AU674340B2 - Hair conditioning shampoo - Google Patents

Description

OPI DATE 12/04/94 APPLN. ID 49285/93 IlllIII 1111111111111111111 111111111111 I AOJP DATE 07/07/94 PCT NUMBER PCT/US93/08823 I llllllllllllllllll AU9349285

'CT)

(51) International Patent Classification 5 International Publication Number; WO 94/06403 A61K 7/06, 7/50 Al (43) International Publication Date: 31 March 1994 (31.03.94) (21) International Application Number: PCT/US93/08823 (22) International Filing Date: 22 September 1993 (22.09.93) Priority data: 07/948,517 08/118,412 22 September 1992 (22.09.92) US 13 September 1993 (13.09.93) US (74)Agent: ANCEL, Richard, Colgate-Palmolive Company, 909 River Road, Piscataway, NJ 08855-1343 (US).

(81) Designated States: AU, BB, BG, BR, BY, CA, CZ, FI, HU, JP, KP, KR, KZ, LK, MG, MN, MW, NO, NZ, PL, PI, RO, RU, SD, SK, UA, VN, European patent (AT, BE, CH, DE, DK, ES, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OAPI patent (BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR, NE, SN, TD, TG).

Published illth international search report.

(71)Applicant: COLGATE-PALMOLIVE COMPANY [US/ US]; 300 Park Avenue, New York, NY 10022 (US).

(72) Inventors: REICH, Charles 413 Lincoln Avenue, Highland Park, NJ CHENG, Wei-Ming 531 Blue Ridge Avenue, Piscataway, NJ ROBBINS, Clarence, R. 1726 Woodfield Road, Martinsville, NJ (US).

PATEL, Amrit 35 Wetherhill Way, Dayton, NJ (US).

(54)Title: HAIR CONDITIONING SHAMPOO KI Z- 1i c~= (57) Abstract A hair conditioning shampoo in stable emulsion or suspension form comprising: 5 to 40 by weight of at least one anionic surfactant; (ii) 0.01 to 5 by weight of a vinyl-type cationic polymer, including a copolymer of acrylamide or a derivative thereof and a dialkyl (CI-C 5 diallyl ammonium salt; or a terpolymer of acrylamide, acrylic acid and dialkyl (CI-Cs) diallyl ammonium salt; or a copolymer of vinylimidazolium methochloride and vinyl pyrrolidone or mixtures thereof having a hair conditioning effect and a charge density ranging between 150 and 400; (iii) 0.1 to 10 by weight of at least one dispersed water-insoluble hair conditioning agent; (iv) 0.5 to 10 by weight of at least one dispersing agent which functions to stabilize the emulsion or suspension; and the remainder water.

WO 94/06403 PCT/US93/08823 1 HAIR CONDITIONING SHAMPOO BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to hair conditioning shampoo compositions which are useful to clean human hair while simultaneously conditioning it to render it more easily manageable (combable and relatively low static charge) after shampooing than if it had been washed with a conventional shampoo.

The Prior Art Hair conditioning shampoos are well known in the cosmetic art and are described in various patents and literature references.

Considerable past research underlies efforts to discover new and better conditioning agents for incorporation into hair shampoos to provide so-called "two-in-one" fo.-mulations which cleanse the hair as well as provide a hair conditioning effect. These efforts have proved problematic since the combination of hair conditioning agents with the conventional ingredients found in shampoos often results in unstable compositions. The properties of hair conditioning agents and the other ingredients in ,ypical shampoo formulations tend to be mutually antagonistic, rendering the simultaneous washing and conditioning of the hair difficult to achieve. Indeed, the haircleansing and hair conditioning properties of these "two-in-one" compositions are usually very inferior to those produced by the utilization of separate shampoo and conditioning formulations.

Among the conditioning agents currently employed in shampoo compositions are silicones and other water-insoluble conditioning agents such as oils, waxes and various polymers. Also utilized are a variety of cationic hair conditioning agents such as cationic quaternary synthetic and cellulose polymers, cationic polysaccharides, etc.

WO 94/06403 PC/US93/08823 2 It has been suggested, for example, to employ certain copolymers of acrylamide (or derivatives thereof) and dialkyl diallyl ammonium salts or terpolymers of acrylamide, acrylic acid and dialkyl diallyl ammonium salts as hair conditioning agents in shampoos. Exemplary of such teachings are U.S. Patent Nos.

