Non-petrochemically derived cationic emulsifiers that are neutralized amino acid esters and related compositions and methods
RE048770 · 2021-10-12
Assignee
Inventors
Cpc classification
A61K8/44
HUMAN NECESSITIES
International classification
A61K8/44
HUMAN NECESSITIES
Abstract
The invention includes a method of increasing the substantivity of a personal care composition to hair, skin or nails by preparing a composition of an aqueous phase, a non-aqueous phase and a neutralized amino acid ester that is a reaction product of a neutral amino acid having a non-polar side chain with a long chain fatty alcohol and is represented by formula (I): ##STR00001##
wherein R.sup.1 is an alkyl group; R.sup.2 is a linear or branched carbon chain; and the amine group of the amino acid is neutralized with an acid. The composition is substantially free of petrochemicals and/or derivatives of petrochemical materials. The aqueous phase and the non-aqueous phase are emulsified by the neutralized amino acid ester. Other methods and an emulsifiers that is the neutralized amino acid ester are included. Because the neutralized amino acid ester and the compositions do not contain petrochemical-derived ingredient, the products are natural.
Claims
1. A method of increasing the substantivity of a personal care composition to hair, skin or nails comprising: preparing a composition that comprises an aqueous phase, a non-aqueous phase and a neutralized amino acid ester that is a reaction product of a neutral amino acid having a non-polar side chain with a long chain fatty alcohol and is represented by formula (I): ##STR00007## wherein R.sup.1 is a linear or branched alkyl group; R.sup.2 is a linear or branched carbon chain; and the amine group of the amino acid is neutralized with an acid, and wherein the composition is substantially free of petrochemicals and/or derivatives of petrochemical materials, and the aqueous phase and the non-aqueous phase are emulsified by the neutralized amino acid ester; and applying the personal care composition to a surface of hair, skin or nails.
2. The method of claim 1, wherein R.sup.1 of formula (I) is chosen from a branched alkyl and a linear alkyl group.
3. The method of claim 1, wherein R.sup.1 of formula (I) .[.is.]. has 1 to 10 carbon atoms.
4. The method of claim 1, wherein the carbon chain of R.sup.2 in formula (I) comprises at least one unsaturated carbon atom.
5. The method of claim 1, wherein R.sup.2 of formula (I) .[.is.]. has 10 to 50 carbon atoms.
6. The method of claim 1, wherein the neutral amino acid is chosen from L-alanine, L-valine, L-leucine, and L-isoleucine.
7. The method of claim 1, wherein the neutral amino acid is L-isoleucine.
8. The method of claim 1, wherein the neutral amino acid is obtained from vegetable matter.
9. The method of claim 1, wherein the long chain fatty alcohol is chosen from the coconut fatty alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, lignoceryl alcohol, isostearyl alcohol, and/or mixtures thereof.
10. The method of claim 1, wherein the amine group of the amino acid is neutralized by an ethanesulfonic acid that is derived from an ethanol that is derived from fermentation of vegetable matter.
11. The method of claim 1, wherein the amine group of the amino acid is neutralized by an acid chosen from hydrochloric acid, phosphoric acid, sulfuric acid, boric acid, and nitric acid.
12. The method of claim 1, wherein the personal care composition further comprise at least one of a surfactant, a colorant, a pearlizing agent, an acrylate polymer, an antioxidant, an opacifying agent, mica, an oil, a lipid, a protein, a pH modifier, a vitamin, a fatty acid, a fatty alcohol, a humectant, and a conditioning agent.
13. The method of claim 1, wherein the composition is chosen from a hair detergent, shampoo, rinse, hair cream conditioner, conditioning shampoo, hair lotions, hair treatment, hair cream, hair spray, hair liquid, hair wax, hair-styling preparation, permanent wave liquids, hair colorant, acidic hair colorant, hair manicure, glaze, skin lotion, milky lotion, face wash, makeup remover, cleansing lotion, emollient lotion, nourishing cream, emollient cream, massage cream, cleansing cream, body shampoo, hand soap, bar soap, shaving creams, sunscreen, sunburn treatment, deodorants, makeup removing gel, moisture gel, moisture essence, UV exposure-preventing essence, shaving foam, face powder, foundation, lipstick, blush, eyeliner, wrinkle and anti-aging cream, eye shadow, eyebrow pencils, mascara, mouthwash, toothpaste, an oral care composition, a skin cleansing composition, a textile cleansing compositions, a dish cleaning composition, a hair or fur cleansing composition, a deodorant or antiperspirant, a cosmetic, a hair styling composition, a skin moisturizer, a skin conditioner, a hair conditioner and a nail conditioner.
.Iadd.14. A method of increasing the substantivity of a personal care composition to hair, skin or nails comprising: preparing a composition that comprises an aqueous phase, a non-aqueous phase and a neutralized amino acid ester that is a reaction product of one or more of L-alanine, L-valine, L-leucine, and L-isoleucine with a long chain fatty alcohol and is represented by formula (1): ##STR00008## wherein R.sup.1 is a linear or branched alkyl group; R.sup.2 is a linear or branched carbon chain; and the amine group of the amino acid is neutralized with an acid, and wherein the composition is substantially free of petrochemicals and/or derivatives of petrochemical materials, and the aqueous phase and the non-aqueous phase are emulsified by the neutralized amino acid ester; and applying the personal care composition to a surface of hair, skin or nails..Iaddend.
.Iadd.15. The method of claim 14, wherein the neutral amino acid is obtained from vegetable matter..Iaddend.
.Iadd.16. The method of claim 14, wherein the long chain fatty alcohol is chosen from Brassica alcohol, coconut fatty alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, lignoceryl alcohol, isostearyl alcohol, and/or mixtures thereof..Iaddend.
.Iadd.17. The method of claim 14, wherein the amine group of the amino acid is neutralized by an ethanesulfonic acid that is derived from an ethanol that is derived from fermentation of vegetable matter..Iaddend.
.Iadd.18. The method of claim 14, wherein the amine group of the amino acid is neutralized by an acid chosen from hydrochloric acid, phosphoric acid, sulfuric acid, boric acid, and nitric..Iaddend.
