CN101906630B - Black surface treatment process of electrolytic copper foil - Google Patents
Black surface treatment process of electrolytic copper foil Download PDFInfo
- Publication number
- CN101906630B CN101906630B CN2010102456862A CN201010245686A CN101906630B CN 101906630 B CN101906630 B CN 101906630B CN 2010102456862 A CN2010102456862 A CN 2010102456862A CN 201010245686 A CN201010245686 A CN 201010245686A CN 101906630 B CN101906630 B CN 101906630B
- Authority
- CN
- China
- Prior art keywords
- copper foil
- additive
- copper
- temperature
- current density
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention relates to a black surface treatment process of an electrolytic copper foil, belonging to the technical field of production processes of high and precision electrolytic copper foils. The black surface treatment process of an electrolytic copper foil is characterized in that a VLP (Very Low Profile) electrolytic copper foil of 8-12 mu is used as an electrode, and then copper or copper alloy is roughened, solidified, weakly roughened and electrically deposited at a running speed of 25.0+/-0.1m/min; a layer of nano-scale nickel or cobalt alloy and a layer of nano-scale zinc alloyare sequentially and electrically deposited; and then alkaline chromate passivation is carried out and a layer of coupling agent is coated. In the invention, the black copper foil for an FPC (Flexible Printing Circuit) is obtained by carrying out a series of special surface treatments on the ultrathin and VLP electrolytic copper foil of 8-12 mu, wherein the surface roughness Ra of the obtained copper foil is smaller than or equal to 0.30 mu, Rz is smaller than or equal to 2.5 mu; the thickness of the copper foil subjected to the surface treatments is increased by 1.40-1.80 mu; the copper foil does not contain elements having serious damages to the human body, such as lead, mercury, cadmium, stibium, and the like and has excellent oxidation resistance as well as corrosion and etching resistance; the peel strength of the copper foil on a PI (Polyimide) film reaches higher than 1.0N/mm, and the folding strength on the PI film reach more than 100 thousand numbers of times; the copper foil has good appearance characteristics after the copper foil is microetched, and after the copper foil is made into an FCCL (Flexible Copper Clad Laminate), the copper foil has similar appearance characteristics to a rolled copper foil; and the properties of the copper foil product are equivalent to that of an electrolytic copper foil with the same specification for the FCCL.
Description
Technical field
The present invention relates to a kind of black surface treatment process of electrolytic copper foil, belong to the high-precision electrolytic copper foil technical field of producing.
Background technology
Flexible print wiring board (Flexible Printed Circuit, FPC), have advantages such as softness, light, thin and deflection, at the information electronic product fast under light, thin, short, the little trend of trend, products such as notebook computer, digital camera, mobile phone, pick up camera, liquid-crystal display, telecommunications, aviation be electric have been widely used in.From the mid-90 in 20th century to now, FPC market turns to civilianly from military rapidly, turns to consumer electronics product to attach most importance to, and has formed the situation that the nearly all high-tech electronic product that emerges in recent years all adopts FPC in a large number.
FCCL (FCCL is the processing base material of flexible print wiring board) is the special CCL of a class (copper clad laminate), thin except that having, the light and flexual advantage, also has the characteristics of electrical property, thermal characteristics, excellent heat resistance.It than low-k (Dk) property, make electrical signal be transmitted fast.Good thermal characteristics can make assembly be easy to cooling.Higher second-order transition temperature (Tg) can make assembly well move under higher temperature.Because the most product of FCCL is to offer its client with continuous one-tenth web-like form, therefore, adopt FCCL to produce printed circuit board, can be beneficial to automatic continuous production that realizes FPC and the continuity surface mounting of on FPC, carrying out components and parts.Can be for electric interconnection provide the thinnest insulation support plate, under the extreme case, can produce the flexible sheet of 0.002 inch of the whole thickness less than that comprises tectum, significantly reduce the weight of Electronic Packaging.Can be fully with external form, assembling, and function combine, shortened the settling time of product.In addition, using FPC is the best approach that reduces electric encapsulation interconnection number of times, and can be in the installation line drive test examination of advancing.In addition, the homogeneity aspect thickness and electrical property has determined its application in high speed circuit; Many electronic products have the array of a lot of input and output, usually need to occupy the one side of more than product, so just need design on three-dimensional and make, and FPC then realizes easily.The feasible used printed circuit board of complete machine electronic product in recent years of These characteristics, very fast turns to FPC from rigidity.
Copper Foil is one of main raw material of FCCL production, can divide calendering and two kinds of manufacture crafts of electrolysis by production method.Rolled copper foil has excellent performances such as unit elongation, anti-bending and high temperature recrystallization, and this also is the reason that former FCCL manufacturer only uses rolled copper foil.In recent years, raising along with the electrolytic copper foil production technology, Japan part Copper Foil producer has developed and has been suitable for the electrolytic copper foil that FCCL requires, and the FPC that puts on display recently is suitable with the same specification rolled copper foil with resistance to bend(ing) with its unit elongation of electrolytic copper foil, also has the certain high temperature recrystallization.Because PFC has been extensive use of electrolytic copper foil and has replaced rolled copper foil to be used in FPC with the rapid lifting of electrolytic copper foil production technology and advantage in price, increasing FCCL manufacturer.
China is the second largest printed circuit board big export country that is only second to after the Japan, has big gap because the production technology of domestic high-grade electrolytic copper foil is compared with the U.S., Japan, has caused high-grade Copper Foil mainly to rely on the situation of import.For the FCCL Copper Foil of high technology content and high added value, in the numerous domestic Copper Foil manufacturer, there is not a family to produce in batches, almost whole FCCL Copper Foils all are from regional imports such as Japan, Korea S, Taiwan.
