JP2005154815A - Copper electrolytic solution in manufacturing electrolytic copper foil, and method for manufacturing electrolytic copper foil - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a copper electrolytic solution in manufacturing an electrolytic copper foil, which imparts a rough surface having the uniform shape and size of crests and small roughness to a deposited foil to be peeled off, without substantially lowering the yield of the deposited foil owing to difficulty of the control for the molecular weight and concentration of protein, and to provide a method for manufacturing the electrolytic copper foil with the use of the solution. <P>SOLUTION: The copper electrolytic solution in manufacturing the electrolytic copper foil includes 2 to 4.5 ppm protein with a number average molecular weight M<SB>n</SB>of 1,000 to 2,300. The electrolytic solution preferably includes 60 to 100 g/l Cu<SP>2+</SP>, 60 to 250 g/l free SO<SB>4</SB><SP>2-</SP>, and 0.5 to 2.0 ppm Cl<SP>-</SP>. The method for manufacturing the electrolytic copper foil uses the above copper electrolytic solution. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は、電解銅箔製造用銅電解液及び電解銅箔の製造方法に関し、詳しくは粗面の山の形状及び大きさが揃い、低粗度の電解銅箔を製造することに適した電解銅箔製造用銅電解液及び電解銅箔の製造方法に関するものである。 The present invention relates to a copper electrolytic solution for producing electrolytic copper foil and a method for producing electrolytic copper foil, and more specifically, an electrolytic suitable for producing a low-roughness electrolytic copper foil having a uniform shape and size of crests on a rough surface. The present invention relates to a copper electrolyte for producing copper foil and a method for producing an electrolytic copper foil.

電解銅箔は、銅イオンを含む銅電解液からチタン等からなる陰極上に銅を電析させて得られる箔（析離箔）又は該析離箔の表面にコブ等を形成したり金属層や有機成分層を設けたりした箔（表面処理箔）であり、プリント配線板の形成材料等として広く用いられている。なお、析離箔は、上記のように陰極上に電析して得られるものであるため、一般的に、陰極側の面（光沢面、シャイニー面又はＳ面）と、シャイニー面の反対側の面（粗面、マット面又はＭ面）とは、表面の形状や粗度が異なっている。すなわち、一般的に、析離箔のシャイニー面は略陰極表面の形状が略転写されて平滑状を呈し、一方粗面は電析の際に成長した銅の表面が高低差（粗度）数μｍ程度の数多くの山状突起を呈するものとなる。また、表面処理箔は、通常、析離箔の粗面の山状突起を特に研磨等することなく、略そのままの状態でさらにコブを形成する等の表面処理を行ったものであるから、その粗面の表面形状は析離箔の粗面の表面形状の影響を強く残したものとなる。すなわち、電解銅箔においては、析離箔の粗面の山状突起（以下、単に「山」ともいう。）の形状及び大きさの制御は重要である。 The electrolytic copper foil is a foil (deposited foil) obtained by electrodepositing copper on a cathode made of titanium or the like from a copper electrolytic solution containing copper ions, or a metal layer on the surface of the separated foil. And a foil (surface-treated foil) provided with an organic component layer, and is widely used as a material for forming a printed wiring board. In addition, since the separation foil is obtained by electrodeposition on the cathode as described above, generally, the cathode side surface (glossy surface, shiny surface or S surface) and the opposite side of the shiny surface. This surface (rough surface, mat surface or M surface) is different in surface shape and roughness. That is, generally, the shiny surface of the separating foil has a smooth shape with substantially the shape of the cathode surface, while the rough surface has a difference in height (roughness) in the surface of copper grown during electrodeposition. A large number of ridges of about μm are exhibited. In addition, the surface-treated foil is usually subjected to a surface treatment such as forming a bump in a substantially as-is state without particularly polishing the rough projections on the rough surface of the separation foil. The surface shape of the rough surface strongly retains the influence of the surface shape of the rough surface of the separating foil. That is, in the electrolytic copper foil, it is important to control the shape and size of the rough protrusions (hereinafter also simply referred to as “mountains”) on the rough surface of the separating foil.

ところで、電解銅箔がプリント配線板の形成材料として用いられる場合、銅箔にはプリプレグ等の他種材料との接着性等が高いことが要求されるため、表面形状の制御等により接着強度等が改善された表面処理箔が主に用いられる。しかし、表面処理箔は上記のように、その表面形状は基となる析離箔の表面形状の影響が強く残るものとなるため、接着強度等の物性を安定したものとしたり積層の際に絶縁性等を確保したりするには、析離箔の粗面の山の形状及びその大きさが揃ったものであることが望まれている。一方、近年のプリント配線板への薄型化の要請より銅箔自体の薄型化が要求されているため、表面処理箔、ひいては析離箔の粗面の山の粗度が小さいことも望まれている。析離箔の粗面の山の粗度としては、具体的には、析離箔の厚さが３５μｍのものでＲ_ｚが４．２μｍ以下であることが望まれている。 By the way, when an electrolytic copper foil is used as a material for forming a printed wiring board, the copper foil is required to have high adhesiveness with other materials such as a prepreg. The surface-treated foil with improved is mainly used. However, as described above, since the surface shape of the surface-treated foil remains strongly influenced by the surface shape of the base separation foil, it is possible to stabilize the physical properties such as adhesive strength and to insulate the laminated foil. In order to ensure the properties and the like, it is desired that the shape and size of the rough crests of the separation and separation foil are uniform. On the other hand, since the copper foil itself is required to be thinner due to the recent demand for thinner printed wiring boards, it is also desired that the roughness of the rough surface of the surface-treated foil, and hence the separation foil, be small. Yes. Specifically, the roughness of the crest of the rough surface of the separation foil is desired to be that the thickness of the separation foil is 35 μm and _Rz is 4.2 μm or less.

析離箔の粗面について、山の形状を揃え且つ粗度を低くする技術としては、従来、銅電解液中の各種イオンの濃度の制御等種々の技術が開示されている。このうち銅電解液にタンパク質やにかわ（以下、「タンパク質等」ともいう。）を溶解した水溶液（以下、「タンパク質等水溶液」ともいう。）を所定量継続して添加しつつ電解して析離箔を製造することは、低粗度箔の作製に重要な要因として知られている。 Conventionally, various techniques such as controlling the concentration of various ions in the copper electrolyte have been disclosed as techniques for aligning the shape of the peaks and reducing the roughness of the rough surface of the separating foil. Of these, a predetermined amount of an aqueous solution (hereinafter also referred to as “protein aqueous solution”) in which protein or glue (hereinafter also referred to as “protein etc.”) is dissolved in a copper electrolyte is electrolyzed and separated. Manufacturing a foil is known as an important factor in the production of low roughness foils.

すなわち、銅電解液中におけるタンパク質等の濃度や分子量は析離箔の粗面の山の形状や粗度その他の物性に影響を与えるものと考えられており、このため、銅電解液中におけるタンパク質等の濃度及び分子量を測定する方法が知られている（特許文献１）。また、タンパク質等は銅電解液中に放置するだけで分解して分子量が小さくなること、及び電解時においては消費されて銅電解液中の濃度が低くなることが知られている。 That is, it is thought that the concentration and molecular weight of proteins and the like in the copper electrolyte affect the shape, roughness and other physical properties of the rough surface of the separating foil. A method for measuring the concentration and molecular weight of these is known (Patent Document 1). In addition, it is known that proteins and the like are decomposed by simply leaving them in a copper electrolyte solution to reduce the molecular weight, and are consumed during electrolysis to reduce the concentration in the copper electrolyte solution.

特開２００１−３３７０８１号公報（第２頁第１欄）JP 2001-337081 A (2nd page, 1st column)

しかしながら、現場での操業においては、タンパク質等の濃度及び分子量を制御する方法として、溶解するタンパク質等の銘柄を特定することによりタンパク質等水溶液の作製の際における初期の分子量を制御し、且つ該タンパク質等水溶液を所定量継続して添加することにより銅電解液中の濃度を一定量に制御することが経験的に行われているにすぎないというのが実情である。すなわち、現場での操業においては、所定銘柄のタンパク質等を用いたタンパク質等水溶液を所定量継続して添加するという定常状態を作り出さないと、粗面の山の形状及びその大きさが揃ったもので且つ低粗度の析離箔を作製することが困難になる。 However, in on-site operation, as a method for controlling the concentration and molecular weight of proteins and the like, the initial molecular weight in the production of aqueous solutions of proteins and the like is controlled by specifying the brands of proteins and the like that are dissolved, and the proteins The actual situation is that the concentration in the copper electrolyte is controlled to a constant amount by adding a predetermined amount of an aqueous solution continuously. In other words, in on-site operation, the shape and size of rough peaks are aligned unless a steady state in which a predetermined amount of a protein aqueous solution using a predetermined brand of protein is continuously added is created. In addition, it is difficult to produce a low roughness precipitation foil.

例えば、電解時にタンパク質等水溶液の添加時間や添加量を誤った場合や新たに銅電解液を作製する場合、前者の場合には、タンパク質等の不足分を追って添加することになるが、このように不足分を添加しても、得られる析離箔の粗面の山の形状や粗度を定常状態の良好な状態、すなわち、山の形状が整い且つ粗度が低い状態に戻すことが困難でありこの間の析離箔の歩留まりが著しく低下するという問題があった。また、後者の場合には、操業の定常状態の条件でタンパク質等水溶液を添加しても粗面の山の形状が整い且つ粗度が低い箔を得ることが困難であり、操業開始初期における析離箔の歩留まりが著しく低くなるという問題があった。さらに、たとえ同一銘柄のタンパク質を用いても、電解製造のラインが異なるだけで、得られる箔のＭ面の山の形状等が変化してしまうこともあるという問題があった。 For example, if the addition time or amount of an aqueous solution such as protein is wrong during electrolysis or if a new copper electrolyte is prepared, in the former case, protein or the like will be added shortly. Even if a deficiency is added, it is difficult to return the rough shape and roughness of the rough surface of the resulting separation foil to a steady state, that is, a state where the shape of the peak is uniform and the roughness is low. However, there was a problem that the yield of the separation foil during this period was remarkably lowered. Further, in the latter case, it is difficult to obtain a foil having a rough crest shape and low roughness even when an aqueous protein solution is added under the steady state conditions of the operation. There has been a problem that the yield of the release foil is remarkably lowered. Furthermore, even if proteins of the same brand are used, there is a problem in that the shape of the mountain on the M surface of the obtained foil may change only by the difference in the electrolytic production line.

従って、本発明の目的は、タンパク質等の分子量及び濃度の管理に起因する析離箔の歩留まりを実質的に生じさせないまま、析離箔の粗面の山の形状及び大きさが揃い且つ低粗度の箔を得ることができる電解銅箔製造用銅電解液及びこれを用いた電解銅箔の製造方法を提供することにある。 Therefore, the object of the present invention is to achieve a uniform shape and size of the ridges on the rough surface of the separation foil, while maintaining substantially no yield of the separation foil due to the control of the molecular weight and concentration of proteins and the like. It is providing the copper electrolyte solution for electrolytic copper foil manufacture which can obtain the foil of a degree, and the manufacturing method of an electrolytic copper foil using the same.

かかる実情において、本発明者は鋭意検討を行った結果、電解銅箔製造用の銅電解液中に含まれるタンパク質の数平均分子量及び濃度がそれぞれ所定範囲内にある銅電解液を用いると、析離箔の粗面の山の形状及び大きさが揃い且つ低粗度になることを見出し、本発明を完成するに至った。 In such a situation, the present inventor has intensively studied, and as a result, when using a copper electrolyte in which the number average molecular weight and the concentration of the protein contained in the copper electrolyte for producing an electrolytic copper foil are within a predetermined range, It has been found that the shapes and sizes of the peaks of the rough surface of the release foil are uniform and have low roughness, and the present invention has been completed.

すなわち、本発明（１）は、電解銅箔製造用の銅電解液であって、該銅電解液中に含まれるタンパク質は、数平均分子量Ｍ_ｎが１０００〜２３００、且つ、濃度が２ｐｐｍ〜４．５ｐｐｍであることを特徴とする電解銅箔製造用銅電解液を提供するものである。 That is, the present invention (1) is a copper electrolyte for producing an electrolytic copper foil, and the protein contained in the copper electrolyte has a number average molecular weight _Mn of 1000 to 2300 and a concentration of 2 ppm to 4 The present invention provides a copper electrolyte solution for producing an electrolytic copper foil, characterized by being 0.5 ppm.

また、本発明（２）は、本発明（１）において、前記銅電解液は、Ｃｕ^２＋濃度が６０ｇ／ｌ〜１００ｇ／ｌであることを特徴とする電解銅箔製造用銅電解液を提供するものである。 In addition, the present invention (2) provides the copper electrolyte for producing an electrolytic copper foil according to the present invention (1), wherein the copper electrolyte has a Cu ²⁺ concentration of 60 g / l to 100 g / l. To do.

また、本発明（３）は、本発明（１）又は（２）において、前記銅電解液は、フリーＳＯ_４ ^２−濃度が６０ｇ／ｌ〜２５０ｇ／ｌであることを特徴とする電解銅箔製造用銅電解液を提供するものである。 Further, the present invention (3) is the electrolytic copper foil according to the present invention (1) or (2), wherein the copper electrolyte has a free SO ₄ ²⁻ concentration of 60 g / l to 250 g / l. A copper electrolyte for production is provided.

