CN106559961A - A kind of conduction liquid and preparation method thereof and conductive processing method - Google Patents

A kind of conduction liquid and preparation method thereof and conductive processing method Download PDF

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Publication number
CN106559961A
CN106559961A CN201610796813.5A CN201610796813A CN106559961A CN 106559961 A CN106559961 A CN 106559961A CN 201610796813 A CN201610796813 A CN 201610796813A CN 106559961 A CN106559961 A CN 106559961A
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nano
conduction liquid
silver
carbon powder
pcb substrate
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CN201610796813.5A
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CN106559961B (en
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梁怀舒
刘江波
章晓冬
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GUANGZHOU SKYCHEM Ltd
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GUANGZHOU SKYCHEM Ltd
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
    • H05K3/42—Plated through-holes or plated via connections
    • H05K3/429—Plated through-holes specially for multilayer circuits, e.g. having connections to inner circuit layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/0545—Dispersions or suspensions of nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0779—Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved

Abstract

The invention discloses a kind of conduction liquid and preparation method thereof and conductive processing method.The conduction liquid of the present invention, by mass percentage, including following raw material：0.5～5% nano-carbon powder, 5～10% Nano silver grain, 0.5～5% anion surfactant, balance of deionized water；By the proportioning for adjusting each raw material, nano-carbon powder and Nano silver grain are homogeneously dispersed in water in the presence of anion surfactant, and the conduction liquid being prepared into is used for the insulating barrier of PCB substrate hole wall when carrying out conductive processing, with good electric conductivity；The preparation method of the conduction liquid of the present invention, causes nano-carbon powder and Nano silver grain to be homogeneously dispersed in conduction liquid by ultrasonic disperse first；Then the conduction liquid of finely dispersed small particle nano-carbon powder and Nano silver grain mixing is obtained after the conduction liquid ball milling after will be scattered, the ultrasound and ball milling mixing method of employing increased jointly the electric conductivity of conduction liquid, improve the make efficiency of PCB electroplates.

Description

A kind of conduction liquid and preparation method thereof and conductive processing method
Technical field
The present invention relates to the heavy copper technology fields of PCB, more particularly to a kind of conduction liquid and preparation method thereof and conductive processing side Method.
Background technology
Printed circuit board (PCB) (PCB) is the substrate for connecting each electronic component, planar relies primarily on shape after exposure etching Into copper wire connection, and need between the layers by metallized hole realize interconnect.In printed circuit board (PCB) manufacturing technology In, most critical is exactly heavy copper process, and its main effect is exactly the nonmetallic hole for making single or multiple lift printed circuit board (PCB), is passed through One layer of uniform conductive layer is deposited on hole wall, then copper facing is thickeied through plating, reach the purpose in loop. this purpose will be reached just Conductive processing must be carried out to the insulating barrier of the hole wall of PCB substrate, can just be easy to follow-up plating to sink copper.Use of the prior art Conductive processing conduction liquid is carried out in the insulating barrier of the hole wall to PCB substrate, usually using conduction liquid made by graphite or carbon black, But graphite or carbon black cause which to the electric conductivity after insulating barrier conductive processing because its particle diameter is big and the defect such as poor dispersion Difference, hole copper adhesion be not good.
The content of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of conduction liquid, and electric conductivity is excellent.
It is that, up to this purpose, the present invention is employed the following technical solutions：
A kind of conduction liquid, by mass percentage, including following raw material：0.5～5% nano-carbon powder, 5～10% silver Nano-particle, 0.5～5% anion surfactant, balance of deionized water, wherein, the Nano silver grain by silver from Sub- reducing agent and silver ion complex are with (1～4)：The mass ratio of (1～4) Jing reduction reactions under ultrasonic agitation are prepared； For example, the mass percent of nano-carbon powder is 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%； The mass percent of Nano silver grain be 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%8.5%, %, 9%, 9.5%, 10%；The mass percent of anion surfactant be 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%th, 5%；Balance of deionized water.
