CN109097759B - A kind of gold and silver coating Anti- tarnishing protective agent and preparation method thereof and application method - Google Patents
A kind of gold and silver coating Anti- tarnishing protective agent and preparation method thereof and application method Download PDFInfo
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- CN109097759B CN109097759B CN201811095449.5A CN201811095449A CN109097759B CN 109097759 B CN109097759 B CN 109097759B CN 201811095449 A CN201811095449 A CN 201811095449A CN 109097759 B CN109097759 B CN 109097759B
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- 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
- C23C22/02—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 non-aqueous solutions
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Abstract
The present invention relates to a kind of metal-plated post-treatment agents, and in particular to a kind of gold-plated, silver plating anti-color changing protecting agent and preparation method thereof and application method.One kind is gold-plated, silver plating anti-color changing protecting agent includes benzimidazole compound, xanthic acid ester type compound, oil-in-water dispersing agent, mercaptan modified aromatic radical guanidine salt, polymer, suspending agent；Preparation method are as follows: under heating water bath steady temperature, in oil-in-water dispersing agent that benzimidazole compound and xanthic acid ester type compound are placed in, polymer and suspending agent is added, adds mercaptan modified arylation guanidine salt.Its application method are as follows: Anti- tarnishing protective agent is soluble in water, plated workpiece is immersed.Anti- tarnishing protective agent of the invention is anti-oxidant and curability is prominent, and technological operation is simple, wearability is strong, does not influence the welding performance of workpiece, workpiece easy cleaning, environmental sound, on coating electric property substantially without influence the advantages that.
Description
Technical field
The present invention relates to a kind of metal-plated post-treatment agents, and in particular to the gold-plated, silver plating anti-color changing protecting agent of one kind and its system
Preparation Method and application method.
Background technique
The surfacecti proteon of traditional gold, silver layer mainly has chemical passivation, electrochemical passivation, electrophoresis, coating solvent type to protect
Protect the methods of agent, thermocouple passivation, electroplate precious metal, organic complex passivating film.Chemical passivation and electrochemical passivation need using
Chromic anhydride, potassium bichromate, passivation layer contain Cr (VI), do not meet the requirement of EC regulations RoHS instruction and WEEE instruction；It coats molten
Dosage form protective agent often uses toxic solvent, causes environmental pollution and staff's health problem, and electricity after the solvent volatilization coated
Swimming method can change the electric property of metal layer, increase contact resistance；Thermocouple passivation and the equal higher cost of electroplate precious metal, need to increase
Add new process, management needs certain level；Organic complex passivating film is used as novel gold-plated, silver layer Anti- tarnishing protection in recent years
Agent, it forms single-layer or multi-layer organic matter film in gold-plated, silver layer surface, and playing prevents gold-plated, silver layer to be oxidized and vulcanize
Effect.But gold, silver Protective reagent in the prior art is difficult to be washed off rapidly by scaling powder in welding, and holds at high temperature
Easily lead to the phenomenon that weldering is refused in the generation of gold, silver coating.
Summary of the invention
The present invention is intended to provide a kind of gold, silver coating Anti- tarnishing protective agent, which has with Anti- tarnishing protective agent
Having that Anti-tarnish property is good, the electric property of silver plate and appearance is not influenced, while there is solderability, operating procedure is simple,
It is low in cost, the advantages that not causing environmental pressure.
The object of the invention to solve the technical problems adopts the following technical solutions to realize:
A kind of gold and silver coating Anti- tarnishing protective agent, is calculated, including following components is made as mass fraction:
Benzimidazole compound is 2- aromatic radical benzimidazole compound, and suspending agent is low aromatic carboxyl acid and trichlorine oxygen
The mixture of phosphorus；Mercaptan modified arylation guanidine salt has chirality；Oil-in-water dispersing agent includes water phase and oily phase, and water phase includes allantois
Element, butanediol, deionized water and 3% Sodium Hyaluronate, oil are mutually poly- comprising sucrose stearate, glyceryl isostearate and hydrogenation
Alkene certain herbaceous plants with big flowers.
