CN108424502B - Multifunctional monomer and low-sheet-resistance flexible transparent conductive film based on same - Google Patents
Multifunctional monomer and low-sheet-resistance flexible transparent conductive film based on same Download PDFInfo
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Abstract
The invention discloses a multifunctional monomer and a low sheet resistance flexible transparent conductive film based on the multifunctional monomer, which are characterized in that: firstly, reacting polyisocyanate with polyether polyol to prepare an intermediate 1, then reacting the intermediate 1 with a sealing agent to prepare semi-closed isocyanate, and finally reacting the semi-closed isocyanate with a complexing agent to prepare a multifunctional monomer; uniformly stirring the multifunctional monomer, the polyhydroxy resin, the dispersing thickening auxiliary agent, the nano silver wire and the deionized water to prepare the conductive ink; and finally, coating the conductive ink on a flexible substrate by utilizing the micro-concave coating and drying to obtain the low sheet resistance flexible transparent conductive film. The transparent conductive film obtained by the invention has the film thickness as low as 10-100nm, the sheet resistance as low as 1-10 omega/□, the bending resistance radius as low as 2mm, the light transmittance as high as 89-91%, excellent adhesive force, water resistance and solvent resistance, simple process, safe operation of an aqueous system, no pollution and capability of realizing industrial production.
Description
Technical Field
The invention relates to the technical field of electronic display, in particular to a preparation method of a multifunctional monomer and a preparation method of a low-sheet resistance flexible transparent conductive film prepared from the multifunctional monomer.
Background
Transparent conductive films play an important role in various optical devices, such as touch screens, solar cells, organic light emitting devices, etc., which affect the characteristics of these products. Particularly in recent years, flexible transparent conductive films and consumer demand have rapidly increased, and lighter and more portable products have been required.
Currently, ITO (indium tin oxide) is the most important material for preparing transparent conductive films on the market, but ITO has some insurmountable defects: the ITO film cannot obtain very low sheet resistance and cannot be applied to equipment with larger size; when the film is bent, the surface of the film is easy to crack and break, and the film cannot be used for preparing flexible equipment with good bending resistance; meanwhile, the storage capacity of ITO is limited, the price is gradually increased along with the increase of consumption, and expensive vacuum sputtering equipment is needed for preparing an ITO film.
In recent years, researchers have developed various new technologies to substitute for ITO materials, such as carbon nanotubes, graphene, silver nanowires, metal grids, etc., which have better flexibility than ITO; however, carbon nanotubes and graphene have certain defects in electrical properties and optical properties of metal grids, and are still in the research stage; the nano silver wire has simple coating process and better optical property and sheet resistance than ITO, and can be used for preparing large-size equipment.
Patent CN 104332215A proposes a preparation method of a low-resistivity transparent conductive film, but the conductive film needs to be thermally treated for 20-200min at a high temperature of more than 200 ℃, and the base film can deform and shrink at the temperature; patent CN 104700928A proposes a preparation method of a low sheet resistance transparent conductive film, but the conductive layer prepared by the method is very thick and reaches 20-30 μm, which exceeds the thickness of the existing ITO, and silver paste or copper with the thickness of 2-10 μm is used for filling in the groove, so the optical performance of the conductive film is poor, and the high temperature treatment is required for 15-30min after the final polymer conductive layer is coated, which is not beneficial to the improvement of the production line yield; patent CN 106782769 a proposes a preparation method of a low-roughness low-sheet resistance flexible transparent conductive composite film, but it is doped with metal oxides such as ITO, and can only be used on stainless steel bands and flexible glass, and the minimum bearing radius is 2mm bending, so its flexibility is poor, and it is not suitable for being used on foldable equipment.
Therefore, there is a need in the art for a low sheet resistance flexible transparent conductive film that can be used in flexible devices, and can meet the requirements of large-sized devices with rapidly increasing demands, and that has high sensitivity, high stability, simple production process, and can be industrially produced.
