CA2115154A1

CA2115154A1 - Hair spray compositions with ionic styling polymer

Info

Publication number: CA2115154A1
Application number: CA002115154A
Authority: CA
Inventors: Marjorie M. Peffly; Nelson J. Holzschuh; Peter M. Torgerson
Original assignee: Individual
Current assignee: Procter and Gamble Co
Priority date: 1991-08-19
Filing date: 1992-08-18
Publication date: 1993-03-04
Also published as: JPH06509807A; SK19294A3; CZ35294A3; WO1993003704A1; CN1071331A; MA22628A1; AU2502892A; HUT67488A; EP0600008A1; PT100791A; FI940771A7; NZ243996A; FI940771A0; FI940771L; BR9206388A; HU9400475D0; MX9204802A

Abstract

2115154 9303704 PCTABS00020 Liquid hair styling composition useful for spray application to hair which comprises: (a) an ionic hair styling polymer having a weight average molecular weight of at least about 300,000; (b) a liquid vehicle selected from the group consisting of water, C1-C6 monohydric alcohols, and mixtures thereof; (c) an effective amount of an ionic strength modifier system for reducing viscosity of the composition, said system consisting essentially of a mixture of non-surface active cations and anions, wherein said cations and anions are at least partially soluble in said liquid carrier; said composition having a pH of about 10 or less. In yet another aspect of this invention, provided are reduced volatile organic solvent hair spray compositions having improved hair feel comprising silicone-containing hair setting polymer, an effective amount of an ionic strength modifier system for reducing viscosity of the compositions, as described above, and a liquid vehicle which comprises a mixture of water with one or more C1-C6 monohydric alcohols, wherein said composition comprises at least about 10 %, by weight, water.

Description

W~ 93/~370~ PCI~/US9~/06975 211515~
. 1 -HAIR SPRAY CoMPOSITIONS WITH ION~C STYLING POLYMER

7ECHN~CAL FiELD
The present invention relates to hair spray compositions which comprise a high molecular weight hair stylin~ polymer. More particularly, this invention relates to hair spray compss~tions containing high molecular wei~ht hair styling polymer and having improved sprayability.
BACKGROUND OF THE INYENTION
~he desire to have the hair retain a particu1ar shape is widely held. A common methodolo~y for accomplijhin~ this is applying hair styling, or hair "sett~ng" compositions to the hair, typically to damp or dry hair. These compositions proYide tem-porary setting benefits, and should be removable by water and/or by shampooing. The materials used in the compositions to provide the setting benefits are senerally applied in the form of mouss~s, gels, lotions sr sprays.
High levels o~ style retention, or hold, are typically ` expected from hair sty~ing compositions applied as a spray. Style retentlon is :typically achieved by the use o~ rasi~s, such as AMPHOMER, supplied by National Starch, and GAN7REZ SP 22S, sup-plied by GAF. As used in commerc:ially sold hair spray prsducts, these resins generally have a weight a~erage molecular weight of from about 40,000 to about ~150,000. ~hen such resins are incQr-porated into pump and aerosol hair sprays, they can provide a combination of suitable style ~etention and good sprayability.
"Sprayability" refers to the spray quality and pattern. Good : sprayability for hair spray formulations is characterized by a wide spray pattern without:~a wet, drippy center, and by suf-~iciently small droplet sizc to provide a fine mist.

:

WO 93/037~4 P~/US92/06975 211~15~

- 2 -It remains desirable, however, to provide hair spray com-positions that have improved hold and style retention performance.
One technique for providing i~proved style retent1On for liquid hair spray compositions wauld be to utilize higher mo1ec~1ar weight hair styling resin. Alternately, this could reduce the amount of resin needed to provide a particular level of style retention High molecular weight hair styl~n~ polymers, when utillzed commercially, have typically been formulated as gels, lot1Ons, ur other non-spray compositions. Unfortunately, high 1~ molecular weight resins in liquid hair spray formulations tend ko su~fer from poor sprayability. More specifically, such formulations tend to have spray quality characterized by reduced spray pattern diameter, increased incidence of wet, drippy centers, and a tendency toward larger droplet size or streaming upon spraying, as opposed to a fine mist. This can result in overly heavy concentrations of hair spray in regions of the hair, causing the hair to be too stiff in those re~ons, whereas other areas may have too little hair spray applied and, c~nsequently, ha~e poor style retention and hold.
Thus, it is an object of this invention to provide liquid hair spray compositions utilizing high molecular weight styling resins that can provide improved style retention and retain good sprayability characteristics.
Recently, it has been found that certain polymers having ~5 silicone macromer portions can provide good style retention bene~its to the hair while also providing improved hair feel. In other words, such sil1cone macromer-containing polymers can impart a tactile sense~of softness and conditioning to the hair relative to conventional, non~silicone-containing resins. Silicone macromer-containlng hair styling polymers and formulations containing them are disclosed, for example, in EPO Application 90307528.l, published as EPO Application 0 408 311 A2 on January : 11, 1991, Hayama,: et al., U.:S. Patent 5,061,481, issued October29, l991, Suzuki et al., U~S. Patent 5,l06~609, Bolich et al., issued April 21, 1992, U.S. Patent 5,100t658, Bolich et al., ~: .

WO 93/03704 P~/US92/06975 211~1~4 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., iss~ed 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, l99Il all of which are incorporated by reference herein.
Whereas these silicone macromer-containing hair styling polymers can provide good overall hair styling performance with a desirable hair cond~tioning effect, they are preferably used in hair spray at relatively high molecular weights, compared to most commercial products (although they can also be used at more conventional hair spray resin molecular weights (eg., about 50,000 to about 150,000 weight average molecular weight). Furthermore, they are difficult to formulate into a hair spray composition with good sprayability characteristics.
Therefore, it is another object of this invent~on to provide liquid hair spray compositions con~aining h~gh molecular weight silicone-containing hair styling polymers wh~ch have improved spray characteristics.
It is also desirable to formulate hairspray compositions with reduced leve1s of volatile organic solvents, e.g., ethanol, propanol, etc. One way~ to do this is to increase the amount o~
water present in the composition at the expense of the volatile organic solvent. Unfortunately, this tends to adverselg affect hairspray performance, especially drying time upon app1ication, spray quality, and ha1r feel. This is particularly a problem for reduced volatile organic solvent compositions utilizing silicone macromer-containing hair setting resins. It is especially diffi-cult to obtain good spray quality and hair feel from high water content compositions.
It is yet another object of this invention to obtain improved ~` hairspray compositions containing silicone macromer-containing hair setting resins having reduced volatile organic solvents.
` These and other objects as may be apparent to one skilled in the art can be obtained by the invention hereof, which is des-~ cribed in the description which follows. Unless otherwise in-: (*equivalent to;EP 0412704 and 0412707, published 13 February 1991 ` ~: :

211~15 i dicated, all percentages and ratios herein are by weight.
SUMMARY OF THE INVENTION
The present invention prov~des improved spray~bility hair spray compositions with high molecular weight hair styling poly-mers that can provide excellent hair styling/hold benefits upon spray application to the ha~r.
According to the present i m ent~on, sprayability of high molecular wetght polymers c~n be improved thro~gh the use of ionic strength modifier systems consisting essentially of mixtures of non-surface active anions and cations. It is an essential aspect of the invention that the hair styling polymer also be of an ionlc character.
More specifica11y, the present invention relates to a liquid hair styling composition usefut for spray application to hair which comprises:
(a) an ionic hair styling polymer having a weight average molecular weight of at least about 300,000;
~b) a liquid vehicle`selected from the group consisting of water, Cl-C6, preferably C2-C~, monohydric alcohols, and mixtures thereof;
(c) an effective amount of an ionic strength modifier system for reducing viscosity o~ the composition, said system consisting essential~ly of a mixture of non-surface active cations and anions, wherein said cations and anions are at least partially soluble in said liquid carrier;
said composition having a pH of about 10 or less.
In one aspect of the invention, the high molecular weight hair styling polymer can be any of the conventional classes of hair ~tyling or hair setting polymers in the art, i.e , polymers free of silicone portions. ~
In~another aspect of the invention, the high molecular weight polymer is a silicone macromer-containing hair setting polymer that can provide hair styl~lng and hold benefits while also providing improved softness to the hair relative to non-silicone-containing polymers. In yet another aspect of this :

w o 93/~37~ PcT/us92/o6s7s 211~1~4 invention, provided are reduced volatile organic solvent hairspray compositions having improved hair feel comprising silicone-containing hair setting polymer, an effective amount of an ionic strength moditier system for reducing viscosity of the compositions, as described above, ~nd a liquid vehicle which comprises a mixtur~ of water with one or mor0 Cl-C6, pref~rably C2-C~, monohydric alcoho1s, wherein said composition comprises at least about lOX, by we~ght, water.
DETAILED DESCRIPTION Of THE INVENTION
The essential as well as various optional components are described below.
Hair StYlinq PolYmer The compositions of the present invention contain an effec-tive amount of a high molecular weight hair styling polymer to impart styling benefits upon application to hair. As ~sed herein, "hair styling polymer" means any polymer1 natural or synthetic, that can provide hair setting benefits. Polymers of this type are well known in the art. Generally, the level of hair styling polymer used will be at least about 0.1~., by weight, of the compo-sition. Typically, it will be present at a level of from about 0.1% to about 15%, preferably from about 0.5% to about 8%.
The hair styling polymers hereof also are of ionic character.As used herein, ~ionic hair styling polymer~, or the term "io~ic character~ in reference to hair styling polymers or monomers of which such hair styling polymers are comprised, means hair styling polymers that are anionic, cationic, amphoteric, zwitterionic, or otherwise can exist in the liquid vehicle of the hair styling composition in dissociated form.
Any type of ilonic hair styling polymer which is soluble or dispersible in the liquid carrier can be used in the present invention. A wide variety cf such types of hair styling polymers are known in the art.
The ionic hair styling polymers hereof can be homopolymers, copolymers, terpolymers, etc. As used herein, the term "polymer~
shall encompass~ al;l of such types of polymeric materials.

.

