, JIS standard 1000 systems,
2000 systems, 3000 systems, 5000 systems, 6000 systems, any one in 7000 systems aluminium alloy plate, wherein the H24 of particularly preferred 1100 system
Material.The thickness of Al substrate 10 is not particularly limited, according to the purposes of the component as electronic equipment, forms thickness appropriate
Degree, preferably 0.1~0.5mm.
<sulfur-bearing plates Ni layer 20>
It is Ni layers of plating for containing sulphur atom with 0.01~0.13 weight % that sulfur-bearing, which plates Ni layer 20, such as is led on Al substrate 10
It crosses and implements plating Ni using the plating Ni bath comprising sulphur atom and formed.Sulfur-bearing plating Ni layer 20 can be arranged directly on Al substrate 10,
But in order to form sulfur-bearing plating Ni layer 20 well, it is preferred that formed on Al substrate 10 by displacement plating be used as substrate in advance
After the Zn layer of layer, it is formed on sulfur-bearing plating Ni layer 20.
It is not particularly limited, can be enumerated as the method for the Zn layer of basal layer for being formed: for composition Al substrate 10
Pure aluminum plate or aluminium alloy plate carry out ungrease treatment, then, after pickling carry out the method for the displacement plating of Zn.The displacement plating of Zn is to pass through
Implement via hydrogen nitrate dipping processing, the first Zn replacement Treatment, zinc nitrate lift-off processing, each process of the 2nd Zn replacement Treatment,
Secondary soaking zinc (double zincate) processing and carry out.At this point, implementing washing process after the processing of each process.It needs
Bright, the Zn layer formed by the first Zn replacement Treatment and the 2nd Zn replacement Treatment is slightly dissolved when implementing to plate Ni.It is right
In Zn layers, in order to form good sulfur-bearing plating Ni layer 20, it is generally desirable to become 5 preferably with the epithelium amount in the state of plating after Ni~
The range of 500mg/m2, the mode more preferably as the range of 30~300mg/m2 are formed.It should be noted that Zn layers of epithelium
Amount can be by being suitable for being impregnated in treatment fluid in the concentration and the 2nd Zn replacement Treatment for select the Zn ion in treatment fluid
Time adjusts.In addition, the displacement plating of Zn can also be handled by only implementing hydrogen nitrate dipping and the work of the first Zn replacement Treatment
Sequence implements primary leaching zinc processing to carry out.At this point, Zn layers of epithelium amount can be by being suitable for the Zn ion selected in treatment fluid
Concentration and the first Zn replacement Treatment in be impregnated in the time in treatment fluid to adjust.
Then, sulfur-bearing is formed and implementing plating Ni on Zn layer plate Ni layer 20.Plating can be used in sulfur-bearing plating Ni layer 20
The plating method of any one in method or electroless plating method and formed, it is preferable to use galvanoplastic.The thickness that sulfur-bearing plates Ni layer 20 is preferably 0.2
μm or more, more preferably 0.2~3.0 μm, further preferably 0.5~2.0 μm.
As plating Ni bath, can enumerate: usually used plating Ni bath, i.e. watt is bathed, sulfamic acid is bathed, boron fluoride bath, chlorine
Compound bath etc., in these, preferably watt is bathed.Use watt bath as plating Ni bathe when, can be used for example nickel sulfate 200~
The substance of the bath composition of 350g/L, 20~60g/L of nickel chloride, 10~50g/L of boric acid.
In present embodiment, the brightener containing sulphur atom is preferably added in advance in the plating Ni bath for implementing to plate Ni.
When adding brightener in plating Ni bath, two kinds of compounds of the 1st brightener and the 2nd brightener can be used as brightener.Wherein,
1st brightener is the organic compound with sulphur atom, and having prevents from being formed by Ni layers of impurity being mixed into plating bath of plating
Effect, and have the function of the internal stress for inhibiting to be formed by Ni layers of plating.2nd brightener is to be easily adsorbed at metal surface
Organic compound, have the function of assigning gloss, and by being applied in combination have to improve and be formed by with the 1st brightener
The gloss of Ni layers of plating and the effect of flatness.
In present embodiment, it is preferable to use the 1st at least the above brightener is as light when adding brightener in plating Ni bath
Bright dose.That is, above-mentioned 1st brightener and the 2nd brightener is preferably applied in combination or the 1st light is used alone as brightener
Agent.As a result, in present embodiment, plating Ni is implemented to Al substrate 10 using the plating Ni bath added with this brightener, is consequently formed
Sulfur-bearing plating Ni layer 20 can also containing be originated from the 1st brightener sulphur atom.
As the 1st brightener, as long as the organic compound containing sulphur atom, such as inferior such as can be enumerated have
Aromatic rings and with the aromatic rings Direct Bonding organic compound of sulfonyl: the sulfimides such as saccharin, saccharin sodium；Tolysulfonyl
The sulfonamide such as amine, benzsulfamide；1,5- naphthalene disulfonate, 1,6- naphthalene disulfonate or 2,5- naphthalene disulfonate, 1,3,6- naphthalene three
The sulfonic acid such as sodium sulfonate；The sulfonate such as benzene sulfonic acid.In these, particularly preferred sulfimide, sulfonamide.
