KR20080025143A - Blackening surface treated copper foil and electromagnetic wave shielding conductive mesh for front panel of plasma display using the blackening surface treated copper foil - Google Patents

Abstract

A blackening surface treated copper foil capable of improving a phenomenon of causing clouding of the surface of an adhesive layer exposed between mesh circuits on completion of etching of a conductive mesh used for shielding a plasma display panel against an electromagnetic wave. The blackening surface treated copper foil is used which is a surface treated copper foil having a blackening treated surface provided on the surface of an untreated electrolytic copper foil, characterized in that the untreated electrolytic copper foil has a surface of which surface roughness Ra is up to 45 nm as measured with a three-dimensional surface structure analysis microscope, and the surface is provided with a blackening treated surface. The surface of the untreated electrolytic copper foil provided with a blackening treated surface more preferably has a surface roughness Rz of up to 850 nm as measured with a three-dimensional surface structure analysis microscope. ® KIPO & WIPO 2008

Description

TECHNICAL WAVE SHIELDING CONDUCTIVE MESH FOR FRONT PANEL OF PLASMA DISPLAY USING THE BLACKENING SURFACE TREATED COPPER FOIL}

The present invention relates to a blackened surface-treated copper foil and an electromagnetic shielding conductive mesh for a front panel of a plasma display using the blackened surface-treated copper foil.

BACKGROUND OF THE INVENTION Conductive meshes for shields in plasma display panels have changed from metallized fiber fabrics to conductive meshes. In recent years, a technique of using a transparent conductive film having excellent transparency such as silver or ITO on the surface of a glass or plastic substrate is used instead of the conductive mesh. However, these transparent conductive films have high electromagnetic shielding properties in comparison with the conductive mesh. Falls. Therefore, there is no change in the electromagnetic wave shielding conductive mesh obtained by etching using metal foil as the mainstream.

Several techniques are employ | adopted for the manufacturing method of the electromagnetic shielding conductive mesh using metal foil. Among them, a typical manufacturing method will be described. That is, as shown to Fig.5 (a), the PET film 4 is prepared and the adhesive bond layer 5 is provided in the surface, and it is set as the state shown to Fig.5 (b). And as shown in FIG.5 (c), the blackening surface treated copper foil provided with the blackening process surface 3 on the adhesive bond layer 5, The said blackening process surface 3 is the said Adhesion is made to contact the adhesive layer 5. And blackening surface treatment copper foil 2 is provided in the surface, as shown in FIG.5 (d).

Then, an etching resist layer 6 is formed on the blackened surface-treated copper foil 2 as shown in FIG. 5E, and as shown in FIG. 6F in the etching resist layer 6. The conductive mesh pattern 7 is exposed, developed as shown in Fig. 6G to form an etching resist pattern shape, and etched, thereby bringing the state shown in Fig. 6H. At this time, the etching resist layer 6 is peeled off, and the state shown in FIG.

Subsequently, as shown in FIG. 7 (j), the first transparent substrate 9a constituting the front filter is brought into contact with the conductive mesh 8 and pressed, as shown in FIG. 7 (k). The conductive mesh 8 is pushed into the adhesive layer 5 to perform a transparent treatment. And the PET film 4 is peeled off as shown to Fig.7 (l). Finally, as shown in FIG.7 (m), the adhesive agent layer 5 and the 2nd transparent substrate 9b are adhere | attached, and the front surface filter 1 is completed.

Non-Patent Document 1: Technical Trends of PDP Materials Hitachi Kasei Technical Report 33 (1999-7)

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

Patent Document 2: Japanese Patent Application Laid-Open No. 2000-315889

Patent Document 3: Japanese Patent Laid-Open No. 2004-35918

Patent Document 4: Japanese Patent Application Laid-Open No. 2004-162144

Patent Document 5: Japanese Patent Application Laid-Open No. 2004-107786

Patent Document 6: Japanese Patent Application Laid-Open No. 2004-137588

[Problem to Solve Invention]

However, in accordance with recent demands for power saving, development is in progress aiming at a plasma generation signal voltage of 200V to 50V level, and in response to a decrease in luminance accompanying a decrease in the voltage, the circuit width of the conductive mesh is increased. It has become thin and advanced in the direction which reduces the coverage of the front glass panel by a conductive mesh.

On the other hand, since the conductive mesh itself is inserted into the front panel and can be seen directly from the surface to the eye through the front glass, one side of the surface-treated copper foil processed with this conductive mesh is formed from dark brown to black to produce a good black mask. It is necessary to process in a dark state to raise the brightness of transmitted light.

Further, digitalization of radio waves of television terrestrial broadcasting is expected in the future, and the transmission speed of image signals is also increased, and high definition of images corresponding to high resolution is required.

In view of the above phenomena, when the light passing through the mesh circuit of the electromagnetic wave shielding conductive mesh is used more sharply and with higher brightness, there are the following problems. As shown in FIG.7 (i), when the etching of an electroconductive mesh shape is complete | finished, the surface shape of the adhesive bond layer 5 exposed between circuits is the shape of the blackening process surface 3 of the blackening surface-treated copper foil 2 It is being transferred. This transfer shape is also different depending on the constituent components constituting the adhesive layer, but remains at the interface with the first transparent substrate 9a without being lost even after applying the transparent treatment of FIGS. 8 (i) to 8 (k). There is a case.

In such a case, clouding is caused by the transfer shape to cause an obstacle, so that the luminance of light passing through the mesh circuits is reduced, so that a clear image is not obtained. If the quality of an image cannot be improved due to such a physical factor, there is a limit even if an attempt is made to solve the pseudo contour obstacle by performing the pixel data control by performing the computation of the image data so well.

From the above, the phenomenon that the surface shape of the adhesive bond layer exposed between the circuits was terminated by the etching of the conductive mesh shape was observed to cause a blur phenomenon, and a copper foil having a blackening treatment surface on which this problem does not occur has been demanded. In order to solve this problem, the surface of the untreated copper foil which forms a blackening process surface is employ | adopted the technique disclosed by the said patent documents 3-6, etc., and it has been tried to use the low profile copper foil. . Hereinafter, the technique disclosed by patent document 3-the said patent document 6 is demonstrated briefly.

Patent Literature 3 discloses an electrolytic copper foil comprising a sulfuric acid copper plating solution containing a copolymer of diallyl dialkyl ammonium salt and sulfur dioxide in a method for producing an electrolytic copper foil using a sulfuric acid acidic copper plating solution. It is said that it is desirable to contain polyethylene glycol, chlorine, and 3-mercapto-1-sulfonic acid in the sulfuric acid acidic copper plating solution. In the case of electrolytic copper foil having a small roughness (precipitation surface roughness) of the surface facing the insulating substrate and having a thickness of 10 μm, a low profile of about Rz = 1.0 ± 0.5 μm with a tactile roughness meter ( Illuminance) is obtained.

Patent Document 4 describes a method for producing an electrolytic copper foil having a small surface roughness of the precipitated surface and excellent in elongation. In the method for producing an electrolytic copper foil by electrolysis of an acidic copper sulfate acid solution, polyethylene glycol, chlorine and 3-mercapto-1 It is proposed to use a sulfuric acid acidic copper plating solution characterized by containing sulfonic acid. And the roughness (precipitation surface roughness) of the adhesive surface with an insulating base material is small, and in the case of the electrolytic copper foil with a thickness of 10 micrometers, the low profile (roughness) of about Rz = 1.5 +/- 0.5 micrometer is obtained with a stylus roughness meter.

