TW200533251A - Surface-treated copper foil having grayed surface, process for producing the same and electromagnetic wave shielding conductive mesh for front panel of plasma display wherein use is made of the surface-treated copper foil - Google Patents

Abstract

To provide a surface-treated copper foil having excellent gray color and workable in a regular copper etching process, and a conductive mesh for PDP manufactured by the surface-treated copper foil. In the surface-treated copper foil having a grayish-treated surface on one side, a cobalt sulfide plated layer is provided on a coarse surface of a copper foil layer, and a surface-treated copper foil or the like having the grayish-treated surface having a rustproof layer is employed. The surface-treated copper foil is manufactured by performing electrolysis at the predetermined current density by using cobalt plating liquid containing cobalt sulfide (7-hydrate) to form the rustproof layer on the coarse surface of an electrolytic copper foil or the like, and a method for water-rinsing and drying the rustproof layer is employed.

Description

200533251 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a plasma display front panel having a grayed-out surface using the surface-treated copper foil; an electrical mesh. In particular, it provides a surface-treated copper foil suitable for the manufacture of plasma-sensitive magnetic wave shielding conductive mesh. [Prior art] A conductive mesh for shielding a φ electric display panel is transformed into a conductive mesh. Here, a conductive method is established. One is to produce a surface-treated steel foil film using a photo-etching method. Next, the copper foil and the supporting substrate were surface-treated on the other surface, and then the conductive mesh of the surface-treated steel foil alone was known. Furthermore, in recent years, due to the requirements of power saving, the voltage generated by the slurry has been reduced from 2000v to 50V. The brightness of the Cheng Guangyu voltage has been reduced, the conductive network has been reduced, and the front glass panel has been reduced by the conductive mesh. It is also performed by reducing the thickness of the conductive mesh sheet. One of the methods is to use the thin layer of the coin-evaporation method (origin), and then use a layer of electrolytic copper to make the net m 胄 # using the light-money engraving method. Regardless of the method used to make the conductive mesh, it is incorporated into the front panel and can be passed through the front of Bronze 2213-6894-PF; Ahddub surface-treated copper pigs and the electromagnetic wave shielding guides are used for the panel. The metallized fiber mesh sheet has been manufactured by laminating and laminating it to PET thin film. It is obtained by peeling off the supporting substrate at the same time with a light-cut method. Narrow coverage etc. try. To make it easier to form the conductive mesh as a kind of electroplating, plating and thin steel, the conductive mesh itself 7 is confirmed by the surface vision 5 200533251. It is recognized by all industry players. Surface-treated copper foil on the surface or chemically treated surface. Wood brown (the current surface-treated copper pig with a blackened surface) The single side of the surface-treated copper box processed with this conductive mesh is treated as black to increase the brightness of transmitted light. In the past, this process was diverted: to improve the adhesion between the inner layer circuit of the multilayer printed circuit board and the resin layer; to blacken the copper oxide layer. / Of course ... the blackening process described above has major problems. It is also true that when a copper-containing black oxide is reported on the surface, a good blackened surface can be obtained. However, the black oxide of copper formed on the surface of copper is more likely to fall off the blackened surface, which causes the so-called powder falling phenomenon, which makes the blackened surface easily damaged and the processing becomes difficult. In addition, there is a lack of tuning stability. …, If the powder falling phenomenon occurs in Ba-e-eup, the black oxide falling off will be mixed and useless. It is an important cause of the deterioration of transparency when it is dispersed in the transparent adhesive layer during the transparent treatment integrated with the front panel glass. On the other hand, as a coloring treatment that can form a good blackened surface, there is also a review of the general coloring and jealousy ", 'Bahua Department Stem / — ,, color recording electric clock, sulfur recording The problem of electroplating and Mingdian cannot be treated by blackening the surface with the usual copper coin engraving procedure. In particular, it has a surface-treated copper box that enables the rich or precipitating surface to be chemically treated, which cannot solve the problem of falling powder. It is an expensive product because it uses expensive nickel or the like. (Currently, the surface-treated copper foil with tan-colored surface) The manufacturing technology of the surface electric water display panel is mature. In the past, the surface-treated steel box with only a good black daylight surface was accompanied by the advancement of manufacturing technology and official management. It is not necessary to require high-level electromagnetic shielding nets 2213-6894-PF; Ahddub ^ 200533251 / mesh with stable light transmittance is required by the market. The black density of the film is instead the electromagnetic wave shielding of the mesh pattern with a low price and high aperture ratio. That is, the cobalt falling on the market today generates cobalt using an etchant of copper. It is difficult to change the color of tea brown. It ’s a problem for those who try to reduce the amount of dissimilar metals and try 0. Indeed, we must consider that the conditions for low prices are met.

Al ju i has been reviewing the reduction of the surface of copper foil with surface treatment 4,

The initial attachment amount of the dark brown state is reduced.叩 L 、, · The feeling from the mouth to the market is gone. In the past, it has " vv 1BJ reason n points, because the color of its brown brown surface is not uniform, and the lack of white J J is in full production. That is to say, the reason why the brown-smoothed homogenization cannot be achieved in the same plane: the reason for the difference in the cross-sectional shape of the mesh obtained by the engraving. However, the I brown surface is easily susceptible only by gently rubbing its surface. Therefore, it is urgently required to have a treatment layer with a uniform tea brown 'on the market, and it can be easier to etch money, tan, brown, and etch in a hurry. Machined surface treated steel foil. However, with the above-mentioned blackening treatments, there are problems with the stability of color tone. In order to finish the copper ^, it is necessary to strictly manage the manufacturing conditions, process management labor, and expenses in order to close the small batches. [Thus reducing the price of products to their limits. -Generally considered to be related advance technologies: there are technical trends in materials, Hitachi Chemical Technology has the following PDP 1T loc (Technical Report No. 33 (1 999_7) Kaisen 1 1 -1 86785, etc. shows two special Relevant literature on technical standards. : ,,,, the above have the blackened virtual king? But, & a foil, the steel slabs with the treatment surface and the remaining brown treatment surface have problems with the hue that can be confirmed in the state of copper treatment. "Not tested 22l3-6894-PF; Ahddub 7 200533251 Considering the color tone when processed into an electromagnetic wave shielding conductive mesh and incorporated into the front panel of a plasma display. Here, a method for manufacturing the most general front filter (f i 11 e Γ) will be briefly described. When the conductive mesh sheet 15 with a pitch of 200 "and a line width of 20" is manufactured, a pE thin film is prepared as shown in Fig. 14 (a), and an adhesive layer 20 is provided on the surface as shown in Fig. 14 status. Next, as shown in FIG. 14 (c), a metal shielding layer s below ip is formed on the adhesive 2Q by using a rhenium method, an electroless bond method, and the like, and then formed by electrolytic copper plating as shown in FIG. 14 (a). 3 ... the copper layer c below. Then, on the copper layer c, etchmg resists R are formed as shown in FIG. 14 (.), And a conductive mesh pattern is exposed on the resist layer R as shown in FIG. 15 (g). The development shown in the figure and the remaining time become as evil as shown in Figure _5 (h), and the resist layer r is peeled to the state shown in Figure 15 by peeling off. Then, the conductive mesh # 15's is processed by blackening. The surface, as shown in Fig. 15: shows that a blackened layer is formed on the surface of the conductive mesh sheet. At the end of this blackening treatment, the front filter: = 1 transparent substrate 19a is abutted as shown in Fig. 16 Press on the already colored conductive mesh 5, 'as shown in Fig. 16 (a). The color: processed conductive mesh 15' is pressed into the adhesive layer 20 for penetration; Next: Pull and peel the m film as shown in Fig.16. Finally, as shown in -II), the "adhesive layer 20" and the second transparent substrate 19b are attached to the elementary surface filter 11. ^ As can be seen from the above steps, Even if the black is not seen before the transparentization treatment, as long as it can be adhered to the transparent tree 5 ~ and the bright substrate after the transparentization treatment, it is black. You can visually check the conductive mesh 2213-6894-PF; Ahddub 〇200533251 * Only the surface is required. In the future, the digitization of 'wireless TV' is scheduled to be carried out, and the speed of transmission of image signals will also be unavoidable. Considering that The impact on the human body and other electronic devices can be imagined to have stronger legal restrictions on electromagnetic wave shielding. The requirements for front filters that use conductive meshes to provide excellent electromagnetic wave shielding properties will be further increased. An inexpensive and high-quality conductive mesh is urgently needed. [Summary of the Invention] As a result of intensive research, the inventors of the present invention have thought of using a surface-treated copper box with a grayed surface as described below to manufacture electromagnetic wave shielding. Use a conductive mesh. By using this surface-treated copper surface with a graying surface, the color tone of the surface of the conductive mesh for electromagnetic wave shielding before the transparent processing of the manufacturing process of the front filter of the plasma display panel. Gray, the surface of the conductive mesh for electromagnetic wave shielding is blackened after transparent treatment, and can be visually confirmed.

