CN1250775C - Method for producing anti-folding electrolytic copper foil - Google Patents
Method for producing anti-folding electrolytic copper foil Download PDFInfo
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- CN1250775C CN1250775C CN 02159066 CN02159066A CN1250775C CN 1250775 C CN1250775 C CN 1250775C CN 02159066 CN02159066 CN 02159066 CN 02159066 A CN02159066 A CN 02159066A CN 1250775 C CN1250775 C CN 1250775C
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- copper foil
- electrolytic copper
- electrolytic
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- anode
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000011889 copper foil Substances 0.000 title claims abstract description 62
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 230000002742 anti-folding effect Effects 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 23
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 8
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 11
- 241000370738 Chlorion Species 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 9
- 238000009713 electroplating Methods 0.000 claims description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001431 copper ion Inorganic materials 0.000 claims description 3
- 239000008151 electrolyte solution Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 abstract description 11
- 239000000460 chlorine Substances 0.000 abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 abstract description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 abstract 2
- -1 chlorine ions Chemical class 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 16
- 238000000137 annealing Methods 0.000 description 12
- 239000000499 gel Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 8
- 238000012545 processing Methods 0.000 description 7
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 238000007747 plating Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004320 controlled atmosphere Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- NHDHVHZZCFYRSB-UHFFFAOYSA-N pyriproxyfen Chemical compound C=1C=CC=NC=1OC(C)COC(C=C1)=CC=C1OC1=CC=CC=C1 NHDHVHZZCFYRSB-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000246 remedial effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The present invention discloses a method for manufacturing folding resisting electrolytic copper foil, which comprises the following steps: an electrolytic groove holding cupric sulfate electrolytic liquid is provided, the electrolytic liquid comprises gel with the concentration range of lower than 1.5 ppm and chlorine ions with the concentration range of lower than 30 ppm, and the electrolytic groove is provided with an anode and a cathode; current flows through the anode and the cathode, and copper in the cupric sulfate electrolytic liquid can be generated on the cathode to form the electrolytic copper foil.
Description
Technical field
The invention relates to a kind of manufacture method of electrolytic copper foil, be particularly to a kind ofly be applicable to the flexible printed wiring board purposes, and have the manufacture method of the electrolytic copper foil of good folding quality.
Background technology
Flexible printed wiring board is the product that electronic machine often uses, and main being suitable for needs the occasion that bends when mounted, for example the dashboard of automobile; Or instrument has repeatedly the needs of motion, for example magnetic head of disc drive and printer head repeatedly in operating process.Therefore, must have good folding quality as the Copper Foil of the constituent material of the conducting wire on the above-mentioned flexible printed wiring board and can meet the use needs, avoid repeatedly losing its effectiveness after the bending.
The kind of Copper Foil is originated according to processing procedure, generally can be divided into electrolytic copper foil and rolled copper foil two big classes.Traditionally, therefore electrolytic copper foil only is used in single or the bigger bending part of rate radius in the wrong at most because tired ductility is lower.Otherwise rolled copper foil is as the term suggests be to carry out the repeatedly deformation processing of slab copper sheet and get via rolling press, and it has good tired ductility, so has been adopted as the main Copper Foil raw material on the flexible printed wiring board in a large number.
Yet the price of rolled copper foil is high, and mechanical properties has the difference of obvious directivity, and is subject to processing units and processing procedure ability, thereby the Copper Foil width generally can only reach about 60 centimeters, and thickness also is not easy to reduce.Therefore the also requirement of the processing procedure efficient of fit printed circuit board and compact development trend fully of rolled copper foil.
In recent years, process technique improvement along with electrolytic copper foil, relevant Copper Foil dealer is just at the shortcoming of above-mentioned rolled copper foil, for example Japanese patent laid-open 6-269807 is described successively to propose to have the solution that compromise first electrolysis rolls again, or further thoroughly with the electrolytic copper foil processing procedure after the improvement, advocate as U.S. Pat Patent No.6132887 and Japanese kokai publication hei 8-283886, directly replaced rolled copper foil.Though used electroplate liquid additive all belongs to electrolytic copper foil gel (glue) and chlorion commonly used traditionally in above-mentioned two pieces of patents, but through finding that both are on the additive concentration orientation after the comparison in detail, present antipodal trend, be low chlorine that both are all low as US ' 887 is carried (<5ppm) hang down gel (<0.2ppm), otherwise be exactly both all high high gels of high chlorine (20ppm) (68ppm) as Te Kaiping ' 886.
