EP0991400A1 - Hair styling composition - Google Patents

Abstract

A hair styling composition is provided which is particularly suitable for use in the form of a mousse. The composition comprises up to 10 % by weight of an organic adhesive polymer and up to 5 % by weight of an ethoxylated alcohol having an aliphatic chain length of up to 16 carbon atoms and a degree of ethoxylation of from 3 to 20 ethoxy groups per mole, and a solvent such as water. The composition provides a foam which is stable at rest but which readily breaks down under shear to form a creamy liquid which can easily be worked into the hair.

Description

HAIR STYLING COMPOSITION

TECHNICAL FIELD

The present invention relates to a hair styling composition which provides flexible and good holding film texture. The invention relates, in particular to a hair styling composition in the form of a mousse.

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 styling 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. Furthermore, these styling compositions are formulated for additional purposes such as shampooing, conditioning, treating, dyeing, and combinations thereof.

A major desire by the consumer regarding performance of styling compositions has been the ability to hold the hair. Good hold has often been associated with strong and long styling and/or setting of the hair. However, it was also noticed that styling compositions having holding ability beyond a certain degree can also leave the hair feel rough, difficult to comb out, and can be difficult to remove upon shampooing. Further, in recent years, some consumers have expressed a desire to have hair styling products which can allow re-arrangement of hair without compromise to hair holding ability. As styling compositions with good holding ability commonly provide a rigid film texture, it was difficult to provide a composition with flexible film texture which would allow re-arrangement of hair. Thus, there is a desire to have hair styling compositions which have a good hold without compromise to ability to re-arrange hair, can provide supple, soft feeling to the hair, and can be removed easily from the hair upon shampooing.

It is also desired to have a hair styling composition in the form of a mousse which provides foams which have improved stability under rest but which undergo rapid collapse to form creamy liquids under shear.

SUMMARY OF THE INVENTION

Thus, the present invention provides a hair styling composition comprising by weight:

(a) up to about 10% of at least one organic adhesive polymer;

(b) up to about 5% of at least one surfactant comprising an ethoxylated alcohol having an alkyl chain length of up to about 16 carbon atoms and a degree of ethoxylation of from about 3 to about 20 ethoxy groups per mole; and

(c) a solvent.

The hair styling composition according to the invention may be in any suitable form for application to the hair such as mousses, gels, lotions or sprays. However, it is preferred for the composition to be in the form of a mousse additionally comprising a propellant.

DETAILED DESCRIPTION

The organic polymer (a) is present in the composition in an amount of up to about 10% by weight preferably up to about 5% by weight, more preferably from about 1 to 3% by weight and most preferably from about 2 to 2-5% by weight. The polymer may be any conventional organic styling polymer suitable for use as a hair fixitive including cationic, anionic, amphoteric and neutral- polymers. Cationic, anionic and amphoteric polymers are preferred. The ethoxylated alcohol (b) is present in an amount of up to about 5% by weight, most preferably from about 0- 1 to about 1 % by weight. The ethoxylated alcohol may be used as sole surfactant or in conjunction with a co-surfactant.

According to the present invention it has been found that improved foams are provided by incorporating a small amount of an ethoxylated alcohol in a hair styling composition including a styling polymer. The styling polymer is also incorporated in a small amount relative to conventional hair styling compositions.

It is known that surfactants stabilise the liquid wails or lamellae within foam structures. According to the invention . it has been found that the use of ethoxylated alcohols having a specified chain length and a specified degree of ethoxylation leads to enhanced stability of the lamellae. Furthermore, under conditions of shear, the foam collapses rapidly to leave a creamy liquid that can be rapidly applied to the hair for styling. The chain length of the parent alcohol and the degree of ethoxylation can be adjustedwithin the specified ranges to influence the ability of the surfactant to stabilise the lamellae under differing shear conditions.

The composition according to the invention is described in more detail in the following.

All percentages herein are by weight of the compositions unless otherwise indicated. All ratios are weight ratios unless otherwise indicated. The total of components except for propellant is hereinafter defined as a "concentrate". For non-aerosol products containing no propellant, the concentrate is equal to the entire composition. All percentages, ratios, and levels of ingredients referred to herein are based on the actual amount of the ingredient, and do not include solvents, fillers, or other materials with which the ingredient may be combined as commercially available products, unless otherwise indicated.

Any adhesive polymers suitable for application to the hair can be used as the- adhesive polymer in the present invention. These include but are not limited to honnopolymers and copolymers (including block copolymers and random copolymers) and silicone-containing polymers. As used herein, cc olymers refers to any polymers containing two or more different types of roπ- lers. Random copolymers are most commonly used. 5 The polymer may be an amphoteric polymer selected for ex -pie, from amongst the following polymers (1) to (5).

(1) Polymers of betainised dialkylaminoalkyl (meth)acrylate or dialkylaminoalkyl (meth)acryiamide containing at least units of the formula:

1 0 R¹ ( I )

cκ₂

I

CCO^" 20 wherein R¹ denotes a hydrogen atom or a methyl group, R² denotes an alkylene group having 1 to about 4 carbon atoms, Y denotes O or -NH- and R³ and R⁴ independently of one another denote hydrogen or alkyl having 1 to about 4 carbon atoms, and one cationic derivative consisting of a cationic surfactant containing 5 at least one nitrogen atom joined to one or more fatty chains and optionally quaternised, or consisting of a cationic polymer of the poiyamine, polyaminopolyamide or poly-(quatemary ammonium) type, the amine or ammonium groups forming part of the polymer chain or being joined thereto. These polymers usually have a molecular weight of about 500 r sDout 2,000,000. 0 The amphoteric polymers containing units corresponding tc above formula

(I) are generally in the form of copolymers which contain, in ET _n to the units, of the above mentioned formula (I), at least units of the for us R^{x (} ID

