CN104080278B - The production technology of wiring board conductive polymer fenestra technique and its collocation graphic plating - Google Patents
The production technology of wiring board conductive polymer fenestra technique and its collocation graphic plating Download PDFInfo
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- CN104080278B CN104080278B CN201410286508.2A CN201410286508A CN104080278B CN 104080278 B CN104080278 B CN 104080278B CN 201410286508 A CN201410286508 A CN 201410286508A CN 104080278 B CN104080278 B CN 104080278B
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Abstract
The invention discloses a kind of wiring board conductive polymer fenestra technique,Including adjustment,Promote,High molecular polymerization,The step such as microetch afterwards,The characteristic of copper face is not adhere to using regulator,Manganese dioxide layer is only formed on the nonmetallic surface with regulator during promotion,And form high molecular polymer conducting film on manganese dioxide surface under acidic catalyst,The technique has operation simple,Liquid medicine consumption is low,Sewage yield is low,Water consumption is low,Without harmful chemical,The environmental benefit such as low chelate and few sediment,Also have and do not receive palladium price,Occupy little space,The economic benefit such as low cost and high yield,It is more selective,Without copper particle production,Blind hole ability,It is horizontal and vertical,Outstanding internal layer adhesion,The blind hole windowing position technical advantage such as non-foaming,And the graphic plating technique that can directly arrange in pairs or groups,With more line width and BGA systems easy to control in size,Do not result in line carefully and BGA becomes minor issue,And without being filled in after a bronze medal,Reduce cost.
Description
Technical field
The invention belongs to field of printed circuit board fabrication, it is related to a kind of processing method of printed circuit board (PCB) via and is somebody's turn to do
The production method of method collocation graphic plating technique, after specifically a kind of conductive polymer fenestra chemical industry skill and the technique
The production technology of direct graphic plating.
Background technology
In the prior art, the via of printed circuit board (PCB) is usually that metal in hole is realized using the method for chemical plating
Change, i.e., before printed circuit board (PCB) carries out electric plating of whole board operation, through sensitization plays, activation after, with chemical plating hole metallization method,
After depositing last layer metal in non metallic substrate, then copper plating process is carried out, referred to as the electroplates in hole (PTH) technique.This kind of PTH
Although technique technology maturation, there is following drawback：1. containing reducing agent formaldehyde and easily it is carcinogenic；2. chelating agent EDTA is contained；
3. change copper groove and be also easy to produce crystallization, be difficult maintenance；4. activation needs precious metals pd, and price is higher；5. waste water contains a large amount of nuisances
Matter, processing cost is high.
In view of the above-mentioned many disadvantages of PTH, industry occurs in that the way for replacing PTH techniques with black holes chemical industry skill.For example, in
State's patent application：91100028.3, a kind of non-chemical plating hole metallizing is disclosed, its cardinal principle
Be using the black holes liquid containing graphite or carbon dust hole wall formed one layer of black holes film, drying, go film process after
Electroplated.And such as Chinese patent：200710196528.0, a kind of hole electricity conduction method of printed circuit board (PCB) is disclosed,
It is a kind of black holes method.For another example, Japan Patent：No.3284489 and Japan Patent：No.3261569 is disclosed makes carbon sink
Product is processed from copper surface to go out carbon elimination and implement electric plating method on the surface, in an acidic solution.And for example, China
Patent：It is a kind of for two-sided and multi-layer flexible printed circuit board graphic plating method disclosed in 200610061925.2, with
And Chinese patent：It is a kind of for two-sided and multi-layer flexible printed circuit board electro-plating method disclosed in 201010219125.5,
Wherein also all employ black holes chemical industry skill.But these black holes chemical industry skill PCB scrappages in actual production are higher.