Nano-carbon powder is the major part for constituting conduction liquid, plays electric action, when in solution, content is less than 0.5%, Conductive capability is deteriorated；When in solution, content is higher than 5%, nano-carbon powder dispersion is uneven, also leads to conductive capability variation.Silver The advantages such as nano-particle is because its granularity is little, active big, good conductivity and color light are applied in conduction liquid, work as nano grain of silver When sub- content is less than 5%, solution conductivity reduced capability, PCB spaces of a whole page electroplating effect are deteriorated；When Nano silver grain content is higher than 10% When, solution solid content increases, and solution dispersion is uneven.Commercial metals Nano silver grain size is larger, disperses uneven and valency Lattice are expensive, cause its poorly conductive, and stability is poor, and Nano silver grain of the present invention is matched somebody with somebody by silver ion reducing agent and silver ion Compound is with (1～4)：The mass ratio of (1～4) Jing reduction reactions under the conditions of ultrasonic agitation are prepared, such as silver ion reduction The mass ratio of agent and silver ion complex is 1:1、1:2、1:3、1:4、2:1、2:3、3:1、3:2、3:4、4:1、4:3；Wherein, silver Silver ion in ionic complex is reduced the nano particle that agent molecule is reduced into silver, further forms controllable little by ball milling The Nano silver grain of size, selects mass ratio to be (1～4)：The silver ion reducing agent of (1～4) and the synthesis of silver ion complex are little The Nano silver grain of particle diameter, the Nano silver grain of the synthesis spy such as have good stability, good dispersion, good conductivity and size less Point, it and nano-carbon powder is uniformly dispersed in medium in the presence of anion surfactant, has can conduction liquid Excellent electric conductivity, stability and associativity.Anion surfactant can promote the stability of carbon dust suspension and wetting Performance, it can be combined together with nano-carbon powder well in certain proportion, when anionic surfactant concentration is less than When 0.5%, cause nano-carbon powder excess, solution dispersion is uneven；When anionic surfactant concentration is higher than 5%, solution is steady Determine degradation.The present invention makes nano-carbon powder and Nano silver grain in anion surface active by the proportioning of each raw material of regulation It is homogeneously dispersed in the presence of agent in medium in i.e. deionized water, makes solution equal using the anion surfactant in solution Even nano-carbon powder and silver nanoparticle suspension keep stable, and possess good wettability, make nano-carbon powder and Yin Na Rice corpuscles mixing suspension is sufficiently attracted on non-conductor hole wall surface, forms uniform, compact conductive layer.
Wherein, the specific surface area of the nano-carbon powder be 300～1500m2/g, such as 300m2/g, 400m2/g、500m2/ g、600m2/g、700m2/g、800m2/g、900m2/g、1000m2/g、1100m2/g、1200m2/g、1300m2/g、1400m2/g、 1500m2/g。
Wherein, the average grain diameter of the nano-carbon powder be 100～200nm, such as 100nm, 105nm, 110nm, 115nm, 120nm、125nm、130nm、135nm、140nm、145nm、150nm、155nm、160nm、165nm、170nm、175nm、 180nm、185nm、190nm、195nm、200nm；Preferably, the average grain diameter of the nano-carbon powder is 105nm.
Wherein, the silver ion reducing agent be potassium permanganate, ascorbic acid, sodium borohydride, three sodium citrates, gold chloride and One kind in TGA Nano silver grain；
Preferably, during the silver ion complex is silver nitrate, silver chlorate, silver sulfide, silver iodide, silver oxide and silver bromide One kind；
Preferably, the average grain diameter of the Nano silver grain be 10～40nm, for example, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, the Nano silver grain of small particle are easily uniformly dispersed, and make the good conductivity of conduction liquid, stability strong.
Nano-sized carbon and Nano silver grain are easily reunited in aqueous together and cause dispersion uneven, and being can be It is fully dispersed in the aqueous solution, add a certain amount of surfactant to be necessary.The surfactant that adopts of the present invention for the moon from Sub- surfactant, can be such that nano-sized carbon and Nano silver grain spreads more evenly across in the aqueous solution.Wherein, the anion table Face activating agent is sodium xanthogenate or neopelex.