<Surface-treated copper foil with graying surface> The surface-treated copper with graying surface and the anti-recording treatment layer are provided, but in order to ensure that the surface description is relevant to this document, the foil with graying region is related to this invention, and can be classified as not having In the case of anti-rust treatment layer. That is, the anti-rust treatment layer is not necessary, and long-term storage of the copper foil is necessary. Hereinafter, the surface-treated copper foil is clear. The first surface-treated copper foil ... The surface-treated copper system related to this invention "is provided with a graying treatment on the rough surface of an electrolytic copper box, and this graying treatment surface is a weight body provided on one side of a copper foil layer. 20 0mg / m2 ~ 35Gmg / m2 thiopyrite ore layer, and its graying place == 2213-6894-PF; Ahddub 9 200533251 A surface-treated copper foil characterized by a surface height of 200 nm or less (hereinafter referred to as "the first surface Handling Copper Foil "). FIG. 1 schematically shows the cross-sectional layer structure of this surface-treated copper foil i a. Here, FIG. 1 schematically illustrates that the sulfuric acid starting plating layer 4 is formed on the rough surface of the electrolytic copper foil 7 and the opposite surface (equivalent to the glossy surface in the case of the electrolytic copper foil).

The surface-treated copper foil 1a in a state where the fine copper particles 3 are roughened is taken as an example. However, the opposite side of the copper province used at this time may be used with or without roughening. Here, FIG. 2 schematically shows the surface-treated copper foil lb when the roughening process is omitted on the opposite side. The roughening treatment layer 2 composed of the fine copper particles 3 is formed for the purpose of improving adhesion to a substrate or the like, and may be formed if necessary. The method for forming the roughening treatment layer 2 may be a method of forming fine copper particles by adhesion as described above, and a method of attaching fine copper oxide, etc., and is not particularly limited to the roughening treatment method.

Next, a sulfuric acid recording plating layer 4 is provided on the roughened surface of the copper foil layer 7 which is 々nnrT ^ W 疋 uneven. Here, the rough surface has another rough ancestral roughness. The thickness of the electrolytic copper foil, which is equivalent to a nominal thickness of 3 5 // m or less, is the most suitable. The radius of curvature of the part is 2 # ττο η. The average thickness (R) determined by JIS B 060 1 at the time of cypress needle-type coarseness meter measurement, y = 1 〇 / zm or less, 1 0:00 point sentence thickness (Rz) Those who are in the range below 4. 0 // m ”are those who have entered seven a ’s λα *, and those who are better than others. A thicker job than this, a thick job, a warrior ’s son-in-law, and etching The accuracy of etching processed into the shape of the mesh is inferior to that of the conductive guide for electromagnetic wave shielding, which is used for the quality of the guillotine I, and the quality of the conductive mesh for the shielding of the electromagnetic wave is worse. ) Is less than 0.5 / Zm, and less than 10 points. The gray color of the surface-treated steel box, ^) is 2.8㈣ high, on the front of the panel of the electrically destroyed display: color: female qualitative can make a leap forward 2213 &gt; 6894-PF / Ahddub Λ Λ 200533251 After the surface panel manufacturing process is made transparent, there are also few differences in the color tone of black. The so-called lead sulfate layer 4 here means The layer formed by the electro-mine method using a starting solution of sulfuric acid was used. Then, the state of the sulfuric acid layer 4 in the surface-treated copper box can be visually confirmed to be gray. However, the manufacturing steps of the front panel of the above-mentioned electropolymer display panel are performed The transparent treatment becomes a state in which a resin film or an adhesive resin is covered on the graying treatment surface, and then it becomes a visual disc that is considered black. Such a tone change is like a thick-toned suit wet with water, The surface of the clothes, which should have been rough and matte, was formed with a water curtain, which prevents the exposure to light because it forms a smooth surface.

The random reflection of the light can be regarded as the principle of the same color tone. This cobalt sulfate plating layer 4 adopts a manufacturing method described later as a weight thickness of mmg / m2 to 350,000 mg / m2 'to obtain excellent solubility in a copper etchant and to form a gray surface. In the past, the cobalt layer of the copper flute provided with a black-type electric clock coating on the plutonium layer had a weight and thickness of 10%. Before and after 〇_2, it was considered very thick, but the quality of the solubility of the bell layer was different. As a result, the dissolution rate of the copper engraving solution becomes slow due to the thickness, and the element itself is accumulated in the copper engraving solution at a high concentration, which becomes an important reason for the decrease in the power value of the engraving solution. The conversion weight of this invention is the value converted to the weight of the inscription. The weight change is to dissolve the surface-treated copper pig in an acid solution, and determine the equivalent weight per square meter of copper foil per unit area by electro-luminescence spectroscopy. In other words, the change is surface treatment. In addition, I also learned whether the ore layer is easy to dissolve in the copper coin engraving solution, which is greatly affected by the condition of the electric clock when the coin is deposited. a The cobalt plating film obtained in the method for producing a surface-treated copper drop has the best etching characteristics. 2213-6894-PF / Ahddub 11 200533251 Related to the second feature of the surface-treated copper foil of the present invention, a The surface shape of the graying surface is not extremely rough, and the graying treatment: The cross-section height is Below 200 nm is an important feature. That is, it can be referred to as an extremely smooth grayed surface. In #, in order to avoid misunderstanding, it is indicated here: ¾ Of course there are differences in the scope of common manufacturing steps, and it is not necessary that the cross-sectional height of all positions is below 20 °, and it will also reflect the manufacturing There may be cases where the height of the cross-section is different to the extent of the difference in the steps. In order to correlate the cross-sectional height of the sulfide bell layer 4 with the surface treatment m of the present invention, the FIB observation image of the cross-section viewed at ㈣m is shown in FIG. 3. Here, the figure shows a case where a gray-treated surface is formed on the glossy surface of the electrolytic copper box. In addition, the observation image is 60% sandwiched between the observed surface. The direction of the angle From this figure 3, it can be seen that there is unevenness in the cross-section of the grayed-out surface. It is obvious that the unevenness of the unevenness and surface roughness are monitored. However, from the scale of Fig. 3, the roughness of the grade of roughness can be accurately measured by the surface roughness meter. ', &Quot; The mountain and valley in the field of view of the FIB observation image are clearly stated ^ Benfa &lt; taken · large difference as "Li 丨 1 Ayou", as the corresponding to the surface roughness measured Rmax. The place where "d" is shown in Fig. 3 is about 80 nm in the cross section of Fig. 3. Moreover, in Figure 3, the extremely uniform thickness along the shape of the surface of the concrete is completely in close contact with the secondary system, and no sulphuric acid coating has been found, and no premises have been predicted to fall. In this regard, the black, +, 丄 1, U, ..., Bahua processed surfaces formed on the surface of the previous copper foil, and the fibrous observations made from the cross section of the same copper plate will become the knots 22l3 shown in Figs. -6894-PF; Ahddub 12 200533251. In other words, it can be seen that the shape of the structure is blackened to become a protruding shape from the bottom of the copper box, and the shape grows into a tree shape. That is, it was determined that about A 97ησ, the spoon was 480 nm, and the cutout in Fig. 5 and * 0 was 270 nm. It can be understood that the black surface with a tree-like shape prepared by the mouth was rough. Moreover, this can be called a surface that is vulnerable to damage. Of course, the dendritic part is easily broken, and it will fall, and μ &amp; and if the broken piece falls off, it is considered to be caused by the blackened surface. 5 reasons for tolerant stains. The heart-boiled jacket is related to the surface-treated copper box of the present invention as described above. Observing the image on the surface can understand that it has a very sharp ^ 'The L value of the Lab color system of this gray-processed surface is 43 Hereinafter, it is described as M or less, and ° is the lower limit. Wood 衧 is not limited, empirically, 38 ′ is related to the graying treatment of the surface-treated copper box of the invention. Product: 2 gloss ′ is the degree of its gloss, and the use of gloss is not too bad. The glossiness of the grayed-out surface related to the present invention. The result of forming the grayed-out surface on the rough surface of the electrolytic copper box is

