MXPA01008964A - Aerosol hair spray compositions comprising combinations of silicone-grafted copolymers - Google Patents

Abstract

Disclosed are aerosol hair spray compositions which comprise a first and a second silicone-grafted copolymer, wherein the copolymers exhibit a dichotomous viscosity behaviour which results in superior hold and excellent hair feel benefits, and a method of styling hair comprising applying to the hair an effective amount of the above composition. The aerosol hair spray compositions comprise:(A) from about 0.1%to about 10%by weight of said composition, of a first silicone-grafted copolymer, (B) from about 0.1%to about 5%by weight of said composition, of a second silicone-grafted copolymer, (C) a neutralizng system, (D) from about 20%to about 50%by weight of said composition, of a propellant;and (E) the balance comprising a carrier.

Description

SPRAY COMPOSITIONS FOR SPRAY HAIR COMPRISING COMBINATIONS OF COPOLYMERS GRAFTED WITH SILICONE TECHNICAL FIELD The present invention relates to aerosol hair spray compositions comprising a first and second silicone-grafted copolymer, having defined molecular weights and being present in a specific proportion to each other, wherein the copolymers impart a behavior of Dichotomous viscosity to hair spray. In particular, the hair spray exhibits certain viscosity characteristics when supplied from the can and other viscosity characteristics when present in the hair. This dichotomous behavior results in a superior fixation and excellent benefits of sensation in the hair, at the time of application of the hair spray composition.

BACKGROUND OF THE INVENTION Hair styling compositions are well known in the art and are commercially available in a variety of forms including, for example, mousses, gels, lotions and hair sprays. Many other compositions contain resins to stylize the hair to provide temporary styling benefits or "fixation" for the hair. Silicone-grafted copolymers are known in the art to be particularly effective resins for styling hair because these polymers can provide good styling retention benefits while also providing a desirable hair feel. In particular, the silicone-grafted copolymers can impart a tactile feeling of softness and conditioning relative to conventional resins that do not contain silicone. Silicone grafted copolymers are typically used as neutralized copolymers because, when these copolymers are used in at least a partially neutralized form, the copolymers are provided for a hair spray composition that can be easily removed by water and / or wash with shampoo and have a good stylization performance. U.S. Patent No. 5,565,193 (Midha), issued October 15, 1996, shows hair spray compositions incorporating silicone-grafted copolymers. While hair spray compositions containing silicone-grafted copolymers provide a superior combination of good styling and desirable hair feel in relation to hair sprays incorporating other types of resins, consumers still desire products of hair spray that provides even better styling and hair-styling benefits. Unfortunately, it is difficult to obtain a better combination of styling and hair feel than is achieved by the incorporation of silicon-grafted copolymers. The viscosity of the hair spray is an important element with respect to both styling and hair feel. In general, the lower the viscosity of the hair spray composition as it is present in the hair, the better (ie, less viscous) the hair feel will be. This is because the low viscosity of the composition allows it to reach the tips and disperse efficiently on the hair. However, sprays for low viscosity hair typically result in a size. of small drop of the composition as it is supplied from the can. The small droplet size generally results in a hair spray with decreased fixation, while a larger droplet size is typically associated with increased fixation. In these low viscosity systems, attempts to increase droplet size by using alternate inserts and spray buttons have not provided the desired droplet size and can also lead to other undesirable changes in other properties of hair spray, negatively impacting the sensation and the fixation of the hair. Therefore, from the point of view of styling, hair spray compositions having high viscosity at the point where they are supplied from the can are preferred. One way of providing a hair spray with enhanced hair styling and feel anteriorly and beyond that achieved by the incorporation of the silicone-grafted copolymers could be imparting dichotomous viscosity characteristics to the hair spray. In other words, it would be desirable to develop a hair spray composition having a high viscosity when supplied from the aerosol can (i.e., under high shear conditions), but having a low viscosity at the time of depositing. in the hair (that is, in conditions of low shear). Previous attempts to achieve the benefits of a dual viscosity system in a hair spray have failed. Attempts to increase the high shear viscosity of a low viscosity hair spray composition to increase fixation, such as, for example, by making the composition more concentrated or by increasing the molecular weight of the silicone-grafted copolymer, have also resulting in higher viscosity at low shear stress. Therefore, the hair sensation imparted by the hair spray composition negatively impacts. However, at present applicants have found a way to impart the dual viscosity characteristics mentioned above to a hair spray composition and to provide hair spray compositions that provide a superior combination of styling and hair feel. before and beyond what is achieved by the simple incorporation of a copolymer grafted with silicone in a mist for the hair. These characteristics are achieved by combining a first silicone-grafted copolymer with a second silicone-grafted copolymer, wherein the monomers forming the respective silicone-grafted copolymers are present in the copolymers at a particular weight percentage and wherein the first and second silicone-grafted copolymers are present in the hair spray composition at a particular ratio to each other. Hair spray compositions containing combinations of silicone-grafted copolymers are generally described in U.S. Patent No. 5,618,524 (Bolich), issued April 8, 1997. However, the '524 patent does not show Specifically, the silicone-grafted polymers wherein the monomers are present in proportions as described herein and, accordingly, the hair spray compositions show therein not necessarily a supply of the same combination of good stylization and good sensation in the hair as the compositions of the present invention.

An objective of the present invention. is to provide hair spray formulations that exhibit a dichotomous viscosity behavior at high shear and low shear stress, resulting in superior fixation and excellent hair feeling benefits. It is also another object of this invention to provide a method for styling hair. These and other objects will become readily apparent from the following detailed description.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to aerosol hair spray compositions that provide excellent styling and sensation benefits in hair. These hair spray compositions comprise: (A) between about 0.1% and 10% by weight of a first silicone-grafted copolymer; (B) between about 0.1% and 5% by weight of a second silicone-grafted copolymer; (C) a neutralizing system comprising at least one base selected from the group consisting of an organic base an inorganic base and mixtures thereof, wherein the system is present at a level sufficient to neutralize between about 30% and 95% of the acid groups in the first silicone-grafted copolymer; (D) between about 20% and 50% by weight of a propellant; and (E) the moiety comprising a carrier, wherein the carrier is suitable for solubilizing the first and second copolymers grafted with silicone and the carrier is suitable for application to the hair. The first silicone-grafted copolymer has a weight average molecular weight of between about 10,000 and 500,000. It comprises a polymeric vinyl structure and a polysiloxane macromer grafted to the structure. The polymeric vinyl structure is formed from the copolymerization of randomly repeating hydrophilic monomer units, hereinafter designated A and may further include randomly repeating hydrophobic monomer units, hereinafter designated B. The polymeric vinyl structure comprises from about 10. % and 50% by weight of the copolymer of copolymerizable (hydrophilic) monomers A, and between about 0% and 85% by weight of the copolymer of copolymerizable (hydrophobic) B monomers. The polysiloxane macromer comprises from about 5% to 50% by weight of the copolymer of the monomeric units containing polysiloxane and has a weight average molecular weight of between about 500 and 50,000. The second silicon-grafted polymer has a weight average molecular weight of between about 300,000 and 5,000,000. It also comprises a polymeric vinyl structure and a polysiloxane macromer grafted to the structure. The polymeric vinyl structure is formed from the copolymerization of randomly repeating (hydrophobic) monomeric units B. The polysiloxane macromer comprises from about 10% to 40% by weight of the copolymer, of monomeric units containing polysiloxane and has a weight average molecular weight of between about 5,000 and 50,000. The polymeric vinyl structure of the second silicone-grafted copolymer contains essentially non-A (hydrophilic) monomers. The first silicone-grafted copolymer is present, in relation to the second silicone-grafted copolymer, by weight, in a ratio between about 2: 1 and 26: 1. The present invention furthermore relates to a method for styling hair comprising applying to the hair an amount of the composition described above that is effective to provide styling benefits.

