CN106898434B - A kind of manufacturing method of conductive heater transparent electrode - Google Patents
A kind of manufacturing method of conductive heater transparent electrode Download PDFInfo
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- CN106898434B CN106898434B CN201710110236.4A CN201710110236A CN106898434B CN 106898434 B CN106898434 B CN 106898434B CN 201710110236 A CN201710110236 A CN 201710110236A CN 106898434 B CN106898434 B CN 106898434B
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- transparent electrode
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- heating wire
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
- B60J1/00—Windows; Windscreens; Accessories therefor
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2203/00—Other substrates
- B05D2203/30—Other inorganic substrates, e.g. ceramics, silicon
- B05D2203/35—Glass
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2505/00—Polyamides
- B05D2505/50—Polyimides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2518/00—Other type of polymers
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/114—Deposition methods from solutions or suspensions by brushing, pouring or doctorblading
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/119—Deposition methods from solutions or suspensions by printing
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/32—After-treatment
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- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Surface Heating Bodies (AREA)
- Resistance Heating (AREA)
Abstract
A kind of manufacturing method of conductive heater transparent electrode, is related to transparent electrode.Benzene ring structure high polymer ink will be contained to be deposited on base material, form the thin layer working fluid of patterned array linear or micro-nano thickness；It will be oxygen-containing in the strand of the ink of high polymer containing benzene ring structure, functional group's gasification volatilization of the elements such as hydrogen, C C are left on strand, the functional groups such as C=C, complete the carbonizing and modifying of the polymer containing benzene ring structure, the thin layer working fluid of patterned array linear or micro-nano thickness on base material becomes the carbonization electric heating wire structure of transparent electrode, the carbonization electric heating wire structure mechanical performance on base material of transparent electrode is promoted again, the carbonization electric heating wire structure of transparent electrode after adhesive force is promoted completes building for conductive structure by power sourced electric busbar and connection terminal, obtain conductive heater transparent electrode.
Description
Technical field
The present invention relates to transparent electrodes, more particularly, to a kind of manufacturing method of conductive heater transparent electrode.
Background technology
Due to transparent electrode simultaneously have both high light transmittance and electric current input/output characteristic, as flat-panel screens,
The core material of the industrial fields such as solar cell, touch panel, transparent transistors, automobile heating glass electrode.Nowadays it dominates
Tin indium oxide (ITO) electrode in transparent electrode market is badly in need of seeking since increasingly lacking for indium resource causes its cost to be continuously improved
Seek some alternative transparent electrode materials；And ITO anti-seismic performances are poor, it is difficult to be applied to automobile and heat glass.F.Mirri
Deng (F.Mirri, et al, High-Performance Carbon Nanotube, 11,6 (2012) 9737-9744.) in forefathers
On the basis of combine fluosulfonic acid use dip-coating method, the obtained transparent electrode based on carbon nanotube, transparency 90%, sheet resistance
100Ω/sq.But the prior art is also difficult to manufacture high-purity single-walled carbon on a large scale, limits its commercialization.In recent years,
Metal based transparent electrode has obtained rapid development, and the existing wired heating windshield glass of automobile is also based on metal grill
Transparent electrode.U.S. patent Nos US5540961, which is disclosed, a kind of to be laid on superfine metal tungsten wire (20~50 μ m diameter)
Electric heated defrosting, demisting and the function of deicing, this scheme cost may be implemented in technical solution in the interlayer of automobile front windshield
It is higher, and can obviously observe the presence of filament in certain light-facing angle, influence beautiful and sight.Therefore have
Person proposes is applied to the wired heating windshield glass of automobile by the transparent electrode based on nano-silver thread.In the prior art, nanometer
The production method of silver wire transparent electrode is extremely complex, and such as world patent of invention WO2015/180222A1 discloses a kind of utilize and revolves
Nano-silver thread suspension is formed by curing nano-silver thread layer by painting technology coated on glass substrate surface, nano-silver thread mutually overlap and
Electrically conduct, but can only whole spin coating on the glass substrate, technological requirement is high, and the utilization rate of material is relatively low.Above method institute
The manufacture of the transparent electrode of announcement is very high to technological requirement, and production cost is higher.
Invention content
It is an object of the invention to be directed to existing conductive heater transparent electrode manufacturing cost height, complex process, heating
Defect in the electrode structure manufacturing method of automobile wind shield glass provides a kind of manufacturing method of conductive heater transparent electrode.
