CN104962133B - A kind of nanometer water electrically conductive ink and preparation method thereof - Google Patents
A kind of nanometer water electrically conductive ink and preparation method thereof Download PDFInfo
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Abstract
A kind of nanometer water electrically conductive ink, it is composed of the following components according to mass percent：Multi-walled carbon nano-tubes 8~10%, hexamethylene diisocyanate 20~22%, polyethylene glycol 2000 8~10%, dihydromethyl propionic acid 1~3%, N methyl pyrrolidones 2~4%, 1, 6 hexylene glycols 0.3~3%, triethylamine 1~3%, deionized water 20~30%, butyl tin dilaurate 0.1~1%, acetone 1~3%, ethylene glycol 6~9%, monoethanolamine 2~4%, polyethylene glycol 200 1~2%, polyacrylamide 1~2%, polypropylene ethyl ester 1~2%, polypropylene wax 1~2%, polyoxypropylene ethylene oxide glycerin ether 1~2% and bright red mill base 10%, said components mass percent value and be 100%.Nanometer water electrically conductive ink viscosity of the present invention is small, and curing rate is fast, there is preferable rub resistance and resistance after layer of ink solidification, and its preparation method is simple, and equipment cost is low.
Description
Technical field
The invention belongs to printing material technical field, and in particular to a kind of nanometer water electrically conductive ink, the invention further relates to
The preparation method of the nanometer water electrically conductive ink.
Background technology
Nanometer water electrically conductive ink be it is a kind of not only there is water-based ink characteristic but also conductive energy with the addition of nanoscale
The new function ink of conductive filler.
Wherein Nano Silver water-soluble conducting ink：The relatively costly of nano silver material is prepared, and by nano-Ag particles again
Being distributed in solvent needs extra dispersion technology (such as ball milling dispersion, ultrasonic disperse), and the operation is complex, and redisperse
The more difficult control of nano-Ag particles stability in solvent.
Compound nanometer water electrically conductive ink：As Nanometer Copper surface forms one layer of Nano Silver, printing figures can be strengthened
Electric conductivity, inoxidizability, while again can be with reduces cost.But the compatibility between such ink conductive component is poor, mixing
Easily condensed between grain.
The content of the invention
It is an object of the invention to provide a kind of nanometer water electrically conductive ink, existing composite Nano water-soluble conducting ink is solved
The problem easily condensed between compatibility difference and hybrid particles between conductive component.
It is a further object to provide a kind of preparation method of nanometer water electrically conductive ink.
The technical solution adopted in the present invention is, a kind of nanometer water electrically conductive ink, according to mass percent by with the following group
It is grouped into：Multi-walled carbon nano-tubes 8~10%, hexamethylene diisocyanate 20~22%, Polyethylene glycol-2000 8~10%, two
Hydroxymethyl propionic acid 1~3%, 1-METHYLPYRROLIDONE 2~4%, 1,6-HD 0.3~3%, triethylamine 1~3%, deionization
Water 20~30%, butyl tin dilaurate 0.1~1%, acetone 1~3%, ethylene glycol 6~9%, monoethanolamine 2~4%, poly- second two
Alcohol 2001~2%, polyacrylamide 1~2%, polypropylene ethyl ester 1~2%, polypropylene wax 1~2%, polyoxypropylene ethylene oxide
Glycerin ether 1~2% and bright red mill base 10%, said components mass percent value and be 100%.
