US20190110963A1 - Graphene-based multifunctional cosmetic compositions - Google Patents

Graphene-based multifunctional cosmetic compositions Download PDF

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US20190110963A1
US20190110963A1 US16/163,182 US201816163182A US2019110963A1 US 20190110963 A1 US20190110963 A1 US 20190110963A1 US 201816163182 A US201816163182 A US 201816163182A US 2019110963 A1 US2019110963 A1 US 2019110963A1
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composition
hair
water
graphene
substrate
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Lingye Zhou
Jiaxing Huang
Chong Luo
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Northwestern University
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Northwestern University
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Assigned to NORTHWESTERN UNIVERSITY reassignment NORTHWESTERN UNIVERSITY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LUO, CHONG, ZHOU, LINGYE, HUANG, JIAXING
Publication of US20190110963A1 publication Critical patent/US20190110963A1/en
Priority to US17/467,705 priority patent/US20210401689A1/en
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/67—Vitamins
    • A61K8/676—Ascorbic acid, i.e. vitamin C
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A61K8/736—Chitin; Chitosan; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/81—Preparation or application process involves irradiation

Definitions

  • Hair dyes are widely used for altering the cosmetic appearance of hair.
  • the color of hair is determined by the abundance and relative concentrations of melanin pigments, the degradation of which results in grey or white hair.
  • 1,2 The majority of hair dye products permanently change the hair color by a series of oxidative, dye-forming chemical reactions under alkaline conditions.
  • 1,3 The process typically involves the use of a base (e.g., ammonia) to swell and open up the cuticle scales on the hair surface, so that aromatic amine and/or phenol-based colorants (e.g., para-phenylenediamine and para-aminophenol) can penetrate deeply inside the hair.
  • a base e.g., ammonia
  • aromatic amine and/or phenol-based colorants e.g., para-phenylenediamine and para-aminophenol
  • An oxidant e.g., hydrogen peroxide
  • An oxidant is also needed to bleach the natural melanin pigments and to initiate reactions between the colorants to synthesize the final dye compounds. 1 Since the entire process is typically diffusion-limited, it can take hours to complete. Many of these molecular ingredients are toxic, and some are even carcinogenic. 3 If they are absorbed through the skin or inhaled, they could cause allergic reactions, 4-6 or even more severe consequences. 7-12 Treating hair with a weaker alkaline base or at near-neutral pH avoids the opening of the cuticles, and is less likely to inflict permanent hair damage. However, this limits the diffusion of colorants, leading to insufficient loading or semi-permanent to temporary coloration that can be reversed after a few washes. 13
  • a cosmetic composition may comprise graphene oxide (GO), reduced graphene oxide (r-GO), or both; a water dispersible polymer; and water.
  • a method of using a cosmetic composition may comprise applying a cosmetic composition comprising graphene oxide (GO), reduced graphene oxide (r-GO), or both; a water dispersible polymer; and water, to a keratin-based substrate to form a coating of the composition thereon and drying the coated substrate.
  • a cosmetic composition comprises graphene oxide (GO), reduced graphene oxide (r-GO), or both; a water dispersible polymer; and water.
  • the composition provides a coating on a keratin-based substrate to which the composition is applied after applying the composition to the substrate, rinsing the coated substrate, and drying the coated substrate.
  • the coating of the coated substrate has an average thickness of at least 1 ⁇ m and the average thickness varies by no more than ⁇ 10% across the surface of the coated substrate.
  • the composition is a hair coloring composition which changes a lightness (L*) value of the hair to which the composition is applied after applying the composition to the substrate, rinsing the substrate, and drying the substrate.
  • the composition comprises the r-GO and the r-GO is chemically reduced GO. In embodiments, the composition comprises the GO. In embodiments, the composition comprises both the GO and the r-GO and the r-GO is chemically reduced GO.
  • the water dispersible polymer is a compound which is soluble in water below a pH of 7 but which is insoluble in water above a pH of 7. In embodiments, the water dispersible polymer comprises amine groups. In embodiments, the water dispersible polymer is chitosan.
  • the composition comprises a second type of dispersant. In embodiments, the second type of dispersant is an acid. In embodiments, the second type of dispersant is ascorbic acid.
  • the composition comprises an amount of r-GO selected to provide a predetermined L* value to hair to which the composition is applied using a predetermined application procedure.
  • the composition comprises an amount of GO selected to provide a predetermined L* value to hair to which the composition is applied using a predetermined application procedure and after exposure to a predetermined amount of UV radiation or a predetermined amount of heat.
  • the composition comprises an amount of GO and an amount of an additional coloring agent, both selected to provide a predetermined L* value to hair to which the composition is applied using a predetermined application procedure.
  • the composition is free of any other coloring agents besides GO or r-GO.
  • the composition comprises at least 0.01 wt.
