WO2016034113A1 - Pedot/pss conductive ink and transparent electrode - Google Patents

Pedot/pss conductive ink and transparent electrode Download PDF

Info

Publication number
WO2016034113A1
WO2016034113A1 PCT/CN2015/088806 CN2015088806W WO2016034113A1 WO 2016034113 A1 WO2016034113 A1 WO 2016034113A1 CN 2015088806 W CN2015088806 W CN 2015088806W WO 2016034113 A1 WO2016034113 A1 WO 2016034113A1
Authority
WO
WIPO (PCT)
Prior art keywords
pedot
pss
conductive
conductive ink
ink
Prior art date
Application number
PCT/CN2015/088806
Other languages
French (fr)
Chinese (zh)
Inventor
李大忠
李葰
李元尨
宋立文
陶志刚
李红光
黄心毅
Original Assignee
李大忠
李葰
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from CN201410445544.9A external-priority patent/CN104212243B/en
Priority claimed from CN201410445623.XA external-priority patent/CN104183303B/en
Application filed by 李大忠, 李葰 filed Critical 李大忠
Publication of WO2016034113A1 publication Critical patent/WO2016034113A1/en

Links

Images

Classifications

    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports

Definitions

  • the invention relates to a PEDOT/PSS conductive ink and a coating and a related stable transparent coating structure electrode, and belongs to the field of organic optoelectronic applications.
  • Transparent conductive films especially transparent electrodes, play an important role in the display and solar industries.
  • ITO indium tin oxide
  • many research institutions around the world are looking for viable alternatives.
  • materials replacing ITO have been proposed.
  • PEDOT/PSS The conductive polymer poly 3,4-ethylenedioxythiophene-polyvinylbenzenesulfonic acid
  • EDOT 3,4-ethylenedioxythiophene
  • PEDOT/PSS is one of the most widely used conductive polymers in the field of optoelectronic components.
  • transparent conductive film made of PEDOT/PSS has the unmatched advantages of traditional ITO materials in the large-scale production and flexible electronics industries.
  • the PEDOT/PSS conductive ink required for the printing film forming process has a certain viscosity, and the thickening agent is often required in the existing high viscosity ink preparation process. Due to the addition of a non-conductive thickener, the conductivity of the transparent conductive film made of the PEDOT/PSS conductive ink is lowered, the haze is increased, and the like;
  • the prepared transparent electrode has excellent electrical, optical and mechanical properties and has been the direction of the industry.
  • researchers have proposed a method for preparing transparent electrodes based on materials such as conductive polymers, carbon nanotubes, graphene, metal grids, and nano-silver wires.
  • the performance of the transparent electrode materials prepared by most of these methods is not comparable to that of ITO transparent electrodes.
  • transparent electrodes prepared based on nano-silver wires have been proved to be the most excellent performance, and they have an electrical property of 100 ⁇ / ⁇ or less while maintaining 90% transmittance. Bend, good adhesion, become a substitute The preferred material for ITO transparent electrodes.
  • Nano silver wire has outstanding performance in many ITO replacement materials, but there are also technical defects that are difficult to avoid. Mainly in the following aspects: (1) organic matter has an advantage in the preparation process of the film-forming device, which requires the transparent electrode material to have a matching energy level, which is also a so-called work function requirement in the industry. In this respect, the nano silver wire material is difficult to interface with other organic functional layer materials; (2) The flatness of the transparent electrode surface has a significant influence on the photoelectric conversion efficiency of the thin film solar cell. Therefore, the evaluation of the quality of the transparent electrode material should not only refer to the transmittance, conductivity, bending, etc., and the surface flatness has become a very important evaluation index for the transparent electrode material.
  • the nano silver wire material is still insufficient;
  • the transparent electrode material is required to have high stability, and the performance of the electrode film such as conductivity and light transmittance is relatively stable as the device is used for a long time.
  • a very critical evaluation indicator for transparent electrode materials is required.
  • PEDOT/PSS has a work function that matches most organic materials, as well as good conductivity and light transmittance, and can be processed by a solution/print process.
  • the conductivity of PEDOT/PSS is difficult to meet the requirements of transparent electrodes for OLED and other components. It takes a long time to make breakthroughs in the use of transparent electrodes alone.
  • the combination of nano-silver wire and PEDOT/PSS can make the properties of the two conductive materials complement each other, that is, while ensuring the conductivity, the problem of energy level matching can be solved, and PEDOT/PSS can also be used for improvement.
  • the non-uniformity of the surface of the nano-silver wire material coating provides a new solution for mass production of transparent electrodes in the flexible device field in the future.
  • the object (1) of the present invention is to provide a neutralizable PEDOT/PSS conductive ink having low viscosity properties and good environmental resistance, and the solution is to solve the problem of neutralization and viscosity during the reaction.
  • a PEDOT/PSS conductive ink is prepared.
  • the neutral conductive ink can be applied on a large scale by screen printing or the like, and the resulting conductive coating has high transparency and a low haze value.
  • the object (2) of the present invention is to provide a novel transparent electrode of a PEDOT/PSS conductive layer composited with a nanosilver layer and a preparation method thereof. Based on the solution method/printing method, the nano-silver wire conductive layer and the PEDOT/PSS conductive layer or the conductive layer formed by blending the PEDOT/PSS and the nano silver wire are sequentially coated on the transparent substrate layer to form a stacked layer. Electrode structure.
  • the laminated transparent electrode effectively reduces the sheet resistance of the entire transparent electrode film layer; by covering the neutralized PEDOT/PSS conductive polymer layer on the nano silver wire conductive layer, it is isolated from the outside air, thereby avoiding
  • the effect of the PEDOT/PSS conductive layer on the increase of the sheet resistance due to the corrosive action of the acidic PEDOT/PSS and the nano-silver line; and the coating of the PEDOT/PSS conductive layer can also improve the conductivity of the nano-silver conductive layer and the surface during coating. Inhomogeneity.
  • the transparent conductive layer electrode provided by the invention ensures the stability of the transparent electrode in terms of heat resistance and current resistance.
  • the addition of a non-conductive thickener in the PEDOT/PSS dispersion and the effect of neutralizing ions by direct neutralization are avoided, resulting in a film made of the neutral conductive ink.
  • the conductivity, light transmittance, and haze properties are greatly improved; this ion-free neutral PEDOT/PSS material provides a mixture with other types of conductive materials such as nanosilver wires, metal meshes, etc. Possibility to effectively reduce the corrosion of metals due to acidity It is possible to ensure that the conductivity and stability of the resulting conductive coating are not affected.
  • an organic functional additive by appropriately adding an organic functional additive, the environmental resistance of the transparent conductive film, such as stability against water, solvent, and the like, is improved.
  • the PEDOT/PSS conductive inks described above can be prepared by adding organic functional additives on the basis of different types of PEDOT/PSS dispersions.
  • the organic functional additive includes at least one condensate of a guanamine and at least one carbonyl compound as an adhesive.
  • the condensate of guanamine and at least one carbonyl compound, preferably guanamine, is condensed with an aldehyde or a ketone.
  • Suitable aldehydes or ketones are: formaldehyde, acetaldehyde, butyraldehyde, acetone or methyl ethyl ketone.
  • Particularly preferred is formaldehyde;
  • a particularly preferred condensate of guanamine and at least one carbonyl compound is a guanamine-formaldehyde condensate having the structure of formula (I)
  • R 1 represents H or a linear or branched C1 to C8 alkyl group, a phenyl group or a mono-, di-, or tri-substituted phenyl group, preferably H or a linear or branched C1 to C4 alkyl group, a phenyl group, Particularly preferred is H or a methyl group, an ethyl group and a phenyl group.
  • R 2 to R 5 independently of each other represent H or CH 2 -OR 6 , at least one of the groups R 2 to R 5 is not H, and R 6 represents H or a linear or branched C1 to C8 alkyl group, preferably H Or a linear or branched C1-C4 alkyl group, particularly preferably R 2 to R 5 each represent H or CH 2 -OR 6 .
  • such a particularly preferred guanamine-formaldehyde condensate may be a condensation product of the condensate of the formula (I) with each other or with another guanamine.
  • the particularly preferred guanamine-formaldehyde condensate may be partially or fully etherified. Additionally or alternatively, the particularly preferred guanamine-formaldehyde condensate may be modified by reaction with an amine, an aminocarboxylic acid or a sulfite, or by reacting with other compounds reactive with the aldehyde, such as phenols. Or urea co-condensation to modify to improve solubility in water.
  • the content of the condensate of the guanamine and the at least one carbonyl compound in the PEDOT/PSS conductive ink is 0.001 to 15% by weight, preferably 0.1 to 2% by weight based on the weight of the PEDOT/PSS dispersion.
  • the PEDOT/PSS conductive inks are prepared by adding organic functional additives on the basis of different types of PEDOT/PSS dispersions.
  • the organic functional additive includes at least one non-aqueous solvent type polyester solution dissolved in a solvent such as an alcohol, an ether or a ketone as an adhesive.
  • the non-aqueous solvent-type polyester adhesive used specifically refers to polyglycol dicarboxylate (n ⁇ 10) and its modifications or diethylene glycol dicarboxylate and its modifications;
  • the alcohol may be methanol, ethanol, n-propanol, isopropanol, butanol, n-octanol, glycol or glycol ether such as ethylene glycol, 1,2-propanediol, 1,3-propanediol or diethylene glycol;
  • the ether may be diethyl ether, n-propyl ether, n-butyl ether, methyl butyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, 1,4-dioxane.
  • the ketone may be acetone, methyl ethyl ketone, methyl isobutyl ketone or methyl t-butyl ketone;
  • the polymer content in the polyester solution is from 0.5 to 85%, preferably from 25 to 30%;
  • the content of the nonaqueous solvent-type polyester solution dissolved in a solvent such as an alcohol, an ether or a ketone in the PEDOT/PSS conductive ink is 0.001 to 15% by weight, preferably 0.1 to 2% by weight based on the weight of the PEDOT/PSS dispersion.
  • the above two types of adhesives can also be added at the same time, the weight ratio of the two is 1:10 to 1:1, and the total content is 0.001 to 15% by weight based on the weight of the neutral dispersion respectively. It is preferably 0.1 to 2% by weight.
  • the dispersion liquid of the conductive ink of the invention may be water type or solvent type; the provided adhesive agent can be made of acidic PEDOT/PSS conductive ink, or can be made of ordinary neutralized PEDOT/PSS conductive ink.
  • the latter is to adjust the pH to near-neutral using an alkaline additive in the acidic PEDOT/PSS dispersion, wherein some neutral ions are generated due to the acid-base reaction, and if not removed, the performance of the conductive coating is seriously affected.
  • Neutralization in the polymerization reaction while solving the viscosity characteristics is the core of the PEDOT/PSS conductive ink involved in the present invention.
  • Phosphate ester may be added as a viscosity modifier during the polymerization reaction (may, before, after), and the ester moiety may be methyl, ethyl, propyl, n-butyl, isopropyl, and combinations thereof; 0.0005 to 1% by weight, preferably 0.01 to 0.2% by weight.
  • Neutralizing the reaction solution after the polymerization reaction using a basic additive to adjust the pH to near neutral;
  • the alkaline additive used may be an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide, an alkali metal carbonate or a hydrogencarbonate such as lithium carbonate, sodium carbonate, potassium carbonate or sodium hydrogencarbonate, carbonic acid.
  • an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide
  • an alkali metal carbonate or a hydrogencarbonate such as lithium carbonate, sodium carbonate, potassium carbonate or sodium hydrogencarbonate, carbonic acid.
  • alkaline earth metal hydroxides such as magnesium hydroxide, calcium hydroxide, alkaline earth carbonates or hydrogencarbonates such as magnesium carbonate, calcium carbonate, ammonia, aliphatic alkylamines, for example with optionally substituted C1 to C20 a mono-, di- or tri-alkylamine of an alkyl group such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethanolamine or dimethylethanolamine, an aromatic amine such as aniline, Diphenylamine, o-diphenylamine, m-diphenylamine or p-diphenylamine.
  • alkaline earth metal hydroxides such as magnesium hydroxide, calcium hydroxide, alkaline earth carbonates or hydrogencarbonates such as magnesium carbonate, calcium carbonate, ammonia, aliphatic alkylamines, for example with optionally substituted C1 to C20 a mono-, di- or tri-alkylamine of
  • the alkaline additive is preferably used in the form of a solution, preferably the solvent may be water and/or an alcohol for neutralizing the PEDOT/PSS dispersion.
  • the alcohol may be methanol, ethanol, n-propanol, isopropanol, butanol, n-octanol, glycol or glycol ether such as ethylene glycol, 1,2-propanediol, 1,3-propanediol or diethylene glycol;
  • the above basic additives are also suitable for the preparation of the above generally neutralized PEDOT/PSS conductive ink.
  • the PEDOT/PSS conductive ink provided by the invention adds the alkaline additive to the PEDOT/PSS dispersion, adjusts the pH value of the system through the pH agent, and the pH ranges from 5.0 to 9.0, preferably the pH ranges from 6.0 to 8.0, more preferably the pH.
  • the value is 6.5 to 7.2;
  • the viscosity ranges from 1 000 to 50 000 mPa ⁇ s, preferably the viscosity ranges from 2 000 to 20 000 mPa ⁇ s; more preferably, the viscosity range is 5 000 to 8 000 mPa ⁇ s;
  • the organic functional additive added in the preparation of the conductive ink includes other organic functional additives such as a conductive enhancer, a surfactant and a leveling agent;
  • a functionalized conductive coating is applied to a substrate such as a composition or laminate.
  • a novel transparent electrode having a neutralized PEDOT/PSS conductive layer, comprising a transparent substrate layer and covering the through A conductive layer on the substrate layer, the conductive layer comprising a nano-silver wire conductive layer overlying the transparent substrate layer, and a neutralized PEDOT/PSS conductive layer overlying the nano-silver wire conductive layer.
  • the transparent substrate layer is selected from transparent materials: glass, glass resin, fluoropolymer, silicone, polyolefin, polyether hydrocarbon, PET, PEN, PMMA, and copolymer or composition of PC, PI and combinations thereof. Or laminate, etc.;
  • the conductive layer has a thickness of 50 to 300 nm;
  • the neutralized PEDOT/PSS conductive layer constituting the above is made of a neutralized PEDOT/PSS conductive ink:
  • the nano silver wire conductive ink used in the present invention has a mass percentage concentration of 0.05 to 8%, a nano silver wire length of 10 to 50 ⁇ m, and a nano silver wire diameter of 5 to 300 nm;
  • a preparation method for a neutralized PEDOT transparent stable electrode comprising the following steps:
  • a neutralized PEDOT/PSS conductive ink is coated on the nano silver wire conductive layer, or a blend thereof with the nano silver wire is cured to form a polymer conductive layer.
  • the present invention has the following beneficial effects:
  • the transparent electrode having a neutralized PEDOT/PSS composite conductive layer has a sheet resistance of 10 to 150 ⁇ / ⁇ and a light transmittance of 85 to 91% at a wavelength of 550 nm, thereby obtaining high conductivity and high. Transmittance; by covering the neutralized PEDOT/PSS conductive polymer layer on the nano-silver wire conductive layer to isolate it from the outside air, and avoiding corrosion due to contact with silver nanowires with acidic PEDOT/PSS The effect of increasing the sheet resistance is to significantly improve the stability of the transparent electrode in terms of heat resistance and current resistance.
  • the transparent electrode film having the neutralized PEDOT/PSS composite conductive layer of the present invention has the advantages of high conductivity, good light transmittance, simple manufacturing process, weather resistance and current resistance, and can be used for organic solar cells and organic light-emitting. Diode or touch display and medical devices, capacitors and other fields.
  • Figure 1 is a schematic cross-sectional view showing the structure of the present invention
  • Figure 2 shows the stability of transparent electrodes made of different conductive materials at different temperatures.
  • Figure 3 is a scanning electron microscope image (SEM) of a transparent electrode made of different conductive materials.
  • Examples 1 to 5 and Comparative Examples 1 and 2 are preparations of a neutralized PEDOT/PSS dispersion based on the above polymerization process.
  • Example 1 After the completion of the PEDOT/PSS polymerization reaction, the reaction was stopped, 2-amino-2-methyl-1-propanol was added, and the pH was adjusted to neutral after monitoring by a pH meter, and aged for 2 hours, as in Example 1. After the method of yin and yang resin exchange treatment, the viscosity is measured by a rotary viscometer;
  • Example 1 After the completion of the PEDOT/PSS polymerization reaction, the reaction was stopped, 2-amino-2-methyl-1-propanol was added, and the pH was adjusted to neutral after monitoring by a pH meter, and aged for 5 hours, as in Example 1. After the method of yin and yang resin exchange treatment, the viscosity is measured by a rotary viscometer;
  • Example 2 After completion of the PEDOT/PSS polymerization reaction in Example 1, the reaction was stopped, aged for 2 hours, and after the cation-yang resin exchange treatment was carried out in the same manner as in Example 1, 2-amino-2-methyl-1-propanol was added thereto. After the pH meter monitors the pH to near neutral, the viscosity is measured by a rotary viscometer;
  • Example 2 After the completion of the PEDOT/PSS polymerization reaction in Example 1, the reaction was stopped, aged for 5 hours, and the cation-yang resin exchange treatment was carried out in the same manner as in Example 1, and 2-amino-2-methyl-1-propanol was added thereto. After the pH meter is adjusted to monitor the pH to near neutral, the viscosity is measured by a rotary viscometer;
  • Table 1 Viscosity and pH of PEDOT/PSS dispersions in Examples 1 to 5 and Comparative Examples 1 and 2.
  • Example 2 0.5 4500 7.5
  • Example 3 1 2354 7.6
  • Example 4 2 4672 8.0
  • Example 5 5 4736 7.8 Comparative example 1 2 25 7.5 Comparative example 2 5 33 7.6
  • the difference between the operation of the examples and the comparative example is that in the embodiment, the alkali is first added to adjust the pH value, and then aged for different time (0.5 hour, 1 hour, 2 hours, 5 hours), and then treated by anion-cation exchange resin.
  • the comparison ratio is first aged for different time (2 hours, 5 hours), and then treated by anion-cation exchange resin, and then alkali is added to adjust the pH.
  • the viscosity of the neutralized PEDOT/PSS dispersion prepared in Examples 1, 3, 4 and 5 increased with the aging time, and the viscosity after 2 hours of aging time Basically stable; and in Example 2, triethyl phosphate was added as a material, and after 0.5 hours of aging, the viscosity was nearly stable (substantially the same as the viscosity values in Examples 4 and 5); prepared in Comparative Examples 1 and 2.
  • the viscosity of the neutralized PEDOT/PSS dispersion does not change with the aging time, and is a low-viscosity dispersion. In the coating process such as screen printing, it is necessary to add a thickener to the desired viscosity before use.
  • Examples 6 to 10 are based on the neutralized PEDOT/PSS dispersion prepared in Example 4, and an adhesive, a surfactant, and a conductivity enhancer are added to prepare a neutralized PEDOT/PSS conductive ink; 3-7 is a neutralized PEDOT/PSS conductive ink prepared on the basis of Comparative Example 1 and a commercially available PH500 product by adding a thickener, an adhesive, a surfactant, and a conductive reinforcing agent.
  • Benzoin amine-formaldehyde resin WH-03 and adipic acid diethylene glycol polyester methyl ethyl ketone solution SJS-2 or polyethylene glycol dicaprate isopropanol solution SJS- used in the examples and comparative examples 3 are all synthetically produced by Shanghai Synthetic Resin Research Institute.
  • the PEDOT/PSS conductive inks prepared in Examples 6 to 10 and Comparative Examples 3 to 7 were made of a 100 ⁇ m high transparent PET film (Dongli) as a substrate (light transmittance > 92.0%, haze ⁇ 0.5%).
  • a wet film thickness of 20 ⁇ m was applied to the bar, and cured at 135 ° C for 5 minutes to prepare a transparent conductive film, and the relevant performance data was tested (Table 2).
  • the four-probe resistance meter was used to test the resistance of the coating sheet; the transmittance and haze were tested according to the standard GB/T 2410-2008; the pencil hardness was tested according to GB/T6739-2006; the coating adhesion test was GB. /T9286-1998 (Hundred Grid Knife) experimental test;
  • the film made of conductive ink with Benzene guanamine-formaldehyde resin WH-03 has higher pencil hardness, but the haze is too large.
  • WH-03 is mixed with SJS-2SJS-3. After that, the obtained performance data of the conductive ink is optimized in all aspects; and the conductive ink after adjusting the viscosity by adding TT-615 as a thickener, the sheet resistance and the haze value of the film are large.
  • the resistance of the transparent conductive film coating to the solvent was measured by rubbing the cotton wool ball infiltrated with different solvents at a pressure of 1 kg for 10 times.
  • Table 3 Solvent resistance of transparent conductive film coatings prepared in Examples 6 to 10 and Comparative Examples 3 to 7
  • the stabilized PEDOT/PSS conductive layer electrode of the present invention comprises a transparent substrate layer 1 and a transparent electrode layer, and the transparent electrode layer covers the transparent substrate layer 1 and has a thickness of 25 ⁇ 1000 nm, comprising a nano-silver wire conductive layer 2 coated on the substrate layer 1, and a neutral PEDOT/PSS polymer conductive layer coated on the surface of the nano-silver wire conductive layer 2 or blended with the nano-silver wire
  • the polymer conductive layer 3 is formed later.
  • the transparent substrate layer 1 is made of a transparent material such as glass, PET, PEN, PMMA or PI as a substrate material.
  • the nano silver wire conductive layer 2 is formed by coating a nano silver wire conductive ink on a transparent substrate layer.
  • the nano silver wire conductive ink has a mass percentage concentration of 0.05 to 8%, a nano silver wire length of 10 to 50 ⁇ m, a nano silver wire diameter of 5 to 300 nm, and a polymer conductive layer 3 of a nano silver wire.
  • the unique laminated structure of the neutral PEDOT/PSS conductive polymer layer and the nano silver wire conductive layer greatly reduces the sheet resistance of the transparent electrode conductive layer while maintaining good light transmittance, haze and the like. It is worth mentioning that the transparent electrode made of this structure also has very stable environmental resistance such as heat resistance, solvent resistance and current resistance.
  • a method for preparing a stable PEDOT/PSS conductive layer electrode using the above structure comprising the steps of:
  • a neutralized PEDOT/PSS conductive ink is coated on the nano silver wire conductive layer, or a blend thereof with the nano silver wire, and the polymer conductive layer 3 is formed by curing optimization.
  • the substrate material is subjected to surface pretreatment as the transparent substrate layer 1.
  • the optical PET film was selected as the substrate material, and the surface was cleaned before use, and ultrasonic cleaning was carried out in the ultrasonic cleaning bath for 10 minutes with washing liquid, deionized water, isopropyl alcohol and deionized water, and then dried in a nitrogen stream.
  • a nano-silver wire conductive layer 2 is prepared by coating on the transparent substrate layer 1.
  • the nano silver wire conductive ink is selected as the material, and the nano silver wire conductive ink (XFNANO Agnws-60nm/20 ⁇ m isopropanol solvent, solid content 5%, Nanjing Xianfeng nanometer) is adopted by a roll coating process. Material Technology Co., Ltd.) was coated on the surface of the transparent substrate layer 1 with a wet film thickness of 12 ⁇ m. After coating, the coating was dried at 150 ° C for 5 minutes to prepare a nano-silver wire conductive layer 2.
  • the nano silver wire conductive ink XFNANO Agnws-60nm/20 ⁇ m isopropanol solvent, solid content 5%, Nanjing Xianfeng nanometer
  • a neutral PEDOT/PSS polymer conductive layer 3 is coated on the nano silver wire conductive layer 2.
  • a neutral PEDOT/PSS conductive ink was prepared as in Example 10.
  • a blend of a neutral PEDOT/PSS conductive ink and a nano silver wire conductive ink is coated on the nano silver wire conductive layer 2 to form a polymer conductive layer 3.
  • the preparation process of the neutral PEDOT/PSS conductive ink preparation is also the same as that of the embodiment 11;
  • a blend of a neutral PEDOT/PSS conductive ink and a nano silver wire conductive ink was printed on the surface of the nano silver wire conductive layer 2, and the process liquid was the same as in Example 11, thereby completing the entire stable PEDOT/PSS conduction. Layer electrode.
  • the Heraeus PEDOT/PSS CLEVIOS TM PH1000 dispersion was selected as the comparative experimental material, and the following four comparative conductive layer electrodes were designed and fabricated at different temperatures (90, 120, 150, 180, The stability of the surface resistance of each conductive layer electrode was tested at 210 ° C):
  • the nano-silver wire conductive ink was coated into a conductive layer electrode according to the method of Example 11, and the surface resistance curve with temperature was tested (the block line AgNW in Fig. 2) );
  • the nano silver wire conductive ink was coated into a nano silver wire conductive layer according to the method of Example 11, and then coated on the conductive layer to prepare PH1000 to be electrically conductive.
  • Example 11 The conductive layer electrode prepared in Example 11 was tested for the surface resistance as a function of temperature (upper triangle line AgNW/Neutral-pH PEDOT in Fig. 2);
  • the conductive layer prepared by the composite of nano-silver wire and PH1000 shows that the square resistance decreases sharply and the conductivity decreases sharply after the temperature rises to 150 ° C.
  • the conductive film which is made of neutral PEDOT/PSS conductive ink and nano silver wire is used. Its sheet resistance is very stable with temperature changes.
  • the conductive layer made of nano silver wire, PH1000 and neutral PEDOT/PSS conductive ink alone has stable performance with temperature change. Therefore, the PEDOT/PSS conductive ink after neutral treatment is used in combination with a metallic conductive material such as a nano silver wire.
  • the PH1000 product shows good compatibility and stability.

