CLIAMS:1. A personal care composition comprising in-situ generated micronized particles functionalized with an active ingredient, wherein said particles comprise:
a) At least one metal precursors in the range of from about 0.05 to about 50% by weight;
b) At least one alkali in the range of from about 0.2 to about 15% by weight;
c) At least one emulsifier in the range of from about 0.5 to about 50% by weight; and
d) At least one surfactant in the range of from about 0.5 to about 40% by weight.

2. The composition as claimed in claim 2 wherein said active ingredient is selected from lightening agents, darkening agents such as self-tanning agents, anti-acne agents, shine control agents, anti-microbial agents, anti-inflammatory agents, anti-aging agents, in particular anti-wrinkle agents, anti-mycotic agents, anti-parasite agents, external analgesics, sunscreens, photoprotectors, antioxidants, keratolyticagents, detergents/surfactants, moisturizers, nutrients, vitamins, energy enhancers, anti-perspiration agents, astringents, deodorants, hair removers, firming agents, anti-callous agents, and agents for hair, nail, and/or skin conditioning.

3. The composition as claimed in claim 2 wherein said active ingredient is present in an amount from 0.001% to 10% by weight, preferably from 0.1% to 5% by weight.

4. The composition as claimed in claim 1 wherein said metal precursor is selected from selected from Zn Acetate, TiCl2, ZnSO4, ZnNO3, Zn Stearate, Zn Acetylacetonate, Zn Laurate, Zn Palmitate, Zn Myristate, Mg Acetate, ZnCl2, ZnSO4, ZnNO3, Zn Stearate, Zn Acetylacetonate, Zn Laurate, Zn Palmitate, Zn Myristate and combinations thereof.
5. The composition as claimed in claim 1, wherein said alkali is selected from sodium hydroxide, potassium hydroxide, magnesium hydroxide, ammonium hydroxide and combinations thereof.

6. The composition as claimed in claim 1 wherein said emulsifier is selected from long chain fatty acids and their derivatives, long chain fatty alcohols and their derivatives, long chain amines and their derivatives, long chain amides, polyacrylates, polyols, sugar derivatives and combinations thereof.

7. The composition as claimed in claim 1 wherein said surfactant is selected from anionic, non-ionic, amphoteric, cationic surfactants and combinations thereof.

8. The composition as claimed in claim 1 wherein said composition is formulated into cream, lotion, facewash, shampoo, bodywash, shower gel, facial cleanser, leave on gel, conditioner, body conditioner, shaving gel/cream, after shave cream/gel and sunscreen.

9. The composition as claimed in claim 1 wherein said composition further comprises cosmetically acceptable excipients selected from preservative, structurant, active agent, humectants, conditioner, binders, emollient, emulsifiers, fragrance and emotives.

10. A process for preparation of a personal care composition as claimed in claim 1 comprising the steps of :
(i) melting metal oxide precursor along with solvents, emulsifiers and surfactants at around 65°C to 75°C;
(ii) adding active ingredient to the mixture obtained from (i) and mixing it at 50 to 60°C;
(iii) adding alkali solution drop-wise to the mixture obtained from (ii) to obtain in-situ generated metal oxide composite functionalized with active ingredients;
(iv) optionally, adding oil, polymers, to the mixture obtained from (iii);
(v) making up the volume of the mixture obtained from (iv) with water and homogenizing it to obtain the final formulation. ,TagSPECI:Field of the Invention
The present invention relates to cosmetic/personal care formulations, more specifically to sunscreen compositions.

Background and the prior art
Sunscreen is a substance that helps protect the skin from the sun’s harmful rays and are widely used for photo-protection. Consequently, the greatest advances have been in the development of a cosmetically appealing sunscreen that provides lasting broad-spectrum protection. Sunscreens reflect, absorb, and scatter both ultraviolet A and B radiation to provide protection against both types of radiation. Using lotions, creams, or gels that contain sunscreens can help protect the skin from premature aging and damage that may lead to skin cancer. In order to improve the UV protective function of the stratum corneum, chemical and physical compounds are added to sunscreens. The former are absorbing organic chemical substances while the latter are nanoparticles or micronized particles of titanium dioxide (TiO2) and zinc oxide (ZnO) which both absorb and scatter UV light. Topical sunscreens provide a means of sun protection and function by the absorption of light effecting an electronic excitation of the sunscreen molecule (from its ground state to the first excited singlet state). According to investigations, UV-induced radicals include reactive oxygen species (ROS) and lipid radicals as well as melanin radicals. With human skin in vivo, the UVA is mainly responsible for the generation of free radicals (80-90% of total amount) because of higher penetration depth, in contrast to UVB light which contributes to radical generation only in the epidermis.

In sunscreens containing physical UV screening agents the transparency decreases with increasing concentration of the physical sunscreen particles. This is because of an increased scattering of light by the particles, which causes a whitening effect in the layer of the sunscreen. Thus, for a given layer thickness there is typically a trade-off between the transparency of the layer and the concentration of physical screening agents in the layer. In commercially available sunscreens the whitening effect limits the maximum concentration of physical UV screening agents, such as zinc oxide or titanium oxide, to values which are sometimes unable to provide adequate UVA/UVB protection. One of the main limitations of the use of physical UV screening agents in sunscreens is the problem of whiteness left on the skin after the sunscreen has been applied.

Present day formulators try to use small particles to improve the transparency of the cosmetic formulations in the cosmetic sunscreen industry to improve the cosmetic acceptability. Proper surface treatment is also required to make the particles stable in formulation and will stop the particles from coagulations during its shelf life without the change in particle size or sensorial properties. In applications such properties are essential in order to enable a pigment powder to be formed and later re-dispersed or to provide long-term stability to a liquid formulation. In the case of insufficient stabilization, random coagulation of particles will occur, resulting in decreased transparency of films and coatings formed from them. Many recent developments try to provide this by producing primary particles smaller than e.g. 50 nm and by stabilizing them against aggregation by various means.

