CN104212243B - A kind of preparation method of PEDOT/PSS electrically conductive ink and coating - Google Patents
A kind of preparation method of PEDOT/PSS electrically conductive ink and coating Download PDFInfo
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Abstract
The present invention relates to the preparation methods for including PEDOT/PSS electrically conductive ink and coating.The preparation process of electrically conductive ink are as follows: with the PEDOT/PSS dispersion liquid that acid PEDOT/PSS dispersion liquid or neutralisation are handled, addition thickener reaches viscosity needed for ink；And 3,4- ethylenedioxy thiophene (EDOT) polymerize in the presence of polyvinylbenzenesulfonic acid (PSS) forms PEDOT/PSS, added alkalinity additive adjusts pH value to weakly acidic pH, aged technique reaches using after viscosity, remove inorganic salts, after obtaining the PEDOT/PSS dispersion liquid of neutral inks viscosity, dispersion liquid addition to these ink viscosities includes guanamine and at least one carbonyls at least one condensation product formed and/or the polyester liquid of non-aqueous dosage form as adhesive, and the other function additives matched are up to PEDOT/PSS electrically conductive ink.It is coated with using these electrically conductive inks up to PEDOT/PSS conductive coating, wherein neutral PEDOT/PSS conductive coating is stablized, performance is best.
Description
Technical field
The present invention relates to it is a kind of can the PEDOT/PSS electrically conductive ink of neutralisation and the preparation method of coating, belong to conductive height
Molecular functional materials field.
Background technique
Transparent conductive film has highly important status in display and solar energy industry.In recent years, because plane is aobvious
Show the mass production of device, almost exhaust currently used for make transparent conductive film indium tin oxide (Indium Tin Oxide,
ITO) the supply of material.For this purpose, the whole world has many research institutions all finding viable option.In addition, more because of ITO material
The continuous hurricane of price rise and limitation of the ITO material on large scale processing procedure replaces along with the rise of flexible electronic industry
The material of ITO is put forward one after another.
Conductive polymer poly 3,4-ethylene dioxythiophene-polyvinylbenzenesulfonic acid (PEDOT/PSS) is 3,4- enedioxy thiophene
The polymer of pheno (EDOT) monomer.Currently, PEDOT/PSS is the most widely used conducting polymer in photoelectric component field
One of.As novel transparent conductive material, transparent conductive film made of PEDOT/PSS makes and flexible electrical in large scale
Sub- industrial field has traditional ITO material to be difficult to the advantage being equal to.
However, the development of the transparent conductive film of conducting polymer PEDOT/PSS production is still by organic polymer itself
The limitation of defect, is mainly manifested in:
(1) printing film-forming process requires the PEDOT/PSS electrically conductive ink used to have certain viscosity, existing high viscosity
Addition thickener is generally required in ink preparation process.Due to the addition of dielectric thickener, so that being led by PEDOT/PSS
The electric conductivity of the transparent conductive film of electric printing ink to manufacture declines, mist degree rises etc.；
(2) the PEDOT/PSS transparent conductive film based on polymer is environment resistant, for example, in terms of water-fast, solvent resistant
Stability is compared to ITO and other type transparent electrode new materials still have deficiency；
It (3), can be because of its corrosivity when being contacted with metal further, since the PEDOT/PSS dispersion liquid prepared shows highly acid
And metallic conductivity is caused to decline, seriously limiting the metallic conductions material such as itself and nano-silver thread, metal grill and mixing makes
The compatibility of used time, and production transparent electrode stability.
Therefore, in order to make conducting polymer PEDOT/PSS transparent conductive film field realize large-scale application, it is still necessary to
Overcome the above problem.
Summary of the invention
The purpose of the present invention is to provide a kind of viscosity characteristics influence performance it is small, it is environment resistant it is good can neutralisation
PEDOT/PSS electrically conductive ink, scheme are to solve neutralisation and viscosity problem during the reaction.
In PEDOT/PSS polymerization reaction late stage, neutralisation processing is first carried out, viscosity tune is then carried out by ageing process again
Section thickens finally except deionization is to get to PEDOT/PSS dispersion liquid neutral, with ink viscosity to avoid being added
Agent after continuously adding at least one function additive, obtains PEDOT/PSS electrically conductive ink.The neutral conductive ink can use silk screen
The extensive coating of the methods of printing, resulting conductive coating has high transparency and lower haze value, compound with nano-silver thread
The conductive coating obtained after coating film forming has astonishing and stable electric conductivity.
