MXPA99008289A - Compositions to style the hair, of rig touch - Google Patents

Abstract

The present invention relates to a method for increasing the performance of resins that fix the hair in compositions for styling the hair, by the use of selected polymers, which have certain compositions. In particular, the present invention involves a method to improve the performance of the stiffness of the resins that fix the hair, by the use of polymers containing from 5 to 95% of alkyl methacrylate (C1-Cl0), from 0 to 70 % of a hydroxyalkyl (meth) acrylate, 0 to 50% of a monocarboxylic acid monomer and 1 to 25% of a dicarboxylic acid monomer. The selected polymers are particularly useful in aqueous compositions for styling hair, which contain low concentrations of volatile organic compounds (VOC) (80% or less).

Description

COMPOSITIONS TO SMOKE THE HAIR. FROM RIGID TACT BACKGROUND The present invention relates to compositions for styling the hair and to a method for increasing the performance of the resins that fix the hair. More particularly, the present invention relates to a method for improving the rigidity performance of the resins that fix the hair. In a preferred embodiment, the present invention also relates to aqueous compositions for styling hair, which contain low concentrations (80 percent or less) of volatile organic compounds (VOC). Styling products for hair, such as hair sprays , gels to stylize the same, gels and spray creams, are used on the hair to keep it in a particular shape or configuration. These styling products, when applied, form a thin film or resin solder on the hair, more efficiently, in the seam between fibers of adjacent hair or at a point where the fibers cross each other, and as a result , keep the hair in a particular shape or configuration. Styling products can be applied to hair in different ways. For example, the styling product can be applied by spraying using an impeller (such as in a styling product for spray hair), using a hand pump, or, in the case of a gel, applied to the hair directly with hand. These styling products typically contain one or more VOCs. These VOCs contribute to air pollution at a basic level, in the presence of sunlight and air, and are volatile under environmental conditions. Legislation in New York, California and other states, states that the amount of VOC formulated in hair styling products, which are sprayed, such as sprays for aerosol and pump hair, should not exceed 80 percent. (%) in the product. In June 1999, the amount of VOC in styling products that are sprayed should be reduced to 55% in California. Other states have acted similarly in legislation, mandating the reduction of VOCs in products to stylize hair that is sprayed. The present hair styling products in the United States of America, which are sprayed, typically have VOC levels of 80% or less. Such VOCs include, for example, ethanol, dimethyl ether and hydrocarbons; the most likely replacement for VOCs is water. In order for a resin to be suitable in a composition for styling hair, it must exhibit a combination of desirable performance attributes. They include, but are limited to, the compatibility of the resin in the hair spray composition, satisfactory retention of high moisture waves, satisfactory stiffness in the hair, low tackiness after spraying on the hair, short drying times, no visible residue on the hair, easy shampoo removal and easy spraying ability, resulting in a uniform spray mist delivered to the hair. Hair fixing resins, now available commercially, for example the Amphomer LV-71 (octylacrylamide methacrylate / acrylates / butylaminoethyl copolymer) and Resyn 28-2930 (vinyl acetate / crotonic acid / vinyl neodecanoate copolymer) meet many of these performance attributes, but only in hair spray compositions containing a limited amount of water formulated, for example, less than 15%, such as those usually found in compositions for hair spraying with 80% VOC ( Amphomer and Resyn are trademarks of the National Starch and Chemical Company). These resins are compatible in the hair spray composition and give a firm, stiff touch to the hair, but are deficient in their waste properties or wave retention. In particular, these resins are not suitable in hair spraying compositions with 55% VOC (containing significant amounts of formulated water) due to the poor high viscosity spraying properties, incompatibility in the hair spray composition or they have times of prolonged drying. U.S. Patent No. 4,196,190 discloses hair-fixing acrylic resins, which contain from 10 to 30% of an alkyl acrylate, 41 to 60% of methyl methacrylate, from 5 to 20% of hydroxyethyl methacrylate, and from 10 to 30% of methacrylic acid. Although hair-fixing acrylic resins are disclosed, which are compatible with hair spray compositions with 55% VOC, which contain large amounts of water formulated, which give excellent retention of high moisture waves, excellent water removal capacity. shampoo, short drying times, low or no stickiness, but give a natural, soft touch to the hair, this reference- does not reveal or suggest how to improve the stiffness of the resin on the hair. Although a soft touch to the hair is suitable for those formulations that address a more manageable, natural-touch hair style, a significant portion of the population prefers a firm, rigid hold on the hair. U.S. Patent No. 5,658,558, although it reveals how to improve the performance of acrylic resins in low VOC systems, does not reveal how to improve the stiffness or firmness of the hair. The present invention seeks improvements in the prior art for a resin that fixes the hair, using polymers selected as resins for fixing the hair, which are compatible in hair setting compositions, which contain large amounts of water, for example, compositions containing hair. % VOC, while retaining other beneficial properties to fix the hair, such as (i) low tackiness, (ii) short drying times, (iii) easy removal of the shampoo, (iv) excellent retention of high humidity waves, ( v) easy spraying capacity, and in addition, the delivery of a rigid, firm retention to the hair, rather than a soft touch to it.