I

- [CK₂ - C] - ^z i

I COOR³

wherein R¹ is as defined above and R⁵ represents an alkyl or alkenyl radical having from about 4 to about 24 carbon atoms or a cycloalkyl radical having from about 4 to about 24 carbon atoms. It is also possible to use terpolymers, tetrapolymers or pentapolymers which contain, in addition to the units (I) and (II) . defined above, units of the formula:

R¹ : ιιi)

- [CH- - C] -

C ' OOR 6⁵

wherein R⁶ preferably denotes an alkyl or alkenyl group having 1 to about 3 carbon atoms and R¹ is as defined above. The units of the formula (I) are preferably present in an amount of 25 to 45% by weight, units of the formula (II) are preferably present in an amount of 5 to 65% by weight, and units of the formula (111) are preferably present in an amount up to 50% by weight, relative to the total weight of the polymer.

A preferred polymer is the copolymer containing units of the formulae (I), (II) and (III) in which Y denotes an oxygen atom, R² denotes the group -C₂H₄-, R¹, R³ and R⁴ denote methyl, R⁵ denotes an alkyl group having about 4 to about 18 carbon atoms and R⁶ denotes an alkyl group having 1 to about 3 carbon atoms. The average rnolecular weight of this polymer is preferably from about 70,000 to about 90,000. This polymer is sold under the trademark "Yukaformer" or "Diaformer" supplied by Mitsubishi Chemical Corporation.

(2) Polymers resulting from the copolymerisation of a vinyl monomer carrying^{^} a carboxyl group, such as acrylic acid, methacrylic acid, maleic acid or alphachloroacryiic acid, and a basic monomer which is a substituted vinyl compound containing at least one basic nitrogen atom, such as dialkylaminoalkyl methacrylates and acryiates and dialkylaminoalkylmethacrylamides and - acryiamides. (3) Polymers containing units derived from i) at least one monomer chosen from amongst acryiamides or methacrylamides substituted on the nitrogen by an alkyl radical, ii) at least one acid comonomer containing one or more reactive carboxyl groups, and iii) at least one basic comonomer, such as esters, with primary, secondary and tertiary amine substituents and quarternary ammonium substituents, of acrylic and methacrylic acids, and the product resulting from the quaternisation of dimethylaminoethyl methacrylate with dimethyl or diethyl sulphate.

The N-substituted acryiamides or methacrylamides which are most particularly preferred are the groups in which the alkyl radicals contain from about 2 to about 12 carbon atoms, especially N-ethylacryiamide, N-tert.-butylacrylamide, N-tert- octylacrylamide, N-octylacryiamide, N-decylacryiamide and N-dodecylacryiamide and also the corresponding methacrylamides. The acid comonomers are chosen more particularly from amongst acrylic, methacrylic, crotonic, itaconic, maleic and fumaric acids and also the alkyl monoesters of maleic acid or fumaric acid in which alkyl has 1 to about 4 carbon atoms.

The preferred basic comonomers are aminoethyl, butylaminoethyl, N,N'- dimethylaminoethyl and N-tert.-butylaminoethyl methacrylates.

(4) Crosslinked and alkylated polyaminoamides partially or totally derived from polyaminoamides of the general formula:

-[OC-R-CO-Z]- (I) wherein R represents a divalent radical derived from a saturated dicarboxylic acid... from a monocarboxylic or dicarboxylic aliphatic acid with an ethylenic double bond, or from an ester of a lower alkanol having 1 to about 6 carbon atoms and of these acids or of a radical derived from the addition of any one of the said acids onto a bis-primary or bis-secondary amine, and Z denotes a radical of a bis- primary or mono- or bis-secondary polyalkylene-polyamine, and preferably 5 represents: i) in proportions of about 60 to about 100 mol %, the radical -[NH-(CH₂)_χ-NH]- (II) wherein x is 2 and N is 2 or 3 or alternatively x is 3 and n is 2, this radical being derived from diethylenetriamine, triethylenetetramine or dipropylenetriamine; ι o ii) in proportions of 0 to about 40 mol %, the above radical (II) wherein x is 2 and n is 1 and which is derived from ethyienediamine, or the radical

/ \

-N N-

1 5

\— /

derived from piperazine; and iii) in proportions of 0 to about 20 mol %, the radical -NH-(CH₂)₆-NH-, derived 0 from hexamethylenediamine, these polyaminoamides being crosslinked by the addition of a difunctional crosslinking agent chosen from amongst epihalogenohydrins, diepoxides, dianhydrides, and bis-unsaturated derivatives, using about 0.025 to about 0.35 mol of crosslinking agent per amine group of the polyaminoamide, and being alkylated by reaction with acrylic acid, chloroacetic 5 acid or an alkane-sultone or their salts.

The saturated carboxyiic acids are preferably chosen from amongst acids having about 6 to about 10 carbon atoms, such as adipic acid, 2,2,4- and 2,4,4- trimethyladipic acids, terephthalic acid and acids with an ethylenic double bond, such as acrylic, methacryiic and itaconic acids. The alkane-sultones used in the alkylation are preferably propane- or butane- sultone, and the salts of the alkylating agents are preferably the sodium or potassium salts.

(5) Polymers containing zwitterionic units derived form the formula: R² R⁴

I I

I I

R¹- [-C-] -.-N" - ( CH, ) y- COO^"" i ^x i ^z i _ I -.

R R⁵ wherein R¹ denotes a polymerisable unsaturated group, such as an acrylate, methacrylate, acrylamide or methacrylamide group, x and y independently represent an integer from 1 to 3, R² and R³ independently represent hydrogen, methyl, ethyl or propyl, and R⁴ and R⁵ independently represent a hydrogen atom or an alkyl radical such that the sum of the carbon atoms in R⁴ and R⁵ does not exceed 10.

