CN103572335A - Copper plating solution for PCB (printed circuit board) through holes, and preparation method and plating method thereof - Google Patents
Copper plating solution for PCB (printed circuit board) through holes, and preparation method and plating method thereof Download PDFInfo
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- CN103572335A CN103572335A CN201310585201.8A CN201310585201A CN103572335A CN 103572335 A CN103572335 A CN 103572335A CN 201310585201 A CN201310585201 A CN 201310585201A CN 103572335 A CN103572335 A CN 103572335A
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Abstract
The invention relates to the technical field of PCB (printed circuit board) plating, in particular to a copper plating solution for PCB through holes, and a preparation method and a plating method thereof. Each liter of the copper plating solution comprises the following components according to contents: 70-150g of copper sulfate pentahydrate, 100-300g of sulfuric acid, 30-100ppm of chlorine ions, 5-50g of brightener, 3-30g of carrier, 2-20g of leveling agent and the balance of deionized water, wherein the concentration ratio of the copper sulfate pentahydrate to the sulfuric acid is 1: (1.5-2). The plating method comprises the following steps: putting a PCB with through holes into a plating bath with the copper plating solution; plating during air agitation to obtain a copper plating layer. The copper plating layer formed by the plating method has a good uniform plating capability as high as 95% above, and is dense, smooth, relatively good in malleability, good in gloss, high in toughness and low in internal stress.
Description
Technical field
The present invention relates to PCB electroplating technology field, be specifically related to a kind of PCB the electroplates in hole copper solutions and preparation method thereof and electro-plating method.
Background technology
Hydrosulphate copper-plating technique, because its solution basal component is simple, solution-stabilized, current efficiency is high, adds suitable additive just can obtain the copper plate that light is smooth, toughness is good, therefore in printing plate hole metallization is electroplated, is used widely.
China is that the pcb board of the large pcb board of the first in the world big producing country ，Dan China is produced the still low side in industry now, and the pcb board of domestic production is mainly the pcb board of low and middle-end, and the pcb board of middle and high end is produced on slave unit or on starting material all under one's control.External dye-type additive is all generally more expensive, pcb board for production low and middle-end is high expensive, the electroplating liquid medicine that therefore a lot of domestic medium and small Electroplate Factories use is not external dye additive, they use great majority is electroplating additives that domestic manufacturers produce, and the covering power of these additives and dispersive ability are not special height, therefore develop a kind of be applicable to electroplating additive that domestic low and middle-end pcb board produces in China still highly significant with necessity.
The manufacturer production of recent year many outstanding electroplating intermediates, and produce a kind of good electroplating additive system, focus on the composite of intermediate, utilize domestic liquid medicine manufacturer and certainly synthetic electroplating intermediate reflexs to join electroplating liquid medicine and request external control and minimizing production cost to have great importance to China's electroplating liquid medicine industry.
When electroplating liquid medicine of the prior art is electroplated PCB through hole, the copper plate covering power obtaining is poor, copper plate unfairness, and ductility, gloss and toughness are poor, therefore, be necessary to develop a kind of copper plate covering power of obtaining of making good, copper plate is smooth, and the good PCB the electroplates in hole of ductility, gloss and toughness copper solutions and preparation method thereof and using method.
Summary of the invention
In order to overcome the shortcoming and defect existing in prior art, the object of the present invention is to provide a kind of PCB the electroplates in hole copper solutions and preparation method thereof, this copper electroplating solution has good covering power and dispersive ability, can improve copper layer in printed circuit board through hole hole is uniformly distributed, can also effectively reduce the ratio of surface copper layer thickness and hole central copper layer thickness, be applicable to low and middle-end printing plate the electroplates in hole, and bath stability, life-span are long; This preparation method is simple to operate, has reduced production cost, is applicable to suitability for industrialized production.
Another object of the present invention is to provide a kind of using method of PCB the electroplates in hole copper solutions, form copper plate covering power good by the method, fine and close smooth, ductility is better, has good gloss, high tenacity, low internal stress.
Object of the present invention is achieved through the following technical solutions: a kind of PCB the electroplates in hole copper solutions, and each component of described copper electroplating solution and content thereof are:
Cupric sulfate pentahydrate: 70 ~ 150g/L
Sulfuric acid: 100 ~ 300g/L
Chlorion: 30 ~ 100ppm
Brightening agent: 5 ~ 50g/L
Carrying agent: 3 ~ 30g/L
Leveling agent: 2 ~ 20g/L
Deionized water surplus;
And the concentration ratio of cupric sulfate pentahydrate and sulfuric acid is 1:1.5 ~ 2.
