MXPA99003287A - Non-ionic derivative starches and their uses in capillary cosmetic compositions in aero - Google Patents

Abstract

The present invention relates to hair cosmetic compositions of low volatile organic compounds, made in aerosol, which contain nonionically derived starches optionally hydrolyzed and / or ionically modified. Such compositions provide a clear solution with low viscosity, good azation characteristics, a clear film, which is non-tacky, has good stiffness and improved moisture resistance

Description

NON-IONIC DERIVATIVE STARCHES AND THEIR USES IN AEROSOL CAPILLARY COSMETIC COMPOSITIONS DESCRIPTION OF THE INVENTION The present invention relates to hair cosmetic compositions made in aerosol, particularly hair setting compositions, which contain nonionic derived starches and to a process for fixing the hair using such compositions. In its most basic forms, the cosmetic hair compositions contain a polymer that forms a film, which acts as the cosmetic system, and a delivery system, which is usually one or more alcohols, a mixture of alcohol and water, or water . In the case of the delivery system, it will also contain a propellant, typically a volatile hydrocarbon. The process of fixing or styling the hair ordinarily involves the application of an aqueous solution or dispersion of one or more film-forming materials to comb the hair which has been previously moistened or submerged in water where after the treated hair is curled or otherwise styled and dried form. The alternative application of this solution or dispersion can be done to the hair which has already been styled or dried. Once the aqueous solution or dispersion is dried, the individual hairs will have a film deposited in the same presence that will prolong the curl retention or other desired configurations in the wearer's hair. Additionally, the presence of such films will impart such desirable properties as body and homogeneity. To be effective, the ingredients forming the film of a hair cosmetic composition preferably meet a number of requirements. The film derived from these ingredients must be flexible, yet have strength and elasticity. The ingredients must exhibit good adhesion to the hair to avoid dirt or flaking over time or when the hair is stressed; they should not interfere with the combing and brushing of the hair; they must remain free of stickiness or gumminess under humid conditions; They should be clear, transparent, and shiny, and should maintain clarity after aging. Additionally, the ingredients should maintain good antistatic properties and should be easy to remove by washing with water and either soap or shampoo. Many film forming agents have been used in hair cosmetic compositions including, for example, a colloidal solution containing a gum such as tragacanth or a resin such as shellac. The films formed of these materials are, however, very fragile and the shape that holds the fixation is easily broken down if the hair is disturbed. This not only reduces the hair's maintenance power of the material, but also leads to undesirable flaking. In addition, some of these film formers, particularly resins, are insoluble in water and therefore are not easily removed with soap and water or shampoo. Starches are often preferred over resins since they are more cost effective and natural. Capillary cosmetic compositions containing starches are also known in the art. For example, GB 1,285,547 discloses a hair setting composition containing a highly substituted cationic starch having an amylose content of more than 50% by weight. EP 487 000 describes cosmetic compositions containing optionally cross-linked enzymatically degraded starches. However, such derivatives are not significantly soluble in water. Due to environmental regulations that control the emission of volatile organic compounds (VOC) into the atmosphere, VOC emissions have been restricted to 80% in some states, and will soon be restricted to 55% in California. VOCs are measured as% w / w based on the capillary cosmetic formulation. As used herein, a volatile organic compound containing from 1 to 10 carbon atoms, which has a vapor pressure of at least 0.1 mm Hg at 20 ° C, and is photochemically active. Water is generally replaced by at least a portion of the volatile organic compounds and thus has become a major component in the hair cosmetic compositions. Many fixers, particularly starches, are incompatible with water since they are not totally soluble, resulting in starch precipitates which clog aerosol valves and produce poor atomization aesthetics. In addition, many starch fixatives are also incompatible with the propellant. Surprisingly, it has now been discovered that nonionically derived starches are useful in hair cosmetic compositions with low amount of volatile organic compounds since they provide a clear solution with low viscosity, good aesthetics, improved moisture resistance and good fixing properties. The present invention relates to cosmetic aerosol hair compositions with low volatile organic compounds which contain nonionically derived starches, particularly derivatives with propylene oxide. The nonionically derived starch can be further hydrolyzed, particularly enzymatically hydrolyzed by at least one endo enzyme. In addition, the nonionically derived starch can be ionically modified, particularly by octenylsuccinic anhydride (AOS). The use of such starches is novel and advantageous since they provide a clear solution with low viscosity, and good atomization characteristics. In addition, the resulting composition provides a clear film which is non-tacky, has good firmness, and improved moisture resistance. The present hair cosmetic composition contains by weight from about 0.5 to about 15% of the starch present, from about 5 to about 55% of a propellant, from zero to about 50% of a solvent, and enough water to bring the composition to 100% . An object of this invention is to provide a novel hair cosmetic composition which contains nonionic derived starches and low amount of volatile organic compounds. Another object of this invention is to provide a novel hair cosmetic composition which contains nonionic derived starches which have been hydrolyzed. Yet another object of this invention is to provide a novel hair cosmetic composition which contains starches which have been derived with propylene oxide and enzymatically hydrolysates. Yet another object of this invention is to provide a novel hair cosmetic composition which contains starches that have been nonionic, hydrolyzed and ionically modified derivatives. A further object of this invention is to provide a novel capillary cosmetic composition which contains starches that have been derived with propylene oxide, enzymatically hydrolyzed and modified with octenylsuccinic anhydride. A still further object of this invention is to provide a novel capillary cosmetic composition which has been improved in moisture resistance, superior stability and contains low amount of volatile organic compounds. A still further object of this invention is to provide a novel hair cosmetic composition which contains starch which has been derivatized and co-processed with polyvinylpyrrolidone. These and other objects of the present invention will become apparent to one skilled in the art from the following detailed description and subsequent examples. The present invention is directed to hair cosmetic compositions made in aerosol, ie capillary sprays, which contain nonionic derived starches, particularly starches derived with propylene oxide, with low or no volatile organic compound solution (referred to below VOC), particularly less than 55% VOC, more particularly less than 35% VOC, by weight of the hair setting composition. The starch can be further hydrolyzed, particularly enzymatically hydrolyzed. In addition, the starch can be modified using ionic substituents. The use of such starches is novel and advantageous since it provides a clear solution with low viscosity, and good atomization characteristics. In addition, the resulting composition provides a clear film which is non-tacky, and has good curl retention. The hair cosmetic composition of the present invention contains an effective amount of a nonionically derived starch fixative, particularly from about 0.5 to about 15% starch, more particularly from about 2 to about 10% by weight; from about 5 to about 55% of a propellant, particularly from about 5 to about 40%, from zero to about 50% of a solvent, particularly from about 5 to about 35% by weight; and enough water to bring the composition to 100%. All starches and flours (later in the present "starch") are suitable for use herein and can be derived from any native source. A native starch or flour as used herein, is one which is found in nature. Also suitable are starches and flours derived from a plant obtained by standard breeding techniques including cross-breeding, translocation, inversion, transformation or any other method of machining chromosomes or genes to include variations therein. In addition, starch or flour derived from a plant growing from artificial mutations and variations of the above generic composition which can be produced by known standard breeding methods by mutation are also suitable herein. The typical sources for starches and flours are cereals, tubers, roots, legumes and fruits. The native source can be corn, peas, potatoes, sweet potatoes, bananas, barley, wheat, rice, sago, amaranth, tapioca, arrowroot, cane, sorghum, and fatty varieties or concentrate in amylose. As used herein, the term "fatty" is intended to include a starch or flour containing at least about 95% by weight amylopectin and the term "amylose concentrate" is intended to include a starch or flour containing at least about 45% by weight of amylose. The starch is first derivatized nonionically using an ester or ether which is compatible with the system, particularly with the solvent and the solvent. Methods for nonionically derivatizing are well known in the art and can be found for example in Starch Chemistry and Technology, 2nd ed. , Edited by Whistler, et al., Academic Press, Inc., Orlando (1984) or Modified Starches: Properties and Uses, Wurzburg, O.B., CRC Press, Inc., Florida, (1986). Nonionic reagents include, but are not limited to, alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide, acetic anhydride, and butyl ketene dimer. Particularly suitable nonionic reagents are alkylene oxides, more particularly propylene oxide. The nonionic reagent is added in an amount of about 1 to 50%, particularly about 5 to 25%, more particularly about 7.5 to 18%. For example, the starch can be derivatized using propylene oxide as follows. An aqueous starch suspension containing from about 5 to about 40%, particularly 30 to 40%, solids is prepared. About 20 to about 30 wt% of sodium sulfate is added based on the weight of the starch. The pH is then adjusted to about 11 to about 13 by the addition of a 3% sodium hydroxide solution in an amount of about 40 to about 60% based on the weight of the starch. The desired amount of propylene oxide is added. The temperature is brought to the range of about 35 to 50 ° C, particularly about 40 ° C, and the process is allowed to continue for about 18 to about 24 hours. The starch is generally at least partially gelatinized. If the conversion is to be carried out enzymatically, gelatinization is conventionally carried out before conversion. The gelatinization can be carried out using any technique known in the art, particularly steam-cooked, more particularly cooked by burner and then converted (hydrolyzed). The conversion is important if a reduced molecular weight starch and a reduced viscosity of the starch solution or dispersion are desired, such as when the starch is to be used in hair spray. The conversion can be carried out by any method known in the art, such as by enzymes, acid, dextrinization, manox, or oxidation, particularly by enzymes. The conversion is carried out using acid or oxidation methods, then this can be done before or after the starch is derived. The enzymatic hydrolysis of the starch is carried out using techniques known in the art. Any enzyme or combination of enzymes, known to degrade starch, particularly endo enzymes, can be used, enzymes useful in the present application include, but are not limited to, α-amylase, β-amylase, maltogenase, glucoamylase, pullulanase, particularly -amylase and pullulanase. The amount of the enzyme used depends on the enzyme source and activity, base material used, and the amount of hydrolysis desired. Typically, the enzyme is used in an amount of about 0.01 to about 1.0%, particularly about 0.01 to 0.3%, by weight of the starch.

