Polyurethanes are a well-known class of synthetic polymers with broad utility in multiple industries. This versatility is derived from the ability to prepare polyurethanes from a large and diverse set of potential monomers. These diverse monomer options allow the realization of an equally diverse set of physical properties. Hence, the resulting polyurethanes can be in many different forms including e.g., soft foams, elastomers, adhesive films, or hard plastics, and can be used in many different types of products including bedding, foot wear, adhesives, and automobile parts. Among these many forms of polyurethanes, waterborne polyurethanes (WBPUs) have been used as film forming agents in commercially available personal care products.
A problem with the use of WBPUs has been the lack of performance and overall consistency in application. For example, common polyurethane products such as Luviset® P.U.R (Polyurethane-1), DynamX, and DynamX/H2O (Polyurethane-14 and AMP-Acrylates Copolymer) lack elasticity. This leads to an undesirable stiff feeling when applied to hair. Avalure UR 450 (PPG-17/IPDI/DMPA Copolymer), Baycusan C1004 (Polyurethane-35), Baycusan C1008 (Polyurethane-48), and Polyderm PE/PA ED (Polyurethane-58), on the other hand, are very flexible (i.e., do not lack elasticity). These products, however, have poor initial curl hold and elicit a gummy feeling. Other problems associated with the use of WBPUs include e.g., flaking upon touching or combing (e.g., dusty micro-flakes shown on hair fibers); undesirable tactile feelings upon touch (e.g., brittle, stiff, or tacky, gummy); poor humidity resistance (e.g., styling resins absorb moisture and weigh down hair resulting in a loss of style); lack of movement (e.g., plastic-like mold shape; hair curls don't move with motion; can't easily comb through; gummy; lack of bounciness); and short-lived hair styles (e.g., hair styles, curls, waves, etc. don't last long—on average styles typically last less than a half day).
There is therefore a need for improved and more consistent WBPU-based personal care products including e.g., ones that provide enhanced hold, high humidity curl retention, and/or positive sensory attributes.
A specific combination of selection markers for cationic polyurethanes have now been identified that result in cosmetic compositions (e.g., hair products) which have substantially improved performance and which can be used in a variety of applications. Markers for these cationic polymers include e.g., a Young's modulus above 150 MPa, an elongation at break from about 15% to about 300%, and a moisture uptake of less than 10%.
In one aspect, the disclosed cationic polyurethanes can be used in a two-wave hair styling process comprising anionic polyurethanes. Applying and fixing the disclosed cationic polyurethanes to the hair prior to the application of anionic polyurethanes was found to enhance hold, high humidity curl retention, and positive sensory attributes. See e.g.,
In another aspect, the disclosed cationic polyurethanes can serve as additives for conditioners or leave-in-conditioners. When used in this manner, the disclosed cationic polyurethanes were found to provide better hold, improve stylability, minimize flyaways, and to sustain natural curl enhancement. See e.g.,
A composition, process, or method described herein that “consists essentially of” a cationic polyurethane and other components means that the recited cationic polyurethane is the only polyurethane present in the recited composition, process, or method. Thus, “consists essentially of” or “consisting essentially of” is open ended for all terms except for the inclusion of additional polyurethanes, i.e., only the recited cationic polyurethane is present.
A composition, process, or method described herein that “consists of” a cationic polyurethane and other components means that only the recited components are present. In other words, “consisting of” excludes any element, step, or ingredient not specified. “Consists of” and “consisting of” are used interchangeably.
“Comprising” is inclusive or open-ended and does not exclude additional, un-recited elements or method steps.
As used herein, “cationic polyurethanes” refer to thermoplastic polymers comprising carbamate (urethane) groups and which bear an overall net positive charge at pH<7. In some aspects, the cationic polyurethanes described herein bear an overall net positive charge at pH from about 3.7 to about 6.5, from about 3.7 to about 6.0, or from about 3.7 to about 5.5. Unless otherwise specified, cationic polyurethanes, when used herein, include amphoteric/cationic polyurethanes. In one aspect, however, cationic polyurethanes do not encompass amphoteric/cationic polyurethanes.
As used herein, “anionic polyurethanes” refer to thermoplastic polymers comprising carbamate (urethane) groups and which bear an overall net negative charge at pH≥7. Unless otherwise specified, anionic polyurethanes, when used herein, include amphoteric/anionic polyurethanes. In one aspect, however, anionic polyurethanes do not encompass amphoteric/anionic polyurethanes.
