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WO2004079053A1 - Procede permettant de produire une feuille de cuivre electrolytique - Google Patents

Procede permettant de produire une feuille de cuivre electrolytique Download PDF

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Publication number
WO2004079053A1
WO2004079053A1 PCT/JP2004/002869 JP2004002869W WO2004079053A1 WO 2004079053 A1 WO2004079053 A1 WO 2004079053A1 JP 2004002869 W JP2004002869 W JP 2004002869W WO 2004079053 A1 WO2004079053 A1 WO 2004079053A1
Authority
WO
WIPO (PCT)
Prior art keywords
copper
copper foil
sulfate solution
electrolytic
electrolytic copper
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.)
Ceased
Application number
PCT/JP2004/002869
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English (en)
Japanese (ja)
Inventor
Hisao Sakai
Shinichi Obata
Makoto Dobashi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsui Kinzoku Co Ltd
Original Assignee
Mitsui Mining and Smelting Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mitsui Mining and Smelting Co Ltd filed Critical Mitsui Mining and Smelting Co Ltd
Publication of WO2004079053A1 publication Critical patent/WO2004079053A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/16—Regeneration of process solutions
    • C25D21/18—Regeneration of process solutions of electrolytes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern

Definitions

  • the present invention relates to a method for producing an electrolytic copper foil.
  • electrolytic copper foil was started in the early 1930s by Anaconda (USA), the world's largest copper producer at the time.
  • the origin of the production of this electrolytic copper foil is as follows.In copper refining electrolysis, copper components eluted into sulfuric acid from blister copper are deposited on the seed copper of the cathode by using blister copper containing impurities in the anode and seed copper in the cathode to form copper electrolytic copper. It is collected as. At this time, the amount of copper eluted from the blister copper is greater than the amount of copper precipitated as electrolytic copper, so the copper concentration in the electrolyte gradually increases.
  • the extracted electrolyte The solution is referred to as “sampled copper sulfate solution”.
  • This extracted copper sulfate solution is a so-called copper sulfate solution, and production of electrolytic copper foil was attempted in order to effectively use the copper sulfate solution.
  • the equipment for producing electrolytic copper foil already had a drawn copper sulfate solution, which is a copper sulfate solution, flowing between a rotating cathode in the form of a drum and a lead-based anode placed opposite to the rotating cathode.
  • copper was deposited on the drum surface of the rotating cathode using an electrolytic reaction, and the deposited copper became a foil state, which was continuously peeled off from the rotating cathode and wound up.
  • the electrodeposited copper foil obtained in this way was referred to as an electoru-kappa sheet at that time, and was mainly used for building materials and decorative purposes.
  • the electrolytic copper foil at that time was cheaper in production cost than the rolled copper foil and could be provided at a lower price, but the extracted copper sulfate solution contained many impurities such as zinc, calcium, nickel, and arsenic.
  • the electrical resistance increased compared to copper foil, and the electrical resistance specifications required for electoronics products could not be satisfied.
  • Circuit Oil In order to produce high-purity electrolytic copper foil that can be used in the electronics field, Circuit Oil has given up using conventional copper sulfate solution instead of dissolving copper wire with sulfuric acid and adding copper sulfate solution with less impurities. It was decided to use. This concept is based on the idea that Clevit (later Gould), a manufacturer of electrolytic copper foils for electronics that was established to date, is now an electrolytic copper foil manufacturer in Japan, including the Company, and other Taiwanese companies. It is used by all electrolytic copper foil manufacturers in Korea, China and other countries. The contents related to the technical background described above and the production of conventional copper foil for printed wiring boards are disclosed in various patent documents and technical documents shown below. For example, U.S. Pat. No.
  • Figure 1 shows a comparison of the metal component content in the liquid before and after activated carbon filtration.
  • FIG. 2 shows a comparison of the content of the impurity metal component in the electrolytic copper foil produced using each copper sulfate solution before and after the activated carbon filtration.
  • Fig. 3 shows the roughened surface shape of the electrolytic copper foil produced using each copper sulfate solution before and after activated carbon filtration.
  • the inventors of the present invention as a result of diligent research, returned to the origin of electrolytic copper foil production and found that even with the above-mentioned extracted copper sulfate solution, the same electronics as high-purity electrolytic copper foil supplied to the conventional market were used. They have come up with a method that can produce electrolytic copper foil with a purity that can be used in applications. The idea of producing electrolytic copper foil with a purity that can be used for electronics using the extracted copper sulfate solution has been neglected by those skilled in the art for more than 50 years.
  • the basic technical idea of the present invention is as described in the claim: ⁇
  • the copper sulfate solution is withdrawn from a refining electrolytic cell for obtaining electrolytic copper.
  • the extracted copper sulfate solution is treated with activated carbon.
  • a method for producing an electrolytic copper foil comprising: It is to adopt.
  • the extracted copper sulfate solution extracted from the refining electrolytic cell for obtaining the electrolytic copper contains various impurities in the extracted copper sulfate solution.
  • the most common impurities are nickel, arsenic, iron, calcium, aluminum, zinc, magnesium and the like, and also include glue and thiourea which are intentionally added.
  • the greatest feature of the present invention lies in that this solution is treated with activated carbon.
