CN118127579A - Gold displacement prevention additive and preparation method and application thereof - Google Patents
Gold displacement prevention additive and preparation method and application thereof Download PDFInfo
- Publication number
- CN118127579A CN118127579A CN202211536628.4A CN202211536628A CN118127579A CN 118127579 A CN118127579 A CN 118127579A CN 202211536628 A CN202211536628 A CN 202211536628A CN 118127579 A CN118127579 A CN 118127579A
- Authority
- CN
- China
- Prior art keywords
- gold
- composition
- plating
- salts
- placeholder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 142
- 239000010931 gold Substances 0.000 title claims abstract description 142
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 239000000654 additive Substances 0.000 title claims abstract description 37
- 238000006073 displacement reaction Methods 0.000 title claims abstract description 32
- 230000000996 additive effect Effects 0.000 title claims abstract description 26
- 230000002265 prevention Effects 0.000 title abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000007747 plating Methods 0.000 claims abstract description 111
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000003839 salts Chemical class 0.000 claims abstract description 21
- 239000003381 stabilizer Substances 0.000 claims abstract description 19
- 150000001413 amino acids Chemical class 0.000 claims abstract description 16
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 16
- 239000002270 dispersing agent Substances 0.000 claims abstract description 15
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000002462 imidazolines Chemical class 0.000 claims abstract description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 7
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 7
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000010199 sorbic acid Nutrition 0.000 claims abstract description 7
- 239000004334 sorbic acid Substances 0.000 claims abstract description 7
- 229940075582 sorbic acid Drugs 0.000 claims abstract description 7
- 229940083254 peripheral vasodilators imidazoline derivative Drugs 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 57
- 239000000203 mixture Substances 0.000 claims description 48
- -1 nitrogen heterocyclic compounds Chemical class 0.000 claims description 19
- 238000009713 electroplating Methods 0.000 claims description 18
- 235000001014 amino acid Nutrition 0.000 claims description 15
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- WHHYMBKESAOOSX-UHFFFAOYSA-N 1,3-benzoxazole-2-carboxamide Chemical compound C1=CC=C2OC(C(=O)N)=NC2=C1 WHHYMBKESAOOSX-UHFFFAOYSA-N 0.000 claims description 4
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 claims description 4
- GCZZOZBWAZHCAN-UHFFFAOYSA-N 1-phenyl-3-(1,3-thiazol-2-yl)thiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=NC=CS1 GCZZOZBWAZHCAN-UHFFFAOYSA-N 0.000 claims description 4
- UYWWLYCGNNCLKE-UHFFFAOYSA-N 2-pyridin-4-yl-1h-benzimidazole Chemical compound N=1C2=CC=CC=C2NC=1C1=CC=NC=C1 UYWWLYCGNNCLKE-UHFFFAOYSA-N 0.000 claims description 4
- VNFYMAPAENTMMO-UHFFFAOYSA-N 5-chloro-2-methylquinoline Chemical compound ClC1=CC=CC2=NC(C)=CC=C21 VNFYMAPAENTMMO-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 229940008075 allyl sulfide Drugs 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000006850 spacer group Chemical group 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 2
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 2
- CHHHXKFHOYLYRE-UHFFFAOYSA-M 2,4-Hexadienoic acid, potassium salt (1:1), (2E,4E)- Chemical compound [K+].CC=CC=CC([O-])=O CHHHXKFHOYLYRE-UHFFFAOYSA-M 0.000 claims description 2
- LCYOFVYHDBWYSI-UHFFFAOYSA-N 2-Ethyl-4,5-Dimethyloxazole Chemical compound CCC1=NC(C)=C(C)O1 LCYOFVYHDBWYSI-UHFFFAOYSA-N 0.000 claims description 2
- VGRVKVGGUPOCMT-UHFFFAOYSA-N 2-Ethyl-4-methylthiazole Chemical compound CCC1=NC(C)=CS1 VGRVKVGGUPOCMT-UHFFFAOYSA-N 0.000 claims description 2
- KIGMUEGDKXKNBK-UHFFFAOYSA-N 3-(4,5-dihydroimidazol-1-yl)propanoic acid Chemical group OC(=O)CCN1CCN=C1 KIGMUEGDKXKNBK-UHFFFAOYSA-N 0.000 claims description 2
- FVUXKUDCXYMMEE-UHFFFAOYSA-N 5-benzyl-1,3-oxazole Chemical compound C=1C=CC=CC=1CC1=CN=CO1 FVUXKUDCXYMMEE-UHFFFAOYSA-N 0.000 claims description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 2
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 claims description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 235000018417 cysteine Nutrition 0.000 claims description 2
