HK1006150B - Shampoo compositions with silicone and cationic surfactant conditioning agents - Google Patents

Description

This invention relates to shampoo compositions comprising anionic detersive surfactants, silicone hair conditioning agents, and cationic surfactant hair conditioning agents.

Human hair becomes soiled due to its contact with the surrounding atmosphere and, to a greater extent, from sebum secreted by the head. The build-up of the sebum causes the hair to have a dirty feel and an unattractive appearance. The soiling of the hair necessitates it being shampooed with frequent regularity.

Shampooing the hair cleans by removing excess soil and sebum. However, the shampooing process has disadvantages in that the hair is left in a wet, tangled and generally unmanageable state. Shampooing can also result in the hair becoming dry or "frizzy" due to removal of natural oils or other hair moisturizing materials. After shampooing, the hair can also suffer from a loss of "softness" perceived by the user upon drying. A variety of approaches have been developed to alleviate the after-shampoo problems. These range from the inclusion of hair conditioning aids in shampoos to post-shampoo application of hair conditioners, i.e., hair rinses. Hair rinses are generally liquid in nature and must be applied in a separate step following the shampooing, left on the hair for a length of time, and rinsed with fresh water. This, of course, is time consuming and is not convenient.

While a wide variety of shampoos have been disclosed which contain conditioning aids, they have not been totally satisfactory for a variety of reasons. One problem relates to compatibility problems between good cleaning anionic surfactants and the many conventional cationic agents which historically have been used as conditioning agents.

Whereas efforts have been made to minimize adverse interaction through the use of alternate surfactants and improved cationic conditioning agents, it remains highly desirable to utilize anionic surfactants in shampoo compositions. Furthermore, cationic conditioning agents commonly do not provide optimal overall conditioning benefits, particularly in the area of "softness", when delivered as an ingredient in a shampoo composition. For example, cationic surfactants which are compatible with the anionic detersive surfactants and which have previously been incorporated into shampoo compositions, such as tricetyl methyl ammonium chloride, can provide good anti-static benefits, but are less successful it providing soft, conditioned hair.

Materials which can provide increased softness are nonionic silicones. Silicones in shampoo compositions have been disclosed in a number of different publications. Such publications include US-A-2,826,551, Geen, issued March 11, 1958; US-A-3,964,500, Drakoff, issued June 22, 1976; US-A-4,364,837, Pader, issued December 21, 1982; and GB-A-849,433, Woolston, issued September 28, 1960. While these patents disclose silicone containing compositions, they also did not provide a totally satisfactory product in that it was difficult to maintain the silicone well dispersed and suspended in the product. Recently, stable, insoluble silicone-containing hair conditioning shampoo compositions have been described in US-A-4 741,855, Grote and Russell, issued May 3, 1988. These shampoo compositions can deliver excellent overall conditioning benefits to the hair while maintaining excellent cleaning performance, even with the use of anionic detersive surfactants, for a wide variety of hair types. However, it would be desirable to improve these types of shampoos such that they provided improved conditioning benefits to one type of hair in particular, that type being hair damaged by permanent treatments (i.e., "perms"), color treatments, and bleach treatments, applied either at hair salons or at home.

Furthermore, US-A-3,964,500 and US-A-4,704,242 disclose hair conditioning shampoos which contain silicones and cationic materials and DE-A-3,442,175 and GB-A-2,196,980 disclose hair care compositions containing quaternary ammonium surfactant moieties. Unfortunately, silicone hair conditioner efficacy for permed hair appears to be lower than that for most undamaged hair. It would be desirable to provide a shampoo composition that would provide excellent overall cleaning and conditioning benefits for such hair, as well as other types of hair not subjected to such treatments. This would reduce the need for families or others sharing hair care products to purchase separate shampoo and conditioning products for persons with damaged and undamaged hair.

It is an object of this invention to provide shampoo compositions, which can provide excellent cleaning performance and excellent overall hair conditioning for such damaged hair as well as for hair not subjected to such treatments ("undamaged hair").

It is a further object of this invention to provide improved anionic surfactant-containing shampoo compositions that can provide excellent cleaning performance and conditioning performance for both damaged and undamaged hair types, such that the shampooed hair can have desirable levels of manageability, combability, softness, and low or reduced levels of dryness.

These objects will become apparent from the description which follows, as many other objects become apparent upon a reading of said description.

Unless otherwise indicated, all percentages are calculated by weight of the total composition, and all ratios are calculated on a weight basis.

This invention provides anionic detersive surfactant-containing liquid shampoo compositions that can provide both excellent cleaning performance and hair conditioning benefits to a wide variety of hair types, including treatment damaged and undamaged hair. This can be attained by incorporating into the shampoo composition a nonionic, insoluble, nonvolatile silicone hair conditioning agent and, additionally, critically selected, soluble cationic conditioning surfactants. The shampoo compositions hereof will also comprise an aqueous carrier.

The cationic surfactants of the present invention are quaternary ammonium surfactants and amine surfactants that are positively charged at the pH of the shampoo composition, generally at pH of about 10 or lower and are soluble in the shampoo composition. The cationic surfactants for use herein must also contain one or more nonionic hydrophilic moieties. Without intending to necessarily limit the invention by any particular theory, it is believed that the presence of nonionic hydrophilic moieties enhances the ability of the cationic surfactant to remain soluble in the shampoo compostions, thus enhancing hair conditioning efficacy of the cationic surfactant.

When combined with the nonionic silicone conditioning agents in the shampoo compositions of this invention, these cationic surfactants can provide surprisingly good hair conditioning benefits for permed or other damaged hair characterized by increased anionic character, such as bleached hair and color treated hair. These types of hair that have been damaged and are characterized by increased anionic character shall hereinafter be collectively referred to as "damaged hair". Nonionic silicone conditioning agents suffer from reduced deposition, and therefore reduced efficacy, for these hair types. On the other hand, the use of the cationic surfactants as the sole type of hair conditioning agents to damaged hair when delivered from shampoo compositions may not provide sufficient overall conditioning benefits, especially in the area of softness. The combination of hair conditioning agents, however, results in shampoo compositions with high levels of conditioning for damaged hair, and retains excellent conditioning for undamaged hair and cleaning performance for all hair types. As used herein, undamaged refers to hair that is not damaged by perms or other hair treatments which increase the anionic character of the hair, and does not exclude, for example, oily hair, dry hair, etc., or hair damaged in some other respect, unless such other damage is specifically and expressly indicated. These results are especially important because merely increasing the level of silicone conditioning agent in a particular shampoo that is effective for treating undamaged hair to improve conditioning of damaged hair can result in too high a level of silicone deposition for undamaged hair. This can impart an undesirable greasy feel. On the other hand, the cationic surfactant, by itself, does not provide efficient conditioning of undamaged hair. The present invention provides anionic detersive surfactant-containing shampoo compositions that can provide excellent conditioning to both damaged and normal hair through the use of nonionic silicone and particularly selected hydrophile-containing cationic conditioning surfactants hereof.

The preferred cationic conditioning surfactants for use in the present invention are those which are useful for providing conditioning benefits, particularly hair conditioning benefits and which are quaternary ammonium or amino compounds having at least one N-radical containing one or more hydrophilic moieties selected from alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, and alkylester moieties, and combinations thereof. The amino surfactants must be positively charged at the pH of the shampoo composition. Generally, the pH of shampoo compositions will be less than about 10, typically from about 3 to about 9. A pH of about 9 or less is especially preferred for shampoo compositions containing cationic conditioning surfactants that are dependent upon amino moieties for their cationic charge.

