High concentration retinol compositions

Abstract

A composition, and uses and methods of use of the composition, the composition comprising: (a) at least 0.1 wt.% of a retinoid component selected from the group consisting of retinol, retinaldehyde, retinoic acid, or a combination thereof; (b) one or more water soluble antioxidants; (c) one or more oil soluble antioxidants; (d) 0.1 to 3 wt.% of a thickener component comprising polyacrylic acid, a polyacrylate, a polyacrylamide, a polysaccharide, or a combination thereof; and (e) from 4 to 20 wt.% of an emollient component, the emollient component comprising benzoate, silicone oil, triglyceride, or a combination thereof.

Description

Technical Field

[0001] This invention relates to compositions and methods of using such compositions. More particularly, this invention relates to high-concentration retinol compositions designed to deliver anti-aging skin benefits to the user. Background Technology

[0002] It is well known in the field of cosmetic composition design and manufacturing that skin is negatively affected by both endogenous and exogenous factors. Endogenous factors include hormonal fluctuations, inflammation, disease, and / or the normal aging process. Exogenous factors affecting the skin include environmental influences such as sunlight, wind erosion, humidity, and pollutants. The effects of these factors on the skin lead to problems associated with skin aging, such as the formation of wrinkles, fine lines, age spots, enlarged pores, skin discoloration, roughness, and loss of elasticity.

[0003] A wide variety of over-the-counter and prescription products are available, designed to address signs of aging and / or promote healthier skin. Recently, there has been interest in the use of vitamin A derivatives in this context. Vitamin A and its derivatives are naturally found in the human body and skin, but they need to be converted into retinoic acid by cells to be effective. Therefore, topical application of retinoic acid is highly effective because it does not require any conversion, but it has potential side effects on the skin and is therefore only available by prescription. Since a large proportion of consumers do not have access to products containing retinoic acid, cosmetic manufacturers have turned their attention to retinyl esters in over-the-counter products, and particularly retinol, to address signs of aging and improve skin quality or appearance. Among retinoids, retinol is the most reliable and effective cosmetic alternative to retinoic acid. It binds to surface cell receptors before entering skin cells and is then converted into retinoic acid, which upregulates more than 500 genes related to skin renewal, regeneration, and homeostasis via nuclear receptors, retinoic acid receptors (RAR), and retinoid X receptors (RXR). This is particularly beneficial for sun-exposed skin areas, such as the face, resulting in reduced signs of aging such as dullness and pigmentation. Providing an increased concentration of retinol in the composition enhances these skin benefits.

[0004] In addition to retinol, cosmetic alternatives to retinyl acids are also used, including retinaldehyde and retinyl esters, such as retinyl palmitate.

[0005] One of the major challenges in cosmetic products containing retinoids is stabilizing them. Retinoids can degrade when exposed to oxygen, light, heat, acids, or heavy metals such as iron. Degradation products include β-ionone, cetyl alcohol, or dehydrated vitamin A. Therefore, identifying systems that stabilize retinoids in cosmetic and commercially acceptable compositions is essential to ensuring that retinoids (rather than degradation products) are delivered to the skin.

[0006] Retinyl palmitate is commonly used because esterification stabilizes the compound. However, it has a less pronounced effect on the skin compared to retinol or retinoic acid.

[0007] Retinoids (such as retinol) are known to be stabilized by encapsulation systems. Despite their effectiveness, encapsulation systems still exhibit retinol degradation, and this degradation is exacerbated by increased temperature or exposure to light. Systems in which retinoids are stabilized with antioxidants are also known. Examples of such antioxidants include butylated hydroxytoluene (BHT), ascorbic acid and its derivatives, tocopherols and their esters, butylated hydroxyanisole (BHA), and phenylnaphthalene. Nevertheless, retinoid degradation still occurs in cosmetic compositions, and therefore, stability also depends on physical methods such as oxygen- and light-impermeable packaging, manufacturing and packaging under an inert atmosphere, temperature-controlled storage and transportation, and a short time period (during which the consumer must use the product to obtain the cosmetic benefits of retinoids).

[0008] Formulating cosmetic compositions with retinoid stability requires a trade-off between the overall stability of the cosmetic composition and the desired stability. Typically, ensuring retinoid stability may require components that cause emulsion separation or pH reduction over time.

[0009] The more retinoids incorporated into a composition, the greater these stability challenges become. The necessary increase in stabilizers required to stabilize retinoids reduces the space for other components needed to stabilize the composition.

[0010] Therefore, cosmetic compositions need to be formulated to ensure not only the presence of high levels of retinoids and the long-term stability of the retinoids, but also the long-term stability of the composition as a whole. Summary of the Invention

[0011] The inventors have unexpectedly discovered that a combination of retinoids with water-soluble and oil-soluble antioxidants, as well as specific amounts of thickeners and emollients, provides a stable composition suitable for cosmetic applications, wherein retinoids exhibit enhanced long-term stability even when present at high concentrations.

[0012] Therefore, in a first aspect, the present invention provides a composition comprising: (a) At least 0.1 wt.% of a retinoid component selected from the following: retinol, retinaldehyde, retinoic acid or a combination thereof; (b) One or more water-soluble antioxidants; (c) One or more oil-soluble antioxidants; (d) 0.1 to 3 wt.% of a thickener component, said thickener component comprising polyacrylic acid, polyacrylate, polyacrylamide, polysaccharide, or a combination thereof; and (e) 4 to 20 wt.% of a moisturizing component, said moisturizing component comprising parabens, silicone oils, triglycerides or combinations thereof.

[0013] In a second aspect, the present invention provides the use of the composition of the first aspect in skin application for surface cosmetic purposes.

[0014] In a third aspect, the present invention provides the use of the composition of the first aspect as a non-therapeutic cosmetic treatment to improve skin condition and / or fine lines and / or wrinkles and / or blemishes and / or skin firmness and elasticity.

[0015] In a fourth aspect, the present invention provides a method comprising applying the composition of the first aspect to the skin of a subject.

