WO2022081756A1 - Curable carbon nanotube ink and transparent conductive films created using the ink - Google Patents
Curable carbon nanotube ink and transparent conductive films created using the ink Download PDFInfo
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- WO2022081756A1 WO2022081756A1 PCT/US2021/054845 US2021054845W WO2022081756A1 WO 2022081756 A1 WO2022081756 A1 WO 2022081756A1 US 2021054845 W US2021054845 W US 2021054845W WO 2022081756 A1 WO2022081756 A1 WO 2022081756A1
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- ink
- curable
- carbon nanotube
- cnt
- resin binder
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 97
- 239000011347 resin Substances 0.000 claims abstract description 46
- 229920005989 resin Polymers 0.000 claims abstract description 46
- 239000011230 binding agent Substances 0.000 claims abstract description 43
- 239000003085 diluting agent Substances 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 95
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 94
- 229910052751 metal Inorganic materials 0.000 claims description 35
- 239000002184 metal Substances 0.000 claims description 35
- 239000000758 substrate Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- 239000002070 nanowire Substances 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- 239000004971 Cross linker Substances 0.000 claims description 14
- 238000005530 etching Methods 0.000 claims description 12
- 229920006243 acrylic copolymer Polymers 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 9
- 238000005299 abrasion Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 230000005540 biological transmission Effects 0.000 claims description 7
- 229920000728 polyester Polymers 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 4
- 229920002873 Polyethylenimine Polymers 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 3
- 229920006254 polymer film Polymers 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 239000012949 free radical photoinitiator Substances 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 239000000976 ink Substances 0.000 description 85
- 229920005692 JONCRYL® Polymers 0.000 description 20
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- HXHCOXPZCUFAJI-UHFFFAOYSA-N prop-2-enoic acid;styrene Chemical compound OC(=O)C=C.C=CC1=CC=CC=C1 HXHCOXPZCUFAJI-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 230000005855 radiation Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229920002799 BoPET Polymers 0.000 description 7
- 238000001723 curing Methods 0.000 description 7
- 230000009977 dual effect Effects 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 238000007639 printing Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229920005772 JONCRYL® HPD 671 Polymers 0.000 description 4
- 238000003848 UV Light-Curing Methods 0.000 description 4
- 229920005596 polymer binder Polymers 0.000 description 4
- 239000002491 polymer binding agent Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 150000001735 carboxylic acids Chemical group 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- 229920005731 JONCRYL® 67 Polymers 0.000 description 2
- 229920005732 JONCRYL® 678 Polymers 0.000 description 2
- 229920005733 JONCRYL® 682 Polymers 0.000 description 2
- 229920005734 JONCRYL® 693 Polymers 0.000 description 2
- 229920005934 JONCRYL® 820 Polymers 0.000 description 2
- 229920005776 JONCRYL® ECO 675 Polymers 0.000 description 2
- 229920005777 JONCRYL® ECO 684 Polymers 0.000 description 2
- 229920005773 JONCRYL® HPD 696 Polymers 0.000 description 2
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000013036 cure process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- -1 polyethylene terephthalate Polymers 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 238000001029 thermal curing Methods 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- LYGZOGDWCOYSGJ-UHFFFAOYSA-N 2-hydroxy-1-[4-[4-(2-hydroxy-2-methylpropanoyl)phenoxy]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1OC1=CC=C(C(=O)C(C)(C)O)C=C1 LYGZOGDWCOYSGJ-UHFFFAOYSA-N 0.000 description 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002042 Silver nanowire Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004590 computer program Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
-
- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
-
- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
- C09D11/104—Polyesters
-
- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
Definitions
- This disclosure relates to a curable conductive coating.
- Carbon nanotube ink i.e., conductive coating
- TCF transparent conductive film
- This invention includes a curable carbon nanotube (CNT) ink (i.e., a printable conductive coating), and transparent conductive films (TCFs) that are created (e g., printed) using the ink.
- CNT carbon nanotube
- TCFs transparent conductive films
- the ink contributes to both the conductivity of the film and its ability to stand up to environmental conditions.
- the ink also acts as an etching mask.
- the ink includes one or both of a radiation-curable and a thermally-curable resin that acts as a binder for the CNT when the resin is cured, and also promotes good adhesion, abrasion resistance, and chemical resistance.
