FR2816616A1 - New aminoguanidine alkanoate, alkyl sulfate, alkanesulfonate, alkyl phosphate and alkylphosphonate salts useful as surfactants in cosmetic or pharmaceutical compositions - Google Patents

Abstract

Aminoguanidine alkanoate, alkyl sulfate, alkanesulfonate, alkyl phosphate and alkylphosphonate salts (I) are new. Aminoguanidine salts of formula (NH2-C(=NH)NH-NH3<+>)n (Xn--A-CH3) (I) are new. Xn- = -COO<->, -OSO3<->, -OPO2(OACH3)<->, -OPO3<2--> or -PO3<2->; and A = a 4-30C linear or branched (un)saturated divalent hydrocarbon radical optionally substituted by OH and/or optionally containing heteroatoms selected from O, N and S. An Independent claim is also included for a composition comprising at least one compound (I) in a physiologically acceptable medium.

Description

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The present invention relates to novel anionic amphiphilic compounds, with an aminoguanidium cation, capable of being used in particular in cosmetics, in particular for their surfactant properties. The invention also relates to the compositions thus obtained and the use of these compounds, in particular as a surfactant.

It is known to use guanidine salts of anionic amphiphiles, or of fatty acids, in cosmetics or dermopharmaceutics. One can in particular quote document WO95 / 33443 which describes the use of a guanidine salt of acid. glycolic in topical application, in particular to treat skin conditions such as acne or warts.

Mention may also be made of document WO98 / 06378 which describes the use of a guanidine salt of C4-C22 fatty acids for treating disorders associated with hyperseborrhea of the skin and scalp.

Finally, it is known from document JP2810307 to use in cosmetics amine salts of C12-C22 fatty acids, in combination with a C12-18 N-acylglutamate and a diester of ethylene glycol and of acid. C14-22 fatty, in particular in a detergent composition which exhibits great stability at high temperature, or in the presence of enzymes.

However, none of the documents of the state of the art mentions the potential use, in cosmetics or in pharmacy in particular, of aminoguanidine salts of anionic amphiphiles.

Furthermore, the compounds mentioned in the literature are not described as having good surfactant properties, in particular satisfactory emulsifying, foaming and / or detergent properties.

It is up to the Applicant to have demonstrated that the compounds according to the invention, unlike the compounds of the prior art, could make it possible to obtain compositions, in particular for topical application, advantageously surfactants.

An object of the present invention is a compound corresponding to one of formulas (1) or (II) as defined below.

Another subject of the invention is a composition comprising, in a physiologically acceptable medium, at least one compound as defined below.

Yet another subject of the invention is the use of at least one compound as defined below or of a composition comprising it, as a surfactant, in particular as an emulsifying agent, a foaming agent and / or detergent agent, in particular in cosmetic or pharmaceutical compositions.

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The compounds according to the invention have the advantage of being perfectly soluble in water, unlike certain compounds of the prior art such as potassium laurate, which facilitates their use in aqueous-based cosmetic compositions. .

Furthermore, the compounds according to the invention make it possible to rapidly generate a soft and slippery foam, which is cosmetically very pleasant.

dans un solvant tel que l'eau. La présente invention concerne donc des composés répondant à l'une des formules (1) ou (ici) ci-après :

dans lesquelles : - est choisi parmi les radicaux-COO-,-OSO3-,-SO3-et-OP02 (OA'CH3)' avec A'représentant un radical hydrocarboné divalent en C4-C30, linéaire ou ramifié, saturé ou insaturé, éventuellement substitué par au moins un radical hydroxy et/ou éventuellement renfermant des hétéroatomes choisis parmi 0, N et S ; - X2-est choisi parmi les radicaux-OP03--et-PO3--, - A représente un radical hydrocarboné divalent en C4-C30, linéaire ou ramifié, saturé ou insaturé, éventuellement substitué par au moins un radical hydroxy et/ou éventuellement renfermant des hétéroatomes choisis parmi 0, N et S.

These compounds are also easily synthesized, by a simple chemical reaction, using industrial and economical raw materials, and

in a solvent such as water. The present invention therefore relates to compounds corresponding to one of the formulas (1) or (here) below:

in which: - is chosen from the radicals -COO -, - OSO3 -, - SO3-and -OP02 (OA'CH3) 'with A're representing a divalent C4-C30 hydrocarbon radical, linear or branched, saturated or unsaturated, optionally substituted by at least one hydroxyl radical and / or optionally containing heteroatoms chosen from 0, N and S; - X2 - is chosen from the radicals - OP03 - and - PO3--, - A represents a divalent C4-C30 hydrocarbon radical, linear or branched, saturated or unsaturated, optionally substituted by at least one hydroxyl radical and / or optionally containing heteroatoms selected from 0, N and S.

