Lipophilic dispersed phenolic polymer particles

Abstract

A composition includes phenolic polymer particles and a surfactant on the phenolic polymer particles. The composition is lipophilic. The dispersion comprises phenolic polymer particles, a surfactant, and a carrier medium. The carrier may be a cosmetically acceptable fluid or a lipophilic wax. The present invention relates to lipophilic dispersed phenolic polymer particles.

Description

[0001] This application is a divisional application of the patent application with application number 202080075151.7, application date September 8, 2020, and invention title "Lipophilic Dispersed Phenolic Polymer Particles". Background Art

[0002] Phenolic polymers are a class of organic polymers characterized by the presence of multiple OH-substituted phenyl groups. Phenolic polymers have many unique properties, such as the ability to act as antioxidants or skin conditioners. These properties make phenolic polymers included in topically applied formulations, such as cosmetics and dermatological preparations. Well-known examples of phenolic polymers include lignin, lignosulfonates, humates, and tannins.

[0003] Lignin is a particularly desirable phenolic polymer because it is ubiquitous. Modern papermaking processes involve removing lignin from lignocellulose. The global paper industry produces approximately 40–50 million tons of lignin per year as waste (The International Lignin Institute, “About lignin”, available online at www.ili-lignin.com / aboutlignin.php (published August 30, 2019)). Lignin is also produced as a by-product of sulfite pulping to remove lignin from wood pulp. Typically, waste lignin is burned to provide energy for the paper mill that produces it. Methods have been developed to convert waste lignosulfonates and sulfate lignin into useful commodities. For example, high-quality lignin can be obtained from the black liquor generated in the kraft process for papermaking using the process or the LIGNOFORCE TM process. However, tens of millions of tons of waste lignin are still produced each year, which could be converted into useful chemical products.

[0004] Despite their availability as raw materials, formulation challenges limit the demand for phenolic polymers. Lignin and other phenolic polymers are highly soluble in water. Thus, phenolic polymers are only included in the aqueous phase of formulations. The high water solubility of phenolic polymers also limits their inclusion in topical formulations in solid form, because if the phenolic polymers are exposed to water, they will wash off the skin of the user. These solubility problems limit the ability of manufacturers to fully utilize the useful properties of phenolic polymers. Summary of the Invention

[0005] In a first aspect, the present invention provides a composition comprising phenolic polymer particles and a surfactant on the phenolic polymer particles.

[0006] In a second aspect, the present invention provides a dispersion comprising sodium lignosulfonate particles, a surfactant, and a carrier medium. The sodium lignosulfonate particles have a particle size of 0.1–1.0 micrometers. The dispersion is pourable.

[0007] In a third aspect, the present invention provides a dispersion comprising silanized phenolic polymer particles and a carrier medium.

[0008] In a fourth aspect, the present invention provides lipophilic phenolic polymer particles.

[0009] Definitions

[0010] The term "phenolic polymer" refers to a water-soluble polymer comprising multiple OH-substituted phenyl groups. Examples of phenolic polymers include lignin, humates, tannins, and plant extracts containing water-soluble and / or water-dispersible components.

[0011] The term "ultraviolet radiation" refers to electromagnetic radiation having a wavelength of 10–400 nm. Ultraviolet radiation is also referred to as ultraviolet light, UV radiation, or UV rays. In this application, the abbreviation "UV" may be used interchangeably with the phrase "ultraviolet light".

[0012] The term "high-energy visible radiation" or "HEV radiation" refers to electromagnetic radiation having a wavelength of 400–490 nm. HEV radiation is perceived as blue and violet light in the visible spectrum.

[0013] Unless otherwise specified, the term "particle size" refers to the median (D50) particle size determined by static light scattering based on number distribution (ISO 13320:2009 Particle size analysis - Laser diffraction method).

[0014] The term "highly water-resistant" refers to a composition having a change in monochromatic protection factor (MPF) of less than 50% between the MPF before exposure to water and the MPF after 80 minutes of immersion in water in vitro. (Cosmetics Europe, "Guidelines for evaluating sun product water resistance", available online at www.cosmeticseurope.eu / files / 7914 / 6407 / 7400 / Guidelines_for_Evaluating_Sun_Product_Water_Resistance_-_2005.pdf, page 15 (2005)).

[0015] "Improved DPPH Photostability Test" is a method for measuring the photostability of active materials. The improved DPPH photostability test is a more sensitive test than the DPPH photostability test described in the US patent application with publication number 2018 / 0291210, and has been verified for compositions other than zinc oxide. First, 0.025 g ± 0.001 g of the active material is added to four 50 mL disposable plastic beakers. A 0.0125% DPPH (diphenyl-(2,4,6-trinitrophenyl)iminonitronium, also known as diphenylpicrylhydrazine; CAS number 1898-66-4) is prepared in a BCS (ethylene glycol monobutyl ether) solution. 19.975 g ± 0.001 of the 0.0125% DPPH BCS solution is added to each beaker containing the active material to form a test mixture. The test mixture is thoroughly stirred with a glass stirring rod, and each test mixture is sonicated for 20 seconds to ensure sufficient dispersion of the active material. After sonication, each test mixture is transferred to a labeled liquid scintillation vial. The absorbance of the test mixture is measured on a calibrated colorimeter to obtain pre-irradiation measurement values. After the measurement, using a UVA lamp of 0.35 Wm -2 s -1 in a Q-Labs QUV Weatherometer, the test mixture is exposed to ultraviolet light at a constant temperature of 50 °C for 10 minutes. After irradiation, the absorbance of the test mixture is measured on a colorimeter. The photostability after exposure to UV is determined by the persistence of the purple color produced by the absorption band of the dye at 520 nm.

[0016] The photostability can be expressed as the total color change relative to a standard (ΔE in the L*a*b* color space) for a specified UV exposure time. According to the definition of the International Commission on Illumination standard CIE76, ΔE is calculated by Equation 1 below:

[0017] Equation 1: where L * 2, a * 2, and b * 2 are the color coordinates of the test mixture after irradiation, and L * 1, a * 1, and b * 1 are the color coordinates of the test mixture before irradiation. The data is reported as the average ΔE value of four samples.

[0018] The term "super photostable" refers to a substance with ΔE ≤ 4.5 when using the improved DPPH photostability test.

[0019] "Free radical quenching test" is a method for measuring the ability of an active material to quench free radicals. First, the photo-stability of titanium dioxide (35 nm, rutile phase) is measured according to the improved DPPH photo-stability test to establish a reference photo-stability (ΔE Ref ). Next, a test mixture containing the same weight percentage of titanium dioxide used to establish the reference photo-stability and an equal amount of the active material is prepared. Then, the photo-stability of the test mixture is measured according to the improved DPPH photo-stability test to establish a test photo-stability (ΔE Test ). Then, the percentage difference between the reference photo-stability (ΔE Ref ) and the test photo-stability (ΔE Test ) is calculated to determine the free radical quenching ability of the active material. If the active material can quench at least 70% of the free radicals generated by titanium dioxide (ΔE Test is at least 70% smaller than ΔE Ref ), then the active material passes the free radical quenching test.

[0020] Unless otherwise specified, all percentages (%) are weight / weight percentages. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] The present invention can be better understood with reference to the following drawings and description.

[0022] Figure 1 Is a cartoon schematic of phenol polymer particles modified with a surfactant. DETAILED DESCRIPTION

[0023] The present invention includes phenol polymer particles that have been modified to be lipophilic. Lipophilic phenol polymer particles can be formed by increasing the surface treatment of the particles or by reacting the particles with a silylating agent. Lipophilic modification enables the phenol polymer to exist in the oil phase of the formulation in a solid state. For example, the phenol polymer particles and the surfactant can be dispersed in a lipophilic carrier medium. The ability to use phenol polymer particles in the oil phase greatly expands the possible uses of these particles.

