CN105177659A - Surface treatment process for improving corrosion resistance of copper foil - Google Patents

Surface treatment process for improving corrosion resistance of copper foil Download PDF

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Publication number
CN105177659A
CN105177659A CN201510487702.1A CN201510487702A CN105177659A CN 105177659 A CN105177659 A CN 105177659A CN 201510487702 A CN201510487702 A CN 201510487702A CN 105177659 A CN105177659 A CN 105177659A
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Prior art keywords
copper foil
concentration
treatment
solution
additive
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CN201510487702.1A
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CN105177659B (en
Inventor
王建智
樊斌锋
韩树华
何铁帅
张欣
周赞雄
郭稳平
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Lingbao Wason Copper Foil Co Ltd
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Lingbao Wason Copper Foil Co Ltd
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Abstract

The invention provides a surface treatment process for improving the corrosion resistance of copper foil and belongs to the technical field of surface treatment processes of electrolytic copper foil. The surface treatment process includes the following steps that (1) electrolyte is prepared, i.e., a settled solution is obtained after potassium pyrophosphate, stannous chloride and zinc sulfate of a complexing agent and an additive A are mixed and then dissolved in water, the concentration of K4P2O7 in the solution is 40 g/L-55 g/L, the concentration of Zn2+ in the solution is 0.6 g/L-1.5 g/L, the concentration of Sn2+ in the solution is 0.5 g/L-0.8 g/L, and the concentration of the additive A in the solution is 1 g/L-1.8 g/L; the additive A is at least one of SPS, sodium citrate, Mo, Fe and ammonium carbonate; and (2) the copper foil is electroplated, i.e., preprocessed copper foil is placed in an electroplating tank containing the electrolyte obtained in the step (1) for electroplating. According to the surface treatment process, a Zn-Sn composite coating is electroplated on the surface of the copper foil mainly, and therefore the corrosion resistance of the copper foil is improved.

Description

A kind of process of surface treatment improving Copper Foil corrosion resistance nature
Technical field
The invention belongs to electrolytic copper foil surface treatment process technical field, be specifically related to a kind of process of surface treatment improving Copper Foil corrosion resistance nature.
Background technology
Domestic enterprise is when carrying out surface treatment to electrolytic copper foil, and blocking layer mainly adopts zinc coating.Adopt common zincincation, resistance to heat problem can only be solved, and do not solve the corrosion resisting property problem of Copper Foil completely; When zinc-plated Copper Foil etching, side etching phenomenon can occur, cause the bonding force of Copper Foil and insulating body to decline, time serious, Copper Foil even can come off from insulating body, and this is one of Main Gaps of domestic electrolytic copper foil and external expensive goods performance.In addition, because prussiate galvanizing solution has good dispersive ability and covering power, industrially widely use so far from 20 beginnings of the century, but plating solution is hypertoxic, serious environment pollution, plating solution reclaims and wastewater treatment is difficult and cost is high always.Along with people's environmental consciousness is strengthened, plating is just gradually to without cyaniding future development, and the process of surface treatment tool therefore studying electrolytic copper foil is of great significance.
Summary of the invention
The object of this invention is to provide a kind of process of surface treatment improving Copper Foil corrosion resistance nature.
Based on above-mentioned purpose, this invention takes following technical scheme:
Improve a process of surface treatment for Copper Foil corrosion resistance nature, comprise the steps:
(1) preparation of electrolytic solution: after complexing agent potassium pyrophosphate, tin protochloride, zinc sulfate and additive A being mixed, water-solublely obtain settled solution, and K in solution 4p 2o 7concentration is 40g/L ~ 55g/L, Zn 2+concentration is 0.6g/L ~ 1.5g/L, Sn 2+concentration is 0.5g/L-0.8g/L, and additive A concentration is 1g/L-1.8g/L, and wherein, additive A adopts at least one in SPS, Trisodium Citrate, Mo, Fe, volatile salt; The chemical name of SPS: sodium polydithio-dipropyl sulfonate (molecular formula C 6h 12o 6s 4na 2).
(2) Copper Foil plating: pretreated Copper Foil is put into the plating tank containing (1) electrolytic solution in steps and electroplate.
Preferably, when electroplating in step (2), the pH of electrolytic solution is 9-12, and temperature is 35-45 DEG C, and passing into galvanic current density on positive plate is 1.2-2.6A/dm 2.
The present invention mainly forms Zn-Sn composite deposite in copper foil surface plating, thus improves the corrosion resistance nature of Copper Foil.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but protection scope of the present invention is not limited thereto.
Embodiment 1
Improve a process of surface treatment for Copper Foil corrosion resistance nature, comprise the steps:
(1) preparation of electrolytic solution: after complexing agent potassium pyrophosphate, tin protochloride, zinc sulfate and additive A being mixed, water-solublely obtain settled solution, and K in solution 4p 2o 7concentration is 50g/L, Zn 2+concentration is 1.2g/L, Sn 2+concentration is 1.2g/L, and additive A concentration is 1.5g/L, and additive A is made up of Trisodium Citrate, Fe and volatile salt, and amount of substance is than being 1:2:5.
(2) Copper Foil plating: micron electrolytic copper foil of 18 after alligatoring, solidification treatment is put into the plating tank containing (1) electrolytic solution in steps and electroplate, Copper Foil through the speed of a motor vehicle of electrolytic solution be 35m/min, during plating, electrolytic solution pH is 10.5, and temperature is 40 DEG C, and current density is 1.8A/dm 2, electroplating time is 4s.
The sample room temperature of embodiment 1 is put into corrosive medium (concentration is the NaCl aqueous solution of 5wt%) to test, and record the rust time.
Embodiment 2
Improve a process of surface treatment for Copper Foil corrosion resistance nature, comprise the steps:
(1) preparation of electrolytic solution: after complexing agent potassium pyrophosphate, tin protochloride, zinc sulfate and additive A being mixed, water-solublely obtain settled solution, and K in solution 4p 2o 7concentration is 55g/L, Zn 2+concentration is 1.5g/L, Sn 2+concentration is 0.5g/L, and additive A concentration is 1.8g/L, and wherein, additive A adopts SPS and volatile salt, and amount of substance is than being 7:3;
(2) Copper Foil plating: micron electrolytic copper foil of 18 after alligatoring, solidification treatment is put into the plating tank containing (1) electrolytic solution in steps and electroplate, Copper Foil through the speed of a motor vehicle of electrolytic solution be 25m/min, during plating, electrolytic solution pH is 9, and temperature is 45 DEG C, and current density is 1.2A/dm 2, electroplating time is 7s.
The sample room temperature of embodiment 2 is put into corrosive medium (concentration is the NaCl aqueous solution of 5wt%) to test, and record the rust time.
Embodiment 3
Improve a process of surface treatment for Copper Foil corrosion resistance nature, comprise the steps:
(1) preparation of electrolytic solution: after complexing agent potassium pyrophosphate, tin protochloride, zinc sulfate and additive A being mixed, water-solublely obtain settled solution, and K in solution 4p 2o 7concentration is 40g/L, Zn 2+concentration is 0.6g/L, Sn 2+concentration is 0.6g/L, and additive A concentration is 1.0g/L, and wherein, additive A adopts Trisodium Citrate;
(2) Copper Foil plating: micron electrolytic copper foil of 18 after alligatoring, solidification treatment is put into the plating tank containing (1) electrolytic solution in steps and electroplate, Copper Foil through the speed of a motor vehicle of electrolytic solution be 30m/min, during plating, electrolytic solution pH is 12, and temperature is 35 DEG C, and current density is 2.6A/dm 2, electroplating time is 6s.
The sample room temperature of embodiment 3 is put into corrosive medium (concentration is the NaCl aqueous solution of 5wt%) to test, and record the rust time.
Copper foil sample made by embodiment 1 to 3, test through corrosion resistance nature, the rust time is 350h, 370h and 320h respectively, the rust time is all greatly improved than the Copper Foil (150h) without composite deposite process, adopt the process of surface treatment of the present invention's research and development, form Co and Zn-Sn composite deposite, effectively improve Copper Foil corrosion resistance nature.

