WO2022124303A1 - Electroless gold plating solution - Google Patents
Electroless gold plating solution Download PDFInfo
- Publication number
- WO2022124303A1 WO2022124303A1 PCT/JP2021/044917 JP2021044917W WO2022124303A1 WO 2022124303 A1 WO2022124303 A1 WO 2022124303A1 JP 2021044917 W JP2021044917 W JP 2021044917W WO 2022124303 A1 WO2022124303 A1 WO 2022124303A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- gold plating
- plating solution
- electroless gold
- electroless
- ring compound
- Prior art date
Links
- 238000007747 plating Methods 0.000 title claims abstract description 190
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 185
- 239000010931 gold Substances 0.000 title claims abstract description 185
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 176
- 150000001875 compounds Chemical class 0.000 claims abstract description 63
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 35
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 claims abstract description 31
- 125000001424 substituent group Chemical group 0.000 claims abstract description 14
- 125000004429 atom Chemical group 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000005843 halogen group Chemical group 0.000 claims abstract description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 3
- 239000002738 chelating agent Substances 0.000 claims description 22
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000872 buffer Substances 0.000 claims description 9
- 239000006172 buffering agent Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000007772 electroless plating Methods 0.000 claims description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 4
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical group OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 49
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 48
- 229910052802 copper Inorganic materials 0.000 abstract description 48
- 239000010949 copper Substances 0.000 abstract description 48
- 229910052759 nickel Inorganic materials 0.000 abstract description 24
- 239000000463 material Substances 0.000 abstract description 15
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 2
- JAJIPIAHCFBEPI-UHFFFAOYSA-N 9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O JAJIPIAHCFBEPI-UHFFFAOYSA-N 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 106
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 18
- 239000002585 base Substances 0.000 description 11
- 239000003638 chemical reducing agent Substances 0.000 description 11
- 238000010828 elution Methods 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910052763 palladium Inorganic materials 0.000 description 9
- 238000006467 substitution reaction Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 150000002343 gold Chemical class 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- -1 gold ions Chemical class 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
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- 238000009825 accumulation Methods 0.000 description 5
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- 230000000052 comparative effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- IZLAVFWQHMDDGK-UHFFFAOYSA-N gold(1+);cyanide Chemical compound [Au+].N#[C-] IZLAVFWQHMDDGK-UHFFFAOYSA-N 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
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- 238000005260 corrosion Methods 0.000 description 3
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- 239000003112 inhibitor Substances 0.000 description 3
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- 239000001508 potassium citrate Substances 0.000 description 3
- 229960002635 potassium citrate Drugs 0.000 description 3
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- 125000004434 sulfur atom Chemical group 0.000 description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical group C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 2
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- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
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- 125000003277 amino group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- JCXKHYLLVKZPKE-UHFFFAOYSA-N benzotriazol-1-amine Chemical compound C1=CC=C2N(N)N=NC2=C1 JCXKHYLLVKZPKE-UHFFFAOYSA-N 0.000 description 1
- YYZVLEJDGSWXII-UHFFFAOYSA-N benzotriazol-2-amine Chemical compound C1=CC=CC2=NN(N)N=C21 YYZVLEJDGSWXII-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 235000019258 dehydroacetic acid Nutrition 0.000 description 1
- 229940061632 dehydroacetic acid Drugs 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HUQOFZLCQISTTJ-UHFFFAOYSA-N diethylaminoboron Chemical compound CCN([B])CC HUQOFZLCQISTTJ-UHFFFAOYSA-N 0.000 description 1
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 description 1
- YPTUAQWMBNZZRN-UHFFFAOYSA-N dimethylaminoboron Chemical compound [B]N(C)C YPTUAQWMBNZZRN-UHFFFAOYSA-N 0.000 description 1
- ADPOBOOHCUVXGO-UHFFFAOYSA-H dioxido-oxo-sulfanylidene-$l^{6}-sulfane;gold(3+) Chemical compound [Au+3].[Au+3].[O-]S([O-])(=O)=S.[O-]S([O-])(=O)=S.[O-]S([O-])(=O)=S ADPOBOOHCUVXGO-UHFFFAOYSA-H 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 235000010350 erythorbic acid Nutrition 0.000 description 1
- 239000004318 erythorbic acid Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- SRCZENKQCOSNAI-UHFFFAOYSA-H gold(3+);trisulfite Chemical compound [Au+3].[Au+3].[O-]S([O-])=O.[O-]S([O-])=O.[O-]S([O-])=O SRCZENKQCOSNAI-UHFFFAOYSA-H 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 239000012493 hydrazine sulfate Substances 0.000 description 1
- 229910000377 hydrazine sulfate Inorganic materials 0.000 description 1
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940026239 isoascorbic acid Drugs 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LHVBGABHZSHVGI-UHFFFAOYSA-N methylsulfanylthiourea Chemical compound CSNC(N)=S LHVBGABHZSHVGI-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PHFFANVCGVJLOM-UHFFFAOYSA-N n-diethylboranylethanamine Chemical compound CCNB(CC)CC PHFFANVCGVJLOM-UHFFFAOYSA-N 0.000 description 1
- BORTXUKGEOWSPS-UHFFFAOYSA-N n-dimethylboranylmethanamine Chemical compound CNB(C)C BORTXUKGEOWSPS-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical group 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical group C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 1
- 235000010378 sodium ascorbate Nutrition 0.000 description 1
- 229960005055 sodium ascorbate Drugs 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- OVCXRBARSPBVMC-UHFFFAOYSA-N triazolopyridine Chemical group C=1N2C(C(C)C)=NN=C2C=CC=1C=1OC=NC=1C1=CC=C(F)C=C1 OVCXRBARSPBVMC-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
Definitions
- the present invention relates to an electroless gold plating solution. Further, the present invention comprises a composition for preparing an electrolytic gold plating solution for preparing such an electrolytic gold plating solution, a method for manufacturing an electrolytic gold plating film using the electrolytic gold plating solution, and manufacturing of electronic parts. Regarding the method.
- Patent Document 3 describes a substituted gold plating solution applicable to substitution gold plating (ENIG process) on the surface of a nickel film on a copper surface, wherein a nitrogen-containing aliphatic compound or a nitrogen-containing heterocyclic ring type is used as a gold precipitation inhibitor.
- a substituted gold plating solution to which a compound is added is described.
- the gold precipitation inhibitor in Patent Document 3 suppresses partial and excessive etching or erosion of the base metal generated when gold plating is performed by a substitution reaction with the base metal (nickel), and Patent Document 3 It is said that the gold plating film formed by the replacement gold plating solution of the above has excellent adhesion to the underlying metal.
- Patent Document 4 describes a substituted gold plating solution containing polyethylene glycol, amide sulfuric acid, and amide sulfate as a corrosion inhibitor, which can be applied to the ENEPIG process, and has a high gold precipitation rate and precipitation. It is said that the variation in the film thickness is small.
- a nickel film or a palladium film is formed on a copper material, and a substituted gold plating film is formed on them.
- the copper is not exposed on the base on which the gold plating film is formed, and the copper does not dissolve in the replacement gold plating solution.
- the exposed part of copper is slightly exposed due to the existence of unprecipitated parts of the underlying nickel film and palladium film and structural problems (poor formation of dry film, etc.). Due to its presence, copper gradually accumulates in the gold plating solution.
- Accumulation of copper in the gold plating solution may cause problems such as an increase in plating speed, a decrease in corrosion resistance due to a decrease in the coating property of the gold plating film, and a peeling of the gold film, which may hinder mass production.
- the gold plating solution has to be renewed, and the gold plating solution must be renewed frequently, resulting in high cost.
- Japanese Unexamined Patent Publication No. 2001-107259 Japanese Unexamined Patent Publication No. 2000-219973 Japanese Unexamined Patent Publication No. 2000-14441 Japanese Patent No. 6521553
- the present invention has been made in view of the above background technique, and the problem thereof is that when a gold-plated film is formed on a base such as a nickel film, elution of copper from a copper material is unlikely to occur.
- the purpose is to provide a plating solution, and also to provide a method for manufacturing an electrolytic gold plating film using the plating solution and a method for manufacturing electronic parts.
- the present inventor has added a condensed ring compound having a nitrogen atom in the ring to the electroless gold plating solution to elute copper from the copper material. We have found that it is extremely unlikely to occur, and have completed the present invention.
- the present invention provides an electroless gold plating solution characterized by containing a water-soluble gold salt and a condensed ring compound having a nitrogen atom in the ring.
- the present invention is a composition for preparing an electroless gold plating solution for preparing an electroless gold plating solution by adding water and a water-soluble gold salt, and contains the above-mentioned fused ring compound. It provides a composition for preparing a characteristic electroless gold plating solution.
- the present invention also provides a method for producing an electroless gold plating film, which comprises producing an electroless gold plating film using the above-mentioned electroless gold plating solution.
- the present invention is a method for manufacturing an electronic component, wherein the electronic component has an electroless gold plating film manufactured by the above-mentioned method for manufacturing an electroless gold plating film. It provides a method.
- the present invention also provides a method for manufacturing an electronic component, which comprises a step of forming an electroless gold plating film by using the above-mentioned electroless gold plating solution. It is something to do.
- an electroless gold plating solution in which copper is less likely to elute from a copper material when a gold plating film is formed on a base such as a nickel film.
- the electroless gold plating solution of the present invention In the electroless gold plating solution of the present invention, elution of copper from the copper material is unlikely to occur, and copper is unlikely to accumulate in the plating solution. Therefore, the above-mentioned problem due to the accumulation of copper is less likely to occur, and the frequency of updating the plating solution can be reduced (the life of the plating solution can be extended).
- the electroless gold plating solution of the present invention at the time of mass production, the cost of the expensive gold plating solution can be suppressed and the productivity can be improved.
- the electroless gold plating solution of the present invention contains a water-soluble gold salt and a condensed ring compound having a nitrogen atom in the ring.
- the water-soluble gold salt is a gold source for the electroless gold plating solution of the present invention, is sufficiently stable in the plating solution, is easily dissolved in water, and is suitable as a gold source for the plating solution. If so, there is no particular limitation. Specific examples thereof include gold cyanide, gold chloride, gold sulfite, and gold thiosulfate. A gold cyanide salt (gold cyanide (I) salt, gold cyanide (III) salt) is preferable, and a gold cyanide (I) salt is particularly preferable.
- the anti-cations forming the above salt are not particularly limited, and examples thereof include alkali metal ions and ammonium ions.
- alkali metal ion examples include potassium ion, sodium ion, lithium ion and the like.
- water-soluble gold salts potassium gold (I) cyanide is most preferable from the viewpoint of plating speed, stability and the like.
- the water-soluble gold salt may be used alone or in combination of two or more.
- the concentration of the water-soluble gold salt in the electroless gold plating solution is not particularly limited, but is preferably 0.1 g / L or more in terms of gold. It is more preferably 0.3 g / L or more, and particularly preferably 0.5 g / L or more. Further, it is preferably 5 g / L or less, more preferably 4 g / L or less, and particularly preferably 3 g / L or less.
- concentration of the water-soluble gold salt is at least the above lower limit, the plating rate can be sufficiently increased.
- the concentration of the water-soluble gold salt is not more than the above upper limit, the stability of the plating solution is likely to be maintained.
- a fused ring compound having a nitrogen atom in the ring is a condensed ring compound (a compound in which two or more rings share and bond two or more atoms) and has a nitrogen atom in the ring (that is, constitutes a ring).
- a condensed ring compound a compound in which two or more rings share and bond two or more atoms
- has a nitrogen atom in the ring that is, constitutes a ring.
- the "condensed ring compound having a nitrogen atom in the ring” may be referred to as a "specific condensed ring compound”.
- the specific fused ring compound in the electroless gold plating solution, even if there is an exposed part of the copper material when performing the electroless gold plating, the elution of copper into the electroless gold plating solution is suppressed. be able to. It is presumed that this is because the specific condensed ring compound has strong hydrophobicity and strongly forms a protective layer for copper elution protection on the copper surface.
- Examples of the specific condensed ring compound include a condensed ring compound in which a benzene ring or a pyridine ring and a complex five-membered ring having a nitrogen atom are condensed.
- the specific condensed ring compound has two or more atoms that are not carbon atoms in the ring. Since the specific fused ring compound has at least one nitrogen atom in the ring, in other words, the specific fused ring compound has two or more nitrogen atoms in the ring, or the nitrogen atom and carbon. However, it is preferable to have an atom that is neither nitrogen nor nitrogen. Examples of atoms that are neither carbon nor nitrogen include sulfur atoms, oxygen atoms, phosphorus atoms and the like.
- the specific fused ring compound has a complex five-membered ring having a nitrogen atom, and it is desirable that the complex five-membered ring has two or more atoms that are not carbon atoms.
- the complex five-membered ring has two nitrogen atoms, three nitrogen atoms, one nitrogen atom and one sulfur atom, one nitrogen atom and oxygen. Examples include the case of having one atom, the case of having two nitrogen atoms and one sulfur atom, the case of having two nitrogen atoms and one oxygen atom, and the like.
- the specific fused ring compound has at least one nitrogen atom in the molecule, but may have two nitrogen atoms in the molecule, and has three nitrogen atoms in the molecule. It may have 4 nitrogen atoms in the molecule, and may have 5 or more nitrogen atoms in the molecule.
- the specific fused ring compound may have a substituent containing nitrogen such as an amino group, an alkylamino group and a nitro group.
- nitrogen atom contained in the molecule is not limited to the nitrogen atom contained in the ring, and the nitrogen atom contained in these substituents also corresponds to the "nitrogen atom contained in the molecule”.
- the structure of the specific fused ring compound include indole skeleton, isoindole skeleton, benzoimidazole skeleton, indazole skeleton, purine skeleton, benzothiazole skeleton, benzothiasiazole skeleton, benzotriazole skeleton, quinoline skeleton, isoquinoline skeleton, and quinoxalin.
- Examples thereof include compounds having a structure (basic skeleton) such as a skeleton, a quinazoline skeleton, a synnoline skeleton, a phthalazine skeleton, a pyrazolopyridine skeleton, and a triazolopyridine skeleton.
- the specific condensed ring compound having the above structure may or may not have a substituent.
- substituents include an alkyl group having 1 to 6 carbon atoms, a mercapto group, a hydroxy group, a carboxy group, a nitro group, a halogen group and the like.
- alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group and the like.
- halogen group include a fluorine group, a chlorine group, a bromine group, an iodine group and the like.
- the substituent may be bonded to the benzene ring or the pyridine ring. However, it may be bonded to a complex five-membered ring having a nitrogen atom.
- a plurality of substituents may be bonded to each of a benzene ring, a pyridine ring, and a complex five-membered ring having a nitrogen atom.
- the number of the above-mentioned substituents contained in the specific condensed ring compound may be one, two, three, or four or more. When it has a plurality of substituents, it may have the same substituent at a plurality of locations, or it may have different types of substituents.
- Specific compound names of the specific fused ring compound include benzimidazole, 1-methylbenzimidazole, 2-methylbenzomidazole, 2-mercaptobenzimidazole, 2-amino-benzomidazole, 1,2,3-benzotriazole, and the like.
- 5-Methyl-1H-benzotriazole, 1-methyl-1H-benzotriazole, carboxybenzotriazole, hydroshikibenzotriazole, carboxyhydroxybenzotriazole, nitrobenzotriazole, 1-amino-benzotriazole, 2-aminobenzotriazole, 1H -1,2,3-triazolopyridine, 3-aminoquinoline, 5-aminoindole, etc. may be mentioned.