Abstract

Preparation methods for a PEDOT/PSS conductive ink, a conductive coating and a coated electrode. The preparation process of the conductive ink comprises: obtaining a PEDOT/PSS dispersion with neutral ink viscosity, and then adding at least one condensate formed by guanamine and at least one carbonyl compound and/or a non-aqueous solvent type polyester solution as an adhesive into the dispersion with the ink viscosity and adding other functional additives to obtain the PEDOT/PSS conductive ink. On a transparent substrate (1), a silver nanowire conductive coating (2) is coated on the first layer, and a neutralized PEDOT/PSS conductive ink coating (3) or a conductive coating (3) formed by blending a neutralized PEDOT/PSS conductive ink and a silver nanowire conductive ink is coated on the second layer, so as to form a coated electrode in a laminated structure. Such electrode can be applied in fields such as organic solar cells, organic light emitting diodes or touch display screens and medical devices and capacitors.

Description

一种PEDOT/PSS导电油墨及一种透明电极PEDOT/PSS conductive ink and a transparent electrode 技术领域Technical field
本发明涉及一种PEDOT/PSS导电油墨及涂层和相关的稳定性透明涂层结构电极，属于有机光电子应用领域。The invention relates to a PEDOT/PSS conductive ink and a coating and a related stable transparent coating structure electrode, and belongs to the field of organic optoelectronic applications.
背景技术Background technique
透明导电薄膜特别是透明电极在显示器与太阳能产业中，具有十分重要的地位。近年来，因平面显示器的大量生产，几乎耗尽目前用于制作透明导电薄膜的铟锡氧化物(Indium Tin Oxide,ITO)材料的供应。为此，全球有不少研究机构都在寻找可行的替代方案。此外，更因ITO材料的价格不断飙涨，以及ITO材料在大尺寸制程上的限制，再加上柔性电子产业的兴起，取代ITO的材料相继被提出。Transparent conductive films, especially transparent electrodes, play an important role in the display and solar industries. In recent years, due to the mass production of flat panel displays, the supply of indium tin oxide (ITO) materials currently used for the production of transparent conductive films has been almost exhausted. To this end, many research institutions around the world are looking for viable alternatives. In addition, as the price of ITO materials continues to soar, and the limitations of ITO materials in large-scale processes, coupled with the rise of the flexible electronics industry, materials replacing ITO have been proposed.
导电聚合物聚3,4-乙撑二氧噻吩-聚乙烯苯磺酸(PEDOT/PSS)是3,4-乙撑二氧噻吩(EDOT)单体的聚合物。目前，PEDOT/PSS为光电元器件领域中使用最为广泛的导电聚合物之一。作为新型的透明导电材料，PEDOT/PSS制成的透明导电薄膜在大尺寸制作以及柔性电子产业领域均有着传统的ITO材料难以匹敌的优势。The conductive polymer poly 3,4-ethylenedioxythiophene-polyvinylbenzenesulfonic acid (PEDOT/PSS) is a polymer of 3,4-ethylenedioxythiophene (EDOT) monomer. Currently, PEDOT/PSS is one of the most widely used conductive polymers in the field of optoelectronic components. As a new type of transparent conductive material, transparent conductive film made of PEDOT/PSS has the unmatched advantages of traditional ITO materials in the large-scale production and flexible electronics industries.
然而，导电聚合物PEDOT/PSS制作的透明导电薄膜的发展仍受到有机聚合物自身缺陷的限制，主要表现在：However, the development of transparent conductive films made of conductive polymer PEDOT/PSS is still limited by the defects of organic polymers themselves, mainly in:
(1)印刷成膜工艺要求使用的PEDOT/PSS导电油墨具有一定的粘度，现有的高粘度油墨制备工艺中往往需要添加增稠剂。由于非导电性的增稠剂的添加，使得由PEDOT/PSS导电油墨制作的透明导电薄膜的导电性下降、雾度上升等；(1) The PEDOT/PSS conductive ink required for the printing film forming process has a certain viscosity, and the thickening agent is often required in the existing high viscosity ink preparation process. Due to the addition of a non-conductive thickener, the conductivity of the transparent conductive film made of the PEDOT/PSS conductive ink is lowered, the haze is increased, and the like;
(2)基于聚合物的PEDOT/PSS透明导电薄膜在耐环境性，例如，耐水、耐溶剂方面的稳定性相比ITO以及其它类型透明电极新材料仍有不足；(2) Polymer-based PEDOT/PSS transparent conductive films are still insufficient in environmental resistance, for example, water and solvent resistance, compared to ITO and other types of transparent electrode new materials;
(3)此外，由于制备出的PEDOT/PSS分散液显强酸性，与金属接触时会因其腐蚀性而导致金属导电性下降，严重地限制了其与纳米银线、金属网格等金属性导电材料混合使用时的兼容性，以及制作的透明电极的稳定性。(3) In addition, since the prepared PEDOT/PSS dispersion is strongly acidic, the metal conductivity is lowered due to its corrosiveness when it is in contact with the metal, which seriously limits its metallic properties such as nano silver wire and metal mesh. Compatibility of conductive materials when mixed, and stability of transparent electrodes produced.
因此，为了使导电聚合物PEDOT/PSS在透明导电薄膜领域实现大规模应用，仍需要克服上述问题。Therefore, in order to realize the large-scale application of the conductive polymer PEDOT/PSS in the field of transparent conductive films, it is still necessary to overcome the above problems.
另外能够开发一种相对廉价的制备透明电极材料的方法，且制备出来的透明电极具有优异的电学、光学及力学性能成为业界一直努力的方向。近年来，科研工作者提出了采用基于导电高分子、碳纳米管、石墨烯、金属网格、纳米银线等材料制备透明电极的方法。然而，这其中大部分方法所制备出来的透明电极材料性能尚不能与ITO透明电极相媲美。在这些新兴的透明电极的候选材料中，基于纳米银线制备的透明电极被证实是性能最为优异的，其在具有90％透光率的同时还可以保持100Ω/□以下的电学性能，且耐弯折，附着力好，成为了替 代ITO透明电极的首选材料。In addition, it is possible to develop a relatively inexpensive method for preparing a transparent electrode material, and the prepared transparent electrode has excellent electrical, optical and mechanical properties and has been the direction of the industry. In recent years, researchers have proposed a method for preparing transparent electrodes based on materials such as conductive polymers, carbon nanotubes, graphene, metal grids, and nano-silver wires. However, the performance of the transparent electrode materials prepared by most of these methods is not comparable to that of ITO transparent electrodes. Among the candidate materials for these emerging transparent electrodes, transparent electrodes prepared based on nano-silver wires have been proved to be the most excellent performance, and they have an electrical property of 100 Ω/□ or less while maintaining 90% transmittance. Bend, good adhesion, become a substitute The preferred material for ITO transparent electrodes.
纳米银线在众多的ITO替代材料中性能突出，但也有难以避免的技术缺陷。主要表现在以下几个方面：(1)有机物在成膜器件制备过程具有优势，这就要求透明电极材料需要具备与之匹配的能级，也是业界所谓的功函数要求。这方面纳米银线材料难以与其它有机功能层材料较好的衔接起来；(2)透明电极表面平整度对制备成薄膜太阳能电池的光电转化效率有着显著的影响。所以，评价透明电极材料的好坏不仅要参考透光率及导电性、弯折性等，表面平整度也成为了透明电极材料一个非常关键的评价指标，这方面纳米银线材料尚存在不足；(3)作为元器件中的透明电极，还要求透明电极材料具有高度的稳定性，表现在随着器件使用时间的延长，电极膜的导电性、透光性等性能相对保持稳定，这也成为了透明电极材料的一个非常关键的评价指标。Nano silver wire has outstanding performance in many ITO replacement materials, but there are also technical defects that are difficult to avoid. Mainly in the following aspects: (1) organic matter has an advantage in the preparation process of the film-forming device, which requires the transparent electrode material to have a matching energy level, which is also a so-called work function requirement in the industry. In this respect, the nano silver wire material is difficult to interface with other organic functional layer materials; (2) The flatness of the transparent electrode surface has a significant influence on the photoelectric conversion efficiency of the thin film solar cell. Therefore, the evaluation of the quality of the transparent electrode material should not only refer to the transmittance, conductivity, bending, etc., and the surface flatness has become a very important evaluation index for the transparent electrode material. In this respect, the nano silver wire material is still insufficient; (3) As a transparent electrode in the component, the transparent electrode material is required to have high stability, and the performance of the electrode film such as conductivity and light transmittance is relatively stable as the device is used for a long time. A very critical evaluation indicator for transparent electrode materials.
为了尽可能解决上述技术缺陷，需要将纳米银线材料与PEDOT/PSS材料复合使用。In order to solve the above technical defects as much as possible, it is necessary to use a nano silver wire material in combination with a PEDOT/PSS material.
PEDOT/PSS由于具有与绝大多数有机物匹配的功函数，以及良好的导电性和光透过率，且可以采用溶液法/印刷工艺制程。然而PEDOT/PSS的导电性能难以满足OLED等元器件对透明电极的要求，单独作为透明电极使用尚需要长时间的技术突破。纳米银线与PEDOT/PSS两种材料的复合使用可以将两种导电材料的性质互相取长补短，即在保证电导率的同时，又可以解决能级匹配的问题，同时PEDOT/PSS也可以用于改善纳米银线材料涂布时表面的不均匀性，为未来柔性器件领域大规模量产透明电极提供了一种新型的解决方案。PEDOT/PSS has a work function that matches most organic materials, as well as good conductivity and light transmittance, and can be processed by a solution/print process. However, the conductivity of PEDOT/PSS is difficult to meet the requirements of transparent electrodes for OLED and other components. It takes a long time to make breakthroughs in the use of transparent electrodes alone. The combination of nano-silver wire and PEDOT/PSS can make the properties of the two conductive materials complement each other, that is, while ensuring the conductivity, the problem of energy level matching can be solved, and PEDOT/PSS can also be used for improvement. The non-uniformity of the surface of the nano-silver wire material coating provides a new solution for mass production of transparent electrodes in the flexible device field in the future.
发明内容Summary of the invention
本发明的目的(一)在于提供一种粘度特性影响性能小、耐环境性好的可中性化的PEDOT/PSS导电油墨，其方案为在反应过程中即解决中性化和粘度问题。The object (1) of the present invention is to provide a neutralizable PEDOT/PSS conductive ink having low viscosity properties and good environmental resistance, and the solution is to solve the problem of neutralization and viscosity during the reaction.
在PEDOT/PSS聚合反应后期，先进行中性化处理，然后再通过陈化工艺进行粘度调节，最后除去离子，即得到中性的、具有油墨粘度的PEDOT/PSS分散液，从而避免加入增稠剂，继续加入至少一种功能助剂后，即制得PEDOT/PSS导电油墨。该中性导电油墨可用丝网印刷等方法大规模涂布，所得的导电涂层具有高透明性和较低的雾度值。In the late stage of PEDOT/PSS polymerization, the neutralization treatment is carried out, and then the viscosity adjustment is carried out by the aging process. Finally, the ions are removed to obtain a neutral PEDOT/PSS dispersion with ink viscosity, thereby avoiding the addition of thickening. After continuing to add at least one functional additive, a PEDOT/PSS conductive ink is prepared. The neutral conductive ink can be applied on a large scale by screen printing or the like, and the resulting conductive coating has high transparency and a low haze value.
本发明的目的(二)在于提供一种新型的与纳米银线层复合的PEDOT/PSS导电层的透明电极及其制备方法。基于溶液法/印刷方式，通过在透明基材层上先后涂布纳米银线导电层以及PEDOT/PSS导电层或PEDOT/PSS与纳米银线掺混后形成的导电层，使其形成叠层式的电极结构。这种叠层式的透明电极有效地降低整个透明电极膜层的方块电阻；通过将中性化PEDOT/PSS导电高分子层覆盖于纳米银线导电层之上，使之与外界空气隔绝，避免酸性PEDOT/PSS与纳米银线接触时因腐蚀性作用而导致方块电阻增大的效果；同时PEDOT/PSS导电层的涂覆，还可以改善纳米银线导电层的导电性以及涂布时的表面不均匀性。本发明提供的透明导电层电极保证了透明电极在耐热、耐电流方面的稳定性。The object (2) of the present invention is to provide a novel transparent electrode of a PEDOT/PSS conductive layer composited with a nanosilver layer and a preparation method thereof. Based on the solution method/printing method, the nano-silver wire conductive layer and the PEDOT/PSS conductive layer or the conductive layer formed by blending the PEDOT/PSS and the nano silver wire are sequentially coated on the transparent substrate layer to form a stacked layer. Electrode structure. The laminated transparent electrode effectively reduces the sheet resistance of the entire transparent electrode film layer; by covering the neutralized PEDOT/PSS conductive polymer layer on the nano silver wire conductive layer, it is isolated from the outside air, thereby avoiding The effect of the PEDOT/PSS conductive layer on the increase of the sheet resistance due to the corrosive action of the acidic PEDOT/PSS and the nano-silver line; and the coating of the PEDOT/PSS conductive layer can also improve the conductivity of the nano-silver conductive layer and the surface during coating. Inhomogeneity. The transparent conductive layer electrode provided by the invention ensures the stability of the transparent electrode in terms of heat resistance and current resistance.
