AU2017200676B2 - Photoprotective compositions comprising synergistic combination of sunscreen active compounds - Google Patents

Abstract

Compositions for topical application to skin and/or hair, comprising photoprotecting synergistically effective amounts of sunscreen active agents octinoxate, octocrylene, and amiloxate; methods of protecting skin and/or hair against deleterious effects of sunlight/UV radiation by topical application of compositions.

Description

Phatopratectiw ComposWQOS C&mpHsing

Syn^rgfetie Cbmbioation of Sunscreen Active Compounds

HELP OF THE tWEMTIQH

Th® subject invention is directed to compositions for topical application containing a synergistic combination of sunscreen active compounds, and more particularly to compositions for topical application comprising a synergistic combination of octinoxate, octocrytene, and amiloxate.

BACtCGROOHO OF THE IHyENTW

When applied topically, sunscreen composition®impart a film that protects skin against the damaging effects of exposure to th® sun’s ultreviotet radiation (UVR). Sunscreen active compounds work on skin’s surface by absorbing UVR before ii can interact with and damage skin. A particular ccmpositton's ability to block UVR Is usually expressed in a stm protection factor or SPF rating. Combinations of sunscreen active compounds are typically used in sunscreen composition in order to raise the SPF rating of the composteun.

so U.S. Patent Nos. 6,030,629 and 5,963,461 assert synergistic increase in SPF based on combinations of certain sunscreen active compounds. Further, Andre et al, report a synergistic effect,based on a combination of organic and inorganic sunscreens covering UV-A and UV-B absorption. (V. Andre et at, Cosmetics and Toiletries Manufacture Worldwide 2004, pp. 192s 23.) However, as those authors note, such synergistic increases in SPF are not completely understood, nor is it predictable before hand which combination of compounds will demonstrate a synergistic effect In fact, as demonstrated in the experiments herein, a combination of only two of the three sunscreen actives in the present Invention does not show synergistic an SPF increases*

Thus a cumbination of sunscreen active compounds that demonstrete a synergistic increase in SPF, and thus an enhanced UVR pratectective

2017200676 01 Feb 2017

- 2 ~ capability over what would be pradlcted from their use atone, would be useful and desirable.

These and other objectives are obtained by the invention more fully desoribed and claimed herein.

s

Sy^MARY OF THE IWVEHTIOH

The subject invention provides a topically applicable sunscreen composifion suited for the photoprotection of human skin and/or hair, comprising photopmtechlng synergistically effective amounts of ociinoxate.

io octocry tone, and amiloxate.

The subject invention also provides a cosmetic composition for topical application to human skin and/or hair, comprising photopreteettog synergistically effective amounts of octinoxaie. octocrylene, and amitoxate.

The subject invention further provides a method for protecting human is skin and/or hair against toe deleterious effects of solar radiation, mure particularly ultraviolet radiation (UVR) comprising topically applying thereto an effective amount of the sunscreen compositions as described herein.

DETAILED DESCRIPTION so The subject invention provides a topically applicable sunscreen composition suited for the photoprotectton of human skin and/or hair, comprising phetoprofectfog synetglstlsaliy effective amounts of octinoxate, octocryfene. and amiloxate. Oetfooxate, which fc also known as octyl rnethoxyomnamate or ethylhexyl methoxycinnamate, is listed in Annex VII of a s the EU Cosmetics Directive for use as a sunscreen agent up to a leva! of 10%. In the United States. It is listed by the USFDA for use at level up to 7.5%. Ooiocrylene, whose chemical same is 2-ethylhexyi 2-cyano~3,3~ diphenyl>'2“ptopenaate. is listed by ths USFDA for use up to 10% and in the EU Cosmetics Directive for use up to W%. Amiloxate, whose chemlcsl name

Is 2-beazoic: acid. 2~propenoic s.cid.344mmthaxypheay0~3~methyfoutyi ester and is also known by 4-Methoxycinnamic acidjsoamyl ester or isoamyl p« methoxycinnamate, is being reviewed for approval by the USFDA for use up to 10% and is listed in the EU Cosmetics Directive for use up to 10%. it Is

2017200676 01 Feb 2017 ents sn pn sRtln t'r *£3

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propellant, which «pay be any suitable gas. that can be compressed ar liquefied within a spray dispensing canister and which expands orvotefitizes to vapor ar gas form upon exposure to ambient temperature and pressure conditions to deliver the composition in an aerosol form. Suitable propellants include hydrocarbons having 1 to 5 carbon atoms, including but not limited to methane, ethane, propane, isopropane, butane, isobutene, butene, pentane, isopentane, neopentane, pentone, hydrofluorocarbons (HFCs), chlorofluurocafbons(C4“Cs), nitrogen, ethers including dimethyl ether, and any mixtures thereof, Those of ordinary skill in the art recognize that in a dosed container such as an aluminum nan nr glass bottle, propellants such as dimethyl ether condense to the liquid state at ambient temperature. Thus, ths composition in the aerosol container is liquid formulation which ran contain dissolved propellant, undissoived liquid propellant and gaseous propellant Ail of this Is under pressure due to the vapor pressure of the propellant In the

IS practice of the subject Invention, the propellant can be present In an amount up to about 90 weight percent, preferably from about 2 weight percent to about 56 weight percent, and more preferably about 5 weight percent to about 40 weight percent, most preferably 30 weight percent, based an the total weight of the aerosol composition.

uo The compositions of the invention can also comprise aerosol foams pr so-called mousse compositions. For example, U.S, Patent Na, 6,627,585 describes a mousse-forming ofeansing shampoo oompositton comprising a toamable concentrate comprising at least one surfaetant, dispersed partides of a water-insoluble conditioning agent, an aqueous carrier; and an aerosol propellant. U.S. Patent No. 6,284,964 describes a cosmetic composition including a crosslinked non-emulsifying polymtoxana elastomer and a parttoxyvinyi polymer which Is in the form of a n aerosol foam in a pressurised system, The propellant may be introduced Into ths mousse composition at the time of filling by using a standard aerosol dispenser, e.g. a spray can so arrangement

The subject inventfon contemplates the tocurporatton of the synergistic combination of sunscreen actives to sunscreen and sunblock products and any other topically applied composition where file addltiea of sunscreen

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-5actlve agents would not detract f mm the efficacy of the product nor affect ths sunscreening ability of the sunscreen active agents. Thus the subject invention also provides a cosmetic composition for topical application to human skin and/or hair, comprising photopretectlng synergistically effective amounts of ©ctinoxale, ootacryiena, and amifoxate. Hondimiting examples of such cosmetic compositions may Include such products as moisturizers, cleansers, oonditodem, shampoo, body Wash, styling gsl/lQtinn, eye cmam and aye liner, blush, mascara, foundation, nail polish, polish remover, eye shadow, lipstick, lip gloss, tip liners, lip balms, makeup remover, nail i.o ireatment, foot care compositions, acne treatment, redness/rosacea treatment, variccse/spider vein treatment, anti-aging compositions, sunless tanning compositions, after-sun compositions, conceafers, hair color and bleaching compositfens, skin fadlng/lighfeners, body firming lotion, shaving cream, after shave, rslaxer, antiperspirants and deodorants, exfoliants, is scrubs, liquid hand soap, bubble bath, pain and wound treatment compositions, insect repallani, anthitoh and rash cream, styling mousse and foams, perfume, lubricants, body oil, body spray, baby lotion, diaper cream, baby soap, baby shampoo, baby oil, baby wipes, hairdoss treatment, hair spray, depilatory, hair growth Inhibitors, hair removal waxes, personal go deansing, colognej oil controller, and hand sanitizer.

The compositions of the present invention may contain a wide range of additional, optional components which are referred to herein as cosmetic components’¹, but which can also include components generally known as pharmaceutically active agents.. The CTFA Cosmetic Ingredient Handbook, 25 Seventh Edition, 1997 and the Eighth Edition, 205, which is incorporated by reference herein in its entirety, describes a wide variety of cosmetic and pharmaceutical ingredients commonly used in skin care compositions, which are suitable for use in the compositions of the present invention. Examples of these functional classes disclosed in this reference Indude: absorbents, s o abrasives, anticaking agents, antifoaming agents, antioxidants, binders, biological additives, buffering agents, bulking agents, chelating agents, chemical additives, colorants, cosmetic astringents, cosmetic biocides, denaturants, drug astringents, external analgesics, film formers, fragrance

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- g cbmponants, humectants,, upscifyirw agents, pH adjusters, plasticizers, reducing agents, skin bleaching agents, skin-conditioning agents (emollient, humectants, mlscalteneous, and ocdushte}, skin protectante, solvents, foam boosters, hydrotropes, solubilizing agents, suspendfog agents

S (nonsurfactant), sunscreen agents, ultraviolet light absorbers, SPF boosters, waterproofing agents, and viscosity increasing agents (aqueous and nonaqueous).

In the practice of the foveritium the oomposltten rnay contain one or more sddiftanal sunscreen active agents. For purposes of the present invention, a “sunseraen active agent⁸ or teunsureen active shall include all of those materials, singly or in combination, that are regarded as acceptable for use as active sunsereenlng fogredtents based on their ability to absorb UV radieton. Such compounds are generally described as being UV-A, UV-β, or UV-A/UV-B active agents. Approval by a regulatory agency is generally is required for inclusion of active agents in formulations intended for human use..

Those active, agents which have been or are currently approved for sunscreen use in the United States include organic and inorganic substances including, without limitation, para aminobenzoic acid, avobanzone, cinoxate, dioxybenzone, homosaiate, menthyl anthranilate, octyl salicylate,

0 oxybenzone, padlmate O, phehyibenzimidazote sulfonic acid, sulisobenzoae, trotamine salicylate, titanium dioxide, zinc oxide, diethanolamine methoxycinnamate, digailoy trioleate, ethyl ditiydmxypropyl PASA, glyceryl aminobenzoate, lawsons with dihydroxyacetone, red petrolatum. Examples of additional sunscreen actives that have not yet been approved in the US but are allowed in formulations sold eutside of the US inoluds ethylhexyl biazene, dioctyl butamidu triazonc, benzylidene malonate polysiloxane, terephthalylidane dlcamphor sulfonic acid, disodium phenyl dibenzimidazote tetrasulfonate, diethytamino hydroxybenzoyl hexyl benzoate, bis dfethylamlno hydroxybenzoyi benzoate, bls benzoxazoylphenyl ethylhexylimino tteine, c drometrizule tnsltoane, methylene bl s-benzatriszolyl tetramethyibutylphenoh and bis-eihylhexyfoxyphenol methoxypHenyitdazine, 4methylbenzylidenecamphor, and isopentyl 4-methoxyclnnamate. However, as the list of approved sunscreens is currently expanding, those ef ordinary skill

2017200676 01 Feb 2017

-7wiil recognize that the invention is not limited to sunscreen active agents currently approved for human use hut is readily applicable to those that may be allowed in the future.

