MXPA99001799A - Polyurethanes with functionality carboxylate for cable fixing applications - Google Patents

Abstract

The present invention relates to a polyurethane, soluble or dispersible in water, prepared from diols of organic diisocyanate or other isocyanate reactive materials and a diol of 2,2-hydroxymethyl substituted carboxylic acid neutralized with an organic or inorganic cosmetically acceptable base and formulated in a hair fixative composition containing low amounts of volatile organic solvent. The present invention also relates to a process for the preparation of polyurethanes which comprises dispersing the polyurethane after at least 70% of the theoretical isocyanate reaction has taken place, but before the completion of the reaction.

Description

POLYURETHANES WITH CARBOXYLATE FUNCTIONALITY FOR HAIR FIXING APPLICATIONS DESCRIPTION OF THE INVENTION This invention pertains to hair setting compositions comprising polyurethanes containing long free carboxyl groups neutralized with cosmetically acceptable standard bases, and a process for preparing the polyurethanes. Polyurethanes have been used for a wide variety of applications. Since the early seventies, aqueous dispersions of polyurethanes have expanded in utility. The incorporation of ionic salt groups in the polyurethane prepolymer before dispersing in water greatly facilitates the formation of the aqueous polyurethane dispersion. The aqueous polyurethane dispersion technology has matured considerably, however, the basic polyurethane in the polyurethane dispersion is the result of reacting a diisocyanate, a diol or a diamine (polyether, polyester, etc.) and a hydroxyl molecule or diol ( or analogous amine) containing an ionic salt group. The frequently used ionic saline groups are carboxylic acids, phosphoric sulphonic acids (or acids neutralized with bases), amine (or amine neutralized with acid), or groups of quaternary nitrogens. One of the most frequently used carboxylic reagents is dimethylolpropionic acid.

Aqueous polyurethane dispersions have been used extensively as adhesives and coatings in essentially any synthetic or natural substrate such as paper, wood, cotton, leather, wool and hair. Specific applications have been described in the pharmaceutical, cosmetic and hair setting areas. Recently applications of hair fixatives have focused on using hard polyurethanes which have a vitreous transition, Tg, above about room temperature. These hard, high Tg polyurethanes are used to provide the necessary hold and hold of the curl for hair fixers but suffer from the unpleasant, harsh aesthetic sense in the hair and fragility of the polyurethane which results in the development of flaking, roughness or difficulty for combing property. Most hair setting compositions contain a polymer that forms a film, which acts as the fixative, and a delivery system, which is usually an alcohol or a mixture of alcohol and water. In the case of aerosol delivery, the delivery system will also contain a propellant, which is typically a volatile hydrocarbon. Due to the environmental regulations that control the emission of volatile organic compounds (VOCs) in the atmosphere, these systems of supply with alcohol or hydrocarbons are becoming less acceptable, and it is expected that water will become a major component in the compositions of hair fixers. In addition, several different delivery systems for hair clippers are now used, for example spray for hair, both aerosols and pumps, gels and mousses. Hair fixation polymers taught for use in a water-based system are known, for example those described in Japanese publication JP 47-46332. However, many of these exhibit a loss of behavioral properties in aqueous systems, for example, curl retention and stiffness in the hair are inferior, and in other cases the viscosity of the solution is increased, and if it is supplied by aerosol , the composition foams in the valve actuator and in hair. In addition, current systems may also exhibit poor compatibility with aqueous supply systems. The performance requirements for hair fixers now demand that the hair fixative polymer maintain a high degree of hold, gloss, curl retention, stiffness, and moisture resistance, but still have pleasing aesthetics with a natural soft feel without tackiness adhesive, without roughness or feeling of fragility, without scale development and still be easily removable. These factors have pointed to the search for a polymer for hair fixatives for better performance that would be soluble or dispersible in low VOC or aqueous systems, that is, systems containing 80% or less of VOC. Current systems do not provide this balance of properties required. U.S. Patent No. 5,626,840 discloses polyurethanes prepared from an organic diisocyanate, a diol with a number average molecular weight greater than 1000, and a substituted 2, 2-hydroxymethyl carboxylic acid which are neutralized with an organic or inorganic base cosmetically acceptable and formulated in a hair fixative composition containing low amounts of the volatile organic solvent. The invention is directed to a process for preparing polyurethanes and to the use of polyurethanes in compositions of hair fixatives. The hair fixative composition of the present invention comprises a water soluble or dispersible polyurethane which, in spite of its solubility or dispersibility in water, also demonstrates good hold and flexibility, good compatibility with aerosol propellants, good dew characteristics, retention of the curl, rigidity, not stickiness, and forms a clear, transparent, shiny film that is easily removable with water (good rinsing) or with water and shampoo. The hair setting composition comprises (a) an effective amount of the polyurethane to function as a hair fixative in an entire system of water, alcohol, water, or all organic; (b) an effective amount of a cosmetically acceptable organic or inorganic base to neutralize a sufficient proportion of the carboxyl groups available in the polyurethane to render the polyurethane soluble or dispersible in water or in a mixture of water and an organic diluent; and (c) a diluent comprising (i) water, or (ii) water and 0 to about 90% by weight of an organic solvent, based on the weight of the solvent, or (iii) organic solvent. In order to achieve the balance of required properties, it has been found in the present that two different components with active hydrogen atoms, one that contributes in the rigidity and the other in the flexibility for the main structure of the polymer, in addition to the diol of carboxylic acid, are necessary for the preparation of polyurethane. The prior art has not taught or recognized the need for multiple polyols in the preparation of polyurethane for hair fixatives with the above balance of properties. The polyurethane is a fully reacted carboxylated polyurethane prepared as the reaction product of (i) one or more 2,2-hydroxymethyl substituted carboxylic acids present in an amount to give 0.35 to 2.25 milliequivalents of caarboxyl functionality per gram of polyurethane, (ii) 5 to 90% by weight, based on the weight of the polyurethane, of one or more organic components, other than the 2, 2-hydroxymethyl substituted carboxylic acids, each having at least two active hydrogen atoms, and (iii) one or more organic diisocyanates present in an amount sufficient to react with the active hydrogens of the 2, 2-hydroxymethyl substituted carboxylic acids and the organic components, except hydrogen in the carboxylic acid carboxylic acid 2, 2-hydroxymethyl substituted. The properties can be further improved by chain extension and chain termination. The hair setting composition can be used in sprays, aerosols, pumps, gels, mousses and lotions. In aerosol systems, the hair setting composition will also comprise up to 60% by weight of a propellant based on the weight of the total hair setting composition. The present invention is also directed to a process for preparing polyurethanes wherein the dispersion is carried out after at least 50%, but before completion, of the theoretical isocyanate reaction has taken place. Polyurethanes suitable for use in hair fixative formulations according to this invention are fully reacted carboxylated polymers. These polyurethanes are used in an effective amount to achieve the balance of desired properties, such as restraint, curl retention, stiffness, and moisture resistance, pleasant aesthetics with natural soft feel without adhesive tack, without roughness, or brittle feel, without flake development and that has rinse capacity. They are preferably present in amounts of 1 to 20% by weight of the hair fixative composition, and more preferably in amounts of 1 to 10% by weight. The incorporation of the 2,2-hydroxymethyl substituted carboxylic acid introduces long carboxylic acid groups in the polymer