Indian Patents. 259113:"CONDITIONING SHAMPOOS WITH DETERGENT SOLUBE SILICONES"

Title of Invention	"CONDITIONING SHAMPOOS WITH DETERGENT SOLUBE SILICONES"
Abstract	A conditioning shampoo comprising: (a) 4-25 weight % of an anionic surfactant or mixtures of two or more anionic surfactants; (b) 0.025-3 weight % of a cationic deposition polymer, (c) 0.1-5 weight % of a detergent soluble silicone having a molecular weight less than 100,000 daltons; and (d) water.

Full Text	CONDITIONING SHAMPOOS WITH DETERGENT SOLUBLE SILICONES Field of the Invention This invention relates to improved conditioning shampoos that maybe made without stabilizing agents for silicones. Background of the Invention A variety of conditioning shampoos (also called "2-in-l shampoos") have been sold and/or described in the patent literature. These products characteristically include an insoluble silicone such as dimethicone in combination with some type of stabilizing agent. The stabilizing agents that have been used have included, for example, ethylene glycol distearate (which is also a pearlizing agent), long chain alcohols such as those having C20-40 carbons (commonly referred to as "Unilin" technology), behenyi alcohol, selected acrylates such as ACULYN-33, and other systems such as cetearyl alcohol mixtures. Some of the stabilizers require heat in the manufacturing processes and others made be made at room temperature. U.S. Patent Number 5,945,093 describes an improved stable conditioning shampoo imparts improved physical and cosmetic properties to the hair such as wet and dry comb, wet and dry feel, gloss, static control and manageability, yet does not cause build-up and does not contain any polyhydric compounds. The shampoo includes an anionic surfactant, a water soluble cationic surfactant, a water-insoluble conditioning agent, and a suspending agent where the suspending agent is a mixture of a cellulose derivative and a PVM/MA .decadiene cross polymer. The conditioning shampoo is stable for extended periods. U.S. Patent Number 5,932,203 describes conditioning shampoo compositions which comprise (A) an anionic surfactant component selected from the group consisting of anionic surfactants, zwitterionic or amphoteric surfactants having an attached group that is anionic at (he pH of the composition (B) an organic, cationic, hair conditioning polymer, (C) a selected water insoluble, synthetic ester; and (D) water. U.S. Patent Number 6,287,546 describes improved stabilized shampoo compositions containing siloxysilicate materials commonly referred to as MQ resins, wherein the stabilizers are selected from (i) long chain fatty alcohols with greater than 14 carbons; (ii) acrylates/steareth-20 methacrylate copolymer, acrylates copolymer; and acrylates/C10-30 alkyl acryiate cross polymer; and (iii) selected N,N-disubstituted phthalamic acids and their ammonium salts. Of course the use of soluble silicones can be complex if a product is to be obtained that does not rinse the soluble silicone down the drain during shampooing. Thus, there remains a need for conditioning shampoos that can deliver a higher degree of conditioning. There is also a need for conditioning shampoos that can be made in part or in whole without the need for stabilizing agents required for insoluble silicone materials. Yet another object is to create conditioning shampoos that can use soluble silicones and still achieve good conditioning. Brief Summary of the Invention The conditioning shampoos of this invention comprise: (a) 4-25 weight % of an anionic surfactant or mixtures of more than one such surfactant; (b) 0.025-3 weight % of a canonic deposition polymer; (c) 0.1-5 weight % of a detergent soluble silicone having a molecular weight less than 100,000 daltons, particularly in the range of 1,000-10,000 and, more particularly, in the range of 2,000-4,000; and (d) water (including water that comes in with the ingredients) for example in a range of 57-90 weight %. In addition to these ingredients, one or more optional ingredients selected fiom the group consisting of the following list maybe included: (e) 0-10 weight % (particularly 0.5-10 weight %) of a co-surfectant or mixtures of more than one co-surfactant selected fiom the group consisting of amphoteric, nonionic and zwitterionic surfactants and mixtures thereof; (f) 0-5 weight % of a pearlizer (including ethylene glycol distearate); (g) 0-5 weight % of a salt such as NaCl as a viscosity modifier; (h) 0-0.5 