EXHIBITION OF THE INVENTION One embodiment of the present invention provides an aqueous composition for styling hair, comprising: a) from 1 to 15 weight percent of at least one acrylic resin that fixes the hair, wherein this acrylic resin fixes the hair is a polymer comprising, as polymerized units; (i) from 5 to 95 weight percent of at least one alkyl methacrylate (C1-C10), (ii) from zero to 70 weight percent of at least one hydroxyalkyl (meth) acrylate, (iii) from zero to 50 weight percent of at least one monomer of monocarboxylic acid, monoethylenically unsaturated , C3-C8, and (iv) from 1 to 25 weight percent of at least one monomer of dicarboxylic acid, monoethylenically unsaturated, C4-C8, based on the total weight of the acrylic resin fixing the hair; and (b) at least one neutralizer. In another embodiment, the present invention provides the aforementioned aqueous hair styling composition which further comprises volatile organic compounds in a concentration up to 98 weight percent, based on the total weight of the aqueous composition for styling the hair . In a preferred embodiment, the present invention provides aqueous hair styling compositions, using the aforementioned hair setting resin, in which (a) (C1-C10) alkyl (meth) acrylate is from 2 to 67% by weight. weight percent of at least one C2-C5 alkyl acrylate) and from 5 to 71 weight percent of methyl methacrylate, (b) the hydroxyalkyl (meth) acrylate is from 2 to 26 weight percent of the methacrylate of hydroxyethyl, (c) the monomer of monocarboxylic acid, monoethylenically unsaturated, C3-C8, and from 2 to 30 weight percent of methacrylic acid, and (d) the monomer of dicarboxylic acid, monoethylenically unsaturated, C4-C8, is 2 to 10 weight percent of itaconic acid. The present invention further provides a method for increasing hair stiffness of aqueous compositions for styling hair, comprising introducing 1 to 15 percent of an acrylic resin that fixes hair, based on the total weight of the aqueous composition for styling the hair, in a composition for styling the hair, wherein (a) the acrylic resin that fixes the hair is a polymer comprising, as polymerized units: (i) from 5 to 195 percent of at least one (C 1 -C 10) alkyl (meth) acrylate, (ii) from zero to 70 weight percent of at least one hydroxyalkyl (meth) acrylate, (iii) from zero to 50 weight percent of at least one monomer of monocarboxylic acid, monoethylenically unsaturated, C3-C8, and (iv) from 1 to 25 weight percent of at least one monomer of dicarboxylic acid, monoethylenically unsaturated, C4-C8, based on the total weight of the acrylic resin fix the hair; and (b) the hair styling composition comprises at least one neutralizer.

DETAILED DESCRIPTION The aqueous hair styling compositions of the present invention provide improved performance of the stiffness of the composition to style the hair. It has been found that the use of certain selected acrylic polymers, surprisingly, improves the stiffness in the hair of the hair styling composition, adversely affecting other properties of the hair styling composition. By an "aqueous composition for styling the hair" is meant a hair spray, styling gel, gel or spray cream, which are used on the hair to retain it in a particular shape or configuration. Preferably, the hair styling composition of the present invention is a hair spray. By "hair" is meant the natural human hair, animal hair, artificial hair and hair comprising the wigs and toupees. As used herein, all percentages mentioned (%) will be expressed by weight, unless otherwise specified.

Aqueous hair styling compositions will typically contain at least 2% and up to 96% water, more typically 25 to 70% water, based on the total weight of the aqueous composition to style the hair. By "low VOC" it is meant that the hair styling composition contains 80% or less of volatile organic compounds, that is, usually about 10% or more of water. Preferably, the hair styling composition contains less than 70%, and more preferably 55% or less, of the VOC's. Optionally, the hair styling composition may not contain the VOCs. The term "(meth) acrylate" means both methacrylate and acrylate. The term "(meth) acrylic acid means methacrylic acid or acrylic acid." As used herein, the term "dicarboxylic acid monomer" refers to monoethylenically unsaturated dicarboxylic acids, containing from 4 to 8, preferably from 4 to 6, carbon atoms per molecule, and the anhydrides of the corresponding dicarboxylic acids Monomers of dicarboxylic acids useful in the water-soluble polymers of the present invention include, for example, maleic acid, maleic anhydride, fumaric acid, a-methylene glutaric acid, itaconic acid, itaconic anhydride, citraconic acid, mesaconic acid, cyclohexendicarboxylic acid and their water-soluble salts When the word "soluble" is used to further describe a compound, such as, for example, " soluble resins that fix the hair ", it is understood that the described compound is soluble in the composition to stylize the hair With low VOC content, as used herein, VOCs are compounds that contain at least one carbon atom and are typically used as solvents or impeller in hair styling compositions. VOCs include, for example, alcohols, straight or branched chain, C1-C12, such as methanol, ethanol, propanol, isopropanol and butanol; straight or branched chain hydrocarbons, cl-C12, such as methane, ethane, propane, isopropane, isobutane, pentane, isopentane and butane; or ethers, such as dimethyl ether and dimethoxymethane. Preferred VOCs are selected from one or more of ethanol, isopropanol, n-propanol, dimethoxymethane, dimethyl ether and straight or branched C1-C12 hydrocarbons.

