Process for stabilizing the association of ascorbic acid and ferulic acid

Abstract

Process for stabilizing the association of ascorbic acid and ferulic acid The present invention relates to a process for preparing a cosmetic composition comprising ascorbic acid or one of its derivatives and ferulic acid or one of its derivatives, comprising extemporaneous mixing of: (i) a first aqueous composition comprising ascorbic acid or one of its derivatives and polyquaternium-67, with (ii) a second composition comprising, in at least one glycol, ferulic acid or one of its derivatives. It also relates to a process for the care of keratin materials, in particular the skin, comprising the preparation followed by the application of such a mixture.

Description

[0001] Process for stabilizing the association of ascorbic acid and ferulic acid

[0002] The present invention relates to a process for preparing a composition ensuring the stabilization of the association of ascorbic acid or one of its derivatives and ferulic acid or one of its derivatives.

[0003] In cosmetic applications, it is routine to add ascorbic acid (vitamin C) as an active agent which, thanks to its collagen synthesis stimulation properties, improves skin firmness. Ascorbic acid is also known for its antioxidant properties. It is also routine to use ferulic acid or its derivatives to improve the texture, hydration, evenness, suppleness and / or homogeneity, transparency and / or radiance of the complexion of damaged skin.

[0004] However, ascorbic acid and ferulic acid are compounds that are difficult to stabilize in aqueous medium, and the stabilization conditions are different for ascorbic acid and for ferulic acid. In particular, the best stability condition of ascorbic acid is pH 6, whereas the best stability condition of ferulic acid is pH less than 4. There is no common formulation range in terms of pH for the co-formulation of these two acids.

[0005] Therefore, there is a need for an aqueous cosmetic composition comprising ascorbic acid and ferulic acid which is stable for a period of use of at least one month. There is also a need for an improved packaging suitable for the easy preparation of the said aqueous cosmetic composition and such that this packaging allows otpimum conditions of stability for both ascorbic acid and ferulic acid.

[0006] The aim of the present application is that of solving the stabilization incompatibility in the same product and / or packaging of the association of ascorbic acid and ferulic acid.

[0007] Surprisingly, the Applicant discovered that the association of a composition comprising ascorbic acid or one of its derivatives and polyquaternium-67, and a composition comprising ferulic acid or one of its derivatives and a glycolic solvent, with an extemporaneous process, makes it possible to obtain a composition which is stable for at least 30 days.

[0008] Thus, the present invention relates to a process for preparing a composition comprising ascorbic acid or one of its derivatives and ferulic acid or one of its derivatives, comprising extemporaneous mixing of: (i) a first aqueous composition comprising ascorbic acid or one of its derivatives and polyquaternium-67, with

[0009] (ii) a second composition comprising, in at least one glycol, ferulic acid or one of its derivatives.

[0010] In particular, said extemporaneous mixing is carried out at ambient temperature.

[0011] The term "ambient temperature" denotes a temperature of approximately 20°C to 25°C.

[0012] The cosmetic composition according to the invention, after mixing the first and second compositions (i) and (ii), has a pH between 4 and 8, preferably between 5 and 7. Preferably, the composition according to the invention has a pH of 6.

[0013] The composition according to the invention is stable.

[0014] Preferably, the cosmetic composition according to the invention is stable at ambient temperature.

[0015] A composition is referred to as stable when the macroscopic appearance (clearness and homogeneity) does not change after at least 30 days. In particular, the composition according to the invention has a clear and homogeneous appearance.

[0016] For the purposes of this invention, the term "clear" denotes a composition having a transparent appearance.

[0017] For the purposes of this invention, the term "homogeneous" denotes a composition consisting of a single phase, in other words single-phase.

[0018] In particular, for the purpose of this invention, a composition is referred to as stable when it is stable in terms of chemical losses of ascorbic acid and of ferulic acid, preferably measured with a liquid chromatography method combined with UV detection, for up to 1 month (30 days), preferably up to 2 months (60 days), and more preferably up to 3 months (90 days), at ambient temperature. More particularly, a composition is referred to as stable when the chemical loss of ascorbic acid is less than 20%p / p and the chemical loss of ferulic acid is less than 20%w / w for up to 1 month (30 days), preferably up to 2 months (60 days), and more preferably up to 3 months (90 days), at ambient temperature.

