CN102605360A - Chemical silvering solution based on imidazolium ionic liquid and silvering method - Google Patents
Chemical silvering solution based on imidazolium ionic liquid and silvering method Download PDFInfo
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- CN102605360A CN102605360A CN2011103095989A CN201110309598A CN102605360A CN 102605360 A CN102605360 A CN 102605360A CN 2011103095989 A CN2011103095989 A CN 2011103095989A CN 201110309598 A CN201110309598 A CN 201110309598A CN 102605360 A CN102605360 A CN 102605360A
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- silver
- chemical silvering
- silvering solution
- ionic liquid
- salt
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Abstract
The invention relates to a chemical silvering solution based on an imidazolium ionic liquid system. The chemical silvering solution contains chlorinated imidazolium ionic liquid, silver salt and water. The volume ratio of chlorinated imidazolium ionic liquid to water equals to (1:9)-(9:1), namely, the volume percentage of the chlorinated imidazolium ionic liquid is 10%-90%, and the concentration range of the silver salt is 0.001-0.1mol/L. A very stable complex can be formed by the chlorinated imidazolium ionic liquid and silver ion, so that the chemical silvering solution provided by the invention does not need to be added with cyanide and is very stable. Thus, the chemical silvering solution is environment-friendly, and meanwhile, the potential safety hazard caused by on-site production is eliminated.
Description
Technical field
The present invention relates to a kind of chemical silvering solution and silver-coating method, particularly a kind of based on ion liquid chemical silvering solution of imidazole salts and silver-coating method.
Background technology
Since silver have good weld, advantage such as weather-proof and conduction, so adopt chemical silvering to come the protection method of copper base material is widely used by the printed electronic circuit board industry.At present, copper base chemical silvering commonly used has two kinds of methods: first kind is autocatalysis chemical silvering method.This method is owing to needing to use reductive agent to make chemical silvering solution liquid be in metastable state, extremely unstable; And require the base metallization surface that metal sensitizing layer (commonly used is the Pd/Sn sensitizing layer) is arranged; Make production cost improve greatly, and then hinder its widespread use on industrial production.Simultaneously, in order to increase the stability of silver plating liquid, add Potssium Cyanide in some chemical silvering solution as complexing agent, well-known, Potssium Cyanide is highly toxic substance, is in the use or in environment protection, all has a lot of problems.Second method is the displacement chemical silver plating method, and this method utilizes copper different with the metal activity of silver, directly with copper as reductive agent, through the replacement(metathesis)reaction of copper and silver ions, the purpose of realization copper electroplate.Silver-plated for displacement method, usually use silver nitrate as silver-colored source, the aqueous solution plating bath of silver nitrate is extremely unstable, often needs now with the current.Simultaneously; The silver plating solution of copper base substitution method needs the higher nitric acid of working concentration usually; Also can corrode the copper substrate carrying out the silver plated while, the later stage welding is had a negative impact, the electron device industry that this is increasingly high for integrated level, size is more and more littler is unacceptable.
In order to improve above-mentioned deficiency; People such as Gu Changdong have invented with choline chloride 60 base ionic liquid as the plating bath (application number 201010231683.3) of solvent at copper substrate surface plating porous nano silver; But; The solvent of this plating bath is mixed by choline chloride 60 base ionic liquid and terepthaloyl moietie and forms, and is under anhydrous like this plating bath environment, slightly inadequate with the technology coupling of chemical silvering.
Summary of the invention
The purpose of this invention is to provide that a kind of and existing chemical silvering technology is complementary, the prescription of the chemical plating liquid of the substrate surfaces such as copper, nickel or nickel-phosphor alloy of low-cost, greenization; Base material after the plating has higher erosion resistance and weldability, is enough to satisfy printed circuit board and the requirement of connector surface-treated.
