WO2014016349A1

WO2014016349A1 - Photoprotective composition

Info

Publication number: WO2014016349A1
Application number: PCT/EP2013/065640
Authority: WO
Inventors: Thierry Bernoud; Parfait Ramiandrasoa
Original assignee: Biosynthis SARL
Current assignee: Biosynthis SARL
Priority date: 2012-07-24
Filing date: 2013-07-24
Publication date: 2014-01-30
Anticipated expiration: 2015-01-24
Also published as: FR2993777B1; FR2993777A1

Description

Photoprotective composition

The present invention relates to a photoprotective composition containing, in a physiologically acceptable medium, a karanja oil and at least one polyester resulting from the reaction between (i) a C20-C44 carboxylic acid dimer, (ii) at least one polyol and (iii) optionally at least one C8-C32 monoalcohol and/or at least one C₈-C₃6 monocarboxylic acid. It also relates to the use of this composition for preventing skin and/or hair damage caused by UV radiation. Finally, it relates to a mixture consisting of karanja oil and of the abovementioned polyester, intended for the production of a photoprotective composition.

Karanja is a leguminous plant which originates from Asia. Karanja oil, which is extracted from the seeds, is used, in the Ayurvedic pharmacopea, for skin and haircare, in particular for its antiseptic and antiparasitic properties, and also in the treatment of eczema, psoriasis and scalp diseases. It is also used as an insecticide.

Other cosmetic applications of karanja oil are indicated in application FR 2 762 008, in particular its use in moisturizing or antiwrinkle creams. It is thus found in the composition of various cosmetic products on the market, including antisun products. The inventors have discovered, unexpectedly, that the combination of karanja oil with a particular polyester makes it possible to increase the SPF or sun protection factor of compositions containing this oil. They have demonstrated that it is thus possible to formulate a photoprotect ive composition based on karanja oil which has an SPF of greater than 30, including anhydrous formulations of suntan oil type which are particularly desired owing to their easy and pleasant application on the skin and their water resistance, but which do not generally make it possible to achieve SPFs of greater than 20.

The subject of the present invention is thus a photoprotect ive composition containing, in a physiologically acceptable medium, a karanja oil and at least one polyester resulting from the reaction between (i) a C₂₀-C44 carboxylic acid dimer, (ii) at least one polyol and (iii) optionally at least one C₈-C₃₂ monoalcohol and/or at least one C8-C36 monocarboxylic acid . The subject of the present invention is also a mixture consisting of karanja oil and of the abovement ioned polyester, and also the use thereof for producing a photoprotect ive composition. The composition according to the invention makes it possibler to confer on the skin good protection against UV rays, in particular to obtain an SPF of at least 20, better still of at least 30, or even of at least 50, including effective protection against UVA rays, by means of cosmetic ingredients which can be at least 90% by weight of plant origin. It also advantageously exhibits good persistence with respect to water, a transparent or translucent appearance, an emollient nature and a gliding feel without being tacky.

By way of introduction, it will be noted that, in the description and the claims which follow, the expression "between" should be understood to include the limits cited.

The constituents of the composition according to the invention will now be described in greater detail.

Karanja oil

According to the invention, the term "karanja oil" is intended to mean a water-insoluble fraction, extracted from karanja seeds, which contains predominantly fatty acid triglycerides. Usually, it also contains free fatty acids in amounts such that the acidity of the oil (expressed in grams of free oleic acid per 100 g of oil) is between 5% and 10% and generally from 0.5% to 4% by weight of unsaponifiable substances, such as karanjin and pongamol which are furanoflavones . Karanja oil contains essentially oleic and linoleic acid triglycerides and, in smaller amounts, palmitic acid, stearic acid, linolenic acid, arachidic acid and behenic acid.

This oil can be obtained by cold pressing of karanja seeds, according to processes well known to those skilled in the art and conventionally implemented for obtaining other plant oils. It is used as it is after deodorization according to a steam treatment process under vacuum and under nitrogen (such as that described in document FR 2 762 008), without subjecting it to one or more extractions using polar and/or nonpolar organic solvents. The karanja oil used according to the invention thus differs from alcoholic and aqueous-alcoholic extracts of karanja seeds.

