ANTIMICROBIAL MIXTURE CONTAINING 4-(3-ETHOXY-4-HYDROXYPHENYL)-BUTAN-2-ONE AND 4-HYDROXYACETOPHENONE AND COMPOSITION THEREOF
Patent Information
- Application Number
- DE602019070323
- Authority / Receiving Office
- DE · DE
- Patent Type
- Patents
- Current Assignee / Owner
- Priority Date
- 2019-12-03
- Filing Date
- 2019-12-17
- Publication Date
- 2025-05-21
- Estimated Expiration
- 2039-12-17
AI Technical Summary
Existing antimicrobial compositions face challenges such as reduced efficacy due to solubility incompatibilities, odor issues, and instability over time, especially when combined with other antimicrobials, necessitating the development of stable and effective antimicrobial mixtures for cosmetic, pharmaceutical, and food products.
A combination of 4-(3-ethoxy-4-hydroxyphenyl)butan-2-one and 4-hydroxyacetophenone, or their organic or mineral base salts and solvates, is used to create an antimicrobial mixture that exhibits synergistic activity and stability over time, maintaining effectiveness without odor changes.
The combination achieves improved antimicrobial activity against microorganisms like Aspergillus niger, Escherichia coli, and Candida albicans, while remaining stable and odorless for several weeks or months, even at elevated temperatures.
Description
[0001] The present invention relates to an antimicrobial mixture of i) 4-(3-ethoxy-4-hydroxyphenyl)butan-2-one and ii) 4-hydroxyacetophenone as well as their base salts, their solvates such as hydrates, as well as a cosmetic, pharmaceutical or food composition containing i) and ii). Technical field
[0002] Microorganisms can survive and spread in cosmetic, pharmaceutical, and food products without preservatives. Preservatives are routinely added to all industrial preparations intended for storage or preservation to prevent microbial growth over time.
[0003] Microbial contamination during the manufacturing of industrial products is common, even when the starting ingredients used in the product are "clean," i.e., without the presence of contaminating microorganisms. Water, for example, which is omnipresent in most cosmetic, pharmaceutical, or food products, must be free of contaminating microorganisms. All other ingredients must also be screened for the presence of contaminating microorganisms. Cleanliness during the manufacturing of these industrial products, the processing of contents, and the filling of containers must be scrupulously monitored. Despite these precautions, the microbial integrity of the products may require the presence of one or more preservatives compatible with the product and the stability of the composition. The products must not allow the growth or viability of contaminating microorganisms.Although strict sterile production may be feasible industrially, maintaining sterility during use remains problematic, as fingers, cosmetic applicators, and even ambient air are not sterile. Preservatives are therefore necessary to reduce consumer contamination with microorganisms during normal use. As a general rule, pathogenic microorganisms must be absent from all commercial products, particularly cosmetics. ( Kirk Othmer Encyclopedia, Cosmetics, Martin M. Rieger, 04 / 12 / 2000; https: / / doi.org / 10.1002 / 0471238961.0315191318090507.a01). Over the years, preservation issues have also led to the introduction of spectrum preservatives vs. resistant contaminating microorganisms.
[0004] Furthermore, it appears that some of the commonly used preservatives are inactivated by a variety of surfactants. The more hydrophobic the preservative, the greater the danger that it will become trapped in organized molecular systems such as micelles and subsequently become less effective or ineffective against microorganisms, particularly pathogens. ( Ullmann's Encyclopedia of Industrial Chemistry, "Skin Cosmetics", G. Schneider et al., vol. 33, p. 221, 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002 / 14356007.a24_219).
[0005] Therefore, it is of great interest to propose new antimicrobial associations that address these challenges.
[0006] 4-(3-Ethoxy-4-hydroxyphenyl)butan-2-one i) is an ingredient known as a preservative in cosmetic compositions to protect the compositions from microbial contamination (see e.g. WO 2011 / 039445).
[0007] However, it is desirable to be able to incorporate said ingredient i) in reduced concentration in compositions, in particular cosmetic or dermatological compositions, while maintaining good antimicrobial preservation performance. In addition, antimicrobial compounds do not always have good compositional stability and / or good antimicrobial activity over time, especially when the antimicrobial compound is combined with other antimicrobials which may have solubility incompatibilities, problems with odor, compositional stability over time and / or antimicrobial ineffectiveness. It is of great interest to provide compositions, in particular cosmetic or dermatological compositions, which not only have an identical or even increased antimicrobial effect and which are also found in compositions which are stable over time, avoiding a change in odor, while maintaining its capacity as a preservative over time, i.e.antimicrobial efficacy. In addition, it is also interesting to have a composition that includes several antimicrobials that remains stable in terms of formulation, that is not too viscous, i.e. less than 45 poises, and which does not change in appearance and / or viscosity over time, even after several weeks or even months of storage at a temperature greater than or equal to 25°C, in particular between 37 and 45°C.
[0008] It has been unexpectedly discovered that the combination of: i) 4-(3-ethoxy-4-hydroxyphenyl)butan-2-one or one of its organic or mineral base salts, as well as its solvates such as hydrates; with ii) 4-hydroxyacetophenone or one of its organic or mineral base salts, as well as its solvates such as hydrates; makes it possible to obtain an antimicrobial mixture exhibiting a clear improvement or even synergy of antimicrobial activity. In addition, it appears that the composition comprising i) and ii) remains stable even after several weeks or even months at room temperature or even at temperatures above 25°C, in particular between 37 and 45°C. Furthermore, it appears that the combination of the two compounds i) and ii) does not exhibit an odor or a reduced odor. Furthermore, it appears that neither the combination of ingredients i) and ii) nor the composition presents a change in odor or a bad odor that appears over time.
[0009] The invention also relates to a non-therapeutic cosmetic treatment process for keratin materials comprising the application to the keratin materials of a composition, in particular a cosmetic composition, as described above. The process may be a cosmetic process for caring for, making up, perfuming or cleaning keratin materials.
[0010] The invention also relates to a method for preserving a composition, in particular comprising a physiologically acceptable medium, in particular a cosmetic or pharmaceutical composition, or a food composition, characterized in that it consists of incorporating into said composition an antimicrobial mixture as described above.
[0011] The results of the examples described below show the antimicrobial activity of the combination of i) + ii) is improved according to the minimum inhibitory concentration (MIC) measurements made with several mixtures, vs. i) alone or ii) alone at equivalent quantity. The antimicrobial activity is considered to be synergistic when the antimicrobial mixture makes it possible to obtain a percentage of growth of the strain less than or equal to 25%, or even less than or equal to 20%.
[0012] The combination of i) 4-(3-ethoxy-4-hydroxyphenyl)butan-2-one and its organic or inorganic acid or base salts or solvates such as hydrates with ii) 4-hydroxyacetophenone and its acid or base salts or solvates such as hydrates makes it possible to obtain an antimicrobial mixture exhibiting excellent antimicrobial activity, in particular against Aspergillus niger, Escherichia coli, Staphylococcus aureus, and Candida albicans. IlIt also appears that the improvement was obtained whether with a "simplex" or more "complex" formula support. In addition, the formulas remain stable over time while maintaining antimicrobial activity over time even after 7 days, 15 days, 1 month, and at room temperature.
[0013] More specifically, the invention relates to an antimicrobial mixture comprising, or consisting of (or consisting of), i) 4-(3-ethoxy-4-hydroxyphenyl)butan-2-one and its acid or base salts, organic or mineral, and its solvates such as hydrates and ii) 4-hydroxyacetophenone, and its acid or base salts, organic or mineral, and the solvates such as hydrates, the combination of 80 to 90% by weight, relative to the total weight of said combination.
[0014] For the purposes of the present invention, and unless otherwise indicated: By " polymerthickener" means a polymer which, when introduced at 1% by weight into an aqueous or hydroalcoholic solution containing 30% ethanol, and at pH = 7 or into an oil chosen from vaseline oil, isopropyl myristate or cyclopentadimethylsiloxane, makes it possible to achieve a viscosity of at least 100 cps, preferably at least 500 cps, at 25°C and at a shear rate of 1 s -1< . This viscosity can be measured using a cone / plate viscometer (Haake R600 Rheometer or similar). The thickening polymers can be thickeners of the aqueous phase and / or the fatty phase, preferably of the aqueous phase; By thickening polymer " organic »means a thickening polymer as defined above which is made up of carbon, hydrogen, and optionally nitrogen, oxygen, sulfur, halogens such as fluorine, chlorine, bromine as well as phosphorus, alkali metals such as sodium, potassium, or alkaline earth metals such as magnesium or calcium. The organic polymers according to the invention do not include silicon; By the expression " non-cellulosic organic thickening polymer”, according to the invention, we mean an organic thickening polymer not comprising a cellulose unit; By " surfactant » we hear a "surfactant" " Or "surfactant" which is a compound capable of modifying the surface tension between two surfaces, surfactants are amphiphilic molecules, i.e. which have two parts of different polarity, one lipophilic and apolar and the other hydrophilic and polar; By " fat body",For the purposes of the present invention, an organic compound is understood to be insoluble in water at ordinary temperature (25°C) and atmospheric pressure (760 mm Hg) (solubility less than 5%, and preferably 1%, even more preferably 0.1%); in addition, the fatty substances are soluble in organic solvents under the same temperature and pressure conditions, such as for example in halogenated solvents such as chloroform, dichloromethane, lower alcohols such as ethanol or aromatic solvents such as benzene or toluene. By " salt of organic or mineral acid »more particularly, salts chosen from a salt derived from i) hydrochloric acid HCl, ii) hydrobromic acid HBr, iii) sulfuric acid H 2 SO 4 , iv) alkylsulfonic acids: Alk-S(O) 2 OH such as methylsulfonic acid and ethylsulfonic acid; v) arylsulfonic acids: Ar-S(O) 2 OH such as benzenesulfonic acid and toluenesulfonic acid; vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid, x) alkoxysulfinic acids: Alk-OS(O)OH such as methoxysulfinic acid and ethoxysulfinic acid; xi) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; xii) phosphoric acid H 3 PO 4 ; xiii) acetic acid CH 3 C(O)OH ; xiv) triflic acid CF 3 SO 3 H and xv) tetrafluoroboric acid HBF 4 ; By " salts of organic or mineral bases» means the salts of bases or alkaline agents as defined below as alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines. By "cationic counterion" » means a cation or a cationic group derived from an organic or mineral base salt counterbalancing the anionic charge of the ingredients of formula (I') or (II'); more particularly the cationic counterion is chosen from i) alkali metals such as sodium, potassium, preferably Na +<, ii) alkaline earth metals such as calcium; iii) ammonium R 4 N +< with R, identical or different, represents a hydrogen atom, or a (C 1 -C 6 )alkyl group optionally substituted by one or more hydroxyl groups, preferably R represents a hydrogen atom or a (C 1 -C 4 )alkyl group such as methyl. a hydrocarbon chain is unsaturated when it comprises one or more double bonds and / or one or more triple bonds; an “alkyl radical” is a saturated hydrocarbon radical in C 1 -C 20 , linear or branched, preferably C 1 -C 6 , more preferably C 1 -C 4 such as methyl, or ethyl; A "alkylene radical" is a saturated divalent hydrocarbon radical as defined above which may contain from 1 to 4 double bonds -C=C-, conjugated or not; particularly the alkenylene group contains 1 or 2 unsaturations; the expression " possibly substituted » attributed to the alkyl radical implies that said alkyl radical can be substituted by one or more radicals chosen from the radicals i) hydroxyl, ii) C 1 -C 4 alkoxy, iii) acylamino, iv) amino optionally substituted by one or two alkyl radicals, identical or different, in C 1 -C 4 ,;; a "alkoxy radical"is an alkyl-oxy radical for which the alkyl radical is a hydrocarbon radical, linear or branched, in C 1 -C 16 preferentially in C 1 -C 8; - The expression “ at least one » is equivalent to « one or more » ; and the expression "inclusively » for a concentration range means that the limits of the range are part of the defined interval. he has 4-(3-ethoxy-4-hydroxyphenyl)butan-2-one is a compound of formula (I):
[0015]
[0016] i) 4-(3-ethoxy-4-hydroxyphenyl)butan-2-one can be found in solvated form, in particular hydrated.
[0017] i) 4-(3-ethoxy-4-hydroxyphenyl)butan-2-one can be found in salified form by an organic or mineral base of the following formula (I'):
[0018] Formula (I') in which M +< represents a cationic counterion, in particular an alkali metal such as sodium, or potassium, an alkaline earth metal such as calcium or an ammonium. ii) 4-hydroxyacetophenone, also called 4-hydroxyphenylethanone, p-acetophenol, p-hydroxyphenylmethylketone, piceol is a compound of formula (II):
[0019]
[0020] ii) 4-hydroxyacetophenone can be found in solvated form, in particular hydrated.
[0021] ii) 4-hydroxyacetophenone can be found in salified form by an organic or mineral base of the following formula (II'):
[0022] Formula (II') with M +< represents a cationic counterion, in particular an alkali metal such as sodium, or potassium, an alkaline earth metal such as calcium or an ammonium.
[0023] According to a particular embodiment of the invention, i) 4-(3-ethoxy-4-hydroxyphenyl)butan-2-one and ii) 4-hydroxyacetophenone are present in said mixture or in the composition in a content such that the weight ratio i) / ii) ranges from 0.05 to 5, preferably ranges from 0.08 to 5, preferentially ranges from 0.08 to 0.25, and from 2 to 4, more preferentially ranges from 0.15 to 0.25 and from 3 to 3.8. Such a mixture has good antimicrobial activity on molds, in particular on Aspergillus niger.
[0024] Advantageously, i) 4-(3-ethoxy-4-hydroxyphenyl)butan-2-one and ii) 4-hydroxyacetophenone are present in said mixture or in the composition in a content such that the weight ratio i) / ii) ranges from 0.08 to 0.5, preferably ranges from 0.08 to 0.3, preferentially ranges from 0.08 to 0.25, more preferentially ranges from 0.15 to 0.25. Such a mixture has good antimicrobial activity on molds, in particular on Aspergillus niger.
[0025] According to another particular embodiment of the invention, i) 4-(3-ethoxy-4-hydroxyphenyl)butan-2-one and ii) 4-hydroxyacetophenone are present in said mixture or in the composition in a content such that the weight ratio i) / ii) is 0.5 to 5, preferably 1 to 4 and more preferably 3 to 3.8. Such a mixture has good antimicrobial activity on Aspergillus niger. Escherichia coli, Staphylococcus aureus, and Candida albicans and this over time even after several weeks (1 week, 2 weeks or even a month). The composition
[0026] Another subject of the invention is a composition comprising: (i) one or more 4-(3-ethoxy-4-hydroxyphenyl)butan-2-ones and their organic or mineral acid or base salts and their solvates such as hydrates and (ii) one or more 4-hydroxyacetophenones and their organic or mineral acid or base salts and their solvates such as hydrates.
[0027] The composition is a physiologically acceptable medium. The composition is in particular a cosmetic or pharmaceutical or dermatological composition. The composition can also be a food composition (food). The physiologically acceptable environment:
[0028] The term "physiologically acceptable medium" means a medium suitable for application to keratin materials, also called a formula support, which is a cosmetic or pharmaceutical medium generally consisting of water or a mixture of water and one or more organic solvents or a mixture of organic solvents. Preferably, the composition comprises water and in a content of, inclusively, in particular between 5% and 99.9% relative to the total weight of the composition, more preferably between 10 and 90%, even more preferably between 20% and 80% by weight relative to the total weight of the composition. Organic Solvents:
[0029] By "organic solvent", we mean an organic substance capable of dissolving another substance without chemically modifying it.
[0030] Examples of organic solvents that may be mentioned include a) C 2 -C 6 alkanols, such as ethanol and isopropanol; b) polyols miscible with water at room temperature (25°C), chosen in particular from polyols having in particular from 2 to 10 carbon atoms, preferably having from 2 to 6 carbon atoms, such as glycerin, propylene glycol, 1,3-propanediol, butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol, diethylene glycol, diglycerin; c) polyol ethers such as 2-butoxyethanol, propylene glycol monomethyl ether, monoethyl ether and diethylene glycol monomethyl ether, and d) aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.
[0031] According to a particular embodiment, the composition further comprises one or more polyols, notably chosen from polyols having in particular from 2 to 10 carbon atoms, preferably having from 2 to 6 carbon atoms, such as glycerin.
[0032] In a preferred embodiment, 4-(3-ethoxy-4-hydroxyphenyl)butan-2-one is used in combination with an effective amount of at least one organic solvent which may be selected from ethanol, 1,2-propylene glycol, 1,3-propanediol, PEG-8 (polyethylene glycol containing 8 ethylene glycol units), propylene carbonate, dipropylene glycol, 1,2-hexylene glycol, PEG-4.
[0033] Preferably, the organic solvent is chosen from ethanol, 1,2-propylene glycol, 1,3-propanediol, PEG-8, propylene carbonate.
[0034] Advantageously, the composition according to the invention comprises 1,3-propanediol, in particular in a content ranging from 0.1 to 20% by weight, relative to the total weight of the composition, and preferably ranging from 0.1 to 10% by weight, preferentially ranging from 0.5 to 5% by weight.
[0035] For food composition, water will be preferred and organic solvents suitable for consumption such as ethanol.
