HK1084578A - Shampoo containing a cationic polymer and anti-dandruff particles - Google Patents

Description

Shampoo comprising cationic polymer and anti-dandruff particles

Technical Field

The present invention relates to a cleansing shampoo comprising anti-dandruff particles. More particularly, the present invention relates to shampoos comprising a cationic polymer having a charge density of at least 1.4meq/g and anti-dandruff particles.

Background

Shampoo compositions for cleansing hair which also comprise an antidandruff agent are well known. Among the preferred types of antidandruff agents are particulate crystalline antidandruff agents such as the heavy metal salts of sulfur, selenium disulfide and pyrithione. When these particles deposit on the scalp during use of the shampoo, they can alleviate dandruff symptoms. Therefore, a rinse-off shampoo composition that is capable of depositing an effective amount of anti-dandruff particles on the scalp is highly desirable.

Compositions for depositing solid particulate benefit agents onto hair or skin surfaces are known; however, deposition efficiency has not been satisfactory to date, requiring the use of an excess of solid particulate agent in the composition to affect delivery, or else a slight or unacceptable degree of benefit would be obtained. It is very difficult to effectively deposit and retain solid particulate benefit agents onto a surface from a composition used to clean or wash the surface, such as a shampoo or other personal cleansing product, which contains surfactants and other ingredients for dissolving, suspending and removing particulate and oily materials from the surface it has treated. Nevertheless, it would be highly desirable to provide beneficial effects and convenience by depositing anti-dandruff particles using a simple detergent composition.

Cleansing compositions comprising cationic polymers to enhance deposition of certain conditioning oils, such as silicone oils, are known to impart conditioning or lubricating properties to the treated surfaces thereof. However, these conditioning oils are limited in the range of physical, optical, and aesthetic benefits they provide. In addition, it is known that viscosity, particle size and other conditioning oil related factors can significantly affect their ability to deposit from cleansing components. It is also known to include solid particles into compositions containing cationic polymers; however, these particles are typically added to modify the appearance or stability of the composition itself and are not deposited on the treated surface along with the conditioning oil or cationic polymer. When solid particulate benefit agents are deposited from a detergent composition, currently available compositions suffer from ineffective deposition which requires the use of an excess of particulate agent or ineffective benefit delivery. Specific improvements to solid particulate benefit agents have also been attempted to improve their deposition efficiency or retention from rinse-off compositions; however, this approach has a negative impact on the intrinsic characteristics, availability, usability and cost of the solid particulate benefit agent used.

Thus, it would still be highly desirable to enable rinse-off compositions, preferably cleansing compositions, to contain and effectively deposit and retain anti-dandruff particles on the scalp. It has now been found that selected cationic polymers surprisingly enhance the deposition and retention of anti-dandruff particulate on the treated surface when used in the cleaning compositions of the present invention.

Summary of The Invention

The present invention relates to shampoo compositions comprising:

a) from about 5% to about 505% by weight of a detersive surfactant,

b) at least about 0.15% by weight of anti-dandruff particulate,

c) at least about 0.055% by weight of a cationic polysaccharide polymer having a molecular weight of about 10,000 to about 10,000,000 and a charge density of about 1.4meq/gm to about 7.0meq/gm, and

d) at least about 20.05% by weight of an aqueous carrier.

The invention also relates to methods of using the shampoo compositions.

These and other features, aspects, and advantages of the present invention will become apparent to those skilled in the art from a reading of the present disclosure.

Detailed Description

While the specification concludes with claims particularly pointing out and distinctly claiming the invention, it is believed that the present invention will be better understood from the following description.

The shampoo compositions of the present invention comprise a detersive surfactant, anti-dandruff particles, a cationic polymer, and an aqueous carrier. Each of these essential components and preferred or optional components will be described in detail hereinafter.

All percentages, parts and ratios are based on the total weight of the composition of the present invention, unless otherwise specified. All weights as they pertain to listed ingredients are based on the active level and, therefore, do not include solvents or by-products that may be included in commercially available materials, unless otherwise specified.

All molecular weights used in the present invention are weight average molecular weights expressed as grams/mole, unless otherwise indicated.

The term "charge density" as used herein refers to the ratio of the number of positive charges on the monomeric units making up the polymer to the molecular weight of said monomeric units. The charge density multiplied by the polymer molecular weight determines the number of positive charge sites for a given polymer chain.

In the present invention, "comprising" means that other steps and other ingredients which do not affect the end result can be added. The term includes the terms "consisting of and" consisting essentially of. The compositions and methods/processes of the present invention can comprise, consist of, or consist essentially of the essential elements and limitations of the invention described herein, as well as any additional or optional ingredients, components, steps, or limitations described herein.

The term "polymer" as used herein is intended to include materials polymerized from either one type of monomer or from two (i.e., copolymers) or more types of monomers.

The term "solid particles" as used herein refers to particles that are not liquids or gases.

As used herein, the term "suitable for application to human hair" means that the compositions or components thereof described are suitable for use in contact with human hair, scalp and skin without undue toxicity, incompatibility, instability, allergic response, and the like.

The term "water-soluble" as used herein means that the polymer is soluble in water in the present compositions. Generally, the solubility of the polymer at 25 ℃ is 0.1%, preferably 1%, more preferably 5%, most preferably 15%, wherein the percentages are based on 100% by weight of the water solvent.

All cited references are incorporated herein by reference in their entirety. The citation of any document is not an admission of its availability as prior art to the claimed invention.

A. Detersive surfactant

The shampoo compositions of the present invention include a detersive surfactant. Detersive surfactants are included to provide cleaning performance to the composition. The detersive surfactant component comprises, in order, an anionic detersive surfactant, a zwitterionic or amphoteric detersive surfactant, or a combination thereof. Such surfactants should be physically and chemically compatible with the essential components described herein, or not otherwise unduly impair product stability, aesthetics or performance.

Suitable anionic detersive surfactant components for use in the shampoo compositions of the present invention include those known for use in hair care or other personal care cleansing compositions. The concentration of anionic surfactant component in the shampoo compositions should be sufficient to provide the desired cleansing and lather benefits and is generally from about 5% to about 50%, preferably from about 8% to about 30%, more preferably from about 10% to about 25%, even more preferably from about 12% to about 22%, wherein the percentages are by weight of the composition 100%.

Preferred anionic surfactants suitable for use in the shampoo compositions of the present invention are alkyl and alkyl ether sulfates. These substances have the respective expression ROSO₃M and RO (C)₂H₄O)_xSO₃M, wherein R is an alkyl or alkenyl group having from about 8 to about 18 carbon atoms, x is an integer having a value of from 1 to 10, and M is a cation such as ammonium, alkanolamines such as triethanolamine, monovalent metal cations such as sodium and potassium, and polyvalent metal cations such as magnesium and calcium. The solubility of the surfactant will depend on the particular anionic detersive surfactant and the cation selected.

In the alkyl and alkyl ether sulfates, R has preferably from about 8 to about 18, more preferably from about 10 to about 16, even more preferably from about 12 to about 14 carbon atoms. The alkyl ether sulfates may typically be prepared as condensation products of ethylene oxide and monohydric alcohols having from about 8 to about 24 carbon atoms. The alcohol may be synthetic or derived from fats, such as coconut oil, palm kernel oil, tallow. Lauryl alcohol and straight chain alcohols derived from coconut oil or palm kernel oil are preferred. The above alcohols are reacted with from about 0 to about 10, preferably from about 2 to about 5, more preferably about 3 mole fractions of ethylene oxide, and the resulting mixture of molecular species having, for example, an average of about 3 moles of ethylene oxide per mole of alcohol is sulfated and neutralized.

Specific non-limiting examples of alkyl ether sulfates that can be used in the shampoo compositions of the present invention include the sodium and ammonium salts of cocoalkyltriethylene glycol ether sulfate, tallowalkyltriethylene glycol ether sulfate, and tallowalkylhexaoxirane sulfate. Highly preferred alkyl ether sulfates are those comprising a mixture of individual compounds wherein the compounds in the mixture have an average alkyl chain length of from about 10 to about 16 carbon atoms and an average degree of ethoxylation of from about 1 to about 4 moles of ethylene oxide.

Other suitable anionic detersive surfactants are those of the formula [ R¹-SO₃-M]Water soluble salts of organic sulfuric acid reaction products of (2), wherein R¹Is a straight or branched chain saturated aliphatic hydrocarbon group having from about 8 to about 24 carbon atoms, preferably from about 10 to about 18 carbon atoms; and M is a cation as described above. Non-limiting examples of such detersive surfactants are hydrocarbons of the methane series comprising iso-, neo-, and n-paraffins having from about 8 to about 24, preferably from about 12 to about 18, carbon atoms, and such as SO₃、H₂SO₄According to known sulphonation methods including bleaching and hydrolysis, to obtain the salt of the organic sulphuric acid reaction product. Preference is given to sulfonated C₁₀To C₁₈Alkali metal and ammonium salts of n-paraffins.

Other suitable anionic detersive surfactants are also the reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide, wherein, for example, the fatty acids are derived from coconut oil or palm kernel oil; sodium or potassium salts of methyl tauride fatty acid amides, wherein, for example, the fatty acid is derived from coconut oil or palm kernel oil. Other similar anionic surfactants are described in U.S. Pat. Nos. 2,486,921, 2,486,922 and 2,396,278, the description of which is incorporated herein by reference.