Highiy preferred amphoteric polymers include commercially available material such as octyiacrylamine/acryiates/butylaminoethyl methoacryiate copolymers with the tradenames; AMPHOMER, AMPHOMER LV71 , and AMPHOMER LV47 supplied by National Starch & Chemical, and methoacryloyl ethylbetaine/acrylates copolymers with the tradenames; YUKAFORMER SM, YUKAFORMER 301 , YUKAFORMER 510, YUKAFORMER M-75, and YUKAFORMER R250S supplied by Mitsubishi Chemical Corporation.

Anionic polymers useful in the present invention include polymers containing units derived from a carboxylic, sulphonic or phosphoric acid and usually have a molecular weight of about 500 to about 5,000,000. These polymers are water-soluble polymers, it being possible for this solubility to be obtained by neutralisation.

The carboxylic acid groups can be provided by unsaturated monocarboxylic or dicarboxylic acids, such as those corresponding to the formula: R 'A} -, - 0CK

\ / C=C

/ \

5 R² R^J

wherein n is 0 or an integer from 1 to about 10, A denotes a - -thylene group optionally joined to the carbon atom of the saturated group, c . the adjacent methylene group in the case where n is greater than 1 , via a - ,-eroatom, such ι o as oxygen or sulphur, R¹ denotes a hydrogen atom or a pheny. or benzyl group, R² denotes a hydrogen atom, a lower alkyl group or a carboxyl group and R³ denotes a hydrogen atom, a lower alkyl group, CH-COOH, or a phenyl or benzyl group.

Preferred anionic polymers containing carboxylic acid groups are:

15 (1 ) Hompolymers or copolymers of acrylic or methacrylic acid or salts thereof, and in particular, the products sold under the name VERSICOL E or K by BASF and under the name DARVAN No. 7 by Van der Bilt; acrylic acid/acrylamide copolymers sold in the form of their sodium salt under the name RETEN 421 , 423 or 425 by HERCULES; and the sodium salts of polyhydroxycarboxylic acids, sold 0 under the name HYDAGEN F by HENKEL

(2) Copolymers of acrylic or methacrylic acid with a monoethylenic monomer, such as ethylene, styrene, a vinyl or ailyi ester or acrylic or methacrylic acid ester, optionally grafted onto a poiyalkylene glycol, such as polyethylene glycol, and optionally corsslinked. Other such copolymers contain an optionally N-alkylated 5 and/or N-hydroxylated acrylamide unit in their chain, such as those sold under the name QUADRAMER 5 by American Cyanamid.

(3) Copolymers derived from crotonic acid, such as those containing, in their chain, vinyl acetate or propionate units and optionally other rmo ers such as allyl of methallyl esters, a vinyl ether or a vinyl ester of a i -rated linear or 0 branched carboxylic acid with a hydrocarbon chain of at leas arbon atoms, if appropriate, for these polymers to be grafted and corsslinked, r iso a vinyl, allyl or methallyl ester of an - or -cyclic carboxylic acid. Includeα in this class are those with the tradename RESYN 28-2930, 28-2913, and 28-1310 sold by National Starch & Chemicals

(4) Polymers derived from maleic, fumaric and itaconic acids or anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acryiic acid and its esters, such as those sold under the name GANTREZ A, SP, and ES by ISP Other polymers included in this class are copolymers of maleic, citraconic and itaconic anhydrides with an allyl or methallyl ester optionally containing an acrylamido or methacrylamido group, or with an -olefine, acrylic or methacrylic acid ester, acrylic or methacrylic acid or vinylpyrrolidone unit in their chain; the anhydride groups can be monoesteπfied or monσamidified.

(5) Polyacrylamides containing carboxylate groups. Polymers comprising sulphonic groups include polymers containing vinylsulphonic, styrenesulphonic, ligπosulphonic or naphthalenesulphonic units. These polymers are chosen, in particular, from amongst: i) Polyvmylsulphonic acid salts having a molecular weight of about 1 ,000 to about 100,000, and also copolymers with an unsaturated comonomer, such as acrylic or methacrylic acid or an ester thereof and also substituted or unsubstituted acrylamide or methacrylamide, vinyl esters, vinyl ethers and vinylpyrrolidone. ii) Polystyrenesulphonic acid salts, such as the sodium salt sold by National Starch & Chemicals under the name Flexan 500 and 130. lii) Alkali metal or alkaline earth metal salts of sulphonic acids derived from lignin, and more particularly calcium lignosuiphonates or sodium lignosulphonates, such as the product sold under the name Marasperse C-21 by Ameπcan Can Co. and the C₁₀ to C₁₄ products sold by Avebene. iv) Polymers containing salified alkylnaphthaleπesuiphonic acid units, such as the sodium salt under the name Darvan No. 1 by Van der Bilt. The anionic polymers herein which include anionic monomers are preferably utilised in at least partially neutralised form in order to aid shampoo removability of the liquid hair cosmetic compositions. In the compositions according to the present invention the neutralisation of a polymer may be achieved by use of an 5 inorganic base, preferably KOH. However organic base, preferably AMP (amino methyl propanol) and mixture of inorganic and organic base may also be used to effect the desired level of neutralisation in hair styling compositions according to the present invention. In total from about 50% to about 100%, preferably from about 70% to about 100%. most preferably from about 80% to about 100% of the ι o acidic monomers of each polymer utilised should be neutralised with base.

Any conventionally used base, organic or inorganic, may be used for neutralisation of acidic polymers provided they are utilised as specified herein. Hydroxides of alkali, alkaline earth and amino alcohols are suitable neutralisers for use in the present invention.

