CN104575671A - Ultraviolet-cured polyurethane-based conductive silver paste and preparation method thereof - Google Patents
Ultraviolet-cured polyurethane-based conductive silver paste and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an ultraviolet-cured polyurethane-based conductive silver paste and a preparation method thereof. The preparation method comprises the following steps: heating an active monomer to 40-60 DEG C, dissolving a photoinitiator in the active monomer, cooling to 20-35 DEG C, mixing the active monomer with superfine spherical silver, after ultrasonic dispersion, sequentially adding a polyurethane prepolymer and flake-like silver powder, stirring and grinding to obtain conductive silver paste, wherein the conductivity of the ultraviolet-cured silver paste is 7.59*10<5>S/m to 1.32*10<6>S/m, and the conductivity of the ultraviolet-cured silver paste is still 7.82*10<4>S/m to 3.38*10<5>S/m after a bending test is performed for ten times. The ultraviolet-cured polyurethane-based conductive silver paste prepared by adopting the preparation method is high in conductivity, excellent in flexibility, strong in adhesive force to a polyethylene glycol terephthalate base material, and less in dosage of the photoinitiator, and can be widely applied to flexible printed circuits such as a keyboard, a mobile phone, a flat computer and a digital camera.
Description
Technical field
The present invention relates to electronic chemical product field, particularly relate to a kind of ultraviolet curing urethane base conductive silver paste and preparation method thereof.
Background technology
Along with the fast development of electronic information technology, electronic equipment constantly strides forward towards the direction of microminiaturized, intelligent, environmental protection and low cost, impels people constantly to study, develops and apply the manufacturing technologies such as more advanced inexpensive electronic circuit board, electronic devices and components.Full printed electronics technology is a kind of Novel electronic product manufacturing technology, it utilizes typographic advantage, electronic equipment is fabricated into the organic combinations such as the encapsulation of components and parts from element manufacture, circuit, thus can more efficiently, more produce to environmental protection the electronic product of high-performance, low cost, there is very wide application prospect.And conductive silver paste is as one of material the most key in full printed electronics technical field, cause showing great attention to of industrial quarters and academia.It is hot curing that conventional conductive silver starches the curing mode taked, curing time is long, energy consumption is high, reduce the efficiency of suitability for industrialized production, and UV-curing technology has economy, energy-conservation, solidification rate fast and advantages of environment protection, UV-curing technology is applied to conductive silver paste and not only can accelerates curing rate, and the resolution of printed conductor can be improved.Therefore, ultraviolet light polymerization conductive silver paste is that silver most with prospects at present one of is starched, and becomes the development new direction of conductive silver paste.
At present, existing pertinent literature is reported ultraviolet light polymerization conductive silver paste both at home and abroad, Chinese invention patent CN201110114617.2 discloses a kind of preparation method of ultraviolet light polymerization conductive silver paste, and this silver slurry composition includes silver powder, Conductive inorganic ceramic powder, glass dust, photosensitive resin, activated monomer, light trigger and auxiliary agent.This invention improves the conductivity (solidification sintering after conductive phase content be 89wt%) of silver slurry after solidification sintering by increasing conductive phase (silver powder and Conductive inorganic ceramic powder) content, most high conductivity can reach 5.00 ╳ 10
7s/m, and silver slurry is good with base material adhesive force.But, the light trigger consumption of this invention up to 3wt% ~ 8wt%, because silver-colored slurry system is light tight, solidification energy is high, and in this invention, solvent, up to more than 10wt%, needs high temperature drying before using, still need 520 DEG C of high temperature sintering 20min after solidification, operation is numerous and diverse.Chinese invention patent CN200810167513.6 discloses a kind of ultraviolet light polymerization conductive silver paste making RFID antenna, this silver slurry composition include silver powder, photosensitive resin, activated monomer, light trigger, auxiliary agent and solvent, can on the base materials such as paper substrates, PETG (PET), polyimides (PI), polyvinyl chloride (PVC) the various picture and text of silk screen printing; When silver powder content is 65wt%, most high conductivity reaches 1.19 ╳ 10
6s/m, but photoinitiator levels is up to 3wt%, and the ethyl acetate solvent containing 1wt% ~ 10wt%.US Patent No. 8784697B2 discloses a kind of touch-screen ultraviolet light polymerization conductive silver paste, this silver slurry printing performance is good, with PET base material, there is good adhesive force, its composition includes silver powder, polyester acrylic ester prepolymer, hydroxy-ethyl acrylate, polyvinylpyrrolidone (PVP) and light trigger, wherein dispersant PVP can improve the dispersiveness of silver powder in silver slurry effectively, make printed conductor width error < 10%, but because silver powder surface is covered by insulation PVP, when silver powder content is 75wt%, the most high conductivity of silver slurry is only 1.67 ╳ 10
5s/m.Domestic scholars Jiang Bin (the research and apply of low-temperature cured conductive silver slurry, East China University of Science's master thesis in 2012) then prepare the polyurethane-base conductive silver paste of hot curing, be 69.0wt% at silver powder content, the conductivity of silver slurry is only 6.67 ╳ 10
5s/m, could obtain good resistance to bending performance under high silver powder content.