4,832,872, 4,477,375 and 4,240,450. U.S. Patent Nos. 3,912,808, 3,986,825 and 4,027,008 disclose the use of these and similar polymers to modify the surface characteristics of hair in hair waving and straightening compositions, hair coloring compositions and hair bleaching compositions, respectively.

In U.S. Patent Nos. 4,719,104, 4,954,335 and 4,976,956, the use of certain dialkyl diallyl ammonium chloride polymers in combination with other agents in various hair treating compositions is taught.

1 5 Cationic hair-conditioning agents, especially those of mid-tohigh charge density, present a particularly difficult problem when incorporated in shampoo compositions since they tend to form complexes with the anionic surfactants normally employed in shampoos. This incompatibility of the differently charged agents would be expected to present serious problems in maintaining the stability of the final product, as well as mutually interfere with the intended action of each.

It is an object of the present invention to provide a novel hair conditioning shampoo containing a unique combination of a midto-high charge density cationic hair conditioning polymer and an anionic surfactant, which combination is not subject to the abovenoted disadvantages.

SUMMARY OF THE INVENTION These and other objects are realized by the present 3 0 invention which provides a hair conditioning shampoo in stable emulsion or suspension form comprising: 5 to 40% by weight of at least one anionic surfactant; (ii) 0.01 to 5% by weight of a vinyl-type cationic polymer, including a copolymer of acrylamide or a derivative thereof and at least 50% of a dialkyl (C1-C5) diallyl ammonium salt monomer; or a terpolymer of acrylamide, acrylic acid and a. least 30% of a dialkyl diallyl ammonium salt monomer; or a copolymer of at least vinyl imidazolium methochloride and vinyl pyrrolidone or WO 94/06403 PCT/US93/08823 3 mixtures thereof having a hair conditioning effect and a charge density ranging between 150 -and 400; (iii) 0.1 to 10% by weight of at least one dispersed waterinsoluble hair conditioning agent; (iv) 0.5 to 10% by weight of at least one dispersing agent which functions to stabilize the emulsion or suspension; and the remainder water.

DETAILED DESCRIPTION OF THE INVENTION The invention is predicated on the discovery that certain of the mid-to-high charge density vinyl-type copolymers, such as those copolymers of acrylamide or its derivatives and certain dialkyl diallyl ammonium salts (hereinafter "A-DADAA copolymers") or terpolymers of acrylamide, acrylic acid and dialkyl diallyl ammonium salts (hereinafter "AA-DADAA terpolymers") or copolymers of vinyl imidazolium methochloride and vinyl pyrrolidone, or combinations of these polymers, when incorporated in shampoos with dispersed water-insoluble hair conditioning agents, provide enhanced hair conditioning benefits significantly greater than that provided by other commonly employed "two-in-one" compositions.

The charge density of a cationic polymer is given by the formula: "Charge Density=Cation Molecular Weight/Number of Positive Charges" By this definition, a ratio that is lower numerically represents a higher charge density. Thus, the "Charge Density" of a cationic polymer is a numerical value representing the number of positive charges in a particular cationic polymer. The greater the number of positive charges in a cationic polymer of fixed cation molecular weight, the greater will be the "charge density" of the 3 0 polymer. However, since the charge density, as measured by the above ratio, is inversely proportional to the number of positive charges relative to the cation molecular weight, the greater the number of positive charges and hence the greater the charge density, the lower the numerical value of the above ratio. Thus, for example, a cationic polymer whose charge density as given by the above ratio is 150 will have a "greater" charge density greater number of positive charges per unit of cation molecular weight) than a polymer having a measured "charge density" of 200. By "mid charge density" is meant a charge density greater than 200 and less than 400, and by WO 94/06403 PCr/US93/08823 4 "high charge density" is meant a charge density ranging between 150 and 200.

It will be understood by those skilled in the art that any vinyl-type cationic polymer having a hair conditioning effect which can be crafted having a charge density ranging between 150 and 400 may be employed in the practice of the invention. Exemplary of such cationic polymers are dimethyldiallyl ammonium chloride/acrylamide copolymer containing at least dimethyldiallyl ammonium chloride monomer (Merquat 280TM, 1 0 which has a charge density of 179.5, and Calgon Corp.'s Merquat 0 TM, which has a charge density of 232.5); dimethyldiallyl ammonium chloride/acrylic acid/acryamide terpolymers containing at least 30% dimethyldiallyl ammonium chloride monomer (Calgon Corp.'s Merquat 3 3 30TM, which has a charge density of 304.5); and vinylimidazolium methochloride/vinyl pyrrolidone copolymers containing at least 30% vinylimidazolium (BASF's Luviquat HM552TM, which has a charge density of 255.5). Currently, the preferred cationic polymers are Merquat 550 and Luviquat HM 552.