As the 2nd brightener, it is preferably easily adsorbed at the organic compound of metal surface, for example containing the heterocycle of nitrogen-atoms
Compound has C=O, C=C, C ≡ C, C ≡ N, C=S, N-C-S, N=N or CH2The isostructural organic compound of-CH-O, tool
It for body, can enumerate: quinoline, pyridine, formaldehyde, 2- butine-Isosorbide-5-Nitrae-glycol, cumarin, propilolic alcohol, 3- hydroxypropionitrile, thiocarbamide etc..
In these, particularly preferably with the organic compound (2- butine-Isosorbide-5-Nitrae-glycol) of C ≡ C-structure.
In present embodiment, as described above, sulfur-bearing plating Ni layer 20 is the object for containing sulphur atom with 0.01~0.13 weight %
Matter, the sulphur atom content that sulfur-bearing plates in Ni layer 20 is preferably 0.015~0.13 weight %.According to the present embodiment, make to be formed in
Sulfur-bearing plating Ni layer 20 on Al substrate 10 contains sulphur atom with above range, is surface-treated substrate 100 thus directed towards gained, can
Inhibit the reduction of solder wettability in long-term preservation.
Here, Fig. 2 is to show sulfur-bearing obtained from forming sulfur-bearing plating Ni layer 20 on Al substrate 10 to plate Ni substrate difference
After saving 7 days at 20 DEG C of temperature, saving 7 days at 85 DEG C of humidity 85%RH of temperature, saved 7 days at 100 DEG C, pass through
The curve graph of the result of x-ray photoelectron spectroscopy (ESCA) measurement.In curve graph shown in Fig. 2, horizontal axis is indicated, is made by ESCA
The time for being etched sulfur-bearing plating Ni substrate from outmost surface with Ar gas；The longitudinal axis indicates 525~540eV energy range
The integrated intensity at the peak O1s.
On the other hand, Fig. 3 show to form Ni layers of plating for bathing on Al substrate 10 using plating Ni not containing sulphur atom and
The result that obtained non-sulfur-bearing plating Ni substrate is measured likewise by ESCA.It should be noted that Fig. 2 shows aftermentioned embodiments 1
The measurement result of the sulfur-bearing plating Ni substrate of middle production, Fig. 3 show the measurement of the non-sulfur-bearing plating Ni substrate made in aftermentioned comparative example 1
As a result.
It confirms: in the case that sulfur-bearing shown in Fig. 2 plating Ni substrate saves 7 days in the environment of 20 DEG C, and shown in Fig. 3
Non- sulfur-bearing plating Ni substrate compare, the intensity at the peak O1s is intended to the value close to zero with shorter etching period.Herein, it is believed that:
Fig. 2, the peak O1s shown in 3 are originated from sulfur-bearing plating Ni substrate or the surface of non-sulfur-bearing plating Ni substrate is formed by oxide scale film.As a result,
Confirm: for sulfur-bearing plating Ni substrate shown in Fig. 2 compared with non-sulfur-bearing plating Ni substrate shown in Fig. 3, surface is formed by oxidation
The thinner thickness of epithelium can determine whether out the formation for being able to suppress oxide scale film.
Similarly, it confirms: even if when with the preservation of more rigor condition, temperature 85 i.e. as depicted in figs. 2 and 3
When saving in the environment of DEG C humidity 85%RH, when saving in the environment of 100 DEG C of temperature, sulfur-bearing shown in Fig. 2 plates Ni substrate
Than the formation that non-sulfur-bearing plating Ni substrate shown in Fig. 3 is able to suppress oxide scale film.
It is considered that: the effect for being able to suppress the formation of this oxide scale film is based upon in sulfur-bearing plating Ni substrate
The adsorption H of sulfur-bearing plating Ni layer 202O or O2It is formed by adsorption layer and realizes.
Especially in the present embodiment, it is believed that: it is formed by Al substrate 10 in sulfur-bearing plating Ni layer 20 with above-mentioned
Range contains sulphur atom, therefore causes oxygen and the binding force of plating epithelium to subtract and sulfur-bearing plates Ni layer 20 by containing sulphur atom
Weak effect makes coating surface adsorb H by coating surface smoothing2O or O2The effect that tails off of area, thus sulfur-bearing plates
Ni substrate is able to suppress the film thickness of the oxide scale film on sulfur-bearing plating Ni layer 20 in high temperature and humidity condition long-term preservation.
It should be noted that preferably being added in the plating Ni bath for being used to form sulfur-bearing plating Ni layer 20 in present embodiment
Brightener is stated, but in addition to brightener, the additives such as antioxidant, dispersing agent, anti-pit agent can also be added.Alternatively, with
Other additives containing sulphur atom can also be added in the plating Ni bath for forming sulfur-bearing plating Ni layer 20 to replace without using light
Agent.
<processing epithelium 30>
Processing epithelium 30 is the inorganic agent on above-mentioned sulfur-bearing plating Ni layer 20 by covering with hydrophobic group and hydrophilic group
It is formed.
In present embodiment, as the inorganic agent for being used to form processing epithelium 30, as long as being with hydrophobic group and hydrophilic group
Can, it is not particularly limited, can enumerate: shown in the following general formula (1), being respectively provided with organising for each 1 hydrophobic group and hydrophilic group
Close object.
A-B (1)
(in above-mentioned general formula (1), A is hydrophobic group, and B is hydrophilic group.)