This method by improving polymerization technique, avoids the dielectric thickener in PEDOT/PSS dispersion liquid
Addition and direct neutralisation bring in and ion influence so that the conduction of the film made of the neutral conductive ink
The performances such as rate, light transmittance and mist degree are greatly improved；The neutral PEDOT/PSS material of this no ion is itself and other kinds
The conductive material of class, such as being used in mixed way for nano-silver thread, metal grill provide possibility, significantly reduce due to acidity
The possibility for corroding metal has been particularly ensured that the electric conductivity of gained conductive coating and stability are unaffected.Solution of the invention
In scheme, by pointedly adding organic function additive, the environment resistant of transparent conductive film is improved, it is such as water-fast, resistance to molten
The stability etc. of agent etc..The present invention is achieved by the following technical solutions:
1, the PEDOT/PSS electrically conductive ink, be can on the basis of different types of PEDOT/PSS dispersion liquid,
Organic function additive is added to be prepared.In the organic functions auxiliary agent, a kind of guanamine and at least one carbonyl are included at least
At least one condensation product that based compound is formed is as adhesive.
The condensation product that guanamine and at least one carbonyls are formed, preferably guanamine and aldehydes or ketones are condensed.It is suitble to
Aldehydes or ketones are as follows: formaldehyde, acetaldehyde, butyraldehyde, acetone or methyl ethyl ketone.Particularly preferably formaldehyde；Guanamine and at least one carbonyl
The particularly preferred condensation product of based compound is guanamine-formaldehyde condensation products, such as logical formula (I) of structure
In formula
R1Indicate H or linear chain or branched chain C1~C8 alkyl, phenyl or the mono-, two-, three-phenyl replaced, preferably H or straight
Chain or branch C1~C4 alkyl, phenyl, particularly preferably H or methyl, ethyl and phenyl.
R2To R5H or CH is indicated independently of one another2-OR6, group R2To R5At least one of be not H, and R6Indicate H or
Linear chain or branched chain C1~C8 alkyl, preferably H or linear chain or branched chain C1~C4 alkyl, particularly preferably R2To R5All indicate H or CH2-
OR6。
And guanamine-formaldehyde condensation products particularly preferred in this way can be the condensation product of logical formula (I) to each other or with it is another
The condensation product of outer guanamine.
In addition, the particularly preferred guanamine-formaldehyde condensation products can be partly or entirely etherified.Additionally or alternatively
Ground is selected, the particularly preferred guanamine-formaldehyde condensation products can change by reacting with amine, aminocarboxylic acids or sulphite
Property, or by that can be modified with the compound such as phenols of aldehyde reaction or ureas cocondensation with other, to improve in water molten
Xie Du.
Content of the condensation product of guanamine and at least one carbonyls in the PEDOT/PSS electrically conductive ink is based on
PEDOT/PSS dispersion liquid weight is 0.001~15 weight %, preferably 0.1~2 weight %.
2, the PEDOT/PSS electrically conductive ink, be can on the basis of different types of PEDOT/PSS dispersion liquid,
Organic function additive is added to be prepared.In the organic functions auxiliary agent, include at least a kind of molten with alcohol, ether, ketone equal solvent
The polyester liquid of the non-aqueous dosage form of solution is as adhesive.The polyester adhesive of non-aqueous dosage form used specifically refers to more contracting second
Two acid esters of glycol (n >=10) and its modifier or with two acid esters of diglycol and its modifier, modify mode such as end group
Siliconization etc.；
Alcohol can be methanol, ethyl alcohol, normal propyl alcohol, isopropanol, butanol, n-octyl alcohol, glycol or glycol ethers, such as ethylene glycol, 1,
2- propylene glycol, 1,3-PD or diethylene glycol (DEG)；Ether can be ether, positive propyl ether, n-butyl ether, methyl-n-butyl ether, methyl tertiary butyl ether(MTBE), second
Glycol dimethyl ether, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane.Ketone can be acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl tertbutyl
Ketone；
Polymer content is 20~45%, preferably 25~30% in polyester liquid；
The polyester liquid of the non-aqueous dosage form dissolved with alcohol, ether, ketone equal solvent is in the PEDOT/PSS electrically conductive ink
It is 0.001~15 weight %, preferably 0.1~2 weight % that content, which is based on PEDOT/PSS dispersion liquid weight,.