Other anionic detersive surfactants suitable for use in the shampoo compositions of the present invention are the succinate salts, examples of which include disodium N-octadecyl sulfosuccinate, disodium lauryl sulfosuccinate, diammonium lauryl sulfosuccinate, tetrasodium N- (1, 2-dicarboxyethyl) -N-octadecyl sulfosuccinate, the diamyl ester of sodium sulfosuccinate, the dihexyl ester of sodium sulfosuccinate, and the dioctyl ester of sodium sulfosuccinate.

Other suitable anionic detersive surfactants include olefin sulfonates having from about 10 to about 24 carbon atoms. In the context of the present invention, the term "olefin sulfonate" refers to a compound obtainable by: the alpha-olefin is sulfonated with uncomplexed sulfur trioxide and the acidic reaction mixture is subsequently neutralized under suitable conditions so that any sulfones formed in the reaction are hydrolyzed to give the corresponding hydroxy-alkanesulfonates. The sulphur trioxide may be liquid or gaseous and is usually, but not necessarily, diluted with an inert diluent, for example, liquid SO when used in liquid form₂Diluted with chlorinated hydrocarbons, or, when used in gaseous form, with air, nitrogen, gaseous SO₂And (4) diluting. The alpha-olefins from which the olefin sulfonates are derived are mono-olefins having from about 10 to about 24, preferably from about 12 to about 16 carbon atoms. Preferably, they are linear olefins. In addition to the actual olefin sulfonate and a portion of the hydroxyalkanesulfonate, the olefin sulfonate may also contain minor amounts of other materials, such as olefin disulfonate, depending on the reaction conditions, the proportions of the reactants, the nature of the olefin feedstock and impurities in the olefin feedstock as well as side reactions during sulfonation. Non-limiting examples of the above alpha olefin sulfonate mixtures are described in U.S. Pat. No. 3,332,880, the description of which is incorporated herein by reference.

Another class of anionic detersive surfactants suitable for use in the shampoo compositions is the β -alkoxy alkane sulfonates. These surfactants correspond to the formula

Wherein R is¹Is a straight chain alkyl group having from about 6 to about 20 carbon atoms, R²Is a lower alkyl group having from about 1 to about 3, preferably 1, carbon atoms, and M is a water soluble cation as described above.

Preferred anionic detersive surfactants for use in the shampoo compositions of the present invention include ammonium lauryl sulfate, ammonium laureth sulfate, triethylamine lauryl sulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate, triethanolamine laureth sulfate, monoethanolamine lauryl sulfate, monoethanolamine laureth sulfate, diethanolamine lauryl sulfate, diethanolamine laureth sulfate, sodium lauryl monoglyceride sulfate, sodium lauryl sulfate, sodium laureth sulfate, potassium lauryl sulfate, potassium laureth sulfate, sodium lauryl sarcosinate, sodium lauroyl sarcosinate, lauryl sarcosinate, cocoyl sarcosine, ammonium cocoyl sulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate, sodium lauroyl sulfate, potassium cocoyl sulfate, sodium lauryl sulfate, sodium cocoyl sulfate, ammonium lauryl sulfate, ammonium cocoyl sulfate, ammonium lauryl sulfate, sodium coco, Potassium lauryl sulfate, triethanolamine lauryl sulfate, monoethanolamine cocoyl sulfate, monoethanolamine lauryl sulfate, sodium tridecylbenzene sulfonate, sodium dodecylbenzene sulfonate, and combinations thereof.

Amphoteric or zwitterionic detersive surfactants suitable for use in the shampoo compositions of the present invention include those known for use in hair care or other personal care cleansing. The concentration of the amphoteric detersive surfactant described above is preferably from about 0.5% to about 20%, preferably from about 1% to about 10%, wherein the percentages are by weight of the composition 100%. Non-limiting examples of suitable zwitterionic or amphoteric surfactants are described in U.S. Pat. Nos. 5,104,646(Bolich Jr. et al), 5,106,609(Bolich Jr. et al), the descriptions of which are incorporated herein by reference.

Amphoteric detersive surfactants suitable for use in the shampoo compositions are well known in the art and include those surfactants broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, and phosphonate. Preferred amphoteric detersive surfactants for use in the present invention include cocoamidoethyl-N-hydroxyethyl acetate, cocoamidoethyl-N-hydroxyethyl diacetate, lauroamidoethyl-N-hydroxyethyl acetate, lauroamidoethyl-N-hydroxyethyl diacetate, and mixtures thereof.

Zwitterionic detersive surfactants suitable for use in the shampoo compositions of the present invention are well known in the art and include those surfactants broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight or branched chain, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and wherein one of the aliphatic substituents contains an anionic group, e.g., carboxy, sulfonate, sulfate, phosphate, and phosphonate. Zwitterionic detersive surfactants such as betaines are preferred.

The shampoo compositions of the present invention may further comprise an additional surfactant for combination with the anionic detersive surfactant component described hereinbefore. Suitable optional surfactants include nonionic surfactants. Any of the above surfactants known in the art for use in hair care or personal care products can be used, provided that the optional additional surfactant is also chemically or physically compatible with the essential components of the shampoo composition, or does not otherwise unduly impair product performance, aesthetics or stability. The concentration of the optional additional surfactant in the shampoo compositions of the present invention may vary depending upon the desired cleaning or lathering performance, the optional surfactant selected, the desired product concentration, the other components present in the composition, and other factors well known in the art.

Other non-limiting examples of anionic, zwitterionic, amphoteric or optionally additional surfactants suitable for use in the shampoo compositions are described in McCutcheon, "Emulsifiers and detergents", in the 1989 yearbook, m.c. publishing co, and U.S. patents 3,929,678, 2,658,072, 2,438,091, 2,528,378, the description of which is incorporated herein by reference.

B. Anti-dandruff granule

The compositions of the present invention comprise anti-dandruff particulate. The particles of the present invention preferably have a particle size of less than 300 μm. Typically, the particles have a diameter of from about 0.01 μm to about 80 μm, more preferably still from about 0.1 μm to about 70 μm, and even more preferably from about 1 μm to about 60 μm. Non-limiting examples of suitable anti-dandruff particulate include: pyrithione salts, selenium sulfide, particulate sulfur, and mixtures thereof. Pyrithione salts are preferred.

1. Pyridinethione salts

Pyrithione anti-dandruff particles, especially 1-hydroxy-2-pyridinethione salts, are highly preferred particulate anti-dandruff agents for use in shampoo compositions of the invention. The concentration of the pyrithione anti-dandruff particulate is typically from about 0.1% to about 4%, preferably from about 0.1% to about 3%, most preferably from about 0.3% to about 2%, wherein the percentages are by weight of the composition of 100%. Preferred pyrithione salts include those formed from heavy metals such as zinc, tin, cadmium, magnesium, aluminum and zirconium, preferably zinc, more preferably the zinc salt of 1-hydroxy-2-pyrithione (known as "zinc pyrithione" or "ZPT"), most preferably 1-hydroxy-2-pyrithione salts in the form of platelet particles having an average size of up to about 20 μ, preferably up to about 5 μ, most preferably up to about 2.5 μ. Salts formed from other cations such as sodium are also suitable for use in the present invention. Pyrithione antidandruff agents are described, for example, in U.S. patents 2,809,971, 3,236,733, 3,753,196, 3,761,418, 4,345,080, 4,323,683, 4,379,753, and 4,470,982, all of which are incorporated herein by reference. It is believed that when ZPT is used as the antidandruff agent particles in shampoo compositions of the invention, hair growth or regrowth may be enhanced or regulated or both, or hair loss may be reduced or inhibited, or hair will become thicker or more numerous.

2. Selenium sulfide

Selenium sulfide is a particulate anti-dandruff agent suitable for use in shampoo compositions of the invention,effective concentrations are from about 0.1% to about 4%, preferably from about 0.3% to about 2.5%, more preferably from about 0.5% to about 1.5%, wherein the percentages are by weight of the composition 100%. Selenium sulphide is generally considered to be a compound having one mole of selenium and two moles of sulphur, although it may also be a compound according to the general formula Se_xS_yWherein x + y is 8. The mean particle diameter of the selenium sulphide as measured by a pre-laser light scattering device (e.g. a Malvern 3600 instrument) is typically below 15 μm, preferably below 10 μm. Selenium sulfide compounds are described, for example, in U.S. Pat. No. 2,694,668, U.S. Pat. No. 3,152,046, U.S. Pat. No. 4,089,945, and U.S. Pat. No. 4,885,107, all of which are incorporated herein by reference.

3. Sulfur

Sulfur may also be used in shampoo compositions of the invention as a particulate antidandruff agent. Effective concentrations of particulate sulfur are typically from about 1% to about 4%, preferably from about 2% to about 4%, wherein the percentages are by weight of the composition 100%.

