Patent Application
20170290759
This invention relates generally to low viscosity cellulosic rheology modifiers that are useful in hair care formulations. The low viscosity cellulosics exhibit a gelation temperature of more than 45° C. or a hydration temperature of 25° C. or more.
Hair care products must be effective at delivering active ingredients, such as styling polymers and conditioning polymers, while still having good aesthetic properties. From an end- user perspective, consumers associate good aesthetics, such as pleasant tactile feel and a pleasing visual appearance, with performance and value. For hair fixative compositions in particular, it is also desirable to that such compositions provide high volume and shine in hair, while leaving the hair with a light and natural feel.
To this end, many different types of rheology modifiers have been utilized in hair care compositions. For example, U.S. Patent Application Publication No. US 2014/0202485 discloses personal care compositions incorporating low gelation temperature methylcellulose imparting improved aesthetics. However, the prior art suffers from the disadvantage of requiring cooling to temperatures of 10° C. or less in order to enable the methylcellulose to go into solution, which is necessary to provide a clear appearance and also obtain the desired performance benefit. Such required cooling, however, presents an obstacle to formulators when preparing an end-user composition.
Consequently, there is a need to develop new additives for use in hair care formulations that provide high volume in hair in combination with a light and natural feel, while also eliminating the need to cool such components during preparation of an end-user composition.
One aspect of the invention provides a hair care composition comprising (a) a cellulose ether having (i) a methoxy substitution of from 15 to 42 weight % based upon the weight of the cellulose ether (ii) a viscosity of from 15 cP to less than 4,000 cP in a two percent aqueous solution at 20° C., and (iii) a gelation temperature of greater than 45° C., and (b) at least one hair fixative polymer, conditioning agent, or humectant. In certain embodiments, the cellulose ether is a hydroxypropyl methylcellulose further comprising a hydroxypropyl substitution of up to 32 weight % based upon the weight of the cellulose ether,
In another aspect, the invention provides a hair care composition comprising (a) a cellulose ether having a (i) a methoxy substitution of from 21 to 42 weight % based upon the weight of the cellulose ether (ii) a viscosity of from 15 cP to less than 4,000 cP in a two percent aqueous solution at 20° C., and (iii) a hydration temperature of 25° C. or higher, and (b) at least one hair fixative polymer, conditioning agent, or humectant. In certain embodiments, the cellulose ether is a hydroxypropyl methylcellulose further comprising a hydroxypropyl substitution of up to 32 weight % based upon the weight of the cellulose ether,
Another aspect of the present invention provides a method for inducing volume in hair comprising (1) applying to the hair a hair care composition comprising (a) a cellulose ether having (i) a methoxy substitution of from 21 to 42 weight % based upon the weight of the cellulose ether (ii) a viscosity of from 15 cP to less than 4,000 cP in a two percent aqueous solution at 20° C., and (iii) a gelation temperature of greater than 45° C., and (b) at least one hair fixative polymer, conditioning agent, or humectant; and (2) heat drying the hair. In certain embodiments, the cellulose ether is a hydroxypropyl methylcellulose further comprising a hydroxypropyl substitution of up to 32 weight % based upon the weight of the cellulose ether,
In yet another aspect, the invention provides a method for inducing volume in hair comprising (1) applying to the hair a hair care composition comprising (a) a cellulose ether having (i) a methoxy substitution of from 21 to 42 weight % based upon the weight of the cellulose ether, (ii) a viscosity of from 15 cP to less than 4,000 cP in a two percent aqueous solution at 20° C., and (iii) a hydration temperature of 25° C. or higher, and (b) at least one hair fixative polymer, conditioning agent, or humectant; and (2) heat drying the hair. In certain embodiments, the cellulose ether is a hydroxypropyl methylcellulose further comprising a hydroxypropyl substitution of up to 32 weight % based upon the weight of the cellulose ether,
The inventors have now surprisingly found that cellulose ethers, and in particular methyl cellulose (MC) and hydroxypropyl methyl cellulose (HPMC), are useful as additives in hair care compositions that provide a hair volumizing effect, while also eliminating the need to cool such components during preparation of an end-user composition. Accordingly, the present invention provides in one aspect a hair care formulation comprising a cellulose ether having a methoxy substitution of from 21 to 42 weight % and, optionally a hydroxypropyl substitution of up to 32 weight %, based upon the weight of the cellulose ether, a viscosity of from 15 cP to less than 4,000 cP in a two percent aqueous solution at 20° C., and at least one hair fixative polymer, conditioning agent, or humectant.