Further, xanthic acid ester type compound be ethoxy-dithioformic acid Ethyl formate, it is isopropyl xanthogen ethyl formate, different
The mixture of any one or two kinds in butyl xanthogen ethyl formate or cellulose xanthic acid Ethyl formate.
Further, 2- aromatic radical benzimidazole compound is 2- thiophenyl benzimidazole, 2- (2- aminophenyl) -1H-
Any one in benzimidazole, 2- phenyl -5- benzimidazole sulfonic acid or 2-Phenylbenzimidazole.
Further, low aromatic carboxyl acid be parachlorobenzoic-acid, parafluorobenzoic acid, para Toluic Acid, 4- butylbenzoic acid,
Any one in 3- mercaptobenzoic acid, adjacent iodobenzene acetic acid or o-Tolylacetic acid.
Further, polymer is polyvinyl alcohol, polyvinyl chloride, polystyrene, polystyrene ester, polyethylene glycol or poly- third
The mixture of any one or two kinds in glycol.
Further, it is calculated according to mass fraction, oil-in-water dispersing agent each component content are as follows:
Further, oil-in-water dispersing agent the preparation method comprises the following steps: each component is proportionally added in beaker, water-bath adds
Heat persistently stirs 30min to 50-60 DEG C.
Further, gold and silver coating Anti- tarnishing it is protectant the preparation method is as follows:
(1) at 55-60 DEG C of water bath with thermostatic control, the benzimidazole compound is added in the oil-in-water dispersing agent and is continued
Stir 30min；
(2) keep temperature-resistant, in the state of lasting stirring, to institute is slowly added dropwise after described polymer is added in (1)
Suspended matter is stated, 5min is stirred；
(3) keep temperature-resistant, in the state of lasting stirring, to the addition mercaptan modified aromatic radical guanidine in (2)
Salt continues to stir 1h, can pack use after keeping the temperature 55-60 DEG C of 2-3h after mixing.
Further, a kind of protectant application method of gold and silver coating Anti- tarnishing is as follows:
Gold and silver coating anti-blushing agent is soluble in water, it is immersed gold and silver coating workpiece to form protective film.
Further, gold and silver coating workpiece is before immersing the gold and silver coating anti-blushing agent solution, using micro etch hand
Section pre-processes the gold and silver coating workpiece surface.
Compared with prior art, the present invention has at least the following advantages: gold, silver coating Anti- tarnishing protective agent of the invention
For organic supramolecular protective film, having does not influence appearance and electric conductivity, and vulcanization test period is long, the long characteristic of processing groove life,
It is that one kind is especially formulated in gold, silver coating water solubility antioxidant, one layer of nanometer protective layer can be formed in metal surface, it can be effective
Gold or silver layer metachromatism are prevented, while this gold, silver coating Anti- tarnishing protective agent has inoxidizability and curability prominent,
Operating procedure is simple, cheap, and wear-resisting property is strong, workpiece easy cleaning, environmental sound, on coating electric property without influence etc.
Advantage.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And can be implemented in accordance with the contents of the specification, with presently preferred embodiments of the present invention, detailed description is as follows below.
Specific embodiment
It is of the invention to reach the technical means and efficacy that predetermined goal of the invention is taken further to illustrate, below with reference to
Specific embodiment is come to gold, silver coating of the invention, just color protective agent and preparation method thereof and application method are made specifically with anti-
It is bright.
Gold, silver coating of the invention with anti-just color protective agent and preparation method thereof and made combined with specific embodiments below
It is described in detail with method.
A kind of gold and silver copper coating Anti- tarnishing protective agent disclosed by the invention includes following component, according to weight fraction meter
It calculates:
Xanthic acid ester type compound can be self-assembly of one layer of fine and close protective film outside gold, silver coating, effectively hinder
Only O2、H2O、CO2、H2S、SO2It is contacted with gold, silver coating, plays protective coating, prevent gold, silver coating color.Huang of the present invention
Ortho acid ester type compound silver ion functional group is SP2 hydridization, and the pi-conjugated system with four centers, six electronics makes the negative of sulphur atom
Charge can capture gold, silver ion and form the big pi bond of stable conjugation, bond energy is big compared with Van der Waals force, therefore in biggish spatial dispersion
It is more stable, it is not easy to be destroyed；And the alkyl of xanthate compound has hydrophobicity, can form one in gold, silver coating surface
The fine and close waterproofness organic film of layer, achievees the purpose that gold, silver coating is prevented to be oxidized in the application.