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 2
- 229960003067 cystine Drugs 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 235000010235 potassium benzoate Nutrition 0.000 claims description 2
- 239000004300 potassium benzoate Substances 0.000 claims description 2
- 229940103091 potassium benzoate Drugs 0.000 claims description 2
- 235000010241 potassium sorbate Nutrition 0.000 claims description 2
- 239000004302 potassium sorbate Substances 0.000 claims description 2
- 229940069338 potassium sorbate Drugs 0.000 claims description 2
- LEHYMIDUFPRGJC-UHFFFAOYSA-N sulfanylthiourea Chemical compound NC(=S)NS LEHYMIDUFPRGJC-UHFFFAOYSA-N 0.000 claims description 2
- 150000003536 tetrazoles Chemical class 0.000 claims description 2
- 125000000101 thioether group Chemical group 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 6
- 150000001336 alkenes Chemical group 0.000 claims 1
- 125000003342 alkenyl group Chemical group 0.000 claims 1
- 150000004030 azacyclic compounds Chemical class 0.000 abstract description 7
- 238000001556 precipitation Methods 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 description 35
- 238000009472 formulation Methods 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 28
- 238000006467 substitution reaction Methods 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 239000010949 copper Substances 0.000 description 11
- 230000007797 corrosion Effects 0.000 description 11
- 238000005260 corrosion Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 230000008021 deposition Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000002390 adhesive tape Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 230000002401 inhibitory effect Effects 0.000 description 5
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- MSNOMDLPLDYDME-UHFFFAOYSA-N gold nickel Chemical group [Ni].[Au] MSNOMDLPLDYDME-UHFFFAOYSA-N 0.000 description 4
- MXZVHYUSLJAVOE-UHFFFAOYSA-N gold(3+);tricyanide Chemical compound [Au+3].N#[C-].N#[C-].N#[C-] MXZVHYUSLJAVOE-UHFFFAOYSA-N 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000012797 qualification Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 150000002343 gold Chemical class 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- SFOSJWNBROHOFJ-UHFFFAOYSA-N cobalt gold Chemical compound [Co].[Au] SFOSJWNBROHOFJ-UHFFFAOYSA-N 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000005187 foaming Methods 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
- 239000002932 luster Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention provides a gold displacement prevention additive, a preparation method and application thereof, wherein the gold displacement prevention additive comprises a placeholder, a dispersing agent and a stabilizing agent, the placeholder is selected from one or two of an azacyclic compound and amino acid, the dispersing agent comprises potassium hydroxide, the stabilizing agent is selected from one or more of sorbic acid, salts thereof, benzoic acid, salts thereof and imidazoline derivatives, and the gold displacement prevention additive is used for an electrogilding process. The gold displacement preventing additive can effectively prevent gold and nickel displacement, maintain plating solution stability for a long time, inhibit gold precipitation, and has simple preparation method, and is not limited by the pH of the gold plating solution and the components of the gold plating bath solution when in use.
Description
Technical Field
The invention belongs to the technical field of surface treatment of electronic components, and particularly relates to a gold displacement prevention additive.
Background
Gold has stable chemical properties, low resistivity, easy welding, high temperature resistance and certain wear resistance (such as hard gold doped with a small amount of cobalt and nickel elements). Gold is therefore widely used as a functional plating material for electronic components. Copper or copper alloy is generally used as a substrate for electronic components, however, when gold is deposited on the surface of copper, copper diffuses into the gold film. Therefore, when gold plating is used as the surface treatment of copper, nickel plating is often performed on the copper surface as a barrier layer of the copper substrate, followed by gold plating on the surface of the nickel plating layer.
