KR100772946B1 - Electrodeposited copper foil with low roughness surface and process for producing the same - Google Patents

Abstract

Surface roughness Rz is 2.0 micrometers or less, it is a low roughness electrodeposition copper foil which has the roughening surface uniformly low roughness without the unevenness | corrugation, and the elongation at 180 degreeC is 10.0% or more. This low surface electrodeposited copper foil uses an insoluble anode made of a titanium plate coated with an aqueous sulfuric acid-copper sulfate solution and coated with a white metal element or an oxide element thereof, and a titanium drum is used for the anode facing the anode. In the manufacturing method of the electrodeposited copper foil which let a direct current flow through a negative electrode, it can obtain by making oxyethylene type surfactant, polyethyleneimine or its derivative (s), sulfonate of an active organic sulfur compound, and chlorine ion exist in the said electrolyte solution.

Description

Low surface electrodeposition copper foil and manufacturing method therefor {ELECTRODEPOSITED COPPER FOIL WITH LOW ROUGHNESS SURFACE AND PROCESS FOR PRODUCING THE SAME}

The present invention relates to a low roughness electrodeposited copper foil having a roughened surface that is uniformly low roughness without roughness on the rough surface that can be used for a printed wiring board or a negative electrode current collector for a lithium secondary battery.

As is well known, the electrodeposited copper foil uses a sulfur-containing copper sulfate aqueous solution as an electrolyte and a titanium drum for an insoluble anode made of a titanium plate coated with a white metal element or an oxide element thereof, and a cathode facing the anode. The electrodeposited copper is deposited on the surface of the titanium drum by passing a direct current between the anode and the cathode. At this time, the titanium drum rotates at a constant speed, and the electrodeposited copper is removed from the drum surface and wound up continuously. Is manufactured by.

In addition, in this invention, the surface of the side which contacted the drum surface of electrodeposited copper foil is called "gloss surface", and the opposite surface is called "roughness surface."

Although electrodeposition copper foil is manufactured as mentioned above, this electrodeposition copper foil is called "unprocessed copper foil" among those skilled in the art, and is not normally used in the state of this untreated copper foil, In the case of the electrodeposition copper foil for printed circuits, resin It is made into a product through the roughening process aimed at improving adhesiveness, and the various surface treatment processes aimed at providing heat resistance, chemical resistance, and rust prevention power.

A long time ago, a means of sharpening (roughening) the rough shape of the rough surface by the presence of 10 to 100 mg / L chlorine ions and 0.1 to 4.0 mg / L glue or gelatin in the electrolytic solution in the manufacturing process of the untreated electrodeposited copper foil. In recent years, the roughness of the roughness side is as low as possible in the printed wiring board and the negative electrode current collector for lithium secondary batteries, which are the uses of electrodeposited copper foil, and the roughness difference between the glossy surface and the rough surface is small (the glossy surface is the Since a smooth shape is copied, a roughness difference inevitably arises between a gloss surface and a rough surface), and thin electrodeposited copper foil is calculated | required.

This is because of the demand from the viewpoint of improving the circuit accuracy accompanying the miniaturization of lines and patterns in the case of a printed wiring board, and in the case of a negative electrode current collector for a lithium ion secondary battery, the roughness difference between the gloss surface and the rough surface, that is, This is because there is less need to consider the difference in battery reaction based on the difference in surface area.

However, it is difficult to reduce the roughness difference between the gloss surface and the rough surface, and to satisfy various practical mechanical properties.

Conventionally, in the manufacturing method of electrodeposited copper foil, it is known that the roughness difference of a gloss surface and a rough surface can be made small by appropriately selecting and adding various water-soluble high molecular substance, various surfactant, various organic sulfur type compounds, chlorine ion, etc. to electrolyte solution. For example, in JP 2002-506484 A, a low molecular weight water soluble cellulose ether, a low molecular weight water soluble polyalkylene glycol ether, a low molecular weight water soluble polyethyleneimine and a water soluble sulfonated organic sulfur compound are added to an electrolyte solution. It is disclosed that electrodeposited copper foil (untreated electrodeposited copper foil) having a fine protrusion end of about 3.8 μm or less on the rough surface side is obtained. For example, Japanese Patent No. 3313277 discloses a cellulose ether, a low molecular weight glue, In the case of adding a compound having a mercapto group and chloride ion, the roughness on the rough surface side is low. It is disclosed that the electrodeposited copper foil (untreated electrodeposited copper foil) which has a small roughness difference between Arthur gloss surface and a rough surface and shows high elongation at high temperature is also obtained.

