CN102797000B - Choline-chloride-based chemical silvering solution and application method thereof - Google Patents
Choline-chloride-based chemical silvering solution and application method thereof Download PDFInfo
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- CN102797000B CN102797000B CN201210238246.3A CN201210238246A CN102797000B CN 102797000 B CN102797000 B CN 102797000B CN 201210238246 A CN201210238246 A CN 201210238246A CN 102797000 B CN102797000 B CN 102797000B
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- choline chloride
- silver
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- chemical silvering
- water
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Abstract
The invention relates to a choline-chloride-based chemical silvering solution and an application method thereof, belonging to the technical field of silvering. The chemical silvering solution is composed of choline chloride, silver salt and water. The mol ratio of choline chloride to water is 1:2-1:10, and the concentration of the silver salt is 0.001-0.1mol/L. The choline chloride water solution provided by the invention has the advantages of simple components, high preparation convenience and simple and controllable technique. Since the choline chloride water solution and silver ions can form a very stable complex, the chemical silvering solution does not need to add cyanide or any other complexing agent, and is very stable. Thus, the chemical silvering solution is very environment-friendly, and eliminates the potential safety hazard caused by field production.
Description
Technical field
The present invention relates to a kind of chemical silvering solution based on choline chloride 60 and using method thereof, belong to silver-plated technical field.
Background technology
Good to weld because silver has, the advantage such as weather-proof and conduction, so adopt chemical silvering to widely use the printed circuit-board industry of the protection method of Copper base material.At present, conventional copper base chemical silvering has two kinds of methods: the first is autocatalysis chemical silvering method.This method makes chemical silvering solution liquid be in metastable state, extremely unstable because needs use reductive agent, and require that there is metal sensitizing layer (conventional is Pd/Sn sensitizing layer) on base metallization surface, production cost is improved greatly, and then hinders its widespread use in industrial production.Meanwhile, in order to increase the stability of silver plating liquid, add potassium cyanide as complexing agent in some chemical silvering solution, as everyone knows, potassium cyanide is highly toxic substance, be use on or in environment protection, all there is a lot of problem.Second method is displacement chemical silver plating method, and this method utilizes copper different from the metal activity of silver, directly using copper as reductive agent, by the replacement(metathesis)reaction of copper and silver ions, realizes the object of copper electroplate.Silver-plated for substitution method, usually use Silver Nitrate as silver-colored source, the aqueous solution plating solution extremely unstable of Silver Nitrate, often needs now with the current.Simultaneously, the silver plating solution of copper base substitution method needs the nitric acid that working concentration is higher usually, carry out silver-plated while also can corrode copper substrate, to the later stage welding have a negative impact, be unacceptable the electron device industry that this is more and more higher for integrated level, size is more and more less.
In order to improve above-mentioned deficiency, the human hairs such as Gu Changdong understand the plating solution (application number 201010231683.3) using choline chloride 60 base ionic liquid as solvent at Copper base material plated surface porous nano silver, but, the solvent of this plating solution is the dark congruent melting solvent-borne type ionic liquid formed with ethylene glycol of choline chloride 60, anhydrous to processing requirement, so under anhydrous like this plating solution environment, show slightly not enough with the process matching of chemical silvering.
Summary of the invention
The object of this invention is to provide that a kind of and existing Electroless Silver Plating matches, the formula of low cost, the copper of greenization, the chemical plating liquid of the substrate surface such as nickel or nickel-phosphor alloy, base material after plating has higher erosion resistance and weldability, is enough to meet printed circuit board and the requirement of connector surface-treated.
The technical scheme realizing above-mentioned purpose is:
Chemical silvering solution based on choline chloride 60 is made up of choline chloride 60, silver salt and water;
Wherein the composition of choline chloride 60 and water is: choline chloride 60 Li Ye Ti ︰ water (mol ratio)=1 ︰ 2-1 ︰ 10, the concentration range of silver salt is 0.001-0.1mol/L.
The structural formula of the choline chloride 60 in wherein said chemical silvering solution is as follows:
The optimum mole ratio of chemical silvering Chlorine in Solution aqueous choline base solution of the present invention is 1 ︰ 2-1 ︰ 8.
Silver salt in the present invention in chemical silvering solution can choose one or both the mixture in silver chloride, Sulfuric acid disilver salt, Silver Nitrate and silver acetate; The optimum concentration range of silver salt is 0.01-0.05mol/L.
Based on the using method of the chemical silvering solution of choline chloride 60, carry out according to following step: with copper, nickel or nickel-phosphor alloy for matrix, matrix is placed in the skim soln of 50-70 DEG C, 5-10min after washing; Be placed in the etching solution under room temperature again, 1-3min after washing, to remove the oxide film of matrix surface; Skim soln is composed as follows: NaOH 10g/L, Na
2cO
320g/L, Na
3pO
412H
2o 5g/L, OP-10 emulsifying agent 1g/L; Etching solution is by 50g (NH
3)
2s
2o
8h dense with 90ml
2sO
4add water to 1L formulated;
Finally, the matrix leaching through pre-treatment is placed in the chemical silvering solution of above-mentioned choline chloride 60, at 20-60 DEG C, deposits 1-10min, obtain silvering at matrix surface, with water cleaning, dry up.
