Retinol containing day cream

Abstract

An oil in water emulsion having an SPF of at least 25, comprising: (a) at least 0.01 wt.% of one or more retinoid selected from retinol, retinal, retinoic acid or combinations thereof; (b) one or more water-soluble antioxidant; (c) one or more oil-soluble antioxidant; (d) at least 10 wt.% of one or more oil-soluble or oil-dispersible sunscreen components. Methods of manufacturing said oil in water emulsion and uses and methods of use of said oil in water emulsion.

Description

[0001] RETINOL CONTAINING DAY CREAM

[0002] Field of the Invention

[0003] The present invention relates to emulsions and methods of using such emulsions. More particularly, the present invention relates to emulsions comprising retinol and oilsoluble or oil-dispersible sunscreen components designed to deliver anti-ageing skin benefits and protect skin from the aging effects of UV light.

[0004] Background of the Invention

[0005] It is well known in the field of cosmetic composition design and manufacture that skin is negatively impacted by endogenous and exogenous factors. Endogenous factors include hormonal fluctuations, inflammation, disease, and / or the normal ageing process. Exogenous factors affecting skin include environmental impact, for example, sunlight, wind abrasion, humidity and pollutants. The impact of these factors on the skin result in problems associated with ageing skin such as the formation of wrinkles, fine lines, age spots, enlarged pores, skin discoloration, surface roughness and loss of elasticity.

[0006] Exposure of skin to ultraviolet radiation from sunlight or other sources is linked to dryness, wrinkles and uneven pigmentation. Sunscreen components, which prevent UV light from reaching the skin, being key components of strategies for preventing or reducing skin ageing.

[0007] Many cosmetic day creams contain sunscreen components (UV filters) to protect the skin from ultraviolet radiation and so prevent or reduce skin ageing that would otherwise be caused by UV light. Traditionally, the sunscreen component would be a physical or mineral sunscreen such as titanium dioxide or zinc oxide but in recent years chemical sunscreens have begun to be used alongside or instead of physical sunscreens. Chemical sunscreens absorb light over a broader wavelength than physical sunscreens. They also tend to be waterproof and provide cosmetic benefits to the user in that they do not leave a white film on the skin. Often, two or more chemical sunscreens are combined to provide full spectrum protection from UV light. The majority of chemical sunscreens are oil-soluble or oil dispersible, and so are often provided in cosmetic oil or emulsion compositions. Emulsions are favoured as they allow the incorporation of both hydrophilic and hydrophobic active components and because their texture can be readily adjusted to suit the consumer’s needs. Oil in water emulsions are particularly favoured as consumers prefer the sensation of these emulsions on the skin to other emulsion types, such as water in oil emulsions.

[0008] As the role of UV light in ageing of the skin has become apparent, there has been a drive to provide sunscreens and day creams with a higher sun protection factor (SPF). This has necessitated compositions comprising higher concentrations of oil- soluble sunscreens and / or oil- dispersible sunscreens and consequently larger oil phases. The larger the oil phase, the more difficult to stabilise the emulsion becomes. The requirement of stabilising emulsions with high concentrations of oil phase has limited the use of other, difficult to stabilise, skin care actives as there is less room in the formulation to incorporate the necessary components required for stabilisation of the additional actives.

[0009] One such active is vitamin A and its derivatives. Vitamin A and its derivatives are found naturally in the body and in the skin where it needs to be converted by cells into retinoic acid to be effective. Retinoic acid applied topically is therefore highly efficacious as it does not require any conversion, but it has potential for adverse effects on the skin and it is therefore only available by prescription. Since a large proportion of consumers are not able to access retinoic acid containing products, cosmetic product manufacturers have instead looked toward retinyl esters and particularly retinol in over-the-counter products to treat the signs of ageing and improve the quality or appearance of skin. Retinol is the most proven and effective cosmetic alternative to retinoic acid. It binds to surface cell receptors before it is taken into skin cells and is then converted into retinoic acid which, acting via the nuclear receptors, Retinoic acid receptor (RAR) and Retinoid X receptor, (RXR) upregulates more than 500 genes involved in skin renewal, regeneration and homeostasis. This particularly benefits sun exposed skin sites such as the face, resulting in reduced signs of ageing, such as the evening of skin tone and reduced pigmentation.

[0010] One of the main challenges in retinol-containing cosmetic products is stabilising the retinol or retinoic acid alternative. Retinol exposed to oxygen, light, heat, acids or heavy metals such as iron, can degrade. Degradation products include beta-ionone, kitol, or anhydrovitamin A. However, systems used to stabilise retinol in cosmetic compositions can destabilise the oil phase in emulsions required to solubilise chemical sunscreens, leading to separation which is unacceptable as it limits the efficacy of a cosmetic product and is visually unappealing to the user.

[0011] Retinyl palmitate is commonly used as an alternative to retinol, as the esterification stabilises the compound. However, the impacts on the skin are reduced compared with retinol or retinoic acid.

[0012] There is therefore a need for oil in water emulsions for cosmetic application having a high Sun Protection Factor (SPF) and containing skin care actives such as retinoids that provide benefits to sun exposed skin resulting in reduced signs of ageing, such as the evening of skin tone and reduced pigmentation.

[0013] Summary of the Invention

[0014] The present inventors have identified a stable emulsion having sufficient oil phase to support an SPF 25 sunscreen and sufficient retinoid to provide anti-aging benefits.

[0015] The present invention therefore provides in a first aspect an oil in water emulsion having an SPF of at least 25 , comprising:

[0016] (a) at least 0.01 wt. % of one or more retinoid selected from retinol, retinal, retinoic acid or combinations thereof;

[0017] (b) one or more water-soluble antioxidant;

[0018] (c) one or more oil-soluble antioxidant;

[0019] (d) at least 10 wt. % of one or more oil-soluble and / or oil-dispersible sunscreen components.

[0020] In a second aspect, the present invention provides a use of the oil in water emulsion of the first aspect for a topical cosmetic application to the skin.

[0021] In a third aspect, the present invention provides a use of the oil in water emulsion of the first aspect as a non- therapeutic cosmetic treatment to improve the condition of the skin and / or lines and / or wrinkles and / or imperfections and / or skin firmness and elasticity.

[0022] In a fourth aspect, the present invention provides a method comprising applying the oil in water emulsion of the first aspect to the skin of a subject.

[0023] In a fifth aspect, the present invention provides a cosmetic method for improving the condition and / or appearance of the skin and / or lines and / or wrinkles and / or reduce imperfections (e. g. , pigmentation) and / or improve skin firmness and elasticity, comprising topically administering the oil in water emulsion of the first aspect.

[0024] In a sixth aspect, the present invention provides a method of preparing an oil-in-water emulsion according to the first aspect, the method comprising:

[0025] (i) combining the (d) oil soluble and / or oil dispersible UV filters and heating the combination to at least 50°C to form a liquid oil phase;

[0026] (ii) adding to the liquid oil phase the (a) retinoid, (b) tocopherol and (c) sodium ascorbate, and optionally the (e) triglyceride if present;

[0027] (iii) adding the oil phase to a water phase and homogenising the water phase and the oil phase to form an oil in water emulsion.

[0028] Detailed Description of the Invention

[0029] The present invention is directed towards a stable, oil in water emulsion having an SPF of at least 25 comprising at least 0.01 wt.% of one or more retinoid, one or more one water-soluble antioxidant and one or more one oil-soluble antioxidant. The emulsion comprises at least 10 wt.% of one or more oil-soluble or oil-dispersible UV filters.

[0030] Retinoid System

[0031] The present invention comprises at least 0.01 wt% of one or more retinoid selected from retinol, retinal, retinoic acid or combinations thereof. Retinol may comprise retinol, retinol isomers or combinations thereof. Retinal, also known as retinaldehyde, may comprise retinal, retinal isomers, or combinations thereof. The term "retinol isomers" comprises all-trans-retinol, 13 -cis-retinol, 1 1 -cis-retinol, 9- cis-retinol, 3,4-didehydro-retinol. Preferred isomers are all-trans-retinol, 13 -cis -retinol, 3 ,4-didehydro-retinol, 9-cis-retinol. The retinoid or the retinol may comprise or consist of all-trans-retinol.

[0032] The term “retinal isomers” comprises 1 1 -cis retinal and all-trans-retinal. The retinoid or the retinal may comprise or consist of all-trans-retinal.

[0033] The retinoid may be an all-trans-retinoid, comprising all-trans-retinol, all-trans-retinal, all-trans-retinoic acid, or combinations thereof. The retinoid may be selected from all- trans-retinol, all-trans-retinal, or combinations thereof.

[0034] Retinoids can become unstable when exposed to light, temperature changes and oxygen, degrading to less biologically active forms. Previous technology addressed this instability through encapsulation of the retinoid. Encapsulation is designed to protect the retinoid species to prevent or at least reduce degradation, thereby maximising the bioavailability of retinoid to the skin in use. A variety of mechanisms and materials have been described in the prior art for encapsulating retinoid. Examples of encapsulating materials include polymers, surfactant-based vesicles or liposomes. Retinoids in the prior art may be encapsulated with a material selected from the group consisting of sugar-based emulsifier, co-emulsifier, a positively charged molecule, solvent and mixtures thereof. One example of an encapsuled retinoid raw material ingredient is available commercially under the trade name InuMax sold by Evonik. Other commercially available encapsulated versions of retinol include Cyclasphere Retinol from BASF, Microsponge C l 16A, N720RE and N709RE from Amcol Health & Beauty Solutions and Spherulite-Rl O from Givaudan.

[0035] It is understood that the emulsifiers and stabilisers used to prepare the encapsulation and prevent the decomposition of retinoids in cosmetic compositions would destabilise the high oil content required to provide an SPF of at least 25 in oil in water emulsions. It was therefore thought that retinoid systems wherein the retinoid is selected from retinol, retinal, retinoic acid or combinations thereof are not appropriate for use in day creams having an SPF of at least 25. The present inventors have surprisingly found that retinoids stabilised by one or more water-soluble antioxidant and one or more oil-soluble antioxidant can be incorporated into high SPF, oil in water emulsions without compromising the stability of the oil in water emulsion.

[0036] Antioxidants are substances that slow the oxidation of substances, either directly by reacting with free radicals or indirectly by inhibiting the production of free radicals.

[0037] The retinoid in the retinoid system may be non-encapsulated. By non -encapsulated, it is meant that the retinoid is not contained in or absorbed onto another material that separates it from other components in the emulsion.

[0038] The composition of the present invention comprises a water-soluble antioxidant. The water-soluble antioxidant may comprise ascorbic acid or a derivative thereof, sodium ascorbate, sodium sulfite, sodium metabisulfite, sodium bisulfite, sodium thiosulfite, sodium formaldehyde sulfoxylate, isoascorbic acid, thioglycerol, thiosorbitol, thiourea, thioglycolic acid, 3 cysteine hydrochloride, 1 ,4-diazobicyclo(2.2.2)octane or a combination thereof. The water-soluble antioxidant may comprise or consist of ascorbic acid or a derivative thereof, isoascorbic acid, L-ascorbic acid or cosmetically acceptable salts thereof. Ascorbic acid derivative may comprise ascorbyl glucoside, sodium ascorbyl phosphate, magnesium ascorbyl phosphate, ethyl ascorbic acid or a combination thereof. The water-soluble antioxidant may comprise or consist of sodium ascorbate.

[0039] The water-soluble antioxidant may be present in the composition in an amount of at least 0. 1 wt. %, at least 0.2 wt. % or at least 0.3 wt. %. For example, the one or more water-soluble antioxidant may be present in an amount of from O. 1 to 10 wt.%, such as from 0. 1 to 8 wt.%, or from 0. 1 to 6 wt. %, or from 0.1 to 4 wt.% , or from 0.1 to 3 wt.%, or from 0.2 wt. % to 8 wt. % , or from 0.2 wt.% to 6 wt. % , or from 0.2 wt. % to 3 wt.%, or from 0.3 wt. % to 6 wt. %, or from 0.3 wt.% to 3 wt.%, or from 0.3 to 2 wt.%, or from 0.3 to 1.5 wt. % , or from 0.3 to 1 wt. % .