In PEDOT/PSS electrically conductive ink provided by the invention, the above two classes adhesive, the two weight can also be added simultaneously
Ratio 1: 10~1: 1, add up to content be respectively 0.001~15 weight % based on neutral dispersion liquid weight, preferably 0.1~2
Weight %.
Adhesive provided by the invention can relieving haperacidity PEDOT/PSS electrically conductive ink, common neutralisation can also be made
PEDOT/PSS electrically conductive ink.The latter is to adjust pH value in close using alkalinity additive in acid PEDOT/PSS dispersion liquid
Property, wherein since acid-base reaction can generate part neutral ion, if do not removed, the property of conductive coating can be seriously affected
Energy.
Neutralisation is realized in the polymerization, while solving viscosity characteristics is the conduction of PEDOT/PSS involved in the present invention
The core of ink.Phosphate can be added as viscosity modifier before polymerization reaction, and ester moiety therein can be methyl, second
Base, propyl, normal-butyl, isopropyl and combinations thereof；The neutralisation that reaction solution carries out is handled after polymerization reaction, to use alkalinity to add
Agent is added to adjust pH value to weakly acidic pH；
Used alkalinity additive can be alkali metal hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide, alkali
Metal carbonate or bicarbonate such as lithium carbonate, sodium carbonate, potassium carbonate or sodium bicarbonate, saleratus, alkaline-earth metal hydroxide
Object such as magnesium hydroxide, calcium hydroxide, alkaline earth carbonate or bicarbonate such as magnesium carbonate, calcium carbonate, ammonia, aliphatic alkylamine is for example
The alkylamine of the mono- of alkyl with the C1~C20 optionally replaced, two or three-, such as methylamine, dimethylamine, trimethylamine, ethamine, two
Ethamine, triethylamine, ethanol amine or dimethylethanolamine, aromatic amine such as aniline, diphenylamines, adjacent diphenylamines, diphenylamines or right
Diphenylamines.
Alkalinity additive preferably uses as a solution, and preferred solvent can be water and/or alcohol, for neutralizing PEDOT/
PSS dispersion liquid.Alcohol can be methanol, ethyl alcohol, normal propyl alcohol, isopropanol, butanol, n-octyl alcohol, glycol or glycol ethers, as ethylene glycol,
1,2-PD, 1,3-PD or diethylene glycol (DEG)；
Above-mentioned alkalinity additive is also suitable for the preparation of the PEDOT/PSS electrically conductive ink of the above common neutralisation.
PEDOT/PSS electrically conductive ink provided by the invention, alkalinity additive is added in PEDOT/PSS dispersion liquid, is led to
Cross pH agent regulation system pH value, pH value range is 5.0~9.0, and preferably pH range is 6.0~8.0, more preferable pH value is 6.5~
7.2；
After pH value is adjusted, ageing process need to be passed through, reaction solution is made to reach the range of viscosities of ink requirements, range of viscosities 1
000~50 000mPas, preferred viscosity ranges are 2 000~20 000mPas；More preferable range of viscosities is 5 000~8
000mPa·s；
After ageing to the range of viscosities for reaching ink requirements, it is also necessary to it is operated by certain aftertreatment technology, i.e., it will be anti-
It answers mixture to shift, adds cation-exchanger and anionite, to remove inorganic salts, obtain that neutral, ink is viscous
PEDOT/PSS dispersion liquid spend, without ion, for preparing neutral conductive ink.The organic function added when preparing electrically conductive ink
Energy auxiliary agent further includes other organic functions auxiliary agents, such as conduction-enhancing agent, surfactant and levelling agent in addition to adhesive；
With it is above-mentioned can neutralisation PEDOT/PSS electrically conductive ink, can be in the bases such as glass, PET, PEN, PMMA and PC
Coating obtains the conductive coating of functionalization on bottom.
Detailed description of the invention
Electrode sheet resistance varies with temperature trend after PEDOT/PSS and nano-silver thread are compound
Specific embodiment
The present invention will now be described in detail with reference to examples, which is provided premised on inventive technique scheme
Detailed embodiment and specific operational process of craft, but protection scope of the present invention is not limited solely to following implementation
Example.