通过改进聚合工艺的方法，避免了在PEDOT/PSS分散液中非导电性的增稠剂的添加以及直接中性化带来的中和离子的影响，使得用该中性导电油墨制成的薄膜的导电率、透光率以及雾度等性能得到大幅改善；这种无离子的中性PEDOT/PSS材料为其与其它种类的导电材料，如纳米银线、金属网格等的混合使用提供了可能性，有效地降低了因酸性而腐蚀金属的 可能，特别保证了所得导电涂层的导电性以及稳定性不受影响。本发明的解决方案中，通过针对性地添加有机功能助剂，提高了透明导电薄膜的耐环境性，如耐水、耐溶剂等方面的稳定性等。By improving the polymerization process, the addition of a non-conductive thickener in the PEDOT/PSS dispersion and the effect of neutralizing ions by direct neutralization are avoided, resulting in a film made of the neutral conductive ink. The conductivity, light transmittance, and haze properties are greatly improved; this ion-free neutral PEDOT/PSS material provides a mixture with other types of conductive materials such as nanosilver wires, metal meshes, etc. Possibility to effectively reduce the corrosion of metals due to acidity It is possible to ensure that the conductivity and stability of the resulting conductive coating are not affected. In the solution of the present invention, by appropriately adding an organic functional additive, the environmental resistance of the transparent conductive film, such as stability against water, solvent, and the like, is improved.
本发明目的(一)是通过以下技术方案实现的：The object (1) of the present invention is achieved by the following technical solutions:
1、所述的PEDOT/PSS导电油墨，均是可在不同类型的PEDOT/PSS分散液的基础上，添加有机功能助剂制备而成。所述的有机功能助剂中，至少包括一种鸟粪胺与至少一种羰基化合物形成的至少一种缩合物作为胶黏剂。1. The PEDOT/PSS conductive inks described above can be prepared by adding organic functional additives on the basis of different types of PEDOT/PSS dispersions. The organic functional additive includes at least one condensate of a guanamine and at least one carbonyl compound as an adhesive.
鸟粪胺与至少一种羰基化合物形成的缩合物，优选是鸟粪胺与醛或酮缩合。适合的醛或酮为：甲醛、乙醛、丁醛、丙酮或甲基乙基酮。特别优选为甲醛；鸟粪胺与至少一种羰基化合物的特别优选的缩合物为鸟粪胺-甲醛缩合物，其结构如通式(I)The condensate of guanamine and at least one carbonyl compound, preferably guanamine, is condensed with an aldehyde or a ketone. Suitable aldehydes or ketones are: formaldehyde, acetaldehyde, butyraldehyde, acetone or methyl ethyl ketone. Particularly preferred is formaldehyde; a particularly preferred condensate of guanamine and at least one carbonyl compound is a guanamine-formaldehyde condensate having the structure of formula (I)
Figure PCTCN2015088806-appb-000001
Figure PCTCN2015088806-appb-000001
式中In the middle
R1表示H或直链或支链C1～C8烷基，苯基或单-、二-、三-取代的苯基，优选为H或直链或支链C1～C4烷基，苯基，特别优选为H或甲基、乙基以及苯基。R 1 represents H or a linear or branched C1 to C8 alkyl group, a phenyl group or a mono-, di-, or tri-substituted phenyl group, preferably H or a linear or branched C1 to C4 alkyl group, a phenyl group, Particularly preferred is H or a methyl group, an ethyl group and a phenyl group.
R2至R5彼此独立地表示H或CH2-OR6，基团R2至R5中的至少一个不是H，且R6表示H或直链或支链C1～C8烷基，优选H或直链或支链C1～C4烷基，特别优选为R2至R5都表示H或CH2-OR6。R 2 to R 5 independently of each other represent H or CH 2 -OR 6 , at least one of the groups R 2 to R 5 is not H, and R 6 represents H or a linear or branched C1 to C8 alkyl group, preferably H Or a linear or branched C1-C4 alkyl group, particularly preferably R 2 to R 5 each represent H or CH 2 -OR 6 .
而且这样特别优选的鸟粪胺-甲醛缩合物可以是通式(I)的缩合物彼此间或与另外的鸟粪胺的缩合产物。Further, such a particularly preferred guanamine-formaldehyde condensate may be a condensation product of the condensate of the formula (I) with each other or with another guanamine.
此外，所述特别优选的鸟粪胺-甲醛缩合物可以部分或全部地醚化。此外或者可选择地，所述特别优选的鸟粪胺-甲醛缩合物可通过与胺类、氨基羧酸类或亚硫酸盐反应来改性，或通过与其它可与醛反应的化合物例如酚类或脲类共缩合来改性，以提高在水中的溶解度。Furthermore, the particularly preferred guanamine-formaldehyde condensate may be partially or fully etherified. Additionally or alternatively, the particularly preferred guanamine-formaldehyde condensate may be modified by reaction with an amine, an aminocarboxylic acid or a sulfite, or by reacting with other compounds reactive with the aldehyde, such as phenols. Or urea co-condensation to modify to improve solubility in water.
鸟粪胺与至少一种羰基化合物的缩合物在所述PEDOT/PSS导电油墨中的含量基于PEDOT/PSS分散液重量为0.001～15重量％，优选为0.1～2重量％。The content of the condensate of the guanamine and the at least one carbonyl compound in the PEDOT/PSS conductive ink is 0.001 to 15% by weight, preferably 0.1 to 2% by weight based on the weight of the PEDOT/PSS dispersion.
2、所述的PEDOT/PSS导电油墨，均是可在不同类型的PEDOT/PSS分散液的基础上，添加有机功能助剂制备而成。所述的有机功能助剂中，至少包括一种以醇、醚、酮等溶剂溶解的非水溶剂型的聚酯溶液作为胶黏剂。所用的非水溶剂型的聚酯胶黏剂具体是指多缩乙二醇二酸酯(n≥10)及其修饰物或和一缩二乙二醇二酸酯及其修饰物；2. The PEDOT/PSS conductive inks are prepared by adding organic functional additives on the basis of different types of PEDOT/PSS dispersions. The organic functional additive includes at least one non-aqueous solvent type polyester solution dissolved in a solvent such as an alcohol, an ether or a ketone as an adhesive. The non-aqueous solvent-type polyester adhesive used specifically refers to polyglycol dicarboxylate (n ≥ 10) and its modifications or diethylene glycol dicarboxylate and its modifications;
醇可以是甲醇、乙醇、正丙醇、异丙醇、丁醇、正辛醇，二醇或二醇醚，如乙二醇、1,2-丙二醇、1,3-丙二醇或二甘醇；醚可以是***、正丙醚、正丁醚、甲丁醚、甲基叔丁基醚、乙二醇二甲醚、四氢呋喃、1,4-二氧六环。酮可以是丙酮、甲乙酮、甲基异丁基酮、甲基叔丁基酮；The alcohol may be methanol, ethanol, n-propanol, isopropanol, butanol, n-octanol, glycol or glycol ether such as ethylene glycol, 1,2-propanediol, 1,3-propanediol or diethylene glycol; The ether may be diethyl ether, n-propyl ether, n-butyl ether, methyl butyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, 1,4-dioxane. The ketone may be acetone, methyl ethyl ketone, methyl isobutyl ketone or methyl t-butyl ketone;
聚酯溶液中聚合物含量为0.5～85％，优选为25～30％； The polymer content in the polyester solution is from 0.5 to 85%, preferably from 25 to 30%;
以醇、醚、酮等溶剂溶解的非水溶剂型的聚酯溶液在所述PEDOT/PSS导电油墨中的含量基于PEDOT/PSS分散液重量为0.001～15重量％，优选为0.1～2重量％。The content of the nonaqueous solvent-type polyester solution dissolved in a solvent such as an alcohol, an ether or a ketone in the PEDOT/PSS conductive ink is 0.001 to 15% by weight, preferably 0.1 to 2% by weight based on the weight of the PEDOT/PSS dispersion.
本发明提供的PEDOT/PSS导电油墨中，还可以同时添加以上两类胶黏剂，两者重量比例1:10～1:1，合计含量分别为基于中性分散液重量的0.001～15重量％，优选为0.1～2重量％。In the PEDOT/PSS conductive ink provided by the invention, the above two types of adhesives can also be added at the same time, the weight ratio of the two is 1:10 to 1:1, and the total content is 0.001 to 15% by weight based on the weight of the neutral dispersion respectively. It is preferably 0.1 to 2% by weight.
本发明配导电油墨的分散液，可以是水型也可以是溶剂型的；提供的胶黏剂即可以制酸性的PEDOT/PSS导电油墨，也可以制普通中性化的PEDOT/PSS导电油墨。后者为在酸性PEDOT/PSS分散液中使用碱性添加剂调节pH值至近中性即可，其中由于酸碱反应会产生部分中性离子，如不除去，会严重影响到导电涂层的性能。The dispersion liquid of the conductive ink of the invention may be water type or solvent type; the provided adhesive agent can be made of acidic PEDOT/PSS conductive ink, or can be made of ordinary neutralized PEDOT/PSS conductive ink. The latter is to adjust the pH to near-neutral using an alkaline additive in the acidic PEDOT/PSS dispersion, wherein some neutral ions are generated due to the acid-base reaction, and if not removed, the performance of the conductive coating is seriously affected.
在聚合反应中实现中性化，同时解决粘度特性是本发明中涉及的PEDOT/PSS导电油墨的核心。聚合反应过程中(可以之前，可以之后)可以添加磷酸酯作为粘度调节剂，其酯部分可以为甲基、乙基、丙基、正丁基、异丙基及其组合；添加量为重量的0.0005～1重量％，优选0.01～0.2重量％。聚合反应后对反应液进行的中性化处理，为使用碱性添加剂调节pH值至近中性；Neutralization in the polymerization reaction while solving the viscosity characteristics is the core of the PEDOT/PSS conductive ink involved in the present invention. Phosphate ester may be added as a viscosity modifier during the polymerization reaction (may, before, after), and the ester moiety may be methyl, ethyl, propyl, n-butyl, isopropyl, and combinations thereof; 0.0005 to 1% by weight, preferably 0.01 to 0.2% by weight. Neutralizing the reaction solution after the polymerization reaction, using a basic additive to adjust the pH to near neutral;
所使用的碱性添加剂可以是碱金属氢氧化物如氢氧化锂、氢氧化钠、氢氧化钾，碱金属碳酸盐或碳酸氢盐如碳酸锂、碳酸钠、碳酸钾或碳酸氢钠、碳酸氢钾，碱土金属氢氧化物如氢氧化镁、氢氧化钙，碱土碳酸盐或碳酸氢盐如碳酸镁、碳酸钙，氨，脂肪族烷基胺例如带有任选取代的C1～C20的烷基的单-、二、或三-烷基胺，如甲胺、二甲胺、三甲胺、乙胺、二乙胺、三乙胺、乙醇胺或二甲基乙醇胺，芳香族胺如苯胺、二苯胺、邻二苯胺、间二苯胺或对二苯胺。The alkaline additive used may be an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide, an alkali metal carbonate or a hydrogencarbonate such as lithium carbonate, sodium carbonate, potassium carbonate or sodium hydrogencarbonate, carbonic acid. Potassium hydrogen, alkaline earth metal hydroxides such as magnesium hydroxide, calcium hydroxide, alkaline earth carbonates or hydrogencarbonates such as magnesium carbonate, calcium carbonate, ammonia, aliphatic alkylamines, for example with optionally substituted C1 to C20 a mono-, di- or tri-alkylamine of an alkyl group such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethanolamine or dimethylethanolamine, an aromatic amine such as aniline, Diphenylamine, o-diphenylamine, m-diphenylamine or p-diphenylamine.
碱性添加剂优选以溶液的形式使用，优选溶剂可以是水和/或醇，用于中和PEDOT/PSS分散液。醇可以是甲醇、乙醇、正丙醇、异丙醇、丁醇、正辛醇，二醇或二醇醚，如乙二醇、1,2-丙二醇、1,3-丙二醇或二甘醇；The alkaline additive is preferably used in the form of a solution, preferably the solvent may be water and/or an alcohol for neutralizing the PEDOT/PSS dispersion. The alcohol may be methanol, ethanol, n-propanol, isopropanol, butanol, n-octanol, glycol or glycol ether such as ethylene glycol, 1,2-propanediol, 1,3-propanediol or diethylene glycol;
上述碱性添加剂也适合于以上普通中性化的PEDOT/PSS导电油墨的制备。The above basic additives are also suitable for the preparation of the above generally neutralized PEDOT/PSS conductive ink.
本发明提供的PEDOT/PSS导电油墨，将碱性添加剂加入到PEDOT/PSS分散液中，通过pH剂调节体系pH值，pH值范围为5.0～9.0，优选pH范围为6.0～8.0，更优选pH值为6.5～7.2；The PEDOT/PSS conductive ink provided by the invention adds the alkaline additive to the PEDOT/PSS dispersion, adjusts the pH value of the system through the pH agent, and the pH ranges from 5.0 to 9.0, preferably the pH ranges from 6.0 to 8.0, more preferably the pH. The value is 6.5 to 7.2;
pH值调节后，需经过陈化工艺，使反应液达到油墨要求的粘度范围，粘度范围为1 000～50 000mPa·s，优选粘度范围为2 000～20 000mPa·s；更优选粘度范围为5 000～8 000mPa·s；After the pH value is adjusted, the aging process is required to bring the reaction solution to the viscosity range required by the ink. The viscosity ranges from 1 000 to 50 000 mPa·s, preferably the viscosity ranges from 2 000 to 20 000 mPa·s; more preferably, the viscosity range is 5 000 to 8 000 mPa·s;