chain, which after neutralization leads to the polyurethane soluble or dispersible in water or in mixtures of water with other polar solvents. By using these polyurethanes as the active ingredient, hair setting formulations having a high solid content with low viscosity can be made. A high solids content delivers an effective amount of the polymer to the hair in a minimum amount of solvent to obtain good holding power. The low viscosity allows an effective atomization in the roll nozzle. In this way, a hair fixative product suitable for use in either aerosol or non-aerosol formulations can be obtained. However, in some cases, when high amounts of 2, 2-hydroxymethyl substituted carboxylic acids are incorporated to achieve good rinse capacity, this can be detrimental to flexibility, smooth feel, formulation compatibility and may increase the development of scale and roughness. The substituted 2, 2-hydroxymethyl carboxylic acids are represented by the formula CH, OH and R-C-COOH I CHjOH in which R represents hydrogen, or Ci- C20 alkyl, preferably Ci-Cß alkyl. Specific examples include 2,2-di (hydroxymethyl) acetic acid, 2,2-di (hydroxymethyl) propionic acid, 2,2-di- (hydroxy-methyl) butyric acid, 2,2-di (hydroxymethyl) propionic acid and Similar. The preferred acid is 2,2-di- (hydroxymethyl) propionic acid. The 2,2-hydroxymethyl substituted carboxylic acids are present in an amount to give 0.35 to 2.25, preferably 0.5 to 1.85, milliequivalents of carboxyl functionality per gram of polyurethane, and in general this is about 3 to 30% by weight of the polyurethane polymer. . The organic components which are reactive with isocyanate and which can be used for the preparation of the polyurethane polymers of this invention have at least two active hydrogen atoms (as determined by the Zerewitinoff method). Active hydrogen atoms are usually attached to oxygen, nitrogen or sulfur atoms. The organic components will be present in an amount of 10 to 90% by weight of the polyurethane, preferably in an amount of 15 to 70% by weight and can have a molecular weight less than 1000. Preferably, these components will be linear in such a way that it avoids gel formation during polymerization, but small amounts of non-linear components can be used to increase the properties with the proviso that it does not cause gel formation. One or more different organic components are used with active hydrogens. Alternatively, these different components can be combined into one component. These organic components will be designated components (A), (B) and (C). Component (A) is a polymer with at least two active hydrogen atoms having a Tg less than 5 ° C, preferably less than -10 ° C Tg. Specifically, component (A) can be, but is not limited to, a poly (alkylene oxide), for example a polyethoxylate, a polypropoxylate, a polyethoxylate / propoxylate, polymethylene oxide, polybutylene oxide, polyester diols, diols of polyolefin, poly (meth) acrylate diols, polysiloxane diamines or polysiloxane diols. The component (B) comprises a cyclic ring structure. Specifically (B) includes active hydrogen components containing rings of 5 to 14 members, wherein the rings may be heterocyclic, aliphatic, aromatic, cyclic, alicyclic, and / or spiro rings. Examples of such rings include cyclohexyl, cyclopentyl, norbornyl, phenyl, biphenyl, phenylether, Bisphenol A, hydrogenated bisphenol A, morpholino, pyrrolidinesujection, piperidine, pyridine, pyrrole, tetrahydropyran, furan, oxazole. Also included are the aromatic diols and their saturated hydrocarbon analogs disclosed in U.S. Patents 3,477,990 and 3,948,855. These rings are substituted with zero to sixteen alkoxylated units. Example components include the Synfac® 8000 series which are available from Milliken Chemicals, the Atlas® G-1600 series which is available from ICI Surfactants and the Macol® materials which are available from BASF. Component (C) can be used in place of or in addition to a combination of components (A) and (B), in addition to DMPA, and optionally other organic components containing active hydrogen atoms. Component (C) can be any of the cyclic ring structures described above with respect to component (B), however substituted with more than sixteen alkoxylated units Preferably, active hydrogen compounds of type (C) have selected ring components of the group consisting of Bisphenol A, hydrogenated bisphenol A, and mixtures thereof, wherein the rings are substituted with more than sixteen alkoxylated units The ring structures comprising components (B) and (C) may be substituted with H or with lower alkyl substituents of 1 to 4 carbon atoms.

To avoid unwanted side reactions, in the crosslinking and gelation of the polyurethane, preferably there is no substitution in the rings. This single organic component or more organic components with the active hydrogen component of the present invention can be one or more of A, B or C, specifically (A) + (B); (A) + (C); (B) + (C); (A) + (B) + (C); or (C). In preparing the polyurethanes, the organic components (A), (B) and (C) can be used in any combination in which each component comprises 5 to 90% of the polyurethane composition. For example, (A) and (B) may comprise 5 to 90% by weight of the polyurethane, and (C) may comprise 0 to 90% by weight of the polyurethane. In a preferred embodiment, the polyurethane will have a Tg value of less than about 5 ° C. In one embodiment, the polyurethane is prepared from a major amount of (A) and (B), which has molecular weights less than 1000. In another embodiment, the polyurethane is prepared from a major amount of (A) and (B) ), which have molecular weights greater than 1000. In preparing the polyurethane polymer, in addition to the organic component having at least two active hydrogen atoms, which in many cases is a high molecular weight component, it may be desirable to extend the polymer chain using another organic component that also has active hydrogen atoms. Typical chain extension agents include water, saturated or unsaturated glycols, such as, ethylene glycol, diethylene glycol, triethylene glycol and the like; amino alcohols, such as, ethanolamine, propanolamine, butanolamine, and the like; mono and dialkoxylated, aromatic, cycloaliphatic and heterocyclic primary aliphatic amines, such as, N-methyldiethanolamine, N-oleyldiethanolamine, N-cyclohexyldiisopropanolamine, N, N-dihydroethyl-p-toluidine, N, N-dihydroxypropylnaphthylamine and the like; amines, such as ethylenediamine, diethylene tetramine, triethylenetetramine, piperazine, N-N-bis-gamma-aminopropyl-N-methyl-amine, taurine, silicone diamine, Jeffamines® and the like; ethoxylated polyamines such as Jeffamines® series D and T; carboxylic acids including aliphatic, cycloaliphatic, aromatic and heterocyclic dicarboxylic acids, such as, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, terephthalic acid, 1,5-dicarboxyliconephthalic acid, maleic acid, fumaric acid , diglycolic acid, quinolinic acid, rutinic acid and the like; aminocarboxylic acids, such as, glycine, lysine, aspartic acid, iminodiacetic acid, alpha and beta alanine, 6-aminocaproic acid, 4-aminobutyric acid, p-aminobenzoic acid, 5-aminonaphtholic acid and the like; and amino acids such as glucamine, maltoamine and lactamine and the like.

Chain extenders may also be saccharide amines based on reducing sugars or those composed of glycosyl units linked by glycosidic linkages which are described in U.S. Patent No. 5,494,602. They may be linear or branched, and may be composed of a single type of glycosyl unit or may be composed of two or more different types of glycosyl units. Exemplary saccharides according to the present invention include, without limitation, starches, hydrolyzed starches, glucose, galactose, maltose, lactose, maltodextrins, corn syrup solids, cellulose, hydrolyzed cellulose, dextrans, hydrolyzed dextrans, guar gum, guar gum hydrolyzed, algarrobo bean gum and hydrolyzed algarrobo bean gum. Such starches include, for example, corn, potato, tapioca and rice starches. The saccharides used to prepare the polymers of the present invention are exemplified in U.S. Patent 5,494,602, which is incorporated herein by reference. The polyurethane polymer can also be chain terminated. The chain terminating agents include ethanol, isopropanol, taurine and the like. Also included are amino acids such as glucamine, maltamine, lactamine and the like. The organic polyisocyanates or mixtures of polyisocyanates reacted with the organic component are aliphatic or aromatic polyisocyanates, or mixtures thereof. The polyisocyanates are preferably diisocyanates in order to result in a linear polymer, although smaller amounts of trifunctional isocyanates may be used in conjunction with the diisocyanates. The isocyanate will be present in an amount sufficient to react with the active