Other antimicrobial actives

In addition to the antimicrobial active selected from pyrithione salts, selenium sulfide, particulate sulfur, and mixtures thereof, the present invention may further comprise one or more fungicidal or antimicrobial actives. Suitable antimicrobial actives include coal tar, sulfur, whitfield's ointment, castellani's pigment, aluminum chloride, gentian violet, octopirox (octopirox), ciclopirox, undecylenic acid and its metal salts, potassium permanganate, selenium sulfide, sodium thiosulfate, propylene glycol, bitter orange oil, urea preparations, griseofulvin, 8-hydroxyquinoline chloroiodoxyquinoline, thiodibazole, thiocarbamates, haloprogin, polyalkenes, hydroxypyridinone, morpholine, benzylamine, allylamines (e.g., terbinafine), tea tree oil, clove leaf oil, coriander, rose benorine, berberine, thyme red, cassia oil, cinnamaldehyde, citronellac acid, hinokitiol, ichthammol, Sensiva SC-50, eleesthp-100, azelaic acid, lysozyme, iodopropynyl butyl carbamate (IPBC), isothiazolinones such as octyl isothiazolinone and azoles, and combinations thereof. Preferred antimicrobial agents include itraconazole, ketoconazole, selenium sulfide and coal tar.

Azole compounds

Azole antimicrobials include imidazoles such as benzimidazole, benzothiazole, bifonazole, butoconazole nitrate, climbazole, clotrimazole, croconazole, eberconazole, econazole, elubiol, fenticonazole, fluconazole, flutrimazole, isoconazole, ketoconazole, lanoconazole, metronidazole, miconazole, nyconazole, omoconazole, oxiconazole nitrate, sertaconazole, sulconazole nitrate, tioconazole, thiazole, and triazoles such as terconazole and itraconazole, and combinations thereof. When present in the composition, the azole antimicrobial active is present in an amount of from about 0.01% to about 5%, preferably from about 0.1% to about 3%, and more preferably from about 0.3% to about 2%, wherein the percentages are 100% by weight of the composition. Ketoconazole is particularly preferred in the present invention.

Keratolytic agent

The present invention may further comprise one or more keratolytic agents such as salicylic acid.

Additional antimicrobial actives of the present invention may include Melaleuca extract (Melaleuca alternifolia) and charcoal. The present invention may also include a combination of antimicrobial actives. The compositions may include octopirox and zinc pyrithione compositions, pine tar and sulfur compositions, salicylic acid and zinc pyrithione compositions, octopirox and climbasole compositions and salicylic acid and octopirox compositions, and mixtures thereof.

C. Cationic polymers

The compositions of the present invention comprise cationic deposition polymers of sufficiently high cationic charge density to effectively enhance deposition of the anti-dandruff particulate component of the present invention. At the pH values of the shampoo compositions to be used, which are typically in the range of from about pH3 to about pH9, preferably between about pH4 and about pH8, suitable cationic polymers will have a charge density of at least about 1.4meq/gm, preferably at least about 1.7meq/gm, more preferably at least about 1.9meq/gm, and preferably less than about 7meq/gm, more preferably less than about 5 meq/gm. The average molecular weight of such suitable cationic polymers is generally between about 10,000 and 10,000,000, preferably between about 50,000 and about 5,000,000, more preferably between about 100,000 and about 3,000,000. As used herein, the term "cationic charge density" of a polymer refers to the ratio of the number of positive charges on the monomeric units making up the polymer to the molecular weight of said monomeric units. The cationic charge density multiplied by the polymer molecular weight determines the number of positive charge sites on a given polymer chain.

The concentration of the cationic polymer in the shampoo composition is from about 0.05% to about 3%, preferably from about 0.075% to about 2.0%, more preferably from about 0.1% to about 1.0%, wherein the percentages are by weight of the shampoo composition 100%. The weight ratio of cationic polymer to anti-dandruff particles (described below) in the shampoo composition is preferably from about 2: 1 to about 1: 30, more preferably from about 1: 1 to about 1: 20, and still more preferably from about 1: 2 to about 1: 10.

Cationic polymers useful in the compositions of the present invention include polysaccharide polymers, such as cationic cellulose derivatives and cationic starch derivatives. Suitable cationic polysaccharide polymers include those corresponding to the formula:

wherein A is an anhydroglucose residue, such as a starch or cellulose anhydroglucose residue; r is an alkylene oxide, polyoxyalkylene, or hydroxyalkylene group or combination thereof; r¹、R²And R³Independently an alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl, or alkoxyaryl group, each group containing up to about 18 carbon atoms, and each cationic portionTotal number of carbon atoms (i.e. R)¹、R²And R³The sum of the number of carbon atoms) is preferably about 20 or less; and X is an anionic counterion. Any anionic counter ion may be used in conjunction with the cationic polymers of the present invention, so long as the polymer remains soluble in water, the shampoo composition, or the coacervate phase of the shampoo composition, and so long as the counter ion is physically and chemically compatible with the essential components of the shampoo composition, or does not otherwise unduly impair product performance, stability, or aesthetics. Non-limiting examples of such counterions include halide (e.g., chloride, fluoride, bromide, iodide), sulfate, and methylsulfate. The degree of cationic substitution in these polysaccharide polymers is typically from about 0.01 to 1 cationic group per anhydroglucose unit.

Preferred is a cationic cellulose Polymer salt obtained by reacting hydroxyethyl cellulose with a trimethylammonium substituted epoxide, known in the industry (CTFA) as polyquaternium 10, available from Amerchol Corp, (Edison, n.j., USA) under the trade designation Polymer KG30M, having a charge density of 1.9 and a molecular weight of about 1,250,000.

The cationic polymer of the present invention is soluble in the shampoo composition or in a complex coacervate phase in the shampoo composition, the coacervate phase being formed from the cationic polymer and the anionic detersive surfactant component described above. Complex coacervates of cationic polymers can also be formed from other charged species in the shampoo composition.

Coacervate formation is dependent on various criteria such as molecular weight, component concentration and ratio of interacting ionic components, ionic strength (including changes in ionic strength, e.g., by addition of salts), charge density of cationic and anionic components, pH, and temperature. The coacervate systems and the effects of these parameters have been described, for example, in "ionic and Cationic Compounds in mixed systems" by J.Caelles et al,Cosmetics & Toiletriesvol.106, 4 months 1991, pages 49 to 54, C.J. van Os, "Coacervation, Complex-Coacervation and Flocculation",J. Dispersion Science and Technologyvolume 9(5, 6), 1988-89, pages 561 to 573, and "Practical Analysis of compact cobalt Systems" by D.J. Burgess, J.of colloid and Interface Science, volume 140, first phase, month 11 1990, pages 227 to 238, the description of which is incorporated herein by reference.

It is believed to be particularly advantageous for the cationic polymer to be present in the coacervate phase of the shampoo composition, or to form the coacervate phase when the shampoo is applied to or rinsed from the hair. Complex coacervates are believed to deposit more readily on hair. Thus, the cationic polymer is generally preferably present in the shampoo composition in the coacervate phase or forms a coacervate phase upon dilution.

Techniques for analyzing complex coacervate formation processes are known in the art. For example, microscopic analysis of the shampoo composition can be employed to identify whether a coacervate phase has formed at any selected stage of dilution. The coacervate phase described above will be considered as an additional emulsified phase in the composition. The use of dyes can assist in distinguishing the coacervate phase from other insoluble phases dispersed in the shampoo composition.

In the compositions of the present invention, it is believed that the tendency of the high charge density cationic polymer to form relatively large sized coacervates of from about 20 microns to about 500 microns, which can effectively bind or flocculate with the particles and enhance delivery to the hair, contributes to excellent deposition efficiency. Coacervates with cohesive characteristics evidenced by large, structured floes that dilute to retain a substantial amount of the particulate component and resist deflocculation when subjected to shear enhance deposition and retention of the particles on the hair.

D. Aqueous carrier

The compositions of the present invention include an aqueous carrier. The amount and type of carrier is selected based on compatibility with the other components and other properties desired for the product.

The carrier for use in the present invention comprises water and an aqueous solution of a lower alkyl alcohol. The lower alkyl alcohols useful in the present invention are monohydric alcohols having 1 to 6 carbon atoms, more preferably ethanol and isopropanol.

Preferably, the aqueous carrier is substantially water. Deionized water is preferably used. Water from natural sources containing mineral cations may also be used, depending on the desired characteristics of the product. Generally, the compositions of the present invention comprise from about 20% to about 99%, preferably from about 40% to about 98%, and more preferably from about 60% to about 98% of an aqueous carrier.

The pH of the compositions of the present invention is preferably from about 4 to about 9, more preferably from about 4.5 to about 7.5. Buffers and other pH adjusting agents may be added to achieve the desired pH.

E. Additional Components

The shampoo compositions of the present invention may also comprise one or more optional components known for use in hair care or personal care products, provided that the optional component is physically and chemically compatible with the essential components described herein, or does not otherwise unduly impair product stability, aesthetics or performance. The concentration of each of the aforementioned optional components ranges from about 0.001% to about 10%, wherein the percentages are by weight of the shampoo composition 100%.

Non-limiting examples of optional components for use in the shampoo compositions include cationic polymers, conditioning agents (hydrocarbon oils, fatty esters, silicones), suspending agents, viscosity modifiers, dyes, non-volatile solvents or diluents (water soluble and insoluble), pearlescent aids, foam boosters, additional surfactants or nonionic co-surfactants, pediculicides, pH adjusters, fragrances, preservatives, chelating agents, proteins, skin active agents, sunscreens, uv absorbers and vitamins.

