TW200409589A - Copper foil for plasma display panel and its manufacturing method - Google Patents

Abstract

A copper foil with excellent shielding characteristic for plasma display panel is provided with black nickel plated-layer, in which the black nickel plated-layer has ΔL= 0:white, ΔL=-100:black and ΔL≤-85.00 in the color-difference meter. The invention is capable of providing excellent shielding effect for effectively blocking electromagnetic wave, near infrared light, scattering light, and the external light. In addition, the invented copper foil for plasma display panel is provided with uniform blackening treatment film and excellent etching characteristic without having the generation of stripe pattern such that it is not peeled due to powder-falling and is capable of blackening completely. Furthermore, the manufacture of copper foil is also provided in the present invention.

Description

200409589 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to a plasma display panel (PDP) which can effectively block electromagnetic waves, near infrared rays, stray light, external light, etc. and has excellent shielding characteristics. Copper foil and manufacturing method thereof. [Prior technology] The electric display panel (PDP), which has the remarkable characteristics of easy to enlarge the screen and fast driving speed, has been rapidly used in various display devices. This plasma display panel has the following structure and function: generating plasma using gas discharge, and exciting the phosphors set in the cell by using the linear spectrum of the ultraviolet region generated thereby to generate visible light District of Light. As described above, when a gas discharge is used to generate electrocondensation, a line spectrum is generated not only in the ultraviolet region used by the phosphor, but also in the wide-range wavelength region in the near-infrared region. The above-mentioned near-infrared wavelengths generated from the plasma display panel are close to the wavelengths used in optical communications. Therefore, if they are close to each other, there will be a problem of erroneous operation, and electromagnetic waves such as microwaves or ultra-low frequencies will be generated The problem. The purpose of blocking the spectral leakage of such electromagnetic waves or near-infrared regions is to adopt a #shielding layer made of a copper box in front of the panel. By hanging this copper mooring system, a thin linear network is formed by the concrete treatment to form a screen 200409589 shielding layer. In addition, the copper shielding layer is further above, and a PET resin is coated with an adhesive. However, since the basic copper foil constituting the above-mentioned shielding layer has a metallic luster, it reflects light from the outside of the panel, which causes a problem of deterioration of the day-to-day ratio, and reflects light generated from the screen to reduce light. The tooth penetration rate causes a problem that the visibility of the display panel deteriorates. In order to solve the above problems, the copper foil shielding layer which can effectively block the electromagnetic wave or the near-infrared line spectral leakage is subjected to blackening treatment. Among the conventional copper foils, a copper foil forming a black surface film is known, and it is generally called a black-treated copper foil. However, copper foils such as Hai are used in the formation of circuits in electronic devices. They mainly only require properties such as adhesion to resin and perforation with field light, and the smoothness and uniformity of the blackened film. Such severe surface conditions are not yet required. However, the characteristics of the copper foil appearing in the front of the plasma display panel directly affect the visibility of the display panel, and it is expected to develop a copper box that can meet such requirements. In particular, the blackening treatment film of copper panels used in the display panel of the Yiyi display will be required: the blackening treatment film surface is uniform and there are fewer or fewer streaks, good etchability, no peeling due to powder loss, and sufficient blackening . Based on the above requirements, in addition to the shielding layer formed by the copper box, in addition to being required to have the accompanying guide film of the plasma display panel ^ film protection function, anti-electromagnetic wave function, anti-infrared function, hue correction function, technical resistance Miscellaneous light functions and external light blocking functions, as well as τ, are particularly required to blacken the above-mentioned physical properties and characteristics of the coating. Copper 200409589 foil for plasma display panel that can meet these functions has not been developed in the past. The conventional technology is as follows: a black frame layer is formed on the periphery of one side of a glass substrate of a transparent substrate, and is separated on such sides. The first adhesive layer forms a transparent PET (polyethylene terephthalate) film, and a copper layer pattern of a metal layer pattern is formed on the pET film through an adhesive layer. The copper layer pattern is A technology formed by covering the periphery of a PET film and applying blackening treatment to both sides and sides (for example, refer to Japanese Patent Laid-Open No. 2000-94841 No. △) to form a common electrode and a scanning electrode on the same side. Surface discharge plasma display panels and plasma display modules that cause a surface discharge between the two electrodes (for example, refer to Japanese Patent Laid-Open No. 2000-89692); make the optical filter set in front of the PDP A filter device for improving the transparency of a copper foil sieve filter for blocking electromagnetic waves (for example, refer to Japanese Patent Laid-Open Publication No. 2001-147312); laminating a porous polymer film on a transparent polymer film, And this copper foil is subjected to an etching treatment by a wet etching method to form a grid-like pattern to obtain a laminated body that forms a light penetrating part, and the laminated body is combined with a transparent support and an anti-reflection film, and the electromagnetic wave shielding is made @ Technology (for example, refer to Japanese Patent Laid-Open No. 2001-217589); if Ni plating is performed on a copper or copper alloy plate with Ni plating solution containing saccharin or its salt as a gloss agent, it can be obtained Technology of Ni plating with high gloss and no expansion due to heating (for example, refer to Japanese Patent Laid-Open No. 2000-21 9996); iron and nickel alloys containing nickel alkylsulfonate and compressive stress can be imparted Electroplating of nickel and nickel alloy plating solution composed of an acidic aqueous solution of a stress reducing additive for the plating layer (for example, refer to Japanese Patent Application Laid-Open No. 1 1-71 695); the metal supply source is a bromine salt 200409589 'chain reducing agent Hydrazine is used, and saccharin or a salt thereof or a plating solution of formalin is added (for example, refer to Japanese Patent Laid-Open No. 2001 — 1 77222 and Japanese Laid-Open No. 2000 — 214279). [Summary of the Invention] The present invention has been made in view of the above problems, and an object thereof is to provide characteristics that can effectively block electromagnetic waves, near-infrared rays, stray light, external light, and the like, and have distinctive shielding characteristics, and that the surface of the blackened film is uniform without streaks, Good etching, no cause

