# US 11,111,396 B2 · Transparent films with control of light hue using nanoscale colorants

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- Number: US 11,111,396 B2
- Document ID: US11111396B2
- Status: Granted
- Kind: B2
- Application number: 14/627,400
- Filed: 2015-02-20
- Published: 2016-04-21
- Granted: 2021-09-07
- Earliest claimed: 2014-10-17
- Assignees: C3 Nano, Inc.
- Applicants: C3Nano Inc.
- Inventors: Xiqiang Yang; Yadong Cao; Yongxing Hu; Hua Gu; Ying-Syi Li; Ajay Virkar
- Web page: https://patentgrep.com/patent/US11111396B2

## CPC

- C09D 5/24: Electrically-conducting paints {(conductive materials H01B1/00)}
- C09D 7/61: inorganic
- C09D 7/70: {characterised by shape, e.g. fibres, flakes or microspheres}
- G02B 1/16: having an anti-static effect, e.g. electrically conducting coatings
- G02B 5/008: {Surface plasmon devices (diffractive gratings with a pitch less than or comparable to the wavelength G02B5/1809; surface plasmons in integrated optics G02B6/1226; optical analysis of materials by means of surface plasmons G01N21/553)}
- G02B 5/223: {containing organic substances, e.g. dyes, inks or pigments}
- G06F 1/16: Constructional details or arrangements
- G06F 3/0412: {Digitisers structurally integrated in a display}
- G06F 3/0445: {using two or more layers of sensing electrodes, e.g. using two layers of electrodes separated by a dielectric layer}
- H01B 5/14: comprising conductive layers or films on insulating-supports
- G02B 2207/101: Nanooptics
- G06F 3/045: using resistive elements, e.g. a single continuous surface or two parallel surfaces put in contact
- 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 (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- G02B: OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G06F: ELECTRIC DIGITAL DATA PROCESSING (computer systems based on specific computational models G06N)
- H01B: CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES (selection for magnetic properties H01F1/00; waveguides H01P {; printed circuits H05K})

## Abstract

Nanoscale colorants are introduced to adjust the hue of transparent conductive films, such as to provide a whiter film. The transparent conductive films can have sparse metal conductive layers, which can be formed using silver nanowires. Color of the film can be evaluated using standard color parameters. In particular, values of color parameter b* can be reduced with the nanoscale colorants without unacceptably changing other parameters, such as haze, a* and transparency.

## Claims

### Claim 1

A transparent conductive film comprising a substrate, a transparent conductive layer supported by the substrate, a coating and one or more nanoscale colorants, wherein a value of b* for the film is reduced at least about 0.1 units and total transmittance of visible light in percent is not decreased by more than about 2 relative to the corresponding film without the nanoscale colorants, wherein the nanoscale colorants comprise a metal nanoplate having an average thickness of no more than about 100 nanometers (nm) wherein the nanoscale colorants in a dilute dispersion have a peak absorption between 525 nm and 675 nm.

### Claim 2 (depends on 1)

The transparent conductive film of claim 1 wherein the transparent conductive layer comprises a sparse metal conductive layer.

### Claim 3 (depends on 1)

The transparent conductive film of claim 1 wherein the transparent conductive layer comprises a fused metal nanostructured network.

### Claim 4 (depends on 1)

The transparent conductive film of claim 1 wherein the haze in percent units does not increase by more than 0.5 relative to the corresponding film without the nanoscale colorant.

### Claim 5 (depends on 1)

The transparent conductive film of claim 1 having a total transmittance of visible light of at least about 85% and a haze of no more than about 1.2%, wherein the transparent conductive layer has a sheet resistance of no more than about 100 ohms/sq.

### Claim 6 (depends on 5)

The transparent conductive film of claim 5 wherein the absolute value of b* and a* in the color scale are each no more than about 1.

### Claim 7 (depends on 1)

The transparent conductive film of claim 1 wherein the nanoscale colorants are in the coating at a concentration from about 0.001 wt % to about 10 wt %.

### Claim 8 (depends on 1)

The transparent conductive film of claim 1 wherein transparent conductive film comprises a sparse metal conductive layer and wherein the nanoscale colorants and a polymer binder are in the sparse metal conductive layer and the nanoscale colorants are at a concentration in the layer from about 0.1 wt % to about 50 wt %.

### Claim 9 (depends on 1)

The transparent conductive film of claim 1 wherein the coating has from about 0.1 wt % to about 5 wt % nanoscale colorants.

### Claim 10 (depends on 1)

The transparent conductive film of claim 1 wherein the coating comprises polysiloxanes, polysilsesquioxanes, polyurethanes, acrylic resins, acrylic copolymers, cellulose ethers and esters, nitrocellulose, other water insoluble structural polysaccharides, polyethers, polyesters, polystyrene, polyimide, fluoropolymer, styrene-acrylate copolymers, styrene-butadiene copolymers, acrylonitrile butadiene styrene copolymers, polysulfides, epoxy containing polymers, copolymers thereof, and mixtures thereof.

### Claim 11 (depends on 1)

The transparent conductive film of claim 1 wherein the film is hue adjusted as expressed as an absolute value of the color scale a* being adjusted by at least about 0.1 relative to the equivalent film without the nanoscale colorants.

### Claim 12 (depends on 1)

The transparent conductive film of claim 1 having a total transmittance of visible light of at least about 85% and a haze of no more than about 1.2%.

