CN1854347A - Low roughness copper foil with high strength and manufacture thereof - Google Patents
Low roughness copper foil with high strength and manufacture thereof Download PDFInfo
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- CN1854347A CN1854347A CN 200510066085 CN200510066085A CN1854347A CN 1854347 A CN1854347 A CN 1854347A CN 200510066085 CN200510066085 CN 200510066085 CN 200510066085 A CN200510066085 A CN 200510066085A CN 1854347 A CN1854347 A CN 1854347A
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Abstract
A kind of high strength and low coarseness copper foil and the manufacturing technique. Copper foil with high strength and low coarseness is available by using scrap wire as raw material and adopting compatible additive system. There is no need for apparatus transformation or mechanically-polishing equipment supplement. It has the following characteristics: bond area coarseness of copper foil was lowered; no copper remnant in micro-prefabricated circuit forming process; tensile-strength was enhanced; microcircuit distortion was prevented when jointing electronic part in micro-prefabricated circuit.
Description
Technical field
The invention relates to invention with high-intensity low roughness copper foil and manufacture method thereof, the transformations such as change that need not design existing foliation machine when using method manufacturing copper foil of the present invention, also need not increase the equipment and the operation that are used for mechanical polishing, on the raw-material basis of directly using existing cheap waste electric wire and so on, make up the Copper Foil that optimal additive system can be made the physical properties with high strength and low rugosity, specifically, for the electrolytic copper foil that is adhesive on tellite usefulness (PCB) insulated substrate (Prepreg), reduce the rugosity of the adhesive surface (Matte Side) of Copper Foil, remaining copper not when forming trickle printed circuit pattern, improved the tensile strength of Copper Foil, on fine pattern, in the welding sequence of real apparatus, electronic part, can prevent the distortion of fine circuits.
Background technology
Tellite is widely used in the precision control aspect of industry electrical appliance/electronicss such as civil electric appliance/electronic products such as receiving set, televisor, washing machine and computer, Wireless Telecom Equipment, various control device usually.
At this moment, as the insulated substrate of industry with printed wiring, the main flame retardant resistance insulated substrate that contains the Resins, epoxy formation that is soaked with glass fibre that adopts, like this, under High Temperature High Pressure, the used for printed circuit electrolytic copper foil is bonded on the insulated substrate, carries out obtaining tellite after the etching according to circuit layout.
For the electrolytic copper foil that is bonded in insulated substrate, generally make the living paper tinsel (Raw Foil) of copper by in copper-bath, carrying out continuity electrolysis galvanic deposit, and give birth at copper for the cohesive force of strengthening itself and insulated substrate and to carry out the gold-plated processing of alligatoring on the paper tinsel face to form copper nuclear (Nodule), after barrier (Barrier) layer was set on the surface after the roughening treatment, electrolytic chromate carried out antirust processing and obtains electrolytic copper foil.
Recently, along with the acceleration of compactization of electrical equipment/electronics, substrate with printed wiring also towards miniaturization, high integration of compact development, therefore, by the manufacture method of improvement substrate and printed wiring, exploitation utmost point low roughness copper foil is as the accurate tellite that is fit to.
According to United States Patent (USP) 5215646, knownly can obtain low roughness copper foil by following method.Be about to treat that electrolytic interval is divided into two, make first interval height of current density ratio in second interval, but this method palpus reforming equipment, required appropriate litigation fees height is so be not desirable.
According to United States Patent (USP) the 5431803rd, thereby get the method that cicada is reduced to 1ppm with the chlorine ion concentration in the electrolytic solution or obtained low roughness copper foil below the 1ppm, but use waste copper slag to be starting material mostly when making electrolytic copper foil, in this case the concentration of chlorion is transferred to 1ppm or be impossible below the 1ppm, introduce other equipment even may also need to drop into substantial contribution in addition, so this is a kind of uneconomic method.
According to United States Patent (USP) No. 5897761, No. 5858517 and 6291081B1 number, cicada electrolytic copper foil that usual way is obtained obtains the method for low roughness copper foil after with rumbling compound (Buffing) mechanical polishing, but this method must possess other production unit, if and there have copper to divide when carrying out polishing process to be residual, may when the manufacturing of tellite, left behind, so this method is not the ideal method as residual copper.
