CN108753147A - A kind of curable resin composition and a kind of transparent conductive film - Google Patents
A kind of curable resin composition and a kind of transparent conductive film Download PDFInfo
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- CN108753147A CN108753147A CN201810505551.1A CN201810505551A CN108753147A CN 108753147 A CN108753147 A CN 108753147A CN 201810505551 A CN201810505551 A CN 201810505551A CN 108753147 A CN108753147 A CN 108753147A
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- resin composition
- curable resin
- transparent conductive
- conductive film
- carbon nanotube
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The present invention relates to flexible transparent conducting film technical field more particularly to a kind of curable resin composition and transparent conductive films.In order to which the mist degree for solving existing transparent conductive film is higher, the relatively low problem of full light light transmittance, the present invention provides a kind of curable resin composition and transparent conductive film.And the problem of this invention also solves metal nanometer line and carbon nanotube adhesive force on base material.The curable resin composition includes ionizing radiation solidification reactivity matrix；Photoinitiator；Carbon nanotube；Metal nanometer line.The transparent conductive film includes base material and transparency conducting layer, and the conductive layer includes resin, carbon nanotube and metal nanometer line.The transparency conducting layer is formed after being cured by above-mentioned curable resin composition.Transparent conductive film provided by the invention has low haze, low resistance value, high full light light transmittance, good physical property and flexibility, and can apply to continuous web-like production, and production efficiency is high.
Description
Technical field
The present invention relates to flexible transparent conducting film technical field more particularly to a kind of curable resin composition and transparent lead
Electrolemma.
Background technology
Transparent conductive film refers to being less than 1000 Ω/ with visible light penetration for 80% or more and piece resistance value, according to
The difference of its electric conductivity can be used for liquid crystal display, resistance-type using difference when being less than 1000 Ω/ such as piece resistance value
Touch panel, electromagnetic wave proof, electrostatic prevention film；Piece resistance value can be used for capacitance type touch-control panel, organic in 40~300 Ω/
Light-emitting diode, electrical home appliances liquid crystal display panel, intelligent glass etc.；When piece resistance value is less than 10 Ω/, large-scale liquid crystal can be applied to
Show device, the Related products such as solar cell.
Indium tin oxide (abbreviation ITO) be metal oxide ceramic material, made by transparent conductive film have pole
Good optical transmission (T > 90%) and low-resistance value (piece resistance value is about 130~500 Ω/), being industrial quarters all the time makes
Object, manufacture craft is more mature (large-area coating film technique is made to be made with pattern etching), however the main member in ITO
Plain phosphide element belongs to rare earth mineral reserve, and source rests in a few countries such as China, South Korea, Japan, when reserves become fewer and fewer,
Its cost of material is easily had fluctuation drastically by the market demand.The problem of the problem of in addition to reserves and price, ITO encounters, is also
Have, it is necessary to be made under vacuum conditions using sputter, production equipment is expensive；It is higher that temperature is made, causes selected transparent
Material is limited；ITO material characters itself are more crisp, limit the bending angle of ito thin film, it is more difficult to be applied in Flexible Displays product.
In order to solve the above predicament, researchers develop a series of ITO alternative materials, wherein include the gold of non-ITO
Belong to oxidic transparent conductive film, such as antimony, the stannic oxide of oxygen doping, the zinc oxide etc. of the doping such as aluminium, gallium, although solving former material
The problem of expecting cost, but can not solve the problems, such as electric conductivity；Conducting polymer, such as polyacetylene (Polyacetylene), polyaniline
(Polyaniline), polypyrrole (Polypyrrole), polythiophene (Polythiophene) series etc., raw material be easy to get to and
Flexibility is had both, but electric conductivity and weatherability can not be solved the problems, such as after forming a film；Graphene transparent conductive film has good lead
Conductance hot property, but cost of manufacture is higher, does not have production；Metal grill transparent conductive film has low resistance value and higher wears
The advantage spent thoroughly, but its cable wider width, macroscopic pattern complex manufacturing technology；Carbon nanotube is flexible and price
The advantage of aspect, but because there are conductivity problems for its own characteristic, it is difficult to apply in touch screen；Metal nanometer line has good
Electric conductivity and flexibility, but it has that price and mist degree are higher.
In this case, start in the industry to learn from other's strong points to offset one's weaknesses to all material and develop blending proximate matter material, such as Chinese patent, it is public
The number of opening CN 101669177A (publication date is on March 10th, 2010), it is proposed that fullerene, list is respectively set in one kind in membrane material
The double-layer transparent conductive film of wall carbon nano tube；Chinese patent, (publication date is January 28 in 2015 to publication number CN 104318981A
Day), it is proposed that a kind of metal nanometer line, the compound transparent conductive film of carbon nanotube.