Another technical scheme of the present invention is that a kind of preparation method of nanometer water electrically conductive ink is specifically pressed
Implement according to following steps：
Step 1, multi-walled carbon nano-tubes 8~10%, hexamethylene diisocyanate 20 are weighed according to mass percent respectively
~22%, Polyethylene glycol-2000 8~10%, dihydromethyl propionic acid 1~3%, 1-METHYLPYRROLIDONE 2~4%, 1,6- oneself two
Alcohol 0.3~3%, triethylamine 1~3%, deionized water 20~30%, butyl tin dilaurate 0.1~1%, acetone 1~3%, second
Glycol 6~9%, monoethanolamine 2~4%, polyethylene glycol 200 1~2%, polyacrylamide 1~2%, polypropylene ethyl ester 1~2%,
Polypropylene wax 1~2%, polyoxypropylene ethylene oxide glycerin ether 1~2% and bright red mill base 10%, said components mass percent
Value and be 100%；
Step 2, ultrasonic disperse 30min after magnetic agitation 30min in multi-walled carbon nano-tubes addition ethylene glycol is mixed
Thing A；
Step 3, by hexamethylene diisocyanate and Polyethylene glycol-2000 add with reflux condenser, thermometer and
In the four-hole boiling flask of agitating device, heating water bath adds butyl tin dilaurate reaction 30min after being warming up to 85 DEG C of stirring 2h；So
60 DEG C of mixtures for rapidly joining dihydromethyl propionic acid and 1-METHYLPYRROLIDONE are cooled the temperature to afterwards, then by bath temperature control
System reacts 10min at 60~70 DEG C, 85 DEG C of reaction 2h is continuously heating at 70 DEG C, then cool the temperature to 35 DEG C；
Step 4,1,6- hexylene glycols are dissolved in acetone, and the mixture A obtained with step 2 is well mixed, then slowly
Add in the reaction system of step 3, high-speed stirred shears 1h；The triethylamine that deionized water will be dissolved in is added instead under high velocity agitation
System is answered, remaining deionized water is subsequently adding and is emulsified 25~30min, mixture is carried out into vacuum distillation after the completion of reaction, steamed
Go out cosolvent acetone, obtain the aqueous polyurethane dispersion of carbon nanotubes；
Step 5, the aqueous polyurethane dispersion of the carbon nanotubes that bright red mill base, step 4 are obtained, part polyoxypropylene
Ethylene oxide glycerin ether mix and be slowly stirred after 30min pour into ball grinder carry out ball milling after add monoethanolamine, polyethylene glycol
200th, polyacrylamide, ethyl acrylate, polypropylene wax and remaining polyoxypropylene ethylene oxide glycerin ether, continue ball milling 4h,
Drum's speed of rotation is 400 revs/min, obtains nanometer water electrically conductive ink.
The features of the present invention is also resided in,
Purifying is needed before weighing multi-walled carbon nano-tubes in step 1, specific purification step is：Undressed many wall carbon are received
Mitron calcines 2h in 700 DEG C of air, adds the NaOH solution of 4mol/L, is heated to reflux 2h, and filtering, washing are dried at 80 DEG C
The mixture of concentrated nitric acid and the concentrated sulfuric acid is added after 2h, then is washed with deionized to pH after being heated to reflux 50min at 80 DEG C and is
7, finally the vacuum drying 24h at 50 DEG C obtain final product.
The volume ratio of concentrated nitric acid and the concentrated sulfuric acid is 1 in the mixture of concentrated nitric acid and the concentrated sulfuric acid：3.
Drum's speed of rotation is 400 revs/min in step 5, and Ball-milling Time is 2h.
The beneficial effects of the invention are as follows,
1. nanometer water electrically conductive ink viscosity of the present invention is small, and curing rate is fast, time saving and energy saving energy-conservation；In the absence of waving naturally
Hair, ink viscosity good stability；Wire drawing phenomenon is not had in printing；Glossiness is high, layer of ink solidification after have preferable rub resistance and
Resistance, in the absence of organic volatile, green, environmental protection.
2. the preparation method of nanometer water electrically conductive ink of the present invention, many walls are made by methods such as purifying, magnetic agitation, ultrasounds
CNT is sufficiently separated, is disperseed, and aqueous polyurethane is prepared by prepolymer method, and process of preparing is novel,
CNT is added in preparation process, both are by chemical bonds, with reference to effect is significant, good stability, and its technological process
Simple to operate, equipment cost is low, it is possible to achieve mass production.
Brief description of the drawings
Fig. 1 is the particle diameter and grain size distribution of nanometer water electrically conductive ink prepared by embodiment 1；
Fig. 2 is the particle diameter and grain size distribution of nanometer water electrically conductive ink prepared by embodiment 2.
Specific embodiment
The present invention is described in detail with reference to the accompanying drawings and detailed description.
Nanometer water electrically conductive ink of the present invention, it is composed of the following components according to mass percent：Multi-walled carbon nano-tubes 8~
10%th, hexamethylene diisocyanate 20~22%, Polyethylene glycol-2000 8~10%, dihydromethyl propionic acid 1~3%, N- first
Base pyrrolidones 2~4%, 1,6-HD 0.3~3%, triethylamine 1~3%, deionized water 20~30%, tin dilaurate fourth
Base tin 0.1~1%, acetone 1~3%, ethylene glycol 6~9%, monoethanolamine 2~4%, polyethylene glycol 200 1~2%, polyacrylamide
Amine 1~2%, polypropylene ethyl ester 1~2%, polypropylene wax 1~2%, polyoxypropylene ethylene oxide glycerin ether 1~2% and large red
Slurry 10%, said components mass percent value and be 100%.