hydrogens of the 2,2-substituted hydroxymethyl carboxylic acid and the organic components, except for the hydrogen in the 2,2-hydroxymethyl substituted carboxylic acid carboxylate. This amount will vary depending on the amounts of the carboxylic acid and organic components. Exemplary diisocyanates include, but are not limited to, methylene di-p-phenyldiisocyanate, methylene-bis (4-cyclohexyl isocyanate), isophorone diisocyanate, toluene diisocyanate, 1,5-naphthalenediisocyanate, 4,4"-diphenylmethane diisocyanate, 2, 2"-dimethyl-4,4 '-diphenylmethane diisocyanate, 4,4" -dibenzyldiisocyanate, 1/3-phenylenediisocyanate, 1,4-diphenylene diisocyanate, mixtures of 2,4- and 2,6-toluenediisocyanate, 2,2'-dichloro -4,4"-diisocyanate diphenylmethane, 2,4-dibromo-1,5-diisocyanate naphthalene, butane-1,4-diisocyanate, hexane-1,6-diisocyanate, cyclohexane-1,4-diisocyanate, bis (1-) isocyanato-l-methylethyl) -benzene, and trimethylhexanomethylene diisocyanate. Preferably, the organic diisocyanate is selected from the group consisting of methylene-di-p-phenyl diisocyanate, methylene-bis- (4-cyclohexyl isocyanate), isophorone diisocyanate and toluene diisocyanate. If it is not desired to extend the polymer chain, the reaction of the diisocyanate with the organic component having two active hydrogen atoms is stopped by the addition of a monofunctional active hydrogen containing component to consume any residual isocyanate functionality. Examples of these arrest components are well known in the art; for these systems, such as monofunctional alcohols, monofunctional amines, and monofunctional low molecular weight polymers. The preferred stopping component is ethanol. The urethane polymerization is carried out in the reaction medium with or without typical urethane reaction catalysts known in the art. Suitable catalysts include dibutyl tin dilaurate; the stannous salts of carboxylic acids having 2 to 18 carbon atoms, such as, stannous laurate, stearate stearate, stannous acetate, stannous butyrate, stannous octoate and the like, and mixtures thereof. Other suitable catalysts include dibutyl tin oxide, dibutyl tin sulfide, lead resinate, lead benzoate, lead salicylate, lead 2-ethylhexoate, lead oleate, acetyl iron acetonate, cobalt benzoate, tetra (2-ethylhexyl) ) titanate, tetrabutyltitanate and the like. Many other components accelerate the reaction of a hydroxyl group or other groups with an isocyanate preferably for certain other isocyanate group reactions, and any of these components may be used. Those skilled in the art will select a specific catalyst to impart desired characteristics to individual urethane reactions. The foregoing specific components are the preferred components and are given for the purpose of illustration and not limitation. In addition, any suitable tertiary amine may be used alone or with the metallic catalyst, for example, triethylenedimaine, N-ethyl morpholine, N-methylmorpholine, or 4-dimethylaminoethylpiperazine, triethylamine, diazabicyclooctane. The polymerization is carried out according to the polyurethane polymerization techniques known in the art. With respect to the proportion of the reagents, the reagents must be selected in such a way that the molar ratio of the isocyanate groups to active hydrogen atoms is between 0.5: 1 and 2: 1, also referred to herein as the proportion of isocyanate / hydroxyl. These polymerizations can be either made solvent-free or in the presence of the solvent. In addition, the polymerization can be carried out in the presence of the surfactant or it can be free of surfactant. In systems where the solvent is used, techniques commonly known in the art can be used to remove the solvent, for example, steam distillation, vacuum distillation. Examples of polymerizations and reaction conditions are given in the examples. Other suitable methods are described in D. Dietrich, Progress in Organic Coatings, 9, 281 (1981), "Aqueous Emulsions, Dispersions and Solutions of Polyurethanes: Synthesis and Properties", and in J.. Rosthauser & K. Nachtkamp, Adv. Urethane Science & Technology, p. 121 (1987), "aterborne Polyurethanes", and in K. Tharanikkarasu and B.K. Kim in Progress in Rubber Plastics Technology, 13, p. 26 (1997). In carrying out the polymerization processes described above, for both solvent and solvent-free processes, it has been found here that it is useful to carry out the dispersion in water before the point where the total theoretical reaction of the isocyanate groups has been reached. Preferably, the dispersion is carried out after at least 50%, but before completion, of the theoretical isocyanate reaction has taken place; more preferably at least 70%. Standard analytical techniques, known in the art, can be used to monitor the degree of isocyanate reaction in this process, for example, isocyanate titration or other spectroscopic methods. Furthermore, in some cases, it has been found that the slow addition of the neutralizing base facilitates the polymerization process, for example, to avoid exothermic reactions. This polymerization process can be used to advantage particularly in systems where the isocyanate / hydroxyl ratio is less than 1, preferably where the isocyanate / hydroxyl ratio is 0.8 to 0.99. This facilitates the aqueous dispersion stage avoiding excessively high viscosity in the prepolymer, and has the advantage of allowing chain termination and / or chain extension to occur, as in systems where the isocyanate / hydroxyl ratio is greater than 1. This process can provide performance benefits to the fixing composition of hair. In most cases, polyurethanes are either chain extended or chain terminated. In addition to the polyurethanes, the polymeric hair setting compositions can be polyureas or thiol analogs, particularly in cases where the isocyanate-reactive groups are diamines or thiols or chain-extended with water, amine or alcohol reagents. This process is not limited to the preparation of polyurethanes for hair care compositions, but can be used to prepare any type of polyurethanes for any application, including for example, coatings, fibers, adhesives, sizing agents, etc. The carboxylated polyurethanes are neutralized by standard cosmetically acceptable bases known and used in the art, and these can be used individually or in combination. Preferred levels of neutralization greater than 30% may be used, and in some cases greater than a stoichiometric amount of neutralizing, depending on the acidity of the polymer. Preferred bases are sodium hydroxide, potassium hydroxide, 2-amino-2-methyl-1-propane, histidine, tris (hydroxymethyl) aminomethane, triisopropanolamine, stearamine, triethanolamine and triethylamine. The choice of base and the degree of neutralization also affect the flexibility of the resulting hair fixative when sprayed on the hair, giving a soft or hard hold. One or more of the bases can be used, and the choice of the base or bases to be used and the degree of neutralization required to achieve flexibility are within the experience of a person skilled in the art. The hair fixative polyurethane of the present invention may be used with or without other hair fixation polymers known in the art such as vinyl acetate / vinyl neodecanoate copolymer, octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer, vinyl acetate / crotonates, polyvinylpyrrolidone (PV), polyvinylpyrrolidone / vinyl acetate copolymer, PVP / acrylate copolymer, vinyl acetate / crotonic acid / vinyl propionate, acrylate / hydroxyacrylate copolymer, and polyvinylmethylether / maleic anhydride alkyl esters, copolymers of diglycol / cyclohexanedimethanol / isophthalates / sulfoisophthalates, vinyl acetate / butyl maleate and isobornyl acrylate copolymer, vinylcaprolactam / PVP / dimethylaminoethyl methacrylate terpolymers, vinyl acetate terpolymers / alkylmaleate / N-substituted acrylamide ester, vinyl caprolactam / vinylpyrrolidone / methacrylamidopropyltrimethylammonium chloride, tacrilates / copolymer acrylates / amine salt, polyvinylcaprolactam, other polyurethanes and others. The proportion of the hair fixing polymers in such a mixture can vary depending on the desired functions and can be adjusted by those skilled in the art. The neutralization leads to the polymers to be soluble or dispersible in water for easy formulation in sprays of watery hair (and in this way contributes to elimination capacity). The neutralized polymers can be formulated only in water as the solvent, or the diluent system can be a mixture of the polar organic solvent and water, or can be only an organic solvent. Typically, the organic solvent will be an alcohol or ketone. Particularly suitable solvents are low boiling alcohols which are compatible with other components in the hair setting composition, for example, branched or straight chain alcohols of C 1 -C 4. Examples of polar