In a preferred embodiment, the present invention provides hair conditioning shampoo compositions comprising:

• (a) from 5% to 50%, by weight, of an anionic detersive surfactant component;
• (b) from 0.1% to 10%, by weight, of a dispersed, insoluble, nonionic silicone conditioning agent, said silicone hair conditioning agent comprising a non-volatile, insoluble, nonionic, silicone fluid component;
• (c) from 0.2% to 10%, by weight, of a soluble cationic, amino or quaternary ammonium conditioning surfactant having a single cationic nitrogen atom and at least one N-radical containing one or more hydrophilic moieties that are within 4 carbon atoms (inclusive) of the cationic nitrogen atom said hydrophilic moieties being selected from the group consisting of alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, and alkylester moieties, and mixtures thereof; and
• (d) an aqueous carrier.

As used herein, the terms "soluble" and "insoluble" used in reference to particular ingredients of the shampoo compositions refer to solubility or insolubility, respectively, of that ingredient in the shampoo composition.

All percentages are calculated by weight of the total composition unless otherwise specifically indicated.

The invention, including preferred embodiments thereof, is described in further detail in the Detailed Description of the Invention, which follows.

The essential as well as a variety of preferred and optional components of the compositions of the present invention are described below.

The hair conditioning shampoo compositions of the present invention comprise an anionic detersive surfactant to provide cleaning performance to the composition.

The anionic detersive surfactant will generally be from 5% to 50%, preferably from 8% to 30%, more preferably from 10% to 25%, of the composition. The anionic detersive surfactant of the compositions hereof can be a single species of surfactant or a combination of different surfactants.

Synthetic anionic detersive detergents useful herein include alkyl and alkyl ether sulfates. These materials have the respective formulae ROSO₃M and RO(C₂H₄O)_xSO₃M, wherein R is alkyl or alkenyl of from about 8 to about 24 carbon atoms, x is 1 to 10, and M is a water-soluble cation such as ammonium, sodium, potassium and triethanolamine. The alkyl ether sulfates are typically made as condensation products of ethylene oxide and monohydric alcohols having from about 8 to about 24 carbon atoms. Preferably, R has from about 12 to about 18 carbon atoms in both the alkyl and alkyl ether sulfates. The alcohols can be derived from fats, e.g., coconut oil or tallow, or can be synthetic. Lauryl alcohol and straight chain alcohols derived from coconut oil are preferred herein. Such alcohols are reacted with about 1 to about 10, and especially about 3, molar proportions of ethylene oxide and the resulting mixture of molecular species having, for example, in average of 3 moles of ethylene oxide per mole of alcohol, is sulfated and neutralized.

Specific examples of alkyl ether sulfates which may be used in the present invention are sodium and ammonium salts of coconut alkyl triethylene glycol ether sulfate; tallow alkyl triethylene glycol ether sulfate, and tallow alkyl hexaoxyethylene sulfate. Highly preferred alkyl ether sulfates are those comprising a mixture of individual compounds, said mixture having a average alkyl chain length of from about 12 to about 16 carbon atoms and in average degree of ethoxylation of from about 1 to about 4 moles of ethylene oxide. Such a mixture also comprises from 0 to 20% by weight C₁₂₋₁₃ compounds; from 60 to 100% by weight of C₁₄₋₁₅₋₁₆ compounds, from 0 to 20% by weight of C₁₇₋₁₈₋₁₉ compounds; from 3 to 30% by weight of compounds having a degree of ethoxylation of 0; from 45 to 90% by weight of compounds having a degree of ethoxylation of from about 1 to about 4; from 10 to 25% by weight of compounds having a degree of ethoxylation of from about 4 to about 8; and from 0.1 to 15% by weight of compounds having a degree of ethoxylation greater than about 8.

Another suitable class of anionic detersive surfactants are the water-soluble salts of the organic, sulfuric acid reaction products of the general formula:         R₁-SO₃-M wherein R₁ is chosen from the group consisting of a straight or branched chain, saturated aliphatic hydrocarbon radical having from about 8 to about 24, preferably about 12 to about 18, carbon atoms; and M is a cation. Important examples are the salts of an organic sulfuric acid reaction product of a hydrocarbon of the methane series, including iso-, neo-, ineso-, and n-paraffins, having about 8 to about 24 carbon atoms, preferably about 12 to about 18 carbon atoms and a sulfonating agent, e.g., SO₃, H₂SO₄, oleum, obtained according to known sulfonation methods, including bleaching and hydrolysis. Preferred are alkali metal and ammonium sulfonated C₁₂₋₁₈ n-paraffins.

Additional examples of synthetic anionic detersive surfactants which come within the terms of the present invention are the reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amides of methyl tauride in which the fatty acids, for example, are derived from coconut oil. Other synthetic anionic detersive surfactants of this variety are set forth in US-A-2,486,921; US-A-2,486,922; and US-A-2,396,278.

Still other synthetic anionic detersive surfactants are in the class designated as succinamates. This class includes such surface active agents as disodium N-octadecylsulfosuccinamate; tetrasodium N-(1,2-dicarboxyethyl)-N-octadecylsulfosuccinamate; diamyl ester of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; dioctyl esters of sodium sulfosuccinic acid.

Other suitable anionic detersive surfactants utilizable olefin sulfonates having about 12 to about 24 carbon atoms. The term "olefin sulfonates" is used herein to mean compounds which can be produced by the sulfonation of α-olefins by means of uncomplexed sulfur trioxide, followed by neutralization of the acid reaction mixture in conditions such that any sulfones which have been formed in the reaction are hydrolyzed to give the corresponding hydroxy-alkanesulfonates. The sulfur trioxide can be liquid or gaseous, and is usually, but not necessarily, diluted by inert diluents, for example by liquid SO₂, chlorinated hydrocarbons, etc., when used in the liquid form, or by air, nitrogen, gaseous SO₂, etc., when used in the gaseous form.

The α-olefins from which the olefin sulfonates are derived are mono-olefins having about 12 to about 24 carbon atoms, preferably about 14 to about 16 carbon atoms. Preferably, they are straight chain olefins. Examples of suitable 1-olefins include 1-dodecene; 1-tetradecene; 1-hexadecene; 1-octadecene; 1-eicosene and 1-tetracosene.

In addition to the true alkene sulfonates and a proportion of hydroxy-alkanesulfonates, the olefin sulfonates can contain minor amounts of other materials, such as alkene disulfonates depending upon the reaction conditions, proportion of reactants, the nature of the starting olefins and impurities in the olefin stock and side reactions during the sulfonation process.

A specific α-olefin sulfonate mixture of the above type is described more fully in the US-A-3,332,880, Pflaumer and Kessler, issued July 25, 1967.

Another class of anionic detersive surfactants are the β-alkyloxy alkane sulfonates. These compounds have the following formula: where R₁ is a straight chain alkyl group having from about 6 to about 20 carbon atoms, R₂ is a lower alkyl group having from about 1 (preferred) to about 3 carbon atoms: and M is a water-soluble cation as hereinbefore described.

Specific examples of β-alkyloxy-alkane-1-sulfonates, or alternatively 2-alkyloxy-alkane-1-sulfonates, having low hardness (calcium ion) sensitivity useful herein include: potassium-β-methoxydecanesulfonate, sodium 2-methoxy-tridecanesulfonate, potassium 2-ethoxytetradecylsulfonate, sodium 2-isopropoxyhexadecylsulfonate, lithium 2-t-butoxytetradecyl-sulfonate, sodium β-methoxyoctadecylsulfonate, and ammonium β-n-propoxydodecylsulfonate.

