CN102418129A - Surface treatment process of copper foil for high-Tg halogen-free plate - Google Patents
Surface treatment process of copper foil for high-Tg halogen-free plate Download PDFInfo
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- CN102418129A CN102418129A CN2011103660828A CN201110366082A CN102418129A CN 102418129 A CN102418129 A CN 102418129A CN 2011103660828 A CN2011103660828 A CN 2011103660828A CN 201110366082 A CN201110366082 A CN 201110366082A CN 102418129 A CN102418129 A CN 102418129A
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Abstract
The invention relates to a surface treatment process of a copper foil for a high-Tg halogen-free plate, belonging to the technical field of a production process of a high-precision electrolytic copper foil. In the surface treatment process provided by the invention, a structure shape of a coarsening layer is changed by using a special mixed additive in a coarsening step so as to improve anti-stripping strength; an ultra-fine nanoscale electroplated nickel-zinc alloy is used as a barrier layer to assure the corrosion resistance of the copper foil. Internal properties and pressure plate back color of the copper foil which is treated by the process provided by the invention are similar with those of the copper foil which is imported abroad; the anti-stripping strength on the high-Tg (Tg170) and the halogen-free plate is more than 1.5 N/mm; and the copper foil has characteristic of environmental friendliness and does not contain harmful matters, such as arsenic, antimony, mercury, cadmium, hexavalent chromium and the like.
Description
Technical field
The present invention relates to the process of surface treatment of a kind of high Tg, halogen board-use copper-clad, belong to the high-precision electrolytic copper foil technical field of producing.
Background technology
The electronics Copper Foil is important foundation starting material of making CCL (copper clad laminate) and PCB (printed substrate).In recent years, the various electronics and IT products technology in the world obtain high speed development, have promoted the new development of PCB towards multiple stratification, slimming, densification.Today of electronics and information industry high speed development, Copper Foil is " neural network " of electronic product signal and power transmission, communication already by the analogy of image.When the development of electronics and IT products proposes high request to CCL and PCB, also stricter requirement has been proposed aspects such as the performance of Copper Foil, environmental protection.
The develop rapidly of PCB technology, a lot of environment, condition, method have been different from the past, and development of technology is used to material and is brought a series of requirements.For example, during micro hole machining, in order to obtain good hole wall quality, the PCB processing procedure adopts penetration rate faster, can bring the hole wall problems of excessive heat; Multi-ply wood is pressing repeatedly, because the base material and the Copper Foil coefficient of expansion there are differences, may cause circuit copper to split; Hot air leveling in the sheet material course of processing, and element welding replaced by pb-free solder technology through after the thermal shocking repeatedly, is prone to that hole wall turning copper splits and problem such as hole wall contraction; Under the high-density installation technical qualification, the dimensional stabilizing problem of sheet material; Environmental safety is to the restriction of halogen flame.Given this, each CCL factory is devoted to improve the thermotolerance of sheet material, and reduces CTE (coefficient of expansion) and non-halogen.Tend to adopt the polymeric hardener agent of high heat resistance, cooperate the resin modified epoxy resin of polyfunctional group to make sheet material have high Tg (second-order transition temperature) and thermotolerance; Add an amount of mineral filler (silicon powder commonly used) in addition, reduce the coefficient of expansion; Use inorganic combustion inhibitor (white lake commonly used) to substitute halogen.When pursuing its high Tg, low CTE, halogen; Make substrate resin reduce to the engaging force of Copper Foil; The PS of last 35 μ m (1OZ) Copper Foils of general FR-4 can reach 2.0N/mm (11.4 lbf/in), and the Tg value can only reach about 1.4 N/mm (8 lbf/in) in the PS value on the Halogen-free plate about 150.At present, the state of the art of domestic Copper Foil, the halogen sheet material usage level of Tg in can both satisfying greatly; And be applied in the sheet material more than the Tg170; PS value or not enough, its technological difficulties are the hair paper tinsel of low Rz, and the mountain peak is even and sharp auspicious; The surface-treated roughened layer is grown to the mountain valley, and has good thermotolerance and environmental friendliness characteristic.