1 5 Examples of suitable organic neutralizing agents which may be included in the compositions of the present invention include amines, especially amino alcohols such as 2-amino-2-methyl-1 , 3-propanediol (AMPD), 2-amine-2ethyl-1 , 3- propanediol(AEPD), 2-amino-2-methyl-1-propanol (AMP), 2-amino-1-butanol(AB), monethanolamine (MEA), diethanolamine (DEA), triethanoiamine (TEA), 0 monoisopropanolamine (MIPA), diisopropanolamine (DIPA), triisopropanolamine (TIPA), dimethylsteramine (DMS) and amino methyl propanol (AMP) and mixtures thereof.

Preferred neutralising agents for use in hair styling compositions of the present invention are potassium and sodium hydroxides. 5 Highly preferred anionic polymers include commercially available material such as vinyl acetate/crotonic acid/vinyl πeodecanoate copolymers and vinyl acetate/crotonic acid copolymers with the tradenames RESYN 28-2930, RESYM_ 28-2913, and RESYN 28-1310 supplied by National Starch & Chemicals, and acrylates copolymers and acrylates/acrylamide copolymers with tradenames LUVIMER 100P, ULTRAHOLD 8, and ULTRAHOLD STRONG supplied by BASF Corporation.

Cationic polymers useful in the present invention include: (1) Vinylpyrrolidone / quatemized dialkylaminoalkyl acrylate or methacrylate copolymers such as those sold under the tradename Gafquat 734 and 755N by the Gaf Corp.

(2) Cellulose ether derivatives containing quaternary ammonium groups.

(3) Cationic polysaccharides. (4) Cationic polymers chosen from the group comprising: i) polymers containing units of the formula:

-A-Z¹-A-Z²- (I) wherein A denotes a radical containing two amino groups, preferably a piperazinyl radical, and Z¹ and Z² independently denote a divalent radical which is a straight- chain or branched-chain alkylene radical which contains up to about 7 carbon atoms in the main chain, is unsubstituted or substituted by one or more hydroxyl groups and can also contain one or more oxygen, nitrogen and sulphur atoms and 1 to 3 aromatic and/or heterocyclic rings, the oxygen, nitrogen and sulphur atoms generally being present in the form of an ether or thioether, sulphoxide, sulphone, sulphonium, amine, alkylamine, alkenylamine, beπzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol, ester and/or urethane group; ii) polymers containing units of the formula:

-A-Z^'-A-Z- (II) wherein A denotes a radical containing two amino groups, preferably a piperazinyl radical, and Z denotes the symbol Z³ and Z⁴ while denoting the symbol Z⁴ at least once; Z³ denotes a divalent radical which is a straight-chain or branched- chain alkylene or hydroxyalkylene radical having up to about 7 carbon atoms in the main chain, and Z⁴ is a divalent radical which is a straight-chain or branched- chain alkylene radical whicn has up to about 7 carbon atoms in the main chain, is unsubstituted and suDstituted by one or more hydroxyl radicals and is interrupted by one or more nitrogen atoms, the nitrogen atom being substituted by an alkyl chain having from 1 to about 4 carbon atoms, preferably 4 carbon 5 atoms, which is optionally interrupted by an oxygen atom and optionally contains one or more hydroxyl groups; and m) the alkylation products, with alkyl and benzyl halides of 1 to 6 carbon atoms, alkyl tosylates or mesylates, and the oxidation products, of the polymers of the formulae (I) and (II) indicated above under i) and ii). ι o (5) Polyamino-polyamides prepared by the polycondensation of an acid compound with a polyamine. The acid compound can be organic dicarboxylic acids, aliphatic monocarboxylic and dicarboxylic acids containing a double bond, esters of the abovementioned acids, preferably the esters with lower alkanols having from 1 to 6 carbon atoms, and mixtures thereof. The polyamine is a bis- 5 primary or mono- or bis-secondary polyalkylene-polyamine wherein up to 40 moi% of this polyamine can be a bis-primary amine, preferably ethylenediamine, or a bis-secondary amine, preferably piperazine, and up to 20 mol% can be hexamethylenediamine.

(6) The above mentioned polyamino-polyamides can be alkylated and/or 0 crosslinked. The alkylation can be carried out with glycidol, ethylene oxide, propylene oxide or acrylamide. The crosslinking is carried out by means of a crosslinking agent such as: i) epihalogenohydrins, diepoxides, dianhydrides, unsaturated anhydrides and bis-saturated derivatives, in proportions of about 0.025 to about 0.35 mol of 5 crosslinking agent per amine group of the polyamino-polyamide; ii) bis-halogenohydπns. bis-azetidinium compounds, bishalogeno acyldiamines and bis-(alkyl halides); iii) oligomers obtained by reacting a compound chosen -orn the group comprising bis-halogenohydrins, bis-azetidinium compounds, t -halogeπoacyl- diamines, bis-(alkyl halides), epihalogenohydrins, diepoxides an: is-unsaturated derivatives, with another compound which is a difunctional ;c~ ound which is

5 reactive towards the compound; and iv) the quaternisation product of a compound chosen from r— - compounds ii) and the oligomers iii) and containing one or more tertiary amine groups which can be totally or partially alkylated with an alkylating agent preferably chosen from methyl or ethyl chlorides, bromides, iodides, sulphates, mesylates and tosylates, ι o benzyl chloride or bromide, ethylene oxide, propylene oxide and glycidol, the crosslinking being carried out by means of about 0.025 to about 0.35 mol, in particular of about 0.025 to about 0.2 mol and more particularly of about 0.025 to about 0.1 mol, of crosslinking agent per amine group of the polyamiπo-polyamide.

(7) Polyamino-polyamide derivatives resulting from the condensation of a 15 polyalkylene-polyamine with a polycarboxylic acid, followed by alkylation by means of difunctional agents, such as the adipic acid/dialkylaminohydroxyaikyl- dialkyienetriamine copolymers in which the alkyl radical contains 1 to 4 carbon atoms and preferably denotes methyi, ethyl or propyl.