Preferably, the compounds according to the invention correspond to formula (1) in which: - is chosen from the radicals -COO -, - OSO3-and -OP02 (OA'CH3) 'with A ′ representing a divalent hydrocarbon radical in C6-C22, linear or branched, saturated or unsaturated, in particular comprising 10, 12, 14, 16 or 18 carbon atoms, and advantageously a divalent C6-C18, linear and saturated hydrocarbon radical, and - A represents a hydrocarbon radical divalent in C6-C22, linear or branched, saturated or unsaturated, in particular comprising 10,12, 14,16 or 18 carbon atoms

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bone, and advantageously a divalent C6-C18 linear and saturated hydrocarbon radical.

Preferably also, the compounds according to the invention correspond to formula (it) in which: - X-is-OP03 - and - A represents a divalent C6-C22 hydrocarbon radical, linear or branched, saturated or unsaturated, in particular comprising 10, 12, 14, 16 or 18 carbon atoms, and advantageously a divalent linear and saturated C6-C18 hydrocarbon radical.

- le stéarate d'aminoguanidine (X :-COO et A :-Ci6H32-linéaire) ; - le 12-hydroxy-stéarate d'aminoguanidine (X-.-COO et A :-Cl8H35OH-linéaire), - le laurylsulfate d'aminoguanidine (X :-OS03 et A :-CioH2o-tinéaire). Among the compounds of formula (1) which may be used in the present invention, there may be mentioned: - aminoguanidine laurate in which X represents —COO and A represents a linear — C10H20-radical; - aminoguanidine myristate (X: -COO and A: -C12H24-linear); - aminoguanidine palmitate (X: -COO and A: -Ci4H28-linear);

- aminoguanidine stearate (X: -COO and A: -Ci6H32-linear); - aminoguanidine 12-hydroxy-stearate (X -.- COO and A: -Cl8H35OH-linear), - aminoguanidine laurylsulphate (X: -OS03 and A: -CioH2o-linear).

The compounds according to the invention can be present in the compositions, alone or as a mixture, in an amount of 0.01% to 50% by weight relative to the total weight of the composition, in particular in an amount of 0.5-40% in weight. weight, and preferably in an amount of 1 to 30% by weight.

The compounds according to the invention can be easily prepared by a person skilled in the art on the basis of his general knowledge, in particular by adding the acid corresponding to aminoguanidine hydrogencarbonate in a solvent such as water, optionally in admixture with an organic co-solvent such as an alcohol or a ketone.

The compounds of formula (1) can in particular be used, alone or as a mixture, in a composition which comprises a physiologically acceptable medium, in particular in a cosmetic or pharmaceutical composition which therefore also comprises a pharmaceutically acceptable medium.

This physiologically acceptable medium, its constituents, their amount, the dosage form of the composition and its method of preparation, can be chosen by a person skilled in the art on the basis of his general knowledge as a function of the type of composition sought.

In general, this medium can be anhydrous or aqueous. When the composition comprises an aqueous phase, said phase can comprise

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prendre de l'eau, une eau florale et/ou une eau minérale.

take water, floral water and / or mineral water.

Said phase may further comprise alcohols such as C 1 -C 6 monoalcohols and / or polyols such as glycerol, butylene glycol, isoprene glycol, propylene glycol, polyethylene glycol.

The composition can also comprise a fatty phase, in particular constituted by fatty substances which are liquid at 25OC, such as oils of animal, vegetable, mineral or synthetic origin, volatile or not; fatty substances which are solid at 25 ° C., such as waxes of animal, vegetable, mineral or synthetic origin; pasty fatty substance; gums; of their mixtures.

Volatile oils are generally oils having, at 25OC, a saturated vapor pressure of at least 0.5 millibar (ie 50 Pa).