The surface treatment color of electrolytic copper foil has reddening, ashing and three kinds of representative colors of melanism usually.Wherein the melanism Copper Foil is usually used in FPC (flexible PCB) and EMI (electromagnetic shielding; Be used for plasm TV (PDP); Prevent that electromagnetic radiation is to the human injury), for the FR-4 plate that occupies CCL 90% above market, the High Tg of sheet material and Halogen-free popularized in ten minutes; The reddening Copper Foil becomes the main flow in market, and the trend that replaces the ashing Copper Foil is gradually arranged.Rely on external import because High Tg and Halogen-free board-use copper-clad are long-term, and the Copper Foil of these imports have the AOI detection of darker pressing plate back of the body look when producing to adapt to PCB, in CCL and PCB manufacturer's thinking, has formed specific color demand.
Summary of the invention
The object of the present invention is to provide a kind of high Tg, halogen plate process of surface treatment, be intended to solve high Tg (Tg170) and halogen plate peel strength, pressing plate back of the body look and environmental friendliness problem with the reddening Copper Foil with electrolytic copper foil.
The present invention realizes through following technical scheme:
The process of surface treatment of a kind of high Tg, halogen board-use copper-clad, its special character is
Adopt 35 μ m HTE electrolytic copper foils to do negative electrode and, the hair side of Copper Foil is carried out the roughened layer processing through the process step of overpickling-alligatoring-curings-melanism-zinc-plated-passivation-silane treatment-oven dry with the operation of the speed of 20m/min.The present invention is through in the alligatoring step, using special mixed additive, changing the roughened layer structural form, to reach the purpose that improves peel strength.Melanism step of the present invention, the solution of employing ultralow density salt, the ultra tiny nickel zinc alloy technology of electroplating nano substitutes traditional barrier function that arsenic blackization is arranged.The present invention adopts the trivalent chromium passivation treatment technology, has avoided sexavalent chrome in the current production to the harm of environment and human body.
Concrete treatment step of the present invention is following:
1, pickling: electrolytic copper foil is immersed in the sulphuric acid soln, to remove the zone of oxidation of copper foil surface; H wherein
2SO
4100-200 g/L, temperature 25-40 ℃, treatment time 4-5s;
2, alligatoring: with cathode copper, the vitriol oil, soft water, steam dissolving, generate copper-bath, in copper-bath, add additive T again, the abundant back of mixing gets into the alligatoring groove and electroplates; Cu wherein
2+10-25g/L, H
2SO
480-220g/L, additive T 5-150mg/L, temperature 20-35 ℃, current density 20-50A/dm
2, treatment time 2-15s;
Said additive T is a kind of mixed additive, is selected from phenanthroline, chloro-phenyl-acridine, thiocarbamide, soluble saccharin, Sodium orthomolybdate, sodium wolframate, stannous sulfate, ferrous sulfate, rose vitriol, the titanium sulfate two or more;
Alligatoring is on the hair side mountain peak of Copper Foil, to form dendrite, for the formation of " knurl " shape structure provides vegetative point; Adopt mixed additive, in galvanized process, play the negative electrode resistance and turn usefulness into, dendrite is grown to the mountain valley, improve the peel strength of Copper Foil on high Tg, halogen sheet material;
3, curing: with cathode copper, the vitriol oil, soft water, steam dissolving, generate copper-bath, pump into the curing groove after the mixing fully and electroplate; Cu wherein
2+40-75g/L, H
2SO
460-150g/L, temperature 40-65 ℃, current density 20-50 A/dm
2, treatment time 8-25s;
The solidified purpose be on the dendrite that alligatoring forms with the laminated form deposited copper, form nodular texture, play the effect that improves Copper Foil peel strength in copper-clad plate;
4, melanism: complexing agent, single nickel salt, zinc sulfate are dissolved respectively, under stirring state, single nickel salt and zinc sulfate are added in the complexing agent, pump into the melanism groove after the mixing fully and electroplate; Ni wherein