  • the composition consists essentially of the GO, the r-GO, or both; the water dispersible polymer; the water; optionally, the second type of dispersant; optionally, the co-solvent; and optionally, the additional coloring agent.
  • the composition consists essentially of the GO, the r-GO, or both; the water dispersible polymer; the water; optionally, a second type of dispersant; and optionally, a co-solvent.
  • the water dispersible polymer is chitosan and the second type of dispersant is an acid.
  • hair treated with the composition exhibits an L* value after 30 washes which has increased by no more than a factor of 1.75 as compared to an L* value of the treated hair before washing; wherein hair treated with the composition exhibits a surface static voltage after 30 washes which has increased by no more than a factor of 5 as compared to a surface static voltage of the treated hair before washing; or both.
  • hair treated with the composition has a coating of the composition thereon having an average thickness after 30 washes which has decreased by no more than 50% as compared to an average thickness of the treated hair before washing.
  • a method comprises applying a cosmetic composition comprising graphene oxide (GO), reduced graphene oxide (r-GO), or both; a water dispersible polymer; and water, to a keratin-based substrate to form a coating of the composition thereon and drying the coated substrate.
  • the substrate is hair having an L* value and the coated hair exhibits a changed L* value.
  • the coating of the coated substrate has an average thickness of at least 1 ⁇ m and the average thickness varies by no more than ⁇ 10% across the surface of the coated substrate.
  • the substrate is hair and the coated hair is curled prior to drying.
  • the method further comprises exposing the coated substrate or a region of the coated substrate to a predetermined amount of UV radiation or a predetermined amount of heat to provide a predetermined L* value for the coated substrate. In embodiments, the method further comprises exposing a plurality of regions of the coated substrate to different predetermined amounts of UV radiation or different predetermined amounts of heat to provide each region with a different predetermined L* value.
  • FIGS. 1A-1D demonstrate the graphene dyeing of light-colored hair.
  • FIG. 1A shows bundles of blonde hair before and after coating with r-GO/chitosan dye with increasing graphene concentrations, in comparison with another sample treated with a commercial permanent black hair dye.
  • FIG. 1B shows SEM images showing the surfaces of uncoated and coated hair (0.25 wt. %).
  • FIG. 1C shows the lightness of uncoated and graphene coated hairs, and those treated with the commercial permanent black hair dye, measured directly with a fiber optics spectrometer.
  • FIG. 1D show representative stress-strain curves of a strand of hair before and after graphene coating, showing no apparent change in tensile properties.
  • FIGS. 2A-2D demonstrate the antistatic property of graphene coated hair.
  • FIG. 2A shows strands of uncoated hair
  • FIG. 2B shows strands of hair treated with a commercial black dye
  • FIG. 2C shows graphene coated hair before (top row) and after (bottom row) electrostatic charging.
  • the strands are tied with an insulating cotton string on the top. Uncoated hairs and hairs treated with commercial dye cannot dissipate the electrostatic charges, and show strong “flyaway” effect.
  • the antistatic effect of graphene coating (0.25 wt. %) is evident.
  • FIG. 2D shows the surface static voltage of the hair bundles decreased drastically with graphene coatings.
  • FIGS. 3A-3D demonstrate the durability of graphene coated hair against washing. Images showing bundles of ( FIG. 3A ) carbon black/chitosan coated and ( FIG. 3B ) graphene-dyed hair (0.25 wt. %) before and after repeated shampoo washing. FIGS. 3C and 3D compare the corresponding changes in lightness and surface static voltage, respectively. The 2D morphology of r-GO may provide barrier properties that better protect the composite against washing. Additional exhaustive washing tests showed that graphene-coated hair can sustain at least over 30 times of washing ( FIG. 3C ), which already approaches the performance requirement of commercial permanent hair dyes.
  • FIGS. 4A-4B demonstrate gradient dyeing using GO/chitosan triggered by UV irradiation.
  • Gradient coloring FIG. 4A
  • reduction in lightness FIG. 4B
  • FIGS. 4A-4B demonstrate gradient dyeing using GO/chitosan triggered by UV irradiation.
  • Gradient coloring FIG. 4A
  • reduction in lightness FIG. 4B
  • FIGS. 4A-4B demonstrate gradient dyeing using GO/chitosan triggered by UV irradiation.
  • Gradient coloring FIG. 4A
  • reduction in lightness FIG. 4B
  • FIG. 5 demonstrates that graphene coated hair can fix the curvature of the coated hair without extra heat treatment or without applying small molecular chemicals.
  • FIG. 6 shows the lightness of uncoated and graphene/polyaniline coated hair measured directly with a fiber optics spectrometer.
  • the cosmetic compositions comprise graphene oxide (GO), reduced graphene oxide, or both.
