MXPA00002629A - Improved hair spray and consumer sprays with reduced volatile organic compounds - Google Patents

Abstract

A consumer article comprising a hand-held spray container, and a sprayable composition contained within the spray container comprising ethanol or isopropanol and methyl acetate or t-butyl acetate, a hair care composition comprising a fixative, ethanol, and methyl acetate or t-butyl acetate, and a method of fixing hair comprising spraying the compositions of this invention onto hair.

Description

SPRAYED FOR HAIR AND DECEPTS IMPROVED CONSUMABLES WITH LOW CONTENT OF VOLATILE ORGANIC COMPOUNDS DESCRIPTION OF THE INVENTION This invention relates generally to consumable sprays containing ethanol as a solvent for active ingredients in the sprayer, and to the replacement of ethanol by alkyl acetates, especially methyl acetate and t-buyl acetate. The invention also has application to consumable sprinklers containing isopropanol, and the replacement of isopropanol by these alkyl acetates. The hair sprinklers were introduced to the public before 1940 and were an immediate success. The first sprinklers were pump-type systems, but public demand for a better product led to the development of the spray sprinkler. The aerosol spray was based on the Goodhue and Sullivan patent for low pressure propellants (fluorocarbon 12) and a patented Abplanalp valve design. The first aerosol hair sprayer was introduced to the public in 1949 in Chicago by The Global Liqinet Corporation, and created a multi-million dollar business. The lacquer was the first fixative polymer used in aerosols; But the lacquer had several major disadvantages that followed the development of synthetic polymers with properties that could be better controlled. Many of the formulations gave good fixing properties, but contained solvents and propellants sensitive to the environment. In 1979, chlorofluorocarbon (CFC) propellants from aerosol formulations were banned in most industrialized nations, and manufacturers began subtracting popular cosolvent methylene chloride from hair spray formulations. The ethyl alcohol and alcohol / water systems replaced methylene chloride in the solvent system of many hair sprays. Dimethyl ether and 80/20 isobutane / propane replaced CFCs in the propellant systems of many aerosol sprayers. However, these propellants and solvents are VOC (volatile organic compounds) and should be considered as such in the hair spray formulations in which they are used. The United States Environmental Protection Agency (EPA) has ordered a reduction in the VOC content of hair sprayers to 80% or less in 1998. In addition, Section 183 (e) of the Amendments to the Act for the Clean Air in the United States of 1990, required by the EPA to develop a control strategy to reduce VOC emissions from consumable and commercial products that take into account the potential that forms ozone or "reactivations" of such emissions. In 1992, the EPA published requirements for the State Implementation Plans to reduce VOC emissions. The policy gave a definition of "volatile organic compound" that excludes specific VOC species from negligible reactivation, and makes the distinction between "reactive" VOCs and "negligible reactants" VOCs. Currently, the EPA favors the distinctions between "reactive" and "insignificant reactive" based on whether some species have greater or less atmospheric reactivation compared with ethane. The state of California has established an even stricter requirement for VOC in hair sprays than EPA, limiting VOCs to 55% by June 1999. Currently, the main solvent in most hair sprays is alcohol Ethyl and is present in the amounts of 60% to 95% depending on whether the sprinkler is aerosol or pump type. Ethanol solubilizes polymer systems and provides an optimal delivery system that is easy to use, and dries quickly in the application. In addition, ethanol has a pleasant smell, and has no serious toxicological limitations in use. However, alcohol is a VOC and is reported as such in hair spray systems. To decrease the VOC content of the sprinkler, many manufacturers have replaced ethanol in their sprinklers with water. However, an increase in water concentration can adversely affect the development of the hair sprayer by accelerating the curl drop and / or increasing the drying time in the hair. Manufacturers have cited numerous lists of solvent washes that could theoretically be used in a hair sprayer. For example, U.W.E. Bergemann, et al, (US Patent 4,243,548) discloses a pressurized aerosol formulation in which the solvent can be one of the 21 compounds, or any mixture of these compounds. The listed compounds include ethylmethyl ketone, dimethoxymethane, diethyl carbonate, n-propanol, ethyl chloride, 1,1-dichloroethane, 1-chlorobutane, ethanol, isopropanol, diethyl ether, acetone and methyl acetate among others. Other patents provide similar lists of solvents. See, for example, U.S. Patent No. 5,686,066 to Harada et al. , U.S. Patent No. 5,605,647 to Nimitz et al. , and US Patent No. 4,173,627 to Mandrage et al. Most of these chemicals could be undesirable to consumers or manufacturers for use in personal care products such as hair sprays. For example, some of the solvents, such as acetates, hydrolyze in the presence of water to form harmful acids. Many of the solvents have penetrating odor chemicals, or stain clothes. As a result, ethanol and water remain the predominant solvents of choice for the consumable hair spray formulations. Applicants have unexpectedly discovered that the cosmetically unacceptable odor associated with alkyl acetates such as methyl acetate is substantially reduced when combined with alcohols such as ethanol, and that the alkyl acetates can thus replace some of the alcohol in consumable sprinkler formulations without decrease in consumable acceptance. Applicants have also unexpectedly discovered that ethanol inhibits the hydrolysis of methyl acetate in the presence of water, thereby reducing the formation of harmful acids in formulations containing water. Ethanol also inhibits the damaging effects that methyl acetate itself can cause to some fabrics. Thus, certain alkyl acetates (particularly methyl acetate and / or t-butyl acetate) can unexpectedly be used to replace part of the alcohol (particularly isopropanol and / or ethanol) in consumable spray formulations without adversely affecting development, odor, or sprinkler self-stability will stop the hair. This is an important consideration, because methyl acetate is a "negligible reagent" VOC and thus more environmentally acceptable than ethanol. The measurements show that methyl acetate generates 0.03 grams of ozone per gram of solvent, compared to ethanol that generates 0.42 grams of ozone per gram of solvent. Therefore, it is possible to formulate an improved hair sprayer that provides more of the properties considered desirable for hair repair and that has a low potential to generate ozone at a low level. In accordance with the purposes of this invention, as embodied and broadly described herein, this invention, in one aspect, relates to a hair care composition comprising a fixative, ethanol, and methyl acetate and / or t-butyl acetate. In another aspect, the invention provides a consumable article comprising a hand-held sprinkler container and a composition capable of causing sprinkling within the sprinkler container comprising ethanol and methyl acetate and / or t-butyl acetate. In still another aspect, the invention provides a consumable article comprising a hand-held sprinkler container, and a sprinkling-capable composition that can be sprinkled within the sprinkler container comprising isopropanol and methyl acetate and / or t-acetate. butyl. In yet another aspect, the invention provides a fixation method for hair comprising spraying the compositions of this invention on the hair. These and other objects of this invention are achieved in hair sprayer and consumable sprayer formulations which: (1) releases reduced amounts of reactive VOCs into the atmosphere; (2) it has good storage stability