[0019] To evaluate the stability of the composition, the measurement of chemical losses of ascorbic acid and of ferulic acid are preferably measured as follows:

[0020] The chemical losses of ascorbic acid and of ferulic acid are measured with a liquid chromatography method combined with UV detection, according to the following parameters: Eluent: 0.006 mol / L Di-Sodium Hydrogen Phosphate buffer, pH 2.1 / ACN (20 / 80 v / v) Flow rate: 0.35ml / min

[0021] Injection volume: 1 l

[0022] Temperature: 50°C

[0023] A detection: U.V. from 200 to 300 nm:

[0024] Ascorbic acid extraction is at 250nm, and ferulic acid extraction is at 320nm.

[0025] The invention also relates to a stable cosmetic composition, notably a cosmetic composition stable at room temperature in terms of chemical losses of ascorbic acid and ferulic acid, measured by a liquid chromatography method combined with UV detection, for at least 30 days, (hereinafter "stable cosmetic composition") comprising, with respect to the total weight of the composition:

[0026] - from 0.1 to 15% by weight of ascorbic acid or one of its derivatives, and

[0027] - from 0.01 to 1% by weight of ferulic acid or one of its derivatives, said composition having a pH between 4 and 8, preferably between 5 and 7, and preferably a pH of 6.

[0028] According to an embodiment, the composition according to the invention is substantially free from tocopherol. "Substantially free from tocopherol" means that the composition according to the invention has a tocopherol concentration less than or equal to 2% by weight, with respect to the total weight of the composition, preferably less than or equal to 1 % by weight, preferably between 0.01 % and 2% by weight. Preferably, the composition according to the invention is totally free from tocopherol.

[0029] According to an embodiment, the composition according to the invention is substantially free from vitamin E. "Substantially free from vitamin E" means that the composition according to the invention has a vitamin E concentration less than or equal to 2% by weight, with respect to the total weight of the composition, preferably less than or equal to 1 % by weight, preferably between 0.01% and 2% by weight. Preferably, the composition according to the invention is totally free from vitamin E.

[0030] The invention also relates to a cosmetic process for the care of keratin materials, in particular the skin, which comprises (1) the process for preparing a cosmetic composition according to the invention, then (2) the application of this cosmetic composition on keratin materials, in particular the skin. In particular, the step (2) of applying the cosmetic composition takes place no later than one month (i.e. no later than 30 or 31 days) after the step (1) of preparing said composition.

[0031] Moreover, the invention also relates to the use of said composition in the cosmetic field, in particular for the care of keratin materials, in particular the skin.

[0032] For the purposes of this invention, the term keratin materials denotes the skin.

[0033] The term "skin" denotes facial skin and / or body skin, and the scalp.

[0034] The invention also relates to a kit for the care and / or treatment of keratin materials, in particular the skin, comprising (i) a first aqueous composition comprising ascorbic acid or one of its derivatives and polyquaternium-67, and (ii) a second composition comprising, in at least one glycol, ferulic acid or one of its derivatives.

[0035] First aqueous composition (i)

[0036] The invention comprises (i) a first aqueous composition comprising ascorbic acid or one of its derivatives and polyquaternium-67.

[0037] Ascorbic acid or one of its derivatives

[0038] The ascorbic acid according to the invention may be in D or L form.

[0039] Preferably, the ascorbic acid for the purposes of the invention corresponds to L- ascorbic acid, or vitamin C. It has a structure according to the following formula (I):

[0040] [Chem 1]

[0041] The composition (i) may also comprise an ascorbic acid derivative which is an ascorbic acid salt, for example sodium ascorbate, magnesium or sodium ascorbylphosphate, and glycosylated ascorbic acid. The composition (i) may also comprise an ascorbic acid derivative. Mention may be made for example of ascorbic acid sugar esters and phosphorylated ascorbic acid metal salts.

[0042] Among the ascorbic acid sugar esters, mention may be made of glycosylated, mannosylated, fructosylated, fucosylated, galactosylated N-acetylglucosamine, N- acetylmuramic derivatives of ascorbic acid and mixtures thereof and more especially ascorbyl-2 glucoside or 2-0-a-D glucopyranosyl of L-ascorbic acid or 6-O-p-D- galactopyranosyl of L-ascorbic acid. The latter compounds as well as their preparation processes are in particular described in documents EP 487 404, EP 425 066 and J05213736.