  • the GO and r-GO colorants can be formulated in water without hazardous ingredients or solvents, and applied to hair (including blonde, grey and/or white hair) by spraying or brushing to yield various shades of brown to black colors. They can also sustain vigorous shampoo washing for dozens of times.
  • the GO and r-GO have much better film-forming capabilities and durability as compared to other conventional carbon-based colorants.
  • embodiments of the graphene-based hair coloring compositions impart a broad range of new optical, electrical, thermal, and biochemical properties to hair, enhancing comfort level and cosmetic performance.
  • cosmetic compositions are provided.
  • the cosmetic compositions are formulated for topical application to a variety of substrates in order to alter the appearance thereof.
  • the substrates may include keratin-based substrates such as the hair, fur skin, nails, etc. of a mammal, including humans.
  • the term “hair” includes hair anywhere on the human body, e.g., hair on the scalp, eyelashes, eyebrows, etc.
  • a cosmetic composition comprises graphene oxide (GO), reduced graphene oxide (r-GO), or both and water.
  • graphene-based refers to compositions comprising GO, r-GO, or both.
  • the GO/r-GO in the cosmetic compositions is used as a coloring agent.
  • the GO/r-GO is in the form of a plurality of thin, flexible sheets. Each sheet may comprise from one to several (e.g., 3 - 10 ) monolayers of GO or r-GO. Thus, the thickness of the sheets may be less than about 10 nm, less than about 5 nm, less than about 1 nm, or in the range of from a monolayer to about 1 nm.
  • the lateral dimensions of the sheets may be on the order of microns, e.g., 1 ⁇ m, 10 ⁇ m, 50 ⁇ m, 100 ⁇ m, providing an aspect ratio of at least >1000.
  • the thinness and flexibility of the sheets facilitates the formation of a conformal coating of GO/r-GO on the surfaces of the substrates to which the cosmetic compositions are applied.
  • Known methods may be used to form the GO and the r-GO of the cosmetic compositions, including the methods described in the Example below (i.e., modified Hummers' method to form GO and chemical reduction of GO via a reducing agent, e.g., ascorbic acid, to form r-GO).
  • the r-GO is chemically reduced GO.
  • Such r-GO is physically and chemically distinguishable from GO which has been reduced by other methods.
  • Such r-GO is also physically and chemically distinguishable from graphene formed by other methods.
  • the r-GO is characterized by a resistivity of 10 4 ohms/square or less, of 10 5 ohms/square or less, or in the range of from 10 4 to 10 5 ohms/square.
  • GO/r-GO may be used in the cosmetic compositions, depending upon the desired application and/or the desired properties for the treated substrates.
  • the composition may include an amount of r-GO selected to provide a desired darkness.
  • FIG. 1A shows samples of light-colored hair (in this embodiment, blonde hair) onto which a hair coloring composition comprising various amounts of r-GO from 0.025 wt. % to 0.25 wt. % was applied.
  • wt. % it is meant weight of the named component as compared to the total weight of the cosmetic composition.
  • the composition comprises an amount of r-GO selected to provide a predetermined lightness value (L*) to a surface of a substrate to which the composition is applied using a predetermined application procedure.
  • the predetermined application procedure may refer to, e.g., combing, brushing, spraying, rubbing, dip-coating, soaking the substrate; waiting a period of time, e.g., 5 minutes; rinsing the coated substrate with water; and drying the coated substrate.
  • the predetermined application procedure may be provided as a set of instructions with the cosmetic composition.
  • the amount of r-GO is selected to provide a L* value of no more than about 40, no more than about 35, no more than about 20, or in the range of from 20 to 40. (See FIG. 1C .)
  • GO absorbs ultraviolet (UV) radiation, which can convert transparent GO to dark r-GO.
  • UV ultraviolet
  • the cosmetic composition may include an amount of GO selected to provide a desired level of UV protection to the substrate to which the cosmetic composition is applied.
  • the level of UV protection may be quantified as a sun protection factor (SPF), similar to sunscreens.
  • SPF value may refer to that measured from a 1 ⁇ m to 5 ⁇ m, e.g., 2 ⁇ m, thick layer of the cosmetic composition (after application and drying) using the measurement method described in Dutra, Elizangela Abreu, et al.
  • the cosmetic composition includes an amount of GO selected to provide a predetermined SPF value to a surface of a substrate to which the cosmetic composition is applied using a predetermined application procedure.
  • the predetermined application procedure may refer to, e.g., combing, brushing, spraying, rubbing, dip-coating, soaking the substrate; waiting a period of time, e.g., 5 minutes; and drying the coated substrate.
  • the predetermined application procedure may be provided as a set of instructions with the cosmetic composition.
  • the amount of GO is selected to provide a SPF value of at least 10, at least 30, or at least 50.
  • the UV-absorbing property of GO may also be used to provide an indicator of UV exposure. Specifically, the darkness of a substrate treated with a GO-containing cosmetic composition may be compared to a predetermined calibration chart (correlating darkness to length of UV exposure) in order to determine the length of time the treated substrate must have been exposed to UV light.