The optimal parameters for the enzymatic activity will vary depending on the enzyme used. The rate of degradation of the enzyme depends on factors known in the art, including enzyme concentration, substrate concentration, pH, temperature, the presence or absence of inhibitors, and the degree and type of modification. These parameters can be adjusted to optimize the digestion ratio of the starch base. Generally, the treatment of the enzyme is carried out in an aqueous or buffered suspension at a level of starch solids of about 10 to about 40%, depending on the base starch being treated. Particularly useful is a solids level of about 15 to 35%, about 18 to 25% more particularly useful, in the present invention. In the alternative process, the process can use an enzyme immobilized on a solid support. Typically, digestion of enzymes is performed at the highest feasible solids content without reducing the reduction ratios in order to facilitate any desired subsequent drying of the starch composition. The reaction rates can be reduced by high solids content as soon as the agitation becomes difficult or inefficient and the dispersion of the starch becomes more difficult to handle. The pH and temperature of the suspension can be adjusted to provide effective enzymatic hydrolysis. These parameters are dependent on the enzyme to be used and are known in the art. In general, a temperature of about 22 to about 65 ° C, particularly about 50 to about 62 ° C, is used. in general, the pH is adjusted to about 3.5 to about 7.5, particularly about 4.0 to about 6.0, using techniques known in the art. In general, the enzymatic reaction will take from about 0.5 to about 24 hours, particularly about 0.5 to about 4 hours. The reaction time depends on the type of starch used, the amount of enzyme used, and the reaction parameters of percent solids, pH and temperature. The enzymatic degradation is then terminated by any technique known in the art such as acid or base deactivation, heat deactivation, ion exchange, and solvent extraction. For example, acid deactivation can be performed by adjusting the pH to less than 2.0 for at least 30 minutes or heat deactivation can be performed by increasing the temperature to about 85 to about 95 ° C and maintaining it at that temperature for at least approximately 10 minutes to completely deactivate the enzyme. Heat deactivation is not suitable if a granular product is desired since the heat necessary to deactivate the enzyme will generally gelatinize the starch. The conversion reaction is continued until the starch is sufficiently degraded to provide appropriate spraying characteristics, particularly for a viscosity of from about 7 to about 80 seconds, more particularly from about 10 to about 60 seconds, measured at 19% w / w of concentration of solids at room temperature using a standard funnel method. The resulting product can be further characterized by a dextrose equivalent (ED) of from about 2 to about 40 and / or a water flow of from about 60 to 80. The funnel viscosity, as used herein, is defined by the following procedure. The starch dispersion to be tested is adjusted to 19% (w / w) measured by refractometer. The temperature of the dispersion is controlled at 22 ° C. A total of 100 ml of the starch dispersion is measured in a graduated cylinder. This is then emptied into a calibrated funnel while a finger is used to close the hole. A small amount is allowed to flow in the graduated cylinder to remove any trapped air and the equilibrium in the funnel is emptied again. The graduated cylinder is then inverted in the funnel in such a way that the contents drain (flow) into the funnel while the sample is running. The time required for the sample of 100 ml to flow through the apex of the funnel is recorded, using a stopwatch. The glass portion of the funnel is 58 ° standard, thick-walled, resistance glass funnel, whose upper diameter is approximately 9 to approximately 10 cm with the internal diameter of the rod approximately 0.381 cm. The glass rod of the funnel is cut to a length of about 2.86 cm from the apex, carefully polished by fire, and refined with a long stainless steel strut which is approximately 5.08 cm in length with an external diameter of approximately 0.9525 cm. The internal diameter of the steel strut is approximately 0.5992 cm at the upper end where it joins the glass rod and approximately 0.4445 cm at the end of external flow with the restriction in width that occurs approximately 2.54 cm from the ends. The steel strut is attached to the glass funnel by means of a Teflon tube. The funnel is calibrated to allow 100 ml of water to go through six seconds using the above procedure. Finally, the starch can be ionically modified, either anionically, cationically, or zwitterionically. Starch modification techniques are well known in the art and can be found, for example, in Starch Chemistry and Technology, 2nd ed. , Edited by Whistler, et al., Academic Pressi, Inc., Orlando (1984) or Modified Starches: Properties and Uses, Wurzburg, O.B., CRC Press, Inc., Florida, (1986). The anionic modification can be carried out by any agent known in the art, such as alkenyl succinic anhydrides, inorganic phosphates, sulfates, phosphonates, sulfonates and chloroacetic sodium acids. Particularly suitable anionic reagents are alkenyl succinic anhydrides and sodium chloroacetic acids, more particularly octenylsuccinic anhydride. Modification of the starch using octenylsuccinic anhydride by reacting the selected starch with sufficient octenylsuccinic anhydride reagent can be carried out in such a way that the resulting starch is sufficiently soluble or dispersible in the water or water solvent delivery system. In particular, the starch can be modified to have a degree of substitution of from about 0.2 to about 3.0, preferably from about 0.3 to about 1.6. the degree of substitution (GS) is used herein to describe the number of ester substituted groups per anhydrous glucose unit of the starch molecule. The cationic modification should be at a low degree of substitution, particularly less than about 0.3 equivalents per 100 grams of starch. The cationic modification can be performed by any reagent known in the art including those containing amino, imino, ammonium, sulfonium or phosphonium groups. Such