The dispersing agent and the water-insoluble hair conditioning agent combine to lend stability to the final emulsion or suspension product, as well as lessen the effects of the mutual antagonism between the anionic and cationic components of the composition. The result is a stable "two-in-one" hair conditioning shampoo, wherein the normally incompatible hair cleansing component and conditioning agents can function free of interference from each other to achieve their full effect.

The following 14 C radiotracer studies using hair and wool swatches as substrates show that Polymer JR 400 (a quaternary ammonium derivative of hydroxyethyl cellulose) and Merquat 550, in the absence of water-insoluble silicone conditioning agents, bind to the same extent on keratin substrates. In the presence of dimethicone in a stable formulation, however, it is found that Polymer JR binding is decreased by 55%, while Merquat 550 binding was unaffected. The reason for this is not fully understood, but is 3 5 thought to be a function of charge density.

WO 94/06403 PCT/US93/08823 SHAMPOOS mg Polyquat/g Hair mg Polyquat/g Swatch Wool Swatch Merquat 550 0.086 0.006 0.784 0.119 Merquat 550 Si 0.069 0.016 0.820 0.057 Polymer JR 400 0.068 0.045 0.758 0.119 Polymer JR 400 Si 0.037 0.006 0.340 0.039 These are surprising and unexpected result since one would expect vinyl-type copolymers (such as Merquat 550) to bind to keratin substrates such as these to about the same extent as other common cationic polymeric hair conditioning agents (such as the cationic cellulosic polymers of the Polymer JR type) and thus would not be expected to provide superior conditioning.

1 0 Although the vinyl-type cationic polymers disclosed herein may be incorporated in the aqueous shampoo system in amounts ranging from about 0.01 to about 5% by weight, it is preferred to utilize an amount of such polymers in the range of from about 0.1 to about 2% by weight.

1 5 Any anionic surfactant commonly employed in shampoos may be utilized in the practice of the invention.

Suitable anionic detergents include those described in McCutcheon's Detergents and Emulsifiers, North American ed., published in 1984. Exemplary of these anionic detergents are alkyl sulfates, alkyl ether sulfates, ethoxylated and propoxylated alkyl ether sulfates containing 1 to 10 ethylene oxide or propylene oxide units per molecule and mixtures thereof wherein said alkyl groups contain 8 to 18 carbon atoms and may be unsaturated, alkyl ether sulfonates, alpha-olefin sulfonates, alkyl aryl sulfonates or 2 5 combinations thereof.

Whereas the amount of surfactant incorporated in the shampoo may vary from about 5 to about 40% by weight, it is preferred to employ from about 5 to about 30% by weight thereof.

Any of the well known water-insoluble hair conditioning 3 0 agents conventionally employed in aqueous shampoos may be used in conjunction with the vinyl-type cationic polymers described above in the practice of the invention. Exemplary of suitable waterinsoluble conditioning agents are silicones, aminosilicones, WO 94/06403 PCr/US93/08823 6 polyalkylenes and oxidized derivatives thereof, paraffins, petrolatums, microcrystalline waxes, C18-C36 (mixed) fatty acids and mixed triglycerides thereof and stearyl stearates (and other higher esters), as well as mixtures thereof.

The organosilicon compounds and the silicones that may be employed in the practice of the present invention include any of those which are hair conditioning agents intended for use in conditioning shampoos, various of which have been described in the patents mentioned hereinabove. They are preferably of non-volatile 1 0 types. It has been found that the polyalkyl and/or polyaryl siloxanes are effective, with polydimethyl siloxane (CTFA designation: "dimethicone") being especially preferred. Aminosilicones are also effective conditioning agents in the compositions of this invention, and are even more effective than are conventional silicones and, with respect to these aminosilicones, the present special types described herein are better yet. Thus, it is much preferred to utilize an aminosilicone of the formula:

R

1 c R

R

2 Si (Si-O) -(Si Si R x y I 6 I 1 I I

R

3 C13 R 4

R

7 wherein R 1

R

2

R

3

R

5

R

6 and R 7 are alkyls of 1 to 6 carbon atoms, and most preferably of 1 carbon atom each. R 4 is -R 8 -NH-CH2CH2- NH2, R 8 is alkylene of 3 to 6 carbon atoms and most preferably is an isobutyl group, y is an average number in the range of 1 to 10, more preferably less than 5 and most preferably 1, which is of an amine equivalent in the range of 4,000 to 60,000. Preferably, x is in the range of 200 or 300 to 10,000, more preferably 500 to 10,000 and most preferably 750 to 800 or 850, about 800, and y is in the range of 1 to 10, more preferably being less than 5 and most preferably being about 1. The amine equivalent of such aminosilicone is preferably in the range of 5,000 to 50,000, and more preferably 10,000 to 40,000. For the specific preferred aminosilicone utilized in the experiments reported herein, the molar percentage of amine is about 0.125, the degree of polymerization is about 800, x is WO 94/06403 PCF/US93/08823 7 797, y is one and the molecular weight is about 60,000 daltons.

Because molecular weights of high polymers sometimes vary, depending on the measurement technique utilized, it is suggested that primary reference should be to the formula for identification of the aminosilicones described, rather than placing primary reliance on the molecular weights provided.

The polyalkylenes that may be employed in the present invention as water-insoluble conditioning agents are preferably those of a molecular weight in the range of 1,000 to 5,000, more preferably 1,000 to 4,000 and most preferably 2,000 to 2,500, about 2,000.

Oxidized versions of these polyalkylene polymers may also be used which create larger hydrocarbons with terminal carboxyl groups.

Although the alkylenes of these polymers will usually be ethylene, it is within the scope of the present invention to employ polymers of hydrocarbons of 2 to 5 carbon atoms each, and preferably 2 to 3 carbon atoms, in which the molecular weight range may be from 1,000 to 10,000 or even more under some conditions. Usually, however, the polymers will be of ethylene and/or propylene, and almost always of ethylene.

Paraffins that may be utilized will normally be of chain lengths of 20 to 50 carbon atoms, and preferably 20 to 40 carbon atoms, and isoparaffins can be of chain lengths in the range of 12 to 16 carbon atoms, and preferably 13 to 14 carbon atoms. The petrolatums are petroleum jellies or mineral jellies which melt in the range of 38 0 C to 60 0 C and the microcrystalline waxes are of an average molecular weight in the range of about 500 to 800 (which is about twice that of the paraffins). C18-36 fatty acid triglycerides are higher triglycerides which are available from Croda Chemical Corporation under the tradename Syncrowax HGL-C. The CTFA designation for this material is C18-36 Acid Triglyceride. Stearyl stearate, which is representative of useful esters of both higher fatty alcohols and higher fatty acids, is available from Inolex Corporation as Lexol SS. This and related compounds such as other high fatty esters may also act as stabilizers for the shampoo composition, preventing settling out of components and phase separations.

Further examples of suitable water-insoluble conditioning agents are set forth in U.S. patent application Serial No. 07/507,335 WO 94/06403 PCZ/US93/08823 8 filed April 9, 1990, and U.S. Patent No. 4,997,641, the entire contents of both being incorporated herein by reference.

Although the water-insoluble conditioning agents can be incorporated in the shampoos of the invention in amounts ranging from about 0.1 to about 10% by weight, it is preferred to utilize from about 0.1 to about 5% by weight thereof.

It is essential to also employ a dispersing agent since many of the shampoo formulations of the invention require it in order to maximize the stability of the emulsion or suspension.

Suitable dispersing agents include long chain saturated primary aliphatic alcohols or derivatives thereof. Additionally useful dispersing agents include long chain acyl derivatives, long chain alkyl dimethyl amine oxides, cross-linked anionic synthetic polymers, polysaccharides or quaternized derivatives thereof.

Suitable long chain primary aliphatic alcohols which may constitute the dispersing agent in the shampoo of the invention are saturated compounds with the hydroxy group being terminally located. Such alcohols will normally be of a distribution of homologous alcohols and typically all are of even numbers of carbon atoms, averaging 24 to 45 carbon atoms (on a weight basis), preferably 28 to 42 carbon atoms, and more preferably about 30 to carbon atoms. When the average number of carbon atoms in the chain is less than 24, the desired effectiveness of such alcohols in the present formulations is decreased, with the stabilization, fiber conditioning and pearlescing actions being diminished. When such chain length is more than 45 carbon atoms, of an average of about 50 carbon atoms, such alcohols are not satisfactorily dispersible in the described compositions.