Patent Literature 5 discloses using a coin dissolving solution containing an amine compound and an organic sulfur compound having a specific skeleton obtained by addition reaction of a compound having at least one epoxy group and an amine compound in one molecule, as an additive, for the production of an electrolytic copper foil. have. And the surface roughness Rz of the electrolytic copper foil obtained by this manufacturing method is 0.90 micrometer-1.20 micrometer with the stylus roughness meter from the technique of the Example.

Patent Literature 6 discloses a coin dissolving solution containing a quaternary amine compound and an organosulfur compound having a specific skeleton obtained by quaternizing nitrogen after addition reaction of a compound having at least one epoxy group and an amine compound in one molecule. It is disclosed to use for manufacture of an electrolytic copper foil. And the surface roughness Rz of the electrolytic copper foil obtained by this manufacturing method is 0.94 micrometer-1.23 micrometers by the stylus roughness meter from the technique of the Example.

Therefore, when an electrolytic copper foil is manufactured using such a manufacturing method, the precipitation surface of the outstanding low profile will be surely formed, and it shows the extremely outstanding property as a low profile electrolytic copper foil. However, even when using such a low profile copper foil, the quality variation was large and the phenomenon that the surface shape of the adhesive layer exposed between the circuits was terminated because the etching of the conductive mesh shape was terminated was observed, which did not solve the problem. .

[Means for solving the problem]

Here, as a result of intensive studies, the inventors of the present invention have achieved the above problems by using a surface-treated copper foil having a blackened surface as shown below.

In order to achieve the said subject, as a surface-treated copper foil which provides a blackening process surface on the surface of an untreated electrolytic copper foil, the untreated electrolytic copper foil has the surface roughness Ra measured using the three-dimensional surface structure analysis microscope the surface of 45 nm or less In addition, the blackening surface-treated copper foil which uses the blackening treatment surface on the said surface is used.

And as for the surface which provides the blackening process surface of the said untreated electrolytic copper foil, it is preferable that surface roughness Rz measured using the three-dimensional surface structure analysis microscope is 850 nm or less.

In addition, the surface which provides the blackening process surface of the said unprocessed electrolytic copper foil has a low profile whose surface roughness (Rzjis) is less than 0.8 micrometer when measured based on JIS B 0601, and also glossiness (Gs (60 degrees)). It is preferable that is 400 or more.

It is preferable to provide a rust prevention process layer in the said blackening process surface.

It is preferable that glossiness [Gs (60 degrees)] of the said blackening process surface is 35 or less.

As the blackening treatment surface, it is preferable to use either a nickel-based blackening treatment surface or a cobalt-based blackening treatment surface.

By using the blackened surface-treated copper foil described above, it becomes possible to provide the high-frequency shielding conductive mesh for the front panel of a high quality plasma display.

[Effects of the Invention]

The blackening surface-treated copper foil which concerns on this invention is excellent in the flatness of the surface, the grade which produces an electroconductive mesh using this blackening surface-treated copper foil, and the etching is complete | finished and the clouding phenomenon arises on the surface of the adhesive bond layer exposed between circuits. Since is low, it is possible to greatly contribute to eliminating pseudo contour obstacles by controlling light emission of the pixel without degrading the luminance of the plasma display panel.

In addition, it is preferable that the blackening process surface of the blackening surface-treated copper foil which concerns on this invention employ | adopts either nickel-based blackening process surface or cobalt-based blackening process surface, and the blackening process formed on a certain condition is There is no powder falling off, and a good black color is exhibited, and the blackening process layer can be etched away by a normal copper etching process. Thus, the process of manufacturing a printed wiring board can be used to provide a high quality electromagnetic shielding conductive mesh of a plasma display panel.

1 is an observation image of a blackened surface-treated copper foil when SEM (scanning electron microscope) is observed at a high magnification of 10,000 times.

2 is an observation image of a blackened surface-treated copper foil when SEM observation is performed at a high magnification of 10,000 times.

FIG. 3 is an observation image of a blackened surface-treated copper foil when SEM observation of the surface as shown in FIG. 1 is performed at 500 times lower magnification. FIG.

4 is an observation image of a blackened surface-treated copper foil when SEM observation of the surface as shown in FIG. 2 is performed at 500 times lower magnification.

5 is a schematic cross-sectional view for illustrating a manufacturing process of an electromagnetic shielding conductive mesh of a plasma display panel.

6 is a schematic cross-sectional view for illustrating a manufacturing process of an electromagnetic shielding conductive mesh of a plasma display panel.

7 is a schematic cross-sectional view for illustrating a manufacturing process of an electromagnetic shielding conductive mesh of a plasma display panel.

[Description of the code]

One… Front filter

2… Blackening Surface Treatment Copper Foil

3... Blackened surface

4… PET film

5... Adhesive layer

6... Etching resist layer

7... Conductive mesh pattern

8… Conductive Mesh (Electromagnetic Shielding Conductive Mesh)

9a... First transparent substrate

9b... Second transparent substrate

The surface-treated copper foil provided with the blackening process surface which concerns on this invention has the following forms. That is, as a surface-treated copper foil which has a blackening process surface on the surface of an untreated electrolytic copper foil, the said unprocessed electrolytic copper foil had the surface roughness Ra measured using the three-dimensional surface structure analysis microscope, the surface of 45 nm or less, and the said surface The blackened surface-treated copper foil is used, which provided the blackening process surface.

Untreated copper foil: First, an untreated copper foil is demonstrated. The untreated copper foil here does not apply any surface treatment, such as antirust, to a bulk copper foil, and can use both an electrolytic copper foil or a rolled copper foil. However, it is preferable to use an electrolytic copper foil from a cost point of view. This electrolytic copper foil flows a copper sulfate type solution between the drum-shaped rotating cathode, the lead-based anode etc. which are arrange | positioned along the shape of this rotating cathode, and deposits copper on the drum surface of a rotating cathode using an electrolytic reaction, The precipitated copper is in a foil state and is continuously peeled off and wound up from the rotating cathode. Copper foil of this stage is an untreated copper foil.

The surface which peeled in the state which contacted the rotating cathode of this untreated copper foil is what the shape of the surface of the rotating cathode surface mirrored | finished was transferred, and is generally called a gloss surface. If the roughness of the surface of the rotating cathode is excessively smooth, the deposited copper is immediately peeled off the surface of the rotating cathode, and a good electrolytic copper foil is not obtained. On the other hand, since the surface shape of the untreated foil of the side which was the precipitation surface differs for each crystal surface of the copper crystal growth rate which precipitates, it usually shows a mountain-shaped uneven | corrugated shape, and this is called roughness (precipitation surface). However, in the case of the electrolytic copper foil manufactured on some fixed conditions, the uneven shape precipitation surface lower than a gloss surface may be obtained.

