USE OF A GLYCINE BETAINE DERIVATIVE AS AN AGENT FOR CONDITIONING KERATIN FIBRES
20220409507 · 2022-12-29
Inventors
Cpc classification
A61K8/342
HUMAN NECESSITIES
A61K8/463
HUMAN NECESSITIES
A61K8/44
HUMAN NECESSITIES
International classification
Abstract
The present invention relates to a method for conditioning keratin fibres, comprising topically applying, to the keratin fibres, a cosmetic composition in the form of an emulsion containing, in a cosmetically acceptable medium, a surfactant composition containing at least one ester or amide salt of glycine betaine comprising from 14 to 24 carbon atoms. The invention also relates to the use of a surfactant composition as defined above as an agent for conditioning the keratin fibres.
Claims
1-12. (canceled)
13. A cosmetic method for conditioning keratin fibers, comprising the topical application to the keratin fibers of a cosmetic composition in the form of an emulsion comprising, in a cosmetically acceptable medium, a surfactant composition comprising at least one glycine betaine derivative of formula (1): X.sup.n−[(CH.sub.3).sub.3N.sup.+—CH.sub.2—COZ—R].sub.n where Z denotes an oxygen atom or an —NH group, R is a saturated or unsaturated, linear or branched alkyl group comprising from 14 to 24 carbon atoms, X is an organic or inorganic anion, and n is equal to 1 or 2, provided that said surfactant composition does not contain alkyl polyglycosides.
14. The method according to claim 13, wherein the R radical is selected from the group consisting of: myristyl (C14:0), cetyl (C16:0), palmitoleyl (C16:1), stearyl (C18:0), oleyl (C18:1), linoleyl (C18:2), linolenyl (C18:3), arachidyl (C20:0), arachidonyl (C20:4), behenyl (C22:0), 2-hexyldecyl, 2-octyldodecyl and 2-decyltetradecyl.
15. The method according to claim 13, wherein the X anion is selected from the group consisting of: a chloride, a sulfate, a perchlorate, an alkylsulfate ion, decylsulfate, laurylsulfate, an arylsulfonate ion, an alkylsulfonate ion, and a sulfosuccinate ion.
16. The method according to claim 13, wherein the surfactant composition comprises the following constituents: (a) at least one glycine betaine ester salt of formula (1): X.sup.n−[(CH.sub.3).sub.3N.sup.+—CH.sub.2—COO—R].sub.n where R is a saturated or unsaturated, linear or branched alkyl group comprising from 14 to 24 carbon atoms, (b) at least one fatty alcohol of formula R—OH, (c) an organic or inorganic acid of formula XH, and (d) a glycine betaine salt of formula X.sup.n−[(CH.sub.3).sub.3N.sup.+—CH.sub.2—COOH].sub.n where X is an organic or inorganic anion and n is equal to 1 or 2.
17. The method according to claim 16, wherein the surfactant composition comprises: (a) from 15% to 45% by weight of glycine betaine ester salt, (b) from 55% to 80% by weight of fatty alcohol, (c) from 0 to 5% by weight of organic or inorganic acid, (d) from 0 to 3% by weight of glycine betaine salt, (e) from 0 to 15% by weight of dialkyl ether.
18. The method according to claim 13, wherein the surfactant composition comprises the following constituents: (a) one or more glycine betaine amide salts of formula (1): X.sup.n−[(CH.sub.3).sub.3N.sup.+—CH.sub.2—CONH—R].sub.n where R is a saturated or unsaturated, linear or branched alkyl group comprising from 14 to 24 carbon atoms; (b) one or more alkylammonium salts of formula (2): X.sup.n−[NH.sub.3.sup.+R].sub.n where R is a saturated or unsaturated, linear or branched alkyl group comprising from 14 to 24 carbon atoms; (c) one or more glycine betaine ester salts of formula (3): X.sup.n−[(CH.sub.3).sub.3 N.sup.+—CH.sub.2—COOR′].sub.n where R′ is a saturated or unsaturated, linear or branched alkyl radical containing from 4 to 8 carbon atoms; and (d) glycine betaine of formula (4): (CH.sub.3).sub.3N.sup.+—CH.sub.2—COO.sup.− where X is an organic or inorganic anion and n is equal to 1 or 2.