The technical scheme that realizes above-mentioned purpose is that chemical silvering solution is made up of imidazolium chloride salt ionic liquid, silver salt and water.The composition of imidazolium chloride salt ionic liquid and water is: the imidazolium chloride salt ionic liquid: water (volume ratio)=1: 9-9: 1, and promptly the ion liquid volumn concentration of imidazolium chloride salt is 10%-90%, the concentration range of silver salt is 0.001-0.1mol/L.Because imidazolium chloride salt ionic liquid and silver ions can form highly stable complex compound, so chemical silvering solution of the present invention need not to add prussiate and stablizing very.
The ion liquid structural formula of imidazolium chloride salt in the chemical silvering solution of the present invention is following:
R wherein
1Be methyl, R
2Can be ethyl or butyl, choose, can choose R for imidazolium chloride salt in the chemical plating liquid is ion liquid
2Be ethyl, butyl or both mixtures.
The ion liquid volumn concentration of imidazolium chloride salt is 10%-90% in the chemical silvering solution of the present invention; When ion liquid ratio is lower than 10%; Can cause the solubleness of silver salt in this mixing solutions to reduce, thereby cause plating bath unstable, on the contrary when the ratio of imidazolium chloride salt ionic liquid and water greater than 90% the time; Because the imidazolium chloride salt ionic liquid can cause the plating time elongated with the complexing action of silver, the plating prompt drop is low.Imidazolium chloride salt ionic liquid optimum volume ratio percentage composition is 30%-80% in the chemical silvering solution of the present invention.
Silver salt among the present invention in the chemical silvering solution can be chosen one or both the mixture in Silver monochloride, Sulfuric acid disilver salt, Silver Nitrate and the silver acetate.The add-on of silver salt is 0.001-0.1mol/L.When the concentration of silver salt was lower than 0.001mol/L, because silver salt concentration is low excessively, it was low to cause plating prompt drop, otherwise when the add-on of silver salt during greater than 0.1mol/L, the stability of plating bath is with variation, and the optimum concentration range of silver salt is 0.01-0.05mol/L.
The invention has the beneficial effects as follows: chemical silvering solution of the present invention can be complementary with existing chemical silvering technology, low-cost, greenization; Base material after the plating has higher erosion resistance and weldability, is enough to satisfy printed circuit board and the requirement of connector surface-treated.Because imidazolium chloride salt ionic liquid and silver ions can form highly stable complex compound; So chemical silvering solution of the present invention need not to add prussiate and very stable; So this chemical silvering solution is very friendly to environment, has also eliminated the potential safety hazard that situ production is brought simultaneously.
Specific embodiment
The preparation of embodiment 1 1L chemical plating liquid
With imidazolium chloride salt ionic liquid (R
1=-CH
3, R
2=-CH
2CH
2CH
2CH
3) be example, its compound method describes.After getting the deionized water thorough mixing of above-mentioned imidazolium chloride salt ionic liquid 800mL and 200mL, add Silver monochloride, the concentration that makes Silver monochloride is 0.1mol/L.Use the chemical silvering technology of chemical silvering solution of the present invention to be: at first copper-clad plate to be placed 60 ℃ skim soln (NaOH 10g/L, Na
2CO
320g/L, Na
3PO
412H
2O 5g/L, OP-10 emulsifying agent 1g/L) in, the 5min after washing; Place the etching solution ((NH under the room temperature again
3)
2S
2O
850g/L, H
2SO
4100ml/L), the 1min after washing is to remove the sull of copper foil surface; The copper-clad plate that to pass through pre-treatment places 50 ℃ chemical silvering solution 2min after washing of the present invention, and removes the surface water mark immediately, uses hot blast drying.The result of the stability of plating bath, thickness of coating and weldability lists in table 1.
The preparation of embodiment 2 1L chemical plating liquids
With imidazolium chloride salt ionic liquid (R
1=-CH
3, R
2=-CHCH
3CH
2CH
3) be example, its compound method describes.After getting the deionized water thorough mixing of above-mentioned imidazolium chloride salt ionic liquid 900mL and 100mL, add Silver monochloride, the concentration that makes Silver monochloride is 0.05mol/L.The operating procedure of chemical silvering is referring to embodiment 1, and the result of the stability of plating bath, thickness of coating and weldability lists in table 1.Use in this embodiment and cover the nickel plate as base material.