Summary of the invention
The shortcoming that object of the present invention exists for existing ultraviolet light polymerization conductive silver paste, provides high-performance ultraviolet cured polyurethane-base conductive silver paste that a kind of conductivity is high, pliability good, light trigger consumption is low and preparation method thereof.
The present invention selects self-control high-flexibility polyurethane prepolymer, composite as organic phase with the activated monomer HDDA (solidifying post-shrinkage ratio is 18%) of high shrinkage, adopt ultra-fine ball silver/flake silver powder composite as conductive phase simultaneously, under keeping silver slurry to have the prerequisite of excellent mechanical performances, starch the shrinkage after solidifying by improving silver and adopt ultra-fine ball silver to be filled in the space of flake silver powder, define good conductive network, be 65.0wt% at silver powder content, when light trigger consumption is only 1.0wt%, silver slurry conductivity is up to 1.32 ╳ 10
6s/m, after 10 bending tests, conductivity is still 3.38 ╳ 10
5s/m.
Object of the present invention is achieved through the following technical solutions.
A kind of preparation method of ultraviolet curing urethane base conductive silver paste, it is characterized in that: after activated monomer being warming up to 40 DEG C ~ 60 DEG C, light trigger is dissolved in activated monomer, be cooled to 20 DEG C ~ 35 DEG C, mix with ultra-fine ball silver, after ultrasonic wave dispersion, add polyurethane prepolymer and flake silver powder successively, after stirring, grinding, obtain described conductive silver paste;
The particle diameter of described flake silver powder is 3 μm ~ 10 μm; Preferred model is TL-187, is produced by Dongguan Betely New Materials Co., Ltd.;
The particle diameter of described ultra-fine ball silver is 100nm ~ 400nm, and its preparation method comprises the steps:
1) by polyvinylpyrrolidone (PVP), softex kw (CTAB) and dissolution of ascorbic acid in deionized water, be configured to reducing solution, by NaOH regulate reaction pH be 12 ~ 12.5;
2) by silver nitrate (AgNO
3) to be dissolved in deionized water and to be diluted to 0.5 ~ 1.0mol/L, under the mixing speed of 200r/min ~ 500r/min, controlling reaction temperature is 0 DEG C ~ 50 DEG C, silver nitrate aqueous solution is dropped in reducing solution, wherein time for adding is 10min ~ 30min, is added dropwise to complete rear continuation reaction 20min ~ 60min;
3) reacted suspension centrifuge is isolated ultra-fine ball silver, then by the washing of deionized water, absolute ethyl alcohol and acetone;
4) by the ultra-fine ball silver after washed at drying under reduced pressure;
The mol ratio of described ascorbic acid and silver nitrate is 1:1; The mass ratio of described polyvinylpyrrolidone and silver nitrate is 1:1 ~ 4:1, and the mass ratio of described softex kw and silver nitrate is 1:34 ~ 1:34;
Described polyurethane prepolymer is self-control end-vinyl polyurethane prepolymer, by toluene di-isocyanate(TDI) (TDI), polyethylene glycol (PEG) and hydroxyethyl methacrylate (HEMA) reaction obtain, its preparation method is as follows: dropwise instilled in toluene di-isocyanate(TDI) by polyethylene glycol, reaction temperature is 30 DEG C ~ 50 DEG C, time for adding is 1h ~ 2h, be added dropwise to complete rear continuation reaction 1 ~ 2h, be warming up to 60 DEG C ~ 80 DEG C subsequently, add disposable for the hydroxyethyl methacrylate being dissolved with dibutyl tin laurate, continue reaction 2h ~ 3h, discharging while hot, keep in Dark Place, the mol ratio of described polyethylene glycol, toluene di-isocyanate(TDI) and hydroxyethyl methacrylate is 1:2:1 ~ 1:2:1.05, the mass ratio of described dibutyl tin laurate and toluene di-isocyanate(TDI) is 1:348 ~ 1:116, the structural formula of polyurethane prepolymer is shown below,
Wherein n=6 ~ 15;
Described activated monomer is 1-6 hexylene glycol double methacrylate (HDDA) and/or NVP (NVP), and its molecular structural formula is as follows respectively:
Described light trigger is two (2,4, the 6-trimethylbenzoyl) phosphine oxide (819) of 2-isopropyl thioxanthone (ITX) and phenyl, and its molecular structural formula is as follows;
For realizing the object of the invention further, preferably, raw material consists of
Preferably, the mass ratio 1:9 ~ 1:19 of described ultra-fine ball silver and flake silver powder.