Claims (2)

1. improve a process of surface treatment for Copper Foil corrosion resistance nature, it is characterized in that, comprise the steps:
(1) preparation of electrolytic solution: after complexing agent potassium pyrophosphate, tin protochloride, zinc sulfate and additive A being mixed, water-solublely obtain settled solution, and K in solution 4p 2o 7concentration is 40g/L ~ 55g/L, Zn 2+concentration is 0.6g/L ~ 1.5g/L, Sn 2+concentration is 0.5g/L-0.8g/L, and additive A concentration is 1g/L-1.8g/L, and wherein, additive A is at least one in SPS, Trisodium Citrate, Mo, Fe and volatile salt;
(2) Copper Foil plating: pretreated Copper Foil is put into the plating tank containing (1) electrolytic solution in steps and electroplate.
2. the process of surface treatment of raising Copper Foil corrosion resistance nature according to claim 1, is characterized in that, when electroplating in step (2), the pH of electrolytic solution is 9-12, and temperature is 35-45 DEG C, and passing into galvanic current density on positive plate is 1.2-2.6A/dm 2.
CN201510487702.1A 2015-08-10 2015-08-10 A kind of process of surface treatment for improving copper foil corrosion resistance Expired - Fee Related CN105177659B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN111534839A (en) * 2020-05-12 2020-08-14 建滔(连州)铜箔有限公司 Plating solution of high-temperature-resistant and oxidation-resistant alloy copper foil and application thereof

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CN101935856A (en) * 2010-08-03 2011-01-05 山东金宝电子股份有限公司 Back face treatment process of electrolytic copper foil
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CN102618902A (en) * 2012-04-24 2012-08-01 山东金宝电子股份有限公司 Surface treatment process of copper foil for flexible copper-clad plate
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CN1962994A (en) * 2005-11-07 2007-05-16 东海工业缝纫机株式会社 Sewing machine
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CN101906630A (en) * 2010-08-03 2010-12-08 山东金宝电子股份有限公司 Black surface treatment process of electrolytic copper foil
CN101935856A (en) * 2010-08-03 2011-01-05 山东金宝电子股份有限公司 Back face treatment process of electrolytic copper foil
CN101935836A (en) * 2010-08-03 2011-01-05 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
JP2012219368A (en) * 2011-04-14 2012-11-12 Nan Ya Plastics Corp Ultra thin copper foil with very low profile copper foil as carrier and manufacturing method therefor
CN102618902A (en) * 2012-04-24 2012-08-01 山东金宝电子股份有限公司 Surface treatment process of copper foil for flexible copper-clad plate

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN111534839A (en) * 2020-05-12 2020-08-14 建滔(连州)铜箔有限公司 Plating solution of high-temperature-resistant and oxidation-resistant alloy copper foil and application thereof

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