CN116103707A - Electrolytic copper foil and manufacturing method and application thereof - Google Patents

Electrolytic copper foil and manufacturing method and application thereof Download PDF

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CN116103707A
CN116103707A CN202211726668.5A CN202211726668A CN116103707A CN 116103707 A CN116103707 A CN 116103707A CN 202211726668 A CN202211726668 A CN 202211726668A CN 116103707 A CN116103707 A CN 116103707A
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copper foil
electrolytic copper
foil
raw
roughening
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汪光志
郑小伟
许衍
汪巍
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Hefei Tongguan Electronic Copper Foil Co ltd
Tongling Tongguan Electronic Copper Foil Co ltd
Anhui Tongguan Copper Foil Group Co ltd
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Hefei Tongguan Electronic Copper Foil Co ltd
Tongling Tongguan Electronic Copper Foil Co ltd
Anhui Tongguan Copper Foil Group Co ltd
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Priority to CN202211726668.5A priority Critical patent/CN116103707A/en
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    • 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
    • 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
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • 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
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
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    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
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    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
    • 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
    • H05K7/00—Constructional details common to different types of electric apparatus
    • H05K7/20—Modifications to facilitate cooling, ventilating, or heating

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Abstract

The embodiment of the invention relates to the technical field of OLED display, and particularly discloses an electrolytic copper foil, a manufacturing method and application thereof. The electrolytic copper foil prepared by the method has good tensile strength and can meet the manufacturing requirements of high-end OLED screens. The raw materials of the raw foil additive comprise hydrolyzed gelatin, sodium benzene sulfinate, hydroxyethyl cellulose and hydrochloric acid, and the tensile strength of the copper foil is improved through the raw foil electrolysis process, so that the problems that the tensile strength of the conventional electrolytic copper foil is low and the manufacturing requirement of an OLED screen cannot be met are solved. Moreover, the electrolytic copper foil provided by the embodiment of the invention has simple manufacturing method and wide market prospect.

Description

Electrolytic copper foil and manufacturing method and application thereof
Technical Field
The embodiment of the invention belongs to the technical field of OLED display, and particularly relates to an electrolytic copper foil, a manufacturing method and application thereof.
Background
Along with the continuous development of technology and the gradual progress of display technology, the application range of OLED screens is also increasing in the market at present. Among them, OLED (Organic Light-Emitting Diode) is also called an Organic Light-Emitting Diode, and an OLED screen formed by the Organic Light-Emitting Diode is used as a product, and can be used as a display screen in some electronic devices such as a tablet, a mobile phone, a computer, etc., so that the Organic Light-Emitting Diode is a display with very good performance.
In the manufacture of OLED screens, foils such as copper foil and aluminum foil are usually used, and their main functions in OLED screens are supporting and heat dissipation. However, the prior art solutions described above have the following drawbacks: the traditional electrolytic copper foil in the prior art has low tensile strength due to the electrolytic process, is difficult to be suitable for manufacturing the OLED screen, and cannot meet the manufacturing requirement of the high-end OLED screen.
Disclosure of Invention
The embodiment of the invention aims to provide an electrolytic copper foil, which solves the problems that the tensile strength of the conventional electrolytic copper foil provided in the background art is low and the manufacturing requirement of an OLED screen cannot be met.
In order to achieve the above object, the embodiment of the present invention provides the following technical solutions:
an electrolytic copper foil is prepared by putting a cathode roller into electrolyte to electrolyze to generate a raw foil, and then sequentially coarsening, solidifying, zinc-nickel plating, chromium plating and coupling agent coating the raw foil; wherein the electrolyte contains a raw foil additive, and raw materials of the raw foil additive comprise hydrolyzed gelatin, sodium benzene sulfinate, hydroxyethyl cellulose and hydrochloric acid.
Preferably, the raw materials of the raw foil additive comprise 200-1000ppm of hydrolyzed gelatin, 100-300ppm of sodium benzene sulfinate, 200-500ppm of hydroxyethyl cellulose and 20-40ppm of hydrochloric acid.
Preferably, the raw materials of the raw foil additive comprise 300-900ppm of hydrolyzed gelatin, 150-280ppm of sodium benzene sulfinate, 240-420ppm of hydroxyethyl cellulose and 23-30ppm of hydrochloric acid.
Another object of the embodiment of the present invention is to provide a method for manufacturing an electrolytic copper foil, which includes the following steps:
and (3) electrolyzing the cathode roller in electrolyte to generate raw foil, coarsening the raw foil at the temperature of 30-40 ℃, solidifying at the temperature of 25-45 ℃, then carrying out zinc-nickel plating, chromium plating, coating a coupling agent, drying and cutting to obtain the electrolytic copper foil.
Another object of the embodiment of the present invention is to provide an electrolytic copper foil prepared by the above method for manufacturing an electrolytic copper foil.
The embodiment of the invention also aims to provide an application of the electrolytic copper foil in preparation of an OLED screen.