solvents are ethanol, propanol, isopropanol, butane, pethane, acetone, dimethyl ether, methyl ethyl ketone, methyl acetate and dimethoxymethane. The organic solvent is present in an amount up to about 99% by weight of the total hair setting composition. In a modality, the hair setting composition is anhydrous. Hair setting compositions that are proposed to be delivered in an aerosol system will additionally require a propellant. While any of the known propellants in these compositions may be used, preferred propellants include hydrocarbons, particularly lower boiling hydrocarbons such as straight or branched chain hydrocarbons of C3-C6, eg, propane, butane, isobutane and mixtures of these. Other preferred propellants include the ethers, such as dimethyl ether, hydrofluorocarbons, such as 1,1-difluoroethane; and compressed gases, such as nitrogen, air and carbon dioxide. The amount of propellant used in the hair setting compositions of this invention may vary from about 0 to 70% by weight of the hair spray composition and preferably from about 0 to 40% by weight, based on the weight of the total composition . An important consideration in determining the amount of the organic solvent, or organic solvent and propellant, to be used in the hair setting composition is the total amount of volatile organic component (VOC) content, and any upper limit of VOC content that can be used. be regulated by environmental regulations. While these compositions may have a broad range of VOC content, from completely aqueous to completely anhydrous, due to current environmental regulations it is preferred that it be less than about 80%, more preferably less than about 55%, and more preferably less than about 20% by weight of the VOC content, based on the weight of the composition. The balance of the hair setting composition will be water and polyurethane. Optional conventional additives may also be incorporated into the hair setting composition of this invention to provide certain modifying properties to the composition. Included among these plasticizer additives, such as glycerin, glycol esters and phthalate; silicones, emollients, lubricants and penetrants, such as lanolin components, fragrances and perfumes; UV absorbers; dyes and other colorants; specifiers; anticorrosion agents; detaching agents; styling aids; antistatic agents; conservatives; and foam stabilizers. These additives are present in small amounts, effective to perform their function and will generally comprise from about 0.1 to 10% by weight of each, and from about 0.1 to 20% by total weight, based on the weight of the composition. The resulting hair setting compositions exhibit all of the required characteristics of such a system product in the range from fully aqueous to completely anhydrous. The compositions can be used in cosmetic applications, particularly in hair fixatives such as aerosol sprays, pumps, mousses, lotions and gels. The following examples of the present invention are illustrated and are not intended to limit the scope of the present invention in any way. EXAMPLES Preparation of polyurethanes Example 1 A 2-liter reaction vessel, equipped with a stirrer, heating blanket, and a condenser and nitrogen purge is charged with 76 g of 1025 molecular weight polypropylene glycol and 42 g of Synfac® 8031 (Milliken Chemicals). The mixture is heated at 120 ° for 30 minutes and then cooled to 80 ° C. 47.5 g of dimethylolpropionic acid are added to the mixture and dispersed for 10 minutes. The mixture is cooled to 60 ° C and acetone is added followed by 125 g of isophorone diisocyanate. The mixture is heated to 77 ° C and allowed to react for 45 minutes. Finally, 39.5 grams of triethylamine are added, and the prepolymer is dispersed with vigorous stirring in 613 g of water. An additional 5.4 g of triethylamine is then added. The resulting dispersion is stable, and the dry polymer exhibits a Tg of -7 ° C (DSC). Example 2 A 2 liter reaction vessel, equipped with a stirrer, heating mantle, and a condenser and nitrogen purge is charged with 76 g of 1025 molecular weight polypropylene glycol and 67.3 g of Synfac® 8009 (Milliken Chemicals). The mixture is heated at 120 ° for 30 minutes and then cooled to 80 ° C. 47.5 g of dimethylolpropionic acid are added to the mixture and dispersed for 10 minutes. The mixture is cooled to 60 ° C and 30 g of acetone are added followed by 125 g of isophorone diisocyanate. Reagents are heated to 77 ° C and reacted for 1 hour. After one hour, 39.5 grams of triethylamine are added, and the prepolymer is dispersed with vigorous stirring in 783 g of water. Finally, an additional 5.4 g of triethylamine is added. EXAMPLE 3 A 2-liter reaction vessel equipped with a stirrer, heating mantle, and a condenser and nitrogen purge is charged with 76 g of 1025 molecular weight polypropylene glycol and 42 g of Synfac® 8031 (Milliken Chemicals). The mixture is heated at 120 ° for 30 minutes and then cooled to 80 ° C. 48 g of dimethylolpropionic acid are added to the mixture and dispersed for 10 minutes. The mixture is cooled to 40 ° C and 66 g of acetone are added followed by 133 g of isophorone diisocyanate. After stirring for 10 minutes, 39.5 g of triethylamine is added dropwise. The reaction temperature is brought to 60 ° C. The reaction is allowed to proceed for about 40 minutes at 60 ° C. The prepolymer is dispersed with vigorous stirring in 179 g of water in which 44.5 g of Jeffamine® M-1000 has been predisposed. 418 g of water are used to dilute the dispersion. The resulting stable white dispersion is then treated with steam to remove the acetone. EXAMPLE 4 A 2 liter reaction vessel, equipped with a stirrer, heating mantle, and a nitrogen purge and condenser is charged with 67 g of 1025 molecular weight polypropylene glycol, 26.8 g of molecular weight polypropylene glycol 425 and 21 g of Synfac® 8009 (Milliken Chemicals). The mixture is heated at 120 ° for 30 minutes and then cooled to 80 ° C. 72 g of dimethylolpropionic acid are added to the mixture and dispersed for 10 minutes. The mixture is cooled to 40 ° C and 177 g of methylene-bis (4-cyclohexyl isocyanate) is added. After stirring for 10 minutes, 60 g of triethylamine is added dropwise for one hour, 30 g of acetone is also added. The reaction temperature is brought to 60 ° C. The reaction is allowed to proceed for an additional 20 minutes at 60 ° C. The prepolymer is then dispersed in 79 g of water with vigorous stirring. An additional 613 g of water is used to dilute the dispersion. The resulting stable white dispersion is then treated with steam to remove the acetone. Example 5 A 2-liter reaction vessel, equipped with a stirrer, heating blanket, and a condenser and nitrogen purge is charged with 152 g of 1025 molecular weight polypropylene glycol and 84 g of Synfac® 8031 (Milliken Chemicals) . The mixture is heated at 120 ° for 30 minutes and then cooled to 80 ° C. 96 g of dimethylolpropionic acid are added to the mixture and dispersed for 10 minutes. The mixture is cooled to 70 ° C and 266.4 g of isophorone diisocyanate are added. The mixture is heated to 80 ° C and allowed to react for 90 minutes, until the NCO level is 4.3% (after the 71.3% isocyanate reaction has taken place). Finally, 79.74 grams of triethylamine are added, and the prepolymer is dispersed with vigorous stirring in 1196.8 g of water. An additional .87 g of triethylamine followed by 250 g of water is then added. The resulting dispersion is stable, at 29.9% solids, at a viscosity of 30 cps at a pH of 8.8.