Preferably, each component of described copper electroplating solution and content thereof are:
Cupric sulfate pentahydrate: 90 ~ 130g/L
Sulfuric acid: 150 ~ 250g/L
Chlorion: 45 ~ 80ppm
Brightening agent: 15 ~ 35g/L
Carrying agent: 10 ~ 20g/L
Leveling agent: 5 ~ 15g/L
Deionized water surplus;
And the concentration ratio of cupric sulfate pentahydrate and sulfuric acid is 1:1.67 ~ 1.92.
More preferred, each component of described copper electroplating solution and content thereof are:
Cupric sulfate pentahydrate: 110g/L
Sulfuric acid: 200g/L
Chlorion: 60ppm
Brightening agent: 25g/L
Carrying agent: 15g/L
Leveling agent: 10g/L
Deionized water surplus;
And the concentration ratio of cupric sulfate pentahydrate and sulfuric acid is 1:1.82.
Cupric sulfate pentahydrate is the main salt of copper electroplating solution, is Cu in solution
2+source, concentration is wanted appropriateness.The too low sedimentation rate of cupric sulfate pentahydrate concentration is slower, and cupric sulfate pentahydrate excessive concentration sedimentation rate is too fast, and crystalline particle is thick, and in plate face and hole, the difference of thickness of coated copper layer is excessive.Cupric sulfate pentahydrate of the present invention is defined as 70 ~ 150g/L, can guarantee sedimentation rate, can make again copper plate densification smooth, and preferred, cupric sulfate pentahydrate is defined as 90 ~ 130g/L, and more preferred, cupric sulfate pentahydrate is defined as 110g/L.
Sulfuric acid mainly increases the conductive capability of copper electroplating solution, and prevents Cu
2+hydrolysis, it is appropriate that concentration is also wanted.The too high meeting of sulfuric acid concentration makes copper electroplating solution dispersive ability poor, and too low meeting increases copper plate fragility, and toughness declines.Sulfuric acid of the present invention is defined as 100 ~ 300g/L, both can guarantee the dispersive ability of copper electroplating solution, again can be so that the copper plate toughness arriving be higher, and preferred, sulfuric acid is defined as 150 ~ 250g/L, and more preferred, sulfuric acid is defined as 200g/L.
In the operation of pcb plating through hole, to keep cupric sulfate pentahydrate and sulfuric acid in certain ratio, just can reach and all plate preferably effect.And the covering power of through hole is better under the low copper bar part of peracid, cupric sulfate pentahydrate of the present invention: the concentration ratio of sulfuric acid is defined as 1:1.5 ~ 2, belong to the low copper electroplating liquid of peracid, have and all plate preferably effect, preferably, cupric sulfate pentahydrate: the concentration ratio of sulfuric acid is defined as 1:1.67 ~ 1.92, more preferred, cupric sulfate pentahydrate: the concentration ratio of sulfuric acid is defined as 1:1.82.
Chlorion can improve the activity of anode, promotes that anode normally dissolves, and prevents anode passivation; Can also reduce " copper powder " that because of anode dissolution, not exclusively produce, improve light and the leveling ability of copper plate, improve copper plate quality.Chlorion of the present invention is defined as 30 ~ 100ppm, can make copper plate densification smooth, and preferred, chlorion is defined as 45 ~ 80ppm, and more preferred, chlorion is defined as 60ppm.
The additive using in current production be take commercial additive as main, the copper plate quality that different additive is brought, and bath stability and production efficiency are also different.The effect of additive is mainly to reduce plating solution surface tension, improves covering power and the dispersive ability of plating solution, improves electrode process and improves copper plate quality.Conventional additive mainly contains brightening agent, carrying agent and leveling agent.
Brightening agent (Hrightener): meeting can produce a kind of " depolarize " or force down the action of " overpotential " under chlorion is assisted, thereby there will be the copper-plated effect of acceleration, therefore be called again accelerator (Accelerator).Brightening agent itself can also enter in copper plate and participate in crystalline texture, and impact or intervention, to the spontaneous nucleation mode of copper atom deposition, impel and become more fine and smooth tissue, therefore be called again grain-refining agent (GrainRefiner).Brightening agent of the present invention is defined as 5 ~ 50g/L, can make copper plate densification smooth, and preferred, brightening agent is defined as 15 ~ 35g/L, and more preferred, brightening agent is defined as 25g/L.
Preferably, the mixture that the 2-mercaptobenzimidazole that described brightening agent is 1.5 ~ 3.5:1 by weight ratio and ethylene thiourea form.
2-mercaptobenzimidazole (M) is white crystalline powder.Nontoxic, there is bitter taste, relative density 1.40 ~ 1.44, fusing point is not less than 300 ℃.2-mercaptobenzimidazole, as copper brightener, can make copper plate light, and have smooth effect, also can improve working current density.Normal and copper brightener N, SPS etc. are used in conjunction with.