In the present invention, “hair care” relates to personal care compositions to be topically applied to a person (i.e., not ingested), and in particular a person's hair. Examples of hair care compositions include, but are not limited to, shampoos, leave-on conditioners, styling gels, hairsprays, and mousses. In certain preferred embodiments, the hair care composition is a mousse. Preferably, the hair care compositions are cosmetically acceptable. As used herein, “cosmetically acceptable” refers to ingredients typically used in personal care compositions, and is intended to underscore that materials that are toxic when present in the amounts typically found in personal care compositions are not contemplated as part of the present invention. The compositions of the invention may be manufactured by processes well known in the art, for example, by means of conventional mixing, dissolving, granulating, emulsifying, encapsulating, entrapping, or lyophilizing processes.
Cellulose has a polymeric backbone repeating structure of anhydroglucose units joined by 1-4 linkages. Each anhydroglucose unit contains hydroxyl groups at the 2, 3, and 6 positions. Substitution of these hydroxyls creates cellulose derivatives. For example, treatment of cellulosic fibers with caustic solution, followed by a methylating agent such as methyl chloride, yields cellulose ethers substituted with one or more methoxy groups. If not further substituted with other alkyls, this cellulose derivative is known as methyl cellulose. The cellulose ethers useful in the present invention are also substituted with one or more methoxy groups. In certain embodiments, cellulose ethers containing both methoxy and hydroxypropyl substitutions are known as hydroxypropyl methylcellulose. In certain embodiments, the hydroxypropyl substituent group, —OCH2CH(OH)CH3, contains a secondary hydroxyl and may also be considered to form a propylene glycol ether of cellulose. The varying ratios of hydroxypropyl and methyl substitution is a factor which influences properties such as organic solubility and the thermal gelation temperature of aqueous solutions. In certain embodiments, the cellulose ethers useful in the present invention have a methoxy substitution of from 21 to 42 weight %, preferably of from 21 to 35 weight %, and more preferably of from 25 to 35 weight %, based upon the weight of the cellulose ether. In certain embodiments, the cellulose ethers useful in the present invention have a hydroxypropyl substitution of from 32 weight % or less, preferably of from 1 to 14 weight %, and more preferably of from 3 to 12 weight %, based upon the weight of the cellulose ether. The substitution is determined according to ASTM D2363-79. In certain embodiments, the cellulose ether polymers of the present invention have the following repeating structure:
The difference in molecular weight of various methyl cellulose and hydroxypropyl methylcellulose polymers is reflected in the viscosity of an aqueous solution of a standard concentration. Viscosity of polymer solutions is the result of hydration of polymer chains, primarily through H-bonding of water molecules to the oxygen atoms in the numerous hydroxyl groups and ether linkages and the conformation rigidity of the anhydroglucose units in the polymer backbone, causing them to extend and form relatively open random coils. A given hydrated random coil is further H-bonded to additional water molecules, entrapping water molecules within, and may be entangled with other random coils. All of these factors contribute to larger effective size and increased frictional resistance to flow. As used herein, the term “viscosity” and the associated value for the 2% w/w aqueous solution is frequently used as a way to refer to the molecular weight of the polymer. In certain embodiments, the cellulose ethers useful in the present invention has a viscosity of from 15 cP to less than 4,000 cP, preferably from 19 cP to 1,500 cP, and more preferably from 19 cP to 99 cP, in a two percent aqueous solution at 20° C. Viscosities of aqueous solutions are determined by Ubbelohde tube according to ASTM D1347-72 and D2363-79.
One unusual property of cellulose ethers of the present invention is that they exhibit reverse thermal gelation. In other words, aqueous solutions of MC and HPMC will form gels at elevated temperature and give viscous solutions at cooler temperatures. Without wishing to be bound by theory, it is believed that thermal gelation temperature is governed by the nature and quantity of the substituent groups attached to the anhydroglucose ring and will thus vary according to the amount of methyl and hydroxypropyl substitution. Thus, hair care compositions comprising MC or HPMC may be applied to hair followed by heating (e.g., blow-drying) to form a gel. In certain embodiments, the cellulose ethers useful in the present invention have a gelation temperature measured as a 2% aqueous solution of greater than 45° C., preferably from 58° C. to 90° C., from 64° C. to 70° C., or from 62° C. to 68° C. In certain embodiments, the cellulose ether has a gelation temperature of from 58° C. to 64° C. In certain embodiments, the cellulose ether has a gelation temperature of from 70° C. to 90° C.