[0016] In a fifth aspect, the invention also relates to a cosmetic method for improving skin condition and / or appearance and / or fine lines and / or wrinkles and / or reducing blemishes (e.g., pigmentation) and / or improving skin firmness and elasticity, comprising surface application of the composition of the first aspect. Detailed Implementation

[0017] This invention relates to compositions having a high concentration of retinol, which provide enhanced retinol-like stability while maintaining overall composition stability.

[0018] retinoids This invention comprises at least 0.1 wt% of one or more retinols selected from the following: retinol, retinaldehyde, retinoic acid, or combinations thereof. Retinol may include retinol, retinol isomers, or combinations thereof. Retinal (also known as retinaldehyde) may include retinaldehyde, retinaldehyde isomers, or combinations thereof.

[0019] The term "retinol isomers" includes: all-trans-retinol, 13-cis-retinol, 11-cis-retinol, 9-cis-retinol, and 3,4-didehydro-retinol. Preferred isomers are all-trans-retinol, 13-cis-retinol, 3,4-didehydro-retinol, and 9-cis-retinol. Retinol-like substances or retinols may include or consist of all-trans-retinol.

[0020] The term "retinaldehyde isomers" includes 11-cis-retinaldehyde and all-trans-retinaldehyde. Retinols or retinaldehydes can include or consist of all-trans-retinaldehyde.

[0021] Retinoids can be all-trans-retinoids, including all-trans-retinol, all-trans-retinaldehyde, all-trans-retinic acid, or combinations thereof. Retinoids can be selected from all-trans-retinol, all-trans-retinaldehyde, or combinations thereof.

[0022] Retinols become unstable when exposed to light, temperature changes, and oxygen, degrading into less bioactive forms. Previous technologies addressed this instability by encapsulating retinols. Encapsulation is designed to protect retinol substances from or at least reduce degradation, thereby maximizing the bioavailability of retinols to the skin during use. Various mechanisms and materials for encapsulating retinols have been described in the prior art. Examples of encapsulating materials include polymers, surfactant-based vesicles, or liposomes. Retinols in the prior art can be encapsulated using materials selected from the group consisting of: glycosyl emulsifiers, co-emulsifiers, positively charged molecules, solvents, and combinations thereof. One example of an encapsulated retinol raw material is commercially available from Evonik under the trade name InuMax. Other commercially available encapsulated forms of retinol include Cyclasphere retinol from BASF, Microsponge C116A, N720RE, and N709RE from Amcol Health & Beauty Solutions, and Spherulite-R10 from Givaudan.

[0023] The inventors have discovered that a combination of a water-soluble and oil-soluble antioxidant-stabilized retinoid system and specific amounts of thickeners and emollients provides a stable composition suitable for cosmetic applications, wherein retinol exhibits enhanced long-term stability even when present at high concentrations.

[0024] The system of this invention utilizes one or more water-soluble antioxidants and one or more oil-soluble antioxidants to stabilize retinoids. Antioxidants are substances that reduce or prevent the oxidation of substances, either directly by reacting with free radicals or indirectly by inhibiting the generation of free radicals.

[0025] The retinols in a retinol system can be unencapsulated. Unencapsulated means that the retinols are not contained in or absorbed by other materials, thus separating them from the other components in the composition. If the composition is an emulsion, the unencapsulated retinols are in contact with all components of the oil phase in which they reside.

[0026] The compositions of the present invention comprise water-soluble antioxidants. Water-soluble antioxidants may include ascorbic acid or derivatives thereof, sodium ascorbate, sodium sulfite, sodium metabisulfite, sodium bisulfite, sodium thiosulfite, sodium formaldehyde sulfoxylate, isoascorbic acid, thioglycerol, thiosorbitol, thiourea, mercaptoacetic acid, 3-cysteine ​​hydrochloride, 1,4-diazabicyclo(2.2.2)octane, or combinations thereof. Water-soluble antioxidants may include or consist of: ascorbic acid or derivatives thereof, isoascorbic acid, L-ascorbic acid, or cosmetically acceptable salts thereof. Ascorbic acid derivatives may include ascorbate glucoside, sodium ascorbate phosphate, magnesium ascorbate phosphate, ethyl ascorbic acid, or combinations thereof. Water-soluble antioxidants may include or consist of sodium ascorbate.

[0027] 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, one or more water-soluble antioxidants may be present in amounts of 0.1 to 10 wt.%, such as 0.1 to 8 wt.%, or 0.1 to 6 wt.%, or 0.1 to 4 wt.%, or 0.1 to 3 wt.%, or 0.2 wt.% to 8 wt.%, or 0.2 wt.% to 6 wt.%, or 0.2 wt.% to 3 wt.%, or 0.3 wt.% to 6 wt.%, or 0.3 wt.% to 3 wt.%, or 0.3 to 2 wt.%, or 0.3 to 1.5 wt.%, or 0.3 to 1 wt.%.

[0028] One or more oil-soluble antioxidants may include butylated hydroxytoluene (BHT), ascorbyl palmitate, butylated hydroxyanisole (BHA), tocopherol (e.g., [α]-tocopherol) or derivatives thereof, phenyl-[α]-naphthylamine, or combinations thereof. Oil-soluble antioxidants may include or consist of tocopherol (e.g., α-tocopherol or γ-tocopherol). Tocopherol derivatives may include tocopheryl acetate and ascorbyl tetraisopalmitate, or combinations thereof. Oil-soluble antioxidants may include (R,R,R)-α-tocopherol, (all-rac)-α-tocopherol, or combinations thereof.

[0029] In recent years, the use of BHA and BHT has raised safety concerns, and some countries may restrict their use. Therefore, one or more oil-soluble antioxidants may not include BHT, BHA, or a combination thereof. The composition may not contain one or both of BHT and BHA.

[0030] One or more oil-soluble antioxidants may be present in the composition in amounts of at least 0.01 wt.%, such as 0.05 wt.%, 0.1 wt.%, 0.2 wt.%, or 0.3 wt.%. For example, one or more oil-soluble antioxidants may be present in the composition in amounts of: 0.01 to 10 wt.%, such as 0.05 to 10 wt.%, or 0.05 to 8 wt.%, or 0.05 to 6 wt.%, or 0.05 to 4 wt.%, or 0.05 to 3 wt.%, or 0.05 to 1 wt.%, or 0.1 to 10 wt.%, or 0.1 to 6 wt.%, or 0.1 to 4 wt.%, or 0.1 to 2 wt.%, or 0.1 to 1 wt.%, or 0.3 to 10 wt.%, or 0.3 to 6 wt.%, or 0.3 to 4 wt.%, or 0.3 to 2 wt.%, or 0.3 to 1 wt.%.

