CN103572334B - A kind of PCB through hole blind hole copper electroplating solution and preparation method thereof and electro-plating method - Google Patents
A kind of PCB through hole blind hole copper electroplating solution and preparation method thereof and electro-plating method Download PDFInfo
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- CN103572334B CN103572334B CN201310585153.2A CN201310585153A CN103572334B CN 103572334 B CN103572334 B CN 103572334B CN 201310585153 A CN201310585153 A CN 201310585153A CN 103572334 B CN103572334 B CN 103572334B
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Abstract
The present invention relates to PCB electroplating technology field, being specifically related to a kind of PCB through hole blind hole copper electroplating solution and preparation method thereof and electro-plating method, each component of described copper electroplating solution and content thereof is: copper sulphate pentahydrate: 100 ~ 250g/L, sulphuric acid: 100 ~ 200g/L, chloride ion: 30 ~ 100ppm, brightener: 5 ~ 50g/L, carrying agent: 3 ~ 30g/L, leveling agent: 2 ~ 20g/L, deionized water surplus；And the concentration ratio of copper sulphate pentahydrate and sulphuric acid is 1 ~ 1.25:1。The electro-plating method of the present invention is: is put into by the pcb board with through hole and blind hole in the electroplating bath equipped with described copper electroplating solution and electroplates under air stirring, obtains copper plate。Good by the method copper plate depth capability, reach more than 92%, filling perforation rate is high, reaches more than 96%, and copper plate densification is smooth, and ductility is better, has good gloss, high tenacity, low internal stress。
Description
Technical field
The present invention relates to PCB electroplating technology field, be specifically related to a kind of PCB through hole blind hole copper electroplating solution and preparation method thereof and electro-plating method。
Background technology
Printed circuit board (pcb) is in manufacturing process, the making of through hole and blind hole can be carried out, through hole machine dimensions drill and drill point come outbreak out, blind hole is with the laser ablation of laser drill out, through hole is used for the conducting interconnection realizing in multi-layer sheet between random layer, and blind hole is used for the conducting interconnection that realizes between multi-layer sheet ectomesoderm and sublevel。
In the copper sulfate electroplating technology that printed circuit board (pcb) is follow-up, requirement when electroplating for through hole on circuit board and blind hole is different, the low copper of peracid is generally adopted, to improve covering power (thoughpower) for high plate thickness aperture ratio through hole liquid medicine component；The low acid of high-copper is generally adopted, to improve blind hole throwing power for laser Microvia liquid medicine component。It can thus be appreciated that the liquid medicine component of the electroplates in hole and blind hole plating is contrary。
When high plate thickness aperture ratio through hole and laser Microvia are electroplated simultaneously, can there is problems in that
When ensureing high plate thickness aperture ratio through hole quality, it is necessary to adopting the low copper of peracid to electroplate, this occurs the problem that blind hole copper thickness is not enough often, in thermal stress and thermal shock test process, blind hole easily produces copper and breaks, and resistance becomes big and lost efficacy；
When ensureing laser Microvia electroplating quality, it is necessary to adopt the low acid of high-copper to electroplate, through hole " Os Canitis " phenomenon often occurs, namely Kong Biantong is thick, hole central copper is logical thick not enough, easily produces fracture in thermal stress and thermal shock test process mesopore copper, and resistance becomes big even open failure。
When filling perforation is electroplated, not only to consider blind hole filling perforation, also to consider the electroplates in hole simultaneously。Blind hole plating is effective under the low acid of high-copper, and through hole covering power is better under the low copper bar part of peracid, both are in opposition phenomenon, so in actual production, copper sulfate and sulfuric acid concentration to be found an equilibrium point, makes blind hole fill quality and through hole copper thickness reaches requirement simultaneously。
One in PCB through hole or PCB blind hole can only be electroplated by electroplating liquid medicine of the prior art, in the market but without PCB through hole and PCB blind hole carry out the liquid medicine that plating can be general。Therefore, it is necessary to PCB through hole can be electroplated by exploitation one, PCB blind hole can be electroplated again, the copper plate depth capability obtained can also be made good, filling perforation rate is high, and copper plate is smooth, good PCB through hole blind hole copper electroplating solution of ductility, gloss and toughness and preparation method thereof and using method。
Summary of the invention
In order to overcome the shortcoming and defect existed in prior art, it is an object of the invention to provide a kind of PCB through hole blind hole copper electroplating solution and preparation method thereof, PCB through hole can be electroplated by this copper electroplating solution, PCB blind hole can be electroplated again, the copper plate depth capability obtained can also be made good, and filling perforation rate is high, and copper plate is smooth, ductility, gloss and toughness are better, and bath stability, life-span are long；This preparation method is simple to operate, reduces production cost, is suitable for industrialized production。
Another object of the present invention is to provide the using method of a kind of PCB through hole blind hole copper electroplating solution, copper plate depth capability is formed good by the method, filling perforation rate is high, fine and close smooth, without empty, seamless, surface deposit thickness is low, ductility is better, has good gloss, high tenacity, low internal stress。