Acrylic resins that fix the hair, useful in the present invention, are soluble in the hair styling composition, of low VOC "as is" or in the neutralization of some or all of the acid groups contained in the acrylic resins that fix the hair . The acrylic resins that fix the hair of the present invention comprise, as polymerized units, (1) from 5 to 95%, preferably from 45 to 90%, and more preferably from 70 to 80% of at least one (meth) monomer alkyl acrylate, straight or branched chain, C1-C10, (2) from zero to 70%, preferably from 2 to 26%, and more preferably from 5 to 20% of at least one hydroxyalkyl (meth) acrylate monomer , (3) from zero to 50%, preferably from 2 to 30%, and more preferably from 12 to 26% of at least one monomer of monocarboxylic acid, monoethylenically unsaturated, C3-C8, and (4) from 1 to 25% , preferably from 2 to 10% and more preferably from 3 to 8% of at least one monomer of dicarboxylic acid, monoethylenically unsaturated, C4-C8, based on the total monomer used, to form the acrylic resin that fixes the hair.

Preferably, the alkyl (meth) acrylate (Cl-C10) is selected from one or more alkyl (meth) acrylates (C1-C5), such as, for example, methyl (meth) acrylate, (meth) ethyl acrylate, propyl (meth) acrylate, (me) butyl acrylate and pentyl (meth) acrylate. More preferably, the (C 1 -C 10) alkyl (meth) acrylate component comprises at least one (C 1 -C 3) alkyl methacrylate and at least one (C 2 -C 5) alkyl acrylate. More preferably, the alkyl (meth) acrylate component comprises methyl methacrylate and butyl acrylate. The amount of at least one (C 1 -C 3) alkyl methacrylate in the hair setting resin is preferably 5 to 71%, more preferably 41 to 60%, based on the total monomers used to form the resin that fixes The hair. The amount of the alkyl acrylate (C2-C5) is preferably 2 to 67% and more preferably 10 to 30%, based on the total monomer used to form the acrylic resin that fixes the hair. The alkyl group of the hydroxyalkyl (meth) acrylate is preferably a (C1-C5) alkyl group. For example, the hydroxyalkyl (meth) acrylate is preferably selected from one or more of the hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and hydroxypentyl (meth) acrylate. More preferably, the hydroxyalkyl (meth) acrylate is selected from one or more of the hydroxyethyl methacrylate and hydroxypropyl acrylate. The monomer of monocarboxylic acid, monoethylenically unsaturated, C3-C8, is preferably selected from one or more of the (meth) acrylic acid and crotonic acid. More preferably, the monocarboxylic acid, monoethylenically unsaturated, C3-C8, is methacrylic acid. The monomer of dicarboxylic acid, monoethylenically unsaturated, C4-C8, is preferably selected from one or more of itaconic acid, maleic acid and the corresponding anhydrides. Preferably, the monomer of the dicarboxylic acid, monoethylenically unsaturated, C4-C8, is itaconic acid. The combined amount of unsaturated monocarboxylic acid and unsaturated dicarboxylic acid monomer is typically 3 to 60%, preferably 12 to 50% and more preferably 15 to 25%, based on the total weight of the resin that fixes the hair. At lower levels of the combined monosarboxylic acid and dicarboxylic monomer, the degree of rigidity increase of the resin that sets the hair is reduced. While not wishing to be bound by the theory, we believe that, in the case of the present invention, the monomers comprising the acrylic resins that fix the hair impart the following properties to the resins: (1) the alkyl acrylate component of the acrylic resins that fix the hair plasticize or reduce the brittle state of the resins, (2) the alkyl methacrylate (C1-C3) component provides hardness to give the resins non-retaining properties. sticky, when applied to the hair as a film, (3) the components of hydroxyalkyl methacrylate and methacrylic acid provide the removability of the shampoo without compromising the retention or stickiness of resin waves, and (4) the dicarboxylic acid component. It strengthens the modulus of the resulting film and, in combination with the increased molecular weight, imparts greater rigidity to the hair. The proportions of the monomers comprising the acrylic resin fixing the hair are selected to select an optimum hydrophilic / hydrophobic balance. This optimal balance provides, in a composition for styling the hair, low VOC, wave retention, under wet conditions, moisture resistance, shampoo removability and aesthetics convenient to the hair, such as the minimum flange of the resin that fixes The hair. The acrylic resins that fix the hair preferably have a glass transition temperature (Tg) of 35 to 140 ° C, more preferably greater than 50 ° C and up to 100 ° C, and especially preferred, of 55 to 90 ° C. The acrylic resins that fix the hair are preferably added to the hair styling composition and provide a total concentration of 1 to 15%, more preferably 2 to 10%, and especially preferred 4 to 7%, of the acrylic resins that Fix the hair, based on the total weight of the composition to stylize the hair. The acrylic resins that fix the hair can be prepared by conventional method, well known to those skilled in the art. These acrylic resins that fix the hair are preferably prepared by the emulsion polymerization, more preferably by a continuous online emulsification process. U.S. Patent Nos. 3,245,932, 3,453,245 and 4,196,190 can be consulted for additional general and specific details in suitable emulsion polymerization methods. The emulsifiers used in the preparation of the polymer maintains the hair-fixing acrylic resins suspended in the emulsion of acrylic resin for the hair. Typical emulsifiers used to prepare the hair-fixing acrylic resins include, for example, one or more alcohol sulfates (C8-C18) (such as sodium lauryl sulfate and sodium tridecyl ether sulfate, diester sulfosuccinates, esters of phosphoric acid (such as long-chain alkyloxypoly (alkylene oxide), long chain alkylaryloxypoly (alkylene oxide), long chain alkyl mono- and di-esters and long-chain alkylaryl phosphoric acid, for example, the alkyl (C8) -C18) -aryloxypoly (alkylene oxide), (C10-C18) alkyl-oxypoly (alkylene oxide), mono- and di-esters of (C10-C18) alkyl and (C8-C18) alkyl (phosphoric acid), sulfonate alkaryl (such as dodecylbenzene sulphonate, alkyl or aryl polyester sulfonates, alkyl or aryl polyether alcohols, ethylene oxide condensates of propylene oxide adducts and propylene glycol.) Preferably, the emulsifiers used are emulsifiers of the anhydride type. ionic, such as the long chain alkyloxypoly (alkylene oxide), long chain alkylaryloxy poly (alkylene oxide), long chain alkyl mono- and di-esters and long chain alkylaryl, phosphoric acid. The soluble resins that fix the hair, which are useful in the present embodiment, are soluble in the composition to stylize the hair, with low VOC "as such", or in the neutralization of some or all of the acid groups contained in the resins soluble that fix the hair. These soluble resins that fix the hair, if sprayed, preferably have a viscosity less than or equal to 15 x 10 '3 Pases • second (Pa-sec) (15 centipoises), when dissolved in a composition to stylize pump-type hair, at a resin concentration of about 5% or less, based on the total weight of the composition to stylize the hair, and less than 25 x 10 ~ 3 Pa-sec in an aerosol concentrate.