  • the UV-absorbing property of GO may also be used in applications in which different regions of GO-coated substrates are exposed to different amounts of UV-radiation (e.g., different intensities or exposure times) in order to provide a substrate having different levels of darkness in the different regions.
  • the UV-exposure may be controlled and/or combined with masks/filters to achieve any number of predetermined patterns, e.g., the gradient or “ombre” effect shown in FIG. 4A . Since GO may also be converted to r-GO by using heat, patterning a substrate with different levels of darkness in different regions thereon may be carried out using heat instead of UV-radiation.
  • the cosmetic composition may comprise an amount of GO selected to provide a predetermined L* value to a surface of a substrate to which the cosmetic composition is applied using a predetermined application procedure (see above) and after exposure to a predetermined amount of UV radiation (e.g., exposure to a UV lamp for 1, 2, 3, 5, 10 hours) or a predetermined amount of heat (e.g., exposure to a hair drier for 5, 20, 30, 45, 60 minutes).
  • a predetermined amount of UV radiation e.g., exposure to a UV lamp for 1, 2, 3, 5, 10 hours
  • a predetermined amount of heat e.g., exposure to a hair drier for 5, 20, 30, 45, 60 minutes.
  • the predetermined application procedure/amount of UV radiation/amount of heat may be provided as a set of instructions with the cosmetic composition.
  • the amount of r-GO in the cosmetic composition is in the range of from 0 to about 1 wt. %. In embodiments, the amount of GO in the cosmetic composition is in the range of from 0 to about 1 wt. %. In both cases, this includes amounts in the range of from about 0.1 wt. % to about 0.75 wt. %, or from about 0.2 wt. % to about 0.5 wt. %. In embodiments, the only coloring agents used in the cosmetic composition are GO and r-GO; i.e., the composition is free of any other coloring agents.
  • the only coloring agent used in the composition is GO, r-GO, or both GO and r-GO.
  • the cosmetic compositions may also include a dispersant selected to facilitate dispersion of the GO/r-GO within the water.
  • the dispersant may also be selected to facilitate the binding of the GO/r-GO to the substrate to which it is applied.
  • Water dispersible or water soluble polymers may be used as dispersants, e.g., polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, and polysaccharides, e.g., starch. Sucrose, glucose, keratin, acrylic acid, and cysteine may also be used as dispersants.
  • the dispersant is a compound which is soluble in water below a pH of 7 (e.g., pH of 1, 2, 3, 4, 5, 6), but which is insoluble in water above a pH of 7 (e.g., 8, 9, 10, 11, 12, 13, 14).
  • the dispersant is a water dispersible polymer comprising amine groups.
  • the dispersant is chitosan.
  • Water dispersible or water soluble polymers capable of strongly adhering to hair and to GO or to r-GO simultaneously through hydrogen bonding, pi-pi stacking and/or forming covalent bonds, such as other polysaccharides, or other amine-containing polymers or short chain oligomers, including conducting polymer polyanilines and non-conducting, amine-containing polyelectrolytes may be used.
  • the GO/r-GO and chitosan function synergistically to provide a uniform and durable coating on hair.
  • More than one type of dispersant may be used.
  • ascorbic acid an acid dispersant
  • a co-dispersant may be included in the cosmetic composition as a second type of dispersant, i.e., a co-dispersant.
  • co-dispersants include acetic acid, formic acid and hydrochloric acid.
  • Other of the water dispersible/soluble polymers as described above may be used as a co-dispersant.
  • the amount of a first type of dispersant is in the range of from about 0.1 wt. % to about 1 wt. %. This includes embodiments in which the amount of a first type of dispersant is in the range of from about 0.2 wt. % to about 0.75 wt. % or from about 0.4 wt. % to about 0.6 wt. %.
  • the amount of a second type of dispersant is in the range of from about 1 wt. % to about 10 wt. %. This includes embodiments in which the amount of a second type of dispersant is in the range of from about 2 wt. % to about 8 wt. % or from about 4 wt. % to about 6 wt. %.
  • the cosmetic composition is free of a hair binding peptide, including the hair binding peptides disclosed in U.S. Pat. No. 7,452,528, which is hereby incorporated by reference for its disclosure of hair binding peptides.
  • the cosmetic composition is free of a diethylene triamine copolymer, a polymeric quaternary ammonium salt, and a quaternized polyvinyl pyridine.
  • the cosmetic compositions may also include other additives depending upon the application.
  • Illustrative additives include those generally found in cosmetic compositions formulated for use on hair, skin, nails, e.g., hair coloring compositions, hair shampoos, hair conditioners, hair spray, hair gel, hair mousse, sunscreen, make-up, lotion, nail polish, etc.