In order to ensure nano-sized carbon and Nano silver grain it is dispersed in aqueous after stability, it usually needs to its pH Value is adjusted, and pH adjusting agent, such as NaOH or pH adjusting agent commonly used in the art are usually added in conduction liquid, which is adjusted PH value is 10～12.
In order to ensure the quality of conduction liquid, the additives such as stabilizer, dispersant in conduction liquid, are also added, the present invention is used Stabilizer and dispersant be additive commonly used in the art.
The second object of the present invention is to provide a kind of preparation method of conduction liquid, makes nano-carbon powder and Nano silver grain equal It is scattered in conducting solution evenly, dispersive property is good, and the particle diameter of nano-carbon powder and Nano silver grain is little, the conduction of conduction liquid Performance is good, comprises the following steps, and by mass percentage, weighs 0.5～5% nano-carbon powder, 5～10% nano grain of silver Son, 0.5～5% anion surfactant be added in the deionized water of surplus, be sufficiently mixed it is rearmounted enter ultrasonic mixing channel Middle ultrasonic agitation, makes nano-carbon powder and Nano silver grain be dispersed in deionized water, finely dispersed mixed liquor is inserted Ball milling is carried out in ball mill, the finely dispersed conduction liquid of small particle is prepared.
Wherein, the power of the ultrasonic agitation be 80～500W, such as 80W, 100W, 200W, 300W, 500W, ultrasonic work( Rate is too small, and nano-carbon powder and silver nanoparticle suspension dispersion are uneven；Ultrasonic power is excessive, finely dispersed nano-carbon powder and Silver nanoparticle suspension is reunited together again, it is preferable that the power of the ultrasonic agitation is 300W.
Wherein, the time of the ultrasonic agitation be 10～120min, such as 10min, 20min, 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min, 120min, ultrasonic time are too short, nano-carbon powder and silver Nanoparticle suspension can not be completely dispersed in media as well；Ultrasonic time is long, nano-carbon powder and silver nanoparticle suspension grain Footpath becomes big.Preferably, the time of the ultrasonic agitation is 30min.
Wherein, the rotating speed of the mechanical milling process be 100～500rpm, such as 100rpm, 200rpm, 300rpm, 400rpm, 500rpm, rotating speed are too high, and solution reaction acutely causes very much electroplating effect to be deteriorated；Rotating speed is too low, and ball milling is insufficient, and solution disperses not Uniformly.Preferably, the rotational speed of ball-mill is 300rpm.
Wherein, the detailed process of the ball milling is：Finely dispersed mixed liquor is inserted into ball milling in comprehensive ball mill, it is first First turn clockwise ball milling 3min, static 1～5min, then rotate counterclockwise ball milling 5min, static 1～5min, as one Individual ball milling circulation is circulated, and controls whole Ball-milling Time for 1～6h, such as 1h, 2h, 3h, 4h, 5h, 6h；Preferably, it is described The time of ball milling is 2h.
Wherein, a diameter of 3～10mm of the abrading-ball that the mechanical milling process is adopted, such as 3mm, 4mm, 5mm, 6mm, 7mm, 8mm、9mm、10mm。
The third object of the present invention is to provide a kind of method of the conductive processing of conduction liquid, the PCB Jing after conductive processing Substrate has good electric conductivity and outstanding hole wall binding ability.
The method of the conductive processing include being adjusted PCB substrate liquid pretreatment, washing, conduction liquid conductive processing, Drying, microetch, the step of wash, dry up.
