CN108424502A - A kind of multifunctional monomer and the low square resistance flexible transparent conducting film based on it - Google Patents
A kind of multifunctional monomer and the low square resistance flexible transparent conducting film based on it Download PDFInfo
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- CN108424502A CN108424502A CN201810161413.6A CN201810161413A CN108424502A CN 108424502 A CN108424502 A CN 108424502A CN 201810161413 A CN201810161413 A CN 201810161413A CN 108424502 A CN108424502 A CN 108424502A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/343—Polycarboxylic acids having at least three carboxylic acid groups
- C08G18/346—Polycarboxylic acids having at least three carboxylic acid groups having four carboxylic acid groups
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- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
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- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/40—High-molecular-weight compounds
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
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- C09D11/00—Inks
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Abstract
The invention discloses a kind of multifunctional monomer and based on its low square resistance flexible transparent conducting film, it is characterised in that：Polyisocyanates and polyether polyol reaction are prepared into intermediate 1 first, then intermediate 1 is reacted with sealer and prepares semiclosed isocyanates, semiclosed isocyanates is reacted with complexing agent finally, multifunctional monomer is made；Multifunctional monomer and polyhydroxy resin, dispersion thickening aids, nano-silver thread and deionized water are stirred into uniform obtained conductive ink；Finally conductive ink is coated on flexible parent metal using dimple coating and is dried, low square resistance flexible transparent conducting film is obtained.Gained transparent conductive film film thickness of the invention reaches 89% 91% down to 1 10 Ω/, bending resistance bilge radius down to 10 100nm, sheet resistance down to 2mm, light transmittance, adhesive force, water-fast and solvent resistance are excellent, it is simple for process, it is water-based system safe operation, pollution-free, industrialized production may be implemented.
Description
Technical field
The present invention relates to electronic display technology field, more particularly to the preparation of a kind of multifunctional monomer and thus multi-functional
The preparation method of low square resistance flexible transparent conducting film prepared by monomer, the transparent conductive film have low square resistance, flexibility good, stable
Property it is good, preparation process is simple, be suitble to industrialized production the features such as, be the important of the fields such as Touch Panel, OLED, LCD, PDP
Material.
Background technology
Transparent conductive film plays key player, such as touch screen, solar cell, You Jifa in various optical devices
Optical device etc., it affects the feature of these products.Especially in recent years flexible transparent conducting film and consumer demand quick
Increase, needs lighter and portable product.
ITO (tin indium oxide) is to prepare the most important material of transparent conductive film, but ITO has some not currently on the market
Surmountable defect：Ito film is unable to get very low sheet resistance, can not apply in large-size equipment；Surface when film bends
It is susceptible to slight crack and is crushed, cannot be used for preparing the good flexible apparatus of resistance to bend(ing)；ITO reserves are limited simultaneously, with consumption
Amount increases, and price gradually rises, and prepares ito film and need expensive vacuum sputtering equipment.
Researchers develop the material that various new technologies are used for substituting ITO in succession in recent years, such as carbon nanotube, stone
Black alkene, nano-silver thread, metal grill etc., their flexibility are superior to ITO；But carbon nanotube and graphene electrical property,
Metal grill has certain defect in optical property, still in conceptual phase；Nano-silver thread coating process is simple, optical
It can be superior to ITO with sheet resistance, can be used for preparing large scale equipment.
104332215 A of patent CN propose a kind of preparation method of low resistivity, transparent conductive film, but this method is led
Electrolemma needs are heat-treated 20-200min under more than 200 DEG C hot conditions, and basement membrane will appear deformation and contraction at a temperature of this；Specially
Sharp CN 104700928A propose a kind of preparation method of low square resistance transparent conductive film, but conductive layer prepared by this method is very thick
Reach 20-30 μm, already exceed the thickness of current ITO, while 2-10 μm of silver paste or copper being used to be used as filling in its groove,
So the optical property of the conductive film is poor, and coating needs high-temperature process 15- after the last conductive polymer layer of this method
30min is unfavorable for the raising of producing line yield；106782769 A of patent CN propose a kind of low roughness low square resistance flexible and transparent
The preparation method of conductive composite film, but it is doped with the metal oxides such as ITO, can be used only on stainless steel band and flexible glass,
The minimum radius that bears bends for 2mm, so its flexibility is poor, is unsuitable to apply on foldable device.
