CN108221010B - Preparation process of high-molecular conductive film of PCB (printed circuit board) - Google Patents
Preparation process of high-molecular conductive film of PCB (printed circuit board) Download PDFInfo
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- CN108221010B CN108221010B CN201810081731.1A CN201810081731A CN108221010B CN 108221010 B CN108221010 B CN 108221010B CN 201810081731 A CN201810081731 A CN 201810081731A CN 108221010 B CN108221010 B CN 108221010B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/30—Electroplating: Baths therefor from solutions of tin
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
Abstract
The invention discloses a preparation process of a high-molecular conductive film of a PCB (printed circuit board), which comprises a Desmear process and a DMSE (dimethyl formamide seine) process. The Desmear procedure comprises expansion, triple washing, degumming, triple washing and neutralization triple washing. The DMSE process comprises sensitization, triple washing, catalysis, triple washing, polymerization, triple washing, drying and plate discharging. The experiment proves that the copper plating rate reaches 8mm/min, the stability is high, the copper plating rate is still more than 3mm/min after the copper plating device is used for more than 30 days, and the TP value of the brightness of the copper plating matched with ST-302 reaches more than 90 percent. In addition, the process is particularly suitable for circuit boards with extremely small apertures.
Description
Technical Field
The invention relates to a manufacturing process of a polymer conductive film, in particular to a manufacturing process of a polymer conductive film of a PCB.
Background
The polymer conductive film process has been used for several years, and the new process has various advantages of environmental protection, high aging, low cost and the like, but has the defects of slow copper coating rate and the like.
Patent No. CN 105097127a, a method and dispersion for manufacturing a polymer transparent conductive film, comprising: providing a conductive polymer aqueous solution, wherein the conductive polymer aqueous solution comprises poly (3, 4-dioxyethyl thiophene) and polystyrene sulfonic acid (PEDOT: PSS); adding a conductive additive into the conductive polymer aqueous solution to prepare a dispersion liquid; disposing the dispersion on the surface of the substrate to form a dispersion film; drying the dispersion liquid film at the temperature of more than 140 ℃ to prepare a polymer transparent conductive film; wherein the conductive additive is malonic acid, and the addition amount of the conductive additive accounts for 3-20 weight percent of the total weight of the dispersion liquid. According to the preparation method, malonic acid is used as a conductive aid and is added to PEDOT (PSS), so that the surface impedance of the conductive polymer is reduced and the conductivity is improved. After the dispersion liquid containing the conductive polymer is dried to form a film, malonic acid remains in the conductive film without forming crystals, and the film surface is transparent. Therefore, the method of the invention is quite suitable for manufacturing the transparent conductive film with high transparency and low impedance.
Disclosure of Invention
The invention aims to provide a preparation process of a high-molecular conductive film of a PCB (printed circuit board), so as to make up for the defects of the prior art.
In order to achieve the purpose, the invention adopts the following specific technical scheme:
a preparation process of a PCB high-molecular conductive film comprises a Desmear process and a DMSE process.
Further, the Desmear process comprises the following steps:
(1) expansion: NaOH 80-120g/L and ST-101A 180-300ml/L are adopted for treatment, and the temperature is controlled at 78-82 ℃;
(2) thirdly, washing with water;
(3) degumming: by adopting KMnO460-80g/L of NaOH and 40-50g/L of NaOH, and the temperature is 80-88 ℃;
(4) thirdly, washing with water;
(5) neutralizing: with 50% H2SO460-70ml/L, 35% H2O2 50-70ml/L，Cu2+Processing at a temperature of 20-30 ℃ at a concentration of less than or equal to 20 g/L;
(6) and (5) washing with water.
Further, the specific parameters in the third water washing in the above steps are as follows: conductivity < 100us/cm2The chloride ion is less than 100ppm, the pH value is 5-8, the flow rate is more than or equal to 8L/min, and the washing pressure is 1.5-2.5kg/cm2。
Further, the DMSE process comprises the steps of:
(1) sensitizing;
(2) thirdly, washing with water;
(3) catalyzing;
(4) thirdly, washing with water;
(5) polymerizing;
(6) thirdly, washing with water;
(7) drying and discharging.
