CN115044894B - Water-based protective agent shared by gold and tin plating layers and preparation method thereof - Google Patents
Water-based protective agent shared by gold and tin plating layers and preparation method thereof Download PDFInfo
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- CN115044894B CN115044894B CN202210712555.3A CN202210712555A CN115044894B CN 115044894 B CN115044894 B CN 115044894B CN 202210712555 A CN202210712555 A CN 202210712555A CN 115044894 B CN115044894 B CN 115044894B
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- 238000007747 plating Methods 0.000 title claims abstract description 42
- 239000003223 protective agent Substances 0.000 title claims abstract description 31
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 21
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000010931 gold Substances 0.000 title claims abstract description 21
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title description 13
- 230000007797 corrosion Effects 0.000 claims abstract description 77
- 238000005260 corrosion Methods 0.000 claims abstract description 77
- 239000000126 substance Substances 0.000 claims abstract description 24
- JVPLOXQKFGYFMN-UHFFFAOYSA-N gold tin Chemical compound [Sn].[Au] JVPLOXQKFGYFMN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 19
- 239000003112 inhibitor Substances 0.000 claims abstract description 16
- 239000004094 surface-active agent Substances 0.000 claims abstract description 16
- 239000000654 additive Substances 0.000 claims abstract description 10
- 230000000996 additive effect Effects 0.000 claims abstract description 10
- 239000012224 working solution Substances 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 13
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 12
- -1 alkyl sulfonic acid Chemical compound 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- QDCPNGVVOWVKJG-VAWYXSNFSA-N 2-[(e)-dodec-1-enyl]butanedioic acid Chemical compound CCCCCCCCCC\C=C\C(C(O)=O)CC(O)=O QDCPNGVVOWVKJG-VAWYXSNFSA-N 0.000 claims description 5
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 5
- 239000013556 antirust agent Substances 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- IYPXPGSELZFFMI-UHFFFAOYSA-N 1-phenyltetrazole Chemical compound C1=NN=NN1C1=CC=CC=C1 IYPXPGSELZFFMI-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- YTLQFZVCLXFFRK-UHFFFAOYSA-N bendazol Chemical compound N=1C2=CC=CC=C2NC=1CC1=CC=CC=C1 YTLQFZVCLXFFRK-UHFFFAOYSA-N 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 210000003298 dental enamel Anatomy 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 2
- 239000003876 biosurfactant Substances 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000006260 foam Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 37
- 238000009472 formulation Methods 0.000 description 34
- 150000003839 salts Chemical class 0.000 description 22
- 239000007921 spray Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 230000001681 protective effect Effects 0.000 description 9
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910001369 Brass Inorganic materials 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- PYIDGJJWBIBVIA-UYTYNIKBSA-N lauryl glucoside Chemical compound CCCCCCCCCCCCO[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O PYIDGJJWBIBVIA-UYTYNIKBSA-N 0.000 description 2
- 229940048848 lauryl glucoside Drugs 0.000 description 2
- 229920005792 styrene-acrylic resin Polymers 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 229910001361 White metal Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229940080421 coco glucoside Drugs 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 150000002338 glycosides Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010969 white metal Substances 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention discloses a water-soluble protective agent shared by gold-tin plating layers, which comprises the following substances in parts by mass: 5-15 parts of film forming substances; 3-8 parts of corrosion inhibitor; 20-40 parts of surfactant; 3-10 parts of film forming auxiliary agent; 2-8 parts of additive; 30-50 parts of pure water. The water-soluble protective agent solution shared by the gold and tin plating layers provided by the invention is stable in state, the working solution is free from foam, the appearance of a coated workpiece is uniform, the operation process is simple, the rapid film forming effect is realized, and the use of a high-speed continuous plating production line can be satisfied.
Description
Technical Field
The invention belongs to the field of metal coating protection, and particularly relates to a water-soluble metal coating protective agent.
