CN105907181B - A kind of light sensitivity PEDOT:The preparation and application of PSVMA/AuNPs conductive inks - Google Patents
A kind of light sensitivity PEDOT:The preparation and application of PSVMA/AuNPs conductive inks Download PDFInfo
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- CN105907181B CN105907181B CN201610412478.4A CN201610412478A CN105907181B CN 105907181 B CN105907181 B CN 105907181B CN 201610412478 A CN201610412478 A CN 201610412478A CN 105907181 B CN105907181 B CN 105907181B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
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Abstract
The invention discloses a kind of light sensitivity PEDOT:The preparation and application of PSVMA/AuNPs conductive inks, the mass percent of component and each component contained by the conductive ink are：PEDOT:PSVMA/AuNPs conductive powders 0.1~5%, moisturizer 1~10%, dopant 0.5~10%, surfactant 0.1~5%, solvent 73~98%；The conductive ink is made after each component is mixed, and by home ink jet printer spray printing in PET base material.Conductive ink of the present invention solves traditional PEDOT inks electrical property and flexibility is poor, the more complex problem of preparation process, has the advantages that cheap, preparation is simple, and flexibility is excellent, water-tolerant, good conductivity.
Description
Technical field
The present invention relates to conductive material technical fields, disperse more particularly, to a kind of PSVMA using light sensitivity
PEDOT, and growth in situ gold nanoparticle (AuNPs), the method that conductive ink is made.
Background technology
Inkjet printing technology has precision height, and resolution ratio prepares simple, the advantages such as at low cost up to 50 μm.And it is current
Also it is applied gold nanoparticle as ink in inkjet printing technology extensively.Nanogold due to its dimensional effect, dielectric effect,
The characteristic of catalytic performance and unique gold-sulfydryl interaction, photothermal conversion, (biology) chemical sensor, optoelectronic switch,
The fields such as catalysis, electrode material have a wide range of applications.Therefore, PEDOT/ nanogold composite materials are prepared, such nanometer is explored
The excellent properties that composite material synergistic effect is brought become new research hotspot.
Maitane etc. is prepared for PEDOT and gold nanorods respectively, and two kinds of solution are mixed, and double pentafluoroethane sulphurs are added dropwise
Acid imide lithium salts makes mixed solution settle, and the PEDOT/ being dispersed in organic phase (acetonitrile, DMF) has finally been prepared
AuNRs composite materials, the composite material are used in the preparation of transparent OLED device.Since the method for fractional steps prepares PEDOT/Au
The comparatively laborious complexity of process of composite material, many researchers put into the research that one-step method prepares PEDOT.
Phani seminars for the first time to one kettle way prepare PEDOT/Au nanocomposites reported, EDOT in acid condition by
Gold chloride oxidation and initiated oxidation, which polymerize, has finally obtained PEDOT, meanwhile, the gold chloride as oxidant is obtained by in-situ reducing
PEDOT/Au Micelle-like Nano-structure of Two is arrived.
After this, many scientists put into the research work of this material, to its reaction condition, mechanism and answer
With in depth being studied, and progress is achieved in electrochemical sensor, electrochromic property etc..But it is sharp
The PEDOT/Au prepared with one kettle way is usually formed sheet of aggregation, this gives prepares flexible electronic device using inkjet printing
Cause difficulty；And the nanogold of in-situ reducing has major part free in dispersions, can not more efficiently be fixed on
On PEDOT.Therefore, the grain size for the PEDOT/Au nanocomposites that control is prepared by one kettle way and fixed in-situ reducing
Nanogold becomes the key for improving the material property and application range.
Invention content
In view of the above-mentioned problems existing in the prior art, the applicant provides a kind of light sensitivity PEDOT:PSVMA/AuNPs
The preparation and application of conductive ink.Conductive ink of the present invention solves traditional PEDOT inks water resistance and flexibility is poor, prepares
The problem of complex process, conductive ink of the invention have cheap, prepare simple, water-tolerant, flexibility and electric conductivity
The advantages that good.