WO g3/03704 PCI'/US92/06975 2ll~

As an essential aspect, the polymers hereof must comprise monomers of an ionic character. For convenience in describing the po1ymers hereof, monomeric units present in the polymers may be referred to as the monomers from which they can be derived. The ionic monomers can be derived from polymerizable ionic starting monomers, or from polymerizable nonionic monomers which are modified subsequent to polymerization to be o~ ionic character Also included are corresponding salts, acids and bases of the monomers exemplified~
l~ Examples of anionic monomers include:
(i) unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid, maleic acid, maleic acid half ester, itaconic acid, fumaric acid, and crotonic acid;
(ii) half esters of an unsaturated polybasic acid anhydride ~5 such as succinic anhydride, phthalic anhydride or the like reacted with a hydroxyl group-containing acrylate and/or methacrylate such as hydroxyethyl acrylate and, hydroxyethyl methacrylate, hydroxy-propyl acrylate and the like;
(iii) monomers having a sulfonic acid group such as styrene-sulfonic acid, sulfoethyl acrylate and methacrylate, and the like;
and (iv) monomers havlng a phosphoric acid group such as acid phosphooxyethyl acrylate and methacrylate, 3-chloro-2-acid phos-phooxypropyl acrylate and methacrylate, and the like. -~Examples of the cationic monomers include:
(i) monomers derived from acrylic acid or methacrylic acid, ; which is referred to hereinafter collectively as (meth)acrylic acid, and a quaternarized epihalohydrin product of a trialkylamine having 1 to 5 carbon atoms in the alkyl such as (meth)acryl-oxypropyltrimethylammonium chloride and (meth)acryloxypropyl-triethylammonium bromide;
(ii) amine der1vatives of ~meth)acrylic acid or amine derivatives of (meth)acrylamide derived from (meth)acrylic acid or (meth)acrylamide and~ a dialkylalkanolamine having Cl-C4 alkyl groups such as dimethylaminoethyl (meth)acrylate, diethylamino-`~ ~ ethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, or :~` ~ : :

: :

W O 93/03704 ` 2 1 1 ~ 1 ~ 4 P~/U~92/06975 dimethylaminopropyl ~meth)acrylamidei and (iii) derivatives of the products of the group ~ti) above by (1) neutralization with an acid such as hydrochloric acid, or lactic acid, (2) modification with a halogenated alkyl, such as methyl chloride, ethyl chloride, methyl bromtde, or ethyl iodide,

(3) modification with a halogenated fatty acid ester such as ethyl monochloroacetate, or methyl monochloropropionate, and (4) modification with a d~alkyl sulfate such as dimethyl sulfate, or diethyl sulfate.
10Furthermore9 the cationic unsaturated monomers include amine derivatives of allyl compounds such as diallyldimethylammontum chloride and the like.
These cationic unsaturated monomers can be polymerized in cationic form, or as an alternative they can be polymerized in the form of their precursors, which are then modi~ied to be cationic, for example, by a quaternizing agent (e.g. ethyl monochloro-acetate, dimethyl sulfate, etc.).
Examples of the amphoteric monomers 1nclude zwitterionized derivatives of the ~aforementioned amine derivatives of (meth)-acrylic acids or the amine derivatives of ~meth)acrylamide such astimethylaminoethyl (meth)acrylate, dimethylaminopropyl(meth)acryl-amide by a `halogenated fatty acid salt such as potassium mono-;~ chloroacetate, sodium monobromopropionate, aminomethylpropanol salt of monochloroacetic acid, triethanolamine salts of mono-chloroacetic~acid and~the like; and amine derivatives of (meth)-acrylic acid or (meth~acrylamide, as discussed above, modified with propanesultone.~
These amphoteric monomers, like the aforementioned cationic monomers, can be polymerizedlin amphoteric form or, as an alterna-tive, they ~can also be polgmerized in the form of their pre-cursors, which are then converted into the amphoteric state.
~` `Preferred ionic monomers include acrylic acid, methacrylic acid, dimethylaminoethyl methacrylate, quaternized dimethyl-~; aminoethyl ~methacrylate, maleic acid, maleic anhydride hal~
esters, croto~nic~ acid, itaconic acid, diallyldimethyl ammonium chloride, polar~vlnyl heterocyclics such as vinyl imidazole, ~inyl ~ :

.

4 PCI/US9~/06975 21151~i4 pyridine, styrene sulfonate, and mixtures thereof. Especially pre~erred ionic monomers include acrylic acid, dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate, and mixtures thereof.
Salts of acid and amine monomers listed above can also be used, e.g., sodium, potass1um, or other alkali or alkaltne earth metal salts.
The polymers hereof should contain at least about 1%, by weight, ionic monomer, preferably at least about 2Y" more pre-ferably at least about 5%.
The hair styling polymers hereof can also contain nonionic monomers including, both high polarity monomers and low polarity monomers.
The ionic polymers hereof will generally comprise from about 1% to 100% ionic monomers and from 0% to about 9g% nonionic monomers, preferably from about 2% to about 75% ionic monomers and from about 25% to about 98% nonionic monomers, more preferably from about 5% to about 50% ionic monomers and from about 50X to about 95% nonionic monomers.
Representative examples of low polarity nonionic monomers are acrylic or methacrylic acid esters of Cl-C2~ alcohols, such as methanol, ethanol, l-propanol, 2-propanol. l-butanol, 2-methyl-1-propanol, l-pen~tanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, l-methyl-l-butanol, 3-methyl-1-butanol, l-methyl-l-pentanol, 2-methyl-1-pentanol,~3-methyl-1-pentanol, t-butanol, cyclohexanol, 2-ethyl-1-butanol, ;3-heptanol, benzyl alcohol, 2-octanol, 6-methyl-l-heptanol, 2-ethyl-1-hexanol. 3,5-dimethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, l decanol, l-dodecanol, l-hexadecanol, l-octadecanol, !and the like, the alcohols having from about ! 1-24 carbon atoms with the verage number of carbon atoms preferably being from about 4-18, more preferably from about 4-12; styrene;
chlorostyrene; vinyl esters such as vinyl acetate; vinyl chloride;
vinylidene chloride; ~acrylonitrile; alpha-methylstyrene; t-butyl-` ~ styrene; butadiene~; cyclohexadiene; ethylene; propylene; vinyl3S toluene; alkoxyalkyl (meth)acrylate, such as methoxy ethyl ~meth)-acrylate, butoxyethyl ~meth)acrylate; and mixtures thereof. Other w o 93/03704 2 1 1 ~ 1 ~ 4 P~/US92/06975 nonionic monvmers include acrylate and methacrylate derivatives such as allyl acrylate and methacrylate, cyclohexyl acrylate and methacrylate, and methacrylate, oleyl acrylate and methacrylate, benzyl acrylate and methacrylate, tetrahydrofurfuryl acrylate and methacrylate, ethylene glycol di-acrylate and -methacrylate, 1,3-butyleneglycol di-acrylate and -meth~crylate, diacetonacryl-amide, tsobornyl (meth)acrylate, and the like~
Preferred nonionic monomers ~nclude n-butyl methacrylate, isobutyl m~thacrylate, 2-ethylhexyl methacrylat~, methyl meth-acrylate, t-butylacrylate, t-butytmethacrylate, and mixtures thereof.
Representative polar nonionic monomers include acrylamide, N,N-dimethylacrylamide, methacrylamide, H-t-butyl acrylamide, methacrylonitrile, acrylamide, acrylate alcohols (e.g. ~2-C6 ~5 acrylate alcohols such as hydroxyethyl acrylate and hydroxyproxyl acrylate), methacrylate, and hydroxypropyl methacrylate, vinyl pyrrolidone, vinyl ethers, such as methyl vinyl ether, acyl lactones, vinyl pyridine, allyl alcohols, vinyl alcohols and vinyl caprolactam.
Examples of anionic hair spray polymers are copolymers of vinyl acetate and crotonic acid, terpolymers of vinyl acetate, crotonic acid and a vinyl ester o~ an alpha-branched saturated aliphatic monocarboxylic acid such as vinyl neodecanoate; and copolymers of methyl vinyl ether and maleic anhydride-(molar ratio about 1:1) wherein such copolymers are 50~ esterified with a saturated aliphatic alcohol containing from 1 to 4 carbon atoms such as ethanol or butanol; and acry1ic copolymers and terpolymers containing acryl:ic acid or methacrylic acid as the anionic radical containing moiety such as copolymers with methacrylic acid, butyl acrylàte, ethyl methacrylate~ etc. Another example of an acrylic polymer which can be employed in the compositions of the present - invention is a polymer of tertiary-butyl acrylamide, acrylic acid, and ethyl acrylate.
: An example of~an amphoteric polymer which can be used in the present invention is Octylacrylamide/Acrylates/Butylaminoethyl Methacrylate Copolymer, described generally in U.S. Pat. No.

211~

4,192,861 as being a polymer of N-tert-octyl acrylamide, methyl methacrylate, hydroxypropyl methacrylate, acrylic acid and t-butyl aminoethyl methacrylate, of appropriate molecular weight for purposes hereof.
Examples of cationic hair spray polymers are copolymers of amino-functional acrylate monomers such as lawer alkylamino alkyl acrylate or methacrylate monomers such as dimethyl aminoethyl-methacrylate with compatible monomers such as H-vinylpyrroltdone or alkyl methacrylates such as methyl methacrylate and ethyl methacrylate and alkyl acrylates such as methyl acrylate and butyl acrylate. Cationic polymers containing N-vinylpyrrol~done are commercially available from GAF Corp.
Still other organic, ionic hair styling polymers ~nclude carboxymethyl cellulose, copolymers of PVA and crotonic acid, copolymers of PVA and maleic anhydride, sodium polystyrene sul-fonate, PVP/ethylmethacrylate/methacrylic acid terpolymer, vinyl acetate/croton1c acid/vinyl neodecanoate copolymer, octylacryl-amide/acrylates copolymer, monoethyl ester of poly(methyl vinyl ether-maleic acid)~ and octylacrylamide/acrylate/butylaminoethyl methacrylate copolymers. Mixtures of polymers may also be used.
Silicone-Containinq Hair Stvlinq Polvmers Preferred ionic hair styling polymers are si1icone-containing polymers. Ionic silicone macromer-containing polymers are de-scribed, for example, 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, Suzuk~i 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-~ackson, 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. Seri~al~ No. 07/758,320* Torgerson et al., filedAugust 27, 1991~7 all~ of which are incorporated by reference herein. ~
Examples~ of~useful polymers and how they are made are also : : (*eguivalent to EP 0412704 and 0412707, published 13 February 1991) `

,, ~ .. ........... .

