WO2005064044A1 - Feuille de cuivre traitee en surface par coloration chimique, son procede de production, treillis conducteur de blindage electromagnetique pour panneau avant d'ecran plasma faisant appel a ladite feuille de cuivre traitee en surface par coloration chimique - Google Patents

Feuille de cuivre traitee en surface par coloration chimique, son procede de production, treillis conducteur de blindage electromagnetique pour panneau avant d'ecran plasma faisant appel a ladite feuille de cuivre traitee en surface par coloration chimique Download PDF

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Publication number
WO2005064044A1
WO2005064044A1 PCT/JP2004/019006 JP2004019006W WO2005064044A1 WO 2005064044 A1 WO2005064044 A1 WO 2005064044A1 JP 2004019006 W JP2004019006 W JP 2004019006W WO 2005064044 A1 WO2005064044 A1 WO 2005064044A1
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Prior art keywords
copper foil
plating
treated
browned
treated copper
Prior art date
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PCT/JP2004/019006
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English (en)
Japanese (ja)
Inventor
Tsutomu Higuchi
Original Assignee
Mitsui Mining & Smelting Co.,Ltd.
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Application filed by Mitsui Mining & Smelting Co.,Ltd. filed Critical Mitsui Mining & Smelting Co.,Ltd.
Publication of WO2005064044A1 publication Critical patent/WO2005064044A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/003—3D structures, e.g. superposed patterned layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/04—Wires; Strips; Foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C25D5/611—Smooth layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2211/00—Plasma display panels with alternate current induction of the discharge, e.g. AC-PDPs
    • H01J2211/20—Constructional details
    • H01J2211/34—Vessels, containers or parts thereof, e.g. substrates
    • H01J2211/44—Optical arrangements or shielding arrangements, e.g. filters or lenses
    • H01J2211/446—Electromagnetic shielding means; Antistatic means
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating

Definitions

  • the present invention relates to a browned surface-treated copper foil, a method for producing the same, and an electromagnetic wave shielding conductive mesh for a front panel of a plasma display using the browned surface-treated copper foil.
  • the present invention relates to a surface-treated copper foil having a browned surface, a method for producing the surface-treated copper foil, and an electromagnetic shielding conductive mesh for a front panel of a plasma display using the surface-treated copper foil.
  • the conductive mesh for shielding of a plasma display panel has changed from a metallized fiber fabric to a conductive mesh.
  • Several methods have been established for the production of this conductive mesh.
  • One method is to laminate the surface-treated copper foil on a PET film and attach them together, and then to manufacture them using photolithographic etching.
  • the other is a conductive mesh of the surface-treated copper foil alone, in which the surface-treated copper foil is etched together with the supporting substrate by photolithographic etching, and then the supporting substrate is peeled off.
  • the conductive mesh is manufactured by the method of V, the conductive mesh itself is incorporated in the front panel and the surface force can be visually recognized through the front glass.
  • One side of the surface-treated copper foil is processed from dark brown to black to enhance the brightness of transmitted light.
  • this processing is a technique of a multilayer printed wiring board, and is a technique for improving adhesion between an inner layer circuit and a resin layer. It has been diverted to surface treatment using different metals such as nickel or cobalt.
  • Non-Patent Document 1 Technical Trends of PDP Materials Hitachi Chemical Technical Report No. 33 (1999
  • Patent Document 1 JP-A-11-186785
  • Patent Document 2 JP-A-2000-31588
  • the dropped black oxide is mixed into an unnecessary portion, or is dispersed in the transparent adhesive layer during the transparency treatment for integrating with the glass of the front panel, and the transparency is reduced. Can also be a factor of deteriorating.
  • the drawback of the conventional surface-treated copper foil having a brownish surface is that the brownish surface is not uniform in color but has unevenness on the entire surface. In other words, it is not possible to uniformize the brown treatment in the same plane. Strictly speaking, when trying to etch from the brown surface, the cross-sectional shape of the mesh obtained by etching may vary. It had become. Moreover, the brown surface is in a matte state, and is easily damaged by rubbing the surface lightly! Was the thing.
  • the electromagnetic wave of the plasma display panel is provided with a browning treatment layer having a uniform brownish color, and not containing a dissimilar metal which becomes an etching hindrance so that etching can be performed more easily.
  • Surface-treated copper foil for shielding mesh has been desired.