Compared with the prior art, the embodiment of the invention has the beneficial effects that:
compared with the prior art, the electrolytic copper foil provided by the embodiment of the invention is prepared by placing the cathode roller in the electrolyte to electrolyze to generate the green foil, and then sequentially carrying out the procedures of roughening, curing, zinc-nickel plating, chromium plating, coupling agent coating and the like on the green foil. The raw materials of the raw foil additive comprise hydrolyzed gelatin, sodium benzene sulfinate, hydroxyethyl cellulose and hydrochloric acid, and the tensile strength of the copper foil is improved through the raw foil electrolysis process, so that the problems that the tensile strength of the conventional electrolytic copper foil is low and the manufacturing requirement of an OLED screen cannot be met are solved. Moreover, the manufacturing method of the electrolytic copper foil provided by the embodiment of the invention is simple, can be used for preparing other types of copper foil, and has wide market prospect.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following description will briefly introduce the drawings that are needed in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are only some embodiments of the present invention.
FIG. 1 is a 1000-fold SEM image of the smooth surface of a copper foil according to one embodiment of the present invention.
Fig. 2 is a 1000-fold SEM image of the appearance of a copper foil according to an embodiment of the present invention.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clearly apparent, the technical schemes in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention and the accompanying drawings. It will be apparent that the following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the present invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the spirit of the embodiments of the invention. These are all within the scope of embodiments of the present invention.
Specific implementations of the invention are described in detail below in connection with specific embodiments.
Firstly, it should be noted that in the prior art, in the manufacture of OLED screens, foils such as copper foil and aluminum foil are generally used, and the main function of the foils in OLED screens is supporting and heat dissipation. Copper foil is generally classified into rolled copper foil and electrolytic copper foil, wherein the electrolytic copper foil has a suitable dyne value (surface tension) and is generally suitable for the production of general OLED panels. However, the tensile strength of the traditional electrolytic copper foil is low due to the electrolytic process, and the manufacturing requirement of the high-end OLED screen cannot be met.
Therefore, in order to solve the problem that the tensile strength of the existing electrolytic copper foil in the prior art is low, the manufacturing requirement of the OLED screen cannot be met. The embodiment of the invention provides an electrolytic copper foil, and a manufacturing method and application thereof. The electrolytic copper foil is particularly suitable for OLED screens, the electrolytic copper foil is particularly prepared by placing a cathode roller in electrolyte to electrolyze to generate raw foil, and then sequentially carrying out processes such as roughening, curing, zinc-nickel plating, chromium plating, coupling agent coating and the like on the raw foil. Wherein the coupling agent is used as a treating agent, namely the coupling agent process is also the treating agent process.
As another preferable embodiment of the invention, the cathode roller further comprises a step of performing polishing pretreatment to control the surface roughness of the cathode roller to ra=0.25±0.1 μm before the cathode roller is put into the electrolyte.
As another preferable embodiment of the invention, the cathode roller polishing pretreatment procedure is as follows: the surface of the cathode roll was polished with a silicon carbide polishing roll to control the surface roughness to ra=0.25±0.1 μm. The polishing pretreatment method comprises three steps, namely, a 1000-mesh silicon carbide polishing roller is used, the rotating speed is 160-200 rpm, the left and right speeds are 120-160 rpm, the load is 8-16%, the rotating speed of a cathode roller is 1.4-1.6 m/rpm, and the polishing is carried out for 30-45 minutes; polishing with 2000 mesh silicon carbide polishing roller at 200-240 rpm and 160-200 rpm, with load of 4-8% and cathode roller at 1.1-1.3 m/rpm for 35-50 min; finally, cleaning the roller surface, and carrying out polishing pretreatment again after 4-8 days of production, wherein the production time between two polishing pretreatment is called a polishing period.
As another preferable mode of the embodiment of the invention, the electrolyte used for the electrolysis comprises a raw foil additive, wherein the raw foil additive comprises 200-1000ppm of hydrolyzed gelatin, 100-300ppm of sodium benzene sulfinate, 200-500ppm of hydroxyethyl cellulose and 20-40ppm of hydrochloric acid. Sodium benzene sulfinate and hydroxyethyl cellulose play a role in changing the crystal lattice of the copper foil, and improving and stabilizing the tensile strength and the elongation of the copper foil.
As another preferred embodiment of the invention, the electrolyte used for the electrolysis comprises a raw foil additive, wherein the raw foil additive comprises 300-900ppm of hydrolyzed gelatin, 150-280ppm of sodium benzene sulfinate, 240-420ppm of hydroxyethyl cellulose and 23-30ppm of hydrochloric acid.
Further preferably, in the electrolytic foil formation step, the electrolytic foil formation step includes: electroplating at 30-40deg.C and current density of 30-50A/dm2 with 65-115g/L sulfuric acid and 85-105g/L cupric ion electrolyte to obtain green foil on the surface of cathode roller, wherein the electrolyte contains green foil additive comprising 200-1000ppm hydrolyzed gelatin, 100-300ppm sodium benzene sulfinate, 200-500ppm hydroxyethyl cellulose, and 20-40ppm hydrochloric acid. Sodium benzene sulfinate and hydroxyethyl cellulose play a role in changing the crystal lattice of the copper foil, and improving and stabilizing the tensile strength and the elongation of the copper foil.
As another preferable mode of the embodiment of the invention, the roughening solution used for roughening comprises a roughening additive, wherein the roughening additive comprises 5-20ppm of sodium citrate and 2-6ppm of molybdate. The sodium citrate plays a role of a complexing agent, stabilizes the electrolyte, ensures uniformity of the coarsened plating layer, and improves uniform plating property by molybdate.
As another preferable mode of the embodiment of the invention, the curing liquid used for curing comprises a curing additive, and the curing additive comprises 10-25ppm of sodium citrate and 0.5-5ppm of alkyl quaternary ammonium salt.