WO 93/03704 21 1 5 I 5 4 PCr/lJS92/06975 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 incorporated herein by reference.
Preferred ionic silicone macromer-containing polymers com^
prise an organic polymeric backbone, pre~erably a v1nyl backbone, having a Tg above about -20'C (more preferably above about 20'C) and, grafted to the backbone, a siloxane macromer hav~ng a we~ght average molecular weight of preferably at least about 500 preferably from abo~t I,000 to about 100,000, more preferably from I0 about 2,000 to about 50,000, mast pr~ferably about 5,aoo to about 20,000. In addit,ion to the graft copo1ymers described above, silicone-containing polymers also include block copolymers prefer-ably containing up to about 50% (more preferably ~rom about I0% to ibout 40%) by weight of one or more siloxane blocks and one or more non-silicone blocks (such as acrylates or~v1nyls).
~he silicone macromer-containtng polymers preferred for use herein are such that when formulated into the finished hair care composition, and dried, the polymer phase separates into a dis-continuous ~phase which ~ncludes the silicone portion and a con-tinuous phase which i~ncludes the organic port~on.
The silicone macromer-containing ionic hair styling po1ymers generally compr1se noni~onic silicone-containing monomers together with ionic monomers as described above, and can also contain non-silicone-containing nonionic monomers, also described above.
~he silicone-containing monomers also can be ionically charged and, as such, contribute, in part or in whole, to the overa11 charge density of the polymer.
; The silicone-jcontaining hair styling polymers hereof will generally comprise about 0.01% to about 50% of silicone-containing monomer,~ preferably~ from about 0.5% to about 40X, more preferably from about 2X to about 25%. ~ 1 The silicone-containing monomer will generally have the :
formula: ~
X~Y)nSi(R)3-mZm `:
~ wherein X is a vlnyl group copolymerizable with the other monomers WO 93/037~4 PCI~/US92/06975 211~

of the polymer; Y is a divalent linking group; R is a hydrogen, lower alkyl (eg. Cl-C~), aryl, alkaryl, alkylamino, or alkoxy; Z
1s a monoYalent siloxane polymeric mniety having a number average molecular weight of at least about S00, and is pendant from the S organic polymeric backbone; n ~s 0 or l; and m ~s an lnteger from 1 to 3. Of course, Z should be essent~ally unreactive under polymer~zation conditions. The s11icone-containing monsmer preferabl~ has a we1ght average molecular weight of at least about 500, preferabl~ from about 1,000 to about lO0,000? more preferably from about 2,000 to about 50,000, most preferab1y from about 5,000 to about 20,000. Preferably, it is of the formula:

X-C-0-(CH2~q~(0)p-Si(R )3-m Zm wherein m is 1, Z or 3 (preferably m ~ 1); p ~s 0 or 1; q is an integer from 2 to 6; % is CH-C- ;

R~ is hydrogen or -COOH (preferably R2 is hydrogen); R3 is hydro-: gen, methyl or -SH2COOH (preferably R3 is methyi); Z is R~ i--)r;

R3, R4, R5, R6 independently are alkyl, alkoxy, alkylamino, aryl, alkaryl, hydrogen, or hydroxyl (preferably alkyl, more preferably : methyt); and~r is an integer of at least about 10, preferably from about 5 to about~l500 (m;orq preferably r is from about 75 to ?bout 700, most preferably from about 100 to about 250. Particuiarly : preferred are monomers when pzO and q=3.
The silicone-containing monomers of the ionic polymers hereo~
can be polymerized~in a silicone-containing monomer form. Alter-natively, they can be polymerized in the form of their non-sili-:: 35 cone containing precursor, and a silicone group can then be added.
For examp7e, carboxylate-containing monomers, such as acrylic - 13 ~
acid, can be polymerized and then reacted with a silicone-contain-ing compound with a terminal epoxy group. The result will, in general, be a silicone-containing monomer in the polymer having an equivalent structure to the formula X(Y)nSi(R)3 mZm, described above, and is intended to be encompassed herein.
The preferred stlicone-containing polymers useful in the present invent~on generally compr~se from 0% to about 98X ~prefer-ably from about 5% to about 98%, more preferably from about 50% to about 90~.) of nonionic monomer, from 1% to about 98% ~preferably from about 15% to about 80%) of ionic monomer, w~th from about 0.1% to about 50% ~preferably from about 0.5% to about 40X, most preferably from about 2% to about 25%) of the monomers being silicone-containing monomer. The combination of the non-silicone-containing monomers preferably is from about 50% to about 9gX
(more preferably about 60% to about 99%, most preferably from about 75% to about 95%) of the polymer.
Exemplary silicone-containing po1ymers for use in the present invention include the following:
(i) acrylic acid/n-butylmethacrylate/polyd~methyls11Oxane ~PDMS) macromer-20,000 molecular weight (ii) dimethylaminoethyl methacrylate/isobutyl methacrylate/2-ethylhexy1-methacrylate/PDMS macromer-20,000 molecular weight ~ ~ ~
(iii)t-butylacryl?te/acrylic acid/POMS macromer-10,000 molecular weight (iv)t-butylacrylate/acrylic acid/PDMS macromer-10,000 molecular weight ~; The ionic hair styling polymers, including both silicone-containing andl oon-silicone containing polymers, having car-boxylate or other acidic functionalities will preferably be utilized in~ at~ least partially neutralized form in the com-.
positions hereof to ~promote ~solubility or dispersibility of the polymer in the vehicle.~ In addition, use of the neutralized form ; ~ aids in shampoo removabil1ty~ o~ the hair spray compositions. In general, it is preferred that from about lOX to 100~, more preferably from about 20X to about 9~%, even more preferably from WO 93/03704 PCr/US92/06975 2~ 15~

about 40% to about 85X, of the acidic monomers of the polymer be neutralized.
Any conventionally used base, organic or metallic, may be used for neutralization of acidic polymers. Hydroxides of alkali metal and alkaline earth metal are suitable neutralizers for use in the present hair spray compos~tions. It will be recognized by those skilled in the art that various of the cat~ons supplied neutralizing the polymer w1ll also contribute to the ionic strength modifter system, as described here~n.
Preferred neutralizing agents for use in hair spray com-positions of the present `invention are potassium hydroxide and sodtum hydroxide.
Examples of other suitable neutralizing agents which may be included in the hair spray compositions of the present invention include amines, especially amino alcohols such as 2-amino-2-methyl-1,3-propanediol (AMPD), 2-amtne-2-eth~l-1,3-propanediol (AEPD), 2-amino-2-methyl-1-propanol (AMP), 2-amino-1-butanol (AB), monethanolamine ~MEA), diethanolamin:e (DEA), trtethanolamine (TEA), moniospropanolamine (MIPA), diisopropanol-amine (DIPAJ, triisopropanol-mine~(TIPA) and dimethyl steramine (DMS1. Par-ticularly useful for neutralization are mixturès of amines and metallic bases.
; Polymers~ having~ba~sic functionalities, e.g., amino groups, are preferably at;least~partially neutraltzed with an ~cid, e.g~, hydrogen chloride.
Liquid Vehicle The hair spray compositions of the present invention also 1nclude a liquid vehicle. This can comprise any of those conven-tionally used i~n~ res1n Iha~ir spray~ formulations. The liquid vehicle is present in the hair spray compositions at from about 807, to about~99%, preferably from about 85% to about 99%. More - preferabiy, the 1iqu1d vehicle~is present at from about 90~ to about 98X of the total composition.
Organic solvents suitable for use in the liquid vehicle of ~; 35 the present compositions are CI~C6 alkanols, carbitol, acetone and mixtures thereof. Cl-C6 alkanols preferred for use in the present ~ : :

w o 93/03704 2 1 1 ~ 1 ~ I PCT/US92/06~7~

compositions are C2-C~ monohydric alcohols such as ethanol, isopropanol and mixtures thereof. Water is also a preferred solvent for use in the liquid vehicle of the present hair spray compositions.
Pre~erably, the liquid vehicle for the present composittons is selec$ed from the group consisting of Cl-C~ alkanols, water, carb~tol, acetone and mixtures thereof. More preferably, the liquid vehicle of the present composition is selected from the group consistin~ of water and G2-C~ monohydrk alcohols such as ethanol and isopropanol, and mixtures thereo~.
In general, water may be absent from the llquid vehicle or may comprise all of the liquid Yehicle. Most preferably, the liquid vehicle is a mixture of water and organic solvents.
Where water and organic solvent 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 50X by weight of the total composition. In such mixtures, the organic solvents are generally present in the range of from 0.5X to a~out 99%~ preferably from about 50Y. to about 9~%, by weight of the total composition.
In one aspect of the invention, the hair setting resin is of particularly high weight average molecular weight, i.e. weight average molecular weight above about 30Q,000, especially above about 500,000. It has been found that surprising1y effective hair spray performance can be obtained using these high molecular weight resins in combination with ionic strength modifier system.
This invention is especially effective at providing the resins with characteristics in hairispray compositions such that thqy can be sprayed with good spray quality, especially with respect to silicone macromer-containing hair setting resins, which are ` ` preferably used at relatively high molecular weights.
In another aspect of the invention, what is provided is a low volatile organic solvent hair;spray composition which comprises a ; 35 silicone macromer-containing ionic hair setting resin, an ionic ~ strength modlfler system as described herein, and a liquid :: :

WO 93/037~)4 PCI/US92/06975 vehicle. A reduced volatile organic solvent hair spray composi-tion of the present invention comprises no more than 80X volatile organic solvents (which include, for purposes hereof, volatile silicone fluids and excludes water). In other embodiments hereof, the hair spray compositions can comprise no more than about 65%, 55%, 50Y., or other levels of vol~t~le organic solvents, as may be chosen by product formulators. In the reduced volatile organic solvent hair spray products hereof, the hair spray compos1tions comprise at least I0~9, by weight, of water. It ~s also specifically contemplated that they may contain at least about llYo~ 12%~ 13%~ 14%~ 15%, or more water. The weight average molecular weight of the silicone macromer-contalning hair setting resins can be of any level suitabte for providing ef~ective hair styling. Typically, it will be at least about 50,000, more typically at least about 70,000, preferably at least about 100,000. As used herein, volatile organic solvents means solYents which have at least on~ carbon atom and exhibit a vapor pressure of greater than 0.1 mm Hg at 20-C.
In the more preferred embodiments of thls aspect of the invention, the weight average molecular weight of the resin is from about 70,000 to about l,000,040, most prefèrably from about lO0,000 to about 750,000.
In general, the reduced volatile organic solvent compositions hereof will comprise up to aDout 90Yo~ preferably up t~ about 70%, more preferably up to abcut 60X, even more preferably up to about 50X water; and from about lOY. to about 80%, preferably from about 20~ to about 80Y., more preferably from about 40~. $o about 80%, of volatile organic solvents. ~t is also specifically contemplated that the compositions can ~e limitedito no more than other m~ximum limits on volatile organic solvents, eg., no more than about 75%, 65X, or 55%, etc In general, for tho compositions hereof, the weight average molecular weight of the styling polymer is limited only by practical concerns. Generally, it will be below about 10,000,000, preferably below about 3,000,000, more preferably below about 1,000,000.