In addition to the aforementioned long chain alcohols, related compounds such as corresponding alkoxylated alcohols, corresponding fatty acids and long chain saturated primary alcohol esters nmay .e substituted, at least in part. Of such "derivatives," the alkoxylated alcohols are preferred, and the most preferred of these are the ethoxylated alcohols which will normally contain up to about 20 ethoxy groups per mole, about 10 to 20. However, the alcohols which are the preferred embodiments of the invention normally will be employed alone or in mixture with related compounds from the "derivatives" group, with the alcohol being the major proportion of the total "alcohol plus derivatives" content.

WO 94/06403 PCr/US93/08823 9 Examples of commercial materials which may be employed in the present compositions are those manufactured by Petrolite Corporation and sold through their Petrolite Specialty Polymers Group under the name UnilinTM Alcohols as described in the technical bulletin of the Petrolite Corporation entitled UnilinT M Alcohols copyrighted in 1985 and identified as SP-1040. Such alcohols may be 75 to 90%, 80 to 85%, of the commercial product, with the balance of such products being substantially all saturated hydrocarbons of corresponding chain lengths. In such products, the distribution curve for the alcohol is substantially bell-shaped, with no chain length of alcohol being more than 10% of the total content thereof and with the corresponding hydrocarbon content being of a substantially flat distribution curve, with about 1 or 2% of each of the hydrocarbons being present. Such distribution curves, as bar graphs, 1 5 are provided in the Petrolite bulletin mentioned above. The alcohols (and corresponding hydrocarbons) present will normally be of chain lengths such that at least 80% are in the range of 18 or 20 to 54 carbon atoms, with at least 80% being in the range of about 18 or to 44 carbon atoms for an alcohol averaging about 30 carbon atoms, and with at least 80% being in the range of about 28 or 30 to 54 carbon atoms when the alcohol averages about 40 carbon atoms.

Examples of the long chain primary alcohols are Unilin-425 alcohol which averages 30 carbon atoms in its chain, Unilin-550 alcohol which averages 40 carbon atoms in its chain, and Unilin-350 which averages about 26 carbon atoms in its chain. A derivative, Unithox- 550, is an ethoxylated such alcohol having an average of 40 carbon atoms in the alkyl chain, ethoxylated with up to 20 ethoxy groups, 13.

Suitable long chain acyl derivatives useful as dispersing 3 0 agents in the shampoos of the invention include those described in U.S. Patent No. 4,741,855, the entire content of which is incorporated herein by reference, ethylene glycol esters of fatty acids having from about 16 to about 22 carbon atoms. Other acyl derivatives which are useful are alkanolamides of fatty acids having from about 16 to about 22 carbon atoms, preferably about 16 to 18 carbon atoms, stearic monoethanolamide, stearic diethanolamide, stearic monoisopropanolamide, stearic monoethanolamide stearate, etc. Also useful are long chain esters of long chain fatty acids such as stearyl stearate, cetyl palmitate, etc.; glyceryl esters, glyceryl distearate; WO 94/06403 TPCr/US93/08823 and long chain esters of long chain alkanolamides, stearamide DEA distearate, stearamide MEA stearate, etc.

Additionally useful dispersing agents include the alkyl (C16- C22) dimethyl amine oxides, stearyl dimethyl amine oxide.

Cross-linked anionic synthetic polymers may also be used as dispersing agents in the practice of the invention. Exemplary of such polymers are polymers of acrylic or methacrylic acid or their derivatives or copolymers with other olefinic comonomers or olefinic compounds with a lipophilic side group or polymers of vinyl sulfonic acid or deriatives or copolymers thereof with other conventional monomers compatible with the objects of the present invention, i.e., polyvinyl sulfate or polystyrene sulfonate.

Useful dispersing agents also include polysaccharides as well as quaternized derivatives thereof, hydroxyethylcellulose or 1 5 methylcellulose, guar gum, xanthan gum or quaternary derivatives of the above such as Polymer JR or cationic guar gum.

