CN103014787A - Copper-electroplating solution and electroplating process thereof - Google Patents

Copper-electroplating solution and electroplating process thereof Download PDF

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Publication number
CN103014787A
CN103014787A CN2012105864294A CN201210586429A CN103014787A CN 103014787 A CN103014787 A CN 103014787A CN 2012105864294 A CN2012105864294 A CN 2012105864294A CN 201210586429 A CN201210586429 A CN 201210586429A CN 103014787 A CN103014787 A CN 103014787A
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Prior art keywords
electroplating
copper
copper electroplating
liquid
solution
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CN2012105864294A
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CN103014787B (en
Inventor
陈蔡喜
罗迎花
蔡志华
刘红霞
牛艳丽
黄超玉
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GUANGDONG DAZHI ENVIRONMENTAL PROTECTION TECHNOLOGY Co Ltd
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GUANGDONG DAZHI ENVIRONMENTAL PROTECTION TECHNOLOGY Co Ltd
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Abstract

The invention provides a copper-electroplating solution and an electroplating process thereof, belonging to the technical field of electroplating. The electroplating solution mainly comprises a complexing agent, a main salt, a conductive salt and a brightening agent; and the pH value of the electroplating solution is 9.0-11.0. Aiming at the problem of environment pollution caused by the plating solution commonly containing cyanide in the existing alkaline copper-plating process, the invention provides a copper-electroplating environmental-friendly process through a cyanide-free alkaline copper-plating process. The electroplating solution has the advantages of absence of cyanide and strong binding force between the copper-plating layer and the substrate; and the electroplating solution can be widely applied to the electroplating field.