cationic derivatives include those with nitrogen-containing groups comprising primary, secondary, tertiary and quaternary amines and sulfonium and phosphonium groups linked through either ether or ester linkages. Cationic modification, particularly tertiary amines or quaternary ammonium etherification of starch, typically prepared by treatment with 3-chloro-2-hydroxypropyltrimethylammonium chloride, 2-diethylaminoethyl chloride, 3-chloro-2-hydroxypropyltrimethylammonium chloride, 2-chloride diethylaminoethyl, epoxypropyltrimethylammonium chloride, 3-chloro-2-hydroxypropyl dimethyldodecylammonium chloride, and 4-chloro-2-butenyltrimethylammonium chloride. The zwitterionic modification can be carried out using any reagents known in the art, such as N- (2-chloroethyl) -iminobis (methylene) diphosphonic acid and 2-chloroethylaminodipropionic acid (ACEP). In general, the degree of desired non-ionic derivatization will be greater when the starch is not ionically modified than when the starch is ionically modified. Optionally, the starch can then be neutralized by increasing the pH of the solution from about 5 to about 9. This can be done by any method known in the art., particularly by the addition of aminomethylpropanol, sodium hydroxide, potassium hydroxide, or other bases known in the art. The starch solution is generally filtered to remove impurities, particularly fragmented starch. The filtration can be performed by any method known in the art, particularly by filtration through the diatomaceous earth. The starch can be used as a solution or it can be recovered in powder form by conventional techniques, such as drum drying or spray drying. The modified starch can also be mixed or co-processed with other fixative or conditioning polymers. Such a polymer can be selected from polymers known in the art, such as vinyl acetate / crotonates / vinyl neodecanoate copolymer, octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer, vinyl acetate / crotonates copolymer, polyvinylpyrrolidone (PVP), copolymer of polyvinylpyrrolidone / vinyl acetate, PVP acrylate copolymer, vinyl acetate / crotonic acid / vinyl propionate, acrylates / acrylamide, acrylates / octylacrylamide, acrylate copolymer, acrylate / hydroxyacrylate copolymer, and polyvinylmethylether / anhydride alkyl esters maleic, diglycol copolymer / cyclohexanedimethanol / isophthalates / sulfoisophthalates, vinyl acetate / butyl maleate copolymer and isobornyl acrylate, vinylcaprolactam / PVP / dimethylaminoethyl methacrylate, vinyl acetate / alkyl ester maleate, middle ester / terpolymers of N-substituted acrylamide , vinylcaprolactam / vinylpyrrolidone / metacri chloride terpolymer loamidopropyltrimethylammonium, methacrylates / acrylates copolymer / amine salt, polyvinylcaprolactam, polyurethanes, polyquaternium-4, polyquaternium-10, polyquaternium-11, polyquaternium-6, guar of hydroxypropyl, guar of hydroxypropyl hydroxypropyltrimonium chloride, polyvinylformamide, polyquaternium-7 and guar of hydroxypropyltrimonium chloride, particularly polyvinylpyrrolidone. To co-process the starch and the polymer, the polymer is dissolved in water. The modified starch is then formed in suspension in the dispersed polymer and the suspension is processed. Processing includes cooking and drying, particularly burner cooking and spray drying, and includes the methods described in U.S. Patent No. 5,149,799; No: 4,280,851; No. 5,188,674 and 5,571,552 incorporated herein by reference. The supply system in most cases will be a mixture of water and one or more volatile organic compounds that act as solvents. The amount of the solvent will be present in an amount of from zero to about 50%, particularly from about 5 to about 35% by weight of the composition. However, it is possible to prepare hair cosmetic compositions containing the starches present in which the delivery system comprises essentially water or even essentially no solvent. Typically, the organic solvent will be a lower alcohol (defined herein as an alcohol having 1 to 7 carbon atoms), particularly methanol, ethanol, propanol, isopropanol or butanol. Acétals, esters, and ketones are also suitable, particularly dimethoxymethane and acetone. A propellant is added to formulate the cosmetic aerosol hair composition. Propellants useful in the present invention include, but are not limited to, ethers, such as dimethyl ether; one or more lower boiling hydrocarbons such as straight or branched chain hydrocarbons of C3-C5, eg, propane, butane, and isobutane; halogenated hydrocarbons, such as hydrocarbons, for example, 1,1-difluoroethane and 1,1,1,1-tetrafluoroethane, present as a liquefied gas; and compressed gases, for example, nitrogen, air and carbon dioxide. The amount of the propellant used in the hair cosmetic compositions of this invention may vary from about 5 to about 55%, particularly from about 5 to about 40% by weight of the composition. It should be noted that the above propellants are volatile organic compounds. However, the emission of halogenated hydrocarbons such as hydrofluorocarbons, and compressed gases are not subject to environmental regulations at this time; therefore, these compounds can be formulated in the hair sprayers of this invention without inclusion in the total content of the VOC. Optional conventional additives may be incorporated in the capillary spray compositions of this invention to provide certain modifying properties to the composition. Included among these additives are the plasticizers, such as glycerin, glycol and phthalate esters; emollients, lubricants and penetrants, such as lanolin compounds; fragrances and perfumes; UV absorbers; dyes and other colorants; thickeners; anti-corrosion agents; detaching agents; styling auxiliaries and conditioning agents; antistatic agents; neutralizers; brighteners; conservatives; emulsifiers; surfactants; viscosity modifiers; gelling agents; opacifiers; stabilizers; sequestering agents, chelating agents; pearl agents; and clarifying agents. Such additives are commonly used in hair cosmetic compositions known hitherto. These additives are present in small amounts, effective to perform their function, and generally comprise from about 0.1 to 10% by weight each, and from about 0.1 to 20% by total weight, based on the weight of the composition.

