SOLVENT

TECHNICAL FIELD The present invention relates to hair styling compositions containing both silicone and non-si cone organic polymers as a hair setting agents. More particularly, the present invention relates to hairs styling compositions containing these polymers which are solubilized in a hydrocarbon solvent.

BACKGROUND OF THE INVENTION The desire to have the hair retain a particular shape is widely held The most common methodology for accomplishing this is the application of a composition to dampened hair, after shampooing and/or conditioning, or to dry, styled hair These compositions provide temporary setting benefits and they can be removed by water or by shampooing The materials used in the compositions to provide the setting benefits have generally been resins and have been applied in the form of mousses, gels, lotions or sprays

Many people desire a high level of style retention, or hold, from a hair spray composition. In typical hair sprays, hold is achieved by the use of resins, such as AMPHOMER ^R , supplied by National Starch and Chemical Company, and GANTREZ ^R SP 225, supplied by GAF. In general, as hair hold for hair spray compositions is increased, the tactile feel of the hair becomes stiffer and hence, less desirable It is desirable to provide hair spray products which could provide an improved combination of hair hold and hair feel characteristics.

Hair sprays have been conventionally formulated with high amounts of monohydric alcohol solvents, such as ethanol and isopropanol, and relatively low amounts of water since the presence of water adversely affects spray quality However, it is now particularly desirable to formulate hair spray compositions with reduced levels of volatile organic compounds, such as ethanol, isopropanol, and other volatile matenals, such as aerosol propellants. One way to do this is to increase the levels of water in the formulations. In doing so, it would be highly desirable to provide reformulated products which overcome the problems conventionally associated with the addition of water to hair spray products. In particular, higher levels of water can negatively impact hair feel.

Recently, it has become known to utilize silicone grafted organic backbone polymers as hair setting agents in hairspray compositions and other hair styling compositions, e g hair tonics, lotions, rinses, mousses, etc Silicone grafted polymers can be used to make hair spray compositions which provide hair setting ability with improved hair feel, e g , increased softness relative to conventional polymeric hair setting agents

However, it remains desirable to improve the hair feel performance these silicone grafted polymers can provide at a particular level of hair hold, or conversely, to improve hair hold (after application and drying of such compositions) for a particular level of hair feel performance It is an object of this invention to provide hair spray compositions, and other aqueous, alcohol, or hydroalcoho c-based hair setting solutions containing both non-sihcone as well as silicone grafted organic backbone polymeric hair setting agents that provide such improved combinations of hair feel/hair hold performance It is a further object of this invention to provide hair setting compositions, as described above, that provide both improved hair feel and improved hair hold ability for a particular level of silicone grafted polymer in the composition

It is yet a further object of this invention to provide compositions that meet the above objects for conventional volatile organic solvent level (conventional VOC) compositions, which typically contain greater than 80% of volatile organic compounds, as well as for reduced volatile organic solvent level (reduced VOC) compositions, i e compositions having 80% or less volatile organic solvents

These and other benefits as may be apparent from the descπption below can be obtained by the present invenbon The present compositions can compπse, consist of, or consist essentially of any of the required or optional ingredients and/or limitations descnbed herein

All percentages and ratios are calculated on a weight basis unless otherwise indicated All percentages are calculated based upon the total composition unless otherwise indicated All ingredient levels are refer to the active level of that ingredient, and are exclusive of solvents, by-products, or other impurities that may be present in commercially available sources, unless otherwise indicated

SUMMARY OF THE INVENTION The present invention relates to hair styling compositions comprising

(a) from about 0 1% to about 15%, by weight, of an adhesive polymer having a weight average molecular weight of greater than about 20,000, said polymer being characterized by an organic polymeric backbone wherein said polymer is substantially free of silicone,

(b) from about 0 1% to about 15%, by weight, of a silicone grafted adhesive polymer, said polymer being characterized by an organic polymeric backbone, compatible with said adhesive polymer of (a) wherein said silicone grafted adhesive polymer has silicone macromers grafted to said backbone and wherein the number average molecular weight of said silicone macromers is greater than about 500,

(c) from about 0 1% to about 15%, by weight, of a hydrocarbon solvent selected from the group consisting of C10- 14 branched chain hydrocarbons, and mixtures thereof having a boiling point of from about

105°C to about 260°C,

(d) a polar solvent phase compnsing from about 80% to about 99%, by weight of the composition, of a polar solvent selected from the group consisting of water and C2-C3 monohydnc alcohols, and mixtures thereof, wherein said composition contains no more than about 15%, by weight, of C3 monohydric alcohol, wherein said organic polymer backbones of (a) and (b) are soluble in said polar solvent phase, and said silicone macromers of said hair setting polymer are soluble in said hydrocarbon solvent By "sutstanttally free" is meant that the polymer contains less than about 0 5%, preferably less than about 0 1%, more preferably less than about 0 05% silicone

In preferred embodiments, the compositions hereof additionally compπse a plasticizer for the silicone grafted hair setting polymer Especially preferred plasticizers include di-isobutyl adepate and acetyl U-1-C2-C8 alkyl citrates, particularly acetyl tπethyl citrate

DETAILED DESCRIPTION OF THE INVENTION The essential components of the present invention are descnbed below Also included is a nonexclusive descnption of various optional and preferred components useful in embodiments of the present inventon Adhesive Polvmer

The compositions of the present invention essentially comprise an adhesive polymer as a hair setting agent The compositions hereof will generally compπse from about 0 1% to about 15%, preferably from 0 5% to about 8%, more preferably from about

1% to about 8%, by weight of the composition, of the adhesive polymer It is not intended to exclude the use of higher or lower levels of the polymers, as long as an effective amount is used to provide adhesive or film-forming properties to the composition and the composition can be formulated and effectively applied for its intended purpose By adhesive polymer what is meant is that when applied as a solution to a surface and dried, the polymer forms a film Such a film will have adhesive and cohesive strength, as is understood by those skilled in the art

The adhesive polymer will preferably be a carbon chain derived from polymerization of ethylenically unsaturated monomers but can also be cellulosic chains or other carbohydrate-derived polymeric chains The backbone can also include ether groups, ester groups, amide groups urethanes and the like

The adhesive polymer should have a weight average molecular weight of at least about 20,000, preferably greater than about 25,000, more preferably greater than about 30,000, most preferably greater than about 35,000 There is no upper limit for molecular weight except that which limits applicability of the invention for practical reasons, such as processing, aesthetic characteristics, formulateability, etc In general, the weight average molecular weight will be less than about 10,000,000, more generally less than about 5,000,000, and typically less than about 2,000,000 Preferably, the weight average molecular weight will be between about 20,000 and about 2,000,000, more preferably between about 30,000 and about 1 ,000,000, and most preferably between about 40,000 and about 500,000

Preferably, the adhesive hereof when dπed to form a film have a Tg or Tm of at least about -20°C, more preferably at least about 20°C, so that they are not unduly sticky, or "tacky" to the touch As used herein, the abbreviation "Tg" refers to the glass transition temperature of the backbone of the polymer, and the abbreviation "Tm" refers to the crystalline melting point of the backbone, if such a transition exists for a given polymer Preferably, both the Tg and the Tm, if any, are above about -20°C, more preferably above about 20°C.

