KR20050063784A - Surface-treated copper foil having blackening-treated surface, process for producing the surface-treated copper foil and, using the surface-treated copper foil, electromagnetic wave shielding conductive mesh for front panel of plasma display - Google Patents

Abstract

A surface-treated copper foil exhibiting excellent black color which can be worked by the customary copper etching process; and a conductive mesh for PDP produced from such a surface- treated copper foil. In particular, use is made of, for example, a surface-treated copper foil having a blackening-treated surface on a glossy surface side, characterized in that a cobalt sulfate plating layer is disposed on a glossy surface and a rustproof treated layer disposed thereon. For the production of this surface-treated copper foil, there is employed, for example, a process comprising subjecting a glossy surface of copper foil to electrolysis in a black cobalt plating solution containing cobalt sulfate (hexahydrate) at a current density of 2 A/dm 2 or higher so as to form a rustproof treated layer and thereafter carrying out water washing and drying.

Description

Surface-treated copper foil having a blackened surface, a manufacturing method of the surface-treated copper foil, and an electromagnetic shielding conductive mesh for a front panel of a plasma display using the surface-treated copper foil {Surface-treated copper foil having blackening-treated surface, process for producing the surface-treated copper foil and, using the surface-treated copper foil, electromagnetic wave shielding conductive mesh for front panel of plasma display}

A surface-treated copper foil having a blackened surface and an electromagnetic wave shielding metal mesh for a front panel of a plasma display using the surface-treated copper foil.

BACKGROUND OF THE INVENTION Conductive meshes for shields in plasma display panels have evolved from metallized fiber fabrics to conductive meshes in advance. Several methods are established for manufacture of this conductive mesh. One of them is to laminate the surface-treated copper foil onto a PET film and to bond the same, and to manufacture the photolithographic etching method. The other is a single conductive mesh of the surface-treated copper foil obtained by etching the surface-treated copper foil together with the supporting substrate by a photolithography etching method, and then peeling the support shell.

In addition, with the recent demand for energy saving, development is underway aiming at a plasma generation signal voltage of 200V to 50V, and the circuit width of the conductive mesh is increased in response to the decrease in luminance accompanying the voltage drop. Attempts have been made to linearize and reduce the coverage of the front glass panel by the conductive mesh. To this end, attempts have been made to make the thickness of the conductive mesh thin and to facilitate the etching process. One of them forms a seed layer which becomes a seed of electroplating by sputtering deposition on a PET film, and then forms a thin copper layer by electrolytic copper plating or the like, and a mesh line width by a photolithography etching method. The conductive mesh which refined | miniaturized has been performed.

Even if the conductive mesh is manufactured by any of these methods, the conductive mesh itself is inserted into the front panel and can be directly identified from the surface to the eye through the front glass, so that one side of the surface-treated copper foil processed with the conductive mesh is black. To increase the luminance of the transmitted light. Conventionally, the blackening process etc. which form a copper oxide layer performed in order to improve the adhesiveness with the resin layer of an inner layer circuit of a multilayer printed wiring board have been dedicated to this process.

Non-Patent Document 1: Technical Trends of PDP Materials Hitachi Chemical Technical Report No. 33 (1999-7)

Patent Document 1: Japanese Patent Application Laid-Open No. 11-186785

Patent Document 2: Japanese Patent Application Laid-Open No. 2000-31588

FIG. 1: is a figure which shows typically the cross-sectional layer structure of the surface-treated copper foil provided with the blackening process surface.

FIG. 2: is a figure which shows typically the cross-sectional layer structure of the surface-treated copper foil provided with the blackening process surface.

3 is an FIB observation image of a cross-sectional layer structure of a surface-treated copper foil having a blackened surface.

4 is an FIB observation image of a cross-sectional layer structure of a surface-treated copper foil having a blackened surface.

5 is an FIB observation image of a cross-sectional layer structure of a surface-treated copper foil having a blackened surface.

It is a figure which shows typically the cross-sectional layer structure of the surface-treated copper foil provided with the blackening process surface.

FIG. 7: is a figure which shows typically the cross-sectional layer structure of the surface-treated copper foil provided with the blackening process surface.

FIG. 8: is a figure which shows typically the cross-sectional layer structure of the surface-treated copper foil provided with the blackening process surface.

It is a figure which shows typically the cross-sectional layer structure of the surface-treated copper foil provided with the blackening process surface.

10 is a scanning electron microscope image of the roughened copper foil surface.

11 is a scanning electron microscope image of a cobalt sulfate layer observed.

12 is a scanning electron microscope image of an etching test pattern.

13 is a scanning electron microscope image of the surface of a copper foil on which a cobalt sulfate plating layer is formed without performing a roughening treatment.

14 is a scanning electron microscope image of the surface of a copper foil on which a cobalt sulfate plating layer is formed without performing a roughening treatment.

[Description of the code]

1a, 1b, 1c, 1d, 1e, 1f ... surface treated copper foil

2 .. Rough Treatment Layer

3..fine copper particles

4..Cobalt sulfate plated layer

5. Antirust layer (zinc-nickel alloy layer or zinc-cobalt alloy layer)

6..Chromated Treatment Layer

7. Copper foil layer

However, the above-mentioned blackening process had a serious problem. In other words, if a large amount of copper black oxide is deposited on the surface of the copper foil, a good black screen with strong black color can be obtained surely. However, the black oxide of copper formed on the copper foil surface tends to drop off from the black screen as the adhesion amount increases, and the phenomenon that powder falls easily occurs.

When the powder falling phenomenon occurs, the dropped black oxide is mixed in an unnecessary place, or during the transparent treatment for integrating with the glass of the front panel, may be dispersed in the transparent adhesive layer to deteriorate the transparency.

On the other hand, as a blackening treatment capable of forming a good black surface without the powder fall like blackening treatment, general black nickel plating, nickel sulfide plating, cobalt plating, and the like have been studied, but the blackening treatment surface side in a normal copper etching process The problem that the etching process from this process was impossible has arisen.

Here, the problem regarding nickel plating has been disclosed by the present inventors in Japanese Patent Application 2003-045669. However, the problem solving regarding the surface-treated copper foil provided with the blackening process surface using cobalt plating was still not tried. In particular, there has been a problem that the etching process of the cobalt layer using a copper etchant is difficult for copper foil provided with a cobalt black plating film that is currently distributed in the market.

Therefore, there is a need in the market for a surface treated copper foil having a blackening treatment layer having a good black color and having a cobalt plated coating that can be easily etched in a conventional copper etching process, and a conductive mesh made of such a surface treated copper foil. It has been.

Here, the inventors of the present invention have repeatedly studied, and by using the surface-treated copper foil as shown below, even if the surface-treated copper foil having a black cobalt plating layer can be easily etched with a copper etchant, The electromagnetic shielding conductive mesh for the front panel of the plasma display can be obtained.

<Surface treated copper foil with a blackened surface>

The surface-treated copper foil provided with the blackening process surface which concerns on this invention includes the case where a rustproofing layer is not provided and the case where a rustproofing layer is provided. Therefore, although an antirust process layer is not essential, it is necessary in order to ensure long-term storage property as surface-treated copper foil. Hereinafter, the surface-treated copper foil which concerns on this invention is demonstrated.