The benzimidazole compound is preferably 2- aromatic radical benzimidazole compound, can effectively enhance gold, silver coating
Solderability.
The mercaptan modified arylation guanidine salt can effectively prevent the vulcanization of gold, silver coating while film forming, preferably just
The modified arylation guanidine salt of chirality thiol is selected in case, because it is with higher thermal stability, gold, silver coating is effectively prevent to protect
Agent is influenced by high temperature in welding and is decomposed.
The oil-in-water dispersing agent includes water phase and oily phase, and the water phase includes allantoin, butanediol, deionized water, 3%
Sodium Hyaluronate, the oil include mutually sucrose stearate, glyceryl isostearate, hydrogenated polyolefin certain herbaceous plants with big flowers, can effectively solve the problem that sulphur
The solubility problem of alcohol modified arylation guanidine salt and xanthic acid ester type compound.
Phosphorus oxychloride in the suspending agent ingredient can be reacted with the alcohols in auxiliary coalescing agent generates OPA, effectively
It prevents from settling, since 2- aryl benzimidazole dissolubility in PH higher is poor, and easily precipitate crystal, low aromatic carboxyl acid can
PH is adjusted, the dissolubility of 2- aromatic radical benzimidazole compound is improved.
The polymer can select for the auxiliary film forming matter and mix liquor-saturated polyethylene, polyvinyl chloride, polystyrene, poly- third second
It is added in protective agent one or both of when enol, aliphatic alcohol polyethenoxy etc. with arbitrary proportion, effect is acceleration protection
The formation of film, and film forming matter defect caused by the endless all standing in metal surface is made up, enhance the cation protection of protective layer
Effect.
The protectant configuration method of gold, silver coating Anti- tarnishing of the invention are as follows:
(1) at 55-60 DEG C of water bath with thermostatic control, the benzimidazole compound is added in the oil-in-water dispersing agent and is continued
Stir 30min；
(2) keep temperature-resistant, in the state of lasting stirring, to institute is slowly added dropwise after described polymer is added in (1)
Suspended matter is stated, 5min is stirred；
(3) keep temperature-resistant, in the state of lasting stirring, to the addition mercaptan modified aromatic radical guanidine in (2)
Salt continues to stir 1h, can pack use after keeping the temperature 55-60 DEG C of 2-3h after mixing.
The protectant application method of gold, silver coating Anti- tarnishing of the invention are as follows:
The gold and silver coating anti-blushing agent is soluble in water, it is immersed gold and silver coating workpiece to form protective film, it is excellent
Selecting scheme is by the gold and silver coating workpiece before immersing the gold and silver coating anti-blushing agent solution, using micro etch means pair
The gold and silver coating workpiece surface is pre-processed.Micro etch processing be capable of increasing gold, silver coating with it is protectant in the application
Contact area forms more stable protective film.
Following specific embodiments are given below.
Specific embodiment 1 (for 1kg)
2- thiophenyl benzimidazole 100g
Ethoxy-dithioformic acid Ethyl formate 50g
Oil-in-water dispersing agent 480g
Chirality thiol modified aromatic base guanidine salt 110g
Polyvinyl alcohol 250g
O-Tolylacetic acid 6g；
Phosphorus oxychloride 4g
Preparation method:
(1) at 55 DEG C of water bath with thermostatic control, 100g 2- thiophenyl benzimidazole and 50g ethoxy-dithioformic acid Ethyl formate are added
30min is persistently stirred into oil-in-water dispersing agent；
(2) keep temperature-resistant, in the state of lasting stirring, to being slowly added dropwise after 250g polyvinyl alcohol is added in (1)
4g phosphorus oxychloride and 6g o-Tolylacetic acid stir 5min；
(3) keep temperature-resistant, in the state of lasting stirring, to addition 110g chirality thiol modified aromatic base in (2)
Change guanidine salt, continues to stir 1h, use can be packed after keeping the temperature 55 DEG C of 3h after mixing.
Application method:
(1) 500g deionized water is placed in a beaker, the protective agent composition of 50g embodiment 1 is added, stirring makes it completely
Dissolution, adds deionized water and is settled to 1L.
(2) keeping its temperature is 42 DEG C, by gold and silver coating workpiece before immersing the gold and silver coating anti-blushing agent solution,
The gold and silver coating workpiece surface is pre-processed using micro etch means.
(3) gold and silver coating workpiece pretreated in (2) is immersed in 1min in the solution of (1), takes out drying.
Ethoxy-dithioformic acid Ethyl formate in the gold, silver coating Anti- tarnishing protective agent as disclosed in the present embodiment is to gold
The chelation of category is stronger, therefore the immersion time of gold and silver coating workpiece is unsuitable too long, and gold and silver coating is prevented to be corroded.
Specific embodiment 2 (for 1kg)
Chirality thiol modified aromatic base guanidine salt 100g
Polystyrene 80g
Polyethylene glycol 150g
O-Tolylacetic acid 13g；
Phosphorus oxychloride 7g
Preparation method:
(1) at 58 DEG C of water bath with thermostatic control, by 50g2- phenyl -5- benzimidazole sulfonic acid and 150g cellulose xanthic acid formic acid second
Ester is added in 480g oil-in-water dispersing agent and persistently stirs 30min；
(2) keep temperature-resistant, in the state of lasting stirring, to addition 80g polystyrene and the poly- second two of 150g in (1)
7g phosphorus oxychloride and 13g o-Tolylacetic acid are slowly added dropwise after alcohol, stirs 5min；
(3) keep temperature-resistant, in the state of lasting stirring, to addition chirality thiol modified aromatic base guanidine in (2)
Salt continues to stir 1h, can pack use after keeping the temperature 58 DEG C of 2.5h after mixing.
Application method:
(1) 500g deionized water is placed in a beaker, the protective agent composition of 50g embodiment 2 is added, stirring makes it completely
Dissolution, adds deionized water and is settled to 1L.
(2) keeping its temperature is 45 DEG C, by gold and silver coating workpiece before immersing the gold and silver coating anti-blushing agent solution,
The gold and silver coating workpiece surface is pre-processed using micro etch means.
(3) gold and silver coating workpiece pretreated in (2) is immersed in 3min in the solution of (1), takes out drying.
Cellulose xanthic acid Ethyl formate in the present embodiment is optimal selection, and wherein cellulose group can be to the ester of rigidity
Base carries out winding flexible, forms the protective film coupled hardness with softness, and improves the protectant wearability of gold, silver coating Anti- tarnishing, together
When, since the steric hindrance of cellulose group is larger, keep the compactness of protective film stronger.
Specific embodiment 3 (for 1kg)
Preparation method:
(1) at 60 DEG C of water bath with thermostatic control, by 80g 2- (2- aminophenyl) -1H- benzimidazole and 100g isobutyl group xanthic acid
Ethyl formate is added in 550g oil-in-water dispersing agent and persistently stirs 30min；
(2) keep temperature-resistant, in the state of lasting stirring, to being slowly added dropwise after 100g polyvinyl chloride is added in (1)
3g phosphorus oxychloride and 2g3- mercaptobenzoic acid stir 5min；
(3) keep temperature-resistant, in the state of lasting stirring, to addition 165g chirality thiol modified aromatic base in (2)
Change guanidine salt, continues to stir 1h, use can be packed after keeping the temperature 60 DEG C of 3h after mixing.
Application method:
(1) 500g deionized water is placed in a beaker, the protective agent composition of 50g embodiment 3 is added, stirring makes it completely
Dissolution, adds deionized water and is settled to 1L.
(2) keeping its temperature is 45 DEG C, by gold and silver coating workpiece before immersing the gold and silver coating anti-blushing agent solution,
The gold and silver coating workpiece surface is pre-processed using micro etch means.
(3) gold and silver coating workpiece pretreated in (2) is immersed in 2min in the solution of (1), takes out drying.
To using gold, silver coating of the invention, with Anti- tarnishing protective agent, treated that workpiece is tested for the property below.
By the wiring board after plating, the gold, silver coating protection of above-described embodiment 1-3 is carried out.
1.K2S discoloration experiment
By 5% K2S is dripped on the wiring board using the gold, silver coating Anti- tarnishing protective agent protection of above-described embodiment 1-3,
Coloring Time is more than 8 minutes layer by layer for gold, silver plating, has preferable Anti-tarnish property.
2. salt spray resistance is tested
Wiring board after protection is subjected to 5% neutrality NaCl salt mist experiment, salt-fog resistant time reaches 96 hours or more.
3. being placed in air the experiment that changes colour
Wiring board after protection is placed in air and is placed, in the time more than 8 months, gold, silver plate sandwich circuit board not
Metachromatism occurs.
4. solderability is tested
Will by gold, silver coating Anti- tarnishing protective agent disclosed in the present application it is processed gold and silver plating piece steam ageing 24~
Then 96h is subjected to IR reflow process.Test parameter is as follows:
Preheat 120~200 DEG C (1min), more than 200 DEG C (0.5min)
230 DEG C of maximum temperature
Parameter of wave-soldering
120~130 DEG C of preheating
250 DEG C of welding temperature
Scaling powder selects the no-clean scaling powder of 4 kinds of different manufacturers
As a result as follows:
Performance test, which shows gold, silver coating Anti- tarnishing protective agent disclosed by the invention, has good protective value,
Meanwhile gold, silver coating of the invention is organic supramolecular protective film with Anti- tarnishing protective agent, having does not influence appearance and conduction
Property, it does not influence welding and is impregnated with rate, vulcanization test period is long, the long characteristic of processing groove life, can effectively prevent gold or silver layer discoloration
Phenomenon, wear-resisting property is strong, workpiece easy cleaning, environmental sound, on coating electric property substantially without influencing the advantages that.
The above described is only a preferred embodiment of the present invention, be not intended to limit the present invention in any form, though
So the present invention has been disclosed as a preferred embodiment, and however, it is not intended to limit the invention, any technology people for being familiar with this profession
Member, without departing from the scope of the present invention, when the technology contents using the disclosure above are modified or are modified
For the equivalent embodiment of equivalent variations, but anything that does not depart from the technical scheme of the invention content, according to the technical essence of the invention
Any simple modification, equivalent change and modification to the above embodiments, all of which are still within the scope of the technical scheme of the invention.
Claims (10)
1. a kind of gold and silver coating Anti- tarnishing protective agent, which is characterized in that calculate as mass fraction, including following components is made:
5 ~ 20 parts of benzimidazole compound
5 ~ 15 parts of xanthic acid ester type compound
30 ~ 80 parts of oil-in-water dispersing agent
10 ~ 20 parts of mercaptan modified aromatic radical guanidine salt
20 ~ 30 parts of polymer
1 ~ 5 part of suspending agent；
The benzimidazole compound is 2- aromatic radical benzimidazole compound, and the suspending agent is low aromatic carboxyl acid and three
The mixture of chlorethoxyfos；The mercaptan modified arylation guanidine salt has chirality；The oil-in-water dispersing agent includes water phase and oily phase,
The water phase includes allantoin, butanediol, deionized water and 3% Sodium Hyaluronate, and the oil is mutually comprising sucrose stearate, different
Tristerin and hydrogenated polyolefin certain herbaceous plants with big flowers.
2. a kind of gold and silver coating Anti- tarnishing protective agent according to claim 1, which is characterized in that the xanthic acid esters
Compound is ethoxy-dithioformic acid Ethyl formate, isopropyl xanthogen ethyl formate, isobutyl group xanthic acid Ethyl formate or cellulose
The mixture of any one or two kinds in xanthic acid Ethyl formate.
3. a kind of gold and silver coating Anti- tarnishing protective agent according to claim 1, which is characterized in that the 2- aromatic radical benzene
Benzimidazole compounds are 2- thiophenyl benzimidazole, 2- (2- aminophenyl) -1H- benzimidazole, 2- phenyl -5- benzimidazole sulphur
Acid or 2-Phenylbenzimidazole in any one.