The traditional gold plating comprises two kinds of cyanide gold plating and cyanide-free gold plating according to the process characteristics. Cyanide gold plating is the most widely used gold plating technique with the earliest history at present. In the cyanide gold plating solution, cyanide ions and monovalent gold ions form stable ligands, so that the plating solution is stable and the plating quality is excellent. However, the cyanide gold plating solution contains extremely toxic cyanide, which threatens the safety production of operators and causes environmental pollution. With the increase of environmental protection consciousness, cyanide-free gold plating has become a trend. Cyanide-free gold plating mainly comprises citric acid type and sulfite type systems, but cyanide-free gold plating solutions do not contain cyanide compounds which form stable ligands with gold in aqueous solutions, so that the plating solutions are unstable and easy to decompose, gold is abnormally precipitated on plating tanks or jigs, gold salts are wasted, and the plating operation is hindered. The stability of sulfurous acid subtype is worse, and at present, citric acid type gold plating is the mainstream.
In addition, due to the potential difference of nickel and gold, when the nickel plating substrate of the electronic element is plated with gold, the traditional gold plating solution inevitably generates gold and nickel substitution, and the gold layer obtained by the gold and nickel substitution has loose and porous structure and is doped in the electroplated gold layer, so that the compactness, corrosion resistance and binding force of the gold plating layer are seriously affected. In order to solve the problem of gold-nickel substitution in electroplating, a cyanide electrolytic hard gold plating solution is disclosed in the prior art, such as CN107709628a, which can inhibit gold substitution reaction on the bottom of a nickel electrode, but cannot be completely inhibited, and a thiol-containing compound is adsorbed too strongly on the gold surface, which may cause miss-plating, and still has hidden danger in practical application. CN113832509a discloses a sulfite gold plating solution, which contains organic phosphonic acid, electroplating Jin Shiyou machine phosphonic acid can selectively adsorb on nickel surface to form a barrier layer, and effectively inhibit nickel-gold substitution, thereby realizing preparation of gold plating layer with uniform appearance and good binding force by cyanide-free electroplated gold. However, the organic phosphonic acid substances are extremely strong in complexation and often have side reactions, so that the stress in the gold plating layer is large, the plating effect is affected, and sulfite ions in the gold plating solution and Jin Peiwei are extremely easy to oxidize by oxygen in the solution or oxygen in the atmosphere, so that the concentration of the organic phosphonic acid substances is reduced, the oxidation stability of gold complexes is reduced, and the gold plating solution is decomposed.
In summary, in order to solve the defects existing in the prior art, a technology capable of effectively preventing gold and nickel replacement, maintaining the stability of the plating solution for a long time and inhibiting gold precipitation is sought, and the technology has great application prospect and practical significance.
Disclosure of Invention
The present invention provides a composition comprising a spacer, a dispersant and a stabilizer.
In some embodiments, the placeholder is selected from one or both of an azacyclic compound and an amino acid.
In some embodiments, the dispersant comprises potassium hydroxide.
In some embodiments, the stabilizer is selected from one or more of sorbic acid and salts thereof, benzoic acid and salts thereof, imidazoline derivatives.
In some embodiments, the composition is a gold displacement preventing additive.
In some embodiments, the composition comprises the following components in parts by weight: the space occupying agent is 5-12 parts by weight, the dispersant is 3-8 parts by weight, and the stabilizer is 0-5 parts by weight.
In some embodiments, the stabilizer is 1 to 5 parts by weight.
In some embodiments, the mass ratio of the azacyclic compound to the amino acid in the spacer is 1.6-3:1.
In some embodiments, the mass ratio of the azacyclic compound to the amino acid in the spacer is 2-3:1.
In some embodiments, the azacyclic compound is an azole compound, and the azole compound is one or more selected from oxazole and its derivatives, imidazole and its derivatives, thiazole and its derivatives, tetrazole and its derivatives.
In some embodiments, the azole compound is selected from one or more of 2-ethyl-4-methyl-thiazole, 2-ethyl-4, 5-dimethyl-oxazole.
In some embodiments, the azole compound contains one or more of phenyl, benzyl, alkylene, mercapto, thiourea, thioether, and amide groups.
In some embodiments, the azole compound contains a phenyl group and further contains one or more of a benzyl group, an alkylene group, a mercapto group, a thiourea group, a thioether group, and an amide group.