Preferably, the curing process comprises the following steps: electroplating the coarsened green foil at 25-45deg.C and current density of 60-80A/dm2 with 140-170g/L sulfuric acid, 40-60g/L cupric ion, and 15-25ppm chloride ion.
As another preferred embodiment of the present invention, the coupling agent is coated. And (3) coating the raw foil with a coupling agent with the concentration of 0.2g/L, and drying and cutting to obtain the finished copper foil. The copper foil is mainly used for enhancing the combination property of the copper foil with other materials when being used for manufacturing an OLED screen, has a certain high-temperature oxidation resistance to the copper foil, and has a protection effect on the copper foil with a heat dissipation function in an OLED.
As another preferable example of the present invention, 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-based coupling agent, and an acryl-based coupling agent, specifically, the epoxy-based coupling agent, the amino-based coupling agent, and the acryl-based coupling agent are mixed according to 3-5:1:2, and is compounded according to the proportion. Preferably, the coupling agent is epoxy, amino and propenyl treating agent according to 4:1:2, and is compounded according to the proportion.
Specifically, the coupling agent may be a product in the prior art, for example, an epoxy coupling agent KH-560 silane coupling agent, etc., and reference may be made to the prior art, which is not described herein.
As another preferable example of the embodiment of the invention, the raw materials of the electrolyte include sulfuric acid and cupric ions; the raw foil additive comprises 400-1000ppm of hydrolyzed gelatin, 100-300ppm of sodium benzene sulfinate, 300-450ppm of hydroxyethyl cellulose and 25-40ppm of hydrochloric acid.
The electrolytic copper foil provided by the embodiment of the invention has proper smooth surface roughness, excellent thickness uniformity, good heat dissipation performance and ultrahigh tensile strength, and has proper dyne value (surface tension), and is suitable for manufacturing OLED screens. The OLED screen is light and thin, low in energy consumption, high in brightness and good in luminous efficiency, can display pure black and can be bent, and OLED technology is widely applied to the fields of large screens, televisions, computer monitors, mobile phones, flat plates and the like.
In addition, when a copper foil is used: 1) The smooth surface of the copper foil is required to have proper roughness and flat surface, and a concave or high-low wavy surface is not obtained; the polishing method of the cathode roller of copper foil production equipment needs to be optimized; 2) The traditional electrolytic copper foil has lower tensile strength due to the electrolytic process, and is difficult to be suitable for manufacturing an OLED screen; 3) The dyne value (surface tension) of the electrolytic copper foil is controlled.
It should be further noted that the main function of the electrolytic copper foil in the OLED screen is supporting and radiating, the domestic OLED screen disclosed in the prior art mainly uses rolled copper foil or aluminum foil, the rolled foil has high processing cost, the width of more than 800mm cannot be achieved, the aluminum foil has poor hardness, the radiating effect is far lower than that of the copper foil, and the manufacturing requirement of the high-end OLED screen cannot be met. According to the embodiment of the invention, the prepared electrolytic copper foil has good tensile strength through the steps of cathode roller polishing pretreatment, electrolytic foil production, roughening, curing, zinc and nickel plating, oxidation prevention, treating agent treatment and the like, and can meet the manufacturing requirements of high-end OLED screens.
Preferably, the zinc-nickel plating process comprises the following steps: the raw foil treated by the curing process is subjected to a zinc and nickel plating process, and the zinc and nickel plating process is divided into two steps, wherein the first step is to plate in alkaline electrolyte with the temperature of 35-45 ℃, the divalent nickel ion concentration of 2-4g/L, the zinc ion concentration of 1-2g/L, the potassium pyrophosphate ion concentration of 10-40g/L, the pH value of 7.0-8.0 and the current density of 5-10A/dm < 2 >, and the potassium pyrophosphate mainly acts as a complexing agent to complex nickel ions, prevent nickel ions from hydrolyzing, and reduce the deposition rate of nickel so as to obtain a uniform and compact electroplated layer. And secondly, electroplating is carried out in alkaline electrolyte with the temperature of 30-40 ℃, the zinc ion concentration of 6-8g/L, the potassium pyrophosphate ion concentration of 20-50g/L and the pH value of 9.0-10.0 and the current density of 4-8A/dm < 2 >, and the potassium pyrophosphate mainly acts as a complexing agent to complex the zinc ions, prevent the zinc ions from hydrolyzing and reduce the deposition rate of zinc so as to obtain a uniform and compact electroplated layer. Specifically, the selection is made according to need, and is not limited herein.
The embodiment of the invention also provides a manufacturing method of the electrolytic copper foil, which comprises the following steps:
and (3) electrolyzing the cathode roller (subjected to polishing pretreatment) in an electrolyte to generate a green foil, coarsening the green foil at the temperature of 30-40 ℃, solidifying at the temperature of 25-45 ℃, then carrying out zinc-nickel plating, chromium plating (anti-oxidation process) and coupling agent coating (treating agent treatment), drying and cutting to obtain a finished product copper foil, and obtaining the electrolytic copper foil.
Specifically, the electrolytic copper foil is prepared by placing a cathode roller in electrolyte to electrolyze to generate a raw foil, and then sequentially carrying out processes such as roughening, curing, zinc-nickel plating, chromium plating, treating agent treatment and the like on the raw foil.