  • hair coloring compositions e.g., hair shampoos, hair conditioners, hair spray, hair gel, hair mousse, sunscreen, make-up, lotion, nail polish, etc.
  • cosmetic compositions are characterized by the absence of ingredients found in certain conventional cosmetic compositions, e.g., conventional hair coloring compositions.
  • the cosmetic composition is free of such components.
  • bases e.g., ammonia
  • oxidants e.g., peroxides
  • coloring agents e.g., para-phenylenediamine, para-aminophenol, pigments such as carbon black, carbon-based colorants such as carbon nanotubes.
  • the cosmetic composition is free of such components.
  • free has a meaning analogous to that described above.
  • the cosmetic compositions may include other coloring agents besides GO/r-GO.
  • Such other coloring agents include molecular dyes or pigment particles, including dyes/pigments typically used in temporary and semi-permanent hair coloring compositions.
  • Illustrative dyes/pigments include conducting polymer polyaniline (naturally blue, but turns green in the presence of an acid), rhodamine 6G (red), Coomassie violet 8200 (purple). This list is not exhaustive as any dye/pigment may be used.
  • the GO/r-GO extends the durability of the treated substrate against washing, effectively converting a temporary or semi-permanent dye/pigment into a more permanent one.
  • the two-dimensional and flexible morphology of GO/r-GO may act as a barrier to protect the other coloring agents against washing, making the colorization effect last longer.
  • the cosmetic composition may include a non-graphene, two-dimensional material, e.g., a clay.
  • the combination of GO/r-GO with molecular dyes/pigments also provides the treated substrate with additional antistatic and/or chromic properties.
  • the cosmetic composition may comprise an amount of GO/r-GO/additional colorant selected to provide a predetermined L* value to a surface of a substrate to which the cosmetic composition is applied using a predetermined application procedure (see above).
  • the balance of the cosmetic composition is made up of water, i.e., the cosmetic compositions are aqueous in nature.
  • the water content is generally greater than about 50 wt. %, 60 wt. %, 75 wt. %, 85 wt. %, or 95 wt. %.
  • Co-solvents e.g., a short chain alcohol such as ethanol, may be used but are not required.
  • An illustrative hair coloring composition comprises at least 0.01 wt. % of GO, r-GO, or both; no more than 5 wt. % of a dispersant; no more than 10 wt. % of a co-dispersant; no more than 10 wt. % of a co-solvent; from 0 wt. % to 10 wt. % of an additional colorant; and water.
  • the hair coloring composition consists essentially of or consists of these components.
  • the present disclosure provides methods of using the cosmetic compositions described herein.
  • a method comprises applying the cosmetic composition to a surface of a desired substrate to form a coating of the cosmetic composition thereon.
  • the application may be carried out in various ways including combing, brushing, spraying, rubbing, dip-coating, soaking, etc.
  • the method may further comprise drying the coated substrate.
  • the drying may be in air or may be facilitated by using heat.
  • the drying may be carried out for a period of time and at a temperature selected to remove water from the coating and/or to provide a desired darkness of the coated substrate (e.g., when converting GO to r-GO using heat).
  • the method may further comprise exposing the coated substrate to UV radiation under conditions (e.g., wavelength, intensity, time) to provide a desired darkness of the coated substrate.
  • the method may further comprise the step of washing the coated substrate with water (or a cleaning composition such as a shampoo) to remove excess colorant.
  • the drying step is carried out without first washing with water or a cleaning composition.
  • the coated substrate is curled (including bending, twisting, etc.) prior to drying.
  • the present disclosure provides substrates which have been treated with the cosmetic compositions described herein.
  • Illustrative substrates have been listed above and include hair, e.g. human hair.
  • Treated hair may characterized by the thickness of the graphene-based coating thereon.
  • the coating has an average thickness of at least about 1 ⁇ m, at least about 2 ⁇ m, at least about 3 ⁇ m, or in the range of from about 1 ⁇ m to about 5 ⁇ m.
  • average thickness it is meant an average over a representative number of hairs. The average thickness may be determined from scanning electron microscope (SEM) images of cross-sections of coated hairs.
  • Treated hair may be characterized by the uniformity of the graphene-based coating thereon.
  • the coating has an average thickness that does not deviate by more than about ⁇ 10%, about ⁇ 5%, or about ⁇ 2% along the length of the hair from one end to an opposing end. Uniformity may also be determined from SEM images of treated hair. (See FIG. 1B .) Embodiments of the present cosmetic compositions provide darker and more uniform coatings as compared to hair treated with carbon particle-based compositions from corresponding dyes with the same loading levels, between 0.025 to 0.25 wt. %.
  • At least some embodiments of the present cosmetic compositions provide treated hair with increased antistatic properties and/or increased thermal conductivity as compared to untreated hair.