As used herein, “amphoteric polyurethanes” refer to thermoplastic polymers comprising carbamate (urethane) groups and which can act as a cationic or anionic polyurethane. An “amphoteric/cationic polyurethane” means that the described amphoteric species is one which is acting as an acid under the defined methods and/or conditions. Similarly, an “amphoteric/anionic polyurethane” means that the described amphoteric species is one which is acting as a base under the defined methods and/or conditions.
“Young's modulus (or the modulus of elasticity, tensile modulus)” is a measure of the stiffness of a solid polymer film. Young's modulus, E, can be calculated by dividing the tensile stress by the extensional strain in the elastic (initial, linear) portion of the stress-strain curve. The Young's modulus of the cationic polyurethane can be determined by a protocol defined to measure mechanical properties, and is developed in reference to ASTM D638, ASTM D412, test guidelines as described below in Example 2.
The “elongation at break (also known as fracture strain, ultimate elongation)” is the ratio between changed length and initial length after breakage of the solid polymer film. The elongation at break of the cationic polyurethane can be determined by a protocol defined to measure mechanical properties, and is developed in reference to ASTM D638, ASTM D412, test guidelines as described below in Example 2.
The “moisture uptake” is the measure of water adsorbed by the solid polymer film. The method for determining the moisture uptake of the solid polymer film is provided in Example 3.
The “sensory score” is determined by the performance of the hair fixative. In particular, the tress with the composition applied is blow dried for 90 seconds. The tresses are prepared in duplicate and blinded randomly and evaluated for natural feeling and overall sensory attributes on a scale of −2 to 2 by trained sensory analysts under blinded conditions. Sensory analysts are licensed hair stylists and cosmetic scientists with significant long-term experience evaluating sensory attributes of hair. Sensory analysts assign a score of −2 to tresses deemed entirely undesirable, a score of +2 to entirely soft, natural feeling and appearing hair, and intermediate scores between these two extremes.
Provided herein are specific combinations of WBPU properties that have been found to result in cosmetic compositions (e.g., hair products) having substantially improved performance. Those properties include e.g., a combination of certain mechanical properties, a combination of certain chemical properties, or a combination of both mechanical and chemical properties.
Young's Modulus, Elongation at Break, and Moisture Uptake
The combination of mechanical properties described herein include the Young's modulus (e.g., above 150 MPa), the elongation at break (e.g., from about 15% to about 300%), and hydrophobicity (moisture uptake, e.g., less than 10%).
In one aspect, the Young's modulus of the cationic polyurethane should be above about 150 MPa. For example, the Young's modulus of the cationic polyurethane in the disclosed compositions may be above about 160 MPa, above about 170 MPa, above about 180 MPa, above about 190 MPa, above about 200 MPa, above about 210 MPa, above about 220 MPa, above about 230 MPa, above about 240 MPa, above about 250 MPa, above about 260 MPa, above about 270 MPa, above about 280 MPa, above about 290 MPa, above about 300 MPa, above about 310 MPa, above about 320 MPa, above about 330 MPa, above about 340 MPa, above about 350 MPa, above about 360 MPa, above about 370 MPa, above about 380 MPa, above about 390 MPa, above about 400 MPa, above about 410 MPa, above about 420 MPa, above about 430 MPa, above about 440 MPa, above about 450 MPa, above about 460 MPa, above about 470 MPa, above about 480 MPa, above about 490 MPa, above about 500 MPa, above about 510 MPa, above about 520 MPa, above about 530 MPa, above about 540 MPa, or above 550 MPa. In other aspects, the Young's modulus of the cationic polyurethane should be between about 150 MPa and about 500 MPa. For example, the Young's modulus of the cationic polyurethane in the disclosed compositions may be between about 150 MPa and about 400 MPa, between about 150 MPa and about 350 MPa, between about 170 MPa and about 390 MPa, between about 180 MPa and about 320 MPa, between about 190 MPa and about 300 MPa, between about 200 MPa and about 290 MPa, or between about 210 MPa and about 280 MPa.
In one aspect, the elongation at break of the cationic polyurethane should be from about 15% to about 300%. For example, the elongation at break of the cationic polyurethane in the disclosed composition may be from about 20% to about 300%, from about 25% to about 300%, from about 40% to about 280%, from about 100% to about 280%, from about 100% to about 250%, from about 150% to about 250%, from about 200% to about 250%, from about 210% to about 250%, about 30% to about 150%, from about 15% to about 150%, from about 150% to about 300%, from about 50% to about 250%; from about 75% to about 225%, or from about 100 to about 200%. The elongation break may be optionally combined with one or more of the Young's modulus values described in the paragraph above or any one of the Young's modulus values described in the remainder of the disclosure.