and produces a limited amount of acidic products corrosive to aging; and (3) they are not sticky, and have a fast drying speed, low odor, and acceptable viscosity and curl retention. The additional advantages of the invention will be set forth in part in the description that follows, and in part will be obvious from the description, or may be learned by the practice of the invention. The advantages of the invention will be realized and achieved by means of the elements and combinations particularly pointed out in the appended claims. It will be understood that the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed. The accompanying drawings, which are incorporated in, and constitute a part of this specification, illustrate various embodiments of the invention and together with the description, serve to explain the principles of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a triangular plot of concentrations of ethanol, water and methyl acetate in various compositions of this invention, showing the compositions in which the components are immiscible. The present invention can be more readily understood by reference to the following detailed description of the preferred embodiments of the invention and the Examples included herein to the Figure and its previous and following description. Prior to the present compounds, the compositions and methods are described and described, it will be understood that this invention is not limited to the specific methods, or to the particular formulations, as such may of course vary. It will also be understood that the terminology used herein is for the purpose of describing particular modalities only and, unless otherwise imposed by the context, is not intended to be limiting. It should be noted that, as used in the specification and the appended claims, the singular formulas "a" "an" and "the" include plural references unless the context clearly imposes otherwise. Thus, for example, with respect to "an aromatic compound" includes mixtures of aromatic compounds, with respect to "a fixative" includes mixtures of two or more such fixatives, and the like. The ranges are often expressed herein as "approximately" a particular value, and / or "approximately" another particular value. When such a range is expressed, another modality includes a particular value and / or the other particular value. Similarly, when the values are expressed as approximations, by use of the "approximately" antecedent, it will be understood that the particular value forms another modality. In this specification and in the claims that follow, the reference will be made to a number of terms that will be defined to have the following meanings: Parts by weight, of a particular element or component in a composition or article, means the weight ratio between the element or component and any other elements or components in the composition or article for which a part by weight is expressed. Thus, in a compound containing 2 parts by weight of component X and 5 parts by weight of component Y, X and Y are present in a weight ratio of 2: 5, and are present in such ratio with respect to whether the additional components they are contained in the compound. "_ A percentage by weight of a component, unless specifically stated otherwise, is based on the total weight of the formulation or composition in which the component is included. A residue of a chemical species, as used in the Specification and terminal claims, refers to the portion that is the resulting product of the chemical species in a particular reaction scheme or subsequent formulation or chemical product, as to whether the portion is currently obtained from the chemical species. Ethylene glycol in a polyester refers to one or more units -OCH2CH20- in the polyester, with respect to whether the ethylene glycol was used to prepare the polyester, Similarly, a sodium chloride residue in water refers to sodium and chloride ions in the polyester. the solution, as to whether the ions are obtained by dissolving sodium chloride in water The term "alkyl" as used herein refers to an organic group or saturated, branched or unbranched of 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like . Preferred alkyl groups herein contain from 1 to 12 carbon atoms. The term "lower alkyl" means a cyclic alkyl group of three to eight, preferably five or six carbon atoms. _ "Optional" or "optionally" means that the subsequently described case or circumstance may or may not occur, and that the description includes examples where such a circumstance only occurs and the examples where it does not occur. For example, the phrase "optionally substituted lower alkyl" means that the lower alkyl group may or may not be substituted and that the description includes unsubstituted lower alkyl and lower alkyl where there is substitution. By the term "effective amount" of a compound or property as provided herein, this means that such amount is capable of developing the fuon of the compound or property for which an effective amount is expressed. As will be pointed out in the following, the exact amount required will vary from process to process, depending on recognized variables such as the compounds used and the observed processing conditions. Thus, it is not possible to specify an exact "effective amount". However, an appropriate effective amount can be determined by one of ordinary skill in the art using only "routine experimentation." The term "polymer" includes copolymers, and copolymers recited herein include copolymers, unless the context dictates. Another way.The term "fixer" refers to one or more groups of polymers or resins that, when applied to the hair, retain hair in the desired formation and inhibit curl drop.The polymer or resin used in the hair sprayer or group of polymers and / or resins when presented as a mixture, refers to the present and the claims as a fixative.The term "ethanol" or "ethyl alcohol" refers to CH3CH2OH. Ethanol weight is given, percentage by weight refers only to such portions of ethanol, and does not include other ingredients that may be present in commercially available ethanol. Thus, while various types of commercially available alcohol compositions can be used in the formulations and compositions of this invention, such as denatured alcohol and azoteotropic alcohol 95/5, the percent methanol by weight is based solely on the ethanol component of the commercially available composition. For example, a composition containing 50% azeotropic ethanol 95/5 only contains 47.5"ethanol, however, a composition substantially free of solvents other than ethanol allowed for the presence of small amounts of water or other solvents that are present in many commercially available ethanols, including azeotropic and denatured alcohols The term "propellant" means a composition that can be used to expel the contents of a container through a suitable valve in the form of a fine dispersion. as liquid solvents in many formulations of the invention, they are distinguished from the solvent system of those formulations by the fact that the propellants are gases at room temperature and atmospheric pressure.A propellant may include one or more particular propellant compounds. in organic solvent "refers to a ation in which the ingredients are soluble, dispersible, or miscible in an organic solvent, but can not tolerate water well. Water may be present in such formulations, but is typically present, if at all, at concentrations that do not materially interfere with the fuon of the formulation or consistency of administration. Organic solvent-based formulations typically contain no more than 15% by weight of water and more typically contain no more than 5% by weight of water. A "water-based solvent" formulation refers to a formulation in which the ingredients are soluble, dispersible or miscible in water or a water / organic solvent mixture. Organic solvents may also be present in such formulations. Typically at any level. Nevertheless, the organic solvents preferably do not exceed 55% by weight of the formulation.

