IP Library › Granted Patent US 12,391,836
Granted Patent B2
US 12,391,836 · App. 18/118,853 · Granted Aug 19, 2025

Lidar reflective material and marking system

Inventors: Michael P. Rowe (Pinckney, MI); Frederick W. Mau, II (McKinney, TX); Songtao Wu (Ann Arbor, MI); Debasish Banerjee (Ann Arbor, MI)
Assignees: Toyota Motor Engineering & Manufacturing North America, Inc.; Toyota Jidosha Kabushiki Kaisha
C09D5/004C09D5/021C09D5/028C09D7/20C09D7/61C09D7/67C09D175/04C08K3/04C08K2003/2248C08K2003/2265
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Quick Facts
Patent No.
US 12,391,836
App. No.
18/118,853
Granted
Aug 19, 2025
Kind
B2
Abstract

Disclosed here are a method of marking a dark-colored surface with a dark-colored LiDAR-reflective material and a marking composition comprising the dark-colored LiDAR-reflective material and a marking carrier. Particularly, the dark-colored LiDAR-reflective material comprises has a reflectivity in the visible spectrum of electromagnetic radiation that is ≤10% and a reflectivity in the near-IR and LiDAR spectrum of electromagnetic radiation that is ≥10%.

Claims (45)

1. A method of marking a surface with a marking material, the method comprising:

selecting a surface to be marked;

applying the marking material to the surface, wherein

the marking material comprises:

a LiDAR-reflective material; and

a marking carrier, and

the LiDAR-reflective material comprises:

an average particle size that is from 5 nm to 15 nm;

a blackness My that is from 130 to 170;

a reflectivity in the visible spectrum of electromagnetic radiation that is ≤10%; and

a reflectivity in the near-IR and LiDAR spectrum of electromagnetic radiation that is ≥10%.

2. The method of claim 1 , wherein applying the LiDAR-reflective material to the surface comprises spraying the surface with the LiDAR-reflective material.

3. The method of claim 1 , wherein applying the LiDAR-reflective material to the surface comprises applying the LiDAR-reflective material on the surface with an applicator.

4. The method of claim 3 , wherein the applicator is selected from at least one of the group consisting of a stamp, a brush, a marker, a pen, a stylus, a roller, and a needle.

5. The method of claim 1 , wherein applying the LiDAR-reflective material to the surface comprises:

contacting a membrane encasing the LiDAR-reflective material to the surface, wherein the membrane is selected from the group consisting of gelatin, polyethylene terephthalate (PET), polystyrene, gelatin, nylon, polycarbonate, epoxy, phenol formaldehyde resin, urethane, polyesters, vinyl esters, polyethylene, polypropylene, polyvinyl chloride, polymethyl methacrylate, acrylonitrile-butadiene-styrene (ABS), polydimethylsiloxane, polysulfide, or a combination of two or more thereof; and

fracturing the membrane upon contact with the surface.

6. The method of claim 1 , wherein the LiDAR-reflective material is applied to the surface as a unique marking design.

7. The method of claim 6 , wherein the unique marking design is a glyph, bar code, or QR code.

8. A marking composition, comprising:

a LiDAR-reflective material; and

a marking carrier,

wherein the LiDAR-reflective material comprises:

an average particle size that is from 5 nm to 15 nm;

a blackness My that is from 130 to 170;

a reflectivity in the visible spectrum of electromagnetic radiation that is ≤10%; and

a reflectivity in the near-IR and LiDAR spectrum of electromagnetic radiation that is ≥ 10%.

9. The marking composition of claim 8 , wherein the marking composition is encased in a membrane selected from the group consisting of gelatin, polyethylene terephthalate (PET), polystyrene, gelatin, nylon, polycarbonate, epoxy, phenol formaldehyde resin, urethane, polyesters, vinyl esters, polyethylene, polypropylene, polyvinyl chloride, polymethyl methacrylate, acrylonitrile-butadiene-styrene (ABS), polydimethylsiloxane, polysulfide, and combinations thereof.

10. The marking composition of claim 8 , wherein the composition further comprises a propellant selected from the group consisting of difluorochloromethane, dimethyl ether, methyl ethyl ether, tetrafluoroethane, heptafluoropropane, hydrofluoroolefin, low-molecular weight hydrocarbons, butane, isobutene, propane, nitrous oxide, carbon dioxide, nitrogen, and combinations thereof.

11. The marking composition of claim 8 , wherein the marking carrier is a gas selected from the group consisting of argon, nitrogen, oxygen, difluorochloromethane, dimethyl ether, methyl ethyl ether, tetrafluoroethane, heptafluoropropane, hydrofluoroolefin, chlorofluorocarbons, low-molecular weight hydrocarbons, butane, isobutene, propane, nitrous oxide, carbon dioxide, and combinations thereof.

