CN104141120A - Cuprous chemical copper plating solution - Google Patents
Cuprous chemical copper plating solution Download PDFInfo
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- CN104141120A CN104141120A CN201410305591.3A CN201410305591A CN104141120A CN 104141120 A CN104141120 A CN 104141120A CN 201410305591 A CN201410305591 A CN 201410305591A CN 104141120 A CN104141120 A CN 104141120A
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Abstract
一价铜化学镀铜液，本发明涉及一价铜化学镀铜液的配制及使用方法。本发明是要解决目前化学镀铜镀速较低且消耗甲醛较多的技术问题。一价铜化学镀铜液含有氯化亚铜、氯化钾、氨水、辅助络合剂、甲醛、稳定剂以及抗氧化剂等组分，在使用时需要升温至40~70℃且装载量为0.2~4.0dm2/L。本发明的一价铜化学镀铜液可以在消耗等当量甲醛的情况下沉积出更多的金属铜，不仅可以提高化学镀铜的镀速，而且可以节省甲醛的使用量，有利于生产效率的提高以及生产成本的控制。
Monovalent copper electroless copper plating solution, the invention relates to the preparation and use method of monovalent copper electroless copper plating solution. The invention aims to solve the technical problems of low electroless copper plating speed and high consumption of formaldehyde at present. The monovalent copper electroless copper plating solution contains components such as cuprous chloride, potassium chloride, ammonia water, auxiliary complexing agent, formaldehyde, stabilizer, and antioxidant. It needs to be heated to 40~70°C and the loading capacity is 0.2 ~ 4.0dm2 /L. The electroless copper plating solution for monovalent copper of the present invention can deposit more metal copper under the condition of consuming equivalent formaldehyde, not only can improve the plating speed of electroless copper plating, but also can save the amount of formaldehyde used, which is beneficial to the improvement of production efficiency Improve and control production costs.
Description
Technical field
The invention belongs to electroless copper field, relate to preparation and the using method of monovalence copper chemical bronze plating liquid.
Background technology
Along with social high speed development, single metallic substance or non-metallic material can not meet people's demand.In order to have the feature such as portability, insulativity of non-metallic material and the feature such as glossiness, electroconductibility of metal concurrently, the conductive treatment of non-metallic material has become the important research field of modern material science and technology.In the conductive treatment process of non-metallic material, electroless copper, usually used as the first step operation, can provide initial continuity homogeneous conductive substrate for the electroconductive coating of the complete excellence of follow-up acquisition.Because to adopt formaldehyde be reductive agent, electroless copper not only has lower production cost, and can obtain at catalytic matrix surface that purity is higher, the good copper coating of electroconductibility, therefore in industrial production, obtains a wide range of applications.Such as, conductive treatment and the preparation of electromagnetic shielding box etc. of the metallization of through hole and blind hole on plastic electroplating, printed circuit board (PCB), pottery, generally all adopt the electroless copper bottoming taking formaldehyde as reductive agent.
For electroless plating system, the autocatalyzed oxidation process of reductive agent is the control step of whole process often.Chemical copper plating solution taking formaldehyde as reductive agent, only has when the pH of solution value is higher than 11.0 time, and formaldehyde can be oxidized on active matrix surface, the cupric ion in chemical reduction plating solution.So the chemical copper plating solution taking formaldehyde as reductive agent is often all worked under strong alkaline condition, also require to have a large amount of complexing agents in plating solution, prevent the hydrolysis of metal ion.But the electroless copper plating speed taking formaldehyde as reductive agent is on the low side, not only can cause the decline of production efficiency, and electroless copper overlong time easily causes the unstable of quality of coating.Therefore the plating speed that, how to improve electroless copper has become the key issue of electroless copper technology.
In the chemical copper plating solution system taking formaldehyde as reductive agent; often there is threshold value in the autocatalyzed oxidation speed of formaldehyde; if the valence state of copper is reduced to positive monovalence by positive divalence in plating solution; can chemical reduction in the situation that consuming equivalent formaldehyde go out the metallic copper of larger equivalent; plating speed and production efficiency are not only improved; ensure the stability of quality product; and the usage quantity that can save formaldehyde in electroless copper process, be conducive to the control of production cost and the environmental protection of electroless copper process.