[0043] The phosphorylated ascorbic acid metal salt may be chosen from alkali metal ascorbyl phosphates, alkaline earth metal ascorbyl phosphates and transition metal ascorbyl phosphates.

[0044] Ascorbic acid is in particular available under the commercial reference Ascorbic Acid (L) from Reckon Organics, and under the reference Ascorbic Acid Ultra Fine Powder from DSM Nutritional Products.

[0045] Suitable ascorbic acid derivatives according to the present invention may be chosen from 5,6-di-O-dimethylsilylascorbate marketed under the reference PRO-AA by Exsymol, dl-alpha-tocopheryl-dl-ascorbyl-phosphate potassium salt marketed under the reference Sepivital EPC by Senju Pharmaceutical, magnesium ascorbyl phosphate, sodium ascorbyl phosphate marketed under the reference Stay-C 50 by Roche and ascorbyl glucoside marketed by Hayashibara.

[0046] Preferably, the first composition (i) comprises from 0.12% to 20% by weight of ascorbic acid or one of its derivatives, with respect to the total weight of composition (i), preferably from 1% to 18% by weight, preferably from 10% to 17% by weight.

[0047] The stable cosmetic composition according to the invention comprises from 0.1% to 15% by weight of ascorbic acid or one of its derivatives with respect to the total weight of the composition, preferably from 1% to 14% by weight, preferably from 5% to 13% by weight.

[0048] Polyquaternium-67 Preferably, the first composition (i) comprises from 0.1 to 1% by weight of polyquaternium-67 with respect to the total weight of composition (i), preferably from 0.2 to 0.8% by weight, preferably from 0.2 to 0.5% by weight.

[0049] Polyquaternium-67 is for example marketed under the reference Softcat Polymer SL-100 by Amerchol (Dow Chemical).

[0050] Preferably, the stable cosmetic composition according to the invention comprises from 0.1 to 1% by weight of polyquaternium-67 with respect to the total weight of the composition, preferably from 0.2% to 0.8% by weight, preferably from 0.2% to 0.6% by weight, and more preferably from 0.2 to 0.5% by weight.

[0051] Water

[0052] Preferably, the first composition (i) comprises at least 40% by weight of water with respect to the total weight of composition (i), preferably at least 45% by weight of water, preferably at least 50% by weight of water, preferably at least 55% by weight of water, and preferably at least 60% by weight of water.

[0053] The water used may be sterile demineralized water and / or floral water such as rose water, cornflower water, chamomile water or linden water, and / or a spring or natural mineral water, such as for example: Vittel water, water from the basin of Vichy, llriage water, la Roche Posay water, la Bourboule water, Enghien-les-Bains water, Saint Gervais-les-Bains water, Neris-les-Bains water, Allevar-les-Bains water, Digne water, Maizieres water, Neyrac-les-Bains water, Lons-le-Saunier water, les Eaux Bonnes, Rochefort water, Saint Christau water, Fumades water and Tercis-les-bains water, Avene water.

[0054] Preferably, composition (i) according to the invention is an aqueous solution. Preferably, the composition according to the invention is a single-phase composition. The term "single-phase" means that the composition according to the invention has no dispersed phase (also known as discontinuous phase) in droplet form in a dispersing phase (also known as continuous phase). Such a composition may be called "serum". The term "serum" denotes a composition of fluid, flowing texture.

[0055] Solvents

[0056] Preferably, composition (i) according to the invention is totally free from water- soluble organic solvent. Preferably, the term water-soluble organic solvent denotes organic solvents chosen from among alcohols, polyols and mixtures thereof.

[0057] Among the alcohols, mention may be made of C1-C10, more preferably C1-C5, alcohols, such as ethanol, isopropanol, propanol and butanol.

[0058] The polyol may be chosen from among polyols having from 2 to 20 carbon atoms, such as glycerol, diglycerol, propylene glycol, isoprene glycol, dipropylene glycol, butylene glycol, caprylyl glycol, hexylene glycol, 1 ,3-propanediol, pentylene glycol, polyethylene glycols having from 2 to 200 ethylene oxide units and mixtures thereof.

[0059] In particular, composition (i) comprises at least one organic solvent chosen from among glycerol, pentylene glycol, caprylyl glycol and mixtures thereof.

