JP2001123289A - Electrolytic copper foil and method for manufacturing the same - Google Patents
Electrolytic copper foil and method for manufacturing the sameInfo
- Publication number
- JP2001123289A JP2001123289A JP30554499A JP30554499A JP2001123289A JP 2001123289 A JP2001123289 A JP 2001123289A JP 30554499 A JP30554499 A JP 30554499A JP 30554499 A JP30554499 A JP 30554499A JP 2001123289 A JP2001123289 A JP 2001123289A
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- Prior art keywords
- copper foil
- electrolytic
- electrolytic copper
- cathode
- producing
- 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.)
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- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、折り曲げ実装性の
要求されるプリント配線板用電解銅箔とその製造方法に
関し、詳しくは電解液中の添加剤の種類と濃度を規制す
ることにより機械的特性（常温での抗張力および耐折
度）と銅箔製造時のカソードとの密着性を向上させたプ
リント配線用電解銅箔およびその製造方法に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrolytic copper foil for a printed wiring board, which is required to be folded and mounted, and a method for producing the same. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrolytic copper foil for printed wiring which has improved characteristics (tensile strength and bending resistance at ordinary temperature) and adhesion to a cathode during copper foil production, and a method for producing the same.
【０００２】[0002]
【従来の技術】一般的に電解銅箔は、不溶性金属製の陽
極（アノード）と表面を鏡面研磨された金属製陰極（カ
ソード）胴（ドラム）との間に電解液を通しながら、両
極間に直流電流を流してカソード表面に銅箔を電着さ
せ、このカソードに電着した銅箔を連続的に剥離するこ
とによって製造される。電解液は銅イオンと硫酸イオン
を含有し、これに様々な有機添加剤を加えて、また塩素
イオン濃度を管理することにより銅箔の特性を制御して
いる。2. Description of the Related Art In general, an electrolytic copper foil is formed by passing an electrolytic solution between an insoluble metal anode (anode) and a metal cathode (cathode) body (drum) having a mirror-polished surface. A copper current is applied to the cathode surface by applying a direct current to the cathode, and the copper foil electrodeposited on the cathode is continuously peeled off. The electrolyte contains copper ions and sulfate ions, to which various organic additives are added, and the properties of the copper foil are controlled by controlling the chloride ion concentration.
【０００３】例えば、公表平４−５０１８８７号特許公
報には、ゼラチン（具体的には膠）および活性硫黄含有
成分（具体的にはチオ尿素）を添加することにより、低
プロファイルでかつＩＰＣ１級または３級と同等以上の
特性を持つ銅箔の製造方法に関する技術が開示されてい
る。[0003] For example, Japanese Patent Publication No. 4-50187 discloses a low profile and IPC grade 1 or 2 by adding gelatin (specifically, glue) and an active sulfur-containing component (specifically, thiourea). A technique relating to a method for producing a copper foil having characteristics equivalent to or higher than the third class is disclosed.
【０００４】また、特公平６−４９９５８号公報には、
塩素イオンを１〜３０ｐｐｍ以下，トリイソアミルアミ
ン，塩素イオンおよびゼラチンを添加することにより、
高温（１８０℃）での伸び率１０％以上，室温での抗張
力が３８〜４４Ｋｇｆ／ｍｍ 2の銅箔の製造方法につい
ての技術が開示されている。In Japanese Patent Publication No. 6-49958,
Chloride ion of 1 to 30 ppm or less, triisoamylamine
, Chloride ions and gelatin,
Elongation 10% or more at high temperature (180 ° C), tensile at room temperature
Force is 38-44Kgf / mm TwoAbout the method of manufacturing copper foil
All techniques are disclosed.
【０００５】さらには、特開平１０−３３０９８３号公
報にはオキシエチレン系界面活性剤（具体的にはポリエ
チレングリコール）を0.1〜1.0g／Ｌ、塩化物５０〜２
５０ｍｇ/L、膠またはゼラチン１〜１０ｍｇ／Lを添加
することにより高いビッカース硬さと熱安定性に優れた
銅箔の製造方法が記載されている。このように、膠、チ
オ尿素等の有機物を添加することにより、銅箔の室温お
よび／または高温での機械的特性の改善がなされてき
た。Further, JP-A-10-330983 discloses that 0.1 to 1.0 g / L of an oxyethylene surfactant (specifically, polyethylene glycol) and 50 to 2 g of chloride are used.