.Iadd.19. A method of preparing a personal care composition comprising preparing a composition that comprises an aqueous phase, a non-aqueous phase and a neutralized amino acid ester that is a reaction product of one or more of L-alanine, L-valine, L-leucine, and L-isoleucine with a long chain fatty alcohol and is represented by formula (I): ##STR00009## wherein R.sup.1 is a linear or branched alkyl group; R.sup.2 is a linear or branched carbon chain, wherein an amine group of the amino acid is neutralized with an acid, wherein the composition is substantially free of petrochemicals and/or derivatives of petrochemical materials, emulsifying the aqueous phase and the non-aqueous phase with the neutralized amino acid ester, and applying the personal care composition to a surface of hair, skin or nails..Iaddend.
.Iadd.20. The method of claim 19, wherein the neutral amino acid is obtained from vegetable matter..Iaddend.
.Iadd.21. The method of claim 19, wherein the long chain fatty alcohol is chosen from Brassica alcohol, coconut fatty alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, lignoceryl alcohol, isostearyl alcohol, and/or mixtures thereof..Iaddend.
.Iadd.22. The method of claim 19, wherein the amine group of the amino acid is neutralized by an ethanesulfonic acid that is derived from an ethanol that is derived from fermentation of vegetable matter..Iaddend.
.Iadd.23. The method of claim 19, wherein the amine group of the amino acid is neutralized by an acid chosen from hydrochloric acid, phosphoric acid, sulfuric acid, boric acid, and nitric..Iaddend.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The foregoing summary, as well as the following detailed description of preferred embodiments of the invention, will be better understood when read in conjunction with the appended drawings. It should be understood that the invention is not limited to the precise arrangements and instrumentalities shown. In the drawings:
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DETAILED DESCRIPTION OF THE INVENTION
(14) This invention includes neutralized amino acid ester cationic emulsifiers and compositions that are natural, as they are not derived from petrochemical materials, and also may be produced from non-animal derived and non-GMO reactants, and prepared by processes that utilize Green Chemistry principles. Because of the ester's cationic structure, it is well suited for personal care applications, particularly for compositions used in the conditioning of hair and skin. At the time of the invention, no other personal care compositions containing a cationic emulsifier that was not petrochemically-derived were known. Accordingly, up to the time of discovery of the invention, no natural personal care compositions exhibited the performance characteristics provided by a cationic emulsifier and expected by the consumer, particularly with respect to substantivity, skin feel, and shelf stability.
(15) The invention encompasses personal care compositions that contain this emulsifying ester, particularly hair and skin conditioning compositions. Such natural compositions may be substantially free of petrochemicals, petrochemical derivatives, materials derived from genetically modified organisms (such as GMO plant materials), and/or any animal materials or derivatives.
(16) In addition, the neutralized amino acid ester has been found to be non-toxic to animals (including humans) and plants, unlike some cationic emulsifiers that may harm wildlife and/or plants when discharged into the environment.
(17) The invention includes methods of increasing the substantivity (absorbance to a negatively charged substrate, such as hair, skin and nails) of a personal care composition that is substantially free of petrochemicals, petrochemical derivatives, and/or materials derived from genetically modified organisms (such as GMO plant materials), and/or any animal materials or derivatives; therefore the composition itself is natural.
(18) The neutralized amino acid ester of the invention is derived from the esterification of (i) an amino acid having a non-polar side chain wherein the amine group of the amino acid has been neutralized with an acid; with (ii) a long chain fatty alcohol. In particular, suitable amino acid esters are derived from the esterification of a neutral amino acid with a non-polar side chain with a long chain fatty alcohol.
(19) The amino acid ester of the invention may be represented by the structure of formula (I):
(20) ##STR00006##
(21) In (I), R.sup.1 represents an alkyl group, which may be branched or linear. It may have one to ten carbon atoms or two to six carbon atoms.
(22) R.sup.2 represents a carbon chain that may be linear or branched. It may contain ten to fifty carbon atoms or twenty-four to thirty-two carbon atoms. The chain of R.sup.2 may contain at least one unsaturated carbon atom. In an embodiment, R.sup.2 is an alkyl group having eight to twenty four carbon atoms.
(23) Amino acids for the formation of the ester include any that are neutral. In an embodiment, one may select L-alanine, L-valine, L-leucine and L-isoleucine. Particularly preferred, in some embodiments of the invention, is L-isoleucine.
(24) It is preferred that the selected neutral amino acid is not derived from animal sources or GMO sources. In an embodiment, it may be preferred that the amino acid(s) are synthetic and/or derived from plants, algae, or other non-animal organisms. They may be obtained, for example, from vegetable matter by a fermentation process.
(25) To obtain the ester of the invention, the amine group of the amino acid is neutralized with an acid, and is reacted with a long chain fatty alcohol. Suitable fatty alcohols may be linear and/or branched and may additionally be saturated and/or unsaturated. It may be preferred that the fatty alcohol contains about ten to about fifty or about twenty-four to about thirty-two carbon atoms. In an embodiment, linear and/or branched fatty alcohols containing from about twelve to about twenty-two carbon atoms may be preferred.
(26) Examples of suitable fatty alcohols include lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol, isostearyl alcohol, arachidyl alcohol, behenyl alcohol and mixtures or combinations thereof. It is advisable that the fatty alcohols are derived from non-petrochemical sources.
(27) The amine group of the amino acid ester may be fully or partially neutralized by an acid, to facilitate its cationic behavior. Any acid may be used, including organic and inorganic acids. Suitable acids include, without limitation, mineral acids, amino acids, hydrochloric acid, phosphoric acid, sulfuric acid, boric acid, and nitric acid. Suitable organic acids may be citric acid, ethanesulfonic acid, acetic acid, formic acid, and oxalic acid. Suitable amino acids may include glutamic acid and aspartic acid. In an embodiment, one may prefer ethanesulfonic acid that is derived from non-GMO ethanol.