  • the antistatic properties of hair may be quantified by measuring the surface static voltage of the hair using a surface DC voltmeter under the conditions and using the application method described in the Example, below.
  • Treated hair may be characterized by a surface static voltage that is at least 6 times lower than untreated hair, at least 10 times lower, at least 50 times lower, or at least 100 times lower.
  • the amount of GO/r-GO in the cosmetic composition may be selected to provide a desired antistatic performance. (See FIG.
  • the thermal conductivity of hair may be quantified by measuring the heating or cooling rate of hair using an infrared (IR) camera under the conditions and using the application method described in the Example, below.
  • Treated hair may be characterized by a heating/cooling rate that is at least 2 times faster, at least 3 times faster, or at least 5 times faster than untreated hair.
  • Treated hair may also be characterized by its durability, i.e., its resistance to a change in a property after washing.
  • the durability may be quantified by measuring the L* value of the treated hair (treated as per the application method described in the Example, below) after washing (under the conditions described in the Example, below).
  • the treated hair exhibits an L* value after a predetermined number of washes (e.g., 5, 10, 15, 20, 25, 30, 35) which has increased by no more than a factor of 1.75, 1.70, 1.65, or 1.60 as compared to an L* value of the treated hair before washing. (See FIG.
  • the durability may be quantified by measuring the surface static voltage of the treated (treated as per the application method described in the Example, below) after washing (under the conditions described in the Example, below).
  • the treated hair exhibits a surface static voltage after a predetermined number of washes (e.g., 5, 10, 15, 20, 25, 30, 35) which has increased by no more than a factor of 5, 4, 3, or 2 as compared to a surface static voltage of the treated hair before washing.
  • the durability may also refer to a resistance to a change in other properties, e.g., coating thickness, coating uniformity, coating coverage (measurable via SEM), curvature, etc.
  • the average thickness of the coating of the treated hair (treated as per the application method described in the Example, below) after a predetermined number of washes under the conditions described in the Example, below has not decreased by more than 50% as compared to the average thickness of the treated hair before washing. This includes decreases of no more than 40%, 30%, or 20%.
  • hair coloring compositions provided herein are significantly less damaging to hair. This may be quantified by measuring the tensile properties of treated hair using a mechanical analyzer under the conditions described in the Example, below.
  • the treated hair exhibits a tensile stress-strain curve which is about the same (e.g., does not deviate by more than 10%) as a tensile stress-strain curve of untreated hair. (See FIG. 1D .)
  • This Example demonstrates that graphene-based sheets are found to be excellent hair dyes.
  • graphene oxide (GO) and its reduced form r-GO water-based formulations can be obtained to form smooth and continuous coatings on hair. This not only avoids the use of toxic, small molecular ingredients in common black hair dyes, but also renders new properties of hair for enhanced comfort, such as greatly improved antistatic performance and heat dissipation.
  • the graphene hair dyes can form a strongly adhering coating on hair surfaces, which can resist repetitive shampoo washing, reaching the performance requirement of permanent hair dyes.
  • the color of the GO coating can be gradually darkened or patterned to create the effect of gradient dyeing, and the lightness of the resulting r-GO coating can be adjusted through loading level to produce different shades.
  • GO was prepared through a modified Hummers' method 19 and purified with two-step washing. 51 GO (5 mg/mL in water, 10 mL) was then reduced with ascorbic acid (5 wt %, 10 mL) under stirring and heating at 90° C. for 1 hour. The resulting black r-GO product was washed 3 times with DI water through exhaustive centrifugation (10000 rpm, 5 min). Next, 50 mg of chitosan (Sigma-Aldrich, medium molecular weight) was dissolved in 20 mL of warm ascorbic acid solution (60° C., 2.5 mg/mL) to create a chitosan gel, in which the sheets were better dispersed. Chitosan gel also improves the adhesion to the hair surface.
  • chitosan Sigma-Aldrich, medium molecular weight
  • Bundled hair coated with r-GO/chitosan was soaked in 5 vol. % of shampoo (Pantene Pro-V) in 40 mL of water sealed in a 50 mL centrifugation tube (Falcon). The tube was then horizontally fixed on a vortex mixer and vigorously shaken for 5 minutes. The frequency is determined to be about 10-12 Hz by counting the tube's movement from a recorded video. After washing, the hair was rinsed with water and dried in air or at 60° C. The r-GO/chitosan coating can sustain over 30 washes without significant decoloration.
  • the lightness of hair (L*), 52 which is an indicator of the darkness of hair was measured directly using a Jaz fiber optics spectrometer (Ocean Optics Inc.).
  • the spectrometer was first calibrated with a hemispherical reflectance black standard and printer paper ( 92 bright).
  • the L* measured from the printing papers was set to be 100, and L* from the black standard was set to be 0.
  • the original lightness of the blonde hair was measured to be around 75. For every sample, lightness was measured 10 times to calculate the average value.
