CN104694939A - Surface treatment technology for ultralow-surface-roughness copper foil - Google Patents
Surface treatment technology for ultralow-surface-roughness copper foil Download PDFInfo
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Abstract
The invention discloses a surface treatment technology for ultralow-surface-roughness copper foil. The technological process includes the steps that acid pickling is carried out on an ultralow-surface-roughness copper foil base material to remove oxides on the surface of the copper foil; the treated crude copper foil serves as an anode, an insoluble electrode or a copper plate serves as a cathode, sulfuric acid serves as electrolyte, and under the action of impressed currents, electrochemical corrosion occurs on the surface of the anode crude copper foil; barrier layer treatment is carried out on the copper foil treatment surface; the surface of the copper foil is treated in an antioxidative mode; the treated surface of the copper foil is organically treated and dried to obtain finished product foil. The copper foil produced through the technology is low in surface roughness and large in specific area and meets the requirement of an FPC for low roughness and high peel strength of the copper foil.
Description
Technical field
The invention belongs to electrolytic copper foil production technical field, be specifically related to a kind of ultra-low profile electrolytic copper foil surface treatment process.
Background technology
Along with the small of electronic product, printed-wiring board (PWB) (PCB) is also towards " close, thin, the flat " future development based on high-density interconnect technology, make the share of market of flexible PCB (FPC) more and more higher, Copper Foil as printed-wiring board (PWB) PCB important foundation material also thereupon towards slimming, low profile future development.Method mainly electrolytic process and the rolling process of existing market manufacturing copper foil, electrolytic copper foil production process mainly contains three large processes: raw paper tinsel electrolysis, surface treatment and product are cut.
FPC electrolytic copper foil has low profile (surperficial low roughness), high-elongation, high-tensile and higher peel strength.The surfaceness of Copper Foil is lower, and the mechanical thickness making FPC can reduce, and resist bending (MIT) performance will significantly improve.Higher unit elongation, can split problem by the copper effectively solved when FPC bends.High-tensile then can improve Copper Foil fatigue property.Higher peel strength ensures the cohesive force between Copper Foil and substrate.
The tensile strength and the unit elongation that are applied to low profile (LP) electrolytic copper foil of FPC are at present higher, but the shortcoming that surfaceness is enough not low, make the thick increase of glue in FPC product, result in MIT performance sharply to decline, and the too high meeting of roughness makes FPC plate there is insulativity safety problem; And too low roughness Copper Foil makes cohesive force not easily cause Copper Foil to depart from substrate.
The peel strength of Copper Foil is mainly relevant with the surface-area on paper tinsel surface, and the cohesive force that copper foil surface amasss larger itself and PCB or FPC substrate is larger, and the peel strength of Copper Foil is larger.But one deck branch dendrite can be adhered in Copper Foil its surface after conventional surface process roughening treatment, peel strength to be met the requirements of under this kind of crystal habit and the roughness of Copper Foil treated side will be made to become large thus do not reach the roughness requirements of FPC Copper Foil.
When solving the contradiction of Copper Foil low roughness and peel strength in prior art, mainly start with from the crystal habit changing copper foil surface, make Copper Foil Copper Foil treat surface in low roughness situation have the specific surface area highly launched.The way realizing this object general is: in alligatoring electrolytic solution, add mixed additive to obtain the fine effect of copper foil surface crystallization thus to realize the effect of electrolytic copper foil low profile high peel strength, although the surfaceness that this kind of method to a certain degree can reduce Copper Foil reaches crystallite effect, the roughness obtaining Copper Foil can't meet the technical requirements of some special FPC Copper Foil completely; By the micro-etching solution containing hydrochloric acid and copper sulfate, pure chemistry corrosion is carried out to Copper Foil hair side exactly in addition, obtain low profile copper foil and ensure that the peel strength requirement of Copper Foil, this kind of technology can solve the peel strength problem of low profile copper foil preferably, but in process of production because hydrochloric acid has stronger volatility can produce adverse influence to staff and environment and be unfavorable for management and control, because its etching time is longer, under certain processing speed, make surface disposing line longer, improve production cost.