In one aspect, the moisture uptake of the cationic polyurethane should be less than about 10%. For example, the moisture uptake of the cationic polyurethane in the disclosed compositions may be less than about 9.5%, less than about 9%, less than about 8.5%, less than about 8%, less than about 7.5%, less than about 7%, less than about 6.5%, less than about 6%, less than about 5.5%, less than about 5%, less than about 4.5%, less than about 4%, less than about 3.5%, less than about 3%, less than about 2.5%, less than about 2%, less than about 1.5%, less than about 1%, less than about 0.5%, or is about 0%. In one aspect, the moisture uptake of the cationic polyurethane in the disclosed compositions should be from about 0% to about 10%. For example, the moisture uptake may be from about 0% to about 8%, from about 2% to about 8%, or from about 3% to about 7%. The moisture uptake may be optionally combined with one or more of the Young's modulus values, one or more of the elongation break values, or both as described in the paragraphs above or in the remainder of the disclosure.
As shown in the Exemplification section below, cationic polyurethanes having the Young's modulus, elongation at break, and moisture uptake described above have improved performance (e.g., enhanced hold, high humidity curl retention, positive sensory attributes, improved stylability, natural curl enhancement, and minimization of flyaways.
In addition to the Young's modulus, elongation at break, and moisture uptake, other indicators may be used to identify the capability of cationic polyurethanes to provide long lasting, moisture-resistant hold hair product with favorable sensory attributes. Such indicators include e.g., change in tress length and sensory score.
Thus, in certain aspects, the cationic polyurethane may be selected such that the composition, after being applied to a curled hair tress and dried thereon, provides less than about 80% change in tress length as measured by the high humidity mechanical stress test. For example, the cationic polyurethane may be selected such that the composition, after being applied to a curled hair tress and dried thereon, provides less than about 75%, about 70%, about 65%, about 60%, about 55%, about 50%, about 45%, about 40%, about 35%, about 30%, about 25%, about 20%, about 15%, about 10%, about 5%, or about 0% change in tress length as measured by the high humidity mechanical stress test. The change in tress length as described herein may also be combined with any one of the Young's modulus values, elongation at break values, and moisture uptake values described above and herein.
In other aspects, the cationic polyurethane may be selected such that the composition, after being applied to a hair tress and dried thereon, provides a sensory score of at least about 0. For example, the cationic polyurethanes in the disclosed compositions may be selected such that the composition, after being applied to a hair tress and dried thereon, provides a sensory score of at least about 0.1, about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0.7, about 0.8, about 0.9, about 1.0, about 1.1, about 1.2, about 1.3, about 1.4, or about 1.5. The sensory score feature as described herein may also be combined with any one of the change in tress length values, the Young's modulus values, the elongation at break values, and the moisture uptake values described above and herein.
As shown in the Exemplification section below, cationic polyurethanes having the Young's modulus, elongation at break, and moisture uptake described above, and optionally one or more of the alternative indicators (e.g., sensory score, change in tress length, etc.) provide hair styling products with improved mechanical properties, sensory properties and performance.
Provided herein are compositions (e.g., hair treatment compositions) comprising a cationic polyurethane having a Young's modulus above 150 MPa, an elongation at break from about 15% to about 300%, and a moisture uptake of less than 10%. Also provided are composition consisting essentially of a cationic polyurethane; a neutralizer; and an oil, wherein the cationic polyurethane has a Young's modulus above 150 MPa; an elongation at break from about 15% to about 300%; and a moisture uptake of less than 10%.