Methyl cellulose and hydroxypropyl methylcellulose dissolve in cold water by swelling and subsequent hydration. Without wishing to be bound by theory, it is believed that in a solution state at the hydration temperature, molecules are hydrated and there is little polymer-polymer interaction. As the temperature increases, the molecules gradually lose their water of hydration, and gelation will occur once a sufficient dehydration of the polymer occurs. Thus, the cellulose ether must be cooled to its hydration temperature in order to achieve a solution state in the inventive hair care formulations. In certain embodiments, the cellulose ethers useful in the present invention have a hydration temperature of 13° C. or higher, 20° C. or higher, 25° C. or higher, or 29.5° C. or higher.
Methods of making methyl cellulose and hydroxypropyl methylcellulose are described in detail in U.S. Pat. No. 6,235,893. Generally, cellulose pulp is treated with a caustic solution, for example an alkali metal hydroxide, followed by an etherifying agent, e.g., methyl chloride (to achieve methoxy substitution) and/or propylene oxide (to achieve hydroxypropyl substitution). The resulting methyl cellulose or hydroxypropyl methylcellulose is washed to remove salt and other reaction by-products. Before or after washing, the cellulose ether may be stripped by exposure to steam to reduce residual organic content. The cellulose ether is then dried to a reduced moisture and volatile content of preferably 0.5 to 10.0 weight % water and more preferably 0.8 to 5.0 weight % water and volatiles based upon the weight of the HPMC. The reduced moisture and volatiles content enables the cellulose ether to be milled into particulate form. The cellulose ether is milled to particulates of desired size.
Once milled, aqueous solutions of MC or HPMC may be prepared by dispersion technique. In certain embodiments, the milled MC or HPMC is dispersed in heated water, and then cooled while agitating until hydration is complete. It is desirable to have adequate cooling after dispersion of the MC or HPMC in hot water to ensure complete hydration. For improved clarity and reproducible control of viscosity, solutions of MC or HPMC may require cooling in to a hydration temperature of from 13° C. to 29.5° C., preferably of from 20° C. to 25° C.
A person of ordinary skill in the art can readily determine the effective amount of MC or HPMC that should be used in a particular composition in order to provide the desired benefits described herein (e.g., increased volume in hair) via a combination of general knowledge of the applicable field as well as routine experimentation where needed. By way of non-limiting example, the amount of MC or HPMC in the hair care compositions of the invention may be in the range of from 0.01 to 10 weight %, preferably of from 0.05 to 5.0 weight %, and even more of from 0.1 to 1.0 weight %, based on the total weight of the composition.
In certain embodiments, the hair care compositions of the present invention include a hair fixative polymer. Suitable hair fixative polymers include, for example, PVP/VA copolymer, ethyl ester of PVM/MA copolymer, butyl ester of PVM/MA copolymer, vinyl acetate/crotonic acid copolymer, vinyl acetate/crotonic acid/vinyl neodecanoate, VA/butyl maleate/isobornyl acrylate copolymer, acrylates copolymer, diglycol/CHDM/isophthalates/SIP copolymer, acrylates/hydroxyester acrylates copolymer, methacrylates/acrylates copolymer/amine salt, AMP-acrylates/diacetone-acrylamide copolymer, AMPD-acrylates/diacetone-acrylamide copolymer, acrylates/methacrylate polymers, acrylates/acrylamide copolymer, PVP/vinyl caprolactam/DMAPA acrylates copolymer, polyvinylcaprolactam, isobutylene/ethylmaleimide/hydroxyethylmaleimide copolymer, acrylates/succinates/hydroxyacrylates copolymer, polyurethane-1, octylacrylamide/acrylates/butylaminoethyl methacrylate copolymer, vinyl caprolactam/VP/dimethylaminoethyl methacrylate copolymer, acrylates/t-butylacrylamide copolymer, acrylates/C1-2 succinates/hydroxyacrylates copolymer, acrylamide/sodium acryloyldimethyltaurate/acrylic acid polymer and mixtures thereof. The amount of hair fixative polymer effective for achieving the desired property provided by such components can be readily determined by one skilled in the art. In certain embodiments, the hair fixative polymer is present in a range of from 0.1 to 8.0 weight %, preferably of from 0.5 to 5.0 weight %, and more preferably of from 1.0 to 3.0 weight %. In certain embodiments, the hair care compositions of the present invention include a conditioning agent. Suitable conditioning agents include, for example, quaternary ammonium salts of hydroxyethyl cellulose (e.g., Polyquaternium 67) commercially available from The Dow Chemical Company under the tradename SOFTCAT, polymeric quaternary ammonium salts of hydroxyethyl cellulose polymers (e.g., Polyquaternium 10) commercially available from The Dow Chemical Company under the tradename UCARE, and quaternary trialkylammonium halide compounds including, for example, dihydroxypropyl trialkyl ammonium chloride commercially available from The Down Chemical Company under the tradename PD QUAT. In certain embodiments, the conditioning agent is present in a range of from 0.1 to 20 weight %, preferably of from 0.5 to 10 weight %, and more preferably of from 1.0 to 3.0 weight %.