The invention has the beneficial effects as follows: chemical silvering solution of the present invention can match with existing Electroless Silver Plating, low cost, greenization, base material after plating has higher erosion resistance and weldability, is enough to meet printed circuit board and the requirement of connector surface-treated.Because the choline chloride 60 aqueous solution and silver ions can form highly stable complex compound, so chemical silvering solution of the present invention is without the need to adding prussiate and very stable, so this chemical silvering solution is very friendly to environment, also eliminates the potential safety hazard that situ production is brought simultaneously.
Specific embodiment
The preparation of embodiment 1 1L chemical plating liquid
Get choline chloride 60 to mix according under mol ratio 1 ︰ 2 room temperature with deionized water, magnetic agitation is warmed up to 75 DEG C, obtains the choline chloride 60 aqueous solution for subsequent use as silver plating liquid solvent.Get the solvent 1L prepared, add silver chloride, make the concentration of silver chloride be 0.1mol/L.The Electroless Silver Plating of chemical silvering solution of the present invention is used to be: skim soln (NaOH 10g/L, Na of first copper-clad plate being placed in 60 DEG C
2cO
320g/L, Na
3pO
412H
2o 5g/L, OP-10 emulsifying agent 1g/L) in, 5min after washing; Be placed in the etching solution ((NH under room temperature again
3)
2s
2o
850g/L, H
2sO
4100ml/L), 1min after washing, to remove the oxide film of copper foil surface; Copper-clad plate through pre-treatment is placed in the chemical silvering solution 2min after washing of the present invention of 50 DEG C, and removes surface water mark immediately, use hot blast drying.Thickness of coating and weldability the results are shown in table 1.
The preparation of embodiment 2 1L chemical plating liquid
Get choline chloride 60 to mix according under mol ratio 1 ︰ 2 room temperature with deionized water, magnetic agitation is warmed up to 75 DEG C, obtains the choline chloride 60 aqueous solution as solvent, adds silver chloride, makes the concentration of silver chloride be 0.05mol/L.The operating procedure of chemical silvering see embodiment 1, thickness of coating and weldability the results are shown in table 1.Use in this embodiment and cover nickel plate as base material.
The preparation of embodiment 31 L chemical plating liquid
Get choline chloride 60 to mix according under mol ratio 1 ︰ 8 room temperature with deionized water, magnetic agitation is warmed up to 75 DEG C, obtains the choline chloride 60 aqueous solution as solvent, adds silver chloride, makes the concentration of silver chloride be 0.01mol/L.The operating procedure of chemical silvering see embodiment 1, thickness of coating and weldability the results are shown in table 1.
The preparation of embodiment 41 L chemical plating liquid
Get choline chloride 60 to mix according under mol ratio 1 ︰ 10 room temperature with deionized water, magnetic agitation is warmed up to 75 DEG C, obtains the choline chloride 60 aqueous solution as solvent, adds silver chloride, makes the concentration of silver chloride be 0.001mol/L.The operating procedure of chemical silvering see embodiment 1, thickness of coating and weldability the results are shown in table 1.
The preparation of comparative example 1 1L chemical plating liquid
20g Silver Nitrate is dissolved in the deionized water of 500ml, slowly adds ammoniacal liquor, generate precipitation, continue to add ammoniacal liquor until resolution of precipitate; Separately 100g Seignette salt is dissolved in the deionized water of 500mL; At room temperature, slowly added in potassium sodium tartrate solution by the silver ammino solution configured, the cumulative volume obtaining chemical silvering solution is 1L.The operating procedure of chemical silvering see embodiment 1, thickness of coating and weldability the results are shown in table 1.
the weldability of embodiment 5 embodiment 1-4, comparative example 1 and thickness of coating
Weldability testing method after silver plate electroplate to be plated is tested according to GB/T 2423 weldability standard.The SKC-8H Weldability detector that the instrument used is produced for Shanghai Run Pu test set company limited.Concrete testing method is as follows: 30s is put in sample leaching in immersed solder agent (volume fraction is 75% staybelite+25% dehydrated alcohol), after taking out dry 10s, sample is hung on equipment, preheating 30s, scrapes off the oxide compound of solder surface, starts weldability test at 235 ± 2 DEG C.
After matrix is silver-plated, the measuring method of silver thickness is: first dissolved by silver layer with chloroazotic acid, then uses the concentration of silver ions in aas determination solution, finally calculates thickness of coating by concentration of silver ions.The thicker then weldability of coating is stronger.