The preparation of embodiment 3 1L chemical plating liquids
With imidazolium chloride salt ionic liquid (R
1=-CH
3, R
2=-CHCH
3CH
2CH
3) be example, its compound method describes.After getting the deionized water thorough mixing of above-mentioned imidazolium chloride salt ionic liquid 300mL and 700mL, add Silver monochloride, the concentration that makes Silver monochloride is 0.01mol/L.The operating procedure of chemical silvering is referring to embodiment 1, and the result of the stability of plating bath, thickness of coating and weldability lists in table 1.
The preparation of embodiment 4 1L chemical plating liquids
With imidazolium chloride salt ionic liquid (R
1=-CH
3, R
2=-CH
2CH
3) be example, its compound method is described.After getting the deionized water thorough mixing of above-mentioned imidazolium chloride salt ionic liquid 100mL and 900mL, add Silver monochloride, the concentration that makes Silver monochloride is 0.001mol/L.The operating procedure of chemical silvering is referring to embodiment 1, and the result of the stability of plating bath, thickness of coating and weldability lists in table 1.
The preparation of comparative example 1 1L chemical plating liquid
The 20g Silver Nitrate is dissolved in the deionized water of 500ml, slowly adds ammoniacal liquor, generate deposition, continue to add ammoniacal liquor until resolution of precipitate; In addition the 100g Seignette salt is dissolved in the deionized water of 500mL; At room temperature, the silver ammino solution that configures is slowly added in the potassium sodium tartrate solution, the TV that obtains chemical silvering solution is 1L.The operating procedure of chemical silvering is referring to embodiment 1, and the result of the stability of plating bath, thickness of coating and weldability lists in table 1.
Stability, weldability and the thickness of coating of the plating bath of embodiment 5 embodiment 1-4, comparative example 1
Method for estimating stability is: get plating bath 2mL and place quartz colorimetric utensil, use spectrophotometer to scan from 200-400nm, near 300nm, measure the absorbancy (A of the plating bath of preparation completion just
0), disposed 1,3,7,10,15 day the absorbancy (A) in back, calculate absorbance situation over time, be designated as absorbancy rate of descent %=(A
0-A)/A
0, the result sees table 1.
After silver plate to be plated was silver-plated, the measuring method of silver thickness was: at first with chloroazotic acid silver layer is dissolved, then with the concentration of silver ions in the aas determination solution, calculate thickness of coating by concentration of silver ions at last.The thick more then weldability of coating is strong more.
Weldability testing method behind the silver plate electroplate to be plated is: the tin ball of Sn/0.5Cu is placed on the silver plated backing material plate, in 260 ℃ molten tin bath, heat 10s, judge and calculate the expansion size of tin ball, be designated as the rate of spread, the result sees table 1.The rate of spread greater than 85% be qualified, and the rate of spread more greatly then weldability is strong more.
The stability of table 1 silver plating liquid and the performance of silvering
(*: plating time is 20min)
Can find out through embodiment 1-4 and comparative example 1, use chemical silvering solution of the present invention can reach the purpose of chemical silvering within a short period of time, and have good weldability.
With above-mentioned foundation desirable embodiment of the present invention is enlightenment, and through above-mentioned description, the related work personnel can carry out various change and modification fully in the scope that does not depart from this invention technological thought.The technical scope of this invention is not limited to the content on the specification sheets, must confirm its technical scope according to the claim scope.
Claims (6)
1. one kind is applicable to that copper, nickel and nickel-phosphor alloy are the chemical silvering solution of base material, is characterized in that: be made up of imidazolium chloride salt ionic liquid, silver salt and water.