19. The method according to claim 13, wherein the surfactant composition comprises at least 90% by weight of glycine betaine derivative.
20. The method according to claim 13, wherein the keratin fibers are selected from the group consisting of hair, beard and eyebrows.
21. The method according to claim 20, wherein the composition is applied to weakened and/or damaged hair or hair weakened and/or damaged by chemical treatments, mechanical treatments, dyeing, bleaching, permanent waving, straightening or by brushing.
22. The method according to claim 13, the conditioned keratin fibers having improved combability and/or softness and/or suppleness and/or manageability and/or sheen and/or smoothness and/or hydration and/or reduced static electricity.
23. The method according to claim 13, wherein the cosmetic composition is applied to hair that has been washed and rinsed beforehand.
24. The method according to claim 13, wherein the X anion is selected from the group consisting of alkylsulfonates and arylsulfonates.
25. The method according to claim 16, wherein R is a saturated or unsaturated, linear or branched alkyl group comprising from 18 to 22 carbon atoms.
26. The method according to claim 18, wherein R is a saturated or unsaturated, linear or branched alkyl group comprising from 16 to 22 carbon atoms.
27. The method according to claim 24, wherein the alkylsulfonate is methanesulfonate or ethanesulfonate.
28. A keratin fiber conditioning agent, comprising a surfactant composition comprising at least one glycine betaine derivative of formula (1): X.sup.n−[(CH.sub.3).sub.3N.sup.+—CH.sub.2—COZ—R].sub.n where Z denotes an oxygen atom or an —NH group, R is a saturated or unsaturated, linear or branched alkyl group comprising from 14 to 24 carbon atoms, X is an organic or inorganic anion, and n is equal to 1 or 2.
Description
FIGURES
[0093]
[0094]
EXAMPLES
[0095] The invention will be better understood in light of the following examples, which are given for purely illustrative purposes and are not intended to limit the scope of the invention, defined by the appended claims.
Example 1: Synthesis of Surfactant Compositions Based on Glycine Betaine Ester Salts
[0096] Synthesis of Methanesulfonic Acid Salts
[0097] Glycine betaine (1.0 eq) and a mixture of C18 to C22 fatty alcohols (1.4 eq) are introduced into a reactor. The setpoint temperature in the mixture is set at 170° C. and the pressure is reduced to a value of 60 mbar. Once the pressure and temperature setpoints are reached, a 70% methanesulfonic acid solution (1.6 eq) is added to the reaction mixture. As soon as the addition is completed, the setpoint temperature is brought to 150° C. and the pressure is maintained at a value of 30 mbar. Five hours after the start of the introduction of the acid, the reaction mixture is cooled to 80° C., then the product is recovered, cooled to room temperature, and constitutes the surfactant composition according to the invention, which contains the following constituents:
TABLE-US-00001 TABLE 1 Composition by weight C18-C22 alkyl betainate mesylate 66.3% Glycine betaine mesylate 3.4% C18-C22 fatty alcohols 14.2% Methanesulfonic acid 7.4% C18-C22 alkyl ethers 8.7%
[0098] Synthesis of Ethanesulfonic Acid Salts
[0099] Glycine betaine (1.0 eq) and a mixture of C18 to C22 fatty alcohols (5.0 eq) are introduced into a reactor. The setpoint temperature in the mixture is set at 170° C. and the pressure is reduced to a value of 60 mbar. Once the pressure and temperature setpoints are reached, a 70% ethanesulfonic acid solution (1.05 eq) is added to the reaction mixture. As soon as the addition is completed, the setpoint temperature is brought to 150° C. and the pressure is maintained at a value of 30 mbar. Six hours after the start of the introduction of the acid, the reaction mixture is cooled to 80° C., then the product is recovered, cooled to room temperature, and constitutes the surfactant composition according to the invention, which contains the following constituents:
TABLE-US-00002 TABLE 2 Composition by weight C18-C22 alkyl betainate esylate 27.7% Glycine betaine esylate 0.4% C18-C22 fatty alcohols 66.7% Ethanesulfonic acid 0.6% C18-C22 alkyl ethers 4.5%
Example 2: Synthesis of Surfactant Compositions Based on Glycine Betaine Amide Salts
[0100] Synthesis of Methanesulfonic Acid Salts
[0101] Glycine betaine (1.0 eq), butanol (3.0 eq) and a 70% methanesulfonic acid solution (1.1 eq) are introduced into a reactor on which a condenser is mounted. The mixture is heated to 140° C. at atmospheric pressure. After 3 hours of reaction, a Dean-Stark trap filled with butanol is mounted on the reactor. The mixture is left at atmospheric pressure since the distillation of the water-butanol azeotrope is sufficiently pronounced at the start. After a further 3 hours of reaction, when the distillation rate of the water-butanol azeotrope has decreased, the pressure is reduced to 700 mbar in order to accelerate the removal of the water and to enable the equilibrium to be shifted towards the glycine betaine butyl ester. The degree of conversion is monitored by .sup.1H NMR analyses.