The purpose of the present invention is achieved through the following technical solutions: a kind of PCB through hole blind hole copper electroplating solution, and each component of described copper electroplating solution and content thereof is:
Copper sulphate pentahydrate: 100 ~ 250g/L
Sulphuric acid: 100 ~ 200g/L
Chloride ion: 30 ~ 100ppm
Brightener: 5 ~ 50g/L
Carrying agent: 3 ~ 30g/L
Leveling agent: 2 ~ 20g/L
Deionized water surplus；
And the concentration ratio of copper sulphate pentahydrate and sulphuric acid is 1 ~ 1.25:1。
Preferably, each component of described copper electroplating solution and content thereof are:
Copper sulphate pentahydrate: 140 ~ 220g/L
Sulphuric acid: 120 ~ 180g/L
Chloride ion: 45 ~ 80ppm
Brightener: 15 ~ 35g/L
Carrying agent: 10 ~ 20g/L
Leveling agent: 5 ~ 15g/L
Deionized water surplus；
And the concentration ratio of copper sulphate pentahydrate and sulphuric acid is 1.17 ~ 1.22:1。
Being more highly preferred to, each component of described copper electroplating solution and content thereof is:
Copper sulphate pentahydrate: 180g/L
Sulphuric acid: 150g/L
Chloride ion: 60ppm
Brightener: 25g/L
Carrying agent: 15g/L
Leveling agent: 10g/L
Deionized water surplus；
And the concentration of copper sulphate pentahydrate and sulphuric acid is than for 1.2:1。
Copper sulphate pentahydrate is the main salt of copper electroplating solution, is Cu in solution2+Source, concentration want appropriateness。The too low then sedimentation rate of copper sulphate pentahydrate concentration is relatively slow, and too high then sedimentation rate is too fast, and crystalline particle is thick, and affects the covering power of plating solution, and plate face is excessive with the difference of thickness of coated copper layer in hole。The copper sulphate pentahydrate of the present invention is defined to 100 ~ 250g/L, both can guarantee that sedimentation rate, does not affect again the covering power of plating solution, it is preferred that copper sulphate pentahydrate is defined to 140 ~ 220g/L, is more highly preferred to, and copper sulphate pentahydrate is defined to 180g/L。
Sulphuric acid mainly increases the conductive capability of copper electroplating solution, and prevents Cu2+Hydrolysis, concentration also wants appropriate。The too high meeting of sulfuric acid concentration makes copper electroplating solution dispersibility poor, and too low meeting makes copper plate fragility increase, and toughness declines。The sulphuric acid of the present invention is defined to 100 ~ 200g/L, both can ensure that the dispersibility of copper electroplating solution, again can so that the copper plate toughness obtained is higher, it is preferred that sulphuric acid is defined to 120 ~ 180g/L, is more highly preferred to, and sulphuric acid is defined to 150g/L。
When filling perforation is electroplated, not only to consider blind hole filling perforation, also to consider the electroplates in hole simultaneously。Blind hole plating is effective under the low acid of high-copper, and through hole covering power is better under the low copper bar part of peracid, both are in opposition phenomenon, so in actual production, copper sulfate and sulfuric acid concentration to be found an equilibrium point, makes blind hole fill quality and through hole copper thickness reaches requirement simultaneously。The copper sulphate pentahydrate of the present invention: the concentration ratio of sulphuric acid is defined to 1 ~ 1.25:1, both had and deeply plated effect preferably, there is again good filling perforation rate, preferably, copper sulphate pentahydrate: the concentration ratio of sulphuric acid is defined to 1.56 ~ 1.88:1, it is more highly preferred to, copper sulphate pentahydrate: the concentration ratio of sulphuric acid is defined to 1.67:1。
Chloride ion can improve the activity of anode, promotes that anode normally dissolves, it is prevented that anodic passivity；" copper powder " because anodic solution not exclusively produces can also be reduced, improve light and the leveling ability of copper plate, improve copper plate quality。The chloride ion of the present invention is defined to 30 ~ 100ppm, it is possible to make copper plate densification smooth, it is preferred that chloride ion is defined to 45 ~ 80ppm, is more highly preferred to, and chloride ion is defined to 60ppm。
Electroplating in theory in tradition, blind via bottom is low current region, and liquid medicine exchange is few, and its electroplating effect is often difficult to reach perfect condition。Blind hole plating process for filling hole is ripe gradually along with development and the optimization of filling perforation photo etching, plays key player in HDI plate manufacturing process。On market, filling perforation photo etching kind is more, but its cardinal principle is close。Filling perforation photo etching main component has three kinds: brightener, carrying agent, leveling agent。
Brightener (Hrightener): can produce one " depolarization " or force down the action of " overpotential " under chloride ion is assisted, thus there will be the copper-plated effect of acceleration, therefore be also called accelerator (Accelerator)。Brightener itself can also pass into participation crystalline texture in copper plate, impact or the spontaneous nucleation mode intervened to copper atom deposition, promotes to become more fine and smooth tissue, therefore is also called grain refiner (GrainRefiner)。In filling perforation is electroplated, brightener primary attachment, in blind via bottom, utilizes thio-alcohol Organic substance and Cu2+Form complex, to accelerate the copper deposition at blind via bottom；The brightener of the present invention is defined to 5 ~ 50g/L, it is possible to make copper plate densification smooth, it is preferred that brightener is defined to 15 ~ 35g/L, is more highly preferred to, and brightener is defined to 25g/L。