[0040] All weight percentages disclosed herein are by weight of the emulsion unless otherwise specified. The one or more oil-soluble antioxidant may comprise butylated hydroxy toluene (BHT), ascorbyl palmitate, butylated hydroxyanisole (BHA) , tocopherol (e. g. [alpha]- tocopherol) or a derivative thereof, phenyl-[alpha] -naphthylamine or combinations thereof. The oil-soluble antioxidant may comprise or consist of tocopherol (e.g. alphatocopherol or gamma tocopherol). Derivatives of tocopherol may include tocopheryl acetate and ascorbyl tetraisopalmitate or a combination thereof. The oil- soluble antioxidant may comprise tocopherol and tocopherol acetate. The oil-soluble antioxidant may comprise (R,R,R)-alpha-tocopherol, (all-rac)-alpha- tocopherol or a combination thereof.

[0041] In recent years the use of BHA and BHT is raising safety concerns and their use may be restricted in some countries. Thus, it may be that the one or more oil-soluble antioxidant does not comprise BHT, BHA or a combination thereof. It may be that the composition is free from one or both of BHT and BHA.

[0042] The one or more oil-soluble antioxidant may be present in the composition in an amount of at least 0.001 wt.%, such as at least 0.01 , at least 0.05 wt. %, at least 0.1 wt.%, at least 0.2 wt.% or at least 0.3 wt. %. For example, the one or more oil-soluble antioxidant may be present in the composition in an amount of from 0.01 to 10 wt.%, such as from 0.05 to 10 wt.%, or from 0.05 to 8 wt.%, or from 0.05 to 6 wt.%, or from 0.05 to 4 wt.%, or from 0.05 to 3 wt. %, or from 0.05 to 1 wt. %, or from 0. 1 to 10 wt.% , or from 0.1 to 6 wt. % , or from 0.1 to 4 wt. %, or from 0.1 to 2 wt.%, or from 0. 1 to 1 wt.%, or from 0.3 to 10 wt. % , or from 0.3 to 6 wt. %, or from 0.3 to 4 wt. %, or from 0.3 to 2 wt.%, or from 0.3 to 1 wt. % .

[0043] The ratio of (a) retinoid: (b) water-soluble antioxidant: (c) oil-soluble antioxidant may be 1 : at least 1 : at least 0. 1 . For example, the weight ratio of (a) :(b): (c) may be from 1 : 1 :0.1 to 1 : 100:100, or from 1 : 1 : 1 to 1 : 10:3 , or from 1 : 1: 1 to 1 : 10:5, or from 1 : 5:1 to 1 : 10: 1 , or from 1 : 8 :2 to 1 : 10:3, or from 1 : 1 :1 to 1 : 5: 10, or 1 :1 :1 to 1 : 3: 10, or 1 : 1:5: to 1 : 1 : 10, or 1 :2: 8 to 1 : 3 : 10.

[0044] The emulsion may further comprise, as part of the retinoid system, a triglyceride. The triglyceride may be a C3 to C 16 triglyceride for example a C6 to C 12 triglyceride. Examples include tripalmitin and caprylic / capric triglyceride. In one example the triglyceride is caprylic / capric triglyceride. The triglyceride may be present in a (a) retinoid: (e) triglyceride ratio of l:at least 10. The ratio of (a) retinoid: (b) water-soluble antioxidant: (c) oil-soluble antioxidant: (e) triglyceride may be 1 :at least 1 : at least 0.1: at least 10. For example, the weight ratio of (a) :(b):(c):(e) may be from 1 : 1 :0.1: 10 to 1 : 100: 100: 100, or 1 : 1 :1 :10 to 1 :5 : 10:50, or 1:1:1:10 to 1:3:10:50, or 1:1:5:10 to 1:1:10:50, or 1:2:8:10 to 1:3:10:50, or from 1 : 1 : 1 : 10 to 1 : 10:5 TOO. For example, the composition may comprise (e) caprylic / capric triglyceride in a ratio of from 1 : 1:0.1 :10 to 1 : 100:100:100, or an amount of from 0.1 to 5 wt.%.

[0045] The retinoid may be present in an amount of at least 0.01 wt.%, such as at least 0.02 wt.%, or at least 0.04 wt.%. For example, the retinoid may be present in an amount of from 0.01 wt. % to 3 wt. %, or 0.02 wt.% to 3 wt. %, or 0.02 wt. % to 3 wt. %, or 0.02 to 2 wt. % , or 0.04 to 1.5 wt.%. Preferably, the retinoid is present in an amount of from 0.01 to 1 wt. %, more preferably 0.01 to 0.3 wt.%, and most preferably from 0.01 to 0.1 wt.%.

[0046] The emulsion may further comprise PEG-40 hydrogenated castor oil. The emulsion may further comprise PEG-40 hydrogenated castor oil in an amount of 0.001 wt.% to 1 wt.%, such as 0.005 wt.% to 0.9 wt.%, 0.005 wt.% to 0.8 wt.%, 0.005 wt.% to 0.8 wt.%, 0.007 wt.% to 0.7 wt.%, or 0.01 wt.% to 0.5 wt.%. Preferably, the emulsion may further comprise PEG-40 hydrogenated castor oil in an amount of 0.01 wt.% to 0.5 wt.%

[0047] A retinoid stabilised by a water-soluble antioxidant and an oil- soluble antioxidant is commercially available under the trade name RetiSTAR, available from BASF. The retinoid of the present invention may be provided to the composition in the form of RetiSTAR (BASF). RetiSTAR (BASF) comprises a dispersion of retinol, tocopherol, sodium ascorbate and PEG-40 hydrogenated castor oil in caprylic / capric triglycerides. The dispersion comprises 5.0 to 5.9% Retinol - INCI listing: Caprylic / Capric Triglyceride (and) Sodium Ascorbate (and) Tocopherol (and) Retinol.

[0048] Oil in Water Emulsion

[0049] The emulsion of the present invention is an oil in water emulsion. Oil in water emulsions are preferred by consumers as they have a lighter feel on the skin due to them being water based. Oil based emulsions such as water in oil emulsions are typically heavier and greasier. A greater preference for the product will increase the use of the product and so consumers will be better protected from the harmful effects of UV radiation.

[0050] The oil in water emulsion may be a cosmetic product. A cosmetic product is a product designed for use by a consumer and is preferably a skincare cosmetic emulsion, more preferably a facial skincare cosmetic emulsion. A cosmetic product comprises only cosmetically acceptable components. The skilled person is able to identify cosmetically acceptable components, and these are well known in the field of the invention.

[0051] As the person skilled in the art would be aware, emulsions have at least one water phase and at least one oil phase.

[0052] The oil in water emulsion of the present invention has a water phase. The oil in water emulsion of the present invention may therefore comprise at least 35 wt.% water, such as at least 40 wt. %, at least 45 wt.% or at least 50 wt.%. The oil in water emulsion of the present invention may comprise 70 wt.% water or less, such as 65 wt. % or less, 60 wt. % or less, or 55 wt.% or less. The oil in water emulsion of the present invention may comprise from 35 to 70 wt.% water, such as from 40 to 65 wt.% of water, or from 45 to 60 wt. % of water. Water may comprise purified water, deionised water, filtered water, spring water, rose water or combinations thereof.

[0053] The water phase may comprise other components, such as C 1 -C8 alcohols including monohydric alcohols, diols and triols. The oil in water emulsion of the present invention may comprise glycerine. The oil in water emulsion of the present invention may comprise at least 3 wt. % glycerine, such as at least 4 wt. % or 5 wt. % . The oil in water emulsion of the present invention may comprise 10 wt.% of glycerine or less, such as 9 wt. % or less or 8 wt. % or less.

[0054] It will be appreciated that the water phase may comprise further components as part of a cosmetic emulsion. The water phase may comprise additional components such as other humectants including hyaluronic acid and its salts, chelating agents such as tetrasodium EDTA or Tetrasodium glutamate diacetate, pH adjusters, thickeners, such as xanthan gum or Carbomer, active ingredients such as peptides or other anti-ageing ingredients, and combinations thereof. The emulsion may comprise at least 20 wt. % of an oil phase. For example, the emulsion may comprise at least 25 wt.% of oil phase, such as at least 30 wt.%, or at least 35 wt.%. The emulsion may comprise from 20 wt.% to 60 wt. % of an oil phase, such as from 20 wt. % to 50 wt. % or from 20 wt. % to 40 wt. % of an oil phase.

[0055] The oil phase may comprise oils (such as liquid oils, semi-solid oils, and solid oils), emulsifiers, higher alcohols, and higher fatty acids. In addition, oil-soluble colorants and oil- soluble proteins, etc. are also encompassed. Further, a combination thereof such as a variety of vegetable oils and animal oils may be included. Further, oil-soluble preservatives, oil- soluble drugs, antioxidants, and perfumes may be included in the oil phase.

[0056] The oil phase of the emulsion may comprise oil at a level of at least 50% by weight of the oil phase, such as at least 60 % by weight of the oil phase, at least 70 % by weight of the oil phase, or at least 80 % by weight of the oil phase.

[0057] Suitable oils for the oil phase may comprise for example: (a) hydrocarbon oils, such as paraffin or mineral oils; (b) waxes, such as beeswax or paraffin wax; (c) natural oils, such as sunflower oil, apricot kernel oil, shea butter or jojoba oil; (d) silicone oils, such as dimethicone and / or dimethiconol, silicone elastomer, cyclomethicone or cetyl dimethicone; (e) fatty acid esters and ethers, such as isopropyl palmitate or isopropyl myristate and polypropylene glycol-15 stearyl ether; (f) fatty alcohols, such as cetyl alcohol or stearyl alcohol; or (g) combinations thereof, for example, the blend of waxes available commercially under the trade name Cutina® (BASF) .

[0058] Alternatively, the oil phase of the emulsion may comprise a combination of oil, wax or butter. Waxes and butters are hydrocarbons that consist of long aliphatic alkyl chains and may include aromatic groups. They are generally lipophilic and typically solid or malleable at room temperature. Melting points vary depending on the alkyl chain, chain length and associations. Silicone waxes are a type of suitable wax based on alkylmethylsiloxane. Oils are typically lipophilic and liquid at room temperature with lower molecular weights than waxes. Where present wax or butter may be present at up to 40% of the oil phase of the emulsion. The oil phase may contain wax or butter at levels of up to 20% by weight of the oil phase of the emulsion. The oil phase may contain wax or butter at levels of up to 10% by weight of the oil phase of the emulsion.

[0059] The oil phase may comprise silicone oils which are silicone elastomers. Suitable for use herein are silicone elastomers which can be emulsifying or non-emulsifying crosslinked siloxane elastomers or combinations thereof. No specific restriction exists as to the type of curable organopolysiloxane composition that can serve as starting material for the crosslinked organopolysiloxane elastomer. Examples in this respect are addition reaction-curing organopolysiloxane compositions which cure under platinum metal catalysis by the addition reaction between SiH- containing diorganopolysiloxane and organopolysiloxane having silicon- bonded vinyl groups; condensation-curing organopolysiloxane compositions which cure in the presence of an organotin compound by a dehydrogenation reaction between hydroxyl-terminated diorganopolysiloxane and SiH- containing diorganopolysiloxane and condensation-curing organopolysiloxane compositions which cure in the presence of an organotin compound or a titanate ester. Preferred silicone elastomers include dimethicone crosspolymer and Polysilicone- 1 1 .