weight % of a dictating agent such as EDTA; (i) 0-1 weight % of a buffering agent (which may also have some chelating properties) such as sodium dihydrogen phosphate monohydrate; (j) 0-5.0 weight % fragrance (particularly 0.2-2.0%); (k) 0-1 weight % of a pH adjuster (such as citric acid); (1) 0-5 weight % of a coloring agent; (m) 0-8 weight % of an insoluble silicone; (n) 0-5 weight % of a silicone resin; (o) 0-10 weight % of a stabilizing agent for the insoluble silicone and/or the silicone resin (particularly 0-5.0%); and (p) 0-2 weight % of a preservative. Note that for ingredients (a) and (b), these ingredients may be added as aqueous solutions (for example, having 8-90% of the active ingredient). For optional ingredients (e) and (f), they may be added as a pre-formed aqueous solution or suspension. For optional ingredients (g), (h), (i), (k), (1), (o) and (p) these ingredients may be added as aqueous solutions. For optional ingredients (m) and (n), these ingredients may be added as pre-formed stabilized emulsions. Detailed Description of the Invention The shampoos of this invention may be made as clear, translucent or opaque products which are colored or colorless. In addition, the compositions of this invention may be made with soluble silicones only and without the need for any stabilizers for the silicones, or they may be made by supplementing the system with a portion of insoluble silicone with a conventional stabilizing system for those silicones. Additionally, in a special embodiment, an MQ resin is used hi the formulation to form a 3-in-l product with special styling capabilities. The anionic surfactants useful in the compositions of the invention include those familiar to skilled practioners. The anionic surfactant of component (a) will generally be present at a level from about 4 weight % to about 25%, particularly from about 6 weight % to about 19 weight %, with an amount of about 7-17 weight % being of particular interest. Anionic detersive surfactants useful herein include those that are disclosed in U.S. Patent Number 5,573,709, the disclosure of which is incorporated herein by reference in its entirety as to the description of such surfactants. Examples of the anionic surfactants useful in mis invention include alkyl and alkyl ether sulfates, particularly those having from 7-25 carbons. Specific examples of alkyl ether sulfates which may be used in the present invention are sodium and ammonium salts of lauryl sulfate, lauryl ether sulfate, coconut alkyl triethylene glycol ether sulfate; tallow alkyl triethylene glycol ether sulfate, and tallow alkyl hexaoxyethylene sulfate. A particular group of anionic surfactants includes alkyl ether sulfates comprising a mixture of individual compounds, said mixture having an average alkyl chain length of from about 12 to about 16 carbon atoms and an average degree of ethoxylation of from about 1 to about 6 moles of ethylene oxide. Another suitable class of anionic detersive surfactants are the alkyl sulfuric acid salts. 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, for example, SCb, H2SO4, oleum (fuming sulfuric acid) obtained according to known sulfonation methods, including bleaching and hydrolysis. Preferred are alkali metal and ammonium sulfated Cn n-para£6ns. Additional examples of synthetic anionic detersive surfactants which come within the terms of the present invention are the olefin sulfonates, the beta-alkyloxy alkane sulfonates, and the reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide, as well as succinamates. Specific examples of succinamates include disodium N-octadecyl sulfofosuccinamate; tetrasodium N-(l,2-dicarboxyethyl)-N-octadecylsulfosuccinamate; diamyl eater of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; and dioctyl esters of sodium sulfosuccinic acid. Many additional synthetic anionic surfactants are described in McCutcheon's Emulsifiers and Detergents, 1989 Annual, published by M. C. Publishing Co., which descriptions are incorporated herein by reference in their entirety as to the listing of such surfactants. Finally, U.S. Patent Number 3,929,678, Laughlin et al., discloses many other anionic as well as other surfactant types and is incorporated herein by reference in its entirety as to descriptions of such surfactants. A particular group of anionic detersive surfactants for use in the present shampoo compositions include one or more members selected from the group consisting of ammonium