Wherein, the detailed process of the adjustment liquid pretreatment is：The PCB substrate for being provided with hole is placed in adjustment liquid, room temperature Lower stirring immersion 1.5min, stirring dynamics are moderate, pre-process to increase the electric conductivity of hole wall；
The detailed process of the washing is：The PCB substrate deionized water of adjustment liquid pretreatment is washed 3～5 times repeatedly, To remove the adjustment liquid of the residual on surface；
The detailed process of the conduction liquid conductive processing is：PCB substrate after washing is placed in into the preparation of embodiment 1～6 Conduction liquid in, stirring immersion 1.5min under room temperature condition, stirring dynamics are moderate, Jing conductive processings, nano-carbon powder and silver nanoparticle Particle can have hole wall good with reference to conductive portion resin and glass Shu Jinhang metallization on hole wall on hole wall, is made Electric conductivity is so as to follow-up electro-coppering；
The detailed process of the drying is：The PCB substrate of Jing conductive processings is placed in in baking oven 15min at 100～150 DEG C Lower drying, the too high conduction liquid for making remnants of temperature solidify in hole wall, and temperature is too low to cause solidification incomplete, too high or too low for temperature Electric conductivity can be affected, therefore must strictly control drying temperature；
The detailed process of the microetch is：The PCB substrate of drying is placed in the NPS micro-corrosion liquids that concentration is 8%, under room temperature 1～2min of microetch, removes the organic pollution of substrate surface；
The detailed process of the washing is：The further deionized water of PCB substrate after microetch is washed 3～5 times repeatedly, To remove the conduction liquid and residual oily substance of the residual on surface；
The detailed process that dries up is：PCB substrate after having washed is dried up with hair-dryer at once, is first blown away with cold wind Remained on surface material and moisture content, then with hot blast drying, prevent PCB substrate oxidation and remained on surface impurity.
Compared with prior art, beneficial effects of the present invention are：The conduction liquid of the present invention, by mass percentage, including Following raw material：0.5～5% nano-carbon powder, 5～10% Nano silver grain, 0.5～5% anion surfactant, it is remaining Measure as deionized water；By the proportioning for adjusting each raw material, nano-carbon powder and Nano silver grain are made in anion surfactant It is homogeneously dispersed under effect in medium in i.e. deionized water, makes solution uniform using the anion surfactant in solution Nano-carbon powder and silver nanoparticle suspension keep stable, and possess good wettability, make nano-carbon powder and nano grain of silver Sub- mixing suspension is sufficiently attracted on non-conductor hole wall surface, forms uniform, compact conductive layer；The present invention Described Nano silver grain is by silver ion reducing agent and silver ion complex with (1～4)：The mass ratio of (1～4) is in ultrasonic agitation Under the conditions of Jing reduction reactions prepare, the silver ion in silver ion complex be reduced agent molecule be reduced into silver nanometer Grain, further forms controllable undersized Nano silver grain by ball milling, selects mass ratio to be (1～4)：The silver of (1～4) from Sub- reducing agent and silver ion complex synthesize the Nano silver grain of small particle, and the Nano silver grain of synthesis has good stability, divides Scattered property is good, good conductivity and the features such as less size, will be it and nano-carbon powder uniform in the presence of anion surfactant Dispersion in media as well, can make conduction liquid that there is excellent electric conductivity, stability and associativity.
The preparation method of the conduction liquid of the present invention, first by ultrasonic disperse so that nano-carbon powder and Nano silver grain are equal It is scattered in conduction liquid evenly；Then finely dispersed small particle is obtained after the conduction liquid ball mill ball milling after will be scattered Nano-carbon powder and the conduction liquid of Nano silver grain mixing, the ultrasound and ball milling mixing method of employing increased the conduction of conduction liquid jointly Performance and hole wall adhesion, the insulating barrier for the hole wall of PCB substrate enable nonconducting insulation hole wall to have good conduction Power, and the hole copper adhesion of its hole wall is improve, it is easy to follow-up electroplating technology, improves the make efficiency of PCB electroplates. The method of the conductive processing of the conduction liquid of the present invention, the technique for simplifying plated through-hole are saved man-hour, reduce material materials, PCB substrate Jing after conductive processing has good electric conductivity and outstanding hole wall binding ability, can be widely applied to PCB bases The manufacture of plate.
