Electrolytic copper foil and method of manufacturing and use thereof

Abstract

The embodiment of the present application relates to the technical field of OLED display, and specifically discloses an electrolytic copper foil, a manufacturing method and application thereof, the electrolytic copper foil is generated by electrolysis in an electrolyte with a cathode roller, then the green foil is sequentially subjected to roughening, solidification, zinc-nickel plating, chromium plating and coupling agent coating processes to be made into the electrolytic copper foil.The electrolytic copper foil prepared by the present application has good tensile strength and can meet the manufacturing requirements of high-end OLED screens.The raw material of the green foil additive contains hydrolyzed gelatin, sodium benzenesulfinate, hydroxyethyl cellulose and hydrochloric acid, which improves the tensile strength of the copper foil through the green foil electrolysis process, solves the problem of low tensile strength of the existing electrolytic copper foil, and cannot meet the manufacturing requirements of OLED screens.Furthermore, the manufacturing method of the electrolytic copper foil is simple and has a broad market prospect.

Description

TECHNICAL FIELD

[0001] The embodiment of the present application belongs to the technical field of OLED display, and particularly relates to an electrolytic copper foil and a manufacturing method and application thereof. BACKGROUND

[0002] With the continuous development of science and technology and the increasing progress of display technology, the application range of OLED screens is increasing in the market. OLED (Organic Light-Emitting Diode) is also called organic light-emitting diode, and the OLED screen formed by the OLED is used as a display screen in some flat panels, mobile phones, computers and other electronic devices, and is a kind of display with excellent performance.

[0003] In the manufacturing of OLED screens, copper foil, aluminum foil and other foils are usually used, and the main function of the foils in the OLED screen is support and heat dissipation. However, the prior art in the above has the following defects: the traditional electrolytic copper foil in the prior art has low tensile strength due to the electrolysis process, and is difficult to be applied to the manufacturing of OLED screens, and cannot meet the manufacturing requirements of high-end OLED screens. SUMMARY

[0004] The embodiment of the present application aims to provide an electrolytic copper foil to solve the problem of low tensile strength of the existing electrolytic copper foil in the background art.

[0005] To achieve the above-mentioned purpose, the embodiment of the present application provides the following technical scheme:

[0006] An electrolytic copper foil, specifically, a green foil is generated by placing a cathode roller in an electrolyte for electrolysis, and then the green foil is sequentially subjected to roughening, solidification, zinc-nickel plating, chromium plating and coupling agent coating to obtain the electrolytic copper foil; wherein the electrolyte contains a green foil additive, and the raw material of the green foil additive contains hydrolyzed gelatin, sodium benzenesulfinate, hydroxyethyl cellulose and hydrochloric acid.

[0007] Preferably, the raw material of the green foil additive includes 200-1000ppm hydrolyzed gelatin, 100-300ppm sodium benzenesulfinate, 200-500ppm hydroxyethyl cellulose and 20-40ppm hydrochloric acid.

[0008] Preferably, the raw material of the green foil additive includes 300-900ppm hydrolyzed gelatin, 150-280ppm sodium benzenesulfinate, 240-420ppm hydroxyethyl cellulose and 23-30ppm hydrochloric acid.

[0009] Another object of the embodiment of the present application is to provide a manufacturing method of an electrolytic copper foil, and the manufacturing method of the electrolytic copper foil comprises the following steps:

[0010] The cathode roller is electrolyzed in the electrolyte to generate a green foil, and then the green foil is roughened at a temperature of 30-40 DEG C, solidified at a temperature of 25-45 DEG C, then plated with zinc-nickel, plated with chromium, and coated with a coupling agent, dried, cut, to obtain the electrolytic copper foil.

[0011] Another purpose of the embodiment of the present application is to provide an electrolytic copper foil prepared by the above-mentioned method.

[0012] Another purpose of the embodiment of the present application is to provide an application of the above-mentioned electrolytic copper foil in preparing an OLED screen.

[0013] Compared with the prior art, the embodiment of the present application has the following beneficial effects:

[0014] Compared with the prior art, the electrolytic copper foil provided by the embodiment of the present application is generated by placing a cathode roller in an electrolyte for electrolysis to generate a green foil, and then the green foil is sequentially subjected to roughening, solidification, zinc-nickel plating, chromium plating, and coupling agent coating processes to be made, and the prepared electrolytic copper foil has good tensile strength and can meet the manufacturing requirements of high-end OLED screens. Since the raw material of the green foil additive contains hydrolyzed gelatin, sodium benzenesulfinate, hydroxyethyl cellulose, and hydrochloric acid, the tensile strength of the copper foil is improved through the green foil electrolysis process, solving the problem of low tensile strength of the existing electrolytic copper foil, which cannot meet the manufacturing requirements of OLED screens. Moreover, the manufacturing method of the electrolytic copper foil provided by the embodiment of the present application is simple, can be used to prepare other types of copper foils, and has a broad market prospect. BRIEF DESCRIPTION OF DRAWINGS

[0015] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following will briefly introduce the drawings needed to be used in the embodiments or the prior art description. Obviously, the drawings in the following description are only some embodiments of the present application.

[0016] Figure 1 The 1000 times SEM picture of the smooth surface of the copper foil provided by an embodiment of the present application.