- a catalyst facilitates curing of the resin.
- the ink also includes a viscous diluent that fully evaporates during the ink drying/curing process.
- the diluent helps to accomplish a desired viscosity of the ink that allows it to be coated onto an underlying substrate, such as by screen printing.
- the viscosity of the ink is from about 1,000 cP to about 50,000 cP.
- the curable carbon nanotube ink is composed of single-wall carbon nanotube component and an UV and/or a thermally curable polymer binder component.
- the CNT ink is a screen printable ink containing no surfactants. In general, CNTs require surfactants to remain as a dispersion, or else they may agglomerate. Once a coating with surfactants is printed or dried, the surfactants must be washed out.
- the present ink can be used in the creation of a TCF.
- the TCF includes a substrate, a metal nano-wire coating or a metal mesh (MM) layer on the substrate surface, and the ink over the nanowire or MM layer.
- the resulting multilayer structure demonstrates excellent electrical conductivity, high visible light transmission, and excellent adhesion of the metal nanowire (or metal mesh)/CNT composite structure to the substrate.
- the TCF also includes a substrate (polymer film, glass panel, etc.) without metal-nanowire or metal mesh coating, with the printed CNT ink.
- This invention results in creation of novel curable carbon nanotube ink and printed film, which shows advantages of better adhesion to a metal-nano wire coating or a metal mesh layer, improved abrasion resistance, and better solvent and chemical resistance during the etching process as compared to TCFs prepared using non-curable CNT inks, while maintaining excellent electrical conductivity, high visible light transmission and low haze.
- a curable carbon nanotube ink includes a curable resin binder, a catalyst that is configured to be activated and cure the resin binder, a viscous to vapor diluent, and carbon nanotubes (CNTs).
- the CNT concentration range in the ink is from about 0.001% to about 0.2% by weight. Some examples include one of the above and/or below features, or any combination thereof.
- the resin binder concentration range in the ink is from about 0.1% to about 5% by weight.
- the catalyst concentration range in the ink is from about 0.001% to about 1.0% by weight.
- the diluent concentration range in the ink is from about 90% to about 99% by weight.
- the curable carbon nanotube ink further includes a filler resin with a concentration range in the ink of from about 0.1% to about 5% by weight.
- the resin binder comprises a mixture of UV and thermal curable resins.
- the curable carbon nanotube ink has a viscosity of from about 1,000 cP to about 50,000 cP.
- the CNT comprises single-wall CNT.
- the curable carbon nanotube ink further includes one or more of a non-UV curable resin, a multifunctional oligomer, or a monomer.
- the catalyst comprises a type I or type II free radical photo-initiator.
- the resin binder is thermally curable.
- the resin binder comprises one or more of an acrylic co-polymer with an acidic functional group, a urethane polymer, or a polyester.
- the catalyst comprises at least one of a polyaziridine crosslinker, a polycarbodiimide crosslinker, or a peroxide type catalyst.
- a transparent conductive film in another aspect, includes a polymer film substrate, a metal nanowire layer or metal mesh layer on a surface of the film, and a cured carbon nanotube (CNT) ink covering at least some of the metal nanowire layer or metal mesh layer.
- the CNT ink comprises a curable resin binder, a catalyst that is configured to be activated and cure the resin binder, a viscous to vapor diluent, and CNTs.
- the CNT concentration range in the ink is from about 0.001% to about 0.2% by weight.
- the TCF demonstrates excellent electrical conductivity, high visible light transmission, and excellent adhesion of the metal nanowire layer or metal mesh layer and cured CNT ink to the substrate.
- the TCF demonstrates better adhesion to the metal nanowire layer or metal mesh layer, improved abrasion resistance, and better solvent and chemical resistance during the etching process as compared to a TCF prepared using a non-curable CNT ink.
- the TCF maintains excellent electrical conductivity, high visible light transmission, and low haze.
- Fig. 1 is a schematic side view of a TCF.
- Figs. 2A-2D illustrate a method of creating a TCF.
- Fig. 3 illustrates the steps of a process for creating a TCF.
- Fig. 4 is a graph illustrating ink viscosity for different levels of CNT.