2+0.1-2.5g/L, Zn
2+0.05-1.5g/L, complexing agent 20-100g/L, temperature 20-55 ℃, current density 0.5-10A/dm
2, treatment time 0.5-5s;
Described complexing agent is selected from any one in potassium pyrophosphate, Hydrocerol A, Hydrocerol A ammonia, EDTA (sodium ethylene diamine tetracetate), the tartrate;
Melanism is after alligatoring, solidification treatment, forms the fine and close ultra tiny coating of one deck at copper foil surface, improves the erosion resistance of Copper Foil.In the scope that the present invention requires, improve Ni
2+Concentration or reduce Zn
2+Concentration helps improving the nickel content in the coating, helps to improve the erosion resistance of coating.Add Zn
2+Purpose be control coating erosion resistance in suitable scope; Make the Copper Foil of handling through the present invention both be adapted to the acid etching technology of PCB; Be suitable for alkali etching technology again; And when PCB makes, do not occur crossing the residual copper problem that occurs by force, do not occur the bar problem that goes offline yet because of occurring a little less than the erosion resistance because of erosion resistance;
5, zinc-plated: as potassium pyrophosphate and zinc sulfate to be dissolved respectively,, pump in the zinc bath after mixing and electroplate constantly under the stirring state zinc sulfate being added in the potassium pyrophosphate; Zn wherein
2+1-7 g/L, K
4P
2O
750-180 g/L, PH 8-11, temperature is 25-50 ℃, current density is 0.50-1.5 A/dm
2Treatment time 0.5-5s;
Galvanized effect is oxidation-resistance and the erosion resistance that improves Copper Foil;
6. passivation: chromium sulphate, zinc sulfate, sodium sulfate, additive P are dissolved respectively, mix the back and use sulfuric acid and Pottasium Hydroxide to regulate pH value, pump into deactivation slot again and electroplate; Cr wherein
3+1.0-3.0g/L, Zn
2+0.5-2 g/L, Na
2SO
420-30 g/L, additive P 0.2-1.0 g/L, pH 4-5, temperature 25-30 ℃, current density 2.0-4.5A/dm
2, treatment time 4-5s;
Said additive P is a kind of phosphorated mineral compound, is selected from a kind of in phosphoric acid, phosphorous acid, metaphosphoric acid, potassium hydrogen phosphate, the potassium primary phosphate;
The effect of passivation is to improve the zinc coating erosion resistance, and the zinc-Chrome metal powder that forms simultaneously helps improving the oxidation-resistance of Copper Foil.
7, silane treatment: epoxy silane coupling and tetraethoxysilane are added in the entry, be sprayed at copper foil surface after being stirred to abundant dissolving; Epoxy silane coupling 0.2-0.4 % wherein, tetraethoxysilane (TEOS) 0.4-0.6%, PH 5-6, temperature 25-30 ℃, treatment time 2-3s;
Using the main purpose of silane coupling agent is in order to improve the peel strength of Copper Foil in copper-clad plate;
8. oven dry: temperature 100-300 ℃, treatment time 2-10s;
The purpose of oven dry is to remove the moisture content of copper foil surface, as long as can make Copper Foil dry.
The process of surface treatment of a kind of high Tg of the present invention, halogen board-use copper-clad; Select for use 35 μ m HTE electrolysis hair paper tinsels to do negative electrode and with the operation of the speed of 20m/min; According to the step of alligatoring-curing-melanism-zinc-plated-passivation-silane treatment-oven dry the hair side of Copper Foil is carried out roughened layer and handle, Copper Foil has the internal performance close with the external high Tg board-use copper-clad of import and similar pressing plate is carried on the back look after the surface treatment; Hair side roughness Rz is at 5-8 μ m, and roughness is lower, is suitable for fine circuitry and makes; Have eco-friendly characteristic, do not contain hazardous substances such as arsenic, antimony, mercury, lead, cadmium, sexivalent chromium; Peel strength on High Tg (Tg170) and Halogen-free plate reaches more than the 1.5N/mm, and salt tolerant acid deterioration rate is below 5%; Have higher peel strength and erosion resistance; 200 ℃ of not oxidations of following 60min, at 85 ℃, under the condition of relative humidity 90%, not oxidation in 48 hours has good oxidation-resistance.