But it although can be reached by product obtained by above-mentioned patent document reduces piece resistance value, is led applied to transparent
On electrolemma, but mist degree is higher, and full light light transmittance is relatively low, to be improved in physical property, and may not apply to continuous web-like
Production.
Invention content
In order to which the mist degree for solving existing transparent conductive film is higher, the relatively low problem of full light light transmittance, the present invention provides one
Kind curable resin composition and a kind of transparent conductive film.This invention also solves metal nanometer line and carbon nanotube are on base material
The relatively low problem of adhesive force.Transparent conductive film provided by the invention has low haze, low resistance value, high full light light transmittance, good
Good physical property and flexibility, and continuous web-like production is can apply to, production efficiency is high.
In order to solve the above technical problems, the present invention adopts the following technical scheme that：
A kind of curable resin composition, the curable resin composition include：
(1) ionizing radiation solidification reactivity matrix；
(2) photoinitiator；
(3) carbon nanotube；
(4) metal nanometer line；
Wherein, the carbon nanotube and the solid content accounting of metal nanometer line are 5~20%, the solid content accounting
Ionizing radiation solidification reactivity matrix, carbon nanotube and metal nanometer line are accounted for for the sum of the weight of carbon nanotube and metal nanometer line
The ratio of the sum of three's weight；The mass ratio of the carbon nanotube and metal nanometer line is 3-4:5.
Ionizing radiation solidification reactivity matrix is alternatively referred to as light-cured resin.
When carbon nanotube and the solid content accounting of metal nanometer line are more than 20% or carbon nanotube and metal nanometer line
Mass ratio is less than 3:When 5, mist degree can be caused to get higher；When carbon nanotube and the solid content accounting of metal nanometer line be less than 5% or
The mass ratio of carbon nanotube and metal nanometer line is more than 4:When 5, transparency variation, electric conductivity can be caused to be deteriorated.
Further, a diameter of 30~60nm of the metal nanometer line, length are 10~30 μm.
Further, a diameter of 5~20nm of the carbon nanotube, length are 5~20 μm.
When the diameter of metal nanometer line is excessive or the long transparency conducting layer that can be resulted in of length, the transparency declines, mist
Degree increases；The electrically conducting transparent synusia resistance value that can be resulted in when the diameter of carbon nanotube is too short or length is too short is higher, conductive
Degradation.
Further, the metal nanometer line in nano silver wire, copper nano-wire, nanowires of gold or aluminium nano wire one
Kind or at least two combination.
Further, the metal nanometer line is preferably nano silver wire.
Further, the ionizing radiation solidification reactivity matrix is selected from aliphatic urethane acrylate, polyurethane (first
Base) in acrylate, epoxy (methyl) acrylate, polyester (methyl) acrylate or acrylic resin
One kind or at least two combination.
Aforementioned acrylic resin refers to pure acrylic resin.
Further, the ionizing radiation solidification reactivity matrix is selected from aliphatic urethane acrylate oligomer, fat
Fat race urethane diacrylate oligomer, tripropylene glycol diacrylate or aliphatic dipentaerythritol acrylate monomer
In one kind or at least two combination.
Further, the ionizing radiation solidification reactivity matrix includes the first response matrix and the second response matrix.Institute
It states the first response matrix and is selected from aliphatic urethane acrylate oligomer；Second response matrix is selected from aliphatic polyurethane
Diacrylate ester oligomer, tripropylene glycol diacrylate, aliphatic dipentaerythritol acrylate monomer or aliphatic poly ammonia
One kind in ester acrylate oligomer or at least two combination.
Further, second response matrix is preferably aliphatic urethane diacrylate oligomer or tripropylene glycol
One kind in diacrylate or combination.
Hard conating is formed in order to make the resin in curable resin composition crosslink reaction, in curable resin composition
It is also added into photoinitiator.Photoinitiator used in the present invention does not specially require, as long as curing of coatings may be implemented
Various types of photoinitiators.
Further, the photoinitiator is selected from cracking type initiator or one kind in photoinitiator (hydrogen-abstraction) or extremely
Few two kinds of combination.
Further, the cracking type initiator is selected from 1- hydroxy-cyclohexyls phenyl ketone (184), 2- hydroxy-methyl phenyl
Propane -1- ketone (1173), 2- methyl-1s-(4- methyl mercaptos phenyl) -2- morpholinyl -1- acetone (907), benzoin dimethylether
(651) or one kind in 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxides (TPO) or at least two combination.
Further, the photoinitiator (hydrogen-abstraction) is selected from benzophenone (BP) or 2- isopropyl thioxanthones
(ITX) one kind in or combinations thereof.
Further, the photoinitiator is preferably 1- hydroxy-cyclohexyls phenyl ketone (184).
Further, the curable resin composition further includes levelling agent and solvent.