In addition to above-mentioned PTH techniques and black holes chemical industry skill, also tin palladium colloid technique and organic colloid palladium technique, for example：
Japan Patent No.2660002, disclosing can be changed into metal chalcogenide by with vulcanizing treatment by Pd-Sn colloid catalysts
Compound film implements electric plating method；Japan Patent No.2799076, discloses stabilized with carrying out through organic polymer
After the treatment of precious metal colloid shape acid solution, vulcanizing treatment is carried out in the method for the generation metal coating under electro ultrafiltration；It is Chinese special
Profit：200680056449.3, a kind of direct coating method and solution for palladium conductor layer formation are disclosed, using by palladium conductor shape
Into solution palladium conductor layer is formed on insulated part, then on palladium conductor layer directly formed electrolytic copper plated film.But
The processing procedure cost of these techniques is all directly very big by the price of precious metal palladium.
In addition, Japan Patent No.3117216, discloses and is adjusted to the potassium permanganate water that pH value is 0~6 with sulfonic acid etc.
In solution formed thin-oxide film layer after, formed azole derivatives conductive polymer coating, then carry out electric plating method.
The content of the invention
In order to solve the above-mentioned technical problem, the invention provides a kind of wiring board conductive polymer fenestra technique and its collocation
The production technology of graphic plating, the wiring board conductive polymer fenestra technique has that operation is simple, liquid medicine consumption is low, sewage is produced
It is raw to measure that low, water consumption is low, environmental benefit is produced etc. without harmful chemical, low chelate and few sediment, also have
Not by palladium price, take up room the economic benefits such as low, economization cost of investment, low production cost and high yield, has more
Selective operation, without copper particle production, blind hole ability, horizontal and vertical, outstanding internal layer adhesion, blind hole windowing position it is non-foaming
Etc. technical advantage, the production technology of wiring board conductive polymer fenestra technique collocation graphic plating is big with more line width and BGA
It is small easy to control, do not result in line carefully and BGA becomes minor issue, and without being filled in after a bronze medal, reduce cost.
The technical scheme that is used to solve its technical problem of the present invention is：
The invention provides a kind of wiring board conductive polymer fenestra technique, including following processing steps：
1) high molecular polymerization → 4) of adjustment → 2) promote → 3) microetch afterwards；
Wherein,
1) adjust：Soaked in regulator and cleaned and adjusted with to nonmetallic surface, carbon is contained in the regulator
Sour sodium and NaOH, and the concentration of sodium carbonate is 55~75ml/L, and it is 10.5~12.5 control the pH value of regulator, is worked
At 60 ± 3 DEG C, the activity duration controls in 62 ± 5sec temperature control；
2) promote：Immersion is so that in step 1 in the accelerator) manganese dioxide covering is formed on nonmetallic surface after adjustment
Layer, contains MnO in permanganate and boric acid, and accelerator in the accelerator4 -Concentration is 80~120g/L, MnO4 2-Concentration is 0
~3g/L and boric acid concentration are 8~19g/L, and it is 5~7 control the pH value of accelerator, and operating temperature is controlled at 90 ± 3 DEG C, work
Industry time control is in 70 ± 5sec；
3) high molecular polymerization：Immersion is so that in step 2 in the organic liquid) on the surface of manganese dioxide coating that is formed
High molecular polymer conducting film is formed, the organic liquid contains organic acid and can form the list of the high molecular polymer
Body, and the monomer concentration be 8.3~13.2ml/L and the concentration of organic acid be 11.5~25ml/L, and control organic liquid
PH value be 1.8~2.5, at 16~22 DEG C, the activity duration is controlled in 75 ± 5sec for operating temperature control；
4) microetch afterwards：Soaked in rear microetch liquid medicine to be cleaned to copper face and be stung erosion, contained in the rear microetch liquid medicine
There are hydrogen peroxide and sulfuric acid, and concentration is H2O213~21ml/L and H2SO420~30ml/L, operating temperature is controlled 30 ± 3
DEG C, the activity duration is controlled in 18 ± 5sec.
It is preferred that carrying out step 1) before, it is necessary to carry out microetching step：Soaked in microetch liquid with to copper surface
Clean and micro- coarse, sodium peroxydisulfate and sulfuric acid are contained in the microetch liquid, and concentration is Na2S2O830~70g/L and
H2SO4Copper ion concentration ＜ 20g/L in 30~50ml/L, and control microetch liquid, operating temperature is controlled at 30 ± 3 DEG C, during operation
Between control in 55 ± 5sec.