- the specific condensed ring compound may be used alone or in combination of two or more.
- the concentration of the specific condensed ring compound in the electroless gold plating solution is not particularly limited, but is preferably 0.1 ppm or more, more preferably 0.5 ppm. As mentioned above, it is particularly preferably 2 ppm or more. Further, it is preferably 1000 ppm or less, more preferably 500 ppm or less, and particularly preferably 100 ppm or less.
- concentration of the specific fused ring compound is at least the above lower limit, the effect of copper elution is likely to be sufficiently exerted.
- the concentration of the specific condensed ring compound is not more than the above upper limit, the cost can be suppressed and the precipitation of the component exceeding the solubility can be prevented.
- the electroless gold plating solution of the present invention may further contain a chelating agent.
- the chelating agent has the effect of preventing the precipitation of metals such as nickel, copper, palladium, iron, chromium, lead, and cobalt that accumulate in the plating tank as the electroless gold plating solution is operated, and stably dissolving the metal. be.
- the chelating agent is not particularly limited as long as it is coordinated with a metal such as nickel, copper, palladium, iron, chromium, lead, and cobalt and stably dissolved in water, but for nickel, copper, palladium, and the like. Those having good chelating properties are preferable.
- Particularly preferable chelating agents include a chelating agent having an iminodiacetic acid structure in the molecule and a chelating agent having a methylenephosphonic acid structure. These chelating agents have good chelating properties for nickel, copper, palladium and the like.
- Examples of the chelating agent having an imino2 acetic acid structure in the molecule include ethylenediaminetetraacetic acid, nitrilo3acetic acid, hydroxyethylethylenediamine3acetic acid, diethylenetriamine5acetic acid, triethylenetetramine6acetic acid, dicarboxymethylglutamic acid, propanediamine4acetic acid, 1, Examples thereof include carboxylic acids such as 3-diamino-2-hydroxylpropane-4acetic acid and salts thereof.
- Examples of the chelating agent having a methylenephosphonic acid structure include phosphonic acids such as aminotrimethylenephosphonic acid, hydroxyethylidene diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, and hexamethylenediaminetetramethylenephosphonic acid, and these.
- phosphonic acids such as aminotrimethylenephosphonic acid, hydroxyethylidene diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, and hexamethylenediaminetetramethylenephosphonic acid, and these.
- An example is salt.
- ethylenediaminetetraacetic acid, nitrilotriacetic acid, aminotrimethylenephosphonic acid, and ethylenediaminetetramethylenephosphonic acid are particularly preferable from the viewpoint of chelating characteristics and cost.
- the chelating agent may be used alone or in combination of two or more.
- the concentration of the chelating agent in the electroless gold plating solution is not particularly limited, but is preferably 0.5 g / L or more, more preferably 1 g / L or more. Particularly preferably, it is 2 g / L or more. Further, it is preferably 30 g / L or less, more preferably 20 g / L or less, and particularly preferably 10 g / L or less.
- concentration of the chelating agent is at least the above lower limit, a sufficient chelating effect is exhibited, and it is easy to prevent abnormal precipitation of metal accumulated in the plating tank.
- concentration of the chelating agent is not more than the above upper limit, it is advantageous in terms of cost, and it is possible to prevent the components exceeding the solubility from precipitating.
- the electroless gold plating solution of the present invention may further contain a buffer.
- the buffer has an action of stabilizing the pH of the electroless gold plating solution. If there is such an action, the type of the buffer is not particularly limited, and an acid, a base or a salt may be appropriately blended and used regardless of whether it is an organic compound or an inorganic compound.
- the buffering agent include adipic acid, benzoic acid, citric acid, malic acid, succinic acid, formic acid, acetic acid, lactic acid, malonic acid, phthalic acid, oxalic acid, tartrate acid, glycine, glutamic acid, glutaric acid and imino2acetic acid.
- Dehydroacetic acid maleic acid, fumaric acid and other carboxylic acids and salts thereof; amine compounds such as ethylenediamine, hydroxyamine, ethanolamine, diethanolamine, triethanolamine and their salts; boric acid, phosphoric acid, pyrophosphate, sub Examples thereof include inorganic acids such as phosphoric acid, thiosulfate, sulfite, nitric acid, sulfuric acid, hydrochloric acid and thiosicic acid, and salts thereof.
- Preferred buffering agents include acids containing atoms having an intermediate oxidation number or salts thereof. Further, a compound having a potential intermediate between the oxidizing agent and the reducing agent can be mentioned.
- Particularly preferable buffering agents include phosphorous acid and its salts, sulfurous acid and its salts, and the like.
- salts of phosphoric acid and sulfite include lithium salt, sodium salt, potassium salt, magnesium salt, calcium salt, barium salt, ammonium salt and the like.
- the most preferable buffering agent includes sodium sulfite, potassium sulfite, sodium sulfite and the like because it is difficult to form an insoluble salt in the plating solution.
- the buffer may be used alone or in combination of two or more.
- the concentration of the buffer in the electroless gold plating solution is not particularly limited, but is preferably 1 g / L or more, more preferably 2 g / L or more, and particularly preferably. Is 3 g / L or more. Further, it is preferably 300 g / L or less, more preferably 200 g / L or less, and particularly preferably 100 g / L or less.
- concentration of the buffering agent is at least the above lower limit, a sufficient buffering effect is likely to be exhibited.
- the concentration of the buffering agent is not more than the above upper limit, it is advantageous in terms of cost, and it is possible to prevent the components exceeding the solubility from precipitating.
- the pH of the electroless gold plating solution of the present invention is kept stable mainly by the above buffer, but the preferable range of pH is preferably 4 or more, more preferably 4.5 or more, and particularly preferably 5 or more. Is. Further, it is preferably 8 or less, more preferably 7.5 or less, and particularly preferably 7 or less.
- the pH is at least the above lower limit, the water-soluble gold salt can stably exist in the liquid.
- the resist on the substrate is less likely to be eroded.
- the electroless gold plating solution of the present invention may be a substitution type electroless gold plating solution, a reduction type electroless gold plating solution, or a substitution reduction type electroless gold plating solution.
- the reducing agents contained in the electroless gold plating solution of the present invention include ascorbic acid, erythorbic acid, glyoxylic acid, formic acid and thioglycolic acid.
- thiourea 1-allyl-2-thiourea, 1-allyl-3- (2-Hydroxyethyl) -2-thiourea, 1,3-diethyl-2-thiourea, trimethylthiourea, 1,3-dimethylthiourea, 1-acetylthiourea, N-allylthiourea, ethylenethiourea, N-methylthio Thiourea such as urea; hydrazine derivatives such as thiosemicarbazide, hydrazine, p-hydrazinobenzenesulfonic acid, isonicotinic acid hydrazide, hydrazine sulfate; dimethylaminoborane, trimethylaminoborane, sodium hydride, potassium hydride , Borone compounds such as
- ascorbic acid Ascorbic acid, salts thereof, and thioureas are particularly preferable from the viewpoint of the stability of the plating solution.
- the reducing agent may be used alone or in combination of two or more.
- the concentration of the reducing agent in the electroless gold plating solution is not particularly limited, but is preferably 0.01 g / L or more, more preferably 0.05 g / L.
- the above is particularly preferably 0.2 g / L or more. Further, it is preferably 50 g / L or less, more preferably 20 g / L or less, and particularly preferably 5 g / L or less.
- the concentration of the reducing agent is at least the above lower limit, stable plating precipitateability can be obtained.
- the concentration of the reducing agent is not more than the above upper limit, it is advantageous in terms of cost and the stability of the plating solution is excellent.
- the electroless gold plating solution of the present invention may further contain a metal ion sequestering agent, a surfactant, a crystal adjusting agent and the like.
- the sequestrant has an action of removing the influence of impurity metals mixed in the electroless gold plating solution.
- the surfactant has an action of controlling the wetting characteristics of the electroless gold plating solution.
- the crystal modifier has an action of controlling the crystal structure of the deposited electroless gold plating film.
- composition for preparing electroless gold plating solution is a composition for preparing an electroless gold plating solution for preparing an electroless gold plating solution by adding water and a water-soluble gold salt, and is characterized by containing the above-mentioned specific condensed ring compound. It also relates to a composition for preparing a non-electrolytic gold plating solution.
- the water-soluble gold salt which is an essential component of the electroless gold plating solution of the present invention, is very expensive and is usually traded at the market price. In addition, it may be uneconomical to store the water-soluble gold salt in the state of being contained in the aqueous solution, and if the water-soluble gold salt is stored in the form of an aqueous solution, various performances as a plating solution deteriorate. May be done. For this reason, the water-soluble gold salt should be stored separately in a state where it is not dissolved in water, and when using the electroless gold plating solution, other components (all components contained in the electroless gold plating solution) should be used. It is preferable to add a water-soluble gold salt to the aqueous solution containing the mixture (which may be present or may be a part of the components).
- composition for preparing an electroless gold plating solution of the present invention contains the above-mentioned specific condensed ring compound, and if necessary, the above-mentioned chelating agent, buffer, metal ion sequestering agent, surfactant, crystal modifier, etc. It may contain a reducing agent.
- the form of the composition for preparing an electroless gold plating solution of the present invention is not limited, and may be in the form of powder or in the form of an aqueous solution.
- the concentration of the specific condensed ring compound is higher than the concentration of the specific condensed ring compound in the above-mentioned electroless gold plating solution, and water is further added when the specific condensed ring compound is used as the electroless gold plating solution (specific condensed ring).
- the concentration of the compound may be diluted).
- the electroless gold plating solution of the present invention is prepared by separately adding a water-soluble gold salt to the composition for preparing an electroless gold plating solution of the present invention, or by separately adding a water-soluble gold salt and water. can do.
- the composition for preparing an electroless gold plating solution of the present invention includes all or all of the other components of the electroless gold plating solution (chelating agent, buffering agent, metal ion sequestering agent, surfactant, crystal modifier, reducing agent, etc.). It may not include a part. In other words, these components may be separately added to the composition for preparing the electroless gold plating solution when preparing the electroless gold plating solution, like the water-soluble gold salt and water.
- the present invention also relates to a method for producing an electroless plating film using the above-mentioned electroless gold plating solution to produce an electroless gold plating film.
- the process to which the method for producing an electroless plating film of the present invention is applied is not particularly limited, and for example, a process of forming an electroless gold plating film on an electroless nickel film formed on a copper material (a process of forming an electroless gold plating film on an electroless nickel film formed on a copper material).
- ENIG a process of forming an electroless palladium film on an electroless nickel film formed on a copper material and further forming an electroless gold plating film on it (ENEPIG), formed on a copper material. It can be applied to a process (ENEAG) of forming a substituted gold plating film on an electroless nickel plating film and further forming a reduced gold plating on the substituted gold plating film.
- the method for producing an electroless gold plating film of the present invention even if an unprecipitated portion such as a nickel film or an exposed portion of copper due to poor formation of a dry film is slightly present, the exposed portion can be used. Elution of copper can be suppressed. Therefore, in the method for producing the electroless gold plating film of the present invention, problems caused by the accumulation of copper in the electroless gold plating solution are less likely to occur, and the frequency of updating the electroless gold plating solution can be reduced. Production efficiency increases.
- the thickness of the electroless gold plating film is particularly limited. However, it is preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, and particularly preferably 0.02 ⁇ m or more. Further, it is preferably 1 ⁇ m or less, more preferably 0.7 ⁇ m or less, and particularly preferably 0.5 ⁇ m or less. When it is at least the above lower limit, the performance as a film can be sufficiently exhibited. Further, if it is not more than the above upper limit, it is advantageous in terms of cost.
- film is not limited to a film that is uniformly flat, and a film that has pores or granular parts is also called a “film”.
- Film is synonymous with "layer”.
- the temperature of the electroless gold plating solution when forming the electroless gold plating film is preferably 10 ° C. or higher, more preferably 15 ° C. or higher, and more preferably 20 ° C. The above is particularly preferable. Further, it is preferably 100 ° C. or lower, more preferably 95 ° C. or lower, and particularly preferably 90 ° C. or lower. Further, depending on the method for producing the electrolytic gold plating film, the time (plating time) for forming the electrolytic gold plating film is preferably 0.5 minutes or more, more preferably 1 minute or more, and 2 It is particularly preferable that it is at least a minute.
- the film thickness is likely to be within the above ranges.
- the present invention is a method for manufacturing an electronic component, wherein the electronic component has an electroless gold plating film manufactured by the above-mentioned method for manufacturing an electroless gold plating film. Also related.
- the present invention also relates to a method for manufacturing an electronic component, which comprises a step of forming an electroless gold plating film by using the above-mentioned electroless gold plating solution.
- Examples 19-20 The condensed ring compound having a nitrogen atom shown in Table 1 was dissolved in the base liquid B in which each component was dissolved in ion-exchanged water at the concentration shown below so as to be 10 ppm with respect to the entire electroless plating solution, and the pH was 6.5.
- the electroless gold plating solution of Examples 19 to 20 was prepared. When adjusting the pH, an aqueous solution of sodium hydroxide was used to raise the pH, and sulfuric acid was used to lower the pH.
- Examples 21-22 The condensed ring compound having a nitrogen atom shown in Table 1 was dissolved in the base liquid C in which each component was dissolved in ion-exchanged water at the concentration shown below so as to be 10 ppm with respect to the entire electroless plating solution, and the pH was 6.5.
- the electroless gold plating solution of Examples 21 to 22 was prepared. When adjusting the pH, an aqueous solution of sodium hydroxide was used to raise the pH, and sulfuric acid was used to lower the pH.
- the electroless gold plating solution using the base liquid C is a reduction type electroless plating solution.
- a substrate 40 mm ⁇ 40 mm ⁇ 1 mmt in which a copper foil is attached to a glass cloth epoxy material (FR-4) and an opening having a diameter of 0.5 mm is provided with a solder resist is used as a plated body, and plating is laminated in the process of Table 3.
- the body was made.
- electroless gold plating the electroless gold plating solution prepared in each example was used.
- the electroless gold plating solution of the present invention containing the specific fused ring compound was able to form a high-quality gold plating layer with almost no elution of copper.
- the electroless gold plating solution of the present invention contains a specific condensed ring compound, it is difficult for copper to elute from the copper material when forming a gold plating film on a base such as a nickel film. It is widely used to form a gold-plated film for connection terminals of electronic parts.
Abstract
[Problem] To provide: an electroless gold plating solution which is not susceptible to dissolution of copper from a copper material in cases where a gold plating film is formed on a base material such as a nickel film; and a method for producing an electroless gold plating film and a method for producing an electronic component, each of said methods using this electroless gold plating solution. [Solution] The above-described problem has been solved by an electroless gold plating solution which is characterized by containing a water-soluble gold salt and a fused ring compound that has a nitrogen atom in a ring. Examples of the fused ring compound may include a fused ring compound that has two or more atoms other than carbon atoms in a ring, and a fused ring compound wherein a benzene ring or a pyridine ring is fused with a five-membered heterocyclic ring that has a nitrogen atom. The fused ring compound may have a substituent such as an alkyl group having from 1 to 6 carbon atoms, a mercapto group, a hydroxy group, a carboxy group, a nitro group and a halogen group.