Example 6 A 2 liter reaction vessel, equipped with a stirrer, heating mantle, and a condenser and nitrogen purge is charged with 76 g of 1025 molecular weight polypropylene glycol and 67.3 g of Synfac® 8009 (Milliken Chemicals). The mixture is heated at 120 ° for 30 minutes and then cooled to 80 ° C. 47.5 g of dimethylolpropionic acid are added to the mixture and dispersed for 10 minutes. The mixture is cooled to 70 ° C and 125 g of isophorone diisocyanate is added. The reactants are heated to 80 ° C and allowed to react for approximately ninety minutes. The reaction mixture is cooled to about 65 ° C and then 39.5 grams of triethylamine is added, and the prepolymer is dispersed with vigorous stirring in 688.1 g of water. Finally, an additional 5.4 g of triethylamine is added. The final solids are in 29.9%, pH 7.8 and viscosity of 95 cps. Example 7 A 2 liter reaction vessel, equipped with a stirrer, heating mantle, and a nitrogen purge and condenser is charged with 152 g of 1025 molecular weight polypropylene glycol and 84 g of Synfac® 8031 (Milliken Chemicals). The mixture is heated at 120 ° for 30 minutes and then cooled to 80 ° C. 96 g of dimethylolpropionic acid are added to the mixture and dispersed for 10 minutes. The mixture is cooled to 65 ° C and 266.4 g of isophorone diisocyanate is added. The temperature of the reaction is allowed to increase to about 80 ° C. After one hour, 0.5 g of dibutyl tin dilaurate is added. The reaction is allowed to continue for approximately 30 minutes more. The reaction mixture is cooled to about 65 ° C and then 79.74 g of triethylamine is added. The prepolymer is then dispersed with vigorous stirring in 359 g of water in which 89 g of Jeffamine® M-1000 has been pre-dissolved. An additional 837.8 g of water is used to dilute the dispersion. This is followed by the addition of 10.87 g of triethylamine. The resulting stable dispersion has 36% solids, a viscosity of 126 cps and a pH of 8.4. Example 8 A 2 liter reaction vessel, equipped with a stirrer, heating mantle, and a nitrogen purge and condenser is charged with 67 g of 1025 molecular weight polypropylene glycol, 26.8 g of polypropylene glycol of molecular weight of 425, and 21 g of Synfac® 8009 (Milliken Chemicals). The mixture is heated at 120 ° for 30 minutes and then cooled to 80 ° C. 72 g of dimethylolpropionic acid are added to the mixture and dispersed for 10 minutes. The mixture is cooled to 65 ° C and 177 g of methylene-bis (4-cyclohexyl isocyanate) is added. The reaction temperature is then increased to about 80 ° C and maintained for about 90 minutes at this temperature, followed by the addition of 59.8 g of triethylamine. The prepolymer is then dispersed with vigorous stirring in 79 g of water. An additional 369 g of water is used to dilute the dispersion. The resulting stable dispersion is initially foamy and then becomes translucent after the foam disappears. EXAMPLE A 2 liter reaction vessel, equipped with a stirrer, heating mantle, and a condenser and nitrogen purge is charged with 76 g of 1025 molecular weight polypropylene glycol and 42 g of Synfac® 8031 (Milliken Chemicals). The mixture is heated at 120 ° for 30 minutes and then cooled to 80 ° C. 48 g of dimethylolpropionic acid are added to the mixture and dispersed for 10 minutes. The mixture is cooled to 70 ° C and 266.4 g of isophorone diisocyanate is added followed by the addition of 0.2 g of dibutyl tin dilaurate. The mixture is heated to 80 ° C and allowed to react for one hour. The prepolymer is cooled to 55 ° C. 30 g of Ploronic® F108 are dissolved in 90 g of acetone and added to the reaction vessel. The mixture is dispersed with vigorous stirring in 440 g of water. The acetone is then removed by distillation in vacuo. The resulting dispersion is stable at 43.1% solids, at a viscosity of less than 50 cps. EXAMPLE 10 A 2-liter reaction vessel equipped with a stirrer, heating mantle, and a condenser and nitrogen purge is charged with 76 g of 1025 molecular weight polypropylene glycol and 42 g of Synfac® 8031 (Milliken Chemicals). The mixture is heated at 120 ° for 30 minutes and then cooled to 80 ° C. 48 g of dimethylolpropionic acid are added to the mixture and dispersed for 10 minutes. The mixture is cooled to 60 ° C and 133.2 g of isophorone diisocyanate is added. The reaction temperature is allowed to increase to about 80 ° C. After one hour, 0.2 g of dibutyltin dilaurate is added. The reaction is allowed to continue for another hour and a half. The reaction mixture is cooled to about 55 ° C. 44.5 g of Jeffamine® M-1000 is dissolved in 35 g of acetone and added to the reaction vessel. The mixture is dispersed with vigorous stirring in 300 g of water. The acetone is then removed by vacuum distillation. The resulting dispersion is stable at 50.6% solids, at a viscosity of less than 1000 cps. Example 11 A 2-liter reaction vessel equipped with a stirrer, heating mantle, and a condenser and nitrogen purge is charged with 76 g of 1025 molecular weight polypropylene glycol and 42 g of Synfac® 8031 (Milliken Chemicals). The mixture is heated at 120 ° for 30 minutes and then cooled to 80 ° C. 47.5 g of dimethylolpropionic acid are added to the mixture and dispersed for 10 minutes. The mixture is cooled to 65 ° C and 133.2 g of isophorone diisocyanate is added. The reaction temperature is allowed to increase to about 65 ° C and then 39.46 g of triethylamine is added. The mixture is dispersed with vigorous stirring in 179.2 g of water in which 22.25 g of Jeffamine® M-1000 and 22.5 g of reductively aminated maltodextrin, saccharide monoamine (molecular weight 2560) have been predisposed. An additional 418.2 g of water is used to dilute the dispersion. This is followed by the addition of 5.38 g of triethylamine. The resulting stable dispersion has solids at 36.9%, viscosity of 165 cps and pH of 7.9. Example 12 A 2 liter reaction vessel, equipped with a stirrer, heating mantle, and a condenser and nitrogen purge is charged with 76 g of 1025 molecular weight polypropylene glycol and 42 g of Synfac® 8031 (Milliken Chemicals). The mixture is heated at 120 ° for 30 minutes and then cooled to 80 ° C. 47.5 g of dimethylolpropionic acid are added to the mixture and dispersed for 10 minutes. The mixture is cooled to 60 ° C and 133.2 g of isophorone diisocyanate is added. The reaction temperature is allowed to increase to about 80 ° C. The reaction is allowed to continue for approximately two and a half hours. The reaction mixture is cooled to about 65 ° C and then 39.46 g of triethylamine is added. The prepolymer is dispersed with vigorous stirring in 179.2 g of water in which 44.5 g of reductively aminated maltodextrin, monoamine saccharide (molecular weight 2560) has been predisposed. An additional 418.2 g of water is used to dilute the dispersion. This is followed by the addition of 5.38 g of triethylamine. The resulting stable dispersion has 36% solids, a viscosity of 190 cps and a pH of 8. EXAMPLE 13 A 2-liter reaction vessel equipped with a stirrer, heating blanket, and a condenser and nitrogen purge with 76 g of polypropylene glycol of 1025 molecular weight and 42 g of Synfac® 8031 (Milliken Chemicals). The mixture is heated at 120 ° for 30 minutes and then cooled to 80 ° C. 48 g of dimethylolpropionic acid are added to the mixture and dispersed for 10 minutes. The mixture is cooled to 65 ° C and 133.2 g of isophorone diisocyanate is added. The reaction temperature is allowed to increase to about 80 ° C. After one hour, 0.25 g of dibutyl tin dilaurate is added. The reaction is allowed to continue for about an hour and a half. The reaction mixture is cooled to about 65 ° C and then 35.8 g of triethylamine is added. The prepolymer is then dispersed with vigorous stirring in 179.2 g of water in which 5.92 g of iminodiacetic acid has been predisposed after neutralization with triethylamine. An additional 418.9 g of water is used to dilute the dispersion. This is followed by the additional addition of 100 g of water. The resulting stable dispersion has 31.1% solids, viscosity of 52 cps and a pH of 8. Example 14 A 2 liter reaction vessel, equipped with a stirrer, heating mantle, and a condenser and nitrogen purge is charged with 76 g of 1025 molecular weight polypropylene glycol and 42 g of Synfac® 8031 (Milliken Chemicals). The mixture is heated at 120 ° for 30 minutes and then cooled to 80 ° C. 47.5 g of dimethylolpropionic acid is added to the mixture and added and allowed to disperse for 10 minutes. The mixture is cooled to 65 ° C and 133.2 g of isophorone diisocyanate is added. It is allowed to increase the reaction temperature to about 80 ° C. The reaction is allowed to continue for approximately 2 hours. The reaction mixture is cooled to about 65 ° C and then 39.46 grams of triethylamine is added. The prepolymer is dispersed with vigorous stirring in 179.2 g of water in which 22.5 g of Jeffamine® M-1000 and 5.29 g of iminodiacetic acid have been predisposed. An additional 418.2 g of water is used to dilute the dispersion. This is followed by the addition of 5.38 g of triethylamine. The resulting stable dispersion has 35.6% solids, viscosity 110 cps and pH 7.1. Example 15 A 2 liter reaction vessel, equipped with a stirrer, heating mantle, and a condenser and nitrogen purge is charged with 76 g of 1025 molecular weight polypropylene glycol and 42 g of Synfac® 8031 (Milliken Chemicals). The mixture is heated at 120 ° for 30 minutes and then cooled to 80 ° C. 47.5 g of dimethylolpropionic acid are added to the mixture and dispersed for 10 minutes. The mixture is cooled to 60 ° C and 133.2 g of isophorone diisocyanate is added. It is allowed to increase the reaction temperature to about 80 ° C. The reaction is allowed to continue for approximately 2 hours. The reaction mixture is cooled to about 65 ° C and then 39.46 grams of triethylamine is added. The prepolymer is dispersed with vigorous stirring in 179.2 g of water in which 5.0 g of taurine has been predisposed. An additional 418.2 g of water is used to dilute the dispersion. This is followed by the addition of 5.38 g of triethylamine. The resulting stable dispersion has 34.8% solids, viscosity