Preferably, the mixture that described brightener is made up of the 3-sulfydryl-1-propane sulfonic acid sodium that weight ratio is 1.5 ~ 3.5:1 and ethylene thiourea。
3-sulfydryl-1-propane sulfonic acid sodium (MPS) is white or buff powder, and the easy moisture absorption, water solublity is strong；3-sulfydryl-1-propane sulfonic acid sodium is used as acid copper plating brightening agent, can make copper plate light, and have smooth effect, also can improve working current density。Often and copper brightener N etc. with the use of。
Ethylene thiourea (N) is white powder, and fusing point is 198 DEG C。Ethylene thiourea is used as copper brightener, often and acid copper plating brightening agent M, MPS etc. with the use of。
The present invention adopt 3-sulfydryl-1-propane sulfonic acid sodium and ethylene thiourea with the use of, and limit the weight ratio of 3-sulfydryl-1-propane sulfonic acid sodium and ethylene thiourea as 1.5 ~ 3.5:1, copper plate smooth can be made, preferably, the weight ratio of 3-sulfydryl-1-propane sulfonic acid sodium and ethylene thiourea is 2 ~ 3:1, being more highly preferred to, the weight ratio of 3-sulfydryl-1-propane sulfonic acid sodium and ethylene thiourea is 2.5:1。
Carrying agent (Carrier): with Cl-The suppression to copper deposition can be strengthened under combined effect, brightener can be assisted to go to negative electrode depression to be distributed everywhere, therefore be called carrying agent。Carrying agent can present " increasing polarization " in groove or increase the effect of " overpotential " in liquid reaction, copper facing deposition can produce the phenomenon of " deceleration ", be namely demonstrated by the effect of " constraining ", therefore be also called repressor (Suppresser)。But carrying agent yet separately has the reduction capillary effect of tank liquor, or increases its moistening effect, is then frequently referred to again wetting agent (WettingAgentorWetter)。Carrying agent can assist polishing material in the distribution of surfacing, it is possible to makes copper face increase glossiness。In filling perforation is electroplated, carrying agent is mainly macro-radical, is adsorbed in copper surface, utilizes Adsorption of Organic Cu2+, play the effect suppressing surface copper ion deposition；The carrying agent of the present invention is defined to 3 ~ 30g/L, it is possible to increase the gloss of copper plate, it is preferred that carrying agent is defined to 10 ~ 20g/L, is more highly preferred to, and carrying agent is defined to 15g/L。
Preferably, described carrying agent by the Polyethylene Glycol that molecular weight is 5000 ~ 15000 and polypropylene glycol that molecular weight is 500 ~ 1500 by weight 1.8 ~ 2.6:1 mixture formed。
Polyethylene Glycol (PEG), along with the increase of PEG molecular weight, the micropore filling power of copper electroplating solution significantly improves。When electric current density is 2A/dm2, when additive PEG molecular weight is more than 6000, plating solution can be filled up completely with blind hole, and copper plate occurs without any cavity and gap。This is owing to additive PEG can substantially strengthen electro-coppering plating solution cathodic polarization, it is suppressed that the deposition of electro-coppering；Meanwhile, PEG diffusion coefficient in the plating solution also reduces with the increase of its molecular weight, thus adding M absorption affinity bottom micropore, accelerates electro-coppering deposition bottom micropore；Further, increase PEG molecular weight deposition copper film table and roughness, copper film degree of crystallinity and resistivity all decrease。Therefore, the molecular weight of the Polyethylene Glycol of the present invention is defined to 5000 ~ 15000, it is possible to increases filling perforation rate, and makes copper plate densification smooth。
Polypropylene glycol (PPG) can substantially strengthen electro-coppering plating solution cathodic polarization, it is suppressed that the deposition of electro-coppering；Meanwhile, PPG diffusion coefficient in the plating solution also reduces with the increase of its molecular weight, thus adding SPS absorption affinity bottom micropore, accelerates electro-coppering deposition bottom micropore；Further, increase PPG molecular weight deposition copper film table and roughness, copper film degree of crystallinity and resistivity all decrease。Therefore, the molecular weight of the Polyethylene Glycol of the present invention is defined to 500 ~ 1500, it is ensured that PPG diffusion coefficient in copper electroplating solution, and makes copper plate densification smooth。
The present invention adopt Polyethylene Glycol and ethylene thiourea with the use of, and limit the weight ratio of Polyethylene Glycol and polypropylene glycol as 1.8 ~ 2.6:1, filling perforation rate can be increased, preferably, the weight ratio of Polyethylene Glycol and polypropylene glycol is 2 ~ 2.4:1, being more highly preferred to, the weight ratio of Polyethylene Glycol and polypropylene glycol is 2.2:1。
Leveling agent (Leveler): with very strong electropositive, it is easily absorbing at plating piece surface current density larger part, compete with copper ion, copper ion is made not easily to deposit at high electric current place, but do not affect the copper deposition in low current district, up-and-down surface originally is made to become more smooth, because of referred to herein as leveling agent。In filling perforation is electroplated, leveling agent Main Function is the CURRENT DISTRIBUTION of balance aperture, high Current Zone and low current district angle of spot hole, modifies blind hole hole shape。The leveling agent of the present invention is defined to 2 ~ 20g/L, it is ensured that copper plate smooth, it is preferred that leveling agent is defined to 5 ~ 15g/L, is more highly preferred to, and leveling agent is defined to 10g/L。