In some embodiments, the azacyclic compound is selected from one or a combination of several of 1-vinylimidazole, 5-benzyloxazole, 1-phenyl-5-mercapto-tetrazole, 2-benzimidazole allylsulfide, 1-phenyl-3- (2-thiazolyl) -2-thiourea, 2-benzoxazole carboxamide.
In some embodiments, the azacyclic compound is selected from one or more of 1-phenyl-5-mercapto-tetrazole, 2-benzimidazole allyl sulfide, 1-phenyl-3- (2-thiazolyl) -2-thiourea, 2-benzoxazole carboxamide.
In some embodiments, the amino acid is a sulfur-containing amino acid.
In some embodiments, the sulfur-containing amino acid is selected from one or both of cysteine and cystine.
In some embodiments, the stabilizer is selected from one or more of sorbic acid and salts thereof, benzoic acid and salts thereof, imidazoline derivatives.
In some embodiments, the sorbic acid and salts thereof are potassium sorbate.
In some embodiments, the benzoic acid and salts thereof are potassium benzoate.
In some embodiments, the imidazoline derivative is one or both of a carboxyalkyl imidazoline and a polyoxyethylene ether.
In some embodiments, the imidazoline derivative is a carboxyalkyl imidazoline and the alkyl is a C1-C5 alkyl.
In some embodiments, the imidazoline derivative is carboxyethyl imidazoline.
In some embodiments, the compositions of the present invention further comprise water.
In some embodiments, the water is present in an amount of 75 to 91 parts by weight.
The invention also provides a preparation method of the gold displacement prevention additive.
In some embodiments, the method of making comprises the steps of: adding the placeholder, the dispersing agent, the stabilizing agent and the pure water into a container, heating and stirring to obtain the product.
In some embodiments, the method of making comprises the steps of: adding the dispersing agent and pure water into a container, stirring and dissolving, and heating the solution to 50 ℃; adding the placeholder into a container, and heating at 50 ℃ until the obtained mixed solution is completely melted; and finally, adding the stabilizer into a container, and heating at 50 ℃ until the obtained mixed solution is completely melted to obtain the product.
The gold displacement preventing additive provided by the invention can be applied to an electro-gold plating process.
In some embodiments, the gold electroplating process is electroplating gold on a nickel plating layer;
In some embodiments, the application comprises the steps of: based on the actual content of gold element in the gold plating bath solution, adding 100ml of the composition into each 68 g of gold element, and stirring uniformly.
Compared with the prior art, the invention has the following beneficial effects:
(1) Whether the gold plating solution has current or not, the replacement of gold on the substrate nickel metal can be prevented, the compactness and the binding force of the gold layer are improved, and the corrosion resistance of the gold layer is improved;
(2) Maintaining the stability of the plating solution, prolonging the service life of the plating solution, and inhibiting gold precipitation on equipment such as a gold plating tank, a jig and the like;
(3) When the gold displacement preventing additive provided by the invention is used, the gold element in the bath solution is taken as a reference, and the gold displacement preventing additive is added into the gold plating bath solution according to a proportion and stirred uniformly, so that the gold displacement preventing additive is not limited by the pH value of the gold plating solution and the components of the gold plating bath solution, is suitable for any cyanide-containing or cyanide-free gold plating solution, and has the advantages of wide application range and simplicity and convenience in operation.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples, which do not represent limitations on the scope of the present invention. Some insubstantial modifications and adaptations of the invention based on the inventive concept by others remain within the scope of the invention.
Example 1 formulation and method of making an anti-gold displacement additive
TABLE 1 gold displacement preventing additive formulations
The preparation method of the gold displacement prevention additive comprises the following steps: the additives were prepared according to 8 formulations of table 1, respectively, and the specific steps were: adding the dispersing agent and pure water into a container, stirring and dissolving, and heating the solution to 50 ℃; adding the placeholder into a container, and heating at 50 ℃ until the obtained mixed solution is completely melted; and finally, adding the stabilizer into a container, and heating at 50 ℃ until the obtained mixed solution is completely melted to obtain the gold displacement preventing additive.
Example 2 evaluation of gold-nickel substitution inhibiting ability of gold-substitution inhibiting additive
Testing a workpiece: copper is electroplated with a bright nickel workpiece, nickel layer thickness 110u "(2.75 μm).