The term "karanja" is intended to mean in this description the plant also known under the following botanical names: Pongamia pinnata, Pongamia glabra, Millettia pinnata, Derris indica and Gadelupa pinnata .

The composition according to the invention may, for example, contain from 1% to 60% by weight, preferably from 5% to 50% by weight and better still from 15% to 30% by weight of karanja oil, relative to the total weight of the composition. The mixture used for the production of this composition may, for example, contain from 50% to 80% by weight and preferably from 60% to 70% by weight of karanj a oil . Polyester

The polyester used according to the invention results from the reaction between (i) a C₂₀-C44 carboxylic acid dimer, (ii) at least one polyol and (iii) optionally at least one C₈-C₃₂ monoalcohol and/or at least one C₈-C₃6 monocarboxylic acid.

The C₂₀-C44 carboxylic acid dimers are oligomers of two identical or different monomers, which are obtained from two linear or cyclic, unsaturated C₁0-C₂₂ monocarboxylic acids, according to a reaction well known to those skilled in the art. Examples of such unsaturated fatty acids are usually contained in pin oil (Tall oil), rapeseed oil, corn oil, sunflower oil, soybean oil, grapeseed oil and linseed oil, and are also eicosapentaenoic acid and docosahexaenoic acid which are found in fish oils. Cis fatty acids derived from pine oil, soybean oil or rapeseed oil are preferably used.

These dimers are often present as a mixture with trimers and possibly monomers of these fatty acids. As examples of fatty acid dimer/trimer mixtures, mention may be made of the products sold by the company Croda under the trade name Pripol^®, by the company Cognis under the trade name Empol^®, by the company Oleon under the trade name Radiacid^® and by the company Arizona Chemicals under the trade name Unidyme^®.

According to the invention, use is preferably made of mixtures of oligomers comprising:

• 0 to 5% by weight of fatty acid monomers,

• 90% to 100% by weight of fatty acid dimers, and

• 0 to 5% by weight of fatty acid trimers and higher oligomers.

It is also preferable for these oligomers to be present in hydrogenated form, in order to provide better stability with respect to oxidation and less coloration of the cosmetic composition. Examples of such products include those sold by the company Croda under the trade names Pripol^® 1006 and 1009, by the company Cognis under the trade name Empol^® 1008 and by the company Oleon under the trade name Radiacid^® 0976.

It is preferred to use a dimer of linoleic acid, also called dilinoleic acid, in this invention. In order to obtain the polyester used according to the invention, the acid dimer is copolymerized with at least one polyol, preferably an alkanediol. It may be a C₂-C₁₀ alkanediol comprising a hydroxyl function at each end of its linear or branched alkylene chain. It may advantageously be chosen from 1, 3-propanediol, 2-methyl- 1 , 3-propanediol , 1 , 4-butanediol , neopentyl glycol (or 2 , 2-dimethyl-l , 3-propanediol ) , 1 , 6-hexanediol and 12- hydroxystearyl alcohol. 1 , 3-Propanediol is preferably used according to the invention. As a variant, the polyol may be chosen from a dimer diol such as dilinoleyl alcohol, (poly ) glycerols such as diglycerol and (poly ) alkylene glycols such as diethylene glycol.

According to one preferred embodiment of the invention, the polyester used according to the invention may be obtained solely from the abovementioned acid dimer (or the mixture of oligomers containing it) and from the abovementioned polyol. Such a polyester based on an alkanediol ( 1 , 3-propanediol or 1 , 4-butanediol in particular) is in particular commercially available from the company Biosynthis under the trade names Viscoplast Green 3000 and Viscoplast 14436H. Another polyol-based polyester, obtained from a dimer diol, such as the product of hydrogenation of the dilinoleic acid dimer, is the one sold in particular by the company Biosynthis under the trade name Viscoplast^® Green 3636.