A method for producing a copper foil excellent in high Vickers hardness and heat stability by adding 50 mg / L, glue or gelatin at 1 to 10 mg / L is described. As described above, by adding an organic substance such as glue or thiourea, the mechanical properties of the copper foil at room temperature and / or high temperature have been improved.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、膠（ゼ
ラチン）、チオ尿素といった有機物は、生成した電解銅
箔中に取り込まれるため、銅箔とカソードとの密着性を
阻害し、銅箔の生成過程中にカソードから剥離しやすく
なるという問題点があり、このため、カソードドラムの
回転速度または電解液の送液速度を調整したり、あるい
は電解液の撹拌を調整するなど、電解銅箔生成時の条件
出しに熟練と経験が要求され、またこのことは同時に、
高電流密度下で連続操業を実施しようとする場合の障害
となっていた。However, since organic substances such as glue (gelatin) and thiourea are taken into the produced electrolytic copper foil, the adhesion between the copper foil and the cathode is hindered, and the process of producing the copper foil takes place. During the production of electrolytic copper foil, such as adjusting the rotation speed of the cathode drum or the speed of feeding the electrolytic solution, or adjusting the stirring of the electrolytic solution, there is a problem that it is easy to peel off from the cathode. Skill and experience are required to set the conditions, and at the same time,
This has been an obstacle to attempting continuous operation at high current densities.
【０００７】さらには、電気・電子部品の軽薄、短小化
に伴い、銅箔のより薄箔化が要求されているが、これに
伴い機械的特性のさらなる向上も要求されている。具体
的には５００Ｎ／ｍｍ2を越える抗張力と１５０回を越
える耐折度であるが、これまでの添加剤を用いた電解銅
箔の製造方法では、抗張力は３５０〜４５０Ｎ／ｍｍ 2
程度であり、また耐折度も１００回以下とのこの要求に
答えられない。[0007] Furthermore, light and thin and short electric / electronic parts.
As a result, thinner copper foil is required,
Accordingly, further improvement in mechanical properties is also required. Concrete
Typically 500N / mmTwoStrength exceeding 150 times
Electrolytic copper using conventional additives
In the method for producing a foil, the tensile strength is 350 to 450 N / mm. Two
To meet this requirement that the folding endurance is 100 times or less.
Unanswerable.
【０００８】このように、従来提供される電解銅箔およ
びその製造方法では、機械的特性のさらなる改善ができ
ないばかりか、カソードとの密着性が劣化するという問
題点があった。なお、カソードとの密着性を維持するた
め、添加剤を全く除去した場合、抗折力をはじめとした
機械的特性が劣り、プリント配線板用の銅箔として使用
ができない。As described above, the conventionally provided electrolytic copper foil and the method of manufacturing the same have problems that not only the mechanical properties cannot be further improved but also the adhesion to the cathode is deteriorated. When the additive is completely removed to maintain the adhesion to the cathode, mechanical properties such as bending strength are inferior and cannot be used as a copper foil for a printed wiring board.
【０００９】プリント配線板用電解銅箔においては、近
年コストダウンの要求から広幅化および連続操業での大
量生産が行われるようになってきている。このため、カ
ソードに高電流密度を通電し、また供給する液流速を高
めることでカソードドラムの回転数を早め、高負荷連続
操業が実施されるようになってきているが、この際カソ
ードに一旦生成した銅箔が電解析出中に剥離してしまう
という問題が起こることが知られている。[0009] In recent years, in order to reduce the cost of electro-deposited copper foil for printed wiring boards, widening and mass production by continuous operation have been performed. For this reason, a high current density is supplied to the cathode, and the flow rate of the supplied liquid is increased to increase the number of revolutions of the cathode drum and to carry out continuous high-load operation. It is known that a problem occurs that the generated copper foil is peeled off during electrolytic deposition.
【００１０】すなわち、高負荷連続操業では、１００Ａ
／ｄｍ2以上の高電流密度を通電し、かつ銅イオンの濃
度偏析を防ぐため、電解液の液流速を３ｍ／ｓｅｃ以上
とすることが一般的である。このため、一旦生成した銅
箔が撹拌および電解液の流れにより自然剥離を起こして
しまう問題が起きている。That is, in the continuous operation under high load, 100 A
In general, the flow rate of the electrolytic solution is set to 3 m / sec or more in order to apply a high current density of / dm 2 or more and to prevent the concentration of copper ions from segregating. For this reason, there has been a problem that the copper foil once formed is spontaneously exfoliated by the stirring and the flow of the electrolytic solution.
【００１１】すなわち、高電流密度下で連続操業を実施
することが可能なカソードとの密着性が良好でかつ銅箔
の機械的特性（特に常温での抗張力と耐折度）が良好な
電解銅箔の提供が望まれている。That is, electrolytic copper having good adhesion to a cathode capable of performing continuous operation under a high current density and having good mechanical properties (particularly tensile strength and bending resistance at room temperature) of a copper foil. Providing foil is desired.