[0017] Figure 2 The 1000 times SEM picture of the appearance surface of the copper foil provided by an embodiment of the present application. DETAILED DESCRIPTION

[0018] In order to make the technical problems to be solved by the present application, technical solutions and beneficial effects clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below in combination with the embodiments of the present application and the drawings. Obviously, the following embodiments will help those skilled in the art to further understand the embodiments of the present application, but do not limit the embodiments of the present application in any form. It should be noted that, for those skilled in the art, without departing from the concept of the embodiments of the present application, a number of modifications and improvements can also be made. These all belong to the protection scope of the embodiments of the present application.

[0019] The specific implementation of the present application is described in detail below in combination with specific embodiments.

[0020] First of all, it needs to be pointed out that in the production of OLED screens, copper foil, aluminum foil and other foils are usually used in the prior art, and their main functions in OLED screens are support and heat dissipation. Copper foil is generally divided into rolled copper foil and electrolytic copper foil, among which electrolytic copper foil has a suitable daoyin value (surface tension) and is usually suitable for the production of general OLED screens. However, the traditional electrolytic copper foil has a low tensile strength due to the electrolysis process, which cannot meet the production requirements of high-end OLED screens.

[0021] Therefore, in order to solve the problem of low tensile strength of the existing electrolytic copper foil in the prior art, which cannot meet the production requirements of OLED screens, the embodiments of the present application provide an electrolytic copper foil and a production method and application thereof. The electrolytic copper foil is specifically an electrolytic copper foil for OLED screens, which is suitable for OLED screens. The electrolytic copper foil is specifically a green foil generated by electrolysis in an electrolyte with a cathode roller, and then the green foil is sequentially subjected to roughening, solidification, zinc-nickel plating, chromium plating and coupling agent coating processes to be made. The prepared electrolytic copper foil has good tensile strength and can meet the production requirements of high-end OLED screens. Among them, the coupling agent is a treatment agent, and the coupling agent process is also a treatment agent process.

[0022] As another preferred embodiment of the present application, the cathode roller is further subjected to a polishing pretreatment process before being placed in the electrolyte to control the surface roughness of the cathode roller to Ra=0.25±0.1 μm.

[0023] As another preferred embodiment of the present application, the cathode roller polishing pretreatment process is: using a polishing roller made of silicon carbide to polish the surface of the cathode roller, and controlling the surface roughness to Ra=0.25±0.1 μm. The polishing pretreatment method is divided into three steps. First, using a 1000-mesh polishing roller made of silicon carbide, the speed is 160 rpm-200 rpm, the left and right speed is 120 rpm-160 rpm, the load is 8-16%, the cathode roller speed is 1.4 m / rpm-1.6 m / rpm, and the polishing time is 30-45 minutes. Then, using a 2000-mesh polishing roller made of silicon carbide, the speed is 200 rpm-240 rpm, the left and right speed is 160 rpm-200 rpm, the load is 4-8%, the cathode roller speed is 1.1 m / rpm-1.3 m / rpm, and the polishing time is 35-50 minutes. Finally, the roller surface is cleaned, and the polishing pretreatment is performed again after 4-8 days of production. The production time between two polishing pretreatments is called a polishing cycle.

[0024] As another preferred embodiment of the present application, the electrolyte used in the electrolysis contains a green foil additive, which includes 200-1000 ppm hydrolyzed gelatin, 100-300 ppm sodium benzenesulfinate, 200-500 ppm hydroxyethyl cellulose, and 20-40 ppm hydrochloric acid. Sodium benzenesulfinate and hydroxyethyl cellulose change the copper foil lattice, and improve and stabilize the tensile strength and elongation of the copper foil.

[0025] As another preferred embodiment of the present application, the electrolyte used in the electrolysis contains a green foil additive, which includes 300-900 ppm hydrolyzed gelatin, 150-280 ppm sodium benzenesulfinate, 240-420 ppm hydroxyethyl cellulose, and 23-30 ppm hydrochloric acid.

[0026] Further preferably, in the electrolysis to generate a green foil, the electrolysis green foil process is: using an electrolyte containing 65-115 g / L sulfuric acid and 85-105 g / L divalent copper ions to generate a green foil on the surface of the cathode roller under the conditions of a temperature of 30-40 ℃ and a current density of 30-50 A / dm2. The electrolyte contains a green foil additive, which includes 200-1000 ppm hydrolyzed gelatin, 100-300 ppm sodium benzenesulfinate, 200-500 ppm hydroxyethyl cellulose, and 20-40 ppm hydrochloric acid. Sodium benzenesulfinate and hydroxyethyl cellulose change the copper foil lattice, and improve and stabilize the tensile strength and elongation of the copper foil.

[0027] As another preferred embodiment of the present application, the roughening solution used in the roughening contains a roughening additive, which includes 5-20 ppm sodium citrate and 2-6 ppm molybdate. Sodium citrate acts as a complexing agent, stabilizes the electrolyte, and ensures the uniformity of the roughening coating. Molybdate improves the uniformity of plating.

[0028] As another preferred embodiment of the present application, the solidification employs a solidification liquid containing a solidification additive, which contains 10-25 ppm sodium citrate and 0.5-5 ppm alkyl quaternary ammonium salt.