As a variant, the polyester according to the invention can be obtained from the abovementioned compositions and also from a C8-C32 monoalcohol, preferably chosen from C₁₂-C30 saturated linear alcohols, and more preferentially C16-C24 saturated linear alcohols, such as octyldodecanol . An example of such a polyester is sold by the company Biosynthis under the trade name Viscoplast^® Green 20000. As a further variant, the polyester according to the invention can be obtained from the carboxylic acid dimmer and the polyol mentioned above and also from at least one optionally hydroxylated and/or alkoxylated, C8-C36 monocarboxylic acid chosen from linear or branched, saturated C₈-C₂o acids such as hydroxystearic acid, isostearic acid and isononanoic acid or from the cinnamic acid derivatives such as ferulic acid.

Polyesters of this type are in particular the products Viscoplast^® Green 1836G and 1836TG from the company Biosynthis. Mention can also be made of a copolyester obtained by copolymerizing dilinoleic acid, ferulic acid and propanediol.

The polyester according to the invention generally does not contain any monomer other than those previously described .

The composition according to the invention can, for example, contain from 5% to 30% by weight, and preferably from 8% to 15% by weight, of polyester, relative to the total weight of the composition. The mixture used for the production of this composition can contain from 20% to 50% by weight, and preferably from 30% to 40% by weight, of the polyester previously described.

Other constituents

As previously indicated, the composition according to the invention contains a physiologically acceptable medium, i.e. a medium which is compatible with the skin or the mucous membranes and optionally the skin appendages, more particularly a cosmetically acceptable medium, i.e. a medium which has a pleasant color, odor and feel and which does not cause any unacceptable discomfort for the user after application, such as tingling, tautness or red blotches.

In this regard, this medium preferably does not contain alcohol.

In addition to the polyester and the karanja oil previously described, this composition generally comprises at least one other oil. For the purpose of the present invention, the term "oil" is intended to mean a compound which is liquid at ambient temperature (25°C) and which, when it is introduced at at least 1% by weight into water at 25°C, is not at all soluble in the water, or is soluble in an amount of less than 10% by weight, relative to the weight of oil introduced into the water.

Examples of oils include: hydrocarbons, (poly) esters and (poly) ethers and in particular (poly) esters of C₂-C₂4 (preferably C₆-C₂o) acids or hydroxy acids and of advantageously branched, C₂-C₂4 (preferably C₆-C₂₀) alcohols or polyols and the plant oils containing same, dialkyl carbonates such as dicaprylyl carbonate, branched and/or unsaturated fatty acids (such as linoleic acid and linolenic acid), branched and/or unsaturated fatty alcohols (such as octyldodecanol and hexyldodecanol), silicone oils, fluorosilicone oils, fluoro oils, and also mixtures thereof. Among these oils, as hydrocarbons, mention may be made of branched volatile hydrocarbons, such as isododecane or isohexadecane, and also non-volatile hydrocarbons such as polybutene, hydrogenated polyisobutene, polydecenes, hydrogenated polydecene, liquid paraffins and squalane. Mention may also be made of Cs-Ci₄ linear volatile alkanes, derived in particular from plant sources, used alone or as mixtures of two alkanes differing by one or two carbon atoms, and in particular a mixture consisting: (i) of from 70% to 99% by weight of at least one linear alkane chosen from Cs, Cio and C₁₂ alkanes and mixtures thereof, preferably a C₁₂ alkane, and (ii) of from 1% to 30% by weight of at least one Ci₄ to C24 linear alkane, preferably a C14 alkane. Such a mixture is described more specifically in patent application WO 2010/115973 to which reference may be made for further details. It is also available from the company Biosynthis (INCI name: Coconut Alkanes) under the trade name Vegelight^® 1214.

As (poly) esters, mention may in particular may be made of emollient mono-, di-, tri- and tetraesters, such as ethyl acetate, isopropyl acetate, oleyl acetate, isononyl isononanoate, ethylhexyl isononanoate, hexyl neopentanoate, ethylhexyl neopentanoate, isodecyl neopentanoate, isostearyl neopentanoate, heptyl undecylenate, neopentyl glycol diheptanoate, neopentyl glycol diethyl hexanoate, pentaerythrityl tetraethylhexanoate, pentaerythrityl tetraisostearate, propanediol dicaprylate, neopentyl glycol dicaprylate/dicaprate, isopropyl myristate, isopropyl palmitate, hexyl laurate, the coco caprate/caprylate mixture, and Cs-Cio fatty acid triglycerides, and mixtures thereof .

