JP4349690B2 - Method for producing electrolytic copper foil - Google Patents
Method for producing electrolytic copper foil Download PDFInfo
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- JP4349690B2 JP4349690B2 JP18352899A JP18352899A JP4349690B2 JP 4349690 B2 JP4349690 B2 JP 4349690B2 JP 18352899 A JP18352899 A JP 18352899A JP 18352899 A JP18352899 A JP 18352899A JP 4349690 B2 JP4349690 B2 JP 4349690B2
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- copper
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Electrolytic Production Of Metals (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、電子部品の回路やリチウム二次電池の負極に好適に用いられる電解銅箔の製造方法に関する。
【０００２】
【従来の技術】
電解銅箔の製造工程は、銅原料を電解液に溶解させる溶解工程と銅原料を溶解した電解液を用いて電気分解により銅を析出させる銅析出工程とからなる複合工程であり、析出する銅に見合うだけの銅原料を電解液に溶解させる必要がある。銅原料としては安価であり、表面積の大きな銅くずが使用されている。銅くずとしては、スクラップ銅線を細断したものを用いるのが一般的であるが、その他、溶融押出品を細断したものなども用いられている。これらの銅くずは、押出加工時の伸線油や被覆材料由来の不純物、スクラップ化及び細断時に付着した不純物により汚染されている。
【０００３】
近年、高密度電子回路を実現するため、微細回路形成に適した薄い電解銅箔が望まれている。銅原料を硫酸水溶液に溶解させた硫酸銅水溶液にゼラチンなど有機物や塩化物などを添加した電解液を用い、電気分解により薄い電解銅箔を製造する方法が知られているが、この方法により得られた電解銅箔は引張強度が小さく、剛性に乏しいため取扱が難しいという難点があった。また、この製造方法で得られた電解銅箔は銅箔析出面側の表面粗さが比較的大きく、厚さが不均一であるため、薄銅箔ではしわなどの原因となる傾向があった。さらに、表面粗さが大きいことはオーバーエッチングの原因となり、微細回路の形成に支障をきたすという問題があった。
【０００４】
【発明が解決しようとする課題】
本発明の目的は、従来から使用されている安価な銅くずから得られる電解液を用いて、薄くて引張強度が大きく、剛性が高いことから取扱性に優れ、両面が平滑で同等の表面粗さを有し、伸び率に優れた電解銅箔を製造することができる電解銅箔の製造方法を提供することにある。
【０００５】
【課題を解決するための手段】
本発明者らは、前記目的を達成するために鋭意研究を重ねた結果、電解液に溶解する銅原料として銅くずを用い、銅くずを焼成処理した後、酸洗処理して得られた処理銅くずを用いることにより、薄くて引張強度が大きく、剛性が高いことから取扱性に優れ、両面が平滑で同等の表面粗さを有し、伸び率に優れた電解銅箔を製造することができることを見出し、この知見に基づいて本発明を完成するに至った。
【０００６】
すなわち、本発明は、銅くずを焼成処理した後、酸洗処理して得られた処理銅くずを硫酸水溶液に溶解して電解液を作製し、得られた電解液を用いて電気分解により銅析出を行うことを特徴とする電解銅箔の製造方法を提供するものである。
【０００７】
本発明により得られた電解銅箔は、薄くて引張強度が大きく、微細回路の形成に適し、伸び率に優れていることから、例えば、内層回路として用いた場合に熱膨張に基づく断線不良を防止することができ、電子回路用銅箔として極めて優れた特性を有している。さらに、両面が平滑で同等の表面粗さを有し、剛性が高いことから二次電池用活物質合剤の両面塗工が容易であり、また、伸び率に優れることから、リチウムイオン二次電池の負極板用銅箔としても極めて有用な銅箔である。
【０００８】
【発明の実施の形態】
本発明において用いられる銅くずとしては、好ましくは、異物、異材を混入しない銅分が９９％以上のものが用いられる。より好ましくは、ＪＩＳ Ｈ ２１０９に規定される１号ナゲット銅が用いられる。これは、安価に入手できる銅くずで、銅線又は銅より線をナゲット加工した（短切線）純良なもので、銅分が９９．９％以上のものである。また、銅覆鋼線など異材及び異物が混入していないものである。また、ＪＩＳ Ｈ ２１０９に規定される１号銅線くずも使用可能である。本発明においては、この銅くずに焼成処理と酸洗処理を行って得られた処理銅くずを硫酸に溶解して電解液を作製する。
【０００９】
焼成処理を行うことにより、銅くずの表面付着物が酸化・燃焼するとともに、酸化された表面が酸で容易に浸食されるため、酸洗効率が向上し、油分などの付着物が容易に除去できるようになる。焼成処理の条件は銅くずの表面に薄い酸化銅層が形成される条件が適切であり、好ましくは銅くずを５００℃〜８００℃の酸化雰囲気に、好ましくは１分〜３０分間さらすことにより行われる。この操作を繰り返し行ってもよい。具体的には被処理物に５００〜８００℃の熱風を１分〜３０分送風することにより行われる。焼成処理に用いられる焼成処理装置の形式は問わないが、内部で銅くずを流動させることで酸化が進むため、適切な揺動機構や撹拌機構を有するものが好ましく用いられる。