Summary of the invention
The present invention proposes a kind of ultra-low profile electrolytic copper foil surface treatment process, and for solving the problem, the copper foil surface roughness gone out through this explained hereafter is low, specific surface area large, meets the low roughness of FPC to Copper Foil and the requirement of high-peeling strength.
Technical scheme of the present invention is achieved in that
A kind of ultra-low profile electrolytic copper foil surface treatment process, technical process is:
First, the raw paper tinsel oxide on surface of pickling removing Copper Foil is carried out to low profile copper foil base material;
Secondly, using raw for the Copper Foil after process paper tinsel as anode, insoluble electrode is as negative electrode or copper coin as negative electrode, and sulfuric acid is as electrolytic solution, and under the effect of impressed current, galvanic corrosion occurs on anode Copper Foil raw paper tinsel surface;
Again, blocking layer process is done to Copper Foil treated side;
Then, antioxidation treatment is done to copper foil surface;
Finally, organic-treating post-drying is done to Copper Foil treated side and obtain finished product paper tinsel.
Preferably, the process of described blocking layer plates one deck Zinc-nickel alloys inside Copper Foil place; Described oxide treatment plates one deck chromium at copper foil surface; Described organic-treating is coated with spray one deck silane coupling agent at copper foil surface.
Preferably, the mass concentration per-cent of electrolytic solution sulfuric acid is 15% ~ 35%, and electrolytic current density is 5 ~ 25A/dm
2, electrolysis time 2 ~ 8s.
Further, processing step is as follows,
1) pickling: pure for technique diluting concentrated sulfuric acid is become mass concentration per-cent be 8% ~ 12% dilution heat of sulfuric acid, pump in pickling tank, then copper foil base material is put into pickling tank soak 3s ~ 5s;
2) galvanic corrosion: pure for technique diluting concentrated sulfuric acid is become mass concentration per-cent be 15% ~ 25% dilution heat of sulfuric acid, pumping in electrolyzer, with step 1) Copper Foil that obtains does anode after process, and copper coin is as negative electrode, carry out electrolytic corrosion at normal temperatures, electrolytic current density is 5 ~ 25A/dm
2, electrolysis time 2 ~ 6s;
3) blocking layer process: zinc sulfate, single nickel salt and potassium pyrosulfate are mixed with after water dissolution respectively, mix rear sulfuric acid or potassium hydroxide and regulate PH, mixed mixed solution pumps in aqueduct, with step 2) Copper Foil that obtains after process does negative electrode, carry out electroplating processes, Zn in mixed solution
2+concentration is 0.5 ~ 2g/l, Ni
2+concentration is 0.5 ~ 3g/l, K
4p
2o
7concentration is 45 ~ 55g/l, and the pH value of mixed solution is 9 ~ 9.5, temperature 25 ~ 35 DEG C, current density are 5 ~ 15A/dm
2, electroplating time is 2 ~ 6S;
4) anti-oxidation process: chromic anhydride, potassium pyrophosphate are mixed with after water dissolution respectively, mix rear sulfuric acid or potassium hydroxide adjustment pH value, mixed mixed solution pumps in coating bath, with step 3) Copper Foil that obtains does negative electrode and carries out electroplating processes, CrO in mixed solution after process
3concentration 1 ~ 5g/l, K
4p
2o
7concentration 15 ~ 25g/l, the pH value of mixed solution is 9 ~ 9.5, temperature 25 ~ 35 DEG C, current density 4 ~ 8A/dm
2, electroplating time is 1 ~ 5S;
5) organic-treating: silane coupling agent is added to the water, step 4 is sprayed at after mixing) copper foil surface that obtains after process, silane coupling agent is γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane (KBM-403), the concentration of KBM-403 solution is 1 ~ 6g/l, the pH value of KBM-403 solution is 6 ~ 8, temperature normal temperature, treatment time 1 ~ 3S;
6) dry: by step 5) to carry out bake out temperature be 150 ~ 250 DEG C for the Copper Foil that obtains, drying time is 3 ~ 6S, namely obtains finished product paper tinsel.