Description

A kind of copper electroplating liquid and electroplating technology thereof
Technical field
The present invention relates to a kind of electroplating technology, more particularly relate to a kind of cyanide-free alkaline copper plating technology.
Background technology
Industrialized development, problem of environmental pollution is more and more serious, and for protection of the environment, cleaning, environmental protection, energy-conservation production more and more are subject to the attention of industry.In the electroplating industry cyanide copper plating process, production process must be used the prussiate cyanide copper plating process, exists the prussiate of hypertoxicity, and its environmental pollution is extremely serious, causes serious threat to the workman is healthy; Along with the enhancing of people's environmental consciousness, the copper-plating technique of an urgent demand development environment-protecting clean substitutes traditional cyanide copper plating technique.Therefore, develop new environmental protection copper-plating technique, solve problem of environmental pollution and direct labor's health problem, positive social effect is arranged.In fact, countries in the world are being carried out the research and development to cyanideless electro-plating all the time in the electroplating technology field, and along with the progress of correlation technique, and new electroplating additive comes into the market, and the level of cyanogenless electroplating technology is progressively improving.
Summary of the invention
In view of this, the present invention proposes a kind of copper electroplating liquid and electroplating technology thereof, be a kind of Alkali CyanideFree Copper Electroplating Technology, be applied in the electro-coppering production, copper layer and basal body binding force well can reach the requirement of production technique cleaning, environmental protection, can substitute traditional cyanide copper plating technique, solve the prior art environmental pollution and to direct labor's health threat problem.
Technical scheme of the present invention is achieved in that a kind of copper electroplating liquid, and described electroplate liquid mainly comprises complexing agent, main salt, conducting salt, brightening agent, wherein:
Complexing agent content is 100 ~ 200 grams per liters;
Main salts contg is 30 ~ 100 grams per liters;
Conducting salt content is 20 ~ 50 grams per liters;
Brightening agent content is 10 ~ 100 mg/litre;
The pH value of electroplate liquid is 9.0 ~ 11.0; Solvent is water.
Described complexing agent is by one or more the combination in Trisodium Citrate, thionamic acid sodium, Sunmorl N 60S, the disodium ethylene diamine tetraacetate.
Described complexing agent is disodium ethylene diamine tetraacetate and Trisodium Citrate.
Described main salt is by in copper sulfate, the ventilation breather one or both.
Described main salt is ventilation breather, and its content is 50 ~ 80 grams per liters.
Described conducting salt is one or both in vitriolate of tartar, the saltpetre.
Described brightening agent is one or more the combination in Sulfothiorine, potassium sulfocyanate, the furans.
Described pH value is with ammoniacal liquor or sulfuric acid adjustment.
The electroplating technology of a kind of copper electroplating liquid of the present invention is characterized in that: may further comprise the steps:
(1) metallic copper is put into above-mentioned copper electroplating solution, as anode;
(2) workpiece is put into above-mentioned copper electroplating solution, as negative electrode;
(3) pass into direct supply, 0.5 ~ 3 ampere/square decimeter of cathode current density, 40 ~ 55 ℃ of temperature of electroplating solution, electroplating time 2 ~ 8 minutes.
Cathode current density is 1.0 ~ 2.0 amperes/square decimeter in the described step (3); Temperature of electroplating solution is 45 ~ 50 ℃; Electroplating time is 4 ~ 6 minutes.
Compared with prior art, electroplate liquid of the present invention adopts New Chelating Agents to replace the prussiate complexing agent, and the beneficial effect that has is:
1) electroplate liquid does not contain prussiate, reaches the requirement of environment-protecting clean production technique, can direct labor's health problem not threatened.
2) coating and basal body binding force are good, reach the technical requirements of electrolytic coating bonding force.
Embodiment
The present invention is described in further detail below in conjunction with specific embodiment, but any limitation of the invention that does not consist of.
Embodiment 1
A kind of copper electroplating liquid, described electroplate liquid mainly comprise complexing agent, main salt, conducting salt, brightening agent, wherein:
The pH value is 10.0, with ammoniacal liquor or sulfuric acid adjustment.
Electro-plating method: adopt rectangle iron plate 70 * 100mm, electroplate test in the Hull Cell of 267ml, condition is: temperature 50 C, galvanic current are 1.0 amperes, electroplated 5 minutes, and anode uses copper coin, obtains test piece A1.
Electroplating effect is estimated: observe test piece A1 outward appearance, light evenly, crystallization is careful for coating.
Coat binding strength is estimated: according to ASTM B571(Usa Metals coating adhesive power qualitative test) standard, test piece A1 is heated to 240 ~ 260 ℃ in stove, then take out the water of putting into room temperature and cool off, observe whether bubbling or come off of coating.If the copper layer has bubbling or comes off, then copper layer and substrate combinating strength are defective; If the copper layer does not have bubbling or comes off, then copper layer and substrate combinating strength are qualified.
Embodiment 2
Electroplating bath components:
The pH value is 10.0, with ammoniacal liquor or sulfuric acid adjustment.
Electro-plating method: adopt rectangle iron plate 70 * 100mm, electroplate test in the Hull Cell of 267ml, condition is: temperature 50 C, galvanic current are 1.0 amperes, electroplated 8 minutes, and anode uses copper coin, obtains test piece A2.
Electroplating effect is estimated: observe test piece A2 outward appearance, light evenly, crystallization is careful for coating.
Coat binding strength is estimated: according to ASTM B571 standard, test piece A2 is heated to 240 ~ 260 ℃ in stove, then takes out the water of putting into room temperature and cool off, observe whether bubbling or come off of coating.If the copper layer has bubbling or comes off, then copper layer and substrate combinating strength are defective; If the copper layer does not have bubbling or comes off, then copper layer and substrate combinating strength are qualified.
Embodiment 3
Electroplating bath components:
The pH value is 11.0, with ammoniacal liquor or sulfuric acid adjustment.
Electro-plating method: adopt rectangle iron plate 70 * 100mm, electroplate test in the Hull Cell of 267ml, condition is: temperature 50 C, galvanic current are 1.0 amperes, electroplated 6 minutes, and anode uses copper coin, obtains test piece A3.
Electroplating effect is estimated: observe test piece A3 outward appearance, light evenly, crystallization is careful for coating.
Coat binding strength is estimated: according to ASTM B571 standard, test piece A3 is heated to 240 ~ 260 ℃ in stove, then takes out the water of putting into room temperature and cool off, observe whether bubbling or come off of coating.If the copper layer has bubbling or comes off, then copper layer and substrate combinating strength are defective; If the copper layer does not have bubbling or comes off, then copper layer and substrate combinating strength are qualified.
