CN106521564A - Composite additive for producing low-profile electrolytic copper foil and sedimentation process of composite additive - Google Patents
Composite additive for producing low-profile electrolytic copper foil and sedimentation process of composite additive Download PDFInfo
- Publication number
- CN106521564A CN106521564A CN201610958473.1A CN201610958473A CN106521564A CN 106521564 A CN106521564 A CN 106521564A CN 201610958473 A CN201610958473 A CN 201610958473A CN 106521564 A CN106521564 A CN 106521564A
- Authority
- CN
- China
- Prior art keywords
- compound additive
- electrolyte
- 30ppm
- copper foil
- content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention belongs to the technical field of electrolytic copper foil and particularly relates to a composite additive for producing low-profile electrolytic copper foil and a sedimentation process of the composite additive. The composite additive comprises four or more compounds of 3-sulfydryl propane sodium sulfonate, ethylene thiourea, small-molecule gelatin, sodium dodecyl sulfonate and hydroxyethyl cellulose. The copper foil made of the additive is high in tensile strength and elongation; grains at the rough-face side of the copper foil are refined; surface roughness is lowered, but certain peeling strength is still maintained; and the composite additive has great market prospect and economic value.
Description
Technical field
The invention belongs to electrolytic copper foil technical field, and in particular to a kind of to add for producing the compound of low-profile electrolytic copper foil
Plus agent and its depositing operation.
Background technology
With electronics, communication, space flight, electrical network, automobile and other industries fast development, powerful PCB also obtained quickly
Development.The high-power circuit plate of the equipment such as electronics, communication is larger because of electric current, easily generates heat.Nerve of the Copper Foil as circuit board, if
Copper thickness is less and if surface roughness is higher, it is easy to causes rupture of line because of heating, causes entire plate to break down, because
This thickness and surface roughness to Copper Foil needs certain requirement.In the production technology that 70 μm of copper thickness ＜, can pass through
The roughness of Copper Foil hair side is controlled with conventional leveling agent, but when the production technology of copper thickness >=70 μm, is added conventional
Leveling agent can not possibly controlling the roughness of Copper Foil hair side.Copper Foil is thicker, and the crystal grain of its hair side is bigger, coarse
Degree is bigger.
The content of the invention
For this purpose, the technical problem to be solved is the technical bottleneck for overcoming prior art, so as to propose one kind
For producing the compound additive of low-profile electrolytic copper foil.
For solving above-mentioned technical problem, the invention discloses a kind of compound addition for producing low-profile electrolytic copper foil
Agent, the compound additive include 3- mercaptopropanesulfonic acid sodium, ethylene thiourea, small molecule gelatin, dodecyl sodium sulfate, hydroxyl second
At least four compounds in base cellulose.
Preferably, the compound additive includes following component：3- mercaptopropanesulfonic acid 10～100ppm of sodium content, ethylene
Thiourea 5～50ppm of content, small molecule 10～100ppm of gelatin, 20～150ppm of dodecyl sodium sulfate, hydroxyethyl cellulose 20
～200ppm.
Preferably, the compound additive includes following component：3- mercaptopropanesulfonic acid sodium 30ppm, ethylene thiourea
20ppm, small molecule gelatin 30ppm, dodecyl sodium sulfate 50ppm, hydroxyethyl cellulose 50ppm.
Preferably, the compound additive includes following component：3- mercaptopropanesulfonic acid sodium 50ppm, ethylene thiourea
30ppm, small molecule gelatin 30ppm, dodecyl sodium sulfate 100ppm, hydroxyethyl cellulose 100ppm.
, for the technique during depositing Copper Foil, the technological process is as follows for compound additive described in a kind of any one：
It is 60～100g/L to take copper content, and sulfuric acid content is 80～150g/L, and chloride ion is 30ppm, and temperature is 35～60
DEG C electrolyte, then add the compound additive in the electrolyte, make electrolyte flow be 40～70m3/ h, electricity
4500～9000A/m of current density2Parameter under carry out electro-deposition.
Preferably, the processing step is as follows：
It is 60～80g/L to take copper content, and sulfuric acid content is 80～120g/L, and chloride ion is 30ppm, and temperature is 35～45 DEG C
Electrolyte, then add the compound additive in the electrolyte, make electrolyte flow be 40～50m3/ h, electric current
4500～6000A/m of density2Parameter under carry out electro-deposition.