Beneficial effect:
1) in the present invention Copper Foil through electrolytic corrosion, many small pits are gone out in its surface crystallization galvanic corrosion, the impact of this pit on Copper Foil roughness is minimum, the specific area of Copper Foil treated side significantly increases simultaneously, Copper Foil through present invention process process has excellent heat-and corrosion-resistant performance, and there is good anti-normal temperature, high temperature oxidation resistance, there is ultralow low profile and comparatively high-peeling strength, be specially adapted to the production of FPC.
2) through present invention process process Copper Foil containing the element that harmful arsenic, antimony, lead, mercury, cadmium etc. is harmful, meet health environment-friendly theory now.
3) anodic corrosion of the present invention only needs an electrolyzer to save more equipment than original roughening treatment, reduces production cost; And sulfuric acid is stable acid, is convenient to management and control.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is process flow diagram of the present invention.
Fig. 2 is that in the present invention, after Copper Foil galvanic corrosion, hair side 2000 times of SEM scheme.
Fig. 3 is that in the present invention, after Copper Foil galvanic corrosion, 2000 times, light face SEM schemes.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Shown in Figure 1, a kind of ultra-low profile electrolytic copper foil surface treatment process, processing step is as follows,
A kind of ultra-low profile electrolytic copper foil surface treatment process, technical process is:
First, the raw paper tinsel oxide on surface of pickling removing Copper Foil is carried out to low profile copper foil base material;
Secondly, using raw for the Copper Foil after process paper tinsel as anode, insoluble electrode is as negative electrode or copper coin as negative electrode, and sulfuric acid is as electrolytic solution, and under the effect of impressed current, galvanic corrosion occurs on anode Copper Foil raw paper tinsel surface;
Again, blocking layer process is done to Copper Foil treated side;
Then, antioxidation treatment is done to copper foil surface;
Finally, organic-treating post-drying is done to Copper Foil treated side and obtain finished product paper tinsel.
Preferably, the process of described blocking layer plates one deck Zinc-nickel alloys inside Copper Foil place; Described oxide treatment plates one deck chromium at copper foil surface; Described organic-treating is coated with spray one deck silane coupling agent at copper foil surface.
Preferably, the mass concentration per-cent of electrolytic solution sulfuric acid is 15% ~ 35%, and electrolytic current density is 5 ~ 25A/dm
2, electrolysis time 2 ~ 8s.
Further, processing step is as follows,
1) pickling: pure for technique diluting concentrated sulfuric acid is become mass concentration per-cent be 8% ~ 12% dilution heat of sulfuric acid, pump in pickling tank, then copper foil base material is put into pickling tank soak 3s ~ 5s;
2) galvanic corrosion: pure for technique diluting concentrated sulfuric acid is become mass concentration per-cent be 15% ~ 25% dilution heat of sulfuric acid, pumping in electrolyzer, with step 1) Copper Foil that obtains does anode after process, and copper coin is as negative electrode, carry out electrolytic corrosion at normal temperatures, electrolytic current density is 5 ~ 25A/dm
2, electrolysis time 2 ~ 6s;
3) blocking layer process: zinc sulfate, single nickel salt and potassium pyrosulfate are mixed with after water dissolution respectively, mix rear sulfuric acid or potassium hydroxide and regulate PH, mixed mixed solution pumps in aqueduct, with step 2) Copper Foil that obtains after process does negative electrode, carry out electroplating processes, Zn in mixed solution
2+concentration is 0.5 ~ 2g/l, Ni
2+concentration is 0.5 ~ 3g/l, K
4p
2o
7concentration is 45 ~ 55g/l, and the pH value of mixed solution is 9 ~ 9.5, temperature 25 ~ 35 DEG C, current density are 5 ~ 15A/dm
2, electroplating time is 2 ~ 6S;
4) anti-oxidation process: chromic anhydride, potassium pyrophosphate are mixed with after water dissolution respectively, mix rear sulfuric acid or potassium hydroxide adjustment pH value, mixed mixed solution pumps in coating bath, with step 3) Copper Foil that obtains does negative electrode and carries out electroplating processes, CrO in mixed solution after process
3concentration 1 ~ 5g/l, K
4p
2o
7concentration 15 ~ 25g/l, the pH value of mixed solution is 9 ~ 9.5, temperature 25 ~ 35 DEG C, current density 4 ~ 8A/dm
2, electroplating time is 1 ~ 5S;
5) organic-treating: silane coupling agent is added to the water, step 4 is sprayed at after mixing) copper foil surface that obtains after process, silane coupling agent is γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane (KBM-403), the concentration of KBM-403 solution is 1 ~ 6g/l, the pH value of KBM-403 solution is 6 ~ 8, temperature normal temperature, treatment time 1 ~ 3S;
6) dry: by step 5) to carry out bake out temperature be 150 ~ 250 DEG C for the Copper Foil that obtains, drying time is 3 ~ 6S, namely obtains finished product paper tinsel.
