CN103619129B - A kind of method of inkjet printing copper conductive traces - Google Patents
A kind of method of inkjet printing copper conductive traces Download PDFInfo
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- CN103619129B CN103619129B CN201310606821.5A CN201310606821A CN103619129B CN 103619129 B CN103619129 B CN 103619129B CN 201310606821 A CN201310606821 A CN 201310606821A CN 103619129 B CN103619129 B CN 103619129B
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- inkjet printing
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Abstract
A kind of method that the invention discloses inkjet printing copper conductive traces, using low-solid content and low viscous nano silver conductive ink as activator, inkjet printing, on matrix, is treated that ink marks carries out electroless copper the most again, is finally given copper conductive traces.The nano silver conductive ink viscosity that preparation method of the present invention is used is low, and particle diameter is little, favorable dispersibility, common ink-jet printer can be used to print, do not block jet orifice；Nano-Ag particles consumption is the least, low production cost；And without carrying out high temperature sintering after this method making wiring board inkjet printing, to stock matrix without heatproof requirement, significantly expanded the range of application of nano metal inkjet technology.
Description
Technical field
The present invention relates to wiring board and manufacture field, a kind of method particularly relating to inkjet printing copper conductive traces.
Background technology
By the inkjet printing printed circuit board (PCB) (Printed Circuit Board, PCB) of nano metal conductive ink
Printed electronic (Printed Electronics) technology bring revolution to modern electronics industry.This addition
Method production technology is not only simple and environmentally-friendly, efficient than traditional photoengraving subtractive process technique, and can realize close
Collection wiring, makes electronic product be more easy to miniaturization, or more frivolous.It can realize circuit layout card from CAD
Design drawing to the flexible continuous prodution of " What You See Is What You Get " formula of product, make the manufacture of PCB become as
As office's mimeograph documents easily.
Conventional nano metal conductive ink is Jin Mo, silver inks and copper ink.Nanometer gold or silver in Jin Mo, silver inks
Granule is relatively fine, and chemical property is the most more stable, is difficult to oxidized, is relatively easily disperseed, but valency is expensive.
Copper is inexpensive, and weldability is good, without ion migration phenomenon, additionally, the electric property of copper conductor is good, and thermal conductivity
Height, intermetallic compound growth rate is slow, is preferable circuit board conductive metal.But copper chemical property is relatively active,
Specific surface energy is big, and nano-particle is oxidizable, and particle diameter is the biggest, it is more difficult to dispersion, causes ink free settling, stifled
Plug jet orifice.
Golden ink, silver inks or copper ink, in order to make nano-particle can be linked to be line after ensureing inkjet printing and sintering,
Must have certain nano metal content in conductive ink, usual solid content need to be about 30%.Due to gold,
Silver, copper proportion are relatively big, for preventing nano metal from assembling and sedimentation, need add surfactant and need in ink
Increase viscosity.High viscosity adds the difficulty of ink-jet, needs special industrial inkjet to fill during printing.Nanometer
Metal line to be linked to be, and there is higher electrical conductivity simultaneously, it is necessary for being sintered, makes nano-metal particle
Reguline metal is connected into by diffusion.This process that " metallizes " is generally the temperature range of 220～350 DEG C
Carrying out, this just requires that stock or matrix material must heatproofs.But, some is applied, as at thing
In order to substitute the FRID antenna of bar code in popular industry, need to be printed upon circuit the plastics of common not heatproof
On packing box, now matrix heatproof has just become the restraining factors that technology is applied.
Summary of the invention
A kind of method that it is an object of the invention to provide inkjet printing copper conductive traces plate, to solve existing skill
Art ink inside sedimentation blocking jet orifice, sinters temperature required too high problem.
The present invention realizes above-mentioned purpose and be employed technical scheme comprise that a kind of inkjet printing copper conductive traces of offer
Plate, comprises the following steps: nano silver conductive ink described in inkjet printing on matrix, is dried to obtain conducting wire
Plate；Described conducting wire plate carries out electroless copper.
Further, described nano silver conductive ink includes nano-Ag particles, dispersant and solvent；Described receive
The mass fraction of rice Argent grain is 0.5～5wt%, and viscosity is 1.2～2.0 centipoises, and mean diameter is 50nm；
Further, described chemical bronze plating liquid includes: mantoquita, chelating agent, reducing agent, stabilizer, pH adjust
Joint agent.