Preferably, the processing step is as follows：
It is 80～100g/L to take copper content, and sulfuric acid content is 100～150g/L, and chloride ion is 30ppm, and temperature is 40～60
DEG C electrolyte, and add the compound additive in the electrolyte, make flow of electrolyte be 50～70m3/ h, electric current are close
6000～9000A/m of degree2Under the conditions of carry out electro-deposition.
The above-mentioned technical proposal of the present invention has advantages below compared to existing technology：There is provided the crystal grain of a kind of mao of paper tinsel more
For uniform, more tiny, moderately reduction hair side roughness, and the novel hair paper tinsel with high tension, elongation percentage performance, hair paper tinsel
Manufacture used new additive agent, this kind of electrolytic copper foil properties are adapted to the high-power circuits such as automobile industry, electrical network, communication
Plate is used.The Copper Foil electrocrystallization granule manufactured with additive of the present invention is more uniform, refinement, and Copper Foil has higher tension
With elongation percentage performance, and certain peel strength is maintained.
Specific embodiment
Embodiment 1：
Present embodiment discloses a kind of compound additive for producing low-profile electrolytic copper foil, the component of the additive
It is as follows:
The compound additive is consisted of：3- mercaptopropanesulfonic acid sodium 30ppm, ethylene thiourea 20ppm, small molecule gelatin
30ppm, dodecyl sodium sulfate 50ppm, hydroxyethyl cellulose 50ppm, the organic blending additive flow are 400mL/min.
, for the technique during depositing Copper Foil, the technological process is as follows for a kind of compound additive：
It is 70g/L to take copper content, and sulfuric acid content is 100g/L, and chloride ion is 30ppm, and temperature is 40 DEG C of electrolyte, so
Add the compound additive in backward electrolyte, make electrolyte be 45m in flow3/ h, electric current density 5000A/m2Parameter under
Carry out electro-deposition.
Embodiment effect：140 microns of electrolytic copper foils manufactured in the present embodiment, its hair side roughness Rz≤5m, normality tension
Intensity >=400Mpa, normality elongation percentage >=15%, 180 DEG C of tensile strength >=250Mpa, 180 DEG C of elongation percentage >=10%, anti-stripping >=
3.0N/cm。
Embodiment 2：Present embodiment discloses a kind of compound additive for producing low-profile electrolytic copper foil, the addition
The component of agent is as follows:
The compound additive is consisted of：3- mercaptopropanesulfonic acid sodium 50ppm, ethylene thiourea 30ppm, small molecule gelatin
30ppm, dodecyl sodium sulfate 100ppm, hydroxyethyl cellulose 100ppm, the organic blending additive flow are 500mL/
min。
, for the technique during depositing Copper Foil, the technological process is as follows for a kind of compound additive：
Using copper content 90g/L in electrolyte, sulfuric acid content 120g/L, chloride ion 30ppm, the parameter of temperature 50 C match somebody with somebody
Close, and add organic blending additive in electrolyte, make flow of electrolyte be 60m3/ h, electric current density 7500A/m2Under the conditions of
Carry out electro-deposition.
Embodiment effect：210 microns of electrolytic copper foils manufactured in the present embodiment, its hair side roughness Rz≤8m, normality tension
Intensity >=400Mpa, normality elongation percentage >=15%, 180 DEG C of tensile strength >=250Mpa, 180 DEG C of elongation percentage >=10%, anti-stripping >=
4.0N/cm。
Obviously, above-described embodiment is only intended to clearly illustrate example, and the not restriction to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description other multi-forms change or
Change.There is no need to be exhaustive to all of embodiment.And thus it is extended obvious change or
Among changing still in the protection domain of the invention.
Claims (7)
1. a kind of compound additive for producing low-profile electrolytic copper foil, it is characterised in that the compound additive includes 3-
At least four changes in mercaptopropanesulfonic acid sodium, ethylene thiourea, small molecule gelatin, dodecyl sodium sulfate, hydroxyethyl cellulose
Compound.
2. compound additive as claimed in claim 1, it is characterised in that the compound additive includes following component：3- mercaptos
Base propane sulfonic acid 10～100ppm of sodium content, ethylene thiourea 5～50ppm of content, small molecule 10～100ppm of gelatin, dodecyl
20～150ppm of sodium sulfonate, 20～200ppm of hydroxyethyl cellulose.
3. compound additive as claimed in claim 2, it is characterised in that the compound additive includes following component：3- mercaptos
Base propane sulfonic acid sodium 30ppm, ethylene thiourea 20ppm, small molecule gelatin 30ppm, dodecyl sodium sulfate 50ppm, ethoxy are fine
Dimension element 50ppm.