[0060] Components of the oil phase may contribute to dissolving oil soluble sunscreens that aren’ t liquid and so prevent them from precipitating and may contribute to supporting oil dispersible sunscreen components in the emulsion.

[0061] The oil in water emulsion of the present invention may comprise alkyl benzoates, also known as alcohol benzoates, such as C IO to C20 alkyl benzoates, C l l to Cl 8 alkyl benzoates or Cl 2 to C 15 alkyl benzoates. Alkyl benzoates are emollients and form part of the oil phase in which the oil soluble and / or oil dispersible UV filters reside in the emulsion of the present invention. When present, the alkyl benzoates contribute to dissolving oil soluble sunscreens that aren’t liquid and prevent them from precipitating. The oil in water emulsion of the present invention may comprise at least 5 wt.% of alkyl benzoates, such as at least 7 wt. % or at least 9 wt. % . The oil in water emulsion of the present invention may comprise 20 wt.% or less of alkyl benzoates, such as 18 wt.% or less or 16 wt. % or less alkyl benzoates. The oil in water emulsion of the present invention may comprise from 5 to 20 wt. % of alkyl benzoates, such as from 7 to 18 wt. % or from 9 to 16 wt. % of alkyl benzoates. In some examples, the combination of (a) one or more retinoid, (b) one or more water- soluble antioxidant, (c) one or more oil-soluble antioxidant, (d) one or more oil-soluble or oil-dispersible sunscreen components, water, and optionally glycerine, alkyl benzoates and triglyceride, forms at least 50 wt. % of the emulsion, such as at least 60 wt. % , or forms 90wt.% or less of the emulsion, such as 80 wt. % or less, or forms from 50 wt. % to 90 wt.% of the emulsion, such as from 60 wt.% to 80 wt.% of the emulsion.

[0062] Sunscreen Component

[0063] The oil in water emulsion comprises at least 10 wt.% by weight of the emulsion of one or more oil-soluble and / or oil-dispersible sunscreen components, also referred to herein as oil-soluble and / or oil- dispersible UV filters. The oil in water emulsion may comprise at least 10 wt. % , at least 1 1 wt. %, at least 12 wt. %, at least 15 wt. %, at least 17 wt.%, at least 20 wt. %, from 10 to 30 wt.%, from 12 to 25 wt.%, from 15 to 20 wt.%, no more than 35 wt. % , no more than 30 wt. %, no more than 25 wt.%, no more than 22 wt.%, or no more than 20 wt.% of one or more oil-soluble and / or oil-dispersible UV filters by weight of the emulsion.

[0064] The oil-soluble or oil-dispersible UV filters will form part of the oil phase. In some examples the oil-soluble or oil-dispersible UV filters form at least 20 wt.% of the oil phase, such as at least 30 wt. % of the oil phase or at least 40 wt. % of the oil phase. In some examples the UV filters form from 20 wt. % to 70 wt. % of the oil phase, such as from 30 wt.% to 60 wt. % of the oil phase or from 40 wt.% to 50 wt.% of the oil phase.

[0065] The one or more oil-soluble and / or oil-dispersible sunscreen components may comprise both oil-soluble and oil dispersible sunscreen components.

[0066] The one or more oil-soluble and / or oil-dispersible sunscreen components may comprise or consist of ethylhexyl methoxycinnamate, octocry lene, ethylhexyl salicylate, isoamyl p- methoxycinnamate, poly silicone- 15 , homosalate (homomenthyl salicylate) , menthyl anthranilate bis-ethylhexyloxyphenol methoxyphenyl tri azine, drometrizole trisiloxane, butyl methoxydibenzoylmethane, diethylamino hydroxybenzoyl hexyl benzoate, benzopheno ne-3 , diethylhexyl butamido triazone, methylbenzylidene camphor, ethylhexyl triazone, methoxypropylamino cyclohexenylidene ethoxyethylcyanoacetate, or combinations thereof. The one or more oil-soluble and / or oil-dispersible sunscreen component may comprise one or more broad-spectrum UV filter, one or more UV-A filter, one or more UV-B filter or combinations thereof.

[0067] Broad- spectrum, oil-soluble or oil-dispersible, UV filters include bisethylhexyloxyphenol methoxyphenyl triazine, drometrizole trisiloxane, benzylidene camphor sulfonic acid, hydrophobically coated titanium dioxide, hydrophobically coated zinc oxide, and combinations thereof.

[0068] The one or more oil-soluble or oil-dispersible UV filters may comprise at least 2 wt.% of one or more broad- spectrum UV filters, such as at least 3 wt.%, at least 5 wt.%, at least 7 wt. % or at least 10 wt.% of one or more broad-spectrum UV filters by weight of the emulsion.

[0069] Oil-soluble or oil-dispersible UV-A filters include butyl methoxy dibenzoylmethane, diethylamino hydroxy benzoyl hexyl benzoate, methoxypropylamino cyclo he xenylidene ethoxyethylcyanoacetate and combinations thereof.

[0070] The one or more oil-soluble or oil-dispersible UV-filters may comprise at least 2 wt.% of one or more UV-A filters, such as at least 3 wt. %, at least 5 wt.%, at least ? wt.% or at least 10 wt. % of one or more UV-A filters by weight of the emulsion.

[0071] It will be appreciated that broad-spectrum UV and UV-A filters both absorb in the UV- A region, and therefore in some examples the one or more oil-soluble or oil-dispersible UV-filters may comprise one or more broad-spectrum UV and UV-A filters together in an amount of at least at least 5 wt.% , at least 7 wt.% or at least 10 wt.% by weight of the emulsion.

[0072] Oil-soluble or oil-dispersible UV-B filters include ethylhexyl triazone, ethylhexyl methoxycinnamate, benzophenone-3 , octocrylene, ethylhexylsalicylate, homosalate (homomenthyl salicylate), isoamyl p-methoxy cinnamate, polysilicone-15 , diethylhexyl butamido triazone, 4-methylbenzylidene camphor, tris-biphenyl triazine and combinations thereof. The one or more oil-soluble or oil-dispersible UV filters may comprise at least 2 wt.% of one or more UV-B filters, such as at least 3 wt. %, at least 5 wt. %, at least 7 wt.% or at least 10 wt. % of one or more UV-B filters by weight of the emulsion.

[0073] The one or more oil-soluble or oil-dispersible sunscreen components may comprise or be selected from butyl methoxydibenzoylmethane, ethylhexyl methoxycinnamate, octocrylene, ethylhexyl salicylate, bis- ethylhexyl oxyphenol methoxyphenyl triazine, ethylhexyl triazone, and combinations thereof. The one or more oil- soluble or oil- dispersible sunscreen component may comprise or be selected from butyl methoxydibenzoylmethane, ethylhexyl salicylate, bis- ethylhexyl oxyphenol methoxyphenyl triazine, and ethylhexyl triazone or combinations thereof.

[0074] The oil in water emulsion may have an SPF of at least 25 , such as at least 30, at least 35 , at least 40, at least 45, at least 50, at least 60 or at least 70. The oil in water emulsion may have an SPF of 80 or less, such as 75 or less, 70 or less, or 60 or less.

[0075] The oil-soluble or oil-dispersible sunscreen component may be present in an amount sufficient to provide an emulsion with an SPF of at least 25 , such as at least 30, at least 35 , at least 40, at least 45 , at least 50, at least 60 or at least 70. Alternatively, a water- soluble or water-dispersible sunscreen component may be present, wherein together the oil-soluble or oil-dispersible sunscreen component and the water-soluble or water- dispersible sunscreen component are together present in an amount sufficient to provide an emulsion with an SPF of at least 25, such as at least 30, at least 35 , at least 40, at least 45 , at least 50, at least 60 or at least 70.

[0076] SPF is a measure of how much UV radiation is required to produce sunburn on skin protected by a composition relative to the amount of UV radiation required to produce sunburn on unprotected skin. As the SPF value increases, sunburn protection increases. SPF may be determined according to ISO24442019 produced by the International Organization for Standardization. The skilled person may utilise a sunscreen predictor, such as the sunscreen predictor available from BASF (https: / / sunscreensimulator.basf.com / Sunscreen Simulator / computatioii) to predict the SPF of a formulation. To ensure adequate protection the emulsion preferably comprises a blend of UV filters providing protection from UV-A and UV-B radiation.

[0077] Generally speaking, sunscreen compositions known in the art provide greater protection for skin against UV-B radiation than UV-A radiation. One method of assessing a product’ s efficiency across the UV spectrum is the Star Rating (UVA / UVB Ratio) according to the Boots Star Rating System. The Star Rating is calculated as an indicator of the UVA absorbance properties of a sunscreen product, relative to UVB as described in the Revised Guidelines to the practical measurement of UVA: UVB ratios according to Boots Star Rating System.

[0078] The calculation of the UVA / UVB absorbance ratio will typically yield values from zero (equal to no UVA absorbance) up to 1 .0 (UVA absorbance equal to UVB). A UV-A / UV- B absorbance ratio between 0.6 to 0.79 is equivalent to a 3 star rating. A UV- A / UV-B absorbance ratio between 0.8 to 0.89 is equivalent to a 4 star rating. A UV- A / UV-B absorbance ratio of 0.9 or greater is equivalent to a 5 star rating.

[0079] Most UV-A filters are oil soluble or oil dispersible. Therefore, to achieve the desired UV-A / UV-B ratio a large oil phase must be stable in the oil-in-water emulsion to accommodate sufficient UV-A filters. UV-A sunscreens such as butyl methoxydibenzoylmethane and diethylamino hydroxybenzoyl hexyl benzoate are powders that require solubilisation in the oil phase. Provision of UV-A sunscreens therefore requires an oil phase that is larger than would be required if these components were not present.

[0080] The present inventors have surprisingly found that the stability provided by the retinoid system of the present invention allows the incorporation of sufficient oil-soluble and / or oil-dispersible UV-filters to provide broad spectrum UV protection. Oil in water emulsions of the present invention may have a UV-A / UV-B absorbance ratio of 0.6 or greater, such as 0.7 or greater, 0.8 or greater, or 0.9 or greater.

[0081] The Boots in-vitro test method (known as the Boots Star Rating Test), is an industry standard test that is used test to the SPF provided by a product. The product to be tested is uniformly spread on 3 PolyMethylMethAcrylate (PMMA) plates using an application rate of 1 . 3mg / cm2. The transmittance of a UV light through the plates is then detected in the UVA-B region to quantify the UVA and B amounts being ‘blocked’ by the product and compared to the transmittance of a PMMA plate that is uncoated. Details of this test have been publicly published and are available directly from Boots.

[0082] The UV-A / UV-B absorbance ratio can be determined using the Boots Star Rating Test. The test provides a UV -A / UV-B rating of from one to five stars. Oil in water emulsions of the present invention may have at least a three star rating as determined by this test, equivalent to a UV-A absorbance ratio of from 0.6 to 0.79. for example, emulsions of the present invention may have at least a four star rating, where the UVA / UVB ratio is between 0. 8-0.89, or a five star rating, where the UVA / UVB ratio is 0.9 or greater.

[0083] The oil in water emulsion of the present invention may therefore comprise one or more oil-soluble and / or oil-dispersible UV-A filter and one or more oil-soluble and / or oil- dispersible UV-B filter, one or more oil-soluble and / or oil-dispersible UV-A filter and one or more oil-soluble and / or oil-dispersible broad-spectrum UV filter, or one or more oil-soluble and / or oil-dispersible UV-B filter and one or more oil-soluble and / or oil- dispersible broad spectrum UV filter. Preferably the emulsion may comprise a combination of one or more UV-A filters and one or more UV-B filters.

[0084] The oil in water emulsion may comprise one or more oil-soluble and / or oil-dispersible UV-A filter, one or more oil-soluble and / or oil-dispersible UV-B filter, and one or more oil- soluble and / or oil-dispersible broad spectrum UV filter.