of 150 cps and pH of 7.1. Example 16 A 2 liter reaction vessel, equipped with a stirrer, heating mantle, and a condenser and nitrogen purge is charged with 76 g of 1025 molecular weight polypropylene glycol and 42 g of Synfac® 8031 (Milliken Chemicals). The mixture is heated at 120 ° for 30 minutes and then cooled to 80 ° C. 47.5 g of dimethylolpropionic acid are added to the mixture and dispersed for 10 minutes. The mixture is cooled to 65 ° C and 133.2 g of isophorone diisocyanate is added. It is allowed to increase the reaction temperature to about 80 ° C. The reaction is allowed to continue for approximately 2 hours. The reaction mixture is cooled to about 65 ° C and then 39.46 grams of triethylamine is added. The prepolymer is then dispersed with vigorous stirring in 89.6 g of water in which 5.0 g of taurine has been dissolved. This is immediately followed by the addition of 89.6 g of water in which 22.25 g of Jeffamine® M-1000 has been predisposed. An additional 418.2 g of water is used to dilute the dispersion. This is followed by the addition of 5.38 g of triethylamine. The resulting stable dispersion has 35.2% solids, viscosity of 65 cps and pH of 8.4. Example 17 A 2 liter reaction vessel, equipped with a stirrer, heating mantle, and a condenser and nitrogen purge is charged with 100 g of polypropylene glycol of 1025, 20 g of polypropylene glycol of molecular weight 425 and 5 g of bisphenol A hydrogenated (Milliken Chemicals). The mixture is heated at 120 ° for 30 minutes and then cooled to 80 ° C. 72 g of dimethylolpropionic acid are added to the mixture and dispersed for 10 minutes. The mixture is cooled to 40 ° C and 83 g of acetone are added followed by 177 g of methylene-bis (4-cyclohexyl isocyanate). After stirring for 10 minutes, 60 g of triethylamine is added in drops. The reaction is allowed to proceed for an additional 70 minutes at 60 ° C. The prepolymer is then dispersed in 79 g of water with vigorous stirring. An additional 613 g of water is used to dilute the dispersion. Example 18 A 2-liter reaction vessel equipped with a stirrer, heating mantle, and a condenser and nitrogen purge is charged with 76 g of 1025 molecular weight polypropylene glycol and 50.5 g of Synfac® 8031 (Milliken Chemicals). The mixture is heated at 120 ° for 30 minutes and then cooled to 80 ° C. 36.1 g of cyclohexanedimethanol and 47.5 g of dimethylolpropionic acid are added to the mixture and dispersed for 10 minutes. The mixture is cooled to 65 ° C and 125 g of isophorone diisocyanate is added. The reaction is allowed to continue for approximately one hour. The reaction mixture is cooled to about 65 ° C and then 39.46 grams of triethylamine is added. The prepolymer is dispersed with vigorous stirring in 467 g of water. The resulting stable dispersion is white and foamy. Example 19 A 2-liter reaction vessel, equipped with a stirrer, heating mantle, and a condenser and nitrogen purge is charged with 76 g of 1025 molecular weight polypropylene glycol and 42 g of Synfac® 8031 (Milliken Chemicals). The mixture is heated at 120 ° for 30 minutes and then cooled to 80 ° C. 47.5 g of dimethylolpropionic acid are added to the mixture and dispersed for 10 minutes. The mixture is cooled to 60 ° C and 64 g of acetone is added followed by 144 g of 4,4"-methylenebis (phenylisocyanate) The mixture is allowed to react for 45 minutes Finally, 39.5 grams of triethylamine are added and The prepolymer is dispersed with vigorous stirring in 179 g of water and diluted with an additional 613 g of water, then an additional 5.4 g of triethylamine is added Example 20 A 2 liter reaction vessel equipped with a stirrer is charged. heating, and a nitrogen purge and condenser with 76 g of 1025 molecular weight polypropylene glycol and 42 g of Synfac® 8031 (Milliken Chemicals) The mixture is heated at 120 ° for 30 minutes and then cooled to 80 ° C. 47.5 g of dimethylolpropionic acid is added to the mixture and allowed to disperse for 10 minutes, the mixture is cooled to 60 ° C and 64 g of acetone are added, followed by 70 g of 4,4"-methylenebis (phenylisocyanate) and 73.5 g. g of 4,4"-methylenebis (cyclohexyl isocyanate). ionar the mixture for 45 minutes. Finally, 39.5 grams of triethylamine are added, and the prepolymer is dispersed with vigorous stirring in 179 g of water, and diluted with an additional 613 g of water. An additional 5.4 g of triethylamine is then added.

Example 21 A 2 liter reaction vessel, equipped with a stirrer, heating mantle, and a condenser and nitrogen purge is charged with 76 g of 1025 molecular weight polypropylene glycol and 42 g of Synfac® 8031 (Milliken Chemicals). The mixture is heated at 120 ° for 30 minutes and then cooled to 80 ° C. 47.5 g of dimethylolpropionic acid are added to the mixture and dispersed for 10 minutes. The mixture is cooled to 60 ° C and 64 g of acetone is added followed by 70 g of 4,4"-methylenebis (phenylisocyanate) After 15 minutes, 73.5 g of 4,4" -methylenebis (cyclohexyl isocyanate) is added. The mixture is allowed to react for 20 minutes. Finally, 39.5 grams of triethylamine are added, and the prepolymer is dispersed with vigorous stirring in 179 g of water, and diluted with an additional 613 g of water. An additional 5.4 g of triethylamine is then added. Example 22 A 2 liter reaction vessel, equipped with a stirrer, heating mantle, and a nitrogen purge and condenser is charged with 152 g of 1025 molecular weight polypropylene glycol and 84 g of Synfac® 8031 (Milliken Chemicals). The mixture is heated at 120 ° for 30 minutes and then cooled to 80 ° C. 96 g of dimethylolpropionic acid are added to the mixture and dispersed for 10 minutes. The mixture is cooled to 70 ° C and 266.4 g of isophorone diisocyanate are added. The mixture is heated to 80 ° C and allowed to react for 120 minutes. The prepolymer is dispersed with vigorous stirring in 35.82 g of NaOH dissolved in 1146.8 g of water. Example 23 A 2 liter reaction vessel, equipped with a stirrer, heating mantle, and a condenser and nitrogen purge is charged with 35 g of 1025 molecular weight polypropylene glycol and 79 g of TONE 201 (Union polyester polyol). Carbide). The mixture is heated at 120 ° for 30 minutes and then cooled to 80 ° C. 46.9 g of dimethylolpropionic acid are added to the mixture and dispersed for 10 minutes. The mixture is cooled to 65 ° C and 100 g of isophorone diisocyanate is added. The reaction temperature is allowed to increase to approximately 80 ° C. The reaction is allowed to continue for approximately one and a half hours, 5.77% NCO, until 60% of the isocyanate reaction takes place. The reaction mixture is cooled to about 65 ° C and then 38.96 grams of triethylamine is added. The prepolymer is then dispersed with vigorous stirring in 184.5 g of water. This is immediately followed by the addition of 250 g of water and 5.3 g of triethylamine. The resulting stable dispersion has 34.28% solids, a viscosity of 90 cps and a pH of 9. Comparative Example A A 2 liter reaction vessel, equipped with a stirrer, heating mantle, and a condenser and nitrogen purge is charged with 150 g of polypropylene glycol of 2025 molecular weight. The mixture is heated at 120 ° for 30 minutes and then cooled to 80 ° C. 12 g of dimethylolpropionic acid are added to the mixture and dispersed for 10 minutes. The mixture is cooled to 60 ° C and 66 g of isophorone diisocyanate is added. The mixture is allowed to react for 3 hours at 80 ° C. Finally, 10 grams of triethylamine are added, and the prepolymer is dispersed with vigorous stirring in 464 g of water. Preparation of hair formulation compositions and working examples Example 24 Hair setting formulations The polyurethanes of the previous examples are formulated in spray hair spray systems with few VOCs according to the following formulations. All values are reported in parts by weight, based on the total weight of the hair spray composition.

Ingredient Parts by weight (dry basis) Alcohol-free 55% VOC (33% VOC) Polyurethane polymer 5.0 5.0 Anhydrous ethanol 22.0 Deionized water 62.0 40.0 Dimethyl ether 33.0 33.0 100.0 100.0 Mix polyurethane polymer, ethanol and deionized water until dissolved ho ogenity. The solutions are filtered and filled with these aerosol containers. The cans are loaded with dimethyl ether propellant. Spray formulations for hair are tested for spray characteristics and samples of 2 grams of European brown hair. Sprays are supplied with a SEAQUIST NS-34 valve (steam cap 0. 013 inches x 0.013 inch root hole x 0.040 inch deep pipe diameter) that have acted EXCEL 200 MISTY (0.016 inch hole) in a second rut from a distance of six inches (15.24 cm). The formulas are compared to control A (comparative example A in 5% solids, 33% aerosol VOC) and Control B (commercially available VA / crotonate / vinyl neodecanoate copolymers in 5% solids, anhydrous aerosol).