4. compound additive as claimed in claim 2, it is characterised in that the compound additive includes following component：3- mercaptos
Base propane sulfonic acid sodium 50ppm, ethylene thiourea 30ppm, small molecule gelatin 30ppm, dodecyl sodium sulfate 100ppm, ethoxy are fine
Dimension element 100ppm.
5. a kind of compound additive as described in any one of claim 1-4 is for the technique during depositing Copper Foil, its feature
It is that the technological process is as follows：
It is 60～100g/L to take copper content, and sulfuric acid content is 80～150g/L, and chloride ion is 30ppm, and temperature is 35～60 DEG C
Electrolyte, then adds the compound additive in the electrolyte, makes electrolyte be 40～70m in flow3/ h, electric current are close
4500～9000A/m of degree2Parameter under carry out electro-deposition.
6. technique as claimed in claim 5, it is characterised in that the processing step is as follows：
It is 60～80g/L to take copper content, and sulfuric acid content is 80～120g/L, and chloride ion is 30ppm, and temperature is 35～45 DEG C of electricity
Solution liquid, then adds the compound additive in the electrolyte, makes electrolyte be 40～50m in flow3/ h, electric current density
4500～6000A/m2Parameter under carry out electro-deposition.
7. technique as claimed in claim 5, it is characterised in that the processing step is as follows：
It is 80～100g/L to take copper content, and sulfuric acid content is 100～150g/L, and chloride ion is 30ppm, and temperature is 40～60 DEG C
Electrolyte, and add the compound additive in the electrolyte, make flow of electrolyte be 50～70m3/ h, electric current density
6000～9000A/m2Under the conditions of carry out electro-deposition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610958473.1A CN106521564A (en) | 2016-10-27 | 2016-10-27 | Composite additive for producing low-profile electrolytic copper foil and sedimentation process of composite additive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610958473.1A CN106521564A (en) | 2016-10-27 | 2016-10-27 | Composite additive for producing low-profile electrolytic copper foil and sedimentation process of composite additive |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106521564A true CN106521564A (en) | 2017-03-22 |
Family
ID=58325738
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610958473.1A Pending CN106521564A (en) | 2016-10-27 | 2016-10-27 | Composite additive for producing low-profile electrolytic copper foil and sedimentation process of composite additive |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106521564A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109183081A (en) * | 2018-08-24 | 2019-01-11 | 邵武永太高新材料有限公司 | A kind of preparation method of additive for electrolytic copper foil and dual light electrolytic copper foil |
| CN109943868A (en) * | 2019-04-19 | 2019-06-28 | 山东金盛源电子材料有限公司 | A kind of compound additive for the electrolytic copper foil being used to prepare high-tensile |
| CN111020644A (en) * | 2020-01-03 | 2020-04-17 | 甘肃德福新材料有限公司 | Method for manufacturing electrolytic copper foil for lithium ion secondary battery |
| CN111286745A (en) * | 2018-12-06 | 2020-06-16 | 湖北工程学院 | Additive for high-tensile electrolytic copper foil, preparation method of electrolytic copper foil and lithium ion battery |
| CN111364072A (en) * | 2020-04-23 | 2020-07-03 | 广东嘉元科技股份有限公司 | High-ductility electrolytic copper foil and preparation method thereof |
| EP3798336A4 (en) * | 2019-07-22 | 2021-08-04 | Tex Technology Inc. | Method for producing electrolytic copper foil |
| CN113638016A (en) * | 2021-08-06 | 2021-11-12 | 佛冈建滔实业有限公司 | Additive for improving stripping resistance of electrolytic copper foil and preparation method thereof |
| CN114182310A (en) * | 2021-12-21 | 2022-03-15 | 深圳先进电子材料国际创新研究院 | Electrolyte for manufacturing electrolyte copper foil and application thereof |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001000905A1 (en) * | 1999-06-28 | 2001-01-04 | Eltech Systems Corporation | Method of producing copper foil |
| CN1500915A (en) * | 2002-11-14 | 2004-06-02 | 日进素材产业（株） | Electrolyte solution for manufacturing electrolytic copper foil and electrolytic copper foil manufacturing method using the same |
| US20040104118A1 (en) * | 2002-11-29 | 2004-06-03 | Lg Cable Ltd. | Method for manufacturing very low roughness electrodeposited copper foil and electrodeposited copper foil manufactured thereby |