Conditioning agent

Conditioning agents include any material used to provide a particular conditioning benefit to the hair and/or skin. In hair treatment compositions, suitable conditioning agents are those which deliver one or more benefits relating to shine, softness, combability, antistatic properties, wet handling, marring, finish, stickiness and greasiness. The conditioning agents for use in the shampoo compositions of the present invention typically comprise a water-insoluble, water-dispersible, non-volatile liquid which forms emulsified liquid particles or is solubilised by surfactant micelles in the anionic detersive surfactant component (as described above). Conditioning agents suitable for use in the shampoo compositions are those which are typically characterized as silicones (e.g., silicone oils, cationic silicones, silicone gums, high refractive silicones, and silicone resins), organic conditioning oils (e.g., hydrocarbon oils, polyolefins, and fatty esters) or combinations thereof, or those which additionally form liquid, dispersed particles in the aqueous surfactant base of the present invention. Such conditioning agents should be physically and chemically compatible with the essential components of the composition and should not unduly impair product stability, aesthetics or performance.

The concentration of the conditioning agent in the shampoo composition should be sufficient to provide the desired conditioning benefits and will be apparent to those of ordinary skill in the art. The above concentrations may vary with the conditioning agent, the desired conditioning performance, the average particle size of the conditioning agent particles, the type and concentration of other components, and other similar factors.

1. Siloxanes

The conditioning agent in the shampoo compositions of the present invention is preferably an insoluble silicone conditioning agent. The silicone conditioning agent particles can comprise volatile silicones, non-volatile silicones, or combinations thereof. Non-volatile silicone conditioning agents are preferred. If a volatile silicone is present, it will typically be included as a solvent or carrier for the ingredients of the non-volatile silicone material, such as silicone gums and resins in commercially available forms. The silicone conditioning agent particles may comprise a silicone liquid conditioning agent, and may also comprise other ingredients, such as including a silicone resin to improve silicone liquid deposition efficiency or enhance hair gloss, especially when high refractive index (e.g., above about 1.46) silicone conditioning agents are used (e.g., highly phenylated silicones).

The concentration of silicone conditioning agent is typically from about 0.01% to about 10%, preferably from about 0.1% to about 8%, more preferably from about 0.1% to about 5%, most preferably from about 0.2% to about 3%, wherein the percentages are 100% by weight of the composition. Non-limiting examples of suitable silicone conditioning agents and optional silicone suspending agents are described in U.S. reissue patent 34,584, U.S. patent 5,104,646 and U.S. patent 5,106,609, the descriptions of which are incorporated herein by reference. The silicone conditioning agents useful in the shampoo compositions of the present invention preferably have a viscosity of from about 20 to about 2,000,000 centistokes ("csk"), more preferably from about 1,000 to about 1,800,000 centistokes, even more preferably from about 50,000 to about 1,500,000 centistokes, most preferably from about 100,000 to about 1,500,000 centistokes, as measured at 25 ℃.

The dispersed silicone conditioning agent particles typically have a number average particle diameter of from about 0.01 μm to about 50 μm. For small particles applied to hair, the number average particle diameter is typically from about 0.01 μm to about 4 μm, preferably from about 0.01 μm to about 2 μm, more preferably from about 0.01 μm to about 0.5 μm. For larger particles to be applied to hair, the number average particle diameter is typically from about 4 μm to about 50 μm, preferably from about 6 μm to about 30 μm, more preferably from about 9 μm to about 20 μm, and most preferably from about 12 μm to about 18 μm. Conditioning agents having an average particle size of less than about 5 μm can be more effectively deposited on the hair. It is believed that the small size particles of conditioning agent are contained in a coacervate that forms between the anionic surfactant component (as described above) and the cationic polymer component (as described below) upon dilution with shampoo.

Background information on silicones, including discussion of silicone fluids, gums and resins, and silicone preparation, is described in Encyclopedia of Polymer Science and Engineering, Vol.15, second edition, p.204-308, John Wiley & Sons, Inc. (1989), which is incorporated herein by reference.

a. Silicone oil

The silicone fluid includes silicone oils, which are flowable silicone materials having a viscosity of less than 1,000,000 centistokes, preferably from about 5 centistokes to about 1,000,000 centistokes, more preferably from about 10 centistokes to about 100,000 centistokes, measured at 25 ℃. Silicone oils suitable for use in the shampoo compositions of the present invention include polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, polyether siloxane copolymers, and mixtures thereof. Other insoluble non-volatile silicone liquids having hair conditioning properties may also be used.

Silicone oils include polyalkyl or polyaryl siloxanes, which correspond to the following formula (III):

wherein R is an aliphatic group, preferably an alkyl or alkenyl group, or an aryl group, R may be substituted or unsubstituted, and x is an integer from 1 to about 8,000. Unsubstituted R groups suitable for use in shampoo compositions of the invention include, but are not limited to: alkoxy, aryloxy, alkaryl, aralkyl, arylalkenyl, alkylamino and ether substituted, hydroxy substituted and halogen substituted aliphatic and aryl groups. Suitable R groups also include cationic amines and quaternary ammonium groups.

The aliphatic or aryl groups substituted on the silicone chain can have any structure so long as the resulting silicone remains liquid at room temperature, is hydrophobic, is neither irritating, toxic nor otherwise harmful when applied to hair, is compatible with the other components of the shampoo composition, is chemically stable under normal use and storage conditions, is insoluble in the shampoo compositions of the present invention, and is capable of being deposited on and conditions the hair. The two R groups on the silicon atom of each monomeric siloxane unit may represent the same or different groups. Preferably, both R groups represent the same group.

The alkyl and alkenyl substituents are preferably C₁To C₅More preferably C₁To C₄Most preferably C₁To C₂Alkyl and chain ofAn alkenyl group. The aliphatic portion of other alkyl, alkenyl or alkynyl containing groups (e.g., alkoxy, alkaryl, and alkylamino) may be straight or branched chain, and is preferably C₁To C₅More preferably C₁To C₄Even more preferably C₁To C₃Most preferably C₁To C₂. As discussed above, the R substituent may also contain an amino functionality (e.g., alkylamino), which may be a primary, secondary or tertiary amine or a quaternary ammonium. These groups include mono-, di-and trialkylamino and alkoxyamino groups, with preferred aliphatic moiety chain lengths as described above. The R substituent may also be substituted with other groups such as halogens (e.g., chlorine, fluorine, and bromine), halogenated aliphatic or aryl groups, hydroxyl groups (e.g., hydroxyl-substituted aliphatic groups), and mixtures thereof. Suitable halo R groups may include, for example, trihalo (preferably trifuoro) alkyl groups such as-R¹CF₃Wherein R is¹Is C₁-C₃An alkyl group. Examples of such polysiloxanes include, but are not limited to, polymethyl 3,3, 3-trifluoropropyl siloxane.

Suitable R groups for use in the shampoo compositions of the present invention include, but are not limited to, methyl, ethyl, propyl, phenyl, methylphenyl and phenylmethyl. Specific non-limiting examples of preferred siloxanes include polydimethylsiloxane, polydiethylsiloxane, and polymethylphenylsiloxane. Polydimethylsiloxane is particularly preferred. Other suitable R groups include methyl, methoxy, ethoxy, propoxy, and aryloxy. The three R groups on the siloxane end-caps may represent the same or different groups.

Non-volatile polyalkylsiloxane fluids that may be used include, for example, low molecular weight polydimethylsiloxanes. These silicones can be obtained, for example, from the General Electric Company, the Viscasil R and SF 96 series, and the Dow Corning 200 series from Dow Corning. Polyalkylaryl siloxane fluids that may be used also include, for example, polymethylphenylsiloxane. These silicones may be available, for example, as SF 1075 methylphenyl fluid from General Electric Company, or as 556 cosmetic grade fluid from Dow Corning. Polyether siloxane copolymers that may be used include, for example, polypropylene oxide modified polydimethylsiloxanes (e.g., Dow Corning DC-1248), although ethylene oxide or mixtures of ethylene oxide and propylene oxide may also be used. The concentration of ethylene oxide and polypropylene oxide must be low enough to prevent dissolution in water and the compositions described herein.

Suitable alkylamino substituted silicones for use in the shampoo compositions of the present invention include, but are not limited to, those corresponding to the following general formula (IV):

wherein x and y are integers. This polymer is also known as "amino-terminated polydimethylsiloxane".

b. Cationic siloxanes

Cationic silicone liquids suitable for use in shampoo compositions of the invention include, but are not limited to, those conforming to the general formula (V):

(R₁)_aG_3-a-Si-(-OSiG₂)_n-(-OSiG_b(R₁)_2-b)_m-O-SiG_3-a(R₁)_a

wherein G is hydrogen, phenyl, hydroxy or C₁-C₈Alkyl of (a), preferably methyl; a is 0 or an integer having a value of 1 to 3, preferably 0; b is 0 or 1, preferably 1; n is a number from 0 to 1,999, preferably from 49 to 149; m is an integer from 1 to 2,000, preferably from 1 to 10; the sum of n and m is a number from 1 to 2,000, preferably from 50 to 150; r₁Is in accordance with the general formula CqH_2qA monovalent group of L, wherein q is an integer having a value of 2 to 8; and L is selected from the following groups:

-N(R₂)CH₂-CH₂-N(R₂)₂

-N(R₂)₂

-N(R₂)₃A^-

-N(R₂)CH₂-CH₂-NR₂H₂A^-

wherein R is₂Is hydrogen, phenyl, benzyl or a saturated hydrocarbon radical, preferably about C₁To about C₂₀And A-is a halide.