1st surface-treated copper foil: The surface-treated copper foil which concerns on this invention is a surface-treated copper foil provided with the blackening process surface on the gloss surface, sulfuric acid whose weight thickness is 200 mg / m <2> -400 mg / m <2> on one side of a copper foil layer. A cobalt plating layer is provided, and the cross-sectional height of this blackening process surface is 200 nm or less (The surface-treated copper foil is called hereafter. "). FIG. 1: shows the cross-sectional layer structure of this surface-treated copper foil 1a typically.

In this FIG. 1, the cobalt sulfate plating layer 4 is formed on the gloss surface of the electrolytic copper foil 7, and on the opposite surface (corresponding to the rough surface in the case of electrolytic copper foil), the coarse treatment is performed with fine copper particles 3. The surface-treated copper foil 1a is typically described as an example. However, the opposite surface of the copper foil used at this time may or may not be roughened. Therefore, in FIG. 2, the surface-treated copper foil 1b when the roughening process of the opposite surface is abbreviate | omitted is shown typically. The roughened layer 2 composed of the fine copper particles 3 is formed for the purpose of improving the adhesiveness to the substrate or the like and may be provided as necessary. As the method for forming the roughened layer 2, a method of attaching and forming fine copper particles and attaching fine copper oxide may be employed as described above. There is no limit. In addition, the copper foil layer 7 mainly uses the electrolytic copper foil obtained by the electrolytic method and the rolled copper foil obtained by the rolling method.

And the cobalt sulfate plating layer 4 is provided in the smooth gloss surface of this copper foil layer 7. The cobalt sulfate plating layer 4 used here means a layer formed by a plating method using a cobalt sulfate solution. The cobalt sulfate plating layer 4 is formed into a layer having a weight thickness of 200 mg / m 2 to 400 mg / m 2 by employing the manufacturing method described later, so that the cobalt sulfate plating layer 4 is excellent in solubility in the copper etching solution and sufficient blackening is possible. The cobalt layer of the copper foil provided with the black plating film using the conventional cobalt layer was very thick about 1000 mg / m <2> in weight thickness, and there existed a difference in the quality of the solubility of a plating layer. As a result, the dissolution rate by the copper etchant was slowed due to the thickness, and cobalt element itself accumulated at a high concentration in the copper etchant, resulting in a decrease in the titer of the etchant. In addition, the converted weight in this invention is the value converted into cobalt weight. The converted weight is obtained by dissolving the surface-treated copper foil in an acid solution, obtaining an amount of cobalt per unit area by plasma emission spectrometry, etc., and converting it to the weight per 1 m 2 of the surface-treated copper foil.

It has also been found that whether the cobalt plating layer becomes easily soluble in the copper etching solution can be greatly influenced depending on the plating conditions when the cobalt plating is performed. That is, the cobalt plating film obtained when employ | adopting the manufacturing method of the surface-treated copper foil which concerns on this invention mentioned later becomes the thing excellent in the etching characteristic most.

The second characteristic of the surface-treated copper foil according to the present invention is that the surface shape of this blackening treatment surface is not extremely rough, and the cross-sectional height of the blackening treatment surface is 200 nm or less. That is, a very smooth and glossy blackened surface is produced. However, in order to avoid misunderstanding, it is obvious that there is a deviation within the normal manufacturing process range, and the cross-sectional height at all positions does not necessarily need to be 200 nm or less, and reflects the deviation of the manufacturing process. Naturally, the cross-sectional height exceeding 200 nm may exist. In order to measure the cross-sectional height of the cobalt sulfate plating layer 4 of the surface-treated copper foil 1 which concerns on this invention, the FIB observation image observed with the cross section using the FIB analyzer is shown in FIG. 3, the blackening process surface was formed in the glossy surface of the electrolytic copper foil. In addition, this FIB observation image is observed with a 60 degree angle direction with respect to an observation surface.

As can be seen in FIG. 3, it is understood that a certain unevenness exists in the cross section of the blackened surface, and when monitoring such unevenness, it is common to use a stylus type surface roughness measuring system. . However, as can be seen from the scale of FIG. 3, it is considered that the surface roughness measurement system is an unevenness at a level at which accurate roughness measurement is impossible. Therefore, in the present invention, as the value corresponding to Rmax when measured by the surface roughness measurement system, the maximum difference between the ridge and the valley in the field of view on the FIB observation is 'cross-section height'. The place shown by "d" in this FIG. 3 becomes the cross-sectional height of FIG. 3, and can be judged as about 100 nm. In addition, in FIG. 3, the cobalt sulfate plating layer 4 is formed along the shape of the copper foil surface with a very uniform thickness, maintains a state of being completely in contact with the copper foil surface of the underlying, sulfuric cobalt plating layer 4 The place where the defect such as this glass is generated is not found, and the place where powder fall is expected is not found.

On the other hand, when the blackening process surface formed on the surface of the conventional copper foil is FIB observed from the cross section similarly to the above-mentioned, the result as shown in FIG. 4 and FIG. That is, it turns out that the shape which comprises the blackening process surface grows in resin shape, and is in the state which protruded considerably from the copper foil of a base. Therefore, when the cross-sectional height d at this time is measured, it turns out that the case of FIG. 4 is about 480 nm, and the case of FIG. 5 is about 270 nm, and it is a very rough surface. In addition, such a blackened surface having a resinous shape may be said to be a surface prone to breakage and damage of the dendritic portion. It is thought that it causes color bleeding when the blackening process surface is seen visually.

It can be seen that the surface-treated copper foil according to the present invention described above has a very smooth surface from the FIB cross-sectional view of FIG. 3. However, although it is a gloss blackening treatment, it does not have a gloss enough to diffusely reflect light received by the blackening treatment surface, and even when blackening treatment is performed on the glossy surfaces of the electrolytic copper foil and the rolled copper foil, L value becomes 27 or more. As described above, the upper limit is not particularly limited, but about 41 seems to be the upper limit empirically.

In order to show the glossiness of a blackening process surface, it is more preferable to show glossiness than Lab color system. As for the glossiness of the blackening process surface which concerns on this invention, when the said blackening process surface was formed in the gloss surface of an electrolytic copper foil or a rolled copper foil, it is preferable that glossiness [Gs (60 degrees)] is 30 or less. This is because when the glossiness is 30 or more, it becomes a so-called black light state and the metallic luster becomes noticeable. In addition, although the lower limit of glossiness is not determined here, it is about 18 empirically.

2nd surface treatment copper foil: This surface treatment copper foil forms the antirust process layer in order to ensure long-term storage property on the surface of the 1st surface treatment copper foil mentioned above. The cross-sectional layer structure of the surface-treated copper foil 1c provided with the antirust process layer 5 on both surfaces of FIG. 6 was typically illustrated. In addition, in FIG. 7, the surface-treated copper foil 1d when the roughening process with respect to the rough surface side is omitted is shown. As long as it is only for rust prevention as copper foil, organic rust prevention, such as imidazole and benzotriazole, inorganic rust prevention by zinc alloys, such as zinc or brass which are generally used, can be used widely. Do. In addition, although the antirust process layer at the time of forming a cobalt sulfate plating layer on one side should be provided in the opposite surface which provided the cobalt sulfate plating layer of the surface-treated copper foil which concerns on this invention at least, it does not interfere even if it is provided in both surfaces.