【００１２】[0012]
【課題を解決するための手段】本発明はこのような問題
点に鑑み、製造上の要求特性および製品としての電解銅
箔からくる要求特性の両者を満足する電解銅箔およびそ
の製造方法を提供するものである。本発明者らは、電解
銅箔の生成条件について鋭意検討を行ったところ、従来
から使用されている膠，活性硫黄含有成分および塩化物
イオンを含む硫酸酸性硫酸銅電解液において、添加剤と
してオキシエチレン系界面活性剤を併せて添加すること
でカソードとの密着性が良好で連続操業も耐えうる電解
銅箔が製造可能であることを見いだした。SUMMARY OF THE INVENTION In view of the above problems, the present invention provides an electrolytic copper foil which satisfies both required characteristics in production and characteristics required from an electrolytic copper foil as a product, and a method for producing the same. Is what you do. The present inventors have conducted intensive studies on the conditions for forming an electrolytic copper foil, and found that, in a conventionally used sulfuric acid acidic copper sulfate electrolytic solution containing a glue, an active sulfur-containing component and chloride ions, oxy as an additive was used. It has been found that by adding an ethylene-based surfactant, it is possible to produce an electrolytic copper foil which has good adhesion to the cathode and can withstand continuous operation.
【００１３】すなわち、オキシエチレン系界面活性剤だ
けではカソードとの密着性は改善されるものの、充分な
機械的特性（耐折度、抗張力、耐熱性等）が得られな
い。また、従来公知の膠（ゼラチン），活性硫黄含有成
分，塩化物イオンの組み合わせだけでは機械的特性は改
善されるものの、充分なカソードとの密着性が得られ
ず、高電流密度下での連続操業に耐え得ることができな
いことがわかった。That is, although the adhesion to the cathode is improved by using only the oxyethylene-based surfactant, sufficient mechanical properties (such as bending resistance, tensile strength and heat resistance) cannot be obtained. In addition, although mechanical properties are improved only by a combination of conventionally known glue (gelatin), active sulfur-containing components, and chloride ions, sufficient adhesion to a cathode cannot be obtained and continuous operation under a high current density is not possible. It turns out that the operation cannot be tolerated.
【００１４】しかしながら、ここにオキシエチレン系界
面活性剤を膠（ゼラチン），活性硫黄含有成分および塩
化物イオンを含む硫酸酸性硫酸銅電解液に併せて使用す
ることで、従来では予知できなかったカソード密着性に
優れた電解銅箔の製造が可能になり、はじめて高電流密
度操業下でも耐えうる電解銅箔が製造できることが判明
した。However, by using an oxyethylene-based surfactant in combination with a sulfuric acid-acidic copper sulfate electrolyte containing glue (gelatin), an active sulfur-containing component and chloride ions, a cathode which could not be predicted in the past was used. It has become clear that it is possible to produce an electrolytic copper foil having excellent adhesion, and it is possible to produce an electrolytic copper foil that can withstand high current density operation for the first time.
【００１５】本発明は、次の点に特徴を有する電解銅箔
およびその製造方法である。 １．抗張力が５００Ｎ／ｍｍ2以上であり、かつ耐折度
が１５０回以上であることを特徴とする電解銅箔。The present invention is an electrolytic copper foil having the following features and a method for producing the same. 1. An electrolytic copper foil having a tensile strength of 500 N / mm 2 or more and a fold resistance of 150 times or more.
【００１６】２．前記電解銅箔中の塩素含有量が１０〜
５００ｐｐｍであることを特徴とする電解銅箔。2. The chlorine content in the electrolytic copper foil is 10
An electrolytic copper foil having a concentration of 500 ppm.
【００１７】３．前記電解度箔がカソードとの密着性に
優れていることを特徴とする電解銅箔。3. An electrolytic copper foil, wherein the electrolytic foil has excellent adhesion to a cathode.
【００１８】４．硫酸銅と硫酸を主成分とする酸性銅電
解浴を用いて電解銅箔を製造するにあたり、該電解浴に
塩素イオン，膠またはゼラチン，活性硫黄含有成分およ
びオキシエチレン系界面活性剤を添加して電解処理を行
うことを特徴とするカソード密着性の良好な電解銅箔の
製造方法。4. In producing an electrolytic copper foil using an acidic copper electrolytic bath containing copper sulfate and sulfuric acid as main components, chlorine ion, glue or gelatin, an active sulfur-containing component and an oxyethylene surfactant are added to the electrolytic bath. A method for producing an electrolytic copper foil having good cathode adhesion, comprising performing an electrolytic treatment.
【００１９】５．前記活性硫黄含有成分がチオ尿素であ
り、前記オキシエチレン系界面活性剤がポリエチレング
リコールである電解銅箔の製造方法。5. A method for producing an electrolytic copper foil in which the active sulfur-containing component is thiourea and the oxyethylene-based surfactant is polyethylene glycol.
【００２０】６．前記電解浴中の添加剤濃度が、塩素イ
オン：５〜２８０ｐｐｍ，膠またはゼラチン：0.１〜５
０ｐｐｍ，チオ尿素：１〜５０ｐｐｍおよびポリエチレ
ングリコール：0.5〜3.5ｇ／Ｌである電解銅箔の製造方
法。6. The concentration of the additive in the electrolytic bath is 5 to 280 ppm for chloride ions, 0.1 to 5 for glue or gelatin.