Background
In recent years, high-speed continuous gold plating technology is often adopted in the field of miniature connector terminals, and the problems of thinner plating layer, poor crystallization condition, increased porosity of a gold layer, easy oxidation and color change, reduced weldability, salt mist intolerance and the like exist. Tin is a silvery white metal, is ductile, has good weldability and conductivity, and is widely applied to industries of electronics, communication, new energy sources and the like. However, tin plating is particularly susceptible to oxidative discoloration during storage, severely affecting solderability. And the tin junction of the semi-gold tin terminal is particularly easy to corrode due to the large electrode potential difference, and the plating layer at the junction has poor crystallization condition, so that the electrochemical corrosion is further accelerated by the residue of the electroplating solution, the protection difficulty is high, and the method is a serious difficulty in the protective agent industry. At present, the water-soluble protective agent on the market hardly meets the salt spray resistance requirement of the gold-tin coating at the same time, so that the solution of the problems is of great significance.
Disclosure of Invention
In view of one of the technical problems described in the foregoing, the present invention provides a water-soluble protective agent shared by gold-tin plating layers. The water-soluble protective agent solution shared by the gold and tin plating layers provided by the invention is stable in state, the working solution is free from foam, the appearance of a coated workpiece is uniform, the operation process is simple, the rapid film forming effect is realized, and the use of a high-speed continuous plating production line can be satisfied.
On one hand, the invention provides a water-soluble protective agent shared by gold-tin plating layers, which comprises the following substances in parts by mass: 5-15 parts of film forming substances; 3-8 parts of corrosion inhibitor; 20-40 parts of surfactant; 3-10 parts of film forming auxiliary agent; 2-8 parts of additive; 30-50 parts of pure water.
In particular, the film-forming materials of the present invention are unsaturated fatty acids or esters.
Specifically, the film forming material is one or a combination of more of dodecenyl succinic acid, dodecenyl succinic acid half ester or dodecenyl succinic acid ester. The fatty acid or ester substance has good film forming property, and can be adsorbed on the metal surface to form a firm protective film, so that oxidation discoloration of the gold and tin surfaces can be effectively prevented.
Preferably, the film forming material of the present invention is dodecenyl succinate.
Specifically, the corrosion inhibitor is an azacyclic substance.
Specifically, the corrosion inhibitor is one or a combination of more of imidazole compounds, azole compounds and thiazole compounds.
Preferably, the corrosion inhibitor is a combination of three of 2-mercaptobenzothiazole, 1-phenyl-1H-tetrazole and 2- (phenylmethyl) -1H-benzimidazole. The small molecular nitrogen heterocyclic substances in the corrosion inhibitor can play a role in filling, are adsorbed on the metal surface through physical and chemical effects, improve the compactness of a film layer, and have a synergistic effect when being combined with unsaturated acid and ester substances, so that the protective performance is further improved.
Specifically, the surfactant described in the present invention is a biosurfactant and a synthetic surfactant.
Specifically, the biological surfactant is a glycoside surfactant, preferably lauryl glucoside and coco glucoside; the synthetic surfactant is a nonionic hydrocarbon surfactant, and preferably one or more of fatty alcohol ethers and modified fatty alcohol ethers are compounded.
Specifically, the film forming auxiliary agent is a polymer, is selected from aqueous styrene and acrylic acid copolymer resin or modified resin thereof, preferably has a molecular weight of 1-2 ten thousand, can effectively promote film formation, further increases the compactness and uniformity of film formation, and improves the protective performance.
Specifically, the additive is one of alkyl sulfonic acid or dimerized oleic acid. The alkyl sulfonic acid is preferred, so that the corrosion resistance of the gold-tin plating layer can be further enhanced, the dehydration property of the protective agent system can be improved, and the coated workpiece is good in cleaning and free of flow marks.
In the invention, the total amount of the film forming substance and the corrosion inhibitor is 8-23%, the film forming integrity cannot be ensured due to the too low content, and the concentrated solution is easy to separate out due to the unstable placement caused by the high content. In order to ensure that the mass ratio of the compact film forming substance of the film layer to the corrosion inhibitor is 1:1-3:1.
In another aspect, the invention also provides a preparation method of the water-soluble protective agent shared by the gold-tin plating layers, wherein the preparation method comprises a preparation method of concentrated solution and a preparation method of working solution.
The preparation method of the water-soluble protective agent concentrated solution comprises the following steps: sequentially adding mercaptan substances, a surfactant, a corrosion inhibitor, an antirust agent and an additive into an enamel container according to a formula, heating to 60-70 ℃, fully stirring until the mercaptan substances, the surfactant, the corrosion inhibitor, the antirust agent and the additive are completely dissolved into transparent liquid, adding pure water according to the formula amount, and continuously stirring for 2 hours to obtain the protective agent concentrated solution.