Ethylene thiourea (N) is white powder, and fusing point is 198 ℃.Ethylene thiourea is used as copper brightener, normal and acid copper plating brightening agent M, and SPS etc. are used in conjunction with.
The present invention adopts 2-mercaptobenzimidazole and ethylene thiourea to be used in conjunction with, and the weight ratio that limits 2-mercaptobenzimidazole and ethylene thiourea is 1.5 ~ 3.5:1, can make copper plate smooth, preferably, the weight ratio of 2-mercaptobenzimidazole and ethylene thiourea is 2 ~ 3:1, more preferred, the weight ratio of 2-mercaptobenzimidazole and ethylene thiourea is 2.5:1.
Carrying agent (Carrier): with Cl
-under acting in conjunction, can strengthen the inhibition to copper deposition, can assist brightening agent to go to negative electrode depression distributed throughout, therefore be called carrying agent.Carrying agent can present " increasing polarization " or increase the effect of " overpotential " in groove in liquid reaction, to copper facing deposition, can produce the phenomenon of " deceleration ", has namely showed the effect of " constraining ", therefore be called again repressor (Suppresser).But carrying agent yet separately has the capillary effect of the tank liquor of reduction, or increases its moistening effect, so be often called again wetting agent (Wetting Agent or Wetter).Carrying agent can assist gloss-imparting agent in the distribution of surfacing, also can make copper face increase glossiness.Carrying agent of the present invention is defined as 3 ~ 30g/L, can increase the gloss of copper plate, and preferred, carrying agent is defined as 10 ~ 20g/L, more preferred, and carrying agent is defined as 15g/L.
Preferably, described carrying agent is that molecular weight is 2000 ~ 8000 polyoxyethylene glycol.
Polyoxyethylene glycol (PEG) can obviously be strengthened the cathodic polarization of electro-coppering plating solution, has suppressed the deposition of electro-coppering; Meanwhile, the spread coefficient of PEG in plating solution also reduces with the increase of its molecular weight, thereby increased the adsorptive power of M in micropore bottom, accelerated the deposition of electro-coppering in micropore bottom; Further, increase the table of PEG molecular weight depositing copper film and roughness, copper film degree of crystallinity and resistivity all decrease.Therefore, the molecular weight of polyoxyethylene glycol of the present invention is defined as 2000 ~ 8000, can guarantee the spread coefficient of PEG in copper electroplating solution, and makes copper plate densification smooth.
Leveling agent (Leveler): with very strong positive polarity, be easy to be adsorbed on plating piece surface current density larger part, compete with cupric ion, make cupric ion at high electric current place, be difficult for deposition, but the copper that does not affect low current district deposits, make up-and-down surface originally become more smooth, be therefore called leveling agent.Leveling agent of the present invention is defined as 2 ~ 20g/L, can guarantee the smooth of copper plate, and preferred, leveling agent is defined as 5 ~ 15g/L, and more preferred, leveling agent is defined as 10g/L.
Early 1970s, sour copper is electroplated and is progressively tending towards ripe.There is the patent of a large amount of discussion leveling agents this period, wherein used the product after the sub-limb alkylation of polyhexene, as a leveling agent, alkylating reagent used has benzyl chloride, methyl-sulfate, sulfuric acid two ester, propenyl bromine, propane sultone etc.This quaternary ammonium salt is compared with polyhexene imines in the past used, water-soluble better, with other the composite better effects if of additive, has expanded the range of current in bright district, and copper plate is bright, smooth, high tenacity, low internal stress.
The product of having used another synthetic leveling agent Epicholorohydrin and substance reaction gained containing one or more N functional group this period, the material containing N functional group of using has pyridine, quinoline, isoquinoline 99.9, benzoglyoxaline etc.The introducing of this additive is mainly the low problem of additive utilization ratio existing in original sour copper plating system in order to solve.Additive system originally makes plating piece surface irregularity, leveling poor effect, and new leveling agent has but made up this deficiency to a certain extent.In electroplating process, allow protruding local copper plate partially thin, partially thick at pit copper plate accordingly, and can not cause high internal stress, and both reached leveling object, make again copper plate possess good mechanical property.
Preferably, the mixture that the leveling agent A that described leveling agent is 1.2 ~ 2.4:1 by weight ratio and leveling agent B form; Wherein, leveling agent A is polyvinyl imidazol quaternary ammonium compound, and leveling agent B is the polymkeric substance of N-vinyl imidazole and epoxy compounds.
Preferably, the structural formula of described leveling agent A is:
Wherein, R1 is that carbonatoms is the epoxy alkyl that 1 ~ 10 alkyl, aromatic base or the carbonatoms cycloalkyl that is 3 ~ 10 or carbonatoms are 2 ~ 10, and X is halogen atom or hydrogen sulfate ion, and n and m are greater than 2 and be less than 100 integer.