陈化至达到油墨要求的粘度范围后，还需要经过一定的后处理工艺操作，即将反应混合物转移，再加入阳离子交换剂和阴离子交换剂，以除去无机盐，得到中性的、油墨粘度的、无离子的PEDOT/PSS水型分散液；可以加入溶剂蒸发带去大部分水，方便得到油墨粘度的溶剂型分散液；分散液可供制备水型或溶剂型的中性导电油墨。制备导电油墨时添加的有机功能助剂除胶黏剂外，还包括其它有机功能助剂，如导电增强剂、表面活性剂及流平剂等；After aging to reach the viscosity range required by the ink, it is also necessary to undergo a certain post-treatment process, that is, transfer the reaction mixture, and then add a cation exchanger and an anion exchanger to remove the inorganic salt to obtain a neutral, ink viscosity, Non-ionic PEDOT/PSS water-type dispersion; solvent-type dispersion which can be used to obtain most of the water by solvent evaporation, and convenient to obtain the viscosity of the ink; the dispersion can be used to prepare water- or solvent-based neutral conductive ink. In addition to the adhesive, the organic functional additive added in the preparation of the conductive ink includes other organic functional additives such as a conductive enhancer, a surfactant and a leveling agent;
用上述的可中性化的PEDOT/PSS导电油墨，可以在玻璃、玻璃树脂、含氟聚合物、硅酮、聚烯烃、聚醚烃、PET、PEN、PMMA以及PC、PI及其组合的共聚或组合物或层压物等基底上涂布得到功能化的导电涂层。Copolymerization of glass, glass resin, fluoropolymer, silicone, polyolefin, polyether hydrocarbon, PET, PEN, PMMA, PC, PI and combinations thereof using the above-mentioned neutralizable PEDOT/PSS conductive ink A functionalized conductive coating is applied to a substrate such as a composition or laminate.
本发明目的(二)是通过以下技术方案实现的：The object (2) of the present invention is achieved by the following technical solutions:
一种新型的具有中性化PEDOT/PSS导电层的透明电极，包括透明基材层以及覆盖于该透 明基材层上的导电层，该导电层包括覆盖于透明基材层上的纳米银线导电层，以及覆盖于纳米银线导电层上的中性化PEDOT/PSS导电层。A novel transparent electrode having a neutralized PEDOT/PSS conductive layer, comprising a transparent substrate layer and covering the through A conductive layer on the substrate layer, the conductive layer comprising a nano-silver wire conductive layer overlying the transparent substrate layer, and a neutralized PEDOT/PSS conductive layer overlying the nano-silver wire conductive layer.
所述的透明基材层，选材为透明材料：玻璃、玻璃树脂、含氟聚合物、硅酮、聚烯烃、聚醚烃、PET、PEN、PMMA以及PC、PI及其组合的共聚或组合物或层压物等；The transparent substrate layer is selected from transparent materials: glass, glass resin, fluoropolymer, silicone, polyolefin, polyether hydrocarbon, PET, PEN, PMMA, and copolymer or composition of PC, PI and combinations thereof. Or laminate, etc.;
所述导电层厚度为50～300nm；The conductive layer has a thickness of 50 to 300 nm;
构成所述的中性化PEDOT/PSS导电层由中性化PEDOT/PSS导电油墨制得：The neutralized PEDOT/PSS conductive layer constituting the above is made of a neutralized PEDOT/PSS conductive ink:
本发明中所使用的纳米银线导电油墨，其质量百分比浓度为0.05～8％，纳米银线长度在10～50μm之间，纳米银线的直径在5～300nm；The nano silver wire conductive ink used in the present invention has a mass percentage concentration of 0.05 to 8%, a nano silver wire length of 10 to 50 μm, and a nano silver wire diameter of 5 to 300 nm;
本发明中所使用的中性PEDOT/PSS导电油墨与纳米银线导电油墨的掺混物，其中纳米银线导电油墨占中性化PEDOT/PSS导电油墨重量为0.5～25％；The blend of the neutral PEDOT/PSS conductive ink and the nano silver wire conductive ink used in the present invention, wherein the nano silver wire conductive ink accounts for 0.5 to 25% by weight of the neutralized PEDOT/PSS conductive ink;
一种具有中性化PEDOT透明稳定电极的制备方法，其包括如下步骤：A preparation method for a neutralized PEDOT transparent stable electrode, comprising the following steps:
(1)对基材材料进行表面预处理，作为基材层；(1) subjecting the substrate material to surface pretreatment as a substrate layer;
(2)在基材层上面涂布纳米银线导电油墨，固化优化后形成纳米银线导电层；(2) coating a nano silver wire conductive ink on the substrate layer, and forming a nano silver wire conductive layer after curing optimization;
(3)然后在纳米银线导电层上面涂布中性化PEDOT/PSS导电油墨，或者为其与纳米银线的掺混物，固化优化后形成高分子导电层。(3) Then, a neutralized PEDOT/PSS conductive ink is coated on the nano silver wire conductive layer, or a blend thereof with the nano silver wire is cured to form a polymer conductive layer.
由于采用本发明的技术方案，本发明具有的有益效果是：Due to the adoption of the technical solution of the present invention, the present invention has the following beneficial effects:
具有中性化PEDOT/PSS复合导电层的透明电极，其导电层的方块电阻值为10～150Ω/□，光透过率在550nm波长处为85～91％，从而获得了高导电性以及高透光性；通过将中性化PEDOT/PSS导电高分子层覆盖于纳米银线导电层之上，使之与外界空气隔绝，且避免如用酸性PEDOT/PSS与银纳米线接触时因腐蚀性作用而导致方块电阻增大的效果，显著地提高透明电极耐热、耐电流方面的稳定性。同时由于采用溶液法/印刷工艺的成膜制备方法，相对于ITO薄膜采用真空蒸镀工艺而言，大大降低了设备和制造成本。因此，本发明所述的具有中性化PEDOT/PSS复合导电层的透明电极膜具有导电性高、透光性好、制造工艺简单以及耐候、耐电流等优点，可用于有机太阳能电池、有机发光二极管或触摸显示屏及医疗器件、电容等领域。The transparent electrode having a neutralized PEDOT/PSS composite conductive layer has a sheet resistance of 10 to 150 Ω/□ and a light transmittance of 85 to 91% at a wavelength of 550 nm, thereby obtaining high conductivity and high. Transmittance; by covering the neutralized PEDOT/PSS conductive polymer layer on the nano-silver wire conductive layer to isolate it from the outside air, and avoiding corrosion due to contact with silver nanowires with acidic PEDOT/PSS The effect of increasing the sheet resistance is to significantly improve the stability of the transparent electrode in terms of heat resistance and current resistance. At the same time, due to the film formation preparation method using the solution method/printing process, the vacuum evaporation process is used in comparison with the ITO film, which greatly reduces equipment and manufacturing costs. Therefore, the transparent electrode film having the neutralized PEDOT/PSS composite conductive layer of the present invention has the advantages of high conductivity, good light transmittance, simple manufacturing process, weather resistance and current resistance, and can be used for organic solar cells and organic light-emitting. Diode or touch display and medical devices, capacitors and other fields.
附图说明DRAWINGS
图1是本发明的结构剖面示意图Figure 1 is a schematic cross-sectional view showing the structure of the present invention
图2是不同导电材料制得的透明电极在不同温度下的稳定性Figure 2 shows the stability of transparent electrodes made of different conductive materials at different temperatures.
图3是不同导电材料制得的透明电极的扫描电镜图像(SEM)Figure 3 is a scanning electron microscope image (SEM) of a transparent electrode made of different conductive materials.
具体实施方式detailed description
下面结合实施例对本发明进行详细的说明，该实施例以发明技术方案为前提给出了详细的实施方式和具体的工艺操作过程，但本发明的保护范围不仅仅局限于下述的实施例。The present invention will be described in detail below with reference to the embodiments, which show detailed embodiments and specific process operations on the premise of the technical solutions of the present invention, but the scope of protection of the present invention is not limited only to the embodiments described below.
第一部分：中性PEDOT/PSS分散液的制备Part I: Preparation of Neutral PEDOT/PSS Dispersion
PEDOT/PSS分散液的聚合工艺(参照Bayer AG.EP0686662,1995)：将250g水、2.5g 聚苯乙烯磺酸、55mg的10％硫酸铁(III)以及2.35g的过硫酸钠加入到反应容器中，调节温度，搅拌溶解。温度降低至常温，加入1.0g亚乙基二氧基噻吩(EDOT)，进行反应。Polymerization process of PEDOT/PSS dispersion (refer to Bayer AG. EP0686662, 1995): 250 g of water, 2.5 g Polystyrenesulfonic acid, 55 mg of 10% iron (III) sulfate, and 2.35 g of sodium persulfate were added to the reaction vessel, the temperature was adjusted, and the mixture was stirred and dissolved. The temperature was lowered to normal temperature, and 1.0 g of ethylenedioxythiophene (EDOT) was added to carry out a reaction.
实施例1～5及对比例1～2为上述聚合工艺基础上，中性化PEDOT/PSS分散液的制备。Examples 1 to 5 and Comparative Examples 1 and 2 are preparations of a neutralized PEDOT/PSS dispersion based on the above polymerization process.
实施例1：Example 1:
PEDOT/PSS聚合反应结束后，停止反应。加入2-氨基-2-甲基-1-丙醇，通过pH计监测调节pH值至近中性后，陈化0.5小时。将混合物转移至烧杯中，再加入50毫升的阳离子交换剂(Lewatit S100H，Lanxess AG)和29毫升的阴离子交换剂(Lewatit MP62，Lanxess AG)除去无机盐。将此混合物搅拌6小时后，过滤出交换剂，旋转粘度仪测试粘度；After the completion of the PEDOT/PSS polymerization reaction, the reaction was stopped. 2-Amino-2-methyl-1-propanol was added and the pH was adjusted to near neutral by monitoring with a pH meter and aged for 0.5 hours. The mixture was transferred to a beaker, and 50 ml of a cation exchanger (Lewatit S100H, Lanxess AG) and 29 ml of an anion exchanger (Lewatit MP62, Lanxess AG) were added to remove the inorganic salt. After the mixture was stirred for 6 hours, the exchanger was filtered off, and the viscosity was measured by a rotary viscometer;
实施例2：Example 2:
PEDOT/PSS反应前加入0.2g磷酸三乙酯，聚合反应结束后，停止反应。然后再加入2-氨基-2-甲基-1-丙醇，通过pH计监测调节pH值至近中性后，陈化0.5小时。按照实施例1中相同方法，进行阴阳树脂交换处理后，旋转粘度仪测试粘度；0.2 g of triethyl phosphate was added before the PEDOT/PSS reaction, and the reaction was stopped after the completion of the polymerization reaction. Then, 2-amino-2-methyl-1-propanol was further added, and the pH was adjusted to near-neutral by a pH meter to be aged for 0.5 hours. After the cation-yang resin exchange treatment was carried out in the same manner as in Example 1, the viscosity was measured by a rotary viscometer;
实施例3：Example 3:
PEDOT/PSS聚合反应结束后，停止反应，加入2-氨基-2-甲基-1-丙醇，通过pH计监测调节pH值至近中性后，陈化1小时。按照实施例1中相同方法，进行阴阳树脂交换处理后，旋转粘度仪测试粘度；After completion of the PEDOT/PSS polymerization reaction, the reaction was stopped, 2-amino-2-methyl-1-propanol was added, and the pH was adjusted to near neutral by monitoring with a pH meter, and aged for 1 hour. After the cation-yang resin exchange treatment was carried out in the same manner as in Example 1, the viscosity was measured by a rotary viscometer;
实施例4：Example 4:
PEDOT/PSS聚合反应结束后，停止反应，加入2-氨基-2-甲基-1-丙醇，通过pH计监测调节pH值至经中性后，陈化2小时，按照实施例1中相同方法进行阴阳树脂交换处理后，旋转粘度仪测试粘度；After the completion of the PEDOT/PSS polymerization reaction, the reaction was stopped, 2-amino-2-methyl-1-propanol was added, and the pH was adjusted to neutral after monitoring by a pH meter, and aged for 2 hours, as in Example 1. After the method of yin and yang resin exchange treatment, the viscosity is measured by a rotary viscometer;
实施例5：Example 5:
PEDOT/PSS聚合反应结束后，停止反应，加入2-氨基-2-甲基-1-丙醇，通过pH计监测调节pH值至经中性后，陈化5小时，按照实施例1中相同方法进行阴阳树脂交换处理后，旋转粘度仪测试粘度；After the completion of the PEDOT/PSS polymerization reaction, the reaction was stopped, 2-amino-2-methyl-1-propanol was added, and the pH was adjusted to neutral after monitoring by a pH meter, and aged for 5 hours, as in Example 1. After the method of yin and yang resin exchange treatment, the viscosity is measured by a rotary viscometer;
对比例1：Comparative example 1:
实施例1中PEDOT/PSS聚合反应结束后，停止反应，陈化2小时，按照实施例1中相同方法进行阴阳树脂交换处理后，加入2-氨基-2-甲基-1-丙醇，通过pH计监测调节pH值至近中性后，旋转粘度仪测试粘度；After completion of the PEDOT/PSS polymerization reaction in Example 1, the reaction was stopped, aged for 2 hours, and after the cation-yang resin exchange treatment was carried out in the same manner as in Example 1, 2-amino-2-methyl-1-propanol was added thereto. After the pH meter monitors the pH to near neutral, the viscosity is measured by a rotary viscometer;
对比例2：Comparative example 2:
实施例1中PEDOT/PSS聚合反应结束后，停止反应，陈化5小时，按照实施例1中相同方法进行阴阳树脂交换处理后，加入2-氨基-2-甲基-1-丙醇，通过pH计调节监测pH值至近中性后，旋转粘度仪测试粘度；After the completion of the PEDOT/PSS polymerization reaction in Example 1, the reaction was stopped, aged for 5 hours, and the cation-yang resin exchange treatment was carried out in the same manner as in Example 1, and 2-amino-2-methyl-1-propanol was added thereto. After the pH meter is adjusted to monitor the pH to near neutral, the viscosity is measured by a rotary viscometer;
