CN101760730A - Low-temperature chemical tinning solution and tinning method - Google Patents
Low-temperature chemical tinning solution and tinning method Download PDFInfo
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- CN101760730A CN101760730A CN 201010113531 CN201010113531A CN101760730A CN 101760730 A CN101760730 A CN 101760730A CN 201010113531 CN201010113531 CN 201010113531 CN 201010113531 A CN201010113531 A CN 201010113531A CN 101760730 A CN101760730 A CN 101760730A
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Abstract
The invention provides low-temperature chemical tinning solution and a tinning method; the tinning solution is divided into A solution and B solution, the A solution comprises stannous sulfate, stannous chloride or stannic chloride, concentrated sulfuric acid, polyethylene glycol, triethanolamine and the like; B solution comprises thiocarbamide and concentrated sulfuric acid; the tinning method is as follows: copper or copper alloy is soaked in the A solution for 30-180s, and then is soaked in the B solution for 60-300s, so as to carry out tinning and obtain silvery white bright tinning layer, the solution working temperature is 10-35 DEG C; in the invention, the tinning is stable, tinning speed is rapid, the cost is low, the solution is energy saving and environment-protection and has practical value.
Description
Technical field
The present invention relates to the chemical plating to metal material surface, specifically is a kind of cryochemistry tin plating solution and tin plating method that is used for copper or copper alloy substrate surface.
Background technology
Along with miniaturization of electronic products, as the also miniaturization day by day of printed-wiring board (PWB) (PCB) of fine circuit and microelectronic device carrier, traditional hot air leveling technology (HASL) can not satisfy the requirement of electronic industry.And chemical tin plating process is because its good repeatedly weldability, coating even compact, technological operation is simple, security is good etc., and advantage more and more comes into one's own.If people expected especially to find a kind of chemical plating stannum method of with low cost, simple and efficient, energy-conserving and environment-protective.
About chemical plating stannum, the method for main employing main salt+reductive agent+coordination agent (promotor)+other additive (complexing agent, antioxidant and tensio-active agent etc.) is carried out the research of chemical plating stannum both at home and abroad at present.Wherein main salt mainly adopts inorganic tin salts system (tin protochloride or stannous sulfate or fluoroborate) and organic tin salt system (methyl sulfonic acid tin or ethane sulfonic acid tin); Reductive agent mainly adopts ortho phosphorous acid, hypophosphite, formaldehyde, sodium borohydride etc.; Coordination agent mainly adopts thiocarbamide and derivative thereof, and purpose is effectively to reduce the redox potential of copper, makes Sn
2+Generate tin coating with copper generation replacement(metathesis)reaction; Complexing agent and antioxidant are to improve Sn
2+Stability, prevent Sn
2+Be oxidized to Sn
4+Tensio-active agent can make the more smooth exquisiteness of coating.
Chinese patent application CN101403112A " chemical tin plating liquor of copper and copper alloy " discloses the tin plating electrolyte of organic tin salt systems such as comprising tin methane sulfonate, methylsulfonic acid, thiocarbamide and derivative thereof, inferior sodium phosphate, Resorcinol and OP-10.
Chinese patent CN100547111C " a kind of chemical plating stannum solution " disclose comprise stannous sulfate, the vitriol oil, inferior sodium phosphate, Pyrithioxine hydrochloride, 4,4 '-tin plating electrolyte of inorganic tin salts system such as (2-pyridine methylene) biphenol, Schiff alkali, amidinothiourea, polyethylene glycol 6000.
Chen Chuncheng (chemical tin plating process research is electroplated and 2002 the 5th phases of finish on the copper base), provide the tin plating electrolyte of organic tin salt systems such as comprising methyl sulfonic acid tin, methyl sulfonic acid, reductive agent (inferior sodium phosphate, hydrazine hydrate), promotor (thiocarbamide, thiosinamine etc.), complexing agent (citric acid, gluconic acid, EDTA etc.), antioxidant, 50～70 ℃ of plating temperatures.