The adhesive polymer monomer units can be deπved from polar, or hydrophilic, monomers, "A" monomers, low polanty, or hydrophobic, "B" monomers, or mixtures of polar hydrophilic "A" monomers and low polanty, hydrophobic, "B" monomers

Hydrophobic monomers means monomers which form substantially water insoluble homopolymers Hydrophilic monomers means monomers which fonn homopolymers which are substantially water soluble Substantially water soluble shall refer to monomers that form homopolymers that are soluble in distilled (or equivalent) water, at 25°C, at a concentration of 0 2% by weight, and are preferably soluble at 1 0% by weight Substantially water insoluble shall refer to monomers that form homopolymers that are not soluble in distilled (or equivalent) water, at 25°C, at a concentration of 0 2%

by weight, and preferably not soluble at 0 1% by weight The weight average molecular weight for purposes of determining substantial water solubility or insolubility shall be about 40,000, although solubility at higher molecular weight shall also be indicative of solubility at about 40,000 The particular relative amounts of A and B monomers can vary as long as the polymer is soluble in the polar solvent hereof

Representative examples of A monomers include acrylic acid, methacrylic acid, N,N-dιmethylacrylamιde, dimethyl aminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate, methacrylamide, N-t-butyl acrylamide maleic acid, maleic anhydride and its half esters, crotonic acid itaconic acid, acrylamide, acrylate alcohols, hydroxyethyl methacrylate, diallyldimethyl ammonium chloride, vinyl pyrrolidone, vinyl ethers (such as methyl vinyl ether) maleimides, vinyl pyridine, vinyl imidazole, other polar vinyl heterocyclics, styrene sulfonate, allyl alcohol, vinyl alcohol (such as that produced by the hydrolysis of vinyl acetate after polymerization), salts of any acids and amines listed above, and mixtures thereof Preferred A monomers include acrylic acid, N,N-dιmethyl acrylamide, dimethylaminoethyl methacrylate, quaternized dimethyl aminoethyl methacrylate, vinyl pyrrolidone salts of acids and amines listed above, and mixtures thereof

Representative examples of B monomers are acrylic or methacrylic acid esters of Cι-C-18 alcohols, such as methanol, ethanol, methoxy ethanol, 1-propanol, 2- propanol, 1 -butanol, 2-methyl-1 -propanol, 1-pentanol 2-pentanol, 3-pentanol, 2-methyl- 1 -butanol, 1-methyl-1 -butanol, 3-methy 1-1 -butanol, 1-methyl-1-pentanol, 2-methyl-1- pentanol, 3-methyl-1-pentanol, t-butanol(2-methyl-2-propanol), cyclohexanol, neodecanol, 2-ethy 1-1 -butanol, 3-heptanol, benzyl alcohol, 2-octanol, 6-methyl-1- heptanol, 2-ethyl-1-hexanol, 3, 5-dιmethyl-1 -hexanol, 3,5,5-tπ methyl-1 -hexanol, 1- decanol, 1-dodecanol, 1-hexadecanol, 1-octa decanol, and the like, the alcohols having from about 1-18 carbon atoms with the number of carbon atoms preferably being from about 1-12, styrene, polystyrene macromer, vinyl acetate, vinyl chlonde, vinylidene chloπde, vinyl propionate, alpha-methylstyrene, t-butylstyrene, butadiene, cyclohexadiene, ethylene; propylene, vinyl toluene, and mixtures thereof Preferred B monomers include n-butyl methacrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, methyl methacrylate, and mixtures thereof Most preferably, B is selected from t-butyl acrylate, t-butyl methacrylate, and mixtures thereof The level of A monomer units can be from about 0% to about 100%, preferably from about 5% to about 80%, more preferably from about 10% to about 50%, most preferably from about 15% to about 40%, the level of B monomer units, can be from 0% to about

100%, preferably from about 20% to about 95%, more preferably from about 50% to about 90%, most preferably from about 60% to about 85%

The composition of any particular adhesive polymer will help determine its formulational properties By appropriate selection and combination of particular A and B components, the adhesive polymer can be optimized for inclusion in specific vehicles The adhesive polymer included in the compositions hereof must be soluble in the polar solvent This is determined according to whether the polymer can stay in solution or precipitates out of solution at 25°C at the concentration present in the composition It is well within the skill of one in the art to select monomers for incorporation into the polymers for formulateability and solubility in selected polar solvent systems

Exemplary adhesive polymers for use in the present invention include the following, where the numbers following the structure indicate the weight ratios of monomers as loaded into the polymerization reactor (i) acrylic acid/t-butyl acrylate 25/75 (n) dimethylaminoethyl methacrylate/isobutyl metfιacrylate/2-

-ethylhexyl-methacrylate 40/40/20 (in) t-butylacrylate/acrylic acid 65/35 (iv) polymer (n) quaternized by treatment with methyl choπde The adhesive polymers can be synthesized by free radical polymerization of the monomers The general principles of free radical polymerization methods are well understood See, for example, Odian, "Pπnciples of Polymerization", 3nd edition, John Wiley & Sons, 1991, pp 198-334 The desired monomers are all placed in a reactor, along with a sufficient amount of a mutual solvent so that when the reaction is complete the viscosity of the reaction is reasonable Typical monomer loadings are from about 20% to about 50% Undesired terminators, especially oxygen, are removed as needed This is done by evacuation or by purging with an inert gas, such as argon or nitrogen The initiator is introduced and the reaction brought to the temperature needed for initiation to occur, assuming thermal initiators are used Alternatively, redox or radiation initiation can be used The polymeπzation is allowed to proceed as long as needed for a high level of conversion to be achieved, typically from a few hours to a few days The solvent is then removed, usually by evaporation or by precipitating the polymer by addition of a nonsolvent The polymer can be further puπfied, as desired