In the control of electroplate liquid additive,, will increase the puzzlement in the follow-up utilization of Copper Foil and the raising of cost because chlorine ion concentration causes the excessively coarse of copper-clad surface when too high easily; Otherwise cross the shortcoming that then has the control of electroplate liquid concentration to be difficult for when hanging down again.And if the gel strength aspect similarly excessive concentration, also can cause the recrystallize of electrolytic copper foil to be difficult for carrying out, and and then cause the tired ductility of electrolytic copper foil to reduce, unfavorable for the application of flexible printed wiring board; Otherwise cross the excessively coarse of the corrosion that also can cause electroplating device when low and copper-clad surface.Therefore how in traditional acid copper sulfate electroplate liquid, the concentration range of suitably allocating gel and chlorion to produce with the electrolytic copper foil of tired ductility of height and high temperature elongation feature, is a free-revving engine of the present invention.
Summary of the invention
In view of this, the invention provides a kind of manufacture method of electrolytic copper foil of tool folding resistance, explanation via electrochemistry differential capacity test result and electrochemistry capillary theory, learn that the Cl ionic concn is when 10ppm is following, help downgrading of Copper Foil differential capacity value, related increase copper foil surface energy then has the opposite effect when 10ppm is above.If this moment is again further combined with the unpolarizing of chlorion, then behind the viewpoint analysis that adopts metallic crystal to learn, expection also contains Cl through real example electroplate liquid trace and (under<10ppm) the state, helps the grain-size of electrolytic copper foil to become big and preferable Copper Foil extensibility.These features just in time meet the demand of folding electrolytic copper foil.Shown in Fig. 1 a, Fig. 1 b, Fig. 1 a is the SEM figure that shows chlorine ion concentration (2ppm) effect of electrolytic copper foil surface crystalline form; Fig. 1 b is the SEM figure that shows chlorine ion concentration (8ppm) effect of electrolytic copper foil surface crystalline form, can be found out that by above-mentioned illustrative example the size of electrolytic copper foil surface crystal grain increases and obviously increases with chlorine ion concentration really.Fig. 2 then is the graphic representation that shows the chlorine ion concentration effect of electrolytic copper foil high temperature elongation values, and wherein X-axis is represented chlorine ion concentration (ppm), and Y-axis is the high temperature elongation.When chlorine ion concentration when 30ppm is following, electrolytic copper foil can have good high temperature elongation, it is between 6~12ppm that preferable high temperature elongation values then appears at chlorine ion concentration, so chlorine ion concentration has the effect of raising to the high temperature elongation in this scope.
Because appropriateness increases chlorine ion concentration (as 12ppm) to 10ppm in the electroplate liquid, newly-increased elongation help to increase electrolytic copper foil for the upper limit tolerance of gel strength in the electroplate liquid to 1.5ppm.Therefore just can reach the optimization of the concentration range of gel and chlorion, and when chlorine ion concentration was 0~4ppm, gel was 0ppm.Add the cooperation of the acid copper sulfate electroplate liquid of felicity condition, but actual production goes out to have simultaneously excellent high elongation [HTE>15%] and good tired extension characteristics [℃ of-15 minutes low-temperature annealings of intact plating paper tinsel>30%, 177 handle-30 minutes anneal of back paper tinsel>50% and 200 ℃ after paper tinsel>70%] and meets can the anneal electrolytic copper foil of folding resistance electrolytic copper foil performance requriementss at different levels such as the level-E10 and the level-E4 that annealed of the relevant level-E11 that can anneal, low temperature in the IPC-4562 standard (as shown in table 1).