Many additional synthetic anionic surfactants are described in McCutcheon's, Emulsifiers and Detergents, 1989 Annual, published by M. C. Publishing Co. Also US-A-3,929,678, Laughlin et al., issued December 30, 1975, discloses many other anionic as well as other surfactant types.

Preferred anionic detersive surfactants for use in the present shampoo compositions 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, lauric monoglyceride sodium sulfate, sodium lauryl sulfate, sodium laureth sulfate, potassium lauryl sulfate, potassium laureth sulfate, sodium lauryl sarcosinate, sodium lauroyl sarcosinate, lauryl sarcosine, cocoyl sarcosine, ammonia cocoyl sulfate, ammonia lauroyl sulfate, sodium cocoyl sulfate, sodium lauroyl sulfate, potassium cocoyl sulfate, potassium lauroyl sulfate, triethanolamine lauryl sulfate, triethanolamine lauroyl sulfate, monoethanolamine cocoyl sulfate, monoethanolamine lauroyl sulfate, sodium tridecyl benzene sulfonate, and sodium dodecyl benzene sulfonate.

In addition to the anionic detersive surfactant, the compositions of the present invention can optionally contain other detersive surfactants. These include nonionic surfactants, amphoteric surfactants, zwitterionic surfactants. Optional detersive surfactants, when used, are typically present at levels of from 0.5% to 20%, more typically from 1% to 10% by weight. Also, the total amount of detersive surfactant in compositions containing optional detersive surfactants in addition to the anionic surfactant will generally be from 5.5% to 50%, preferably from 8% to 30%, more preferably from 10% to 25% by weight. Cationic detersive surfactants can also be used, but are generally less preferred because they can adversely interact with the anionic detersive surfactant. Cationic detersive surfactants, if used, are preferably used at levels no greater than 5% by weight.

Nonionic detersive surfactants which can be used include those broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. Examples of preferred classes of nontonic detersive surfactants are

• 1. The polyethylene oxide condensates of alkyl phenols, e.g., the concensation products of alkyl phenols having an alkyl group containing from about 5 to about 20 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to from about 10 to about 60 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds lay be derived from polymerized propylene, diisobutylene, octane, or nonane, for example.
• 2. Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine products which lay be varied in composition depending upon the balance between the hydrophobic and hydrophilic elements which is desired. For example, compounds containing from 40% to 80% polyoxyethylene by weight and having a molecular weight of from 5,000 to 11,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product of ethylene diamine and excess propylene oxide, said base having a molecular weight of the order of 2,500 to 3,000, are satisfactory.
• 3. The condensation product of aliphatic alcohols having from about 8 to about 18 carbon atoms, in either straight chain or branched chain configuration, with ethylene oxide, e.g., a coconut alcohol ethylene oxide condensate having from about 10 to about 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from about 10 to about 14 carbon atoms.
• 4. Long chain tertiary amine oxides corresponding to the following general formula: R₁R₂R₃N -> Owherein R₁ contains an alkyl, alkenyl or monohydroxy alkyl radical of from about 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties, and from 0 to about 1 glyceryl moiety, and R₂ and R₃ contain from about 1 to about 3 carbon atoms and from 0 to about 1 hydroxy group, e.g., methyl, ethyl, propyl, hydroxyethyl, or hydroxypropyl radicals. The arrow in the formula is a conventional representation of a semipolar bond. Examples of amine oxides suitable for use in this invention include dimethyldodecylamine oxide, oleyldi(2-hydroxyethyl) amine oxide, dimethyl-octylamine oxide, dimethyl-decylamine oxide, dimethyl-tetradecylamine oxide, 3,6,9-trioxaheptadecyldiethylamine oxide, di(2-hydroxyethyl)-tetradecylamine oxide, 2-dodecoxyethyldimethylamine oxide, 3-dodecoxy-2-hydroxypropyldi(3-hydroxypropyl) amine oxide, dimethylhexadecylamine oxide.
• 5. Long chain tertiary phosphine oxides corresponding to the following general formula: RR'R''P -> Owherein R contains an alkyl, alkenyl or monohydroxyalkyl radical ranging from about 8 to about 18 carbon atoms in chain length, from 0 to about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety and R' and R'' are each alkyl or monohydroxyalkyl groups containing from about 1 to about 3 carbon atoms. The arrow in the formula is a conventional representation of a semipolar bond. Examples of suitable phosphine oxides are: dodecyldimethylphosphine oxide, tetradecyldimethylphosphine oxide, tetradecylmethylethylphosphine oxide. 3,6,9,-trioxaoctadecyldimethylphosphine oxide, cetyldimethylphosphine oxide, 3-dodecoxy-2-hydroxypropyldi(2-hydroxyethyl) phosphine oxide, stearyldimethylphosphine oxide, cetylethylpropylphosphine oxide, oleyldiethylphosphine oxide, dodecyldiethylphosphine oxide, tetradecyldiethylphosphine oxide, dodecyldipropylphosphine oxide, dodecyldi(hydroxymethyl)phosphine oxide, dodecyldi(2-hydroxyethyl)phosphine oxide, tetradecylmethyl-2-hydroxypropylphosphine oxide, oleydimethylphosphine oxide, 2-hydroxydodecyldimethylphosphine oxide.
• 6. Long chain dialkyl sulfoxides containing one short chain alkyl or hydroxy alkyl radical of from about 1 to about 3 carbon atoms (usually methyl) and one long hydrophobic chain which include alkyl, alkenyl, hydroxy alkyl, or keto alkyl radicals containing from about 8 to about 20 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety. Examples include: octadecyl methyl sulfoxide, 2-ketotridecyl methyl sulfoxide, 3,6,9,-trixaoctadecyl 2-hydroxyethyl sulfoxide, dodecyl methyl sulfoxide, oleyl 3-hydroxypropyl sulfoxide, tetradecyl methyl sulfoxide, 3-methoxytridecyl methyl sulfoxide, 3-hydroxytridecyl methyl sulfoxide, 3-hydroxy-4-dodecoxybutyl methyl sulfoxide.

Zwitterionic detersive surfactants are exemplified by those which can be 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 one contains an anionic group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. A general formula for these compounds is: wherein R² contains an alkyl, alkenyl, or hydroxy alkyl radical of from about 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety; Y is selected from the group consisting of nitrogen, phosphorus, and sulfur atoms; R³ is an alkyl or monohydroxyalkyl group containing about 1 to about 3 carbon atoms; X is 1 when Y is a sulfur atom, and 2 when Y is a nitrogen or phosphorus atom; R⁴ is an alkylene or hydroxyalkylene of from about 1 to about 4 carbon atoms and Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups.

Examples of such surfactants include: 4-[N,N-di(2-hydroxyethyl)-N-octadecylammonio]-butane-1-carboxylate; 5-[S-3-hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentane-1-sulfate; 3-[P,P-diethyl-P-3,6,9-trioxatetradexocylphosphonio]-2-hydroxy-propane-1-phosphate; 3-[N,N-dipropyl-N-3-dodecoxy-2-hydroxypropylammonio]-propane-1-phosphonate; 3-(N,N-dimethyl-N-hexadecylammonio)propane-1-sulfonate; 3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate; 4-[N,N-di(2-hydroxyethyl)-N-(2-hydroxydodecyl)ammonio]-butane-1-carboxylate; 3-[S-ethyl-S-(3-dodecoxy-2-hydroxypropyl)sulfonio]-propane-1-phosphate; 3-[P,P-dimethyl-P-dodecylphosphonio]-propane-1-phosphonate; and 5-[N,N-di(3-hydroxypropyl)-N-hexadecylammonio]-2-hydroxy-pentane-1-sulfate.

