CN104744974A - Improved activation liquor for PCB and production technology for generating conductive polymer films in through hole and blind hole of PCB - Google Patents
Improved activation liquor for PCB and production technology for generating conductive polymer films in through hole and blind hole of PCB Download PDFInfo
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- CN104744974A CN104744974A CN201510102929.XA CN201510102929A CN104744974A CN 104744974 A CN104744974 A CN 104744974A CN 201510102929 A CN201510102929 A CN 201510102929A CN 104744974 A CN104744974 A CN 104744974A
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Abstract
The invention discloses improved activation liquor for a PCB. The improved activation liquor for the PCB comprises 1-100g/L of a compound or a mixture containing permanganic acid radical ions, 0.1-20g/L of a compound or a mixture containing at least one of ferrous ion, ferric ion and ammonium ion and the balance of deionized water. The improved activation liquor for the PCB contains one or at least two of ferrous ion, ferric ion and ammonium ion, so that an activation reaction can be carried out at low temperature, and energy consumption is reduced compared with the traditional technological conditions; meanwhile, activating treatment requirements of a hard board and a flexible board can be met at the same time, and the problems that an activation tank needs to be prepared from a high-temperature-resistant and strong-oxidation-resistant material as the traditional activation liquor has strong oxidizing property and equipment cost is high can be solved. The activation liquor is improved, so that the energy consumption is reduced, the equipment cost is reduced, and product application range is expanded.
Description
Technical field
The invention belongs to PCB and make field, be specifically related to a kind of PCB modified version activation solution and in PCB through hole and blind hole, generate the production technique of macromolecule conductive film.
Background technology
PCB is the element that in information society, various electronics generally needs.PCB is upper is when setting up electrical connection between multilayer circuit board different layers, usually will through certain pre-treatment, make resin and glass yarn surface between layers produce electroconductibility, the mode further by plating forms thick layer copper, thus the electrical connection on realizing circuit plate between different layers.The technique producing electroconductibility in the through hole at circuit card common at present or blind hole has the thin copper method of electroless plating and conductive polymers method.
The thin copper method of electroless plating uses comparatively early, and technics comparing is ripe, but environmental protection not; Conductive polymer embrane method common is at present mainly with aniline, and pyrroles, thiophene and its derivative are substrate, initiated polymerization under suitable chemistry and physical condition, thus generate conducting film at material surface.
Method described by patent CN102036509A deposits the thin chemical copper of one deck with in electroless copper plating method micropore between the two layers, then thicken or filling perforation through plating, thus realize the electrical connection of interlayer.But reductive agent used in electroless copper plating method is generally formaldehyde, volatile have very strong carcinogenesis, not environmentally; In addition, electroless copper plating reaction has autocatalytic nature, the easy Auto-decomposition of plating solution, and thus operational condition harshness, complex steps, add production cost undoubtedly.
It is monomer that patent US5403467 describes with pyrroles, take alkaline permanganate solution as activation solution, and through whole hole → activation → preimpregnation → film forming → electro-coppering, five steps realize the electrical connection of interlayer between the two layers.In this patent, the working temperature of activation solution is up to 90 DEG C, and not only activated bath energy consumption is high, and cell body must use oxidation resistant material, causes production cost to increase.
It is monomer that patent DE19903108A1 describes with thiophene and derivatives, to add the potassium permanganate solution of boric acid for activation solution, prepares the method for conducting film through the step of similar patent US5403467.The working temperature of this method activation solution 85 ~ 90 DEG C is also higher.
The temperature of activation treatment of the prior art is all higher, is not suitable for the production of PCB soft board, and activation solution has strong oxidizing property simultaneously, and activated bath must adopt and can high temperature resistantly make with the material of powerful oxidation corrosion resistance, and such as 316 stainless steels, cause equipment cost higher.
Summary of the invention
An object of the present invention is to provide a kind of PCB modified version activation solution, can reduce the working temperature of modified version activation solution under the condition of one-tenth film quality not reducing macromolecule conductive film.
Two of object of the present invention is to provide a kind of production technique generating macromolecule conductive film in PCB through hole and blind hole, have employed above-mentioned modified version activation solution in the activating process of this production technique.