- references to examples, components, elements, acts, or functions of the computer program products, systems and methods herein referred to in the singular may also embrace embodiments including a plurality, and any references in plural to any example, component, element, act, or function herein may also embrace examples including only a singularity. Accordingly, references in the singular or plural form are not intended to limit the presently disclosed systems or methods, their components, acts, or elements.
- the use herein of “including,” “comprising,” “having,” “containing,” “involving,” and variations thereof is meant to encompass the items listed thereafter and equivalents thereof as well as additional items. References to “or” may be construed as inclusive so that any terms described using “or” may indicate any of a single, more than one, and all of the described terms.
- the CNT ink can be printed on flexible and rigid substrates.
- the substrates may be inorganic and/or organic, including but not limited to glass, silicon wafer, plastic films of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), thermoplastic polyurethane (TPU), cyclic olefin polymer (COP), Silicone, or polyimide (CPI).
- Plastic substrates could have a primer layer or have a surface treatment to improve surface tension (e.g., Corona Treatment, flame treatment, other plasma, etc.), and in some examples the film thickness is in the range of 12.5 microns to 300 microns.
- the substrates, the nanowire layer (e.g., silver nanowire (AgNW) or the metal mesh (MM) layer, and the fabrication methods of the TCF according to this disclosure can be of the types disclosed in International Patent Application Publication No. WO 2016/172315 and/or International Patent Application Publication No. WO 2020/102392, the entire disclosures of which are incorporated herein by reference for all purposes.
- the nanowire layer e.g., silver nanowire (AgNW) or the metal mesh (MM) layer
- MM metal mesh
- the TCF is fabricated in accordance with the following procedures.
- a UV CNT ink formulation consists of a viscous to vapor (“V2V”) diluent that fully evaporates during the ink drying/curing process, a CNT dispersion in alcohols and amines, a radiation curable resin binder, a photoinitiator, and optionally a non-UV curable resin added to the UV resin mixture.
- V2V viscous to vapor
- the CNT concentrations are in the 0.01 to 2.0 g/L range (i.e., from about 0.001% to about 0.2% by weight in the ink).
- the range of CNT to UV resin or resin mixture binder concentration ratios (CNT/binder) is from about 1 : 1 to about 1 : 1200.
- the V2V diluent helps to accomplish a desired viscosity of the ink that allows it to be coated onto an underlying substrate, such as by screen printing.
- the V2V diluent is of the types disclosed in US Patents 9,777,167, and 9,777,168, the entire disclosures of which are incorporated herein by reference for all purposes.
- UV resin binders include but are not limited to:
- Multi-functional UV curable oligomers and monomers such as Ebecryl 4859, Ebecryl 4858, Ebecryl 8701, Ebecryl 8605, Ebecryl 225, Ebecryl 4740, Ebecryl 4859, Ebecryl 8405, Ebecryl 1290, Ebecryl 4738, Ebecryl 4513, Ebecryl 284 from Allnex, SR 399, SR368, CN 9210, CN 9276, CN 9196, CN 9209, CN 2306 from Sartomer.
- Miramer M140 Miramer Ml 50, Miramer Ml 182, Miramer M200, Miramer M 262, Miramer M 300, Miramer M 3130, Miramer M 420.
- Multi-functional UV curable acrylic copolymers NeoRad-A 20 from DSM, Ebecryl 4654 from Allnex, Lumicryl U- 72 IS, Lumicryll02, Lumicryl2882 and Lumicryl 245 from Enstron.
- the UV photo-initiators include, but are not limited to, Irgacure 651, Irgacure369, Irgacure901, Irgacurel84, Irgacure 2959, Irgacure TPO, Irgacure 819 and Darocur 1173 from BASF, Omnirad 500, Esacure kip 160, Esacure kip 100F, Esacure kip 150, Esacure TZT, Esacure 3644, Esacure 1001M, Omnirad 4-PBZ, Omnirad BP, from IGM.