DETAILED DESCRIPTION OF THE INVENTION The aerosol hair spray compositions of the present invention provide a combination of excellent styling and feeling benefits in the hair. This combination of benefits is achieved because the compositions of the present are formulated in such a way as to exhibit dichotomical viscosity characteristics. By "dichotomous viscosity characteristics" it is to be understood that hair spray compositions exhibit high viscosity characteristics under conditions of high shear stress (e.g. at the point at which they are supplied from the aerosol can) but exhibit characteristics of low viscosity under conditions of low shear stress (for example as it is present in the hair). The aerosol hair spray compositions of the present invention may comprise, consist of, or consist essentially of, essential elements and limitations of the invention described herein, as well as any of the additional or optional ingredients, components or limitations described herein. In particular, the spray hair spray compositions of the present invention comprise A) a first silicone-grafted copolymer, B) a second silicone-grafted copolymer, C) a neutralizing system, D) a propellant and E) a carrier . Each of these components, as well as the methods for making and using the hair spray compositions herein, is described in detail below.

I. COMPONENTS A. First silicone-grafted styling copolymer The aerosol hair spray compositions of the present invention comprise between about 0.1% and 10% by weight of the composition of a first styling graft copolymer. These copolymers are characterized by polysiloxane entities covalently bonded to a polymeric carbon based and pendant structure of the same.

The first silicone-grafted copolymers suitable for use herein include "silicone-containing" (or "polysiloxane-containing") monomers, which form the pendant silicone macromer of the structure and the non-silicone-containing monomers, which form the structure polymer organic The monomeric units that do not contain silicone for the first silicone-grafted copolymer can be derived from monomeric units A (hydrophilic). They may also include monomeric units B (hydrophobic). Therefore, the silicone-grafted copolymers for use herein may comprise combinations of monomeric A (hydrophilic) and polysiloxane-containing units described herein, with or without B (hydrophobic) monomers as described herein, with the condition that the resulting styling polymer have the required characteristics as described herein. As used herein, "A (hydrophilic) monomers" are those monomers selected from the group consisting of unsaturated mono and polycarboxylic organic acids, unsaturated (meth) acrylate alcohols, unsaturated organic acid anhydrides and mixtures thereof. As used herein, "B (hydrophobic) monomers" are those monomers selected from the group consisting of esters of acrylic acid, esters of methacrylic acid, vinyl compounds, vinylidene compounds, unsaturated hydrocarbons, esters of Ci-Ciß alcohol or organic acids, organic acid anhydrides and mixtures thereof. The first silicone-grafted copolymers generally comprise between about 5% and 50%, preferably between about 5% and 40%, more preferably between about 10% and about 25% by weight of the copolymer of monomeric units containing polysiloxane; between about 10% and 50%, preferably between about 10% and 30%, more preferably between about 15% and 25% by weight of the monomer copolymer A (hydrophilic). The first copolymers generally comprise between about 0% and 85%, preferably between about 30% and 85%, more preferably between about 50% and 75% by weight of the copolymer of monomers B (hydrophobic). The total level of monomers A (hydrophilic) and monomers B (hydrophobic) is preferably between about 50% and 95%, more preferably between about 60% and 95%, most preferably between about 75% and 90%. % by weight of the copolymer. The first preferred silicone-grafted copolymers for use herein are those that when formulated into the finished, dried hair spray composition, the copolymer phase is separated into a discontinuous phase that includes the polysiloxane macromer and a phase continuous that includes the structure. It is believed that this phase separation property provides a specific orientation of the copolymer in the hair which results in the conditioning and styling benefits desired. Silicone graft copolymers of the type incorporated in the hair spray compositions of the present invention and which are referred to herein as "silicone-grafted first copolymers" are known in the art. See U.S. Patent Nos. 5,618,524 (Bolich), issued April 8, 1997 and 5,658,557 (Bolich), issued August 19, 1997., both are incorporated herein by reference in their entirety. Copolymers are silicone-engrafted copolymers that provide a thin polymeric film on the hair from the hair spray composition that can be removed with a shampoo. The polymeric structure and macromeric silicone components of these first silicone-grafted copolymers as well as the characteristics of the copolymers are described in further detail below. i. Polymeric Structure The polymeric structure of the first silicon-grafted copolymer is an organic structure, preferably a carbon chain structure derived from the polymerization of ethylenically unsaturated monomers, such as a vinyl polymer structure although they may also include cellulose chains or other polymer chains derivatives of carbohydrate to which the polysiloxane entities are suspended. The structure can also include ether groups, ester groups, urethane groups and the like. The first silicone-grafted copolymer is formed from monomers A (hydrophilic), as described above. Importantly, the first silicon-grafted copolymer should contain al. less about 10% by weight of the copolymer of the copolymerizable (hydrophilic) monomers. Specific non-limiting examples of suitable (hydrophilic) monomers include, but are not limited to: acrylic acid, methacrylic acid, maleic acid, maleic anhydride, maleic esters of maleic anhydride, crotonic acid and itaconic acid. These monomers are functional groups with a carbon base and contain acid that can be neutralized with the neutralizing system defined below. Preferred (hydrophilic) monomers include acrylic acid, methacrylic acid, and mixtures thereof. Non-limiting examples of suitable (hydrophobic) B monomers include, but are not limited to: esters of acrylic or methacrylic acid of C? -Ci8 alcohols such as, for example, methanol, ethanol, methoxy ethanol, 1-propanol, 2-propanol, 1-butanol , 2-meth i 1- 1 -propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 1-meth i 1-butanol, 3-methyl-1-butanol, 1 -met i 1-1 -pent anol, 2-met i 1- 1 -pent anol, 3-yl-1-pentanol, t-butanol (2-met i 1- 1 -propanol), cyclohexanol, neodecanol, 2 -et-1-butyl anol, 3-heptanol, benzyl alcohol, 2-octanol, 6-methyl-1-heptanol, 2 -et i 1-1-hexanol, 3, 5-dimet i 1- 1 -hexanol, 3, 5, 5-1 ri -me ti 1-1-hexanol, 1-decanol, 1-dodecanol, 1-hexadecanol, 1-octadecanol and the like, alcohols having from about 1-18 carbon atoms with the average number of carbon atoms that is approximately 4-12; styrene; polystyrene macromer; vinyl acetate; vinyl chloride; vinylidene chloride; vinyl propionate; α-methylstyrene; t-butyl styrene; butadiene; cyclohexadiene; ethylene; propylene; vinyl toluene and mixtures thereof. Preferred (hydrophobic) monomers B include n-butyl methacrylate, isobutyl methacrylate; methacrylate of 2-ethylhexyl, methyl methacrylate, t-butyl acrylate, t-butyl methacrylate and mixtures thereof. The polymeric vinyl structure of the first silicone-grafted copolymer preferably has a glass transition temperature (Tg) or crystalline melting point (Tm) of at least about -20 ° C, preferably between about 20 ° C and 80 ° C. C, more preferably between about 20 ° C and 60 ° C. Styling polymers having these Tg or Tm values form hair styling films that are not excessively tacky or adhesive to the touch. In the sense in which it is used herein, the abbreviation refers to the glass transition temperature of the polymer structure and the abbreviation "Tm" refers to the crystalline melting point of the structure, if this transition exists for a polymer determined. Preferably both the Tg and the Tm, if any, are within the ranges mentioned above. ii. Silicone-containing macromer The first silicon-graft copolymer also comprises a polysiloxane macromer (idialkyl polyols, more preferably polydimet i 1 if loxane) grafted to the structure are especially preferred. The polysiloxane entities can be substituted in the polymer or can be produced by the copolymerization of polymerizable monomers containing polysiloxane with polymerizable monomers that do not contain polysiloxane. Suitable polymerizable polysiloxane-containing monomers for the first silicone-grafted copolymers include, but are not limited to, those monomers which are suitable for the formula: X (Y) nSi (R) 3_mZt I) wherein X is an ethylenically unsaturated group, such as for example a vinyl group, which may be copolymerized with the non-silicone-containing monomers described herein; And it is a divalent linking group; R is a hydrogen atom, lower alkyl (for example C? -C4), aryl alkylamino tri (C? -C4 alkyl) siloxy or Ci-C4 alkoxy; Z is a monovalent siloxane polymer entity; n is O or 1; and m is an integer from 1 to 3. These polymerizable polysiloxane containing monomers have a weighted average molecular weight as described above. Preferably, the polysiloxane-containing monomer is selected from one or more nonomers that are suitable for the following formulas (II to VII): X-C-O- (CH * 2n) '"q-- (R4) •, mZ, (II) X-Si (R4) 3-p ^ m (III) - (CH2) q- (0) p-Si (R4) 3_? PZm (IV) or H OR R- X-C-O- (CH2) 2 -N-C-N- -Si (R4) (V) 3-mZm O OH X-C-0-CH., - CH-CH -N- (CH,) _.- Si (R4) -, "VI) 3 - arZr (m H O R '• X-C-O- (CH2) 2-N-C-N- (CH2) q-Si (R4) 3_mZm < VI1) wherein m is 1, 2 or 3 (preferably m = 1); p is 0 or 1; q is an integer from 2 to 6; R "is alkyl or hydrogen, X is conformed to the formula: CH = C- wherein R1 is hydrogen or -COOH (preferably R1 is hydrogen) R2 is hydrogen, methyl or -CH2COOH (preferably R2 is methyl); conforms to the formula: CH, R '4_ (_Si_0-) CH- wherein R 4 is alkyl, alkoxy, alkylamino, aryl, or hydroxyl (preferably R 4 is alkyl); and r is an integer between about 5 and 700, preferably between about 50 and 500 (most preferably r is between about 150 and 300). Of the above formulas, formula II is the most preferred, particularly when p = 0 and q = 3. The polysiloxane macromer for the first silicone-grafted copolymer should have a weight average molecular weight of at least about 500, preferably between about 1,000 and 50,000, more preferably between about 5,000 and 40,000, most preferably between about 10,000 and 20,000. The first preferred silicone-grafted copolymers comprise monomer units derived from at least one monomer B (hydrophobic) of free radically polymerizable vinyl and at least one monomer A (hydrophilic) which can be copolymed with the vinyl monomer and at least one polysiloxane macromer. Other examples of suitable silicone graft copolymers and their methods of preparation are described in U.S. Patent No. 4,693,935 (azurek), issued September 15, 1987; and U.S. Patent No. 4,728,571 (Clemens), issued March 1, 1988, the disclosures of which are incorporated herein by reference. iii. Characteristics, preparation and examples of the first silicone-grafted copolymer The first silicone-grafted copolymers preferably have a weight average molecular weight of between about 10,000 and 500,000, more preferably between approximately 50,000 and 300,000, even more preferred between approximately 90,000 and 165,000. The concentration of the first silicone-grafted copolymer in the hair spray composition should be sufficient to provide the styling performance for the desired hair and generally varies for the first copolymer of between about 0.1% and 10%, preferably between about 2% and 9%, more preferably between about 3% and 7% by weight of the composition. The first silicone-grafted copolymers can be produced by any conventional polymerization techniques or otherwise known in the art. The first silicone-grafted copolymers described above and the second silicone-grafted copolymers described below can be synthesized by the free-radical polymerization of the monomers containing silicone or polysiloxane with monomers that do not contain silicone or polysiloxane. The general principles of free radical polymerization methods are well understood. See, Odian, "Principies of Polimeri zat ion", 3- ed., John Wiley & amp;; Sons, (1991), in 198-334. Non-limiting examples of some of the first preferred silicone-grafted copolymers for use in the aerosol hair spray compositions herein are listed below. Each listed polymer is followed by its monomer composition as part by weight of the monomer used in the synthesis: (i) t-butyl acrylate macromer / acrylic acid / poly idimet i ls i loxane - weighted average molecular weight macromer 10,000 (60/20/20); (ii) macromer of t-butyl acrylate / acrylic acid / polydimethylsiloxane-macromer of 10,000 weighted average molecular weight (70/10/20); (iii) macromer of t-butyl methacrylate / acrylic acid / poly idimet ils i loxane - weighted average molecular weight macromer - 10,000 (65/15/20); (iv) macromer of t-butyl acrylate / acrylic acid / poly idimet ilsiloxane-macromer of average molecular weight 10,000 (75/15/10); It may be desirable to purify the first silicone-grafted copolymer by removing the unreacted silicone-containing monomer and the polymer grafted with the silicone macromer with viscosities at 25 ° C of about 10,000,000 centistokes and less. This can be done, for example, by extraction of hexane. After drying, the resin forms its reaction solvent, the hexane extraction of the reaction product can be carried out by adding an excess of hexane to the reaction product and heating to almost the Tg of the silicone-free portion of the polymer. The mixture is kept at this temperature with stirring for about 30 minutes and cooled to room temperature. The hexane is removed by vacuum suction. Preferably, two additional hexane extraction cycles are conducted in the same manner as above. After the third cycle, the residual hexane remaining with the product is removed by distillation and vacuum drying. The low molecular weight polysiloxane containing monomer and polymer are solubilized by supercritical carbon dioxide and transported out of the remaining polymer by a transfer line, which is maintained at the identical temperature and pressure as the fraction vessel. The extracted materials are collected in an extraction vessel. After extraction, the system is depressurized and dried, the extracted copolymer is recovered from the extraction vessel.