One of in order to reach the goal, the present invention is by the following technical solutions:
A kind of PCB modified version activation solution, comprise compound or mixture that 1 ~ 100g/L contains high manganese ion, 0.1 ~ 20g/L contains compound or the mixture of at least one ion in ferrous ion, iron ion, ammonium ion, balance deionized water.Containing appropriate high manganese ion in PCB activation solution of the prior art, improvements of the present invention are to add the appropriate compound or the mixture that contain at least one ion in ferrous ion, iron ion, ammonium ion in PCB activation solution in the prior art, under the condition not being lowered into film quality, the temperature that described high manganese ion impels PCB to activate can be reduced.The concentration of the compound containing high manganese ion of the present invention is 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; Of the present invention is 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 containing the compound of at least one ion or the concentration of mixture in ferrous ion, iron ion, ammonium ion.
" g/L " of the present invention is concentration unit, refer to this compound contained in modified version activation solution described in unit volume or the quality of mixture, this compound described is the above-mentioned compound containing high manganese ion or the compound containing a kind of ion in above-mentioned ferrous ion, iron ion, ammonium ion such as; Described mixture is the above-mentioned mixture containing high manganese ion or the mixture containing at least one ion in above-mentioned ferrous ion, iron ion, ammonium ion such as.
Preferably, described modified version activation solution comprises compound or the mixture that 4 ~ 60g/L contains high manganese ion, 0.5 ~ 10g/L contains compound or the mixture of at least one ion in ferrous ion, iron ion, ammonium ion, balance deionized water, the activation effect of the modified version activation solution under this concentration is better.
Wherein, described ferrous ion is from the compound of at least one in ferrous ammonium sulphate, ferrous sulfate, iron protochloride, ferrous phosphate, Iron nitrate or mixture; The mixture of described mixture such as ferrous ammonium sulphate and ferrous sulfate, the mixture of ferrous ammonium sulphate and iron protochloride, the mixture of iron protochloride and ferrous phosphate, the mixture of ferrous sulfate and Iron nitrate, the mixture of ferrous ammonium sulphate, ferrous sulfate and iron protochloride, the mixture of iron protochloride, ferrous phosphate and Iron nitrate, the mixture of ferrous ammonium sulphate, ferrous sulfate, iron protochloride, ferrous phosphate and Iron nitrate.
Wherein, described iron ion is from the compound of at least one in ferric ammonium sulfate, ferric sulfate, iron(ic) chloride, iron nitrate, tertiary iron phosphate or mixture; The mixture of described mixture such as ferric ammonium sulfate and ferric sulfate, the mixture of ferric ammonium sulfate and iron(ic) chloride, the mixture of ferric sulfate and tertiary iron phosphate, the mixture of ferric ammonium sulfate, ferric sulfate and iron(ic) chloride, the mixture of ferric ammonium sulfate, ferric sulfate, iron nitrate and tertiary iron phosphate, the mixture of ferric ammonium sulfate, ferric sulfate, iron(ic) chloride, iron nitrate and tertiary iron phosphate.
Wherein, described ammonium ion is from the compound of at least one in ammonium sulfate, ferrous ammonium sulphate, ammonium chloride, ammonium nitrate or mixture; The mixture of described mixture such as ammonium sulfate and ferrous ammonium sulphate, the mixture of ammonium sulfate and ammonium chloride, the mixture of ammonium chloride and ammonium nitrate, the mixture of ammonium sulfate, ferrous ammonium sulphate and ammonium chloride, the mixture of ammonium sulfate, ferrous ammonium sulphate and ammonium nitrate, the mixture of ammonium sulfate, ferrous ammonium sulphate, ammonium chloride and ammonium nitrate.
Wherein, described high manganese ion, from potassium permanganate and/or sodium permanganate, also can be that other contain the permanganate of free high manganese ion;
Preferably, described high manganese ion is the SkyPoly 393C of Guangzhou Tian Cheng Chemical Co., Ltd., and namely poly-hole leads to
tMactivation solution SkyPoly 393, wherein " C " the trade(brand)name code name that is this activation solution; Sodium permanganate containing 40 ~ 90g/L in described SkyPoly393C or potassium permanganate, described " g/L " refers to the concentration of sodium permanganate or potassium permanganate in SkyPoly 393C, the sodium permanganate namely contained in unit volume SkyPoly 393C or the quality of potassium permanganate.