A "sprayable" composition is a liquid composition that can be sprayed in a finely dispersed form through hand-held sprayers and aerosol cans, such as containers that typically contain consumable hair sprays. "sprayable", is a function of the cohesive energy of liquid surface, which is related to viscosity. Sprayable compositions generally have viscosities between about 40 cP, preferably have viscosities between about 30 cP, and even more preferably between about 20 cP, or are thinned by breaking such viscosities that meet these limits at the high breakthrough rates typically experienced by a liquid being forced through a sprinkler nozzle. This invention is generally applicable to all consumable spray compositions containing ethanol and / or isopropanol, but is particularly useful in compositions that are used for hair care. Such compositions include, for example, hair sprays, bubblers, sprinkler gels, fixation lotions, frostings, and foams. The invention is especially useful in hair sprays. In one embodiment, the invention provides a hair care composition comprising: a fixative, ethanol and methyl acetate and / or t-butyl acetate. The composition is preferably substantially free of any organic non-propelling solvents, other than ethanol, methanol acetate and / or t-butyl acetate, and more preferably is substantially free of any non-propellant organic solvents other than ethanol and methyl acetate. The composition may also contain water and / or a propellant. _ When water is included in the formulation, it is important to ensure that the components are miscible, to ensure that a consistent formulation (in terms of uniformity of pressure and product uniformity) is released as a sprinkler. Referring to Figure 1, a phase diagram graph of ethanol, methyl acetate and water concentrations is shown, showing the region where the three components are immiscible. The water-containing compositions of this invention can generally comprise water, ethanol, and methyl acetate in any range of concentrations outside the immiscibly graded range in Figure 1, providing the other ingredients of the formulation that are compatible with the solvent system. In a modality that is particularly suitable for the hair care compositions of the present invention, especially hair spray, the fixative is used in the amount of about 1 to 7 weight percent, based on the total weight of the hair. formulation of hair sprayer. Preferred amounts of fixative are in the range of 2% to 6%, while the most preferred range is 4% to 6%, based on the total weight of the hair spray formulation. In another embodiment of this invention that is particularly well suited for use in pump formulations for the hair sprayer (i.e., formulations that do not use a propellant), the hair care composition of this invention preferably comprises from about 1 to about 12% by weight of the fixative, from about 20 to about 90% by weight of ethanol, and from about 1 to about 60% by weight of acetate (methyl acetate and / or t-butyl acetate). These compositions more preferably comprise from about 4 to about 8% by weight of the fixative. These compositions may also contain water. If the compositions comprise water, they preferably comprise from about 0.01 to about 45% by weight of water, and more preferably from about 0.01 to about 30% by weight of water. The invention also encompasses numerous combinations of ethanol and acetate ranges within the percent by weight ranges mentioned immediately above. Thus the lower end of the range% by weight can, in alternative modalities, be 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight, or 50% by weight. "" The upper end of the ethanol% by weight can, in alternative modalities, be 85% by weight, 80% by weight, 75% by weight, 70% by weight, 65% by weight, 60% by weight 55% by weight , 50% by weight, 45% by weight, or 40% by weight. The upper end of the acetate% by weight can, in alternative embodiments, be 55% by weight, 50% by weight, 45% by weight, 40% by weight, 35% by weight, or 30% by weight. The lower end of the acetate% by weight can, in alternative modalities, be 3% by weight, 5% by weight, 10% by weight, 15% by weight, 20% by -weight, 25% by weight, 30% by weight. weight, 35% by weight, 40% by weight, or 45% by weight. The end points of these four sets of alternate endpoints, for the percentages by weight of acetate and ethanol can be selected and combined in any combination that is mathematically possible, and can be combined with the preferred weight and water fixator ranges or more preferred. For example, in a preferred embodiment, the compositions of this invention comprise from about 30 to about 55% by weight of ethanol, and from about 10 to about 40% by weight of acetate (methyl acetate and / or t-butyl acetate) ) and from about 4 to about 8% by weight of the fixative. The invention also provides hair care compositions containing a propellant. Thus, in another embodiment, the invention provides a hair care composition that is particularly suitable for use in hair sprays comprising a fixative, ethanol and methyl acetate and / or t-butyl acetate and a propellant. Preferably the composition comprises: from about 1 to about 10% by weight of fi brous; from about 20 to about 75% by weight of ethanol; from about 1 to about 60% by weight of acetate (methyl acetate and / or t-butyl acetate); and from about 15 to about 45% by weight of propellant. More preferably the composition comprises from about 2 to about 8% by weight of fixative; and from about 20 to about 35% by weight of propellant. The above formulations may also contain water, which, when present, preferably comprises from about 0.01 to about 45% by weight of the composition, and more preferably from about 0.01 to about 30% by weight of the composition. The invention also encompasses numerous combinations of ethanol and acetate ranges within the percent by weight ranges mentioned immediately above. Thus, the lower end of the range of% by weight of ethanol can, in alternative modalities, be 25% by weight, 7"30"% by weight, "" 35% by weight, 40% by weight, 45% by weight , or 50% by weight. The upper end of% by weight of ethanol can, in alternative embodiments, be 70% by weight, 65% by weight, 60% by weight, 55% by weight, 50% by weight, 45% by weight, or 40% by weight. The upper end of the% by weight of the acetate, in alternative modalities, is 55% by weight, 50% by weight, 45% by weight, 40% by weight, 45% by weight or 30% by weight. The lower end of the% by weight of the acetate can, in alternative modalities, be 3% by weight, 5% by weight, 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight , 35% by weight, 40% by weight, or 45% by weight. The endpoints of these four sets of alternative endpoints for the percentages by weight of acetate and ethanol can be selected and combined in any combination that is mathematically possible, and can be combined with the preferred or most preferred fixative, propellant and weight ranges in water For example, in a more preferred embodiment, the compositions of this invention comprise from about 20 to about 55% by weight