Gold plating bath solution: the main stream of citric acid type gold-cobalt cyanide-free gold plating solution in the current market is selected, and the gold content of the gold plating solution in the embodiment is 2g/L, and the pH=4.2.
The testing method comprises the following steps: the gold displacement preventing additives of the formulations 1 to 8 of the example 1 were added to the gold plating bath solution in a ratio of 3ml/L, respectively, and stirred uniformly. The copper nickel plating work piece was immersed in the gold plating bath solution without being energized at 50 c, left for 1min under magnetic stirring, and then the thickness of the displacement gold was measured with XRF. Meanwhile, a blank control group is arranged, namely the gold plating solution is not added with the gold substitution preventing additive, and the rest test conditions are the same. The test results are shown in Table 2.
TABLE 2 test results of the ability of gold-nickel substitution inhibiting additives to inhibit gold substitution
Note that: 1 μm.apprxeq.40 u ', u' is a thickness unit commonly used in the industry, and is read as Michael or micro-inch.
EXAMPLE 3 evaluation of the ability of gold displacement prevention additive to improve coating quality
Testing a workpiece: as in example 2.
Gold plating bath solution: as in example 2.
The testing method comprises the following steps: the gold displacement preventing additives of the formulations 1 to 8 of the example 1 were added to the gold plating bath solution in a ratio of 3ml/L, respectively, and stirred uniformly. Immersing the copper nickel-plated workpiece into the gold plating bath solution for electroplating. Electroplating parameters: plating temperature 50 ℃, current density 10A/dm 2, ph=4.2, plating for 30 seconds, and measuring gold layer thickness with XRF. Meanwhile, a blank control group is arranged, namely the gold plating solution is not added with the gold substitution preventing additive, and the rest test conditions are the same. The test results are shown in Table 3.
The test evaluation criteria were as follows:
(1) Appearance of the plating layer: the coating is required to be bright, golden yellow and smooth, and the coating is fine and not rough in crystallization. The pass is marked as "v", and the fail is marked as "x".
(2) Corrosion resistance of the plating: the corrosion resistance of the plating layer is evaluated by neutral salt fog, and the specific test method refers to GB/T2423.17-2008 test standard. The neutral salt spray test period was set to 24 hours considering that the sample was a thin gold plating. The plating is required to be corrosion-free. Observations were made every 3 hours.
(3) Coating binding force: the neutral salt spray test is firstly carried out on the workpiece, and after 24h, 32h, 40h and 48h of salt spray, the 3M adhesive tape tearing test is carried out on the plating layer. The specific method comprises the following steps: the 3M600 adhesive tape is firmly stuck on the surface of a tested workpiece, the adhesive tape is tightly attached to the surface without bubbles, one end of the adhesive tape is grasped by hands after 2 minutes, the adhesive tape is instantly torn up by the force of a vertical receiving side (90 degrees), and the phenomenon that a plating layer on the surface of the workpiece is free from foaming and falling is required.
TABLE 3 test results of the ability of gold displacement prevention additives to improve coating quality
EXAMPLE 4 Effect of gold displacement prevention additive on electroplating deposition Rate
Testing a workpiece: as in example 2.
Gold plating bath solution: as in example 2.
The testing method comprises the following steps: the gold displacement preventing additives of the formulations 1 to 8 of the example 1 were added to the gold plating bath solution in a ratio of 3ml/L, respectively, and stirred uniformly. Immersing the copper nickel-plated workpiece into the gold plating bath solution for electroplating. Electroplating parameters: plating temperature 50 ℃, current density 10A/dm 2, ph=4.2, plating for 30 seconds, and measuring gold layer thickness with XRF. Meanwhile, a blank control group is arranged, namely the gold plating solution is not added with the invention, and the rest test conditions are the same.
Test evaluation criteria: deposition rate of gold layer: compared with a blank control group, the deposition thickness of the gold plating layer is reduced by less than 5 percent, the gold plating layer is qualified, the qualification is marked as 'V', and the disqualification is marked as 'X'. The test results are shown in Table 4.