The inventors conducted several experiments in which an electrodeposited copper foil was obtained by appropriately adding various water-soluble high molecular substances, various organic sulfur compounds, chlorine ions, and the like described in the above publications to an electrolyte solution composed of a sulfuric acid-copper sulfate aqueous solution. As a result, although the roughness of the roughening side of the obtained electrodeposited copper foil could be made low, the roughness of the uneven | corrugated unevenness (refer FIG. 7 below) generate | occur | produced in this roughening surface.

The undulations of the smooth unevenness occurring in the rough surface of the electrodeposited copper foil (untreated electrodeposited copper foil) become a factor causing abnormal precipitation of copper crystal grains in the roughening treatment step, thereby increasing the elongation (Rz) of the product.

Moreover, in the flexible printed wiring board use, copper foil receives thermal history in the process of adhering with an insulating film, and when copper crystal grains are small, the copper crystal grains grow and coarsen by this thermal history.

Therefore, the present invention provides a low roughness electrodeposited copper foil having a roughly low roughened roughness without roughness on the rough surface that can be used for a printed wiring board or a negative electrode current collector for a lithium secondary battery, specifically, an elongation Rz of 2.0 μm or less. On the other hand, it is a technical problem to provide the low roughness electrodeposition copper foil which has the roughness uniformly low roughness without the unevenness | corrugation, and whose elongation at 180 degreeC is 10.0% or more.

The inventors of the present invention have made extensive studies to achieve the above-mentioned problems. As a result, polyoxyethylene surfactants, polyethyleneimine or derivatives thereof, sulfonates and chlorine ions of active organic sulfur compounds are used in an electrolyte solution composed of sulfuric acid-copper sulfate solution. In the presence of four additives, a low roughness electrodeposited copper foil having a surface roughness Rz of 2.0 μm or less, substantially free of unevenness and uniformly low roughness, and an elongation at 180 ° C. of 10.0% or more is obtained. I learned that it was remarkable, and achieved the subject.

Disclosure of the Invention

That is, the present invention is a low roughness electrodeposited copper foil having a surface roughness Rz of 2.0 µm or less and having a rough surface uniformly low roughness without undulation of unevenness, and an elongation at 180 ° C of 10.0% or more.

Moreover, in this low roughening electrodeposition copper foil, this invention is a mirror surface glossiness of the roughening surface measured by Gs (85 degrees) based on JIS (Japanese Industrial Standards: same) Z8741 is 100 or more.

In addition, the present invention uses a titanium drum for an insoluble anode composed of a titanium plate coated with a platinum group element or an oxide element thereof and an anode opposite to the anode, using a sulfuric acid-copper sulfate aqueous solution as an electrolyte, between the anode and the cathode. In the method for producing an electrodeposited copper foil which allows a direct current to flow through, the surface roughness Rz is 2.0 µm or less by providing oxyethylene surfactant, polyethyleneimine or a derivative thereof, sulfonate and chlorine ions of an active organic sulfur compound in the electrolyte solution. It is a manufacturing method of the low roughness electrodeposition copper foil which has the roughening surface uniformly low roughness without the undulation of, and obtains the low roughness electrodeposition copper foil whose elongation at 180 degreeC is 10.0% or more.

Moreover, this invention is a manufacturing method of the said low roughening electrodeposited copper foil which can obtain the low roughening electrodeposition copper foil whose mirror surface glossiness of the roughening surface measured by Gs (85 degree) based on JISZ8741 is 100 or more.

Moreover, this invention is a manufacturing method of the said low rough surface electrodeposition copper foil whose density | concentration of the oxyethylene type surfactant in electrolyte solution is 10-200 mg / L.

