CN101032750A - Method of producing sheet shaped silver-plated copper powder - Google Patents
Method of producing sheet shaped silver-plated copper powder Download PDFInfo
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- CN101032750A CN101032750A CN 200710073999 CN200710073999A CN101032750A CN 101032750 A CN101032750 A CN 101032750A CN 200710073999 CN200710073999 CN 200710073999 CN 200710073999 A CN200710073999 A CN 200710073999A CN 101032750 A CN101032750 A CN 101032750A
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Abstract
The process of preparing flaky silver plated copper powder includes the following steps: 1. adding ammonia water and ammonium chloride to waste copper etching liquid through stirring at 50-100 deg.c, adding aluminum chips to reduce and obtain amorphous copper powder, washing and centrifugally drying to obtain clean copper powder; 2. vacuum ball milling the copper powder in a ball mill with steel balls for 10-60 hr after adding lubricant, solder resistant, complexing agent and deoxidant, separating, washing and centrifugally drying to obtain flaky copper powder; and 3. adding flaky copper powder into water solution of silver nitrate with wetting dispersant, complexing agent and reductant to react and to obtain flaky silver plated copper powder, washing with distilled water and organic solvent, and vacuum drying to obtain the product.
Description
[technical field]
The present invention relates to the recovery and utilization technology of the metallic copper that contains in the printed circuit board industry etching waste liquor, particularly relate to a kind of preparation method of flake silver-plated copper powder.
[background technology]
At present, the printed circuit board industry can produce a large amount of copper-containing etching waste solutions in etching and processing printed circuit board process, and only annual just generation the in area, Pearl River Delta surpasses 200,000 tons copper-containing etching waste solution.Because copper-containing etching waste solution contains the high concentration copper ion of (being about 5%-15%), unprocessedly will form serious water environment pollution hidden danger, belong to national hazardous waste.
The existing recoverying and utilizing method of copper-containing etching waste solution is to make mantoquita fine chemical products such as copper sulphate, basic copper carbonate, basic copper chloride, No. 200610038080.5 applications for a patent for invention disclose a kind of method that reclaims hydrochloric acid and copper sulphate from acidic etching liquid as CN, the CN200510029724.X application for a patent for invention discloses a kind of method of utilizing printed circuit board etching waste liquid to prepare stannous chloride, and No. 200610041265.1 applications for a patent for invention of CN disclose a kind of method of producing copper oxychloride with circuitboard etching waste liquid.Though these methods differ from one another, the economic worth of its practical application is lower.Be necessary that for this reason searching can fully utilize copper-containing etching waste solution, to obtain the approach of higher economic worth.
Patent of invention CN 02139151.3 discloses a kind of high performance silver-plated copper powder and preparation method thereof; Patent of invention CN 95111554.5 discloses the preparation method of a kind of electromagnetic-shielding conductive coating with silver-plated copper powder; Application for a patent for invention CN 200410037056.0 discloses a kind of preparation method of silver-plated copper powder; Application for a patent for invention CN 200610089631.0 discloses the silver-plated method of a kind of copper powder surface chemistry.These documents provide with the silver-plated method of chemical replacement.Yet in the silver plating reaction process, the form of silver-colored ammonium ion and copper generation displacement reaction has two kinds: direct replacement reaction and galvanic cell reaction.Wherein, the direct replacement reaction makes the copper surface superscribe the silver of monolayer, the galvanic cell reaction makes silver-colored ammonium ion be reduced at silver surface, expose the oxidized solution that enters of copper in solution simultaneously, thereby form the discontinuous coating of erosion with holes, so the galvanic cell reaction is the reason of infringement coating weight, and above method does not all suppress the measure of galvanic cell reaction.
With regard to copper powder, be that atomized copper powder, electrolytic copper powder or electronation copper powder all are loose and porous structures, surface irregularity causes the not fine and close and plating leakage phenomenon of coating easily.Long-pending because of their real surface simultaneously greatly greater than projected area, thereby the plating area is bigger, causes silver-colored consumption excessive.After copper powder was made into sheet, its surface texture densification was smooth, and therefore the long-pending projected area that equals of copper powder real surface can improve the problems referred to above.Because of copper powder is the tile stack, thereby increased conductive channel greatly, coating layer thickness just has favorable conductive and shielding properties for 20 microns.Also disclosed the preparation method of relevant flake copper in the disclosed document, disclose a kind of chemical method of using ascorbic acid reduction copper ion to prepare ultrafine flake copper powder as application for a patent for invention CN 200310114035.X; Zhong Lianyun etc. [coatings industry Vol33.No9.2003.P12] adopt Zn granulation displacement method to prepare superfine cupper powder, obtain flake copper through ball-milling treatment, carry out ball milling modification behind the electroplate again and obtain flake silver-plated copper powder.Yet because ascorbic acid and Zn grain reduction cost are higher, silver-plated back ball milling makes copper powder Kufil aurification, and the surface is exposed copper still, reduces the copper powder oxidation resistance, and ball milling causes oxidization of copper powder and cupric oxide to sneak into inside easily.Patent of invention CN 03805844.8 discloses a kind of powder thin thickness, and the conductive paste with the powder characteristics that can be used for forming accurate electrode or circuit etc. is with flake copper and manufacture method thereof.This method utilizes wind-force or centrifugal force to carry out copper powder particle resolution process, compresses this copper powder powder by machines such as sand mill, vertical ball mills and makes it plastic deformation, is made into sheet.Because the ball milling copper powder can cause oxidization of copper powder under the condition of secluding air not, ball milling also makes copper oxide particle enter copper powder inside, thereby influences the copper powder conductive capability.