The hair care compositions containing the present starch may also be combined with other modified or unmodified starches that provide added functional benefits. For example, formulations with 2-chloroethylaminopropionic acid derivatives of potato starch or hydroxypropyl starch phosphate can be incorporated for modification of the thickening or rheology in lotions and creams for hair styling, and starches such as tapioca starch, corn starch , octenyl starch aluminum succinate, or modified corn starch may be used in hair care compositions as aesthetics enhancers to provide more silky, uniform formulations. Modified starches, as used herein, are proposed to include, without limitation, converted starches, cross-linked starches, organically esterified and acetylated starches, hydroxypropylated and hydroxyethylated starches, inorganically esterified and inorganically esterified starches, cationically modified, anionically ozionically, and starches succinados and succinados replaced. Such modified starches are known in the art for example in Modified Starches: Properties and Uses by Wurzburg. Particularly suitable modified starches include hydroxypropylated starches, octenyl succinate derivatives and 2-chloroethylaminodipropionic acid derivatives.

To prepare the hair cosmetic aerosol composition, a solution of the starch is prepared in the water or water / solvent mixture. Then any optional additives can be added. The mixture is then pressurized with a propellant according to conventional standards known in the art to form the cosmetic aerosol hair composition. The pressures used are those conventionally used to prepare aerosol sprays, such as from about 30 psi to about 110 psi. Hair cosmetic compositions include, but are not limited to, hair setting compositions and styling aids, such as hair sprays and mousses. An advantage of the hair care compositions containing the present starch is that the starches are substantially soluble in water and compatible with the propellant. This allows a composition substantially free of solvent or reduced solvent to be formulated. The solubility is important since the presence of the particulate matter (ie, undissolved starch) can clog the valves of the pump, interfering with the delivery of the composition by aerosol. Another advantage of the present compositions which are of relatively low viscosity. This helps eliminate the undesirable stickiness and heaviness associated with many conventional hair cosmetic compositions. An additional advantage of the hair cosmetic compositions present is that they do not become sticky at high relative humidity (RH), unlike many cosmetic hair compositions containing conventional water-based starch. Starches present in the skin, oral and other applications may also be used, such as lotions, creams, sunscreens, lip balm, tanning products, mouth rinses, antiperspirants, shampoos and conditioners. The following examples are presented to further illustrate and explain the present invention and should not be taken as limiting in any aspect. EXAMPLES All percentages are calculated in the examples on the weight / weight basis. The following test procedures are used in all examples. A. Determination of the curl retention at high humidity of capillary atomizations. The properties of capillary spray starch at 72 ° F (22 ° C) / 90% relative humidity are measured over a period of 24 hours. Equipment: Brown hair Remi Blue String European 8"Scissors for cutting Nylon comb White cotton thread (size # 8) Teflon tubes 3" xl / 2"Forced air oven @ 120 ° F (49 ° C) Retaining plate plaxiglass Camera environmental (precision at ± 2 HR @ 72 ° F (22 ° C) Pre-shampoo 10 Procedure; Preparation of curl samples 1. Separate the hair into small samples of approximately 2 grams by weight 2. Secure the hair sample 3A "(1.9 cm) from the end of the root winding with cotton thread. 3. Fold over the end of the root and secure the hair in a small loop with thread. Leave about 6"(15.24 cm) of the loose strand to secure the identification tag. 4. In order to avoid losing the axis of the individual hair during combing, gum the end of the root to the windings with thread with epoxy cement. Allows it to harden the cement.

