The method for coarsening surface of epoxide resin type or polyimide type tellite
Technical field
The invention belongs to the printed circuit board processing technique field, particularly relate to a kind of method for coarsening surface of simple to operate, PCB substrate that environmental pollution is lower.
Background technology
In electroless plating, electroless copper is crucial plating.Particularly electronic product, electronics are applied in our daily life more in recent years, and two-sided and multilayer printed circuit board (PCB) becomes the indispensable basic component of high-tech product.In the printed electronic circuit manufacturing process, electroless copper is one important operation, and the surface coarsening of plating substrate is one of committed step in the electroless copper pre-treatment.Alligatoring whether proper has very big influence for the outward appearance of product after the bonding force of coating and substrate and the plating.
Common chemical copper facing pretreated substrate method of roughening has following several: (1) mechanical alligatoring; (2) chemical roughen; (3) organic solvent alligatoring; Wherein modal is the chemical roughen method.Wu Xiaoen etc. (" material protection "; 2006; 39 (12): 19-22), the superfine people of Yu De (" electroplate with cover with paint, lacquer, colour wash, etc. "; 2007; 26 (10): 33-35), Wang Xiuwen etc. (" electroplating and finish "; 2006,28 (6): 9-13) wait the researchist in above article, to summarize and studied existing electroless copper substrate chemical roughen technology, and compared.From above three pieces of articles as can be seen, in view of the widespread use of printed circuit board (PCB) (PCB) and huge commercial value, both at home and abroad the research of PCB technology is extremely paid close attention to, therefore, the optimization of substrate roughening process also becomes a big research focus of printed electronic circuit technology.
For printed circuit board (PCB), its baseplate material mainly is Resins, epoxy and polyimide (PI).Be mainly the printed circuit board (PCB) of Resins, epoxy for baseplate material, its surface coarsening treating processes is normally finished by chromic anhydride-vitriol oil system.Yet because Cr (VI) ion is to cause environmental pollution and one of the harmful heavy metal that is detrimental to health, use probably was under an embargo in today of promotion environmental protection.In addition,, so just make chromic anhydride be deposited on the roughening solution bottom, bring inconvenience to actually operating because the solubleness of chromic anhydride in the vitriol oil is less.In order to reduce environmental pollution, promote the development of printed electronic circuit electroless copper, people are exploring novel process, the novel method of electroless plating pre-treatment always.Abroad the someone proposes to replace chromic anhydride-vitriol oil system and done a large amount of work in this respect with alkaline permanganate solution.F.Tomaiuolo, P.Montangero, people such as Schroer and X.Roizard have studied the alligatoring effect of alkaline permanganate solution to epoxy resin base plate from different angles respectively, yet the alligatoring condition are not optimized, and because employed neutralization solution is H
2O
2-H
2SO
4Mixed solution, the unstable of hydrogen peroxide causes solution often to lose efficacy, and makes troubles to operation.To this, people such as the Wang Xiuwen of Shaanxi Normal University have done corresponding Supplementary Study to the alkalinity potassium permanganate coarsening solution, adopt H
2C
2O
42H
2O-H
2SO
4System is as neutralization solution, and optimized the concentration ratio of coarsening solution.But, adopt the alkalinity potassium permanganate alligatoring because this step of neutralization must be arranged, increase the operation steps of whole process flow virtually, influenced the enforcement efficient of whole copper-plating technique.
Summary of the invention
The invention provides the method for coarsening surface of a kind of epoxide resin type or polyimide type tellite, this method adopts alkaline coarsening solution to carry out the substrate alligatoring, oil removing, alligatoring unite two into one, and have characteristics easy and simple to handle, that environmental pollution is little, cost is low, are suitable for producing in enormous quantities.
Detailed technology scheme of the present invention:
The method for coarsening surface of epoxide resin type or polyimide type tellite may further comprise the steps:
Step 1: preparation coarsening solution.