Preferably, R1 is ethyl group, propyl, butane group, phenyl, benzyl, cyclopropane base, propylene oxide base; X is chlorine, bromine, iodine or hydrogen sulfate ion.
More preferred, R1X is monochloroethane, N-PROPYLE BROMIDE, butyl iodide, benzyl chlorine, epoxy chloropropane.
Preferably, the structural formula of described leveling agent B is:
Wherein, R2 is that carbonatoms is epoxy alkyl or the R3X that 1 ~ 10 alkyl, aromatic base, ether, ester group or the carbonatoms cycloalkyl that is 3 ~ 10 or carbonatoms are 2 ~ 10; Wherein, R3 is that carbonatoms is the epoxy alkyl that 1 ~ 10 alkyl, aromatic base or the carbonatoms cycloalkyl that is 3 ~ 10 or carbonatoms are 2 ~ 10, and X is halogen atom or hydrogen sulfate ion.
Preferably, R2 is ethyl group, propyl, butane group, phenyl, benzyl, cyclopropane base, propylene oxide base, or chloroethene alkyl, N-PROPYLE BROMIDE base, butyl iodide base, benzyl chloro, epoxy chloropropionate alkyl.
The present invention adopts the polymkeric substance of polyvinyl imidazol quaternary ammonium compound and N-vinyl imidazole and epoxy compounds with the composite use of weight ratio of 1.2 ~ 2.4:1, can make that copper plate is bright, smooth, high tenacity, low internal stress.
A preparation method for PCB the electroplates in hole copper solutions, comprises the steps:
(1) in container, add the deionized water of deionized water volume 1/2 ~ 2/3, under the state stirring, by proportioning, add cupric sulfate pentahydrate, be stirred to completely and dissolve;
(2) under the state stirring, by proportioning, add sulfuric acid, continue to stir 5 ~ 10min;
(3) after cooling, under the state stirring, by proportioning, add chlorion, brightening agent, carrying agent and leveling agent, after completing, 5 ~ 10min is stirred in continuation;
(4) supplement remaining deionized water, stir, make a kind of PCB the electroplates in hole copper solutions.
Another object of the present invention is achieved through the following technical solutions: a kind of electro-plating method of PCB the electroplates in hole copper solutions, and the pcb board with through hole is put into the plating tank that described copper electroplating solution is housed and under pneumatic blending, electroplate, obtain copper plate.
Preferably, the current density of described plating is 1 ~ 5A/dm
2, electroplating temperature is 18 ~ 30 ℃, electroplating time is 30 ~ 60min; The radius-thickness ratio of described through hole is 2 ~ 6.
The influence factor that acid copper plating bath is electroplated has:
1, current density: current density with the service temperature of plating solution, the concentration of copper sulfate and alr mode are relevant.Temperature is high, allows the current density upper limit of use also high, and while having pressurized air to stir, current density can reach 1 ~ 5A/dm
2.In the normal current density range using, with the raising of electric current density, sedimentation velocity is accelerated, and copper plate bright range increases, and leveling property also can improve.It is 1 ~ 5A/dm that current density of the present invention is controlled
2, preferred, current density is 2 ~ 4A/dm
2, more preferred, current density is 3A/dm
2.
2, electroplating temperature: improve the temperature of plating solution, can add high current density, thereby improve light and the leveling property of copper plate, and guarantee good toughness.It is relevant with the brightening agent using that the temperature of acid bright copper plating is controlled, the most of brightening agent using at present, and when temperature surpasses 30 ℃, cathodic polarization significantly declines, and the low current density district of copper plate produces white mist and obfuscation; Temperature is high again, and while surpassing 35 ℃, copper plate is all dimmed, thus electroplating temperature general control 18 ~ 30 ℃ more suitable, preferred, electroplating temperature is 22 ~ 28 ℃, more preferred, electroplating temperature is 25 ℃.
3, stir: stirring can reduce the concentration polarization of plating solution, improve current density, prevent that copper plate from producing striped, improve the homogeneity of copper plate, accelerate sedimentation velocity.The mode that the present invention adopts pressurized air to stir, contributes to be oxidized the univalent copper ion producing in plating solution, is conducive to eliminate the generation of " copper powder ".When stirring, preferably can adopt circulating filtration, to eliminate the trace " copper powder " that may exist in electrolytic solution and degradation production and the suspended impurity of brightening agent, be conducive to like this improve copper plate quality, stability and the work-ing life of raising electrolytic solution.