As another preferable aspect of the embodiment of the invention, in the method for manufacturing an electrolytic copper foil, the roughening includes two steps, wherein one step of roughening is: electroplating the raw foil generated by the electrolytic foil production process under the conditions of the temperature of 30-40 ℃ and the current density of 60-80A/dm < 2 >, and using 130-160g/L sulfuric acid, 10-20g/L bivalent copper ions and roughening liquid of 5-20ppm chloride ions; the roughening step two is as follows: electroplating the raw foil produced by the roughening step under the conditions of the temperature of 30-40 ℃ and the current density of 40-60A/dm < 2 >, and using 130-160g/L sulfuric acid, 10-20g/L bivalent copper ions and a roughening solution of 5-20ppm chloride ions.
Wherein the roughening liquid used for roughening comprises a roughening additive, and the roughening additive comprises 5-20ppm sodium citrate and 2-6ppm molybdate. The sodium citrate plays a role of a complexing agent, stabilizes the electrolyte, ensures uniformity of the coarsened plating layer, and improves uniform plating property by molybdate.
In another preferred embodiment of the present invention, in the method for producing an electrolytic copper foil, the oxidation preventing step comprises: electroplating is carried out in chromium plating anti-oxidation liquid with the temperature of 25-35 ℃, the current density of 5-10A/dm < 2 >, the hexavalent chromium ions of 1.0-1.4g/L and the pH value of 10.5-11.5, and the electroplated chromium layer can be passivated in air and can strengthen the anti-oxidation capability of the copper foil at normal temperature.
In another preferred embodiment of the present invention, in the method for producing an electrolytic copper foil, the treating agent treatment step comprises: the method comprises the steps of coating the raw foil after the anti-oxidation process with a coupling agent with the concentration of 0.2g/L, wherein the coupling agent is an epoxy group, an amino group and an propenyl treating agent according to the following weight ratio of 4:1:2, and is compounded according to the proportion. And after the working procedure of the treating agent, drying and cutting are carried out to obtain the finished copper foil. The compounded treating agent is mainly used for enhancing the combination property of the copper foil with other materials when the copper foil is used for manufacturing an OLED screen, and has a certain high-temperature oxidation resistance to the copper foil and a protection effect to the copper foil with a heat dissipation function in an OLED.
Preferably, the method for manufacturing the electrolytic copper foil comprises the steps of a cathode roller polishing pretreatment process, an electrolytic foil producing process, a first roughening process, a second roughening process, a curing process, a zinc-nickel plating process, an oxidation preventing process and a treating agent process. The method comprises the following steps that 1) the thickness uniformity and the surface flatness of the existing electrolytic copper foil used for the PCB and the lithium battery are insufficient, and the display quality and the touch screen effect can be influenced when the electrolytic copper foil is used for an OLED screen; 2) The tensile strength of the existing electrolytic copper foil is lower due to process factors, and the tensile strength of the rolled foil meets the requirements, but the production process flow is complex, the processing cost is more than twice that of the electrolytic copper foil, the limit width can only reach 800mm at present, and the manufacturing of a large-screen OLED can not be met; 3) The aluminum foil is poor in hardness, the heat dissipation effect is far lower than that of the copper foil, the corona value is insufficient, and the manufacturing requirement of the high-end OLED screen cannot be met. The electrolytic copper foil prepared by the polishing pretreatment process, the electrolytic foil production process, the first roughening process, the second roughening process, the curing process, the zinc-nickel plating process, the oxidation prevention process and the treating agent process has good tensile strength, and can meet the requirement of manufacturing the large-screen OLED.
The embodiment of the invention also provides the electrolytic copper foil prepared by the preparation method of the electrolytic copper foil.
The embodiment of the invention also provides application of the electrolytic copper foil in preparing large screens, televisions, computer monitors, mobile phones and flat panels and other various display products. In particular for the preparation of OLED screens.
The technical effects of the electrolytic copper foil according to the embodiment of the present invention will be further described below by referring to specific examples.
Example 1
The method for manufacturing the electrolytic copper foil comprises the steps of a cathode roller polishing pretreatment process, an electrolytic foil production process, a first roughening process, a second roughening process, a curing process, a zinc-nickel plating process, an oxidation prevention process and a treating agent process.
In this embodiment, the method for manufacturing the electrolytic copper foil is specifically as follows:
1) The polishing pretreatment process of the cathode roller comprises the following steps: firstly, polishing a 1000-mesh silicon carbide polishing roller with the rotating speed of 160rpm, the speed of about 120rpm and the load of 8 percent, and the rotating speed of a cathode roller of 1.4m/rpm for 45 minutes; then a 2000 mesh silicon carbide polishing roller is used, the rotating speed is 200rpm, the speed is about 160rpm, the load is 4 percent, the rotating speed of the cathode roller is 1.1m/rpm, and the polishing is carried out for 50 minutes; and finally, cleaning the roller surface.
2) The electrolytic foil production process comprises the following steps: electroplating at a temperature of 32℃and a current density of 33A/dm2 on the surface of the cathode roll using an electrolyte of 110g/L sulfuric acid and 100g/L cupric ions to produce a green foil, the electrolyte comprising a green foil additive comprising 300ppm hydrolyzed gelatin, 150ppm sodium benzene sulfinate, 240ppm hydroxyethyl cellulose, and 25ppm hydrochloric acid.