A method for producing an electrolytic copper foil having 0 ppm, thiourea: 1 to 50 ppm, and polyethylene glycol: 0.5 to 3.5 g / L.
【００２１】７．前記ポリエチレングリコールの平均分
子量が２０００〜２００００であることを特徴とする電
解銅箔の製造方法。7. A method for producing an electrolytic copper foil, wherein the average molecular weight of the polyethylene glycol is 2,000 to 20,000.
【００２２】８．前記電解浴に通電する電流密度が１０
０Ａ／ｄｍ2以上で、かつ供給する液流速が３ｍ／ｓｅ
ｃ以上での高負荷連続操業であることを特徴とする電解
銅箔の製造方法。8. The current density for passing the electrolytic bath is 10
0 A / dm 2 or more, and the supplied liquid flow rate is 3 m / sec
c. A method for producing an electrolytic copper foil, which is a high-load continuous operation at or above c.
【００２３】[0023]
【作用】以下に、本発明について、その範囲限定理由を
詳細に述べる。ポリエチレングリコールの濃度範囲を0.
5〜3.5ｇ／Ｌとしたのは、3.5ｇ／Ｌを超えると他の添
加剤（塩素イオン、膠またはゼラチンおよびチオ尿素）
が含有されていても生成される電解銅箔が脆くなり、機
械的特性が劣る。また、0.5ｇ／Ｌ以下ではカソード密
着性を改善する効果は少ない。従って、ポリエチレング
リコールの濃度範囲は0.5〜3.5ｇ／Ｌとし、好ましくは
1.5〜2.5ｇ／Ｌとする。The reasons for limiting the scope of the present invention will be described below in detail. Adjust the concentration range of polyethylene glycol to 0.
The range of 5 to 3.5 g / L is that if it exceeds 3.5 g / L, other additives (chloride ion, glue or gelatin and thiourea)
, The resulting electrolytic copper foil becomes brittle and has poor mechanical properties. When the content is 0.5 g / L or less, the effect of improving the cathode adhesion is small. Therefore, the concentration range of polyethylene glycol is 0.5 to 3.5 g / L, preferably
1.5 to 2.5 g / L.
【００２４】また、ポリエチレングリコールの平均分子
量を２０００〜２００００としたのは、平均分子量２０
０００を超えると硫酸酸性電解液に対する溶解度が小さ
く、作業性が劣るうえ、カソード密着性を改善する効果
も飽和し、これ以上期待できない。また、平均分子量２
０００以下では、カソード密着性を改善する効果が小さ
い。従って、添加剤として使用するポリエチレングリコ
ールの平均分子量は２０００〜２００００とし、好まし
くは平均分子量５０００〜１００００とする。The reason why the average molecular weight of polyethylene glycol is set to 2000 to 20,000 is that the average molecular weight is 20
If it exceeds 000, the solubility in the sulfuric acid acidic electrolyte is small, the workability is poor, and the effect of improving the cathode adhesion is saturated, so that it cannot be expected any more. In addition, the average molecular weight 2
If it is less than 000, the effect of improving the cathode adhesion is small. Therefore, the average molecular weight of polyethylene glycol used as an additive is 2,000 to 20,000, preferably 5,000 to 10,000.
【００２５】塩素イオンを塩素イオン５〜２８０ｐｐｍ
としたのは、カソード密着性を維持するためである。す
なわち、塩素イオンが５ｐｐｍ以下ではポリエチレング
リコールの濃度範囲を0.5〜3.5ｇ／Ｌであっても、充分
なカソード密着性を維持することができない。また、２
８０ｐｐｍ以上添加しても効果が飽和し、これ以上カソ
ード密着性の改善は期待できず、むしろ他の機械的特性
（特に常温における伸び率）が低下する。従って、塩素
イオンは５〜２８０ｐｐｍとし、好ましくは６０〜１６
０ｐｐｍとする。[0025] Chlorine ion is converted to chlorine ion 5-280 ppm.
The reason for this is to maintain the cathode adhesion. That is, when the chlorine ion is 5 ppm or less, sufficient cathode adhesion cannot be maintained even when the concentration range of polyethylene glycol is 0.5 to 3.5 g / L. Also, 2
Even if it is added in an amount of 80 ppm or more, the effect is saturated, and no further improvement in cathode adhesion can be expected. Rather, other mechanical properties (especially, elongation at room temperature) decrease. Therefore, the chlorine ion should be 5 to 280 ppm, preferably 60 to 16 ppm.
0 ppm.
【００２６】膠またはゼラチン、チオ尿素をそれぞれ0.