Therefore, this field is badly in need of one kind and can be used to flexible apparatus at present, and can be satisfied with what current needs increased dramatically
The high sensitivity of large scale equipment, high stability, simple production process, can be with the low square resistance flexible and transparent conductive of industrialized production
Film.
Invention content
In order to avoid above-mentioned prior art shortcoming, the present invention is intended to provide a kind of sensitivity and stability are high, produce
It is simple for process, can be with the low square resistance flexible transparent conducting film of industrialized production.
In order to achieve the above object, the present invention adopts the following technical scheme that：
The present invention discloses a kind of synthetic method of multifunctional monomer first comprising following steps：
A, polyisocyanates is heated to 30-80 DEG C, then according to the molar ratio 2 of polyisocyanates and polyether polyol:
1, polyether polyol is added dropwise, is added dropwise to complete subsequent continuation of insurance temperature to the reaction was complete, intermediate 1 is made；The polyisocyanates
Average functionality be n+1；Reaction equation is as follows：
B, the intermediate 1 is warming up to 40-70 DEG C, is then 1 according to the molar ratio of intermediate 1 and sealer：N, by
It is added dropwise in sealer to the intermediate 1, reacts 3-5h, semiclosed isocyanates is made；Reaction equation is as follows：
C, by the semiclosed isocyanates and complexing agent in molar ratio 1：1.1n reacts, and until the reaction was complete, that is, obtains
Target product multifunctional monomer；Reaction equation is as follows：
Preferably, the polyisocyanates is polyphenyl polymethylene polyisocyanates (PAPI, average face) and toluene
Diisocyanate (TDI), methyl diphenylene diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone two
A kind of mixture in isocyanates (IPDI), benzene dimethylene diisocyanate (XDI).
Preferably, the polyether polyol is polyethylene glycol (PEG-200, PEG-400, PEG-600, PEG-800, PEG-
1000), one or two kinds of mixed in polypropylene glycol (PPG-200, PPG-400, PPG-600, PPG-800, PPG-1000)
Close object.
Preferably, the sealer is methyl ethyl ketoxime (MEKO) or hydrogen cyanide (HCN).
Preferably, complexing agent is ethylenediamine tetra-acetic acid (EDTA).
In above-mentioned synthetic method, judgment step a and the step c methods whether the reaction was complete are this field conventional method, tool
Body can be used such as under type：
Step a：It utilizes " phthalic anhydride pyridine method ", weighs 2g intermediates 1, diluted with 10mL phthalic anhydride pyridine solutions, at 115 DEG C
Oil bath heating reflux 1.5h, then cools to room temperature, and 5 drop phenolphthalein indicators are added, and to terminal with potassium hydroxide solution titration, protects
It is colour-fast to hold 15s；Similarity condition is into line blank test, to calculate the hydroxyl value of surveyed solution；When the hydroxyl value of intermediate 1 is zero
When, show that the reaction was complete.
Step c：Utilize " acetone method ", weigh a certain amount of step c initial reactants solution or multifunctional monomer, with acetone into
Then row dissolved dilution is added 4 drop phenolphthalein indicators, is titrated to solution with potassium hydroxide solution and slightly reddens, then calculate
Acid value；When the acid value of multifunctional monomer be reduced to step c initial reactant solution 77.27% and it is following when, show that the reaction was complete.
The invention also discloses the multifunctional monomers obtained by above-mentioned synthetic method.