At the nano level alloy layer of ultra-thin, the ultralow profile electrolytic copper foil surface of 8-12 μ m galvanic deposit, the character of its coating has very big difference with the plating of general meaning.Performances such as corrosion-resistant, anti-oxidant, the High temperature diffusion of used for printed circuit board copper foil surface coating must be in suitable scope, can not cross by force or excessively.The erosion resistance of copper foil surface coating is strong excessively, and it is clean etching to occur during the online etching of PCB, short circuit can occur when making high-density fine electronic circuit; Erosion resistance excessively a little less than, then lateral erosion can appear, can go out lines when making the ultra fine pitch circuit and come off.The antioxygen on surface is strong excessively, and it is clean microetch to occur when slim copper-clad plate or flexibility coat copper plate microetch, and the overlay film that influences postorder is made, and then the Copper Foil oxidation can occur a little less than antioxygen is crossed.The copper foil surface roughness is too small, and the density of Copper Foil raises, and the peel strength of the last Copper Foil of FCCL descends, and resistance to bend(ing) improves; The Copper Foil roughness is excessive, and the compactness of Copper Foil descends, and the peel strength of the last Copper Foil of FCCL raises, and resistance to bend(ing) descends, and may occur back side pressure when suppressing two-sided thin plate and wear and cause short circuit.
Above-mentioned performance requriements, what show in the FCCL field is stricter, and most advanced FPC technology is embodied in graph thinning and slimming, and the target of graph thinning is to draw close to semiconductor technology, developing to minimum 10 μ m pitches (each 5 μ m of live width/line-spacing) direction, is to adopt additive process technology basically; Slimming is the FPC of thin paper type, and is thinner than present 25 μ m Pl, and can be fit to the high frequency performance requirement, will develop halogen and the matrix resin that can be recycled, nano composite material etc. simultaneously, and this has higher requirement to the FPC base material.
Summary of the invention
But technical problem to be solved by this invention is to provide a kind of high anti-buckling problem that can solve FPC, solve the development of FPC pitch to the requirement of Copper Foil etching and the black surface treatment process that solves the Copper Foil of the appearance of black problem when using electrolytic copper foil to substitute rolled copper foil to be used in FPC, all can reach FPC Copper Foil requirement through the anti-bending of Copper Foil that obtains behind this treatment process, unit elongation, surfaceness, peel strength, moisture resistance, thermotolerance and performance such as anti-oxidant.
The present invention is achieved by the following technical solutions:
The black surface treatment process of electrolytic copper foil, its special character is to adopt 8-12 μ m VLP electrolytic copper foil (very low profile electrolytic copper foil) to move as electrode and with the speed of 25.0 ± 0.1m/min, through roughening solution preparation, curing solution preparation, weak alligatoring acid copper or copper alloy, galvanic deposit one deck sodium meter level nickel or cobalt-base alloy again, the zinc alloy of galvanic deposit one deck sodium meter level passes through basic chromium hydrochlorate Passivation Treatment again and applies one deck coupling agent again.
Concrete treatment step of the present invention is as follows:
1, roughening solution preparation: with cathode copper, the vitriol oil, soft water, vapor mixing dissolving, generate copper-bath, add additive A again in copper-bath, the abundant back of mixing is squeezed into the alligatoring groove with pump and is electroplated; Cu wherein
2+10-30g/L, H
2SO
480-200g/L, additive A 1.5-50ppm, temperature is 25-50 ℃, current density is 20-35A/dm
2Solution circulated is filtered in the electroplating process, per hour each composition in the solution is once tested, and is adjusted concentration to above-mentioned scope according to test result;
Described additive A is a class surfactant, and this surfactant is selected from a kind of in gelatin, thiocarbamide, Natvosol, benzotriazole, Sudan Gum-arabic, the propenyl thiocarbamide.
2, curing solution preparation: cathode copper, the vitriol oil, soft water, vapor mixing are dissolved, generate copper-bath, the abundant back of mixing is squeezed into the curing groove with pump and is electroplated; Cu wherein
2+50-100g/L, H
2SO
480-200g/L, temperature is 35-55 ℃, current density is 20-35A/dm
2Solution circulated is filtered in the electroplating process, per hour each composition in the solution is once tested, and is adjusted concentration to above-mentioned scope according to test result.
3, weak roughening solution preparation: with cathode copper, the vitriol oil, soft water, vapor mixing dissolving, generate copper-bath, add addition of C again in copper-bath, the abundant back of mixing is squeezed into weak alligatoring groove with pump and is electroplated; Cu wherein
2+6-20g/L, H
2SO
480-200g/L, addition of C 1-3g/L, temperature is 25-50 ℃, current density is 6-15A/dm
2In the electroplating process, solution circulated is filtered, and per hour each composition in the solution is once tested, and is adjusted concentration to above-mentioned scope according to test result.
Described addition of C is a kind of nonmetallic compound, and this nonmetallic compound is selected from one or both in N, P, S, As, F, the Cl compound.
