CN100554528C - Electrolytic copper foil coating surface treatment method with excellent in chemical resistance and cohesive force - Google Patents
Electrolytic copper foil coating surface treatment method with excellent in chemical resistance and cohesive force Download PDFInfo
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- CN100554528C CN100554528C CNB200610009872XA CN200610009872A CN100554528C CN 100554528 C CN100554528 C CN 100554528C CN B200610009872X A CNB200610009872X A CN B200610009872XA CN 200610009872 A CN200610009872 A CN 200610009872A CN 100554528 C CN100554528 C CN 100554528C
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Abstract
Electrolytic copper foil coating surface treatment method with excellent in chemical resistance and cohesive force relates to a kind of ternary alloy coating treatment process.In order to solve the problem that causes operational inconvenience in the existing surface treatment process of copper foil because of the substep electrochemical plating, with acidproof deterioration rate of existing surface treatment copper foil and not satisfied present situation, in the electrolytic copper foil coating of the present invention, the quality percentage composition of Zn is 65～75%, the quality percentage composition of Ni is 20～30%, the quality percentage composition of Sn is 3～7%.Its treatment process is: one, preparation electroplate liquid; Two, the selection of additive; Three, electrolytic copper foil pre-treatment; Four, galvanic deposit.The present invention adopts step electrochemical plating to carry out the deposition of ternary alloy.The FR4 copper-clad laminate that the Copper Foil that obtains with the method for the invention is pressed into can repeatedly obtain above stripping strength of 1.9～2.0N/mm and 2% following salt tolerant acid deterioration rate.
Description
Technical field
The present invention relates to a kind of ternary alloy coating treatment process.
Background technology
Electrolytic copper foil is the important materials of making printed circuit board (pcb).PCB is mainly used in fields such as robot calculator, Industry Control, aerospace and all consumer electrical equipment.Along with the fast development of electronics and information industry, China is also growing to the demand of printed circuit board, and this has brought good market outlook and opportunity to develop for the electrolytic copper foil industry.As a kind of important copper converted products, the importance of Copper Foil in industry, the modernization of national defense is more and more obvious, we can say the height of Copper Foil production technology level, has reflected the level of national Industrial products to a certain extent.
Electrolytic copper foil will pass through circuit etching in being processed into the printed-wiring board (PWB) process, etching process carries out in severe corrosive etching solutions such as acidity or alkalescence, printed-wiring board (PWB) in use also can run into corrosive atmosphere sometimes, and this just requires Copper Foil should have good resistance to corrosive chemicals energy.Electrolytic copper foil can experience repeatedly hot procedure in making the printed circuit board process, weld and solder resist curing etc. when electron device being installed thereon.Therefore, also need Copper Foil to have good resistance toheat.At present, when producing, China's electrolytic copper foil, in its surface treatment process, mainly adopts the method for electroplating Zn in order to satisfy its requirement.The electrolytic copper foil chemical resistant properties of being produced and thermotolerance and bond strength are compared with Copper Foil beautiful, that day produce and are had a long way to go, and have caused China's high-performance Copper Foil mainly to rely on the difficult situation of import.Therefore, a kind of electrolytic copper foil surface treatment process that can effectively improve chemical resistant properties and bond strength of exploitation becomes the task of top priority.
Compare the characteristic with a lot of excellences with zinc coating owing to electroplate the Zn alloy layer, particularly its good solidity to corrosion and low hydrogen embrittlement have caused people's very big interest and concern.The kind of electroplating the zinc-base binary alloy at copper foil surface mainly is Zn-Ni, Zn-Sn alloy, and its corrosion resisting property is better than pure Zn coating, but Copper Foil its chemical resistant properties after long storage after handling like this is still unsatisfactory.And the bibliographical information of taking to electroplate the Zn base ternary alloy on electrolytic copper foil only limits to partial monopoly, two step of employing electrochemical plating as relevant patent report are plated one deck Zn-Sn alloy earlier on Copper Foil, plate layer of Ni coating again, though this kind method has solved Copper Foil chemical-resistant problem after long storage, but operation is complicated, and promoting the use of of this technology is restricted.