Copper foil for plasma display panel (pDp) which is peeled off and fully blackened and its manufacturing method. A From the above, the present invention provides the following inventions: 1 · A copper foil for a plasma display panel with excellent shielding characteristics, characterized in that: · It is provided with a black nickel plating layer. 0: White, AL = — 100: In the case of black, ΔΙ ^-85.00. 2. —A copper foil for a plasma display panel with excellent shielding characteristics, characterized in that it is provided with a black nickel plating layer. The black nickel plating layer is one of eight in the color difference meter. 1 ^ 0: white, AL =-100: black In this case,-8500; and the powdering of the black nickel plating layer does not occur. 3 · The copper foil for a plasma display panel having excellent shielding properties as described in 1 or 2 above, wherein the black nickel plating layer contains the words 500-2000 # g / dm2, nickel 100-500 // g / dm2 〇4. The copper foil for a plasma display panel having excellent shielding properties as described in 1 or 2 above, wherein the peel strength is 0.3 kg / cm or more. 5. Plasma display panel with excellent shielding properties as described in 1 or 2 above. 200409589 The copper foil used in the "Steel Foil" is a rolled copper foil or electrolytic copper foil of 5 to 35 m. ^ Plasma display panel with excellent shielding properties as described in 1 or 2 above. Copper is used on the black nickel plating layer-further provided with anti-rust treatment layer. Bing 7. The copper name for the plasma display panel having excellent shielding properties as described in the above 6, and the medium 'antirust treatment layer contains chromium and / or zinc. In addition, the present invention further provides the following inventions .... 8. A method for producing a copper foil for a plasma display panel having excellent shielding properties. The feature is that the use of a sulfuric acid containing 50-50 g / L, ammonium sulfate 1 〇 ~ 50g / L, sulfuric acid 20 ~ 50g / L, sodium thiocyanate 10 ~ 30g / L, and saccharin sodium 0.05. 3g / L plating bath, depending on pH: 4 ~ 7, temperature : Room temperature (20 ~ 25.〇) Electric density w · 5 ~ 2 · OA / dm2, using a stainless steel anode or nickel anode to form a black nickel plating layer, the black nickel plating layer in the color difference meter ΔL = 0: white, AL =-100: in the case of black, ΔΙ ^ -85 〇. 9 · The method for manufacturing copper for plasma display panels with excellent shielding properties as described in the above 8; The plating layer does not lose powder. I 0 · The method for producing copper foil for plasma display panels with excellent shielding properties as described in 8 or 9 above, wherein the black nickel plating layer contains zinc 500 to 20000 // g / dm2, nickel 100-500 # g / dm2. II. A method for producing a copper junction for a plasma display panel having excellent shielding properties as described in 8 or 9 above, wherein the peel strength is 0.3 kg / cni or more. 12. The method for producing a copper foil for a plasma display panel having excellent shielding properties as described in 8 or 9 above, wherein the copper foil is a rolled copper foil or electrolytic copper fii of 5 to 35 / zm. 1 3 · Plasma display panel with excellent shielding properties as described in 8 or 9 above 10 200409589 It is a layer treated with a copper foil manufacturing method on a black nickel power ore layer. Further formation of rust prevention [Embodiment] The plasma of the present invention The display panel is made of copper and has a black recording and recording layer: Δί = 0: white, al = _ _: black in the color difference meter of the black nickel plating layer. 'Heart-85.00. This blackening condition is used The stable 'black nickel plating layer was formed on copper foil, and it was achieved for the first time. In other words, using this black nickel electric key layer, it can have the following functions: it can effectively block electromagnetic waves, near infrared rays, stray light, external light, etc. It has excellent shielding characteristics, so there are no streaks that would be observed on the surface of black nickel nickel ore layers, no powder loss, and excellent etching properties. Moreover, if there are streaks, the pDp shielding layer The required premium is not β, so it is undesirable In addition, the powder-derived treatment 'is prone to friction and causes uneven characteristics, so it is best not to have streaks and powder loss. Moreover, it is possible to obtain a peeling strength of 0.3 kg / cm or more and an average centerline. Thickness Ra. 