B. Second silicone-grafted styling copolymer The aerosol hair spray compositions of the present invention comprise between about 0.1% and 5% by weight of the composition, of a second styling graft copolymer. When combined with the first silicone-grafted copolymer, at proportions specified herein, the second silicone-grafted copolymers provide a thin polymeric film on the hair from the hair spray composition that is removed with a shampoo. These copolymers, similar to the first silicone-grafted copolymers, are known in the art, and are also characterized by polysiloxane entities covalently bonded to and suspended from a polymeric carbon based structure. Similar to the first silicone-grafted copolymers, the second silicone-grafted copolymers comprise "silicone-containing" monomers (or "containing polysiloxane"), which form the pendant silicone macromer of the structure and monomers that do not contain silicone, which form the organic structure of the polymer. The monomeric units that do not contain silicone for the second silicone-grafted copolymer can be derived from monomeric units B (Hydrophobic). Therefore, the second silicone-grafted copolymers for use herein may comprise combinations of monomeric B (hydrophobic) and polysiloxane-containing units described herein, with the proviso that the resulting styling polymer has the necessary characteristics as described above. describes in the present. However, other than the first silicone-grafted copolymers, the second silicone-grafted copolymers are practically free of (hydrophilic) A monomers. The second styling copolymers grafted with silicones generally comprise between about 10% and 40%, preferably about 10% and 30%, more preferably between about 15% and 25% by weight of the copolymer of monomeric units containing polysiloxane. The second preferred silicone-grafted copolymers for use herein are such that when formulated into the finished, dried hair spray composition, the copolymers are phase separated into a discontinuous phase including the polysiloxane macromer and a continuous phase that includes the structure. The polymer structure and the silicone macromer components of these second silicone-grafted copolymers, as well as the characteristics of the copolymers are described in greater detail below. i. Polymeric Structure The polymeric structure of the second silicon-grafted copolymer is an organic structure, preferably a carbon chain derived from the polymerization of ethylenically unsaturated monomers, such as for example the vinyl polymeric structure but may also include chains or other polymeric chains derived of carbohydrate to which the polysiloxane entities are suspended. The structure may also include ether groups, ester groups, urethane groups and the like. The structure of the second silicone-grafted copolymer is practically free of monomers A (hydrophilic). The polymeric vinyl structure of the second silicone-grafted copolymer preferably has a glass transition temperature (Tg) or crystalline melting point (Tm) of at least about -20 ° C, preferably between about 20 ° C and 80 ° C. C, more preferably between about 20 ° C and 60 ° C. Preferably, both the Tg and the Tm, if any, are within the ranges mentioned above. ii. Silicone-containing macromer The second silicon-grafted copolymer also comprises a polysiloxane macromer (especially polydialkylsiloxane is preferred), most preferably polydimethexysiloxane) grafted to the structure. The polysiloxane entities can be substituted in the polymer or can be produced by the co-polymerization of polymerizable monomers containing polysiloxane with polymerizable monomers that do not contain polysiloxane. Suitable polymerizable polysiloxane-containing monomers for the second silicone-grafted copolymers include, but are not limited to, those monomers which are formed with the formula: X (Y) nSi (R) 3-mZm (I)wherein X is an ethylenically unsaturated group, such as for example a vinyl group, which may be copolymed with the non-silicone-containing monomers described herein; And it is a divalent linking group; R is a hydrogen atom, lower alkyl (for example C? -C4), aryl alkylamino tri (C? -C4 alkyl) siloxy or Ci-C alkoxy; Z is a monovalent siloxane polymer entity; n is 0 or 1; and m is an integer from 1 to 3. These polymerizable polysiloxane containing monomers have a weighted average molecular weight as described above.