The raw paper tinsel specification of Copper Foil is used: 12 μm of raw paper tinsels, raw paper tinsel hair side roughness≤2.0 μm in following embodiment and comparative example.
Embodiment 1
The concrete implementation step of the present embodiment is as follows:
1) pickling: H
2sO
4mass concentration 8%, temperature: normal temperature, treatment time 3S, its objective is the oxide compound of removing copper foil surface.
2) galvanic corrosion: H
2sO
4mass concentration 15%, temperature: normal temperature, current density 5A/dm
2, treatment time 3S, its objective is and lose many small pits by electrolytic corrosion at copper foil surface, increase the specific surface area in paper tinsel face.
3) blocking layer process: ZnSO
40.5g/l, NiSO
40.5g/l, K
4p
2o
748g/l, PH9.2, temperature 30 DEG C, current density 5A/dm
2, treatment time 6S, its objective is the thermotolerance, resistance to lateral erosion and the antioxidant property that improve Copper Foil and prevent from occurring copper atom transport phenomena when follow-up and substrate pressing.
4) zone of oxidation process: CrO
31g/l, K
4p
2o
715g/l, PH 9.0, temperature 30 DEG C, current density 4A/dm
2, treatment time 5S, its object improves normal temperature, the high-temperature oxidation resistance of Copper Foil.
5) organic-treating: KBM-4031g/l, temperature: normal temperature, PH8, treatment time 2S, its objective is the peel strength increasing Copper Foil.
6) dry: temperature 150 DEG C, treatment time 6S, its objective is the moisture content of removing copper foil surface.
Embodiment 2
The concrete implementation step of the present embodiment is as follows:
1) pickling: H
2sO
4mass concentration 8.5%, temperature: normal temperature, treatment time 3.5S.
2) galvanic corrosion: H
2sO
4mass concentration 15%, temperature: normal temperature, current density 10A/dm
2, treatment time 4S.
3) blocking layer process: ZnSO
40.5g/l, NiSO
41g/l, K
4p
2o
750g/l, PH 9.1, temperature 25 DEG C, current density 6A/dm
2, treatment time 3S.
4) zone of oxidation process: CrO
32g/l, K
4p
2o
716g/l, PH 9.2, temperature 30 DEG C, current density 5A/dm
2, treatment time 3S.
5) organic-treating: KBM-4035g/l, temperature: normal temperature, PH6.9, treatment time 1S.
6) dry: temperature 180 DEG C, treatment time 4S.
Embodiment 3
The concrete implementation step of the present embodiment is as follows:
1) pickling: H
2sO
4mass concentration 9%, temperature: normal temperature, treatment time 3.5S.
2) galvanic corrosion: H
2sO
4mass concentration 15%, temperature: normal temperature, current density 15A/dm
2, treatment time 5S.
3) blocking layer process: ZnSO41g/l, NiSO
41.5g/l, K
4p
2o
746g/l, PH 9.1, temperature 31 DEG C, current density 10A/dm
2, treatment time 3S.
4) zone of oxidation process: CrO
33g/l, K
4p
2o
720g/l, PH 9.4, temperature 25 DEG C, current density 5A/dm
2, treatment time 3S.