  • the inventors of the present invention have conducted intensive studies and found that when a surface-treated copper foil is manufactured by the following manufacturing method, a surface treatment that does not include a dissimilar metal, which is a conventional etching inhibiting factor, does not exist. I came up with the idea that copper foil could be obtained.
  • the browned surface-treated copper foil described below is a copper foil provided with a browned surface formed by copper plating performed in multiple stages, as in a manufacturing method described later.
  • the “multi-stage copper plating” refers to a copper plating process that employs two or more plating processes instead of being formed by a single plating process.
  • the base copper foil either an electrolytic copper foil or a rolled copper foil can be used.
  • electrolytic copper foil either its glossy surface or rough surface is selectively used. It becomes possible.
  • the first characteristic of the surface-treated copper foil according to the present invention is that the browned surface has a cross-sectional height of 150 nm or less, which is not extremely rough. Is the first feature. That is, it can be said that the surface is extremely smooth and has a glossy browning. However, to avoid misunderstanding, it should be specified, but it is natural that there is variation within the normal manufacturing process, and it is not necessary that the cross-sectional height at all positions be 150 nm or less. It is natural that there may be cross-sectional heights exceeding 150 nm that reflect variations in the manufacturing process. FIG.
  • FIG. 1 shows a FIB observation image obtained by observing a cross section using a FIB analyzer in order to measure the cross-sectional height of the browned surface 2 of the surface-treated copper foil 1 according to the present invention.
  • FIG. 1 shows an electro-deposited copper foil formed with a browned surface on a glossy surface. This FIB observation image was observed from a direction having an angle of 60 ° with respect to the surface to be observed.
  • the cross section of the browned surface has certain irregularities.
  • a stylus-type surface roughness is used. It is common to use a meter.
  • the maximum difference between the peak and the valley in the field of view of the FIB observation image is defined as the “cross-sectional height” as a value corresponding to Rmax measured by a surface roughness meter.
  • the local force indicated by "d" in Fig. 1 is the cross-sectional height of Fig. 1, which can be determined to be about 80nm.
  • the browning surface 2 in Fig. 1 is formed with an extremely uniform thickness along the shape of the copper foil surface, and maintains a state of perfect adhesion to the underlying copper foil surface. No trouble spots such as the raised browning surface 2 were found, and no spots that would give a sense of powder falling were found.
  • the surface-treated copper foil according to the present invention described above has an extremely smooth surface even from the FIB cross-sectional observation image in FIG.
  • it is a glossy browning treatment, it does not have a gloss enough to diffusely reflect the light received by the browning treated surface, and the browning treatment was applied to the glossy surface of the electrolytic copper foil and the surface of the rolled copper foil.
  • the a value in the Lab color system is less than 4.0.
  • it includes a matte state showing a negative value as gloss.
  • Such a browned surface in the matte state is easily formed when the roughened surface of the electrolytic copper foil is subjected to the browning process.
  • the glossiness of the browned surface according to the present invention should be classified according to the type of the substrate forming the browned surface.
  • the glossiness [Gs (60 °;)] is obtained. It is preferable that it is 10 or less.
  • the degree of gloss is 10 or more, a so-called black glow is created, and the metallic luster becomes conspicuous.
  • the browning-treated surface has a gloss [Gs (60 °)] of 3 or less. is there.
  • the glossiness is 3 or more, it is more likely that the surface has a surface that is easy to fall off due to the relationship between the browning surface and the shrinkage.
  • the browning surface is provided with a water-proof treatment layer.
  • This is a glass that can ensure long-term storage properties of the surface-treated copper foil according to the present invention.
  • the protective layer does not cause discoloration of the browning layer, and if it can be easily dissolved by a copper etchant, it can be an inorganic protective layer such as zinc or brass, benzotriazole, imidazole, or the like. It is also possible to use deviations such as organic protection.
  • the basic method for producing a surface-treated copper foil having a blackened surface according to the present invention includes the following steps a to e.
  • the feature is that the copper plating that forms the browned surface is divided into multiple plating processes instead of being formed by a single plating operation, and copper plating is performed in multiple stages. Hereinafter, each step will be described.
  • Step a This is the first plating treatment for browning the surface of the copper foil using the copper sulfate plating solution under the plating condition (hereinafter referred to as “basic plating treatment”). This is called the basic plating process.