Technical scheme is as follows：
A kind of light sensitivity PEDOT:PSVMA/AuNPs conductive inks are made of the raw material of following degree：
The PEDOT:PSVMA/AuNPs conductive powders are random amphiphilic polymers：Poly- (sodium styrene sulfonate-co-
(7- (4- vinyl benzyls oxygroup) -4- methylcoumarins)-co- acrylic acid) and poly- 3,4- ethene dioxythiophenes and gold nanoparticle
Mixture；
The PEDOT:The preparation method of PSVMA/AuNPs conductive powders is：By PEDOT, that is, poly- 3,4- ethylene dioxy thiophenes
Pheno, PSVMA, that is, poly- (sodium styrene sulfonate-co- (7- (4- vinyl benzyls oxygroup) -4- methylcoumarins)-co- acrylic acid), with
Gold chloride is according to 10:1:1~10:5:5 mass ratio, mixes in water, and at 25~45 DEG C, redox polymerization obtains
PEDOT:PSVMA/AuNPs electrically conductive composites, then by freeze-drying, the PEDOT is made:PSVMA/AuNPs conductive powders.
The preparation method of the conductive ink, is as follows：
(1) by 0.1~5% PEDOT:PSVMA/AuNPs conductive powders are dissolved in 73~98% solvent, are added
0.5~10% dopant, 1~10% moisturizer and 0.1~5% surfactant, agitated, ultrasound is uniformly divided
Scattered mixed solution；
(2) filtering with microporous membrane for being 0.10 μm~0.45 μm by aperture by step (1) gained mixed liquor, you can obtain
The conductive ink.
Stirring is using magnetic agitation in the step (1), under conditions of speed of agitator is 200~600rpm, stirring 1~
36h；The ultrasound condition is：Ultrasonic power is 50W~600W, and the time is 20~60 minutes.
The preparation method of the PSVMA is：
With 1~2.5g 7- (4- vinyl benzyls oxygroup) -4- methylcoumarins) i.e. VM, 0.1~0.8g sodium styrene sulfonate
That is SS, 0.02~0.27g acrylic acid, that is, AA are as reaction monomers, using 0.01~0.15g azodiisobutyronitriles, that is, AIBN as instead
The initiator answered causes free radicals copolymerization reaction；
The mass ratio that VM, SS, AA and AIBN are dissolved in 30~50ml is 1:4~4:1 DMSO and DMF mixed solution
In, 60~75 DEG C of 22~30h of reaction；It is repeatedly settled in toluene after reaction, obtains white solid powder after purification
Last PSVMA；
PSVMA after purification is dried in vacuo at 50~70 DEG C until constant weight；The PSVMA weight average molecular weight being prepared
It is 10000~20000, molecular weight distribution 1.02-1.31, the wherein ratio shared by acrylic acid groups are 5~20%, cumarin
Ratio shared by group is 3~15%, and the ratio shared by gold nanoparticle is 15~30%.
The PEDOT:The grain size of PSVMA/AuNPs conductive powders is 42nm~100nm.
The moisturizer is one or more in sorbierite, propylene glycol, glycerine, butanediol, hexylene glycol.
The dopant is one or more in ethylene glycol, butanediol, DMSO.
The surfactant is neopelex, kayexalate, polyethylene glycol, polyvinylpyrrolidine
It is one or more in ketone.
The solvent is one kind in deionized water, methanol, ethyl alcohol, isopropanol, butanol, tetrahydrofuran, butyl glycol ether
Or it is a variety of.
The application of the conductive ink, the conductive ink are used for inkjet printing.
The present invention is beneficial to be had technical effect that：
(1) PEDOT is made by one kettle way in the present invention:PSVMA/AuNPs aqueous dispersions, method is simple and fast, simultaneously
The addition of PSVMA makes PEDOT have high dispersion in water, and gold nanoparticle is added, and can act synergistically with PEDOT
To improve the electrical property of conductive ink.
(2) present invention by be added can photodimerization PSVMA, make conductive ink that can be carried out under 365nm ultra violet lamps
Photo-crosslinking improves the water resistance and bending resistance of conductive pattern.
(3) present invention makes conductive ink surface by the way that the surfactant of different proportion, moisturizer, dopant is added
Power, viscosity, grain size wait and are suitable for 1390 type printers of EPSON progress inkjet printing.
(4) present invention is by by PEDOT:PSVMA/AuNPs conductive inks spray printing is on transparent base PET, due to PET bases
The hydrophobicity of material, ink are not easy spray printing on the surface of PET, and the present invention is made by the way that pet sheet face to be modified by ink jet printing
It is possibly realized in PET base material.
Specific implementation mode
With reference to embodiment, the present invention is specifically described.