Preferably, the polysiloxane-containing monomer is selected from one or more monomers which are suitable for the following formulas (II to VII): OR X-C-O- (CH2) q- (0) p-Si (R4) 3_mZm (ID X-Si (R4) 3_mZm (III) O H O R.

X-C-O- (CH2) 2 (V) OH X-C-0-CH2-CH-CH2-N- (CH2) q-YES (R4) 3 _mZ. (VI) m H O R " X-C-O- (CH2) 2-N-C-N- (CH2) -Si (R i *) 3_mZ, (VII) m wherein m is 1, 2 or 3 (preferably m = 1); p is 0 or 1; q is an integer from 2 to 6; R "is alkyl or hydrogen, X conforms to the formula: CH = C- wherein R1 is hydrogen or -COOH (preferably R1 is hydrogen) R is hydrogen; methyl-CH2COOH (preferably R2 is methyl); Z conforms to the formula: wherein R 4 is alkyl, alkoxy, alkylamino, aryl, or hydroxyl (preferably R 4 is alkyl); and r is an integer between about 60 and 700, preferably between about 60 and 500 (most preferably r is between about 100 and 350). Of the above formulas, formula II is the most preferred, particularly when p = 0 and q = 3. The polysiloxane macromer for the second copolymer should have a weight average molecular weight of between about 5,000 and 50,000 preferably between about 5,000 and 30,000 more preferably between about 8,000 and 25,000. iii. Characteristics, preparation and examples of the first silicone-grafted copolymer The second silicone-grafted polymers preferably have a weight average molecular weight of between about 300,000 and 5,000,000, more preferably between about 500,000 and 2,000,000, even more preferably between about 60,000 and 1,500,000. The concentration of the second silicone-grafted copolymer in the hair spray composition should be sufficient to provide styling performance for the desired hair and generally varies for the second copolymer of between about 0.1% and 5%, preferably between about 0.25% and 3%, more preferably between about 0.25% and 1.5% by weight of the composition. The second silicone-grafted styling copolymers can be produced by any of the conventional polymerization techniques or otherwise known in the art, including those techniques described above for the synthesis of the first silicone-grafted copolymers. Non-limiting examples of some of the second silicone-grafted copolymers for use in the aerosol hair spray compositions of the present are listed below. Each listed polymer is followed by its monomer composition as a part by weight of the monomer used in the synthesis: (i) t-butyl acrylate / polydimethylsiloxane macromer macromer of weighted average molecular weight 10,000 (80/20); (ii) t-butyl acrylate / polydimethylsiloxane macromer macromer of weight average molecular weight 10,000 (75/25); (iii) acrylate macromer of t-butyl, polymethyl, and loxane-weighted average molecular weight macromer - 20,000 (80/20); (iv) t-butyl acrylate / poly idimet il s i loxane macromer macromer of 10,000 weighted average molecular weight (85/15); C. Neutralizing System The aerosol hair spray compositions of the present invention comprise a neutralizing system comprising an organic base, an inorganic base or mixtures thereof, to neutralize or partially neutralize the first silicon-grafted styptic copolymer as described herein. The aerosol hair spray compositions of the present invention contain a total amount of a neutralizing system with which they are neutralized between about 30% and 95%, preferably between about 80% and 95% of the acid monomers of the first copolymer grafted with silicone. Any conventional organic materials and inorganic base materials can be used in the hair spray composition herein, provided they are used in accordance with the necessary neutralization capabilities described herein. Non-limiting examples of inorganic base materials suitable for use herein include ammonium hydroxide and alkali metal and alkaline earth metal hydroxides including potassium hydroxide, sodium hydroxide and mixtures thereof. Preferred inorganic base materials include po hydroxideSo, sodium hydroxide and mixtures of the same.

Non-limiting examples of organic base materials suitable for use herein include amines, especially amino alcohols such as for example 2-amino-2-metyl-1,3-propanediol (A PD), 2-amine-2-ethyl -l, 3-propanediol (AEPD), 2-amino-2-methyl-1-propanol (AMP), 2-amino-1-but-anol (AB), monetanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA) ), monoi sopropanolamine (MIPA), diisopropanolamine (DIPA), trii sopropanolamine (TIPA), dimethyl teramin (DMS), dimet i lmiri s tamina (DMM), dimethyl illauramine (DML), amino methyl propanol (AMP), and mixtures of the same. A preferred organic base material is amino methyl propanol. The amount, in grams, of the organic and inorganic base materials (Z) required to neutralize an acidic polymer can be deduced from calculations that take into account the acid value of the polymer (A); the amount of the polymer (W); the molar weight of the base (B); the molar weight of the acidic entity (M) and the degree of neutralization required (N).

Z (g) = W x A / lOOx 1 / M x B x N% In the following example, the amount of KOH required to neutralize 2.6 g of acrylic acid copolymer (with an acid value of 20) is calculated at a level of neutralization at 60%.

Z (g) = 2.6 x 20/100 x 1/72 x 56 x 0.60 Z = 0.24g Note that the acid value can be determined experimentally by titrating a specific amount of the polymer based on or theoretically by considering the original acid content of the polymer, for example, a polymer with 20% acidic monomer has an acid value of 20.

D. Propellant The aerosol hair spray compositions of the present invention comprise between about 20% and 50% by weight of the composition, of a propellant suitable for delivering spray of the hair spray composition to the desired application surface. . It has been found that the spray performance benefits of aerosol hair spray compositions are improved by minimizing the concentration of the hydrocarbon propellants to less than about 10% by weight of the composition. In the sense in which it is used herein, "hydrocarbon propellants" are those liquids that can be liquefied and that contain only carbon and hydrocarbon atoms, most notably of which are propane, butane and isobutane. The spray hair spray compositions of the present invention preferably contain less than about 10%, more preferably less than about 5% and most preferably 0%, by weight of the hydrocarbon propellant composition. Non-limiting examples of hydrocarbon propellants suitable for use herein include n -butane, isobutane, supplied as A-31, by Exxon Corporation, and isobutane / propane, supplied as A-46, by Exxon Corporation and mixtures thereof. The total concentration of the hydrocarbon-free oroprene in the aerosol hair spray composition may include one or more propellants without hydrocarbon; the concentration of propellant without total hydrocarbon typically ranges from about 20% to 50%, most preferably from about 35% to 40% by weight of the composition. As used herein, "hydrocarbon-free propellants" are all liquefiable gases suitable for use in topical application to human hair or skin, excluding the hydrocarbon propellants identified above. Non-limiting examples of hydrocarbon-free propellants suitable for use herein include: nitrogen, carbon dioxide, nitrous oxide, atmospheric gas 1,2-di f luoroethane (Hydrofluorocarbon 152A) supplied as Dimel 152A by EI Du Pont de'Nemours Corporation , dimethyl ether and mixtures thereof. A preferred hydrocarbon-free propellant is dimethyl ether.