4, anode material: in acidic copper-plating of bright, quality of anode is very important factor, generally should not use electrolytic copper, and the present invention adopts the phosphorous copper anode of anaerobic.When this is because uses oxygen containing electrolytic copper anode, surface easily produces Red copper oxide (copper powder), the consumption of brightening agent is increased, and reduce copper plate quality, when phosphorus can make the electrochemical dissolution of anode, surface produces one deck black rete, has avoided uneven dissolution.
5, through hole radius-thickness ratio: the radius-thickness ratio of through hole is larger on covering power impact, in order to make perforation plating also can have good covering power, radius-thickness ratio of the present invention is defined as 2 ~ 6, and preferred, radius-thickness ratio is defined as 2 ~ 5, and more preferred, radius-thickness ratio is defined as 4.
Beneficial effect of the present invention is: the present invention adopts 2-mercaptobenzimidazole and ethylene thiourea as the composite use of brightening agent, can make copper plate smooth; The present invention adopts polyoxyethylene glycol as carrying agent, can make copper plate densification smooth; The present invention adopts the polymkeric substance of polyvinyl imidazol quaternary ammonium compound and N-vinyl imidazole and epoxy compounds as the composite use of leveling agent, can make that copper plate is bright, smooth, high tenacity, low internal stress.
Copper electroplating solution of the present invention has good covering power and dispersive ability, can improve copper layer in printed circuit board through hole hole is uniformly distributed, can also effectively reduce the ratio of surface copper layer thickness and hole central copper layer thickness, be applicable to low and middle-end printing plate the electroplates in hole, and bath stability, life-span are long.
The preparation method of a kind of PCB the electroplates in hole copper solutions of the present invention, simple to operate, reduced production cost, be applicable to suitability for industrialized production.
The using method of a kind of PCB the electroplates in hole copper solutions of the present invention, forms copper plate covering power by the method good, reaches more than 95%, and copper plate densification is smooth, and ductility is better, has good gloss, high tenacity, low internal stress.
embodiment:
For the ease of those skilled in the art's understanding, 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 electroplates in hole copper solutions, each component of described copper electroplating solution and content thereof are:
Cupric sulfate pentahydrate: 70g/L
Sulfuric acid: 105g/L
Chlorion: 30ppm
Brightening agent: 5g/L
Carrying agent: 3g/L
Leveling agent: 2g/L
Deionized water surplus;
And the concentration ratio of cupric sulfate pentahydrate and sulfuric acid is 1:1.5.
The mixture that the 2-mercaptobenzimidazole that described brightening agent is 1.5:1 by weight ratio and ethylene thiourea form; Described carrying agent is that molecular weight is 2000 polyoxyethylene glycol.
The mixture that the leveling agent A that described leveling agent is 1.2:1 by weight ratio and leveling agent B form; Wherein, leveling agent A is polyvinyl imidazol quaternary ammonium compound, and leveling agent B is the polymkeric substance of N-vinyl imidazole and epoxy compounds.
The structural formula of described leveling agent A is:
Wherein, R
1for ethyl group, X is chlorine atom, n=2, m=2.
The structural formula of described leveling agent B is:
Wherein, R
2for chloroethene alkyl.
A preparation method for PCB the electroplates in hole copper solutions, comprises the steps:
(1) in container, add the deionized water of deionized water volume 1/2, under the state stirring, by proportioning, add cupric sulfate pentahydrate, be stirred to completely and dissolve;
(2) under the state stirring, by proportioning, add sulfuric acid, continue to stir 5min;
(3) after cooling, under the state stirring, by proportioning, add chlorion, brightening agent, carrying agent and leveling agent, after completing, 5min is stirred in continuation;
(4) supplement remaining deionized water, stir, make a kind of PCB the electroplates in hole copper solutions.
An electro-plating method for PCB the electroplates in hole copper solutions, puts into by the pcb board with through hole the plating tank that described copper electroplating solution is housed and electroplates under pneumatic blending, obtains copper plate.
The current density of described plating is 1A/dm
2, electroplating temperature is 18 ℃, electroplating time is 30min; The radius-thickness ratio of described through hole is 2.
The analytical test result of the copper plate that the present embodiment obtains is as shown in table 1.
Embodiment 2
A electroplates in hole copper solutions, each component of described copper electroplating solution and content thereof are:
Cupric sulfate pentahydrate: 90g/L
Sulfuric acid: 150g/L
Chlorion: 45ppm
Brightening agent: 15g/L
Carrying agent: 10g/L
Leveling agent: 5g/L
Deionized water surplus;
And the concentration ratio of cupric sulfate pentahydrate and sulfuric acid is 1:1.67.
The mixture that the 2-mercaptobenzimidazole that described brightening agent is 2:1 by weight ratio and ethylene thiourea form; Described carrying agent is that molecular weight is 3500 polyoxyethylene glycol.