Particularly preferred cationic siloxanes according to formula (V) are the polymers known as "trimethylsilylaminopolydimethylsiloxanes" which are represented by the following formula (VI):

other silicone cationic polymers useful in shampoo compositions of the invention are represented by the general formula (VII):

wherein R is³Is C₁To C₁₈A monovalent hydrocarbon group of (a), preferably an alkyl group or an alkenyl group such as a methyl group; r₄Is a hydrocarbon radical, preferably C₁To C₁₈Alkylene or C₁₀To C₁₈Alkyleneoxy, more preferably C₁To C₈Alkenyloxy of (a); q^-Is a halide, preferably chloride; r is an average statistical value of 2 to 20, preferably 2 to 8; s is an average statistical value of 20 to 200, preferably 20 to 50. A preferred polymer of this type is known as UCARESILICONE ALE 56^TMAvailable from Union Carbide.

c. Silicone gums

Other silicone liquids suitable for use in shampoo compositions of the invention are insoluble silicone gums. These gums are polyorganosiloxane materials having a viscosity greater than or equal to 1,000,000 centistokes, measured at 25 ℃. Silicone gums are described in U.S. Pat. nos. 4,152,416; "Chemistry and Technology of Silicones" by Noll and Walter, New York: academic Press (1968); and General Electric silicon Rubber Product Data Sheets SE 30, SE 33, SE 54 and SE 76, all of which are incorporated herein by reference. The silicone gum will typically have a weight average molecular weight in excess of about 200,000, preferably from about 200,000 to about 1,000,000. Specific non-limiting examples of silicone gums for use in the shampoo compositions of the present invention include dimethicone, (dimethicone) (methylvinylsiloxane) copolymer, poly (dimethicone) (diphenylsiloxane) (methylvinylsiloxane) copolymer, and mixtures thereof.

d. High refractive index siloxanes

Other non-volatile insoluble silicone liquid conditioning agents suitable for use in the shampoo compositions of the present invention are those known as "high refractive index silicones" which have a refractive index of at least about 1.46, preferably at least about 1.48, more preferably at least about 1.52, most preferably at least about 1.55. The refractive index of the polysiloxane liquid will generally be less than about 1.70, typically less than about 1.60. In the context of the present invention, silicone "liquids" include oils as well as gums.

The high refractive index silicone fluid includes those represented by the above general formula (III), and cyclic silicones such as those represented by the following formula (VIII):

wherein R is as defined above and n is a number from about 3 to about 7, preferably from about 3 to about 5.

The high refractive index polysiloxane fluids contain an amount of aryl-containing R substituents sufficient to increase the refractive index to the desired level as described above. In addition, R and n must be selected so that the material is non-volatile.

IncludedSubstituents for aryl groups include those containing five-and six-membered aromatic rings including alicyclic and heterocyclic rings and those containing fused five-or six-membered rings. The aryl ring itself may be substituted or unsubstituted. Substituents include aliphatic substituents, and may also include alkoxy substituents, acyl substituents, ketones, halogens (e.g., Cl and Br), amines, and the like. Examples of aryl-containing groups include, but are not limited to, substituted or unsubstituted aromatic hydrocarbons, such as phenyl and phenyl derivatives, e.g. having C₁-C₅Alkyl or alkenyl substituted phenyl. Specific non-limiting examples include: allylphenyl, methylphenyl and ethylphenyl, vinylphenyl (e.g. styryl) and phenylalkyne (e.g. phenyl C)₂-C₄Alkyne of (ii). Heterocyclic aryl groups include, but are not limited to, substituents derived from furan, imidazole, pyrrole, pyridine, and the like. Examples of fused aromatic ring substituents include, but are not limited to, naphthalene, coumarin, and purine.

Generally, the high refractive index polysiloxane fluids will have a degree of substitution comprising aryl groups of at least about 15%, preferably at least about 20%, more preferably at least about 25%, even more preferably at least about 35%, most preferably at least about 50%. Typically, the degree of aryl substitution will be less than about 90%, more typically less than about 85%, preferably from about 55% to about 80%.

High refractive index polysiloxane liquids are also characterized by their aryl substitution resulting in higher surface tension. Generally, the polysiloxane liquid will have at least about 24 dynes/cm²Typically at least about 27 dynes/cm². Surface tension, for its use, can be measured by de Nouy ring tensiometer according to Dow Corning corporation eTest Method CTM 0461 (11/23 1971). The change in surface tension can be measured according to the test methods described above or according to ASTM Method D1331.

Preferred high refractive index polysiloxane fluids have phenyl or phenyl derivative substituents (most preferably phenyl) and alkyl substituents, preferably C₁-C₄Alkyl (most preferably methyl), hydroxy or C₁-C₄Alkylamino (especially with-R)¹NHR²A combination of NH2 wherein each R¹And R²Independently is C₁-C₃Alkyl, alkenyl and/or alkoxy) groups. High refractive index polysiloxanes are available from Dow Corning, HulsAmerica and General Electric.

When high refractive index silicones are used in the shampoo compositions of the invention, they are preferably used in solution with a spreading agent, such as a silicone resin or surfactant, to reduce the surface tension sufficiently to enhance spreadability and thus shine (after drying) of hair treated with the composition. Generally, the spreading agent is used in an amount sufficient to reduce the surface tension of the high refractive index polysiloxane liquid by at least about 5%, preferably at least about 10%, more preferably at least about 15%, even more preferably at least about 20%, most preferably at least about 25%. The reduction of surface tension by the silicone liquid/spreading agent mixture can improve the shine of the hair.

The spreading agent may also reduce the surface tension, preferably by at least about 2 dynes/cm²Preferably at least about 3 dynes/cm²Even more preferably at least about 4 dynes/cm²Most preferably at least about 5 dynes/cm²。

The surface tension of the mixture of silicone fluid and spreading agent is preferably less than or equal to about 30 dynes/cm at the proportions present in the final product²More preferably less than or equal to about 28 dynes/cm²Most preferably less than or equal to about 25 dynes/cm². Typically, the surface tension will be about 15 dynes/cm²To about 30 dynes/cm²More typically about 18 dynes/cm²To about 28 dynes/cm²And most typically about 20 dynes/cm²To about 25 dynes/cm²。

Typically, the weight ratio of highly arylated polysiloxane liquid to spreading agent will be from about 1000: 1 to about 1: 1, preferably from about 100: 1 to about 2: 1, more preferably from about 50: 1 to about 2: 1, most preferably from about 25: 1 to about 2: 1. When fluorinated surfactants are used, particularly high ratios of silicone liquid and spreading agent can be effective due to the efficiency of these surfactants. Thus, it is contemplated that ratios significantly higher than 1000: 1 may be used.

Silicone liquids suitable for use in shampoo compositions of the invention are disclosed in U.S. patent No. 2,826,551, U.S. patent No. 3,964,500, U.S. patent No. 4,364,837, british patent No. 849,433, and Silicon Compounds, petrich Systems, Inc (1984), which are all incorporated herein by reference.

e. Siloxane resins

Silicone resins may be included in the silicone conditioning agents of the shampoo compositions of the present invention. These resins are highly crosslinked polymeric siloxane systems. Crosslinking is introduced during the preparation of the silicone resin by blending trifunctional and tetrafunctional silanes with monofunctional or difunctional or both silanes. It will be apparent to those of ordinary skill in the art that the degree of crosslinking required to obtain a silicone resin will vary depending on the silane units specifically incorporated into the silicone resin. Generally, silicone materials having a sufficient level of trifunctional and tetrafunctional silane monomer units (and thus, a sufficient level of crosslinking) to become rigid or hard films upon drying are considered to be silicone resins. The ratio of oxygen atoms to silicon atoms is an indicator of the level of crosslinking in a particular silicone material. Silicone resins suitable for use in shampoo compositions of the invention typically have at least about 1.1 oxygen atoms per silicon atom. Preferably, the ratio of oxygen to silicon atoms is at least about 1.2: 1.0. Silanes used in the preparation of silicone resins include, but are not limited to, monomethyl-, dimethyl-, trimethyl-, monophenyl-, diphenyl-, methylphenyl-, monovinyl-, and methylvinyl-chlorosilanes, and tetrachlorosilane, with methyl-substituted silanes being most commonly used. Preferred resins are available from General Electric as GE SS4230 and GE SS 4267. Commercially available silicone resins are generally provided in a form that dissolves in low viscosity volatile or nonvolatile silicone liquids. The silicone resins useful in the present invention should be provided and incorporated into the present compositions in the dissolved form described above, as will be apparent to those of ordinary skill in the art.

In particular, the silicone material and silicone resin may be conveniently identified as "MDTQ" according to shorthand nomenclature known to those of ordinary skill in the art. Under this system, the siloxane is described in terms of the various siloxane monomer units present that make up the siloxane. Briefly, the symbol M represents a functional unit (CH)₃)₃SiO_0.5(ii) a D represents a difunctional unit (CH)₃)₂SiO; t represents a trifunctional unit (CH)₃)SiO_1.5(ii) a Q represents a tetrafunctional unit SiO₂. The base unit symbols (e.g., M ', D', T ', and Q') represent substituents other than methyl, and must be specifically defined at each occurrence. Typical alternating substituents include, but are not limited to, groups such as vinyl, phenyl, amine, hydroxyl, and the like. The molar ratios of the units, either in the total number of units of each type in the siloxane (or average number thereof) as subscripts to the symbols, or in combination with molecular weight as specifically indicated, complete the description of the siloxane material in terms of the MDTQ system. Higher relative molar amounts of T, Q, T ' and/or Q pairs D, D ', M and/or M ' in the silicone resin indicate higher levels of crosslinking. However, as discussed above, the overall level of crosslinking can also be indicated by the oxygen to silicon ratio.