In some aspects, the cationic polyurethane in the provided compositions is a salt of the formula: [W, V, Y and Z]X−, wherein W is the product formed from polycarbonate polyol monomer; V is the product formed from polyisocyanate monomer; Y is the product formed from C1-8alkyldiol monomer; Z is the product formed from C1-8aminoalkyldiol monomer; X is a neutralizing ion; the molecular weight of W is about 1,000 g/mol; the molar ratio of V:W is 1:0.18 to about 1:0.32; the molar ratio of V:Y is 1:0.24 to about 1:0.72; and the molar ratio of V:Z is 1:0.08 to about 1:0.47. In one alternative, the cationic polyurethane in the provided compositions is a salt of the formula: [W, V, Y and Z]X−, wherein W is the product formed from polycarbonate polyol monomer; V is the product formed from polyisocyanate monomer; Y is the product formed from C1-8alkyldiol monomer; Z is the product formed from C1-8aminoalkyldiol monomer; X is a neutralizing ion; the molecular weight of W is about 2,000 g/mol; the molar ratio of V:W is 1:0.08 to about 1:0.18; the molar ratio of V:Y is 1:0.36 to about 1:0.82; and the molar ratio of V:Z is 1:0.08 to about 1:0.49. In another alternative, the cationic polyurethane in the provided compositions is a salt of the formula: [W, V, Y and Z]X−, wherein W is the product formed from polycarbonate polyol monomer; V is the product formed from polyisocyanate monomer; Y is the product formed from C1-8alkyldiol monomer; Z is the product formed from C1-8aminoalkyldiol monomer; X is a neutralizing ion; the molecular weight of W is about 3,000 g/mol; the molar ratio of V:W is 1:0.05 to about 1:0.13; the molar ratio of V:Y is 1:0.4 to about 1:0.85; and the molar ratio of V:Z is 1:0.08 to about 1:0.49.
In one alternative the cationic polyurethane is a salt of the formula: [W, V, Y, Z, and Z1]X−, wherein W is the product formed from polycarbonate polyol monomer; V is the product formed from polyisocyanate monomer; Y is the product formed from C1-8alkyldiol monomer; Z is the product formed from C1-8aminoalkyldiol monomer; Z1 is the product formed from ethoxylated polyol monomer; X is a neutralizing ion; the molecular weight of W is about 1,000 g/mol; the molar ratio of V:W is 1:0.19 to about 1:0.33; the molar ratio of V:Y is 1:0.19 to about 1:0.7; the molar ratio of V:Z is 1:0.08 to about 1:0.49; and the molar ratio of V:Z1 is 1:0 to about 1:0.03. In another alternative, the cationic polyurethane in the provided compositions is a salt of the formula: [W, V, Y, Z, and Z1]X−, wherein W is the product formed from polycarbonate polyol monomer; V is the product formed from polyisocyanate monomer; Y is the product formed from C1-8alkyldiol monomer; Z is the product formed from C1-8aminoalkyldiol monomer; Z1 is the product formed from ethoxylated polyol monomer; X is a neutralizing ion; the molecular weight of W is about 2,000 g/mol; the molar ratio of V:W is 1:0.09 to about 1:0.18; the molar ratio of V:Y is 1:0.31 to about 1:0.8; the molar ratio of V:Z is 1:0.09 to about 1:0.51; and the molar ratio of V:Z1 is 1:0 to about 1:0.03. In another alternative, the cationic polyurethane in the provided compositions is a salt of the formula: [W, V, Y, Z, and Z1]X−, wherein W is the product formed from polycarbonate polyol monomer; V is the product formed from polyisocyanate monomer; Y is the product formed from C1-8alkyldiol monomer; Z is the product formed from C1-8aminoalkyldiol monomer; Z1 is the product formed from ethoxylated polyol monomer; X is a neutralizing ion; the molecular weight of W is about 3,000 g/mol; the molar ratio of V:W is 1:0.05 to about 1:0.13; the molar ratio of V:Y is 1:0.36 to about 1:0.83; the molar ratio of V:Z is 1:0.09 to about 1:0.52; and the molar ratio of V:Z1 is 1:0 to about 1:0.03. In another alternative, the cationic polyurethane in the provided compositions is a salt of the formula: [W, V, Y, Z, and Z2]X−, wherein W is the product formed from polycarbonate polyol monomer; V is the product formed from polyisocyanate monomer; Y is the product formed from C1-8alkyldiol monomer; Z is the product formed from C1-8aminoalkyldiol monomer; Z2 is the product formed from hydroxylated alkyl acid monomer; X is a neutralizing ion; the molecular weight of W is about 1,000 g/mol the molar ratio of V:W is 1:0.19 to about 1:0.33; the molar ratio of V:Y is 1:0.14 to about 1:0.44; the molar ratio of V:Z is 1:0.08 to about 1:0.47; and the