Examples of plant oils are, in particular, wheatgerm oil, sunflower oil, grapeseed oil, sesame oil, corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy oil, pumpkin oil, sesame oil, marrow oil, rapeseed oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passionflower oil, musk rose oil or camellia oil. The term "silicone oil" is intended to mean an oil comprising at least one silicon atom, and in particular at least one Si-0 group. As non-volatile silicone oil, mention may in particular be made of polydimethyl- siloxanes containing at least 8 silicon atoms, polyalkylmethylsiloxanes, the alkyl chain of which contains from 8 to 20 carbon atoms, and the oils identified by the INCI name phenyl trimethicone . As volatile silicone oils, mention may be made of cyclomethicones or cyclopolysiloxanes.

Volatile linear alkanes (having a flashpoint below 100°C), plant oils, fatty acid and/or fatty alcohol esters such as coco caprylate/caprate and mixtures thereof (such as the product Vegelight^® 1214LC from Biosynthis, which is a mixture of C12 and C14 linear alkanes and of coco caprylate/caprate) are preferred for use in the present invention, owing to their plant origin . These oils can represent from 20% to 80% by weight, preferably from 30% to 70% by weight and better still from 40% to 60% by weight, relative to the total weight of the composition.

The composition according to the invention can also contain at least one of the following constituents: a fatty-phase gelling or structuring agent other than the abovementioned polyester, in particular at least one constituent chosen from: a plant, animal or hydrocarbon- based wax or else a linear fatty alcohol such as cetyl alcohol or a linear fatty acid such as stearic acid, a silicone gum, an olefin copolymer, in particular of Kraton^® type, a silicone elastomer, a polyamide resin or a polyester of a polyol of high molecular weight; a film- forming agent, such as a silicone resin or a hydrocarbon- based resin; an active agent; an organic or inorganic photoprotective agent or UV-screening agent other than karanja oil; a filler; an organic or inorganic pigment of spherical and/or lamellar structure (such as silica, talc, mica, etc) , which is optionally hydrophobically treated; a dye; a fragrance; a preservative; and mixtures thereof .

It is in particular preferred for the composition according to the invention to contain at least one inorganic UV-screening agent, such as micronized titanium dioxide and micronized zinc oxide, and/or at least one organic UV-screening agent, such as octyl methoxy- cinnamate . This composition is preferably anhydrous, i.e. it contains less than 5% by weight of water, or even less than 1% by weight of water, and better still less than 0.5% by weight of water, the water not being added during the preparation of the composition, but corresponding to the residual water introduced by the ingredients that it contains. It may be in fluid form (solution or dispersion) , optionally packaged in a spray or impregnated in a wipe, in the form of a gel or in solid form, in particular in the form of a stick or of a bar.

As a variant, the composition according to the invention may contain at least 5% by weight of water and may, in this case, constitute a milk, a cream or a foam. The photoprotective properties of the composition according to the invention can be taken advantage of both in the cosmetics field, for preventing or limiting the effects on the skin of photoaging, in particular the formation of wrinkles and of pigmentary marks and slackening of the skin, and in the pharmaceutical field, in particular for preventing or limiting erythema, immunosuppression, photodermatosis and skin cancers.

The subject of the present invention is therefore the cosmetic use of the composition previously described, for preventing aesthetic damage to the skin and/or hair caused by UV radiation, in particular for preventing or limiting the formation of wrinkles and of pigmentary marks and slackening of the skin.

The subject of the present invention is also a composition as previously described, for use in the prevention of skin damage caused by UV radiation, in particular for preventing or limiting erythema, immunosuppression, photodermatosis and skin cancers.

In addition to its photoprotective properties, the composition according to the invention may contain various ingredients which enable it to be used, in the cosmetics field, as a care (in particular anti-aging and/or depigmenting and/or slimming) and/or makeup product for facial and/or body skin and/or the lips or else as a hair product such as a shampoo, a leave-on or rinse-off hair conditioning product, or a hair dyeing product .

The invention will be understood more clearly from reading the following nonlimiting examples, given solely for the purposes of illustration.