  • the surface static voltage was measured using a surface DC voltmeter (SVM2, Alphalab, Inc.) Electrostatic charges were induced by rubbing a Scotch® polypropylene sheet against a strand of hair for 10 times, which was tied and suspended with an insulating cotton thread. A surface DC voltmeter was placed 1 inch away from the sample to record the induced static voltages. For every sample, 5 measurements were made to calculate the average value.
  • SVM2 Surface DC voltmeter
  • IR images and temperatures of the hair were recorded using an IR camera (Optotherm, InfraSight MI320).
  • the hair samples were placed on top of a heating element set at 34° C., the typical temperature of human skin, right before IR recording.
  • the hair samples were first heated to the same temperature of 36° C., and the heating element was removed immediately before IR recording. Room temperature during the experiments was around 24° C.
  • Blonde hair samples were used to test the performance of graphene dyes.
  • the typical composition of the dye solutions includes r-GO sheets as the colorants, chitosan polymer as the dispersing agent 31,32 and vitamin C (i.e., ascorbic acid) as the co-dispensing agent, which was also used to reduce GO.
  • the atomic force microscopy (AFM) images showed that the lateral dimensions of GO sheets are a few microns, with a thickness of around 1 nm. After reacting with ascorbic acid, GO sheets in the brown colloidal dispersion turned into black r-GO sediment. Chitosan was utilized as a dispersing agent for r-GO and a binder to improve the adhesion of the graphene hair dye.
  • both GO and r-GO/chitosan dispersions can easily form uniform coatings on a surface by drop casting.
  • the UV-Vis spectra obtained show that r-GO indeed has much stronger absorption than GO in both the UV and visible range of wavelengths, due to partial restoration of the conjugated carbon network after reduction. This is a much simpler and safer formulation than organic hair dyes, as it does not contain any toxic molecular specifies or volatile components.
  • the water-based dye solution can be directly applied to hair by spraying and/or combing to generate a uniform coating, without the need for any pre-treatment. After drying the r-GO dye in air or with a hair dryer, the color of the hair turned into a uniform shade of black. This coating-based dyeing process can be completed in less than 10 minutes, which is much faster than using diffusion-based molecular hair dyes.
  • FIG. 1A gradient shades of black can be achieved by varying the concentration of graphene in the dye solution from 0.025 to 0.25 wt. %.
  • SEM scanning electron microscope
  • FIG. 1B The thickness of the graphene layer was found to be typically around 2 ⁇ m.
  • the difference in hair darkness was quantified by lightness measurements based on optical reflectance ( FIG. 1C ), which suggests that the lightness of r-GO coated hair can be continuously decreased by increasing the loading of r-GO. It was found that 0.025 wt.
  • % graphene dispersion started to yield a visually uniform coating on hair, and the 0.25 wt. % dispersion already dyed the hair in dark black, approaching the appearance and lightness rendered by a commercial black hair dye.
  • the cuticles In conventional hair dyeing, the cuticles must be opened to allow the diffusion and reaction of colorants inside hair. This significantly degrades the hair's mechanical properties, which may not fully recover afterward.
  • the graphene coating does not react with hair and does not weaken the hair based on the results of tensile tests ( FIG. 2D ).
  • FIG. 3C shows that the graphene coating rendered hair excellent antistatic performance to avoid static build up.
  • the surface static voltages on rubbed hair were measured using a surface DC voltmeter.
  • FIG. 3D shows that rubbing induced a surface static voltage of around 5 kV for both the uncoated hair and hair treated with commercial dye, and only about 0.8 kV and 0.05 kV for hair treated with 0.025 and 0.25 wt.% of graphene dye, respectively.
  • the r-GO coating used in this work was only lightly reduced by ascorbic acid to render black color, and typically has a resistivity on the order of 10 4 to 10 5 ohms/square, which is already sufficient for antistatic purposes.'
  • graphene hair dye does not change hair color through chemical reactions, the graphene/chitosan coating strongly adheres to hair after drying and cannot be easily washed off. This is attributed to the following factors: First, GO and r-GO sheets are highly flexible due to their high aspect ratio, and they can strongly interact with chitosan through hydrogen bonding. 36,37 This soft sheet-like shape also helps to yield a thin and uniform composite coating after drying. Next, chitosan can bind strongly with and keratin, the key structural protein at the surface of hair, through its amino and hydroxyl groups. More interestingly, chitosan is insoluble in water under near neutral to basic conditions, but becomes soluble in the presence of weak acid such as ascorbic acid. 40 When excess ascorbic acid is rinsed off after hair dyeing, the r-GO/chitosan coating becomes insoluble. These properties of chitosan make it a very suitable binder for graphene-based hair dyes.
  • graphene coated hair retains its excellent antistatic properties even after exhaustive washing for 30 times ( FIG. 3D ).