Example 25 Spray Characteristics Assessments The spray characteristics of alcohol-free aerosols (33% VOC) and 55% VOCs are classified on a scale from A to F, with A being the best spray. An "A" rating indicates a wide spray cone, fine spray, small particle size and no foam in the hair or actuator. A "F" rating indicates narrow spray cone, dividing in the actuator, large particle size and obvious foam in the hair or actuator. The average particle size of the sprays is measured by a 2600 series particle and droplet analyzer from Malvern Instruments Inc. of Southborouggh, MA. The results are listed in Table 1: Table 1: Spray characteristics Polymer% VOC in Particle size Classification aerosol medium (μ) dsl dew Example 6 33 31.34 A Example 7 33 32.87 B + Example 8 33 29.43 A Example 9 33 40.66 B + Example 10 33 3.51 A- Example 13 33 42.10 B + Example 14 33 32.73 A- Example 15 33 32.27 A- Example 16 33 29.58 A- Control A 48.40 B + PolllTlßr * r > % VOC in uarticj-ÜLa _ _average aerosol size (μ) ro_cj_o. Example 6 55 45.25 B + Example 7 55 41.42 B Example 8 55 34.94 A- Example 9 55 56.03 c + Example 10 55 48.51 c + Example 13 55 51.71 B- Example 14 55 44.87 c + Example 15 55 42.58 C + Example 16 55 46.81 C + Control A 55 > 150 F The data clearly shows that these exemplary polymers provide acceptable spraying capacity in both water based and alcohol / water based aerosol systems, while control a has difficulty in spraying from systems containing alcohol. EXAMPLE 26 Taber Stiffness Testing Procedure Spray formulations for alcohol free spray hair prepared from Examples 5, 6, 7 and 8 are tested as described in Example 24, for stiffness in three 4 1/2 inch samples ( 11.43 cm) of European brown virgin hair and the results are averaged and averaged. The samples are first dried in an oven at 110 ° F (43 °) for 30 minutes to remove moisture and then dried in a desiccator for 15 minutes. The samples are weighed and the weight recorded as x. Each sample is sprayed with a hair spray formulation for one second and then attached to a retainer board and dried in an oven at 110 ° F (43 ° C) for 15 minutes. The samples are cooled in the desiccator and reweighed. This weight is recorded as W2. The samples are then placed for equilibrium overnight at 50% relative humidity and 23 ° C.

Stiffness is tested using a stiffness tester Taber V-5 from Taber Industries of North Tonawanda, NY, designed to evaluate the stiffness and elasticity of paper, cardboard and other flexible materials. The following procedure and calculation are adapted for use with the samples. When the machine is turned on, the interior optical encoder must be oriented before use. To do this, turn the impulse disk to the left and right beyond zero, using the control lever switch; then it returns to zero. Then, balance the pendulum by adjusting the levers on the lower part of the two front ends until the line on the pendulum is directly below the zero line on the graduated scale at 100. Sliding the weight of 500 units on the ledge in the lower part of the pendulum. This weight multiplies each dial indication by five times. The sample is inserted between the clamping jaws, with the lower edge resting slightly on the lower caliber. Fasten the clamping jaws by changing the screws on either side of the clamp. The sample is centered between the lower rollers using the left screw to move the manual roller to the left until it makes contact with the sample, do not deviate the pendulum from zero. The right hand roller is then brought into contact with the sample using the right roller screw. With one finger, light pressure is applied to the control lever switch and the drive disk is shifted to the left until the pendulum line is under the 15 ° deviation mark. The stiffness reading is recorded on the outer scale that falls opposite the zero line on the drive disk (LS). The same sample is deviated by 15 ° and that stiffness reading (RS) is taken. The left and right readings are averaged and multiplied by five to give the stiffness value for that sample. The results of the rigidity evaluations are listed in Table 2: Table 2: Taber stiffness evaluation test Polymer Rigidity Example 5 223 Example 6 273 Example 7 243 Example 8 242 Control A 191 Control B 250 All exemplary polymers are superior to stiffness to control A, and are equivalent in stiffness to control B. EXAMPLE 27 Removal test procedure Eight hair samples are sprayed, using alcohol-free formula with the formulations described in Example 24 and eight with control A and be allowed to dry environmental conditions for one hour. Each sample is rinsed under running water for 1 minute while working with the fingers in the hair after drying in an oven at 110 ° C (43 ° C). The elimination capacity by shampoo is determined, the results are shown in Table 3: Table 3: Shampoo removal capacity assessments Polymer Ability to remove by shampoo Example 6 + Example 7 + Example 8 + Example 9 + Example 10 + Example 14 + Example 16 An n + "indicates better results when compared to control A. All examples have a high capacity for improved elimination of the hair, and are superior to control A. Example 28 Curl retention test procedure Each of the alcohol-free aerosol formulations prepared from the polymer of examples 5, 6, 7 and 8 is tested in nine samples of hair chains. European coffee Rem Blue String for curl retention at 90% relative humidity, 22 ° C (72 ° F), and the results are pooled and averaged The test procedure is as follows: The hair is separated into samples of approximately grams in weight and attached to one end with epoxy rubber cotton thread, each sample is then washed in a 10% shampoo solution, and rinsed in lukewarm running water.The hair is cut into 6 inch lengths s (15.24 cm) from the insured end and dry at 49 ° C (120 ° F). The samples are then moistened and combed, and the excess water is squeezed. The hair sample is then rolled and secured in an inch Teflon® mandrel (1.54 cm) in diameter, and dry at 49 ° C (120 cm). ° F). When it dries, it is removed from the mandrel and the resulting curl is suspended by its attached end. For each sample, the height of the curl is measured, and then the curl is evenly sprayed. The curl is left on a horizontal surface and allowed to air dry for one hour. The dry curl is then suspended again and fixed in a chamber of 22 ° C (72 ° F), with 90% relative humidity, and mid the height of the curl immediately, at 15, 30, 60 minutes, 9 minutes and intervals of 2, 3, 4, 5, and 24 hours. The retention of the curl is calculated in percentage by the formula (L-Lfc) / (LL °) x 100 where L is the length of the hair fully extended, L ° is the hair length before spraying and exposure, and Lfc is the hair length after spraying and exposure. The results indicated in Table 4 show that the hair fixative polymers and the alcohol free aerosol formulations prepared from the polymers according to the methods of Examples 5, 6, 7 and 8 effectively retain the curl when compared to the Control B: Table 4: retention of the curl at high humidity (90%) average retention values Polymer 15 min 30 min 60 min 90 min 2 h 3 h 4h 5 h 24 h Example 5 97.78 93.14 88.45 87.19 86.12 84.26 84.26 83. 47 78. 59 Example 6 91.76 82.21 76.92 74.12 73.83 71.65 70.76 69.47 63 .43 Example 7 91.99 84.27 75.53 74.46 71.20 71.10 70.20 69 .36 49 .69 Example 8 94.86 91.43 87.46 85.43 84.37 83.23 82.06 82. 00 73 .40 Control B 90.78 85.37 78.11 73.25 72.99 70.18 69.12 65. 70 53. 86 All examples are either superior equivalents in moisture resistance when compared to control B.

Claims (36)

1. CLAIMS 1. A hair setting composition characterized in that it comprises (a) an effective percent by weight, based on the total weight of the fixed hair composition, of a polyurethane prepared from (i) one or more carboxylic acids 2,2- hydroxymethyl substituted, represented by the formula CH2OH i R- C-COOH I CHjOH in which R represents hydrogen, or alkyl of C1-C20 / present in an amount sufficient to give 0.35-2.25 milliequivalents of the carboxyl functionality per gram of polyurethane, (ii) about 5 to about 90% by weight based on the weight of the polyurethane, of organic components containing active hydrogen, other than 2, 2-hydroxymethyl substituted carboxylic acids, which comprise a combination of at least one component of type (A) and at least one component of type (B); or at least one component of the tpip (C) in combination with (A) and / or (B), or at least one component of type (C), wherein the component (A) comprises a polymer with at least two active hydrogen atoms having a Tg of less than 5 ° C, preferably less than -10 ° C of Tg; component (B) comprises components containing active hydrogen comprising rings of 5 to 14 members, wherein the ring structure is heterocyclic, 10 aliphatic, aromatic, cyclic, alicyclic and / or spiral, and rings of 5 to 14 members are substituted with zero to sixteen alkoxylated units; and component (C) comprises hydrogen-containing components 15 active comprising rings of 5 to 14 members, wherein the ring structure are heterocyclic, aliphatic, aromatic, cyclic, alicyclic and / or spiral rings and rings of 5 to 14 members 20 are substituted with more than sixteen alkoxylated units. (iii) One or more organic diisocyanates present to react with active hydrogens of the organic components, with the exception of Hydrogen in the carboxylic acid carboxylic acid 2,2-substituted hydroxymethyl; (b) a diluent comprising (i) water or (ii) water and 0 to 90% by weight of the solvent of one or more organic solvents, or (iii) organic solvent.