また、本発明（４）は、本発明（１）〜（３）のいずれかにおいて、前記銅電解液は、温度が４０℃〜６０℃であることを特徴とする電解銅箔製造用銅電解液を提供するものである。 In addition, the present invention (4) is any one of the present inventions (1) to (3), wherein the copper electrolyte has a temperature of 40 ° C to 60 ° C. A liquid is provided.

また、本発明（５）は、本発明（１）〜（４）のいずれかにおいて、前記銅電解液は、Ｃｌ⁻濃度が０．５ｐｐｍ〜２．０ｐｐｍであることを特徴とする電解銅箔製造用銅電解液を提供するものである。 Further, the present invention (5) is the electrolytic copper foil according to any one of the present inventions (1) to (4), wherein the copper electrolyte has a Cl ⁻ concentration of 0.5 ppm to 2.0 ppm. A copper electrolyte for production is provided.

また、本発明（６）は、本発明（１）〜（５）のいずれかに記載の電解銅箔製造用銅電解液を用いる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。 Moreover, this invention (6) provides the manufacturing method of the electrolytic copper foil characterized by using the copper electrolyte solution for electrolytic copper foil manufacture in any one of this invention (1)-(5). is there.

また、本発明（７）は、本発明（６）において、電解電流密度が３０Ａ／ｃｍ^２〜７０Ａ／ｃｍ^２である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。 Further, the present invention (7), in the present invention (6), there is provided a method of manufacturing an electrolytic copper foil, wherein the electrolytic current density of ^{30A / cm 2 ~70A / cm 2} .

本発明に係る電解銅箔製造用銅電解液によれば、電解時における銅電解液中に含まれるタンパク質の数平均分子量Ｍ_ｎ及び濃度を所定範囲内に特定したため、析離箔の粗面の山の形状が整い且つ低粗度の箔を得ることができる。また、タンパク質は通常銅電解液中で容易に分解されるため、数平均分子量Ｍ_ｎが上記所定範囲以上のタンパク質であっても、これを原料として用いることができることから、使用可能なタンパク質の選択の幅が広がる。さらに、析離箔の粗面の山の形状が整い且つ低粗度の箔を得るためのタンパク質の分子量及び濃度の管理範囲が明確になったため、従来、タンパク質の使用銘柄を特定して銅電解液中の初期の数平均分子量Ｍ_ｎを実質的に管理したり、該タンパク質の水溶液を銅電解液に所定量加えたりするといった経験的な作業標準工程に拘束されることなく、析離箔の粗面の山の形状が整い且つ低粗度の箔を製造するのに好ましい銅電解液を短時間で調製することができる。また、このように銅電解液を短時間で調製することができるため、銅電解液中のタンパク質の管理に起因する析離箔の歩留まりを極めて小さくすることができる。さらに、電解液中におけるタンパク質の目標分子量及び濃度を所定の管理値に合わせるだけでタンパク質の管理が済むため、ライン毎の電解液の調製が容易に行え、ラインの立ち上げを早くすることができる。また、本発明に係る電解銅箔の製造方法によれば、上記銅電解液を用いることにより、析離箔の粗面の山の形状が整い且つ低粗度の箔を得ることができる。 According to the copper electrolytic solution for producing an electrolytic copper foil according to the present invention, the number average molecular weight M _n and the concentration of the protein contained in the copper electrolytic solution during electrolysis are specified within a predetermined range. It is possible to obtain a foil having a uniform mountain shape and low roughness. In addition, since proteins are usually easily decomposed in a copper electrolyte solution, even if the number average molecular weight M _n is a protein having the above predetermined range or more, it can be used as a raw material. The width of. In addition, the control range of protein molecular weight and concentration in order to obtain a rough surface crest of the separating and separating foil and to obtain a low roughness foil has been clarified. The initial number average molecular weight _Mn in the liquid is substantially controlled, and the analysis of the separation foil is not constrained by empirical standard operations such as adding a predetermined amount of the aqueous solution of the protein to the copper electrolyte. It is possible to prepare a copper electrolyte solution that is suitable for producing a foil having a rough crest shape and a low roughness in a short time. In addition, since the copper electrolyte can be prepared in a short time as described above, the yield of the separation foil resulting from the management of the protein in the copper electrolyte can be extremely reduced. Furthermore, since protein management is completed simply by adjusting the target molecular weight and concentration of the protein in the electrolyte solution to the predetermined control values, the electrolyte solution for each line can be easily prepared, and the line can be started up quickly. . Moreover, according to the manufacturing method of the electrolytic copper foil which concerns on this invention, the shape of the peak of the rough surface of separation | separation foil can be prepared and foil with low roughness can be obtained by using the said copper electrolyte solution.

（本発明に係る電解銅箔製造用銅電解液）
本発明に係る電解銅箔製造用銅電解液は、電解銅箔製造用の銅電解液である。該銅電解液としては、銅イオン（Ｃｕ^２＋）を含む電解可能な液であればよく、例えば酸性浴を用いることができ、酸性浴としては、例えば、硫酸浴等を用いることができる。硫酸浴は、得られる析離箔の物性がよく、廃水処理が容易であり、また、銅電解液の原料である銅線等を容易に溶解することができるため好ましい。 (Copper electrolyte for producing electrolytic copper foil according to the present invention)
The copper electrolyte solution for producing an electrolytic copper foil according to the present invention is a copper electrolyte solution for producing an electrolytic copper foil. The copper electrolytic solution may be any electrolytic solution containing copper ions (Cu ²⁺ ). For example, an acidic bath may be used. As the acidic bath, for example, a sulfuric acid bath may be used. A sulfuric acid bath is preferable because the obtained foil has good physical properties, can be easily treated with waste water, and can easily dissolve a copper wire or the like as a raw material for the copper electrolyte.

上記銅電解液は、Ｃｕ^２＋濃度が通常６０ｇ／ｌ〜１００ｇ／ｌ、好ましくは７０ｇ／ｌ〜９０ｇ／ｌである。Ｃｕ^２＋濃度が６０ｇ／ｌ未満であると溶液抵抗が高くなるため好ましくなく、また、１００ｇ／ｌを超えると硫酸銅の結晶が析出し易くなるため好ましくない。 The copper electrolyte has a Cu ²⁺ concentration of usually 60 g / l to 100 g / l, preferably 70 g / l to 90 g / l. If the Cu ²⁺ concentration is less than 60 g / l, the solution resistance becomes high, which is not preferable, and if it exceeds 100 g / l, copper sulfate crystals tend to precipitate, which is not preferable.

上記銅電解液は、硫酸浴である場合、フリーＳＯ_４ ^２−濃度が通常６０ｇ／ｌ〜２５０ｇ／ｌ、好ましくは１００ｇ／ｌ〜２００ｇ／ｌである。ここでフリーＳＯ_４ ^２−濃度とは、銅電解液中のＣｕ^２＋濃度をＣｕＳＯ_４に換算して得られるＳＯ_４ ^２−濃度を、銅電解液中に含まれる全ＳＯ_４ ^２−濃度から減じた残余のＳＯ_４ ^２−濃度を示す。フリーＳＯ_４ ^２−濃度が６０ｇ／ｌ未満であると溶液抵抗が高くなるため好ましくなく、また２５０ｇ／ｌを超えると析離箔に析出異常が生じ易いため好ましくない。本発明において析離箔とは、銅イオンを含む銅電解液からチタン等からなる陰極上に銅を電析させて得られる銅箔であってコブ処理等の表面処理をしていない銅箔、すなわち、未表面処理銅箔を意味する。 When the copper electrolyte is a sulfuric acid bath, the free SO ₄ ²⁻ concentration is usually 60 g / l to 250 g / l, preferably 100 g / l to 200 g / l. Here, the free _SO ^{4 2-concentration} reduces the _SO ^{4 2-density} obtained by converting the ^{Cu 2+} concentration in the copper electrolyte solution to CuSO _4, from the total _SO ^{4 2-concentration} in the copper electrolyte solution The remaining SO ₄ ²⁻ concentration is shown. If the free SO ₄ ²⁻ concentration is less than 60 g / l, the solution resistance becomes high, which is not preferable, and if it exceeds 250 g / l, an abnormal precipitation tends to occur in the separation foil, which is not preferable. In the present invention, the separation foil is a copper foil obtained by electrodepositing copper on a cathode made of titanium or the like from a copper electrolyte containing copper ions, and a copper foil that is not subjected to a surface treatment such as a lump treatment, That is, it means an unsurface-treated copper foil.

上記銅電解液は、Ｃｌ⁻濃度が通常０．５ｐｐｍ〜２．０ｐｐｍ、好ましくは１．５ｐｐｍ〜１．９ｐｐｍである。なお、本明細書においてｐｐｍとは、ｍｇ／ｌを示す。Ｃｌ⁻濃度が０．５ｐｐｍ未満であると本発明のタンパク質濃度において山の形状が良好でなくなるため好ましくなく、また、２．０ｐｐｍを超えると析離箔にマイクロポロシティーが発生し易いため好ましくない。本発明では、このようにタンパク質の濃度及び分子量と、Ｃｌ⁻濃度とがそれぞれ所定範囲内にある場合に析離箔の山の形状等が良好であることから、析離箔の山の形状の制御に関し、タンパク質の濃度及び分子量と、Ｃｌ⁻濃度との間になんらかの相関関係があるものと推測される。 The copper electrolyte has a Cl ⁻ concentration of usually 0.5 ppm to 2.0 ppm, preferably 1.5 ppm to 1.9 ppm. In addition, in this specification, ppm shows mg / l. When the Cl ⁻ concentration is less than 0.5 ppm, the shape of the mountain is not good at the protein concentration of the present invention, and when it exceeds 2.0 ppm, it is not preferable because microporosity tends to occur in the separation foil. . In the present invention, when the protein concentration and molecular weight and the Cl ⁻ concentration are within the predetermined ranges, the shape of the separation foil crest is good. With respect to control, it is assumed that there is some correlation between protein concentration and molecular weight and Cl ⁻ concentration.

上記銅電解液は、タンパク質を含む。タンパク質としては、例えば、ゼラチン、にかわ等が挙げられる。また、銅電解液にタンパク質を含有させるためには、通常タンパク質を水に溶解した後、該タンパク質水溶液を銅電解液に添加するが、該タンパク質水溶液を作製する場合に用いる原料のタンパク質としては、数平均分子量Ｍ_ｎが
１７００以上のものが用いられる。この理由は、タンパク質は、銅電解液中又は水溶液で分解される等により数平均分子量Ｍ_ｎが低下するものであるため、銅電解液中における数平均分子量Ｍ_ｎを後述の１０００〜２３００とするには分解を考慮して該下限値よりも若干高いと好ましいからである。 The copper electrolyte contains protein. Examples of the protein include gelatin and glue. In order to contain protein in the copper electrolyte, the protein is usually dissolved in water, and then the protein aqueous solution is added to the copper electrolyte. As a raw material protein used for preparing the protein aqueous solution, Those having a number average molecular weight _Mn of 1700 or more are used. This is because the protein, the number-average molecular weight M _n by the like which is decomposed by the copper electrolyte solution or aqueous solution is one that decreases, the number average molecular weight M _n in the copper electrolyte solution and 1000-2300 will be described later This is because it is preferably slightly higher than the lower limit in consideration of decomposition.

原料のタンパク質としては、例えば、銅電解液中における数平均分子量Ｍ_ｎを該範囲内のものとすることができるものであればよいため特に限定されないが、例えば、旭陽化学工業株式会社製ＤＶＭ８０、新田ゼラチン株式会社製ＵＤＢ、新田ゼラチン株式会社製ＳＣＰ５０００、新田ゼラチン株式会社製７００Ｆ等を用いることができる。 The raw material protein is not particularly limited, for example, as long as the number average molecular weight _Mn in the copper electrolyte solution can be within the above range. For example, DVM80 manufactured by Asahi Chemical Industry Co., Ltd. UDB manufactured by Nitta Gelatin Co., Ltd., SCP5000 manufactured by Nitta Gelatin Co., Ltd., 700F manufactured by Nitta Gelatin Co., Ltd., and the like can be used.

上記銅電解液中に含まれるタンパク質は、数平均分子量Ｍ_ｎが通常１０００〜２３００、好ましくは１２００〜２１００であり、且つ、濃度が通常２ｐｐｍ〜４．５ｐｐｍ、好ましくは２．０ｐｐｍ〜３．６ｐｐｍ、さらに好ましくは２．５ｐｐｍを超え３．６ｐｐｍ以下である。銅電解液中のタンパク質の数平均分子量Ｍ_ｎ及び濃度が上記範囲内にあると、析離箔の粗面の山の形状及び大きさが揃い且つ低粗度の箔を得ることができるため好ましい。なお、本発明において、タンパク質の数平均分子量Ｍ_ｎ及び濃度とは、数平均分子量Ｍ_ｎが７９０以上のタンパク質の数平均分子量Ｍ_ｎ及び濃度をいう。 The protein contained in the copper electrolyte has a number average molecular weight _Mn of usually 1000 to 2300, preferably 1200 to 2100, and a concentration of usually 2 ppm to 4.5 ppm, preferably 2.0 ppm to 3.6 ppm. More preferably, it is more than 2.5 ppm and not more than 3.6 ppm. It is preferable that the number average molecular weight M _n and the concentration of the protein in the copper electrolyte solution are within the above-mentioned ranges because the rough surface of the separation foil has a uniform shape and size of the crest and a low roughness foil can be obtained. . In the present invention, the number average molecular weight M _n and the concentration of the protein, the number-average molecular weight M _n refers to the number-average molecular weight M _n and density of 790 or more proteins.