The present invention also provides a kind of transparent conductive film, the transparent conductive film includes base material and transparency conducting layer, described to lead
Electric layer includes resin, carbon nanotube and metal nanometer line；The carbon nanotube and metal nanometer line are by resin-bonded in base material
Surface.
The transparency conducting layer is also known as conductive layer.
Further, the transparency conducting layer is obtained by curable resin composition by coating, dry, film-forming.
Further, the mist degree of the transparent conductive film is less than 1.0%, and total light transmittance is more than 90%, piece resistance value 50
~150 Ω/.
Further, a diameter of 30~60nm of the metal nanometer line, length are 10~30 μm；The carbon is received
A diameter of 5~20nm of mitron, length are 5~20 μm.
Further, the resin is selected from polyurethane (methyl) acrylate, epoxy (methyl) acrylate tree
Fat, polyester (methyl) acrylate or one kind in acrylic resin or at least two combination.
Further, the conductive layer is formed after being cured by curable resin composition of the present invention.
Further, the base material is plastic film.
Further, the material of the plastic film is selected from polyethylene terephthalate (PET), poly- naphthalenedicarboxylic acid
Glycol ester PEN (polyethylene naphthalate), polycarbonate film (PC), polymethyl methacrylate film
(PMMA), acrylonitrile-butadiene-styrol copolymer (ABS) and PET laminated films, the laminated film of PC and PMMA, polyethers
Ether ketone (polyether ether ketone；PEEK), cellulose diethylester (diacetylcellulose), cellulose iii second
Ester (triacetylcellulose；TAC), under acrylic resin (acrylic resin) or aromatic metal class catalyst action
The one kind polymerizeing in obtained cyclic olefine copolymer (metallocene catalyzed cyclo olefin copolymer)
Or at least two combination.
Further, the base material is preferably polyethylene terephthalate (PET) film, polycarbonate film (PC)
Or cellulose iii ethyl ester (TAC) film.
Further, the base material is most preferably polyethylene terephthalate (PET) film.
Further, the thickness of the base material is 50 μm~250 μm.When the thickness is less than 50 μm, mechanical strength will not
It is enough, and cured film deformation is too big in solidification；When thickness is more than 250 μm, increase difficulty of processing, therefore, above range it
Outer thickness is worthless.
Further, the thickness of the plastic film is preferably 125~250 μm.
Further, the base material preferably clear, the light transmission rate of the transparent membrane is in 400nm~700nm wavelength
Total light transmittance is preferably 90% or more in range.
Further, the transparent conductive film further includes priming coat, the primer-layer-coated base material one or two
Surface.
Further, one or two surface of base material can be handled or be surface-treated with priming coat.Into one
Step, the surface treatment forms rough surface selected from sandblasting or etching or oxidation is surface-treated, and is applied to enhance surface
The adhesive force of layer and base material.
Further, the oxidation carries out surface treatment and is selected from Corona discharge Treatment, using the processing of flame, utilize etc. from
The processing of son, or handled using ultraviolet irradiation in the presence of ozone.
It is surface-treated the demand processed with back segment according to the characteristic of stromal surface suitably to be selected, in general, from operable
Property with performance consider consider, preferentially select bottom precoating treatment.
Further, the thickness of the transparency conducting layer is 1 μm~3 μm.
To the painting thickness of the transparency conducting layer (also referred to as flexible and transparent conductive layer) in transparent conductive film provided by the invention
Degree control is at 1 μm~3 μm, and when more than 3 μm, the flexibility of transparent conductive film is deteriorated, and when being less than 1 μm, hardness is bad, in the later stage
Scuffing is easy tod produce in roll-to-roll production process, difficulty of processing becomes larger.
Further, the hardness of the transparency conducting layer is 1H.
Further, the transparency conducting layer is formed by the coating production of continuous web-like.
Further, polyurethane (methyl) acrylate is selected from aliphatic polyurethane three (methyl) acrylate, fat
Fat adoption urethane four (methyl) acrylate, aliphatic polyurethane five (methyl) acrylate, aliphatic polyurethane six (methyl)
Acrylate, aromatic urethane three (methyl) acrylate, aromatic urethane four (methyl) acrylate, fragrant adoption ammonia
(methyl) acrylate of ester five or one kind in aromatic urethane six (methyl) acrylate or at least two combination.
Further, epoxy (methyl) acrylate is selected from epoxy acrylate, epoxy methacrylates, modification
Epoxy acrylate, 2- hydroxyl -3- benzene oxygen propyl groups acrylate, fatty acid modified epoxy acrylate, modified bisphenol A epoxy third
Olefin(e) acid ester, epoxy soybean oil acrylate or one kind in modified six function based epoxy acrylates or at least two combination.