It as hydrophobic group A shown in above-mentioned general formula (1), such as can enumerate: the aliphatic alkyl containing halogen.It can contain
The structure of the aliphatic alkyl of halogen can be that any one of straight-chain, branched or ring-type can also be in turn to combine this
Structure made of a little structures, but the structure of preferably straight-chain or branched.In addition, the carbon of the aliphatic alkyl containing halogen
Atomicity is preferably 6~20, more preferably 8~18.
It as this aliphatic alkyl containing halogen, can preferably enumerate: substituent group shown in the following general formula (2).It needs
It is noted that hydrophilic group B Direct Bonding shown in substituent group shown in the following general formula (2) and above-mentioned general formula (1).
In above-mentioned general formula (2), R1~R5Separately for hydrogen atom, halogen atom, carbon atom number 1~18 alkyl or
The halogenated alkyl of carbon atom number 1~18.As halogen atom, preferably fluorine atom, chlorine atom or bromine atom, more preferably fluorine is former
Son.As halogenated alkyl, preferably fluoroalkyl, chlorine alkyl or bromine alkyl, more preferably fluoroalkyl.In above-mentioned general formula (2), table
When the n for showing number of repeat unit is 2 or more, R2Each other, R3Each other, R4Each other and R5It each other can be identical, or different.
It should be noted that the integer that the n in above-mentioned general formula (2) is 1~10, preferably 4~8.
In the substituent group shown in above-mentioned general formula (2), as hydrophobic group A, preferably substituent group shown in the following general formula (3).
It should be noted that hydrophilic group B Direct Bonding shown in substituent group shown in the following general formula (3) and above-mentioned general formula (1).
In above-mentioned general formula (3), R6For fluorine atom, hydrogen atom or CR7R8R9(R7~R9It is separately former for fluorine atom or hydrogen
Son).Integer that p in above-mentioned general formula (3) is 1~10, preferably 4~8.It is integer that q in above-mentioned general formula (3) is 0~5, excellent
It is selected as 1~3.
It as hydrophilic group B shown in above-mentioned general formula (1), is not particularly limited, such as can enumerate: the group of phosphate ester salt (-
OPO3HM or-OPO3M2), the group (- COOM) of carboxylate, sulfuric acid group (- OSO3M), the group (- SO of sulfonate3M)
Deng.It should be noted that can be enumerated as the M in above-mentioned hydrophilic group B: the alkali metal such as sodium, potassium, ammonium, alkanol amine salt etc., this
In a little, particularly preferred sodium.
In present embodiment, this processing epithelium 30 is formed on Ni layer 20 by plating in sulfur-bearing, can be improved gained surface
Handle the solder wettability of substrate 100.That is, being sent out in processing epithelium 30 because constituting the hydrophobic group of inorganic agent of processing epithelium 30
Waterproof action is waved, therefore can prevent attachment of moisture from plating Ni layer 20 in the sulfur-bearing of gained surface treatment substrate 100, inhibits oxide scale film
Formation, thus, it is possible to prevent as caused by oxide scale film be surface-treated substrate 100 solder wettability reduction.In addition, place
It manages in epithelium 30, the hydrophilic group of the inorganic agent by constituting processing epithelium 30, can make to handle epithelium 30 and be adsorbed in well to contain
Sulphur plates Ni layer 20, in turn, solder wettability when forming solder layer on surface treatment substrate 100 can be improved.
In particular, the hydrophobic group for constituting the inorganic agent of processing epithelium 30 is arranged to above-mentioned general formula (2) in present embodiment
R1~R5In (when the n for indicating number of repeat unit is 2 or more, multiple R1~R5In) at least one be the fluorine containing fluorine atom
Carbochain, the waterproofness for thus handling epithelium 30 improve, and can more efficiently prevent from the shape of the oxide scale film of surface treatment substrate 100
At.
In present embodiment, as the inorganic agent for constituting processing epithelium 30, as long as there is hydrophobic group and hydrophilic group to be above-mentioned
Compound, be just not particularly limited, such as preferably anionic surfactant.
As the method for forming processing epithelium 30, for example, the following methods can be used: water-soluble dissolved with above-mentioned inorganic agent
Sulfur-bearing is impregnated in liquid and plates Ni substrate, is then washed and is dried, and the sulfur-bearing plating Ni substrate is to be formed to contain on Al substrate 10
Sulphur plates obtained from Ni layer 20.At this point, preferably being impregnated to form processing epithelium 30 well with following condition.That is, water
The concentration of inorganic agent in solution is preferably 1~30 weight %, more preferably 1~20 weight %.In addition, dip time is preferably
2~30 seconds, more preferably 5~20 seconds.In turn, temperature when dipping is preferably 10~80 DEG C, more preferably 20~60 DEG C.
In present embodiment, processing epithelium 30 is constituted and with the inorganic agent of hydrophobic group and hydrophilic group as described above
, therefore Ni layer 20 can be plated with sulfur-bearing by the hydrophilic group of inorganic agent contained in processing epithelium 30 and adsorbed well, and
When forming solder layer on being surface-treated substrate 100, solder wettability can be improved, in turn, by contained in processing epithelium 30
Inorganic agent hydrophobic group, can prevent attachment of moisture in sulfur-bearing plate Ni layer 20, inhibit the formation of oxide scale film, so as to prevent
Only because of the reduction of the solder wettability of surface treatment substrate 100 caused by oxide scale film.Therefore, in present embodiment, this is formed
The solder wettability of the surface treatment substrate 100 of kind processing epithelium 30 is excellent, in turn, can effectively be pressed down by handling epithelium 30
The formation of the oxide scale film of sulfur-bearing processed plating Ni layer 20, therefore even if solder wettability is also excellent when long-term preservation.