Other zwitterionics such as betaines can also useful in the present invention. Examples of betaines useful herein include the high alkyl betaines, such as coco dimethyl carboxymethyl betaine, cocoamidopropyl betaine, cocobetaine, lauryl amidopropyl betaine, oleyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alphacarboxyethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis-(2-hydroxyethyl) carboxymethyl betaine, stearyl bis-(2-hydroxypropyl) carboxymethyl betaine, oleyl dimethyl gamma-carboxypropyl betaine, and lauryl bis-(2-hydroxypropyl)alpha-carboxyethyl betaine. The sulfobetaines may be represented by coco dimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, lauryl bis-(2-hydroxyethyl) sulfopropyl betaine and the like; amidobetaines and amidosulfobetaines, wherein the RCONH(CH₂)₃ radical is attached to the nitrogen atom of the betaine are also useful in this invention. Preferred betaines for use in the present compositions are cocoamidopropyl betaine, cocobetaine, lauryl amidopropyl betaine, and oleyl betaine.

Examples of amphoteric detersive surfactants which can be used in the compositions of the present invention are those which are 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, or phosphonate. Examples of compounds falling within this definition are sodium 3-dodecyl-aminopropionate, sodium 3-dodecylaminopropane sulfonate, sodium lauryl sarcosinate, N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teaching of US-A-2,658,072, N-higher alkyl aspartic acids such as those produced according to the teaching of US-A-2,438,091, and the products sold under the trade name "MIRANOL"™ and described in US-A-2,528,378.

The most preferred shampoos of the present invention contain specific combinations of anionic surfactants, zwitterionic surfactants, and amphoteric surfactants. The preferred shampoos contain from 2% to 16% of alkyl sulfates, from 0% to 14% of ethoxylated alkyl sulfates, and from 0% to 10% by weight of an optional detersive surfactant selected from the nonionic, amphoteric, and zwitterionic detersive surfactants, with a total surfactant level of from 10% to 25% by weight.

An essential component of the present invention is a nonionic silicone hair conditioning agent which is insoluble in the shampoo compositions hereof. The silicone conditioning agent comprises a silicone fluid component which contains a nonvolatile insoluble silicone fluid and optionally comprises a silicone gum which is insoluble in the shampoo composition as a whole but is soluble in the silicone fluid. The silicone hair conditioning agent can also comprise a silicone resin to enhance silicone fluid component deposition efficiency. The silicone hair conditioning agent may comprise volatile silicone components; however, such volatile silicones will preferably exceed no more than 0.5%, by weight, of the shampoo composition.

The silicone hair conditioning agent for use herein will preferably have viscosity of from 1,000 to 2,000,000 mm²s⁻¹ (1,000 to 2,000,000 centistokes) at 25°C, more preferably from 10,000 to 1,800,00 mm²s⁻¹ (10,000 to 1,800,000), even more preferably from 100,000 to 1,500,000 mm²s⁻¹ (100,000 to 1,500,000). The viscosity can be measured by means of a glass capillary viscometer as set forth in Dow Corning Corporate Test Method CTM0004, July 20, 1970.

The shampoo compositions hereof will generally comprise from 0.1% to 10%, by weight, of the silicone hair conditioning agent, preferably from 0.5% to 8%, more preferably from 1% to 5% by weight.

Suitable insoluble, nonvolatile silicone fluids include polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, polyether siloxane copolymer and mixtures thereof. However, other insoluble, nonvolatile silicone fluids having hair conditioning properties nay be used. The term "nonvolatile" as used herein shall mean that the silicone material exhibits very low or no significant vapor pressure at ambient conditions, as is well understood in the art. The term "silicone fluid" shall mean flowable silicone materials having a viscosity of less than 1,000,000 mm²s⁻¹ (centistokes) at 25°C. Generally, the viscosity of the fluid will be between about 5 and 1,000,000 mm²s⁻¹ (centistrokes) at 25°C, preferably between about 10 and about 100,000 mm²s⁻¹. The term "silicone", as used herein, shall be synonomous with the term "polysiloxane".

The nonvolatile polyalkylsiloxane fluids that may be used include, for example, polydimethyl siloxanes. These siloxanes are available, for example, from the General Electric Company as a Viscasil (RTM) series and from Dow Corning as the Dow Corning 200 (RTM) series.

The polyalkylaryl siloxane fluids that may be used, also include, for example, polymethylphenylsiloxanes. These siloxanes ire available, for example, from the General Electric Company as SF 1075 methyl phenyl fluid or from Dow Corning as 556 Cosmetic Grade Fluid.

The polyether siloxane copolymers that lay be used include, for example, a polypropylene oxide modified dimethylpolysiloxane (e.g., Dow Corning DC-1248 (RTM)) ethylene oxide or mixtures of ethylene oxide and propylene oxide lay also be used. The ethylene oxide and polypropylene oxide level must be sufficiently low to prevent solubility in water and the composition hereof.

Silicone fluids hereof also include polyalkyl or polyaryl slloxanes with the following structure: wherein R is alkyl or aryl, and x is an integer from about 7 to about 8,000 may be used. "A" represents groups which block the ends of the silicone chains.

The alkyl or aryl groups substituted on the siloxane chain (R) or at the ends of the siloxane chains (A) may have any structure as long as the resulting silicones remain fluid at room temperature, are hydrophobic, are neither irritating, toxic nor otherwise harmful when applied to the hair, are compatible with the other components of the composition, are chemically stable under normal use and storage conditions, and are capable of being deposited on and of conditioning hair.

Suitable A groups include methyl, methoxy, ethoxy, propoxy, and aryloxy. The two R groups on the silicone atom may represent the same group or different groups. Preferably, the two R groups represent the same group. Suitable R groups include methyl, ethyl, propyl, phenyl, methyl phenyl and phenylmethyl. The preferred silicones are polydimethyl siloxane, polydiethylsiloxane, and polymethylphenylsiloxane. Polydimethylsiloxane is especially preferred.

References disclosing suitable silicone fluids include US-A-2,826,551, Geen; US-A-3,964,500, Drakoff, issued June 22, 1976; US-A-4,364,837, Pader; and GB-A-849,433, Woolston Silicon Compounds distributed by Petrarch Systoms, Inc., 1984 provides an extensive (though not exclusive) listing of suitable silicone fluids.

Another silicone material that can be especially useful in the silicone conditioning agents is insoluble silicone gum. The term "silicone gum", as used herein, means polyorganosiloxane materials having a viscosity at 25°C of greater than or equal to 1,000,000 mm²s⁻¹ (centistokes). Silicone gums are described by Petrarch and others including US-A-4,152,416, Spitzer et al., issued May 1, 1979 and Noll, Walter, Chemistry and Technology of Silicones, New York: Academic Press 1968. Also describing silicone gums are General Electric Silicone Rubber Product Data Sheets SE 30, SE 33, SE 54 and SE 76. The "silicone gums" will typically have a mass molecular weight in excess of 200,000, generally between 200,000 and 1,000,000. Specific examples include polydimethylsiloxane, (polydimethylsiloxane) (methylvinylsiloxane) copolymer, poly(dimethylsiloxane) (diphenyl siloxane)(methylvinylsiloxane) copolymer and mixtures thereof.