ethanol; from about 10 to about 40% by weight of methyl acetate; from about 4 to about 8% by weight of the fixative; and from about 20 to about 35% by weight of the propellant. In hair spray pumps of this invention the solvent system generally comprises at least 88% by weight of the formulation, and preferably at least 92% by weight of the formulation. The solvent system in pump-type hair sprinklers generally comprises less than 98% by weight of the formulation, and preferably less than 96% by weight. In hair sprinklers of the propellant type of this invention the solvent system (excluding the propellant) generally comprises at least 45% by weight of the formulation, and preferably at least 60% by weight of the formulation. The solvent system in hair sprinklers of the propellant type generally comprises less than 80% by weight of the formulation, and preferably less than 75% by weight. If a propellant is present, it is preferably present in an amount of about 15 to about 45 weight percent of the propellant, and more preferably it is present in an amount of about 20 to about 35 weight% of the propellant. The solvent system in the sprinklers. for pump-type hair and propellant of this invention comprise ethanol, methyl acetate and / or t-butyl acetate, and sometimes water. According to this invention, acetate (methyl acetate and / or t-butyl acetate) can be substituted by various amounts of ethanol in the solvent system. Thus, the acetate can be replaced by less than 70% by weight, 65% by weight, 60% by weight, 55% by weight, 50% by weight, 45% by weight, 40% by weight, 35% by weight, 30% by weight, or 25% by weight of ethanol, and / or more than 5% by weight, 10% by weight, 15% by weight, 20 by weight, 25% by weight, 30% by weight, or 35% by weight of ethanol, in various modalities in any overlapping range of maximum and minimum percentages, for either pump-type or propeller-type hair sprinklers, to the presence of amounts of other compounds. A composition in which the acetate has been replaced by less than x% ethanol, refers to a composition in which ethanol and acetate are present in a ratio of more than (l-x) / x. Similarly, a composition in which acetate has been substituted more than x% ethanol, refers to a composition in which ethanol and acetate are present in a ratio of less than (1-x) / x. Alkyl acetates, including methyl acetate, are known to hydrolyze in the presence of water. However, it is determined experimentally that the presence of ethanol significantly limits the hydrolysis of methyl acetate. The molar ratio of water to ethanol in pump and aerosol compositions of this invention should be kept below the maximum given in Table 1 to minimize the formation of acetic acid. TABLE 1 Methyl acetate,% by weight Molar ratio of Water / Ethanol (Maximum) 1 to 10 10 11 to 20 5 21 to 30 3 31 to 40 2 In a separate embodiment shown in Table 2, the ratio of water to ethanol it is kept under the maximum in Table 2 to the minimum in the formation of acetic acid. Table 2 Methyl acetate,% by weight Molar ratio of Water / Ethanol (Maximum Approximate) 5 to 10 10.0 11 to 15 6.0 16 to 20 3.5 21 to 25 2.5 26 to 30 _ 2.0 31 to 40 1.6 The propellant used in the compositions for hair care and other compositions of this invention is typically one or more aliphatic hydrocarbons of C_ to C4, dimethyl ether, one or more hydrofluorocarbons (preferably Ci or C2), fluoropropanes, and mixtures thereof. The aliphatic hydrocarbons can be branched or straight-chain and include methane, ethane, propane, butanes (especially isobutane), pentanes and mixtures thereof. Preferred propellants for use in this invention include propane, isobutane, butane, dimethyl ether, 1,1-difluoroethane, 1, 1, 2-f.etrafluoroethane and mixtures thereof. In a particularly preferred embodiment, the propellant comprises 1,1-difluoroethane. In another embodiment a particularly preferred propellant, especially in organic solvent based systems, is a mixture of propane and isobutane. The propellant preferably comprises from about 5 to about 50 parts by weight of propane, and from about 50 to about 95 parts by weight of isobutane. If any water is present in the formulation, and especially if the formulation contains more than 15% by weight of water, then the propellant system preferably also comprises, in addition to propane and butane, dimethyl ether or one of the hydrofluorocarbons mentioned above. Another particularly preferred propellant, especially in solvent-based water systems, is dimethyl ether. The hair spray formulations of this invention contain a fixative, which is typically one or more of a group of hair care polymers that are commercially available and routinely used in hair sprays. Thus, for example, in one embodiment the fixative is: one or more polymers or copolymers of acrylic acid and / or methacrylic acid or one of its polymerizable esters; one or more polymers or copolymers of acrylamide, hydroxy acrylate, t-butylaminoethyl methacrylate, octyl acrylate, octylacrylamide, vinyl caprolactam, crotonic acid, dimethylaminopropylacrylamide, vinylpyrrolidone, vinyl acetate, vinyl propionate, vinylcaprolactam, and / or dimethicone; one or more ethyl, propyl, or butyl esters of polyvinyl methyl ether and maleic anhydride copolymer; one or more vinyl acetate / crotonates / vinyl neodecanoate copolymers; or a mixture of them. Examples of suitable polymers are polyvinylpyrrolidone (PVP), polyvinylcaprolactam, polyvinyl acetate, polyacrylates, and polymethacrylates; and VP / VA copolymers and terpolymers (vinyl pyrrolidone / vinyl acetate), VA / crotonic acid / vinyl neodecanoate, VA / crotonic acid, or octylacrylamide / acrylates / butylaminoethyl methacrylate, VA, mono-n-butyl maleate, and Isobornyl acrylate, and VP / VC (vinylpyrrolidone / vinylcaprolactam) / methacrylate. of dimethylaminoethyl, VA Copolymer / Crotonates / Vinyl Neodecanate supplied by National Starch under the trademark Resyn 28-2930 is typical of hair care polymers that can be used in formulations of the present invention. Many of the above fixatives are not very water tolerant, and thus are usually employed in solvent-based organic systems.Other fixatives are more suitable for use in solvent-based water systems.For example, in one embodiment the invention provides a hair care composition further comprising water, wherein the fixative is a water-dispersible sulfopolyester.A preferred water-dispersible polyester is known by the name INCI diglycol / cyclohexane dimethanol / isophthalates / sodium sulfoisophthalate copolymer, which contains sodium and hydroxyl substituents and more preferably has a Tg of 40 ° C to 50 ° C and an inherent viscosity of 0.24 to 0.60 dl / g and consists essentially of repeating units of (a) a dicarboxylic acid component consisting essentially of 20 to 26 mole percent of dimethyl-5-sodiosulfoisophthalate and 74 to 80 mole percent of isophthalic acid, based on 100 mole percent of ac dicarboxylic acid, and (b) a diol component consisting essentially of 10 to 30 mole percent of 1,4-cyclohexanedimethanol and 70 to 90 mole percent of. diethylene glycol, based on 100 