It should be noted that the thickness of processing epithelium 30 is preferably 1~100nm, more preferably 1~50nm.If handling skin
The thickness of film 30 is excessively thin, then in surface treatment substrate 100, there is the effect of the formation for the oxide scale film for inhibiting sulfur-bearing plating Ni layer 20
Reduced worry.On the other hand, if the thickness of processing epithelium 30 is blocked up, there is the solder profit on the surface of surface treatment substrate 100
Moist reduced worry.
<manufacturing method of surface treatment substrate 100>
Then, it is illustrated for the manufacturing method of the surface treatment substrate 100 of present embodiment.
Firstly, preparing the aluminium sheet for constituting Al matrix 10, on Al matrix 10, such as the plating Ni containing sulphur atom is used
Plating Ni is implemented in bath, and sulfur-bearing plating Ni layer 20 is consequently formed.It should be noted that due to be difficult to Al matrix 10 Al directly on a surface
Sulfur-bearing is set and plates Ni layer 20, therefore preferably first passes through in advance and Al matrix 10 is implemented at above-mentioned secondary soaking zinc processing or primary leaching zinc
Reason is to form Zn layers, to form sulfur-bearing plating Ni layer 20 on Zn layers.At this point, galvanoplastic or chemical plating can be used in plating Ni layer 20
Any plating method in method is formed, it is preferable to use galvanoplastic.
Use galvanoplastic as formed sulfur-bearing plating Ni layer 20 method when, following method can be used for example: as plating
Ni bath is bathed using the watt of the bath composition of 200~350g/L of nickel sulfate, 20~60g/L of nickel chloride, 10~50g/L of boric acid, to plating
Above-mentioned brightener is added in Ni bath, in pH3~4.8,40~70 DEG C of bath temperature, 10~40A/dm of current density2(preferably 20~
30A/dm2) under conditions of implement plating Ni, the method then washed.
Then, processing epithelium 30 is formed on being formed by sulfur-bearing plating Ni layer 20.For handling epithelium 30, can enumerate as follows
Method: it is for example impregnated in dissolving aqueous solution obtained by the inorganic agent with hydrophobic group and hydrophilic group and has formd Ni layers of sulfur-bearing plating
20 Al substrate 10, the method then washed and dried.
It should be noted that in present embodiment, when forming processing epithelium 30, preferably on the surface of sulfur-bearing plating Ni layer 20
On by sulfur-bearing plating Ni layer 20 washed after, in the state of remaining the ejected wash water used for washing formed handle epithelium
30.It as a result, due to the remained on surface ejected wash water of sulfur-bearing plating Ni layer 20, therefore is acted on, can inhibited by the epitheliumization of ejected wash water
Sulfur-bearing plating Ni layer 20 forms processing epithelium 30 in the state of contacting with air, therefore can effectively inhibit sulfur-bearing plating Ni layer 20
The formation of oxide scale film.
Sulfur-bearing plating Ni layer 20 and processing are sequentially formed from 10 side of Al substrate on Al substrate 10 as described above, can manufacture
Substrate 100 is surface-treated obtained from epithelium 30.The surface treatment substrate 100 of present embodiment is by containing sulphur atom in containing
Sulphur plates Ni layer 20 and leads to the effect of the binding force of oxygen and plating epithelium decrease, makes coating surface by coating surface smoothing
Adsorb H2O or O2The effect that tails off of area and antioxidation by 30 bring sulfur-bearing of processing epithelium plating Ni layer 20, i.e.,
Formation, the solder wettability for making also to be able to suppress oxide scale film when long-term preservation are excellent.Therefore, the surface treatment of present embodiment
Substrate 100 is excellent the solder wettability in long-term preservation, therefore can be especially suitable for conductive materials such as lead frames.
It should be noted that surface treatment substrate 100 is preferably: passing through x-ray photoelectron spectroscopy in present embodiment
(ESCA) peak C1s detected by 280~300eV energy range of most surface part obtain, processing epithelium 30 is measured
Integrated value be present in the depth (O1s at the peak O1s of 525~540eV of energy range relative to being not detected for sulfur-bearing plating Ni layer 20
Non- detection layers) the Ni2p detected by 845~865eV energy range3/2The ratio of the integrated value at peak is with " the integral at the peak C1s
Value/Ni2p3/2The ratio of the integrated value at peak " is calculated as 4.3 × 10-2~8.01 × 10-2。
In present embodiment, by making the above-mentioned " integrated value/Ni2p at the peak C1s3/2The integrated value at peak " (is set as " A belowC/
ANi".) in above range, the solder wettability of surface treatment substrate 100 is can be improved in control, and then can effectively inhibit by
The formation of oxide scale film when the surface treatment progress long-term preservation of substrate 100.That is, above-mentioned " AC/ANi" it is excessive when, constitute processing skin
Carbon atom in the inorganic agent of film 30 there are the hydrophobic group in ratio, i.e. inorganic agent there are ratios to become excessively, due to dredging
Water base influence, the worry for thering is solder wettability to reduce.On the other hand, above-mentioned " AC/ANi" it is too small when, constitute processing epithelium 30
Hydrophobic group in inorganic agent that there are ratios is very few, have causes waterproof action to reduce, inhibits oxide scale film by processing epithelium 30
The worry that the effect of formation reduces.