Ms (6 (T)] is preferably 10 or less. If the glossiness is ι0 or more, metallic gloss becomes noticeable. Also, the lower limit value of glossiness is not determined here, but it is derived from experience. It is said that the lower limit is about 0.5. The more preferable range is 0.5 to 30. The gray hue stability of the occasions with gloss in this range is best to dry the graying treatment of the surface-treated copper foil described above. Called co-surface close contact: When a transparent resin film is placed, it can be visually recognized as black. When the grayed surface is directly observed at this time, the black concentration is 0 · 7 ~ 1 · 2 (Measurement conditions ·

StatusT 'Sampling aperture 1. 5 X 2mm, no polarizing tear mirror), when the surface of this graying surface is closely arranged with a transparent resin film, the black concentration is 13 2213-6894-PF; Ahddub 200533251 is 4 or more ( The upper limit of the experience value is dry; 4 · King of Spears). In the past, the black concentration of the π-electrically treated surface used to shield the electromagnetic waves of the electric water panel was directly observed = the blackening of the copper surface was greater than 1.0. The concentration is about 1.30 ~ le67). When the Qiming resin coating is taken from this blackened part, the black concentration is! The surface tightly arranged above 5 is transparent. ^ In ancient times (the inventor of this invention and other test equipment related to the grayed-out surface of this invention. Therefore, a transparent tree is used to tightly arrange this surface: cover: hour "Table: Meili Steel, considering that the black concentration when each H Hoga film is applied is about 1.4 or more ..." Say 疋 becomes a sufficient black concentration. In addition, this series is based on Jis B 9620, ns B 9622. The test condition of the ybZZ technique is to use the above-mentioned second surface-treated copper box. This surface-treated copper box is formed on the surface of the above-mentioned surface-treated copper drop to ensure long-term storage. Record prevention layer 2 Figure 6 is a schematic illustration of the cross-sectional structure of a surface-treated copper foil lc provided with a rust-proof treatment layer 5 on both sides. Next, Figure 7 shows the surface-treated copper foil 1 when roughening is omitted on one side. d. The limitation of copper foil is only for the purpose of rust prevention. 'Imidazole, Cbenzotriazoi, etc. can be widely used for organic rust prevention, or zinc alloys such as zinc or brass are generally used. Inorganic antirust and so on. In addition, the rust-preventive treatment layer in the case where a cobalt sulfate layer is formed on one side should be provided at least on the opposite side of the surface-treated copper box related to the invention provided with a cobalt sulfate coating, but on both sides. However, If the rust-resistant treatment layer 5 is provided on both sides, these rust-resistant treatment layers' function as a roughening treatment layer 2 to prevent the fine copper particles from falling off and as a protective layer of the sulfuric acid recording layer 4, and also to maintain the long-term maintenance 2213-6894-PF; Ahddub 14 200533251 = Used in combination with sulfuric acid starting ore layer 4 and can function as a dissolving protective layer when Yingu = 4. That is, in the case where the ^: layer 4 exists alone, if the alloy layer or the alloy layer is provided, the dissolution of the cobalt sulfate plating layer 4 proceeds more rapidly.

Further, Figs. 8 and 9 schematically show the cross-sectional layer structure of a surface-treated copper wire ^ provided with a recording prevention treatment layer 5 "chromate treatment layer 6 on both sides. The comparison is made by comparing Figs. 6 and 8 respectively. Figures 7 and 9 show that the difference from the surface-treated copper box provided with the anti-recording treatment layer 5 is only that the salt treatment layer 6 is provided, and the other structures are the same. This chromate treatment layer 6, After forming the rust-resistant treatment layer 5 composed of zinc-nickel alloy or zinc-cobalt alloy =, it is formed on one or both sides: Next, due to the presence of this chromate treatment layer 6, the surface treatment of the copper foil The oxidation resistance is significantly improved to effectively prevent decorative corrosion such as oxidative discoloration. &Lt; Manufacturing method of surface-treated copper thread with graying surface &gt; (1st method of manufacturing surface-treated copper box) The manufacturing method of the first surface-treated copper foil is preferably a manufacturing method using the steps described below. This manufacturing method is premised on the use of a stirred bath. The manufacturing method of the surface-treated copper foil related to this invention The used copper and moor's are not official as above Whether or not roughening is performed on the opposite side of the cobalt sulfate plating layer. It is specifically described here, but the conditions for the roughening treatment are not particularly limited. For example, a field where extremely fine copper particles are formed a &amp; &Amp; Use a copper-containing copper electrolyte. For example, use copper sulfate series 2213-6894-PF; Ahddub 15 200533251 • Solution, where the copper concentration is 5 to 10 g / l, the sulfuric acid concentration is 100 to I20 g / 1, chlorine : Chendu 20 ~ 30ppm, 9-phenyl £ 1 Ah. 9-phenylacridine 50 ~ 300mg / l, liquid temperature 30 ~ 40 ° C, current density 5 ~ 20A / dm2, etc. in a) In the step, on the rough surface of the above copper foil, cobalt sulfate electroplating containing 10 g / l to 40 g / l of cobalt sulfate (7 water and substance), a pH value of 4.0 or higher, and a liquid temperature of 30 ° C or lower is used. The liquid is used as a stirring bath, and electrolysis is performed at a current density of 4 A / dm2 or less to form a gray cobalt sulfate coating. That is, the fundamental difference between this and the 丨 surface treatment copper foil manufacturing method A is that the cobalt sulfate electric spring is used. During plating, the aforementioned cobalt sulfate plating solution is continuously stirred to perform electrolysis. The concentration of cobalt sulfate includes cobalt sulfate. The lower the degree, the better the tendency of graying. However, when the cobalt sulfate (7 hydrates) in the cobalt sulfate plating solution becomes less than 10 g / l, the electrodeposition speed of the cobalt sulfate coating layer formed by the stirring bath is used. Slower, and the tendency of the thickness of the nickel sulfate layer to become non-uniform becomes stronger, resulting in a lack of industrial productivity. For this reason, when the cobalt sulfate (7 water) exceeds 40 g / l, the formed cobalt sulfate coating is not easy. A dense unevenness is formed, and as a result, it is not in a good gray state.