According to No. the 5863410th, United States Patent (USP), get a kind of method that obtains low roughness copper foil of cicada, wherein, by add an amount of accommodating property of lower molecular weight cellulose ester, accommodating property of lower molecular weight polyalkylene glycol ester, low molecule is accommodated property polyethylene imines, accommodating property sulfanilamide (SN) salt (サ Le Off ア ネ-テ イ Star De) organic sulfide, obtain low roughness copper foil, but the situation that makes the Copper Foil of making in this way is rugosity (Rz) value of uneven surface reaches 3.81 μ m, can't satisfy nearest requirement to low roughness copper foil.
According to United States Patent (USP) No. 5958209 and the 6194056th B1 number, cicada uses and to contain a small amount of polyoxyethylene glycol, tin ion, iron ion and be less than or the electrolytic solution that equals the chlorion of 0.1ppm is made the method for the Copper Foil of low rugosity, but as previously mentioned, in fact chlorine ion concentration is maintained 0.1ppm or be impossible below the 0.1ppm, so this method neither ideal.
Mainly make low roughness copper foil in the prior art with four kinds of methods.
First kind, described in No. the 5215646th, United States Patent (USP), producing apparatus foliation machine is transformed the device that so-called super anode (Super Anode) is installed in the back.Use this super anode to change the size of nuclear when examining by regulating the super anode and the kidney-Yang interpolar magnitude of current at the generation initial stage.By being carried out fine adjustments, the size of initial stage nuclear can make low roughness copper foil, but single low roughness copper foil that can't obtain being fit to present fine circuits pattern in this way.
Second kind, in United States Patent (USP) No. 5431803, No. 5958209 and 6194056B1 number etc., introduction is arranged, wherein the amount of chlorion is adjusted to 1ppm or indivisible below the 0.1ppm, change the polarization when electroplating, identical with the example in the first method, can carry out trickle adjustment to the size of initial stage nuclear.As previously mentioned, the amount of chlorion can be maintained 1ppm or the level production below the 1ppm, but what use during mass production is copper scrap and also do not have economic method can prevent from the chlorion that accounts for the most electric wire of copper scrap now at laboratory level.Therefore, this method lacks practicality.
The third method has detailed introduction in United States Patent (USP) No. 5858517, No. 5897761 and 6291081B1 etc., identical with existing method, is to polish the method that reduces rugosity by mechanicalness after making electrolytic copper foil.Because this method is to reduce the rugosity of Copper Foil by mechanical polishing method, so can make the extremely low Copper Foil of rugosity by the degree of control polishing.But need during manufacturing copper foil additional investment to introduce polissoir in this way, the application of new process can cause productivity to reduce and cost increase, so the method for a kind of economy of can not saying so.
A kind of at last, in No. the 5863410th, United States Patent (USP), introduction is arranged, be to regulate the method for the surface shape (Morphology) of Copper Foil by changing the additive that in electrolytic solution, adds.This method need not change and transforms existing foliation machine, the additive that need only change electrolytic solution can obtain required low roughness copper foil, both need not to polish such mechanical polishing, also the amount of chlorion need not be maintained extremely low-level, so be most economical, optimal method.Mention in No. the 5863410th, the United States Patent (USP), accommodating property of lower molecular weight cellulose ester can significantly reduce the quantity (Peak Count:Number Of Peaks Per Surface Area) at peak, and accommodating property of lower molecular weight polyalkylene glycol ester can improve the homogeneity of the microscopic structure of Copper Foil.
On the other hand, described low molecule and accommodated the property polyethylene imines and make peak shape become sharp, help to increase cohesive force when resin-bonded in follow-up engineering, accommodating property sulfanilamide (SN) salt organic sulfide can increase the quantity at peak, reduces peak value.
Summary of the invention
The present invention proposes in view of above-mentioned existing issue, first purpose of the present invention provides has high-intensity low roughness copper foil and manufacture method thereof, with respect to being bonded in the electrolytic copper foil of tellite with insulated substrate, reduced the rugosity of Copper Foil adhesive surface, even also remaining copper not when forming trickle printed wiring, improve the tensile strength of Copper Foil, can prevent the distortion of fine circuits when actual welding is installed electronic component in fine pattern.
Second purpose of the present invention provides has high-intensity low roughness copper foil and manufacture method thereof, it need not be to having the transformations such as change that the foliation machine designs now, also need not increase the equipment and the operation that are used for mechanical polishing, on the raw-material basis of directly using existing cheap waste electric wire and so on, make up the Copper Foil that optimal additive system can obtain having the physical properties of high strength and low rugosity.