Disclosure of Invention
In order to avoid the defects of the prior art, the invention aims to provide the low-sheet resistance flexible transparent conductive film which has high sensitivity and stability and simple production process and can be industrially produced.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention firstly discloses a method for synthesizing a multifunctional monomer, which comprises the following steps:
a. heating polyisocyanate to 30-80 ℃, then dropwise adding polyether polyol according to the molar ratio of polyisocyanate to polyether polyol of 2:1, and continuously preserving heat until the reaction is complete after dropwise adding is finished to obtain an intermediate 1; the polyisocyanate has an average functionality of n + 1; the reaction formula is shown as follows:
b. heating the intermediate 1 to 40-70 ℃, and then adding a solvent according to a molar ratio of the intermediate 1 to the sealant of 1: n, dropwise adding a blocking agent into the intermediate 1, and reacting for 3-5h to obtain semi-blocked isocyanate; the reaction formula is shown as follows:
c. and (2) mixing the semi-blocked isocyanate and a complexing agent according to a molar ratio of 1: 1.1n until the reaction is complete, thus obtaining the target product multifunctional monomer; the reaction formula is shown as follows:
preferably, the polyisocyanate is a mixture of polyphenyl polymethylene polyisocyanate (PAPI, average pentafunctionality) and one of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), and Xylylene Diisocyanate (XDI).
Preferably, the polyether polyol is one or a mixture of two of polyethylene glycol (PEG-200, PEG-400, PEG-600, PEG-800 and PEG-1000) and polypropylene glycol (PPG-200, PPG-400, PPG-600, PPG-800 and PPG-1000).
Preferably, the blocking agent is Methyl Ethyl Ketoxime (MEKO) or hydrocyanic acid (HCN).
Preferably, the complexing agent is ethylenediaminetetraacetic acid (EDTA).
In the above synthesis method, the method for determining whether the reaction in step a and step c is complete is a conventional method in the art, and specifically, the following method can be adopted:
step a: weighing 2g of the intermediate 1 by using a phthalic anhydride pyridine method, diluting the intermediate 1 by using 10mL of phthalic anhydride pyridine solution, heating and refluxing for 1.5h at 115 ℃ in an oil bath, cooling to room temperature, adding 5 drops of phenolphthalein indicator, titrating to the end point by using potassium hydroxide solution, and keeping the color constant for 15 s; carrying out a blank test under the same conditions, thereby calculating the hydroxyl value of the measured solution; when the hydroxyl value of intermediate 1 was zero, the reaction was complete.
Step c: weighing a certain amount of initial reactant solution or multifunctional monomer obtained in the step c by using an acetone method, dissolving and diluting the initial reactant solution or the multifunctional monomer by using acetone, adding 4 drops of phenolphthalein indicator, titrating the solution by using a potassium hydroxide solution until the solution turns red slightly, and calculating the acid value; the reaction was complete when the acid number of the multifunctional monomer had dropped to 77.27% and below of the starting reactant solution in step c.
The invention also discloses the multifunctional monomer obtained by the synthesis method.
The invention further discloses a low sheet resistance flexible transparent conductive film based on the multifunctional monomer, which is characterized in that: the conductive ink is prepared by mechanically and uniformly mixing the multifunctional monomer, polyhydroxy resin, a dispersing thickening auxiliary agent, nano silver wires and deionized water in proportion; coating the conductive ink on a flexible substrate through a micro-concave coating process, and drying and rolling the flexible substrate at 100 ℃ for 2min by using a tunnel furnace to obtain a target product, namely the low sheet resistance flexible transparent conductive film;
the conductive ink comprises the following raw materials in percentage by mass:
multifunctional monomer: 0.1 to 1 percent;
polyhydroxy resin: 0.2-2%;
dispersing and thickening auxiliary agent: 0.05 to 0.5 percent;
nano silver wire: 0.02-0.2%;
deionized water: 96 to 99.7 percent.