[0024] Experimental tests show that formulations comprising lipophilic phenol polymer particles have many desirable physical and chemical properties. These formulations are highly water-resistant and are strong HEV light blockers, indicating that they are very suitable for use in sunscreen formulations. When the improved DPPH photo-stability test is performed, the formulations are also super photo-stable. In addition, the formulations have also passed the free radical quenching test, demonstrating their strong antioxidant properties.

[0025] Without wishing to be bound by theory, it is believed that these properties stem from the presence of solid phenolic polymers. Physical interactions between phenolic polymer molecules enable pi (π)-stacking of aromatic groups, thereby enhancing the ability of these molecules to accept electrons due to orbital mixing. Although pi-stacking occurs when phenolic polymers are in solution, the solution must have a high enough concentration. Delivery of phenolic polymers as particles (i.e., in the solid state) ensures that they have pi-stacking.

[0026] Formulations containing phenolic polymer particles also have many commercial advantages. Phenolic polymers, especially lignin, are economically advantageous raw materials as they are abundantly available as waste. Capturing waste that would otherwise be burned is an environmentally friendly process as it prevents carbon emissions. Phenolic polymers derived from natural sources can be sold as natural products, which is particularly attractive to consumers. In addition, dispersions of phenolic polymer particles can be prepared using conventional chemical processing techniques that do not require expensive reactants, extreme temperatures, long reaction times, or hazardous reactants and do not generate hazardous waste. All of these advantages will encourage manufacturers to incorporate phenolic polymers into commercial formulations.

[0027] Figure 1 A cartoon schematic of phenolic polymer particles modified with a surfactant is shown. Composition 100 includes phenolic polymer particles 110 and surfactant 120 on the particle surface. The surfactant is a surface treatment agent that renders the phenolic polymer particles lipophilic and insoluble in water. A dispersion can be prepared by mixing the phenolic polymer particles, the surfactant, and a carrier medium. Preferably, the dispersion is pourable.

[0028] The phenolic polymer particles can be any polymer having multiple OH-substituted phenyl groups. Preferably, the phenolic polymer particles are lignin, humate, tannin, plant extracts containing water-soluble and / or water-dispersible components, or combinations thereof. Examples of suitable lignins include lignosulfonates, sulfate lignin, sulfonated sulfate lignin, oxidized lignin, sulfonated oxidized lignin, lignosulfonates copolymerized with monomers (such as acrylate, acrylic acid, acrylamide, styrene sulfonate, and naphthalene sulfonate derivatives), azo sulfonates, azo lignin, lignosulfonate-formaldehyde condensates, lignin formaldehyde condensates, hydrophobically modified lignosulfonates, hydrophobically modified lignin, cationically modified lignosulfonates, cationically modified lignin, amino lignosulfonates, amino lignin, alkylated lignosulfonates, alkylated lignin, crosslinked lignosulfonates, and crosslinked lignin. Examples of suitable humates include sulfonated humates, humate-formaldehyde condensates, hydrophobically modified humates, cationically modified humates, amino humates, and alkylated humates. Examples of suitable tannins include tannate, sulfonated tannate, tannate-formaldehyde condensates, hydrophobically modified tannate, and cationically modified tannate.

[0029] Examples of plant extracts containing water-soluble and / or water-dispersible components include extracts derived from plants known by the following names: Acacia, Afzelia, Synsepalum dulcificum, Albizia, alder (e.g., Alnus glutinosa and Alnus rubra), applewood, Arbutus, ash (e.g., F. nigra, F. quadrangulata, F. excelsior, F. pennsylvanica lanceolata, F. latifolia, F. profunda, and F. americana), poplar (e.g., P. grandidentata, P. tremula, and P. tremloides), Australian red cedar (Toona ciliata), ayan (Distemonanthus benthamianus), balsa (Ochroma pyramidale), basswood (e.g., T. americana and T. heterophylla), beech (e.g., F. sylvatica and F. grandifolia), birch (e.g., Betula populifolia, B. nigra, B. papyrifera, B. lenta, B. alleghaniensis, B. lutea, B. pendula, and B. pubescens), black bean, blackwood, bocote, boxelder, boxwood, brazilwood, bubinga, buckeye (e.g., Aesculus hippocastanum, Aesculus glabra, and Aesculus flava / Aesculus octandra), butternut, catalpa, cherry (e.g., Prunus serotina, Prunus pennsylvanica, and Prunusavian), crabwood, chestnut, coachwood, cocobolo, corkwood, cottonwood (e.g., Populus balsamifera, Populus deltoides, Populus sargentii, and Populus heterophylla), cucumbertree, dogwood (e.g., Cornus florida and Cornus nuttallii), ebony (e.g., Diospyros kurzii, Diospyros melanida, and Diospyros crassiflora), elm (e.g., Ulmus americana, Ulmus procera, Ulmus thomasii, Ulmus rubra, and Ulmus glabra), eucalyptus, greenheart, grenadilla, gum (e.g., Nyssa sylvatica, Eucalyptus globulus, Liquidambar styraciflua, and Nyssa aquatica), hickory (e.g., Carya alba, Carya glabra, Carvaovata, and Carya laciniosa), hornbeam, hophornbeam, ipe, iroko, ironwood (e.g., Bangkirai, Carpinus caroliniana, Casuarina equisetifolia, Choricbangarpia subargentea, Copaifera spp., Eusideroxylon zwageri, Guaiacum officinale, Guaiacum sanctum, Hopea odorata, Krugiodendron ferreum, Lyonothamnus ivonii (L. floribundus), Mesuaferrea), Olea spp., Olneyatesota, American hophornbeam (Ostrya virginiana), Persian ironwood (Parrotia persica) and serrate-leaved tabebuia (Tabebuia serratifolia)), jacaranda, jojoba, lacewood, laurel, limba, Lignum vitae, locust (e.g., black locust (Robinia pseudoacacia) and honey locust (Gleditsia triacanthos)), mahogany, maple (e.g., sugar maple (Acer saccharum), black maple (Acer nigrum), box elder (Acer negundo), red maple (Acer rubrum), silver maple (Acer saccharinum) and sycamore maple (Acer pseudoplatanus)), meranti, mpingo, oak (e.g., bur oak (Quercus macrocarpa), white oak (Quercus alba), post oak (Quercus stellata), swamp white oak (Quercus bicolor), southern live oak (Quercus virginiana), swamp chestnut oak (Quercus michauxii), chestnut oak (Quercus prinus), yellow chestnut oak (Quercus muhlenbergii), canyon live oak (Quercus chrysolepis), overcup oak (Quercus lyrata), English oak (Quercus robur), sessile oak (Quercus petraea), northern red oak (Quercus rubra), black oak (Quercus velutina), laurel oak (Quercus laurifolia), Spanish oak (Quercus falcata), water oak (Quercus nigra), willow oak (Quercus phellos) and Texas oak (Quercus texana)), obeche, okoumé, Oregon myrtle, California bay laurel, pear, poplar (e.g., balsam poplar (P. balsamifera), European black poplar (P. nigra) and hybrid poplar (Populus X canadensis)), ramin, redcedar), rosewood, sal, sandalwood, sassafras, satinwood, silky oak, silver wattle, snakewood, sourwood, Spanish cedar, American sycamore, teak, walnut (e.g., Juglans nigra and Juglans regia), willow (e.g., Salix nigra and Salix alba), yellow poplar (Liriodendron tulipifera), Araucaria (e.g., A. cunninghamii, A. angustifolia, and A. araucana), softwood cedar (e.g., Juniperus virginiana, Thuja plicata, Thuja occidentalis, Chamaecyparis thyoides, and Callitropsis nootkatensis), cypress (e.g., Chamaecyparis, Cupressus taxodium, Cupressus arizonica, Taxodium distichum, Chamaecyparis obtusa, Chamaecyparis lawsoniana, and Cupressus semperviren), Rocky Mountain Douglas fir, European yew, fir (e.g., Abies balsamea, Abies alba, Abies procera, and Abies amabilis), hemlock (e.g., Tsuga Canadensis, Tsugamertensiana), Tsuga heterophylla, kauri, kaya, larch (e.g., Larix decidua, Larix kaempferi, Larix laricina, Larix occidentalis, Larix europea), pine (e.g., Pinus nigra, Pinus banksiana, Pinus contorta, Pinus radiata, Pinus ponderosa, Pinus resinosa, Pinus sylvestris, Pinus strobus, Pinus monticola, Pinus lambertiana, Pinus taeda, Pinus palustris, Pinus rigida, Pinus echinata), redwood, rimu, spruce (e.g., Picea abies, Picea mariana, Picea rubens, Picea sitchensis, Picea glauca), sugi and mixtures / hybrids thereof. Preferred plant extracts containing water-soluble and / or water-dispersible components include those derived from spruce (also known as Norway spruce or European spruce), Larix europaea (also known as larch or European larch), and maple species (a mixture of Acer saccharum, Acer saccharinum, and Acer negundo).