[0060] Preferably, composition (i) comprises a mixture of glycerol, pentylene glycol and caprylyl glycol.

[0061] Preferably, composition (i) according to the invention comprises from 0.1 % to 35% by weight, preferably from 1% to 30% by weight, preferably from 5% to 25% by weight, preferably from 10% to 20% by weight, preferably from 15% to 19% by weight of organic solvent with respect to the total weight of composition (i).

[0062] Base

[0063] Composition (i) may optionally comprise at least one base.

[0064] The base may be an organic base or a mineral base.

[0065] By way of example of organic base, mention may be made of primary, secondary or tertiary alkylamines, for example triethylamine or butylamine.

[0066] By way of example of mineral base, mention may be made of metal or ammonium hydroxides, such as LiOH, NaOH, KOH, Ca(OH)2, NH4OH, Mg(OH)2or Zn(OH)2.

[0067] Preferably, the base is chosen from mineral bases, preferably from alkaline metal hydroxide, preferably is sodium hydroxide or potassium hydroxide, advantageously is sodium hydroxide.

[0068] Preferably, when it comprises a base, composition (i) comprises from 0.1% to 10% by weight of base with respect to the total weight of composition (i), preferably from 0.5% to 6% by weight, preferably from 1% to 5% by weight, preferably from 2% to 4% by weight.

[0069] The composition may also comprise one or more additive(s) conventionally used in cosmetic compositions, preferably chosen from among active agents, chelating agents, preservatives and perfumes. Preferably, among the additives that can be used, adenosine, sodium hyaluronate, trisodium ethylenediamine disuccinate, hydroxyacetophenone or mixtures thereof.

[0070] Second composition (ii)

[0071] The invention comprises a second composition (ii) comprising, in at least one glycol, ferulic acid or one of its derivatives.

[0072] Ferulic acid

[0073] Composition (ii) according to the invention comprises ferulic acid or one of its derivatives.

[0074] Ferulic acid is the common name of [(hydroxy-4-methyl-3)-3-phenyl]-3-propene-2- oic acid. It has a structure according to the following formula (II):

[0075] [Chem 2]

[0076] "Derivatives" of ferulic acid denotes in particular its esters and / or salts and / or plant extracts containing it.

[0077] As ferulic acid "esters", mention may be made in particular of esters of ferulic acid and C1-C30 alcohols, in particular methyl ferulate, ethyl ferulate, isopropyl ferulate, octyl ferulate and oryzanyl ferulate.

[0078] As ferulic acid "salts", mention may be made in particular of organic ferulic acid salts, in particular sodium salts such as sodium ferulate and sodium isoferulate.

[0079] As "plant extracts" containing ferulic acid, mention may be made in particular of rice, wheat, barley, oats, tree bark, poplar buds, asparagus, olives, berries. Preferably, the bran fraction of rice, wheat, barley, or oats is used. According to a particular embodiment, wheat bran extract will be used.

[0080] Preferably, the ferulic acid derivatives are chosen from among esters of ferulic acid and C1-C30 alcohols, organic ferulic acid salts, plant extracts containing ferulic acid, and mixtures thereof. Ferulic acid is in particular available under the sales reference Oryza Ferulix from Oryza Oil & Fat Chemicals.

[0081] Preferably, the second composition (i) according to the invention comprises from 0.04 to 5% by weight of ferulic acid or one of its derivatives, with respect to the total weight of composition (ii), preferably from 0.5 to 4% by weight, and even more preferably from 1 to 3% by weight.

[0082] The stable cosmetic composition according to the invention comprises from 0.01 to 1% by weight of ferulic acid or one of its derivatives with respect to the total weight of the composition, preferably from 0.1 % to 0.8% by weight, preferably from 0.3% to 0.7% by weight.

[0083] Glycol

[0084] Composition (ii) according to the invention comprises at least one glycol. The term glycol denotes a diol wherein the two hydroxyl groups are carried by two different carbon atoms.

[0085] The glycol can be chosen from among polyols having from 2 to 20 carbon atoms, such as glycerol, diglycerol, propylene glycol, isoprene glycol, dipropylene glycol, butylene glycol, caprylyl glycol, hexylene glycol, 1 ,3-propanediol, pentylene glycol, polyethylene glycols having from 2 to 200 ethylene oxide units or mixtures thereof.

[0086] Preferably, the glycol is dipropylene glycol.