[0036] The organic solvents are preferably present in proportions preferably inclusively between 0.1 and 40% by weight approximately relative to the total weight of the composition, and more preferably between 1 and 20% by weight approximately and even more particularly inclusively between 5% and 10% by weight relative to the total weight of the composition. The pH:
[0037] The pH of the composition according to the invention is generally between approximately 2 and 12 inclusive, and preferably between approximately 3 and 11. It can be adjusted to the desired value using acidifying or alkaline agents usually used in dyeing keratin fibers or even using conventional buffer systems.
[0038] The pH of the composition is preferably between 6 and 9 inclusive, particularly between 7 and 9 and more particularly around neutral pH 7.
[0039] Among the acidifying agents, mention may be made, for example, of mineral or organic acids as defined above, in particular hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acids.
[0040] Among the bases or alkaline agents, mention may be made, for example, of ammonia, alkali carbonates, alkanolamines and other alkaline agents as defined below, preferably alkanolamines such as mono-, di- and triethanolamines. The surfactant(s)
[0041] According to a particular embodiment of the invention, the composition comprises one or more surfactants. The surfactant(s) may be non-ionic, anionic, cationic, zwitterionic or amphoteric, preferably the surfactant(s) are non-ionic or anionic.
[0042] Among the non-ionic surfactants according to the invention, mention may be made, alone or in mixtures, of a) fatty alcohols, b) alpha-diols, c) alkylphenols, these 3 types of compounds a) to c) being polyethoxylated, polypropoxylated and / or polyglycerolated, and having a fatty chain comprising, for example, 8 to 30 carbon atoms, in particular comprising 10 to 22 carbon atoms, the number of ethylene oxide or propylene oxide groups being able to range in particular from 2 to 200, in particular from 10 to 100 and the number of glycerol groups being able to range in particular from 2 to 200, in particular from 10 to 100.Mention may also be made of copolymers of ethylene oxide (EO) and propylene oxide (PO), condensates of ethylene oxide and propylene oxide on fatty alcohols; polyethoxylated fatty amides preferably having from 2 to 30 moles EO, polyglycerolated fatty amides comprising on average 1 to 5 glycerol groups and in particular 1.5 to 4; oxyethylenated sorbitan fatty acid esters having from 2 to 200 moles EO, in particular from 10 to 100 EO; sucrose fatty acid esters, polyethylene glycol fatty acid esters, alkylpolyglycosides, N-alkyl glucamine derivatives, amine oxides such as (C 10 -C 14 ) alkyl amine oxides or N-acylaminopropylmorpholine oxides.
[0043] Preferably, the non-ionic surfactant is chosen from: (poly)ethoxylated fatty alcohols; glycerolated fatty alcohols; alkylpolyglycosides. Preferably mono and diesters of oxyethylenated sorbitan fatty acids having from 2 to 200 moles EO, in particular from 10 to 100 EO.
[0044] More preferably, the surfactants are chosen from mono and diesters of oxyethylenated sorbitan fatty acids having from 2 to 200 moles EO, in particular from 10 to 100 EO such as propylene glycol stearate having from 10 to 30 EO such as 20 EO; glyceryl mono distearate / polyethylene glycol stearate (100 EO).
[0045] By fatty chain is meant a hydrocarbon chain comprising 6 to 30 carbon atoms, preferably 8 to 24 carbon atoms, linear or branched, saturated or unsaturated, such as stearyl.
[0046] As regards alkylpolyglycosides, these compounds are well known and can be more particularly represented by the following general formula: R 1 O-(R 2 O) t (G) v (III) Formula (III) in which: R 1 represents a linear or branched alkyl and / or alkenyl radical comprising approximately 8 to 24 carbon atoms, an alkylphenyl radical whose linear or branched alkyl radical comprises 8 to 24 carbon atoms; R 2 represents an alkylene radical comprising approximately 2 to 4 carbon atoms; G represents a sugar unit comprising 5 to 6 carbon atoms; t denotes an integer between 0 and 10 inclusive, preferably between 0 and 4, preferably between 0 and 4; and v denotes an integer between 1 and 15 inclusive.
[0047] Preferred alkylpolyglycosides according to the present invention are compounds of formula (III) in which R 1 more particularly denotes a saturated or unsaturated, linear or branched alkyl radical comprising from 8 to 18 carbon atoms, t denotes a value ranging from 0 to 3 and more particularly still equal to 0, G can denote glucose, fructose or galactose, preferably glucose. The degree of polymerization, i.e. the value of v in formula (III), can range from 1 to 15, preferably from 1 to 4. The average degree of polymerization is more particularly between 1 and 2 and even more preferably from 1.1 to 1.5.
[0048] The glycosidic bonds between the sugar units are of the 1-6 or 1-4 type and preferably 1-4.
[0049] Compounds of formula (III) are notably represented by the products sold by the company COGNIS under the names PLANTAREN ®< (600 CS / U, 1200 and 2000) or PLANTACARE ®< (818, 1200 and 2000). It is also possible to use the products sold by the company SEPPIC under the names TRITON CG 110 (or ORAMIX CG 110) and TRITON CG 312 (or ORAMIX ®< NS 10), the products sold by the company BASF under the name LUTENSOL GD 70 or those sold by the company CHEM Y under the name AG10 LK.
[0050] It is also possible to use, for example, C8 / C16 alkyl polyglucoside 1,4 in 53% aqueous solution marketed by COGNIS under the reference PLANTACARE ®< 818 UP.
[0051] With regard to mono or polyglycerolated surfactants, they preferably comprise on average from 1 to 40 glycerol groups, more particularly from 10 to 30 glycerol groups such as 20.
[0052] According to a particular embodiment of the invention, the surfactants are monoglycerolated or polyglycerolated and are preferably chosen from the compounds of the following formulas: RO[CH 2 CH(CH 2 OH)O] m H, RO[CH 2 CH(OH)CH 2 O] m H or RO[CH(CH 2 OH)CH 2 O] m H;
[0053] Formulas in which: R represents a saturated or unsaturated, linear or branched hydrocarbon radical comprising from 8 to 40 carbon atoms and preferably from 10 to 30 carbon atoms; m is a number between 1 and 30, preferably between 1 and 10, more particularly from 1.5 to 6. R may optionally comprise heteroatoms such as, for example, oxygen and nitrogen. In particular, R may optionally comprise one or more hydroxyl and / or ether and / or amide groups. R preferably denotes C 10 -C 20 alkyl and / or alkenyl radicals, optionally mono or polyhydroxylated.
[0054] Preferably, the composition of the invention comprises one or more (poly)ethoxylated fatty alcohols suitable for implementing the invention are more particularly chosen from alcohols comprising from 8 to 30 carbon atoms, and preferably from 12 to 22 carbon atoms.
[0055] The (poly)ethoxylated fatty alcohols more particularly have one or more linear or branched, saturated or unsaturated hydrocarbon groups, comprising 8 to 30 carbon atoms, optionally substituted, in particular by one or more hydroxyl groups (in particular 1 to 4). If they are unsaturated, these compounds may comprise one to three carbon-carbon double bonds, conjugated or not.
[0056] The (poly)ethoxylated fatty alcohol(s) preferably have the following formula: R a < -[O-CH 2 -CH 2 ] n -OH with R a< representing a linear or branched C 1 -C 40 alkyl group, or linear or branched C 2 -C 30 alkenyl (preferably C 8 -C 30 alkyl); and n represents an integer between 1 and 200 inclusive, preferably between 2 and 100, more particularly between 10 and 50 inclusive, even more particularly between 15 and 30 inclusive such as 100 or 20.
[0057] (Poly)ethoxylated fatty alcohols are more particularly fatty alcohols containing 8 to 22 carbon atoms and oxyethylenated by 1 to 30 moles of ethylene oxide (1 to 100 EO). Among them, we can cite more particularly lauryl alcohol 20 EO, lauryl alcohol 30 EO, decyl alcohol 3 EO, decyl alcohol 5 EO and oleyl alcohol 20 EO.
[0058] Mixtures of these (poly)oxyethylenated fatty alcohols can also be used.
[0059] Among the non-ionic surfactants, C 6 -C 24 alkyl polyglucosides and (poly)ethoxylated fatty alcohols are preferably used, and C 8 -C 16 alkyl polyglucosides are more particularly used.
[0060] The amount of non-ionic surfactants preferably ranges from 0.5% to 20% by weight, in particular from 1% to 10% by weight, and more particularly from 2 to 5% by weight relative to the total weight of the composition of the invention.
[0061] According to another particular embodiment of the invention, the composition comprises one or more anionic surfactants.
[0062] By "we mean anionic surfactant",a surfactant comprising only anionic groups as ionic or ionizable groups. These anionic groups are preferably chosen from the groups -C(O)OH, -C(O)O -< , -SO 3 H, -S(O) 2 O -< , -OS(O) 2 OH, -OS(O) 2 O -< , -P(O) 2 OH, -P(O) 2 O -< , -P(O)O 2 -< , -P(OH) 2 , =P(O)OH, -P(OH)O -< , =P(O)O -< , =POH, =PO -< , the anionic parts comprising a cationic counterion such as an alkali metal, an alkaline earth metal, or an ammonium, more preferably the groups are carboxy-C(O)OH, or carboxylate -C(O)O -< .
[0063] Examples of anionic surfactants that can be used in the composition according to the invention include alkylcarboxylic acids, alkyl sulfates, alkyl ether sulfates, alkylamidoether sulfates, alkylarylpolyether sulfates, monoglyceride sulfates, alkylsulfonates, alkylamidesulfonates, alkylarylsulfonates, alpha-olefin sulfonates, paraffin sulfonates, alkylsulfosuccinates, alkylethersulfosuccinates, alkylamidesulfosuccinates, alkylsulfoacetates, acylsarcosinates, acylglutamates, alkylsulfosuccinamates, acyl isethionates and N-acyltaurates, salts of alkyl monoesters and polyglycoside-polycarboxylic acids, salts of diesters. alkyl and polyglycoside-polycarboxylic acids, acyllactylates, salts of D-galactoside-uronic acids, salts of alkyl ether-carboxylic acids, salts of alkylaryl ether-carboxylic acids, salts of alkyl amidoether-carboxylic acids,and the corresponding unsalified forms of all these compounds, the alkyl and acyl groups of all these compounds having from 8 to 30 carbon atoms, preferably from 10 to 22 carbon atoms and the aryl group denoting a phenyl group.,
[0064] These compounds can be oxyethylenated and then preferably comprise from 1 to 50 ethylene oxide units.
[0065] The salts of C 6 -C 24 alkyl monoesters and polyglycoside-polycarboxylic acids may be chosen from C 6 -C 24 alkyl polyglycoside-citrates, C 6 -C 24 alkyl polyglycoside-tartrates and C 6 -C 24 alkyl polyglycoside-sulfosuccinates.
[0066] When the anionic surfactant(s) are in salt form, they may be chosen from alkali metal salts such as sodium or potassium salt and preferably sodium salt, ammonium salts, amine salts and in particular amino alcohol salts or alkaline earth metal salts such as magnesium salts.
[0067] Examples of amino alcohol salts include mono-, di- and triethanolamine salts, mono-, di- or triisopropanolamine salts, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol and tris(hydroxymethyl)aminomethane salts.
[0068] Preferably, salts of alkali or alkaline earth metals are used, particularly sodium or magnesium salts.
[0069] Among the anionic surfactants cited, it is preferred to use alkyl(C 6 -C 24 )carboxylic acids, in particular alkyl(C 10 -C 20 )carboxylic acids, preferably of natural origin, in particular plant origin, such as stearic acid, which may be in the form of salts of alkali metals, ammonium, amino alcohols, and alkaline earth metals, or a mixture of these compounds.
[0070] The amount of anionic surfactants preferably ranges from 0.5% to 20% by weight, in particular from 1% to 10% by weight, and more particularly from 2 to 5% by weight relative to the total weight of the composition of the invention.
[0071] The amount of surfactants preferably ranges from 0.5% to 30% by weight, in particular from 1% to 20% by weight, and more particularly from 2 to 10% by weight, more preferably between 4 and 6% relative to the total weight of the composition of the invention. The fatty substance(s)
[0072] The composition of the invention comprises one or more fatty substances. The fatty substances of the invention are not oxyalkylenated.
[0073] Preferably, the fatty substances of the invention are chosen from hydrocarbons, fatty alcohols, fatty esters, silicones and fatty ethers or their mixtures.
[0074] The fatty substances of the invention may be liquid or non-liquid at room temperature (25°C) and at atmospheric pressure (760 mm Hg; or 1,013.105 Pa).
[0075] The liquid fatty bodies of the invention preferably have a viscosity less than or equal to 2 Pa.s, better still less than or equal to 1 Pa.s and even better still less than or equal to 0.1 Pa.s at a temperature of 25°C and at a shear rate of 1 s-1.
[0076] Liquid hydrocarbon means a hydrocarbon composed solely of carbon and hydrogen atoms which is liquid at room temperature (25°C) and atmospheric pressure (760 mm Hg; or 1,013.105 Pa).
[0077] More particularly, the liquid hydrocarbons are chosen from: linear or branched C 6 -C 16 alkanes, possibly cyclic. Examples include hexane, undecane, dodecane, tridecane, isoparaffins such as isohexadecane, isododecane and isodecane. linear or branched hydrocarbons of mineral, animal or synthetic origin with more than 16 carbon atoms, such as paraffin oils, vaseline oil, polydecenes, hydrogenated polyisobutene such as Parléam ®, squalane.
[0078] In a preferred variant, the liquid hydrocarbon(s) are chosen from paraffin oils and vaseline oil.
[0079] Liquid fatty alcohol means a non-glycerolated and non-oxyalkylenated fatty alcohol which is liquid at room temperature (25°C) and atmospheric pressure (760 mm Hg; or 1,013.105 Pa).
[0080] Preferably, the liquid fatty alcohols of the invention comprise from 8 to 30 carbon atoms, more preferably in C 10 -C 22 , even more preferably in C 14 -C 20 , better still in C 16 -C 18 .
[0081] The liquid fatty alcohols of the invention may be saturated or unsaturated.
[0082] Saturated liquid fatty alcohols are preferably branched. They may optionally include at least one aromatic or non-aromatic ring in their structure. Preferably, they are acyclic.
[0083] More particularly, the liquid saturated fatty alcohols of the invention are chosen from octyldodecanol, isostearyl alcohol, 2-hexyldecanol.
[0084] According to another variant of the invention, the fatty substance(s) are chosen from liquid unsaturated fatty alcohols. These liquid unsaturated fatty alcohols have at least one double or triple bond in their structure. Preferably, the fatty alcohols of the invention have one or more double bonds in their structure. When several double bonds are present, they are preferably 2 or 3 in number and they may or may not be conjugated.
[0085] These unsaturated fatty alcohols can be linear or branched.
[0086] They may optionally include in their structure at least one aromatic cycle or not. Preferably, they are acyclic.
[0087] More particularly, the liquid unsaturated fatty alcohols of the invention are chosen from oleic (or oleyl) alcohol, linoleic (or linoleyl) alcohol, linolenic (or linolenyl) alcohol, undecylenic alcohol.
[0088] Oleic alcohol is particularly preferred.
[0089] Liquid fatty esters mean an ester derived from a fatty acid and / or a fatty alcohol and liquid at room temperature (25°C) and atmospheric pressure (760 mm Hg; or 1,013.105 Pa).
[0090] The esters are preferably liquid esters of saturated or unsaturated, linear or branched C 1 -C 26 aliphatic mono or polyacids and of saturated or unsaturated, linear or branched C 1 -C 26 aliphatic mono or polyalcohols, the total number of carbon atoms of the esters being greater than or equal to 10.
[0091] Preferably, for the monoalcohol esters, at least one of the alcohol or acid from which the esters of the invention are derived is branched.
[0092] Among the monoesters of monoacids and monoalcohols, mention may be made of ethyl and isopropyl palmitates, alkyl myristates such as isopropyl myristate, ethyl myristate, isocetyl stearate, ethyl-2-hexyl isononanoate, isodecyl neopentanoate, isostearyl neopentanoate, and C 10 -C 22 alkyl (iso)stearates, preferably C 12 -C 20 such as isopropyl isostearate.
[0093] Also useful are esters of C 4 -C 22 di or tricarboxylic acids and C 1 -C 22 alcohols and esters of mono di or tricarboxylic acids and non-sugar C 4 -C 26 di, tri, tetra or pentahydroxy alcohols.
[0094] Examples include: diethyl sebacate; diisopropyl sebacate; di(2-ethylhexyl) sebacate; diisopropyl adipate; di-n-propyl adipate; dioctyl adipate; di(2-ethylhexyl) adipate; diisostearyl adipate; di(2-ethylhexyl) maleate; triisopropyl citrate; triisocetyl citrate; trisostearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate; neopentyl glycol diheptanoate; diethylene glycol diisononate.
[0095] The composition may also comprise, as liquid fatty ester, esters and diesters of sugars of C 6 -C 30 fatty acids, preferably C 12 -C 22 . It is recalled that the term "sugar" means oxygenated hydrocarbon compounds which have several alcohol functions, with or without aldehyde or ketone function, and which comprise at least 4 carbon atoms. These sugars may be monosaccharides, oligosaccharides or polysaccharides.
[0096] Suitable sugars include, for example, sucrose (or saccharose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, lactose, and their derivatives, in particular alkylated ones, such as methylated derivatives such as methylglucose.
[0097] The esters of sugars and fatty acids may be chosen in particular from the group comprising the esters or mixtures of esters of sugars described above and of C 6 -C 30 fatty acids, preferably C 12 -C 22 , linear or branched, saturated or unsaturated. If they are unsaturated, these compounds may comprise one to three carbon-carbon double bonds, conjugated or not.