In order to reach the goal two, the present invention by the following technical solutions:
In PCB through hole and blind hole, generate a production technique for macromolecule conductive film, described production technique comprises activation, and described activation have employed above-mentioned modified version activation solution;
Described activation refers to: in described activated bath, add described modified version activation solution by proportioning, regulate its pH to 5 ~ 7, the temperature controlling described activated bath is 65 ~ 75 DEG C, PCB after adjustment is placed in activated bath, insulation 1 ~ 4min, washing, the PCB after obtained activation, the PCB Surface Creation manganese dioxide membrane after described activation.
When adopting traditional activation solution to activate, activation temperature is 85 ~ 90 DEG C, and high manganese ion has very strong oxidisability, therefore the production of PCB soft board is not suitable for, and when being applied in PCB hardboard production technique, activated bath must adopt can high temperature resistantly be prepared with the material of powerful oxidation corrosion resistance, such as 316 stainless steels, strongly limit the scope of application of activation solution, cause equipment cost higher simultaneously.And adopting modified version activation solution of the present invention, activation temperature significantly reduces, and is applicable to the production of PCB soft board, and activated bath adopts PP plastics to prepare, and not only expands the use range of modified version activation solution of the present invention, also reduces energy consumption and equipment cost.
PCB is simultaneously containing resin, glass yarn, Copper Foil three kinds of differing materials, PCB is placed in the activated bath containing modified version activation solution, be 5 ~ 7 at pH, activate under the condition of 65 ~ 75 DEG C, the ferrous ion of Adsorption of Organic layer in described modified version activation solution on resin and glass yarn, iron ion, in ammonium ion a kind of ion or at least two kinds of ions effect under be oxidized by high manganese ion, generate the manganese dioxide membrane of one deck even compact simultaneously, described ferrous ion, iron ion, ammonium ion is the catalyzer of the Adsorption of Organic layer on high manganese ion resene and glass yarn, under the effect of this catalyzer, priming reaction can carry out under the low temperature of 65 ~ 75 DEG C, priming reaction mechanism is as Fig. 1, shown in chemical equation (1):
Preferably, the mass area ratio of described manganese dioxide membrane is 1 ~ 10mg/dm
2, such as 1.2mg/dm
2, 1.5mg/dm
2, 1.8mg/dm
2, 2mg/dm
2, 2.5mg/dm
2, 3mg/dm
2, 3.5mg/dm
2, 4mg/dm
2, 5mg/dm
2, 6mg/dm
2, 7mg/dm
2, 8mg/dm
2, 9mg/dm
2, more preferably 4 ~ 6mg/dm
2.
Above-mentioned modified version activation solution is adopted in the reactivation process of production technique of the present invention, under not reducing described macromolecule conductive film and becoming the condition of film quality and activation effect, greatly reduce the working temperature of activation solution, as long as the working temperature 65-75 DEG C of activation solution, greatly reduce energy consumption compared with treatment condition under traditional 90 DEG C of high temperature; And make this technique can meet the process of hardboard and soft board, solving conventional activation liquid has strong oxidizing property simultaneously simultaneously, activated bath must adopt can the material of high temperature resistant and Strong oxdiative, the problem that equipment cost is higher.
Preferably, the present invention adopts phosphoric acid and/or boric acid to regulate pH to 5 ~ 7 of described modified version activation solution, described pH 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 technique of the present invention, also comprised the steps: before above-mentioned PCB activation
Clean: PCB to be placed in PCB clean-out system, at 25 ~ 35 DEG C of insulation 0.5 ~ 1min, washing, obtains the PCB after cleaning;
Adjust: the PCB after described cleaning is placed in PCB and adjusts liquid, at 58 ~ 62 DEG C of insulation 0.5 ~ 4min, washing, obtains the PCB after adjusting.
In Electronic Assemblies work, PCB is cleaned effectively, guarantee that related electronic products has an important ring of high reliability, by selecting suitable PCB clean-out system, good surface resistivity can be ensured, prevent electric leakage and cause PCB to lose efficacy, contribute to the electrical property and the reliability that improve PCB assembly, extend the life-span of product in itself.The temperature of PCB clean-out system cleaning PCB of the present invention is 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 DEG C.