Reach the object of the invention by following method: using rotary drum 10 to be arranged in electrolyzer 50 and be positioned at described relatively rotary drum 10 has the foliation machine of the positive plate 20 of predetermined distance to make, and it is characterized in that described method comprises the steps:
Step S1000 provides electrolytic solution 60 not have rotary drum 10 and positive plate 20 in described electrolyzer 50;
Step S2000 adds the additive 61 of the EU (ethylene thiourea) of the SPS (sodium polydithio-dipropyl sulfonate) contain the gelatin of 0.1ppm～100ppm, the HEC of 0.05ppm～50ppm (Natvosol), 0.05ppm～20ppm and 0.05ppm～30ppm in the electrolytic solution 60 in being provided to described electrolyzer 50;
Step S3000 applies corresponding polarity electric current to described rotary drum 10 and positive plate 20, obtains by the Copper Foil 40 of electrolysis galvanic deposit on rotary drum 10.
Gelatine molecular weight among the described step S2000 is preferably greater than and equals 10000.
Gelatin addition among the described step S2000 is preferably 2ppm～5ppm.
HEC addition among the described step S2000 is preferably 1ppm～3ppm.
The addition of SPS among the described step S2000 is preferably 0.5ppm～3ppm.
The addition of EU among the described step S2000 is preferably 0.1ppm～1ppm.
After the described step S3000, preferably carry out following steps again:
Step S3100, nucleation is to increase the cohesive force of described Copper Foil 40;
Step S3200 places obstacles to prevent Copper Foil 40 diffusions;
Step S3300 carries out antirust to prevent the oxidized of Copper Foil 40;
Step S3400 in order to strengthen the cohesive force of Copper Foil 40, handles with silane coupling agent.
Preferred described Copper Foil 40 is applied to copper and opens laminated plates, tellite, lithium ion battery or flexible circuit base board.
And then, purpose of the present invention is reached by having the high-intensity low roughness copper foil of having of following characteristics, described Copper Foil is made by the 1st to 7 any described method, it is characterized in that, in described electrolytic solution 60, add the additive 61 that the EU by the SPS of HEC, the 0.05ppm～20ppm of the gelatin of 0.1ppm～100ppm, 0.05ppm～50ppm and 0.05ppm～30ppm constitutes; Obtain by the Copper Foil 40 of electrolysis galvanic deposit on described rotary drum 10 after described rotary drum 10 and positive plate 20 applied corresponding polarity electric current.
According to the following detailed description relevant and preferred embodiment etc. with accompanying drawing etc. can clearer other purposes of the present invention, certain benefits and new feature etc.
Being characterized as of above manufacture method: need not append new installation and the operation of introducing mechanical polishing with high-intensity low roughness copper foil, need only directly use the starting material of existing cheap waste electric wire class, make up the Copper Foil that optimal additive system can be made the physical properties with high strength and low rugosity.
In addition, be bonded in the electrolytic copper foil of tellite relatively with insulated substrate, reduced the rugosity of the adhesive surface of Copper Foil, even also remaining copper not when forming fine printed wiring, improve the tensile strength of Copper Foil, can prevent the distortion of fine circuits when actual welding is installed electronic component in fine pattern.
Description of drawings
The pie graph of the electrolysis foliation machine of drum structure among [Fig. 1] the present invention.
The precedence diagram that has high-intensity low roughness copper foil manufacture method among [Fig. 2] the present invention.
The precedence diagram that comprises postprocessing working procedures of [Fig. 3] Fig. 2.
The electron microscope SEM photo of the made Copper Foil of [Fig. 4] embodiment of the invention.
The electron microscope SEM photo of the made Copper Foil of [Fig. 5] comparative example.
[nomenclature]
10: rotary drum
20: positive plate
30: roller
40: Copper Foil
50: electrolyzer
60: electrolytic solution
61: additive
Embodiment
Below, the manufacture method that present invention will be described in detail with reference to the accompanying with high-intensity low roughness copper foil.
Fig. 1 is the structure iron of the electrolysis foliation machine of drum structure of the present invention, and Fig. 2 is the precedence diagram that manufacturing of the present invention has high-intensity low roughness copper foil.As shown in Figures 1 and 2, the foliation machine be can be in mechanicalness calendering with the representative shaped device of Copper Foil 40 moulding.
Wherein, electrolyzer 50 is equipped with electrolytic solution 60, adds the additive 61 of the EU (ethylene thiourea) of the SPS (sodium polydithio-dipropyl sulfonate) contain the gelatin of 0.1ppm～100ppm, the HEC of 0.05ppm～50ppm (Natvosol), 0.05ppm～20ppm and 0.05ppm～30ppm again in electrolytic solution 60.