The mixture that the leveling agent A that described leveling agent is 1.5:1 by weight ratio and leveling agent B form; Wherein, leveling agent A is polyvinyl imidazol quaternary ammonium compound, and leveling agent B is the polymkeric substance of N-vinyl imidazole and epoxy compounds.
The structural formula of described leveling agent A is:
Wherein, R
1for propyl, X is bromine atoms, n=20, m=80.
The structural formula of described leveling agent B is:
Wherein, R
2for benzyl.
A preparation method for PCB the electroplates in hole copper solutions, comprises the steps:
(1) in container, add the deionized water of deionized water volume 2/3, under the state stirring, by proportioning, add cupric sulfate pentahydrate, be stirred to completely and dissolve;
(2) under the state stirring, by proportioning, add sulfuric acid, continue to stir 6min;
(3) after cooling, under the state stirring, by proportioning, add chlorion, brightening agent, carrying agent and leveling agent, after completing, 6min is stirred in continuation;
(4) supplement remaining deionized water, stir, make a kind of PCB the electroplates in hole copper solutions.
An electro-plating method for PCB the electroplates in hole copper solutions, puts into by the pcb board with through hole the plating tank that described copper electroplating solution is housed and electroplates under pneumatic blending, obtains copper plate.
The current density of described plating is 2A/dm
2, electroplating temperature is 21 ℃, electroplating time is 40min; The radius-thickness ratio of described through hole is 3.
The analytical test result of the copper plate that the present embodiment obtains is as shown in table 1.
Embodiment 3
A electroplates in hole copper solutions, each component of described copper electroplating solution and content thereof are:
Cupric sulfate pentahydrate: 110g/L
Sulfuric acid: 200g/L
Chlorion: 60ppm
Brightening agent: 25g/L
Carrying agent: 15g/L
Leveling agent: 10g/L
Deionized water surplus;
And the concentration ratio of cupric sulfate pentahydrate and sulfuric acid is 1:1.82.
The mixture that the 2-mercaptobenzimidazole that described brightening agent is 2.5:1 by weight ratio and ethylene thiourea form; Described carrying agent is that molecular weight is 5000 polyoxyethylene glycol.
The mixture that the leveling agent A that described leveling agent is 1.8:1 by weight ratio and leveling agent B form; Wherein, leveling agent A is polyvinyl imidazol quaternary ammonium compound, and leveling agent B is the polymkeric substance of N-vinyl imidazole and epoxy compounds.
The structural formula of described leveling agent A is:
Wherein, R
1for butane group, X is iodine atom, n=50, m=50.
The structural formula of described leveling agent B is:
Wherein, R
2for epoxy chloropropionate alkyl.
A preparation method for PCB the electroplates in hole copper solutions, comprises the steps:
(1) in container, add the deionized water of deionized water volume 1/2, under the state stirring, by proportioning, add cupric sulfate pentahydrate, be stirred to completely and dissolve;
(2) under the state stirring, by proportioning, add sulfuric acid, continue to stir 7min;
(3) after cooling, under the state stirring, by proportioning, add chlorion, brightening agent, carrying agent and leveling agent, after completing, 7min is stirred in continuation;
(4) supplement remaining deionized water, stir, make a kind of PCB the electroplates in hole copper solutions.
An electro-plating method for PCB the electroplates in hole copper solutions, puts into by the pcb board with through hole the plating tank that described copper electroplating solution is housed and electroplates under pneumatic blending, obtains copper plate.
The current density of described plating is 3A/dm
2, electroplating temperature is 24 ℃, electroplating time is 45min; The radius-thickness ratio of described through hole is 4.
The analytical test result of the copper plate that the present embodiment obtains is as shown in table 1.
Embodiment 4
A electroplates in hole copper solutions, each component of described copper electroplating solution and content thereof are:
Cupric sulfate pentahydrate: 130g/L
Sulfuric acid: 250g/L
Chlorion: 80ppm
Brightening agent: 35g/L
Carrying agent: 20g/L
Leveling agent: 15g/L
Deionized water surplus;
And the concentration ratio of cupric sulfate pentahydrate and sulfuric acid is 1:1.92.
The mixture that the 2-mercaptobenzimidazole that described brightening agent is 3:1 by weight ratio and ethylene thiourea form; Described carrying agent is that molecular weight is 6500 polyoxyethylene glycol.
The mixture that the leveling agent A that described leveling agent is 2.1:1 by weight ratio and leveling agent B form; Wherein, leveling agent A is polyvinyl imidazol quaternary ammonium compound, and leveling agent B is the polymkeric substance of N-vinyl imidazole and epoxy compounds.
The structural formula of described leveling agent A is:
Wherein, R
1for benzyl, X is chlorine atom, n=80, m=20.
The structural formula of described leveling agent B is:
Wherein, R
2for propyl.