Preferably, the polyhydroxy resin is Bayhydrol xp 2470,
VP LS 2227 or Bayhydrol VP LS 2306.
Preferably, the dispersion thickening aid is methylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, carboxymethyl cellulose or sodium polyacrylate.
Preferably, the diameter of the nano silver wire is 10-100nm, and the aspect ratio is 500-1500.
Preferably, the deionized water is obtained by purifying an ultra-pure water machine, and the TDS content is 0 ppm.
Preferably, the flexible substrate is polyethylene terephthalate (PET) or Polyimide (PI).
Compared with the prior art, the invention has the following beneficial effects:
1. the synthesis of the multifunctional monomer firstly introduces a large amount of polyether chain segments, and has good water solubility, so that the subsequently prepared conductive ink is aqueous and has the characteristic of environmental friendliness;
2. blocking partial isocyanate in the multifunctional monomer, and reacting the residual isocyanate with a complexing agent to introduce a metal complexing group, so that the multifunctional monomer can stably exist in the ink;
3. after the conductive ink is coated, the conductive ink can be completely dried at 100 ℃ for 2min in a tunnel furnace, the blocked isocyanate group is deblocked to perform a crosslinking reaction with hydroxyl in the ink, and a complexing agent is complexed with ions on the surface of the nano silver wire, so that the conductive network of the conductive film is more compact, and the square resistance below 10 omega/□ can be achieved under the lower concentration of the nano silver wire; meanwhile, isocyanate can also react with hydrophilic groups on the surface of the base material, so that the binding force between the conductive film and the base material is improved, and the stability of the conductive film is improved;
4. the thickness of the obtained conductive film is 10-100nm, so that the bending resistant radius reaches 2mm, and the light transmittance is more than 89%;
5. the invention only needs one-time coating, has simple process, safe operation of a water-based system, no pollution and high efficiency of coating by using the micro-pits, can completely realize industrial production, and the prepared conductive film has low cost.
Drawings
FIG. 1 is a flow chart of a method for preparing a low sheet resistance flexible transparent conductive film in accordance with an embodiment of the present invention;
fig. 2 is an optical microscope photograph of the low sheet resistance flexible transparent conductive film prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in detail with reference to the following examples, which are carried out on the premise of the technical solution of the present invention, and give detailed embodiments and specific procedures, but the scope of the present invention is not limited to the following examples.
Comparative example
Sequentially adding 150g of Bayhydrol xp 2470 resin, 25g of hydroxyethyl cellulose, 10g of nano silver wire with the diameter of about 50nm and 9815g of deionized water into a dispersion cylinder, and mechanically stirring at room temperature for 30min to obtain conductive ink; coating the conductive ink on a PET (polyethylene terephthalate) base film by utilizing a micro-concave coating method, drying at 100 ℃ for 2min, and rolling to obtain a low sheet resistance flexible transparent conductive film; and finally, carrying out performance test on the prepared conductive film.
Example 1
(1) Synthesizing multifunctional monomers: sequentially adding 70g of PAPI (Mn is 700g/mol, 0.1mol) and 17.4g of TDI (0.1mol) into a four-neck flask, heating to 60 ℃, then gradually dropwise adding 40g of PEG-400(0.1mol) into the four-neck flask at a constant speed, and after dropwise adding is completed, preserving heat for 2h until the reaction is completed to obtain an intermediate 1;
keeping the temperature of the intermediate 1 at 60 ℃, gradually dropwise adding 21.75g of MEKO (0.25mol) into the intermediate 1, and reacting for 4 hours to obtain semi-closed isocyanate;
the semi-blocked isocyanate was finally reacted with 80.3g EDTA (0.275mol) until the isocyanate reaction was complete to obtain the multifunctional monomer.