Summary of the invention
The purpose of this invention is to provide a kind of electrolytic copper foil coating surface treatment method with excellent in chemical resistance and cohesive force, this method is at the electroplating surface Zn-Ni-Sn of electrolytic copper foil ternary metal alloy layer, handle through chromating again and coating one deck silane coupling agent, not only solve the problem that causes operational inconvenience in the existing surface treatment process of copper foil because of the substep electrochemical plating, also solved acidproof deterioration rate of existing surface treatment copper foil and not satisfied present situation.In the Zn-Ni-Sn ternary alloy electrolytic copper foil coating of the present invention, the quality percentage composition of Zn is 65～75%, the quality percentage composition of Ni is 20～30%, the quality percentage composition of Sn is 3～7%.The present invention handles electrolytic copper foil surface according to following steps: one, electroplate liquid preparation: (1) uses dissolved in distilled water respectively with potassium pyrophosphate 140～240g/L, zinc sulfate 10～30g/L, single nickel salt 10～30g/L, the stannous sulfate 5～30g/ that weighs up, when the potassium pyrophosphate solution stirring when clarifying, at first the stannous sulfate aqueous solution is joined in the potassium pyrophosphate solution, stir, heat, treat that it dissolves fully, again solvent solution of zinc sulfate is also added wherein, stirred solution is to clarification, again solvent single nickel salt is added, stir to clarify; At last load weighted sodium sulfate 50～100g/L is dissolved fully with distilled water, join in the solution, stir to clarify; (2) treat solution cooling after, add the hydrogen peroxide 1～10ml/L of aequum, stir till no longer producing bubble; Two, the selection of additive: add additive in electroplate liquid successively, described additive is one or more a mixture in 2-butyne-1.4 glycol, quadrol, Sodium dodecylbenzene sulfonate, the piperonylaldehyde; Three, electrolytic copper foil pre-treatment: electrolytic copper foil is immersed in the oxide film of removing copper foil surface in the dilution heat of sulfuric acid, takes out the back and remove the residual S0 of copper foil surface with distilled water flushing
4 2-Four, galvanic deposit: anode adopts Graphite Electrodes, and negative electrode is 2: 1～1: 1 with anodic area ratio, and the distance between the anode and cathode is 5～8cm, and temperature is controlled at 20～30 ℃, and current density is 2～5A/dm
2, electroplating time is 2s～15min.
The present invention adopts step electrochemical plating to carry out the deposition of ternary alloy.The FR4 copper-clad laminate that the Copper Foil that obtains with the method for the invention is pressed into can repeatedly obtain above stripping strength of 1.9～2.0N/mm and 2% following salt tolerant acid deterioration rate.Salt tolerant acid deterioration rate is exactly an important measurement index of Copper Foil chemical resistance, after being meant Copper Foil compacting copper-clad laminate, record its stripping strength A1 by the peel strength test machine, this copper-clad laminate is immersed 18% aqueous hydrochloric acid again and soak at normal temperatures and measure its stripping strength A2 after 60 minutes again, its salt tolerant acid deterioration rate B is calculated by following formula:
The present invention has following advantage:
Even 1 printed-wiring board (PWB) is to make with the old Copper Foil that this method of long storage is handled, the interface between copper circuit and the base material can be by acidic solution or basic solution corrosion yet;
Even 2 in forming the process of copper foil covered plywood this Copper Foil contact with containing organic acid varnish, the interface of Copper Foil and base material also hardly can be owing to organic acid variation, the bond strength between them is enough big;
3, use this technology that electrolytic copper foil is carried out aftertreatment, its anti-erosion intensity is 1.9～2.0N/mm, and the deterioration rate is less than 5%.
4, the copper alms bowl of handling through the technology of the present invention does not use arsenide, helps cleaner production.
Description of drawings
Fig. 1 is the structural representation of the method for the invention electroplanting device, wherein 1: anode, 2: thermometer, 3: negative electrode, 4: constant current source, 5: coating bath; Fig. 2 is the shape appearance figure (2s) of electrolytic copper foil after electroplating the aftertreatment of Zn-Sn-Ni ternary alloy; Fig. 3 is the shape appearance figure (15min) of electrolytic copper foil after electroplating the aftertreatment of Zn-Sn-Ni ternary alloy.
Embodiment
Embodiment one: in the electrolytic copper foil coating in the present embodiment, the quality percentage composition of Zn is 65～75%, the quality percentage composition of Ni is 20～30%, the quality percentage composition of Sn is 3～7%.
Embodiment two: what present embodiment and embodiment one were different is, the quality percentage composition of Zn is 75% in the electrolytic copper foil coating, the quality percentage composition of Ni is 22%, the quality percentage composition of Sn is 3%.