.

WO 93/03704 PCI'/US92/06975 211~1~4 lon~c Strenqth Modifier SYstem The compositions of the present invention include, as an essential element, an effective amount of an ionic strength modifier system for reducing the viscosity of the hair styling composition, relative to the same compos1tion absent the ionic strength modifiers. In general, the present compositions will compr~se at least about 0.01%, by weight, oi the ionic strength modifier. As will be understood by those skilled in the art, as the ionic strength of th~ composition is increased, the hair styling polymer will eventually fall out of solution, or otherwise no longer remain solubilized or dispersed in the liquid carrier.
The upper limit of the ionic stren9th modifier system level will vary depending upon the partlcular ionic strength modifiers, liquid vehicle, hair styling polymer, and other ingredients present in the composition. Thus, for example, the maximum amount of the ionic strength modifiers that can be used w1ll tend to be lower for compositions wlth liquid vehicles conta~ning less water, compared to compositions with more water. Generally, the com-positions will comprise about 4%, by weight, or less of the ionic strength modifiers, more 9enerally about 2% or less, and typically about 1% or less. Preferably, the compositions hereof will comprise from about 0.01X to about 0.5%, more preferably from about O.OIX~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 significantl!y reduce surface tension. For purposes hereof, , ~
non-surface active~sh-ll méan the ions, which at a 0.5% aqueous solution concentration, requce surface tension by no more than S.0 dynes~cm2. Generally, the ions of the ionic strength modifier system hereof;will~be~characterized by having, at maximum, four or `~ less ~arbon~atoms per cha;rge, preferably two or less carbon atoms, ; in any aliphatic~ chain or straight or branched organic hetero-ch~in.
The ionic strength~modifier system comprises monomeric ions of the type which~;are products of acid-base reactions. Thus, WO g3/0370q PCr~US92/06975 211~

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 tncorporated into the composition in a form such that they can exist in the com-position as free ions, i.e., in dissociated form. It is notnecessary that all of the ions added exist in the compos~tion as free ionst but they must be at least part~ally soluble or dis-sociated in the composit~on. The ionic strength modifiers can be incorporated into the hair styling compositions, for example, by ~o 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 includes ~or example, alkali metals, such ~s l~th1um, sodium, and potass~um, and alkaline-earth metals, such as magnesium, calcium, and stronttum. Preferred of the divalent cations is m?gnesium. Preferred monovalent metal ions are lithium, sodium, and potassium, particularly sodium and potassium.
Suitable means o~ addition to the compos~tions hereof include, for example, addition as bases, eg., hydroxides, sodium hydroxide and potassium hydroxide, and such as salts that are soluble in the liquid carrier, eg. salts of monomeric anions such as those described below.
Other suitable cations include organic ions, such as quater-nary ammonium ions and cationic amines, such as ammonium mono-, di-, and tri-ethanolamines, triethylamine, morpholine, amino-methylpropanol (AMP), aminoethylpropanediol, etc. Ammonium and the amines are preferably provided in the forms of salts, such as hydrochloride salts.
Monomeric ànions that can be used include halogen ions, such as chloride, fluoride,~bromide, and iodide, particularly chloride, sulfate, ethyl sulfate, methyl sulfate, cyclohexyl sulfamate, thiasulfate, toluene `sulfonate, xylene sulfonate, citrate, ni-trate, bicarbonate, adipat:e, succinate, saccharinate, benzoate, lactate, borate, isethionate, tartrate, and other monomeric anions W(~ ~3/03704 PCr/US92/06975 211~

that can exist in dissociated form in the hair styling composi-tion. The anions can be added to the compositions hereof, for example, in the form of acids or salts which are at least par-tially soluble in the liquid vehicle, eg., sodium or potassium salts of acetate, citrate, nitrate, chloride, sulfate, etc.
Preferably, such salts are entirely soluble in the veh1cle.
The compositions hereof have a water-equivalent pH of about 10 or less, pre~erably from about 3 to about 10, mor~ preferably from about i to about IO. For purposes hereof, water-equiv~lent 1~ pH shall correspond to the pH of a compositian containing all of the components of the ~omposit~on, except that any non-aqueous coponent of the carrier is replaced by an equal weight of double reverse osmosis (DRO) water.
A preferred reduced volatile organic solvent hairspray composition of the present invention contains from about .OlY. to about 2~ of ~ fluorosurfactant; from ab~ut 0.1% to about 15X of an ionic resin, inc1uding those having a weight average molecular weight of 300,000 and above, as well as those be10w 300,000, and also including those having silicone macromer portions as well as those without; an ionic strength modifier system as described herein, and a liquid vehicle comprising about 10% to about 45%, by weight of the compos~tion water and about 50% to about 80~o~ by weight of the composition, of an organic solvent, prefera~ly selected from the group consisting of ethanol, isopropanol and '~ mixtures thereof.
The level of ionic strength modifier system used, in general, is given above. It is to be recognized, however, that the par-ticutar level of ionic~strength modifier system which must be used to achieve an improvementlin hair spray performance, or to achieve optimùm performance, for a particular hair spray composition can ~` vary depending upon a variety of factors, in~luding the particular type of resin chosen and its molecular weight, and level in the composition, the specific ionic strength modifier system, the level of water and the type and level of volatile organic solvent, ~ 35 and the presence of option-l components in the system. In gene-'~: `

WO 93/03704 PCI/US9~/06975 2~151~

ral, higher levels of ionic strength modifier system may be needed to achieve a performance benefit as restn molecular wei~ht and/or water levels are reduced. In general, the compositions hereof should contain at least an effectiYe amount of the ionic strength S modifier system provide an improvement in hair feel for a given level of hair hold performance or ~or i~proved spray quality (?).
ODt1onal Inqredients In addition to the ~onic strength modifier system described above~ the compositions hereof can optionally conta~n other materials to improve sprayability of the compositions. In par-ticular, it is contemplated to utilize ionic surfactants in combination with the non~surface active anions and cations of the ionic strength modifier system hereof.
A wide variety of surfactants may be advantageously incorporated into the compositions hereof. These include an~onic, cationic, amphoteric, and zwitterionic surfactants, and further include both fluorinated surfactants, as described below, and nonfluorinated surfactants.
Anionic surfactants include, for example: alkyl and alkenyl sulfates; alkyl and alkenyl ethoxylated sulfates; (preferably having an average degree of ethoxylation of 1 to lO), succinamate surfactants, such as alkylsut~osuccinamates and dialkyl esters of sulfosuccinic aci~d; neutralized fatty acid esters of isethion~c acid; and alkyi and alkenyl su1fonates, including, for example, olefin sulfonates and beta-alkoxy alkane sulfonates. Preferred are alkyl and alkenyl sulfates and alkyl and alkenyl ethoxylated sulfates such as the sodium and ammonium salts of Cl2-C~ sul~ates and ethoxylated sulfates with a degree of ethoxylation of from 1 to about 6, preferably from l to about 4, e.g., lauryl sulfate and , ~ j laureth (3.0) sulfate.
- Amphoteric surfactants include those which can be broadly described as derivatives of al~iphatic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to~about l8 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sul~ate, WO 93/n3704 PCl'/US92/06975 ~151~

phosphate, or phosphonate. Examples of compounds falling within this definition are sodium 3-dodecylaminopropionate, N-alkyl-taurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teaching of U.S. Patent 2,658,07Z, N-higher alkyl aspart k acids such as those produced according to the teaching of U.S. Patent 2,438,091, and the products sold under the trade name ~Mirano1~ and described in U.S.
Patent 2,528,378. Others include alkyl, preferably C6-C22 and most preferably Cg-Cl2, amphoglycinates; alkyl, preferably C6~C22 and most preferably Cg-C12, amphopropionates; and mixtures thereof.
Suitable zwitterionic surfactants for use in the present compositions can be exemplified by those which can be broadly described as derivatives of aliphatic quaternary ammonium, phos-phonium, and sulfonium compounds, in which the aliphatic radicals can be straight chain or branched, and wherein one of the ali-phatic substituents contains from about 8 to 18 carbon atoms and one contains an an~onic water-so1ubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. A general form~la for these compounds is:
;, ~ (R3)X
1:
R2 -- Y(+)~ CH2 --- R~ --- Z(-) wherein R2 contains an alkyl, alkenyl, or hydroxy alk~l radical of from about 8 to about 18 carbon atoms, from O to about 10 ethylene oxide moieties and from O to 1 glyceryl moiety; Y is selected from the group consisting of nitrogen, phosphorus, and sulfur atoms; R3 is an alkyl or monohydroxyalkyl group containing 1 to about 3 carbon atoms; x is l whenlY~is sulfur or phosphorus, 1 or 2 when Y
is nitrogen; R4 is an alkylene or hydroxyalkylene of from 1 to about 4 carbon atoms and Z is a radical selected from the group .
consisting of carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups.~ Classes of zwitterionics include alkyl amino sulfonates, alkyl betaines, and alkyl amido betaines.
Cationlc surfactants useful in compositions of the present ;~ invention contain mino or quaternary ammonium hydrophilic moi-~: :

eties which are positively charged when dissolved in the aqueous composition of the present invention. Cationic surfactants among those useful herein are disclosed in the following documents, all incorporated by reference herein: M. C Publishing Co~, McCut-S cheon's, Detergents ~ Emuls1f~ers, (North American edition 1979);
Schwartz, et al., Surface Act1ve Agents, The~r Che~1stry and Technology, New York: Intersc~ence Publ~shers, 1949; U.S. Pat. No.
3,1S5,591, Hilfer, issued Nov. 3, 1964; U.S. Pat. No. 3,929~678, Laughl~n, et al., issued Oec. 30, 1975; U.S. Pat. No. 3,959,461, Bailey, et al., issued May 25, 1976; and U.S. Pat. No. 4,387,090, Bolich, Jr., issued June 7, 1983.
Among the quaternary ammonium-containing cationic surfactant materials useful herein are those of the general formula:

@ / N ~ ~ X-wherein R~ is an aliphatic group of from 1 to 22 carbon atoms, or an aromatic, aryl or alkylaryl group having from 12 to 22 carbon atoms; R2 is an aliphatic group having from 1 to 22 carbon atoms;
R3 and R~ are each alkyl groupS having from 1 to 3 carbon atoms, ` and X is an anion selected from halogen, acetate, phosphate, nitrate and alkylsulfate radicals. The aliphatic groups may contain, in addition to carbon and hydrogen atoms, ether linkages, ` and other groups such as amido groups. Other quaternary ammonium salts useful herein are diquaternary ammonium salts.
Preferred~quaternary ammonium salts include dialkyldimethyl-ammonium chlorides?~wherein in the alkyl groups have from 12 to 22 carbon atoms~and are derived from long-chain fatty acids, such as hydrogenated tallow fatty acild. (Tallow fatty acids give rise to quaternary compounds wherein~R~ and R2 have pre~ominately from 16 `~` to 18 carbon ?toms.) Salts of primary, secondary and tertiary fatty amines are also suitable cationic surfactants for use herein. The alkyl groups of such~amines;~preferably have from 12 to 22 carbon atoms, ~and may be subst~itutèd or unsubstituted. Secondary and tertiary amines are preferred, tertiary amines are particularly preferred.
Such amines,-useful herein, include stearamido propyl dimethyl ~: :

WO 93/03704 P~/US92/06975 211S15 l amine, diethyl amino ethyl stearamide, dimethyl stearamine, dimethyl soyamine, soyamine, myristyl amine, tridecyl amine, ethyl stearylamine, N-tallowpropane diamine, ethoxylated ~5 moles EØ) stearylamine, dihydroxy ethyl stearylamine, and araehidyl-behenylamine. Cationic a~ine surfactants in~luded among those useful in the present inventlon ~re d1sclosed in U.S. Pat. No.
4,275,055, Nachtigal, et al., issued June 23, 1981 ~ncorporated by reference herein).
Suitable cationic surfactant salts include ~he ha1ogen, acetate, phosphate, nitrate, cttrate, lactate and alkyl sulfate salts.
Nonionic surfactants can also be included in the compositions hereof. Preferably, the nonionic surfactants have an average HLB
~Hydrophile-Lipophile Balance) of less than or equal to about 7.
Methods of determ~ning HLB are wel1 known in the art and any of such methods may be used ~or HLB determinatlon. A description of the HLB System and methods for HLB determination are described in ~The HLB System a time saving 9uide to emuls1f~er selection, "
ICI Americas Inc.; Wilmington, Delaware; 1976.
Nonionic surfactants inc1ude polyethylene oxide condensates : of al kyl phenols (preferably G6 -Cl 2 alkyl, with a degree of ethoxylation of about 1 to about 6), condensation products of ethylene oxide with the reaction product of propylene oxide and ethylene diamine, condensation products of aliphatic a~cohols with ethylene oxide, long chain (i.e., typically Cl2-C22) ter~iary amine oxides, long chain tertiary phssphine oxides, dialkyl sulfoxides containing one long chain alkyl or hydroxy alkyl radical and one short chain (preferably Cl-c3) radical, silicone copolyols, and Cl-C4 alkanol!amides o~ acids having a C8-Cz? acyl moiety.
Fluorosurfactants ( i . e ., fl uori nated surfactants) use~ul in the present compositions can~be linear or branched alkyl, alkenyl or alkylaryl fluorohydrocarbons having a chain ~length of prefer-ably 3 ta 18 carbon atoms and being f~lly or partially fluori-nated. The hydrophilic moiety can be, for example, sulfate, .
' WO ~3/0370~ PCI/US92/06975 211~154 phosphate, phosphonate, sulfonate, amine, amine salts, quaternary ammonium, carboxylate, and any combination thereof. Also, there can be a bridging moiety between the hydrophilic and hydrophobic moieties, such as an amido alka1ene group for example.
Ionic fluorosurfactants useful ~n the present compositions include perfluorinated compounds represented by the formula CF3-(CF2)x~(CH2)y-z where Z is a water solubilizing group of either organic or in-organic character, x is an integer whtch is generally from 2 to 17, particularly from 7 to 11, and y ~s an integer from O to 4, and said compounds may be cationic, anionic, amphoteric or zwit-terionic, depending upon the nature of the grouping or groupings encompassed by Z. The Z groups may be or may comprise sulfate, sulfonate, carboxylate, amine salt, ~uaternary ammonium, phos-phate, phosphonate~ and combinations thereof. The perfluorinated compounds are known in the art. These compounds are described tn U.S. Patent 4,176,176~ Cella et al., ~ssued November 27, 1979;
V.S. Patent 3,993,745, Cella et al., issued November 23, 1976~ and U.S. Patent 3?993~744~ Cella et al., issued NoYember 23~ 1976?
each being incorporated herein by reference.
Cationic fluorosur~actants preferred for use in the present compositions include fluorinated alkyl quaternary ammonium salts having a variety of anionic counter ions, including iodi~e, ` chloride, methosulfate, phosphate, and nitrate saltsr preferably an iodide; and those fluorosurfactants conforming to the formula RfCH2CH25CH2CH2N~(CH3)3~CH350~]- wherein Rf-F(CF2CF2)3 ~, such as ZONYL FSC supplied by E. I. DuPont deNemours and Company (Wi1ming-ton, Delaware, USA; DuPont). A preferred fluorinated alkyl quaternary ammonium iodide is FL W RAD FC 135 supplied by Minnesota 3~ Mining & Manufacturing (St. Paul, Minnesota, USA; 3M).
Anionic fluorosurfactants preferred for use in the present compositions:are mono-, and bis-perfluoroalkyl phosphates, such as ZONYL FSP supplied by DuPont and conforming to the general formu-lae (RfCH2cH2o)p(~)(oNH~)2(RfcH2c~2o)2p~o)(oNH4) wherein : : 35 R~=F(CF2CF2)3 8; mono- and bis~fluoroalkyl phosphates, having a WO 93/fl3704 PCI/US92/06975 vartety of cationic counterions such as ammonium, sodium, potas-sium, triethanolamine and diethanolamine salts, preferably ammo-nium salts, complexed with non-fluorinated quats, preferably aliphatic quaternary methosulfates, such as ZONY~ FSJ supp1ied by DuPont; perfluoroalkyl sulfonic acid having a Yariety of cationic counterions such as ammon~um, sodium, potassium, triethanolamine and d~ethanolamine 5alts, preferably ammonium salts, such as ZONYL
TBS supplied by DuPont and conforming to the formula RfCH2CH2SO3X
wherein Rf~F(CF2CF2)3 ~ and X~H or NH4; telomer phosphates, having a variety of cationic counterions such as ammonium, sodtum, potassium, triethanolamine and diethanolamine salts, preferably diethanolamine salts, such as ZONYL RP supplied by DuPont; amine perfluoroalkyl sulfonates, such as FLUORAD FC-99 supplied by 3M;
ammonium perfluoroalkyl sulfonates, such as FLUORAD fC-93, FLUO MD
FC-120 and ~-12402, supplied by 3M; potassium perfluoroalkyl sulfonates, suc~h as FLUORAD-95 and FLUORAD fC-98 suppl~ed by 3M;
potassium fluorinated: alkyl carboxylates, such as FLW RAO FC-129 :: and FLUORAD FC-109 supplied by 3M; ammonium perfluoroalkyl car-boxylates, such ~s Fluorad FC-143~ supplied by 3M; and those ~ 20 fluorosurfactants conforming to the general formula :~; : RfCH2CH2SCH2CH~CO2Li wherein Rf-F~CF2CF2)3~, such as ZOHYL FSA
~: supplied by:DuPont.
:~ Preferred ~ anionic fluorosurfactants are mixed mono- a~nd bis-perfluoroalkyl phosphates, ammonium salts; mixed mono- and bis-fluoroalkyl phosph~ate;, ammonium salts, complexed with ali-. phatic quaternary~ methosulfates; perfluoroalkyl .sulfonic acid, ammonium sal~ts;: mixed ~telomer phosphate diethanolamine salts;
amine perfluoroalkyl: sulfonates; ammonium perfluoroalkyl sul-h fonates; potassium perfluoroalkyl sulfonates; potassium fluori-.
nated:;alkyl carboxylateSi ammonium perfluoroalkyl sulfonates, and ::. : ammonium perfluoroalkyl carboxylates.
Amphoteric fluorosurfactants preferred for use in the present compositions~:are~fluor;inated alkyl amphoteric surfactants avail-: able commerci:ally as~FLUORAD FC-100 from 3M.
Zwitterlonic~ fluorosurfactants preferred for use in the : .

WO 93/03704 PCI`/US92/06975 2l1S1 5~

present compositions are those fluorosurfactants confonming to the formula RfCH2CH(OCOCH3)CH2N+(CH3)2CH2CO2 wherein Rf~F(CF2CF2) such as ZONYL FSK supplied by DuPont.
Preferably, mixtures of amphoteric or zwitterionic fluoro-surfactants with anionic fluorosurfactants or mixturss of anionicand cationic fluorosurfactan~s are used.
The use of fluorosurfactants is espec~ally desirable in reduced volatile organic solvent composit~ons, and most especially those w~th silicone macromer-containing polymers.
Surfactants are preferably included in the compositions at a level of from about 0AO1% to about 2%, more preferably from about 0 01X to about 1.5%, most preferably from about 0.01~ to about 1%.