(2) Sequentially adding 50g of the multifunctional monomer prepared in the step (1), 100g of Bayhydrol xp 2470 resin, 25g of hydroxyethyl cellulose, 10g of nano silver wire with the diameter of about 50nm and 9815g of deionized water into a dispersion cylinder, and mechanically stirring at room temperature for 30min to obtain conductive ink;
coating the conductive ink on a PET (polyethylene terephthalate) base film by utilizing a micro-concave coating method, drying at 100 ℃ for 2min, and rolling to obtain a low sheet resistance flexible transparent conductive film; and finally, carrying out performance test on the prepared conductive film.
Example 2
(1) Synthesizing multifunctional monomers: adding 70g of PAPI (Mn is 700g/mol, 0.1mol) and 16.8g of HDI (0.1mol) into a four-neck flask in sequence, heating to 50 ℃, then gradually dropwise adding 40g of PEG-400(0.1mol) into the four-neck flask at a constant speed, and after dropwise adding is completed, preserving heat for 2h till the reaction is completed to obtain an intermediate 1;
keeping the temperature of the intermediate 1 at 60 ℃, gradually dropwise adding 21.75g of MEKO (0.25mol) into the intermediate 1, and reacting for 4 hours to obtain semi-closed isocyanate;
the semi-blocked isocyanate was finally reacted with 80.3g EDTA (0.275mol) until the isocyanate reaction was complete to obtain the multifunctional monomer.
(2) Sequentially adding 50g of the multifunctional monomer prepared in the step (1), 100g of Bayhydrol xp 2470 resin, 25g of hydroxyethyl cellulose, 10g of nano silver wire with the diameter of about 50nm and 9815g of deionized water into a dispersion cylinder, and mechanically stirring at room temperature for 30min to obtain conductive ink;
coating the conductive ink on a PET (polyethylene terephthalate) base film by utilizing a micro-concave coating method, drying at 100 ℃ for 2min, and rolling to obtain a low sheet resistance flexible transparent conductive film; and finally, carrying out performance test on the prepared conductive film.
Example 3
(1) Synthesizing multifunctional monomers: sequentially adding 105g of PAPI (Mn is 700g/mol, 0.15mol) and 8.7g of TDI (0.05mol) into a four-neck flask, heating to 60 ℃, then gradually dropwise adding 60g of PEG-600(0.1mol) into the four-neck flask at a constant speed, and after dropwise adding is completed, preserving heat for 2h until the reaction is completed to obtain an intermediate 1;
keeping the temperature of the intermediate 1 at 70 ℃, gradually dropwise adding 28.28g of MEKO (0.325mol) into the intermediate 1, and reacting for 4 hours to obtain semi-closed isocyanate;
the semi-blocked isocyanate was finally reacted with 104.4g EDTA (0.3575mol) until the isocyanate reaction was complete to obtain the multifunctional monomer.
(2) Sequentially adding 50g of the multifunctional monomer prepared in the step (1), 100g of Bayhydrol xp 2470 resin, 25g of hydroxyethyl cellulose, 10g of nano silver wire with the diameter of about 50nm and 9815g of deionized water into a dispersion cylinder, and mechanically stirring at room temperature for 30min to obtain conductive ink;
coating the conductive ink on a PET (polyethylene terephthalate) base film by utilizing a micro-concave coating method, drying at 100 ℃ for 2min, and rolling to obtain a low sheet resistance flexible transparent conductive film; and finally, carrying out performance test on the prepared conductive film.
Example 4
(1) Synthesizing multifunctional monomers: adding 105g of PAPI (Mn is 700g/mol, 0.15mol) and 8.4g of HDI (0.05mol) into a four-neck flask in sequence, heating to 50 ℃, then gradually dropwise adding 60g of PEG-600(0.1mol) into the four-neck flask at a constant speed, and after dropwise adding is completed, preserving heat for 2h till the reaction is completed to obtain an intermediate 1;
keeping the temperature of the intermediate 1 at 70 ℃, gradually dropwise adding 28.28g of MEKO (0.325mol) into the intermediate 1, and reacting for 4 hours to obtain semi-closed isocyanate;
the semi-blocked isocyanate was finally reacted with 104.4g EDTA (0.3575mol) until the isocyanate reaction was complete to obtain the multifunctional monomer.