Summary of the invention
The present invention will solve fast slow, the more problem of consumption formaldehyde of existing electroless copper technology plating, and a kind of monovalence copper chemical bronze plating liquid is provided.
Monovalence copper chemical bronze plating liquid of the present invention is prepared according to following steps:
(1) auxiliary complex-former of the ammoniacal liquor of the Repone K of 40 ~ 120g/L, 30 ~ 100mL/L (25% ~ 28%) and 5 ~ 60g/L is dissolved in deionized water, stirs, join to obtain solution A; (2) formaldehyde of 5 ~ 30mL/L (37%), the stablizer of 1 ~ 100mg/L and the antioxidant of 0.5 ~ 20.0g/L are dissolved in solution A, and adjust pH value to 11.0 ~ 13.5 with hydrochloric acid or potassium hydroxide, preparation obtains solution B; (3) take cuprous chloride 5 ~ 30g/L, slowly add in solution B and be stirred to dissolving, monovalence copper chemical bronze plating liquid is joined to obtain in ageing after 24 hours.
The described auxiliary complex-former of step (1) is a kind of in quadrol, trisodium citrate, disodium ethylene diamine tetraacetate, Sunmorl N 60S, trolamine, Seignette salt or Sodium Glutamate or wherein several combination; The described stablizer of step (2) is thiocarbamide, 2, the combination of two kinds in 2-dipyridyl, polyoxyethylene glycol (molecular weight 6000), tween 80 or potassium sulfocyanate, described antioxidant is a kind of in Sulfothiorine, inferior sodium phosphate, Resorcinol, pyrocatechol, Resorcinol or S-WAT or wherein several combination.
Monovalence copper chemical bronze plating liquid of the present invention must be warming up to 40 ~ 70 DEG C and could normally work at the matrix surface with catalytic activity, and the loading capacity of plating solution is 0.2 ~ 4.0dm
2/ L.
Monovalence copper chemical bronze plating liquid of the present invention by adding complexing agent-chlorion, ammonia and other auxiliary complex-former of cuprous ion in basic solution, and can prevent that cuprous ion from the antioxidant of oxidation occurring in the aqueous solution, maintain the stable of cuprous ion in plating solution, and ensured the basis of the normal work of whole chemical copper plating solution system.Therefore in the time that plating solution is warming up to suitable temperature and existence and has the interface of catalytic activity, can carry out chemical reduction cuprous ion to the catalyzed oxidation of formaldehyde in solution by catalytic activity interface, thereby obtain copper coating.When the present invention carries out electroless copper by monovalence copper chemical bronze plating liquid; because the valence state of copper in plating solution is+1 valency; therefore can chemical reduction in the situation that consuming equivalent formaldehyde go out the metallic copper of larger equivalent; not only improve production efficiency; and the usage quantity that can save formaldehyde in electroless copper process; the production burden that has reduced enterprise, the environmental protection to electroless copper production process and resources conservationization can play great pushing effect.
Brief description of the drawings
Fig. 1 is that the monovalence copper chemical bronze plating liquid of test one preparation is that 50 DEG C, loading capacity are 1.0dm at plating temperature
2the metaloscope photo of electroless plating gained coating after 30 minutes under the condition of/L;
Fig. 2 is that the monovalence copper chemical bronze plating liquid of test one preparation is that 50 DEG C, loading capacity are 1.0dm at plating temperature
2the electron scanning micrograph of electroless plating gained coating after 30 minutes under the condition of/L;
Fig. 3 is that the monovalence copper chemical bronze plating liquid of test one preparation is that 50 DEG C, loading capacity are 1.0dm at plating temperature
2the copper distribution plan of electroless plating gained coating after 30 minutes under the condition of/L.