Hair-fixing acrylic resins, which contain acid groups, such as carboxylic acid groups, are neutralized by conventional techniques with at least one base, to dissolve the resins in the hair styling composition. Bases that will neutralize the soluble resins, which fix the hair, can be selected from one or more amines, alkaline or alkaline earth metal hydroxides and ammonium hydroxide. Suitable amine neutralizers include, for example, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, N, N-dimethyl-2-amino-21-methyl -1-propanol, monoisopropanolamine, triisopropanolamine, ethanolamine, triethanolamine and morpholine. Suitable hydroxides of alkali or alkaline earth metals include, for example, sodium hydroxide and potassium hydroxide. Preferably, the neutralizer is selected from one or more of 2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, N, N-dimethyl-2-amino-2-methyl -l-propanol, potassium hydroxide, triethanolamine and triisopropanolamine. The amount of neutralizer added to the composition for styling the hair is that necessary to provide the solubility of the soluble resins that fix the hair in the composition to stylize the hair. Typically, from 5 to 100%, preferably from 10 to 100%, more preferably from 50 to 100% and especially preferred from 75 to 100%, based on the molar equivalents, of the acid groups in the resins that fix the hair, they are neutralized. Low-VOC hair styling compositions can also be mixed with one or more other resins that fix the hair. Suitable soluble resins, which fix the hair, include, for example, hair-fixing acrylic resins, described previously, and other hair-soluble resins, such as, for example, butyl acrylate / ethyl acrylate / copolymers. methacrylic acid, vinyl pyrrolidone / vinyl acetate copolymers, octylacrylamide / acrylates / butylaminoethyl methacrylate copolymers, vinyl caprolactam / vinyl pyrrolidone / dimethylaminoethyl methacrylate copolymers, methacryloyl-ethyl betaine / methacrylate copolymers, methacrylic acid copolymer / methacrylic ester, copolymer of acrylates / acrylates of hydroxyesters and copolymers of ethacrylic acid / acrylic acid ether. Preferably, the soluble resins that fix the hair are the acrylic resins, previously described. One or more surfactants may be added to the hair styling composition, with low VOC content, typically to reduce the surface tension of the composition. When surfactants are present in the hair styling composition, they are preferably present at a concentration of 0.001 to 1%, based on the total weight of the composition. Surfactants that can be used in the hair styling composition include, for example, anionic, cationic, nonionic and amphoteric agents. For example, suitable surfactants include PPG 28 Buteth 35, PEG 75 lanolin, perfluoropolymethyl isopropyl ether, octoxynol-9, hydrogenated castor oil of PEG-25, polyethylene terephthalate, glyceryl trioleate of polyethylene glycol 25, phosphate of oleth-3, phosphate of PPG-5-ceteth-10, methyl-glucose-ether of PEG 20, 7-triacetate of glycereth and lactam substituted by n-alkyl (such as n-octyl-pyrrolidone). One or more plasticizers can be added to the composition to style the hair of the present invention. When the plasticizers are present in the composition to stylize the hair, they are preferably present in a concentration of 0.001 to 1%, based on the total weight of the composition. Plasticizers that can be used in the hair styling composition include, for example, dimethicon-copolyol, dimethicone, phenyltrimethicones, trialkyl citrates, and others that are known and typically used in the art. One or more solvents may be added to the hair styling composition of the present invention. When solvents are added to this composition, they preferably comprise up to 70%, more preferably up to 55% of the total hair styling composition, based on the total weight of this composition. Suitable solvents include, for example, the C2-C6 organic alcohols (such as ethanol, isopropanol, propyl alcohol) and acetone. In a low VOC hair styling composition using an aerosol spray, one or more impellers are used. Preferably, the impellents are used at a total concentration of 10 to 70%, more preferably 30 to 60%, based on the total weight of the composition for styling the hair. Suitable impellents include, for example, one or more of n-butane, isobutane, dimethyl ether, difluoroethane, chloro-difluoroethane, chlorodifluoromethamo, and other chloro-fluorocarbons. Preferred propellants are selected from one or more of the dimethyl ether, 1,1-difluoroethane, n-butane and isobutane. These impellers are commercially available. Condoms can be used in the hair styling composition of low VOCs, including, for example, one or more of the isothiazolones, iodopropynylbutyl carbamate, benzyl alcohol, imidazolidinylurea and alkyl parabens. A preferred antimicrobial agent is iodopropynylbutylcarbamate (commercially available from Lonza Inc., Fairlawn, New Jersey). The condoms preferably comprise from 0.001 to 1% of the active ingredient, in the resin emulsion that fixes the hair. One or more thickeners may be suitable in a hair styling composition, with low VOC, which is applied to the hair in the form of a styling gel. Suitable thickeners include, for example, thickeners of the polycarboxylic acid, such as the acrylates / methacrylate copolymer of estearth-20. Acrylates copolymer, or cross-linked polymer of Acrylates and C10-C30 alkyl acrylate; polyethoxylated urethane thickeners and polyamide thickeners. The thickeners, when used preferably, are present in a total concentration of 0.001 to 5%, based on the total weight of the composition. Other additives, such as those commonly used by those skilled in the art, can be added to the styling composition at low VOC. These other additives used in the composition for styling the hair will depend on the type of the composition for styling the desired hair. Other additives include, for example, one or more fragrances, humectants (such as hydrolyzed silk protein and hydrolyzed wheat protein), unraveling aids, such as panthenol; conditioning agents (U.S. Patent No. 5,164,177 can be consulted for general and specific additional details in suitable conditioning agents); emulsifiers; antistatic auxiliaries; extracts, proteins; vitamins; tinctures, dyes; colorants; UV radiation protectors; and corrosion inhibitors. The other additives typically comprise from 0.005 to 5%, and more preferably from 0.01 to 1%, of the hair styling composition. Other additional additives, as well as surfactants, solvents, other preservatives and additional thickeners, which may be suitable in the composition for styling hair, can be found in the International Cosmetic Ingredients Dictionary, 5th Edition, 1993, published by Cosmetics Toiletres Fragrances Association (CFTA), Washington, DC Examples 1 to 23 describe the preparation of polymer compositions representing the hair fixing resin polymers of the present invention, which include the comparative compositions (Polymers ID # 2-6, 20, 21 and 23). All ratios, parts and percentages are expressed by weight, unless otherwise specified, and all reagents used are of good commercial quality, unless otherwise specified. The abbreviations for the monomers, emulsifiers and other materials described in the Examples are presented in Table 1. The monomeric binding composition of the hair fixing resin / emulsifier information is summarized in Table 2. Table 1 BA = butyl acrylate BMA = butyl methacrylate IBMA = isobutyl methacrylate TBMA = tertiary butyl methacrylate IBOA = isobornyl acrylate IBOMA = isobornyl methacrylate MMA = methyl methacrylate HEMA = hydroxyethyl methacrylate DMAM = N, N-dimethylacrylamide MAA = methacrylic acid IA = itaconic acid DDM = dodecyl mercaptan SLS = sodium lauryl sulphate PPE-1 = mono / diester (55/45) of tridecyloxypoly (ethylene oxide) phosphate 6 Table 2 Composition ID of Resin Fixing Hair Polymer # 1 25 BA / 47 MMA / 10 HEMA / 13 MAA / 5 IA with PPE-1 ÍA 25 BA / 47 MMA / 10 HEMA / 13 MAA / 5 AI with SLS 2 (Comp) 25 BA / 47 MMA / 10 HEMA / 18 MAA with SLS 3 (Comp) 25 IBMA / '47 MMA / 10 HEMA / 18 MAA with SLS 4 (Comp) 25 TBMA / 47 MMA / 10 HEMA / 18 MAA with SLS 5 (Comp) 10 IBOA / 15 BA / 47 MMA / 10 HEMA / 18 MAA with SLS 6 (Comp) 10 IBOMA / 15 BA / 47 MMA / 10 HEMA / 18 MAA with SLS 7 25 BA / 52 MMA / 10 HEMA / 8 MAA / 5 AI with PPE-1 8 25 BMA / 47 MMA / 10 HEMA / 13 MAA / 5 IA with SLS 9 25 BMA / 47 MMA / 5 HEMA / 5 DMAM / 13 MAA / 5 IA co SLS 9A 30 BMA / 47 MMA / 10 HEMA / 8 MAA / 5 IA with SLS 25 BA / 42 MMA / 10 HEMA / 5 DMAM / 13 MAA / 5 IA co SLS 11 23 BA / 2 IBOMA / 47 MMA / 10 HEMA / 13 MAA / 5 IA co PPE-1 12 21 BA / 4 IBOMA / 47 MMA / 10 HEMA / 13 MAA / 5 IA co PPE-1 13 18 BA / 7 IBOMA / 47 MMA / 10 HEMA / 13 MAA / 5 IA co PPE-1 14 25 BA / 57 MMA / 13 MAA / 5 AI with PPE -1 15 25 BA / 55 MMA / 2 HEMA / 13 MAA / 5 AI with PPE-1 16 25 BA / 47 MMA / 10 HEMA / 11 MAA / 7 AI with PPE-1 17 25 BA / 47 MMA / 10 HEMA / 8 MAA / 10 AI with PPE-1 18 25 BA / 2 IBOA / 47 MMA / 10 HEMA / 13 MAA / 5 IA with PPE-1 19 21 BA / 4 IBOA / 47 MMA / 10 HEMA / 13 MAA / 5 AI with PPE-1 20 (Comp ..) 21 BA / 4 IBOA / 47 MMA / 10 HEMA / 18 MAA with SLS 21 (Comp.) 18 BA / 7 IBOA / 47 MMA / 10 HEMA / 18 MAA with SLS 22 21 BA / 4 IBOMA / 47 MMA / 10 HEMA / 13 MAA / 5 IA with SLS 23 (Comp.) 21 BA / 4 IBOMA / 47 MMA / 10 HEMA / 18 MAA with SLS The hair styling compositions for the test were prepared as follows: 5% of the hair resin polymer (% active solids), 50-100% neutralized with the l-amino-2-methyl-l- propanol, 55% ethanol (100%), and rest is composed of water. The compositions of Table 3 were evaluated at 55% VOC, 50% neutralization, unless otherwise indicated. A polymer containing non-dicarboxylic acid (Polymer # 2) was used as a control to determine the increase in stiffness of the acrylic resins that fix the hair, of the present invention. The ratio of the "stiffening factor", (SEF) is the ratio of the stiffness of the composition to styling the hair, which contains a resin that fixes the hair, in relation to that of the composition to stylize the hair containing the hair. Polymer # 2 The hair fixation performance data, presented in Table 2, is based on several different properties, firstly the increase in rigidity of the treated hair, clarity / uniformity of the stretched film, and wave retention properties. high moisture, were satisfactory, unless otherwise indicated.The hair styling compositions of the present invention contain hair-fixing resins that provide a firm touch ("increased stiffness") to the hair, as measured by the compression of the waves in the treated hair, in relation to the hair treated with the resins that fix the hair of the prior art (that is, those resins that fix the hair). beautiful that do not contain the dicarboxylic acid monomer). The "stiffness increase factor" (or SEF) is a relative measure of eta better. Preferably, hair styling compositions of the present invention provide an SEF of at least 1.2, more preferably at least 1.5 and especially preferred at least 1.7, based on the compression of the waves of the hair samples treated with the hair. resin that fixes the hair. Example 24 describes these tests in detail. The data in Table 3 show the increase in stiffness for the resins that fix the hair, which have weight average molecular weights that vary from 48, 000 to 153,000. Resins that fix hair containing a non-dicarboxylic acid monomer (# 2,3, 4, 5, 6, 20, 21 and 23) are deficient in the properties of increased stiffness, clarity of wave retention film. The neutralization levels of the carboxylic groups in the resins that fix the hair at 75 and 100% (# 1, ÍA, 8 and 12-15) provide satisfactory properties other than the neutralization level of 50%. Various levels of the hydroxyalkyl (meth) acrylate monomer component (from zero to 10%) provide satisfactory properties (# 1, 9, 14 and 15). Various levels of the monomer component of dicarboxylic acid (from 5 to 10%) provide satisfactory properties (-15, 16 and 17). Additional resins that fix the hair in Table 3 represent various combinations of different components of (C 1 -C 10) alkyl (meth) acrylate monomers (BA, IBOA, IBOMA, MMA and BMA).