[0085] For example, the oil soluble and / or oil dispersible UV-filters in oil in water emulsion may comprise or consist of UV-A filter butyl methoxydibenzoylmethane, UV-B filters ethylhexylsalicylate, octocry lene and ethylhexyl triazone, and broad spectrum UV filter bis-ethylhexyloxyphenol methoxyphenyl triazine.

[0086] The oil in water emulsion may comprise at least 2 wt. % of a one or more oil-soluble and / or oil-dispersible UV-A filters, such as at least 3 wt.%, at least 2 wt.% of one or more oil-soluble and / or oil-dispersible UV-B filters, such as at least 3 wt.%, and at least

[0087] 2 wt. % of an oil-soluble and / or oil-dispersible broad-spectrum UV filter, such as at least

[0088] 3 wt. % . In some examples the oil in water emulsion may comprise at least 3 wt.% of one or more oil- soluble and / or oil-dispersible UV-A filters, at least 5 wt. % of one or more oil-soluble and / or oil-dispersible UV-B filters, and at least 1 wt.% of one or more oil-soluble and / or oil-dispersible broad-spectrum UV filter.

[0089] In some examples the oil in water emulsion may comprise at least 3 wt.% of oil-soluble and / or oil-dispersible UV-A filter butyl methoxy dibenzoylmethane, at least 5 wt.% of one or more oil-soluble and / or oil-dispersible UV-B filters comprising or consisting of from ethylhexylsalicylate, octocrylene and ethylhexyl triazone, and at least 1 wt.% of oil-soluble and / or oil-dispersible broad-spectrum UV bis- ethylhexyl oxyphenol methoxyphenyl triazine.

[0090] The emulsion may further comprise water-soluble and / or water-dispersible UV filters. Water-dispersible UV filters are those that are not soluble in water but that are present in the water phase of the emulsion. Water-soluble and / or water-dispersible UV filters include uncoated titanium oxide particles, uncoated zinc oxide particles, methylene bis- benzotriazoyl tetramethylbutylphenol, phenylbenzimidazole sulfonic acid, terephthalylidene dicamphor sulfonic acid, disodium phenyl dibenzimidazole tetrasulfonate, benzophenone-4, and combinations thereof.

[0091] Methylene bis-benzotriazoyl tetramethylbutylphenol, sometimes abbreviated to methylene bis-benzo triazolyl, is a water dispersible broad spectrum UV-filter. Phenylbenzimidazole sulfonic acid is a water soluble UV-B filter. Titanium oxide particles and zinc oxide particles are water dispersible broad spectrum UV-filters, although they may be hydrophobically coated to make them oil dispersible, terephthalylidene dicamphor sulfonic acid, disodium phenyl dibenzimidazole tetrasulfonate, and benzophenone-4 are water soluble, broad spectrum UV filters.

[0092] The emulsion may comprise at least 1 wt.% of water-soluble and / or water-dispersible UV filters, such as at least 2 wt. % , at least 3 wt. % or at least 4 wt. % . However, oil soluble and oil dispersible UV filters provide water resistance and cosmetic benefits to the emulsion and so in some examples the emulsion contains equal to or less than 6 wt. % of water-soluble and / or water-dispersible UV filters, such as equal to or less than 5 wt. % , equal to or less than 4 wt. %, equal to or less than 3 wt.%, or equal to or less than 2 wt. % . In some examples the emulsion is free of water-soluble and / or water- dispersible UV filters.

[0093] In some examples, the oil in water emulsion may comprise at least 3 wt. % of an oil soluble UV-A filter, at least 5 wt.% of a UV-B filter, and at least 2 wt. % of a broadspectrum filter as defined above. The oil in water emulsion may further comprise at least 2 wt. % , such as 3 wt. % or 3.5 wt% of one or more water soluble or water dispersible UV filter, optionally selected from uncoated titanium oxide particles, uncoated zinc oxide particles, methylene bis-benzotriazoyl and phenylbenzimidazole sulfonic acid, terephthalylidene dicamphor sulfonic acid, disodium phenyl dibenzimidazole tetrasulfonate, and benzophenone-4, and combinations thereof, preferably selected from methylene bis-benzotriazoyl and phenylbenzimidazole sulfonic acid or a combination thereof. In the most preferred examples, where present the one or more water soluble or water dispersible UV filter comprises or is selected from methylene bis-benzotriazolyl tetramethylbutylphenol.

[0094] The oil in water emulsion may comprise at least 3 wt. % of a UV-A filter comprising or consisting of butyl methoxydibenzoylmethane, diethylamino hydroxybenzoyl hexyl benzoate, methoxypropylamino cyclohexenylidene ethoxyethylcyanoacetate or combinations thereof. For example, the oil in water emulsion may comprise at least 3.5 wt. % of butyl methoxydibenzoylmethane.

[0095] Therefore, in some examples the oil in water emulsion may comprise at least 3 wt.% of oil-soluble and / or oil-dispersible UV-A filter butyl methoxy di benzoylmethane, at least 5 wt. % of one or more oil-soluble and / or oil-dispersible UV-B filters comprising or consisting of from ethylhexylsalicylate, octocry lene and ethylhexyl triazone, at least 1 wt. % of oil-soluble and / or oil-dispersible broad-spectrum UV bis- ethylhexyl oxyphenol methoxyphenyl triazine, and at least 3 wt. % of water dispersible broad spectrum UV filter methylene bis-benzotriazoyl tetramethylbutylphenol.

[0096] The oil in water emulsion may comprise at least 2 wt. % of a broad spectrum filter comprising or consisting of bis-ethylhexyloxyphenol methoxyphenyl triazine, drometrizole trisiloxane, benzylidene camphor sulfonic acid, hydrophobically coated titanium dioxide, hydrophobically coated zinc oxide, or combinations thereof, preferably bis-ethylhexyloxyphenol methoxyphenyl triazine, drometrizole trisiloxane or combinations thereof. In some examples the oil in water emulsion comprises at least 2 wt. % of a UV filter which is bis-ethylhexyloxyphenol methoxyphenyl triazine.

[0097] The oil in water emulsion may comprise at least 5 wt.% of a combined UV-A and broad spectrum UV filter comprising or consisting of bis-ethylhexyloxyphenol methoxyphenyl triazine, drometrizole trisiloxane, benzylidene camphor sulfonic acid, hydrophobically coated titanium dioxide, hydrophobically coated zinc oxide butyl methoxydibenzoylmethane, diethylamino hydroxybenzoyl hexyl benzoate, methoxypropylamino cyclohexenylidene ethoxyethylcyanoacetate or combinations thereof.

[0098] The oil in water emulsion may comprise at least 5 wt.% of a UV-B filter comprising or consisting of ethylhexyl triazone, ethylhexyl methoxy cinnamate, benzophenone-3, octocrylene, ethylhexylsalicylate, homosalate (homomenthyl salicylate) isoamyl p- methoxycinnamate, polysilicone-15 , tris-biphenyl triazine, diethylhexyl butamido triazone, 4-methylbenzylidene camphor or combinations thereof. For example, the oil in water emulsion may comprise at least 5 wt. % of a UV-B filter comprising or consisting of ethylhexylsalicylate, octocrylene, ethylhexyl triazone, benzophenone-3, 4-methylbenzylidene camphor, or combinations thereof, such as two or more thereof or three or more thereof. For example, the oil in water emulsion may comprise at least 5 wt. % of a UV-B filter consisting of two or more of ethylhexylsalicylate, octocrylene and ethylhexyl triazone. In a preferred example, the UV-B filter comprises at least 4.5 wt. % of ethylhexylsalicylate, at least 0.5 wt. % of octocrylene, and at least 0. 1 wt.% of ethylhexyl triazone.

[0099] The oil in water emulsion having at least 10 wt. % of an oil soluble / oil dispersible UV filter may comprise: a) from 2 to 10 wt. % , for example from 4 to 10 wt. % , of an oil soluble / oil dispersible UV-A filter comprising or consisting of butyl methoxydibenzoylmethane, diethylamino hydroxybenzoyl hexyl benzoate, methoxypropylamino cyclohexenylidene ethoxyethylcyanoacetate or combinations thereof, b) from 4 to 15 wt.%, such as 5.5 to 15 wt.%, of an oil soluble / oil dispersible UV-B filter comprising or consisting of ethylhexyl triazone, ethylhexyl methoxycinnamate, benzophenone-3, octocrylene, ethylhexylsalicylate, homosalate (homomenthyl salicylate) , isoamyl p-methoxycinnamate, polysilicone-15 , tris-biphenyl triazine, diethylhexyl butamido triazone, 4- methylbenzylidene camphor or combinations thereof; and c) from 1 to 10 wt. %, such as from 2 to 10 wt.%, of an oil soluble / oil dispersible broad spectrum UV filter comprising or consisting of bisethylhexyloxyphenol methoxyphenyl triazine, drometrizole trisiloxane, benzylidene camphor sulfonic acid, hydrophobically coated titanium dioxide, hydrophobically coated zinc oxide, or combinations thereof; and d) from 3 to 15 wt. % such as from 4 to 10 wt. % , of a water soluble / water dispersible UV filter comprising or consisting of titanium oxide particles, uncoated zinc oxide particles, methylene bis-benzotriazoyl tetramethyl butylphenol and phenylbenzimidazole sulfonic acid, terephthalylidene dicamphor sulfonic acid, disodium phenyl dibenzimidazole tetrasulfonate, and benzophenone-4, or combinations thereof.

[0100] In some examples, the UV-A protection is provided by a combination of one or more UV-A filters and / or one or more broad spectrum UV filters. Therefore, in some examples the oil in water emulsion having at least 10 wt. % of an oil soluble / oil dispersible UV filter may comprise: a) from 3 to 15 wt.%, for example from 5 to 15 wt.%, of a soluble / oil dispersible UV-A filter comprising or consisting of butyl methoxydibenzoylmethane, diethylamino hydroxybenzoyl hexyl benzoate, methoxy propylamino cyclohexenylidene ethoxyethylcyanoacetate or combinations thereof and / or an soluble / oil dispersible broad spectrum UV filter consisting of bisethylhexyloxyphenol methoxyphenyl triazine, drometrizole trisiloxane, benzylidene camphor sulfonic acid, hydrophobically coated titanium dioxide, hydrophobically coated zinc oxide, or combinations thereof, b) from 4 to 15 wt.%, such as 5.5 to 15 wt.%, of an oil soluble / oil dispersible UV-B filter comprising or consisting of ethylhexyl triazone, ethylhexyl methoxycinnamate, benzophenone-3, octocrylene, ethylhexylsalicylate, homomenthyl salicylate, isoamyl p-methoxycinnamate, polysilicone-15, homosalate, ethylhexyl triazone, tris-biphenyl triazine, diethylhexyl butamido triazone, 4- methylbenzylidene camphor or combinations thereof; and c) from 3 to 10 wt.% or from 4 to 10 wt.% , of a water soluble / water dispersible UV filter comprising or consisting of titanium oxide particles, uncoated zinc oxide particles, methylene bis-benzotriazoyl tetramethyl butylphenol and phenylbenzimidazole sulfonic acid, terephthalylidene dicamphor sulfonic acid, disodium phenyl dibenzimidazole tetrasulfonate, and benzophenone-4, or combinations thereof.