The present invention further discloses the low square resistance flexible transparent conducting film based on above-mentioned multifunctional monomer, feature exists
In：It is mechanical in proportion by above-mentioned multifunctional monomer and polyhydroxy resin, dispersion thickening aids, nano-silver thread, deionized water
It is uniformly mixed, conductive ink is made；It is coated on flexible parent metal by dimple coating process by conductive ink again, uses tunnel
100 DEG C of stove, 2min drying windings, obtain target product low square resistance flexible transparent conducting film；
The composition of each raw material of the conductive ink by mass percentage is：
Multifunctional monomer：0.1-1%；
Polyhydroxy resin：0.2-2%；
Disperse thickening aids：0.05-0.5%；
Nano-silver thread：0.02-0.2%；
Deionized water：96%-99.7%.
Preferably, the polyhydroxy resin be Bayhydrol xp 2470,VP LS 2227 or
Bayhydrol VP LS 2306。
Preferably, the dispersion thickening aids methylcellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, carboxylic first
Base cellulose or Sodium Polyacrylate.
Preferably, a diameter of 10-100nm of the nano-silver thread, draw ratio 500-1500.
Preferably, the deionized water is that ultrapure water machine purification obtains, and TDS contents are 0ppm.
Preferably, the flexible parent metal is poly- to stupid naphthalate (PET) or polyimides (PI).
Compared with prior art, the invention has the advantages that：
1, synthesis multifunctional monomer first introduces a large amount of polyether segments, has water solubility well, to make subsequently to prepare
Conductive ink be it is aqueous, have environmental-friendly characteristic；
2, part isocyanates is blocked in multifunctional monomer, and residual isocyanate is reacted with complexing agent introduces metal network
Group is closed, to make the multifunctional monomer that can be stabilized in the ink；
3, it after conductive ink coating is completed, can be completely dried through 100 DEG C of continuous tunnel furnace, 2min, the isocyanic acid of sealing end
Ester group deblocking is crosslinked with the hydroxyl in ink to react, and complexing agent is complexed with nano-silver thread surface ion, to
Keep the conductive network of conductive film finer and close, 10 Ω/ or less sheet resistances can be reached under lower nano-silver thread concentration；Simultaneously
Isocyanates can also be reacted with the hydrophilic radical of substrate surface, the binding force between conductive film and base material be improved, to improve
The stability of conductive film；
4, gained conduction film thickness is 10-100nm, so bending resistance bilge radius reaches 2mm, light transmittance is more than 89%；
5, the present invention only needs primary coating, and simple for process, water-based system safe operation is pollution-free, is coated with using dimple
It is efficient, completely can be with industrialized production, the conductive film of preparation is at low cost.
Description of the drawings
Fig. 1 is the flow chart of low square resistance flexible transparent conducting film preparation method in the specific embodiment of the invention；
Fig. 2 is the optical microscope photograph of low square resistance flexible transparent conducting film prepared by the embodiment of the present invention 1.
Specific implementation mode
It elaborates to the present invention with reference to embodiment, following embodiments are under based on the technical solution of the present invention
Implemented, give detailed embodiment and specific operating process, but protection scope of the present invention be not limited to it is following
Embodiment.
Comparative example
By the nano-silver thread of 2470 resin 150g of Bayhydrol xp, hydroxyethyl cellulose 25g, diameter 50nm or so
10g, deionized water 9815g, sequentially add in dispersion cylinder, and room temperature mechanical stirs 30min, obtain conductive ink；By conductive ink
Be coated with, be coated on PET basement membranes using dimple, then 100 DEG C, 2min drying, winding, low square resistance flexible and transparent conductive is made
Film；Finally conductive film obtained is tested for the property.