[0030] The surfactant can be any surfactant that has strong acid-base interactions with the phenolic polymer particles and provides a lipophilic surface treatment on the particles. Examples of suitable surfactants include fatty alcohols and polyols (such as stearyl alcohol, behenyl alcohol, and cetearyl alcohol), fatty acids (such as stearic acid and oleic acid), amino acids (such as lauroyl lysine and myristoyl glutamate), polyglycerol esters (such as polyglycerol-3 ricinoleate, polyglycerol-6 ricinoleate, polyglycerol-10 pentastearate, and polyglycerol-4 oleate), polyglycerol polyesters (such as polyglycerol-4 diisostearate / polyhydroxystearate / sebacate, polyglycerol-2 dimer hydroxystearate, and polyglycerol-3 stearate / isostearate / dimer dilinoleate crosslinked polymer), polyesters having affinic hydroxyl, amine, or amide groups (such as polyhydroxystearic acid), polyurethanes having affinic hydroxyl, amine, or amide groups, polyamides having affinic hydroxyl, amine, or amide groups, polyacrylates having affinic hydroxyl, amine, or amide groups, phosphate esters (such as tris(laureth-4) phosphate and tris(ceteareth-4) phosphate), polymeric phosphates (such as 1,2-ethylenediamine, polymers having aziridine, N-[3-[(2-ethylhexyl)oxy]-3-oxopropyl] derivatives, and compounds including polyethylene-polypropylene glycol), phospholipids, ceramides, sphingosides (such as lecithin, lysophosphatidylcholine, and ceramide 3), substituted silicones having an affinity group (such as cetyldiglyceryl tris(trimethylsiloxy)silylethyl dimethicone, CAS No. 104780-66-7 (siloxanes and silicones, dimethyl, 3-hydroxypropyl terminated), CAS No. 102782-61-6 (siloxanes and silicones, dimethyl, 3-hydroxypropyl methyl), and CAS No. 106214-84-0 (siloxanes and silicones, dimethyl, 3-aminopropyl)) and combinations thereof.

[0031] Alternatively, lipophilic phenolic polymer particles can be formed by reacting the particles with a silylating agent. The silylating agent can be any substance that provides a functionalized polysiloxane on the surface of the phenolic polymer particles. Examples of suitable silylating agents include reactive siloxanes and silane hydrophobing surface treatment agents (such as triethoxyoctylsilane, octadecyltriethoxysilane, hydrogen dimethylsiloxane (CAS No. 68037-59-2 / 69013-23-6 / 70900-21-9), and CAS No. 69430-47-3 (siloxanes and silicones, dimethyl, reaction product of methylhydrosiloxane and 1,1,3,3-tetramethyldisiloxane)).

[0032] The carrier medium can be any cosmetically acceptable lipophilic fluid or wax. Examples of suitable carrier media include triglycerides (such as caprylic / capric triglyceride), esters (such as C12-C15 alkyl benzoate, isopentyl laurate, isopropyl isostearate, coco-caprylate, ethylhexyl isononanoate, tridecyl salicylate, ethylhexyl isononanoate, isodecyl salicylate, octyldodecyl neopentanoate, butyloctyl salicylate, jojoba esters, and shea butter ethyl ester), natural oils and butters (such as Simmondsia chinensis (jojoba) seed oil, shea butter, Argania spinosa (Argan) oil, pongami (karanja) oil, and Limnanthes alba (white meadowfoam) seed oil), alkanes (such as squalane, squalene, isododecane, and isocetane), silicones (such as dimethicone, behenyl dimethicone, cetyl dimethicone, cetearyl methicone, and phenyl dimethicone), waxes (such as natural waxes, synthetic waxes, and silicone waxes), and combinations thereof.

[0033] The amount of phenolic polymer particles in the dispersion can be 0.1–75.0 wt%, including 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%, 2.0 wt%, 3.0 wt%, 4.0 wt%, 5.0 wt%, 6.0 wt%, 7.0 wt%, 8.0 wt%, 9.0 wt%, 10.0 wt%, 15.0 wt%, 20.0 wt%, 25.0 wt%, 30.0 wt%, 35.0 wt%, 40.0 wt%, 45.0 wt%, 50.0 wt%, 55.0 wt%, 60.0 wt%, 65.0 wt%, and 70.0 wt%. Preferably, the amount of phenolic polymer particles is 0.5–50.0 wt%. More preferably, the amount of phenolic polymer particles is 1.0–40.0 wt%.

[0034] The amount of surfactant in the dispersion can be 1.0–100.0% of the mass of the phenolic polymer particles, including 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 6.5%, 7.0%, 7.5%, 8.0%, 8.5%, 9.0%, 9.5%, 10.0%, 15.0%, 20.0%, 25.0%, 30.0%, 35.0%, 40.0%, 45.0%, 50.0%, 55.0%, 60.0%, 65.0%, 70.0%, 75.0%, 80.0%, 85.0%, 90.0% and 95.0% of the mass of the phenolic polymer particles. Preferably, the amount of surfactant is 10.0–60.0% of the mass of the phenolic polymer particles. More preferably, the amount of surfactant is 20.0–50.0% of the mass of the phenolic polymer particles.

[0035] The amount of the carrier medium in the dispersion depends on the amount of the phenolic polymer particles and the amount of the surfactant in the dispersion. After mixing the phenolic polymer particles and the surfactant, the carrier medium can be added in any suitable amount required to produce the desired dispersion.

[0036] The dispersion can be prepared by conventional formulation techniques. For example, the phenolic polymer particles, the surfactant and the carrier medium can be mixed in a container and stirred until homogeneous. Appropriate mixing conditions such as temperature, stirring speed and mixing time can be varied to obtain the desired dispersion. Then the dispersion can be transferred to a grinder (such as a media grinder) and pulverized to obtain the desired particle size.

