CN106298077B - The preparation method of flexible transparent conductive film with super-amphiphobic function - Google Patents
The preparation method of flexible transparent conductive film with super-amphiphobic function Download PDFInfo
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Abstract
The present invention relates to a kind of flexible transparent conductive film preparation method with super-amphiphobic function, feature is to be the step of including：Nano Silver is dispersed in add-on type transparent silicone rubber solution, fluorochemical polyether nanoparticle is added, obtains mixing liquid；The mass ratio of nano-silver thread, add-on type transparent silicone rubber solution and fluorochemical polyether nanoparticle is：1：20‑100：0.1‑0.5；Then the mixing liquid in step one is printed in release liners, progress is heated to solidify 0.5 1 hours at 100 150 DEG C, then demoulding, you can obtain the flexible transparent conductive film with super-amphiphobic function.The electric conductivity of its transparent conductive film prepared is well a lot, with good pliability and chemical resistance, realizes constructing for super-double-hydrophobic surface.
Description
Technical field
The present invention relates to the flexible transparent conductive film applied in the flexible display field of electronic product, more particularly to
A kind of preparation method of the flexible transparent conductive film with super-amphiphobic function.
Background technology
In recent years, hand-held electronic product development with rapid changepl. never-ending changes and improvements, giant-screen, fine definition liquid crystal display rapidly popularization and
Demand is continuously increased, and huge opportunity and development space is provided for transparent conductive film.Transparent conductive film refers to ripple
The transmitance of long scope visible ray between 380 ~ 780 nm is more than 80%, resistivity and is less than l0-3 Ω .cm film, its
High Resolution and Large Size flat-panel screens, solar cell, energy-saving infrared reflectance coating, transparency electromagnetic wave shield material, dye sensitization
There is quite varied application prospect and the market space in the electron-optical such as solar cell, electrochromic field.
Currently, transparent conductive film is mainly the hard transparent conductive material based on oxide semiconductor film (TCO)；Oxygen
It is most commonly used transparent conductive film in research and application to change indium tin (ITO), but ITO raw material resources are increasingly rare, also lack
Bending property, pliability are poor and film matter is crisp.In recent years, the transparent conductive film using flexible macromolecule as substrate not only possesses
ITO identical photoelectric characteristics, and also there are many distinctive advantages, such as：Can bending deformation, it is non-breakable, can roll up, can industrialize
Continuous production, is conducive to improving efficiency, frivolous portable, convenient transport etc..On flexible and transparent macromolecule membrane surface, coating height is led
The conductive filler (such as CNT, graphene and metal wire) of electric rate, assigns its excellent electric conductivity, can obtain flexible and transparent
Conductive film.
This film not only possesses good transparency, flexibility, while also excellent conductance, in theory for completely
It is alternative current just in wide variety of ITO types transparent conductive film.Therefore, in flexible and transparent macromolecule surface with conductive filler
Build the method for electrically conducting transparent network turns into the main development direction of current conductive film, is also the forward position heat of new material research
Point problem.
Flexible transparent conductive film does not require nothing more than satisfactory electrical conductivity, also to there is excellent visible light transmissivity.But from physics
Angle sees that material translucency and electric conductivity are a pair of basic contradictions, can with intrinsic conductivity (Direct Current, DC) with
The ratio between photoconductivity (Optic Current, OP) (SDC/SOP) height the performance of transparent conductive film described.SDC/SOPMore
Height, shows that the transmitance of film is higher, square resistance is lower.It is reported that transparent conductive film prepared by CNT is best
SDC/SOPIt is worth for 25 ~ 35, and the S based on grapheneDC/SOPValue, then only 2 or so, but the electrically conducting transparent based on nano-silver thread
The S of filmDC/SOPValue then can reach 450.Therefore, the flexible transparent conductive film that is prepared based on nano-silver thread it is most possible into
To substitute the next-generation of ito thin film, also to realize flexible touch screen, bent light emitting diode（LED）Display etc. is provided
The chance realized.
At present, prepare transparent conductive film and its application on nano-silver thread turns into study hotspot both domestic and external.Such as day
State-owned a large amount of researchers such as sheet, South Korea, the U.S., Germany, Canada are engaged in the research in the field and acquisition of technology breaks through.
The country, Tsing-Hua University, Peking University, South China Science ＆ Engineering University, Jilin University, Shanghai Communications University, Suzhou nanometer institute, national nanometer
The units such as research center, Guangzhou chemistry institute, Shenzhen Xianjin Technology Academe have also carried out the research and formation of related fields
Respective advantage.Generally speaking, also there is following Railway Project and need emphasis in the transparent conductive film for being currently based on nano-silver thread
Research and solution, such as：(a) compatibility between nano-silver thread and PET (PET) film is poor, causes transparent
The wearability of conductive film is bad；(b) presence contact resistance between nano-silver thread and cause conductance excessively relatively low；(c) nanometer
The poor dispersion of silver wire, causes transparency not high enough；(d) conductive coating is afraid of water, mist is short-circuit, or Yi Beishui, oil substances
Pollution, the also not chemical attack such as acid and alkali-resistance.Up to the present, it can propose to integrate what is solved the above problems in also no document report
Method.Therefore, once the exploitation of Related product can not only be promoted by having method to solve the above problems, and for the reason of association area
By research with very big novelty.
There is many plant leafs and animal feather to have a super-hydrophobic phenomenon in nature, such as lotus leaf have mud without dye spy
Property (self-cleaning function).If assigning a certain material surface " lotus leaf effect ", the material obtains self-cleaning function.It is thin relative to super
For water surface, super-double-hydrophobic surface is hydrophobic and oleophobic, possesses anti-fingerprint, waterproof and oilproof, anti-fog freeze proof, acid and alkali-resistance corrosion-resistant etc.