Described PCB clean-out system is H
2sO
4with the mixing solutions of NaPS, be preferably 35mL/L H
2sO
4with the mixing solutions of 90g/L NaPS; Described " mL/L " refers in unit volume PCB clean-out system containing H
2sO
4volume, described H
2sO
4massfraction be 50%; Adopt H
2sO
4with the mixing solutions of NaPS as clean-out system, can remove and assemble at PCB the postwelding residue and other processing pollution things that are formed in the course of processing, wherein, described postwelding residue comprises the weldering auxiliary agent (main component is rosin, ethanol, diethanolamine etc.) do not volatilized completely in the soldering paste (main component is rosin) that do not volatilize completely in manual welding process and immersed solder, wave-soldering process, if the impression of the hand in described other processing pollution owner processes process, (main component is Na to sweat stain
+, K
+, grease and human secretion), equipment frock chucking surface adhere to greasy dirt (main component is grease) and turnover, wrapping process surface contaminant (being mainly fiber, absorbability particle and polyvinyl chloride particles).After PCB cleans in PCB clean-out system, its surface cleaning, visual inspection is less than the residue on its surface.
Because PCB comprises these three kinds of unlike materials of resin, glass yarn and Copper Foil simultaneously, so usually will through a series of chemical treatment generate conducting film on PCB before, Si-OH group on adjusting stage glass yarn surface can adsorb the organism electrically contrary with-OH group by the mode of electrostatic interaction and form tectum, as shown in Figure 2.PCB of the present invention adjusts the SkyPoly 391C that liquid is Guangzhou Tian Cheng Chemical Co., Ltd., and namely poly-hole leads to
tMadjustment liquid SkyPoly 391, wherein " C " is the trade(brand)name code name of this PCB adjustment liquid.
In production technique of the present invention, also comprise film forming after described activation, described film forming refers to: the PCB after described activation is placed in PCB film forming liquid, at 18 ~ 22 DEG C of insulation 1 ~ 4min, washing, dries, can obtain described macromolecule conductive film in described PCB through hole and blind hole.The working temperature of described film forming is 18 ~ 22 DEG C, such as 18.5 DEG C, 19 DEG C, 20 DEG C, 21 DEG C.PCB after activation immerses in described PCB film forming liquid, and the active substance (thiophene or aniline monomer) in film forming liquid and Manganse Dioxide react and generates conductive organic thin film, i.e. macromolecule conductive film of the present invention.
Described PCB film forming liquid is SkyPoly 396A, the SkyPoly 396B of Guangzhou Tian Cheng Chemical Co., Ltd., the mixture of SkyPoly 396M, and namely poly-hole leads to
tMadjustment liquid SkyPoly 396, wherein " A ", " B ", " M " are respectively the trade(brand)name code name that this PCB adjusts the three types of liquid, and the film forming liquid of three types combinationally uses usually; Preferably, the formula of described PCB film forming liquid is: 30m L/L SkyPoly 396A, 20m L/LSkyPoly 396B, 20m L/L SkyPoly 396M, surplus is deionized water.
Compared with prior art, beneficial effect of the present invention is: a kind of PCB modified version activation solution, comprise compound or mixture that 1 ~ 100g/L contains high manganese ion, 0.1 ~ 20g/L contains the compound of a kind of ion in ferrous ion, iron ion, ammonium ion or the mixture of mixture or at least two kinds of ions, balance deionized water.A kind of ion or at least two kinds of ions in the ferrous ion contained in PCB modified version activation solution of the present invention, iron ion, ammonium ion, the Adsorption of Organic layer that can be used as in high manganese ion oxidation PCB on glass yarn and resin generates the catalyzer of evenly fine and closely woven manganese dioxide membrane, to priming reaction, there is very strong katalysis, priming reaction can be realized at 65 ~ 75 DEG C, greatly reduce energy consumption compared with treatment condition under traditional 90 DEG C of high temperature; And this technique can meet the process of hardboard and soft board simultaneously, solve conventional activation liquid has strong oxidizing property simultaneously, and activated bath must adopt can be high temperature resistant and can the material preparation of powerful oxidation corrosion resistance, the problem that equipment cost is higher.The present invention, by improving activation solution formula, reduces energy consumption, reduces equipment cost, expands the scope of application of product, achieves good economic benefit.
PCB modified version activation solution of the present invention is mainly used in the conducting technique of bilayer and multi-layer PCB through hole and blind hole.
Accompanying drawing explanation
Fig. 1 is priming reaction mechanism of the present invention.
Fig. 2 is adjustment liquid of the present invention adsorption mechanism on the glass fibers.
Fig. 3 is the SEM/EDS spectrogram on the PCB hardboard surface of the activated process of the embodiment of the present invention 1.
Fig. 4 is the section after the electroplates in hole copper of the embodiment of the present invention 1 conducting after thermal shock experiment.