Sun Wu etc. (cryochemistry tin plating technique condition influences plating and environmental protection in May, 2006 to tin thickness) provide the tin plating electrolyte of inorganic tin salts systems such as comprising stannous sulfate, the vitriol oil, coordination agent, inferior sodium phosphate, 45 ℃ of plating temperatures.
Above tin plating method, perhaps working temperature is higher, and more energy need be provided; Perhaps additive is of a great variety, has increased zinc-plated cost; Perhaps use the hypophosphite of higher concentration, increased the expense that waste plating solution is handled.
Summary of the invention
The object of the present invention is to provide a kind of cryochemistry tin plating solution and tin plating method, this tin plating solution and the tin plating method cost is low, energy consumption is low, stability of solution is good, silvery white bright tin plating layer can be obtained on the surface of copper and alloy thereof, the environmental protection load can be effectively reduced simultaneously.
A kind of cryochemistry tin plating solution provided by the invention is divided into A solution and B solution, and its component and proportioning are respectively:
A solution:
Stannous sulfate 20～45g/L
98% vitriol oil, 20～50mL/L
Polyethylene glycol 6000 0.05～0.25g/L
Trolamine 0.1～0.4g/L
Paregal O 0-0.02g/L
All the other are deionized water or distilled water;
B solution:
Thiocarbamide 20～100g/L
98% vitriol oil, 20～50mL/L
All the other are deionized water or distilled water.
Described stannous sulfate can replace with tin protochloride or tin tetrachloride pentahydrate.
Described trolamine can replace with diethanolamine or thanomin.
The preparation method of described cryochemistry tin plating solution, comprise the steps: the preparation (by said components and proportioning) of A solution: at first the vitriol oil is slowly added in part deionized water or the distilled water, successively stannous sulfate, polyethylene glycol 6000, trolamine, paregal O are added then, fully the dissolving back is assigned to prescribed volume with deionized water or distilled water.The preparation of B solution (by said components and proportioning): the vitriol oil is slowly added in part deionized water or the distilled water, add thiocarbamide then, fully the dissolving back is assigned to prescribed volume with deionized water or distilled water.
The tinned method of the above-mentioned low temperature electroless plating solution of tin of a kind of usefulness provided by the invention, plating material copper or copper alloy were soaked in A solution 30～180 seconds earlier, in B solution, soaked 60～300 seconds again, can finish plating, 10～35 ℃ of A solution, B solution working temperatures.
Advantage compared with prior art of the present invention and effect: the present invention adopts two groups of solution of A, B to carry out plating, has realized the tinned possibility of low temperature (10～35 ℃).Plating material effect multilayer by static, Van der Waals force, hydrogen bond in A solution is adsorbed Sn
2+(or Sn
4+) ion, in B solution, reducing the redox potential of copper by thiocarbamide and derivative thereof, the tin ion that makes absorption is reduced into tin by replacement(metathesis)reaction closely, makes so zinc-platedly just can carry out fast at low temperatures.In A solution because chemical reaction does not take place, so solution can preserve for a long time, even if a small amount of Sn is arranged in air
2+Be oxidized to Sn
4+, Sn
4+Also can in B solution, be reduced into metallic tin.The hydrolysis reaction of pink salt belongs to thermo-negative reaction, because present method plating temperature is low, suitable acidity just can suppress the hydrolysis of pink salt, needn't add complexing agent in addition; Because Sn
4+A solution utilize present method also more easily to be reduced into tin, so also needn't add oxidation inhibitor; In B solution, not or a small amount of Sn arranged
2+Or Sn
4+, there is an amount of acid just to exist and hydrolysis can not take place, but also prolonged preservation of solution.All do not add reductive agent, antioxidant, complexing agent in two groups of solution of A, B, the amount of other additive is very little, so that the processing of waste plating solution will be easy to is many.
In a word, tin plating solution chemical material kind of the present invention is few, and cost is low; Plating method temperature is low, and power consumption is few, and technological process is easy to control; Waste plating solution is handled easily.Zinc-plated surface compact, smooth, bright has practical value.
Embodiment:
Embodiment 1
A solution:
Stannous sulfate 20g/L
98% vitriol oil 20mL/L
Polyethylene glycol 6000 0.05g/L
Trolamine 0.1g/L
Paregal O 0.02g/L
All the other are deionized water or distilled water.