表1：实施例1～5及对比例1～2中PEDOT/PSS分散液粘度及pH值Table 1: Viscosity and pH of PEDOT/PSS dispersions in Examples 1 to 5 and Comparative Examples 1 and 2.
  陈化时间(小时)Aging time (hours) 粘度(mPa·s)Viscosity (mPa·s) pH值pH value
实施例1Example 1 0.50.5 537537 7.47.4
实施例2Example 2 0.50.5 45004500 7.57.5
实施例3Example 3 11 23542354 7.67.6
实施例4Example 4 22 46724672 8.08.0
实施例5Example 5 55 47364736 7.87.8
对比例1Comparative example 1 22 2525 7.57.5
对比例2Comparative example 2 55 3333 7.67.6
结论：实施例与对比例操作上的差异在于：实施例中先加入碱调节pH值，然后陈化不同时间(0.5小时、1小时、2小时、5小时)，再经过阴阳离子交换树脂后处理；而对比例则是先陈化不同时间(2小时、5小时)，然后经过阴阳离子交换树脂后处理，再加入碱调节pH值。Conclusion: The difference between the operation of the examples and the comparative example is that in the embodiment, the alkali is first added to adjust the pH value, and then aged for different time (0.5 hour, 1 hour, 2 hours, 5 hours), and then treated by anion-cation exchange resin. The comparison ratio is first aged for different time (2 hours, 5 hours), and then treated by anion-cation exchange resin, and then alkali is added to adjust the pH.
从表1可以清楚地看出，实施例1、3、4及5中制得的中性化PEDOT/PSS分散液的粘度随陈化时间的延长而递增，至陈化时间2小时后，粘度基本稳定；而实施例2，加入了磷酸三乙酯作为物料，陈化0.5小时后，粘度即接近稳定(与实施例4和5中粘度值基本相同)；对比例1～2中制得的中性化PEDOT/PSS分散液的粘度不随陈化时间改变而改变，均为低粘度的分散液，在丝网印刷等涂布工艺中，需要预先添加增稠剂达到所需粘度才能使用。As is clear from Table 1, the viscosity of the neutralized PEDOT/PSS dispersion prepared in Examples 1, 3, 4 and 5 increased with the aging time, and the viscosity after 2 hours of aging time Basically stable; and in Example 2, triethyl phosphate was added as a material, and after 0.5 hours of aging, the viscosity was nearly stable (substantially the same as the viscosity values in Examples 4 and 5); prepared in Comparative Examples 1 and 2. The viscosity of the neutralized PEDOT/PSS dispersion does not change with the aging time, and is a low-viscosity dispersion. In the coating process such as screen printing, it is necessary to add a thickener to the desired viscosity before use.
第二部分：中性PEDOT/PSS导电油墨的制备及透明导电薄膜性能测试Part II: Preparation of Neutral PEDOT/PSS Conductive Ink and Performance Test of Transparent Conductive Film
实施例6～10为在实施例4制得的中性化PEDOT/PSS分散液的基础上，添加胶黏剂、表面活性剂以及导电增强剂，制备中性化PEDOT/PSS导电油墨；对比例3～7为在对比例1和市购的PH500产品基础上，添加增稠剂、胶黏剂、表面活性剂以及导电增强剂，制备中性化PEDOT/PSS导电油墨。实施例及对比例中使用的苯鸟粪胺-甲醛树脂WH-03及己二酸一缩二乙二醇聚酯甲乙酮溶液SJS-2或聚乙二醇二壬酸酯异丙醇溶液SJS-3均由上海合成树脂研究所合成生产。Examples 6 to 10 are based on the neutralized PEDOT/PSS dispersion prepared in Example 4, and an adhesive, a surfactant, and a conductivity enhancer are added to prepare a neutralized PEDOT/PSS conductive ink; 3-7 is a neutralized PEDOT/PSS conductive ink prepared on the basis of Comparative Example 1 and a commercially available PH500 product by adding a thickener, an adhesive, a surfactant, and a conductive reinforcing agent. Benzoin amine-formaldehyde resin WH-03 and adipic acid diethylene glycol polyester methyl ethyl ketone solution SJS-2 or polyethylene glycol dicaprate isopropanol solution SJS- used in the examples and comparative examples 3 are all synthetically produced by Shanghai Synthetic Resin Research Institute.
实施例6：Example 6
实施例4中制得的中性PEDOT/PSS分散液中，添加WH-03(1重量％)，
Figure PCTCN2015088806-appb-000002
(0.1重量％)以及乙二醇(5重量％)；In the neutral PEDOT/PSS dispersion prepared in Example 4, WH-03 (1% by weight) was added,
Figure PCTCN2015088806-appb-000002
(0.1% by weight) and ethylene glycol (5% by weight);
实施例7：Example 7
实施例4中制得的中性PEDOT/PSS分散液中，添加SJS-2(1重量％)，
Figure PCTCN2015088806-appb-000003
(0.1重量％)以及乙二醇(5重量％)；In the neutral PEDOT/PSS dispersion prepared in Example 4, SJS-2 (1% by weight) was added,
Figure PCTCN2015088806-appb-000003
(0.1% by weight) and ethylene glycol (5% by weight);
实施例8：Example 8
实施例4中制得的中性PEDOT/PSS分散液中，添加SJS-3(1重量％)，
Figure PCTCN2015088806-appb-000004
(0.1重量％)以及乙二醇(5重量％)；In the neutral PEDOT/PSS dispersion prepared in Example 4, SJS-3 (1% by weight) was added,
Figure PCTCN2015088806-appb-000004
(0.1% by weight) and ethylene glycol (5% by weight);
实施例9：Example 9
实施例4中制得的中性PEDOT/PSS分散液中，WH-03(0.5重量％)，SJS-2(0.5重量％)，
Figure PCTCN2015088806-appb-000005
(0.1重量％)以及乙二醇(5重量％)；In the neutral PEDOT/PSS dispersion prepared in Example 4, WH-03 (0.5% by weight), SJS-2 (0.5% by weight),
Figure PCTCN2015088806-appb-000005
(0.1% by weight) and ethylene glycol (5% by weight);
实施例10：Example 10:
实施例4中制得的中性PEDOT/PSS分散液中，WH-03(0.5重量％)，SJS-3(0.5重量％)，
Figure PCTCN2015088806-appb-000006
(0.1重量％)以及乙二醇(5重量％)；In the neutral PEDOT/PSS dispersion prepared in Example 4, WH-03 (0.5% by weight), SJS-3 (0.5% by weight),
Figure PCTCN2015088806-appb-000006
(0.1% by weight) and ethylene glycol (5% by weight);
对比例3：Comparative example 3:
对比例1中制得的中性PEDOT/PSS分散液中，添加TT-615(0.5重量％)，WH-03(1重量％)，
Figure PCTCN2015088806-appb-000007
(0.1重量％)以及乙二醇(5重量％)；In the neutral PEDOT/PSS dispersion prepared in Comparative Example 1, TT-615 (0.5% by weight) and WH-03 (1% by weight) were added.
Figure PCTCN2015088806-appb-000007
(0.1% by weight) and ethylene glycol (5% by weight);
对比例4：Comparative example 4:
对比例2中制得的中性PEDOT/PSS分散液中，添加TT-615(0.5重量％)，SJS-2(1重量％)，
Figure PCTCN2015088806-appb-000008
(0.1重量％)以及乙二醇(5重量％)；In the neutral PEDOT/PSS dispersion prepared in Comparative Example 2, TT-615 (0.5% by weight) and SJS-2 (1% by weight) were added.
Figure PCTCN2015088806-appb-000008
(0.1% by weight) and ethylene glycol (5% by weight);
对比例5：Comparative example 5:
市购贺利氏公司的CLEVIOS TM PH500PEDOT/PSS分散液，加入2-氨基-2-甲基-1-丙醇，通过pH计监测调节pH值至近中性，在制得的中性PEDOT/PSS分散液中，添加TT-615(0.5重量％)，WH-03(1重量％)，
Figure PCTCN2015088806-appb-000009
(0.1重量％)以及乙二醇(5重量％)；Purchase of Heraeus's CLEVIOS TM PH500PEDOT/PSS dispersion, add 2-amino-2-methyl-1-propanol, adjust pH to near-neutral by pH meter, and obtain neutral PEDOT/PSS To the dispersion, TT-615 (0.5% by weight), WH-03 (1% by weight),
Figure PCTCN2015088806-appb-000009
(0.1% by weight) and ethylene glycol (5% by weight);
对比例6：Comparative example 6:
市购贺利氏公司的CLEVIOS TM PH500PEDOT/PSS分散液，加入2-氨基-2-甲基-1-丙醇，通过pH计监测调节pH值至近中性，在制得的中性PEDOT/PSS分散液中，添加TT-615(0.5重量％)，SJS-2(1重量％)，
Figure PCTCN2015088806-appb-000010
(0.1重量％)以及乙二醇(5重量％)；Purchase of Heraeus's CLEVIOS TM PH500PEDOT/PSS dispersion, add 2-amino-2-methyl-1-propanol, adjust pH to near-neutral by pH meter, and obtain neutral PEDOT/PSS To the dispersion, TT-615 (0.5% by weight), SJS-2 (1% by weight),
Figure PCTCN2015088806-appb-000010
(0.1% by weight) and ethylene glycol (5% by weight);
对比例7：Comparative example 7:
市购贺利氏公司的CLEVIOS TM PH500PEDOT/PSS分散液，加入2-氨基-2-甲基-1-丙醇，通过pH计监测调节pH值至近中性，在制得的中性PEDOT/PSS分散液中，添加TT-615(0.5重量％)，SJS-2(0.5重量％)，WH-03(0.5重量％)
Figure PCTCN2015088806-appb-000011
(0.1重量％)以及乙二醇(5重量％)；Purchase of Heraeus's CLEVIOS TM PH500PEDOT/PSS dispersion, add 2-amino-2-methyl-1-propanol, adjust pH to near-neutral by pH meter, and obtain neutral PEDOT/PSS To the dispersion, TT-615 (0.5% by weight), SJS-2 (0.5% by weight), and WH-03 (0.5% by weight) were added.
Figure PCTCN2015088806-appb-000011
(0.1% by weight) and ethylene glycol (5% by weight);
透明导电薄膜的制备：Preparation of transparent conductive film:
实施例6～10及对比例3～7中制得的PEDOT/PSS导电油墨，使用100μm高透明PET薄膜(东丽)作为基材(透光率>92.0％，雾度<0.5％)，以湿膜厚度20μm进行棍涂，135℃下，固化5分钟，制得透明导电薄膜，测试相关性能数据(表2)。其中，采用四探针电阻仪测试涂层方块电阻；透光率及雾度参照标准GB/T 2410-2008进行测试；铅笔硬度参照GB/T6739-2006进行测试；涂层粘附力测试以GB/T9286-1998(百格刀)实验测试；The PEDOT/PSS conductive inks prepared in Examples 6 to 10 and Comparative Examples 3 to 7 were made of a 100 μm high transparent PET film (Dongli) as a substrate (light transmittance > 92.0%, haze < 0.5%). A wet film thickness of 20 μm was applied to the bar, and cured at 135 ° C for 5 minutes to prepare a transparent conductive film, and the relevant performance data was tested (Table 2). Among them, the four-probe resistance meter was used to test the resistance of the coating sheet; the transmittance and haze were tested according to the standard GB/T 2410-2008; the pencil hardness was tested according to GB/T6739-2006; the coating adhesion test was GB. /T9286-1998 (Hundred Grid Knife) experimental test;
表2：实施例5～7及对比例3～5制得的透明导电薄膜性能数据Table 2: Performance data of transparent conductive films prepared in Examples 5 to 7 and Comparative Examples 3 to 5
Figure PCTCN2015088806-appb-000012
Figure PCTCN2015088806-appb-000012
Figure PCTCN2015088806-appb-000013
Figure PCTCN2015088806-appb-000013
结论：相同条件下，添加苯鸟粪胺-甲醛树脂WH-03的导电油墨制成的薄膜，其铅笔硬度相较高，但雾度偏大，WH-03与SJS-2SJS-3掺混使用后，所得到的导电油墨各方面性能数据达到最优；而添加了TT-615作为增稠剂调节粘度后的导电油墨，制成薄膜的方块电阻以及雾度值均较大。Conclusion: Under the same conditions, the film made of conductive ink with Benzene guanamine-formaldehyde resin WH-03 has higher pencil hardness, but the haze is too large. WH-03 is mixed with SJS-2SJS-3. After that, the obtained performance data of the conductive ink is optimized in all aspects; and the conductive ink after adjusting the viscosity by adding TT-615 as a thickener, the sheet resistance and the haze value of the film are large.
通过用浸润不同溶剂的脱脂棉球以1kg压力摩擦10次后，测定透明导电薄膜涂层对溶剂的耐性。The resistance of the transparent conductive film coating to the solvent was measured by rubbing the cotton wool ball infiltrated with different solvents at a pressure of 1 kg for 10 times.
结果汇总于表3中：The results are summarized in Table 3:
O＝耐溶剂，涂层未被破坏；O = solvent resistant, the coating is not damaged;
×＝不耐溶剂，涂层被破坏。× = not resistant to solvents, the coating was destroyed.
表3：实施例6～10及对比例3～7制得的透明导电薄膜涂层对溶剂的耐性Table 3: Solvent resistance of transparent conductive film coatings prepared in Examples 6 to 10 and Comparative Examples 3 to 7
Figure PCTCN2015088806-appb-000014
Figure PCTCN2015088806-appb-000014
Figure PCTCN2015088806-appb-000015
Figure PCTCN2015088806-appb-000015
实验结果清楚地表明，与用对比例的分散液制备的涂层相比，用本发明的分散液制备的涂层对溶剂的耐性较高。The experimental results clearly show that the coating prepared with the dispersion of the present invention is more resistant to solvents than the coating prepared with the dispersion of the comparative example.
第三部分：导电涂层和稳定的PEDOT导电层电极的制备Part III: Preparation of Conductive Coatings and Stable PEDOT Conductive Layer Electrodes
如图1所示，本发明所述的稳定的PEDOT/PSS导电层电极包括透明基材层1以及透明电极层，所述透明电极层覆盖于所述的透明基材层1上且厚度为25～1000nm，包括涂布在基材层1上的纳米银线导电层2，以及涂布在纳米银线导电层2表面上的中性PEDOT/PSS高分子导电层或其与纳米银线掺混后形成的高分子导电层3。As shown in FIG. 1, the stabilized PEDOT/PSS conductive layer electrode of the present invention comprises a transparent substrate layer 1 and a transparent electrode layer, and the transparent electrode layer covers the transparent substrate layer 1 and has a thickness of 25 ～1000 nm, comprising a nano-silver wire conductive layer 2 coated on the substrate layer 1, and a neutral PEDOT/PSS polymer conductive layer coated on the surface of the nano-silver wire conductive layer 2 or blended with the nano-silver wire The polymer conductive layer 3 is formed later.
