CN104651884A - Compound additive for electrolytic copper foil - Google Patents

Compound additive for electrolytic copper foil Download PDF

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Publication number
CN104651884A
CN104651884A CN201410173400.2A CN201410173400A CN104651884A CN 104651884 A CN104651884 A CN 104651884A CN 201410173400 A CN201410173400 A CN 201410173400A CN 104651884 A CN104651884 A CN 104651884A
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CN
China
Prior art keywords
copper foil
electrolytic copper
mercaptobenzimidazole
polyglycerine
gelatin
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Pending
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CN201410173400.2A
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Chinese (zh)
Inventor
雷磊
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Individual
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Individual
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Priority to CN201410173400.2A priority Critical patent/CN104651884A/en
Publication of CN104651884A publication Critical patent/CN104651884A/en
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Abstract

The invention relates to a compound additive for an electrolytic copper foil. The compound additive is characterized by consisting of five raw materials, namely sodium 3,3'-dithiodipropane sulfonate, polyglycerol, 2-mercaptobenzimidazole, hydrolyzed gelatin and rare earth sulfate.

Description

A kind of electrolytic copper foil complex additive
Technical field
The present invention relates to a kind of electrolytic copper foil complex additive, belong to high-end electrolytic copper foil technical field of producing.
Background technology
Along with informationized society development, the electronic products such as ultra-slim features equipment, wearable device, intelligent machine emerge in an endless stream, and novel electron equipment develops to portability precise treatment.Electrolytic copper foil is the important source material manufacturing copper-clad plate and printed circuit board, is the nerve net winding thread laying each element of modern electronic product.
Flexible PCB (Flexible Printed Circuit, FPC), has frivolous property, resistance to bending, the advantage such as scalable, is widely used in modern electronic product and traffic, space flight, military field.The FPC that mass-producing manufactures high-quality must have high performance electrolytic copper foil.China's low side Copper Foil production capacity surplus, but market lacks domestic high-rank copper foil product always.
The quality of electrolytic copper foil quality directly restricts the development of modern electronic product, allocate suitable electrolytic copper foil additive and can control copper electrodeposition process, effectively can improve the dispersive ability of electrolyte of copper foil, sedimentation rate, conductive capability, current efficiency, leveling ability and covering power, improve the unit elongation, resistance to bending, surface uniformity etc. of Copper Foil.Additive is the gordian technique point manufacturing high-end electrolytic copper foil product.
Summary of the invention
The object of the present invention is to provide a kind of complex additive that can be used for manufacturing superelevation unit elongation electrolytic copper foil, use the electrolytic copper foil that time complex additive manufactures, 12 micron thickness Copper Foil normal temperature unit elongation >=15%, high temperature unit elongation >=18%, improves the snappiness of Copper Foil product and resistance to bending performance greatly.Little and the even particle size distribution of this Copper Foil product microcosmic crystal grain, has low profile, hair side roughness Rz≤1.0 micron, meets high-frequency high-speed electric signal transmission demand, be suitable for the service requirements of high-end flexible PCB, and production control technique is simple, with low cost.
The technical solution used in the present invention is as follows:
A kind of electrolytic copper foil complex additive, be made up of sodium polydithio-dipropyl sulfonate (Sodium 3,3-dithiodipropane sulfonate), Polyglycerine (polyglycerol), 2-mercaptobenzimidazole (2-Mercaptobenzimidazole), gelatin hydrolysate (Gelatin), rare earth sulfate five kinds of raw materials;
The consumption of above-mentioned five kinds of raw materials is: containing 5 ~ 500mg sodium polydithio-dipropyl sulfonate (Sodium 3,3-dithiodipropane sulfonate), 5 ~ 800mg Polyglycerine (Polyglycerol), 0.5 ~ 50mg 2-mercaptobenzimidazole (2-Mercaptobenzimidazole), 5 ~ 800mg gelatin hydrolysate (Gelatin), 0.2 ~ 50mg rare earth sulfate in often liter of electrolytic copper foil electrolytic solution.