Preferably, the mass ratio 1:1 ~ 1:1.5 of described activated monomer and polyurethane prepolymer.
Preferably, described light trigger ITX and the mass ratio 1:1 ~ 1:1.5 of light trigger 819.
Preferably, the gross mass of described polyurethane prepolymer and activated monomer and the total mass ratio 1:1.5 ~ 1:2.0 of silver powder.
Preferably, described polyethylene glycol is first at 80 DEG C ~ 100 DEG C decompression distillation 1 ~ 2h before using; Adopt anhydrous calcium chloride dry before described hydroxyethyl methacrylate uses.
Described centrifugation isolates ultra-fine ball silver with centrifuge in the centrifugal 10min ~ 30min of 8000r/min ~ 10000r/min; The number of times of described washing is 2 ~ 4 times; Described drying under reduced pressure is at 30 DEG C ~ 50 DEG C drying under reduced pressure 24h ~ 48h by the ultra-fine ball silver after washed.
A kind of ultraviolet curing urethane base conductive silver paste, is obtained by above-mentioned preparation method.The conductivity of described ultraviolet light polymerization silver slurry is 7.59 ╳ 10
5s/m ~ 1.32 ╳ 10
6s/m (silver powder content is 65.0wt%), after 10 bending tests, conductivity is still 7.82 ╳ 10
4s/m ~ 3.38 ╳ 10
5s/m.
Compared with prior art, ultraviolet curing urethane base conductive silver paste of the present invention and technology of preparing thereof have the following advantages:
1) adopt the activated monomer HDDA of the rear high shrinkage of the end-vinyl polyurethane prepolymer of high-flexibility and solidification as organic adhesive phase, the ultraviolet light polymerization silver slurry of the high comprehensive performances such as high connductivity, high adhesion force and Gao Nai bending can be obtained.
2) adopt deep layer quick-setting light trigger 819 and surface quick-setting light trigger ITX composite, can rapid curing when light trigger addition is less, have broad application prospects.
3) using flake silver powder and ultra-fine ball silver composite as conductive phase, ultra-fine ball silver can be filled in flake silver powder gap, to the formation of conductive path serve linking and supplementary function, can effectively improve silver slurry conductivity.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction spectrogram that embodiment 1 prepares ultra-fine ball silver;
Fig. 2 is the infrared spectrum of embodiment 1 polyurethane preformed polymer;
Fig. 3 is the infrared spectrum of embodiment 4 polyurethane preformed polymer.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but embodiments of the invention are not limited to this.
Embodiment 1
Prepare ultraviolet curing urethane base conductive silver paste according to the following formulation:
(1) preparation of ultra-fine ball silver: by 1.70gPVP, 0.50gCTAB and 1.76g dissolution of ascorbic acid in deionized water, adds NaOH simultaneously and regulates pH to be 12.5, prepare the reducing solution of 50ml; By 1.70g AgNO
3to be dissolved in deionized water and to be diluted to 1.0mol/L, by AgNO under 300r/min rotating speed
3drop in reducing solution, control time for adding is 20min, and reaction temperature is 30 DEG C, is added dropwise to complete rear continuation reaction 30min; By reacted suspension centrifuge (high speed tabletop centrifuge: GT10-1, Beijing epoch Bei Li centrifuge Co., Ltd) in the centrifugal 30min of 10000r/min, centrifugal product uses deionized water, absolute ethyl alcohol and acetone respectively to wash once; By the ultra-fine ball silver after washed at 30 DEG C, dry 48h under 0.1mmHg, prepare ultra-fine ball silver powder for subsequent use, detect (BI-90PLUS, Brookhaven company of the U.S.) through laser nano Particle Size Analyzer, the average grain diameter of obtained ultra-fine ball silver is 135nm.Fig. 1 is the X-ray diffraction spectrogram of this ultra-fine ball silver, inquire about through PDF card, 2 θ values are 38.10 °, 44.09 °, 64.36 °, 77.29 °, 81.31 °, correspond respectively to (111), (200), (220) of silver-colored crystal, (311), (222) crystal face, prove that this pressed powder is pure silver powder.