[0031] The ratio of (a) retinoids:(b) water-soluble antioxidants:(c) oil-soluble antioxidants can be at least 1:1:at least 0.1. For example, the weight ratio of (a):(b):(c) can 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 from 1:1:1 to 1:3:10, or from 1:1:5 to 1:1:10, or from 1:2:8 to 1:3:10.

[0032] The compositions of the present invention may include retinoids as defined above, which are stabilized by sodium ascorbate as one or more water-soluble antioxidants and tocopherol as one or more oil-soluble antioxidants.

[0033] The composition may further include (f) triglycerides. Triglycerides are emollients. The triglycerides may be C3 to C16 triglycerides, such as C6 to C12 triglycerides. Examples include tripalmitin and caprylic / capric triglycerides. In one example, the triglyceride is caprylic / capric triglyceride.

[0034] Triglycerides may be present in a ratio of at least 1:10 of (a) retinoids:(f) triglycerides. The ratio of (a) retinoids:(b) water-soluble antioxidants:(c) oil-soluble antioxidants:(f) triglycerides may be at least 1:1:0.1:10. For example, the weight ratio of (a):(b):(c):(f) may be from 1:1:0.1:10 to 1:100:100:100, or from 1:1:1:10 to 1:5:10:50, or from 1:1:1:10 to 1:3:10:50, or from 1:1:5:10 to 1:1:10:50, or from 1:2:8:10 to 1:3:10:50, or from 1:1:1:10 to 1:10:5:100.

[0035] Retinols may be present in amounts of at least 0.1 wt.%, such as at least 0.2 wt.%, or at least 0.3 wt.%. For example, retinols may be present in amounts of 0.1 wt.% to 3 wt.%, or 0.2 wt.% to 3 wt.%, or 0.3 wt.% to 3 wt.%, or 0.2 to 2 wt.%, or 0.3 to 1.5 wt.%.

[0036] By using high-concentration retinol-like compositions, such as compositions comprising at least 0.1 wt.% retinol, retinoic acid, and / or retinal, particularly compositions comprising at least 0.3 wt.% retinol, retinoic acid, and / or retinal, more significant beneficial effects on skin renewal, regeneration, and homeostasis can be achieved compared to compositions comprising less than 0.1 wt.% retinol, retinoic acid, and / or retinal.

[0037] Retinoids stabilized by water-soluble and oil-soluble antioxidants are commercially available under the trade name RetiSTAR (BASF). The retinoids of the present invention can be provided in the composition as RetiSTAR (BASF).

[0038] Stable Composition The inventors have unexpectedly discovered that combining retinoids, water-soluble antioxidants, and oil-soluble antioxidants with specific amounts of thickener components and emollient components produces a stable composition in which the retinoids exhibit superior stability compared to retinoids, water-soluble antioxidants, and oil-soluble antioxidants without specific amounts of thickener and emollient components.

[0039] Not wanting to be bound by theory, these components are believed to provide stability to retinoids through two mechanisms. Thickeners reduce the amount of free water in the composition by binding with water. This mechanism theoretically reduces the amount of water available for retinoid oxidation. Specific amounts of thickeners and emollients in the composition also enhance the stability of the oil phase of the composition where retinoids reside. This stable oil phase more effectively isolates water and oxygen, meaning that retinoids are protected from oxidation by these compounds.

[0040] Thickener components The composition comprises 0.1 to 3 wt.% of a thickener component.

[0041] Thickener components may include or consist of the following: polyacrylic acid, polyacrylate, polyacrylamide, polysaccharides, or combinations thereof.

[0042] Typically, thickeners are added to compositions to modify their rheological properties to suit the intended application. In this invention, they have been found to stabilize both the composition and the retinoids within it. Thickeners may also be referred to as viscosity modifiers or gelling agents.

[0043] Polyacrylic acid can include homopolymers and copolymers. Acrylic polymers may or may not be crosslinked to form crosslinked polymers. Polyacrylic acid is also known as carbomer.

[0044] Polyacrylates can be alkyl acrylate crosspolymers or copolymers. Polyacrylates may be selected from acrylic / C10-30 alkyl acrylate crosspolymers, acrylic / behenol-25 methacrylate copolymers, acrylamide / sodium acryloyl dimethyl taurate copolymers, polyacrylate-13, hydroxyethyl acrylate / sodium acryloyl dimethyl taurate copolymers, sodium polyacrylate, polyacrylate crosspolymer-6, or combinations thereof.

[0045] Polyacrylamide can include homopolymers and copolymers. Polyacrylamide can be selected from polyacrylamide, acrylamide / sodium acryloyldimethyl taurate copolymer, ammonium acryloyldimethyl taurate / VP copolymer, or combinations thereof.

[0046] Acrylic / C10-30 alkyl acrylate crosspolymers are copolymers. Acrylic / C10-30 alkyl acrylate crosspolymers are formed when C10-30 acrylates are combined with monomers of acrylic acid and methacrylic acid. Carbomer is a polymer of acrylic acid monomers, while acrylic / C10-30 alkyl acrylate crosspolymers include mixtures of acrylic acid and methacrylic acid. The specific acrylic / C10-30 alkyl acrylate crosspolymers used in the polymer blends and compositions in this example are CARBOPOL ULTREZ-21, available from Lubrizol, or Pemulen EZ-4U, both with the INCI name: "Acrylic / C10-30 alkyl acrylate crosspolymer".