[0098] The esters according to this variant can also be chosen from mono-, di-, tri- and tetra-esters, polyesters and their mixtures.
[0099] These esters may be, for example, oleate, laurate, palmitate, myristate, behenate, cocoate, stearate, linoleate, linolenate, caprate, arachidonates, or mixtures thereof, such as in particular the mixed esters oleopalmitate, oleostearate, palmitostearate.
[0100] More particularly, mono- and di-esters are used, and in particular mono- or di-oleate, stearate, behenate, oleopalmitate, linoleate, linolenate, oleostearate, of sucrose, glucose or methylglucose.
[0101] An example is the product sold under the name Glucate ®< DO by the company Amerchol, which is a methylglucose dioleate.
[0102] Finally, natural or synthetic esters of mono, di or triacids with glycerol can also be used.
[0103] Among these we can cite vegetable oils.
[0104] As oils of vegetable origin or synthetic triglycerides, which can be used in the composition of the invention as liquid fatty esters, we can cite for example: triglyceride oils of vegetable or synthetic origin, such as liquid triglycerides of fatty acids containing 6 to 30 carbon atoms such as triglycerides of heptanoic or octanoic acids or, for example, sunflower, corn, soybean, pumpkin, grape seed, sesame, hazelnut, apricot, macadamia, arara, sunflower, castor, avocado oils, triglycerides of caprylic / capric acids such as those sold by the company Stearineries Dubois or those sold under the names Miglyol ®< 810, 812 and 818 by the company Dynamit Nobel, jojoba oil, shea butter oil.
[0105] Preferably, liquid fatty esters derived from monoalcohols will be used as esters according to the invention.
[0106] Isopropyl myristate or palmitate are preferred.
[0107] Liquid silicone means an organopolysiloxane that is liquid at room temperature (25°C) and atmospheric pressure (760 mm Hg; or 1,013.105 Pa).
[0108] Preferably, the silicone is chosen from liquid polydialkylsiloxanes, in particular liquid polydimethylsiloxanes (PDMS), and liquid polyorganosiloxanes comprising at least one aryl group.
[0109] These silicones can also be organomodified. The organomodified silicones that can be used in accordance with the invention are liquid silicones as defined above and comprising in their structure one or more organofunctional groups attached via a hydrocarbon group.
[0110] Organopolysiloxanes are further defined in Walter Noll's "Chemistry and Technology of Silicones" (1968), Academy Press. They can be volatile or non-volatile.
[0111] When they are volatile, silicones are more particularly chosen from those having a boiling point between 60°C and 260°C, and more particularly still from: (i) cyclic polydialkylsiloxanes containing from 3 to 7, preferably from 4 to 5, silicon atoms. These include, for example, octamethylcyclotetrasiloxane sold in particular under the name VOLATILE SILICONE ®< 7207 by UNION CARBIDE or SILBIONE ®< 70045 V2 by RHODIA, decamethylcyclopentasiloxane sold under the name VOLATILE SILICONE ®< 7158 by UNION CARBIDE, and SILBIONE ®< 70045 V5 by RHODIA, dodecamethylcyclopentasiloxane sold under the name SILSOFT 1217 by MOMENTIVE PERFORMANCE MATERIALS, or cyclohexadimethylsiloxane and mixtures thereof. We can also cite cyclocopolymers of the dimethylsiloxane / methylalkylsiloxane type, such as SILICONE VOLATILE ®< FZ 3109 marketed by the company UNION CARBIDE, with the formula:Mention may also be made of mixtures of cyclic polydialkylsiloxanes with organic compounds derived from silicon, such as the mixture of octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol (50 / 50) and the mixture of octamethylcyclotetrasiloxane and oxy-1,1'-(hexa-2,2,2',2',3,3'-trimethylsilyloxy) bis-neopentane. (ii) linear volatile polydialkylsiloxanes having 2 to 9 silicon atoms and having a viscosity less than or equal to 5.10-6 m 2 < / s at 25 °C. This is, for example, decamethyltetrasiloxane marketed in particular under the name "SH 200" by the company TORAY SILICONE. Silicones falling within this class are also described in the article published in Cosmetics and Toiletries, Vol. 91, Jan. 76, P. 27-32 - TODD & BYERS "Volatile Silicone fluids for cosmetics". The viscosity of silicones is measured at 25 °C according to ASTM 445 Appendix C. Non-volatile polydialkylsiloxanes can also be used.These non-volatile silicones are more particularly chosen from polydialkylsiloxanes, among which we can mainly cite polydimethylsiloxanes with trimethylsilyl end groups. Among these polydialkylsiloxanes, we can cite, without limitation, the following commercial products: SILBIONE ®< oils of the 47 and 70 047 series or MIRASIL ®< oils marketed by RHODIA such as, for example, oil 70 047 V 500 000, the oils of the MIRASIL ®< series marketed by the company RHODIA; oils of the 200 series from the company DOW CORNING such as DC200 having a viscosity of 60,000 mm2 / s; VISCASIL ®< oils from GENERAL ELECTRIC and certain oils of the SF series (SF 96, SF 18) from GENERAL ELECTRIC. We can also cite polydimethylsiloxanes with dimethylsilanol end groups known as dimethiconol (CTFA), such as the oils of the 48 series from the company RHODIA.Among the silicones with aryl groups are polydiaryl siloxanes, in particular polydiphenylsiloxanes, and polyalkyl-arylsiloxanes. Examples include products marketed under the following names: SILBIONE ®< oils of the 70 641 series from RHODIA; oils of the RHODORSIL ®< 70 633 and 763 series from RHODIA; DOW CORNING 556 COSMETIC GRAD FLUID oil from DOW CORNING; silicones of the PK series from BAYER such as the product PK20; certain oils of the SF series from GENERAL ELECTRIC such as SF 1023, SF 1154, SF 1250, SF 1265. Organomodified liquid silicones may in particular have polyethyleneoxy and / or polypropyleneoxy groups. Examples include KF-6017 silicone offered by SHIN ETSU and SILWET ® oils < L 722, L 77 from UNION CARBIDE.
[0112] Liquid fatty ethers are selected from liquid dialkyl ethers such as dicaprylyl ether.
[0113] Fats may be non-liquid at room temperature and atmospheric pressure.
[0114] By non-liquids is preferably meant a solid compound or a compound having a viscosity greater than 2 Pa.s at a temperature of 25°C and at a shear rate of 1 s-1.
[0115] More particularly, the non-liquid fatty substances are chosen from fatty alcohols, fatty acid esters and / or fatty alcohol esters, non-silicone waxes, silicones, fatty ethers, non-liquid and preferably solid.
[0116] The non-liquid fatty alcohols suitable for implementing the invention are more particularly chosen from saturated or unsaturated, linear or branched alcohols, comprising from 8 to 30 carbon atoms, more preferably in C 10 -C 22 , even more preferably in C 14 -C 20 , better still in C 16 -C 18 ..
[0117] Cetyl alcohol and stearyl alcohol and their mixture (cetylstearyl alcohol) are particularly preferred.
[0118] As regards non-liquid fatty acid and / or fatty alcohol esters, mention may in particular be made of solid esters derived from C 9 -C 26 fatty acids and C 9 -C 26 fatty alcohols.
[0119] Among these esters, we can cite octyldodecyl behenate; isocetyl behenate; cetyl lactate; stearyl octanoate; octyl octanoate; cetyl octanoate; decyl oleate; myristyl stearate; octyl palmitate; octyl pelargonate; octyl stearate; alkyl myristates such as cetyl, myristyl, stearyl myristate; hexyl stearate, more particularly myristyl myrystate.
[0120] Still within the framework of this variant, it is also possible to use esters of C 4 -C 22 di or tricarboxylic acids and C 1 -C 22 alcohols and esters of mono di or tricarboxylic acids and C 2 -C 26 di, tri, tetra or pentahydroxy alcohols.
[0121] Examples include: diethyl sebacate; diisopropyl sebacate; diisopropyl adipate; di-n-propyl adipate; dioctyl adipate; dioctyl maleate.
[0122] Among all the additional esters mentioned above, it is preferred to use myristyl, cetyl, stearyl palmitates, alkyl myristates such as cetyl myristate, myristyl stearyl myristate.
[0123] The wax or waxes (non-silicone) are chosen in particular from Carnauba wax, Candelilla wax, and Alfa wax, paraffin wax, ozokerite, vegetable waxes such as olive wax, rice wax, hydrogenated jojoba wax or absolute flower waxes such as the essential wax of blackcurrant flower sold by the company BERTIN (France), animal waxes such as beeswax, modified beeswax (cerabellina), white beeswax such as those sold by KOSTER KEUNEN; other waxes or waxy raw materials that can be used according to the invention are in particular marine waxes such as that sold by the company SOPHIM under the reference M82, polyethylene or polyolefin waxes in general.
[0124] The non-liquid silicones according to the invention may be in the form of waxes, resins or gums.
[0125] Preferably, the non-liquid silicone is chosen from polydialkylsiloxanes, in particular polydimethylsiloxanes (PDMS), and organomodified polysiloxanes comprising at least one functional group chosen from poly(oxyalkylene) groups, amine groups and alkoxy groups.
[0126] The silicone gums that can be used in accordance with the invention are in particular polydialkylsiloxanes, preferably polydimethylsiloxanes having high number-average molecular masses of between 200,000 and 1,000,000, used alone or as a mixture in a solvent. This solvent can be chosen from volatile silicones, polydimethylsiloxane oils (PDMS), polyphenylmethylsiloxane oils (PPMS), isoparaffins, polyisobutylenes, methylene chloride, pentane, dodecane, tridecane or mixtures thereof.
[0127] Products which can be used more particularly in accordance with the invention are mixtures such as: mixtures formed from a polydimethylsiloxane hydroxylated at the chain end, or dimethiconol (CTFA) and a cyclic polydimethylsiloxane also called cyclomethicone (CTFA) such as the product Q2 1401 marketed by the company DOW CORNING; mixtures of a polydimethylsiloxane gum and a cyclic silicone such as the product SF 1214 Silicone Fluid from the company GENERAL ELECTRIC, this product is an SF 30 gum corresponding to a dimethicone, having a number average molecular weight of 500,000 solubilized in the oil SF 1202 Silicone Fluid corresponding to decamethylcyclopentasiloxane; mixtures of two PDMS of different viscosities, and more particularly of a PDMS gum and a PDMS oil, such as the product SF 1236 from the company GENERAL ELECTRIC. The SF 1236 product is the mixture of an SE 30 gum defined above having a viscosity of 20 m 2 < / s and an SF 96 oil with a viscosity of 5.10 6 m 2 < / s.This product preferably contains 15% SE 30 gum and 85% SF 96 oil.
[0128] The organopolysiloxane resins which can be used in accordance with the invention are crosslinked siloxane systems containing the units: R 2 SiO 2 / 2 , R 3 SiO 1 / 2 , RSiO 3 / 2 and SiO 4 / 2 Formulas in which: R, identical or different, preferably identical, represents an alkyl having 1 to 16 carbon atoms. Among these products, those which are particularly preferred are those in which R denotes a lower C1-C4 alkyl group, more particularly methyl.
[0129] Among these resins, we can cite the product marketed under the name "DOW CORNING 593" or those marketed under the names "SILICONE FLUID SS 4230 and SS 4267" by the company GENERAL ELECTRIC and which are silicones with a dimethyl / trimethyl siloxane structure.
[0130] We can also cite the trimethylsiloxysilicate type resins marketed in particular under the names X22-4914, X21-5034 and X21-5037 by the company SHIN-ETSU.
[0131] Among the additional organomodified silicones, we can cite polyorganosiloxanes comprising: substituted or unsubstituted amino groups such as the products marketed under the names Q2 8220 and DOW CORNING 929 or 939 by the company DOW CORNING. The substituted amino groups are in particular C 1 -C 4 aminoalkyl groups; alkoxylated groups, such as the product marketed under the name ABIL WAX ®< 2428, 2434 and 2440 by the company GOLDSCHMIDT.
[0132] The non-liquid fatty ethers are chosen from dialkyl ethers and in particular dicetyl ether and distearyl ether, alone or as a mixture.
[0133] The composition according to the invention may comprise one or more butters, identical or different, preferably of plant origin.
[0134] According to a preferred embodiment of the invention, the weight content of the butter(s) according to the invention, in C 16 fatty acids of the triglycerides expressed relative to the total fatty acids of the triglycerides is less than 23%.
[0135] By " butter» (also called « pasty fatty body ») for the purposes of the present invention, is understood to mean a lipophilic fatty compound with a reversible solid / liquid state change and comprising at a temperature of 25°C a liquid fraction and a solid fraction, and at atmospheric pressure (760 mm Hg). In other words, the starting melting temperature of the pasty compound may be lower than 25°C. The liquid fraction of the pasty compound measured at 25°C may represent 9 to 97% by weight of the compound. This liquid fraction at 25°C preferably represents between 15 and 85%, more preferably between 40 and 85% by weight.
[0136] Preferably, the butter(s) have an end of melting temperature of less than 60°C.
[0137] Preferably, the butter(s) have a hardness less than or equal to 6 MPa.
[0138] Preferably, the pasty fatty bodies have an anisotropic crystalline organization in the solid state, visible by X-ray observations.
[0139] For the purposes of the invention, the melting temperature corresponds to the temperature of the most endothermic peak observed in thermal analysis (DSC) as described in standard ISO 11357-3; 1999. The melting point of a paste or a wax can be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name "DSC Q2000" by the company TA Instruments.
[0140] Regarding the measurement of the melting temperature and the determination of the end-of-melting temperature, the sample preparation and measurement protocols are as follows:
[0141] A 5 mg sample of pasty fat, previously heated to 80°C and taken under magnetic stirring using a heated spatula, is placed in a hermetic aluminum capsule, or crucible. Two tests are carried out to ensure the reproducibility of the results.
[0142] The measurements are carried out on the calorimeter mentioned above. The furnace is subjected to a nitrogen sweep. Cooling is ensured by the RCS 90 heat exchanger. The sample is then subjected to the following protocol by first being brought to a temperature of 20 °C, then subjected to a first temperature rise from 20 °C to 80 °C, at a heating rate of 5 °C / minute, then cooled from 80 °C to -80 °C at a cooling rate of 5 °C / minute and finally subjected to a second temperature rise from -80 °C to 80 °C at a heating rate of 5 °C / minute. During the second temperature rise, the variation of the difference in power absorbed by the empty crucible and by the crucible containing the butter sample as a function of temperature is measured.The melting point of the compound is the temperature value corresponding to the top of the peak of the curve representing the variation of the difference in absorbed power as a function of temperature.
[0143] The end-of-melting temperature corresponds to the temperature at which 95% of the sample has melted.
[0144] The liquid fraction by weight of butter at 25°C is equal to the ratio of the enthalpy of fusion consumed at 25°C to the enthalpy of fusion of the butter.
[0145] The heat of fusion of a pasty compound is the heat consumed by the compound to change from a solid to a liquid state. Butter is said to be in a solid state when its entire mass is in crystalline solid form. Butter is said to be in a liquid state when its entire mass is in liquid form.
[0146] The heat of fusion of butter is equal to the integral of the entire melting curve obtained using the above calorimeter, with a temperature rise of 5 or 10 °C per minute, according to ISO 11357-3:1999. The heat of fusion of butter is the amount of energy required to change the compound from the solid to the liquid state. It is expressed in J / g.
[0147] The enthalpy of fusion consumed at 25°C is the amount of energy absorbed by the sample to pass from the solid state to the state it presents at 25°C consisting of a liquid fraction and a solid fraction.
[0148] The liquid fraction of the butter measured at 32°C preferably represents from 30 to 100% by weight of the compound, preferably from 50 to 100%, more preferably from 60 to 100% by weight of the compound. When the liquid fraction of the butter measured at 32°C is equal to 100%, the temperature at the end of the melting range of the pasty compound is less than or equal to 32°C.
[0149] The liquid fraction of butter measured at 32°C is equal to the ratio of the enthalpy of fusion consumed at 32°C to the enthalpy of fusion of the pasty compound. The enthalpy of fusion consumed at 32°C is calculated in the same way as the enthalpy of fusion consumed at 23°C.
[0150] Regarding hardness measurement, the sample preparation and measurement protocols are as follows:
[0151] The composition according to the invention or the butter is placed in a 75 mm diameter mold which is filled to approximately 75% of its height. In order to avoid the thermal past and to control crystallization, the mold is placed in the Vötsch VC0018 programmable oven where it is first heated to 80°C for 60 minutes, then cooled from 80°C to 0°C at a cooling rate of 5°C / minute, then left at the stabilized temperature of 0°C for 60 minutes, then subjected to a temperature increase from 0°C to 20°C, at a heating rate of 5°C / minute, then left at the stabilized temperature of 20°C for 180 minutes.
[0152] The compression force measurement is carried out with the Swantech TA / TX2i texturometer. The mobile used is chosen according to the texture: 2 mm diameter cylindrical steel mobile for very rigid raw materials; 12 mm diameter cylindrical steel mobile for less rigid raw materials;
[0153] The measurement involves 3 steps: a 1st step after automatic detection of the surface of the sample where the mobile moves at the measuring speed of 0.1 mm / s, and penetrates into the composition according to the invention or the butter at a penetration depth of 0.3 mm, the software notes the value of the maximum force reached; a 2nd step called relaxation where the mobile remains in this position for one second and where the force is noted after 1 second of relaxation; finally a 3rd step called withdrawal where the mobile returns to its initial position at the speed of 1 mm / s and the withdrawal energy of the probe (negative force) is noted.