(2) preparation of polyurethane prepolymer: before reaction starts to PEG-400 (molecular weight is the PEG of 400) at 80 DEG C, decompression distillation 1h under 0.1mmHg, be warming up to 100 DEG C subsequently, decompression distillation 1h under 0.1mmHg; HEMA then adopts anhydrous calcium chloride dry before using; In the four-hole boiling flask of 150ml, add the TDI of 0.100mol, when temperature constant is at 40 DEG C, dropwise instilled in four-hole boiling flask by the PEG-400 of 0.050mol, time for adding is 1h, continues reaction 2h; Be warming up to 70 DEG C subsequently, add disposable for the HEMA of the 0.051mol being dissolved with 0.15gDBTDL, reaction 3h discharging while hot, keeps in Dark Place, prepares polyurethane prepolymer for subsequent use.Fig. 2 is the infrared spectrum of polyurethane preformed polymer, 1600cm
-1for the absorption vibration peak of carbon-carbon double bond-C=C, 1735cm
-1for the absorption vibration peak of ester group-C=O, 3200-3700cm
-1for-NH absorbs vibration peak, 2280cm
-1place is substantially without absworption peak, and the OH complete reaction of NCO completely and in PEG-400 and HEMA in TDI is described, product is the end-vinyl polyurethane acrylate prepolymer of two degrees of functionality.
(3) preparation of ultraviolet curing urethane base conductive silver paste: first HDDA is warming up to 50 DEG C, then light trigger ITX and 819 is dissolved in HDDA, to be cooled to after 30 DEG C, add ultra-fine ball silver, through ultrasonic wave dispersion 1h (Kunshan City, Jiangsu Province Shu Mei ultrasonic cleaner KQ218, supersonic frequency is 40kHz), (particle diameter is 3 μm ~ 10 μm to add polyurethane prepolymer and flake silver powder subsequently, model is TL-187, produced by Dongguan Betely New Materials Co., Ltd.), high speed dispersor is used to stir the mixture 20min in 800r/min, and then three roller dispersion machine grinding 5min are adopted, obtain ultraviolet curing urethane base conductive silver paste, (PET film is thick is approximately 50 μm to adopt screen process press slurry to be printed onto PET film, printing before with absolute ethyl alcohol wiping and dry) on, subsequently by uv cure machine (Co., Ltd Fusion UV S300 in Spectris, uviol lamp power is 4000W, wavelength is 365nm) solidify 30s, after solidification, silver slurry thickness is 10 ~ 15 μm.Sample performance is as shown in table 1.
As can be seen from Table 1, when total silver powder content is 65.0wt%, when wherein ultra-fine ball silver content is 3.3wt%, after solidification, the conductivity of silver slurry is 7.19 ╳ 10
5s/m, the conductivity after 10 bendings is still 7.82 ╳ 10
4s/m, has good adhesive force with PET base material, and its hundred lattice test grade reaches 5B rank; And to add separately the conductivity that flake silver powder starches as the silver of conductive phase (comparative example 1) be 4.02 ╳ 10
5s/m, the conductivity after 10 bendings is 5.75 ╳ 10
4s/m, shows to carry out using ultra-fine ball silver/flake silver powder conductivity that the composite silver as conductive phase starches and the silver that resistance to bending performance will obviously be better than using independent sheet silver powder as conductive phase is starched.
Embodiment 2
Prepare ultraviolet curing urethane base conductive silver paste according to the following formulation:
(1) preparation of ultra-fine ball silver: by 1.70gPVP, 0.50gCTAB and 1.76g dissolution of ascorbic acid in deionized water, adds NaOH simultaneously and regulates pH to be 12.5, prepare the reducing solution of 50ml; By 1.70gAgNO
3to be dissolved in deionized water and to be diluted to 0.5mol/L, by AgNO under 500r/min rotating speed
3drop in reducing solution, control time for adding is 10min, and reaction temperature is 50 DEG C, is added dropwise to complete rear continuation reaction 20min; By reacted suspension centrifuge (high speed tabletop centrifuge: GT10-1, Beijing epoch Bei Li centrifuge Co., Ltd) in the centrifugal 30min of 10000r/min, centrifugal product uses deionized water, absolute ethyl alcohol and acetone respectively to wash once; By the ultra-fine ball silver after washed at 50 DEG C, dry 24h under 0.1mmHg, prepare ultra-fine ball silver powder for subsequent use, detect (BI-90PLUS, Brookhaven company of the U.S.) through laser nano Particle Size Analyzer, the average grain diameter of obtained ultra-fine ball silver is 132nm.
(2) preparation of polyurethane prepolymer: before reaction starts to PEG-400 at 80 DEG C, decompression distillation 1h under 0.1mmHg, be warming up to 100 DEG C subsequently, decompression distillation 1h under 0.1mmHg; HEMA then adopts anhydrous calcium chloride dry before using; In the four-hole boiling flask of 150ml, add the TDI of 0.100mol, when temperature constant is at 30 DEG C, dropwise instilled in four-hole boiling flask by the PEG-400 of 0.050mol, time for adding is 2h, continues reaction 2h; Be warming up to 60 DEG C subsequently, add disposable for the HEMA of the 0.050mol being dissolved with 0.05gDBTDL, reaction 3h discharging while hot, keeps in Dark Place, prepares polyurethane prepolymer for subsequent use.