TABLE 4 Effect of gold displacement prevention additives on deposition Rate
EXAMPLE 5 Effect of gold displacement prevention additive on bath stability
Gold plating bath solution: same as in example 2
The testing method comprises the following steps: the gold displacement preventing additives of the formulations 1 to 8 of the example 1 were added to the gold plating bath solution in a ratio of 3ml/L, respectively, and stirred uniformly. A blank control group was also set to evaluate the effect of the invention on bath stability, and the test results are shown in Table 5.
Test evaluation criteria: evaluation of load stability at normal temperature: the natural environment is at the normal temperature of 25 ℃, the plating solution is continuously plated for 2.5 hours per day at the temperature of 50 ℃ for 60 days, and the plating solution is required to be free from turbidity and gold precipitation. Observations were recorded every 15 days. (during the period, the gold plating solution is regularly added, the gold content is kept at 2g/L, and the gold substitution preventing additive is added proportionally), the qualification is marked as 'V', and the disqualification is marked as 'X'. The test results are shown in Table 5.
TABLE 5 Effect of gold displacement prevention additives on bath stability
Comparative example 1 Effect of different amounts of the Components on the Properties of the invention
Table 6 comparative formulations 1-6
Table 6 shows the specific compositions of comparative formulations 1-6 of the present invention. The invention was prepared according to 6 comparative formulations of table 6. Comparative formulations 1-6 were prepared in the same manner as in example 1.
Testing a workpiece: same as in example 2
Gold plating bath solution: as in example 2.
The testing method comprises the following steps: the gold displacement preventing additives of the comparative formulas 1 to 6 of comparative example 1 were added to the gold plating bath solution at a ratio of 3ml/L, respectively, and stirred uniformly. Immersing the copper nickel-plated workpiece into the gold plating bath solution for electroplating. Electroplating parameters: plating temperature 50 ℃, current density 10A/dm 2, ph=4.2, plating for 30 seconds, and measuring gold layer thickness with XRF.
The performance evaluation of the invention is as follows, the qualification is marked as 'v', and the disqualification is marked as 'x':
(1) Appearance of the plating layer: same as in example 3.
(2) Corrosion resistance of the plating: the corrosion resistance of the plating layer was evaluated by neutral salt spray. The specific test method refers to GB/T2423.17-2008 test standard, and the test period is 48 hours. The plating is required to be corrosion-free.
(3) Coating binding force: same as in example 3.
(4) Deposition rate of gold layer: same as in example 4.
(5) High temperature and high humidity load plating solution stability: the plating solution is continuously applied for 2.5 hours at the temperature of 35 ℃ and the relative humidity of 90 ℃ every day, and the period is 120 days, so that the plating solution is required to be free from turbidity, discoloration and gold precipitation. (during the period, the gold plating solution is regularly added, the gold content is kept at 2g/L, and the gold substitution preventing additive is added proportionally)
The test results are shown in Table 7.
Table 7 effect of different amounts of the components on the properties of the invention.
Comparative formulation 1: the content of the placeholder is too low, the replacement preventing capability is weak, and the corrosion resistance, the binding force and the stability are all affected.
Comparative formulation 2: the high content of the placeholder influences the deposition efficiency of the gold layer, and the appearance of the plating layer is qualified after electroplating is finished, but the thickness of the gold layer can not meet the requirement, and the corrosion resistance and the binding force of the plating layer are influenced.
Comparison formula 3: the insufficient content of the dispersing agent affects the stability of the system, and solid particles are separated out after standing in the preparation process, which is not consistent.
Comparative formulation 4: the too high content of the dispersing agent affects the pH value of the gold tank and the electroplating.
Comparative formulation 5: the plating layer performance is affected without stabilizer.
Comparative formulation 6: the content of the stabilizer is too high, so that the electroplating appearance is affected, the gold layer is not uniformly crystallized, and the gold layer has no metallic luster and is matte. The gold layer is not crystallized carefully, further affecting corrosion resistance and binding force.
Comparative example 2 Effect of the placeholder on the ability of the invention to improve coating quality
Table 8 comparative formulations 7-12
Table 8 shows the specific compositions of comparative formulations 7-12 of the present invention. The invention was prepared according to 6 comparative formulations of table 8. Comparative formulations 7-12 were prepared in the same manner as in example 1.
Testing a workpiece: as in example 2.
Gold plating bath solution: as in example 2.