1〜５０ｐｐｍ、１〜５０ｐｐｍとしたのは、いずれも
耐折度、伸び率、抗張力を維持し、かつカソード密着性
を改善するためである。膠またはゼラチン、チオ尿素が
それぞれ0.1ｐｐｍ以下、１ｐｐｍ以下である場合、耐
折度、伸び率、抗張力およびカソード密着性のいずれも
が劣り、高電流密度下での連続操業が実施できない。ま
た、それぞれ５０ｐｐｍ以上の場合、添加剤の効果が飽
和し、これ以上の機械的特性の向上が期待できないばか
りか、膠またはゼラチンおよび／またはチオ尿素から生
成した分解物により、特に抗張力が低下する。従って、
膠またはゼラチンは0.1〜５０ｐｐｍとし、チオ尿素は
１〜５０ｐｐｍとする。なお、好ましくは膠またはゼラ
チンの濃度を0.5〜２０ｐｐｍ、チオ尿素を５〜２０ｐ
ｐｍとする。Glue, gelatin, and thiourea are each added to 0.1 g.
The reason for using 1 to 50 ppm and 1 to 50 ppm is to maintain the bending resistance, elongation, and tensile strength, and to improve the cathode adhesion. When the amount of glue, gelatin, and thiourea is 0.1 ppm or less and 1 ppm or less, respectively, the bending resistance, elongation, tensile strength, and cathode adhesion are all inferior, and continuous operation at a high current density cannot be performed. When the content is 50 ppm or more, the effect of the additive is saturated, and further improvement in mechanical properties cannot be expected. In addition, the tensile strength is particularly reduced due to the decomposition products generated from glue or gelatin and / or thiourea. . Therefore,
The glue or gelatin is 0.1-50 ppm and the thiourea is 1-50 ppm. Preferably, the concentration of glue or gelatin is 0.5 to 20 ppm, and thiourea is 5 to 20 ppm.
pm.
【００２７】なお、オキシエチレン系界面活性剤として
ポリエチレングリコールの代わりに同様の働きがある高
分子界面活性剤（例えばポリプロピレングリコール等）
を使用しても差し支えない。また、塩化物イオンは電解
液中に可溶であれば特に制限されるものではなく、例え
ば塩酸、塩化ナトリウム、塩化カリウム等が添加剤とし
て挙げられる。さらには、上述の膠またはゼラチンと
は、動物の白色結合組織である皮や骨を構成する主要タ
ンパク質あるいはそのタンパク質を加水分解して得られ
たタンパク質を指し、これらを原料としてタンパク質分
解酵素により分解し精製して得られた低分子量水溶性ゼ
ラチンもこれに含まれる。活性硫黄含有成分はチオ尿素
［ＳＣ（ＮＨ2）2］の代わりに、チオ尿素の誘導体（例
えばアセチルチオ尿素等）を使用しても差し支えない。In addition, instead of polyethylene glycol, a high molecular surfactant (for example, polypropylene glycol or the like) having the same function as the oxyethylene surfactant.
Can be used. The chloride ion is not particularly limited as long as it is soluble in the electrolytic solution, and examples thereof include hydrochloric acid, sodium chloride, potassium chloride and the like. Further, the above-mentioned glue or gelatin refers to a main protein constituting skin or bone, which is white connective tissue of an animal, or a protein obtained by hydrolyzing the protein, and is degraded by proteolytic enzymes using these as raw materials. And low-molecular-weight water-soluble gelatin obtained by purification. As the active sulfur-containing component, a derivative of thiourea (for example, acetylthiourea) may be used instead of thiourea [SC (NH 2 ) 2 ].
【００２８】また、本発明によれば電流密度が１００Ａ
／ｄｍ2以上でかつ液流速３ｍ／ｓｅｃ以上での高負荷
連続操業を実施することが可能となる。しかし、電流密
度が４００Ａ／ｄｍ2以上の場合、電解反応以外に消費
するロス分が大きく、電流効率が低下するため実用的で
はない。したがって、電流密度は１００Ａ／ｄｍ2以上
４００Ａ／ｄｍ2以下とし、好ましくは２００〜３５０
Ａ／ｄｍ2とする。さらに、液流速についても２０ｍ／
ｓｅｃ以上の高速では、外気の巻き込みにより生成した
電解銅箔に気泡が混入し、機械的特性が低下するうえ、
撹拌動力も嵩み操業上好ましいとはいえない。従って、
液流速については３〜２０ｍ／ｓｅｃとし、好ましくは
４〜１０ｍ／ｓｅｃとする。According to the present invention, the current density is 100 A
/ Dm 2 or more and a liquid flow velocity of 3 m / sec or more, it is possible to carry out a high-load continuous operation. However, when the current density is 400 A / dm 2 or more, a large amount of loss is consumed other than the electrolytic reaction, and the current efficiency is lowered, which is not practical. Therefore, the current density was set to 100A / dm 2 or more 400A / dm 2 or less, preferably 200 to 350
A / dm 2 . Further, the liquid flow velocity is 20 m /
At a high speed of more than sec, bubbles are mixed into the electrolytic copper foil generated by the entrainment of the outside air, and the mechanical properties are reduced.