所述透明基材层1选用玻璃、PET、PEN、PMMA或PI等透明材料作为衬底材料。构成所述的纳米银线导电层2是将纳米银线导电油墨涂布在透明基材层上面得到的。所述的纳米银线导电油墨，其质量百分比浓度为0.05～8％，纳米银线长度在10～50μm之间，纳米银线的直径在5～300nm；高分子导电层3为在纳米银线导电层2上涂布的中性PEDOT/PSS导电油墨或其与纳米银线导电油墨掺混的形成的导电层，其中纳米银线导电油墨规格与纳米银线导电层2所用材料相同。The transparent substrate layer 1 is made of a transparent material such as glass, PET, PEN, PMMA or PI as a substrate material. The nano silver wire conductive layer 2 is formed by coating a nano silver wire conductive ink on a transparent substrate layer. The nano silver wire conductive ink has a mass percentage concentration of 0.05 to 8%, a nano silver wire length of 10 to 50 μm, a nano silver wire diameter of 5 to 300 nm, and a polymer conductive layer 3 of a nano silver wire. The neutral PEDOT/PSS conductive ink coated on the conductive layer 2 or the conductive layer formed by blending with the nano silver wire conductive ink, wherein the nano silver wire conductive ink has the same specifications as the nano silver wire conductive layer 2.
这种特有的中性PEDOT/PSS导电高分子层和纳米银线导电层的叠层电极结构，大大降低了透明电极导电层的方块电阻，同时保持了良好的光透过率、雾度等。值得一提的是，这种结构制得的透明电极还具有非常稳定的耐环境性，如耐热、耐溶剂以及耐电流等。The unique laminated structure of the neutral PEDOT/PSS conductive polymer layer and the nano silver wire conductive layer greatly reduces the sheet resistance of the transparent electrode conductive layer while maintaining good light transmittance, haze and the like. It is worth mentioning that the transparent electrode made of this structure also has very stable environmental resistance such as heat resistance, solvent resistance and current resistance.
用上述结构制备稳定的PEDOT/PSS导电层电极的方法，其包括如下步骤：A method for preparing a stable PEDOT/PSS conductive layer electrode using the above structure, comprising the steps of:
(1)对基材材料进行表面预处理，作为透明基材层1；(1) surface pretreatment of the substrate material as a transparent substrate layer 1;
(2)在基材层上面涂布纳米银线导电油墨，固化优化后形成纳米银线导电层2；(2) coating a nano silver wire conductive ink on the substrate layer, after curing optimization to form a nano silver wire conductive layer 2;
(3)然后在纳米银线导电层上面涂布中性化PEDOT/PSS导电油墨，或者为其与纳米银线的掺混物，固化优化后形成高分子导电层3。(3) Then, a neutralized PEDOT/PSS conductive ink is coated on the nano silver wire conductive layer, or a blend thereof with the nano silver wire, and the polymer conductive layer 3 is formed by curing optimization.
实施例11：Example 11
(1)对基材材料进行表面预处理，作为透明基材层1。(1) The substrate material is subjected to surface pretreatment as the transparent substrate layer 1.
选用光学PET膜作为基材材料，使用前先进行表面清洁，依次用清洗液、去离子水、异丙醇以及去离子水在超声清洗池中进行超声波清洗10分钟，然后在氮气流中吹干，作为透明基材层1。The optical PET film was selected as the substrate material, and the surface was cleaned before use, and ultrasonic cleaning was carried out in the ultrasonic cleaning bath for 10 minutes with washing liquid, deionized water, isopropyl alcohol and deionized water, and then dried in a nitrogen stream. As the transparent substrate layer 1.
(2)在透明基材层1上涂布制备纳米银线导电层2。(2) A nano-silver wire conductive layer 2 is prepared by coating on the transparent substrate layer 1.
本实施例中，选用纳米银线导电油墨为材料，采用滚涂的涂布工艺方法，将纳米银线导电油墨(XFNANO Agnws-60nm/20μm异丙醇溶剂，含固5％，南京先丰纳米材料科技有限公司)涂布在透明基材层1表面上，湿膜厚度12μm。涂布后，涂层在150℃下干燥5分钟，制得纳米银线导电层2。In this embodiment, the nano silver wire conductive ink is selected as the material, and the nano silver wire conductive ink (XFNANO Agnws-60nm/20μm isopropanol solvent, solid content 5%, Nanjing Xianfeng nanometer) is adopted by a roll coating process. Material Technology Co., Ltd.) was coated on the surface of the transparent substrate layer 1 with a wet film thickness of 12 μm. After coating, the coating was dried at 150 ° C for 5 minutes to prepare a nano-silver wire conductive layer 2.
(3)在纳米银线导电层2上涂布中性PEDOT/PSS高分子导电层3。(3) A neutral PEDOT/PSS polymer conductive layer 3 is coated on the nano silver wire conductive layer 2.
中性PEDOT/PSS导电油墨按实施例10制备。A neutral PEDOT/PSS conductive ink was prepared as in Example 10.
将中性PEDOT/PSS导电油墨印刷涂布在纳米银线导电层2表面上，丝网印刷所用的丝网 目数200的纱网。丝网印刷涂布后，涂层在150℃下干燥5分钟，制得中性PEDOT/PSS高分子层3，至此完成了整个稳定的PEDOT/PSS导电层电极。Printing and coating a neutral PEDOT/PSS conductive ink on the surface of the nano silver wire conductive layer 2, the screen used for screen printing A gauze with a mesh number of 200. After screen printing, the coating was dried at 150 ° C for 5 minutes to obtain a neutral PEDOT/PSS polymer layer 3, thus completing the entire stable PEDOT/PSS conductive layer electrode.
实施例12：Example 12
对基材材料进行表面预处理作为透明基材层1及在透明基材层1上涂布制备纳米银线导电层2的工艺与实施例11相同；Surface pretreatment of the substrate material as the transparent substrate layer 1 and coating of the nano silver wire conductive layer 2 on the transparent substrate layer 1 is the same as in the embodiment 11;
在纳米银线导电层2上涂布中性PEDOT/PSS导电油墨与纳米银线导电油墨的掺混物，形成高分子导电层3。其中，中性PEDOT/PSS导电油墨制备的制备工艺也与实施例11相同；A blend of a neutral PEDOT/PSS conductive ink and a nano silver wire conductive ink is coated on the nano silver wire conductive layer 2 to form a polymer conductive layer 3. Wherein, the preparation process of the neutral PEDOT/PSS conductive ink preparation is also the same as that of the embodiment 11;
本实施例中所使用的中性PEDOT/PSS导电油墨与纳米银线导电油墨的掺混物，其中纳米银线导电油墨占中性PEDOT/PSS导电油墨重量为2％；a blend of a neutral PEDOT/PSS conductive ink and a nano silver wire conductive ink used in the embodiment, wherein the nano silver wire conductive ink accounts for 2% by weight of the neutral PEDOT/PSS conductive ink;
然后涂布中性PEDOT/PSS导电油墨与纳米银线导电油墨的掺混物，形成高分子导电层3；Then coating a blend of neutral PEDOT / PSS conductive ink and nano silver wire conductive ink to form a polymer conductive layer 3;
将中性PEDOT/PSS导电油墨与纳米银线导电油墨的掺混物印刷涂布在纳米银线导电层2表面上，其工艺液与实施例11相同，至此完成了整个稳定的PEDOT/PSS导电层电极。A blend of a neutral PEDOT/PSS conductive ink and a nano silver wire conductive ink was printed on the surface of the nano silver wire conductive layer 2, and the process liquid was the same as in Example 11, thereby completing the entire stable PEDOT/PSS conduction. Layer electrode.
第四部分：PEDOT/PSS导电层电极稳定性测试Part IV: PEDOT/PSS Conductive Layer Electrode Stability Test
如附图2所示，选择贺利氏公司的PEDOT/PSS CLEVIOSTM PH1000分散液作为对比实验材料，设计制备以下四个对比导电层电极，并在不同温度下(90，120，150，180，210℃)下测试各个导电层电极表面电阻的稳定性：As shown in Figure 2, the Heraeus PEDOT/PSS CLEVIOS TM PH1000 dispersion was selected as the comparative experimental material, and the following four comparative conductive layer electrodes were designed and fabricated at different temperatures (90, 120, 150, 180, The stability of the surface resistance of each conductive layer electrode was tested at 210 ° C):
(1)在表面处理过的透明PET基材表面上，按实施例11中方法将纳米银线导电油墨涂布制备成导电层电极，测试表面电阻随温度的变化曲线(图2中方框线AgNW)；(1) On the surface of the surface-treated transparent PET substrate, the nano-silver wire conductive ink was coated into a conductive layer electrode according to the method of Example 11, and the surface resistance curve with temperature was tested (the block line AgNW in Fig. 2) );
(2)在表面处理过的透明PET基材表面上，按实施例11中方法将PH1000涂布制备成导电层电极，测试表面电阻随温度的变化曲线(图2中下三角线PH1000)；(2) On the surface of the surface-treated transparent PET substrate, PH1000 was coated into a conductive layer electrode according to the method of Example 11, and the surface resistance curve with temperature was tested (lower triangle line PH1000 in Fig. 2);
(3)在表面处理过的透明PET基材表面上，按实施例11中方法将上述中性PEDOT/PSS导电油墨涂布制备成导电层电极，测试表面电阻随温度的变化曲线(图2中左三角线Neutral-pH PEDOT)；(3) On the surface of the surface-treated transparent PET substrate, the above-mentioned neutral PEDOT/PSS conductive ink was coated into a conductive layer electrode according to the method of Example 11, and the surface resistance was measured as a function of temperature (Fig. 2 Left triangle Neutral-pH PEDOT);
(4)在表面处理过的透明PET基材表面上，按实施例11中方法将纳米银线导电油墨涂布制备成纳米银线导电层，再在该导电层上面涂布制备PH1000制备成导电层电极，测试表面电阻随温度的变化曲线(图2中圆点线AgNW/PH1000)；(4) On the surface of the surface treated transparent PET substrate, the nano silver wire conductive ink was coated into a nano silver wire conductive layer according to the method of Example 11, and then coated on the conductive layer to prepare PH1000 to be electrically conductive. Layer electrode, test surface resistance curve with temperature (point line AgNW/PH1000 in Figure 2);
(5)实施例11中制备的导电层电极，测试表面电阻随温度的变化曲线(图2中上三角线AgNW/Neutral-pH PEDOT)；(5) The conductive layer electrode prepared in Example 11 was tested for the surface resistance as a function of temperature (upper triangle line AgNW/Neutral-pH PEDOT in Fig. 2);
(6)实施例12中制备的导电层电极，测试表面电阻随温度的变化曲线(图2中右三角线AgNW/Neutral-pH PEDOT+AgNW)；(6) The conductive layer electrode prepared in Example 12, the surface resistance curve as a function of temperature was tested (the right triangle line AgNW/Neutral-pH PEDOT+AgNW in FIG. 2);
实验结果清楚地表明，温度条件(90，120，150，180，210℃)不同，方块电阻也存在差异。尤其是纳米银线与PH1000复合制备的导电层，表现为温度升至150℃后，方阻陡然上升，导电率急剧下降；而使用中性PEDOT/PSS导电油墨与纳米银线复合的导电薄膜，其方块电阻随温度变化方面表现得非常稳定。此外单独使用纳米银线、PH1000以及中性PEDOT/PSS导电油墨制成的导电层，随温度变化方块电阻也均表现稳定的性能。因此，经过中性处理后的PEDOT/PSS导电油墨在与纳米银线等金属性导电材料复合使用时，相比较酸 性PH1000产品，表现出了较好的兼容性以及稳定性。The experimental results clearly show that the temperature resistance (90, 120, 150, 180, 210 ° C) is different, and the sheet resistance is also different. In particular, the conductive layer prepared by the composite of nano-silver wire and PH1000 shows that the square resistance decreases sharply and the conductivity decreases sharply after the temperature rises to 150 ° C. The conductive film which is made of neutral PEDOT/PSS conductive ink and nano silver wire is used. Its sheet resistance is very stable with temperature changes. In addition, the conductive layer made of nano silver wire, PH1000 and neutral PEDOT/PSS conductive ink alone has stable performance with temperature change. Therefore, the PEDOT/PSS conductive ink after neutral treatment is used in combination with a metallic conductive material such as a nano silver wire. The PH1000 product shows good compatibility and stability.
上面实验结果得出的结论，在图3中所示的扫描电镜图像(SEM)得到了进一步的验证。SEM中可以清晰地看出，按照上述(4)中方法将纳米银线与PH1000先后涂布制备成导电层电极，在SEM图像中纳米银线出现了明显的遭腐蚀而断裂的现象，这就导致了该电极的方块电阻在高温条件下的急剧上升。而实施例11和实施例12以及上述(1)中方法涂布制备的导电层电极，在SEM图像中纳米银线结构均没有被破坏的现象，结构完整，从而保证了方块电阻数据稳定。综上所述，中性化PEDOT/PSS与纳米银线复合使用制备成的叠层式结构的电极具有高稳定性。 The conclusions obtained from the above experimental results are further verified by the scanning electron microscope image (SEM) shown in Fig. 3. It can be clearly seen in the SEM that the nano silver wire and the PH1000 are coated successively to form a conductive layer electrode according to the method in the above (4), and the nano silver wire appears to be corroded and broken in the SEM image, which is This causes a sharp rise in the sheet resistance of the electrode under high temperature conditions. In the SEM image, the nano silver wire structure is not destroyed in the SEM image, and the structure is complete, thereby ensuring the stability of the sheet resistance data. In summary, the neutralized PEDOT/PSS and nano-silver wire composite use of the prepared laminated structure electrode has high stability.