(3) preparation of ultraviolet curing urethane base conductive silver paste: its preparation method is as embodiment 1.Sample performance is as shown in table 1.
As can be seen from Table 1, when total silver powder content is 65.0wt%, wherein ultra-fine ball silver content increases to 6.6wt%, and after solidification, the conductivity of silver slurry is 1.32 ╳ 10
6s/m, after 10 bendings, conductivity is 3.38 ╳ 10
5s/m, illustrates that improving ultra-fine ball silver content is conducive to forming good conductive network, improves conductivity.
Embodiment 3
Prepare ultraviolet curing urethane base conductive silver paste according to the following formulation:
(1) preparation of ultra-fine ball silver: by 6.40gPVP, 0.05gCTAB and 1.76g dissolution of ascorbic acid in deionized water, adds NaOH simultaneously and regulates pH to be 12.0, prepare the reducing solution of 50ml; By 1.70gAgNO
3to be dissolved in deionized water and to be diluted to 1.0mol/L, by AgNO under 200r/min rotating speed
3drop in reducing solution, control time for adding is 30min, and reaction temperature is 0 DEG C, is added dropwise to complete rear continuation reaction 60min; By reacted suspension centrifuge (high speed tabletop centrifuge: GT10-1, Beijing epoch Bei Li centrifuge Co., Ltd) in the centrifugal 30min of 8000r/min, centrifugal product uses deionized water, absolute ethyl alcohol and acetone respectively to wash once; By the ultra-fine ball silver after washed at 30 DEG C, dry 48h under 0.1mmHg, prepare ultra-fine ball silver powder for subsequent use, detect (BI-90PLUS, Brookhaven company of the U.S.) through laser nano Particle Size Analyzer, the average grain diameter of obtained ultra-fine ball silver is 170nm.
(2) preparation of polyurethane prepolymer: before reaction starts to PEG-200 (molecular weight is the PEG of 200) at 80 DEG C, decompression distillation 1h under 0.1mmHg, be warming up to 100 DEG C subsequently, decompression distillation 1h under 0.1mmHg; HEMA then adopts anhydrous calcium chloride dry before using; In the four-hole boiling flask of 150ml, add the TDI of 0.100mol, when temperature constant is at 50 DEG C, dropwise instilled in four-hole boiling flask by the PEG-200 of 0.05mol, time for adding is 2h, continues reaction 1h; Be warming up to 80 DEG C subsequently, add disposable for the HEMA of the 0.053mol being dissolved with 0.10gDBTDL, reaction 2h discharging while hot, keeps in Dark Place, prepares polyurethane prepolymer for subsequent use.
(3) preparation of ultraviolet curing urethane base conductive silver paste: its preparation method is as embodiment 1.Sample performance is as shown in table 1.
Learnt by table 1, when total silver powder content is 60.0wt%, the conductivity of silver slurry is 4.51 ╳ 10
5s/m, after 10 bendings, conductivity is 2.04 ╳ 10
5s/m, and starch (comparative example 2) conductivity using DY5200 and HDDA as the silver of organic phase and be only 7.83 ╳ 10
4s/m, breaks after 6 bendings, indicates self-control high-flexibility end-vinyl polyurethane prepolymer and can improve the conductivity of silver slurry and resistance to bending performance.
Embodiment 4
Prepare ultraviolet curing urethane base conductive silver paste according to the following formulation:
(1) preparation of ultra-fine ball silver: by 3.40gPVP, 0.30gCTAB and 1.76g dissolution of ascorbic acid in deionized water, adds NaOH simultaneously and regulates pH to be 12.3, prepare the reducing solution of 50ml; By 1.70gAgNO
3to be dissolved in deionized water and to be diluted to 0.7mol/L, by AgNO under 400r/min rotating speed
3drop in reducing solution, control time for adding is 20min, and reaction temperature is 30 DEG C, is added dropwise to complete rear continuation reaction 30min; By reacted suspension centrifuge (high speed tabletop centrifuge: GT10-1, Beijing epoch Bei Li centrifuge Co., Ltd) in the centrifugal 10min of 10000r/min, centrifugal product uses deionized water, absolute ethyl alcohol and acetone respectively to wash once; By the ultra-fine ball silver after washed at 40 DEG C, dry 48h under 0.1mmHg, prepare ultra-fine ball silver powder for subsequent use, detect (BI-90PLUS, Brookhaven company of the U.S.) through laser nano Particle Size Analyzer, the average grain diameter of obtained ultra-fine ball silver is 110nm.