B solution:
Thiocarbamide 50g/L
98% vitriol oil 40mL/L
All the other are deionized water or distilled water.
Plating method: earlier copper sheet was soaked 180 seconds in A solution, in B solution, soaked 300 seconds again, can finish plating, obtain silvery white bright tin plating layer, 20 ℃ of solution working temperatures.
Embodiment 2
A solution:
Stannous sulfate 45g/L
98% vitriol oil 50mL/L
Polyethylene glycol 6000 0.25g/L
Trolamine 0.4g/L
Paregal O 0g/L
All the other are deionized water or distilled water.
B solution:
Thiocarbamide 20g/L
98% vitriol oil 20mL/L
All the other are deionized water or distilled water.
Plating method: earlier copper sheet was soaked 30 seconds in A solution, in B solution, soaked 60 seconds again, can finish plating, 15 ℃ of solution working temperatures.
Embodiment 3
A solution:
Stannous sulfate 30g/L
98% vitriol oil 30mL/L
Polyethylene glycol 6000 0.1g/L
Trolamine 0.2g/L
Paregal O 0.01g/L
All the other are deionized water or distilled water.
B solution:
Thiocarbamide 40g/L
98% vitriol oil 30mL/L
All the other are deionized water or distilled water.
Plating method: earlier copper alloy was soaked 90 seconds in A solution, in B solution, soaked 180 seconds again, can finish plating, 25 ℃ of solution working temperatures.
Embodiment 4
A solution:
Stannous sulfate 40g/L
98% vitriol oil 45mL/L
Polyethylene glycol 6000 0.2g/L
Trolamine 0.3g/L
Paregal O 0.005g/L
All the other are deionized water or distilled water.
B solution:
Thiocarbamide 100g/L
98% vitriol oil 50mL/L
All the other are deionized water or distilled water.
Plating method: earlier copper sheet was soaked 90 seconds in A solution, in B solution, soaked 300 seconds again, can finish plating, 10 ℃ of solution working temperatures.
Embodiment 5
A solution:
Stannous sulfate 30g/L
98% vitriol oil 30mL/L
Polyethylene glycol 6000 0.15g/L
Trolamine 0.25g/L
Paregal O 0.01g/L
All the other are deionized water or distilled water.
B solution:
Thiocarbamide 20g/L
98% vitriol oil 20mL/L
All the other are deionized water or distilled water.
Plating method: earlier copper alloy was soaked 80 seconds in A solution, in B solution, soaked 200 seconds again, can finish plating, 35 ℃ of solution working temperatures.
Claims (4)
1. a cryochemistry tin plating solution is characterized in that being divided into A solution and B solution, and its component and proportioning are respectively:
A solution:
Stannous sulfate 20～45g/L
98% vitriol oil, 20～50mL/L
Polyethylene glycol 6000 0.05～0.25g/L
Trolamine 0.1～0.4g/L
Paregal O 0-0.02g/L
All the other are deionized water or distilled water;
B solution:
Thiocarbamide 20～100g/L
98% vitriol oil, 20～50mL/L
All the other are deionized water or distilled water.
2. a kind of cryochemistry tin plating solution as claimed in claim 1 is characterized in that, described stannous sulfate replaces with tin protochloride or tin tetrachloride pentahydrate.
3. a kind of cryochemistry tin plating solution as claimed in claim 1 is characterized in that, described trolamine replaces with diethanolamine or thanomin.