EXAMPLES

Example 1 : Cosmetic compositions

The cosmetic compositions containing the constituents identified in upper case letters below by their INCI name (with reference to the CTFA Dictionary, 13^th edition, 2010), in the percentages by weight indicated opposite these constituents, were prepared in a manner conventional for those skilled in the art.

Sun protection gel

PONGAMIA GLABRA SEED OIL 55.0%

OCTYLDODECYL DILINOLEIC ACID /

PROPANEDIOL COPOLYMER (Viscoplast^® Green 20000 from BIOSYNTHIS) 20.0%

COCONUT ALKANES (Vegelight^® 1214LC

from BIOSYNTHIS) 15.0%

ETHYLHEXYL METHOXYCINNAMATE 10.0%

This gel has an SPF of 30, measured in vitro according to the HelioTest No. 1 protocol (Helioscience) and also provides effective protection against UVA radiation (PA+++) , evaluated according to HelioTest No. 2. The protocol of these tests is described in

Cosmetic and Toiletries, Vol 18, No. 10, 63-72 (2003) .

Antisun fluid emulsion TITANIUM DIOXIDE AND COCONUT

ALKANES AND POLYHYDROXYSTEARIC ACID AND STEARIC

ACID AND ALUMINA AND COCO CAPRYLATE /

CAPRATE (Vegelight^® Ti02 60 from BIOSYNTHIS) 20.0%

DIMER DILINOLEYL DIMER DILINOLEATE

(Viscoplast^® Green 3636 from BIOSYNTHIS) 1.0%

DILINOLEIC ACID / PROPANEDIOL COPOLYMER

(Viscoplast^® Green 3000 from BIOSYNTHIS) 1.0%

OCTYLDODECYL DILINOLEIC ACID / PROPANEDIOL

COPOLYMER AND PHYTOSTERYL SUNFLOWERSEEDATE AND HYDROGENATED VEGETABLE GLYCERIDES

(Bioshine^® 5000S from BIOSYNTHIS) 6.0%

BUTYL OCTYL SALICYLATE 10.0%

PONGAMIA GLABRA SEED OIL 6.0%

COCOS NUCIFERA OIL 1.0% COCONUT ALKANES AND COCO CAPRYLATE / CAPRATE

(Vegelight^® 1214LC from BIOSYNTHIS) 13.0%

CETYL PEG/PPG 10/1 DIMETHICONE 3.5'o

ETHYL HEXYL GLYCERIN 1.0% SODIUM CHLORIDE 0.8% PENTYLENE GLYCOL 0.6% PROPANEDIOL 4.0% Water qs 100.0%

Transparent lipstick

DILINOLEIC ACID / PROPANEDIOL COPOLYMER

(Viscoplast^® Green 3000 from BIOSYNTHIS) 35.0% DI I SOSTEARYL MALATE 20.0%

ETHYLHEXYL METHOXYCINNAMATE 7.0%

ETHYLHEXYL ISONONANOATE 20.0%

PONGAMIA GLABRA SEED OIL 13.0%

DIBUTYL LAUROYL GLUTAMIDE 3.0% DIBUTYL ETHYLHEXANOYL GLUTAMIDE 2.0%

Amber suntan oil

PONGAMIA GLABRA SEED OIL 65.0% OCTYLDODECYL DILINOLEIC ACID /

PROPANEDIOL COPOLYMER 12.0%

COCOS NUCIFERA OIL 22.2%

Fragrance 0.8%

This composition has an SPF of 20, measured in vitro, leaves a very soft and water-resistant film on the skin

Repair care COCONUT ALKANES & DIMETHICONOL

(Vegelight Si-1517 from BIOSYNTHIS) 69.0%

ETHYLHEXYL METHOXYCINNAMATE 7.0%

PONGAMIA GLABRA SEED OIL 16.0% OCTYLDODECYL DILINOLEIC ACID /

PROPANEDIOL COPOLYMER 2.0% ARGANIA SPINOSA KERNEL OIL 5.0% Fragrance 0.8% TOCOPHEROL 0.2%

This oil can be applied to dry and damaged hair in order to repair the fibers thereof and to protect them against the sun.