[0101] In some embodiments of the above examples, the UV-B filter may comprise or consist of two or more of ethylhexyl tri azone, ethylhexyl methoxy cinnamate, benzoph enone-3, octocrylene, ethylhexylsalicylate, homosalate (homomenthyl salicylate), isoamyl p- methoxycinnamate, polysilicone-15 , tris-biphenyl triazine, diethylhexyl butamido triazone, 4-methylbenzylidene camphor, such as three or more from this list. Therefore, the UV-B filter may comprise at least 2 wt.%, such as at least 4 wt.% or at least 5 wt.% of a first UV-B filter selected from ethylhexyl triazone, ethylhexyl methoxycinnamate, benzophenone-3 , octocrylene, ethylhexylsalicylate, homosalate (homomenthyl salicylate), isoamyl p-methoxycinnamate, polysilicone-15, homosalate, tris-biphenyl triazine, diethylhexyl butamido triazone, 4-methylbenzylidene camphor, and at least 0.5 wt. % , such as at least 1 wt. % or at least 2 wt. % of a second UV-filter selected from ethylhexyl triazone, ethylhexyl methoxycinnamate, benzophenone-3 , octocrylene, ethylhexylsalicylate, homosalate (homomenthyl salicylate), isoamyl p- methoxycinnamate, polysilicone-15 , tris-biphenyl triazine, diethylhexyl butamido triazone, 4-methylbenzylidene camphor, wherein the first UV-B filter and the second UV-B filter are different. The UV-B filter may comprise at least 0. 1 wt.%, such as at least 0.2 wt. % , of a third UV-B filter selected from ethylhexyl triazone, ethylhexyl methoxycinnamate, benzophenone-3, tris-biphenyl triazine, and 4-methylbenzylidene camphor wherein the third UV -B filter is different from the first and second UV-B filter and wherein preferably the third UV filter is ethylhexyl triazone.

[0102] For example, the oil in water emulsion may comprise UV-A filter butyl methoxydibenzoylmethane, UV-B filters ethylhexylsalicylate, octocrylene and ethylhexyl triazone, and broad spectrum UV filter bis- ethylhexyloxyphenol methoxyphenyl triazine in the oil phase, and methylene bis-benzotriazolyl tetramethylbutylphenol in the aqueous phase. The oil in water emulsion having at least 10 wt. % of an oil soluble / oil dispersible UV filter may comprise: a) from 2 to 10 wt. %, for example from 4 to 10 wt.%, of oil soluble / oil dispersible UV-A filter butyl methoxydibenzoylmethane; b) from 4 to 10 wt. %, such as 5.5 to 15 wt.%, of an oil soluble / oil dispersible UV- B filter consisting of ethylhexylsalicylate, octocrylene, ethylhexyl triazone or combinations thereof; c) from 1 to 10 wt. % , such as from 2 to 10 wt. % , of the broad spectrum UV filter bis-ethylhexyloxyphenol methoxyphenyl triazine; and d) from 3 to 10 wt. % of methylene bis-benzotriazolyl tetramethylbutylphenol.

[0103] The oil in water emulsion may comprise from 4 to 10 wt. % of UV-A filter butyl methoxydibenzoylmethane, from 5.5 to 15 wt.% of UV-B filters ethylhexylsalicylate, octocrylene and ethylhexyl triazone, and from 2 to 10 wt.% of broad spectrum UV filter bis-ethylhexyloxyphenol methoxyphenyl triazine in the oil phase, and from 4 to 10 wt.% of methylene bis-benzotriazolyl tetramethylbutylphenol in the aqueous phase.

[0104] Where the oil in water emulsion is free from water-soluble and / or water-dispersible UV filters, the amount of oil soluble / oil dispersible sunscreen may be increased to provide an SPF of at least 25. Therefore, where the oil in water emulsion is free from water- soluble and / or water-dispersible UV filters, the oil in water emulsion may comprise at least 15 wt. % of one or more oil-soluble and / or oil-dispersible UV filters by weight of the emulsion, such as at least 17 wt.%, at least 20 wt.%, from 15 to 30 wt.%, or from 15 to 25 wt. % , of one or more oil-soluble and / or oil-dispersible UV filters by weight of the emulsion. The oil-soluble and / or oil-dispersible UV filters may comprise UV-A, UV-B and / or broad spectrum UV filters as described above. A combination of one or more UV-A filters and one or more UV-B filters, or of one or more broad spectrum UV filters and one or more UV-B filters, or of one or more UV-A filters, one or more UV- B filters and one or more broad spectrum UV filters provides UV protection across the spectrum.

[0105] Where the oil in water emulsion is free from water-soluble and / or water-dispersible UV filters, the oil-soluble and / or oil-dispersible UV filters may comprise at least 6, wt.% a UV-A filter, such as at least 7 wt. % , at least 6 wt. % , such as at least 7 wt. %, of a UV- B filter, and at least 3 wt. % such as at least 4 wt. % or at least 7 wt. % of a UV-B filter. Such an oil in water emulsion with an oil phase large enough to accommodate this amount of oil -soluble and / or oil-dispersible UV filter is facilitated by the retinoid system disclosed herein.

[0106] As noted above, in some preferred examples the emulsion comprises a combination of one or more UV-A filters and one or more UV-B filters.

[0107] In some examples, where the emulsion comprises a combination of one or more UV-A filters and one or more UV-B filters, the oil in water emulsion having at least 10 wt.%, such as at least 15 wt. %, of an oil soluble / oil dispersible UV filter may comprise: a) from 3 to 20 wt. % , such as from ? to 15 wt. % or from 10 to 20 wt. %, of an oil soluble / oil dispersible UV-A filter comprising or consisting of butyl methoxydibenzoylmethane, diethylamino hydroxybenzoyl hexyl benzoate, methoxypropylamino cyclohexenylidene ethoxyethylcyanoacetate or combinations thereof; b) from 5 to 30 wt. % , such as from ? to 25 wt. % or from 10 to 25 wt. %, of an oil soluble / oil dispersible UV-B filter comprising or consisting of ethylhexyl triazone, ethylhexyl methoxycinnamate, benzophenone-3, octocrylene, ethylhexylsalicylate, homosalate (homomenthyl salicylate), isoamyl p- methoxycinnamate, poly silicone- 15 , tris-biphenyl triazine, diethylhexyl butamido triazone, 4- methylbenzylidene camphor or combinations thereof; and c) from 0 to 10 wt.%, such as from O to 5 wt.%, of an oil soluble / oil dispersible broad spectrum UV filter comprising or consisting of bisethylhexyloxyphenol methoxyphenyl triazine, drometrizole trisiloxane, benzylidene camphor sulfonic acid, hydrophobically coated titanium dioxide, hydrophobically coated zinc oxide, or combinations thereof; and d) 0 to 15 wt. % such as from 0 to 10 wt.%, of a water soluble / water dispersible UV filter comprising or consisting of titanium oxide particles, uncoated zinc oxide particles, methylene bis-benzotriazoyl tetramethyl butylphenol and phenylbenzimidazole sulfonic acid, terephthalylidene dicamphor sulfonic acid, disodium phenyl dibenzimidazole tetrasulfonate, and benzophenone-4, or combinations thereof. In some embodiments of examples where the emulsion comprises a combination of one or more UV-A filters and one or more UV-B filters, the emulsion comprises two or more of ethylhexyl triazone, ethylhexyl methoxycinnamate, benzopheno ne-3 , octocrylene, ethylhexylsalicylate, homosalate (homomenthyl salicylate), isoamyl p- methoxycinnamate, polysilicone-15 , tris-biphenyl triazine, diethylhexyl butamido triazone, and 4-methylbenzylidene camphor, such as three or more from this list.

[0108] In some embodiments of examples where the emulsion comprises a combination of one or more UV-A filters and one or more UV-B filters, the emulsion comprises two or more of butyl methoxy dibenzoylmethane, diethylamino hydroxybenzoyl hexyl benzoate, and methoxypropylamino cyclohexenylidene ethoxyethylcyanoacetate, or comprises all three of these filters.

[0109] In some embodiments of examples where the emulsion comprises a combination of one or more UV -A filters and one or more UV -B filters, oil in water emulsion may comprise at least 15 wt. % , such as 20 wt. % , of an oil soluble / oil dispersible UV filter may comprise: a) from 3 to 20 wt of an oil soluble / oil dispersible UV-A filter comprising or consisting of butyl methoxydibenzoylmethane, diethylamino hydroxybenzoyl hexyl benzoate, methoxypropylamino cyclohexenylidene ethoxyethylcy anoacetate or combinations thereof; and b) from 15 to 30 wt. % , such as from 20 to 30 wt. % , of an oil soluble / oil dispersible UV-B filter comprising two or more of ethylhexyl triazone, ethylhexyl methoxycinnamate, benzopheno ne-3, octocrylene, ethylhexylsalicylate, homosalate (homomenthyl salicylate), isoamyl p- methoxycinnamate, polysilicone-15 , tris-biphenyl triazine, diethylhexyl butamido triazone, 4-methylbenzylidene camphor or combinations thereof.

[0110] The skilled person will appreciate that using the above amounts and lists of filters a combination providing an SPF of at least 25 can be achieved through routine optimisation. The oil in water emulsion of the present invention having the above defined retinoid system allows this combination to be stabilised in a retinoid containing oil in water emulsion. Emulsifiers

[0111] The emulsion may comprise one or more emulsifiers, also referred to as surfactants, to help stabilise the emulsion. Suitable emulsifiers include all those suitable for the purpose and known by those skilled in the art for use in skin care products. Where the emulsion is a water in oil emulsion the emulsifiers may have an HLB value of or less than 14, such as from 2 to 14, or from 2 to 10. Where the emulsion is an oil in water emulsion, the surfactants may have a HLB value of greater than 8, such as from 8 to 18, or from 10 to 16. HLB may be determined using the Davies’ method, which is known to the person skilled in the art.

[0112] The one or more emulsifier may comprise one or more silicone emulsifiers. Silicone emulsifiers are typically organically modified organopolysiloxanes, also known to those skilled in the art as silicone surfactants. Useful silicone emulsifiers include dime thicone copolyols. These materials are polydimethyl siloxanes which have been modified to include polyether side chains such as polyethylene oxide chains, polypropylene oxide chains, mixtures of these chains, and chains comprising moieties derived from both ethylene oxide and propylene oxide. Other examples include alkyl -modified dimethicone copolyols, i. e., compounds which comprise C2 -C30 pendant side chains. Still other useful dimethicone copolyols include materials having various cationic, anionic, amphoteric and zwitterionic pendant moieties.

[0113] Nonlimiting examples of dimethicone copolyols and other silicone surfactants useful as emulsifiers herein include polydimethylsiloxane polyether copolymers with pendant polyethylene oxide side chains, polydimethylsiloxane polyether copolymers with pendant polypropylene oxide side chains, polydimethylsiloxane polyether copolymers with pendant mixed polyethylene oxide and polypropylene oxide side chains, polydimethylsiloxane polyether copolymers with pendant mixed poly (ethylene) (propylene) oxide side chains, poly dimethylsiloxane polyether copolymers with pendant organobetaine side chains, polydimethylsiloxane polyether copolymers with pendant carboxylate side chains, polydimethylsiloxane polyether copolymers with pendant quaternary ammonium side chains; and also further modifications of the preceding copolymers comprising pendant C2-C30 straight, branched, or cyclic alkyl moieties. The emulsifier may comprise PEG / PPG- 18 / 18 dimethicone. Other nonlimiting examples of dimethicone copolyols also include lauryl dimethicone copolyol, dimethicone copolyol acetate, diemethicone copolyol adipate, dimethicone copolyolamine, dimethicone copolyol behenate, dimethicone copolyol butyl ether, dimethicone copolyol hydroxy stearate, dimethicone copolyol isostearate, dimethicone copolyol laurate, dimethicone copolyol methyl ether, dimethicone copolyol phosphate, and dimethicone copolyol stearate.