Embodiment three: what present embodiment and embodiment one were different is, the quality percentage composition of Zn is 70% in the electrolytic copper foil coating, the quality percentage composition of Ni is 25%, the quality percentage composition of Sn is 5%.
Embodiment four: what present embodiment and embodiment one were different is, the quality percentage composition of Zn is 65% in the electrolytic copper foil coating, the quality percentage composition of Ni is 28%, the quality percentage composition of Sn is 7.
Embodiment five: present embodiment is achieved in that
One, electroplate liquid preparation: (1) uses dissolved in distilled water respectively with potassium pyrophosphate 140～240g/L, zinc sulfate 10～30g/L, single nickel salt 10～30g/L, the stannous sulfate 5～30g/L that weighs up, when the potassium pyrophosphate solution stirring when clarifying, at first the stannous sulfate aqueous solution is joined in the potassium pyrophosphate solution, stir, heat, treat that it dissolves fully, more solvent solution of zinc sulfate also added wherein that stirred solution is to clarification, again solvent single nickel salt is added, stir to clarify; At last load weighted sodium sulfate 50～100g/L is dissolved fully with distilled water, join in the solution, stir to clarify; (2) treat solution cooling after, add the hydrogen peroxide 1～10ml/L of aequum, stir till no longer producing bubble;
Two, the selection of additive: add additive in electroplate liquid successively, described additive is one or more a mixture in 2-butyne-1.4 glycol, quadrol, Sodium dodecylbenzene sulfonate, the piperonylaldehyde;
Three, electrolytic copper foil pre-treatment: electrolytic copper foil is immersed in the oxide film of removing copper foil surface in the dilution heat of sulfuric acid, takes out the back and remove the residual S0 of copper foil surface with distilled water flushing
4 2-
Four, galvanic deposit: anode adopts Graphite Electrodes, and negative electrode is 2: 1～1: 1 with anodic area ratio, and the distance between the anode and cathode is 5～8cm, and temperature is controlled at 20～30 ℃, and current density is 2～5A/dm
2, electroplating time is 2s～15min, electroplanting device is as shown in Figure 1.
Embodiment six: what present embodiment and embodiment two were different is to add piperonylaldehyde 0.05～0.15g/L and 2-butyne-1.4 glycol 0.01～0.05g/L and can make the refinement of coating light compact crystal in plating bath; Interpolation Sodium dodecylbenzene sulfonate 0.01～0.05g/L can effectively suppress the hydrogen evolution phenomenon in the electroplating process; Add quadrol (analytical pure) 0.5～1.5ml/L and can enlarge the working current density scope, improve current efficiency, and make coating even.
Embodiment seven: electrolytic solution is formed: potassium pyrophosphate 0.5mol/L, [Zn
2+]: [Ni
2+]: [Sn
2+] ratio be 5: 4: 2 (total ion concentration is 0.2mol/L), add 0.5mol/L anhydrous sodium sulphate, 1.2ml/L quadrol, 0.05g/L piperonylaldehyde.Control current density 4A/cm
2, 20 ℃, electroplate 2s～10min during pH=8.5 and can obtain the careful alloy layer of light.Test result shows under this kind processing condition that anti-erosion intensity is 1.92N/mm, deterioration rate 1.35%.As can be seen from Figure 2: through the plating in two seconds, the Zn-Ni-Sn alloy has only deposited very thin one deck.As can be seen from Figure 3: through 15 minutes plating, alloy layer covered copper foil surface fully, and the crystallization of Zn-Ni-Sn alloy is careful evenly, coating is also smooth.
Embodiment eight: electrolytic solution is formed: potassium pyrophosphate 0.5mol/L, [Zn
2+]: [Ni
2+]: [Sn
2+] ratio be 5: 4: 2 (total ion concentration is 0.2mol/L), add 0.2mol/L anhydrous sodium sulphate, 0.8ml/L quadrol, 0.03g/L piperonylaldehyde, 0.02g/L Sodium dodecylbenzene sulfonate.Control current density 4A/cm
2, 20 ℃, electroplate 2s～10min during pH=8.5 and can obtain the careful alloy layer of light.Test result shows under this kind processing condition that anti-erosion intensity is 1.95N/mm, deterioration rate 2.1%.