Among the electrolytic copper foils, if the surface providing the blackened surface of the untreated electrolytic copper foil has a surface roughness Ra measured using a three-dimensional surface structure analysis microscope having a surface of 45 nm or less, as described above, The etching of the conductive mesh shape to be placed in the front panel is terminated so that the surface shape of the adhesive layer exposed between the mesh circuits does not cause blur. As will be described later, as a method of evaluating the occurrence of this cloudy phenomenon, an epoxy-based adhesive is applied to the blackened surface of the surface-treated copper foil according to the present invention and dried, and the surface-treated copper foil is subjected to full etching. It removed by making it into the adhesive sheet state, and the haze (cloudiness) was measured using the haze meter (turbidimeter NDH2000 by Nippon Denshoku Industries Co., Ltd.). Hereinafter, this test is called haze measurement test. In an Example, the value of haze is shown.

As described above, it has conventionally been pointed out that the etching of the conductive mesh shape to be placed in the front panel of the plasma display panel is terminated and the surface shape of the adhesive layer exposed between the mesh circuits causes blurring to lower the luminance of transmitted light. At this time, the person skilled in the art has considered the relationship with the roughness of the blackening process surface of an untreated copper foil and a surface-treated copper foil. Then, when the SEM was observed at a magnification of 1500 times or higher as shown in Figs. 1 and 2, the surface appeared smooth, and the roughness was monitored using a stylus roughness meter. 1 and 2 show clearly different haze values in the haze measurement test, but no significant difference is seen.

However, as a result of extensive studies by the present inventors, it has been concluded that the blur phenomenon cannot be solved even from the above point of view. Here, FIG. 3 and FIG. 4 show the state when the surface of the surface-treated copper foil which did not have the difference of FIG. 1 and FIG. 2 was observed by SEM at 500 times the low magnification. 3 and 4 clearly show a difference. That is, the relationship with a haze value cannot be known about the narrow area | region at the time of high magnification, and the illuminance in the short range scan measured with the stylus type illuminometer. Therefore, by employing the illuminance value in the region of 144 µm x 108 µm using a three-dimensional surface structure analysis microscope capable of region scanning, the flatness of the surface viewed macroscopically was a problem.

In addition, when the roughness of the surface of the untreated copper foil is expressed by the surface roughness Rz measured using a three-dimensional surface structure analysis microscope, when the surface having a surface of 850 nm or less is provided, it is placed on the front surface of the plasma display panel as described above. It can be said that the etching of the conductive mesh shape is terminated so that the surface shape of the adhesive layer exposed between the mesh circuits does not cause blur.

Here, roughness measurement using a three-dimensional surface structure analysis microscope will be described. In the present invention, the surface irregularities were measured by a laser using a 100 times objective lens using NewView5032 manufactured by Zygo. And at this time, the threshold value was determined so that the high spatial frequency component of wavelength 3 micrometers or less and the low spatial frequency component of wavelength 10 micrometers or more were cut, and Ra and Rz were calculated | required from the measurement result. Therefore, Ra and Rz here are not the roughness calculated | required by the stylus roughness meter.

The threshold value was set so as to cut a high spatial frequency component having a wavelength of 3 μm or less, which was observed visually in a haze test using an untreated foil and a surface treated foil before and after the blackening treatment in a region having a wavelength of 3 μm or less. This is because it was judged that it was not an appropriate range for the haze test because there was no difference in the haze value even if there was a difference in the level of keratin. On the other hand, the threshold value is set so as to cut low spatial frequency components with a wavelength of 10 μm or more, when the wavelength is 10 μm or more, too large unevenness occurs. As described above, too large unevenness is not related to the occurrence of haze and the haze value. It is because it becomes meaningless even if it measures.

In addition, the surface of the said untreated electrolytic copper foil which provides a blackening process surface can be observed as having a low profile whose surface roughness (Rzjis) when measured with the stylus roughness meter based on JIS B 0601 is less than 0.8 micrometer. In addition to this surface roughness, the glossiness (Gs (60 °)) is preferably 400 or more. In general, the value of Rzjis has been used as an index indicating the smoothness of untreated electrolytic copper foil. However, Rzjis alone can only obtain information in the height direction of the unevenness, and cannot obtain information such as 'period' or 'relief' of the unevenness. Therefore, by using the concept of glossiness, which is a parameter containing information of 'period' and 'relief' of the unevenness of the surface of the untreated electrolytic copper foil, by combining this with the surface roughness, the surface of the conventional low profile electrolytic copper foil The difference can be clearly understood.

And as the surface of this untreated electrolytic copper foil is as smooth as possible, it becomes advantageous for formation of the smooth blackening process surface of blackening surface-treated copper foil. In general, when the electrolytic copper foil is manufactured by tracing the production method disclosed in the Patent Documents 3 to 6, the roughness (Rzjis) value on the precipitation surface side is at a level exceeding 0.8 µm. On the other hand, when the surface roughness of the untreated copper foil used by this invention employ | adopts the manufacturing method mentioned later, it becomes possible to obtain the low profile whose surface roughness Rzjis on the precipitation surface side is 0.6 micrometer or less. Here, although the lower limit of surface roughness is not specifically limited, The lower limit of roughness is about 0.1 micrometer empirically. From this, the surface roughness Rzjis on the precipitation surface side is 0.6 µm or less, and the glossiness (Gs (60 °)) is 600 or more for formation of the blackened surface of the blackened surface-treated copper foil according to the present invention. It is more preferable. On the other hand, in the actual measurement of the surface roughness described above, it is natural that a constant deviation occurs in the measured value, and it is considered that the lower limit of the measured value that can be guaranteed is about 0.2 μm.

The glossiness used in the present invention was measured by irradiating measurement light on the surface of the copper foil along the flow direction (MD direction) of the electrolytic copper foil at an incident angle of 60 ° and measuring the intensity of light reflected at a reflection angle of 60 °. It measured according to JIS Z 8741-1997 which is a glossiness measuring method using the glossmeter VG-2000 type from the full color industry corporation. As a result, traces the production methods disclosed in Patent Documents 3 to 6 to produce an electrolytic copper foil having a thickness of 18 µm, and measuring the glossiness [Gs (60 °)] of the precipitated surface, about 250 to 380. Enter the range. On the other hand, it can be seen that the electrolytic copper foil according to the present invention has a glossiness [Gs (60 °)] of over 400 and has a smoother surface. Moreover, as shown in the Example, glossiness [Gs (60 degrees)] 700 or more can also be attained by optimization of conditions. In addition, here, although the upper limit of glossiness is not determined, about 780 is an upper limit on an empirical judgment.

The surface of the untreated copper foil which forms the blackening process surface of the surface-treated copper foil which concerns on this invention described above is a precipitation surface rather than the gloss surface of the said electrolytic copper foil. This is because it is difficult to require this level of smoothness on the surface of the rotating cathode, and the precipitated copper is likely to peel off from the surface of the rotating cathode simultaneously with electroprecipitation.

It is preferable to use the following manufacturing conditions for manufacture of the unprocessed copper foil mentioned above. At least one of 3-mercapto-1-propanesulfonic acid (hereinafter referred to as 'MPS') or bis (3-sulfonpropyl) disulfide (hereinafter referred to as 'SPS') and a cyclic structure It is preferable to use the sulfuric acid-based coin solution obtained by adding a quaternary ammonium salt polymer having chlorine and chlorine. By using the sulfuric acid-based coin dissolving liquid of this composition, manufacture of the untreated copper foil which has the above-mentioned quality is attained. The presence of the three components of MPS or SPS, the quaternary ammonium salt polymer which has a cyclic structure, and chlorine contained in a sulfuric acid type | mold solution used here is essential. On the other hand, the copper concentration of the sulfuric acid-based coin solution according to the present invention assumes a solution having a concentration of 50 g / l to 120 g / l and a free sulfuric acid of about 60 g / l to 250 g / l.

It is preferable that the sum total concentration of MPS or SPS in the said sulfuric acid type | system | group solution is 0.5 ppm-100 ppm, More preferably, it is 0.5 ppm-50 ppm, More preferably, it is 1 ppm-30 ppm. When the combined concentration of this MPS or SPS is less than 0.5 ppm, the precipitation surface of the electrolytic copper foil becomes rough, and it becomes difficult to obtain a low profile electrolytic copper foil. On the other hand, even if the combined concentration of MPS or SPS exceeds 100 ppm, the effect of smoothing the precipitated surface of the obtained electrolytic copper foil is not improved and only causes an increase in the cost of wastewater treatment. Meanwhile, MPS or SPS used in the present invention is used in the meaning including MPS salt and SPS salt, and the stated value of the concentration is 3-mercapto-1-propanesulfonic acid sodium salt (hereinafter referred to as 'MPS-Na'). It is a conversion value as.

In the sulfuric acid-based coin solution according to the present invention, MPS may be dimerized, and in this case, SPS structure is obtained. Therefore, the combined concentration of MPS or SPS includes those added as SPS in addition to salts such as 3-mercapto-1-propanesulfonic acid monomer and MPS-Na, and modified products polymerized in SPS and the like after being added in electrolyte solution as MPS. Concentration. Hereinafter, the structural formula of MPS is represented by Chemical Formula 1, and the structural formula of SPS is represented by Chemical Formula 2.

In addition, the concentration of the quaternary ammonium salt polymer in the sulfuric acid-based coin solution used in the method for producing an electrolytic copper foil according to the present invention is preferably 1 ppm to 150 ppm, more preferably 10 ppm to 12 ppm, still more preferably 15 ppm to 40 ppm. Here, a variety of quaternary ammonium salt polymers having a cyclic structure can be used, but considering the effect of forming a low profile precipitation surface, diallyl dimethyl ammonium chloride (hereinafter referred to as 'DDAC') Most preferably, a polymer is used. DDAC forms a cyclic structure when taking a polymer structure, and part of the cyclic structure is composed of nitrogen atoms of quaternary ammonium. In addition, since the DDAC polymer is considered to be one of the four- to seven-membered rings or a mixture thereof, the cyclic structure is represented by the following formula (3) as a representative of a compound having a five-membered ring structure among these polymers. It was. As can be seen from the general formula (3), the DDAC polymer is one in which DDAC has a dimer or more polymer structure.

And when the density | concentration of the DDAC polymer in this sulfuric acid type | system | group solution is less than 1 ppm, even if it raises the sum total density | concentration of MPS or SPS, the precipitation surface of an electrolytic copper foil becomes rough, and it becomes difficult to obtain a low profile electrolytic copper foil. On the other hand, even if the concentration of the DDAC polymer in the sulfuric acid-based coin solution exceeds 150 ppm, the precipitation state of copper becomes unstable, and it becomes difficult to obtain a low profile electrolytic copper foil.

In addition, the chlorine concentration in the sulfuric acid-based coin solution is preferably 5ppm to 60ppm. When this chlorine concentration is less than 5 ppm, the precipitation surface of an electrolytic copper foil becomes rough and it cannot become low profile. On the other hand, when the chlorine concentration exceeds 60 ppm, the rough surface of the electrolytic copper foil becomes rough, and the electric precipitation state is not stabilized, and a low profile precipitation surface cannot be formed.

As mentioned above, the balance of components of MPS and / or SPS, DDAC polymer and chlorine in the sulfuric acid-based coin solution is most important, and if these quantitative balances are out of the above ranges, as a result, untreated copper foil of the above quality cannot be obtained. do.

In the case of producing the untreated copper foil using the sulfuric acid-based coin dissolving solution, the liquid temperature is 20 ° C. to 60 ° C., more preferably 40 ° C. to 55 ° C., and the current density is 15 A / dm 2 to 90 A / dm 2, Preferably, electrolysis is performed at 50 A / dm 2 to 70 A / dm 2. If the liquid temperature is less than 20 ° C, the precipitation rate is lowered, and the variation in mechanical properties such as elongation and tensile strength is increased. On the other hand, when liquid temperature exceeds 60 degreeC, the amount of evaporation moisture will increase, and fluctuation | variation of liquid concentration will be fast, and the precipitation surface of the electrolytic copper foil obtained cannot maintain favorable smoothness. In addition, when the current density is less than 15 A / dm 2, the precipitation rate of copper is slow, resulting in low industrial productivity. On the other hand, when a current density exceeds 90 A / dm <2>, the roughness of the precipitation surface of the untreated copper foil obtained becomes large and it cannot maintain a low profile.

Moreover, it is also preferable to provide a rust prevention process layer in the said blackening process surface. It is because long-term storage property of the surface-treated copper foil which concerns on this invention can be ensured. In this antirust treatment layer, inorganic discoloration prevention layers such as zinc and brass, benzotriazole, imidazole, and the like can be used as long as they do not cause discoloration of the blackened surface and can be easily dissolved by copper etching solution. It is possible to use either an organic rust prevention layer or the like.

Blackening surface-treated copper foil: It is preferable that the blackening process surface is provided in the surface of the said untreated copper foil, and the glossiness [Gs (60 degrees)] of the blackening process surface is 35 or less. If the glossiness exceeds 35, it becomes a so-called black light state and the metallic luster becomes conspicuous.

And the formation of this blackening process surface can employ | adopt various manufacturing methods as described below.

[Nickel-based Blackening Treatment Method]

As the nickel-based blackening treatment method, it is preferable to employ the blackening treatment method described below in that it becomes a good blackening treatment and can be removed with a copper etching solution.

The nickel sulfate layer is formed on the precipitation surface of the above-mentioned untreated copper foil. This nickel sulfate layer contains 10 g / l to 300 g / l of nickel sulfate (pentahydrate) and is supplied at a current density of 1 A / dm 2 or more by using a nickel sulfate plating solution having a pH range of 5.5 to 6.0 with alkali metal hydroxide salts. By decomposition, it forms in a black nickel plating layer. Here, when nickel sulfate (pentahydrate) in a nickel sulfate plating liquid is less than 10 g / l, the electrodeposition rate of the nickel sulfate layer formed will become slow, and the thickness of a nickel sulfate layer will become nonuniform. On the other hand, when nickel sulfate (pentahydrate) exceeds 300 g / l, the color tone of the nickel sulfate layer formed will not become a favorable blackening state. This nickel sulfate plating solution is characterized in that it does not contain a pH buffer.

In addition, the solution pH of the nickel sulfate plating liquid at this time is adjusted to the range of 5.5-6.0. If it is out of this range, a favorable black color cannot be obtained. Alkali hydroxide metal salts, such as sodium hydroxide or potassium hydroxide, are used for this pH adjustment.

In addition, a current of 1 A / dm 2 or more is used for the current density at the time of performing electrolysis. In the nickel sulfate plating solution described above, even if an excessive electrolytic current flows, the smoothness of the plated surface to be formed is maintained. Therefore, in the present invention, the plating treatment is performed without using the pH buffer generally used intentionally, so that the increase in pH in the vicinity of the negative electrode surface during electrolysis is actively used. That is, by performing electrolysis substantially in a strong alkali environment, nickel oxide etc. are included in a nickel sulfate layer, and a black plating film is formed. Therefore, the upper limit of the current density does not need to be set in particular, and may be arbitrarily determined in consideration of the productivity in the process.

In the case of nickel-based blackening treatment, it is particularly preferable to provide a zinc-nickel alloy layer as a rust prevention treatment layer on the blackening treatment surface. This is because it becomes a dissolution promoter for etching removal by the coin dissolution solution of the nickel-based blackening treatment layer. Formation of the zinc-nickel alloy layer and the like will be described later.

The blackened surface-treated copper foil is obtained by washing with water and drying through 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.

[Cobalt-based blackening treatment method]

As the cobalt-based blackening treatment method, it is preferable to adopt one of the two types of cobalt-based blackening treatment method A and the cobalt-based blackening treatment method B described below to obtain a satisfactory blackening treatment. It is preferable at the point which becomes possible.

Cobalt-based blackening treatment method A: This cobalt-based blackening treatment method is a blackening treatment method in the case of using an unstirred bath. A cobalt sulfate plating layer is formed on the precipitation surface of the above-mentioned untreated copper foil. This cobalt sulfate plating layer contains 8 g / l to 10 g / l of cobalt sulfate (hexahydrate), and uses a cobalt sulfate plating solution having a pH of 4.0 or more as an unstirred bath, and electrolysis at a current density of 2 A / dm 2 or more. To form a black cobalt sulfate plating layer. That is, it is the cobalt sulfate plating condition in the case of not performing solution stirring. 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 becomes uneven. 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.

In addition, it is preferable to adjust the solution pH of the cobalt sulfate plating liquid at the target of 4.5-5.5 range at this time. Within this range, a good black cobalt plating layer can be obtained with high yield. It is not preferable to add another electrolyte such as sodium hydroxide or potassium hydroxide to make this pH adjustment. This is because black of the cobalt plating layer tends to be changed into a metallic color.

Thus, the solution pH is stabilized in the range of 4.0 or more by keeping the concentration of metal ions in the solution constant. In order to stabilize the cobalt ion concentration in the solution as described above, the cobalt ion concentration is dissolved by supplying the cobalt ion powder electrodeposited 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 the electric current density at the time of electrolysis uses 2 A / dm <2> or more. The cobalt sulfate plating solution described above causes an excessive electrolytic current, and even if a plated surface having a slight unevenness is formed, powder dropout phenomenon rarely occurs there. 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.

After passing through the above process, it washes and dries and the blackening surface-treated copper foil which makes a cobalt sulfate plating layer a blackening process surface is obtained. 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.

Cobalt-based blackening treatment method B: Here, the blackening treatment method in the case of using a stirring bath is demonstrated. By employ | adopting the following conditions, it becomes a dense blackening process surface similarly to the cobalt sulfate plating layer formed by the unstirred cobalt sulfate plating bath.

The cobalt sulfate plating solution containing 10 g / l to 40 g / l of cobalt sulfate (7-hydrate) on the precipitated surface of the untreated copper foil described above and having a pH of 4.0 or more and a liquid temperature of 30 ° C. or lower is used as a stirring bath of 4 A / dm 2 or less. Electrolysis is carried out at a current density to form a black cobalt sulfate plating layer. That is, the fundamental difference from the cobalt-based blackening treatment method A is that the cobalt sulfate plating solution is electrolyzed while stirring the cobalt sulfate plating. This cobalt sulfate concentration tends to be able to produce a good blackening state as the cobalt sulfate concentration is lower. 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 tends to be uneven. The result is a lack of enemy 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, the solution pH of the cobalt sulfate plating solution at this time is 4.0 or more, and it is preferable to adjust especially 4.5 to 5.5 range. Within this range, it is possible to stably obtain a good black cobalt plating layer with a high yield. It is not preferable to add another electrolyte such as sodium hydroxide or potassium hydroxide in this pH adjustment. It is as mentioned above that black of a cobalt plating layer becomes easy to change into metal color. The solution pH is also as described above by stabilizing the concentration of metal ions in the solution, resulting in a range of 4.0 or more.

In addition, it is preferable to use the cobalt sulfate plating liquid at this time, making the liquid temperature 30 degrees C or less. The lower the liquid temperature at this time, the better the blackening treatment surface tends to be obtained. If the liquid temperature is set to 30 ° C. or lower, it is possible to obtain a better blackened surface.

And the electric current of 4 A / dm <2> or less is used for the current density at the time of electrolysis. It is possible to form a cobalt sulfate plating layer having good fine unevenness that is excellent in adhesion to an organic material and the like even without roughening the surface of the copper foil in this range. Usually, in order to obtain the black-plated surface with unevenness, a method of flowing an electrolytic current flowing into an excessively burned plating region is employed. However, in this case, the smaller the current density used for electrolysis, the more stable blackening treatment tends to be possible. 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 determined as the lower limit. On the other hand, when a current density exceeds 4 A / dm <2>, it will become the blackening process surface of the same level as blackening process was performed to the copper foil surface which is not subjected to roughening process in the manufacturing method A of the said 1st surface treatment copper foil, and a manufacturing method The meaning of adopting B is lost. In addition, the powder blackening process surface formed in the range of the current density mentioned above does not generate | occur | produce a powder fall-out phenomenon there.

Water-washed and dried through the above process, and the surface-treated copper foil which makes a cobalt sulfate plating layer into a blackening process surface is obtained. 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.

Rust prevention treatment: It is preferable to apply a rust prevention treatment to the surface of the blackening surface treatment copper foil obtained by making it above. Therefore, the formation process of a rust prevention process layer is demonstrated here. The use of conventionally known organic rust prevention such as imidazole and benzotriazole, and inorganic rust prevention by zinc alloys such as zinc or brass, which are generally used, does not require special explanation, The detailed description thereof will be omitted since it is considered to be followed.

Hereinafter, the case where the antirust process layer is formed by plating by using a zinc-nickel alloy plating solution or a zinc-cobalt alloy plating solution will be described. First, zinc-nickel alloy plating will be described. There is no particular limitation on the zinc-nickel alloy plating solution used here. For example, the nickel concentration is 1 g / l to 2.5 g / l using nickel sulfate and the zinc concentration is 0.1 g / l to 1 g / l using zinc pyrophosphate. , Potassium pyrophosphate 50 g / l to 500 g / l, liquid temperature 20 ° C. to 50 ° C., pH 8 to pH 11, and current density of 0.3 A / dm 2 to 10 A / dm 2.