[0029] Preferably, the solidification process is that the roughened raw foil is electroplated using a solidification liquid containing 140-170 g / L sulfuric acid, 40-60 g / L divalent copper ions and 15-25 ppm chloride ions at a temperature of 25-45℃ and a current density of 60-80 A / dm2.

[0030] As another preferred embodiment of the present application, the coupling agent is applied by coating. The raw foil is coated with a coupling agent at a concentration of 0.2 g / L, and then dried and cut to obtain the finished copper foil. The coupling agent mainly enhances the bonding of the copper foil with other materials when used in the manufacture of OLED screens, and also has a certain high-temperature oxidation resistance, thereby protecting the copper foil that functions as a heat sink in the OLED.

[0031] As another preferred embodiment of the present application, the coupling agent treatment is a treatment agent treatment, and the coupling agent is one or more of an epoxy-based coupling agent, an amino coupling agent and an acryl-based coupling agent, specifically, an epoxy-based coupling agent, an amino coupling agent and an acryl-based coupling agent are compounded in a ratio of 3-5:1:2. Preferably, the coupling agent is compounded in a ratio of 4:1:2 from an epoxy-based, an amino and an acryl-based treatment agent.

[0032] Specifically, the coupling agent can be a product in the prior art, such as an epoxy-based coupling agent KH-560 silane coupling agent, etc. Reference can be made to the prior art, which will not be described here.

[0033] As another preferred embodiment of the present application, the raw material of the electrolyte includes sulfuric acid and divalent copper ions; and the raw foil additive includes 400-1000 ppm hydrolyzed gelatin, 100-300 ppm sodium benzenesulfinate, 300-450 ppm hydroxyethyl cellulose and 25-40 ppm hydrochloric acid.

[0034] The electrolytic copper foil of the present application has a suitable matte roughness, excellent thickness uniformity, good heat dissipation performance and ultra-high tensile strength, and has a suitable dyne value (surface tension), and is suitable for the manufacture of OLED screens. The OLED screen is not only light and thin, has low energy consumption, high brightness, good luminous efficiency, can display pure black, and can be bent. The OLED technology has been widely applied in large screens, televisions, computer displays, mobile phones and tablets.

[0035] In addition, it needs to be explained that when the copper foil is used: 1) the copper foil light surface not only requires appropriate roughness but also requires flatness, and cannot have concave or undulating wave surface; the polishing method of the cathode roller of the copper foil production equipment needs to be optimized; 2) the traditional electrolytic copper foil has low tensile strength due to the electrolysis process, and is difficult to be applied to the production of the OLED screen; 3) the dyne value (surface tension) of the electrolytic copper foil is controlled.

[0036] It also needs to be explained that the main function of the electrolytic copper foil in the OLED screen is support and heat dissipation, and the domestic OLED screen disclosed in the prior art mainly uses the calendered copper foil or the aluminum foil. The calendered foil has high processing cost, and cannot reach a width of more than 800 mm. The aluminum foil has poor hardness, and the heat dissipation effect is far lower than that of the copper foil, and cannot meet the production requirements of the high-end OLED screen. The electrolytic copper foil prepared by the cathode roller polishing pretreatment process, the electrolytic foil production process, the roughening and solidification process, the zinc-nickel plating process, the anti-oxidation process and the treatment agent process has good tensile strength, and can meet the production requirements of the high-end OLED screen.

[0037] Preferably, the zinc-nickel plating process is that the foil treated by the solidification process is subjected to the zinc-nickel plating process, which is divided into two steps. In the first step, the electrolytic plating is carried out in an alkaline electrolyte with a temperature of 35-45 ℃, 2-4 g / L divalent nickel ions, a zinc ion concentration of 1-2 g / L, a potassium pyrophosphate ion concentration of 10-40 g / L, a pH value of 7.0-8.0 and a current density of 5-10 A / dm2. The potassium pyrophosphate mainly acts as a complexing agent to complex the nickel ions, prevent the hydrolysis of the nickel ions and reduce the deposition speed of the nickel to obtain a uniform and dense electroplated layer. In the second step, the electrolytic plating is carried out in an alkaline electrolyte with a temperature of 30-40 ℃, a zinc ion concentration of 6-8 g / L, a potassium pyrophosphate ion concentration of 20-50 g / L, a pH value of 9.0-10.0 and a current density of 4-8 A / dm2. The potassium pyrophosphate mainly acts as a complexing agent to complex the zinc ions, prevent the hydrolysis of the zinc ions and reduce the deposition speed of the zinc to obtain a uniform and dense electroplated layer. The specific selection is not limited here.

[0038] The embodiment of the present application also provides a production method of the electrolytic copper foil.

[0039] The cathode roller (after the polishing pretreatment) is subjected to electrolysis in an electrolyte to generate a foil, then the foil is roughened at a temperature of 30-40 ℃, and then is solidified at a temperature of 25-45 ℃, and then is subjected to zinc-nickel plating, chromium plating (anti-oxidation process) and coupling agent coating (treatment agent treatment), and is dried, cut and then is the finished copper foil, thereby obtaining the electrolytic copper foil.