[0102] The NMR method consists in acquiring a .sup.1H spectrum of the sample dissolved in a CDCl.sub.3/CD.sub.3OD mixture (1/1, v/v), taking the methanol signal at 3.31 ppm as reference. The characteristic signals of the various compounds are then integrated: MsOGBOBu (4.35 ppm, s, 2H), MsOGB (4.28 ppm, s, 2H), butanol (3.53 ppm, t, 2H), methanesulfonate (2.74 ppm, s, 3H), dibutyl ether (3.40 ppm, t, 4H), where XOGBOBu denotes the glycine betaine ester sulfonate salt formed and XOGB denotes the glycine betaine sulfonate formed. The characteristic signal of the methanesulfonate takes into account both the methanesulfonic acid present in the medium, and also the methanesulfonate which is the counterion of glycine betaine and of butyl betainate mesylate (MsOGBOBu).
[0103] The degree of conversion of the reaction is obtained by means of the integration values via the following calculation:
[0104] where:
[0105] is the degree of conversion
[0106] I.sub.i is the integration value of the characteristic signal of the compound i.
[0107] Once the degree of conversion of the esterification reaction reaches 96%, the reaction mixture is allowed to cool to 60° C. During this cooling phase, the Dean-Stark assembly is replaced with distillation apparatus and the reactor is placed under reduced pressure so as to remove a portion of the butanol and the remaining traces of water in the reaction mixture. Once the mixture is at 60° C., the mixture of C16-C22 fatty amines (1.1 eq) which have been melted beforehand is added. The reaction mixture is then heated to 150° C. under reduced pressure. The pressure is gradually reduced to 10 mbar. After total distillation of the butanol (about 4 hours), the reaction mixture is recovered and constitutes the surfactant composition according to the invention, containing the following constituents:
TABLE-US-00003 TABLE 3 Composition by weight Betainylamino(C16-C22)alkane 73.1% mesylate (C16-C22)Alkylammonium mesylate 17.7% Butyl mesylate betainate 8.0% Glycine betaine 1.2% Butanol 0.0%
[0108] Synthesis of Ethanesulfonic Acid Salts
[0109] Glycine betaine (1.0 eq) and hexanol (3.0 eq) are introduced into a reactor on which a Dean-Stark trap filled with hexanol is mounted. Fixed to the cover of the reactor is an isobaric dropping funnel containing a 70% ethanesulfonic acid solution (1.1 eq). The mixture is stirred and heated to 150° C. under pressure reduced to 600 mbar. Once the reaction conditions are reached, the 70% ethanesulfonic acid solution is gradually introduced into the reaction mixture. Once the addition is completed, the pressure is steadily reduced until it reaches 400 mbar in order to accelerate the removal of the water and to enable the equilibrium to be shifted towards the glycine betaine ester. The degree of conversion is monitored by .sup.1H NMR analyses.