Moreover, this invention is a manufacturing method of the said low roughening electrodeposited copper foil whose density | concentration of the polyethylenimine or its derivative in electrolyte solution is 0.5-30.0 mg / L.

Moreover, this invention is a manufacturing method of the said low roughening electrodeposited copper foil whose density | concentration of the sulfonate of the active organic sulfur compound in electrolyte solution is 5.5-450 micromol / L.

Moreover, this invention is a manufacturing method of the said low surface electrodeposition copper foil whose density | concentration of chlorine ion in electrolyte solution is 20-120 mg / L.

The configuration of the present invention in more detail, as follows.

In the present invention, the additive to be added to the electrolyte solution composed of sulfuric acid-copper sulfate solution includes four additives of oxyethylene-based surfactant, polyethyleneimine or a derivative thereof, sulfonate of active organic sulfur and chlorine ion. Moreover, about the water-soluble polymer group, the target low roughness electrodeposition copper foil can be obtained only when it exists in a fixed molecular weight area | region.

First, as the oxyethylene surfactant used in the present invention, the polyethylene glycol has an average molecular weight of 2000 to 35000 and the polyoxyethylene polyoxypropylene copolymer has an average molecular weight of 2000 to 4000 and a starch molecular weight. The weight ratio of oxyethylene in the thing is 80 wt% or more, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, bisphenol A- ethylene oxide addition product, etc. are mentioned. Further, the weight ratio of oxyethylene in the starch molecular weight of 80 wt% or less is not dissolved in the electrolyte solution composed of sulfuric acid-copper sulfate aqueous solution.

When the average molecular weight of polyethyleneglycol is 2000 or less, abnormal electrodeposition occurs on the surface of electrodeposited copper foil.

In this invention, one type, or two or more types in the said compound are combined, and it adds to electrolyte solution so that the density | concentration in the electrolyte solution of the single or total may be 10-200 mg / L. The lower limit of this concentration range is important, and even if the polyethylenimine and its derivatives, the sulfonates and chlorine ions of the active organic sulfur are adjusted to the respective preferred concentration ranges described below, the target low roughness electrodeposited copper foil cannot be obtained. have. On the other hand, the upper limit is not a threshold for determining whether or not a low roughness electrodeposited copper foil can be obtained as indicated by the lower limit region. However, under industrial operating conditions, it is not an active value to maintain the concentration at a high value from an economic point of view. Does not have Therefore, although the upper limit prescribed | regulated here is not for defining the characteristic of the electrodeposited copper foil obtained, even if the objective low roughness electrodeposition copper foil can be obtained even in the area | region exceeding an upper limit area, it is not practical.

Moreover, the lower limit of an average molecular weight is also important, and when the average molecular weight 2000 is not satisfied, the target low roughness electrodeposition copper foil is not obtained. In addition, an upper limit can be said to be the same as the upper limit of a density | concentration range, For example, even if it uses the polyethyleneglycol exceeding an average molecular weight of 35000, it can fully predict that a low roughness electrodeposition copper foil is obtained.

Next, although the roughness of the unevenness | corrugation arises in the roughening surface of the electrodeposited copper foil obtained by adding an oxyethylene type surfactant, an active organic sulfur compound, and chlorine ion in electrolyte solution, generation of such an ups and downs can be suppressed by adding polyethyleneimine.

It is preferable that the weight average molecular weights of the polyethyleneimine used for this invention are 600 or more, and it is more preferable that it is 10000 or more. As long as a weight average molecular weight is 600 or more, you may use the linear form shown by following formula (1), the branched form shown by formula (2), and a mixture of both can also be used.

Moreover, as a commercial item, "Epomin: brand name, article number: P-1000, Nippon-catalyst manufacture and weight average molecular weight: 70000" are mentioned, for example.

As a polyethyleneimine derivative, it is preferable that the weight average molecular weight is 1000 or more as a propylene oxide addition product, and it is preferable that the molecular weight of the polyethyleneimine to which propylene oxide is added is 600 or more.

Moreover, as shown to following General formula (3), it is preferable to become a substituent with respect to the primary and secondary amine hydrogens of polyethyleneimine.