ここで、上記銅電解液中に含まれるタンパク質の数平均分子量Ｍ_ｎ及び濃度と、析離箔の常態の抗張力との関係を図１９に示し、上記銅電解液中に含まれるタンパク質の数平均分子量Ｍ_ｎ及び濃度と、析離箔の粗面の粗度Ｒ_ｚとの関係を図２０に示す。図１９において、横軸は銅電解液中に含まれるタンパク質分子量Ｍ_ｎを示し、縦軸は析離箔の常態の抗張力を示す。また、図２０において、横軸は銅電解液中に含まれるタンパク質分子量Ｍ_ｎを示し、縦軸は析離箔の粗面の粗度Ｒ_ｚを示す。 Here, the relationship between the number average molecular weight _Mn and concentration of the protein contained in the copper electrolyte and the normal tensile strength of the separation foil is shown in FIG. 19, and the number average of the protein contained in the copper electrolyte is shown in FIG. FIG. 20 shows the relationship between the molecular weight M _n and concentration and the roughness R _z of the rough surface of the separating foil. In FIG. 19, the horizontal axis represents the protein molecular weight _Mn contained in the copper electrolyte, and the vertical axis represents the normal tensile strength of the separation foil. Further, in FIG. 20, the horizontal axis indicates the protein molecular weight M _n contained in the copper electrolyte, and the vertical axis shows the roughness R _z of the rough surface of the deposited foil.

また、図１９及び図２０において、銅電解液中のタンパク質の濃度が１．５ｐｐｍ未満の試料を正方形のプロット（以下、「プロットＡ」といい、プロットＡの形成する群を「プロットＡ群」という。）、１．５ｐｐｍ〜２．５ｐｐｍの試料を三角のプロット（以下、「プロットＢ」といい、プロットＢの形成する群を「プロットＢ群」という。）、２．５ｐｐｍを超える試料を縦に菱形のプロット（以下、「プロットＣ」といい、プロットＣの形成する群を「プロットＣ群」という。）で示す。 19 and 20, a sample having a protein concentration of less than 1.5 ppm in the copper electrolyte is referred to as a square plot (hereinafter referred to as “plot A”, and the group formed by plot A is referred to as “plot A group”. A sample of 1.5 ppm to 2.5 ppm is a triangular plot (hereinafter referred to as “plot B”, a group formed by the plot B is referred to as “plot B group”), and a sample exceeding 2.5 ppm. A vertical diamond plot (hereinafter referred to as “plot C”, and a group formed by plot C is referred to as “plot C group”) is shown.

図１９及び図２０より、プロットＡ群、プロットＢ群及びプロットＣ群を比較すると、銅電解液中に含まれるタンパク質の濃度が同程度であれば、銅電解液中に含まれるタンパク質の数平均分子量Ｍ_ｎが小さくなるほど、析離箔の常態の抗張力が高く且つ粗度Ｒ_ｚが小さくなる傾向にあることが判る。また、プロットＡ群、プロットＢ群及びプロットＣ群を比較すると、銅電解液中に含まれるタンパク質の数平均分子量Ｍ_ｎが同程度であれば、銅電解液中に含まれるタンパク質の濃度が高くなるほど、析離箔の常態の抗張力が高く且つ粗度Ｒ_ｚが小さくなる傾向にあることが判る。従って、タンパク質の数平均分子量Ｍ_ｎが小さくなり且つタンパク質の濃度が高くなるほど、析離箔の常態の抗張力が高く且つ粗度Ｒ_ｚが小さくなる傾向にあることが判る。 From FIG. 19 and FIG. 20, when the plot A group, the plot B group, and the plot C group are compared, if the concentration of the protein contained in the copper electrolyte solution is approximately the same, the number average of the proteins contained in the copper electrolyte solution It can be seen that the smaller the molecular weight _{Mn, the} higher the normal tensile strength of the separating foil and the lower the roughness _Rz . Moreover, when the plot A group, the plot B group, and the plot C group are compared, if the number average molecular weight _Mn of the protein contained in the copper electrolyte is approximately the same, the concentration of the protein contained in the copper electrolyte is high. It can be seen that the normal tensile strength of the separating and separating foil tends to be high and the roughness _Rz tends to be small. Therefore, it can be seen that as the number average molecular weight M _n of the protein decreases and the protein concentration increases, the normal tensile strength of the separation foil tends to be high and the roughness R _z tends to decrease.

上記のようにタンパク質の数平均分子量Ｍ_ｎが小さくなり且つタンパク質の濃度が高くなるほど析離箔の常態の抗張力が高く且つ粗度Ｒ_ｚが小さくなるため好ましい。しかし、一方で、タンパク質の濃度が高すぎると銅電解液の粘度が高くなりすぎて起泡し易く好ましくないという問題があり、また、タンパク質の数平均分子量Ｍ_ｎが小さすぎると、銅電解液中に必要なタンパク質の濃度が高くなって上記のように銅電解液の粘度が高くなりすぎて起泡し易く好ましくないという問題があるため、本発明では、上記のようにタンパク質の数平均分子量Ｍ_ｎの下限値及びタンパク質の濃度の上限値を設けている。 As described above, the lower the number average molecular weight _Mn of the protein and the higher the protein concentration, the higher the normal tensile strength of the separation foil and the lower the roughness _{Rz, which} is preferable. However, on the other hand, if the protein concentration is too high, there is a problem that the viscosity of the copper electrolyte solution is too high and foaming is not preferable, and if the number average molecular weight M _{n of the} protein is too small, the copper electrolyte solution is too low. In the present invention, the number average molecular weight of the protein is as described above because the concentration of the necessary protein is high and the viscosity of the copper electrolyte solution is too high as described above, which is not preferable. A lower limit value of M _{n and} an upper limit value of protein concentration are provided.

さらに、銅電解液中に含まれるタンパク質の数平均分子量Ｍ_ｎが小さくなるのに対して析離箔の常態の抗張力が高くなる度合い、すなわち、図１９の横軸（タンパク質の数平均分子量Ｍ_ｎ）に対するプロットＡ群、プロットＢ群及びプロットＣ群それぞれの形成する傾きは、プロットＡ群の形成する傾き、プロットＢ群の形成する傾き及びプロットＣ群の形成する傾きの順番に、前者ほど傾きの右肩下がりになる度合いが大きくなっており、後者ほど傾きの右肩下がりになる度合いが小さくなって傾きが水平に近づいていることが判る。このため、銅電解液中のタンパク質の濃度が高くなるほどタンパク質の数平均分子量Ｍ_ｎの変化に対する析離箔の常態の抗張力の変化が鈍感になって、銅電解液中のタンパク質の濃度の変化の影響による析離箔の常態の抗張力のばらつきが少なくなり易いことがわかる。一方、銅電解液中のタンパク質の濃度が低くなるほどタンパク質の数平均分子量Ｍ_ｎの変化に対する析離箔の常態の抗張力の変化が鋭敏になって、銅電解液中のタンパク質の濃度の変化の影響による析離箔の常態の抗張力のばらつきが大きくなり易いことが判る。 Furthermore, while the number average molecular weight M _{n of the} protein contained in the copper electrolyte decreases, the normal tensile strength of the separation foil increases, that is, the horizontal axis (number average molecular weight M _{n of the} protein in FIG. 19). The slope formed by each of the plot A group, the plot B group, and the plot C group in the order of the slope formed by the plot A group, the slope formed by the plot B group, and the slope formed by the plot C group is inclined as the former. It can be seen that the degree of the lowering of the right shoulder is greater, and the latter the smaller the degree of the lowering of the right shoulder, and the inclination approaches the horizontal. For this reason, as the protein concentration in the copper electrolyte increases, the change in the normal tensile strength of the separation foil with respect to the change in the number average molecular weight _Mn of the protein becomes less sensitive, and the change in the concentration of the protein in the copper electrolyte becomes less sensitive. It can be seen that the variation in the normal tensile strength of the separating foil due to the influence tends to be reduced. On the other hand, the lower the protein concentration in the copper electrolyte solution, the more sensitive the change in the normal tensile strength of the separation foil with respect to the change in the number average molecular weight _Mn of the protein, and the influence of the change in the protein concentration in the copper electrolyte solution. It can be seen that the variation in the normal tensile strength of the deposited foil due to the film tends to increase.

また、銅電解液中に含まれるタンパク質の数平均分子量Ｍ_ｎが小さくなるのに対して粗度Ｒ_ｚが小さくなる度合い、すなわち、図２０の横軸（タンパク質の数平均分子量Ｍ_ｎ）に対するプロットＡ群、プロットＢ群及びプロットＣ群それぞれの形成する傾きは、プロットＡ群の形成する傾き、プロットＢ群の形成する傾き及びプロットＣ群の形成する傾きの順番に、前者ほど傾きの右肩上がりになる度合いが大きくなっており、後者ほど傾きの右肩上がりになる度合いが小さくなって傾きが水平に近づいていることが判る。このため、銅電解液中のタンパク質の濃度が高くなるほどタンパク質の数平均分子量Ｍ_ｎの変化に対する析離箔の粗度Ｒ_ｚの変化が鈍感になって、銅電解液中のタンパク質の濃度の変化の影響による析離箔の粗度Ｒ_ｚのばらつきが少なくなり易いことがわかる。一方、銅電解液中のタンパク質の濃度が低くなるほどタンパク質の数平均分子量Ｍ_ｎの変化に対する析離箔の粗度Ｒ_ｚの変化が鋭敏になって、銅電解液中のタンパク質の濃度の変化の影響による析離箔の粗度Ｒ_ｚのばらつきが大きくなり易いことが判る。 Further, the degree to which the roughness R _z is reduced while the number average molecular weight M _{n of the} protein contained in the copper electrolyte is reduced, that is, a plot with respect to the horizontal axis (number average molecular weight M _{n of the} protein) in FIG. The slope formed by each of the A group, the plot B group, and the plot C group is in the order of the slope formed by the plot A group, the slope formed by the plot B group, and the slope formed by the plot C group. It can be seen that the degree of rising is larger, and the latter is less inclined to the right and the inclination is closer to the horizontal. For this reason, as the protein concentration in the copper electrolyte increases, the change in the roughness _Rz of the separating foil with respect to the change in the number average molecular weight _Mn of the protein becomes insensitive, and the change in the protein concentration in the copper electrolyte it can be seen that the likely less variation in roughness R _z of the deposited foil due. On the other hand, the lower the protein concentration in the copper electrolyte solution, the more sensitive the change in the roughness _Rz of the separation foil with respect to the change in the number average molecular weight _Mn of the protein, and the change in the protein concentration in the copper electrolyte solution. variations in the roughness R _z of deposited foil due is seen that tends to increase.

ここで、銅電解液中に含まれるタンパク質の数平均分子量Ｍ_ｎ及び濃度の測定方法について説明する。該測定方法は、特開２００１−３３７０８１号公報に開示されている方法を用いることができ、具体的には、カラムスイッチング法を併用した高速液体クロマトグラフィ、好ましくはゲルパーミエーションクロマトグラフィにより測定するタンパク質の濃度及び分子量分布の測定方法である。該測定方法においては、移動相としてアセトニトリル３容量％以上、濃度０．００２Ｍ〜０．０１Ｍの希硫酸９７容量％以下の混合溶液を用い、前処理カラムの充填剤として排除限界分子量が２５００以下のサイズ排除モードの充填剤を用い、分離カラムの充填剤として排除限界分子量が１００００以上のサイズ排除モードの充填剤を用いることが好ましく、また、上記分離カラムは２本以上直列に接続したものであることが好ましい。上記の測定方法を用いることにより、銅電解液中に含まれるタンパク質の分子量分布及び濃度を測定し、該分子量分布より数平均分子量Ｍ_ｎを算出する。 Here, a method for measuring the number average molecular weight M _n and the concentration of the protein contained in the copper electrolyte will be described. As the measurement method, the method disclosed in Japanese Patent Application Laid-Open No. 2001-337081 can be used, and specifically, a high-performance liquid chromatography combined with a column switching method, preferably a gel permeation chromatography. This is a method for measuring concentration and molecular weight distribution. In this measurement method, a mixed solution of 3% by volume or more of acetonitrile and 97% by volume or less of dilute sulfuric acid having a concentration of 0.002M to 0.01M is used as a mobile phase, and an exclusion limit molecular weight of 2500 or less is used as a packing for a pretreatment column. It is preferable to use a size exclusion mode packing, and use a size exclusion mode packing having an exclusion limit molecular weight of 10,000 or more as a packing for the separation column. Further, two or more separation columns are connected in series. It is preferable. By using the above measurement method, the molecular weight distribution and concentration of the protein contained in the copper electrolyte are measured, and the number average molecular weight M _n is calculated from the molecular weight distribution.