However, when the antirust treatment layer 5 is provided on both sides, the antirust treatment layer serves as a protective layer of the cobalt sulfate layer 4 and preventing the falling of the fine copper particles 3 of the roughening layer 2. At the same time, it will serve to maintain the appearance as a surface-treated copper foil for a long time. As this antirust process layer 5, it is especially preferable to provide a zinc-nickel alloy layer or a zinc-cobalt layer. By using these antirust process layers 5 in combination with the cobalt sulfate plating layer 4, it is thought that they function as the dissolution promoter at the time of etching-dissolving the cobalt sulfate plating layer 4. That is, the dissolution of the cobalt sulfate plating layer 4 occurs more quickly in the case where the cobalt sulfate plating layer 4 is present alone than the zinc-nickel alloy layer or zinc-cobalt layer.

In addition, the cross-sectional layer structure of the surface-treated copper foil 1c which provided the antirust process layer 5 and the chromate treatment layer 6 on both surfaces in FIG. 8 and FIG. 9 is shown typically. As can be seen by contrasting each of FIGS. 6 and 8, 7 and 9, the difference from the surface-treated copper foil with the rust-preventing layer 5 is only the point with the chromate-treated layer 6. And other structures are the same.

The chromate treatment layer 6 is formed on one side or both sides after the antirust treatment layer 5 made of a zinc-nickel alloy, a zinc-cobalt alloy, or the like is formed. The presence of this chromate treated layer 6 significantly improves the oxidation resistance of the surface-treated copper foil, and effectively prevents cosmetic collimation such as oxidation discoloration.

<Method for producing surface-treated copper foil having a blackened surface>

(Manufacturing method of 1st surface treatment copper foil) It is preferable to employ | adopt the manufacturing method containing the following processes as the manufacturing method of the 1st surface treatment copper foil mentioned above. This manufacturing method can be further subdivided in the case of employ | adopting a stirring bath and the case of using an unstirred bath, and can be further subdivided. Divided into and explained.

Manufacturing method A of 1st surface-treated copper foil: Here, the manufacturing method which employ | adopted the blackening treatment method at the time of using an unstirred bath is demonstrated.

It is irrespective of whether the copper foil used by the manufacturing method of the surface-treated copper foil which concerns on this invention performs a roughening process on the opposite surface to form a cobalt sulfate plating layer as mentioned above. Although it is described here for the sake, there is no particular limitation on the conditions when the rough treatment is carried out. For example, when forming the ultrafine copper particles, it is generally preferable to use a copper electrolyte containing arsenic. It is possible. For example, as a copper sulfate solution, copper concentration 5-10 g / l, sulfuric acid concentration 100-120 g / l, chlorine concentration 20-30 ppm, 9-phenylacridine 50-300 mg / l, liquid temperature 30-40 degreeC, It is set as the conditions of electrolytic density 5-20 A / dm <2>.

In the process of a), a cobalt sulfate plating layer is formed on the gloss surface of the above-mentioned copper foil. The cobalt sulfate plating layer contains 8 g / l to 10 g / l of cobalt sulfate (hexahydrate), uses a cobalt sulfate plating solution having a pH of 4.0 or more as an unstirred bath, and is electrolyzed at a current density of 2 A / dm 2 or more. To form a black cobalt sulfate plating layer. That is, it is a cobalt sulfate plating condition in the case where solution stirring is not performed. When the cobalt sulfate (hexahydrate) in the cobalt sulfate plating solution is less than 8 g / l, the electrodeposition rate of the cobalt sulfate plating layer to be formed is slowed, and the thickness of the nickel sulfate layer is increased. On the other hand, when cobalt sulfate (7-hydrate) exceeds 10 g / l, the color tone of the cobalt sulfate plating layer formed will not be in a favorable blackening state.

Moreover, it is preferable to adjust the pH of the solution of the cobalt sulfate plating solution to the range of 4.5-5.5 at this time. This is because a good yield of a good black cobalt plating layer can be obtained in this range. In order to perform this pH adjustment, it is not preferable to add another electrolyte, such as sodium hydroxide or potassium hydroxide. This is because the black color of the cobalt plating layer is easily changed to a metallic color.

Therefore, the pH of the solution is to stabilize the concentration of the metal ions in the solution as a result, in the range of 4.0 or more. In order to stabilize the cobalt ion concentration in the solution as described above, the cobalt ion concentration is dissolved or supplied by dissolving the electrodeposited cobalt ions using a soluble cobalt electrode, or by continuously monitoring the metal ion concentration and adding an appropriate amount using cobalt hydroxide. It is preferable to employ techniques such as stabilization.

And as a current density at the time of electrolysis, the electric current of 2A / dm <2> or more is used. The cobalt sulfate plating solution described above has a small rate of powder falling phenomenon even if an excessive electrolytic current flows to form a plated surface with a slight unevenness to some extent. Therefore, it is not necessary to particularly set an upper limit of the current density, and may be arbitrarily determined in consideration of the productivity in the process in view of technical common sense.

In the process of b), the copper foil which passed the above process is washed with water and dried, and the surface-treated copper foil which makes a cobalt sulfate plating layer blackening process surface is obtained. There is no restriction | limiting in particular in the washing method and the drying method here, The method which can be normally considered can be employ | adopted.

Manufacturing method B of 1st surface-treated copper foil Here, the manufacturing method which employ | adopted the blackening treatment method at the time of using a stirring bath is demonstrated.

Also in the manufacturing method of the surface-treated copper foil which concerns on this invention, forming a cobalt sulfate plating layer is similar to the cobalt sulfate plating layer formed by the unstirred cobalt sulfate plating bath by employ | adopting the gloss surface of copper foil and the following conditions, It is a cotton.

At this time, in the step a), the gloss surface of the copper foil described above contains 10 g / l to 40 g / l of cobalt sulfate (hexahydrate), and a pH of 4.0 or more and a liquid temperature of 30 ° C. or lower is used for the cobalt sulfate plating solution. It is used as a stirring bath, it electrolyzes with a current density of 4 A / dm <2> or less, and forms a black system cobalt sulfate plating layer. That is, a fundamental difference from the manufacturing method A of a 1st surface-treated copper foil here is the point which electrolytically stirs the said cobalt sulfate plating liquid at the time of performing cobalt sulfate plating. As the cobalt sulfate concentration is lower, the cobalt sulfate concentration tends to be able to produce a satisfactory blackening state. However, when the cobalt sulfate (hexahydrate) in the cobalt sulfate plating solution is less than 10 g / l, the electrodeposition rate of the cobalt sulfate plating layer formed by employing a stirring bath is slowed, and the thickness of the nickel sulfate layer becomes uneven. The result is a lack of industrial productivity. On the other hand, when cobalt sulfate (7-hydrate) exceeds 40 g / l, the cobalt sulfate plating layer formed will become difficult to form dense unevenness, and as a result will not be in a favorable blackening state.

In addition, pH of the cobalt sulfate plating solution at this time is 4.0 or more, It is preferable to adjust especially in the range of 4.5-5.5. This is because a good black cobalt plating layer can be obtained in this range with high yield. It is not preferable to add another electrolyte such as sodium hydroxide or potassium hydroxide to this pH adjustment. The black color of the cobalt plating layer is easily changed to the metallic color as described above. The pH of the solution is as described above by stabilizing the metal ion concentration in the solution at a constant level as a result of 4.0 or more.

And it is preferable to use the cobalt sulfate plating liquid at this time as 30 degrees C or less. The lower the temperature at this time, the better the blackening treatment surface tends to be obtained. When the liquid temperature is set to 30 ° C. or lower, in the manufacturing method A of the first surface-treated copper foil, it is possible to obtain a satisfactory blackened surface than that the blackened surface is not subjected to the roughening treatment.