5) organic-treating: KBM-4035g/l, temperature: normal temperature, PH6.8, treatment time 1S.
6) dry: temperature 170 DEG C, treatment time 4S.
Embodiment 4
The concrete implementation step of the present embodiment is as follows:
1) pickling: H
2sO
4mass concentration 9.5%, temperature: normal temperature, treatment time 4S.
2) galvanic corrosion: H
2sO
4mass concentration 20%, temperature: normal temperature, current density 20A/dm
2, treatment time 6S.
3) blocking layer process: ZnSO
41g/l, NiSO
42g/l, K
4p
2o
752g/l, PH 9.0, temperature 29 DEG C, current density 5A/dm
2, treatment time 4S.
4) zone of oxidation process: CrO
32g/l, K
4p
2o
718g/l, PH 9.2, temperature 30 DEG C, current density 5A/dm
2, treatment time 4S.
5) organic-treating: KBM-4034g/l, temperature: normal temperature, PH6.8, treatment time 2S.
6) dry: temperature 180 DEG C, treatment time 5S.
Embodiment 5
The concrete implementation step of the present embodiment is as follows:
1) pickling: H
2sO
4mass concentration 10%, temperature: normal temperature, treatment time 4S.
2) galvanic corrosion: H
2sO
4mass concentration 20%, temperature: normal temperature, current density 25A/dm
2, treatment time 2S.
3) blocking layer process: ZnSO
41.5g/l, NiSO
42.5g/l, K
4p
2o
754g/l, PH 9.3, temperature 28 DEG C, current density 10A/dm
2, treatment time 3S.
4) zone of oxidation process: CrO
34g/l, K
4p
2o
720g/l, PH 9.2, temperature 27 DEG C, current density 3A/dm
2, treatment time 3S.
5) organic-treating: KBM-4035g/l, temperature: normal temperature, PH6.8, treatment time 1S.
6) dry: temperature 160 DEG C, treatment time 4S.
Embodiment 6
The concrete implementation step of the present embodiment is as follows:
1) pickling: H
2sO
4mass concentration 10.5%, temperature: normal temperature, treatment time 4.5S.
2) galvanic corrosion: H
2sO
4mass concentration 20%, temperature: normal temperature, current density 10A/dm
2, treatment time 4S.
3) blocking layer process: ZnSO
41.5g/l, NiSO
41g/l, K
4p
2o
746g/l, PH 9.4, temperature 29 DEG C, current density 8A/dm
2, treatment time 5S.
4) zone of oxidation process: CrO
32g/l, K
4p
2o
717g/l, PH 9.5, temperature 30 DEG C, current density 8A/dm
2, treatment time 1S.
5) organic-treating: KBM-4033g/l, temperature: normal temperature, PH7.2, treatment time 3S.
6) dry: temperature 200 DEG C, treatment time 3S.
Embodiment 7
The concrete implementation step of the present embodiment is as follows:
1) pickling: H
2sO
4mass concentration 11%, temperature: normal temperature, treatment time 4.5S.
2) galvanic corrosion: H
2sO
4mass concentration 25%, temperature: normal temperature, current density 8A/dm
2, treatment time 5S.
3) blocking layer process: ZnSO
42g/l, NiSO
41.5g/l, K
4p
2o
748g/l, PH 9.1, temperature 35 DEG C, current density 10A/dm
2, treatment time 3S.
4) zone of oxidation process: CrO
35g/l, K
4p
2o
720g/l, PH 9.2, temperature 28 DEG C, current density 5A/dm
2, treatment time 2S.
5) organic-treating: KBM-4035g/l, temperature: normal temperature, PH6.8, treatment time 1S.
6) dry: temperature 180 DEG C, treatment time 4S.
Embodiment 8
The concrete implementation step of the present embodiment is as follows:
1) pickling: H
2sO
4mass concentration 12%, temperature: normal temperature, treatment time 5S.
2) galvanic corrosion: H
2sO
4mass concentration 25%, temperature: normal temperature, current density 8A/dm
2, treatment time 6S.