lauryi 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, ammonium cocoyl sulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate, sodium lauroyl sulfate, potassium cocoyl sulfate, potassium lauryl sulfate, triethanolamine lauryi sulfate, monoethanolamine cocoyl sulfate, monoethanolamine lauryl sulfate, sodium tridecyl benzene sulfbnate, sodium dodecyi benzene sulfbnate, and mixtures of two or more of the foregoing. A particular anionic component is a combination of 5-20 weight % of ammonium lauryl sulfate and 5-20 weight % of ammonium lauryl ether sulfate. The shampoo compositions of the present invention comprise a cationic polymer particularly an organic polymer, as a deposition aid polymer. Such cationic polymers should also be physically and chemically compatible with the essential components described herein, or should not otherwise unduly impair product stability, aesthetics or performance. The concentration of the organic, cationic, conditioning polymer of the shampoo composition should be generally in the range from about 0.025% to about 3%, preferably from about 0.05% to about 2%, more preferably from about 0.1% to about 1%, by weight of the shampoo composition. The cationic deposition polymer contains cationic nitrogen-containing moieties such as quaternary ammonium or cationic protonated amino moieties. The cationic protonated amines can be primary, secondary, or tertiary amines (preferably secondary or tertiary), depending upon the particular species and the selected pH of the shampoo composition. The average molecular weight of the cationic conditioning polymers is between about 10 million and about 5,000, preferably at least about 100,000, more preferably at least about 200,000, but preferably not more than about 2 million, preferably not more than about 1.5 million. The polymers also have a cationic charge density ranging from about 0.2 meq/gm to about 7 meq/gm, preferably at least about 0.4meq/gm, more preferably at least about 0.6meq/gm, but also preferably less than about 5meq/gm, more preferably less than about 2 meq/gm, at the pH of intended use of the shampoo composition, which pH will generally range from about pH 3 to about pH 9, preferably between about pH 4 and about pH7. Any anionic counterions can be used in association with the cationic deposition polymers so long as the polymers remain soluble hi water, in the shampoo composition, or in a coacervate phase of the shampoo composition, and so long as the counterions are physically and chemically compatible with the essential components of the shampoo composition or do not otherwise unduly impair product performance, stability or aesthetics. Non-limiting examples of such counterions include halides (for example, chlorine, fluorine, bromine, iodine), sulfate and methylsulfate). The cationic nitrogen-containing moiety of the cationic polymer is generally present as a substituent on all, or more typically on some, of the monomer units thereof. Thus, the cationic polymer for use in the shampoo composition includes homopolymers, copolymers, terpolymers, and so forth, of quaternary ammonium or cationic amine-substimted monomer units, optionally in combination with non-cationic monomers referred to herein as spacer monomers. Non-limiting examples of such polymers are described in the CTFA Cosmetic Ingredient Dictionary, 3rd edition, edited by Estrin, Crosley, and Haynes (The Cosmetic, Toiletry, and Fragrance Association, Inc., Washington, D.C. (1982)), which description is incorporated herein by reference as to the description of these polymers. Non-limiting examples of suitable cationic polymers include copolymers of vinyl monomers having cationic protonated amine or quaternary ammonium functionalities with water soluble spacer monomers such as acrylamide, methacrylamide, alkyl and dialkyl acrylamides, alkyl and dialkyl methacrylamides, alkyl acrylate, allyl methacrylate, vinyl caprolactone or vinyl pyrrolidone. The alkyl and dialkyl substituted monomers preferably have from Q to C? alkyl groups, more preferably from Ci to Cs alkyl groups. Other suitable spacer monomers include vinyl esters, vinyl alcohol (made by hydrolysis of polyvinyl acetate), maleic anhydride, propylene glycol, and ethylene glycol. Suitable cationic protonated amino and quaternary ammonium monomers, for inclusion in the cationic polymers of the shampoo composition herein, include vinyl compounds substituted with dialkyiaminoalkyl acrylate, dialkylaminoalkyl