[0114] The one or more emulsifier may comprise one or more non- sili cone-comprising emulsifiers. The non-silicone-comprising emulsifiers may comprise various non-ionic and anionic emulsifying agents such as sugar esters and polyesters, alkoxy lated sugar esters and polyesters, C1 -C30 fatty acid esters of C1 -C30 fatty alcohols, alkoxylated derivatives of C1 -C30 fatty acid esters of C 1 -C30 fatty alcohols, alkoxylated ethers of C i -C 30 fatty alcohols, polyglyceryl esters of C1-C30 fatty acids, C1 -C30 esters of polyols, Ci -C 30 ethers of polyols, alkyl phosphates, polyoxy alkylene fatty ether phosphates, fatty acid amides, acyl lactylates, soaps, cetearyl glucoside, polyglyceryl-6 stearate and polyglyceryl-6 behenate, and combinations thereof.

[0115] The one or more emulsifier may comprise non-silicon-comprising emulsifiers selected from polyethylene glycol 20 sorbitan monolaurate (Polysorbate 20) , polyethylene glycol 5 soya sterol, Steareth-20, Ceteareth-20, PPG-2 methyl glucose ether distearate, Ceteth- 10, Polysorbate 80, cetyl phosphate, potassium cetyl phosphate, diethanolamine cetyl phosphate, Polysorbate 60, glyceryl stearate, PEG- 100 stearate, polyoxyethylene 20 sorbitan trioleate (Polysorbate 85) , sorbitan monolaurate, polyoxyethylene 4 lauryl ether sodium stearate, polyglyceryl-4 isostearate, hexyl laurate, steareth-20, ceteareth- 20, PPG-2 methyl glucose ether distearate, ceteth-10, diethanolamine cetyl phosphate, glyceryl stearate, PEG- 100 stearate, and combinations thereof.

[0116] The one or more emulsifier may include sesiquioleates such as sorbitan sesiquioleate, ethoxylated esters such as the polyethoxylated ester of hydrogenated castor oil, silicone emulsifiers such as silicone polyols, anionic emulsifiers such as fatty acid soaps including potassium stearate and fatty acid sulphates such as sodium cetostearyl sulphate, ethoxylated fatty alcohol, sorbitan esters, ethoxylated sorbitan esters, ethoxylated fatty acid esters such as ethoxylated stearates, ethoxylated mono, di and triglycerides, non-ionic self-emulsifying waxes, ethoxylated fatty acids, methylglucose esters such as polyglycerol-3 methyl glucose distearate, or combinations thereof. Matrix metalloproteinase inhibitors (MMPi)

[0117] The emulsions of the present invention may optionally comprise matrix metalloproteinase inhibitors. The term " matrix metalloproteinase inhibitor" relates to all molecule and / or plant or bacterial extracts having an inhibitory activity on at least one of the matrix metalloproteinases expressed by or synthesised in the skin. The family of the matrix metalloproteinases is formed of several well-defined groups on the basis of their resemblance regarding structure and substrate specificity (Woessner J. F. 1991, Faseb Journal, vol. 5,-, 2145) . Among these groups, there are collagenases able to degrade fibrillar collagens (MMP-1 or interstitial collagenase, MMP- 8 or neutrophil collagenase, MMP- 13 or collagenase 3 , MMP- 18 or collagenase 4) , gelatinases degrading type IV collagen or other denatured collagen form (MMP-2 or A gelatinase (72 kDa) , MMP-9 or B gelatinase (92 kDa)), stromelysins (MMP-3 or stromelysin 1, MMP- 10 or stromelysin 2, MMP-1 1 or stromelysin 3) whose broad spectrum of activity targets proteins of the dermal extracellular matrix such as glycoproteins (fibronectin, laminin) , proteoglycans etc. , matrilysin (MMP-7), metalloelastase (MMP- 12) or metalloproteinases (MMP-14, MMP- 15, MMP- 16 and MMP- 17). Metalloproteinases (MMPs) are proteases that use a metal, (mostly zinc) coordinated to 3 cysteine residues and to a methionine in their active site, that degrade macromolecular components of the dermal extracellular matrix and of basal layers at neutral pH (collagen, elastin, etc ...). This group of enzymes is inactivated by metal chelators. The principal activity regulators of MMPs are the tissue inhibitors of metalloproteinases or TIMPs such TIMP- 1 , TIMP-2, TIMP-3 and TIMP-4 (Woessner J . F., Faseb Journal, 1991) . Furthermore, MMP expression is also regulated by growth factors, cytokines, oncogene products (ras, jun) , or also matrix constituents.

[0118] The term "matrix metalloproteinase inhibitors" according to the present invention means all molecules able to reduce the MMP’ s activity regarding the gene expression (transcription and translation) or regarding the activation of the zymogen form of the MMP, or else regarding the local control of active forms. Furthermore, the metalloproteinase inhibitors according to the present invention can also be MMP-1 inhibitors of natural or synthetic origin. The terms " natural origin" or " synthetic origin" mean both a metalloproteinase inhibitor at a pure state or in solution at different concentrations, but natural origin termed inhibitors are obtained by different extraction methods from a natural element (for example lycopene from a tomato) whereas the inhibitors of synthetic origin are all obtained via chemical synthesis

[0119] Preferred MMPi are selected from the group consisting of retinoid, N-acetyl cysteine, glutathione, 2-furildioxime, vitamin C, flavones, isoflavones, hydrolysed rice protein, alfalfa extract, white lupin, zizyphus jujube extract, dihydroxy methyl chromone, kudzu extract, vitis vinifera extract, Oenothera biennis extract Anogeissus leiocarpus extract and combinations thereof.

[0120] Where present, MMPi are present at a level of from 0.01 % to 10% , more preferably 0. 1 % to 5 % and most preferably from 0.5 % to 2.5 % by weight of the emulsion.

[0121] Skin Conditioning Agent

[0122] The emulsions of the present invention may optionally comprise a skin conditioning agent. Said skin conditioning agents may preferably be selected from the group consisting of humectants, emollients, moisturisers, or mixtures thereof. Where present, they are preferably present at a level of from 0.01 % to 20%, more preferably from 0.1% to 10% , most preferably from 0.5 % to 7% by weight of the emulsion.

[0123] Preferred skin conditioning agents are selected from the group consisting of guanidine, urea, glycolic acid and glycolate salts, salicylic acid, lactic acid and lactate salts, aloe vera, shea butter, polyhydroxy alcohols, such as sorbitol, mannitol, xylitol, erythritol, glycerol, hexanetriol, butanitriol, (di) propylene glycol, butylene glycol, hexylene glycol, polyethylene glycol, sugars (e. g. fructose, glucose, xylose, honey, mannose, xylose) , gluconodeltalactone, and starches and their derivatives, pyrrolidone, carboxylic acid, hyaluronic acid and salts thereof, lactamide monoethanolamine, acetamide monoethanolamine, panthenol, allantoin and combinations thereof.

[0124] More preferably said skin conditioning agent is selected from the group consisting of glycerine, arabinogalactan, butylene glycol, hyaluronic acid, shea butter, propylene glycol, ethylhexyl glycerine, hyaluronate and combinations thereof. Dipeptide

[0125] The emulsions of the present invention may comprise one or more dipeptide selected from the group consisting of acetyl dipeptide 1 cetyl ester (Tyrosine - Arginine), acetyl dipeptide 3 aminohexanoate (Alanine - Arginine) , azelaoyl bisdipeptide 10 (Alanine - Histidine), coumaroyl dipeptide 3 (Alanine - Arginine) , dicetyl dipeptide 9 (Glutamic acid - Lysine) , dipeptide diamino butyroyl benzylamide diacetate, dipeptide 1 (Tyrosine - Arginine), dipeptide 10 (Alanine - Histidine), dipeptide 1 1 (Cysteine - Lysine), dipeptide 12 (Lysine - Lysine) , dipeptide 14 (Alanine - Threonine), (dipeptide 15 (Glycine - Glycine), dipeptide 16 (Leucine - Leucine), dipeptide 17 (Glycine - Proline), dipeptide 18 (Glycine - Histidine), dipeptide 19 (Leucine - Glutamic acid) , dipeptide 2 (Valine - Tryptophan), dipeptide 20 (Lysine - Methionine), dipeptide 3 ( Alanine - Arginine), dipeptide 4 (Cysteine - Glycine), dipeptide 5 (Lysine - Valine), dipeptide 6 (Proline - Hydroxyproline) , dipeptide 7 (Lysine - Threonine), dipeptide 8 (Alanine - Hydroxyproline), dipeptide 8 HCL (Alanine - Hydroxyproline), dipeptide 9 (Glutamic acid - Lysine) , hexanoyl dipeptide 3 norleucine acetate (Alanine - Arginine), methyl undecylenoyl dipeptide 16 (Leucine - Leucine) , nicotinoyl dipeptide 22 (Serine - Valine) , nicotinoyl dipeptide 23 (Proline - Serine), nicotinoyl dipeptide 24 (Glutamic acid - Threonine), nicotinoyl dipeptide 26 (Arginine - Valine), oleoyl dipeptide 15 (Glycine - Glycine), palmitoyl dipeptide 10 (Alanine - Histidine), palmitoyl dipeptide 13 (Tryptophan and Glutamic acid) , palmitoyl dipeptide 17 (Glycine - Proline), palmitoyl dipeptide 5 di aminobutyroyl hydroxy threonine (Lysine - Valine), palmitoyl dipeptide 5 diaminohydroxybutyrate (lysine - Valine), palmitoyl dipeptide 7 (Lysine - Threonine) and combinations thereof.

[0126] Dipeptides are preferably incorporated into the emulsion of the present invention at a level of from 0. 1 to 50,000ppm, more preferably from 1 to 5 ,000 ppm, most preferably from 10 to 500ppm.

[0127] Other Optional Ingredients

[0128] The emulsions of the present invention may also optionally comprise one or more of the following optional ingredients. Preservatives may be added to the emulsion such as 2- bromo-2-nitropropane-l,3-diol (bronopol, which is available commercially under the trade name Myacide RTM) , benzyl alcohol, diazolidinyl urea, imidazolidinyl urea, methyl paraben, phenoxyethanol, ethyl paraben, propyl paraben, sodium methyl paraben, sodium dehydroacetate, polyhexamethylenebiguanide hydrochloride, isothiazolone and sodium propyl paraben, suitably in an amount of from 0.01% to 10% by weight of the emulsion.

[0129] Thickeners, viscosity modifying agents and / or gelling agents may be added to the emulsion, such as acrylic acid polymers e. g. available commercially under the trade name Carbopol or Ultrez (Lubrizol) or modified cellulose e.g. hydroxyethylcellulose available commercially under the trade name Natrosol (Hercules) or hydroxypropylmethyl cellulose, amine oxides, block polymers of ethylene oxide and propylene oxide (for example, those available from BASF Wyandotte under the trade name "Pluronic" ®), PVM, MA, or a decadiene crosspolymer (available under the trade name Stabilez 60) , ethoxylated fatty alcohols, salt (magnesium chloride, sodium chloride), Aristoflex AVC (Clariant), phthalic acid amide, xanthan gum, sodium polyacrylate, polyvinyl alcohols, fatty alcohols and alkyl galactomannans available under the trade name N-Hance from Hercules, suitably in an amount of from 0.5% to 10% by weight of the emulsion.

[0130] Sequestering agents may be added to the emulsion, such as ethylenediamine tetraacetic acid and salts thereof, suitably in an amount of from 0.005% to 0.5 % by weight of the emulsion.

[0131] The emulsion may also include waxes such as cocoa butter suitably in an amount of from 1 % to 99% by weight of the emulsion.

[0132] The emulsion may also comprise suitable, cosmetically acceptable diluents, carriers and / or propellants such as dimethyl ether.

[0133] The emulsion may also include pearlising agents such as stearic monoethanolamide and / or mica, suitably in an amount of from 0.01% to 10% by weight of the emulsion.