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 g / l to 2.5 g / l using cobalt sulfate and the zinc concentration is 0.1 g / l to 1 g / l using zinc pyrophosphate. , Potassium pyrophosphate 50 g / l to 500 g / l, liquid temperature 20 ° C. to 50 ° C., pH 8 to pH 11, and current density of 0.3 A / dm 2 to 10 A / dm 2. The antirust process layer which combined this zinc-cobalt alloy plating and the chromate treatment mentioned later shows especially outstanding corrosion resistance.

Moreover, when forming a chromate layer after forming a zinc-nickel alloy layer, a zinc-cobalt alloy layer, etc. on the surface of copper foil as a rust prevention process, it becomes possible to obtain more excellent corrosion resistance. That is, what is necessary is just to provide the chromate processing process after formation of the above-mentioned antirust process layer. In this chromate treatment step, either the substitution treatment in which the chromate solution and the copper foil surface are brought into contact with each other, or the electrolytic chromate treatment in which the chromate film is electrolyzed in the chromate solution may be employed. Moreover, also about the chromate solution used here, it is possible to use the thing of the range used by a conventional method. And the water-washed and dried after that, and blackening surface-treated copper foil which is more excellent in corrosion resistance is obtained.

<Electromagnetic shielding conductive mesh> The blackening surface-treated copper foil which concerns on this invention mentioned above is excellent in the flatness of the surface, manufactured the conductive mesh using this blackening surface-treated copper foil, and the etching is complete | finished, and Since blurring does not occur on the surface, it is possible to greatly contribute to the elimination of the pseudo contour disturbance by the emission control of the pixel without deteriorating the luminance of the plasma display panel.

In addition, the blackening process used for formation of a blackening process surface in this invention does not fall out of a powder, and exhibits favorable black color, and the blackening process layer can be etched out by a normal copper etching process. Therefore, it is possible to easily process to arbitrary shapes using the process of manufacturing a printed wiring board. Considering this, it can be said that it is optimal for the use of the electromagnetic shielding conductive mesh put in the front panel of the plasma display panel.

Hereinafter, the relationship between the roughness measured using the stylus roughness meter and the three-dimensional surface structure analysis microscope is described, for example. Since both the tactile roughness meter and the three-dimensional surface structure analysis microscope are used to obtain the same index of roughness for the same object, it is generally considered that these values will coincide. However, since the measurement accuracy is different in the case of a stylus roughness meter and in the case of a three-dimensional surface structure analytical microscope depending on the probe beam diameter, the measurement is different. In general, when a certain level of unevenness exists on the measurement surface, the roughness measurement value of the stylus roughness meter tends to be larger than the roughness measurement value using a three-dimensional surface structure analysis microscope. On the other hand, as the measurement surface becomes flat and the surface of the low profile without undulation, the roughness measurement value of the stylus roughness meter tends to be smaller than the roughness measurement value using a three-dimensional surface structure analysis microscope.

Example 1

Hereinafter, it demonstrates in order of manufacture of an untreated copper foil, manufacture of a blackening surface treatment copper foil, an etching test result, and a haze measurement test result.

Preparation of untreated copper foil: copper sulfate solution as copper sulfate solution, copper concentration 80g / l, free sulfuric acid 140g / l, MPS concentration 5ppm, DDAC polymer (using UNICEN FPA100L manufactured by Senka Co., Ltd.) 3ppm, chlorine concentration 10ppm, liquid temperature Using a 50 ° C. solution, electrolysis was carried out at a current density of 60 A / dm 2 to obtain an untreated foil having a thickness of 18 μm. The polished surface to which the surface shape of the titanium electrode of this untreated copper foil was transferred was Rzjis (Tamper roughness meter) = 1.02 micrometer, and the roughness and glossiness of the precipitation surface of the other surface were Ra (3-dimensional surface structure analysis microscope) = 29.2 nm , Rz (three-dimensional surface structure analysis microscope) = 200 nm, Ra (tactile roughness meter) = 0.22 m, Rzjis (tactile roughness meter) = 0.47 m, glossiness [Gs (60 °)] = 699.

Production of blackening surface-treated copper foil: And the untreated copper foil mentioned above was pickled and cleaned. This pickling treatment condition was a dipping time of 30 seconds using a dilute sulfuric acid solution having a concentration of 100 g / l and a liquid temperature of 30 ° C.

After the pickling process was completed, a nickel sulfate layer was formed on the precipitated surface of the untreated copper foil. The formation of the nickel sulfate layer was performed by electrolyzing at a current density of 1 A / dm 2 using a nickel sulfate plating solution having a nickel sulfate (pentahydrate) adjusted to pH 6.0 with 100 g / l and sodium hydroxide and having a liquid temperature of 30 ° C., A black nickel sulfate plating layer was formed.

In addition, the zinc-nickel alloy layer was formed on both surfaces by plating by using a zinc-nickel alloy plating solution on both surfaces of the copper foil in which the formation of the black nickel sulfate plating layer was completed as a rust prevention process. The zinc-nickel alloy layer has nickel concentration of 2.0g / l using nickel sulfate, zinc concentration of 0.5g / l using zinc pyrophosphate, potassium pyrophosphate 250g / l, liquid temperature 35 ℃, pH 10, current density 5A Electrolysis was carried out for 5 seconds under the condition of / dm 2 to be uniformly and smoothly electroprecipitated on both sides.

When the formation of the zinc-nickel alloy 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 to blow out moisture, thereby producing a blackened surface of very good color tone. The surface-treated copper foil provided with this was obtained. The glossiness [Gs (60 °)] of the blackened surface of this blackened surface-treated copper foil was 27. In addition, powder dropout phenomenon could not be confirmed by the tape test by sticking and peeling an adhesive tape to the said blackening process surface.

Etching test: The dry film which becomes an etching resist was stuck to both surfaces of the blackening surface treatment copper foil obtained by making it above. The conductive film having a mesh pitch of 200 mu m, a mesh line width of 10 mu m, a mesh bias angle of 45 DEG, and a superimposed mask film for starting the electromagnetic wave shielding conductive mesh are superposed only on the dry film on the blackened surface. The pattern was exposed to ultraviolet light. At this time, ultraviolet rays were also exposed to the entire surface of the etching resist layer on the opposite side, so that it could not be removed by subsequent development. Then, it developed using alkaline solution and the etching resist pattern was formed.

Then, copper etching was performed on the blackening treatment surface side using a copper chloride etching solution as the copper etching solution, 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.

Haze measurement test: The resin film layer was formed in the blackening process surface of the said blackening surface treatment copper foil as follows. First, BP3225-50P made by Nippon Kayaku Co., Ltd. which is commercially available as a mixed varnish with an o-cresol novolak-type epoxy resin (YDCN-704 manufactured by Dongwha Chemical Co., Ltd.), an aromatic polyamide resin polymer soluble in a solvent, and cyclopentanone as a solvent. It was used as a raw material. The mixed varnish was added with VH-4170 manufactured by Nippon Ink Co., Ltd. and 2E4MZ manufactured by Shikoku Kasei Kogyo Co., Ltd. as a curing accelerator, to obtain a resin mixture having a blending ratio shown below.