Embodiment 1
(1) multifunctional monomer synthesizes：By 70g PAPI (Mn=700g/mol, 0.1mol) and 17.4g TDI (0.1mol)
60 DEG C are heated to after sequentially adding four-hole boiling flask, 40g PEG-400 (0.1mol) are gradually at the uniform velocity then added drop-wise to four-hole boiling flask
In, after being added dropwise to complete, heat preservation 2h obtains intermediate 1 to the reaction was complete；
By 1 constant temperature of intermediate at 60 DEG C, 21.75g MEKO (0.25mol) are gradually added dropwise in intermediate 1, react 4h
Terminate, semiclosed isocyanates is made；
Finally semiclosed isocyanates is reacted with 80.3g EDTA (0.275mol), until the reaction was complete for isocyanates,
Multifunctional monomer is made.
(2) multifunctional monomer 50g, 2470 resin 100g of Bayhydrol xp, the hydroxy ethyl fiber prepared step (1)
Nano-silver thread 10g, the deionized water 9815g of plain 25g, diameter 50nm or so, sequentially add in dispersion cylinder, room temperature mechanical stirring
30min obtains conductive ink；
By conductive ink using dimple be coated with, be coated on PET basement membranes, then 100 DEG C, 2min drying, winding, be made it is low
Sheet resistance flexible transparent conducting film；Finally conductive film obtained is tested for the property.
Embodiment 2
(1) multifunctional monomer synthesizes：By 70g PAPI (Mn=700g/mol, 0.1mol) and 16.8g HDI (0.1mol)
50 DEG C are heated to after sequentially adding four-hole boiling flask, 40g PEG-400 (0.1mol) are gradually at the uniform velocity then added drop-wise to four-hole boiling flask
In, after being added dropwise to complete, heat preservation 2h obtains intermediate 1 to the reaction was complete；
By 1 constant temperature of intermediate at 60 DEG C, 21.75g MEKO (0.25mol) are gradually added dropwise in intermediate 1, react 4h
Terminate, semiclosed isocyanates is made；
Finally semiclosed isocyanates is reacted with 80.3g EDTA (0.275mol), until the reaction was complete for isocyanates,
Multifunctional monomer is made.
(2) multifunctional monomer 50g, 2470 resin 100g of Bayhydrol xp, the ethoxy prepared step (1)
Nano-silver thread 10g, the deionized water 9815g of cellulose 25g, diameter 50nm or so, sequentially add in dispersion cylinder, room temperature mechanical stirs
30min is mixed, conductive ink is obtained；
By conductive ink using dimple be coated with, be coated on PET basement membranes, then 100 DEG C, 2min drying, winding, be made it is low
Sheet resistance flexible transparent conducting film；Finally conductive film obtained is tested for the property.
Embodiment 3
(1) multifunctional monomer synthesizes：By 105g PAPI (Mn=700g/mol, 0.15mol) and 8.7g TDI
(0.05mol) is heated to 60 DEG C after sequentially adding four-hole boiling flask, and then 60g PEG-600 (0.1mol) are gradually at the uniform velocity added dropwise
Into four-hole boiling flask, after being added dropwise to complete, heat preservation 2h obtains intermediate 1 to the reaction was complete；
By 1 constant temperature of intermediate at 70 DEG C, 28.28g MEKO (0.325mol) are gradually added dropwise in intermediate 1, react 4h
Terminate, semiclosed isocyanates is made；
Finally semiclosed isocyanates is reacted with 104.4g EDTA (0.3575mol), until isocyanates has reacted
Entirely, multifunctional monomer is made.
(2) multifunctional monomer 50g, 2470 resin 100g of Bayhydrol xp, the ethoxy prepared step (1)
Nano-silver thread 10g, the deionized water 9815g of cellulose 25g, diameter 50nm or so, sequentially add in dispersion cylinder, room temperature mechanical stirs
30min is mixed, conductive ink is obtained；
By conductive ink using dimple be coated with, be coated on PET basement membranes, then 100 DEG C, 2min drying, winding, be made it is low
Sheet resistance flexible transparent conducting film；Finally conductive film obtained is tested for the property.