Function, therefore have more excellent automatically cleaning effect and broader practice prospect.According to triumphant western Irving Baxter (Cassie-
Baxter) theoretical, the surface wettability of super-amphiphobic material can mainly be determined, roughness by the surface roughness of material and surface
More low more preferable ultra-amphosphobic (self-cleaning property) can then can be achieved in bigger, surface.For super hydrophobic surface, super-double-hydrophobic surface
Construction technology is increasingly complex and difficulty, large roughness and require in addition to low-surface-energy, also to form coarse as far as possible except that need to try one's best
The nano-particle of degree has certain concaveconvex structure pattern (Re-entrant Structure), in addition, also requiring low-surface energy substance
In should contain long chain fluorine-containing unit (CnF2n+1(n >=8)) or fluorinated liquid crystal construction unit.Therefore, super-amphiphobic self-cleaning surface is constructed
It is more difficult to, the report of this respect is also less.In addition, long chain fluorine-containing material of the current application in super-amphiphobic field, it is typically all pair
Environment and the harmful material of human body.
Super-hydrophobic or super-amphiphobic coating the preparation method of tradition, can cause the pattern and color of material surface to be applied by super-amphiphobic
Layer covers and becomes opaque.In recent years, transparent super-amphiphobic material, because it will not change the apparent colour and shape of substrate surface
Looks, and it is studied more and more.Constructing the method for transparent hydrophobic or super-double-hydrophobic surface mainly has：It is plasma etching method, soft
Photolithography method, sol-gal process, phase separation method, nano-particle and polymer self assembles method etc..Wherein, nano-particle gathers with fluorine-containing
Compound self-assembly method is that application is most wide and method of Maximum Value, mainly uses the inorganic of certain particle size and distribution
Nano-particle constructs roughness (its particle diameter should be less than visible wavelength, while there is good dispersion), then is grafted fluoropolymer
Low-surface-energy drops in thing, with this realizes transparent super-double-hydrophobic surface.Generally speaking, current transparent super-double-hydrophobic surface also exists following several
Individual problem needs primary study and solution：(a) roughness on surface is difficult while taking into account with transparency；(b) receiving for roughness is constructed
Rice corpuscles hardly possible is scattered, easily reunite；(c) bonding force between super-amphiphobic coating and base material is weak, and mill property is not good；(d) preparation technology is multiple
It is miscellaneous, be difficult large-scale production.
No matter transparent conductive film uses hand-held electronic display（Such as mobile phone, tablet personal computer, electronic reader or notes
This computer）Or during the field such as industrial large-sized electronic console, its surface is all inevitably polluted by dust or grease, and mostly
It is difficult to clean up in the case of number, so as to influence the service life and performance of transparent conductive film.If therefore in its surface construction
Layer of transparent super-amphiphobic coating, then can be achieved the super-amphiphobic automatically cleaning effect of transparent conductive film so that it has excellent resist
The performance such as fingerprint, acid rain resistant, resistant to dust, wear-resisting.According to statistics, the world market value of transparent conductive film is pre- in 2015
Meter reaches 10,000,000,000 dollars, if assigning the transparent conductive film self-cleaning performance, can further improve its performance and additional
Value, its output value is expected to reach 200 ~ 30,000,000,000 dollars；Therefore, transparent conductive film self-cleaning property how is assigned, is national warp
The Key Scientific And Technical Problems urgently solved are needed in Ji and social development, with highly important application prospect and innovative significance.
The present inventor and its partner propose in patent 201410093705.2, using the mixed of epoxy resin and curing agent
Compound as primary coat, and in this, as binding agent face apply, then substrate surface bond one layer change via fluorine-containing or silicon-containing compound
The nano-silver thread of property, constructs the conductive coating with self-cleaning function.Although this method can be prepared into certain automatically cleaning effect
The electrically-conducting paint of fruit, but be due in the method, to need first to be modified nano-silver thread surface with fluorine silicon resin, it is clear that in silver
Surface, which carries out chemical modification, can cause nano-silver thread to form very big resistance when conductive network is built, simultaneously as fluorine
Compatibility between silicon polymer and epoxy resin is not fine, therefore on the one hand can influence the transparency of electrically-conducting paint, so that
Transparent conductive film can not be prepared into, while epoxy resin is also hard and crisp compound, therefore can not be realized current flexible saturating
The need for bright conductive film.Still further aspect, due to the phase between the nano-silver thread and epoxy resin by fluorine silicon resin modification
Capacitive is bad so that the bonding force of the conductive coating and base material is also very weak.Therefore, although the invention is realized on electrically-conducting paint surface
Self-cleaning function.But it can only be confined to some specific fields in the process of application, and it can not apply currently just
In the flexible electronics field of fast development.
Furthermore, the present inventor and its partner proposed that a kind of spike structure was received in patent 201410109348.4
There is rice silver wire, the spike structure nano silver wire spherical nano-silver thread and linear nano silver line to assemble the nanometer to be formed/micro-
The multi-level roughness of rice, is modified using fluorochemical, using epoxy resin as binding agent, and obtaining can be with surpassing with superior electrical conductivity
The conductive self-cleaning coating of double thin performances, is coated on base material, not only assigns substrate surface excellent electric conductivity, also assigns base
Basal surface self-cleaning function, can be widely applied to field of electronics.In the patent, using the roughness on nano-silver thread surface,
Further increase self-cleaning performance.But still there is above mentioned problem, such as transparency is not high enough, flexible bad, conductive
The shortcomings of coated adhesive performance is not good enough.
The content of the invention
The primary and foremost purpose of the present invention is the shortcoming and deficiency for overcoming prior art and provides a kind of with super-amphiphobic function
Flexible transparent conductive film preparation method, the flexible transparent conductive film produced by the preparation method has self-cleaning performance
Good, transparency is high, it is flexible the advantages of, the demand of user can be met.