- Irgacure 651, Irgacure369, Irgacure901, Irgacurel84, Irgacure 2959, Irgacure TPO, Irgacure 819 and Darocur 1173 from BASF Omnirad 500, Esacure kip 160, Esacure kip 100F, Esacure
- non-UV cured (i.e., non-curable) resin binders when used, include but are not limited to Neocryl 819, Neocryl 817, Neocryl 890 and Neocryl 813 from DSM; Joncryl 857, Joncryl 586, loncryl 611, Joncryl 678, Joncryl 680, Joncryl 682, Joncryl 683, Joncryl 693, JoncrylECO 675, Joncryl ECO684, Joncryl 817, Joncryl 819, Joncryl 820, Joncryl 821, Joncryl 901, Joncryl 903 Joncryl 843, Joncryl 848, Joncryl 67, Joncryl 690 , Joncryl HPD 671 and Joncryl HPD 696 from BASF.
- Neocryl 819, Neocryl 817, Neocryl 890 and Neocryl 813 from DSM Joncryl 857, Joncryl 586, loncryl 611, Joncryl 678, Jonc
- a thermally curable CNT ink formulation consists of a V2V diluent, carbon nanotubes, a thermally-curable resin binder, and a crosslinking agent or crosslinker.
- the CNT concentrations and the CNT/binder ratios are as described above.
- the cross-linkable resin binders include but are not limited to: 1.
- Acrylic copolymers with carboxyl function groups including but not limited to Neocryl 818, Neocryl 819, Neocryl 890 from DSM.
- Crosslinkers include: (A) polycarbodiimide crosslinker including but not limited to Crosslinker CX-300 and Crosslinker XL-1 from DSM; Picassian® XL-702, XL-712, XL- 752, XL-762 from STAHL, ZOLDINE®XL-29SE from ANGUS; (B) polyaziridine crosslinker including but not limited to Crosslinker CX-100 and NeoAddTM PAX-521 from DSM, Picassian® XL-048 and Picassian® XL-706 from STAHL, PZ-28 and PZ-33 from Poly Aziridine LLC.
- the curing process is temperature and time dependent.
- a UV and thermal dual cure CNT ink formulation consists of a “V2V” diluent, CNT dispersion in alcohols and/or amines, a binder resin mixture of radiation curable acrylic copolymers and acrylic copolymers with carboxylic acid function groups, a photoinitiator, and a crosslinker.
- UV curable acrylic copolymer, thermal curable acrylic copolymers with carboxy function groups, photoinitiator and thermal crosslinkers are defined above.
- the CNT concentrations and CNT/binder ratios are as described above.
- a radiation curing system place coated sample (coating towards radiation source) under the radiation source, for example a UV lamp for certain time period to achieve needed radiation dosage.
- the radiation cure set up can be a static one or a conveyor system.
- a conveyor UV system equipped with mercury, LED or Xenon lamp and set conveyor belt speed to achieve UV curing dosage of 1400 mJ/cm ⁇ 2, placed above UV CNT coated film on to the feeding end of the UV conveyor system and the UV curing process is completed after the coated film passes through the UV radiation zone and exits the conveyor system.
- the UV curing process can also be done without a conveyor system, as long as the dosage is in the range of from about 400 to about 1800 mJ/cm ⁇ 2.
- the sample is cured at 110oC for 60 seconds. (60-600 seconds is a preferred range).
- curing can be accomplished by 1 st UV cure/2 nd thermal cure, or 1 st thermal cure/2 nd UV cure.
- Pattern Etching Process The radiation cured samples were then sprayed with a 1-20% ferric nitrate (Fe(NO 3 ) 3 ) in water solution for 5-200 seconds.
- Abrasion test is performed by rubbing the printed ink surface with a cloth fabric, and any printed ink removal is considered as a failure.
- Ethanol resistance rubbing test is performed by wiping the printed ink surface with an ethanol soaked cloth, sheet resistance is then measured after 30 seconds drying time at ambient temperature. After 5 repetitive wiping passes, if the sheet resistance change is less than 10% of the original value, the sample is considered to pass the test.
- a CNT -based hybrid TCF 10, fig. 1 comprises a MM layer 13 that includes metal traces 14-16, and an overlying CNT ink layer 18 that bonds to the top surface of substrate 12 and encapsulates MM layer 13 with a conductive medium.