A preparation method for PCB the electroplates in hole copper solutions, comprises the steps:
(1) in container, add the deionized water of deionized water volume 2/3, under the state stirring, by proportioning, add cupric sulfate pentahydrate, be stirred to completely and dissolve;
(2) under the state stirring, by proportioning, add sulfuric acid, continue to stir 8min;
(3) after cooling, under the state stirring, by proportioning, add chlorion, brightening agent, carrying agent and leveling agent, after completing, 8min is stirred in continuation;
(4) supplement remaining deionized water, stir, make a kind of PCB the electroplates in hole copper solutions.
An electro-plating method for PCB the electroplates in hole copper solutions, puts into by the pcb board with through hole the plating tank that described copper electroplating solution is housed and electroplates under pneumatic blending, obtains copper plate.
The current density of described plating is 4A/dm
2, electroplating temperature is 21 ℃, electroplating time is 50min; The radius-thickness ratio of described through hole is 5.
The analytical test result of the copper plate that the present embodiment obtains is as shown in table 1.
Embodiment 5
A electroplates in hole copper solutions, each component of described copper electroplating solution and content thereof are:
Cupric sulfate pentahydrate: 150g/L
Sulfuric acid: 300g/L
Chlorion: 100ppm
Brightening agent: 50g/L
Carrying agent: 30g/L
Leveling agent: 20g/L
Deionized water surplus;
And the concentration ratio of cupric sulfate pentahydrate and sulfuric acid is 1:2.
The mixture that the 2-mercaptobenzimidazole that described brightening agent is 3.5:1 by weight ratio and ethylene thiourea form; Described carrying agent is that molecular weight is 8000 polyoxyethylene glycol.
The mixture that the leveling agent A that described leveling agent is 2.4:1 by weight ratio and leveling agent B form; Wherein, leveling agent A is polyvinyl imidazol quaternary ammonium compound, and leveling agent B is the polymkeric substance of N-vinyl imidazole and epoxy compounds.
The structural formula of described leveling agent A is:
Wherein, R
1for cyclopropane base, X is cyclopropane base atom, n=100, m=100.
The structural formula of described leveling agent B is:
Wherein, R
2for cyclopropane base.
A preparation method for PCB the electroplates in hole copper solutions, comprises the steps:
(1) in container, add the deionized water of deionized water volume 1/2, under the state stirring, by proportioning, add cupric sulfate pentahydrate, be stirred to completely and dissolve;
(2) under the state stirring, by proportioning, add sulfuric acid, continue to stir 10min;
(3) after cooling, under the state stirring, by proportioning, add chlorion, brightening agent, carrying agent and leveling agent, after completing, 10min is stirred in continuation;
(4) supplement remaining deionized water, stir, make a kind of PCB the electroplates in hole copper solutions.
An electro-plating method for PCB the electroplates in hole copper solutions, puts into by the pcb board with through hole the plating tank that described copper electroplating solution is housed and electroplates under pneumatic blending, obtains copper plate.
The current density of described plating is 5A/dm
2, electroplating temperature is 30 ℃, electroplating time is 60min; The radius-thickness ratio of described through hole is 6.
The analytical test result of the copper plate that the present embodiment obtains is as shown in table 1.
The analytical 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 |
| Covering power | 88% | 97% | 95% | 98% | 97% | 96% |
| Ductility | 4% | 8% | 9% | 10% | 9% | 8% |
| Stretching force | 220 | 320 | 300 | 330 | 340 | 320 |
| Thermal shocking | Good | Outstanding | Outstanding | Outstanding | Outstanding | Outstanding |
| Planeness | Good | Outstanding | Outstanding | Outstanding | Outstanding | Outstanding |
| Brightness | Light | Light | Light | Light | Light | Light |
| Electroconductibility | 53.3 | 56.4 | 55.1 | 56.9 | 57.2 | 55.8 |
| Hardness | 140HV | 160 HV | 165 HV | 155 HV | 170 HV | 168 HV |
Copper electroplating solution of the present invention has good covering power and dispersive ability, can improve copper layer in printed circuit board through hole hole is uniformly distributed, can also effectively reduce the ratio of surface copper layer thickness and hole central copper layer thickness, be applicable to low and middle-end printing plate the electroplates in hole, and bath stability, life-span are long.
The copper plate covering power that the present invention obtains is good, reaches more than 95%, and copper plate densification is smooth, and ductility is better, has good gloss, high tenacity, low internal stress.
Above-described embodiment is preferably implementation of the present invention, 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 (10)
1. a PCB the electroplates in hole copper solutions, is characterized in that: each component of described copper electroplating solution and content thereof are:
Cupric sulfate pentahydrate: 70 ~ 150g/L
Sulfuric acid: 100 ~ 300g/L
Chlorion: 30 ~ 100ppm
Brightening agent: 5 ~ 50g/L
Carrying agent: 3 ~ 30g/L
Leveling agent: 2 ~ 20g/L
Deionized water surplus;
And the concentration ratio of cupric sulfate pentahydrate and sulfuric acid is 1:1.5 ~ 2.