[0110] The NMR method consists in acquiring a .sup.1H spectrum of the sample dissolved in a CDCl.sub.3/CD.sub.3OD mixture (1/1, v/v), taking the methanol signal at 3.31 ppm as reference. The characteristic signals of the various compounds are then integrated: EsOGBOC6 (4.35 ppm, s, 2H), EsOGB (4.28 ppm, s, 2H), hexanol (3.53 ppm, t, 2H), ethanesulfonate (2.82 ppm, q, 3H), dihexyl ether (3.40 ppm, t, 4H), where XOGBOC6 denotes the glycine betaine ester sulfonate salt formed and XOGB denotes the glycine betaine sulfonate formed. The characteristic signal of the ethanesulfonate takes into account both the ethanesulfonic acid present in the medium, and also the ethanesulfonate which is the counterion of glycine betaine and of hexyl betainate esylate (EsOGBOC6).
[0111] The degree of conversion of the reaction is obtained by means of the integration values via the following calculation:
[0112] where:
[0113] is the degree of conversion
[0114] I.sub.i is the integration value of the characteristic signal of the compound i.
[0115] Once the degree of conversion of the esterification reaction reaches 96%, the reaction mixture is allowed to cool to 80° C. During this cooling phase, the Dean-Stark assembly is replaced with distillation apparatus and the reactor is placed under reduced pressure so as to remove a portion of the hexanol and the remaining traces of water in the reaction mixture. Once the mixture is at 80° C., a mixture of C16-C22 fatty amines (1.1 eq) which have been melted beforehand is added. The reaction mixture is then heated to 150° C. under reduced pressure. The pressure is gradually reduced to 5 mbar. After total distillation of the hexanol (about 4 hours), the reaction mixture is recovered and constitutes the surfactant composition according to the invention, which contains the following constituents:
TABLE-US-00004 TABLE 4 Composition by weight Betainylamino(C16-C22)alkane esylate 71.4% (C16-C22) Alkylammonium esylate 18.9% Hexyl esylate betainate 8.8% Glycine betaine 1.0% Hexanol 0.0% Dihexyl ether 0.0%
Example 3: Disentangling Test (Sensory Test)
[0116] A comparative test was carried out for disentangling a lock of hair using a fatty alcohol-in-water emulsion containing, as conditioning agent, either a mixture of C18 to C22 glycine betaine ester salts or a mixture of C16 to C22 glycine betaine amide salts according to the invention, or a conditioning agent, namely behentrimonium chloride (Varisoft® BT 85 from EVONIK).
[0117] The glycine betaine ester and amide salts corresponded respectively to the compositions presented in table 1 of example 1 and in table 3 of example 2.
[0118] These emulsions had the following composition:
TABLE-US-00005 Cetyl alcohol 6.00%-10.00%* Conditioning agent (as active material) 3.00% Preservative 0.60% Buffer solution qs pH 4.0-5.0 Demineralized water QS for 100.00% *So as to achieve a viscosity of from 7000 to 22,000 mPa .Math. s (LV4, 20 rpm, 20° C.)
[0119] All these emulsions had the appearance of an opaque viscous cream.
[0120] Tap water (hardness 30° F., temperature: 37° C.) was furthermore used as control.
[0121] To carry out this test, 2 locks of hair were dampened beforehand then wrung out and finally rubbed 15 times in the palm of the hand to entangle the hair. 1 g of each product was then applied to one of the two damp locks which was then massaged 8 times over its entire length to distribute the product properly. After a leave-on time of 3 minutes, the locks were rinsed with tap water then wrung out by hand. After having laid them on a flat surface, the number of comb strokes necessary to obtain a lock which could be combed without constraint was measured. This procedure was repeated three times per product, on 3 different locks. Only one test was carried out with tap water (30° F.).
[0122] The results of these tests are illustrated in
[0123] Sensory analysis of the softness of the locks thus obtained was then carried out by a trained panel, in comparison with a lock treated in the same way as above, but with a commercial disentangling product (Elsève® Total Repair Rapid Restore) containing the same content of cationic conditioning agent (behentrimonium chloride) and having the same pH and substantially the same viscosity as the emulsions above.