4. 0 It is better to adjust 5 to 5 _ 5 gray or hydroxide ore layer to maintain such cobalt or ^ V ^ team failure value is in the above range. Next, a range of 4 is more preferable. Within this range, the productivity is good, and a good cobalt plating layer can be obtained. To adjust this pH value, the addition of other electrolytic values such as sodium hydroxide or potassium chloride is not welcome. Because ^ gray is easy to add metallic color. 'Stomach H name' is the solution pH value, and the concentration of the metal in the solution can be determined. As a result, it can be technicalized. The range of 4 G or more = generally stabilizes the concentration of cobalt ions in the solution. It is the use of dissolving electrodes to supplement the supply of cobalt attached to the plating in a dissolving manner. =, 2213-6894-PF; Ahddub 16 200533251 A method such as using cobalt hydroxide to stabilize the ion concentration is added. Next, the lower the liquid temperature at this time, the more the good grayed-out surface tends to be obtained. Set the liquid temperature to 3Qt: In the following case, with the above-mentioned i-th surface. Process copper manufacturing method A, it is possible to obtain a better grayed surface than the blackened surface of the surface of the copper pig that has not been roughened. . In this case, it is preferable that the flow rate of the solution after the stirring reaches a range of 20 cm / s to 2 cm / s. When the flow rate of the solution is less than 20cni / s, the composition of the above solution / combined liquid will slow down the supply of the coated surface ions of the cobalt, which will take longer to write and the resulting graying. The hue of the treated surface is also prone to differences. On the other hand, where the flow rate of the solution exceeds, the ion supply speed caused by the stirring is too large, so that the graying treatment surface is close to blackening, and the metallic luster becomes strong, which becomes a graying treatment surface which is not the object of the invention. The current density at the time of electrolysis was 4 A / dm2 or less. Within this range, even if the surface of the copper foil is not roughened, it is possible to form a cobalt sulfate coating layer having excellent fine unevenness with good adhesion to organic materials. In general, to obtain a black-based plated surface with unevenness, a method of passing an electrolytic current in an excessively-sintered area is adopted. However, the smaller the electrolytic density used for the electrolysis here, the more stable and good graying tends to be. In other words, it is sufficient to use the minimum current density within the possible limit, but considering the industrial productivity, it can be judged that the current density should be 0.5A / dm2 as the lower limit. On the other hand, if the current density exceeds 4α / _2, the color tone approaching the blackening treatment tends to be obtained, and the significance of adopting this manufacturing method is lost. In addition, the grayed-out surface formed in the above-mentioned range of electrolytic density did not have excessive powder falling. 2213-6894-PF; Ahddub 17 200533251 In step b), the copper foil that has undergone the above steps is washed with water and dried to obtain the sulfuric acid inscription layer # grayed out. The surface treated copper is washed and dried here. It is not specific and can be considered. ^ (Manufacturing method of the second surface-treated copper foil) In the case where the second surface-treated copper is dropped, it is different from the above-mentioned method for manufacturing the surface-treated copper poise, and the surface treatment is performed using a cobalt sulfate plating layer as a graying treatment surface The copper falls, and thereafter the formation of a recording prevention layer is performed. That is, the manufacturing process is "(a) forming a gray rhenium sulfate layer on the glossy surface of ㈣. ⑴ on both sides of the copper foil forming the gray cobalt sulfate plating layer or a single anti-recording treatment layer. ⑷ ' Dry. "Process. That is to say, it is only necessary to add a step of preventing the recording from the first surface treatment method. Therefore, only the steps for forming the recording prevention processing layer will be described here. After the formation of the gray hafnium sulfate layer on both sides, antirust treatment is performed. Regarding the use of the 防 treatment layer in the conventionally known use of organic rusts such as imidazole, benzazotriazole, or the like: Ordinary: the use of zinc alloys such as zinc or brass The field of inorganic rust prevention does not need to be described in detail, but it can be performed in accordance with a conventional method, and detailed description is omitted here. The following is a description of the occasions where a zinc-nickel alloy plating solution or zinc is used. First, the description about zinc = ^ ♦ The zinc-nickel alloy plating solution used is not particularly limited. Nickel sulfate can be used in the column, where the nickel concentration and the temperature are 20 to 50 and the calcium pyrophosphate scale is 50 to 5000 g /. 1. Liquid, pH value 8 ~ 11, current density 0.3 ~ 10A / dm2 strip 2213-6894-PP / Ahddub ^ 200533251 pieces, etc. Next, it is explained that the zinc-cobalt alloy lightning solution is not particularly limited. The zinc-cobalt alloy plating used here occupies 1 ~ 2.5g / 1, the use of which can be used to drill the concentration of acid ... Second: the conditions of heart U ~ UUAW and so on. 0C, acid test value 8 ~ U, combined with current dense salt treatment: zinc-cobalt alloy plating and chromic acid energy described later. Rust-treated layer shows particularly excellent corrosion resistance

After the second surface-treated copper foil alloy layer or zinc-cobalt alloy layer, etc., ":, the surface of copper is formed of nickel, and it has excellent money resistance. That is," ", which forms chromate, can be further modified. The chromate treatment step is sufficient. In the case of m-^, in this chromium phosphonium salt treatment step, whether the method of contacting the complex salt> valley liquid with the copper foil surface, listening, six + public cymbals, or various methods of chromic acid Both. In addition, the electrolytic chromate treatment, etc. of the film is used in the range used in the conventional method. After receiving / combining the liquid, the mourner was washed with water and selected strips to obtain a surface-treated copper foil with a gray surface. ', <Electromagnetic wave shielding conductive mesh sheet> The above-mentioned related to the present invention is provided with a "colored core surface surface treated copper collar, without powder falling from the grayized surface, and the towel has a good gray color." Its graying treatment Layers can be removed by the copper foil program through f. Therefore, it is possible to easily add two to an arbitrary shape using a procedure for manufacturing a printed circuit board. In view of these circumstances, it can be said that it is most suitable for the use of the electromagnetic wave shielding conductive mesh in the front panel of the plasma display panel. 7 Advantages of the invention 22l3-6894-PF; Ahddub 19 200533251 The surface-treated copper provided with the grayed-out surface of the present invention, even if the cobalt sulfate plating layer is very thin, the electromagnetic wave shielding conductive screen of the front panel of the plasma-resistant display panel is exhibited Good gray for tablet use. Next, since the cobalt content is small, the etching characteristics are good, and the strength of the conventional copper chloride etching solution of ferric chloride and sulfuric acid-hydrogen peroxide is not reduced, and the life of the solution can be prolonged. In addition, the method for producing a surface-treated copper foil according to the present invention can produce the surface-treated copper foil with high productivity, and the cobalt sulfate plating layer formed by using the above-mentioned production conditions has the best efficiency in dissolving in a copper etchant. [Embodiment] The following shows the results of producing a surface-treated copper foil having the above-mentioned graying-treated surface, and producing an electromagnetic wave shielding conductive mesh using a copper etchant.苐 1 Example In this example, the first surface-treated copper 羯 1a shown in Fig. 1 was manufactured, and the shape of an electromagnetic wave-shielding conductive mesh was tested by an etching method to confirm the engraving performance. In this embodiment, a copper foil having a nominal thickness of 15 / m obtained by electrolytic copper sulfate solution is used. Next, the copper foil was immersed in this solution for 30 seconds using a dilute sulfuric acid solution having a sulfuric acid concentration of 150 g / i and a liquid temperature of 30 C to clean the surface. Then, the glossy surface of the electrolytic copper foil with a nominal thickness of 15 m was subjected to a roughening treatment. In this roughening process, the fine copper particles 3 are adhered and formed on one side of the copper foil 7, and a copper sulfate-based solution is used, in which the copper concentration is 10, the sulfuric acid concentration is 100 g / l, the chlorine concentration is 20 to 30 ppm, and the chlorine concentration 25ppm, g-phenylacridine (9-phenylacridine) 140mg / l, liquid temperature 38 ° C 'current density 2213-6894-PF; Ahddub 20 200533251 1 5 A / drn1, electrolysis time 2 seconds Electrolytic conditions. Figure 丨 〇 shows the roughened copper foil surface. As step (a), a cobalt sulfate plating layer is formed on the rough surface of the electrolytic copper foil. The formation of the cobalt sulfate plating layer is based on the use of cobalt sulfate electroplating solution with cobalt sulfate (7 water and substance) of 20 g / pH value adjusted to 5.5 and a liquid temperature of 27 ° C as a stirring bath. Electrolysis was performed at a current density of / dm1 for 12 seconds to form a gray cobalt sulfate plating layer (equivalent thickness was 270 mg / m1). At this time, the cobalt ion concentration in the solution was not specifically adjusted. Because of the short-term electrolysis, it is not considered necessary to adjust the metal ion concentration. Figures U and 12 show a scanning electron microscope image of the formed cobalt sulfate coating. Figure 11 shows a scanning electron microscope image viewed at a low magnification. Figure 12 shows a scanning electron microscope image viewed at a double magnification. From Figure 12 it can be seen that the rough shape of the bottom electrolytic copper foil can be clearly grasped, and that the graying treatment layer itself is extremely thin. As step (b), shower clean with sufficient pure water, and heat the ambient temperature to 15 ° (rc) to stay in the drying furnace for 4 seconds, and go to gray with a very good hue. The surface treatment of the treated surface ° &amp; Between the above steps, a 15-second pure water washing step is provided in principle to prevent the solution from being brought into the pre-treatment step., Water properties of surface-treated copper foil / / The cross-section of the gray-colored copper foil obtained after the above steps was treated with FIB # 6 ®, and the gray-colored texture obtained the cross-section height of the flame-colored processed surface as shown in FIG. 3. Τ is the τ of the Lab color season of 80n, including 4 people. In addition, the grayness [GS (60.)] Of gray is 1.5. There is no color spot on # ^, and the surface is adhered to the surface.脒 冉 Ran torn the tape, mesh, 14 kf 丨 Wang I belt, 胗 f / test also confirmed that there is no falling powder. Furthermore, the surface treatment of the obtained 矣 J was grayed out of the copper foil. Surface, 21 1 2l3 ~ 6894-pF is added; Ahddub 200533251 is used: the electromagnetic wave shielding mesh for the poly display, Transparent, ::: Judgment of whether blackening is seen. The black concentration of the physical surface before forming the transparent resin film is 0.9, and coating with this graying treatment surface = as a transparent resin film, drying to harden, Through the hardened Ermei, the so-called substitute 彳 ,, Ό, which observed the change in hue of the grayed surface, the blacked surface with a black density of 1.5 was observed. <Electromagnetic wave shielding mesh for plasma display Manufacture> The double-sided adhesion of the surface-treated copper foil obtained as described above can be used as a corrosion inhibitor. The "# 者 '" only overlaps the dry film on the gray-treated surface side and overlaps. 1. Test mask for electromagnetic wave shielding of conductive mesh 1. Electricity &quot; test mask film for green wither sheet; 'mesh spacing between 200 mesh lines, S 10㈣, mesh deflection angle 45., UV around Exposure of the conductive mesh with the mesh electrode part—M is not at this time, and at the same time, the entire corrosion resist layer is covered, and II is removed by ultraviolet exposure and development. After that, the test and liquid-containing core become Cannot be developed by the stool test solution after the stool, shape . I then patterned by engraving, ferric chloride, money coins engraved engraved liquid solution, the treatment by the gray side into the Ding copper etching, thereafter, the resist by peeling sound, - Xi; m electromagnetic wave shielding gas