Further, polyester (methyl) acrylate is selected from polyester acrylate, modified polyester acrylate ester, four officials
It can base polyester acrylate, fatty acid modified polyester hexaacrylate, polyester chloride acrylic acid or hyperbranched polyester acrylic ester
In one kind or at least two combination.
Further, the ionizing radiation matrix preferred aliphat urethane acrylate.
Further, the curable resin composition further includes levelling agent.
Further, the levelling agent can improve the flatness of coating, the defects of to reduce volcanic crater, pin hole.
Further, the levelling agent is selected from fluorine system, organosiloxane or organic-silicon-modified acrylic acid levelling agent.
Further, the levelling agent is preferably organosiloxane.
Further, it is chemical (Dainippon Ink& Chemicals) to be selected from big Japanese ink for the levelling agent
MEGAFACE F440, F445, F470, F553, F554, F556, Bi Ke chemistry (BYK Additive&Instruments)
BYK-333, BYK-377, BYK-378 win Flow 300, Flow 370, Flow 425, the Rad of wound Degussa (EVONIK)
2200N, Rad 2250, Rad 2300, the Levaslip 835 of the modest chemistry of moral, Levaslip 837, Levaslip 867 or
One kind in Levaslip 879 or at least two combination.
Further, the curable resin composition includes：First 4-6 parts of response matrix, the second response matrix 1.2-3.1
Part, 0.02-0.03 parts of levelling agent, 0.30-0.34 parts of photoinitiator, 0.13-0.7 parts of carbon nanotube, nano silver wire 0.22-0.88
Part.The number is parts by weight.
Further, the curable resin composition includes：First 4-6 parts of response matrix, the second response matrix 1.2-3.1
Part, 0.02-0.03 parts of levelling agent, 0.30-0.34 parts of photoinitiator, 0.13-0.7 parts of carbon nanotube, nano silver wire 0.22-0.88
Part, 17-25.5 parts of organic solvent.The number is parts by weight.
Further, the curable resin composition includes：First 4-5.1 parts of response matrix, the second response matrix 1.5-
3.1 parts, 0.03 part of levelling agent, 0.31-0.33 parts of photoinitiator, 0.13-0.31 parts of carbon nanotube, nano silver wire 0.22-0.48
Part.The number is parts by weight.
Further, the curable resin composition includes：First 4-5.1 parts of response matrix, the second response matrix 1.5-
3.1 parts, 0.03 part of levelling agent, 0.31-0.33 parts of photoinitiator, 0.13-0.31 parts of carbon nanotube, nano silver wire 0.22-0.48
Part, 19.1-20.5 parts of organic solvent.The number is parts by weight.
Further, the curable resin composition further includes solvent, to form hard coat layer coating solution of the present invention.
As needed, solvent can also be added in curable resin composition, to form hard coat layer coating solution of the present invention.It is described
Solvent is selected from organic solvent.The organic solvent is in alcohols, aliphatic hydrocarbon, arene, halogenated hydrocarbons, ketone or ester
One kind or at least two combination.
Further, the alcohols is selected from methanol, ethyl alcohol, normal propyl alcohol, isopropanol, one kind in n-butanol or isobutanol or
At least two combination.
Further, the combination of the one kind or at least two of aliphatic hydrocarbon in hexane, heptane or hexamethylene.
Further, the combination of the one kind or at least two of the arene in benzene, toluene or dimethylbenzene.
Further, the halogenated hydrocarbons is selected from dichloromethane, one kind or at least two in dichloroethanes or carbon tetrachloride
Combination.
Further, the ketone is selected from acetone, butanone, methyl ethyl ketone, and one in methyl iso-butyl ketone (MIBK) or cyclohexanone
Kind or at least two combination.
Further, the ester is selected from methyl acetate, ethyl acetate, one kind in propyl acetate or butyl acetate or extremely
Few two kinds of combination.
Further, one kind in the preferred butanone of the solvent, toluene or isopropanol or at least two combination.
The concentration and viscosity of coating fluid can purpose according to the present invention suitably selected, with the subsequent processing of profit.
Further, the preparation method of the curable resin composition is：By ionizing radiation solidification reactivity stromatolysis
Into solvent, carbon nanotube and nano silver wire are added after stirring, levelling agent and photoinitiator are added after stirring, is consolidated after stirring
Change resin combination.
Further, the preparation method of the transparent conductive film is：Curable resin composition is applied to substrate surface, is done
It is dry, then with ultraviolet light curing, formation transparency conducting layer.
The coating method of flexible and transparent conductive layer to forming the present invention is not particularly limited, as long as this hair can be formed
Bright hard conating.
Further, the coating method is selected from stick coating method, scraper for coating method, Mayer stick coating methods, rolling method, scraper plate painting
Cloth method, item stitch rubbing method or micro-gravure coating process.
Further, the coating method is preferably item seam rubbing method.