Description
本発明は、無電解金めっき液に関する。また、本発明は、かかる無電解金めっき液を調製するための無電解金めっき液調製用組成物や、かかる無電解金めっき液を使用した無電解金めっき皮膜の製造方法や電子部品の製造方法に関する。
The present invention relates to an electroless gold plating solution. Further, the present invention comprises a composition for preparing an electrolytic gold plating solution for preparing such an electrolytic gold plating solution, a method for manufacturing an electrolytic gold plating film using the electrolytic gold plating solution, and manufacturing of electronic parts. Regarding the method.
プリント基板等の電子部品の接続端子部等に使用されるめっきにおいて、端子部の腐食を防止し、ワイヤ接合、はんだ接合等を行うためのプロセスとして、銅素材上の無電解ニッケルめっき皮膜上に、金皮膜を積層させる方法として、無電解ニッケルめっき皮膜上に置換金めっきを施すプロセス（ＥＮＩＧ；Electroless Nickel Immersion Gold）、無電解ニッケルめっき皮膜上に無電解パラジウム皮膜を介して置換金めっきを施すプロセス（ＥＮＥＰＩＧ；Electroless Nickel Electroless Palladium Immersion Gold）、無電解ニッケルめっき皮膜上に置換金めっきを施し、更に、その上に還元金めっきを施して金の膜厚を上げるプロセス（ＥＮＥＡＧ；Electroless Nickel Electroless Autocatalytic Gold）等が使用されている。
In plating used for connection terminals of electronic parts such as printed boards, as a process for preventing corrosion of the terminals and performing wire bonding, solder bonding, etc., on the electroless nickel plating film on the copper material. , As a method of laminating a gold film, a process of performing substitution gold plating on an electroless nickel plating film (ENIG; Electroless Nickel Immersion Gold), and applying substitution gold plating on an electroless nickel plating film via an electroless palladium film. Process (ENEPIG; Electroless Nickel Electroless Palladium Immersion Gold), a process of applying substitution gold plating on an electroless nickel plating film and then applying reduction gold plating on it to increase the film thickness of gold (ENEAG; Electroless Nickel Electroless Autocatalytic). Gold) etc. are used.
上記各プロセスに使用される置換金めっきは、下地の金属がイオンとなって金めっき液中に溶出する際に放出される電子が金イオンに与えられ、金イオンが金となって下地金属表面に析出し金皮膜を形成するものである。
置換金めっきは、金イオンが下地金属と置換して金が析出するため、下地金属の表面が金で覆われるとそれ以上反応は進行せず、金皮膜の厚膜化は困難である。このため、置換型無電解金めっき液に還元剤を添加し、金めっき液中で金の還元反応を行わせて金めっき皮膜を形成させ、置換反応による金皮膜形成の割合を少なくする方法（置換還元型金めっき）が知られている（例えば、特許文献１、特許文献２）。 In the replacement gold plating used in each of the above processes, the electrons emitted when the underlying metal becomes ions and elutes into the gold plating solution are given to the gold ions, and the gold ions become gold and become the surface of the underlying metal. It precipitates in and forms a gold film.
In the replacement gold plating, gold ions are replaced with the base metal and gold is deposited. Therefore, when the surface of the base metal is covered with gold, the reaction does not proceed any further and it is difficult to thicken the gold film. For this reason, a method of adding a reducing agent to a replacement type electroless gold plating solution to form a gold plating film by performing a gold reduction reaction in the gold plating solution to reduce the rate of gold film formation due to the substitution reaction (a method). Substitution reduction type gold plating) is known (for example, Patent Document 1 and Patent Document 2).
置換金めっきは、金イオンが下地金属と置換して金が析出するため、下地金属の表面が金で覆われるとそれ以上反応は進行せず、金皮膜の厚膜化は困難である。このため、置換型無電解金めっき液に還元剤を添加し、金めっき液中で金の還元反応を行わせて金めっき皮膜を形成させ、置換反応による金皮膜形成の割合を少なくする方法（置換還元型金めっき）が知られている（例えば、特許文献１、特許文献２）。 In the replacement gold plating used in each of the above processes, the electrons emitted when the underlying metal becomes ions and elutes into the gold plating solution are given to the gold ions, and the gold ions become gold and become the surface of the underlying metal. It precipitates in and forms a gold film.
In the replacement gold plating, gold ions are replaced with the base metal and gold is deposited. Therefore, when the surface of the base metal is covered with gold, the reaction does not proceed any further and it is difficult to thicken the gold film. For this reason, a method of adding a reducing agent to a replacement type electroless gold plating solution to form a gold plating film by performing a gold reduction reaction in the gold plating solution to reduce the rate of gold film formation due to the substitution reaction (a method). Substitution reduction type gold plating) is known (for example, Patent Document 1 and Patent Document 2).
ワイヤ接合、はんだ接合の接合強度を良好なものとするためには、金皮膜と、下地金属との密着性を良好とする必要がある。このような観点から、金めっき液に関して、様々な改良がなされている。
In order to improve the bonding strength of wire bonding and solder bonding, it is necessary to improve the adhesion between the gold film and the base metal. From this point of view, various improvements have been made to the gold plating solution.
特許文献３には、銅表面のニッケル皮膜表面への置換金めっき（ＥＮＩＧプロセス）に適用可能な置換金めっき液であって、金析出抑制剤として、窒素含有脂肪族化合物や窒素含有複素環式化合物を添加した置換金めっき液が記載されている。特許文献３における金析出抑制剤は、下地金属（ニッケル）との置換反応によって金めっきを行なう際に生じる下地金属の部分的かつ過剰なエッチング又は浸食を抑制する、というものであり、特許文献３の置換金めっき液により製膜した金めっき皮膜は、下地金属との密着性に優れる、とされている。
Patent Document 3 describes a substituted gold plating solution applicable to substitution gold plating (ENIG process) on the surface of a nickel film on a copper surface, wherein a nitrogen-containing aliphatic compound or a nitrogen-containing heterocyclic ring type is used as a gold precipitation inhibitor. A substituted gold plating solution to which a compound is added is described. The gold precipitation inhibitor in Patent Document 3 suppresses partial and excessive etching or erosion of the base metal generated when gold plating is performed by a substitution reaction with the base metal (nickel), and Patent Document 3 It is said that the gold plating film formed by the replacement gold plating solution of the above has excellent adhesion to the underlying metal.
特許文献４には、腐食抑制剤として、ポリエチレングリコール、アミド硫酸、アミド硫酸塩を含有する、ＥＮＥＰＩＧプロセスに適用可能な置換金めっき液が記載されており、金の析出速度が速く、かつ、析出皮膜の膜厚のばらつきが小さい、とされている。
Patent Document 4 describes a substituted gold plating solution containing polyethylene glycol, amide sulfuric acid, and amide sulfate as a corrosion inhibitor, which can be applied to the ENEPIG process, and has a high gold precipitation rate and precipitation. It is said that the variation in the film thickness is small.
ＥＮＩＧ、ＥＮＥＰＩＧ、ＥＮＥＡＧ等のプロセスにおいては、銅素材上の上に、ニッケル皮膜やパラジウム皮膜を形成し、それらの上に置換金めっき皮膜を形成する。理想状態であれば、金めっき皮膜を製膜する下地には銅の露出はなく、置換金めっき液に銅が溶解する事はない。
しかし、実際のプリント基板等の量産時には、下地のニッケル皮膜、パラジウム皮膜の未析出部分の存在や、構造上の問題（ドライフィルムの形成不良等）に起因して、銅の露出部がわずかながら存在する為、徐々に金めっき液中に銅が蓄積する。
金めっき液中に銅が蓄積することにより、めっき速度の上昇、金めっき皮膜の被覆性低下による耐食性低下、金皮膜の剥離等の問題が発生し量産に支障をきたす場合がある。このような場合、金めっき液を更新せざるを得なくなり、頻繁に金めっき液を更新しなければならなくなることで、コスト高となる。 In processes such as ENIG, ENEPIG, and ENEAG, a nickel film or a palladium film is formed on a copper material, and a substituted gold plating film is formed on them. In the ideal state, the copper is not exposed on the base on which the gold plating film is formed, and the copper does not dissolve in the replacement gold plating solution.
However, at the time of mass production of actual printed circuit boards, the exposed part of copper is slightly exposed due to the existence of unprecipitated parts of the underlying nickel film and palladium film and structural problems (poor formation of dry film, etc.). Due to its presence, copper gradually accumulates in the gold plating solution.
Accumulation of copper in the gold plating solution may cause problems such as an increase in plating speed, a decrease in corrosion resistance due to a decrease in the coating property of the gold plating film, and a peeling of the gold film, which may hinder mass production. In such a case, the gold plating solution has to be renewed, and the gold plating solution must be renewed frequently, resulting in high cost.
しかし、実際のプリント基板等の量産時には、下地のニッケル皮膜、パラジウム皮膜の未析出部分の存在や、構造上の問題（ドライフィルムの形成不良等）に起因して、銅の露出部がわずかながら存在する為、徐々に金めっき液中に銅が蓄積する。
金めっき液中に銅が蓄積することにより、めっき速度の上昇、金めっき皮膜の被覆性低下による耐食性低下、金皮膜の剥離等の問題が発生し量産に支障をきたす場合がある。このような場合、金めっき液を更新せざるを得なくなり、頻繁に金めっき液を更新しなければならなくなることで、コスト高となる。 In processes such as ENIG, ENEPIG, and ENEAG, a nickel film or a palladium film is formed on a copper material, and a substituted gold plating film is formed on them. In the ideal state, the copper is not exposed on the base on which the gold plating film is formed, and the copper does not dissolve in the replacement gold plating solution.
However, at the time of mass production of actual printed circuit boards, the exposed part of copper is slightly exposed due to the existence of unprecipitated parts of the underlying nickel film and palladium film and structural problems (poor formation of dry film, etc.). Due to its presence, copper gradually accumulates in the gold plating solution.
Accumulation of copper in the gold plating solution may cause problems such as an increase in plating speed, a decrease in corrosion resistance due to a decrease in the coating property of the gold plating film, and a peeling of the gold film, which may hinder mass production. In such a case, the gold plating solution has to be renewed, and the gold plating solution must be renewed frequently, resulting in high cost.
プリント基板等の複雑化、高密度化に伴い、銅の蓄積は発生しやすくなる傾向にあり、このため、銅の蓄積を抑制することのできる技術の開発が望まれている。
With the increasing complexity and density of printed circuit boards, copper accumulation tends to occur, and for this reason, the development of techniques that can suppress copper accumulation is desired.
本発明は上記背景技術に鑑みてなされたものであり、その課題は、ニッケル皮膜等の下地に対して金めっき皮膜を形成する際に、銅素材からの銅の溶出が発生しにくい無電解金めっき液を提供することにあり、またそれを用いた無電解金めっき皮膜の製造方法や電子部品の製造方法を提供することにある。
The present invention has been made in view of the above background technique, and the problem thereof is that when a gold-plated film is formed on a base such as a nickel film, elution of copper from a copper material is unlikely to occur. The purpose is to provide a plating solution, and also to provide a method for manufacturing an electrolytic gold plating film using the plating solution and a method for manufacturing electronic parts.
本発明者は、上記の課題を解決すべく鋭意検討を重ねた結果、無電解金めっき液に、環中に窒素原子を有する縮合環化合物を添加することによって、銅素材からの銅の溶出が極めて発生しにくくなることを見出して、本発明を完成するに至った。
As a result of diligent studies to solve the above problems, the present inventor has added a condensed ring compound having a nitrogen atom in the ring to the electroless gold plating solution to elute copper from the copper material. We have found that it is extremely unlikely to occur, and have completed the present invention.
すなわち、本発明は、水溶性金塩と、環中に窒素原子を有する縮合環化合物とを含有することを特徴とする無電解金めっき液を提供するものである。
That is, the present invention provides an electroless gold plating solution characterized by containing a water-soluble gold salt and a condensed ring compound having a nitrogen atom in the ring.
また、本発明は、水と水溶性金塩を添加することによって無電解金めっき液を調製するための無電解金めっき液調製用組成物であって、前記の縮合環化合物を含有することを特徴とする無電解金めっき液調製用組成物を提供するものである。
Further, the present invention is a composition for preparing an electroless gold plating solution for preparing an electroless gold plating solution by adding water and a water-soluble gold salt, and contains the above-mentioned fused ring compound. It provides a composition for preparing a characteristic electroless gold plating solution.
また、本発明は、前記の無電解金めっき液を使用して、無電解金めっき皮膜を製造することを特徴とする無電解金めっき皮膜の製造方法を提供するものである。
The present invention also provides a method for producing an electroless gold plating film, which comprises producing an electroless gold plating film using the above-mentioned electroless gold plating solution.
また、本発明は、電子部品の製造方法であって、該電子部品が、前記の無電解金めっき皮膜の製造方法により製造された無電解金めっき皮膜を有することを特徴とする電子部品の製造方法を提供するものである。
Further, the present invention is a method for manufacturing an electronic component, wherein the electronic component has an electroless gold plating film manufactured by the above-mentioned method for manufacturing an electroless gold plating film. It provides a method.
また、本発明は、電子部品の製造方法であって、前記の無電解金めっき液を使用して、無電解金めっき皮膜を形成させる工程を有することを特徴とする電子部品の製造方法を提供するものである。
The present invention also provides a method for manufacturing an electronic component, which comprises a step of forming an electroless gold plating film by using the above-mentioned electroless gold plating solution. It is something to do.
本発明によれば、ニッケル皮膜等の下地に対して金めっき皮膜を形成する際に、銅素材からの銅の溶出が発生しにくい無電解金めっき液を提供することができる。
According to the present invention, it is possible to provide an electroless gold plating solution in which copper is less likely to elute from a copper material when a gold plating film is formed on a base such as a nickel film.
本発明の無電解金めっき液は、銅素材からの銅の溶出が発生しにくく、めっき液中に銅が蓄積しにくい。このため、前記した銅の蓄積による問題が発生しにくく、めっき液の更新の頻度を少なくする（めっき液の寿命を長くする）ことができる。
量産の際に本発明の無電解金めっき液を使用することにより、高価な金めっき液のコストを抑制でき、また、生産性を向上させることができる。 In the electroless gold plating solution of the present invention, elution of copper from the copper material is unlikely to occur, and copper is unlikely to accumulate in the plating solution. Therefore, the above-mentioned problem due to the accumulation of copper is less likely to occur, and the frequency of updating the plating solution can be reduced (the life of the plating solution can be extended).
By using the electroless gold plating solution of the present invention at the time of mass production, the cost of the expensive gold plating solution can be suppressed and the productivity can be improved.
量産の際に本発明の無電解金めっき液を使用することにより、高価な金めっき液のコストを抑制でき、また、生産性を向上させることができる。 In the electroless gold plating solution of the present invention, elution of copper from the copper material is unlikely to occur, and copper is unlikely to accumulate in the plating solution. Therefore, the above-mentioned problem due to the accumulation of copper is less likely to occur, and the frequency of updating the plating solution can be reduced (the life of the plating solution can be extended).
By using the electroless gold plating solution of the present invention at the time of mass production, the cost of the expensive gold plating solution can be suppressed and the productivity can be improved.
以下、本発明について説明するが、本発明は以下の実施の形態に限定されるものではなく、任意に変形して実施することができる。
Hereinafter, the present invention will be described, but the present invention is not limited to the following embodiments, and can be arbitrarily modified and carried out.