Description of drawings
The process of surface treatment schema of a kind of high Tg of Fig. 1 the present invention, halogen board-use copper-clad.
35 μ m Copper Foil electronic scanning Electronic Speculum (SEM) photos before Fig. 2 art breading of the present invention.
35 μ m Copper Foil electronic scanning Electronic Speculum (SEM) photos after Fig. 3 art breading of the present invention.
Embodiment
Provide embodiment of the present invention below, further specify technical solution of the present invention, but embodiment of the present invention is not limited to following embodiment.
The process of surface treatment of a kind of high Tg, halogen board-use copper-clad; Adopt 35 μ m HTE (high temperature unit elongation; High Temperature Elongation) the electrolytic copper foil electrolytic copper foil is done negative electrode and with the operation of the speed of 20m/min, through the process step of overpickling-alligatoring-curings-melanism-zinc-plated-passivation-silane treatment-oven dry the hair side of Copper Foil is carried out the roughened layer processing.The present invention is through in the alligatoring step, using special mixed additive, changing the roughened layer structural form, to reach the purpose that improves peel strength.Melanism step of the present invention, the solution of employing ultralow density salt, the ultra tiny nickel zinc alloy technology of electroplating nano substitutes traditional barrier function that arsenic blackization is arranged.The present invention adopts the trivalent chromium passivation treatment technology, has avoided sexavalent chrome in the current production to the harm of environment and human body.
Concrete treatment step of the present invention is following:
1, pickling: electrolytic copper foil is immersed in the sulphuric acid soln, and (fall the cupric oxide of copper foil surface with sulfuric acid reaction, reactional equation is: H with the zone of oxidation of removing copper foil surface
2SO
4+ CuO===CuSO
4+ H
2O); H wherein
2SO
4100-200 g/L, temperature 25-40 ℃, treatment time 4-5s;
2, alligatoring: with cathode copper, the vitriol oil, soft water, steam dissolving, generate copper-bath, in copper-bath, add additive T again, the abundant back of mixing gets into the alligatoring groove and electroplates; Cu wherein
2+10-25g/L, H
2SO
480-220g/L, additive T 5-150mg/L, temperature 20-35 ℃, current density 20-50A/dm
2, treatment time 2-15s;
Said additive T is a kind of mixed additive, is selected from phenanthroline, chloro-phenyl-acridine, thiocarbamide, soluble saccharin, Sodium orthomolybdate, sodium wolframate, stannous sulfate, ferrous sulfate, rose vitriol, the titanium sulfate two or more;
Alligatoring is on the hair side mountain peak of Copper Foil, to form dendrite, for the formation of " knurl " shape structure provides vegetative point; Adopt mixed additive, in galvanized process, play the negative electrode resistance and turn usefulness into, dendrite is grown to the mountain valley, improve the peel strength of Copper Foil on high Tg, halogen sheet material;
3, curing: with cathode copper, the vitriol oil, soft water, steam dissolving, generate copper-bath, pump into the curing groove after the mixing fully and electroplate; Cu wherein
2+40-75g/L, H
2SO
460-150g/L, temperature 40-65 ℃, current density 20-50 A/dm
2, treatment time 8-25s;
The solidified purpose be on the dendrite that alligatoring forms with the laminated form deposited copper, form nodular texture, play the effect that improves Copper Foil peel strength in copper-clad plate;
4, melanism: complexing agent, single nickel salt, zinc sulfate are dissolved respectively, under stirring state, single nickel salt and zinc sulfate are added in the complexing agent, pump into the melanism groove after the mixing fully and electroplate; Ni wherein