[summary of the invention]
The present invention is intended to address the above problem, and provides a kind of coating not have the preparation method of the anaerobic flake silver-plated copper powder that pitting, electric conductivity are good, silver content is lower.
Method of the present invention relates to following factor:
At first, the printed circuit board copper-containing etching waste solution is a kind of copper ion purity and all higher solution of concentration, aluminium bits price is lower than Zn grain and ascorbic acid, the reducing equivalent of aluminium is 9, the reducing equivalent of zinc is 33, and the reducing equivalent of ascorbic acid is 88, so the reduction consumption of aluminium is much smaller than zinc and ascorbic acid, make the reducing agent cost far below zinc and ascorbic acid with the aluminium bits, utilize copper-containing etching waste solution can further reduce cost for the feedstock production copper powder.
Secondly, the configuration of surface of copper powder and structure are the key factors that influences copper powder electroplate and conductive capability, flake copper is flakey or flat, contact area between the powder strengthens, thereby flake copper can improve conductive capability, the compactness on flake copper surface and fineness influence the quality of silver coating, and the oxygen content of flake copper influences its conductive capability.
In addition, oxygen is that the catalyst that the galvanic cell reaction makes the oxidized generation pitting of copper takes place in the silver plating reaction process.
For achieving the above object, and take all factors into consideration above-mentioned factor, the invention provides a kind of preparation method of flake silver-plated copper powder, this method comprises the steps:
A, in the copper-containing etching waste solution raw material, add ammoniacal liquor regulator solution and ammonium chloride, making the acidity in the copper-containing etching waste solution raw material is 0.05～0.5mol/L, concentration is 5～15%, cupric concentration is 50～100g/L, under 50～100 ℃ of temperature stir, add the aluminium bits, reduction obtains amorphous copper powder, obtains clean copper powder through washing, centrifugal dehydration again;
B, copper powder and steel ball are packed in the ball grinder of planetary ball mill, and add lubricant, solder resist, complexing agent, oxygen scavenger, under vacuum condition, carried out ball milling 10-60 hour with planetary ball mill, with screen cloth ball is separated with copper powder then, obtain flake copper through washing, centrifugal dehydration again;
C, add wetting dispersing agent, complexing agent and reducing agent respectively in silver nitrate aqueous solution and in the copper powder water body, both obtain silver-plated copper powder at reaction, repeatedly wash the final vacuum drying with distilled water, organic solvent again and obtain product.
Among the step a, described copper-containing etching waste solution is printed circuit board industry etching waste liquor or the mantoquita that contains metal copper ion.
Among the step a, aluminium is 1～2: 1 with equivalent thickness of copper ratio.
Among the step b, the addition of described lubricant, solder resist, complexing agent, oxygen scavenger respectively is 1～5% of a copper powder weight, more particularly, described lubricant is nonionic or anion surfactant, as the APEO glycol ester, neopelex, content are 1% of copper powder weight; Described solder resist is one or more a mixture of polyethylene glycol, PVP, polyvinyl alcohol, polyacrylate, and content is 1% of copper powder weight; Described complexing agent is one or more a mixture of citrate, tartrate, triethanolamine, EDTA, pyrophosphate, and content is 2% of copper powder weight; The mixture of one or more that described oxygen scavenger is sodium sulfite, inferior sodium phosphate, N-isopropyl oxyammonia, substitute quinoline, nitrogen four replaces amine, content is 2% of copper powder weight.
Among the step b, the temperature that planetary ball mill carries out ball milling is 50～60 ℃ of constant temperature, ball grinder is 100～500 rev/mins around the speed of ball mill rotating disk revolution, 200～1000 rev/mins of the rotational velocities of ball grinder, the diameter of the used steel ball of ball milling is 5～5cm, ball and copper powder weight ratio are 10: 1～2, the tinning amount be the volume of ball and copper powder be not more than the ball grinder capacity 2/3, ball grinder is the stainless cylinder of steel that can carry out vacuum pumping.