Alkaline peroxide, peroxysulphate, inorganic salt, OP emulsifying agent and surface dispersant are mixed, add deionization and form solution, more than the regulator solution pH value to 12, obtain coarsening solution after stirring.Described alkaline peroxide is the mixture a kind of or arbitrary proportion between them in sodium peroxide, Potassium peroxide or the barium peroxide, and the consumption in coarsening solution is 1.25~2.50M; Described peroxysulphate is the mixture a kind of or arbitrary proportion between them in Sodium persulfate, Potassium Persulphate or the ammonium peroxydisulfate, and the consumption in coarsening solution is 0.06~0.25M; Described inorganic salt are the mixture a kind of or arbitrary proportion between them in yellow soda ash or the salt of wormwood, and the consumption in coarsening solution is 0.15~0.20M; The consumption of described OP emulsifying agent in coarsening solution is 3.5~6.0g/L; Described surface dispersant is the mixture a kind of or arbitrary proportion between them in Sodium dodecylbenzene sulfonate, Potassium dodecylbenzenesulfonate or the n-octyl sodium sulfate, and the consumption in coarsening solution is 2.5 * 10
-4~5.5 * 10
-4M.
Step 2: surface coarsening is handled.
The coarsening solution of step 1 preparation is heated to 50~80 ℃, then epoxide resin type or polyimide type tellite are soaked in the coarsening solution, stir and soaked 5~20 minutes, at last epoxide resin type or polyimide type tellite are taken out from coarsening solution, clean up with deionized water, can obtain oil removing, epoxide resin type or polyimide type tellite that surface coarsening is good.Wherein, described epoxide resin type tellite is for being that binding agent, glass fibre are the tellite of packing material with Resins, epoxy; Described polyimide type tellite is for being the tellite of baseplate material with the polyimide.
Need to prove, in preparation coarsening solution process,, can cause alkaline peroxide or peroxysulphate to cross thermolysis accidentally if having because alkaline peroxide or peroxysulphate can produce a large amount of heats in the dissolution process of water solvent.Therefore in order to prevent that alkaline peroxide or peroxysulphate from crossing thermolysis, alkaline peroxide or peroxysulphate slowly should be added in the water solvent.
The present invention adopt strong basicity that alkaline peroxide, peroxysulphate, inorganic salt are mixed with, the strong oxidizing property aqueous solution to Resins, epoxy in the tellite or polyimide explain, oxygenizement, reach the surface coarsening purpose.The main effect of the OP emulsifying agent that is wherein added is a greasy dirt of removing the tellite surface, has surperficial dissemination concurrently; The main effect of the surface dispersant that is added is the surface tension that reduces coarsening solution, thereby makes the alligatoring better effects if.
To adopt the epoxide resin type or the polyimide type tellite of roughening treatment of the present invention to pass through operations such as sensitization, activation, electroless copper again, just can obtain the plating piece of the red copper coating of glitter powder, splendid through the bonding force and the conductivity of performance test sample.The FR-4 epoxy resin base plate that surface coarsening is not handled, carry out the FR-4 epoxy resin base plate that surface coarsening handles and adopt the present invention to carry out after FR-4 epoxy resin base plate surface that surface coarsening handles all carries out the metal spraying processing with the potassium permanganate system, (SEM) observes its surface topography with the surface sweeping Electronic Speculum.Can find out obviously that from the SEM scanning result aperture, microetch hole that the FR-4 epoxy resin base plate surface of adopting the potassium permanganate system to carry out the surface coarsening processing forms is bigger, and skewness; And adopting the present invention to carry out the small and dense collection in aperture, FR-4 epoxy resin base plate surface micro etching hole that surface coarsening is handled, the copper even compact ground that has so just guaranteed to generate in the copper facing process forms good coating morphology attached to substrate surface.
The invention has the beneficial effects as follows:
Adopt method for coarsening surface provided by the invention that epoxide resin type or polyimide type tellite are carried out the surface coarsening processing, oil removing, two technologies of alligatoring are settled at one go, its technological process simply, operate easily and apply, be suitable for and produce in enormous quantities, can in producing the PCB process, finish process of surface treatment more at low cost.Owing to need not add heavy metallic salt in the operating process, avoided in the past producing a large amount of Cr (VI) ion in chromic anhydride-vitriol oil system and caused environmental pollution, the chroma in waste water height that the potassium permanganate system is brought, need problem such as neutralizing treatment.