percent mol of diol. An especially preferred sulfopolyester is sold by Eastman Chemical Company under the trademark Eas tman AQ 48 Ultra polymer. The hair care compositions of this invention may also contain a neutralizer, if neutralized acidic sites in the fixative. Thus, in another embodiment the invention provides an additional hair care composition comprising from about 0.1 to about 5% by weight of a neutralizer. Exemplary neutralizers include aminomethylpropanol; dimethylaminomethylpropanol; triisopropylamine; dimethyl stearamine; hydrogenated bait dimethyl amine; triethanolamine; tris (hydroxymethyl) aminomethane; sodium hydroxide; potassium hydroxide; ammonium hydroxide; diethylpropylamine, and mixtures thereof. Preferred neutralizers include AMP-95 (2-amino, 2-methyl, 1-propanol), DMS (dimethyl stearamine) and potassium hydroxide, with AMP-96 being especially preferred. Other conventional additives such as preservatives, fragrances, antifoaming agents, hair conditioners, dispersants, corrosion inhibitors, wetting agents, emulsifiers, gloss enhancers, and plasticizers can be added in amounts as desired, up to about 5% by weight of the total formulation. The invention is also applicable to consumable sprayer products other than hair care products. For example, the invention is also applicable to deodorants for transpiration, and antiperspirants that are applied to human skin with manually held sprinkler containers. The invention is also applicable to manual fastening spaces and surface sprinklers, which are used to deodorize and / or disinfect interior environments and surfaces. Thus, the invention also provides a consumable article comprising a manually held sprinkler container, and a sprayable composition contained within the sprinkler vessel comprising ethanol and methyl acetate and / or t-butyl acetate. The invention is also applicable to sprayable compositions comprising isopropanol in place of, or in addition to, ethanol, and sprayable compositions comprising t-butyl acetate in addition to, or in place of, methyl acetate. The sprinkler containers of this invention are those that are fastened in, and operable by only one hand. Recent exemplary sprinklers thus include pressurized aerosol cans, trigger-type sprinkler bottles, and other pump sprinkler bottles that can be held and pumped simultaneously by one hand. The pump-type sprayable composition preferably comprises from about 20 to about 90% by weight of alcohol (ethanol and / or isopropanol) and from about 1 to about 60% by weight of acetate (methyl acetate and / or t-butyl acetate) ). The propellant type sprayable composition of this invention preferably comprises from about 20 to about 75% by weight of alcohol (methanol and / or isopropanol); from about 1 to about 60% by weight of acetate (methyl acetate and / or t-butyl acetate), and from about 15 to about 60% by weight of propellant. More preferably, the composition comprises about 20 to about 35% by weight of propellant. The sprayable composition may further comprise other ingredients, including water, active agents, and mixtures thereof. If water is included in the composition, it is preferably present in an amount of from about 0.01 to about 45% by weight, and more preferably from about 0.01 to about 20% by weight. The invention also encompasses numerous combinations of alcohol ranges (ethanol and / or isopropanol) and acetate (methyl acetate and / or t-butyl acetate) within the percent by weight ranges mentioned immediately above. Thus, the lower end of the% by weight alcohol range can, in alternative embodiments of the pump and propellant type compositions, be 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight, or 50% by weight. The upper end of the% by weight of the alcohol can, in alternative embodiments of the pump-type composition, be 85% by weight, 80% by weight, 75% by weight, 70% "by weight, 65% by weight, 60% by weight, 55% by weight, 50% by weight, 45% by weight or 40% by weight The upper end of the% by weight of the alcohol can, in alternative embodiments of the propellant type composition, be 70% by weight, 65 % by weight, 60% by weight, 55% by weight, 50% by weight, 45% by weight, or 40% by weight The upper end of the% by weight of the acetate can, in alternative embodiments of the propellant-type compositions and pump will be 55% by weight, 50% by weight, 45% by weight, 40% by weight, 35% by weight, or 30% by weight.The lower end and the% by weight of acetate can, in alternative embodiments of the propellant and pump type composicones, be 3% by weight, 5% by weight, 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, or 45% by weight. * The final points of These four sets of alternative endpoints for the percentages by weight of acetate and alcohol can be selected and combined in any combination that is mathematically possible, and can be combined with the preferred or most preferred fixative, propellant, and water weight ranges. For example, in a preferred embodiment, the compositions of this invention comprise from about 30 to about 55% by weight of alcohol (ethanol and / or isopropanol), and from about 10 to about 40% by weight of acetate (methyl acetate and or t-butyl acetate) and from about 4 to about 8% by weight of the fixative. In the pump-type spray compositions of this invention, the solvent system generally comprises at least 80% by weight of the formulation, and preferably at least 90% by weight of the formulation. The solvent system in pump-type spray compositions generally comprises at least 99.99% by weight of the formulation, and preferably less than 99% by weight. In the propellant type sprayable compositions of this invention the solvent system (excluding the propellant) generally comprises at least 40% by weight of the formulation, and preferably at least 60% by weight of the formulation. The solvent system in spray type propellant compositions generally comprises less than 85% by weight of the formulation, and preferably less than 80% by weight. If a propellant is present, it is preferably present in the composition in an amount of about 15 to about 60 weight percent propellant, and more preferably is present in an amount of about 20 to about 35 weight percent of the propellant. The solvent system in the pump and propellant type sprayable compositions of this invention comprises ethanol, methyl acetate (and / or t-butyl acetate), and sometimes water. According to this invention, the acetate can be substituted by several amounts of ethanol in the solvent system. Thus, the acetate can be replaced by less than 70% by weight, 65% by weight, 60% by weight, 55% by weight, 50% by weight, 45% by weight, 40% by weight, 35% by weight, 30% by weight, or 25% by weight of ethanol, and / or more than 5% by weight, 10% by weight, 15% by weight, 20% by weight, 25% "by weight, 30% by weight or % by weight of ethanol, in various modalities in any overlapping range of maximum and minimum percentages, for either pump or propellant type sprays, with respect to the presence or quantities of other components.In an alternative embodiment, sprayable compositions may comprising isopropanol in place of, or in addition to, ethanol, and / or t-butyl acetate in addition to, or # in place of methyl acetate, in the various ratios cited above.The active agents which may be included in the composition sprayable include (1) perspiration deodorants, antiperspirants, and mixtures thereof, and (2) environmental deodorants, disinfectants, fragrances and mixtures thereof. The active agents are preferably present in the spray composition in an amount of about 0.01 to about 10% by weight. Exemplary antiperspirants and perspiration deodorants include zinc salts such as "zinc sulfate and zinc chloride, glycinates such as aluminum-zirconium glycinate, aluminum chlorohydrate, aluminum-zirconium tetrachlorohydrex, and zinc carbonate." Disinfectants and deodorants examples include phenolic-type disinfectants such as orthophenylphenol and quaternary ammonium compounds such as dimethylbenzylammonium chloride and hexa -tonium chloride, Additional examples are given in U.S. Patent Nos. 4,565,693 and 3,832,459, and the descriptions of these patents are incorporated herein by reference. The following examples are proposed to provide those of ordinary skill in the art with a full description and description of how the compositions claimed herein are made and evaluated, and are intended to be purely exemplary of the invention and are not intended to be pretended as to limit the scope of the inventors regarding their invention. Efforts have been made to ensure truthfulness regarding numbers (eg, amounts, temperature, etc.), but some errors and deviations could be counted. At least indicated otherwise, parts are parts by weight, temperature is in ° C or is at room temperature, and pressure is a, or almost atmospheric. The concentration of acetic acid was determined by gas chromatography. • Balance 47, Resyn 28-2930, and Ap ojner LV-71 are from National Starch and Chemical Company, Bridgewater, NJ. • AQ 48 Ultra is available from Eastman Chemical Company, Kingsport Tennessee. • INCI Designation for Balance 41 is Octylacrylamide Copolymer / Acrylates / Butylaminoethyl methacrylate.

• INCI Designation of Resyn 28-2930 is "" VA Copolymer / Crotonates / Vinyl Neodecanoate. • INCI Designation of Amphomer LV-71 is Copolymer of Octylacrylamide / Acrylates / Butylaminoethyl methacrylate.

• INCI designation of AQ 48 Ultra es- Copolymer of Diglycol / Cyclohexan Dimetanol / Isophthalates / Sulfoisophthalate of Sodium. • AMP-95 is 2-Amino, 2-Methyl, 1-Propanol with approximately 5% by weight of water. • Alcohol SD 50 is etandl denatured with t-butanol (0.125 gal / 100 gal) and brucine sulfate (1.5 oz / 100 gal), available from Eastman Chemical Company, Kingsport, TN. • Dymel A is dimethyl ether, available from DuPont Company, Wilmington, DE. • Propeller A-46 is a product of Aeropres Corporation, Shreveport, LA, and is 16/84 p / p propane / isobutane. To illustrate the utility of methyl acetate in pump-type hair sprayers, the formulations were prepared from two vinyl polymers, and a water dispersible polyester available from Eastman Chemical Company, Kingsport, Tennessee. The formulations containing the vinyl polymers were prepared by dissolving the polymers in ethanol / AMP-95 and then adding the other ingredients. The water dispersible polyester Eastman was dispersed in water and the other ingredients were added to make the sprinklers for the hair. All the aging of the samples was carried out at room temperature. The following examples show the formulations and results of the sprinklers for pump-type hair. Example 1 Component Percent in Weight Analysis for the indicated acetic acid < 0.1% _ by weight present after 12 months of aging. Example 2 Component Percent in Weight Analysis for indicated acetic acid < 0.1% by weight present after 3 months of aging. Analysis for indicated acetic acid < 0.1% by weight present after 12 months of aging. Example 3 _ Component Percent in Weight Analysis for indicated acetic acid < 0.1% by weight present after 3 months of aging, and 0.3% by weight of acetic acid after 12 months. months of aging. Example 4 Component Percent in Weight Analysis for indicated acetic acid not present after < 0.1"% by weight present after 5 months of aging, and 0.3% by weight present after 12 months of aging Example 5 Component Weight percent Analysis for indicated acetic acid < 0.1% by weight present after 6 months of aging, and < 0.1% by weight present after 12 months of aging. Example 6 Component Percent in Weight Analysis for indicated acetic acid < 0.1% by weight present after 3 months of aging, 0.2% by weight present after 10 months of aging, and 0.5% by weight after 13 months of aging. The formulation became cloudy during the time. Example 7 Component Percent in Weight Analysis for indicated acetic acid < 0.1% by weight present after 6 months of aging, and 0.2% by weight present after 7 months of aging. Example 8 Component Percent in Weight Analysis for indicated acetic acid < 0.1% by weight present after 6 months of aging, 0.25% by weight after 7 months of aging and 0.34% by weight after 10 months of aging. The formulation became cloudy during the time. To illustrate the utility of methyl acetate in aerosol hair sprayers, the formulations "were prepared from an Eastman water dispersible polymer and a vinyl polymer.The aerosol" concentrates "were prepared using the same procedure as the die For the pump hair sprinklers, the propellant was then added to the concentrate to make the spray hair spray composition.The following examples are for aerosol hair sprayers, Example 9 This is an example to replace water with methyl acetate in a typical aerosol formula Eas tman AQ 48 to reduce drying time Component Percent in Weight Percent in in Concentrate Weight in Aerosol Analysis of concentrate for acetic acid indicated 0.2% by weight present after of 6 * months of aging, and 0.5% by _ weight after 9 months of aging.The aerosol formulation remains clear after of 12 months of aging. Example 10 Component Percent in Weight Percent in in Concentrate Weight in Aerosol Analysis of the indicated concentrate 0.26% by weight of acid after 5 months of aging, and 1.0% by weight of acetic acid after 12 months of aging. The formulation remains clear after 12 months of aging. Example 11 Component Percent in Weight percent in Weight in Concentrated Spray Throughout this application, several publications are mentioned. The descriptions of these publications in their entirety are incorporated herein for reference in this application to more fully describe the state of the art to which this invention pertains. It will be apparent to those skilled in the art that various modifications and variations may be made in the present invention without departing from the scope or spirit of the invention Other embodiments of the invention will be apparent to those skilled in the art from the consideration of The specification and practice of the invention described herein It is intended that the specification and examples are considered as exemplary only, with true scope and spirit of the invention being indicated by the following claims.