〇〇5 ～ l.〇 " m, maximum height Rt: 〇5 ~ 3 〇 ", ten-point average thickness Rz.o · 05 2 · 0 // m, etc. Foil for display panel. Soil-peeling strength is less than 0.3 kg / cm, the adhesiveness with laminating film (such as • PET) will be reduced, and the reason for peeling will occur. The best peeling strength is 11 200409589 degrees. · 3kg / cm. This black nickel plating layer contains 5,000 to 2000 # g / dra2 and nickel 500 # g / dm 2. Thereby, the black nickel plating layer can be sufficiently blackened, and a plasma display panel copper foil having excellent shielding properties can be obtained. Moreover, it can be blackened with a shielding property that can effectively block electromagnetic waves, near infrared rays, stray light, and external light. The copper stone series can use 5 ~ 35 // m rolled copper foil or electrolytic copper foil. Although rolled copper foil is generally used, electrolytic copper foil may be used. For the formation of a black nickel plating layer, nickel sulfate 5010 g / L, nickel ammonium sulfate 1 10 to 50 g / L, zinc sulfate 2 0 to 5 (^ several, sodium thiocyanate 10 to 30 g / L) can be used. L, and saccharin sodium plating bath of 0.05 ~ 3g / L. By using this plating bath, depending on pH · 4 ~ 7, temperature · room temperature (not ~ 2 5 π), current density 0 · 5 ~ UA / dm2 conditions, made of stainless steel anode or nickel anode ': it can form a better black nickel plating layer for plasma display panel: when stainless steel anode is used, the life of the plating solution will be shortened, so it is usually the most It is good to use a nickel anode. Generally, as known, saccharin is used. However, in this case, it is used at the premise of improving glossiness. In addition, when using a glossing agent, saccharin is used as the first glossing agent. The second gloss agent uses Foma #, butanediol, propanol, etc. These combinations can have the function of a gloss agent. Generally, when only the second gloss agent is used, tensile stress will occur, and when only the second gloss agent is used, In the case of the first gloss agent, compressive stress will be generated. However, if- However, it is expected that the effect of reducing stress will be obtained. 12 200409589 However, in the present invention, the use of saccharin is not for the function of such a gloss agent. In other words, in the present invention, it is considered to form absorption. It is used as a means of blackening the film. Therefore, this is obviously different from the conventional technology in order to maintain glossiness, that is, to use it as a glossing agent. Furthermore, in the tenth aspect of the present invention, it is implemented as described later. The example shows that the ancient nickel mask has an effective function in suppressing the powder fall of the black nickel electric money layer. Therefore, it is obviously different from the well-known saccharin use, function, and effect. As shown in the examples and comparative examples described below, The effect of increasing peeling strength and effectively preventing powder fall is quite obvious. This feature of preventing powder fall and improving peel strength is a major feature of the present invention. After the black nickel electric money layer is formed, it can be further formed on it. Anti-rust treatment layer. This anti-error treatment layer is made of 3 chromium and / or words. The anti-rust treatment method or treatment liquid is not particularly limited. Of course, this anti-rust treatment requires the above-mentioned 4¾ iron treatment surface. On the other hand, it does not damage the characteristics of copper foil used for plasma display panel copper foil and white copper. The anti-rust treatment of the present invention will fully meet these conditions. Moreover, this anti-rust treatment hardly competes with plastics. Double to ring: The shielding characteristics of the blackened film of the present invention are blocking characteristics of electromagnetic waves, near infrared rays, ^ ^ I miscellaneous radiation, external light, etc., resistance to streaks, etching, and resistance to fruit drop. Improving the rust prevention effect The rust prevention treatment of the present invention can be applied such as AA ,,, L, and the following electroplating treatment. The following are representative examples. In addition, this rust prevention treatment is only illustrative and not limited to these examples ·· Bhair 13 200409589 (Chrome antirust treatment)