［無電解金めっき液］
本発明の無電解金めっき液は、水溶性金塩と、環中に窒素原子を有する縮合環化合物とを含有する。 [Electroless gold plating solution]
The electroless gold plating solution of the present invention contains a water-soluble gold salt and a condensed ring compound having a nitrogen atom in the ring.
本発明の無電解金めっき液は、水溶性金塩と、環中に窒素原子を有する縮合環化合物とを含有する。 [Electroless gold plating solution]
The electroless gold plating solution of the present invention contains a water-soluble gold salt and a condensed ring compound having a nitrogen atom in the ring.
水溶性金塩は、本発明の無電解金めっき液の金源となるものであり、めっき液中で十分安定であり、水に溶解しやすいものであり、めっき液の金源として適したものであれば特に限定はない。
具体的には、シアン化金塩、塩化金塩、亜硫酸金塩、チオ硫酸金塩等が挙げられる。好ましくは、シアン化金塩（シアン化金（Ｉ）塩、シアン化金（III）塩）であり、特に好ましくは、シアン化金（Ｉ）塩である。
上記の塩を形成する対陽イオンとしては、特に限定はないが、アルカリ金属イオン、アンモニウムイオン等が挙げられる。アルカリ金属イオンとしては、カリウムイオン、ナトリウムイオン、リチウムイオン等が例示できる。
水溶性金塩の中でも、めっき速度、安定性等の観点から、シアン化金（Ｉ）カリウムが最も好ましい。 The water-soluble gold salt is a gold source for the electroless gold plating solution of the present invention, is sufficiently stable in the plating solution, is easily dissolved in water, and is suitable as a gold source for the plating solution. If so, there is no particular limitation.
Specific examples thereof include gold cyanide, gold chloride, gold sulfite, and gold thiosulfate. A gold cyanide salt (gold cyanide (I) salt, gold cyanide (III) salt) is preferable, and a gold cyanide (I) salt is particularly preferable.
The anti-cations forming the above salt are not particularly limited, and examples thereof include alkali metal ions and ammonium ions. Examples of the alkali metal ion include potassium ion, sodium ion, lithium ion and the like.
Among the water-soluble gold salts, potassium gold (I) cyanide is most preferable from the viewpoint of plating speed, stability and the like.
具体的には、シアン化金塩、塩化金塩、亜硫酸金塩、チオ硫酸金塩等が挙げられる。好ましくは、シアン化金塩（シアン化金（Ｉ）塩、シアン化金（III）塩）であり、特に好ましくは、シアン化金（Ｉ）塩である。
上記の塩を形成する対陽イオンとしては、特に限定はないが、アルカリ金属イオン、アンモニウムイオン等が挙げられる。アルカリ金属イオンとしては、カリウムイオン、ナトリウムイオン、リチウムイオン等が例示できる。
水溶性金塩の中でも、めっき速度、安定性等の観点から、シアン化金（Ｉ）カリウムが最も好ましい。 The water-soluble gold salt is a gold source for the electroless gold plating solution of the present invention, is sufficiently stable in the plating solution, is easily dissolved in water, and is suitable as a gold source for the plating solution. If so, there is no particular limitation.
Specific examples thereof include gold cyanide, gold chloride, gold sulfite, and gold thiosulfate. A gold cyanide salt (gold cyanide (I) salt, gold cyanide (III) salt) is preferable, and a gold cyanide (I) salt is particularly preferable.
The anti-cations forming the above salt are not particularly limited, and examples thereof include alkali metal ions and ammonium ions. Examples of the alkali metal ion include potassium ion, sodium ion, lithium ion and the like.
Among the water-soluble gold salts, potassium gold (I) cyanide is most preferable from the viewpoint of plating speed, stability and the like.
水溶性金塩は、１種単独で用いてもよいし、２種以上を併用してもよい。
The water-soluble gold salt may be used alone or in combination of two or more.
無電解金めっき液中の水溶性金塩の濃度（２種以上の水溶性金塩を併用する場合は合計濃度）に特に限定はないが、金換算として、好ましくは０．１ｇ／Ｌ以上、より好ましくは０．３ｇ／Ｌ以上、特に好ましくは０．５ｇ／Ｌ以上である。また、好ましくは５ｇ／Ｌ以下、より好ましくは４ｇ／Ｌ以下、特に好ましくは３ｇ／Ｌ以下である。
水溶性金塩の濃度が上記下限以上であると、めっき速度を十分に大きくすることができる。水溶性金塩の濃度が上記上限以下であると、めっき液の安定性が保たれやすい。 The concentration of the water-soluble gold salt in the electroless gold plating solution (total concentration when two or more kinds of water-soluble gold salts are used in combination) is not particularly limited, but is preferably 0.1 g / L or more in terms of gold. It is more preferably 0.3 g / L or more, and particularly preferably 0.5 g / L or more. Further, it is preferably 5 g / L or less, more preferably 4 g / L or less, and particularly preferably 3 g / L or less.
When the concentration of the water-soluble gold salt is at least the above lower limit, the plating rate can be sufficiently increased. When the concentration of the water-soluble gold salt is not more than the above upper limit, the stability of the plating solution is likely to be maintained.
水溶性金塩の濃度が上記下限以上であると、めっき速度を十分に大きくすることができる。水溶性金塩の濃度が上記上限以下であると、めっき液の安定性が保たれやすい。 The concentration of the water-soluble gold salt in the electroless gold plating solution (total concentration when two or more kinds of water-soluble gold salts are used in combination) is not particularly limited, but is preferably 0.1 g / L or more in terms of gold. It is more preferably 0.3 g / L or more, and particularly preferably 0.5 g / L or more. Further, it is preferably 5 g / L or less, more preferably 4 g / L or less, and particularly preferably 3 g / L or less.
When the concentration of the water-soluble gold salt is at least the above lower limit, the plating rate can be sufficiently increased. When the concentration of the water-soluble gold salt is not more than the above upper limit, the stability of the plating solution is likely to be maintained.
環中に窒素原子を有する縮合環化合物は、縮合環化合物（２以上の環が２以上の原子を共有して結合した化合物）であり、環中に窒素原子を有する（すなわち、環を構成する原子の何れか１つ以上が窒素原子である）化合物であれば、特に限定はない。以下、「環中に窒素原子を有する縮合環化合物」を「特定縮合環化合物」という場合がある。
A fused ring compound having a nitrogen atom in the ring is a condensed ring compound (a compound in which two or more rings share and bond two or more atoms) and has a nitrogen atom in the ring (that is, constitutes a ring). There is no particular limitation as long as it is a compound (in which any one or more of the atoms is a nitrogen atom). Hereinafter, the "condensed ring compound having a nitrogen atom in the ring" may be referred to as a "specific condensed ring compound".
特定縮合環化合物を無電解金めっき液に含有させることにより、無電解金めっきを施す際に、銅素材の露出部があったとしても、無電解金めっき液中への銅の溶出を抑制することができる。
これは、特定縮合環化合物は疎水性が強く、銅表面に銅溶出保護のための保護層を強固に形成するためであると推定される。 By containing the specific fused ring compound in the electroless gold plating solution, even if there is an exposed part of the copper material when performing the electroless gold plating, the elution of copper into the electroless gold plating solution is suppressed. be able to.
It is presumed that this is because the specific condensed ring compound has strong hydrophobicity and strongly forms a protective layer for copper elution protection on the copper surface.
これは、特定縮合環化合物は疎水性が強く、銅表面に銅溶出保護のための保護層を強固に形成するためであると推定される。 By containing the specific fused ring compound in the electroless gold plating solution, even if there is an exposed part of the copper material when performing the electroless gold plating, the elution of copper into the electroless gold plating solution is suppressed. be able to.
It is presumed that this is because the specific condensed ring compound has strong hydrophobicity and strongly forms a protective layer for copper elution protection on the copper surface.
特定縮合環化合物の例としては、ベンゼン環又はピリジン環と、窒素原子を有する複素五員環とが縮合した縮合環化合物が挙げられる。
Examples of the specific condensed ring compound include a condensed ring compound in which a benzene ring or a pyridine ring and a complex five-membered ring having a nitrogen atom are condensed.
特定縮合環化合物は、環中に炭素原子でない原子を２個以上有することが望ましい。特定縮合環化合物は、環中に少なくとも１個の窒素原子を有しているので、言い換えれば、特定縮合環化合物は、環中に窒素原子を２個以上有するか、又は、窒素原子と、炭素でも窒素でもない原子を有しているのが好ましい。炭素でも窒素でもない原子の例としては、硫黄原子、酸素原子、リン原子等が挙げられる。
It is desirable that the specific condensed ring compound has two or more atoms that are not carbon atoms in the ring. Since the specific fused ring compound has at least one nitrogen atom in the ring, in other words, the specific fused ring compound has two or more nitrogen atoms in the ring, or the nitrogen atom and carbon. However, it is preferable to have an atom that is neither nitrogen nor nitrogen. Examples of atoms that are neither carbon nor nitrogen include sulfur atoms, oxygen atoms, phosphorus atoms and the like.
特定縮合環化合物は、窒素原子を有する複素五員環を有しており、該複素五員環中に、炭素原子でない原子を２個以上有するのが望ましい。
具体的には、該複素五員環中に、窒素原子を２個有する場合、窒素原子を３個有する場合、窒素原子を１個と硫黄原子を１個有する場合、窒素原子を１個と酸素原子を１個有する場合、窒素原子を２個と硫黄原子を１個有する場合、窒素原子を２個と酸素原子を１個有する場合、等が挙げられる、 The specific fused ring compound has a complex five-membered ring having a nitrogen atom, and it is desirable that the complex five-membered ring has two or more atoms that are not carbon atoms.
Specifically, when the complex five-membered ring has two nitrogen atoms, three nitrogen atoms, one nitrogen atom and one sulfur atom, one nitrogen atom and oxygen. Examples include the case of having one atom, the case of having two nitrogen atoms and one sulfur atom, the case of having two nitrogen atoms and one oxygen atom, and the like.
具体的には、該複素五員環中に、窒素原子を２個有する場合、窒素原子を３個有する場合、窒素原子を１個と硫黄原子を１個有する場合、窒素原子を１個と酸素原子を１個有する場合、窒素原子を２個と硫黄原子を１個有する場合、窒素原子を２個と酸素原子を１個有する場合、等が挙げられる、 The specific fused ring compound has a complex five-membered ring having a nitrogen atom, and it is desirable that the complex five-membered ring has two or more atoms that are not carbon atoms.
Specifically, when the complex five-membered ring has two nitrogen atoms, three nitrogen atoms, one nitrogen atom and one sulfur atom, one nitrogen atom and oxygen. Examples include the case of having one atom, the case of having two nitrogen atoms and one sulfur atom, the case of having two nitrogen atoms and one oxygen atom, and the like.
特定縮合環化合物は、分子中に少なくとも１個の窒素原子を有しているが、分子中に２個の窒素原子を有していてもよく、分子中に３個の窒素原子を有していてもよく、分子中に４個の窒素原子を有していてもよく、分子中に５個以上の窒素原子を有していてもよい。
The specific fused ring compound has at least one nitrogen atom in the molecule, but may have two nitrogen atoms in the molecule, and has three nitrogen atoms in the molecule. It may have 4 nitrogen atoms in the molecule, and may have 5 or more nitrogen atoms in the molecule.
特定縮合環化合物は、アミノ基、アルキルアミノ基、ニトロ基等の窒素を含む置換基を有していてもよい。その場合、「分子中に有する窒素原子」とは、環中の窒素原子には限られず、これらの置換基に含まれる窒素原子も「分子中に有する窒素原子」に該当する。
The specific fused ring compound may have a substituent containing nitrogen such as an amino group, an alkylamino group and a nitro group. In that case, the "nitrogen atom contained in the molecule" is not limited to the nitrogen atom contained in the ring, and the nitrogen atom contained in these substituents also corresponds to the "nitrogen atom contained in the molecule".
特定縮合環化合物の具体的な構造の例としては、インドール骨格、イソインドール骨格、ベンゾイミダゾール骨格、インダゾール骨格、プリン骨格、ベンゾチアゾール骨格、ベンゾチアジアゾール骨格、ベンゾトリアゾール骨格、キノリン骨格、イソキノリン骨格、キノキサリン骨格、キナゾリン骨格、シンノリン骨格、フタラジン骨格、ピラゾロピリジン骨格、トリアゾロピリジン骨格等の構造（基礎骨格）を有する化合物が挙げられる。
Specific examples of the structure of the specific fused ring compound include indole skeleton, isoindole skeleton, benzoimidazole skeleton, indazole skeleton, purine skeleton, benzothiazole skeleton, benzothiasiazole skeleton, benzotriazole skeleton, quinoline skeleton, isoquinoline skeleton, and quinoxalin. Examples thereof include compounds having a structure (basic skeleton) such as a skeleton, a quinazoline skeleton, a synnoline skeleton, a phthalazine skeleton, a pyrazolopyridine skeleton, and a triazolopyridine skeleton.
上記構造（基礎骨格）を有する特定縮合環化合物は、置換基を有していてもよいし、有していなくてもよい。
The specific condensed ring compound having the above structure (basic skeleton) may or may not have a substituent.
置換基を有する場合、置換基の具体例としては、炭素数１～６のアルキル基、メルカプト基、ヒドロキシ基、カルボキシ基、ニトロ基、ハロゲン基等が例示できる。
アルキル基の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、等が例示できる。
ハロゲン基の具体例としては、フッ素基、塩素基、臭素基、ヨウ素基、等が例示できる。
上記の置換基を有する場合、特定縮合環化合物の疎水性が強くなる為、銅溶出保護のための保護層をより強く形成でき、銅溶出の抑制効果がより顕著になる。 When it has a substituent, specific examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a mercapto group, a hydroxy group, a carboxy group, a nitro group, a halogen group and the like.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group and the like.
Specific examples of the halogen group include a fluorine group, a chlorine group, a bromine group, an iodine group and the like.
When the above substituent is provided, the hydrophobicity of the specific condensed ring compound becomes stronger, so that a protective layer for protecting copper elution can be formed more strongly, and the effect of suppressing copper elution becomes more remarkable.
アルキル基の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、等が例示できる。
ハロゲン基の具体例としては、フッ素基、塩素基、臭素基、ヨウ素基、等が例示できる。
上記の置換基を有する場合、特定縮合環化合物の疎水性が強くなる為、銅溶出保護のための保護層をより強く形成でき、銅溶出の抑制効果がより顕著になる。 When it has a substituent, specific examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a mercapto group, a hydroxy group, a carboxy group, a nitro group, a halogen group and the like.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group and the like.
Specific examples of the halogen group include a fluorine group, a chlorine group, a bromine group, an iodine group and the like.
When the above substituent is provided, the hydrophobicity of the specific condensed ring compound becomes stronger, so that a protective layer for protecting copper elution can be formed more strongly, and the effect of suppressing copper elution becomes more remarkable.
特定縮合環化合物が、ベンゼン環又はピリジン環と、窒素原子を有する複素五員環とが縮合した縮合環化合物である場合、置換基は、ベンゼン環又はピリジン環の方に結合していてもよいし、窒素原子を有する複素五員環の方に結合していてもよい。複数の置換基が、ベンゼン環又はピリジン環、窒素原子を有する複素五員環のそれぞれに結合していてもよい。
When the specific fused ring compound is a condensed ring compound obtained by condensing a benzene ring or a pyridine ring and a complex five-membered ring having a nitrogen atom, the substituent may be bonded to the benzene ring or the pyridine ring. However, it may be bonded to a complex five-membered ring having a nitrogen atom. A plurality of substituents may be bonded to each of a benzene ring, a pyridine ring, and a complex five-membered ring having a nitrogen atom.
