CN110230061A - A kind of gold and silver surface anti-oxidation Anti- tarnishing protective agent and its preparation method and application - Google Patents
A kind of gold and silver surface anti-oxidation Anti- tarnishing protective agent and its preparation method and application Download PDFInfo
- Publication number
- CN110230061A CN110230061A CN201910563375.1A CN201910563375A CN110230061A CN 110230061 A CN110230061 A CN 110230061A CN 201910563375 A CN201910563375 A CN 201910563375A CN 110230061 A CN110230061 A CN 110230061A
- Authority
- CN
- China
- Prior art keywords
- parts
- gold
- acid
- wax
- ether
- 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
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
- C23C22/06—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 using aqueous acidic solutions with pH less than 6
- C23C22/48—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 using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
-
- 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
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention discloses a kind of gold and silver surface anti-oxidation Anti- tarnishing protective agents and its preparation method and application, belong to gold and silver Protective reagent technical field.Protective agent of the invention includes following components according to parts by weight: 15-30 parts of anti-blushing agent; 10-15 parts of film forming agent; 3-8 parts of alcohol ether solvents; 30-50 parts of emulsifier, 2-5 parts of cationic germicide, carboxylic acid type deoxygenates agent 5-10 parts; 1-3 parts of corrosion inhibiter; 0.5-1 parts of antioxidant, 1-3 parts of brightener, 5-20 parts of water.Protective agent prepared by the present invention, which can form double shielding film, can effectively prevent gold and silver coating oxidation by air, by acid and alkali corrosion, while improve coating surface resisting discoloration performance, increase the bright property of coating, assign the more bright and clear appearance of coating and efficient performance；This protective agent can also be used in the surfacecti proteon of Copper base material, and effect matches in excellence or beauty chromic salts protecting film, copper surface can be kept for a long time non-discolouring, and effect low toxicity treatment process is simple.
Description
Technical field
The invention belongs to gold and silver Protective reagent technical field, in particular to a kind of gold and silver surface anti-oxidation Anti- tarnishing protection
Agent and its preparation method and application.
Background technique
Gold and silver belongs to precious metal, since its chemical activity is relatively stable and brightness effect is good, has been widely applied
In Surface Processing Industry.Gold-plated silver layer, which can be applied, improves the inoxidizability and electric conductivity of product on electronic product surface, can also
To improve the bright property of five gold ornaments, and led in automobile, medical instrument, building, machine-building, Aeronautics and Astronautics, ship etc.
Domain is applied.However gold and silver coating is chronically exposed to air or is immersed in the oxidation film for being also easy to produce black in river water seawater,
This layer of oxidation film had both seriously affected the brightness of coating, can also damage its weldability, and the metal for destroying gold and silver in coating is former
Son sequence and the transmitting of electronics cause its resistance to increase, and electric conductivity is deteriorated；Some requirements of more demanding coating to salt spray resistance
Also relatively high, and this is that general gold and silver coating is unable to reach.
Gold and silver Protective reagent refers to for gold and silver coating material surface, can play prevent coating to be oxidized, corrode and
The industrial protective agent of blackening effect.Simple gold and silver Protective reagent is typically all hole envelope agent, passivator and protection oil etc
's.This kind of protective agents will affect the weldability and electric conductivity of coating, and brightness effect duration is also poor while to go
Except oil layer protection is also more difficult and can injure coating surface, thus cost is caused to increase indirectly, the wasting of resources.
In addition to this, protective agent of the simple dependence alkyl hydrosulfide as anti-blushing agent on the market, thin protective layer
Also it is easy the destruction by extraneous factor, to lose the protection to coating.In view of such reason, seek double shielding film, and
And it is man skilled in the art one that the shiny appearance of coating can be improved again, do not influence the protective agent of coating electric conductivity
The important topic directly studied.
Summary of the invention
To solve the deficiencies in the prior art, it is anti-that primary and foremost purpose of the present invention is to provide a kind of gold and silver surface anti-oxidation
Change colour protective agent.The protective agent utilize anti-blushing agent and film forming agent double action, one side strict protection coating completely every
Exhausted air improves the bright property of coating simultaneously；Another aspect complexing agent and surfactant combined use can be removed by coating table
The impurity and greasy dirt in face ensure the cleaning of coating.
Another object of the present invention is to provide the above-mentioned protectant preparation method of gold and silver surface anti-oxidation Anti- tarnishing.
Still a further object of the present invention is to provide the above-mentioned protectant application of gold and silver surface anti-oxidation Anti- tarnishing.
The purpose of the invention is achieved by the following technical solution:
A kind of gold and silver surface anti-oxidation Anti- tarnishing protective agent includes following components: anti-blushing agent 15-30 according to parts by weight
Part, 10-15 parts of film forming agent, 3-8 parts of alcohol ether solvents, 30-50 parts of emulsifier, 2-5 parts of cationic germicide, carboxylic acid type deoxygenates agent
5-10 parts, 1-3 parts of corrosion inhibiter, 0.5-1 parts of antioxidant, 1-3 parts of brightener, 5-20 parts of water.
Wherein, the anti-blushing agent is the compound containing thiol group, includes: n- dodecyl mereaptan, tert-dodecyl mercaptan, ten
Four mercaptan, 16 mercaptan, Stearyl mercaptan, two lauryl mercaptans, Thiodiglycol, in Thiodiglycol polyoxyethylene ether extremely
Few one kind.
Wherein, the film forming agent is that 80 DEG C of waxes below of fusing point are used in compounding or commercially available with 100 DEG C of fusing point or more of wax
One of wax emulsion；Described 80 DEG C of waxes below of fusing point are atoleine, semi-refined paraffin wax, fully refined paraffin wax, microwax, illiteracy
At least one of denier wax, lignite wax, Organosilicon wax；100 DEG C of fusing point or more of the wax be polyethylene wax, polypropylene wax,
At least one of PAO synthetic wax, oxidized polyethylene wax；The commercially available wax emulsion is paraffin wax emulsions, polythene wax emulsion, oxygen
Change one of polythene wax emulsion, silicon wax emulsion.In order to which high temperature resistant uses or improves the hardness of protecting film, it is necessary to compound one
Divide fusing point at 100 DEG C with waxing；It, can be in advance by wax, emulsifier, water etc. in order to which wax can be evenly dispersed in water and prevents from agglomerating
Substance is emulsified into the lotion of stable homogeneous, it is contemplated that oneself dispersion when complex process and lotion it is unstable, market can also be selected
On scattered wax emulsion.
Wherein, the alcohol ether solvents are benzyl alcohol, ethylene glycol phenyl ether, propylene glycol phenylate, Isosorbide-5-Nitrae-butynediols, propine
Alcohol, butynediols diethoxy ether, propilolic alcohol list propoxyl group ether, butyl, diethylene glycol, dipropylene glycol methyl ether, benzyl
At least one of ether.
Wherein, the emulsifier is polyethylene glycol, poly glycol monomethyl ether, polyethylene glycol dimethyl ether, isomery alcohol polyoxy
Vinethene, alkyl phenol polyoxyethylene ether, aliphatic amine polyoxyethylene ether, soybean oleyl amine polyoxyethylene ether, rilanit special polyoxy second
Alkene ether, polyoxyethylene oleic acid ester, SYNPERONIC PE/F68 (polyethers), laruyl alcohol atactic polyether, beef tallow amine polyoxy second
At least one of alkene ether.It is preferred that the alkyl phenol ether compound with special construction, specifically includes bisphenol A polyethenoxy ether, 2-
Naphthols polyoxyethylene ether, tert-butyl benzene phenol polyethenoxy ether, 4- cumylphenol polyoxyethylene ether, tert-octylphenol polyoxyethylene ether
(Qula leads to 114, Triton X-100), cardanol polyoxyethylene ether, styrylphenol polyoxyethylene ether (agriculture breast 400#, agriculture breast
600#-1), at least one of Rhodia Soprophor 796/P, Triton X-100 (triton X-100), these
Surfactant has excellent emulsibility, dispersibility and permeance property.
Wherein, the cationic germicide is dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, ten
Six alkyl trimethyl ammonium chlorides, octadecyltrimethylammonium chloride, dodecyl trimethyl ammonium bromide, dodecyl dimethyl benzyl
At least one of ammonium chloride, myristyl benzyl chloride, hexadecyl benzyl dimethly ammonium chloride etc..
Wherein, carboxylic acid type deoxidation agent is lactic acid, citric acid, tartaric acid, malic acid, hydroxyacetic acid, amino second
Acid, gluconic acid, octylphosphonic acid, thiomalic acid, thioacetic acid, mercaptopropionic acid, two mercaptan dihydroxy acetic acids, di-2-ethylhexylphosphine oxide sulphur
For at least one of acetic acid, (ethylene is thio) oxalic acid, dithiodipropionic acid etc.；In view of deoxidation and Anti- tarnishing
The synergistic effect of property, preferably thiomalic acid, thioacetic acid, mercaptopropionic acid, two mercaptan dihydroxy acetic acids, di-2-ethylhexylphosphine oxide are thio
The organic acid of at least one of acetic acid, (ethylene is thio) oxalic acid, dithiodipropionic acid sulfur atom-containing.
Wherein, the corrosion inhibiter is benzotriazole, methyl benzotriazazole, 2-mercaptobenzothiazole, 2- hydroxy benzenes
And thiazole, 2- methylbenzothiazole, 2-mercaptobenzimidazole, 2- amino -5- sulfydryl -1,3,4- thiadiazoles (AMT), glucose,
At least one in sucrose, mannitol, sodium benzoate, chain alkyl imidazoline, hydrazine hydrate, thiocarbamide, phosphine carboxylic acid and lignosulfonate
Kind.
Wherein, the antioxidant be 2,2'- di-2-ethylhexylphosphine oxide-(4- methyl-6-tert-butylphenol), ethoxyquinoline,
1- naphthylamino benzene, N- phenyl-2-naphthylamine, nickel dibutyl dithiocarbamate, 4,4'- dioctyl diphenylamine, bis- (benzene of 4,4'-
Base isopropyl) diphenylamines, one of N- cyclohexylthiophthalimide.
Wherein, the brightener is Brazil wax, candelila wax, soybean oil, palm oil, polyethyleneimine, tristearin
One of acid, palmitinic acid, dimethicone.
Wherein, the water is at least one of deionized water, high purity water, pure water.
The above-mentioned protectant preparation method of gold and silver surface anti-oxidation Anti- tarnishing, comprising the following steps:
1) prepare the raw material of the above parts by weight；
2) carboxylic acid type is deoxygenated into agent, emulsifier, cationic germicide, is added to the water, dissolution is sufficiently stirred；
3) alcohol ether solvents, antioxidant, anti-blushing agent, brightener are continuously added, and is heated to 60-80 DEG C, keeps this temperature
Then degree stirs 20-40 minutes, obtain lotion；
4) corrosion inhibiter, film forming agent are finally added, stirs, obtains gold and silver surface anti-oxidation Anti- tarnishing protective agent.
Above-mentioned gold and silver surface anti-oxidation Anti- tarnishing protective agent is used as gold, silver, copper (brass, red copper, bronze) metal surface
Protective agent.This protective agent can also be used in the surfacecti proteon of Copper base material, and effect matches in excellence or beauty chromic salts protecting film, can keep copper for a long time
Surface is non-discolouring, and effect low toxicity treatment process is simple.It is applicable in in Copper base material, belong to that this product drops to a lower level, is
Increase the popularity of this product using face.
The protectant protection philosophy of gold and silver surface anti-oxidation Anti- tarnishing of the invention is: 1. mainly passing through alkyl hydrosulfide
Sulfydryl one end and precious metals silver simple substance form one layer of fine and close thin-layered protective film by complexing, and film forming agent is again and alkane later
The alkyl segment of base mercaptan combines to form one layer of bright protective layer.It is applicable to the different technique requirement such as spray, immersion；
2. adding the auxiliary agent of the function admirables such as corrosion inhibiter and antioxidant, long-acting anticorrosion ability can be played；3. faintly acid deoxygenates
Silver surface can have been aoxidized the part removal of blackening by agent, while these organic acids also have complexing power, can remove impurity elimination
Matter ion, it is ensured that perfection of lattice.
The present invention has the following advantages and effects with respect to the prior art:
Gold and silver surface anti-oxidation Anti- tarnishing protective agent of the invention utilizes the double action of anti-blushing agent and film forming agent, a side
Strict protection coating in face completely cuts off air completely while improving the bright property of coating；Another aspect complexing agent and surfactant combine
Using the cleaning for being ensured coating by the impurity of coating surface and greasy dirt can be removed.The present invention mainly passes through alkyl hydrosulfide
Sulfydryl one end and precious metals silver simple substance form one layer of fine and close thin-layered protective film by complexing, and film forming agent is again and alkane later
The alkyl segment of base mercaptan combines to form one layer of bright protective layer；It is applicable to the different technique requirement such as spray, immersion.
The auxiliary agent of the function admirables such as added corrosion inhibiter and antioxidant, can play long-acting anticorrosion ability；Faintly acid used
Agent is deoxygenated, silver surface can have been aoxidized to the part removal of blackening, while these organic acids also have complexing power, can remove
Decontamination ion, it is ensured that perfection of lattice.Gold and silver surface anti-oxidation Anti- tarnishing protective agent of the invention, and in particular to Yi Zhongke
For silvering faintly acid protective agent, there is anticorrosion, anti-oxidant, inhibition, bright effect, can effectively protect silvering.
Protective agent prepared by the present invention, which can form double shielding film, can effectively prevent gold and silver coating oxidation by air, sour
Caustic corrosion, while improving coating surface resisting discoloration performance increases the bright property of coating, assign the more bright and clear appearance of coating and
Efficient performance；This protective agent can also be used in the surfacecti proteon of Copper base material, and effect matches in excellence or beauty chromic salts protecting film, can be protected for a long time
It is non-discolouring to hold copper surface, and effect low toxicity treatment process is simple.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the contents of the present invention, those skilled in the art can
To make various changes or modifications to the present invention, such equivalent forms equally fall within limited range of the present invention.
Embodiment 1
A kind of gold and silver surface anti-oxidation Anti- tarnishing protective agent includes following components according to parts by weight: 15 parts of stearylmercaptan,
8 parts of lactic acid, 35 parts of tert-octylphenol polyoxyethylene ether (triton X-100), 5 parts of benzyl oxide, dodecyl benzyl dimethyl ammonium chloride
3 parts, 0.5 part of 1- naphthylamino benzene, 1 part of benzotriazole, 11 parts of paraffin wax emulsions, 2 parts of palm wax, 19.5 parts of water.
The above-mentioned protectant preparation method of gold and silver surface anti-oxidation Anti- tarnishing, comprising the following steps:
1) prepare the raw material of the above weight；
2) it by 8 parts of lactic acid, 35 parts of tert-octylphenol polyoxyethylene ether, 3 parts of dodecyl benzyl dimethyl ammonium chloride, is added
Into 19.5 parts of water, dissolution is sufficiently stirred；
3) 3 parts of benzyl oxide, 0.3 part of 1- naphthylamino benzene, 15 parts of Stearyl mercaptan are continuously added, 2 parts of palm wax, and be heated to
It 70 DEG C, keeps this temperature then to stir 30 minutes, obtains lotion.
4) 0.5 part of benzotriazole, 11 parts of paraffin wax emulsions are finally added, is stirred, the protection of faintly acid silver is obtained
Agent.
Embodiment 2
A kind of gold and silver surface anti-oxidation Anti- tarnishing protective agent includes following components according to parts by weight: 10 parts of lauryl mercaptan,
Two 5 parts of lauryl mercaptans, 30 parts of styrylphenol polyoxyethylene ether (agriculture breast 600#-1), laruyl alcohol atactic polyether (CPE1500)
15 parts, 5 parts of thioacetic acid, 4 parts of benzyl alcohol, 5 parts of PAO synthetic wax, 2 parts of dodecyl trimethyl ammonium bromide, ethoxyquinoline 0.5
Part, 0.5 part of phosphine carboxylic acid, 1 part of soybean oil, 22 parts of water.
The above-mentioned protectant preparation method of gold and silver surface anti-oxidation Anti- tarnishing, comprising the following steps:
1) prepare the raw material of the above weight；
2) by 30 parts of styrylphenol polyoxyethylene ether, 15 parts of polyethers (CPE1500), 4 parts of benzyl alcohol, dodecyl three
2 parts of methyl bromide ammonium, 5 parts of citric acid additions obtain that dissolution is sufficiently stirred in 22 parts of water；
3) after continuously adding 5 parts of PAO synthetic wax, 10 parts of lauryl mercaptan, 5 parts of two lauryl mercaptan, 1 part of soybean oil addition, add
Heat is to 70 DEG C and continues stirring 30 minutes, to obtain lotion.
4) 0.5 part of ethoxyquinoline, 0.5 part of phosphine carboxylic acid are finally added, faintly acid silver protecting agent is obtained.
Embodiment 3
A kind of gold and silver surface anti-oxidation Anti- tarnishing protective agent includes following components: two lauryl mercaptans 15 according to parts by weight
Part, 20 parts of bisphenol A polyethenoxy ether, 15 parts of hydrogenated castor oil polyoxyethylene ether, 5 parts of malic acid, 3 parts of propylene glycol phenylate, 2- mercapto
1 part of base benzothiazole, 8 parts of oxidized polyethylene wax emulsion, 2 parts of dodecyl trimethyl ammonium chloride, 2,2'- di-2-ethylhexylphosphine oxide-(4- first
Base -6- tert-butyl phenol) 1 part, 1 part of dimethicone, 29 parts of water.
A kind of protectant preparation method of gold and silver surface anti-oxidation Anti- tarnishing, comprising the following steps:
1) prepare the raw material of the above weight；
2) by 20 parts of bisphenol A polyethenoxy ether, 15 parts of hydrogenated castor oil polyoxyethylene ether, 5 parts of malic acid, propylene glycol phenylate
3 parts, 2 parts of dodecyl trimethyl ammonium chloride, are added in 29 parts of water, dissolution are sufficiently stirred；
3) 15 parts of two lauryl mercaptan, 1 part of 2,2' methylene bis-(4- methyl-6-tert-butylphenol), diformazan are continuously added
It 1 part of base silicone oil, is heated to 70 DEG C and continues stirring 30 minutes, obtain lotion；
4) it is eventually adding 1 part of 2-mercaptobenzothiazole, 8 parts of oxidized polyethylene wax emulsion, is stirred, faintly acid
Silver protecting agent.
Embodiment 4
A kind of gold and silver surface anti-oxidation Anti- tarnishing protective agent includes following components according to parts by weight: 20 parts of stearylmercaptan,
8 parts of lactic acid, 5 parts of butynediols diethoxy ether, 15 parts of beef tallow amine polyoxyethylene ether, 28 parts of Triton X-100, liquid
8 parts of body paraffin, 3 parts of dodecyl benzyl dimethyl ammonium chloride, 0.5 part of 4,4'- dioctyl diphenylamine, 1 part of sodium benzoate, poly- second
2 parts of alkene imines, 9.5 parts of water.
The above-mentioned protectant preparation method of gold and silver surface anti-oxidation Anti- tarnishing, comprising the following steps:
1) prepare the raw material of the above weight；
2) by 15 parts of beef tallow amine polyoxyethylene ether, 28 parts of Triton X-100,8 parts of lactic acid, dodecylbenzyl
3 parts of alkyl dimethyl ammonium chloride, 5 parts of butynediols diethoxy ether, are added in 9.5 parts of water, dissolution are sufficiently stirred；
3) 20 parts of stearylmercaptan, 8 parts of atoleine, 0.5 part of 4,4'- dioctyl diphenylamine are continuously added, is heated to 60 DEG C
And continue stirring 30 minutes, obtain lotion；
4) 1 part of sodium benzoate, 2 parts of polyethyleneimine are finally added, faintly acid silver protecting agent is stirred to get.
<resistance to potassium sulfide experiment>
The potassium sulfide solution that 2% is prepared in the volumetric flask of 5L, it is spare to tighten bottle cap.
Take processed silver plate, with pure water clean up and after surface air-dry after, prepared 2% potassium sulfide is molten
Liquid pours into beaker, and test sample is put into beaker and is completely immersed in solution and starts timing, impregnates 1 minute, 3 minutes, 5 respectively
Minute, 7 minutes, 9 minutes, taking out the device after impregnating and washing wash clean with clear water (need to clean three times, it is ensured that in test product
Potassium sulfide cleans up), surface moisture is dried with non-dust cloth.
Visually confirm: there is discoloration (redden or blackening) area and is no more than 1% for qualification in silver coating, and silver coating changes colour area
Determine more than 1% unqualified.
The experimental result of 1 embodiment of table and the resistance to potassium sulfide of reference examples
As can be seen from the results, the corrosion-resistant Anti- tarnishing silver protecting agent provided by this patent, silver-colored part after being processed, 2% vulcanization
Potassium test (25 DEG C) can achieve 7 minutes it is non-discolouring；And common silver protecting agent on the market, be only capable of reaching 3-5 minutes it is non-discolouring；
Untreated silver part, changes colour in 1 minute.
<neutral salt spray test>
Neutral salt spray test: in specific chamber (electroplating device), will be containing (5 scholar 0.5) % sodium chloride, pH value
6.5~7.2 salt water is sprayed by spraying device, is allowed salt fog to be deposited on part to be tested, is observed by certain time
Its surface corrosion state.The temperature requirement of chamber is in (50 ± 2) DEG C, and humidity is greater than 95%, and amount of fog is 1~2mL/ (h
cm2), nozzle exit pressure is 78.5~137.3kPa (0.8~1.4kgf/cm2).Sample placed angle: it is disposed vertically.
It cleans up and silver protecting agent treated silver features after surface air-dries with pure water, does neutral salt spray test,
Assess the corrosion resistance of this protecting film.
2 embodiment of table and reference examples neutral salt spray test result
As can be seen from the results, the corrosion-resistant Anti- tarnishing silver protecting agent provided by this patent, silver-colored part, neutral salt spray after being processed
Time generally can achieve 60 hours or more, and certain cases are even up to 75 hours or more, far superior to similar its on the market
His product.
Salt mist experiment:
Through the invention patent treated silver plate, it is non-discolouring that potassium sulfide is tested 7 minutes or more, and neutral salt spray test is 60
Hour or more, lead over similar product both domestic and external；Electronic device, electronic connector, jewellery etc. are applicable to, to welding performance
It has no effect, contact resistance is influenced atomic；All raw material is nontoxic, and environmental protection grade is high, is applicable to spray and soak
The different process such as bubble.
It should be noted that and understand, in the feelings for not departing from the spirit and scope of the present invention required by appended claims
Under condition, various modifications and improvements can be made to the present invention of foregoing detailed description.It is therefore desirable to the model of the technical solution of protection
It encloses and is not limited by given any specific exemplary teachings.
The Applicant declares that the present invention is explained by the above embodiments method detailed of the invention, but the present invention not office
Be limited to above-mentioned method detailed, that is, do not mean that the invention must rely on the above detailed methods to implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of gold and silver surface anti-oxidation Anti- tarnishing protective agent, it is characterised in that: according to parts by weight include following components: preapring for an unfavorable turn of events
15-30 parts of toner, 10-15 parts of film forming agent, 3-8 parts of alcohol ether solvents, 30-50 parts of emulsifier, 2-5 parts of cationic germicide, carboxylic acid
Type deoxygenates agent 5-10 parts, 1-3 parts of corrosion inhibiter, 0.5-1 parts of antioxidant, 1-3 parts of brightener, 5-20 parts of water.
2. gold and silver surface anti-oxidation Anti- tarnishing protective agent according to claim 1, it is characterised in that: the anti-blushing agent
For the compound containing thiol group, include: n- dodecyl mereaptan, tert-dodecyl mercaptan, tetradecanylthioalcohol, 16 mercaptan, octadecyl sulphur
At least one of alcohol, two lauryl mercaptans, Thiodiglycol, Thiodiglycol polyoxyethylene ether.
3. gold and silver surface anti-oxidation Anti- tarnishing protective agent according to claim 1, it is characterised in that: the film forming agent is
80 DEG C of waxes below of fusing point are used in compounding with 100 DEG C of fusing point or more of wax or one of commercially available wax emulsion；The fusing point 80
DEG C wax below be atoleine, semi-refined paraffin wax, fully refined paraffin wax, microwax, montanin wax, lignite wax, in Organosilicon wax extremely
Few one kind；100 DEG C of fusing point or more of the wax is polyethylene wax, in polypropylene wax, PAO synthetic wax, oxidized polyethylene wax
It is at least one；The commercially available wax emulsion is paraffin wax emulsions, in polythene wax emulsion, oxidized polyethylene wax emulsion, silicon wax emulsion
One kind.
4. gold and silver surface anti-oxidation Anti- tarnishing protective agent according to claim 1, it is characterised in that: the alcohol ether solvents
For benzyl alcohol, ethylene glycol phenyl ether, propylene glycol phenylate, 1,4- butynediols, propilolic alcohol, butynediols diethoxy ether, propilolic alcohol
At least one of single propoxyl group ether, butyl, diethylene glycol, dipropylene glycol methyl ether, benzyl oxide.
5. gold and silver surface anti-oxidation Anti- tarnishing protective agent according to claim 1, it is characterised in that: the emulsifier is
Polyethylene glycol, poly glycol monomethyl ether, polyethylene glycol dimethyl ether, isomeric alcohol polyethenoxy ether, alkyl phenol polyoxyethylene ether, fat
Amine polyoxyethylene ether, soybean oleyl amine polyoxyethylene ether, hydrogenated castor oil polyoxyethylene ether, polyoxyethylene oleic acid ester, ethylene oxide
Epoxy propane copolymer, laruyl alcohol atactic polyether, beef tallow amine polyoxyethylene ether, bisphenol A polyethenoxy ether, beta naphthal polyoxyethylene
Ether, tert-butyl benzene phenol polyethenoxy ether, 4- cumylphenol polyoxyethylene ether, tert-octylphenol polyoxyethylene ether (triton X-100,
X114), cardanol polyoxyethylene ether, styrylphenol polyoxyethylene ether, Rhodia Soprophor 796/P, at least one
Kind.
6. gold and silver surface anti-oxidation Anti- tarnishing protective agent according to claim 1, it is characterised in that: the cation kills
Microbial inoculum is dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, hexadecyltrimethylammonium chloride, octadecyl
Trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide, dodecyl benzyl dimethyl ammonium chloride, myristyl benzyl dimethyl
At least one of ammonium chloride, hexadecyl benzyl dimethly ammonium chloride.
7. gold and silver surface anti-oxidation Anti- tarnishing protective agent according to claim 1, it is characterised in that: the carboxylic acid type is gone
Oxidant is lactic acid, citric acid, tartaric acid, malic acid, hydroxyacetic acid, amion acetic acid, gluconic acid, octylphosphonic acid, thio apple
Tartaric acid, thioacetic acid, mercaptopropionic acid, two mercaptan dihydroxy acetic acids, di-2-ethylhexylphosphine oxide thioacetic acid, (ethylene is thio) diethyl
At least one of acid, dithiodipropionic acid；
The antioxidant is 2,2' methylene bis-(4- methyl-6-tert-butylphenol), ethoxyquinoline, 1- naphthylamino
Benzene, N- phenyl-2-naphthylamine, nickel dibutyl dithiocarbamate, 4,4'- dioctyl diphenylamine, 4,4'- bis- (propyloxy phenyl base)
One of diphenylamines, N- cyclohexylthiophthalimide.
8. gold and silver surface anti-oxidation Anti- tarnishing protective agent according to claim 1, it is characterised in that: the corrosion inhibiter is
Benzotriazole, methyl benzotriazazole, 2-mercaptobenzothiazole, 2- hydroxybenzothiazole, 2- methylbenzothiazole, 2- sulfydryl
Benzimidazole, 2- amino -5- sulfydryl -1,3,4- thiadiazoles, glucose, sucrose, mannitol, sodium benzoate, chain alkyl imidazoles
At least one of quinoline, hydrazine hydrate, thiocarbamide, phosphine carboxylic acid and lignosulfonate；
The brightener be Brazil wax, candelila wax, soybean oil, palm oil, polyethyleneimine, stearic acid, palmitinic acid,
One of dimethicone.
9. the described in any item protectant preparation methods of gold and silver surface anti-oxidation Anti- tarnishing of claim 1-8, it is characterised in that:
The following steps are included:
1) prepare the raw material of the above parts by weight；
2) carboxylic acid type is deoxygenated into agent, emulsifier, cationic germicide, is added to the water, dissolution is sufficiently stirred；
3) alcohol ether solvents, antioxidant, anti-blushing agent, brightener are continuously added, and is heated to 60-80 DEG C, keeps this temperature right
It stirs 20-40 minutes afterwards, obtains lotion；
4) corrosion inhibiter, film forming agent are finally added, stirs, obtains gold and silver surface anti-oxidation Anti- tarnishing protective agent.
10. the described in any item gold and silver surface anti-oxidation Anti- tarnishing protective agents of claim 1-8 are used as gold, silver, copper metallic face
Protective agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910563375.1A CN110230061A (en) | 2019-06-26 | 2019-06-26 | A kind of gold and silver surface anti-oxidation Anti- tarnishing protective agent and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910563375.1A CN110230061A (en) | 2019-06-26 | 2019-06-26 | A kind of gold and silver surface anti-oxidation Anti- tarnishing protective agent and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110230061A true CN110230061A (en) | 2019-09-13 |
Family
ID=67857402
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910563375.1A Pending CN110230061A (en) | 2019-06-26 | 2019-06-26 | A kind of gold and silver surface anti-oxidation Anti- tarnishing protective agent and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110230061A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111636083A (en) * | 2020-06-05 | 2020-09-08 | 江苏艾森半导体材料股份有限公司 | Protective agent for preventing high-temperature reflow soldering from tin gathering, and preparation method and use method thereof |
| CN112143348A (en) * | 2020-09-22 | 2020-12-29 | 广州三孚新材料科技股份有限公司 | Protective agent applied to cyanide-free silver plating layer and preparation method thereof |
| CN113563989A (en) * | 2021-08-04 | 2021-10-29 | 上海淑苑科技有限公司 | Jewelry cleaning agent and preparation method thereof |
| CN113957498A (en) * | 2020-07-21 | 2022-01-21 | 江苏汉宜新材料有限公司 | Modification liquid for reducing surface energy of silver-plated layer of cavity |
| CN114773989A (en) * | 2022-03-14 | 2022-07-22 | 苏州瑞港环保科技有限公司 | Anti-silver colloid diffusion agent, preparation method and application thereof |
| CN114921787A (en) * | 2022-06-08 | 2022-08-19 | 天津六0九电缆有限公司 | Corrosion inhibitor for passivating silver-plated copper wire surface and use method thereof |
| CN115125541A (en) * | 2022-05-19 | 2022-09-30 | 宁波博曼特工业有限公司 | Surface oxidation resistance treatment process of tin bronze |
| CN115558424A (en) * | 2022-10-21 | 2023-01-03 | 安徽上氟表面处理技术有限公司 | Noble metal surface protective agent and preparation method thereof |
| CN115595567A (en) * | 2022-08-30 | 2023-01-13 | 胜宏科技（惠州）股份有限公司（Cn） | Anti-tarnishing chemical silver plating solution |
| CN115746605A (en) * | 2022-11-14 | 2023-03-07 | 郎溪县科宏科技有限公司 | Water-soluble gold protective agent and preparation and use method thereof |
| CN116355452A (en) * | 2023-04-12 | 2023-06-30 | 东莞市促裕新材料有限公司 | Sulfur-resistant salt-fog-resistant metal protective agent and preparation method thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0578866A (en) * | 1991-09-25 | 1993-03-30 | Matsushita Electric Works Ltd | Liquid for preventing discoloration of silver plating |
| CN1804015A (en) * | 2005-12-26 | 2006-07-19 | 中国人民解放军总装备部军械技术研究所 | Ultra-thin layered wax film antirust composition for firearm |
| CN101503798A (en) * | 2009-01-19 | 2009-08-12 | 江西科技师范学院 | Silver-plated anti-tarnish protective agent composition |
| CN101514457A (en) * | 2009-04-02 | 2009-08-26 | 西安创联华特表面处理技术有限责任公司 | Multi-purpose metal surface protectant and preparation method thereof |
| CN101925553A (en) * | 2007-11-21 | 2010-12-22 | 恩索恩公司 | Anti-tarnish coating |
| CN101974759A (en) * | 2010-11-23 | 2011-02-16 | 海宁市科泰克金属表面技术有限公司 | Post-treatment protective agent for rare and precious metals |
| 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 |
| CN105779992A (en) * | 2016-04-21 | 2016-07-20 | 常州北化澳联环保科技有限公司 | Water-borne self-assembled metal passivator |
| 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 |
| CN108611628A (en) * | 2016-12-09 | 2018-10-02 | 段钰 | A kind of metal anti-corrosion protection agent |
| CN109097759A (en) * | 2018-09-19 | 2018-12-28 | 深圳市傲新源科技有限公司 | A kind of gold and silver coating Anti- tarnishing protective agent and preparation method thereof and application method |
-
2019
- 2019-06-26 CN CN201910563375.1A patent/CN110230061A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0578866A (en) * | 1991-09-25 | 1993-03-30 | Matsushita Electric Works Ltd | Liquid for preventing discoloration of silver plating |
| CN1804015A (en) * | 2005-12-26 | 2006-07-19 | 中国人民解放军总装备部军械技术研究所 | Ultra-thin layered wax film antirust composition for firearm |
| CN101925553A (en) * | 2007-11-21 | 2010-12-22 | 恩索恩公司 | Anti-tarnish coating |
| CN101503798A (en) * | 2009-01-19 | 2009-08-12 | 江西科技师范学院 | Silver-plated anti-tarnish protective agent composition |
| CN101514457A (en) * | 2009-04-02 | 2009-08-26 | 西安创联华特表面处理技术有限责任公司 | Multi-purpose metal surface protectant and preparation method thereof |
| CN101974759A (en) * | 2010-11-23 | 2011-02-16 | 海宁市科泰克金属表面技术有限公司 | Post-treatment protective agent for rare and precious metals |
| 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 |
| CN105779992A (en) * | 2016-04-21 | 2016-07-20 | 常州北化澳联环保科技有限公司 | Water-borne self-assembled metal passivator |
| 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 |
| CN108611628A (en) * | 2016-12-09 | 2018-10-02 | 段钰 | A kind of metal anti-corrosion protection agent |