As an alternative to a batch reaction, the adhesive polymer can be made by a semi-continuous or continuous process In the semi-continuous process, two or more additions of monomers are made duπng the polymeπzation reaction This is advantageous when the polymer is made of several monomers which react duπng the polymeπzation at different rates The proportions of monomers added to the reaction at the separate points of addition can be adjusted by one of ordinary skill in the art such

that the polymers of the final product have a more uniform structure In other words, the polymers of the final product will have a more consistent monomer content distribution for each of the monomer types charged to the reaction

As is known in the art, polymers which have acidic functionalities, such as carboxyl groups, are usually used in at least partially neutralized form to promote solubihty/dispersibility of the polymer In addition, use of the neutralized form aids in the ability of the hair care compositions to be removed from the hair by shampooing In general, it is preferred that from about 10% to 100%, more preferably from about 20% to about 90%, and most more preferably from about 40% to about 85%, of the acidic monomers of the polymer be neutralized

Any conventionally used base, organic or metallic, may be used for neutralization of the polymers Metallic bases are particularly useful in the present compositions Hydroxides, where the cation is an alkali metal or an alkaline earth metal are suitable neutralizers for use in the present hair spray compositions Preferred neutralizing agents for use in hair spray compositions of the present invention are potassium hydroxide and sodium hydroxide

Examples of other suitable neutralizing agents which may be included in the hair spray compositions of the present invention include amines, especially ammo alcohols such as 2-amιno-2-methyl-1,3-propanedιol (AMPD), 2-amιne-2-ethyl-1,3-propanedιol (AEPD), 2-amιno-2-methyl-1 -propanol (AMP), 2-amιno-1 -butanol (AB), monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), monoisopropanolamine (MIPA), dnsopropanol-amine (DIPA), tri-isopropanolamine (TIPA) and dimethyl steramine (DMS) Particularly useful neutralizing agents are mixtures of amines and metallic bases Polymers having basic functionalities, e g , ammo groups, are preferably at least partially neutralized with an acid, e g , hydrogen chlonde

Solubility of the adhesive polymer, as described above, should be determined after neutralization, if any, as well as after addition of other ingredients that may be included in the polar solvent phase, such as surfactants, solubilizers, etc Silicone Grafted Adhesive Polymer

In addition to the adhesive hair styling polymer the compositions according to the invention compnse, as a second essential component, a silicone-containing hair styling resin which is compatible with the adhesive polymer descπbed above This silicone containing hair styling resm is preferably colloidally dispersed or solubilized in the hair cosmetic earner along with the adhesive hair styling polymer Keeping the two hair styling agents dispersed and solubihsed in the hair spray solvent is believed to be important for providing the unique hair setting benefits in combination with excellent hair

feel characteristics which are delivered by compositions according to the present invention.

The compositions hereof will generally comprise from about 0.1 % to about 15%, preferably from 0.5% to about 8%, more preferably from about 1% to about 8%, by weight of the composition, of the silicone grafted polymer. It is not intended to exclude the use of higher or lower levels of the polymers, as long as an effective amount is used to provide adhesive or film-forming properties to the composition and the composition can be formulated and effectively applied for its intended purpose. By adhesive polymer what is meant is that when applied as a solution to a surface and dried, the polymer forms a film. Such a film will have adhesive and cohesive strength, as is understood by those skilled in the art.

The silicone grafted polymers are characterized by polysiloxane moieties covalently bonded to and pendant from a polymeric carbon-based backbone. The polymeric backbone is chosen such that it is compatible with the non-silicone adhesive styling polymer. By "compatible" is meant is that, when placed in a suitable solvent, the polymers form a stable solution, i. e., the polymers do not compete for solubility and therefore, cause no phase separation and when the solution is dried a uniform film is formed, with no macrophase separation of the two polymers. A suitable solvent is a solvent which substantially completely dissolves the non-silicone and silicone grafted polymers at the levels described herein. The polymer blend forms a relatively clear hairspray system (% transmittance at 450 nm is generally greater than 80%). It is recognized that certain plasticizers can form cloudy films as well as incorrect neutralization levels. Therefore, this would fall outside this definition of compatibility. The compatibility can be tested by dissolving the adhesive polymer and the silicone grafted hair styling resin in a mutual solvent, and then evaporating the solvent to form a film. Incompatible polymers will form a cloudy film with poor mechanical properties, due to the large scale phase separation of the two polymers. Alternatively, after drying the polymer solution to a film, compatibility can be evaluated by measuring the Tg. Compatible polymers will have a single Tg, while incompatible polymers will exhibit two Tg's. Although compatibility can occur between two polymers of completely different structures, it is preferred that compatibility be obtained by making the composition of the non-silicone backbone of the silicone grafted polymer similar to or identical to the composition of the adhesive polymer.

The backbone will preferably be a carbon chain derived from polymerization of ethylenically unsaturated monomers, but can also be cellulosic chains or other carbohydrate-derived polymeric chains to which polysiloxane moieties are pendant. The backbone can also include ether groups, ester groups, amide groups, urethane groups and the like. The polysiloxane moieties can be substituted on the polymer or can be

made by co-polymerization of polysiloxane-containing polymerizable monomers (e g ethylenically unsaturated monomers, ethers, and/or epoxides) with non-polysiloxane- containing polymerizable monomers

The polysiloxane-grafted polymer should have a weight average molecular weight of at least about 20,000 There is no upper limit for molecular weight except that which limits applicability of the invention for practical reasons, such as processing, aesthetic characteristics, formulateability, etc In general, the weight average molecular weight will be less than about 10,000,000, more generally less than about 5,000,000, and typically less than about 3,000,000 Preferably, the weight average molecular weight will be between about 50,000 and about 2,000,000, more preferably between about 75,000 and about 1 ,000,000, most preferably between about 100 000 and about 750,000

Preferably, the adhesive hereof when dried to form a film have a Tg or Tm of at least about -20°C, more preferably at least about 20°C so that they are not unduly sticky, or "tacky" to the touch As used herein, the abbreviation "Tg" refers to the glass transition temperature of the backbone of the polymer and the abbreviation "Tm" refers to the crystalline melting point of the backbone, if such a transition exists for a given polymer Preferably, both the Tg and the Tm, if any are above about -20°C, more preferably above about 20°C

The silicone grafted polymers for the compositions of the present invention comprise "silicone-containing" (or "polysiloxane-containing") monomers, which form the silicone macromer pendant from the backbone, and non-silicone-containing monomers, which form the organic backbone of the polymer

The silicone grafted polymers should satisfy the following three cπteπa

(1) when dried, either alone or in the presence of the adhesive polymer, the polymer phase-separates into a discontinuous phase which includes the polysiloxane portion and a continuous phase which includes the non- poly siloxane portion,