Above-mentioned five kinds of raw material optimum amounts are: containing 8 ~ 100mg sodium polydithio-dipropyl sulfonate (Sodium 3,3-dithiodipropane sulfonate), 5 ~ 200mg5 ~ 800mg Polyglycerine (Polyglycerol), 0.8 ~ 20mg 2-mercaptobenzimidazole (2-Mercaptobenzimidazole), 10 ~ 200mg gelatin hydrolysate (Gelatin), 0.2 ~ 30mg rare earth sulfate in often liter of electrolytic copper foil electrolytic solution.
Described rare earth sulfate is lanthanum sulfat, cerous sulfate or two kinds of mixtures.
Described gelatin hydrolysate is the gelatin of the small-molecular-weight of molecular weight between 1000 ~ 4000.
Described Polyglycerine is three Polyglycerine (Triglycerol).
The object of the present invention is to provide a kind of complex additive that can be used for manufacturing superelevation unit elongation electrolytic copper foil, use the electrolytic copper foil that time complex additive manufactures, 12 micron thickness Copper Foil normal temperature unit elongation >=15%, high temperature unit elongation >=20%, improves the snappiness of Copper Foil product and resistance to bending performance greatly.Little and the even particle size distribution of this Copper Foil product microcosmic crystal grain, has low profile, hair side roughness Rz≤1.0 micron, meets high-frequency high-speed electric signal transmission demand, be suitable for the service requirements of high-end flexible PCB, and production control technique is simple, with low cost.
Accompanying drawing explanation
Fig. 1: adopt the complex additive in the present invention manufacturing the SEM figure under superelevation unit elongation electrolytic copper foil 2000 times.
Embodiment
Below in conjunction with specific embodiment of the invention scheme, further illustrate technical scheme of the present invention, but embodiments of the present invention are not limited to following specific embodiments.
Complex additive of the present invention manufacture superelevation unit elongation electrolytic copper foil time, electrolytic solution content of copper ion 60 ~ 120g/L, sulfuric acid 90 ~ 150g/L, chlorion 10 ~ 60mg/L, temperature 45 ~ 55 DEG C, current density 50 ~ 75A/dm 2, in process of production by following for interpolation complex additive, adopt conventional electrolytic copper foil electrodeposition technology to produce.
Case study on implementation 1: a kind of complex additive that can be used for manufacture superelevation unit elongation electrolytic copper foil, containing 20mg sodium polydithio-dipropyl sulfonate, 30mg tri-Polyglycerine, 5mg 2-mercaptobenzimidazole, 50mg gelatin hydrolysate, 5mg rare earth sulfate in often liter of electrolytic copper foil electrolytic solution.
Case study on implementation 2: a kind of complex additive that can be used for manufacture superelevation unit elongation electrolytic copper foil, containing 20mg sodium polydithio-dipropyl sulfonate, 50mg tri-Polyglycerine, 5mg 2-mercaptobenzimidazole, 50mg gelatin hydrolysate, 5mg rare earth sulfate in often liter of electrolytic copper foil electrolytic solution.
Case study on implementation 3: a kind of complex additive that can be used for manufacture superelevation unit elongation electrolytic copper foil, containing 20mg sodium polydithio-dipropyl sulfonate, 75mg tri-Polyglycerine, 5mg 2-mercaptobenzimidazole, 50mg gelatin hydrolysate, 2mg rare earth sulfate in often liter of electrolytic copper foil electrolytic solution.
Case study on implementation 4: a kind of complex additive that can be used for manufacture superelevation unit elongation electrolytic copper foil, containing 20mg sodium polydithio-dipropyl sulfonate, 75mg tri-Polyglycerine, 5mg 2-mercaptobenzimidazole, 50mg gelatin hydrolysate, 5mg rare earth sulfate in often liter of electrolytic copper foil electrolytic solution.
Case study on implementation 5: a kind of complex additive that can be used for manufacture superelevation unit elongation electrolytic copper foil, containing 20mg sodium polydithio-dipropyl sulfonate, 75mg tri-Polyglycerine, 5mg 2-mercaptobenzimidazole, 50mg gelatin hydrolysate, 8mg rare earth sulfate in often liter of electrolytic copper foil electrolytic solution.
The present invention manufacture superelevation unit elongation electrolytic copper foil after testing: thickness≤12.0 μm, hair side roughness Rz≤1.0 μm, normal temperature unit elongation >=15%, room temperature tensile strength >=500MPa, high temperature unit elongation >=20%, Testing Tensile Strength at Elevated Temperature >=400MPa, the flexible copper-clad plate FPC bending resistance folding endurance made more than 200,000 times, as table one.