Description of the drawings
Fig. 1 is the schematic diagram of backlight level criterion of the prior art.
Specific embodiment
Technical scheme is further illustrated below by specific embodiment.
As no specific instructions, various raw materials of the invention are commercially available buys, or is prepared according to the conventional method of this area Obtain.
Embodiment 1
By mass percentage, weigh 0.5% nano-carbon powder, 5% Nano silver grain, 0.5% detergent alkylate Sodium sulfonate, 2% NaOH, 1% stabilizer, 2% dispersant are added in 89% deionized water, wherein, Yin Na Rice corpuscles be by mass ratio be 1:What 1 potassium permanganate and nitric acid galactic longitude reduction reaction were prepared, it is sufficiently mixed the rearmounted excess of imports Ultrasonic agitation 30min under 300W power in sound mixing channel, finely dispersed mixed liquor is inserted to be carried out in comprehensive ball ball mill Ball milling, it is 300rpm to control rotational speed of ball-mill, and turn clockwise ball milling 3min first, static 2min, then rotate counterclockwise ball milling 5min, static 2min, are circulated as a ball milling circulation, control whole Ball-milling Time for 1h, the diameter of abrading-ball used For 3mm, conduction liquid is prepared.
Embodiment 2
By mass percentage, weigh 1% nano-carbon powder, 6% Nano silver grain, 1% sodium xanthogenate, 1.5% NaOH, 1.5% stabilizer, 2% dispersant be added in 87% deionized water, wherein, Nano silver grain is It is 1 by mass ratio:What 2 ascorbic acid and chlorination galactic longitude reduction reaction were prepared, be sufficiently mixed it is rearmounted enter ultrasonic mixing channel Ultrasonic agitation 30min under middle 300W power, finely dispersed mixed liquor is inserted carries out ball milling in comprehensive ball ball mill, control Rotational speed of ball-mill is 400rpm, and turn clockwise ball milling 3min first, static 3min, and then rotate counterclockwise ball milling 5min, static 3min, is circulated as a ball milling circulation, controls whole Ball-milling Time for 2h, a diameter of 5mm of abrading-ball used, preparation Obtain conduction liquid.
Embodiment 3
By mass percentage, weigh 2% nano-carbon powder, 7% Nano silver grain, 2% sodium xanthogenate, 1% NaOH, 3% stabilizer, 1% dispersant are added in 84% deionized water, wherein, Nano silver grain is by matter Amount is than being 1:What 3 sodium borohydride and sulfuration galactic longitude reduction reaction were prepared, be sufficiently mixed it is rearmounted enter ultrasonic mixing channel in Ultrasonic agitation 30min under 300W power, finely dispersed mixed liquor is inserted in comprehensive ball ball mill carries out ball milling, control ball Mill rotating speed is 200rpm, and turn clockwise ball milling 3min first, static 5min, and then rotate counterclockwise ball milling 5min, static 5min, is circulated as a ball milling circulation, controls whole Ball-milling Time for 3h, a diameter of 6mm of abrading-ball used, preparation Obtain conduction liquid.
Embodiment 4
By mass percentage, weigh 3% nano-carbon powder, 8% Nano silver grain, 3% DBSA Sodium, 1% NaOH, 1% stabilizer, 3% dispersant are added in 81% water, wherein, Nano silver grain be by Mass ratio is 1:What 4 three sodium citrates and iodate galactic longitude reduction reaction were prepared, be sufficiently mixed it is rearmounted enter ultrasonic mixing channel Ultrasonic agitation 30min under middle 300W power, finely dispersed mixed liquor is inserted carries out ball milling in comprehensive ball ball mill, control Rotational speed of ball-mill is 500rpm, and turn clockwise ball milling 3min first, static 5min, and then rotate counterclockwise ball milling 5min, static 5min, is circulated as a ball milling circulation, controls whole Ball-milling Time for 4h, a diameter of 7mm of abrading-ball used, preparation Obtain conduction liquid.