First part: the preparation of neutral PEDOT/PSS dispersion liquid
The polymerization technique (referring to Bayer AG.EP0686662,1995) of PEDOT/PSS dispersion liquid: by 250g water, 2.5g
The sodium peroxydisulfate of polystyrolsulfon acid, 10% ferric sulfate (III) of 55mg and 2.35g is added in reaction vessel, adjusts temperature
Degree, stirring and dissolving.Temperature is reduced to room temperature, is added 1.0g ethene-dioxythiophene (EDOT), is reacted.
Examples 1 to 5 and comparative example 1~2 are the system of neutralisation PEDOT/PSS dispersion liquid on the basis of above-mentioned polymerization technique
It is standby.
Embodiment 1:
After PEDOT/PSS polymerization reaction, stop reaction.2-amino-2-methyl-1-propanol is added, is supervised by pH meter
It surveys after adjusting pH value to weakly acidic pH, is aged 0.5 hour.Mixture is transferred in beaker, 50 milliliters of cation is added and hands over
Change agent (Lewatit S100H, Lanxess AG) and 29 milliliters of anionite (Lewatit MP62, Lanxess AG)
Remove inorganic salts.After this mixture is stirred 6 hours, exchanger, rotary viscometer tested viscosity are filtered out；
Embodiment 2:
After PEDOT/PSS polymerization reaction, stop reaction.0.2g triethyl phosphate is added, then adds 2- amino-
2- methyl-1-propyl alcohol is monitored after adjusting pH value to weakly acidic pH by pH meter, is aged 0.5 hour.According to Xiang Tongfang in embodiment 1
Method, after carrying out yin and yang resin exchange processing, rotary viscometer tested viscosity；
Embodiment 3:
After PEDOT/PSS polymerization reaction, stop reaction, 2-amino-2-methyl-1-propanol is added, is supervised by pH meter
It surveys after adjusting pH value to weakly acidic pH, is aged 1 hour.According to same procedure in embodiment 1, after carrying out yin and yang resin exchange processing,
Rotary viscometer tested viscosity；
Embodiment 4:
After PEDOT/PSS polymerization reaction, stop reaction, 2-amino-2-methyl-1-propanol is added, is supervised by pH meter
It surveys and adjusts pH value to after neutrality, be aged 2 hours, after carrying out yin and yang resin exchange processing according to same procedure in embodiment 1, rotation
Turn viscosity apparatus tested viscosity；
Embodiment 5:
After PEDOT/PSS polymerization reaction, stop reaction, 2-amino-2-methyl-1-propanol is added, is supervised by pH meter
It surveys and adjusts pH value to after neutrality, be aged 5 hours, after carrying out yin and yang resin exchange processing according to same procedure in embodiment 1, rotation
Turn viscosity apparatus tested viscosity；
Comparative example 1:
In embodiment 1 after PEDOT/PSS polymerization reaction, stop reaction, is aged 2 hours, according to identical in embodiment 1
After method carries out yin and yang resin exchange processing, 2-amino-2-methyl-1-propanol is added, is monitored by pH meter and adjusts pH value to close
After neutrality, rotary viscometer tested viscosity；
Comparative example 2:
In embodiment 1 after PEDOT/PSS polymerization reaction, stop reaction, is aged 5 hours, according to identical in embodiment 1
After method carries out yin and yang resin exchange processing, 2-amino-2-methyl-1-propanol is added, monitoring pH value is adjusted to close by pH meter
After neutrality, rotary viscometer tested viscosity；
Table 1: PEDOT/PSS dispersion viscosity and pH value in Examples 1 to 5 and comparative example 1~2
| Digestion time (hour) | Viscosity (mPas) | PH value | |
| Embodiment 1 | 0.5 | 537 | 7.4 |
| Embodiment 2 | 0.5 | 4500 | 7.5 |
| Embodiment 3 | 1 | 2354 | 7.6 |
| Embodiment 4 | 2 | 4672 | 8.0 |
| Embodiment 5 | 5 | 4736 | 7.8 |
| Comparative example 1 | 2 | 25 | 7.5 |
| Comparative example 2 | 5 | 33 | 7.6 |
Conclusion: embodiment is with the operational difference of comparative example: alkali being first added in embodiment and adjusts pH value, is then aged
Different time (0.5 hour, 1 hour, 2 hours, 5 hours), post-processes using anion-cation exchange resin；And comparative example is then
Different time (2 hours, 5 hours) first are aged, are then post-processed by anion-cation exchange resin, alkali is added and adjusts pH value.