【００１０】
焼成処理を行った後、焼成処理された銅くずに酸洗処理を行う。酸洗処理において、酸洗液としては０．１〜２．０ｍｏｌ／ｌの硫酸水溶液が好ましく用いられる。硫酸水溶液のほか、電気分解に用いる電解液を用いることもできる。その他の無機酸や有機酸の水溶液は、電解液の汚染原因となることから好ましくない。水洗装置も形式を問わないが、銅くずと十分に接触するための機構を有することが好ましい。このような装置は、酸洗液の循環機構を設けて被処理物を揺動させるなどによって実現可能である。酸洗処理は硫酸水溶液中で被処理物を好ましくは１０℃〜６０℃の温度で、１分〜３０分間揺動させることにより行われる。酸洗処理後に純水を用いて処理銅くずを十分に洗浄し、付着物を除去する。
【００１１】
次に、上記で得られた処理銅くずを硫酸水溶液に溶解する。この硫酸水溶液としては、濃度が０．１〜５ｍｏｌ／ｌのものが好ましく、０．５〜３ｍｏｌ／ｌのものがより好ましい。銅くずの溶解は硫酸水溶液に空気を送り込みながら行うことが好ましい。次いで得られた電解液を用いて電気分解を行い、陰極に銅を析出させる。電気分解の条件は特に限定されず、通常の電解銅箔製造の電解条件で行われる。好ましくは、電流密度５〜１５０Ａ／ｄｍ2、電解時間１〜３０分間の条件で行われ、厚さ２μｍ以上の電解銅箔が得られる。薄い、すなわち、２〜１０μｍの電解銅箔を得るためには、電流と電解時間適宜制御して行う。更に必要ならば、銅箔面に粗化処理や防錆処理を行うことができる。
【００１２】
【実施例】
以下、本発明の実施例及びその比較例によって本発明を更に具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
【００１３】
実施例１
ＪＩＳ Ｈ ２１０９に規定される１号ナゲット銅（平均重量０．２ｇ／個）５００ｇを白金製金網に入れ、下から７００℃の熱風を１分間送風した。ナゲット銅を十分に混合した後、再度７００℃の熱風を１分間送風した。この送風操作を１０回繰り返して行うことで、焼成処理を行った。
【００１４】
試薬硫酸から調製した１ｍｏｌ／ｌの硫酸水溶液に焼成処理されたナゲット銅を投入し、硫酸水溶液中で３分間揺動させた。次いでナゲット銅を純水中に移して３分間揺動させた。この二つの操作を三回繰り返した。
【００１５】
試薬硫酸から調製した２ｍｏｌ／ｌの硫酸水溶液に酸洗処理したナゲット銅を投入し、空気を送り込みながらナゲット銅を完全に溶解させた。なお、空気は硫酸水溶液、水酸化ナトリウム水溶液とシリカゲルとを通気させた後、０．５μｍフィルタを介してゴミや不純物の混入を防止したものを用いた。
【００１６】
次いで硫酸と純水とで硫酸銅２８０ｇ／ｌ、硫酸８０ｇ／ｌに濃度を調節し、電解液とした。
【００１７】
陰極として、径５ｃｍのチタン製円筒状電極を用い、表面を２０００番の研磨紙を用いて研磨を行った。表面粗さはＲａで０．２０μｍであった。陽極板には円筒状の鉛板を用い、上記の電解液を用いて液温４０℃、電流密度１０Ａ／ｄｍ2で５分間電気分解を行い、銅箔を析出させた。ただし円筒状電極の回転数は３００ｒｐｍとした。銅箔は両面ともに光沢を有し、重量法により求めた厚さは１２μｍであった。機械特性の測定結果を表１に示す。
【００１８】
比較例１
焼成処理を行わないほかは実施例１と同様に銅箔を調製し、機械特性を評価した。結果を表１に示した。
【００１９】
比較例２
酸洗処理を行わないほかは実施例１と同様に銅箔を調製し、機械特性を評価した。結果を表１に示した。
【００２０】
比較例３
焼成処理と酸洗処理を行わないほかは実施例１と同様に銅箔を調製し、機械特性を評価した。結果を表１に示した。
【００２１】
【表１】
引張強度は常態（２３℃）及び１８０℃で１時間加熱後の引張強度をＪＩＳ Ｃ６５１５に基づいて測定した。
伸び率は常態（２３℃）及び１８０℃で１時間加熱後の引張強度をＪＩＳ Ｃ ６５１５に基づいて測定した。
【００２２】
【発明の効果】
本発明の製造方法により得られた電解銅箔は、薄くて引張強度が大きく、剛性が高いことから取扱性に優れ、両面が平滑で同等の表面粗さを有し、伸び率に優れた、微細回路を有する電子回路用銅箔やリチウムイオン二次電池の負極板用銅箔として極めて有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing an electrolytic copper foil suitably used for a circuit of an electronic component or a negative electrode of a lithium secondary battery.
[0002]
[Prior art]