4, nickel plating (or cobalt) alloy solution preparation: potassium pyrophosphate, single nickel salt (or rose vitriol), zinc sulfate, additive M, additive N are dissolved respectively, squeeze into nickel plating (or cobalt) groove with pump behind the thorough mixing and electroplate; Wherein, K
4P
2O
7140-300g/L, Ni
2+2.5-15g/L (or Co
2+2-20g/L), Zn
2+0.5-7g/L, additive M 30-450ppm, additive N 1.0-10g/L, PH 8-11, temperature is 25-50 ℃, current density 5-15A/dm
2Solution circulated is filtered in the electroplating process, per hour each composition in the solution is once tested, and is adjusted concentration to above-mentioned scope according to test result.
Described additive M is selected from one or both in Ag, Mo, In, Co, Al, Cu, Mg, Fe, the Sn compound; Additive N is selected from NH
4 +, SCN
-, S
2O
3 2-, AC
-, tartrate anion, citrate, EDTA
-In the compound one or both.
5, galvanized alloy formulations prepared from solutions: potassium pyrophosphate, zinc sulfate are dissolved respectively, again solution of zinc sulfate is added in the potassium pyrophosphate solution, generate zinc pyrophosphate solution, add additive D again, enter the galvanized alloy groove after the mixing fully and electroplate; Wherein, K
4P
2O
7140-300g/L, Zn
2+2-7g/L, additive D 60-150ppm, PH 8-11, temperature is 25-50 ℃, current density is 0.50-1.5A/dm
2Solution circulated is filtered in the electroplating process, per hour each composition in the solution is once tested, and is adjusted concentration to above-mentioned scope according to test result;
Described additive D is selected from one or both in Mo, In, Co, Ni, Al, Cu, Fe, the Sn compound.
6, chromating formulations prepared from solutions: chromic salt is dissolved in soft water, squeeze in the deactivation slot with pump and electroplate, chromic salt 2-10g/L wherein, PH 8-12, temperature is 25-50 ℃, current density is 2.0-8.0A/dm
2Solution circulated is filtered in the electroplating process, per hour each composition in the solution is once tested, and is adjusted concentration to above-mentioned scope according to test result;
Described chromic salt is meant Sodium chromate or potassiumchromate.
7, spraying coupling agent: silane coupling agent is dissolved in the soft water, plays circulation and be sprayed on copper foil surface with pump.
This silane coupling agent is selected from a kind of in amino, vinyl, sulfenyl, the epoxy group(ing), concentration of volume percent 0.1-2%, temperature 15-40 ℃; Per hour each composition in the solution is once tested, and adjusted concentration to above-mentioned scope according to test result.
The surface treatment of Copper Foil of the present invention comprises alligatoring, curing, weak alligatoring, nickel plating (or cobalt) alloy, galvanized alloy, passivation and is coated with seven steps of coupling agent, during processing Copper Foil with the speed operation of 25.0 ± 0.1m/min, each treatment step time 2-4 second.Alligatoring, cathode plane appearance tiny and uniform " ball " shape structure of solidifying the back electrolytic copper foil, forming tiny and fine and close point-like copper alloy on " ball " surface after the weak alligatoring must be brilliant.Alligatoring, solidified main purpose are to strengthen the peel strength of Copper Foil on base material; Weak alligatoring main purpose is the color that strengthens peel strength, enhancing coating erosion resistance and the change coating of Copper Foil on base material; Nickel plating (or cobalt) alloy main purpose provides black coating, the anti-oxidant and erosion resistance of Copper Foil is provided; The main purpose of galvanized alloy is to improve anti-oxidant, corrosion-resistant, the moisture resistance of Copper Foil; The main purpose of passivation is anti-oxidant, the erosion resistance that strengthens coating; The main purpose of spraying coupling agent is to strengthen the peel strength of Copper Foil on FCCL.After surface treatment was finished, copper thickness increased 1.4-1.8 μ m.
The black surface treatment process of electrolytic copper foil of the present invention adopts ultra-thin, the ultralow profile electrolytic copper foil of 8-12 μ m, the FPC black Copper Foil that obtains after handling through a series of special surfaces; Surface roughness Ra≤0.30 μ m, Rz≤2.5 μ m; Increase 1.40-1.80 μ m through copper thickness after the surface treatment; Not containing lead, mercury, cadmium, antimony etc. has the element of serious harm to human body; Have excellent oxidation-resistance, erosion resistance and etching; Peel strength on the PI film reaches more than the 1.0N/mm; Reach more than 100,000 times in the folding on the PI film; Has the good surface appearance characteristic after the microetch; Behind the FCCL that makes, have the similar in appearance feature with using rolled copper foil, product performance are equivalent to the same specification FCCL electrolytic copper foil of import, have filled up domestic this art blank.
Description of drawings
Fig. 1 ultra-thin, ultralow profile electrolytic copper foil technological process of production of the present invention.
Fig. 2 is that black surface of the present invention is handled the Copper Foil technical process.
Fig. 3 surface-treated layer erosion resistance is strong excessively.
The erosion resistance of coating is strong excessively, and it is residual that coating appears in making pitch fine circuits, can form short circuit;
Fig. 4 surface-treated layer erosion resistance excessively a little less than.
The erosion resistance of coating excessively a little less than, side corrosion appears in electronic circuit, the ultra fine pitch circuit lines can occur and come off.
Fig. 5 is ultra-thin, the ultralow profile electrolytic copper foil of 12 μ m that the present invention adopts, and handles the SEM photo under preceding 2000 times.
Fig. 6 is ultra-thin, the ultralow profile electrolytic copper foils of 12 μ m of the present invention, the SEM photo after the surface treatment under 2000 times.
Embodiment
Provide specific embodiments of the present invention below in conjunction with accompanying drawing, further specify technical solution of the present invention, but embodiments of the present invention are not limited to following specific embodiments.