12. The marking composition of claim 11 , wherein the LiDAR-reflective material comprises a dark-colored pigment selected from the group consisting of CuO crystallites, carbon black, chromium iron oxide and its derivatives, or a combination of two or more thereof.

13. The marking composition of claim 12 , wherein the dark-colored pigment comprises CuO crystallites with a ratio of (−111)/(111) intensity that is from 0.5 to 1.5.

14. The marking composition of claim 12 , wherein the dark-colored pigment comprises CuO crystallites with a ratio of (−111)/(111) intensity that is from 0.9 to 1.1.

15. The marking composition of claim 8 , wherein the marking carrier is a fluid selected from the group consisting of water, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketones, isophorene, diacetone alcohol, diisobutyl ketone, ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, glycol ether esters, propylene glycol mono methyl ether acetate, ethanol, butanol, propanol, ethylene glycol monobutyl ether, ethylene glycol mono-n-propyl ether, diethylene glycol monobutyl ether, propylene glycol mono methyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, and combinations thereof.

16. The marking composition of claim 8 , wherein the marking carrier is a polymer selected from the group consisting of gelatin, polyethylene terephthalate (PET), polystyrene, gelatin, nylon, polycarbonate, epoxy, phenol formaldehyde resin, urethane, polyesters, vinyl esters, polyethylene, polypropylene, polyvinyl chloride, polymethyl methacrylate, acrylonitrile-butadiene-styrene (ABS), polydimethylsiloxane, polysulfide, and combinations thereof.

17. The marking composition of claim 8 , wherein the marking carrier is a combination of a gas and a fluid, wherein

the gas is selected from the group consisting of argon, nitrogen, oxygen, difluorochloromethane, dimethyl ether, methyl ethyl ether, tetrafluoroethane, heptafluoropropane, hydrofluoroolefin, chlorofluorocarbons, low-molecular weight hydrocarbons, butane, isobutene, propane, nitrous oxide, carbon dioxide, and combinations thereof; and

the fluid is selected from the group consisting of water, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketones, isophorene, diacetone alcohol, diisobutyl ketone, ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, glycol ether esters, propylene glycol mono methyl ether acetate, ethanol, butanol, propanol, ethylene glycol monobutyl ether, ethylene glycol mono-n-propyl ether, diethylene glycol monobutyl ether, propylene glycol mono methyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, and combinations thereof.

18. The marking composition of claim 8 , wherein the marking carrier is a combination of a fluid and a polymer, wherein

the fluid is selected from the group consisting of water, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketones, isophorene, diacetone alcohol, diisobutyl ketone, ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, glycol ether esters, propylene glycol mono methyl ether acetate, ethanol, butanol, propanol, ethylene glycol monobutyl ether, ethylene glycol mono-n-propyl ether, diethylene glycol monobutyl ether, propylene glycol mono methyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, and combinations thereof; and

the polymer is selected from the group consisting of gelatin, polyethylene terephthalate (PET), polystyrene, gelatin, nylon, polycarbonate, epoxy, phenol formaldehyde resin, urethane, polyesters, vinyl esters, polyethylene, polypropylene, polyvinyl chloride, polymethyl methacrylate, acrylonitrile-butadiene-styrene (ABS), polydimethylsiloxane, polysulfide, and combinations thereof.

19. The marking composition of claim 8 , wherein the LiDAR-reflective material comprises an average particle size that is from 8 nm to 12 nm.

20. The marking composition of claim 8 , wherein the LiDAR-reflective material comprises a blackness M y that is from 150 to 170.

21. The marking composition of claim 8 , wherein the LiDAR-reflective material comprises a reflectivity in the visible spectrum of electromagnetic radiation that is ≤5%.

22. The marking composition of claim 8 , wherein the LiDAR-reflective material comprises a reflectivity in the near-IR and LiDAR spectrum of electromagnetic radiation that is ≥20%.