methacrylate, monoalaylaminoalkyl acrylate, monoalkylaminoalkyl methacrylate, trialkyl methacryloxyalkyl ammonium salt, trialkyl acryloyalyl ammonium salt, diallyi quaternary ammonium salts, and vinyl quaternary ammonium monomers having cyclic cationic nitrogen-containing rings such as pyridinium, imidazolium, and quatemized pyrrolidone, e.g., alkyl vinyl imidazolium, alkyl vinyl pyridinium, alkyl vinyl pyrrolidone salts. The alkyl portions of these monomers are preferably lower alkyls such as Ci, €2 or €3 alkyls. Suitable amine-substituted vinyl monomers for use herein include dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, dialkylaminoalkyl acrylamide, and dialkylaminoalkyl methacrylamide, wherein the alkyl groups are preferably d -C? hydrocarbyls, more preferably Cj -Ca, alkyls. Other suitable cationic polymers for use in the shampoo composition include copolymers of 1 -vinyl-2-pvnolidone and 1 -vinyl-3-methylimidazolium salt (for example, chloride salt) (referred to in the industry by the Cosmetic, Toiletry, and Fragrance Association, "CTFA", as Polyquatemium-16), such as those commercially available from BASF Wyandotte Corp. (Parsippany, NJ.) under the LUVIQUAT trade name (for example, LUVIQUAT FC 370); copolymers of l-vinyl-2-pyrrolidone and dimethylaminoethyl methacrylate (referred to in the industry by CTFA as Polyquaternium-11) such as those commercially available from ISP Corporation (Wayne, NJ.) under the GAFQUAT trade name (for example, GAFQUAT 755N); cationic diallyi quaternary ammonium-containing polymers, including, for example, dimethyldiallylammonium chloride homopolymer and copolymers of acrylamide and dimethyldiallylammonium chloride, referred to in the industry (CTFA) as Polyquaternium-6 and Polyquatemium-7, respectively; and mineral acid salts of amino-alkyl esters of homopolymers and copolymers of unsaturated carboxylic acids having from 3 to 5 carbon atoms, as described in U.S. Patent Number 4,009,256, which description is incorporated herein by reference as to the description of these polymers. Other suitable cationic polymers for use in the shampoo composition include polysaccharide polymers, such as cationic cellulose derivatives and cationic staich derivatives. Suitable cationic polysaccharide polymers include those which conform toccc wherein A is an anhydroglucose residual group, such as a starch or cellulose anhydroglucose residual; R7 is an alkylene oxyalkylene, polyoxyalkylene, or hydroxyalkylene group, or combination thereof, R8, R9, and R10 independently are alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl, or alkoxyaryl groups, each group containing up to about 18 carbon atoms, and the total number of carbon atoms for each cationic moiety (i.e., the sum of carbon atoms in R8, R9 and R10) preferably being about 20 or less; and X is an anionic counterion as described in hereinbefore. Preferred cationic cellulose polymers are those polymers available from Amerchol Corp. (Edison, N.J.,) in their Polymer JR and LR series of polymers, as salts of hydroxyethyl cellulose reacted with trimethyl ammonium substituted epoxide, referred to in the industry (CTFA) as Polyquaternium-10. Another type of preferred, cationic cellulose includes the polymeric quaternary ammonium salts of acrylamide and dimethyl diallyl ammonium chloride monomers, referred to in the industry (CTFA) as Polyquatemium-7. These materials are available from Nalco Company (Naperville, IL) under the trade name Merquat 550. Other suitable cationic polymers include cationic guar gum derivatives, such as guar hydroxypropyltrimonium chloride, specific examples of which include the Jaguar series commercially available from Celanese Corporation. Other suitable cationic polymers include quaternary nitrogen-containing cellulose ethers, some examples of which are described in U.S. Patent Number 3,962,418, which description is incorporated herein by reference herein as to these polymers. Other suitable cationic polymers include copolymers of ethcrified cellulose, guar and starch, some examples of which are described in U.S. Patent Number 3,958,581, which description is incorporated herein by reference. The detergent soluble silicones include the following categories: (a) water soluble, and (b) detergent soluble, water dispersible, but not water soluble. With regard to the soluble silicones used in the compositions of this invention, the silicones are soluble hi the aqueous surfactant-containing