2+0.1-2.5g/L, Zn
2+0.05-1.5g/L, complexing agent 20-100g/L, temperature 20-55 ℃, current density 0.5-10A/dm
2, treatment time 0.5-5s;
Described complexing agent is selected from any one in potassium pyrophosphate, Hydrocerol A, Hydrocerol A ammonia, EDTA (sodium ethylene diamine tetracetate), the tartrate;
Melanism is after alligatoring, solidification treatment, forms the fine and close ultra tiny coating of one deck at copper foil surface, improves the erosion resistance of Copper Foil.In the scope that the present invention requires, improve Ni
2+Concentration or reduce Zn
2+Concentration helps improving the nickel content in the coating, helps to improve the erosion resistance of coating.Add Zn
2+Purpose be control coating erosion resistance in suitable scope; Make the Copper Foil of handling through the present invention both be adapted to the acid etching technology of PCB; Be suitable for alkali etching technology again; And when PCB makes, do not occur crossing the residual copper problem that occurs by force, do not occur line transfer bar problem yet because of occurring a little less than the erosion resistance because of erosion resistance;
5, zinc-plated: as potassium pyrophosphate and zinc sulfate to be dissolved respectively,, pump in the zinc bath after mixing and electroplate constantly under the stirring state zinc sulfate being added in the potassium pyrophosphate; Zn wherein
2+1-7 g/L, K
4P
2O
750-180 g/L, PH 8-11, temperature is 25-50 ℃, current density is 0.50-1.5 A/dm
2Treatment time 0.5-5s;
Galvanized effect is oxidation-resistance and the erosion resistance that improves Copper Foil;
6. passivation: chromium sulphate, zinc sulfate, sodium sulfate, additive P are dissolved respectively, mix the back and use sulfuric acid and Pottasium Hydroxide to regulate pH value, pump into deactivation slot again and electroplate; Cr wherein
3+1.0-3.0g/L, Zn
2+0.5-2 g/L, Na
2SO
420-30 g/L, additive P 0.2-1.0 g/L, pH 4-5, temperature 25-30 ℃, current density 2.0-4.5A/dm
2, treatment time 4-5s;
Said additive P is a kind of phosphorated mineral compound, is selected from a kind of in phosphoric acid, phosphorous acid, metaphosphoric acid, potassium hydrogen phosphate, the potassium primary phosphate;
The effect of passivation is to improve the zinc coating erosion resistance, and the zinc-Chrome metal powder that forms simultaneously helps improving the oxidation-resistance of Copper Foil.
7, silane treatment: epoxy silane coupling and tetraethoxysilane are added in the entry, be sprayed at copper foil surface after being stirred to abundant dissolving; Epoxy silane coupling 0.2-0.4 % wherein, tetraethoxysilane (TEOS) 0.4-0.6%, PH 5-6, temperature 25-30 ℃, treatment time 2-3s;
Using the main purpose of silane coupling agent is in order to improve the peel strength of Copper Foil in copper-clad plate;
8. oven dry: use the electrothermal tube heating, the moisture of evaporation copper foil surface makes copper foil surface dry; Wherein temperature 100-300 ℃, treatment time 2-10s;
The purpose of oven dry is to remove the moisture content of copper foil surface, as long as can make Copper Foil dry.
Embodiment 1
The process of surface treatment of a kind of high Tg, halogen board-use copper-clad, concrete treatment condition are following:
(1), pickling: H
2SO
4150 g/L, 35 ℃ of temperature, treatment time 4s.
(2), alligatoring: Cu
2+18g/L, H
2SO
4120g/L, additive T 55 mg/L, 25 ℃ of temperature, current density 25A/dm
2, treatment time 6.2s.
(3), solidify: Cu
2+55g/L, H
2SO
480g/L, 43 ℃ of temperature, current density 35A/dm
2, treatment time 8s.
(4), melanism: Ni
2+0.8g/L, Zn
2+0.25g/L, potassium pyrophosphate 40g/L, 45 ℃ of temperature, current density 2.5A/dm
2, treatment time 1.5s.