The performance of table 1 silvering
| ? | Infiltrating time t b | Thickness of coating |
| Embodiment 1 | 1.46s | 0.34μm |
| Embodiment 2 | 1.43s | 0.36μm |
| Embodiment 3 | 1.53s | 0.13μm |
| Embodiment 4 | 1.61s | 0.08μm |
| Comparative example 1 | 1.54s | 0.14μm * |
(*: plating time is 5min)
Can be found out by embodiment 1-4 and comparative example 1, use chemical silvering solution of the present invention can reach the object of chemical silvering within a short period of time, and there is good weldability.
Because the choline chloride 60 aqueous solution and silver ions can form highly stable complex compound, so chemical silvering solution of the present invention is without the need to adding prussiate and very stable.
The composition of chemical silvering Chlorine in Solution choline of the present invention and water is: Lvization Dan Jian ︰ water (mol ratio)=1 ︰ 2-1 ︰ 10, when the ratio of choline chloride 60 and water is lower than 1 ︰ 2, choline chloride 60 can not dissolve completely, and because choline chloride 60 and the complexing action of silver can cause the plating time elongated, plating prompt drop is low; Otherwise, when the ratio of choline chloride 60 and water is higher than 1 ︰ 8, the solubleness of silver salt in this mixing solutions can be caused to reduce, thus cause plating solution unstable.The optimum mole ratio of chemical silvering Chlorine in Solution aqueous choline base solution of the present invention is 1 ︰ 2-1 ︰ 8.
Silver salt in the present invention in chemical silvering solution can choose one or both the mixture in silver chloride, Sulfuric acid disilver salt, Silver Nitrate and silver acetate.The add-on of silver salt is 0.001-0.1mol/L.When the concentration of silver salt is lower than 0.001mol/L, because silver salt concentrations is too low, plating prompt drop can be caused low, otherwise when the add-on of silver salt is greater than 0.1mol/L, the stability of plating solution will be deteriorated, the optimum concentration range of silver salt is 0.01-0.05mol/L.
With above-mentioned according to desirable embodiment of the present invention for enlightenment, by above-mentioned description, relevant staff in the scope not departing from this invention technological thought, can carry out various change and amendment completely.The technical scope of this invention is not limited to the content on specification sheets, must determine its technical scope according to right.
Claims (2)
1., based on the chemical silvering solution of choline chloride 60, it is characterized in that being made up of choline chloride 60, silver salt and water;
Wherein the composition of choline chloride 60 and water is: Lvization Dan Jian ︰ water mol ratio is 1 ︰ 2-1 ︰ 8;
The structural formula of wherein said choline chloride 60 is as follows:
；
Silver salt is wherein one or both the mixture in silver chloride, Sulfuric acid disilver salt, Silver Nitrate or silver acetate; The concentration range of silver salt is 0.01-0.05mol/L.
2. based on the using method of the chemical silvering solution of choline chloride 60 according to claim 1, carry out according to following step: based on the using method of the chemical silvering solution of choline chloride 60, carry out according to following step: with copper, nickel or nickel-phosphor alloy for matrix, matrix is placed in the skim soln of 50-70 DEG C, 5-10min after washing; Be placed in the etching solution under room temperature again, 1-3min after washing, to remove the oxide film of matrix surface; Skim soln is composed as follows: NaOH 10g/L, Na
2cO
320g/L, Na
3pO
412H
2o 5g/L, OP-10 emulsifying agent 1g/L; Etching solution is by 50g (NH
3)
2s
2o
8h dense with 90ml
2sO
4add water to 1L formulated; Finally, the matrix leaching through pre-treatment is placed in the chemical silvering solution of above-mentioned choline chloride 60, at 20-60 DEG C, deposits 1-10min, obtain silvering at matrix surface, with water cleaning, dry up.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210238246.3A CN102797000B (en) | 2012-07-11 | 2012-07-11 | Choline-chloride-based chemical silvering solution and application method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210238246.3A CN102797000B (en) | 2012-07-11 | 2012-07-11 | Choline-chloride-based chemical silvering solution and application method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN102797000A CN102797000A (en) | 2012-11-28 |
| CN102797000B true CN102797000B (en) | 2014-12-31 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103013523B (en) * | 2012-12-13 | 2014-05-14 | 北京七星华创电子股份有限公司 | Etching agent as well as preparation method and application thereof |
| CN110714212B (en) * | 2019-10-12 | 2021-04-30 | 常州大学 | Method for preparing super-hydrophobic nickel film in aqueous solution system by nickel chloride one-step method |
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2012
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Non-Patent Citations (2)
| Title |
|---|
| PRELIMINARY STUDIES OF SILVER COATINGS FORMATION FROM CHOLINE CHLORIDE BASED IONIC LIQUIDS;Andreea FLOREA et al.;《U.P.B. Sci. Bull.》;20101231;第72卷(第2期);115-126 * |
| Zn2+作为化学镀镍溶液稳定剂的研究;陈智栋等;《材料保护》;20080430;第41卷(第4期);33-36 * |
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