Fig. 5 is the section after the electroplates in hole copper of the embodiment of the present invention 2 conducting after thermal shock experiment.
Fig. 6 is the section after the blind hole electro-coppering of the embodiment of the present invention 3 conducting.
Fig. 7 is that the embodiment of the present invention 4, embodiment 5 are respectively at PCB hardboard (A) and the upper macromolecule conductive film generated of PCB soft board (B).
Fig. 8 is that comparative example 1 of the present invention, comparative example 2 are respectively at PCB hardboard (A) and the upper macromolecule conductive film generated of PCB soft board (B).
Embodiment
Technical scheme of the present invention is further illustrated by embodiment below in conjunction with accompanying drawing 3-8.
As no specific instructions, various raw material of the present invention all can commercially availablely be buied, or prepares according to the ordinary method of this area.
Embodiment 1
Hardboard vertical line generates macromolecule conductive film in the through hole of 250 μm, aperture, dark 1.6mm.
Modified version activation solution formula is as follows:
Film forming liquid formula is as follows:
PCB is placed in 35mL/L H
2sO
4(50%w/w) with in the mixing solutions of 90g/L NaPS, at 30 DEG C of insulation 1min, washing; Then PCB is placed in 65mL/L and adjusts liquid SkyPoly 391C, at 62 DEG C of insulation 2min, washing; Again PCB is placed in activated bath, adds above-mentioned modified version activation solution by proportioning, adopt boric acid to regulate the pH to 6.5 of modified version activation solution, the temperature controlling activated bath is 70 DEG C, insulation 3min, and washing, in PCB Surface Creation manganese dioxide membrane; Finally PCB is placed in the mixed solution of above-mentioned film forming liquid SkyPoly396A, SkyPoly 396B, SkyPoly 396M, at 20 DEG C of insulation 4min, washing, dries, can obtain macromolecule conductive film in PCB through hole and blind hole.
The PCB getting above-mentioned activation rear surface generation manganese dioxide membrane carries out SEM/EDS analysis under scanning electron microscope, the results are shown in Figure 3.Known from the EDS collection of illustrative plates Fig. 3, all generate Manganse Dioxide on the glass fibre (Glass Fiber) of PCB, epoxy resin (Epoxy resin) and Copper Foil (Copper) surface, the mass area ratio of manganese dioxide membrane is 5mg/dm
2.
In the PCB through hole after above-mentioned process, the thin copper of flash one deck carries out backlight test, result >=10 grade again.
PCB through hole is again through electro-coppering process after above-mentioned process conducting, and wicking 8 times, each 10s at 288 DEG C, carry out thermal shock test, test result is shown in Fig. 4.As can be seen from Figure 4, PCB imperforate wall separation phenomenon occurs.
Embodiment 2
Hardboard sea line adopts production technique of the present invention to generate macromolecule conductive film in the through hole of 250 μm, aperture, thickness of slab 2.4mm.
Modified version activation solution formula is as follows:
SkyPoly 393C 110m L/L
Ferrous sulfate 5g/L
Deionized water surplus
Film forming liquid formula is as follows:
PCB is placed in 35mL/L H
2sO
4(50%w/w) with in the mixing solutions of 90g/L NaPS, at 30 DEG C of insulation 1min, washing; Then PCB is placed in 65mL/L and adjusts liquid SkyPoly 391C, at 60 DEG C of insulation 1min, washing; Again PCB is placed in activated bath, adds above-mentioned modified version activation solution by proportioning, adopt sulfuric acid to regulate the pH to 6 of modified version activation solution, the temperature controlling activated bath is 65 DEG C, insulation 80s, and washing, in PCB Surface Creation manganese dioxide membrane; Finally PCB is placed in the mixed solution of film forming liquid SkyPoly 396A, SkyPoly 396B, SkyPoly 396M, at 20 DEG C of insulation 70s, washing, dries, can obtain macromolecule conductive film in PCB through hole and blind hole.
In the PCB through hole after above-mentioned process, the thin copper of flash one deck carries out backlight test, result >=10 grade again.
PCB through hole is again through electro-coppering process after above-mentioned process conducting, and wicking 8 times, each 10s under 288 DEG C of conditions, carry out thermal shock test, test result is shown in Fig. 5.As can be seen from Figure 5, PCB imperforate wall separation phenomenon occurs.
Embodiment 3
Hardboard sea line adopts production technique of the present invention to generate macromolecule conductive film in 100 μm, aperture, the blind hole of dark 100 μm.