2. 2. A hair setting composition according to claim 1 characterized in that it additionally comprises up to about 10% of an ingredient selected from plasticizers, emollients, lubricants, penetrants, fragrances, perfumes, UV absorbers, dyes, colorants, thickeners, agents of anti-corrosion, detaching agents, combing aids, antistatic agents, preservatives, defoamers and mixtures thereof.
3. 3. The hair setting composition according to claim 1, characterized in that the polyurethane is present in an amount of about 1 to 20% by weight of the hair setting composition.
4. 4. The hair setting composition according to claim 1, characterized in that the polyurethane is neutralized with one or more cosmetically acceptable organic or inorganic bases.
5. 5. The hair fixing composition according to claim 1, characterized in that the polyurethane is not neutralized.
6. 6. The hair setting composition according to claim 1, characterized in that the 2, 2-hydroxymethyl substituted carboxylic acid is present in an amount to give 0.5 to 1.85 milliequivalents per gram of polyretin.
7. 7. The hair setting composition according to claim 1, characterized in that the 2,2-hydroxymethyl substituted carboxylic acid is 2,2-di (hydroxymethyl) propionic acid.
8. 8. The hair fixing composition according to claim 1, characterized in that the components (A), (B) and (C) are diols.
9. 9. The hair setting composition according to claim 1, characterized in that the active hydrogen compounds of the type (A) are selected from the group consisting of poly (alkylene oxide)., for example polyethoxylate, polypropoxylate, a polyethoxylate / propoxylate, polymethylene oxide, polybutylene oxide, polyester diols, polyolefin diols, poly (meth) acrylate diols, polysiloxane diamines or polysiloxane diols and mixtures thereof.
10. The hair setting composition according to claim 1, characterized in that the active hydrogen compounds of type (B) have ring components selected from the group cyclohexyl, cyclopentyl, norbornyl, phenyl, biphenyl, phenylether, Bisphenol A, hydrogenated bisphenol A , morpholino, pyrrolidinesujection, piperidine, pyridine, pyrrole, tetrahydropyran, furan, oxazole, and mixtures thereof, wherein the rings are substituted with zero to sixteen alkoxylated units.
11. The hair setting composition according to claim 1 characterized in that the active hydrogen compounds of type (B) have ring components selected from the group consisting of Bisphenol A, hydrogenated bisphenol A and mixtures thereof, wherein the rings are substituted with zero to sixteen alkoxylated units.
12. The hair setting composition according to claim 1, characterized in that the active hydrogen compounds of type (B) have ring components selected from the group cyclohexyl, cyclopentyl, norbornyl, phenyl, biphenyl, phenylether, Bisphenol A, hydrogenated bisphenol A , morpholino, pyrrolidine, piperidine, pyridine, pyrrole, tetrahydropyran, furan, oxazole, and mixtures thereof, wherein the rings are substituted with more than sixteen alkoxylated units.
13. 13. The hair setting composition according to claim 12, characterized in that the active hydrogen compounds of type (C) have ring components selected from the group consisting of Bisphenol A, hydrogenated bisphenol A and mixtures thereof, wherein the rings are substituted with more than sixteen alkoxylated units.
14. The hair setting composition according to claim 1, characterized in that the diisocyanate compound is selected from the group consisting of methylene-p-phenyl diisocyanate, methylene-bis- (4-cyclohexyl isocyanate), isophorone diisocyanate and toluene diisocyanate.
15. 15. The hair setting composition according to claim 1, characterized in that the diisocyanate compound is selected from the group consisting of methylene-p-phenyl diisocyanate, methylene-bis- (4-cyclohexyl isocyanate).
16. 16. The hair setting composition according to claim 4, characterized in that the neutralizing base is selected from the group consisting of sodium hydroxide, potassium hydroxide, 2-amino-2-methyl-1-propanol, histidine, tris (hydroxymethyl) ) -aminomethane, trisopropanolamine, stearamine, triethanolamine and triethylamine.
17. 17. The hair setting composition according to claim 4, characterized in that the amount of base for neutralization is sufficient to neutralize at least 30% of the total acidity of the polymer.
18. 18. The hair setting composition according to claim 4, characterized in that the base for neutralization can be added before, during or after the dispersion step.
19. 19. The hair setting composition according to claim 1 characterized in that the organic solvent is selected from the group consisting of ethanol, propanol, isopropanol, butane, pentane, acetone, methyl ethyl ketone, methylacetate, and dimethoxymethane.
20. The hair setting composition according to claim 1 characterized in that the organic solvent is present in an amount up to about 99% by weight of the total hair setting composition.
21. 21. The hair fixing composition according to claim 1, characterized in that the composition is anhydrous.
22. 22. The hair setting composition according to claim 1 characterized in that the organic solvent is present in an amount up to about 50% by weight of the total hair setting composition.
23. 23. The hair setting composition according to claim 1 characterized in that the organic solvent is present in an amount up to about 20% by weight of the total hair setting composition.
24. 24. The hair setting composition according to claim 1, characterized in that it also comprises up to 70% by weight of a propellant based on the weight of the total hair fixed composition.
25. 25. The hair setting composition according to claim 24, characterized in that the propellant is selected from the group consisting of dimethyl ether, straight and branched chain hydrocarbons of C3-C6, hydrofluorocarbons, compressed gases, and mixtures thereof.
26. 26. The hair setting composition according to claim 1 characterized in that R represents C? -C8 alkyl.
27. 27. The hair setting composition according to claim 1, characterized in that it is provided as a spray, gel, lozenge or mousse.
28. 28. The hair setting composition according to claim 1, characterized in that the polyolurethane is a finished chain.
29. 29. The hair fixing composition according to claim 1, characterized in that the polyurethane is an extended chain.
30. 30. The hair setting composition according to claim 1, characterized in that it is used in combination with other hair fixing polymers.
31. 31. A process for preparing a polyurethane polymer characterized in that it comprises dispersing the polymer after at least 50% of the theoretical isocyanate reaction has taken place, but before the completion of the reaction.
32. 32. A process for preparing a polyurethane polymer according to claim 31, characterized in that the dispersion step occurs after at least 70% of the theoretical isocyanate reaction has taken place, but before the completion of the reaction.
33. 33. The process according to claim 31, characterized in that the ratio of equivalents of isocyanate to equivalents of reactive hydrogen in the polyurethane is less than 1.
34. 34. A process for preparing the hair setting composition according to claim 1 characterized in that it comprises dispersing the pooliurethane polymer after at least 50% of the theoretical isocyanate reaction has taken place, but before the termination of the isocyanate reaction.
35. 35. The process according to claim 34, characterized in that the ratio of equivalents of isocyanate to equivalents of reactive hydrogen in the polyurethane is less than 1.
36. 36. A process according to claim 31 characterized in that the polyurethane polymer is prepared from (i) one or more 2,2-hydroxymethyl substituted carboxylic acids, represented by the formula CH 2 OH I R-C-COOH CH 20 H in which R represents hydrogen, or C 1 -C 2 alkyl, present in an amount sufficient to give 0.35-2.25 milliequivalents of the carboxyl functionality per gram of polyurethane, (ii) about 5 to about 90% by weight based on the weight of the polyurethane, of organic components containing active hydrogen, other than the 2, 2-hydroxymethyl substituted carboxylic acids , comprising a combination of at least one component of type (A) and at least one component of type (B); or at least one component of the tpip (C) in combination with (A) and / or (B), or at least one component of type (C), wherein the component (A) comprises a polymer with at least two active hydrogen atoms having a Tg of less than 5 ° C, preferably less than -10 ° C of Tg; component (B) comprises components containing active hydrogen comprising rings of 5 to 14 members, wherein the ring structure is heterocyclic, aliphatic, aromatic, cyclic, alicyclic and / or 10 spiral, and the rings of 5 to 14 members are substituted with zero to sixteen alkoxylated units; and component (C) comprises components containing active hydrogen comprising rings of 5 to 14 15 members, wherein the ring structure is the heterocyclic, aliphatic, aromatic, cyclic, alicyclic and / or coil rings and the rings of 5 to 14 members are substituted with more than sixteen 20 alkoxylated units. (iii) One or more organic diisocyanates present to react with active hydrogens of the organic components, except hydrogen in the carboxylate of the acid 2, 2-substituted hydroxymethyl carboxylic acid; (b) a diluent comprising (i) water or (ii) water and 0 to 90% by weight of the solvent of one or more organic solvents, or (iii) organic solvent.