3) The roughening process comprises the following steps: electroplating the green foil produced by the electrolytic foil producing step at a temperature of 33 ℃ and a current density of 65A/dm2 by using a roughening solution of 155g/L sulfuric acid, 18g/L cupric ion and 18ppm chloride ion;
4) The roughening step two is as follows: electroplating the raw foil produced in the roughening step at a temperature of 33 ℃ and a current density of 55A/dm2 by using a roughening solution of 155g/L sulfuric acid, 18g/L cupric ion and 18ppm chloride ion; wherein the coarsening additive comprises 8ppm sodium citrate and 3ppm molybdate.
5) The curing procedure is as follows: electroplating the green foil processed by the roughening two steps at the temperature of 28 ℃ and the current density of 75A/dm2 by using a curing solution of 160g/L sulfuric acid, 45g/L cupric ions and 18ppm chloride ions; wherein the curing additive comprises 12ppm sodium citrate, 1ppm alkyl quaternary ammonium salt.
6) The zinc and nickel plating process comprises the following steps: and (3) carrying out a zinc and nickel plating process on the green foil treated by the curing process, wherein the first step is to carry out electroplating in an alkaline electrolyte with the temperature of 37 ℃, the divalent nickel ion concentration of 2.2g/L, the zinc ion concentration of 1.2g/L, the potassium pyrophosphate ion concentration of 18g/L, the pH value of 7.5 and the current density of 10A/dm < 2 >. And in the second step, electroplating is carried out in alkaline electrolyte with the temperature of 32 ℃, the zinc ion concentration of 6.5g/L, the potassium pyrophosphate ion concentration of 30g/L, the pH value of 9.2 and the current density of 8A/dm 2.
7) The oxidation prevention procedure is as follows: electroplating is carried out in chromium plating anti-oxidation liquid with the temperature of 27 ℃ and the current density of 5.5A/dm < 2 >, hexavalent chromium ions of 1.1g/L and the pH value of 11, and the electroplated chromium layer can be passivated in air, so that the anti-oxidation capability of the copper foil at normal temperature can be enhanced.
8) The working procedure of the treating agent is as follows: the method comprises the steps of coating the raw foil after the anti-oxidation process with a coupling agent with the concentration of 0.2g/L, wherein the coupling agent is an epoxy group, an amino group and an propenyl treating agent according to the following weight ratio of 4:1:2, and is compounded according to the proportion. And after the working procedure of the treating agent, drying and cutting to obtain the finished copper foil, thereby obtaining the electrolytic copper foil.
In this example, a sample of the copper foil was subjected to Scanning Electron Microscope (SEM) inspection, wherein a 1000-fold SEM image of the smooth surface is shown in fig. 1. An SEM image of the appearance surface 1000 times of the copper foil produced in example 1 is shown in fig. 2.
It can be seen that the electrolytic copper foil prepared by the method has good smooth surface roughness and overall flatness, and the tensile strength of the prepared copper foil is good and the thickness uniformity is good by adopting the raw foil additive combination formula for improving the tensile strength of the copper foil in the raw foil electrolysis process and adopting the raw foil process condition for improving the thickness uniformity of the raw foil.
Example 2
The method for manufacturing the electrolytic copper foil for the OLED screen comprises the steps of a cathode roller polishing pretreatment process, an electrolytic foil production process, a first roughening process, a second roughening process, a curing process, a zinc-nickel plating process, an oxidation prevention process and a treating agent process.
Wherein, the cathode roller polishing pretreatment procedure is as follows: firstly, polishing by using a 1000-mesh silicon carbide polishing roller with the rotating speed of 170rpm, the left and right speeds of 130rpm and the load of 10 percent and the rotating speed of a cathode roller of 1.45m/rpm for 40 minutes; then a 2000 mesh silicon carbide polishing roller is used, the rotating speed is 210rpm, the left and right speeds are 170rpm, the load is 5 percent, the rotating speed of the cathode roller is 1.15m/rpm, and the polishing is carried out for 45 minutes; and finally, cleaning the roller surface.
The electrolytic foil production process comprises the following steps: electroplating at a temperature of 34℃and a current density of 37A/dm2 on the surface of the cathode roll using an electrolyte of 105g/L sulfuric acid and 95g/L cupric ions to produce a green foil, the electrolyte comprising a green foil additive comprising 500ppm hydrolyzed gelatin, 180ppm sodium benzene sulfinate, 280ppm hydroxyethylcellulose, and 23ppm hydrochloric acid.
The roughening first procedure is as follows: electroplating the green foil produced by the electrolytic foil producing step at 35 ℃ and a current density of 70A/dm2 by using a roughening solution of 150g/L sulfuric acid, 16g/L cupric ion and 16ppm chloride ion;
the roughening two procedures are as follows: electroplating the raw foil produced in the roughening step at 35 ℃ and a current density of 50A/dm2 by using a roughening solution of 150g/L sulfuric acid, 16g/L cupric ion and 16ppm chloride ion;
wherein the coarsening additive comprises 12ppm sodium citrate, 4ppm molybdate.
The curing process comprises the following steps: electroplating the raw foil processed by the roughening two steps at the temperature of 28 ℃ and the current density of 70A/dm < 2 >, and using a curing solution of 155g/L sulfuric acid, 50g/L cupric ions and 20ppm chloride ions;
wherein the curing additive comprises 18ppm sodium citrate, 2ppm alkyl quaternary ammonium salt.