[0037] The particle size of the phenolic polymer particles can be from 0.001 to 10.0 micrometers (μm) (1 - 10,000 nm), including 0.002 μm, 0.003 μm, 0.004 μm, 0.005 μm, 0.006 μm, 0.007 μm, 0.008 μm, 0.009 μm, 0.01 μm, 0.02 μm, 0.03 μm, 0.04 μm, 0.05 μm, 0.06 μm, 0.07 μm, 0.08 μm, 0.09 μm, 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1.0 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm, 1.6 μm, 1.7 μm, 1.8 μm, 1.9 μm, 2.0 μm, 2.5 μm, 3.0 μm, 3.5 μm, 4.0 μm, 4.5 μm, 5.0 μm, 5.5 μm, 6.0 μm, 6.5 μm, 7.0 μm, 7.5 μm, 8.0 μm, 8.5 μm, 9.0 μm, and 9.5 μm. Preferably, the particle size of the phenolic polymer is from 0.01 to 5.0 μm (10 - 5,000 nm). More preferably, the particle size of the phenolic polymer is from 0.1 to 1.0 μm (100 - 1,000 nm). The maximum particle size of the phenolic polymer particles is 10.0 μm to prevent the particles from being perceived on the skin and to avoid a formulation having a gritty or granular texture for the user.

[0038] The lipophilic phenolic polymer particles can be obtained by removing the carrier medium from a dispersion of phenolic polymer particles, a surfactant, and a carrier medium. For example, the carrier medium can be a volatile substance that evaporates at ambient temperature and pressure. Similarly, the dispersion can be heated above the boiling point of the carrier medium until the carrier medium is removed.

[0039] The lipophilic phenolic polymer particles can also be prepared directly without separation from a dispersion. First, the particle size of the phenolic polymer particles is reduced by dry milling. Any suitable dry milling technique can be used, such as high-performance air milling, vibratory milling, media milling, hammer milling, and jet milling. The milling can be carried out alone or with auxiliary materials such as polymer particles or oxides (e.g., metal oxides and silicates (such as mica or silica)). Next, a solution is prepared by dissolving a surfactant or a silanizing agent in a suitable solvent. Examples of suitable solvents include USP heptane, USP acetone, USP isopropyl alcohol, and USP ethanol. Then, the solution is sprayed onto the milled phenolic polymer particles under stirring in a stirrer / mixer. The solution and the milled phenolic polymer particles can optionally be heated to facilitate the reaction of binding the surfactant or the silanizing agent to the particles. Finally, a vacuum is applied to remove the solvent.

[0040] Lipophilic phenolic polymer particles can be present in the oil phase of the formulation or can be added to a powder formulation. Preferably, the formulation is suitable for topical application. Examples of suitable formulations include emulsions (oil-in-water emulsions and water-in-oil emulsions), sprays, balms, sticks, powders, powder-to-cream preparations, lipophilic formulations, and anhydrous formulations. The formulation containing lipophilic phenolic polymer particles can be evaluated by one or more tests. Preferably, the formulation containing lipophilic phenolic polymer particles is highly water-resistant, super photo-stable, and passes the free radical quenching test.

[0041] Formulations containing lipophilic phenolic polymer particles can be formulated for a variety of different uses. Examples of suitable formulations include cosmetics (such as blush, powder, foundation, lipstick, base makeup, and rouge), skin care products (such as skin cleansing creams, lotions (lition), liquids and pads; face creams and neck creams, lotions, powders, and sprays; body creams and hand creams, lotions, powders, and sprays; foot powders and sprays; moisturizers; night creams, lotions, powders, and sprays; paste masks / clay packs; and skin fresheners) and sunscreens. Sunscreens are particularly preferred formulations. The formulation can be provided in any form suitable for topical administration, such as in the form of a topical suspension, lotion, cream, ointment, gel, hydrogel, foam, paste, tincture, liniment, sprayable liquid, aerosol, stick, or powder. The formulation can optionally include inactive ingredients, adjuvants, and / or additives (such as co-emulsifiers, fats, waxes, stabilizers, thickeners, bioactive ingredients, film formers, fragrances, dyes, pearlescent agents, preservatives, pigments, electrolytes, and pH regulators).

[0042] The sunscreen can contain lipophilic phenolic polymer particles and a UV radiation protecting agent. The UV radiation protecting agent can be any substance that absorbs, reflects, and / or scatters UV radiation. The sunscreen can optionally contain a sun protection factor (SPF) enhancer or stabilizer, such as methoxy acrylate and polyester-8.

[0043] Examples of suitable UV radiation protecting agents include zinc oxide (ZnO), titanium dioxide (TiO2), p-aminobenzoic acid (PABA), octyl dimethyl PABA (padimate O) (OD-PABA, octyl dimethyl-PABA, σ-PABA), phenylbenzimidazole sulfonic acid (ensulizole, 232, PBSA, HS), cinoxate (2-ethoxyethyl p-methoxycinnamate), dioxybenzone (benzophenone-8), oxybenzone (benzophenone-3, 4360, 567), homosalate (homomethylsalicylate, HMS), menthyl anthranilate (meradimate), octocrylene ( OCR, 2-cyano-3,3-diphenylacrylic acid, 2-ethylhexyl ester), octinoxate (EMC, OMC, ethylhexyl methoxycinnamate, 557, 2-ethylhexyl p-methoxycinnamate, MCX), octisalate (2-ethylhexyl salicylate, 587), sulisobenzone (2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 3-benzoyl-4-hydroxy-6-methoxybenzenesulfonic acid, benzophenone-4, 577), triethanolamine salicylate, avobenzone (1-(4-methoxyphenyl)-3-(4-tert-butylphenyl)propane-1,3-dione, butyl methoxydibenzoylmethane, BMDBM, 1789, 9020), ecamsule ( SX, terephthaloyl dicamphor sulfonic acid), cerium oxide (CeO2), polymethylsilsesquioxane ( XL), bis-ethylhexyloxyphenol methoxyphenyl triazine ( S), bis-s-triazine ( M, MILESTAB TM 360) and combinations thereof. Preferred UV radiation protectants include zinc oxide (ZnO), titanium dioxide (TiO2) and combinations thereof. Preferably, the UV radiation protectant has been approved by at least one regulatory agency in the United States (Food and Drug Administration or FDA), Canada, the European Union, Australia, Japan, South Korea, China, Mercosur, the Association of Southeast Asian Nations (ASEAN), the Commonwealth of Independent States (CIS) and the Gulf Cooperation Council (GCC).

[0044] Compared with traditional sunscreens, sunscreens containing lipophilic phenolic polymer particles have many advantages. The addition of phenolic polymer particles results in a very water-resistant sunscreen. In addition, phenolic polymer particles allow the sunscreen to block or attenuate UV radiation and HEV radiation. Phenolic polymer particles can also resist photoinduced free radicals generated by UV radiation and HEV radiation.

[0045] Preparations containing lipophilic phenolic polymer particles can provide a variety of health benefits. The phenolic polymer particles act as antioxidants because they are very effective in neutralizing free radicals. These properties enable the phenolic polymer particles to treat or prevent oxidative stress or damage to the skin, hair, and nails. For example, the phenolic polymer particles can be used to protect keratinous materials (such as hair, fingernails, toenails, and the outer layer of the skin), protect human skin, inhibit lipid peroxidation, prevent or reduce fine lines and wrinkles on the skin, prevent loss of skin elasticity, prevent thinning of the skin, and prevent skin pigmentation. These health benefits can be obtained by applying a preparation containing lipophilic phenolic polymer particles to the skin area.

[0046] The present invention includes the following aspects / embodiments / features in any order and / or any combination:

[0047] 1. A composition comprising:

[0048] Phenolic polymer particles, and

[0049] A surfactant on the phenolic polymer particles.

[0050] 2. A dispersion comprising:

[0051] The composition of 1 of any of the foregoing or following embodiments / features / aspects, and

[0052] A carrier medium.

[0053] 3. A dispersion comprising:

[0054] Sodium lignosulfonate particles,

[0055] A surfactant, and

[0056] A carrier medium,

[0057] wherein the particle size of the sodium lignosulfonate particles is 0.1 - 1.0 microns, and

[0058] the dispersion is pourable.