The preparation method of above-mentioned nanometer water electrically conductive ink, specifically implements according to following steps：
Step 1,2h is calcined by undressed multi-walled carbon nano-tubes in 700 DEG C of air, adds the NaOH of 4mol/L molten
Liquid, is heated to reflux 2h, and filtering, washing dry mixture (concentrated nitric acid and the dense sulphur of addition concentrated nitric acid and the concentrated sulfuric acid after 2h at 80 DEG C
The volume ratio of acid is 1：3) it is 7 to be washed with deionized after, then being heated to reflux 50min at 80 DEG C to pH, finally at 50 DEG C
The vacuum drying 24h multi-walled carbon nano-tubes that obtains after purification；
Step 2, multi-walled carbon nano-tubes 8~10% after purification, hexa-methylene two is weighed according to mass percent different respectively
Cyanate 20~22%, Polyethylene glycol-2000 8~10%, dihydromethyl propionic acid 1~3%, 1-METHYLPYRROLIDONE 2~4%,
1,6-HD 0.3~3%, triethylamine 1~3%, deionized water 20~30%, butyl tin dilaurate 0.1~1%, acetone 1
~3%, ethylene glycol 6~9%, monoethanolamine 2~4%, polyethylene glycol 200 1~2%, polyacrylamide 1~2%, polypropylene ethyl ester
1~2%, polypropylene wax 1~2%, polyoxypropylene ethylene oxide glycerin ether 1~2% and bright red mill base 10%, said components quality
Percent value and be 100%；
Step 3, by ultrasonic disperse 30min after magnetic agitation 30min in multi-walled carbon nano-tubes addition ethylene glycol after purification,
Obtain mixture A；
Step 4, by hexamethylene diisocyanate and Polyethylene glycol-2000 add with reflux condenser, thermometer and
In the four-hole boiling flask of agitating device, heating water bath adds butyl tin dilaurate reaction 30min after being warming up to 85 DEG C of stirring 2h；So
60 DEG C of mixtures for rapidly joining dihydromethyl propionic acid and 1-METHYLPYRROLIDONE are cooled the temperature to afterwards, then by bath temperature control
System reacts 10min at 60~70 DEG C, 85 DEG C of reaction 2h is continuously heating at 70 DEG C, then cool the temperature to 35 DEG C；
Step 5,1,6- hexylene glycols are dissolved in acetone, and the mixture A obtained with step 3 is well mixed, then slowly
Add in the reaction system of step 4, high-speed stirred shears 1h；The triethylamine that deionized water will be dissolved in is added instead under high velocity agitation
System is answered, remaining deionized water is subsequently adding and is emulsified 25~30min, mixture is carried out into vacuum distillation after the completion of reaction, steamed
Go out cosolvent acetone, obtain the aqueous polyurethane dispersion of carbon nanotubes；
Step 6, the aqueous polyurethane dispersion of the carbon nanotubes that bright red mill base, step 5 are obtained, part polyoxypropylene
Ethylene oxide glycerin ether mixes and is slowly stirred after 30min to pour into carries out ball milling in ball grinder, drum's speed of rotation is 400 revs/min,
Ball-milling Time is 2h, is subsequently adding monoethanolamine, polyethylene glycol 200, polyacrylamide, ethyl acrylate, polypropylene wax and is left
Polyoxypropylene ethylene oxide glycerin ether, continue ball milling 4h, drum's speed of rotation be 400 revs/min, obtain nanometer water conductive oil
Ink.