(28) An exemplary preferred neutralized amino acid ester may be Brassicyl L-isoleucine esylate (BLIE) or leucine isostearyl ester esylate (LIEE). Brassicyl L-isoleucine esylate (BLIE) may be derived from the esterification of Brassica alcohol with L-isoleucine esylate. L-isoleucine esylate may be prepared by reacting the amine group on isoleucine with ethanesulfonic acid. Brassica alcohol is a fatty alcohol that is derived from the splitting of high erucic acid rapeseed oil obtained from the Brassica genus of plants followed by hydrogenation. Brassica alcohol consists predominantly of stearyl (C.sub.18), arachidyl (C.sub.20) and behenyl (C.sub.22) alcohols with minor quantities of lower and higher alkyl chain length alcohols.
(29) The neutralized amino acid ester of the invention may be synthesized by methods commonly known in the art.
(30) The invention also includes personal care compositions that contain the neutralized amino acid ester; such compositions may contain a non-aqueous phase and an aqueous phase that are emulsified by the ester. The compositions are preferably substantially free of petrochemical or petrochemical derivatives. To form such compositions, an exemplary process may be mixing or otherwise incorporating the neutralized amino acid ester with other ingredients of the composition to formulate the finished product.
(31) In an exemplary hair conditioner base formulation, the neutralized amino acid ester is mixed with fatty alcohol and an emollient and is warmed to about 75° C. to about 85° C. This mixture is then added to hot water and allowed to cool slowly with agitation. In such compositions, the neutralized amino acid ester of the invention serves multiple roles—it emulsifies the aqueous and non-aqueous phases of the invention, it increases the substantively of the personal care composition to skin, hair or nails, and it conditions/lubricates the surfaces of the hair, skin or nail substrates to which it is applied.
(32) The composition of the invention may be formulated to be any type of personal care composition, cosmetic, or pharmaceutical delivery formulation (for example, to deliver therapeutic agents to the skin or gums).
(33) Other suitable compositions may include a hair detergent, hair cream conditioner, shampoo, rinse, conditioning shampoo, hair lotions, hair treatment, hair cream, hair spray, hair liquid, hair wax, hair-styling preparation, permanent wave liquids, hair colorant, acidic hair colorant, hair manicure, glaze, skin lotion, milky lotion, face wash, makeup remover, cleansing lotion, emollient lotion, nourishing cream, emollient cream, massage cream, cleansing cream, body shampoo, hand soap, bar soap, shaving creams, sunscreen, sunburn treatment, deodorants, makeup removing gel, moisture gel, moisture essence, UV exposure-preventing essence, shaving foam, face powder, foundation, lipstick, blush, eyeliner, wrinkle and anti-aging cream, eye shadow, eyebrow pencils, mascara, mouthwash, toothpaste, an oral care composition, a skin cleansing composition, a textile cleansing compositions, a dish cleaning composition, a hair or fur cleansing composition, a deodorant or antiperspirant, a cosmetic, a hair styling composition, a skin moisturizer, a skin conditioner, a hair conditioner and a nail conditioner.
(34) The compositions may include various additives, as are known in the personal care composition art. Suitable additives include various anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, waxes, other oils and fats and derivatives thereof, fatty acid esters of varying chain lengths, synthetic oils and fats, polymers, alcohols, polyhydric alcohols, extracts useful for providing fragrance, amino acids, nucleic acids, vitamins, hydrolyzed proteins and derivatives thereof, glycerine and derivates thereof, enzymes, anti-inflammatory and other medicaments, microbiocides, antifungals, antiseptics, antioxidants, UV absorbers, dyes and pigments, sunscreen active agents, chelating agents, sweat retardants, oxidizers, pH balancing agents, glyceryl monoesters, moisturizers, peptides and derivatives thereof, anti-aging actives, hair growth promoters, anti-cellulite actives and the like acceptable for use in formulations for human use. Others include EDTA, glutamic acid, glycerine, panthenol, stearyl alcohol, cetyl alcohol, cyclomethicone, dimethicone, pH adjustment additives, and preferably a water base.
(35) Methods that are included within the scope of the invention include methods of conditioning the hair and/or skin by applying the personal care compositions described above. It may be desirable that the composition is in the form of an oil-in-water emulsion, but can also be in a form of, for example, creams, lotions, solutions, gels, pastes, mousses, sprays and combinations thereof. The proportion of the neutralized amino acid ester used in the hair condition composition is preferably from about 0.1 to about 10.0 weight percent, and more preferably from about 0.25 to about 5.0 weight percent.
(36) The compositions may contain a single neutralized amino acid ester or more than one. In an embodiment, the preferred neutralized amino acid ester may be leucine isostearyl ester esylate (LIEE) or Brassicyl L-isoleucinate esylate (BLIE). In some embodiments, it may be preferred to include a mixture of LIEE and BLIE. LIEE and BLIE may be included in any proportion, including, for example, in parts by weight, 1:1, 1:2, 1:3, 1:4, 1:5; ‘1:6; 1:7; 1:8; 1:9; and 1:10.
(37) Also included are methods of forming an emulsion that includes incorporating the amino acid ester of the invention into a mixture containing at least an aqueous phase and non-aqueous phase.
EXAMPLES
Example 1
Synthesis of Brassicyl L-Isoleucinate Esylate (BLIE)
(38) To a one liter round bottom flask affixed with vapor column, total condenser, nitrogen sparge and agitator, 508.5 grams (1.629 moles) of Brassicyl alcohol and 106.9 grams (0.8147 moles) of L-isoleucine were charged. The mixture was warmed to 90° C. with stirring, and 134.5 grams (0.8551 moles) of a 70% solution of ethanesulfonic acid was added dropwise over about a twenty-minute period. The mixture was then heated to 140° C. and was held for about 16 hours. The mixture was then cooled to 90° C. and the excess of ethanesulfonic acid was neutralized with 1.8 grams of sodium carbonate dissolved in 5.6 grams of water. The mixture was then dried under hard vacuum for about one hour. The mixture was then cooled to about 70° C. and flaked off, yielding a pale yellow solid product.