Assignments (3)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 4, 2025
From: TOYOTA JIDOSHA KABUSHIKI KAISHA
To: TOYOTA MOTOR ENGINEERING & MANUFACTURING NORTH AMERICA, INC.
Reel/Frame 072779/0486 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 11, 2025
From: WU, SONGTAO; BANERJEE, DEBASISH
To: TOYOTA MOTOR ENGINEERING & MANUFACTURING NORTH AMERICA, INC.; TOYOTA JIDOSHA KABUSHIKI KAISHA
Reel/Frame 070473/0960 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 8, 2023
From: ROWE, MICHAEL P.; MAU, FREDERICK W., II
To: TOYOTA MOTOR ENGINEERING & MANUFACTURING NORTH AMERICA, INC.; TOYOTA JIDOSHA KABUSHIKI KAISHA
Reel/Frame 062918/0122 →
Continuity (1)
Related Publication 20240301215A1 · Sep 12, 2024
References Cited (33)
US 8842015B2 · Scott · 2014 [cited by applicant]
US 9683107B2 · Milliken et al. · 2017 [cited by applicant]
US 9921297B2 · Jungwirth · 2018 [cited by applicant]
US 11118062B2 · Banerjee et al. · 2021 [cited by applicant]
US 20020030742A1 · Aman et al. · 2002 [cited by applicant]
US 20040261655A1 · Newbacher · 2004 [cited by examiner]
US 20080134941A1 · Sanada · 2008 [cited by examiner]
US 20150122146A1 · Gruner et al. · 2015 [cited by applicant]
US 20170015836A1 · Milliken · 2017 [cited by examiner]
US 20200349338A1 · Lagmanson · 2020 [cited by applicant]
US 20220012555A1 · Duarte et al. · 2022 [cited by applicant]
US 20220195201A1 · Wu · 2022 [cited by examiner]
CA 3147350A1 · 2021 [cited by applicant]
CN 103480377B · 2015 [cited by applicant]
CN 109270963A · 2019 [cited by applicant]
WO 2014070116A1 · 2014 [cited by applicant]
WO 2015153129A1 · 2015 [cited by applicant]
WO 2020021306A1 · 2020 [cited by applicant]
“What is the Working Principle of Reflective Fabric?” Hangzhou Chinastars, https://www.chinareflective.com/faqs/How_does_reflective_fabric_work.html. [cited by applicant]
“Reflective Strips”, Spacio Innovations, https://www.spacioinnovations.com/brilliant.html. [cited by applicant]
Kim, J.H. et al., “Design of Near Infrared Reflective Effective Pigment for LiDAR Detectable Paint,” MRS Advances, vol. 5, Issue 11 (Energy and Environment), Jan. 21, 2020, pp. 515-522 (Abstract only). [cited by applicant]
International Search Report and Written Opinion for application PCT/US2021/041571 mail date Oct. 15, 2021 (14 pages). [cited by applicant]
Braga et al: “Copper oxide and niobium pentoxide supported on silica·alumina: Synthesis, characterization, and application on diesel soot oxidation”, Journal of Catalysis, Academic Press, Duluth, MN, US, vol. 247, No. 1… [cited by applicant]
Akgul Funda Aksoy et al: “Influence of thermal annealing on microstructural, morphological, optical properties and surface electronic structure of copper oxide thin films”, Materials Chemistry and Physics, vol. 147, No.… [cited by applicant]
Sekhar R: “Preparation of copper oxide thin film by the sol-gel-like dip technique and study of their structural and optical properties”, Solar Energy Materials and Solar Cells, Elsevier Science Publishers, Amsterdam, N… [cited by applicant]
Tangale Nilesh Pet Al: “Dehydrogenation of cyclohexanol over Cu/ Al2O3catalysts prepared with different precipitating agents”, Applied Catalysis A: General, Elsevier, Amsterdam, NL, vol. 467, Aug. 18, 2013 (Aug. 18, 201… [cited by applicant]
Zhang Fan et al: “Effect of Al-containing precursors on Cu/ZnO/AI203 catalyst for methanol production”, Fuel Processing Technology, vol. 178, Sep. 1, 2018 (Sep. 1, 2018), pp. 148-155, XP055847608, NL ISSN: 0378-3820, DO… [cited by applicant]
Wu Songtao Et Al: “Pitch-Black Nanostructured Copper Oxide as an Alternative to Carbon Black for Autonomous Environments”, Advanced Intelligent Systems, vol. 3, No. 9, Jun. 29, 2021 (Jun. 29, 2021), p. 2100049, XP055846… [cited by applicant]
Prabu R. David, et al.: “Studies on copper oxide think films prepared by simple spray technique”, Journal of Materials Science: Materials in Electronics, Chapman and Hall, London, GB, vol. 28, No. 9 Jan. 28, 2017 (Jan. … [cited by applicant]
Chang Ming-Hui, et al.: “Preparation of coper oxide nanoparticles and its application in nanoparticles and its application in nanofluid”, Powder Technology, vol. 207, No. 1-3, Dec. 1, 2010 (Dec. 1, 2010)m pp. 378-386, x… [cited by applicant]
International Search Report and Written Opinion for Application No. PCT/US2022/032693, date of mailing Sep. 27, 2022 (13 pages). [cited by applicant]
Invitation to Pay Additional Fees dated Jun. 28, 2024, pertaining to Int'l Patent Application No. PCT/US2024/018868, 10 pgs. [cited by applicant]
International Search Report and Written Opinion for Application No. PCT/US2024/018868 mail dated Aug. 20, 2024 (19 pages). [cited by applicant]