### Claim 13 (depends on 1)

The transparent conductive film of claim 1 having a thickness from about 5 microns to about 1 mm.

### Claim 14

A transparent conductive film comprising a substrate and a transparent conductive layer comprising a sparse metal conductive element and a polymer binder, wherein the transparent conductive layer comprises metal nanostructures having an absorption at 580 nm at least about 2 times the absorption at 475 nm, wherein the transparent conductive film has a value of b* lowered by at least about 0.1 and a value of % TT lowered by no more than about 2 relative to an equivalent transparent conductive layer without the metal nanostructures.

### Claim 15 (depends on 14)

The transparent conductive film of claim 14 wherein the sparse metal conductive element comprises a fused metal nanostructured network and wherein the metal nanostructures may or may not be fused into the fused metal nanostructured network.

### Claim 16 (depends on 14)

The transparent conductive film of claim 14 wherein the metal nanostructures comprise metal nanoplates, metal nanoshells or combinations thereof, which may be fused into the fused metal nanostructured network.

### Claim 17 (depends on 14)

The transparent conductive film of claim 14 having a total transmittance of visible light of at least about 85% and absolute value of b* of no more than about 1.2 and a haze of no more than about 1.2%, and wherein the sparse metal conductive layer has a sheet resistance of no more than about 100 ohms/sq.

### Claim 18

A coating solution comprising from about 0.02 wt % to about 80 wt % non-volatile polymer binder precursor compounds, from about 0.0001 wt % to about 2.5 wt % metal nanostructures, from about 0.01 wt % to about 1 wt % metal nanowires and solvent wherein the metal nanostructures have an absorption at 580 nm at least about 2 times the absorption at 475 nm.

### Claim 19 (depends on 18)

The coating solution of claim 18 wherein the metal nanostructures comprise metal nanoplates, metal nanoshells, or metal nanoribbons or combinations thereof and wherein metal nanostructures in a dilute dispersion in water have a peak absorption between 525 nm and 675 nm.

### Claim 20 (depends on 18)

The coating solution of claim 18 wherein the polymer comprises polysiloxanes, polysilsesquioxanes, polyurethanes, acrylic resins, acrylic copolymers, cellulose ethers and esters, nitrocellulose, other water insoluble structural polysaccharides, polyethers, polyesters, polystyrene, polyimide, fluoropolymer, styrene-acrylate copolymers, styrene-butadiene copolymers, acrylonitrile butadiene styrene copolymers, polysulfides, epoxy containing polymers, copolymers thereof, and mixtures thereof.

### Claim 21 (depends on 18)

The coating solution of claim 18 wherein the solution can be coated to dry into a film with a thickness of no more than about 1 mm while having a total transmittance of visible light of at least 85% while adjusting the hue of the dried film as expressed as an absolute value of the color scale b*, a* or both being adjusted by at least about 0.1 relative to the equivalent film without the metal nanostructures.

### Claim 22

A transparent conductive film comprising a substrate, a transparent conductive layer supported by the substrate, a coating and one or more nanoscale colorants, wherein a value of b* for the film is reduced at least about 0.1 units and total transmittance of visible light in percent is not decreased by more than about 2 relative to the corresponding film without the nanoscale colorants, wherein the transparent conductive layer comprises a fused metal nanostructured network.

### Claim 23 (depends on 22)

The transparent conductive film of claim 22 wherein the nanoscale colorants comprise a metal nanoshell with a ceramic core having an average diameter of the primary particles of no more than about 100 nm.

### Claim 24 (depends on 22)

The transparent conductive film of claim 22 wherein the haze in percent units does not increase by more than 0.5 relative to the corresponding film without the nanoscale colorant.

### Claim 25 (depends on 22)

The transparent conductive film of claim 22 having a total transmittance of visible light of at least about 85% and a haze of no more than about 1.2%, wherein the transparent conductive layer has a sheet resistance of no more than about 100 ohms/sq.

### Claim 26 (depends on 25)

The transparent conductive film of claim 25 wherein the absolute value of b* and a* in the color scale are each no more than about 1.

### Claim 27 (depends on 22)

The transparent conductive film of claim 22 wherein the nanoscale colorants are in the coating at a concentration from about 0.001 wt % to about 10 wt %.

### Claim 28 (depends on 22)

The transparent conductive film of claim 22 wherein the nanoscale colorants comprise metal nanoribbons.

### Claim 29 (depends on 22)

The transparent conductive film of claim 22 wherein the coating has from about 0.1 wt % to about 5 wt % nanoscale colorants.

### Claim 30 (depends on 22)

The transparent conductive film of claim 22 wherein the coating comprises polysiloxanes, polysilsesquioxanes, polyurethanes, acrylic resins, acrylic copolymers, cellulose ethers and esters, nitrocellulose, other water insoluble structural polysaccharides, polyethers, polyesters, polystyrene, polyimide, fluoropolymer, styrene-acrylate copolymers, styrene-butadiene copolymers, acrylonitrile butadiene styrene copolymers, polysulfides, epoxy containing polymers, copolymers thereof, and mixtures thereof.

### Claim 31 (depends on 22)

The transparent conductive film of claim 22 wherein the film is hue adjusted as expressed as an absolute value of the color scale a* being adjusted by at least about 0.1 relative to the equivalent film without the nanoscale colorants.