The present invention includes the following steps：
1) benzene ring structure high polymer ink will be contained to be deposited on base material, form patterned array linear or micro-nano thickness
Thin layer working fluid；
2) functional group of the elements such as oxygen-containing, hydrogen in the strand of the ink of high polymer containing benzene ring structure is gasified volatilization,
The functional groups such as C-C, C=C are left on strand, complete the carbonizing and modifying of the polymer containing benzene ring structure, the patterning battle array on base material
The thin layer working fluid of row linear or micro-nano thickness becomes the carbonization electric heating wire structure of transparent electrode, then promotes transparent electricity
The carbonization electric heating wire structure mechanical performance on base material of pole, the carbonization electric heating wire of the transparent electrode after adhesive force is promoted
Structure completes building for conductive structure by power sourced electric busbar and connection terminal, obtains conductive heater transparent electrode.
In step 1), the benzene ring structure high polymer ink that will contain is deposited on base material, by static spray printing or can be scraped
Coating method will contain benzene ring structure high polymer ink and be deposited on base material；Glass baseplate, PET base material, PVB bases can be used in the base material
One kind in material etc., preferably PVB base materials；It is contour that the high polymer ink can be selected from polyimides (PI), polyethyleneimine (PEI)
One kind in polymers；
In step 2), the function of the elements such as described oxygen-containing, hydrogen by the strand of the ink of high polymer containing benzene ring structure
Group's gasification volatilization, can be by the method for laser high energy induction regulating controlling, by containing in the strand of the ink of high polymer containing benzene ring structure
Functional group's gasification volatilization of the elements such as oxygen, hydrogen；The functional groups such as C-C, C=C are left on strand, to improve high polymer ink
Electric conductivity；The carbonization electric heating wire structure mechanical performance on base material for promoting transparent electrode again, can pass through microplating
Enhancement Method promotes the carbonization electric heating wire structure mechanical performance on base material of transparent electrode again；The high polymer ink is optional
One kind from the high polymers such as polyimides (PI), polyethyleneimine (PEI)；The setting of the electric heating wire be by with connect
Terminal provides thermal energy after being connected with power sourced electric busbar；Electric heating wire can be processed into different shapes according to design；The electricity
The line width of heater strip can be 1~50 μm, and thickness can be 100nm~5 μm；The light transmittance of gained conductive heater transparent electrode can be
About 50 Ω of 80%~95%, 5mm long lines impedance.The supply voltage applied on the electrode can be 5~220V, preferably 12V.
The present invention forms patterned lines structure by static spray printing or knife coating procedure on glass or transparent plastic substrate
Array or micro-nano thin layer working fluid utilize laser to scan the line image according to setting rule, induce it after dry
As conductive array structure, electric heating wire is configured to this, mechanicalness is obtained eventually by plating enhancing adhesive force technology
The excellent conductive heater transparent electrode manufacturing method of energy.Using the transparent electrode as the electrode knot of electrical heating automobile wind shield glass
Structure has many advantages, such as that translucency is good, impedance is low, electrode line width is small.
Description of the drawings
Fig. 1 is static spray printing/laser Collaborative Manufacturing apparatus platform schematic diagram used by the embodiment of the present invention.In Fig. 1,
Label A is taylor cone.
Fig. 2 is that the induced with laser high polymer ink carbonization of the embodiment of the present invention is patterned electricity heater strip schematic diagram.
Fig. 3 is blade coating/laser Collaborative Manufacturing apparatus platform schematic diagram used by the embodiment of the present invention.
Specific implementation mode
Invention is further described in detail in the following with reference to the drawings and specific embodiments.Specific implementation described herein
Example is only used to explain the present invention, is not intended to limit the present invention.
Referring to Fig. 1~3.
Embodiment 1
Static spray printing is to contain the materials such as benzene ring structure polymer ink such as polyimides (Polyimide) as workflow
Body, experimental provision plateform system is by glass evoked electrode 1, laser 2, XY motion platforms 3, pulsed high voltage generator 4 and collecting board 5
Compositions such as (glass, PET, PVB films).Direct write platform is powered by pulsed high voltage generator, is pumped using precise injection and is carried out solution
Supply, capillary glass electrode forms taylor cone under the action of electric field force, when the surface tension of electric field dynamic balance ink, ink
The on-demand spray printing direct write of water jet is in substrate.Carry out the experiment of spray printing direct write jet stream pin deposition, driving based on precision movement platform
Motion platform is by pre-set code track operation high polymer ink logo micro-nano structure deposition.While spray printing, laser association
Isogeneous induction is deposited on the patterning high polymer ink in substrate, and laser is as a kind of energetic particle beam, potential photon effect
The ink of high polymer containing phenyl ring is irradiated in short pulse with heat effect and carry out pyrolysis carbonization, finally realize that low-resistivity, carbon system are uniform
The conductive patterned electric heating wire 6 of distribution completes building for conductive structure by busbar and connection terminal 7, completes transparent electrode
Integrated circuit structure.
EHD spray printing partial parameters include that (the special limited public affairs of science and technology of alliance are moulded in Polyimide, Mw~300,000, Hangzhou to polyimides
Department) solution concentration：1%~10%, pulse voltage：<10kV；Frequency：<1kHz, platform movement speed：<30cm/s；Receive away from
From：10 μm~10mm, the material of glass evoked electrode is quartz glass；Tip dimensions are 1~500 μm, and laser is preferably joined
Number includes power：1~30W；Pulse frequency：1~1000Hz；Duty ratio：1%~100%；Wavelength：10.6μm；Movement speed：<
30cm/s；Waveform is pulse square wave.
Embodiment 2
Blade coating is to contain the materials such as benzene ring structure polymer ink such as polyimides (Polyimide) as working fluid.
Experimental provision platform is knife type coater, and system is by groups such as base material 8, scraper 9, feed bin 10, drying box 11 and conveyer systems 12
At.Under the drive of transmission system, base material is moved along direction of transfer.High polymer ink is scratched on base material using scraper,
The width of the baffle adjustable coating on scraper both sides.Scraping coating is subjected to certain pulling force, is continuously moved forward with cloth base, forms one
The thin layer high polymer ink of the micro-nano thickness of layer utilizes laser 13 under the control of XY motion platforms 14 according to default generation after dry
The code track scanning thin layer high polymer ink induces its carbonization for patterning micro-nano conductive array structure, realizes low-resistivity, carbon
It is equally distributed conductive patterned electric heating wire 6, building for conductive structure is completed by busbar and connection terminal 7, completes saturating
The integrated circuit structure of prescribed electrode.
It includes that polyimides (Polyimide, Mw~300,000, Hangzhou Surmount Science and Technology Co., Ltd.) is molten to scratch partial parameters
Liquid concentration：1%~50%；Working fluid thickness：100nm~5 μm；Conveyer belt movement speed：<30cm/s, laser are preferred
Parameter includes power：1W~30W；Pulse frequency：1-1000Hz；Duty ratio：1%~100%；Wavelength：10.6μm；Mobile speed
Degree：<30cm/s；Waveform is pulse square wave.
In order to improve the mechanical performance of conductive heater electrode structure, enhance carbon system electrode structure by the way of microplating
Adhesive force, ductility etc..Under the premise of not influencing electrode structure grid transparency, large-size carbon polarizing electrode structure machine may be implemented
The raising of tool performance etc., the metallic electrode structure of low impedance, narrow linewidth, size uniform, surfacing is obtained with this, and satisfaction is led
The use environment requirement of electrical heating automobile wind shield glass.
Using the above manufacturing method, advantageously process environments requirement is low, is manufactured into for the present invention and the prior art
This low, achievable large area continuously manufactures.Transparent electrode light transmittance obtained by this method is 80%~95%, 5mm long lines
About 50 Ω of impedance, electric heating wire line width are 1-50 μm, thickness is 100nm~5 μm, adhesive force >=4B, therefore can be satisfied with and lead
The electrode structure requirement of electrical heating automobile wind shield glass.
Claims (9)
1. a kind of manufacturing method of conductive heater transparent electrode, it is characterised in that include the following steps：
1) benzene ring structure high polymer ink will be contained to be deposited on base material, form patterned array linear or micro-nano thick thin
Layer working fluid；
2) functional group of the elements such as oxygen-containing, hydrogen in the strand of the ink of high polymer containing benzene ring structure is gasified volatilization, in molecule
C-C, C=C functional group are left on chain, complete the carbonizing and modifying of the polymer containing benzene ring structure, the patterned array lines on base material
The thin layer working fluid of structure or micro-nano thickness becomes the carbonization electric heating wire structure of transparent electrode, then promotes the carbon of transparent electrode
Change electric heating wire structure mechanical performance on base material, the carbonization electric heating wire structure of the transparent electrode after adhesive force is promoted is led to
It crosses power sourced electric busbar and connection terminal completes building for conductive structure, obtain conductive heater transparent electrode.
2. a kind of manufacturing method of conductive heater transparent electrode as described in claim 1, it is characterised in that described in step 1)
Benzene ring structure high polymer ink will be contained to be deposited on base material, be that benzene ring structure high polymer will be contained by static spray printing or knife coating procedure
Ink is deposited on base material.
3. a kind of manufacturing method of conductive heater transparent electrode as described in claim 1, it is characterised in that described in step 1)
Base material is using one kind in glass baseplate, PET base material, PVB base materials.
4. a kind of manufacturing method of conductive heater transparent electrode as claimed in claim 3, it is characterised in that the base material is PVB bases
Material.
5. a kind of manufacturing method of conductive heater transparent electrode as described in claim 1, it is characterised in that described in step 1)
The one kind of high polymer ink in polyimides, polyethyleneimine high polymer.
6. a kind of manufacturing method of conductive heater transparent electrode as described in claim 1, it is characterised in that described in step 2)
Oxygen-containing, protium functional group in the strand of the ink of high polymer containing benzene ring structure is gasified and is volatilized, is by laser high energy
Oxygen-containing, protium functional group in the strand of the ink of high polymer containing benzene ring structure is gasified and is volatilized by the method for induction regulating controlling,
C-C, C=C functional group are left on strand.
7. a kind of manufacturing method of conductive heater transparent electrode as described in claim 1, it is characterised in that described in step 2)
The carbonization electric heating wire structure mechanical performance on base material for promoting transparent electrode again, is promoted again by microplating Enhancement Method
The carbonization electric heating wire structure mechanical performance on base material of transparent electrode.
8. a kind of manufacturing method of conductive heater transparent electrode as described in claim 1, it is characterised in that described in step 2)
The setting of electric heating wire is by providing thermal energy after being connect with connection terminal and power sourced electric busbar.
9. a kind of manufacturing method of conductive heater transparent electrode as described in claim 1, it is characterised in that described in step 2)
The line width of electric heating wire is 1~50 μm, and thickness is 100nm~5 μm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710110236.4A CN106898434B (en) | 2017-02-28 | 2017-02-28 | A kind of manufacturing method of conductive heater transparent electrode |
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| CN201710110236.4A CN106898434B (en) | 2017-02-28 | 2017-02-28 | A kind of manufacturing method of conductive heater transparent electrode |
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| CN106898434A CN106898434A (en) | 2017-06-27 |
| CN106898434B true CN106898434B (en) | 2018-08-10 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1675059A (en) * | 2002-08-17 | 2005-09-28 | 3M创新有限公司 | Flexible electrically conductive film |
| CN101558456A (en) * | 2006-12-19 | 2009-10-14 | 陶氏环球技术公司 | Improved composites and methods for conductive transparent substrates |
| JP4401592B2 (en) * | 2001-03-30 | 2010-01-20 | 帝人株式会社 | Polymer resin laminate and automotive window material comprising the same |
| CN101687992A (en) * | 2007-07-06 | 2010-03-31 | 株式会社理光 | Diamine compound, polyamic acid, soluble polyimide, composition, wettability changing film, electrode, and method of manufacturing a wettability changing film |
| CN102474999A (en) * | 2009-08-03 | 2012-05-23 | 3M创新有限公司 | Process for forming optically clear conductive metal or metal alloy thin films and films made therefrom |
| CN104303267A (en) * | 2012-05-18 | 2015-01-21 | 尤尼皮克塞尔显示器有限公司 | Forming conductive patterns using ink comprising metal nanoparticles and nanowires |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6847024B2 (en) * | 1998-06-15 | 2005-01-25 | Trustees Of Dartmouth College | Prevention of ice formation by applying electric power to a liquid water layer |
| DE10015430C1 (en) * | 2000-03-28 | 2001-05-10 | Preh Elektro Feinmechanik | Capacitive sensor for detecting surface condensation, has passivation layer covering metallized capacitor electrodes covered by hydrophilic layer |
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- 2017-02-28 CN CN201710110236.4A patent/CN106898434B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4401592B2 (en) * | 2001-03-30 | 2010-01-20 | 帝人株式会社 | Polymer resin laminate and automotive window material comprising the same |
| CN1675059A (en) * | 2002-08-17 | 2005-09-28 | 3M创新有限公司 | Flexible electrically conductive film |
| CN101558456A (en) * | 2006-12-19 | 2009-10-14 | 陶氏环球技术公司 | Improved composites and methods for conductive transparent substrates |
| CN101687992A (en) * | 2007-07-06 | 2010-03-31 | 株式会社理光 | Diamine compound, polyamic acid, soluble polyimide, composition, wettability changing film, electrode, and method of manufacturing a wettability changing film |
| CN102474999A (en) * | 2009-08-03 | 2012-05-23 | 3M创新有限公司 | Process for forming optically clear conductive metal or metal alloy thin films and films made therefrom |
| CN104303267A (en) * | 2012-05-18 | 2015-01-21 | 尤尼皮克塞尔显示器有限公司 | Forming conductive patterns using ink comprising metal nanoparticles and nanowires |
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