molar ratio of V:Z2 is 1:0.05 to about 1:0.33. In another alternative, the cationic polyurethane in the provided compositions is a salt of the formula: [W, V, Y, Z, and Z2]X−, wherein W is the product formed from polycarbonate polyol monomer; V is the product formed from polyisocyanate monomer; Y is the product formed from C1-8alkyldiol monomer; Z is the product formed from C1-8aminoalkyldiol monomer; Z2 is the product formed from hydroxylated alkyl acid monomer; X is a neutralizing ion; the molecular weight of W is about 2,000 g/mol; the molar ratio of V:W is 1:0.09 to about 1:0.18; the molar ratio of V:Y is 1:0.26 to about 1:0.53; the molar ratio of V:Z is 1:0.09 to about 1:0.49; and the molar ratio of V:Z2 is 1:0.05 to about 1:0.35. In another alternative, the cationic polyurethane in the provided compositions is a salt of the formula: [W, V, Y, Z, and Z2]X−, wherein W is the product formed from polycarbonate polyol monomer; V is the product formed from polyisocyanate monomer; Y is the product formed from C1-8alkyldiol monomer; Z is the product formed from C1-8aminoalkyldiol monomer; Z2 is the product formed from hydroxylated alkyl acid monomer; X is a neutralizing ion; and the molecular weight of W is about 3,000 g/mol; the molar ratio of V:W is 1:0.05 to about 1:0.13; the molar ratio of V:Y is 1:0.3 to about 1:0.56; the molar ratio of V:Z is 1:0.09 to about 1:0.5; and the molar ratio of V:Z2 is 1:0.05 to about 1:0.35.
In yet another alternative, V is the product formed from isophorone diisocyanate monomer; Y is the product formed from 1,4-butanediol monomer; and Z is the product formed from 3-(dimethylamino)-1,2-propanediol monomer. In yet another alternative, the cationic polyurethane is a salt of the formula:
wherein n is 6 to 21 and m is 19 to 31.
In some aspects, the cationic polyurethane in the provided compositions is selected from PU-363, PU-399, PU-400, PU-377, PU-404, PU-378, PU-383, PU-398, PU-401, PU-402, PU-403, PU-385, PU-376, PU-408, PU-409, PU-396, PU-413, PU-414, PU-362, and PU-372. In another aspect, the cationic polyurethane is selected from PU-362, PU-376, PU-377, PU-378, and PU-404. In yet another aspect, the cationic polyurethane is selected from PU-363, PU-377, and PU-378.
Also provided is a hair treatment composition comprising a cationic polyurethane having the formula:
wherein n is 6 to 21 and m is 19 to 31.
Further provided is a hair treatment composition consisting essentially of a cationic polyurethane having the formula:
wherein n is 6 to 21 and m is 19 to 31; a neutralizer; and an oil.
In some aspects, the cationic polyurethane is dispersed in water.
In some aspects, the cationic polyurethane is in the form of a particle.
In some aspects, the cationic polyurethane comprises uniform particles having an average particle diameter of about 20 to about 80 nm.
In some aspects, the cationic polyurethane comprises bimodal or multimodal particles having an average particle diameter of about 100 to about 300 nm.
In some aspects, the cationic polyurethane is present in an amount of 25% to 35% based on the total weight of the composition.
In some aspects, the compositions described herein further comprise a neutralizer. The neutralizer may be e.g., an acid neutralizer such as lactic acid. In some aspects, the neutralizer:C1-8aminoalkyldiol monomer ratio is from about 0.8 to about 1.2.
In some aspects, the compositions described herein further comprise an oil. Oils for use in the disclosed compositions can be selected from mineral, animal, plant or synthetic oils. In one aspect, the oil is linoleic acid or a mixture of fatty acids. Examples include, but are not limited to fragrance oils, emollients, monoterpenoids, fatty alcohols, fatty acids, fatty esters, fatty ethers, fluorinated small molecules (e.g., perfluoromethylcyclopentane, perfluoroperhydrophenanthrene, perfluoro-1,3-dimethylcyclohexane, perfluoromethyldecalin, and perfluoroperhydrobenzyltetralin), and mixtures thereof. In another aspect, the oil is present in an amount ranging from about 0.2 to about 1.65% based on the total weight of the composition. In another aspect, the oil is present in an amount of about 0.2 to about 0.25% based on the total weight of the composition.
In one aspect, the disclosed compositions are applied to the hair with water.
In one aspect, the disclosed compositions, when applied to the hair, change the texture and appearance.