[0154] The hardness value measured in the first step corresponds to the maximum compression force measured in Newtons divided by the surface area of the texturometer cylinder expressed in mm 2< in contact with the butter or the composition according to the invention. The hardness value obtained is expressed in mega-pascals or MPa.
[0155] According to a preferred embodiment of the invention, the particular butter(s) are of vegetable origin such as those described in Ullmann's Encyclopedia of Industrial Chemistry (“Fats and Fatty Oils”, A. Thomas, Published Online: 15 JUN 2000, DOI: 10.1002 / 14356007.a10_173, point 13.2.2.2. Shea Butter, Borneo Tallow, and Related Fats (Vegetable Butters)).
[0156] We can cite more particularly shea butter, Nilotica Shea butter (Butyrospermum parkii), Galam butter (Butyrospermum parkii), Borneo butter or fat or tengkawang tallow) (Shorea stenoptera), Shorea butter, Illipé butter, Madhuca butter or Bassia Madhuca longifolia, mowrah butter (Madhuca Latifolia), Katiau butter (Madhuca mottleyana), Phulwara butter (M. butyracea), mango butter (Mangifera indica), Murumuru butter (Astrocaryum murumuru), Kokum butter (Garcinia Indica), Ucuuba butter (Virola sebifera), Tucuma butter, Painya butter (Kpangnan) (Pentadesma butyracea), coffee butter (Coffea arabica), apricot butter (Prunus Armeniaca), macadamia butter (Macadamia Ternifolia), grape seed butter (Vitis vinifera), avocado butter (Persea gratissima), olive butter (Olea europaea), sweet almond butter (Prunus amygdalus dulcis) and sunflower butter.Preferably, the butter(s) according to the invention are chosen from Murumuru butter, Ucuuba butter, Shorea butter, Illipé butter, Shea butter, Cupuaçu butter and even more preferably Shea butter.
[0157] In a preferred variant of the invention, the weight content of C 16 fatty acids in the triglycerides expressed relative to the total fatty acids in the triglycerides varies from 0 to 22%, better still from 0 to 15%, even better still from 2 to 12%.
[0158] The composition according to the invention comprises one or more butters in an amount particularly inclusively between 0.01 and 30% by weight relative to the total weight of the composition, more particularly inclusively between 0.1 and 20% by weight, preferentially inclusively between 0.5 and 10% by weight, and more preferentially inclusively between 1 and 5% by weight.
[0159] Preferably, the compositions of the invention contain one or more fatty substances which are liquid at room temperature (25°C) and at atmospheric pressure (760 mm Hg; i.e. 1,013.105 Pa), optionally combined with one or more non-liquid fatty substances under the same conditions.
[0160] Preferably, the fatty substance is chosen from a) butters, preferably shea butter, b) waxes, preferably beeswax, c) non-liquid fatty alcohols, particularly chosen from saturated or unsaturated, linear or branched alcohols, containing from 8 to 30 carbon atoms, preferably C 10 -C 22 , more preferably C 14 -C 20 , better still C 16 -C 18 such as cetyl alcohol and stearyl alcohol and their mixture, d) non-liquid fatty acid and / or fatty alcohol esters, in particular solid esters derived from C 9 -C 26 fatty acids and C 9 -C 26 fatty alcohols, in particular alkyl myristates such as cetyl, mirystyle or stearyl myristate; hexyl stearate, more specifically myristyl myrystate;e) esters of monoalcohols, at least one of the alcohol or acid derived from said esters is branched, such as ethyl and isopropyl palmitates, alkyl myristates such as isopropyl myristate, ethyl myristate, isocetyl stearate, ethyl-2-hexyl isononanoate, isodecyl neopentanoate, isostearyl neopentanoate, and C 10 -C 22 alkyl (iso)stearates, preferably C 12 -C 20 alkyl (iso)stearates, such as isopropyl isostearate; f) cyclic polydialkylsiloxanes comprising from 3 to 7, preferably from 4 to 5, silicon atoms such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclopentasiloxane, or cyclohexadimethylsiloxane and mixtures thereof, preferably cyclohexadimethylsiloxane;(g) oils of vegetable origin or synthetic triglycerides, such as liquid triglycerides of fatty acids containing 6 to 30 carbon atoms such as triglycerides of heptanoic or octanoic acids or sunflower, corn, soybean, pumpkin, grape seed, sesame, hazelnut, apricot, macadamia, arara, sunflower, castor, avocado oils, triglycerides of caprylic / capric acids, jojoba oil, shea butter oil, preferably triglycerides of caprylic / capric acids.;
[0161] The fatty substance(s) used in the composition according to the present invention may be present in the composition in an amount varying from 1 to 40% by weight, preferably in an amount varying from 5 to 30% by weight, and even more preferably in an amount varying from 10 to 20% by weight relative to the total weight of the composition. The alkaline agent(s);
[0162] According to a particular embodiment of the invention, the composition of the invention comprises one or more alkaline agents (also called bases). This agent may be chosen from mineral or organic or hybrid alkaline agents or mixtures thereof.
[0163] The mineral alkaline agent(s) are preferably chosen from ammonia, alkali carbonates or bicarbonates such as sodium or potassium carbonates and sodium or potassium bicarbonates, sodium or potassium hydroxides or mixtures thereof.
[0164] According to an advantageous embodiment of the invention, the alkaline agent(s) are organic amines, i.e. they contain at least one substituted or unsubstituted amino group.
[0165] The organic alkaline agent(s) are more preferably chosen from organic amines whose pK b at 25°C is less than 12, and preferably less than 10, even more advantageously less than 6. Il It should be noted that this is the pK b corresponding to the highest basicity function.
[0166] As hybrid compounds, we can mention the salts of the amines mentioned above with acids such as carbonic acid and hydrochloric acid.
[0167] The organic alkaline agent(s) are, for example, chosen from alkanolamines, oxyethylenated and / or oxypropylenated ethylenediamines, amino acids and compounds of the following formula (IV): Formula (IV) in which: W is a divalent C 1 -C 6 alkylene radical optionally substituted by a hydroxyl group or a C 1 -C 6 alkyl radical, and / or optionally interrupted by one or more heteroatoms such as oxygen or NR u< ; R x< , R y< , R z< R t< and R u< , identical or different, represent a hydrogen atom, a C 1 -C 6 alkyl or C 1 -C 6 hydroxyalkyl, C 1 -C 6 aminoalkyl radical.
[0168] Examples of such amines include 1,3 diaminopropane, 1,3 diamino 2 propanol, spermine, spermidine.
[0169] By alkanolamine is meant an organic amine comprising a primary, secondary or tertiary amine function, and one or more linear or branched C1-C8 alkyl groups carrying one or more hydroxyl radicals.
[0170] Particularly suitable for carrying out the invention are alkanolamines such as mono-, di- or tri-alkanolamines, comprising one to three hydroxyalkyl radicals, identical or not, in C 1 -C 4 .
[0171] Among such compounds, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N-dimethylaminoethanolamine, 2-amino-2-methyl-1-propanol, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanediol, 3-dimethylamino-1,2-propanediol, tris-hydroxymethyl-aminomethane may be mentioned.
[0172] More particularly, the amino acids that can be used are of natural or synthetic origin, in their L, D, or racemic form and comprise at least one acid function chosen more particularly from carboxylic, sulfonic, phosphonic or phosphoric acid functions. The amino acids can be in neutral or ionic form.
[0173] As amino acids that can be used in the present invention, mention may in particular be made of aspartic acid, glutamic acid, alanine, arginine, ornithine, citrulline, asparagine, carnitine, cysteine, glutamine, glycine, histidine, lysine, isoleucine, leucine, methionine, N-phenylalanine, proline, serine, taurine, threonine, tryptophan, tyrosine and valine.
[0174] Advantageously, the amino acids are basic amino acids comprising an additional amine function optionally included in a cycle or in a ureido function, notably chosen from histidine, lysine, arginine, ornithine, citrulline.
[0175] The organic amine can also be chosen from heterocyclic organic amines. In addition to histidine already mentioned in the amino acids, mention may in particular be made of pyridine, piperidine, imidazole, triazole, tetrazole and benzimidazole.
[0176] The organic amine may also be chosen from amino acid dipeptides. As amino acid dipeptides which may be used in the present invention, mention may in particular be made of carnosine, anserine and whale.
[0177] The organic amine is chosen from compounds comprising a guanidine function. As amines of this type which can be used in the present invention, mention may in particular be made, in addition to arginine already mentioned as an amino acid, of creatine, creatinine, 1,1-dimethylguanidine, 1,1-diethylguanidine, glycocyamine, metformin, agmatine, n-amidinoalanine, 3-guanidinopropionic acid, 4-guanidinobutyric acid and 2-([amino(imino)methyl]amino)ethane-1-sulfonic acid.
[0178] As hybrid compounds, it is possible to mention in particular the use of guanidine carbonate or monoethanolamine hydrochloride.
[0179] The composition of the invention preferably contains one or more alkanolamines, and / or one or more basic amino acids, more advantageously, one or more alkanolamines. Even more preferably the organic amine is monoethanolamine.
[0180] According to a particular embodiment, the composition of the invention comprises as alkaline agent one or more alkanolamines.
[0181] Preferably, the alkanolamine is triethanolamine.
[0182] Advantageously, the composition according to the invention has a content of alkaline agent(s) ranging from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight, better still from 0.1 to 1% by weight relative to the weight of said composition. The organic thickening polymer(s):
[0183] According to a particular embodiment of the invention, the composition comprises one or more thickening organic polymers.
[0184] By " polymerthickener" means a polymer which, when introduced at 1% by weight into an aqueous or hydroalcoholic solution containing 30% ethanol, and at pH = 7 or into an oil chosen from vaseline oil, isopropyl myristate or cyclopentadimethylsiloxane, makes it possible to achieve a viscosity of at least 100 cps, preferably at least 500 cps, at 25°C and at a shear rate of 1 s -1< . This viscosity can be measured using a cone / plate viscometer (Haake R600 Rheometer or similar). The thickening polymers can be thickeners of the aqueous phase and / or the fatty phase, preferably of the aqueous phase.
[0185] By thickening polymer " organic »means a thickening polymer as defined above which is made up of carbon, hydrogen, and optionally nitrogen, oxygen, sulfur, halogens such as fluorine, chlorine, bromine as well as phosphorus, alkali metals such as sodium, potassium, or alkaline earth metals such as magnesium or calcium. The organic polymers according to the invention do not include silicon.
[0186] The organic thickening polymers according to the invention may be of natural or synthetic origin.
[0187] Thickening polymers can be anionic, cationic, amphoteric or non-ionic polymers, associative or not.
[0188] They can be thickeners of aqueous or oily phases.
[0189] As aqueous phase thickening polymers, mention may be made of associative or non-associative, preferably non-associative, thickening polymers with sugar units.
[0190] By reason " sugar " for the purposes of the present invention, a unit derived from a carbohydrate of formula C n (H 2 O) n-1 or (CH 2 O) n which may optionally be modified by substitution, and / or by oxidation and / or by dehydration is understood to mean.
[0191] The sugar units which may be included in the composition of the thickening polymers of the invention are preferably derived from the following sugars: glucose; galactose; arabinose; rhamnose; mannose; xylose; fucose; anhydrogalactose; galacturonic acid; glucuronic acid; mannuronic acid; galactose sulfate; anhydrogalactose sulfate and fructose.
[0192] As thickening polymers of the invention, mention may in particular be made of native gums such as: (a) exudates of trees or shrubs including: gum arabic (branched polymer of galactose, arabinose, rhamnose and glucuronic acid); gum ghatti (polymer of arabinose, galactose, mannose, xylose and glucuronic acid); gum karaya (polymer of galacturonic acid, galactose, rhamnose and glucuronic acid); gum tragacanth (or tragacanth) (polymer of galacturonic acid, galactose, fucose, xylose and arabinose); (b) gums derived from algae including: agar (polymer of galactose and anhydrogalactose); alginates (polymers of mannuronic acid and glucuronic acid); carrageenans and furcellerans (polymers of galactose sulfate and anhydrogalactose sulfate); c) gums derived from seeds or tubers including: guar gum (polymer of mannose and galactose); locust bean gum (polymer of mannose and galactose); fenugreek gum (polymer of mannose and galactose);tamarind gum (polymer of galactose, xylose and glucose); konjac gum (polymer of glucose and mannose); d) microbial gums including: xanthan gum (polymer of glucose, mannose acetate, mannose / pyruvic acid and glucuronic acid); gellan gum (polymer of partially acylated glucose, rhamnose and glucuronic acid); scleroglucan gum (polymer of glucose); e) plant extracts including: cellulose (polymer of glucose); starch (polymer of glucose) and inulin.
[0193] These polymers can be modified physically or chemically. Physical treatment includes, in particular, temperature.
[0194] Chemical treatments include esterification, etherification, amidation and oxidation reactions. These treatments produce polymers that can be non-ionic, anionic or amphoteric.
[0195] Preferably these chemical or physical treatments are applied to guar gums, locust bean gums, starches and celluloses.
[0196] The non-ionic guar gums which can be used according to the invention can be modified by C 1 -C 6 (poly)hydroxyalkyl groups.
[0197] Among the C 1 -C 6 (poly)hydroxyalkyl groups, we can mention by way of example, the hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups.
[0198] These guar gums are well known in the state of the art and can, for example, be prepared by reacting corresponding alkene oxides such as, for example, propylene oxides with guar gum so as to obtain a guar gum modified by hydroxypropyl groups.
[0199] The hydroxyalkylation rate preferably varies from 0.4 to 1.2 and corresponds to the number of alkylene oxide molecules consumed by the number of free hydroxyl functions present on the guar gum.
[0200] Such non-ionic guar gums, possibly modified by hydroxyalkyl groups, are for example sold under the trade names JAGUAR HP8, JAGUAR HP60 and JAGUAR HP120 by the company RHODIA CHIMIE.
[0201] The starch molecules used in the present invention may have a botanical origin from cereals or tubers. Thus, the starches are, for example, chosen from corn, rice, cassava, barley, potato, wheat, sorghum and pea starches.
[0202] Starches can be modified chemically or physically: in particular by one or more of the following reactions: pregelatinization, oxidation, crosslinking, esterification, etherification, amidation, heat treatments.
[0203] Distarch phosphates or compounds rich in distarch phosphate will preferably be used, such as the product offered under the references PREJEL VA-70-T AGGL (gelatinized hydroxypropyl cassava distarch phosphate) or PREJEL TK1 (gelatinized cassava distarch phosphate) or PREJEL 200 (gelatinized acetylated cassava distarch phosphate) by the company AVEBE or STRUCTURE ZEA from NATIONAL STARCH (gelatinized corn distarch phosphate).
[0204] According to the invention, amphoteric starches can also be used, these amphoteric starches comprise one or more anionic groups and one or more cationic groups. The anionic and cationic groups can be linked to the same reactive site of the starch molecule or to different reactive sites, preferably they are linked to the same reactive site. The anionic groups can be of the carboxylic, phosphate or sulfate type and preferably carboxylic. The cationic groups can be of the primary, secondary, tertiary or quaternary amine type.
[0205] Starch molecules can be derived from any plant source of starch, including corn, potato, oat, rice, tapioca, sorghum, barley, or wheat. Hydrolyzates of the starches listed above can also be used. The starch is preferably derived from potatoes.
[0206] The non-associative thickening polymers of the invention may be cellulosic polymers not comprising C 10 -C 30 fatty chains in their structure.
[0207] By polymer "cellulosic", according to the invention, we mean any polysaccharide compound having in its structure chains of glucose residues united by β-1,4 bonds; in addition to unsubstituted celluloses, cellulose derivatives can be anionic, cationic, amphoteric or non-ionic.
[0208] Thus, the cellulose polymers of the invention can be chosen from unsubstituted celluloses including in microcrystalline form and cellulose ethers.
[0209] Among these cellulose polymers, we distinguish cellulose ethers, cellulose esters and cellulose ether esters.
[0210] Cellulose esters include inorganic cellulose esters (cellulose nitrates, sulfates, or phosphates, etc.), organic cellulose esters (cellulose monoacetates, triacetates, amidopropionates, acetatebutyrates, acetatepropionates, or acetatetrimellitates, etc.), and mixed organic / inorganic cellulose esters such as cellulose acetatebutyrate sulfates and acetatepropionate sulfates. Cellulose ether esters include hydroxypropylmethylcellulose phthalates and ethylcellulose sulfates.
[0211] Among the non-ionic cellulose ethers without fatty chain in C 10 -C 30 ie “non-associative”,Examples include (C 1 -C 4 )alkylcelluloses such as methylcelluloses and ethylcelluloses (e.g. Ethocel standard 100 Premium from DOW CHEMICAL); (poly)hydroxy(C 1 -C 4 )alkylcelluloses such as hydroxymethylcelluloses, hydroxyethylcelluloses (e.g. Natrosol 250 HHR offered by AQUALON) and hydroxypropylcelluloses (e.g. Klucel EF from AQUALON); mixed celluloses (poly)hydroxy(C 1 -C 4 )alkyl-(C 1 -C 4 )alkylcelluloses such as hydroxypropylmethylcelluloses (e.g. Methocel E4M from DOW CHEMICAL), hydroxyethylmethylcelluloses, hydroxyethylethylcelluloses (e.g. Bermocoll E 481 FQ from AKZO NOBEL) and hydroxybutylmethylcelluloses.