The current density at the time of electrolysis is to use a current of 4 A / dm 2 or less. Within this range, a cobalt sulfate plating layer having good fine irregularities excellent in adhesion to organic materials and the like can be formed without roughening the copper foil surface. In general, in order to obtain a black-plated surface with irregularities, a method of flowing an electrolytic current flowing into an excessive burned plating region is employed. However, in this case, the smaller the current density used for electrolysis, the more stable the blackening treatment tends to be. Therefore, although the current density should be adopted as small as possible, considering the industrial productivity, the current density of 0.5 A / dm 2 can be judged as the lower limit. On the other hand, when current density exceeds 4 A / dm <2>, in the manufacturing method A of the said 1st surface treatment copper foil, it will become blackening process surface of the same level as blackening process on the copper foil surface which was not subjected to a roughening process, and it manufactured The meaning of adopting method B becomes obscure. Moreover, the powder fall phenomenon does not occur in the blackening process surface formed in the range of the above-mentioned current density.

In the process of b), the surface-treated copper foil which makes a cobalt sulfate plating layer blackening process surface can be obtained by washing with water and drying the copper foil which passed the above process. There is no restriction | limiting in particular in the washing method and the drying method here, It is possible to employ | adopt the method which can be normally considered.

(Manufacturing method of 2nd surface treatment copper foil)

In the case of the 2nd surface-treated copper foil, like the manufacturing method of the 1st surface-treated copper foil mentioned above, after manufacturing the surface-treated copper foil which makes a cobalt sulfate plating layer into a blackening process surface, it forms an antirust process layer. Thus, the production flow 'a) forms a black cobalt sulfate plating layer on the glossy surface of the copper foil. b) An antirust process layer is formed in the both surfaces or single side | surface of the copper foil in which the black cobalt sulfate layer was formed. c) then washed with water and dried. That is, the formation process of an antirust process layer only increased in the manufacturing method (manufacturing method A and the manufacturing method B) of a 1st surface treatment copper foil.

Therefore, only the formation process of a rustproof treatment layer is demonstrated here. An antirust process layer is formed in the both surfaces or single side | surface of the copper foil with which the formation of the black cobalt sulfate plating layer was completed. In the case of using conventionally known organic rust inhibitors such as imidazole and benzotriazole, inorganic rust inhibitors such as zinc alloys such as zinc or brass which are generally used, explanation is not particularly required. In consideration of this, detailed description is omitted here.

Hereinafter, the case where the rust-prevented layer is formed by plating by using a zinc-nickel alloy plating solution or a zinc-cobalt alloy plating solution will be described. First, the zinc-nickel alloy plating will be described. There is no particular limitation on the zinc-nickel alloy plating solution used here, but for example, the nickel concentration is 1 to 2.5 g / l using nickel sulfate and the zinc concentration is 0.1 to 1 g / l using zinc pyrrolate. , Potassium pyrrolate 50-500 g / l, liquid temperature 20-50 degreeC, pH 8-11, conditions of 0.3-10 A / dm <2> of current density, etc. are employ | adopted.

Next, zinc-cobalt alloy plating is demonstrated. The zinc-cobalt alloy plating solution used herein is not particularly limited, but for example, the cobalt concentration is 1 to 2.5 g / l using cobalt sulfate and the zinc concentration is 0.1 to 1 g / using zinc pyrrolate. The conditions of l, potassium pyrrolate 50-500 g / l, liquid temperature 20-50 degreeC, pH 8-11, and current density of 0.3-10 A / dm <2> are employ | adopted. The antirust process layer which combined this zinc-cobalt alloy plating and chromate treatment mentioned later shows especially outstanding corrosion resistance.

In the case of the second surface-treated copper foil, after forming a zinc-nickel alloy layer, a zinc-cobalt alloy layer, or the like on the surface of the copper foil, forming a chromate layer makes it possible to obtain more excellent corrosion resistance. That is, what is necessary is just to provide a chromate processing process after formation of the above-mentioned antirust process layer. In this chromate treatment process, you may employ | adopt any method of the substitution process which contacts a chromate solution and the said copper foil surface, or the electrolytic chromate process which electrolyzes in a chromate solution and forms a chromate film. Moreover, also about the chromate solution used here, the thing of the range used by a normal method can be used. Then, the surface-treated copper foil provided with the blackening process surface can be obtained by washing with water and drying after that.

<Electromagnetic shielding conductive mesh> The surface-treated copper foil provided with the blackening process surface which concerns on this invention described above does not have the fall of the powder from the blackening process surface, and also has the blackness, and the blackening process layer Silver can be etched away by conventional copper etching processes. Therefore, it is possible to easily process to arbitrary shapes using the process of manufacturing a printed wiring board. Considering these points, it can be said that it is optimal as an application of the electromagnetic shielding conductive mesh inserted into the front panel of the plasma display panel.

The surface-treated copper foil provided with the blackened surface according to the present invention has a good black color to be used for the electromagnetic shielding conductive mesh of the front panel of the plasma display panel, even though the cobalt sulfate plating layer is very thin. have. And since there is little cobalt content, etching property is favorable and it becomes possible to prolong solution life, without dropping the titer of normal iron chloride and sulfuric acid-hydrogen peroxide-type copper etching liquid.

Moreover, in the manufacturing method of the surface-treated copper foil which concerns on this invention, it is possible to manufacture the said surface-treated copper foil with high yield, and the cobalt sulfate plating layer formed using the manufacturing conditions mentioned above is melt | dissolved in the copper etching liquid most efficiently. .

Below, the surface-treated copper foil provided with the blackening process surface mentioned above is manufactured, and the result of having produced the electromagnetic wave shielding conductive mesh using a copper etching liquid is shown.

Example 1

In this embodiment, the 1st surface treatment copper foil 1a shown in FIG. 1 was manufactured, the electromagnetic wave shielding conductive mesh shape was experimentally manufactured by the etching method, and the etching performance was confirmed.

In this embodiment, the copper foil of 15 micrometers of nominal thickness obtained by electrolyzing a copper sulfate solution was used. And copper foil was immersed in this solution for 30 second using the sulfuric acid concentration 150g / l and the dilute sulfuric acid solution of 30 degreeC of liquid temperature, and the surface was cleaned.

And the roughening process was performed to the rough surface of the electrolytic copper foil of 15 micrometers of nominal thickness. At this time, the roughening treatment causes the microcopper particles 3 to adhere to one side of the copper foil B, and is a copper sulfate-based solution with a concentration of 10 g of copper, 100 g / l of sulfuric acid, 25 ppm of chlorine, and 9-phenyl. The solution of acridine 140 mg / l, the liquid temperature of 38 degreeC, the current density of 15 A / dm <2>, and electrolysis conditions of 2 second electrolysis time was employ | adopted. 10 shows the roughened copper foil surface.

As a process of a), the cobalt sulfate plating layer 4 was formed on the glossy surface of the said electrolytic copper foil. Formation of the cobalt sulfate plating layer 4, cobalt sulfate (7-hydrate) 10g / l, pH adjusted to 5.0, using a cobalt sulfate plating solution with a liquid temperature of 30 ° C as an unstirred bath, current density of 2A / dm 2 By electrolysis for 8 seconds to form a black cobalt sulfate plating layer (320 mg / m 2 in terms of thickness). At this time, the cobalt ion concentration in the solution was not particularly adjusted. This is because it is thought that adjustment of the metal ion concentration is unnecessary because it is a short time electrolysis. The cobalt sulfate plating layer formed in FIG. 11 is shown.