(39) Acid value was determined on the product using ASTM (American Society of Testing and Materials, West Conshohocken, Pa.) official method number D-972, the contents of which are incorporated herein by reference, and was found to be 2.67 mg KOH/g (95.9% conversion.) The amine value was determined through the use of multi-endpoint titration with base using a modern automatic titrator. In the method, a sample is weighed and dissolved in un-neutralized denatured ethanol. The mixture is then titrated with dilute sodium hydroxide to the appearance of two endpoints, the first being related to the consumption of carboxylate, and the second being related to the titration of the amine salt. The value found was 64.3 mg KOH/g. The infrared spectrum was determined using a Perkin-Elmer (Waltham, Mass.) Spectrum 100 FT-IR spectrophotometer fitted with a Pike (Madison, Wis.) MIRacle ATR (Attenuated Total Reflectance) accessory with ZnSe crystal. The spectrum is displayed in
Example 2
(40) Additional analogs of BLIE were prepared and analyzed using the general methods described in Example 1, and the properties are summarized in Table 1.
(41) TABLE-US-00001 TABLE 1 Amine Value Acid Value (mg Melting Point Amino Acid Fatty Alcohol (mg KOH/g) KOH/g) (° C.) L-Alanine Coconut 0.0 106.6 78 L-Alanine Brassicyl (Hyd.) 3.4 71.9 99 L-Alanine Stearyl 5.5 114.6 114 L-Alanine Isostearyl 1.7 76.9 Paste at R.T. L-Valine Coconut 2.5 109.0 Paste at R.T. L-Valine Brassicyl (Hyd.) 0.4 67.2 60 L-Valine Stearyl 0.0 75.6 62 L-Valine Isostearyl 1.2 73.7 Liquid at R.T. L-Leucine Coconut 2.0 97.7 Liquid at R.T. Leucine Brassicyl (Hyd.) 3.5 65.4 62 L-Leucine Stearyl 2.1 73.0 59 L-Leucine Isostearyl 1.8 72.1 Liquid at R.T. L-Isoeucine Coconut 5.3 103.1 Liquid at R.T. L-Isoeucine Stearyl 1.1 72.8 53
Example 3
(42) To demonstrate the emulsification behavior achieved by the present invention, an exemplary hair conditioning base formulation was prepared. The composition of the formulation is shown in Table 2.
(43) TABLE-US-00002 TABLE 2 Ingredients % w/w Part A Deionized water 90.40 L-Arginine 0.20 Part B Stearyl alcohol 5.90 Brassicyl L-Isoleucinate Esylate 3.50 Total 100.00
(44) The formulation was prepared using the following procedure. Part A, deionized water and L-arginine were combined in a vessel with propeller agitation and heated to about 70 to about 75° C. and agitated until a clear solution was obtained. In a separate vessel, stearyl alcohol, cetyl alcohol, and Brassicyl L-isoleucinate esylate (BLIE) were combined and heated to about 70° C. to about 75° C., then agitated until a uniform mixture was obtained. The contents of the second vessel were added to the first, and agitated at a temperature of about 70 to about 75° C. until a milky dispersion was obtained (about 10 minutes.) The mixture was then allowed to cool with sweep agitation to about 30° C. to about 35° C. Agitation was then stopped, and the completed conditioner formulation was poured off to containers. What resulted was a white, creamy emulsion that showed no signs of instability for 1 month at 45° C.
Example 4
(45) To illustrate the ability of the invention to create stable emulsions, a stability study was performed. Forty-four formulations were prepared using the general method described in Example 3.
(46) TABLE-US-00003 TABLE 3 Formula 1 2 3 4 5 6 7 8 Ingredients % w/w % w/w % w/w % w/w % w/w % w/w % w/w % w/w Deionized Water 88.20 86.20 84.20 82.20 88.03 85.99 83.95 81.90 L-Arginine 0.00 0.00 0.00 0.00 0.17 0.21 0.25 0.30 KB Natural 8.00 10.00 12.00 14.00 8.00 10.00 12.00 14.00 Natural Oil 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 Preservative 0.80 0.80 0.80 0.80 0.80 0.80 0.80 0.80 100.00 100 100 100 100.00 100.00 100.00 100.00 Formula 9 10 11 12 13 14 15 16 Ingredients % wt/wt % wt/wt % wt/wt % wt/wt % wt/wt % wt/wt % wt/wt % wt/wt Deionized Water 88.02 88.01 88.01 87.98 85.98 87.96 85.95 85.93 Arginine 0.18 0.19 0.202 0.216 0.22 0.235 0.25 0.27 BLIE 2.79 2.98 3.17 3.39 3.49 3.73 3.97 4.24 Cetyl Alcohol 2.60 2.51 2.41 2.305 3.255 2.135 3.015 2.88 Stearyl Alcohol 2.60 2.51 2.41 2.305 3.255 2.135 3.015 2.88 Natural Oil 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 Preservative 0.80 0.80 0.80 0.80 0.80 0.80 0.80 0.80 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Formula 17 18 19 20 21 22 23 24 Ingredients % wt/wt % wt/wt % wt/wt % wt/wt % wt/wt % wt/wt % wt/wt % wt/wt Deionized Water 83.938 83.92 83.902 83.883 81.886 81.864 81.843 81.818 Arginine 0.262 0.28 0.298 0.317 0.314 0.336 0.357 0.382 BLIE 4.19 4.48 4.76 5.09 4.89 5.22 5.56 5.93 Cetyl Alcohol 3.905 3.76 3.62 3.455 4.55 4.39 4.22 4.035 Stearyl Alcohol 3.905 3.76 3.62 3.455 4.55 4.39 4.22 4.035 Natural Oil 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 Preservative 0.80 0.80 0.80 0.80 0.80 0.80 0.80 0.80 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Formula 25 26 27 28 29 30 31 32 Ingredients % wt/wt % wt/wt % wt/wt % wt/wt % wt/wt % wt/wt % wt/wt % wt/wt Deionized Water 88.11 86.09 84.08 82.05 88.09 88.09 88.09 88.07 Arginine 0.085 0.105 0.124 0.147 0.1068 0.114 0.1212 0.1296 BLIE 2.67 3.33 4.00 4.67 2.79 2.98 3.17 3.39 Cetyl Alcohol 2.67 3.33 4.00 4.67 2.605 2.51 2.41 2.305 Stearyl Alcohol 2.67 3.33 4.00 4.67 2.605 2.51 2.41 2.305 Natural Oil 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 Preservative 0.80 0.80 0.80 0.80 0.80 0.80 0.80 0.80 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Formula 