| CN1854347A (en) * | 2005-04-20 | 2006-11-01 | Lg电线有限公司 | Low roughness copper foil with high strength and manufacture thereof |
| JP2006299320A (en) * | 2005-04-19 | 2006-11-02 | Ls Cable Ltd | High strength low roughness copper foil and method of manufacturing 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 |
| CN102002737A (en) * | 2010-11-24 | 2011-04-06 | 山东金宝电子股份有限公司 | Composite additive for producing electrolytic copper foil with high bending resistance and low outline |
| CN102277597A (en) * | 2011-08-12 | 2011-12-14 | 合肥铜冠国轩铜材有限公司 | Preparation of double-sided photoelectrolytic copper foil for special lithium battery |
| CN102363891A (en) * | 2011-11-18 | 2012-02-29 | 山东金宝电子股份有限公司 | Double photoelectrolysis copper foil replacing rolled copper foil and used for production of flexible copper clad laminate, and production process of double photoelectrolysis copper foil |
| CN103173812A (en) * | 2013-03-21 | 2013-06-26 | 山东金宝电子股份有限公司 | Mixed additive for removing internal stress of electrolytic copper foil and method for producing low-stress copper foil |
| CN104928740A (en) * | 2015-07-07 | 2015-09-23 | 安徽铜冠铜箔有限公司 | Surface treatment method for reducing copper powder on rough surface of copper foil |
| CN105862089A (en) * | 2016-06-17 | 2016-08-17 | 泉州师范学院 | Electrolyte solution used for preventing positive pole from scaling and producing electrolytic copper foil and preparing method thereof |
-
2016
- 2016-10-27 CN CN201610958473.1A patent/CN106521564A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001000905A1 (en) * | 1999-06-28 | 2001-01-04 | Eltech Systems Corporation | Method of producing copper foil |
| CN1500915A (en) * | 2002-11-14 | 2004-06-02 | 日进素材产业（株） | Electrolyte solution for manufacturing electrolytic copper foil and electrolytic copper foil manufacturing method using the same |
| US20040104118A1 (en) * | 2002-11-29 | 2004-06-03 | Lg Cable Ltd. | Method for manufacturing very low roughness electrodeposited copper foil and electrodeposited copper foil manufactured thereby |
| JP2006299320A (en) * | 2005-04-19 | 2006-11-02 | Ls Cable Ltd | High strength low roughness copper foil and method of manufacturing the same |
| CN1854347A (en) * | 2005-04-20 | 2006-11-01 | Lg电线有限公司 | Low roughness copper foil with high strength and manufacture thereof |
| 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 |
| CN102002737A (en) * | 2010-11-24 | 2011-04-06 | 山东金宝电子股份有限公司 | Composite additive for producing electrolytic copper foil with high bending resistance and low outline |
| CN102277597A (en) * | 2011-08-12 | 2011-12-14 | 合肥铜冠国轩铜材有限公司 | Preparation of double-sided photoelectrolytic copper foil for special lithium battery |
| CN102363891A (en) * | 2011-11-18 | 2012-02-29 | 山东金宝电子股份有限公司 | Double photoelectrolysis copper foil replacing rolled copper foil and used for production of flexible copper clad laminate, and production process of double photoelectrolysis copper foil |
| CN103173812A (en) * | 2013-03-21 | 2013-06-26 | 山东金宝电子股份有限公司 | Mixed additive for removing internal stress of electrolytic copper foil and method for producing low-stress copper foil |
| CN104928740A (en) * | 2015-07-07 | 2015-09-23 | 安徽铜冠铜箔有限公司 | Surface treatment method for reducing copper powder on rough surface of copper foil |
| CN105862089A (en) * | 2016-06-17 | 2016-08-17 | 泉州师范学院 | Electrolyte solution used for preventing positive pole from scaling and producing electrolytic copper foil and preparing method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 张胜涛: "《电镀实用技术》", 30 November 2011 * |
| 蒙延双等: "添加剂对阴极电铜表面质量的影响", 《云南冶金》 * |
| 金荣涛等: "《电解铜箔生产》", 31 December 2010 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109183081A (en) * | 2018-08-24 | 2019-01-11 | 邵武永太高新材料有限公司 | A kind of preparation method of additive for electrolytic copper foil and dual light electrolytic copper foil |
| CN111286745A (en) * | 2018-12-06 | 2020-06-16 | 湖北工程学院 | Additive for high-tensile electrolytic copper foil, preparation method of electrolytic copper foil and lithium ion battery |
| CN109943868A (en) * | 2019-04-19 | 2019-06-28 | 山东金盛源电子材料有限公司 | A kind of compound additive for the electrolytic copper foil being used to prepare high-tensile |
| EP3798336A4 (en) * | 2019-07-22 | 2021-08-04 | Tex Technology Inc. | Method for producing electrolytic copper foil |