Further, described mantoquita is copper sulfate or copper sulphate pentahydrate.
Further, described chelating agent is disodiumedetate.
Further, described reducing agent is formaldehyde.
Further, described stabilizer is α-α ' bipyridyl.
Further, described pH adjusting agent is sodium hydroxide or sodium tetraborate decahydrate.
Further, described chemical bronze plating liquid every liter includes: copper sulphate pentahydrate 2～20g, ethylenediamine tetrem
Acid disodium 5～35g, formaldehyde 5～30ml, α-α ' bipyridyl 0.01～0.05g, potassium ferrocyanide 0.01～0.10
G and deionized water.
Further, the technique of described electroless copper is: with 0.5～6M NaOH aqueous solution by the pH of plating solution
Value is adjusted to 11～14, is warming up to 35～70 DEG C, adds reducing agent, and the time of electroless copper is 2～30 minutes.
The beneficial effects of the present invention is: the nano silver conductive ink viscosity used is low, and particle diameter is little, dispersion
Property good, common ink-jet printer can be used to print, not block jet orifice；After making wiring board inkjet printing
Without carrying out high temperature sintering, to stock matrix without heatproof requirement, significantly expand nano metal inkjet printing
The range of application of technology；And nano-Ag particles consumption is the least, low production cost.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the sample after the embodiment of the present invention 1 inkjet printing；
Fig. 2 is the pictorial diagram of the sample after the embodiment of the present invention 1 copper facing；
Fig. 3 is the scanning electron microscope (SEM) photograph of the sample after the embodiment of the present invention 1 copper facing；
Fig. 4 is the sectional view of copper conductive traces plate obtained by the embodiment of the present invention 1.
Detailed description of the invention
In order to make the technical problem to be solved, technical scheme and beneficial effect clearer,
Below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that this place is retouched
The specific embodiment stated only in order to explain the present invention, is not intended to limit the present invention.
The present invention provides a kind of inkjet printing copper conductive traces plate, comprises the following steps: on matrix, ink-jet is beaten
Print described nano silver conductive ink, be dried to obtain conducting wire plate；Described conducting wire plate carries out chemical plating
Copper.
Specifically, nano silver conductive ink includes nano-Ag particles, dispersant and solvent, and viscosity is 1.2～2.0
Centipoise, pH value is 7～9.Wherein, the mean diameter of nano-Ag particles is 50nm, and mass fraction is 0.5
～5wt%；Dispersant can promote Argent grain to be dispersed in medium formation stable suspension, and dispersant is preferred
Polyvinylpyrrolidone (PVP)；Solvent is water and alcohol mixture, water and the preferred 1:0 of volume ratio of ethanol
～2.Gained nano silver conductive ink is the mixed liquor low containing fine particle, favorable dispersibility and viscosity, Gu
Body agent particle size is much smaller than normal printer ink-jet aperture, does not block jet orifice.
Specifically, chemical bronze plating liquid includes: mantoquita, chelating agent, reducing agent, stabilizer, PH regulator.
Wherein, mantoquita is copper sulfate, copper chloride, basic copper carbonate, cupric tartrate, Schweinfurt green or their hydration
Thing, preferably sulfuric acid copper or copper sulphate pentahydrate；Chelating agent can be sodium potassium tartrate tetrahydrate, sodium citrate, glucose
Acid sodium, triethanolamine, tetrahydroxypropyl ethylenediamine, glycerol, glycolic acid, ethylenediaminetetraacetic acid (EDTA),
At least one in disodiumedetate (EDTA-2Na), sodium potassium tartrate tetrahydrate, potassium ferrocyanide,
Preferably EDTA-2Na；Reducing agent can be formaldehyde, sodium hypophosphite, sodium borohydride, dimethylamino borine,
At least one in hydrazine, preferably formaldehyde；Stabilizer selected from methanol, Cyanogran., thio urea, alkyl hydrosulfide,
At least one in dihydroxy pyridine, α-α ' bipyridyl, preferably α-α ' bipyridyl.PH adjusting agent can be hydrogen
At least one in sodium oxide, potassium hydroxide, sodium carbonate, sodium tetraborate decahydrate, preferably sodium hydroxide or ten
Water sodium tetraborate.