The manufacturing process of the electrolytic copper foil is a composite process composed of a dissolution process for dissolving a copper raw material in an electrolytic solution and a copper precipitation process for depositing copper by electrolysis using an electrolytic solution in which the copper raw material is dissolved. It is necessary to dissolve in the electrolyte a copper raw material sufficient to meet the requirements. Copper scrap is inexpensive and has a large surface area. As the copper scrap, it is common to use a scrap copper wire that has been chopped, but other than that, a melt-extruded product that has been chopped is also used. These copper scraps are contaminated by wire drawing oil during extrusion, impurities derived from coating materials, and impurities attached during scrapping and shredding.
[0003]
In recent years, in order to realize a high-density electronic circuit, a thin electrolytic copper foil suitable for forming a fine circuit is desired. A method for producing a thin electrolytic copper foil by electrolysis using an electrolytic solution in which an organic substance such as gelatin or chloride is added to an aqueous copper sulfate solution obtained by dissolving a copper raw material in an aqueous sulfuric acid solution is known. The obtained electrolytic copper foil had a difficulty that it was difficult to handle because of its low tensile strength and poor rigidity. In addition, the electrolytic copper foil obtained by this manufacturing method has a relatively large surface roughness on the copper foil deposition surface side, and the thickness is not uniform, so the thin copper foil tended to cause wrinkles and the like. . Further, the large surface roughness causes over-etching, and there is a problem that the formation of a fine circuit is hindered.
[0004]
[Problems to be solved by the invention]
The object of the present invention is to use an electrolytic solution obtained from an inexpensive copper scrap that has been conventionally used, and is thin, has high tensile strength, and has high rigidity. It is providing the manufacturing method of the electrolytic copper foil which can manufacture the electrolytic copper foil which has thickness and was excellent in elongation rate.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventors have used copper scrap as a copper raw material that dissolves in the electrolytic solution, and after the copper scrap is baked, the treatment obtained by pickling treatment By using copper scrap, it is possible to produce an electrolytic copper foil that is thin, has high tensile strength, has high rigidity, has excellent handleability, is smooth on both sides, has the same surface roughness, and has excellent elongation. Based on this finding, the present invention has been completed.