Plasticizer The per~ormance of the hair styling pol~mers can be improved through the optional incorporation of a nonv~latile plasticizer into the compositlon. The plast~cizer will generally be present in the compositions at a plasticizer: stylin~ polymer weight ratio of about 1:20: to about 1 19 preferably from about 1:15 to about 1:2. As used herein, "nonvolatile" in regard to plasticizers means that the plasticizer exhibits essentially no vapor pressure at atmospheric pressure and 25~C. The polymer-liquid vehicle solution should not suffer from substantial plasticizer weight loss while the volatile carrier is evaporating, since this may excessively reduce plasticization of the polymer during us~. The plasticizers for use herein should generally have boiling points of about 250-C or higher. ~
Plastlcizers are well known in the art and are generally described in Kirk-Othmer EncYcloPedia of Chemical TechnoloqY, second edition, Volume 15, pp. 72Q-789 (~ohn Wiley & Ssns, Inc.
New York, 1968) under the topic heading "Plasticizers", and by J.
Kern Sears and Joseph R. Darby in the text The Technologv Qf Plasticizers (John ~Wiley ~ Sons, Inc., New York, 1982), both incorporated herein by reference. See especially in the Appendix of Sears/Darby Table A.9 at pages 983-1063 where a wîde variety of plasticizers are disclosed.

W O 93/03704 2 1 1 S 1 ~ ~ PC~r/US92/06975 Plasticizers include both cyclic and acyclic nonvolatile materials. Suitable categories of nonvolatile plasticizers include adipates, phthalates, isophthalates, azelates, stearates, citrates, trimellitates, silicnne copolyols, iso Cl~-C22 alcohols, methyl alkyl silicones, carbonates, sebacates, isobutgrates, oleates, phosphates, myr~states, rictnoleates, pelargonates, valerates, oleates, camphor, and castor o~l, and silicone co^
polyo~s.
Examples of adipate plastici~ers ~nclude adipic acid deriva-tives such as diisobutyl adtpate, bis(~-ethylhexyl) adipatef dilsodecyl adipate, bis(2-butoxyeth~l) adipate, and di-n-hexyl adipate.
Examples of phthalate plasticizers include phthalic acid derivatives such as dibutyl phthalate, butyl octyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, b~s(2-ethylhexyl) phthalate, n-actyl n-decyl phthalate, di-n-hexyl phthalate~
iso~ctyl isodecyl phthalate, diisodecyl phthalate, ditridecyl phthalate, butyl eyclohexyl phthalate, butyl benzyl phthalate, dicyclohexyl phthalate, diphenyl phthalate, isodecyl benzyl phthalate, and bis(2-butoxyethyl) phthalate.
Isophthalate plasticizers include bis(2-ethylhexyl) iso-phthalate.
Examples of azelate plasticizers include azelaic acid deri-vatives such as di~(2-ethylhexyl) azelate, and bis(2~ethylhexyl) azelate Examp7es of stearate plasticizers include stearic acid derivatives such as n-butyl stearate, butyl acetoxystearate, and butoxyethyl stearate.
Examples of citrate plasticizers include citric acid deriva-tiYes such as acetyl tri-n-butyl citrate, tri-n-butyl citrate, and acetyl tri-2-ethylhexyl citrate.
Examples of trimellitate plasticizers include tri-(2-ethyl-hexyl) trimellitate, and triisooctyl trimellitate.
Other examples of plasticizers incl~de dibutyl carbonate, butyl oleate, n-butyl, butyrate, isobutyl butyrate, isopropyl ;

W O g3/03704 P(~r/US92/06975 21151~

butyrate, dibutyl carbonate, ethyl palmitate, isooctyl palmitate, methyl ricinoleate, butyl ricinoleate, ditsooctyl sebacate, triisobutyl phosphate, isodecy pelargonate, ethyl val~rate, isocetyl alcohol, octododecanol, isopropyl myristate, isostearyl alcohol and methyl alkyl silicones having C2-C20 alkyl and from 1 to about 500 siloxane monomer units, silicone copolyols, eg.
dimethicone copolyol.
Hair Spray Compositions Hair spray compositions of the present inventton can be dispensed from containers which ~re 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 variety of manufacturers, including American National Can Corp. 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 pro-pellants which can include liquified lower hydrocarbons of 3 to 4 carbon atoms such as propane, butane and isobutane. Other suit-able propellants are hydrofluorccarbons s~ch as 1,2~dif-luoroethane (Hydrofluorocarbon 152A) supplied as Dymel 152A by DuPont. Other examples of propellants are dimethylether, nitrogen, carbon dioxide, ni;trous oxide and atmospheric gas.
The hydrocarbons, particularly isobutane~ used singly or admixed with other hydrocarbons are preferred.
fhe aerosol propeliant may be mixed with the present compo-sitions and the amount of propellant to be mixed is governed by normal ~actors well known in~ the aerosol art. Generally, for liquifiable propellants, the level of propellant is from about l~X
to about 60% by weight of the total composition, preferably ~rom about 15% to about 50X by weight of the total composition.

~:

~: :: ;

WO 93/03704 2 1 1 5 1 ~ ~ PC~/US92/06975 ~ 29 -Alternatively, pressurized 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 Americal Nationa1 Can Corp.
Other suitable aerosol dispensers are those characterized by the propellant being compr~ssed air which can be filled into the dispenser by means of a pump or equivalent device prior to use.
Such dispensers are describ0d in U~S. Patents 4sO77~441~ March 7~
1978~ Olofsson and 4,850,577, July 25, 1989, T~rStege, both incorporated by reference herein, and in U.S. Serial No.
07/839,648, Gosselin et al., filed February 21, 1992, also incorporated by refer~nce herein. Compressed air aerosol containers suitable for use are also currently marketed by The Procter & &amble Company under their tradename VIDAL SASSOON
AIRSPRAY6 hair sprays.
Conventional non-aerosol pump spray dispensers, i.e., atomizers, can also be used.
Other Inaredients The hair spray formulations of the present invention can optionally contain a variety of other hair spray adjuvants as are known in the art. Generally, the compositions will comprise from about 0.05% to 5%, by weiyht, preferably f,ram about ~.lr. to 3%, by weight, of adjuvants. Hair spray adjuvants include: silicones;
emollients; lubricants and penetrants such as various lanolin compounds; protein hydrolysates and other protein derivatives;
ethylene adducts and polyoxyethylene cholesterol; dyes, tints and other colorants; sunscreens; and perfume.
METHOD OF USE
The hair spray 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 spraying an effective amount of the product to dry or damp hair before or after the hair is styled, or both. By "effective amount" is meant an amount sufficlent to provide the hair volume and style benefits desired considering the length and texture of the hair.

211~

The fol~owing Examples illustrate the present invention. The Examples are given solely for the purposes of illustration and are not to be construed as limitations of the pres~nt invention as many variations of the invent~on are possible without departing from its spirit and scope.
EXAMPLES
ExamDles I-XVI
Hair spray compositions of the present invention are prepared according to the following formulations.
Exa~ple # (Weight Percent) Inqredient _I _LI_ _111 IV V _YI_ _Yll_ YIII
Ethanol, 200 proof 79.3 79.3 79.2 79.2 79.1 79.1 79.2 79.2 Isopropanol -- 10.4 10.4 10.4 10.4 10.4 10.4 10.4 Hair Styling 4.0 2.6 2.6 2.6 2.6 2.6 2.6 2.6 Polymer ' KOH ~45X aqueous 0.82 0.7 0.8 0.8 n.8 0.8 0.8 0.8 solution) 2 DRO Water~ 17.4 7.0 7.Q 7.0 7.0 7.9 7.0 7.0 Potassium Chloride 0.02 0.05 0.02 Potassium Acetat~ - - - - o,ogMagnesium Acetate - - - - -Acetic Acid - - - - 0.06 - - - 0.06 Fluorssurfactant~ - - 0.1 0.05 AM P S -- -- -- -- ~
Example # (Weight Percent) Inqredient~ IX _ X XI XII_ XILI XIV XV XYI
Ethanol, 200 pro~f 79.2 86.6 86.3 43.3 86.6 80.0 75.9 75.8Isopropanol 10:.4 10.4 10.4 10.4 10.4 10.4 Hair Styling 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 P'olymer 1 :: ~ KOH2 : 0.8 - - - - - 3.3 3.3 DRO Water3 7.0 0.1 0.3 42.9 - 7.0 15.0 15.0 Potassium Chloride - 0.03 - - - 0.03 Potassium Acetate ~ 0.09 - 0.1 - - - - 0.2 : 35 Magnesium Acetate - - - - - 0.1 : Acetic Ac;d - - - 0.5 :

WO 93/03704 P~/US9~/06g75 Fluorosurfactant4 - - - - O.O5 AMP5 0.3 0.3 0.3 0.3 60X t-butyl acrylate/20X acrylic acid/20% silicone (PDMS) macromer - Example I, weight average molecular weight of about 150,000. Examples II-VI~ weight average molecu1ar weight of about 1.7 m111ion; Examples YII-XIV, wei9ht av~rage molecular weight of ~bout 800,000; Examples XV-XVI, weight average molecular we~ght of about 1.2 million.
2 Potassium hydrox~de solution, containin~ 45% potassium hydroxide and 55X water and minors, except Examples XV and XVI, utilizin~ a 10% aqueous solution of potassium hydroxide.
3 Double reverse osmosis water.
~ ZONYL FSK containing 47% fluorosurfactant conforming to the formula RfcH2cH(ococH3~H2N+(cH3)z(c~2co2- wherein Rf3F~CF2CF2~3 ~ and 53X Acetic Acid and minors, supplied by E.I. DuPont de Nemours & Co., Inc. (Wilmington, Delaware, USA~.

5 2-Amino-2-methyl-1-propanol.
The hair spray formulations are prepared by forming a prem~x of the polymer in isopropanol, and then adding the ethanol. For Examples I, XV and XVI9 the~ polymer is added directly to the ethanol. A magnetic or air driven stirrer is used to mix the ingredients unti1 the polymer is dissolved, typically about l to 2 hours. If used, the neutralizing a~ent (KOH or AMP; or both) is then added and mixed into the premix. Then, fluorosurfactant, any of the salts, and water, as may be applicable, are mixed into the composition.
Adjuvants may aiso be added to the compositions, including, f~r example, perfume orlfragrance. The hair spray compositions prepared are especially suitable for pump spray application. The compositions will characterized by good sprayability character-istics and hair:styling performance Example XVII
A hair spr~y composition, of the present invention, which is suitable for pump spray dispensers, is prepared as follows:

~ 93~3~04 PCI~/US92/06975 2il51~4 Inqredient ~5h~ %
Ethanol, 200 proof 78~5 Isopropanol 10.4 Hair Styling Polymer1 2.6 KOH (45%) ~ 7 DRO Water 7.0 fLUORAD FC-1202 0.4 ZONYL FSK 0,5 1 60% t-bukyl acrylate/20% acrylate acid/20% PDMS macromer, having a we;ght av~rage molecu~ar w~ight af about 1,700,000.
2 FLUO~AD FC~120 supplied by Minnesota Mining and Manufacturiny Co. ~3M~, (St. Paul, Minnesota, USA) containing 25% ammonium perfluoroalkyl sulfonates, 37.5% ethanol and 37.5Y. water and minors.
Prepared as in Examples I-XVI.
Example XVIII
A hair spray composition9 of the pr2sent invention, which ~s suitable for pump spray dispensers, is prepared as follows:
Tnqredient Weiqht %
Ethanol, 200 proof 8g.1 Hair Styling Polymer1 2.6 KO~ (45~) 0.7 DRO Water 7.0 FLUO~AD FC-1202 0.1 ZONYL FSK 0,5 6070 t-butyl acrylate/20~ acrylate acid/20% PDMS macro~er, having a weight average molecular weight of about 1,700jOOO.
Prepared as in Examples I-XVI.
Example XIX
A hair spray composition of the present invention, which is suitable for pump spray dispensers, is prepared as follows:
In~redient Weiqht YO
Ethanol, 200 proof 78.8 W ~ g3/03704 2 1 ~ 4 PCT/USg2/06975 Isopropanol 10.4 Hair Styling Polymer1 2.6 KOH (45%) 0~8 DRO Water 7.0 FLUORAD FC-1202 4.4 ZONYL FSK o.a4 60X t-but~l acrylate/20% acr~late ac1d/2~% PDMS macromer, having a weight average molecular we~ght of about 580,000.
Prepared as in Examples I-XVI.
Examples XX-XXII
A hair spray composition, of th@ present invention, which is suitable for pump spray dispensers, is prepared as follows:
Example Example Example XX XXI XXII
In~redient ~Wt %~ (Wt %) (Wt %) Ethanol, 200 proof 71.1 71.2 71.2 Isopropanol 9.5 9,5 9,~
Hair Styling Polymer1 2.4 2.4 2.4 KOH (45%) 0.6 0.6 D.6 : DRO Water 16.2 16.2 16.2 ZONYL TBS2 O.lS - 0,05 ZONYL FSK 0.05 0.1 0.07 :
~ 60% t-butyl acrylate/20~ acrylic acid/20Y, PDMS macromer, having a weight average molecular weight of about 800,000.
2 ZONYL TBS, an anionlc surfactant suppl ied by DuPunt, con-taining 30-35% perfluoralkyl sulfonic acid ammonium salt, I ; 2.4~ acetic acid~a!nd 65X-70% water.
Prepared as in Examples I-XVI.
Examples XXIII-XXV
Example Example Example - ~ ~ XXIII XXIV XXVInqredient (Wt %) ~Wt %) (Wt %) Ethanol, 200 proof 78.9 79.4 78.2 Isopropanol 10.4 10.4 11.2 ;

wV 93/0370~ Pcr/uss~/0697s ~llSl''~

Hair Styling Polymer1 2.6 2.6 2.8 AMP 0.2 KOH (45%~ 0.6 0.4 0.5 DRO Water 7.0 7.0 7.0 FLUORAD FC-120 9.1 0.1 0/2 ZONYL FSK 0.05 0.05 0,09 ZONYL T8S 0.07 Fragrance 0.07 0.03 1 60% t~butyl acrylate/20% acry1ic acid/20% sl1tcone macromer, haviny a wcight average molecular we~ght of about 860,000 (Example XXIII), and 1.5 m~llion (Example XXIV); and 1.7 milllon (Example XXV).
Prepared as in Examples IX-X~I.
EXAMPLE XXV~
A hair spray concentrate composition, of the present inven-tion, which is suitable for aerosol dispensers, is prepared as follows:
Inqredient ~ ÇI9 Ethanol, 200 proof 95.8 Hair Styling Polymer~ 3.0 KOH 0.6 AMP 0.4 ZONYL FSK 0.25 60% t-butyl acrylate/20X acryl ic acid/20% sil icone macromer, having average molecul:ar weight of about 690,000, 2 ZONYL FSK supplied by DuPont, containing 40~ mono- andbis-fluoroalky 1 phosphates, an~Tonium . salt1 complexed with aiiphatic quaternary methosulfate, 15% isopropyl alcohol and 40-45% water.
Prepared as in Examples l-XVI. The concentrate is packaged in a conventional aerosol spray can and char~ed with a conven-tional liquifiable propellant at a propellant:conccntrate weight ratio of 30:70.

~ .:

W o 93/03704 2 1 1 ~ 1 5 I P~/US92/0697s Examples XXVII-XXX

Inqredient (wt.%) XXVII XXVIII XXIX ~
Ethanol, 200 proof 79.3 80.1 79.3 79.5 Isopropanol 10.4 10.4 10.4 10.4 Hair Styling Polymer1 2.6 - - -Hair Styling Polymer2 - 1.8 Halr Styl~ng Polymer3 - - 2.0 Hair Styl~ng Polymer4 - - - 1.8 KOH (10% aqueous solution) - - 1.2 1.2 HCl (10% aqueous solution) 0.6 0.6 DRO Water 7.0 7.0 7.0 7.0 Potassi~m Chloride 0.10 0.10 0.10 0.10 ' 15X t-butylaminoethylmethacrylate/15% t-butylacrylamide/70 ethylmethacrylate, having a weight average molecular weight of ahout 1.2 million.
2 }5X t-butylaminoethylmethacrylate/15% t-butylacrylamide/60 ethylmethacrylate/10% PDMS~ macromer (weight average molecular weight of about lO,OOOJ, having a weight average molecular weight of about 1.2 million.
3 15% N~N dimethylacrylamide/70% isobutylmethacrylate/15 acrylic acid, having a weight average molecular weight of about 1.2 million.
4 15% N,N dimethylacrylamide/60X isobutylme~hacrylate/15%
acryl;ic -cid/10%~ PDMS~ macromer (weight average mol~cular weight o~ ~about 10,000), having a weight average molecular weight of about 1.2 million).
Prepared~as in Exa-ples I-XVI, except for Examples XXVII and XXVIII, the HCl ~is added as the neutralizer.
The above compositions will exhibit good sprayability and when applied to the hair, provide`good hair styling benefits.
In the above examples and the compositions hereof utilizing ;~ ~ silicone macromer-grafted styling resins, it can be desirab~e to purify the~styling resin by removing unreacted silicone-containing monomer and silicone macromer-grafted polymer with ~iscosities at ~:

WO g3/~370q PCI'/US92~06975 211S15~ - 36 -25~C of about 10,000,000 centistokes and less. This can be done, for the example, by hexane extraction. After drying the resin from 1ts reaction solvent hexane extraction of the react1On product can be performed by adding an excess of hexane to the reaction product and heating to near the Tg of the non-silicon~
portion of the polymsr. The mixture is held at this temperature with st~rring ~or about 30 minutes ~nd cooled t~-room t~mperature.
The hexane is removed by vacuum suct~on. Two more hexane extraction cycles are pr0fQrably conducted ~n the same manner as above. After the third cycle, res~dual hexane remaining with the product is removed by distillation and vacuum dry~ng.
Low molecular weight polysiloxane-containing monomer and po1ymer about 1 hour is so1ub~1~zed by the supercrit k al carbon dioxide and transported away from the remaining polymer via a transfer line, which is maintained at identical temperature and IS pressure as the extraction vessel. The extracted materials are collected in an extract~on vessel. Following extraction~ the system is depressurized and dry, extracted polymer is recovered from the extraction vessel.
In the above examples and the compositions hereof utilizing silicone macromer-grafted styling resins, the resin can be purified by removing unreacted silicone-containing monomer and silicone macromer-grafted polymer with viscosities at 25-C~ o~
about 10,000,000 centistokes and less. This can be done, for the example, by hexane extraction. After drying the resin from its reaction solvent, hexane extraction of the reaction product can be performed by adding an excess of hexane to the reaction product and heating to near the Tg of the non-silicone portion of the polymer. The mixture is held at this temperature with stirring fbr about 30 minutes and cooled to room témperature. The!hexane is removed by vacuum suction. Two more hexane extraction cycles are preferably con~ucted in the same manner as above. After the third cycle, residual~hexane remaining with the product is remov~d by distillation and vacuum drying.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A liquid hair styling composition useful for spray application to hair, said composition comprising:
(a) an ionic hair styling polymer having a weight average molecular weight of at least about 300,000;
(b) a liquid vehicle selected from the group consisting of water, C1-C? monohydric alcohols, and mixtures thereof;
(c) an effective amount of an ionic strength modifier system for reducing viscosity of the composition, said system consisting essentially of a mixture of monomeric cations and monomeric anions, wherein said cations and anions are non-surface active and are at least partially soluble in said liquid vehicle;
said composition having a pH of about 10 or less.

2. A liquid hair styling composition as in Claim 1, com-prising from about 0.1% to about 15%, by weight, of said hair styling polymer, from about 80% to about 99.5%, by weight, of said liquid vehicle, and from about 0.01% to about 4%, by weight of said ionic strength modifier system.

3. A liquid hair styling composition as in Claim 2, wherein said monomeric cations are selected from the group consisting of monovalent metals, divalent metals, quaternary ammonium, and cationic amines.

4. A liquid hair styling composition as in Claim 3, wherein said cation is sodium, potassium, magnesium, or a mixture thereof.

5. A liquid hair styling composition as in Claim 3, wherein said monomeric anions are selected from the group consisting of chloride, sulfate, acetate, citrate, and nitrate.

6. A liquid hair styling composition as in Claim 5, wherein said anions are sulfate, acetate, chloride, or a mixture thereof.