(2) the polysiloxane portion is covalently bonded to the non-polysiloxane portion, and (3) the molecular weight of the polysiloxane portion is at least about 500

When used in a composition, such as a personal care composition for application to the hair or skin, the non-polysiloxane portion should permit the polymer to deposit on the intended surface, such as hair or skin

Without being limited by theory, it is believed that the phase separation property provides a specific onentation of the polymer which results in the desired combination of tactile feel, and film-forming or adhesive benefits The phase-separating nature of the compositions of the present invention may be determined as follows

The polymer is cast as a solid film out of a solvent (i e , a solvent which dissolves both the backbone and the polysiloxane-graft portions) This film is then sectioned and examined by transmission electron microscopy Microphase separation is demonstrated by the observation of inclusions in the continuous phase These inclusions should have the proper size to match the size of the silicone chain (typically a few hundred nm or less) and the proper density to match the amount of silicone present This behavior is well documented in the literature for polymers with this structure (see, for example, S D Smith, Ph D Thesis, University of Virginia, 1987, and references cited therein, said thesis incorporated by reference herein) A second method for determining phase-separating characteristics involves examining the enrichment of the concentration of silicone at the surface of a polymer film relative to the concentration in the bulk polymer Since the silicone prefers the low energy air interface, it preferentially orients on the polymer surface This produces a surface with the silicone oriented at the surface of the film This can be demonstrated experimentally by ESCA (electron spectroscopy for chemical analysis) of the dried film surface Such an analysis shows a high level of silicone and a greatly reduced level of backbone polymer when the film surface is analyzed (Surface here means the first few tens of Angstroms of film thickness ) By varying the angle of the interrogating beam the surface can be analyzed to varying depths The preferred silicone grafted polymers comprise an organic backbone preferably a carbon backbone deπved from ethylenically unsaturated monomers, such as a vinyl polymeric backbone, and a polysiloxane macromer (especially prefeπed are polydialkylsiloxane, most preferably polydimethylsiloxane) grafted to the backbone The polysiloxane macromer should have a weight average molecular weight of at least about 500, preferably from about 1 ,000 to about 100,000, more preferably from about 2,000 to about 50,000, most preferably about 5,000 to about 20,000 Organic backbones contemplated include those that are deπved from polymerizable, ethylenically unsaturated monomers, including vinyl monomers, and other condensation monomers (e g , those that polymerize to form polyamides and polyesters), ring-opening monomers (e g , ethyl oxazoline and caprolactone), etc Also contemplated are backbones based on cellulosic chains, ether-containing backbones, etc

Preferably the weight ratio of the non-si cone polymer to silicone grafted polymer ranges from about 1 10 to about 1 1 , preferably from about 1 5 to about 1 1

Examples of useful polymers and how they are made are described in detail in U S Patent 4,693,935, Mazurek, issued September 15, 1987, U S Patent 4,728,571 , Clemens et al , issued March 1, 1988, both of which are incoφorated herein by reference

Suitable silicone grafted polymers are also disclosed in EPO Application 90307528 1 , published as EPO Application 0 408 311 A2 on January 11 1991, Hayama et al , U S Patent 5,061,481, issued October 29, 1991, Suzuki et al , U S Patent 5,106,609, Bolich et al , issued April 21 , 1992 U S Patent 5,100 658 Bolich et al issued March 31 , 1992, U S Patent 5,100,657, Ansher-Jackson, et al issued March 31 1992, U S Patent 5 104,646, Bolich et al , issued April 14, 1992 U S Serial No 07 758,319, Bolich et al, filed August 27, 1991 , and U S Serial No 07/758,320, Torgerson et al , filed August 27, 1991 , all of which are incorporated by reference herein The preferred silicone grafted polymers are comprised of monomer units derived from at least one free radically polymerizable ethylenically unsaturated monomer or monomers and at least one free radically polymerizable polysiloxane-containing ethylenically unsaturated monomer or monomers

The silicone grafted polymers hereof generally compπse from about 1% to about 50%, by weight, of polysiloxane-containing monomer units, i e , monomer units polysiloxane-containing monomers (referred to herein as "C" monomers), and from about 50% to about 99% by weight, of non-polysiloxane-containing monomers

The non-polysiloxane-containing monomer units can be derived from polar, or hydrophilic, monomers, "A" monomers, or mixtures of polar hydrophilic monomers, low polanty, or hydrophobic, "B" monomers or mixtures of the two The definitions of the "A" and "B" monomers, and representative examples of the "A" and "B" monomers, are the same as those use for the "A" and "B" monomers in the adhesive polymer

The particular relative amounts of A, B, and C monomers can vary as long as the polymer backbone is soluble in the polar solvent hereof, the polymer backbone is compatible with the adhesive polymer, and the silicone grafted copolymer exhibits phase separation when dned

Polymerizable polysiloxane-containing monomers (C monomer) are exemplified by the general formula

X(Y)nS«R)3-mZm wherein X is an ethylenically unsaturated group copolymerizable with the A and B monomers, such as a vinyl group, Y is a divalent linking group, R is a hydrogen, hydroxyl, lower alkyl (e g C1-C4), aryl, alkaryl, alkoxy, or alkylamino, Z is a monovalent siloxane polymeπc moiety having a number average molecular weight of at least about 500, is essentially unreactive under copolymenzation conditions, and is pendant from the vinyl polymeπc backbone descπbed above, n is 0 or 1 , and m is an integer from 1 to 3 C has a weight average molecular weight as descπbed above Preferably, the C monomer has a formula selected from the following group

II

X-C-0-(CH ₂ ) _q -(0)p-Si(Rl ) ₃ _ _m Z _m

In this structure, m is 1 , 2 or 3 (preferably m = 1 ), p is 0 or 1; q is an integer from 2 to 6; R ¹ is hydrogen, hydroxyl, lower alkyl, alkoxy, alkylamino, aryl, or alkaryl (preferably R is alkyl); X is

CH=C-

I I R2 R3

R ² is hydrogen or -COOH (preferably R ² is hydrogen), R ³ is hydrogen, methyl or - CH ₂ COOH (preferably R ³ is methyl); Z is R5

I R ⁴ -(-Sι-0-)r;

I

R6 R ⁴ , R ⁵ , and R*> independently are lower alkyl, alkoxy, alkylamino, aryl, arkaryl, hydrogen or hydroxyl (preferably R ⁴ , R ⁵ , and R^ are alkyls); and r is an integer of about 5 or higher, preferably about 10 to about 1500 (most preferably r is from about 100 to about 250). Most preferably, R ⁴ , R ⁵ , and R ⁶ are methyl, p=0, and q=3. Also preferred, the C monomer has the formula selected from the group:

or

X-CH ₂ — (CH ₂ )s-Si(Ri) ₃ -m-Zm wherein: s is an integer from 0 to about 6, preferably 0, 1 , or 2, more preferably 0 or 1 ; m is an integer from 1 to 3, preferably 1; R ² is C1-C10 alkyl or C7-C10 alkylaryl, preferably C1-C6 alkyl or C7-C10 alkylaryl, more preferably C1-C2 alkyl; n is an integer from 0 to 4, preferably 0 or 1 , more preferably 0.