In one embodiment of the inveniinn the add monel sunscreen active

B agent comprises a photeprotecilng effective amount of particulates of at least one inorganic pigment or nanapigment, nondimiting examples of which include titanium dioxide, zinc oxide, iron oxide, zirconium oxide, cerium oxide, or mixture thereof..

The compositions of the invention may also include materials that also io increase the 8PF of the final compmltioa by such mechanisms as UV radiation scattering and dispersion. Such materials are referred to herein as “UV-radiaiion scattering agents” and comprise materials that exhibit UV absorbing activity cr exhibit no UV absorbing activity. An example of such UVvMiaton scattering agents include polymeric materials, such as the is product known as SunSpheres™ (Rohm and Haas; Philadelphia, PA) which are described by their manufacturer as hollow styrane/acrylates copolymer spheres manufactured by emulsion polymerization. The polymer spheres are said to raise SPF values across the UVA and UVB region by dispersing and/or scattering the incident UV radiation throughput the film of sunscreen 20 present on a surface, such as human skin. It is understood that the spheres cause less UV radiation to penetrate into the skin by redirecting the radiation towards the UV~absorbing sunscreen actives In the sunscreen formulation, where ths radiation reacts with the sunscreen active molecules and the energy is dissipated as heat. As used herein, ths terms “spheres” or “scattering agents are not limited by chemical makeup or shape, but comprise any agent that produces te effect of lengthening the path of incident UV radiation, increasing the statistical likelihood that the radiation will contact a sunscreen active molecule, i.e.., a UV absorbing active agent. These materials may also include UV absorbing materials that also exhibit & scattering properties such as ZnO (examples include Z«Cote™ products available from BASF), 11¾ (examples include te Solavsil™ products available from Uniqoma (New Castle, DE. USA]), compounds such as methylene bis-benzotriazclyl tetramethytetyiphenol. (“Ttesorb™ M

2017200676 01 Feb 2017 io

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- 9 ~ (40) stearate, polyoxyethylene fatty alcohol ethers such as polyoxyethylene (20) stearyl ether, polyoxyethylene sorbitan fatty add esters such as polyoxyethylene sorbitaa monostearate, sorbitan esters suets as sorbitan monostearate, alkyl glycosides such as cetearyl glucoside, fatty add efhanoiamides and their dehvatives such as the dtethanolamide of stearic add, and the like. Examples of suitabte anionic surfactants are soaps including alkali soaps, such as sodium, potassium and ammonium salts of aliphatic carboxylic adds, usually fatty adds, such as sodium stearate. Organic amine soaps indude organic amine safe of aliphatic carboxylic adds, 10 usually fetty adds, such as triethanolamine stearate. Metallic soaps include salts of polyvalent metals and aliphatic carboxylic acids, usually fatty acids, such as aluminium stearate, Other classes Of suitable anionic surfactants include sulfated fatty add alcohols such as sodium lauryl sulfate, sulfated oils such as the sulfuric ester of rfcinoleic acid disodium sail, and sulfonated is compounds such as alkyl sultanates including sodium cetane sulfonate, amide sulfonates such as sodium N-melhyl-N-oteyl laurate, sulfonated dibasic add esters such as sodium dioctyl sulfosuccinate, alkyl aryl sulfonates such as sodium dodscylbenzen© sulfonate, alkyl nsphthatehe sulfonates such a sodium isopropyl naphthalene sulfonate, petroleum sulfonate such as aryl c nspthalene with alkyl substitutes. Examples of suitable cationic surfactants include amine safe such as octadecyl ammonium chloride, quarternary ammonium compounds such as benzalkonium chloride.

An emollient Is an oleaginous or oily substance which helps to smooth sad soften the skin, and may also reduce its roughness, cracking or Inflation, s s Typical suitable emollients induds mineral oil having a viscosity In the range of 50 to SOU centipoise (cps), lanolin oil, coconut oil, cocoa batten olive oil, almond oil, macadamia out ail, aloo extracts such as aloe vara lipoqulnone, synthetic jojoba oils, natural sonora jojoba oils, safflower oil, corn oil, liquid lanolin, cottonseed Oil and peahut oil Preferably, the emollient is a o cocogiyceride, which is a mixture bf mono, di arid triglycerides of cocoaoil, sold under the trade name of Myritol 331 from Henkel KGaA, or Dlcaprylyl Ether available under the trade name Cetiol GE from Henkel KGaA nr a G«~ C?s Alkyl Benzoate sold under the trade name Rnsolv TN from Rnetex, One

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-10 or mom emollients may be present ranging In amounts from about 1 percent to about 10 percent by weight, preferably about S percent by weight. Another suftable emollient Is DC 200 Fluid OSO, a silicone fluid, available Dow Coming Corp.

Other suitable emollients indude squalane, castor oil, polybufene, sweet almond nil, avocado oil, catophyllum oil, ricin oil, vitamin E acetate» olive OH, siftcone oils such as dimethytopelysitaane and cyclometoiccne, rteotenic alcohcl, oleyl alcohol, the oil of cereal geons such as the oil of wheat germ, isopropyl palmitate, octyl palmitate, isopropyl myristate, hexadecyl ία stearate, butyl stearate, decyl oleate, acetyl glycerides, the octanoates and bencoates of (C^ -Q_{s) alcohols, the octanoates and decanoates of alcohols and polyalcohols such as those of glycol and glyceryl ricincleates esters such as Isopropyl adipate, hexyl laurate and octyl dodecanotee, dicaprylyl maleate, hydrogenated vegetable oil, phenyltrimethluune, jojoba oft and aloe vera is extract

Other suitable emofttenis which are solids or semi-solids at ambient temperatures may be used. Such solid or semi-solid cosmetic emollients include glyceryl dilaurate, hydrogenated lanolin, hydroxylated lanolin, acetylated lanolin.. pmroiatem, isopropyl lanoiate, butyl myristate, cetyl myristate, myristyl myristate, myristyl lactate, cetyl alcohol, isostearyl alcohol and Isecatyl lanolate. One or more emollients can optionally be included In the formulation.

A humectant is a moistening agent that promotes retention of water due to its hygroscopic properties. Suitable humectants include glycerin, s polymeric glycols such as polyethylene glycol and polypropyterm glycol, mannitol and sorbitol Preferably, the humectant is Sorbitol 70¾ USP or polyethylene glycol 400, NF, One or more humectants can optionally be Included to the formulation in amounts from about 1 percent to about TO peroent by weight, preferably about S percent by weight.

A dry-feel modifier is an agent which when added to an emulsion,

Imparts a dry feel to tbs skin when the emuteion dries. Dry feel modifiers can include talc, kaolin, chalk, mnc oxide, silicone fluids, inorganic salts such as barium sulfate, surface treated silica, precipitated silica, fumed silica such

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-11as an Aerosil available from Oegussa Inc. of New York, N.Y. U.S.A. Another dry feel modifier is an epichlorohydrin cross-linked glyceryl starch of the type that Is di sclosed in U.S. Patent No, 6,488,916.

It may be advantageous to incorporate additional thickening agents, a such as, for instance, various Carbopols available from Novena Co, Particularly preferred are those agents which would not disrupt the lamellar structure in the formulation of the final product, such as nun-ionic thickening agents. The selection of additional Wakening agenta is well within the skill of one in the art.

An tantioxidanU Is a natural or synthetic substance added lathe sunscreen to protect from ar delay its deterioration due to the action of oxygen in ths air (oxidation). They may also reduce oxidation reactions in skin tissue. Anti-oxidants prevent oxidative deterioration which may lead to the generation of rancidity and nonenyxymatic browning reaction products.

is Typical suitable antioxidants Include propyl, octyl and dodecyl esters of gallic acid, butylated hydroxyanisole (BHA, usually purchased as a mixture of ortho and mete isomers). butylated hydroxytoluene· {BUT)., green tea extract, uric acid, cysteine, pyruvate, nordihydroguaiaretic acid, Vitamin A, Vitamin E and Vitamin C and their defiYatives. One or more antioxidanta can optionally be included in the sunscreen composition in an amount ranging horn about 8,001 to about § wight percent, preferably about 0.01 to about 0.8 percent.

Ghclating agents* am substances used to chelate or bind metallic ions, such as with a hetemuyiie ring structure so that ths ion is held by chemical bonds from each of th® participating rings. Suitable chelating agents as include ethylene dlaminetefraacetic add (EDTA), EDTA disodium, calcium dlsodium edefate, EDTA trisodium, albumin, transferrin, desferoxamine, desferal, desferoxamine mesylate, EDTA tetrasodium and EDTA dipotasstam, or combinations of any of these,

Tragtanoes* are aromatic substances which can impart an aesthetically pleasing aroma to ths sunscreen composition, Typical fragrances include aromatic materials extracted from botanical sources (i.e., rose petals, gardenia blossoms, jasmine bowers, etc.) which can be used alone ar in any combination to create essential oils. Alternatively, alcoholic

2017200676 01 Feb 2017 extracts may be prepared for compounding fragrances. However, do© to the relatively high costs of obtaining fragrances from natural substances, the modern trend is to us© synthetically prepared fragrances, particularly in highvolume products, One or more fragrances can optionally be included in the S sunscreen composition in an amount ranging from about 0,001 to about 5 weight percent preferably about<01 to about 0,5 percent by weight Additional preservatives may also be used if desired and include well known preservative compositions such as benzyl alcohol, phenyl ethyl alcohol and benzoic acid, diaznlydinyl, urea, chferphanasi< todoprcpynyl and butyl io carbamate, among others.

The compositions of the invention can further comprise skin protectent active agents. Suitable examples include (with preferred weight percent ranges), Allantoin (0.5 to 2 percent); Aluminum hydroxide gei (0,15 to 5 percent): Calamine (1 to 25 percent); Cocoa bettor (greater than 50); Cod liver is oil (5 to 14 percent); Colloidal oatmeal; Dimethicone (1 to 30 percent);

Glycerin (20 to 45 percent); Hard fat (greater than 50); Kaolin (4 to 20 percent); Landin (12,5 to 50 percent); Mineral oil (greater than 50 percent); Petrolatum (greater than 30 percent); Sodium bicarbonate; Topical starch (10 to 98 percent); While petrolatum (greater than 30 percent); Zinc acetate (0,1 3c to 2 percent); Zinc carbonate (0..2 to 2 percent); and Zinc oxide (1 to 25 percent),

T|ia ecmpcsitiens of the invention may further include insect repelling components. The most widely used insect repelling active agent for personal care products is NiH-DiethyKrn’toiuamide, frequently called *DEET' and as available In the form of a concentrate containing at least about 95 percent DEEx other synthetic ctemical repellents include ethyl butytacetylaniinopropriunate (also known as IR 3535), dimethyl phthalate, ethyl hexanediol, indaione, di-mpnapyllsoclnchoronate, blcyctoheptene, dicarboximide and tetrahydrafuraidehyde. Certain plant-dewed materials 3 c also have insect repellent activity, including dtronefe ail and other sources of citronella (including lemon grass oil), limonene, rosemary oil and eucalyptus oil. Choice of an insect repellent for incorporation into the sunscreen emulsion will frequently be influenced by the odor of the repellent The

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-13~ amount of repellent agent used will depend upon the choice of agent; DEBT is useful at high conoentrabons. such as up to about 15 percent or more, white some of the plant-derived subsianoee are typically used in much lower amounts, such as 0.1 percent or less,.

s Tepical application of the compositions of the invention described herein to the hair or skin of a human will provide enhanced protection against deleterious effects of ultraviolet radiate (UVR), Thus, the subject invention further provides a method for protecting human skin and/or hair against the defetertous effects of solar radiate, more particularly UVR, whichmethod io comprises topically applying thereto an effective amount of the sunscreen compositions as described herein. An esthetlcaliy beneficial result of exposure of sklh to UVR (I.e., light raditlon wavelengths of from 2SQ nm to 400 nm) is the promotion of tanning of the human epidermis. Another benefit of sun exposure comes from production of vitamin 0 within the skin, UVR is

I S typically divided into UV-A (fight wavelengths from 320 to 400 nm) and UV-B (wavelengths ranging from 28(1 to 320 nm) regions.. Overexposure to UV-B Irradiation is generally understood to lead to skin bums and erythema. In addition, overexposure to UV-A radiation may cause a loss of elasticity of the skin and the appearance of wrinkles, promoting premature skin aging. Such irradiation promotes triggering of the erythemal reaction or amplifies this reaction in certain individuate and may even be the source of phototoxic or photoalterglc reactions. It is increasingly believed that overexposure to UV*A may also lead to melanoma. Thus, the application of the composites of the invention to the skin and/or hair of an individual will provide enhanced UVR

2S phgtoprotectlun (UV-A and/or UV-B) of the skin and/or hair of the individual The compositions of the Invention are intended to provide a sun protection factor (SPF) rating of at least 2, with additional preferable embodiments having a sun protection factor of at least 5, at least 10, at least 15, at least 2,0, at least 25, at least 30, at least 35, at least 40, at least 45, at least 50. and at least 55.

The invention will be further described by means of the following examples. which are not Intended to limit the invention, as defined by the

2017200676 01 Feb 2017 ~ u appended olalms, in any manner

EXAMPLES

Formulation of Sunscreen Lotions

Several oil-in-water formu'attans comprising the sunscreen active compounds amiloxato, octmoxate, and octucrytene, Individually and in various oombinattoris, were tested in to wtoo SPF experimentsk Tables 1 and 2 lst the ingredients for the formulations containing either one or two sunscreen actives io used for comparative purposes* Table 3 contains ingredients for formulations that contain combinations of all three sunscreen setives_f which illustrate the surprising synergy between amiloxafo, octinoxste, and octocrylene. Ail formulations were prepared according to the following general method;

1. Kaltrol and Veegum were added to ths water of Part A in a suitable

1.5 container and mixed with mechanical stirrer rm® completely hydrated. The remainder of the P art A ingredients are then added with mixing to form the water phase and heated to 165-175 'T.

2. In a separate container all of the Part B ingredients are combined and heated to 180-185 β 3. The Part B Ingredients are then added to the water phase of PM A, mixed end cooled slowly to 120-125 *F.

4. The Garmaben II of Part C is then added and mixed well .

5. Tim formulation is then cooled to room temperature and then Part O water is added QB to weight.

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-ISTable 1

Fwmalatmns Cmrtaintog Single Sunscrew ActW

	IHCI Name	Trade Name	Ex. 1	Bid 2	Ex. 3	Be 4	Be 5 I
A	Pudifed ww	Water	M75	77.25	77.25	72.25	72.25
A	Sodium Cetssryi Sulfeie	Sodium Cetearyl Sulfate	G.30	0.3d	0.30	«	0.30
A	Pmpyfehe Giywt	Prapylenss Gley ci	5.00	5.00 =	5.00	5.00	5.00
A ;	Magnesium Afemlnum SScale	Vacuum dltra	1.00	i.8o	TOO	l.GG	1.00 [ 0.35 1
: A	ΧοηΤοο Gum	KG&dCGF	0 35	3.35	0.35	0.35
j B	WopWyi Glycol Dihspfesrmste	Lexfbsl ‘7	s.oo	5.00	5.00	5.00	5.00
B	nvp Eioos&nc Copolymer	GawxVSgSh	2 GO	3.00	2.00	3.00	W |
iir	Araohldyi Alcohol (and) Behenyl Alcohol (arid} Araohidyl Glucoside	Monlonov BOS	2.00	2.00	2.00	2.00	2.00 j
B	OcOuoxate	Parscl MCX	7.50	0.00	b.oo	b.oo	0.00
B	Amitoxoie	Heoh&Sp» ε-1000	0.00	5.00	o.bo	o.ob	W.00
I 8	Gctocryiena	UvinGNSSS T	G00	0.00	5.00	13.00	b.ob
B	Pcg-30 rsp&iyhydrnxystaafate	Artec®! F 135	0 10	a to	0.10	0.18	o.lo |
B	- DiwdhWne	Bow Coming 208 Fluid. 350 GST	1.00	'1.00	1.00	too	too | I
C '	Prnpyiarm glycol (and) Digzolidinyl KBii (end) methyl paraben (and) propyi parabaa	Ger-mahen ll	1.00	1.00	1.00	1.00	•log
L°	PunhadW&ter	Water	QS	' as	as	OS	QD
I		Wai	100..00	100.00	120.00	ΪΟΟ.ΟΟ	100.00 1

’’ Ah amounts listed as percent by weight.

2017200676 01 Feb 2017

Tabte 2 ftsmwlatimw Containing Two Sbm©re®n Actives-

pwT	8NC1 Wame	Trade Hama	Be 8	Bx.7	Be 8	Be 9 I
j A L_™	Atefed Wster	Water	S9.7S	S2.2S	S7J55	54.75
	Sodium Cstuary? Sulfate	Sodium : CteWyl Sulfate	0.30	0.,30	0.3(3 :	0.30 H
j A	Pmp’yterie Glyfeel	Pmpyiarte Gtoyol	5.00	S.OO	5,90	5.00
A	Magnasiura Aluminum Siliauls	Ver-gum Ultra	1.00	1.00	1.00	1.00 I
|™A~~	Xanthan Gum	OCSF	0.3S	9.35	0,35	0.35 |
B	Meopefeyl Glyeai Pihaatenwte	LeXfeal ?	5.00	S.OO	0.00	5.00 i
B	PVP Oossana Copdiymer	Gbrwx v'-OOO	2.00	2.00 i	2.00	2.00 I
1 B	Araohidyl Alcohol (arid) Beheayl Alcohol (anti) Arachidyi Glycosida	Montanov 202	3.00	2.00	2.00	2.,00 I
B	Oainoxaie	Pared MGX	7.00	0.00	0.00	7.50
	.Arnsluxate	btebtedtepar-i E- 100(3	5,00	10.00	5.09	0 0(3 |
B	Qofeeryfene	Uvinul N 535 T	: 0.0(3	io.bo	1(3.00	10.00 j
B	Fag-30 Dlpolyhytirosiystesrate	Arlacei P 135	0.10	0..1(1	0.1(3	0.10 1
[ B	Otatehfeorte	Dow bomfeg 200 Fluid. 350 CST	1.00	LOO	1.60	1.00
j c	Propylene giyutil (and) Diasoiidfeyl urea (and) methyi paraben (and) propyl paraben	GenasbmMl	1.00	1.00	1.00	“ΰϊΰΊ
1 b	Funifecl Water-	| Wafer	QS	OS	as	as
| | j w	Ϊ 00.00	100.00	: WS 00 | 100 0(3

⁵ Ail amounts listed as percant by weight,

2017200676 01 Feb 2017

j Fart	IMGI Warn®	Tmcfe H ama	EX, 10	W. 11	Bl 121
A	PurGted Water	Water	Ϊ4.75 :	5S 35	St. 75 |
A	Sorbum Cteteufte Sulfate	Sodium Cotearyi Suifete	o	0.30	0.30 1
A	Prepyteri® Giyete	Propylene Gicyoi	5.00	5,00	5.00
A	Masnssium Aluminum OiU3fe	Veepum Gibe	1.00	WO	too
ί A	Xanthsn Gum	kstwcep	OS	0.35·	w
i B	Neopentyl Glycol 1 fjihapl'teuat®	Lexfeei 7	5.00	5300 ;	0.00 :
I 8	PVP Bcosene Copolymer	cswv-sad	zoo	zoo	ZOO 1
| B	Arachldyi Ateohol {and} Sehenyi Alcohol (and) Arechteyl GiiKWid®	Moatenov 302	2.00	2.00	2.00
j B	Gditesxata	Parsec MQX	7.50	7.50 .......................	7.50
B	Amfexete	Neoheitepan ts-ioob	5.00	5.00	10.00 I
B	Gctedrytens	LMrteiNSSGT \ :........ .......____.........	5.00	10.00	15.00 i
B	P©g-B DipeSytrydroxystearaie	Msto®lP135	0.10	0,10	o.wH ....
I B	GimetHserte	Daw Coming 200 Fluid, 350 CST	1.00	1.00	LOO /
j <F~	Propyiaoe glysoi | (and) Dteseildinyl I urea (and) methyl pareben (and) propyl 1 paraben	Garmaben II	1.00	LOO ,	LOO
I 0	j PurifiedWater	Water	QS	| os	OS
|.......	1 ,L„ .	Total	: 100.00	150.00	155.00

SRF Retirement®

2017200676 01 Feb 2017

-18instructions. Test formulations were applied to the substrates at 2 mg/cmT mounted in 6X7 photographic slide mounts (B&H Photo Video, New York, NY; USA) and atiswed to dry for 20 minutes. An untreated, hydrated Vitru-Skin® substrate was also mounted in a slide mount and stowed to air dry for 20 minutes to serve aS a reference and blank. The In vitro SPF of each formula was determined using an Optomtenca $PF 298$ Analxyer (Optometries LLC, Ayer, MA; USA) equipped with a computer-controlled X-Y sampling stage and operated according to the manufacterer's instruedons. A total of 12 In vitro

PF values were obtained for each formula using a different, non-overlapping io poTtfan on each mounted substrate. The resulting in vitro SPF values are shown in Tabfe 4. AH the SPF values reported ere the average of 12 values measured for each formulation.

Table 4

Measured vs, Expected SPF

Formula Example	Octinoxate (¾ w/v)	Amlfoxate (%w/v)	Octoorytens (%w/v) :........ .... .......	Measured SPF(s<	Expected SPF*
1	7.5			10.5 0.0)
2	—	5.0		8.6(0) ...........................
3.....	: --.............................		5.0 ;	5.6(0.4)	' I ; ,..
4	άΛ·		40	15.5 (3,0)
8	—	10.0		13.1 (1.5)
	7..5	5.0	—	18.0(1.3)	19.1
7	A** ................................	10.0	10.0	30.2(3.7)	28.7
8		5.0	10.0	24.6 (3.3)	24.2
§	7.5		10.0	20.5 (3.9)	26.1
ΐδ	7.5	§43	5,0	30.0 (2.4)	24.7
11	7.5	5.0 . .......	ιαΟ	42.0 (5,9)	34 7
12	7.5	10.0	10.0	48.2 (5.0)	L2!±-

’Measured SPF represents Ute mean of three different determinations. ^Expected SPF values reported for Examples 6-12 were calculated by adding the sum of the individual SPF’s from each sunscreen at the sama concentration.