Preferred silicone resins for use in the shampoo compositions of the present invention include, but are not limited to, MQ, MT, MTQ, MDT and MDTQ resins. Methyl is a preferred siloxane substituent. A particularly preferred silicone resin is an MQ resin, wherein the ratio of M to Q is from about 0.5: 1.0 to about 1.5: 1.0 and the average molecular weight of the silicone resin is from about 1000 to about 10,000.

The weight ratio of non-volatile silicone fluid having a refractive index of less than 1.46 to silicone resin component (when used) is preferably from about 4: 1 to about 400: 1, more preferably from about 9: 1 to about 200: 1, most preferably from about 19: 1 to about 100: 1, especially when the silicone fluid component is a polydimethylsiloxane fluid or a mixture of polydimethylsiloxane fluid and polydimethylsiloxane gum as described above. Because the silicone resin forms part of the same phase as the silicone fluid, i.e., the conditioning active, in the compositions of the present invention, the sum of the fluid and resin should be included in determining the silicone conditioning agent content of the composition.

2. Organic conditioning oil

The conditioning component of the shampoo compositions of the present invention further comprise from about 0.05% to about 3%, preferably from about 0.08% to about 1.5%, more preferably from about 0.1% to about 1%, by weight of the composition, of at least one organic conditioning oil as a conditioning agent, which may be used alone or in combination with other conditioning agents such as silicones (as described above).

These organic conditioning oils are believed to provide improved conditioning performance to the shampoo compositions when used in combination with the essential components of the composition, and particularly when used in combination with a cationic polymer (as described below). The conditioning oil can add shine and shine to the hair. In addition, they also enhance dry combing and dry hair feel. Most or all of these organic conditioning oils are believed to be soluble in the surfactant micelles of the shampoo compositions. It is also believed that this solubilization in the surfactant micelles may help to improve the hair conditioning performance of the shampoo compositions herein.

Organic conditioning oils suitable for use as the conditioning agents of the present invention are preferably low viscosity water insoluble liquids selected from hydrocarbon oils, polyolefins, fatty esters and mixtures thereof. The organic conditioning oil preferably has a viscosity of from about 1 centipoise to about 200 centipoise, more preferably from about 1 centipoise to about 100 centipoise, and most preferably from about 2 centipoise to about 50 centipoise, measured at a temperature of 40 ℃.

a. Hydrocarbon oil

Organic conditioning oils suitable for use as the conditioning agent in the shampoo compositions of the present invention include, but are not limited to, hydrocarbon oils having at least about 10 carbon atoms, such as cyclic hydrocarbons, straight chain aliphatic hydrocarbons (saturated or unsaturated), and branched chain aliphatic hydrocarbons (saturated or unsaturated), including polymers and mixtures thereof. The linear hydrocarbon oil is preferably about C₁₂To about C₁₉. Branched hydrocarbon oils, including hydrocarbonsThe polymer, typically will contain more than 19 carbon atoms.

Specific non-limiting examples of these hydrocarbon oils include paraffin oil, mineral oil, saturated and unsaturated dodecane, saturated and unsaturated tridecane, saturated and unsaturated tetradecane, saturated and unsaturated pentadecane, saturated and unsaturated hexadecane, polybutene, polydecene, and mixtures thereof. Branched chain isomers of these compounds, as well as higher chain length hydrocarbons, may also be used, examples of which include highly branched, saturated or unsaturated alkanes, such as the highly methyl-substituted isomers of hexadecane and eicosane, for example, the highly methyl-substituted isomers of 2, 2,4, 4,6, 6, 8, 8-dimethyl-10-methylundecane and 2, 2,4, 4,6, 6-dimethyl-8-methylnonane, available from Permethyl Corporation. Hydrocarbon polymers such as polybutene and polydecene. Preferred hydrocarbon polymers are polybutenes, such as copolymers of isobutylene and butene. Such a commercially available material is L-14 polybutene, available from Amoco Chemical Corporation.

b. Polyolefins

The organic conditioning oils used in shampoo compositions of the invention may also include liquid polyolefins, more preferably liquid poly(s)Olefin, most preferably hydrogenated, liquid polyAn olefin. Polyolefins for use in the present invention by C₄To about C₁₄Preferably about C₆To about C₁₂The olefin monomer (b) is polymerized.

Non-limiting examples of olefin monomers useful in preparing the polyolefin liquids of the present invention include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, branched chain isomers such as 4-methyl-1-pentene, and mixtures thereof. Refinery feedstocks or effluents comprising olefins are also suitable for producing polyolefin liquids. Preferred hydrogenated alpha olefin monomers include, but are not limited to, 1-hexene to 1-hexadecene, 1-octene to 1-tetradecene, and mixtures thereof.

c. Aliphatic esters

Other suitable organic conditioning oils for use as conditioners in the shampoo compositions of the invention include, but are not limited to, fatty esters having at least 10 carbon atoms. These aliphatic esters include esters having hydrocarbyl chains derived from fatty acids or alcohols (e.g., monoesters, polyol esters, and di-and tricarboxylic esters). Thus, the hydrocarbon group of the aliphatic ester can include or have covalently bonded thereto other compatible functional groups such as amide and alkoxy moieties (e.g., ethoxy or ether linkages, etc.).

Suitable for use in shampoo compositions of the present invention are those having about C₁₀To about C₂₂Fatty acid alkyl and alkenyl esters of aliphatic chains of, and having a structure derived from C₁₀To about C₂₂Alkyl and alkenyl fatty alcohol carboxylic acid esters of the aliphatic chain of alkyl and/or alkenyl alcohols of (a), and mixtures thereof. Specific examples of preferred aliphatic esters include, but are not limited to, isopropyl isostearate, hexyl laurate, isohexyl palmitate, isopropyl palmitate, decyl oleate, isodecyl oleate, cetyl stearate, decyl stearate, isopropyl isostearate, dihexyldecyl adipate, lauryl lactate, myristyl lactate, cetyl lactate, oleyl stearate, oleyl oleate, oleyl myristate, lauryl acetate, cetyl propionate, and oleyl adipate.

Other fatty esters suitable for use in the shampoo compositions of the present invention are monocarboxylic acid esters of the formula R ' COOR wherein R ' and R are alkyl or alkenyl groups and the sum of the carbon atoms in R ' and R is at least 10, preferably at least 20. The monocarboxylic acid ester need not contain at least one chain having at least 10 carbon atoms; and the total number of aliphatic chain carbon atoms must be at least 10. Specific non-limiting examples of monocarboxylic acid esters include: isopropyl myristate, ethylene glycol stearate, and isopropyl laurate.

Other suitable for use in the shampoo of the present inventionAliphatic esters in the composition are also di-and trialkyl and alkenyl esters of carboxylic acids, e.g. C₄To C₈Dicarboxylic acid esters (e.g. C for succinic, glutaric, adipic, caproic, heptanoic and octanoic acids)₁To C₂₂Esters of (5), preferably C₁To C₆Esters of (ii). Specific non-limiting examples of di-and tri-alkyl and alkenyl carboxylic acids include isocetyl stearyl stearate, diisopropyl adipate, and tristearyl citrate.

Other fatty esters suitable for use in shampoo compositions of the invention are those known as polyol esters. The above-mentioned polyhydric alcohol esters include alkylene glycol esters such as ethylene glycol mono-and di-fatty acid esters, diethylene glycol mono-and di-fatty acid esters, polyethylene glycol mono-and di-fatty acid esters, propylene glycol mono-and di-fatty acid esters, polypropylene glycol monooleate, polypropylene glycol 2000 monostearate, ethoxylated propylene glycol monostearate, glycerol mono-and di-fatty acid esters, polyglycerol poly-fatty acid esters, ethoxylated glycerol mono-stearate, 1, 3-butylene glycol monostearate, 1, 3-butylene glycol distearate, polyoxyethylene polyol fatty acid esters, sorbitan fatty acid esters and polyoxyethylene sorbitan fatty acid esters.

Other fatty esters also suitable for use in shampoo compositions of the invention are glycerides, including but not limited to mono-, di-and triglycerides, preferably di-and triglycerides, most preferably triglycerides. The glyceride esters for use in the shampoo compositions of the present invention are preferably long chain carboxylic acids such as C₁₀-C₂₂Mono-, di-and triglycerides of carboxylic acids. Several such substances are obtained from vegetable and animal fats and oils, such as castor oil, safflower oil, cottonseed oil, corn oil, olive oil, cod liver oil, almond oil, avocado oil, palm oil, sesame oil, lanolin and soybean oil. Synthetic oils include, but are not limited to, triolein and dilaurin tristearate.