(2) preparation of polyurethane prepolymer: before reaction starts to PEG-400 at 80 DEG C, decompression distillation 1h under 0.1mmHg, be warming up to 100 DEG C subsequently, decompression distillation 1h under 0.1mmHg; HEMA then adopts anhydrous calcium chloride dry before using; In the four-hole boiling flask of 150ml, add the TDI of 0.100mol, when temperature constant is at 40 DEG C, dropwise instilled in four-hole boiling flask by the PEG-400 of 0.050mol, time for adding is 1.5h, continues reaction 2h; Be warming up to 70 DEG C subsequently, add disposable for the HEMA of the 0.052mol being dissolved with 0.15gDBTDL, reaction 3h discharging while hot, keeps in Dark Place, prepares polyurethane prepolymer for subsequent use.Fig. 3 is the infrared spectrum of this embodiment polyurethane preformed polymer, and the position of its absworption peak is similar to embodiment 1 to pattern, demonstrates the structural similarity of prepared polyurethane prepolymer.
(3) preparation of ultraviolet curing urethane base conductive silver paste: its preparation method is as embodiment 1.Sample performance is as shown in table 1.
As can be seen from Table 1, when total silver powder content is that 65.0wt%, HDDA content is down to 13.6wt%, when polyurethane prepolymer content increases to 20.4wt%, the conductivity of silver slurry is 8.45 ╳ 10
5s/m, the conductivity after 10 bendings is still 3.01 ╳ 10
5s/m, has good adhesive force with PET base material, shows that the minimizing of activated monomer content can cause the decline of silver slurry cure shrinkage, thus reduces the conductivity of silver slurry, but still maintain good adhesive force and resistance to bending performance.
Embodiment 5
Prepare ultraviolet curing urethane base conductive silver paste according to the following formulation:
(1) preparation of ultra-fine ball silver: by 1.70gPVP, 0.50gCTAB and 1.76g dissolution of ascorbic acid in deionized water, adds NaOH simultaneously and regulates pH to be 12.5, prepare the reducing solution of 50ml; By 1.70gAgNO
3to be dissolved in deionized water and to be diluted to 0.8mol/L, by AgNO under 300r/min rotating speed
3drop in reducing solution, control time for adding is 20min, and reaction temperature is 30 DEG C, is added dropwise to complete rear continuation reaction 40min; By reacted suspension centrifuge (high speed tabletop centrifuge: GT10-1, Beijing epoch Bei Li centrifuge Co., Ltd) in the centrifugal 20min of 10000r/min, centrifugal product uses deionized water, absolute ethyl alcohol and acetone respectively to wash once; By the ultra-fine ball silver after washed at 30 DEG C, dry 48h under 0.1mmHg, prepare ultra-fine ball silver powder for subsequent use, detect (BI-90PLUS, Brookhaven company of the U.S.) through laser nano Particle Size Analyzer, the average grain diameter of obtained ultra-fine ball silver is 130nm.
(2) preparation of polyurethane prepolymer: before reaction starts to PEG-400 at 80 DEG C, decompression distillation 1h under 0.1mmHg, be warming up to 100 DEG C subsequently, decompression distillation 1h under 0.1mmHg; HEMA then adopts anhydrous calcium chloride dry before using; In the four-hole boiling flask of 150ml, add the TDI of 0.100mol, when temperature constant is at 40 DEG C, dropwise instilled in four-hole boiling flask by the PEG-400 of 0.050mol, time for adding is 2h, continues reaction 2h; Be warming up to 70 DEG C subsequently, add disposable for the HEMA of the 0.051mol being dissolved with 0.15gDBTDL, reaction 2.5h discharging while hot, keeps in Dark Place, prepares polyurethane prepolymer for subsequent use.
(3) preparation of ultraviolet curing urethane base conductive silver paste: its preparation method is as embodiment 1.Sample performance is as shown in table 1.
Can be learnt by table 1, when total silver powder content is 65.0wt%, after adopting solidification, the NVP (solidification post-shrinkage ratio is 13%) of low-shrinkage replaces the HDDA (solidification post-shrinkage ratio is 18%) of wherein half, and the conductivity of silver slurry is 7.59 ╳ 10
5s/m, silver slurry is better with the adhesive force of PET base material, and the conductivity after 10 bendings is 3.28 ╳ 10
5s/m, this may diminishing due to cure shrinkage, causes the decline of silver slurry conductivity, but still maintain good adhesive force and resistance to bending performance.