In general, the silicone grafted polymer will preferably comprise from about 50% to about 99%, more preferably from about 60% to about 98%, most preferably from about 75% to about 95%, by weight of the polymer, of non-silicone macromer-containing monomer units, e.g. the total A and B monomer units, and from about 1% to about 50%,

preferably from about 2% to about 40%, more preferably from about 5% to about 25% of silicone macromer-containing monomer units, e g the C monomer units The level of A monomer units can be from about 0% to about 99%, preferably from about 5% to about 80%, more preferably from about 10% to about 50%, most preferably from about 15% to about 40%, the level of B monomer units, can be from 0% to about 99%, preferably from about 1% to about 90%, more preferably from about 5% to about 85%, most preferably from about 15% to about 80%, and the level of C monomer units, from about 1% to about 50%, preferably from about 2% to about 40%, more preferably from about 5% to about 25% The combination of the A and B monomers preferably comprises from about

50 0% to about 99 9% (more preferably about 60% to about 99% most preferably from about 75% to about 95%) of the polymer The composition of any particular copolymer will help determine its formulational properties In fact by appropriate selection and combination of particular A, B and C components, the copolymer can be optimized for inclusion in specific vehicles For example, polymers which are soluble in an aqueous formulation preferably have the composition from about 0% to about 70% (preferably from about 5% to about 70%) monomer A, from about 30% to about 98% (preferably from about 30% to about 80%) monomer B, and from about 1% to about 40% monomer C Polymers which are dispersible have the preferred composition from about 0% to about 70% (more preferably from about 5% to about 70%) monomer A, from about 20% to about 80% (more preferably from about 20% to about 60%) monomer B, and from about 1 % to about 40% monomer C

The composition of any particular silicone grafted polymer will help determine its formulational properties By appropnate selection and combination of particular A, B and C components, the silicone grafted polymer can be optimized for inclusion in specific vehicles The backbone of the silicone grafted polymer included in the compositions hereof must be soluble in the polar solvent, which is hereinafter referred to as the silicone grafted polymer, as a whole, being soluble in the polar solvent This is determined according to whether the polymer can stay in solution or precipitates out of solution at 25° C at the concentration present in the composition or whether the range of concentrations for silicone grafted polymer discπbed herein. It is well within the skill of one in the art to select monomers for incoφoration into the polymers for formulateability and solubility in selected polar solvent systems.

Exemplary silicone grafted polymers for use in the present invention include the following, where the composition is given as weight part of monomer used in the synthesis

(i) acrylic acid/n-butylmethacrylate/polydimethylsiloxane (PDMS) macromer

20,000 molecular weight macromer 20/70/10

(n) dimethylaminoethyl methacrylate/isobutyl methacrylate/2-

-ethylhexyl-methacrylate/PDMS macromer-20,000 molecular weight macromer 40/30/15/15 (in) t-butylacrylate/acryiic acid/PDMS macromer-10,000 molecular weight macromer 63 5/20/16 5

(iv) t-butylacrylate/acrylic acid/PDMS macromer-20,000 molecular weight macromer 60/20/20 The silicone grafted polymers can be synthesized by free radical polymerization of the polysiloxane-containing monomers with the non-polysiloxane-containing monomers The synthetic procedures are in general the same as those described for the adhesive copolymer The silicone macromer is added in to the reactor along with the "A" and "B" monomers, and the reaction proceeds as for the adhesive copolymer examples Compared to the adhesive copoymer, it may be necessary to choose different solvents for the polymenzation reaction, as apparent to one skilled in the art, to keep the monomers and polymers in solution thrroughout the polymerization

Without being limited by theory, it is believed that in forming the above-described silicone grafted polymers, there is some polymer which does not encorporate the silicone graft, such polymers have a relatively low weight average molecular weight e g , below 20,000 Polar Solvent Phase

The liquid care compositions of the present invention also include a polar solvent phase as a liquid vehicle for the silicone grafted polymer The polar solvent phases compπse one or more polar solvents that are present in the hair care compositions at a level of from about 80% to about 99%, preferably from about 85% to about 98%, more preferably from about 90% to about 95% of the total composition

The polar solvents essential to the present compositions are selected from the group consisting of water, C2-C3 monohydric alkanols, and mixtures thereof If present, C3 alkanols, such as isopropanol, should be used at levels no greater than about 15% by weight of the composition, preferably no greater than about 12%, more preferably no greater than about 10% High levels of C3 monohydπc alcohols are undesirable in the present compositions due to potential odor issues they can create Preferred polar solvent phases contain water, ethanol, or mixtures thereof Preferably the organic polymer backbones of the adhesive polymer and the silicone grafted polymer are insoluble in said polar solvent Where water and alcohol mixtures are used, for instance, water-ethanol or water-isopropanol-ethanol, the water content of the compositions is generally in the range of from about 0 5% to about 99%, preferably from about 5% to about 50% by weight of the total composition In such mixtures, the alcohol solvents are generally

present in the range of from 0 5% to about 99%, preferably from about 50% to about 95%, by weight of the total composition

In yet another aspect of this invention are provided hair styling products, such as hair spray compositions, which contain reduced levels of volatile organic solvents A reduced volatile organic solvent hair spray composition of the present invention contains no more than 80% volatile organic solvents (which include, for example, alkanols but not water) As used herein, volatile organic solvents means solvents which have at least one carbon atom and exhibit a vapor pressure of greater than 0 1 mm Hg at 20°C

In the reduced volatile organic solvent hair styling products hereof, the compositions generally comprise at least 10%, by weight, of water It is also specifically contemplated that they may contain at least about 11%, 12%, 13%, 14%, 15%, or more water

The reduced volatile organic solvent compositions hereof will comprise up to about 90%, preferably up to about 70%, more preferably up to about 60% even more preferably no more than about 50%, water, and from about 10% to about 80%, preferably from about 20% to about 80%, more preferably from about 40% to about 80%, of volatile organic solvent It is also contemplated that the compositions can be limited to containing no more than about 75%, 65%, 55%, or other levels of volatile organic solvents Nonpolar, Branched Chain Hydrocarbon