systems described above and are generally classified as dimethicone copolyols having a molecular weight less than 100,000 daltons, particularly in the range of 1,000-10,000 daltons and, more particularly, hi the range of 2,000-4,000 daltons. Examples of suitable materials include PEG-12 Dimethicone (silicone glycol copolymer- water soluble) (sold as DC-193 by Dow Corning Corp., Midland, Michigan) and PEG-12 dimethicone (a detergent soluble, water dispersible silicone copolyol with a molecular weight of about 2300 and sold as DC-5324 by Dow Coming). The compositions of Ibis invention may be made using the detergent soluble silicone as the only silicone conditioning component Alternatively, the compositions of this invention may be made with a portion of the silicone component for conditioning contributed by insoluble silicones. A particular embodiment of interest is one that further comprises a co-surfactant, for example, 0-10 weight % (particularly 0.5-10 weight %) of a co-surfactant or mixtures of more man one co-surfactant selected from the group consisting of amphoteric, nonionic and zwitterionic surfactants and mixtures thereof. Nonionic detersive surfactants which can be used in the invention include those selected from the group described in U.S. Patent No. 4,741,855 to Grote et al and incorporated by reference herein including: (i) polyethylene oxide condensates of alkyl phenols wherein the alkyl portion of the alkyl phenol has 6-12 carbons and may be straight chain or branched and the ethylene oxide portion is present in an amount of 10-60 moles of ethylene oxide per mole of alkyl phenol; (ii) condensation products of ethylene oxide with a product resulting from the reaction of propylene oxide and ethylene diamine varied according to the hydrophobic/hydrophilic balance desired (for example, compounds containing from 40-80% polyoxyethylene by weight and having a molecular weight of ftom 5,000-11,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product of ethylene diamine and excess propylene oxide, wherein the base has a molecular weight of 2500-3,000); (iii) condensation products of C8-18 straight or branched chain aliphatic alcohols with ethylene oxide (for example, coconut alcohol ethylene oxide condensate with 10-30 moles of ethylene oxide per mole of coconut alcohol wherein the coconut fraction has 10-14 carbon atoms); (iv) long chain tertiary amine oxides of formula (R^XR'XR3)—N ->O, wherein R1 is an C8-18 alkyl, alkenyl or monohydroxy alkyls; which has from 0-10 ethylene moieties and from 0-1 glyceryl moiety; and R2 and R3 may be the same or different and are each independently selected from the group consisting of Cl-3 alkyls with 0-1hydroxy group; the atrow in the structure is a conventional representation of a semi-polar bond (examples of suitable long chain tertiary amine oxides including cocamidopropylamine oxide and lauramine oxide); (v) long chain tertiary phosphine oxides of Formula: R4 R5 R6 P-^O where R4 contains a C8-18 alkyl, alkenyl or monohydroxyalkyl radical; 0-10 ethylene oxide moieties and 0-1 glyceryl moiety, and R5 and R6 are each independently Cl-3 alkyl or monohydroxyalkyl with the arrow in the formula being a conventional representation of a semi-polar bond; and (vi) long chain dialkyi sulfoxides containing one short chain alkyl or hydroxy alkyl radical of 1-3 carbons (particularly methyl) and one long hydrophobic chain having a C8-20 alkyl, alkenyl, hydroxy alkyl or keto alkyl group, with 0-10 ethylene oxide moieties and 0-1 glyceryl moiety. Other representative nonionic surfactants include esters of polyols or sugars; fatty acid alkanolamides having 7-25 carbons; pyrrolidones; and the condensation products of ethylene oxide and C7-C25 long chain amides. These nonionic surfactants, as well as numerous others not cited herein, are well known in the art .and are fully described in the literature, such as McCutcheon's Detergents and Emulsifiers. which is incorporated herein by reference as to a description of these nonionic surfactants. hi particular, a nonionic alkanolamide can be included in the composition to provide foam stability. The alkanolamide can be included in an amount of 0% to about 5% by weight of the composition. Accordingly, suitable alkanolamides include, but are not limited to, those known in the art of hair care formulations, such as cocamide MEA, cocamide DBA, soyamide DBA, lauramide DBA, oleamide MIP A, stearamide MEA, myristamide MEA, lauramide MEA, capramide DEA, ricinoleamide DBA, myristamide DBA, stearamide DEA, oleylamide DEA, tallowamide DEA, lauramide MEA, tallowamide MEA, isostearamide DEA, isostearamide MEA, and combinations thereof where DEA means diethanolamide; MEA means monoethanolamide; and MIP A means monoisopropyl amide. la the compositions of the present invention, amphoteric surfactants may also be included. 