3) blocking layer process: ZnSO
42g/l, NiSO
43g/l, K
4p
2o
750g/l, PH 9.5, temperature 30 DEG C, current density 10A/dm
2, treatment time 2S.
4) zone of oxidation process: CrO
35g/l, K
4p
2o
720g/l, PH 9.1, temperature 30 DEG C, current density 6A/dm
2, treatment time 3S.
5) organic-treating: KBM-4036g/l, temperature: normal temperature, PH8, treatment time 1S.
6) dry: temperature 250 DEG C, treatment time 6S.
| Embodiment | H 2SO 4Mass concentration | Temperature | Treatment time (s) |
| Embodiment 1 | 8％ | Normal temperature | 3 |
| Embodiment 2 | 8.5％ | Normal temperature | 3.5 |
| Embodiment 3 | 9％ | Normal temperature | 3.5 |
| Embodiment 4 | 9.5％ | Normal temperature | 4 |
| Embodiment 5 | 10％ | Normal temperature | 4 |
| Embodiment 6 | 10.5％ | Normal temperature | 4.5 |
| Embodiment 7 | 11％ | Normal temperature | 4.5 |
| Embodiment 8 | 12％ | Normal temperature | 5 |
Table 1 is the parameter of acid pickling step in specific embodiment
Table 2 is the parameter of galvanic corrosion step in specific embodiment
Table 3 is the parameter of blocking layer treatment step in embodiment
Table 4 is the parameter of zone of oxidation treatment step in embodiment
| Embodiment | KBM-403(g/l) | Temperature (DEG C) | PH | Treatment time (s) |
| Embodiment 1 | 1 | Normal temperature | 8 | 2 |
| Embodiment 2 | 5 | Normal temperature | 6.9 | 1 |
| Embodiment 3 | 5 | Normal temperature | 6.8 | 1 |
| Embodiment 4 | 4 | Normal temperature | 6.8 | 2 |
| Embodiment 5 | 5 | Normal temperature | 6.8 | 1 |
| Embodiment 6 | 3 | Normal temperature | 7.2 | 3 |
| Embodiment 7 | 5 | Normal temperature | 6.8 | 1 |
| Embodiment 8 | 6 | Normal temperature | 8 | 1 |
Table 5 is the parameter of organic-treating step in embodiment
| Embodiment | Temperature (DEG C) | Treatment time (s) |
| Embodiment 1 | 150 | 6 |
| Embodiment 2 | 180 | 4 |
| Embodiment 3 | 170 | 4 |
| Embodiment 4 | 180 | 5 |
| Embodiment 5 | 160 | 4 |
| Embodiment 6 | 200 | 3 |
| Embodiment 7 | 180 | 4 |
| Embodiment 8 | 250 | 6 |
Table 6 is the parameter of baking step in embodiment
Through the Copper Foil hair side roughness of above embodiment process and peel strength (peel strength adopts the soft board of polyimide material to detect) as following table
Table 7 is the coarse contrast of hair side and stripping strength contrast table before and after process
Can find out that the copper foil surface crystallization after process of surface treatment of the present invention has much small pit according to table 7 and Fig. 2 and 3, make Copper Foil under the state of ultra-low profile, have higher unfolded surface and amass.Increase by 0.3 ~ 0.5 μm than untreated Copper Foil roughness through its surfaceness≤2.5 of Copper Foil of process of the present invention μm, peel strength >=1.0N/mm, is specially adapted to the production of FPC.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (4)
1. a ultra-low profile electrolytic copper foil surface treatment process, is characterised in that its technical process is:
First, the raw paper tinsel oxide on surface of pickling removing Copper Foil is carried out to low profile copper foil base material;
Secondly, using raw for the Copper Foil after process paper tinsel as anode, insoluble electrode is as negative electrode or copper coin as negative electrode, and sulfuric acid is as electrolytic solution, and under the effect of impressed current, galvanic corrosion occurs on anode Copper Foil raw paper tinsel surface;
Again, blocking layer process is done to Copper Foil treated side;
Then, antioxidation treatment is done to copper foil surface;
Finally, organic-treating post-drying is done to Copper Foil treated side and obtain finished product paper tinsel.