Embodiment 4
(1) multifunctional monomer synthesizes：By 105g PAPI (Mn=700g/mol, 0.15mol) and 8.4g HDI
(0.05mol) is heated to 50 DEG C after sequentially adding four-hole boiling flask, and then 60g PEG-600 (0.1mol) are gradually at the uniform velocity added dropwise
Into four-hole boiling flask, after being added dropwise to complete, heat preservation 2h obtains intermediate 1 to the reaction was complete；
By 1 constant temperature of intermediate at 70 DEG C, 28.28g MEKO (0.325mol) are gradually added dropwise in intermediate 1, react 4h
Terminate, semiclosed isocyanates is made；
Finally semiclosed isocyanates is reacted with 104.4g EDTA (0.3575mol), until isocyanates has reacted
Entirely, multifunctional monomer is made.
(2) multifunctional monomer 50g, 2470 resin 100g of Bayhydrol xp, the ethoxy prepared step (1)
Nano-silver thread 10g, the deionized water 9815g of cellulose 25g, diameter 50nm or so, sequentially add in dispersion cylinder, room temperature mechanical stirs
30min is mixed, conductive ink is obtained；
By conductive ink using dimple be coated with, be coated on PET basement membranes, then 100 DEG C, 2min drying, winding, be made it is low
Sheet resistance flexible transparent conducting film；Finally conductive film obtained is tested for the property.
Embodiment 5
(1) multifunctional monomer synthesizes：By 122.5g PAPI (Mn=700g/mol, 0.175mol) and 6.25g MDI
(0.025mol) is heated to 65 DEG C after sequentially adding four-hole boiling flask, then by 20g PEG-400 (0.05mol) and 30g PEG-
600 (0.05mol) are gradually at the uniform velocity added drop-wise in four-hole boiling flask, and after being added dropwise to complete, heat preservation 2h obtains centre to the reaction was complete
Body 1；
By 1 constant temperature of intermediate at 70 DEG C, 31.54g MEKO (0.3625mol) are gradually added dropwise in intermediate 1, are reacted
4h terminates, and semiclosed isocyanates is made；
Finally semiclosed isocyanates is reacted with 116.46g EDTA (0.3988mol), until isocyanates has reacted
Entirely, multifunctional monomer is made.
(2) multifunctional monomer 50g, 2470 resin 100g of Bayhydrol xp, the ethoxy prepared step (1)
Nano-silver thread 10g, the deionized water 9815g of cellulose 25g, diameter 50nm or so, sequentially add in dispersion cylinder, room temperature mechanical stirs
30min is mixed, conductive ink is obtained；
By conductive ink using dimple be coated with, be coated on PET basement membranes, then 100 DEG C, 2min drying, winding, be made it is low
Sheet resistance flexible transparent conducting film；Finally conductive film obtained is tested for the property.
Embodiment 6
(1) multifunctional monomer synthesizes：By 122.5g PAPI (Mn=700g/mol, 0.175mol) and 5.55g IPDI
(0.025mol) is heated to 60 DEG C after sequentially adding four-hole boiling flask, then by 20g PEG-400 (0.05mol) and 30g PEG-
600 (0.05mol) are gradually at the uniform velocity added drop-wise in four-hole boiling flask, and after being added dropwise to complete, heat preservation 2h obtains centre to the reaction was complete
Body 1；
By 1 constant temperature of intermediate at 70 DEG C, 31.54g MEKO (0.3625mol) are gradually added dropwise in intermediate 1, are reacted
4h terminates, and semiclosed isocyanates is made；
Finally semiclosed isocyanates is reacted with 116.46g EDTA (0.3988mol), until isocyanates has reacted
Entirely, multifunctional monomer is made.