[0059] 4. A sunscreen composition comprising:

[0060] The composition of 1 of any of the foregoing or following embodiments / features / aspects, and

[0061] A UV radiation protectant.

[0062] 5. A dispersion comprising:

[0063] Silanized phenolic polymer particles, and

[0064] A carrier medium.

[0065] 6. Lipophilic phenolic polymer particles.

[0066] 7. A composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects, wherein the phenolic polymer particles comprise a substance selected from: lignin, humate, tannin, plant extracts containing water-soluble and / or water-dispersible components, and combinations thereof.

[0067] 8. A composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects, wherein the phenolic polymer particles comprise lignin, and the lignin is selected from lignosulfonate, sulfate lignin, sulfonated sulfate lignin, oxidized lignin, sulfonated oxidized lignin, lignosulfonate copolymerized with monomers, azosulfonate, azo lignin, lignosulfonate-formaldehyde condensate, lignin formaldehyde condensate, hydrophobically modified lignosulfonate, hydrophobically modified lignin, cationically modified lignosulfonate, cationically modified lignin, amino lignosulfonate, amino lignin, alkylated lignosulfonate, alkylated lignin, crosslinked lignosulfonate, crosslinked lignin, and combinations thereof; the monomers in the lignosulfonate copolymerized with monomers are, for example, acrylate, acrylic acid, acrylamide, styrene sulfonate, and naphthalene sulfonate derivatives.

[0068] 9. A composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects, wherein the phenolic polymer particles comprise humate, and the humate is selected from sulfonated humate, humate-formaldehyde condensate, hydrophobically modified humate, cationically modified humate, amino humate, alkylated humate, and combinations thereof.

[0069] 10. A composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects, wherein the phenolic polymer particles comprise tannin, and the tannin is selected from tannate, sulfonated tannate, tannate-formaldehyde condensate, hydrophobically modified tannate, cationically modified tannate, and combinations thereof.

[0070] 11. A composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects, wherein the phenolic polymer particles comprise a plant extract containing water-soluble and / or water-dispersible components,

[0071] The plant extract containing water-soluble and / or water-dispersible components is selected from extracts of: spruce (Norway spruce or European spruce), European larch (larch or European larch), and a mixture of maple species (sugar maple, silver maple, and boxelder maple).

[0072] 12. A composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects, wherein the surfactant comprises a substance selected from: fatty alcohols and polyols, fatty acids, polyglycerol esters, polyglycerol polyesters, polyesters having an affinity for hydroxyl, amine or amide groups, polyurethanes having an affinity for hydroxyl, amine or amide groups, polyamides having an affinity for hydroxyl, amine or amide groups, polyacrylates having an affinity for hydroxyl, amine or amide groups, phosphate esters, polymeric phosphates, phospholipids, ceramides, sphingosine, and combinations thereof, copolymers thereof and crosslinked polymers thereof.

[0073] 13. A composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects, wherein the phenolic polymer particles have a particle size of 0.001–10.0 microns.

[0074] 14. A composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects, wherein the phenolic polymer particles have a particle size of 0.01–5.0 microns.

[0075] 15. A composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects, wherein the phenolic polymer particles have a particle size of 0.1–1.0 microns.

[0076] 16. A composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects, wherein the carrier medium comprises a cosmetically acceptable fluid.

[0077] 17. A composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects, wherein the carrier medium comprises a substance selected from: triglycerides, esters, natural oils and butters, alkanes, silicones and combinations thereof.

[0078] 18. A composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects, wherein the carrier medium comprises wax.

[0079] 19. A composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects, wherein the amount of the phenolic polymer particles is 0.1–75.0% by weight, and

[0080] the amount of the surfactant is 1.0–100.0% of the mass of the phenolic polymer particles.

[0081] 20. A composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects, wherein the amount of the phenolic polymer particles is 0.5–50.0% by weight, and

[0082] the amount of the surfactant is 10.0–60.0% of the mass of the phenolic polymer particles.

[0083] 21. A composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects, wherein the amount of the phenolic polymer particles is 1.0–40.0% by weight, and

[0084] the amount of the surfactant is 20.0–50.0% of the mass of the phenolic polymer particles.

[0085] 22. A composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects, wherein the dispersion is highly water-resistant.

[0086] 23. A composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects, wherein the dispersion is super light-stable.

[0087] 24. A composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects, wherein the dispersion has passed the free radical quenching test.

[0088] 25. A composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects, wherein the surfactant includes polyglyceryl-2 dimer hydroxystearate.

[0089] 26. A composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects, wherein the carrier medium includes triglyceride of caprylic / capric acid.

[0090] 27. A composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects, wherein the surfactant includes polyglyceryl-2 dimer hydroxystearate,

[0091] the carrier medium includes triglyceride of caprylic / capric acid,

[0092] the amount of the sodium lignosulfonate is 1.0–40.0% by weight, and

[0093] the amount of the polyglyceryl-2 dimer hydroxystearate is 15.0–50.0% by weight.

[0094] 28. A composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects, wherein the UV radiation protecting agent is selected from zinc oxide (ZnO), titanium dioxide (TiO2), para-aminobenzoic acid (PABA), ethylhexyl dimethyl PABA, phenylbenzimidazole sulfonic acid, cinoxate (2-ethoxyethyl p-methoxycinnamate), dioxybenzone (benzophenone-8), oxybenzone (benzophenone-3), homomethyl salicylate, menthyl anthranilate (meradimate), octocrylene (2-cyano-3,3-diphenylacrylic acid), octinoxate, octyl salicylate (2-ethylhexyl salicylate), sulisobenzone (2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 3-benzoyl-4-hydroxy-6-methoxybenzenesulfonic acid, benzophenone-4), triethanolamine salicylate, avobenzone (1-(4-methoxyphenyl)-3-(4-tert-butylphenyl)propane-1,3-dione), ecamsule (terephthalylidene dicamphor sulfonic acid), cerium oxide (CeO2), polymethylsilsesquioxane, bis-ethylhexyloxyphenol methoxyphenyl triazine, bis-s-triazine and combinations thereof.

[0095] 29. A composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects, wherein the UV radiation protecting agent is selected from zinc oxide (ZnO), titanium dioxide (TiO2) and combinations thereof.

[0096] 30. A method for preparing a dispersion of any of the foregoing or subsequent embodiments / features / aspects, comprising:

[0097] Mixing phenolic polymer particles, a surfactant and a carrier medium in a container to form a dispersion;

[0098] Stirring the dispersion until homogeneous; and

[0099] Optionally, grinding the dispersion.

[0100] 31. A method for treating or preventing skin oxidative damage, comprising:

[0101] Applying a composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects to the skin.

[0102] 32. A method for protecting a keratinous material, comprising:

[0103] Applying a composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects to the keratinous material,

[0104] wherein the keratinous material is selected from hair, fingernails, toenails and the outer layer of the skin.

[0105] 33. A method for protecting human skin, comprising:

[0106] administering a composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects to human skin.

[0107] 34. A method for inhibiting lipid peroxidation in the skin, comprising:

[0108] administering a composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects to the skin.

[0109] 35. A method for preventing or reducing the appearance of fine lines and wrinkles on the skin, comprising:

[0110] administering a composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects to the skin.

[0111] 36. A method for preventing skin from losing elasticity, comprising:

[0112] administering a composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects to the skin.

[0113] 37. A method for preventing skin from thinning, comprising:

[0114] administering a composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects to the skin.

[0115] 38. A method for preventing skin from darkening in pigmentation, comprising:

[0116] administering a composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects to the skin.