Claims (48)

1. CLAIMS 1. A composition for hair care, characterized in that it comprises: a. a fixative; b. ethanol; and c. methyl acetate and / or t-butyl acetate.
2. 2. The composition for hair care according to claim 1, characterized in that it comprises:. to . from about 1 to about 12% by weight of fixative; b. from about 20 to about 90% by weight of ethanol; and c. from about 1 to about 60% by weight of methyl acetate.
3. 3. The hair care composition according to claim 1, characterized in that it comprises: a. from about 4 to about 8% "by weight" of fixative; b. from about 30 to about 55% by weight of ethanol; and c. from about 10 to about 40% by weight of methyl acetate.
4. 4. The composition for hair care of. according to claim 1, characterized in that the fixator comprises: a. a polymer or copolymer of acrylic acid and / or methacrylic acid or one of its polymerizable esters; b. a polymer or copolymer of acrylamide, hydroxy acrylate, t-butylaminoethyl methacrylate, octyl acrylate, octylacrylamide, vinylcaprolactam, crotonic acid, dimethylaminopropylacrylamide, vinylpyrrolidone, vinyl acetate, vinyl propionate, vinylcaprolactam, and / or dimethicone; c. an ethyl, propyl, or butyl ester of polyvinyl methyl ether and maleic anhydride copolymer; d. a vinyl acetate / crotonates / vinyl neodecanate copolymer; and. an octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer; or f. a mixture of it.
5. The hair care composition according to claim 1, characterized in that the fixative is a copolymer of vinyl acetate / crotonates / vinyl neodecanoate or octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer.
6. 6. The hair care composition according to claim 1, characterized in that it additionally comprises water, wherein the fixative is a sulfopolyester dispersible in water.
7. The hair care composition according to claim 1, characterized in that it additionally comprises water, wherein the fixative is a diglycol / cyclohexane dimethanol / isophthalates / sodium sulfoisophthalate copolymer.
8. 8. The hair care composition according to claim 1, characterized in that it additionally comprises a propellant.
9. The hair care composition according to claim 1, characterized in that it additionally comprises water and a propellant, wherein the propellant comprises dimethyl ether.
10. 10. The hair care composition according to claim 1, characterized in that it additionally comprises a propellant, wherein the propellant comprises methane, ethane, propane, isobutane, n-butane, dimethyl ether, 1,1-difluoroethane, 1, 1, i, 2-tetra "fluoroethane or a mixture thereof 11.
11. The hair care composition according to claim 1, characterized in that it additionally comprises a propellant, wherein the propellant comprises propane and isobutane.
12. The hair care composition according to claim 1, characterized in that it additionally comprises a propellant, wherein the propellant comprises from about 5 to about 50 parts by weight of propane, and from about 50 to about 95 parts by weight of isobutane
13. 13. The hair care composition according to claim 1, characterized in that it additionally comprises a propellant, in The propellant comprises 1,1-difluoroethane.
14. 14. The hair care composition according to claim 1, characterized in that it comprises: a. from about 1 to about 10% by weight of fixative; b. from about 20 to about 75% by weight of ethanol; c. from about 1 to about 60% by weight of methyl acetate; and d. from about 15 to about 45% by weight of propellant.
15. 15. The hair care composition according to claim 1, characterized in that it comprises: a. from about 2 to about 8% by weight of fixative; ~ b. from about 20 to about 55% by weight of ethanol; c. from about 10 to about 40% by weight of methyl acetate; and d. from about 20 to about 35% by weight of propellant.
16. 16. The hair care composition according to claim 1, characterized in that it additionally comprises water.
17. 17. The hair care composition according to claim 1, characterized in that it comprises: a. from about 1 to about 12% by weight of fixative; b. from about 20 to about 90% by weight of ethanol; c. from about 1 to about 60% by weight of methyl acetate; and d. from about 0.01 to about 45% by weight of water.
18. 18. The hair care composition according to claim 1, characterized in that it comprises: a. from about 4 to about 8% by weight of fixative; b. from about 30 to about 55% by weight of ethanol; c. from about 10 to about 40% by weight of methyl acetate; and d. from about 0.01 to about 30% by weight of water.
19. 19. The hair care composition according to claim 1, characterized in that it comprises: a. from about 1 to about 10% by weight of fixative; b. from about 20 to about 75% by weight of ethanol; c. from about 1 to about 60% by weight of methyl acetate; and d. from about 0.01 to about 45% by weight of propellant.
20. The hair care composition according to claim 1, characterized in that it comprises: a. from about 2 to about 8% by weight of fixative; b. from about 20 to about 55% by weight of ethanol; c. from about 10 to about 40% by weight of methyl acetate; d. from about 0.01 to about 30% by weight of water; and e. from about 20 to about 35% by "propellant weight" 21.
21. The hair care composition according to claim 1, characterized in that it additionally comprises water, wherein the composition comprises from about 5 to about 10% by weight of methyl acetate, and the molar ratio of water to ethanol does not exceed about 10.
22. The hair care composition according to claim 1, characterized in that it additionally comprises water, wherein the composition comprises from about 11 to about 15. % by weight of methyl acetate, and the molar ratio of water to ethanol does not exceed about 6.
23. 23. The hair care composition according to claim 1, characterized in that it additionally comprises water, wherein the composition comprises from about 16 to about 20% by weight of methyl acetate, and the molar ratio of water to ethanol is not Xcede approximately 3.5.
24. 24. The hair care composition according to claim 1, characterized in that it additionally comprises water, wherein the composition comprises from about 21 to about 25% by weight of methyl acetate, and the molar ratio of water to ethanol is not exceeds approximately 2.5.
25. 25. The hair care composition according to claim 1, characterized in that it additionally comprises water, wherein the composition comprises from about 26 to about 30% by weight of methyl acetate, and the molar ratio of water to ethanol is not exceeds approximately 2.0.
26. 26. The hair care composition according to claim 1, characterized in that it additionally comprises water, wherein the composition comprises from about 31 to about 40% by weight of methyl acetate, and the molar ratio of water to ethanol does not exceed approximately 1.6.
27. 27. The hair care composition according to claim 1, characterized in that it additionally comprises a * neutralizer.
28. 28. The hair care composition according to claim 1, characterized in that it additionally comprises from about 0.1 to about 5% by weight of a neutralizer, wherein the neutralizer comprises aminomethylpropanediol, aminomethylpropanol; dimethylaminomethylpropanol; triisopropylamine; dimethylsteramine; Hydrogenated baking dimethylamine; triethanolamine; tris (hydroxymethyl) aminomethane; sodium hydroxide; potassium hydroxide; ammonium hydroxide; or diethylpropylamine.
29. 29. The hair care composition according to claim 1, characterized in that it additionally comprises from about 0.1 to about 5% by weight of a neutralizer, wherein the neutralizer comprises 2-amino, 2-methyl, 1-propanol.
30. 30. The hair care composition according to claim 1, characterized in that it is substantially free of any additional organic non-propellent solvents.
31. 31. The hair care composition according to claim 1, characterized in that it is selected from the group consisting of bubblers, a sprinkler gel, a fixing lotion, a glaze, and a foam.
32. 32. The composition for hair care according to claim 1, characterized in that it is selected from a group consisting of a hair sprayer.
33. 33. A hair care composition, characterized in that it comprises: a. from about 1 to about 7% by weight of fixative; b. from about 20 to about 90% by weight of ethanol; and c. from about 1 to about 40% by weight of ethyl acetate.
34. 34. A consumable article, characterized in that it comprises: a. a manual sprinkler container; and b. a sprayable composition contained within the sprinkler vessel comprising: i. from about 20 to about 90% by weight of ethanol; and ii. from about 1 to about 60% by weight of methyl acetate and / or t-butyl acetate.
35. 35. The consumable article according to claim 34, characterized in that the sprayable composition comprises: a. from about 20 to about 90% by weight of ethanol; and b. from about 1 to about 60% by weight of methyl acetate.
36. 36. The consumable article according to claim 34, characterized in that the sprayable composition comprises: a. from about 30 to about 55% by weight of ethanol; and b. from about 10 to about 40% by weight of methyl acetate.
37. 37. The consumable article according to claim 34, characterized in that the sprayable composition comprises: a. from about 20 to about 75% by weight of ethanol; b. from about 1 to about 60% by weight of methyl acetate; and c. from about 15 to about 60% by weight of propellant
38. 38. The consumable article according to claim 34, characterized in that the sprayable composition comprises: a. from about 20 to about 55% by weight ethanol; b. 10 to about 40% by weight of methyl acetate, and C. of about 20 to about 35% by weight of propellant
39. 39. The article, consumable according to claim 34, characterized in that the sprayable composition further comprises about 0.01. at about 45% by weight of water
40. 40. The article -consumable according to claim 34, characterized in that the sprayable composition further comprises about 0.01 to about 20% by weight of water
41. 41. The consumable article in accordance with the claim 34, characterized in that the sprayable composition further comprises a perspiration deodorant, antiperspirant, or mixture thereof.
42. 42. The consumable article according to claim 34, characterized in that the sprayable composition further comprises deodorant or environmental disinfectant, fragrance, or mixture thereof.
43. 43. A consumable item, characterized in that it comprises: a. a sprinkler container for manual fastening; and b. a sprayable composition contained within the sprinkler vessel comprising: i. from about 20 to about 90% by weight of isopropanol; and ii. from about 1 to about 60% by weight of methyl acetate and / or t-butyl acetate.
44. 44. The consumable article according to claim 34, characterized in that the sprayable composition comprises: a. from about 20 to about 90% by weight of isopropanol; and b. from about 1 to about 60% by weight of methyl acetate.
45. 45. The consumable article according to claim 34, characterized in that the sprayable composition comprises: a. from about 30 to about 55% by weight of isopropanol; and b. from about 10 to about 40% by weight of methyl acetate.
46. 46. The consumable article according to claim 34, characterized in that the sprayable composition comprises: a. from about 20 to about 75% by weight of isopropanol; b. from about 1 to about 60% by weight of methyl acetate, and c from about 15 to about 60% by weight of propellant
47. 47. The consumable article according to claim 34, characterized in that the spray composition comprises: a from about 20 to about 55% by weight of isopropanol, b from about 10 to about 40% by weight of methyl acetate, and from about 20 to about 35% by weight of propellant,
48. 48. A method of hair fixation. , characterized in that it comprises spraying the composition according to claim 1 on the hair.