Here, Fig. 4 (A) be show: for surface treatment substrate 100, will by ESCA when being etched from most appearance
Facing towards thickness direction measurement until 275~305eV energy range when in sulfur-bearing plating Ni layer 20 is with each defined etch depth
The curve graph for the result that measurement is 12 times.In the curve graph of Fig. 4 (A), resulting determination data will be measured by 12 times and be arranged in the longitudinal axis,
More it is in the measurement number that the determination data of downside more measures in the region on the most surface layer close to surface treatment substrate 100
According to more the determination data in upside is more surface-treated the measurement that the region of the inside of substrate 100 measures in direction
Data.In addition, similarly, Fig. 4 (B) is the curve graph for showing the result of measurement 525~540eV energy range, Fig. 4 (C) is to show
The curve graph of the result of 845~885eV energy range is measured out.It should be noted that Fig. 4 (A)~Fig. 4 (C) shows aftermentioned reality
Apply the measurement result of the surface treatment substrate 100 made in example 1.
In present embodiment, for above-mentioned " AC/ANi" calculation method be not particularly limited, such as such as Fig. 4 (A)~Fig. 4
(C) shown in, by ESCA from surface treatment substrate 100 processing epithelium 30 outmost surface when being etched towards thickness side
To until being measured in sulfur-bearing plating Ni layer 20, the method that can be calculated based on gained measurement result using following operation.
Specifically, firstly, the layer at the peak O1s for being present in 525~540eV energy range is not detected by ESCA confirmation
The depth present in sulfur-bearing plating Ni layer 20 in surface treatment substrate 100 is thus detected in the position of (the non-detection layers of O1s).That is, logical
When crossing ESCA and being measured when being etched, as shown in Fig. 4 (B), in the most surface layer of surface treatment substrate 100, clearly detect
The peak O1s of 525~540eV energy range, but etch depth deepens, direction is surface-treated the inside of substrate 100, the peak O1s
Become smaller, it is shown in dotted line in Fig. 4 (B), it is able to confirm that the non-detection layers of O1s.Here, the peak O1s is to be derived mainly from processing skin
The peak of film 30, therefore, it is possible to judge that going out: the non-detection layers of O1s that the peak O1s is not detected do not handle epithelium 30, quite
In the layer of sulfur-bearing plating Ni layer 20.Therefore, by ESCA, the non-detection layers of O1s of 525~540eV energy range are confirmed, thus, it is possible to
Enough depth present in detection sulfur-bearing plating Ni layer 20, by with the depth (" the sulfur-bearing plating Ni layer 20 being represented by dashed line in Fig. 4 (C)
Range ") calculate 845~865eV energy range detected by Ni2p3/2The integrated value at peak, so as to find out sulfur-bearing plating Ni
The Ni2p of layer 203/2The integrated value at peak.
It should be noted that at this point, the non-detection layers of O1s can be confirmed by operating as follows: for example with surface treatment
The peak O1s of 525~540eV energy range detected by the outmost surface of substrate 100 is compared, and the intensity for detecting peak is less than extremely
10% or less such depth, thereby confirms that.
In turn, above-mentioned " A can be found out by calculating following ratioC/ANi": processing epithelium 30 most surface part
The integrated value at the peak C1s detected by 280~300eV energy range (" the most surface layer C1s " is represented by dashed line in Fig. 4 (A)) with such as
Ni2p of the upper resulting sulfur-bearing plating Ni layer 20 in the non-detection layers of O1s3/2The ratio of the integrated value at peak.
In addition, being directed to the surface treatment substrate 100 of present embodiment, in above-mentioned example, shows and made using Al substrate 10
The example of the substrate of substrate 100, but the substrate as surface treatment substrate 100 are surface-treated for composition, as long as having conduction
The metal of property is just not particularly limited, can be used for example beryllium copper, iron castings, copper alloy, germanium, inconel (Inconel),
Kovar alloy, magnesium, monel metal, nichrome, rhodium, steel, stainless steel, zinc, zinc die casting etc. replace above-mentioned Al substrate 10.
Embodiment
Hereinafter, enumerating embodiment, it is specifically described for present embodiment, but present embodiment is not implemented by these
Example limitation.
<embodiment 1>
As the material for being used to form Al substrate 10, prepare aluminum material (A1100-H24, thickness 0.30mm).Also, it uses
Lye (NIPPONPAINT Co., Ltd. system, aqueous solution made of EC370 is diluted in a manner of as the concentration of 5g/L) will
The Al substrate 10 of preparation impregnates 30 seconds at 70 DEG C of liquid temperature and carries out degreasing, and is washed.Then, by making Al substrate 10 exist
It is impregnated in the aqueous sulfuric acid that concentration is 7 weight % 30 seconds under room temperature and carries out pickling, and after being washed, by using city
The zincic acid saline solution sold impregnates 20 seconds progress Zn replacement Treatments at 25 DEG C of liquid temperature, with 100~300mg/m on Al substrate 102's
Epithelium amount forms Zn layers.
Then, plating Ni is carried out under the following conditions for the Al substrate 10 for forming Zn layers, 1.0 μm of thickness are formed on Zn layers
Sulfur-bearing plate Ni layer 20.