The preparation method of the water-soluble protective agent working solution comprises the following steps: when in use, the barrel filled with the concentrated solution is placed in hot water with the temperature of about 80 ℃ to be fully melted and shaken uniformly, and then the solution is diluted into 5 percent working solution by pure water with the temperature of 50-55 ℃.
By implementing the technical scheme of the invention, the following beneficial effects can be achieved:
(1) The water-soluble protective agent shared by the gold and tin plating layers forms a semi-solid film on the metal surface, the film forming thickness does not influence conductivity, the washing effect is good, the natural color of the metal is not influenced, the oxidation of the plating layers can be effectively prevented, and the weldability is ensured.
(2) The water-soluble protective agent for the common use of the gold-tin plating layers can meet the requirement of the common use of the gold-tin plating layers, can effectively solve the problem that the gold-tin junction is easy to corrode and difficult to protect, and meets the requirement of tin plating layer salt fog for 24 hours.
(3) The water-soluble protective agent shared by the gold and tin plating layers can be rapidly formed into a film, and a compact protective film can be formed on the surface of the plating layer within 3-5 seconds, so that the requirement of a high-speed continuous electroplating production line is met.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The disclosure of the present invention will be further understood in conjunction with the following detailed description of the preferred embodiments of the invention, including examples.
The preparation method of the water-soluble protective agent shared by the gold-tin plating layers in the embodiment of the example comprises the preparation method of the concentrated solution and the preparation method of the working solution.
The preparation method of the protective agent concentrated solution comprises the following steps: sequentially adding mercaptan substances, a surfactant, a corrosion inhibitor, an antirust agent and an additive into an enamel container according to a formula, heating to 60-70 ℃, fully stirring until the mercaptan substances, the surfactant, the corrosion inhibitor, the antirust agent and the additive are completely dissolved into transparent liquid, adding pure water according to the formula amount, and continuously stirring for 2 hours to obtain the protective agent concentrated solution.
The preparation method of the protective agent working solution comprises the following steps: when in use, the barrel filled with the concentrated solution is placed in hot water with the temperature of about 80 ℃ to be fully melted and shaken uniformly, and then the solution is diluted into 5 percent working solution by pure water with the temperature of 50-55 ℃.
The formula of the water-soluble protective agent shared by the gold and tin plating layers is calculated according to the total weight of 100kg, and the specific formula is shown in Table 1.
Table 1: formula of water-soluble protective agent shared by gold and tin plating layers
Example 1: salt spray resistance test on thin gold strips requires 48 hours of salt spray passing.
A base material of the belt material: the phosphor brass base gold plating (thickness is 0.025-0.03 mu m), the above work piece is immersed in the working solution for 3s, taken out, washed 1 time with water at normal temperature, and dried in an oven at 80 ℃. After 24 hours of standing, a neutral salt fog experiment is carried out, the specific operation is carried out according to GB/T2423.117-93 standard, observation is carried out every 12 hours, and the results are shown in Table 2.
Table 2: salt spray resistance test 48h result on thin gold strip
| Formulation of | Corrosion time and corrosion condition |
| Formulation 1 | No corrosion phenomenon on the surface of 60 hours |
| Formulation 2 | No corrosion phenomenon on the surface of 60 hours |
| Formulation 3 | No corrosion phenomenon on the surface of 60 hours |
| Formulation 4 | No corrosion phenomenon on the surface of 60 hours |
| Formulation 5 | No corrosion phenomenon on the surface of 60 hours |
| Formulation 6 | No corrosion phenomenon on the surface of 60 hours |
| Existing commercial products | 48 Hours have slight corrosion |
| Blank space | For 24 hours have slight corrosion phenomenon |
As can be seen from the table, the blank in the example 1 is corroded in 24 hours, the commercial product has a slight corrosion phenomenon in 48 hours, the salt fog of the formula does not corrode in 60 hours, and the commercial product adopts an experiment carried out by a product of Shenzhen company model K737C.
Example 2: and (3) testing the salt spray resistance of the selectively gold-plated tin belt material, wherein the gold-plated area passes through salt spray for 72 hours, and the gold-tin junction and the tin-plated area pass through salt spray for 24 hours.