Modified version activation solution formula is as follows:
Film forming liquid formula is as follows:
PCB is placed in 35mL/L H
2sO
4(50%w/w) with in the mixing solutions of 90g/L NaPS, at 30 DEG C of insulation 1min, washing; Then PCB is placed in adjustment liquid SkyPoly 391C, at 60 DEG C of insulation 3min, washing; Again PCB is placed in activated bath, adds above-mentioned modified version activation solution by proportioning, adopt phosphoric acid to regulate the pH to 6.5 of modified version activation solution, the temperature controlling activated bath is 75 DEG C, insulation 1min, and washing, in PCB Surface Creation manganese dioxide membrane; Finally PCB is placed in the mixed solution of film forming liquid SkyPoly 396A, SkyPoly396B, SkyPoly 396M, at 20 DEG C of insulation 3min, washing, dries, can obtain macromolecule conductive film in PCB through hole and blind hole.
Pass through with the blind hole of upper type activation treatment, then after flash copper, section detects, in hole, cover complete (Fig. 6).
Embodiment 4
Hardboard vertical line adopts the modified version activation solution identical with embodiment 1 and processing condition to generate macromolecule conductive film on PCB hardboard (A), and the macromolecule conductive film generated is shown in Fig. 7 A.
Embodiment 5
Soft board vertical line adopts the modified version activation solution identical with embodiment 1 and processing condition to generate macromolecule conductive film on PCB soft board (B), and the macromolecule conductive film generated is shown in Fig. 7 B.
Comparative example 1
Hardboard vertical line adopts following conventional activation liquid, and other processing condition are identical with embodiment 1, and PCB hardboard (A) generates macromolecule conductive film, and the macromolecule conductive film generated is shown in Fig. 8 A.
Activation solution formula is as follows:
SkyPoly 393C 110m L/L
Deionized water surplus
Comparative example 2
Soft board vertical line adopts the conventional activation liquid of comparative example 1, and other processing condition are identical with embodiment 1, and PCB soft board (B) generates macromolecule conductive film, and the macromolecule conductive film generated is shown in Fig. 8 B.
Test the conductive capability of the macromolecule conductive film obtained by embodiment 4 and comparative example 1, test result is 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 contrast, film forming again after adopting modified version activation solution of the present invention to activate pcb board, the resistance only 14K Ω of the macromolecule conductive film on obtained PCB hardboard, the resistance only 11K Ω of the macromolecule conductive film on PCB soft board, illustrates that this modified version activation solution is highly suitable for the activation treatment of PCB hardboard, PCB soft board; Adsorption of Organic layer in activating process on glass yarn and resin is generated the manganese dioxide membrane of q.s by high manganese ion oxidation, and the thiophene in Manganse Dioxide and film forming liquid or aniline monomer react and generate complete macromolecule conductive film; And film forming again after adopting traditional activation solution to activate pcb board, the resistance of the macromolecule conductive film on obtained PCB hardboard reaches 114K Ω, the resistance of the macromolecule conductive film especially on PCB soft board reaches 530K Ω unexpectedly, this illustrates that traditional activation solution is not enough to the Adsorption of Organic layer generation oxidizing reaction made on high manganese ion and pcb board 70 DEG C time, thus hinder follow-up film formation reaction, cause its resistance to increase, namely conductive capability is very poor.
Therefore, compared with traditional technology, modified version activation solution of the present invention is adopted not reduce under the condition that activation effect becomes film quality with macromolecule conductive film, priming reaction can be completed under adopting relatively low temperature, reduce energy consumption and production cost, expand the scope of application of this modified version activation solution, good economic benefit can be obtained.
Above embodiment is only used for method detailed of the present invention is described, the present invention is not limited to above-mentioned method detailed, does not namely mean that the present invention must rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. a PCB modified version activation solution, it is characterized in that, comprise compound or mixture that 1 ~ 100g/L contains high manganese ion, 0.1 ~ 20g/L contains compound or the mixture of at least one ion in ferrous ion, iron ion, ammonium ion, balance deionized water.
2. modified version activation solution according to claim 1, it is characterized in that, comprise compound or mixture that 4 ~ 60g/L contains high manganese ion, 0.5 ~ 10g/L contains compound or the mixture of at least one ion in ferrous ion, iron ion, ammonium ion, balance deionized water.