2. ultra-low profile electrolytic copper foil surface treatment process as claimed in claim 1, is characterized in that: the process of described blocking layer plates one deck Zinc-nickel alloys inside Copper Foil place; Described oxide treatment plates one deck chromium at copper foil surface; Described organic-treating is coated with spray one deck silane coupling agent at copper foil surface.
3. ultra-low profile electrolytic copper foil surface treatment process as claimed in claim 1, is characterized in that: the mass concentration per-cent of electrolytic solution sulfuric acid is 15% ~ 35%, and electrolytic current density is 5 ~ 25A/dm
2, electrolysis time 2 ~ 8s.
4. ultra-low profile electrolytic copper foil surface treatment process as claimed in claim 2, is characterized in that: processing step is as follows,
1) pickling: pure for technique diluting concentrated sulfuric acid is become mass concentration per-cent be 8% ~ 12% dilution heat of sulfuric acid, pump in pickling tank, then copper foil base material is put into pickling tank soak 3s ~ 5s;
2) galvanic corrosion: pure for technique diluting concentrated sulfuric acid is become mass concentration per-cent be 15% ~ 25% dilution heat of sulfuric acid, pumping in electrolyzer, with step 1) Copper Foil that obtains does anode after process, and copper coin is as negative electrode, carry out electrolytic corrosion at normal temperatures, electrolytic current density is 5 ~ 25A/dm
2, electrolysis time 2 ~ 6s;
3) blocking layer process: zinc sulfate, single nickel salt and potassium pyrosulfate are mixed with after water dissolution respectively, mix rear sulfuric acid or potassium hydroxide and regulate PH, mixed mixed solution pumps in aqueduct, with step 2) Copper Foil that obtains after process does negative electrode, carry out electroplating processes, Zn in mixed solution
2+concentration is 0.5 ~ 2g/l, Ni
2+concentration is 0.5 ~ 3g/l, K
4p
2o
7concentration is 45 ~ 55g/l, and the pH value of mixed solution is 9 ~ 9.5, temperature 25 ~ 35 DEG C, current density are 5 ~ 15A/dm
2, electroplating time is 2 ~ 6S;
4) anti-oxidation process: chromic anhydride, potassium pyrophosphate are mixed with after water dissolution respectively, mix rear sulfuric acid or potassium hydroxide adjustment pH value, mixed mixed solution pumps in coating bath, with step 3) Copper Foil that obtains does negative electrode and carries out electroplating processes, CrO in mixed solution after process
3concentration 1 ~ 5g/l, K
4p
2o
7concentration 15 ~ 25g/l, the pH value of mixed solution is 9 ~ 9.5, temperature 25 ~ 35 DEG C, current density 4 ~ 8A/dm
2, electroplating time is 1 ~ 5S;
5) organic-treating: silane coupling agent is added to the water, step 4 is sprayed at after mixing) copper foil surface that obtains after process, silane coupling agent is γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane (KBM-403), the concentration of KBM-403 solution is 1 ~ 6g/l, the pH value of KBM-403 solution is 6 ~ 8, temperature normal temperature, treatment time 1 ~ 3S;
6) dry: by step 5) to carry out bake out temperature be 150 ~ 250 DEG C for the Copper Foil that obtains, drying time is 3 ~ 6S, namely obtains finished product paper tinsel.