2. a kind of PCB the electroplates in hole copper solutions according to claim 1, is characterized in that: each component of described copper electroplating solution and content thereof are:
Cupric sulfate pentahydrate: 90 ~ 130g/L
Sulfuric acid: 150 ~ 250g/L
Chlorion: 45 ~ 80ppm
Brightening agent: 15 ~ 35g/L
Carrying agent: 10 ~ 20g/L
Leveling agent: 5 ~ 15g/L
Deionized water surplus;
And the concentration ratio of cupric sulfate pentahydrate and sulfuric acid is 1:1.67 ~ 1.92.
3. a kind of PCB the electroplates in hole copper solutions according to claim 1, is characterized in that: each component of described copper electroplating solution and content thereof are:
Cupric sulfate pentahydrate: 110g/L
Sulfuric acid: 200g/L
Chlorion: 60ppm
Brightening agent: 25g/L
Carrying agent: 15g/L
Leveling agent: 10g/L
Deionized water surplus;
And the concentration ratio of cupric sulfate pentahydrate and sulfuric acid is 1:1.82.
4. a kind of PCB the electroplates in hole copper solutions according to claim 1, is characterized in that: the mixture that the 2-mercaptobenzimidazole that described brightening agent is 1.5 ~ 3.5:1 by weight ratio and ethylene thiourea form; Described carrying agent is that molecular weight is 2000 ~ 8000 polyoxyethylene glycol.
5. a kind of PCB the electroplates in hole copper solutions according to claim 1, is characterized in that: the mixture that the leveling agent A that described leveling agent is 1.2 ~ 2.4:1 by weight ratio and leveling agent B form; Wherein, leveling agent A is polyvinyl imidazol quaternary ammonium compound, and leveling agent B is the polymkeric substance of N-vinyl imidazole and epoxy compounds.
6. a kind of PCB the electroplates in hole copper solutions according to claim 5, is characterized in that: the structural formula of described leveling agent A is:
Wherein, R
1the epoxy alkyl that the cycloalkyl that alkyl, aromatic base or the carbonatoms that is 1 ~ 10 for carbonatoms is 3 ~ 10 or carbonatoms are 2 ~ 10, X is halogen atom or hydrogen sulfate ion, n and m are greater than 2 and be less than 100 integer.
7. a kind of PCB the electroplates in hole copper solutions according to claim 5, is characterized in that: the structural formula of described leveling agent B is:
Wherein, R
2epoxy alkyl or R that the cycloalkyl that alkyl, aromatic base, ether, ester group or the carbonatoms that is 1 ~ 10 for carbonatoms is 3 ~ 10 or carbonatoms are 2 ~ 10
3x; Wherein, R
3the epoxy alkyl that the cycloalkyl that alkyl, aromatic base or the carbonatoms that is 1 ~ 10 for carbonatoms is 3 ~ 10 or carbonatoms are 2 ~ 10, X is halogen atom or hydrogen sulfate ion.
8. according to the preparation method of a kind of PCB the electroplates in hole copper solutions described in claim 1 ~ 7 any one, it is characterized in that: comprise the steps:
(1) in container, add the deionized water of deionized water volume 1/2 ~ 2/3, under the state stirring, by proportioning, add cupric sulfate pentahydrate, be stirred to completely and dissolve;
(2) under the state stirring, by proportioning, add sulfuric acid, continue to stir 5 ~ 10min;
(3) after cooling, under the state stirring, by proportioning, add chlorion, brightening agent, carrying agent and leveling agent, after completing, 5 ~ 10min is stirred in continuation;
(4) supplement remaining deionized water, stir, make a kind of PCB the electroplates in hole copper solutions.
9. the electro-plating method of a kind of PCB the electroplates in hole copper solutions described in claim 1 ~ 7 any one, is characterized in that: the pcb board with through hole is put into the plating tank that described copper electroplating solution is housed and under pneumatic blending, electroplate, obtain copper plate.
10. the electro-plating method of a kind of PCB the electroplates in hole copper solutions according to claim 9, is characterized in that: the current density of described plating is 1 ~ 5A/dm
2, electroplating temperature is 18 ~ 30 ℃, electroplating time is 30 ~ 60min; The radius-thickness ratio of described through hole is 2 ~ 6.
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| CN113445086A (en) * | 2021-04-17 | 2021-09-28 | 珠海松柏科技有限公司 | Copper plating additive and copper electroplating solution suitable for printed circuit board |
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