WO2009101016 discloses particles P, which can be obtained by the reaction of inorganic nanoparticles N with organic molecules M, which contain functional groups Z, wherein: a) said inorganic nanoparticles N are provided in a dispersion D, through the reaction of compounds V in a solvent, and b), immediately after step (a), said organic molecules M are added to said dispersion D. Furthermore, the invention discloses liquid and solid formulations, containing particles P, methods for the production of particles P, method for suppressing the photocatalytic activity of inorganic nanoparticles N, methods for stabilizing UV absorbers, methods for stabilizing polymers against the effect of light, radicals, or heat, and the use of particles in cosmetic applications. WO2009101016 mentions that UV absorber preferably organic molecules are used as M and lists a wide range of UV organic absorbers such as cinnamate, salicylates, p-amino benzoic acid, p-amino benzoic esters, anthranilates, etc. According to WO’016, the inorganic nanoparticles may be metal or semi-metal oxides, metal or semi-metal sulfides, selenides, nitrides, sulfates or carbonates. Very particular preference is as metal oxides ZnO, TiO2, ZrO2, CeO2, Ce2O3, SnO2, SnO, Al2O3, SiO2, and Fe2O3. The process described in WO2009101016 is a multistep process and the material used is not cosmetic friendly and requires preformed nanoparticles being added to the UV absorbers.

US2004197359 discloses fine particles for cosmetics which are excellent in smoothness upon application to the skin or hydrophilic nature and powdery texture. These modified inorganic fine particles comprise, on the surface of inorganic fine particles, a polymer layer (I) prepared by plasma-polymerizing one of monomers selected from among fluorinated monomers, silicone-based monomers, aromatic monomers and alicyclic monomers; a polymer layer (II) obtained by plasma graft-polymerizing a monomer having a functional group; or a polymer layer (III) prepared by plasma graft-polymerizing a monomer having a functional group modified with a functional organic compound(s). The functional organic compound(s) are one or more members selected from among dyes, UV absorbers and skin-chapping inhibitors. US2004197359 discloses the preparation of inorganic fine particles by plasma graft polymerization which is a multistep process.

CN102675568 discloses a preparation method for an organic-inorganic hybrid skin-friendly efficient sunscreen product. The method comprises the following steps of: performing macromolecular self-assembly on a synthesized amphiphilictriblock polymer PEO-b-PDMA-b-PS to obtain polymer nanoparticles with uniform particle size distribution; and performing in-situ reaction on a deposited titanium precursor on the nanoparticles, drying in-situ reaction products to obtain organic-inorganic hybrid titanium dioxide nanoparticles, and further calcining the organic-inorganic hybrid titanium dioxide nanoparticles to obtain titanium dioxide nanoparticles. The method is characterized in that the skin-friendly titanium dioxide nanoparticles with high sunscreen performance can be prepared, are harmless to skin, have good ultraviolet resistant effects, and have high dispersion performance in water; the particle sizes of the ultraviolet resistant nanoparticles can be randomly controlled; and the preparation method is simple and wider in application range. It describes the preparation of inorganic fine particles by plasma graft polymerization which is a multistep process.

KR20090056658 discloses an organic-inorganic complex powder of which an organic UV protector and metal oxide are mixed and dipped in a mesoporous silica molecule. This provides increase UV protection effect and the protection area of UV-A and UV-B, and improves stability. An organic-inorganic complex is made by dipping a metal oxide and organic UV protector in a pore of mesoporous silica molecule. The metal oxide is an UV-B protection component of cerium oxide(CeO2) or titanium oxide(TiO2) and UV-A protection component of ferric oxide(Fe2O3) or zinc oxide(ZnO). The organic UV protector is a cinnamate, salicylate, benzophenone, triazine or the triazone based UV protector. The silica molecule is a porous silica having 200~900m2/g of specific surface area, 0.3-1.5cc/g of pore volume (Vp), and 5-15nm range of pore size. KR20090056658 further discloses a method for manufacturing the mesoporous organic-inorganic complex powder comprises: a step of dipping the mesoporous silica molecule in solution in which the cerium chloride or titanium alkoxide is resolved to produce a metal oxide-dipped mesoporous complex powder which protects the UV-B; a step of dipping the produced powder in solution in which a ferric chloride or zinc chloride is resolved to produce a metal oxide-dipped mesoporous complex powder which protects the UV-A; and a step of mixing 1-26 weight% of complex powder and organic UV protector. KR20090056658 thus describes a method of preparing organic-inorganic complex in a pore of mesoporous silica molecule. These are not cosmetically relevant and the preparation process is multistep process.

US5733531 discloses a topical sunblock agent for shielding skin from ultraviolet radiation, and a composite sunblocking component thereof. The sunblocking component of the formula includes an effective amount of a plurality of particles having diameters in the range of about 0.01-100 microns, each particle including a matrix and a UV-attenuating compound incorporated into the matrix. US5733531 mentions that the invention encompasses first and second UV-attenuating compounds that are together encapsulated in a matrix. The first and second UV-attenuating compounds may be organic or inorganic sunscreen agents. Organic agents include but are not limited to chemical sunscreens such as benzophenones, PABA and PABA derivatives, cinnamates, salicylates, anthranilates such as menthylanthranilate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, 2-phenyl benzimidazole-5-sulfonic acid, digalloyltrioleate, 3-(4-methyl benzylidene) camphor, 4-isopropyl dibenzoyl methane, butyl methoxydibenzoylmethane, 2-ethyl-2-cyano-3,3'-diphenyl acrylate. Inorganic agents include but are not limited to kaolin, talc, titanium dioxide, and zinc oxide. US5733531 discloses the preparation of a typical sunblocking agent for shielding skin from ultraviolet radiation where both organic and inorganic molecules are encapsulate in matrix. US5733531 does not disclose anything related to stabilization of the organic sunscreen.

US 20120263769 provides an ultraviolet absorber-including clay mineral, which allows an ultraviolet absorber to be blended, as a powder component, into cosmetic preparations, can effectively absorb a wide range of ultraviolet light, and has excellent inclusion amount and inclusion strength; and cosmetics containing the same. The ultraviolet absorber-including clay mineral is characterized in that a polybase and an anionic ultraviolet absorber are intercalated between the layers of a water-swellable clay mineral. The polybase is preferably a polymer having a nitrogen-containing group that can become a cation. The anionic ultraviolet absorber is preferably one or more selected from 2-phenylbenzimidazole-5-sulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, and their sodium salts. However the process is a multistep process and hence time consuming while yield of the final product is less.

The main challenges of manufacturing small particles are the post-processing steps e.g. depositing and dispersing, are significantly more complicated. Therefore generation of composite materials in-situ during the batch making process is always the demand from a formulator. Further, the delivery of an active through rinse-off product is a real practical challenge to the product formulator.

Objects of the Invention
It is an objective of the present invention to overcome the drawback of the prior arts.
It is another objective of the present invention to overcome the problem of depositing and dispersing the inorganic UV absorber in the formulation.
It is yet another objective of the present invention to provide an in-situ generation of the composite material during the batch making of personal care rinse-off products.
It is further objective of the present invention to avoid post-processing steps of the composite materials to be incorporated in the formulations.
It is further another objective of the present invention to deposit the personal care active ingredients through a rinse-off product and provide a broad UV protection.
It is yet another objective of the present invention to improve the sensorial properties of the personal care rinse-off product.
It is further objective of the present invention to provide better and broad spectrum sun protection, anti-acne activity, skin softness, skin smoothness, conditioning, colour protection etc.

Brief description of accompanying figures
Figure 1 illustrates the SEM image of the facewash composition containing in-situ generated composite material in the formulation.
Figure 2 illustrates the Electron Dispersive X-ray analysis (EDX pattern) of the facewash formulation confirming the presence of ZnO.
Figure 3 illustrates the EDX pattern of skin sample after treated with facewash formulation containing in-situ generated composite material on carbon tape
Figure 4 illustrates the EDX pattern of untreated skin sample on a carbon tape
Figure 5 illustrates the EDX pattern of skin sample after treated with facewash formulation containing physical mixture of ZnO and OMC on a carbon tape

Summary of the Invention
According to one aspect of the present invention there is provided a personal care composition comprising in-situ generated micronized particles functionalized with an active ingredient, wherein said particles comprise:
a) At least one metal precursors in the range of from about 0.05 to about 50% by weight;
b) At least one alkali in the range of from about 0.2 to about 15% by weight;
c) At least one emulsifier in the range of from about 0.5 to about 50% by weight; and
d) At least one surfactant in the range of from about 0.5 to about 40% by weight.

According to another aspect of the present invention there is provided a rinse off personal care composition comprising the in-situ generated micronized particles of the present invention.

According to a further aspect of the present invention there is provided a process for preparation of a personal care composition comprising in-situ generated micronized particles comprising the steps of:
(i) Melting metal oxide precursor along with solvents, emulsifiers and surfactants at around 65°C to 75°C;
(ii) Addition of active ingredient (anti-acne, anti-ageing, skin lightening, moisturizing,
organic UV-absorber etc.) to the mixture obtained from step (i) and mixing it at 50 to 60°C;
(iii) Addition of alkali solution drop-wise to the mixture obtained from step (ii) to obtain in-
situ generated metal oxide composite functionalized with active ingredients;
(iv) Optionally adding oil, polymers to the mixture obtained from step (iii);
(v) Making up the volume of the mixture obtained from step (iv) with water and
homogenizing it to obtain the final formulation.

Details description of the present invention

The present invention discloses the process of in-situ generation of metal oxide particles and functionalization of the same with different active ingredients such as skin lightning actives, UV absorber, anti-aging actives, anti-microbial actives, moisturizing actives etc. to enhance the stability and effective delivery of the same.

In-situ generation of the composite material herein refers to the generation of active (composite material) in the formulation itself i.e. in the course of batch making process of the particular formulation of choice. In this case the composite material is not added to the formulation separately.
The present invention discloses the in-situ functionalization of metal oxide particles with active ingredients during the batch making process of a personal care formulation, wherein the process comprises steps of :
(i) Melting metal oxide precursor along with solvents, emulsifiers and surfactants at around 65°C to 75°C;
(ii) Addition of active ingredient (anti-acne, anti-ageing, skin lightening, moisturizing, organic UV-absorber etc.) to the mixture obtained from (i) and mixing it at 50 to 60°C;
(iii) Addition of alkali solution drop-wise to the mixture obtained from (ii) to obtain in-situ generated metal oxide composite functionalized with active ingredients;
(iv) Optionally adding oil, polymers to the mixture obtained from (iii);
(v) Making up the volume of the mixture obtained from (iv) with water and homogenizing it to obtain the final formulation.

In accordance with the present invention the particle size of the in-situ generated composite in the formulation is 0.5 µm – 1000 µm preferably from 10 µm – 500 µm.

In accordance with the present invention the deposition of active ingredients can be achieved through personal care rinse-off products such as bodywash, facewash, soap, shampoo, conditioner etc.

The cosmetic ingredient of choice could be generated in-situ while improving the sensory properties. The particles are distributed well through the product and make the mixture homogeneous. In-situ generation of these composite active ingredients, in the rinse-off product formulation provides several skin benefits such as UV protection, anti-acne, anti-microbial, anti-dandruff, anti-aging, skin softness, skin smoothness, hair conditioning, colour protection etc. It can also provide strong conditioning and colour protection the hair.

The present inventors have found that such in-situ functionalization of metal oxide particles with active ingredients, in a formulation, can be obtained only when the said unique combination of components are used. Such unique combination comprises:
a. At least one metal Precursor in the range of from about 0.05 to about 50%
b. At least one alkali in the range of from about 0.2 to about 15%
c. At least one emulsifier in the range of from about 0.5 to about 50%.
d. At least one surfactant in the range of from about 0.5 to about 40%.

The inventors of the present invention have found that when the above stated components are within the above specified ranges the delivery of actives, especially from rinse off formulations, deposition and delivery of the active ingredients are enhanced.
Emulsifiers according to the present invention are long chain fatty acids and their derivatives, long chain fatty alcohols and their derivatives, long chain amines and their derivatives, long chain amides, polyacrylates, polyols, sugar derivatives etc.

Fatty acids according to the present invention are saturated fatty acids selected from C10-C20 fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and the like. The preferable saturated fatty acids for the preparation of composite material in the present invention are lauric acid, myristic acid, palmitic acid, stearic acid and combinations thereof. The amount of the saturated fatty acids ranges from 1 to 30% by wt, preferably from 4 to 15% by wt.

Surfactants are selected from group comprising of anionic, non-ionic, amphoteric and cationic surfactants. The anionic surfactants that may be used in the present invention include but are not limited to acyl isethionates, Sodium cocoyl isethionate, sodium isethionate, sodium lauroyl isethionate, Sodium lauroyl methyl isethionate, sodium methyl cocoyl taurate, and the series, sodium alkyl sulfate, alkyl sulfates, anionic acyl sarcosinates, methyl acyl taurates, N-acyl glutamates, acyl isethionates, alkyl ether sulfates, alkyl sulfosuccinates, alkyl phosphate esters, ethoxylated alkyl phosphate esters, trideceth sulfates, protein condensates, mixtures of ethoxylated alkyl sulfates and the like. Alkyl chains for these surfactants are C8-22, preferably C10-18 and, more preferably, C12-14 alkyls. Most preferred anionic surfactant includes sodium cocoyl isethionate which is a mixture of (C8-C20) alkyl chain distribution.

The amphoteric surfactants which can be used in the compositions of the present invention are those which can be broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. Examples of compounds falling within this definition are CDMA, sodium 3-dodecylaminopropionate, sodium 3-dodecylaminopropane sulfonate. Other amphoterics such as betaines are also useful in the present composition. Examples of betaines useful herein include the high alkyl betaines such as coco dimethyl carboxymethyl betaine, lauryl dimethyl carboxy-methyl betaine, lauryl dimethyl alpha-carboxyethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis-(2-hydroxyethyl)carboxy methyl betaine, stearyl bis-(2-hydroxypropyl)carboxymethyl betaine, oleyl dimethyl gamma-carboxypropyl betaine, lauryl bis-(2-hydro-xypropyl)alpha-carboxyet-hyl betaine, etc. The sulfobetaines may be represented by coco dimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, amido betaines, amidosulfobetaines, and the like.

The nonionic surfactants useful in this invention can be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. Non-limiting examples of preferred nonionic surfactants for use herein are those selected form the group consisting of glucose amides, alkyl polyglucosides, sucrose cocoate, sucrose laurate, alkanolamides, ethoxylated alcohols and mixtures thereof. In a preferred embodiment the nonionic surfactant is selected from the group consisting of glyceryl monohydroxystearate, isosteareth-2, trideceth-3, hydroxystearic acid, propylene glycol stearate, PEG-2 stearate, sorbitan monostearate, glyceryl laurate, laureth-2, cocamide monoethanolamine, lauramide monoethanolamine, decyl glucoside and mixtures thereof. The composition of the present invention may also comprise one or more sugar based surfactants selected from but not limited to condensation products of long chain alcohols with sugar or starch polymers (e.g. decyl polyglucoside and lauryl polyglucoside), amides (e.g. cocoamide diethanolamine and cocoamide monoethanolamine), alkylene oxide derived surfactants (e.g. ceteth-6, ceteareth6, steareth-6, PEG-12 stearate, and PEG-200 glyceryl tallowate), Maltooligosyl Glucoside/Hydrogenated Starch Hydrolysate and mixtures thereof.

The aqueous carrier may be used in the present invention include but are not limited to water, aqueous – alcoholic solutions such as sorbitol, polyols and combinations thereof.
These cosmetic /personal care formulations may further comprise cosmetically acceptable excipients selected from preservative, structurant, active agent, humectants, conditioner, binders, emollient, emulsifiers, fragrance and emotives.

Preservatives according to the present invention include BHT, EDTA, phenoxy ethanol. Preservatives can be present in the range of from about 0.01% by weight to about 0.1% by weight, preferably from about 0.02% by weight to about 0.05% by weight.

Active agents that may be used in the present invention include lipophilic or hydrophilic active ingredients. As used herein an 'active agent is meant to comprise a compound that has a cosmetic or therapeutic effect on the skin, hair, or nails, e.g., lightening agents, darkening agents such as self-tanning agents, anti-acne agents, shine control agents, anti-microbial agents, anti-inflammatory agents, anti-aging agents, in particular anti-wrinkle agents, anti-mycotic agents, anti-parasite agents, external analgesics, sunscreens, photoprotectors, antioxidants, keratolyticagents, detergents/surfactants, moisturizers, nutrients, vitamins, energy enhancers, anti-perspiration agents, astringents, deodorants, hair removers, firming agents, anti-callous agents, and agents for hair, nail, and/or skin conditioning. Active ingredients may be added in the range of from about 0.001% by weight to about 10% by weight, preferably from about 0.1% by weight to about 5% by weight.

The conditioners as used herein are selected from but not limited to linear and/or branched chain Silicones and/or ethoxylatedamodimeticones, and or non-ethoxylatedamodimethocones and/or linear chain polyquarterniumHydroxy ethyl cellulose and/or branched hydrophobically modified polyquarternium hydroxyl ethyl cellulose.

The humectant in accordance with the present invention is selected from group comprising polyhydric alcohols, water soluble alkoxylated nonionic polymers, and mixtures thereof such as glycerin, sorbitol, propylene glycol, butylene glycol, hexylene glycol, ethoxylated glucose, 1, 2-hexane diol, hexanetriol, dipropylene glycol, erythritol, trehalose, diglycerin, xylitol, maltitol, maltose, glucose, fructose, sodium chondroitin sultate, sodium hyaluronate, sodium adenosin phosphate, sodium lactate, pyrrolidone carbonate, glucosamine, cyclodextrin, and mixtures thereof. The humectants herein are preferably used at levels by weight of the composition of from about 0.1% to about 20%, more preferably from about 0.5% to about 15%, and more preferably from about 1% to about 10%.

The structurant in accordance with the present invention is selected from group comprising biopolymers such as starch, modified starch, guar gum, tamarind kernel polysaccharide or psyllium husk; inorganics particles such as talc, calcite, clays, alumino silicate, calcium silicate, calcium alumino silicate, boro silicate, boroalumino silicate, alumina, sodium phosphate, aluminophospho silicate or silica and combinations thereof. The structurant is present in 2 to 35%, preferably 4 to 25%, more preferably 5 to 15% by weight of the composition.

Binders according to the present invention includes high molecular weight PEGs like PEG 6000, PEG 8000, poly acrylates, high molecular weight poly-ox, silicates, fatty alcohols, lanolin, sugars, tallow alcohol ethoxylates, and mixtures thereof. Other plastic binders are identified in the published literature, such as J. Amer. Oil Chem. Soc. 1982, 59, 442. Binders can be present in amounts 0.2 to 4 % by weight in the final product.

Emollients are substance which soften or improve the elasticity, appearance, and youthfulness of the skin (stratum corneum) by increasing its water content, and keeps it soft by retarding the decrease of its water content. Emollients that may be used in the present invention include but are not limited to silicone oils and modifications thereof such as linear and cyclic polydimethylsiloxanes; polyols such as glycerol, sorbitol; amino, alkyl, alkylaryl, and aryl silicone oils; fats and oils including natural fats and oils such as jojoba, soybean, sunflower, rice bran, avocado, almond, olive, sesame, persic, castor, coconut, mink oils; cacao fat; beef tallow, lard; hardened oils obtained by hydrogenating the aforementioned oils; and synthetic mono, di and triglycerides such as myristic acid glyceride and 2-ethylhexanoic acid glyceride; waxes such as carnauba, spermaceti, beeswax, lanolin, and derivatives thereof; hydrophobic plant extracts; hydrocarbons such as liquid paraffin, petrolatum, microcrystalline wax, ceresin, squalene, pristan and mineral oil; higher fatty acids such as lauric, myristic, palmitic, stearic, behenic, oleic, linoleic, linolenic, lanolic, isostearic, arachidonic and poly unsaturated fatty acids (PUFA); higher alcohols such as lauryl, cetyl, stearyl, oleyl, behenyl, cholesterol and 2-hexydecanol alcohol; esters such as cetyloctanoate, myristyl lactate, cetyl lactate, isopropyl myristate, myristylmyristate, isopropyl palmitate, isopropyl adipate, butyl stearate, decyloleate, cholesterol isostearate, glycerol monostearate, glycerol distearate, glycerol tristearate, alkyl lactate, alkyl citrate and alkyl tartrate; essential oils and extracts thereof such as mentha, jasmine, camphor, white cedar, bitter orange peel, ryu, turpentine, cinnamon, bergamot, citrus unshiu, calamus, pine, lavender, bay, clove, hiba, eucalyptus, lemon, starflower, thyme, peppermint, rose, sage, sesame, ginger, basil, juniper, lemon grass, rosemary, rosewood, avocado, grape, grapeseed, myrrh, cucumber, watercress, calendula, elder flower, geranium, linden blossom, amaranth, seaweed, ginko, ginseng, carrot, guarana, tea tree, jojoba, comfrey, oatmeal, cocoa, neroli, vanilla, green tea, penny royal, aloe vera, menthol, cineole, eugenol, citral, citronelle, borneol, linalool, geraniol, evening primrose, camphor, thymol, spirantol, penene, limonene and terpenoid oils; and mixtures of any of the foregoing components, and the like. Advantageously emollients may be used from about 0.5 to about 3 % by weight in the final product.

Further the composition of the present invention may comprise 0.5 to 1.5 % by weight of fragrance, 0.005 to 0.5 % by weight of emotives.

Further the composition of the present invention may comprise secondary emulsifiers. Secondary emulsifiers that may be added to compositions of the present invention can be of the W/O type or O/W type. The addition of an emulsifier allows the incorporation of hydrophilic components or agents into the wax phase. Preferred are non-ionic emulsifiers which typically have good skin compatibility. Non-ionic emulsifiers of the present invention may be selected from group comprising addition products of 2 to 50 moles of ethylene oxide and/or 0 to 20 moles propylene oxide to linear fatty alcohols having 8 to 40 C-atoms, to fatty acids with 12 to 40 C-atoms and to alkylphenols with 8 to 15 C-atoms in the alkyl rest; C12-18-fatty acid mono- and -diesters of addition products of 1 to 50 moles of ethylene oxide and glycerine; glycerine mono- and -diesters and sorbitan mono- and -diesters of saturated and unsaturated fatty acids with 6 to 22 C-atoms and their ethylene oxide addition products; alkyl mono- and -oligoglycosides with 8 to 22 C-atoms in the alkyl rest and their ethoxylated analogs; addition products of 7 to 60 moles of ethylene oxide to castor oil and/or hardened castor oil; Polyol- and in particular polyglycerine esters, such as e.g. polyol poly-12-hydroxystearate, polyglycerinepolyricinoleate, polyglycerinediisostearate or polyglycerinedimerate. Also applicable are mixtures of compounds of several of these substance classes; addition products of 2 to 15 moles of ethylene oxide to castor oil and/or hardened castor oil; partial esters derived from linear, branch chained, unsaturated or saturated C6-C22-fatty acids, ricinoleic acid as well as 12-hydroxystearic acid and glycerine, polyglycerine, pentaerythrite, dipentaerythrit, sugar alcohols (e.g. sorbitol), alkylglucosides (e.g. methylglucoside, butylglucoside, laurylglucoside), as well as polyglucosides (e.g. cellulose), or mixed esters such as e.g. glyceryl stearate/citrate and glyceryl stearate/lactate;Wool wax alcohols; Polysiloxane-polyalkyl-polyether-copolymers and derivatives thereof; Mixed esters from pentaerythrite, fatty acids, citric acid and fatty alcohols and/or mixed esters of fatty acids with 6 to 22 C-atoms with methylglucose and polyols, respectively glycerine or polyglycerine; Polyalkylene glycols. Emulsifiers can be present in amounts 0.5 to 5 % by weight in the final product.

The metal precursor of the present invention may be selected from a group comprising but not limited to metal salts such as Zn Acetate, TiCl2, ZnSO4, ZnNO3, Zn Stearate, Zn Acetylacetonate, Zn Laurate, Zn Palmitate, Zn Myristate, Mg Acetate, ZnCl2, ZnSO4, ZnNO3, Zn Stearate, Zn Acetylacetonate, Zn Laurate, Zn Palmitate, Zn Myristate and combinations thereof. These precursors of micronized particles may be present in the composition of the present invention in the range of from about 0.05% by weight to about 50% by weight, preferably from about 1% by weight to about 25% by weight.
Alkali solution as may be added during the process of preparation of the composite material of the present invention may be selected from a group comprising but not limited to sodium hydroxide, potassium hydroxide, magnesium hydroxide, ammonium hydroxide etc. The preferable alkali for the preparation of composite material of the present invention is sodium hydroxide and potassium hydroxide and combinations thereof. The amount of the base ranges from 0.2 to 15% by wt, preferably from 0.5 to 10% by wt.

The personal care formulations of the present invention can be in the form of a facewash, shampoo, bodywash, shower gel, facial cleanser, leave on gel, conditioner, body conditioner, shaving gel/cream, after shave cream/gel, sunscreen, etc.

The present invention is now being illustrated by way of non-limiting examples.

Example 1: Face wash Formulation

SI No Ingredients Wt(%) Function
1 Stearic Acid 2.0 Fatty Acid
2 Myristic Acid 2.0 Fatty Acid
3 Zinc Acetate 2.0 Metal precursor
4 Propylene Glycol 3.0 Humectants
5 Potassium Hydroxide 1.8 Base
6 Octylmethoxy Cinnamate 2.0 Active Ingredient
7 Ethyleneglycol Distearate 2.0 Emulsifier
8 Cocamide MEA 2.0 Emulsifier
9 Butylatedhydroxy Toluene 0.05 Anti-oxidant
10 Steareth 20 2.5 Emulsifier
11 Decyl Glucoside 5.0 Surfactant
12 SLES (28%) 8.0 Surfactant
13 CAPB (27%) 5.0 Surfactant
14 AOS 1.0 Surfactant
15 DI Water q.s. to 100 Water
16 Fragrance 0.5 Perfume
17 Tetrasodium EDTA 0.05 Chelating Agent

Process:
Step 1: Melting the fatty acid/acids at 75°C for 5 minutes under continuous stirring
Step 2: Addition of zinc acetate (zinc acetate is the precursor for ZnO, a UV A absorber) and propylene glycol to the mixture obtained from step 1 and mixing it for 15 minutes at 75°C.
Step 3: Addition of octylmethoxy cinnamate to the mixture obtained from step 2 at 70°C and mixing for 5 minutes.
Step 4: Addition of KOH solution (50%) in water drop-wise to the mixture obtained from step 3 under continuous stirring for 15 minutes at 70°C to obtain the in-situ generated metal oxide composite functionalized with octylmethoxy cinnamate
Step 5: Addition of ethyleneglycol distearate and cocamide MEA to the mixture obtained from step 4 and mixing at 70°C for 15 minutes
Step 6: Addition of butylatedhydroxy toluene and tetrasodium EDTA at 70°C and mixing for 2 minutes obtained from step 5.
Step 7: Addition of steareth 20 to the mixture obtained from step 6 at 70°C and mixing for 5 minutes
Step 8: Addition of all the surfactants to the mixture obtained from step 7 at 70°C and mixing for 10 minutes
Step 9: Addition of DI water drop-wise to the mixture obtained from step 8 at 60°C and the concoction was homogenized for 10 minutes at 5000 rpm.
Step 10: Addition of phenoxyethanol along with fragrance to the mixture obtained from step 9 at 40°C and mixing for 2 minutes.
Step 11: Collect the facewash in a container and store it at room temperature.

The scanning electron microscopy (SEM) image of the facewash composition containing in-situ generated composite material in the formulation is shown in Figure 1. Figure 2 shows the Electron Dispersive X-ray analysis (EDX pattern) of the facewash formulation confirming the presence of ZnO in the samples.

Example 2: Deposition of composite material through a face wash formulation

The facewash formulation prepared in Example 1 was applied on face for 30 seconds and rinsed off with water. The skin sample was collected using a carbon tape and the EDX analysis was done on the carbon tape containing skin sample to confirm the deposition of composite material on face. The EDX pattern of the skin sample collected is shown in Figure 3.
The EDX analysis confirms the presence of Zn and O in the skin sample and thereby proves that the composite material was deposited on the skin through face wash.

Example 3: Body wash Formulation

Process:

Step 1: Melting the fatty acid/acids at 75°C for 5 minutes under continuous stirring
Step 2: Addition of zinc acetate and propylene glycol to the mixture obtained from step 1 and mixing it for 15 minutes at 75°C.
Step 3: Addition of octylmethoxy cinnamate to the mixture obtained from step 2 at 70°C and mixing for 5 minutes.
Step 3: Addition of KOH solution (50%) in water drop-wise to the mixture obtained from step 2 under continuous stirring for 15 minutes at 70°C to obtain the in-situ generated metal oxide composite functionalized with octylmethoxy cinnamate
Step 4: Addition of ethyleneglycol distearate and cocamide MEA to the mixture obtained from step 3 and mixing at 70°C for 15 minutes
Step 5: Addition of butylatedhydroxy toluene and tetrasodium EDTA at 70°C and mixing for 2 minutes obtained from step 4.
Step 6: Addition of steareth 20 to the mixture obtained from step 5 at 70°C and mixing for 5 minutes
Step 7: Addition of all the surfactants to the mixture obtained from step 6 at 70°C and mixing for 10 minutes
Step 8: Addition of DI water drop-wise to the mixture obtained from step 7 at 60°C and the concoction was homogenized for 10 minutes at 5000 rpm.
Step 9: Addition of phenoxyethanol along with fragrance to the mixture obtained from step 8 at 40°C and mixing for 2 minutes.
Step 10: Collect the bodywash in a container and store it at room temperature

Example 4: Body Lotion Formulation

Process:
Step 1: Melting the fatty acid/acids at 75°C for 5 minutes under continuous stirring
Step 2: Addition of zinc acetate and propylene glycol to the mixture obtained from step 1 and mixing it for 15 minutes at 75°C.
Step 3: Addition of octylmethoxy cinnamate to the mixture obtained from step 2 at 70°C and mixing for 5 minutes.
Step 4: Addition of KOH solution (50%) in water drop-wise to the mixture obtained from step 3 under continuous stirring for 15 minutes at 70°C to obtain the in-situ generated metal oxide composite functionalized with octylmethoxy cinnamate
Step 5: Addition of butylatedhydroxy toluene and tetrasodium EDTA at 70°C and mixing for 2 minutes obtained from step 4.
Step 6: Addition of microcrystalline wax along with PEG-7 hydrogenated castor oil, hydrogenated poly-isobutane and 65°C to the mixture obtained from step 5 and mix it for 10 minutes.
Step 7: Addition of p-Dimethylaminobenzoic acid 2-ethylhexyl ester and dimethicone to the mixture obtained from step 6 and mixing it for 5 minutes at 65°C.
Step 8: Addition of propylene glycol and glycerine to the mixture obtained from step 7 and mixing at 65°C for 15 minutes
Step 9: Addition of DI water drop-wise to the mixture obtained from step 8 at 65°C and the concoction was homogenized for 20 minutes at 5000 rpm
Step 10: Addition of phenoxyethanol along with fragrance to the mixture obtained from step 9 at 40°C and mixing for 2 minutes
Step 11: Collect the body lotion in a container and store it at room temperature.