As the process of b), pure water is sufficiently showered and washed, convection is carried out for 4 seconds in a drying furnace with an atmospheric temperature of 150 ° C. with an electric heater, and the water is blown out to provide a surface treatment having a blackened surface of very good color tone. Copper foil 1a was obtained. In addition, between each process mentioned above, the washing | cleaning process by the pure water for 15 second is provided in principle, and the import of the solution of a pretreatment process is prevented.

<Physical Properties of Surface-treated Copper Foil>

When the cross section of the surface-treated copper foil provided with the blackening process surface obtained through the above process was observed with the FIB apparatus, the cross section shown in FIG. 3 can be obtained, and the cross-sectional height d of the said blackening process surface is 100 nm. In the Lab color system of the blackening treatment surface, L value was 30 and glossiness [Gs (60 °)] was 19. In addition, it was not able to confirm that the powder dropped in the tape test by attaching and detaching the adhesive tape to the blackened surface.

<Production of electromagnetic shielding mesh for plasma display>

The dry film which becomes an etching resist was stuck to both surfaces of the surface-treated copper foil obtained as mentioned above. Then, the test film for starting the electromagnetic wave shielding conductive mesh is superimposed only on the dry film on the blackened surface side, and the conductive film has a mesh electrode portion at a mesh pitch of 200 µm, a mesh line width of 10 µm, and a mesh bias angle of 45 ° C. The mesh pattern was exposed to ultraviolet light. At this time, the entire surface of the etching resist layer on the opposite side was also exposed to ultraviolet rays, so that it could not be removed by subsequent development. Then, it developed using the alkali solution and formed the etching pattern.

Then, using an iron chloride etching solution which is a copper etching solution, copper etching was performed on the blackening treatment side, and then the etching resist layer was peeled off to prepare an electromagnetic wave shielding conductive mesh. As a result, very good etching was performed without etching residues. In FIG. 12, the etching state of the test pattern (13 micrometer width circuit) for evaluating etching property is shown. As can be seen from FIG. 12, a beautiful circuit having an extremely excellent etching factor can be obtained without etching residues.

Example 2

In this embodiment, as shown in Fig. 6, a second surface-treated copper foil 1c having a zinc-nickel alloy layer as an antirust layer was produced, and an electromagnetic shielding conductive mesh shape was experimentally produced by an etching method. The etching performance was confirmed. Therefore, since it is common to Example 1 until the blackening process layer by a cobalt sulfate plating layer is formed, only rust prevention process conditions are demonstrated. In addition, the conversion thickness of the black cobalt sulfate plating layer is 320 mg / m <2> similar to Example 1.

Here, plating is performed on both surfaces of the copper foil on which the black cobalt sulfate plating layer is formed on one side of Example 1 by using a zinc-nickel alloy plating solution to form a zinc-nickel alloy layer on both sides. The zinc-nickel alloy layer has a nickel concentration of 2.0 g / l using nickel sulfate, a zinc concentration of 0.5 g / l using zinc pyrrolate, 250 g / l of potassium pyrrolate, a liquid temperature of 35 ° C., pH 10, and current density. It electrolyzed for 5 second on 5 A / dm <2> conditions, and made it electroporated uniformly and smoothly on both surfaces.

In the same manner as in Example 1, pure water was sufficiently showered and washed, convection was carried out for 4 seconds in a drying furnace at an atmospheric temperature of 150 ° C. with an electric heater, and the water was blown out to provide a surface having a blackened surface of a very good color tone. Processed copper foil (1c) was obtained. In addition, between each process mentioned above, the washing | cleaning process by the pure water for 15 second is provided in principle, and the import of the solution of a pretreatment process is prevented.

<Physical Properties of Surface-treated Copper Foil>

When the cross section of the surface-treated copper foil provided with the blackening process surface obtained through the above process was observed with the FIB apparatus, the cross section as shown in FIG. 3 can be obtained, The cross-sectional height of the said blackening process surface is 115 nm, L value in the Lab colorimeter of the said blackening process surface was 28, and glossiness [Gs (60 degrees)] was 21. In addition, it was not able to confirm that the powder dropped in the tape test by attaching and detaching the adhesive tape to the blackened surface.

<Production of electromagnetic shielding mesh for plasma display>

Similarly to Example 1, the electromagnetic wave shielding conductive mesh was started using the obtained surface-treated copper foil. As a result, even if the rust-prevented layer existed, there was no problem in the etching operation, there was no etching residue and very good etching was performed.

Example 3

As shown in FIG. 8, this Example manufactures the 2nd surface treatment copper foil 1e provided with the zinc-nickel alloy layer and the chromate treatment layer as an antirust process layer, and tests the electromagnetic shielding conductive mesh shape by the etching method. Preparation was carried out to confirm the etching performance. Therefore, since it is common to Example 1 until the blackening process layer by a cobalt sulfate plating layer is formed, only rust prevention process conditions are demonstrated. In addition, the conversion thickness of the black cobalt sulfate plating layer is 320 mg / m <2> similar to Example 1.

The formation of the rust-preventing layer was performed in the same manner as in Example 2, after the zinc-nickel alloy layer was formed on both surfaces using a zinc-nickel alloy plating solution, followed by chromate treatment on both surfaces. Here, chromate treatment was employed, and the electrolytic conditions were 5.0 g / l of chromic acid, pH 11.5, a liquid temperature of 35 ° C., a current density of 8 A / dm 2, and an electrolysis time of 5 seconds.

When the formation of the chromate layer is completed, the pure water is sufficiently showered and washed, and condensed for 4 seconds in a drying furnace having an atmospheric temperature of 150 ° C. with an electric heater, and blows out moisture to provide a blackened surface having a very good color tone. One surface-treated copper foil (1e) was obtained. In addition, between each process mentioned above, the washing | cleaning process by the pure water for 15 second is provided in principle, and the import of the solution of a pretreatment process is prevented.

<Physical Properties of Surface-treated Copper Foil>

When the cross section of the surface-treated copper foil provided with the blackening process surface obtained through the above process was observed with the FIB apparatus, the cross section as shown in FIG. 3 can be obtained, The cross-sectional height of the said blackening process surface is 121 nm, L value in the Lab color system of the said blackening process surface was 27, and glossiness [Gs (60 degrees)] was 23. In addition, it was not able to confirm that the powder dropped in the tape test by attaching and detaching the adhesive tape to the blackened surface.

<Production of electromagnetic shielding mesh for plasma display>

Similarly to Example 1, the electromagnetic wave shielding conductive mesh was started using the obtained surface-treated copper foil. As a result, even if the rust-prevented layer existed, there was no problem in the etching operation, there was no etching residue and very good etching was performed.

Example 4

In this embodiment, as shown in Fig. 6, a second surface-treated copper foil 1c having a zinc-cobalt alloy layer as an antirust treatment layer was produced, and an electromagnetic shielding conductive mesh shape was experimentally produced by an etching method. The etching performance was confirmed. Therefore, since it is common to Example 1 until the blackening process layer by a cobalt sulfate plating layer is formed, only rust prevention process conditions are demonstrated. In addition, the conversion thickness of the black cobalt sulfate plating layer is 320 mg / m <2> similar to Example 1.