Embodiment 1
The black surface treatment process of electrolytic copper foil, concrete operation is as follows
1, roughening solution preparation: with cathode copper, the vitriol oil, soft water, vapor mixing dissolving, generate copper-bath, add additive A again, the abundant back of mixing is squeezed into the alligatoring groove with pump and is electroplated; Cu wherein
2+15g/L, H
2SO
4150g/L, additive A 50ppm, temperature is 40 ℃, current density 25A/dm
2, additive A is selected thiocarbamide for use.
2, curing solution preparation: with cathode copper, the vitriol oil, soft water, vapor mixing dissolving, generate copper-bath, squeeze into the curing groove with pump and electroplate; Cu wherein
2+65g/L, H
2SO
485g/L, temperature is 80 ℃, current density is 32A/dm
2
3, weak alligatoring: with cathode copper, the vitriol oil, soft water, vapor mixing dissolving, generate copper-bath, in copper-bath, add addition of C again, squeeze into weak alligatoring groove with pump after the mixing fully and electroplate; Addition of C is selected ammonium sulfate for use; Cu wherein
2+12g/L, H
2SO
4110g/L, addition of C 2g/L, temperature is 28 ℃, current density is 10.5A/dm
2
4, nickel plating alloy formulations prepared from solutions: potassium pyrophosphate, single nickel salt, zinc sulfate, additive M, additive N are dissolved respectively, enter nickel bath and electroplate; Additive M selects CoSO for use
47H
2O; It is 1: 3 NH that additive N selects the amount of substance ratio for use
4Cl and KSCN mixture; Wherein, K
4P
2O
7200g/L, Ni
2+10g/L, Zn
2+2.5g/L current density is 10A/dm
2, additive M 200ppm, additive N 5g/L, PH 8.5, and temperature is 30 ℃.
5, galvanized alloy formulations prepared from solutions: potassium pyrophosphate, zinc sulfate are dissolved respectively, mix the back and generate zinc pyrophosphate solution, doping D squeezes into the galvanized alloy groove with pump behind the thorough mixing and electroplates again; Additive D selects Na for use
2MoO
42H
2O, K
4P
2O
7145g/L, Zn
2+3g/L, additive D 65ppm, PH 10.5, and temperature is 30 ℃, current density 1.2A/dm
2
6, chromating formulations prepared from solutions: chromium acid sodium solution is dissolved in the soft water, and the abundant back of mixing is squeezed in the deactivation slot with pump and is electroplated; Sodium chromate 3g/L wherein, PH 11, and temperature is 29 ℃, and current density is 5.2A/dm
2
7, spraying coupling agent: silane coupling agent is soluble in water by the processing requirement index, be sprayed on copper foil surface by recycle pump; This silane coupling agent is selected from a kind of in amino, vinyl, sulfenyl, the epoxy group(ing), concentration of volume percent 0.2%, 38 ℃ of temperature.
Embodiment 2
The difference of present embodiment and embodiment 1 is:
1, alligatoring: Cu
2+20g/L, H
2SO
4150g/L, additive A 10ppm, temperature is 26 ℃, current density 30A/dm
2, additive A is selected gelatin for use.
2, solidify: Cu
2+58g/L, H
2SO
4160g/L, temperature is 40 ℃; Current density 25A/dm
2
3, weak alligatoring: Cu
2+8g/L, H
2SO
4180g/L, addition of C 1.2g/L, temperature is 40 ℃, current density 7.5A/dm
2, addition of C is NaAsO
3
4, cobalt plating alloy: K
4P
2O
7140-300g/L, Co
2+15g/L, Zn
2+1.5g/L, additive M 420ppm, additive N 8.5g/L, PH 9.2, and temperature is 35 ℃, current density 12A/dm
2, additive M is Ag
2SO
4, additive N is NH
4AC.
5, galvanized alloy: K
4P
2O
7220g/L, Zn
2+6.8g/L, additive D 145ppm, PH 9.6, and temperature is 40 ℃, current density 1.6A/dm
2, additive D selects CuSO for use
4
6, passivation: potassiumchromate 8.5g/L, PH 10.6, and temperature is 35 ℃, current density 6.5A/dm
2
7, spraying coupling agent: the coupling agent concentration of volume percent is 0.5%, 33 ℃ of temperature.
Embodiment 3:
The difference of present embodiment and embodiment 1 is:
1, alligatoring: Cu
2+12g/L, H
2SO
4142g/L, additive A 5.5ppm, temperature is 45 ℃, current density 25 A/dm
2, additive A is selected Natvosol for use.
2, solidify: Cu
2+70g/L, H
2SO
495g/L, temperature is 52 ℃; Current density 30A/dm
2
3, weak alligatoring: Cu
2+14g/L, H
2SO
4180g/L, addition of C 1.8g/L, temperature is 50 ℃, current density 9.2A/dm
2, addition of C is selected NH for use
4Cl.
4, nickel plating alloy: K
4P
2O
7180g/L, Ni
2+12g/L, Zn
2+0.5g/L, additive M 120ppm, additive N 3g/L, PH 10.8, and temperature is 40 ℃, current density 12A/dm
2, additive M selects CoSO for use
47H
2O, additive N selects Triammonium citrate for use.
5, galvanized alloy: K
4P
2O
7260g/L, Zn
2+5g/L, additive D 140ppm, PH 10.6, and temperature is 39 ℃, current density 0.68A/dm
2, additive D selects NiSO for use
46H
2O.