The zinc and nickel plating process comprises the following steps: and (3) carrying out a zinc and nickel plating process on the green foil treated by the curing process, wherein in the first step, electroplating is carried out in an alkaline electrolyte with the temperature of 40 ℃, the divalent nickel ion concentration of 2.6g/L, the zinc ion concentration of 1.4g/L, the potassium pyrophosphate ion concentration of 27g/L, the pH value of 7.6 and the current density of 8A/dm < 2 >. And in the second step, electroplating is carried out in alkaline electrolyte with the temperature of 34 ℃, the zinc ion concentration of 7.0g/L, the potassium pyrophosphate ion concentration of 37g/L, the pH value of 9.4 and the current density of 7A/dm 2.
The oxidation prevention procedure is as follows: electroplating is carried out in chromium plating anti-oxidation liquid with the temperature of 30 ℃ and the current density of 7.0A/dm < 2 >, hexavalent chromium ions of 1.2g/L and the pH value of 10.8, and the electroplated chromium layer can be passivated in air, so that the anti-oxidation capability of the copper foil at normal temperature can be enhanced.
The working procedure of the treating agent is as follows: the method comprises the steps of coating the raw foil after the anti-oxidation process with a coupling agent with the concentration of 0.2g/L, wherein the coupling agent is an epoxy group, an amino group and an propenyl treating agent according to the following weight ratio of 4:1:2, and is compounded according to the proportion. And after the working procedure of the treating agent, drying and cutting are carried out to obtain the finished copper foil.
Example 3
The method for manufacturing the electrolytic copper foil specifically comprises the steps of a cathode roller polishing pretreatment process, an electrolytic foil production process, a first roughening process, a second roughening process, a curing process, a zinc-nickel plating process, an oxidation prevention process and a treating agent process:
the polishing pretreatment process of the cathode roller comprises the following steps: firstly, polishing by using a 1000-mesh silicon carbide polishing roller with the rotating speed of 180rpm, the speed of about 140rpm and the load of 13 percent, wherein the rotating speed of a cathode roller is 1.5m/rpm for 35 minutes; then a 2000 mesh silicon carbide polishing roller is used, the rotating speed is 220rpm, the left and right speeds are 180rpm, the load is 6%, the rotating speed of the cathode roller is 1.20m/rpm, and the polishing is carried out for 40 minutes; and finally, cleaning the roller surface.
The electrolytic foil production process comprises the following steps: electroplating at 36℃and a current density of 40A/dm2 on the surface of the cathode roll using an electrolyte of 100g/L sulfuric acid and 90g/L cupric ions to produce a green foil, the electrolyte comprising a green foil additive comprising 700ppm hydrolyzed gelatin, 220ppm sodium benzene sulfinate, 350ppm hydroxyethylcellulose, and 26ppm hydrochloric acid.
The roughening first procedure is as follows: electroplating the green foil produced by the electrolytic foil producing step at 37 ℃ and a current density of 65A/dm2 by using a roughening solution of 140g/L sulfuric acid, 14g/L cupric ion and 12ppm chloride ion;
the roughening two procedures are as follows: electroplating the raw foil produced in the roughening step at 37 ℃ and a current density of 45A/dm2 by using a roughening solution of 140g/L sulfuric acid, 14g/L cupric ion and 12ppm chloride ion;
wherein the coarsening additive comprises 15ppm sodium citrate and 5ppm molybdate.
The curing process comprises the following steps: electroplating the green foil processed by the roughening two steps at the temperature of 35 ℃ and the current density of 65A/dm < 2 >, and using a curing solution of 150g/L sulfuric acid, 45g/L cupric ions and 22ppm chloride ions;
wherein the curing additive comprises 20ppm sodium citrate, 3ppm alkyl quaternary ammonium salt.
The zinc and nickel plating process comprises the following steps: and (3) performing zinc and nickel plating on the green foil treated by the curing process, wherein the first step is to perform electroplating in an alkaline electrolyte with a temperature of 42 ℃, a divalent nickel ion concentration of 3.0g/L, a zinc ion concentration of 1.6g/L, a potassium pyrophosphate ion concentration of 32g/L, a pH value of 7.7 and a current density of 7A/dm < 2 >. In the second step, electroplating is carried out in alkaline electrolyte with the temperature of 37 ℃, the zinc ion concentration of 7.5g/L, the potassium pyrophosphate ion concentration of 40g/L, the pH value of 9.6 and the current density of 6A/dm 2.
The oxidation prevention procedure is as follows: electroplating is carried out in chromium plating anti-oxidation liquid with the temperature of 32 ℃ and the current density of 8.0A/dm < 2 >, hexavalent chromium ions of 1.3g/L and the pH value of 10.7, and the electroplated chromium layer can be passivated in air, so that the anti-oxidation capability of the copper foil at normal temperature can be enhanced.
The working procedure of the treating agent is as follows: the method comprises the steps of coating the raw foil after the anti-oxidation process with a coupling agent with the concentration of 0.2g/L, wherein the coupling agent is an epoxy group, an amino group and an propenyl treating agent according to the following weight ratio of 4:1:2, and is compounded according to the proportion. After the working procedure of treating agent, the copper foil is dried and cut to obtain the finished product
Example 4
The method for manufacturing the electrolytic copper foil specifically comprises the steps of a cathode roller polishing pretreatment process, an electrolytic foil production process, a first roughening process, a second roughening process, a curing process, a zinc-nickel plating process, an oxidation prevention process and a treating agent process:
the polishing pretreatment process of the cathode roller comprises the following steps: firstly, polishing for 30 minutes by using a 1000-mesh silicon carbide polishing roller with the rotating speed of 200rpm, the speed of about 150rpm and the load of 15 percent and the rotating speed of a cathode roller of 1.6 m/rpm; then a 2000 mesh silicon carbide polishing roller is used, the rotating speed is 230rpm, the speed is 190rpm, the load is 8 percent, the rotating speed of the cathode roller is 1.25m/rpm, and the polishing is carried out for 35 minutes; and finally, cleaning the roller surface.