| CN111020644A (en) * | 2020-01-03 | 2020-04-17 | 甘肃德福新材料有限公司 | Method for manufacturing electrolytic copper foil for lithium ion secondary battery |
| CN111020644B (en) * | 2020-01-03 | 2021-06-15 | 甘肃德福新材料有限公司 | Method for manufacturing electrolytic copper foil for lithium ion secondary battery |
| CN111364072A (en) * | 2020-04-23 | 2020-07-03 | 广东嘉元科技股份有限公司 | High-ductility electrolytic copper foil and preparation method thereof |
| CN111364072B (en) * | 2020-04-23 | 2021-01-26 | 广东嘉元科技股份有限公司 | High-ductility electrolytic copper foil and preparation method thereof |
| CN113638016A (en) * | 2021-08-06 | 2021-11-12 | 佛冈建滔实业有限公司 | Additive for improving stripping resistance of electrolytic copper foil and preparation method thereof |
| CN114182310A (en) * | 2021-12-21 | 2022-03-15 | 深圳先进电子材料国际创新研究院 | Electrolyte for manufacturing electrolyte copper foil and application thereof |
| WO2023116705A1 (en) * | 2021-12-21 | 2023-06-29 | 深圳先进电子材料国际创新研究院 | Electrolytic solution for copper foil, and electrolytic copper foil |
| CN114182310B (en) * | 2021-12-21 | 2023-08-22 | 深圳先进电子材料国际创新研究院 | Electrolyte for manufacturing electrolytic copper foil and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106521564A (en) | Composite additive for producing low-profile electrolytic copper foil and sedimentation process of composite additive | |
| WO2017219797A1 (en) | Electric copper plating liquid and electric copper plating process thereof | |
| JP3058445B2 (en) | Characterized electrodeposited foils for printed circuit boards and methods for producing the same and electrolytic cell solutions | |
| JP4344714B2 (en) | Low-roughness copper foil having high strength and method for producing the same | |
| CN105441993A (en) | Electroplating solution and electroplating method for electroplating through holes and blind holes of circuit boards | |
| CN110760898A (en) | Preparation method of high-tensile electrolytic copper foil for lithium battery | |
| JP5706045B2 (en) | Electrolytic copper foil and manufacturing method thereof | |
| CN107236973A (en) | Preparation method, product and its application of flexibility coat copper plate additive for electrolytic copper foil | |
| JP2022008856A (en) | Electrolytic copper foil for secondary battery and method for producing the same | |
| CN104651884A (en) | Compound additive for electrolytic copper foil | |
| KR101535853B1 (en) | Manufacturing method of high strength copper foil using micro-hardening and high strength copper foil manufactured by the same | |
| CN103060859B (en) | An additive for improving the peak shape of the rough surface of rough foil, and a production process for electrolytic copper foil | |
| JP2022027830A (en) | Electrolytic copper foil for secondary battery having excellent physical properties at low temperature and method for producing the same | |
| CN107099823A (en) | Compound additive and its depositing operation for electrolytic copper foil | |
| US5171417A (en) | Copper foils for printed circuit board applications and procedures and electrolyte bath solutions for electrodepositing the same | |
| JP2022120813A (en) | Ultrathin copper foil, and method of producing the same | |
| CN108914170B (en) | Composite electroplating solution, preparation method of composite electroplating solution and electroplating method | |
| WO2019208368A1 (en) | Surface-treated copper foil, copper-cladded laminate plate, and printed wiring board | |
| Lai et al. | Rapid metallization by copper electroplating on insulating substrate using silver nanowires conductive composite as seed layer | |
| TWI736325B (en) | Advanced reverse-treated electrodeposited copper foil having long and island-shaped structures and copper clad laminate using the same | |
| CN106939432B (en) | A kind of compound additive and its process for producing of think gauge copper foil | |
| CN116180170A (en) | Copper electroplating solution for through holes of flexible printed circuit board | |
| CN102877098B (en) | Multi-waveband output pulse plating method | |
| KR102495997B1 (en) | Surface-treated copper foil with low surface roughness and low flexural strain, copper foil laminate comprising the same, and printed wiring board comprising the same | |
| JP2015155563A (en) | Apparatus and method for continuous electrolytic plating, metalized resin film and production method of the film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170322 |