Embodiment
Embodiment one:
(1) takes by weighing 5g sodium peroxide, 2g Sodium Persulfate, 0.8g yellow soda ash, 0.005g Sodium dodecylbenzene sulfonate with electronic balance and transfer in the beaker and mix, measure 0.175g OP emulsifying agent and add in the beaker, measure the 50ml deionized water with graduated cylinder again;
(2) earlier small amount of deionized water is slowly added in the beaker of step (1), the limit edged stirs rapidly;
(3) treat that solid dissolves fully in the beaker after, remaining deionized water is added, continue to stir;
(4) pH value that records the solution of step (3) gained is 13, after beaker is put into cold water and cooled off 3~5 minutes, in 50 ℃ thermostat water bath;
(5) with weighing after the epoxy resin base plate drying of 2cm * 2cm, writing down its quality is 0.14047g;
(6) after weighing finishes substrate is put into this mixture and react 5min, will at the uniform velocity stir therebetween;
(7) epoxy resin base plate after the alligatoring is taken out, rinse well with deionized water and carry out sensitization, activation, electroless copper;
(8) sample is taken out, dry up with blower at once after rinsing well with deionized water, claim that again its quality is 0.14100g.
Adopt weighting method to measure plating speed, the plating speed that records sample is 7.35 μ m/h; With the resistance of four probe method measure sample side, useful range is at 0.01-1.00 Ω .cm.Measuring result is 0.13 Ω/.
Embodiment two:
Taking by weighing 5g Potassium peroxide, 2g ammonium peroxydisulfate, 0.9g yellow soda ash, 0.006g Sodium dodecylbenzene sulfonate transfers in the beaker and mixes, measuring 0.3g OP emulsifying agent adds in the beaker, according to the step of embodiment one with its wiring solution-forming, alligatoring 10min in 55 ℃ thermostat water bath; Sensitization, activation, electroless copper after drying.Weighting method is measured plating speed, and the plating speed that records sample is 5.57 μ m/h; The resistance of four probe method measure sample side, useful range is at 0.01-1.00 Ω .cm.Measuring result is 0.25 Ω/.
Embodiment three:
Take by weighing the 10g sodium peroxide, 3g Potassium Persulphate, 0.8g yellow soda ash, 0.007g Sodium dodecylbenzene sulfonate are transferred in the beaker and are mixed, measure 0.2g OP emulsifying agent and add in the beaker, according to the step of embodiment one with its wiring solution-forming, alligatoring 5min in 60 ℃ thermostat water bath; Sensitization, activation, electroless copper after drying.Weighting method is measured plating speed, and the plating speed that records sample is 4.60 μ m/h; The resistance of four probe method measure sample side, useful range is at 0.01-1.00 Ω .cm.Measuring result is 0.10 Ω/.
Embodiment four:
Taking by weighing 10g Potassium peroxide, 1g Sodium Persulfate, 0.75g yellow soda ash, 0.008g Sodium dodecylbenzene sulfonate transfers in the beaker and mixes, measuring 0.25g OP emulsifying agent adds in the beaker, according to the step of embodiment one with its wiring solution-forming, alligatoring 10min in 65 ℃ thermostat water bath; Sensitization, activation, electroless copper after drying.Weighting method is measured plating speed, and the plating speed that records sample is 7.88 μ m/h; The resistance of four probe method measure sample side, useful range is at 0.01-1.00 Ω .cm.Measuring result is 0.25 Ω/.
Embodiment five:
Taking by weighing 5g sodium peroxide, 1g ammonium peroxydisulfate, 1.0g yellow soda ash, 0.01g Sodium dodecylbenzene sulfonate transfers in the beaker and mixes, measuring 0.3g OP emulsifying agent adds in the beaker, according to the step of embodiment one with its wiring solution-forming, alligatoring 15min in 60 ℃ thermostat water bath; Sensitization, activation, electroless copper after drying.Weighting method is measured plating speed, and the plating speed that records sample is 3.27 μ m/h; The resistance of four probe method measure sample side, useful range is at 0.01-1.00 Ω .cm.Measuring result is 0.20 Ω/.