E. Carrier Aerosol hair spray compositions of the present invention comprise a suitable liquid carrier, preferably a liquid carrier at concentrations ranging from about 35% to 79.8%, preferably between about 50% and 75%, most preferably between about 55% and 70% by weight of the composition. The liquid carrier for use herein may comprise any liquid carrier known or otherwise effective for use in aerosol formulations intended for topical application to human hair or skin, for example, liquid carriers for use in spray formulations for the hair spray. The liquid holder may include solvents and other optional ingredients of the hair spray compositions of the present invention. However, it is preferred that aerosol hair spray compositions contain less than about 3% water. Suitable liquid carriers for use in the hair spray compositions of the present invention include organic solvents such as, for example, C? -C6 alkanes, carbitol, acetone, C7-C10 isoparaffins and mixtures thereof. Preferred liquid carriers are C alca-C6 alkanols and C7-C10 isoparaffins. Non-limiting examples of preferred Ci-C alca alkanols include C2-C monohydric alcohols such as, for example, ethanol, isopropanol and mixtures thereof. Non-limiting examples of C7-C isoparaffins are Isopar CMR, Isopar EMR and Isopar GMR, all available from Exxon Corporation.

II. OPTIONAL COMPONENTS A. Plasticizer Spray hair spray compositions of the present invention may, in some embodiments, comprise a non-volatile plasticizer at concentrations effective to provide. an improved hair style performance. These concentrations generally range from about 0% to 2%, preferably from about 0.2% to 0.6% by weight of the composition. In the sense in which it is used herein, "non-volatile" with respect to plasticizers means that the plasticizer does not have a vapor pressure that can be measured under ambient conditions. The copolymer-liquid carrier solution must not experience a substantial loss of weight of the plasticizer while the liquid carrier is evaporating, as this may excessively reduce the amount of the copolymer during use. The plasticizers to be used in the present generally should have boiling points greater than or equal to about 250 ° C. These materials are well known in the art and are described in Kirk-Othmer Encyclopedia of Chemical Technology, 2- ed., Vol. 15, at 720-789 (John Wiley &Sons, Inc. New York, (1968)) under the topic heading "Plasticizers"; in The Technology of Pious Technicians, by J. Kern Sears and J. R. Darby (John Wiley &Sons, Inc., New York, (1982)); and in the Sears / Darby Appendix, Table A.9, at 983-1063; whose descriptions are incorporated herein by reference. Suitable plasticizers for use in the aerosol hair spray compositions of the present invention include both cyclic and acyclic volatile materials. Non-limiting examples of suitable non-volatile plasticizers include: adipates, phthalaros, isophthalates, azelates, stearates, citrates, trimethalates, silicone copolyols, C 4 -C 22 iso-alcohols, carbonates, sebacate, isobut irates, oleates, phosphates , myristates, ricinoleat os, pelargonatos, valerate, camphor, glycols, glycerins, citrates and castor oils. Preferred plasticizers for use herein include diisobutyldipate (DIBA) and glycols. Preferred glycols include propylene glycol, dipropylene glycol and mixtures thereof.

B. Conditioner The aerosol hair spray compositions of the present invention may, in some embodiments, additionally comprise a conditioning agent at effective concentrations to modify hair feel. These concentrations generally range from about 0.01% to 5% by weight of the composition. Useful conditioning agents include silicone and silicone copolyols. Additionally, vitamin B5 alcohols, preferably panthenol, can be used. The silicone conditioning agent may comprise a silicone fluid and may also comprise other ingredients such as, for example, silicone resin to enhance the deposition efficiency of the silicone fluid or to enhance the shine of the hair. These additional efficiency and gloss benefits are especially provided when silicone conditioning agents with high refractive index (ie, greater than about 1.46) are used. A preferred high refractive index silicone conditioning agent is phenyl trimethicone. The silicone conditioning agent may comprise a volatile silicone, a non-volatile silicone and mixtures thereof. Suitable silicone fluids for use herein include silicone oils that can flow with a viscosity of less than about 1,000,000 centistokes, preferably between about 5 and 1,000,000 centistokes, more preferably between about 10 and 600,000 centistokes, still more preferred between about 10 and 500,000 centistokes, and most preferably between about 10 and 300, 000 centistokes, at 25 ° C. Suitable silicone oils for use herein include, but are not limited to: polyalkylsiloxanes, polyarylsiloxanes, polyalkylaryl siloxanes, polyethersiloxane copolymers, and mixtures thereof. Other non-volatile, insoluble silicone fluids having conditioning properties for the hair can also be used. A preferred volatile silicone is decamet ilciclopent as siloxane (cyclomethicone D5), supplied by General Electric Corporation.

C. Other Optional Ingredients The aerosol hair spray compositions of the present invention may, in some embodiments, additionally comprise optional components known or otherwise effective for use in hair care products or for personal care, with the condition that the optional components are physically and chemically compatible with the essential components described herein, or that otherwise do not unduly impair the stability, aesthetics or performance of the product. The concentration of these optional ingredients generally ranges from zero to about 25%, more typically from about 0.05% to 25%, even more typically from about 0.1% to 15% by weight of the composition. Non-limiting examples of optional ingredients include: preservatives, surfactants, styling copolymers other than the silicone grafted copolymers and in addition thereto described, thickeners and viscosity modifiers, electrolytes, fatty alcohols, antidandruff active, pediculocides or insecticides for lice, skin active agents, pH adjusting agents, fragrances, perfume oils, perfume solubilizing agents, sequestering agents, emollients, lubricants and penetrants such as for example various lanolin compounds, protein hydrolyzates and other derivatives of protein, ethylene and polyoxyethylene erol adducts, sunscreens and volatile and non-volatile silicone fluids other than the silicone fluids and in addition to the same described herein.

III. MANUFACTURING METHODS The aerosol hair spray compositions of the present invention can be prepared by any known or otherwise effective technique suitable for providing an aerosol hair spray composition with the proviso that the first and second Polymers grafted with silicone are formulated to have and provide the necessary dichotomous viscosity characteristics defined herein. Methods for preparing spray hair spray compositions of the present invention include conventional formulation and mixing techniques. Suitable methods include two main parts: the preparation of the aerosol concentrate and the aerosolization of that concentrate. To prepare the aerosol concentrate, add the solvents (ethanol, isoparaffins) to a suitably sized container. Start mixing with an agitator capable of producing a strong agitation. Add the copolymers to the solvents slowly to avoid agglutination. Mix until the polymers are completely solubilized. Add the neutralizer and mix until everything is homogeneous. Add the remaining ingredients (except the propellants) allowing each one to be incorporated completely before adding the next ingredient. After all the ingredients have been added, leave the mixture for 10 to 15 minutes to ensure homogeneity. To aerosolize the concentrate, fill in a suitable container such as, for example, an aerosol dispenser and then add the propellant to that container. This can be done by any of the commonly accepted methods in the aerosol industry. Finally, equip the container with an actuator such as for example a button for spray. The aerosol hair spray compositions of the present invention may be contained or supplied in any known or otherwise effective container or system for aerosol delivery. All of these containers or delivery systems must be compatible with the essential ingredients and any optional ingredients selected from the hair spray composition of the present invention. Alternatively, pressurized aerosol dispensers can be use wherein the propellant is separated from contact with the hair spray composition by the use of specialized containers such as for example a two-compartment can of the type sold under the trade name SEPRO of the American National Can Corporation. Other suitable aerosol dispensers include those containing compressed air propellant that can be filled into the dispenser by means of a pump or equivalent device before use. These dispensers are described in United States Patent No. 4, 077,441 (Olofsson), granted on March 7, 1978; and U.S. Patent No. 4,850,577 (TerStege), issued July 25, 1989. Aerosol containers with compressed air suitable for use are also currently sold by The Procter & Gamble Company as sprays for hair with its trade name VIDAL SASSOON AIRSPRAY®.