Also suitable dispersing agents are the alkyl dimethyl amine oxides, the alkyl group having from about 8 to about 18 carbon atoms. Additional suitable dispersing agents are those described in U.S. Patent No. 4,997,641 and U.S. patent application Serial No.

07/507,335 filed April 9, 1990, the entire content and disclosure of each being incorporated herein by reference.

The shampoos herein may also contain a variety of nonessential optional components or adjuvants suitable for rendering 2 5 such compositions more acceptable to the consumer. These conventional adjuvants are well known to those skilled in the art and include those set forth in the Hartnett Patent No. 4,997,641.

To manufacture the present shampoo, no complex procedures have to be foll6wed, but to obtain best stability, viscosity 3 0 and appearance, and greatest conditioning activity, it will be desirable to form a dispersion of the water-soluble anionic detergent(s) and adjuvants in water at an elevated temperature such as 70 0 C to 95 0 C, melt together and/or dissolve lipophilic materials such as quaternary ammonium salt, hydrocarbons including 3 5 polyethylene, mineral oil, microcrystalline wax, petrolatum, paraffin and isoparaffin, long chain alcohol and/or "derivative," C18-36 fatty acids and/or triglyceride and higher fatty ester, stearyl stearate, to produce a melt or liquid mix at elevated temperature and admix the two mixes at such elevated temperature, after which heated WO 94/06403 PCT/US93/08823 11 silicone and/or aminosilicone may be admixed with the resulting mix (it may sometimes also be included with the lipophiles), with the various mixings taking place with the parts to be mixed being at appioximately the same temperature. It is sometimes desirable for the silicone or aminosilicone to be mixed in after the main premixing to promote better stability of the product. When adjuvants are present, those which are water-soluble and/or dispersible may be mixed in with the aqueous phase materials and those which 'are not water-soluble or dispersible in the aqueous medium may be blended in with the lipophilic materials such as the hydrocarbons, or in some instances may be added to the mixture of the hydrophilic and lipophilic materials either before or after cooling to room temperature. Normally, perfume will be added to the other mixed components after cooling to room temperature, but the silicone and/or aminosilicone will usually be added at elevated temperature and before such cooling. The perfume is added to the cooled composition to avoid losses thereof due to volatilizations of components and to prevent any degradation due to heating it. When the procedure described is not followed, as when the various components of the compositions are blended indiscriminately, less stable products can result which can separate on storage.

All percentages of components expressed herein, unless otherwise indicated, are by weight, based on the weight of the composition in which the component is present.

The invention is illustrated by the following non-limiting examples.

EXAMPLE 1 The above procedure was utilized to prepare the compositions tabulated below, it being noted that Examples 1-1 and 1-2 are comparative examples: WO 94/06403 PC/US93/08823 12 Formula Examples Ingredients Deionized Water Ammonium Lauryl S04 Sodium Deceth-3 Sulfate Cocediethanolamide Cocamidopropyl Betaine Polydimethylsiloxane 1 0 Polymer JR 400 Polymer JR 30M Guar Hydroxypropyltrimonium chloride Merquat 550 Luviquat HM552 Distearyldimonium chloride C20-40 Alcohol Sodium Dihydrogen Phosphate Perfume Preservative Sodium Cumene Sulfonate 1

QS

7.5 7.5 4.0 4.0 0.3 2

QS

7.5 7.5 4.0 4 0 3

Q,

7.

7.

4.

wt 4 5 QS 5 7.5 5 7.5 0 4.0 5

QS

7.5 7.5 4.0 6 15.0 15.0 7

QS

A I- 4.0 4.0 4.0 4.U 4.0 0.3 0.7 0.7 0.7 rA 1.0 U.J I.U 0.5 0.5 0.5 0.5 0.5 0.5 3.0 3.0 3.0 3.0 3.0 3.0 0.2 0.6 0.5 1.5 0.2 0.6 0.5 1.5 0.2 0.6 0.5 0.2 0.6 0.5 0.2 0.6 0.5 0.2 0.6 0.5 0.2 0.6 100.0 100.0 100.0 100.0 100.0 100.0 100.0

TOTAL

cationic copolymer of acrylamide and dimethyl diallyl ammonium chloride cationic copolymer of pyrrolidinone and 1-ethenyl-3-methyl-lH- 3 0 imidazolium chloride The following lists the above formulas in order of increasing conditioning: 1<2<5<3-<7<4<6 The following comb test was employed to assess the 3 5 conditioning effects of the various formulations of the examples herein: Virgin or bleached European hair was made into 3.5 g tresses and washed with 20% sodium lauryl sulfate solution. Each tress was treated with the desired conditioning shampoo for one WO 94/06403 PCIIIUS93/08823 13 minute, then rinsed one minute under running tap water set at 105 0 F. Three replicates were employed in the test for each shampoo.