4. a kind of gold and silver coating Anti- tarnishing protective agent according to claim 1, which is characterized in that the low aromatic series carboxylic
Base acid is parachlorobenzoic-acid, parafluorobenzoic acid, para Toluic Acid, 4- butylbenzoic acid, 3- mercaptobenzoic acid, adjacent iodobenzene acetic acid or neighbour
Any one in methylphenyl acetic acid.
5. a kind of gold and silver coating Anti- tarnishing protective agent according to claim 1, which is characterized in that the polymer is poly-
Any one or two kinds in vinyl alcohol, polyvinyl chloride, polystyrene, polystyrene ester, polyethylene glycol or polypropylene glycol it is mixed
Close object.
6. a kind of gold and silver coating Anti- tarnishing protective agent according to claim 1, which is characterized in that according to mass fraction meter
It calculates, the oil-in-water dispersing agent each component content are as follows:
1 ~ 5 part of allantoin
10 ~ 20 parts of butanediol
20 ~ 40 parts of deionized water
1 ~ 5 part of EDTA
3% 1 ~ 5 part of Sodium Hyaluronate
15 ~ 30 parts of sucrose stearate
10 ~ 20 parts of tristerin
20 ~ 25 parts of hydrogenated polyolefin certain herbaceous plants with big flowers.
7. a kind of gold and silver coating Anti- tarnishing protective agent according to claim 1, which is characterized in that the oil-in-water dispersion
Agent the preparation method comprises the following steps: above-mentioned each component is proportionally added in beaker, heating water bath is lasting to stir to 50-60 DEG C
30min。
8. a kind of protectant preparation method of gold and silver coating Anti- tarnishing, which is characterized in that including claim 1-7 any one
The gold and silver coating Anti- tarnishing protective agent, the gold and silver coating Anti- tarnishing it is protectant the preparation method is as follows:
(1) at 55-60 DEG C of water bath with thermostatic control, the benzimidazole compound and xanthic acid ester type compound are added to the water packet
30min is persistently stirred in oil dispersant；
(2) it keeps temperature-resistant, in the state of lasting stirring, institute is slowly added dropwise after the polymer is added in Xiang Suoshu (1)
Suspended matter is stated, 5min is stirred；
(3) it keeps temperature-resistant, in the state of lasting stirring, the mercaptan modified aromatic radical guanidine is added in Xiang Suoshu (2)
Salt continues to stir 1h, can pack use after keeping the temperature 55-60 DEG C of 2-3h after mixing.
9. a kind of protectant application method of gold and silver coating Anti- tarnishing, which is characterized in that including claim 1-7 any one
The gold and silver coating Anti- tarnishing protective agent, the protectant application method of gold and silver coating Anti- tarnishing are as follows: the gold
Silvering anti-blushing agent is soluble in water, is immersed gold and silver coating workpiece to form protective film.
10. a kind of protectant application method of gold and silver coating Anti- tarnishing according to claim 9, which is characterized in that institute
Gold and silver coating workpiece is stated before immersing the gold and silver coating anti-blushing agent solution, using micro etch means to the gold and silver coating
Workpiece surface is pre-processed.
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| CN101705483A (en) * | 2009-11-16 | 2010-05-12 | 海宁市科泰克金属表面技术有限公司 | Water soluble anti-discoloration after treating agent for noble metal, copper and copper alloy |
| CN102162095A (en) * | 2011-03-01 | 2011-08-24 | 济南德锡科技有限公司 | Anti-discoloring protective agent for silver plating and preparation method as well as application method thereof |
| CN102766871A (en) * | 2012-07-13 | 2012-11-07 | 东莞市东辉贸易有限公司 | Silver-plated antitarnish protectant composition |
| CN102747350A (en) * | 2012-07-18 | 2012-10-24 | 深圳市成功科技有限公司 | Gold/silver plating layer surface protective agent |
| CN106319491A (en) * | 2016-08-19 | 2017-01-11 | 张超 | Surface corrosion-preventing and color-fixing agent for metal, preparation method and application |
| CN106282984A (en) * | 2016-08-25 | 2017-01-04 | 贵州苗妹银饰工艺品有限公司 | Anti-silver tarnish agent |
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