It is preferred that in the microetching step and step 1) between, it is necessary to carry out acid pickling step：Carried out using sulfuric acid solution
Pickling, H is contained in the sulfuric acid solution2SO42~5% (percents by volume), operating temperature is controlled in 30 ± 3 DEG C, activity duration
Control is in 49 ± 5sec；
It is preferred that step 2) in permanganate be sodium permanganate.
It is preferred that step 3) in the monomer be thiophene.
It is preferred that step 4) in sting erosion amount control in 2~6 μ ".
It is preferred that step 1) and step 2) in the nonmetallic surface refer to fiberglass surfacing and resin surface.
It is preferred that step 1) to step 4), all need to carry out three road washings after each step.
It is preferred that needing to carry out three road washings after the microetching step, need to carry out San Daoshui after the acid pickling step
Wash.
It is preferred that carrying out de-smear before microetching step is carried out.
It is present invention also offers direct graphic plating production technology after a kind of wiring board conductive polymer fenestra including above-mentioned
Conductive polymer fenestra technique, and carry out in the steps below：
De-smear (Desmear) → conductive polymer fenestra technique → pad pasting → circuit exposure → development → vertical continuous electricity
Plug → pressing after plating (VCP) → fast-etching → automatic optics inspection (AOI) → brown.
The beneficial effects of the invention are as follows：Wiring board conductive polymer fenestra technique of the invention includes adjustment → promotion → height
The steps such as molecule aggregation → rear microetch, the main characteristic that copper face is not adhere to using regulator, are only had during promotion
Manganese dioxide layer is formed on the nonmetallic surface of regulator, and high molecular polymerization is formed on manganese dioxide surface under acidic catalyst
Thing conducting film, the wiring board conductive polymer fenestra technique has that operation is simple, liquid medicine consumption is low, sewage yield is low, water
Consumption is low, environmental benefit is produced etc. without harmful chemical, low chelate and few sediment, also with not receiving palladium price
Influence, take up room the economic benefits such as low, economization cost of investment, low production cost and high yield, more selective operation,
Without copper particle production, blind hole ability, horizontal and vertical, outstanding internal layer adhesion, the blind hole windowing position technical advantage such as non-foaming.
The flow of the production technology of wiring board conductive polymer fenestra technique collocation graphic plating is de-smear → macromolecule conductive film
Filled in after hole technique → pad pasting → circuit exposure → development → vertical continuous plating → fast-etching → automatic optics inspection → brown
→ pressing, the production technology has more line width and BGA systems easy to control in size, does not result in line carefully and BGA becomes minor issue, Er Qiewu
Filled in after needing a bronze medal, reduce cost.
Specific embodiment
Specific embodiment of the invention is illustrated below by way of specific instantiation, those skilled in the art can be by this theory
Content disclosed in bright book understands advantages of the present invention and effect easily.The present invention can also other different modes give reality
Apply, i.e. do not depart from it is disclosed under the scope of, can give different modifications with change.
Embodiment：A kind of wiring board conductive polymer fenestra technique, including following processing steps：
Microetch → pickling → adjustment → promotion → high molecular polymerization → rear microetch.