Embodiment 1
Step 1,2h is calcined by undressed multi-walled carbon nano-tubes in 700 DEG C of air, adds the NaOH of 4mol/L molten
Liquid, is heated to reflux 2h, and filtering, washing dry mixture (concentrated nitric acid and the dense sulphur of addition concentrated nitric acid and the concentrated sulfuric acid after 2h at 80 DEG C
The volume ratio of acid is 1：3) it is 7 to be washed with deionized after, then being heated to reflux 50min at 80 DEG C to pH, finally at 50 DEG C
The vacuum drying 24h multi-walled carbon nano-tubes that obtains after purification；
Step 2, multi-walled carbon nano-tubes 9%, the isocyanic acid of hexa-methylene two after purification is weighed according to mass percent respectively
Ester 20%, Polyethylene glycol-2000 8%, dihydromethyl propionic acid 1%, 1-METHYLPYRROLIDONE 3%, 1,6-HD 1.9%, three
Ethamine 1%, deionized water 28%, butyl tin dilaurate 0.1%, acetone 2%, ethylene glycol 6%, monoethanolamine 2%, polyethylene glycol
2002%th, polyacrylamide 1%, polypropylene ethyl ester 1%, polypropylene wax 2%, polyoxypropylene ethylene oxide glycerin ether 2% and big
Red slurry 10%；
Step 3, by ultrasonic disperse 30min after magnetic agitation 30min in multi-walled carbon nano-tubes addition ethylene glycol after purification,
Obtain mixture A；
Step 4, by hexamethylene diisocyanate and Polyethylene glycol-2000 add with reflux condenser, thermometer and
In the four-hole boiling flask of agitating device, heating water bath adds butyl tin dilaurate reaction 30min after being warming up to 85 DEG C of stirring 2h；So
60 DEG C of mixtures for rapidly joining dihydromethyl propionic acid and 1-METHYLPYRROLIDONE are cooled the temperature to afterwards, then by bath temperature control
System reacts 10min at 60 DEG C, 85 DEG C of reaction 2h is continuously heating at 70 DEG C, then cool the temperature to 35 DEG C；
Step 5,1,6- hexylene glycols are dissolved in acetone, and the mixture A obtained with step 3 is well mixed, then slowly
Add in the reaction system of step 4, high-speed stirred shears 1h；The triethylamine that deionized water will be dissolved in is added instead under high velocity agitation
System is answered, remaining deionized water emulsification 30min is subsequently adding, mixture is carried out into vacuum distillation after the completion of reaction, steamed and help
Solvent acetone, obtains the aqueous polyurethane dispersion of carbon nanotubes；
Step 6, the aqueous polyurethane dispersion of the carbon nanotubes that bright red mill base, step 5 are obtained, part polyoxypropylene
Ethylene oxide glycerin ether mixes and is slowly stirred after 30min to pour into carries out ball milling in ball grinder, drum's speed of rotation is 400 revs/min,
Ball-milling Time is 2h, is subsequently adding monoethanolamine, polyethylene glycol 200, polyacrylamide, ethyl acrylate, polypropylene wax and is left
Polyoxypropylene ethylene oxide glycerin ether, continue ball milling 4h, drum's speed of rotation be 400 revs/min, obtain nanometer water conductive oil
Ink.
The nanometer water electrically conductive ink that embodiment 1 is prepared, solid content is that 45.6%, viscosity is 23s；Use Hunan instrument
H1850 types are centrifuged the stability of machine testing water-based ink, and under 3000 revs/min of rotating speed, centrifugation 5 minutes, are repeated 3 times every time,
Its bottom is observed after discharging a small amount of precipitation, illustrates that the shelf-life of the nanometer water electrically conductive ink is good, and the shelf-life is about 3
Month；Resistance detection analysis is carried out to specification (2cm long, 5mm wide, thick 0.13mm) the electrically conductive ink ink film for preparing using universal meter
It was found that its resistance value scope is 800-2000m Ω；As shown in figure 1, the particle diameter of nanometer water electrically conductive ink prepared by embodiment 1
Scope is 0.04um~2000um, and average grain diameter is 867nm, and average grain diameter is 420nm.Granule of the particle diameter less than 1.995um
Product content accounts for the 90% of whole particles, and volumetric solid concentration of the particle diameter less than 111nm accounts for the 10% of whole particles.Illustrate what is prepared
The particle size range of nanometer water electrically conductive ink is in micro-nano series.