Useful polymers are adipic acid/dimethylaminohydroxypropyl- ₀ diethylenetriamine copolymers sold under the name Cartaretine F, F⁴ or F by SANDOZ.

(8) Polymers obtained by reacting polyalkylenepolyamine containing two primary amine groups and at least one secondary amine group, with a dicarboxylic acid chosen from diglycolic acid and saturated aliphatic dicarboxylic ₅ acids having about 3 to about 8 carbon atoms, the molar ratio r~ e polyalkylene- polyamine to the dicarboxylic acid being from about 0.8:1 to sr 1 1.4:1 , and the resulting poiyamide being reacted with epichlorohydrin ^~ molar ratio o_f epichlorohydrin to the secondary amine groups of the polyamide of from about 0.5:1 to about 1.8:1.

Useful polymers are those sold under the name HERCOSETT 57 by Hercules incorporated, and that sold under the name PD 170 or DELSETTE 101 by Hercules.

(9) Cyclic polymers generally having a molecular weight of about 20,000 to about 3,000,000 such as homopolymers containing, as the main constituent of the chain, units corresponding to the formula (III) or (IIP)

(CH₂)p (III)

/ \

(CH₂) t-R"C CR"-CH,- \ i ²

I I

H,C CH, \ /

N⁺ Y^"

/ \

R R' (CH₂)p (III' )

/ \

(CH_. ) t-R"C CR"-CH,- i i

I I

H₂ CH \ /

N

I i R

in which p and t are 0 or 1 , and p+r=1 , R" denotes hydrogen or methyl, R and R' independently of one another denote an alkyl group having from 1 to about 22 carbon-atoms, a hydroxylalkyl group in which the alkyl group preferably has 1 to about 5 carbon atoms, or a lower amidoalkyl group, and R and R' can denote, together with the nitrogen atom to which they are attached, heterocyciic groups such as piperidinyl or morpholinyl, and Y is bromide, chloride, acetate, borate,_. citrate, tartrate, bisulphate, bisulphite, sulphate or phosphate. Copolymers containing units of the formula III and III' may also contain units derived from acrylamide or from diacetoπeacrylamide.

Amongst the quaternary ammonium polymers of the type defined above, those which are preferred are the dimethyldiallylammonium chloride homopoiymer sold under the name MERQUAT 100 and having a molecular weight of less than about 100,000, and the dimethyldiallylammonium chloride/acrylamide copolymer having a molecular weight of more than about 500,000 and sold under the name MERQUAT 550 by CALGON Corporation.

(10) Poly-<quaterπary ammonium) compounds of the formula R¹ R⁵

I I

I I

- [ -N⁺ A N^" 3 - ] - 2X^" ( IV)

I I

R

Λ *5 _-_ wherein R , R , R , and R are independently aliphatic, alicyclic or arylaliphatic radicals containing a maximum of about 20 carbon atoms, or lower hydroxyaliphatic radicals, or alternatively, with the nitrogen atoms to which they are attached, heterocyclic rings optionally containing a second hetero-atom other than nitrogen, or alternatively R¹, R², R³, and R⁴ represent a group CH₂CHR'³R'⁴ wherein R'³ denoting hydrogen or lower alkyl and R'⁴ denoting SO, CN, CON(R^,6)₂, COOR'⁵, COR'⁵, COOR'⁷D, or CONHR'⁷D; R'⁵ denoting lower alkyl, R'⁶ denoting hydrogen or lower alkyi, R'⁷ denoting alkylene and D denoting a quaternary ammonium group; A and B independently represent a polymethylene group containing from about 2 to about 20 carbon atoms, which can be linear or branched, saturated or unsaturated and can contain, inserted in the main chain one or more groups -CH₂-Y-CH₂- wherein Y denotes benzene, oxygen, sulfur, SO. S0₂, SS, NR'⁸, N⁺(R'⁹)₂X¹-, CHOH, NHCONH, CONR'⁸, or COO; X^1" denoting an anion derived from a mineral or organic acid, R denoting hydrogen- or lower alkyl and R'⁹ denoting lower alkyl, or alternatively A and R¹ and R³ form a piperazine ring with the two nitrogen atoms to which they are attached. If A denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, B can also denote a group:-(CH₂)_n-CO-D-OC-(CH₂)_n-; wherein π is selected so that the molecular weight is generally between 1 ,000 and 5 100,000; and D denotes: i) a glycol radical of the formula -0-Z-0-, in which Z denotes a linear or branched hydrocarbon radical or a group corresponding to the fomuiae: -[CH₂-CH₂-0-]_χ-CH₂-CH₂- or -[CH₂-C(CH₃)H-0-]_y-CH₂-C(CH₃)H- wherein x and y denote an integer from 1 to about 4, representing a definite and unique degree ι o of polymerisation; ii) a bis-secondary diamine radical, such as a piperazine derivative; iii) a bis-primary diamine radical of the formula: -N-H-Y-NH-, in which Y denotes a linear or branched hydrocarbon radical or the divalent radical -CH₂-CH₂-S-S-CH₂-CH₂-; or 5 iv) a ureylene group of the formula -N-H-CO-NH-.

(11 ) Homopolymers or copolymers derived from acrylic or methacrylic acid and containing at least one unit:

R R¹¹ R¹ R¹

I 1 1 1 i1 1 1 0 - - CCHH-- --CC-- ( (VV)) C CHH₉₂ -- - CC-- ( (VV )) - - CCHH₂, --C C-- (V" ) 1 1 1

1 1 1

C=0 C=0 C=0

1 1 1

1 1

O O NH 5 1 1 1

1 1 1

A A A I 1 1

1

N R² - ⁺ -R⁴ R² -

/ \ 1 1 1 0 RR⁵³ RR⁶° RR^3J XX^"" RR^3J X^"

wherein R¹ is H or CH₃, A is a linear or branched alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to about 4 carbon atoms, R , R and R⁴ independently denote an alkyl group having 1 to about 18 carbon atoms or a benzyl group, R⁵ and R° denote H or alkyl having 1 to about 6 carbon atoms and X denotes methosulphate or haiide, such as chloride or bromide.