It is specific as follows：
Wherein, the effect of microetch is that copper surface is carried out to clean and micro- coarse, goes copper removal dirty and ailhead, optimal to ensure
Adhesion of the copper to copper, carries out this microetching step typically after de-smear, if suitable this microetching step right and wrong of preceding operation
It is necessary；The effect of pickling is that further plate face is cleaned, and removes surface oxidation；The effect of adjustment is to nonmetallic surface
Cleaned and adjusted, to reach the purpose of follow-up manganese dioxide layer of most preferably adhering, regulator is not adhere to copper face；The work of promotion
With being to form manganese dioxide coating in nonmetallic surface, it is beneficial to the attachment of follow-up high molecular polymer, because not having on copper face
There is regulator, therefore manganese dioxide coating can not be formed on copper face；Polymerization is then in manganese dioxide coating under acidic catalyst
Surface forms high molecular polymer conducting film；The effect of microetch afterwards is to clean the manganese dioxide of plate face residual and copper face is carried out
It is coarse, rear microetch for liquid medicine selection and sting erosion amount control it is particularly important, consider the present invention using by H2O2With
H2SO4The liquid medicine performance of composition is optimal, easily cleaning plate face manganese dioxide residual, with groove is simple, low cost, is chased after by continuation
Track is compared, and draws following situation：Erosion amount is stung " to sting erosion amount for most safe, hole will not be produced to break risk, and sting erosion amount and be less than less than 6 μ
2 μ " will produce plate face to remain MnO2And power is bad to form the abnormal risk of plating to cause dry film to attach.
Nonmetallic surface described in above-mentioned steps refers to fiberglass surfacing and resin surface.
Above-mentioned each step all needs three roads to wash after completing.
Table 1 below is the operating conditions difference of traditional PTH techniques and conductive polymer fenestra technique of the invention.
Table 1：
Table 2 below is the Cost comparisons of traditional PTH techniques and conductive polymer fenestra technique of the invention.
Table 3 below is that traditional PTH monthly has more cost statistics than conductive polymer membrane process of the present invention.
Table 2 and 3 shows that macromolecule conductive film line can substantially reduce the usage amount of water, and substantially reduce wastewater treatment into
This.
To sum up, above-mentioned wiring board conductive polymer fenestra technique has that operation is simple, liquid medicine consumption is low, sewage yield
Low, water consumption is low, environmental benefit is produced etc. without harmful chemical, low chelate and few sediment, also with not receiving
Palladium price, take up room the economic benefits such as low, economization cost of investment, low production cost and high yield, with more selection
Property operation, without copper particle production, blind hole ability, horizontal and vertical, outstanding internal layer adhesion, the blind hole windowing position skill such as non-foaming
Art advantage.
The technological process of production of above-mentioned wiring board conductive polymer fenestra technique collocation graphic plating (Pattern) is as follows：
De-smear (Desmear) → conductive polymer fenestra technique → pad pasting → circuit exposure → development → vertical continuous plating (VCP)
Plug → pressing after → fast-etching → automatic optics inspection (AOI) → brown.The production technology has line width and BGA easy to control in size
System, does not result in line carefully and BGA becomes minor issue, and without being filled in after a bronze medal, reduces cost.
Embodiment described above description is more specific and detailed, but therefore can not be interpreted as to the scope of the present invention
Limitation.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise,
Various modifications and improvements can be made, these belong to protection scope of the present invention.Therefore, protection scope of the present invention should be with
Claim is defined.