Embodiment 1
It is a kind of it is water-soluble in light sensitivity PSVMA, the preparation method of light sensitivity PSVMA includes the following steps：
The preparation method of the PSVMA is with 1g 7- (4- vinyl benzyls oxygroup) -4- methylcoumarins) (VM), 0.1g benzene
Vinyl sulfonic acid sodium (SS), 0.02 acrylic acid (AA) are used as reaction monomers, using 0.01 azodiisobutyronitrile (AIBN) as reaction
Initiator causes free radicals copolymerization reaction.Reaction dissolvent is that mass ratio is 1:4 DMSO and DMF mixed solution.By VM, SS, AA
It is added in 100mL round-bottomed flasks and is dissolved in DMSO and DMF mixed solutions 30ml with AIBN, 60 DEG C of reaction 22h.Reaction terminates
It is settled in toluene afterwards, obtains PSVMA white solid powders.PSVMA solid powders are dissolved with DMSO, are carried out in toluene
Sedimentation is dried in vacuo at 50 DEG C in triplicate and obtains PSVMA after purification, weight average molecular weight 10000, molecular weight point
Cloth is 1.21；Ratio shared by acrylic acid groups is 8.4%, and the ratio shared by coumarin group is 3.7%.
Embodiment 2
It is a kind of it is water-soluble in light sensitivity PSVMA, the preparation method of light sensitivity PSVMA includes the following steps：
The preparation method of the PSVMA is with 2.5g 7- (4- vinyl benzyls oxygroup) -4- methylcoumarins) (VM), 0.8g
Sodium styrene sulfonate (SS), 0.27g acrylic acid (AA) are used as reaction monomers, using 0.15g azodiisobutyronitriles (AIBN) as instead
The initiator answered causes free radicals copolymerization reaction.Reaction dissolvent is that mass ratio is 4:1 DMSO and DMF mixed solution.By VM,
SS, AA and AIBN are added in 100mL round-bottomed flasks and are dissolved in DMSO and DMF mixed solutions 50ml, 75 DEG C of reaction 30h.Instead
It is settled in toluene after answering, obtains PSVMA white solid powders.PSVMA solid powders are dissolved with DMSO, in toluene
In settled, in triplicate, at 70 DEG C vacuum drying obtain PSVMA after purification.Its weight average molecular weight is 19800, point
Son amount is distributed as 1.17；Ratio shared by acrylic acid groups is 10.2%, and the ratio shared by coumarin group is 13%.
Embodiment 3
It is a kind of it is water-soluble in light sensitivity PSVMA, the preparation method of light sensitivity PSVMA includes the following steps：
The preparation method of the PSVMA is with 1.5g 7- (4- vinyl benzyls oxygroup) -4- methylcoumarins) (VM), 0.4g
Sodium styrene sulfonate (SS), 0.12g acrylic acid (AA) are used as reaction monomers, using 0.07g azodiisobutyronitriles (AIBN) as instead
The initiator answered causes free radicals copolymerization reaction.Reaction dissolvent is that mass ratio is 1:1 DMSO and DMF mixed solution.By VM,
SS, AA and AIBN are added in 100mL round-bottomed flasks and are dissolved in DMSO and DMF mixed solutions 40ml, 60 DEG C of reaction 25h.Instead
It is settled in toluene after answering, obtains white solid powder.The solid is dissolved with DMSO, after reaction in toluene
It is settled, obtains PSVMA white solid powders.PSVMA solid powders are dissolved with DMSO, are settled in toluene, are repeated
Three times, vacuum drying obtains PSVMA after purification at 60 DEG C.Its weight average molecular weight is 16000, molecular weight distribution 1.24；
Ratio shared by acrylic acid groups is 17%, and the ratio shared by coumarin group is 12%.
Embodiment 4
A kind of light sensitivity PEDOT:The preparation method of PSVMA/AuNPs conductive inks, the conductive ink includes the following steps：
(1) by 1g PEDOT:PSVMA/AuNPs conductive powders are dissolved in the mixing of 10.6g deionized waters and 9g ethyl alcohol composition
In solvent, 1g dopant ethylene glycol, 2g moisturizer glycerine, 1.5g surfactant polyvinylpyrrolidones, through magnetic are added
Power stirring (under conditions of rotating speed is 500rpm, stirs 20h), and ultrasound (ultrasonic power 300W, time are 40 minutes) obtains
The mixed liquor of even dispersion；
(2) filtering with microporous membrane for being 0.10 μm by aperture by step (1) gained mixed liquor, you can obtain the ink-jet
Printing conductive ink.