4. one kind with the tinned method of the described cryochemistry tin plating solution of claim 1, plating material copper or copper alloy were soaked in A solution 30～180 seconds earlier, in B solution, soaked 60～300 seconds again, promptly finish plating, 10～35 ℃ of A solution, B solution working temperatures.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010101135313A CN101760730B (en) | 2010-02-21 | 2010-02-21 | Low-temperature chemical tinning solution and tinning method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101135313A CN101760730B (en) | 2010-02-21 | 2010-02-21 | Low-temperature chemical tinning solution and tinning method |
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| CN101760730A true CN101760730A (en) | 2010-06-30 |
| CN101760730B CN101760730B (en) | 2011-04-20 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103261480A (en) * | 2011-01-13 | 2013-08-21 | 安美特德国有限公司 | Immersion tin or tin alloy plating bath with improved removal of cuprous ions |
| RU2491369C1 (en) * | 2012-04-17 | 2013-08-27 | Андрей Анатольевич Усков | Method for chemical application of stannic coating onto parts from copper or its alloys |
| CN104178755A (en) * | 2014-09-16 | 2014-12-03 | 朱忠良 | Coating method for metal coating |
| CN109055921A (en) * | 2018-08-27 | 2018-12-21 | 重庆立道新材料科技有限公司 | A kind of electroless plated tin liquor and preparation method thereof |
| CN111197174A (en) * | 2018-11-16 | 2020-05-26 | 丰田自动车株式会社 | Tin solution for forming tin film and method for forming tin film using same |
| CN114277249A (en) * | 2021-11-26 | 2022-04-05 | 江西瑞亿电子科技有限公司 | Treatment method for recycling tin, copper and waste gas from PCB tin waste liquid in recycling mode |
| CN114317969A (en) * | 2021-11-26 | 2022-04-12 | 江西瑞亿电子科技有限公司 | Method for recycling tin and copper from PCB tin waste liquid in recycling mode |
| CN114481107A (en) * | 2022-02-18 | 2022-05-13 | 深圳市创智成功科技有限公司 | Gold-precipitating solution for cyanide-free chemical heavy gold precipitation and process thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220472A (en) * | 2008-01-25 | 2008-07-16 | 太原师范学院 | Chemical plating stannum solution |
-
2010
- 2010-02-21 CN CN2010101135313A patent/CN101760730B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220472A (en) * | 2008-01-25 | 2008-07-16 | 太原师范学院 | Chemical plating stannum solution |
Non-Patent Citations (2)
| Title |
|---|
| 《材料保护》 20070131 孙武等 化学镀锡液中添加剂的影响研究 35-37页 1-4 第40卷, 第1期 * |
| 《材料导报》 20070531 梁腾平等 酸性镀锡液稳定性的研究进展 129-130页 1-4 第21卷, 第5A期 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103261480A (en) * | 2011-01-13 | 2013-08-21 | 安美特德国有限公司 | Immersion tin or tin alloy plating bath with improved removal of cuprous ions |
| CN103261480B (en) * | 2011-01-13 | 2015-06-10 | 安美特德国有限公司 | Immersion tin or tin alloy plating bath with improved removal of cuprous ions |
| RU2491369C1 (en) * | 2012-04-17 | 2013-08-27 | Андрей Анатольевич Усков | Method for chemical application of stannic coating onto parts from copper or its alloys |
| CN104178755A (en) * | 2014-09-16 | 2014-12-03 | 朱忠良 | Coating method for metal coating |
| CN109055921A (en) * | 2018-08-27 | 2018-12-21 | 重庆立道新材料科技有限公司 | A kind of electroless plated tin liquor and preparation method thereof |
| CN111197174A (en) * | 2018-11-16 | 2020-05-26 | 丰田自动车株式会社 | Tin solution for forming tin film and method for forming tin film using same |
| CN114277249A (en) * | 2021-11-26 | 2022-04-05 | 江西瑞亿电子科技有限公司 | Treatment method for recycling tin, copper and waste gas from PCB tin waste liquid in recycling mode |
| CN114317969A (en) * | 2021-11-26 | 2022-04-12 | 江西瑞亿电子科技有限公司 | Method for recycling tin and copper from PCB tin waste liquid in recycling mode |
| CN114481107A (en) * | 2022-02-18 | 2022-05-13 | 深圳市创智成功科技有限公司 | Gold-precipitating solution for cyanide-free chemical heavy gold precipitation and process thereof |
| CN114481107B (en) * | 2022-02-18 | 2022-11-01 | 深圳市创智成功科技有限公司 | Gold-precipitating solution for cyanide-free chemical heavy gold precipitation and process thereof |
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| CN101760730B (en) | 2011-04-20 |
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Granted publication date: 20110420 Termination date: 20140221 |