Panelists were asked to rank the wet tresses in terms of ease of combing and then to assign a rating for each tress on a scale of one to ten, with ten being the easiest to comb. The results were analyzed using the Friedman test for ranking data and Fisher's PLSD method for rating differences at 95% confidence levels.

EXAMPLE 2 The above procedure was employed to formulate the 1 0 compositions set forth below, which illustrate the use suspending agents: Formula Examples wt (100% Active) of various InorHipnte i 4 7 R ~hlVYIV I CI V r 1 5 Deionized Water Ammonium Lauryl Sulfate Sodium Deceth-3 Sulfate Cocodiethanolamide Polydimethylsiloxane Polyethylene Merquat 550 Merquat 280 Merquat Plus 3330 Distearyldimonium chloride C20-40 Alcohol Glycol Stearate Laureth-23 Sodium Dihydrogen Phosphate Perfume Preservative

QS

10.0 5.0 4.0 4.0

QS

0.5 1.0 0.8 0.2 1.0 1.0 0.5 3.0 0.5 3.0 0.5 3.0 3.0 1.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 TOTAL acrylic acid-dimethyl diallyl ammonium chloride cationic copolymer cationic terpolymer of acrylamide, acrylic acid and dimethyl diallyl ammonium chloride

Claims (16)

1. (Amended) A hair conditioning shampoo in stable emulsion or suspension form comprising: 5 to 40% by weight of at least one anionic surfactant; (ii) 0.01 to 5% by weight of a vinyl-type cationic polymer having a hair conditioning effect and a charge density ranging between 150 and 400; (iii) 0.1 to 10% by weight of at least one dispersed water-insoluble hair conditioning agent selected from the group consisting of silicones, aminosilicones, polyalkylenes and oxidized derivatives thereof, paraffins, petrolatums, microcrystalline waxes, C18-36 (mixed) fatty acids and triglycerides thereof and mixtures thereof; (iv) 0.5 to 10% by weight of at least one dispersing agent which functions to stabilize the emulsion or suspension, said dispersing agent being a long chain saturated primary aliphatic alcohol or a derivative thereof having an average of 24 to 45 carbon atoms in _said chain; and the remainder water.

2. A hair conditioning shampoo according to claim 1, wherein said vinyl-type polymer is selected from the group consisting of dimethyldiallyl ammonium chloride/acrylamide copolymer containing at least 50% dimethyldiallyl ammonium chloride monomer; dimethyldiallyl ammonium chloride/acrylic acid/acryamide terpolymers containing at least 30% dimethyldiallyl ammonium chloride monomer; and vinylimidazolium methochloride/vinyl pyrrolidone copolymers containing at least 30% vinylimidazolium I i AMENDED SHEE T n' 1 I I methochloride.

3. A hair conditioning shampoo according to claim 1 containing 5 to 30% by weight of said surfactant.

4. A hair conditioning shampoo according to claim 1 containing 0.1 to 2% of said cationic copolymer or mixture thereof.

5. A hair conditioning shampoo according to claim 1 containing 0.1 to 5% of said dispersed water-insoluble hair conditioning agent.

6. A hair conditioning shampoo according to claim 1 containing 0.5 to 5% of said dispersing agent.

7. A hair conditioning shampoo according to claim 1 wherein said anionic surfactant is selected from the group consisting of alkyl sulfates, alkyl ether sulfates, ethoxylated and propoxylated alkyl ether sulfates containing 1 to 10 ethylene oxide or propylene oxide units per molecule and mixtures thereof wherein said alkyl groups contain 8 to 18 carbon atoms and may be unsaturated.

8. A hair conditioning shampoo according to claim 1 wherein said cationic copolymer is a copolymer of acrylamide and dimethyl diallyl nammonium chloride.

9. A hair conditioning shampoo according to claim 1 wherein said cationic polymer is a terpolymer of acrylamide, acrylic acid and dimethyl diallyl ammonium chloride.