Hf mesh. As a result, no money remains, and the carving is performed. Fig. 13 shows the etching state of a wide-etched circuit for evaluating etchability. From this, J #, pattern (1 3 # m Liang Fanle U picture can be seen, without leaving a 'can get a beautiful circuit with excellent etching parameters. Brother 2 embodiment This embodiment, as shown in Figure 6, manufacturing equipment The second surface-treated copper box 1 of the alloy anti-rust treatment layer «Under the M-M decorative test method to manufacture the electromagnetic wave shielding conductive mesh shape to confirm the etchability At Moon. That is, until by

Until the sulfuric acid coating is formed into a graying treatment layer, I will only explain the precautionary conditions. In addition, the ash is common to the first embodiment, and the conversion of the colored cobalt sulfate plating layer is 2213-6894-PF; Ahddub 22 200533251 * The thickness is the same as that of the first embodiment, which is 270 mg / m2. Here, on the two sides of the first embodiment, the gray copper-plated copper sulfate plated with copper cobalt sulfate is finished on both sides, and then the nickel-nickel alloy is electro-bonded to form a zinc alloy layer. For the zinc-nickel alloy layer, the concentration of sulfuric acid was 2.0 g / l, the zinc concentration of zinc pyrophosphate was 0.5 g / i, and the pyrophosphate temperature was 225 g / liter. 〇, acid test value 10, the current density of 5A / dm2 strip bow for 5 seconds, uniform and smooth electrolysis on both sides. Next, 'show in the same way as in the first example, wash it with a shower of pure water. • The heater is left in a drying furnace at an ambient temperature of 15 t for 4 seconds, and Z is removed to obtain a grayed surface with a very good hue. Surface: Copper box 1c. In addition, between the above steps, a 15-second pure water washing step is provided in principle to prevent the solution in the pre-treatment step from being brought in. 〈Physical properties of surface-treated copper box〉 # Observe the d-side of the surface-treated copper smelter with the gray-treated surface obtained through the above steps with a FIB device. The same section as shown in Figure 3 was obtained. Bu # w &amp; Λ treatment surface has a cross-sectional height of 75 nm, the L value of the Lab color system of the graying treatment is 39, and the glossiness [Gs (60. is 2.5.) No stains were found on the surface, and adhesive tape was affixed to the surface, and then the tape was tested to confirm that there was no powder falling. The grayed surface of the surface-treated copper foil was processed into a plasma display. The electromagnetic wave was used to shield the mesh sheet, and it was judged whether the blackening can be seen before the transparent treatment was applied. The black concentration of the flame-treated surface before the transparent resin coating was formed was G · 9, which was the same as that of the first working example. In place of the flat surface ^ K's gray processing surface, the dark black & black of the black 6. <Manufacture of electromagnetic wave shielding mesh for plasma display> 2213-6894-PF; Ahddub „200533251 and the first In the same way as in the example, the obtained surface-treated copper foil was used to test electromagnetic The wave shields the conductive mesh. As a result, even if the anti-rust treatment layer is present, the etching operation is not hindered, and there is no etching residue, and very good etching is performed. This Example 3 is manufactured as shown in FIG. The rust-treated layer includes a second surface-treated copper foil le made of a zinc-nickel alloy layer and a chromate-treated layer. The shape of the electromagnetic wave-shielding conductive mesh was confirmed by a money-cut method to confirm its etching properties. Until the graying layer is formed in the first bell layer, it is the same as in the first embodiment, so only the rust prevention processing conditions will be described. The converted thickness of the gray sulfuric acid first plating layer is the same as that in the i-th example, which is 27 mg / m2. The formation of the treatment layer is the same as in the second embodiment. A zinc-nickel alloy plating solution is used to form a zinc-nickel alloy layer on both sides, followed by chromate treatment on both sides. Here, electrolytic chromate treatment is used. Electrolysis was performed for 5 seconds under the conditions of chromic acid 5.0 · g / l, liquid temperature 35 ° C, pH value U · 5, and current density 8A / dm2. Next, after the formation of the chromate layer was completed, the chromate layer was completely purified. Wash with water shower, with electric heater in the environment A 15-generation drying oven is left for 4 seconds to remove the moisture, so as to obtain a surface-treated copper lc with a grayed surface with a very good color tone. In addition, a Η second The pure water washing step prevents μ &amp; &gt; light from the township and prevents the solution from being brought in. 〈Physical properties of surface treated copper foil〉 It is equipped with the fine-colored a 『07 times coloring surface obtained through the above steps. The section of the surface-treated copper berth was observed with the FIB nightmare_ 衮, 丄 田 Η device, and the same section as that shown in Fig. 3 was obtained. The graying is imaginary ^ ', phase jkjs ^ ^, ^ face degree It is 7511111. The gray color of the Lab color system is τ 佶 helm / Λ ο ^ ^ L value is 40, gloss [Gs (60. )] Is 2 ^. In addition, there is no generality in the grayed-out surface — "" is 2.3. Unstained, apply adhesive tape 2213-6894-PF; Ahddub on this surface. 200533251 • The tape test to tear it apart also confirmed that there was no falling powder. Furthermore, the gray-treated surface of the obtained surface-treated copper box was processed into an electromagnetic wave shielding net for an electro-condensation display, and it was judged whether or not blackening was seen when the transparent treatment was applied. The black density of the gray-treated surface before the transparent resin coating was formed was 0.9. As a result of evaluation by the same substitution method as in Example 1, the gray-treated surface was observed to have a black density of i · 5. <Production of electromagnetic wave shielding mesh for plasma display> Φ As in the first embodiment, an electromagnetic wave shielding conductive mesh was trial-produced using the obtained surface-treated copper foil. As a result, even if the anti-rust treatment layer is present, the etching operation is not hindered, no etching remains, and very good etching is performed. Fourth Example In this example, as shown in FIG. 6, a second surface-treated copper foil lc having a zinc-cobalt alloy layer as a rust-preventive treatment layer was manufactured, and an electromagnetic wave shielding conductive mesh shape was manufactured by an etching method test to confirm the etching. performance. That is, until the graying treatment layer is formed by the cobalt sulfate plating layer, it is common to the first embodiment, and therefore only the rust prevention treatment conditions will be described. The converted thickness of the gray cobalt sulfate coating was 270 mg / m2 in the same manner as in the first embodiment. # Here, on the both sides of the copper foil after the gray cobalt sulfate layer is formed on the glossy side of the first embodiment, a zinc alloy plating solution is used for electroplating to form a cobalt alloy layer on both sides. Zinc-cobalt alloy layer, using cobalt sulfate with cobalt concentration of 2.0 g / 1, zinc pyrophosphate with zinc concentration of 0.5 g / 1, calcium pyrophosphate 250 g / l, liquid temperature of 35 ° C, pH value of 10, Electrolysis was performed for 5 seconds under the condition of a current density of 5 A / dm2, and electrolysis was performed uniformly and smoothly on both sides. Next, similar to the first embodiment, the shower was washed with sufficient pure water, and the electric heater was left in a drying furnace at an ambient temperature of 15 ° C for 4 seconds to remove water 2213-6894-PF; Ahddub 200533251 points to obtain With non- 赍 &amp; copper foil lc. In addition, the step of washing the surface of the gray-treated surface with the color tone of the hue is washed with water to prevent the front: ::: between, in principle, a solution of "physical properties of pure <surface treatment copper falling" is brought in The cross section of the copper box obtained through the above steps was treated with the FIB device and the surface treated with Λ-coloring treatment surface. As a result of inspection, the same section with 3 HI%-1 was obtained. The degree of color of the Lab color system that is not treated is 8—'this graying ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, ', and the gloss [Gs (60.)] Is 25. There are no stains on the graying surface. Adhesive tape was affixed to the surface, and then the tape was tested to confirm that there was no powder falling off. # ❹Tape and then the gray surface of the surface-treated patina oil was added to the electromagnetic wave for the electro-hydraulic display device. The mesh was masked to determine whether blackening was visible when transparent geography was applied. The black concentration of the grayed-out surface before forming the transparent resin film was 0.93, and was evaluated using the same substitution method as in the i-th embodiment. As a result, the blackened black was observed on the grayed-up surface. Manufacture of electromagnetic wave shielding mesh for electric display> As in the first embodiment, an electromagnetic wave shielding conductive mesh was trial-tested using the obtained surface-treated copper drop. As a result, even if a rust-preventive treatment layer is present, money is engraved. No hindrance, no etching remains, and a very good rest. 5th embodiment This embodiment 'as shown in FIG. 8' manufactures the 2nd layer which provides a zinc-cobalt alloy layer and a chromate treatment layer as a money-proof treatment layer The surface-treated copper foil 1e was produced by testing the shape of an electromagnetic wave-shielding conductive mesh using a money engraving method, and its etching performance was confirmed. That is, until a graying treatment layer was formed by a cobalt sulfate plating layer, it was common to the first embodiment, and therefore only Describe the anti-rust treatment conditions. Also, the thickness of the varnish-cobalt coating of gray 2213 -6894-PF; Ahddub 26 200533251 is the same as in the first embodiment. The formation of the anti-recording treatment layer is the same as in the fourth embodiment. Zinc-starting alloy electro-hydraulic fluid. After the zinc-cobalt alloy layer was formed on both sides, the chromic acid was treated on both sides with electrolytic chromate treatment. The electrolytic conditions were chromic acid 5.0 · g / 1. Liquid 'serving 35 C, Electrolyte for 5 seconds under the conditions of alkali number 11.5 and current density 8A / dm2. + Then, after the formation of the bundle of chromate layer, wash it with a shower of pure water, and use an electric heater at an ambient temperature of 150. Hold in a drying oven at ° C for 4 seconds, remove the water jet, and wait for the surface with a grayed surface with a very good color tone.