Preferably the silicone hair conditioning agent comprises a mixture of a polydimethylsiloxane gum, having a viscosity greater than about 1,000,000 mm²s⁻¹ (centistokes) and polydimethylsiloxane fluid having a viscosity of from about 10 mm²s⁻¹ (centistokes) to about 100,000 mm²s⁻¹ (centistokes), wherein the ratio of gum to fluid is from about 30:70 to about 70:30, preferably from about 40:60 to about 60:40.

Another optional ingredient that can be included in the silicone conditioning agent is silicone resin. Silicone resins are highly crosslinked polymeric siloxane systems. The crosslinking is introduced through the incorporation of trifunctional and tetrafunctional silanes with monofunctional or difunctional, or both, monomer units during manufacture of the silicone resin. As is well understood in the art, the degree of crosslinking that is required in order to result in a silicone resin will vary according to the specific silane units incorporated into the silicone resin. In general, silicone materials which have a sufficient level of trifunctional and tetrafunctional siloxane monomer units (and hence, a sufficient level of crosslinking) such that they dry down to a rigid, or hard, fill are considered to be silicone resins. The ratio of oxygen atoms to silicon atoms is indicative of the level of crosslinking in a particular silicone material. Silicone materials which have at least about 1.1 oxygen atoms per silicon atom will generally be silicone resins herein. Preferably, the ratio of oxygen:silicon atoms is at least about 1.2:1.0. Silanes used in the manufacture of silicone resins include monomethyl-, dimethyl-, monophenyl-, diphenyl-, methylphenyl-, monovinyl-, and methylvinyl-chlorosilanes, and tetrachlorosilane, with the methyl-substituted silanes being most commonly utilized. Preferred resins are offered by General Electric as GE SS4230 (RTM) and SS4267 (RTM). Commercially available silicone resins will generally be supplied in an unhardened form in a low viscosity volatile or nonvolatile silicone fluid. The silicone resins for use herein should be supplied and incorporated into the present compositions in such unhardened form, as will be readily apparent to those skilled in the art.

Background material on silicones including sections discussing silicone fluids, gums, and resins, as well as manufacture of silicones, can be found in Encyclopedia of Polymer Science and Engineering, Volume 15, Second Edition, pp 204-308, John Wiley & Sons, Inc., 1989.

Silicone materials and silicone resins in particular, can conveniently be identified according to a shorthand nomenclature system well known to those skilled in the art as "MDTQ" nomenclature. Under this system, the silicone is described according to presence of various siloxane monomer units which make up the silicone. Briefly, the symbol M denotes the monofunctional unit (CH₃)₃SiO_0.5; D denotes the difunctional unit (CH₃)₂SiO; T denotes the trifunctional unit (CH₃)SiO_1.5; and Q denotes the quadri- or tetra-functional unit SiO₂. Primes of the unit symbols, e.g., M', D', T', and Q' denote substituents other than methyl, and must be specifically defined for each occurrence. Typical alternate substituents include groups such as vinyl, phenyls, amines, hydroxyls, etc. The molar ratios of the various units, either in terms of subscripts to the symbols indicating the total number of each type of unit in the silicone (or an average thereof) or as specifically indicated ratios in combination with molecular weight complete the description of the silicone material under the MDTQ system. Higher relative molar amounts of T, Q, T' and/or Q' to D, D', M and/or or M' in a silicone resin is indicative of higher levels of crosslinking. As discussed before, however, the overall level of crosslinking can also be indicated by the oxygen to silicon ratio.

The silicone resins for use herein which are preferred are MQ, MT, MTQ, MQ and MDTQ resins. Thus, the preferred silicone substituent is methyl. Especially preferred are MQ resins wherein the M:Q ratio is from about 0.5:1.0 to about 1.5:1.0 and the average molecular weight of the resin is from about 1000 to about 10,000.

The weight ratio of the nonvolatile silicone fluid component to the silicone resin component is from about 4:1 to about 400:1, preferably this ratio is from about 9:1 to about 200:1, more preferably from about 19:1 to about 100:1, particularly when the silicone fluid component is a polydimethylsiloxane fluid or a mixture of polydimethylsiloxane fluid and polydimethylsiloxane gum as described above.

The shampoo compositions of the present invention comprise one or more organic, soluble, cationic surfactants useful for the conditioning of hair, hereinafter "cationic conditioning agent", selected from the group consisting of quaternary ammonium surfactants and amino surfactants that are positively charged at the pH of the shampoo composition. The shampoo compositions will generally contain from 0.2% to 10%, preferably from 0.5% to 8%, more preferably from 1% to 5% by weight, of the soluble cationic conditioning agent. As just discussed, the cationic conditioning surfactant must be soluble in the shampoo composition, i.e., an amount of the cationic conditioning agent within the ranges set forth above should be solubilized in the shampoo composition. The cationic surfactants for use herein also must contain one or more nonionic hydrophilic moieties. Sufficient hydrophilic moieties must be present to maintain solubility subsequent to any ionic complexation that may occur between the cationic conditioning surfactants and the anionic detersive surfactants.

The preferred cationic conditioning surfactants for use in the present invention are those which are useful for providing conditioning benefits, particularly hair conditioning properties and which are quaternary ammonium or amino compounds having at least one N-radical containing one or more nonionic hydrophilic moieties selected from alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, and alkylester moieties, and combinations thereof. The surfactant contains at least one hydrophilic moiety within 4 (inclusive), preferably within 3 (inclusive), carbon atoms of the quaternary nitrogen or cationic amino nitrogen. For purposes herein, this means that the closest non-carbon atom in the hydrophilic moiety to the cationic nitrogen must be within the stated number of carbon atoms relative to said nitrogen. Additionally, carbon atoms that are part of a hydrophilic moiety, e.g., carbon atoms in a hydrophilic polyoxyalkylene (e.g.,-CH₂-CH₂-O-), that are adjacent to other hydrophilic moieties are not counted as when determining the number of hydrophilic moieties within 4, or preferably 3, carbon atoms of the cationic nitrogen. In general, the alkyl portion of any hydrophilic moiety is preferably a C₁-C₃ alkyl. Suitable hydrophile-containing radicals include, for example, ethoxy, propoxy, polyoxyethylene, polyoxypropylene, ethylamido, propylamido, hydroxymethyl, hydroxyethyl, hydroxypropyl, methylester, ethylester, propylester, or mixtures thereof, as nonionic hydrophile moieties. The amino surfactants must be positively charged at the pH of the shampoo compositions. Generally, the pH of the shampoo compositions will be less than about 10, typically from about 3 to about 9, preferably from about 4 to about 8.

Among the quaternary ammonium cationic surfactants useful herein are those of the general formula: wherein R₁, R₂, R₃ and R₄ radicals comprise, independently, substituted or unsubstituted hydrocarbyl chains of from 1 to about 30 carbon atoms, or a hydrocarbyl having from 1 to about 30 carbon atoms and containing one or more aromatic, ether, ester, amido, or amino moieties present as substituents or as linkages in the radical chain, wherein at least one of the R₁-R₄ radicals contains one or more hydrophilic moleties selected from alkoxy (preferably C₁-C₃ alkoxy), polyoxyalkylene (preferably C₁-C₃ polyoxyalkylene), alkylamido, hydroxyalkyl, alkylester, and combinations thereof. Preferably, the cationic conditioning surfactant contains from 2 to about 10 nonionic hydrophile moieties located within the above stated ranges. For purposes herein, each hydrophilic amido, alkoxy, hydroxyalkyl, alkylester, alkylamido or other unit is considered to be a distinct nonionic hydrophile moiety. X is a soluble salt forming anion preferably selected from halogen (especially chlorine), acetate, phosphate, nitrate, sulfonate, and alkyl sulfate radicals.