Table 3 Composition of SEF Ratio Clarity of the Mw Polymer Film Placed 1 1.31 + 48K 1 1.28 * 71K 1 1.36 * 104K 1 1.55 153K 1 1.57 78K 1.45 + 78K ÍA 1.36 + lAb 1.91 + ÍA 1.64 + 116K 2 (Comp.) "1.0+ + 50K 3 (Comp.) 1.12 4 (Comp.) 1.05 5 (Comp.) 1.47 6 (Comp.) 1.08 7 1.0 + 62K 8 1.52 + 1.19 1.27 + 9 2.22 + 63K 9A 1.0 + 10 1.80 + 11 1.72 + 12 1.69 + 12b 1.41 1 13b 1.33 + 14 ° 1.71 + 15b 1.56 + 16 1.52 + 17 1.51 + 18 1.83 + 19 1.28 + 20 (Comp.) 1.31 - 21 (Comp.) - 22 2.00 + 23 (Com.) 1.37 - a = The molecular weight is approximately 50 K (50,000), unless otherwise indicated b = resin that fixes the hair, 75% neutralized c = resin that fixes the hair, 100% neutralized d = poor retention of high humidity waves EXAMPLE 1 To a three-liter four-necked round bottom flask equipped with an overhead stirrer, condenser, nitrogen adapter and thermal pair, 43.5 grams (g) of itaconic acid (IA) powder was added, 255.0 g of deionized water and 8.5 g of a mixed emulsifier of phosphate ester (in water) at 25% as the ammonium salt (55/45 ratio of the mixture of esters of mono-trideciloxipoli (ethylene oxide) and di-trideciloxipoli (ethylene oxide) of phosphoric acid, which have an average of 6 units of ethylene oxide per group [PPE-1 in Table 1], available as Rhodafac RS-610A from Rhdne-Poulenc, - Rhodafc is a trademark of Rhône- Poulenc Inc.). With the activated nitrogen, the reactor and the contents were heated to 83 ° C and an initiator solution of 2.2 g of ammonium persulfate and 17.5 g of deionized water was added, with stirring. After charging the initiator solution, 50 g of the monomer emulsion was added, from a monomer emulsion containing 388 g of deionized water, 12.75 g of a mixed phosphate ester emulsifier, 408.9 g of methyl methacrylate (MMA) ), 217.5 g of butyl acrylate (BA), 87 g of hydroxyethyl methacrylate (HEMA), 113.1 g of methacrylic acid (MAA) and 11.0 g of n-dodecyl-mercaptan (DDM) were charged to the reactor. The residual monomer emulsion charge was then fed in 120 minutes, while maintaining a temperature of 83 ° C. A coker initiator solution containing 0.73 g of ammonium persulfate and 79.0 g of deionized water was added gradually, simultaneously, with the monomer emulsion charge in 120 minutes. After completing the charges of the monomer emulsion and initiator, the reaction mixture was "chased" with ferrous sulfate, t-butyl hydroperoxide, ammonium persulfate and d-isoascorbic acid in combination, to reduce residual monomer levels. The reaction mixture was then cooled to room temperature and filtered. The composition of the resulting polymer was 47 MMA / 25 BA / 10 hEMA / 13 MAA / 5 IA. The amount of the PPE-1 emulsifier was 0.6% based on the total weight of monomers.