  • the copper foil to be plated in the basic plating step may be subjected to a roughening treatment or a roughening treatment, or may be roughened.
  • This roughening treatment is performed in order to obtain good adhesion to a base material to be laminated, for example, by attaching fine copper particles or by attaching a copper-colored oxidized product that looks black. It was intentionally roughened by the method described above.
  • plating processing is performed under so-called copper plating conditions.
  • the plating performed in the basic plating process is for forming a nucleus for forming a certain degree of unevenness on the copper foil surface, and the surface of the copper foil after the basic plating process is observed with a scanning electron microscope. Does not appear to be clearly roughened.
  • the amount of plating to be electrodeposited in the basic plating step is a converted thickness (hereinafter simply referred to as a "converted thickness") assuming that a completely smooth and flat flat surface is plated.
  • 3 OOmgZm 2 - should be 600MgZm 2 about electrodeposition amount. If it is less than 300 mgZm 2 , it cannot be said that nuclei for sufficient roughening have been formed, and even if the additional plating treatment described later is performed, a good browned surface cannot be formed. On the other hand, when it exceeds 600 mgZm 2 , if an additional plating treatment described later is performed, the roughening treatment proceeds excessively, so that the powder easily falls off and a browned surface is formed.
  • the conditions of the damage are not particularly limited, but are determined in consideration of the characteristics of the production line. For example, if a copper sulfate solution is used, the concentration of copper is 5-20 gZl, sulfuric acid is 50-200 gZl, other additives ( ⁇ -naphthoquinoline, dextrin, dika, thiourea, etc.), and the liquid temperature 15- 40 ° C, and the like to a current density of 10- 50AZdm 2.
  • Step b This step is an additional plating treatment step of subjecting the surface of the copper foil that has been subjected to the basic plating treatment to one or more additional plating treatments using a copper sulfate plating solution under a plating condition.
  • step a The same conditions as in step a. Can be used for the scoring conditions in this additional plating treatment step, but since there are nuclei that will form irregularities on the copper foil surface in step a. It is preferable that the current density be less than half of that in step a. To prevent the current from concentrating on the underlying nucleus and prevent unnecessary abnormal deposition. That is, the current density (la) used when performing the scuffing in the step b is set to be 50% or less of the la, while the current density (la) used when performing the scuffing in the step a.
  • the plating surface formed by the basic plating process and the additional plating process at this time uniformly coats the plating surface to be treated, which does not form a visually roughened unevenness, and is somewhat mild. It is only necessary to be able to create a roughened state. Therefore, it should be noted that it is necessary to control the total current and the total electrolysis time between the basic plating process and the additional plating process in order to create a mild rough state.
  • the appropriate electrodeposition amount in the additional plating step should be about 50 mgZm 2 to 300 mgZm 2 in terms of reduced thickness. If it is less than 50 mg / m 2 , it is not possible to impart an appropriate uneven shape to the surface formed with nuclei in step a, and a favorable browned surface cannot be obtained. On the other hand, if it exceeds 300 mgZm 2 , the nucleus formed in step a becomes excessive, and a browned surface that is easy to fall off is formed.
  • Step c This step is a coating plating treatment step of performing plating treatment on the copper foil surface subjected to plating in Steps a and b under a smooth plating condition using a copper plating solution.
  • the coating process is a plating process for smoothing the surface roughened in the steps a and b, and is a process for uniformly depositing copper so as to cover the roughened surface. Therefore, here, it is possible to use all of the copper electrolytes that can smooth copper.
  • the conditions of the smooth plating are determined in consideration of the characteristics of the production line, which is not particularly limited. For example, if a copper sulfate solution is used, the concentration of copper should be 50-80. GZL, and the like to sulfuric 50- 150gZl, liquid temperature 40- 50 ° C, a current density of 10- 50AZdm 2.
  • electrolysis time so that is not too smooth Soi ⁇ shape by Yakemetsuki, as the conversion thickness when formed into a complete and smooth and flat surface Hemetsuki process, 5g / m 2 - 10g Zm
  • the electrodeposition should be about 2 . If it is less than 5 g / m 2 , the effect of smoothing the surface roughened in the steps a and b cannot be obtained. On the other hand, when lOgZm 2 is exceeded, the surface roughened in steps a and b becomes too smooth, and the color of the browned surface increases the metallic luster.