Further, the ultraviolet lamp is selected from high-pressure sodium lamp, merges H lamps or xenon lamp.
Further, the light dosage for being used for irradiation is 200~1000mj/cm2。
Further, it is preferably 200-400mj/cm for the light dosage of irradiation2。
Further, the carbon nanotube and the solid content accounting of metal nanometer line are 5~10%；Carbon nanotube and
The mass ratio of metal nanometer line is 3-3.2:5；A diameter of 10~20nm of carbon nanotube, length are 20 μm；Nano silver wire it is straight
Diameter is 30~60nm, and length is 30 μm；It is low that the ionizing radiation solidification reactivity matrix is selected from aliphatic urethane acrylate
At least two combination in polymers, aliphatic urethane diacrylate oligomer or tripropylene glycol diacrylate；The stream
Flat agent is the levelling agent with polydimethylsiloxaneskeleton skeleton structure；The initiator is 184；The solvent is butanone, toluene
One kind in isopropanol or at least two combination；It is 125-250 μm of light that above-mentioned curable resin composition, which is coated to thickness,
On one face of the pet film of classes and grades in school；After 80 DEG C of coatings to formation are dried 2 minutes, with
200-400mJ/cm2Light quantity, by ultraviolet light irradiation dry coating is cured, obtain flexible transparent conducting film.On
It includes embodiment 1-2 to state technical solution.
Compared with prior art, the present invention by control curable resin composition in carbon nanotube, metal nanometer line it is straight
Diameter, length and additive amount, the mist degree for solving existing transparent conductive film is higher, the relatively low problem of full light light transmittance, piece resistance value
Control solves metal nanometer line and carbon nanotube on base material in 50~150 Ω/ by the way that curable resin composition is made
The relatively low problem of adhesive force, and be applicable to continuous web-like production, improve production efficiency.
Description of the drawings
Fig. 1 is the structural schematic diagram of transparent conductive film provided by the invention.
Specific implementation mode
The present invention is specifically described with reference to specific embodiment, but the present invention is not limited thereto.
The preparation method of curable resin composition provided by the invention is：Ionizing radiation solidification reactivity stromatolysis is arrived
In solvent, carbon nanotube and nano silver wire are added after stirring, levelling agent and photoinitiator are added after stirring, is cured after stirring
Resin combination.
The preparation method of transparent conductive film provided by the invention is：Curable resin composition is applied to substrate surface, is done
It is dry, then with ultraviolet light curing, formation transparency conducting layer.
The test method of the main performance of transparent conductive film provided by the invention is as follows：
(1) coating layer thickness is tested
System is tested using coating thickness detector ETA-SST thickness, the thickness of transparency conducting layer is tested using optical diffraction principle.
(2) mist degree, total light transmittance test
It is surveyed using light transmission using Japanese electric color NDH 2000N type mist degree analyzers according to JIS K-7105 standards
It is fixed.
(3) adhesive force is tested
According to standard JIS K-5600, hundred lattice are marked on hardening coat surface using cross-cut tester, reuse 3M, #600 adhesive tapes
Carry out viscous glutinous, observation coating surface falls off situation.
(4) pencil hardness test
According to GB/T6739-1996 standards product pencil hardness is measured using 3086 pencil hardometers of Elcometer.
Measure gimmick：The use of hardness is that H~3H Mitsubishis pencil marks 5 lines under 500g loadings, then observation hardening membrane coat has
Judged without scuffing, and according to following standard.
Criterion：
0~1 is scratched, is judged " Pass " (qualification)；
2~5 are scratched, is judged " NG " (unqualified).
(5) resistance to steel wool test
Using the Kunshan good instrument A20-339 testing machines of resistance to steel wool of essence in 100g/cm2Loading under, use #0000 steel wires
Suede rubs 10 times back and forth on hard coating surface, and frictional distance is 5~6cm, confirms that whether there is or not scuffings for coating.
Criterion：
0 is scratched, is judged " Pass " (qualification)；
Shang≤1 Hua judges " NG " (unqualified).
(6) flexibility is tested
Print is cut into：The strip of long 10cm × wide 2cm shapes, outward with hardening coat (i.e. transparency conducting layer), Yu Zhi
The case where being wound on the rod iron that diameter is 2.0cm, rear One step development, observing the hair check on hardening coat surface, and according to a subscript
Standard is assessed：
It has no crackle, cracking, is calculated as " ◎ " (outstanding)；
There is slight slight crack, have no cracking, is calculated as " △ " (qualification)；
There is apparent slight crack, cracking, is calculated as "×" (unqualified).
(7) piece resistance value is tested
It is measured using the auspicious four probe piece resistance value analyzer of section's great achievement FT331 types in Ningbo.