[0212] Among the anionic cellulose ethers without fatty chain, mention may be made of (poly)carboxy(C 1 -C 4 )alkylcelluloses and their salts. For example, mention may be made of carboxymethylcelluloses, carboxymethylmethylcelluloses (for example Blanose 7M from the company AQUALON) and carboxymethylhydroxyethylcelluloses and their sodium salts.
[0213] Among the cationic cellulose ethers without fatty chain, mention may be made of cationic cellulose derivatives such as cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer, and described in particular in US patent 4,131,576, such as (poly)hydroxy(C 1 -C 4 )alkyl celluloses, such as hydroxymethyl-, hydroxyethyl- or hydroxypropyl celluloses grafted in particular with a salt of methacryloylethyl trimethylammonium, methacrylmidopropyl trimethylammonium, dimethyl-diallylammonium. The marketed products meeting this definition are more particularly the products sold under the name "Celquat ®< L 200" and "Celquat ®< H 100" by the National Starch Company.
[0214] According to a particular embodiment of the invention, the thickening polymer(s) of the invention are derived from the (co)polymerization of acrylate monomer CH 2 =C(R')-COOR‴ (VIa) and / or acrylamide monomer CH 2 =C(R')-CO-N(R")-LY -< M +< (VIb) Formulae (Via) and (VIb) in which R', and R", identical or different, represent a hydrogen atom or a (C 1 -C 6 )alkyl group such as methyl, preferably hydrogen, R"' represents an alkali metal, an alkaline earth metal, a hydrogen atom or a (C 1 -C 6 )alkyl group optionally substituted in particular by one or more hydroxy, carboxy or amino groups, preferably R"' represents a hydrogen atom, L represents a divalent, cyclic or acyl, saturated or unsaturated, linear or branched, optionally interrupted by one or more heteroatoms such as O, N and comprising from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms,preferably L represents the divalent group -[C(R')(R")] p - with p representing an integer between 1 and 4, preferably 2 and 3 such that 2, R' and R" being as defined above, more particularly L represents -C(R')(R")-CH 2 - or -CH 2 -C(R')(R")- with R' and R" as defined above, preferably R' and R" represent a (C 1 -C 4 )alkyl group such as methyl; Y -< represents an anionic group such as carboxylate, phosphate, phosphonate, sulfonate, or sulfate, preferably -S(O) 2 -O -< , and M +< being a cationic counterion, preferably an alkali metal such as sodium, said copolymer being able to be in direct or inverse emulsion, preferably inverse. More preferably, the thickening polymer(s) of the invention are derived from the copolymerization of acrylate monomer CH 2 =C(R')-COOH (VIa) and acrylamide monomer CH 2 =C(R')-CO-N(R")-LY -< M +< (VIb) as defined previously.
[0215] Among the non-associative thickening polymers without sugar units which can be used, mention may be made of homopolymers or copolymers of crosslinked acrylic or methacrylic acid, crosslinked homopolymers of 2-acrylamido-2-methyl-propanesulfonic acid and their crosslinked or non-crosslinked acrylamide copolymers, homopolymers of ammonium acrylate or copolymers of ammonium acrylate and acrylamide alone or in mixtures.
[0216] A first family of suitable non-associative thickening polymers is represented by crosslinked acrylic acid homopolymers.
[0217] Among the homopolymers of this type, we can cite those crosslinked by an allyl ether of alcohol of the sugar series, such as for example the products sold under the names CARBOPOLS 980, 981, 954, 2984 and 5984 by the company NOVEON or the products sold under the names SYNTHALEN M and SYNTHALEN K by the company 3 VSA.
[0218] Non-associative thickening polymers can also be crosslinked (meth)acrylic acid copolymers such as the polymer sold under the name AQUA SF1 by the company NOVEON.
[0219] The non-associative thickening polymers may be selected from crosslinked homopolymers of 2-acrylamido-2-methylpropanesulfonic acid and their crosslinked acrylamide copolymers.
[0220] Among the crosslinked copolymers of 2-acrylamido-2-methyl-propanesulfonic acid and partially or totally neutralized acrylamide, mention may be made in particular of the product described in example 1 of document EP 503 853 and reference may be made to this document with regard to these polymers.
[0221] The composition may also comprise, as non-associative thickening polymers, ammonium acrylate homopolymers or ammonium acrylate and acrylamide copolymers.
[0222] Examples of ammonium acrylate homopolymers include the product sold under the name SIMULGEL 600 acrylamide / sodium acryloyldimethyltaurate copolymer isohexadecane and polysorbate 80 marketed by SEPPIC, MICROSAP PAS 5193 by the company HOECHST. Among the ammonium acrylate and acrylamide copolymers, mention may be made of the product sold under the name BOZEPOL C NOUVEAU or the product PAS 5193 sold by the company HOECHST. Reference may be made in particular to documents FR 2 416 723, US 2798053 and US 2923692 for the description and preparation of such compounds.
[0223] Among the thickening polymers of aqueous phases, mention may also be made of non-cellulosic associative polymers well known to those skilled in the art and in particular of a non-ionic, anionic, cationic or amphoteric nature.
[0224] It is recalled that the "associative polymers"are polymers capable, in an aqueous medium, of reversibly associating with each other or with other molecules.
[0225] Their chemical structure more particularly comprises at least one hydrophilic zone and at least one hydrophobic zone.
[0226] By "hydrophobic group", we mean a radical or polymer with a hydrocarbon chain, saturated or not, linear or branched, comprising at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferably from 18 to 30 carbon atoms.
[0227] Preferably, the hydrocarbon group comes from a monofunctional compound. For example, the hydrophobic group can come from a fatty alcohol such as stearyl alcohol, dodecyl alcohol, decyl alcohol. It can also designate a hydrocarbon polymer such as, for example, polybutadiene.
[0228] Among the anionic type associative polymers, we can cite: (a)those comprising at least one hydrophilic unit, and at least one fatty chain allyl ether unit, more particularly those in which the hydrophilic unit is constituted by an ethylenically unsaturated anionic monomer, more particularly still by a vinyl carboxylic acid and very particularly by an acrylic acid or a methacrylic acid or mixtures thereof. Among these anionic associative polymers, polymers formed from 20 to 60% by weight of acrylic acid and / or methacrylic acid, from 5 to 60% by weight of lower alkyl (meth)acrylates, from 2 to 50% by weight of fatty chain allyl ether, and from 0 to 1% by weight of a crosslinking agent which is a well-known copolymerizable polyethylene unsaturated monomer, such as diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate, and methylene-bis-acrylamide are particularly preferred according to the invention.Among the latter, particularly preferred are crosslinked terpolymers of methacrylic acid, ethyl acrylate, polyethylene glycol (10 EO) stearyl alcohol ether (Steareth 10), in particular those sold by the company CIBA under the names SALCARE SC80 ®< and SALCARE SC90 ®< which are 30% aqueous emulsions of a crosslinked terpolymer of methacrylic acid, ethyl acrylate and steareth-10-allyl ether (40 / 50 / 10). (b) those comprising i) at least one hydrophilic unit of olefinic unsaturated carboxylic acid type, and ii) at least one hydrophobic unit of unsaturated carboxylic acid (C 10 -C 30 ) alkyl ester type.
[0229] Alkyl (C 10 -C 30 ) esters of unsaturated carboxylic acids useful in the invention include, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate, dodecyl acrylate, and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate, and dodecyl methacrylate.
[0230] Anionic polymers of this type are, for example, described and prepared according to US patents 3,915,921 and 4,509,949.
[0231] Among this type of anionic associative polymers, those consisting of 95 to 60% by weight of acrylic acid (hydrophilic unit), 4 to 40% by weight of C 10 -C 30 alkyl acrylate (hydrophobic unit), and 0 to 6% by weight of crosslinking polymerizable monomer, or those consisting of 98 to 96% by weight of acrylic acid (hydrophilic unit), 1 to 4% by weight of C 10 -C 30 alkyl acrylate (hydrophobic unit), and 0.1 to 0.6% by weight of crosslinking polymerizable monomer such as those described above, will be used more particularly.
[0232] Among the above polymers, the products sold by the company GOODRICH under the trade names PEMULEN TR1 ®< , PEMULEN TR2 ®< , CARBOPOL 1382 ®< , and even more preferably PEMULEN TR1 ®< , and the product sold by the company SEPPIC under the name COATEX SX ®< , are particularly preferred according to the present invention.
[0233] We can also cite the acrylic acid / lauryl methacrylate / vinylpyrrolidone terpolymer marketed under the name Acrylidone LM by the ISP Company. (c) maleic anhydride / C 30 -C 38 α-olefin / alkyl maleate terpolymers such as the product (maleic anhydride / C 30 -C 38 α-olefin / isopropyl maleate copolymer) sold under the name PERFORMA V 1608 ® by the company NEWPHASE TECHNOLOGIES (d)acrylic terpolymers comprising: i) about 20% to 70% by weight of an α,β-monoethylenically unsaturated carboxylic acid [A], ii) about 20 to 80% by weight of a non-surfactant α,β-monoethylenically unsaturated monomer other than [A], iii) about 0.5 to 60% by weight of a non-ionic monourethane which is the reaction product of a monohydric surfactant with a monoethylenically unsaturated monoisocyanate, such as those described in patent application EP-A-0173109 and more particularly that described in Example 3, namely, a methacrylic acid / methyl acrylate / ethoxylated behenyl alcohol dimethyl metaisopropenyl benzyl isocyanate terpolymer (40EO) in 25% aqueous dispersion. (e) copolymers comprising among their monomers an α,β-monoethylenically unsaturated carboxylic acid and an ester of an α,β-monoethylenically unsaturated carboxylic acid and an oxyalkylenated fatty alcohol.
[0234] Preferably, these compounds also comprise as monomer an ester of carboxylic acid with α,β-monoethylenic unsaturation and of C 1 -C 4 alcohol. As an example of this type of compound, mention may be made of ACULYN 22 ®< sold by the company ROHM and HAAS, which is a methacrylic acid / ethyl acrylate / oxyalkylenated stearyl methacrylate terpolymer. (f) Amphiphilic polymers comprising at least one ethylenically unsaturated monomer with a sulfonic group, in free or partially or totally neutralized form and comprising at least one hydrophobic part. These polymers may be crosslinked or non-crosslinked. They are preferably crosslinked.
[0235] The ethylenically unsaturated monomers with a sulfonic group are chosen in particular from vinylsulfonic acid, styrenesulfonic acid, (meth)acrylamido(C 1 -C 22 )alkylsulfonic acids, N-(C 1 -C 22 )alkyl(meth)-acrylamido-(C 1 -C 22 )alkylsulfonic acids such as undecyl-acrylamido-methane-sulfonic acid and their partially or totally neutralized forms.
[0236] More preferably, (meth)acrylamido(C 1 -C 22 ) alkylsulfonic acids will be used, such as, for example, acrylamido-methanesulfonic acid, acrylamido-ethanesulfonic acid, acrylamido-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamido-dodecylsulfonic acid, 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, as well as their partially or totally neutralized forms.
[0237] More specifically, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and its partially or totally neutralized forms will be used.
[0238] The polymers of this family may in particular be chosen from random amphiphilic polymers of AMPS modified by reaction with a C 6 -C 22 n-monoalkylamine or di-n-alkylamine, and such as those described in patent application WO 00 / 31154 (forming an integral part of the content of the description). These polymers may also contain other ethylenically unsaturated hydrophilic monomers chosen for example from (meth)acrylic acids, their β-substituted alkyl derivatives or their esters obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid or mixtures of these compounds.
[0239] Preferred polymers of this family are chosen from amphiphilic copolymers of AMPS and at least one hydrophobic monomer with ethylenic unsaturation.
[0240] These same copolymers may also contain one or more ethylenically unsaturated monomers not comprising a fatty chain such as (meth)acrylic acids, their β-substituted alkyl derivatives or their esters obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid or mixtures of these compounds.
[0241] These copolymers are described in particular in patent application EP-A-750899, US patent 5089578 and in the following publications by Yotaro Morishima: « Self-assembling amphiphilic polyelectrolytes and their nanostructures - Chinese Journal of Polymer Science Vol. 18, N°40, (2000), 323-336. » « Miscelle formation of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and a non-ionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering - Macromolecules, Vol. 33, N° 10 (2000), 3694-3704 » ; « Solution properties of miscelle networks formed by non-ionic moieties covalently bound to an polyelectrolyte : salt effects on rheological behavior - Langmuir, , Vol. 16, N°12, (2000) 5324-5332 » ; « Stimuli responsive amphiphilic copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and associative macromonomers - Polym. Preprint, Div. Polym. Chem., 40(2), (1999), 220-221». Parmi ces polymères, on peut citer : crosslinked or non-crosslinked copolymers, neutralized or not, comprising from 15 to 60% by weight of AMPS units and from 40 to 85% by weight of (C 8 -C 16 )alkyl(meth)acrylamide units or (C 8 -C 16 )alkyl(meth)acrylate units relative to the polymer, such as those described in application EP-A750 899; terpolymers comprising from 10 to 90% by mole of acrylamide units, from 0.1 to 10% by mole of AMPS units and from 5 to 80% by mole of n-(C 6 -C 18 )alkylacrylamide units, such as those described in patent US-5089578.
[0242] Also of interest are copolymers of fully neutralized AMPS and dodecyl methacrylate, as well as copolymers of uncrosslinked and crosslinked AMPS and n-dodecylmethacrylamide, such as those described in the Morishima papers cited above. Cationic associative polymers include: (I) Cationic associative polyurethanes; (II) The compound marketed by the company NOVEON under the name AQUA CC and which corresponds to the INCI name POLYACRYLATE-1 CROSSPOLYMER.
[0243] POLYACRYLATE-1 CROSSPOLYMER is the product of the polymerization of a mixture of monomers comprising: * a di(C 1 -C 4 alkyl)amino(C 1 -C 6 alkyl)methacrylate, * one or more C 1 -C 30 alkyl esters of (meth)acrylic acid, * a polyethoxylated (20-25 moles of ethylene oxide unit) C 10 -C 30 alkyl methacrylate, * a polyethylene glycol / polypropylene glycol 30 / 5 allyl ether, * a hydroxy(C 2 -C 6 alkyl)methacrylate, and * an ethylene glycol dimethacrylate. (III) quaternized (poly)hydroxyethylcelluloses modified by groups comprising at least one fatty chain, such as alkyl, arylalkyl, alkylaryl groups comprising at least 8 carbon atoms, or mixtures thereof. The alkyl radicals carried by the above quaternized celluloses or hydroxyethylcelluloses preferably comprise from 8 to 30 carbon atoms. The aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups. Examples of quaternized alkylhydroxyethylcelluloses with C 8 -C 30 fatty chains include the products QUATRISOFT LM 200 ®< , QUATRISOFT LM-X 529-18-A ®< , QUATRISOFT LM-X 529-18-B ®< (C 12 alkyl) and QUATRISOFT LM-X 529-8 ®< (C 18 alkyl) sold by AQUALON, the products CRODACEL QM ®< , CRODACEL QL ®< (C 12 alkyl) and CRODACEL QS ®< (C 18 alkyl) sold by CRODA and the product SOFTCAT SL 100 ®< sold by AQUALON. (IV) Cationic polyvinyllactam polymers.
[0244] Such polymers are for example described in patent application WO-00 / 68282.
[0245] As cationic poly(vinyllactam) polymers according to the invention, use is made in particular of vinylpyrrolidone / dimethylaminopropylmethacrylamide / dodecyldimethylmethacrylamidopropylammonium tosylate terpolymers, vinylpyrrolidone / dimethylaminopropylmethacrylamide / cocoyldimethylmethacrylamidopropylammonium tosylate terpolymers, vinylpyrrolidone / dimethylaminopropylmethacrylamide / lauryldimethylmethacrylamidopropylammonium tosylate or chloride terpolymers.
[0246] The amphoteric associative polymers are preferably chosen from those comprising at least one non-cyclic cationic unit. More particularly still, those prepared from or comprising 1 to 20 mol% of monomer comprising a fatty chain, and preferably 1.5 to 15 mol% and more particularly still 1.5 to 6 mol%, relative to the total number of moles of monomers, are preferred.
[0247] Amphoteric associative polymers according to the invention are for example described and prepared in patent application WO 9844012.
[0248] Among the amphoteric associative polymers according to the invention, acrylic acid / (meth)acrylamidopropyl trimethyl ammonium chloride / stearyl methacrylate terpolymers are preferred.