Embodiment 4
Electroplating bath components:
The pH value is 9.0, with ammoniacal liquor or sulfuric acid adjustment.
Electro-plating method: adopt rectangle iron plate 70 * 100mm, electroplate test in the Hull Cell of 267ml, condition is: 55 ℃ of temperature, galvanic current are 0.5 ampere, electroplated 8 minutes, and anode uses copper coin, obtains test piece A4.
Electroplating effect is estimated: observe test piece A4 outward appearance, light evenly, crystallization is careful for coating.
Coat binding strength is estimated: according to ASTM B571 standard, test piece A4 is heated to 240 ~ 260 ℃ in stove, then takes out the water of putting into room temperature and cool off, observe whether bubbling or come off of coating.If the copper layer has bubbling or comes off, then copper layer and substrate combinating strength are defective; If the copper layer does not have bubbling or comes off, then copper layer and substrate combinating strength are qualified.
Embodiment 5
Electroplating bath components:
The pH value is 10.0, with ammoniacal liquor or sulfuric acid adjustment.
Electro-plating method: adopt rectangle iron plate 70 * 100mm, electroplate test in the Hull Cell of 267ml, condition is: 40 ℃ of temperature, galvanic current are 0.5 ampere, electroplated 8 minutes, and anode uses copper coin, obtains test piece A5.
Electroplating effect is estimated: observe test piece A5 outward appearance, light evenly, crystallization is careful for coating.
Coat binding strength is estimated: according to ASTM B571 standard, test piece A5 is heated to 240 ~ 260 ℃ in stove, then takes out the water of putting into room temperature and cool off, observe whether bubbling or come off of coating.If the copper layer has bubbling or comes off, then copper layer and substrate combinating strength are defective; If the copper layer does not have bubbling or comes off, then copper layer and substrate combinating strength are qualified.
Embodiment 6
Electroplating bath components:
The pH value is 10.0, with ammoniacal liquor or sulfuric acid adjustment.
Electro-plating method: adopt rectangle iron plate 70 * 100mm, electroplate test in the Hull Cell of 267ml, condition is: 55 ℃ of temperature, galvanic current are 1.5 amperes, electroplated 4 minutes, and anode uses copper coin, obtains test piece A6.
Electroplating effect is estimated: observe test piece A6 outward appearance, light evenly, crystallization is careful for coating.
Coat binding strength is estimated: according to ASTM B571 standard, test piece A6 is heated to 240 ~ 260 ℃ in stove, then takes out the water of putting into room temperature and cool off, observe whether bubbling or come off of coating.If the copper layer has bubbling or comes off, then copper layer and substrate combinating strength are defective; If the copper layer does not have bubbling or comes off, then copper layer and substrate combinating strength are qualified.
Embodiment 7
Electroplating bath components:
The pH value is 10.5, with ammoniacal liquor or sulfuric acid adjustment.
Electro-plating method: adopt rectangle iron plate 70 * 100mm, electroplate test in the Hull Cell of 267ml, condition is: temperature 50 C, galvanic current are 1.0 amperes, electroplated 5 minutes, and anode uses copper coin, obtains test piece A7.
Electroplating effect is estimated: observe test piece A7 outward appearance, light evenly, crystallization is careful for coating.
Coat binding strength is estimated: according to ASTM B571 standard, test piece A7 is heated to 240 ~ 260 ℃ in stove, then takes out the water of putting into room temperature and cool off, observe whether bubbling or come off of coating.If the copper layer has bubbling or comes off, then copper layer and substrate combinating strength are defective; If the copper layer does not have bubbling or comes off, then copper layer and substrate combinating strength are qualified.
Embodiment 8
Electroplating bath components:
The pH value is 11.0, with ammoniacal liquor or sulfuric acid adjustment.
Electro-plating method: adopt rectangle iron plate 70 * 100mm, electroplate test in the Hull Cell of 267ml, condition is: temperature 45 C, galvanic current are 0.5 ampere, electroplated 3 minutes, and anode uses copper coin, obtains test piece A8.
Electroplating effect is estimated: observe test piece A8 outward appearance, light evenly, crystallization is careful for coating.
Coat binding strength is estimated: according to ASTM B571 standard, test piece A8 is heated to 240 ~ 260 ℃ in stove, then takes out the water of putting into room temperature and cool off, observe whether bubbling or come off of coating.If the copper layer has bubbling or comes off, then copper layer and substrate combinating strength are defective; If the copper layer does not have bubbling or comes off, then copper layer and substrate combinating strength are qualified.
Comparative Examples 1
Electroplating bath components: do not add inferior sodium phosphate;
Electro-plating method: adopt rectangle iron plate 70 * 100mm, electroplate test in the Hull Cell of 267ml, condition is: temperature 50 C, galvanic current are 1.0 amperes, electroplated 5 minutes, and anode uses copper coin, obtains test piece B1.
Electroplating effect is estimated: observe test piece B1 outward appearance, light evenly, crystallization is careful for coating.
Coat binding strength is estimated: according to ASTM B571 standard, test piece B1 is heated to 240 ~ 260 ℃ in stove, then takes out the water of putting into room temperature and cool off, observe whether bubbling or come off of coating.If the copper layer has bubbling or comes off, then copper layer and substrate combinating strength are defective; If the copper layer does not have bubbling or comes off, then copper layer and substrate combinating strength are qualified.
Copper facing test piece obtained above, Deposit appearance effect and bonding strength such as table 1.
Table 1: electroplating effect evaluation table
Numbering The plating bath numbering Deposit appearance Coat binding strength
Embodiment 1 A1 Light is even, crystallization is careful Qualified
Embodiment 2 A2 Light is even, crystallization is careful Qualified
Embodiment 3 A3 Light is even, crystallization is careful Qualified
Embodiment 4 A4 Light is even, crystallization is careful Qualified
Embodiment 5 A5 Light is even, crystallization is careful Qualified
Embodiment 6 A6 Light is even, crystallization is careful Qualified
Embodiment 7 A7 Light is even, crystallization is careful Qualified
Embodiment 8 A8 Light is even, crystallization is careful Qualified
Comparative Examples 1 B1 Light is even, crystallization is careful Qualified
Do not contain prussiate in the embodiment 1-8 plating bath, the plating bath of Comparative Examples 1 contains prussiate, and the test piece outward appearance copper layer light of embodiment 1-8 and Comparative Examples 1 is even, crystallization is careful, and is good with substrate combinating strength.In sum, a kind of Alkali CyanideFree Copper Electroplating Technology provided by the invention, electroplate liquid does not contain prussiate, and the copper electroplating layer light is even, careful, good with the substrate combinating strength advantage of crystallization.
The above embodiments only are the preferred embodiments of the present invention, can not limit interest field of the present invention with this, and therefore, the equivalent variations according to the present patent application claim is done still belongs to the scope that the present invention is contained.

