WO2015004365A1 - Vaporizable silicone-free and ethanol-free cosmetic sunscreen composition - Google Patents

Abstract

The invention relates to a vaporizable anhydrous cosmetic sunscreen composition including a silicone substitute or silicone derivative based on a mixture consisting of: (a) from 50 to 100 % by weight of a mixture of linear paraffins consisting of: (i) 70 to 99 % by weight of at least one linear paraffin selected from the group consisting of the C8, C10 and C12 paraffins, alone or in a mixture, (ii) 1 to 30 % by weight of at least one linear paraffin selected from the group including the C14 to C24 paraffins, alone or in a mixture, (b) at least one non-volatile oil representing less than 50 % by weight of the mixture.

Description

 SOLAR COSMETIC COMPOSITION SPRAYABLE WITHOUT SILICONE AND

 ETHANOL FREE

The subject of the invention is a new photoprotective, anhydrous, vaporizable, silicone-free and ethanol-free (denatured alcohol) cosmetic composition having an in vivo SPF value of at least 30.

Light radiation with a wavelength between 290 nm and 400 nm, corresponding to UVA (wavelength between 320 nm and 400 nm) and UVB (wavelength between 290 nm and 320 nm) are necessary for the proper functioning of the human organism. Nevertheless, they also cause many negative effects. UVB is thus more particularly the cause of erythema, skin burns, while UVA is a priori responsible for the formation of free radicals that are likely to induce long-term skin damage. This UV radiation must be filtered.

To reflect or absorb the UV, two types of filters are used, respectively the mineral filters and the organic filters. Mineral (or physical) UV filters or "screen" substances consist of inert microscopic powders. These small particles reflect the UVA / UVB rays and thus protect the skin from solar radiation. The two permitted UV filters are titanium dioxide (TiO 2) and zinc oxide (ZnO) microfm. These filters are a priori stable once they are subjected to UV radiation. Linked to the safety of users, their use is highly regulated. These filters confer a very good performance vis-à-vis the UV protection, but it is difficult to reconcile high SPF, 100% mineral composition filters and a sensory and visually acceptable galenic. To improve the SPF / sensoriality performance ratio, it is recommended to reduce the particle size. The nanoscreens proposed today are thus the most efficient.

Organic UV (or chemical) filters are substances that absorb UV rays and transform them into thermal radiation. Synthetic sunscreens provide photochemical protection by absorbing energy from ultraviolet rays. The fact that these organic UV filters absorb the UV induces their transformation (leading to toxic degradation) and their deactivation and thus causes a loss of their protective power to UV exposure. This is the phenomenon of photoinstability. Organic or mineral filters, authorized in addition to ZnO for the United States, are precisely listed by European regulation 1223/2009 in Appendix VI. They are listed below:

Chemical name / INN / XAN CAS Number

4-Aminobenzoic acid 150-13-0

 N, N, N-Trimethyl-4- (2-oxoborn-3-ylidenemethyl) anilinium methyl 52793-97-2 sulfate

 Benzoic acid, 2-hydroxy-, 3,3,5-trimethylcyclohexyl ester / 118-56-9

homosalate

 2-Hydroxy-4-methoxybenzophenone / Oxybenzone 131-57-7

 2-Phenylbenzimidazole-5-sulphonic acid and its potassium, sodium 27503-81-7 and triethanolamine salts / Ensulizole

 3,3 '- (1,4-Phenylenedimethylene) bis 92761-26-7 / (7,7-dimethyl-2-oxobicyclo [2.2.1] 90457-82-2 hept-1-ylmethanesulfonic acid) its salts / Ecamsule

 1- (4-tert-Butylphenyl) -3- (4-methoxyphenyl) 70356-09-1 propane-1,3-dione / Avobenzone

alpha- (2-Oxoborn-3-ylidene) toluene-4-sulphonic acid and its salts 56039-58-8

2-Cyano-3,3-diphenyl acrylic acid, 2-ethylhexyl ester / Octocrylene 6197-30-4

Polymer of N - {(2 and 4) - [(2-oxoborn-3-113783 -6-ylidene) methyl] benzyl} acrylamide