[0249] The non-ionic associative polymers which can be used according to the invention are preferably chosen from: (a) copolymers of vinyl pyrrolidone and hydrophobic monomers with a fatty chain, including, for example: the products ANTARON V216 ®< or GANEX V216 ®< (vinylpyrrolidone / hexadecene copolymer) sold by the company ISP the products ANTARON V220 ®< or GANEX V220 ®< (vinylpyrrolidone / eicosene copolymer) sold by the company ISP (b) copolymers of C 1 -C 6 alkyl methacrylates or acrylates and amphiphilic monomers comprising at least one fatty chain, such as, for example, the methyl acrylate / oxyethylenated stearyl acrylate copolymer sold by the company GOLDSCHMIDT under the name ANTIL 208 ®<. (c) copolymers of hydrophilic methacrylates or acrylates and hydrophobic monomers comprising at least one fatty chain such as, for example, the polyethylene glycol methacrylate / lauryl methacrylate copolymer.(d) polyether polyurethanes comprising in their chain both hydrophilic sequences, most often polyoxyethylenated in nature, and hydrophobic sequences which may be aliphatic chains alone and / or cycloaliphatic and / or aromatic chains. (e) polymers with an aminoplast ether skeleton having at least one fatty chain, such as the PURE THIX ®< compounds offered by the company SUD-CHEMIE.(f) celluloses or their derivatives, modified by groups comprising at least one fatty chain such as alkyl, arylalkyl, alkylaryl groups or their mixtures where the alkyl groups are C 8 - and in particular: * non-ionic alkylhydroxyethylcelluloses such as the products NATROSOL PLUS GRADE 330 CS and POLYSURF 67 (C 16 alkyl) sold by the company AQUALON * non-ionic nonoxynylhydroxyethylcelluloses such as the product AMERCELL HM-1500 sold by the company AMERCHOL; * non-ionic alkylcelluloses such as the product BERMOCOLL EHM 100 sold by the company BEROL NOBEL; (g) associative guar derivatives such as hydroxypropylguars modified by a fatty chain such as the product ESAFLOR HM 22 (modified by a C 22 alkyl chain) sold by the company LAMBERTI; the product MIRACARE XC 95-3 (modified by a C 14 alkyl chain) and the product RE 205-146 (modified by a C 20 alkyl chain) sold by RHODIA CHIMIE; .
[0250] Preferably, the polyether polyurethanes comprise at least two lipophilic hydrocarbon chains, having from 6 to 30 carbon atoms, separated by a hydrophilic sequence, the hydrocarbon chains possibly being pendant chains or chains at the end of a hydrophilic sequence. In particular, it is possible for one or more pendant chains to be provided. In addition, the polymer may comprise a hydrocarbon chain at one end or at both ends of a hydrophilic sequence.
[0251] Polyether polyurethanes can be multi-block, particularly in triblock form. The hydrophobic blocks can be at each end of the chain (for example: triblock copolymer with a hydrophilic central block) or distributed both at the ends and in the chain (multi-block copolymer for example). These same polymers can also be grafted or star-shaped.
[0252] Nonionic fatty chain polyether polyurethanes can be triblock copolymers whose hydrophilic block is a polyoxyethylene chain containing 50 to 1000 oxyethylene groups. Nonionic polyether polyurethanes contain a urethane bond between the hydrophilic blocks, hence the origin of the name.
[0253] By extension, non-ionic fatty chain polyether polyurethanes also include those whose hydrophilic sequences are linked to the lipophilic sequences by other chemical bonds.
[0254] As examples of non-ionic fatty chain polyurethane polyethers which can be used in the invention, it is also possible to use Rhéolate 205 ®< with urea function sold by the company RHEOX or even Rhéolates ®< 208, 204 or 212, as well as Acrysol RM 184 ®<.
[0255] Other examples include the ELFACOS T210 ®< product with a C 12 -C 14 alkyl chain and the ELFACOS T212 ®< product with a C 18 alkyl chain from AKZO.
[0256] ROHM & HAAS's DW 1206B ®< product with a C 20 alkyl chain and urethane bond, available at 20% dry matter in water, can also be used.
[0257] Solutions or dispersions of these polymers can also be used, particularly in water or in a hydroalcoholic medium. Examples of such polymers include RHEOLATE ®< 255, RHEOLATE ®< 278 and RHEOLATE ®< 244 sold by RHEOX. DW 1206F and DW 1206J, products offered by ROHM & HAAS, can also be used.
[0258] The polyether polyurethanes which can be used according to the invention are in particular those described in the article by G. Fonnum, J. Bakke and Fk. Hansen - Colloid Polym. Sci 271, 380.389 (1993).
[0259] More particularly, it is preferred to use a polyether polyurethane capable of being obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 moles of ethylene oxide, (ii) stearyl alcohol or decyl alcohol and (iii) at least one diisocyanate.
[0260] Such polyether polyurethanes are sold in particular by the company ROHM & HAAS under the names ACULYN 46 ®< and ACULYN 44 ®< [ACULYN 46 ®< is a polycondensate of polyethylene glycol with 150 or 180 moles of ethylene oxide, stearyl alcohol and methylene bis(4-cyclohexylisocyanate) (SMDI), at 15% by weight in a matrix of maltodextrin (4%) and water (81%); ACULYN 44 ®< is a polycondensate of polyethylene glycol with 150 or 180 moles of ethylene oxide, decyl alcohol and methylene bis(4-cyclohexylisocyanate) (SMDI), at 35% by weight in a mixture of propylene glycol (39%) and water (26%)].
[0261] Polymers can also be used to thicken fatty phases.
[0262] Preferably, the polymers structuring the oily phase via physical interactions are chosen from polyamides, silicone polyamides, mono- or poly-alkyl esters of saccharide or polysaccharide, amide derivatives of N-acylated amino acids, copolymers comprising an alkylene or styrene sequence, these copolymers possibly being di-block, tri-block, multi-block, radial-block polymers also called star copolymers, or comb polymers. 1) Polymers carrying at least one crystallizable sequence in the backbone These are also polymers that are soluble or dispersible in oil or oily phase by heating above their melting point pF. These polymers are in particular block copolymers made up of at least two sequences of different chemical nature, one of which is crystallizable.
[0263] As polymers carrying in the skeleton at least one crystallizable sequence suitable for implementing the invention, mention may be made of: i). The polymers defined in US-A-5,156,911; ii). Block copolymers of olefin or cycloolefin with a crystallizable chain such as those resulting from the block polymerization of: cyclobutene, cyclohexene, cyclooctene, norbornene (i.e. bicyclo(2,2,1)heptene 2), 5-methylnorbornene, 5-ethylnorbornene, 5,6-dimethylnorbornene, 5,5,6-trimethylnorbornene, 5-ethylidenenorbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-vinylnorbornene, 1,4,5,8-dimethano-1,2,3,4,4a,5,8a-octahydronaphthalene, dicyclopentadiene, and mixtures thereof; with ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-eicosene or mixtures thereof.
[0264] These block copolymers can be in particular (ethylene / norbornene) block copolymers and (ethylene / propylene / ethylidene-norbornene) block terpolymers.
[0265] It is also possible to use those resulting from the block copolymerization of at least 2 C 2 -C 16 and better still C 2 -C 12 α-olefins, such as those mentioned above and in particular the block bipolymers of ethylene and 1-octene.
[0266] Copolymers having at least one crystallizable sequence, the remainder of the copolymer being amorphous (at room temperature). These copolymers may, in addition, have two crystallizable sequences of different chemical nature.
[0267] The preferred copolymers are those which have at room temperature, both a crystallizable sequence and an amorphous sequence which is both hydrophobic and lipophilic, distributed sequentially; examples which may be mentioned are polymers having one of the following crystallizable sequences and one of the following amorphous sequences: Crystallizable sequence by nature: a) polyester such as poly(alkylene terephthalate), b) polyolefin such as polyethylenes or polypropylenes. Amorphous and lipophilic sequence such as amorphous polyolefins or copoly(olefin)s such as poly(isobutylene), hydrogenated polybutadiene, hydrogenated poly(isoprene).
[0268] Examples of such crystallizable block and amorphous block copolymers include: a) poly(δ-caprolactone)-b-poly(butadiene) block copolymers, preferably hydrogenated, such as those described in the article “Melting behavior of poly(δ-caprolactone)-block-polybutadiene copolymers” by S. Nojima, Macromolecules, 32, 3727-3734 (1999). b) hydrogenated poly(butyleneterephthalate)-b-poly(isoprene) block copolymers, block or multiblock, cited in the article “Study of morphological and mechanical properties of PP / PBT” by B. Boutevin et al., Polymer Bulletin, 34, 117-123 (1995). c) the poly(ethylene)-b-copoly(ethylene / propylene) block copolymers cited in the articles “Morphology of semi-crystalline block copolymers of ethylene-(ethylene-alt-propylene)” by P. Rangarajan et al., Macromolecules, 26, 4640-4645 (1993), and “Polymer aggregates with crystalline cores: the system poly(ethylene)-poly(ethylene-propylene)”, P. Richter et al., Macromolecules, 30, 1053-1068 25 (1997).d) poly(ethylene)-b-poly(ethylethylene) block copolymers cited in the general article “Crystallization in block copolymers” by IW Hamley, Advances in Polymer Science, vol 148, 113-137 (1999).
[0269] The semi-crystalline polymers that can be used in the context of the invention may be non-crosslinked or partially crosslinked, provided that the degree of crosslinking does not hinder their dissolution or dispersion in the liquid oily phase by heating above their melting temperature. This may then be a chemical crosslinking, by reaction with a multifunctional monomer during polymerization. It may also be a physical crosslinking which may then be due either to the establishment of hydrogen or dipolar bonds between groups carried by the polymer, such as for example dipolar interactions between carboxylate ionomers, these interactions being in small quantity and carried by the backbone of the polymer; or to a phase separation between the crystallizable sequences and the amorphous sequences carried by the polymer.
[0270] Preferably, the semi-crystalline polymers suitable for the invention are non-crosslinked.
[0271] As a particular example of a semi-crystalline polymer that can be used in the composition according to the invention, mention may be made of the Intelimer ®< products from the company Landec described in the brochure “Intelimer ®< polymers”. These polymers are in solid form at room temperature (25°C). They carry crystallizable side chains and contain the monomer. Mention may be made in particular of “Landec IP22 ®<”, having a melting point pF of 56°C, which is a viscous product at room temperature, impermeable, non-sticky.
[0272] It is also possible to use the semi-crystalline polymers described in examples 3, 4, 5, 7, 9 of document US-A-5,156,911, resulting from the copolymerization of acrylic acid and C 5 to C 16 alkyl(meth)acrylate like those resulting from the copolymerization: of acrylic acid, hexadecylacrylate and isodecylacrylate in a ratio of 1 / 16 / 3, of acrylic acid and pentadecylacrylate in a ratio of 1 / 19, of acrylic acid, hexadecylacrylate, ethylacrylate in a ratio of 2.5 / 76.5 / 20, of acrylic acid, hexadecylacrylate and methylacrylate in a ratio of 5 / 85 / 10, of acrylic acid, octadecylmethacrylate in a ratio of 2.5 / 97.5.
[0273] It is also possible to use the “Structure O” polymer marketed by the company National Starch, such as that described in document US-A-5,736,125, with a mp of 44°C, as well as the semi-crystalline polymers with crystallizable pendant chains comprising fluorinated groups such as described in examples 1, 4, 6, 7 and 8 of document WO-A-01 / 19333.
[0274] It is also possible to use semi-crystalline polymers obtained by copolymerization of stearyl acrylate and acrylic acid or NVP or by copolymerization of behenyl acrylate and acrylic acid or NVP, as described in document US-A-5,519,063 or EP-A-0 550 745.
[0275] According to a particular embodiment variant, the semi-crystalline polymers suitable for implementing the present invention are in particular alkylated acrylates, among which LANDEC copolymers may be mentioned: Doresco IPA 13-1 ®<: polystearyl acrylate, mp 49 °C and MW 145000; Doresco IPA 13-3 ®<: polyacrylate / methacrylic acid, mp 65 °C and MW 114000; Doresco IPA 13-4 ®<: polyacrylate / vinyl pirrolidone, mp 44 °C and MW 387000; Doresco IPA13-5 ®<: polyacrylate / hydroxyethyl methacrylate, mp 47 °C and MW 397600; Doresco IPA 13-6 ®<: polybehenyl acrylate, mp 66 °C. 2) Non-silicone polyamides
[0276] The particular polyamides used in the composition according to the present invention are preferably those described in document US-A-5,783,657 from the UNION CAMP Company. The part of US-A-5,783,657 devoted to these polymers is incorporated by reference.
[0277] Each of these polyamides satisfies in particular the following formula (V):
[0278] Formula (V) in which: n denotes an integer number of amide units such that the number of ester groups represents from 10% to 50% of the total number of ester and amide groups; R 1< is at each occurrence independently an alkyl or alkenyl group having at least 4 carbon atoms and in particular from 4 to 24 carbon atoms R 2< represents at each occurrence independently a C 4 to C 55 hydrocarbon group provided that at least 50% of the R 2 groups represent a C 30 to C 55 hydrocarbon group; R 3< represents at each occurrence independently an organic group provided with at least 2 carbon atoms, hydrogen atoms and optionally one or more oxygen or nitrogen atoms;and R 4< represents at each occurrence independently a hydrogen atom, a C 1 -C 10 alkyl group or a direct bond to R 3 or another R 4 such that the nitrogen atom to which both R 3 and R 4 are bonded is part of a heterocyclic structure defined by R 4 -NR 3 , with at least 50% of the R 4 representing a hydrogen atom. ;
[0279] In particular, the ester groups of this polyamide represent from 15 to 40% of the total number of ester and amide groups and at best from 20 to 35%. In addition, n advantageously represents an integer ranging from 1 to 10, and better from 1 to 5, limits inclusive.
[0280] Preferably, R 1< is a C 12 to C 22 alkyl group and preferably a C 16 to C 22 alkyl group. Advantageously, R 2< may be a C 10 to C 42 hydrocarbon (alkylene) group. Preferably, at least 50% and more preferably at least 75% of the R 2< are groups having from 30 to 42 carbon atoms. The other R 2< are hydrogenated C 4 to C 19 and preferably C 4 to C 12 groups. Preferably, R 3< represents a C 2 to C 36 hydrocarbon group or a polyoxyalkylene group and R 4< represents a hydrogen atom. Preferably, R 3< represents a C 2 to C 12 hydrocarbon group. The hydrocarbon groups may be linear, cyclic or branched, saturated or unsaturated groups. Furthermore, the alkyl and alkylene groups may be linear or branched, saturated or unsaturated groups. Thickening of the liquid fatty phase may be achieved using one or more polyamides defined above.In general, these polyamides are in the form of mixtures, these mixtures being able to further contain a synthetic product corresponding to a polyamide as defined above with n being 0, i.e. a diester.
[0281] As a structuring polyamide that can be used in the invention, mention may also be made of polyamide resins resulting from the condensation of an aliphatic dicarboxylic acid and a diamine (including compounds having more than two carbonyl groups and two amine groups), the carbonyl and amine groups of adjacent unit units being condensed by an amide bond. These polyamide resins are in particular those marketed under the brand name Versamid ®< by the companies General Mills, Inc. and Henkel Corp., under the brand name Onamid ®< in particular Onamid S or C. These resins have a weight-average molecular mass ranging from 6000 to 9000. For further information on these polyamides, reference may be made to documents US-A-3,645,705 and US-A-3,148,125. More specifically, Versamid ®< 30 or 744 are used.
[0282] Polyamides sold or manufactured by Arizona under the references Uni-Rez (2658, 2931, 2970, 2621, 2613, 2624, 2665, 1554, 2623, 2662) and the product sold under the reference Macromelt 6212 by Henkel can also be used. For more information on these polyamides, please refer to document USA-5500209.
[0283] As an example of structuring polyamides that can be used in the composition according to the invention, mention may also be made of the commercial products sold or manufactured by the Arizona Chemical company under the names Uniclear 80 and Uniclear 100. They are sold respectively in the form of an 80% (active material) and 100% (active material) gel in a mineral oil. They have a softening point of 88 to 105°C. These commercial products are a mixture of a copolymer of a C36 diacid condensed on ethylene diamine, with an average molecular weight of approximately 6000. The terminal ester groups result from the esterification of the remaining acid ends with cetyl alcohol, stearyl alcohol or their mixtures (also called cetylstearyl alcohol). 2) Mono- or polyalkyl esters of saccharide or polysaccharide
[0284] Among the mono or polyalkyl esters of saccharide or polysaccharide suitable for implementing the invention, mention may be made of alkyl or polyalkyl esters of dextrin or inulin.
[0285] This may in particular be a mono- or poly-ester of dextrin and at least one fatty acid and in particular corresponding to the following formula (VI):
[0286] Formula (VI) in which: n is an integer ranging from 3 to 200, in particular ranging from 20 to 150, and in particular ranging from 25 to 50, R 1 , R 2 and R 3 , identical or different, are chosen from hydrogen or an acyl group (RC(O)-) in which the radical R is a hydrocarbon group, linear or branched, saturated or unsaturated, having from 7 to 29, in particular from 7 to 21, in particular from 11 to 19, more particularly from 13 to 17, or even 15, carbon atoms, provided that at least one of said radicals R 1 , R 2 or R 3 is other than hydrogen.
[0287] In particular, R 1 , R 2 and R 3 may represent hydrogen or an acyl group (RC(O)-) in which R is a hydrocarbon radical as defined previously, provided that at least two of said radicals R 1 , R 2 or R 3 are identical and different from hydrogen.
[0288] All of the radicals R 1 , R 2 and R 3 may represent an identical or different acyl group (RC(O)), and in particular an identical one.
[0289] In particular, n previously exposed advantageously varies from 25 to 50, in particular is equal to 38 in the general formula of the saccharide ester usable in the present invention.
[0290] In particular when the radicals R 1 , R 2 and / or R 3 , which are identical or different, comprise an acyl group (RC(O)), these radicals may be chosen from the caprylic, capric, lauric, myristic, palmitic, stearic, arachic, behenic, isobutyric, isovaleric, 2-ethylbutyric, ethylmethylacetic, isoheptanoic, 2-ethylhexanoic, isononanoic, isodecanoic, isotridecanoic, isomyristic, isopalmitic, isostearic, isoaracic, isohexanoic, decenoic, dodecenoic, tetradecenoic, myristoleic, hexadecenoic, palmitoleic, oleic, elaidic, asclepinic, gondoleic, eicosenoic, sorbic, linoleic, linolenic radicals, punicic, stearidonic, arachidonic, stearolic, and mixtures thereof.