A base material of the belt material: the brass semi-gold tin strip (0.03-0.04 μm for partial gold plating and 2-3 μm for partial tin plating) was coated in the same manner as described above, and the results are shown in Table 3.
Table 3: salt spray resistance test result on selective gold-plated tin strip
| Formulation of | Local gold plating area | Local tin plating zone | Gold-tin junction |
| Formulation 1 | 96H surface is free of corrosion | 24H surface has no corrosion | 24H surface has no corrosion |
| Formulation 2 | 96H surface is free of corrosion | 24H surface has no corrosion | 24H surface has no corrosion |
| Formulation 3 | Surface mild corrosion for 96h | 24H surface has no corrosion | Slight corrosion of 24h surface |
| Formulation 4 | 96H surface is free of corrosion | 24H surface has no corrosion | 24H surface has no corrosion |
| Formulation 5 | 96H surface is free of corrosion | 24H surface has no corrosion | 24H surface has no corrosion |
| Formulation 6 | 96H surface is free of corrosion | 24H surface has no corrosion | 24H surface has no corrosion |
| Commercial products | 60H surface slight corrosion | 24H surface has no corrosion | Slight corrosion of 24h surface |
| Blank control | 48H surface slight corrosion | 12H surface slight corrosion | 12H surface slight corrosion |
As shown in the results of Table 3, formulations 1, 2, 4,5 and 6 all met the salt spray resistance requirements on the gold-tin strip. Formula 3 salt spray at the gold-tin junction begins to corrode slightly after 24 hours, and commercial products cannot meet the test of salt spray resistance on gold-tin plated strip materials.
Comparative example 1: the effect of the protective agent on the salt spray performance, which is formed by the film forming material and the azole material in different mass ratios, is shown in table 4.
Table 4: comparative example 1 Experimental formulation
| Composition of the components | Formulation 1 | Formulation 2 | Formulation 3 | Formulation 4 |
| Dodecenyl succinate | 12 | 11.5 | 9 | 7 |
| 2-Mercaptobenzothiazoles | 2.5 | 6 | 5 | 8 |
| Fatty alcohol polyoxyethylene ether | 27 | 27 | 27 | 27 |
| Dimerized oleic acid | 6.5 | 6.5 | 6.5 | 6.5 |
| Styrene acrylic resin | 5 | 5 | 5 | 5 |
| Pure water | 47 | 44 | 47.5 | 46.5 |
The test pieces, the protective agent coating process and the salt spray test standard used in comparative example 1 were the same as in example 2, and were observed every 12 hours, and the salt spray test results are shown in table 5.
Table 5: comparative example 1 experimental results
| Comparative example 1 | Local gold plating area | Local tin plating zone | Gold-tin junction |
| Formulation 1 | Surface mild corrosion for 72h | Slight corrosion of 24h surface | Obvious corrosion of 24h surface |
| Formulation 2 | 96H surface is free of corrosion | 24H surface has no corrosion | 24H surface has no corrosion |
| Formulation 3 | 96H surface is free of corrosion | 24H surface has no corrosion | 24H surface has no corrosion |
| Formulation 4 | Surface mild corrosion for 72h | Slight corrosion of 24h surface | Obvious corrosion of 24h surface |
As can be seen from the experimental results of comparative example 1, the mass ratio of the film forming substance to the azole substance in the formula 1 of comparative example 1 is greater than 3:1, the steric hindrance between molecules of a film forming substance is large, the film forming is thick but the compactness is poor, the azole substance has small mass, the filling effect can not be completely achieved, and certain defects exist in the film layer, so that the protective capability is reduced. The gold-tin boundary part has worse coating quality, so the corrosion is more serious, and the obvious corrosion phenomenon appears in the salt fog for 24 hours.
In addition, in comparative example 1, 2-mercaptobenzothiazole was replaced with the same amounts of the three compositions of 2-mercaptobenzothiazole and 1-phenyl-1H-tetrazole, 1-phenyl-1H-tetrazole and 2- (phenylmethyl) -1H-benzimidazole, 2-mercaptobenzothiazole and 2- (phenylmethyl) -1H-benzimidazole, respectively, and after replacement, it was found that the corrosion resistance of the local gold plating area, the local tin plating area and the gold-tin interface were effectively improved, and the time delay for the same corrosion was 12 hours.