Embodiment
Embodiment one: the monovalence copper chemical bronze plating liquid of present embodiment is prepared according to following steps:
(1) auxiliary complex-former of the ammoniacal liquor of the Repone K of 40 ~ 120g/L, 30 ~ 100mL/L (25% ~ 28%) and 5 ~ 60g/L is dissolved in deionized water, stirs, join to obtain solution A; (2) formaldehyde of 5 ~ 30mL/L (37%), the stablizer of 1 ~ 100mg/L and the antioxidant of 0.5 ~ 20.0g/L are dissolved in solution A, and adjust pH value to 11.0 ~ 13.5 with hydrochloric acid or potassium hydroxide, preparation obtains solution B; (3) take cuprous chloride 5 ~ 30g/L, slowly add in solution B and be stirred to dissolving, monovalence copper chemical bronze plating liquid is joined to obtain in ageing after 24 hours.
The monovalence copper chemical bronze plating liquid of present embodiment, in the time being warming up to suitable temperature and existence and having the interface of catalytic activity, can carry out chemical reduction cuprous ion to the catalyzed oxidation of formaldehyde in solution by catalytic activity interface, thereby obtains copper coating.When present embodiment is carried out electroless copper by monovalence copper chemical bronze plating liquid, because the valence state of copper in plating solution is+1 valency, therefore can chemical reduction in the situation that consuming equivalent formaldehyde go out the metallic copper of larger equivalent, not only improve production efficiency, and can save the usage quantity of formaldehyde in electroless copper process.
Embodiment two: the described auxiliary complex-former of step (1) that what present embodiment was different from embodiment one is is a kind of in quadrol, trisodium citrate, disodium ethylene diamine tetraacetate, Sunmorl N 60S, trolamine, Seignette salt or Sodium Glutamate or wherein several combination, and concentration is 6 ~ 50g/L.Other is identical with embodiment one.
When the auxiliary complex-former of present embodiment is composition, various auxiliary complex-formers are for pressing any combination.
Embodiment three: what present embodiment was different from embodiment one or two is that the described stablizer of step (2) is thiocarbamide, 2, the combination of two kinds in 2-dipyridyl, polyoxyethylene glycol (molecular weight 6000), tween 80 or potassium sulfocyanate, two kinds of stablizers are by any combination, and concentration is 2 ~ 80mg/L.Other is identical with embodiment one or two.
Embodiment four: the described antioxidant of step (2) that what present embodiment was different from one of embodiment one to three is is a kind of in Sulfothiorine, inferior sodium phosphate, Resorcinol, pyrocatechol, Resorcinol or S-WAT or wherein several combination, and concentration is 1.0 ~ 15.0g/L.Other is identical with one of embodiment one to three.
When the antioxidant of present embodiment is composition, various antioxidants are by any combination.
Embodiment five: what present embodiment was different from one of embodiment one to four is, and described monovalence copper chemical bronze plating liquid must be warming up to 40 ~ 70 DEG C could normally work at the matrix surface with catalytic activity, and the loading capacity of plating solution is 0.2 ~ 4.0dm
2/ L.Other is identical with one of embodiment one to four.
With following verification experimental verification beneficial effect of the present invention:
Test one: the monovalence copper chemical bronze plating liquid of this test is prepared according to the following steps:
(1) disodium ethylene diamine tetraacetate of the ammoniacal liquor of the Repone K of 100g/L, 80mL/L (25% ~ 28%) and 40g/L is dissolved in deionized water, stirs, join to obtain solution A; (2) by 2 of the potassium sulfocyanate of the formaldehyde of 10mL/L (37%), 2mg/L, 5mg/L, the inferior sodium phosphate of 2-dipyridyl, 2.5g/L and 2.0g/L Resorcinol are dissolved in solution A, and adjust pH value to 12.5 with hydrochloric acid or potassium hydroxide, preparation obtains solution B; (3) take cuprous chloride 15g/L, slowly add in solution B and be stirred to dissolving, monovalence copper chemical bronze plating liquid is joined to obtain in ageing after 24 hours.
Above-mentioned monovalence copper chemical bronze plating liquid is that 50 DEG C, loading capacity are 1.0dm at plating temperature
2under the condition of/L, the metaloscope photo of electroless plating gained coating after 30 minutes and electron scanning micrograph are respectively as depicted in figs. 1 and 2, careful, smooth from Fig. 1 and the crystallization of the known gained chemical plating copper layer of Fig. 2.