(2) Sequentially adding 50g of the multifunctional monomer prepared in the step (1), 100g of Bayhydrol xp 2470 resin, 25g of hydroxyethyl cellulose, 10g of nano silver wire with the diameter of about 50nm and 9815g of deionized water into a dispersion cylinder, and mechanically stirring at room temperature for 30min to obtain conductive ink;
coating the conductive ink on a PET (polyethylene terephthalate) base film by utilizing a micro-concave coating method, drying at 100 ℃ for 2min, and rolling to obtain a low sheet resistance flexible transparent conductive film; and finally, carrying out performance test on the prepared conductive film.
Example 5
(1) Synthesizing multifunctional monomers: sequentially adding 122.5g of PAPI (Mn is 700g/mol, 0.175mol) and 6.25g of MDI (0.025mol) into a four-neck flask, heating to 65 ℃, then gradually dropwise adding 20g of PEG-400(0.05mol) and 30g of PEG-600(0.05mol) into the four-neck flask at a constant speed, and after dropwise adding is completed, preserving heat for 2h until the reaction is completed to obtain an intermediate 1;
keeping the temperature of the intermediate 1 at 70 ℃, gradually dropwise adding 31.54g of MEKO (0.3625mol) into the intermediate 1, and reacting for 4 hours to obtain semi-closed isocyanate;
the semi-blocked isocyanate was finally reacted with 116.46g EDTA (0.3988mol) until the isocyanate reaction was complete to obtain the multifunctional monomer.
(2) Sequentially adding 50g of the multifunctional monomer prepared in the step (1), 100g of Bayhydrol xp 2470 resin, 25g of hydroxyethyl cellulose, 10g of nano silver wire with the diameter of about 50nm and 9815g of deionized water into a dispersion cylinder, and mechanically stirring at room temperature for 30min to obtain conductive ink;
coating the conductive ink on a PET (polyethylene terephthalate) base film by utilizing a micro-concave coating method, drying at 100 ℃ for 2min, and rolling to obtain a low sheet resistance flexible transparent conductive film; and finally, carrying out performance test on the prepared conductive film.
Example 6
(1) Synthesizing multifunctional monomers: sequentially adding 122.5g of PAPI (Mn is 700g/mol, 0.175mol) and 5.55g of IPDI (0.025mol) into a four-neck flask, heating to 60 ℃, then gradually dropwise adding 20g of PEG-400(0.05mol) and 30g of PEG-600(0.05mol) into the four-neck flask at a constant speed, and after dropwise adding is completed, preserving heat for 2h until the reaction is completed to obtain an intermediate 1;
keeping the temperature of the intermediate 1 at 70 ℃, gradually dropwise adding 31.54g of MEKO (0.3625mol) into the intermediate 1, and reacting for 4 hours to obtain semi-closed isocyanate;
the semi-blocked isocyanate was finally reacted with 116.46g EDTA (0.3988mol) until the isocyanate reaction was complete to obtain the multifunctional monomer.
(2) Sequentially adding 50g of the multifunctional monomer prepared in the step (1), 100g of Bayhydrol xp 2470 resin, 25g of hydroxyethyl cellulose, 10g of nano silver wire with the diameter of about 50nm and 9815g of deionized water into a dispersion cylinder, and mechanically stirring at room temperature for 30min to obtain conductive ink;
coating the conductive ink on a PET (polyethylene terephthalate) base film by utilizing a micro-concave coating method, drying at 100 ℃ for 2min, and rolling to obtain a low sheet resistance flexible transparent conductive film; and finally, carrying out performance test on the prepared conductive film.