Resin mixture: 38 parts by weight of o-cresol novolac epoxy resin

50 parts by weight of aromatic polyamide resin polymer

Phenolic resin 18 parts by weight

0.1 part by weight of curing accelerator

This resin mixture was further used as the resin solution by adjusting resin solid content to 30 weight% using methyl ethyl ketone. The resin solution prepared as mentioned above was apply | coated to the blackening process surface of the blackening surface treatment copper foil mentioned above using the gravure coater. And air drying for 5 minutes was performed, the drying process was performed for 3 minutes in the heating atmosphere of 140 degreeC after that, and it was set as the copper foil with resin which made the resin layer 40 micrometers thick. And blackening surface-treated copper foil was etched in the whole surface in this state, and it was set as the resin film alone, and this was made into the sample for haze measurement. The haze measurement of this sample was found to be 5.8%.

Example 2

Hereinafter, it demonstrates in order of manufacture of an untreated copper foil, manufacture of a blackening surface treatment copper foil, an etching test result, and a haze measurement test result.

Preparation of untreated copper foil: The untreated copper foil manufactured by the method similar to Example 1 was used. Therefore, the roughness and glossiness of the Rzjis of the glossy surface to which the surface shape of the titanium electrode of this untreated copper foil was transferred, and the precipitation surface of the other surface are the same as that of Example 1.

Manufacture of blackening surface-treated copper foil: And the untreated copper foil mentioned above was pickled-treated like Example 1 and cleaned.

And when the pickling process was completed, a cobalt sulfate plating layer was formed on the precipitation surface of the untreated copper foil. The formation of the cobalt sulfate plating layer was performed by adjusting the cobalt sulfate (hexahydrate) to 10 g / l and pH to 5.0, using a cobalt sulfate plating solution having a liquid temperature of 30 ° C. as an unstirred bath, for 8 seconds at a current density of 2 A / dm 2. By electrolysis, it formed as a black cobalt sulfate plating layer (thickness 320 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 of the short time electrolysis. In this example, no special rust prevention treatment was performed.

Through the above steps, 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 to blow out moisture, and the blackening surface treatment is provided with a blackened surface of very good color tone. Copper foil was obtained. The glossiness [Gs (60 °)] of the blackened surface of this blackened surface-treated copper foil was 25. In addition, powder dropout phenomenon could not be confirmed by the tape test by sticking and peeling an adhesive tape to the said blackening process surface.

Etching test: The electromagnetic wave shielding conductive mesh was produced like Example 1 using the blackening surface-treated copper foil obtained as mentioned above. As a result, very good etching was performed without etching residual water.

Haze measurement test: It was made into the copper foil state with resin by the method similar to the said Example 1, In this state, the blackening surface-treated copper foil was etched on the whole surface, it was made as the resin film alone, and it was set as the sample for haze measurement. It was 5.5% when the haze measurement of this sample was performed.

Example 3

Hereinafter, it demonstrates in order of manufacture of an untreated copper foil, manufacture of a blackening surface treatment copper foil, an etching test result, and a haze measurement test result.

Preparation of untreated copper foil: The untreated copper foil manufactured by the method similar to Example 1 was used. Therefore, the roughness and glossiness of the Rzjis of the glossy surface to which the surface shape of the titanium electrode of this untreated copper foil was transferred, and the precipitation surface of the other surface are the same as that of Example 1.

Manufacture of blackening surface-treated copper foil: And the untreated copper foil mentioned above was pickled-treated like Example 1 and cleaned.

And when the pickling process was completed, a cobalt sulfate plating layer was formed on the precipitation surface of the untreated copper foil. 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 15 seconds at a current density of 1 A / dm 2. By electrolysis, it formed into the black cobalt sulfate plating layer (conversion thickness 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 of the short time electrolysis. In this embodiment, no special rust prevention treatment was performed.

Pure water is thoroughly showered and washed through the above steps, and condensed for 4 seconds in a drying furnace with an atmospheric temperature of 150 ° C. with an electric heater to blow out moisture to form a blackened surface-treated copper foil having a blackened surface of very good color tone. Got. The glossiness [Gs (60 °)] of the blackened surface of this blackened surface-treated copper foil was 26. In addition, powder dropout phenomenon could not be confirmed by the tape test by sticking and peeling an adhesive tape to the said blackening process surface.

Etching test: The electromagnetic wave shielding conductive mesh was produced like Example 1 using the blackening surface-treated copper foil obtained as mentioned above. As a result, very good etching was performed without etching residues.

Haze measurement test: It was made into the copper foil state with resin by the method similar to the said Example 1, In this state, the blackening surface-treated copper foil was etched on the whole surface, it was made as the resin film alone, and it was set as the sample for haze measurement. The haze measurement of this sample was found to be 5.4%.

Example 4

Hereinafter, it demonstrates in order of manufacture of an untreated copper foil, manufacture of a blackening surface treatment copper foil, an etching test result, and a haze measurement test result.

Preparation of untreated copper foil: Copper sulfate solution as copper sulfate solution, copper concentration 80g / l, free sulfuric acid 140g / l, SPS concentration 10ppm, DDAC polymer (using Senka Co., Ltd. unisex FPA100L) 20ppm, chlorine concentration 22ppm, Using a solution having a liquid temperature of 50 ° C., electrolysis was performed at a current density of 60 A / dm 2 to obtain an untreated foil having a thickness of 18 μm. The polished surface to which the surface shape of the titanium electrode of this untreated copper foil was transferred was Rzjis (Tampering roughness meter) = 1.02 micrometer, and the roughness and glossiness of the precipitation surface of the other surface were Ra (3-dimensional surface structure analysis microscope) = 26 nm. , Rz (three-dimensional surface structure analysis microscope) = 180 nm, Ra (tactile roughness meter) = 0.10 m, Rzjis (tactile roughness meter) = 0.30 m, glossiness [Gs (60 °)] = 735.

Hereinafter, it carried out similarly to Example 3, and obtained blackening surface-treated copper foil. The glossiness [Gs (60 °)] of the blackened surface of this blackened surface-treated copper foil was 26. In addition, powder dropout phenomenon could not be confirmed by the tape test by sticking and peeling an adhesive tape to the said blackening process surface.

Etching test: The electromagnetic wave shielding conductive mesh was produced like Example 1 using the blackening surface-treated copper foil obtained as mentioned above. As a result, very good etching was performed without etching residues.

Haze measurement test: It was made into the copper foil state with resin by the method similar to the said Example 1, In this state, the blackening surface-treated copper foil was etched on the whole surface, it was made as the resin film alone, and it was set as the sample for haze measurement. It was 5.2% when the haze measurement of this sample was performed.

Comparative example

In a comparative example, the untreated copper foil is manufactured with the manufacturing method described below, the blackening surface treatment of the said Example 2 is added, and the haze measurement test is shown. Therefore, only the manufacture of an untreated copper foil and the haze measurement test result are demonstrated. Other conditions are the same as in Example 2.

Comparative Example 1

Preparation of untreated copper foil: As a tracking experiment of Example 1 disclosed in Patent Document 3, copper sulfate (reagent) and sulfuric acid (reagent) were dissolved in pure water to obtain copper sulfate (pentahydrate equivalent) of 280 g / l and free sulfuric acid concentration of 90 g / l. , Copolymer of diallyldialkylammonium salt and sulfur dioxide (manufactured by Nitto Spinning Co., Ltd., brand name PAS-A-5, weight average molecular weight 4000: 4 ppm), polyethylene glycol (average molecular weight 1000: 10 ppm), and 3-mercapto-1-propane Sulfonic acid (1 ppm) was added, and sulfuric acid acidic copper plating solution was prepared by using sodium chloride to prepare a chlorine concentration of 20 ppm.