3. modified version activation solution according to claim 1, is characterized in that, described ferrous ion is from the compound of at least one in ferrous ammonium sulphate, ferrous sulfate, iron protochloride, ferrous phosphate, Iron nitrate or mixture;
Described iron ion is from the compound of at least one in ferric ammonium sulfate, ferric sulfate, iron(ic) chloride, iron nitrate, tertiary iron phosphate or mixture;
Described ammonium ion is from the compound of at least one in ammonium sulfate, ferrous ammonium sulphate, ammonium chloride, ammonium nitrate or mixture.
4. modified version activation solution according to claim 1, is characterized in that, described high manganese ion is from potassium permanganate and/or sodium permanganate;
Preferably, described high manganese ion is from the SkyPoly 393C of Guangzhou Tian Cheng Chemical Co., Ltd..
5. in PCB through hole and blind hole, generate a production technique for macromolecule conductive film, it is characterized in that, described production technique comprises activation, and described activation have employed the modified version activation solution as described in any one of Claims 1-4;
Described activation refers to: in described activated bath, add described modified version activation solution by proportioning, regulate its pH to 5 ~ 7, the temperature controlling described activated bath is 65 ~ 75 DEG C, PCB after adjustment is placed in activated bath, insulation 1 ~ 4min, washing, the PCB after obtained activation, the PCB Surface Creation manganese dioxide membrane after described activation;
Preferably, the mass area ratio of described manganese dioxide membrane is 1 ~ 10mg/dm
2, more preferably 4 ~ 6mg/dm
2.
6. production technique according to claim 5, is characterized in that, adopts phosphoric acid, boric acid, the mixture of any one or at least two kinds regulates described modified version activation solution in sulfuric acid pH to 5 ~ 7.
7. production technique according to claim 5, is characterized in that, also comprises the steps: before described activation
Clean: PCB to be placed in PCB clean-out system, at 25 ~ 35 DEG C of insulation 0.5 ~ 1min, washing, obtains the PCB after cleaning;
Adjust: the PCB after described cleaning is placed in PCB and adjusts liquid, at 58 ~ 62 DEG C of insulation 0.5 ~ 4min, washing, obtains the PCB after adjusting.
8. production technique according to claim 7, is characterized in that, described PCB clean-out system is H
2sO
4with the mixing solutions of NaPS, be preferably 35mL/L H
2sO
4with the mixing solutions of 90g/L NaPS; Described H
2sO
4massfraction be 50%;
Described PCB adjusts the SkyPoly 391C that liquid is Guangzhou Tian Cheng Chemical Co., Ltd..
9. production technique according to claim 5, it is characterized in that, also film forming is comprised after described activation, described film forming refers to: the PCB after described activation is placed in PCB film forming liquid, at 18 ~ 22 DEG C of insulation 1 ~ 4min, washing, dries, can obtain macromolecule conductive film in described PCB through hole and blind hole.
10. production technique according to claim 9, is characterized in that, described PCB film forming liquid is SkyPoly 396A, the SkyPoly 396B of Guangzhou Tian Cheng Chemical Co., Ltd. and the mixture of SkyPoly 396M;
Preferably, the formula of described PCB film forming liquid is: 30m L/L SkyPoly 396A, 20m L/LSkyPoly 396B, 20m L/L SkyPoly 396M, surplus is deionized water.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510102929.XA CN104744974B (en) | 2015-03-10 | 2015-03-10 | A kind of PCB generates the production technology of macromolecule conductive film with modified activating solution and in PCB through hole and blind hole |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510102929.XA CN104744974B (en) | 2015-03-10 | 2015-03-10 | A kind of PCB generates the production technology of macromolecule conductive film with modified activating solution and in PCB through hole and blind hole |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN108221010A (en) * | 2018-01-29 | 2018-06-29 | 莆田市佳宜科技股份有限公司 | A kind of preparation process of pcb board macromolecule conductive film |
| 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 |
| CN113993303A (en) * | 2021-10-27 | 2022-01-28 | 上海天承化学有限公司 | Method for metallizing holes of mixed-pressure circuit board |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN108221010A (en) * | 2018-01-29 | 2018-06-29 | 莆田市佳宜科技股份有限公司 | A kind of preparation process of pcb board macromolecule conductive film |
| 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 |
| CN113993303A (en) * | 2021-10-27 | 2022-01-28 | 上海天承化学有限公司 | Method for metallizing holes of mixed-pressure circuit board |
| 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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| CN104744974B (en) | 2017-10-17 |
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