A comparison of the conductive films obtained in examples 1-6 with the comparative example is shown in Table 1.
Table 1: EXAMPLES 1 TO 6 the results of the experiments are compared with those of the comparative examples
Example 7
(1) Synthesizing multifunctional monomers: sequentially adding 70g of PAPI (Mn is 700g/mol, 0.1mol) and 17.4g of TDI (0.1mol) into a four-neck flask, heating to 60 ℃, then gradually dropwise adding 40g of PEG-400(0.1mol) into the four-neck flask at a constant speed, and after dropwise adding is completed, preserving heat for 2h until the reaction is completed to obtain an intermediate 1;
keeping the temperature of the intermediate 1 at 60 ℃, gradually dropwise adding 21.75g of MEKO (0.25mol) into the intermediate 1, and reacting for 4 hours to obtain semi-closed isocyanate;
the semi-blocked isocyanate was finally reacted with 80.3g EDTA (0.275mol) until the isocyanate reaction was complete to obtain the multifunctional monomer.
(2) Sequentially adding 10g of the multifunctional monomer prepared in the step (1), 100g of Bayhydrol xp 2470 resin, 25g of hydroxyethyl cellulose, 10g of nano silver wire with the diameter of about 50nm and 9855g of deionized water into a dispersion cylinder, and mechanically stirring at room temperature for 30min to obtain conductive ink;
coating the conductive ink on a PET (polyethylene terephthalate) base film by utilizing a micro-concave coating method, drying at 100 ℃ for 2min, and rolling to obtain a low sheet resistance flexible transparent conductive film; and finally, carrying out performance test on the prepared conductive film.
Example 8
(1) Synthesizing multifunctional monomers: sequentially adding 70g of PAPI (Mn is 700g/mol, 0.1mol) and 17.4g of TDI (0.1mol) into a four-neck flask, heating to 60 ℃, then gradually dropwise adding 40g of PEG-400(0.1mol) into the four-neck flask at a constant speed, and after dropwise adding is completed, preserving heat for 2h until the reaction is completed to obtain an intermediate 1;
keeping the temperature of the intermediate 1 at 60 ℃, gradually dropwise adding 21.75g of MEKO (0.25mol) into the intermediate 1, and reacting for 4 hours to obtain semi-closed isocyanate;
the semi-blocked isocyanate was finally reacted with 80.3g EDTA (0.275mol) until the isocyanate reaction was complete to obtain the multifunctional monomer.
(2) Sequentially adding 100g of the multifunctional monomer prepared in the step (1), 100g of Bayhydrol xp 2470 resin, 25g of hydroxyethyl cellulose, 10g of nano silver wire with the diameter of about 50nm and 9765g of deionized water into a dispersion cylinder, and mechanically stirring at room temperature for 30min to obtain conductive ink;
coating the conductive ink on a PET (polyethylene terephthalate) base film by utilizing a micro-concave coating method, drying at 100 ℃ for 2min, and rolling to obtain a low sheet resistance flexible transparent conductive film; and finally, carrying out performance test on the prepared conductive film.
Example 9
(1) Synthesizing multifunctional monomers: sequentially adding 70g of PAPI (Mn is 700g/mol, 0.1mol) and 17.4g of TDI (0.1mol) into a four-neck flask, heating to 60 ℃, then gradually dropwise adding 40g of PEG-400(0.1mol) into the four-neck flask at a constant speed, and after dropwise adding is completed, preserving heat for 2h until the reaction is completed to obtain an intermediate 1;
keeping the temperature of the intermediate 1 at 60 ℃, gradually dropwise adding 21.75g of MEKO (0.25mol) into the intermediate 1, and reacting for 4 hours to obtain semi-closed isocyanate;
the semi-blocked isocyanate was finally reacted with 80.3g EDTA (0.275mol) until the isocyanate reaction was complete to obtain the multifunctional monomer.