In order to achieve the above object, the technical proposal of the invention is realized in this way, and it is a kind of with super-amphiphobic function
Flexible transparent conductive film preparation method, it is characterised in that comprise the following steps：
Step one
Nano-silver thread is dispersed in add-on type transparent silicone rubber solution, fluorochemical polyether nanoparticle is added, is mixed
Close liquid；The mass ratio of nano-silver thread, add-on type transparent silicone rubber solution and fluorochemical polyether nanoparticle is：1：20-100：
0.1-0.5；
Step 2
Then the mixing liquid in step one is printed in release liners, progress is heated to solidify at 100-150 DEG C
0.5-1 hours, then demoulding, you can obtain the flexible transparent conductive film with super-amphiphobic function.
In the technical program, the preparation method of described nano-silver thread is as follows：
Silver salt, guiding agent, metal salt are dissolved in solvent, 120-160 degrees Celsius is warming up to, after reacting 4-8 hours, warp
Centrifugation is crossed, then is washed with ethanol, you can nano-silver thread is obtained；Wherein the mass ratio of silver salt, guiding agent, metal salt and solvent is 1:
0.5-5：0.001-0.005:20-50；
Wherein described silver salt is silver nitrate, silver perchlorate or silver fluoride；
The guiding agent is polyethylene glycol, polyoxyethylene, polyvinyl alcohol or PVP；
The metal salt is sodium chloride, sodium bromide, vulcanized sodium, potassium chloride, KBr, potassium hydroxide, iron chloride, protochloride
At least one of iron, copper chloride, stannous chloride, platinum chloride, sodium citrate, ascorbic acid and ammonium chloride；
The solvent is ethylene glycol, propane diols, glycerine, diglycol, Diethylene Glycol, butanediol, new penta
At least one of glycol and polyethylene glycol.
In the technical program, the preparation method of the add-on type transparent silicone rubber solution is as follows：
Platinum catalyst is added in low viscosity vinyl polysiloxane, containing hydrogen silicone oil, MQ resins and inhibitor system, stirred
Mix and uniformly can obtain organic siliconresin；Wherein low viscosity vinyl polysiloxane, containing hydrogen silicone oil, MQ resins, inhibitor and platinum
The mass ratio of catalyst is respectively：1：0.05 - 0.1：0.005 - 0.01：0.0001 - 0.0002：0.0001 -
0.0005；
Wherein, the platinum catalyst is the platinum complex of divinyl tetramethyl disiloxane, and the platinum content is
2000-7000 ppm；
The contents of ethylene of the low viscosity vinyl polysiloxane is 0.2 mol% -2 mol%, and viscosity is 200mPa.S-
10000mPa.S straight chain and side chain and silicone oil；
The containing hydrogen silicone oil is trimethyl or dimethyl or hydroxy-end capped polymethyl hydrogen siloxane, and hydrogen content is in molecule
0.5-1.6%, viscosity is 30-85mPas；
The MQ resins be molecule medium vinyl mass content be 0.1-6.5% vinyl MQ silicones, viscosity is
4000-10000mPa•s；
The inhibitor is：3- methyl isophthalic acids-butine -3- alcohol, methylpentynol, 3,5- dimethyl -1- hexins -
One kind in 3- alcohol, 1- acetenyl -1- cyclohexanol and 3-Phenyl-1-butyn-3-ol.
In the technical program, the preparation method of the fluorochemical polyether nanoparticle is as follows：
Step one
Silicon dioxide microsphere is added in solvent B, poly (glycidyl methacrylate) is added, 80-150 is warming up to
DEG C, react 2-6 hour, then centrifuge, surface must be arrived and connect the silicon dioxide microsphere for propping up and having epoxide group by washing；Wherein silica is micro-
The particle diameter of ball is 50-500nm, and the molecular weight of poly (glycidyl methacrylate) is 5000-20000, silicon dioxide microsphere, molten
The mass ratio of agent B and poly (glycidyl methacrylate) is：1: 10-50: 1-5；
Step 2
The silicon dioxide microsphere that the surface obtained in step one is connect into branch epoxide group is added in solvent B, is added
The Fluoropolyether compound of sulfydryl is held, 80-150 DEG C is warming up to, reacted 2-6 hours, then is centrifuged, surface must be arrived and meet Zhi Youhan by washing
The silicon dioxide microsphere of perfluoroalkyl polyether compound, i.e. fluorochemical polyether nanoparticle；Wherein, surface, which connects branch, the titanium dioxide of epoxide group
Silicon microballoon, solvent B and hold sulfydryl Fluoropolyether compound mass ratio be：1: 10-50: 1-5；
The solvent B is：One kind in cyclohexanone, tetrahydrofuran, toluene, dimethylbenzene, butanone and the alkane of dioxy six.
In the technical program, the synthetic method of the end sulfydryl Fluoropolyether compound is as follows：
Fluorochemical polyether is dissolved in tetrahydrofuran after adding lithium aluminium hydride reduction reaction 5-10 hours, obtains end and contain
The fluorochemical polyether solution of hydroxyl；Thiocarbamide and hydrochloric acid, the concentration of hydrochloric acid are added in the fluorochemical polyether solution that terminad contains hydroxyl again
For 37%, react 2-5 hour, add excessive sodium hydroxide, react 5-10 hours, you can obtain the fluorochemical polyether of end sulfydryl
Compound；
Wherein the mass ratio of fluorochemical polyether, tetrahydrofuran, lithium aluminium hydride reduction, thiocarbamide, hydrochloric acid and sodium hydroxide is 1：10-20：
0.001-0.1：3-6：0.1-0.5：1-3；Described fluorochemical polyether is preferably perfluor -2,5,8- trimethyl -3,6,9- trioxas
Lauroyl fluorine（CAS accession number 27639-98-1）.
Compared with prior art, the present invention has advantages below to the present invention：
1st, dielectric silane sol body is introduced in background technology to be assembled into for CNT, it is directly sharp in this patent
The electric conductivity of the transparent conductive film prepared with nano-silver thread is well a lot；
2nd, flexible transparent film is solidified into using additional organosilicon in this patent, with good pliability and chemically-resistant
Corrosivity, self-cleaning performance is good, and transparency is high；
3rd, connecing to prop up using surface in this patent has the nanoparticle of Fluoropolyether compound to construct the roughness on surface, from
And realize constructing for super-double-hydrophobic surface；
When the 4th, constructing super-amphiphobic material in this patent, it is to avoid presently most widely used toxicity larger perfluor material
(such as FOEA, PFOA, PFOS), using the perfluoropolyether material newly synthesized, the material be it is environment-protecting and non-poisonous, on the whole this
The flexible transparent conductive film with super-amphiphobic function prepared in patent is environmental protection.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Embodiment one
（1）The preparation of linear nano silver line
Silver salt, guiding agent and metal salt are dissolved in solvent, 120 degrees Celsius are warming up to, after reaction 4 hours, by from
The heart, then washed with ethanol, you can obtain linear nano silver line；Wherein the mass ratio of silver salt, guiding agent, metal salt and solvent is 1:
0.5：0.001:20；
The silver salt is silver nitrate；The solvent is ethylene glycol；The guiding agent is polyethylene glycol；The metal salt is chlorine
Change sodium；
（2）The preparation of add-on type transparent silicone rubber solution
Platinum catalyst is added in low viscosity vinyl silicone oil, containing hydrogen silicone oil, MQ resins and inhibitor system, stirred
It is uniform to can obtain organic siliconresin；Wherein low viscosity vinyl silicone oil, containing hydrogen silicone oil, MQ resins, inhibitor and platinum catalysis
The mass ratio of agent is respectively：1：0.05：0.005：0.0001：0.0001；
Wherein, the contents of ethylene of the low viscosity vinyl polysiloxane is 0.2 mol%, and viscosity is straight for 200mPa.S's
Chain silicone oil；
The platinum catalyst is the platinum complex of divinyl tetramethyl disiloxane, and the platinum content is 2000ppm；
The containing hydrogen silicone oil is trimethyl, and hydrogen content is 0.5% in molecule, and viscosity is 30mPas；
The MQ resins are the vinyl MQ silicones of the mass content 0.1% of molecule medium vinyl, and viscosity is
4000mPa•s；
Described inhibitor is：3- methyl isophthalic acids-butine -3- alcohol；
（3）The preparation of fluorochemical polyether nanoparticle
Step one
Silicon dioxide microsphere is added in solvent B, poly (glycidyl methacrylate) is added, 80 DEG C are warming up to,
Reaction 2 hours, then is centrifuged, and surface must arrive and connect the silicon dioxide microsphere for propping up and having epoxide group by washing；Wherein silicon dioxide microsphere
Particle diameter is 50nm, and the molecular weight of poly (glycidyl methacrylate) is 5000, silicon dioxide microsphere, solvent B and poly- methyl-prop
The mass ratio of olefin(e) acid ethylene oxidic ester is：1: 10: 1；
Step 2
The silicon dioxide microsphere that resulting surface in step one is connect into branch epoxide group is added in solvent B, is added
The Fluoropolyether compound of sulfydryl is held, 80 DEG C are warming up to, reacted 2 hours, then is centrifuged, washing to arrive surface and connect to prop up has fluorochemical polyether
The silicon dioxide microsphere of compound, i.e. fluorochemical polyether nanoparticle；Wherein, surface, which connects branch, has the silica of epoxide group micro-
Ball, solvent B and hold sulfydryl Fluoropolyether compound mass ratio be：1: 10: 1；Described solvent B is cyclohexanone；
（4）Hold the preparation of sulfydryl Fluoropolyether compound
Fluorochemical polyether is dissolved in tetrahydrofuran after adding lithium aluminium hydride reduction reaction 5 hours, obtains end and contain hydroxyl
The fluorochemical polyether solution of base, then terminad contain thiocarbamide and hydrochloric acid are added in the fluorochemical polyether solution of hydroxyl, and concentration of hydrochloric acid is
37%, react 2 hours, add excessive sodium hydroxide, react 5 hours, you can obtain holding the Fluoropolyether compound of sulfydryl；
Wherein the mass ratio of fluorochemical polyether, tetrahydrofuran, lithium aluminium hydride reduction, thiocarbamide, hydrochloric acid and sodium hydroxide is 1：10：0.001：3：0.1：
1；The fluorochemical polyether is preferably perfluor -2,5,8- trimethyl -3,6,9- trioxa lauroyl fluorine（CAS accession number 27639-98-
1）；
（5）The preparation of flexible transparent conductive film with super-amphiphobic function
Synthesis wire nano-silver thread is dispersed in add-on type transparent silicone rubber solution, fluorochemical polyether nanometer is added micro-
Ball, obtains mixing liquid, then mixing liquid is printed in release liners, and progress is heated to solidify 0.5 hour at 100 DEG C, then
Demoulding, you can obtain the flexible transparent conductive film with super-amphiphobic function, the flexible and transparent conductive with super-amphiphobic function is thin
Film can be applicable to the flexible display field of electronic product；Wherein nano-silver thread, add-on type transparent silicone rubber solution and fluorine-containing poly-
The mass ratio of ether nanoparticle is：1：20：0.1.
Embodiment two
（1）The preparation of linear nano silver line
Silver salt, guiding agent and metal salt are dissolved in solvent, 160 degrees Celsius are warming up to, after reaction 8 hours, by from
The heart, then washed with ethanol, you can obtain linear nano silver line；Wherein the mass ratio of silver salt, guiding agent, metal salt and solvent is 1:
5： 0.005: 50；
Wherein described silver salt is silver perchlorate；The guiding agent is PVP；The metal salt is chlorination
Potassium；The solvent is propane diols；
（2）The preparation of add-on type transparent silicone rubber solution
Platinum catalyst is added in low viscosity vinyl polysiloxane, containing hydrogen silicone oil, MQ resins and inhibitor system, stirred
Mix and uniformly can obtain organic siliconresin；Wherein low viscosity vinyl polysiloxane, containing hydrogen silicone oil, MQ resins, inhibitor and platinum
The mass ratio of catalyst is respectively：1： 0.1： 0.01： 0.0002： 0.0005；
Wherein, the platinum catalyst is the platinum complex of divinyl tetramethyl disiloxane, and the platinum content is
7000 ppm；
The contents of ethylene of the low viscosity vinyl polysiloxane is 2 mol%, straight chain and branch that viscosity is 10000mPa.S
Chain and silicone oil；
The containing hydrogen silicone oil is dimethyl, and hydrogen content is 1.6% in molecule, and viscosity is 85mPas；
The MQ resins are the vinyl MQ silicones of the mass content 6.5% of molecule medium vinyl, and viscosity is
10000mPa•s；
The inhibitor is in 3-Phenyl-1-butyn-3-ol；
（3）The preparation of fluorochemical polyether nanoparticle
Step one
Silicon dioxide microsphere is added in solvent B, poly (glycidyl methacrylate) is added, 150 DEG C are warming up to,
Reaction 6 hours, then is centrifuged, and surface must arrive and connect the silicon dioxide microsphere for propping up and having epoxide group by washing；Wherein silicon dioxide microsphere
Particle diameter is 500nm, and the molecular weight of poly (glycidyl methacrylate) is 20000, silicon dioxide microsphere, solvent B and poly- methyl
The mass ratio of glycidyl acrylate is：1: 50: 5；
Step 2
The silicon dioxide microsphere that the surface that step one is obtained connects branch and has epoxide group is added in solvent B, adds end
The Fluoropolyether compound of sulfydryl, is warming up to 150 DEG C, reacts 6 hours, then centrifuges, and washing to arrive surface and connect to prop up has fluorochemical polyether
The silicon dioxide microsphere of compound, i.e. fluorochemical polyether nanoparticle；Wherein, surface, which connects branch, has the silica of epoxide group micro-
Ball, solvent B and the mass ratio of Fluoropolyether compound of sulfydryl is held to be：1: 50: 5；The solvent B is tetrahydrofuran；
（4）Hold the preparation of sulfydryl Fluoropolyether compound
Fluorochemical polyether is dissolved in tetrahydrofuran after adding lithium aluminium hydride reduction reaction 10 hours, obtains end and contain hydroxyl
The fluorochemical polyether solution of base, then terminad contain thiocarbamide and hydrochloric acid are added in the fluorochemical polyether solution of hydroxyl, and concentration of hydrochloric acid is
37%, react 5 hours, add excessive sodium hydroxide, react 10 hours, you can obtain holding the Fluoropolyether compound of sulfydryl；
Wherein the mass ratio of fluorochemical polyether, tetrahydrofuran, lithium aluminium hydride reduction, thiocarbamide, hydrochloric acid and sodium hydroxide is 1： 20：0.1： 6：
0.5： 3；The fluorochemical polyether is preferably perfluor -2,5,8- trimethyl -3,6,9- trioxa lauroyl fluorine（CAS accession number
27639-98-1）；
（5）The preparation of flexible transparent conductive film with super-amphiphobic function
Synthesis wire nano-silver thread is dispersed in add-on type transparent silicone rubber solution, fluorochemical polyether nanometer is added micro-
Ball, obtains mixing liquid, then mixing liquid is printed in release liners, and progress is heated to solidify 1 hour at 120 DEG C, then takes off
Film, you can obtain the flexible transparent conductive film with super-amphiphobic function, the flexible transparent conductive film with super-amphiphobic function
It can be applicable to the flexible display field of electronic product；Wherein linear nano silver line, add-on type transparent silicone rubber solution and fluorine-containing
The mass ratio of polyethers nanoparticle is：1： 100： 0.5.
Embodiment three
（1）The preparation of linear nano silver line
Silver salt, guiding agent and metal salt are dissolved in solvent, 140 degrees Celsius are warming up to, after reaction 6 hours, by from
The heart, then washed with ethanol, you can obtain nano-silver thread；Wherein the mass ratio of silver salt, guiding agent, metal salt and solvent is 1:1：
0.004:40；
Wherein described silver salt is silver fluoride；The guiding agent is PVP；The metal salt is ammonium chloride；
The solvent is polyethylene glycol；
（2）The preparation of add-on type transparent silicone rubber solution
Platinum catalyst is added in low viscosity vinyl polysiloxane, containing hydrogen silicone oil, MQ resins and inhibitor system, stirred
Mix and uniformly can obtain organic siliconresin；Wherein low viscosity vinyl polysiloxane, containing hydrogen silicone oil, MQ resins, inhibitor and platinum
The mass ratio of catalyst is respectively：1：0.08：0.008：0.0001：0.0001；
Wherein, the contents of ethylene of the low viscosity vinyl polysiloxane is 1mol%, and viscosity is 8000mPa.S side chain
Silicone oil；
The containing hydrogen silicone oil is hydroxy-end capped polymethyl hydrogen siloxane, and hydrogen content is 1% in molecule, and viscosity is 75mPa
s；
The platinum catalyst is the platinum complex of divinyl tetramethyl disiloxane, and the platinum content is 6000
ppm；
The MQ resins are the vinyl MQ silicones of the mass content 1.5% of molecule medium vinyl, and viscosity is
6000mPa•s；
The inhibitor is 3,5- dimethyl -1- hexin -3- alcohol；
（3）Hold the preparation of sulfydryl Fluoropolyether compound
Fluorochemical polyether is dissolved in tetrahydrofuran after adding lithium aluminium hydride reduction reaction 8 hours, obtains end and contain hydroxyl
The fluorochemical polyether of base.Thiocarbamide and hydrochloric acid are added in the fluorochemical polyether solution that terminad contains hydroxyl again, concentration of hydrochloric acid is 37%, instead
Answer 4 hours, add excessive sodium hydroxide, react 8 hours, you can obtain holding the Fluoropolyether compound of sulfydryl；Wherein contain
Perfluoroalkyl polyether, tetrahydrofuran, lithium aluminium hydride reduction, thiocarbamide, the mass ratio of hydrochloric acid and sodium hydroxide are 1：16：0.06：4：0.35：2；It is described
Fluorochemical polyether be preferably perfluor -2,5,8- trimethyl -3,6,9- trioxa lauroyl fluorine（CAS accession number 27639-98-1）；
（4）The preparation of fluorochemical polyether nanoparticle
Step one
Silicon dioxide microsphere is added in solvent B, poly (glycidyl methacrylate) is added, 120 DEG C are warming up to,
Reaction 3 hours, then is centrifuged, and surface must arrive and connect the silicon dioxide microsphere for propping up and having epoxide group by washing.Wherein silicon dioxide microsphere
Particle diameter is 100nm, and the molecular weight of poly (glycidyl methacrylate) is 10000, silicon dioxide microsphere, solvent B and poly- methyl
The mass ratio of glycidyl acrylate is：1: 20: 2；
Step 2
The silicon dioxide microsphere that surface resulting in step one is connect into branch epoxide group is added in solvent B, then is added
Enter to hold the Fluoropolyether compound of sulfydryl, be warming up to 120 DEG C, react 4 hours, then centrifuge, washing to arrive surface and connect to prop up has fluorine-containing
The silicon dioxide microsphere of polyether compound, i.e. fluorochemical polyether nanoparticle；Wherein, surface, which connects branch, the silica of epoxide group
Microballoon, solvent B and hold sulfydryl Fluoropolyether compound mass ratio be：1: 40: 3；Described solvent B is toluene；
（5）The preparation of flexible transparent conductive film with super-amphiphobic function
Synthesis wire nano-silver thread is dispersed in add-on type transparent silicone rubber solution, fluorochemical polyether nanometer is added micro-
Ball, obtains mixing liquid, then mixing liquid is printed in release liners, and progress is heated to solidify 0.6 hour at 150 DEG C, then
Demoulding, you can obtain the flexible transparent conductive film with super-amphiphobic function, the flexible and transparent conductive with super-amphiphobic function is thin
Film can be applicable to the flexible display field of electronic product；Wherein nano-silver thread, add-on type transparent silicone rubber solution and fluorine-containing poly-
The mass ratio of ether nanoparticle is：1：80：0.3.
Example IV
（1）The preparation of linear nano silver line
Silver salt, guiding agent and metal salt are dissolved in solvent, 120 degrees Celsius are warming up to, after reaction 5 hours, by from
The heart, then washed with ethanol, you can obtain linear nano silver line；Wherein the mass ratio of silver salt, guiding agent, metal salt and solvent is 1:
2：0.003：30；
Wherein described silver salt is silver nitrate；The guiding agent is PVP；The metal salt is vulcanized sodium；
The solvent is neopentyl glycol；
（2）The preparation of add-on type transparent silicone rubber solution
Platinum catalyst is added in low viscosity vinyl polysiloxane, containing hydrogen silicone oil, MQ resins and inhibitor system, stirred
Mix and uniformly can obtain organic siliconresin；Wherein low viscosity vinyl polysiloxane, containing hydrogen silicone oil, MQ resins, inhibitor and platinum
The mass ratio of catalyst is respectively：1： 0.1： 0.01： 0.0002：0.0002；
Wherein, the contents of ethylene of the low viscosity vinyl polysiloxane is 1.2 mol%, and viscosity is 5000mPa.S branch
Chain silicone oil；
The containing hydrogen silicone oil is trimethyl or dimethyl or hydroxy-end capped polymethyl hydrogen siloxane, and hydrogen content is in molecule
1.2%, viscosity is 45mPas；
The MQ resins are the vinyl MQ silicones of the mass content 3.5% of molecule medium vinyl, and viscosity is
5000mPa•s；
The inhibitor is 3- methyl isophthalic acids-butine -3- alcohol；
The platinum catalyst is the platinum complex of divinyl tetramethyl disiloxane, and the platinum content is 3000
ppm；
（3）The preparation of fluorochemical polyether nanoparticle
Step one
Silicon dioxide microsphere is added in solvent B, poly (glycidyl methacrylate) is added, 110 DEG C are warming up to,
Reaction 3 hours, then is centrifuged, and surface must arrive and connect the silicon dioxide microsphere for propping up and having epoxide group by washing；Wherein silicon dioxide microsphere
Particle diameter is 100nm, and the molecular weight of poly (glycidyl methacrylate) is 10000, silicon dioxide microsphere, solvent B and poly- methyl
The mass ratio of glycidyl acrylate is：1: 40: 3；
Step 2
The silicon dioxide microsphere that surface resulting in step one is connect into branch epoxide group is added in solvent B, then is added
Enter to hold the Fluoropolyether compound of sulfydryl, be warming up to 100 DEG C, react 3 hours, then centrifuge, washing to arrive surface and connect to prop up has fluorine-containing
The silicon dioxide microsphere of polyether compound, i.e. fluorochemical polyether nanoparticle；Wherein, surface, which connects branch, the silica of epoxide group
Microballoon, solvent B and hold sulfydryl Fluoropolyether compound mass ratio be：1: 30: 2；The solvent B is the alkane of dioxy six；
（4）Hold the preparation of sulfydryl Fluoropolyether compound
Fluorochemical polyether is dissolved in tetrahydrofuran after adding lithium aluminium hydride reduction reaction 6 hours, obtains end and contain hydroxyl
The fluorochemical polyether solution of base, then terminad contain thiocarbamide and hydrochloric acid are added in the fluorochemical polyether solution of hydroxyl, and concentration of hydrochloric acid is
37%, react 4 hours, add excessive sodium hydroxide, react 7 hours, you can obtain holding the Fluoropolyether compound of sulfydryl；
Wherein the mass ratio of fluorochemical polyether, tetrahydrofuran, lithium aluminium hydride reduction, thiocarbamide, hydrochloric acid and sodium hydroxide is 1：15：0.009：4：0.3：
2；Described fluorochemical polyether is preferably perfluor -2,5,8- trimethyl -3,6,9- trioxa lauroyl fluorine（CAS accession number 27639-
98-1）；
（5）The preparation of flexible transparent conductive film with super-amphiphobic function
Synthesis wire nano-silver thread is dispersed in add-on type transparent silicone rubber solution, fluorochemical polyether nanometer is added micro-
Ball, obtains mixing liquid, then mixing liquid is printed in release liners, and progress is heated to solidify 0.8 hour at 110 DEG C, then
Demoulding, you can obtain the flexible transparent conductive film with super-amphiphobic function, the flexible and transparent conductive with super-amphiphobic function is thin
Film can be applicable to the flexible display field of electronic product；Wherein nano-silver thread, add-on type transparent silicone rubber solution and fluorine-containing poly-
The mass ratio of ether nanoparticle is：1：80：0.4.
Embodiment five
（1）The preparation of linear nano silver line
Silver salt, guiding agent and metal salt are dissolved in solvent, 140 degrees Celsius are warming up to, after reaction 5 hours, by from
The heart, then washed with ethanol, you can obtain nano-silver thread；Wherein the mass ratio of silver salt, guiding agent, metal salt and solvent is 1：3：
0.002：25；
Wherein described silver salt is silver nitrate；The guiding agent is PVP；The metal salt is sodium chloride；
The solvent is butanediol；
（2）The preparation of add-on type transparent silicone rubber solution
Platinum catalyst is added in low viscosity vinyl polysiloxane, containing hydrogen silicone oil, MQ resins and inhibitor system, stirred
Mix and uniformly can obtain organic siliconresin；Wherein low viscosity vinyl polysiloxane, containing hydrogen silicone oil, MQ resins, inhibitor and platinum
The mass ratio of catalyst is respectively：1：0.07：0.009：0.0001：0.0003；
Wherein, the contents of ethylene of the low viscosity vinyl polysiloxane is 1.5 mol%, and viscosity is straight for 500mPa.S's
Chain silicone oil；
The containing hydrogen silicone oil is trimethyl or dimethyl or hydroxy-end capped polymethyl hydrogen siloxane, and hydrogen content is in molecule
1%, viscosity is 45mPas；
The MQ resins are the vinyl MQ silicones of the mass content 1.5% of molecule medium vinyl, and viscosity is
5000mPa•s。
The inhibitor is 3,5- dimethyl -1- hexin -3- alcohol；
The platinum catalyst is the platinum complex of divinyl tetramethyl disiloxane, and the platinum content is 6000
ppm；
（3）The preparation of fluorochemical polyether nanoparticle
Step one
Silicon dioxide microsphere is added in solvent B, poly (glycidyl methacrylate) is added, 100 DEG C are warming up to,
Reaction 3 hours, then is centrifuged, and surface must arrive and connect the silicon dioxide microsphere for propping up and having epoxide group by washing；Wherein silicon dioxide microsphere
Particle diameter is 100nm, and the molecular weight of poly (glycidyl methacrylate) is 10000, silicon dioxide microsphere, solvent B and poly- methyl
The mass ratio of glycidyl acrylate is：1: 20: 2；
Step 2
The silicon dioxide microsphere that surface resulting in step one is connect into branch epoxide group is added in solvent B, then is added
Enter to hold the Fluoropolyether compound of sulfydryl, be warming up to 90 DEG C, react 3 hours, then centrifuge, washing to arrive surface and connect to prop up has fluorine-containing poly-
The silicon dioxide microsphere of ether compound, i.e. fluorochemical polyether nanoparticle；Wherein, surface, which connects branch, has the silica of epoxide group micro-
Ball, solvent B and hold sulfydryl Fluoropolyether compound mass ratio be：1: 20: 2；The solvent B is dimethylbenzene；
（4）Hold the preparation of sulfydryl Fluoropolyether compound
Fluorochemical polyether is dissolved in tetrahydrofuran after adding lithium aluminium hydride reduction reaction 6 hours, obtains end and contain hydroxyl
The fluorochemical polyether of base, then terminad contain thiocarbamide and hydrochloric acid are added in the fluorochemical polyether solution of hydroxyl, and concentration of hydrochloric acid is 37%, instead
Answer 3 hours, add excessive sodium hydroxide, react 6 hours, you can obtain holding the Fluoropolyether compound of sulfydryl；Wherein contain
Perfluoroalkyl polyether, tetrahydrofuran, lithium aluminium hydride reduction, thiocarbamide, the mass ratio of hydrochloric acid and sodium hydroxide are 1： 20：0.001： 6： 0.5：1；
The fluorochemical polyether is preferably perfluor -2,5,8- trimethyl -3,6,9- trioxa lauroyl fluorine（CAS accession number 27639-98-
1）；
（5）The preparation of flexible transparent conductive film with super-amphiphobic function
Synthesis wire nano-silver thread is dispersed in add-on type transparent silicone rubber solution, fluorochemical polyether nanometer is added micro-
Ball, obtains mixing liquid, then mixing liquid is printed in release liners, and progress is heated to solidify 1 hour at 150 DEG C, then takes off
Film, you can obtain the flexible transparent conductive film with super-amphiphobic function, the flexible transparent conductive film with super-amphiphobic function
It can be applicable to the flexible display field of electronic product；Wherein nano-silver thread, add-on type transparent silicone rubber solution and fluorochemical polyether
The mass ratio of nanoparticle is：1： 100：0.1.
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention
Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (3)
1. a kind of flexible transparent conductive film preparation method with super-amphiphobic function, it is characterised in that comprise the following steps：
Step one
Nano-silver thread is dispersed in add-on type transparent silicone rubber solution, fluorochemical polyether nanoparticle is added, obtains mixed liquor
Body；The mass ratio of nano-silver thread, add-on type transparent silicone rubber solution and fluorochemical polyether nanoparticle is：1：20-100：0.1-
0.5；
Step 2
Then the mixing liquid in step one is printed in release liners, it is small that progress is heated to solidification 0.5-1 at 100-150 DEG C
When, then demoulding, you can obtain the flexible transparent conductive film with super-amphiphobic function；
The preparation method of the add-on type transparent silicone rubber solution is as follows：
Platinum catalyst is added in low viscosity vinyl polysiloxane, containing hydrogen silicone oil, MQ resins and inhibitor system, stirring is equal
It is even to can obtain organic siliconresin；Wherein low viscosity vinyl polysiloxane, containing hydrogen silicone oil, MQ resins, inhibitor and platinum catalysis
The mass ratio of agent is respectively：1：0.05 - 0.1：0.005 - 0.01：0.0001 - 0.0002：0.0001 - 0.0005；
Wherein, the platinum catalyst is the platinum complex of divinyl tetramethyl disiloxane, and the platinum content is 2000-
7000 ppm；
The contents of ethylene of the low viscosity vinyl polysiloxane is 0.2 mol% -2 mol%, and viscosity is 200mPa.S-
10000mPa.S straight chain；
The containing hydrogen silicone oil is trimethyl or dimethyl or hydroxy-end capped polymethyl hydrogen siloxane, and hydrogen content is 0.5- in molecule
1.6%, viscosity is 30-85mPas；
The MQ resins be molecule medium vinyl mass content be 0.1-6.5% vinyl MQ silicones, viscosity is
4000-10000mPa•s；
The inhibitor is：3- methyl isophthalic acids-butine -3- alcohol, methylpentynol, 3,5- dimethyl -1- hexins -3-
One kind in alcohol, 1- acetenyl -1- cyclohexanol and 3-Phenyl-1-butyn-3-ol；
The preparation method of the fluorochemical polyether nanoparticle is as follows：
Step one
Silicon dioxide microsphere is added in solvent B, poly (glycidyl methacrylate) is added, 80-150 DEG C is warming up to,
Reaction 2-6 hour, then is centrifuged, and surface must be arrived and connect the silicon dioxide microsphere for propping up and having epoxide group by washing；Wherein silicon dioxide microsphere
Particle diameter be 50-500nm, the molecular weight of poly (glycidyl methacrylate) is 5000-20000, silicon dioxide microsphere, solvent
The mass ratio of B and poly (glycidyl methacrylate) is：1: 10-50: 1-5；
Step 2
The silicon dioxide microsphere that the surface obtained in step one is connect into branch epoxide group is added in solvent B, adds end mercapto
The Fluoropolyether compound of base, is warming up to 80-150 DEG C, reacts 2-6 hours, then centrifuges, and washing to arrive surface and connect to prop up has fluorine-containing poly-
The silicon dioxide microsphere of ether compound, i.e. fluorochemical polyether nanoparticle；Wherein, surface, which connects branch, has the silica of epoxide group micro-
Ball, solvent B and hold sulfydryl Fluoropolyether compound mass ratio be：1: 10-50: 1-5；
The solvent B is：One kind in cyclohexanone, tetrahydrofuran, toluene, dimethylbenzene, butanone and the alkane of dioxy six.
2. the preparation method of the flexible transparent conductive film according to claim 1 with super-amphiphobic function, its feature exists
It is as follows in the preparation method of described nano-silver thread：
Silver salt, guiding agent, metal salt are dissolved in solvent, 120-160 degrees Celsius is warming up to, after reaction 4-8 hours, by from
The heart, then washed with ethanol, you can obtain nano-silver thread；Wherein the mass ratio of silver salt, guiding agent, metal salt and solvent is 1:0.5-
5：0.001-0.005:20-50；
Wherein described silver salt is silver nitrate, silver perchlorate or silver fluoride；
The guiding agent is polyethylene glycol, polyoxyethylene, polyvinyl alcohol or PVP；
The metal salt is sodium chloride, sodium bromide, vulcanized sodium, potassium chloride, KBr, iron chloride, frerrous chloride, copper chloride, chlorine
Change at least one of cuprous, platinum chloride, sodium citrate and ammonium chloride；
The solvent is ethylene glycol, propane diols, glycerine, diglycol, Diethylene Glycol, butanediol, neopentyl glycol
At least one of with polyethylene glycol.
3. the preparation method of the flexible transparent conductive film according to claim 1 with super-amphiphobic function, its feature exists
It is as follows in the synthetic method of the end sulfydryl Fluoropolyether compound：
Fluorochemical polyether is dissolved in tetrahydrofuran after adding lithium aluminium hydride reduction reaction 5-10 hours, obtains end and contain hydroxyl
Fluorochemical polyether solution；Thiocarbamide and hydrochloric acid are added in the fluorochemical polyether solution that terminad contains hydroxyl again, the concentration of hydrochloric acid is
37%, react 2-5 hours, add excessive sodium hydroxide, react 5-10 hours, you can obtain holding the fluorochemical polyether of sulfydryl
Compound；
Wherein the mass ratio of fluorochemical polyether, tetrahydrofuran, lithium aluminium hydride reduction, thiocarbamide, hydrochloric acid and sodium hydroxide is 1：10-20：
0.001-0.1：3-6：0.1-0.5：1-3；Described fluorochemical polyether is perfluor -2,5,8- trimethyl -3,6,9- trioxas 12
Acyl fluorides（CAS accession number 27639-98-1）.
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