In one aspect, the disclosed compositions, when applied to the hair, improve hold, i.e., hair that is formed into a given curl or style retains that curl or style over time.
In one aspect, the disclosed compositions, when applied to the hair, provide sufficient stylability, i.e., the composition applied to hair supplies sufficient rigidity and flexibility to form and maintain a style.
In one aspect, the disclosed compositions, when applied to the hair, minimize flyaways, i.e., there are minimal individual hair fibers that do not conform to the given curl or style.
In one aspect, the disclosed compositions, when applied to the hair, preserves curl shape, i.e., hair that is formed into a given curl retains that curl over time.
In one aspect, the disclosed compositions, when applied to the hair, provides natural curl enhancement, i.e., hair that naturally tends to curl displays a more defined and less diffused curl pattern.
The compositions described herein may further comprise an antioxidant. Antioxidants that may be suitable with the compositions described herein include, but are not limited to, acai oil, alpha lipoic acid, green and white tea, retinol, vitamin C, Vitamin E, butylated hydroxytoluene, butylated hydroxyanisole, coenzyme Q10 (Co Q-10), isoflavones, polyphenols, curcumin, turmeric, pomegranate, rosemary, glutathione, selenium, and zinc.
The compositions described herein may be used for any cosmetic application. Such applications include, but are not limited to, skin-care creams, eye and facial makeup (e.g., mascara, eye liner, eyebrow makeup, and the like), deodorants, lotions, powders, perfumes, baby products, body butters; and hair products (e.g., permanent chemicals, hair colors, hair sprays, and gels).
In one aspect, the compositions described herein are used as a hair product, e.g., in a conventional manner for providing hairstyle/hold benefits.
In an exemplary aspect, an effective amount of a composition described herein may be sprayed or applied onto dry or damp hair before and/or after the hair is styled. As used herein “effective amount” means an amount sufficient to provide the hair hold and style performance desired according to the length and texture of the hair.
In one aspect, the present disclosure provides a method of fixing hair comprising the step of applying a polyurethane disclosed herein. In one aspect, the present disclosure provides a method of retaining the curl of hair comprising the step of applying polyurethane disclosed herein.
In one aspect, the present disclosure also includes a method to determine the curl retention of a hair tress. In one aspect, the method of measuring the curl retention of a hair tress includes the steps of a) measuring the length of the hair tress; b) applying a composition comprising a waterborne polyurethane disclosed herein to the hair tress; c) blow drying the hair tress for 90 seconds without brushing; d) curling the hair tress with a ¾ inch curling rod at 370° F. for 10 seconds; e) mechanically manipulating the hair tress by pulling, combing and brushing; f) measuring the length of the curled hair tress.
In one aspect, the method of measuring the curl retention of a hair tress, includes the steps of a) measuring the length of the hair tress; b) applying the composition comprising a waterborne polyurethane disclosed herein to the hair tress; c) blow drying the hair tress for 90 seconds without brushing; d) curling the hair tress with a ¾ inch curling rod at 370° F. for 10 seconds; e) subjecting the hair tress to humidity; f) measuring the length of the curled hair tress. In one aspect, the curled hair tress is subjected to 60%, 70%, 75%, 80% or 90% relative humidity for 3, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 75, 90, 105, 120, 180 or 210 minutes at a temperature of 25° C.
In one aspect, the method of measuring the curl retention of a hair tress, includes the steps of a) measuring the length of the hair tress; b) applying the composition comprising a waterborne polyurethane disclosed herein to the hair tress; c) blow drying the hair tress for 90 seconds without brushing; d) curling the hair tress with a ¾ inch curling rod at 370° F. for 10 seconds; e) subjecting the hair tress to humidity; f) brushing the hair tress; g) measuring the length of the curled hair tress. In a particular aspect, the curled hair tress is subjected to 60%, 70%, 75%, 80% or 90% relative humidity for 2, 4, 8, 16, 32, or 48 hours at a temperature of 25° C. and brushed 1, 3, 5, 8, 10, 13, 15, or 20 times.
In one aspect, the method of evaluating the curl retention of a hair tress, includes the steps of a) applying the composition comprising a polyurethane disclosed herein to the hair tress; b) blow drying the hair tress for 90 seconds without brushing; c) blinding the prepared hair tress; d) evaluating the sensory properties of the tress in a blinded fashion. In one aspect, the prepared tress is graded on a scale of −2 to 2 for natural feeling and overall sensory attributes.