Embodiment 5
By mass percentage, weigh 4% nano-carbon powder, 9% Nano silver grain, 4% sodium xanthogenate, 0.8% NaOH, 2.5% stabilizer, 1.7% dispersant be added in 78% water, wherein, Nano silver grain is by matter Amount is than being 2:What 1 gold chloride and oxidation galactic longitude reduction reaction were prepared, be sufficiently mixed it is rearmounted enter ultrasonic mixing channel in 300W Ultrasonic agitation 30min under power, finely dispersed mixed liquor is inserted carries out ball milling in comprehensive ball ball mill, control ball milling turns Speed is 300rpm, and turn clockwise ball milling 3min first, static 5min, then rotate counterclockwise ball milling 5min, static 5min, with This is that a ball milling circulation is circulated, and it is 5h, a diameter of 8mm of abrading-ball used to control whole Ball-milling Time, prepares and leads It is electro-hydraulic.
Embodiment 6
By mass percentage, weigh 5% nano-carbon powder, 10% Nano silver grain, 5% DBSA Sodium, 1% NaOH, 3% stabilizer, 3% dispersant are added in 73% water, wherein, Nano silver grain be by Mass ratio is 3:What 1 TGA and bromination galactic longitude reduction reaction were prepared, be sufficiently mixed it is rearmounted enter ultrasonic mixing channel in Ultrasonic agitation 30min under 300W power, finely dispersed mixed liquor is inserted in comprehensive ball ball mill carries out ball milling, control ball Mill rotating speed is 300rpm, and turn clockwise ball milling 3min first, static 5min, and then rotate counterclockwise ball milling 5min, static 5min, is circulated as a ball milling circulation, controls whole Ball-milling Time for 6h, a diameter of 10mm of abrading-ball used, system It is standby to obtain conduction liquid.
Comparative example
By mass percentage, 3% carbon dust, 25% lauryl sodium sulfate, 2% NaOH are weighed and is added to 70% Deionized water in, be sufficiently stirred for 4h, prepare the conduction liquid of comparative example.
Conduction liquid prepared by embodiment 1～6 and comparative example is used for the conductive processing of the hole wall insulation sides layer of PCB substrate, The process of conductive processing includes adjusting liquid pretreatment, washing, conduction liquid conductive processing, drying, microetch, washes, dries up, concrete mistake Journey is as follows：
1) adjust liquid pretreatment：The PCB substrate for being provided with hole is placed in adjustment liquid, under room temperature, stirring immersion 1.5min, stirs Mix that dynamics is moderate, pre-process to increase the electric conductivity of hole wall；
2) wash：The PCB substrate deionized water of adjustment liquid pretreatment is washed 3～5 times repeatedly, to remove the residual of surface The adjustment liquid for staying；
3) conduction liquid conductive processing：PCB substrate after washing is placed in the conduction liquid of the preparation of embodiment 1～6, room temperature Under the conditions of stirring immersion 1.5min, stirring dynamics is moderate, Jing conductive processings, and nano-carbon powder and Nano silver grain can be with reference in hole walls On, conductive portion resin and glass Shu Jinhang metallization on hole wall are made, makes hole wall that there is good electric conductivity so as to follow-up electricity Copper facing；
4) dry：The PCB substrate of Jing conductive processings is placed in 15min in baking oven to dry at 100～150 DEG C, temperature mistake Height makes the conduction liquid of remnants solidify in hole wall, and temperature is too low to cause solidification incomplete, too high or too low for temperature to affect conduction Performance, therefore must strictly control drying temperature；
5) microetch：The PCB substrate of drying is placed in the NPS micro-corrosion liquids that concentration is 8%, 1～2min of microetch under room temperature is removed Remove the organic pollution of substrate surface；
6) wash：The further deionized water of PCB substrate after microetch is washed 3～5 times repeatedly, to remove the residual of surface The conduction liquid for staying and residual oily substance；
7) dry up：PCB substrate after having washed is dried up with hair-dryer at once, first with cold wind blow away remained on surface material and Moisture content, then with hot blast drying, prevents PCB substrate oxidation and remained on surface impurity.