Embodiment 2
Step 1,2h is calcined by undressed multi-walled carbon nano-tubes in 700 DEG C of air, adds the NaOH of 4mol/L molten
Liquid, is heated to reflux 2h, and filtering, washing dry mixture (concentrated nitric acid and the dense sulphur of addition concentrated nitric acid and the concentrated sulfuric acid after 2h at 80 DEG C
The volume ratio of acid is 1：3) it is 7 to be washed with deionized after, then being heated to reflux 50min at 80 DEG C to pH, finally at 50 DEG C
The vacuum drying 24h multi-walled carbon nano-tubes that obtains after purification；
Step 2, multi-walled carbon nano-tubes 8%, the isocyanic acid of hexa-methylene two after purification is weighed according to mass percent respectively
Ester 22%, Polyethylene glycol-2000 9%, dihydromethyl propionic acid 2%, 1-METHYLPYRROLIDONE 4%, 1,6-HD 0.3%, three
Ethamine 2%, deionized water 20%, butyl tin dilaurate 0.5%, acetone 3%, ethylene glycol 8%, monoethanolamine 4%, polyethylene glycol
2001.5%th, polyacrylamide 1.3%, polypropylene ethyl ester 1.2%, polypropylene wax 2%, polyoxypropylene ethylene oxide glycerin ether
1.2% and bright red mill base 10%；
Step 3, by ultrasonic disperse 30min after magnetic agitation 30min in multi-walled carbon nano-tubes addition ethylene glycol after purification,
Obtain mixture A；
Step 4, by hexamethylene diisocyanate and Polyethylene glycol-2000 add with reflux condenser, thermometer and
In the four-hole boiling flask of agitating device, heating water bath adds butyl tin dilaurate reaction 30min after being warming up to 85 DEG C of stirring 2h；So
60 DEG C of mixtures for rapidly joining dihydromethyl propionic acid and 1-METHYLPYRROLIDONE are cooled the temperature to afterwards, then by bath temperature control
System reacts 10min at 65 DEG C, 85 DEG C of reaction 2h is continuously heating at 70 DEG C, then cool the temperature to 35 DEG C；
Step 5,1,6- hexylene glycols are dissolved in acetone, and the mixture A obtained with step 3 is well mixed, then slowly
Add in the reaction system of step 4, high-speed stirred shears 1h；The triethylamine that deionized water will be dissolved in is added instead under high velocity agitation
System is answered, remaining deionized water emulsification 25min is subsequently adding, mixture is carried out into vacuum distillation after the completion of reaction, steamed and help
Solvent acetone, obtains the aqueous polyurethane dispersion of carbon nanotubes；
Step 6, the aqueous polyurethane dispersion of the carbon nanotubes that bright red mill base, step 5 are obtained, part polyoxypropylene
Ethylene oxide glycerin ether mixes and is slowly stirred after 30min to pour into carries out ball milling in ball grinder, drum's speed of rotation is 400 revs/min,
Ball-milling Time is 2h, is subsequently adding monoethanolamine, polyethylene glycol 200, polyacrylamide, ethyl acrylate, polypropylene wax and is left
Polyoxypropylene ethylene oxide glycerin ether, continue ball milling 4h, drum's speed of rotation be 400 revs/min, obtain nanometer water conductive oil
Ink.
The nanometer water electrically conductive ink that embodiment 2 is prepared, solid content is that 47.8%, viscosity is 25s；Use Hunan instrument
H1850 types are centrifuged the stability of machine testing water-based ink, and under 3000 revs/min of rotating speed, centrifugation 5 minutes, are repeated 3 times every time,
Its bottom is observed after discharging a small amount of precipitation, illustrates that the shelf-life of the nanometer water electrically conductive ink is good, and the shelf-life is about 3
Month；Resistance detection analysis is carried out to specification (2cm long, 5mm wide, thick 0.13mm) the electrically conductive ink ink film for preparing using universal meter
It was found that its resistance value scope is 1000-2300m Ω；As shown in Fig. 2 the nanometer water electrically conductive ink for preparing of embodiment 2
The scope of particle diameter is 0.04um~2000um, and average grain diameter is 1.068um, and average grain diameter is 1.050um, and particle diameter is less than
The volumetric solid concentration of 2.045um accounts for the 90% of whole particles, and volumetric solid concentration of the particle diameter less than 0.162um accounts for whole particles
10%.Illustrate the particle size range of the nanometer water electrically conductive ink for preparing in micro-nano series.