(2) Sequentially adding 50g of the multifunctional monomer prepared in the step (1), 200g of Bayhydrol xp 2470 resin, 25g of hydroxyethyl cellulose, 10g of nano silver wire with the diameter of about 50nm and 9715g of deionized water into a dispersion cylinder, and mechanically stirring at room temperature for 30min to obtain conductive ink;
coating the conductive ink on a PET (polyethylene terephthalate) base film by utilizing a micro-concave coating method, drying at 100 ℃ for 2min, and rolling to obtain a low sheet resistance flexible transparent conductive film; and finally, carrying out performance test on the prepared conductive film.
Example 10
(1) Synthesizing multifunctional monomers: sequentially adding 70g of PAPI (Mn is 700g/mol, 0.1mol) and 17.4g of TDI (0.1mol) into a four-neck flask, heating to 60 ℃, then gradually dropwise adding 40g of PEG-400(0.1mol) into the four-neck flask at a constant speed, and after dropwise adding is completed, preserving heat for 2h until the reaction is completed to obtain an intermediate 1;
keeping the temperature of the intermediate 1 at 60 ℃, gradually dropwise adding 21.75g of MEKO (0.25mol) into the intermediate 1, and reacting for 4 hours to obtain semi-closed isocyanate;
the semi-blocked isocyanate was finally reacted with 80.3g EDTA (0.275mol) until the isocyanate reaction was complete to obtain the multifunctional monomer.
(2) Sequentially adding 50g of the multifunctional monomer prepared in the step (1), 100g of Bayhydrol xp 2470 resin, 25g of hydroxyethyl cellulose, 2g of nano silver wire with the diameter of about 50nm and 9823g of deionized water into a dispersion cylinder, and mechanically stirring at room temperature for 30min to obtain conductive ink;
coating the conductive ink on a PET (polyethylene terephthalate) base film by utilizing a micro-concave coating method, drying at 100 ℃ for 2min, and rolling to obtain a low sheet resistance flexible transparent conductive film; and finally, carrying out performance test on the prepared conductive film.
Example 11
(1) Synthesizing multifunctional monomers: sequentially adding 70g of PAPI (Mn is 700g/mol, 0.1mol) and 17.4g of TDI (0.1mol) into a four-neck flask, heating to 60 ℃, then gradually dropwise adding 40g of PEG-400(0.1mol) into the four-neck flask at a constant speed, and after dropwise adding is completed, preserving heat for 2h until the reaction is completed to obtain an intermediate 1;
keeping the temperature of the intermediate 1 at 60 ℃, gradually dropwise adding 21.75g of MEKO (0.25mol) into the intermediate 1, and reacting for 4 hours to obtain semi-closed isocyanate;
the semi-blocked isocyanate was finally reacted with 80.3g EDTA (0.275mol) until the isocyanate reaction was complete to obtain the multifunctional monomer.
(2) Sequentially adding 50g of the multifunctional monomer prepared in the step (1), 100g of Bayhydrol xp 2470 resin, 25g of hydroxyethyl cellulose, 4g of nano silver wires with the diameter of about 50nm and 9821g of deionized water into a dispersion cylinder, and mechanically stirring at room temperature for 30min to obtain conductive ink;
coating the conductive ink on a PET (polyethylene terephthalate) base film by utilizing a micro-concave coating method, drying at 100 ℃ for 2min, and rolling to obtain a low sheet resistance flexible transparent conductive film; and finally, carrying out performance test on the prepared conductive film.
A comparison of the conductive films obtained in examples 1, 7 to 11 and the comparative example is shown in Table 1.
