CN104744974B - A kind of PCB generates the production technology of macromolecule conductive film with modified activating solution and in PCB through hole and blind hole - Google Patents
A kind of PCB generates the production technology of macromolecule conductive film with modified activating solution and in PCB through hole and blind hole Download PDFInfo
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Abstract
The invention discloses a kind of PCB modified activating solutions, contain the compound or mixture of high manganese ion including 1~100g/L, 0.1~20g/L contains the compound or mixture of at least one of ferrous ion, iron ion, ammonium ion ion, balance deionized water.Ferrous ion, iron ion, a kind of ion or at least two ions in ammonium ion contained in the PCB modified activating solutions of the present invention, make priming reaction can be achieved in relatively low temperature, energy consumption are reduced compared with conventional process conditions；And the activation process requirement of hardboard and soft board can be met simultaneously, while solve because conventional activation liquid has a strong oxidizing property, activated bath must using can high temperature resistant and can powerful oxidation corrosion resistance material prepare, equipment cost is higher the problem of.The present invention reduces energy consumption, reduces equipment cost, expand the scope of application of product by being improved to activating solution.
Description
Technical field
Field is made the invention belongs to PCB, and in particular to a kind of PCB is with modified activating solution and in PCB through hole and blind hole
The production technology of interior generation macromolecule conductive film.
Background technology
PCB is the element that various electronic equipments generally need in information-intensive society.Built on PCB for the different interlayers of multilayer circuit board
When standing electrical connection, certain pre-treatment is typically passed through, makes resin between layers and glass fiber surface generation electric conductivity, enters
One step forms a thickness copper by way of plating, so as to realize the electrical connection on circuit board between different layers.It is common at present
The technique of electric conductivity is produced in the through hole or blind hole of circuit board the thin copper method of chemical plating and conducting polymer method.
The thin copper method of chemical plating uses more early, technics comparing maturation, but not environmentally friendly enough；Macromolecule conductive film common at present
Method is mainly with aniline, pyrroles, and thiophene and its derivative are substrate, trigger polymerization under the conditions of suitably chemically and physically, from
And generate conducting film in material surface.
Method described by patent CN102036509A is to deposit one with electroless copper plating method micropore between the two layers
The thin chemical copper of layer, then thickeied or filling perforation by plating, so as to realize the electrical connection of interlayer.But, institute in electroless copper plating method
Reducing agent is generally formaldehyde, volatile to have very strong carcinogenesis, not environmentally；Urged certainly in addition, electroless copper plating reaction has
Change property, the easy Auto-decomposition of plating solution, thus operating condition harshness, complex steps, undoubtedly add production cost.
Patent US5403467 is described using pyrroles as monomer, using alkaline permanganate solution as activating solution, by whole hole →
Activation → preimpregnation → film forming → electro-coppering, five steps realize the electrical connection of interlayer between the two layers.The work of activating solution in the patent
Temperature is up to 90 DEG C, not only activated bath high energy consumption, and cell body must use oxidation resistant material, cause production cost to increase.
Patent DE19903108A1 is described using thiophene and derivatives as monomer, to add the liquor potassic permanganate of boric acid
The method for preparing conducting film for activating solution, the step of by similar patent US5403467.The operating temperature 85 of the method activating solution
It is~90 DEG C, also higher.
The temperature of activation process of the prior art is all higher, is not suitable for the production of PCB soft boards, while activating solution has
Have a strong oxidizing property, activated bath must using can the material of high temperature resistant and powerful oxidation corrosion resistance make, such as 316 stainless steels cause equipment
Cost is higher.
The content of the invention
An object of the present invention is to provide a kind of PCB modified activating solutions, is not reducing macromolecule conductive film
The operating temperature of modified activating solution can be reduced under conditions of into film quality.
The second object of the present invention is to provide a kind of production work for generating macromolecule conductive film in PCB through hole and blind hole
Above-mentioned modified activating solution is employed in skill, the activating process of the production technology.