Embodiment 3
Step 1,2h is calcined by undressed multi-walled carbon nano-tubes in 700 DEG C of air, adds the NaOH of 4mol/L molten
Liquid, is heated to reflux 2h, and filtering, washing dry mixture (concentrated nitric acid and the dense sulphur of addition concentrated nitric acid and the concentrated sulfuric acid after 2h at 80 DEG C
The volume ratio of acid is 1：3) it is 7 to be washed with deionized after, then being heated to reflux 50min at 80 DEG C to pH, finally at 50 DEG C
The vacuum drying 24h multi-walled carbon nano-tubes that obtains after purification；
Step 2, multi-walled carbon nano-tubes 10%, the isocyanic acid of hexa-methylene two after purification is weighed according to mass percent respectively
Ester 21%, Polyethylene glycol-2000 10%, dihydromethyl propionic acid 3%, 1-METHYLPYRROLIDONE 2%, 1,6-HD 3%, three second
Amine 1%, deionized water 21%, butyl tin dilaurate 1%, acetone 1%, ethylene glycol 7%, monoethanolamine 3%, polyethylene glycol
2001%th, polyacrylamide 2%, polypropylene ethyl ester 2%, polypropylene wax 1%, polyoxypropylene ethylene oxide glycerin ether 1% and big
Red slurry 10%；
Step 3, by ultrasonic disperse 30min after magnetic agitation 30min in multi-walled carbon nano-tubes addition ethylene glycol after purification,
Obtain mixture A；
Step 4, by hexamethylene diisocyanate and Polyethylene glycol-2000 add with reflux condenser, thermometer and
In the four-hole boiling flask of agitating device, heating water bath adds butyl tin dilaurate reaction 30min after being warming up to 85 DEG C of stirring 2h；So
60 DEG C of mixtures for rapidly joining dihydromethyl propionic acid and 1-METHYLPYRROLIDONE are cooled the temperature to afterwards, then by bath temperature control
System reacts 10min at 70 DEG C, 85 DEG C of reaction 2h is continuously heating at 70 DEG C, then cool the temperature to 35 DEG C；
Step 5,1,6- hexylene glycols are dissolved in acetone, and the mixture A obtained with step 3 is well mixed, then slowly
Add in the reaction system of step 4, high-speed stirred shears 1h；The triethylamine that deionized water will be dissolved in is added instead under high velocity agitation
System is answered, remaining deionized water emulsification 27min is subsequently adding, mixture is carried out into vacuum distillation after the completion of reaction, steamed and help
Solvent acetone, obtains the aqueous polyurethane dispersion of carbon nanotubes；
Step 6, the aqueous polyurethane dispersion of the carbon nanotubes that bright red mill base, step 5 are obtained, part polyoxypropylene
Ethylene oxide glycerin ether mixes and is slowly stirred after 30min to pour into carries out ball milling in ball grinder, drum's speed of rotation is 400 revs/min,
Ball-milling Time is 2h, is subsequently adding monoethanolamine, polyethylene glycol 200, polyacrylamide, ethyl acrylate, polypropylene wax and is left
Polyoxypropylene ethylene oxide glycerin ether, continue ball milling 4h, drum's speed of rotation be 400 revs/min, obtain nanometer water conductive oil
Ink.
Embodiment 4
Step 1,2h is calcined by undressed multi-walled carbon nano-tubes in 700 DEG C of air, adds the NaOH of 4mol/L molten
Liquid, is heated to reflux 2h, and filtering, washing dry mixture (concentrated nitric acid and the dense sulphur of addition concentrated nitric acid and the concentrated sulfuric acid after 2h at 80 DEG C
The volume ratio of acid is 1：3) it is 7 to be washed with deionized after, then being heated to reflux 50min at 80 DEG C to pH, finally at 50 DEG C
The vacuum drying 24h multi-walled carbon nano-tubes that obtains after purification；
Step 2, multi-walled carbon nano-tubes 8%, the isocyanic acid of hexa-methylene two after purification is weighed according to mass percent respectively
Ester 20%, Polyethylene glycol-2000 8%, dihydromethyl propionic acid 1%, 1-METHYLPYRROLIDONE 2%, 1,6-HD 0.9%, three
Ethamine 3%, deionized water 30%, butyl tin dilaurate 0.1%, acetone 1%, ethylene glycol 9%, monoethanolamine 2%, polyethylene glycol
2001%th, polyacrylamide 1%, polypropylene ethyl ester 1%, polypropylene wax 1%, polyoxypropylene ethylene oxide glycerin ether 1% and big
Red slurry 10%；
Step 3, by ultrasonic disperse 30min after magnetic agitation 30min in multi-walled carbon nano-tubes addition ethylene glycol after purification,
Obtain mixture A；