さらに、タンパク質の数平均分子量Ｍ_ｎ及び濃度の測定方法について図面を参照して詳細に説明する。図２１は本発明におけるタンパク質の数平均分子量Ｍ_ｎ及び濃度の測定方法で用いる装置の一例を示す概略説明図である。図２１に示す測定装置は、送液ポンプ１と、６方切換バルブ３と、送液ポンプ１と６方切換バルブ３の第１の連結口４との間に連結配置されたインジェクタ２と、切換バルブの第２の連結口５に連結配置された前処理カラム１０と、前処理カラム１０と切換バルブの第５の連結口８との間に連結配置された第１検出器１１と、切換バルブの第６の連結口９に２基直列に連結配置された分離カラム１２、１２と、分離カラム１２と切換バルブの第３の連結口６との間に連結配置された第２検出器１３と、第２検出器１３での検出データに基づいてタンパク質の濃度及び分子量分布を求めるためのデータ処理装置（図示せず）と、切換バルブの第４の連結口７に連結配置された排液パイプ１４と、前処理カラム及び該分離カラムを一定温度に保つための恒温槽１５とを有する。配管には好ましくはＰＥＥＫ製又はテフロン（登録商標）製のチューブを用いる。 Further, a method for measuring the number average molecular weight M _n and the concentration of the protein will be described in detail with reference to the drawings. FIG. 21 is a schematic explanatory view showing an example of an apparatus used in the method for measuring the number average molecular weight M _n and concentration of a protein in the present invention. The measuring device shown in FIG. 21 includes a liquid feed pump 1, a 6-way switching valve 3, an injector 2 that is connected between the liquid feed pump 1 and the first connection port 4 of the 6-way switching valve 3, A pretreatment column 10 connected to the second connection port 5 of the switching valve; a first detector 11 connected to the pretreatment column 10 and the fifth connection port 8 of the switching valve; Two separation columns 12 and 12 connected in series to the sixth connection port 9 of the valve, and a second detector 13 connected and arranged between the separation column 12 and the third connection port 6 of the switching valve. And a data processing device (not shown) for determining the concentration and molecular weight distribution of the protein based on the detection data of the second detector 13, and the drainage connected to the fourth connection port 7 of the switching valve. The pipe 14, the pretreatment column and the separation column are kept at a constant temperature. And a thermostatic bath 15 for fit. For piping, a tube made of PEEK or Teflon (registered trademark) is preferably used.

検出器１１及び１３としては、ｍｇ／ｌレベルのタンパク質を検出することのできる、高速液体クロマトグラフィに一般に用いられている検出器を用いることができ、例えば吸光光度検出器を用いることができる。また、本発明においては、検出器１１及び１３で検出したデータに基づいてタンパク質の濃度及び分子量分布を求めるための演算機能を持ったいかなるデータ処理装置も用いることができる。 As the detectors 11 and 13, a detector that can detect a protein at a mg / l level and generally used in high performance liquid chromatography can be used. For example, an absorptiometric detector can be used. In the present invention, any data processing device having a calculation function for obtaining the protein concentration and molecular weight distribution based on the data detected by the detectors 11 and 13 can be used.

上記のような測定装置を用いて測定する際に、まず、６方切換バルブ３により、第１の連結口４と第２の連結口５とを連絡させ、第５の連結口８と第６の連結口９とを連絡させ、かつ第３の連結口６と第４の連結口７とを連絡させる。この状態で、例えば０．００５Ｍ硫酸とアセトニトリルとの容量比９５：５の混合溶液からなる移動相を送液ポンプ１により一定流量で、移動相溜め１６→送液ポンプ１→インジェクタ２→６方切換バルブ３→前処理カラム１０→第１検出器１１→６方切換バルブ３→分離カラム１２、１２→第２検出器１３→６方切換バルブ３→排液パイプ１４の順で流動させる。この状態で、タンパク質を含有している電解液２００μｌを直接に又は純水で希釈した試料２００μｌをインジェクタ２に導入する。電解液は排除限界分子量が２５００以下の水系のサイズ排除モード充填剤を充填した前処理カラム１０、例えば、アマシャムファルマシアバイオテク株式会社製、セファデックスＧ−１５（排除限界分子量１５００）を収容した内径７．５ｍｍ、長さ２５０ｍｍのＰＥＥＫ製カラムに流入する。前処理カラム１０に流入した電解液はサイズ排除クロマトグラフィの分離原理により分離されて分子量の大きいタンパク質が先に溶出し、その後低分子量物質である電解質成分が溶出する。 When measuring using the measuring apparatus as described above, first, the first connection port 4 and the second connection port 5 are connected by the six-way switching valve 3, and the fifth connection port 8 and the sixth connection port 5 are connected. The third connection port 6 and the fourth connection port 7 are communicated with each other. In this state, for example, a mobile phase composed of a mixed solution of 0.005M sulfuric acid and acetonitrile in a volume ratio of 95: 5 is supplied at a constant flow rate by the liquid feed pump 1, and the mobile phase reservoir 16 → liquid feed pump 1 → injector 2 → 6 direction. The flow is made in the order of the switching valve 3 → the pretreatment column 10 → the first detector 11 → the six-way switching valve 3 → the separation column 12, 12 → the second detector 13 → the six-way switching valve 3 → the drain pipe 14. In this state, 200 μl of a sample obtained by diluting 200 μl of an electrolyte containing protein directly or with pure water is introduced into the injector 2. The electrolyte has a pretreatment column 10 packed with an aqueous size exclusion mode filler having an exclusion limit molecular weight of 2500 or less, for example, an inner diameter 7 containing Sephadex G-15 (exclusion limit molecular weight 1500) manufactured by Amersham Pharmacia Biotech Co., Ltd. It flows into a PEEK column having a length of 5 mm and a length of 250 mm. The electrolyte flowing into the pretreatment column 10 is separated according to the separation principle of size exclusion chromatography, and the protein having a large molecular weight is eluted first, and then the electrolyte component that is a low molecular weight substance is eluted.

前処理カラム１０から溶出されたタンパク質及び電解質成分を第１検出器１１、例えば吸光光度検出器において測定波長２１０ｎｍでモニターし、タンパク質が分離カラム１２、１２に導入された後で、大量の電解質成分が分離カラム１２、１２に導入される前に、６方切換バルブを切換えて第１の連結口４と第６の連結口９とを連絡させ、第３の連結口６と第２の連結口５とを連絡させ、かつ第５の連結口８と第４の連結口７とを連絡させる。この状態では移動相は、移動相溜め１６→送液ポンプ１→インジェクタ２→６方切換バルブ３→分離カラム１２、１２→第２検出器１３→６方切換バルブ３→前処理カラム１０→第１検出器１１→６方切換バルブ３→排液パイプ１４の順で流動し、電解質成分を排液パイプ１４経由で系外に排出させる。なお、上記タンパク質の濃度及び分子量分布の測定方法を採用すると、通常分子量７９０以上のタンパク質を測定することが可能であるので、６方切換バルブの切り替えの際には、分子量７９０以上のタンパク質を系外に排出しないように留意する。 The protein and electrolyte components eluted from the pretreatment column 10 are monitored at a measurement wavelength of 210 nm in a first detector 11, for example, an absorptiometric detector, and a large amount of electrolyte components are introduced after the proteins are introduced into the separation columns 12 and 12. Is introduced into the separation columns 12, 12, the six-way switching valve is switched to connect the first connection port 4 and the sixth connection port 9, and the third connection port 6 and the second connection port are connected. 5 and the fifth connecting port 8 and the fourth connecting port 7 are connected. In this state, the mobile phase is the mobile phase reservoir 16 → liquid feed pump 1 → injector 2 → 6-way switching valve 3 → separation columns 12, 12 → second detector 13 → 6-way switching valve 3 → pretreatment column 10 → first. 1 detector 11 → 6-way switching valve 3 → drainage pipe 14 flows in this order, and the electrolyte component is discharged out of the system via drainage pipe 14. In addition, since it is possible to measure a protein having a molecular weight of 790 or more by adopting the method for measuring the protein concentration and molecular weight distribution, a protein having a molecular weight of 790 or more is used when the 6-way switching valve is switched. Be careful not to discharge outside.

分離カラム１２に導入されたタンパク質は、その分子量の大きさ、分子量分布に従って分離させ、溶出する。溶出したタンパク質を第２検出器、例えば、吸光光度検出器において測定波長２１０ｎｍで検出し、その検出データに基づいてデータ処理装置でタンパク質の濃度及び分子量分布を求める。 The proteins introduced into the separation column 12 are separated and eluted according to the molecular weight and molecular weight distribution. The eluted protein is detected at a measurement wavelength of 210 nm by a second detector, for example, an absorptiometric detector, and the concentration and molecular weight distribution of the protein are obtained by a data processor based on the detected data.

上記測定方法においては、分離カラムの前に前処理カラムを接続することにより、移動相の流れの中でタンパク質と電解質成分を自動的に分離できるのでインジェクタに注入する前の予備処理が不要であり、そのため測定中のタンパク質の分解を極力抑えることが可能となる。また、大量に共存する電解質成分は６方切換バルブを切換えることにより系外に排出されるので、共存物質の影響を受けることも少ない。さらに、分離カラムでタンパク質の分子量分布を測定することができるので、分子量の情報も得られることから、タンパク質の分解の経時変化も測定することが可能である。 In the above measurement method, by connecting a pretreatment column before the separation column, protein and electrolyte components can be automatically separated in the flow of the mobile phase, so no pretreatment before injection into the injector is required. Therefore, it is possible to suppress the degradation of the protein being measured as much as possible. In addition, since the electrolyte component coexisting in large quantities is discharged out of the system by switching the 6-way switching valve, it is less affected by the coexisting substances. Furthermore, since the molecular weight distribution of the protein can be measured with a separation column, information on the molecular weight can also be obtained, so that it is also possible to measure a change in protein degradation over time.

上記銅電解液は、銅電解時における温度を、通常４０℃〜６０℃、好ましくは４５℃〜５５℃とする。温度が該範囲内にあると、得られる析離箔は、粗面の山の形状及び大きさが揃い、且つ低粗度になり易いため好ましい。なお、温度が４０℃未満であると粗面の山の形状が荒れ易いため好ましくなく、また、６０℃を超えると塩ビ配管等の設備の老朽化が加速され易いため好ましくない。 The said copper electrolyte solution shall be the temperature at the time of copper electrolysis normally 40 to 60 degreeC, Preferably it is 45 to 55 degreeC. When the temperature is within this range, the obtained separation / separation foil is preferable because the shape and size of the crests of the rough surface are uniform and low roughness tends to be obtained. In addition, it is not preferable that the temperature is less than 40 ° C. because the shape of the rough crest is likely to be rough, and if it exceeds 60 ° C., it is not preferable because aging of facilities such as polyvinyl chloride piping is easily accelerated.

上記銅電解液は、公知の製法により製造することができる。例えば、銅濃度は、既存の銅電解液で銅線屑等の銅原料を溶解して高めることができ、フリーＳＯ_４ ^２−濃度やＣｌ⁻濃度は硫酸や塩酸を添加することにより高めることができる。また、銅電解液中のタンパク質の数平均分子量Ｍ_ｎ及び濃度は、上記測定方法により測定した後、必要な数平均分子量Ｍ_ｎに調整したタンパク質水溶液を必要量添加することにより調整することができる。 The said copper electrolyte solution can be manufactured by a well-known manufacturing method. For example, the copper concentration can be increased by dissolving copper raw materials such as copper wire scraps with an existing copper electrolyte, and the free SO ₄ ²⁻ concentration or Cl ⁻ concentration can be increased by adding sulfuric acid or hydrochloric acid. it can. In addition, the number average molecular weight M _n and the concentration of the protein in the copper electrolyte can be adjusted by adding a necessary amount of an aqueous protein solution adjusted to the required number average molecular weight M _n after measuring by the above measurement method. .

（本発明に係る電解銅箔の製造方法）
次に、本発明に係る電解銅箔の製造方法について説明する。該方法は上記電解銅箔製造用銅電解液を用いて析離箔を製造するものであり、析離箔を製造方法としては、公知の方法を用いることができる。公知の析離箔の製造方法としては、例えば、回転するチタン製ドラム状陰極の曲面状陰極表面と陽極との間に銅電解液を供給し、電解して、陰極表面に析離箔を析出し、これを連続的に巻き取る方法が挙げられる。 (Method for producing electrolytic copper foil according to the present invention)
Next, the manufacturing method of the electrolytic copper foil which concerns on this invention is demonstrated. In this method, a deposited foil is produced using the copper electrolytic solution for producing an electrolytic copper foil, and a known method can be used for producing the separated foil. As a known method for producing a separation foil, for example, a copper electrolyte is supplied between the curved cathode surface of a rotating titanium drum-like cathode and the anode, and electrolysis is performed to deposit a separation foil on the cathode surface. In addition, a method of continuously winding it up can be mentioned.

本発明で用いられる銅電解液の電解時における温度は、通常４０℃〜６０℃、好ましくは４５℃〜５５℃とする。温度が該範囲内にあると、得られる析離箔は、粗面の山の形状及び大きさが揃い、且つ低粗度になり易いため好ましい。なお、温度が４０℃未満であると粗面の山の形状が荒れ易いため好ましくなく、また、６０℃を超えると塩ビ配管等の設備の老朽化が加速され易いため好ましくない。 The temperature during electrolysis of the copper electrolyte used in the present invention is usually 40 ° C to 60 ° C, preferably 45 ° C to 55 ° C. When the temperature is within this range, the obtained separation / separation foil is preferable because the shape and size of the crests of the rough surface are uniform and low roughness tends to be obtained. In addition, it is not preferable that the temperature is less than 40 ° C. because the shape of the rough crest is likely to be rough, and if it exceeds 60 ° C., it is not preferable because aging of facilities such as polyvinyl chloride piping is easily accelerated.