Bath composition: the plating Ni bath 3L of 6 hydrate 300g/L of nickel sulfate, 6 hydrate 25g/L of nickel chloride, boric acid 45g/L
1st brightener: dissolution has aromatic rings and has been bonded aqueous solution obtained by the organic compounds containing sulfur of sulfonyl
10ml/L
2nd brightener: it dissolves the heterocyclic compound containing nitrogen-atoms and has been bonded the non-of the substituent group with C ≡ C-structure
Aqueous solution 3ml/L obtained by organic compounds containing sulfur
Anti- pit agent: the anti-pit agent 0.5g/L containing NaLS
PH:4.6
Bath temperature: 45 DEG C
Current density: 10A/dm2
Also, it for the Al substrate 10 for being formed with sulfur-bearing plating Ni layer 20, is filled using inductively coupled plasma atomic emission
It sets (Shimadzu Corporation's system, ICPE-9000) to be measured, as a result, with (weight/sulphur atom weight of sulphur atom
With the total value of the weight of nickle atom) ratio find out sulfur-bearing plating Ni layer 20 in sulphur atom content ratio.Show the result in table
1。
Then, it for the Al substrate 10 for being formed with sulfur-bearing plating Ni layer 20, is impregnated in following conditions with hydrophobic group and parent
After in the aqueous solution of water base inorganic agent, washed and dried, thus sulfur-bearing plating Ni layer 20 on formation thickness 0.1~
The waterproof membrane A (processing epithelium 30) of 10nm, to obtain surface treatment substrate 100.
The aqueous solution of inorganic agent: aqueous solution obtained by following inorganic agent is dissolved with 20ml/L, the inorganic agent includes conduct
Substituent group shown in the above-mentioned general formula (3) of hydrophobic group (it should be noted that in above-mentioned general formula (3), R6For trifluoromethyl, p 3,
The group that q is 1.) and the phosphoric acid as hydrophilic group substituent group
Liquid temperature: room temperature
Dip time: 10 seconds
Then, gained surface treatment substrate 100 cutting is made into multiple test films.Also, for made multiple
One in test film, according to JIS C60068-2-54 and JIS Z3198-4, under the following conditions using solder bath balancing method
It measures zero crossing time (zero cross time), it is ascending thus to evaluate solder.That is, making to be surface-treated the leaching of substrate 100
For stain when fusion weld hopper, measuring solder under the following conditions makes the moistened surface for being surface-treated substrate 100 rise, reach melting
Time until the liquid level of solder bath, zero crossing time is thus found out, evaluation solder is ascending.Show the result in table 1.It needs
The case where being noted that in table 1, the evaluation ascending about solder, zero crossing time is lower than 10 seconds is set as 〇, will
Zero crossing time be 10 seconds or more situations be set as ×.
Test chip size: thickness 0.3mm, width 7mm, length 20mm
Experimental rig: wetability tester (Malcom Co., Ltd. system, SWB-2)
Solder: Ag3.0 weight %, Cu0.5 weight %, surplus Sn
Solder bath temperature: 245 DEG C
Solder flux: commercially available solder flux (TAMURA Corporation system, EC-19s-8)
The solder dip time: 5 seconds
Solder flux pull rate: 5mm/s
Drying time: 30 seconds
Solder dipping speed: 20mm/s
The solder dipping time: 10 seconds
Solder dipping depth: 2mm
Solder pull rate: 20mm/s
In addition, being saved under following environmental condition using the test film for making gained surface treatment substrate 100 cutting
Afterwards, zero crossing time is measured as described above, and it is ascending thus to evaluate solder.That is, by test film 7 at 20 DEG C of temperature
It, saved respectively under conditions of 7 days, 85 DEG C of humidity 85%RH of temperature lower 7 days at 100 DEG C of temperature after, measure zero crossing time,
It is ascending to evaluate solder.Show the result in table 1.
Then, using the test film for making gained surface treatment substrate 100 cutting, pass through ESCA (Japan Electronics strain
Formula commercial firm system, JPS-9200), in radiographic source: monochromatic AlK α, apply voltage: 12kV, emission current: 25mA, energy value:
1486.6eV, measurement range: 3mm × 1mm, etching: 99.999%Ar gas, air pressure: 7 × 10-2Under conditions of Pa, measure outermost
The integrated value at the peak C1s detected by 280~300eV energy range and 525~540eV energy range is not detected in surface
The peak O1s depth the Ni2p detected by 845~865eV energy range3/2Peak integrated value, calculate these integrals
Ratio " integrated value/the Ni2p at the peak C1s of value3/2The integrated value at peak " (" AC/ANi").Show the result in table 1.
<embodiment 2,3>
By the dosage of the 1st brightener and the 2nd brightener on change Al substrate 10 when formation sulfur-bearing plating Ni layer 20, make to contain
The ratio of sulphur atom contained in sulphur plating Ni layer 20 changes as shown in table 1, in addition to this, makes similarly to Example 1
Make surface treatment substrate 100, and is equally evaluated.Show the result in table 1.
<embodiment 4,5>
As the inorganic agent for being used to form processing epithelium 30, using will have the non-fluorine-containing of carbon atom number 12~18 or so
The hydrophobic group of hydrocarbon chain, the aqueous solution that 150ml/L is diluted to the surface treating agent of the hydrophilic group with carboxyl, by the water of inorganic agent
The liquid temperature of solution is changed to 50 DEG C, waterproof membrane B (processing epithelium 30) is consequently formed, in addition to this, similarly to Example 1
Production surface treatment substrate 100, is equally evaluated.Show the result in table 1.