The comonomer or comonomers which can be used typically belong to the 5 family comprising: acrylamide, methacrylamide, diacetone-acrylamide, acrylamide and methacrylamide substituted on the nitrogen by one or more lower alkyls, alkyl esters of acrylic and methacrylic acids, vinylpyrrolidone and vinyl esters.

Useful polymers are Quaternium 38, 37, 49 and 42 in the CTFA, acrylamide/beta-methacryloyloxyethyl-trime-thylammonium methosulphate ι o copolymers sold under the names Teten 205,210,220 and 240 by Hercules, and aminoethyiacryiate phosphate/acrylate copolymer sold under the name Catrex by National Starch & Chemicals, and the crosslinked graft cationic copolymers having a molecular weight of about 10,000 to about 1 ,000,000, and preferably of about 15,000 to about 500,000, and resulting from the copolymerisation of: at least one 5 cosmetic monomer, dimethylaminoethyl methacrylate, polyethylene glycol and a polyunsaturated crosslinking agent, such as those mentioned in the CTFA dictionary under the name AMODIMETHICONE, such as the product marketed as a mixture with other ingredients under the name DOW CORNING 929 cationic emulsion. 0 (12) Other cationic polymers which can be used are polyalkyleneimines, in particular polyethyleneimines, polymers containing vinylpyridine units or vinylpyridinium units in the chain, condensates of polyamines and of epichlorohydrin, poly-(quaternary ureylenes) and chitin derivatives.

Silicone-containing adhesive polymers that can be used include any polymers 5 containing one or more silicone portions and one or more adhesive carbon, chain- based portions, where upon drying of the solvent the product typically separates into a continuous phase and a discontinuous phase, wherein one of said phases. be any carbon, or other carbohydrate material, and provider the adhesive properties of the polymer. Preferably the silicone forms a disc -tinuous phase upon drying and the carbon or carbohydrate portion forms the c. :inuous phase. Alternately, the silicone-containing polymers can be in e -^'orm of block 5 copolymers wherein both portions form discontinuous phases. - '^'erred silicone- containing polymers are silicone grafted vinyl-backbone poiyme*-. such as those disclosed in EP 0 412 704, incorporated herein by reference, especially silicone grafted polymers comprising acrylic acid/t-butyl acrylate backbones.

Other adhesive polymers that can be used include, without limitation, ι o thermoplastic elastomeric polymers, such as those disclosed in PCT/US/07387 (WO 95/01384), incorporated herein by reference.

Highly preferred cationic polymers include commercially available material such as Polyquatemium 4 under the tradenames CELQUAT H100 and CELQUAT L200 supplied by National Starch & Chemicals, and Polyquatemium 11 under the 15 tradename GAFQUAT 755N supplied by ISP.

The surfactant component (b) of the composition according to the invention essentially comprises an ethoxylated alcohol having an aliphatic, preferably alkyl chain length of up to about 22 carbon atoms and a degree of ethoxylation of from about 3 to about 30 ethoxy groups per mole, corresponding to the following 0 structure:

CH₃ - (CH₂)_a - (OCH₂CH₂)_n - OH (I) where a has an average value of 1 to about 22, preferably and n has an average value of 3 to 30.

The aliphatic preferably alkyl chain length of the ethoxylated alcohol is ₅ preferably up to 16 carbon atoms, more preferably up to 1^ -arbon atoms and most preferably up to 12 carbon atoms. A Cg.^ ethoxyla** alcohol is most preferred. The degree of ethoxylation of the ethoxylated alcohol is preferably about 4 to 20, more preferably about 5 to 16, most preferably about 6 to 12 and with particular preferance about 7 to 9 ethoxy groups per mole.

The ratio of alcohol aliphatic chain length to degree of ethoxylation of the 5 ethoxylated alcohol is preferably from about 7:4 to 4:7, more preferably from about 6:4 to 5:6, with particular preferance from about 6:4 to 1 :1 and most preferably about 5:4.

Examples include, Cg.^ Pareth 8; C^.^ Pareth 8; and C^.^ Pareth 9.

A particularly preferred ethoxylated alcohol is Cg.^ Pareth 8. ι o The ethoxylated alcohol may be used alone or in conjunction with a co- surfactant. Examples of suitable co-surfactants include other nonionic surfactants which provide softness to the foam, when the composition is in the form of a mousse, such as polyxyethylene, a polyoxy propylene, and mixtures thereof. 15 Non-limiting examples of additional nonionic surfactants for use in the styling composition of the present invention are as follows:

( 1 ) Polyoxyethylene alkenyl ether having the following general structure; CH₃ - (CH₂)_b - CH = CH (CH₂)_C - (OCH₂CH₂)_n - OH (II) wherein b has an average value from 1 to 10, c has an average value from about 0 1 to about 10, n has an average value from about 2 to about 200;

(2) Polyoxypropylene polyoxyethylene alkyl or alkenyl or iso-alkyl or iso- alkenyl or dimethylpolysiloxane ether having the following general structure;

R¹ - [OCH (CH₃) CH₂]_χ - (OCH₂CH₂)_y - OH (III) wherein R¹ is selected from the group consisting of alkyl, alkenyl, iso-alkyl 5 alkenyl, and dimethylpolysiloxane derivatives, x has an average value from about 2 to about 100; and y has an average value from about 2 to about 100;