As clearly seen from Table 1, in embodiment 1,3,4 and 5 neutralisation PEDOT/PSS dispersion liquid obtained viscosity
It is incremented by with the extension of digestion time, until viscosity is basicly stable after digestion time 2 hours；And embodiment 2, it joined tricresyl phosphate
Ethyl ester is as material, and after ageing 0.5 hour, viscosity with the medium viscosity of embodiment 4 and 5 i.e. close to stable (being worth essentially identical)；Comparison
The viscosity of neutralisation PEDOT/PSS dispersion liquid obtained does not change with digestion time and is changed in example 1~2, is low viscosity
Dispersion liquid, in the coating process such as silk-screen printing, needing to add thickener in advance and reaching required viscosity could be used.
Second part: the preparation and transparent conductive film performance test of neutral PEDOT/PSS electrically conductive ink
Embodiment 6~10 be made from embodiment 4 on the basis of neutralisation PEDOT/PSS dispersion liquid, addition adhesive,
Surfactant and conduction-enhancing agent prepare neutralisation PEDOT/PSS electrically conductive ink；Comparative example 3~7 is in 1 He of comparative example
On the basis of commercially available PH500 product, addition thickener, adhesive, surfactant and conduction-enhancing agent prepare neutralisation
PEDOT/PSS electrically conductive ink.Benzene birds droppings amine-formaldehyde resin WH-0.3 used in embodiment and comparative example and the contracting of adipic acid one two
Polyglycol ester methyl ethyl ketone solution SJS-2 or polyethylene glycol dipelargonate aqueous isopropanol SJS-3 are ground by Shanghai synthetic resin
Study carefully synthesized production.
Embodiment 6:
In embodiment 4 in neutrality PEDOT/PSS dispersion liquid obtained, add WH-03 (1 weight %),(0.1
Weight %) and ethylene glycol (5 weight %)；
Embodiment 7:
In embodiment 4 in neutrality PEDOT/PSS dispersion liquid obtained, add SJS-2 (1 weight %),(0.1
Weight %) and ethylene glycol (5 weight %)；
Embodiment 8:
In embodiment 4 in neutrality PEDOT/PSS dispersion liquid obtained, add SJS-3 (1 weight %),(0.1
Weight %) and ethylene glycol (5 weight %)；
Embodiment 9:
In embodiment 4 in neutrality PEDOT/PSS dispersion liquid obtained, WH-03 (0.5 weight %), SJS-2 (0.5 weight
Measure %),(0.1 weight %) and ethylene glycol (5 weight %)；
Embodiment 10:
In embodiment 4 in neutrality PEDOT/PSS dispersion liquid obtained, WH-03 (0.5 weight %), SJS-3 (0.5 weight
Measure %),(0.1 weight %) and ethylene glycol (5 weight %)；
Comparative example 3:
In comparative example 1 in neutrality PEDOT/PSS dispersion liquid obtained, add DOW company's T T-615 (0.5 weight %), WH-
03 (1 weight %),(0.1 weight %) and ethylene glycol (5 weight %)；
Comparative example 4:
In comparative example 1 in neutrality PEDOT/PSS dispersion liquid obtained, add TT-615 (0.5 weight %), SJS-2 (1 weight
Measure %),(0.1 weight %) and ethylene glycol (5 weight %)；
Comparative example 5:
Commercially available Heraeus Inc. CLEVIOSTM2- amino-2-methyl -1- third is added in the PEDOT/PSS dispersion liquid of pH500
Alcohol is monitored by pH meter and adjusts pH value to weakly acidic pH, in neutrality PEDOT/PSS dispersion liquid obtained, addition TT-615 (0.5
Weight %), WH-03 (1 weight %),(0.1 weight %) and ethylene glycol (5 weight %)；
Comparative example 6:
Commercially available Heraeus Inc. CLEVIOSTM2- amino-2-methyl -1- third is added in the PEDOT/PSS dispersion liquid of PH500
Alcohol is monitored by pH meter and adjusts pH value to weakly acidic pH, in neutrality PEDOT/PSS dispersion liquid obtained, addition TT-615 (0.5
Weight %), SJS-2 (1 weight %),(0.1 weight %) and ethylene glycol (5 weight %)；
Comparative example 7:
Commercially available Heraeus Inc. CLEVIOSTM2- amino-2-methyl -1- third is added in the PEDOT/PSS dispersion liquid of PH500