K2Cr2〇7 (Na2Cr207 or Cr03): 2 ~ 10 g / L

NaOH or KOH: 10 ~ 50g / L ZnO or ZnS (V7H20: 0 · 05 ~ 10g / L ρΗ: 3.0 · 4.0, electrolyte temperature: 20 ~ 80 ° C, current density: 0.0 5 ~ 5A / dm2, plating Time: 5 ~ 30 seconds The second embodiment will be described based on the embodiment. In addition, this embodiment is a preferred example, and the invention is not limited to these embodiments. Therefore, the deformation, Other examples or aspects are included in the present invention. In addition, in order to compare with the present invention, a comparative example is disclosed in the following paragraph. (Example 1) A rolled copper foil with a thickness of 18 // m is subjected to degreasing. After washing with water, pickling, and washing, it contains: nickel sulfate (NiS04) 100g / L, nickel ammonium sulfate ((NH4) 2Ni (SO4) 2) 20g / L, zinc sulfate (ZnS04) 37.5g / L A 15g / L electroplating bath of sodium thiocyanate · sodium (NaSCN), according to pH: 6, temperature: room temperature, current density 0 · 5 ~ 2. OA / dm2 conditions, to form a black nickel plating layer. The anode uses a nickel anode. For degreasing, a common degreasing solution is used to perform electrolytic degreasing. In addition, the pickling system is H2S04: 100 g / L, which is performed at 100 sec and room temperature. 〇 The results are shown in Table 1. 14 200409589 As shown in Table 1, in the examples of the present invention, the color tone AL is better than the reference value (-85 · 00 or less), and no streaks occur, which satisfies a better black nickel plating. The conditions for the use of copper foil for layer plasma display panels. However, powder loss will occur under these conditions. Further observation is made on those who lose powder, although there are negligible ones, but the conditions are not stable. In order to judge whether there are streaks or not, visually observe the streaks. In addition, when the powder is dropped, the transparent tape is pasted on the electroplated surface and peeled off.