  • activated carbon treatment of a plating solution or the like is generally used for cleaning a solution, and it is apparent that the same cleaning effect can be obtained by filtering the extracted copper sulfate solution with activated carbon.
  • the cleaning effect referred to here is to remove so-called organic substances such as glue in a solution and decomposition residues of the organic substances, and to adsorb and remove a part of metal components that are ionized. It has been considered promising.
  • Figure 1 shows the results.
  • the content of each metal component in the liquid hardly changed before and after activated carbon filtration.
  • a titanium plate was placed on the cathode and an insoluble DSE electrode was placed on the anode so that the distance between the electrodes was 10 mm, and the solution temperature was 48 ° C and the current density was An electrolytic copper foil of 35 m was produced at 35 AZ dm 2 .
  • the rough surface of the copper foil produced using the extracted copper sulfate solution treated with activated carbon (Fig. 3 (A)) and the extracted copper sulfate solution not treated with activated carbon were used. Comparing with the rough surface of copper foil manufactured using the liquid (Fig. 3 (B)), the latter rough surface of the copper foil has many abnormal deposition spots and is not uniform. Therefore, by using the extracted copper sulfate solution that has been treated with activated carbon, the stability of copper precipitation can be maintained.
  • the activated carbon treatment used in the present invention removes only organic additives such as glue and thiourea in the solution, and does not remove contained metal ions.
  • organic additives such as glue and thiourea in the solution
  • metal ions I think that when the organic additive is removed from the sampled copper sulfate solution, copper electrolysis using the solution suppresses the precipitation of impurity metal components other than copper, and satisfies the copper purity required for electrolytic copper foil for printed wiring boards. It is thought that the product which was obtained is obtained.
  • the electrolytic copper foil may be produced by adding an additive such as glue to a copper sulfate solution for controlling physical properties. Therefore, the inventors of the present invention have filtered the extracted copper sulfate solution extracted from the refining electrolytic cell for obtaining the electrolytic copper with activated carbon, and then added an additive for improving the physical properties of the copper foil. As described above, they have found that it is possible to produce an electrolytic copper foil without containing the impurity component contained in the extracted copper sulfate solution.
  • the additives mentioned here mainly refer to organic additives such as glue, gelatin, and surfactants.
  • organic additives such as glue, gelatin, and surfactants.
  • electrolytic copper foil the purity of its components is a problem, and it is hardly conceivable to use metal additives except when trying to produce copper alloy foil.
  • the current density used during electrolysis will be described.
  • a copper component is deposited on the surface of the cathode in a manner to make it smooth, and this is stripped off. Therefore, it is clear that the current density must be within the range that allows smooth copper plating. That is, the relationship between the copper concentration and the current density largely determines the condition of copper smoothness. If the copper concentration is low, the current density will normally be low unless the current density is set low.
  • the copper concentration in the copper sulfate solution used for the production of copper foil for printed wiring boards has been increased to 80 g Z1 as a solution with a high copper concentration and high current density electrolysis to improve production efficiency. Have been.
  • the copper concentration of the extracted copper sulfate solution extracted from the electrolytic cell for obtaining electrolytic copper The density is usually 55 g / 1 or less, and it is not possible to perform electrolysis at a high current density exceeding 5 OAZdm 2 used in the production of the current copper foil for printed wiring boards. Therefore, by setting the current density lower, it is possible to produce electrolytic copper foil that satisfies the purity of copper foil for printed wiring boards.
  • the low current density since there is no particular problem regarding the low current density, it is not necessary to particularly consider the lower limit of the current density.
  • considering the industrial base it is advantageous to secure high productivity at the highest possible current density, and operating conditions near the upper limit current density will be determined.
  • Electrical resistance shows the physical properties of HTE class 0. 160 ⁇ - g / m 2 or more of the properties I PC standard, ordinary Japanese Patent wire ratio Comparative Examples 1 described below was obtained by dissolving in sulfuric acid There is no difference between the physical properties of the electrolytic copper foil (HTE) obtained using the copper sulfate solution. Therefore, it is clear that the properties as an electrolytic copper foil for a printed wiring board can be sufficiently satisfied.
  • each of the above physical properties indicates the physical properties of the HTE foil of the IPC standard obtained by the usual method for producing an electrolytic copper foil. These are to be compared with the first embodiment described above. As can be seen from this, the physical properties of the electrolytic copper foil obtained in the first example are not inferior to those of the copper foil of the first comparative example.
  • the technique that a person skilled in the art has given up for many years is improved from a new point of view, so that it can be said that the origin of the copper foil is ⁇ extracted from the electrolytic cell for obtaining electrolytic copper ''
  • the origin of the copper foil is ⁇ extracted from the electrolytic cell for obtaining electrolytic copper ''
  • the process of dissolving the conductive wire with sulfuric acid is not required, and the production line can be significantly shortened.
  • the extracted copper sulfate solution generated from the electrolytic refining of copper untitled use of resources can be suppressed, and extremely inexpensive copper foil can be supplied.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)