[0047] Polysaccharides may include cellulose, modified cellulose (such as hydroxyethyl cellulose or hydroxymethyl cellulose), hemicellulose, lignocellulose, starch, inulin, guar gum, xanthan gum, pullulan, agar-agar, sodium alginate, potassium alginate or ammonium alginate, carrageenan, dextran, red alginic acid, gellan gum, gum arabic, astragalus gum, hyaluronic acid, konjac mannan, lignin sulfonate, carob gum, partially N-acetylated chitin, pectin, polydextrose, rhamsan gum, galactomannan, alkyl galactomannan (e.g., C1-C5 alkyl galactomannan), velan gum, scleotium gum, gum arabic, or combinations thereof. For example, polysaccharides may include or consist of: modified cellulose, xanthan gum, carrageenan, galactomannan, alkyl galactomannan, gum arabic, scleotium gum, gum arabic, or combinations thereof. Polysaccharides may include or consist of xanthan gum.

[0048] Polysaccharides can have a molecular weight of 10,000 to 20,000,000 g / mol, for example, 30,000 to 10,000,000 g / mol.

[0049] Thickeners may include or consist of the following: acrylic / C10-30 alkyl acrylate crosspolymers, ammonium acryloyldimethyl taurate / VP copolymers, xanthan gum, alkyl galactomannan, or combinations thereof. For example, thickeners may include or consist of the following: a combination of acrylic / C10-30 alkyl acrylate crosspolymers, ammonium acryloyldimethyl taurate / VP copolymers, and xanthan gum.

[0050] The thickener is present in the composition in an amount of 0.1 to 3 wt.%. For example, the thickener may be present in amounts of 0.3 to 3 wt.%, 0.5 to 3 wt.%, 0.7 to 3 wt.%, 0.1 to 2.5 wt.%, 0.1 to 2 wt.%, or 0.1 to 1.5 wt.%. (d) The thickener may also be present in a (a) retinol:(d) thickener weight ratio of 1:1 to 1:30, such as 1:1 to 1:20.

[0051] emollient components The composition comprises 4 to 20 wt.% of an emollient component. The emollient component includes parabens, silicone oils, triglycerides, or combinations thereof.

[0052] Typically, emollients are added to compositions to soothe and soften the skin. In this invention, they have been found to stabilize both the composition and the retinoids within it.

[0053] Benzoate esters are organic compounds made from benzoic acid, wherein the hydroxyl functional group is replaced by different functional groups. The benzoate esters of the present invention may include or consist of: alkyl benzoate esters (also known as alcohol benzoate esters), wherein the alcohol component has a carbon chain length of C3 to C20, for example C5 to C20, C10 to C20, C12 to C20, C3 to C15, C10 to C15, or C12 to C15. The benzoate esters of the present invention may include or consist of C12-15 alkyl benzoate esters.

[0054] Silicone oil may include or consist of the following: polydimethylsiloxane, polydimethylsiloxane alcohol, or a combination thereof.

[0055] Silicone oils may include or consist of polydimethylsiloxanes. Polydimethylsiloxanes may include alkyl-substituted polydimethylsiloxanes with neutralized high molecular weights, such as cetyl polydimethylsiloxane and octyl polymethylsiloxane, or combinations thereof. The molecular weight of the polydimethylsiloxane can be defined by the viscosity of the resulting fluid; for example, the polydimethylsiloxane may be defined as a 20 centitrate (Cst) polydimethylsiloxane. Therefore, silicone oils may include or consist of polydimethylsiloxanes of 1 to 1000 Cst, such as polydimethylsiloxanes of 1.5 to 800 Cst, 2 to 600 Cst, or 10 to 50 Cst.

[0056] Silicone oils may include or be composed of polydimethylsiloxane alcohols. Polydimethylsiloxane alcohols may include neutralized high molecular weight polydimethylsiloxane alcohols.

[0057] Emollients may include or consist of triglycerides. Triglycerides may be C3 to C16 triglycerides, such as C6 to C12 triglycerides. Examples include tripalmitin and caprylic / capric triglycerides. In one example, the triglyceride is caprylic / capric triglyceride.

[0058] Emollient components may include or consist of the following: C12-15 alkyl benzoate, glycerin, caprylyl glycol, ethylhexylglycerin, or combinations thereof. For example, an emollient may include or consist of the following: a combination of C12-15 alkyl benzoate, glycerin, caprylyl glycol, and ethylhexylglycerin.

[0059] The emollient component is present in the composition in an amount of 4 to 20 wt.%. For example, the emollient may be present in the following amounts: 4.5 to 10 wt.%, 5 to 10 wt.%, 5.5 to 6 wt.%, 4 to 18 wt.%, 4 to 15 wt.%, 4 to 10 wt.%, 4 to 9.5 wt.%, 4 to 8.5 wt.%, 4 to 8 wt.%, 4 to 7.5 wt.%, or 4 to 7 wt.%. (e) The emollient may also be present in a weight ratio of (a) retinol to (e) emollient, such as 1:10 to 1:100, from 1:1 to 1:2000.

[0060] The emollient component can be water-insoluble. That is, the emollient component can have a solubility in water at 20°C of less than 0.1 g / 100 g. If the composition is an emulsion, the emollient can be located in the oil phase.

[0061] Stable active ingredients The inventors further identified several active ingredients that further contribute to the stability of retinol. These active ingredients are: (i) pentaerythritol tetra(bis-tert-butylhydroxyhydrocinnamic acid) ester, (ii) camellia (Camellia japonica) flower extract, (iii) quercus petraea fruit extract, (iv) phyllanthus emblica, (v) PEG-7 glyceryl cocoate, (vi) bis-ethylhexylhydroxydimethoxybenzyl malonate, (vii) trioleic acid glyceride, and (viii) dimethylmethoxychromol. In the presence of these stabilizing active ingredients, the stability of retinol in the composition is improved compared to compositions in which these active ingredients are absent.

[0062] The compositions of the present invention may further include one or more of these stable active ingredients (i) to (viii).

[0063] To stabilize the retinoids in the composition, one or more of these stabilizing active ingredients (i) to (viii) may be used instead of the water-soluble antioxidants, oil-soluble antioxidants, thickeners, and emollients as defined above. Such compositions are referred to herein as retinoid compositions with active ingredients.