Claims (22)

  1. 一种由PEDOT/PSS分散液和胶黏剂等功能助剂复配成的导电油墨，其特征在于，添加至少一种鸟粪胺与至少一种羰基化合物形成的至少一种缩合物作为其中一种功能助剂。A conductive ink formulated by a functional auxiliary agent such as a PEDOT/PSS dispersion and an adhesive, characterized in that at least one condensate formed by adding at least one guanamine and at least one carbonyl compound is added as one of a functional additive.
  2. 一种由PEDOT/PSS分散液和胶黏剂等功能助剂复配成的导电油墨，其特征在于，添加至少一种以醇、醚、酮等溶剂溶解的非水溶剂型的聚酯溶液作为其中一种功能助剂。A conductive ink formulated by a functional auxiliary agent such as a PEDOT/PSS dispersion and an adhesive, characterized in that at least one non-aqueous solvent type polyester solution dissolved in a solvent such as an alcohol, an ether or a ketone is added as a solvent A functional additive.
  3. 根据权利要求1或2所述的导电油墨，其特征在于，添加鸟粪胺与至少一种羰基化合物形成的至少一种缩合物和/或以醇、醚、酮等溶剂溶解的非水溶剂型的聚酯溶液作为其中一种功能助剂，其添加量为0.001％～15％wt。The conductive ink according to claim 1 or 2, wherein at least one condensate formed by adding guanamine and at least one carbonyl compound and/or a nonaqueous solvent type dissolved in a solvent such as an alcohol, an ether or a ketone is added. As a functional auxiliary, the polyester solution is added in an amount of 0.001% to 15% by weight.
  4. 根据权利要求1～3中所述的导电油墨，其特征在于，以酸性分散液或中性化处理的分散液，添加增稠剂达到油墨所需粘度，且添加其它功能助剂，制得酸性或中性化导电油墨。The conductive ink according to any one of claims 1 to 3, which is characterized in that an acidic dispersion or a neutralized dispersion is added with a thickener to achieve a desired viscosity of the ink, and other functional additives are added to obtain an acidity. Or neutralized conductive ink.
  5. 根据权利要求1-3所述的导电油墨，其特征在于，可用于导电或抗静电的涂层。The conductive ink according to claims 1-3, which is useful for a conductive or antistatic coating.
  6. 一种由PEDOT/PSS分散液和胶黏剂等功能助剂复配成的导电油墨的制备方法，采用中性化的PEDOT/PSS分散液，所述中性化的PEDOT/PSS分散液由EDOT和PSS聚合而成，其特征在于，当聚合反应结束后，添加碱性添加剂调pH至5.0～9.0，陈化至达到所需粘度后，除去无机盐，制得中性的具有油墨粘度的PEDOT/PSS分散液，向所述中性的具有油墨粘度的PEDOT/PSS分散液中添加功能助剂，得到中性化的导电油墨。A method for preparing a conductive ink prepared by functional additives such as PEDOT/PSS dispersion and an adhesive, using a neutralized PEDOT/PSS dispersion, the neutralized PEDOT/PSS dispersion by EDOT And PSS polymerization, characterized in that, after the end of the polymerization reaction, an alkaline additive is added to adjust the pH to 5.0 to 9.0, and after aging until the desired viscosity is reached, the inorganic salt is removed to obtain a neutral PEDOT having ink viscosity. /PSS dispersion, a functional additive is added to the neutral PEDOT/PSS dispersion having ink viscosity to obtain a neutralized conductive ink.
  7. 根据权利要求6所述的制备方法，其特征在于，在EDOT和PSS的聚合反应过程中，添加磷酸酯作为粘度调节剂。The production method according to claim 6, wherein a phosphate ester is added as a viscosity modifier during the polymerization of EDOT and PSS.
  8. 根据权利要求6所述的制备方法，其特征在于，所述PEDOT/PSS分散液的粘度范围为1000～50000mPa·s。The method according to claim 6, wherein the PEDOT/PSS dispersion has a viscosity in the range of 1,000 to 50,000 mPa·s.
  9. 根据权利要求6所述的制备方法，其特征在于，其制备过程中利用达到所需油墨粘度的中性分散液，可以不添加增稠剂，且添加其它功能助剂，制得中性化导电油墨。The preparation method according to claim 6, wherein a neutral dispersion which reaches a desired ink viscosity is used in the preparation process, and a neutralizer can be obtained without adding a thickener and adding other functional additives. Ink.
  10. 根据权利要求6所述的制备方法，其特征在于，其制备过程中利用达到所需油墨粘度的 中性分散液，可以不添加增稠剂，且添加权利要求1～3中所述功能助剂，制得中性化导电油墨。The preparation method according to claim 6, wherein a viscosity of the desired ink is used in the preparation process. The neutral dispersion may be prepared by adding the thickening agent without adding a thickening agent as described in claims 1 to 3.
  11. 一种中性化PEDOT/PSS分散液的制备方法，所述分散液由EDOT和PSS聚合而成，其特征在于，在聚合反应结束后，添加碱性添加剂调pH至5.0～9.0，经陈化工艺，达到所需粘度后，除去无机盐，得到中性的PEDOT/PSS分散液。A method for preparing a neutralized PEDOT/PSS dispersion, wherein the dispersion is polymerized by EDOT and PSS, characterized in that after the end of the polymerization reaction, an alkaline additive is added to adjust the pH to 5.0 to 9.0, and the aging is performed. After the process reaches the desired viscosity, the inorganic salt is removed to obtain a neutral PEDOT/PSS dispersion.
  12. 根据权利要求11所述的制备方法，其特征在于，所述碱性添加剂优选为2-氨基-2-甲基-1-丙醇。The process according to claim 11, wherein the basic additive is preferably 2-amino-2-methyl-1-propanol.
  13. 根据权利要求11所述的制备方法，其特征在于，在聚合反应前加入磷酸三乙酯做为粘度调节剂。The process according to claim 11, wherein triethyl phosphate is added as a viscosity modifier before the polymerization.
  14. 根据权利要求11所述的制备方法，其特征在于，所述PEDOT/PSS分散液的粘度范围为1000～50000mPa·s。The method according to claim 11, wherein the PEDOT/PSS dispersion has a viscosity in the range of 1,000 to 50,000 mPa·s.
  15. 一种透明电极，包括透明基材层以及涂覆于所述透明基材层上的导电层，其特征在于，所述导电层依次包括：(1)涂布于所述透明基材层表面上的纳米银线导电层，(2)涂布于所述纳米银线导电层表面上的中性化PEDOT/PSS高分子导电层或其与纳米银线掺混后形成的高分子导电层。A transparent electrode comprising a transparent substrate layer and a conductive layer coated on the transparent substrate layer, wherein the conductive layer comprises: (1) coating on a surface of the transparent substrate layer a nano-silver wire conductive layer, (2) a neutralized PEDOT/PSS polymer conductive layer coated on the surface of the nano-silver wire conductive layer or a polymer conductive layer formed by blending with the nano-silver wire.
  16. 根据权利要求15所述的透明电极，其特征在于，所述导电层厚度为25～1000nm。The transparent electrode according to claim 15, wherein the conductive layer has a thickness of 25 to 1000 nm.
  17. 根据权利要求15所述的透明电极，其特征在于，所述纳米银线导电层为将纳米银线导电油墨涂布在透明基材层上面得到的。The transparent electrode according to claim 15, wherein the nano silver wire conductive layer is obtained by coating a nano silver wire conductive ink on the transparent substrate layer.
  18. 根据权利要求15所述的透明电极，其特征在于，所述中性化PEDOT/PSS高分子导电层采用权利要求1-10所述的导电油墨。The transparent electrode according to claim 15, wherein the neutralized PEDOT/PSS polymer conductive layer is the conductive ink according to any one of claims 1-10.
  19. 根据权利要求15所述的透明电极，其特征在于，所叙中性化PEDOT/PSS高分子导电层采用权利要求11～14所述的中性PEDOT/PSS分散液。The transparent electrode according to claim 15, wherein the neutralized PEDOT/PSS polymer conductive layer is the neutral PEDOT/PSS dispersion according to any one of claims 11 to 14.
  20. 根据权利要求15所述的透明电极，其特征在于，所述中性化PEDOT/PSS与纳米银线掺混后形成的高分子导电层，纳米银线导电油墨占中性化PEDOT/PSS导电油墨的重量为 0.5～25％。The transparent electrode according to claim 15, wherein the polymerized conductive layer formed by blending the neutralized PEDOT/PSS with the nano silver wire, and the nano silver wire conductive ink occupying the neutralized PEDOT/PSS conductive ink The weight is 0.5 to 25%.
  21. 根据权利要求15所述的透明电极，其特征在于，所述透明基材层可以为：玻璃、玻璃树脂、含氟聚合物、硅酮、聚烯烃、聚醚烃、PET、PEN、PMMA以及PC、PI及其组合的共聚或组合物或层压物。The transparent electrode according to claim 15, wherein the transparent substrate layer is: glass, glass resin, fluoropolymer, silicone, polyolefin, polyether hydrocarbon, PET, PEN, PMMA, and PC. Copolymers or compositions or laminates of PI, PI, and combinations thereof.
  22. 一种制备PEDOT/PSS导电层电极的方法，其特征在于，包括如下步骤：A method for preparing a PEDOT/PSS conductive layer electrode, comprising the steps of:
    (1)对基材材料进行表面预处理，作为透明基材层；(1) subjecting the substrate material to surface pretreatment as a transparent substrate layer;
    (2)在所述透明基材层上面涂布纳米银线导电油墨，固化优化后形成纳米银线导电层；(2) coating a nano silver wire conductive ink on the transparent substrate layer, and forming a nano silver wire conductive layer after curing optimization;
    (3)然后在所述纳米银线导电层上面涂布中性化PEDOT/PSS导电油墨，或者涂布中性化PEDOT/PSS导电油墨与纳米银线的掺混物，固化优化后形成高分子导电层。 (3) then coating a neutralized PEDOT/PSS conductive ink on the nano silver wire conductive layer, or coating a neutralized PEDOT/PSS conductive ink and a nano silver wire blend, and forming a polymer after curing optimization Conductive layer.
PCT/CN2015/088806 2014-09-03 2015-09-02 Pedot/pss conductive ink and transparent electrode WO2016034113A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN201410445544.9A CN104212243B (en) 2014-09-03 2014-09-03 A kind of preparation method of PEDOT/PSS electrically conductive ink and coating
CN201410445623.X 2014-09-03
CN201410445544.9 2014-09-03
CN201410445623.XA CN104183303B (en) 2014-09-03 2014-09-03 A kind of stable PEDOT/PSS conducting layer electrode and preparation method thereof