And the surface was grind | polished using the titanium plate electrode as a cathode, and the surface was grind | polished 2000 times. Surface roughness was adjusted to 0.20 mu m with Ra. And the positive electrode was electrolyzed at 40 degreeC and current density of 50 A / dm <2> with the said electrolyte solution using the lead plate for the positive electrode, and the 18-micrometer-thick untreated copper foil was obtained. The roughness and glossiness of this untreated copper foil was Rzjis (Temperature Roughness Meter) = 1.02 µm, and the roughness and glossiness of the precipitated surface of the other surface were Ra (three-dimensional surface structure analysis). Microscope) = 124.5 nm, Ra (3-D Surface Structure Analysis Microscope) = 1532 nm, Ra (Tamper Roughness Meter) = 0.18 µm, Rzjis (Tamper Roughness Meter) = 0.88 µm, Glossiness [Gs (60 °)] = 283 It was.

Thereafter, a blackened surface-treated copper foil was obtained in the same manner as in Example 2. The glossiness [Gs (60 °)] of the blackened surface of this blackened surface-treated copper foil was 22. In addition, powder dropout phenomenon could not be confirmed by the tape test by sticking and peeling an adhesive tape to the said blackening process surface.

Haze measurement test: It was made into the copper foil state with resin by the method similar to the said Example 1, In this state, the blackening surface-treated copper foil was etched on the whole surface, it was made as the resin film alone, and it was set as the sample for haze measurement. The haze measurement of this sample was found to be 12.3%.

Comparative Example 2

Preparation of untreated copper foil: A copper sulfate solution, a copper sulfate solution of 80 g / l, a free sulfuric acid 140 g / l, a DDAC polymer (using UNICEN FPA100L manufactured by Senka Co., Ltd.), a chlorine concentration of 15 ppm and a solution temperature of 50 ° C. It used and electrolyzed at the current density of 60 A / dm <2>, and obtained the untreated copper foil of 18 micrometers thickness. The roughness and glossiness of this untreated copper foil was Rzjis (Temperature Roughness Meter) = 1.02 µm, and the roughness and glossiness of the precipitated surface of the other surface were Ra (three-dimensional surface structure analysis). Microscope) = 422 nm, Rz (3-dimensional surface structure analysis microscope) = 5240 nm, Ra (tactile roughness meter) = 0.57 µm, Rzjis (tactile roughness meter) = 3.80 µm, glossiness [Gs (60 °)] = 0.7 It was.

Thereafter, a blackened surface-treated copper foil was obtained in the same manner as in Example 2. The glossiness [Gs (60 °)] of the blackened surface of this blackened surface-treated copper foil was 0.5. In addition, powder dropout phenomenon could not be confirmed by the tape test by sticking and peeling an adhesive tape to the said blackening process surface.

Haze measurement test: It was made into the copper foil state with resin by the method similar to the said Example 1, In this state, the blackening surface-treated copper foil was etched on the whole surface, it was made into the resin film alone, and it was set as the sample for haze measurement. The haze measurement of this sample was found to be 42.0%.

Comparative Example 3

Preparation of untreated copper foil: Copper sulfate solution as copper sulfate solution, copper concentration 80 g / l, free sulfuric acid 140 g / l, DDAC polymer concentration 4 ppm (using Unisce FPA10OL manufactured by Senka Co., Ltd.), low molecular weight glue (number average molecular weight) 1560: 6 ppm), a chlorine concentration of 15 ppm and a solution temperature of 50 ° C. were used to electrolyze at a current density of 60 A / dm 2 to obtain an untreated copper foil having a thickness of 18 μm. The roughness and glossiness of this untreated copper foil was Rzjis (Temperature Roughness Meter) = 1.02 µm, and the roughness and glossiness of the precipitated surface of the other surface were Ra (three-dimensional surface structure analysis). Microscope) = 360 nm, Rz (three-dimensional surface structure analysis microscope) = 4530 nm, Ra (tactile roughness meter) = 0.42 µm, Rzjis (tactile roughness meter) = 3.89 µm, glossiness [Gs (60 °)] = 1.1 It was.

Thereafter, a blackened surface-treated copper foil was obtained in the same manner as in Example 2. The glossiness [Gs (60 °)] of the blackened surface of this blackened surface-treated copper foil was 0.5. In addition, powder dropout phenomenon could not be confirmed by the tape test by sticking and peeling an adhesive tape to the said blackening process surface.

Haze measurement test: It was made into the copper foil state with resin by the method similar to the said Example 1, In this state, the blackening surface-treated copper foil was etched on the whole surface, it was made as the resin film alone, and it was set as the sample for haze measurement. It was 45.0% when the haze measurement of this sample was performed.

The blackened surface-treated copper foil which concerns on this invention is excellent in the flatness of the blackened surface, and produced the conductive mesh using this blackened surface-treated copper foil, and the etching is complete | finished and the blur phenomenon on the surface of the adhesive bond layer exposed between circuits. Because of the low degree of occurrence of the fluorescence, it is possible to greatly contribute to eliminating pseudo contour obstacles by controlling the light emission of the pixel without degrading the luminance of the plasma display panel.

Moreover, if the blackening process surface of the blackening surface-treated copper foil which concerns on this invention adopts the blackening process which has as a nickel-based blackening process surface or cobalt-based blackening process surface formed on the fixed conditions, there will be no powder fall-off, In addition, it exhibits good black color, and the blackening treatment layer can be etched away by a common copper etching process. Therefore, no special facility investment is required, and the process of manufacturing a printed wiring board can be used to provide a high-frequency black mask plasma display panel of an electromagnetic shielding conductive mesh.

Claims (7)

A surface-treated copper foil that provides a blackened surface on the surface of an untreated electrolytic copper foil, wherein the untreated electrolytic copper foil has a surface having a surface roughness Ra of 45 nm or less measured using a three-dimensional surface structure analysis microscope, and blackened to the surface. The blackening surface-treated copper foil characterized by providing the process surface. The method of claim 1, The surface which provides the blackening process surface of the said untreated electrolytic copper foil is blackening surface-treated copper foil whose surface roughness Rz measured using the three-dimensional surface structure analysis microscope is 850 nm or less. The method according to claim 1 or 2, The surface which provides the blackening process surface of the said unprocessed electrolytic copper foil has the low profile whose surface roughness (Rzjis) is less than 0.8 micrometer when measured based on JISB0601, and the glossiness (Gs (60 degrees)) Blackening surface-treated copper foil which is 400 or more. The method according to any one of claims 1 to 3, The blackening surface-treated copper foil provided with the antirust process layer on the said blackening process surface. The method according to any one of claims 1 to 4, The said blackening process surface is the blackening surface-treated copper foil whose glossiness [Gs (60 degrees)] is 35 or less. The method according to any one of claims 1 to 5, The blackened surface-treated copper foil is a nickel-based blackened surface or a cobalt-based blackened surface. An electromagnetic wave shielding conductive mesh for a front panel of a plasma display using the blackened surface-treated copper foil according to any one of claims 1 to 6.

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