Early 1970s, acid copper plating progressively tends to ripe。Occur in that a large amount of patent that leveling agent is discussed this period, wherein use the product after the limb alkylation of polyhexene Asia, a kind of quaternary amine is as leveling agent, and alkylating reagent used has benzyl chloride, dimethyl sulfate, sulphuric acid two ester, acrylic bromine, propane sultone etc.。This quaternary ammonium salt is compared with previously used polyhexene imines, and water solublity is better, and the composite better effects if of other additive, expands the current range in light clear zone, and copper plate is bright, smooth, high tenacity, low internal stress。
Having used the product of the leveling agent chloropropylene oxide of another synthesis and the substance reaction gained containing one or more N functional groups this period, the material containing N functional group used has pyridine, quinoline, isoquinolin, benzimidazole etc.。The introducing of this additive is primarily to the problem that the additive utilization rate solving exist in original acid copper plating system is low。Additive system originally makes plating piece surface irregularity, flattens poor effect, and it is not enough that new leveling agent but compensate for this to a certain extent。Electroplating process allow protruding local copper plate partially thin, partially thick at pit copper plate accordingly, and do not result in high internal stress, both reach leveling purpose, made again copper plate possess good mechanical performance。
Preferably, the mixture that described leveling agent is made up of the leveling agent A that weight ratio is 1.2 ~ 2.4:1 and leveling agent B；Wherein, leveling agent A is polyvinyl imidazol quaternary ammonium compound, and leveling agent B is N-vinyl-N '-1-Butyl-1H-imidazole-ethyl acrylate copolymer。
Preferably, the structural formula of described leveling agent A is:
Wherein, R1Being the epoxy alkyl of 2 ~ 10 for alkyl that carbon number is 1 ~ 10, aromatic radical or cycloalkyl or carbon number that carbon number is 3 ~ 10, X is halogen atom or hydrogen sulfate ion, and n and m is greater than 2 and integer less than 100。
Preferably, R1For ethyl group, propyl, butane group, phenyl, benzyl, cyclopropane base, expoxy propane base；X is chlorine, bromine, iodine or hydrogen sulfate ion。
It is more highly preferred to, R1X is ethyl chloride, N-Propyl Bromide, iodobutane, benzyl chlorine, epoxychloropropane。
Preferably, the structural formula of described leveling agent B is:
Wherein, R2Being the epoxy alkyl of 2 ~ 10 for alkyl that carbon number is 1 ~ 10, aromatic radical, ether, ester group or cycloalkyl or carbon number that carbon number is 3 ~ 10, X is halogen atom or hydrogen sulfate ion, and n and m is greater than 2 and integer less than 100。
Preferably, R2For ethyl group, propyl, butane group, phenyl, benzyl, cyclopropane base, expoxy propane base。
The present invention adopts polyvinyl imidazol quaternary ammonium compound and N-vinyl-N '-1-Butyl-1H-imidazole-ethyl acrylate copolymer with the composite use of weight ratio of 1.2 ~ 2.4:1, it is possible to make that copper plate is bright, smooth, high tenacity, low internal stress。
The preparation method of a kind of PCB through hole blind hole copper electroplating solution, comprises the steps:
(1) adding the deionized water of deionized water volume 1/2 ~ 2/3 in a reservoir, when stirring, add copper sulphate pentahydrate by proportioning, stirring is to being completely dissolved；
(2) when stirring, add sulphuric acid by proportioning, continue stirring 5 ~ 10min；
(3) after cooling, when stirring, add chloride ion, brightener, carrying agent and leveling agent by proportioning, after completing, continue stirring 5 ~ 10min；
(4) supplement remaining deionized water, stir, prepare a kind of PCB through hole blind hole copper electroplating solution。
Another object of the present invention is achieved through the following technical solutions: the electro-plating method of a kind of PCB through hole blind hole copper electroplating solution, the pcb board with through hole and blind hole is put in the electroplating bath equipped with described copper electroplating solution and electroplate under air stirring, obtain copper plate。
Preferably, described plating is divided into three sections:
First paragraph electric current density is 8 ~ 12ASF, and electroplating time is 15 ~ 35min；
Second segment electric current density is 10 ~ 14ASF, and electroplating time is 15 ~ 35min；
3rd section of electric current density is 16 ~ 24ASF, and electroplating time is 15 ~ 35min。
The influence factor of acid copper plating bath plating has:
1, electric current density: when filling perforation is electroplated, often adopts low current density can obtain good blind hole filling perforation effect and through hole covering power, but the low current density production time is long, and production efficiency is low, and cost is high。In existing market with keen competition, cost consciousness and production efficiency are rooted in the hearts of the people already。So to reduce electric current density, to carry out guaranteed quality be not long-term plan, will improve electric current density as far as possible, improves production efficiency, it is achieved the bumper harvests of cost and quality。
Being experimentally confirmed, high current density blind hole filling effect is poor, for promoting electroplating efficiency, can take segmentation electric plating method, and electric current density steps up, and can according to circumstances be divided into two-stage nitration or three sections, is the better method solving filling perforation production efficiency and quality。The present invention adopts three sections of galvanoplastic, can effectively solve filling perforation production efficiency and quality。
2, through hole radius-thickness ratio: the radius-thickness ratio of through hole is relatively big on covering power impact, in order to make perforation plating also can have good covering power, the radius-thickness ratio of the present invention is defined to 2 ~ 6, it is preferred that radius-thickness ratio is defined to 2 ~ 5, is more highly preferred to, and radius-thickness ratio is defined to 4。