<comparative example 1>
When forming sulfur-bearing plating Ni layer 20 on Al substrate 10, brightener is not used, forms non-sulfur-bearing plating Ni with following conditions
Layer replaces the sulfur-bearing to plate Ni layer 20, and then not formed processing epithelium 30, in addition to this, similarly to Example 1 at production surface
Substrate 100 is managed, is equally evaluated.Show the result in table 1.
Bath composition: the plating Ni bath 3L of 6 hydrate 250g/L of nickel sulfate, 6 hydrate 40g/L of nickel chloride, boric acid 30g/L
Anti- pit agent: the anti-pit agent 0.5g/L containing NaLS
PH:4.3
Bath temperature: 45 DEG C
Current density: 10A/dm2
<comparative example 2>
When forming sulfur-bearing plating Ni layer 20 on Al substrate 10, the light formed by the organic compound without containing sulphur atom is used
The bright dose of organic compounds containing sulfur replaced as the 1st brightener forms non-sulfur-bearing with following conditions and plates Ni layers and not formed place
Epithelium 30 is managed, in addition to this, production surface treatment substrate 100, is equally evaluated similarly to Example 1.It shows the result in
Table 1.
Bath composition: the plating Ni bath 3L of 6 hydrate 260g/L of nickel sulfate, 6 hydrate 45g/L of nickel chloride, boric acid 45g/L
1st brightener: aqueous solution 4ml/L obtained by the brightener formed as non-organic compounds containing sulfur is dissolved
2nd brightener: aqueous solution 4ml/L obtained by the brightener formed as non-organic compounds containing sulfur is dissolved
Anti- pit agent: commercially available anti-pit agent 1ml/L (WORLD METAL CO., LTD. system, NS-AP)
PH:4.3
Bath temperature: 45 DEG C
Current density: 10A/dm2
<comparative example 3~6>
By adjusting the dosage of the 1st brightener and the 2nd brightener on Al substrate 10 when formation sulfur-bearing plating Ni layer 20, make
The ratio of sulphur atom contained in sulfur-bearing plating Ni layer 20 changes as shown in table 1, and then not formed processing epithelium 30, removes this
Except, production surface treatment substrate 100, is equally evaluated similarly to Example 1.Show the result in table 1.
<comparative example 7>
Equally operated with comparative example 1, form non-sulfur-bearing on Al substrate 10 and plate Ni layers, then, on it with implementation
Example 1 is identically formed waterproof membrane A, and thus production surface treatment substrate 100, is equally evaluated.Show the result in table 1.
<comparative example 8>
Equally operated with comparative example 1, form non-sulfur-bearing on Al substrate 10 and plate Ni layers, then, on it with implementation
Example 4 is identically formed waterproof membrane B, and thus production surface treatment substrate 100, is equally evaluated.Show the result in table 1.
<comparative example 9>
Equally operated with comparative example 2, form non-sulfur-bearing on Al substrate 10 and plate Ni layers, then, on it with implementation
Example 1 is identically formed waterproof membrane A, and thus production surface treatment substrate 100, is equally evaluated.Show the result in table 1.
<comparative example 10>
Use aqueous polyurethane resin (ADEKA CORPORATION system, ADEKA BONTIGHTER without hydrophobic group
HUX350 inorganic agent) forms non-waterproof membrane (processing epithelium 30), in addition to this, equally operates with comparative example 1, makes table
Surface treatment substrate 100, is equally evaluated.Show the result in table 1.
[table 1]
As shown in table 1, for sequentially forming on the surface of Al substrate 10 from 10 side of Al substrate with 0.01~0.13 weight
The sulfur-bearing plating Ni layer 20 and handle epithelium 30 by what the inorganic agent with hydrophobic group and hydrophilic group was formed that amount % contains sulphur atom
Examples 1 to 5, the ascending evaluation result of solder is good, is surface-treated substrate 100 for gained, can press down well
The reduction of solder wettability when long-term preservation processed.It should be noted that Fig. 2 is to show to measure by ESCA to be made by embodiment 1
The curve graph of the result of Al substrate 10 making, being formed with sulfur-bearing plating Ni layer 20.In addition, Fig. 4 (A)~Fig. 4 (C) is to show to pass through
The curve graph of the result for the surface treatment substrate 100 that ESCA measurement is made by embodiment 1.
On the other hand, as shown in table 1, for the comparative example 1~6 of not formed processing epithelium 30, gained is surface-treated substrate
100 under conditions of 85 DEG C of humidity 85%RH of temperature, 7 days when saving, and the ascending evaluation result of solder is poor, thus may be used
It confirms: when long-term preservation, the ascending reduction of solder.In addition, as shown in table 1, although for foring processing epithelium 30,
But the sulfur-bearing ratio of Ni layer of plating is the comparative example 7~9 of 0 (zero), in 100 DEG C of temperature, temperature 85 DEG C of humidity 85%RH
Under the conditions of solder when saving 7 days it is ascending evaluation result it is poor, thus confirm: when long-term preservation, solder
It is ascending to further decrease.In turn, the sulfur-bearing ratio for Ni layers of plating is 0 (zero) and then uses the water without hydrophobic group
It is the comparative example 10 that polyurethane resin forms processing epithelium 30, the similarly ascending evaluation result of solder is poor, thus
Confirm: when long-term preservation, solder is ascending to be further decreased.It should be noted that Fig. 3 is to show to survey by ESCA
The curve graph of fixed result being made by comparative example 1, being formed with non-Ni layers of sulfur-bearing plating of Al substrate 10.