[0124] The results of this evaluation are presented in
[0125] An additional test was carried out under the same conditions, using the surfactant composition presented in table 2 of example 1. All of the results are assembled in the table below:
TABLE-US-00006 TABLE 5 Mean number of comb Product tested passes Mean softness GBE Table 1 - Ex 1 5.0 0.7 GBE Table 2 - Ex 1 5.7 2.0 GBA Table 3 - Ex 2 3.0 0.3 Control product 5.0 0.3
[0126] It is observed that the performance of this surfactant composition is much better than that of a surfactant composition that is similar but that is prepared in the presence of a smaller amount of fatty alcohol and a greater amount of acid.
Example 4: Disentangling Test (Mechanical Test)
[0127] Materials and Method
[0128] Use is made of a Diastron® Fibra One machine equipped with a comb in order to measure the work (in Joules) needed to travel through a lock of hair.
[0129] To do this, five calibrated flat locks (3.5 g; 28 cm) of bleached Caucasian hair are firstly washed using 1 ml of sodium lauryl ether sulfate solution (28% active material). The locks are rubbed 20 times between the hands, then rinsed for 1 min 30 sec in water. This washing is then repeated twice, and then the excess water is removed by wringing out the lock 3 times between 2 fingers. The machine is regulated in the following:
[0130] Starting position: 75 mm
[0131] Combing length: 200 mm
[0132] Speed: 2000 mm/min
[0133] Three measurements are carried out for each lock, namely one measurement after each rinsing step, then the mean of the three measurements is calculated.
[0134] The same conditioner treatment (0.5 ml) is then applied on one side of each of the five locks, then the product is spread 10 times with two fingers before being applied (0.5 ml) to the other side of the lock and then spread 10 times with two fingers. The locks are then each rinsed for 16 seconds with tap water (changing side every 8 sec). The excess water is removed by wringing out 3 times between 2 fingers with the same force. The locks are then again tested on the Diastron® as described above. Next, they are subjected to two successive rinsings (passing under tap water for 10 seconds then removal of the excess water by wringing out 3 times between 2 fingers) and are again passed to the Diastron® after each rinsing. The mean of the three measurements obtained is calculated.
[0135] For each lock, the percentage decrease in force needed for the disentangling of the lock is then determined using the following formula: D=(W.sub.T−W.sub.O)/100, where W.sub.T is the work measured after treatment and W.sub.O is the work measured before treatment. The mean DM of the decrease percentages obtained for the five locks is then calculated.
[0136] The conditioner products tested were the following:
[0137] 1—Surfactant composition according to example 2, containing approximately 1% by weight of glycine betaine ester and 3% by weight of C18-22 alcohols,
[0138] 2—Comparative surfactant composition, containing 1% by weight of nonionic surfactant (sorbitan stearate) and 3% by weight of C18-22 alcohols,
[0139] 3—Comparative surfactant composition, containing 1% by weight of behentrimonium chloride as cationic surfactant and 3% by weight of C18-22 alcohols,
[0140] 4—Comparative surfactant composition, containing 1% by weight of cetrimonium chloride as cationic surfactant and 3% by weight of C18-22 alcohols,
[0141] where “C18-22 alcohols” denotes a mixture of fatty alcohols containing from 18 to 22 carbon atoms (Stenol® 1822A from BASF).
[0142] Results
[0143] The results of the tests described above are assembled in table 6 below.
TABLE-US-00007 TABLE 6 Standard Conditioner product DM (%) deviation 1 91.1 0.4 2 23.5 12.7 3 91.4 2.4 4 83.6 3.2
[0144] As it emerges from this table, the product according to the invention (product 1) gives the treated locks an ease of disentangling, which is expressed by the reduction in the work measured for combing the locks. This reduction is of the same order as that obtained with a non-biodegradable cationic surfactant which is customarily used in disentangling products (product 3) and higher than that obtained with a commercial cationic surfactant having a lower biodegradability than the product according to the invention (product 4). The performance of the product according to the invention is moreover much better than that obtained with a nonionic surfactant (product 2).
Example 5: Formulations
[0145] Several types of products can be prepared using surfactant compositions according to the invention, based respectively on palmityl (GBE C16:0 or GBA C16:0), stearyl (GBE C18:0 or GBA C18:0), arachidyl (GBE C20:0 or GBA C20:0), or behenyl (GBE C22:0 or GBA C22:0) ester or amide salts or mixtures thereof, and more particularly esters according to the second variant of the invention, containing at least 55% by weight of fatty alcohol.
[0146] Examples of such products are indicated below, the ingredients in capitals being identified by their INCI names.
[0147] Conditioner:
TABLE-US-00008 Ingredients % Material GBE C16:0/C18:0 12% Lactic acid/sodium lactate qs for pH 4.0 buffer solution Fragrance 0.25% Colorant 0.02% Preservative 0.01% Demineralized water QS for 100%
[0148] Hair Mask:
TABLE-US-00009 Ingredients % Material GBEC18:0/C22:0 12% Olive oil 5.00% Gluconic acid/sodium qs pH 4.0 gluconate buffer solution Panthenol 0.15% Fragrance 0.05% Colorant 0.02% Preservative 0.01% Demineralized water qs for 100%
[0149] 2 in 1 Solid Shampoo:
TABLE-US-00010 Ingredients % Material SODIUM COCOYL 35% ISETHIONATE STEARIC ACID (AND) 15% PALMITIC ACID SODIUM OLIVOYL 10% GLUTAMATE GBAC16:0/C22:0 15% GLYCERIN 8% CORYLUS AVELLANA 5% SEED OIL Cornstarch 4% SUCROSE STEARATE GLYCERYL STEARATE 4%
[0150] 2 in 1 Liquid Shampoo:
TABLE-US-00011 Ingredients % Material SODIUM LAURYL SULFATE 14% COCAMIDOPROPYL 7% BETAINE GBEC18:0/C22:0 17% GLYCERIN 4% POLYSORBATE 80 2% SUCROSE PALMITATE 2.5% GLYCERYL BEHENATE 1.5 CAESALPINIA SPINOSA 1% GUM PHENOXYETHANOL (AND) 1% CAPRYLYL GLYCOL Colorant 0.30% Demineralized water qs for 100%
[0151] Hair Smoothing Product:
TABLE-US-00012 Ingredients % Material GBEC18:0/C22:0 10% Propylene Glycol 5% AMODIMETHICONE 2% Thioglycolic acid qs for pH 1.5-2 PANTHENOL 0.50% Fragrance 0.25% Demineralized water qs for 100%
[0152] Post-Dyeing Hair Treatment:
TABLE-US-00013 Ingredients % Material Propylene Glycol 10% GBAC16:0/C22:0 8% GBEC16:0 6% AMODIMETHICONE 2% ISOPROPYL ALCOHOL 2% PANTHENOL 0.50% Fragrance 0.25% Colorant 0.02% Preservative 0.01% Demineralized water qs for 100%
[0153] Solid Conditioner:
TABLE-US-00014 Ingredients INCI % Material GBEC 18:0/C22:0 ARACHIDYL/BEHENYL 40 BETAINATE ESYLATE (AND) ARACHIDYL/BEHENYL ALCOHOL 1-Hexadecanol 98% HEXADECANOL 20 Shea butter BUTYROSPERMUM PARKII 7 BUTTER Cocoa butter THEOBROMA CACAO SEED 3 BUTTER Argan oil ARGANIA SPINOSA KERNEL 3 OIL Refined hazelnut oil CORYLUS AVELLANA SEED 3 OIL Montanov 82 ARACHIDYL ALCOHOL (AND) 9.67 BEHENYL ALCOHOL (AND) ARACHIDYL GLUCOSIDE L(+)-Sodium lactate SODIUM LACTATE (AND) 3.33 60% AQUA Wheat starch TRITICUM VULGARE STARCH 8
[0154] Beard Balm:
TABLE-US-00015 Ingredients % Material Shea butter 50 Castor oil 15 Sesame seed oil 15 Coconut oil 10 GBEC18:0/C22:0 9 Tocopherol 1