  • Step d is a plating treatment for finishing the copper foil surface to a brown color by using a copper plating solution under the plating condition on the surface subjected to the smooth plating treatment after the completion of the step c (hereinafter referred to as “the plating treatment”). This is referred to as “finish plating processing”).
  • the difference between the plating process and the above-mentioned basic plating process and additional plating process is that in this process, the roughening treatment is performed using extremely fine copper particles (hereinafter, referred to as “ultra-fine copper particles”). It is done using it.
  • a copper electrolyte containing arsenic is generally used.
  • One example of electrolysis conditions cases according, a a copper sulfate solution, the concentration of copper 10gZl, 1 OOg / U arsenic 1. 5GZl sulfate, liquid temperature 38 ° C, equal to the current density 30AZdm 2 was.
  • a copper electrolyte to which 9-phenylacrylidine is added instead of arsenic is used as an additive having a lower possibility of affecting the human body due to the rise of environmental problems in recent years.
  • 9 Ferracridine plays a role similar to that of arsenic in the field of copper electrolysis, enabling the sizing effect of fine copper particles deposited and uniform electrodeposition. That is, as a copper electrolyte for forming ultra-fine copper particles added with 9-phenylacridine, the concentration of copper is 5 to 15 gZl, free sulfuric acid is 40 to 100 gZl, 9-phenylatalidine is 50 to 300 mg / l, A chlorine concentration of 20 ppm to 32 ppm, a liquid temperature of 30 to 40 ° C, and a current density of 20 to 40 A / dm 2 are within the range where extremely stable electrolytic operation can be performed.
  • copper is 10 to 15 gZl
  • free sulfuric acid is 40 to 70 gZl
  • 9 phenylacridine is 100 to 200 mg / U
  • chlorine concentration is 25 ppm to 30 ppm
  • liquid temperature is 30 to 40.
  • current density is in the range of 20-40 AZdm2. This range is most excellent in operation stability and solution stability as a plating solution, The production yield of the surface-treated copper foil according to the present invention is increased.
  • Step e This step is a washing and drying step after completion of each of the above steps, washing with water and drying to obtain a browned surface-treated copper foil.
  • the rinsing referred to here simply means the final rinsing, and rinsing that can be considered within a common sense is appropriately provided between each process so as not to bring the solution of the previous process into the subsequent process. Please note that.
  • This production method is a method for producing a browned surface-treated copper foil including the following steps a to f.
  • Step a Basic plating treatment in which the first plating treatment for browning the surface of the copper foil (hereinafter referred to as “basic plating treatment”) is performed using a copper sulfate plating solution under the covering condition.
  • Process b An additional plating process in which a copper sulfate-based plating solution is subjected to one or more additional plating processes on the surface of the copper foil that has been subjected to the basic plating process, under a plating condition.
  • Step c A coating plating treatment step in which the copper foil surface subjected to plating in Steps a and b is plated with a copper sulfate plating solution under smooth plating conditions.
  • Step d On the surface that has been subjected to the step c and has been subjected to the smooth plating treatment, a plating treatment for finishing the copper foil surface to brown using a copper sulfate plating solution under the plating condition (hereinafter referred to as ⁇ finish plating treatment ''). Finishing process for applying a finish.
  • ⁇ finish plating treatment '' a plating treatment for finishing the copper foil surface to brown using a copper sulfate plating solution under the plating condition
  • Step e a water-proofing treatment step of performing a water-proofing treatment on the surface of the copper foil which has been subjected to the browning treatment by the above steps.
  • Step f After each of the above steps, a washing and drying step of washing and drying to obtain a browned surface-treated copper foil.
  • this is a step in which a protection process is added to the manufacturing method 1. Therefore, in order to avoid redundant description, only the protection process will be described.
  • the surface of the surface-treated copper foil is prevented from being oxidized and corroded without causing discoloration of the browned surface and being easily removed by etching with a copper etching solution.
  • Benzotriazole, imidazole, etc. are used for this protection treatment. It does not matter whether the organic barrier used or the inorganic barrier using zinc, chromate, zinc alloy or the like is adopted. What is necessary is just to select the protection in accordance with the intended use of the surface-treated copper foil. In the case of organic protection, it is possible to adopt a method such as dip coating, showering coating, and electrodeposition of an organic protection agent.
  • a protection element is deposited on the surface of the surface-treated copper foil by electrolysis, or a so-called displacement deposition method.
