CN102363885B - Pretreatment solution for selective stripping of silver coating and quantitative analysis of elements in silver coating - Google Patents
Pretreatment solution for selective stripping of silver coating and quantitative analysis of elements in silver coating Download PDFInfo
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- CN102363885B CN102363885B CN 201110308949 CN201110308949A CN102363885B CN 102363885 B CN102363885 B CN 102363885B CN 201110308949 CN201110308949 CN 201110308949 CN 201110308949 A CN201110308949 A CN 201110308949A CN 102363885 B CN102363885 B CN 102363885B
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- acid
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Abstract
The invention relates to a solution for selective stripping of a silver coating. The solution consists of the following components in percentage by mass: 0.01 to 10 percent of chloroacetic acid, 0.01 to 10 percent of carboxylic acid, 1 to 20 percent of hydrogen peroxide, and the balance of deionized water. The solution has the advantages that: the solution does not contain nitric acid, hydrochloric acid, sulfuric acid and other strong acid, so when the silver coating is stripped, the solution can greatly improve the environment of field production operation; and the solution has the property of selectively corroding silver, so that the solution slightly influences the surface of a base material and can be used as the pretreatment solution for the quantitative analysis of elements in the silver coating.
Description
Technical field
The present invention relates to the pre-treatment solution of quantitative elementary analysis in a kind of selective detachment silvering and the silvering.
Background technology
In printed circuit board or electronic connector manufacturing process, in order to protect base material and to increase weldability, usually carry out silver-plated at substrate surface.In the process of making printed circuit board, also may again the part silvering be peeled off according to the needs of technology, also may be when Processing Ag coating unacceptable product, silvering is peeled off, also may silvering be peeled off in order to analyze the content of metallic element in the silvering.
The solution of peeling off for silvering adopts prussiate, chromic salt and strong acid solution usually.Well-known prussiate is highly toxic substance, and environmental pollution is very big; And chromic salt also is not used gradually owing to its pollution to environment; Because strong acid is easy to generate acid mist, can cause bad influence to the production scene.Simultaneously, silvering stripping solution commonly used is the corrosion base material directly, and silvering is not had selectivity.
Summary of the invention
The technical problem to be solved in the present invention is: very big for solving the solution environmental pollution that present silvering peels off; Can directly corrode base material, silvering there is not optionally technical problem, the invention provides the pre-treatment solution of quantitative elementary analysis in a kind of selective detachment silvering and the silvering, the pre-treatment solution of quantitative elementary analysis does not corrode base material in this selective detachment silvering and the silvering, and it is very fast to remove silver-colored speed.Because the pre-treatment solution of quantitative elementary analysis does not contain prussiate and strong acid in selective detachment silvering of the present invention and the silvering, so the pre-treatment solution solution of quantitative elementary analysis is environmentally friendly in this selective detachment silvering and the silvering.
The technical scheme that the present invention solves its technical problem employing is: the pre-treatment solution of quantitative elementary analysis is made of Mono Chloro Acetic Acid, carboxylic acid, hydrogen peroxide and deionized water in a kind of selective detachment silvering and the silvering.
Chloroacetic mass percentage concentration is 0.01～10%, and the mass percentage concentration of carboxylic acid is 0.01～10%, and the mass percentage concentration of hydrogen peroxide is 1～20%, and all the other are deionized water.
Mono Chloro Acetic Acid is selected from one or more mixture of Monochloro Acetic Acid, dichloro acetic acid trichoroacetic acid(TCA).When chloroacetic mass percentage concentration greater than 10% the time, corrode base material easily, selectivity descends; When chloroacetic mass percentage concentration was lower than 0.01%, to the poor effect of peeling off of silvering, splitting time was long.Chloroacetic mass percentage concentration scope is 0.01～10%, and best in quality percentage concentration scope is 0.1～5%.