Table 1
Characteristic | Hoz | ||
The E11 level of can annealing | The E10 low temperature level of can annealing | The E4 level of having annealed | |
23 ℃ of [73.4] tensile strength ductility: tired ductility elongation | 276MPa 40ksi NA 5% | 103MPa 15ksi 25% 5% | 103MPa 15ksi 65% 5% |
At 180 ℃ of tensile strength elongations | 138MPa 20ksi 15% | --- --- | TBD [TBD] TBD |
NA reaches---represent normal value failed call, TBD to represent normal value to wait to set up.
In order to reach the present invention, manufacture method with folding resistance electrolytic copper foil of the present invention, it comprises: an electrolyzer that copper sulfate electrolyte is housed is provided, wherein this electrolytic solution comprises the chlorion that concentration range is lower than the gel of 1.5ppm and is lower than 30ppm, and this electrolyzer is equiped with anode and negative electrode; And by electric current in this anode and negative electrode, make the copper in the copper sulfate electrolyte be created on negative electrode and form electrolytic copper foil.
According to embodiments of the invention, below the preferable 30ppm of the concentration of chlorion, being more preferred from is 6~12ppm, and when chlorine ion concentration was 0~4ppm, gel was 0ppm.Copper ion concentration is preferably 40~70g/L in this copper sulfate electrolyte, and sulfuric acid concentration is preferably 60~120g/L.In electroplating parameter control, the temperature of copper sulfate electrolyte is preferable between 40~70 ℃, and the current density that electroplating process uses is preferably 0.4~1.0A/cm2.
According to the manufacture method with folding resistance electrolytic copper foil of the present invention, have the following advantages:
Do not need special additive;
Distinctive Cl chlorine ion concentration: be lower than 30ppm, be more preferred from 6~12ppm;
Low copper ion concentration does not have the maintenance issues that causes the copper crystallization to separate out in processing procedure;
After low-temperature annealing was handled, electrolytic copper foil of the present invention can satisfy standard (E10, the E4) required value of relevant electrolytic copper foil anneal material among all IPC 4562 simultaneously.
Description of drawings
Fig. 1 a is the SEM figure that shows chlorine ion concentration (2ppm) effect of electrolytic copper foil surface crystalline form;
1b is the SEM figure that shows chlorine ion concentration (8ppm) effect of electrolytic copper foil surface crystalline form;
Fig. 2 is the graphic representation that shows the chlorine ion concentration effect of electrolytic copper foil high temperature elongation values.
Embodiment
Embodiment 1
Utilize the rotating electrode column system to be fixed as at the electrode surface rotating speed under the condition of 1.24m/sec, carry out actual plating.The system cathode material is that commercial pure titanium metal is made, and anode then is the insoluble anode DSA (Dimension Stabilized Anode) with the cathode wheel concentric circles.
Electroplating bath components is:
Copper 63.5g/L; Sulfuric acid 100g/L; Chlorion 2ppm; Gel 0ppm; Temperature is 60 ℃
After forming electrolytic copper foil via aforesaid device, the test piece of getting thickness and be 18 μ m is carried out 177 ℃ of low-temperature annealings of 15 minutes respectively and is handled (A) in the tube furnace of controlled atmosphere, or 200 ℃ of The high temperature anneal (B) of 30 minutes.Afterwards, test its tensile strength, elongation and tired ductility respectively, the results are shown in table 2.
Table 2
The test piece code name | Current density | Tensile strength (Ksi) | Elongation (%) | Tired ductility | IPC standard rank accordance | Annealing conditions | ||||
A/cm 2 | Room temperature | 180℃ | Room temperature | 180℃ | Df(%) | E11 | E10 | E4 | ||
1-1 | 0.6 | 52.6 | 25.9 | 6.35 | 16.3 | 66.4 | ○ | ○ | ○ | |
1-2 | 0.6 | 43.1 | --- | 6.40 | --- | 70.6 | ○ | ○ | A | |
1-3 | 0.6 | 39.2 | --- | 7.75 | --- | 81.8 | ○ | ○ | B | |
1-4 | 0.6 | 56.0 | 25.3 | 5.69 | 19.0 | 59.9 | ○ | ○ | ||
1-5 | 0.6 | 43.7 | --- | 7.35 | --- | 80.0 | ○ | ○ | A | |
1-6 | 0.6 | 39.8 | --- | 8.65 | --- | 88.8 | ○ | ○ | B |
Annotate:---representative does not have normal value, and other required value of standard level is satisfied in zero representative.