Above-mentioned monovalence copper chemical bronze plating liquid is that 50 DEG C, loading capacity are 1.0dm at plating temperature
2under the condition of/L, as shown in Figure 3, as can be seen from Figure 3, copper is evenly distributed the copper distribution plan of electroless plating gained coating after 30 minutes in gained copper coating.
Thickness Analysis according to X-ray fluorescence spectra analysis to coating, above-mentioned monovalence copper chemical bronze plating liquid is that 50 DEG C, loading capacity are 1.0dm at plating temperature
2under the condition of/L, the thickness of electroless plating gained coating after 30 minutes is 5.3 μ m, and therefore plating speed is 10.6 μ m/h.
Test two: the monovalence copper chemical bronze plating liquid of this test is prepared according to the following steps:
(1) trolamine of the ammoniacal liquor of the Repone K of 80g/L, 60mL/L (25% ~ 28%) and 20g/L is dissolved in deionized water, stirs, join to obtain solution A; (2) by 2 of the thiocarbamide of the formaldehyde of 12mL/L (37%), 3mg/L, 5mg/L, the inferior sodium phosphate of 2-dipyridyl, 2.5g/L and 0.5g/L S-WAT are dissolved in solution A, and adjust pH value to 12.5 with hydrochloric acid or potassium hydroxide, preparation obtains solution B; (3) take cuprous chloride 12g/L, slowly add in solution B and be stirred to dissolving, monovalence copper chemical bronze plating liquid is joined to obtain in ageing after 24 hours.
Thickness Analysis according to X-ray fluorescence spectra analysis to coating, above-mentioned monovalence copper chemical bronze plating liquid is that 50 DEG C, loading capacity are 1.0dm at plating temperature
2under the condition of/L, the thickness of electroless plating gained coating after 30 minutes is 6.0 μ m, and therefore plating speed is 12.0 μ m/h.
Test three: the monovalence copper chemical bronze plating liquid of this test is prepared according to the following steps:
(1) trisodium citrate of the ammoniacal liquor of the Repone K of 80g/L, 60mL/L (25% ~ 28%) and 30g/L is dissolved in deionized water, stirs, join to obtain solution A; (2) pyrocatechol and the 0.1g/L Sulfothiorine of the tween 80 of the polyoxyethylene glycol of the formaldehyde of 10mL/L (37%), 15mg/L (molecular weight 6000), 12mg/L, 3.0g/L are dissolved in solution A, and adjust pH value to 12.5 with hydrochloric acid or potassium hydroxide, preparation obtains solution B; (3) take cuprous chloride 10g/L, slowly add in solution B and be stirred to dissolving, monovalence copper chemical bronze plating liquid is joined to obtain in ageing after 24 hours.
Thickness Analysis according to X-ray fluorescence spectra analysis to coating, above-mentioned monovalence copper chemical bronze plating liquid is that 50 DEG C, loading capacity are 1.0dm at plating temperature
2under the condition of/L, the thickness of electroless plating gained coating after 30 minutes is 4.3 μ m, and therefore plating speed is 8.6 μ m/h.
Claims (6)
1. monovalence copper chemical bronze plating liquid, it is characterized in that realizing by the formaldehyde chemical reduction cuprous ion in monovalence copper chemical bronze plating liquid the deposition of copper coating, in plating solution, except containing formaldehyde and providing the cuprous chloride of cuprous ion, also contain the components such as Repone K, ammoniacal liquor, auxiliary complex-former, stablizer and antioxidant.
2. monovalence copper chemical bronze plating liquid, is characterized in that the compound method of monovalence copper chemical bronze plating liquid is carried out according to the following steps:
(1) auxiliary complex-former of the ammoniacal liquor of the Repone K of 40 ~ 120g/L, 30 ~ 100mL/L (25% ~ 28%) and 5 ~ 60g/L is dissolved in deionized water, stirs, join to obtain solution A; (2) formaldehyde of 5 ~ 30mL/L (37%), the stablizer of 1 ~ 100mg/L and the antioxidant of 0.5 ~ 20.0g/L are dissolved in solution A, and adjust pH value to 11.0 ~ 13.5 with hydrochloric acid or potassium hydroxide, preparation obtains solution B; (3) take cuprous chloride 5 ~ 30g/L, slowly add in solution B and be stirred to dissolving, monovalence copper chemical bronze plating liquid is joined to obtain in ageing after 24 hours.
3. monovalence copper chemical bronze plating liquid according to claim 1 and 2, it is characterized in that described auxiliary complex-former is a kind of in quadrol, trisodium citrate, disodium ethylene diamine tetraacetate, Sunmorl N 60S, trolamine, Seignette salt or Sodium Glutamate or wherein several combination, concentration is 6 ~ 50g/L.
4. monovalence copper chemical bronze plating liquid according to claim 1 and 2, is characterized in that described stablizer is thiocarbamide, 2, the combination of two kinds in 2-dipyridyl, polyoxyethylene glycol (molecular weight 6000), tween 80 or potassium sulfocyanate, and concentration is 2 ~ 80mg/L.
5. monovalence copper chemical bronze plating liquid according to claim 1 and 2, it is characterized in that described antioxidant is a kind of in Sulfothiorine, inferior sodium phosphate, Resorcinol, pyrocatechol, Resorcinol or S-WAT or wherein several combination, concentration is 1.0 ~ 15.0g/L.
6. according to the monovalence copper chemical bronze plating liquid described in aforementioned any one claim, it is characterized in that described monovalence copper chemical bronze plating liquid must be warming up to 40 ~ 70 DEG C and could normally work at the matrix surface with catalytic activity, and the loading capacity of plating solution is 0.2 ~ 4.0dm
2/ L.
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| CN201410305591.3A CN104141120B (en) | 2014-07-01 | 2014-07-01 | Cuprous chemical copper plating solution |
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|---|---|---|---|
| CN201410305591.3A CN104141120B (en) | 2014-07-01 | 2014-07-01 | Cuprous chemical copper plating solution |
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| CN104141120B CN104141120B (en) | 2017-04-19 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105040044A (en) * | 2015-07-21 | 2015-11-11 | 安徽江威精密制造有限公司 | Electroplating solution for copper plating and preparation method thereof |
| CN106435541A (en) * | 2016-09-26 | 2017-02-22 | 四川大学 | Aluminium alloy grain refiner based on titanium carbonitride, and preparation method thereof |
| CN108193197A (en) * | 2018-03-19 | 2018-06-22 | 四川省劲腾环保建材有限公司 | The method of chemical bronze plating liquid and electroless copper |
| CN108468039A (en) * | 2018-05-24 | 2018-08-31 | 江苏时瑞电子科技有限公司 | A kind of chemical bronze plating liquid and its copper-plating technique applied in zinc oxide varistor copper electrode |
| CN110846646A (en) * | 2019-12-10 | 2020-02-28 | 卢桂珍 | A kind of ABS plastic chemical copper plating solution and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105040044A (en) * | 2015-07-21 | 2015-11-11 | 安徽江威精密制造有限公司 | Electroplating solution for copper plating and preparation method thereof |
| CN106435541A (en) * | 2016-09-26 | 2017-02-22 | 四川大学 | Aluminium alloy grain refiner based on titanium carbonitride, and preparation method thereof |
| CN106435541B (en) * | 2016-09-26 | 2019-02-19 | 四川大学 | A kind of aluminum alloy grain refiner based on titanium carbonitride and preparation method thereof |
| CN108193197A (en) * | 2018-03-19 | 2018-06-22 | 四川省劲腾环保建材有限公司 | The method of chemical bronze plating liquid and electroless copper |
| CN108468039A (en) * | 2018-05-24 | 2018-08-31 | 江苏时瑞电子科技有限公司 | A kind of chemical bronze plating liquid and its copper-plating technique applied in zinc oxide varistor copper electrode |
| CN110846646A (en) * | 2019-12-10 | 2020-02-28 | 卢桂珍 | A kind of ABS plastic chemical copper plating solution and preparation method thereof |
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