[0291] Preferably, at least one dextrin palmitate is used as the ester of dextrin and fatty acid(s). This can be used alone or in a mixture with other esters.
[0292] Advantageously, the dextrin and fatty acid ester has a degree of substitution less than or equal to 2.5 based on a glucose unit, in particular varying from 1.5 to 2.5, preferably from 2 to 2.5. The weight-average molecular weight of the dextrin ester may be in particular from 10,000 to 150,000, in particular from 12,000 to 100,000 and even from 15,000 to 80,000.
[0293] Dextrin esters, particularly dextrin palmitates, are commercially available under the name RHEOPEARL TL or RHEOPEARL KL from Chiba Flour. 3) amide derivatives of N-acylated amino acids
[0294] The N-acylated amino acid amides that can be used are, for example, the diamides of the association of an N-acylamine acid with amines comprising from 1 to 22 carbon atoms such as those described in document FR 2 281 162. These are, for example, alkyl glutamic acid amide derivatives such as laurylglutamic acid dibutylamide, marketed by the company Ajinomoto under the name “Gelling agent GP-1” or 2-ethylhexanoyl glutamic acid dibutylamide marketed by the company Ajinomoto under the name “Gelling agent GA-01”. 4) Copolymers comprising an alkylene or styrene sequence
[0295] Copolymers may have a comb or block structure of di-block, tri-block, multi-block and / or radial or star type and may comprise at least two thermodynamically incompatible segments.
[0296] The structuring agent may comprise, for example, a styrene segment block as described in applications EP 0 497 144, WO98 / 42298, US 6 225 690, US 6 174 968, US 6 225 390, an ethylene / butylene segment, an ethylene / propylene segment as described in applications US 6 225 690, US 6 174 968, US 6 225 390, a butadiene segment, an isoprene segment, a polyvinyl segment such as for example poly(meth)alkyl acrylate, or polyvinyl alcohol or polyvinyl acetate, a silicone segment as described in applications US 5 468 477 and US 5 725 882 or a combination of these segments.
[0297] A diblock copolymer is usually defined as AB type in which a hard segment (A) is followed by a soft segment (B).
[0298] A triblock copolymer is usually defined as ABA type or as a ratio of a hard segment, a soft segment, and a hard segment.
[0299] A multi-block or radial or star copolymer may have any type of combination of hard segments and soft segments, provided that the characteristics of the hard segments and soft segments are retained.
[0300] As an example of hard block copolymer segments, mention may be made of styrene, and as an example of soft block copolymer segments, mention may be made of ethylene, propylene, butylene, and a combination thereof.
[0301] The tri-block copolymers, and in particular those of the polystyrene / polyisoprene or polystyrene / polybutadiene type, suitable for implementing the invention may be those marketed under the reference LUVITOL HSB by the company BASF. Mention may also be made of tri-block copolymers of the polystyrene / copoly(ethylene-propylene) or polystyrene / copoly(ethylene-butylene) type, such as those marketed under the reference KRATON by the company SHELL CHEMICAL CO, or under the reference GELLED PERMETHYL 99 A by the company PENRECO. Such tri-block copolymers are particularly preferred according to the invention.
[0302] As another example of block copolymers that may be suitable for implementing the present invention, mention may also be made of the block copolymers marketed under the reference VERSAGEL by the company PENRECO, those marketed under the reference KRATON by the company SHELL and those marketed under the reference GEL BASE by the company BROOKS INDUSTRIES.
[0303] Among the thickening polymers for fatty phase, polymers carrying at least one crystallizable sequence in the skeleton are preferred.
[0304] Thickening polymers for aqueous or fatty phase can be used alone or in mixtures in any proportion.
[0305] Preferably the thickeners are aqueous phase thickeners.
[0306] Preferably, the polymers of the cosmetic compositions in accordance with the present invention advantageously have, in solution or in dispersion, at 1% of active material in water, a viscosity measured using the Rhéomat RM 180 rheometer, at 25°C, greater than 0.1 ps, and more advantageously still greater than 0.2 cp, at a shear rate of 200 s-1.
[0307] According to a preferred embodiment of the invention, the thickening polymer(s) of the invention are non-associative and preferably derived from the (co)polymerization of acrylate monomer CH 2 =C(R')-COOR‴ (VIa) and / or of acrylamide monomer CH 2 =C(R')-CO-N(R")-LY -< M +< (VIb) Formulae (Via) and (VIb) in which R', and R", identical or different, represent a hydrogen atom or a (C 1 -C 6 )alkyl group such as methyl, preferably hydrogen, R'" represents an alkali metal, an alkaline earth metal, a hydrogen atom or a (C 1 -C 6 )alkyl group optionally substituted in particular by one or more hydroxy, carboxy or amino groups, L representing a divalent, cyclic or acyl, saturated or unsaturated, linear or branched, optionally interrupted hydrocarbon group and / or substituted by one or more heteroatoms such as O, N and comprising from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms,preferably L represents the divalent group -[C(R')(R")] p - with p representing an integer between 1 and 4, preferably 2 and 3 such that 2, R' and R" being as defined previously, more particularly L represents -C(R')(R")-CH 2 - or -CH 2 -C(R')(R")- with R' and R" as defined previously, preferably R' and R" represent a (C 1 -C 4 )alkyl group such as methyl; Y-represents an anionic group such as carboxylate, phosphate, phosphonate, sulfonate, or sulfate preferably -S(O) 2 -O -< , and M+ being a cationic counterion preferably an alkali metal such as sodium, said copolymer being able to be in direct or inverse emulsion,preferably inverse. More preferably, the thickening polymer(s) of the invention are derived from the copolymerization of acrylate monomer CH 2 =C(R')-COOH (VIla) and acrylamide monomer CH 2 =C(R')-CO-N(R")-LY -< M +< (VIb) as defined above. Among the thickening polymers, mention may be made of; preferably, the thickening organic polymers are chosen from crosslinked or non-crosslinked acrylic or methacrylic acid copolymers, crosslinked or non-crosslinked homopolymers of 2-acrylamido-2-methyl-propanesulfonic acid and their crosslinked or non-crosslinked acrylamide copolymers, ammonium acrylate homopolymers or ammonium acrylate and acrylamide copolymers alone or as mixtures.,
[0308] According to an advantageous variant, the composition of the invention comprises one or more associative or non-associative, preferably non-associative, thickening polymers with sugar units, in particular derived from the following sugars: glucose; galactose; arabinose; rhamnose; mannose; xylose; fucose; anhydrogalactose; galacturonic acid; glucuronic acid; mannuronic acid; galactose sulfate; anhydrogalactose sulfate and fructose, preferably galactose anhydrogalactose, preferably agar.
[0309] Preferably, the organic thickening polymer(s) is or are present in the composition according to the invention in a content ranging from 0.01 to 10% by weight, more preferably from 0.1 to 5% by weight relative to the total weight of the composition.
[0310] According to a particular embodiment, the weight ratio of fatty substances / surfactants is inclusively between 5 and 20, preferably between 8 and 15, even more preferably between 10 and 13 such as 11.8.
[0311] According to one embodiment of the invention, the weight ratio of fatty substances / sum of surfactant(s) and polymer(s) [surfactant(s) + polymer] is inclusively between 0.8 and 10, particularly between 1 and 5, more particularly between 1.5 and 2.5, such as 1.9.
[0312] Preferably, the composition comprises i) 4-(3-ethoxy-4-hydroxyphenyl)butan-2-one as well as its acid or base salts, organic or mineral, and its solvates such as hydrates in a content ranging from 0.02 to 2% by weight, relative to the total weight of the composition, preferably ranging from 0.03 to 1% by weight, and better still ranging from 0.04 to 0.8% by weight.
[0313] The invention also relates to a composition comprising, in a physiologically acceptable medium, the antimicrobial mixture described above.
[0314] A physiologically acceptable medium is understood to mean a medium compatible with human keratin materials such as skin, scalp, nails and keratin fibres such as hair.
[0315] Said medium may comprise one or more additional ingredients, distinct from ingredients i) and ii).
[0316] The composition may comprise one or more additional ingredients or adjuvants chosen from gelling agents other than organic thickening polymers as defined above, non-thickening non-anionic, cationic, non-ionic, zwitterionic, natural or synthetic polymers, film-forming or not, coloring materials such as organic or mineral pigments, perfumes, fillers, UV filters, plant extracts, cosmetic and dermatological active ingredients, and salts.
[0317] The composition according to the invention may be in the form of oil-in-water (O / W) or water-in-oil (W / O) or multiple (triple: W / O / W or O / W / O) emulsions, oily solutions, oily gels, aqueous solutions, aqueous gels, solid compositions. The composition of the invention is prepared according to the usual methods.
[0318] The composition according to the invention preferably comprises water, i.e. it is aqueous. According to one embodiment of the invention, the composition comprises an aqueous phase and an organic or oily phase. Preferably, the composition of the invention is a direct emulsion of the O / W type.
[0319] According to another particular embodiment of the invention, the composition is aqueous and does not comprise surfactants.
[0320] The compositions according to the invention may be more or less fluid and have the appearance of a white or colored cream, an ointment, a milk, a lotion, a serum, a paste, a mousse. They may optionally be applied to the skin in the form of an aerosol. They may also be in solid form, for example in the form of a stick or compact powder.
[0321] The composition according to the invention may in particular be presented in the form: of a makeup product, in particular for the skin of the face, body or lips or eyelashes; of an aftershave gel or lotion; of a shaving product; of a deodorant (stick, roll-on, aerosol) of a depilatory cream; in the form of a body hygiene composition such as a shower gel or a shampoo; of a pharmaceutical composition; of a solid composition such as a soap or a cleaning bar; of an aerosol composition also comprising a pressurized propellant; of a hair-styling lotion, a styling cream or gel, a dye composition, a perm composition, an anti-hair loss lotion or gel, a conditioner; of a skin care or cleansing composition. The process of preparing the composition :
[0322] The invention also relates to a process for preparing a composition, in particular cosmetic or pharmaceutical or food, comprising a step of mixing i) 4-(3-ethoxy-4-hydroxyphenyl)butan-2-one, one of its base salts or solvates, ii) 4-hydroxyacetophenone one of its base salts or solvates, and optionally one or more additional ingredients or adjuvants, in particular cosmetic or pharmaceutical or food, such as those described above, and optionally water, and one or more organic solvents. Antimicrobial activity and their use :
[0323] The antimicrobial activity, in particular synergistic activity, of the mixture i) and ii) according to the invention on fungi, in particular on the species Candida albicansis of interest in water treatment. Indeed, fungi represent one of the sources of water contamination as mentioned in the article “Fungal Contaminants in drinking water regulation?, A tale of ecology, exposure, purification and clinical relevance” Int. J. Environ. Res. Public Health 2017, 14, 636.
[0324] The present invention also relates to the use of the antimicrobial mixture in the treatment of water, where said water is selected from domestic or industrial water, water from aquatic environments, swimming pool / spa water, and air conditioning system water.
[0325] "Water treatment" means a treatment consisting of adding a substance to a sample of water to be treated or to a continuous or discontinuous flow of water to be treated (batch type) with a view either to preventing contamination of the water by a contaminating agent or to partially or totally decontaminating said water to be treated from said contaminating agent.
[0326] Preferably, the water treatment carried out within the framework of the present invention consists of adding a substance to a sample of water to be treated or to a continuous or discontinuous flow of water to be treated in order to partially or totally decontaminate said water to be treated from a contaminating agent.
[0327] The contaminating agent may be a microorganism, particularly a bacterium and / or a fungus.
[0328] Even more preferably, said water treatment is a treatment of water contaminated by one or more microorganisms, preferably by Gram + / - bacteria or fungi of the species Enterococcus faecalis, Candida albicans, Pseudomonas aeruginosa.
[0329] "Waters of aquatic environments" means waters of lakes, rivers, ponds, streams, sea or ocean bathing areas, groundwater such as well water and water tables, and aquarium water.
[0330] For the purposes of the present invention, "domestic or industrial water" includes wastewater before its treatment in a treatment plant, water during treatment in a treatment plant, water before its treatment in a drinking water treatment plant, water during treatment in a drinking water treatment plant, as well as water circulating in potable or non-potable urban networks, such as, for example, water circulating in pipes.
[0331] The present invention also relates to a water treatment method comprising at least one step of bringing a sample of water to be treated or a continuous or discontinuous flow of water to be treated into contact, said water to be treated being chosen from domestic or industrial water, water from aquatic environments, swimming pool / spa water, and air conditioning system water, with the antimicrobial mixture according to the invention.
[0332] Preferably, said step of bringing the water to be treated into contact with the antimicrobial mixture according to the invention can in particular be carried out by injecting said compound in liquid form, by passing it over a filter or a filter cartridge comprising said compound, or by administering said compound in solid form, in particular in the form of granules, pebbles or even tablets.
[0333] i) 4-(3-ethoxy-4-hydroxyphenyl)butan-2-one and its acid or base salts, organic or inorganic, and its solvates such as hydrates may be used at a rate of at least 0.06% by weight, preferably at least 0.1% by weight, even better at least 0.5% by weight relative to the total weight of water to be treated. In a particular embodiment, the compounds of formula (I) or (I') or its solvates such as hydrates may be used at a rate of at least 1% by weight relative to the total weight of water to be treated.
[0334] i) 4-(3-ethoxy-4-hydroxyphenyl)butan-2-one as well as its acid or base salts, organic or inorganic, and its solvates such as hydrates can be used in a concentration ranging from 0.06% to 10% by weight, preferably from 0.1% to 5% by weight, even better from 0.5% to 2% by weight relative to the total weight of water to be treated. In a preferred embodiment, 4-(3-ethoxy-4-hydroxyphenyl)butan-2-one can be used in a concentration ranging from 0.1% to 1% by weight relative to the total weight of water to be treated.
[0335] The solvent may be used in a content ranging from 0.05% to 10% by weight, relative to the total weight of the water to be treated, preferably ranging from 0.1% to 5% by weight, and preferentially ranging from 0.1% to 2.5% by weight relative to the total weight of the water to be treated.
[0336] The invention is illustrated in more detail in the following example. The contents of the ingredients are expressed as a percentage by weight. EXAMPLES Example 1: Determination of antimicrobial activity synergy in MIC
[0337] The demonstration of a synergistic effect of antimicrobial activity with a mixture of 4-(3-ethoxy-4-hydroxyphenyl)butan-2-one (called substance A) and an alcohol compound (called substance B) was carried out by calculating the synergy index (or FIC index), according to the following formula:
[0338] FIC Index = CMI de A avec B / CMI de A + CMI de B avec A / CMI de B with : MIC of A with B: minimum concentration of product A in the combination A + B allowing an inhibitory effect to be obtained; MIC of B with A: minimum concentration of product B in the combination A + B allowing the inhibitory effect to be obtained; MIC of A: minimum inhibitory concentration of product A alone; MIC of B: minimum inhibitory concentration of product B alone.
[0339] This formula was first described in the article by FC Kull, PC Eisman, HD Sylwestrowka, and RL Mayer, Applied Microbiology 9:538-541, 1961.
[0340] For each compound tested alone, the MIC is considered to be the first concentration allowing a percentage of microbial growth to be obtained less than or equal to 25%.
[0341] Regarding the tested associations, MIC of A with B and MIC of B with A are the respective concentrations of A and B in the associations allowing the obtaining of a percentage of microbial growth less than or equal to 25%. Interpretation of the FIC Index :
[0342] When the FIC index value is less than or equal to 1, the combination of tested compounds is considered to have a synergistic effect.
[0343] The summary of the results obtained is presented in the following tables.
[0344] The combination of compounds A and B, and the compositions containing them, were tested on the following strains or part thereof: Aspergillus niger, Escherichia coli, Staphylococcus aureus, and Candida albicans.
[0345] The microbial strain was used Aspergillus nigerATCC 6275, and a liquid culture medium Sabouraud broth supplemented with polyoxyethylenated sorbitan monopalmitate (20 EO) (Tween 40 from Croda) and Phytagel ©< BioReagent, at double concentration (i.e. a mixture of 5 g of Phytagel + 0.6 g tween 40 + 60 g Sabouraud broth).
[0346] The microbial strain was used Staphylococcus aureus ATCC 6538 and a double strength nutrient broth liquid culture medium.
[0347] The microbial strain was used Candida albicans ATCC 10231 and a liquid culture medium Sabouraud broth, at double concentration (i.e. a mixture of 5 g of Phytagel + 0.6 g tween 40 + 60 g Sabouraud broth).
[0348] A 96-well microplate is used at an incubation temperature of 32.5°C.