One of in order to reach the goal, the present invention uses following technical scheme：
A kind of PCB modified activating solutions, including 1~100g/L contain compound or the mixing of high manganese ion
Thing, 0.1~20g/L contains the compound or mixture of at least one of ferrous ion, iron ion, ammonium ion ion, surplus
Deionized water.Contain appropriate high manganese ion in PCB activating solutions of the prior art, of the invention thes improvement is that
Added in PCB activating solutions in the prior art and contain at least one of ferrous ion, iron ion, ammonium ion ion in right amount
Compound or mixture, under conditions of film quality is not reduced into, it is possible to decrease the high manganese ion promotes what PCB was activated
Temperature.The concentration of compound of the present invention containing high manganese ion be 1~20g/L, such as 1.2g/L, 1.3g/L,
1.4g/L、1.5g/L、1.8g/L、2g/L、2.2g/L、2.5g/L、3g/L、4g/L、5g/L、6g/L、7g/L、8g/L、9g/L、
10g/L、12g/L、15g/L、18g/L、19g/L、20g/L、25g/L、30g/L、35g/L、40g/L、45g/L、50g/L、60g/
L、70g/L、80g/L、90g/L；Change of the present invention containing at least one of ferrous ion, iron ion, ammonium ion ion
The concentration of compound or mixture be 0.1~20g/L, such as 0.12g/L, 0.13g/L, 0.15g/L, 0.18g/L, 0.2g/L,
0.3g/L、0.4g/L、0.5g/L、0.8g/L、1g/L、1.5g/L、2g/L、2.5g/L、3g/L、3.5g/L、4g/L、5g/L、6g/
L、7g/L、8g/L、9g/L、10g/L、12g/L、15g/L、16g/L、18g/L、19g/L。
" g/L " of the present invention is concentration unit, is referred in modified activating solution described in unit volume contained
The quality of the compound or mixture, for example above-mentioned compound containing high manganese ion of the compound or be
Contain a kind of compound of ion in above-mentioned ferrous ion, iron ion, ammonium ion；The mixture is for example above-mentioned to contain permanganic acid
The mixture of radical ion or the mixture containing at least one of above-mentioned ferrous ion, iron ion, ammonium ion ion.
Preferably, the modified activating solution includes compound or the mixing that 4~60g/L contains high manganese ion
Thing, 0.5~10g/L contains the compound or mixture of at least one of ferrous ion, iron ion, ammonium ion ion, surplus
The activation effect of modified activating solution under deionized water, the concentration is preferable.
Wherein, the ferrous ion is come from iron ammonium sulfate, ferrous sulfate, frerrous chloride, ferrous phosphate, ferrous nitrate
At least one compound or mixture；The mixture of the mixture such as iron ammonium sulfate and ferrous sulfate, sulfuric acid is sub-
The mixture of the mixture of the mixture of iron ammonium and frerrous chloride, frerrous chloride and ferrous phosphate, ferrous sulfate and ferrous nitrate,
The mixture of iron ammonium sulfate, ferrous sulfate and frerrous chloride, the mixture of frerrous chloride, ferrous phosphate and ferrous nitrate, sulphur
Sour ferrous ammonium, ferrous sulfate, frerrous chloride, the mixture of ferrous phosphate and ferrous nitrate.
Wherein, change of the iron ion from least one of ammonium ferric sulfate, ferric sulfate, iron chloride, ferric nitrate, ferric phosphate
Compound or mixture；The mixture of the mixture such as ammonium ferric sulfate and ferric sulfate, the mixing of ammonium ferric sulfate and iron chloride
The mixture of thing, ferric sulfate and ferric phosphate, the mixture of ammonium ferric sulfate, ferric sulfate and iron chloride, ammonium ferric sulfate, ferric sulfate, nitre
The mixture of sour iron and ferric phosphate, ammonium ferric sulfate, ferric sulfate, iron chloride, the mixture of ferric nitrate and ferric phosphate.