6, passivation: Sodium chromate 6.2g/L, PH 11.6, and temperature is 29 ℃, current density 6.5A/dm
2
7, spraying coupling agent: the coupling agent concentration of volume percent is 0.8%, 26 ℃ of temperature.
Embodiment 4:
The difference of present embodiment and embodiment 1 is:
1, alligatoring: Cu
2+18g/L, H
2SO
4160g/L, additive A 29ppm, temperature is 26 ℃, current density 27.6A/dm
2, additive A is selected benzotriazole for use.
2, solidify: Cu
2+62g/L, H
2SO
4120g/L, temperature is 50 ℃; Current density 28A/dm
2
3, weak alligatoring: Cu
2+6.2g/L, H
2SO
4192g/L, addition of C 2.6g/L, temperature is 40 ℃, current density 7.6A/dm
2, addition of C is selected Trisodium trimetaphosphate [(NaPO for use
3)
3].
4, cobalt plating alloy: K
4P
2O
7160g/L, Co
2+9.4g/L, Zn
2+2.6g/L, additive M 220ppm, additive N 6g/L, PH 9.4, and temperature is 42 ℃, current density 9.6A/dm
2Additive M selects CuSO for use
4, additive N selects Na for use
2S
2O
3And ammonium citrate [C
6H
5O
7(NH
4)
3] by the amount of substance ratio 1: 1 mixture.
5, galvanized alloy: K
4P
2O
7180g/L, Zn
2+4.9g/L, additive D 85ppm, PH 8.95, and temperature is 36 ℃, current density 0.75 A/dm
2, additive D selects Al for use
2(SO
4)
3
6, passivation: potassiumchromate 6g/L, PH 10.5, and temperature is 29 ℃, current density 5.5A/dm
2
7, spraying coupling agent: the coupling agent concentration of volume percent is 0.3%, 35 ℃ of temperature.
Embodiment 5:
The difference of present embodiment and embodiment 1 is:
1, alligatoring: Cu
2+14g/L, H
2SO
4100g/L, additive A 32ppm, temperature is 40 ℃, current density 22A/dm
2, additive A is selected the propenyl thiocarbamide for use.
2, solidify: Cu
2+55g/L, H
2SO
4150g/L, temperature is 40 ℃; Current density 30A/dm
2
3, weak alligatoring: Cu
2+7g/L, H
2SO
482g/L, addition of C 2.6g/L, temperature is 29 ℃, current density 12A/dm
2, addition of C is selected NH for use
4HSO
3
4, nickel plating alloy: K
4P
2O
7280g/L, Ni
2+14g/L, Zn
2+0.6g/L, additive M 48ppm, additive N 9g/L, PH 9.5, and temperature is 30 ℃, current density 5.9A/dm
2Additive M selects InSO for use
4, additive N selects cream of tartar (C for use
4H
9NO
6) and sodium-acetate (NaAC) press 1: 1.5 mixture of amount of substance.
5, galvanized alloy: K
4P
2O
7195g/L, Zn
2+5.6g/L, additive D 100ppm, PH 9.5, and temperature is 35 ℃, current density 1.4A/dm
2, additive D selects CoSO for use
47H
2O.
6, passivation: Sodium chromate 9g/L, PH 10.9, and temperature is 33 ℃, current density 5.2A/dm
2
7, spraying coupling agent: the coupling agent concentration of volume percent is 0.6%, 30 ℃ of temperature.
Example 1-5 performance such as table 1
Table 19 μ m surface treatment copper foils
Illustrate: because of the formula variation of each producer's base material and glue, the peel strength data are only for reference.
Above embodiment has solved extra thin copper foil dissatisfactory defective of anti-oxidizing ability when the ultra-fine circuit of etching; The defective of resistance to bend(ing) difference when having solved general electrolytic copper foil and being used for FPC; Solved of the low profile requirement of signal high-frequency transmission to copper foil surface; Can substitute the import rolled copper foil and be applied to flexibility coat copper plate, fill up this technical field blank of China.
The present invention has following advantage:
(1) Copper Foil of the present invention does not contain lead, mercury, cadmium, antimony etc. have serious harm to human body element.
(2) have excellent resistance to bend(ing), the folding of the FCCL that makes reaches more than 100,000 times.
(3) have excellent oxidation-resistance, less than 35 ℃, humidity is less than depositing not oxidation in a year under 50% the condition in temperature; Bubbling air stirs non-oxidation after 2 hours in 200 ℃ high temperature; In temperature is 85 ℃, and humidity is non-oxidation in following 48 hours of 90% the condition.
(4) have excellent erosion resistance and etching, compacting FCCL plate, be etched into behind the electronic circuit board in mass percent concentration is 12% hydrochloric acid soln and soak 30min, the peel strength rate of loss is in 10%, and (200 times) observe lines under electron microscope does not have corrosion.
(5) peel strength made behind the FCCL of (4) and PI reaches more than the 1.0N/mm.