33 34 35 36 37 38 39 40 Ingredients % wt/wt % wt/wt % wt/wt % wt/wt % wt/wt % wt/wt % wt/wt % wt/wt Deionized Water 86.07 88.06 86.05 86.04 84.07 84.06 84.051 84.041 Arginine 0.132 0.141 0.15 0.1602 0.131 0.14 0.149 0.159 BLIE 3.49 3.73 3.97 4.24 4.19 4.48 4.76 5.09 Cetyl Alcohol 3.255 2.135 3.015 2.88 3.905 3.76 3.62 3.455 Stearyl Alcohol 3.255 2.135 3.015 2.88 3.905 3.76 3.62 3.455 Natural Oil 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 Preservative 0.80 0.80 0.80 0.80 0.80 0.80 0.80 0.80 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Formula 41 42 43 44 Ingredients % wt/wt % wt/wt % wt/wt % wt/wt Deionized Water 81.42 82.032 82.022 82.01 Arginine 0.785 0.168 0.178 0.191 BLIE 4.89 5.22 5.56 5.93 Cetyl Alcohol 4.55 4.39 4.22 4.035 Stearyl Alcohol 4.55 4.39 4.22 4.035 Natural Oil 3.00 3.00 3.00 3.00 Preservative 0.80 0.80 0.80 0.80 100.00 100.00 100.00 100.00
(47) The pH and viscosity at 25° C. were performed on each of the formulations, and the results are found in Table 4. The pH was measured using an Orion 420A pH meter with a glass electrode that was calibrated using aqueous buffer solutions. The clean, dry electrode was placed in each sample at 25° C. for approximately 1 minute and the pH was recorded directly from the meter display. The viscosity was determined using a Brookfield RVT dial viscometer with helipath stand and T-bar spindles. The test emulsion was equilibrated at 25° C. before taking each measurement. The spindle was attached to the instrument and lowered into the test formula. The viscometer and helipath stand were turned on and the viscosity measurement was recorded after a period of 60 seconds.
(48) TABLE-US-00004 TABLE 4 Formula 1 2 3 4 5 6 7 8 9 10 11 pH 4.25 4.35 4.4 4.48 5.38 5.66 5.73 5.76 4.92 4.97 5.02 Viscosity 18500 20000 22800 66500 41000 54000 69000 75500 4000 6000 7000 Formula 12 13 14 15 16 17 18 19 20 21 22 pH 4.98 5.15 4.94 5.39 5.33 5.16 5.23 5.22 5.16 5.24 5.33 Viscosity 11500 35500 9000 6000 43500 57000 61000 47000 54000 51000 77000 Formula 23 24 25 26 27 28 29 30 31 32 33 pH 5.55 5.54 5.09 5.26 5.27 5.49 5.05 5.16 4.99 4.98 5.17 Viscosity 69000 80000 35000 59000 73000 83000 23000 16000 25000 27000 46000 Formula 34 35 36 37 38 39 40 41 42 43 44 pH 4.99 5.05 5.07 5.11 5.14 4.87 4.84 5.3 5.17 5.08 5.07 Viscosity 24000 42000 47500 91000 65000 18000 72000 92000 Too thick Too thick 81000
(49) All formulations were transferred to canisters to test for stability. Stability is defined as the ability of the emulsion to retain its initial, creamy uniform texture, and to not separate. The test was performed at room temperature for a period of four weeks. Formulation pH was monitored weekly.
Example 5
(50) To demonstrate the conditioning properties of the inventive cationic emulsifiers, a model hair conditioning formulation was prepared to test for the reduction in flyaway hair. The composition of the inventive formulation (Inventive Formulation A) is shown in Table 5 below:
(51) TABLE-US-00005 TABLE 5 Inventive Formulation A Ingredients % w/w Part A Deionized water 88.060 L-Arginine 0.141 BLIE 3.730 Part B Stearyl alcohol 2.135 Cetyl Alcohol 2.135 Almond Oil 3.000 Part C Preservative 0.800 Total 100.000
(52) The Inventive Formulation A was tested against industry leader commercial products Pantene Pro-V Daily Moisture Renewal and Gamier Fructis Fortifying Cream Conditioner. The cationic emulsifier utilized in Pantene Pro-V Daily Moisture Renewal is stearamidopropyl dimethylamine, while the Gamier Fructis Fortifying Cream Conditioner utilizes behentrimonium chloride.
(53) Ten tresses of hair were washed with Pantene clarifying shampoo and rinsed under deionized water for 1 minute. The tresses were combed, and were immersed in conditioner for 1 minute, then rinsed under deionized water for 1 minute and hung to dry for 2 hours. The tresses were then dried with a hair dryer on low for 5 minutes and hung to dry another 15 minutes. The width at the bottom of the tress was recorded, it was combed 20 times, and the width was recorded again. The data obtained are recorded in Tables 6, 7, and 8.
(54) TABLE-US-00006 TABLE 6 Inventive Pre comb Post-comb Formulation A width (cm) width (cm) Difference % Fly Away 1 5.0 7.3 2.3 31.51 2 4.3 5.4 1.1 20.37 3 5.7 5.8 0.1 1.72 4 4.8 6.2 1.4 22.58 5 5.2 6.8 1.6 23.53 6 5.3 5.9 0.6 10.17 7 5.2 4.4 −0.8 −18.18 8 4.3 4.8 0.5 10.42 9 4.5 6.2 1.7 27.42 10 4.9 5.1 0.2 3.92 Average 4.92 5.79 0.87 13.35
(55) TABLE-US-00007 TABLE 7 Pre comb width Post-comb Pantene (cm) width (cm) Difference % Fly Away 1 4.1 5.5 1.4 25.45 2 4.5 5.1 0.6 11.76 3 3.9 4.2 0.3 7.14 4 2.9 4.5 1.6 35.56 5 4.5 5.3 0.8 15.09 6 3.9 4.2 0.3 7.14 7 4.1 5.3 1.2 22.64 8 4.5 5.5 1.0 18.18 9 4.1 4.1 0.0 0.00 10 3.2 4.3 1.1 25.58 Average 4.0 4.8 0.8 16.86
(56) TABLE-US-00008 TABLE 8 Pre comb width Post-comb width Garnier (cm) (cm) Difference % Fly Away 1 3.0 4.3 1.3 30.23 2 2.9 4.8 1.9 39.58 3 3.7 4.4 0.7 15.91 4 3.1 4.3 1.2 27.91 5 2.1 3.2 1.1 34.38 6 3.0 3.9 0.9 23.08 7 2.9 3.3 0.4 12.12 8 3.2 4.2 1.0 23.81 9 2.2 3.3 1.1 33.33 10 3.0 4.1 1.1 26.83 Average 2.9 4.0 1.1 26.72
(57) The results show that there was less fly-away using Inventive Formulation A when compared with Pantene and Gamier conditioners. Therefore, the Inventive Formulation A is just as effective, if not more effective, than Pantene and Gamier (both of which contain petrochemicals and/or petrochemical-derived materials) at conditioning hair.