Step 4, by hexamethylene diisocyanate and Polyethylene glycol-2000 add with reflux condenser, thermometer and
In the four-hole boiling flask of agitating device, heating water bath adds butyl tin dilaurate reaction 30min after being warming up to 85 DEG C of stirring 2h；So
60 DEG C of mixtures for rapidly joining dihydromethyl propionic acid and 1-METHYLPYRROLIDONE are cooled the temperature to afterwards, then by bath temperature control
System reacts 10min at 70 DEG C, 85 DEG C of reaction 2h is continuously heating at 70 DEG C, then cool the temperature to 35 DEG C；
Step 5,1,6- hexylene glycols are dissolved in acetone, and the mixture A obtained with step 3 is well mixed, then slowly
Add in the reaction system of step 4, high-speed stirred shears 1h；The triethylamine that deionized water will be dissolved in is added instead under high velocity agitation
System is answered, remaining deionized water emulsification 28min is subsequently adding, mixture is carried out into vacuum distillation after the completion of reaction, steamed and help
Solvent acetone, obtains the aqueous polyurethane dispersion of carbon nanotubes；
Step 6, the aqueous polyurethane dispersion of the carbon nanotubes that bright red mill base, step 5 are obtained, part polyoxypropylene
Ethylene oxide glycerin ether mixes and is slowly stirred after 30min to pour into carries out ball milling in ball grinder, drum's speed of rotation is 400 revs/min,
Ball-milling Time is 2h, is subsequently adding monoethanolamine, polyethylene glycol 200, polyacrylamide, ethyl acrylate, polypropylene wax and is left
Polyoxypropylene ethylene oxide glycerin ether, continue ball milling 4h, drum's speed of rotation be 400 revs/min, obtain nanometer water conductive oil
Ink.
Claims (5)
1. a kind of nanometer water electrically conductive ink, it is characterised in that composed of the following components according to mass percent：Multi-wall carbon nano-tube
Pipe 8~10%, hexamethylene diisocyanate 20~22%, Polyethylene glycol-2000 8~10%, dihydromethyl propionic acid 1~3%,
1-METHYLPYRROLIDONE 2~4%, 1,6-HD 0.3~3%, triethylamine 1~3%, deionized water 20~30%, two bays
Acid butyl tin 0.1~1%, acetone 1~3%, ethylene glycol 6~9%, monoethanolamine 2~4%, polyethylene glycol 200 1~2%, poly- third
Acrylamide 1~2%, polyethyl acrylate 1~2%, polypropylene wax 1~2%, the and of polyoxypropylene ethylene oxide glycerin ether 1~2%
Bright red mill base 10%, said components mass percent value and be 100%；
Specifically preparation method is：
Step 1, by ultrasonic disperse 30min after magnetic agitation 30min in multi-walled carbon nano-tubes addition ethylene glycol, obtains mixture A；
Step 2, hexamethylene diisocyanate and Polyethylene glycol-2000 is added and carries reflux condenser, thermometer and stirring
In the four-hole boiling flask of device, heating water bath adds butyl tin dilaurate reaction 30min after being warming up to 85 DEG C of stirring 2h；Then will
Temperature is down to 60 DEG C of mixtures for rapidly joining dihydromethyl propionic acid and 1-METHYLPYRROLIDONE, and then bath temperature control exists
60~70 DEG C of reaction 10min, are further continued for being warming up to 85 DEG C of reaction 2h, then cool the temperature to 35 DEG C；
Step 3,1,6- hexylene glycols are dissolved in acetone, and the mixture A obtained with step 1 is well mixed, and is then slowly added into
In the reaction system of step 2, high-speed stirred shearing 1h；The triethylamine that deionized water will be dissolved in adds reactant under high velocity agitation
System, is subsequently adding remaining deionized water and emulsifies 25~30min, and mixture is carried out into vacuum distillation after the completion of reaction, steams and helps
Solvent acetone, obtains the aqueous polyurethane dispersion of carbon nanotubes；
Step 4, the aqueous polyurethane dispersion of the carbon nanotubes that bright red mill base, step 3 are obtained, the oxidation of part polyoxypropylene
Ethylene Glycol ether mix and be slowly stirred after 30min pour into ball grinder add after ball milling monoethanolamine, polyethylene glycol 200,
Polyacrylamide, polyethyl acrylate, polypropylene wax and remaining polyoxypropylene ethylene oxide glycerin ether, continue ball milling 4h, ball
Mill speed is 400 revs/min, obtains nanometer water electrically conductive ink.