Here, the zinc-cobalt alloy layer was formed on both surfaces of the copper foil by which the black cobalt sulfate plating layer was formed on the gloss surface of Example 1 using the zinc-cobalt alloy plating solution. The zinc-cobalt alloy layer has a cobalt concentration of 2.0 g / l using cobalt sulfate, a zinc concentration of 0.5 g / l using zinc pyrrolate, 250 g / l of potassium pyrrolate, a liquid temperature of 35 ° C., pH 10, and current density. It electrolyzed for 5 second on 5 A / dm <2> conditions, and made it deposit uniformly and smoothly on both surfaces.

Then, in the same manner as in Example 1, the pure water was sufficiently showered and washed, and condensed for 4 seconds in a drying furnace having an atmospheric temperature of 150 ° C. with an electric heater to blow out moisture, thereby providing a surface treatment with a blackened surface having a very good color tone. Copper foil (1c) was obtained. In addition, between each process mentioned above, the washing | cleaning process by the pure water for 15 second is provided in principle, and the import of the solution of a pretreatment process is prevented.

<Physical Properties of Surface-treated Copper Foil>

When the cross section of the surface-treated copper foil provided with the blackening process surface obtained through the above process was observed with the FIB apparatus, the cross section as shown in FIG. 3 can be obtained, The cross-sectional height of the said blackening process surface is 128 nm, L value in the Lab color system of the said blackening process surface was 28, and glossiness [Gs (60 degrees)] was 20. In addition, it was not able to confirm that the powder dropped in the tape test by attaching and detaching the adhesive tape to the blackened surface.

<Production of electromagnetic shielding mesh for plasma display>

Similarly to Example 1, the electromagnetic wave shielding conductive mesh was started using the obtained surface-treated copper foil. As a result, even if the rust-prevented layer existed, there was no problem in the etching operation, there was no etching residue and very good etching was performed.

Example 5

As shown in FIG. 8, this Example manufactures the 2nd surface treatment copper foil 1e provided with the zinc-cobalt alloy layer and the chromate treatment layer as an antirust process layer, and tests the electromagnetic shielding conductive mesh shape by the etching method. Preparation was carried out to confirm the etching performance. Therefore, since it is common to Example 1 until the blackening process layer by a cobalt sulfate plating layer is formed, only rust prevention process conditions are demonstrated. In addition, the conversion thickness of the black cobalt sulfate plating layer is 320 mg / m <2> similar to Example 1.

Formation of a rust-preventing layer was carried out similarly to Example 4, after forming a zinc-cobalt alloy layer on both surfaces using the zinc-cobalt alloy plating liquid, and chromate-processing on both surfaces. Here, electrolytic chromate treatment was employed, and the electrolytic conditions were 5.0 g / l of chromic acid, pH 11.5, a liquid temperature of 35 ° C., a current density of 8 A / dm 2, and an electrolysis time of 5 seconds.

When the formation of the chromate layer is completed, the pure water is sufficiently showered and washed, convection is performed for 4 seconds in a drying furnace with an atmospheric temperature of 150 ° C. with an electric heater, and the water is blown out to give a blackened surface of very good color tone. The surface-treated copper foil 1e which was provided was obtained. In addition, between each process mentioned above, the washing | cleaning process by the pure water for 15 second is provided in principle, and the import of the solution of a pretreatment process is prevented.

<Physical Properties of Surface-treated Copper Foil>

When the cross section of the surface-treated copper foil provided with the blackening process surface obtained through the above process was observed with the FIB apparatus, the cross section as shown in FIG. 3 can be obtained, The cross-sectional height of the said blackening process surface is 120 nm, L value in the Lab color system of the said blackening process surface was 29, and glossiness [Gs (60 degrees)] was 22. In addition, it was not able to confirm that the powder dropped in the tape test by attaching and detaching the adhesive tape to the blackened surface.

<Production of electromagnetic shielding mesh for plasma display>

Similarly to Example 1, the electromagnetic wave shielding conductive mesh was started using the obtained surface-treated copper foil. As a result, even if the rust-prevented layer existed, there was no problem in the etching operation, there was no etching residue and very good etching was performed.

Example 6

Unlike the first embodiment, the present embodiment is not subjected to rough treatment on the rough surface of the electrolytic copper foil, and in the same manner as in Example 1 below, a blackening treatment layer is formed on the glossy surface side of the electrolytic copper foil by the cobalt sulfate plating layer, and FIG. 2. The 2nd surface treatment copper foil 1b shown to was manufactured, and the same evaluation as Example 1 was performed. Therefore, since description of a process overlaps with Example 1, description here is abbreviate | omitted. Moreover, the conversion thickness of the black cobalt sulfate plating layer was 310 mg / m <2>. The black screen (cobalt sulfate plating layer) of the surface-treated copper foil obtained here in FIG. 13 is shown.

<Physical Properties of Surface-treated Copper Foil>

When the cross section of the surface-treated copper foil provided with the blackening process surface obtained through the above process was observed with the FIB apparatus, the cross section as shown in FIG. 3 can be obtained, The cross-sectional height of the said blackening process surface is 116 nm, L value in the Lab color system of the said blackening process surface was 27, and glossiness [Gs (60 degrees)] was 23. In addition, it was not able to confirm that the powder dropped in the tape test by attaching and detaching the adhesive tape to the blackened surface.

<Production of electromagnetic shielding mesh for plasma display>

Similarly to Example 1, the electromagnetic wave shielding conductive mesh was started using the obtained surface-treated copper foil. As a result, there was no problem in the etching operation, no etching residues, and very good etching was performed.

Example 7

In the present embodiment, as in Example 6, the roughening process of the electrolytic copper foil is not performed, but the blackening treatment is performed using the copper foil which has not been subjected to the above roughening treatment, and the first surface-treated copper foil 1b shown in FIG. ) And the electromagnetic wave shielding conductive mesh shape was experimentally prepared by the etching method to confirm the etching performance.

In this embodiment, the nominal 15 micrometers copper foil obtained by electrolyzing a copper sulfate solution was used. And copper foil was immersed in this solution for 30 second using the sulfuric acid concentration 150g / l and the dilute sulfuric acid solution of 30 degreeC of liquid temperature, and the surface was cleaned.

And the cobalt sulfate plating layer 4 was formed in the gloss surface of the said copper foil as a) process. Formation of the cobalt sulfate plating layer 4, cobalt sulfate (7-hydrate) is adjusted to 20g / l, pH to 5.5, using a cobalt sulfate plating solution with a liquid temperature of 27 ℃ as a stirring bath, current density of 1A / dm 2 Electrolysis for 15 seconds, thereby forming a black cobalt sulfate plating layer (equivalent thickness of 334 mg / m 2). At this time, the cobalt ion concentration in the solution was not particularly adjusted. This is because it is thought that adjustment of the metal ion concentration is unnecessary because it is a short time electrolysis. The cobalt sulfate plating layer formed in FIG. 14 is shown.

As the process of b), pure water is sufficiently showered and washed, convection is carried out for 4 seconds in a drying furnace with an atmospheric temperature of 150 ° C. with an electric heater, and the water is blown out to provide a surface treatment having a blackened surface of very good color tone. Copper foil (1) was obtained. In addition, between each process mentioned above, the washing | cleaning process by the pure water for 15 second is provided in principle, and the import of the solution of a pretreatment process is prevented.