また、本発明において銅電解液の電解時における電解電流密度は、通常３０Ａ／ｃｍ^２〜７０Ａ／ｃｍ^２、好ましくは４０Ａ／ｃｍ^２〜６０Ａ／ｃｍ^２である。電解電流密度が該範囲内にあると、得られる析離箔は、粗面の山の形状及び大きさが揃い、且つ低粗度になり易いため好ましい。また、陰極表面は適宜研磨することが好ましく、例えば、Ｒ_ｚを１．２〜１．５とすることが好ましい。 In the present invention, the electrolytic current density during electrolysis of the copper electrolyte is usually 30 A / cm ^{2 to} 70 A / cm ² , preferably 40 A / cm ^{2 to} 60 A / cm ² . When the electrolytic current density is within this range, the obtained separation foil is preferable because the shape and size of the crests of the rough surface are uniform and low roughness tends to be obtained. Moreover, it is preferable to grind | polish the cathode surface suitably, for example, it is preferable to set _Rz to 1.2-1.5.

上記銅電解液は、粗面の山の形状及び大きさが揃い、低粗度の析離箔を製造する原料として使用することができる。該低粗度の析離箔は、箔厚が３５μｍの析離箔で、粗面の粗度Ｒ_ｚが通常４．２μｍ以下、好ましくは２μｍ〜３．２μｍであり、且つ、常態の引張り強さが通常４５．０ｋｇｆ/ｍｍ^２以上である。ここで、Ｒ_ｚとは十点平均粗さを意味し、常態とは常温での測定値を意味する。また、本発明に係る電解銅箔の製造方法は、上記析離箔の製造に用いることができる。 The copper electrolyte solution can be used as a raw material for producing a low-roughness separating / separating foil having a rough crest shape and size. Drum foil of low roughness, with drum foil of foil thickness is 35 [mu] m, the roughness _{R z} of the rough surface is normally less than 4.2 .mu.m, preferably 2Myuemu～3.2Myuemu, and the tensile strength of the normal Is usually 45.0 kgf / mm ² or more. Here, R _z means ten-point average roughness, and normal means a measured value at normal temperature. Moreover, the manufacturing method of the electrolytic copper foil which concerns on this invention can be used for manufacture of the said separating foil.

以下に実施例を示すが、本発明はこれらに限定されて解釈されるものではない。 Examples are shown below, but the present invention is not construed as being limited thereto.

比較例１Comparative Example 1

析離箔を作製する電解装置として、アノード−カソード間の流路が断面矩形であり、且つ循環ポンプを用いてアノード−カソード間に電解液を連続して供給しつつ電解可能な下記仕様のものを用いた。
・槽内液量 ：４．５ｌ
・アノード面及びカソード面の大きさ ：６ｃｍ×１１ｃｍ
・アノードの材質 ：ＤＳＥ
・カソードの材質 ：チタン板
・アノード−カソード間の距離 ：５ｍｍ As an electrolysis apparatus for producing a separating foil, the anode-cathode flow path has a rectangular cross section, and the following specifications are available for electrolysis while continuously supplying an electrolyte solution between the anode and cathode using a circulation pump Was used.
・ Liquid volume in the tank: 4.5 l
-Size of anode surface and cathode surface: 6 cm x 11 cm
・ Anode material: DSE
-Cathode material: Titanium plate-Anode-cathode distance: 5 mm

銅電解液として、純水に、硫酸、硫酸銅５水和物及び塩酸を添加し溶解して、下記組成の溶液（基本液Ａ）を調製した。
・Ｃｕ^２＋濃度 ：８２．５ｇ／ｌ
・フリーＳＯ_４ ^２−濃度 ：１５０ｇ／ｌ
・Ｃｌ⁻濃度 ：１．７ｐｐｍ As a copper electrolyte, sulfuric acid, copper sulfate pentahydrate and hydrochloric acid were added to pure water and dissolved to prepare a solution (basic solution A) having the following composition.
Cu ²⁺ concentration: 82.5 g / l
Free SO ₄ ^2- concentration: 150 g / l
-Cl ^- concentration: 1.7 ppm

一方、ゼラチンとして新田ゼラチン株式会社製ＵＤＢを用い、これを純水に溶解して１ｇ／ｌのゼラチン水溶液（ゼラチン水溶液Ａ）を調製した。
次に、基本液Ａにゼラチン水溶液Ａをゼラチン濃度が１．８ｐｐｍになるまで添加し十分に攪拌して、電解液Ａを調製した。電解液Ａ中のゼラチンの数平均分子量Ｍ_ｎ及び濃度を表１に示す。 On the other hand, UDB manufactured by Nitta Gelatin Co., Ltd. was used as gelatin, and this was dissolved in pure water to prepare a 1 g / l gelatin aqueous solution (gelatin aqueous solution A).
Next, an aqueous gelatin solution A was added to the basic solution A until the gelatin concentration reached 1.8 ppm, and stirred sufficiently to prepare an electrolytic solution A. Table 1 shows the number average molecular weight M _n and the concentration of gelatin in the electrolytic solution A.

なお、ゼラチンの数平均分子量Ｍ_ｎ及び濃度は、図２１記載の装置を用い、下記測定条件で求めたものである。
（測定条件）
前処理カラム ：アマシャムファルマシアバイオテク（株）社製、セファデックスＧ−１５の粒径６６マイクロメータ以下の充填剤（排除限界分子量１５００）を収容した内径７．５ｍｍ、長さ２５０ｍｍのＰＥＥＫ製カラム
分離カラム ：昭和電工（株）社製、Ａｓａｈｉｐａｋ ＧＳ−３２０ＨＱ
（排除限界分子量４００００、内径７．６ｍｍ、長さ３００ｍｍ）
温度 ：２５℃
移動相の種類と流量：アセトニトリル２０容量％と希硫酸（０．００５Ｍ）８０容量％の混合液０．６ｍｌ／分
注入量 ：２００マイクロリッター
検出法 ：２１０ｎｍのＵＶ吸収 In addition, the number average molecular weight M _n and the concentration of gelatin are obtained under the following measurement conditions using the apparatus shown in FIG.
(Measurement condition)
Pretreatment column: PEEK column separation with 7.5 mm inner diameter and 250 mm length containing a filler (exclusion limit molecular weight 1500) of Sephadex G-15 particle size of 66 micrometers or less manufactured by Amersham Pharmacia Biotech Co., Ltd. Column: Showa Denko Co., Ltd., Asahipak GS-320HQ
(Exclusion limit molecular weight 40000, inner diameter 7.6 mm, length 300 mm)
Temperature: 25 ° C
Type and flow rate of mobile phase: A mixture of 20% by volume of acetonitrile and 80% by volume of dilute sulfuric acid (0.005M) 0.6 ml / min Injection amount: 200 microliters Detection method: 210 nm UV absorption

なお、ゼラチンの数平均分子量Ｍ_ｎの測定において、検量線の作成に用いた試薬は以下のとおりである。また、ゼラチンの濃度は、同種のゼラチンの濃度既知の水溶液を用いて検量線を作成することにより測定した。
（試薬）
・ＡＬＢＵＭＩＮ，ＢＯＶＩＮＥ ＳＥＲＵＭ（シグマアルドリッチジャパン株式会社製、分子量６６０００）
・ＣＹＴＯＣＨＲＯＭＥ Ｃ（シグマアルドリッチジャパン株式会社製、分子量１２４００）
・ＡＰＲＯＴＩＮＩＮ（シグマアルドリッチジャパン株式会社製、分子量６５００）
・ＩＮＳＵＬＩＮ（シグマアルドリッチジャパン株式会社製、分子量５７３４）
・ＩＮＳＵＬＩＮ ＣＨＡＩＮ Ｂ，ＯＸＩＤＩＺＥＤ（シグマアルドリッチジャパン株式会社製、分子量３４９６）
・ＮＥＵＲＯＴＥＮＳＩＮ（シグマアルドリッチジャパン株式会社製、分子量１６７３）
・ＡＮＧＩＯＴＥＮＳＩＮ ＩＩ（シグマアルドリッチジャパン株式会社製、分子量１０４６）
・ＶＡＬ−ＧＬＵ−ＧＬＵ−ＡＬＡ−ＧＬＵ（シグマアルドリッチジャパン株式会社製、分子量５７６） In the measurement of the number average molecular weight _Mn of gelatin, the reagents used for preparing a calibration curve are as follows. The concentration of gelatin was measured by preparing a calibration curve using an aqueous solution of the same type of gelatin with known concentration.
(reagent)
・ ALBUMIN, BOVINE SERUM (Sigma Aldrich Japan Co., Ltd., molecular weight 66000)
CYTOCHROME C (Sigma Aldrich Japan Co., Ltd., molecular weight 12400)
・ APROTININ (Sigma Aldrich Japan Co., Ltd., molecular weight 6500)
INSULIN (Sigma Aldrich Japan Co., Ltd., molecular weight 5734)
INSULIN CHAIN B, OXIDIZED (Sigma Aldrich Japan Co., Ltd., molecular weight 3496)
・ NEUROTENSIN (manufactured by Sigma Aldrich Japan Co., Ltd., molecular weight 1673)
・ ANGIOTENSIN II (Sigma Aldrich Japan Co., Ltd., molecular weight 1046)
VAL-GLU-GLU-ALA-GLU (Sigma Aldrich Japan, molecular weight 576)

電解液Ａを調製してから直ぐに、下記条件で電解して析離箔を作製した。
・銅電解液の温度 ：５２℃
・電解電流密度 ：５０Ａ／ｃｍ^２
・析離箔の厚さ ：３５μｍ Immediately after the electrolytic solution A was prepared, electrolysis was performed under the following conditions to prepare a deposited foil.
・ Copper electrolyte temperature: 52 ℃
Electrolytic current density: 50 A / cm ²
・ Thickness of separation foil: 35μm

得られた析離箔について、粗面の粗度Ｒ_ａ、Ｒ_ｍａｘ及びＲ_ｚ、常態の引張り強さ、並びに常態の伸びを測定した。測定方法は、以下のとおりである。測定結果を表２及び表３に示す。また、得られた析離箔の粗面の表面の走査型電子顕微鏡（ＳＥＭ）写真を撮影した。その結果を図１に示す。
・粗度Ｒ_ａ、Ｒ_ｍａｘ及びＲ_ｚ：先端がφ２μｍのダイヤモンドボールである接触式の表面粗度計（小坂株式会社製、商品名：ＳＥＦ−３０Ｄ）を用いて、得られた析離箔の粗面の表面粗度を測定した。測定長さは０．８ｍｍとした。Ｒ_ａ、Ｒ_ｍａｘ及びＲ_ｚはＪＩＳＢ０６０１に準拠して測定したものであり、具体的にはＲ_ａは中心線平均粗さ、Ｒ_ｍａｘは最大粗さ、Ｒ_ｚは十点平均値粗さを示す。
・常温引張り強さ：得られた析離箔を裁断して幅１ｃｍ×長さ１０ｃｍの測定試料を作製し、該試料の長さ方向の両端をそれぞれ、装置の上下方向の２箇所に設けられた万力類似のチャックで挟み込んで試料の長さ方向が上下方向になるようにセットし、常温下で、下方のチャックを試料を挟みこんだまま、速度５０ｍｍ／ｍｉｎで下方に引っ張り、測定される引張り強さの最大荷重を常温引張り強さとした。
・常温伸び：常温引張り強さの測定の際に、測定される伸びの最大値を常温伸びとした。 The obtained separation / separation foil was measured for roughness R _a , R _max and R _z of the rough surface, normal tensile strength, and normal elongation. The measuring method is as follows. The measurement results are shown in Tables 2 and 3. Moreover, the scanning electron microscope (SEM) photograph of the surface of the rough surface of the obtained separating / separating foil was image | photographed. The result is shown in FIG.
Roughness R _a , R _max and R _z : Separation foil obtained using a contact-type surface roughness meter (trade name: SEF-30D, manufactured by Kosaka Co., Ltd.) which is a diamond ball having a tip of φ2 μm. The surface roughness of the rough surface was measured. The measurement length was 0.8 mm. R _a , R _max and R _z are measured in accordance with JISB0601, and specifically, R _a is center line average roughness, R _max is maximum roughness, and R _z is ten-point average roughness. Show.
-Tensile strength at normal temperature: Cut the obtained separation foil to prepare a measurement sample having a width of 1 cm and a length of 10 cm, and both ends in the length direction of the sample are provided at two locations in the vertical direction of the apparatus. The sample is sandwiched between vise-like chucks and set so that the length of the sample is in the vertical direction. At room temperature, the lower chuck is sandwiched and the sample is pulled downward at a speed of 50 mm / min. The maximum load of tensile strength to be used was the room temperature tensile strength.
-Room temperature elongation: When measuring room temperature tensile strength, the maximum value of elongation measured was defined as room temperature elongation.