3, the shape of blind hole: the blind hole of waist-drum-shaped and vertical-type is when filling perforation is electroplated, and Shi Gao Current Zone, aperture, as bad in controlled, its deposition velocity is higher than blind via bottom deposition velocity, will produce filling perforation bubble。Ramp type liquid medicine circulation is good compared with the above two, is not likely to produce filling perforation bubble, and manufacture difficulty is easy compared with the above two。Good blind hole shape is the basis of filling perforation plating, and the quality of laser drill to be had strict monitoring, the quality of guarantee blind hole filling perforation plating。The blind hole that the present invention adopts is ramp type, and specifically, for falling isosceles trapezoid, and the length ratio on top margin (long limit) and base (minor face) is 1.5 ~ 2.5:1, it is preferred that the length ratio on top margin and base is 2:1。
4, blind hole radius-thickness ratio: use different filling perforation photo etchings, its blind hole aperture is different on the impact of filling perforation。But it is bigger than normal that major effect is radius-thickness ratio, aperture hour, when filling perforation is electroplated, liquid medicine exchange is poor, the defect in filling perforation cavity easily occurs, and the filling perforation time is long, and production efficiency is low；When aperture is bigger than normal, blind via bottom not easily adsorbs accelerator under the effect of jet flow, and its filling perforation effect is poor。So the qualitative reliability of filling perforation is affected bigger by suitable aperture and aspect ratio。The blind hole radius-thickness ratio that the present invention adopts is 0.8 ~ 1.2:1, can reach good filling effect, it is preferred that blind hole radius-thickness ratio is 1:1。
5, stirring: in plating, liquid medicine circulation directly influences electroplating effect, and blind hole is enclosed due to one end, and liquid medicine circulation is than through hole difficulty, so liquid medicine agitation cycle effect during filling perforation plating is extremely important。Liquid medicine circulation is poor, is easily generated bubble in blind hole；Liquid medicine circulation is excessively strong, then blind via bottom can not active adsorption accelerator, filling perforation effect is not good on the contrary。Different photo etchings are different with the requirement of strength of jet flow to liquid medicine circulation, the blind hole of different pore size is also otherwise varied to jet strength, so selecting suitable liquid medicine alr mode and intensity that filling perforation effect is extremely important, the present invention adopts the mode of compression air stirring, and via depth ability and blind hole filling perforation effect are all better。
6, anode material: in acidic copper-plating of bright, quality of anode is very important factor, generally should not use cathode copper, and the present invention adopts the copper anode that anaerobic is phosphorous。This is because when using oxygen containing electrolytic copper anode, surface easily produces Red copper oxide (copper powder), make the consumption of brightener increase, and reduce copper plate quality, when phosphorus can make the electrochemical dissolution of anode, surface produces one layer of black rete, it is to avoid uneven dissolution。
The beneficial effects of the present invention is: the present invention adopts 3-sulfydryl-1-propane sulfonic acid sodium and ethylene thiourea as the composite use of brightener, can make copper plate smooth；The present invention adopts Polyethylene Glycol and polypropylene glycol as carrying agent, copper plate densification can be made smooth, the present invention adopts polyvinyl imidazol quaternary ammonium compound and N-vinyl-N '-1-Butyl-1H-imidazole-ethyl acrylate copolymer as the composite use of leveling agent, it is possible to make that copper plate is bright, smooth, high tenacity, low internal stress。
PCB through hole can be electroplated by the copper electroplating solution of the present invention, can PCB blind hole be electroplated again, moreover it is possible to makes the copper plate depth capability obtained good, and filling perforation rate is high, and copper plate is smooth, and ductility, gloss and toughness are better, and bath stability, life-span are long。
A kind of preparation method of the PCB through hole blind hole copper electroplating solution of the present invention, simple to operate, reduce production cost, be suitable for industrialized production。
A kind of using method of the PCB through hole blind hole copper electroplating solution of the present invention, good by the method copper plate depth capability, reach more than 92%, filling perforation rate is high, reaches more than 96%, and copper plate densification is smooth, without empty, seamless, surface deposit thickness is low, ductility is better, has good gloss, high tenacity, low internal stress。
Detailed description of the invention:
For the ease of the understanding of those skilled in the art, below in conjunction with embodiment, the present invention is further illustrated, and the content that embodiment is mentioned not is limitation of the invention。
Embodiment 1
A kind of PCB through hole blind hole copper electroplating solution, each component of described copper electroplating solution and content thereof is:
Copper sulphate pentahydrate: 100g/L
Sulphuric acid: 100g/L
Chloride ion: 30ppm
Brightener: 5g/L
Carrying agent: 3g/L
Leveling agent: 2g/L
Deionized water surplus；
And the concentration of copper sulphate pentahydrate and sulphuric acid is than for 1:1。
The mixture that described brightener is made up of the 3-sulfydryl-1-propane sulfonic acid sodium that weight ratio is 1.5:1 and ethylene thiourea；Described carrying agent by the Polyethylene Glycol that molecular weight is 5000 and polypropylene glycol that molecular weight is 500 by weight the 1.8:1 mixture formed。