  • a zinc pyrophosphate plating bath, a cyanide zinc plating bath, a zinc sulfate plating bath, or the like can be used as the zinc prevention treatment.
  • the plating treatment is performed using a zinc-nickel alloy plating solution or a zinc-cobalt alloy plating solution as an inorganic protection.
  • a zinc-nickel alloy plating solution or a zinc-cobalt alloy plating solution as an inorganic protection.
  • zinc-nickel alloy plating will be described.
  • the zinc-nickel alloy plating solution used here is not particularly limited.Examples include, for example, nickel sulfate having a nickel concentration of 12.5 gZl, zinc pyrophosphate having a zinc concentration of 0.1 lgZl, and pyrophosphoric acid. Potassium acid salt 50-500gZl, liquid temperature 20-50. C, pH 8-11, current density 0.3-IOAZdm 2 etc. are adopted.
  • the zinc-conoleto alloy plating solution used here is not particularly limited, but, for example, for example, the cobalt concentration is 1-2.5 g / l using cobalt sulfate, and the zinc concentration is 0.1-2.5 g using zinc pyrophosphate. lg / l, potassium pyrophosphate 50-500 gZl, liquid temperature 20-50. C, pH8-11, current density. 3—Use the conditions of lOAZdm 2 .
  • the anti-corrosion treatment layer obtained by combining this zinc-cobalt alloy plating with the chromate treatment described later exhibits particularly excellent corrosion resistance.
  • the chromate treatment may be performed after the formation of the above-described heat-resistant treatment layer.
  • any of a substitution treatment in which a chromate solution is brought into contact and an electrolytic chromate treatment in which a chromate film is formed by electrolysis in a chromate solution may be employed.
  • the chrome used here Regarding the salt solution it is possible to use those in the range used in a usual manner. After that, it is washed with water and dried to obtain a surface-treated copper foil having a browned surface.
  • the surface-treated copper foil provided with the browned surface according to the present invention described above does not fall off from the browned surface, and has a very uniform brown color without unevenness.
  • the browning layer can be removed by etching using a normal copper etching process. Therefore, it is possible to easily process the printed wiring board into an arbitrary shape by using a process for manufacturing the printed wiring board. Considering these facts, it can be said that it is the most suitable for the application of the electromagnetic wave shielding conductive mesh incorporated in the front panel of the plasma display panel.
  • the method for producing a surface-treated copper foil according to the present invention is a conventional method in which a browned surface is efficiently formed on the surface of a copper foil by employing a multi-stage copper plating method. This made it possible to minimize the variation in the color tone of the surface-treated copper foil having the browned surface.
  • the surface is subjected to a roughening treatment! / ⁇
  • a browning treatment is performed on the glossy surface using an electrolytic copper foil! Was experimentally manufactured by the etching method, and the etching performance was confirmed.
  • a copper foil with a nominal thickness of 10 Pm obtained by electrolyzing a copper sulfate solution was used. Then, the electrolytic copper foil was immersed in a dilute sulfuric acid solution having a sulfuric acid concentration of 150 gZl and a liquid temperature of 30 ° C. for 30 seconds to clean the surface.
  • a dilute sulfuric acid solution having a sulfuric acid concentration of 150 gZl and a liquid temperature of 30 ° C. for 30 seconds to clean the surface.
  • the basic plating treatment condition used at this time was a copper sulfate solution, which was electrolyzed under the following conditions: copper concentration 18gZl, free sulfuric acid concentration 100gZl, solution temperature 25 ° C, current density (la) lOAZdm 2. It was done by doing. As a result, in the plating performed in the basic plating process, only a nucleus for forming a certain degree of unevenness on the copper foil surface was formed, and the electrodeposition amount was 300 mg Zm 2 in terms of reduced thickness.
  • Step b In this additional plating treatment step, one plating treatment was performed on the surface of the copper foil that had been subjected to the basic plating treatment, using a copper sulfate-based plating solution under scorching conditions.
  • the additional plating treatment conditions at this time were the same concentration and liquid temperature of copper sulfate solution as in step a., But the current density (lb) used when performing plating was changed to 15% of la As 1.5AZdm 2 , current concentration on the nuclei formed on the surface of the copper foil in step a. was prevented to prevent unnecessary abnormal precipitation.
  • the electrodeposition amount during this additional plating step was an electrodeposition amount of 50 mgZm 2 as a converted thickness.