The result of checking whether there is any powder on the tape side. When powder is attached, it can be regarded as powder fall. The following are the same. When the powder drop phenomenon is given special attention, and it is required to reduce the powder drop and stabilize it, it is known that some measures must be taken for the first embodiment. Furthermore, 'not mentioned in Table 1', because when the current density is lower than 1.0A / dm2, sufficient plating cannot be formed, and thus the color tone exceeds -85 · 00, and sufficient blackening cannot be obtained.

Furthermore, if the current density exceeds 2.0 A / dm2, more streaks will occur, and the color tone will be lower than the reference, and sufficient blackening will not be obtained. Table — Sample number Current density Dk A / dm2 Plating time sec

〇: No streaks or streaks are in a negligible range X: It is confirmed that there is powder loss. 15 200409589 (Example 2) Take the above example! The representative conditions of the obtained good color tone and no streaks were electro-m / w, 30-second electricity conditions, and a plating bath containing saccharin sodium 0.05 to 3 g / L was used (other conditions are the same as those in Example i). Similarly, a black nickel plating layer is formed. The results are shown in Tables 2 and 3. 0 As shown in Tables 2 and 3, with the addition of saccharin, the hue showed a better value than the reference value, and no streaks occurred. This means that the addition of saccharin will not be a major factor hindering good color tone AL and preventing the occurrence of streaks. Furthermore, it will result in no powder loss and peel strength of 33 kg / cm or more. Copper foil for plasma display panels with optimum black nickel plating.

Table 2 Sample number Saccharin current density Dk (A / dm2) Plating time sec Zn βg / dm2 Ni β g / dm2 5 0.1 1.2 30 7968 217 6 0.5 1.2 30 8472 219 7 1.0 1.2 Π 30 16128 209 Table 3 Sample number Hue △ L Streak peeling strength (kg / cm) 5-94 · 38 〇〇0.33 6-94 · 34 〇〇1 0.48 ~ 7-92 · 45 〇0.53 〇: No streaks or streaks can be ignored In the range. X ·· Check for powder loss. 16 200409589 (Example 3) After forming the black nickel plating layer under the same conditions as those in the implementation, Cr0: 2.5g / L, Zn: 0.4g / L, Na2S04: 10g / L, and ρ4 · 8. Room temperature, plating time: 10 seconds, rust prevention treatment. As a result, the film characteristic values of the copper foil for a plasma display panel obtained the same results as in Example 2. From this, it can be seen that the anti-rust treatment of the present invention does not hinder the shielding properties of the blackening treatment film, such as blocking electromagnetic waves, near infrared rays, stray light, external light, and the like, resistance to streaks, etching, and powder resistance

Under the premise of the peelability, it can improve the rust prevention effect. (Comparative Example 1) A rolled copper foil having a thickness of 18 / zm was subjected to degreasing, water washing, acid washing, and water washing, and then used as in Example 丨, containing: nickel sulfate (NiS04) 100 g / L, nickel ammonium sulfate ((NH4) 2Ni (s〇4) 2) 20g / L, zinc sulfate (ZnSO4) 37.5g / L, sodium thiocyanate (NaSCN) 15g / L electroplating bath electroplating. At this time, a black nickel plating layer was formed according to the conditions of pH: 6, temperature: room temperature, and current density of 3.0 to 5.0 A / dm2. The anode is a stainless steel anode. In terms of degreasing, the conditions were the same as in Example 1. Gn cleaning solution was used at 87: 30g / L, 15A / dm2, 5 seconds, 40 ° C, stainless steel anode, and electrolytic degreasing was performed. Moreover, H2S04: 100g / L was used for pickling, and it implemented at room temperature for 10 second. The results are shown in Table 4. As shown in Table 4, the hue AL of Comparative Example 1 was all worse than the reference value (−85 · 00), and streaks occurred. In addition, a large amount of powder loss also occurred under these conditions. 17 200409589 The person whose hue AL is worse than the reference value of 85 · 00) has poor shielding properties and does not pass through the copper foil for plasma display panels. Table 4