Moreover, as a commercial item, "Epomin: brand name, article number: PP-061, Nippon-catalyst manufacture and weight average molecular weight: 1200" are mentioned, for example.

When the weight average molecular weight of polyethyleneimine is less than 600 and the weight average molecular weight of the polyethyleneimine derivative is less than 1000, the roughness of the unevenness of the electrodeposited copper foil obtained irrespective of the concentration occurs, resulting in a smooth unevenness and glossiness (uniform low roughness). Is not. In addition, when the roughness of the roughness does not occur and the roughness is uniformly low roughness, the appearance has a gloss, but when the roughness and the roughness of the roughness occurs, the appearance is not uniformly low roughness. Becomes semi-gloss or not clear.

As a general tendency of the relationship between the concentration region of polyethyleneimine and its derivatives and its molecular weight, as the molecular weight increases, the concentration threshold at which the rough surface begins to change from semi-gloss to gloss rises, and powdery copper precipitation does not form a plating film. The concentration that begins to change to the "burnt deposits" area also shifts to the higher concentration side. Moreover, even if it is in the gloss region, when the concentration of polyethyleneimine is raised, the elongation at the time of high temperature will generate | occur | produce. After considering the molecular weight of polyethyleneimine and its derivatives and the effect of the concentration, it is necessary to determine each range of molecular weight and concentration, and the molecular weight of polyethyleneimine and its derivatives is preferably 600 to 70000, and the concentration in the electrolyte Is in the range of 0.5 to 30.0 mg / L, preferably in the range of 1.0 to 10.0 mg / L.

When the concentration of polyethyleneimine and its derivatives in the electrolyte solution is less than 0.5 mg / L, the rough surface shows an unclear appearance, and when it exceeds 30 mg / L, it moves to the "sintering" region, and further electrodeposited copper foil can be obtained. none.

Next, although the active organic sulfur compound used for this invention is a compound which solubilized the lightly soluble alkylthiol of the lightly soluble in water, when the hydroxyl group or the carboxyl group is added in order to solubilize, the desired low surface electrodeposition is carried out. Can not get copper foil. Therefore, it is necessary to solubilize in the form of sulfonate. Representative compounds of the sulfonate salts of the active organic sulfur compounds preferred in the present invention are represented by the following general formulas (4), (5), (6) and (7).

It is not suitable to express the addition amount of these compounds as mass concentration. Note that these compounds have a thiol group present in the structure whose effect is determined, the compound of formula (5) is a two-molecule association of 3-mercapto-1-propanesulfonic acid represented by formula (4) The group is formed, and even one molecule exhibits twice the effect of sodium 3-mercapto-1-propanesulfonate, which can be defined by the number of moles of thiol groups present in the molecule.

Therefore, when the amount of thiol group present is expressed in molar concentration, the amount (molar concentration) of the active organic sulfur compound in the present invention to the preferred electrolyte solution is in the range of 5.5 to 450 µmol / L, preferably 55 to 180 µmol / L. It is preferable that it is the range of. When the concentration in the electrolyte solution is not satisfied at 5.5 μmol / L, gentle unevenness of the rough surface occurs, uniform appearance is not reduced, and the appearance is not clear, and glossiness does not occur. Moreover, the elongation at 180 ° C is also low. Although the addition amount exceeds 450 μmol / L, there is no effect on the roughness or the elongation at 180 ° C. However, maintaining a high concentration of the active organic sulfur compound in the electrolyte is expensive for high anode potential when an electrodeposited copper foil is obtained using an insoluble anode. It is not realistic because organic sulfur compounds are decomposed and consumed unnecessarily.

Next, in the present invention, the presence of chlorine ions is very important, and even if the sulfonate of the oxyethylene surfactant, polyethyleneimine or its derivatives and the active organic sulfur compound is adjusted to each of the above-mentioned preferred concentration ranges, the desired low concentration is achieved. No electrodeposited copper foil. The object of the present invention is achieved only when chlorine ions coexist.