. Wash the hair sample in a 10% shampoo solution. Then rinse thoroughly with lukewarm running water. 6. Comb the hair shafts to untangle the hair shafts. 7. Cut the hair sample to measure 6"(15.24 cm) from the root end in curl, dry @ 120 ° F (49 ° C), prepare and expose the test samples 1. Moisten the hair and comb through it to untangle. 2. Squeeze the excess water by taking the sample between the thumb and forefinger. 3. Straighten hair in a coil configuration by rolling it into a Teflon tube of W diameter. Secure the hair in the tube with plastic fasteners. 4. Dry hair, tube and bra 120 ° F (49 ° C). 5. When the hair is dry and cold, remove carefully fasteners and curly hair from the tube. 6. Suspend the hair curl of the curly end. Apply a controlled amount of capillary spray in a controlled manner. In the evaluation, uniformly applies a non-aerosol hair spray, a second "blowout" to both the front and back of the curl from a distance of 6"(15.24 cm) 7. Leave the newly sprayed curl on a horizontal surface and allow air to dry 8. Suspend the dry curls in a random fashion from clear, transparent, graduated plexiglass retention boards 9. Take the initial curl height reading (L0) and fix the curl retention boards in the environmental chamber 10. Record the length of the curl (Lt) in the intervals of 15, 30, 60 and 90 minutes, 2, 3, 4, 5, and 24 hours Calculation of percent of curl retention by:% curl retention = (L-Lt) / (L-L0) x 100 where: L Fully extended hair length Ls hair length before exposure L hair length after exposure B. Initial curl drop Reach defines the initial curl drop (CRI) as the interm loss Edia of the integrity of the curl after spraying with a formulation containing water, the curl dry, suspended. Equ or Brown hair 6"(15.24 cm) (9 samples rolled per sample) Plexiglass retention board Digital stopwatches or stop watches Procedure 1. Determine both the spray ratio and polymer deposition of each sample not prepared in aerosol before Test 2. Roll samples in white Teflon tubes 3. Allow coiled hair to cool and equilibrate at 50% RH, 72 ° F (22 ° C) for at least three hours before removing tube. Suspend the curl of hair from the rolled end on the retaining board using the attached fastener, make sure the curl bottom is aligned with the "0" mark on the board 5. Spray the first side of the curly hair from the left to Right for the specified period of time to keep the deposition of the polymer uniform following the total dew time Pivot the curl 180 degrees using the fastener and complete the spray cycle on the other side before turning back to the original position. All spraying should be done from a distance of six inches (15.24 cm) (nozzle to hair). 6. Record the length of the curl after 30, 60 and 90 seconds, as well as 2, 4 and 6 minutes following the initial spray, using markers on the board. 7. In order to test more than one curl at a time, start spraying a second curl after the first curl has been followed by 2-4 minutes. Using another stopwatch, repeat the procedure as described above. Take care that the spray does not contact the initial curl. Repeat this process once the initial loop has been followed for 6 minutes. Results Calculate the percent retention of the curl for each time interval. C. Taber stiffness test procedure. Unprayed hair spray formulations for stiffness are tested on three 4U "(11.43 cm) samples of European virgin brown hair and the results are pooled and averaged.The samples are first dried in an oven at 110 ° F ( 43 ° C) for 30 minutes to remove moisture and then dry in a desiccator for 15 minutes, weigh the samples and record the weight as Wx, spray each sample with a hair spray formulation by two burners and then attach to a holding board and dry in an oven at 110 ° F (43 ° C) for 15 minutes.The samples are cooled in the desiccator and reweighed.The weight is recorded as W2. equilibrate overnight at 50% relative humidity and 23 ° C. Stiffness is tested using a Taber V-5 stiffness tester from Taber Industries of North Tona Anda, NY, designed to evaluate the rigidity and elasticity of paper, cardboard, and other flexible materials. following procedures and calculation with hair samples. When the machine is first turned on, the optical encoder inside the unit is oriented and the pendulum is balanced according to the manufacturer's instructions. The hair sample is inserted between the jaws of the clamp, with the lower edge resting slightly on the bottom gauge. Fasten the clamping jaws by turning the screws on either side of the clamp. The sample is centered between the bottom rollers. With one finger, light pressure is applied to the control lever switch and the drive disc is deflected to the left until the line on the pendulum is below the deflection mark of 15 °. Use a uniform, continuous motion without starts and stops Record the stiffness reading on the external scale that falls opposite the zero line on the drive disk (LS) Now deflect the same sample to the right by 15 ° and take that stiffness reading (RS). Average the left and right readings and multiply by five. The product is the stiffness value for that sample. D. Elimination test procedure Use formulas made in aerosol, spray eight hair samples with an experimental formulation and eight with a control formulation and allow to dry at ambient conditions for one hour. For each sample, rinse under running water for 1 minute while working with the fingers on the hair. Put the wet samples in an oven at 110 ° F (43 ° C). Form pairs of experimental samples against control samples, and subjectively evaluate for residual stiffness, desquamation, and tactile sensation properties. Analyze the data for statistical differences at a confidence level of 95%. E. Test procedure for time tackiness and drying time Suspend eight groups of two untreated hair samples, each separately. Spray a sample of each group with an experimental formulation and another sample with a control formulation simultaneously. Immediately feel the samples for tack time and drying time. Record the time when the tack starts, the stickiness ends, and when each sample feels dry. Subtract the tack start time from the tack end time to obtain the total tack time. The shorter the stickiness and drying time, the better. Analyze the results by statistical differences at a confidence level of 95%. Example 1 - Preparation of. starch modified with alkylene oxide a. A 40% aqueous solution of fatty starch is prepared and 25% sodium sulfate is added. The pH is then adjusted to approximately 11.5 using a 3% sodium hydroxide solution. The starch is treated with 7.5% propylene oxide. The pH is then adjusted to 5.5 using dilute sulfuric acid. b. The example is repeated using a 15% propylene oxide level. c. The example is repeated using a 3% propylene oxide level. d. The example is repeated using a 50% amylose corn starch. and. The example is repeated using a 70% amylose corn starch. f. Example Ib is repeated using a tapioca starch. g. The example is repeated using potato starch. Example 2 - Preparation of modified hydrolyzed starch with propylene oxide a. The suspension starch from Example la is adjusted to a pH of 5.5 using sulfuric acid and cooked until completely gelatinized. The starch is then hydrolyzed using α-amylase at a funnel viscosity of about 30 seconds. b. Example 2a is repeated using a starch of 70% amylose. c. Example 2a is repeated by hydrolyzing at a funnel viscosity of 10 seconds. d. Example 2a is repeated by hydrolyzing at a funnel viscosity of 60 seconds. Example 3 - Preparation of modified hydrolyzed starch with propylene oxide and octenylsuccinic anhydride a. A 40% aqueous suspension of Amioca ™ starch is prepared. 25% sodium sulfate is added. The pH is then adjusted to approximately 11.50 by the addition of a 3% sodium hydroxide solution. The starch is then treated with propylene oxide at a level of 7.5%. After the reaction the pH is adjusted to 3.5 using sulfuric acid. The solution is allowed to stir for one hour and the pH is then adjusted to 5.5 with 3% sodium hydroxide. The starch is then stitched until it is fully gelatinized and hydrolysed with alpha amylase for a funnel viscosity of 30 seconds. The cooked starch is cooled to room temperature. Octenyl succinic anhydride is then added at a level of 6% while maintaining the pH at 7.5 using a 25% sodium hydroxide solution. The starch is allowed to react until caustic consumption is stopped. The pH is then adjusted to 5.5 using dilute hydrochloric acid solution. The pH is then filtered through Celite (Celite 512 is a diatomaceous earth commercially available from Celite Corporation). b. Example 3a is repeated using propylene oxide at a level of 15%. c. Example 3a is repeated using propylene oxide at a level of 3%. d. Example 3a is repeated by hydrolyzing the starch to a funnel viscosity of less than 10 seconds. and. Example 3a is repeated by hydrolyzing the starch to a funnel viscosity of 15 seconds. f. Example 3a is repeated by hydrolyzing the starch to a funnel viscosity of 60 seconds. g. Example 3a is repeated by hydrolyzing the starch using concentrated hydrochloric acid for sixteen hours and then neutralizing by the addition of sodium carbonate and sodium hydroxide. h. Example 3a is repeated by hydrolyzing the starch using sodium hypochlorite solution for sixteen hours.

A solution of 10% sodium bisulfite is added to remove residual hypochlorite and neutralized using dilute hydrochloric acid. i. Example 3a is repeated using potato starch instead of Amioca. Example 4 - Preparation of other modified hydrolyzed starches a. A 40% aqueous suspension of Amioca ™ starch is prepared. The pH is adjusted to approximately 11.5 using 3% NaOH. The suspension is treated with 3-chloro-2-hydroxypropyltrimethylammonium chloride. The suspension is allowed to react for 10-12 hours while maintaining the pH = 11.5 using 3% NaOH. It is then adjusted to the starch at pH = 5.5 using dilute hydrochloric acid solution; it is filtered and washed. The starch is then stitched until it is fully gelatinized and hydrolyzed with alpha amylase at a funnel viscosity of 30 seconds. The cooked starch is cooled to room temperature. The octenylsuccinic anhydride is then added at a level of 6%. The pH is maintained at 7.5 using 25% sodium hydroxide solution. The starch is allowed to react until the consumption of the caustic is stopped. The pH is then adjusted to 5.5 using dilute hydrochloric acid solution. The starch is then filtered through Celite (Celite 512 is a diatomaceous earth commercially available from Celite Corporation). b. Example 4a is repeated using 3-chloro-2-hydroxypropyltrimethylammonium chloride at a level of 10%. c. Example 4a is repeated substituting the use of 2-chloroethylaminodipropionic acid at a level of 5% by the use of 3-chloro-2-hydroxypropyltrimethyl. d. A 40% aqueous suspension of Amioca ™ starch is prepared. Sodium sulfate is added to 25%. The pH is then adjusted to approximately 11.50 by the addition of a 3% sodium hydroxide solution. The starch is then treated with propylene oxide at a level of 7.5%. After the reaction the pH is adjusted to 3.5 using sulfuric acid. The solution is allowed to stir for one hour and the pH is then adjusted to 5.5 with 3% sodium hydroxide. The starch is then stitched until it is fully gelatinized and hydrolysed with alpha amylase for a funnel viscosity of 30 seconds. The cooked starch is cooled to room temperature. The acetic anhydride is added at a level of 7.5%, while maintaining the suspension at pH = 7.5 with 25% NaOH. The starch is then allowed to react until the consumption of the caustic is stopped. The pH is then adjusted to 5.5 using dilute hydrochloric acid solution. The starch is then filtered through Celite (Celite 512 is a diatomaceous earth commercially available from Celite Corporation). and. A 40% aqueous suspension of Amioca ™ starch is prepared. 25% sodium sulfate is added. The pH is then adjusted to approximately 11.50 by the addition of a 3% sodium hydroxide solution. The starch is then treated with propylene oxide at a level of 7.5%. After the reaction the pH is adjusted to 3.5 using sulfuric acid. The solution is allowed to stir for one hour and the pH is adjusted to 5.5 with 3% sodium hydroxide. After the starch is sewn until it is fully gelatinized and hydrolyzed with alpha amylase at a funnel viscosity of 30 seconds. The cooked starch is cooled to room temperature. Acetic anhydride is added at a level of 7.5%, while maintaining the suspension at pH = 7.5 with 25% NaOH. The octenylsuccinic anhydride is then added at a level of 6%, maintaining the pH = 7.5 using 25% NaOH. It is allowed to react the starch until the consumption of the caustic is stopped. The pH is then adjusted to 5.5 using dilute hydrochloric acid solution. The starch is then filtered through Celite (Celite 512 is a diatomaceous earth commercially available from Celite Corporation). Example 5 - Coprocessing of the starch with a polymer 5 g of polyvinylpyrrolidone (PVP) are dissolved in 900 grams of water. 100 g of the starch of example lg is then suspended in the solution of the polymer. The suspension is sewn by burner at 150-155 ° C and then transported under pressure directly to a spray dryer to prevent retrogradation. The cooked suspension is spray-dried with an inlet temperature of 230 ° C and an outlet temperature of 120 ° C. Example 6 - Neutralization of Starch The starches of Examples 1-5 are neutralized by the addition of 2-amino-2-methyl-1-propanol. Example 7 - Preparation of capillary spray solution a) each of the starches of examples 1-6 is made in a capillary spray solution using the following method. The starch is diluted with water to a 7.5% solids solution. Dimethyl ether propellant is added to make the final concentration of 5% starch, 33% propellant, and 62% water. Example 8 - Behavior of starches in an aerosol capry spray model The starches of Examples 3a and 3b are formulated in aerosol capry atomizer systems with low VOC amount according to the following formulations. All reported values are in parts by weight, based on the total weight of the capry atomizing composition. Ingredient Parts by weight (dry basis) alcohol-free (33% VOC) Polymer starch 5.0 Deionized water 62.0 Dimethyl ether 33.0 The starch polymer is sieved with stirring in deionized water until homogeneous. The solutions are filtered and fd into containers made in aerosol. The cans are loaded with dimethyl ether propellant. Capry atomization formulations are tested for spray characteristics on samples of 2 grams of European brown hair. Sprays are supplied with a Seaquist NS-34 valve (Vapor cap 0.013 inches x vapor hole 0.013 inches x 0.040 inch deep tube diameter) that has an Excel 200 Misty actuator (0.016 inch hole) in a second burner from a distance of six inches. The formulas are compared to: Control A (d-glycol copolymer / CHDM / isophthalates / SIP at 5% solids, 33% COV aerosol, commercially available from Eastman Chemical Company, Kingsport, Tennessee); Control B (AV / crotonates / neodecanoat vinyl copolymer in 5% solids, anhydrous aerosol type commercially available from National Starch and Chemica Company, Bridgewater, New Jersey); Control C (acrylate / octylacrylamide copolymer at 5% solids, of the anhydrous aerosol type commercially available from National Starch and Chemical Company, Bridgewater, New Jersey); and / or Control D (octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer in an anhydrous 5% solids aerosol type commercially available from National Starch and Chemical Company, Bridgewater, New Jersey). Ingredient Anhydrous formulations parts by weight (dry basis) Polymer 5.0 2-amino-2-methyl-1-propanol (AMP) at 1.0 anhydrous ethanol 69.0 Hydrocarbon A- 6 25.0 a commercially available from Angus Chemical Company b isobutane / propane Solubility in aerosol The solubility of the starches in the capillary atomizing composition is determined by checking the clarity immediately after the formulation and after 12 hours. The results are shown in Table I below.

Spray characteristics Spray characteristics of alcohol-free aerosols are classified on a scale from A to F, with A being the best spray. An "A" rating indicates a wide spray cone, fine spray, small particle size and no foam in the hair or actuator. A rating of "F" indicates a narrow spray cone, dividing in the actuator, large particle size, and obvious foam in the hair or actuator. The average particle size of the sprays is measured by Malvern Seerie 2600 and particle size analyzers from Malvern Instruments Inc. of Southborough, MA. The results are listed in Table II: Table II Retention of the curl (90%) in high humidity The average retention values of nine samples are listed in Table III, below.

Table III Polymer 15 min 30 min 60 min 90 min 2 h 3 h 4 h 5 h 24 h Example 3a 95.5 91.8 89.5 88. .8 86.6 85.0 84.3 84.3 80.5 Example 3b 94.0 90.8 89.2 86, .2 83.9 82.2 78.4 78.4 67.9 Control A 95.6 92.0 89.0 87, .6 84.0 80.4 80.4 80.4 70.4 Control B 90.7 85.4 78.1 73, .3 73.0 70.2 69.1 65.7 53.9 Control D 97.9 96.6 93.1 93, .1 92.5 91.2 91.2 91.2 90.5 All examples of starch are comparable in moisture resistance with controls. Shampoo removal evaluations It is listed in Table IV, after shampoo removal compared to a control C.

Descamed Rigidity Polymer Example 3a The results are statistically equivalent to the control. Taber stiffness Table V Polymer% control stiffness D Example 3a 65% Control A 72% Tack time and drying The stickiness and drying time is compared to control D.

Table VI Polymer Total tack time Drying time Example 3a + + Example 3a is statistically superior (less stickiness, faster drying time) than the control. Initial curl drop The compositions are tested at 50% relative humidity (RH). The retention values of the average% ripple of nine values per sample are shown in Table X below. Table VII Example 9 - Preparation of starch / polymer in ousse Ingredient Quantity (q) Polymer 3.00 Surfactant3 Tergitol NP-9 0.60 Dowicil 200b 0.20 Water 88.20 Propellant A-46c 8.00 to nonoxynol-9 is commercially available from Union Carbide bquaternium-15 is commercially available from Dow Chemical Co. cisisobutane / propane. The polymer disperses slowly in the water with agitation. Tergitol and Dowicil are added with continuous agitation. The resulting solution is filtered and used to fill aerosol cans. The cans are loaded with the propellant. Polymers Starch of example 5 Luviskol VA 64 (PVP / VA 60/40), commercially available from BASF Gafquat, commercially available from International Specialty Products blend 50:50 mixture of Example 5: Gafquat. Wet combing ability and feeling to the touch The mousse is supplied in a wet hair sample and combed. Both the wet combability and tactile feel of the formulation using the starch of example 5 are equivalent to that of Luviskol. Both the ability to wet comb and feel to the touch of the formulation using the 50:50 mixture example 5: Gafquat are equivalent to that of the Gafquat alone. Subjective rigidity The starch of Example 5 provides more rigidity than that of Luviskol. The mousse is then reformulated using 2.25 % and 1.5% starch of example 5, using water to replace the starch removed. The comparison with Luviskol (3%) is shown below. Example 5 at 3% Stiffer than Luviskol Example 5 at 2.25% Luvi-kol equivalent stiffness Example 5 at 1.5% Less stiffness than Luviskol The stiffness of the 50:50 mixture, example 5: Gufquat is equal to that of Gafquat. Retention of the curl in high humidity Polymer Medium retention (%) Example 5 43.49 Gafquat 36.84 Luviskol 15.57 Example IQ = preparation of. an all natural texturizing fixing lotion Ingredients% by weight Phase A; Deionized water 55.85 (1) Modified potato starch 1.75 (2) Brij 78 2.00 Phase B: (3) DC 345 7.50 (4) DC 200 2.50 Phase C: (5) Lanette 0 1.40 (6) Germall II 1.00 Phase D: Propylene glycol 5.00 Example 1 e 3.00 Phase E: Deionized water 20.00 100.00 INCI designations: (1) Modified potato starch (National Starch and Chemical) (2) Steareth-20 (ICI Surfactants) (3) Cyclomethicone (Dow Corning) (4) Dimethicone (Dow Corning) (5) Alcohol Cetearyl (Henkel) (6) Diazolidinylurea (Sutton Labs) Procedure: Add a modified potato starch to cold water and mix for 2 minutes. The starch solution is heated to 80 ° C with mixing at a moderate speed. Mixing is continued for 25 minutes at 80 ° C. Brij 78 is added and mixed until dissolved. Phase B is premixed and added to Phase A under high speed (8,000-10,000 RPM). Lanette O is added at 80 ° C and mixed and then Germall II is added. Phase D is premixed and then Phase E is added to Phase D and mixed well. Stage DE is added to Phase ABC and mixing is continued for approximately 10-15 minutes.