7. A liquid hair styling composition as in Claim 1, wherein said ionic hair styling polymer has a weight average molecular weight of at least about 500,000.

8. A liquid hair styling composition as in Claim 1, wherein said ionic hair styling monomer comprises from about 2% to about 75% ionic monomers, and from about 25% to about 98% nonionic monomers.

9. A liquid hair spray composition as in Claim 8, wherein said ionic monomer is acrylic acid, methacrylic acid, dimethyl-aminoethyl methacrylate, quaternized dimethylaminoethyl meth-acrylate, maleic acid, half esters of maleic anyhydride, crotonic acid, itaconic acid, diallyldimethyl ammonium chloride, vinyl pydridine, vinyl imidazole, styrene sulfonate, or a mixture thereof.

10. A liquid hair spray composition as in Claim 9, wherein said nonionic monomer is selected from the group consisting of acrylic acid esters of C1-C24 alcohols, methacrylic acid esters of C1-C24 alcohols, styrene, polystyrene macromer, vinyl acetate, vinyl chloride, vinyl propionate, vinylidene chloride, alpha-methylstyrene, t-butylstyrene, butadiene, cyclohexadiene, ethylene, propylene, vinyl toluene, and mixtures thereof.

11. A liquid hair styling composition useful for spray application to hair, said composition comprising:
(a) an ionic hair styling polymer having a weight average molecular weight of at least about 300,000; said ionic hair styling polymer comprising silicone-containing monomers, wherein when the composition is dried, the hair styling polymer separates into a discontinuous phase which includes the silicone portion of said polymer and a continuous phase which includes the non-silicone portion;

(b) a liquid vehicle selected from the group consisting of water, C2-C4 monohydric alcohols, and mixtures thereof;
(c) an effecttve amount of an ionic strength modifier system for reducing viscosity of the composition, said system consisting essentially of a mixture of monomeric cations and monomeric anions, wherein said cations and anions are non-surface active and are at least partially soluble in said liquid vehicle;
said composition having a pH of about 10 or less.

12. A liquid hair styling composition is in Claim 11, wherein said polymer comprises at least about 0.5% of silicone macromer-containing monomers.

13. A liquid hair styling composition is in Claim 12, com-prising from about 5% to about 95% of ionic monomers and from about 5% to about 95% of nonionic monomers.

14. A liquid hair styling composition is in Claim 11, wherein said monomeric cations are selected from the group consisting of monovalent metals, divalent metals, quaternary ammonium, and cationic amines.

15. A liquid hair styling composition as in Claim 12, wherein said cation is sodium, potassium, magnesium, or a mixture thereof.

16. A liquid hair styling composition as in Claim 12 wherein said monomeric anions are selected from the group consisting of chloride, sulfate, acetate, citrate, and nitrate.

17. A liquid hair styling composition as in Claim 16, wherein said anions are sulfate, acetate, chloride, or a mixture thereof.

18 A liquid hair styling composition as in Claim 11, wherein said ionic hair styling polymer has a weight average molecular weight of at least about 500 000.

19. A liquid hair styling composition useful for spray application to hair, said composition comprising:
(a) an ionic hair styling polymer having a weight average molecular weight of at least about 300,000; said ionic monomer comprising silicone macromer-containing monomers having the formula:
X(Y)nSi(R)3-mZm wherein X is a vinyl group; Y is a divalent linking group; R is hydrogen, lower alkyl, aryl or alkoxy; Z is a monovalent silioxane polymeric moiety having a number average molecular weight of at least about 500; n is 0 or 1; and m is an integer from 1 to 3;
(b) a liquid vehicle selected from the group consisting of water, C2-C4 monohydric, alcohols, and mixtures thereof;
(c) an effective amount of an ionic strength modifier system for reducing viscosity of the composition said system consisting essentially of a mixture of monomeric cations and monomeric anions, wherein said cations and anions are non-surface active and are at least partially soluble in said liquid vehicle; said composition having a pH of about 10 or less.

20. A liquid hair spray composition is in Claim 19, wherein said silicone macromer-containing monomer is:

X-?-(CH2)q-(O)-p-Si(R )3-mZm wherein m is 1, 2, or 3, p is 0 or 1, q is an integer from 2 to 6, X is R1 is -H or - COOH, R2 is -H, -CH3, or CH2 COOH, R4 is alkyl, alkoxy, alkylamino, aryl or hydroxyl, and Z is wherein r is an integer from about 5 to about 700.

21. A liquid hair spray composition as in Claim 11, wherein said ionic monomer is acrylic acid, methacrylic acid, dimethyl-aminoethyl methacrylate, quaternized dimethylaminoethyl meth-acrylate, maleic acid, half esters of maleic anhydride, crotonic acid, itaconic acid, diallyldimethyl ammonium chloride, vinyl pyridine, vinyl imidazole, styrene sulfonate, or a mixture thereof.

22. A liquid hair spray composition as in Claim 21, wherein said polymer comprises about 15% to about 80% of said ionic monomer, about 50% to about 90% of nonionic monomer selected from the group consisting of acrylic acid esters of C1-C24 alcohols, methacrylic acid esters of C1-C24 alcohols, styrene, polystyrene macromer, vinyl acetate, vinyl chloride, vinyl propionate, vinyli-dene chloride, alphamethylstyrene, t-butylstyrene, butadiene, cyclohexadiene, ethylene, propylene, vinyl toluene, and mixtures thereof and about 2% to about 25% of said silicone-containing monomer.

23 A liquid hair spray composition as in Claim 20, wherein said ionic monomer is acrylic acid, methacrylic acid, dimethyl-aminoethyl methacrylate, quaternized dimethylaminoethyl meth-acrylate, maleic acid, half esters of maleic anhydride, crotonic acid, itaconic acid, diallyldimethyl ammonium chloride, vinyl pyridine, vinyl imidazole, styrene sulfonate, or a mixture thereof

24. A liquid hair spray composition as in Claim 22, wherein said polymer comprises about 15% to about 80% of said ionic monomer, about 50% to about 90% of nonionic monomer selected from the group consisting of acrylic acid esters of C1-C24 alcohols, methacrylic acid esters of C1-C24 alcohols, styrene, polystyrene macromer, vinyl acetate, vinyl chloride, vinyl propionate, vinyli-dene chloride, alphamethylstyrene, t-butylstyrene, butadiene, cyclohexadiene, ethylene, propylene, vinyl toluene, and mixtures thereof and about 2% to about 25% of said silicone-containing monomer.

A liquid hairspray product comprising a hairspray composition and a spray dispenser means for containing and spraying said composition, said composition being contained in said spray dispenser means, said hairspray composition comprising:
(a) an ionic, silicone macromer-containing hair styling polymer;
(b) a liquid vehicle selected from the group consisting of water, C1-C6 monohydric alcohols, and mixtures thereof, (c) an effective amount of an ionic strength modifier system for reducing viscosity of the composition, said system consisting essentially of a mixture of monomeric cations and monomeric anions, wherein said cations and anions are non-surface active and are at least partially soluble in said liquid vehicle;
said composition having a pH of about 10 or less and comprising from about 10% to about 90%, by weight, water, and from about 10% to about 80%, by weight, of said monohydric alcohols.

26. A liquid hairspray product as in Claim 25, comprising from about 0.1% to about 15%, by weight, of said hair styling polymer, from about 80% to about 99.5%, by weight, of said liquid vehicle selected from the group consisting of C2-C4 monohydric alcohols and water, and from about 0.01% to about 4%, by weight, of said ionic strength modifier system.

27. A liquid hairspray product is in Claim 26, wherein said nonomeric cations are selected from the group consisting of monovalent metals, divalent metals, quaternary ammonium, and cationic amines.

28. A liquid hairspray product is in Claim 27, wherein said cation is sodium, potassium, magnesium, or a mixture thereof.

29. A liquid hairspray product styling composition as in Claim 27, wherein said monomeric anions are selected from the group consisting of chloride, sulfate, acetate, citrate, and nitrate.

30. A liquid hairspray product as in Claim 29, wherein said anions are sulfate, acetate, chloride, or a mixture thereof.

31. A liquid hair styling composition is in Claim 12, comprising from about 5% to about 95% of ionic monomers and from about 5% to about 95% of nonionic monomers, wherein said polymer comprises at least about 0.5% of silicone macromer-containing monomers.

32. A liquid hairspray product as in Claim 31, wherein said ionic hair styling polymer monomer comprising silicone macromer-containing monomers having the formula:

X(Y)nSi(R)3-mZm wherein X is a vinyl group; Y is a divalent linking group; R is a hydrogen, hydroxyl, lower alkyl, aryl, alkylamino, alkaryl, or alkoxy; Z is a monovalent siloxane polymeric moiety having a number average molecular weight of at least about 500; n is 0 or 1;
and m is an integer from 1 to 3.

33. A liquid hairspray product as in Claim 32, wherein said ionic monomer is acrylic acid, methacrylic acid, dimethylamino-ethyl methacrylate, quaternized dimethylaminoethyl methacrylate, maleic acid, half esters of maleic anhydride, crotonic acid, itaconic acid, diallyldimethyl ammonium chloride, vinyl pyridine, vinyl imidazole, styrene sulfonate, salts of amines or acids above, or a mixture thereof.

34. A liquid hairspray product as in Claim 33, wherein said polymer comprises about 15% to about 80% of said ionic monomer, about 50% to about 90% of nonionic monomer selected from the group consisting of acrylic acid esters of C1-C24 alcohols, methacrylic acid esters of C1-C24 alcohols, styrene, polystyrene macromer, vinyl acetate, vinyl chloride, vinyl propionate, vinylidene chloride, alphamethylstyrene, t-butylstyrene, butadiene, cyclo-hexadiene, ethylene, propylene, vinyl toluene, and mixtures thereof and about 2% to about 25% of sa1d silicone-containing monomer.

35. A method for providing hair setting benefits to the hair, comprising spraying an effective amount of the composition of Claim 1 to hair.

36. A method for providing hair setting benefits to the hair, comprising spraying an effective amount of the composition of Claim 11 to hair.

37. A method for providing hair setting benefits to the hair, comprising spraying an effective amount of the composition of Claim 19 to hair.

38. A method for providing hair setting benefits to the hair, comprising spraying an effective amount of the composition from the product of Claim 25 to hair.