Table 2: example 1, example 7 to example 11 the results of the experiments are compared with the comparative example
According to the embodiment of the invention, the sheet resistance of the obtained conductive film can be reduced to below 10 omega/□ by adding the self-made multifunctional monomer which can react with the organic resin in the ink and the silver ions into the ink; meanwhile, the multifunctional monomer can react with hydrophilic groups on the surface of the substrate, so that the adhesive force is greatly improved, and the prepared conductive film has the advantages of obviously improved light transmittance and improved water and solvent resistance wiping performance by tens of times due to low silver content and film thickness of less than 100 nm; the multifunctional monomer is simple in synthesis process, only needs to be stirred in the air atmosphere, ink only needs to be stirred in a conventional machine, and the coating of the conductive film can be completed only by one-time coating by using the mature dimple coating in the current industrial production, so that the efficiency and the yield are high; therefore, the low sheet resistance flexible transparent conductive film prepared according to the embodiment of the invention has great advantages and application potential in flexible devices and large-size devices.
The present invention is not limited to the above exemplary embodiments, and any modifications, equivalent replacements, and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A method for synthesizing a multifunctional monomer is characterized by comprising the following steps:
a. heating polyisocyanate to 30-80 ℃, then dropwise adding polyether polyol according to the molar ratio of the polyisocyanate to the polyether polyol of 2:1, and continuously preserving heat until the reaction is complete after the dropwise addition is finished to obtain an intermediate 1; the polyisocyanate has an average functionality of n + 1;
the polyisocyanate is a mixture of polyphenyl polymethylene polyisocyanate with the average functionality of 5 and one of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and xylylene diisocyanate;
the polyether polyol is one or a mixture of two of polyethylene glycol and polypropylene glycol;
b. heating the intermediate 1 to 40-70 ℃, and then adding a solvent according to a molar ratio of the intermediate 1 to the sealant of 1: n, dropwise adding a blocking agent into the intermediate 1, and reacting for 3-5h to obtain semi-blocked isocyanate;
the sealing agent is methyl ethyl ketoxime or hydrocyanic acid;
c. and (2) mixing the semi-blocked isocyanate and a complexing agent according to a molar ratio of 1: 1.1n until the reaction is complete, thus obtaining the target product multifunctional monomer;
the complexing agent is ethylenediamine tetraacetic acid.
2. A multifunctional monomer obtainable by the synthesis process of claim 1.
3. The utility model provides a flexible transparent conducting film of low sheet resistance which characterized in that: the conductive ink is prepared by mechanically and uniformly mixing the multifunctional monomer of claim 2 with polyhydroxy resin, a dispersing thickening aid, nano silver wires and deionized water in proportion; coating the conductive ink on a flexible substrate through a micro-concave coating process, and drying and rolling the flexible substrate at 100 ℃ for 2min by using a tunnel furnace to obtain a target product, namely the low sheet resistance flexible transparent conductive film;
the conductive ink comprises the following raw materials in percentage by mass:
multifunctional monomer: 0.1 to 1 percent;
polyhydroxy resin: 0.2-2%;
dispersing and thickening auxiliary agent: 0.05 to 0.5 percent;
nano silver wire: 0.02-0.2%;
deionized water: 96% -99.7%;
the sum of the mass percentages of the raw materials is 100 percent.
4. The low sheet resistance flexible transparent conductive film of claim 3, wherein: the polyhydroxy resin is Bayhydrol xp 2470,
VP LS 2227 or Bayhydrol VP LS 2306; the dispersing thickening aidThe agent is methylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, carboxymethyl cellulose or sodium polyacrylate.
5. The low sheet resistance flexible transparent conductive film of claim 3, wherein: the diameter of the nano silver wire is 10-100nm, and the length-diameter ratio is 500-1500.
6. The low sheet resistance flexible transparent conductive film of claim 3, wherein: the deionized water is obtained by purifying an ultrapure water machine, and the TDS content is 0 ppm.
7. The low sheet resistance flexible transparent conductive film of claim 3, wherein: the flexible substrate is polyethylene terephthalate or polyimide.
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