Other fatty esters suitable for use in shampoo compositions of the invention are water insoluble synthetic fatty esters. Some preferred synthetic esters correspond to the following general formula (IX):

wherein R is¹Is C₇To C₉Alkyl, alkenyl, hydroxyalkyl or hydroxyalkenyl of (a), preferably saturated alkyl, more preferably saturated straight-chain alkyl; n is a positive integer having a value of 2 to 4, preferably 3; and Y is an alkyl, alkenyl, hydroxy or carboxy substituted alkyl or alkenyl group having from about 2 to about 20 carbon atoms, preferably from about 3 to about 14 carbon atoms. Other preferred synthetic esters correspond to the following general formula (X):

wherein R is²Is C₈To C₁₀Alkyl, alkenyl, hydroxyalkyl or hydroxyalkenyl of (a); preferably saturated alkyl, more preferably saturated straight-chain alkyl; n and Y are as defined above for formula (X).

It is believed that the preferred synthetic esters provide improved wet hair feel when used in combination with the essential components of the shampoo compositions of the invention, particularly when used in combination with a cationic polymer component (as described below). These synthetic esters improve wet hair feel by reducing the perception of excess conditioning of wet hair that is pasty or has been conditioned by cationic polymers.

Specific non-limiting examples of synthetic fatty esters suitable for use in the shampoo compositions of the present invention include: p-43 (C of trimethylolpropane)₈-C₁₀Triester), MCP-684(3, 3-diethanol-1, 5-pentanediol tetraester), MCP 121 (adipic acid C)₈-C₁₀Diesters), all of which are available from Mobil chemical company.

3. Other Conditioning Agents

Also suitable for use in the compositions of the present invention are the conditioners described in U.S. Pat. Nos. 5,674,478 and 5,750,122 by the Procter & Gamble Company, both of which are incorporated herein by reference in their entirety. Also suitable for use herein are those conditioning agents described in U.S. Pat. Nos. 4,529,586(Clairol), 4,507,280(Clairol), 4,663,158(Clairol), 4,197,865(L 'Oreal), 4,217,914 (L' Oreal), 4,381,919(L 'Oreal), and 4,422,853 (L' Oreal), the descriptions of which are incorporated herein by reference.

Other preferred silicone conditioning agents suitable for use in the compositions of the present invention include: abil from Goldschmidt^S201 (dimethicone/PG-propyldimethicone sodium thiosulfate copolymer); DC Q2-8220 (trimethylsilylaminopolydimethylsiloxane) from Dow Corning; DC 949 from Dow Corning (amino-terminated polydimethylsiloxane, cetyltrimethylammonium chloride and trideceth-12); DC 749 (cyclomethicone and trimethylsiloxysilicate) from Dow Corning; DC2502 (cetyl dimethicone) from Dow Corning; BC97/004 and BC 99/088 (amino-functionalized silicone microemulsions) from Basildon Chemicals; GE SME253 and SM2115-D2 and SM2658 and SF1708 from General Electric (amino-functionalized silicone microemulsions); silicified canola oil from Croda; and those silicone conditioning agents described by GAF corp. in us patent 4,834,767 (quaternary ammonium based lactams), by Biosil Technologies in us patent 5,854,319 (reactive silicone emulsions comprising amino acids), and by Dow Corning in us patent 4,898,585 (silicones), the descriptions of which are incorporated herein by reference.

Wetting agent

The compositions of the present invention may comprise a humectant. The wetting agent of the present invention is selected from the group consisting of polyols, water-soluble alkoxylated nonionic polymers, and mixtures thereof. When used in the present invention, the wetting agent is preferably used in an amount of about 0.1% to about 20%, more preferably about 0.5% to about 5%, wherein the percentages are based on 100% by weight of the composition.

Polyols useful in the present invention include glycerin, sorbitol, propylene glycol, butylene glycol, hexylene glycol, ethoxylated glucose, 1, 2-hexanediol, hexanetriol, dipropylene glycol, erythritol, trehalose, diglycerin, xylitol, maltitol, maltose, glucose, fructose, sodium chondroitin sulfate, sodium hyaluronate, sodium adenosine phosphate, sodium lactate, pyrrolidone carbonate, glucosamine, cyclodextrin, and mixtures thereof.

Water-soluble alkoxylated nonionic polymers useful in the present invention include polyethylene glycols and polypropylene glycols having a molecular weight of up to about 1000, such as those having the CTFA designation PEG-200, PEG-400, PEG-600, PEG-1000, and mixtures thereof.

Commercially available humectants in the present invention include: glycerol is given the trade name STAR^TMAnd SUPEROL^TMFrom Procter& Gamble Company，CRODEROL GA7000^TMAvailable from Universal Ltd., PRECERIN^TMSeries are available from Unichema and are available from NOF under the same chemical name; propylene glycol is available under the trade name LEXOL PG-865/855^TMFrom Inolex, 1, 2-PROPYLENE GLYCOLUSP from BASF; sorbitol is sold under the trade name LIPONIC^TMSeries are available from Lipo, SORBO^TM、ALEX^TM、A-625^TMAnd A-641^TMDerived from ICI, and UNISWEET 70^TM、UNISWEETCONC^TMFrom UPI; dipropylene glycol is available from BASF under the same trade name; DIGLYCEROL is sold under the trade name digylcerol^TMFrom Solvay GmbH; xylitol is available from Kyowa and eizai under the same trade name; maltitol is available from Hayashibara under the trade name malbi; sodium chondroitin SULFATE is available under the same trade name from Freeman and Bioiberica, and from Atomeric Chemicals under the trade name ATOMIC SODIUMCHONDROITIN SULFATE; SODIUM HYALURONATE is available from Active Organics under the trade name ACTIMIOIST, the AVIAN SODIUM HYALURONATE series from Intergen, HYALUNIC ACID Na from Ichimaru Pharcos; sodium adenosine phosphate is available under the same trade name from Asahikasei, Kyowa and Daiichi Seiyaku; sodium lactate is available from Merck, Wako and Showa Kako under the same trade name; cyclodextrins are available from America under the trade name CAVITRONan Maize, RHODOCAP series from Rhone-Poulenc and DEXPEARL from Tomen; and polyethylene glycol is available from Union Carbide under the trade name CARBOWAX series.

Suspending agent

The shampoo compositions of the present invention may further comprise a suspending agent in a dispersed form of the shampoo composition at a concentration effective to suspend particles or other water insoluble materials or to adjust the viscosity of the composition. Such concentrations are from about 0.1% to about 10%, preferably from about 0.3% to about 5.0%, wherein the percentages are by weight of the shampoo composition 100%.

Suspending agents useful in the present invention include anionic polymers and nonionic polymers. Suitable for use in the present invention are vinyl polymers, such as cross-linked acrylic polymers, with the CTFA name carbomer; cellulose derivatives and modified cellulose polymers, such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, nitrocellulose, sodium cellulose sulfate, sodium carboxymethylcellulose, crystalline cellulose, cellulose powder, polyvinylpyrrolidone, polyvinyl alcohol, guar gum, hydroxypropyl guar gum, xanthan gum, gum arabic, tragacanth gum, galactan, carob gum, karaya gum, locust bean gum, carrageenan, pectin, agar, quince seed (quince seed), starch (rice, corn, potato, wheat), seaweed gum (seaweed extract), microbial polymers such as dextran, succinoglucan, pulleran; starch-based polymers such as carboxymethyl starch, methyl hydroxypropyl starch; alginic acid based polymers such as sodium alginate, propylene glycol alginate; acrylate polymers such as sodium polyacrylate, polyalkylene glycols having a molecular weight greater than about 1000, polyethylacrylate, polyacrylamide, polyethyleneimine; and inorganic water-soluble substances such as bentonite, magnesium aluminum silicate (laponite), hectorite (hectorite) and anhydrous silicic acid.

Other optional Components

The compositions of the invention may also comprise vitamins and amino acids, such as: water-soluble vitamins such as vitamin B1, B2, B6, B12, C, pantothenic acid, panthenyl ethyl ether, panthenol, biotin, and derivatives thereof; water-soluble amino acids such as asparagine, alanine, indole, glutamic acid and salts thereof; water-insoluble vitamins such as vitamin A, D, E and their derivatives; water insoluble amino acids such as tyrosine, tryptamine and their salts.

The compositions of the present invention may also contain pigment materials such as inorganic, nitroso, monoazo, disazo, carotenoids, triphenylmethane, triarylmethane, xanthenes, quinolines, oxazines, azines, anthraquinones, indigoids, thioninoids, dihydroxyquinoacridines, phthalocyanines, botanicals, natural pigments including: water-soluble components, such as dyes having the following c.i. designations: acid red 18, 26, 27, 33, 51, 52, 87, 88, 92, 94, 95, acid yellow 1, 3, 11, 23, 36, 40, 73, food yellow 3, food green 3, food blue 2, food red 1, 6, acid blue 5, 9, 74, pigment red 57-1, 53(Na), basic violet 10, solvent red 49, acid orange 7, 20, 24, acid green 1, 3, 5, 25, solvent green 7, acid violet 9, 43; water-insoluble components, such as dyes having the following c.i. designations: pigment red 53(Ba), 49(Na), 49(Ca), 49(Ba), 49(Sr), 57, solvent red 23, 24, 43, 48, 72, 73, solvent orange 2, 7, pigment red 4, 24, 48, 63(Ca)3, 64, vat red 1, vat blue 1, 6, pigment orange 1,5, 13, solvent yellow 5,6, 33, pigment yellow 1, 12, solvent green 3, solvent violet 13, solvent blue 63, pigment blue 15, titanium dioxide, copper chlorophyllin complex, ultramarine, aluminum powder, bentonite, calcium carbonate, barium sulfate, silver bismuth ore, calcium sulfate, carbon black, bone char, chromic acid, cobalt blue, gold, iron oxide, hydrated iron oxide, iron ferrocyanide, magnesium carbonate, magnesium phosphate, silver, and zinc oxide.