Among the constituents of the fatty phase, mention may be made of: - volatile cyclic silicones having from 3 to 8 silicon atoms, preferably from 4 to 6; - cyclocopolymers of the dimethylsiloxane / methylalkylsiloxane type, - volatile linear silicones having from 2 to 9 silicon atoms; - volatile hydrocarbon oils, such as isoparaffins and in particular isododecane and fluorinated oils, - polyalkyl (Ci-C20) siloxanes and in particular those containing tn-methylsilyl end groups, among which there may be mentioned linear polydimethylsiloxanes and alkylmethylpolysiloxanes such as cetytdimeth! cone (CTFA name), - silicones modified by aliphatic and / or aromatic groups, optionally fluorinated, or by functional groups such as hydroxyl, thiol and / or amine groups - phenylated silicone oils, - oils of animal, vegetable or mineral origin, and in particular animal or vegetable oils formed by esters of fatty acids and of alcohols or polyols, in particular liquid triglycerides, for example sunflower, corn or soybean oils , squash, grape seeds, sesame, hazelnut, apricot, almonds or avocado; fish oils, glycerol tricaprocaprylate, or vegetable or animal oils of formula R1COOR2 in which Ri represents the residue of a higher fatty acid comprising from 7 to 19 carbon atoms and R2 represents a branched hydrocarbon chain containing from 3 to 20 carbon atoms, for example, Purcellin oil; paraffin oil, petroleum jelly, perhydrosqualene, wheat germ oil, calophyllum, sesame, macadamia, grape seed, rapeseed, copra, peanut, palm, castor oil, jojoba, olive or grain sprouts; esters of fatty acids, alcohols; acetylglycerides, octanoates, decanoates or ricinoleates of alcohols or polyalcohols; fatty acid triglycerides; glycerides; - fluorinated and perfluorinated oils.

- silicone gums; - waxes of animal, vegetable, mineral or synthetic origin such as waxes

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microcristallines, la paraffine, le pétrolatum, la vaseline, l'ozokérite, la cire de 1, d'Ourimontan ; la cire d'abeilles, la lanoline et ses dérivés ; les cires de Candellila, d'Ouri- cury, de Carnauba, du Japon, le beurre de cacao, les cires de fibres de lièges ou de canne à sucre ; les huiles hydrogénées concrètes à 25OC, les ozokérites, les esters gras et les glycérides concrets à 25 C ; les cires de polyéthylène et les cires obtenues par synthèse de Fischer-Tropsch ; des huiles hydrogénées concrètes à 25OC ; des lanolines ; des esters gras concrets à 25 C ; les cires de silicone ; les cires fluorées.

microcrystalline, paraffin, petrolatum, petrolatum, ozokerite, wax 1, Ourimontan; beeswax, lanolin and its derivatives; Candellila, Uricury, Carnauba and Japanese waxes, cocoa butter, waxes of cork fibers or of sugar cane; hydrogenated oils which are solid at 25 ° C., ozokerites, fatty esters and glycerides which are solid at 25 ° C.; polyethylene waxes and waxes obtained by Fischer-Tropsch synthesis; hydrogenated oils which are solid at 25OC; lanolins; fatty esters which are solid at 25 C; silicone waxes; fluorinated waxes.

(The composition may furthermore comprise a surfactant compound usually employed in the field under consideration.

essentielles, des conservateurs, des actifs cosmétiques ou pharmaceutiques, des hydratants, des vitamines, des acides gras essentiels, des sphingolipides, des agents autobronzants, des filtres solaires, des polymères filmogènes, des épais- sissants, des colorants, des pigments, des charges, des nacres. The composition can also comprise any additive usually used in the field of application envisaged, such as antioxidants, perfumes, oils.

essential, preservatives, cosmetic or pharmaceutical active ingredients, moisturizers, vitamins, essential fatty acids, sphingolipids, self-tanning agents, sun filters, film-forming polymers, thickeners, dyes, pigments, fillers , mother-of-pearl.

Of course, a person skilled in the art will take care to choose the possible additional compounds and their quantity, in such a way that the advantageous properties of the composition according to the invention are not, or not substantially, altered by the addition envisaged.
The compositions according to the invention are intended to be applied to the skin of the face and the body, to the mucous membranes and / or to keratin fibers such as the nails, the eyelashes or the hair.

They can be in all the galenic forms that can be envisaged, such as an oily or aqueous solution; oily or aqueous gel; oil-in-water, water-in-oil or multiple emulsion; oil-in-water or water-in-oil dispersion; multiphase system including two-phase.