Preferred quaternary ammonium salt surfactants include those of the formula wherein n is from 8-28, preferably 16, $\text{x+y = 2 to about 15}$ . Z is a short chain alkyl, preferably a C₁-C₃ alkyl, more preferably methyl, and X is a water soluble salt forming anion (e.g., Cl, sulfate, etc.)

Other preferred quaternary ammonium salt surfactants include those of the formula wherein Z₁ and Z₂ are, independently, substituted or unsubstituted hydrocarbyls, and, preferably, Z₁ is an alkyl, preferably a C₁-C₃ alkyl, more preferably methyl, and Z₂ is a short chain hydroxyalkyl, preferably hydroxymethyl or hydroxyethyl, n and m independently are integers from 2 to 4, inclusive, preferably from 2 to 3, inclusive, more preferably 2, R' and R'', independently, are substituted or unsubstituted hydrocarbyls, preferably C₁₂₋C₂₀ alkyl or alkenyl, and X is a soluble salt-forming anion (e.g., sulfate, Cl, etc.).

Still other quaternary ammonium salt surfactants are of the formulas: wherein R is a hydrocarbyl, preferably a C₁-C₃ alkyl, more preferably methyl, Z₁ and Z₂ are, independently, short chain hydrocarbyls, preferably C₂-C₄ alkyl or alkenyl, more preferably ethyl, n is from about 2 to about 40, preferably from about 7 to about 30, and X is a soluble-salt forming anion, as set forth previously; wherein R₁ and R₂, independently, are C₁₂-C₂₀ hydrocarbyls, preferably C₁₆-C₁₈ alkyl or alkenyls (e.g., those derived from tallow acid), Z is a C₁-C₃ hydrocarbyl, preferably methyl, n is 2 or 3, and X is a soluble salt forming anion; and wherein n is 2 or 3, R₁ and R₂, independently are C₁ - C₃ hydrocarbyls preferably methyl, and X is as defined above.

Specific examples of preferred quaternary ammonium salts include polyoxyethylene (2) stearyl methyl ammonium chloride, methyl bis (hydrogenated tallowamidoethyl) 2-hydroxyethyl ammonium methyl sulfate, polyoxypropylene (9) diethyl methyl ammonium chloride, tripolyoxyethylene (total PEG=10) stearyl ammonium phosphate, bis(N-hydroxyethyl -2-oleyl imidazolinium chloride) polyethylene glycol (12), and isododecylbenzyl triethanolammonium chloride.

Other ammonium quaternary and amino surfactants include those of the above general formula 1 in the form of ring structures formed by covalently linking of the radicals. Examples of such cationic surfactants include imidazolines, imidazoliniums, and pyridiniums, etc., wherein said surfactant has at least one nonionic hydrophile-containing radical as set forth above. Specific examples include 2-heptadecyl-4,5- dihydro-1H-imidazol -1-ethanol, 4,5- dihydro-1-(2-hydroxyethyl)-2-isoheptadecyl -1-phenylmethylimidazolium chloride, and 1-[2-oxo-2-[[2-[(1-oxooctadecyl)oxy]ethyl]amino]ethyl] pyridinium chloride. See also, for example formula V

Salts of primary, secondary and tertiary fatty amines are also preferred cationic surfactant materials. The alkyl groups of such amines preferably have from about 1 to about 30 carbon atoms and must contain at least one, preferably 2 to about 10, nonionic hydrophilic moieties selected from alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, and alkylester moleties, and mixtures thereof. Secondary and tertiary amines are preferred, tertiary amines are particularly preferred. Specific examples of suitable amines include diethyl aminoethyl polyoxyethylene (5) laurate, coco-polyglyceryl-4 hydroxypropyl dihydroxy ethylamine, and dihydroxyethyl tallowamine hydrochloride.

The shampoo compositions of the present invention are liquids which, preferably, and are pourable at room temperature. The compositions hereof will comprise an aqueous carrier, i.e., water, which will generally be present at a level of 20% to 95% by weight of the composition, preferably from 60% to 85% by weight for pourable, liquid formulations. The compositions of the present invention can also be in other forms, such as gels, mouse, etc. In such cases, appropriate components known in the art such as gelling agents (e.g., hydroxyethyl cellulose), etc. can be included in the compositions. Gels will typically contain from 20% to 90% by weight water. Mousses will contain aeresol propellant in a low viscosity composition and are packaged in an aerosol can, according to techniques well know in the art.

Since the silicone conditioning agent used in the present compositions is an insoluble silicone dispersed in the compositions, it is preferred to utilize a suspending agent for the silicone. Suitable suspending agents are long chain acyl derivatives, long chain amine oxides, and mixtures thereof, wherein such suspending agents are present in the shampoo compositions in crystalline form. A variety of such suspending agents are described in US-A-4,741,855, Grote et al., issued May 3, 1988. Especially preferred is ethylene glycol distearate.

Also included among the long chain acyl derivatives useful as suspending agents are the N,N-di(hydrogenated) C₁₆-C₁₈ amido benzoic acid, or soluble salt (e.g., K, Na salts) thereof particularly N,N-di(hydrogenated)tallow amido benzoic acid which is commercially marketed by Stepan Company (Northfield, Illinois, USA).

Another useful suspending agent for the silicone conditioning agents of the present compositions is xanthan gum as described in US-A-4,788,006, Bolich et al., issued June 5, 1984. The combination of long chain acyl derivatives and xanthan gum as a suspending system for silicone is described in US-A-4,704,272, Oh et al., issued November 3, 1987, and may also be used in the present compostions.

Generally, the shampoo compositions will comprise from 0.1% to 5.0%, preferably from 0.5% to 3.0% by weight, of the suspending agent to suspend the silicone conditioning agent.

The present compositions may also comprise a variety of non-essential, optional shampoo components suitable for rendering such compositions more cosmetically or aesthetically acceptable or to provide them with additional usage benefits. A variety of such ingredients are well-known to those skilled in the art, and these include without limiting the invention thereto: pearlescent aids, such as TiO₂ coated mica, ethylene glycol distearate; opacifiers; preservatives, such as benzyl alcohol, 1,3-bis(hydroxymethyl)-5,5 dimethyl-2,4-imidazolidinedione (e.g. Glydant® (RTM), Glyco, Inc., Greenwich, CT, USA), methylchloroisothizolinone (e.g. Kathon® (RTM), Rohm & Haas Co., Philadelphia, PA, USA), methyl paraben, propyl paraben, and imidizolidinyl urea; fatty alcohols, such as cetearyl alcohol, cetyl alcohol, and stearyl alcohol; sodium chloride; sodium sulfate; ethyl alcohol; pH adjusting aids, such as citric acid, sodium citrate, succinic acid, phosphoric acid, monosodium phosphate, disodium phosphate, sodium hydroxide, and sodium carbonate; coloring agents or dyes; perfumes; and sequestering agents, such as disodium ethylenediamine tetra-acetate.