The electrolytic foil production process comprises the following steps: electroplating at a temperature of 39 ℃ and a current density of 45A/dm2 using an electrolyte of 90g/L sulfuric acid and 85g/L cupric ions to produce a green foil on the cathode roll surface, the electrolyte comprising a green foil additive comprising 900ppm hydrolyzed gelatin, 280ppm sodium benzene sulfinate, 420ppm hydroxyethyl cellulose, and 30ppm hydrochloric acid.
The roughening first procedure is as follows: electroplating the green foil produced by the electrolytic foil producing step at 39 ℃ and a current density of 60A/dm2 by using a roughening solution of 135g/L sulfuric acid, 12g/L cupric ion and 10ppm chloride ion;
the roughening two procedures are as follows: electroplating the raw foil produced in the roughening step at 39 ℃ and a current density of 40A/dm2 by using a roughening solution of 135g/L sulfuric acid, 12g/L cupric ion and 10ppm chloride ion;
wherein the roughening additive comprises 18ppm sodium citrate, 5.5ppm molybdate.
The curing process comprises the following steps: electroplating the raw foil processed by the roughening two steps at the temperature of 35 ℃ and the current density of 60A/dm < 2 >, and using a curing solution of 145g/L sulfuric acid, 42g/L cupric ions and 24ppm chloride ions;
wherein the curing additive comprises 23ppm sodium citrate, 4ppm alkyl quaternary ammonium salt.
The zinc and nickel plating process comprises the following steps: and (3) a zinc and nickel plating process is carried out on the green foil treated by the curing process:
in the first step, electroplating is carried out in alkaline electrolyte with the temperature of 45 ℃, the concentration of divalent nickel ions of 3.7g/L, the concentration of zinc ions of 1.8g/L, the concentration of potassium pyrophosphate ions of 37g/L, the pH value of 7.8 and the current density of 6A/dm 2.
And in the second step, electroplating is carried out in alkaline electrolyte with the temperature of 40 ℃, the zinc ion concentration of 8.0g/L, the potassium pyrophosphate ion concentration of 45g/L, the pH value of 9.8 and the current density of 5A/dm 2.
The oxidation prevention procedure is as follows: electroplating is carried out in chromium plating anti-oxidation liquid with the temperature of 35 ℃ and the current density of 10.0A/dm < 2 >, hexavalent chromium ions of 1.38g/L and the pH value of 10.5, and the electroplated chromium layer can be passivated in air, so that the anti-oxidation capability of the copper foil at normal temperature can be enhanced.
The working procedure of the treating agent is as follows: the method comprises the steps of coating the raw foil after the anti-oxidation process with a coupling agent with the concentration of 0.2g/L, wherein the coupling agent is an epoxy group, an amino group and an propenyl treating agent according to the following weight ratio of 4:1:2, and is compounded according to the proportion. And after the working procedure of the treating agent, drying and cutting are carried out to obtain the finished copper foil.
Example 5
The electrolytic copper foil for the OLED screen is prepared by placing a cathode roller in an electrolyte to carry out electrolysis to generate a green foil, and then sequentially carrying out the procedures of roughening, curing, zinc-nickel plating, chromium plating, coupling agent coating and the like on the green foil. Sodium benzene sulfinate and hydroxyethyl cellulose play a role in changing the crystal lattice of the copper foil, and improving and stabilizing the tensile strength and the elongation of the copper foil.
In this embodiment, the method for manufacturing the electrolytic copper foil refers to embodiment 1, and is not described herein.
Example 6
The electrolytic copper foil for the OLED screen is prepared by placing a cathode roller in an electrolyte to carry out electrolysis to generate a green foil, and then sequentially carrying out the procedures of roughening, curing, zinc-nickel plating, chromium plating, coupling agent coating and the like on the green foil.
In this embodiment, the method for manufacturing the electrolytic copper foil refers to embodiment 1, and is not described herein.
Example 7
The procedure of example 1 was repeated except that the green foil additive was 300ppm of hydrolyzed gelatin, 150ppm of sodium benzene sulfinate, 420ppm of hydroxyethyl cellulose, and 30ppm of hydrochloric acid.
Example 8
The procedure of example 1 was repeated except that the green foil additive was prepared from 900ppm of hydrolyzed gelatin, 280ppm of sodium benzene sulfinate, 240ppm of hydroxyethyl cellulose and 23ppm of hydrochloric acid.
Performance detection
The raw foils prepared by electrolysis in examples 1 to 4 were subjected to performance test, specifically, roughness, tensile strength and dyne value of the raw foils, and the data were obtained as shown in table 1 below.
Table 1 table of test results
Group of 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
As can be seen from the data in Table 1, the raw foil electrolytically prepared by the method for preparing electrolytic copper foil provided by the embodiment of the invention has good tensile strength which can reach more than 50kgf/mm < 2 >.
In order to further examine the effect of the electrolytic copper foil, the roughness, tensile strength, oxidation resistance, and dyne value of the electrolytic copper foil finally prepared by the manufacturing method in examples 1 to 4 were examined, and specific performance examination results are shown in table 2.