In one aspect, the cationic polymers described herein are for use in a conditioner or leave-in-conditioner.
In one aspect, provided is a method for styling hair comprising a) applying a cationic polyurethane-based composition described herein (the so-called “first wave”; b) heating the hair to a temperature sufficient to induce curl; and c) applying an anionic polyurethane having a Young's modulus above 150 MPa, an elongation at break from about 15% to about 300%, and a moisture uptake of less than 10% (the so-called “second wave”). In one aspect, steps a), b), and c) are repeated.
Cationic waterborne polyurethanes were synthesized primarily using polycarbonate diol, 1,4-butanediol (BD), isophorone diisocyanate (IPDI), and 3-(dimethylamino)-1,2-propanediol (DMAPD); selectively, the nonionic chain extenders Tegomer D3403 (ethoxylated polyether-1,3-diol) and 2,2-bis(hydroxymethyl)butyric acid (DMBA) were incorporated in cationic waterborne polyurethanes respectively to achieve desired physical properties. A mild acid, lactic acid, was used as a neutralizer. For each monomer, the molar ratio to NCO is listed in Table 1. Moreover, a beneficial oil could be also incorporated into cationic waterborne polyurethanes to provide improved sensory attributes.
Overall, inventive cationic waterborne polyurethanes possessed optimal physical properties as defined herein: (1) Young's modulus >150 MPa, (2) Elongation at break between 15% and 300%, and (3) Water uptake (a) below 10% for WBPUs without additive (b) below 8% for WBPUs with additive. See Table 2.
Particle size and distribution of cationic waterborne polyurethanes can be divided by two types. Depending on chemical compositions, one type of cationic waterborne polyurethanes showed uniform particle size distribution and average particle diameter was in the range of about 20 to about 80 nm. The other type of cationic waterborne polyurethane showed large particle size and bimodal/multimodal particle size distribution as indicated by average particle sizes in the range of 100 to approximately 300 nm and large standard deviation of particle size. See Table 3.
The Young's modulus is a measure of the ability of a material to withstand changes in length when under uniaxial tension or compression. A higher Young's modulus typically indicates that the material is more rigid. The elongation at break, also known as fracture strain, is the ratio between changed length and initial length after breakage of the test specimen. A higher elongation at break expresses the capability of a material to resist fracture. For a composition applied to hair to hold the shape of the hair, the Young's modulus and elongation at break of the composition should be such that the composition provides rigidity to the hair but is not brittle.
A comparison of Young's modulus and the elongation at break for the some of the polyurethanes disclosed herein was made to several commercially available polyurethane products. The Young's modulus and the elongation at break can be determined by a protocol defined to measure mechanical properties is developed in compliance with ASTM D638, ASTM D412, test guidelines. In particular, the following protocol can be used to determine the Young's modulus and elongation at break (or ultimate elongation) of dry film of polyurethanes. Testing requires approximately 10-20 min per sample to complete.
Materials:
>25 g polyurethane aqueous dispersion
1 clean rectangular mold (2 mm×20 mm×45 mm) grooved on Teflon sheet per sample
1 clean razor blade
Scotch tape
Universal Testing Machine mounted with extension grip geometry
Sample Preparation:
Sample Testing
The moisture uptake properties, under highly humid environment, of WBPU dry films have been linked to their long lasting hold performance. As such, it is important to be able to reproducibly and accurately evaluate such moisture uptake properties to enable predictive in vitro and in vivo evaluation of WBPU dry films. The following protocol can be used to determine moisture uptake ability of WBPU dry films under high humid environment. Test requires about 2-3 days per sample set to complete
Materials
>15 g WBPU solution
1 clean cell culture petri dish (60 mm dia×15 mm H) per sample
Humidity chamber with flexibility to control temperature and relative humidity (RH)
Sample Testing
Sample Analysis
Calculate % moisture uptake using the following equation:
Since the isoelectric point (IEP, the pH at which a molecule or a substance carries no net electrical charge) of hair is about 3.67 (see Chemical and Physical Behavior of Human Hair, 5th ed.; p 388), the surface of hair bears a net negative charge at pHs above its IEP, where most hair care products are formulated. Anionic WBPUs which are often used in different hair care products, are therefore more likely to bind to hair surfaces by polar and Van der Waals interactions (see Chemical and Physical Behavior of Human Hair). By contrast, cationic WBPUs that carry opposite charges such as those described herein can bind to hair surfaces through the formation of ionic bonds. To achieve more enhanced performance, a new two-wave styling technology was developed, in which cationic and anionic WBPUs are used together to create synergistic styling properties. The detailed mechanism is shown in
To test the two-wave styling concept, systematic in vitro testing of cationic and anionic WBPUs was conducted. In all in vitro testing, a cationic WBPU was applied to a tress as an aqueous dispersion at 3 wt % polymer, and then an anionic WBPU was applied as an aqueous dispersions at 3 wt % polymer. The tress was blow dried for 90 seconds, then curled using ¾″ curling rod at 370° F. for 10 seconds and cooled in coiled formation. The tress was then subjected to 75% relative humidity at 25° C. for 15 minutes and then mechanically stressed by extending the tress to its original length, holding for 1 second, and releasing. Results show that both excellent high humidity curl retention and good sensory properties could be achieved.