(2) multifunctional monomer 50g, 2470 resin 100g of Bayhydrol xp, the ethoxy prepared step (1)
Nano-silver thread 10g, the deionized water 9815g of cellulose 25g, diameter 50nm or so, sequentially add in dispersion cylinder, room temperature mechanical stirs
30min is mixed, conductive ink is obtained；
By conductive ink using dimple be coated with, be coated on PET basement membranes, then 100 DEG C, 2min drying, winding, be made it is low
Sheet resistance flexible transparent conducting film；Finally conductive film obtained is tested for the property.
The comparison of conductive film is referring to table 1 obtained by above-described embodiment 1~6 and comparative example.
Table 1：1~embodiment of embodiment, 6 experimental result is compared with example is compared
Embodiment 7
(1) multifunctional monomer synthesizes：By 70g PAPI (Mn=700g/mol, 0.1mol) and 17.4g TDI (0.1mol)
60 DEG C are heated to after sequentially adding four-hole boiling flask, 40g PEG-400 (0.1mol) are gradually at the uniform velocity then added drop-wise to four-hole boiling flask
In, after being added dropwise to complete, heat preservation 2h obtains intermediate 1 to the reaction was complete；
By 1 constant temperature of intermediate at 60 DEG C, 21.75g MEKO (0.25mol) are gradually added dropwise in intermediate 1, react 4h
Terminate, semiclosed isocyanates is made；
Finally semiclosed isocyanates is reacted with 80.3g EDTA (0.275mol), until the reaction was complete for isocyanates,
Multifunctional monomer is made.
(2) multifunctional monomer 10g, 2470 resin 100g of Bayhydrol xp, the hydroxy ethyl fiber prepared step (1)
Nano-silver thread 10g, the deionized water 9855g of plain 25g, diameter 50nm or so, sequentially add in dispersion cylinder, room temperature mechanical stirring
30min obtains conductive ink；
By conductive ink using dimple be coated with, be coated on PET basement membranes, then 100 DEG C, 2min drying, winding, be made it is low
Sheet resistance flexible transparent conducting film；Finally conductive film obtained is tested for the property.
Embodiment 8
(1) multifunctional monomer synthesizes：By 70g PAPI (Mn=700g/mol, 0.1mol) and 17.4g TDI (0.1mol)
60 DEG C are heated to after sequentially adding four-hole boiling flask, 40g PEG-400 (0.1mol) are gradually at the uniform velocity then added drop-wise to four-hole boiling flask
In, after being added dropwise to complete, heat preservation 2h obtains intermediate 1 to the reaction was complete；
By 1 constant temperature of intermediate at 60 DEG C, 21.75g MEKO (0.25mol) are gradually added dropwise in intermediate 1, react 4h
Terminate, semiclosed isocyanates is made；
Finally semiclosed isocyanates is reacted with 80.3g EDTA (0.275mol), until the reaction was complete for isocyanates,
Multifunctional monomer is made.
(2) multifunctional monomer 100g, 2470 resin 100g of Bayhydrol xp, the hydroxy ethyl fiber prepared step (1)
Nano-silver thread 10g, the deionized water 9765g of plain 25g, diameter 50nm or so, sequentially add in dispersion cylinder, room temperature mechanical stirring
30min obtains conductive ink；
By conductive ink using dimple be coated with, be coated on PET basement membranes, then 100 DEG C, 2min drying, winding, be made it is low
Sheet resistance flexible transparent conducting film；Finally conductive film obtained is tested for the property.
Embodiment 9
(1) multifunctional monomer synthesizes：By 70g PAPI (Mn=700g/mol, 0.1mol) and 17.4g TDI (0.1mol)
60 DEG C are heated to after sequentially adding four-hole boiling flask, 40g PEG-400 (0.1mol) are gradually at the uniform velocity then added drop-wise to four-hole boiling flask
In, after being added dropwise to complete, heat preservation 2h obtains intermediate 1 to the reaction was complete；
By 1 constant temperature of intermediate at 60 DEG C, 21.75g MEKO (0.25mol) are gradually added dropwise in intermediate 1, react 4h
Terminate, semiclosed isocyanates is made；
Finally semiclosed isocyanates is reacted with 80.3g EDTA (0.275mol), until the reaction was complete for isocyanates,
Multifunctional monomer is made.