2. a kind of preparation method of nanometer water electrically conductive ink, it is characterised in that specifically implement according to following steps：
Step 1, weighed respectively according to mass percent multi-walled carbon nano-tubes 8~10%, hexamethylene diisocyanate 20~
22%th, Polyethylene glycol-2000 8~10%, dihydromethyl propionic acid 1~3%, 1-METHYLPYRROLIDONE 2~4%, 1,6-HD
0.3~3%, triethylamine 1~3%, deionized water 20~30%, butyl tin dilaurate 0.1~1%, acetone 1~3%, second two
Alcohol 6~9%, monoethanolamine 2~4%, polyethylene glycol 200 1~2%, polyacrylamide 1~2%, polyethyl acrylate 1~2%,
Polypropylene wax 1~2%, polyoxypropylene ethylene oxide glycerin ether 1~2% and bright red mill base 10%, said components mass percent
Value and be 100%；
Step 2, by ultrasonic disperse 30min after magnetic agitation 30min in multi-walled carbon nano-tubes addition ethylene glycol, obtains mixture A；
Step 3, hexamethylene diisocyanate and Polyethylene glycol-2000 is added and carries reflux condenser, thermometer and stirring
In the four-hole boiling flask of device, heating water bath adds butyl tin dilaurate reaction 30min after being warming up to 85 DEG C of stirring 2h；Then will
Temperature is down to 60 DEG C of mixtures for rapidly joining dihydromethyl propionic acid and 1-METHYLPYRROLIDONE, and then bath temperature control exists
60~70 DEG C of reaction 10min, are further continued for being warming up to 85 DEG C of reaction 2h, then cool the temperature to 35 DEG C；
Step 4,1,6- hexylene glycols are dissolved in acetone, and the mixture A obtained with step 2 is well mixed, and is then slowly added into
In the reaction system of step 3, high-speed stirred shearing 1h；The triethylamine that deionized water will be dissolved in adds reactant under high velocity agitation
System, is subsequently adding remaining deionized water and emulsifies 25~30min, and mixture is carried out into vacuum distillation after the completion of reaction, steams and helps
Solvent acetone, obtains the aqueous polyurethane dispersion of carbon nanotubes；
Step 5, the aqueous polyurethane dispersion of the carbon nanotubes that bright red mill base, step 4 are obtained, the oxidation of part polyoxypropylene
Ethylene Glycol ether mix and be slowly stirred after 30min pour into ball grinder add after ball milling monoethanolamine, polyethylene glycol 200,
Polyacrylamide, polyethyl acrylate, polypropylene wax and remaining polyoxypropylene ethylene oxide glycerin ether, continue ball milling 4h, ball
Mill speed is 400 revs/min, obtains nanometer water electrically conductive ink.
3. the preparation method of nanometer water electrically conductive ink according to claim 2, it is characterised in that weighed in step 1 many
Purifying is needed before wall carbon nano tube, specific purification step is：Undressed multi-walled carbon nano-tubes is calcined in 700 DEG C of air
2h, adds the NaOH solution of 4mol/L, is heated to reflux 2h, and filtering, washing add concentrated nitric acid and the concentrated sulfuric acid after 2h is dried at 80 DEG C
Mixture, then it is 7 to be washed with deionized after being heated to reflux 50min at 80 DEG C to pH, and finally the vacuum at 50 DEG C is done
Dry 24h is obtained final product.
4. the preparation method of nanometer water electrically conductive ink according to claim 3, it is characterised in that concentrated nitric acid and the concentrated sulfuric acid
Mixture in concentrated nitric acid and the concentrated sulfuric acid volume ratio be 1：3.
5. the preparation method of nanometer water electrically conductive ink according to claim 2, it is characterised in that ball mill in step 5
Rotating speed is 400 revs/min, and Ball-milling Time is 2h.
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| CN101541894A (en) * | 2006-11-27 | 2009-09-23 | 富士胶卷迪马蒂克斯股份有限公司 | Carbon nanotube ink |
| CN103333315A (en) * | 2013-07-09 | 2013-10-02 | 汕头市东和机械有限公司 | Preparation method of modified polyurethane used for printing ink |
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| US20140302296A9 (en) * | 2012-09-24 | 2014-10-09 | C3Nano Inc. | Transparent conductive films with carbon nanotubes, inks to form the films and corresponding processes |
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| CN101284966A (en) * | 2008-05-29 | 2008-10-15 | 西安理工大学 | Polyurethane based water-based ink and method for preparing same |
| CN103333315A (en) * | 2013-07-09 | 2013-10-02 | 汕头市东和机械有限公司 | Preparation method of modified polyurethane used for printing ink |
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