Wherein, compound of the ammonium ion from least one of ammonium sulfate, iron ammonium sulfate, ammonium chloride, ammonium nitrate
Or mixture；The mixture of the mixture of the mixture such as ammonium sulfate and iron ammonium sulfate, ammonium sulfate and ammonium chloride, chlorine
Change the mixture of ammonium and ammonium nitrate, the mixture of ammonium sulfate, iron ammonium sulfate and ammonium chloride, ammonium sulfate, iron ammonium sulfate and nitre
The mixture of sour ammonium, ammonium sulfate, iron ammonium sulfate, the mixture of ammonium chloride and ammonium nitrate.
Wherein, the high manganese ion comes from potassium permanganate and/or sodium permanganate or other contain free height
The permanganate of Manganate ions；
Preferably, the high manganese ion is the SkyPoly 393C of Guangzhou Tian Cheng Chemical Co., Ltd.s, i.e., poly- hole leads toTM
Activating solution SkyPoly 393, wherein " C " is the trade name code name of the activating solution；In the SkyPoly 393C containing 40~
90g/L sodium permanganate or potassium permanganate, " g/L " refers to the concentration of sodium permanganate or potassium permanganate in SkyPoly 393C,
That is the sodium permanganate or the quality of potassium permanganate contained in unit volume SkyPoly 393C.
In order to reach the goal two, the present invention uses following technical scheme：
A kind of production technology that macromolecule conductive film is generated in PCB through hole and blind hole, the production technology includes activation,
The activation employs above-mentioned modified activating solution；
The activation refers to：The modified activating solution is added in the activated bath by proportioning, its pH is adjusted to 5~7,
The temperature for controlling the activated bath is 65~75 DEG C, and the PCB after adjustment is placed in activated bath, is incubated 1~4min, is washed, system
PCB after must activating, the PCB surface generation manganese dioxide membrane after the activation.
When being activated using traditional activating solution, activation temperature is 85~90 DEG C, and high manganese ion is with very strong
Oxidisability, therefore be not suitable for the production of PCB soft boards, and when in applied to PCB hardboard production technologies, activated bath is necessary
Using high temperature resistant and being resistant to the material of strong oxidizing property and prepare, such as 316 stainless steels strongly limit the applicable model of activating solution
Enclose, also result in equipment cost higher.And the modified activating solution of the present invention is used, activation temperature is greatly reduced, is applicable to
The production of PCB soft boards, activated bath is prepared using PP plastics, not only expands the use model of the modified activating solution of the present invention
Enclose, also reduce energy consumption and equipment cost.
PCB contains resin, glass fiber, three kinds of different materials of copper foil simultaneously, and PCB is placed in the activation containing modified activating solution
In groove, activated under conditions of pH is 5~7,65~75 DEG C, the organic matter adsorption layer on resin and glass fiber changes described
Enter in the ferrous ion in type activating solution, iron ion, ammonium ion in the presence of a kind of ion or at least two ions by Gao Meng
Acid ion is aoxidized, while generating the manganese dioxide membrane of one layer of even compact, the ferrous ion, iron ion, ammonium ion are
For the catalyst of the organic matter adsorption layer on high manganese ion resene and glass fiber, in the presence of the catalyst, live
Changing reaction can be carried out in a low temperature of 65~75 DEG C, shown in priming reaction mechanism such as Fig. 1, chemical equation (1)：
Preferably, the mass area ratio of the manganese dioxide membrane is 1~10mg/dm2, such as 1.2mg/dm2、
1.5mg/dm2、1.8mg/dm2、2mg/dm2、2.5mg/dm2、3mg/dm2、3.5mg/dm2、4mg/dm2、5mg/dm2、6mg/dm2、
7mg/dm2、8mg/dm2、9mg/dm2, more preferably 4~6mg/dm2。
Above-mentioned modified activating solution is used in the activation process of production technology of the present invention, the high score is not being reduced
Subconductivity film greatly reduces the operating temperature of activating solution, the work temperature of activating solution under conditions of film quality and activation effect
As long as 65-75 DEG C of degree, energy consumption is greatly reduced compared with treatment conditions under 90 DEG C of traditional high temperature；And make this technique can
The processing of hardboard and soft board is met simultaneously, while solving conventional activation liquid has strong oxidizing property, activated bath must be used can high temperature resistant
With the material of Strong oxdiative, the problem of equipment cost is higher.