The basic parameter of embodiment 1～6 and the conduction liquid of comparative example is tested, and is applied to PCB substrate Conductive processing, plating, and to having processed after PCB substrate solderability (foundation IPC TM-650) and backlight level carry out Test, the experimental data surveyed are as shown in table 1.
Table 1
Backlight be to sinking a checking examination of copper effect, be under 50X microscopes by light source dim after could observe and see Whether base material light leakage phenomenon is had.Printing opacity more save your breath obvious results fruit it is better, typically with 10 grades as standard of assessing (as shown in Figure 1), At least up to 8 grades are asked, if backlight level is too low, it is easy to cause having no copper in the holes, affect the electric conductivity and reliability of PCB.The back of the body Light grade illustrates that hole wall adhesion can be preferably more than D8 levels.Embodiments of the invention 1～6 use slicing experiment method, lead to Inverted metallurgic microscope observation is crossed, and diagram is judged according to plating backlight level, show that the backlight level of this six embodiments is equal More than or equal to 8 grades, backlight effect is illustrated preferably, the conduction liquid electroplating effect for further illustrating the present invention is good.
Conduction liquid prepared by the present invention, the good dispersion of nano-carbon powder and Nano silver grain in conduction liquid, median particle size are protected Hold in 100～200nm, illustrate that solution is uniform, good dispersion property；The electric conductivity of solution is maintained at below 10k Ω, illustrates molten The electric conductivity of liquid is good；Glass bar absorption property is observed, and illustrates that the adsorptivity of glass bar is stronger, and solution is scattered more equal Even, hole wall adhesion is better, and the electric conductivity of PCB substrate is more preferable；Heavy copper backlight level is in more than D8, it was demonstrated that the method Effective and feasible property.Conduction liquid prepared by the present invention is applied to into the insulating barrier of PCB substrate hole wall, has can PCB substrate good Good electric conductivity and outstanding hole wall binding ability.
Applicant states that the present invention illustrates the detailed process equipment of the present invention and technological process by above-described embodiment, But above-mentioned detailed process equipment and technological process are the invention is not limited in, that is, does not mean that the present invention has to rely on above-mentioned detailed Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention, Addition, the selection of concrete mode to the equivalence replacement and auxiliary element of each raw material of product of the present invention etc., all fall within the present invention's Within the scope of protection domain and disclosure.

Claims (10)

1. a kind of conduction liquid, it is characterised in that by mass percentage, including following raw material：0.5～5% nano-carbon powder, 5 ～10% Nano silver grain, 0.5～5% anion surfactant, balance of deionized water, wherein, the silver nanoparticle Particle is by silver ion reducing agent and silver ion complex with (1～4)：The mass ratio of (1～4) Jing reduction under the conditions of ultrasonic agitation Reaction is prepared.
2. conduction liquid according to claim 1, it is characterised in that the specific surface area of the nano-carbon powder is 300～ 1500m2/g。
3. conduction liquid according to claim 1, it is characterised in that the average grain diameter of the nano-carbon powder is 100～ 200nm；
Preferably, the average grain diameter of the nano-carbon powder is 105nm.
4. conduction liquid according to claim 1, it is characterised in that the silver ion reducing agent is potassium permanganate, Vitamin C One kind in acid, sodium borohydride, three sodium citrates, gold chloride and TGA Nano silver grain；
Preferably, the silver ion complex is in silver nitrate, silver chlorate, silver sulfide, silver iodide, silver oxide and silver bromide Kind；
Preferably, the average grain diameter of the Nano silver grain is 10～40nm.
5. conduction liquid according to claim 1, it is characterised in that the anion surfactant is sodium xanthogenate or ten Dialkyl benzene sulfonic acids sodium.
6. conduction liquid according to claim 1, it is characterised in that the raw material also includes pH adjusting agent, stabilizer, dispersion Agent.