The PEDOT:PSVMA/AuNPs conductive powders are the poly- (sodium styrene sulfonate-co- (7- of random amphiphilic polymers
(4- vinyl benzyls oxygroup) -4- methylcoumarins)-co- acrylic acid) and poly- 3,4- ethene dioxythiophenes and gold nanoparticle is mixed
Close object, the PEDOT:The preparation method of PSVMA/AuNPs conductive powders is：By PEDOT, PSVMA, (such as case study on implementation 1 is made
It is standby) with gold chloride according to 10:5:2 mass ratio, mixes in water, and at 37 DEG C, PEDOT is made by stirring, ultrasonic disperse:
PSVMA/AuNPs aqueous dispersions, then by freeze-drying, the PEDOT is made:(grain size is PSVMA/AuNPs conductive powders
55nm)。
Using 1390 type printers of EPSON, using PET as print substrate, inkjet printing experiment is carried out.Duplicate printing 30 times
Conductive pattern is obtained on printing paper, under 360nm UV ultra violet lamps, the conductive ink patterns after photo-crosslinking is obtained, under ultrasound
Its water resistance is tested, its flexibility is tested by bending, is led before and after being used in combination the double electrical measurement four-point probes of RTS-9 types to compare bending
The resistance of electrical pattern, after bending, the resistance of conductive pattern is without significant change.And pass through UV-vis spectrophotometer testing films
Light transmittance.Test data is shown in Table 1.
Embodiment 5
A kind of light sensitivity PEDOT:The preparation method of PSVMA/AuNPs conductive inks, the conductive ink includes the following steps：
(1) by 1g PEDOT:PSVMA/AuNPs conductive powders be dissolved in 20g deionized waters and 10g butyl glycol ethers composition
In the mixed solvent, adds 3g dopant ethylene glycol, 2g moisturizer sorbierites, 2.5g surfactant polyvinylpyrrolidones,
Through magnetic agitation (under conditions of rotating speed is 300rpm, stirring 20h), ultrasound (ultrasonic power 200W, time are 60 minutes) obtains
To evenly dispersed mixed liquor；
(2) filtering with microporous membrane for being 0.22 μm by aperture by step (1) gained mixed liquor, you can obtain the ink-jet
Printing conductive ink.
The PEDOT:PSVMA/AuNPs conductive powders are the poly- (sodium styrene sulfonate-co- (7- of random amphiphilic polymers
(4- vinyl benzyls oxygroup) -4- methylcoumarins)-co- acrylic acid) and poly- 3,4- ethene dioxythiophenes and gold nanoparticle is mixed
Close object, the PEDOT:The preparation method of PSVMA/AuNPs conductive powders is：By PEDOT, PSVMA, (such as case study on implementation 1 is made
It is standby) with gold chloride according to 10:5:2 mass ratio, mixes in water, and at 30 DEG C, PEDOT is made by stirring, ultrasonic disperse:
PSVMA/AuNPs aqueous dispersions, then by freeze-drying, the PEDOT is made:(grain size is PSVMA/AuNPs conductive powders
63nm)。
Using 1390 type printers of EPSON, using PET as print substrate, inkjet printing experiment is carried out.Duplicate printing 30 times
Conductive pattern is obtained on printing paper, under 360nm UV ultra violet lamps, the conductive ink patterns after photo-crosslinking is obtained, under ultrasound
Its water resistance is tested, its flexibility is tested by bending, is led before and after being used in combination the double electrical measurement four-point probes of RTS-9 types to compare bending
The resistance of electrical pattern, after bending, the resistance of conductive pattern is without significant change.And pass through UV-vis spectrophotometer testing films
Light transmittance.Test data is shown in Table 1.
Embodiment 6
A kind of light sensitivity PEDOT:The preparation method of PSVMA/AuNPs conductive inks, the conductive ink includes the following steps：
(1) by 1g PEDOT:PSVMA/AuNPs conductive powders are dissolved in 20g deionized waters and 10g ethyl alcohol and 10g isopropanols
The in the mixed solvent of composition adds 3g dopant butanediols, 4g moisturizer glycerine, 2g surfactant polystyrolsulfon acids
Sodium, through magnetic agitation (under conditions of rotating speed is 500rpm, stirring 27h), ultrasound (ultrasonic power 300W, time are 40 minutes)
Obtain evenly dispersed mixed liquor；
(2) filtering with microporous membrane for being 0.10 μm by aperture by step (1) gained mixed liquor, you can obtain the ink-jet
Printing conductive ink.