Preferably, the pH of the invention using phosphoric acid and/or the boric acid regulation modified activating solution is described pH to 5~7
Such as 5.2,5.3,5.4,5.5,5.7,5.8,6,6.1,6.3,6.5,6.7,6.9.
In production technology of the present invention, also comprise the following steps before above-mentioned PCB activation：
Cleaning：PCB is placed in PCB cleaning agents, 0.5~1min is incubated at 25~35 DEG C, washing is made after cleaning
PCB；
Adjustment：PCB after the cleaning is placed in PCB adjustment liquid, 0.5~4min is incubated at 58~62 DEG C, washes, system
PCB after must adjusting.
In Electronic Assemblies work, PCB is effectively cleaned, is to ensure that related electronic products have high reliability
An important ring, by selecting suitable PCB cleaning agents, it is ensured that good sheet resistance, prevent from leaking electricity and causing PCB to fail,
The electrical property and reliability of PCB components are favorably improved, extends the life-span of product in itself.PCB cleanings of the present invention
Agent cleaning PCB temperature be 25~35 DEG C, such as 26 DEG C, 27 DEG C, 28 DEG C, 29 DEG C, 30 DEG C, 31 DEG C, 32 DEG C, 33 DEG C, 34 DEG C, 35
℃。
The PCB cleaning agents are H2SO4With NaPS mixed solution, preferably 35mL/L H2SO4With 90g/L NaPS's
Mixed solution；" mL/L " refers to contain H in unit volume PCB cleaning agents2SO4Volume, the H2SO4Mass fraction
For 50%；Using H2SO4Mixed solution with NaPS can remove the postwelding formed in PCB assembling process as cleaning agent
Residue and other processing pollution things, wherein, the postwelding residue includes the soldering paste not volatilized completely during manual welding
(main component is rosin, ethanol, diethyl to the weldering auxiliary agent not volatilized completely in (main component is rosin) and immersed solder, wave-soldering process
Alcohol ammonia etc.), if impression of the hand in other processing pollutions owner technique process, (main component is Na to sweat stain+、K+, oil
Fat and human secretion), equipment frock chucking surface adhesion greasy dirt (main component is grease) and turnover, packaging process table
Face pollutant (predominantly fiber, absorbability particle and polyvinyl chloride particles).After PCB is cleaned in PCB cleaning agents, its surface
Cleaning, visually observes the residue less than its surface.
Because PCB is simultaneously comprising these three unlike materials of resin, glass fiber and copper foil, so generating conducting film on PCB
Before be typically passed through a series of chemical treatment, the Si-OH groups on adjusting stage glass fiber surface can pass through electrostatic interaction
Mode adsorbs the organic matter formation coating electrically opposite with-OH groups, as shown in Figure 2.PCB of the present invention adjusts liquid
The SkyPoly 391C of Guangzhou Tian Cheng Chemical Co., Ltd.s, i.e., poly- hole leads toTMLiquid SkyPoly 391 is adjusted, wherein " C " is the PCB
Adjust the trade name code name of liquid.
In production technology of the present invention, film forming is also included after the activation, the film forming refers to：By the work
PCB after change is placed in PCB into film liquid, is incubated 1~4min at 18~22 DEG C, washes, drying, you can in the PCB through hole and
The macromolecule conductive film is made in blind hole.The operating temperature of the film forming be 18~22 DEG C, such as 18.5 DEG C, 19 DEG C, 20 DEG C,
21℃.PCB after activation immerses the PCB into film liquid, into the active material (thiophene or aniline monomer) and dioxy in film liquid
Change the conductive organic thin film of manganese reaction generation, i.e., macromolecule conductive film of the present invention.