The mixture that described leveling agent is made up of the leveling agent A that weight ratio is 1.2:1 and leveling agent B；Wherein, leveling agent A is polyvinyl imidazol quaternary ammonium compound, and leveling agent B is N-vinyl-N '-1-Butyl-1H-imidazole-ethyl acrylate copolymer。
The structural formula of described leveling agent A is:
Wherein, R1For ethyl group, X is chlorine atom, n=2, m=2。
The structural formula of described leveling agent B is:
Wherein, R2For cyclopropane base, n=100, m=100。
The preparation method of a kind of PCB through hole blind hole copper electroplating solution, comprises the steps:
(1) adding the deionized water of deionized water volume 1/2 in a reservoir, when stirring, add copper sulphate pentahydrate by proportioning, stirring is to being completely dissolved；
(2) when stirring, add sulphuric acid by proportioning, continue stirring 5min；
(3) after cooling, when stirring, add chloride ion, brightener, carrying agent and leveling agent by proportioning, after completing, continue stirring 5min；
(4) supplement remaining deionized water, stir, prepare a kind of PCB through hole blind hole copper electroplating solution。
The electro-plating method of a kind of PCB through hole blind hole copper electroplating solution, puts into the pcb board with through hole and blind hole in the electroplating bath equipped with described copper electroplating solution and electroplates under air stirring, obtain copper plate。
Described plating is divided into three sections:
First paragraph electric current density is 8ASF, and electroplating time is 15min；
Second segment electric current density is 10ASF, and electroplating time is 15min；
3rd section of electric current density is 16ASF, and electroplating time is 15min。
The analysis test result of the copper plate that the present embodiment obtains is as shown in table 1。
Embodiment 2
A kind of PCB through hole blind hole copper electroplating solution, each component of described copper electroplating solution and content thereof is:
Copper sulphate pentahydrate: 140g/L
Sulphuric acid: 120g/L
Chloride ion: 45ppm
Brightener: 15g/L
Carrying agent: 10g/L
Leveling agent: 5g/L
Deionized water surplus；
And the concentration of copper sulphate pentahydrate and sulphuric acid is than for 1.17:1。
The mixture that described brightener is made up of the 3-sulfydryl-1-propane sulfonic acid sodium that weight ratio is 2:1 and ethylene thiourea；Described carrying agent by the Polyethylene Glycol that molecular weight is 8000 and polypropylene glycol that molecular weight is 800 by weight the 2:1 mixture formed。
The mixture that described leveling agent is made up of the leveling agent A that weight ratio is 1.5:1 and leveling agent B；Wherein, leveling agent A is polyvinyl imidazol quaternary ammonium compound, and leveling agent B is N-vinyl-N '-1-Butyl-1H-imidazole-ethyl acrylate copolymer。
The structural formula of described leveling agent A is:
Wherein, R1For propyl, X is bromine atoms, n=20, m=80。
The structural formula of described leveling agent B is:
Wherein, R2For benzyl, n=80, m=20。
The preparation method of a kind of PCB through hole blind hole copper electroplating solution, comprises the steps:
(1) adding the deionized water of deionized water volume 2/3 in a reservoir, when stirring, add copper sulphate pentahydrate by proportioning, stirring is to being completely dissolved；
(2) when stirring, add sulphuric acid by proportioning, continue stirring 6min；
(3) after cooling, when stirring, add chloride ion, brightener, carrying agent and leveling agent by proportioning, after completing, continue stirring 6min；
(4) supplement remaining deionized water, stir, prepare a kind of PCB through hole blind hole copper electroplating solution。
The electro-plating method of a kind of PCB through hole blind hole copper electroplating solution, puts into the pcb board with through hole and blind hole in the electroplating bath equipped with described copper electroplating solution and electroplates under air stirring, obtain copper plate。
Described plating is divided into three sections:
First paragraph electric current density is 9ASF, and electroplating time is 20min；
Second segment electric current density is 11ASF, and electroplating time is 20min；
3rd section of electric current density is 18ASF, and electroplating time is 20min。
The analysis test result of the copper plate that the present embodiment obtains is as shown in table 1。
Embodiment 3
A kind of PCB through hole blind hole copper electroplating solution, each component of described copper electroplating solution and content thereof is:
Copper sulphate pentahydrate: 220g/L
Sulphuric acid: 180g/L
Chloride ion: 80ppm
Brightener: 35g/L
Carrying agent: 20g/L
Leveling agent: 15g/L
Deionized water surplus；
And the concentration of copper sulphate pentahydrate and sulphuric acid is than for 1.22:1。
The mixture that described brightener is made up of the 3-sulfydryl-1-propane sulfonic acid sodium that weight ratio is 2.5:1 and ethylene thiourea；Described carrying agent by the Polyethylene Glycol that molecular weight is 10000 and polypropylene glycol that molecular weight is 1000 by weight the 2.2:1 mixture formed。
The mixture that described leveling agent is made up of the leveling agent A that weight ratio is 1.8:1 and leveling agent B；Wherein, leveling agent A is polyvinyl imidazol quaternary ammonium compound, and leveling agent B is N-vinyl-N '-1-Butyl-1H-imidazole-ethyl acrylate copolymer。
The structural formula of described leveling agent A is:
Wherein, R1For butane group, X is atomic iodine, n=50, m=50。
The structural formula of described leveling agent B is:
Wherein, R2For propyl, n=50, m=50。
The preparation method of a kind of PCB through hole blind hole copper electroplating solution, comprises the steps:
(1) adding the deionized water of deionized water volume 1/2 in a reservoir, when stirring, add copper sulphate pentahydrate by proportioning, stirring is to being completely dissolved；
(2) when stirring, add sulphuric acid by proportioning, continue stirring 7min；
(3) after cooling, when stirring, add chloride ion, brightener, carrying agent and leveling agent by proportioning, after completing, continue stirring 7min；