<Physical Properties of Surface-treated Copper Foil>

When the cross section of the surface-treated copper foil provided with the blackening process surface obtained through the above process was observed with the FIB apparatus, the cross section as shown in FIG. 3 can be obtained, The cross-sectional height of the said blackening process surface is 131 nm, L value in the Lab color system of the said blackening process surface was 31, and glossiness [Gs (60 degrees)] was 24. In addition, it was not able to confirm that the powder dropped in the tape test by attaching and detaching the adhesive tape to the blackened surface.

<Production of electromagnetic shielding mesh for plasma display>

Similarly to Example 1, the electromagnetic wave shielding conductive mesh was started using the obtained surface-treated copper foil. As a result, there was no problem in the etching operation, no etching residues, and very good etching was performed.

Example 8

In the present embodiment, as in Example 6, the roughening process of the electrolytic copper foil is not performed, but the blackening treatment is performed using the copper foil which has not been subjected to the above roughening treatment, and the first surface-treated copper foil 1b shown in FIG. ) And the electromagnetic wave shielding conductive mesh shape was experimentally prepared by the etching method to confirm the etching performance.

In this embodiment, the copper foil of 15 micrometers of nominal thickness obtained by electrolyzing a copper sulfate solution was used. And copper foil was immersed in this solution for 30 second using the sulfuric acid concentration 150g / l and the dilute sulfuric acid solution of 30 degreeC of liquid temperature, and the surface was cleaned.

And the cobalt sulfate plating layer was formed in the gloss surface of the said copper foil as a) process. The formation of the cobalt sulfate plating layer was performed by adjusting the cobalt sulfate (hexahydrate) to 20 g / l and pH to 5.5, using a cobalt sulfate plating solution having a liquid temperature of 27 ° C. as a stirring bath for 7 seconds at a current density of 2 A / dm 2. By electrolysis, it forms as a black cobalt sulfate plating layer (conversion thickness is 340 mg / m <2>). At this time, the cobalt ion concentration in the solution was not particularly adjusted. This is because it is thought that adjustment of the metal ion concentration is unnecessary because it is a short time electrolysis. The form of the formed cobalt sulfate plating layer is observed as shown in FIG.

As the process of b), pure water is sufficiently showered and washed, convection is carried out for 4 seconds in a drying furnace with an atmospheric temperature of 150 ° C. with an electric heater, and the water is blown out to provide a surface treatment having a blackened surface of very good color tone. Copper foil (1b) was obtained. In addition, between each process mentioned above, the washing | cleaning process by the pure water for 15 second is provided in principle, and the import of the solution of a pretreatment process is prevented.

<Physical Properties of Surface-treated Copper Foil>

When the cross section of the surface-treated copper foil provided with the blackening process surface obtained through the above process was observed with the FIB apparatus, the cross section as shown in FIG. 3 can be obtained, The cross-sectional height of the said blackening process surface is 124 nm, L value in the Lab color system of the said blackening process surface was 33, and glossiness [Gs (60 degrees)] was 20. In addition, it was not able to confirm that the powder dropped in the tape test by attaching and detaching the adhesive tape to the blackened surface.

<Production of electromagnetic shielding mesh for plasma display>

Similarly to Example 1, the electromagnetic wave shielding conductive mesh was started using the obtained surface-treated copper foil. As a result, there was no problem in the etching operation, no etching residues, and very good etching was performed.

Example 9

In this embodiment, the roughening surface of the electrolytic copper foil is not subjected to roughening in the same manner as in Example 6, but the blackening treatment is performed on the glossy surface to produce the first surface-treated copper foil 1b shown in FIG. The mesh shape was experimentally prepared by the etching method to confirm the etching performance.

In this embodiment, the copper foil of 15 micrometers of nominal thickness obtained by electrolyzing a copper sulfate solution was used. And copper foil was immersed in this solution for 30 second using the sulfuric acid concentration 150g / l and the dilute sulfuric acid solution of 30 degreeC of liquid temperature, and the surface was cleaned.

And the cobalt sulfate plating layer was formed in the gloss surface of the said copper foil as a) process. The formation of the cobalt sulfate plating layer was performed by adjusting the cobalt sulfate (hexahydrate) to 40 g / l and pH to 5.5, using a cobalt sulfate plating solution having a liquid temperature of 27 ° C. as a stirring bath for 15 seconds at a current density of 1 A / dm 2. By electrolysis, it forms as a black cobalt sulfate plating layer (conversion thickness is 338 mg / m <2>). At this time, the cobalt ion concentration in the solution was not particularly adjusted. This is because it is thought that adjustment of the metal ion concentration is unnecessary because it is a short time electrolysis. The form of the cobalt sulfate plating layer is observed as shown in FIG.

As the process of b), pure water is sufficiently showered and washed, convection is carried out for 4 seconds in a drying furnace with an atmospheric temperature of 150 ° C. with an electric heater, and the water is blown out to provide a surface treatment having a blackened surface of very good color tone. Copper foil (1b) was obtained. In addition, between each process mentioned above, the washing | cleaning process by the pure water for 15 second is provided in principle, and the import of the solution of a pretreatment process is prevented.

<Physical Properties of Surface-treated Copper Foil>

When the cross section of the surface-treated copper foil provided with the blackening process surface obtained through the above process was observed with the FIB apparatus, the cross section as shown in FIG. 3 can be obtained, The cross-sectional height of the said blackening process surface is 134 nm, L value in the Lab color system of the said blackening process surface was 34, and glossiness [Gs (60 degrees)] was 21. In addition, it was not able to confirm that the powder dropped in the tape test by attaching and detaching the adhesive tape to the blackened surface.

<Production of electromagnetic shielding mesh for plasma display>

Similarly to Example 1, the electromagnetic wave shielding conductive mesh was started using the obtained surface-treated copper foil. As a result, there was no problem in the etching operation, no etching residues, and very good etching was performed.

Example 10

In the present embodiment, as shown in Fig. 7, a second surface-treated copper foil 1d having a zinc-cobalt alloy layer as an antirust layer was produced, and an electromagnetic shielding conductive mesh shape was experimentally produced by an etching method. The etching performance was confirmed. Therefore, since it is common to Example 7 until the blackening process layer by a cobalt sulfate plating layer is formed, only rust prevention process conditions are demonstrated. In addition, the conversion thickness of the black cobalt sulfate plating layer is 334 mg / m <2> similar to Example 7.

Here, the zinc-cobalt alloy layer was formed on both surfaces of the copper foil by which the formation of the black cobalt sulfate plating layer was finished on the single side | surface of Example 7 on both surfaces under the same conditions as Example 4. FIG. In the same manner as in Example 1, pure water was sufficiently showered and washed, convection was carried out for 4 seconds in a drying furnace at an atmospheric temperature of 150 ° C. with an electric heater, and the water was blown out to provide a surface having a blackened surface of a very good color tone. Processed copper foil (1d) was obtained. In addition, between each process mentioned above, the washing | cleaning process by the pure water for 15 second is provided in principle, and the import of the solution of a pretreatment process is prevented.

<Physical Properties of Surface-treated Copper Foil>

When the cross section of the surface-treated copper foil provided with the blackening process surface obtained through the above process was observed with the FIB apparatus, the cross section as shown in FIG. 3 can be obtained, The cross-sectional height of the said blackening process surface is 128 nm, L value in the Lab color system of the said blackening process surface was 28, and glossiness [Gs (60 degrees)] was 30. In addition, it was not able to confirm that the powder dropped in the tape test by attaching and detaching the adhesive tape to the blackened surface.