The PCB into film liquid be the SkyPoly 396A of Guangzhou Tian Cheng Chemical Co., Ltd.s, SkyPoly 396B,
SkyPoly 396M mixture, i.e., poly- hole leads toTMLiquid SkyPoly 396 is adjusted, wherein " A ", " B ", " M " are respectively that the PCB is adjusted
The trade name code names of the three types of whole liquid, three types are generally applied in combination into film liquid；Preferably, the PCB is into film liquid
Formula be：30m L/L SkyPoly 396A, 20m L/L SkyPoly 396B, 20m L/L SkyPoly 396M, surplus
For deionized water.
Compared with prior art, beneficial effects of the present invention are：A kind of PCB modified activating solutions, including 1~100g/L
Compound or mixture containing high manganese ion, 0.1~20g/L contain a kind of in ferrous ion, iron ion, ammonium ion
The compound or mixture of ion or the mixture of at least two ions, balance deionized water.The PCB of the present invention is with changing
Enter a kind of ion or at least two ions in the ferrous ion contained in type activating solution, iron ion, ammonium ion, Gao Meng can be used as
The catalysis of the uniform fine and closely woven manganese dioxide membrane of organic matter adsorption layer generation in acid ion oxidation PCB on glass fiber and resin
Agent, has very strong catalytic action to priming reaction, priming reaction is can be achieved at 65~75 DEG C, with 90 DEG C of traditional high temperature
Lower treatment conditions are compared and greatly reduce energy consumption；And this technique can meet the processing of hardboard and soft board simultaneously, while solving to pass
System activating solution has a strong oxidizing property, activated bath must using can high temperature resistant and can the material of powerful oxidation corrosion resistance prepare, equipment cost is higher
The problem of.The present invention reduces energy consumption, reduces equipment cost, expand product by being improved to activation formula of liquid
The scope of application, achieves good economic benefit.
The PCB of the present invention is mainly used in the conducting technique of double-deck and multi-layer PCB through hole and blind hole with modified activating solution
In.
Brief description of the drawings
Fig. 1 is priming reaction mechanism of the invention.
Adsorption mechanisms of the Fig. 2 for adjustment liquid of the invention on the glass fibers.
Fig. 3 is the SEM/EDS spectrograms on the PCB hardboards surface of the activated processing of the embodiment of the present invention 1.
Section after the electroplates in hole copper that Fig. 4 turns on for the embodiment of the present invention 1 after thermal shock experiment.
Section after the electroplates in hole copper that Fig. 5 turns on for the embodiment of the present invention 2 after thermal shock experiment.
Fig. 6 is the section after the blind hole electro-coppering that the embodiment of the present invention 3 is turned on.
Fig. 7 is the macromolecule that the embodiment of the present invention 4, embodiment 5 are generated on PCB hardboards (A) and PCB soft boards (B) respectively
Conducting film.
Fig. 8 is the macromolecule that comparative example 1 of the present invention, comparative example 2 are generated on PCB hardboards (A) and PCB soft boards (B) respectively
Conducting film.
Embodiment
3-8 and technical scheme is further illustrated by embodiment below in conjunction with the accompanying drawings.
Unless specific instructions, various raw materials of the invention are commercially available buys, or is prepared according to the conventional method of this area
Obtain.
Embodiment 1
Hardboard vertical line generates macromolecule conductive film in 250 μm of aperture, depth 1.6mm through hole.
Modified activation formula of liquid is as follows：
Film forming formula of liquid is as follows：
PCB is placed in 35mL/L H2SO4In (50%w/w) and 90g/L NaPS mixed solution, 1min is incubated at 30 DEG C,
Washing；Then PCB is placed in 65mL/L adjustment liquid SkyPoly 391C, 2min, washing is incubated at 62 DEG C；PCB is placed in again
In activated bath, above-mentioned modified activating solution is added by proportioning, the pH to 6.5 of modified activating solution is adjusted using boric acid, control is lived
The temperature for changing groove is 70 DEG C, is incubated 3min, and washing generates manganese dioxide membrane in PCB surface；Finally by PCB be placed in it is above-mentioned into
In film liquid SkyPoly 396A, SkyPoly 396B, SkyPoly 396M mixed liquor, 4min is incubated at 20 DEG C, is washed, is dried
It is dry, you can macromolecule conductive film is made in PCB through hole and blind hole.