  • Step c In this coating plating treatment step, the copper foil surface subjected to plating in steps a and b was subjected to plating treatment under a smooth plating condition using a copper plating solution.
  • a copper sulfate solution, the copper concentration 65GZl, free sulfuric acid concentration 150GZl, liquid temperature 4 5 ° C, and electrolysis was performed with smooth plated a current density 15AZdm 2.
  • the surface subjected to the roughening treatment in the steps a and b was smoothed.
  • the converted thickness of the smooth plating was 4 gZ m (?
  • Step d In this finish plating treatment step, the surface subjected to the step c and subjected to the smooth plating treatment is subjected to a plating treatment for finishing the surface of the copper foil to brown using a copper plating solution under the plating condition. Thus, extremely fine copper particles were adhered and formed.
  • the following copper sulfate solution prepared by adding 9-phenylacrylidine was used.
  • a copper concentration of 13 gZl, free sulfuric acid of 50 gZl, 9-phenylacridine of 150 mgZl, a chlorine concentration of 28 ppm, a liquid temperature of 35 ° C., and a current density of 24 AZdm 2 were used.
  • the electrodeposition amount in the finish plating process was an electrodeposition amount of 300 mgZm 2 as a converted thickness.
  • Step e In this washing / drying step, after the above-mentioned step d.
  • the deionized water is sufficiently washed by washing, and placed in a drying furnace with an atmosphere temperature of 150 ° C. from an electric heater.
  • the sample was allowed to stay for 4 seconds to remove moisture, and a surface-treated copper foil having a browned surface with a very good color tone was obtained.
  • water washing not only the water washing here, but also water washing between the steps was appropriately provided between the steps so that the solution of the previous step was not carried into the subsequent step.
  • the cross section shown in FIG. 1 was obtained, and the cross-sectional height of the browned surface ( d) was 80 nm, the a value of the browned surface in the Lab color system was 3.5, and the gloss [Gs (60 °;)] was 2.8.
  • a sticky tape was applied to the browned surface, and a powder test in peeling off the adhesive tape was confirmed.
  • a dry film serving as an etching resist was bonded to both surfaces of the surface-treated copper foil obtained as described above. Then, only the dry film on the browned surface side is overlaid with a mask film for testing to produce an electromagnetic shielding conductive mesh, and the mesh pitch is 200 m, the mesh line width is 10 ⁇ m, and the mesh bias angle is 45 °. Then, a conductive mesh pattern having a mesh electrode portion on the periphery was exposed to ultraviolet light. At this time, the entire surface of the etching resist layer on the opposite side was also exposed to ultraviolet light so that it could not be removed by subsequent development. Thereafter, development was performed using an alkaline solution to form an etching pattern.
  • This embodiment is different from the first embodiment only in that a protection process is provided between step d and step e of the first embodiment. Therefore, the steps a, b, and d are the same as those in the first embodiment, and a duplicate description is avoided, and only the step e. I will explain it.
  • Step e In this protection treatment step, a plating treatment was performed using a zinc-nickel alloy plating solution to form a zinc-nickel alloy layer on both surfaces.
  • Zinc-nickel alloy layer the nickel concentration with sulfate nickel 2.
  • OgZl zinc concentration using pyrophosphate zinc 0. 5 GZL, potassium pyrophosphate 250GZl, liquid temperature 35 ° C, pH 10, the current density 5AZdm 2 Electrolysis was performed for 5 seconds under the same conditions to uniformly and uniformly deposit on both surfaces.
  • Step f This washing / drying step corresponds to step e. Of Example 1. After the above-mentioned step e. Is completed, it is sufficiently washed with water, dried by heating, and provided with a browned surface. The surface-treated copper foil was used, and the details are the same as in Example 1.
  • Example 2 In the same manner as in Example 1, an electromagnetic wave shielding conductive mesh was prototyped using the obtained surface-treated copper foil. As a result, very good etching was performed with no residual etching that hindered the etching operation even when the anti-reflection treatment layer was present.
  • Example 1 a blackened surface was formed on the glossy surface of the copper foil with a nominal thickness of 10 ⁇ m, which is an electrolytic copper foil. They produced surface-treated copper foil with a treated surface. First, in the same manner as in Example 1, the electrolytic copper foil was immersed in a dilute sulfuric acid solution having a sulfuric acid concentration of 150 gZl and a liquid temperature of 30 ° C. for 30 seconds to clean the surface. Hereinafter, each process will be described.