2. the described chemical silvering solution of claim 1, it is characterized in that: the ion liquid volumn concentration of imidazolium chloride salt is 10%-90%, the concentration range of silver salt is 0.001-0.1mol/L.
3. the described chemical silvering solution of claim 1, it is characterized in that: the ion liquid volumn concentration of imidazolium chloride salt is 30%-80%, the concentration range of silver salt is 0.01-0.05mol/L.
4. the described chemical silvering solution of claim 1 is characterized in that: the ion liquid structural formula general formula of imidazolium chloride salt does,
In the formula, R
1Be CH
3, R
2Be CH
2CH
3Or CH
2CH
2CH
2CH
3
5. the described chemical silvering solution of claim 1 is characterized in that: silver salt is one or both the mixture in Silver monochloride, Sulfuric acid disilver salt, Silver Nitrate and the silver acetate.
6. an employing such as each described chemical silvering solution of claim 1-4 silver plated method on copper, nickel or nickel-phosphor alloy base material: it is characterized in that: silver plate to be plated is placed 50-70 ℃ skim soln, the 5-10min after washing; Place the etching solution under the room temperature again, the 1-3min after washing is to remove the sull on silver plate to be plated surface; At last, the silver plate to be plated that will pass through pre-treatment places 20-60 ℃ chemical silvering solution 1-10min after washing, and removes the surface water mark immediately.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110309598.9A CN102605360B (en) | 2011-10-12 | 2011-10-12 | Chemical silvering solution based on imidazolium ionic liquid and silvering method |
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|---|---|---|---|
| CN201110309598.9A CN102605360B (en) | 2011-10-12 | 2011-10-12 | Chemical silvering solution based on imidazolium ionic liquid and silvering method |
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|---|---|
| CN102605360A true CN102605360A (en) | 2012-07-25 |
| CN102605360B CN102605360B (en) | 2014-11-12 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106086834A (en) * | 2016-08-22 | 2016-11-09 | 西安建筑科技大学 | A kind of by adding the method that ionic liquid prepares high corrosion-resistant Ni P chemical deposit |
| CN109338343A (en) * | 2018-09-26 | 2019-02-15 | 长沙理工大学 | A kind of chemical plating liquid and silver-coating method |
| CN109560439A (en) * | 2018-11-12 | 2019-04-02 | 中国科学院电工研究所 | A kind of preparation method of high-temperature superconductor belt lacing |
| CN111620365A (en) * | 2019-02-28 | 2020-09-04 | 中国科学院化学研究所 | High-concentration silver halide solution, preparation method thereof and regeneration method of silver halide |
| CN115261833A (en) * | 2022-08-05 | 2022-11-01 | 深圳市天熙科技开发有限公司 | Chemical silver plating solution for printed circuit board, preparation method and chemical silver plating method |
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| CN1786268A (en) * | 2005-12-15 | 2006-06-14 | 复旦大学 | Self assembly chemical silver plating method on non metal material surface |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106086834A (en) * | 2016-08-22 | 2016-11-09 | 西安建筑科技大学 | A kind of by adding the method that ionic liquid prepares high corrosion-resistant Ni P chemical deposit |
| CN109338343A (en) * | 2018-09-26 | 2019-02-15 | 长沙理工大学 | A kind of chemical plating liquid and silver-coating method |
| CN109560439A (en) * | 2018-11-12 | 2019-04-02 | 中国科学院电工研究所 | A kind of preparation method of high-temperature superconductor belt lacing |
| CN111620365A (en) * | 2019-02-28 | 2020-09-04 | 中国科学院化学研究所 | High-concentration silver halide solution, preparation method thereof and regeneration method of silver halide |
| CN115261833A (en) * | 2022-08-05 | 2022-11-01 | 深圳市天熙科技开发有限公司 | Chemical silver plating solution for printed circuit board, preparation method and chemical silver plating method |
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| Publication number | Publication date |
|---|---|
| CN102605360B (en) | 2014-11-12 |
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