The PCB of Surface Creation manganese dioxide membrane after above-mentioned activation is taken to carry out SEM/EDS analyses under ESEM, as a result
See Fig. 3.It was found from from the EDS collection of illustrative plates in Fig. 3, in PCB glass fibre (Glass Fiber), epoxy resin (Epoxy
Resin) and copper foil (Copper) surface generates manganese dioxide, the mass area ratio of manganese dioxide membrane is 5mg/
dm2。
As a result >=10 grade the one layer thin copper of flash carries out backlight test again in the PCB through hole after above-mentioned processing,.
PCB through hole electroplated Copper treatment again, wicking 8 times, each 10s at 288 DEG C after above-mentioned processing conducting, are carried out
Thermal shock test, test result is shown in Fig. 4.As can be seen from Figure 4, PCB imperforate walls segregation phenomenon occurs.
Embodiment 2
Hardboard horizontal line generates high score using the production technology of the present invention in 250 μm of aperture, thickness of slab 2.4mm through hole
Subconductivity film.
Modified activation formula of liquid is as follows：
SkyPoly 393C 110m L/L
Ferrous sulfate 5g/L
Deionized water surplus
Film forming formula of liquid is as follows：
PCB is placed in 35mL/L H2SO4In (50%w/w) and 90g/L NaPS mixed solution, 1min is incubated at 30 DEG C,
Washing；Then PCB is placed in 65mL/L adjustment liquid SkyPoly 391C, 1min, washing is incubated at 60 DEG C；PCB is placed in again
In activated bath, above-mentioned modified activating solution is added by proportioning, the pH to 6 of modified activating solution, control activation are adjusted using sulfuric acid
The temperature of groove is 65 DEG C, is incubated 80s, and washing generates manganese dioxide membrane in PCB surface；PCB is finally placed in into film liquid
In SkyPoly 396A, SkyPoly 396B, SkyPoly 396M mixed liquor, 70s is incubated at 20 DEG C, is washed, drying, you can
Macromolecule conductive film is made in PCB through hole and blind hole.
As a result >=10 grade the one layer thin copper of flash carries out backlight test again in the PCB through hole after above-mentioned processing,.
PCB through hole electroplated Copper treatment again after above-mentioned processing conducting, wicking 8 times, each 10s under the conditions of 288 DEG C,
Thermal shock test is carried out, test result is shown in Fig. 5.As can be seen from Figure 5, PCB imperforate walls segregation phenomenon occurs.
Embodiment 3
Hardboard horizontal line generates macromolecule using the production technology of the present invention in 100 μm of aperture, deep 100 μm blind hole
Conducting film.
Modified activation formula of liquid is as follows：
Film forming formula of liquid is as follows：
PCB is placed in 35mL/L H2SO4In (50%w/w) and 90g/L NaPS mixed solution, 1min is incubated at 30 DEG C,
Washing；Then PCB is placed in adjustment liquid SkyPoly 391C, 3min, washing is incubated at 60 DEG C；PCB is placed in activated bath again
In, above-mentioned modified activating solution is added by proportioning, the pH to 6.5 of modified activating solution is adjusted using phosphoric acid, control activated bath
Temperature is 75 DEG C, is incubated 1min, and washing generates manganese dioxide membrane in PCB surface；PCB is finally placed in into film liquid SkyPoly
In 396A, SkyPoly 396B, SkyPoly 396M mixed liquor, 3min is incubated at 20 DEG C, is washed, drying, you can logical in PCB
Macromolecule conductive film is made in hole and blind hole.