- a circuit pattern results after any exposed MM (i.e., the regions where the CNT ink is not printed) is removed via chemical etching. Note that the circuit pattern can alternatively or additionally be created from a metal nanowire layer rather than a metal mesh layer.
- FIGs. 2A-2D illustrate results of a process for creating a TCF of the present disclosure. Note that the dimensions and other aspects of figs. 2A-2D are not to scale and may be exaggerated, for the sake of illustration only. Actual examples are set forth below.
- Assembly 20, fig. 2A comprises substrate 22 that carries a MM comprising traces 24-27.
- the MM can be created on the substrate by various means as described herein. Also the MM can comprise various conductive materials (e.g., metals), as further described herein.
- the MM comprises a series of thin traces (lines) that are electrically connected. The traces are typically but not necessarily laid out in a regular pattern.
- Fig. 2B illustrate a further assembly 30 wherein the MM is over-plated with a second metal (in this non-limiting example the second metal being copper).
- traces 24-27 are covered by a generally thicker layer of a second metal comprising portions 34-37, to create thickened and less-porous MM traces 40-43, respectively.
- Fig. 2C illustrates a further assembly 50 wherein CNT ink 48 is printed or otherwise placed over some or all of the MM layer illustrated in fig. 2B.
- ink 48 is printed over traces 41 and 42 but not over traces 40 and 43. Traces 40 and 43 are thus exposed while traces 41 and 42 are covered by a conductive medium that creates a conductive line or conductive area 49.
- Fig. 2D illustrates the final TCF 60 wherein exposed traces 40 and 43 have been removed by etching, as explained in more detail elsewhere herein. This leaves conductor 49 on substrate 22.
- a suitable substrate is provided.
- a metal mesh is printed on a surface of the substrate.
- a second metal e.g., copper
- Step 76 is optional, as if the MM itself has an acceptable Rs the thickness (i.e., the height) of the MM lines may not need to be increased.
- the added plated metal increases the volume of the MM traces and so decreases its resistance. Also it may help to make the thin MM more robust and better able to bond with the conductive ink.
- a curable conductive medium (termed an “ink”) is printed in selected areas of the MM to form parts of a circuit.
- the curable ink comprises carbon nanotubes as its conductive medium, and also contains a binder and other components as described herein. CNT inks are further described elsewhere herein.
- the ink is cured in a manner appropriate for the particular ink and as further described elsewhere herein.
- the final step 82 contemplates etching exposed MM/copper, to leave behind on the substrate only the circuit.
- Fig. 4 is a graph illustrating ink viscosity for different levels of CNT.
- the CNT concentration has a direct effect on the viscosity of the ink, as evidenced by the curve of Fig. 4.
- the inks herein should have viscosities in the range of from about 1,000 cp to about 50,000 cp in order for them to be screen printed using normal printing techniques, and be useful without the need for a surfactant as discussed above.
- 1 gram/liter of CNT equates to about 0.1%, which equates to a viscosity of about 50,000 cp. From the viscosity graph of Fig. 4 it is clear that including 3 grams/liter CNT would likely push the ink into a non-usable regime for printing, into the millions of cp. Even 0.2% CNT would extrapolate to about 700,000 cp.
- UV and/or thermally curable CNT ink creates the advantages of superior adhesion to substrates having a layer of metal-nanowire coating or metal mesh layer, superior abrasion resistance and chemical resistance during etching process over the same TCF designs but using non-cured resin binders, while maintaining equivalent electrical and optical properties of VLT and haze number.
- Example 1 A UV-curable CNT ink with CNT concentration of 0.1 g/l and CNT/binder ratio of 1:120.
- the binder resin is composed of 60%wt of a UV curable polymer Lumicryl 245 from Enstron, and 40%wt of Neocryl B-890 a non-UV curing polymer from DSM.
- a photoinitiator Esacure KIP 100F is used, with photoinitiator to binder ratio of 1:50.
- a non-UV cure CNT ink (identified as VC200), was tested for comparison (as a control baseline).
- VC200 has the same CNT, polymer binder and diluent concentrations as the UV CNT ink, but the resin binder is a non-curable thermal plastic polymer, for example 100% NeoCryl® B-890.
- the UV CNT ink and VC200 were screen printed on a C3 Nano AgNW coated PET film (125 um thick ) with a sheet resistance of 30 +/- 2 ⁇ / ⁇ .