At this moment, above-mentioned electrolytic solution 60 basic composition is H
2SO
4: 50g/l～200g/l, Cu
2+: 30g/l～150g/l, Cl
-: smaller or equal to 200mg/l, the temperature of electrolytic solution 60 is 80 ℃ of normal temperature, and current density is 20A/dm
2～150A/dm
2
Be cut into circular positive plate 20 and rotary drums 10 this electrolytic solution 60 mid-being placed with, it is corresponding with the depression position of described positive plate 20 that rotary drum 10 has the function of cathode electrode.At this moment, corresponding each polarity applies electric current on above-mentioned rotary drum 10 and positive plate 20, and roller 30 is positioned at the right side on electrolytic solution 60 tops on the sense of rotation of above-mentioned rotary drum 10.
Thus, in above-mentioned rotary drum 10 rotation that is applied in (-) electric current, from rotary drum 10 and be applied between the positive plate 20 of (+) electric current and separate out copper, Copper Foil 40 is by the surface of galvanic deposit at drum 10.Take out volume by above-mentioned roller 30, receive web-like electro-deposition copper foil 40.
Preferably according to through last handling process can be selectively used for copper open the mode of the electrode materials of laminated plates (CopperClad Laminate), tellite, lithium ion battery, flexible circuit base board receive this Copper Foil 40.
Fig. 2 is the precedence diagram that manufacturing of the present invention has high-intensity low roughness copper foil.As shown in Figure 2, manufacturing has in the method for high-intensity low roughness copper foil, carries out the electrolysis galvanic deposit in type Copper Foil 40 before aftertreatment, and then manufacturing has high-intensity low roughness copper foil.
At first carry out step S1000, in electrolyzer 50, provide electrolytic solution 60 not have rotary drum 10 and positive plate 20.At this moment, electrolytic solution 60 basic composition is H
2SO
4: 50g/l～200g/l, Cu
2+: 30g/l～150g/l, Cl
-: smaller or equal to 200mg/l, the temperature of electrolytic solution 60 is 80 ℃ of normal temperature, and current density is 20A/dm
2～150A/dm
2
Next carry out step S2000, in the electrolytic solution 60 of essentially consist, add the additive 61 of EU of SPS, 0.05ppm～30ppm of HEC, the 0.05ppm～20ppm of the gelatin contain 0.1ppm～100ppm, 0.05ppm～50ppm.
Carry out step S3000 afterwards, on above-mentioned rotary drum 10 and positive plate 20, apply corresponding polarity electric current, obtain the electrolysis galvanic deposit at the high-intensity low roughness copper foil 40 of having of rotary drum 10.
Hereinafter different according to each additive 61 additions describes its physical properties.
The purpose of using gelatin is in order to increase the physical strength of Copper Foil 40 electrolytic coatings, adds the reasons are as follows of gelatin of 0.1ppm～100ppm.If the not enough 0.1ppm of addition though can obtain the initial stage tissue, along with the growth of electrolytic copper foil, obtains the electrolytic copper foil 40 of thick tissue, the peak value height of this thick tissue can't obtain desirable low roughness copper foil 40.
If add the gelatin that surpasses 100ppm, though suppressed the Copper Foil 40 that the thick growth of Copper Foil 40 can obtain low rugosity, shortcoming is when forming fine circuits, as the high temperature unit elongation (HTE of one of main characteristic; High Temperature Elongation, 180 ℃ of mensuration) significantly descend.
Above also mention HEC and SPS, gelatin and EU interaction and make Copper Foil 40 have stabile low rugosity, the reason of the HEC that adds 0.05～50ppm is described at this.When adding the HEC of not enough 0.05ppm, descend with the interaction ability of SPS and gelatin, the electrolytic copper foil 40 of manufacturing is inhomogeneous, as surpassing 50ppm, can cause separating out copper on the electrolytic copper foil 40, cause the reason of bad phenomenon such as remaining copper when making tellite.
The gloss-imparting agent of SPS when electroplating undertaken by the interaction of HEC and gelatin and to be reduced the main effect of organizing rugosity of electroplating, in the reason of the SPS of this explanation interpolation 0.05～20ppm.Because, if add the SPS be less than 0.05ppm, descend with the interaction ability of other materials, the electrolytic copper foil 40 rugosity height, inhomogeneous of manufacturing, and addition surpasses the not special effect of 20ppm, only can increase expense.