The stirring power is also bulky and not preferable for operation. Therefore,
The liquid flow velocity is 3 to 20 m / sec, preferably 4 to 10 m / sec.
【００２９】上記の諸条件（構成要件）に従い作成され
た電解銅箔は、抗張力が５００Ｎ／ｍｍ2、耐折力が１
５０回以上の特性を有する電解銅箔となる。また、ここ
で電解銅箔中の塩素は通常１０〜５００ｐｐｍの範囲で
ある。電解銅箔中の塩素が１０ｐｐｍ以下では機械的特
性、特に耐折度が劣る。また、５００ｐｐｍを越えると
機械的特性、特に常温における抗張力が劣る。従って、
銅箔中の塩素は１０〜５００ｐｐｍとし、好ましくは１
００〜３００ｐｐｍとする。The electrolytic copper foil prepared in accordance with the above conditions (constituent requirements) has a tensile strength of 500 N / mm 2 and a bending strength of 1
It becomes an electrolytic copper foil having characteristics of 50 times or more. Here, chlorine in the electrolytic copper foil is usually in the range of 10 to 500 ppm. If the chlorine in the electrolytic copper foil is 10 ppm or less, the mechanical properties, particularly the folding resistance, are inferior. On the other hand, when the content exceeds 500 ppm, the mechanical properties, particularly the tensile strength at room temperature, are poor. Therefore,
The content of chlorine in the copper foil is 10 to 500 ppm, preferably 1 to 500 ppm.
It is set to 00 to 300 ppm.
【００３０】[0030]
【発明の実施の形態】実施例 以下、本発明の実施の形態を実施例により、さらに具体
的に説明する。硫酸銅・５水和物２４０ｇ／Ｌ、硫酸５
５ｇ／Ｌを含む硫酸酸性硫酸銅電解液に表１に示した添
加剤組成となるように各添加剤を調整した。このように
して調整した硫酸酸性硫酸銅電解液を用いて、陽極には
不溶性アノード、陰極には回転式円筒型ステンレス製カ
ソ−ド（ＳＵＳ３０４製）を使って、所定の電解条件で
箔の厚みが所定の厚さになるように回転式円筒型ステン
レス製カソ−ドを回転させながら銅を電解析出させ、こ
れをカソードからひき剥がすことによって未処理銅箔を
製造し、公知の防錆処理を施した。この場合の防錆処理
であるクロメート処理は浸漬または電解のいずれも選択
され、このどちらの場合においてもクロム付着量は１〜
１０ｍｇ／ｍ2である。また、防錆処理の前にあらかじ
め少なくとも一面に粗面化処理を行い、さらにバリアー
処理を施して、プリント配線用電解銅箔を製造した。Embodiments Hereinafter, embodiments of the present invention will be described more specifically with reference to embodiments. Copper sulfate pentahydrate 240 g / L, sulfuric acid 5
Each additive was adjusted so that the additive composition shown in Table 1 was obtained in the sulfuric acid acidic copper sulfate electrolyte containing 5 g / L. Using the sulfuric acid acidic copper sulfate electrolyte prepared in this manner, using an insoluble anode as the anode and a rotary cylindrical stainless steel cathode (made of SUS304) as the cathode, the thickness of the foil under predetermined electrolytic conditions Copper is electrolytically deposited while rotating a rotary cylindrical stainless steel cathode so as to have a predetermined thickness, and this is peeled off from the cathode to produce an untreated copper foil. Was given. In this case, chromate treatment, which is rust prevention treatment, is selected from either immersion or electrolysis.
10 mg / m 2 . Before the rust prevention treatment, at least one surface was previously subjected to a surface roughening treatment, and further subjected to a barrier treatment to produce an electrolytic copper foil for printed wiring.
【００３１】カソードとの密着性はテープ剥離試験によ
り評価を実施した。具体的には、住友３Ｍ製プラスチッ
クフィルムテープ♯８１０（初期引き剥がし強さ：0.35
Ｎ／ｍｍ）を銅箔の生成したカソード面に貼り、これを
引き剥がすことにより銅箔とカソードの密着性を評価し
た。このとき引き剥がし前にカソードから剥離，脱落が
起きているか、0.05Ｎ／ｍｍ以下の剥離力により銅箔が
カソードから剥がれてしまうものを×、0.05〜0.35Ｎ／
ｍｍ、すなわちフィルムテープと同等程度の密着力を有
するものを△、0.35Ｎ／ｍｍ以上の密着力、すなわちフ
ィルムテープにより剥離試験を行っても銅箔がカソード
から剥離しないものを○として評価した。The adhesion to the cathode was evaluated by a tape peel test. Specifically, Sumitomo 3M plastic film tape # 810 (initial peel strength: 0.35
N / mm) was adhered to the cathode surface on which the copper foil was formed, and this was peeled off to evaluate the adhesion between the copper foil and the cathode. At this time, whether the copper foil was peeled off from the cathode before peeling or the copper foil was peeled off from the cathode by a peeling force of 0.05 N / mm or less.
mm, that is, those having the same level of adhesion as the film tape, were evaluated as Δ, and those having an adhesion of 0.35 N / mm or more, that is, those in which the copper foil did not peel from the cathode even when the peeling test was performed with the film tape, were evaluated as ○.