Abstract

L'invention concerne un procédé permettant de produire une feuille de cuivre électrolytique au moyen d'une solution de sulfate de cuivre échantillonnée issue d'un procédé d'affinage du cuivre afin de lancer sur le marché une feuille de cuivre électrolytique à bas prix pour une carte imprimée. Le procédé selon l'invention, qui permet de produire une feuille de cuivre électrolytique, par l'électrolyse d'une solution de sulfate de cuivre, est caractérisé en ce que la solution de sulfate de cuivre échantillonnée à partir d'une cellule électrolytique d'affinage afin d'obtenir du cuivre électrique est utilisée après avoir été soumise à un traitement par charbon actif. Ledit procédé est également caractérisé en ce que la solution de sulfate de cuivre est échantillonnée à partir d'une cellule électrolytique d'affinage afin d'obtenir du cuivre électrique et soumise à un traitement par charbon actif, puis additionnée d'un additif afin de renforcer les propriétés physiques de la feuille de cuivre.
PCT/JP2004/002869 2003-03-07 2004-03-05 Procede permettant de produire une feuille de cuivre electrolytique Ceased WO2004079053A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2003061174A JP2004269950A (ja) 2003-03-07 2003-03-07 電解銅箔の製造方法
JP2003-061174 2003-03-07

Publications (1)

Publication Number Publication Date
WO2004079053A1 true WO2004079053A1 (fr) 2004-09-16

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PCT/JP2004/002869 Ceased WO2004079053A1 (fr) 2003-03-07 2004-03-05 Procede permettant de produire une feuille de cuivre electrolytique

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JP (1) JP2004269950A (fr)
WO (1) WO2004079053A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115094486A (zh) * 2022-05-26 2022-09-23 刘润华 一种电解铜箔生箔系统

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3742144B2 (ja) * 1996-05-08 2006-02-01 ソニー株式会社 非水電解液二次電池及び非水電解液二次電池用の平面状集電体
JP6860339B2 (ja) 2016-12-16 2021-04-14 株式会社Uacj 電解アルミニウム箔の製造方法および製造装置
KR102395519B1 (ko) * 2021-12-13 2022-05-09 주식회사 남동금속 금속 표면의 도금방법

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0207244A2 (fr) * 1985-07-05 1987-01-07 Mitsui Mining & Smelting Co., Ltd. Feuille de cuivre obtenue par électrodéposition
JPH0488185A (ja) * 1990-07-30 1992-03-23 Nippon Denkai Kk 銅メッキ液とこれを用いる電解銅箔の製造方法
WO1994024338A1 (fr) * 1993-04-19 1994-10-27 Magma Copper Company Procede pour fabriquer des feuilles de cuivre
EP1059367A2 (fr) * 1999-06-08 2000-12-13 Mitsui Mining & Smelting Co., Ltd. Méthode de fabrication d'une feuille de cuivre déposée par électrolyse, feuille de cuivre déposée par électrolyse, laminé revêtu de cuivre et plaque à circuit imprimé
US20010042686A1 (en) * 2000-05-18 2001-11-22 Mitsui Mining & Smelting Co., Ltd. Electrodeposition apparatus for producing electrodeposited copper foil and electrodeposited copper foil produced by use of the apparatus

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0207244A2 (fr) * 1985-07-05 1987-01-07 Mitsui Mining & Smelting Co., Ltd. Feuille de cuivre obtenue par électrodéposition
JPH0488185A (ja) * 1990-07-30 1992-03-23 Nippon Denkai Kk 銅メッキ液とこれを用いる電解銅箔の製造方法
WO1994024338A1 (fr) * 1993-04-19 1994-10-27 Magma Copper Company Procede pour fabriquer des feuilles de cuivre
EP1059367A2 (fr) * 1999-06-08 2000-12-13 Mitsui Mining & Smelting Co., Ltd. Méthode de fabrication d'une feuille de cuivre déposée par électrolyse, feuille de cuivre déposée par électrolyse, laminé revêtu de cuivre et plaque à circuit imprimé
US20010042686A1 (en) * 2000-05-18 2001-11-22 Mitsui Mining & Smelting Co., Ltd. Electrodeposition apparatus for producing electrodeposited copper foil and electrodeposited copper foil produced by use of the apparatus

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115094486A (zh) * 2022-05-26 2022-09-23 刘润华 一种电解铜箔生箔系统

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