[0064] The compositions of the present invention or retinoid compositions having active ingredients may include one or more of the following: (i) pentaerythritol tetra(bis-tert-butylhydroxyhydrocinnamic acid) ester, (ii) herbal plant extract Camellia extract, (iii) herbal plant extract Quercus sessiliflora fruit extract, (iv) natural extract Phyllanthus emblica, (v) PEG-7 glyceryl cocoate, (vi) bis-ethylhexylhydroxydimethoxybenzylmalonate, (vii) trioleic acid glyceride, and (viii) dimethylmethoxychromol, such as two or more, three or more, four or more, five or more, six or more, or a combination of all stable active ingredients (i) to (viii).

[0065] One or more of the stable active ingredients may be present in the following amounts: at least 0.01 wt.%, such as at least 0.05 wt.%, such as at least 0.1 wt.%, such as at least 1 wt.%, such as at least 3 wt.%, at least 5 wt.% or at least 7 wt.%, 0.01 to 15 wt.%, 1 to 12 wt.%, 1 to 10 wt.%, 3 to 12 wt.% or 5 to 12 wt.%. One or more of the stable active ingredients may be present in the following amounts: not more than 20 wt.%, such as not more than 15 wt.%, not more than 12 wt.% or not more than 10 wt.%.

[0066] The compositions of the present invention, or retinoid compositions having active ingredients, may include specific amounts of each stable active ingredient. For example, the composition may include 0.01 to 1 wt.% of (i) pentaerythritol tetra(bis-tert-butylhydroxyhydrogenated cinnamic acid) ester, such as 0.05 to 0.5 wt.%. The composition may include 0.01 to 4 wt.% of (ii) the herbal extract Camellia oleifera extract, such as 1 to 3 wt.%. The composition may include 0.01 to 4 wt.% of (iii) the herbal extract Quercus sessiliflora fruit extract, such as 1 to 3 wt.%. The composition may include 0.01 to 4 wt.% of (iv) the natural extract Phyllanthus emblica, such as 1 to 3 wt.%. The composition may include 0.01 to 4 wt.% of (v) PEG-7 glyceryl cocoate, such as 1 to 3 wt.%. The composition may include 0.01 to 4 wt.% of (vi) bis-ethylhexylhydroxydimethoxybenzyl malonate, such as 0.1 to 2.5 wt.%. The composition may include 0 to 4 wt.% of (vii) trioleic acid glyceride, such as 1 to 3 wt.%. The composition may include 0 to 4 wt.% of (viii) dimethylmethoxychromolate, such as 1 to 3 wt.%.

[0067] The compositions of the present invention or retinoid compositions having active ingredients may include specific amounts of each stable active ingredient in combination with other stable active ingredients. For example, the composition may include 0 to 1 wt.% of (i) pentaerythritol tetra(bis-tert-butylhydroxyhydrogenated cinnamic acid) ester (such as 0.05 to 0.5 wt.%), combined with 0 to 4 wt.% of (ii) herbal plant extract camellia flower extract (such as 1 to 3 wt.%), combined with 0 to 4 wt.% of (iii) herbal plant extract ossificans oak fruit extract (such as 1 to 3 wt.%), combined with 0 to 4 wt.% of (iv) natural extract amla (such as 1 to 3 wt.%), combined with 0 to 4 wt.% of (v) PEG-7 glyceryl cocoate (such as 1 to 3 wt.%), combined with 0 to 4 wt.% of (vi) bis-ethylhexylhydroxydimethoxybenzyl malonate (such as 0.1 to 2.5 wt.%), combined with 0 to 4 wt.% of (vii) trioleic acid glyceride (such as 1 to 3 wt.%), combined with 0 to 4 wt.% of (vii) trioleic acid glyceride (such as 1 to 3 wt.%), combined with 0 to 4 wt.% of (viii) dimethylmethoxychromogenol (such as 1 to 3 wt.%).

[0068] Composition The composition may be a cosmetic composition. A cosmetic composition refers to a product designed for consumer use, and is preferably a skin care cosmetic composition, more preferably a facial skin care cosmetic composition.

[0069] The compositions of the present invention can be single-phase or multiphase systems. The compositions can be, but are not limited to, liquids, gels, balms, oils, or solids. Single-phase or multiphase compositions are contemplated. Multiphase systems include, but are not limited to, microemulsions, emulsions, and products having discrete phases. Emulsions include water-in-oil emulsions, oil-in-water emulsions, and multiple emulsions (e.g., water-in-oil-in-water emulsions or oil-in-water-in-oil emulsions). Products having discrete phases include two-phase or three-phase systems in which a separate aqueous or oil phase can be clearly seen. Preferably, the composition is an emulsion.

[0070] When the composition is an emulsion, it comprises an oil phase and an aqueous phase. The oil phase of the emulsion may be provided by any suitable oily component. Suitable oils for the oil phase may include, for example: (a) hydrocarbon oils, such as alkanes or mineral oils; (b) waxes, such as beeswax or paraffin wax; (c) natural oils, such as sunflower oil, almond oil, shea butter, or jojoba oil; (d) silicone oils, such as polydimethylsiloxane, organosilicon elastomers, cyclodimethylsiloxane, or cetyldimethylsiloxane; (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, such as blends of waxes commercially available under the trade name Cutina® (BASF).

[0071] The emulsion may include 0.1% to 55% of an oil phase by weight. The emulsion may include 3% to 25% of an oil phase by weight, such as 5% to 20% by weight. The emulsion may include 10% to 50% of an oil phase by weight, such as 25% to 50% by weight.

[0072] The oil phase of an emulsion may comprise a combination of oils, waxes, or seed fats. Waxes and seed fats are hydrocarbons composed of long aliphatic alkyl chains and may include aromatic groups. They are typically lipophilic and are usually solid or malleable at room temperature. Melting points vary depending on the alkyl chain, chain length, and association. Silicone waxes are a preferred type of suitable wax based on alkylmethylsiloxanes. Oils are typically lipophilic and are liquid at room temperature, with a lower molecular weight than waxes. When present, waxes or seed fats may be present in the oil phase of an emulsion up to 40%. The oil phase may contain up to 20% of the emulsion oil phase level of waxes or seed fats. The oil phase may contain up to 10% of the emulsion oil phase level of waxes or seed fats.

[0073] When the composition is an emulsion, it may include an emulsifier. The composition may include 0.1% to 10% by weight of an emulsifier, such as 0.25% to 7.5% or 0.5% to 5% emulsifier. The emulsifier helps to disperse and suspend the aqueous phase in the oil phase.