The compositions of the present invention may also include antimicrobial agents, which are useful as cosmetic insecticides and anti-dandruff agents, including: water-soluble components such as copper octopirox ethanolamine, and water-insoluble components such as 3, 4, 4' -trichlorodiphenylurea (triclosan), triclocarban and 1-oxo-2-mercaptopyridine zinc.

The compositions of the present invention may also include chelating agents, such as: 2, 2' -dipyridylamine; 1, 10-phenanthroline { phenanthroline }; di-2-pyridylketone; 2, 3-bis (2-pyridyl) pyrazine; 2, 3-bis (2-pyridyl) -5, 6-dihydropyrazine; 1, 1' -carbonyldiimidazole; 2, 4-bis (5, 6-diphenyl-1, 2, 4-triazin-3-yl) pyridine; 2,4, 6-tris (2-pyridyl) -1, 3, 5-triazine; 4,4 '-dimethyl-2, 2' -bipyridine; 2, 2' -biquinoline; di-2-pyridylglyoxal {2, 2' -pyridil }; 2- (2-pyridyl) benzimidazole; 2, 2' -bipyrazinyl; 3- (2-pyridyl) -5, 6-diphenyl-1, 2, 4-triazine; 3- (4-phenyl-2-pyridyl) -5-phenyl-1, 2, 4-triazine; 3- (4-phenyl-2-pyridyl) -5, 6-diphenyl-1, 2, 4-triazine; 2,3, 5, 6-tetrakis- (2' -pyridyl) -pyrazine; 2, 6-pyridinedicarboxylic acid; 2,4, 5-trihydroxypyrimidine; phenyl 2-pyridylketoxime; 3-amino-5, 6-dimethyl-1, 2, 4-triazine; 6-hydroxy-2-phenyl-3 (2H) -pyridazinone; 2, 4-pteridine diol {2, 4-dioxotetrahydropteridine }; 2, 2' -bipyridine; and 2, 3-dihydroxypyridine.

Application method

The shampoo compositions of the present invention are used in a conventional manner to cleanse hair or skin and provide enhanced deposition of anti-dandruff particles and other benefits of the present invention. An effective amount of the composition for cleansing hair or skin is applied to hair or skin that has preferably been wetted with water and then rinsed off. The effective amount is generally from about 1g to about 50g, preferably from about 1g to about 20 g. Application to hair typically involves rubbing the composition into the hair so that most or all of the hair comes into contact with the composition.

The method of cleansing hair and skin comprises the steps of:

a) wetting the hair and/or skin with water, b) applying an effective amount of the shampoo composition to the hair and/or skin, and c) rinsing the composition from the hair and/or skin with water. These steps can be repeated as many times as desired to achieve the desired cleaning and particle deposition benefits.

The following examples further describe and demonstrate preferred embodiments within the scope of the present invention. The examples are for the purpose of illustration only and should not be construed as limiting the invention as many variations thereof are possible without departing from the scope thereof.

Examples

The shampoo compositions described in the following examples describe specific embodiments of the shampoo compositions of the present invention, but are not intended to be limiting thereof. Other variations may be made by those skilled in the art without departing from the spirit and scope of the invention. These exemplary embodiments of the shampoo compositions of the present invention provide enhanced particle deposition efficiency benefits.

The shampoo compositions described in the examples below are prepared by conventional formulation and mixing methods, examples of which are set forth below. Unless otherwise indicated, all exemplified amounts are listed as weight percentages and exclude minor ingredients such as diluents, preservatives, colored solutions, hypothetical ingredients, botanical drugs, and the like.

Shampoo compositions of the invention may be prepared by conventional formulation and mixing techniques. When melting or dissolution of the solid surfactant or wax component is necessary, these may be added to the surfactant premix, or some portion of the surfactant, mixed and heated to melt the solid component, for example at a temperature of about 72 ℃. The mixture may then optionally be processed through a shear mill and cooled, and then the remaining components are mixed. The anti-dandruff particulate component may be added by a high shear mill prior to treatment, or preferably added to the final mixture after cooling as a pre-dispersed suspension. The polydimethylsiloxane may be prepared as a premix of the desired particle size and then added to the final mixture. The composition typically has a final viscosity of about 2000 to about 20,000 cps. The viscosity of the composition can be adjusted by conventional methods, including the addition of sodium chloride or ammonium xylene sulfonate as needed. Thus, the listed formulations includeA component and any minor components associated with the component.

	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6	Example 7
								Ammonium lauryl polyoxyethylene ether sulfate			2.00	2.00		2.00	2.00
Ammonium dodecyl sulfate			2.00	2.00		2.00	2.00
								Sodium lauryl Ether sulfate	12.00	12.00			12.00
Sodium lauryl sulfate	2.00	2.00			2.00
								Cocoamidopropyl betaine	2.00	2.00		2.00	2.00	4.00	2.00
N-lauroylaminoethyl-N-hydroxyethyl sodium acetate	2.00	2.00	4.00	2.00	2.00		2.00
								Ethylene glycol distearate	1.50	1.50	1.50	1.50	1.50	1.50	1.50
CMEA	0.800	0.800	0.800	0.800	0.800	0.800	0.800
								Cetyl alcohol	0.900	0.900	0.600	0.600	0.900	0.600	0.600
Lauryl alcohol	0.200	0.200			0.200
								Guar hydroxypropyl trimonium chloride (1)					0.250
Polyquaternary ammonium salt-10 (2)	0.500	0.500	0.500	0.500			0.500
								Polyquaternary ammonium salt-10 (3)						0.500
Polydimethylsiloxane (4)		1.35				1.35
								Polydimethylsiloxane (5)	1.00		1.00	1.00	1.00		1.00
Trimethylolpropane tricaprylate/tricaprate (6)							0.10
								Hydrogenated polydecene (7)			0.25			0.25	0.40
ZPT(8)	1.00	1.00	1.00	1.00	1.00	1.00	1.00
								Citric acid sodium salt			0.40	0.40		0.40	0.40
Citric acid			0.39	0.39		0.39	0.39
								Hydrochloric acid	0.600	0.600	0.600	0.600	0.600	0.600	0.600
Sodium xylene sulfonate	1.00	1.00	1.00	1.00	1.00	1.00	1.00
								Perfume	0.400	0.400	0.400	0.400	0.400	0.400	0.400
Sodium benzoate	0.250	0.250	0.250	0.250	0.250	0.250	0.250
								Kathon	0.0008	0.0008	0.0008	0.0008	0.0008	0.0008	0.0008
Benzyl alcohol	0.0225	0.0225	0.0225	0.0225	0.0225	0.0225	0.0225
								Water (W)	Proper amount of	Proper amount of	Proper amount of	Proper amount of	Proper amount of	Proper amount of	Proper amount of

(1) Jaguar C17 available from Rhodia

(2) Polymer KG30M available from Amerchol/Dow Chemical

(3) Polymer JR30M available from Amerchol/Dow Chemical

(4) Viscasil 330M from General Electric Silicones

(5) DC1664 available from Dow Corning Silicones

(6) Mobil P43, available from Mobil.

(7) Puresyn 6, available from mobil.

(8) ZPT having an average particle size of about 2.5m, available from Arch/Olin.

It is understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art without departing from the scope of the present invention.

Claims (8)

1. A shampoo composition comprising:

a) from about 5% to about 50% by weight of a detersive surfactant,

b) at least about 0.1% by weight of anti-dandruff particulate,

c) at least about 0.05% by weight of a cationic polysaccharide polymer having a molecular weight of from about 10,000 to about 10,000,000 and a charge density of from about 1.4meq/gm to about 7.0meq/gm, and

d) at least about 20.0% by weight of an aqueous carrier.

2. The shampoo composition according to claim 1 wherein said cationic polysaccharide polymer corresponds to the general formula:

a) wherein A is an anhydroglucose residue;

b) wherein R is selected from the group consisting of alkylene oxides, polyoxyalkylenes, hydroxyalkylenes, and mixtures thereof;

c) wherein R is¹、R²And R³Independently selected from the group consisting of alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl, and alkoxyaryl; each radical containing up to about 18 carbon atoms, and R¹、R²And R³A total number of carbon atoms less than about 20; and

d) wherein X is selected from the group consisting of chloride, fluoride, bromide, iodide, sulfate, methylsulfate, and mixtures thereof.

3. The composition of claim 1 wherein said cationic polysaccharide polymer has a charge density of from about 1.7meq/gm to about 7 meq/gm.

4. The composition of claim 1 wherein said cationic polysaccharide polymer has a charge density of from about 1.9meq/gm to about 5 meq/gm.

5. The composition of claim 1, wherein said anti-dandruff particulate comprises a zinc salt of 1-hydroxy-2-pyridinethione.

6. The composition of claim 4, wherein said anti-dandruff particulate comprises a zinc salt of 1-hydroxy-2-pyridinethione.

7. The composition of claim 1, wherein the weight ratio of said cationic polysaccharide polymer to said anti-dandruff particulate is from about 1: 1 to about 1: 20.

8. A method of treating hair by applying a safe and effective amount of the composition of claim 1.