Among the step c, the addition that adds the wetting dispersing agent of silver nitrate aqueous solution is 0.1～1% of a copper powder weight, and the addition of complexing agent and reducing agent respectively is 1～5% of a copper powder weight; The addition that adds the wetting dispersing agent of copper powder water body is 0.1～1% of a copper powder weight, and the addition of complexing agent and reducing agent respectively is 1～5% of a copper powder weight; The silver nitrate aqueous solution of adding additive is 1: 2 with the mixed proportion of the copper powder water body that adds additive.
Among the step c, described silver nitrate aqueous solution silver concentration is 10～50g/l, and silver-colored consumption is 5～20% of a copper powder weight.
Among the step c, described wetting dispersing agent is Tween 80, polyethylene glycol, polyxyethylated; Described complexing agent is one or more a mixture of citrate, tartrate, pyrophosphate, potassium rhodanide; Described reducing agent is one or more a mixture of inferior sodium phosphate, N-isopropyl oxyammonia, sodium hydrosulfite, potassium borohydride.
In technique scheme, for fineness that improves the flake copper surface and the oxygen content that reduces copper powder, the present invention adopts planetary ball mill to make flake copper, and its operation principle is on the circumference of rotating disc, is equipped with 4 not only with the rotating disk revolution but also do the ball grinder of high speed rotation.Doing revolution at ball grinder adds under the effect of high speed rotation, mill ball in the ball grinder forms high-speed tangent line friction to copper powder under the effect of inertia force, ball grinder vacuumizes simultaneously, add auxiliary agents such as lubricant, solder resist, complexing agent, oxygen scavenger in jar, the flake copper of making like this than before with general sand mill and ball grinder at oxygen barrier not and the flake copper do not made under the deoxygenation, have higher surface smoothness and lower oxygen content.Simultaneously, in order to suppress the galvanic cell reaction, the present invention has taked reaction vessel is vacuumized the technical measures of carrying out inert gas replacement, makes that reaction system is complete and oxygen is isolated.By in reaction solution, adding reducing agent, then full consumption the dissolved oxygen in the aqueous solution, and suppressed the oxidation of copper, promoted silver-colored reduction.
By above-mentioned technical scheme, the present invention has effectively overcome in the prior art such as damaging coating weight owing to galvanic cell reacts the discontinuous coating that forms erosion with holes, because the loose and porous structure of copper powder, surface irregularity and cause the not fine and close and plating leakage phenomenon of coating easily, and existing ball milling is produced flake copper technology and is caused oxidization of copper powder and cupric oxide to sneak into defectives such as inside easily.By selection and control to reaction density, acidity, temperature and additive, and the measure that suppresses the galvanic cell reaction such as vacuumize and adopt planetary ball mill to make the technology of flake copper, make the flake silver-plated copper powder of being produced have higher surface smoothness and lower oxygen content, and coating does not have pitting, electric conductivity is good, and silver content is lower.
[specific embodiment]
The following example is to further explanation of the present invention and explanation, and the present invention is not constituted any limitation.
Get 220 liters of acid copper-containing etching waste solutions (copper concentration 100 grams per liters), add ammoniacal liquor, add water to 500 liters to PH1, add 5 kilograms of sal-ammoniacs, be heated to 80 ℃, slowly add 6.4 kilograms of aluminium bits, stirred 1 hour, reaction obtains amorphous copper powder, and deionized water centrifuge washing copper powder is standby.
Get 1 kilogram of copper powder in 5 liters of vacuum ball grinders, add 5000 gram stainless steel balls, APEO glycol ester 10 grams, polyethylene glycol 10 grams, potassium citrate 20 grams, 400 milliliters in water, sodium sulfite 20 grams.Vacuumize in jar, obtained flake copper in 24 hours with 1000 rev/mins of ball millings of planetary ball mill.
Get 1 kilogram of flake copper in 20 liters of reactors, add 10 premium on currency, 1 gram tween, 20 gram potassium citrates, 20 gram N-isopropyl oxyammonias.Other joins (silver nitrate 157.5 grams, 5 premium on currency, 1 gram tween, the concentrated ammonia liquor of 100 grams 20%, 20 gram inferior sodium phosphate) solution is in feeder, whole reaction system sealing and isolate from outer air, vacuumize, filling with inert gas makes oxygen concentration be lower than 10ppm, silver nitrate adds in the reactor, stirred 1 hour, and obtained flake silver-plated copper powder, suction filtration, the washing of centrifugal, deionized water, absolute ethanol washing are three times in the oxygen barrier system, 80 ℃ of vacuum drying obtain the flake silver-plated copper powder product, and its technical performance sees Table 1.