  • Commercial permanent hair dyes generally are not affected by washing since the chemical reactions changes the composition of the hair. However, they also need to be re-applied, typically after about one month or 30 washes due to hair growth. 2 r-GO/chitosan coated hair can resist at least 30 shampoo washes without significant degradation in color and antistatic properties. Therefore, the durability of such graphene hair dyes is already sufficient to render a “permanent” coloring effect.
  • Gradient hair dyeing also known as “ombre” has recently grown in popularity. This is usually done by applying more than one hair dye along the length of the hair strands, which requires more sophisticated control over timing and colorant compositions during dyeing procedures. Since GO sheets can gradually darken from transparent to black when they are converted to r-GO, they can be used to achieve the ombre hairstyle by controlling their degree of reduction through chemical, thermal, and light based approaches. 27-30 A proof-of-concept is shown in FIG. 4A , where a bundle of hair strands was first coated with a GO/chitosan solution (0.25 wt.%), followed by UV irradiation to reduce GO.
  • Photomasks were used to control the exposure time of different parts of the hair to generate a gradient of shades from blonde to dark brown, corresponding to gradually decreased lightness ( FIG. 4B ). More rapid darkening can be achieved by using a higher intensity of UV light, or by applying chemical or thermal treatment based on various reduction mechanisms of GO. 27-30 On the other hand, since GO sheets absorb strongly UV light, 25,26 GO-based coatings can also serve as a light colored UV block to protect hair from irradiation damage, as well as a colorimetric indicator of the accumulative dose of UV exposure.
  • graphene-based coatings In many engineering applications using graphene-based coatings, the black color of graphene is usually not a desirable feature. Using graphene coating for hair dye turns this compromise into a significant advantage. Unlike many other graphene applications that rely on the use of highly conductive and structurally more perfect r-GO or graphene sheets, hair—or in extension fiber dyeing—is very tolerant to the variations in their structures and electrical properties. Graphene-based hair dyes can be formulated without hazardous additives or volatile components, and do not impart permanent chemical and structural changes of hair. Therefore, they are safer to use than molecular dyes.
  • GO- and graphene-based sheets with large micron-sized lateral dimensions are much less likely to penetrate the dermal barrier, 41-43 especially when they are in a polymer matrix such as the chitosan gel used in this Example.
  • Graphene-based hair dyes can be applied simply by spraying and combing, which helps to complete the dyeing process more quickly than molecular dyes. Yet the coloration is quite durable, which is already comparable to commercial permanent hair dyes. In addition to their main function of dark or gradient coloration, r-GO and GO based hair dyes offer a number of enhancements to hair properties, including better antistatic and heat dissipation performances as demonstrated above.
  • graphene hair dyes have other uses. For example, they could be applied to coat animal furs to reduce electrostatically induced irritation in livestock farming. Antistatic hair will be useful for the development of humanoid robots to reduce the level of static interruption to embedded electronics. Highly conductive hair strands may also be repurposed as in-situ electrodes to interface with skin or “dermal electronics”, 47 or become functional elements in wearable devices. Finally, at the end of their use, graphene coated hair waste can be readily repurposed or converted to make energy storage or sensing devices. 48-50
  • the r-GO and GO hair dyes prepared as described above were applied to human hair samples as described above. However, prior to drying, the hair samples were curled. After curling, the hair samples were dried. The results shown in FIG. 5 demonstrate that the r-GO/GO coating can increase the bending stiffness of hair so as to fix its curvature. No extra heat treatment or chemicals are needed to change the chemical structure of the hair.
  • Hair dyes containing various amounts of polyaniline (PANI) and GO were prepared in water.
  • Various relative amounts of PANI and GO were used, from 10:1 to 1:10, including 1:1.
  • the relative amount of PANI and GO may be used to tune the color from blue (excess of PANI) to black (excess of GO).
  • the hair dyes were applied to blonde human hair samples as described above.
  • the treated blonde hair darkened (decreased L* values).
  • FIG. 6 shows the lightness of uncoated and PANI/GO coated hairs (using compositions from 0.1 wt. % to 0.4 wt. % of PANI/GO), measured directly with a fiber optics spectrometer as described above. SEM images confirmed that the coating was uniform on individual strands of hair.
  • PANI/GO coated hair was also confirmed as described above (results similar to those shown in FIG. 2C ). Finally, portions of PANI/GO coated hairs were “doped” with acid by exposing to an acidic vapor or solution (pH ⁇ 6) to induce a color change of dark blue/black to green.
  • Hair dyes containing GO and molecular dye either Rhodamine 6G or Coomassie Violet R200
  • the hair dyes were applied to blonde human hair samples as described above.
  • the treated blonde hair darkened to either red (Rhodamine 6G) or purple (Coomassie Violet R200).
  • Durability tests conducted as described above showed that the treated hair retained the red/purple color after multiple rounds of washing.

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