Surface treatment copper foil〗 P. V, L In addition, between the above steps, in principle, a pure water washing step is provided for a second, and the L 1 Α β p _ Youai step prevents the solution of the limulus treatment step from being brought in. <Physical properties of the surface-treated copper drop> The cross-section of the gray-treated surface-treated copper box provided with the above steps was observed with a FIB apparatus, and the same cross-section as shown in FIG. 3 was obtained. The cross-section of the gray-treated surface The height is-, the l value of the Lab color system of the graying process is 41, and the gloss [Gs (60.)] Is 24.

No gray spots were observed on the grayed surface, and adhesive tape was affixed to the surface, and then the tape was peeled off. Furthermore, the gray-treated surface of the obtained surface-treated copper foil was processed into an electromagnetic wave shielding net for a plasma display, and it was judged whether or not blackening was seen when the transparent treatment was performed. The black concentration of the gray-treated surface before being coated with the transparent resin was 0.9%. As a result of the evaluation by the same substitution method as in the i-th example, the gray-treated surface was observed to have a black density of black dense I 6 0 < Manufacture of electromagnetic wave shielding mesh for plasma display device> Same as in the first embodiment, using the obtained surface-treated steel box to test electricity 2213-6894-PF; Ahddub 27 200533251. As a result, even if a rust-preventive treatment layer is present, no etching remains, and very good etching is performed. The roughening treatment is performed, and the electrolysis is as follows: The rough surface of the WM rough surface t electrolytic copper treatment is grayed out. 1 The second surface treatment copper box lb shown in FIG. 2 and the first embodiment Perform a π-like evaluation. That is, since the explanation of the steps of the helmet __ unsubscribe is the same as that of the i-th embodiment, the description is omitted here. In addition, the gray sulfate key bond layer converts thick sound:

The morphology of the 268 mg / m, cobalt sulfate layer formed was remarkably observed. The physical properties of the surface-treated copper foil in the U figure: Prepare the gray-treated surface of the gray-treated surface obtained by the above steps. The cross-section of the surface is treated with FIB, and the results are as follows: In the mouth 1J surface shown in FIG. 3, the gray and white Lab surface color season of this grayed surface is "value: 78nm in breadth, grayed", the value is 42, and the gloss [Gs (60.)] Is 2 · 5β

In addition, the grayed surface is removed. # D Γ Put an adhesive tape on the surface.

The magnetic wave shields the conductive mesh. The operation is not hindered. Sixth Embodiment In this embodiment, a knee strap test that did not tear the same as in the sixth embodiment also confirmed that there was no falling powder. Work: Ϊ: Show the grayed surface of the surface-treated steel pig, when it is added; :: Use electromagnetic waves to shield the mesh, and judge whether to apply transparency .., coloration. The black concentration of the grayed surface before forming the transparent resin coating is ^ Lu Bei ♦ It seems that t is used as a transparent tree if the grayed surface is used for private use. ^ If 4 Μ ^ The hardened, through the hardened jade clothes milk tree month layer observation gray multi-service method "Shiguo, ^ Λ tone changes the so-called replacement of the colorization treatment surface observation to obtain a black density of 1.6 color. "Electricity: Manufacturing of electromagnetic wave shielding mesh for display and display" "", same as in the first embodiment. "Using the obtained surface-treated copper pig, try to make electricity 2213 -6894-PF / Ahddub 2 8 200533251 v Magnetic wave shielding conductivity Mesh. As a result, the etching operation was not hindered, and there was no etching residue. Very good etching was performed. Example 7 In this example, unlike the first example, the glossy surface of the electrolytic copper foil was not roughened. As in the first embodiment, a graying treatment layer is formed on the rough side of the electrolytic copper box by a cobalt sulfate plating layer, and the first surface-treated copper foil 1 b shown in FIG. 2 is manufactured, and the electromagnetic wave shielding is manufactured by a money-cut method. The shape of the conductive mesh was confirmed for its etching performance. Φ In this embodiment, a copper foil having a nominal thickness of 15 / zm obtained by electrolytic copper sulfate solution was used. Next, a sulfuric acid concentration of 15 g / 1 and a liquid temperature of 30 C were used. The dilute sulfuric acid solution was used to immerse the copper foil in this solution for 30 seconds to clean the surface. Then, as step (a), a cobalt sulfate coating was formed on the rough surface of the electrolytic copper foil. The formation of the cobalt sulfate coating was Use of sulfuric acid (7 water and substance) was adjusted to 20 g / ls, the test value was 5.5, and the liquid temperature was 27 ° C. The sulfuric acid residual electric clock liquid was used as a stirring bath, and electrolysis was performed at a current density of 2 A / dm2 for 6 seconds. Formation of gray cobalt sulfate coating (converted thickness is 275mg / m2). At this time, the adjustment of cobalt ions / degrees in the solution is not specifically performed. Because of the short-term electrolysis, the mouth = not to adjust the concentration of metal ions The morphology of the formed cobalt sulfate layer was observed in the same manner as shown in Figs. 11 and 12. As a step (b), the shower was washed with sufficient pure water, and the ambient temperature was heated by electric heating 2 to 15.0 Let it stay in the drying furnace for 4 seconds, and remove the water. Surface treatment with a grayed-out surface with a non-f good hue =. In addition, between the above steps, 15 seconds of pure water is provided in principle. / v step 'to prevent the solution from being brought into the pre-treatment step. <Physical properties of surface-treated copper box> 22l3'6894 ^ F; Ahddub 29 200533251 The cross-section of the surface-treated copper cymbal with the gray-treated surface obtained through the above steps is FIB As a result of the device observation, a cross-section as shown in FIG. 3 was obtained. The cross-section height (d) of the physical surface is 80 °, and the [color value] 39 'gloss [Gs (6〇e') of the Lab color system of the graying treatment is 2_2. In addition, there is no stain on the graying treatment surface. The adhesive tape was affixed with an adhesive tape on the surface, and then the tape was tested to confirm that there was no powder falling off. "The gray surface of the surface-treated copper foil obtained was processed into an electromagnetic wave shielding net for plasma display. It is judged whether or not blackening can be seen when the transparentization treatment is applied. The black concentration AU of the grayed-out treatment surface before the transparent resin film is formed is evaluated by the same substitution method as in the f! Observation of the treated surface revealed the black color of the black dense tincture 16. <Manufacture of electromagnetic wave shielding mesh for plasma display> In the same manner as in the first embodiment, an electromagnetic wave shielding conductive mesh was trial-produced using the obtained surface-treated copper foil. As a result, the etching operation was not hindered, and very good money engraving was performed without etching residue. In the eighth embodiment, as in the sixth embodiment, the glossy surface of the electrolytic copper pig is not roughened, and the rough surface is grayed to produce the first surface-treated copper box lb shown in FIG. 2. The etching performance was used to test the electromagnetic wave shielding conductive mesh shape. In this embodiment, a copper box having a nominal thickness of 15 # m obtained by electrolytic copper sulfate solution is used. Next, the copper foil was immersed in this solution for 30 seconds using a dilute sulfuric acid solution having a sulfuric acid concentration of 15 g / i and a liquid temperature of 30 ° C to clean the surface. Next, as step (a), sulfuric acid 2213-6894-PF; Ahddub 30 • 200533251, and 9 are formed on the rough surface of the electrolytic steel box. The formation of the cobalt sulfate coating is based on the use of cobalt sulfate (7 water and substances) as the test value for 5 weeks, 5 · 5, and a liquid temperature of 27 ° C as the electroplating solution of sulphuric acid as ^ .jl /. / dm2 electrolyzed at a current density of 12 seconds to form a gray cobalt sulfate coating (equivalent thickness is 268 mg / m2). At this time, the adjustment of the cobalt ion concentration in the solution was not specifically performed. Because of short-term electrolysis, it is considered that the concentration of metal ions must be adjusted. The morphology of the formed cobalt sulfate layer / as shown in Figs. 11 and 12 was similarly observed. ^ As step (b), perform shower washing with sufficient pure water, and heat the ambient temperature to 15 by electric heating _ 2 (rc to stay in the drying furnace for 4 seconds, and remove the water knife 5 &gt; 1 The surface treatment lb of the gray-treated surface with very good color tone is provided with a pure water washing step of 15 seconds in principle between the above steps to prevent the solution from being brought into the pre-treatment step. Physical properties> — # The cross-section of the surface-treated copper surface of the gray-treated surface obtained through the above steps was observed with a FIB device, and as shown in FIG. 3