ADVANTAGE OF THE INVENTION The copper foil for a plasma display panel (PDP) of the present invention has a shielding characteristic of six feet of interrupted electromagnetic waves, near-infrared light, stray light, and external light. It has excellent effects such as spotting, good etchability, no peeling due to powder loss, and sufficient blackening. In addition, it has the remarkable effect of stably manufacturing copper sheets for plasma display panels (PDP).疋 [Schematic description] None

18

Claims (1)

200409589 Scope of patent application: 1 · A copper foil for plasma display panels with excellent shielding characteristics, characterized in that it is provided with a black nickel plating layer, which is Δί = 0: white, 100 in the color difference meter : In the case of black,-85.00. 2. —A copper foil for a plasma display panel with excellent shielding characteristics, characterized in that it is provided with a black nickel plating layer, and the black nickel plating layer has a color difference meter from = 0: white, Δί = 100: black In the case, ALS-85 · 〇 ;; and the black nickel plating layer powder does not occur. 3. The copper foil for plasma display panel with excellent shielding properties as described in item 1 or 2 of the patent application, where the black nickel plating layer contains zinc 500 ~ 20,000 Wdm2, nickel 100 ~ 500 / zg / dm2. 4. For the steel foil for plasma display panels with excellent shielding properties, such as item No. 丨 or No. 2, the peel strength is 0.3 kg / cm or more. 5. For the copper foil for plasma display panel with excellent shielding properties in the scope of patent application No. 丨 or No. 2, the copper foil is 5 ~ 35 rolled copper foil or electrolytic copper foil. 6. The copper foil for plasma display panels with excellent shielding properties as described in item 1 or 2 of the scope of patent application, in which a black nickel plating layer is further provided with an anti-iron treatment layer. 7. A plasma display panel with excellent shielding properties as described in item 6 of the patent application, wherein the anti-rust treatment layer contains chromium and / or zinc. 8. A method for manufacturing a copper pig for a plasma display panel with excellent shielding characteristics, which is characterized by using nickel sulfate containing ^ ~ 丨 50 g / L, ammonium ammonium sulfate 10 ~ 50 g / L, and zinc sulfate 20 ~ 50g / L, sodium thiocyanate 10 ～ 30g / L, and 409589 saccharin soda ^ ϋ h / L plating bath, pH: 4 ~ 7, temperature: room temperature 25C), current density 0.5 ~ 2.0A / dm2 conditions, using a stainless steel anode or nickel anode to form a black nickel plating layer, the black nickel electric money layer in the color difference meter of AU0 · account ΛΤ • white, ΔΙ ^-100: black case,-85.00 . 9 · For the plasma display panel with excellent shielding properties, such as copper foil disk for panel No. 8]; skin _ ^ ^ ^ heart watch k method, in which the black nickel plating layer does not lose powder. 10. The method for manufacturing a steel box for a plasma display panel with excellent shielding properties as described in item 8 or 9 of the scope of patent application, wherein the black nickel plating layer contains 500 ~ 20,000 ag / dm2 and nickel 100 ~ 500 // g / dm2. 11. The method for manufacturing a copper foil for a plasma display panel having excellent shielding properties as described in the patent application No. 8 or 9, wherein the peel strength of the copper foil is 0.3 kg / cm or more. 12. A method for manufacturing a copper foil for a plasma display panel with excellent shielding properties, such as item 8 or 9 of the scope of patent application, wherein the copper foil is a rolled copper foil or electrolytic copper foil of 5 to 3 5 # m. 13. A method for manufacturing a copper foil for an electric panel _ display panel having excellent shielding properties as described in claim 8 or 9, wherein a rust-preventive treatment layer is further formed on the black nickel plating layer. 14. The method for manufacturing a copper foil for a plasma display panel having excellent shielding properties as described in item 13 of the patent application scope, wherein the anti-rust treatment layer contains chromium and / or zinc. 20 200409589 (1) Designated representative map: (1) The designated representative map in this case is: (none) map. (2) Brief description of the representative symbols of the components in this representative drawing: None 捌 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention