CN106448804B - The preparation method of flexible transparent conductive film with self-cleaning function - Google Patents
The preparation method of flexible transparent conductive film with self-cleaning function Download PDFInfo
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
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- H—ELECTRICITY
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Abstract
The present invention relates to a kind of preparation method of the flexible transparent conductive film with self-cleaning function, feature is to be the step of including：The nano-silver thread that there is spherical Nano Silver on a kind of surface is added in organic siliconresin, while adding end sulfydryl Fluoropolyether compound, stirs, obtains mixing liquid；Wherein, planting surface has the mass ratio of the nano-silver thread, organic siliconresin and end sulfydryl Fluoropolyether compound of spherical Nano Silver to be respectively 1:10‑50:0.01‑0.05；Mixing liquid obtained by above-mentioned steps is sprayed on flexible transparent film surface, 80 120 DEG C are heated to, toasts 0.5 2 hours, obtains the flexible transparent conductive film with self-cleaning function.This flexible transparent conductive film with self-cleaning function can be applicable to the field such as hand-held electronic display or industrial large-sized electronic console.With self-cleaning function, transparency is high, flexible, the advantages of conductive coating adhesive property is good.
Description
Technical field
The present invention relates to a kind of preparation method of the flexible transparent conductive film with self-cleaning 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), its
In, tin indium oxide (ITO) is most commonly used transparent conductive film in research and application, but ITO raw material resources are increasingly rare,
Lack bending property, pliability is poor and film matter is crisp.In recent years, the transparent conductive film using flexible macromolecule as substrate is not only
Possess ITO identical photoelectric characteristics, and also there are many distinctive advantages, such as：Can bending deformation, it is non-breakable, can volume to volume
The continuous mode of production is industrialized to be conducive to improving efficiency, frivolous portable, convenient transport etc..On flexible and transparent macromolecule membrane surface
The conductive filler (such as CNT, graphene and metal wire) of high conductivity is coated, its excellent electric conductivity is assigned, be can obtain
Flexible 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.
Prepare transparent conductive film and its application on nano-silver thread at present 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 and cause conductance excessively relatively low；(c) Nano Silver
Poor dispersion, cause transparency not high enough；(d) conductive coating is afraid of water, mist is short-circuit, or the pollution of Yi Beishui, oil substances,
Also the not chemical attack such as acid and alkali-resistance.Up to the present, comprehensive result of the above problems can be proposed in also no document report.
Therefore, once the exploitation of Related product can not only be promoted by having method to solve the above problems, and ground for the theory of association area
Study carefully 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 200-300 hundred million 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
Rice silver wire, it is many that there is the spike structure nano silver wire spherical Nano Silver and linear nano silver to assemble the Nano/micron to be formed
Level roughness, is modified using fluorochemical, using epoxy resin as binding agent, is obtained with superior electrical conductivity energy and super-amphiphobic
The conductive self-cleaning coating of performance, is coated on base material, not only assigns substrate surface excellent electric conductivity, also assigns substrate table
Face self-cleaning function, can be widely applied to field of electronics.In the patent, using the roughness on nano-silver thread surface, enter one
Step improves self-cleaning performance.But still there is above mentioned problem, such as transparency is not high enough, flexible bad, conductive coating
The shortcomings of adhesive property 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 self-cleaning function
Flexible transparent conductive film preparation method, the performance of the product prepared by this method is more beneficial, and transparent conductive film has
Self-cleaning function, transparency is high, and flexible, conductive coating adhesive property is good.
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 self-cleaning function
Flexible transparent conductive film preparation method, it is characterised in that comprise the following steps：
Step one
The nano-silver thread that there is spherical Nano Silver on a kind of surface is added in organic siliconresin, contained while adding end sulfydryl
Perfluoroalkyl polyether compound, stirs, and obtains mixing liquid；Wherein, planting surface has the nano-silver thread of spherical Nano Silver, organosilicon tree
The mass ratio of fat and end sulfydryl Fluoropolyether compound is respectively 1:10-50:0.01-0.05；
Step 2
Mixing liquid obtained by step one is sprayed on flexible transparent film surface, 80-120 DEG C, baking is heated to
It is roasting 0.5-2 hours, obtain the flexible transparent conductive film with self-cleaning function；Wherein mixing liquid is in flexible transparent film table
The quantity for spray ratio in face is 1 gram and is sprayed on 0.5-1 square metres.
In the technical program, the surface has the preparation method of the nano-silver thread of spherical Nano Silver as follows：
Step one
Polyalcohol is added in reactor, is warming up to 120-200 DEG C, after nitrogen, then silver salt, metal salt is added dropwise
And guiding agent is added in reactor, reacts 2-6 hours, obtain linear nano silver line；Wherein silver salt, polyalcohol, metal salt and
The mass ratio of guiding agent is respectively：1：20-200：0.1-0.5：0.5-5；
Step 2
Linear nano silver line obtained by step one is redispersed in polyalcohol, silver salt and guiding agent is added,
After 50-60 DEG C are reacted 1-3 hours, then it is transferred into stainless steel autoclave, increases the temperature at 160 DEG C-200 DEG C
React again 4-8 hours, you can obtaining a kind of surface has the nano-silver thread of spherical Nano Silver；Wherein linear nano silver line, polyalcohol,
The mass ratio of silver salt and guiding agent is respectively：1：1 0-50：0.01-0.05:1-5；
Wherein described polyalcohol is：At least one of ethylene glycol, propane diols, glycerine, butanediol, neopentyl glycol；
The 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, iron chloride, frerrous chloride, copper chloride, chlorination
Platinum, sodium citrate, ascorbic acid or ammonium chloride.
In the technical program, the preparation method of the organic siliconresin 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 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 are the mass content 0.1-6.5% of molecule medium vinyl vinyl MQ silicones, and 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；
The platinum catalyst is the platinum complex of divinyl tetramethyl disiloxane, and the platinum content is 2000-
7000 ppm。
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 of hydroxyl, then terminad contain thiocarbamide and hydrochloric acid are added in the fluorochemical polyether solution of hydroxyl, and concentration of hydrochloric acid is 37%,
Reaction 2-5 hours, adds excessive sodium hydroxide, reacts 5-10 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 1：10-20：
0.001-0.1：3-6：0.1-0.5：1-3；The fluorochemical polyether is preferably perfluor -2,5,8- trimethyl -3,6,9- trioxas ten
Two acyl fluorides（CAS accession number 27639-98-1）.
In the technical program, the flexible transparent film is the high molecule plastic with certain pliability and excellent performance
Film, is preferably commercialized PET（PET）Film.
Compared with prior art, the present invention has advantages below to the present invention：
1st, nano-silver thread surface introduces spherical Nano Silver, can form a kind of multi-level roughness of micrometer/nanometer rank, carry
High ultra-amphosphobic；
2nd, for dielectric silane sol body is introduced in document and is assembled into CNT, in this project directly
The electric conductivity that roughness is constructed using the spherical Nano Silver of electric conductivity is well a lot；
3rd, due to Yin Yi and sulfydryl, carboxyl or amino surface formation chelate bonds, it is easier to realize the surface of fluoropolymer
Chemical graft；
4th, add-on type liquid silicon rubber coating is used in this patent as the cementability coating between nano-silver thread and base material,
Relative to conventional method（Nano Silver is directly sprayed on PET substrate surfaces）For, it is greatly improved conductive network and base material
Between bonding force, while also can to carry out chemical graft with end sulfydryl fluorochemical containing end anti-for the add-on type liquid organosilicon
Should, while ensure that the flexibility of transparent conductive film；With self-cleaning function, transparency is high, flexible, conductive coating cementability
Can be good；
When the 5th, constructing self-cleaning surface 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
The embodiment to the present invention is described further below.Herein it should be noted that for these implementations
The explanation of mode is used to help understand the present invention, but does not constitute limitation of the invention.In addition, invention described below
As long as involved technical characteristic does not constitute conflict and can be just combined with each other each other in each embodiment.
Embodiment one
（1）There is the synthesis of the nano-silver thread of spherical Nano Silver on a kind of surface
Step one
Polyalcohol is added in reactor, is warming up to 120 DEG C, after nitrogen, then silver salt, metal salt is added dropwise and draws
Lead agent to be added in reactor, react 2 hours, obtain linear nano silver line；Wherein silver salt, polyalcohol, metal salt and guiding agent
Mass ratio be respectively：1：20：0.1：0.5；
Step 2
Linear nano silver line obtained by step one is redispersed in polyalcohol, silver salt and guiding agent is added,
After 50 DEG C are reacted 1 hour, then it is transferred into stainless steel autoclave, increases the temperature to and reacted again at 160 DEG C 4 hours,
Can obtain surface has the nano-silver thread of spherical Nano Silver；The wherein quality of linear nano silver line, polyalcohol, silver salt and guiding agent
Than being respectively：1：10：0.01:1；
The polyalcohol is：Ethylene glycol；The silver salt is silver nitrate；The guiding agent is polyethylene glycol；The metal salt
For sodium chloride；
（2）The preparation of organic siliconresin
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：1：0.05：0.005：0.0001：0.0001；
Wherein, the contents of ethylene of the low viscosity vinyl polysiloxane is 0.2 mol%, and viscosity is straight for 200mPa.S's
Chain 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%, 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；
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 2000ppm；
（3）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）；
（4）The preparation of self-cleaning type flexible transparent conductive film
Step one
The nano-silver thread that there is spherical Nano Silver on a kind of surface is added in organic siliconresin, contained while adding end sulfydryl
Perfluoroalkyl polyether compound, stirs, and obtains a kind of mixing liquid；Wherein, there are the nano-silver thread of spherical Nano Silver, organosilicon in surface
The mass ratio of resin and end sulfydryl Fluoropolyether compound is respectively 1:10:0.01；
Step 2
Mixing liquid obtained by step one is sprayed on flexible transparent film surface, 80 DEG C are heated to, baking 0.5 is small
When, the flexible transparent conductive film with self-cleaning function is obtained, the flexible transparent conductive film with self-cleaning function can be answered
Used in hand-held electronic display（Such as mobile phone, tablet personal computer, electronic reader or notebook computer）Or industrial large-sized electronic display
Show the fields such as device；Wherein quantity for spray ratio of the mixing liquid on flexible transparent film surface is that 1g is sprayed on 0.5 square metre, and flexibility is thoroughly
Bright film is commercialized PET（PET）Film.
Embodiment two
（1）There is the synthesis of the nano-silver thread of spherical Nano Silver on a kind of surface
Step one
Polyalcohol is added in reactor, is warming up to 200 DEG C, after nitrogen, then silver salt, metal salt, guiding is added dropwise
Agent is added in reactor, is reacted 6 hours, is obtained linear nano silver line；Wherein silver salt, polyalcohol, metal salt and guiding agent
Mass ratio is respectively：1：200：0.5：5；
Step 2
Linear nano silver line obtained by step one is redispersed in polyalcohol, silver salt and guiding agent is added,
After 60 DEG C are reacted 1 hour, then it is transferred into stainless steel autoclave, increases the temperature to and reacted again at 200 DEG C 8 hours,
Can obtain surface has the nano-silver thread of spherical Nano Silver；The wherein quality of linear nano silver line, polyalcohol, silver salt and guiding agent
Than being respectively：1： 50： 0.05: 5；
The polyalcohol is：Propane diols；The silver salt is silver fluoride；The guiding agent is PVP；Institute
Metal salt is stated for ammonium chloride；
（2）The preparation of organic siliconresin
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；
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 trimethyl or dimethyl or hydroxy-end capped polymethyl hydrogen siloxane, and hydrogen content is in molecule
1.6%, 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；The platinum catalyst is the silicon of divinyl tetramethyl two
The platinum complex of oxygen alkane, the platinum content is 7000 ppm；
（3）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）；
（4）The preparation of self-cleaning type flexible transparent conductive film
Step one
The nano-silver thread that there is spherical Nano Silver on above-mentioned surface is added in organic siliconresin, contained while adding end sulfydryl
Perfluoroalkyl polyether compound, stirs, and obtains a kind of mixing liquid；Wherein, there are the nano-silver thread of spherical Nano Silver, organosilicon in surface
The mass ratio of resin and end sulfydryl Fluoropolyether compound is respectively 1:50:0.05；
Step 2
Mixing liquid obtained by step one is sprayed on flexible transparent film surface, 120 DEG C are heated to, baking 2 is small
When, obtain the flexible transparent conductive film with self-cleaning function；Wherein quantity for spray ratio of the mixing liquid in flexible transparent film
1 square metre is sprayed on for 1g, and flexible transparent film is commercialized PET（PET）Film.Have
The flexible transparent conductive film of self-cleaning function can be applicable to hand-held electronic display（Such as mobile phone, tablet personal computer, electronic reading
Device or notebook computer）Or the field such as industrial large-sized electronic console.
Embodiment three
（1）There is the synthesis of the nano-silver thread of spherical Nano Silver on a kind of surface
Step one
Polyalcohol is added in reactor, is warming up to 150 DEG C, after nitrogen, then silver salt, metal salt, guiding is added dropwise
Agent is added in reactor, is reacted 4 hours, is obtained linear nano silver line；Wherein silver salt, polyalcohol, metal salt and guiding agent
Mass ratio is respectively：1：100：0.4：2；
Step 2
Linear nano silver line obtained by step one is redispersed in polyalcohol, silver salt and guiding agent is added,
After 55 DEG C are reacted 2 hours, then it is transferred into stainless steel autoclave, increases the temperature to and reacted again at 180 DEG C 7 hours,
Can obtain surface has the nano-silver thread of spherical Nano Silver；The wherein quality of linear nano silver line, polyalcohol, silver salt and guiding agent
Than being respectively：1：40：0.04：4；
The polyalcohol is：Neopentyl glycol；The silver salt is silver nitrate；The guiding agent is polyvinyl alcohol；The metal
Salt is vulcanized sodium；
(2) preparation of machine silicones
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：1：0.08：0.008：0.0001：0.0004；
The contents of ethylene of the low viscosity vinyl polysiloxane is 1 mol%, straight chain and branch that viscosity is 8000mPa.S
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
1%, viscosity is 45mPas；
The MQ resins are the vinyl MQ silicones of the mass content 2% of molecule medium vinyl, and viscosity is 8000mPa
s；
The inhibitor is：1- acetenyl -1- cyclohexanol；
The platinum catalyst is the platinum complex of divinyl tetramethyl disiloxane, and the platinum content is 5000
ppm；
(3) preparation of sulfydryl Fluoropolyether compound is held
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 6 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 1：10：0.005：4：0.4：
2；The fluorochemical polyether is preferably perfluor -2,5,8- trimethyl -3,6,9- trioxa lauroyl fluorine（CAS accession number 27639-98-
1）；
（4）The preparation of self-cleaning type flexible transparent conductive film
Step one
The nano-silver thread that there is spherical Nano Silver on above-mentioned surface is added in organic siliconresin, contained while adding end sulfydryl
Perfluoroalkyl polyether compound, stirs, and obtains a kind of mixing liquid；Wherein, there are the nano-silver thread of spherical Nano Silver, organosilicon in surface
The mass ratio of resin and end sulfydryl Fluoropolyether compound is respectively 1:10:0.04；
Step 2
Mixing liquid obtained by step one is sprayed on flexible transparent film surface, 110 DEG C, baking 1 are heated to
Hour, obtain the flexible transparent conductive film with self-cleaning function；Wherein quantity for spray of the mixing liquid in flexible transparent film
Than being sprayed on 0.8 square metre for 1g, flexible transparent film is commercialized PET（PET）Film table
Face.Flexible transparent conductive film with self-cleaning function can be applicable to hand-held electronic display（As mobile phone, tablet personal computer,
Electronic reader or notebook computer）Or the field such as industrial large-sized electronic console.
Example IV
（1）There is the synthesis of the nano-silver thread of spherical Nano Silver on a kind of surface
Step one
Polyalcohol is added in reactor, is warming up to 180 DEG C, after nitrogen, then silver salt, metal salt, guiding is added dropwise
Agent is added in reactor, is reacted 5 hours, is obtained linear nano silver line；Wherein silver salt, polyalcohol, metal salt and guiding agent
Mass ratio is respectively：1：120：0.4：4；
Step 2
Linear nano silver line obtained by step one is redispersed in polyalcohol, silver salt and guiding agent is added,
After 40 DEG C are reacted 2 hours, then it is transferred into stainless steel autoclave, increases the temperature to and reacted again at 190 DEG C 3 hours,
Can obtain surface has the nano-silver thread of spherical Nano Silver；The wherein quality of linear nano silver line, polyalcohol, silver salt and guiding agent
Than being respectively：1：40：0.04:3；
The polyalcohol is：Glycerine；The silver salt is silver perchlorate；The guiding agent is polyoxyethylene；The metal
Salt is platinum chloride；
（2）The preparation of organic siliconresin
Platinum catalyst is added in second low viscosity vinyl polysiloxane, containing hydrogen silicone oil, MQ resins and inhibitor system,
Stir and can obtain organic siliconresin；Wherein low viscosity vinyl polysiloxane, containing hydrogen silicone oil, MQ resins, inhibitor and platinum
The mass ratio of Au catalyst is respectively：1：0.1：0.007：0.0002：0.0002；
The contents of ethylene of the low viscosity vinyl polysiloxane is 1.2 mol%, straight chain and branch that viscosity is 500mPa.S
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
1%, viscosity is 34mPas；
The MQ resins are the vinyl MQ silicones of the mass content 1.5% of molecule medium vinyl, and viscosity is
8000mPa•s；
The inhibitor is：1- acetenyl -1- cyclohexanol；
The platinum catalyst is the platinum complex of divinyl tetramethyl disiloxane, and the platinum content is 4000
ppm；
（3）Hold the preparation of sulfydryl Fluoropolyether compound
Fluorochemical polyether is dissolved in tetrahydrofuran after adding lithium aluminium hydride reduction reaction 4 hours, obtains end and contain hydroxyl
The fluorochemical polyether solution of base；Thiocarbamide and hydrochloric acid are added in the fluorochemical polyether solution that terminad contains hydroxyl again, concentration of hydrochloric acid is
37%, react 3 hours, add excessive sodium hydroxide, react 6 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 1：14：0.008：4：0.4：
2；The fluorochemical polyether is preferably perfluor -2,5,8- trimethyl -3,6,9- trioxa lauroyl fluorine（CAS accession number 27639-98-
1）；
（4）The preparation of self-cleaning type flexible transparent conductive film
Step one
The nano-silver thread that there is spherical Nano Silver on above-mentioned surface is added in organic siliconresin, contained while adding end sulfydryl
Perfluoroalkyl polyether compound, stirs, and obtains a kind of mixing liquid；Wherein, there are the nano-silver thread of spherical Nano Silver, organosilicon in surface
The mass ratio of resin and end sulfydryl Fluoropolyether compound is respectively 1:30:0.04；
Step 2
Mixing liquid obtained by step one is sprayed on flexible transparent film surface, 110 DEG C, baking 1 are heated to
Hour, obtain the flexible transparent conductive film with self-cleaning function；Wherein quantity for spray of the mixing liquid in flexible transparent film
Than being sprayed on 0.8 square metre for 1g, flexible transparent film is commercialized PET（PET）Film.
Flexible transparent conductive film with self-cleaning function can be applicable to hand-held electronic display（Such as mobile phone, tablet personal computer, electronics
Reader or notebook computer）Or the field such as industrial large-sized electronic console.
Above is embodiments of the present invention are explained in detail, but the present invention is not limited to described embodiment party
Formula.For the ordinary skill in the art, in the case where not departing from the principle and objective of the present invention to these implementations
Mode carries out a variety of changes, modification, replacement and deformation and still fallen within the scope of the present invention.
Claims (5)
1. a kind of preparation method of the flexible transparent conductive film with self-cleaning function, it is characterised in that comprise the following steps：
Step one
The nano-silver thread that there is spherical Nano Silver on a kind of surface is added in organic siliconresin, while it is fluorine-containing poly- to add end sulfydryl
Ether compound, stirs, and obtains mixing liquid；Wherein, plant surface have the nano-silver thread of spherical Nano Silver, organic siliconresin and
The mass ratio for holding sulfydryl Fluoropolyether compound is respectively 1:10-50:0.01-0.05；
Step 2
Mixing liquid obtained by step one is sprayed on flexible transparent film surface, 80-120 DEG C, baking is heated to
0.5-2 hours, obtain the flexible transparent conductive film with self-cleaning function；Wherein mixing liquid is on flexible transparent film surface
Quantity for spray ratio be sprayed on 0.5-1 square metres for 1 gram.
2. the preparation method of the flexible transparent conductive film according to claim 1 with self-cleaning function, its feature exists
There is the preparation method of the nano-silver thread of spherical Nano Silver as follows in the surface：
Step one
Polyalcohol is added in reactor, is warming up to 120-200 DEG C, after nitrogen, then silver salt, metal salt is added dropwise and draws
Lead agent to be added in reactor, react 2-6 hours, obtain linear nano silver line；Wherein silver salt, polyalcohol, metal salt and guiding
The mass ratio of agent is respectively：1：20-200：0.1-0.5：0.5-5；
Step 2
Linear nano silver line obtained by step one is redispersed in polyalcohol, silver salt and guiding agent is added, 50-
After 60 DEG C are reacted 1-3 hours, then it is transferred into stainless steel autoclave, increases the temperature to anti-again at 160 DEG C -200 DEG C
Answer 4-8 hours, you can obtaining a kind of surface has the nano-silver thread of spherical Nano Silver；Wherein linear nano silver line, polyalcohol, silver salt
And the mass ratio of guiding agent is respectively：1：10-50：0.01-0.05:1-5；
Wherein described polyalcohol is：At least one of ethylene glycol, propane diols, glycerine, butanediol, neopentyl glycol；
The 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, iron chloride, frerrous chloride, copper chloride, platinum chloride, lemon
Lemon acid sodium, ascorbic acid or ammonium chloride.
3. the preparation method of the flexible transparent conductive film according to claim 1 with self-cleaning function, its feature exists
It is as follows in the preparation method of the organic siliconresin：
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 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 0.5- in molecule
1.6%, viscosity is 30-85mPas；
The MQ resins are the mass content 0.1-6.5% of molecule medium vinyl vinyl MQ silicones, and 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 platinum catalyst is the platinum complex of divinyl tetramethyl disiloxane, and the platinum content is 2000-7000
ppm。
4. the preparation method of the flexible transparent conductive film according to claim 1 with self-cleaning 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, then terminad contains thiocarbamide and hydrochloric acid added in the fluorochemical polyether solution of hydroxyl, and concentration of hydrochloric acid is 37%, reaction
2-5 hours, excessive sodium hydroxide is added, is reacted 5-10 hours, you can obtains 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 1：10-20：
0.001-0.1：3-6：0.1-0.5：1-3；The fluorochemical polyether is perfluor -2,5,8- trimethyl -3,6,9- trioxa lauroyls
Fluorine（CAS accession number 27639-98-1）.
5. the preparation method of the flexible transparent conductive film according to claim 1 with self-cleaning function, its feature exists
In the flexible transparent film be the macromolecule plastic film with certain pliability and excellent performance, the macromolecule plastic film
For commercialized PET（PET）Film.
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| CN106683795A (en) * | 2017-03-02 | 2017-05-17 | 苏州维业达触控科技有限公司 | Coating method of transparent conducting film and device for forming hydrophobic and oleophobic substance |
| CN107190295A (en) * | 2017-07-14 | 2017-09-22 | 中国科学院宁波材料技术与工程研究所 | A kind of super-double-hydrophobic surface of conductive material and preparation method thereof |
| CN110076070A (en) * | 2019-03-08 | 2019-08-02 | 广州碧然环保有限公司 | A kind of coating method for the super hydrophilic plastic film of the antifouling antistatic of automatically cleaning covering inorganic coating |
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