  • a basic plating treatment for browning the surface of the copper foil was performed.
  • the surface roughness of the rough surface of the single-profile copper foil with a belly opening was such a low profile that it did not hinder the glossy surface.
  • steps a basic plating processing step
  • step b additional plating processing step
  • step c Coating plating processing step
  • step d finishing plating processing step
  • step e standarde as in Example 1 After washing and drying steps), a surface-treated copper foil having a browned surface was obtained.
  • Example 2 In the same manner as in Example 1, an electromagnetic wave shielding conductive mesh was prototyped using the obtained surface-treated copper foil. As a result, very good etching was performed with no residual etching that hindered the etching operation even when the anti-reflection treatment layer was present.
  • Example 2 a blackened surface was formed on the glossy surface of a copper foil with a nominal thickness of 10 ⁇ m, which is an electrolytic copper foil, and the blackened surface was formed on the rough side in the present embodiment. They produced surface-treated copper foil with a treated surface. First, the surface of the electrolytic copper foil was cleaned using the procedure of Example 1 as in Example 2. Hereinafter, each step will be described.
  • Steps a basic plating processing step
  • step b additional plating processing step
  • step c. Coating plating processing step
  • step d finish plating processing step
  • step e. A protection step
  • step f a surface-treated copper foil provided with was obtained.
  • the zinc-nickel alloy layer was formed in the same procedure as in the second embodiment. Therefore, the above steps have been described in the above embodiment, and the duplicate description will be omitted.
  • Gs (60 °;)] was 1.5.
  • a sticky tape was applied to the browned surface, and a powder test in peeling off the adhesive tape was confirmed.
  • Example 2 In the same manner as in Example 1, an electromagnetic wave shielding conductive mesh was prototyped using the obtained surface-treated copper foil. As a result, very good etching was performed with no residual etching that hindered the etching operation even when the anti-reflection treatment layer was present.
  • Step d In this finishing step, the copper concentration of the following copper sulfate solution to which 9-fluoroacrylidine used in Example 1 was added was set to 8 gZl. Then, the electrodeposition amount in the finish plating process was 300 mgZm 2 as the converted thickness in the same manner as in Example 1.
  • Example 2 In the same manner as in Example 1, an electromagnetic wave shielding conductive mesh was prototyped using the obtained surface-treated copper foil. As a result, the browning-treated surface of the surface-treated copper foil obtained in this comparative example was rubbed at the time of handling, although the etching operation was not hindered even when the heat-resistant treatment layer was present. It was difficult to maintain the browned surface of the area immediately after the completion of the etching process.
  • the surface-treated copper foil provided with the browned surface according to the present invention has no unevenness in color.
  • the browned surface having excellent scratch resistance is provided, and the power to remove powder from the blackened surface is also high.
  • the etching force can be reduced using a normal copper etching solution, and a high-quality black mask can be formed by using a conductive mesh for shielding electromagnetic waves on a front panel of a plasma display panel. Further, by supplying as a surface-treated copper foil having a browning-treated surface, it is possible to omit the blackening process in the front panel manufacturing process.
  • a multi-step copper plating method is employed, and a production method of performing smooth plating and finishing plating is employed, whereby the surface-treated copper foil according to the present invention is obtained. Since production can be performed with a high yield, production costs can be reduced.
  • FIG. 1 is a diagram schematically showing a cross-sectional layer configuration of a surface-treated copper foil having a browned surface.
  • FIG. 2 is a diagram schematically showing a cross-sectional layer configuration of a surface-treated copper foil having a browned surface. Explanation of symbols

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Abstract

L'invention concerne une feuille de cuivre traitée en surface, exempte de chute de poudre, qui présente une couche, traitée par coloration chimique, de teinte uniforme et qui ne contient pas de métaux étrangers, pouvant constituer un facteur d'inhibition d'attaque, de façon à faciliter l'attaque. Cette feuille de cuivre présente une surface traitée par coloration chimique, formée par placage de cuivre réalisé en plusieurs étapes. La hauteur en coupe transversale de cette surface est inférieure ou égale à 150 nm. Cette surface est caractérisée par exemple en ce qu'elle présente une valeur a dans le système CIELAB inférieure ou égale à 4,0. Cette feuille de cuivre traitée en surface est produite fondamentalement selon un procédé comprenant les étapes de (a) placage de base, (b) placage supplémentaire, (c) plaque de revêtement, (d) placage de finition et (e) lavage/séchage.