[0087] Dipropylene glycol is in particular available under the sales reference Dipropylene Glycol from Ineos.

[0088] Preferably, composition (ii) according to the invention comprises at least 20% by weight, preferably at least 30% by weight, preferably at least 40% by weight, preferably at least 50% by weight, preferably at least 60% by weight, preferably at least 70% by weight, preferably at least 80% by weight, preferably at least 85% by weight, preferably at least 90% by weight, preferably at least 95% by weight, preferably at least 98% by weight of glycol with respect to the total weight of composition (ii).

[0089] The composition according to the invention may be obtained conventionally by those skilled in the art. The expressions "between ... and ..." and "ranging from ... to ..." are to be understood to be inclusive of the limits, unless specified otherwise.

[0090] The following examples make it possible to understand the invention better, without being in anyway limitative. The raw materials are referred to with the chemical or INCI name thereof. The amounts indicated are as a % by weight of raw materials with respect to the total weight of the composition (% w / w), unless specified otherwise.

[0091] EXAMPLES

[0092] I - Preparation of an extemporaneous composition according to the invention

[0093] A first composition (i) C1 based on ascorbic acid and a second composition (ii) C2 based on ferulic acid, according to the invention, are prepared according to the ingredients of Table 1 below:

[0094] [Table 1]

[0095] A composition 11 (stable cosmetic composition according to the invention) is then prepared by extemporaneously mixing 75% by weight of C1 and 25% by weight of C2 with respect to the total weight of the mixture C1+C2. The composition obtained is as follows:

[0096] [Table 2] 11 - Stability of the extemporaneous composition according to the invention

[0097] The stability of composition 11 (stable cosmetic composition according to the invention) was tested in duplicated tests. To evaluate the stability of the composition, the chemical losses of ascorbic acid and of ferulic acid are evaluated on day 1 , day 4, day 7, day 14, day 21 , day 30 and day 60 after mixing C1 + C2, and at ambient temperature.

[0098] Measurement of chemical losses:

[0099] The chemical losses of ascorbic acid and of ferulic acid are measured with a liquid chromatography method combined with UV detection, according to the following parameters:

[0100] Column: ACQUITY UPLC HSS T3 RP18 100x2.1 mm in 1.7pm

[0101] Eluent: 0.006 mol / L Di-Sodium Hydrogen Phosphate buffer, pH 2.1 / ACN (20 / 80 v / v)

[0102] Flow rate: 0.35ml / min

[0103] Injection volume: 1 l

[0104] Temperature: 50°C

[0105] A detection: U.V. from 200 to 300 nm:

[0106] Ascorbic acid extraction is at 250nm, and ferulic acid extraction is at 320nm.

[0107] The results obtained are compiled in Table 3 below:

[0108] [Table 3]

[0109] Vitamin C (ascorbic acid) is stable for up to 2 months at ambient temperature (chemical loss <20%).

[0110] The stability of ferulic acid is conforming at ambient temperature for up to 1 month (at 3 weeks of use: 10% loss; at 4 weeks: 13% loss). From 2 months, the chemical loss is 30% which is no longer acceptable.

[0111] In conclusion, good stability of ascorbic acid and ferulic acid is observed in composition 11 for up to 1 month at ambient temperature after the first use (5 drops per day) of the extemporaneous mixture at pH6. II - Stability of the extemporaneous composition according to the invention as a function of temperature

[0112] The stability of composition 11 (stable cosmetic composition according to the invention) was tested at ambient temperature (AT) and at 45°C according to two independent tests.

[0113] To evaluate the stability of the composition, the chemical losses of ascorbic acid and of ferulic acid are evaluated on day 7, day 14, day 21 , day 28, day 21 and day 60 after mixing C1 + C2, at ambient temperature or at 45°C (protocol above).

[0114] Test 1 :

[0115] [Table 4] Test 2:

[0116] [Table 5]

[0117] It is observed that at ambient temperature, ascorbic acid is stable for up to two months (less than 9% losses), and ferulic acid is stable for at least 4 weeks. At a temperature of 45°C, ascorbic acid remains stable for up to at least 4 weeks, but ferulic acid is degraded substantially from 1 week (30% losses). A ferulic acid loss of more than 96% is observed after 2 months at 45°C.