Example 5: Skin Cream Formulation

Process:

Step 1: Melting the fatty acid/acids at 75°C for 5 minutes under continuous stirring
Step 2: Addition of zinc acetate and propylene glycol to the mixture obtained from step 1 and mixing it for 15 minutes at 75°C.
Step 3: Addition of octylmethoxy cinnamate to the mixture obtained from step 2 at 70°C and mixing for 5 minutes.
Step 4: Addition of KOH solution (50%) in water drop-wise to the mixture obtained from step 3 under continuous stirring for 15 minutes at 70°C to obtain the in-situ generated metal oxide composite functionalized with octylmethoxy cinnamate
Step 5: Addition of butylatedhydroxy toluene and tetrasodium EDTA at 70°C and mixing for 2 minutes obtained from step 4.
Step 6: Addition of microcrystalline wax along with mineral oil to the mixture obtained from step 5 at 65°C and mixing for 15 minutes
Step 7: Addition of PEG-7 hydrogenated castor oil, hydrogenated poly-isobutane and dimethicone to the mixture obtained from step 6 mixing it for 15 minutes at 65°C
Step 8: Addition of glyceryl stearate and myristyl myristate to the mixture obtained from step 7 mixing it for 20 minutes at 65°C
Step 9: Addition of p-Dimethylaminobenzoic acid 2-ethylhexyl ester and dimethicone to the mixture obtained from step 8 and mixing it for 5 minutes at 65°C.
Step 10: Addition of propylene glycol and glycerine to the mixture obtained from step 9 and mixing at 65°C for 15 minutes
Step 11: Addition of DI water drop-wise to the mixture obtained from step 10 at 65°C and the concoction was homogenized for 20 minutes at 5000 rpm
Step 12: Addition of phenoxyethanol along with fragrance to the mixture obtained from step 11 at 40°C and mixing for 2 minutes
Step 13: Collect the skin cream in a container and store it at room temperature.

Example 6: Conditioning Shampoo Formulation

Process:
Step 1: Melting the fatty acid/acids at 75°C for 5 minutes under continuous stirring
Step 2: Addition of zinc acetate to the mixture obtained from step 1 and mixing it for 15 minutes at 75°C.
Step 3: Addition of octylmethoxy cinnamate to the mixture obtained from step 2 at 70°C and mixing for 5 minutes.
Step 4: Addition of KOH solution (50%) in water drop-wise to the mixture obtained from step 3 under continuous stirring for 15 minutes at 70°C to obtain the in-situ generated metal oxide composite functionalized with octylmethoxy cinnamate
Step 5: Addition of butylatedhydroxy toluene and tetrasodium EDTA at 70°C and mixing for 2 minutes obtained from step 4.
Step 6: Addition of Cocamide MEA and Ethylene Glycol Distearate at 70°C and mixing for 10 minutes obtained from step 5
Step 7: Addition of Cetearyl alcohol and cetereth 20 at 70°C and mixing for 10 minutes obtained from step 6
Step 8: Addition of all the surfactant/surfactants to the mixture obtained from step 7 and mixing at 40°C for 15 minutes.
Step 9: Addition of Dimethicone to the mixture obtained from step 8 and mixing it for 5 minutes at 40°C
Step 10: Addition of DI water drop-wise to the mixture obtained from step 9 at 65°C and the concoction was homogenized for 20 minutes at 5000 rpm
Step 11: Addition of phenoxyethanol along with fragrance to the mixture obtained from step 5 at 40°C and mixing for 2 minutes
Step 12: Collect the conditioning shampoo in a container and store it at room temperature.

Example 7: Facewash Formulations without in-situ generated composite material

Process:
Step 1: Melting the fatty acid/acids at 75°C for 5 minutes under continuous stirring
Step 2: Addition of propylene glycol to the mixture obtained from step 1 and mixing it for 15 minutes at 75°C.
Step 3: Addition of octylmethoxy cinnamate to the mixture obtained from step 2 at 70°C and mixing for 5 minutes.
Step 4: Addition of ethyleneglycol distearate and cocamide MEA to the mixture obtained from step 3 and mixing at 70°C for 15 minutes
Step 5: Addition of butylatedhydroxy toluene and tetrasodium EDTA at 70°C and mixing for 2 minutes obtained from step 4.
Step 6: Addition of steareth 20 to the mixture obtained from step 5 at 70°C and mixing for 5 minutes
Step 7: Addition of all the surfactants to the mixture obtained from step 6 at 70°C and mixing for 10 minutes
Step 8: Addition of zinc acetate to the mixture obtained from step 7 and mixing it for 15 minutes at 75°C.
Step 9: Addition of KOH solution (50%) in water drop-wise to the mixture obtained from step 8 under continuous stirring for 15 minutes at 70°C to generate fatty acid soaps along with the zinc oxide particles.
Step 10: Addition of DI water drop-wise to the mixture obtained from step 9 at 60°C and the concoction was homogenized for 10 minutes at 5000 rpm.
Step 11: Addition of phenoxyethanol along with fragrance to the mixture obtained from step 10 at 40°C and mixing for 2 minutes.
Step 12: Collect the facewash obtained from step 11 in a container and store it at room temperature

Observation: The facewash formulation was generated without the in-situ generated composite material. In this case both the UV A and UV B absorbers are present but did not form of composite.

Example 8 : EDX analysis to demonstrate deposition of ZnO (Zn acetate used) composite in accordance with the present invention on the skin
The facewash formulation prepared in Example 1 was applied on face for 30 seconds and rinsed off with water. The skin sample was collected using a carbon tape and the EDX analysis was done on the carbon tape containing skin sample to confirm the deposition of composite material (ZnO) on face. The EDX pattern of the skin sample collected is shown is Figure 3.
EDX spectra as shown in Figure 3 confirmed the deposition of ZnO (acetate used) composite on the skin. The EDX spectra of the skin samples without treatment of the facewash did not show any ZnO. Therefore, it was concluded that composite material deposits on the skin through facewash.
The sample was collected from the untreated skin and the EDX spectra of untreated skin sample are shown in Figure 4.

Example 9

The facewash formulation containing the physical mixture of ZnO and OMC is provided below.