| CN109097759A (en) * | 2018-09-19 | 2018-12-28 | 深圳市傲新源科技有限公司 | A kind of gold and silver coating Anti- tarnishing protective agent and preparation method thereof and application method |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111636083B (en) * | 2020-06-05 | 2022-08-12 | 江苏艾森半导体材料股份有限公司 | Protective agent for preventing high-temperature reflow soldering from tin gathering, and preparation method and use method thereof |
| CN111636083A (en) * | 2020-06-05 | 2020-09-08 | 江苏艾森半导体材料股份有限公司 | Protective agent for preventing high-temperature reflow soldering from tin gathering, and preparation method and use method thereof |
| CN113957498A (en) * | 2020-07-21 | 2022-01-21 | 江苏汉宜新材料有限公司 | Modification liquid for reducing surface energy of silver-plated layer of cavity |
| CN112143348A (en) * | 2020-09-22 | 2020-12-29 | 广州三孚新材料科技股份有限公司 | Protective agent applied to cyanide-free silver plating layer and preparation method thereof |
| CN113563989A (en) * | 2021-08-04 | 2021-10-29 | 上海淑苑科技有限公司 | Jewelry cleaning agent and preparation method thereof |
| CN114773989A (en) * | 2022-03-14 | 2022-07-22 | 苏州瑞港环保科技有限公司 | Anti-silver colloid diffusion agent, preparation method and application thereof |
| CN115125541B (en) * | 2022-05-19 | 2024-04-12 | 宁波博曼特工业有限公司 | Surface antioxidation treatment process for tin bronze |
| CN115125541A (en) * | 2022-05-19 | 2022-09-30 | 宁波博曼特工业有限公司 | Surface oxidation resistance treatment process of tin bronze |
| CN114921787A (en) * | 2022-06-08 | 2022-08-19 | 天津六0九电缆有限公司 | Corrosion inhibitor for passivating silver-plated copper wire surface and use method thereof |
| CN114921787B (en) * | 2022-06-08 | 2024-05-28 | 天津六0九电缆有限公司 | Anticorrosive agent for passivating silver-plated copper wire surface and application method thereof |
| CN115595567A (en) * | 2022-08-30 | 2023-01-13 | 胜宏科技（惠州）股份有限公司（Cn） | Anti-tarnishing chemical silver plating solution |
| CN115595567B (en) * | 2022-08-30 | 2023-09-22 | 胜宏科技（惠州）股份有限公司 | Anti-discoloration chemical silver plating solution |
| CN115558424A (en) * | 2022-10-21 | 2023-01-03 | 安徽上氟表面处理技术有限公司 | Noble metal surface protective agent and preparation method thereof |
| CN115746605A (en) * | 2022-11-14 | 2023-03-07 | 郎溪县科宏科技有限公司 | Water-soluble gold protective agent and preparation and use method thereof |
| CN116355452A (en) * | 2023-04-12 | 2023-06-30 | 东莞市促裕新材料有限公司 | Sulfur-resistant salt-fog-resistant metal protective agent and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110230061A (en) | A kind of gold and silver surface anti-oxidation Anti- tarnishing protective agent and its preparation method and application | |
| CN102162095B (en) | Anti-discoloring protective agent for silver plating and preparation method as well as application method thereof | |
| CN1914356B (en) | Surface-treating agent for metal | |
| CN108193209A (en) | A kind of water base plating silver protecting agent of high stability and preparation method thereof | |
| CA2751684C (en) | Silver-containing alloy plating bath and method for electrolytic plating using same | |
| CN103361682A (en) | Method of preventing silver tarnishing | |
| CN101974759A (en) | Post-treatment protective agent for rare and precious metals | |
| CN108396325A (en) | A kind of solderable nickel protective agent of water solubility | |
| CN101851761B (en) | Sulfuric acid washing corrosion-retarding fog inhibitor and preparation method thereof | |
| CN107635676A (en) | The preprocess method of electroless plating | |
| CN1930323B (en) | Metal surface treating agent | |
| JP6370658B2 (en) | Antioxidant for Ni plating film of electronic component, electronic component, and method of manufacturing electronic component | |
| KR100962268B1 (en) | Electric conductivity electric conductivity cus nano corpuscular composition and electric conductivity acryl fiber manufacturing method | |
| CA2769569C (en) | Tin-containing alloy plating bath, electroplating method using same, and substrate with the electroplating deposited thereon | |
| Shibli et al. | Inhibitive effect of calcium gluconate and sodium molybdate on carbon steel | |
| US4483887A (en) | Metal plating iron-containing substrates | |
| CN104746062B (en) | Surface processing solution | |
| CN110079142A (en) | A kind of surface protection water solubility protective agent and method, 5G communications electronics product | |
| JP4397376B2 (en) | Sealing treatment agent, sealing treatment method, and printed circuit board treated with the treatment agent | |
| US3199989A (en) | Corrosion inhibitor and method of using the same | |
| RU2463145C2 (en) | Flux for low-temperature soldering | |
| KR20130069591A (en) | Sealing agent and sealing method | |
| CN106555180B (en) | The guard method of coat of metal protective agent and preparation method thereof and the coat of metal | |
| CN111636083A (en) | Protective agent for preventing high-temperature reflow soldering from tin gathering, and preparation method and use method thereof | |
| GB1217414A (en) | Long term silver dip |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190913 |
|
| RJ01 | Rejection of invention patent application after publication |