Example 6
(58) The Rubine Dye Test was used to evaluate the sub stantivity of Inventive Formulation A versus market standards Pantene and Garnier as in Example 5. Rubine Dye is an anionic dye which will readily react with cationic materials. When light blonde hair or wool is treated with a cationic conditioner and rinsed, the hair or wool turns reddish pink when dipped into a dilute solution of Rubine Dye. This study was performed to evaluate the deposition of Direct Red, an anionic dye solution, onto conditioned hair to measure the degree of cationic charge due to substantivity of the conditioner to the hair.
(59) A stock dye solution was prepared by combining deionized water (99.37%,) Direct Red 80 dye (0.50%) and glacial acetic acid (0.13%) until a uniform solution was obtained. This solution was further diluted by mixing the stock dye solution with deionized water at a ratio of one to four to create the Test Dye Solution. Prebleached hair was glued to plastic strips weighing 0.60+/−0.02 grams each. Ten swatches were prepared for each conditioner to be tested. Each swatch was individually wet under warm running water, then washed with two grams of cationic conditioner for one minute. Each sample was then rinsed under warm running water for two minutes and excess water was removed by blotting with a paper towel. Each hair sample was then immersed in 200 ml if Test Dye Solution for 10 seconds, then rinsed under running water for 5 seconds. Excess water was removed by blotting between two paper towels and then hung to dry. Qualitative and quantitative comparisons of dye uptake and relative substantivity of each cationic conditioner was evaluated using a digital camera and Minolta Chroma Meter.
ΔE=ΔL.sup.2+Δa.sup.2+Δb.sup.2
(60) The results of this study indicate that Formulation A performs comparably to behentrimonium chloride (Garnier) and stearamidopropl dimethylamine (Pantene) based conditioners. The Formulation A conditioner was slightly more substantive than the Pantene, but less than Gamier, and well within commercially acceptable parameters. The results are expressed as ΔE, which accounts for variations in tone and hue versus the unconditioned tresses.
Example 7
(61) Exemplary formulations for hair and skin care compositions are shown below (formulations A to M). None contains petrochemicals and/or petrochemical-derived materials.
(62) A. Daily Conditioner for Normal Hair
(63) TABLE-US-00009 Ingredients % w/w Part A Deionized water 84.05 L-Arginine 0.15 BLIE 4.50 Part B Stearyl alcohol 3.75 Cetyl Alcohol 3.75 Caprylic/Capric Triglycerides 3.00 Part C Preservative 0.80 Total 100.00
B. Intense Moisturizing Hair Conditioner
(64) TABLE-US-00010 Ingredients % w/w Part A Deionized water 74.34 L-Arginine 0.16 BLIE 5.20 Glycerine 5.00 Part B Cetearyl Alcohol 7.50 Helianthus Annuus (Sunflower) Seed Oil 6.50 Hydrolyzed Silk Protein 0.50 Part C Preservative 0.80 Total 100.00
C. Leave-In Hair Conditioning Treatment
(65) TABLE-US-00011 Ingredients % w/w Part A Deionized water 89.11 L-Arginine 0.14 BLIE 3.75 Part B Cetyl Alcohol 2.10 Stearyl Alcohol 2.10 Olea Europaea (Olive) Fruit Oil 2.00 Part C Preservative 0.80 Total 100.00
D. Rich Conditioning Treatment (Hair)
(66) TABLE-US-00012 Ingredients % w/w Part A Deionized water 81.05 L-Arginine 0.15 BLIE 4.50 Part B Cetyl Alcohol 3.75 Stearyl Alcohol 3.75 Olea Europaea (Olive) Fruit Oil 2.00 Part C Preservative 0.80 Total 100.00
E. Baby Lotion (Skin)
(67) TABLE-US-00013 Ingredients % w/w Part A Deionized water 80.25 L-Arginine 00.25 Glycerin 2.00 Part B BLIE 3.00 Brassica Alcohol 3.00 Brassica Glycerides 2.00 Heptyl Undecylenate 4.00 Helianthus Annuus (Sunflower) Seed Oil 4.00 Glyceryl Monocaprylate 1.00 Part C Natural Fragrance 0.30 Total 100.00
F. Rich Body Butter (Skin)
(68) TABLE-US-00014 Ingredients % w/w Part A Deionized water 68.04 L-Arginine 0.16 Glycerine 4.00 Aloe Barbadensis Leaf Juice 1.00 Part B BLIE 5.20 Cetyl Alcohol 3.50 Behenyl Alcohol 3.50 Heptyl Undecylenate 5.00 Olea Europaea (Olive) Fruit Oil 7.00 Butyrospermum Parkii (Shea) Butter 1.50 Part C Preservative 0.80 Natural Fragrance 0.30 Total 100.00
G. Conditioning Cream (Hair)
(69) TABLE-US-00015 Ingredients % w/w Part A Deionized water 85.30 L-Arginine 0.15 Glycerine 0.50 Part B BLIE 3.70 Brassica Alcohol 6.55 Helianthus Annuus (Sunflower) Seed Oil 3.00 Part C Preservative 0.80 Total 100.00
H. Deep Conditioning Treatment (Hair)
(70) TABLE-US-00016 Ingredients % w/w Part A Deionized water 76.55 L-Arginine 0.25 Glycerine 0.50 Part B BLIE 4.00 Brassica Alcohol 7.00 Heptyl Undecylenate 3.00 Caprylic/Capric Triglyceride 1.00 Cetyl Alcohol 5.00 Polyester-11 0.50 Part C Keratin Amino Acids 1.00 Glyceryl Monocaprylate 1.20 Total 100.00
I. Moisturizing Conditioner for Curly Hair