Claims (10)

1. copper electroplating liquid, described electroplate liquid mainly comprises complexing agent, main salt, conducting salt, brightening agent, wherein:
Complexing agent content is 100 ~ 200 grams per liters;
Main salts contg is 30 ~ 100 grams per liters;
Conducting salt content is 20 ~ 50 grams per liters;
Brightening agent content is 10 ~ 100 mg/litre;
The pH value of electroplate liquid is 9.0 ~ 11.0; Solvent is water.
2. a kind of copper electroplating liquid as claimed in claim 1 is characterized in that: described complexing agent is by one or more the combination in Trisodium Citrate, thionamic acid sodium, Sunmorl N 60S, the disodium ethylene diamine tetraacetate.
3. a kind of copper electroplating liquid as claimed in claim 2, it is characterized in that: described complexing agent is disodium ethylene diamine tetraacetate and Trisodium Citrate.
4. a kind of copper electroplating liquid as claimed in claim 1 is characterized in that: described main salt by in copper sulfate, the ventilation breather one or both.
5. a kind of copper electroplating liquid as claimed in claim 4, it is characterized in that: described main salt is ventilation breather, its content is 50 ~ 80 grams per liters.
6. a kind of copper electroplating liquid as claimed in claim 1, it is characterized in that: described conducting salt is one or both in vitriolate of tartar, the saltpetre.
7. a kind of copper electroplating liquid as claimed in claim 1 is characterized in that: described brightening agent is one or more the combination in Sulfothiorine, potassium sulfocyanate, the furans.
8. a kind of copper electroplating liquid as claimed in claim 1 is characterized in that: described pH value is with ammoniacal liquor or sulfuric acid adjustment.
9. the electroplating technology of a kind of copper electroplating liquid as claimed in claim 1 is characterized in that: may further comprise the steps:
(1) metallic copper is put into above-mentioned copper electroplating solution, as anode;
(2) workpiece is put into above-mentioned copper electroplating solution, as negative electrode;
(3) pass into direct supply, 0.5 ~ 3 ampere/square decimeter of cathode current density, 40 ~ 55 ℃ of temperature of electroplating solution, electroplating time 2 ~ 8 minutes.
10. the electroplating technology of a kind of copper electroplating liquid as claimed in claim 9 is characterized in that: cathode current density is 1.0 ~ 2.0 amperes/square decimeter in the described step (3); Temperature of electroplating solution is 45 ~ 50 ℃; Electroplating time is 4 ~ 6 minutes.
CN201210586429.4A 2012-12-28 2012-12-28 A kind of copper electroplating liquid and electroplating technology thereof Active CN103014787B (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104388991A (en) * 2014-11-14 2015-03-04 无锡信大气象传感网科技有限公司 Copper electroplate liquid and preparation method thereof
CN107604392A (en) * 2017-09-29 2018-01-19 佛山市春暖花开科技有限公司 A kind of electroplate liquid of copper
CN107740146A (en) * 2017-10-27 2018-02-27 桐城运城制版有限公司 A kind of intaglio plate copper plating additive
CN109825861A (en) * 2019-03-18 2019-05-31 辽宁科技大学 A kind of pure iron base basic plating copper coating technique
CN109868492A (en) * 2018-05-18 2019-06-11 临海市伟星电镀有限公司 A kind of no cyanogen alkali copper electroplating liquid and preparation method thereof
CN110760905A (en) * 2019-11-28 2020-02-07 汕头市铠嘉模具有限公司 Application of alkaline cyanide-free copper plating process in gravure industry
CN110923757A (en) * 2019-12-27 2020-03-27 广州三孚新材料科技股份有限公司 Cyanide-free alkali copper electroplating solution and use method thereof