Another optional ingredient that can be advantageously used is an anti-static agent. The anti-static agent should not unduly interfere with the in-use performance and end-benefits of the shampoo; particularly, the anti-static agent should not interfere with (i.e., it should be compatible with) the anionic detersive surfactant. An especially suitable anti-static agent is tricetyl methyl ammonium salt (e.g., the chloride salt, "TCMAC").

Preferred compositions herein comprise anionic surfactant, silicone conditioning agent, TCMAC (or other salt thereof), and soluble cationic conditioning surfactant selected from the compounds of Formula III, above, especially the preferred embodiments of Formula III. Surprisingly, such compositions can exhibit enhanced silicone conditioning agent deposition relative to similar compositions absent the soluble cationic conditioning surfactant.

Typically, from 0.1% to 5% by weight of such anti-static agent is incorporated into the shampoo compositions when they are to be utilized.

Though the silicone suspending agent component may act to thicken the present compositions to some degree, the present compositions may also optionally contain other thickeners and viscosity modifiers such as an ethanolamide of a long chain fatty acid (e.g., polyethylene (3) glycol lauramide and coconut monoethanolamide).

These optional components generally are used individually in the compositions of the present invention at a level of from 0.01% to 10% , preferably from 0.05% to 5.0% by weight of the shampoo composition.

The pH of the present compositions sill generally be in the range of from about 2 to about 10, preferably from about 3 to about 9.

The compositions of the present invention, in general, can be made by mixing the materials together at elevated temperature, e.g., about 72°C. The silicone resin, if any, and silicone fluid component are first mixed together before being mixed with the other ingredients. The complete mixture is mixed thoroughly at the elevated temperature and is then pumped through a high shear mill and then through a heat exchanger to cool it to ambient temperature. The average particle size of the silicone is preferably from about 0.5 µm (microns) to about 20 µm (microns). Alternately, the silicone conditioning agent can be mixed with anionic surfactant and fatty alcohol, such as cetyl and stearyl alcohols, at elevated temperature, to form a premix containing dispersed silicone. The premix can then be added to and mixed with the remaining materials of the shampoo, pumped through a high shear mill, and cooled.

The shampoo compositions of the present invention are utilized conventionally, i.e., the hair is shampooed by applying an effective amount of the shampoo composition to the scalp, and then rinsing it out. Application of the shampoo to the scalp in general, encompasses massaging or working the shampoo in the hair such that all or most of the hair on the scalp is contacted. The term an "effective amount" as used herein, is an amount which is effective in cleaning and conditioning the hair. Generally, from 1 g to 20 g of the composition is applied for cleaning and conditioning the hair.

EXAMPLES

The following examples illustrate the present invention.

All parts, percentages, and ratios herein are by weight unless otherwise specified. Some components may come from suppliers as solutions. The levels given reflect the active weight percent of such materials, unless otherwise specifically indicated.

Example I

The following is a shampoo composition of the present invention.

Component	Weight %
Ammonium Lauryl Sulfate	13.5
Ammonia Laureth (3) Sulfate	4.0
Methyl bis(hydrogenated tallow amidoethyl) 2-hydroxyethyl ammonium methyl sulfate *	1.5
Coconut Monoethanol Amide	1.0
Ethylene Glycol Distearate	1.5
Ammonium Xylene Sulfonate	1.0
Xanthan Gum	0.5
Polydinethylsiloxane **	3.0
Cetyl Alcohol	0.4
Stearyl Alcohol	0.2
Perfume	1.2
Color Solution	0.6
Preservative	0.2
Water and Minor	-- to 100% --

* Available under the tradename VARISOFT 110 (RTM) from Sherex Chemical Co. (Dublin, Ohio, USA)

** A 40/60 weight ratio blend of polydimethylsiloxane gum (GE SE76 (RTM), General Electric Co., Silicone Products Div., Waterford. NY, USA) and a polydimethylsiloxane fluid (about 350 mm²s⁻¹ (centistokes)).

The composition can provide excellent in-use hair cleaning and conditioning, for both damaged and undamaged, hair types.

Example II

The following is an example of a shampoo composition of the present invention.

Component	Weight %
Ammonium Lauryl Sulfate	13.0
Ammonium Laureth (3) Sulfate	5.0
Polyoxyethylene (2) stearyl methyl ammonium chloride *	1.0
Coconut Monoethanol Amide	1.5
Ethylene Glycol Distearate	2.0
Ammonium Xylene Sulfonate	1.0
Polydlmethylsiloxane **	2.5
Cetyl Alcohol	0.4
Stearyl Alcohol	0.2
Perfume	1.2
Color Solution	0.6
Preservative	0.2
Water and Minors	-- to 100% --

* Available under the tradename ETHOQUAD 18/12 from Armak Company (McCook, Illinois, USA).

** A 40/60 weight ratio blend of polydimethyl siloxane gum (GE SE76 (RTM), General Eleactric Co. Silicone Products Div., Waterford, NY, USA) and a polydimethylsiloxane fluid (about 350 mm²s⁻¹ (centistokes)).

The composition can provide excellent in-use hair cleaning and conditioning, for both damaged and undamaged, hair types.

Example III

The following is an example of a shampoo composition of the present invention.

Component	Weight %
Ammonium Lauryl Sulfate	13.5
Ammonia Laureth (3) Sulfate	4.0
Polyoxyethylene (2) stearyl methyl ammonium chloride *	1.5
Coconut Monoethanol Amide	1.5
Ethylene Glycol Distearate	2.0
Trimethylsiloxysilicate	0.1
Polydimethylsiloxane **	2.0
Cetyl Alcohol	0.4
Stearyl Alcohol	0.2
Perfume	1.2
Color Solution	0.6
Preservative	0.2
Water and Minors	-- to 100% --

* Available under the tradename ETHOQUAD 18/12 from Armak Company (McCook, Illinois, USA).

** A 40/60 weight ration blend of polydimethylsiloxane gum (GE SE76 (RTM), General Eleactric Co., Silicone Products Div., Waterford, NY, USA) and a polydimethylsiloxane fluid (about 350 mm²s⁻¹ (centistokes)).

The composition can provide excellent in-use hair cleaning and conditioning, for both damaged and undamaged, hair types.

Example IV

The following is an example of a shampoo composition of the present invention.

Component	Weight %
Ammonium Lauryl Sulfate	4.0
Cocoamidopropyl Betaine	3.5
Ammonium Laureth (3) Sulfate	9.0
Sodium N-Lauryl β-Iminodipropionate	4.0
Methyl bis (hydrogenated tallow amidoethyl) 2-hydroxyethyl ammonium methyl sulfate *	1.0
Coconut Monoethanol Amide	2.0
Ethylene Glycol Distearate	2.0
Xanthan Gum	0.5
Polydimethylsiloxane **	2.0
Cetyl Alcohol	0.4
Stearyl Alcohol	0.2
Perfume	1.2
Color Solution	0.6
Preservative	0.2
Water and Minors	-- to 100% --

* Available under the tradename VARISOFT 110 (RTM) from Sherex Chemical Co. (Dublin, Ohio, USA)

** A 40/60 weight ratio blend of polydimethylsiloxane gum (GE SE76 (RTM), Eleactric Co., Silicone Products Div., Waterford, NY, USA) and a polydimethylsiloxane fluid (about 350 mm²s⁻¹ (centistokes)).

The composition can provide excellent in-use hair cleaning and conditioning, for both damaged and undamaged, hair types.

Example V

The following is a shampoo composition of the present invention.