Claims (6)

1. an electrolytic copper foil complex additive, be characterised in that and be made up of sodium polydithio-dipropyl sulfonate (Sodium 3,3-dithiodipropane sulfonate), Polyglycerine (Polyglycerol), 2-mercaptobenzimidazole (2-Mercaptobenzimidazole), gelatin hydrolysate (Gelatin), rare earth sulfate five kinds of raw materials.
2. according to electrolytic copper foil complex additive a kind of described in claim 1, it is characterized in that the consumption of above-mentioned five kinds of raw materials is: containing 5 ~ 500mg sodium polydithio-dipropyl sulfonate (Sodium 3,3-dithiodipropane sulfonate), 5 ~ 800mg Polyglycerine (Polyglycerol), 0.5 ~ 50mg 2-mercaptobenzimidazole (2-Mercaptobenzimidazole), 5 ~ 800mg gelatin hydrolysate (Gelatin), 0.2 ~ 50mg rare earth sulfate in often liter of electrolytic copper foil electrolytic solution.
3. according to electrolytic copper foil complex additive a kind of described in claim 2, it is characterized in that above-mentioned five kinds of raw material optimum amounts are: containing 8 ~ 100mg sodium polydithio-dipropyl sulfonate (Sodium 3,3-dithiodipropane sulfonate), 5 ~ 200mg Polyglycerine Polyglycerine (Polyglycerol), 0.8 ~ 20mg 2-mercaptobenzimidazole (2-Mercaptobenzimidazole), 10 ~ 200mg gelatin hydrolysate (Gelatin), 0.2 ~ 30mg rare earth sulfate in often liter of electrolytic copper foil electrolytic solution.
4., according to electrolytic copper foil complex additive a kind of described in claim 2, the rare earth sulfate described in its feature is lanthanum sulfat, cerous sulfate or two kinds of mixtures.
5., according to electrolytic copper foil complex additive a kind of described in claim 2, the gelatin hydrolysate described in its feature is the gelatin of the small-molecular-weight of molecular weight between 1000 ~ 4000.
6., according to electrolytic copper foil complex additive a kind of described in claim 2, the Polyglycerine described in its feature is three Polyglycerine (Triglycerol).
CN201410173400.2A 2014-04-28 2014-04-28 Compound additive for electrolytic copper foil Pending CN104651884A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410173400.2A CN104651884A (en) 2014-04-28 2014-04-28 Compound additive for electrolytic copper foil

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410173400.2A CN104651884A (en) 2014-04-28 2014-04-28 Compound additive for electrolytic copper foil

Publications (1)

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CN104651884A true CN104651884A (en) 2015-05-27