Claims (25)

1. CLAIMS 1. A hair cosmetic composition characterized in that it comprises: a) an effective fixing amount of a nonionically derived starch; b) from about 5 to about 55% of a propellant; c) up to about 50% of a solvent; and d) water. The composition according to claim 1, characterized in that the starch is present in an amount of about 0.5 to 15% by weight of the composition. 3. The composition according to claim 1, characterized in that the starch is present in an amount of about 2 to 10% by weight of the composition. 4. The composition according to claim 1, characterized in that the starch is a fatty starch. 5. The composition according to claim 1, characterized in that the starch is a starch concentrated in amylose. The composition according to claim 1, characterized in that the starch is nonionically derived using from about 1 to about 50% of a nonionic modifying reagent. The composition according to claim 6, characterized in that the starch is nonionically derived using from about 5 to about 25% of a nonionic modifying reagent. The composition according to claim 1, characterized in that the starch is derived nonionically using a reagent selected from the group consisting of alkylene oxide, acetic anhydride, and butyl ketene dimer. 9. The composition according to claim 8, characterized in that the starch is nonionically derived using an alkylene oxide. 10. The composition according to claim 9, characterized in that the starch is nonionically derived using propylene oxide. 11. The composition according to claim 1, characterized in that the starch is also at least partially hydrolyzed. 12. The composition according to claim 1, characterized in that the starch is further modified anionically or zwitterionically. The composition according to claim 1, characterized in that the starch is further modified cationically at a level of less than about 0.03 equivalents per 100 grams of starch. The composition according to claim 12, characterized in that the starch is anionically modified using a reagent selected from the group consisting of alkenyl succinic anhydrides, inorganic phosphates, sulphates, phosphonates, sulfonates, and sodium chloroacetic acids. 15. The composition according to claim 14, characterized in that the starch is anionically modified using the octenylsuccinic anhydride reagent. 16. The composition according to claim 12, characterized in that the starch is zwitterionically modified using a reagent selected from the group consisting of N- (2-chloroethyl) -iminobis (methylene) diphosphonic acid and 2-chloroethylaminodipropionic acid. 17. The composition according to claim 13, characterized in that the starch is cationically modified using a reagent containing a group selected from the group consisting of amino, imino, ammonium, sulfonium and phosphonium. 18. The composition according to claim 17, characterized in that the starch is cationically modified using a reagent selected from the group consisting of 3-chloro-2-hydroxypropyltrimethylammonium chloride, 2-diethylaminoethyl chloride, epoxypropyltrimethylammonium chloride and sodium chloride. -chloro-2-butenyltrimethylammonium. 19. The composition according to claim 1, characterized in that it also comprises a fixing or conditioning polymer. 20. The composition according to claim 1, characterized in that it further comprises a polymer selected from the group consisting of vinyl acetate / crotonates / vinyl neodecanoate copolymer, octylacrylamide / acrylates / butylaminolethyl methacrylate copolymer, vinyl acetate / crotonates, polyvinylpyrrolidone (PVP), polyvinylpyrrolidone / vinyl acetate copolymer, PVP acrylate copolymer, vinyl acetate / crotonic acid / vinyl propionate, acrylates / acrylamide, acrylates / octylacrylamide, acrylate copolymer, acrylate / hydroxy acrylate copolymer, and alkyl esters of polyvinylmethylether / maleic anhydride, diglycol / cyclohexanedimethanol / isophthalates / sulfoisophthalates copolymer, vinyl acetate / butyl maleate, and isobornyl acrylate copolymer vinylcaprolactam / PVP / dimethylaminoethyl methacrylate, terpolymers of vinyl acetate / alkylmaleate ester / N-substituted acrylamide, terpolymer of vinylcaprolactam / vinylpyrrolidone / methacrylolamidopropytrimethylammonium chloride, methacrylates / acrylate copolymer / amine salt, polyvinylcaprolactam, polyurethanes, polyquaternium- 4, polyquaternium-10, polyquaternium-11; polyquaternium-46, hydroxypropyl guar, hydroxypropyl guar, hydroxypropyltriamonium chloride, polyvinylformamide, polyquaternium-7, and guar of hydroxypropyltriamonium chloride. 21. The composition according to claim 20, characterized in that the polymer is polyvinylpyrrolidone. 22. The composition according to claim 20, characterized in that the starch and the polymer are formed in suspension together, sewed and dried. 23. A hair cosmetic composition characterized in that it comprises: a) an effective fixing amount of a mixture of concentrated starch in modified amylose with propylene oxide / polyvinylpyrrolidone (PVP) prepared by suspending the starch modified with the PVP, burned and dried by sprinkling; b) from about 5 to about 55% of a propellant; c) up to about 50% of a solvent; and d) water. The composition according to claim 1, characterized in that the compositions are substantially free of solvent. 25. The composition according to claim 23, characterized in that the composition is substantially free of solvent. 26. The composition according to claim 1, characterized in that it also comprises at least one additional modified or unmodified starch. 27. The composition according to claim 26, characterized in that the additional starch is selected from the group consisting of hydroxypropylated starches, octenylsuccinate derivatives, and 2-chloroethylaminodipropionic acid derivatives. 28. The composition according to claim 23, characterized in that the rest comprises at least one additional modified or unmodified starch. 29. The composition according to claim 28, characterized in that additional starch is further selected from the group consisting of hydroxypropylated starches, octenylsuccinate derivatives, and 2-chloroethylaminodipropionic acid derivatives. 30. A method for styling hair characterized in that it comprises applying to the hair the composition according to claim 1. 31. A method for styling hair characterized in that it comprises applying to the hair the composition according to claim 23. 32. A method for styling the hair characterized in that it comprises applying to the hair the composition according to claim 24. 33. A method for styling hair characterized in that it comprises applying to the hair the composition according to claim 25.