(3) Polyoxyethylene long chain alkyl fatty acid or benzene derivative ether having the following general structure; R² - (OCH₂CH₂)_n -OH (IV) wherein R is selected from the group consisting of castor oil triglyceride castorate, cholesterol, coconut oil triglyceride cocoate, alkyl phenol, glyceryl laurate, glyceryl oleate, glyceryl cocoate, glyceryl isostearate, glyceryl stearate, hydrogenated castor oil triglyceride hydrogenated castorate, hydrogenated lanolin, nonyl phenyl and dimethylpolysiloxane derivatives, and n has an average value from about 2 to about 200;

(4) Polyoxyethylene alkyl, or alkenyl ether having the following general structure; R³ - C (O) - (OCH₂CH₂)_n - O - C(O) -R⁴ (V) wherein R³ and R⁴ are independently selected from the group consisting of alkyl, iso-alkyl, and alkenyl, and n has an average value from about 2 to about 200;

(5) Polyoxypropylene alkyl, iso-alkenyl or long chain alkyl fatty acid ether having the following general structure; R⁵ - [OCH (CH₃) CH₂]_n OH (VI) wherein R⁵ is selected from the group, consisting of alkyl, iso-alkyl and alkenyl, and n has an average value of about 2 to about 200.

Solvents used in the present invention are selected depending on variables such as the remainder of components, viscosity, and desired foaming characteristic of the composition.

Non-limiting examples of solvents useful in the present invention are: water, lower alcohols having 1 to about 6 carbons such as ethanol and isopropanol, and polyhydric alcohols such as propylene glycol, hexylene glycol, glycerin, and propane diol, and mixtures thereof. For mousse compositions, the solvent comprises at least about 80% water, more preferably at least about 90% water. The solvent is preferably comprised at a level by weight of from about 60% to about 99%, more preferably from about 80 to about 99%, most preferably from about 85% to about 98% of the concentrate. OPTIONAL COMPONENTS

Optional components can be included in the hair styling compositions of the present invention, depending on the needs of the product. Non-limiting examples of such optional components include conditioning agents, preservatives, perfume, ultraviolet and infrared screening and absorbing agents, colorants, pH adjusters, dyes, vitamins, proteins, plant extracts, and nutrients. Conditioning agents

Conditioning agents may be comprised in the hair styling composition of the present invention. Suitable conditioning agents include fatty alcohols, fatty acids, hydrocarbons and siiicones including volatile and non-volatile silicone fluids preferably of low molecular weight.

The fatty alcohols useful herein are those having from about 10 to about 30 carbon atoms, preferably from about 12 to about 22 carbon atoms, and more preferably from about 16 to about 22 carbon atoms. These fatty alcohols can be straight or branched chain alcohols and can be saturated or unsaturated. Nonlimiting examples of fatty alcohols include decyl alcohol, undecyl alcohol, dodecyl, myristyl, cetyl alcohol, stearyi alcohol, isostearyl alcohol, isocetyl alcohol, behenyl alcohol, linalool, oleyl alcohol, cholesterol, c s-4- -butylcyclohexanol, myricy alcohol and mixtures thereof. Especially preferred fatty alcohols are those selected from the group consisting of cetyl alcohol, stearyi alcohol, isostearyl alcohol, oleyl alcohol, and mixtures thereof. The fatty acids useful herein are those having from about 10 to about 30 carbon atoms, preferably from about 12 to about 22 carbon atoms, and more preferably from about 16 to about 22 carbon atoms. These fatty acids can be straight or branched chain acids and can be saturated or unsaturated. Also included are diacids, triacids, and other multiple acids which meet the carbon number requirement herein. Also included herein are salts of these fatty acids. Nonlimiting examples of fatty acids include lauric acid, palmitic acid, stearic acid, behenic acid, arichidonic acid, oieic acid, isosteaπc acid, sebacic acid, and mixtures thereof. Especially preferred for use herein are the fatty acids selected from the group consisting of palmitic acid, steaπc acid, and mixtures thereof.

Hydrocarbons are useful herein as conditioning agents. Useful hydrocarbons 5 include straight chain, cyclic, and branched chain hydrocarbons which can be either saturated or unsaturated. The hydrocarbons preferably will have from about 12 to about 40 carbon atoms, more preferably from about 12 to about 30 carbon atoms, and most preferably from about 12 to about 22 carbon atoms. Also encompassed herein are polymeric hydrocarbons of alkenyl monomers, such ι o as polymers of C2-C6 alkenyl monomers. These polymers can be straight or branched chain polymers. The straight chain polymers will typically be relatively short in length, having a total number of carbon atoms as described above in this paragraph. The branched chain polymers can have substantially higher chain lengths. The number average molecular weight of such materials can vary widely, 5 but will typically be up to about 500, preferably from about 200 to about 400, and more preferably from about 300 to about 350. Also useful herein are the various grades of mineral oils. Mineral oils are liquid mixtures of hydrocarbons that are obtained from petroleum. Specific examples of suitable hydrocarbon materials include paraffin oil, mineral oil, dodecane, isododecane, hexadecane, 0 isohexadecane, eicosene, isoeicosene, tridecane, tetradecane, polybutene, polyisobutene, and mixtures thereof. Isododecane, isohexadeance, and isoeicosene are commercially available as Permethyl 99A, Permethyl 101 A, and Permethyl 1082, from Presperse, South Plainfield, NJ. A copolymer of isobutene and normal butene is commercially available as Indopoi H-100 from Amoco ₅ Chemicals. Preferred for use herein are hydrocarbon conditioning agents selected from the group consisting of mineral oil, isododecane, isohexadecane, polybutene, polyisobutene, and mixtures thereof. When included, these conditioning agents are comprised at a level by weight of from Ξ__oout 0.01% to about 2% of the concentrate.