比較例２Comparative Example 2

基本液Ａにゼラチン水溶液Ａをゼラチン濃度が１．８ｐｐｍになるまで添加した後、ゼラチンを添加しないで該液を５０℃で８０時間保持して、電解液Ｂを調製した。電解液Ｂ中のゼラチンの数平均分子量Ｍ_ｎ及び濃度を表１に示す。
電解液Ｂを用い、ゼラチン水溶液Ａを添加してから８０時間後に、比較例１と同条件で電解して析離箔を作製した。
得られた析離箔について、比較例１と同様にして、粗面の粗度Ｒ_ａ、Ｒ_ｍａｘ及びＲ_ｚ、常態の引張り強さ、並びに常態の伸びを測定した。測定結果を表２及び表３に示す。また、得られた析離箔の粗面の表面のＳＥＭ写真を撮影した。その結果を図２に示す。 After adding the gelatin aqueous solution A to the basic solution A until the gelatin concentration became 1.8 ppm, the solution was kept at 50 ° C. for 80 hours without adding gelatin to prepare an electrolytic solution B. Table 1 shows the number average molecular weight M _n and the concentration of gelatin in the electrolytic solution B.
Using the electrolytic solution B, 80 hours after adding the gelatin aqueous solution A, electrolysis was performed under the same conditions as in Comparative Example 1 to prepare a separating foil.
The obtained deposited foil, in the same manner as in Comparative Example 1, the roughness of the rough surface R _a, R _max and R _z, normal tensile strength, as well as to measure the elongation of normal. The measurement results are shown in Tables 2 and 3. Moreover, the SEM photograph of the surface of the rough surface of the obtained separating / separating foil was photographed. The result is shown in FIG.

比較例３Comparative Example 3

銅電解液として、純水に、硫酸、硫酸銅５水和物及び塩酸を添加し溶解して、下記組成の溶液（基本液Ｂ）を調製した。
・Ｃｕ^２＋濃度 ：８４．０ｇ／ｌ
・フリーＳＯ_４ ^２−濃度 ：１５０ｇ／ｌ
・Ｃｌ⁻濃度 ：１．７ｐｐｍ As a copper electrolyte, sulfuric acid, copper sulfate pentahydrate and hydrochloric acid were added and dissolved in pure water to prepare a solution (basic solution B) having the following composition.
Cu ²⁺ concentration: 84.0 g / l
Free SO ₄ ^2- concentration: 150 g / l
-Cl ^- concentration: 1.7 ppm

次に、基本液Ｂにゼラチン水溶液Ａをゼラチン濃度が２．７ｐｐｍになるまで添加し十分に攪拌して、電解液Ｃを調製した。電解液Ｃ中のゼラチンの数平均分子量Ｍ_ｎ及び濃度を表１に示す。
電解液Ｃを調製してから直ぐに、下記条件で電解して析離箔を作製した。
・銅電解液の温度 ：５２℃
・電解電流密度 ：５０Ａ／ｃｍ^２
・析離箔の厚さ ：３５μｍ Next, an aqueous gelatin solution A was added to the basic solution B until the gelatin concentration reached 2.7 ppm, and stirred sufficiently to prepare an electrolytic solution C. Table 1 shows the number average molecular weight M _n and the concentration of gelatin in the electrolytic solution C.
Immediately after preparing the electrolytic solution C, electrolysis was performed under the following conditions to prepare a deposited foil.
・ Copper electrolyte temperature: 52 ℃
Electrolytic current density: 50 A / cm ²
・ Thickness of separation foil: 35μm

得られた析離箔について、比較例１と同様にして、粗面の粗度Ｒ_ａ、Ｒ_ｍａｘ及びＲ_ｚ、常態の引張り強さ、並びに常態の伸びを測定した。測定結果を表２及び表３に示す。また、得られた析離箔の粗面の表面のＳＥＭ写真を撮影した。その結果を図３に示す。 The obtained deposited foil, in the same manner as in Comparative Example 1, the roughness of the rough surface R _a, R _max and R _z, normal tensile strength, as well as to measure the elongation of normal. The measurement results are shown in Tables 2 and 3. Moreover, the SEM photograph of the surface of the rough surface of the obtained separating / separating foil was photographed. The result is shown in FIG.

電解液Ｃに対し、ゼラチン水溶液Ａを、１日かけて電解液中の濃度に換算して０．５ｐｐｍずつ６回（計３ｐｐｍ）添加し十分に攪拌する操作を行い、電解液Ｃに対してゼラチン水溶液Ａを最初に添加してから１日経った電解液Ｄを調製した。電解液Ｄ中のゼラチンの数平均分子量Ｍ_ｎ及び濃度を表１に示す。
電解液Ｄを用い、比較例３と同条件で電解して析離箔を作製した。
得られた析離箔について、比較例１と同様にして、粗面の粗度Ｒ_ａ、Ｒ_ｍａｘ及びＲ_ｚ、常態の引張り強さ、並びに常態の伸びを測定した。測定結果を表２及び表３に示す。また、得られた析離箔の粗面の表面のＳＥＭ写真を撮影した。その結果を図４に示す。 The electrolyte solution C was added with the gelatin aqueous solution A in terms of the concentration in the electrolyte solution over the course of one day, 0.5 ppm each 6 times (3 ppm in total) and sufficiently stirred. An electrolyte solution D was prepared 1 day after the gelatin aqueous solution A was first added. Table 1 shows the number average molecular weight M _n and the concentration of gelatin in the electrolytic solution D.
Using the electrolytic solution D, electrolysis was performed under the same conditions as in Comparative Example 3 to prepare a separation / separation foil.
The obtained deposited foil, in the same manner as in Comparative Example 1, the roughness of the rough surface R _a, R _max and R _z, normal tensile strength, as well as to measure the elongation of normal. The measurement results are shown in Tables 2 and 3. Moreover, the SEM photograph of the surface of the rough surface of the obtained separating / separating foil was photographed. The result is shown in FIG.

電解液Ｄに対し、ゼラチン水溶液Ａを、１日かけて電解液中の濃度に換算して０．５ｐｐｍずつ６回（計３ｐｐｍ）添加し十分に攪拌する操作をさらに５日間繰り返して、電解液Ｃに対してゼラチン水溶液Ａを最初に添加してから６日経った電解液Ｅを調製した。電解液Ｅ中のゼラチンの数平均分子量Ｍ_ｎ及び濃度を表１に示す。
電解液Ｅを用い、比較例３と同条件で電解して析離箔を作製した。
得られた析離箔について、比較例１と同様にして、粗面の粗度Ｒ_ａ、Ｒ_ｍａｘ及びＲ_ｚ、常態の引張り強さ、並びに常態の伸びを測定した。測定結果を表２及び表３に示す。また、得られた析離箔の粗面の表面のＳＥＭ写真を撮影した。その結果を図５に示す。 The operation of adding the aqueous gelatin solution A to the electrolytic solution D in six times 0.5 ppm each in terms of the concentration in the electrolytic solution over a day (3 ppm in total) and sufficiently stirring is further repeated for 5 days. An electrolytic solution E was prepared 6 days after the gelatin aqueous solution A was first added to C. Table 1 shows the number average molecular weight M _n and the concentration of gelatin in the electrolytic solution E.
Using the electrolytic solution E, electrolysis was performed under the same conditions as in Comparative Example 3 to prepare a separation / separation foil.
The obtained deposited foil, in the same manner as in Comparative Example 1, the roughness of the rough surface R _a, R _max and R _z, normal tensile strength, as well as to measure the elongation of normal. The measurement results are shown in Tables 2 and 3. Moreover, the SEM photograph of the surface of the rough surface of the obtained separating / separating foil was photographed. The result is shown in FIG.

電解液Ｅに対し、ゼラチン水溶液Ａを、１日かけて電解液中の濃度に換算して０．５ｐｐｍずつ６回（計３ｐｐｍ）添加し十分に攪拌する操作をさらに７日間繰り返して、電解液Ｃに対してゼラチン水溶液Ａを最初に添加してから１３日経った電解液Ｆを調製した。電解液Ｆ中のゼラチンの数平均分子量Ｍ_ｎ及び濃度を表１に示す。
電解液Ｆを用い、比較例３と同条件で電解して析離箔を作製した。
得られた析離箔について、比較例１と同様にして、粗面の粗度Ｒ_ａ、Ｒ_ｍａｘ及びＲ_ｚ、常態の引張り強さ、並びに常態の伸びを測定した。測定結果を表２及び表３に示す。また、得られた析離箔の粗面の表面のＳＥＭ写真を撮影した。その結果を図６に示す。 The operation of adding the aqueous gelatin solution A to the electrolytic solution E in a concentration of 0.5 ppm 6 times (3 ppm in total) in terms of the concentration in the electrolytic solution over one day and stirring sufficiently for another 7 days An electrolytic solution F was prepared 13 days after the gelatin aqueous solution A was first added to C. Table 1 shows the number average molecular weight M _n and the concentration of gelatin in the electrolytic solution F.
Using the electrolytic solution F, electrolysis was performed under the same conditions as in Comparative Example 3 to prepare a separation / separation foil.
The obtained deposited foil, in the same manner as in Comparative Example 1, the roughness of the rough surface R _a, R _max and R _z, normal tensile strength, as well as to measure the elongation of normal. The measurement results are shown in Tables 2 and 3. Moreover, the SEM photograph of the surface of the rough surface of the obtained separating / separating foil was photographed. The result is shown in FIG.

比較例４Comparative Example 4

ゼラチンとして新田ゼラチン株式会社製ＳＣＰ５０００を用い、これを純水に溶解して１ｇ／ｌのゼラチン水溶液（ゼラチン水溶液Ｂ）を調製した。
次に、基本液Ｂにゼラチン水溶液Ｂをゼラチン濃度が４．５ｐｐｍになるまで添加し十分に攪拌して、電解液Ｇを調製した。電解液Ｇ中のゼラチンの数平均分子量Ｍ_ｎ及び濃度を表１に示す。
電解液Ｇを調製してから直ぐに、比較例３と同条件で電解して析離箔を作製した。
得られた析離箔について、比較例１と同様にして、粗面の粗度Ｒ_ａ、Ｒ_ｍａｘ及びＲ_ｚ、常態の引張り強さ、並びに常態の伸びを測定した。測定結果を表２及び表３に示す。また、得られた析離箔の粗面の表面のＳＥＭ写真を撮影した。その結果を図７に示す。 As the gelatin, SCP5000 manufactured by Nitta Gelatin Co., Ltd. was used and dissolved in pure water to prepare a 1 g / l gelatin aqueous solution (gelatin aqueous solution B).
Next, an aqueous gelatin solution B was added to the basic solution B until the gelatin concentration reached 4.5 ppm, and stirred sufficiently to prepare an electrolytic solution G. Table 1 shows the number average molecular weight M _n and the concentration of gelatin in the electrolytic solution G.
Immediately after the electrolytic solution G was prepared, electrolysis was performed under the same conditions as in Comparative Example 3 to prepare a separation / separation foil.
The obtained deposited foil, in the same manner as in Comparative Example 1, the roughness of the rough surface R _a, R _max and R _z, normal tensile strength, as well as to measure the elongation of normal. The measurement results are shown in Tables 2 and 3. Moreover, the SEM photograph of the surface of the rough surface of the obtained separating / separating foil was photographed. The result is shown in FIG.

電解液Ｇに対し、ゼラチン水溶液Ｂを、１日かけて電解液中の濃度に換算して０．５ｐｐｍずつ６回（計３ｐｐｍ）添加し十分に攪拌する操作を行い、電解液Ｇに対してゼラチン水溶液Ｂを最初に添加してから１日経った電解液Ｈを調製した。電解液Ｈ中のゼラチンの数平均分子量Ｍ_ｎ及び濃度を表１に示す。
電解液Ｈを用い、比較例３と同条件で電解して析離箔を作製した。
得られた析離箔について、比較例１と同様にして、粗面の粗度Ｒ_ａ、Ｒ_ｍａｘ及びＲ_ｚ、常態の引張り強さ、並びに常態の伸びを測定した。測定結果を表２及び表３に示す。また、得られた析離箔の粗面の表面のＳＥＭ写真を撮影した。その結果を図８に示す。 The electrolyte solution G was added with the gelatin aqueous solution B in terms of the concentration in the electrolyte solution over the course of one day, 0.5 ppm each 6 times (3 ppm in total) and sufficiently stirred. An electrolyte solution H was prepared 1 day after the gelatin aqueous solution B was first added. Table 1 shows the number average molecular weight M _n and the concentration of gelatin in the electrolytic solution H.
Using the electrolytic solution H, electrolysis was carried out under the same conditions as in Comparative Example 3 to prepare a separation / separation foil.
The obtained deposited foil, in the same manner as in Comparative Example 1, the roughness of the rough surface R _a, R _max and R _z, normal tensile strength, as well as to measure the elongation of normal. The measurement results are shown in Tables 2 and 3. Moreover, the SEM photograph of the surface of the rough surface of the obtained separating / separating foil was photographed. The result is shown in FIG.