The adding of carboxylic acid, help to increase the peeling rate to silvering, carboxylic acid is monoprotic acid or diprotic acid, wherein contain carbon number for being not more than 5, as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, propanedioic acid, Succinic Acid, pentanedioic acid etc., when the mass percentage concentration of carboxylic acid greater than 10% the time, merely concerning peeling off silvering, have no effect, but when with stripping solution as the pretreatment liquid of peeling off silvering, when other elements carried out quantitative analysis in the silvering, too much carboxylic acid can cause measurement result on the low side.When the mass percentage concentration of carboxylic acid was lower than 0.01%, the influence that the acceleration silvering is peeled off was difficult to manifest.The mass percentage concentration of carboxylic acid is 0.01～10%, and its best in quality percentage concentration scope is 1～5%.
In selective detachment silvering of the present invention and silvering in the pre-treatment solution of quantitative elementary analysis, the add-on of hydrogen peroxide is that mass percentage concentration is 1～20%, when the mass percentage concentration of hydrogen peroxide greater than 20% the time, solution is very fast to the peeling rate of silvering, but this solution also can produce corrosion to base material simultaneously, causes selectivity to descend.When the mass percentage concentration of hydrogen peroxide less than 1% the time, the pre-treatment solution of quantitative elementary analysis is low excessively to the peeling rate of silvering in selective detachment silvering and the silvering, the optimum range of hydrogen peroxide mass percentage concentration is 5～10%.
Use the pre-treatment solution methods of quantitative elementary analysis in selective detachment silvering of the present invention and the silvering to be: the print of desire being removed silvering places 45 ℃ degreasing cleaning fluid (NaOH 10g/L, Na
2CO
320g/L, Na
3PO
412H
2O 5g/L, OP-10 emulsifying agent 1g/L) 5min, after the washing print is placed the pre-treatment solution of selective detachment silvering of the present invention and silvering quantitative elementary analysis, until all exposing the substrate layer color, take out the after washing hot-air seasoning.
Technique effect of the present invention is: do not contain just like strong acid such as nitric acid, hydrochloric acid and sulfuric acid, when silvered film was peeled off, the use of this solution can greatly improve the environment of situ production operation; Simultaneously because this solution has the characteristic of selective corrosion silver, so this solution is little to the influence of substrate surface, and can be directly as the pretreatment liquid of quantitative elementary analysis in the silvering.
Specific embodiment
Introduce effect of the present invention below by specific embodiment.
The preparation of the pre-treatment solution of quantitative elementary analysis in embodiment 1 1000g selective detachment silvering and the silvering
Mono Chloro Acetic Acid is example with the Monochloro Acetic Acid, carboxylic acid is example with acetic acid, compound method to the silvering stripping liquid describes, the Monochloro Acetic Acid of getting 0.1g joins in the deionized water of 600g, fully mix the acetic acid that the back adds 100g, treat that fully mixing the back adds hydrogen peroxide 200g, the deionized water and stirring that adds 99.9g is again mixed.
The preparation of the pre-treatment solution of quantitative elementary analysis in embodiment 2 1000g selective detachment silvering and the silvering
Mono Chloro Acetic Acid is example with the dichloro acetic acid, carboxylic acid is example with formic acid, compound method to the silvering stripping liquid describes, the dichloro acetic acid of getting 1g joins in the deionized water of 600g, fully mix the formic acid that the back adds 50g, treat that fully mixing the back adds hydrogen peroxide 100g, the deionized water and stirring that adds 240g is again mixed.
The preparation of the pre-treatment solution of quantitative elementary analysis in embodiment 3 1000g selective detachment silvering and the silvering
Mono Chloro Acetic Acid is example with the trichoroacetic acid(TCA), carboxylic acid is example with acetic acid, compound method to the silvering stripping liquid describes, the Monochloro Acetic Acid of getting 50g joins in the deionized water of 600g, fully mix the pentanedioic acid that the back adds 1g, treat that fully mixing the back adds hydrogen peroxide 50g, the deionized water and stirring that adds 290g is again mixed.