Claims (1)
1. the black surface treatment process of electrolytic copper foil is characterized in that
Adopt 8-12 μ m VLP electrolytic copper foil to move as electrode and with the speed of 25.0 ± 0.1m/min, through roughening solution preparation, curing solution preparation, weak alligatoring acid copper or copper alloy, galvanic deposit one deck sodium meter level nickel or cobalt-base alloy again, the zinc alloy of galvanic deposit one deck sodium meter level passes through basic chromium hydrochlorate Passivation Treatment again and applies one deck coupling agent again;
Concrete treatment step is as follows:
1), roughening solution preparation: with cathode copper, the vitriol oil, soft water, vapor mixing dissolving, generate copper-bath, add additive A again in copper-bath, the abundant back of mixing is squeezed into the alligatoring groove with pump and is electroplated; Cu wherein
2+10-30g/L, H
2SO
480-200g/L, additive A 1.5-50ppm, temperature is 25-50 ℃, current density is 20-35A/dm
2
Described additive A is a class surfactant, and this surfactant is selected from a kind of in gelatin, thiocarbamide, Natvosol, benzotriazole, Sudan Gum-arabic, the propenyl thiocarbamide;
2), curing solution preparation: cathode copper, the vitriol oil, soft water, vapor mixing are dissolved, generate copper-bath, the abundant back of mixing is squeezed into the curing groove with pump and is electroplated; Cu wherein
2+50-100g/L, H
2SO
480-200g/L, temperature is 35-55 ℃, current density is 20-35A/dm
2
3), weak roughening solution preparation: with cathode copper, the vitriol oil, soft water, vapor mixing dissolving, generate copper-bath, add addition of C again in copper-bath, the abundant back of mixing is squeezed into weak alligatoring groove with pump and is electroplated; Cu wherein
2+6-20g/L, H
2SO
480-200g/L, addition of C 1-3g/L, temperature is 25-50 ℃, current density is 6-15A/dm
2
Described addition of C is a kind of nonmetallic compound, and this nonmetallic compound is selected from N, P, S, As, F, the Cl compound one or both;
4), nickel plating or cobalt-base alloy formulations prepared from solutions: potassium pyrophosphate, single nickel salt or rose vitriol, zinc sulfate, additive M, additive N are dissolved respectively, squeeze into nickel bath with pump behind the thorough mixing or the cobalt plating groove is electroplated; Wherein, K
4P
2O
7140-300g/L, Ni
2+2.5-15g/L or Co
2+2-20g/L, Zn
2+0.5-7g/L, additive M 30-450ppm, additive N 1.0-10g/L, pH 8-11, temperature is 25-50 ℃, current density 5-15A/dm
2
Described additive M is selected from the vitriol of one or both metals among Ag, Mo, In, Co, Al, Cu, Mg, Fe, the Sn; Additive N is selected from NH
4 +, SCN
-, S
2O
3 2-, AC
-, tartrate anion, citrate, EDTA
-In the compound one or both;
5), galvanized alloy formulations prepared from solutions: potassium pyrophosphate, zinc sulfate are dissolved respectively, again solution of zinc sulfate is added in the potassium pyrophosphate solution, generate zinc pyrophosphate solution, add additive D again, enter the galvanized alloy groove after the mixing fully and electroplate; Wherein, K
4P
2O
7140-300g/L, Zn
2+2-7g/L, additive D 60-150ppm, pH 8-11, temperature is 25-50 ℃, current density is 0.50-1.5A/dm
2
Described additive D is selected from Mo, In, Co, Ni, Al, Cu, Fe, the Sn compound one or both;
6), chromating formulations prepared from solutions: chromic salt is dissolved in soft water, squeeze in the deactivation slot with pump and electroplate; Chromic salt 2-10g/L wherein, pH 8-12, temperature is 25-50 ℃, current density is 2.0-8.0A/dm
2
7), spraying coupling agent: silane coupling agent is dissolved in the soft water, plays circulation and be sprayed on copper foil surface with pump; This silane coupling agent is selected from a kind of in amino, vinyl, sulfenyl, the epoxy group(ing), concentration of volume percent 0.1-2%, temperature 15-40 ℃; Per hour silane coupled agent concentration in the solution is once tested, and adjusted concentration to above-mentioned scope according to test result.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102456862A CN101906630B (en) | 2010-08-03 | 2010-08-03 | Black surface treatment process of electrolytic copper foil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102456862A CN101906630B (en) | 2010-08-03 | 2010-08-03 | Black surface treatment process of electrolytic copper foil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101906630A CN101906630A (en) | 2010-12-08 |
| CN101906630B true CN101906630B (en) | 2011-08-10 |
Family
ID=43262208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102456862A Active CN101906630B (en) | 2010-08-03 | 2010-08-03 | Black surface treatment process of electrolytic copper foil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101906630B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105603480A (en) * | 2016-03-02 | 2016-05-25 | 山东天和压延铜箔有限公司 | Black surface treatment method for rolled copper foil |
Families Citing this family (39)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212853B (en) * | 2011-04-30 | 2012-11-14 | 山东金宝电子股份有限公司 | Surface treatment coarsening process for improving peel strength of copper foil |
| CN102797021B (en) * | 2011-05-23 | 2015-03-25 | 东强（连州）铜箔有限公司 | Method for preparing electrolytic copper foil applied to high-Tg glass cloth plates, halogen-free plates and high-CTICEM-1 plates |