(71) TABLE-US-00017 Ingredients % w/w Part A Deionized water 75.05 L-Arginine 0.25 Sorbitol 2.00 Glyceryl Monocaprylate 1.00 Panthenol 0.50 Glycerine 2.50 Polyester-11 0.50 Part B BLIE 4.00 Cetearyl Alcohol 10.00 Caprylic/Capric Triglyceride 1.00 Olea Europaea (Olive) Oil 2.00 Part C Hydrolyzed Wheat Protein 1.00 Total 100.00
J. Light Daily Conditioner (Hair)
(72) TABLE-US-00018 Ingredients % w/w Part A Deionized water 89.20 L-Arginine 0.20 Glycerine 0.50 Glyceryl Monocaprylate 1.00 Part B BLIE 1.80 Brassica Alcohol 3.20 Heptyl Undecylenate 1.00 Cetyl Alcohol 3.00 Part C Natural Fragrance 0.10 Total 100.00
K. Leave-In Conditioning Spary (Hair)
(73) TABLE-US-00019 Ingredients % w/w Part A Deionized water 91.25 L-Arginine 0.15 Glycerine 0.50 Glyceryl Monocaprylate 1.00 Part B BLIE 1.25 Brassica Alcohol 2.25 Heptyl Undecylenate 1.00 Cetyl Alcohol 1.50 Olea Europaea (Olive) Oil 0.50 Part C Hydrolyzed Silk Protein 0.50 Natural Fragrance 0.10 Total 100.00
L. Deluxe Moisturizier
(74) TABLE-US-00020 Ingredients % w/w Part A Deionized water 56.85 L-Arginine 0.15 Glycerine 5.00 Part B BLIE 4.50 Brassica Alcohol 4.50 Brassica Glycerides 3.00 Caprylic/Capric Triglyceride 25.00 Glyceryl Monocaprylate 1.00 Total 100.00
M. Sprayable Hydrating Lotion (Skin)
(75) TABLE-US-00021 Ingredients % w/w Part A Deionized water 84.30 L-Arginine 0.20 Glycerine 5.00 Glyceryl Monocaprylate 1.00 Part B BLIE 2.05 Brassica Alcohol 2.05 Brassica Glycerides 1.40 Caprylic/Capric Triglyceride 4.00 Total 100.00
Example 8
(76) Two conditioning formulations in accordance with the invention were prepared specifically to evaluate the aesthetic characteristics of the formulations. Each was prepared with out any petrochemical materials. Formulation K included both leucine isostearyl ester esylate (LIEE) and Brassicyl L-isoleucinate esylate (BLIE). Formulation C included BLIE only.
(77) The formulations were prepared simultaneously using the following procedure. With reference to Table 8 below, Part A, deionized water, glycerine and arginine were combined in a vessel with propeller agitation and heated to about 70 to about 75° C. and agitated until a clear solution was obtained. In a separate vessel, Brassica alcohol, cetyl alcohol, heptyl undecylenate, caprylic/capric triglyceride, glyceryl monocaprylate and Brassicyl L-isoleucinate esylate (BLIE) were combined and heated to about 70° C. to about 75° C., then agitated until a uniform mixture was obtained. The contents of the second vessel were added to the first, and agitated at a temperature of about 70 to about 75° C. until a milky dispersion was obtained (about 10 minutes.) The mixture was then allowed to cool with sweep agitation to about 30° C. to about 35° C. Agitation was then stopped, and the completed conditioner formulation was poured off to containers.
(78) TABLE-US-00022 TABLE 8 K C Ingredients % w/w % w/w Part A Deionized water 77.05 78.05 L-Arginine 0.25 0.25 Glycerine 0.50 0.50 Part B BLIE 4.00 4.00 Brassica Alcohol 7.00 7.00 Heptyl Undecylenate 3.00 3.00 Caprylic/Capric Triglyceride 1.00 1.00 Cetyl Alcohol 5.00 5.00 Leucine Isostearyl Ester Esylate 1.00 0 Glyceryl Monocaprylate 1.20 1.20 Total 100.00 100.00
(79) Test formula K was a milky, creamy emulsion while hot and cooled to a smooth uniform emulsion with a glossy finish. Test formula C was thicker and the resulting emulsion was grainy and dull in appearance. Test formula C, without LIEE, was less stable at elevated temperature. Test formula K was stable for 90 days at 25° C. and 45° C.
Example 9
(80) A conditioning cream in accordance with the invention was prepared by incorporating the ingredients of Part A (Table 9, below) and Part B (Table 9, below), and subsequently mixing Parts A and B together.
(81) TABLE-US-00023 TABLE 9 Conditioning Cream Ingredients % w/w Part A Deionized water 85.30 L-Arginine 0.15 Glycerin 0.50 Part B BLIE 3.70 Brassica Alcohol 6.55 Helianthus Annuus (Sunflower) Seed Oil 3.00 Part C Preservative 0.80 Total 100.00
(82) The resulting conditioning cream was evaluated against commercially available products (containing petrochemical derivatives) for various performance characteristics in Examples 10-12.
Example 10
Wet Combining Evaluation
(83) The primary technical function of most conditioning products is to lubricate the hair surface, and in doing so to facilitate manageability and mediate degrading feel properties. Thus, protection, conditioning, and manageability properties of a product may be evaluated through combing experiments that quantify the lubrication magnitude. Accordingly, the conditioning cream of Example 9 (“CC9”) was evaluated for these properties in a wet combing study. Virgin (un-colored or unbleached) European medium brown hair test tresses (supplied by International Hair Importers) were prepared to be 1 inch wide, 8 inches long and contained 3 grams of hair.