[0074] emulsifier The compositions of the present invention may include emulsifiers. Suitable emulsifiers include all those suitable for this purpose and known to those skilled in the art for use in skin care products. When the emulsion is a water-in-oil emulsion, these emulsifiers have an HLB value of 14 or less, more preferably 2 to 14, and still more preferably 4 to 14. When the emulsion is an oil-in-water emulsion, the surfactant may have an HLB value greater than 8, such as 8 to 18, or 10 to 16.

[0075] Emulsifiers may include one or more types of emulsifiers. The emulsifiers used herein are various nonionic and anionic emulsifiers, such as sugar esters and polyesters, alkoxylated sugar esters and polyesters, C... l -C 30 C of fatty alcohols l -C 30 Fatty acid esters, C l -C 30 C of fatty alcohols l -C 30 Alkoxylated derivatives of fatty acid esters, C l -C 30 Alkoxylated ethers of fatty alcohols, C l -C 30 Polyglycerol esters of fatty acids, C of polyols l -C 30 C of esters and polyols l -C 30 Ethers, alkyl phosphates, polyoxyethylene fatty ether phosphates, fatty acid amides, acyl lactates, soaps, and combinations thereof. Non-limiting preferred examples of these non-silicone-containing emulsifiers include: polyethylene glycol 20 dehydrated sorbitol monolaurate (polysorbate 20), polyethylene glycol 5 soybean sterol, stearyl alcohol polyether-20, cetearyl alcohol polyether-20, PPG-2 methyl glucose ether distearate, cetyl alcohol polyether-10, polysorbate 80, cetyl phosphate, cetyl phosphate potassium, diethanolamine cetyl phosphate, polysorbate 60, glyceryl stearate, PEG. -100 stearate, polyoxyethylene 20 dehydrated sorbitol trioleate (polysorbate 85), dehydrated sorbitol monolaurate, polyoxyethylene 4 lauryl ether sodium stearate, polyglycerol-4 isostearate, hexyl laurate, stearyl alcohol polyether-20, cetearyl alcohol polyether-20, PPG-2 methyl glucose ether distearate, cetyl alcohol polyether-10, diethanolamine cetyl phosphate, glyceryl stearate, PEG-100 stearate and combinations thereof.

[0076] sunscreen The compositions of the present invention may optionally include a sunscreen component. The sunscreen may include organic or inorganic sun filters, or a combination of both. Suitable inorganic sun filters include those selected from the group consisting of: fine titanium dioxide, fine zinc oxide, boron nitride, and combinations thereof.

[0077] Suitable organic sunscreens include those selected from the group consisting of: a) p-aminobenzoic acid, their esters and derivatives (e.g., 2-ethylhexyl p-dimethylaminobenzoate), b) methoxycinnamates (e.g., 2-ethylhexyl p-methoxycinnamate, 2-ethoxyethyl p-methoxycinnamate, or α, p-di-(p-methoxycinnamoyl)-α'-(2-ethylhexanoyl)-glycerol), c) benzophenones (e.g., oxybenzophenone), d) benzoylmethanes, such as 4-(tert-butyl)-4'-methoxydibenzoylmethane, e) 2-phenylbenzimidazole-5-sulfonic acid and its salts, f) alkyl-ss, ss-diphenylacrylates, such as α-cyano-ss, ss-alkyl diphenylacrylate, such as octocrylene, g) triazine, such as 2,4,6-triphenylamino-(p-carbonyl-2-ethyl-hexyl-1-oxo)-1,3,5-triazine, h) camphor derivatives such as methylbenzyl camphor, and i) combinations thereof. Other preferred sunscreen ingredients include those selected from the group consisting of: homosalate, ethylhexyl salicylate, diethylhexylbutamidotriazine, bis-ethylhexyloxyphenol methoxyphenyltriazine, diethylaminohydroxybenzoylhexyl benzoate, butyl methoxydibenzoylmethane, methylene bis-benzotriazolyl tetramethylbutylphenol, polysiloxane-15, ethylhexyltriazine, octocrylene, phenylbenzimidazole sulfonic acid, and combinations thereof. The sunscreen agent is optionally present in an amount of 0.1% to 20% by weight of the composition, such as 0.1% to 15% by weight of the composition.

[0078] Dipeptide: The compositions of the present invention may include one or more dipeptides selected from the group consisting of: acetyl dipeptide 1 cetyl ester (tyrosine-arginine), acetyl dipeptide 3 aminohexanoate (alanine-arginine), azeloyl dipeptide 10 (alanine-histidine), coumaroyl dipeptide 3 (alanine-arginine), diceryl dipeptide 9 (glutamic acid-lysine), dipeptide diaminobutyryl benzylamide diacetate, dipeptide 1 (tyrosine-arginine), dipeptide 10 (alanine-histidine), dipeptide 11 (cysteine-lysine), and 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 leucine acetate (alanine-arginine), methyl undecenoyl dipeptide 16 (leucine-leucine), nicotinyl dipeptide 22 (serine-valine), nicotinyl dipeptide 23 (proline-serine), nicotinyl dipeptide 24 (glutamic acid-threonine), nicotinyl 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 diaminobutyryl hydroxythreonine (lysine-valine), palmitoyl dipeptide 5 diaminohydroxybutyrate (lysine-valine), palmitoyl dipeptide 7 (lysine-threonine), and combinations thereof.

[0079] The dipeptide is preferably incorporated into the emulsion of the present invention at a level of 0.1 to 50,000 ppm, more preferably 1 to 5,000 ppm, and most preferably 10 to 500 ppm.

[0080] Purpose and usage The present invention further relates to the use of the compositions of the present invention in skin application for surface cosmetic purposes.

[0081] The present invention also relates to the use of the compositions according to the invention as non-therapeutic cosmetic treatments to improve skin condition and / or fine lines and / or wrinkles and / or blemishes and / or skin firmness and elasticity.

[0082] This invention relates to a method comprising applying a composition according to the invention to the skin of a subject. The subject may be a human being.