Further, 20 wt% of methyl sulfate homopolymer aqueous solution is adopted for sensitization to prepare 10% aqueous solution, the slotting ratio is 30ml/L, N-methyl-2-pyrrolidone is prepared to prepare 10% aqueous solution, the slotting ratio is 10ml/L, sodium carbonate is adopted, the slotting ratio is 5.0g/L, and the temperature is selected to be 55-65 ℃.
Further, the catalyst is specifically: 350g/L of sodium permanganate aqueous solution is adopted, the grooving proportion is 200ml/L, the grooving proportion is 10.0g/L, and the temperature is 85-95 ℃.
Further, the polymerization is specifically as follows: adopting a solution A: dissolving 3-4-ethylenedioxythiophene 1kg in tristyrylphenol polyoxyethylene polyoxypropylene ether 2kg, adding 7.5L water to prepare 10L solution, wherein the grooving ratio is 15ml/L, preparing 10% aqueous solution from B solution N-methyl-2-pyrrolidone, the grooving ratio is 10ml/L, and the temperature is 18-22 ℃.
Carrying out copper plating by utilizing the PCB process, wherein the copper plating solution comprises the following components: 60-90g/L of copper sulfate; sulfuric acid 160-200 g/L; chloride ion, 30-80 ppm; ST-302 copper plating gloss agent 0.25-1.0%; the temperature is 20-38 ℃; current density 1-80 ASF; stirring air, continuously filtering, and obtaining a cathode-anode area ratio of 1: 2-1.
Further, the copper plating solution comprises the following components: the copper sulfate is 75 g/L; the sulfuric acid is 180 g/L; chloride ion was 50 ppm; ST-302 copper plating gloss agent is 0.5%; the temperature is 24 ℃; the current density is 25-35 ASF; stirring air, continuously filtering, and obtaining a cathode-anode area ratio of 1: 2.
the PCB is utilized for tinning, wherein the tinning solution is as follows: stannous sulfate 20-35g/L, sulfuric acid 160-200g/L, ST-4023-5%, current, density 5-30ASF, area ratio of cathode and anode 1:2-1, and temperature range 18-25 ℃.
Further, the tin plating solution is: 30g/L of stannous sulfate, 180g/L of sulfuric acid, ST-4024 percent of current, 15ASF of density, 1:2 of area ratio of cathode to anode and 20 ℃ of temperature range.
The invention has the advantages and technical effects that:
the experiment proves that the copper plating rate reaches 8mm/min, the stability is high, the copper plating rate is still more than 3mm/min after the copper plating device is used for more than 30 days, and the TP value of the brightness of the copper plating matched with ST-302 reaches more than 90 percent. In addition, the process is particularly suitable for circuit boards with extremely small apertures.
Detailed Description
The invention is further illustrated and described below by means of specific examples.
Example 1:
a preparation process of a PCB high-molecular conductive film comprises the following steps:
1. the Desmear process comprises the following steps: expansion: NaOH 80-120g/L and ST-101A 180-300ml/L are adopted for treatment, and the temperature is controlled at 78-82 ℃; thirdly, washing with water; removing glue: by adopting KMnO460-80g/L of NaOH and 40-50g/L of NaOH, and the temperature is 80-88 ℃; thirdly, washing with water; neutralizing: with 50% H2SO460-70ml/L, 35% H2O2 50-70ml/L，Cu2+Processing at a temperature of 20-30 ℃ at a concentration of less than or equal to 20 g/L; and (5) washing with water.
Further, the specific parameters in the third water washing in the above steps are as follows: conductivity < 100us/cm2Chloride ion less than 100ppm, pH value 5-8, flow rate not less than8L/min, washing pressure 1.5-2.5kg/cm2。
2. The DMSE procedure comprises the following steps: sensitizing; thirdly, washing with water; catalyzing; thirdly, washing with water; polymerizing; thirdly, washing with water; drying and discharging.