= Face 'The cross-section height of the grayed-out surface is 78 nm, and the L value of the Lab color system of the grayed-out processing is 40%. The glossiness [Gs (60.)] Is 2.6. In addition, the non-pigmented spots on the grayed surface were coated with adhesive tape on the surface, and the peeled tape test also confirmed that there was no falling powder. Furthermore, the gray-treated surface of the obtained surface-treated copper foil was added as an electromagnetic wave shielding mesh for an electric display, and then subjected to transparency. Before forming the transparent resin film, the black density of the treated surface was u. The result of the same color substitution method as in the i-th example was 4 shells. The gray density of the treated surface was observed to be black & Manufacture of electromagnetic wave shielding mesh for plasma display> 2213-6894-PF; Ahddub 31 200533251 In the same manner as in the first embodiment, an electromagnetic wave shielding conductive mesh was produced using the obtained surface-treated copper foil. As a result, the operation of money engraving is not hindered, no money engraving remains, and very good money engraving is performed. Ninth Example In this example, as shown in FIG. 7, a second surface-treated copper foil including a zinc alloy layer as a rust-preventive treatment layer was produced for 1 d, and was experimentally manufactured by an etching method. Electromagnetic wave shielding conductive mesh shape Confirm its etching performance. That is, until the graying treatment layer of the sulfuric acid misforged layer is formed, it is common to the seventh embodiment. Therefore, only the rust prevention treatment conditions will be described. The converted thickness of the gray cobalt sulfate coating was 268 mg / m2 as in the seventh embodiment. Here, on both sides of the copper foil after the formation of a gray cobalt sulfate plating layer on one side of the seventh embodiment is completed, a cobalt alloy layer is formed on both sides under the same conditions as in the fourth embodiment. Next, similar to the first embodiment, the shower was washed with sufficient pure water, and the ambient temperature was heated to 150 by an electric heater. 〇Stay in a drying furnace for 4 seconds, remove moisture, and obtain a surface-treated copper drop 1 (1 with a grayed surface with a very good color tone. In addition, between the above steps, Lu = 15 seconds The step of pure water washing with bell to prevent the physical properties of the surface-treated copper box with the pre-treatment step. The surface of the copper box with the gray surface obtained through the above steps was observed with a FIB device. The results are as follows: In cross section, the cross section height of the grayed surface was 80 nm, the L value of the gray Ub color system was 41, and the glossiness [Gs (6〇.)] Was not seen outside the grayed surface. Spotted, affixed with adhesive tape on the surface = tested by tearing the tape to confirm that there is no falling powder., Τ Further, the gray surface of the surface-treated copper box obtained was added 2213-6894-PF; Ahddub. 200533251 • The electromagnetic wave shielding mesh used for the electro-condensation display is judged whether blackening can be seen when transparentized. The black concentration of the grayized surface before the transparent resin coating is formed is 0.9. , Using the same code as the first embodiment As a result of the method evaluation, a black surface with a black density of 丨 · 5 was observed on the grayed-out surface. <Production of Electromagnetic Wave Shielding Mesh for Plasma Display> As in the first embodiment, a test was performed using the obtained surface-treated copper foil. Electromagnetic waves were used to shield the conductive mesh. As a result, the etching operation was not hindered, and there was no etching residue. Very good etching was performed. Stomach 10th Example In this example, as shown in FIG. The second surface-treated copper foil If of the cobalt alloy layer and the chromate-treated layer was manufactured by a test method using an epitaxial method to confirm the shape of the electromagnetic shielding shielding conductive mesh. That is, until the gray treatment layer of the cobalt sulfate coating was formed. So far, it is common to the seventh embodiment, so only the rust prevention treatment conditions will be described. The converted thickness of the gray cobalt sulfate coating is the same as that of the seventh embodiment, which is 270 mg / m2. The formation of the rust prevention treatment layer is the same as that of the fourth embodiment. In the same embodiment, a zinc-cobalt alloy layer was formed on both sides using the Ci-Ming alloy electric clock liquid, and then the same chromate treatment was performed on both sides as in the fifth embodiment. Shower clean with sufficient pure water, heat the ambient temperature to 150 ° C with an electric heater and leave it in the drying furnace for 4 seconds, remove the moisture, and obtain a grayed surface with a very good color tone. Treatment of copper alloy 1 f. In addition, between the above steps, a 15-second pure water washing step is provided in principle to prevent the solution from being brought into the pre-treatment step. <Physical properties of surface-treated copper knot> Obtained surface treatment of the grayed-out surface 2213-6894-PP; Ahddub 33 200533251 Observed by the F1 β device of the two sides of the second surface, as shown in FIG. 3, the cross section of the grayed-out surface is obtained. The height is 78njn, the L value of this graying 7 Lab color system is 4 (), gloss ... )] Is 2.4. This • No stains were seen on the coloring surface. The adhesive tape was affixed to the surface, and the tape was peeled off to test it. Furthermore, the gray-treated surface of the obtained surface-treated copper flute was processed into a thunder for a plasma display, and the electromagnetic wave shielding mesh was made transparent.

If you can see if you can see the blackening in the process. Prior to the formation of the transparent resin film: The black concentration of the colorization-treated surface was 0.9, and the result of the same evaluation as in Example J was used. The gray color of the treatment-treated surface was observed to have a black color of 1.6. "Production of electromagnetic wave shielding net for plasma display"-Same as in the first θ example 'Using the obtained surface-treated copper box, an electromagnetic wave shielding conductive net was tested. As a result, even if the anti-money management layer is present, the etching # is not hindered, and there is no surname engraving remaining, and a very good etching is performed.