The compositions hereof contain as an essential element a volatile, nonpolar, branched chain hydrocarbon, which acts as a solvent for the silicone portion of the silicone grafted copolymer and is safe for topical application to the skin and hair The branched chain hydrocarbon solvent hereof is present at a level of from about 0 1 % to about 15%, preferably from about 0.5% to about 10%, more preferably from about 2% to about 8%, by weight of the composition

The branched chain hydrocarbon solvent is charactenzed by a boiling point of at least about 105°C, preferably at least about 110°C, more preferably at least about 125°

C, most preferably at least about 150°C The boiling point is also generally about 260°C or less, preferably about 200°C or less The hydrocarbon chosen should also be safe for topical application to the hair and skin

The branched chain hydrocarbon solvents are selected from the group consisting of C^Q-C^ branched chain hydrocarbons, and mixtures thereof, preferably

C11-C13 branched chain hydrocarbons, more preferably C12 branched chain hydrocarbons Saturated hydrocarbons are preferred, although it isn't necessarily intended to exclude unsaturated hydrocarbons.

Examples of suitable nonpolar solvents include isoparaffins of the above chain sizes. Isoparaffins are commercially available from Exxon Chemical Co Examples

include Isopar™ G (C-I Q- H isoparaffins), Isopar™ H and K (C11-C12 isoparaffins) and Isopar™ L (C^ -j-C^ isoparaffins) The most preferred nonpolar solvent are C-J2 branched chain hydrocarbons, especially isododecane Isododecane is commercially available from Preperse, Inc (South Plainfield NJ USA) as Permethyl™ 99A The silicone macromer portion of the silicone grafted polymer is soluble in the nonpolar hydrocarbon solvent in the present compositions This can be easily determined by verifying whether a silicone macromer of the same composition and molecular weight as that grafted to the silicone grafted polymer is soluble in the nonpolar hydrcarbon solvent In general, the macromer should be soluble at 25°C at a concentration of 0 1% by weight of the hydrocarbon solvent preferably at 1 % more preferably at 5%, most preferably at 15%

The nonpolar hydrocarbon solvent, however is insoluble in the polar solvent of the composition This is determined in the absence of the silicone grafted polymer or other emulsifying agents and can easily be verified by observing whether the polar and nonpolar solvents form separate phases after being mixed together

Without intending to be necessarily limited by any particular theory, it is believed that the nonpolar hydrocarbon solvent solubilizes the silicone macromer portion of the silicone grafted polymer This is believed to aid in obtaining a smoother polymer film upon drying Since the hydrocarbon solvent is less volatile than the polar solvent phase, the hydrocarbon solvent maintains the silicone portions in solubilized form for a relatively long period as the composition dries, thus minimizing aggregation of the silicone portions and, therefore, allowing the polymer to dry as a smoother film Plasticizer

The compositions hereof can optionally contain a plasticizer for the silicone grafted polymer Any plasticizer suitable for use in hair care products or for topical application to the hair or skin can be used A wide vaπety of plasticizers are known in the art These include acetyl tnethylcitrate, tnethycitrate, glycerin, dnsobutyl adipate, butyl stearate, and propylene glycol Plasticizers are typically used at levels of from about 0 01% to about 10%, by weight of the composition, preferably from about 0 05% to about 3%, more preferably from about 005% to about 1 %

Optional Ingredients The present compositions can contain a wide variety of optional ingredients, including among them any of the types of ingredients known in the art for use in hair setting compositions, especially hair spray compositions and hair setting tonics These ingredients include, but are not limited to, surfactants (including fluorinated surfactants and silicone copolyols), and ionic strength modifiers, propellants, hair conditioning agents (e g , silicone fluids, fatty esters, fatty alcohols, long chain hydrocarbons, cationic surfactants, etc )

Ionic Strength Modifier Svstem

Optionally, the compositions of the present invention can contain an effective amount of a non-surface active ionic strength modifier system for reducing the viscosity of the hair spray composition. When used, the ionic strength modifiers will be present in the present compositions at a level of at least about 0.01 %, by weight of the composition. The upper limit is dependent upon the maximum amount of the ionic strength modifiers that can be present in the particular compositions hereof such that the hair setting resin remains solubilized or dispersed. As will be understood by those skilled in the art, as the ionic strength of the composition is increased, the resin will eventually fall out of solution, or otherwise no longer remain solubilized or dispersed in the polar liquid carrier. The upper limit of the ionic strength modifier system level will vary depending upon the particular ionic strength modifiers, liquid vehicle, resin, and other ingredients present in the composition. Thus, for example, the maximum amount of the ionic strength modifiers that can be used will tend to be lower for compositions with liquid vehicles containing less water, compared to compositions with more water Generally, the compositions will comprise about 4%, by weight, or less of the ionic strength modifiers, more generally about 2% or less, and typically about 1 % or less. Preferably, the compositions hereof will comprise from about 0.01% to about 0.5%, more preferably from about 0.01% to about 0.1%, of the ionic strength modifier system. The ionic strength modifier system comprises a mixture of monomeric cations and anions. The ions of the ionic strength modifier system hereof are non-surface active, i.e. they do not significantly reduce surface tension. For purposes hereof, non-surface active shall mean the ions, which at a 0.5% aqueous solution concentration, reduce surface tension by no more than 5.0 dynes/cm2. Generally, the ions of the ionic strength modifier system hereof will be characterized by having, at maximum, four or less carbon atoms per charge, preferably two or less carbon atoms, in any aliphatic chain or straight or branched chain organic heterochain.

The ionic strength modifier system comprises monomeric ions of the type which are products of acid-base reactions. Thus, basic and acidic ions OH ^' and H do not constitute part of the ionic strength modifier system hereof, although they may be present in the composition. The ions hereof are incoφorated into the composition in a form such that they can exist in the composition as free ions, i.e., in dissociated form. It is not necessary that all of the ions added exist in the composition as free ions, but must be at least partially soluble or dissociated in the composition. The ionic strength modifiers can be incorporated into the hair styling compositions, for example, by addition of soluble salts, or by addition of mixtures of acids and bases, or by a combination thereof. It is a necessary aspect of the invention that both anions and cations of the ionic strength modifier system be included in the composition.