IV. METHODS OF USE Spray hair spray compositions of the present invention are used in a conventional manner to provide hair style / fixation benefits. An effective amount of the composition is sprayed onto dry or wet hair before and / or after the hair is styled. In the sense in which it is used in the present "effective amount" it means an amount sufficient to provide the hair volume and performance of desired style, according to the length and texture of the hair.

ANALYTICAL METHODS Various parameters used to characterize the elements of the present invention, including molecular weight and molecular weight distribution, are to be quantified by particular experimental analytical procedures. Those procedures are described below. The molecular weights and molecular weight distributions of the copolymers suitable for use in the hair spray compositions of the present invention can be determined by Size Exclusion Chromatography (SEC) techniques. known in this field. One of these techniques includes the separation of the molecules by the use of a reticulated poly (rene-divinylbenzene) column (molecular weight range = 100-107), a differential refractive index detector and a differential viscometer. A universal calibration curve is prepared for the monodispersed polystyrene standards of known molecular weight (MW) and molecular weight distribution (MWD). The indicated MW and MWD of the polymer are determined based on the concentration and viscosity responses in relation to the calibration. This method for measuring the molecular weights of the silicone-grafted copolymers of the present invention, using gel permeation chromatography (GPC) with differential viscometric and refractive index detection, is detailed below.

TO . Principle Polymer samples are dissolved in tetrahydrofuran (THF) containing toluene. The sample is subjected to chromatography using a series of GPC columns with a THF mobile phase. The detection is made by detection of differential refractive index and viscometric. The changes in the velocity of circulation are adjusted using toluene as a marker of time retention. A universal calibration curve using polystyrene is constructed and used to determine the molecular weight of the sample. The separation by GPC includes the separation through a hydrodynamic volume of the molecular distribution. The universal calibration is based on the theories of Flory who showed theoretically that the hydrodynamic volume of a molecule in solution is to provide the molecular weight multiplied by the intrinsic viscosity. Benoit showed that polymers from different chemical structures would be on the same calibration graph if the intrinsic viscosity parameter is taken into account for calibration. The Viscotek GPC-viscomet ry module uses the continuous intrinsic viscosity distribution and a molecular weight multiplied by the intrinsic viscosity calibration curve to take into account changes in chemical structure and generate true molecular weights and distributions of molecular weight of the polymer samples.

B. HPLC equipment Variain 5000 or 9010 series pump, or HP 1050 or HP 1100 and self-testing or equivalent Rl Waters 410 Refractive Index detector or equivalent DV detector Viscotek differential viscometer Model 100 or H502B or equivalent Viscotek Trisec data system Version 2.7 or equivalent Balance Exacto F O.OOOlg Volumetric flasks with lOOOml plugs Volumetric probes 20ml, lOml Self-testing Vials & Caps For use.,. ^ E with a suitable self-tester Glass jars Scintillation flasks of 8 drachms and 4 drachmas with screw caps coated with Teflon C. Reagents 1. Tetrahydrofuran, 99.5 +%, grade J. T. Baker HPLC, stabilized with 250 ppm of BHT, Cat. # JT9440-3 2. Toluene, 99 +%, J. T. Baker, Cat. # JT9460-3 3. Polystyrene of standard molecular weight, adjusted to 12, individual TSK standards, TOSOH Corporation.

D. System adaptability As a system is verified, a verified sample of the polymer must be analyzed to ensure that the system is functioning properly. NBS706 is a polystyrene sample from the National Bureau of Standards of known molecular weight. When preparing to analyze the samples, NBS 706 should be analyzed as a verification sample. The molecular weight for NBS706 should be 257k +/- 30k. If the molecular weight for NBS706 falls outside this range, this could indicate that the GPC system is not working properly and should be verified by an experienced analyst.

E. Experimental procedures: 1. Preparation of sample diluent / sample Transfer 100 μl of toluene into a 1000 ml volumetric flask. Add tetrahydrofuran to the volume and mix well. The resulting solution contains 100 ppm toluene (as a retention time marker) in tetrahydrofuran. 2. Preparation of Standard Solutions for Polystyrene Calibration a) Using the table below, transfer the quantity listed for each TOSO polystyrene molecular weight standard into an 8-drachma bottle separately (the bottle equipped with a Teflon-coated screw cap) .

Standard TOSO Quantity A- -2500 0.0200 g A- -5000 0.0200 g F- -2 0.0200 g F- -4 0.0200 g F- -10 0.0100 g F- -20 0.0100 g F- -40 0.0100 g F- -80 0.0100 g F- -128 0.0050 g F- -288 0.0050 g F- -450 0.0050 g F- -700 0.0050 g b) Add exactly 20.0 ml of the solvent for dilution of the sample / standard to each flask. Cover each vial safely but do not shake. Allow to settle overnight, then mix gently with your hand. These solutions can be maintained indefinitely, provided they are stored in a refrigerator (4-6 ° C) and sealed in a safe manner (screw cap and paraffin). c) Transfer a small portion of each standard solution in separate self-testing bottles for a GPC analysis. 3. Preparation of polymer samples a) Weigh 0.040 g (± 0.001 g) of the polymer directly into a tared 4-drachma flask equipped with a screw-cap coated with Teflon. b) Accurately add 10.0 ml of solvent for sample / standard dilution. Cover the bottle safely, but do not shake. Allow to settle during night, and then mix gently with your hand. c) Transfer a small portion to each of the three self-testing bottles for a triplicate GPC analysis. 4. Chromatography Samples should be analyzed using the chromatographic conditions described below.

GPC Columns: S odex KF-807 Shodex KF-80RM (Linear) Waters. '-rastyragel 100 A Pre-column Shodex KF-800P Column temperature: 31.0 ° C Mobile phase: r etrahydr - > Uranium, 1.0 ml / min Sample loop: 100 μl Detector Rl Waters 410 Sensitivity 128 Factor d > - 100 'scale. constant temperature 1 temperature 31.0 ° C Differential viscometer: Differential viscometer: Viscotek Model 100. : -. 502B Full scale PA recorder 20 Temperature 31.0CC Input pressure (Typical) 18.5 KPA Differential pressure (typical) 0 PA Flow division: 50:50 DV: RI Software: v's-otek Trisec 2.7 í Jtilizar TOSO F- 40 to adjust the file c. Parameter "Ro Peak" F. Molecular weight determination The procedure described below uses the Viscotek software to determine the molecular weight of the polymer sample. This determination can not be made without the software and requires an experienced analyst in the use of the software. 1. Peak parameter file The TOSO polystyrene standard F-40 should be used to adjust the peak parameter file.

The peak parameter file is used by the software to compensate for detector deviation and peak magnification effects. 2. Time retention marker Toluene is added to the THF used to prepare the sample used as a time retention marker to correct the lower circulation velocity variation. The time retention marker is adjusted to a flow rate of 1,000 using the retention time of toluene in the polystyrene standard TOSO F-40. The circulation speed is adjusted as appropriate for all other standards and samples based on this. 3. Universal calibration curve The universal calibration curve is constructed using the narrow polystyrene standards described above. A new calibration file opens. The file is opened for a standard of polystyrene, the speed of circulation is corrected, and it is performed continuously on the differential viscometric trace (continuation to a time with a factor of 9). Baseline lines and appropriate integration limits are drawn (as it closes at the beginning and end of the peak as possible) on the Rl and DV traces. Under the calculated heading, a narrow standard is selected and the results of this standard are added to the calibration curve. This must be done for each calibration standard until the calibration curve is completed. A calibration curve can be used for an extended period of time if there are no obvious changes in the system (ie, a significant change in circulation speeds, new columns, analysis of polymers with change in chromatography, etc.). The adjustment order selected for the calibration curves must be the third order. 4. Determination of molecular weight and polydispersity With the calibration file and appropriate open peak parameter, the molecular weight of the sample can be determined. The file for the sample is opened, the circulation speed is corrected and it is performed continuously on the differential viscometric trace (continuation to a time with a factor of 9). Baseline lines and appropriate integration limits are drawn (as close to the start and end of the peak as possible) on the Rl and DV traces. Under the calculated heading, the molecular weight is selected. The results can be displayed and printed from the results heading as a MWD summary report. Under the advanced options head, a third order graph must be selected and the averages must be calculated from the non-fixed data.