The industrial utilization possibility has a surface-treated copper foil that is related to the gray-human-treated surface of the invention. There is no treacherous gray-treated surface, and powder does not fall from the surface. Moreover, a common copper etching solution can be used. Plasma display panel The front panel of the front panel is treated with high-quality black to form a non-colored spot. The surface-treated copper foil on the surface of the blackened step in the copper manufacturing process is processed by using the front copper foil. The surface treatment process does not need to be engraved, and can be covered by using it to shield the conductive mesh by electromagnetic waves. In addition, if it can be supplied as a ', the front panel can be omitted. Furthermore, the above-mentioned manufacturing method provided with this graying process can be applied to new manufacturing equipment. That is, 2213-6894-PP; Ahddub 200533251 is a product that can produce high-quality, non-stained products with high yield, so the production cost can be reduced. [Simplified illustration of the drawing] The first picture of the steel foil shows the graying of the damage. A diagram of a cross-sectional layer structure on the surface of a treatment surface. Figure 2 is a diagram showing a table with a grayed-out surface to process the structure of the section layers you have. ~ Cold Fig. 3 is a surface-treated surface with a grayed-out surface 锢 ~ A surface FIB observation image composed of a cross-section of J v white. Surface layer Fig. 4 is an F IB observation image of a standing structure of a surface-treated steel having a grayed-out surface.口 Figure 5 is a surface-treated steel pig with a grayed-out surface

F IB observation image consisting of w Μ plane R. Fig. 6 is a diagram schematically showing the structure of a cross-sectional layer having a surface treated with a grayed-out surface. Fig. 7 is a diagram schematically showing a cross-sectional layer structure of a table having a grayed-out surface. Fig. 8 is a diagram schematically showing the structure of a cross-section layer provided with graying processing. Fig. 9 is a diagram schematically showing the configuration of a cross-section layer provided with graying processing. Surface treatment of steel foil Surface treatment of surface Surface treatment of surface Steel drop Steel foil Figure 10 is a broadcast image of the surface of copper foil after roughening treatment. Tian 1 Electron Microscope Figure 11 is a low magnification observation of the gray sulfuric acid ^ β money deposit layer sweep: te and 丨 β microscope images. Tracing electricity 2213-6894 ~ PF; Ahddub 35 200533251 Figure 12 is a scanning electron microscope image of a gray cobalt sulfate coating observed at a high magnification. Figure 13 is a scanning electron microscope image of the etching test pattern. Figures 14 (a) to 14 (e) are schematic diagrams of a manufacturing process of a front panel of a plasma display panel. Figures 15 (f) to 15 (j) are schematic diagrams of the manufacturing process of the front panel of the plasma display panel. Figures 16 (k) to 16 (n) are schematic diagrams of the manufacturing process of the front panel of the plasma display panel. [Description of main component symbols] 2 ~ roughened treatment layer; 3 ~ fine copper particles; 4 ~ cobalt sulfate coating; 6 ~ chromate treatment layer; 7 ~ copper foil layer; la, lb, lc, Id, le, If ~ Surface-treated copper foil; 5 ~ Record-proof treatment layer (dictionary alloy layer or initial alloy layer).

2213-6894-PF; Ahddub 36

Claims (1)

200533251 X. Patent application: 1. A surface-treated copper foil having a grayed surface on the rough surface of electrolytic copper foil, characterized in that the grayed surface is the weight of one side of the copper foil layer The thickness of the cobalt sulfate coating is 20Omg / m2 ~ 35Omg / m2, and the cross section of the graying treatment surface is less than 200nm. 2 _ If the surface-treated copper foil of item 1 of the scope of the patent application, the gray-treated surface is provided with an anti-money treatment layer. 3 · If the surface-treated copper foil in item 2 of the patent application scope, the anti-recording treatment layer is made of zinc or zinc alloy. 4_ For the surface-treated copper foil with gray processing surface as described in item 2 of the scope of patent application, the anti-rust treatment layer is composed of a layer made of zinc or alloy and a chromate treatment layer. 5. The surface-treated copper foil according to item 1 of the scope of patent application, in which the l value of the aforementioned gray-treated surface is Lab surface color system is 43 or less.丨 6 If the surface-treated copper foil of item 1 of the scope of patent application, wherein the gray-treated surface is formed on the rough surface of the electrolytic copper foil to form the gray-treated surface, and the glossiness [Gs (60.)] Is 10 the following. 7_ The surface-treated copper foil according to item 1 of the scope of the patent application, wherein the aforementioned graying-treated surface has a black concentration of 7-12. 8 · The surface-treated copper foil as described in item 1 of the Patent Scope, wherein the graying-treated surface is visually confirmed to be black when the transparent resin film is closely arranged on the surface. 9 · The surface-treated copper foil as described in item 1 of the Patent Scope, in which the black concentration in the ash 2213-6894-PF; Ahddub 37 200533251 ‘when the transparent resin coating is provided on the color treated surface is above 1.2. i〇 · —A method for producing a surface-treated copper thread, a method for producing a surface-treated copper foil having a gray-treated surface, which is characterized by having the following steps (a) and (b): (a) a rough surface of a copper box ， Cobalt sulfate plating solution containing sulfuric acid (7 hydrates) 〇g / L-~ Wg / L, pH 4.0 or higher, liquid temperature below 30 ° C | Stirring bath, with a current below 4A / dm2 Density electrolysis to form a gray sulfuric acid initial plating layer; and (b) thereafter, washing with water and drying. 11. A method for producing a surface-treated copper foil, a method for producing a surface-treated copper foil having a grayed-out surface, characterized by having the following steps (a), (b), and (C): (a) For rough surface, use a stirred bath containing sulfuric acid starting plating solution containing cobalt sulfate (7 water and substance) 10g / L 4 0 g / L 'p Q value 4 · 0 or higher' liquid temperature 3 0 C or lower, 4 A / dm2 or less Electrolysis at a current density to form a gray cobalt sulfate plating layer; (b) forming a rust-proof treatment layer on both or one side of the copper foil forming the gray cobalt sulfate plating layer; and (c) thereafter, washing with water and drying. 1 2. An electromagnetic wave shielding conductive mesh, characterized in that the electromagnetic wave shielding conductivity for a plasma display front panel formed of a surface-treated copper foil provided with a gray-treated surface as described in item 1 of the scope of patent application is used. Mesh. 1 3-An electromagnetic wave shielding conductive mesh, characterized in that the electromagnetic wave for the front panel of the electrocondensation display panel formed by copper lining at the surface provided with the grayed-out surface described in item 2 of the patent application scope is used. Shield conductive mesh. 1 4 _ An electromagnetic wave shielding conductive mesh characterized by using a plasma-treated plasma foil formed of a surface-treated copper foil having a gray-treated surface as described in item 3 of the patent application scope 2213-6894-PF; Ahddub 38 200533251 The electromagnetic wave for the front panel of the display shields the conductive mesh. 1 5-An electromagnetic wave shielding conductive mesh, characterized in that the electromagnetic wave shielding conductivity for a plasma display front panel formed of a surface-treated copper foil provided with a gray-treated surface as described in item 4 of the scope of patent application is used. Mesh. 16. · An electromagnetic wave shielding conductive mesh, characterized in that the electromagnetic wave shielding conductivity of a plasma display front panel formed of a surface-treated copper foil with a gray-treated surface described in item 5 of the patent application scope is used. Mesh. 17. An electromagnetic wave-shielding conductive mesh, characterized in that the electromagnetic wave-shielding conductivity of a plasma display front panel formed of a surface-treated copper foil with a gray-treated surface as described in item 6 of the patent application scope is used. Sex mesh. 1 8 · — An electromagnetic wave shielding conductive mesh, characterized in that the electromagnetic wave shielding conductive mesh for a front panel of a plasma display is formed by using a surface-treated copper foil having a gray-treated surface as described in item 7 of the patent application scope. sheet. 19. An electromagnetic wave-shielding conductive mesh, characterized in that an electromagnetic wave-shielding conductive mesh for a plasma display front panel formed of a surface-treated copper foil having a gray-treated surface as described in item 8 of the scope of patent application is used. . _ 20 · —Electromagnetic wave shielding conductive mesh, characterized in that the electromagnetic wave shielding conductive mesh for the front panel of a plasma display is formed by using a surface-treated copper foil with a gray-treated surface as described in item 9 of the patent application scope. sheet. 39 2213-6894-PF; Ahddub