In addition, the relationship between the chlorine ion concentration and the active organic sulfur compound concentration is also important, and the concentration region in which the rough surface exhibits a glossy appearance (a state in which the rough surface is not uniformly low in the roughness of the rough surface is not generated) is characterized in that the chlorine ion concentration and the active organic phase. It is almost determined by the sulfur compound concentration, and the gloss range tends to shrink as the chlorine ion concentration rises, so that it is preferable to reduce the concentration of chlorine ions to lower the concentration of the active organic sulfur compound. Therefore, the chlorine ion concentration in the electrolyte solution is preferably in the range of 20 to 120 mg / L, preferably in the range of 30 to 100 mg / L. When the concentration of chlorine ion is not satisfied at 20 mg / L, the rough surface does not lower the surface roughness to 2.0 µm or less. When chlorine ion exceeds 120 mg / L, a plated surface will become rough.

The source of chlorine ions may be an inorganic salt that dissociates in an aqueous solution to release chlorine ions, and examples thereof include NaCl, HCl, and the like.

In the present invention, four sulfuric acid-copper sulfates are prepared by adjusting the oxyethylene surfactant, the polyethyleneimine or a derivative thereof, the four additives of sulfonate and chlorine ions of the active organic ion compound to the respective preferred concentration ranges described above. By using an aqueous solution as an electrolyte solution, using a white metal oxide-coated titanium plate for the positive electrode and a titanium drum for the negative electrode, the electrolytic solution was electrolyzed under the conditions of an electrolyte solution temperature of 35 to 50 ° C. and an electrolytic current density of 30 to 50 A / dm 2. Low electrodeposited copper foil can be obtained.

BRIEF DESCRIPTION OF THE DRAWINGS It is an electron micrograph (magnification x 1000) which image | photographed the rough surface of the electrodeposition copper foil (untreated electrodeposition copper foil) obtained by the best form for implementing this invention.

FIG. 2 is an electron micrograph (magnification × 1000) of the rough surface of the electrodeposited copper foil (untreated electrodeposited copper foil) obtained in Comparative Example 1. FIG.

3 is an electron micrograph (magnification × 1000) of the rough surface of the electrodeposited copper foil (untreated electrodeposited copper foil) obtained in Comparative Example 3. FIG.

4 is an electron micrograph (magnification × 1000) of the rough surface of the electrodeposited copper foil (untreated electrodeposited copper foil) obtained in Comparative Example 4. FIG.

5 is an electron micrograph (magnification × 1000) of the rough surface of the electrodeposited copper foil (untreated electrodeposited copper foil) obtained in Comparative Example 6. FIG.

FIG. 6 is an electron micrograph (magnification × 1000) of the rough surface of the electrodeposited copper foil (untreated electrodeposited copper foil) obtained in Comparative Example 7. FIG.

FIG. 7 is an electron micrograph (magnification × 1000) of the rough surface of electrodeposited copper foil (untreated electrodeposited copper foil) obtained by using an electrolyte solution without adding polyethyleneimine.

Best mode for carrying out the present invention is as follows.

Sulfuric acid (H ₂ SO ₄ ): 100 g / L, copper sulfate pentahydrate (CuSO ₄ · 5H ₂ O): An electrolyte solution consisting of 280 g / L sulfuric acid-copper sulfate solution was prepared (hereinafter, this electrolyte solution is referred to as “basic electrolyte solution”). ).

Polyethyleneglycol (average molecular weight 20000., acidification | purification production), polyethyleneimine (Epomin: brand name, article number: P-1000, Nippon-catalyst manufacture, weight average molecular weight: 70000) as an additive, 3-mercapto-1- Sodium propanesulfonic acid and hydrochloric acid were added to the basic electrolyte solution to polyethylene glycol: 30 mg / L, polyethyleneimine: 0.5 mg / L, 3-mercapto-1-propanesulfonate: 220 μmol / L and chlorine ion: 35 mo1 / L. Adjusted.

An electrolyte solution containing this additive is introduced between a platinum group oxide-coated titanium plate as an anode and a titanium drum as a cathode to be electrocrystallized at an electrolytic current density of 45 A / dm 2 and an electrolyte temperature of 40 ° C. to 18 µm in thickness. Obtained low surface electrodeposition copper foil. In addition, it was confirmed by visual observation that the rough surface of this low roughness electrodeposition copper foil had glossiness.