EXAMPLE A composition of emulsion polymers was prepared again, according to Example 1, except for the surfactant employed and its total amount based on the monomer. Sodium lauryl sulfate (28% aqueous solution) was charged to 8.5 g as part of the initial reactor charge and 4.25 g as part of the monomer emulsion.

EXAMPLES 2 TO 23 Polymer compositions 2 to 23 were prepared similarly to Examples 1 and IA and are representative of the hair-fixing resin polymers of the present invention, which include the comparative compositions. Additional information was presented in Table 2.

Example 24: Performance Tests of Hair Formulation Hair Rigidity Previous Treatment: Hair Braids (European chestnut virgin hair, obtained from International Hair Importers and Products, White Plains, NY), before waving, were on average 15 cm long and weighed 3.5 ± 0.1 grams. They were washed in soft shampoo before use and rippled in wet on a 22 mm curling iron (mm) by 70 mm, and held in place with a pressure fork. The wavy braids were allowed to dry on the laboratory bench overnight.

Measurement of stiffness: The undulated braids were sprayed evenly twice in front and twice in the back, at a distance of 20.3 centimeters (cm), with a hair spray formulation containing the resins that fix the hair, as described in Table 1. They were placed in the laboratory bench to dry for 1 hour. The crimper was placed in the miniature voltage tester, model MTT 160 instrument (Dia-Stron Limited, Unit 9 Focus 303 Business Center, Andover, Hampshire SP10 5NY UK, or 390 Reed Road, Broomall, PA 19008, USA) and measured the work measured to compress the waves to 40% of its initial diameter. The spray device delivered 140 microliters (μl) of formulation to the hair with each compression of the pump. The product of the spray device was 'Euromist II', and was manufactured by Sequist Perfect, Cay, Illinois. For untreated hair braids, the wave compression work was approximately 4.5 milliJoules (mJoule); for the hair braids treated with Polymer # 2, the wave compression work typically varied from 10 to 15 mJoules; For hair braids treated with the polymers useful in the present invention, the wave compression work typically varied from 15 to 25 mJoules.

Wax Retention, with High Moisture The amount of formulation that fixes the hair, sprayed on the hair was the same as described before for stiffness measurements. The following procedure was used to evaluate each test composition to stylize the hair. Each test composition for styling the hair was sprayed on a 2 gram sample of European chestnut virgin hair, which is 16.5 cm long, previously gummed at the root end and supplied by International Hair Importers, White Plains, NY. Each hair sample was washed with a diluted shampoo solution "Suave" (trademark of Helene Curtis), followed by rinsing with deionized water at room temperature. Each test composition for styling the hair was sprayed onto the hair sample, using a Euromist II spray valve; This valve distributed around 140 μl per stroke of the pump. The percentage of retention of waves for each test composition to stylize the hair was evaluated by winding the hair sample, previously described, on a curler having a diameter of about 3 cm. The hair was then sprayed with about 700 μl of the test composition to stylize the hair. The hair was allowed to dry completely. After drying, the curler was removed from the hair and that hair was placed in a chamber that has 95 percent relative humidity for 8 hours. The percentage of retention of waves was measured by measuring the length of the hair initially after undulating (Li), the length of the hair after exposure to moisture (Lt) and the length of the hair fully extended, before undulating. The following equation (Formula I was used to calculate the waviness retention percentage) The waviness satisfactory retention values are greater than 70%, preferably greater than 80%, and more preferably greater than 85%.

(Li-Lt) x 100 Rippling Retention = (Li-L, e) Formula I Effects on Molecular Weight Hair-setting acrylic resins, useful in the present invention, were evaluated for the effect of the weight-average molecular weight (Mw) of the resin in the performance of hair styling compositions, with low VOC content. The acrylic resins that fix the hair preferably have an Mw of 40,000 to 200,000, more preferably 50,000 to 150,000 and especially preferred of 75,000 to 130,000, as measured by gel permeation chromatography (GPC), using a methacrylate polymer of methyl with molecular weight of 100,000 as the standard. Resins that fix hair, which have an Mw below 40,000, do not pde the hair stiffness required by the present invention; those resins having an Mw greater than 200,000, do not allow a satisfactory spray capacity of the composition to stylize the hair, due to the high viscosity. Clarity of the Film A formulation was prepared to fix the hair, mixing the following components: 5% active polymer, 55% ethanol (100%), 0.7% of the 2-amino-2-methyl-1-propanol and 30% deionized water Approximately 2 milliliters (ml) of the formulation were placed on a clean glass plate and a film was spread through the plate, with a thickness of 102 microns on the block. The film was observed in its opacity, while it was dried and after drying: if the film remains completely clear, passes the test (+), and if it has any opacity or fracture, while the film dries or after it has dried, it fails the proof (-) .

Claims (10)

1. CLAIMS 1. An aqueous composition for styling the hair, which comprises: a) from 1 to 15 weight percent of at least one acrylic resin fixing the hair, wherein said acrylic resin fixing the hair is a polymer comprising , as polymerized units; (i) from 5 to 95 weight percent of at least one (C1-C10) alkyl methacrylate, (ii) from zero to 70 weight percent of at least one hydroxyalkyl (meth) acrylate, (iii) from zero to 50 weight percent of at least one monomer of monocarboxylic acid, monoethylenically unsaturated, C3-C8, and (iv) from 1 to 25 weight percent of at least one monomer of dicarboxylic acid, monoethylenically unsaturated, C4-C8, based on the total weight of the acrylic resin fixing the hair; and (b) at least one neutralizer.
2. 2. The composition of claim 1, wherein: (i) (C1-C10) alkyl (meth) acrylate is from 2 to 67 weight percent of at least one (C2-C5) alkyl acrylate and from 5 to 71 weight percent of methyl methacrylate; (ii) the hydroxyalkyl (meth) acrylate is from 2 to 26 weight percent of the hydroxyethyl methacrylate; (iii) the monomer of monocarboxylic acid, monoethylenically unsaturated, C3-C8, is from 2 to 30 weight percent of methacrylic acid, and (iv) the monomer of dicarboxylic acid, monoethylenically unsaturated, C4-C8, is from 2 to 10 weight percent of itaconic acid.
3. 3. The composition of claim 1, wherein the neutralizer is selected from one or more of 2-amino-2-methyl-1-propanediol, 2-amino-2-methyl-1-propanol, N, N-dimethyl-2- amino-2-methyl-1-propanol, potassium hydroxide, triethanolamine and triisopropanolamine.
4. 4. The composition of claim 1, further comprising volatile organic compounds in a concentration up to 98 weight percent, based on the total weight of the aqueous composition for styling the hair.
5. 5. The composition of claim 4, wherein the concentration of the volatile organic compounds is 80 weight percent or less.
6. 6. The composition of claim 1, wherein this composition has a stiffness increase factor of at least 1.2, based on the undulation compression of the hair samples treated with the resin that fixes the hair.
7. 7. The composition of claim 1, wherein: the polymer has a weight average molecular weight of 40,000 to 200,000.
8. 8. The composition of claim 1, wherein: the monomer of monocarbonylic acid, monoethylenically unsaturated, C3-C8, and the monomer of dicaboxylic acid, monoethylenically unsaturated, C4-C8, are present in a combined amount of 3 to 60 percent in weight, based on the total weight of the acrylic resin that fixes the hair.
9. 9. A method for increasing the stiffness in the hair of aqueous compositions for styling the hair, which comprises introducing from 1 to 15 weight percent of an acrylic resin fixing the hair, based on the total weight of the aqueous composition for styling the hair, in this composition to stylize the hair, in that: a) the acrylic resin fixing the hair is a polymer comprising, as polymerized units: (i) from 5 to 95 weight percent of at least one (C 1 -C 10) alkyl (meth) acrylate, (ii) zero to 70 weight percent of at least one hydroxyalkyl (meth) acrylate, (iii) from zero to 50 weight percent of at least one monomer of monocarboxylic acid, monoethylenically unsaturated, C3-C8, and (iv) 1 to 25 weight percent of at least one monomer of dicarboxylic acid, monoethylenically unsaturated, C4-C8, based on the total weight of the acrylic resin fixing the hair; and (b) the composition for styling the hair comprises at least one neutralizer.
10. 10. The method of claim 9, wherein: (i) (C 1 -C 10) alkyl (meth) acrylate is from 2 to 67 weight percent of at least one (C 2 -C 5) alkyl acrylate and from 5 to 71 weight percent of methyl methacrylate; (ii) the hydroxyalkyl (meth) acrylate is from 2 to 26 weight percent of the hydroxyethyl methacrylate, - (iii) the monomer of monocarboxylic acid, monoethylenically unsaturated, C3-C8, is from 2 to 30 weight percent of methacrylic acid, and (iv) the monomer of dicarboxylic acid, monoethylenically unsaturated, C4-C8, is from 2 to 10 weight percent of itaconic acid.