[0134] Perfumes may be added suitably in an amount of from 0.01 % to 2% by weight of the emulsion, as may water soluble dyes such as tartrazine, suitably in an amount of from a trace amount (such as 1 x 10- 5 %) to 0. 1 % by weight of the emulsion. The emulsion may also include pH adjusting agents such as sodium hydroxide, aminomethyl propanol, triethanolamine, suitably in an amount of from 0.01 % to 10% by weight of the emulsion. The emulsion may be buffered by means well known in the art, for example by use of buffer systems comprising succinic acid, citric acid, lactic acid, and acceptable salts thereof, phosphoric acid, mono-or disodium phosphate and sodium carbonate. Suitably, the emulsion may have a pH between 3 and 10, preferably between 4 and 8.

[0135] High Oil Phase Emulsions

[0136] Further aspects of the invention are defined by the following clauses:

[0137] Clause 1 : An emulsion having an SPF of at least 25 , comprising:

[0138] (a) at least 0.01 wt. % of one or more retinoid;

[0139] (b) one or more one water-soluble antioxidant;

[0140] (c) one or more one oil-soluble antioxidant; wherein the emulsion further comprises at least 40 wt. % of an oil phase and at least 10% of one or more oil-soluble or oil-dispersible sunscreen components by weight of the emulsion.

[0141] Clause 2: The emulsion of clause 1, wherein in the weight ratio of a: b:c is l : at least

[0142] 1 : at least 0. 1 .

[0143] Clause 3 : The emulsion of any one of clauses 1 or 2, wherein the one or more oilsoluble or oil-dispersible sunscreen components comprises one or more of a broadspectrum UV filter, a UV-A filter, a UV-B filter, or a combination thereof, wherein, optionally: i) the broad- spectrum UV filter comprises bis- ethylhexyl oxyphenol methoxyphenyl triazine, drometrizole trisiloxane or a combination thereof, and / or ii) the UV-A filter comprises butyl methoxydibenzoylmethane, diethylamino hydroxybenzoyl hexyl benzoate, terephthalylidene dicamphor sulfonic acid, disodium phenyl dibenzimidazole tetrasulfonate, or a combination thereof, and / or iii) the UV-B filter comprises ethylhexyl triazone, ethylhexyl methoxycinnamate, benzophenone-3 , octocry lene, ethylhexyl salicylate, homomenthyl salicylate, isoamyl p-methoxycinnamate, polysili cone-15, diethylhexyl butamido triazone, 4-methylbenzylidene camphor, trisbiphenyl triazine or a combination thereof.

[0144] Clause d: The emulsion of any one of clauses 1 to 3 , wherein the one or more oil-soluble or oil-dispersible sunscreen components comprise butyl methoxydibenzoylmethane, ethylhexyl salicylate, bis-ethylhexyloxyphenol methoxyphenyl triazine, ethylhexyl triazone, or combinations thereof.

[0145] Clause 5 : The emulsion of any one of clauses 1 to 4, wherein the emulsion comprises at least 15 wt. % of one or more oil-soluble or oil-dispersible sunscreen components by weight of the emulsion.

[0146] Clause 6: The emulsion of any one of clauses 1 to 5, wherein the one or more emulsion further comprises (d) a triglyceride, wherein, optionally: i) the triglyceride is a C3-C12 triglyceride, optionally caprylic / capric triglyceride; and / or ii) the triglyceride is present in an amount of at least 10 parts by weight of the retinoid, such that the ratio of a:b:c:d is l : at least 1 : at least 0. 1 : at least 10.

[0147] Clause 7 : The emulsion of any one of clauses 1 to 6, wherein the one or more retinoid: i) is an all-trans retinoid, and / or ii) comprises retinol, retinal, or a combination thereof.

[0148] Clause 8 : The emulsion of any one of clauses 1 to 7, wherein the one or more water soluble antioxidant comprises: i) ascorbic acid, sodium ascorbate, sodium sulfite, sodium metabisulfite, sodium bisulfite, sodium thiosulfite, sodium formaldehyde sulfoxylate, isoascorbic acid, thioglycerol, thiosorbitol, thiourea, thioglycolic acid, cysteine hydrochloride, 1,4- diazobicyclo(2.2.2)octane, or combinations thereof; or ii) ascorbic acid, isoascorbic acid, L-ascorbic acid, ascorbyl glucoside, ethyl ascorbic acid, sodium ascorbyl phosphate, magnesium ascorbyl phosphate or cosmetically acceptable salts thereof; or iii) comprises sodium ascorbate.

[0149] Clause 9 : The emulsion of any one of clauses 1 to 8, wherein the oil-soluble antioxidant comprises ascorbyl palmitate, alpha- tocopherol, phenyl-[alpha]- naphthylamine, tocopherol acetate, ascorbyl tetraisopalmitate or combinations thereof, optionally wherein the oil-soluble antioxidant is alpha- tocopherol and / or gamma- tocopherol.

[0150] Clause 10: The emulsion of any one of clauses 1 to 9, wherein the oil phase comprises one or more emulsifier.

[0151] Clause 1 1 : The emulsion of clause 10, wherein the one or more emulsifier comprises polyethylene glycol 20 sorbitan monolaurate (Polysorbate 20) , polyethylene glycol 5 soya sterol, Steareth-20, Ceteareth-20, PPG-2 methyl glucose ether distearate, Ceteth- 10, Polysorbate 80, cetyl phosphate, potassium cetyl phosphate, diethanolamine cetyl phosphate, Polysorbate 60, glyceryl stearate, PEG- 100 stearate, polyoxyethylene 20 sorbitan trioleate (Polysorbate 85) , sorbitan monolaurate, polyoxyethylene 4 lauryl ether sodium stearate, polyglyceryl-4 isostearate, hexyl laurate, steareth-20, ceteareth- 20, PPG-2 methyl glucose ether distearate, ceteth-10, diethanolamine cetyl phosphate, glyceryl stearate, PEG-100 stearate, cetearyl glucoside, polyglyceryl- 6 stearate and polyglyceryl-6 behenate and combinations thereof.

[0152] Clause 12: Use of the emulsion according to any one of clauses 1 to 1 1 for a topical cosmetic application to the skin.

[0153] Clause 13 : Use of the emulsion according to any one of clauses 1 to 1 1 as a non- therapeutic cosmetic treatment to improve the condition of the skin and / or lines and / or wrinkles and / or imperfections and / or skin firmness and elasticity.

[0154] Clause 14: A method comprising applying the emulsion according to any one of clauses 1 to 1 1 to skin of the subject. Clause 15 : A cosmetic method for improving the condition and / or appearance of the skin and / or lines and / or wrinkles and / or reduce imperfections and / or improve skin firmness and elasticity, comprising topically administering the emulsion according to any one of clauses 1 to 1 1.

[0155] In the above clauses, the oil phase of the emulsion will comprise water-insoluble substances having a solubility in water of less than 1 g / 100g at 20°C, such as 0. 1g / 100g at 20°C, the oil-soluble or oil-dispersible sunscreen components, and emulsifiers used to stabilise the emulsion. The water phase will comprise all other substances.

[0156] In the above clauses, the emulsion may be a water-in-oil emulsion, an oil-in-water emulsion, or a multiple emulsion such as water-in-oil-in-water or oil-in-water-in-oil. For example, the emulsion may be an oil-in-water emulsion.

[0157] Methods of Use

[0158] The present invention further relates to a use of the emulsion of the present invention for a topical cosmetic application to the skin.

[0159] The present invention also relates to a use of the emulsion of the present invention as a non- therapeutic cosmetic treatment to improve the condition of the skin and / or lines and / or wrinkles and / or imperfections and / or skin firmness and elasticity.

[0160] The present invention relates to a method comprising applying the emulsion of the present invention to the skin of the subject. The subject may be a human.

[0161] The invention also relates to a cosmetic method for improving the condition and / or appearance of the skin and / or lines and / or wrinkles and / or reduce imperfections (e.g., pigmentation) and / or improve skin firmness and elasticity, comprising topically administering the emulsion of the present of the invention.

[0162] The methods and uses of the present invention comprise applying the emulsion to the skin. The skin may be the skin of a human. The methods and uses may comprise applying the emulsion to the skin in the morning. The methods and uses may comprise applying the emulsion to the skin before exposing the skin to direct sunlight. Method of Manufacture

[0163] The present invention further provides a method of preparing the oil-in-water emulsion of the invention. The method comprises:

[0164] (i) combining the oil soluble and / or oil dispersible UV filters and heating the combination to at least 50°C, such as at least 60 °C to form a liquid oil phase;

[0165] (ii) adding to the liquid oil phase the retinoid, tocopherol and sodium ascorbate, and optionally the triglyceride if present;

[0166] (iii) adding the oil phase to a water phase and homogenising the water phase and the oil phase, optionally with stirring, to form an oil in water emulsion.

[0167] The method may further comprise in step (i) combining further components of the oil phase as defined herein with the oil soluble and / or oil dispersible UV filters to form the oil phase. The method may further comprise in step (i) combining emulsifiers with the other components of step (i). The method may further comprise in step (i) combining the oil soluble and / or oil dispersible UV filters with one or more oil and / or one or more emollient.

[0168] The water phase contains water and optionally glycerine. The water phase may comprise other components as defined herein.

[0169] The temperature of step (i) is at least 50°C, such as at least 60°C, at least 70°C. The temperature of step (i) may be 95 °C or less, such as 90°C or less, 85°C or less or 80°C or less, or from 50°C to 95°C.

[0170] The method may further comprise in step (ii) after adding to the liquid oil phase the retinoid, tocopherol and sodium ascorbate, and optionally the triglyceride if present, combining the components, for example with stirring. Step (ii) may be performed at the same temperature as step (i), such as at least 50°C, 95 °C or less, or from 50°C to 95°C.

[0171] The method may further comprise after step (iii) , step (iv) comprising cooling the emulsion to 45°C or less, such as 40°C or less or 35 °C or less and adding one or more water soluble and / or water dispersible UV filter, such as methylene bis-benzotriazolyl tetramethylbutylphenol or phenylbenzimidazole sulfonic acid, optionally with stirring. Step (iv) may comprise cooling the emulsion to 15 °C or greater or 20°C or greater, or from or from 15 °C to 45 °C, such as from 20°C to 40°C.

[0172] All the embodiments and features described herein (including any accompanying claims and abstract), and / or all of the steps of any method or process so disclosed, may be combined with any of the above aspects or embodiments in any combination, unless stated otherwise with reference to specific combinations, for example, combinations where at least some of such features and / or steps are mutually exclusive.

[0173] Examples

[0174] Compositions

[0175] A retinoid day cream composition was prepared having an SPF of 30 and comprising 0.025 wt.% retinol in RetiSTAR (BASF) and 1 1 .7 wt.% of oil soluble or oil dispersible UV filters.

[0176] RetiSTAR (BASF) is a retinol formulation further comprising caprylic / capric triglyceride and retinol and tocopherol and sodium ascorbate.

[0177] The oil soluble or oil dispersible UV filters in the example composition consist of butyl methoxydibenzoylmethane, ethylhexylsalicylate bis- ethylhexyl oxyphenol methoxyphenyl triazine, octocrylene and ethylhexyl triazone.

[0178] The example composition further comprises the water dispersible UV filter methylene bis-benzotriazolyl tetramethylbutylphenol.

[0179] Example 1: Day Cream with 0.025% retinol in RetiSTAR (BASF)

[0180] Method of Manufacture

[0181] 1. To water add Glycerin and dissolve Tetrasodium EDTA. 2. Using homogenisation sprinkle in Xanthan gum and continue to homogenise for

[0182] 3 minutes or until hydrated.

[0183] 3. Using homogenisation sprinkle in Carbomer and continue to homogenise for 5 minutes or until hydrated.