The preparation of the pre-treatment solution of quantitative elementary analysis in embodiment 4 1000g selective detachment silvering and the silvering
Mono Chloro Acetic Acid is example with Monochloro Acetic Acid and trichoroacetic acid(TCA), carboxylic acid is example with the propanedioic acid, compound method to the silvering stripping liquid describes, getting the Monochloro Acetic Acid of 50g and the trichoroacetic acid(TCA) of 50g joins in the deionized water of 600g, fully mix the propanedioic acid that the back adds 0.1g, treat that fully mixing the back adds hydrogen peroxide 10g, the deionized water and stirring that adds 289.9g is again mixed.
The preparation of comparative example 1 1L silvering stripping liquid
Be example with the Sulfothiorine stripping liquid, the compound method of stripping liquid is described, get in the deionized water that 300g Sulfothiorine is dissolved in 1000ml, stir solid is fully dissolved.(because the strong acid type stripping liquid is too big to base material corrodibility, do not compare example so do not select here.Select the Sulfothiorine silvering stripping liquid of mild herein as a comparison.)
In embodiment 5 selective detachment silvering and the silvering pre-treatment solution of quantitative elementary analysis when removing silvering to the influence of substrate surface
After removing silvering, again the silver-plated sample of doing over again, need to keep the planeness of substrate surface extremely important, thus estimated use quantitative elementary analysis in selective detachment silvering of the present invention and the silvering pre-treatment solution when removing silvering to the influence of substrate surface.Concrete grammar is: at first, utilize microscope to measure the roughness of copper-clad plate surface Copper Foil, after this sample surfaces is silver-plated, after the silvering stripping liquid of the pre-treatment solution of quantitative elementary analysis and comparative example 1 is peeled off silver layer in the selective detachment silvering of use embodiment of the invention 1-4 and the silvering, measure the roughness of copper foil surface again, its roughness changes and to be not more than 10%, be labeled as ◎, its roughness changes greater than 10% and is not more than 20%, be labeled as zero, roughness changes greater than 20%, is labeled as X.The results are shown in Table 1.
The pre-treatment solution of quantitative elementary analysis and silvering stripping liquid are handled the variation of back copper foil surface roughness in table 1 selective detachment silvering and the silvering
| Example | Handle back copper foil surface roughness velocity of variation |
| Embodiment 1 | ◎ |
| Embodiment 2 | ◎ |
| Embodiment 3 | ◎ |
| Embodiment 4 | ○ |
| Comparative example 1 | ○ |
The content analysis of other elements in embodiment 6 silvering
For the content of analyzing other elements in the silvering, as the Cd in the RoHS instruction
2+, Hg
2+, Pb
2+And Cr
6+, it is particularly important that the selective detachment of silvering shows.Because if silvering stripping liquid excessive corrosion base material can be brought into the micro impurity element in the base material to be measured peeling off in the silver-colored solution.Therefore, estimated the selectivity of using the pre-treatment solution of quantitative elementary analysis in selective detachment silvering of the present invention and the silvering, its method places the pre-treatment solution (room temperature) of 50mL embodiment of the invention 1-4 selective detachment silvering and silvering quantitative elementary analysis and the silvering stripping liquid (70 ℃) of comparative example 1 for the copper-clad plate that 2 * 2cm is silver-plated, after treating to expose the copper substrate surface fully, take out copper-clad plate.The pre-treatment solution and the silver-colored stripping liquid that have dissolved quantitative elementary analysis in silver-colored selective detachment silvering and the silvering are transferred to respectively in the volumetric flask of 100ml, be diluted to scale, with the content of cupric ion in the atomic absorption spectroscopy determination stripping liquid, judge the selectivity of the pre-treatment solution of quantitative elementary analysis in selective detachment silvering of the present invention and the silvering.The results are shown in Table 2.