Claims (9)
1. a kind of wiring board conductive polymer fenestra technique, it is characterised in that including following processing steps：
1) high molecular polymerization → 4) of adjustment → 2) promote → 3) microetch afterwards；
Wherein,
1) adjust：Soaked in regulator and cleaned and adjusted with to nonmetallic surface, sodium carbonate is contained in the regulator
And NaOH, and sodium carbonate 55~75ml/L of concentration, and it is 10.5~12.5, operating temperature control to control the pH value of regulator
At 60 ± 3 DEG C, the activity duration controls in 62 ± 5sec system；
2) promote：Immersion is so that in step 1 in the accelerator) manganese dioxide coating is formed on nonmetallic surface after adjustment,
Contain MnO in permanganate and boric acid, and accelerator in the accelerator4 -Concentration is 80~120g/L, MnO4 2-Concentration be 0~
3g/L and boric acid concentration are 8~19g/L, and it is 5~7 control the pH values of accelerator, and operating temperature control is in 90 ± 3 DEG C, operation
Time control is in 70 ± 5sec；
3) high molecular polymerization：Immersion is so that in step 2 in the organic liquid) formed on the surface of manganese dioxide coating that is formed
High molecular polymer conducting film, the organic liquid contains organic acid and can form the monomer of the high molecular polymer, and
The concentration of the monomer is 8.3~13.2ml/L and the concentration of organic acid is 11.5~25ml/L, and controls the pH of organic liquid
It is 1.8~2.5 to be worth, and at 16~22 DEG C, the activity duration is controlled in 75 ± 5sec for operating temperature control；
4) microetch afterwards：Soaked in rear microetch liquid medicine to be cleaned to copper face and be stung erosion, contained in the rear microetch liquid medicine
Hydrogen oxide and sulfuric acid, and concentration is H2O213~21ml/L and H2SO420~30ml/L, operating temperature is controlled at 30 ± 3 DEG C, is made
Industry time control stings the control of erosion amount in 2~6 μ in 18 ± 5sec "；
Carrying out step 1) before, it is necessary to carry out microetching step：Soaked in microetch liquid with to copper surface carry out cleaning and it is micro-
It is coarse, sodium peroxydisulfate and sulfuric acid are contained in the microetch liquid, and concentration is Na2S2O830~70g/L and H2SO430~
Copper ion concentration ＜ 20g/L in 50ml/L, and control microetch liquid, operating temperature controls 30 ± 3 DEG C, and the activity duration is controlled 55
±5sec。
2. wiring board conductive polymer fenestra technique as claimed in claim 1, it is characterised in that in the microetching step and step
It is rapid 1) between, it is necessary to carry out acid pickling step：Pickling is carried out using sulfuric acid solution, H is contained in the sulfuric acid solution2SO42~5%
(percent by volume), at 30 ± 3 DEG C, the activity duration is controlled in 49 ± 5sec for operating temperature control.
3. wiring board conductive polymer fenestra technique as claimed in claim 1, it is characterised in that step 2) in permanganate
It is sodium permanganate.
4. wiring board conductive polymer fenestra technique as claimed in claim 1, it is characterised in that step 3) in the monomer
It is thiophene.
5. wiring board conductive polymer fenestra technique as claimed in claim 1, it is characterised in that step 1) and step 2) in
The nonmetallic surface refers to fiberglass surfacing and resin surface.
6. wiring board conductive polymer fenestra technique as claimed in claim 1, it is characterised in that step 1) to step 4), often
All need to carry out three road washings after individual step.
7. wiring board conductive polymer fenestra technique as claimed in claim 2, it is characterised in that needed after the microetching step
Three road washings are carried out, needs to carry out three road washings after the acid pickling step.
8. wiring board conductive polymer fenestra technique as claimed in claim 1, it is characterised in that before microetching step is carried out
Carry out de-smear.
9. direct graphic plating production technology after a kind of wiring board conductive polymer fenestra, it is characterised in that will including such as right
The conductive polymer fenestra technique described in 1 is sought, and is carried out in the steps below：
De-smear → conductive polymer fenestra technique → pad pasting → circuit exposure → development → vertical continuous plating → fast-etching
Plug → pressing after → automatic optics inspection → brown.
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| CN104582324B (en) * | 2015-01-07 | 2018-04-10 | 台山市精诚达电路有限公司 | Flexible PCB hole metallization method |
| 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 |
| CN106507613A (en) * | 2016-10-11 | 2017-03-15 | 江苏博敏电子有限公司 | A kind of HDI method for manufacturing circuit board of employing conductive polymer polymerization technique |
| CN108221010B (en) * | 2018-01-29 | 2021-02-12 | 莆田市佳宜科技股份有限公司 | Preparation process of high-molecular conductive film of PCB (printed circuit board) |
| CN109413894B (en) * | 2018-10-30 | 2022-02-08 | 生益电子股份有限公司 | Manufacturing method of bottom graph of stepped groove |
| CN110505768A (en) * | 2019-08-05 | 2019-11-26 | 江西志博信科技股份有限公司 | A kind of HDI method for manufacturing circuit board using conductive polymer polymerization technique |
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