[0040] Specifically, the electrolytic copper foil is prepared by placing a cathode roller in an electrolyte to generate green foil through electrolysis, and then the green foil is sequentially subjected to roughening, solidification, zinc-nickel plating, chromium plating and treatment agent treatment processes, so that the prepared electrolytic copper foil has good tensile strength and can meet the manufacturing requirements of high-end OLED screens.

[0041] As another preferred embodiment of the present application, in the manufacturing method of the electrolytic copper foil, the roughening includes two processes, wherein the first roughening process is to use a roughening solution containing 130-160 g / L of sulfuric acid, 10-20 g / L of divalent copper ions and 5-20 ppm of chloride ions to electroplate the green foil generated in the electrolytic green foil process under the conditions of a temperature of 30-40 DEG C and a current density of 60-80 A / dm2; and the second roughening process is to use the roughening solution to electroplate the green foil generated in the first roughening process under the conditions of a temperature of 30-40 DEG C and a current density of 40-60 A / dm2.

[0042] The roughening solution used in the roughening process contains a roughening additive, and the roughening additive contains 5-20 ppm of sodium citrate and 2-6 ppm of molybdate. The sodium citrate acts as a complexing agent to stabilize the electrolyte and ensure the uniformity of the roughening plating layer, and the molybdate improves the uniformity of plating.

[0043] As another preferred embodiment of the present application, in the manufacturing method of the electrolytic copper foil, the anti-oxidation process is to use a chromium plating anti-oxidation solution containing 1.0-1.4 g / L of hexavalent chromium ions, a pH value of 10.5-11.5, a temperature of 25-35 DEG C and a current density of 5-10 A / dm2 to electroplate the green foil, so that the chromium layer formed by the electroplating can be passivated in air and can enhance the anti-oxidation ability of the copper foil at room temperature.

[0044] As another preferred embodiment of the present application, in the manufacturing method of the electrolytic copper foil, the treatment agent treatment process is to coat the green foil after the anti-oxidation process with a coupling agent having a concentration of 0.2 g / L, and the coupling agent is a compound of an epoxy group, an amino group and an acryl group in a ratio of 4:1:2. After the treatment agent treatment process, the green foil is dried and cut to obtain the finished copper foil. The compound of the coupling agent mainly enhances the bonding property of the copper foil with other materials when the copper foil is used to manufacture an OLED screen, and also has a certain high-temperature oxidation resistance and a protective effect on the copper foil for heat dissipation in the OLED.

[0045] Preferably, the method for manufacturing the electrolytic copper foil includes a cathode roller polishing pretreatment process, an electrolytic foil production process, a roughening process, a solidification process, a zinc-nickel plating process, an oxidation prevention process, and a treatment agent process.

[0046] The present application also provides an electrolytic copper foil manufactured by the method.

[0047] The present application also provides an application of the electrolytic copper foil in manufacturing large-screen, television, computer display, mobile phone, tablet and other display products.

[0048] The technical effects of the electrolytic copper foil of the present application are further described below by listing specific embodiments.

[0049] Embodiment 1

[0050] A method for manufacturing an electrolytic copper foil, in particular a method for manufacturing an electrolytic copper foil for OLED screen, includes a cathode roller polishing pretreatment process, an electrolytic foil production process, a roughening process, a solidification process, a zinc-nickel plating process, an oxidation prevention process, and a treatment agent process.

[0051] In the present embodiment, the method for manufacturing the electrolytic copper foil is as follows:

[0052] 1) The cathode roller polishing pretreatment process is as follows: first, use a 1000-mesh silicon carbide polishing roller at a speed of 160 rpm, left and right speed of 120 rpm, load of 8%, cathode roller speed of 1.4 m / rpm, and polish for 45 minutes; then use a 2000-mesh silicon carbide polishing roller at a speed of 200 rpm, left and right speed of 160 rpm, load of 4%, cathode roller speed of 1.1 m / rpm, and polish for 50 minutes; finally, clean the roller surface.

[0053] 2) The electrolytic foil forming step is: under the conditions of temperature 32℃ and current density 33A / dm2, using 110g / L sulfuric acid and 100g / L divalent copper ions electrolyte to form the foil on the surface of the cathode roller, the electrolyte contains foil additives, the foil additives include 300ppm hydrolyzed gelatin, 150ppm sodium benzenesulfinate, 240ppm hydroxyethyl cellulose, and 25ppm hydrochloric acid.

[0054] 3) The roughening step one is: using 155g / L sulfuric acid, 18g / L divalent copper ions, and 18ppm chlorine ions roughening solution to form the foil on the surface of the cathode roller under the conditions of temperature 33℃ and current density 65A / dm2.

[0055] 4) The roughening step two is: using 155g / L sulfuric acid, 18g / L divalent copper ions, and 18ppm chlorine ions roughening solution to form the foil on the surface of the cathode roller under the conditions of temperature 33℃ and current density 55A / dm2; wherein the roughening additives contain 8ppm sodium citrate, 3ppm molybdate.

[0056] 5) The solidification step is: using 160g / L sulfuric acid, 45g / L divalent copper ions, and 18ppm chlorine ions solidification solution to form the foil on the surface of the cathode roller under the conditions of temperature 28℃ and current density 75A / dm2; wherein the solidification additives contain 12ppm sodium citrate, 1ppm alkyl quaternary ammonium salt.

[0057] 6) The zinc-nickel plating step is: using the foil treated by the solidification step to form the foil in the zinc-nickel plating solution under the conditions of temperature 37℃, 2.2g / L divalent nickel ions, zinc ion concentration 1.2g / L, potassium pyrophosphate ion concentration 18g / L, pH value 7.5, and current density 10A / dm2 in the first step, and under the conditions of temperature 32℃, zinc ion concentration 6.5g / L, potassium pyrophosphate ion concentration 30g / L, pH value 9.2, and current density 8A / dm2 in the second step.

[0058] 7) The anti-oxidation step is: using the foil treated by the anti-oxidation step to form the foil in the chromium plating anti-oxidation solution under the conditions of temperature 27℃, current density 5.5A / dm2, hexavalent chromium ions 1.1g / L, and pH value 11, and the chromium layer formed by the plating can be passivated in the air and can enhance the anti-oxidation ability of the copper foil at room temperature.

[0059] 8) The treatment agent step is: using the foil treated by the anti-oxidation step to form the foil in the treatment agent solution under the conditions of temperature 27℃, current density 5.5A / dm2, hexavalent chromium ions 1.1g / L, and pH value 11, and the chromium layer formed by the plating can be passivated in the air and can enhance the anti-oxidation ability of the copper foil at room temperature.

[0060] In the present embodiment, the copper foil sample prepared is subjected to scanning electron microscope (SEM) detection, wherein the 1000 times SEM picture of the smooth surface is as shown in FIG. 1. Figure 1 The 1000 times SEM picture of the appearance surface of the copper foil prepared in Example 1 is as shown in FIG. 2. Figure 2

[0061] It can be seen that the roughness of the smooth surface and the overall flatness of the electrolytic copper foil prepared by using the preparation method of the present embodiment are good. By using the foil additive combination formula for improving the tensile strength of the copper foil in the foil electrolysis process, and by using the foil process condition for improving the thickness uniformity of the foil, the copper foil prepared has good tensile strength and good thickness uniformity.

[0062] Example 2

[0063] A method for preparing an electrolytic copper foil, in particular a method for preparing an electrolytic copper foil for an OLED screen, which comprises a cathode roller polishing pretreatment process, an electrolytic foil production process, a roughening process 1, a roughening process 2, a solidification process, a zinc-nickel plating process, an anti-oxidation process, and a treatment agent process.

[0064] The cathode roller polishing pretreatment process is as follows: first, a 1000 mesh silicon carbide polishing roller is used at a speed of 170 rpm, a left-right speed of 130 rpm, a load of 10%, a cathode roller speed of 1.45 m / rpm, and polishing for 40 minutes; then, a 2000 mesh silicon carbide polishing roller is used at a speed of 210 rpm, a left-right speed of 170 rpm, a load of 5%, a cathode roller speed of 1.15 m / rpm, and polishing for 45 minutes; finally, the roller surface is cleaned.

[0065] The electrolytic foil production process is as follows: under the conditions of a temperature of 34℃ and a current density of 37 A / dm2, a foil is produced by electroplating a cathode roller surface using an electrolyte containing 105 g / L sulfuric acid and 95 g / L divalent copper ions, wherein the electrolyte contains a foil additive, and the foil additive comprises 500 ppm hydrolyzed gelatin, 180 ppm sodium benzenesulfinate, 280 ppm hydroxyethyl cellulose, and 23 ppm hydrochloric acid.

[0066] The roughening process 1 is as follows: the foil produced by the electrolytic foil production process is electroplated using a roughening solution containing 150 g / L sulfuric acid, 16 g / L divalent copper ions, and 16 ppm chloride ions under the conditions of a temperature of 35℃ and a current density of 70 A / dm2.

[0067] The roughening process 2 is as follows: the foil produced by the roughening process 1 is electroplated using a roughening solution containing 150 g / L sulfuric acid, 16 g / L divalent copper ions, and 16 ppm chloride ions under the conditions of a temperature of 35℃ and a current density of 50 A / dm2.

[0068] ​The roughing additive comprises 12 ppm sodium citrate and 4 ppm molybdate.

[0069] The solidification process is to use a solidification solution of 155 g / L sulfuric acid, 50 g / L divalent copper ions and 20 ppm chlorine ions to electroplate the roughened foil at a temperature of 28℃ and a current density of 70 A / dm2.

[0070] The solidification additive comprises 18 ppm sodium citrate and 2 ppm alkyl quaternary ammonium salt.

[0071] The zinc-nickel plating process is to use an alkaline electrolyte solution of 2.6 g / L divalent nickel ions, 1.4 g / L zinc ions, 27 g / L potassium pyrophosphate ions, a pH value of 7.6 and a current density of 8 A / dm2 to electroplate the foil at a temperature of 40℃. Then, an alkaline electrolyte solution of 7.0 g / L zinc ions, 37 g / L potassium pyrophosphate ions, a pH value of 9.4 and a current density of 7 A / dm2 is used to electroplate the foil at a temperature of 34℃.

[0072] The anti-oxidation process is to use a chromium plating anti-oxidation solution of 1.2 g / L hexavalent chromium ions and a pH value of 10.8 to electroplate the foil at a temperature of 30℃ and a current density of 7.0 A / dm2. The chromium layer formed by the electroplating can be passivated in air and can enhance the anti-oxidation ability of the copper foil at room temperature.

[0073] The treatment agent process is to coat the foil after the anti-oxidation process with a coupling agent at a concentration of 0.2 g / L. The coupling agent is a compound of epoxy, amino and acryl treatment agents at a ratio of 4:1:2. After the treatment agent process, the foil is dried and cut to obtain the finished copper foil.

[0074] Example 3

[0075] The method for manufacturing an electrolytic copper foil, in particular, a method for manufacturing an electrolytic copper foil for an OLED screen, includes a cathode roller polishing pretreatment process, an electrolytic foil process, a roughening process, a solidification process, a zinc-nickel plating process, an anti-oxidation process and a treatment agent process.

[0076] The cathode roller polishing pretreatment process is to first use a 1000-mesh silicon carbide polishing roller at a speed of 180 rpm, a left-right speed of 140 rpm and a load of 13% with a cathode roller speed of 1.5 m / rpm for 35 minutes. Then, a 2000-mesh silicon carbide polishing roller is used at a speed of 220 rpm, a left-right speed of 180 rpm and a load of 6% with a cathode roller speed of 1.20 m / rpm for 40 minutes. Finally, the roller surface is cleaned.

[0077] The electrolytic green foil process is: under the conditions of temperature 36℃ and current density 40A / dm2, using 100g / L sulfuric acid and 90g / L divalent copper ion electrolyte to electroplate green foil on the surface of cathode roller, the electrolyte contains green foil additive, the green foil additive includes 700ppm hydrolyzed gelatin, 220ppm sodium benzenesulfinate, 350ppm hydroxyethyl cellulose, and 26ppm hydrochloric acid.

[0078] The roughening first process is: using 140g / L sulfuric acid, 14g / L divalent copper ion, and 12ppm chlorine ion roughening liquid to electroplate the green foil generated by the electrolytic green foil process under the conditions of temperature 37℃ and current density 65A / dm2;

[0079] The roughening second process is: using 140g / L sulfuric acid, 14g / L divalent copper ion, and 12ppm chlorine ion roughening liquid to electroplate the green foil generated by the roughening first process under the conditions of temperature 37℃ and current density 45A / dm2;

[0080] The roughening additive contains 15ppm sodium citrate and 5ppm molybdate.

[0081] The solidification process is: using 150g / L sulfuric acid, 45g / L divalent copper ion, and 22ppm chlorine ion solidification liquid to electroplate the green foil processed by the roughening second process under the conditions of temperature 35℃ and current density 65A / dm2;

[0082] The solidification additive contains 20ppm sodium citrate and 3ppm alkyl quaternary ammonium salt.

[0083] The zinc-nickel plating process is: the green foil processed by the solidification process is subjected to the zinc-nickel plating process, the first step is electroplating in an alkaline electrolyte with temperature 42℃, 3.0g / L divalent nickel ion, zinc ion concentration 1.6g / L, potassium pyrophosphate ion concentration 32g / L, pH value 7.7, and current density 7A / dm2. The second step is electroplating in an alkaline electrolyte with temperature 37℃, zinc ion concentration 7.5g / L, potassium pyrophosphate ion concentration 40g / L, pH value 9.6, and current density 6A / dm2.

[0084] The anti-oxidation process is: electroplating in a chromium plating anti-oxidation liquid with temperature 32℃, current density 8.0A / dm2, hexavalent chromium ion 1.3g / L, and pH value 10.7, the electroplated chromium layer can be passivated in air and can strengthen the anti-oxidation ability of copper foil at room temperature.

[0085] The treatment agent process is to coat the foil after the oxidation prevention process with a coupling agent with a concentration of 0.2 g / L, the coupling agent being a compound of epoxy, amino and acryl type in a ratio of 4:1:2. After the treatment agent process, drying and slitting, the copper foil is the finished product

[0086] Example 4

[0087] A method for manufacturing an electrolytic copper foil, in particular a method for manufacturing an electrolytic copper foil for an OLED screen, comprising the following steps: a cathode roller polishing pretreatment process, an electrolytic foil production process, a roughening process 1, a roughening process 2, a solidification process, a zinc-nickel plating process, an oxidation prevention process, and a treatment agent process.

[0088] The cathode roller polishing pretreatment process is as follows: first, using a 1000-mesh silicon carbide polishing roller, the speed is 200 rpm, the left and right speed is 150 rpm, the load is 15%, the cathode roller speed is 1.6 m / rpm, and the polishing time is 30 minutes; then using a 2000-mesh silicon carbide polishing roller, the speed is 230 rpm, the left and right speed is 190 rpm, the load is 8%, the cathode roller speed is 1.25 m / rpm, and the polishing time is 35 minutes; finally, cleaning the roller surface.