Suitable cations for use include, for example, alkali metals such as lithium sodium, and potassium, and alkaline-earth metals, such as magnesium, calcium, and strontium Preferred of the divalent cations is magnesium Preferred monovalent metal ions are lithium, sodium, and potassium, particularly sodium and potassium Suitable means of addition to the compositions hereof include for example, addition as bases, e g , hydroxides, sodium hydroxide and potassium hydroxide, and such as salts that are soluble in the liquid carrier, e g salts of monomeric anions such as those described below

Other suitable cations include organic ions, such as quaternary ammonium ions and cationic amines, such as ammonium mono- di- and tn-ethanolamines triethylamine morpholine, aminomethylpropanol (AMP) aminoethylpropanediol, etc

Ammonium and the amines are preferably provided in the forms of salts, such as hydrochloride salts

Monomeric anions that can be used include halogen ions, such as chloride, fiuonde, bromide, and iodide, particularly chloride, sulfate ethyl sulfate, methyl sulfate, cyclohexyl sulfamate, thiosulfate, toluene sulfonate, xylene sulfonate citrate, nitrate, bicarbonate, adipate, succinate, sacchaπnate, benzoate, lactate, borate, isethionate, tartrate, and other monomeπc anions that can exist in dissociated form in the hair styling composition The anions can be added to the compositions hereof, for example, in the form of acids or salts which are at least partially soluble in the liquid vehicle, e g , sodium or potassium salts of acetate, citrate, nitrate, chloπde sulfate, etc Preferably, such salts are entirely soluble in the vehicle

The use of ionic strength modifiers are especially useful in reduced volatile organic solvent compositions, most especially those utilizing silicone macromer-containing polymers

Hair Styling Compositions The present invention encompasses a wide variety of hair styling compositions, including hair spray compositions, mousses, and hair setting tonics In general, the compositions will be flowable, low viscosity compositions that, preferably, are suitable for spray application Higher viscosity compositions are also contemplated, however

Hair spray compositions and mousses of the present invention can be dispensed from containers which are aerosol dispensers or pump spray dispensers Such dispensers, i e , containers, are well known to those skilled in the art and are commercially available from a vaπety of manufacturers, including American National Can Coφ and Continental Can Corp

When the hair spray compositions are to be dispensed from a pressurized aerosol container, a propellant which consists of one or more of the conventionally-known aerosol propellants may be used to propel the compositions A

suitable propellant for use can be generally any liquifiable gas conventionally used for aerosol containers

Suitable propellants for use are volatile hydrocarbon propellants which can include liquified lower hydrocarbons of 3 to 4 carbon atoms such as propane, butane and isobutane Other suitable propellants are hydrofluorocarbons such as 1 ,2-dιfluoroethane (Hydrofluorocarbon 152A) supplied as Dymel 152A by DuPont Other examples of propellants are dimethylether, N-butane, isobutane, propanes nitrogen, carbon dioxide, nitrous oxide and atmospheric gas and mixtures thereof

The aerosol propellant may be mixed with the present compositions and the amount of propellant to be mixed is governed by normal factors well known in the aerosol art Generally, for liquifiable propellants, the level of propellant is from about 10% to about 60% by weight of the total composition, preferably from about 15% to about 40% by weight of the total composition

Alternatively, pressuπzed aerosol dispensers can be used where the propellant is separated from contact with the hair spray composition such as a two compartment can of the type sold under the tradename SEPRO from American National Can Coφ

Other suitable aerosol dispensers are those charactenzed by the propellant being compressed air which can be filled into the dispenser by means of a pump or equivalent device prior to use Such dispensers are descnbed in U S Patents 4,077,441, March 7, 1978, Olofsson and 4,850,577, July 25, 1989, TerStege, both incorporated by reference herein, and in U S Seπal No 07/839,648, Gosselin et al , filed February 21 , 1992, also incoφorated by reference herein Compressed air aerosol containers suitable for use are also currently marketed by The Procter & Gamble Company under their tradename VIDAL SASSOON AIRSPRAY® hair sprays Conventional non-aerosol pump spray dispensers, i e , atomizers, can also be used

Other hair styling compositions include tonics and lotions, which are typically dispensed in a conventional bottle or tube, and applied directly to the hair or first dispensed to the hand and then to the hair The hair styling formulations of the present invention can optionally contain conventional hair care composition adjuvants Generally, adjuvants collectively can compπse from about 0 05% to about 5% by weight and preferably from about 0 1% to about 3%, by weight Such conventional optional adjuvants are well known to those skilled in the art and include in addition to those discussed above, emollients, lubπcants and penetrants such as vaπous lanolin compounds, protein hydrolysates and other protein denvatjves, ethylene adducts and polyoxyethylene cholesterol, dyes, tints, bleaches, reducing agents and other colorants, pH adjusting agents sunscreens,

preservatives, thickening agents (e g polymeπc thickeners, such as xanthan gum), and perfume

METHOD OF MAKING

The hair styling compositions of the present invention can be made using conventional formulation and mixing techniques It is critical to have the silicone grafted polymer completely dissolved in the ethanol as the first making step Completely dissolved means no visible solids, solution is crystal clear This can be done as a premix with ethanol so long as the polymer concentration in the premix does not exceed 15%

Alternatively, the polymer can simply be dissolved in the entire ethanol amount required for the batch If ethanol is not to be used in the composition, a premix of the polymer with C3 alkanol is prepared Premixes with water are not feasible The other ingredients can then be added with mixing to provide a homogeneous mixture The neutra zer is preferably added to the premix pπor to addition of other ingredients A preferred order of addition is Isododecane Isododecane is added prior to the addition of water, this is especially important for water levels above 15%

METHOD OF USE

The compositions of the present invention are used in conventional ways to provide the hair styling/holding benefits of the present invention Such method generally involves application of an effective amount of the product to dry, slightly damp, or wet hair before and/or after the hair is arranged to a desired style The composition is then dned or allowed to dry By "effective amount" is meant an amount sufficient to provide the hair hold and style benefits desired considering the length and texture of the hair In general, from about 0 5g to about 50g of product will be applied to the hair, depending upon the particular product formulation, dispenser type, length of hair, and type of hair style

The following Expeπmentals and Examples further illustrate embodiments within the scope of the present invention They are given solely for the purposes of illustration and are not to be construed as limitations of the present invention as many vanations of the invention are possible without departing from its sp t and scope EXPERIMENTALS

The following synthesis exemplify silicone grafted polymers useful in the present compositions