 2-Ethylhexyl 4-methoxycinnamate / Octinoxate 5466-77-3

 Ethoxylated Ethyl-4-Aminobenzoate 116242-27-4

Isopentyl-4-methoxycinnamate / Amiloxate 71617-10-2

2,4,6-Trianilino- (p-carbo-2'-ethylhexyl-1'-oxy) -1,3,5-triazine 88122-99-0

Phenol, 155633-54-8

2- (2H-Benzotriazol-2-yl) -4-Methyl-6- (2-Methyl-3- (1,,3,3,3-tetramethyl-1- (trimethylsilyl) oxy) -Disiloxanyl) Propyl)

 Benzoicacid, 154702-15-5

4,4- {[6 - [[4 - [[(1,1-dimethylethyl) amino] carbonyl] phenyl] amino] -1,3,5-triazine-2,4-diyl] diimino} bis-, bis (2-ethylhexyl) ester / Iscotrizinol

 3- (4'-Methylbenzylidene) -dl-camphor / Enzacamene 36861-47-9 /

38102-62-4

 Benzoic acid, 2- [4- (diethylamino) -2-hydroxybenzoyl] - hexyl ester 302776-68-7

Moreover, most of these organic filters have the characteristic of being fat-soluble. Therefore, their formulation involves the implementation of a fatty phase, in proportion even higher than the desired SPF is high. The high fat content combined with organoleptic characteristics intrinsic to organic filters, led to the generalization of silicones in solar products to counterbalance the greasy and sticky touch often reproached to solar products. Silicones have the advantage of offering a spectrum of broad and attractive organoleptic characteristics (non-greasy touch, fast drying). However, silicones are increasingly criticized on the market because of their lack of affinity with the skin and their lack of biodegradability.

Combined with silicones, today's solar compositions on the market mostly contain ethanol, which helps to improve the drying speed and improve the touch. However, here again, the safety of ethanol vis-à-vis the skin especially in the sun (risk of drying and sensitization) is increasingly questioned, so that we are currently looking for alternative solutions . Although organic filters are currently one of the most effective solutions to fight against solar radiation, they are increasingly criticized. Indeed, their over-use has made them potentially harmful to humans and the environment. Thus, during repeated application of solar protectors with high SPF, there is a risk of accumulation in the body of these synthetic molecules photoabsorbent, which can lead to sensitization or (photo) allergies. For example, photosensitization reactions of para-aminobenzoic acid (PABA) and its derivatives have encouraged the use of products without PABA. These filters are also suspected of causing endocrine disruption. When released into the environment, these filters destabilize the environment of flora and fauna (coral reef, natural pool).

The document WO 2009/064790 A1 describes a combination of two volatile oils, C12-C14 and C13-C16, respectively, with a non-volatile oil that is supposed to substitute for silicone oils. This product is incorporated in various cosmetic compositions described in Examples 1 to 4. None of them relate to a solar composition.

The document WO 2010/068661 A1 describes solar compositions containing inorganic filters, and in particular titanium dioxide in the presence of the oils mentioned in the previous document. Example 1 describes an oil-in-water suntan lotion. The proportion of water in the composition is 36.45%. Example 2 describes a sprayable solar milk with a proportion of water of 25%. Example 3 relates to a suntan lotion in which water represents 50.15% by weight of the composition. The presence of water and emulsifier gives the formula a certain instability in contact with water. In other words, the properties of water resistance are not optimal.

WO 2010/115973 A1 discloses cosmetic compositions, in particular for makeup, lips, eyes and nose. The purpose of this document is also to replace silicone oils. To do this, a mixture of parrafines is described. The UV filters appear as possible agents of the composition and are listed in a list among other components. Example 2 describes a dry oil that does not contain a filter and is therefore not a solar composition. The documents MINTEL XP002721446, MINTEL XP002721447 and MINTEL XP002721448 describe compositions respectively having one of SPF 15, 15 and 30. Each of the compositions contains water and coconut alkanes, which do not correspond to the INCI name of the paraffin mixture described in WO 2010/115973 A1.

The problem that the invention proposes to solve is that of developing a solar cosmetic composition devoid of at least silicones or derivatives, advantageously also free of ethanol and preferably free of organic filters, in particular the filters listed herein. -above.

Another object of the invention is to develop a vaporizable solar composition which has optimum properties of water resistance.

In summary, the objective of the invention is to develop a vaporizable composition, resistant to water, containing the least possible substances considered increasingly harmful to the body, and which has a SPF in vivo at least 30 and a pleasant touch, ensuring good compliance.

The Applicant has discovered that the use of a specific non-silicone oil mixture in a photoprotective composition makes it possible to solve the problem posed. More specifically, the subject of the invention is an anhydrous vaporizable solar cosmetic composition comprising a silicone substitute or silicone derivative based on a mixture consisting of:

a mixture of:

 (a) from 50 to 100% by weight of a mixture of linear paraffins consisting of:

 (i) 70 to 99% by weight of at least one linear paraffin selected from the group consisting of C8, C10 and C12 paraffins, alone or in admixture, (ii) 1 to 30% by weight of at least one linear paraffin chosen from the group comprising C 14 to C 24 paraffins, alone or as a mixture,

 (b) at least one non-volatile oil representing less than 50% by weight of the mixture,

In other words, the composition is free of silicone or silicone derivatives.

In the remainder of the description and in the claims, the term "silicone or silicone derivative" denotes chain molecules having an Si-O- unit.

The mixture of a / and b / is described in WO2010 / 115973. The Applicant has found that the implementation of this mixture in a solar composition made it possible to overcome the presence of silicone, while ensuring a fast drying speed and a non-sticky satin feel. In an advantageous embodiment, the silicone substitute or silicone derivative consists solely of the mixture a / + b /.

In addition, it turns out that the organoleptic qualities of the composition (touch and speed of drying) are not affected by the absence of ethanol in the composition. Therefore, and in an advantageous embodiment, the composition of the invention does not contain ethanol.

According to the invention, the linear paraffin mixture is preferably composed of a mixture of dodecane and tetradecane.

In a preferred embodiment, a / consists of dodecane and tetradecane and b / is cococaprylate caprate. Advantageously, the product a / + b / meets the INCI name coconutalkanes (and) cococaprylate caprate.

In addition and according to another characteristic, the mixture of a / and b / represents at least 25% by weight of the composition, preferably at least 40% by weight, advantageously at least 50% by weight of the composition.

To give the composition a protection against solar radiation, the composition contains filters consisting exclusively of mineral filters. In other words, the composition advantageously does not contain organic filters, in particular those listed in the European regulation 1223/2009 in Appendix VI.

To enhance the protective effect, the composition further contains karanja oil preferably between 10 and 50% by weight of the composition. The karanja oil is in practice extracted from the seeds of the Pongamia glabra tree and known under the INCI name "pongamia glabra seed oil". It is known to have UV absorbing properties in the UVB mainly.

According to another essential characteristic of the invention, the composition is anhydrous. Under these conditions, it is devoid of water and advantageously does not contain surfactants. Therefore, the composition of the invention is particularly stable in the presence of water (sea in particular) conferring on it an optimum character of water resistance. The composition of the invention may also contain adjuvants such as those conventionally used in the field of cosmetics, such as active agents, SPF booster agents, antioxidants, complexing agents, solvents, fragrances, fillers, bactericides, electrolytes, odor absorbers, dyes or lipid vesicles. The choice of these adjuvants, as well as their concentrations, must be determined in such a way that they do not modify the properties and advantages sought for the composition of the present invention.

The invention also relates to a method for protecting the skin, the lips, the mucous membranes or the hair with respect to the UVA / B radiation, which consists in applying the composition to the skin, the hair, the lips or the mucous membranes. previously described.

The invention and the advantages thereof will be apparent from the following example.

Example of composition according to the invention:

In vivo SPF and in vitro UVA protection are measured according to the following protocols. AI PROTOCOLS I / SPF in vivo

In vivo SPF is measured according to the method prescribed by Colipa (May 2006) METHOD

 The study takes place over two days.

 1. Day 1 1.1 Determination of skin type

Fitzpatrick's definitions of skin phototypes were based on a primary exposure of the sun 30-40 minutes after winter or a non-exposure period of equal duration.

• Type I: always burns easily, never tans

 • Type II: always burn easily, lightly bronze

 • Type III: moderately burned, bronze

 • Type IV: burns weakly, bronze always easily

 · Type V: rarely burns, intensely burns

 • Type VI: never burns, highly pigmented

The skin color categories were defined according to the color criteria of A. Chardon et al. (1990) using the color space of the International Commission on Illumination (CIE) L * a * b * (1976):

 • Very Claire: value ITA °> 55 °

 • Clear: value ITA ° 41 ° - 55 °

 • Intermediate: value ITA ° 28 ° - 4 F

 • Mate: value ITA ° 10 ° - 28 °

 · Brown: value ITA ° - 30 ° - 10 °

 • Black: value ITA ° <- 30 °

ITA is calculated by chromometric measurements performed on subjects. Three successive measurements were taken for the calculation of the angle.

This angle is calculated using the following formula:

ITA ° = [Arctan (L * - 50) / b *)] x 180 / π 1.2. Determination of zones

A number between 1 and n is assigned to each volunteer, according to their order of arrival in the study.

The subjects are placed in a ventral position and must not move or change position for the entire duration of the exposure. The position must be the same for both the exposure and the evaluation of DEM [Minimal Erythema Dose].

The measurements and the application of the studied products were carried out on the back of the subject, each zone is located between the shoulder blades and the size on both sides of the spine and an area of 40 cm ² (8 x 5 cm). The back is divided into six areas that have been randomized (see diagram below): Scapulae

Cut

On test sites 1-6, there are:

 - An unprotected site

 - A test site with the reference product P

 - One to four sites with the tested product (4 products tested maximum by volunteers)

1.3. UV exposure of the control site and immediate registration of the skin reaction

A geometric series of 6 exposures (r = 1.25) was administered on the control site, with 1 sub-site corresponding to the lowest UV dose, the 4th sub-site corresponding to the theoretical DEM. After the UV exposure was completed, all immediate skin reactions were recorded (reddening, pigmentation, etc.). 1.4. Product Application and Exposure

The product was applied with a fingerstall, at a rate of 2 mg / cm ² for 20 to 50 seconds, with a slight pressure.

The application of the product is followed by a waiting period of at least 15 minutes.

 For each site, there are 6 doses exposed to UV, with a UV dosage adjusted according to the desired sun protection factor of the tested product (SPF X):

Après la fin de l'exposition, toutes les réponses immédiates ont été enregistrées (le rougissement immédiat, la pigmentation immédiate, etc.).

After the end of the exposure, all immediate responses were recorded (immediate reddening, immediate pigmentation, etc.).

2. Day 2 2.1. Determination of DEM

The observer evaluated the erythema responses on each subject blindly, without knowledge of the randomization of the sites. Erythemal Minimal Dose is defined as the amount of energy required to produce the first unambiguous visible erythema with bounded margins, evaluated 16-24 hours after exposure to a solar simulator, with 6 increasing doses of UV (25% progression) . 2.2. Determination of DEM on protected sites

The DEM on the protected sites (tested products and reference product) was determined in the same way as on the control site. DATA ANALYSIS

1. Determination of the SPF The individual SPF was calculated as follows:

MED p (ml / cm ² )

 SPFi = -

MED np (m / cm ² )

p = protected skin

np = unprotected skin The average SPF for each tested product and the reference product was calculated as follows

ΣSPFi

 Average SPF

 11

n = number of volunteers analyzed

The standard deviation was calculated as follows:

The SEM was calculated as follows:

SEM = ^s i

n = number of volunteers analyzed in the study

s = standard deviation of the average FPS

 SEM% = standard error as% of average

s = écart type de la moyenne du FPS individuel The 95% confidence interval (A) is calculated as follows

s = standard deviation of the average individual SPF

t = value found in the Student's table with an alpha error of a = 0.05 and a degree of freedom dev = n-1 The claimed SPF is the lower limit of the 95% confidence interval, that is, the nearest whole number obtained by the following formula:

Average SPF - 95% CI

To validate the method, the mean SPF found for the reference must be such that [average SPF ± s] is within [16.3 ± 3.43]. If this is not the case, then inclusion continues with a maximum of 13 subjects. The range given by the determined SPF +/- the confidence interval to the mean (95% CI) must contain the value x.

2. Classification

The average SPF value classifies the product into one of the following categories:

For SPF 6 and 10: "low protection" (SPF measured between 6 and 14.9)

For SPF 15, 20 and 25: "Medium Protection" (SPF measured between 15 and 29.9)

For SPF 30 and 50: "High Protection" (SPF measured between 30 and 59.9)

For SPF 50+: "Very high protection" (SPF measured above 60)

Thus, a vivo SPF measured at 17 should be displayed at 15, and be classified as medium protection.

II / In Vitro UVA protection

In vitro UVA protection is expressed from the entire UVA residual spectrum that has passed through the same cream layer according to the following equation:

The average protection index of the preparation studied was obtained by calculating the arithmetic mean of the protection indices of each test. B / RESULTS

The tests were carried out on 3 subjects for a critical wavelength of 370 results are shown below:

UVA in vitro 16

As shown by these results, the vaporizable, anhydrous, silicone-free, and ethanol-free composition of the invention has an SPF value of greater than 30 and in vitro UVA protection of 16.

Example 2: Sensory properties of the above composition The protocol is as follows: over 5 people, application of the product: 2 sprays on the forearms

Penetration by massage: 6 passages

 Evaluation of the sensory characteristics immediately after the 6 passes: satin, non sticky touch,

 Scale of 1 to 5, indication of the average score. The results are shown in the following table:

Average

 Satin touch: 5 3.9

 Non-sticky: 5 4.8

Claims

1 / vaporizable anhydrous solar cosmetic composition comprising a silicone substitute or silicone derivative based on a mixture consisting of: (a) from 50 to 100% by weight of a mixture of linear paraffins consisting of:  (i) 70 to 99% by weight of at least one linear paraffin selected from the group consisting of C8, C10 and C12 paraffins, alone or as a mixture, (ii) 1 to 30% by weight of at least one linear paraffin selected from the group consisting of C 14 to C 24 paraffins, alone or as a mixture, (b) at least one non-volatile oil representing less than 50% by weight of the mixture, Composition according to Claim 1, characterized in that the silicone substitute or silicone derivative consists solely of the mixture a / + b /. 3 / Composition according to one of the preceding claims, characterized in that it is devoid of ethanol. 4 / Composition according to one of the preceding claims, characterized in that it is devoid of surfactant. 5 / Composition according to one of the preceding claims, characterized in that the paraffin mixture consists of a mixture of dodecane and tetradecane. 6 / Composition according to one of the preceding claims, characterized in that the non-volatile oil is cococaprylate caprate. 7 / Composition according to one of the preceding claims, characterized in that the mixture of a / and b / is at least 25%> by weight of the composition. 8 / Composition according to one of the preceding claims, characterized in that the mixture of a / and b / meets the INCI name: coconut alkanes (and) cococaprylate caprate. 91 Composition according to one of the preceding claims, characterized in that it contains as filters, only mineral filters. 10 / Composition according to one of the preceding claims, characterized in that it further contains karanja oil. 11 / Composition according to claim 8, characterized in that the karanja oil represents between 10 and 50% by weight of the composition.