[0089] The electrolytic foil production process is as follows: under the conditions of a temperature of 39℃ and a current density of 45 A / dm2, using an electrolyte of 90 g / L sulfuric acid and 85 g / L divalent copper ions to electroplate a foil on the surface of the cathode roller, the electrolyte containing a foil additive, the foil additive including 900 ppm hydrolyzed gelatin, 280 ppm sodium benzenesulfinate, 420 ppm hydroxyethyl cellulose, and 30 ppm hydrochloric acid.

[0090] The roughening process 1 is as follows: using a roughening solution of 135 g / L sulfuric acid, 12 g / L divalent copper ions, and 10 ppm chloride ions to electroplate the foil produced in the electrolytic foil production process under the conditions of a temperature of 39℃ and a current density of 60 A / dm2.

[0091] The roughening process 2 is as follows: using a roughening solution of 135 g / L sulfuric acid, 12 g / L divalent copper ions, and 10 ppm chloride ions to electroplate the foil produced in the roughening process 1 under the conditions of a temperature of 39℃ and a current density of 40 A / dm2.

[0092] The roughening additive contains 18 ppm sodium citrate and 5.5 ppm molybdate.

[0093] The solidification process is as follows: using a solidification solution of 145 g / L sulfuric acid, 42 g / L divalent copper ions, and 24 ppm chloride ions to electroplate the foil processed in the roughening process 2 under the conditions of a temperature of 35℃ and a current density of 60 A / dm2.

[0094] The solidification additive comprises 23 ppm sodium citrate and 4 ppm alkyl quaternary ammonium salt.

[0095] The galvanizing nickel process is to perform the galvanizing nickel process on the raw foil treated by the solidification process.

[0096] The first step is to perform the electroplating in an alkaline electrolyte with the temperature of 45℃, the divalent nickel ion concentration of 3.7 g / L, the zinc ion concentration of 1.8 g / L, the potassium pyrophosphate ion concentration of 37 g / L, the pH value of 7.8 and the current density of 6 A / dm2.

[0097] The second step is to perform the electroplating in an alkaline electrolyte with the temperature of 40℃, the zinc ion concentration of 8.0 g / L, the potassium pyrophosphate ion concentration of 45 g / L, the pH value of 9.8 and the current density of 5 A / dm2.

[0098] The anti-oxidation process is to perform the electroplating in a chromium plating anti-oxidation solution with the temperature of 35℃, the current density of 10.0 A / dm2, the hexavalent chromium ion of 1.38 g / L and the pH value of 10.5, so that the chromium layer can be passivated in the air and the anti-oxidation ability of the copper foil at normal temperature can be enhanced.

[0099] The treatment agent process is to coat the raw foil after the anti-oxidation process with the coupling agent with the concentration of 0.2 g / L, and the coupling agent is the epoxy, amino and acryl-based treatment agent compounded according to the ratio of 4:1:2. After the treatment agent process, the raw foil is dried and cut to be the finished copper foil.

[0100] Example 5

[0101] An electrolytic copper foil for OLED screen, specifically, a raw foil is generated by electrolysis in an electrolyte with a cathode roller, and then the raw foil is sequentially subjected to roughening, solidification, galvanizing nickel, chromium plating and coupling agent coating processes. The electrolyte used in the electrolysis contains a raw foil additive, and the raw foil additive includes 200 ppm hydrolyzed gelatin, 100 ppm sodium benzenesulfinate, 200 ppm hydroxyethyl cellulose and 20 ppm hydrochloric acid. The sodium benzenesulfinate and the hydroxyethyl cellulose change the copper foil lattice, and improve and stabilize the tensile strength and elongation of the copper foil.

[0102] In the present embodiment, the method for manufacturing the electrolytic copper foil is the same as that in Example 1, which is not described herein.

[0103] Example 6

[0104] An electrolytic copper foil for OLED screen, specifically, a green foil is generated by electrolysis with a cathode roller in electrolyte, and then the green foil is sequentially subjected to roughening, solidification, zinc-nickel plating, chromium plating, and coupling agent coating processes to be made, wherein the electrolyte used in the electrolysis contains a green foil additive, and the green foil additive comprises 1000 ppm of hydrolyzed gelatin, 300 ppm of sodium benzenesulfinate, 500 ppm of hydroxyethyl cellulose, and 40 ppm of hydrochloric acid.

[0105] In the present embodiment, the manufacturing method of the electrolytic copper foil is referred to the manufacturing method of the electrolytic copper foil of Embodiment 1, and thus is not described herein.

[0106] Embodiment 7

[0107] Compared with Embodiment 1, the green foil additive comprises 300 ppm of hydrolyzed gelatin, 150 ppm of sodium benzenesulfinate, 420 ppm of hydroxyethyl cellulose, and 30 ppm of hydrochloric acid, and the other conditions are the same as those of Embodiment 1.

[0108] Embodiment 8

[0109] Compared with Embodiment 1, the green foil additive comprises 900 ppm of hydrolyzed gelatin, 280 ppm of sodium benzenesulfinate, 240 ppm of hydroxyethyl cellulose, and 23 ppm of hydrochloric acid, and the other conditions are the same as those of Embodiment 1.

[0110] Performance detection

[0111] The green foils prepared by electrolysis in Embodiments 1-4 are subjected to performance detection, specifically, the roughness, tensile strength, and dyne value of the green foils are detected, and the data are shown in Table 1.