EXAMPLES The following are non-limiting examples of the spray hair spray compositions of the present invention. The examples further describe and demonstrate the embodiments within the scope of the present invention. The examples are provided solely for the purposes of illustration and are not intended to be limitations of the present invention, as many variations thereof are possible without departing from the spirit and scope of the invention, which could be recognized by someone with ordinary experience in the art. technique. In the examples, all concentrations are listed as percent by weight, unless otherwise specified.

TO . Examples of the first silicone-grafted polymer (The monomer proportions are expressed as a percentage by weight as they are loaded into the reactor.The SI monomer containing polysiloxane has a molecular weight of about 10,000.) Copolymer # 1 60/20/20 SI monomer containing t-butyl acrylate / acrylic acid / polysiloxane (weight average molecular weight copolymer 135,000) Copolymer # 2 70/10/20 monomer YES containing t-butyl acrylate / acrylic acid / po.isiloxane (copolymer of ≥ 100,000 molecular weight pioneered) Copolymer # 3 65/15/20 monomer SI qr ^ contains t-butyl methacrylate, acetic acid / pc? S? Loxane (weight copolymer or pproper 110,000) Copolymer # 4 75/15/10 monomerc SI containing t-butyl acrylate / acrylic acid / pc-isiloxane (copolymer of promising nolecule weight 90,000) B. Examples of the second silicone-grafted copolymer (The monomer proportions are expressed as a percentage by weight as they are loaded into the reactor) The SI monomer containing polysiloxane has a molecular weight of about 10,000 The S2 monomer containing polysiloxane has a molecular weight of approximately 20,000.) Copolymer # 5 80/20 SI monomer containing t-butyl acrylate / polysiloxane (weight average molecular weight copolymer 1,000,000) Copolymer # 6 75/25 SI monomer containing t-butyl acrylate / polysiloxane (weight average molecular weight copolymer 700,000) Copolymer # 7 80/20 monomer S2 containing t-butyl acrylate / polysiloxane (weight average molecular weight copolymer 1,300,000) Copolymer # 8 85/15 SI monomer containing t-butyl acrylate / polysiloxane (weight average molecular weight copolymer 900,000) C. Examples of aerosol hair spray compositions of the present invention Each of the compositions exemplified below is in the form of an aerosol hair spray, comprising a concentrate and a propellant, which is suitable for the application using a aerosol dispenser. As used herein, the abbreviated term "KOH" designates potassium hydroxide solution, which contains 45% potassium hydroxide and 55% water and other minor ingredients, and the term "AMP" designates 2-amino-2-methyl-1-propanol. The asterisk (*) designates a volatile branched hydrocarbon supplied by Exxon Corporation. Many perfumes are available for use in the following examples. A preferred perfume is Elyssa 100A, supplied by The Proctor & Gamble Company. The proportion expressed in each example is the weight ratio of the first silicone-grafted copolymer for the second silicone-grafted copolymer.

Example I Component% by weight Ethanol c. b. p. 100 Isopar C (*) 22. 7% Copolymer # 1 5 1"6 Copolymer # 5 1 Potassium hydroxide (45% active) 1.4 Diisobutyl adipate 0.5% Perfume 0.4% Panthenoi 0. 04 Dimethylether 35% 80% neutralized KOH Proportion 5: 1 Example II Component% by weight Ethanol c.b.p. 100% Isopar C (*) 15% Isopar G (*) 5% Copolymer # 2 3% Copolymer # 6 0.5% Potassium hydroxide (45% active) 0.42% Diisobutyl Adipate 0.6% Perfume 0.4% Panthenol 0.04 Dimethylether 35% 80% neutralized KOH Proportion 6: 1 Example III Component% by weight Ethanol c.b.p. 100% Isopar C (*) 12% Isopar G (*) 3% Copolymer # 1 5.5% Copolymer # 5 0.5% Potassium hydroxide (45% active) 0.86% .Aminomethyl propanol 0.60% Diisobutyl adipate 0.10% Perfume 0.4% Panthenol 0.04 Dimethylether 40% Neutralized to 90% [45% KOH / 45% AMP] Proportion 11: 1 Example IV Component% by weight Ethanol c.b.p. 100% Isopar C (*) 10% Isopar G (*) 10% Copolymer # 3 4.5% Copolymer # 7 .75% Potassium hydroxide (45% active) 0.70% Ammonomethyl propanol 0.25% Dipropylene glycol 0.40% Perfume 0.4% Panthenol 0.08 % Dimethylether Propellant A46 10% Neutralized to 90% [60% KOH / 30% AMP] Proportion 6: 1 Example V Component% by weight Ethanol c.b.p. 100 Isopar C (*) 20% Isopar G (*) 5% Copolymer # 4 5.5% Copolymer # 8 1.0% Potassium hydroxide (45% active) 0.43% Ammonomethyl propanol 0.61% Propylene glycol 0.80% Perfume 0.4% Phenyl tri ethicone 0.60% Dimethylether 30% Neutralized to 90% [30% KOH / 60% AMP] Proportion 5.5 1 Example VI Component% by weight Ethanol c.b.p. 100% Isopar C (*) 10% Isopar E (*) 5% Copolymer # 4 2% Copolymer # 5 0.5% .Aminomethyl propanol - 0.42% Diisobutyl Adipate 0.60% Perfume 0.4% Phenyltrimethicone 1.00% Dimethylether 25% Propellant A46 10% AMP neutralized at 90% Proportion 5: 1 Example VII Component% by weight Ethanol c.b.p. 100% Isopar C (*) 15% Copolymer # 1 2.0% Copolymer # 8 0.3% Potassium hydroxide (act1 45%) 0.55% Diisobutyl Adipate 0.40% Propylene glycol 0.20% Cyclomethicone D5 0.50% Perfume 0.4% Propellant A46 30% 80% neutralized KOH Proportion 6.7: 1 Example VIII Component% by weight Ethanol c.b.p. 100% Isopar C (*) 35% Copolymer # 1 2.8% Copolymer # 8 1.2% Potassium hydroxide (45% act 0.87% Diisobutyl Adipate 0.20% 0.10% trimethicone phenyl Cyclomethicone D5 0.30% Perfume 0.6% Dimethylether 25% Propellant A46 10% 90% neutralized KOH Proportion 2.3: 1 Example IX Component% by weight Ethanol c.b.p. 100% Isopar C (*) 13% Isopar E (*) 13% Copolymer # 2 6.0% Copolymer # 6 0.5% .Aminomethyl propanol 0.67% Diisobutyl adipate 0.10% 0.2% perfume Panthenol 0.05 Dimethylether 35% A46 5% AMP neutralized at 90% Proportion 12: 1 Example X Component% by weight Ethanol c.b.p. 100% Isopar C (*) 13% Copolymer # 4 4.5% Copolymer # 8 1.5% Potassium hydroxide (45% act 0.93% Perfume 0.4% Panthenol 0.04 Dimethylether 20% Dy 152a 10% KOH neutralized at 80% Proportion 3: 1 Example XI Component 6 in weight Ethanol C .b.p. 100% Isopar G (*) 10.3% Copolymer # 3 3% Copolymer # 5 0.5% .Aminomethyl propanol 0.53% Dipropylene glycol 0.05% Perfume 0.1% Panthenol 0.1 A31 27% AMP neutralized at 95% Proportion 6: 1 Example XII Component% by weight Ethanol c.b.p. 100% Isopar C (*) 5% Isopar G (*) 2% Copolymer # 1 5.5% Copolymer # 5 1% Potassium hydroxide (45% act 1.52% Propylene glycol 0.10% 0.2% perfume Panthenol 0.1% Dimethylether 40% 80% neutralized KOH 5.5: 1 ratio Example XIII Component% by weight Ethanol c.b.p. 100 ^ Isopar C (*) 7% Copolymer # 2 4.5% Copolymer # 5 0.5% Potassium hydroxide (45% act 0.70% Dipropylene glycol 0.07% 0.2% perfume Panthenol 0.5% A31 10% Dimethylether 20% 90% neutralized KOH Proportion 9: 1 Example XIV Component% by weight Ethanol c.b.p. 100% Isopar C (*) 13% Isopar E (*) 2% Copolymer # 3 5.5% Copolymer # 7 0.71% Potassium hydroxide (45% act 0.46% .Aminomethyl propanol 0.77% 0.2% perfume Panthenol 0.1% Dimethylether 40% 50% neutralized KOH / 45% neutralized AMP Proportion 7.7: 1 Example XV Component% by weight Ethanol c.b.p. 100% Isopar C (*) 28% Copolymer # 4 1.5% Copolymer # 7 0.5% Potassium hydroxide (45% act 0.31% Diisobutyl Adipate 0.2% Perfume 0.3% Panthenol 0.1% Dimethylether 35% 80% neutralized KOH Proportion 3: 1

Claims (10)

1. CLAIMS 1. A spray hair spray composition characterized in that it comprises: A) from 0.1% to 10% by weight of the composition of a first silicone-grafted copolymer comprising a polymeric vinyl structure and a grafted polysiloxane macromer the polymeric vinyl structure, i) wherein the first silicone-grafted copolymer is formed from the copolymerization of randomly repeating hydrophilic monomer units, herein designated A, hydrophobic monomer units, herein designated B and at least one polysiloxane macromer, a) wherein the vinyl polymer structure comprises from 10% to 50% by weight of the first silicone-grafted copolymer of the copolymerizable hydrophilic monomers A, b) wherein the vinyl polymer structure comprises from 0% to 85% % by weight of the first copolymer grafted with silicone of copolymerizable hydrophobic B monomers, c) wherein the copolymer in silicon coated comprises from 5% to 50% by weight of the first silicone-grafted copolymer of the polysiloxane macromers, ii) wherein the polysiloxane macromer has a weight average molecular weight of 500 to 50,000; and iii) wherein the first silicone-grafted copolymer has a weight-average molecular weight of 10,000 to 500,000, B) of 0.1% and 5% by weight of the composition, of a second silicone-grafted copolymer, comprising a polymer structure of vinyl and a polysiloxane macromer grafted to the structure vinyl polymer, i) wherein the second silicone-grafted copolymer is formed from the copolymerization of the randomly repeating hydrophobic monomer units, herein designated B and at least one polysiloxane macromer, a) wherein the structure vinyl polymer comprises from 60% to 90% by weight of the second copolymer grafted with silicone of copolymerizable hydrophobic monomers B, b) wherein the second copolymer grafted with silicone comprises from 10% to 40% by weight of the second copolymer grafted with silicone of polysiloxane macromers, ii) wherein the polysiloxane macromer has a weight average molecular weight of 5,000 and 50,000, iii) wherein the second silicone-grafted copolymer has a weight average molecular weight of 300,000 and 5,000,000, and iv) wherein the The first copolymer grafted with silicone is present in relation to the second copolymer grafted with silicone by weight in a proportion from 2: 1 to 26: 1; C) a neutralizing system, i) wherein the neutralizing system comprises at least one base selected from the group consisting of an organic base, an inorganic base and mixtures thereof, ii) wherein the neutralizing system is present at a sufficient level to neutralize from 30% to 95% of the acid groups on the first silicone-grafted copolymer; D) from 20% to 50% in. weight of the composition of a propellant; and E) the remainder comprises a carrier, i) wherein the carrier is suitable for solubilizing the first and second copolymers grafted with silicone, and ii) wherein the carrier is suitable for application to the hair.
2. 2. The composition according to claim 1, characterized in that it further comprises up to 2% by weight of a plasticizer, wherein the plasticizer is preferably selected from the group consisting of diisobutyl adipate, propylene glycol, dipropylene glycol and mixtures thereof.
3. 3. The composition according to any of the preceding claims, characterized in that it further comprises 0.01% to 5% of a conditioning agent, wherein the conditioning agent is preferably selected from the group consisting of phenyl trimethicone, decamethylcyclopentasi loxane, Panthenol and mixtures thereof. same.
4. 4. The composition according to any of the preceding claims, characterized in that: (a) the vinyl polymer structure of the first silicone-grafted copolymer comprises hydrophilic A monomers selected from the group consisting of acrylic acid, methacrylic acid and mixtures thereof; (b) the polymeric vinyl structure of the first silicone-grafted copolymer comprises hydrophobic B-monomers selected from the group consisting of n-butyl acrylate, isobutyl methacrylate; methacrylate of 2-ethylhexyl, methyl methacrylate, t-butyl acrylate, t-butyl methacrylate and mixtures thereof; and (c) the vinyl polymer structure of the second silicone-grafted copolymer comprises hydrophobic B-monomers selected from the group consisting of n-butyl ether, isobutyl methacrylate; methacrylate of 2-ethexyl, methyl methacrylate, t-butyl acrylate, t-butyl methacrylate and mixtures thereof.
5. 5. The composition according to any preceding claim, characterized in that the neutralizing system comprises bases selected from the group consisting of potassium hydroxide, sodium hydroxide, 2-amino-2-met i-1-propanol and mixtures thereof.
6. 6. The composition according to any preceding claim, characterized in that the propellant is selected from the group consisting of isobutane, n-butane, propane, dimethyl ether and mixtures thereof.
7. 7. The composition according to any preceding claim, characterized in that the carrier is selected from the group consisting of Ci-C6 alkanols, C7-C6 isoparaffins and mixtures thereof.
8. 8. The composition according to any preceding claim containing less than 3% water.
9. 9. The composition according to any preceding claim, characterized in that: (a) the first silicone-grafted copolymer is selected from the group consisting of: (i) t-butyl acrylate macromer / acrylic acid / pol idimet i Is i loxane - 10,000-weighted average molecular weight macromer (60/20/20); (ii) macromer of t-butyl c-acrylate / acrylic acid / poly idimet i 1 s i loxane - weighted average molecular weight macromer i0,000 (70/10/20); (iii) macromer of t-butyl methacrylate / acrylic acid / polydimethylsiloxane - macromer of weighted average molecular weight - 10,000 (65/15/20); (iv) macromer of t-butyl acrylate / acrylic acid / polydimethylsiloxane-macromer of average molecular weight 10,000 (75/15/10); (v) and mixtures thereof; and (b) the second polymeric silicone-grafted L.sub.o is selected from the prupo consisting of: (i) t-butyl acrylate / polydimethylsiloxane macromer macromer of 10,000 weighted average molecular weight (80/20); (ii) macromer of t-butyl acrylate / poly idimethe ils iloxane-macromer of weight average molecular weight 10,000 (75/25); (iii) macromer of t-butyl acrylate / pol idimet i 1 if loxane - weight average molecular weight macromer - 20,000 (80/20); (iv) macromer of t-butyl acrylate / polydimethylsiloxane-macromer of average molecular weight 10,000 (85/15); and mixtures thereof.
10. 10. A method to stylize the hair characterized in that it comp re not to apply an effective amount of ana c.t. osition according to any preceding claim.