[0083] The present invention also relates to a cosmetic method for improving skin condition and / or appearance and / or fine lines and / or wrinkles and / or reducing blemishes (e.g., pigmentation) and / or improving skin firmness and elasticity, the method comprising surface application of a composition according to the present invention.

[0084] All features described herein (including any appended claims and abstract) and / or all steps of any method or process so disclosed may be combined with any of the foregoing aspects or embodiments in any combination, unless otherwise stated with reference to a particular combination, for example, where at least some of such features and / or steps are mutually exclusive combinations.

[0085] definition Unless otherwise stated, all percentages provided herein are by weight percentages of the composition. Unless otherwise stated, all ratios provided herein are by weight.

[0086] Example Composition High-concentration retinol-like compositions were prepared, comprising 0.3 wt.% or 1 wt.% retinol. In comparative examples, retinol was provided in an encapsulated form in an Inumax system comprising retinol. In embodiments of the invention, retinol was provided in an unencapsulated form in a RetiSTAR (BASF) system comprising retinol, caprylic / capric triglycerides, tocopherol, and sodium ascorbate.

[0087] Comparative Example 1: 0.3 wt.% retinol (in Inumax)

[0088] Comparative Example 2: 1.0 wt.% retinol (in Inumax)

[0089] Example 3: 0.3% retinol (in RetiSTAR (BASF))

[0090] Example 4: 1.0% retinol (in RetiSTAR (BASF))

[0091] Stability test The composition was placed in a glass jar for physical stability analysis.

[0092] Viscosity: The viscosity of the samples was determined using a Brookfield LVT viscometer with rotor #4 at 12 rpm for 30 seconds. The viscosity of all compositions followed a similar trend for all samples, initially decreasing over four weeks and then remaining stable up to 13 weeks. The viscosity of the compositions according to the invention is moderately stable for commercial products.

[0093] pH: The pH of the samples was determined using a Mettler Toledo Compact Severn pH meter. The pH of the samples showed natural changes over 13 weeks, but the shift did not exceed + / - 0.5 pH units from the initial pH.

[0094] The pH of the compositions according to the present invention is moderately stable for commercial products.

[0095] Stability analysis To determine the retinol content over time, the composition was saponified, extracted from the aqueous phase, evaporated to dryness, and redissolved in a solvent suitable for HPLC quantification.

[0096] The unsaponifiable material was then extracted into ether. The retinol in this phase was detected by reversed-phase HPLC.

[0097] The comparative analysis shows the retinol content at 0 months (initial) and 3 months. Tests were conducted according to embodiments of the invention after storage at 23°C or 40°C for 0 months (initial), 3 months, and 7 months.

[0098] The retinol content of RetiSTAR (BASF) at 0 months (initial) and 3 months in the base O / W emulsion is also provided. This base O / W emulsion does not contain the specific amounts of thickener and emollient components required by this invention.

[0099] Table 1: Results of Comparative Example 1 containing 0.3% retinol (in Inumax)

[0100] Table 2: Results of Comparative Example 2 containing 1.0% retinol (in Inumax)

[0101] Table 3: Results of O / W base emulsions including 0.1% retinol (in RetiSTAR (BASF))

[0102] Table 4: Results of Example 3 containing 0.3% retinol (in RetiSTAR (BASF))

[0103] Table 5: Results of Example 4 containing 1.0% retinol (in RetiSTAR (BASF))

[0104] The analytical results according to embodiments of the present invention were compared with those of comparative examples containing 0.3% retinol (Inumax) or 1.0% retinol (Inumax) and with the results of RetiSTAR in O / W base emulsions.

[0105] Based on the percentage of retinol remaining after 3 months, the results of Comparative Example 1 showed that 83.33% retinol was detected after 3 months at 23°C, and 63.33% retinol was detected after 3 months at 40°C. The results of Comparative Example 2 showed that 90.29% retinol was detected after 3 months at 23°C, and 82.52% retinol was detected after 3 months at 40°C.

[0106] RetiSTAR in the O / W base emulsion showed that after 3 months at 40°C, the retinol content was 92%.

[0107] Based on the percentage of retinol remaining after 3 months, Example 3 showed a retinol remaining amount of 79.31% after 3 months at 23°C and 93.10% after 3 months at 40°C; while Example 4 showed a retinol remaining amount of 98.95% after 3 months at 23°C and 93.10% after 3 months at 40°C. Example 3 also showed a retinol remaining amount of 106.90% after 7 months at 23°C and 93.10% after 7 months at 40°C. Example 4 showed a retinol remaining amount of 106.32% after 7 months at 23°C and 98.95% after 7 months at 40°C.

[0108] Examples 3 and 4 of the invention demonstrate improved retinol stability, exceeding that of Comparative Examples 1 and 2 (wherein the retinol was encapsulated). Examples 3 and 4 also demonstrate improved retinol stability, exceeding that of RetiSTAR (BASF) in O / W base emulsions, although the amounts of retinol contained in Examples 3 and 4 are four times and twelve times, respectively, the amount in O / W bases containing RetiSTAR.

[0109] Stable active ingredients The effects of the following stabilizing active ingredients on the stability of retinol were also investigated: (i) pentaerythritol tetra(bis-tert-butylhydroxyhydrocinnamic acid) ester, (ii) camellia flower extract, (iii) Quercus sessiliflora fruit extract, (iv) amla, (v) dioctyl carbonate, (vi) bis-ethylhexylhydroxydimethoxybenzylmalonate, and (vii) trioleic acid glyceride.

[0110] Example 5: 0.3% retinol (in RetiSTAR (BASF)) + stabilized active ingredient

[0111] Example 6: 1.0% retinol (in RetiSTAR (BASF)) + stabilized active ingredient

[0112] The stability of retinol was assessed using the methods described above. Data were collected at 0 months (initial), 3 months, and 7 months.

[0113] Table 6: Analysis Results of Example 5

[0114] Table 7: Analysis Results of Example 6

[0115] Based on the percentage of retinol remaining after 3 months, Example 5 showed a retinol remaining of 89.66% after 3 months at 23°C and 96.55% after 3 months at 40°C; while Example 6 showed a retinol remaining of 98.86% after 3 months at 23°C and 106.82% after 3 months at 40°C. Example 5 also showed a retinol remaining of 106.90% after 7 months at 23°C and 96.55% after 3 months at 40°C. Example 6 showed a retinol remaining of 111.36% after 7 months at 23°C and 110.23% after 7 months at 40°C. The physical stability of the compositions of Examples 5 and 6 was evaluated, and the results are comparable to those of Examples 3 and 4.