Alcohol is monitored by pH meter and adjusts pH value to weakly acidic pH, in neutrality PEDOT/PSS dispersion liquid obtained, addition TT-615 (0.5
Weight %), WH-03 (0.5 weight %), SJS-2 (0.5 weight %),(0.1 weight %) and ethylene glycol (5 weights
Measure %)；
The preparation of transparent conductive film:
PEDOT/PSS electrically conductive ink obtained in embodiment 6~10 and comparative example 3~7 is thin using 100 μm of high transparency PET
Film (east beautiful) is used as substrate (light transmittance > 92.0%, mist degree < 0.5%), with 20 μm of progress roller coating of wet-film thickness, at 135 DEG C,
Transparent conductive film is made in solidification 5 minutes, tests correlated performance data (table 2).Wherein, it is tested and is applied using four probe resistance instrument
Layer square resistance；Light transmittance and mist degree reference standard GB/T 2410-2008 are tested；Pencil hardness is referring to GB/T6739-
2006 are tested；Coating adhesion test is tested with GB/T9286-1998 (cross-cut tester) to be tested；
Table 2: transparent conductive film performance data made from embodiment 6~10 and comparative example 3~7
Conclusion: under the same terms, film made of the electrically conductive ink of benzene birds droppings amine-formaldehyde resin WH-03, pencil are added
Hardness compares height, but mist degree is bigger than normal, after WH-03 and SJS-2 or SJS-3 blending use, obtained electrically conductive ink various aspects
Energy data are optimal；And be added to TT-615 and adjust the electrically conductive ink after viscosity as thickener, the square electricity of film is made
Resistance and haze value are larger.
After being rubbed 10 times with the rayon balls of infiltration different solvents with 1kg pressure, transparent conductive film coating is measured
To the patience of solvent.
As a result it is summarized in table 3:
Zero=solvent resistant, coating are not destroyed；
The solvent resistant of ×=not, coating are destroyed.
Table 3: the patience of transparent conductive film coating versus solvents made from embodiment 6~10 and comparative example 3~7
Experimental result clearly illustrates, compared with the coating prepared with the dispersion liquid of comparative example, with dispersion liquid of the invention
The patience of the coating versus solvents of preparation is higher.
Part III: neutral PEDOT/PSS electrically conductive ink and nano-silver thread are compound
In the field of new materials of transparent electrode, to obtain high electric conductivity, light transmission rate and being made jointly with other materials
PEDOT/PSS and two kinds of Material claddings of nano-silver thread usually can be got up to use by the consideration of level-density parameter when standby device etc..It is real
The nano-silver thread solution used in example 11 and comparative example 8 is applied as the production of Nanjing Xian Feng Nono-material Science & Technology Ltd..
Embodiment 11:
Nano-silver thread solution and the neutral PEDOT/PSS electrically conductive ink in embodiment 10 are sequentially successively coated with
(being denoted as with modified PEDOT) uses 100 μm of high transparency PET films (east is beautiful) as substrate (light transmittance >
92.0%, mist degree < 0.5%), with 20 μm of progress roller coating of wet-film thickness, at 135 DEG C, solidifies 5 minutes, it is thin that electrically conducting transparent is made
Film；
Comparative example 8:
By Heraeus Inc. CLEVIOSTMThe PEDOT/PSS dispersion liquid of PH1000 is applied according to same procedure in embodiment 11
Cloth (is denoted as with PH1000), and transparent conductive film is made.
In embodiment 11 and comparative example 8 in obtained film, with nano-silver thread (AgNW), PH1000 and embodiment 10
Neutral PEDOT/PSS electrically conductive ink (modified PEDOT) made from film, under condition of different temperatures, square resistance survey
Examination, experimental result are as shown in Fig. 1.