Table 2 is dissolved in the concentration of pre-treatment solution and the cupric ion in the silvering stripping liquid of quantitative elementary analysis in selective detachment silvering and the silvering
| Example | Copper ion concentration in the stripping liquid (μ g/ml) |
| Embodiment 1 | 98 |
| Embodiment 2 | 79 |
| Embodiment 3 | 158 |
| Embodiment 4 | 220 |
| Comparative example 1 | 178 |
(the embodiment 1-4 glass time at room temperature is about 6min, 4min, 5min, 8min respectively, and the splitting time of comparative example 1 under 70 ℃ is 9min)
Be enlightenment with above-mentioned foundation desirable embodiment of the present invention, by 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 determine its technical scope according to the claim scope.
Claims (3)
1. one kind is applicable to the pre-treatment solution of peeling off quantitative elementary analysis in silvering and the silvering, it is characterized in that: the formation of this solution is counted by mass percentage concentration, the hydrogen peroxide of the Mono Chloro Acetic Acid of 0.01-10%, the carboxylic acid of 0.01-10%, 1-20%, all the other are deionized water, and Mono Chloro Acetic Acid is selected from one or more mixtures in Monochloro Acetic Acid, dichloro acetic acid, the trichoroacetic acid(TCA); Carboxylic acid is selected from formic acid, acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, propanedioic acid, Succinic Acid or pentanedioic acid.
2. the described pre-treatment solution of claim 1 is characterized in that chloroacetic mass percentage concentration is 0.1-5%, and the mass percentage concentration of carboxylic acid is 0.1-10%, and the mass percentage concentration of hydrogen peroxide is 5-10%, and all the other are deionized water.
3. the described pre-treatment solution of claim 1 is characterized in that silvering is that plating is on copper, steel or iron nickel alloy base material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110308949 CN102363885B (en) | 2011-10-12 | 2011-10-12 | Pretreatment solution for selective stripping of silver coating and quantitative analysis of elements in silver coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110308949 CN102363885B (en) | 2011-10-12 | 2011-10-12 | Pretreatment solution for selective stripping of silver coating and quantitative analysis of elements in silver coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102363885A CN102363885A (en) | 2012-02-29 |
| CN102363885B true CN102363885B (en) | 2013-08-21 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 201110308949 Expired - Fee Related CN102363885B (en) | 2011-10-12 | 2011-10-12 | Pretreatment solution for selective stripping of silver coating and quantitative analysis of elements in silver coating |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103074497A (en) * | 2013-01-24 | 2013-05-01 | 惠州Tcl环境科技有限公司 | Method for recovering silver from waste film |
| CN105256325A (en) * | 2015-10-28 | 2016-01-20 | 湖南赛奥硅业股份有限公司 | Stripping agent for silver plating layer |
| CN108425145A (en) * | 2018-05-09 | 2018-08-21 | 泉州市蓝水环保科技有限公司 | A kind of nontoxic copper and iron base silver decoating liquid and its withdrawal plating |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1476489A (en) * | 2001-10-09 | 2004-02-18 | 长濑化成株式会社 | Etchant composition |
| CN1678714A (en) * | 2002-08-26 | 2005-10-05 | 默克专利有限公司 | Etching pastes for titanium oxide surfaces |
| CN1237207C (en) * | 2003-06-25 | 2006-01-18 | 铼宝科技股份有限公司 | Silver alloy etching solution |
-
2011
- 2011-10-12 CN CN 201110308949 patent/CN102363885B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1476489A (en) * | 2001-10-09 | 2004-02-18 | 长濑化成株式会社 | Etchant composition |
| CN1678714A (en) * | 2002-08-26 | 2005-10-05 | 默克专利有限公司 | Etching pastes for titanium oxide surfaces |
| CN1237207C (en) * | 2003-06-25 | 2006-01-18 | 铼宝科技股份有限公司 | Silver alloy etching solution |
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| CN102363885A (en) | 2012-02-29 |
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Granted publication date: 20130821 Termination date: 20161012 |