Description of symbols
100 ... surface treatment substrates
10 ... Al substrates
20 ... sulfur-bearings plate Ni layers
30 ... processing epitheliums
Claims (5)
1. a kind of surface treatment substrate, which is characterized in that successively include with 0.01 from substrate side on the surface of the substrate~
The nickel coating that 0.13 weight % contains sulphur atom and the processing epithelium formed by the inorganic agent with hydrophobic group and hydrophilic group,
The inorganic agent with hydrophobic group and hydrophilic group is with optionally containing the aliphatic alkyl of halogen as described hydrophobic
Base has the base in the group of group selected from phosphate ester salt, the group of carboxylate, the group of sulfuric acid and sulfonate
Inorganic agent of the group as the hydrophilic group,
For the nickel coating, the most surface section of the processing epithelium obtained by x-ray photoelectron spectroscopy (ESCA) measurement, described
Presence is not detected relative to the nickel coating in the integrated value at the peak C1s detected by 280~300eV energy range divided
In the peak O1s of 525~540eV of energy range depth (the non-detection layers of O1s) detected by 845~865eV energy range
Ni2p3/2The ratio of the integrated value at peak is with " integrated value/the Ni2p at the peak C1s3/2The ratio of the integrated value at peak " is calculated as 4.3 × 10-2~
8.01×10-2Range.
2. surface treatment substrate according to claim 1, which is characterized in that the processing epithelium with a thickness of 1~
100nm。
3. surface treatment substrate according to claim 1 or 2, which is characterized in that the inorganic agent is to make with fluorocarbon chain
For the compound of hydrophobic group.
4. surface treatment substrate according to claim 1 or 2, which is characterized in that the processing epithelium is to utilize cleaning
Water, which to the surface of the nickel coating remain in washing and its surface, to be formed in the state of the ejected wash water.
5. surface treatment substrate according to claim 3, which is characterized in that the processing epithelium is to utilize ejected wash water pair
The surface of the nickel coating, which remain on washing and its surface, to be formed in the state of the ejected wash water.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014081648A JP6405109B2 (en) | 2014-04-11 | 2014-04-11 | Surface treatment substrate |
| JP2014-081648 | 2014-04-11 | ||
| PCT/JP2015/061229 WO2015156390A1 (en) | 2014-04-11 | 2015-04-10 | Surface-treated base |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106103802A CN106103802A (en) | 2016-11-09 |
| CN106103802B true CN106103802B (en) | 2019-06-04 |
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| CN201580014157.2A Active CN106103802B (en) | 2014-04-11 | 2015-04-10 | It is surface-treated substrate |
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| JP (1) | JP6405109B2 (en) |
| CN (1) | CN106103802B (en) |
| WO (1) | WO2015156390A1 (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57200588A (en) * | 1981-06-04 | 1982-12-08 | Nec Corp | Nickel plating solution |
| JP2000244084A (en) * | 1999-02-24 | 2000-09-08 | Kyocera Corp | Wiring board |
| JP2004323926A (en) * | 2003-04-25 | 2004-11-18 | Ishihara Chem Co Ltd | Post treatment liquid for plated surface and post treatment method |
| JP2005141693A (en) * | 2003-11-10 | 2005-06-02 | Dainippon Printing Co Ltd | Ic card and ic module |
| CN101705480A (en) * | 2009-11-03 | 2010-05-12 | 燕山大学 | Chemical modification technology of chemical nickel phosphorus plating alloy coating |
| JP2012172190A (en) * | 2011-02-21 | 2012-09-10 | Daiwa Fine Chemicals Co Ltd (Laboratory) | Sealing agent solution, and sealing method using the same |
-
2014
- 2014-04-11 JP JP2014081648A patent/JP6405109B2/en active Active
-
2015
- 2015-04-10 CN CN201580014157.2A patent/CN106103802B/en active Active
- 2015-04-10 WO PCT/JP2015/061229 patent/WO2015156390A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57200588A (en) * | 1981-06-04 | 1982-12-08 | Nec Corp | Nickel plating solution |
| JP2000244084A (en) * | 1999-02-24 | 2000-09-08 | Kyocera Corp | Wiring board |
| JP2004323926A (en) * | 2003-04-25 | 2004-11-18 | Ishihara Chem Co Ltd | Post treatment liquid for plated surface and post treatment method |
| JP2005141693A (en) * | 2003-11-10 | 2005-06-02 | Dainippon Printing Co Ltd | Ic card and ic module |
| CN101705480A (en) * | 2009-11-03 | 2010-05-12 | 燕山大学 | Chemical modification technology of chemical nickel phosphorus plating alloy coating |
| JP2012172190A (en) * | 2011-02-21 | 2012-09-10 | Daiwa Fine Chemicals Co Ltd (Laboratory) | Sealing agent solution, and sealing method using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015156390A1 (en) | 2015-10-15 |
| JP2015203123A (en) | 2015-11-16 |
| CN106103802A (en) | 2016-11-09 |
| JP6405109B2 (en) | 2018-10-17 |
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