[0116] Therefore, the addition of a stabilizing agent to the composition further improves the stability of retinol compared to the compositions of Examples 3 and 4, in which no stabilizing active agent is present.

[0117] As previously stated, RetiSTAR is sourced from BASF. RetiSTAR 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% of retinol - INCI list: caprylic / capric triglycerides (and) sodium ascorbate (and) tocopherol (and) retinol.

Claims

1. A composition comprising: (a) At least 0.1 wt.% of a retinoid component selected from the following: retinol, retinaldehyde, retinoic acid or a combination thereof; (b) One or more water-soluble antioxidants; (c) One or more oil-soluble antioxidants; (d) 0.1 to 3 wt.% of a thickener component, said thickener component comprising polyacrylic acid, polyacrylate, polyacrylamide, polysaccharide, or a combination thereof; and (e) 4 to 20 wt.% of a moisturizing component, said moisturizing component comprising parabens, silicone oils, triglycerides or combinations thereof.

2. The composition according to claim 1, wherein, The weight ratio of a:b:c is at least 1:at least 0.

1.

3. The composition according to any one of the preceding claims, wherein: i) The emollient includes triglycerides, optionally in combination with one or more of parabens and silicone oils, and / or ii) The triglyceride thereon is a C3-C12 triglyceride, optionally a dioctanoic acid / capric acid triglyceride.

4. The composition according to any one of the preceding claims, wherein: i) One or more types of retinol are all-trans retinols, and / or ii) The one or more types of retinol include retinol, retinaldehyde, or combinations thereof, and / or iii) The one or more types of retinol are present in an amount of at least 0.3 wt.%, and / or iv) The one or more types of retinol are present in an amount of 0.1 wt.% to 3 wt.%, optionally 0.03 wt.% to 3 wt.%.

5. The composition according to any one of the preceding claims, wherein, The weight ratio of a:b:c is from 1:1:0.1 to 1:100:

100.

6. The composition according to any one of the preceding claims, wherein, The one or more water-soluble antioxidants include ascorbic acid, sodium ascorbate, sodium sulfite, sodium metabisulfite, sodium bisulfite, sodium thiosulfite, sodium formaldehyde sulfoxylate, isoascorbic acid, thioglycerol, thiosorbitol, thiourea, mercaptoacetic acid, cysteine ​​hydrochloride, 1,4-diazabicyclo(2.2.2)octane or combinations thereof, optionally, wherein the one or more water-soluble antioxidants include ascorbic acid, isoascorbic acid, L-ascorbic acid, ascorbate glucoside, ethyl ascorbic acid, sodium ascorbate phosphate, magnesium ascorbate phosphate or cosmetically acceptable salts thereof, or wherein.

7. The composition according to any one of the preceding claims, wherein, The oil-soluble antioxidant includes ascorbyl palmitate, α-tocopherol, phenyl-[α]-naphthylamine, tocopheryl acetate, ascorbyl tetraisopalmitate, or combinations thereof, wherein the oil-soluble antioxidant is optionally α-tocopherol.

8. The composition according to any one of the preceding claims, wherein: i) The silicone oil is selected from polydimethylsiloxane, polydimethylsiloxane alcohol, or a combination thereof, or ii) The emollients include C12-15 alkyl benzoate, polydimethylsiloxane, polydimethylsiloxane alcohol, caprylic / capric triglyceride, or combinations thereof.

9. The composition according to any one of the preceding claims, wherein, The thickener includes acrylic / C10-30 alkyl acrylate crosspolymers, ammonium acryloyl dimethyl taurate / VP copolymers, xanthan gum, polyacrylic acid, acrylic / C10-30 alkyl acrylate crosspolymers, acrylic / behenol polyether-25 methacrylate copolymers, acrylamide / sodium acryloyl dimethyl taurate copolymers, polyacrylate-13, hydroxyethyl acrylate / sodium acryloyl dimethyl taurate copolymers, sodium polyacrylate, polyacrylate crosspolymer-6, polyacrylamide, acrylamide / sodium acryloyl dimethyl taurate copolymers, or combinations thereof, optionally. The thickeners mentioned above include acrylic / C10-30 alkyl acrylate crosspolymers, ammonium acryloyl dimethyl taurate / VP copolymers, xanthan gum, or combinations thereof.

10. The composition according to any one of the preceding claims, wherein: i) The composition further comprises one or more peptides selected from the group consisting of palmitoyl oligopeptide, palmitoyl tetrapeptide 3, acetyl dipeptide-1 cetyl ester, and combinations thereof, optionally in an amount of 4 to 10 wt.%, and / or ii) The composition further comprises one or more of the following: pentaerythritol tetra(bis-tert-butylhydroxyhydrocinnamic acid) ester, camellia japonica flower extract, quercus petraea fruit extract, phyllanthus emblica, PEG-7 glyceryl cocoate, bis-ethylhexylhydroxydimethoxybenzyl malonate, trioleic acid glyceride, dimethyl methoxychromogenol, or combinations thereof.

11. The composition according to any one of the preceding claims, wherein, The composition is an emulsion, optionally an oil-in-water emulsion, a water-in-oil emulsion, a water-in-oil-in-water emulsion, or an oil-in-water-in-oil emulsion.

12. Use of the composition according to any one of claims 1 to 11 for application to the skin for cosmetic purposes.

13. Use of the composition according to any one of claims 1 to 11 as a non-therapeutic cosmetic treatment to improve skin condition and / or fine lines and / or wrinkles and / or blemishes and / or skin firmness and elasticity.

14. A method comprising applying the composition according to any one of claims 1 to 11 to the skin of a subject.

15. A cosmetic method for improving skin condition and / or appearance and / or fine lines and / or wrinkles and / or reducing blemishes and / or improving skin firmness and elasticity, comprising surface application of the composition according to any one of claims 1 to 11.

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