特定縮合環化合物が有する上記置換基の数は、１個でもよいし、２個でもよいし、３個でもよいし、４個以上でもよい。
複数の置換基を有する場合、同一の置換基を複数箇所に有していてもよいし、種類の異なる置換基を有していてもよい。 The number of the above-mentioned substituents contained in the specific condensed ring compound may be one, two, three, or four or more.
When it has a plurality of substituents, it may have the same substituent at a plurality of locations, or it may have different types of substituents.
複数の置換基を有する場合、同一の置換基を複数箇所に有していてもよいし、種類の異なる置換基を有していてもよい。 The number of the above-mentioned substituents contained in the specific condensed ring compound may be one, two, three, or four or more.
When it has a plurality of substituents, it may have the same substituent at a plurality of locations, or it may have different types of substituents.
特定縮合環化合物の具体的な化合物名としては、ベンゾイミダゾール、１－メチルベンゾイミダゾール、２－メチルベンゾイミダゾール、２－メルカプトベンゾイミダゾール、２－アミノ－ベンゾイミダゾール、１，２，３－ベンゾトリアゾール、５－メチル－１Ｈ－ベンゾトリアゾール、１－メチル－１Ｈ－ベンゾトリアゾール、カルボキシベンゾトリアゾール、ヒドロシキベンゾトリアゾール、カルボキシヒドロキシベンゾトリアゾール、ニトロベンゾトリアゾール、１－アミノ－ベンゾトリアゾール、２－アミノベンゾチアゾール、１Ｈ－１，２，３－トリアゾロピリジン、３－アミノキノリン、５－アミノインドール、等が挙げられる。
Specific compound names of the specific fused ring compound include benzimidazole, 1-methylbenzimidazole, 2-methylbenzomidazole, 2-mercaptobenzimidazole, 2-amino-benzomidazole, 1,2,3-benzotriazole, and the like. 5-Methyl-1H-benzotriazole, 1-methyl-1H-benzotriazole, carboxybenzotriazole, hydroshikibenzotriazole, carboxyhydroxybenzotriazole, nitrobenzotriazole, 1-amino-benzotriazole, 2-aminobenzotriazole, 1H -1,2,3-triazolopyridine, 3-aminoquinoline, 5-aminoindole, etc. may be mentioned.
特定縮合環化合物は、１種単独で用いてもよいし、２種以上を併用してもよい。
The specific condensed ring compound may be used alone or in combination of two or more.
無電解金めっき液中の特定縮合環化合物の濃度（２種以上の特定縮合環化合物を併用する場合は合計濃度）に特に限定はないが、好ましくは０．１ｐｐｍ以上、より好ましくは０．５ｐｐｍ以上、特に好ましくは２ｐｐｍ以上である。また、好ましくは１０００ｐｐｍ以下、より好ましくは５００ｐｐｍ以下、特に好ましくは１００ｐｐｍ以下である。
特定縮合環化合物の濃度が上記下限以上であると、銅溶出の効果が十分に発揮されやすい。特定縮合環化合物の濃度が上記上限以下であると、コストが抑制でき、また、溶解度を超えた成分が沈殿することを防止できる。 The concentration of the specific condensed ring compound in the electroless gold plating solution (total concentration when two or more specific condensed ring compounds are used in combination) is not particularly limited, but is preferably 0.1 ppm or more, more preferably 0.5 ppm. As mentioned above, it is particularly preferably 2 ppm or more. Further, it is preferably 1000 ppm or less, more preferably 500 ppm or less, and particularly preferably 100 ppm or less.
When the concentration of the specific fused ring compound is at least the above lower limit, the effect of copper elution is likely to be sufficiently exerted. When the concentration of the specific condensed ring compound is not more than the above upper limit, the cost can be suppressed and the precipitation of the component exceeding the solubility can be prevented.
特定縮合環化合物の濃度が上記下限以上であると、銅溶出の効果が十分に発揮されやすい。特定縮合環化合物の濃度が上記上限以下であると、コストが抑制でき、また、溶解度を超えた成分が沈殿することを防止できる。 The concentration of the specific condensed ring compound in the electroless gold plating solution (total concentration when two or more specific condensed ring compounds are used in combination) is not particularly limited, but is preferably 0.1 ppm or more, more preferably 0.5 ppm. As mentioned above, it is particularly preferably 2 ppm or more. Further, it is preferably 1000 ppm or less, more preferably 500 ppm or less, and particularly preferably 100 ppm or less.
When the concentration of the specific fused ring compound is at least the above lower limit, the effect of copper elution is likely to be sufficiently exerted. When the concentration of the specific condensed ring compound is not more than the above upper limit, the cost can be suppressed and the precipitation of the component exceeding the solubility can be prevented.
本発明の無電解金めっき液は、更に、キレート剤を含有していてもよい。キレート剤は、無電解金めっき液を運転するに伴い、めっき槽内に蓄積されるニッケル、銅、パラジウム、鉄、クロム、鉛、コバルト等の金属の析出を防止し、安定に溶解させる作用がある。
The electroless gold plating solution of the present invention may further contain a chelating agent. The chelating agent has the effect of preventing the precipitation of metals such as nickel, copper, palladium, iron, chromium, lead, and cobalt that accumulate in the plating tank as the electroless gold plating solution is operated, and stably dissolving the metal. be.
キレート剤としては、ニッケル、銅、パラジウム、鉄、クロム、鉛、コバルト等の金属に配位して、水に安定に溶解させるものであれば特に限定はないが、ニッケル、銅、パラジウム等に対するキレート特性が良好なものが好ましい。
The chelating agent is not particularly limited as long as it is coordinated with a metal such as nickel, copper, palladium, iron, chromium, lead, and cobalt and stably dissolved in water, but for nickel, copper, palladium, and the like. Those having good chelating properties are preferable.
特に好ましいキレート剤として、分子内にイミノ２酢酸構造を有するキレート剤、メチレンホスホン酸構造を有するキレート剤が挙げられる。
これらのキレート剤は、ニッケル、銅、パラジウム等に対するキレート特性が良好である。 Particularly preferable chelating agents include a chelating agent having an iminodiacetic acid structure in the molecule and a chelating agent having a methylenephosphonic acid structure.
These chelating agents have good chelating properties for nickel, copper, palladium and the like.
これらのキレート剤は、ニッケル、銅、パラジウム等に対するキレート特性が良好である。 Particularly preferable chelating agents include a chelating agent having an iminodiacetic acid structure in the molecule and a chelating agent having a methylenephosphonic acid structure.
These chelating agents have good chelating properties for nickel, copper, palladium and the like.
分子内にイミノ２酢酸構造を有するキレート剤としては、エチレンジアミン４酢酸、ニトリロ３酢酸、ヒドロキシエチルエチレンジアミン３酢酸、ジエチレントリアミン５酢酸、トリエチレンテトラミン６酢酸、ジカルボキシメチルグルタミン酸、プロパンジアミン４酢酸、１，３－ジアミノ－２－ヒドロキシルプロパン４酢酸等のカルボン酸類や、これらの塩が例示できる。
Examples of the chelating agent having an imino2 acetic acid structure in the molecule include ethylenediaminetetraacetic acid, nitrilo3acetic acid, hydroxyethylethylenediamine3acetic acid, diethylenetriamine5acetic acid, triethylenetetramine6acetic acid, dicarboxymethylglutamic acid, propanediamine4acetic acid, 1, Examples thereof include carboxylic acids such as 3-diamino-2-hydroxylpropane-4acetic acid and salts thereof.
メチレンホスホン酸構造を有するキレート剤としては、アミノトリメチレンホスホン酸、ヒドロキシエチリデンジホスホン酸、エチレンジアミンテトラメチレンホスホン酸、ジエチレントリアミンペンタメチレンホスホン酸、ヘキサメチレンジアミンテトラメチレンホスホン酸等のホスホン酸類や、これらの塩が例示できる。
Examples of the chelating agent having a methylenephosphonic acid structure include phosphonic acids such as aminotrimethylenephosphonic acid, hydroxyethylidene diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, and hexamethylenediaminetetramethylenephosphonic acid, and these. An example is salt.
上記のキレート剤の中でも、キレート特性やコストの点等から、エチレンジアミン４酢酸、ニトリロ３酢酸、アミノトリメチレンホスホン酸、エチレンジアミンテトラメチレンホスホン酸が特に望ましい。
Among the above chelating agents, ethylenediaminetetraacetic acid, nitrilotriacetic acid, aminotrimethylenephosphonic acid, and ethylenediaminetetramethylenephosphonic acid are particularly preferable from the viewpoint of chelating characteristics and cost.
キレート剤は、１種単独で用いてもよいし、２種以上を併用してもよい。
The chelating agent may be used alone or in combination of two or more.
無電解金めっき液中のキレート剤の濃度（２種以上のキレート剤を併用する場合は合計濃度）に特に限定はないが、好ましくは０．５ｇ／Ｌ以上、より好ましくは１ｇ／Ｌ以上、特に好ましくは２ｇ／Ｌ以上である。また、好ましくは３０ｇ／Ｌ以下、より好ましくは２０ｇ／Ｌ以下、特に好ましくは１０ｇ／Ｌ以下である。
キレート剤の濃度が上記下限以上であると、十分なキレート効果を発揮し、めっき槽内に蓄積される金属の異常析出を防止しやすい。キレート剤の濃度が上記上限以下であると、コスト的に有利であり、また、溶解度を超えた成分が沈殿することを防止できる。 The concentration of the chelating agent in the electroless gold plating solution (total concentration when two or more kinds of chelating agents are used in combination) is not particularly limited, but is preferably 0.5 g / L or more, more preferably 1 g / L or more. Particularly preferably, it is 2 g / L or more. Further, it is preferably 30 g / L or less, more preferably 20 g / L or less, and particularly preferably 10 g / L or less.
When the concentration of the chelating agent is at least the above lower limit, a sufficient chelating effect is exhibited, and it is easy to prevent abnormal precipitation of metal accumulated in the plating tank. When the concentration of the chelating agent is not more than the above upper limit, it is advantageous in terms of cost, and it is possible to prevent the components exceeding the solubility from precipitating.
キレート剤の濃度が上記下限以上であると、十分なキレート効果を発揮し、めっき槽内に蓄積される金属の異常析出を防止しやすい。キレート剤の濃度が上記上限以下であると、コスト的に有利であり、また、溶解度を超えた成分が沈殿することを防止できる。 The concentration of the chelating agent in the electroless gold plating solution (total concentration when two or more kinds of chelating agents are used in combination) is not particularly limited, but is preferably 0.5 g / L or more, more preferably 1 g / L or more. Particularly preferably, it is 2 g / L or more. Further, it is preferably 30 g / L or less, more preferably 20 g / L or less, and particularly preferably 10 g / L or less.
When the concentration of the chelating agent is at least the above lower limit, a sufficient chelating effect is exhibited, and it is easy to prevent abnormal precipitation of metal accumulated in the plating tank. When the concentration of the chelating agent is not more than the above upper limit, it is advantageous in terms of cost, and it is possible to prevent the components exceeding the solubility from precipitating.
本発明の無電解金めっき液は、更に、緩衝剤を含有していてもよい。緩衝剤は、無電解金めっき液のｐＨを安定化作用がある。かかる作用があれば、緩衝剤の種類に特に限定はなく、有機化合物、無機化合物を問わず、酸、塩基又は塩を適宜配合して使用される。
The electroless gold plating solution of the present invention may further contain a buffer. The buffer has an action of stabilizing the pH of the electroless gold plating solution. If there is such an action, the type of the buffer is not particularly limited, and an acid, a base or a salt may be appropriately blended and used regardless of whether it is an organic compound or an inorganic compound.
緩衝剤の具体例としては、アジピン酸、安息香酸、クエン酸、リンゴ酸、コハク酸、ギ酸、酢酸、乳酸、マロン酸、フタル酸、シュウ酸、酒石酸、グリシン、グルタミン酸、グルタル酸、イミノ２酢酸、デヒドロ酢酸、マレイン酸、フマル酸等のカルボン酸やこれらの塩；エチレンジアミン、ヒドロキシアミン、エタノールアミン、ジエタノールアミン、トリエタノールアミン等のアミン化合物やそれらの塩；ホウ酸、リン酸、ピロリン酸、亜リン酸、チオ硫酸、亜硫酸、硝酸、硫酸、塩酸、チオシアン酸等の無機酸やそれらの塩；等が挙げられる。
Specific examples of the buffering agent include adipic acid, benzoic acid, citric acid, malic acid, succinic acid, formic acid, acetic acid, lactic acid, malonic acid, phthalic acid, oxalic acid, tartrate acid, glycine, glutamic acid, glutaric acid and imino2acetic acid. , Dehydroacetic acid, maleic acid, fumaric acid and other carboxylic acids and salts thereof; amine compounds such as ethylenediamine, hydroxyamine, ethanolamine, diethanolamine, triethanolamine and their salts; boric acid, phosphoric acid, pyrophosphate, sub Examples thereof include inorganic acids such as phosphoric acid, thiosulfate, sulfite, nitric acid, sulfuric acid, hydrochloric acid and thiosicic acid, and salts thereof.
好ましい緩衝剤としては、酸化数が中間状態にある原子を含む酸又はそれらの塩等が挙げられる。また、酸化剤と還元剤の中間の電位にある化合物が挙げられる。
Preferred buffering agents include acids containing atoms having an intermediate oxidation number or salts thereof. Further, a compound having a potential intermediate between the oxidizing agent and the reducing agent can be mentioned.
特に好ましい緩衝剤としては、亜リン酸やその塩、亜硫酸やその塩等が挙げられる。亜リン酸や亜硫酸の塩の例としては、リチウム塩、ナトリウム塩、カリウム塩、マグネシウム塩、カルシウム塩、バリウム塩、アンモニウム塩等が挙げられる。
Particularly preferable buffering agents include phosphorous acid and its salts, sulfurous acid and its salts, and the like. Examples of salts of phosphoric acid and sulfite include lithium salt, sodium salt, potassium salt, magnesium salt, calcium salt, barium salt, ammonium salt and the like.
最も好ましい緩衝剤としては、めっき液中で不溶性の塩を形成しにくいという理由から、亜硫酸ナトリウム、亜硫酸カリウム、亜リン酸ナトリウム等が挙げられる。
The most preferable buffering agent includes sodium sulfite, potassium sulfite, sodium sulfite and the like because it is difficult to form an insoluble salt in the plating solution.
緩衝剤は、１種単独で用いてもよいし、２種以上を併用してもよい。
The buffer may be used alone or in combination of two or more.
無電解金めっき液中の緩衝剤の濃度（２種以上の緩衝剤を併用する場合は合計濃度）に特に限定はないが、好ましくは１ｇ／Ｌ以上、より好ましくは２ｇ／Ｌ以上、特に好ましくは３ｇ／Ｌ以上である。また、好ましくは３００ｇ／Ｌ以下、より好ましくは２００ｇ／Ｌ以下、特に好ましくは１００ｇ／Ｌ以下である。
緩衝剤の濃度が上記下限以上であると、十分な緩衝効果を発揮しやすい。緩衝剤の濃度が上記上限以下であると、コスト的に有利であり、また、溶解度を超えた成分が沈殿することを防止できる。 The concentration of the buffer in the electroless gold plating solution (total concentration when two or more kinds of buffers are used in combination) is not particularly limited, but is preferably 1 g / L or more, more preferably 2 g / L or more, and particularly preferably. Is 3 g / L or more. Further, it is preferably 300 g / L or less, more preferably 200 g / L or less, and particularly preferably 100 g / L or less.