[0006]
That is, in the present invention, after the copper scrap is fired, the treated copper scrap obtained by pickling is dissolved in an aqueous sulfuric acid solution to prepare an electrolytic solution, and the obtained electrolytic solution is used to electrolyze copper by electrolysis. The present invention provides a method for producing an electrolytic copper foil characterized by performing precipitation.
[0007]
The electrolytic copper foil obtained by the present invention is thin, has a high tensile strength, is suitable for forming a fine circuit, and has an excellent elongation rate.For example, when it is used as an inner layer circuit, it has a disconnection failure due to thermal expansion. It has a very excellent characteristic as a copper foil for electronic circuits. In addition, both sides are smooth, have the same surface roughness, and have high rigidity, so it is easy to apply both sides of the active material mixture for secondary batteries. It is an extremely useful copper foil as a copper foil for a negative electrode plate of a battery.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
As the copper scrap used in the present invention, those having 99% or more of the copper content not containing foreign substances and foreign materials are preferably used. More preferably, No. 1 nugget copper specified in JIS H 2109 is used. This is a copper scrap that can be obtained at a low cost and is a pure one obtained by nuggeting a copper wire or a copper stranded wire (short cut wire), and has a copper content of 99.9% or more. Moreover, foreign materials, such as a copper-clad steel wire, and a foreign material are not mixed. Also, No. 1 copper wire waste as defined in JIS H 2109 can be used. In the present invention, an electrolytic solution is prepared by dissolving a treated copper scrap obtained by firing and pickling the copper scrap in sulfuric acid.
[0009]
By performing the firing treatment, the surface deposits on the copper scrap are oxidized and burned, and the oxidized surface is easily eroded by acid, improving pickling efficiency and easily removing deposits such as oil. become able to. The conditions for the firing treatment are such that a thin copper oxide layer is formed on the surface of the copper scrap, preferably by exposing the copper scrap to an oxidizing atmosphere of 500 ° C. to 800 ° C., preferably for 1 to 30 minutes. Is called. This operation may be repeated. Specifically, it is performed by blowing hot air at 500 to 800 ° C. for 1 minute to 30 minutes to the object to be processed. Although the form of the baking treatment apparatus used for the baking treatment is not limited, since the oxidation proceeds by flowing the copper scrap inside, a device having an appropriate rocking mechanism and stirring mechanism is preferably used.
[0010]
After performing the firing treatment, pickling treatment is performed on the fired copper scrap. In the pickling treatment, a 0.1-2.0 mol / l sulfuric acid aqueous solution is preferably used as the pickling solution. In addition to an aqueous sulfuric acid solution, an electrolytic solution used for electrolysis can also be used. An aqueous solution of other inorganic acid or organic acid is not preferable because it causes contamination of the electrolytic solution. The type of the water washing apparatus is not limited, but it is preferable to have a mechanism for making sufficient contact with the copper scrap. Such an apparatus can be realized by providing a pickling solution circulation mechanism to swing the workpiece. The pickling treatment is performed by oscillating the object to be treated in an aqueous sulfuric acid solution at a temperature of preferably 10 ° C. to 60 ° C. for 1 to 30 minutes. After the pickling treatment, the treated copper scrap is sufficiently washed with pure water to remove the deposits.
[0011]
Next, the treated copper scrap obtained above is dissolved in an aqueous sulfuric acid solution. The sulfuric acid aqueous solution preferably has a concentration of 0.1 to 5 mol / l, more preferably 0.5 to 3 mol / l. It is preferable to dissolve the copper scrap while feeding air into the sulfuric acid aqueous solution. Next, electrolysis is performed using the obtained electrolytic solution, and copper is deposited on the cathode. The electrolysis conditions are not particularly limited, and the electrolysis is performed under the usual electrolysis conditions for producing an electrolytic copper foil. Preferably, it is performed under the conditions of a current density of 5 to 150 A / dm 2 and an electrolysis time of 1 to 30 minutes, and an electrolytic copper foil having a thickness of 2 μm or more is obtained. In order to obtain a thin, that is, 2 to 10 μm, electrolytic copper foil, the current and electrolysis time are appropriately controlled. Further, if necessary, the copper foil surface can be roughened or rust-proofed.