Experimental result clearly illustrates, (90,120,150,180,210 DEG C) of temperature condition are different, square resistance there is also
Difference.Especially nano-silver thread and PH1000 compound conductive film are shown as after temperature rises to 150 DEG C, and square resistance is suddenly
Rise, conductivity sharply declines；And neutrality PEDOT/PSS electrically conductive ink and the compound conductive film of nano-silver thread are used, side
Block resistance varies with temperature aspect and shows highly stable.Furthermore nano-silver thread, PH1000 and neutralisation is used alone
Conductive film is made in PEDOT/PSS, varies with temperature resistance and also shows stable performance.Therefore, by neutrality, treated
PEDOT/PSS electrically conductive ink with the metallic conductions such as nano-silver thread Material cladding in use, compared with comparatively acidic PH1000 product,
Show preferable compatibility and stability.
Claims (8)
1. a kind of electrically conductive ink being re-dubbed by function additives such as PEDOT/PSS dispersion liquid and adhesives, which is characterized in that addition
At least one condensation product and/or addition that at least one guanamine and at least one carbonyls are formed it is at least one with alcohol,
For the polyester liquid for the non-aqueous dosage form that ether, ketone solvent dissolve as adhesive, the polyester of the non-aqueous dosage form is poly- more contracting second
Two acid esters of glycol and its modifier and/or diglycolic acid ester and its modifier；During the PEDOT/PSS dispersion liquid uses
Property PEDOT/PSS dispersion liquid, be polymerized by EDOT and PSS, after polymerization reaction, add alkalinity additive tune
PH value after ageing to required viscosity, removes inorganic salts, the PEDOT/PSS aqueous dispersions of neutralisation is made.
2. electrically conductive ink according to claim 1, which is characterized in that the polyester of the condensation product and/or non-aqueous dosage form
The additive amount of solution is 0.001~15 weight % of PEDOT/PSS dispersion liquid.
3. electrically conductive ink according to claim 1, which is characterized in that in EDOT and PSS polymerization process, add phosphorus
Acid esters is as viscosity modifier.
4. electrically conductive ink according to claim 1, which is characterized in that alkalinity additive is selected from alkali metal hydroxide, alkali
Metal carbonate or bicarbonate, alkaline earth metal hydroxide, alkaline earth metal carbonate or bicarbonate, ammonia, aliphatic alkyl
Amine or aromatic amine.
5. electrically conductive ink according to claim 1, which is characterized in that adjusting pH value range is 5.0~9.0.
6. electrically conductive ink according to claim 1, which is characterized in that PEDOT/PSS dispersion viscosity range be 1000~
50000mPa·s。
7. electrically conductive ink according to claim 1, which is characterized in that during the preparation process, optionally addition thickener and
Other function additives make the dispersion liquid of neutralisation reach required viscosity, and the electrically conductive ink of neutralisation is made.
8. the purposes of electrically conductive ink according to any one of claims 1 to 7, which is characterized in that PEDOT/PSS obtained
Electrically conductive ink is for conductive or antistatic coating.
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| CN201410445544.9A CN104212243B (en) | 2014-09-03 | 2014-09-03 | A kind of preparation method of PEDOT/PSS electrically conductive ink and coating |
| PCT/CN2015/088806 WO2016034113A1 (en) | 2014-09-03 | 2015-09-02 | Pedot/pss conductive ink and transparent electrode |
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| WO2016034113A1 (en) * | 2014-09-03 | 2016-03-10 | 李大忠 | Pedot/pss conductive ink and transparent electrode |
| CN105038411B (en) * | 2015-07-14 | 2018-04-27 | 浙江中科立德新材料有限公司 | A kind of electrically conductive ink and preparation method thereof and application method |
| CN105440802B (en) * | 2015-12-22 | 2017-12-12 | 江南大学 | It is a kind of can ultraviolet photodimerization PEDOT conductive inks and preparation method thereof |
| CN105907181B (en) * | 2016-06-13 | 2018-10-30 | 江南大学 | A kind of light sensitivity PEDOT:The preparation and application of PSVMA/AuNPs conductive inks |
| CN106750449A (en) * | 2016-11-10 | 2017-05-31 | 宁波智锐新材料有限公司 | It is a kind of repeatedly to scribble antistatic PET film of wiping and preparation method thereof |
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