Further, 20 wt% of methyl sulfate homopolymer aqueous solution is adopted for sensitization to prepare 10% aqueous solution, and the slotting proportioning is carried out
30ml/L, preparing 10% water solution with a slotting ratio of 10ml/L and sodium carbonate with a slotting ratio of 5.0g/L and a temperature of 55-65 ℃.
Further, the catalyst is specifically: 350g/L of sodium permanganate aqueous solution is adopted, the grooving proportion is 200ml/L, the grooving proportion is 10.0g/L, and the temperature is 85-95 ℃.
Further, the polymerization is specifically as follows: adopting a solution A: dissolving 3-4-ethylenedioxythiophene 1kg in tristyrylphenol polyoxyethylene polyoxypropylene ether 2kg, adding 7.5L water to prepare 10L solution, wherein the grooving ratio is 15ml/L, preparing 10% aqueous solution from B solution N-methyl-2-pyrrolidone, the grooving ratio is 10ml/L, and the temperature is 18-22 ℃.
Carrying out copper plating by utilizing the PCB process, wherein the copper plating solution comprises the following components: the copper sulfate is 75 g/L; the sulfuric acid is 180 g/L; chloride ion was 50 ppm; ST-302 copper plating gloss agent is 0.5%; the temperature is 24 ℃; the current density is 25-35 ASF; stirring air, continuously filtering, and obtaining a cathode-anode area ratio of 1: 2.
example 2:
a preparation process of a PCB high-molecular conductive film comprises the following steps:
1. the Desmear process comprises the following steps: expansion: NaOH 80-120g/L and ST-101A 180-300ml/L are adopted for treatment, and the temperature is controlled at 78-82 ℃; thirdly, washing with water; removing glue: by adopting KMnO460-80g/L of NaOH and 40-50g/L of NaOH, and the temperature is 80-88 ℃; thirdly, washing with water; neutralizing: with 50% H2SO460-70ml/L, 35% H2O2 50-70ml/L，Cu2+Processing at a temperature of 20-30 ℃ at a concentration of less than or equal to 20 g/L; and (5) washing with water.
Further, the specific parameters in the third water washing in the above steps are as follows: conductivity < 100us/cm2The chloride ion is less than 100ppm, the pH value is 5-8, the flow rate is more than or equal to 8L/min, and the washing pressure is 1.5-2.5kg/cm2。
2. The DMSE procedure comprises the following steps: sensitizing; thirdly, washing with water; catalyzing; thirdly, washing with water; polymerizing; thirdly, washing with water; drying and discharging.
Further, 20 wt% of methyl sulfate homopolymer aqueous solution is adopted for sensitization to prepare 10% aqueous solution, the slotting ratio is 30ml/L, N-methyl-2-pyrrolidone is prepared to prepare 10% aqueous solution, the slotting ratio is 10ml/L, sodium carbonate is adopted, the slotting ratio is 5.0g/L, and the temperature is selected to be 55-65 ℃.
Further, the catalyst is specifically: 350g/L of sodium permanganate aqueous solution is adopted, the grooving proportion is 200ml/L, the grooving proportion is 10.0g/L, and the temperature is 85-95 ℃.
Further, the polymerization is specifically as follows: adopting a solution A: dissolving 3-4-ethylenedioxythiophene 1kg in tristyrylphenol polyoxyethylene polyoxypropylene ether 2kg, adding 7.5L water to prepare 10L solution, wherein the grooving ratio is 15ml/L, preparing 10% aqueous solution from B solution N-methyl-2-pyrrolidone, the grooving ratio is 10ml/L, and the temperature is 18-22 ℃.
The PCB process is utilized for tin plating, wherein the tin plating solution is as follows: 30g/L of stannous sulfate, 180g/L of sulfuric acid, ST-4024 percent of current, 15ASF of density, 1:2 of area ratio of cathode to anode and 20 ℃ of temperature range.
The PCB obtained in the embodiment 1-2 is subjected to quality test, the appearance is bright, and abnormal phenomena such as scorching, fogging, sinking and the like do not exist; uniform electroplating, high heat resistance, high extensibility and high tension strength.
In the embodiment 1, the copper plating rate reaches 8mm/min, the stability is high, the copper plating rate is still more than 3mm/min after the copper plating is used for more than 30 days, and the TP value reaches more than 90% when the copper plating is matched with ST-302 copper plating.
Claims (1)
1. A preparation process of a PCB high-molecular conductive film is characterized by comprising a Desmear process and a DMSE process; the Desmean process comprises the following steps:
(1) expansion: NaOH 80-120g/L and ST-101A 180-300mL/L are adopted for treatment, and the temperature is controlled at 78-82 ℃;
(2) thirdly, washing with water;
(3) removing glue: by adopting KMnO460-80g/L of NaOH and 40-50g/L of NaOH, and the temperature is 80-88 ℃;
(4) thirdly, washing with water;
(5) neutralizing: with 50% H2SO460-70mL/L, 35% H2O2 50-70mL/L，Cu2+Treating at 20-30 deg.C at a concentration of 20-20 g/L;
(6) thirdly, washing with water;
the DMSE process comprises the steps of:
(1) sensitizing;
(3) catalysis, which is specifically: adopting 350g/L sodium permanganate aqueous solution, wherein the slotting ratio is 200mL/L, the boric acid slotting ratio is 10.0g/L, and the temperature is 85-95 ℃;
(5) polymerizing; the polymerization is specifically as follows: adopting a solution A: dissolving 3-4-ethylenedioxythiophene (1 kg) in tristyrylphenol polyoxyethylene polyoxypropylene ether (2 kg), adding water (7.5L) to prepare a solution (10L), wherein the grooving ratio is 15mL/L, preparing a 10% aqueous solution from solution B and N-methyl-2-pyrrolidone, and the grooving ratio is 10mL/L and the temperature is 18-22 ℃;
(6) thirdly, washing with water;
(7) drying and taking out;
the concrete parameters in the third water washing are as follows: conductivity < 100us/cm2The chloride ion is less than 100ppm, the pH value is 5-8, the flow rate is more than or equal to 8L/min, and the washing pressure is 1.5-2.5kg/cm2(ii) a The sensitization adopts 20 wt% methyl sulfate homopolymer aqueous solution to prepare 10% aqueous solution, the slotting ratio is 30mL/L, N-methyl-2-pyrrolidone is prepared into 10% aqueous solution, the slotting ratio is 10mL/L, sodium carbonate, the slotting ratio is 5.0g/L, and the temperature is selected to be 55-65 ℃.
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| CN103087478B (en) * | 2012-12-19 | 2016-12-28 | 厦门市安多特新材料科技有限公司 | A kind of conducting film Compound accelerator |
| CN104080278B (en) * | 2014-06-24 | 2017-06-06 | 柏承科技(昆山)股份有限公司 | The production technology of wiring board conductive polymer fenestra technique and its collocation graphic plating |
| CN104744974B (en) * | 2015-03-10 | 2017-10-17 | 广州市天承化工有限公司 | A kind of PCB generates the production technology of macromolecule conductive film with modified activating solution and in PCB through hole and blind hole |
| CN104703412B (en) * | 2015-04-07 | 2016-04-13 | 深圳市化讯应用材料有限公司 | A kind of method of hole metallization |
| US20170171988A1 (en) * | 2015-12-14 | 2017-06-15 | Rohm And Haas Electronic Materials Llc | Environmentally friendly stable catalysts for electroless metallization of printed circuit boards and through-holes |
| CN107278056A (en) * | 2016-04-08 | 2017-10-20 | 东莞市斯坦得电子材料有限公司 | A kind of technique for printed circuit board Organic Conductive Films hole metallization |
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