Process:
Step 1: Melting the fatty acid/acids at 75°C for 5 minutes under continuous stirring
Step 2: Addition of KOH solution (50%) in water drop-wise to the mixture obtained from step 1 under continuous stirring for 15 minutes at 70°C to obtain the fatty acid soap.
Step 3: Addition of ethyleneglycol distearate and cocamide MEA to the mixture obtained from step 2 and mixing at 70°C for 15 minutes
Step 4: Addition of butylatedhydroxy toluene and tetrasodium EDTA at 70°C and mixing for 2 minutes obtained from step 3.
Step 5: Addition of steareth 20 to the mixture obtained from step 4 at 70°C and mixing for 5 minutes
Step 6: Addition of all the surfactants to the mixture obtained from step 4 at 70°C and mixing for 10 minutes
Step 7: Addition of zinc oxide and propylene glycol to the mixture obtained from step 6 and mixing it for 15 minutes at 75°C.
Step 8: Addition of octylmethoxy cinnamate to the mixture obtained from step 7 at 70°C and mixing for 5 minutes.
Step 9: Addition of DI water drop-wise to the mixture obtained from step 8 at 60°C and the concoction was homogenized for 10 minutes at 5000 rpm.
Step 10: Addition of phenoxyethanol along with fragrance to the mixture obtained from step 9 at 40°C and mixing for 2 minutes.
Step 11: Collect the facewash in a container and store it at room temperature.

The facewash sample from the above was prepared applied on face for 30 seconds and rinsed off with water. The skin sample was collected using a carbon tape and the EDX analysis was done on the carbon tape containing skin sample to confirm the deposition of composite material (ZnO) on face. The EDX pattern of the skin sample collected is shown is Figure 5.

The facewash formulation containing the physical mixture of ZnO and OMC was treated with skin and the EDX spectra of the skin sample shown in Figure 5. The quantification of elements as obtained from Figure 5 is found in Table 3, which shows that ZnO is present in the formulation as a physical mixture. Thus, even though ZnO is present in the formulation as a physical mixture it does not deposit on skin.

Example 10
Studies exhibiting that the composite is unstable beyond the inventive range.

The compositions used for the study were prepared according to the following method.
(i) Melting metal oxide precursor along with emulsifiers and surfactants at around 65°C - 75°C and mixing for 20 minutes.
(ii) Addition of active ingredient, salicylic acid (anti-acne), amounting to 0.5% w/w, to the mixture obtained from step (i) and mixing it at 50 to 60°C;
(iii) Addition of alkali solution drop-wise to the mixture obtained from step (ii); and
(iv) Making up the volume of the mixture obtained from step (iii) with water and homogenizing (5000 rpm for 10 minutes) to obtain the final formulation.

Experiment No Metal Precursors (%) (w/w) Alkali (%) (w/w) Emulsifiers (%) (w/w) Surfactants (%) (w/w) Water % (w/w) Observations
1 0.001 0.2 0.5 10 q.s. to 100 In-situ generation of composite in the formulation was not achieved
2 70 5 5 5 q.s. to 100 Composite was generated in-situ but the formulation was unstable and phase separated within 24 hours
3 2 0.05 5 10 q.s. to 100 The in-situ generated composite was not achieved in the formulation.
4 5 20 5 10 q.s. to 100 Composite was generated in-situ but the formulation was unstable and was phase separated within 4-5 hours.
5 10 20 20 10 q.s. to 100 Composite was generated in-situ but the formulation was unstable and was phase separated within 2-3 days
6 5 5 80 5 q.s. to 100 Composite was generated in-situ but the formulation was unstable and was phase separated within 3-4 days
7 5 5 40 0.05 q.s. to 100 Composite was generated in-situ but the formulation was unstable and was phase separated within 48 hours
8 10 10 10 60 q.s. to 100 The in-situ generated composite was achieved in the formulation but was phase separated within 2-3 hours
9 5 5 0.1 10 q.s. to 100 Composite was generated in-situ but the formulation was unstable and was precipitated from the formulation

Example 11
Facewash Formulation containing an anti-acne active

Process:
Step 1: Melting the fatty acid/acids at 75°C for 5 minutes under continuous stirring
Step 2: Addition of zinc acetate and propylene glycol to the mixture obtained from step 1 and mixing it for 15 minutes at 75°C.
Step 3: Addition of salicylic acid to the mixture obtained from step 2 at 70°C and mixing for 5 minutes.
Step 4: Addition of KOH solution (50%) in water drop-wise to the mixture obtained from step 3 under continuous stirring for 15 minutes at 70°C to obtain the in-situ generated metal oxide composite functionalized with salicylic acid
Step 5: Addition of ethyleneglycol distearate and cocamide MEA to the mixture obtained from step 4 and mixing at 70°C for 15 minutes
Step 6: Addition of butylatedhydroxy toluene and tetrasodium EDTA at 70°C and mixing for 2 minutes obtained from step 5.
Step 7: Addition of steareth 20 to the mixture obtained from step 6 at 70°C and mixing for 5 minutes
Step 8: Addition of all the surfactants to the mixture obtained from step 7 at 70°C and mixing for 10 minutes
Step 9: Addition of DI water drop-wise to the mixture obtained from step 8 at 60°C and the concoction was homogenized for 10 minutes at 5000 rpm.
Step 10: Addition of phenoxyethanol along with fragrance to the mixture obtained from step 9 at 40°C and mixing for 2 minutes.
Step 11: Collect the facewash in a container and store it at room temperature.

Example 12
Comparative deposition studies

Table 1 shows the elemental composition of obtained from EDX spectra as shown in Figure 3.

It shows the quantification of elements present from the EDAX spectra of facewash treated skin samples containing in-situ generated composite material of the present invention.

Therefore it is evident that ZnO was deposited.

Table 2 shows the elemental composition of obtained from EDX spectra as shown in Figure 4.

It shows the quantification of elements present from the EDAX spectra of the untreated skin sample

Therefore it is evident that ZnO composite was not present in the normal skin samples.

Table 3 shows the elemental composition of obtained from EDX spectra shown in Figure 5.
It shows the quantification of elements present from the EDAX spectra of facewash treated skin samples containing the physical mixture of ZnO and OMC.

Therefore it is evident that there was no deposition of ZnO even though the facewash formulation contained physical mixture of ZnO and OMC.