When the concentration of the buffering agent is at least the above lower limit, a sufficient buffering effect is likely to be exhibited. When the concentration of the buffering agent is not more than the above upper limit, it is advantageous in terms of cost, and it is possible to prevent the components exceeding the solubility from precipitating.
緩衝剤の濃度が上記下限以上であると、十分な緩衝効果を発揮しやすい。緩衝剤の濃度が上記上限以下であると、コスト的に有利であり、また、溶解度を超えた成分が沈殿することを防止できる。 The concentration of the buffer in the electroless gold plating solution (total concentration when two or more kinds of buffers are used in combination) is not particularly limited, but is preferably 1 g / L or more, more preferably 2 g / L or more, and particularly preferably. Is 3 g / L or more. Further, it is preferably 300 g / L or less, more preferably 200 g / L or less, and particularly preferably 100 g / L or less.
When the concentration of the buffering agent is at least the above lower limit, a sufficient buffering effect is likely to be exhibited. When the concentration of the buffering agent is not more than the above upper limit, it is advantageous in terms of cost, and it is possible to prevent the components exceeding the solubility from precipitating.
本発明の無電解金めっき液は、主に上記緩衝剤によって、ｐＨが安定に保たれるが、ｐＨの好ましい範囲は、好ましくは４以上、より好ましくは４．５以上、特に好ましくは５以上である。また、好ましくは８以下、より好ましくは７．５以下、特に好ましくは７以下である。
ｐＨが上記下限以上であると、水溶性金塩が安定して液中に存在できる。ｐＨが上記上限以下であると、基板上のレジストが侵食されにくい。 The pH of the electroless gold plating solution of the present invention is kept stable mainly by the above buffer, but the preferable range of pH is preferably 4 or more, more preferably 4.5 or more, and particularly preferably 5 or more. Is. Further, it is preferably 8 or less, more preferably 7.5 or less, and particularly preferably 7 or less.
When the pH is at least the above lower limit, the water-soluble gold salt can stably exist in the liquid. When the pH is not more than the above upper limit, the resist on the substrate is less likely to be eroded.
ｐＨが上記下限以上であると、水溶性金塩が安定して液中に存在できる。ｐＨが上記上限以下であると、基板上のレジストが侵食されにくい。 The pH of the electroless gold plating solution of the present invention is kept stable mainly by the above buffer, but the preferable range of pH is preferably 4 or more, more preferably 4.5 or more, and particularly preferably 5 or more. Is. Further, it is preferably 8 or less, more preferably 7.5 or less, and particularly preferably 7 or less.
When the pH is at least the above lower limit, the water-soluble gold salt can stably exist in the liquid. When the pH is not more than the above upper limit, the resist on the substrate is less likely to be eroded.
本発明の無電解金めっき液は、置換型無電解金めっき液でもよいし、還元型無電解金めっき液でもよいし、置換還元型無電解金めっき液でもよい。
The electroless gold plating solution of the present invention may be a substitution type electroless gold plating solution, a reduction type electroless gold plating solution, or a substitution reduction type electroless gold plating solution.
還元型無電解金めっき液や、置換還元型無電解金めっき液の場合、本発明の無電解金めっき液が含有する還元剤としては、アスコルビン酸、エリソルビン酸、グリオキシル酸、ギ酸、チオグリコール酸、ホルムアミンジスルフィン酸、アスパラギン酸、酒石酸等の有機酸類やそれらの塩；次亜リン酸等の無機酸類やそれらの塩；チオ尿素、１－アリル－２－チオ尿素、１－アリル－３－（２－ヒドロキシエチル）－２－チオ尿素、１，３－ジエチル－２－チオ尿素、トリメチルチオ尿素、１，３－ジメチルチオ尿素、１－アセチルチオ尿素、Ｎ－アリルチオ尿素、エチレンチオ尿素、Ｎ－メチルチオ尿素等のチオ尿素類；チオセミカルバジド、ヒドラジン、ｐ－ヒドラジノベンゼンスルホン酸、イソニコチン酸ヒドラジド、硫酸ヒドラジン等のヒドラジン誘導体類；ジメチルアミノボラン、トリメチルアミノボラン、水素化ホウ素ナトリウム、水素化ホウ素カリウム、ジエチルアミノボラン、トリエチルアミノボラン等のホウ素化合物；ホルムアルデヒド、アセトアルデヒド等のアルデヒド類；ヒドロキシアミン；ハイドロキノン；等が挙げられる。
In the case of the reduction type electroless gold plating solution and the substituted reduction type electroless gold plating solution, the reducing agents contained in the electroless gold plating solution of the present invention include ascorbic acid, erythorbic acid, glyoxylic acid, formic acid and thioglycolic acid. , Formamine disulfic acid, aspartic acid, tartrate and other organic acids and their salts; inorganic acids such as hypophosphite and their salts; thiourea, 1-allyl-2-thiourea, 1-allyl-3- (2-Hydroxyethyl) -2-thiourea, 1,3-diethyl-2-thiourea, trimethylthiourea, 1,3-dimethylthiourea, 1-acetylthiourea, N-allylthiourea, ethylenethiourea, N-methylthio Thiourea such as urea; hydrazine derivatives such as thiosemicarbazide, hydrazine, p-hydrazinobenzenesulfonic acid, isonicotinic acid hydrazide, hydrazine sulfate; dimethylaminoborane, trimethylaminoborane, sodium hydride, potassium hydride , Borone compounds such as diethylaminoborane and triethylaminoborane; aldehydes such as formaldehyde and acetaldehyde; hydroxyamine; hydroquinone; and the like.
上記の還元剤の中でも、めっき液の安定性の点から、アスコルビン酸やその塩、チオ尿素類が特に好ましい。
Among the above reducing agents, ascorbic acid, salts thereof, and thioureas are particularly preferable from the viewpoint of the stability of the plating solution.
還元剤は、１種単独で用いてもよいし、２種以上を併用してもよい。
The reducing agent may be used alone or in combination of two or more.
無電解金めっき液中の還元剤の濃度（２種以上の還元剤を併用する場合は合計濃度）に特に限定はないが、好ましくは０．０１ｇ／Ｌ以上、より好ましくは０．０５ｇ／Ｌ以上、特に好ましくは０．２ｇ／Ｌ以上である。また、好ましくは５０ｇ／Ｌ以下、より好ましくは２０ｇ／Ｌ以下、特に好ましくは５ｇ／Ｌ以下である。
還元剤の濃度が上記下限以上であると、安定しためっき析出性が得られる。還元剤の濃度が上記上限以下であると、コスト的に有利であり、また、めっき液の安定性に優れる。 The concentration of the reducing agent in the electroless gold plating solution (total concentration when two or more kinds of reducing agents are used in combination) is not particularly limited, but is preferably 0.01 g / L or more, more preferably 0.05 g / L. The above is particularly preferably 0.2 g / L or more. Further, it is preferably 50 g / L or less, more preferably 20 g / L or less, and particularly preferably 5 g / L or less.
When the concentration of the reducing agent is at least the above lower limit, stable plating precipitateability can be obtained. When the concentration of the reducing agent is not more than the above upper limit, it is advantageous in terms of cost and the stability of the plating solution is excellent.
還元剤の濃度が上記下限以上であると、安定しためっき析出性が得られる。還元剤の濃度が上記上限以下であると、コスト的に有利であり、また、めっき液の安定性に優れる。 The concentration of the reducing agent in the electroless gold plating solution (total concentration when two or more kinds of reducing agents are used in combination) is not particularly limited, but is preferably 0.01 g / L or more, more preferably 0.05 g / L. The above is particularly preferably 0.2 g / L or more. Further, it is preferably 50 g / L or less, more preferably 20 g / L or less, and particularly preferably 5 g / L or less.
When the concentration of the reducing agent is at least the above lower limit, stable plating precipitateability can be obtained. When the concentration of the reducing agent is not more than the above upper limit, it is advantageous in terms of cost and the stability of the plating solution is excellent.
本発明の無電解金めっき液は、更に、金属イオン封鎖剤、界面活性剤、結晶調整剤等を含有していてもよい。
金属イオン封鎖剤は、無電解金めっき液中に不純物金属が混入した場合にその影響を除去する作用を持つ。
界面活性剤は、無電解金めっき液の濡れ特性を制御する作用を持つ。
結晶調整剤は、析出する無電解金めっき皮膜の結晶構造を制御する作用を持つ。 The electroless gold plating solution of the present invention may further contain a metal ion sequestering agent, a surfactant, a crystal adjusting agent and the like.
The sequestrant has an action of removing the influence of impurity metals mixed in the electroless gold plating solution.
The surfactant has an action of controlling the wetting characteristics of the electroless gold plating solution.
The crystal modifier has an action of controlling the crystal structure of the deposited electroless gold plating film.
金属イオン封鎖剤は、無電解金めっき液中に不純物金属が混入した場合にその影響を除去する作用を持つ。
界面活性剤は、無電解金めっき液の濡れ特性を制御する作用を持つ。
結晶調整剤は、析出する無電解金めっき皮膜の結晶構造を制御する作用を持つ。 The electroless gold plating solution of the present invention may further contain a metal ion sequestering agent, a surfactant, a crystal adjusting agent and the like.
The sequestrant has an action of removing the influence of impurity metals mixed in the electroless gold plating solution.
The surfactant has an action of controlling the wetting characteristics of the electroless gold plating solution.
The crystal modifier has an action of controlling the crystal structure of the deposited electroless gold plating film.
［無電解金めっき液調製用組成物］
本発明は、水と水溶性金塩を添加することによって無電解金めっき液を調製するための無電解金めっき液調製用組成物であって、前記した特定縮合環化合物を含有することを特徴とする無電解金めっき液調製用組成物にも関する。 [Composition for preparing electroless gold plating solution]
The present invention is a composition for preparing an electroless gold plating solution for preparing an electroless gold plating solution by adding water and a water-soluble gold salt, and is characterized by containing the above-mentioned specific condensed ring compound. It also relates to a composition for preparing a non-electrolytic gold plating solution.
本発明は、水と水溶性金塩を添加することによって無電解金めっき液を調製するための無電解金めっき液調製用組成物であって、前記した特定縮合環化合物を含有することを特徴とする無電解金めっき液調製用組成物にも関する。 [Composition for preparing electroless gold plating solution]
The present invention is a composition for preparing an electroless gold plating solution for preparing an electroless gold plating solution by adding water and a water-soluble gold salt, and is characterized by containing the above-mentioned specific condensed ring compound. It also relates to a composition for preparing a non-electrolytic gold plating solution.
本発明の無電解金めっき液の必須成分である水溶性金塩は、非常に高価であり、時価で取引されるのが通常である。また、水溶性金塩は、水溶液中に含有した状態で保存するのは不経済となる場合があり、水溶性金塩を水溶液の形で保存しておくと、めっき液としての諸性能が低下する場合がある。
このため、水溶性金塩は、水に溶解していない状態で別途保管しておき、無電解金めっき液を使用する際に、他の成分（無電解金めっき液が含有する全ての成分であっても一部の成分であってもよい）を配合した水溶液に、水溶性金塩を添加するのが好ましい。 The water-soluble gold salt, which is an essential component of the electroless gold plating solution of the present invention, is very expensive and is usually traded at the market price. In addition, it may be uneconomical to store the water-soluble gold salt in the state of being contained in the aqueous solution, and if the water-soluble gold salt is stored in the form of an aqueous solution, various performances as a plating solution deteriorate. May be done.
For this reason, the water-soluble gold salt should be stored separately in a state where it is not dissolved in water, and when using the electroless gold plating solution, other components (all components contained in the electroless gold plating solution) should be used. It is preferable to add a water-soluble gold salt to the aqueous solution containing the mixture (which may be present or may be a part of the components).
このため、水溶性金塩は、水に溶解していない状態で別途保管しておき、無電解金めっき液を使用する際に、他の成分（無電解金めっき液が含有する全ての成分であっても一部の成分であってもよい）を配合した水溶液に、水溶性金塩を添加するのが好ましい。 The water-soluble gold salt, which is an essential component of the electroless gold plating solution of the present invention, is very expensive and is usually traded at the market price. In addition, it may be uneconomical to store the water-soluble gold salt in the state of being contained in the aqueous solution, and if the water-soluble gold salt is stored in the form of an aqueous solution, various performances as a plating solution deteriorate. May be done.
For this reason, the water-soluble gold salt should be stored separately in a state where it is not dissolved in water, and when using the electroless gold plating solution, other components (all components contained in the electroless gold plating solution) should be used. It is preferable to add a water-soluble gold salt to the aqueous solution containing the mixture (which may be present or may be a part of the components).
本発明の無電解金めっき液調製用組成物は、前記した特定縮合環化合物を含有し、必要に応じて、前記したキレート剤、緩衝剤、金属イオン封鎖剤、界面活性剤、結晶調整剤、還元剤を含有していてもよい。
The composition for preparing an electroless gold plating solution of the present invention contains the above-mentioned specific condensed ring compound, and if necessary, the above-mentioned chelating agent, buffer, metal ion sequestering agent, surfactant, crystal modifier, etc. It may contain a reducing agent.
本発明の無電解金めっき液調製用組成物の形態に限定はなく、粉末状であってもよいし、水溶液であってもよい。
水溶液の場合、特定縮合環化合物の濃度は、前記した無電解金めっき液中における特定縮合環化合物の濃度よりも濃く、無電解金めっき液として使用する際に更に水を添加する（特定縮合環化合物の濃度を薄める）ようにしてもよい。 The form of the composition for preparing an electroless gold plating solution of the present invention is not limited, and may be in the form of powder or in the form of an aqueous solution.
In the case of an aqueous solution, the concentration of the specific condensed ring compound is higher than the concentration of the specific condensed ring compound in the above-mentioned electroless gold plating solution, and water is further added when the specific condensed ring compound is used as the electroless gold plating solution (specific condensed ring). The concentration of the compound may be diluted).
水溶液の場合、特定縮合環化合物の濃度は、前記した無電解金めっき液中における特定縮合環化合物の濃度よりも濃く、無電解金めっき液として使用する際に更に水を添加する（特定縮合環化合物の濃度を薄める）ようにしてもよい。 The form of the composition for preparing an electroless gold plating solution of the present invention is not limited, and may be in the form of powder or in the form of an aqueous solution.
In the case of an aqueous solution, the concentration of the specific condensed ring compound is higher than the concentration of the specific condensed ring compound in the above-mentioned electroless gold plating solution, and water is further added when the specific condensed ring compound is used as the electroless gold plating solution (specific condensed ring). The concentration of the compound may be diluted).
本発明の無電解金めっき液調製用組成物に、水溶性金塩を別途添加することで、又は、水溶性金塩と水を別途添加することで、本発明の無電解金めっき液を調製することができる。
The electroless gold plating solution of the present invention is prepared by separately adding a water-soluble gold salt to the composition for preparing an electroless gold plating solution of the present invention, or by separately adding a water-soluble gold salt and water. can do.