The tensile strength (MPa) and elongation (%) at room temperature (about 25 ° C.) and 180 ° C. of the low rough electrodeposited copper foil (untreated electrodeposited copper foil) obtained here were based on IPC-TM-650. The surface roughness (Rz) of the rough surface was measured using Safkoda SE1700α manufactured by Kosaka Research Institute, based on JISB0601, while measuring using a 2001-type tensile force tester. In addition, as an index indicating the degree of undulation of the unevenness in the rough surface of the low roughness electrodeposition copper foil, Gs using a glossmeter (trade name: Multi-Gloss 268 type) manufactured by Minolta Co., Ltd. based on JISZ8741 It measured with respect to 2 directions of the width direction of a low roughness electrodeposition copper foil in the (85 degree), and a length (flow) direction. Each measurement result is shown in Table 2.

In addition, the said mirror glossiness Gs (85 degree) shows the numerical value of 100 or more, when the roughness of the unevenness | corrugation has not generate | occur | produced roughly, and the numerical value of less than 100 when the smooth unevenness | corrugation of the roughness generate | occur | produces in the rough surface (See Table 2 and FIGS. 1 to 7 below). That is, the value of the mirror glossiness Gs (85 °) can be used as an index of the degree of relief of roughness on the rough surface, and the smaller the value, the greater the degree of relief of the irregularities, and the larger the value, the degree of relief of the irregularities Is small.

FIG. 1 is an electron micrograph (magnification × 1000) of the rough surface of the low roughness electrodeposited copper foil (untreated electrodeposition copper foil) obtained here, and by this figure, roughness is substantially low and uniformly low in the roughness. You can check the state of the rough.

Next, Examples 1-7 and Comparative Examples 1-9 of this invention are as follows.

Except having changed the kind of additive, the density | concentration in electrolyte solution, electrolytic current density, and electrolyte solution temperature as shown in Table 1, it is 18 micrometers in thickness under the conditions similar to each condition in the best form for implementing this invention. Electrodeposited copper foil was obtained. The tensile strength (MPa) and elongation (%) and surface roughness (Rz) (micrometer) in room temperature (about 25 degreeC) and 180 degreeC of each obtained electrodeposition copper foil (untreated electrodeposition copper foil), and the width direction and length in a rough surface ( Table 2 shows the results of measuring the specular glossiness Gs (85 °) in the direction of flow) by the same measuring method as the measuring method in the best mode for carrying out the present invention.

(1) Average molecular weight 70000, (2) Polyethylenimine derivative (Epomin: Brand name and part number: PP-061, Nippon-catalyst manufacture, weight average molecular weight: 1200), (3) Average molecular weight 1000, (4) Average molecular weight 300, (5) an average molecular weight of 600.

2-6 is the electron micrograph (magnification x 1000) which image | photographed the rough surface of each electrodeposited copper foil (untreated electrodeposition copper foil) obtained by the comparative example, and FIG. 2 is the comparative example 1 (the average molecular weight of polyethyleneglycol is low, polyethyleneimine Fig. 3 shows the rough state of Comparative Example 3 (when the weight average molecular weight of polyethyleneimine is low), and Fig. 4 shows the rough state of Comparative Example 4 (low average molecular weight of polyethylene glycol and The roughness state of the case where the concentration is high), FIG. 5 shows the roughness state of the comparative example 6 (when the concentration of polyethyleneimine is low), and FIG. 6 shows the concentration state of the comparative example 7 (sodium 3-mercapto-1-propanesulfonate) Low roughness), respectively.

Fig. 7 is an electron micrograph (magnification × 1000) of a rough surface of an electrodeposited copper foil (untreated electrodeposited copper foil) having a thickness of 18 μm obtained under the same conditions as in the embodiment of the present invention, except that polyethyleneimine is not added. It is possible to confirm the state of the ups and downs of the irregularities. In addition, in contrast to Fig. 7 and Fig. 1 in the best mode for carrying out the present invention, it can be confirmed that the addition of polyethyleneimine does not cause undulation of smooth irregularities on the rough surface and the surface roughness is significantly reduced.

Further, from Tables 1 and 2, in the best mode for carrying out the present invention and in each of the electrolyte solutions of Examples 1 to 7, the tensile strength at room temperature increases as the concentration of polyethyleneimine increases, but the surface roughness (Rz ) Is almost constant.

In addition, the present inventors have shown, by several experiments, that when the polyethylene glycol is not present in the basic electrolyte solution, the rough surface does not have a glossy appearance, and when the polyethyleneimine is not present, the rough surface has a rough and unclear appearance. , Elongation at 180 ° C is low, roughness is very rough when 3-mercapto-1-propanesulfonate is not present, elongation at 180 ° C is low, and electrodeposited surface when no chlorine ion is present (Plating surface) cracked and it discovered that elongation at 180 degreeC was low.

Moreover, when the density | concentration and average molecular weight of water-soluble polymer were increased within the said predetermined range, it discovered that the said mirror glossiness Gs (85 degrees) tends to increase by this. Moreover, in order to obtain the low roughness electrodeposition copper foil whose said mirror glossiness Gs (85 degrees) is 100 or more, although polyethyleneglycol, 3-mercapto- 1- propanesulfonic acid sodium salt, polyethyleneimine, and a chloride ion are suitable to exist in a basic electrolyte solution, When any one of these substances is deficient, or the concentration or average molecular weight is outside the predetermined range, the specular glossiness Gs (85 °) is less than 100.

According to the present invention, the optimum surface roughness Rz is 2.0 µm or less, which is optimal for printed wiring board applications or negative electrode current collector applications for secondary batteries, and the roughness of the roughness is substantially absent, and the mirror glossiness Gz (85 °) is equal to or greater than 100. It is possible to provide a low roughness electrodeposited copper foil (untreated electrodeposited copper foil) having a roughly low roughened surface, having an elongation at 180 ° C of 10.0% or more, and having a small roughness difference between the glossy surface and the rough surface.

Claims (7)

Even roughness of surface roughness Rz of untreated electrodeposited copper foil is 2.0 μm or less, no irregularities of irregularities, and mirror glossiness of 100 or more, measured by Gs (85 °) based on JIS (Japanese Industrial Standards: same as below) Z8741 The low roughness electrodeposition copper foil which has a roughened roughening, and the elongation at 180 degreeC is 10.0% or more. An insoluble anode made of a titanium plate coated with a platinum group element or an oxide element thereof as an electrolyte solution using a sulfuric acid-copper sulfate solution, and a titanium drum are used to pass a direct current between the anode and the cathode using a titanium drum. In the method for producing electrodeposited copper foil, an oxyethylene surfactant, polyethyleneimine or derivative thereof, sulfonate and chlorine ion of an active organic sulfur compound are present in the electrolyte solution so that the surface roughness Rz is 2.0 µm or less and uniform without irregularities. A low roughness electrodeposited copper foil, which has a roughened surface roughly lowered and has an elongation at 180 ° C. of 10.0% or more. The method of claim 2, The manufacturing method of the low roughness electrodeposition copper foil whose mirror surface glossiness of the roughening surface measured by Gs (85 degrees) based on JISZ8741 in low roughness electrodeposition copper foil is 100 or more. The method of claim 2 or 3, The manufacturing method of the low surface electrodeposition copper foil whose density | concentration of the oxyethylene type surfactant in electrolyte solution is 10-200 mg / L. The method of claim 2 or 3, The manufacturing method of the low surface electrodeposition copper foil whose density | concentration of the polyethylenimine or its derivative (s) in electrolyte solution is 0.5-30.0 mg / L. The method of claim 2 or 3, The manufacturing method of the low surface electrodeposition copper foil whose density | concentration of the sulfonate of the active organic sulfur compound in electrolyte solution is 5.5-450 micromol / L. The method of claim 2 or 3, The manufacturing method of the low surface electrodeposition copper foil whose density | concentration of chlorine ion in electrolyte solution is 20-120 mg / L.

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