2017200676 01 Feb 2017

-19The results in Table 4 dearly demonstrate that a uhigue synergy exists for the combination of sunscreen actives of the inventibh, .as demonstrated for example io formulas 10-12 containing various levels of all three sunscreen actives. Farmalas 1(M 2 increase SPF values by 5 to 9 SPF' units relative to the SPFs expected tom the arithmetic sum of the SPFs from individual sunscreen actives at the same concentrations. In contrast, measured SPF values of formulas 6-9 containing two sunscreen actives remain about the same as the expected SFF values, confirming that the Synergies observed for x c the combin alien of all three sunscreen actives do not derive from any possible combination of the two sunscreen actives. The synergistic effect in SPF performance only exists for combinations of all three sunscreen actives in the same formula.

In addition to the αΙΜη-water emulsions described above, additional

X c representative examples of photoprctective compositions according to the invention can be made for example as water-inmii emulsions and alcohol spray compositions. Representative Examples 13 (water-in-oil emulsion) and 14 (albohol spray) are described below.

2017200676 01 Feb 2017

-20 -.

Table S

Waiw-m-OO Bmufeton Formulation (Bx. 13)

Fart	No.	IKCIHamb >	Trade Name	Wt WM |
1 A	1	Octlooxste	Rsrfoi MCX	7,sg
	2 :	Amfcxaie	HecHoisopen 6·1 OOP i	W.00
( A	3	Gutocryteae	URvWNSSQf	10.00
I A	4	Sis-hydroxyetoyoxWmpyl Pimethisenc	OC §SS2 Gafomoi RW i	4.0Q
1 A	5 _	Gyclopenteslteana (end) PBG-12 hlmeihton® Gnmpolyimr	Dow Coming soi 1 Btoxw' :	I
	S	Tocopherol	” dJ -alpha tocopherol .......	..... 0 20
{ s	7	Ateited Water	> Water	5S.T0
Γ B™ L...............	a	Pmpytene Glycol	Prap^mte GiycN	5.90
| B	s	Pslyamifioprapyl BigtteNds	-CosmodiCQ	xon I
a	IQ	Sodium Chkterte	Sodium Chloride	0.50 I
	11	Chiorphene^n	3'(4»ChlQTphenoxyhl .2- Propansdtal	Q.id |
1 .			Total	1-30.00 j

The wteHn-oil fomwhrfon show can be prepared by first adding the oil phase ingredients of part A in a cont^w large enough to hold the entire batch and mixing until uniform. Next. in a separate container add the water of part B followed by th® remaining ingredients of Fart B in the listed order and mix well. Finally, hie water phase of the second step can be added slowly to the oil phase of step one with slow mixing until all of the aqueous phase has been added and then the mixing speed is increased for rapid mixing to complete the emulsification and set the lotion composition.

Tabled

Afcohol Spmy Formulation (Bo14)

2017200676 01 Feb 2017

M	INCI Name	Trade Home	Wt% (w/w)
IA 11 1	Oclinoxafo ................................... ........................	Pansol MCX	7.50
| A Ί2	Amilbxate	Heohefcpan E~ 1000	5.00
A 3	Gctocryiene	WnW	Έο0™
IA j 4	Sb Alcohol 40	SD Alcohol 40	τΟο j
A 5	Copolymer	bermacryl 79	3.00 ί
1A |S	Fragrance .... .................................................... ........	Fragrance	0.20 j
1 |	- ........ ' ' ' '	Total . .	100.00 j

s Th® composition is prepared by adding all ingredients to a suitable sized container in ths order listed and mixing untii uniform.. The compositions can then be loaded, for example, info a pump battle for spray application to the skin and/or hair.

io The composslfoha of foe bwontion can afeo be prepared as aerosol formulations for application as a spray to the skin and/or hair. The followim cornposittan in Table 7 (Example 15) Is an example of the production of an aerosei formulation according to the subject invention.

TebteT

Aerosol Lotion Formuiatioo

2017200676 01 Feb 2017

Pari:	IHGI Hama	Trade Hwie	Wt. % (w/w)
A	Purifed Water	Water	41.83
A	Sodium Qni&mys Suited	Sodium Calsaryl Suftele	0.21
A	P«3p$ms Giyed	Prcpytens Gteyol	3.50
A	&btgn©stem Aluminum Silicate	W&gum ufes	C.ZC
A	Xarxhao Gum	Keitrol CGF	0.24
B	PVP Eteosene Copolymer	OanexWdB >	1.4 i
B	Aractedyi Aicoho> (and) Behenyl Aicoho! {and} Arachidyl Gteotekte	Moutenov SOS	1Λ
B	dstlncteate	Parsai Μ0Χ ....... ...........................	5.25
B	AmSp}®te	Nmtetetetten E-1GGO	7.GG
B	Qcteoyishc	UvteulOSST	Z..00
B	W30 Dipclyhydrexystesralc	Artecte P 135	0.Q7
B	Oimethiconc	□dwQhffltep 2G0 Fluid, 350 CST	0.(0
: C	Prapytena glycd (and) Plazoildlcyi cma (and) methyl paraben (and) propyl paraben	Germabsa 11	b.fo
1 E	Dimethyl Ether	x.x	30.0
		Total	103.00......