- the screen mesh size is 305, and the drying condition is described above.
- the UV CNT ink printed sample was then UV cured with UV dosage of 1400 mj /cm ⁇ 2.
- the UV cured sample and the coated VC200 samples were subsequently etched with 10% ferric nitrate (Fe(NO 3 ) 3 ) in water solution for 12 seconds, then washed with deionized water and oven drying as described above. Performance tests were followed on the dry etched samples and the test results are listed in Table 1. The test is repeated on C3 Nano AgNW PET film of sheet resistances of 10 ⁇ / ⁇ , and 75 ⁇ / ⁇ .
- the test data listed in Tables 1A, 1B, and 1C clearly demonstrates that the UV cured CNT ink shows superior performance in adhesion to AgNW film substrates and superior abrasion and solvent resistance as compared to VC200 control using non-curable CNT ink.
- Example 2 A thermally curable CNT ink with CNT concentration of 0.1 g/l and CNT/binder ratio of 1:120.
- the binder resin is composed of a carboxylic acid functional acrylic resin Joncryl HPD 671 from BASF, a curing agent CX-100 from DSM with crosslinker to polymer ratio of 1:12.
- a non-curable CNT ink VC200 was tested for comparison.
- VC200 has CNT concentration of 0.1g/l and CNT/polymer binder ratio of 1:120, the same as the thermally curable CNT ink.
- the thermally curable CNT ink and VC200 were screen printed (screen size 305) on a C3 Nano AgNW coated PET film (125 um in thickness) with sheet resistance of 75 +/- 2 ⁇ / ⁇ .
- the printed film samples are dried with a conveyor belt oven set at 110C and drying time of 180 seconds.
- the thermal cured sample can be cured at ambient temperature for 120 hours, or acceleratedly cured at 110oC for 600 seconds.
- the VC200 printed and thermal cured samples were subsequently etched with 10% ferric nitrate (Fe(NO 3 ) 3 ) in water solution for 12 seconds, then washed with deionized water and dried in an oven at 110oC for 60 seconds. Performance tests were followed and the test results were listed in Table 2.
- the curable ink shows superior performance in abrasion and solvent wiping and etching resistance.
- Table 2 VC200 and UV CNT ink printed on C3 Nano 75 ⁇ / ⁇ PET film VC 200 non curable Thermally curable Example 3: A dual-cured CNT ink with CNT concentration of 0.1 g/l and CNT/binder ratio of 1:120.
- the binder resin is composed of 30%wt of a UV curable polymer Lumicryl 245 from Enstron, and 70wt% carboxylic acid functional acrylic resin Joncryl HPD 671 from BASF, a type II photoinitiator Omnirad 4PBZ and a co-initiator Esacure A198 both from IGM, and a thermal curing agent CX-100 from DSM.
- a non-curable CNT ink VC200 was tested for comparison.
- VC200 has CNT concentration of 0.1g/l and CNT/polymer binder ratio of 1:120, the same as dual cure CNT ink.
- the dual curable CNT ink and VC200 were screen printed (screen size 305) on a C3 Nano AgNW coated PET film (125 um in thickness) with sheet resistance of 75 +/- 2 ⁇ / ⁇ .
- the printed film samples are dried with a conveyor belt oven set at 110C and drying time of 180 seconds.
- the samples were subsequently UV cured with UV dosage of 1400 mj /cm ⁇ 2, followed by thermal curing at 110oC for 600 seconds.
- the cured samples were then etched with 10% ferric nitrate (Fe(NO 3 ) 3 ) in water solution for 12 seconds. Performance tests were followed and the test results were listed in Table 3.
- the dual cure ink shows superior performance in etching resistance over UV cure only and thermal cure only CNT ink.