Table 1 flake silver-plated copper powder product performance index
| Silver content | Copper content | Diameter D50 | Thickness μ m | Specific area m 2/g | Apparent density g/cm 3 |
| 10％ | 90％ | 10 | 0.5 | 1.5 | 0.85 |
Conducting performance test: get acrylic resin 25 grams, copper powder 75 grams add an amount of coupling agent, levelling agent, diluent, and stir and make electrically-conducting paint, 20 microns of the thickness of spraying, resistance is less than 0.5 ohm, and resistivity is less than 1 * 10
-4Ohm. centimetre.
Claims (10)
1, a kind of preparation method of flake silver-plated copper powder is characterized in that, it comprises the steps:
A, in the copper-containing etching waste solution raw material, add ammoniacal liquor regulator solution and ammonium chloride, making the acidity in the copper-containing etching waste solution raw material is 0.05～0.5mol/L, concentration is 5～15%, cupric concentration is 50～100g/L, under 50～100 ℃ of temperature stir, add the aluminium bits, reduction obtains amorphous copper powder, obtains clean copper powder through washing, centrifugal dehydration again;
B, copper powder and steel ball are packed in the ball grinder of planetary ball mill, and add lubricant, solder resist, complexing agent, oxygen scavenger, under vacuum condition, carried out ball milling 10-60 hour with planetary ball mill, with screen cloth ball is separated with copper powder then, obtain flake copper through washing, centrifugal dehydration again;
C, add wetting dispersing agent, complexing agent and reducing agent respectively in silver nitrate aqueous solution and in the copper powder water body, both obtain silver-plated copper powder at reaction, repeatedly wash the final vacuum drying with distilled water, organic solvent again and obtain product.
2, the method for claim 1 is characterized in that, in the step (a), described copper-containing etching waste solution is printed circuit board industry etching waste liquor or the mantoquita that contains metal copper ion.
3, the method for claim 1 is characterized in that, in the step (a), aluminium is 1～2: 1 with equivalent thickness of copper ratio.
4, the method for claim 1 is characterized in that, in the step (b), the addition of described lubricant, solder resist, complexing agent, oxygen scavenger respectively is 1～5% of a copper powder weight.
5, method as claimed in claim 4, it is characterized in that in the step (b), the temperature that planetary ball mill carries out ball milling is 50～60 ℃ of constant temperature, ball grinder is 100～500 rev/mins around the speed of ball mill rotating disk revolution, 200～1000 rev/mins of the rotational velocities of ball grinder.
6, method as claimed in claim 5 is characterized in that, in the step (b), the diameter of the used steel ball of ball milling is 5～5cm, ball and copper powder weight ratio are 10: 1～2, the tinning amount be the volume of ball and copper powder be not more than the ball grinder capacity 2/3, ball grinder is the stainless cylinder of steel that can carry out vacuum pumping.
7, method as claimed in claim 6 is characterized in that, in the step (b), described lubricant is nonionic or anion surfactant; Described solder resist is one or more a mixture of polyethylene glycol, PVP, polyvinyl alcohol, polyacrylate; Described complexing agent is one or more a mixture of citrate, tartrate, triethanolamine, EDTA, pyrophosphate; The mixture of one or more that described oxygen scavenger is sodium sulfite, inferior sodium phosphate, N-isopropyl oxyammonia, substitute quinoline, nitrogen four replaces amine.
8, the method for claim 1 is characterized in that, in the step (c), the addition that adds the wetting dispersing agent of silver nitrate aqueous solution is 0.1～1% of a copper powder weight, and the addition of complexing agent and reducing agent respectively is 1～5% of a copper powder weight; The addition that adds the wetting dispersing agent of copper powder water body is 0.1～1% of a copper powder weight, and the addition of complexing agent and reducing agent respectively is 1～5% of a copper powder weight; The silver nitrate aqueous solution of adding additive is 1: 2 with the mixed proportion of the copper powder water body that adds additive.
9, the method for claim 1 is characterized in that, in the step (c), described silver nitrate aqueous solution silver concentration is 10～50g/l, and silver-colored consumption is 5～20% of a copper powder weight.
10, method as claimed in claim 9 is characterized in that, in the step (c), described wetting dispersing agent is Tween 80, polyethylene glycol, polyxyethylated; Described complexing agent is one or more a mixture of citrate, tartrate, pyrophosphate, potassium rhodanide; Described reducing agent is one or more a mixture of inferior sodium phosphate, N-isopropyl oxyammonia, sodium hydrosulfite, potassium borohydride.
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