<Production of electromagnetic shielding mesh for plasma display>

Similarly to Example 1, the electromagnetic wave shielding conductive mesh was started using the obtained surface-treated copper foil. As a result, there was no problem in the etching operation, no etching residues, and very good etching was performed.

Example 11

This Example manufactures the 2nd surface treatment copper foil 1f provided with the zinc-cobalt alloy layer and the chromate treatment layer as an antirust process layer as shown in FIG. 9, and tests the electromagnetic wave shielding conductive mesh shape by the etching method. Preparation was carried out to confirm the etching performance. Therefore, since it is common to Example 7 until the blackening process layer by a cobalt sulfate plating layer is formed, only rust prevention process conditions are demonstrated. In addition, the conversion thickness of the black cobalt sulfate plating layer is 334 mg / m <2> similar to Example 7.

The formation of the rust-preventing layer is performed in the same manner as in Example 4, after the zinc-cobalt alloy layer is formed on both surfaces using the zinc-cobalt alloy plating solution, and then subjected to the same chromate treatment as in Example 5 on both surfaces.

When the formation of the chromate layer is completed, the pure water is sufficiently showered and washed, convection is performed for 4 seconds in a drying furnace with an atmospheric temperature of 150 ° C. with an electric heater, and the water is blown out to give a blackened surface of very good color tone. The prepared surface-treated copper foil (1f) was obtained. In addition, between each process mentioned above, the washing | cleaning process by the pure water for 15 second is provided in principle, and the import of the solution of a pretreatment process is prevented.

<Physical Properties of Surface-treated Copper Foil>

When the cross section of the surface-treated copper foil provided with the blackening process surface obtained through the above process was observed with the FIB apparatus, the cross section as shown in FIG. 3 can be obtained, The cross-sectional height of the said blackening process surface is 115 nm, L value in the Lab color system of the said blackening process surface was 29, and glossiness [Gs (60 degrees)] was 22. In addition, it was not able to confirm that the powder dropped in the tape test by attaching and detaching the adhesive tape to the blackened surface.

<Production of electromagnetic shielding mesh for plasma display>

Similarly to Example 1, the electromagnetic wave shielding conductive mesh was started using the obtained surface-treated copper foil. As a result, even if the rust-prevented layer existed, there was no problem in the etching operation, there was no etching residue and very good etching was performed.

The surface-treated copper foil provided with the blackening process surface which concerns on this invention is free of the powder fall from the blackening process surface, and can also be etched using the normal copper etching liquid, and the electromagnetic wave of the front panel of a plasma display panel By using it for a shielding conductive mesh, formation of a high quality black mask is attained. Moreover, if supply as a surface-treated copper foil provided with a blackening process surface is possible, the blackening process process in a manufacturing process of a front panel will be possible. Moreover, the surface-treated copper foil provided with this blackening process surface can use the conventional copper foil surface treatment process by employ | adopting the manufacturing method mentioned above, and does not require new manufacturing equipment. Therefore, a high quality product can be manufactured in a high yield, and production cost can be reduced.

Claims (16)

A surface-treated copper foil having a blackened surface on a glossy surface, The said blackening process surface is a cobalt sulfate plating layer whose weight thickness provided in the single side | surface of the copper foil layer is 200 mg / m <2> -400 mg / m <2>, and the cross-sectional height of this blackening process surface is 200 nm or less, The surface characterized by the above-mentioned. Treatment copper foil. The method of claim 1, The said blackening process surface is surface-treated copper foil whose L value in Lab color system is 27 or more. The method of claim 1, The surface-treated copper foil provided with the antirust process layer on the said blackening process surface. The method of claim 3, wherein The rust-proof layer is a surface-treated copper foil provided with the blackening process surface which uses zinc or a zinc alloy. The method of claim 3, wherein The antirust process layer is the surface-treated copper foil provided with the layer formed using zinc or a zinc alloy, and the blackening process surface which consists of a chromate treatment layer. The method of claim 1, The said blackening process surface formed the said blackening process surface in the gloss surface of an electrolytic copper foil or a rolled copper foil, and the glossiness [Gs (60 degrees)] is 30 or less surface-treated copper foil. A manufacturing method of the surface-treated copper foil provided with the blackening process surface, Comprising: The process of following a) and b) is provided, The manufacturing method of the surface-treated copper foil provided with the blackening process surface. a) At the current density of 2 A / dm 2 or more, using an unstirred bath of a cobalt sulfate plating solution containing 8 g / l to 10 g / l of cobalt sulfate (hexahydrate) on the gloss surface of the copper foil and having a pH of 4.0 or more. Electrolysis is carried out to form a black cobalt sulfate plating layer. b) then washed with water and dried. A manufacturing method of the surface-treated copper foil provided with the blackening process surface, Comprising: The process of following a) and b) is provided, The manufacturing method of the surface-treated copper foil provided with the blackening process surface. a) Cobalt sulfate plating liquid containing 10 g / l-40 g / l of cobalt sulfate (7-hydrate) in the gloss surface of copper foil, and using pH as 4.0 or more and 30 degreeC or less of liquid temperature as a stirring bath, 4A / dm <2> Electrolysis is carried out at the following current densities to form a black cobalt sulfate plating layer. b) then washed with water and dried. The manufacturing method provided with the rust-proof layer and the blackening process surface, Comprising: The process of following a) -c), The manufacturing method of the surface-treated copper foil provided with the blackening process surface characterized by the above-mentioned. a) A cobalt sulfate plating solution containing 8 g / l to 10 g / l of cobalt sulfate (hexahydrate) on the gloss surface of the copper foil and using a cobalt sulfate plating solution having a pH of 4.0 or more as an unstirred bath, at a current density of 2 A / dm 2 or more. Electrolysis is carried out to form a black cobalt sulfate plating layer. b) The antirust process layer is formed in the both surfaces or single side | surface of the copper foil in which the black cobalt sulfate plating layer was formed. c) then washed with water and dried. As a manufacturing method of the surface-treated copper foil provided with the blackening process surface provided with the antirust process layer, The manufacturing method of the surface-treated copper foil provided with the blackening process surface characterized by including the process of the following a) -c). a) 4A / dm <2> using the cobalt sulfate plating liquid which contains 10 g / l-40 g / l of cobalt sulfate (7-hydrate) in the gloss surface of copper foil, and made pH more than 4.0 and 30 degrees C or less of liquid temperature, Electrolysis is carried out at the following current densities to form a black cobalt sulfate plating layer. b) The antirust process layer is formed in the both surfaces or single side | surface of the copper foil in which the black cobalt sulfate plating layer was formed. c) then washed with water and dried. The electromagnetic wave shielding conductive mesh for front panels of the plasma display formed using the surface-treated copper foil provided with the blackening process surface of Claim 1. The electromagnetic wave shielding conductive mesh for a front panel of the plasma display formed using the surface-treated copper foil provided with the blackening process surface of Claim 2. The electromagnetic wave shielding conductive mesh for front panels of the plasma display formed using the surface-treated copper foil provided with the blackening process surface of Claim 3. The electromagnetic wave shielding conductive mesh for front panels of the plasma display formed using the surface-treated copper foil provided with the blackening process surface of Claim 4. The electromagnetic wave shielding conductive mesh for a front panel of the plasma display formed using the surface-treated copper foil provided with the blackening process surface of Claim 5. The electromagnetic wave shielding conductive mesh for a front panel of the plasma display formed using the surface-treated copper foil provided with the blackening process surface of Claim 6.