Example 2 : Evaluation of the SPF-promoting effect of the polyester according to the invention

The SPF and the UVA protection index (PA) of a deodorized karanja oil used, on the one hand, alone

(composition A) and, on the other hand, in combination with a polyester according to the invention, in the case in point Viscoplast^® Green 20000 from Biosynthis (composition B) , in a ratio by weight of the karanja oil to the polyester of 65:35, was measured in vitro, as in example 1.

The results of this test are given in table 1 below:

Table 1

The average SPF of composition B was also measured in vivo on 3 volunteers and was 30. This test demonstrates that the polyester according to the invention makes it possible to significantly increase the SPF and the UVA protection conferred by the karanja oil, since it makes it possible to obtain an SPF and a UVA protection index which are identical to a composition comprising 50% more karanja oil. It is thus possible to take advantage of the photoprotect ive properties of karanja oil while using a smaller amount thereof, and to obtain a composition which has better cosmetic properties.

Example 3 : Comparison of various fatty-phase structuring agents

The effect, on the SPF and the UVA protective index, of a polyester according to the invention (Viscoplast^® Green 20000 from Biosynthis), used in a proportion of 10% by weight, and of another fatty-phase structuring agent, namely hydrogenated castor oil, used in a proportion of

3% by weight, which is the maximum usable amount taking into account its viscosity, was compared. Each of these structuring agents was formulated in combination with 30% by weight of karanja oil, 25% by weight of a dispersion of titanium oxide and zinc oxide (at 33% of active material) and 10% by weight of gelled plant oils (Bioshine^® from Biosynthis), in a medium consisting of a mixture of C₁₂ and C14 linear alkanes and of coco caprylate/caprate (Vegelight^® 1214LC from Biosynthis), the amount of the medium being adjusted so as to obtain a total ingredient content of the composition of 100% by weight . The tests were carried out in a manner similar to example 1, on a PMMA plate.

The results obtained are collated in table 2 below:

Table 2

This test demonstrates that the polyester according to the invention makes it possible to significantly increase the SPF and the UVA protection conferred by karanja oil, contrary to other prior art thickeners.

Claims

1. Photoprotective composition containing, in a physiologically acceptable medium, a karanja oil and at least one polyester resulting from the reaction between

(i) a C₂₀-C44 carboxylic acid dimer, (ii) at least one polyol and (iii) optionally at least one C₈-C₃₂ monoalcohol and/or at least one C8-C36 monocarboxylic acid .

2. Composition according to Claim 1, characterized in that the oil is obtained by cold pressing of karanja seeds .

3. Composition according to either of Claims 1 and

2, characterized in that the acid dimer is a linoleic acid dimer.

4. Composition according to any one of Claims 1 to 3, characterized in that the polyol is an alkanediol such as 1 , 3-propanediol .

5. Composition according to any one of Claims 1 to

4, characterized in that the monoalcohol is chosen from C₁₂-C30, preferably Ci₆-C₂4, saturated linear alcohols, such as octyldodecanol .

6. Composition according to any one of Claims 1 to

5, characterized in that the karanja oil represents from 1% to 60%, preferably from 5% to 50% and more preferentially from 15% to 30% by weight, relative to the weight of the composition.

7. Composition according to any one of Claims 1 to

6, characterized in that the polyester represents from 5% to 30% by weight and preferably from 8% to 15% by weight, relative to the weight of the composition.

8. Composition according to any one of Claims 1 to

7, characterized in that it is anhydrous.

9. Composition according to any one of Claims 1 to

8, characterized in that it also contains at least one oil chosen from: volatile linear alkanes, plant oils, and fatty acid and/or fatty alcohol esters, and mixtures thereof .

10. Composition according to any one of Claims 1 to

9, characterized in that it also contains at least one inorganic or organic UV-screening agent.

11. Cosmetic use of the composition according to any one of Claims 1 to 10, for preventing aesthetic damage to the skin and/or the hair caused by UV radiation.

12. Composition according to any one of Claims 1 to

10, for use in the prevention of skin damage caused by UV radiation .

13. Mixture consisting of karanja oil and of a polyester as described in any one of Claims 1 and 3-5.

14. Use of the mixture according to Claim 13, for the production of a photoprotective composition.