Experimental 1 Batch synthesis Place 20 parts acrylic acid, 60 parts t-butyl acrylate, and 20 parts polysiloxane (10,000 MW) -containing monomer in a flask Add sufficient ethyl acetate or acetone as the reaction solvent to produce a final monomer concentration of 20% Purge the vessel with an inert atmosphere, preferably nitrogen or argon Add initiator, (2,2'-azobιs-(2,4- dimethylvaleronitrile)) to a level appropriate for the desires molecular weight Typically

this is in the range of 0 5% to 1 0% by weight relative to the amount of monomer Purge the vessel with an inert atmosphere, preferably nitrogen or argon Heat to 60°C and maintain this temperature for 8 hours while agitating Terminate the reaction by cooling to room temperature The polymer is purified by drying off the reaction solvent in an oven, or if acetone is used as the solvent precipitating the polymer, by adding water and then drying the precipitate

Experimental 2. Semi-continuous synthesis Place 20 parts acrylic acid, 60 parts t-butyl acrylate, and 30 parts polysiloxane (10,000 MW) -containing monomer in a flask Add sufficient ethyl acetate or acetone as the reaction solvent to produce a final monomer concentration of 25% Purge the vessel with an inert atmosphere, e g. nitrogen or argon Add initiator, (2,2'-azobιs-(2,4- dimethylvaleronitπle)) as in Experimental 1. Heat to 60°C and maintain this temperature After polymerization of these monomers has proceeded about 15 minutes to about 1 hour, e g about 30 minutes, add a second monomer charge of 20 parts acrylic acid and 60 parts t-butyl acrylate, to give a final total monomer charge of approximately 40% by weight Maintain at temperature for 8 hours. Terminate the reaction and purify the polymer as in Experimental 1.

EXAMPLES Examples 1-8 The following examples represent nonaerosol hairspray compositions of the present invention.

Example No

Component (wt. %) 1 2 3 4

Non-Silicone Polymer ¹ 1.00 1.25 1.50 1.00

Silicone Grafted Polymer ² 3.00 3.75 4 50 4.50

Isododecane ³ 1.00 1.00 1 00 3.00

Diisopropyl butyl adipate 0.40 0.75 0.90 0.55

Sodium hydroxide ⁴ 0.96 1.20 1 44 1.6

Potassium hydroxide ⁵ - - - -

Perfume 0.10 0.10 0.10 0.10

Water 17.00 20.00 20.00 18.00

Sodium Benzoate - - - -

Ethanol ⁶ 76.54 71.95 70.56 71.25

Example No

Component (wt. %) 5 6 7 8

Non-Silicone Polymer ¹ 3.50 1.70 4.50 2.0

Silicone Grafted Polymer ² 2.50 4.80 0.50 2.0

Isododecane ³ 0.50 1.0 2.00 0.02

Diisopropyl butyl adipate 1 52 1 30 0 75 0 40

Sodium hydroxide ⁴ - 1 69 - 1 11

Potassium hydroxide ⁵ 1 35 - 0 44 -

Perfume 0 10 0 15 0 10 0 15

Water 11 05 20 00 13 71 39 24

Sodium Benzoate - 0 10 - 0 10

Ethanol ⁶ 79 5 69 26 78 00 54 98

1 75% t-butyl acrylate/25% acrylic acid, having a weight average molecular weight of about 80,000 60% t-butyl acrylate/20% acrylic acιd/20% silicone macromer (weight average molecular weight of silicone macromer of about 10 000) having a weight average molecular weight of about 130,000

³ PERMETHYL 99A, from Presperse Inc , South Plainfield NJ USA

4 Sodium hydroxide is 30% active

5 Potassium hydroxide is 45% active ⁶ SDA 40 ( 100% ethanol)

Examples 9-14 The following examples represent aerosol hairspray compositions of the present invention

Example No

Component (wt %) 9 1 100 11

Non-Silicone Polymer ¹ 1 25 1 1 1133 1 0

Silicone Grafted Polymer ² 3 75 3 3 3388 2 50

Isododecane ³ 0 50 0 0 5500 2 00

Triethyl citrate ⁴ - - 0 21

Diisopropyl butyl adipate 0 50 0 45

Propylene glycol - - 0 02

Sodium hydroxide ⁵ 1 11 0 94

Potassium hydroxide ⁶ - - - - 0 33

Perfume 0 0 1100 0 0 1100 0 10

Water 1 1660000 1 166 0000 7 00

Sodium Benzoate 0 0 1100 0 0 1100 -

Ethanol ⁷ 5 5666699 5 5774422 62 85

Propellant - Isobutane - - - - 702

Propellant - n-butane 1 100 0000 1 100 0000 -

Propellant - Dimethyl ether ⁸ 1 100 0000 1 100 0000 —

Propellant - Hydrofluorocarbon 152a ⁹ — - 15 98

Example No

Component (wt %) 12 13 14

Non-Silicone Polymer ¹ 3 75 2 62 1 00

Silicone Grafted Polymer ² 1 25 0 88 2 50

Isododecane ³ 1 00 0 25 0 50

Triethyl citrate ⁴ - - -

Diisopropyl butyl adipate 0 75 0 53 0 35

Propylene glycol - - -

Sodium hydroxide ⁵ - 0 78 —

Potassium hydroxide ⁶ 1 04 - 0 73

Perfume 0 10 0 10 0 10

Water 15 00 39 94 8 00

Sodium Benzoate 0 10 0 20 —

Ethanol ⁷ 52 99 29 75 54 5

Propellant - Isobutane 15 00 10 00 -

Propellant - n-butane - - -

Propellant - Dimethyl ether ⁸ 15 00 15 00 -

Propellant - Hydrofluorocarbon 152a ⁹ — — 32 3i

1 75% t-butyl acrylate/25% acrylic acid, having a weight average molecular weight of about 80,000

² 60% t-butyl acrylate/20% acrylic acιd/20% silicone macromer (weight average molecular weight of silicone macromer of about 10,000), having a weight average molecular weight of about 150,000

³ PERMETHYL 99A, from Presperse, Inc , South Plainfield, NJ, USA ⁴ CITROFLEX-2, from Morfiex, Inc , Greensboro, NC, USA

5 Sodium hydroxide is 30% active

6 Potassium hydroxide is 45% active

⁷ SDA 40 (100% ethanol)

⁸ DYMEL - A, from Dupont ⁹ DYMEL-152a, from Dupont

In Examples 1-10, the compositions are prepared as descπbed above, by first mixing the polymer with the ethanol, neutralizing the polymer with sodium or potassium hydroxide, then adding sequentially (as applicable) with mixing, isododecane, plasticizer, perfume, and water If sodium benzoate is used, it is added after water addition Most preferably a premix of water and sodium benzoate is made and then added after the

mam water addition. Propellants for aerosol compositions are charged to conventional aerosol containers after the remainder of the prepared composition has been added