PCT/JP2004/019006 2003-12-26 2004-12-20 Feuille de cuivre traitee en surface par coloration chimique, son procede de production, treillis conducteur de blindage electromagnetique pour panneau avant d'ecran plasma faisant appel a ladite feuille de cuivre traitee en surface par coloration chimique WO2005064044A1 (fr)

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JP2003-433053 2003-12-26
JP2003433053A JP4354271B2 (ja) 2003-12-26 2003-12-26 褐色化表面処理銅箔及びその製造方法並びにその褐色化表面処理銅箔を用いたプラズマディスプレイの前面パネル用の電磁波遮蔽導電性メッシュ

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WO2005064044A1 true WO2005064044A1 (fr) 2005-07-14

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JP (1) JP4354271B2 (fr)
KR (1) KR100738164B1 (fr)
CN (1) CN100567584C (fr)
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CN114836801A (zh) * 2022-06-21 2022-08-02 中船九江精达科技股份有限公司 一种铍青铜弹性器件的多层电镀工艺

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JP5124154B2 (ja) * 2006-03-28 2013-01-23 富士フイルム株式会社 導電膜の製造方法
WO2010093009A1 (fr) * 2009-02-13 2010-08-19 古河電気工業株式会社 Feuille de métal, son procédé de fabrication, substrat isolant et tableau de connexions
WO2016035604A1 (fr) * 2014-09-02 2016-03-10 三井金属鉱業株式会社 Feuille de cuivre traitée en surface noircie et feuille de cuivre comprenant une feuille support
JP6782561B2 (ja) * 2015-07-16 2020-11-11 Ｊｘ金属株式会社 キャリア付銅箔、積層体、積層体の製造方法、プリント配線板の製造方法及び電子機器の製造方法
US10470291B2 (en) * 2017-07-21 2019-11-05 Chintung Lin Process for preparing an energy saving anti-burst heat dissipation device
CN109440157B (zh) * 2018-12-05 2021-05-25 常德力元新材料有限责任公司 一种褐色导电海绵的制备方法
EP4296050A1 (fr) 2021-02-19 2023-12-27 Mitsui Mining & Smelting Co., Ltd. Procédé de fabrication de plaque stratifiée ainsi que d'élément chauffant, et dégivreur
WO2022176699A1 (fr) 2021-02-19 2022-08-25 三井金属鉱業株式会社 Procédés de fabrication de plaque stratifiée et générateur de chaleur, et dégivreur
KR20230146517A (ko) 2021-02-19 2023-10-19 미쓰이금속광업주식회사 적층판 및 발열체의 제조 방법 그리고 디프로스터
WO2024122927A1 (fr) * 2022-12-06 2024-06-13 에스케이넥실리스 주식회사 Feuille de cuivre à haute résistance et à allongement élevé, électrode la comprenant, batterie secondaire la comprenant, et son procédé de fabrication

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WO2001056345A1 (fr) * 2000-01-28 2001-08-02 Mitsui Mining & Smelting Co.,Ltd. Feuille de cuivre traitee en surface, son procede de production et stratifie recouvert de cuivre dans lequel ladite feuille est utilisee
JP2003201597A (ja) * 2002-01-09 2003-07-18 Nippon Denkai Kk 銅箔とその製造方法及び該銅箔を用いた電磁波シールド体

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WO1985002870A1 (fr) * 1983-12-19 1985-07-04 Microclad Laminates Limited Production d'une surface mate sur une couche de metal
WO2001056345A1 (fr) * 2000-01-28 2001-08-02 Mitsui Mining & Smelting Co.,Ltd. Feuille de cuivre traitee en surface, son procede de production et stratifie recouvert de cuivre dans lequel ladite feuille est utilisee
JP2003201597A (ja) * 2002-01-09 2003-07-18 Nippon Denkai Kk 銅箔とその製造方法及び該銅箔を用いた電磁波シールド体

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KR100738164B1 (ko) 2007-07-10
TW200526111A (en) 2005-08-01
JP2005187913A (ja) 2005-07-14
TWI301049B (fr) 2008-09-11
KR20060067921A (ko) 2006-06-20
CN100567584C (zh) 2009-12-09
JP4354271B2 (ja) 2009-10-28

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