(4) supplement remaining deionized water, stir, prepare a kind of PCB through hole blind hole copper electroplating solution。
The electro-plating method of a kind of PCB through hole blind hole copper electroplating solution, puts into the pcb board with through hole and blind hole in the electroplating bath equipped with described copper electroplating solution and electroplates under air stirring, obtain copper plate。
Described plating is divided into three sections:
First paragraph electric current density is 10ASF, and electroplating time is 25min；
Second segment electric current density is 12ASF, and electroplating time is 25min；
3rd section of electric current density is 20ASF, and electroplating time is 25min。
The analysis test result of the copper plate that the present embodiment obtains is as shown in table 1。
Embodiment 4
A kind of PCB through hole blind hole copper electroplating solution, each component of described copper electroplating solution and content thereof is:
Copper sulphate pentahydrate: 180g/L
Sulphuric acid: 150g/L
Chloride ion: 60ppm
Brightener: 25g/L
Carrying agent: 15g/L
Leveling agent: 10g/L
Deionized water surplus；
And the concentration of copper sulphate pentahydrate and sulphuric acid is than for 1.2:1。
The mixture that described brightener is made up of the 3-sulfydryl-1-propane sulfonic acid sodium that weight ratio is 3:1 and ethylene thiourea；Described carrying agent by the Polyethylene Glycol that molecular weight is 12000 and polypropylene glycol that molecular weight is 1200 by weight the 2.4:1 mixture formed。
The mixture that described leveling agent is made up of the leveling agent A that weight ratio is 2.1:1 and leveling agent B；Wherein, leveling agent A is polyvinyl imidazol quaternary ammonium compound, and leveling agent B is N-vinyl-N '-1-Butyl-1H-imidazole-ethyl acrylate copolymer。
The structural formula of described leveling agent A is:
Wherein, R1For benzyl, X is chlorine atom, n=80, m=20。
The structural formula of described leveling agent B is:
Wherein, R2For ethyl group, n=20, m=80。
The preparation method of a kind of PCB through hole blind hole copper electroplating solution, comprises the steps:
(1) adding the deionized water of deionized water volume 2/3 in a reservoir, when stirring, add copper sulphate pentahydrate by proportioning, stirring is to being completely dissolved；
(2) when stirring, add sulphuric acid by proportioning, continue stirring 8min；
(3) after cooling, when stirring, add chloride ion, brightener, carrying agent and leveling agent by proportioning, after completing, continue stirring 8min；
(4) supplement remaining deionized water, stir, prepare a kind of PCB through hole blind hole copper electroplating solution。
The electro-plating method of a kind of PCB through hole blind hole copper electroplating solution, puts into the pcb board with through hole and blind hole in the electroplating bath equipped with described copper electroplating solution and electroplates under air stirring, obtain copper plate。
Described plating is divided into three sections:
First paragraph electric current density is 11ASF, and electroplating time is 30min；
Second segment electric current density is 13ASF, and electroplating time is 30min；
3rd section of electric current density is 22ASF, and electroplating time is 30min。
The analysis test result of the copper plate that the present embodiment obtains is as shown in table 1。
Embodiment 5
A kind of PCB through hole blind hole copper electroplating solution, each component of described copper electroplating solution and content thereof is:
Copper sulphate pentahydrate: 250g/L
Sulphuric acid: 200g/L
Chloride ion: 100ppm
Brightener: 50g/L
Carrying agent: 30g/L
Leveling agent: 20g/L
Deionized water surplus；
And the concentration of copper sulphate pentahydrate and sulphuric acid is than for 1.25:1。
The mixture that described brightener is made up of the 3-sulfydryl-1-propane sulfonic acid sodium that weight ratio is 3.5:1 and ethylene thiourea；Described carrying agent by the Polyethylene Glycol that molecular weight is 15000 and polypropylene glycol that molecular weight is 1500 by weight the 2.6:1 mixture formed。
The mixture that described leveling agent is made up of the leveling agent A that weight ratio is 2.4:1 and leveling agent B；Wherein, leveling agent A is polyvinyl imidazol quaternary ammonium compound, and leveling agent B is N-vinyl-N '-1-Butyl-1H-imidazole-ethyl acrylate copolymer。
The structural formula of described leveling agent A is:
Wherein, R1For cyclopropane base, X is cyclopropane base, n=100, m=100。
The structural formula of described leveling agent B is:
Wherein, R2For butane group, n=2, m=2。
The preparation method of a kind of PCB through hole blind hole copper electroplating solution, comprises the steps:
(1) adding the deionized water of deionized water volume 1/2 in a reservoir, when stirring, add copper sulphate pentahydrate by proportioning, stirring is to being completely dissolved；
(2) when stirring, add sulphuric acid by proportioning, continue stirring 10min；
(3) after cooling, when stirring, add chloride ion, brightener, carrying agent and leveling agent by proportioning, after completing, continue stirring 10min；
(4) supplement remaining deionized water, stir, prepare a kind of PCB through hole blind hole copper electroplating solution。
The electro-plating method of a kind of PCB through hole blind hole copper electroplating solution, puts into the pcb board with through hole and blind hole in the electroplating bath equipped with described copper electroplating solution and electroplates under air stirring, obtain copper plate。
Described plating is divided into three sections:
First paragraph electric current density is 12ASF, and electroplating time is 35min；
Second segment electric current density is 14ASF, and electroplating time is 35min；
3rd section of electric current density is 24ASF, and electroplating time is 35min。
The analysis test result of the copper plate that the present embodiment obtains is as shown in table 1。