本発明の無電解金めっき液調製用組成物は、無電解金めっき液の他の成分（キレート剤、緩衝剤、金属イオン封鎖剤、界面活性剤、結晶調整剤、還元剤等）の全部又は一部を含まないものであってもよい。言い換えれば、これらの成分は、水溶性金塩や水と同様に、無電解金めっき液を調製する際に、無電解金めっき液調製用組成物に別途添加してもよい。
The composition for preparing an electroless gold plating solution of the present invention includes all or all of the other components of the electroless gold plating solution (chelating agent, buffering agent, metal ion sequestering agent, surfactant, crystal modifier, reducing agent, etc.). It may not include a part. In other words, these components may be separately added to the composition for preparing the electroless gold plating solution when preparing the electroless gold plating solution, like the water-soluble gold salt and water.
［無電解金めっき皮膜の製造方法］
本発明は、前記した無電解金めっき液を使用して、無電解金めっき皮膜を製造する無電解めっき皮膜の製造方法にも関する。 [Manufacturing method of electroless gold plating film]
The present invention also relates to a method for producing an electroless plating film using the above-mentioned electroless gold plating solution to produce an electroless gold plating film.
本発明は、前記した無電解金めっき液を使用して、無電解金めっき皮膜を製造する無電解めっき皮膜の製造方法にも関する。 [Manufacturing method of electroless gold plating film]
The present invention also relates to a method for producing an electroless plating film using the above-mentioned electroless gold plating solution to produce an electroless gold plating film.
本発明の無電解めっき皮膜の製造方法の適用対象となるプロセスに特に限定はないが、例えば、銅素材の上に形成された無電解ニッケル皮膜の上に無電解金めっき皮膜を形成させるプロセス（ＥＮＩＧ）、銅素材の上に形成された無電解ニッケル皮膜の上に無電解パラジウム皮膜を形成させ、更にその上に無電解金めっき皮膜を形成させるプロセス（ＥＮＥＰＩＧ）、銅素材の上に形成された無電解ニッケルめっき皮膜上に置換金めっき被膜を形成させ、更にその上に還元金めっきを形成させるプロセス（ＥＮＥＡＧ）等に適用することができる。
The process to which the method for producing an electroless plating film of the present invention is applied is not particularly limited, and for example, a process of forming an electroless gold plating film on an electroless nickel film formed on a copper material (a process of forming an electroless gold plating film on an electroless nickel film formed on a copper material). ENIG), a process of forming an electroless palladium film on an electroless nickel film formed on a copper material and further forming an electroless gold plating film on it (ENEPIG), formed on a copper material. It can be applied to a process (ENEAG) of forming a substituted gold plating film on an electroless nickel plating film and further forming a reduced gold plating on the substituted gold plating film.
本発明の無電解金めっき皮膜の製造方法によれば、ニッケル皮膜等の未析出部分や、ドライフィルムの形成不良等に起因する銅の露出部がわずかに存在していても、該露出部からの銅の溶出を抑制することができる。このため、本発明の無電解金めっき皮膜の製造方法では、無電解金めっき液中における銅の蓄積に起因する問題が発生しにくく、無電解金めっき液の更新頻度を減少することができ、生産効率が上昇する。
According to the method for producing an electroless gold plating film of the present invention, even if an unprecipitated portion such as a nickel film or an exposed portion of copper due to poor formation of a dry film is slightly present, the exposed portion can be used. Elution of copper can be suppressed. Therefore, in the method for producing the electroless gold plating film of the present invention, problems caused by the accumulation of copper in the electroless gold plating solution are less likely to occur, and the frequency of updating the electroless gold plating solution can be reduced. Production efficiency increases.
本発明の無電解金めっき皮膜の製造方法により、無電解金めっき皮膜を形成する際に、無電解金めっき皮膜の厚さ（後述の実施例の方法により測定される厚さ）は、特に限定は無いが、０．００５μｍ以上であることが好ましく、０．０１μｍ以上であることがより好ましく、０．０２μｍ以上であることが特に好ましい。また、１μｍ以下であることが好ましく、０．７μｍ以下であることがより好ましく、０．５μｍ以下であることが特に好ましい。
上記下限以上であると、皮膜としての性能を十分に発揮することができる。また、上記上限以下であると、コスト的に有利である。 When forming the electroless gold plating film by the method for producing the electroless gold plating film of the present invention, the thickness of the electroless gold plating film (thickness measured by the method of Examples described later) is particularly limited. However, it is preferably 0.005 μm or more, more preferably 0.01 μm or more, and particularly preferably 0.02 μm or more. Further, it is preferably 1 μm or less, more preferably 0.7 μm or less, and particularly preferably 0.5 μm or less.
When it is at least the above lower limit, the performance as a film can be sufficiently exhibited. Further, if it is not more than the above upper limit, it is advantageous in terms of cost.
上記下限以上であると、皮膜としての性能を十分に発揮することができる。また、上記上限以下であると、コスト的に有利である。 When forming the electroless gold plating film by the method for producing the electroless gold plating film of the present invention, the thickness of the electroless gold plating film (thickness measured by the method of Examples described later) is particularly limited. However, it is preferably 0.005 μm or more, more preferably 0.01 μm or more, and particularly preferably 0.02 μm or more. Further, it is preferably 1 μm or less, more preferably 0.7 μm or less, and particularly preferably 0.5 μm or less.
When it is at least the above lower limit, the performance as a film can be sufficiently exhibited. Further, if it is not more than the above upper limit, it is advantageous in terms of cost.
なお、「皮膜」とは、一様に平坦である膜には限られず、孔があったり、粒状となっている部分があったりするものも、「皮膜」という。「皮膜」とは「層」と同義である。
The "film" is not limited to a film that is uniformly flat, and a film that has pores or granular parts is also called a "film". "Film" is synonymous with "layer".
無電解金めっき皮膜の製造方法により、無電解金めっき皮膜を形成する際の無電解金めっき液の温度は、１０℃以上であることが好ましく、１５℃以上であることがより好ましく、２０℃以上であることが特に好ましい。また、１００℃以下であることが好ましく、９５℃以下であることがより好ましく、９０℃以下であることが特に好ましい。
また、電解金めっき皮膜の製造方法により、無電解金めっき皮膜を形成する際の時間（めっき時間）は、０．５分以上であることが好ましく、１分以上であることがより好ましく、２分以上であることが特に好ましい。また、２４０分以下であることが好ましく、１２０分以下であることがより好ましく、６０分以下であることが特に好ましい。
無電解金めっき液の温度やめっき時間が上記範囲内であると、膜厚を前記した範囲にしやすい。 Depending on the method for producing the electroless gold plating film, the temperature of the electroless gold plating solution when forming the electroless gold plating film is preferably 10 ° C. or higher, more preferably 15 ° C. or higher, and more preferably 20 ° C. The above is particularly preferable. Further, it is preferably 100 ° C. or lower, more preferably 95 ° C. or lower, and particularly preferably 90 ° C. or lower.
Further, depending on the method for producing the electrolytic gold plating film, the time (plating time) for forming the electrolytic gold plating film is preferably 0.5 minutes or more, more preferably 1 minute or more, and 2 It is particularly preferable that it is at least a minute. Further, it is preferably 240 minutes or less, more preferably 120 minutes or less, and particularly preferably 60 minutes or less.
When the temperature and plating time of the electroless gold plating solution are within the above ranges, the film thickness is likely to be within the above ranges.
また、電解金めっき皮膜の製造方法により、無電解金めっき皮膜を形成する際の時間（めっき時間）は、０．５分以上であることが好ましく、１分以上であることがより好ましく、２分以上であることが特に好ましい。また、２４０分以下であることが好ましく、１２０分以下であることがより好ましく、６０分以下であることが特に好ましい。
無電解金めっき液の温度やめっき時間が上記範囲内であると、膜厚を前記した範囲にしやすい。 Depending on the method for producing the electroless gold plating film, the temperature of the electroless gold plating solution when forming the electroless gold plating film is preferably 10 ° C. or higher, more preferably 15 ° C. or higher, and more preferably 20 ° C. The above is particularly preferable. Further, it is preferably 100 ° C. or lower, more preferably 95 ° C. or lower, and particularly preferably 90 ° C. or lower.
Further, depending on the method for producing the electrolytic gold plating film, the time (plating time) for forming the electrolytic gold plating film is preferably 0.5 minutes or more, more preferably 1 minute or more, and 2 It is particularly preferable that it is at least a minute. Further, it is preferably 240 minutes or less, more preferably 120 minutes or less, and particularly preferably 60 minutes or less.
When the temperature and plating time of the electroless gold plating solution are within the above ranges, the film thickness is likely to be within the above ranges.
［電子部品の製造方法］
本発明は、電子部品の製造方法であって、該電子部品が、前記の無電解金めっき皮膜の製造方法により製造された無電解金めっき皮膜を有することを特徴とする電子部品の製造方法にも関する。
また、本発明は、前記の無電解金めっき液を使用して、無電解金めっき皮膜を形成させる工程を有することを特徴とする電子部品の製造方法にも関する。 [Manufacturing method of electronic parts]
The present invention is a method for manufacturing an electronic component, wherein the electronic component has an electroless gold plating film manufactured by the above-mentioned method for manufacturing an electroless gold plating film. Also related.
The present invention also relates to a method for manufacturing an electronic component, which comprises a step of forming an electroless gold plating film by using the above-mentioned electroless gold plating solution.
本発明は、電子部品の製造方法であって、該電子部品が、前記の無電解金めっき皮膜の製造方法により製造された無電解金めっき皮膜を有することを特徴とする電子部品の製造方法にも関する。
また、本発明は、前記の無電解金めっき液を使用して、無電解金めっき皮膜を形成させる工程を有することを特徴とする電子部品の製造方法にも関する。 [Manufacturing method of electronic parts]
The present invention is a method for manufacturing an electronic component, wherein the electronic component has an electroless gold plating film manufactured by the above-mentioned method for manufacturing an electroless gold plating film. Also related.
The present invention also relates to a method for manufacturing an electronic component, which comprises a step of forming an electroless gold plating film by using the above-mentioned electroless gold plating solution.
以下に、実施例及び比較例を挙げて本発明を更に具体的に説明するが、本発明は、その要旨を超えない限りこれらの実施例に限定されるものではない。
なお、「ｐｐｍ」は特に断りがない限り「質量ｐｐｍ」を示す。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples as long as the gist thereof is not exceeded.
In addition, "ppm" indicates "mass ppm" unless otherwise specified.
なお、「ｐｐｍ」は特に断りがない限り「質量ｐｐｍ」を示す。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples as long as the gist thereof is not exceeded.
In addition, "ppm" indicates "mass ppm" unless otherwise specified.
［無電解金めっき液の調製］
実施例１～１８、比較例１～６
下記に示す濃度でイオン交換水に各成分を溶解したベース液Ａに、表１に示す窒素原子を有する縮合環化合物又は比較化合物を無電解めっき液全体に対して１０ｐｐｍになるように溶解させ、ｐＨ６．５になるように調整し、実施例１～１８、比較例１～６の無電解金めっき液を調製した。なお、ｐＨ調整の際には、ｐＨを上げる時は水酸化ナトリウム水溶液を、下げる時は硫酸を使用した。 [Preparation of electroless gold plating solution]
Examples 1 to 18, Comparative Examples 1 to 6
The condensed ring compound or comparative compound having a nitrogen atom shown in Table 1 was dissolved in the base solution A in which each component was dissolved in ion-exchanged water at the concentration shown below so as to be 10 ppm with respect to the entire electroless plating solution. The pH was adjusted to 6.5, and electroless gold plating solutions of Examples 1 to 18 and Comparative Examples 1 to 6 were prepared. When adjusting the pH, an aqueous solution of sodium hydroxide was used to raise the pH, and sulfuric acid was used to lower the pH.
実施例１～１８、比較例１～６
下記に示す濃度でイオン交換水に各成分を溶解したベース液Ａに、表１に示す窒素原子を有する縮合環化合物又は比較化合物を無電解めっき液全体に対して１０ｐｐｍになるように溶解させ、ｐＨ６．５になるように調整し、実施例１～１８、比較例１～６の無電解金めっき液を調製した。なお、ｐＨ調整の際には、ｐＨを上げる時は水酸化ナトリウム水溶液を、下げる時は硫酸を使用した。 [Preparation of electroless gold plating solution]
Examples 1 to 18, Comparative Examples 1 to 6
The condensed ring compound or comparative compound having a nitrogen atom shown in Table 1 was dissolved in the base solution A in which each component was dissolved in ion-exchanged water at the concentration shown below so as to be 10 ppm with respect to the entire electroless plating solution. The pH was adjusted to 6.5, and electroless gold plating solutions of Examples 1 to 18 and Comparative Examples 1 to 6 were prepared. When adjusting the pH, an aqueous solution of sodium hydroxide was used to raise the pH, and sulfuric acid was used to lower the pH.
＜ベース液Ａ＞
シアン化金（Ｉ）カリウム ２ｇ／Ｌ
クエン酸カリウム ３０ｇ／Ｌ <Base liquid A>
Gold (I) Cyanide Potassium 2g / L
Potassium citrate 30 g / L
シアン化金（Ｉ）カリウム ２ｇ／Ｌ
クエン酸カリウム ３０ｇ／Ｌ <Base liquid A>
Gold (I) Cyanide Potassium 2g / L
Potassium citrate 30 g / L
実施例１９～２０
下記に示す濃度でイオン交換水に各成分を溶解したベース液Ｂに、表１に示す窒素原子を有する縮合環化合物を無電解めっき液全体に対して１０ｐｐｍになるように溶解させ、ｐＨ６．５になるように調整し、実施例１９～２０の無電解金めっき液を調製した。なお、ｐＨ調整の際には、ｐＨを上げる時は水酸化ナトリウム水溶液を、下げる時は硫酸を使用した。 Examples 19-20
The condensed ring compound having a nitrogen atom shown in Table 1 was dissolved in the base liquid B in which each component was dissolved in ion-exchanged water at the concentration shown below so as to be 10 ppm with respect to the entire electroless plating solution, and the pH was 6.5. The electroless gold plating solution of Examples 19 to 20 was prepared. When adjusting the pH, an aqueous solution of sodium hydroxide was used to raise the pH, and sulfuric acid was used to lower the pH.
下記に示す濃度でイオン交換水に各成分を溶解したベース液Ｂに、表１に示す窒素原子を有する縮合環化合物を無電解めっき液全体に対して１０ｐｐｍになるように溶解させ、ｐＨ６．５になるように調整し、実施例１９～２０の無電解金めっき液を調製した。なお、ｐＨ調整の際には、ｐＨを上げる時は水酸化ナトリウム水溶液を、下げる時は硫酸を使用した。 Examples 19-20
The condensed ring compound having a nitrogen atom shown in Table 1 was dissolved in the base liquid B in which each component was dissolved in ion-exchanged water at the concentration shown below so as to be 10 ppm with respect to the entire electroless plating solution, and the pH was 6.5. The electroless gold plating solution of Examples 19 to 20 was prepared. When adjusting the pH, an aqueous solution of sodium hydroxide was used to raise the pH, and sulfuric acid was used to lower the pH.