Embodiment 1
A kind of curable resin composition of present invention offer and transparent conductive film, the curable resin composition include that ionization is put
Penetrate solidification reactivity matrix；Photoinitiator；Carbon nanotube；Metal nanometer line；The transparent conductive film includes base material 20 and transparent
Conductive layer 10 (as shown in Figure 1), the conductive layer include resin, carbon nanotube and metal nanometer line；The carbon nanotube and gold
Belong to nano wire by resin-bonded on the surface of base material；The conductive layer is coated with by curable resin composition, is formed after solidification.Gu
The formula for changing resin combination is as follows：
Aliphatic urethane acrylate oligomer (the TaiWan, China Changxing Chemical Industry Co Ltd of 5.1kg
Manufacture, trade name：Etercure 6195-100) and 1.5kg aliphatic urethane diacrylates oligomer (TaiWan, China is long
Learn Industries, Inc's manufacture, trade name in Xinghua：Etercure 611A-85) it is dissolved into the butanone of 19.1kg, it stirs
0.13 kg carbon nanotubes (20 μm of length, diameter 10nm), 0.22kg nano silver wires (30 μm of length, diameter are added after twenty minutes
60nm), after twenty minutes, then adding 0.03kg has levelling agent (the Bi Ke chemistry of polydimethylsiloxaneskeleton skeleton structure for stirring
Manufacture；Trade name：BYK-377) and 0.31kg photoinitiators (TaiWan, China Double Bond Chemical Ind.,Co.,Ltd. manufacture, commodity
Name：Doublecure 184), after stirring 30 minutes, obtain curable resin composition.
Above-mentioned curable resin composition is coated to the pet film that thickness is 250 μm of optical grades
(company's manufacture, trade name are spun by Japanese Japan；A4300 on a face).After 80 DEG C of coatings to formation are dried 2 minutes,
With 200mJ/cm2Light quantity, by ultraviolet light irradiation dry coating is cured, obtain flexible transparent conducting film.Specifically
Evaluation test the results are shown in Table 1.
Embodiment 2
The curable resin composition and transparent conductive film provided such as embodiment 1.
The formula of curable resin composition is as follows：
The aliphatic urethane acrylate oligomer of 4kg, (TaiWan, China Double Bond Chemical Ind.,Co.,Ltd. manufactures, quotient
The name of an article：Doublemer 5812) and 3.1kg tripropylene glycol diacrylates (the limited public affairs of TaiWan, China Changxing chemical industry share
Department's manufacture, trade name：EM 223) it is dissolved in the toluene of 15.5kg and the isopropyl alcohol mixed solvent of 5.0kg, stirring is after twenty minutes
0.31kg carbon nanotubes (20 μm of length, diameter 20nm) are added, 0.48kg nano silver wires (30 μm of length, diameter 60nm) stir
It mixes after twenty minutes, then adding 0.03kg has levelling agent (the Bi Ke chemistry manufacture of polydimethylsiloxaneskeleton skeleton structure；Commodity
Name：BYK-377) and 0.33kg photoinitiators (TaiWan, China Double Bond Chemical Ind.,Co.,Ltd. manufacture, trade name：
Doublecure 184), after stirring 30 minutes, obtain curable resin composition.
Above-mentioned curable resin composition is coated to the pet film that thickness is 125 μm of optical grades
(toray company manufactures, trade name；U483 on a face).After 80 DEG C of coatings to formation are dried 2 minutes, with
400mJ/cm2Light quantity, by ultraviolet light irradiation dry coating is cured, obtain flexible transparent conducting film.Specifically comment
Valence test result is shown in Table 1.
Embodiment 3
The curable resin composition and transparent conductive film provided such as embodiment 1.
The formula of curable resin composition is as follows：
The aliphatic urethane acrylate oligomer of 5.0kg, (Sartomer Chemical Co., Ltd. manufactures, trade name：
) and 1.5kg aliphatic urethane diacrylates oligomer (TaiWan, China Changxing Chemical Industry Co Ltd CN9010NS
Manufacture, trade name：It 611A-85) is dissolved in the butanone of 13.0kg and the isopropyl alcohol mixed solvent of 6.5kg, stirring is after twenty minutes
0.30kg carbon nanotubes (20 μm of length, diameter 20nm) are added, 0.43kg nano silver wires (30 μm of length, diameter 60nm) stir
It mixes after twenty minutes, then adding 0.02kg has levelling agent (the big Japanese ink chemistry manufacture of fluorine element structure；Trade name：
Megaface F444) and 0.30kg photoinitiators (manufacture of TaiWan, China Double Bond Chemical Ind.,Co.,Ltd., trade name：
Doublecure 184), after stirring 30 minutes, obtain curable resin composition.