The analysis test result of the copper plate that table 1 embodiment 1 ~ 5 obtains
| Test event | Standard value | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Depth capability | 82% | 93% | 92% | 94% | 93% | 94% |
| Filling perforation rate | 88% | 97% | 98% | 99% | 97% | 96% |
| Ductility | 4% | 9% | 8% | 10% | 8% | 9% |
| Stretching force | 220 | 330 | 310 | 320 | 320 | 330 |
| Thermal shock | Good | Outstanding | Outstanding | Outstanding | Outstanding | Outstanding |
| Flatness | Good | Outstanding | Outstanding | Outstanding | Outstanding | Outstanding |
| Brightness | Light | Light | Light | Light | Light | Light |
| Electric conductivity | 53.3 | 55.7 | 56.2 | 57.1 | 56.8 | 55.9 |
| Hardness | 140HV | 164HV | 166HV | 158HV | 162HV | 168HV |
The copper electroplating solution of the present invention has good depth capability and dispersibility, can improve layers of copper in printed wiring board through hole hole and be uniformly distributed, moreover it is possible to effectively reduce the ratio of surface copper layer thickness and hole central copper layer thickness, is suitable for low and middle-end printed panel the electroplates in hole。
The copper plate densification that the present invention obtains is smooth, and filling perforation rate is high, reaches more than 95%, and ductility is better, has good gloss, high tenacity, low internal stress。
Above-described embodiment is the present invention preferably implementation, and in addition, the present invention can also realize by alternate manner, and any apparent replacement is all within protection scope of the present invention without departing from the inventive concept of the premise。
Claims (7)
1. a PCB through hole blind hole copper electroplating solution, it is characterised in that: each component of described copper electroplating solution and content thereof is:
Copper sulphate pentahydrate: 100 ~ 250g/L
Sulphuric acid: 100 ~ 200g/L
Chloride ion: 30 ~ 100ppm
Brightener: 5 ~ 50g/L
Carrying agent: 3 ~ 30g/L
Leveling agent: 2 ~ 20g/L
Deionized water surplus；
And the concentration ratio of copper sulphate pentahydrate and sulphuric acid is 1 ~ 1.25:1；
The mixture that described brightener is made up of the 3-sulfydryl-1-propane sulfonic acid sodium that weight ratio is 1.5 ~ 3.5:1 and ethylene thiourea；
Described carrying agent by the Polyethylene Glycol that molecular weight is 5000 ~ 15000 and polypropylene glycol that molecular weight is 500 ~ 1500 by weight 1.8 ~ 2.6:1 mixture formed；
The mixture that described leveling agent is made up of the leveling agent A that weight ratio is 1.2 ~ 2.4:1 and leveling agent B；Wherein, leveling agent A is polyvinyl imidazol quaternary ammonium compound, and the structural formula of leveling agent B is:
Wherein, R2Being the epoxy alkyl of 2 ~ 10 for straight chained alkyl that carbon number is 3 ~ 10, aromatic radical, ether, ester group or cycloalkyl or carbon number that carbon number is 3 ~ 10, X is halogen atom or hydrogen sulfate ion, and n and m is greater than 2 and integer less than 100。
2. a kind of PCB through hole blind hole copper electroplating solution according to claim 1, it is characterised in that: each component of described copper electroplating solution and content thereof is:
Copper sulphate pentahydrate: 140 ~ 220g/L
Sulphuric acid: 120 ~ 180g/L
Chloride ion: 45 ~ 80ppm
Brightener: 15 ~ 35g/L
Carrying agent: 10 ~ 20g/L
Leveling agent: 5 ~ 15g/L
Deionized water surplus；
And the concentration ratio of copper sulphate pentahydrate and sulphuric acid is 1.17 ~ 1.22:1。
3. a kind of PCB through hole blind hole copper electroplating solution according to claim 1, it is characterised in that: each component of described copper electroplating solution and content thereof is:
Copper sulphate pentahydrate: 180g/L
Sulphuric acid: 150g/L
Chloride ion: 60ppm
Brightener: 25g/L
Carrying agent: 15g/L
Leveling agent: 10g/L
Deionized water surplus；
And the concentration of copper sulphate pentahydrate and sulphuric acid is than for 1.2:1。
4. a kind of PCB through hole blind hole copper electroplating solution according to claim 1, it is characterised in that: the structural formula of described leveling agent A is:
Wherein, R1Being the epoxy alkyl of 2 ~ 10 for straight chained alkyl that carbon number is 1 ~ 10, aromatic radical or cycloalkyl or carbon number that carbon number is 3 ~ 10, X is halogen atom or hydrogen sulfate ion, and n and m is greater than 2 and integer less than 100。
5. the preparation method of a kind of PCB through hole blind hole copper electroplating solution described in any one of claim 1 ~ 4, it is characterised in that: comprise the steps:
(1) adding the deionized water of deionized water volume 1/2 ~ 2/3 in a reservoir, when stirring, add copper sulphate pentahydrate by proportioning, stirring is to being completely dissolved；
(2) when stirring, add sulphuric acid by proportioning, continue stirring 5 ~ 10min；
(3) after cooling, when stirring, add chloride ion, brightener, carrying agent and leveling agent by proportioning, after completing, continue stirring 5 ~ 10min；
(4) supplement remaining deionized water, stir, prepare a kind of PCB through hole blind hole copper electroplating solution。
6. the electro-plating method of a kind of PCB through hole blind hole copper electroplating solution described in any one of claim 1 ~ 4, it is characterized in that: the pcb board with through hole and blind hole is put in the electroplating bath equipped with described copper electroplating solution and electroplate under air stirring, obtain one layer of copper electroplating layer。
7. the electro-plating method of a kind of PCB through hole blind hole copper electroplating solution according to claim 6, it is characterised in that: described plating is divided into three sections:
First paragraph electric current density is 8 ~ 12ASF, and electroplating time is 15 ~ 35min；
Second segment electric current density is 12 ~ 14ASF, and electroplating time is 15 ~ 35min；
3rd section of electric current density is 16 ~ 24ASF, and electroplating time is 15 ~ 35min。
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