【００３２】[0032]
【表１】 [Table 1]
【００３３】[0033]
【表２】 [Table 2]
【００３４】電解銅箔の抗張力および伸び率はＩＰＣ規
格のＩＰＣ−ＴＭ−６５０に基づき、また耐折度（回）
はＪＩＳ Ｐ ８１１５に基づきＭＩＴ耐折試験機（荷
重：５００ｇｆ.、折り曲げ速度１５０回／ｍｉｎ、曲
げ半径0.8ｍｍＲ、折り曲げ角度：左右１３５±５°）
を用いて測定した。この場合、銅箔の幅方向と長手方向
の折り曲げを交互に行い、その平均値を耐折度（回）と
した。塩素含有量は供試銅箔を硝酸、硫酸の混酸に溶解
し、この溶液に過剰の硝酸銀水溶液を加えて生成した塩
化銀沈殿の重量を測定する重量分析法により求めた。そ
の結果を表２に示す。The tensile strength and elongation percentage of the electrolytic copper foil are based on IPC-TM-650 of the IPC standard.
Is a MIT bending tester based on JIS P 8115 (load: 500 gf, bending speed 150 times / min, bending radius 0.8 mmR, bending angle: left and right 135 ± 5 °)
It measured using. In this case, the bending in the width direction and the longitudinal direction of the copper foil were alternately performed, and the average value was defined as the bending resistance (times). The chlorine content was determined by dissolving a test copper foil in a mixed acid of nitric acid and sulfuric acid, adding an excess aqueous solution of silver nitrate to the solution, and measuring the weight of silver chloride precipitate formed by a gravimetric analysis method. Table 2 shows the results.
【００３５】本発明内の添加剤範囲組成となるよう調整
した実施例１〜７においては、液流速が速くかつ高電流
密度下においてもカソードとの密着性が良好な銅箔が生
成できることがわかる。一方、本願発明の添加剤組成を
越える比較例Ｎｏ.８〜１０は、カソードとの密着性が
劣り、さらに耐折度が低く、高電流密度下での操業には
耐えることができないことがわかる。また、本願発明の
添加剤組成以下である比較例Ｎｏ.１１,１２は、カソー
ドとの密着性が劣り、さらに機械的特性に劣ることがわ
かる。In Examples 1 to 7 in which the composition of the additive range in the present invention was adjusted, it can be seen that a copper foil having a high liquid flow rate and good adhesion to the cathode even under a high current density can be produced. . On the other hand, Comparative Examples Nos. 8 to 10 exceeding the additive composition of the present invention are inferior in adhesion to the cathode, have low fold resistance, and cannot withstand operation under high current density. . In addition, it can be seen that Comparative Examples Nos. 11 and 12, which are not more than the additive composition of the present invention, are inferior in adhesion to the cathode and further inferior in mechanical properties.
【００３６】また、比較例Ｎｏ.１３は、電解液中の添
加剤組成は本願発明内であるが、電流密度を極端に低く
した例である。この場合、カソード密着性は良好である
が、電解析出に要する時間が大幅に増え、効率的な連続
操業ができない。すなわち、添加剤濃度が塩素イオン５
〜２８０ｐｐｍ、膠またはゼラチン0.1〜５０ｐｐｍ、
チオ尿素１〜５０ｐｐｍおよびポリエチレングリコール
0.5〜3.5ｇ／Ｌという条件を備えた本発明のみ、はじめ
て高電流密度下での連続操業が可能な電解銅箔を得るこ
とができることがわかる。Further, Comparative Example No. 13 is an example in which the additive composition in the electrolytic solution is within the present invention, but the current density is extremely low. In this case, the cathode adhesion is good, but the time required for electrolytic deposition is greatly increased, and efficient continuous operation cannot be performed. That is, when the additive concentration is chlorine ion 5
~ 280 ppm, glue or gelatin 0.1-50 ppm,
Thiourea 1-50 ppm and polyethylene glycol
It is understood that only the present invention having the condition of 0.5 to 3.5 g / L can obtain an electrolytic copper foil capable of continuous operation under a high current density for the first time.