| CN103124473B (en) * | 2011-11-18 | 2016-03-30 | 珠海方正科技高密电子有限公司 | A kind of copper billet is black/brown device and black/oxide method |
| CN102418129A (en) * | 2011-11-18 | 2012-04-18 | 山东金宝电子股份有限公司 | Surface treatment process of copper foil for high-Tg halogen-free plate |
| CN102363891B (en) * | 2011-11-18 | 2013-09-25 | 山东金宝电子股份有限公司 | Double photoelectrolysis copper foil replacing rolled copper foil and used for production of flexible copper clad laminate, and production process of double photoelectrolysis copper foil |
| CN102560584B (en) * | 2012-02-14 | 2014-06-11 | 联合铜箔(惠州)有限公司 | Additive for electrolytic copper foil and surface treatment process of very low profile electrolytic copper foil |
| CN102534710A (en) * | 2012-03-12 | 2012-07-04 | 山东金宝电子股份有限公司 | Black coarsening treatment process for surface of very-low-profile copper foil |
| JP5559288B2 (en) * | 2012-11-13 | 2014-07-23 | メック株式会社 | Printed wiring board manufacturing method and surface treatment apparatus |
| CN103088397B (en) * | 2013-02-07 | 2015-11-18 | 灵宝华鑫铜箔有限责任公司 | A kind of method removing hair side red-way defect in copper foil surface process |
| CN103590077B (en) * | 2013-11-19 | 2016-09-28 | 华纳国际（铜陵）电子材料有限公司 | For printed circuit board and the manufacture method of the electrolytic copper foil of lithium rechargeable battery |
| CN104099652A (en) * | 2014-07-09 | 2014-10-15 | 山东金宝电子股份有限公司 | Surface treatment roughening process for electronic copper foils |
| 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 |
| CN104962965B (en) * | 2015-05-29 | 2017-08-15 | 灵宝金源朝辉铜业有限公司 | The environment-friendly type ashing handling process of rolled copper foil |
| CN105002496B (en) * | 2015-07-28 | 2017-11-28 | 灵宝华鑫铜箔有限责任公司 | A kind of electrolytic copper foil black surface processing method |
| CN105018985B (en) * | 2015-08-10 | 2018-07-31 | 灵宝华鑫铜箔有限责任公司 | A kind of process of surface treatment reducing electrolytic copper foil side etching phenomenon |
| CN105177659B (en) * | 2015-08-10 | 2018-06-05 | 灵宝华鑫铜箔有限责任公司 | A kind of process of surface treatment for improving copper foil corrosion resistance |
| CN105002530A (en) * | 2015-08-10 | 2015-10-28 | 灵宝华鑫铜箔有限责任公司 | Surface treatment process for improving copper foil high-temperature anti-oxidation performance |
| CN105018978B (en) * | 2015-08-10 | 2018-07-27 | 灵宝华鑫铜箔有限责任公司 | A kind of process of surface treatment improving electrolytic copper foil high temperature peeling resistance |
| KR102029139B1 (en) | 2015-11-09 | 2019-10-07 | 케이씨에프테크놀로지스 주식회사 | Electrolytic Copper Foil, Electrode Comprising The Same, Secondary Battery Comprising The Same, and Method for Manufacturing The Same |
| CN105839104B (en) * | 2016-03-30 | 2019-03-08 | 柏弥兰金属化研究股份有限公司 | The manufacturing method of flexible metal laminated material |
| CN109642338B (en) * | 2016-09-12 | 2021-02-09 | 古河电气工业株式会社 | Copper foil and copper-clad plate with same |
| CN106544709B (en) * | 2016-11-03 | 2019-04-05 | 山东金宝电子股份有限公司 | A kind of process of surface treatment improving electrolytic copper foil high-temp antioxidizing performance |
| CN106498467B (en) * | 2016-11-16 | 2018-09-11 | 山东金宝电子股份有限公司 | A kind of preparation method of ultra-thin carrier copper foil that stablizing stripping |
| CN106757245B (en) * | 2016-11-16 | 2019-05-21 | 山东金宝电子股份有限公司 | A kind of process of surface treatment of melanism copper foil |
| CN106757188B (en) * | 2016-12-16 | 2019-02-05 | 山东金宝电子股份有限公司 | A kind of black treatment process on copper Foil for Flexible Copper Clad Laminate surface |
| CN109097748A (en) * | 2017-12-15 | 2018-12-28 | 深圳科诺桥科技股份有限公司 | The preparation method of flexibility coat copper plate |
| CN109097751A (en) * | 2017-12-15 | 2018-12-28 | 深圳科诺桥科技股份有限公司 | The preparation method of flexibility coat copper plate |
| CN108034976B (en) * | 2017-12-21 | 2019-07-19 | 上海理工大学 | A kind of rolled copper foil of surface melanism |
| CN108060443B (en) * | 2017-12-21 | 2019-07-19 | 上海理工大学 | A kind of preparation method of the melanism composite layer on extruded metal foil surface |
| CN108085726A (en) * | 2017-12-21 | 2018-05-29 | 上海理工大学 | The surface Darkening process method of rolled copper foil |
| CN108330517B (en) * | 2018-01-25 | 2019-12-24 | 胡旭日 | Plating solution for stripping layer of carrier copper foil and preparation method of stripping layer |
| CN108930036A (en) * | 2018-07-13 | 2018-12-04 | 铜陵市华创新材料有限公司 | A kind for the treatment of process after extra thin copper foil preparation |
| 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 |
| CN109234772A (en) * | 2018-09-10 | 2019-01-18 | 南亚电子材料(昆山)有限公司 | A kind of Zn-Cr antioxygen chemical plating solution preparation method and the application on lithium ion battery copper foil |
| CN110820021B (en) * | 2019-11-15 | 2021-01-05 | 安徽德科科技有限公司 | Anti-stripping copper foil for circuit board and preparation method thereof |
| CN111304709A (en) * | 2020-04-22 | 2020-06-19 | 山东金宝电子股份有限公司 | Surface treating agent for improving corrosion resistance of electrolytic copper foil |
| CN112064071B (en) * | 2020-09-09 | 2021-08-03 | 松山湖材料实验室 | Bending-resistant copper foil, preparation method thereof and FPC (flexible printed circuit) flexible circuit board |