As a preliminary screening, cationic and anionic WBPUs that were applied either in the first or second wave were tested alone. Results showed that cationic WBPU PU 363 showed better curl length and curl shape retention after high humidity. This was attributed to the strong ionic interactions between the WBPU, which has a relatively high cationic charge density, and inherently anionic hair surfaces. Further screening of all cationic WBPUs of different cationic charge densities showed that cationic WBPUs with higher charge densities provide better high heat curl retention (PU 363, PU 377, and PU 378).
When applied in a two-wave process where a cationic WBPU is first applied to the hair tress, a curl is styled, followed by the application of spray carrying an anionic WBPU; excellent high humidity curl retention was achieved.
In addition to the testing on hair tresses, extensive mannequin testing was conducted to evaluate the hold, sensory properties, and visual effects of the cationic polyurethanes. Both cationic and anionic WBPUs can be applied as either aqueous dispersions (
To validate the in vitro results, and to assess performance under normal hair care product use conditions, cationic and anionic WBPUs were applied as either 3 wt % aqueous dispersions or in different styling formulations. Although performance differences are less pronounced when compared with highly controlled in vitro testing, two-wave styling did consistently show improved performance compared to other styling methods, e.g., only anionic WBPU in both waves, in achieving strong hold and high humidity curl retention. See
When the cationic and the anionic WBPUs were incorporated into NoFrizz Conditioner or Curl Defining Styling Cream (available from Living Proof, Cambridge Mass.), respectively, the two-wave styling provided much better natural curl definition compared to the current formulations. See
In order to create a long-lasting hairstyle, a consumer must typically expend additional time and energy applying dedicated styling products to their hair after shampooing and conditioning. For many consumers, spending the time to apply these additional styling products is not feasible or desirable. Thus, there is a need in the market for more user-friendly, time-saving styling products. The cationic polyurethanes described herein can be leveraged to address this problem.
Hair conditioners are typically low pH (<7) formulations containing smoothening and conditioning molecules functionalized with positively charged quaternium functional groups, and are therefore incompatible with traditional anionic styling polymers used widely in the industry. However, when the cationic polyurethanes described herein are formulated in conditioners or leave-in-conditioners, the formulations were found to provide excellent style hold in addition to smoothing and conditioning. See e.g.,
Table 4 shows an exemplary list of conditioners and leave-in-conditioners comprising the disclosed cationic polyurethanes.
When conditioners containing the disclosed cationic polyurethanes are used in place of conditioners without the cationic polyurethanes, curl hold was significantly improved.
In addition to curl hold, conditioners containing the disclosed cationic polyurethanes can provide hold and stylability for blowout styles in which a stylist brushes the hair while blow drying in order to provide bounce, body and shape to the hair.
The incorporation of the disclosed cationic polyurethanes into conditioner also improves the smooth appearance of hair and minimizes flyaways, presumably by providing a thin, stiff coating around the hair fiber and serving as a hydrophobic layer that helps hairs maintain their straight style after blow drying.
Finally, conditioners containing cationic polyurethanes as described herein preserve curl shape in naturally curly-haired consumers.
The contents of all references (including literature references, issued patents, published patent applications, and co-pending patent applications) cited throughout this application are hereby expressly incorporated herein in their entireties by reference. Unless otherwise defined, all technical and scientific terms used herein are accorded the meaning commonly known to one with ordinary skill in the art.
This application claims priority to U.S. Provisional Application No. 62/655,273, filed Apr. 10, 2018 and U.S. Provisional Application No. 62/557,823, filed Sep. 13, 2017, the entire contents of each of which are incorporated herein by reference.
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