＜ベース液Ｂ＞
シアン化金（Ｉ）カリウム ２ｇ／Ｌ
クエン酸カリウム ３０ｇ／Ｌ
亜硫酸ナトリウム １０ｇ／Ｌ
エチレンジアミン４酢酸ナトリウム ５ｇ／Ｌ <Base liquid B>
Gold (I) Cyanide Potassium 2g / L
Potassium citrate 30 g / L
Sodium sulfite 10 g / L
Ethylenediamine 4 sodium acetate 5 g / L
シアン化金（Ｉ）カリウム ２ｇ／Ｌ
クエン酸カリウム ３０ｇ／Ｌ
亜硫酸ナトリウム １０ｇ／Ｌ
エチレンジアミン４酢酸ナトリウム ５ｇ／Ｌ <Base liquid B>
Gold (I) Cyanide Potassium 2g / L
Potassium citrate 30 g / L
Sodium sulfite 10 g / L
Ethylenediamine 4 sodium acetate 5 g / L
実施例２１～２２
下記に示す濃度でイオン交換水に各成分を溶解したベース液Ｃに、表１に示す窒素原子を有する縮合環化合物を無電解めっき液全体に対して１０ｐｐｍになるように溶解させ、ｐＨ６．５になるように調整し、実施例２１～２２の無電解金めっき液を調製した。なお、ｐＨ調整の際には、ｐＨを上げる時は水酸化ナトリウム水溶液を、下げる時は硫酸を使用した。ベース液Ｃを使用した無電解金めっき液は還元型の無電解めっき液となる。 Examples 21-22
The condensed ring compound having a nitrogen atom shown in Table 1 was dissolved in the base liquid C in which each component was dissolved in ion-exchanged water at the concentration shown below so as to be 10 ppm with respect to the entire electroless plating solution, and the pH was 6.5. The electroless gold plating solution of Examples 21 to 22 was prepared. When adjusting the pH, an aqueous solution of sodium hydroxide was used to raise the pH, and sulfuric acid was used to lower the pH. The electroless gold plating solution using the base liquid C is a reduction type electroless plating solution.
下記に示す濃度でイオン交換水に各成分を溶解したベース液Ｃに、表１に示す窒素原子を有する縮合環化合物を無電解めっき液全体に対して１０ｐｐｍになるように溶解させ、ｐＨ６．５になるように調整し、実施例２１～２２の無電解金めっき液を調製した。なお、ｐＨ調整の際には、ｐＨを上げる時は水酸化ナトリウム水溶液を、下げる時は硫酸を使用した。ベース液Ｃを使用した無電解金めっき液は還元型の無電解めっき液となる。 Examples 21-22
The condensed ring compound having a nitrogen atom shown in Table 1 was dissolved in the base liquid C in which each component was dissolved in ion-exchanged water at the concentration shown below so as to be 10 ppm with respect to the entire electroless plating solution, and the pH was 6.5. The electroless gold plating solution of Examples 21 to 22 was prepared. When adjusting the pH, an aqueous solution of sodium hydroxide was used to raise the pH, and sulfuric acid was used to lower the pH. The electroless gold plating solution using the base liquid C is a reduction type electroless plating solution.
＜ベース液Ｃ＞
シアン化金（Ｉ）カリウム ２ｇ／Ｌ
クエン酸カリウム ３０ｇ／Ｌ
アスコルビン酸ナトリウム ２ｇ／Ｌ <Base liquid C>
Gold (I) Cyanide Potassium 2g / L
Potassium citrate 30 g / L
Sodium ascorbate 2g / L
シアン化金（Ｉ）カリウム ２ｇ／Ｌ
クエン酸カリウム ３０ｇ／Ｌ
アスコルビン酸ナトリウム ２ｇ／Ｌ <Base liquid C>
Gold (I) Cyanide Potassium 2g / L
Potassium citrate 30 g / L
Sodium ascorbate 2g / L
［銅溶出量の評価］
各実施例及び各比較例で調製した無電解金めっき液を８５℃に加熱し、無電解金めっき液１００ｍＬに対して、２．０ｃｍ×２．５ｃｍの銅平板３枚を浸漬した後、無電解金めっき液を室温になるまで冷ました。
なお、使用した銅平板を無解金めっき液に浸漬する前に、表２に示す処理を施した。 [Evaluation of copper elution amount]
The electroless gold plating solution prepared in each Example and each comparative example was heated to 85 ° C., and three 2.0 cm × 2.5 cm copper flat plates were immersed in 100 mL of the electroless gold plating solution, and then none. The electrolytic gold plating solution was cooled to room temperature.
Before immersing the used copper flat plate in the unsolved gold plating solution, the treatment shown in Table 2 was performed.
各実施例及び各比較例で調製した無電解金めっき液を８５℃に加熱し、無電解金めっき液１００ｍＬに対して、２．０ｃｍ×２．５ｃｍの銅平板３枚を浸漬した後、無電解金めっき液を室温になるまで冷ました。
なお、使用した銅平板を無解金めっき液に浸漬する前に、表２に示す処理を施した。 [Evaluation of copper elution amount]
The electroless gold plating solution prepared in each Example and each comparative example was heated to 85 ° C., and three 2.0 cm × 2.5 cm copper flat plates were immersed in 100 mL of the electroless gold plating solution, and then none. The electrolytic gold plating solution was cooled to room temperature.
Before immersing the used copper flat plate in the unsolved gold plating solution, the treatment shown in Table 2 was performed.
室温になった無電解金めっき液をメスフラスコで正確に１００ｍＬにメスアップし撹拌して均質化した後、プラズマ発光分光分析装置ＩＣＰＳ－７５１０（株式会社島津製作所製）にて銅濃度の定量を行ない、銅溶出量を評価した。結果を表１に示す。
After the electroless gold plating solution at room temperature is accurately measured in a volumetric flask to 100 mL and stirred to homogenize, the copper concentration is quantified with the plasma emission spectroscopic analyzer ICPS-7510 (manufactured by Shimadzu Corporation). The copper elution amount was evaluated. The results are shown in Table 1.
［めっき積層体の作製］
ガラスクロスエポキシ材（ＦＲ－４）に銅箔を張り付け、ソルダーレジストにてφ０．５ｍｍ径の開口を設けた基板（４０ｍｍ×４０ｍｍ×１ｍｍｔ）を被めっき体として、表３の工程にてめっき積層体を作製した。無電解金めっきには、各実施例で調製した無電解金めっき液を使用した。 [Preparation of plated laminate]
A substrate (40 mm × 40 mm × 1 mmt) in which a copper foil is attached to a glass cloth epoxy material (FR-4) and an opening having a diameter of 0.5 mm is provided with a solder resist is used as a plated body, and plating is laminated in the process of Table 3. The body was made. For electroless gold plating, the electroless gold plating solution prepared in each example was used.
ガラスクロスエポキシ材（ＦＲ－４）に銅箔を張り付け、ソルダーレジストにてφ０．５ｍｍ径の開口を設けた基板（４０ｍｍ×４０ｍｍ×１ｍｍｔ）を被めっき体として、表３の工程にてめっき積層体を作製した。無電解金めっきには、各実施例で調製した無電解金めっき液を使用した。 [Preparation of plated laminate]
A substrate (40 mm × 40 mm × 1 mmt) in which a copper foil is attached to a glass cloth epoxy material (FR-4) and an opening having a diameter of 0.5 mm is provided with a solder resist is used as a plated body, and plating is laminated in the process of Table 3. The body was made. For electroless gold plating, the electroless gold plating solution prepared in each example was used.
［金めっき層膜厚の測定］
作製しためっき積層体における金めっき層の厚さを、蛍光Ｘ線分光分析装置（ＦＴ－１５０、（株）日立ハイテクサイエンス製）により測定した。結果を表１に示す。 [Measurement of gold plating layer film thickness]
The thickness of the gold-plated layer in the produced plated laminate was measured by a fluorescent X-ray spectrophotometer (FT-150, manufactured by Hitachi High-Tech Science Co., Ltd.). The results are shown in Table 1.
作製しためっき積層体における金めっき層の厚さを、蛍光Ｘ線分光分析装置（ＦＴ－１５０、（株）日立ハイテクサイエンス製）により測定した。結果を表１に示す。 [Measurement of gold plating layer film thickness]
The thickness of the gold-plated layer in the produced plated laminate was measured by a fluorescent X-ray spectrophotometer (FT-150, manufactured by Hitachi High-Tech Science Co., Ltd.). The results are shown in Table 1.
［金めっき層の外観の評価］
作製しためっき積層体のめっき開口部を、光学顕微鏡で１０倍の倍率で観測し、ムラなく金色だった場合、「正常」、橙色や茶色だった場合又はムラがあった場合、「不良」と判定した。結果を表１に示す。 [Evaluation of the appearance of the gold plating layer]
The plating opening of the prepared plated laminate was observed with an optical microscope at a magnification of 10 times, and if it was evenly golden, it was "normal", and if it was orange or brown, or if it was uneven, it was considered "defective". Judged. The results are shown in Table 1.
作製しためっき積層体のめっき開口部を、光学顕微鏡で１０倍の倍率で観測し、ムラなく金色だった場合、「正常」、橙色や茶色だった場合又はムラがあった場合、「不良」と判定した。結果を表１に示す。 [Evaluation of the appearance of the gold plating layer]
The plating opening of the prepared plated laminate was observed with an optical microscope at a magnification of 10 times, and if it was evenly golden, it was "normal", and if it was orange or brown, or if it was uneven, it was considered "defective". Judged. The results are shown in Table 1.
特定縮合環化合物を含有する本発明の無電解金めっき液は、銅の溶出がほとんどなく、良質な金めっき層を形成することができた。
The electroless gold plating solution of the present invention containing the specific fused ring compound was able to form a high-quality gold plating layer with almost no elution of copper.
本発明の無電解金めっき液は、特定縮合環化合物を含有することから、ニッケル皮膜等の下地に対して金めっき皮膜を形成する際に、銅素材からの銅の溶出が発生しにくいので、広く電子部品の接続端子部等の金めっき皮膜形成に使用されるものである。
Since the electroless gold plating solution of the present invention contains a specific condensed ring compound, it is difficult for copper to elute from the copper material when forming a gold plating film on a base such as a nickel film. It is widely used to form a gold-plated film for connection terminals of electronic parts.
Since the electroless gold plating solution of the present invention contains a specific condensed ring compound, it is difficult for copper to elute from the copper material when forming a gold plating film on a base such as a nickel film. It is widely used to form a gold-plated film for connection terminals of electronic parts.
Claims (13)
- 水溶性金塩と、環中に窒素原子を有する縮合環化合物とを含有することを特徴とする無電解金めっき液。 An electroless gold plating solution characterized by containing a water-soluble gold salt and a condensed ring compound having a nitrogen atom in the ring.
- 前記縮合環化合物が、ベンゼン環又はピリジン環と、窒素原子を有する複素五員環とが縮合した縮合環化合物である請求項１に記載の無電解金めっき液。 The electroless gold plating solution according to claim 1, wherein the condensed ring compound is a condensed ring compound in which a benzene ring or a pyridine ring and a complex five-membered ring having a nitrogen atom are condensed.
- 前記縮合環化合物が、環中に炭素原子でない原子を２個以上有する縮合環化合物である請求項１又は請求項２に記載の無電解金めっき液。 The electroless gold plating solution according to claim 1 or 2, wherein the condensed ring compound is a condensed ring compound having two or more atoms that are not carbon atoms in the ring.
- 前記縮合環化合物が、炭素数１～６のアルキル基、メルカプト基、ヒドロキシ基、カルボキシ基、ニトロ基及びハロゲン基からなる群より選ばれた１種以上の置換基を有する縮合環化合物である請求項１ないし請求項３の何れかの請求項に記載の無電解金めっき液。 Claimed that the fused ring compound is a fused ring compound having one or more substituents selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a mercapto group, a hydroxy group, a carboxy group, a nitro group and a halogen group. The electroless gold plating solution according to any one of claims 1 to 3.
- 更に、キレート剤を含有する請求項１ないし請求項４の何れかの請求項に記載の無電解金めっき液。 The electroless gold plating solution according to any one of claims 1 to 4, further comprising a chelating agent.
- 前記キレート剤が、分子内にイミノ２酢酸構造を有するキレート剤及びメチレンホスホン酸構造を有するキレート剤からなる群より選ばれた１種以上のキレート剤を含む請求項５に記載の無電解金めっき液。 The electroless gold plating according to claim 5, wherein the chelating agent contains one or more chelating agents selected from the group consisting of a chelating agent having an iminodiacetic acid structure and a chelating agent having a methylenephosphonic acid structure in the molecule. liquid.
- 更に、緩衝剤を含有する請求項１ないし請求項６の何れかの請求項に記載の無電解金めっき液。 The electroless gold plating solution according to any one of claims 1 to 6, further comprising a buffer.
- 前記緩衝剤が、亜硫酸及び亜リン酸並びにそれらの塩からなる群より選ばれた１種以上の化合物を含む請求項７に記載の無電解金めっき液。 The electroless gold plating solution according to claim 7, wherein the buffering agent contains one or more compounds selected from the group consisting of sulfurous acid, phosphorous acid, and salts thereof.
- 水と水溶性金塩を添加することによって無電解金めっき液を調製するための無電解金めっき液調製用組成物であって、請求項１ないし請求項８の何れかの請求項に記載の縮合環化合物を含有することを特徴とする無電解金めっき液調製用組成物。 The composition for preparing an electroless gold plating solution for preparing an electroless gold plating solution by adding water and a water-soluble gold salt, according to any one of claims 1 to 8. A composition for preparing a electroless gold plating solution, which comprises a fused ring compound.
- 粉末状である請求項９に記載の無電解金めっき液調製用組成物。 The composition for preparing an electroless gold plating solution according to claim 9, which is in the form of powder.
- 請求項１ないし請求項８の何れかの請求項に記載の無電解金めっき液を使用して、無電解金めっき皮膜を製造することを特徴とする無電解めっき皮膜の製造方法。 A method for producing an electroless plating film, which comprises producing an electroless gold plating film using the electroless gold plating solution according to any one of claims 1 to 8.
- 電子部品の製造方法であって、該電子部品が、請求項１１に記載の無電解金めっき皮膜の製造方法により製造された無電解金めっき皮膜を有することを特徴とする電子部品の製造方法。 A method for manufacturing an electronic component, wherein the electronic component has an electroless gold plating film manufactured by the method for manufacturing an electroless gold plating film according to claim 11.
- 電子部品の製造方法であって、請求項１ないし請求項８の何れかの請求項に記載の無電解金めっき液を使用して、無電解金めっき皮膜を形成させる工程を有することを特徴とする電子部品の製造方法。 It is a method for manufacturing an electronic component, and is characterized by having a step of forming an electrolytic gold plating film by using the electrolytic gold plating solution according to any one of claims 1 to 8. How to manufacture electronic components.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03215677A (en) * | 1990-01-18 | 1991-09-20 | N E Chemcat Corp | Electroless gold plating solution |
| JP2003221674A (en) * | 2002-01-30 | 2003-08-08 | Kanto Chem Co Inc | Electroless gold plating liquid |
| JP2005105318A (en) * | 2003-09-29 | 2005-04-21 | Ne Chemcat Corp | Electroless gold-plating liquid |
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2021
- 2021-12-07 WO PCT/JP2021/044917 patent/WO2022124303A1/en active Application Filing
- 2021-12-07 JP JP2022568291A patent/JPWO2022124303A1/ja active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03215677A (en) * | 1990-01-18 | 1991-09-20 | N E Chemcat Corp | Electroless gold plating solution |
| JP2003221674A (en) * | 2002-01-30 | 2003-08-08 | Kanto Chem Co Inc | Electroless gold plating liquid |
| JP2005105318A (en) * | 2003-09-29 | 2005-04-21 | Ne Chemcat Corp | Electroless gold-plating liquid |
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