EU forms precipitated phase during plating in electrolytic coating, increases the physical strength of Copper Foil.The EU that is less than 0.05ppm as interpolation, the formation degree of precipitated phase descends, be difficult to produce and have high-intensity electrolytic copper foil 40, surpass 30ppm as addition, precipitated phase is too much, causes the normal temperature of Copper Foil 40 and high temperature unit elongation sharply to descend, and the frangible mechanical characteristicies such as phenomenon of Copper Foil can occur and worsen, produced with the interaction ability of other materials and descended the shortcoming that rugosity sharply rises.
Fig. 4 is the electron microscope SEM photo by the made Copper Foil of embodiments of the invention, and Fig. 5 then is the electron microscope SEM photo of made Copper Foil in the comparative example.
The method of the comparative example manufacturing copper foil 40 under different condition that below at first provides the embodiment of method constructed in accordance and compare with embodiment.
[embodiment]
Make in following condition.Electrolytic solution consist of H
2SO
4: 100g/l, Cu
2+: 100g/l, Cl
-: smaller or equal to 30mg/l, temperature is 60 ℃ of normal temperature, and current density is 100A/dm
2The addition of additive is shown in [table 1].
[table 1]
| Gelatin | HEC | SPS | EU | |
| Embodiment 1) | 2.5 | 1 | 1.5 | 0.1 |
| Embodiment 2) | 3.5 | 2 | 2.5 | 0.4 |
| Embodiment 3) | 4.5 | 1.5 | 2 | 1 |
[comparative example]
Make in following condition.Electrolytic solution consist of H
2SO
4: 100g/l, Cu
2+: 100g/l, Cl
-: below 30mg/l; Temperature is 60 ℃ of normal temperature; Current density is 100A/dm
2The addition of additive is shown in [table 2].
[table 2]
| Gelatin | HEC | SPS | EU | |
| Comparative example 1) | 2.5 | 1.5 | ||
| Comparative example 2) | 3.5 | 0.4 | ||
| Comparative example 3) | 3.5 | 1.5 | 2 | - |
In above-mentioned, the surface shape of the electrolytic copper foil that embodiment is made is identical with Fig. 4, and the surface shape of the electrolytic copper foil that comparative example is made as shown in Figure 5.
The surface shape of Copper Foil can be found out from photo, and the comparative example of Fig. 5 is higher relatively than the surface roughness of the made Copper Foil of embodiment of Fig. 4.The copper foil surface rugosity of making in the comparative example and other physical propertiess of Copper Foil (rugosity, tensile strength, unit elongation, high temperature tensile strength, high temperature unit elongation) descend, and its result is shown in [table 3].
[table 3]
| RZ (μm) | Tensile strength (kgf/mm 2) | Unit elongation (%) | High temperature tensile strength (kgf/mm 2) | High temperature unit elongation (%) | |
| Embodiment 1) | 2.1 | 47.5 | 6.7 | 24.2 | 13.7 |
| Embodiment 2) | 1.8 | 52.5 | 6.4 | 24.3 | 16.4 |
| Embodiment 3) | 1.9 | 62.7 | 5.4 | 23.4 | 11.4 |
| Comparative example 1) | 2.5 | 34.1 | 5.8 | 20.1 | 8.5 |
| Comparative example 2) | 3.5 | 33.8 | 8.3 | 20.3 | 2.1 |
| Comparative example 3) | 2.0 | 32.5 | 6.9 | 20.4 | 5.7 |
Shown in [table 3], with respect to comparative example, the surface roughness of the made Copper Foil of the embodiment of the invention is lower, and the physical properties of Copper Foil (rugosity, tensile strength, unit elongation, high temperature tensile strength, high temperature unit elongation) all is improved.
Therefore, and compare with the comparative example method, the method that embodiments of the invention are made electrolytic copper foil can obtain to have relative high strength, hang down the Copper Foil of rugosity.
Fig. 3 comprises the postprocessing working procedures stage at interior precedence diagram for Fig. 2's.As shown in Figure 2, made among the embodiment have high-intensity Copper Foil through the postprocessing working procedures among Fig. 3, and the copper that optionally is applied to following explanation is opened in the electrode materials of laminated plates, tellite, lithium ion battery, the flexible circuit base board.
It can pass through following steps: step 3000, receive Copper Foil 40; Step S3100, nucleation increases the cohesive force of Copper Foil 40 and resin with continuity; Step S3200 places obstacles to prevent that Copper Foil 40 from spreading on resin; Step S3300, antirust processing is oxidized to prevent Copper Foil; Step S3400, in order to strengthen the cohesive force of Copper Foil 40, (Silane Coupling Agent) handles with silane coupling agent.