(84) To eliminate any structural differences in the hair, each tress was initially bleached using a 6% hydrogen peroxide solution at pH of 10.2. The tresses were left in contact with the bleach solution for 50 minutes under controlled temperature conditions (40° C.). At the end of this process, tresses were thoroughly rinsed under an Intellifaucet (Hass Mfg. Co., Averill Park, N.Y.) set at 37° C. with a flow rate of 1.0 GPM.
(85) Internal control condition creams were selected from commercially available products that have previously been determined to represent performance extremes for different attributes. Comparative Conditioner 1 (“CC1”) was a bargain brand product that previous studies have consistently shown to be a relatively poor at providing surface lubrication. Control Conditioner 2 (“CC2”) was the moisturizing variant of a commercially successful hair care brand that has consistently shown high levels of surface lubrication. Each of CC1 and CC2 contains petrochemical materials.
(86) Each tress was treated with one of the CC9, CC1 or CC2. All tress treatment was performed using an Intellifaucet set at 37° C. with a flow rate of 1.0 GPM. Tresses were first wetted for 30 seconds. Conditioner was syringe-applied to the hair at a dosage of 15% of the tress weight (i.e., 0.45 g product on a 3 gram tress). The product was massaged into the tress for 30 seconds, and then allowed to remain on the hair for additional 30 seconds. The product was then rinsed under the Intellifaucet for 30 seconds. A negative control consisting of a tress that was not treated with any conditioning cream was also evaluated.
(87) Each tress was subjected to a wet combing evaluating performed in accordance with the widely used method first proposed by Garcia & Diaz (JSCC, 27, (1976) 379-398-Combability Measurements on Hair,) the contents of which are incorporated here in by reference. Wet combing experiments were performed using an Instron 5500 series tensile tester equipped with Bluehill software. Eight replicate hair tresses are used for each sample to ensure statistical relevance.
(88) The results of the wet combing evaluations are shown below, and are plotted graphically in
(89) TABLE-US-00024 Results of Wet Combing Evaluation Treatment N Mean Std Dev Std Err Mean Unconditioned Hair 8 64.3 1.40 0.50 A CC1 8 21.7 1.61 0.57 B CC9 8 18.0 2.06 0.73 C CC2 8 14.3 1.41 0.50 D Levels not connected by same letter are significantly different.
(90) As can be seen from the results, Conditioner of Example 9 (CC9) has properties about intermediate relative to the properties of the two commercial control formulations. Thus, CC9 provides a wet combing performance that is comparable to many commercially available bodifying/volumizing conditioners.
Example 11
(91) CC9 was evaluated for its surface lubrication properties. Repeated brushing experiments provide a means to evaluate a conditioning products' ability to provide surface lubrication, therefore reducing hair snags, entanglements and abrasion which in turn reduces fiber (hair) breakage. The results of such tests are expressed as a count of the number of broken fibers as a function of combing/brushing cycles. Tresses were bleached and treated with CC9, CC1 and CC2 as described in Example 10, above. Each tress was brushed 10,000 times with subsequent counting of broken fibers. Brushing was performed using a repeated combing/brushing device, to ensure uniform application of brushing force across all tress samples. Eight replicate tresses were used. The results are shown below and are plotted graphically in
(92) TABLE-US-00025 Treatment N Mean Std Dev Std Err Mean Unconditioned Hair 10 197.9 16.46 5.21 A CC1 10 61.3 5.87 1.86 B CC2 10 43.5 4.09 1.29 C CC9 10 40.7 5.03 1.59 C Levels not connected by same letter are significantly different
(93) The data demonstrate that CC9 protects against breakage at a level comparable to the positive control (CC2). Results suggest an approximate 80% reduction in the amount of breakage relative to Unconditioned Hair.
Example 12
(94) CC9 was evaluated for its ability to reduce static electricity build up in hair. Under low humidity conditions, hair has an especially low conductivity and so charges resulting from standard grooming practices (such as heat styling and brushing) are not readily dissipated. Many conditioner products aim to reduce static electricity build-up, although the mechanism by which charge is reduces has not yet been definitively elucidated. It appears likely that there is a contribution from lubrication (which reduces the amount of charge build up), and also an increased surface conductivity arising from the deposition of cationic surfactants (which facilitates charge dissipation).
(95) Hair tresses were bleached and treated with CC9, CC1, and CC2, as described in Example 10. The method of Lunn and Evans (JSCC, (1977), 28, 549-569) (the contents of which are incorporated herein by reference) were used to quantify the anti-static benefit. Hair tresses were equilibrated at low humidity and then brushed. An appropriately placed sensor provided real-time measurement of the static build-up. Eight tresses were evaluated per sample. Untreated tresses were also evaluated. The results are shown below and are plotted graphically in
(96) TABLE-US-00026 Treatment N Mean Std Dev Std Err Mean Unconditioned Hair 10 1452.0 216.6 68.48 A CC1 10 483.0 93.2 29.48 B CC2 10 148.6 47.0 14.87 C CC9 10 116.4 26.5 8.38 C Levels not connected by same letter are significantly different
(97) As can been seen from the results, CC9 provides comparable protection against static flyaway as the positive control.
Example 13
(98) Forty-four formulations of the invention were prepared to evaluate longer term shelf stability of the formula. The formulations 1-44 were prepared by mixing together the ingredients as set out in
(99) In each of formulations 9-24, the ingredient called out as “Base I” is: behenyl alcohol 57.61%, stearyl alcohol 57.61%, isoleucine 14.25%, and ethane sulfonic acid 17.94%. In each of formulations 1-8 and 25-28, the ingredient called out as “Base II” is: Base I 33.26%, cetyl alcohol 33.26%, stearyl alcohol 33.26%, and sodium carbonate 0.22%.
(100) The initial physical properties of pH and viscosity for each formulation were evaluated and are shown in
(101) While it has been shown and described several embodiments in accordance with the invention and use thereof, it is understood that the same is not limited thereto, but is susceptible to many changes and modifications to one possessing ordinary skill in the art, and therefore we do not wish to be limited to the details shown and described herein, but intend to cover all such modifications as are encompassed by the scope of the appended claims.