[0117] 39. A method for attenuating HEV radiation exposed to the skin, comprising:

[0118] administering a composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects to the skin.

[0119] 40. A method for quenching free radicals in horny materials, comprising:

[0120] administering a composition, dispersion or particle of any of the foregoing or subsequent embodiments / features / aspects to the horny material,

[0121] wherein the horny material comprises hair or skin.

[0122] 41. A method for preparing a dispersion of any of the foregoing or subsequent embodiments / features / aspects, comprising:

[0123] React phenolic polymer particles with a silylating agent to form silylated phenolic polymer particles;

[0124] Mix the silylated phenolic polymer particles and a carrier medium in a container to form a dispersion;

[0125] Stir the dispersion until homogeneous; and

[0126] Optionally, mill the dispersion.

[0127] 42. A method for preparing lipophilic phenolic polymer particles of any of the foregoing or subsequent embodiments / features / aspects, comprising:

[0128] Mill a phenolic polymer to form phenolic polymer particles; and

[0129] Spray the phenolic polymer particles with a surfactant or a silylating agent in a container under stirring, optionally with heating, to form lipophilic phenolic polymer particles.

[0130] Examples

[0131] Example 1 - Dispersion of sodium lignosulfonate and polyglyceryl-2 dimer hydroxystearate in caprylic / capric triglyceride

[0132] Mix 30.0 parts by weight of sodium lignosulfonate (Vanisperse A, Borregaard LignoTech), 10.5 parts by weight of polyglyceryl-2 dimer hydroxystearate, and 59.5 parts by weight of caprylic / capric triglyceride. Stir the mixture until homogeneous, transfer it to a horizontal media mill, and grind it using 0.3 mm yttria-stabilized zirconia media until the maximum particle size is below 0.5 microns, as shown on a Hegman gauge with 0.5 scale gradations indicated from 0 - 12 microns. The resulting dispersion is pourable. The particle size of sodium lignosulfonate particles in the dispersion is measured to be 0.169 microns by static light scattering, and no particles below 0.1 micron are detected.

[0133] Example 2 - Dispersion of sodium lignosulfonate and polyglyceryl-2 dimer hydroxystearate in caprylic / capric triglyceride

[0134] Mix 30.0 parts by weight of sodium lignosulfonate (Vanisperse A, Borregaard LignoTech), 13.5 parts by weight of polyglyceryl-2 dimer hydroxystearate, and 56.5 parts by weight of caprylic / capric triglyceride. Stir the mixture until homogeneous, transfer it to a horizontal media mill, and grind it using 0.3 mm yttria-stabilized zirconia media until the maximum particle size is below 0.5 microns, as shown on a Hegman gauge with 0.5 scale gradations indicated from 0 - 12 microns. The resulting dispersion is pourable.

[0135] Example 3 - Dispersion of Sodium Lignosulfonate and Polyhydroxystearic Acid in Caprylic Acid Ester

[0136] 30.0 parts by weight of sodium lignosulfonate (Vanisperse A, Borregaard LignoTech) are mixed with 12.0 parts by weight of polyhydroxystearic acid and 58.0 parts by weight of caprylic acid ester. The mixture is stirred until homogeneous, transferred to a horizontal media mill, and comminuted using 0.3 mm yttria-stabilized zirconia media until the maximum particle size is below 0.5 microns, as shown on a Hegman gauge with 0.5 scale gradations indicated from 0 - 12 microns. The resulting dispersion is pourable.

[0137] Example 4 - Dispersion of Sodium Lignosulfonate and Lecithin in Triglyceride Caprylate / Caprate

[0138] 30.0 parts by weight of sodium lignosulfonate (Vanisperse A, Borregaard LignoTech) are mixed with 14.0 parts by weight of lecithin and 56.0 parts by weight of triglyceride caprylate / caprate. The mixture is stirred until homogeneous, transferred to a horizontal media mill, and comminuted using 0.3 mm yttria-stabilized zirconia media until the maximum particle size is below 0.5 microns, as shown on a Hegman gauge with 0.5 scale gradations indicated from 0 - 12 microns. The resulting dispersion is pourable.

[0139] Example 5 - Dispersion of Sodium Lignosulfonate and Polyglyceryl-2 Dimer Dihydroxystearate in C12-C15 Alkyl Benzoate

[0140] 30.0 parts by weight of sodium lignosulfonate (Maracell XE, Borregaard LignoTech) are mixed with 13.5 parts by weight of polyglyceryl-2 dimer dihydroxystearate and 56.5 parts by weight of C12-C15 alkyl benzoate. The mixture is stirred until homogeneous, transferred to a horizontal media mill, and comminuted using 0.3 mm yttria-stabilized zirconia media until the maximum particle size is below 0.5 microns, as shown on a Hegman gauge with 0.5 scale gradations indicated from 0 - 12 microns. The resulting dispersion is pourable.

[0141] Example 6 - Dispersion of a 2:1 Mixture of Sodium Lignosulfonate and Calcium Lignosulfonate and Polyglyceryl-2 Dimer Dihydroxystearate in Triglyceride Caprylate / Caprate

[0142] Mix 30.0 parts by weight of a mixture of sodium lignosulfonate:calcium lignosulfonate (Marasperse C-21, Borregaard LignoTech) at approximately 2:1 with 13.5 parts by weight of polyglyceryl-2 dimer of hydroxystearic acid and 56.5 parts by weight of triglyceride of caprylic / capric acid. Stir the mixture until homogeneous, transfer it to a horizontal media mill, and grind it using 0.3 mm yttria-stabilized zirconia media until the maximum particle size is less than 0.5 microns, as shown on a Hegman gauge with 0.5 scale gradations indicated from 0–12 microns. The resulting dispersion is pourable.

[0143] Example 7 - Dispersion of potassium humate and polyglyceryl-2 dimer of hydroxystearic acid in triglyceride of caprylic / capric acid

[0144] Mix 30.0 parts by weight of potassium humate (Borregro HA-2, Borregaard LignoTech) with 13.5 parts by weight of polyglyceryl-2 dimer of hydroxystearic acid and 56.5 parts by weight of triglyceride of caprylic / capric acid. Stir the mixture until homogeneous, transfer it to a horizontal media mill, and grind it using 0.3 mm yttria-stabilized zirconia media until the maximum particle size is less than 0.5 microns, as shown on a Hegman gauge with 0.5 scale gradations indicated from 0–12 microns. The resulting dispersion is pourable.

[0145] Example 8 - Dispersion of sodium lignosulfonate and cetyl diglycerol tris(trimethylsiloxysilyl)ethyl polydimethylsiloxane in triglyceride of caprylic / capric acid

[0146] Mix 30.0 parts by weight of sodium lignosulfonate (Vanisperse A, Borregaard LignoTech) with 13.5 parts by weight of cetyl diglycerol tris(trimethylsiloxysilyl)ethyl polydimethylsiloxane and 56.5 parts by weight of triglyceride of caprylic / capric acid. Stir the mixture until homogeneous, transfer it to a horizontal media mill, and grind it using 0.3 mm yttria-stabilized zirconia media until the maximum particle size is less than 0.5 microns, as shown on a Hegman gauge with 0.5 scale gradations indicated from 0–12 microns. The resulting dispersion is pourable.

[0147] Example 9 (Comparative Example) - Aqueous slurry of sodium lignosulfonate and alumina

[0148] Prepare an aqueous solution of sodium lignosulfonate according to the descriptions in U.S. Patent No. 6,500,411, U.S. Patent No. 6,716,418, and U.S. Patent Application Publication No. 2010 / 0202985. Add 30 parts by weight of sodium lignosulfonate (Vanisperse A, Borregaard LignoTech) to 70 parts by weight of deionized water. Stir the solution until the sodium lignosulfonate is completely dissolved. Add 60 parts by weight of submicron (D50 = 0.42 μm by volume measured by static light scattering) plate-shaped alumina (E390, Saint-Gobain) to the solution. Use a disperser blade to mix the resulting slurry for 30 minutes. The resulting aqueous slurry is homogeneous and easy to pour.