Comparative example 1
In order to prove the excellent properties that ball silver in the ultraviolet light polymerization conductive silver paste prepared by the present invention/sheet silver is composite, with independent sheet silver powder for conductive phase as a comparison case.
Prepare ultraviolet curing urethane base conductive silver paste according to the following formulation
(1) preparation of polyurethane prepolymer: its preparation method is as embodiment 1.
(2) preparation of ultraviolet curing urethane base conductive silver paste: first HDDA is warming up to 50 DEG C, then light trigger ITX and 819 is dissolved in HDDA, to be cooled to after 30 DEG C, (particle diameter is 3 μm ~ 10 μm to add polyurethane prepolymer and flake silver powder subsequently, model is TL-187, produced by Dongguan Betely New Materials Co., Ltd.), high speed dispersor is used to stir the mixture 20min in 800r/min, and then adopt three roller dispersion machine grinding 5min, obtain ultraviolet curing urethane base conductive silver paste; (PET film is thick is approximately 50 μm to adopt screen process press slurry to be printed onto PET film, printing before with absolute ethyl alcohol wiping and dry) on, subsequently by uv cure machine (Co., Ltd Fusion UV S300 in Spectris, uviol lamp power is 4000W, wavelength is 365nm) solidify 30s, after solidification, silver slurry thickness is 10 ~ 15 μm.Sample performance is as shown in table 1.
Comparative example 2
In order to prove the excellent properties of the polyurethane prepolymer prepared by the present invention, using the urethane acrylate UV-cured resin of two degrees of functionality (Dongyang DY5200) and HDDA as organic phase as a comparison case.
Prepare ultraviolet curing urethane base conductive silver paste according to the following formulation
(1) preparation of ultra-fine ball silver: its preparation method is as embodiment 3.
(2) preparation of ultraviolet curing urethane base conductive silver paste: its preparation method is as embodiment 1.Sample performance is as shown in table 1.
Method of testing relevant in embodiment is below described as follows:
The conductivity test of silver slurry: the resistance value R first testing out printed conductor according to GB/T12631-90, then by formula κ=L/RWH, (wherein κ is conductivity (S/m), L is printed conductor length (m), R is test resistance (Ω), W is printed conductor width (m), and H is printed conductor thickness (m)), calculate conductivity.
Resistance to bending performance test: printed conductor is bent 180 ° to external symmetry, and be pressed on broken line place with 3kg counterweight, keep 1min, again by reverse for printed conductor doubling 180 °, then be pressed on broken line place with 3kg counterweight, keep 1min, then carry out the conductivity test of silver slurry, above step is considered as 1 crooked test, repeats above operation until conductor cord disconnection (testing time≤10 time).
The adhesive force test of silver slurry: by the grade sign silver slurry of hundred lattice tests and the adhesive force size of PET base material, hundred lattice tests measure according to GB9286-98.Wherein, 5B is best hundred lattice test grades, shows that silver slurry and base material have good adhesive force, and 0B then for differing from most hundred lattice test grades, shows the poor adhesive force of silver slurry and base material.
In table 1 sequence number 6 for Chinese invention patent CN200810167513.6 prepared when silver powder content is 65.0wt% ultraviolet light polymerization silver slurry data; Sequence number 7 is Jiang Bin (research and apply of low-temperature cured conductive silver slurry, East China University of Science's master thesis in 2012) prepared hot curing silver slurry data when silver powder content is 69.0wt%.
The performance of table 1 silver slurry and light trigger consumption
By adopt layer quick-setting light trigger 819 and surface quick-setting light trigger ITX composite, the end-vinyl polyurethane prepolymer of high-flexibility and the activated monomer HDDA of the rear high shrinkage of solidification are as organic adhesive phase, and flake silver powder and ultra-fine ball silver composite as conductive phase, be 1.0wt% at light trigger consumption, total silver powder content is 65.0wt%, and the conductivity of prepared ultraviolet light polymerization silver slurry is 7.59 ╳ 10
5s/m ~ 1.32 ╳ 10
6s/m, after 10 bending tests, conductivity is still 7.82 ╳ 10
4s/m ~ 3.38 ╳ 10
5s/m, possesses good adhesive force with PET base material simultaneously, can be widely used in the flexible print circuits such as keyboard, mobile phone, panel computer, digital camera.