The PEDOT:PSVMA/AuNPs conductive powders are the poly- (sodium styrene sulfonate-co- (7- of random amphiphilic polymers
(4- vinyl benzyls oxygroup) -4- methylcoumarins)-co- acrylic acid) and poly- 3,4- ethene dioxythiophenes and gold nanoparticle is mixed
Close object, the PEDOT:The preparation method of PSVMA/AuNPs conductive powders is：By PEDOT, PSVMA, (such as case study on implementation 2 is made
It is standby) with gold chloride according to 10:3:4 mass ratio, mixes in water, and at 32 DEG C, PEDOT is made by stirring, ultrasonic disperse:
PSVMA/AuNPs aqueous dispersions, then by freeze-drying, the PEDOT is made:(grain size is PSVMA/AuNPs conductive powders
65nm)。
Using 1390 type printers of EPSON, using PET as print substrate, inkjet printing experiment is carried out.Duplicate printing 30 times
Conductive pattern is obtained on printing paper, under 360nm UV ultra violet lamps, the conductive ink patterns after photo-crosslinking is obtained, under ultrasound
Its water resistance is tested, its flexibility is tested by bending, is led before and after being used in combination the double electrical measurement four-point probes of RTS-9 types to compare bending
The resistance of electrical pattern, after bending, the resistance of conductive pattern is without significant change.And pass through UV-vis spectrophotometer testing films
Light transmittance.Test data is shown in Table 1.
Embodiment 7
A kind of light sensitivity PEDOT:The preparation method of PSVMA/AuNPs conductive inks, the conductive ink includes the following steps：
(1) by 1g PEDOT:PSVMA/AuNPs conductive powders are dissolved in 15g deionized waters and 8.75g butanediol butyl ether composition
In the mixed solvent, add 1.5g dopant ethylene glycol, 1g moisturizer butanediols, 1.5g surfactant polyethylenes, warp
Magnetic agitation (under conditions of rotating speed is 500rpm, stirring is for 24 hours), ultrasound (ultrasonic power 100W, time are 30 minutes) obtain
Evenly dispersed mixed liquor；
(2) filtering with microporous membrane for being 0.10 μm by aperture by step (1) gained mixed liquor, you can obtain the ink-jet
Printing conductive ink.
The PEDOT:PSVMA/AuNPs conductive powders are the poly- (sodium styrene sulfonate-co- (7- of random amphiphilic polymers
(4- vinyl benzyls oxygroup) -4- methylcoumarins)-co- acrylic acid) and poly- 3,4- ethene dioxythiophenes and gold nanoparticle is mixed
Close object, the PEDOT:The preparation method of PSVMA/AuNPs conductive powders is：By PEDOT, PSVMA, (such as case study on implementation 2 is made
It is standby) with gold chloride according to 10:4:5 mass ratio, mixes in water, and at 37 DEG C, PEDOT is made by stirring, ultrasonic disperse:
PSVMA/AuNPs aqueous dispersions, then by freeze-drying, the PEDOT is made:(grain size is PSVMA/AuNPs conductive powders
69nm)。
Using 1390 type printers of EPSON, using PET as print substrate, inkjet printing experiment is carried out.Duplicate printing 30 times
Conductive pattern is obtained on printing paper, under 360nm UV ultra violet lamps, the conductive ink patterns after photo-crosslinking is obtained, under ultrasound
Its water resistance is tested, its flexibility is tested by bending, is led before and after being used in combination the double electrical measurement four-point probes of RTS-9 types to compare bending
The resistance of electrical pattern, after bending, the resistance of conductive pattern is without significant change.And pass through UV-vis spectrophotometer testing films
Light transmittance.Test data is shown in Table 1.