[0149] Example 10 - Moisturizer with Phenolic Polymer in the Oil Phase

[0150] Prepare the moisturizer composition as a water-in-oil emulsion that contains the dispersion of Example 1 in the oil phase. The components of the moisturizing composition are shown below:

[0151]

[0152] Using a cold process, combine and mix the components of the oil phase until homogeneous, and separately, combine and mix the components of the water phase until homogeneous. Then combine the two phases and homogenize at 5,000 RPM for 4 minutes using a Ross HSM-100LC1 homogenizer. The resulting emulsion is stable after aging at 50 °C for 75 days and is highly water-resistant. The presence of lipophilic dispersed phenolic polymer particles produces a moisturizer with HEV-blocking and antioxidant properties.

[0153] Example 11 - Moisturizing Sunscreen with Phenolic Polymer in the Oil Phase

[0154] Prepare the sunscreen composition as a water-in-oil emulsion that contains the dispersion of Example 1 in the oil phase. The components of the sunscreen composition are shown below:

[0155]

[0156] Using a cold process, combine and mix the components of the oil phase until homogeneous, and separately, combine and mix the components of the water phase until homogeneous. Then combine the two phases and homogenize at 5,000 RPM for 4 minutes using a Ross HSM-100LC1 homogenizer. The resulting emulsion is stable after aging at 50 °C for 75 days and is highly water-resistant. The presence of lipophilic dispersed phenolic polymer particles produces a moisturizing sunscreen with HEV-blocking and antioxidant properties.

[0157] Example 12 - Concealer with Phenolic Polymer in the Oil Phase (Expected)

[0158] The concealer composition is prepared as an anhydrous composition containing the dispersion of Example 1. The ingredients of the concealer are as follows:

[0159]

[0160] Phase A is combined and mixed under high-shear conditions. Phase B is added to Phase A, and the mixture is heated to 85 °C under high-shear conditions. Phase C is dispersed into the mixture under high-shear conditions while maintaining the temperature at 85 °C. Then the batch is cooled under high-shear mixing. Once the mixture has cooled below 65 °C, Phases D and E are gradually added to the mixture under high-shear mixing conditions. The batch is allowed to continue cooling until the temperature reaches 60 °C. Then the batch is dispensed into the final packaging. The presence of the lipophilic-dispersed phenolic polymer particles results in a concealer with HEV-blocking and antioxidant properties.

[0161] Example 13 - HEV Blocking Study

[0162] The HEV blocking of the dispersion of Example 1 and the comparative aqueous slurry of Example 9 was compared. The diffuse transmission method, similar to the methods described in 21 C.F.R. § 201.327 (Over-the-counter sunscreen drug products; labeling based on effectiveness testing requirements) and ISO 24443 (Determination of UVA photoprotection of sunscreens in vitro), was used to measure HEV blocking.

[0163] 1.3 mg / cm 2 of the dispersion of Example 1 was applied to the surface of an optically clear polymethyl methacrylate (PMMA) substrate having a rough three-dimensional surface topography (LabSphere HelioPlate HD6). The dispersion was uniformly applied to the substrate surface to correspond to a delivery dose of 0.39 mg / cm 2 of the phenolic polymer. The aqueous slurry of Example 9 was applied to the substrate in a similar manner to correspond to a delivery dose of 0.39 mg / cm 2 of the phenolic polymer.

[0164] The samples were visually inspected, and both samples showed the characteristic brown color associated with light absorption in the HEV region. Then the samples were left at room temperature for 1 hour. The absorbance of both samples and a control blank optically clear PMMA substrate was measured at the HEV wavelength of 450 nm using a LabSphere UV-2000S spectrophotometer. The net absorbance value was determined by subtracting the absorbance of the control blank substrate measured from the absorbance of the sample on the substrate.

[0165] The monochromatic protection factor (MPF) at 450 nm was determined according to the method of Bleasel, M.D. et al., “In vitro evaluation of sun protection factors of sunscreen agents using a novel UV spectrophotometric technique”, International Journal of Cosmetic Science, Vol. 30, No. 4, pp. 259–270 (2008). The MPF can be expressed by Equation 2 below:

[0166] Equation 2:

[0167] where A(λ) is the net absorbance of the sample at wavelength λ.

[0168] The results are shown in the table below:

[0169] Sample Net absorbance (450nm) MPF (450nm) Dispersion of Example 1 1.224 16.77 Aqueous slurry of Example 9 0.711 5.14

[0170] Compared with the aqueous slurry of Example 9, the dispersion of Example 1 exhibited a greater net absorbance and a greater MPF. These results indicate that the phenolic polymer dispersed in the oil phase has excellent HEV blocking compared to the aqueous slurry of the phenolic polymer.

[0171] Example 14 - Water Resistance Study

[0172] The water resistance of the dispersion of Example 1 and the comparative aqueous slurry of Example 9 was compared. The water resistance was measured using an 80-minute immersion sequence in accordance with COLIPA 2005 (Cosmetics Europe, “Guidelines for evaluating sun product water resistance”, available online at www.cosmeticseurope.eu / files / 7914 / 6407 / 7400 / Guidelines_for_Evaluating_Sun_Product_Water_Resistance_-_2005.pdf, p. 15 (2005)), but performed in vitro.

[0173] A stainless-steel container with a height of 22 cm and a diameter of 16 cm was filled with deionized water and maintained at a temperature between 30–33 °C. Throughout the test, a flat-blade impeller with a diameter of 5 cm was used to stir the container at 350 RPM. Samples of the dispersion of Example 1 and the comparative aqueous slurry of Example 9 were suspended in the container near the container wall, with the applied samples facing the impeller. After 80 minutes of immersion, the samples were removed from the container and dried for 1 hour. The net absorbance and the monochromatic protection factor (MPF) were measured as described in Example 13. The results are shown in the table below:

[0174] Measurement Dispersion of Example 1 Aqueous slurry of Example 9 Net absorbance (450nm) before immersion 1.224 0.711 MPF (450nm) before immersion 16.77 5.14 Net absorbance (450nm) after immersion 1.167 0.012 MPF (450nm) after immersion 14.70 1.03 MPF% retained 88 20

[0175] The dispersion of Example 1 was able to maintain 95% of the net absorbance (450 nm) and retain 88% of the initial MPF (450 nm) value. These results indicate that the dispersion of Example 1 is highly water-resistant. Visual inspection showed that the aqueous slurry of Example 9 lost most of its characteristic brown color associated with HEV attenuation after 120 seconds of immersion. Additionally, the aqueous slurry of Example 9 did not meet the requirements for classification as highly water-resistant. These results demonstrate that the lipophilic dispersed phenolic polymer particles in the oil phase have excellent water resistance compared to the aqueous slurry of phenolic polymers.

[0176] Example 15 - Free Radical Quenching and Photo-Stability Studies

[0177] The free radical quenching and photo-stability of the dispersion of Example 1 were studied. Photo-stability was determined according to the modified DPPH photo-stability test (see the definition section). Free radical quenching was determined according to the free radical quenching test (see the definition section). Titanium dioxide was used as a comparative substance as it is known to be essentially non-photo-stable (photocatalytic) and generates a large number of photo-induced free radicals when exposed to UV radiation.