Embodiment 2
Utilize the rotating electrode column system to be fixed as at the electrode surface rotating speed under the condition of 1.24m/sec, carry out actual plating.The system cathode material is that commercial pure titanium metal is made, and anode then is the DSA with the cathode wheel concentric circles.
Electroplating bath components is:
Copper 63.5g/L; Sulfuric acid 80g/L; Chlorion 8ppm; Gel 1ppm; Temperature is 60 ℃
After forming electrolytic copper foil via aforesaid device, the test piece of getting thickness and be 18 μ m is carried out 177 ℃ of low-temperature annealings of 15 minutes respectively and is handled (A) in the tube furnace of controlled atmosphere, or 200 ℃ of The high temperature anneal (B) of 30 minutes.Afterwards, test its tensile strength, elongation and tired ductility respectively.The results are shown in table 3.
Table 3
The test piece code name | Current density | Tensile strength (Ksi) | Elongation (%) | Tired ductility | IPC standard rank accordance | Annealing conditions | ||||
A/cm 2 | Room temperature | 180℃ | Room temperature | 180℃ | Df(%) | E11 | E10 | E4 | ||
2-1 | 0.5 | 41.9 | 23.2 | 7.30 | 21.6 | 57.7 | ○ | ○ | ||
2-2 | 0.5 | 35.8 | --- | 7.84 | --- | 69.0 | ○ | ○ | A | |
2-3 | 0.5 | 35.0 | --- | 7.57 | --- | 72.1 | ○ | ○ | B | |
2-4 | 0.8 | 49.0 | 25.5 | 8.33 | 20.7 | 58.1 | ○ | ○ | ||
2-5 | 0.8 | 43.6 | --- | 8.16 | --- | 66.3 | ○ | ○ | A | |
2-6 | 0.8 | 40.0 | --- | 7.12 | --- | 72.3 | ○ | ○ | B |
Annotate:---representative does not have normal value, and other required value of standard level is satisfied in zero representative.
Comparative example 1
Get the rolled copper foil that commercially available thickness is 18 μ m (the test piece code name is P-1), the identical anneal of embodiment 1,2-promptly 177 ℃ of low-temperature annealings of 15 minutes are handled (A) (the test piece code name is P-2) through granting, or after 200 ℃ of The high temperature anneal (B) of 30 minutes (the test piece code name is P-3), test its tensile strength, elongation and tired ductility, get result such as table 4.Alphabetical P represents sampling from parallel rolling direction in the table, and front and back two numerals represent the test piece sampling from vertical and parallel rolling direction respectively in the hurdle.X representative in the rank accordance hurdle does not meet the code requirement of IPC, and P then represents has only parallel rolling direction to meet.
Table 4
The test piece code name | Tensile strength (Ksi) | Elongation (%) | Tired ductility | IPC standard rank accordance | Annealing conditions | ||||
Room temperature | 180℃ | Room temperature | 180℃ | Df(%) | E11 | E10 | E4 | ||
P-1 | 33.639.4 | 20.0/P | 0.89-0.92 | 7.74/P | 40.0-79.4 | X | |||
P-2 | 20.2-24.5 | --- | 3.93-5.45 | --- | 58.7-88.0 | P | P | A | |
P-3 | 19.2-24.2 | --- | 3.88-5.92 | --- | 66.1-81.4 | P | P | B |
Annotate:---representative does not have normal value.
Comparative example 2
Getting commercially available thickness is the HTE level electrolytic copper foil (the test piece code name is P-4) of 18 μ m, the identical anneal of embodiment 1,2-promptly 177 ℃ of low-temperature annealings of 15 minutes are handled (A) (the test piece code name is P-5) through granting, or after 200 ℃ of The high temperature anneal (B) of 30 minutes (the test piece code name is P-6), test its tensile strength, elongation and tired ductility, get result such as table 5.Before and after in the hurdle two numerals represent respectively test piece sampling from vertical and parallel producer to.X representative in the rank accordance hurdle does not meet the code requirement of IPC.