More than manufacturing of the present invention have the condition that the method for high-intensity low roughness copper foil mentions in the foregoing description, as long as in the scope of the present invention's prompting, can carry out the enforcement of other various embodiments, obtain having the Copper Foil of varied characteristic therefrom and use this Copper Foil can make corresponding electronic component.
Although above just describe the present invention, only otherwise depart from the main idea and the scope of invention, can do multiple adjustment and distortion with preferred embodiment.Therefore, the scope of claim also comprises corresponding adjustment and the distortion that meets main idea of the present invention.
Claims (9)
1, the manufacture method that has high-intensity low roughness copper foil, it is to use to have rotary drum (10) in the structure and be positioned at described rotary drum (10) in electrolyzer (50) has the foliation machine of the positive plate (20) of predetermined distance to make the method for Copper Foil, it is characterized in that, comprise the steps:
Step S1000 provides electrolytic solution (60) not have rotary drum (10) and positive plate (20) in described electrolyzer (50);
Step S2000, add additive (61) in the electrolytic solution (60) in being provided to described electrolyzer (50), described additive comprises the gelatin of 0.1ppm～100ppm, the Natvosol of 0.05ppm～50ppm, the sodium polydithio-dipropyl sulfonate of 0.05ppm～20ppm and the ethylene thiourea of 0.05ppm～30ppm;
Step S3000 applies corresponding polarity electric current to described rotary drum (10) and positive plate (20), obtains the Copper Foil (40) of electrolysis galvanic deposit on rotary drum (10).
2, the manufacture method with high-intensity low roughness copper foil as claimed in claim 1 is characterized in that, in described step S2000, the molecular weight of described gelatin is more than or equal to 10000.
3, the manufacture method with high-intensity low roughness copper foil as claimed in claim 1 is characterized in that, in described step S2000, the addition of described gelatin is 2ppm～5ppm.
4, the manufacture method with high-intensity low roughness copper foil as claimed in claim 1 is characterized in that, in described step S2000, the addition of described Natvosol is 1ppm～3ppm.
5, the manufacture method with high-intensity low roughness copper foil as claimed in claim 1 is characterized in that, in described step S2000, the addition of described sodium polydithio-dipropyl sulfonate is 0.5ppm～3ppm.
6, the manufacture method with high-intensity low roughness copper foil as claimed in claim 1 is characterized in that, in described step S2000, the addition of described ethylene thiourea is 0.1ppm～1ppm.
7, the manufacture method with high-intensity low roughness copper foil as claimed in claim 1 is characterized in that, further is included in the following steps of carrying out behind the described step S3000:
Step S3100, nucleation is to increase the cohesive force of described Copper Foil (40);
Step S3200 places obstacles to prevent Copper Foil (40) diffusion;
Step S3300, it is oxidized to prevent Copper Foil (40) to carry out antirust processing;
Step S3400 handles to strengthen the cohesive force of Copper Foil (40) with silane coupling agent.
8, the manufacture method with high-intensity low roughness copper foil as claimed in claim 7 is characterized in that, described Copper Foil (40) is used for copper and opens laminated plates, tellite, lithium ion battery or flexible circuit base board.
9, describedly has a high-intensity low roughness copper foil as any one of claim 1 to 7, it is characterized in that, add additive (61) in described electrolytic solution (60), described additive is made of the gelatin of 0.1ppm～100ppm, the Natvosol of 0.05ppm～50ppm, the sodium polydithio-dipropyl sulfonate of 0.05ppm～20ppm and the ethylene thiourea of 0.05ppm～30ppm; Described rotary drum (10) and positive plate (20) are applied corresponding polarity electric current, obtain the Copper Foil (40) of electrolysis galvanic deposit on rotary drum (10).
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| CN102002737B (en) * | 2010-11-24 | 2012-10-31 | 山东金宝电子股份有限公司 | Composite additive for producing electrolytic copper foil with high bending resistance and low outline |
| CN102337566A (en) * | 2011-10-28 | 2012-02-01 | 广东嘉元科技股份有限公司 | Method for manufacturing ultrathin electrolytic copper foil for new energy resource power battery |
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| CN104762642A (en) * | 2015-03-31 | 2015-07-08 | 灵宝华鑫铜箔有限责任公司 | Production process of electrolytic copper foil with low warping degree |
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