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US5750018A (en) * 1997-03-18 1998-05-12 Learonal, Inc. Cyanide-free monovalent copper electroplating solutions
US20060231409A1 (en) * 2005-03-31 2006-10-19 Tdk Corporation Plating solution, conductive material, and surface treatment method of conductive material
CN102234825A (en) * 2010-05-01 2011-11-09 湖北恒鑫金属表面处理有限公司 Industrial method for citrate alkaline non-cyanide copper plating on steel substrate
CN102677116A (en) * 2012-06-12 2012-09-19 山东建筑大学 Method for dipulse preplating non-cyanide alkaline copper on ferro matrix

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5750018A (en) * 1997-03-18 1998-05-12 Learonal, Inc. Cyanide-free monovalent copper electroplating solutions
US20060231409A1 (en) * 2005-03-31 2006-10-19 Tdk Corporation Plating solution, conductive material, and surface treatment method of conductive material
CN102234825A (en) * 2010-05-01 2011-11-09 湖北恒鑫金属表面处理有限公司 Industrial method for citrate alkaline non-cyanide copper plating on steel substrate
CN102677116A (en) * 2012-06-12 2012-09-19 山东建筑大学 Method for dipulse preplating non-cyanide alkaline copper on ferro matrix

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104388991A (en) * 2014-11-14 2015-03-04 无锡信大气象传感网科技有限公司 Copper electroplate liquid and preparation method thereof
CN107604392A (en) * 2017-09-29 2018-01-19 佛山市春暖花开科技有限公司 A kind of electroplate liquid of copper
CN107740146A (en) * 2017-10-27 2018-02-27 桐城运城制版有限公司 A kind of intaglio plate copper plating additive
CN109868492A (en) * 2018-05-18 2019-06-11 临海市伟星电镀有限公司 A kind of no cyanogen alkali copper electroplating liquid and preparation method thereof
CN109825861A (en) * 2019-03-18 2019-05-31 辽宁科技大学 A kind of pure iron base basic plating copper coating technique
CN110760905A (en) * 2019-11-28 2020-02-07 汕头市铠嘉模具有限公司 Application of alkaline cyanide-free copper plating process in gravure industry
CN110923757A (en) * 2019-12-27 2020-03-27 广州三孚新材料科技股份有限公司 Cyanide-free alkali copper electroplating solution and use method thereof

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