Table 5
The test piece code name | Tensile strength (Ksi) | Elongation (%) | Tired ductility | IPC standard rank accordance | Annealing conditions | ||||
Room temperature | 180℃ | Room temperature | 180℃ | Df(%) | E11 | E10 | E4 | ||
P-4 | 47.3-47.7 | 27.9-27.9 | 4.20-4.44 | 10.1-10.3 | 53.3-55.4 | X | |||
P-5 | 45.0-46.2 | --- | 2.66-4.23 | --- | 47.9-53.3 | X | A | ||
P-6 | 43.3-44.1 | --- | 1.84-2.55 | --- | 49.9-55.3 | X | B |
Annotate:---representative does not have normal value.
Data by above-mentioned table 2~3 shows, embodiment 1, no matter 2 prepared electrolytic copper foils are in tensile strength, elongation and tired ductility and the listed E11 of table 1, the standard of E10 or E4 is compared, the performance requriements that all meets all relevant folding purposes level specifications among the general general IPC-4562 of industry, moreover, that compares with table 4~5 is following, the electrolytic copper foil of gained of the present invention obviously has the characteristic more excellent than commercially available electrolytic copper foil, and can under the situation of not sacrificing tired extension performance, overcome the directivity difference of rolled copper foil and low excessively shortcomings such as high temperature elongation again.In addition, the copper concentration of method of the present invention in electrolytic solution, can't produce crystallization and separate out under the operating environment with regard to 20 ℃ of domestic general room temperatures because is to be controlled at lower value, for the carrying out of apparatus for production line remedial operation work, also has no small benefiting.
Though the present invention discloses as above with preferred embodiment; right its is not in order to limiting the present invention, anyly has the knack of this skill person, without departing from the spirit and scope of the present invention; when can doing a little change and retouching, so protection scope of the present invention is as the criterion when looking claims scope person of defining.
Claims (5)
1. the manufacture method of the electrolytic copper foil of a tool folding resistance comprises:
One electrolyzer that copper sulfate electrolyte is housed is provided, and wherein this electrolytic solution comprises that concentration is the gel of 0-1.5ppm and between the chlorion of 6-12ppm, and this electrolyzer is equiped with anode and negative electrode; And
In this anode and negative electrode, make the copper in the copper sulfate electrolyte be created on negative electrode and form electrolytic copper foil by electric current.
2. the manufacture method of the electrolytic copper foil of tool folding resistance according to claim 1, wherein copper ion concentration is 40~70g/L in this copper sulfate electrolyte.
3. the manufacture method of the electrolytic copper foil of tool folding resistance according to claim 1, wherein sulfuric acid concentration is 60~120g/L in this copper sulfate electrolyte.
4. the manufacture method of the electrolytic copper foil of tool folding resistance according to claim 1, wherein the temperature of this copper sulfate electrolyte is between 40~70 ℃.
5. the manufacture method of the electrolytic copper foil of tool folding resistance according to claim 1, wherein the current density of electroplating process use is 0.4~1.0A/cm
2
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CN 02159066 CN1250775C (en) | 2002-12-27 | 2002-12-27 | Method for producing anti-folding electrolytic copper foil |
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TWI619850B (en) * | 2017-02-24 | 2018-04-01 | 南亞塑膠工業股份有限公司 | Electrolyte solution, electrolytic copper foil and manufacturing method thereof |
CN107153084B (en) * | 2017-05-27 | 2020-05-22 | 佛山市承安铜业有限公司 | Method for researching influence of Cl < - > concentration of copper anode on copper plating quality |
CN108950607B (en) * | 2018-07-09 | 2020-07-07 | 山东金宝电子股份有限公司 | Electrolyte for preparing micron-sized porous copper foil through electrodeposition and method for preparing micron-sized porous copper foil by using electrolyte |
CN109208041B (en) * | 2018-09-18 | 2020-06-02 | 山东金宝电子股份有限公司 | Additive for preparing high-performance ultrathin double-sided smooth copper foil |
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