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CN (1) CN104651884A (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105132946A (en) * 2015-09-22 2015-12-09 太原工业学院 Compound additive for high-purity cathode copper
CN107177868A (en) * 2017-06-28 2017-09-19 常州汉唐文化传媒有限公司 A kind of copper facing compounding brightener and preparation method thereof
CN108677224A (en) * 2018-07-11 2018-10-19 九江德福科技股份有限公司 A kind of electrolyte being used to prepare high tensile lithium electrolytic copper foil
CN109208041A (en) * 2018-09-18 2019-01-15 山东金宝电子股份有限公司 Additive is used in a kind of preparation of high-performance ultrathin dual light copper foil
CN110042438A (en) * 2019-04-24 2019-07-23 福建清景铜箔有限公司 The preparation method of electrolytic copper foil
CN112080768A (en) * 2020-09-09 2020-12-15 江西省江铜耶兹铜箔有限公司 Production process of smooth high-speed electrolytic copper foil
CN112981473A (en) * 2021-02-05 2021-06-18 广东嘉元科技股份有限公司 Electrolytic copper foil and preparation method thereof
CN113046797A (en) * 2021-03-10 2021-06-29 四川恒创博联科技有限责任公司 Electrolytic copper foil additive

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Publication number Priority date Publication date Assignee Title
JP2006152420A (en) * 2004-12-01 2006-06-15 Mitsui Mining & Smelting Co Ltd Electrolytic copper foil and method for producing the same
JP2007294923A (en) * 2006-03-31 2007-11-08 Nikko Kinzoku Kk Manufacturing method of copper strip or copper foil having excellent strength, electric conductivity, and bendability, and electronic component using the same
CN101481810A (en) * 2009-01-12 2009-07-15 梅县金象铜箔有限公司 Method for manufacturing two-sided optical ultrathin electrolytic copper foil with high elongation
KR20110135219A (en) * 2010-06-10 2011-12-16 일진머티리얼즈 주식회사 Electrolyte for manufacturing electrolytic copper foil of secondary battery and method for manufacturing electrolytic copper foil therewith

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JP2006152420A (en) * 2004-12-01 2006-06-15 Mitsui Mining & Smelting Co Ltd Electrolytic copper foil and method for producing the same
JP2007294923A (en) * 2006-03-31 2007-11-08 Nikko Kinzoku Kk Manufacturing method of copper strip or copper foil having excellent strength, electric conductivity, and bendability, and electronic component using the same
CN101481810A (en) * 2009-01-12 2009-07-15 梅县金象铜箔有限公司 Method for manufacturing two-sided optical ultrathin electrolytic copper foil with high elongation
KR20110135219A (en) * 2010-06-10 2011-12-16 일진머티리얼즈 주식회사 Electrolyte for manufacturing electrolytic copper foil of secondary battery and method for manufacturing electrolytic copper foil therewith

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105132946A (en) * 2015-09-22 2015-12-09 太原工业学院 Compound additive for high-purity cathode copper
CN107177868A (en) * 2017-06-28 2017-09-19 常州汉唐文化传媒有限公司 A kind of copper facing compounding brightener and preparation method thereof
CN108677224A (en) * 2018-07-11 2018-10-19 九江德福科技股份有限公司 A kind of electrolyte being used to prepare high tensile lithium electrolytic copper foil
CN109208041A (en) * 2018-09-18 2019-01-15 山东金宝电子股份有限公司 Additive is used in a kind of preparation of high-performance ultrathin dual light copper foil
CN110042438A (en) * 2019-04-24 2019-07-23 福建清景铜箔有限公司 The preparation method of electrolytic copper foil
CN112080768A (en) * 2020-09-09 2020-12-15 江西省江铜耶兹铜箔有限公司 Production process of smooth high-speed electrolytic copper foil
CN112981473A (en) * 2021-02-05 2021-06-18 广东嘉元科技股份有限公司 Electrolytic copper foil and preparation method thereof
CN112981473B (en) * 2021-02-05 2021-11-23 广东嘉元科技股份有限公司 Electrolytic copper foil and preparation method thereof
CN113046797A (en) * 2021-03-10 2021-06-29 四川恒创博联科技有限责任公司 Electrolytic copper foil additive

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Application publication date: 20150527