By detection of being cut into slices with the blind hole of upper type activation process, then after flash copper, covered complete (Fig. 6) in hole.
Embodiment 4
Hardboard vertical line is using the modified activating solution same as Example 1 life on PCB hardboards (A) with process conditions
Into macromolecule conductive film, the macromolecule conductive film generated is shown in Fig. 7 A.
Embodiment 5
Soft board vertical line is using the modified activating solution same as Example 1 life on PCB soft boards (B) with process conditions
Into macromolecule conductive film, the macromolecule conductive film generated is shown in Fig. 7 B.
Comparative example 1
Hardboard vertical line uses following conventional activation liquid, and other process conditions are same as Example 1, at PCB hardboards (A)
Upper generation macromolecule conductive film, the macromolecule conductive film generated is shown in Fig. 8 A.
Activate formula of liquid as follows：
SkyPoly 393C 110m L/L
Deionized water surplus
Comparative example 2
Soft board vertical line uses the conventional activation liquid of comparative example 1, and other process conditions are same as Example 1, soft in PCB
Macromolecule conductive film is generated on plate (B), the macromolecule conductive film generated is shown in Fig. 8 B.
Embodiment 4 and the conductive capability of the macromolecule conductive film obtained by comparative example 1 are tested, test result is shown in Table 1.
Table 1
| Conductive capability | Embodiment 4 | Embodiment 5 | Comparative example 1 | Comparative example 2 |
| Resistance/K Ω | 14 | 11 | 114 | 530 |
Found by contrasting, film forming again after being activated using the modified activating solution of the present invention to pcb board is obtained
The resistance only 11K Ω of macromolecule conductive film on the resistance of macromolecule conductive film on PCB hardboards only 14K Ω, PCB soft boards, say
The bright modified activating solution is highly suitable for PCB hardboards, the activation process of PCB soft boards；In activating process on glass fiber and resin
Organic matter adsorption layer aoxidized by high manganese ion and generate the manganese dioxide membrane of sufficient amount, manganese dioxide with into film liquid
Thiophene or the complete macromolecule conductive film of aniline monomer reaction generation；And pcb board is activated using traditional activating solution
The resistance of macromolecule conductive film on film forming again afterwards, obtained PCB hardboards reaches 114K Ω, the especially macromolecule on PCB soft boards
The resistance of conducting film reaches 530K Ω unexpectedly, this illustrate traditional activating solution be insufficient to allow at 70 DEG C high manganese ion with
Oxidation reaction occurs for the organic matter adsorption layer on pcb board, so as to hinder follow-up film formation reaction, causes its resistance to increase, i.e.,
Conductive capability is very poor.
Therefore, compared with traditional handicraft, activation effect and macromolecule are not being reduced using the modified activating solution of the present invention
Conducting film, using that can complete priming reaction at relatively low temperature, reduces energy consumption and production under conditions of film quality
Cost, expands the scope of application of the modified activating solution, can obtain good economic benefit.
Above example is only used for illustrating the method detailed of the present invention, the invention is not limited in above-mentioned method detailed, i.e.,
Do not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Person of ordinary skill in the field is it will be clearly understood that right
Any improvement of the present invention, addition, the selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention
Deng within the scope of all falling within protection scope of the present invention and being open.
Claims (15)
1. a kind of PCB modified activating solutions, it is characterised in that including 1~90g/L contain high manganese ion compound or
Person's mixture, 0.1~20g/L contains compound or the mixing of at least one of ferrous ion, iron ion, ammonium ion ion
Thing, balance deionized water.
2. modified activating solution according to claim 1, it is characterised in that contain high manganese ion including 4~60g/L
Compound or mixture, 0.5~10g/L contains the compound of at least one of ferrous ion, iron ion, ammonium ion ion
Or mixture, balance deionized water.