The aerosol Woo .listed in Table 7 can be easily prepared by combining the totion formulatian described herein with a common propellant eno loaded into a suitable container to allow far storage until applied. In the above Example 15/70% of the tdtton described in Example 12 can be combined with a io common propellant, in this case 30% dimethyl ether, In a closed container, such as an aluminum can or glass bottle.

To prepare the aerosol formulation, ths emulsion is allowed to cool to room temperature and then weighed Into ths appropriate conteiner such as an

2017200676 01 Feb 2017

teated •'Φ

It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission that the publication forms a part of the common general knowledge in the art, in Australia or any other country.

n the claims which follow and in the preceding description of the

Invention, except where the context requires otherwise due to express language or necessary implication, the word “comprise” or variations such as “comprises” or “comprising” is used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention.

Claims (17)

1. The claims defining the invention are as follows:

   1. A topically applicable sunscreen composition suited for the photo protection of human skin and/or hair, comprising a sunscreen active combination consisting of a synergistic amount of octinoxate, octocrylene, and amiloxate, wherein the sunscreen active combination produces a synergistic increase in the SPF rating of the composition, wherein the octocrylene is present in the combination in an amount from about 5.0 to about 10.0 percent by weight.
2. 2. A sunscreen composition according to claim 1, wherein the octocrylene is present in the combination in an amount from about 8.0 to about 10.0 percent by weight.
3. 3. A sunscreen composition according to claim 1 or 2, wherein the amiloxate is present in the combination in an amount from about 1.0 to about 10.0 percent by weight.
4. 4. A sunscreen composition according to any one of claims 1 to 3, wherein the amiloxate is present in the combination in an amount from about 5.0 to about 10.0 percent by weight.
5. 5. A sunscreen composition according to any one of claims 1 to 4, wherein the amiloxate is present in the combination in an amount from about 7.5 to about 10.0 percent by weight.
6. 6. A sunscreen composition according to any one of claims 1 to 5, comprising a nonionic vesicle dispersion, emulsion, cream, milk, gel, cream gel, ointment, suspension, dispersion, powder, solid, stick, foam or spray.
7. 7. A sunscreen composition according to any one of claims 1 to 6, comprising an anhydrous or aqueous solid or paste, emulsion, suspension, or dispersion.
8. 8. A sunscreen composition according to any one of claims 1 to 7, comprising an oil-in-water emulsion.

   10425644_1 (GHMatters) P80621.AU.2

   2017200676 26 Nov 2018
9. 9. A sunscreen composition according to any one of claims 1 to 7, comprising a water-in-oil emulsion.
10. 10. A sunscreen composition according to any one of claims 1 to 7, comprising an aerosol formulation.
11. 11. A sunscreen composition according to any one of claims 1 to 10, having a sun protection factor of at least 30.
12. 12. A cosmetic composition for topical application to human skin and/or hair, containing a combination of sunscreen actives, wherein the sunscreen active agents consist of a synergistically effective amount of octinoxate, octocrylene, and amiloxate present in an amount to produce a synergistic increase in the SPF rating of the composition, wherein the octocrylene is present in the combination in an amount from about 5.0 to about 10.0 percent by weight.
13. 13. A cosmetic composition according to claim 12, wherein the composition comprises a moisturizer, a cleanser, a conditioner, a shampoo, a body wash, a styling gel/lotion, an eye cream, an eye liner, a blush, a mascara, a foundation, a nail polish, a polish remover, an eye shadow, a lipstick, a lip gloss, a lip liner, a lip balm, a makeup remover, a nail treatment, a foot care composition, an acne treatment, a redness/rosacea treatment, a varicose/spider vein treatment, an antiaging composition, a sunless tanning composition, an after-sun composition, a concealer, a hair color and a bleaching composition, a skin fading/lightener, a body firming lotion, a shaving cream, an after shave, a relaxer, an antiperspirant, a deodorant, an exfoliant, a scrub, a liquid hand soap, a bubble bath, a pain and a wound treatment, an insect repellant, an anti-itch/rash cream, a styling mousse, a foam, a perfume, a lubricant, a body oil, a body spray, a baby lotion, a diaper cream, a baby soap, a baby shampoo, a baby oil, a baby wipe, a hair-loss treatment, a hair spray, a depilatory, a hair growth inhibitor, a hair removal wax, a personal cleansing, a cologne, an oil controller, ora hand sanitizer.

    10425644_1 (GHMatters) P80621.AU.2

    2017200676 26 Nov 2018
14. 14. A cosmetic composition according to claim 12 or claim 13, further comprising at least one skin protectant active agent.
15. 15. A cosmetic composition according to claim 14, wherein said skin protectant active agent comprise allantoin, aluminum hydroxide gel, calamine, cocoa butter, cod liver oil, colloidal oatmeal, dimethicone, glycerin, hard fat, kaolin, lanolin, mineral oil, petrolatum, sodium bicarbonate, topical starch, white petrolatum, zinc acetate, zinc carbonate, and zinc oxide.
16. 16. A method for protecting human skin and/or hair against the deleterious effects of ultraviolet solar radiation, comprising topically applying thereto an effective amount of a sunscreen composition according to any one of claims 1 to 11.
17. 17. A method for protecting human skin and/or hair against the deleterious effects of ultraviolet irradiation, comprising topically applying thereto an effective amount of the cosmetic composition according to any one of claims 12 to 16.