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|---|---|---|---|
| CN201510160277.5A CN104694939A (en) | 2015-04-07 | 2015-04-07 | Surface treatment technology for ultralow-surface-roughness copper foil |
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|---|---|---|---|
| CN201510160277.5A CN104694939A (en) | 2015-04-07 | 2015-04-07 | Surface treatment technology for ultralow-surface-roughness copper foil |
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| CN201510160277.5A Pending CN104694939A (en) | 2015-04-07 | 2015-04-07 | Surface treatment technology for ultralow-surface-roughness copper foil |
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| CN105039947A (en) * | 2015-07-07 | 2015-11-11 | 安徽铜冠铜箔有限公司 | Oxidation prevention process used for lithium ion battery copper foil |
| CN105220214A (en) * | 2015-11-13 | 2016-01-06 | 中国科学院上海高等研究院 | A kind of preparation method of graphene film |
| CN107946596A (en) * | 2016-10-12 | 2018-04-20 | Ls美创有限公司 | Easy-to-handle electrolytic copper foil including its electrode and secondary cell and its manufacture method |
| CN108611676A (en) * | 2018-07-04 | 2018-10-02 | 山西沃特海默新材料科技股份有限公司 | A kind of the electrochemical corrosion preparation method and its micropore copper foil of micropore battery copper foil |
| CN108673633A (en) * | 2018-04-28 | 2018-10-19 | 郑玉祥 | A kind of working method of the post-processing split air conditioner with robot for punching |
| CN109137013A (en) * | 2018-07-13 | 2019-01-04 | 铜陵市华创新材料有限公司 | A kind of electrolytic copper foil surface electro-deposition ZN-NI-P-LA alloying technology |
| CN109267113A (en) * | 2018-11-20 | 2019-01-25 | 江东电子材料有限公司 | A kind of anti-oxidation technique of electrolytic copper foil and its system |
| CN109402572A (en) * | 2018-12-25 | 2019-03-01 | 胡旭日 | A kind of production method and equipment of no glue flexible copper-clad plate |
| CN109881221A (en) * | 2019-03-04 | 2019-06-14 | 深圳市汇美新科技有限公司 | A kind of ultrathin film electroplating technology of high fracture elongation |
| CN113973437A (en) * | 2021-09-09 | 2022-01-25 | 九江德福科技股份有限公司 | Surface treatment method of copper foil for high-speed high-frequency signal transmission circuit board |
| CN114196994A (en) * | 2021-12-30 | 2022-03-18 | 山东金宝电子股份有限公司 | Roughening solution and roughening process for surface of copper foil |
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| CN105039947A (en) * | 2015-07-07 | 2015-11-11 | 安徽铜冠铜箔有限公司 | Oxidation prevention process used for lithium ion battery copper foil |
| CN105220214A (en) * | 2015-11-13 | 2016-01-06 | 中国科学院上海高等研究院 | A kind of preparation method of graphene film |
| CN107946596A (en) * | 2016-10-12 | 2018-04-20 | Ls美创有限公司 | Easy-to-handle electrolytic copper foil including its electrode and secondary cell and its manufacture method |
| CN108673633A (en) * | 2018-04-28 | 2018-10-19 | 郑玉祥 | A kind of working method of the post-processing split air conditioner with robot for punching |
| CN108611676A (en) * | 2018-07-04 | 2018-10-02 | 山西沃特海默新材料科技股份有限公司 | A kind of the electrochemical corrosion preparation method and its micropore copper foil of micropore battery copper foil |
| CN109137013A (en) * | 2018-07-13 | 2019-01-04 | 铜陵市华创新材料有限公司 | A kind of electrolytic copper foil surface electro-deposition ZN-NI-P-LA alloying technology |
| CN109267113A (en) * | 2018-11-20 | 2019-01-25 | 江东电子材料有限公司 | A kind of anti-oxidation technique of electrolytic copper foil and its system |
| CN109402572A (en) * | 2018-12-25 | 2019-03-01 | 胡旭日 | A kind of production method and equipment of no glue flexible copper-clad plate |
| CN109881221A (en) * | 2019-03-04 | 2019-06-14 | 深圳市汇美新科技有限公司 | A kind of ultrathin film electroplating technology of high fracture elongation |
| CN113973437A (en) * | 2021-09-09 | 2022-01-25 | 九江德福科技股份有限公司 | Surface treatment method of copper foil for high-speed high-frequency signal transmission circuit board |
| CN113973437B (en) * | 2021-09-09 | 2022-09-09 | 九江德福科技股份有限公司 | Surface treatment method of copper foil for high-speed high-frequency signal transmission circuit board |
| CN114196994A (en) * | 2021-12-30 | 2022-03-18 | 山东金宝电子股份有限公司 | Roughening solution and roughening process for surface of copper foil |
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