Preferably, selecting copper sulfate or copper sulphate pentahydrate is mantoquita, and EDTA-2Na is chelating agent, and formaldehyde is
Reducing agent, α-α ' bipyridyl be stabilizer, sodium hydroxide or sodium tetraborate decahydrate be PH regulator, it is thus achieved that
Electroless copper circuit is bright, fine and close, and electrical conductivity is high.
Further, the optimization formula of chemical bronze plating liquid is: every liter of copper plating bath includes: copper sulphate pentahydrate 2～20
G, disodiumedetate 5～35g, formaldehyde 5～30ml, α-α ' bipyridyl 0.01～0.05g, ferrous cyanogen
Change potassium 0.01～0.10g and deionized water.
The technique of electroless copper is: with 0.5～6M NaOH aqueous solution, the pH value of plating solution is adjusted to 11～14,
Being warming up to 35-70 DEG C, add reducing agent, the time of electroless copper is 2～30 minutes.
Without being sintered in preparation process of the present invention.Sintering is that a Nanometer Copper " metallizes " process, logical
Often the temperature range at 220～350 DEG C is carried out, and this just requires that stock or matrix material must heatproofs.So
And, for some apply, as in logistic industry in order to substitute the FRID antenna of bar code, need by electricity
Road is printed upon on the plastic packing box of common the most not heatproof, now matrix heatproof just become restriction that technology applies because of
Element.The present invention, without sintering, has expanded range of application significantly.
Method inkjet printing copper conductive traces plate of the present invention being described below by way of specific embodiment.
Embodiment 1
Step 1: the inkjet printing of nano silver conductive ink.Being 1.8 centipoises by viscosity, argent solid content is
6g/100ml, nanometer metallic silver mean diameter is about 50nm, and dispersant is polyvinylpyrrolidone (PVP)
K88-96, solvent is water and ethanol volume ratio is the mixture of 1:0.5, and pH value is the nanometer metallic silver of 8
Conductive ink injects in the print cartridge of HP-D2600 type (jet orifice diameter 5 μm) common ink-jet printer,
Print Back Word type testing conductive circuit on polyimide film matrix, treat that ink marks is dried, electron micrograph
Print ink marks, as shown in Figure 1.
Step 2: stamping ink mark is carried out electroless copper.Preparation electroless copper plating solution: weigh 15g
CuSO4·5H2O, 30g EDTA-2Na, 0.03g α-α ' bipyridyl, 0.08g potassium ferrocyanide, 20ml
37wt%HCHO aqueous solution, puts in glass container, adds a small amount of deionized water dissolving, is configured to solution,
Adding deionized water again and be settled to 1L, dropping 5M NaOH aqueous solution regulation pH value is to 12.5.Ink-jet is beaten
The testing conductive circuit of print is immersed in joined plating solution, is warming up to 50 DEG C, then drips 37wt% formalin
Make reducing agent, carry out electroless copper 7 minutes.
Copper test conducting wire after electroless copper is as shown in accompanying drawing 2～4, it is thus achieved that electroless copper circuit light,
Densification, electrical conductivity is high, and it is 5.94 × 10 that four probe method records the resistivity of its copper conductive traces-4Ω·cm。
Embodiment 2
Step 1: the inkjet printing of nano silver conductive ink.Being 1.8 centipoises by viscosity, argent solid content is
1g/100ml, nanometer metallic silver mean diameter is about 20nm, and dispersant is polyvinylpyrrolidone (PVP)
K88-96 Yu OP-10 mass fraction is the mixture of 3:5, and solvent is water and ethanol volume ratio is 1:1's
Mixture, pH value be 8 nanometer metallic silver conductive ink inject Fuji Dimatix type (jet orifice diameter
1 μm) ink-jet printer print cartridge in, on polyimide film matrix print Back Word type testing conductive circuit,
Treating that ink marks is dried, electron micrograph prints ink marks.
Step 2: stamping ink mark is carried out electroless copper.Preparation electroless copper plating solution: weigh 15g
CuSO4·5H2O, 35g sodium citrate, 0.04g dihydroxy pyridine, 0.08g potassium ferrocyanide, 5ml water
Close hydrazine, put in glass container, add a small amount of deionized water dissolving, be configured to solution, then it is fixed to add deionized water
Holding to 1L, dropping 1M sodium tetraborate decahydrate aqueous solution regulation pH value is to 12.0.By the test of inkjet printing
Conducting wire is immersed in joined plating solution, is warming up to 50 DEG C, then drips 10wt% hydrazine hydrate aqueous solution and go back
Former dose, carry out electroless copper 7 minutes.