[0112] Table 1: detection result table

[0113] Group Tensile strength kgf / mm2 High temperature elongation (%) Example 1 50.7 6.2 Example 2 51.3 6.6 Example 3 51.2 6.5 Example 4 50.9 6.3

[0114] As can be seen from the data in Table 1, the green foils prepared by electrolysis using the manufacturing method of the electrolytic copper foil provided in the embodiments have good tensile strength, which can reach more than 50 kgf / mm2.

[0115] In order to further detect the effect of the electrolytic copper foil, the roughness, tensile strength, oxidation resistance, and dyne value of the electrolytic copper foils finally prepared by the manufacturing methods in Embodiments 1-4 are detected, and the specific performance detection results are shown in Table 2.

[0116] Table 2: performance detection result table

[0117]

[0118]

[0119] As can be seen from the data in Table 2, the electrolytic copper foil prepared by using the method for manufacturing electrolytic copper foil provided by the embodiment of the present application has not only good tensile strength, but also good elongation. The method for controlling the roughness of the smooth surface and the overall flatness of the electrolytic copper foil by cathode roller polishing pretreatment process, the foil-making additive combination formula for improving the tensile strength of the copper foil in the foil-making electrolysis process, the foil-making process condition for improving the thickness uniformity of the foil, the process condition of the zinc-nickel plating process, the treatment agent formula for improving the bonding force of the copper foil with other components of the OLED and the oxidation resistance of the copper foil are all key points and points to be protected in the embodiment of the present application.

[0120] According to the above results, it can be seen that the embodiment of the present application has the following beneficial effects: the electrolytic copper foil of the embodiment of the present application has good thickness uniformity and surface flatness, and when used in an OLED screen, the screen display quality and touch screen effect are good; the tensile strength of the electrolytic copper foil of the present application is greater than that of the existing electrolytic copper foil, the processing cost is 50% or less of that of the rolled copper foil, and the width of the electrolytic copper foil can be greater than 800 mm, which cannot be achieved by the rolled copper foil, so that a large-screen OLED screen can be manufactured; when the electrolytic copper foil of the embodiment of the present application is used in an OLED screen, the heat dissipation effect is good. Moreover, the manufacturing method provided by the embodiment of the present application is simple and has a broad market prospect. It should be noted that the hydrolyzed gelatin, sodium benzenesulfinate and hydroxyethyl cellulose in the present application are all products of existing manufacturers. They can be selected according to the needs, and will not be described here.

[0121] The preferred embodiments of the present application are described in detail above, the basic principles, main features and advantages of the present application are described. However, it should be understood by those skilled in the art that the embodiments of the present application are not limited to the above-described embodiments, the above-described embodiments and descriptions in the specification are only preferred examples of the present application, and are not intended to limit the present application. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the purpose of the embodiments of the present application. Here, it is not necessary and impossible to exhaust all the embodiments. The obvious changes or changes derived therefrom are still within the protection scope of the embodiments of the present application.

Claims

1. An electrolytic copper foil, characterized in that, The electrolytic copper foil is produced by electrolyzing a cathode roller in an electrolyte to generate green foil, and then the green foil is successively subjected to roughening, curing, zinc-nickel plating, chromium plating and coating with a coupling agent; wherein, the electrolyte contains green foil additives, and the raw materials of the green foil additives include hydrolyzed gelatin, sodium benzenesulfonate, hydroxyethyl cellulose and hydrochloric acid. The cathode roller also includes a polishing pretreatment process before electrolysis. The raw materials of the raw foil additive include 200-1000ppm hydrolyzed gelatin, 100-300ppm sodium benzenesulfinate, 200-500ppm hydroxyethyl cellulose and 20-40ppm hydrochloric acid.

2. The electrolytic copper foil according to claim 1, characterized in that, The raw materials for the foil additive include 300-900ppm hydrolyzed gelatin, 150-280ppm sodium benzenesulfonate, 240-420ppm hydroxyethyl cellulose, and 23-30ppm hydrochloric acid.

3. The electrolytic copper foil according to claim 1, characterized in that, The roughening process uses a roughening solution containing a roughening additive, wherein the roughening additive contains 5-20 ppm sodium citrate and 2-6 ppm molybdate.

4. The electrolytic copper foil according to claim 1, characterized in that, The curing liquid used for curing contains curing additives, wherein the curing additives contain 10-25 ppm sodium citrate and 0.5-5 ppm alkyl quaternary ammonium salts.

5. The electrolytic copper foil according to claim 1, characterized in that, The coupling agent is any one or more of epoxy-based coupling agents, amino-based coupling agents, and propylene-based coupling agents.

6. A method for manufacturing electrolytic copper foil as described in any one of claims 1-5, characterized in that, Includes the following steps: The cathode roller is electrolyzed in an electrolyte to generate a green foil. The green foil is then roughened at a temperature of 30-40℃, cured at a temperature of 25-45℃, and then plated with zinc and nickel, chromium, and coated with a coupling agent. After drying and slitting, electrolytic copper foil is obtained.

7. An electrolytic copper foil prepared by the method of claim 6.

8. The application of an electrolytic copper foil as described in claim 1, 2, 3, 4, or 5 in the preparation of an OLED screen.

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