Above-mentioned curable resin composition is coated to the pet film that thickness is 125 μm of optical grades
(Mitsubishi Resins Corporation manufactures, trade name；O321E on a face).80 DEG C to the coating of formation dry 2 minutes it
Afterwards, with 400mJ/cm2Light quantity, by ultraviolet light irradiation dry coating is cured, obtain flexible transparent conducting film.Tool
Body evaluation test the results are shown in Table 1.
Embodiment 4
The curable resin composition and transparent conductive film provided such as embodiment 1.
The formula of curable resin composition is as follows：
The aliphatic urethane acrylate oligomer of 6.0kg, (Sartomer Chemical Co., Ltd. manufactures, trade name：
CN9006NS) and 1.2kg aliphatic urethane acrylates oligomer (Sartomer Chemical Co., Ltd. manufacture, trade name：
CN8884NS it) is dissolved in the butanone of 17.0kg and the isopropyl alcohol mixed solvent of 8.5kg, 0.52kg is added in stirring after twenty minutes
Carbon nanotube (5 μm of length, diameter 5nm), 0.75kg nano silver wires (10 μm of length, diameter 30nm), stirring after twenty minutes, connect
Addition 0.03kg has levelling agent (the De Qian Chemical Co., Ltd.s manufacture of polydimethylsiloxaneskeleton skeleton structure；Trade name：
Levaslip 432) and 0.34kg photoinitiators (manufacture of TaiWan, China Double Bond Chemical Ind.,Co.,Ltd., trade name：
Doublecure 184), after stirring 30 minutes, obtain flexible transparent conducting film curable resin composition.
Above-mentioned curable resin composition is coated to the pet film that thickness is 50 μm of optical grades
(Hefei Lucky Science & Technology Industry Co., Ltd. manufactures, trade name；PG52H on a face).It is dried in 80 DEG C of coatings to formation
After 2 minutes, with 500mJ/cm2Light quantity, by ultraviolet light irradiation dry coating is cured, obtain flexible and transparent and lead
Electrolemma.Specific evaluation test the results are shown in Table 1.
Embodiment 5
The curable resin composition and transparent conductive film provided such as embodiment 1.
The formula of curable resin composition is as follows：
The aliphatic urethane acrylate oligomer of 4.0kg, (Sartomer Chemical Co., Ltd. manufactures, trade name：
) and 2.3kg aliphatic dipentaerythritol acrylate monomers (TaiWan, China Changxing Chemical Industry Co Ltd CN9010NS
Manufacture, trade name：EM 2696) it is dissolved in the butyl acetate of 17.0kg, 0.70kg carbon nanotubes are added in stirring after twenty minutes
(10 μm of length, diameter 5nm), 0.88kg nano silver wires (20 μm of length, diameter 30nm), stirring after twenty minutes, are then added
0.03kg has levelling agent (the De Qian Chemical Co., Ltd.s manufacture of polydimethylsiloxaneskeleton skeleton structure；Trade name：Levaslip
432) (TaiWan, China Double Bond Chemical Ind.,Co.,Ltd. manufactures, trade name with 0.30kg photoinitiators：Doublecure 184),
After stirring 30 minutes, curable resin composition is obtained.
Above-mentioned curable resin composition is coated to the pet film that thickness is 50 μm of optical grades
(Hefei Lucky Science & Technology Industry Co., Ltd. manufactures, trade name；PG52H on a face).It is dried in 80 DEG C of coatings to formation
After 2 minutes, with 500mJ/cm2Light quantity, by ultraviolet light irradiation dry coating is cured, obtain flexible and transparent and lead
Electrolemma.Specific evaluation test the results are shown in Table 1.
Comparative example 1
The curable resin composition and transparent conductive film provided such as embodiment 1.
The formula of curable resin composition is as follows：
Conductive film is prepared with step same as Example 1, except that：Change carbon nanotube and nano silver wire
Additive amount improves the mass ratio of carbon nanotube and nano silver wire.Specific evaluation test the results are shown in Table 1.
Comparative example 2
The curable resin composition and transparent conductive film provided such as embodiment 1.
The formula of curable resin composition is as follows：
Conductive film is prepared with step same as Example 1, except that：Change carbon nanotube and nano silver wire
Additive amount reduces the mass ratio of carbon nanotube and nano silver wire.Specific evaluation test the results are shown in Table 1.
Comparative example 3
The curable resin composition and transparent conductive film provided such as embodiment 1.
The formula of curable resin composition is as follows：
Aliphatic urethane acrylate class hardening bath (big Japanese ink chemistry manufacture, the trade name of 15.5kg：
GRANDIC PC11-7041 effectively consolidate ingredient 55%) it is dissolved into the butanone of 19.1kg, 0.11kg is added in stirring after twenty minutes
Carbon nanotube (10 μm of length, diameter 5nm), 0.15kg nano silver wires (20 μm of length, diameter 30nm), stirring after twenty minutes, add
Add 0.02kg that there is levelling agent (the big Japanese ink chemistry manufacture of fluorine element structure；Trade name：Megaface F477), consolidate
Change resin combination.The accounting of carbon nanotube and nano silver wire in the composition is too low.