Claims (10)
1. the preparation method of a ultraviolet curing urethane base conductive silver paste, it is characterized in that: after activated monomer being warming up to 40 DEG C ~ 60 DEG C, light trigger is dissolved in activated monomer, be cooled to 20 DEG C ~ 35 DEG C, mix with ultra-fine ball silver, after ultrasonic wave dispersion, add polyurethane prepolymer and flake silver powder successively, after stirring, grinding, obtain described conductive silver paste;
The particle diameter of described flake silver powder is 3 μm ~ 10 μm;
The particle diameter of described ultra-fine ball silver is 100nm ~ 400nm, and its preparation method comprises the steps:
1) by polyvinylpyrrolidone, softex kw and dissolution of ascorbic acid in deionized water, be configured to reducing solution, by NaOH regulate pH be 12 ~ 12.5;
2) silver nitrate to be dissolved in deionized water and to be diluted to 0.5 ~ 1.0mol/L, under the mixing speed of 200r/min ~ 500r/min, controlling reaction temperature is 0 DEG C ~ 50 DEG C, silver nitrate aqueous solution is dropped in reducing solution, wherein time for adding is 10min ~ 30min, is added dropwise to complete rear continuation reaction 20min ~ 60min;
3) reacted suspension centrifuge is isolated ultra-fine ball silver, then by the washing of deionized water, absolute ethyl alcohol and acetone;
4) by the ultra-fine ball silver after washed at drying under reduced pressure;
The mol ratio of described ascorbic acid and silver nitrate is 1:1; The mass ratio of described polyvinylpyrrolidone and silver nitrate is 1:1 ~ 4:1, and the mass ratio of described softex kw and silver nitrate is 1:3.4 ~ 1:34;
Described polyurethane prepolymer is prepared by the following method for making end-vinyl polyurethane prepolymer by oneself: dropwise instilled in toluene di-isocyanate(TDI) by polyethylene glycol, reaction temperature is 30 DEG C ~ 50 DEG C, time for adding is 1h ~ 2h, be added dropwise to complete rear continuation reaction 1 ~ 2h, be warming up to 60 DEG C ~ 80 DEG C subsequently, add disposable for the hydroxyethyl methacrylate being dissolved with dibutyl tin laurate, continue reaction 2h ~ 3h, discharging while hot, keeps in Dark Place; The mol ratio of described polyethylene glycol, toluene di-isocyanate(TDI) and hydroxyethyl methacrylate is 1:2:1 ~ 1:2:1.05; The mass ratio of described dibutyl tin laurate and toluene di-isocyanate(TDI) is 1:348 ~ 1:116;
Described activated monomer is 1-6 hexylene glycol double methacrylate and/or NVP;
Described light trigger is two (2,4, the 6-trimethylbenzoyl) phosphine oxide of 2-isopropyl thioxanthone and phenyl.
2. the preparation method of ultraviolet curing urethane base conductive silver paste according to claim 1, it is characterized in that, the mass fraction of raw material is as follows:
3. the preparation method of ultraviolet curing urethane base conductive silver paste according to claim 1, is characterized in that: the mass ratio of described ultra-fine ball silver and flake silver powder is 1:9 ~ 1:19.
4. the preparation method of ultraviolet curing urethane base conductive silver paste according to claim 1, is characterized in that: described activated monomer and the mass ratio of polyurethane prepolymer are 1:1 ~ 1:1.5.
5. the preparation method of ultraviolet curing urethane base conductive silver paste according to claim 1; it is characterized in that: described 2-isopropyl thioxanthone X and phenyl two (2; 4,6-trimethylbenzoyl) mass ratio of phosphine oxide is 1:1 ~ 1:1.5.
6. the preparation method of ultraviolet curing urethane base conductive silver paste according to claim 1, is characterized in that: the gross mass of described polyurethane prepolymer and activated monomer and the total mass ratio 1:1.5 ~ 1:2.0 of silver powder.
7. the preparation method of ultraviolet curing urethane base conductive silver paste according to claim 1, is characterized in that: first at 80 DEG C ~ 100 DEG C decompression distillation 1 ~ 2h before described polyethylene glycol uses; Adopt anhydrous calcium chloride dry before described hydroxyethyl methacrylate uses.
8. the preparation method of ultraviolet curing urethane base conductive silver paste according to claim 1, is characterized in that: described centrifugation isolates ultra-fine ball silver with centrifuge in the centrifugal 10min ~ 30min of 8000r/min ~ 10000r/min; The number of times of described washing is 2 ~ 4 times; Described drying under reduced pressure is at 30 DEG C ~ 50 DEG C drying under reduced pressure 24h ~ 48h by the ultra-fine ball silver after washed.
9. a ultraviolet curing urethane base conductive silver paste, is characterized in that it is obtained by preparation method described in any one of claim 1-8.
10. ultraviolet curing urethane base conductive silver paste according to claim 9, is characterized in that, the conductivity of described ultraviolet light polymerization silver slurry is 7.59 ╳ 10
5s/m ~ 1.32 ╳ 10
6s/m, after 10 bending tests, conductivity is still 7.82 ╳ 10
4s/m ~ 3.38 ╳ 10
5s/m.
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