[0349] The incubation time of the microplate is: 24 to 30 hours in aerobiosis for microbial Aspergillus niger ATCC 6275. 18 to 24 hours in aerobiosis for Candida albicans ATCC 10231, Pseudomonas aeruginosa ATCC 9027 and Staphylococcus aureus ATCC 6538. Tests
[0350] For each compound: A = 4-(3-ethoxy-4-hydroxyphenyl)butan-2-one B = 4-hydroxyacetophenone
[0351] A 10% (w / v) stock solution was prepared by mixing 1 g of compound in 9 ml of 1‰ aqueous agar solution. Successive dilutions were made with the 1‰ agar solution. Tests of compounds A and B alone
[0352] 50 µL of each of the daughter solutions obtained containing compound A or B is added to the wells of the microplate. 100 µL of Sabouraud liquid nutrient broth inoculated at double concentration with the strain is also added. Aspergillus niger and 50 µL of 1‰ aqueous agar solution. Tests of compounds A and B in mixture
[0353] 50 µL of each of the daughter solutions obtained containing compound A and 50 µL of each of the daughter solutions obtained containing compound B are added to the wells of the microplate. 100 µL of Sabouraud liquid nutrient broth inoculated at double concentration with the strain are also added. Aspergillus niger. Microbial growth indicator
[0354] A positive control for microbial growth was also performed. The positive control for microbial growth corresponds to the mixture of 100 µL of a 1‰ aqueous agar solution with 100 µL of Sabouraud liquid nutrient broth inoculated at double concentration with the strain Aspergillus niger in the absence of compounds A and B. Absorbance control of compounds A and B alone
[0355] In parallel, an absorbance control of compounds A and B alone was carried out. This control corresponds to 100 µL of sterile Sabouraud liquid nutrient broth at double concentration + 100 µL of compound A or B at double concentration.
[0356] In all three cases (absorbance control, growth control and test) the final volume present in each well of the microplate is 200 µL.
[0357] In both cases (test and control), the inoculum represents the concentration of the strain Aspergillus niger present in the final volume of the wells (200 µL) and is between 2 and 6.10 5< CFU / mL in Aspergillus niger.
[0358] The minimum inhibitory concentration (MIC) of each compound A and B alone and in combination was determined in a known manner using optical density measurements at the wavelength of 620 nm.
[0359] The test as described above (assays, absorbance controls and growth control) was again carried out to test the A + B association on the following strains: Aspergillus niger, Escherichia coli, Staphylococcus aureus, and Candida albicans.
[0360] The following results were obtained with compound B = 4-hydroxy acetophenone: Aspergilus niger
[0361] [Tables 1] Tested concentrations (in % weight) 0 A 0,025 A 0,05 A 0,1 A 0 B - 82 43 5 0,0625 B 86 71 46 3 0,125 B 72 73 20 (FIC 0.75) 2 0,25 B 79 22 (FIC 0.75) 12 (FIC 1) 5 0,5 B 6 2 (FIC 0.75) -19 (FIC 1) 6 [Tables 2] CMI of A alone in % MIC of B alone in % MIC of each compound in mixture FIC Index A / B ratio A % B % 0,1 0,5 0,05 0,25 1 0,2
[0362] The results obtained show an improvement in antimicrobial properties, and in particular a synergy of inhibitory activity for the following mixtures: 0.05% of A and 0.25% of B or ratio A / B = 0.2 0.05% of A and 0.125% of B or ratio A / B = 0.4 0.025% of A and 0.25% of B or ratio A / B = 0.1
[0363] Antimicrobial properties were also evaluated with other compositions, such as those detailed below in Table 3 in which the ingredients are given by weight (g) per 100 g of composition. The properties were evaluated at 7 days, 14 days and 1 month. [table 3] Ingredients Composition 1 Invention Composition 2 Comparative Composition 3 Comparative A 0,7 0,7 - B 0,2 - 0,2 Propylene glycol stearate (20 EO) 0,8 0,8 0,8 Glyceryl mono / distearate / polyethylene glycol stearate blend (100 EO) 2 2 2 Fatty acid (mainly stearic acid) of plant origin 3 3 3 Cetyl alcohol 0,5 0,5 0,5 Stearyl alcohol 0,5 0,5 0,5 Myristyl myristate 2 2 2 White beeswax 1 1 1 Shea butter 2 2 2 Mixture of caprylic and capric acid triglycerides 3,1 3,1 3,1 Isopropyl isostearate 1,2 1,2 1,2 Cyclohexadimethylsiloxane 6 6 6 Glycerin 7,0 7,0 7,0 Acrylamide / sodium acrylamido-2-methyl propane sulfonate copolymer POLYSORBATE 80 / I-C16 2,2 2,2 2,2 Mineral pigment 0,15 0,15 0,15 Organic pigment 0,01 0,01 0,01 Trietanolamine (basic pH agent) 0,15 0,15 0,15 Vitamin E: DL-α-tocopherol 0,5 0,5 0,5 Water Qsp 100 Qsp 100 Qsp 100
[0364] Results on the microbial strain Escherichia coli 7 days are given in the table below: [table 4] Compositions After 7 days number of microbes Composition 1 (invention) <200 Composition 2 (comparative) 2,4.10 4< Composition 3 (comparative) 2,1.10 5<
[0365] Results on the microbial strain Staphylococcus aureus at 7 and 14 days are given in the table below: [Table 5] Compositions After 7 days number of microbes After 7 days number of microbes Composition 1 (invention) 3,7.10 5< 3,4.10 3< Composition 2 (comparative) 2,4.10 6< 9,6.10 5< Composition 3 (comparative) 1,9.10 6< 3,0.10 4<
[0366] The results on other microbial strains at 7, 14 days and then 1 month are given in the table below: [Table 6] Compositions / Targeted strains After 7 days After 14 days After 1 month Composition 1 (invention) - Candida albicans 8,6.10 3< <200 <200 - Aspergillus niger 6,8.10 5< 2.0.10 3< <200 Composition 2 (comparative) - Candida albicans 2,0.10 5< 8,2.10 4< 3,0.10 3< - Aspergillus niger 4,1.10 6< 5,0.10 6< 5,4.10 6< Composition 3 (comparative) - Candida albicans 3,4.10 5< 1.10 5< 3,8.10 4< - Aspergillus niger 3,4.10 6< 3,4.10 6< 2,3.10 6<
[0367] It appears from the results of the tables above that the association of A and B according to the invention allows a clear antimicrobial improvement and this after 7 days, 15 days, or even one month for a wide variety of microbial strains ( Aspergillus niger, Escherichia coli, Staphylococcus aureus, and Candida albicans).
Claims
1. Antimicrobial mixture comprising i) 4-(3-ethoxy-4-hydroxyphenyl)butan-2-one and also the organic or mineral acid or base salts thereof, or the solvates thereof such as hydrates, with ii) 4-hydroxyacetophenone and also the acid or base salts thereof or the solvates thereof such as hydrates.
2. Mixture according to the preceding claim, wherein the weight ratio i) / ii) ranges from 0.05 to 5, preferably ranges from 0.08 to 5, preferentially ranges from 0.08 to 0.25, and from 2 to 4, more preferentially ranges from 0.15 to 0.25 and from 3 to 3.8.
3. Mixture according to Claim 1, wherein the weight ratio i) / ii) ranges from 0.08 to 0.5, preferably ranges from 0.08 to 0.3, preferentially ranges from 0.08 to 0.25, more preferentially ranges from 0.15 to 0.25.
4. Mixture according to Claim 1, wherein the weight ratio i) / ii) ranges from 0.5 to 5, preferentially range from 1 to 4 and more preferentially 3 to 3.8.
5. Composition comprising i) 4-(3-ethoxy-4-hydroxyphenyl)butan-2-one and also the organic or mineral acid or base salts thereof, or the solvates thereof such as hydrates, with ii) 4-hydroxyacetophenone and also the acid or base salts thereof or the solvates thereof such as hydrates, preferentially in a weight ratio i) / ii) as defined in one of Claims 2 to 4.
6. Composition according to the preceding claim, which comprises one or more nonionic, anionic, cationic, zwitterionic or amphoteric surfactants, particularly chosen from nonionic and anionic surfactants, and a mixture thereof.
7. Composition according to Claim 5 or 6, which comprises one or more nonionic surfactants chosen from: (poly)ethoxylated fatty alcohols; glycerolated fatty alcohols; alkylpolyglycosides, preferably oxyethylenated fatty acid mono- and diesters of sorbitan having from 2 to 200 mol of EO, in particular from 10 to 100 EO, such as propylene glycol stearate having from 10 to 30 EO, such as 20 EO, and glyceryl monostearate / distearate / polyethylene glycol stearate (100 EO), or a mixture thereof.
8. Composition according to any one of Claims 5 to 7, which comprises one or more anionic surfactants chosen from: alkyl carboxylic acids, alkyl sulfates, alkyl ether sulfates, alkylamido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkylsulfonates, alkylamidesulfonates, alkylarylsulfonates, α-olefinsulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfoacetates, acyl sarcosinates, acyl glutamates, alkyl sulfosuccinamates, acyl isethionates and N-acyltaurates, salts of alkyl monoesters of polyglycoside-polycarboxylic acids, salts of alkyl diesters of polyglycoside-polycarboxylic acids, acyl lactylates, D-galactoside-uronic acid salts, alkyl ether carboxylic acid salts, alkylaryl ether carboxylic acid salts, alkylamido ether carboxylic acid salts, and the corresponding non-salified forms of all these compounds, the alkyl and acyl groups of all these compounds comprising from 8 to 30 carbon atoms and preferably from 10 to 22 carbon atoms and the aryl group denoting a phenyl group which can be oxyethylenated; preferably the anionic surfactant(s) are chosen from (C6-C24) alkyl carboxylic acids, in particular (C10-C20)alkyl carboxylic acids, preferably of natural origin, in particular of plant origin, such as stearic acid, which may be in the form of alkali metal, ammonium, amino alcohol and alkaline-earth metal salts, or a mixture of these compounds.
9. Composition according to any one of Claims 6 to 8, wherein the amount of surfactants preferably ranges from 0.5% to 30% by weight, in particular from 1% to 20% by weight and more particularly from 2% to 10% by weight, more preferentially between 4% and 6%, relative to the total weight of the composition of the invention.
10. Composition according to any one of Claims 5 to 9, which comprises one or more fatty substances preferably chosen from: a) butters, preferably shea butter; b) waxes, preferably beeswaxes; c) non-liquid fatty alcohols, particularly chosen from saturated or unsaturated, linear or branched alcohols comprising from 8 to 30 carbon atoms, which are preferentially C10-C22, more preferentially C14-C20, better still C16-C18, such as cetyl alcohol and stearyl alcohol and the mixture thereof; d) non-liquid fatty acid and / or fatty alcohol esters, in particular solid esters derived from C9-C26 fatty acids and from C9-C26 fatty alcohols, in particular alkyl myristates such as cetyl, mirystyl or stearyl myristate; hexyl stearate, more particularly myristyl myrystate; e) esters of monoalcohols, at least one of the alcohol or of the acid of which are derived from said esters is branched, such as ethyl palmitate, isopropyl palmitate, alkyl myristates, such as isopropyl myristate or ethyl myristate, isocetyl stearate, 2-ethylhexyl isononanoate, isodecyl neopentanoate, isostearyl neopentanoate and C10-C22, preferably C12-C20, alkyl (iso)stearates, such as isopropyl isostearate; f) cyclic polydialkylsiloxanes comprising from 3 to 7, preferably from 4 to 5 silicon atoms, such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclopentasiloxane, or cyclohexadimethylsiloxane and also mixtures thereof, preferably cyclohexadimethylsiloxane; g) oils of plant origin or synthetic triglycerides, such as liquid triglycerides of fatty acids containing from 6 to 30 carbon atoms, for instance heptanoic or octanoic acid triglycerides, or alternatively sunflower oil, corn oil, soybean oil, marrow oil, grapeseed oil, sesame seed oil, hazelnut oil, apricot oil, macadamia oil, arara oil, sunflower oil, castor oil, avocado oil, caprylic / capric acid triglycerides, jojoba oil, shea butter oil.
11. Composition according to any one of Claims 5 to 10, which comprises one or more fatty substances in an amount ranging from 1% to 40% by weight, preferably in an amount ranging from 5% to 30% by weight and even more preferentially in an amount ranging from 10% to 20% by weight, relative to the total weight of the composition.
12. Composition according to any one of Claims 5 to 11, which comprises one or more thickening organic polymers, in particular of natural or synthetic origin, which are associative or non-associative, preferably non-associative, anionic, cationic, amphoteric or nonionic polymers.
13. Composition according to any one of Claims 5 to 12, which comprises one or more thickening organic polymers resulting from the (co)polymerization: - of acrylate monomer CH2=C(R')-COOR‴ (VIa) and / or - of acrylamide monomer CH2=C(R')-CO-N(R")-L-Y- M+ (VIb) Formulae (VIa) and (VIb) wherein: * R' and R'', which may be identical or different, represent a hydrogen atom or a (C1-C6)alkyl group such as methyl, preferably hydrogen, * R‴ represents an alkali metal, an alkaline-earth metal, a hydrogen atom or a (C1-C6)alkyl group optionally substituted in particular by one or more hydroxyl, carboxy or amino groups; * L representing a linear or branched, saturated or unsaturated, cyclic or acyclic, divalent hydrocarbon group optionally interrupted and / or substituted by one or more heteroatoms such as O or N and comprising from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms, preferably L represents the divalent group - [C(R')(R'')]p- with p representing an integer between 1 and 4, preferably 2 and 3, such as 2, R' and R'' being as defined above, more particularly L represents - C(R')(R")-CH2- or -CH2-C(R')(R")- with R' and R" as defined above, preferably R' and R'' represent a (C1-C4)alkyl group such as methyl; * Y- represents an anionic group such as carboxylate, phosphate, phosphonate, sulfonate or sulfate, preferably - S(O)2-O-, and M+ being a cationic counterion, preferably an alkali metal such as sodium, said copolymer possibly being in a direct or inverse emulsion, preferably an inverse emulsion; more preferentially, the thickening organic polymer(s) of the invention result from the copolymerization of an acrylate monomer CH2=C(R')-COOH (VIa) and an acrylamide monomer CH2=C(R')-CO-N(R")-L-Y- M+ (VIb) as defined above; preferably, the thickening organic polymers are chosen from crosslinked or non-crosslinked acrylic acid or methacrylic acid copolymers, crosslinked or non-crosslinked 2-acrylamido-2-methylpropanesulfonic acid homopolymers and crosslinked or non-crosslinked acrylamide copolymers thereof, ammonium acrylate homopolymers, or copolymers of ammonium acrylate and of acrylamide, alone or as mixtures.
14. Composition according to any one of Claims 5 to 13, which comprises one or more thickening organic polymers with sugar units, in particular derived from the following sugars: glucose; galactose; arabinose; rhamnose; mannose; xylose; fucose; anhydrogalactose; galacturonic acid; glucuronic acid; mannuronic acid; galactose sulfate; anhydrogalactose sulfate and fructose, more particularly galactose and anhydrogalactose, preferably the thickening organic polymer(s) with sugar units are chosen from agar.
15. Composition according to any one of Claims 5 to 14, which comprises one or more thickening organic polymers in a content ranging from 0.01% to 10% by weight, more preferentially from 0.1% to 5% by weight relative to the total weight of the composition.
16. Composition according to any one of Claims 5 to 15, which comprises one or more fatty substances as defined in the claims in Claims 10 or 11, and one or more surfactants as defined in any one of Claims 6 to 9, the fatty substance / surfactant(s) weight ratio of which is inclusively between 5 and 20, preferably between 8 and 15, even more preferentially between 10 and 13, such as 11.8.
17. Composition according to any one of Claims 5 to 16, which comprises one or more fatty substances as defined in the claims in Claims 10 or 11, and one or more surfactants as defined in any one of Claims 6 to 9, and one or more thickening organic polymers as defined in any one of Claims 12 to 15, the weight ratio of the fatty substance / sum of surfactant(s) and polymer(s) [surfactant(s) + polymer] of which is inclusively between 0.8 and 10, particularly between 1 and 5, more particularly between 1.5 and 2.5, such as 1.9.
18. Composition according to any one of Claims 5 to 17, which comprises an aqueous phase and an organic or oily phase, preferably the composition of the invention is a direct emulsion of the oil-in-water (O / W) type.
19. Composition according to any one of Claims 5 and 10 to 15, which is aqueous and does not comprise surfactants.
20. Composition according to any one of Claims 5 to 19, which comprises one or more organic solvents, in particular chosen from a) C2-C6 alkanols, such as ethanol and isopropanol; b) polyols miscible with water at ambient temperature (25°C) chosen in particular from polyols having in particular from 2 to 10 carbon atoms, preferably having from 2 to 6 carbon atoms, such as glycerol, propylene glycol, 1,3-propanediol, butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol, diethylene glycol or diglycerol; c) polyol ethers, such as 2-butoxyethanol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monomethyl ether; and also d) aromatic alcohols, such as benzyl alcohol or phenoxyethanol, and mixtures thereof, preferably the composition comprises one or more polyols in particular chosen from polyols having in particular from 2 to 10 carbon atoms, preferably having from 2 to 6 carbon atoms, such as glycerol.
21. Composition according to any one of Claims 5 to 20, which comprises one or more organic solvents present in amounts of inclusively between 0.1% and 40% by weight approximately relative to the total weight of the composition, more preferentially between 1% and 20% by weight approximately and even more particularly inclusively between 5% and 10% by weight relative to the total weight of the composition.
22. Nontherapeutic cosmetic treatment process for caring for and / or making up and / or cleansing keratin materials, comprising the application to said keratin materials of a composition according to any one of Claims 5 to 21.
23. Process for preserving a composition comprising a physiologically acceptable medium, in particular a cosmetic or dermatological composition, characterized in that it consists in incorporating into said composition an antimicrobial mixture as defined in one of Claims 1 to 4 or a composition as defined in any one of Claims 5 to 21.