It is thin that above-mentioned curable resin composition is coated to the polyethylene terephthalate that thickness is 125 micrometer optical grades
(company's manufacture, trade name are spun to film by Japanese Japan；A4300 on a face).It is dried 2 minutes in the 80-90 DEG C of coating to formation
Later, with 500mJ/cm2Light quantity, by ultraviolet light irradiation dry coating is cured, obtain conductive film.Specific evaluation
Test result is shown in Table 1.
The performance test results for the transparent conductive film that 1 embodiment 1-5 of table and comparative example 1-3 are provided
Transparent conductive film provided by the invention has low haze, low resistance value, high full light light transmittance, good physical
Energy and flexibility, comprehensive performance are good.Particularly, the comprehensive performance for the transparent conductive film that embodiment 1-2 is provided is more preferable, Quan Guang
Line transmitance be at least 90.3%, mist degree be up to 0.83%, adhesive force 5B, pencil hardness 1H, without scratch, flexibility it is excellent
Elegant and piece resistance value is at least 103 Ω/.
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the scope of the present invention.It is every
The equivalent changes and modifications done according to the content of present invention are encompassed by the scope of the claims of the present invention.
Claims (10)
1. a kind of curable resin composition, which is characterized in that the curable resin composition includes：
(1) ionizing radiation solidification reactivity matrix；
(2) photoinitiator；
(3) carbon nanotube；
(4) metal nanometer line；
Wherein, the carbon nanotube and the solid content accounting of metal nanometer line are 5~20%, and the solid content accounting is carbon
The sum of the weight of nanotube and metal nanometer line accounts for ionizing radiation solidification reactivity matrix, carbon nanotube and metal nanometer line three
The ratio of the sum of weight；The mass ratio of the carbon nanotube and metal nanometer line is 3-4:5.
2. curable resin composition according to claim 1, which is characterized in that a diameter of the 30 of the metal nanometer line
~60nm, length are 10~30 μm.
3. curable resin composition according to claim 1, which is characterized in that a diameter of the 5 of the carbon nanotube~
20nm, length are 5~20 μm.
4. curable resin composition according to claim 1, which is characterized in that the ionizing radiation solidification reactivity matrix
Selected from aliphatic urethane acrylate, polyurethane (methyl) acrylate, epoxy (methyl) acrylate, polyester
One kind in (methyl) acrylate or acrylic resin or at least two combination.
5. curable resin composition according to claim 1, which is characterized in that the curable resin composition further includes stream
Flat agent and solvent.
6. a kind of transparent conductive film, which is characterized in that the transparent conductive film includes base material and transparency conducting layer, the conductive layer
Including resin, carbon nanotube and metal nanometer line；The carbon nanotube and metal nanometer line pass through the resin-bonded table in base material
Face.
7. transparent conductive film according to claim 6, which is characterized in that a diameter of the 30 of the metal nanometer line~
60nm, length are 10~30 μm；A diameter of 5~20nm of the carbon nanotube, length are 5~20 μm.
8. transparent conductive film according to claim 6, which is characterized in that the resin is selected from polyurethane (methyl) propylene
Acid ester resin, epoxy (methyl) acrylate, polyester (methyl) acrylate or one kind in acrylic resin or
At least two combination.
9. transparent conductive film according to claim 7, which is characterized in that the conductive layer is by any in claim 1 to 5
It is formed after curable resin composition solidification described in.
10. transparent conductive film according to claim 8, which is characterized in that the thickness of the transparency conducting layer is 1 μm~3 μ
m。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102324462A (en) * | 2006-10-12 | 2012-01-18 | 凯博瑞奥斯技术公司 | Transparent conductor and application thereof based on nano wire |
| KR20140076472A (en) * | 2012-12-12 | 2014-06-20 | 제일모직주식회사 | Transparent Electrode Formed having Improved Transmittance and Transparency |
| CN104837628A (en) * | 2012-12-13 | 2015-08-12 | 卡尔斯特里姆保健公司 | Anticorrosion agents for transparent conductive film comprising at least one organic acid |
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2018
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| CN102324462A (en) * | 2006-10-12 | 2012-01-18 | 凯博瑞奥斯技术公司 | Transparent conductor and application thereof based on nano wire |
| KR20140076472A (en) * | 2012-12-12 | 2014-06-20 | 제일모직주식회사 | Transparent Electrode Formed having Improved Transmittance and Transparency |
| CN104837628A (en) * | 2012-12-13 | 2015-08-12 | 卡尔斯特里姆保健公司 | Anticorrosion agents for transparent conductive film comprising at least one organic acid |
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