(2) multifunctional monomer 50g, 2470 resin 200g of Bayhydrol xp, the hydroxy ethyl fiber prepared step (1)
Nano-silver thread 10g, the deionized water 9715g of plain 25g, diameter 50nm or so, sequentially add in dispersion cylinder, room temperature mechanical stirring
30min obtains conductive ink；
By conductive ink using dimple be coated with, be coated on PET basement membranes, then 100 DEG C, 2min drying, winding, be made it is low
Sheet resistance flexible transparent conducting film；Finally conductive film obtained is tested for the property.
Embodiment 10
(1) multifunctional monomer synthesizes：By 70g PAPI (Mn=700g/mol, 0.1mol) and 17.4g TDI (0.1mol)
60 DEG C are heated to after sequentially adding four-hole boiling flask, 40g PEG-400 (0.1mol) are gradually at the uniform velocity then added drop-wise to four-hole boiling flask
In, after being added dropwise to complete, heat preservation 2h obtains intermediate 1 to the reaction was complete；
By 1 constant temperature of intermediate at 60 DEG C, 21.75g MEKO (0.25mol) are gradually added dropwise in intermediate 1, react 4h
Terminate, semiclosed isocyanates is made；
Finally semiclosed isocyanates is reacted with 80.3g EDTA (0.275mol), until the reaction was complete for isocyanates,
Multifunctional monomer is made.
(2) multifunctional monomer 50g, 2470 resin 100g of Bayhydrol xp, the hydroxy ethyl fiber prepared step (1)
Nano-silver thread 2g, the deionized water 9823g of plain 25g, diameter 50nm or so, sequentially add in dispersion cylinder, room temperature mechanical stirring
30min obtains conductive ink；
By conductive ink using dimple be coated with, be coated on PET basement membranes, then 100 DEG C, 2min drying, winding, be made it is low
Sheet resistance flexible transparent conducting film；Finally conductive film obtained is tested for the property.
Embodiment 11
(1) multifunctional monomer synthesizes：By 70g PAPI (Mn=700g/mol, 0.1mol) and 17.4g TDI (0.1mol)
60 DEG C are heated to after sequentially adding four-hole boiling flask, 40g PEG-400 (0.1mol) are gradually at the uniform velocity then added drop-wise to four-hole boiling flask
In, after being added dropwise to complete, heat preservation 2h obtains intermediate 1 to the reaction was complete；
By 1 constant temperature of intermediate at 60 DEG C, 21.75g MEKO (0.25mol) are gradually added dropwise in intermediate 1, react 4h
Terminate, semiclosed isocyanates is made；
Finally semiclosed isocyanates is reacted with 80.3g EDTA (0.275mol), until the reaction was complete for isocyanates,
Multifunctional monomer is made.
(2) multifunctional monomer 50g, 2470 resin 100g of Bayhydrol xp, the hydroxy ethyl fiber prepared step (1)
Nano-silver thread 4g, the deionized water 9821g of plain 25g, diameter 50nm or so, sequentially add in dispersion cylinder, room temperature mechanical stirring
30min obtains conductive ink；
By conductive ink using dimple be coated with, be coated on PET basement membranes, then 100 DEG C, 2min drying, winding, be made it is low
Sheet resistance flexible transparent conducting film；Finally conductive film obtained is tested for the property.
The comparison of conductive film is referring to table 1 obtained by above-described embodiment 1, embodiment 7~11 and comparative example.