Embodiment 8
A kind of light sensitivity PEDOT:The preparation method of PSVMA/AuNPs conductive inks, the conductive ink includes the following steps：
(1) by 1g PEDOT:PSVMA/AuNPs conductive powders are dissolved in 21g deionized waters and 5g ethyl alcohol and 5g butanol composition
In the mixed solvent, add 3g dopant ethylene glycol, 2g moisturizer sorbierites, 2g surfactant sodium dodecyl base benzene sulfonic acids
Sodium, through magnetic agitation (under conditions of rotating speed is 500rpm, stirring 30h), ultrasound (ultrasonic power 150W, time are 45 minutes)
Obtain evenly dispersed mixed liquor；
(2) filtering with microporous membrane for being 0.22 μm by aperture by step (1) gained mixed liquor, you can obtain the ink-jet
Printing conductive ink.
The PEDOT:PSVMA/AuNPs conductive powders are the poly- (sodium styrene sulfonate-co- (7- of random amphiphilic polymers
(4- vinyl benzyls oxygroup) -4- methylcoumarins)-co- acrylic acid) and poly- 3,4- ethene dioxythiophenes and gold nanoparticle is mixed
Close object, the PEDOT:The preparation method of PSVMA/AuNPs conductive powders is：By PEDOT, PSVMA, (such as case study on implementation 3 is made
It is standby) with gold chloride according to 10:2:2 mass ratio, mixes in water, and at 37 DEG C, PEDOT is made by stirring, ultrasonic disperse:
PSVMA/AuNPs aqueous dispersions, then by freeze-drying, the PEDOT is made:(grain size is PSVMA/AuNPs conductive powders
45nm)。
Using 1390 type printers of EPSON, using PET as print substrate, inkjet printing experiment is carried out.Duplicate printing 30 times
Conductive pattern is obtained on printing paper, under 360nm UV ultra violet lamps, the conductive ink patterns after photo-crosslinking is obtained, under ultrasound
Its water resistance is tested, its flexibility is tested by bending, is led before and after being used in combination the double electrical measurement four-point probes of RTS-9 types to compare bending
The resistance of electrical pattern, after bending, the resistance of conductive pattern is without significant change.And pass through UV-vis spectrophotometer testing films
Light transmittance.Test data is shown in Table 1.
Embodiment 9
A kind of light sensitivity PEDOT:The preparation method of PSVMA/AuNPs conductive inks, the conductive ink includes the following steps：
(1) by 1g PEDOT:PSVMA/AuNPs conductive powders are dissolved in 20g deionized waters and 15g butanol and 7.5g ethylene glycol
The in the mixed solvent of butyl ether composition, adds 4g dopant ethylene glycol, 6g moisturizer glycerine, 3g surfactant polystyrene
Sodium sulfonate, through magnetic agitation (under conditions of rotating speed is 450rpm, stirring 25h), ultrasonic (ultrasonic power 200W, time 40
Minute) obtain evenly dispersed mixed liquor；
(2) filtering with microporous membrane for being 0.10 μm by aperture by step (1) gained mixed liquor, you can obtain the ink-jet
Printing conductive ink.
The PEDOT:PSVMA/AuNPs conductive powders are the poly- (sodium styrene sulfonate-co- (7- of random amphiphilic polymers
(4- vinyl benzyls oxygroup) -4- methylcoumarins)-co- acrylic acid) and poly- 3,4- ethene dioxythiophenes and gold nanoparticle is mixed
Close object, the PEDOT:The preparation method of PSVMA/AuNPs conductive powders is：By PEDOT, PSVMA, (such as case study on implementation 3 is made
It is standby) with gold chloride according to 10:2:4 mass ratio, mixes in water, and at 37 DEG C, PEDOT is made by stirring, ultrasonic disperse:
PSVMA/AuNPs aqueous dispersions, then by freeze-drying, the PEDOT is made:(grain size is PSVMA/AuNPs conductive powders
73nm)。
Using 1390 type printers of EPSON, using PET as print substrate, inkjet printing experiment is carried out.Duplicate printing 30 times
Conductive pattern is obtained on printing paper, under 360nm UV ultra violet lamps, the conductive ink patterns after photo-crosslinking is obtained, under ultrasound
Its water resistance is tested, its flexibility is tested by bending, is led before and after being used in combination the double electrical measurement four-point probes of RTS-9 types to compare bending
The resistance of electrical pattern, after bending, the resistance of conductive pattern is without significant change.And pass through UV-vis spectrophotometer testing films
Light transmittance.Test data is shown in Table 1.