Component	Weight %
Ammonia Lauryl Sulfate	8.5
Ammonia Laureth (3) Sulfate	8.5
Methyl bis(hydrogenated tallow amidoethyl) 2-hydroxyethyl ammonium methyl sulfate *	2.0
Coconut Monoethanol Amide	1.5
Ethylene Glycol Distearate	2.0
Ammonium Xylene Sulfonate	1.5
Tricetyl Methyl Ammonium Chloride	.5
Polydimethylsiloxane Fluid**	1.4
MQ Silicone Resin/Volatile Cyclomethicone***	.1
Cetyl Alcohol	.4
Stearyl Alcohol	.2
Perfume	1.0
Color Solution	.6
Preservative	.03
Water and Minors	-- to 100% --

* Available under the tradename VARISOFT 110 (RTM) from Sherex Chemical Co. (Dublin, Ohio, USA)

**A 40/60 weight ratio blend of polydimethylsiloxane gum (GE SE76 (RTM), General Electric Co., Silicone Products Div., Waterford, NY, USA) and a polydimethylsiloxane fluid (about 350 mm²s⁻¹ (centistokes)).

*** A 60:40 weight ratio blend of the MQ resin in volatile silicone carrier. M:Q molar ratio of about 0.8:1.0.

The composition con provide excellent in-use hair cleaning and conditioning, for both damaged end undamaged, hair types.

The compositions hereof can be made by preparing a premix of the entire amount of silicone conditioniong agent (i.e., the silicone fluid component end, if any, the silicone resin) to be incorporated into the shampoo, along with sufficient ammonium laureth sulfate end cetyl and stearyl alcohol such that the premix comprises 30% by weight silicone conditioning agent, 69% by weight surfactant, and 1% by weight of the alcohols. The premix ingredients are heated end stirred et 72°C for about 10 minutes and the premix is then conventionally mixed with the remaining hot ingredients. The composition is then pumped through a high shear mixer and cooled.

Claims (11)

1. A liquid hair conditioning shampoo composition characterized in that it comprises:

   (a) from 5% to 50%, by weight, of an anionic surfactant component;

   (b) from 0.1% to 10%, preferably from 0.5 to 8%, by weight, of a dispersed, insoluble, nonionic silicone hair conditioning agent, said silicone hair conditioning agent comprising a non-volatile, insoluble, nonionic silicone fluid component;

   (c) from 0.2% to 10%, by weight, of a soluble cationic, amino or quaternary ammonium conditioning surfactant having a single cationic nitrogen atom and at least one N-radical containing one or more hydrophilic moieties that are within 4 carbon atoms, inclusive, of the cationic nitrogen, said hydrophilic moieties being selected from the group consisting of alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, and alkylester moieties, and combinations thereof; preferably from 0.5% to 8% by weight of a cationic conditioning surfactant containing from 2 to 10 of said hydrophilic moieties within 3 carbon atoms, inclusive, of a cationic nitrogen; and

   (d) an aqueous carrier.
2. A liquid hair conditioning shampoo composition as in Claim 1, further comprising a suspending agent for said silicone hair conditioning agent.
3. A liquid hair conditioning agent as in Claim 1 or 2, wherein said soluble, cationic conditioning agent is selected from the group consisting of: wherein n is from 8-28, $\text{x+y = 2 to 15}$ , Z is a C₁-C₂ alkyl, and X is a water soluble salt forming anion; wherein Z₁ is a C₁-C₃ alkyl, Z₂ is a C₁-C₃, hydroxyalkyl, n and m independently are integers from 2 to 4, inclusive, R' and R'', independently, are substituted or unsubstituted hydrocarbyls, and X is a soluble salt-forming anion; wherein R is a C₁-C₃ alkyl, Z₁ and Z₂ are, independently, C₂-C₄ alkyl or alkenyl, n is from 7 to 30, and X is a soluble-salt forming anion; and wherein n is 2 or 3, R₁ and R₂ independently are C₁ - C₃ hydrocarbyls and X is a soluble salt-forming anion; and mixtures thereof.
4. A shampoo composition as in Claim 1, 2, or 3, further comprising from 0.5% to 20% by weight of a detersive surfactant selected from the group consisting of nonionic, zwitterionic, and amphoteric surfactants, and mixtures thereof.
5. A shampoo composition as in Claim 1, 2, 3, or 4, wherein said anionic detersive surfactant component comprises alkyl sulfates, ethoxylated alkyl sulfates, or a mixture thereof, preferably 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, aluric monoglyceride sodium sulfate, sodium lauryl sulfate, sodium laureth sulfate, potassium lauryl sulfate, potassium laureth sulfate, lauryl sarcosine, cocoyl sarcosine, ammonium cocoyl sulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate, sodium lauroyl sulfate, potassium cocoyl sulfate, potassium lauroyl sulfate, triethanolamine lauroyl sulfate, sodium tridecyl benzene sulfonate, sodium dodecyl benzene sulfonate, or a mixture thereof.
6. A shampoo composition as in Claim 4 wherein the composition comprises a detersive surfactant selected from the group consisting of betaines, amido propyl betaines, and mixtures thereof.
7. A shampoo composition as in Claim 1, 2, 3, 4, 5, or 6 wherein the silicone conditioning agent is present at a level of from 1% to 5% by weight and comprises a silicone fluid component containing polydimethylsiloxane gum having a viscosity greater than 1,000,000 mm²s⁻¹(centistokes), and a polydimethylsiloxane fluid having a viscosity of from 10 centistokes to 100,000 mm²s⁻¹ (centistokes), wherein the ratio of gum to fluid is from 30:70 to 70:30.
8. A shampoo composition as in Claim 1, 2, 3, 4, 5, 6, or 7, wherein said silicone conditioning agent comprises a silicone fluid component and a silicone resin component, said resin is soluble in said fluid, and the weight ratio of silicone fluid:silicone resin is from 4:1 to 400:1.
9. A liquid hair conditioning shampoo composition characterized in that it comprises:

   (a) from 5% to 50%, by weight, of an anionic surfactant component;

   (b) from 0.1% to 10%, by weight, of a dispersed, insoluble, nonionic silicone hair conditioning agent, said silicone hair conditioning agent comprising a non-volatile, insoluble, nonionic silicone fluid component;

   (c) from 0.2% to 10%, by weight, of a soluble cationic, amino or quaternary ammonium conditioning surfactant having a single cationic nitrogen atom and at least one N-radical containing one or more hydrophilic moieties that are within 4 carbon atoms, inclusive, of the cationic nitrogen, said hydrophilic moieties being selected from the group consisting of alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, and alkylester moieties, and combinations thereof; and

   (d) an aqueous carrier; and

   (e) from 0.1% to 5% by weight of an anionic surfactant compatible, cationic anti-static agent.
10. A liquid hair conditioning shampoo composition as in Claim 9, wherein said anti-static agent is tricetyl methyl ammonia salt and said soluble, cationic conditioning surfactant is of the formula: wherein Z₁ and Z₂ are, independently, substituted or unsubstituted hydrocarbyls, n and m independently are integers from 2 to 4, R' and R'' independently are substituted or unsubstituted hydrocarbyls, and X is a soluble salt-forming anion; wherein preferably Z₁, is a C₁-C₃ alkyl, Z₂ is a hydroxyethyl or hydroxymethyl, m and n both are 2, and R' and R'' independently are C₁₂-C₂₀ alkyl or alkenyl.
11. A method for cleaning and conditioning the hair comprising applying from 1 g to 20 g of the composition of Claim 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, to the hair and then rinsing said composition from the hair.