Table 2 table of performance test results
Figure BDA0004030313720000121
Figure BDA0004030313720000131
As can be seen from the data in table 2, the electrolytic copper foil prepared by the method for manufacturing an electrolytic copper foil provided by the embodiment of the invention has good tensile strength and good elongation. Wherein, the cathode roller polishing pretreatment procedure controls the roughness of the electrolytic copper foil smooth surface and the overall flatness; a raw foil additive combination formula for improving the tensile strength of the copper foil in a raw foil electrolysis process; foil production process conditions for improving thickness uniformity of the foil; the process conditions of the zinc and nickel plating process; the treatment agent formula for improving the binding force of the copper foil and other components of the OLED, improving the oxidation resistance and the like are key points and points to be protected in the embodiment of the invention.
According to the results, the electrolytic copper foil has the beneficial effects that the thickness uniformity and the surface flatness of the electrolytic copper foil are good, and the screen display quality and the touch screen effect are good when the electrolytic copper foil is used for an OLED screen; the tensile strength of the electrolytic copper foil is greater than that of the existing electrolytic copper foil, the processing cost is less than 50% of that of the rolled copper foil, the rolled copper foil can reach more than 800mm wide, and a large-screen OLED screen can be manufactured; when the electrolytic copper foil provided by the embodiment of the invention is used for an OLED screen, the heat dissipation effect is good. Moreover, the manufacturing method provided by the embodiment of the invention is simple and has wide market prospect. The hydrolyzed gelatin, sodium benzene sulfinate, hydroxyethyl cellulose and the like in the invention are all products of the existing manufacturer. And is specifically selected according to needs, and is not described herein in detail.
The foregoing has outlined the more detailed description of the preferred embodiment of the invention in order that the basic principles, features and advantages of the invention may be described. However, it should be understood by those skilled in the art that the embodiments of the present invention are not limited to the above-described embodiments, and the above-described embodiments and the description are only preferred embodiments of the present invention, and are not intended to limit the present invention, and various changes may be made without departing from the spirit of the embodiments of the present invention, within the knowledge of those skilled in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the embodiments of the present invention.

Claims (10)

1. The electrolytic copper foil is characterized in that a cathode roller is placed in electrolyte to carry out electrolysis to generate a green foil, and then the green foil is sequentially roughened, solidified, galvanized nickel, chromeplated and coated with a coupling agent to prepare the electrolytic copper foil; wherein the electrolyte contains a raw foil additive, and raw materials of the raw foil additive comprise hydrolyzed gelatin, sodium benzene sulfinate, hydroxyethyl cellulose and hydrochloric acid.
2. The electrolytic copper foil according to claim 1, wherein the cathode roll further comprises a step of performing polishing pretreatment before electrolysis.
3. The electrolytic copper foil according to claim 2, wherein the raw materials of the raw foil additive include 200 to 1000ppm of hydrolyzed gelatin, 100 to 300ppm of sodium benzene sulfinate, 200 to 500ppm of hydroxyethyl cellulose, and 20 to 40ppm of hydrochloric acid.
4. The electrolytic copper foil according to claim 3, wherein the raw materials of the raw foil additive comprise 300 to 900ppm of hydrolyzed gelatin, 150 to 280ppm of sodium benzene sulfinate, 240 to 420ppm of hydroxyethyl cellulose, and 23 to 30ppm of hydrochloric acid.
5. The electrolytic copper foil according to claim 1, wherein the roughening solution for roughening contains a roughening additive, wherein the roughening additive contains 5-20ppm sodium citrate and 2-6ppm molybdate.
6. The electrolytic copper foil according to claim 1, wherein the curing solution for the curing contains a curing additive, wherein the curing additive contains 10 to 25ppm sodium citrate and 0.5 to 5ppm alkyl quaternary ammonium salt.
7. The electrolytic copper foil according to claim 1, wherein the coupling agent is any one or more of an epoxy-based coupling agent, an amino-based coupling agent and an acryl-based coupling agent.
8. The method for producing an electrolytic copper foil according to any one of claims 1 to 7, comprising the steps of:
and (3) electrolyzing the cathode roller in electrolyte to generate raw foil, coarsening the raw foil at the temperature of 30-40 ℃, solidifying at the temperature of 25-45 ℃, then carrying out zinc-nickel plating, chromium plating, coating a coupling agent, drying and cutting to obtain the electrolytic copper foil.
9. An electrolytic copper foil produced by the method for producing an electrolytic copper foil according to claim 8.
10. Use of the electrolytic copper foil according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 9 for the preparation of OLED screens.
CN202211726668.5A 2022-12-30 2022-12-30 Electrolytic copper foil and manufacturing method and application thereof Pending CN116103707A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116516425A (en) * 2023-05-17 2023-08-01 安徽铜冠铜箔集团股份有限公司 Manufacturing method and application of extremely-low-profile electronic copper foil for electrolytic high-order communication

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116516425A (en) * 2023-05-17 2023-08-01 安徽铜冠铜箔集团股份有限公司 Manufacturing method and application of extremely-low-profile electronic copper foil for electrolytic high-order communication
CN116516425B (en) * 2023-05-17 2023-12-19 安徽铜冠铜箔集团股份有限公司 Manufacturing method and application of extremely-low-profile electronic copper foil for electrolytic high-order communication

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