The mass ratio of the film forming substance to the azole substance in the formula 4 is less than 1-3:1, the formed protective film is thin, the defects on the surface of a plating layer cannot be completely repaired, corrosive medium cannot be effectively isolated, and the surface of the salt fog 72h gold plating layer is corroded.
Comparative example 2: the rapid prototyping performance test and the formulation table are shown in table 6.
Table 6: comparative example 2 Experimental formulation
| Composition of the components | Formulation 1 | Formulation 2 | Formulation 3 |
| Dodecenyl succinate | / | 10 | 10 |
| 2-Mercaptobenzothiazoles | 1.7 | 1.7 | 1.7 |
| Benzotriazole | 3 | 3 | 3 |
| Styrene acrylic resin | 6.5 | / | 6.5 |
| Lauryl glucoside | 30 | 30 | 30 |
| Dimerized oleic acid | 7 | 7 | 7 |
| Pure water | 51.8 | 48.3 | 41.8 |
The test pieces, coating process and salt spray test criteria used in comparative example 2 were the same as those of example 2, and were observed every 12 hours, and the salt spray test results are shown in table 7.
Table 7: comparative example 2 experimental results
| Comparative example 2 | Local gold plating area | Local tin plating zone | Gold-tin junction |
| Formulation 1 | Surface mild corrosion for 72h | Obvious corrosion of 24h surface | Obvious corrosion of 24h surface |
| Formulation 2 | Surface mild corrosion for 72h | Slight corrosion of 24h surface | Slight corrosion of 24h surface |
| Formulation 3 | 96H surface is free of corrosion | 24H surface has no corrosion | 24H surface has no corrosion |
As can be seen from the results in Table 7, the coating of formulation 3 for 3 seconds can form a complete protective film, has good protective effect, has the effect of rapid film formation, and has obviously poor protective effects of formulations 1 and 2. The results show that the formula product provided by the invention has quick film forming property and can be used in a high-speed continuous electroplating production line.
The present application is described in detail above. It will be apparent to those skilled in the art that the present application can be practiced in a wide range of equivalent parameters, concentrations, and conditions without departing from the spirit and scope of the application and without undue experimentation. While the application has been described with respect to specific embodiments, it will be appreciated that the application may be further modified. In general, this application is intended to cover any variations, uses, or adaptations of the application following, in general, the principles of the application and including such departures from the present disclosure as come within known or customary practice within the art to which the application pertains. The application of some of the basic features may be done in accordance with the scope of the claims that follow.
Claims (4)
1. The water-soluble protective agent shared by the gold and tin plating layers is characterized by comprising the following substances in parts by mass: 5-15 parts of film forming substances; 3-8 parts of corrosion inhibitor; 20-40 parts of surfactant; 3-10 parts of film forming auxiliary agent; 2-8 parts of additive; 30-50 parts of pure water;
the film forming material is one or a combination of more of dodecenyl succinic acid half ester and dodecenyl succinic acid ester;
the ratio of the film forming substance to the corrosion inhibitor is 1:1-3:1, a step of;
the corrosion inhibitor is any two combinations of 2-mercaptobenzothiazole, 1-phenyl-1H-tetrazole and 2- (phenylmethyl) -1H-benzimidazole;
The film forming auxiliary agent is waterborne styrene and acrylic acid copolymer resin or waterborne styrene and acrylic acid modified resin biology;
The additive is one of alkyl sulfonic acid or dimerized oleic acid.
2. A water-soluble protective agent common to gold-tin plating according to claim 1, wherein said film-forming material is dodecenyl succinate.
3. A water-soluble protective agent shared by gold-tin plating layers as claimed in claim 1, wherein the surfactant is a biosurfactant and a synthetic surfactant.
4. A method for preparing a water-soluble protective agent shared by gold-tin plating layers as claimed in any one of claims 1 to 3, comprising the steps of:
(1) Sequentially adding mercaptan substances, a surfactant, a corrosion inhibitor, an antirust agent and an additive into an enamel container according to a formula, heating to 60-70 ℃, fully stirring until the components are completely dissolved into transparent liquid, adding pure water according to the formula, and continuously stirring for 2 hours to obtain a protective agent concentrated solution;
(2) When in use, the barrel filled with the concentrated solution is placed in hot water with the temperature of about 80 ℃ to be fully melted and shaken uniformly, and then the solution is diluted into 5 percent working solution by pure water with the temperature of 50-55 ℃.
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