3. modified activating solution according to claim 1, it is characterised in that the ferrous ion from iron ammonium sulfate,
The compound or mixture of at least one of ferrous sulfate, frerrous chloride, ferrous phosphate, ferrous nitrate；
Compound of the iron ion from least one of ammonium ferric sulfate, ferric sulfate, iron chloride, ferric nitrate, ferric phosphate or
Mixture；
Compound or mixing of the ammonium ion from least one of ammonium sulfate, iron ammonium sulfate, ammonium chloride, ammonium nitrate
Thing.
4. modified activating solution according to claim 1, it is characterised in that the high manganese ion comes from potassium permanganate
And/or sodium permanganate.
5. modified activating solution according to claim 1, it is characterised in that the high manganese ion is held from Guangzhou day
The SkyPoly 393C of Chemical Co., Ltd..
6. a kind of production technology that macromolecule conductive film is generated in PCB through hole and blind hole, it is characterised in that the production technology
Including activation, the activation employs the modified activating solution as described in any one of Claims 1-4；
The activation refers to：The modified activating solution is added in the activated bath by proportioning, its pH to 5~7 is adjusted, controlled
The temperature of the activated bath is 65~75 DEG C, and the PCB after adjustment is placed in activated bath, is incubated 1~4min, and washing is made and lived
PCB after change, the PCB surface generation manganese dioxide membrane after the activation.
7. production technology according to claim 6, it is characterised in that the mass area ratio of the manganese dioxide membrane is
1~10mg/dm2。
8. production technology according to claim 7, it is characterised in that the mass area ratio of the manganese dioxide membrane is
4~6mg/dm2。
9. production technology according to claim 6, it is characterised in that using any one in phosphoric acid, boric acid, sulfuric acid or
At least two mixture adjusts the pH to 5~7 of the modified activating solution.
10. production technology according to claim 6, it is characterised in that also comprise the following steps before the activation：
Cleaning：PCB is placed in PCB cleaning agents, 0.5~1min is incubated at 25~35 DEG C, the PCB after cleaning is made in washing；
Adjustment：PCB after the cleaning is placed in PCB adjustment liquid, 0.5~4min is incubated at 58~62 DEG C, washing is made and adjusted
PCB after whole.
11. production technology according to claim 10, it is characterised in that the PCB cleaning agents are H2SO4With mixing for NaPS
Close solution；The H2SO4Mass fraction be 50%；The PCB adjustment liquid is the SkyPoly of Guangzhou Tian Cheng Chemical Co., Ltd.s
391C。
12. production technology according to claim 11, it is characterised in that the PCB cleaning agents are 35mL/L H2SO4With
90g/L NaPS mixed solution.
13. production technology according to claim 6, it is characterised in that also include film forming, the film forming after the activation
Refer to：PCB after the activation is placed in PCB into film liquid, 1~4min is incubated at 18~22 DEG C, washes, drying, you can
Macromolecule conductive film is made in the PCB through hole and blind hole.
14. production technology according to claim 13, it is characterised in that the PCB holds chemical industry into film liquid for Guangzhou day to be had
SkyPoly 396A, the SkyPoly 396B of limit company and SkyPoly 396M mixture.
15. production technology according to claim 14, it is characterised in that the PCB is into the formula of film liquid：30m L/L
SkyPoly 396A, 20m L/L SkyPoly 396B, 20m L/L SkyPoly 396M, surplus is deionized water.
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| CN107447241A (en) * | 2017-07-27 | 2017-12-08 | 苏州天承化工有限公司 | A kind of activating solution and activating process of environment-friendly type macromolecule conducting film |
| CN107484355A (en) * | 2017-08-01 | 2017-12-15 | 苏州天承化工有限公司 | A kind of catalytic liquid and technique for class support plate hole metallization |
| 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) |
| CN109056015A (en) * | 2018-10-19 | 2018-12-21 | 莆田市涵江区依吨多层电路有限公司 | The mechanical blind brill pattern plating jet apparatus of smart home printed circuit board and its method |
| CN113993303B (en) * | 2021-10-27 | 2023-12-22 | 上海天承化学有限公司 | Method for metallizing holes of mixed-voltage circuit board |
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