Embodiment nine: electrolytic solution is formed: potassium pyrophosphate 0.5mol/L, [Zn
2+]: [Ni
2+]: [Sn
2+] ratio be 5: 4: 2 (total ion concentration is 0.2mol/L), add 0.01g/L 2-butyne-1.4 glycol, 0.5mol/L anhydrous sodium sulphate, 1.2ml/L quadrol.Control current density 4A/cm
2, 20 ℃, electroplate 2s～10min during pH=8.5 and can obtain the careful alloy layer of light.Test result shows under this kind processing condition that anti-erosion intensity is 1.98N/mm, deterioration rate 1.14%.
Embodiment ten: electrolytic solution is formed: potassium pyrophosphate 0.5mol/L, [Zn
2+]: [Ni
2+]: [Sn
2+] ratio be 5: 4: 2 (total ion concentration is 0.2mol/L), add 0.01g/L 2-butyne-1.4 glycol, 0.5mol/L anhydrous sodium sulphate, 1.2ml/L quadrol.Control current density 4A/cm
2, 20 ℃, electroplate 2s～10min during pH=8.5 and can obtain the careful alloy layer of light.Test result shows under this kind processing condition that anti-erosion intensity is 1.98N/mm, deterioration rate 1.14%.
Embodiment 11: electrolytic solution is formed: potassium pyrophosphate 0.5mol/L, [Zn
2+]: [Ni
2+]: [Sn
2+] ratio be 5: 4: 2 (total ion concentration is 0.2mol/L), add 0.04g/L 2-butyne-1.4 glycol, 0.2mol/L anhydrous sodium sulphate, 0.6ml/L quadrol, 0.02g/L Sodium dodecylbenzene sulfonate.Control current density 4A/cm
2, 20 ℃, electroplate 2s～10min during pH=8.5 and can obtain the careful alloy layer of light.Test result shows under this kind processing condition that anti-erosion intensity is 1.99N/mm, deterioration rate 4.12%.
In the coating that the described method in embodiment seven～11 obtains, the content of Zn is about 70%, the content of Ni is about 25%, the content of Sn is about 5%.
Claims (8)
1, a kind of electrolytic copper foil coating surface treatment method with excellent in chemical resistance and cohesive force is characterized in that described method is:
One, electroplate liquid preparation: (1) uses dissolved in distilled water respectively with potassium pyrophosphate 140～240g/L, zinc sulfate 10～30g/L, single nickel salt 10～30g/L, the stannous sulfate 5～30g/L that weighs up, when the potassium pyrophosphate solution stirring when clarifying, at first the stannous sulfate aqueous solution is joined in the potassium pyrophosphate solution, stir, heat, treat that it dissolves fully, more solvent solution of zinc sulfate also added wherein that stirred solution is to clarification, again solvent single nickel salt is added, stir to clarify; At last load weighted sodium sulfate 50～100g/L is dissolved fully with distilled water, join in the solution, stir to clarify; (2) treat solution cooling after, add the hydrogen peroxide 1～10ml/L of aequum, stir till no longer producing bubble;
Two, the selection of additive: add additive in electroplate liquid successively, described additive is one or more a mixture in 2-butyne-1.4 glycol, quadrol, Sodium dodecylbenzene sulfonate, the piperonylaldehyde;
Three, electrolytic copper foil pre-treatment: electrolytic copper foil is immersed in the oxide film of removing copper foil surface in the dilution heat of sulfuric acid, takes out the back and remove the residual S0 of copper foil surface with distilled water flushing
4 2-
Four, galvanic deposit: anode adopts Graphite Electrodes, and negative electrode is 2: 1～1: 1 with anodic area ratio, and the distance between the anode and cathode is 5～8cm, and temperature is controlled at 20～30 ℃, and current density is 2～5A/dm
2, electroplating time is 2s～15min.
2, the surface treatment method with electrolytic copper foil coating of excellent in chemical resistance and cohesive force according to claim 1 is characterized in that [Zn in the described electroplate liquid
2-]: [Ni
2+]: [Sn
2+] ratio be 5: 4: 2, Zn
2+, Ni
2+, Sn
2+Three's total ion concentration is 0.2mol/L.
3, the surface treatment method with electrolytic copper foil coating of excellent in chemical resistance and cohesive force according to claim 1 is characterized in that the composition of described additive and content are: piperonylaldehyde 0.05～0.15g/L, 2-butyne-1.4 glycol 0.01～0.05g/L, Sodium dodecylbenzene sulfonate 0.01～0.05g/L and quadrol 0.5～1.5ml/L.
4, the surface treatment method with electrolytic copper foil coating of excellent in chemical resistance and cohesive force according to claim 1 is characterized in that the composition of described additive and content are: 1.2ml/L quadrol, 0.05g/L piperonylaldehyde.
5, the surface treatment method with electrolytic copper foil coating of excellent in chemical resistance and cohesive force according to claim 1 is characterized in that the composition of described additive and content are: 0.8ml/L quadrol, 0.03g/L piperonylaldehyde, 0.02g/L Sodium dodecylbenzene sulfonate.
6, the surface treatment method with electrolytic copper foil coating of excellent in chemical resistance and cohesive force according to claim 1 is characterized in that the composition of described additive and content are: 0.01g/L2-butine-1.4 glycol, 1.2ml/L quadrol.
7, the surface treatment method with electrolytic copper foil coating of excellent in chemical resistance and cohesive force according to claim 1 is characterized in that the composition of described additive and content are: 0.04g/L 2-butyne-1.4 glycol, 0.6ml/L quadrol, 0.02g/L Sodium dodecylbenzene sulfonate.
8, the surface treatment method with electrolytic copper foil coating of excellent in chemical resistance and cohesive force according to claim 1 is characterized in that current density is 4A/cm
2, electroplating temperature is 20 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI625401B (en) * | 2016-03-31 | 2018-06-01 | Jx Nippon Mining & Metals Corp | Titanium copper foil with plating |
Families Citing this family (4)
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|---|---|---|---|---|
| CN101935836B (en) * | 2010-08-03 | 2012-06-06 | 山东金宝电子股份有限公司 | Surface treatment process of reddened copper foil for high-grade FR-4 copper-clad plate |
| CN103849912A (en) * | 2012-11-29 | 2014-06-11 | 沈阳工业大学 | Electroplating technology of shining tin zinc nickel alloy |
| CN110029373A (en) * | 2019-05-24 | 2019-07-19 | 山东金宝电子股份有限公司 | A kind of compound additive for eliminating the unusual coarsening crystallization of electrolytic copper foil |
| CN111304709A (en) * | 2020-04-22 | 2020-06-19 | 山东金宝电子股份有限公司 | Surface treating agent for improving corrosion resistance of electrolytic copper foil |
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|---|---|---|---|---|
| US4469567A (en) * | 1982-12-01 | 1984-09-04 | Torday & Carlisle Public Limited Company | Treatment of copper foil |
| CN1468327A (en) * | 2000-09-16 | 2004-01-14 | ƽ | Ternary tin zinc alloy, electroplating solutions and galvanic method for producing ternary tin zinc alloy coatings |
| CN1183814C (en) * | 1998-11-30 | 2005-01-05 | 三井金属鉱业株式会社 | Copper foil with good chemicals-resisting and heat-resisting characteristicas for printed circuit board |
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2006
- 2006-03-29 CN CNB200610009872XA patent/CN100554528C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4469567A (en) * | 1982-12-01 | 1984-09-04 | Torday & Carlisle Public Limited Company | Treatment of copper foil |
| CN1183814C (en) * | 1998-11-30 | 2005-01-05 | 三井金属鉱业株式会社 | Copper foil with good chemicals-resisting and heat-resisting characteristicas for printed circuit board |
| CN1468327A (en) * | 2000-09-16 | 2004-01-14 | ƽ | Ternary tin zinc alloy, electroplating solutions and galvanic method for producing ternary tin zinc alloy coatings |
Non-Patent Citations (2)
| Title |
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| 印制板用电解铜箔后处理工艺的研究. 杨培霞，安茂忠，胡旭日，徐树民，蒲宇达.电镀与涂饰，第24卷第8期. 2005 |
| 印制板用电解铜箔后处理工艺的研究. 杨培霞，安茂忠，胡旭日，徐树民，蒲宇达.电镀与涂饰，第24卷第8期. 2005 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI625401B (en) * | 2016-03-31 | 2018-06-01 | Jx Nippon Mining & Metals Corp | Titanium copper foil with plating |
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Assignee: Kaiping Pacific Insulation Material Co.,Ltd. Assignor: Harbin Institute of Technology Contract record no.: 2011440000699 Denomination of invention: Surface treatment method for electrolytic copper foil coating excellent in chemical resistance and cohesive force Granted publication date: 20091028 License type: Exclusive License Open date: 20061011 Record date: 20110719 |
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