After four probe method records electroless copper, the resistivity of copper conductive traces is 7.16 × 10-4Ω·cm。
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all at this
Any amendment, equivalent and the improvement etc. made within bright spirit and principle, should be included in the present invention
Protection domain within.
Claims (10)
1. the method for an inkjet printing copper conductive traces, it is characterised in that comprise the following steps: at matrix
Upper inkjet printing nano silver conductive ink, is dried to obtain conducting wire plate；Utilize chemical bronze plating liquid in described conduction
Electroless copper is carried out on wiring board；Described nano silver conductive ink is stable suspension, including nano-Ag particles,
The mass fraction of described nano-Ag particles is 0.5～5wt%.
Method the most according to claim 1, it is characterised in that described nano silver conductive ink includes receiving
Rice Argent grain, dispersant and solvent；The mass fraction of described nano-Ag particles is 0.5～5wt%, and viscosity is
1.2～2.0 centipoises, mean diameter is 50nm.
Method the most according to claim 1, it is characterised in that described chemical bronze plating liquid includes: mantoquita,
Chelating agent, reducing agent, stabilizer, pH adjusting agent.
The method of inkjet printing copper conductive traces the most according to claim 3, it is characterised in that described
Mantoquita is copper sulfate or copper sulphate pentahydrate.
The method of inkjet printing copper conductive traces the most according to claim 3, it is characterised in that described
Chelating agent is disodiumedetate.
The method of inkjet printing copper conductive traces the most according to claim 3, it is characterised in that described
Reducing agent is formaldehyde.
The method of inkjet printing copper conductive traces the most according to claim 3, it is characterised in that described
Stabilizer is α-α ' bipyridyl.
The method of inkjet printing copper conductive traces the most according to claim 3, it is characterised in that described
PH adjusting agent is sodium hydroxide or sodium tetraborate decahydrate.
The method of inkjet printing copper conductive traces the most according to claim 1, it is characterised in that described
Chemical bronze plating liquid every liter includes: copper sulphate pentahydrate 2～20g, disodiumedetate 5～35g,
Formaldehyde 5～30ml, α-α ' bipyridyl 0.01～0.05g, potassium ferrocyanide 0.01～0.10g
And deionized water.
The method of inkjet printing copper conductive traces the most according to claim 1, it is characterised in that described
The technique of electroless copper is: with 0.5～6M NaOH aqueous solution, the pH value of plating solution is adjusted to 11～14, rises
Temperature, to 35～70 DEG C, adds reducing agent, and the time of electroless copper is 2～30 minutes.
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| CN103820773A (en) * | 2014-03-11 | 2014-05-28 | 上海贺鸿电子有限公司 | Solution used for laser antenna LDS plated copper and use method of solution |
| CN106148923B (en) * | 2016-08-16 | 2018-12-11 | 无锡益联机械有限公司 | A kind of surface treatment method of radial tyre bead steel wire |
| CN107072039A (en) * | 2016-12-23 | 2017-08-18 | 中国科学院深圳先进技术研究院 | The method for preparing conducting wire |
| CN107466167B (en) * | 2017-08-10 | 2020-06-12 | 上海幂方电子科技有限公司 | Method for preparing flexible printed multilayer circuit board by ink-jet printing |
| CN108081781B (en) * | 2017-12-14 | 2019-05-21 | 湖南兴威新材料有限公司 | The method for improving inkjet printing film forming thickness |
| US11237103B2 (en) | 2018-05-31 | 2022-02-01 | Socovar Sec | Electronic device testing system, electronic device production system including same and method of testing an electronic device |
| CN110876255A (en) * | 2018-08-31 | 2020-03-10 | 德州迈特新材料研究中心 | Preparation technology of microwave band metamaterial wave absorber |
| CN110983763A (en) * | 2019-12-18 | 2020-04-10 | 浙江蓝天制衣有限公司 | Chemical copper plating process suitable for clothing cotton fabric |
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| KR101140270B1 (en) * | 2008-12-10 | 2012-04-26 | 엘에스전선 주식회사 | Electroconductive silver nano particle composite, ink and method for preparing the same |
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| CN101754585A (en) * | 2008-11-27 | 2010-06-23 | 富葵精密组件(深圳)有限公司 | Method for manufacturing conductive circuit |
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