These compositions can be in the form of a make-up product for the skin of the face, body or lips or keratin fibers (nails, eyelashes, eyebrows, hair), such as a foundation, a tinted cream, a blush or eye shadow, a loose or compact powder, a concealer stick, a camouflaging stick, an eyeliner, a mascara, a lipstick, a nail polish, a composition of hair makeup; in the form of a hair composition, and in particular a styling cream or gel, a dyeing, oxidation or direct composition, optionally in the form of a coloring shampoo; - a care, treatment, cleansing or protection product for the skin of the face or the body including the scalp, such as a care composition (day, night, moisturizing) for the face or from the body ; an anti-wrinkle composition or

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anti-aging for the face; a matifying composition for the face; a composition for irritated skin; a makeup removing composition; a body milk, especially moisturizer optionally after-sun; - a composition for sun protection, artificial tanning (self-tanning) or after-sun care; - an oral hygiene product such as a toothpaste or an oral rinsing lotion.

The compounds according to the invention, or the compositions comprising them, can very particularly be used as a surfactant, in particular as an emulsifying agent, foaming agent and / or detergent agent, in particular in cosmetic or pharmaceutical compositions. The invention is illustrated in more detail in the following examples Example 1: Preparation of aminoquanidine laurate 350 ml of isopropanol and 220 g (1.1 mol) of auric acid are introduced into a 2-liter flask. Heated to 60oC, with stirring.

When the acid is completely dissolved, 100 ml of water are added and the mixture is heated to 75-800C. 149.6 g (1.1 mol) of aminoguanidine hydrogencarbonate are added in several portions. When about half of the hydrogencarbonate is added, 100 ml of water are added.

20 C, on filtre, on rince à l'acétone et on sèche sous vide On obtient 283 g de laurate d'aminoguanidine, sous forme de poudre de couleur blanche, soit un rendement de 95%. The reaction mixture is left at 800C with stirring for about 30 minutes, then concentrated under vacuum (100 mbar) at 600C, half of the initial volume. Allowed to cool to 400C and 1 liter of acetone is added. Leave to cool until

20 ° C., filtered, rinsed with acetone and dried under vacuum. 283 g of aminoguanidine laurate are obtained in the form of a white powder, ie a yield of 95%.

Example 2 Similarly to Example 1, the following are prepared: - 300 g of aminoguanidine myristate in the form of a white powder, - 318 g of aminoguanidine palmitat in the form of a white powder, - 345 g of aminoguanidine stearate in the form of a powder of white color.

Example 3 An aqueous solution comprising 13% by weight of aminoguanidine laurate is prepared, 1 ml is taken from it and then the hands are rubbed in order to develop the

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foam. Said foam is sensually evaluated, noting from 0 to 10, its volume, its density and the size of the bubbles.

Then add 2 ml of water, mass again to continue to develop the foam then again note the volume, density and size of the bubbles Add a second time 2 ml of water, mass again to continue to develop the foam then note the volume, density and size of the bubbles.

The same observations are made with guanidine laurate and potassium laurate.

(The following results are obtained:

<tb>
<tb> Laurate <SEP> of friend-Laurate <SEP> of <SEP> Laurate <SEP> of
<tb> noguanidine <SEP> guanidine <SEP> potassium
<tb> (invention) <SEP> (comparative) <SEP> (witness)
<tb> Appearance <SEP> of <SEP> the <SEP> solution <SEP> Transparent <SEP> Transparent, <SEP> Opaque, <SEP> with
<tb> initial <SEP> viscous <SEP> of the <SEP> particles <SEP> in
<tb> suspension
<tb> 1 <SEP> er <SEP> volume <SEP> of <SEP> foam <SEP> 3, <SEP> 5 <SEP> 2 <SEP> 5
<tb> Size <SEP> of the <SEP> bubbles <SEP> 6 <SEP> 4 <SEP> 4
<tb> Density <SEP> 7.5 <SEP> 3 <SEP> 9
<tb> 2nd <SEP> volume <SEP> foam <SEP> 7 <SEP> 6 <SEP> 8
<tb> Size <SEP> bubbles <SEP> 6.5 <SEP> 7 <SEP> 7
<tb> Density <SEP> 9 <SEP> 8 <SEP> 9
<tb> 3 "'volume <SEP> of <SEP> foam <SEP> 10
<tb> Size <SEP> of the <SEP> bubbles <SEP> 5 <SEP> 7 <SEP> 8
<tb> Density <SEP> 9 <SEP> 8, <SEP> 5 <SEP> 9
<tb>
It is therefore observed that the foam starts off very well with the compound of the invention, as with the control compound, whereas it does not start with the comparative.

The compound of the invention gives a transparent solution, soluble in water, and which generates an immediate foam.