7. a kind of preparation method of conduction liquid as claimed in claim 1, it is characterised in that comprise the following steps, by quality hundred Point than meter, weigh 0.5～5% nano-carbon powder, 5～10% Nano silver grain, 0.5～5% anion surfactant Be added in the deionized water of surplus, be sufficiently mixed it is rearmounted enter ultrasonic mixing channel in ultrasonic agitation, by finely dispersed mixed liquor Insert, prepare conduction liquid.
8. preparation method according to claim 7, it is characterised in that the power of the ultrasonic agitation is 80～500W, institute The time for stating ultrasonic agitation is 10～120min；The rotating speed of the mechanical milling process is 100～500rpm；
The detailed process of the ball milling is：Finely dispersed mixed liquor is inserted into ball milling in comprehensive ball mill, first clockwise Rotation ball milling 3min, static 1～5min, then rotate counterclockwise ball milling 5min, static 1～5min, follow as a ball milling Ring is circulated, and controls whole Ball-milling Time for 1～6h；
Preferably, the time of the ball milling is 2h；
Preferably, a diameter of 3～10mm of the abrading-ball that the mechanical milling process is adopted.
9. a kind of method of the conductive processing of conduction liquid as claimed in claim 1, it is characterised in that the side of the conductive processing Method includes being adjusted PCB substrate liquid pretreatment, washing, the process of conduction liquid black holes, drying, microetch, the step washed, dry up Suddenly.
10. a kind of method of conductive processing as claimed in claim 9, it is characterised in that the adjustment liquid pretreatment it is concrete Process is：The PCB substrate for being provided with hole is placed in adjustment liquid, stirring immersion 1.5min under room temperature, stirring dynamics are moderate, pretreatment To increase the electric conductivity of hole wall；
The detailed process of the washing is：The PCB substrate deionized water of adjustment liquid pretreatment is washed 3～5 times repeatedly, to go Except the adjustment liquid of the residual on surface；
The detailed process of the conduction liquid conductive processing is：PCB substrate after washing is placed in into leading for the preparation of embodiment 1～6 In electro-hydraulic, stirring immersion 1.5min under room temperature condition, stirring dynamics are moderate, Jing after conductive processing, nano-carbon powder and nano grain of silver Son can make hole wall have good leading with reference to conductive portion resin and glass Shu Jinhang metallization on hole wall on hole wall, is made Electrically so as to follow-up electro-coppering；
The detailed process of the drying is：The PCB substrate of Jing conductive processings is placed in 100～150 DEG C of baking ovens and dries 15min；
The detailed process of the microetch is：The PCB substrate of drying is placed in the NPS micro-corrosion liquids that concentration is 8%, microetch under room temperature 1～2min, removes the organic pollution of substrate surface；
The detailed process of the washing is：The further deionized water of PCB substrate after microetch is washed 3～5 times repeatedly, to go Except the conduction liquid and residual oily substance of the residual on surface；
The detailed process that dries up is：PCB substrate after washing is dried up with hair-dryer at once, first surface is blown away with cold wind residual Material and moisture content are stayed, then with hot blast drying, PCB substrate oxidation and remained on surface impurity is prevented.
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CN111205719A (en) * 2020-03-03 2020-05-29 深圳市利红金科技有限公司 Silver-copper conductive paint and preparation method thereof
CN112105173A (en) * 2020-09-21 2020-12-18 广东硕成科技有限公司 Carbon nano composition for soft board hole metallization and preparation method thereof
CN112159997A (en) * 2020-09-21 2021-01-01 广东硕成科技有限公司 Metal-containing/carbon nanoparticle composition for rigid plate hole metallization

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CN111205719A (en) * 2020-03-03 2020-05-29 深圳市利红金科技有限公司 Silver-copper conductive paint and preparation method thereof
CN112105173A (en) * 2020-09-21 2020-12-18 广东硕成科技有限公司 Carbon nano composition for soft board hole metallization and preparation method thereof
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