In certain embodiments, the hair care compositions of the present invention include a humectant to prevent loss of moisture. Suitable humectants include, for example, glycerin, sorbitol, monoglycerides, lecithins, glycolipids, fatty alcohols, fatty acids, polysaccharides, sorbitan esters, polysorbates (e.g., Polysorbate 20, Polysorbate 40, Polysorbate 60, and Polysorbate 80), diols (e.g., propylene glycol), diol analogs, triols, triol analogs, polymeric polyols, and mixtures thereof. In certain embodiments, the humectant is present in an amount of from 0.1 to 20 weight %, preferably 2 to 15 weight %, and more preferably 5 to 10 weight %, by weight of the hair care composition.
In certain embodiments, the hair care composition contains excipients, such as additional rheology modifiers/thickeners, emollients (e.g., hydrocarbon oils, esters, natural oils, or silicones), waxes, sensory modifiers, preservatives/antioxidants/chelating agents, reducing agents, pH adjusting agents/buffers/neutralizing agents, sunscreen actives, vitamins, proteins/amino acids, plant extracts, natural ingredients, bio-actives, fragrances/perfumes, foaming agents, penetrants, surfactants/detergents/emulsifiers/opacifying agents, volatiles/propellants/solvents/carriers, liquid vehicles/solvents/carriers, salts, anti-static agents, anti-frizz agents, antidandruff agents, hair waving/straightening agents, absorbents, colorants, hard particles, and other silicones. The amount of optional ingredients effective for achieving the desired property provided by such ingredients can be readily determined by one skilled in the art.
The hair care compositions of the present invention also include a dermatologically acceptable carrier. Such material is typically characterized as a carrier or a diluent that does not cause significant irritation to the skin and does not negate the activity and properties of active agent(s) in the composition. Examples of dermatologically acceptable carriers that are useful in the invention include, without limitation, water, such as deionized or distilled water, emulsions, such as oil-in-water or water-in-oil emulsions, alcohols, such as ethanol, isopropanol or the like, acetone, glycols, such as propylene glycol, glycerin or the like, creams, aqueous solutions, oils, ointments, pastes, gels, lotions, milks, foams, suspensions, powders, or mixtures thereof. In some embodiments, the composition contains from about 99.99 to about 50 percent by weight of the dermatologically acceptable carrier, based on the total weight of the composition.
As noted above, the hair care compositions of the present invention are highly effective as additives for providing a volumizing effect on hair because of the reverse thermal gelation properties of the methylcellulose or hydroxypropyl methylcellulose included in the composition. They exhibit volumizing attributes on par with, if not better than, previously known additives for hair care applications, without the disadvantage of a low hydration temperature for purposes of dispersing the MC or HPMC in the composition, thereby simplifying the formulation process for the hair care composition. Accordingly, the hair care compositions of the present invention are useful for the treatment of hair. Thus, in one aspect the present invention provides that the hair care compositions may be used in a method for styling hair.
In practicing the methods of the invention, the hair care compositions are generally administered topically by applying the compositions onto the hair via a spray, mousse, or gel. A person of ordinary skill in the art can readily determine the frequency with which the compositions should be applied. The frequency may depend, for example, on the level of humidity that an individual is likely to encounter in a given day and/or the sensitivity of the individual to low humidity. By way of non-limiting example, administration on a frequency of at least once per day may be desirable.
Some embodiments of the invention will now be described in detail in the following Examples.
Exemplary hair care compositions of the present invention contain the components recited in Table 1.
A 2% solids solution of each hydroxypropyl methylcellulose (i.e., METHOCEL E19 and METHOCEL K99) was prepared by slowly adding the respective HPMC to water heated to 80-90° C. and stirring until well hydrated. The solution was then allowed to cool to room temperature. A mousse was then formulated by charging the 2% solids HPMC solution to water in a mixing vessel. The AMP Ultra PC 2000 was added with stirring. An emulsion polymer of Acudyne 1000 and Aculyn 88 was then added with stirring. The additional components in Phase B were added in order to complete the concentrate formulation. An aerosol can was then filled with 94% of the resulting concentrate solution, and then charged with butane (3%) and propane (3%).
Comparative hair care compositions of the present invention contain the components recited in Table 2.
+METHOCEL SG A7C = Methylcellulose having a viscosity of 700 cP in a two percent aqueous solution at 20° C., a gelation temperature of from about 38-44° C., and a hydration temperature of about 10° C. (available from The Dow Chemical Company)
++METHOCEL K4M = Hydroxypropyl methylcellulose having a viscosity of 4,000 cP in a two percent aqueous solution at 20° C., a gelation temperature of from about 70-90° C., and a hydration temperature of about 29.5° C. (available from The Dow Chemical Company)
Comparative formulation C1 was a control base formulated without volumizing polymer.
Comparative formulations C2 and C3 contained METHOCEL SG A7C and METHOCEL K4M, respectively. A 2% solids solution of METHOCEL SG A7C was prepared by slowly adding the methylcellulose to water heated to 80-90° C. and stirring until well hydrated. The solution was then cooled in an ice bath to about 10° C. while stirring. A 2% solids solution of METHOCEL K4M was prepared by slowly adding the hydroxypropyl methylcellulose to water heated to 80-90° C. and stirring until well hydrated. The solution was then allowed to cool to room temperature while stirring. A mousse was then formulated by charging each of the 2% solids methylcellulose and HPMC solution to water in a mixing vessel. The AMP Ultra PC 2000 was added with stirring. An emulsion polymer of Acudyne 1000 and Aculyn 88 was then added with stirring. The additional components in Phase B were added in order to complete the concentrate formulation. An aerosol can was then filled with 94% of the resulting concentrate solution, and then charged with butane (3%) and propane (3%).
The formulations as prepared in Examples 1 and 2 above were evaluated for the enhancement of hair volume after application to hair. Sample hair tresses were washed with 10% Tergitol 15-S-9 and allowed to air dry overnight. Each test formulation (as prepared in Examples 1 and 2 above from E1, E2, C1, C2, and C3) was applied to three different sample tresses. Each tress of hair was evaluated three times to obtain an initial untreated volume measurement using the Dia-Stron Wet Combing Method: (i) ring size=0.5 inches; (ii) start position=20 mm; (iii) end position of 160 mm for 22.5 cm long hair, 145 mm for 20.5 cm medium hair, and 130 mm for 18.5 cm short hair; (iv) rate=150 mm/min. Each tress was separately hydrated under lukewarm tap water for 20 seconds per side. Excess water was squeezed from the hair tresses using two fingers of a gloved hand. Each tress was then combed through twice with a wide tooth comb and twice with a fine tooth comb. After combing, 0.2 g (10% of hair weight) of each test mousse (as prepared in Examples 1 and 2 above from E1, E2, C1, C2, and C3) was dispensed on each hair tress and massaged into the hair with a gloved hand until all of the mousse appeared to be evenly distributed into the hair. Each hair tress was then hung from a clip or ring stand and dried using an Andis Professional 1800 hair dryer on highest and hottest settings while combing the hair with a 1.75 inch round brush. The temperature of the blow dryer was about 80-85° C. at a distance of approximately 5 cm from the hair. The drying process was kept consistent by completing 3-4 pass-throughs of the hair with the brush and drying the hair completely in 1.5 minutes. The tresses were then allowed to equilibrate to room temperature in the control-temperature room for 1 hour. Post-treatment volume measurements were then collected from the hair using the same Dia-Stron Wet Combing Method described above.
As shown in
The above results demonstrate that the inventive hair care compositions containing hydroxypropyl methylcellulose provide superior hair volume performance when applied to hair as compared to formulations containing methylcellulose having a hydration temperature of less than 10° C. and a gelation temperature of less than 45° C.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US2015/052615 | 9/28/2015 | WO | 00 |
| Number | Date | Country | |
|---|---|---|---|
| 62057327 | Sep 2014 | US |