The testing method comprises the following steps: the gold displacement preventing additives of the formulas 7-12 of the comparative example 2 are respectively added into the gold plating bath solution in the proportion of 3ml/L and are stirred uniformly. Immersing the copper nickel-plated workpiece into the gold plating bath solution for electroplating. Electroplating parameters: plating temperature 50 ℃, current density 10A/dm 2, ph=4.2, plating for 30 seconds, and measuring gold layer thickness with XRF. The effect of the placeholder on the ability of the invention to improve the coating quality was evaluated and the results are shown in Table 9.
(1) Appearance of the plating layer: same as in example 3.
(2) Corrosion resistance of the plating: neutral salt fog, test period is set to 72h.
(3) Coating binding force: after 72h of neutral salt fog, a 3M adhesive tape tearing test is carried out.
The test results are shown in Table 9.
TABLE 9 Effect of placeholders on the ability of the invention to improve coating quality
| Test group | Appearance of coating | Corrosion resistance of plating | Binding force of plating |
| Comparative formulation 7 | × | × | × |
| Comparative formulation 8 | √ | × | × |
| Comparative formulation 9 | √ | × | × |
| Comparative formulation 10 | √ | √ | √ |
| Comparative formulation 11 | √ | √ | √ |
| Comparative formulation 12 | × | × | × |
Remarks: the coating of comparative formulation 7 was partially missing, and the coating of comparative formulation 8 was not thick enough.
As can be seen from table 9:
When the azole in the placeholder: the amino acid (mass ratio) is too low, the substitution preventing capability is weak, and the coating performance is affected (comparative formula 9).
When the azole in the placeholder: too high an amino acid (mass ratio) affects the plating deposition rate and the plating properties are affected (comparative formulation 12).
When the mass ratio of the azoles to the amino acids in the placeholder is 1.6-3:1, the plating performance is better.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made thereto without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. A composition comprising a spacer, a dispersant and a stabilizer;
The placeholder is one or two selected from nitrogen heterocyclic compounds and amino acids;
The dispersant comprises potassium hydroxide;
The stabilizer is one or more selected from sorbic acid and salts thereof, benzoic acid and salts thereof, and imidazoline derivatives;
The composition is a gold displacement preventing additive.
2. The composition of claim 1, comprising the following components in parts by weight: the weight part of the space occupying agent is 5-12 parts, the weight part of the dispersing agent is 3-8 parts, and the weight part of the stabilizing agent is 0-5 parts;
preferably, the weight portion of the stabilizer is 1-5 portions.
3. The composition of claim 1, wherein the mass ratio of the nitrogen heterocyclic compound to the amino acid in the placeholder is 1.6-3:1;
Preferably, in the placeholder, the mass ratio of the nitrogen heterocyclic compound to the amino acid is 2-3:1.
4. The composition according to claim 1, wherein the nitrogen heterocyclic compound is an azole compound selected from one or more of oxazole and its derivatives, imidazole and its derivatives, thiazole and its derivatives, tetrazole and its derivatives;
Preferably, the azole compound is selected from one or more of 2-ethyl-4-methyl-thiazole and 2-ethyl-4, 5-dimethyl-oxazole;
Or preferably, the azole compound contains one or more of phenyl, benzyl, olefin group, sulfhydryl group, thiourea group, thioether group and amide group;
More preferably, the azole compound contains phenyl and further contains one or more of benzyl, alkenyl, mercapto, thiourea, thioether and amide groups;
Or preferably, the nitrogen heterocyclic compound is selected from one or more of 1-vinylimidazole, 5-benzyl oxazole, 1-phenyl-5-mercapto-tetrazole, 2-benzimidazole allyl sulfide, 1-phenyl-3- (2-thiazolyl) -2-thiourea and 2-benzoxazole carboxamide;
Or more preferably, the nitrogen heterocyclic compound is selected from one or more of 1-phenyl-5-mercapto-tetrazole, 2-benzimidazole allyl sulfide, 1-phenyl-3- (2-thiazolyl) -2-thiourea and 2-benzoxazole carboxamide.
5. The composition of claim 1, wherein the amino acid is a sulfur-containing amino acid;
preferably, the sulfur-containing amino acid is selected from one or both of cysteine and cystine.