The comparison also gives a transparent solution, but which is viscous and elastic; the foam start is very bad The witness has a fairly good foam start, but the initial solution is not transparent, the compound not being soluble in water.

Furthermore, the foam according to the invention is very soft and very slippery compared to those of the prior art.

Example 4 A cosmetic composition is prepared comprising (% by weight): - glycerin 7%

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- PEG-8 7% - glycerol stearate 5% - cocoyl-glucoside (50% active ingredient) 2% - aminoguanidine laurate 3% - aminoguanidine myristate 20% - aminoguanidine palmitate 3% - d stearate 'aminoguanidine 3% - preservative qs - ENTA qs - water qsp 100%

Claims (10)

in which: - is chosen from the radicals -COO -, - OSO3 -, - SO3-and -OP02 (OA'CH3) 'with A're representing a divalent C4-C30 hydrocarbon radical, linear or branched, saturated or unsaturated, optionally substituted by at least one hydroxyl radical and / or optionally containing heteroatoms chosen from 0, N and S; - X2 - is chosen from the radicals - OPO - and - PO3--, - A represents a divalent C4-C30 hydrocarbon radical, linear or branched, saturated or unsaturated, optionally substituted by at least one hydroxyl radical and / or optionally containing heteroatoms selected from 0, N and S.

CLAIMS 1. Compound corresponding to one of the formulas (1) or (II) below: 2. Compound according to claim 1, corresponding to formula (1) in which: - is chosen from the radicals -COO-, -OSO3- and -OPO2 (OA'CH3) 'with A're representing a divalent C6 hydrocarbon radical. -C22, linear or branched, saturated or unsaturated, in particular comprising 10, 12, 14, 16 or 18 carbon atoms, and advantageously a divalent C6-C18 hydrocarbon radical, linear and saturated, and - A represents a divalent hydrocarbon radical linear or branched C6-C22, saturated or unsaturated, in particular comprising 10, 12, 14, 16 or 18 carbon atoms, and advantageously a divalent linear and saturated C6-C18 hydrocarbon radical. 3. Compound according to claim 1, selected from aminoguanidine laurate, aminoguanidine myristate, aminoguanidine palmitat, aminoguanidine stearate, aminoguanidine 12-hydroxy-stearate, aminoguanidine lauryl sulphate. 4. Compound according to claim 1, corresponding to the formula (here) in which: - X - is-OP03 - and - A represents a divalent C6-C22 hydrocarbon radical, linear or branched, saturated or unsaturated, in particular comprising 10,12, 14,16 or 18 carbon atoms <Desc / Clms Page number 10> bone, and advantageously a divalent C6-C18 linear and saturated hydrocarbon radical.

5. Composition comprising, in a physiologically acceptable medium, at least one compound as defined in one of claims 1 to 4. 6. Composition according to claim 5, comprising, alone or as a mixture, 0.01% to 50% by weight relative to the total weight of the composition, in particular 0.5-40% by weight, and preferably 1 to 30%. by weight, of compounds according to one of claims 1 to 4. 7. Composition according to one of claims 5 to 6, further comprising a surfactant compound. 8. Composition according to one of claims 5 to 7, which is in the form of a cosmetic or pharmaceutical composition. 9. Composition according to one of claims 5 to 8, in the form of a makeup product for the skin of the face, body or lips or keratin fibers (nails, eyelashes, eyebrows, hair), such as a foundation, a tinted cream, a blush or eyeshadow, a loose or compact powder, a concealer stick, a camouflaging stick, an eyeliner, a mascara, a lipstick, a nail polish, a hair makeup composition; in the form of a hair composition, and in particular a styling cream or gel, a dyeing, oxidation or direct composition, optionally in the form of a coloring shampoo; - a care, treatment, cleansing or protection product for the skin of the face or the body including the scalp, such as a care composition (day, night, moisturizing) for the face or from the body ; an anti-wrinkle or anti-aging composition for the face; a matifying composition for the face; a composition for irritated skin; a makeup removing composition; a body milk, especially moisturizer optionally after-sun; - a composition for sun protection, artificial tanning (self-tanning) or after-sun care; - an oral hygiene product such as a toothpaste or an oral rinsing lotion. 10 Use of at least one compound as defined in one of claims 1 to 4, or of a composition as defined in one of claims 5 to 7, as a surfactant, in particular as a emulsifying agent, foaming agent and / or detergent agent, in particular in cosmetic or pharmaceutical compositions.