[0178] Five photo-stability tests were performed using different amounts of the dispersion of Example 1 and reference titanium dioxide. The results are shown in the table below:

[0179] Test % phenolic polymer in the dispersion of Example 1 <![CDATA[TiO2%]]> ΔE Standard deviation 1 0.115 0 0.65 0.441 2 0.0575 0.0575 3.91 0.166 3 0.115 0.115 1.01 0.082 4 0 0.115 18.84 1.104 5 0 0.0575 14.85 0.398

[0180] The results of Test 1 showed that the dispersion of Example 1 is super photo-stable. In contrast, an equal amount of reference titanium dioxide (Test 4) was not super photo-stable and generated 29 times the concentration of free radicals. Combinations containing equal amounts of the dispersion of Example 1 and titanium dioxide (Tests 2 and 3) were super photo-stable, indicating that the dispersion of Example 1 actively quenched 73.7% to 94.7% of the free radicals generated by the highly photo-active reference material. The dispersion of Example 1 passed the free radical quenching test at both weight percentages.

[0181] The results show that the lipophilic dispersed phenolic polymer particles in the oil phase are super photo-stable and pass the free radical quenching test. The free radical quenching ability is an indicator of the antioxidant performance of the lipophilic phenolic polymer. The results also show that the lipophilic phenolic polymer particles can combine with highly photoactive substances to produce a super light-resistant composition, protecting users from UV-generated free radicals.

[0182] Reference documents

[0183] 1. U.S. Patent No. 6,500,411.

[0184] 2. U.S. Patent No. 6,716,418.

[0185] 3. U.S. Patent No. 8,309,063.

[0186] 4. U.S. Patent No. 8,445,562.

[0187] 5. U.S. Patent No. 8,911,976.

[0188] 6. U.S. Patent No. 10,035,928.

[0189] 7. U.S. Patent Application Publication No. 2007 / 0178057.

[0190] 8. U.S. Patent Application Publication No. 2010 / 0202985.

[0191] 9. U.S. Patent Application Publication No. 2015 / 0166836.

[0192] 10. U.S. Patent Application Publication No. 2018 / 0291210.

[0193] 11. International Patent Application Publication No. WO 2009 / 038477.

[0194] 12. International Patent Application Publication No. WO 2014 / 144746.

[0195] 13. International Patent Application Publication No. WO 2014 / 164418.

[0196] 14. International Patent Application Publication No. WO 2017 / 197530.

[0197] 15. Pan, X. et al., “Organosolv ethanol lignin from hybrid poplar as a radical scavenger: relationship between lignin structure, extraction conditions, and antioxidant activity”, Journal of Agricultural and Food Chemistry, Vol. 54, pp. 5806–5813 (2006).

[0198] 16. Cosmetics Europe, “Guidelines for evaluating sun product water resistance”, available online at www.cosmeticseurope.eu / files / 7914 / 6407 / 7400 / Guidelines_for_Evaluating_Sun_Product_Water_Resistance_-_2005.pdf, 15 pages (2005).

[0199] 17. Bleasel, M.D. et al., “In vitro evaluation of sun protection factors of sunscreen agents using a novel UV spectrophotometric technique”, International Journal of Cosmetic Science, Vol. 30, No. 4, pp. 259–270 (2008).

[0200] 18. The International Lignin Institute, “About lignin”, available online at www.ili-lignin.com / aboutlignin.php (published on August 30, 2019).

Claims

1. A composition comprising: Phenolic polymer particles, and A surfactant on the phenolic polymer particles, Wherein the composition is highly water - resistant, The phenolic polymer is a water - soluble polymer comprising a plurality of OH - substituted phenyl groups, The particles are in a solid state, The phenolic polymer particles comprise a substance selected from: lignin, humate, and combinations thereof; and The surfactant comprises a substance selected from: polyglycerol polyesters, polyesters, phospholipids, substituted silicones, and combinations thereof.

2. The composition according to claim 1, wherein the particle size of the phenolic polymer particles is 0.001–10.0 micrometers (μm).

3. A dispersion comprising: The composition according to claim 1, and A carrier medium, the carrier medium being a cosmetically acceptable lipophilic fluid or wax.

4. The dispersion according to claim 3, wherein the carrier medium comprises a substance selected from: triglycerides, esters, natural oils and butters, alkanes, silicones, and combinations thereof.

5. The dispersion according to claim 3, wherein the amount of the phenolic polymer particles present is 0.1–75.0% by weight, and The amount of the surfactant present is 1.0–100.0% of the mass of the phenolic polymer particles.

6. A dispersion comprising: Sodium lignosulfonate particles, A surfactant, and A lipophilic cosmetically acceptable fluid, Wherein the particle size of the sodium lignosulfonate particles is 0.1–1.0 micrometers, The dispersion is pourable, and the dispersion is highly water - resistant.

7. The dispersion according to claim 6, wherein the surfactant comprises polyglycerol - 2 dimer hydroxystearate, The lipophilic cosmetically acceptable fluid comprises caprylic / capric triglyceride, The amount of sodium lignosulfonate present is 1.0–40.0% by weight, and The amount of polyglycerol - 2 dimer hydroxystearate present is 15.0–50.0% by weight.

8. The dispersion according to claim 7, wherein the dispersion is super light - stable.

9. The dispersion according to claim 7, wherein the dispersion passes the free - radical quenching test.

10. A sunscreen composition comprising: The composition according to claim 1, and A UV radiation protector.

11. The sunscreen composition according to claim 10, wherein the UV radiation protectant is selected from zinc oxide (ZnO), titanium dioxide (TiO2), para - aminobenzoic acid (PABA), octyl dimethyl PABA, phenylbenzimidazole sulfonic acid, cinoxate (2 - ethoxyethyl p - methoxycinnamate), dioxybenzone (benzophenone - 8), oxybenzone (benzophenone - 3), homosalate, menthyl anthranilate, octocrylene (2 - cyano - 3,3 - diphenylacrylic acid), octyl methoxycinnamate, octyl salicylate (2 - ethylhexyl salicylate), sulisobenzone (2 - hydroxy - 4 - methoxybenzophenone - 5 - sulfonic acid, 3 - benzoyl - 4 - hydroxy - 6 - methoxybenzenesulfonic acid, benzophenone - 4), triethanolamine salicylate, avobenzone (1 - (4 - methoxyphenyl)-3 - (4 - tert - butylphenyl)propane - 1,3 - dione), ecamsule (terephthalylidene dicamphor sulfonic acid), cerium oxide (CeO2), polymethacrylamidotriazine, bis - ethylhexyloxyphenol methoxyphenyl triazine, bis - sothriazole, and combinations thereof.

12. An oil - in - water or water - in - oil emulsion comprising the dispersion according to claim 3.

13. A cosmetic composition for protecting human skin, comprising the composition according to claim 1.

14. A cosmetic composition for preventing oxidative damage to the skin, comprising the composition according to claim 1.

15. A cosmetic composition for protecting horny materials, wherein the horny materials are selected from hair, fingernails, toenails, and the outer layer of the skin, and the cosmetic composition comprises the composition according to claim 1.

16. A cosmetic composition for inhibiting lipid peroxidation in the skin, comprising the composition according to claim 1.

17. A cosmetic composition for preventing or reducing the appearance of fine lines and wrinkles on the skin, comprising the composition according to claim 1.

18. A cosmetic composition for preventing loss of skin elasticity, comprising the composition according to claim 1.

19. A cosmetic composition for preventing thinning of the skin, comprising the composition according to claim 1.

20. A cosmetic composition for preventing skin pigment darkening, comprising the composition according to claim 1.

21. A cosmetic composition for attenuating HEV radiation exposure to the skin, comprising the composition according to claim 1.

22. A cosmetic composition for quenching free radicals in horny materials, comprising the composition according to claim 1, wherein the horny materials include hair or skin.

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