| CN113981494B (en) * | 2021-12-10 | 2023-05-30 | 安徽华创新材料股份有限公司 | Surface treatment process for reducing heat loss rate of electrolytic copper foil in peel strength |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1545570A (en) * | 2001-10-30 | 2004-11-10 | 株式会社日矿材料 | Surface-treated copper foil |
| CN1701137A (en) * | 2003-07-28 | 2005-11-23 | 三井金属矿业株式会社 | Surface-treated copper foil having blackening-treated surface, process for producing the surface-treated copper foil and, using the surface-treated copper foil, electromagnetic wave shielding conducti |
| CN1962944A (en) * | 2006-11-28 | 2007-05-16 | 招远金宝电子有限公司 | Gray surface treatment process for electrolytic copper foil |
| CN1995473A (en) * | 2006-11-28 | 2007-07-11 | 招远金宝电子有限公司 | Enivironment-friendly type surface treatment process for electrolytic copper foil |
-
2010
- 2010-08-03 CN CN2010102456862A patent/CN101906630B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1545570A (en) * | 2001-10-30 | 2004-11-10 | 株式会社日矿材料 | Surface-treated copper foil |
| CN1701137A (en) * | 2003-07-28 | 2005-11-23 | 三井金属矿业株式会社 | Surface-treated copper foil having blackening-treated surface, process for producing the surface-treated copper foil and, using the surface-treated copper foil, electromagnetic wave shielding conducti |
| CN1962944A (en) * | 2006-11-28 | 2007-05-16 | 招远金宝电子有限公司 | Gray surface treatment process for electrolytic copper foil |
| CN1995473A (en) * | 2006-11-28 | 2007-07-11 | 招远金宝电子有限公司 | Enivironment-friendly type surface treatment process for electrolytic copper foil |
Non-Patent Citations (1)
| Title |
|---|
| 杨祥魁等.高精电解铜箔环保型表面处理工艺研究.《电镀与涂饰》.2008,第27卷(第3期),第29-32页. * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105603480A (en) * | 2016-03-02 | 2016-05-25 | 山东天和压延铜箔有限公司 | Black surface treatment method for rolled copper foil |
| CN105603480B (en) * | 2016-03-02 | 2019-01-01 | 山东天和压延铜箔有限公司 | The black surface processing method of rolled copper foil |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101906630A (en) | 2010-12-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101906630B (en) | Black surface treatment process of electrolytic copper foil | |
| CN101935856B (en) | Back face treatment process of electrolytic copper foil | |
| US7223481B2 (en) | Method of producing ultra-thin copper foil with carrier, ultra-thin copper foil with carrier produced by the same, printed circuit board, multilayer printed circuit board and chip on film circuit board | |
| KR101853519B1 (en) | Liquid crystal polymer-copper clad laminate and copper foil used for liquid crystal polymer-copper clad laminate | |
| CN101935836B (en) | Surface treatment process of reddened copper foil for high-grade FR-4 copper-clad plate | |
| CN106757245B (en) | A kind of process of surface treatment of melanism copper foil | |
| CN101358361B (en) | Tin electrolysis applying liquid for electronic unit, applying method and electronic unit | |
| CN104962965B (en) | The environment-friendly type ashing handling process of rolled copper foil | |
| JP5885054B2 (en) | A treated copper foil for a copper clad laminate, a copper clad laminate obtained by bonding the treated copper foil to an insulating resin substrate, and a printed wiring board using the copper clad laminate. | |
| EP2557204A1 (en) | Copper foil for printed circuit | |
| JP3295308B2 (en) | Electrolytic copper foil | |
| CN106011965A (en) | Fine roughing treatment technology for surface of electrolytic copper foil | |
| JP2007186797A (en) | Method for producing ultrathin copper foil with carrier, ultrathin copper foil produced by the production method, and printed circuit board, multilayer printed circuit board and wiring board for chip on film using the ultrathin copper foil | |
| US20080261020A1 (en) | Adhesive layer for resin and a method of producing a laminate including the adhesive layer | |
| CN112226790B (en) | Production method of ultrathin high-strength electronic copper foil | |
| CN105408524A (en) | Surface-treated copper foil, copper foil with carrier, substrate, resin substrate, printed circuit board, copper-clad laminate, and method for manufacturing printed circuit board | |
| CN102534710A (en) | Black coarsening treatment process for surface of very-low-profile copper foil | |
| CN112853408A (en) | Preparation method of ultrathin carrier-attached copper foil easy to peel and pure in interface | |
| CN105578779A (en) | Printed circuit board inner-layer fine circuit manufacturing method | |
| CN102548202B (en) | Roughly-processed copper foil and manufacture method thereof | |
| KR101623713B1 (en) | Copper foil for printing circuit | |
| CN102233699B (en) | Extremely thin copper foil using ultralow ridge copper foil as carrier and manufacturing method of extremely thin copper foil | |
| CN107645852A (en) | A kind of two-sided surface treatment process of copper foil of high frequency printed circuit boards | |
| CN108060443A (en) | A kind of preparation method of the melanism composite bed on extruded metal paper tinsel surface | |
| JP4872257B2 (en) | Two-layer plated substrate and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 265400 No.268, Guoda Road, Zhaoyuan City, Yantai City, Shandong Province Patentee after: Shandong Jinbao Electronics Co.,Ltd. Address before: 265400 No. 128, Wenquan Road, Zhaoyuan, Shandong, Yantai Patentee before: SHANDONG JINBAO ELECTRONICS Co.,Ltd. |