[0118] III - Stability of the compositions C1 and C2 according to the invention

[0119] The stability of compositions C1 and C2 was tested at 45°C according to two independent tests.

[0120] To evaluate the stability of these compositions, the chemical losses of ascorbic acid and of ferulic acid are evaluated on day 0 and day 30 after preparation of each of the compositions C1 and C2 at 45°C (protocol above).

[0121] [Table 6]

[0122] Vitamin C (ascorbic acid) is stable for at least 2 months (30 days) at 45°C in composition C1 (chemical loss «20%). Ferulic acid is stable for at least 2 months (30 days) at 45°C in composition C2 (chemical loss «20%).

[0123] In conclusion, ascorbic acid and ferulic acid are stable in compositions C1 and C2 respectively for at least 2 months at 45°C and therefore, a fortiori, at room temperature.

Claims

CLAIMS1. Process for preparing a cosmetic composition comprising ascorbic acid or one of its derivatives and ferulic acid or one of its derivatives, comprising extemporaneous mixing of:(i) a first aqueous composition comprising ascorbic acid or one of its derivatives and polyquaternium-67, with(ii) a second composition comprising, in at least one glycol, ferulic acid or one of its derivatives.

2. Process according to claim 1, wherein the first composition (i) comprises between 0.12 and 20% by weight of ascorbic acid or one of its derivatives, with respect to the total weight of composition (i), preferably from 1 to 18% by weight, preferably from 10 to 17% by weight.

3. Process according to claim 1 or 2, wherein the first composition (i) comprises at least 40% by weight of water with respect to the total weight of composition (i), preferably at least 45% by weight of water, preferably at least 50% by weight of water, preferably at least 55% by weight of water, and preferably at least 60% by weight of water.

4. Process according to one of the preceding claims, wherein the first composition (i) comprises from 0.1 to 1% by weight of polyquaternium-67 with respect to the total weight of composition (i), preferably from 0.2 to 0.8% by weight, preferably from 0.2 to 0.5% by weight.

5. Process according to one of the preceding claims, wherein the second composition (ii) comprises between 0.04 and 5% by weight of ferulic acid or one of its derivatives, with respect to the total weight of composition (ii), preferably from 0.5 to 4% by weight, preferably from 1 to 3% by weight.

6. Process according to one of the preceding claims, wherein the second composition (ii) comprises, with respect to the total weight of the composition (ii), at least 20% by weight, preferably at least 30% by weight, preferably at least 40% by weight, preferably at least 50% by weight, preferably at least 60% by weight, preferably at least 70% by weight, preferably at least 80% by weight, preferably at least 85% by weight, preferably at least 90% by weight, preferably at least 95% by weight, preferably at least98% by weight of glycol preferably chosen among polyols having 2 to 20 carbon atoms, such as glycerol, diglycerol, propylene glycol, isoprene glycol, dipropylene glycol, butylene glycol, caprylyl glycol, hexylene glycol, 1 ,3-propanediol, pentylene glycol, polyethyleneglycols having 2 to 200 ethylene oxide units and mixtures thereof, preferably the glycol is dipropylene glycol.

7. Process according to one of the preceding claims, wherein the cosmetic composition obtained has a pH between 4 and 8, preferably between 5 and 7, preferably a pH of 6.

8. Process for the care of keratin materials, in particular the skin, which comprises (1) the process for preparing a cosmetic composition according to one of the preceding claims, then (2) the application of the cosmetic composition on keratin materials, in particular the skin.

9. Care process according to claim 8, wherein the step (2) of applying the cosmetic composition takes place no later than 30 days after the step (1) of preparing said composition.

10. Stable cosmetic composition comprising, with respect to the total weight of the composition:- from 0.1 to 15% by weight of ascorbic acid or one of its derivatives, and- from 0.01 to 1% by weight of ferulic acid or one of its derivatives, and- from 0.1 to 1% by weight of polyquaternium-67, said composition having a pH between 4 and 8, preferably between 5 and 7, and preferably a pH of 6.

11. Cosmetic composition according to claim 10, characterized in that it is stable at ambient temperature, i.e. between 20°C and 25°C.

12. Kit for the care and / or treatment of keratin materials, in particular the skin, comprising (i) a first aqueous composition comprising ascorbic acid or one of its derivatives and polyquaternium-67, and (ii) a second composition comprising, in at least one glycol, ferulic acid or one of its derivatives.

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