【００３７】[0037]
【発明の効果】本願発明より、機械的特性に優れたカソ
ード密着性の良い銅箔を得ることができる。また、銅箔
中に存在するポリエチレングリコールによって結晶粒径
の微細化が促進され、特に耐折度の高い銅箔を得ること
ができる。これらは、プリント配線用電解銅箔の製造工
程において、高電流密度下での連続操業を可能にし、大
幅なコスト低減を実現できる極めて実用価値の高いもの
である。According to the present invention, a copper foil having excellent mechanical properties and good cathode adhesion can be obtained. In addition, the polyethylene glycol present in the copper foil promotes the miniaturization of the crystal grain size, and it is possible to obtain a copper foil having particularly high folding resistance. These are extremely practical values that enable continuous operation under a high current density in the production process of the electrolytic copper foil for printed wiring and can realize a significant cost reduction.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4E351 BB01 BB30 BB33 CC06 DD04 DD54 DD58 EE02 EE03 EE25 GG01 GG09 4K023 AA04 AA19 BA06 CA01 CA02 CA09 CB33 CB40 DA07 DA11 4K024 AA09 AB01 BA04 BC02 CA01 CA02 CA06 CA10 GA01 GA07 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4E351 BB01 BB30 BB33 CC06 DD04 DD54 DD58 EE02 EE03 EE25 GG01 GG09 4K023 AA04 AA19 BA06 CA01 CA02 CA09 CB33 CB40 DA07 DA11 4K024 AA09 AB01 BA04 BC02 CA01 CA02 GA06 CA10 GA01
Claims (8)
かつ耐折度が１５０回以上であることを特徴とする電解
銅箔。1. A tensile strength of not less than 500 N / mm 2 ,
An electrolytic copper foil having a fold resistance of 150 times or more.
００ｐｐｍであることを特徴とする請求項１記載の電解
銅箔。2. The method according to claim 1, wherein the content of chlorine in the electrolytic copper foil is 10 to 5 or less.
2. The electrolytic copper foil according to claim 1, wherein the content is 00 ppm.
れていることを特徴とする請求項１または２記載の電解
銅箔。3. The electrolytic copper foil according to claim 1, wherein the electrolytic copper foil has excellent adhesion to a cathode.
浴を用いて電解銅箔を製造するにあたり、該電解浴に塩
素イオン，膠またはゼラチン，活性硫黄含有成分および
オキシエチレン系界面活性剤を添加して電解処理を行う
ことを特徴とするカソード密着性の良好な電解銅箔の製
造方法。4. When producing an electrolytic copper foil using an acidic copper electrolytic bath containing copper sulfate and sulfuric acid as main components, the electrolytic bath contains chloride ion, glue or gelatin, an active sulfur-containing component and an oxyethylene-based surfactant. A method for producing an electrolytic copper foil having good cathode adhesion, comprising performing an electrolytic treatment by adding an agent.
り、前記オキシエチレン系界面活性剤がポリエチレング
リコールである請求項４記載の電解銅箔の製造方法。5. The method for producing an electrolytic copper foil according to claim 4, wherein said active sulfur-containing component is thiourea, and said oxyethylene-based surfactant is polyethylene glycol.
ン：５〜２８０ｐｐｍ，膠またはゼラチン：0.１〜５０
ｐｐｍ，チオ尿素：１〜５０ｐｐｍおよびポリエチレン
グリコール：0.5〜3.5ｇ／Ｌである請求項４，５記載の
電解銅箔の製造方法。6. The concentration of an additive in the electrolytic bath is: chloride ion: 5 to 280 ppm, glue or gelatin: 0.1 to 50.
The method for producing an electrolytic copper foil according to claim 4, wherein the content of thiourea is 1 to 50 ppm and the content of polyethylene glycol is 0.5 to 3.5 g / L.
量が２０００〜２００００であることを特徴とする請求
項５または６記載の電解銅箔の製造方法。7. The method for producing an electrolytic copper foil according to claim 5, wherein the average molecular weight of the polyethylene glycol is 2,000 to 20,000.
Ａ／ｄｍ2以上で、かつ供給する液流速が３ｍ／ｓｅｃ
以上での高負荷連続操業であることを特徴とする請求項
４，５，６または７記載の電解銅箔の製造方法。8. The current density applied to the electrolytic bath is 100.
A / dm 2 or more, and supply liquid flow rate is 3 m / sec
The method for producing an electrolytic copper foil according to claim 4, 5, 6, or 7, wherein the high load continuous operation is performed as described above.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30554499A JP4419161B2 (en) | 1999-10-27 | 1999-10-27 | Method for producing electrolytic copper foil |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30554499A JP4419161B2 (en) | 1999-10-27 | 1999-10-27 | Method for producing electrolytic copper foil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001123289A true JP2001123289A (en) | 2001-05-08 |
| JP4419161B2 JP4419161B2 (en) | 2010-02-24 |
Family
ID=17946448
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30554499A Expired - Lifetime JP4419161B2 (en) | 1999-10-27 | 1999-10-27 | Method for producing electrolytic copper foil |
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