Publications (1)

Publication Number Publication Date
WO2016034113A1 true WO2016034113A1 (en) 2016-03-10

Family

ID=55439140

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2015/088806 WO2016034113A1 (en) 2014-09-03 2015-09-02 Pedot/pss conductive ink and transparent electrode

Country Status (1)

Country Link
WO (1) WO2016034113A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106313794A (en) * 2016-10-13 2017-01-11 衡山县佳诚新材料有限公司 Composite heat insulation dimming glass and preparation method thereof
CN110338781A (en) * 2019-07-23 2019-10-18 广西师范大学 A kind of dry electrode of nonmetal flexible and preparation method thereof
US11513410B2 (en) 2017-05-10 2022-11-29 National Institute For Materials Science Electrochromic device using organic/metal hybrid polymer and method for producing same

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101085857A (en) * 2006-06-07 2007-12-12 三星Sdi株式会社 Conducting polymer composition, conductive film formed using the conducting polymer composition, and electronic device including the conductive film
US20090302756A1 (en) * 2005-10-05 2009-12-10 Yuki Murayama Film with Transparent Conductive Layer, Flexible Functional Element and Flexible Dispersion-Type Electroluminescent Element, and Method for Producing the Same and Electronic Device by the Use Thereof
CN102522145A (en) * 2011-12-02 2012-06-27 浙江科创新材料科技有限公司 Nanometer silver transparent electrode material and preparation method thereof
CN102754055A (en) * 2010-02-09 2012-10-24 王子制纸株式会社 Conductive laminate and touch panel using same
CN104183303A (en) * 2014-09-03 2014-12-03 欧依有机光电子科技有限公司 Stable PEDOT/PSS conducting layer electrode and preparing method thereof
CN104212243A (en) * 2014-09-03 2014-12-17 欧依有机光电子科技有限公司 Preparation method of PEDOT/PSS conductive ink and coating

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090302756A1 (en) * 2005-10-05 2009-12-10 Yuki Murayama Film with Transparent Conductive Layer, Flexible Functional Element and Flexible Dispersion-Type Electroluminescent Element, and Method for Producing the Same and Electronic Device by the Use Thereof
CN101085857A (en) * 2006-06-07 2007-12-12 三星Sdi株式会社 Conducting polymer composition, conductive film formed using the conducting polymer composition, and electronic device including the conductive film
CN102754055A (en) * 2010-02-09 2012-10-24 王子制纸株式会社 Conductive laminate and touch panel using same
CN102522145A (en) * 2011-12-02 2012-06-27 浙江科创新材料科技有限公司 Nanometer silver transparent electrode material and preparation method thereof
CN104183303A (en) * 2014-09-03 2014-12-03 欧依有机光电子科技有限公司 Stable PEDOT/PSS conducting layer electrode and preparing method thereof
CN104212243A (en) * 2014-09-03 2014-12-17 欧依有机光电子科技有限公司 Preparation method of PEDOT/PSS conductive ink and coating

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106313794A (en) * 2016-10-13 2017-01-11 衡山县佳诚新材料有限公司 Composite heat insulation dimming glass and preparation method thereof
CN106313794B (en) * 2016-10-13 2023-09-19 衡山县佳诚新材料有限公司 Composite heat-insulating dimming glass and preparation method thereof
US11513410B2 (en) 2017-05-10 2022-11-29 National Institute For Materials Science Electrochromic device using organic/metal hybrid polymer and method for producing same
CN110338781A (en) * 2019-07-23 2019-10-18 广西师范大学 A kind of dry electrode of nonmetal flexible and preparation method thereof

Similar Documents

Publication Publication Date Title
CN104183303B (en) A kind of stable PEDOT/PSS conducting layer electrode and preparation method thereof
KR101489161B1 (en) Method for manufacturing transparent conductive layer and transparent conductive layer manufactured by the method
Jin et al. Annealing-free and strongly adhesive silver nanowire networks with long-term reliability by introduction of a nonconductive and biocompatible polymer binder
Jin et al. Long-term stable silver nanowire transparent composite as bottom electrode for perovskite solar cells
US7973180B2 (en) Process for producing aqueous dispersion of composite of poly(3,4-dialkoxythiophene) with polyanion
JP5728631B2 (en) Process for preparing conductive polymers
CN104212243B (en) A kind of preparation method of PEDOT/PSS electrically conductive ink and coating
US20110001720A1 (en) Conductive film
CN104240798A (en) Transparent conductive film and preparation method thereof
WO2016034113A1 (en) Pedot/pss conductive ink and transparent electrode
WO2010095648A1 (en) Composite conductive polymer composition, method for producing same, solution containing the composition, and use of the composition
CN102892850A (en) Sulphonated polyketones as counter-ion of conductive polymers
CN104465993A (en) Carbon-based composite transparent electrode and manufacturing method thereof
TW201124486A (en) Conductive coating composition and coated member
JP2013152928A (en) Transparent conductive film
CN102134326B (en) Preparation method of polyaniline/zinc oxide flexible composite electrode material
US20130092878A1 (en) Thermoplastic based electronic conductive inks and method of making the same
WO2020037768A1 (en) Flexible conductive film and preparation method therefor
US20160225480A1 (en) Conductive polymer film
JP5554836B2 (en) New polyelectrolyte complexes and their use
WO2012053373A1 (en) Conductive adhesive composition, electronic device, and production method for electronic device
JP5046977B2 (en) Conductive film and method for producing the same
Kwon et al. Effects of Organic Acids and a Fluoropolymer on the Conductivity and Transparency of Poly (3, 4-ethylenedioxythiophene) Films
TW201041988A (en) Conductive coating composition
KR20140145300A (en) Composition for high durable transparent conductive coating, manufacturing method of the composition and transparent conductive film using the composition

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15837674

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC

122 Ep: pct application non-entry in european phase

Ref document number: 15837674

Country of ref document: EP

Kind code of ref document: A1