電解液Ｄに対し、ゼラチン水溶液Ｂを、１日かけて電解液中の濃度に換算して０．５ｐｐｍずつ６回（計３ｐｐｍ）添加し十分に攪拌する操作をさらに５日間繰り返して、電解液Ｇに対してゼラチン水溶液Ｂを最初に添加してから６日経った電解液Ｉを調製した。電解液Ｉ中のゼラチンの数平均分子量Ｍ_ｎ及び濃度を表１に示す。
電解液Ｉを用い、比較例３と同条件で電解して析離箔を作製した。
得られた析離箔について、比較例１と同様にして、粗面の粗度Ｒ_ａ、Ｒ_ｍａｘ及びＲ_ｚ、常態の引張り強さ、並びに常態の伸びを測定した。測定結果を表２及び表３に示す。また、得られた析離箔の粗面の表面のＳＥＭ写真を撮影した。その結果を図９に示す。 The operation of adding the aqueous gelatin solution B to the electrolytic solution D by converting it to the concentration in the electrolytic solution over the course of 1 day and adding 0.5 ppm 6 times (3 ppm in total) and further stirring the solution further for 5 days, An electrolyte solution I was prepared 6 days after the gelatin aqueous solution B was first added to G. Table 1 shows the number average molecular weight M _n and the concentration of gelatin in the electrolytic solution I.
Using the electrolytic solution I, electrolysis was performed under the same conditions as in Comparative Example 3 to prepare a deposited foil.
The obtained deposited foil, in the same manner as in Comparative Example 1, the roughness of the rough surface R _a, R _max and R _z, normal tensile strength, as well as to measure the elongation of normal. The measurement results are shown in Tables 2 and 3. Moreover, the SEM photograph of the surface of the rough surface of the obtained separating / separating foil was photographed. The result is shown in FIG.

電解液Ｅに対し、ゼラチン水溶液Ｂを、１日かけて電解液中の濃度に換算して０．５ｐｐｍずつ６回（計３ｐｐｍ）添加し十分に攪拌する操作をさらに７日間繰り返して、電解液Ｇに対してゼラチン水溶液Ｂを最初に添加してから１３日経った電解液Ｊを調製した。電解液Ｊ中のゼラチンの数平均分子量Ｍ_ｎ及び濃度を表１に示す。
電解液Ｊを用い、比較例３と同条件で電解して析離箔を作製した。
得られた析離箔について、比較例１と同様にして、粗面の粗度Ｒ_ａ、Ｒ_ｍａｘ及びＲ_ｚ、常態の引張り強さ、並びに常態の伸びを測定した。測定結果を表２及び表３に示す。また、得られた析離箔の粗面の表面のＳＥＭ写真を撮影した。その結果を図１０に示す。 Addition of gelatin aqueous solution B to electrolyte solution E over the course of one day in 0.5 ppm increments 6 times (total 3 ppm) and stirring sufficiently for another 7 days Electrolyte J was prepared 13 days after the gelatin aqueous solution B was first added to G. Table 1 shows the number average molecular weight M _n and the concentration of gelatin in the electrolytic solution J.
Using the electrolytic solution J, electrolysis was performed under the same conditions as in Comparative Example 3 to prepare a separation / separation foil.
The obtained deposited foil, in the same manner as in Comparative Example 1, the roughness of the rough surface R _a, R _max and R _z, normal tensile strength, as well as to measure the elongation of normal. The measurement results are shown in Tables 2 and 3. Moreover, the SEM photograph of the surface of the rough surface of the obtained separating / separating foil was photographed. The result is shown in FIG.

比較例５Comparative Example 5

ゼラチンとして新田ゼラチン株式会社製７００Ｆを用い、これを純水に溶解して１ｇ／ｌのゼラチン水溶液（ゼラチン水溶液Ｃ）を調製した。
次に、基本液Ｂにゼラチン水溶液Ｃをゼラチン濃度が１．６ｐｐｍになるまで添加し十分に攪拌して、電解液Ｋを調製した。電解液Ｋ中のゼラチンの数平均分子量Ｍ_ｎ及び濃度を表１に示す。
電解液Ｋを調製してから直ぐに、比較例３と同条件で電解して析離箔を作製した。
得られた析離箔について、比較例１と同様にして、粗面の粗度Ｒ_ａ、Ｒ_ｍａｘ及びＲ_ｚ、常態の引張り強さ、並びに常態の伸びを測定した。測定結果を表２及び表３に示す。また、得られた析離箔の粗面の表面のＳＥＭ写真を撮影した。その結果を図１１に示す。 700F manufactured by Nitta Gelatin Co., Ltd. was used as gelatin, and this was dissolved in pure water to prepare a 1 g / l gelatin aqueous solution (gelatin aqueous solution C).
Next, an aqueous gelatin solution C was added to the basic solution B until the gelatin concentration reached 1.6 ppm, and stirred sufficiently to prepare an electrolytic solution K. Table 1 shows the number average molecular weight M _n and the concentration of gelatin in the electrolytic solution K.
Immediately after preparing the electrolyte solution K, electrolysis was performed under the same conditions as in Comparative Example 3 to prepare a separation / separation foil.
The obtained deposited foil, in the same manner as in Comparative Example 1, the roughness of the rough surface R _a, R _max and R _z, normal tensile strength, as well as to measure the elongation of normal. The measurement results are shown in Tables 2 and 3. Moreover, the SEM photograph of the surface of the rough surface of the obtained separating / separating foil was photographed. The result is shown in FIG.

比較例６Comparative Example 6

基本液Ｂにゼラチン水溶液Ｃをゼラチン濃度が１．６ｐｐｍになるまで添加した後、ゼラチンを添加しないで該液を５２℃で６．５時間保持して、電解液Ｌを調製した。電解液Ｌ中のゼラチンの数平均分子量Ｍ_ｎ及び濃度を表１に示す。
電解液Ｌを用い、比較例３と同条件で電解して析離箔を作製した。
得られた析離箔について、比較例１と同様にして、粗面の粗度Ｒ_ａ、Ｒ_ｍａｘ及びＲ_ｚ、常態の引張り強さ、並びに常態の伸びを測定した。測定結果を表２及び表３に示す。また、得られた析離箔の粗面の表面のＳＥＭ写真を撮影した。その結果を図１２に示す。 An aqueous gelatin solution C was added to the basic solution B until the gelatin concentration reached 1.6 ppm, and then the solution was kept at 52 ° C. for 6.5 hours without adding gelatin to prepare an electrolytic solution L. Table 1 shows the number average molecular weight M _n and the concentration of gelatin in the electrolytic solution L.
Using the electrolytic solution L, electrolysis was performed under the same conditions as in Comparative Example 3 to prepare a separation / separation foil.
The obtained deposited foil, in the same manner as in Comparative Example 1, the roughness of the rough surface R _a, R _max and R _z, normal tensile strength, as well as to measure the elongation of normal. The measurement results are shown in Tables 2 and 3. Moreover, the SEM photograph of the surface of the rough surface of the obtained separating / separating foil was photographed. The result is shown in FIG.

電解液Ｋに対し、ゼラチン水溶液Ｃを、７時間かけて電解液中の濃度に換算して０．５ｐｐｍずつ５回（計２．５ｐｐｍ）添加し十分に攪拌する操作を行い、電解液Ｋに対してゼラチン水溶液Ｃを最初に添加してから７時間経った電解液Ｌを調製した。電解液Ｌ中のゼラチンの数平均分子量Ｍ_ｎ及び濃度を表１に示す。
電解液Ｌを用い、比較例３と同条件で電解して析離箔を作製した。
得られた析離箔について、比較例１と同様にして、粗面の粗度Ｒ_ａ、Ｒ_ｍａｘ及びＲ_ｚ、常態の引張り強さ、並びに常態の伸びを測定した。測定結果を表２及び表３に示す。また、得られた析離箔の粗面の表面のＳＥＭ写真を撮影した。その結果を図１３に示す。 Add the gelatin aqueous solution C to the electrolytic solution K over the course of 7 hours, adding 0.5 ppm each 5 times (total 2.5 ppm), and stir well. On the other hand, an electrolytic solution L was prepared 7 hours after the gelatin aqueous solution C was first added. Table 1 shows the number average molecular weight M _n and the concentration of gelatin in the electrolytic solution L.
Using the electrolytic solution L, electrolysis was performed under the same conditions as in Comparative Example 3 to prepare a separation / separation foil.
The obtained deposited foil, in the same manner as in Comparative Example 1, the roughness of the rough surface R _a, R _max and R _z, normal tensile strength, as well as to measure the elongation of normal. The measurement results are shown in Tables 2 and 3. Moreover, the SEM photograph of the surface of the rough surface of the obtained separating / separating foil was photographed. The result is shown in FIG.

基本液Ｂにゼラチン水溶液Ａを、電解液中の濃度に換算して１日当たり０．５ｐｐｍずつ１０回添加する作業を２日間行い、合計１０ｐｐｍ添加し十分に攪拌して、電解液Ｏを調製した。電解液Ｏ中のゼラチンの数平均分子量Ｍ_ｎ及び濃度を表１に示す。
電解液Ｏを用い、比較例３と同条件で電解して析離箔を作製した。
得られた析離箔について、比較例１と同様にして、粗面の粗度Ｒ_ａ、Ｒ_ｍａｘ及びＲ_ｚ、常態の引張り強さ、並びに常態の伸びを測定した。測定結果を表２及び表３に示す。また、得られた析離箔の粗面の表面のＳＥＭ写真を撮影した。その結果を図１４に示す。 The gelatin aqueous solution A was added to the basic solution B at a concentration of 0.5 ppm per day 10 times in terms of the concentration in the electrolytic solution for 2 days, and a total of 10 ppm was added and stirred thoroughly to prepare an electrolytic solution O. . Table 1 shows the number average molecular weight M _n and the concentration of gelatin in the electrolytic solution O.
Using the electrolytic solution O, electrolysis was performed under the same conditions as in Comparative Example 3 to prepare a separation / separation foil.
The obtained deposited foil, in the same manner as in Comparative Example 1, the roughness of the rough surface R _a, R _max and R _z, normal tensile strength, as well as to measure the elongation of normal. The measurement results are shown in Tables 2 and 3. Moreover, the SEM photograph of the surface of the rough surface of the obtained separating / separating foil was photographed. The result is shown in FIG.

比較例７Comparative Example 7

基本液Ｂにゼラチン水溶液Ｂを、電解液中の濃度に換算して１日当たり０．５ｐｐｍずつ１０回添加する作業を２日間行い、合計１０ｐｐｍ添加後３日間放置して、電解液Ｐを調製した。電解液Ｐ中のゼラチンの数平均分子量Ｍ_ｎ及び濃度を表１に示す。
電解液Ｐを用い、比較例３と同条件で電解して析離箔を作製した。
得られた析離箔について、比較例１と同様にして、粗面の粗度Ｒ_ａ、Ｒ_ｍａｘ及びＲ_ｚを測定した。測定結果を表２及び表３に示す。 The gelatin aqueous solution B was added to the basic solution B 10 times at a concentration of 0.5 ppm per day in terms of the concentration in the electrolyte solution for 2 days, and the electrolyte solution P was prepared by allowing it to stand for 3 days after the addition of 10 ppm in total. . Table 1 shows the number average molecular weight M _n and the concentration of gelatin in the electrolytic solution P.
Using the electrolytic solution P, electrolysis was performed under the same conditions as in Comparative Example 3 to produce a deposited foil.
The obtained deposited foil, in the same manner as in Comparative Example 1, the roughness of the rough surface _{R a,} were measured _{R max} and _{R z.} The measurement results are shown in Tables 2 and 3.

基本液Ｂにゼラチン水溶液Ｂを、電解液中の濃度に換算して１日当たり０．５ｐｐｍずつ１０回添加する作業を２日間行い、合計１０ｐｐｍ添加し十分に攪拌して、電解液Ｑを調製した。電解液Ｑ中のゼラチンの数平均分子量Ｍ_ｎ及び濃度を表１に示す。
電解液Ｑを用い、比較例３と同条件で電解して析離箔を作製した。
得られた析離箔について、比較例１と同様にして、粗面の粗度Ｒ_ａ、Ｒ_ｍａｘ及びＲ_ｚ、常態の引張り強さ、並びに常態の伸びを測定した。測定結果を表２及び表３に示す。また、得られた析離箔の粗面の表面のＳＥＭ写真を撮影した。その結果を図１５に示す。 The gelatin aqueous solution B was added to the basic solution B at a concentration of 0.5 ppm per day 10 times in terms of the concentration in the electrolytic solution for 2 days, and a total of 10 ppm was added and stirred sufficiently to prepare an electrolytic solution Q. . Table 1 shows the number average molecular weight M _n and the concentration of gelatin in the electrolytic solution Q.
Using the electrolytic solution Q, electrolysis was performed under the same conditions as in Comparative Example 3 to prepare a separation / separation foil.
The obtained deposited foil, in the same manner as in Comparative Example 1, the roughness of the rough surface R _a, R _max and R _z, normal tensile strength, as well as to measure the elongation of normal. The measurement results are shown in Tables 2 and 3. Moreover, the SEM photograph of the surface of the rough surface of the obtained separating / separating foil was photographed. The result is shown in FIG.