Preservative

Hair styling compositions of the present invention can -_r- r comprise a preservative. Such preservative is preferably included at a leve ' weight of up to about 5%, more preferably up to about 3% of the concentratr-

Non-limiting examples of preservatives useful in the present invention are DMDM Hydantoin (dimethylol dimethyl hydantoin), Kathon CG, (mixture of methylchloro-isothiazolinone and methyl isothiazolinone), imidazolidinyl urea, phenoxyethanol, EDTA and its salts, benzyl alcohol, and parabens such as methyl paraben, propyi paraben, butyl paraben, and LiquaPar oil (mixture of isobutyl paraben, isopropyl paraben, and butyl paraben). Other Optional Components

Hair styling compositions of the present invention may further comprise a variety of optional components. Such optional components include; thickeners and viscosity modifiers such as diethanolamides of long chain fatty acids, sodium chloride, and sodium sulfate. ultraviolet absorbing agents such as octyl salicylate, pH adjusting agents such as citric acid, succinic acid, sodium hydroxide and triethanolamine, coloring agents, hair oxidizing agents such as hydrogen peroxide, perborate salts and persulfate salts, hair reducing agents such as thioglycolates, perfumes, perfume solubilizing agents such as polyethylene glycol fatty acid esters, sequestering agents, polymer plasticizing agents such as glycerin and propylene glycol. Such optional ingredients are typically included at a level by weight of up to about 20%, preferably up to about 10% of the concentrate. Hair Styling Compositions

The present invention encompasses a wide varie i hair styling compositions, including hair spray compositions, mousses, ar- j- setting tonics. In general, the compositions will be flowable, low viscosity : -.positions 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

5 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 o conventionally-known aerosol propellants may be used to propel the compositions.

A suitable propellant for use can be generally any liquifiabie 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, 5 butane and isobutane. Other suitable propellants are hydrofluorocarbons such as 1 ,2-difluoroethane (Hydrofluorocarbon 152A) supplied as Dymel 152A by DuPont. Other examples of propellants are dimethylether, nitrogen, carbon dioxide, nitrous oxide and atmospheric gas.

The hydrocarbons, particularly isobutane, used singly or admixed with other hydrocarbons are preferred.

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 liquifiabie propellants, the level of propellant is from about 10% to about 60% by weight of the total composition, preferably from about 15%) to about 50%) by weight of the total composition.

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 American National Can Corp.

Other suitable aerosol dispensers are those characterized by the propellant being compressed air which can be filled into the dispenser by means of a pump 5 or equivalent device prior to use. Such dispensers are described in U.S. Patents 4,077,441 , and 4,850,577, and in U.S. Serial No. 07/839,648, Gosselin et al., filed February 21 , 1992. Compressed air aerosol containers suitable for use are also currently marketed by The Procter & Gamble Company under their tradename VIDAL SASSOON AIRSPRAY® hair sprays. ι o 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. 15 Method of Making

The hair styling compositions of the present invention can be made using conventional formulation and mixing techniques. Preferably, a premix of the polymer and the solvent, is made first. The other ingredients can then be added with mixing to provide a homogeneous mixture. 0 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 methods generally involve 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 styie. The ₅ composition is then dried 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 30g 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 present invention is further illustrated by reference to the following Examples. The hair styling compositions are formulated as mousses by conventional techniques known in the art.

All the examples provided foams which were stable under rest for a long period of time but which, when subjected to shear, underwent rapid collapse to form creamy liquids which could easily and efficiently be worked into the hair.

(1) DOBANOL 91-8:- C9-11 Pareth 8 supplied by Shell

(2) DMDM Hydantoin:- dimethylol dimethyl hydantoin

(3) Fragrance Takasago 6397:- perfume supplied by Takasago

The Examples showed^'that the relative proportions of the pc mer and the ethoxylated alcohol can be adjusted to provide optimum foam p oerties.

Specifically, the foams resulting from the compositions of th- ixamples showed that increasing the polymer level from 2-0% (Examp- :o 2-25% ₅ (Example 2) and 2-5% (Example 3) while maintaining the same vel of ethoxylated alcohol provides a higher viscosity build and poore ■ actuation rate. Further, increasing the level of ethoxylated alcohol from 0-25% i, Example 4) to 0-5% (Example 5) 0-75% (Example 6) and 1 -0% (Example 7) while maintaining the same level of polymer results in increased foam "rubberiness" and stiffness ι o and the foam became harder to break under shear.

Claims

CLAIMS:

1. A hair styling composition comprising by weight:

(a) up to 10% of at least one organic adhesive polymer;

(b) up to 5% of at least one surfactant comprising an ethoxylated alcohol having an aliphatic chain length of up to 16 carbon atoms and a degree of ethoxylation of from 3 to 20 ethoxy groups per mole; and

(c) a solvent.

2. A hair styling composition according to Claim 1 which is in the form of a mousse additionally comprising a propellant.

3. A hair styling composition according to Claim 1 or 2, wherein the surfactant (b) comprises from 0-1 % to 1% by weight of the ethoxylated alcohol.

4. A hair styling composition according to any of Claims 1 to 3, wherein the surfactant comprises a Cg.^ ethoxylated alcohol having a degree of ethoxylation of 8 ethoxy groups per mole.

5. A hair styling composition according to any of Claims 1 to 4, wherein the polymer is selected from anionic, cationic and amphoteric organic adhesive polymers.

6. A harr styling composition according to any of claims 1 to 5, which comprises from 1% to 3% by weight of the at least one polymer (a).

7. A hair styling composition according to claim 6, which comprises up to % by weight of the at least one polymer (a).

8. A hair styling composition according to Claim 7, which comprises from % to 2-5%o by weight of the at least one polymer (a).