6. The composition of claim 1, wherein the stabilizer is one or more selected from the group consisting of sorbic acid and salts thereof, benzoic acid and salts thereof, and imidazoline derivatives;
Preferably, the sorbic acid and salts thereof are potassium sorbate;
Preferably, the benzoic acid and its salts are potassium benzoate;
Preferably, the imidazoline derivative is one or two of carboxyalkyl imidazoline and polyoxyethylene ether;
more preferably, the imidazoline derivative is a carboxyalkyl imidazoline, and the alkyl is a C1-C5 alkyl;
Still more preferably, the imidazoline derivative is carboxyethyl imidazoline.
7. The composition of any one of claims 1-6, further comprising water;
preferably, the water is 75-91 parts by weight.
8. A process for preparing the composition of any one of claims 1-7, comprising the steps of:
adding a placeholder, a dispersing agent, a stabilizing agent and pure water into a container, heating and stirring to obtain a product;
preferably, dispersing agent and pure water are added into a container, and after stirring and dissolving, the solution is heated to 50 ℃; adding the placeholder into a container, and heating at 50 ℃ until the obtained mixed solution is completely melted; and finally, adding the stabilizer into a container, and heating at 50 ℃ until the obtained mixed solution is completely melted to obtain the product.
9. Use of a composition according to any one of claims 1 to 7 or a composition obtainable by a process according to claim 8 in a gold electroplating process.
10. The use according to claim 9, wherein the electro-gold plating process is electroplating gold on a nickel plating layer;
Preferably, the application comprises the steps of: based on the actual content of gold element in the gold plating bath solution, adding 100ml of the composition into each 68 g of gold element, and stirring uniformly.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211536628.4A CN118127579A (en) | 2022-12-01 | 2022-12-01 | Gold displacement prevention additive and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211536628.4A CN118127579A (en) | 2022-12-01 | 2022-12-01 | Gold displacement prevention additive and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118127579A true CN118127579A (en) | 2024-06-04 |
Family
ID=91238299
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211536628.4A Pending CN118127579A (en) | 2022-12-01 | 2022-12-01 | Gold displacement prevention additive and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118127579A (en) |
-
2022
- 2022-12-01 CN CN202211536628.4A patent/CN118127579A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4804410A (en) | Palladium-base electroless plating solution | |
| EP2855732B1 (en) | Plating bath for electroless deposition of nickel layers | |
| US5601696A (en) | Silver plating baths and silver plating method using the same | |
| KR101502804B1 (en) | Pd and Pd-Ni electrolyte baths | |
| US9574281B2 (en) | Silver-containing alloy plating bath and method for electrolytic plating using same | |
| US5552031A (en) | Palladium alloy plating compositions | |
| US20040118317A1 (en) | Electroless gold plating solution | |
| US7300501B2 (en) | Electroless gold plating liquid | |
| JPH05222569A (en) | Silver plating solution | |
| JPH0341549B2 (en) | ||
| JP3479639B2 (en) | Electroless nickel plating solution | |
| US20050056545A1 (en) | Gold plating solution and gold plating method | |
| CN118127579A (en) | Gold displacement prevention additive and preparation method and application thereof | |
| JPS609116B2 (en) | Electrodeposition method for palladium and palladium alloys | |
| JP2021181600A (en) | Electrolytic gold alloy plating bath and electrolytic gold alloy plating method | |
| CA2769569C (en) | Tin-containing alloy plating bath, electroplating method using same, and substrate with the electroplating deposited thereon | |
| US5194139A (en) | Pretreating solution for silver plating and silver plating treating process using the solution | |
| US5549810A (en) | Bath for the electrodeposition of palladium-silver alloys | |
| JP2003268586A (en) | Gold plating electrolytic solution and gold plating method | |
| JPH06145997A (en) | Electroless gold plating liquid | |
| JP3208131B2 (en) | Palladium / iron alloy plating solution and palladium alloy plating substrate | |
| JP2011168837A (en) | Electroless gold plating liquid and gold coated film obtained by using the same | |
| US4062736A (en) | Gold and gold alloy deposition | |
| JPH0734258A (en) | Substitution type gold electroless plating liquid | |
| EP3945144B1 (en) | Electroless palladium plating bath |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination |