CN104141120B - Cuprous chemical copper plating solution - Google Patents
Cuprous chemical copper plating solution Download PDFInfo
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- CN104141120B CN104141120B CN201410305591.3A CN201410305591A CN104141120B CN 104141120 B CN104141120 B CN 104141120B CN 201410305591 A CN201410305591 A CN 201410305591A CN 104141120 B CN104141120 B CN 104141120B
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- chemical bronze
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Abstract
The invention discloses a cuprous chemical copper plating solution, relates to preparation and application methods of the cuprous chemical copper plating solution, and aims at solving the technical problems of low chemical copper plating speed and large formaldehyde consumption at present. The cuprous chemical copper plating solution contains the components such as cuprous chloride, potassium chloride, ammonium hydroxide, an auxiliary complexing agent, formaldehyde, a stabilizer, and an antioxidant; the cuprous chemical copper plating solution needs to be warmed up to 40-70 DEG C when in use, and the loading capacity is 0.2-4.0dm<2>/L. According to the cuprous chemical copper plating solution disclosed by the invention, more metal copper can be deposited under the condition of consuming equivalent formaldehyde, the chemical copper plating speed can be increased, the usage amount of formaldehyde can be saved, the production efficiency is improved, and the production cost is controlled.
Description
Technical field
The invention belongs to electroless copper field, is related to preparation and the using method of monovalence copper chemical bronze plating liquid.
Background technology
With the high speed development of society, single metal material or nonmetallic materials can not meet the need of people
Ask.In order to the features such as the portability, the insulating properties that have nonmetallic materials concurrently and metal glossiness, electric conductivity the features such as, non-gold
The conductive treatment of category material has become the important research field of modern material science and technology.At the conducting of nonmetallic materials
During reason, electroless copper can be provided initially usually as first step operation for the complete excellent conductive coating of follow-up acquisition
Seriality homogeneous conductive substrate.Not only there is relatively low production cost for the electroless copper of reducing agent due to adopting formaldehyde, and
And can obtain that purity is higher, the preferable copper coating of electric conductivity in catalytic matrix surface, therefore obtain in the industrial production
It is widely applied.Such as, on plastic electroplating, printed circuit board (PCB) through hole and blind hole metallization, ceramics conductive treatment with
And the preparation of electromagnetic shielding box etc., typically all adopt the electroless copper bottoming with formaldehyde as reducing agent.
For chemical plating system, the autocatalyzed oxidation process of reducing agent is often the rate-determining steps of whole process.With formaldehyde
For the chemical copper plating solution of reducing agent, only when the pH value of solution is higher than 11.0, formaldehyde can be sent out on active matrix surface
Raw oxidation, the copper ion in electronation plating solution.So the chemical copper plating solution with formaldehyde as reducing agent is all often in highly basic
Work under the conditions of property, also require that and exist in plating solution a large amount of chelating agent, prevent the hydrolysis of metal ion.However, with formaldehyde as also
The electroless copper plating speed of former agent is low, not only results in the decline of production efficiency, and electroless copper overlong time is easily caused
Quality of coating it is unstable.Therefore, the plating speed for how improving electroless copper has become the key issue of electroless copper technology.
In the chemical copper plating solution system with formaldehyde as reducing agent, often there is threshold in the autocatalyzed oxidation speed of formaldehyde
Value, if the valence state of copper is reduced to positive monovalence by positive bivalence in plating solution, can change in the case where equivalent formaldehyde is consumed
Restore the metallic copper of bigger equivalent, not only increases plating speed and production efficiency, it is ensured that the stability of product quality, and
The usage amount of formaldehyde during electroless copper can be saved, is conducive to the control of production cost and the environmental protection of electroless copper process
Change.
The content of the invention
The present invention is to solve existing electroless copper technology plating speed is compared with problem slow, that consumption formaldehyde is more, and provide one
Plant monovalence copper chemical bronze plating liquid.
The monovalence copper chemical bronze plating liquid of the present invention is prepared according to following steps：
(1) by the potassium chloride of 40 ~ 120g/L, the ammonia (25% ~ 28%) of 30 ~ 100mL/L and the auxiliary network of 5 ~ 60g/L
Mixture is dissolved in deionized water, is stirred, with solution A；(2) by the formaldehyde (37%) of 5 ~ 30mL/L, 1 ~ 100mg/L it is steady
The antioxidant for determining agent and 0.5 ~ 20.0g/L is dissolved in solution A, and with hydrochloric acid or potassium hydroxide adjust pH value to 11.0 ~
13.5, preparation obtains solution B；(3) 5 ~ 30g/L of Cu-lyt. is weighed, is slowly added to stir in solution B to dissolving, ageing 24 is little
When after with to obtain monovalence copper chemical bronze plating liquid.
Auxiliary complex-former described in step (1) is ethylenediamine, trisodium citrate, disodiumedetate, gluconic acid
One kind or wherein several combinations in sodium, triethanolamine, sodium potassium tartrate tetrahydrate or sodium glutamate；Stabilizer described in step (2)
For thiourea, 2,2- bipyridyls, Polyethylene Glycol（Molecular weight 6000）, two kinds of combination in Tween 80 or potassium thiocyanate, it is described
Antioxidant is in sodium thiosulfate, sodium hypophosphite, hydroquinone, catechol, resorcinol or sodium sulfite
Plant or wherein several combinations.
The monovalence copper chemical bronze plating liquid of the present invention must be warming up to 40 ~ 70 DEG C could be in the matrix surface with catalysis activity
Normal work, and the useful load of plating solution is 0.2 ~ 4.0dm2/L。
The present invention monovalence copper chemical bronze plating liquid by alkaline solution add cuprous ion chelating agent-chloride ion,
Ammonia and other auxiliary complex-formers, and can prevent cuprous ion from the antioxidant for aoxidizing occurring in aqueous, maintain plating
Cuprous ion is stablized in liquid, and ensure that the basis of whole chemical copper plating solution system normal work.Therefore when plating solution heats up
To suitable temperature and exist with catalysis activity interface when, formaldehyde in solution can be urged by catalysis activity interface
Change oxidation and carry out electronation cuprous ion, so as to obtain copper coating.The present invention carries out chemical plating by monovalence copper chemical bronze plating liquid
During copper, because the valence state of copper in plating solution is+1 valency, therefore can be gone out with electronation in the case where equivalent formaldehyde is consumed bigger
The metallic copper of equivalent, not only increases production efficiency, and can save the usage amount of formaldehyde during electroless copper, reduces
The production burden of enterprise, to the environmental protection and resources conservationization of electroless copper production process great impetus can be played.
Description of the drawings
Fig. 1 be test one prepare monovalence copper chemical bronze plating liquid plating temperature be 50 DEG C, useful load be 1.0dm2/ L's
Under the conditions of chemical plating after 30 minutes gained coating metallurgical microscope photo；
Fig. 2 be test one prepare monovalence copper chemical bronze plating liquid plating temperature be 50 DEG C, useful load be 1.0dm2/ L's
Under the conditions of chemical plating after 30 minutes gained coating electron scanning micrograph；
Fig. 3 be test one prepare monovalence copper chemical bronze plating liquid plating temperature be 50 DEG C, useful load be 1.0dm2/ L's
Under the conditions of chemical plating after 30 minutes gained coating copper scattergram.
Specific embodiment
Specific embodiment one：The monovalence copper chemical bronze plating liquid of present embodiment is prepared according to following steps：
(1) by the potassium chloride of 40 ~ 120g/L, the ammonia (25% ~ 28%) of 30 ~ 100mL/L and the auxiliary network of 5 ~ 60g/L
Mixture is dissolved in deionized water, is stirred, with solution A；(2) by the formaldehyde (37%) of 5 ~ 30mL/L, 1 ~ 100mg/L it is steady
The antioxidant for determining agent and 0.5 ~ 20.0g/L is dissolved in solution A, and with hydrochloric acid or potassium hydroxide adjust pH value to 11.0 ~
13.5, preparation obtains solution B；(3) 5 ~ 30g/L of Cu-lyt. is weighed, is slowly added to stir in solution B to dissolving, ageing 24 is little
When after with to obtain monovalence copper chemical bronze plating liquid.
The monovalence copper chemical bronze plating liquid of present embodiment ought be warming up to suitable temperature and exist with catalysis activity
During interface, can by catalysis activity interface to the catalysis oxidation of formaldehyde in solution come electronation cuprous ion, so as to obtain
Copper coating.When present embodiment carries out electroless copper by monovalence copper chemical bronze plating liquid, because the valence state of copper in plating solution is+1 valency,
Therefore the metallic copper that bigger equivalent can be gone out with electronation in the case where equivalent formaldehyde is consumed, not only increases production effect
Rate, and the usage amount of formaldehyde during electroless copper can be saved.
Specific embodiment two：Present embodiment and the auxiliary network described in step (1) unlike specific embodiment one
Mixture is ethylenediamine, trisodium citrate, disodiumedetate, sodium gluconate, triethanolamine, sodium potassium tartrate tetrahydrate or paddy ammonia
One kind or wherein several combinations in sour sodium, concentration is 6 ~ 50g/L.Other are identical with specific embodiment one.
When the auxiliary complex-former of present embodiment is compositionss, various auxiliary complex-formers are by any combination.
Specific embodiment three：Present embodiment from it is steady described in step unlike specific embodiment one or two (2)
Agent is determined for thiourea, 2,2- bipyridyls, Polyethylene Glycol（Molecular weight 6000）, two kinds of combination in Tween 80 or potassium thiocyanate, two
Plant stabilizer and press any combination, concentration is 2 ~ 80mg/L.Other are identical with specific embodiment one or two.
Specific embodiment four：Step (2) is described unlike one of present embodiment and specific embodiment one to three
Antioxidant be sodium thiosulfate, sodium hypophosphite, hydroquinone, catechol, resorcinol or sodium sulfite in
A kind of or wherein several combination, concentration is 1.0 ~ 15.0g/L.Other are identical with one of specific embodiment one to three.
When the antioxidant of present embodiment is compositionss, various antioxidants press any combination.
Specific embodiment five：Described monovalence copper unlike one of present embodiment and specific embodiment one to four
Chemical bronze plating liquid must be warming up to 40 ~ 70 DEG C could be in the matrix surface normal work with catalysis activity, and the loading of plating solution
Measure as 0.2 ~ 4.0dm2/L.Other are identical with one of specific embodiment one to four.
With following verification experimental verification beneficial effects of the present invention：
Test one：The monovalence copper chemical bronze plating liquid of this test is prepared according to the following steps：
(1) by the potassium chloride of 100g/L, the ammonia (25% ~ 28%) of 80mL/L and the disodiumedetate of 40g/L
In being dissolved in deionized water, stir, with solution A；(2) by the formaldehyde (37%) of 10mL/L, the potassium thiocyanate of 2mg/L,
2, the 2- bipyridyls of 5mg/L, the sodium hypophosphite of 2.5g/L and 2.0g/L resorcinol are dissolved in solution A, and with hydrochloric acid or
Potassium hydroxide adjusts pH value to 12.5, and preparation obtains solution B；(3) Cu-lyt. 15g/L is weighed, is slowly added to be stirred in solution B
Mix to dissolving, ageing matches somebody with somebody to obtain monovalence copper chemical bronze plating liquid after 24 hours.
Above-mentioned monovalence copper chemical bronze plating liquid plating temperature be 50 DEG C, useful load be 1.0dm2Chemical plating 30 under conditions of/L
After minute the metallurgical microscope photo and electron scanning micrograph of gained coating respectively as depicted in figs. 1 and 2, from Fig. 1 and
Fig. 2 understands that gained chemical plating copper layer crystallization is careful, smooth.
Above-mentioned monovalence copper chemical bronze plating liquid plating temperature be 50 DEG C, useful load be 1.0dm2Chemical plating 30 under conditions of/L
As shown in figure 3, as can be seen from Figure 3, copper is evenly distributed the copper scattergram of gained coating in gained copper coating after minute.
According to Thickness Analysis of the X-ray fluorescence spectra analysis to coating, above-mentioned monovalence copper chemical bronze plating liquid is in plating temperature
It is 1.0dm for 50 DEG C, useful load2The thickness of chemical plating coating obtained by after 30 minutes is 5.3 μm under conditions of/L, therefore plating speed is
10.6μm/h。
Test two：The monovalence copper chemical bronze plating liquid of this test is prepared according to the following steps：
(1) by the triethanolamine of the potassium chloride of 80g/L, the ammonia (25% ~ 28%) of 60mL/L and 20g/L be dissolved in from
In sub- water, stir, with solution A；(2) 2,2- of the formaldehyde (37%) of 12mL/L, the thiourea of 3mg/L, 5mg/L is joined into pyrrole
Pyridine, the sodium hypophosphite of 2.5g/L and 0.5g/L sodium sulfite are dissolved in solution A, and adjust pH value with hydrochloric acid or potassium hydroxide
To 12.5, preparation obtains solution B；(3) Cu-lyt. 12g/L is weighed, is slowly added to stir in solution B to dissolving, ageing 24 is little
When after with to obtain monovalence copper chemical bronze plating liquid.
According to Thickness Analysis of the X-ray fluorescence spectra analysis to coating, above-mentioned monovalence copper chemical bronze plating liquid is in plating temperature
It is 1.0dm for 50 DEG C, useful load2The thickness of chemical plating coating obtained by after 30 minutes is 6.0 μm under conditions of/L, therefore plating speed is
12.0μm/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 potassium chloride of 80g/L, the ammonia (25% ~ 28%) of 60mL/L and 30g/L is dissolved in
In ionized water, stir, with solution A；(2) by the formaldehyde (37%) of 10mL/L, the Polyethylene Glycol of 15mg/L（Molecular weight
6000）, the Tween 80 of 12mg/L, the catechol of 3.0g/L and 0.1g/L sodium thiosulfate is dissolved in solution A, and uses hydrochloric acid
Or potassium hydroxide adjusts pH value to 12.5, preparation obtains solution B；(3) Cu-lyt. 10g/L is weighed, in being slowly added to solution B
Stir to dissolving, ageing matches somebody with somebody to obtain monovalence copper chemical bronze plating liquid after 24 hours.
According to Thickness Analysis of the X-ray fluorescence spectra analysis to coating, above-mentioned monovalence copper chemical bronze plating liquid is in plating temperature
It is 1.0dm for 50 DEG C, useful load2The thickness of chemical plating coating obtained by after 30 minutes is 4.3 μm under conditions of/L, therefore plating speed is
8.6μm/h。
Claims (9)
1. monovalence copper chemical bronze plating liquid, it is characterised in that by the formaldehyde electronation cuprous ion in monovalence copper chemical bronze plating liquid
To realize the deposition of copper coating, in plating solution in addition to the Cu-lyt. containing formaldehyde and offer cuprous ion, also contain chlorine
Change potassium, ammonia, auxiliary complex-former, stabilizer and antioxidant；The concentration of Cu-lyt. is 5 ~ 30g/L, quality hundred in plating solution
Point concentration be the concentration of 37% formaldehyde be 5 ~ 30mL/L, the concentration of potassium chloride be 40 ~ 120g/L, mass percentage concentration be 25% ~
28% ammonia concn is 30 ~ 100mL/L, the concentration of auxiliary complex-former is 5 ~ 60g/L, the concentration of stabilizer is 1 ~ 100mg/L,
The concentration of antioxidant is 0.5 ~ 20.0g/L；Plating solution hydrochloric acid or potassium hydroxide adjust pH value to 11.0 ~ 13.5.
2. monovalence copper chemical bronze plating liquid according to claim 1, it is characterised in that described auxiliary complex-former be ethylenediamine,
One kind in trisodium citrate, disodiumedetate, sodium gluconate, triethanolamine, sodium potassium tartrate tetrahydrate or sodium glutamate
Or wherein several combination, concentration is 6 ~ 50g/L.
3. monovalence copper chemical bronze plating liquid according to claim 1, it is characterised in that described stabilizer is that thiourea, 2,2- join
Pyridine, molecular weight be 6000 Polyethylene Glycol, Tween 80 or potassium thiocyanate in two kinds of combination, concentration is 2 ~ 80mg/L.
4. monovalence copper chemical bronze plating liquid according to claim 1, it is characterised in that described antioxidant is thiosulfuric acid
One kind or wherein several combinations in sodium, sodium hypophosphite, hydroquinone, catechol, resorcinol or sodium sulfite,
Concentration is 1.0 ~ 15.0g/L.
5. the monovalence copper chemical bronze plating liquid according to any one in claim 1,2,3,4, it is characterised in that described one
Valency copper chemical bronze plating liquid must be warming up to 45 ~ 70 DEG C could be in the matrix surface normal work with catalysis activity, and plating solution
Useful load is 0.2 ~ 4.0dm2/L。
6. the compound method of monovalence copper chemical bronze plating liquid, it is characterised in that the compound method is carried out according to the following steps：
(1) ammonia and 5 ~ 60g/ by the mass percentage concentration of the potassium chloride of 40 ~ 120g/L, 30 ~ 100mL/L for 25% ~ 28%
The auxiliary complex-former of L is dissolved in deionized water, is stirred, with solution A；(2) it is by the mass percentage concentration of 5 ~ 30mL/L
The antioxidant of 37% formaldehyde, the stabilizer of 1 ~ 100mg/L and 0.5 ~ 20.0g/L is dissolved in solution A, and with hydrochloric acid or hydrogen
Potassium oxide adjusts pH value to 11.0 ~ 13.5, and configuration obtains solution B；(3) 5 ~ 30g/L of Cu-lyt. is weighed, solution B is slowly added to
In stir to dissolving, with obtaining monovalence copper chemical bronze plating liquid after ageing 24 hours.
7. the compound method of monovalence copper chemical bronze plating liquid according to claim 6, it is characterised in that described auxiliary complexation
Agent is ethylenediamine, trisodium citrate, disodiumedetate, sodium gluconate, triethanolamine, sodium potassium tartrate tetrahydrate or glutamic acid
One kind or wherein several combinations in sodium, concentration is 6 ~ 50g/L.
8. the compound method of monovalence copper chemical bronze plating liquid according to claim 6, it is characterised in that described stabilizer is
Two kinds of combination in thiourea, 2,2- bipyridyls, the Polyethylene Glycol that molecular weight is 6000, Tween 80 or potassium thiocyanate, concentration is 2
~80mg/L。
9. the compound method of monovalence copper chemical bronze plating liquid according to claim 6, it is characterised in that described antioxidant
For the one kind in sodium thiosulfate, sodium hypophosphite, hydroquinone, catechol, resorcinol or sodium sulfite or wherein
Several combinations, concentration is 1.0 ~ 15.0g/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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| 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 |
| CN106435541B (en) * | 2016-09-26 | 2019-02-19 | 四川大学 | A kind of aluminum grain refiner and preparation method thereof based on titanium carbonitride |
| 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 |
| CN110846646B (en) * | 2019-12-10 | 2022-02-15 | 深圳中塑化工高性能材料有限公司 | ABS plastic chemical copper plating solution and preparation method thereof |
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| JPS59211564A (en) * | 1983-05-17 | 1984-11-30 | Toshiba Corp | Chemical copper plating solution |
| JPS6311676A (en) * | 1986-07-01 | 1988-01-19 | Nippon Denso Co Ltd | Chemical copper plating bath |
| US5750018A (en) * | 1997-03-18 | 1998-05-12 | Learonal, Inc. | Cyanide-free monovalent copper electroplating solutions |
| CN103811725B (en) * | 2014-01-28 | 2016-02-10 | 东南大学 | The surface treatment method of hydrogen bearing alloy |
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