Table 2：Embodiment 1,7~embodiment of embodiment, 11 experimental result are compared with example is compared
By embodiments of the invention described above it is found that by add in the ink it is a kind of it is homemade both can with it is organic in ink
The multifunctional monomer that resin reaction can react again with silver ion, the sheet resistance of obtained conductive film can be reduced to 10 Ω/ with
Under；Simultaneously because multifunctional single physical efficiency is reacted with substrate surface hydrophilic radical, adhesive force is caused to increase substantially, in addition conductive ink
Mercury content is low, and film thickness is less than 100nm, so conductive film light transmittance obtained promotes apparent, water-fast and solvent resistant wiping
Decades of times can be improved；And the multifunctional monomer synthesis technology is simple, it is only necessary to which under air atmosphere, ink only needs routine
Mechanical agitation, the coating of conductive film only need to can be completed using the disposable coating of dimple coating of present industrial production maturation,
It is efficient, yield is high；Therefore, according to the present invention low square resistance flexible transparent conducting film made from embodiment in flexible apparatus and big
Tool has great advantage and application potential on size device.
It these are only exemplary embodiment of the present invention, be not intended to limit the invention, all spirit in the present invention
With within principle made by all any modification, equivalent and improvement etc., should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of synthetic method of multifunctional monomer, which is characterized in that include the following steps：
A, polyisocyanates is heated to 30-80 DEG C, is then 2 according to the molar ratio of polyisocyanates and polyether polyol:1,
Polyether polyol is added dropwise, is added dropwise to complete subsequent continuation of insurance temperature to the reaction was complete, intermediate 1 is made；The polyisocyanates
Average functionality is n+1；
B, the intermediate 1 is warming up to 40-70 DEG C, is then 1 according to the molar ratio of intermediate 1 and sealer：N adds dropwise
Enter in sealer to the intermediate 1, react 3-5h, semiclosed isocyanates is made；
C, by the semiclosed isocyanates and complexing agent in molar ratio 1：1.1n reacts, and until the reaction was complete, that is, obtains target
Product multifunctional monomer.
2. the synthetic method of multifunctional monomer as described in claim 1, it is characterised in that：
The polyisocyanates be average functionality be 5 polyphenyl polymethylene polyisocyanates and toluene di-isocyanate(TDI),
Methyl diphenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, phenylenedimethylidyne diisocyanate
A kind of mixture in ester；
The polyether polyol is one or two kinds of mixture in polyethylene glycol, polypropylene glycol；
The sealer is methyl ethyl ketoxime or hydrogen cyanide；
The complexing agent is ethylenediamine tetra-acetic acid.
3. a kind of multifunctional monomer obtained by synthetic method described in claims 1 or 2.
4. a kind of low square resistance flexible transparent conducting film, it is characterised in that：It is by the multifunctional monomer and polyhydroxy described in claim 3
Base resin, dispersion thickening aids, nano-silver thread, mechanical mixture is uniform in proportion for deionized water, and conductive ink is made；Again by conduction
Ink is coated on by dimple coating process on flexible parent metal, using 100 DEG C of continuous tunnel furnace, 2min drying windings, obtains target production
Product low square resistance flexible transparent conducting film；
The composition of each raw material of the conductive ink by mass percentage is：
Multifunctional monomer：0.1-1%；
Polyhydroxy resin：0.2-2%；
Disperse thickening aids：0.05-0.5%；
Nano-silver thread：0.02-0.2%；
Deionized water：96%-99.7%.
5. low square resistance flexible transparent conducting film according to claim 4, it is characterised in that：The polyhydroxy resin is
Bayhydrol xp 2470、VP LS 2227 or Bayhydrol VP LS 2306；The dispersion thickening aids
For methylcellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose or Sodium Polyacrylate.
6. low square resistance flexible transparent conducting film according to claim 4, it is characterised in that：The nano-silver thread it is a diameter of
10-100nm, draw ratio 500-1500.
7. low square resistance flexible transparent conducting film according to claim 4, it is characterised in that：The deionized water is ultra-pure water
Machine purification obtains, and TDS contents are 0ppm.
8. low square resistance flexible transparent conducting film according to claim 4, it is characterised in that：The flexible parent metal is poly- to stupid
Naphthalate or polyimides.
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