Abstract
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JP2023522468A JP2023546569A (en) | 2020-10-13 | 2021-10-13 | Curable carbon nanotube ink and transparent conductive film made using the ink |
CN202180077377.5A CN116457426A (en) | 2020-10-13 | 2021-10-13 | Curable carbon nanotube ink and transparent conductive film produced using the same |
KR1020237016355A KR20230087579A (en) | 2020-10-13 | 2021-10-13 | Curable carbon nanotube inks and transparent conductive films produced using inks |
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Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100124611A1 (en) * | 2008-11-17 | 2010-05-20 | Xerox Corporation | Phase Change Inks Containing Graphene-Based Carbon Allotrope Colorants |
US20100140564A1 (en) * | 2006-03-07 | 2010-06-10 | Gerardus Cornelis Overbreek | Conductive ink |
US20110104376A1 (en) * | 2004-05-19 | 2011-05-05 | FLEXcon Industrial Park | Liquid formulations for coating and printing substrates |
US20130264390A1 (en) * | 2010-12-16 | 2013-10-10 | 3M Innovative Properties Company | Transparent Micropatterned RFID Antenna and Articles Incorporating Same |
US20140054515A1 (en) * | 2011-02-28 | 2014-02-27 | Nthdegree Technologies Worldwide Inc. | Metallic Nanowire Ink Composition for a Substantially Transparent Conductor |
US20160185990A1 (en) * | 2014-07-30 | 2016-06-30 | Pesolve Co., Ltd. | Conductive ink |
US20180037757A1 (en) * | 2015-02-27 | 2018-02-08 | Perpetuus Research & Development Limited | A particle dispersion |
WO2020092507A2 (en) * | 2018-10-30 | 2020-05-07 | Henkel IP & Holding GmbH | Conductive ink composition |
WO2021175989A1 (en) * | 2020-03-05 | 2021-09-10 | Advanced Material Development Limited | Carbon-based conducting inks |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005119772A2 (en) * | 2004-06-02 | 2005-12-15 | Douglas Joel S | Coatings comprising carbon nanotubes |
CN102648249B (en) * | 2009-08-14 | 2016-04-13 | Nano-C公司 | There is the solvent-based of removable property additive and water base carbon nanotube ink |
US11274223B2 (en) * | 2013-11-22 | 2022-03-15 | C3 Nano, Inc. | Transparent conductive coatings based on metal nanowires and polymer binders, solution processing thereof, and patterning approaches |
CN108574793B (en) * | 2017-03-08 | 2022-05-10 | 三星电子株式会社 | Image processing apparatus configured to regenerate time stamp and electronic apparatus including the same |
CN106883683A (en) * | 2017-03-19 | 2017-06-23 | 宁波工程学院 | A kind of preparation method of UV-curing carbon nano tube base electrically conductive ink |
CN110753588A (en) * | 2017-05-23 | 2020-02-04 | 阿尔法装配解决方案公司 | Graphene reinforced and engineered materials for membrane contact switches and other flexible electronic structures |
CN108610735A (en) * | 2018-03-23 | 2018-10-02 | 东莞市宇康电子材料科技有限公司 | A kind of heat dissipation ink and its construction technology |
-
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Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110104376A1 (en) * | 2004-05-19 | 2011-05-05 | FLEXcon Industrial Park | Liquid formulations for coating and printing substrates |
US20100140564A1 (en) * | 2006-03-07 | 2010-06-10 | Gerardus Cornelis Overbreek | Conductive ink |
US20100124611A1 (en) * | 2008-11-17 | 2010-05-20 | Xerox Corporation | Phase Change Inks Containing Graphene-Based Carbon Allotrope Colorants |
US20130264390A1 (en) * | 2010-12-16 | 2013-10-10 | 3M Innovative Properties Company | Transparent Micropatterned RFID Antenna and Articles Incorporating Same |
US20140054515A1 (en) * | 2011-02-28 | 2014-02-27 | Nthdegree Technologies Worldwide Inc. | Metallic Nanowire Ink Composition for a Substantially Transparent Conductor |
US20160185990A1 (en) * | 2014-07-30 | 2016-06-30 | Pesolve Co., Ltd. | Conductive ink |
US20180037757A1 (en) * | 2015-02-27 | 2018-02-08 | Perpetuus Research & Development Limited | A particle dispersion |
WO2020092507A2 (en) * | 2018-10-30 | 2020-05-07 | Henkel IP & Holding GmbH | Conductive ink composition |
WO2021175989A1 (en) * | 2020-03-05 | 2021-09-10 | Advanced Material Development Limited | Carbon-based conducting inks |
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