A hair conditioning shampoo according to claim 1 wherein said cationic copolymer is a copolymer of vinylimidazolium methochloride and vinyl pyrrolidone.

11. A hair conditioning shampoo according to claim 1 wherein said dispersing agent functions to render said emulsion or 07 i'- I^T^ II 1 SEP 1994 dispersion pearlescent.

12. A hair conditioning shampoo according to claim 1 additionally containing shampoo adjuvants.

13. A hair conditioning shampoo according to claim 1 wherein said dispersing agent is an alcohol containing an average of 30 to carbon atoms in said chain.

14. A hair conditioning shampoo according to claim 1 wherein said hair conditioning agent is polydimethyl-siloxane.

A hair conditioning shampoo according to claim 1 wherein said hair conditioning agent is a polydimethyl-aminosilicone.

16. A hair conditioning shampoo according to claim 1 wherein said vinyl-type cationic polymer has a mid charge density greater than 200. "I jr~EtST INTERNATIONAL SEARCH REPORT Ini .onal Application No PCT/US 93/08823 A. CLASSIFICATION OF SUBJECI' MATTER IPC 5 A61K7/06 A61K7/50 According to International Patent Classification (IPC) or to both national classification and IPC B. FIELDS SEARCHED Minimum documentation searched (classification system followed by clasification symbols) IPC 5 A61K Documentation searched other than mimmum documentation to the extent that such documents are included in the fields searched Electronic data base consulted during the international search (name of data base and, where practical, search terms used) C. DOCUMENTS CONSIDERED TO BE RELEVANT Category' Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No. X FR,A,2 585 947 (JOHNSON PRODUCTS CO. INC.) 1,2,4-7, 13 February 1987 10,11 see the whole document P,X EP,A,O 522 755 (CALGON CORPORATION) 13 1-4,6,7, January 1993 9,11, 13-16,18 see the whole document Y US,A,4 832 872 (RICHARDSON-VICKS INC.) 23 1-8,11, May 1989 13,16,18 cited in the application see the whole document Further documents are listed in the continuation of box C. V Patent family members are listed in annex. Special categories of cited documents SSpecial categories of cited documen later document published after the international filing date document defining the general state of the art which is not or td to undrstand the prin conflict wior the underlying but considered to be of partacular relevance invention earlier document but published on or after the international document of particular relevance; the claimed invention filing date cannot be considered novel or cannot be considered to document which may throw doubts on priority caim(s) or involve an inventive step when the document is taken alone which is cted to establish the publication date of another Y document of paricular relevance; the claimed invention citation or other special reason (as specified) cannot be considered to involve an inventive step when the document referring to an oral disclosure, use, exhibition or document is combined with one or more other such docu- other means ments, such combination being obvious to a person skilled document published prior to the international filing date but in the art. later than the prnonty date claimed document member of the same patent family Date of the actual completion of the internatonal search Date of mailing of the international search report 29 November 1993 1 Name and mailing address of the ISA Authorized officer European Patent Office, P.B. 5818 Patentlaan 2 NL 2280 HV Rijswijk Tel. (+31-70) 340-2040, Tx. 31 651 epo nl, e G nal M Fax: (+31-70) 340-3016 Sierra Gonzalez, M Form PCT/ISA21O (econd shlet) (July 1992) page 1 of 2 INTE RNATIONAL SEARCH REPORT Intemn al Application No PCT/US 93/08823 C.(Continuation) DOCUMENTS CONSIDERED TO BE RELEVANT Category 'ICitation of doctumnt, with inidication, where appropriate, of the relevant pampgs Relevant to claim NO. PATENT ABSTRACTS OF JAPAN vol. 13, no. 461 (C-645)(3809) 18 October 1989 JP,A,01 180 813 (SHISEIDO) 18 July 1989 see abstract 1-8,11, 13,16,1i8 Forin PCT/ISA/1 (continuation o(seond sliact) (July 1992) page 2 of 2 INTERNA1IONAL MEARCH REPORT Infomaton n ptentfamly erncrsIntern. At Application No lnfomatn o paent amiy mmbI PCT/US 93/08823 Patent document Publication Patent family Publication cited in search report date member(s) date FR-A-2585947 13-02-87 NONE EP-A-0522755 13-01-93 AU-A- 1863792 07-01-93 CA-A- 2072328 29-12-92 US-A-4832872 23-05-89 NONE Form PCT/1SA/21 0 (patent family annax) (July 1992)