(5), zinc-plated: Zn
2+5 g/L, K
4P
2O
780g/L, PH 9.2, and temperature is 35 ℃, and current density is 1.2 A/dm
2Treatment time 3s.
(6), passivation: Cr
3+2.0g/L, Zn
2+1.4 g/L, Na
2SO
425 g/L, additive P 0.6 g/L, pH 4.5,28 ℃ of temperature, current density 3.0A/dm
2, treatment time 4s.
(7), silane treatment: epoxy silane coupling 0.4 %, tetraethoxysilane (TEOS) 0.4%, PH 5.5,28 ℃ of temperature, treatment time 2s.
(8), oven dry: 180 ℃ of temperature, treatment time 6s.
Embodiment 2
(1), pickling: H
2SO
4100 g/L, 25 ℃ of temperature, treatment time 4s.
(2), alligatoring: Cu
2+10g/L, H
2SO
480g/L, additive T 5 mg/L, 20 ℃ of temperature, current density 20A/dm
2, treatment time 2s.
(3), solidify: Cu
2+40g/L, H
2SO
460g/L, 40 ℃ of temperature, current density 20A/dm
2, treatment time 8s.
(4), melanism: Ni
2+0.1g/L, Zn
2+0.05g/L, potassium pyrophosphate 20g/L, 20 ℃ of temperature, current density 0.5A/dm
2, treatment time 0.5s.
(5), zinc-plated: Zn
2+1 g/L, K
4P
2O
750g/L, PH 8, and temperature is 25 ℃, and current density is 0.5 A/dm
2Treatment time 0.5s.
(6), passivation: Cr
3+1.0g/L, Zn
2+0.5 g/L, Na
2SO
420 g/L, additive P 0.2 g/L, pH 4,25 ℃ of temperature, current density 2.0A/dm
2, treatment time 4s.
(7), silane treatment: epoxy silane coupling 0.2 %, tetraethoxysilane (TEOS) 0.4%, PH 5.0,25 ℃ of temperature, treatment time 2s.
(8), oven dry: 100 ℃ of temperature, treatment time 2s.
Embodiment 3
(1), pickling: H
2SO
4200 g/L, 40 ℃ of temperature, treatment time 5s.
(2), alligatoring: Cu
2+25g/L, H
2SO
4220g/L, additive T 150 mg/L, 35 ℃ of temperature, current density 50A/dm
2, treatment time 15s.
(3), solidify: Cu
2+75g/L, H
2SO
4150g/L, 65 ℃ of temperature, current density 50A/dm
2, treatment time 25s.
(4), melanism: Ni
2+2.5g/L, Zn
2+1.5g/L, potassium pyrophosphate 100g/L, 55 ℃ of temperature, current density 10A/dm
2, treatment time 5s.
(5), zinc-plated: Zn
2+7 g/L, K
4P
2O
7180g/L, PH 11, and temperature is 50 ℃, and current density is 1.5 A/dm
2Treatment time 5s.
(6), passivation: Cr
3+3.0g/L, Zn
2+2 g/L, Na
2SO
430 g/L, additive P 1 g/L, pH 5,30 ℃ of temperature, current density 4.5A/dm
2, treatment time 5s.
(7), silane treatment: epoxy silane coupling 0.4 %, tetraethoxysilane (TEOS) 0.6%, PH 6.0,30 ℃ of temperature, treatment time 3s.
(8), oven dry: 300 ℃ of temperature, treatment time 10s.
Embodiment 4
Be different from embodiment 1:
(1), alligatoring: Cu
2+20g/L, H
2SO
4150g/L, additive T 120mg/L.
(2), solidify: Cu
2+55g/L, H
2SO
4100g/L, 50 ℃ of temperature, current density 25A/dm
2, treatment time 11s.
(3), melanism: Ni
2+1.5g/L, Zn
2+0.2g/L, complexing agent 80g/L, 45 ℃ of temperature, current density 3A/dm
2, treatment time 1s.
(4), zinc-plated: Zn
2+3 g/L, K
4P
2O
775g/L, PH 10.5, and temperature is 38 ℃, and current density is 1.2 A/dm
2Treatment time 2.5s.
(5), passivation: Cr
3+2.8g/L, Zn
2+1.2g/L, Na
2SO
430 g/L, additive P 0.8 g/L, pH 4,25 ℃ of temperature, current density 4.5A/dm
2, treatment time 4s.
Embodiment 5
Be different from embodiment 1:
(1), alligatoring: Cu
2+15g/L, H
2SO
4160g/L, additive T 100mg/L, 30 ℃ of temperature, current density 25A/dm
2, treatment time 6s.
(2), solidify: Cu
2+65g/L, H
2SO
480g/L, 40 ℃ of temperature, current density 35A/dm
2, treatment time 8s.
(3), melanism: Ni
2+1.8g/L, Zn
2+0.35g/L, complexing agent 30g/L, 45 ℃ of temperature, current density 1.5A/dm
2, treatment time 3s.
(4), zinc-plated: Zn
2+6g/L, K
4P
2O
7135 g/L, PH 10, and temperature is 35 ℃, and current density is 1.4A/dm
2Treatment time 3s.
Embodiment 6
Be different from embodiment 1:
(1), alligatoring: Cu
2+22g/L, H
2SO
4120g/L, additive T 70mg/L, 26 ℃ of temperature, current density 25A/dm
2, treatment time 7s.
(2), melanism: Ni
2+1.5g/L, Zn
2+0.5g/L, complexing agent 60g/L, 40 ℃ of temperature, current density 8A/dm
2, treatment time 1s.
Embodiment 7
Be different from embodiment 1:
(1), alligatoring: Cu
2+10-25g/L, H
2SO
480-220g/L, additive T 5-150mg/L, temperature 20-35 ℃, current density 20-50A/dm
2, treatment time 2-15s.
(2), solidify: Cu
2+45g/L, H
2SO
4130g/L, 50 ℃ of temperature, current density 30A/dm2, treatment time 9s.
(3), melanism: Ni
2+2.2g/L, Zn
2+1.0g/L, complexing agent 100g/L, 25 ℃ of temperature, current density 3A/dm
2, treatment time 1.5s.
The present invention has following advantage:
Copper Foil has performance close with the external high Tg board-use copper-clad of import and similar pressing plate back of the body look after the 35 μ m Copper Foils that the process of surface treatment of a kind of high Tg of the present invention, halogen board-use copper-clad is handled, surface treatment; Have eco-friendly characteristic, do not contain hazardous substances such as arsenic, antimony, mercury, lead, cadmium, sexivalent chromium; Hair side roughness Rz is suitable for fine circuitry and makes at 6-8 μ m; Peel strength on High Tg (Tg170) and Halogen-free plate has good anti-corrosion and oxidation-resistance greater than 1.5N/mm.
Copper Foil after the process of surface treatment of a kind of high Tg of the present invention, halogen board-use copper-clad is handled has performance close with the external high Tg board-use copper-clad of import and similar pressing plate back of the body look; Have lower roughness, be suitable for fine circuitry and make; Have eco-friendly characteristic, do not contain hazardous substances such as arsenic, antimony, mercury, lead, cadmium, sexivalent chromium; On High Tg (Tg170) and Halogen-free plate, have higher peel strength and erosion resistance; Has good oxidation-resistance.
Claims (4)
1. the process of surface treatment of a high Tg, halogen board-use copper-clad is characterized in that
Adopt 35 μ m HTE electrolytic copper foils to do negative electrode and, the hair side of Copper Foil is carried out the roughened layer processing through the process step of overpickling-alligatoring-curings-melanism-zinc-plated-passivation-silane treatment-oven dry with the operation of the speed of 20m/min.
2. the process of surface treatment of a kind of according to claim 1 high Tg, halogen board-use copper-clad is characterized in that
1), pickling: electrolytic copper foil is immersed in the sulphuric acid soln, to remove the zone of oxidation of copper foil surface;
2), alligatoring: with cathode copper, the vitriol oil, soft water, steam dissolving, generate copper-bath, in copper-bath, add additive T again, the abundant back of mixing gets into the alligatoring groove and electroplates;
Said additive T is a kind of mixed additive, is selected from phenanthroline, chloro-phenyl-acridine, thiocarbamide, soluble saccharin, Sodium orthomolybdate, sodium wolframate, stannous sulfate, ferrous sulfate, rose vitriol, the titanium sulfate two or more;
3), curing: with cathode copper, the vitriol oil, soft water, steam dissolving, generate copper-bath, pump into the curing groove after the mixing fully and electroplate;
4), melanism: complexing agent, single nickel salt, zinc sulfate are dissolved respectively, under stirring state, single nickel salt and zinc sulfate are added in the complexing agent, pump into the melanism groove after the mixing fully and electroplate;
Described complexing agent is selected from any one in potassium pyrophosphate, Hydrocerol A, Hydrocerol A ammonia, EDTA, the tartrate;
5), zinc-plated: as potassium pyrophosphate and zinc sulfate to be dissolved respectively,, pump in the zinc bath after mixing and electroplate constantly under the stirring state zinc sulfate being added in the potassium pyrophosphate;
6), passivation: chromium sulphate, zinc sulfate, sodium sulfate, additive are dissolved respectively, mix the back and use sulfuric acid and Pottasium Hydroxide to regulate pH value, pump into deactivation slot again and electroplate;
7), silane treatment: epoxy silane coupling and tetraethoxysilane are added in the entry, be sprayed at copper foil surface after being stirred to abundant dissolving;
8), oven dry.
3. like the process of surface treatment of the said a kind of high Tg of claim 2, halogen board-use copper-clad, it is characterized in that concrete processing condition do
1), pickling: H
2SO
4100-200 g/L, temperature 25-40 ℃, treatment time 4-5s;
2), alligatoring: Cu
2+10-25g/L, H
2SO
480-220g/L, additive T 5-150mg/L, temperature 20-35 ℃, current density 20-50A/dm
2, treatment time 2-15s;
3), solidify: Cu
2+40-75g/L, H
2SO
460-150g/L, temperature 40-65 ℃, current density 20-50 A/dm
2, treatment time 8-25s;
4), melanism: Ni
2+0.1-2.5g/L, Zn
2+0.05-1.5g/L, complexing agent 20-100g/L, temperature 20-55 ℃, current density 0.5-10A/dm
2, treatment time 0.5-5s;
5), zinc-plated: Zn wherein
2+1-7 g/L, K
4P
2O
750-180 g/L, PH 8-11, temperature is 25-50 ℃, current density is 0.50-1.5 A/dm
2Treatment time 0.5-5s;
6), passivation: Cr
3+1.0-3.0g/L, Zn
2+0.5-2 g/L, Na
2SO
420-30 g/L, additive P 0.2-1.0 g/L, pH 4-5, temperature 25-30 ℃, current density 2.0-4.5A/dm
2, treatment time 4-5s;
7), silane treatment: epoxy silane coupling 0.2-0.4 %, tetraethoxysilane (TEOS) 0.4-0.6%, PH 5-6, temperature 25-30 ℃, treatment time 2-3s;
8), the oven dry: temperature 100-300 ℃, treatment time 2-10s.
4. like the process of surface treatment of the said a kind of high Tg of the arbitrary claim of claim 1-3, halogen board-use copper-clad, it is characterized in that
The peel strength of 35 μ m Copper Foils on high Tg, halogen plate of handling is greater than 1.5N/mm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103660828A CN102418129A (en) | 2011-11-18 | 2011-11-18 | Surface treatment process of copper foil for high-Tg halogen-free plate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103660828A CN102418129A (en) | 2011-11-18 | 2011-11-18 | Surface treatment process of copper foil for high-Tg halogen-free plate |
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Family
ID=45942767
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|---|---|---|---|
| CN2011103660828A Pending CN102418129A (en) | 2011-11-18 | 2011-11-18 | Surface treatment process of copper foil for high-Tg halogen-free plate |
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