Table 1
Can see from the data of table 1, the conductive ink that the present invention is prepared have low resistance, high transparency it is excellent
Point；And under the action of 3M adhesive tapes, spray printing pattern can be very good to be adhered on the surface of PET, and adhesive force grade is 1 grade,
Show that the adhesiveness for the conductive ink and PET base material that the present invention is prepared is very high.
Claims (10)
1. a kind of light sensitivity PEDOT:PSVMA/AuNPs conductive inks, it is characterised in that by the raw material group of following degree
At：
PEDOT:PSVMA/AuNPs conductive powders 0.1~5%
The PEDOT:PSVMA/AuNPs conductive powders are random amphiphilic polymers：Poly- (sodium styrene sulfonate-co- (7- (4-
Vinyl benzyl oxygroup) -4- methylcoumarins)-co- acrylic acid) and poly- 3,4- ethene dioxythiophenes and gold nanoparticle mixing
Object；
The PEDOT:The preparation method of PSVMA/AuNPs conductive powders is：By PEDOT, that is, poly- 3,4- ethene dioxythiophenes,
PSVMA, that is, poly- (sodium styrene sulfonate-co- (7- (4- vinyl benzyls oxygroup) -4- methylcoumarins)-co- acrylic acid), with chlorine gold
Acid is according to 10:1:1~10:5:5 mass ratio, mixes in water, and at 25~45 DEG C, redox polymerization obtains PEDOT:
PSVMA/AuNPs electrically conductive composites, then by freeze-drying, the PEDOT is made:PSVMA/AuNPs conductive powders.
2. a kind of preparation method of conductive ink described in claim 1, it is characterised in that be as follows：
(1) by 0.1~5% PEDOT:PSVMA/AuNPs conductive powders are dissolved in 73~98% solvent, add 0.5~
10% dopant, 1~10% moisturizer and 0.1~5% surfactant, agitated, ultrasound obtains evenly dispersed
Mixed solution；
(2) filtering with microporous membrane for being 0.10 μm~0.45 μm by aperture by step (1) gained mixed liquor, you can obtain described
Conductive ink.
3. preparation method according to claim 2, it is characterised in that stirring uses magnetic agitation in the step (1), stirs
Under conditions of mix rotating speed is 200~600rpm, 1~36h is stirred；The ultrasound condition is：Ultrasonic power is 50W~600W, when
Between be 20~60 minutes.
4. conductive ink according to claim 1, it is characterised in that the preparation method of the PSVMA is：
With 1~2.5g 7- (4- vinyl benzyls oxygroup) -4- methylcoumarins) i.e. VM, 0.1~0.8g sodium styrene sulfonate, that is, SS,
0.02~0.27g acrylic acid, that is, AA is as reaction monomers, using 0.01~0.15g azodiisobutyronitriles, that is, AIBN drawing as reaction
It sends out agent and causes free radicals copolymerization reaction；
The mass ratio that VM, SS, AA and AIBN are dissolved in 30~50ml is 1:4~4:In 1 DMSO and DMF mixed solution, 60
~75 DEG C of 22~30h of reaction；It is repeatedly settled in toluene after reaction, obtains white solid powder after purification
PSVMA；
PSVMA after purification is dried in vacuo at 50~70 DEG C until constant weight；The PSVMA weight average molecular weight being prepared is
10000~20000, molecular weight distribution 1.02-1.31, the wherein ratio shared by acrylic acid groups are 5~20%, cumarin base
The shared ratio of group is 3~15%.
5. conductive ink according to claim 1, it is characterised in that the PEDOT:The grain of PSVMA/AuNPs conductive powders
Diameter is 42nm~100nm.
6. conductive ink according to claim 1, it is characterised in that the moisturizer be sorbierite, propylene glycol, glycerine,
It is one or more in butanediol, hexylene glycol.
7. conductive ink according to claim 1, it is characterised in that the dopant is in ethylene glycol, butanediol, DMSO
It is one or more.
8. conductive ink according to claim 1, it is characterised in that the surfactant be neopelex,
It is one or more in kayexalate, polyethylene glycol, polyvinylpyrrolidone.
9. conductive ink according to claim 1, it is characterised in that the solvent is deionized water, methanol, ethyl alcohol, isopropyl
It is one or more in alcohol, butanol, tetrahydrofuran, butyl glycol ether.
10. a kind of application of 1,4~9 any one conductive ink of claim, it is characterised in that the conductive ink is for spraying
Ink printing.
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