[0184] 4. Add Polysorbate 20 and stir until uniform then heat water phase to 70-75°C. 5. In a separate vessel weigh out oil phase and heat to 70-75°C. (Butyl methoxydibenzoylmethane, Ethylhexylsalicylate, Bisethylhexyloxyphenol methoxyphenyl triazine, Octocrylene, Ethylhexyl triazone, Butyrospermum parkii (shea) butter, Cetearyl alcohol, Cetearyl glucoside, C12- 15 alkyl benzoate, Tocopheryl acetate. )

[0185] 6. When the oil phase is at 70-75°C and the solids are dissolved add Caprylic / capric triglyceride and Retinol and Tocopherol and Sodium ascorbate and stir for 2 minutes.

[0186] 7. Stir in Aluminium starch octenylsuccinate, Silica and Potassium cetyl phosphate and stir for 3 minutes or until uniform.

[0187] 8. With both phases at 70-75°C add the oil phase to the water phase and homogenise for 5 minutes at 5000rpm.

[0188] 9. Add Potassium hydroxide and homogenise for a further 2 minutes.

[0189] 10. Cool bulk to below 35°C.

[0190] 1 1. Stir in Methylene bis-benzotriazolyl tetramethylbutylphenol (dispersed in water) and stir until uniform.

[0191] 12. Stir in Phenoxyethanol, Caprylyl glycol & Ethylhexylglycerin, Propanediol & Caprylhydroxamic acid, Fragrance, Palmitoyl oligopeptide & palmitoyl tetrapeptide3 and Panthenol.

[0192] 13. Dissolve Ascorbyl glucoside in a small amount of water and stir into the bulk.

[0193] 14. Make to weight with water and stir smooth.

[0194] Compositions were placed in glass jars for physical stability analysis.

[0195] Viscosity:

[0196] The viscosity of the samples was determined using a Brookfield LVT viscometer spindle number 4, speed 12 rpm for 30 seconds. Viscosity for all compositions followed similar trends for all samples, with an initial settling to four weeks then plateauing to 13 weeks. The viscosity of the compositions according to the invention was suitably stable for a commercial product. pH:

[0197] The pH of the samples was determined using a Mettler Toledo Compact Severn pH meter. The pH of the samples showed natural variation over 13 weeks but no drifting outside + / - 0.5 pH units of Initial pH.

[0198] The pH of the compositions according to the invention was suitably stable for a commercial product.

[0199] Analytical Stability

[0200] To determine retinol content over time, compositions were saponified with ethanolic potassium hydroxide, extracted with ether, evaporated to dryness and re-dissolved in a solvent appropriate to HPLC quantification.

[0201] Saponification hydrolyses esters to their respective alcohols and also removes neutral lipids from the compositions. The un- saponifiable material, including retinol and tocopherol, was then extracted into ether. Retinol was detected by reverse- phase HPLC with UV diode array detection.

[0202] Table 1 : Analytical Results Example 1 - Day Cream with 0.025% retinol in

[0203] RetiSTAR (BASF)

[0204] The analytical results for Example 1 shows that the retinol content is stabilised at acceptable levels in an SPF 30 composition that is physically stable. A further example of a composition in accordance with the present invention is provided below together with a methods of manufacture.

[0205] Example 2: SPF 25 Day Cream with 0.025 % retinol in RetiSTAR (BASF)

[0206] Method of Manufacture

[0207] 1. To water add Glycerin and dissolve Tetrasodium EDTA.

[0208] 2. Using homogenisation sprinkle in Xanthan gum and continue to homogenise for 3 minutes or until hydrated.

[0209] 3. Using homogenisation sprinkle in Carbomer and continue to homogenise for 5 minutes or until hydrated.

[0210] 4. Add Polysorbate 20 and stir until uniform then heat water phase to 70-75°C.

[0211] 5. In a separate vessel weigh out oil phase and heat to 70-75°C. (Butyl methoxydibenzoylmethane, Ethylhexylsalicylate, Homosalate, Octocrylene, Ethylhexyl methoxy cinnamate, Butyrospermum parkii (shea) butter, Cetearyl alcohol, Cetearyl glucoside, C12-15 alcohols benzoate, Tocopheryl acetate. )

[0212] 6. When the oil phase is at 70-75°C and the solids are dissolved add Caprylic / capric triglyceride and Retinol and Tocopherol and Sodium ascorbate and stir for 2 minutes.

[0213] 7. Stir in Aluminium starch octenylsuccinate, Silica and Potassium cetyl phosphate and stir for 3 minutes or until uniform.

[0214] 8. With both phases at 70-75°C add the oil phase to the water phase and homogenise for 5 minutes at 5000rpm.

[0215] 9. Add Potassium hydroxide and homogenise for a further 2 minutes.

[0216] 10. Cool bulk to below 35°C.

[0217] 1 1. Stir in Phenoxyethanol, Caprylyl glycol & Ethylhexylglycerin, Propanediol & Caprylhydroxamic acid, Fragrance, Palmitoyl oligopeptide & palmitoyl tetrapeptide3 and Panthenol.

[0218] 12. Dissolve Ascorbyl glucoside in a small amount of water and stir into the bulk.

[0219] 13. Make to weight with water and stir smooth.

Claims

CLAIMS1. An oil in water emulsion having an SPF of at least 25, comprising:(a) at least 0.01 wt. % of one or more retinoid selected from retinol, retinal, retinoic acid or combinations thereof;(b) one or more water-soluble antioxidant;(c) one or more oil-soluble antioxidant;(d) at least 10 wt. % of one or more oil-soluble and / or oil-dispersible sunscreen components.

2. The oil in water emulsion of claim 1 , wherein in the weight ratio of (a):(b):(c) is l :at least 1 : at least 0. 1.

3. The oil in water emulsion of any one of claims 1 or 2, wherein the one or more oil-soluble or oil-dispersible sunscreen components comprises one or more of a UV-A filter, a UV-B filter, or a combination thereof, wherein, optionally: i) the UV-A filter comprises butyl methoxydibenzoylmethane, diethylamino hydroxybenzoyl hexyl benzoate, methoxypropylamino cyclohexenylidene ethoxyethylcyanoacetate or a combination thereof, and / or ii) the UV-B filter comprises ethylhexyl triazone, ethylhexyl methoxycinnamate, benzophenone-3 , octocry lene, ethylhexyl salicylate, homomenthyl salicylate, isoamyl p-methoxycinnamate, polysili cone-15, diethylhexyl butamido triazone, 4-methylbenzylidene camphor, trisbiphenyl triazine or a combination thereof.

4. The oil in water emulsion of any one of any preceding claim, wherein the one or more oil-soluble or oil-dispersible sunscreen components comprise butyl methoxydibenzoylmethane, ethylhexyl salicylate, bis-ethylhexyloxyphenol methoxyphenyl triazine, ethylhexyl triazone, or combinations thereof.

5. The oil in water emulsion of any preceding claim, wherein the oil in water emulsion comprises:(a) from 0.01 to 1 wt. % of one or more retinoid selected from retinol, retinal, retinoic acid or combinations thereof;(b) from 0. 1 to 8 wt% of one or more water-soluble antioxidant;(c) from 0.01 to 3 wt. % one or more oil-soluble antioxidant;(d) from 10 to 30 wt.% of one or more oil-soluble or oil-dispersible sunscreen components.

6. The oil in water emulsion of any preceding claim, wherein the one or more emulsion further comprises (e) a triglyceride, wherein, optionally: i) the triglyceride is a C3-C 12 triglyceride, optionally caprylic / capric triglyceride; and / or ii) the triglyceride is present in an amount of at least 10 parts by weight of the retinoid, such that the ratio of (a):(b):(c) : (e) is l :at least 1 : at least 0. 1 : at least 10.

7. The oil in water emulsion of any preceding claim, wherein the one or more retinoid is all-trans retinol, all-trans retinal, all-trans retinoic acid or a combination thereof.

8. The oil in water emulsion of any preceding claim, wherein the one or more water soluble antioxidant comprises: i) ascorbic acid, sodium ascorbate, sodium sulfite, sodium metabisulfite, sodium bisulfite, sodium thiosulfite, sodium formaldehyde sulfoxylate, isoascorbic acid, thioglycerol, thiosorbitol, thiourea, thioglycolic acid, cysteine hydrochloride, 1,4- diazobicyclo(2.2.2)octane, or combinations thereof; or ii) ascorbic acid, isoascorbic acid, L-ascorbic acid, ascorbyl glucoside, ethyl ascorbic acid, sodium ascorbyl phosphate, magnesium ascorbyl phosphate or cosmetically acceptable salts thereof; or iii) sodium ascorbate.

9. The oil in water emulsion of any preceding claim, wherein the oil-soluble antioxidant comprises ascorbyl palmitate, alpha- tocopherol, phenyl- [alpha] - naphthylamine, tocopherol acetate, ascorbyl tetraisopalmitate or combinations thereof, optionally wherein the oil-soluble antioxidant is alpha- tocopherol and / or gammatocopherol.

10. The oil in water emulsion of any preceding claim, wherein the one or more oilsoluble or oil-dispersible sunscreen components comprises one or more of broadspectrum UV filter, wherein, optionally, the broad-spectrum UV filter comprises bisethylhexyloxyphenol methoxyphenyl triazine, drometrizole trisiloxane or a combination thereof.1 1 . The oil in water emulsion of any preceding claim, wherein the emulsion further comprises at least 5 wt. % of alkyl benzoates, optionally C 12-C15 alkyl benzoates.

12. The oil in water emulsion of any preceding claim, wherein the emulsion comprises one or more emulsifier and wherein the one or more emulsifier comprises polyethylene glycol 20 sorbitan monolaurate (Polysorbate 20) , polyethylene glycol 5 soya sterol, Steareth-20, Ceteareth-20, PPG-2 methyl glucose ether distearate, Ceteth- 10, Polysorbate 80, cetyl phosphate, potassium cetyl phosphate, diethanolamine cetyl phosphate, Polysorbate 60, glyceryl stearate, PEG- 100 stearate, polyoxyethylene 20 sorbitan trioleate (Polysorbate 85) , sorbitan monolaurate, polyoxyethylene 4 lauryl ether sodium stearate, polyglyceryl-4 isostearate, hexyl laurate, steareth-20, ceteareth- 20, PPG-2 methyl glucose ether distearate, ceteth-10, diethanolamine cetyl phosphate, glyceryl stearate, PEG-100 stearate, cetearyl glucoside, polyglyceryl- 6 stearate and polyglyceryl-6 behenate and combinations thereof.

13. The oil in water emulsion of any preceding claim, wherein the emulsion comprises at least 15 wt. % of one or more oil-soluble or oil-dispersible sunscreen components by weight of the emulsion.

14. A method of preparing an oil-in-water emulsion according to any preceding claim, the method comprising:(i) combining the (d) oil soluble and / or oil dispersible UV filters and heating the combination to at least 50°C to form a liquid oil phase;(ii) adding to the liquid oil phase the (a) retinoid, (b) tocopherol and (c) sodium ascorbate, and optionally the (e) triglyceride if present;(iii) adding the oil phase to a water phase and homogenising the water phase and the oil phase together to form an oil in water emulsion.

15. A method comprising applying the emulsion according to any one of claims 1 to 13 to skin of a subject.

16. The method of claim 15 wherein the subject is a human.

17. A cosmetic method for improving the condition and / or appearance of the skin and / or lines and / or wrinkles and / or reduce imperfections and / or improve skin firmness and elasticity, comprising topically administering the emulsion according to any one of claims 1 to 13.

18. Use of the emulsion according to any one of claims 1 to 12 for a topical cosmetic application to the skin.

19. Use of the emulsion according to any one of claims 1 to 13 as a non -therapeutic cosmetic treatment to improve the condition of the skin and / or lines and / or wrinkles and / or imperfections and / or skin firmness and elasticity.

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