[0012]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples of the present invention and comparative examples thereof, but the present invention is not limited to these examples.
[0013]
Example 1
500 g of No. 1 nugget copper (average weight 0.2 g / piece) specified in JIS H 2109 was placed in a platinum wire mesh, and hot air at 700 ° C. was blown from the bottom for 1 minute. After thoroughly mixing the nugget copper, 700 ° C. hot air was blown again for 1 minute. A baking process was performed by repeating this blowing operation 10 times.
[0014]
The fired nugget copper was put into a 1 mol / l sulfuric acid aqueous solution prepared from the reagent sulfuric acid, and was swung in the sulfuric acid aqueous solution for 3 minutes. Next, the nugget copper was moved into pure water and rocked for 3 minutes. These two operations were repeated three times.
[0015]
The pickled nugget copper was put into a 2 mol / l sulfuric acid aqueous solution prepared from the reagent sulfuric acid, and the nugget copper was completely dissolved while feeding air. The air used was one in which a sulfuric acid aqueous solution, a sodium hydroxide aqueous solution and silica gel were aerated and dust and impurities were prevented from entering through a 0.5 μm filter.
[0016]
Subsequently, the concentration was adjusted to 280 g / l copper sulfate and 80 g / l sulfuric acid with sulfuric acid and pure water to obtain an electrolytic solution.
[0017]
A titanium cylindrical electrode having a diameter of 5 cm was used as the cathode, and the surface was polished using No. 2000 polishing paper. The surface roughness Ra was 0.20 μm. A cylindrical lead plate was used as the anode plate, and electrolysis was performed for 5 minutes at a liquid temperature of 40 ° C. and a current density of 10 A / dm 2 using the above-described electrolytic solution to deposit a copper foil. However, the rotational speed of the cylindrical electrode was 300 rpm. The copper foil was glossy on both sides, and the thickness determined by the gravimetric method was 12 μm. Table 1 shows the measurement results of the mechanical properties.
[0018]
Comparative Example 1
A copper foil was prepared in the same manner as in Example 1 except that the firing treatment was not performed, and the mechanical properties were evaluated. The results are shown in Table 1.
[0019]
Comparative Example 2
A copper foil was prepared in the same manner as in Example 1 except that the pickling treatment was not performed, and the mechanical properties were evaluated. The results are shown in Table 1.
[0020]
Comparative Example 3
A copper foil was prepared in the same manner as in Example 1 except that the baking treatment and the pickling treatment were not performed, and the mechanical properties were evaluated. The results are shown in Table 1.
[0021]
[Table 1]
Tensile strength was measured based on JIS C6515 for tensile strength after heating at normal temperature (23 ° C.) and 180 ° C. for 1 hour.
Elongation rate measured the normal state (23 degreeC) and the tensile strength after 1-hour heating at 180 degreeC based on JISC6515.
[0022]
【The invention's effect】
The electrolytic copper foil obtained by the production method of the present invention is thin and has high tensile strength and high rigidity, so it is excellent in handleability, smooth on both sides, has the same surface roughness, and excellent in elongation. It is extremely useful as a copper foil for electronic circuits having a fine circuit or a copper foil for a negative electrode plate of a lithium ion secondary battery.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18352899A JP4349690B2 (en) | 1999-06-29 | 1999-06-29 | Method for producing electrolytic copper foil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18352899A JP4349690B2 (en) | 1999-06-29 | 1999-06-29 | Method for producing electrolytic copper foil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001011684A JP2001011684A (en) | 2001-01-16 |
| JP4349690B2 true JP4349690B2 (en) | 2009-10-21 |
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|---|---|---|---|
| JP18352899A Expired - Lifetime JP4349690B2 (en) | 1999-06-29 | 1999-06-29 | Method for producing electrolytic copper foil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3768104B2 (en) | 2001-01-22 | 2006-04-19 | ソニーケミカル株式会社 | Flexible printed circuit board |
| JP4583149B2 (en) * | 2004-12-01 | 2010-11-17 | 三井金属鉱業株式会社 | Electrolytic copper foil and method for producing the same |
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