比較例８Comparative Example 8

ゼラチンとして旭陽化学株式会社製Ａ１５７６を用い、これを純水に溶解して１ｇ／ｌのゼラチン水溶液（ゼラチン水溶液Ｃ）を調製した。
次に、基本液Ｂにゼラチン水溶液Ｃを液中の濃度が５ｐｐｍになるように添加し十分に攪拌した後、５時間放置して、電解液Ｒを調製した。電解液Ｒ中のゼラチンの数平均分子量Ｍ_ｎ及び濃度を表１に示す。
電解液Ｒを用い、比較例３と同条件で電解して析離箔を作製した。
得られた析離箔について、比較例１と同様にして、粗面の粗度Ｒ_ａ、Ｒ_ｍａｘ及びＲ_ｚ、常態の引張り強さ、並びに常態の伸びを測定した。測定結果を表２及び表３に示す。また、得られた析離箔の粗面の表面のＳＥＭ写真を撮影した。その結果を図１６に示す。 A1576 manufactured by Asahi Chemical Co., Ltd. was used as gelatin, and this was dissolved in pure water to prepare a 1 g / l gelatin aqueous solution (gelatin aqueous solution C).
Next, an aqueous gelatin solution C was added to the basic solution B so that the concentration in the solution was 5 ppm, and the mixture was sufficiently stirred, and then allowed to stand for 5 hours to prepare an electrolytic solution R. Table 1 shows the number average molecular weight M _n and the concentration of gelatin in the electrolytic solution R.
Using the electrolytic solution R, electrolysis was performed under the same conditions as in Comparative Example 3 to prepare a separation / separation foil.
The obtained deposited foil, in the same manner as in Comparative Example 1, the roughness of the rough surface R _a, R _max and R _z, normal tensile strength, as well as to measure the elongation of normal. The measurement results are shown in Tables 2 and 3. Moreover, the SEM photograph of the surface of the rough surface of the obtained separating / separating foil was photographed. The result is shown in FIG.

基本液Ｂにゼラチン水溶液Ａを、電解液中の濃度に換算して１日当たり０．５ｐｐｍずつ１５回添加する作業を２日間行い、合計１５ｐｐｍ添加して、電解液Ｓを調製した。電解液Ｓ中のゼラチンの数平均分子量Ｍ_ｎ及び濃度を表１に示す。
電解液Ｓを用い、比較例３と同条件で電解して析離箔を作製した。
得られた析離箔について、比較例１と同様にして、粗面の粗度Ｒ_ａ、Ｒ_ｍａｘ及びＲ_ｚ、常態の引張り強さ、並びに常態の伸びを測定した。測定結果を表２及び表３に示す。また、得られた析離箔の粗面の表面のＳＥＭ写真を撮影した。その結果を図１７に示す。 The operation of adding the aqueous gelatin solution A to the basic solution B at a concentration of 0.5 ppm per day 15 times in terms of the concentration in the electrolytic solution was performed for 2 days, and a total of 15 ppm was added to prepare an electrolytic solution S. Table 1 shows the number average molecular weight M _n and the concentration of gelatin in the electrolytic solution S.
Using the electrolytic solution S, electrolysis was performed under the same conditions as in Comparative Example 3 to prepare a separation / separation foil.
The obtained deposited foil, in the same manner as in Comparative Example 1, the roughness of the rough surface R _a, R _max and R _z, normal tensile strength, as well as to measure the elongation of normal. The measurement results are shown in Tables 2 and 3. Moreover, the SEM photograph of the surface of the rough surface of the obtained separating / separating foil was photographed. The result is shown in FIG.

比較例９Comparative Example 9

基本液Ｂにゼラチン水溶液Ａ、電解液中の濃度に換算して１日当たり０．５ｐｐｍずつ１５回添加する作業を２日間行い、合計１５ｐｐｍ添加した後、これを８０時間放置して、電解液Ｔを調製した。電解液Ｔ中のゼラチンの数平均分子量Ｍ_ｎ及び濃度を表１に示す。
電解液Ｔを用い、比較例３と同条件で電解して析離箔を作製した。
得られた析離箔について、比較例１と同様にして、粗面の粗度Ｒ_ａ、Ｒ_ｍａｘ及びＲ_ｚ、常態の引張り強さ、並びに常態の伸びを測定した。測定結果を表２及び表３に示す。また、得られた析離箔の粗面の表面のＳＥＭ写真を撮影した。その結果を図１８に示す。 The basic solution B was added 15 times at a concentration of 0.5 ppm per day in gelatin aqueous solution A and converted to the concentration in the electrolyte solution for 2 days. After adding a total of 15 ppm, this was left for 80 hours. Was prepared. Table 1 shows the number average molecular weight M _n and the concentration of gelatin in the electrolytic solution T.
Using the electrolytic solution T, electrolysis was performed under the same conditions as in Comparative Example 3 to prepare a separation / separation foil.
The obtained deposited foil, in the same manner as in Comparative Example 1, the roughness of the rough surface R _a, R _max and R _z, normal tensile strength, as well as to measure the elongation of normal. The measurement results are shown in Tables 2 and 3. Moreover, the SEM photograph of the surface of the rough surface of the obtained separating / separating foil was photographed. The result is shown in FIG.

表１〜表３より、銅電解液中のゼラチンの数平均分子量Ｍ_ｎ及び濃度が所定範囲内にある電解液は、得られる析離箔の粗面の山の形状及び大きさが揃い且つ低粗度であることが判る。 From Tables 1 to 3, the electrolyte solution in which the number average molecular weight M _n and the concentration of gelatin in the copper electrolyte solution are within a predetermined range is uniform and low in the shape and size of the peaks of the rough surface of the obtained separation foil. It turns out to be roughness.

本発明に係る電解銅箔製造用銅電解液及び電解銅箔の製造方法は、電解銅箔のうちの析離箔の製造に用いることができる。 The copper electrolytic solution for producing an electrolytic copper foil and the method for producing an electrolytic copper foil according to the present invention can be used for producing a separating / separating foil of the electrolytic copper foil.

図１は、比較例１で得られた箔の粗面のＳＥＭ写真である。FIG. 1 is an SEM photograph of the rough surface of the foil obtained in Comparative Example 1. 図２は、比較例２で得られた箔の粗面のＳＥＭ写真である。FIG. 2 is an SEM photograph of the rough surface of the foil obtained in Comparative Example 2. 図３は、比較例３で得られた箔の粗面のＳＥＭ写真である。FIG. 3 is an SEM photograph of the rough surface of the foil obtained in Comparative Example 3. 図４は、実施例１で得られた箔の粗面のＳＥＭ写真である。FIG. 4 is an SEM photograph of the rough surface of the foil obtained in Example 1. 図５は、実施例２で得られた箔の粗面のＳＥＭ写真である。FIG. 5 is an SEM photograph of the rough surface of the foil obtained in Example 2. 図６は、実施例３で得られた箔の粗面のＳＥＭ写真である。6 is a SEM photograph of the rough surface of the foil obtained in Example 3. FIG. 図７は、比較例４で得られた箔の粗面のＳＥＭ写真である。FIG. 7 is an SEM photograph of the rough surface of the foil obtained in Comparative Example 4. 図８は、実施例４で得られた箔の粗面のＳＥＭ写真である。FIG. 8 is an SEM photograph of the rough surface of the foil obtained in Example 4. 図９は、実施例５で得られた箔の粗面のＳＥＭ写真である。FIG. 9 is an SEM photograph of the rough surface of the foil obtained in Example 5. 図１０は、実施例６で得られた箔の粗面のＳＥＭ写真である。FIG. 10 is an SEM photograph of the rough surface of the foil obtained in Example 6. 図１１は、比較例５で得られた箔の粗面のＳＥＭ写真である。FIG. 11 is an SEM photograph of the rough surface of the foil obtained in Comparative Example 5. 図１２は、比較例６で得られた箔の粗面のＳＥＭ写真である。FIG. 12 is an SEM photograph of the rough surface of the foil obtained in Comparative Example 6. 図１３は、実施例７で得られた箔の粗面のＳＥＭ写真である。FIG. 13 is an SEM photograph of the rough surface of the foil obtained in Example 7. 図１４は、実施例８で得られた箔の粗面のＳＥＭ写真である。FIG. 14 is an SEM photograph of the rough surface of the foil obtained in Example 8. 図１５は、実施例９で得られた箔の粗面のＳＥＭ写真である。FIG. 15 is a SEM photograph of the rough surface of the foil obtained in Example 9. 図１６は、比較例８で得られた箔の粗面のＳＥＭ写真である。FIG. 16 is an SEM photograph of the rough surface of the foil obtained in Comparative Example 8. 図１７は、実施例１０で得られた箔の粗面のＳＥＭ写真である。FIG. 17 is a SEM photograph of the rough surface of the foil obtained in Example 10. 図１８は、比較例９で得られた箔の粗面のＳＥＭ写真である。FIG. 18 is an SEM photograph of the rough surface of the foil obtained in Comparative Example 9. 図１９は、銅電解液中に含まれるタンパク質の数平均分子量Ｍ_ｎ及び濃度と、析離箔の常態の抗張力との関係を示すグラフである。FIG. 19 is a graph showing the relationship between the number average molecular weight _Mn and concentration of proteins contained in the copper electrolyte and the normal tensile strength of the separation foil. 図２０は、銅電解液中に含まれるタンパク質の数平均分子量Ｍ_ｎ及び濃度と、析離箔の粗面の粗度Ｒ_ｚとの関係を示すグラフである。Figure 20 is a number-average molecular weight M _n and the concentration of protein contained in the copper electrolyte solution is a graph showing the relationship between roughness R _z of the rough surface of the deposited foil. 図２１は、本発明におけるタンパク質の数平均分子量Ｍ_ｎ及び濃度の測定方法で用いる装置の一例を示す概略説明図である。FIG. 21 is a schematic explanatory diagram illustrating an example of an apparatus used in the method for measuring the number average molecular weight M _n and concentration of a protein in the present invention.

符号の説明Explanation of symbols

１ 送液ポンプ
２ インジェクタ
３ ６方切換バルブ
４ ６方切換バルブの第１の連結口
５ ６方切換バルブの第２の連結口
６ ６方切換バルブの第３の連結口
７ ６方切換バルブの第４の連結口
８ ６方切換バルブの第５の連結口
９ ６方切換バルブの第６の連結口
１０ 前処理カラム
１１ 第１検出器
１２ 分離カラム
１３ 第２検出器
１４ 排液パイプ
１５ 恒温槽
１６ 移動相溜め

DESCRIPTION OF SYMBOLS 1 Liquid feed pump 2 Injector 3 6-way switching valve 4 1st connection port of 6-way switching valve 5 Second connection port of 6-way switching valve 6 Third connection port of 6-way switching valve 7 6-way switching valve 4th connection port 8 5th connection port of 6-way switching valve 9 6th connection port 10 of 6-way switching valve Pretreatment column 11 1st detector 12 Separation column 13 2nd detector 14 Drain pipe 15 Constant temperature Tank 16 Mobile phase reservoir

Claims (7)

電解銅箔製造用の銅電解液であって、該銅電解液中に含まれるタンパク質は、数平均分子量Ｍ_ｎが１０００〜２３００、且つ、濃度が２ｐｐｍ〜４．５ｐｐｍであることを特徴とする電解銅箔製造用銅電解液。 A copper electrolyte for producing an electrolytic copper foil, wherein the protein contained in the copper electrolyte has a number average molecular weight _Mn of 1000 to 2300 and a concentration of 2 ppm to 4.5 ppm. Copper electrolyte for electrolytic copper foil production. 前記銅電解液は、Ｃｕ^２＋濃度が６０ｇ／ｌ〜１００ｇ／ｌであることを特徴とする請求項１記載の電解銅箔製造用銅電解液。 The copper electrolyte for producing an electrolytic copper foil according to claim 1, wherein the copper electrolyte has a Cu ²⁺ concentration of 60 g / l to 100 g / l. 前記銅電解液は、フリーＳＯ_４ ^２−濃度が６０ｇ／ｌ〜２５０ｇ／ｌであることを特徴とする請求項１又は２記載の電解銅箔製造用銅電解液。 The copper electrolyte for producing an electrolytic copper foil according to claim 1, wherein the copper electrolyte has a free SO ₄ ²⁻ concentration of 60 g / l to 250 g / l. 前記銅電解液は、Ｃｌ⁻濃度が０．５ｐｐｍ〜２．０ｐｐｍであることを特徴とする請求項１〜３のいずれか１項記載の電解銅箔製造用銅電解液。 The copper electrolyte for producing an electrolytic copper foil according to claim 1, wherein the copper electrolyte has a Cl ⁻ concentration of 0.5 ppm to 2.0 ppm. 前記銅電解液は、温度が４０℃〜６０℃であることを特徴とする請求項１〜４のいずれか１項記載の電解銅箔製造用銅電解液。 The said copper electrolyte solution is 40 to 60 degreeC, The copper electrolyte solution for electrolytic copper foil manufacture of any one of Claims 1-4 characterized by the above-mentioned. 請求項１〜５のいずれか１項記載の電解銅箔製造用銅電解液を用いることを特徴とする電解銅箔の製造方法。 The manufacturing method of the electrolytic copper foil characterized by using the copper electrolyte solution for electrolytic copper foil manufacture of any one of Claims 1-5. 電解電流密度が３０Ａ／ｃｍ^２〜７０Ａ／ｃｍ^２であることを特徴とする請求項６記載の電解銅箔の製造方法。

Method of manufacturing an electrolytic copper foil according to claim 6, wherein the electrolytic current density of ^{30A / cm 2 ~70A / cm 2} .