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 substituent contains from about 8 to 18 carbon atoms and contains an anionic water solubilizing group, for example, 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 U.S. Patent Number. 2,658,072, N-higher alkyi aspartic acids such as those produced according to the teaching of U.S. Patent Number 2,438,091, and the products sold under the trade name "MIRANOL" as described in U.S. Patent Number 2,528,378. la the present invention, zwitterionics such* as betaines can also useful. Examples of suitable betaines include the high alkyl betaines, such as cocodimethyl carboxymethyl betaine, cocoamidopropyi betaine, cocobetaine, lauryl amidopropyl betaine, oleyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alphacarboxvethyl betaine, cetji 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 maybe represented by cocodimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyi 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. A specific betaine of interest is 0-5 weight % of cocoamidopropyi betaine. With regard to insoluble silicones, such insoluble silicones are characteristically a nonvolatile, nonionic silicone hair conditioning agent which is insoluble hi the shampoo compositions hereof. The silicone hair conditioning agent is intermixed in the shampoo composition so as to be in the form of dispersed, insoluble particles, or droplets. The silicone hair conditioning agent comprises 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 other ingredients, such as a silicone resin to enhance deposition efficiency. These insoluble silicones have particular viscosities of from about 200 to about 2,000,000 centistokes at 25 degrees C., more particularly from about 1,000 to about 1,800,000, even more particularly from about 10,000 to about 1,500,000 cst The viscosity can be measured by means of a glass capillary viscometer as set forth in Dow Coming Corporate test method CTM0004, July 20,1970. The insoluble silicone hair conditioning agent may be used in the shampoo compositions hereof at levels of from about 0 weight % to about 8 weight % based on the weight of the composition, particularly from about 0.5 weight % to about 4 weight%. Suitable insoluble, nonvolatile silicone fluids include polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, polyether siloxane copolymers, and mixtures thereof. Other insoluble, nonvolatile silicones fluids having hair conditioning properties can also 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 understood by those in the art The term "silicone fluid" shall mean flowabJe silicone materials having a viscosity of less than 1,000,000 centistokes at 25 degrees C. Generally, the viscosity of the fluid will be between about 5 and 1,000,000 centistokes at 25 degrees C., preferably between about 10 and about 100,000 centistokes. The nonvolatile polyalkylsiloxane fluids that maybe used include, for example, polydimethyl siloxanes. These siloxanes are available, for example, from the General Electric Company in their Viscasil® and SF 96 series, and from Dow Coming in their Dow Coming 200 series. The polyalkylaryl siloxane fluids that may be used, also include, for example, polvmethylphenylsiloxanes. These siloxanes are available, for example, from the General Electric Company as SF 1075 methyl phenyl fluid or from Dow Coming as 556 Cosmetic Grade Fluid. The polyether siloxane copolymers that may be used include, for example, a polypropylene oxide modified polydimethylsiloxane (for example, Dow Corning DC-1248) although ethylene oxide or mixtures of ethylene oxide and propylene oxide may also be used. The ethylene oxide and polypropylene oxide level must be sufficiently low to prevent solubility in water and the composition hereof. References disclosing suitable silicone fluids include U.S. Patent Number 2,826,551, Geen; U.S. Patent Number 3,964,500, Drakoff; U.S. Patent Number 4,364,837, Pader; U.S. Patent Number 5,573,709, Wells; British Patent 849,433, Woolston; and PCT Patent Application WO 93/08787. All of these patents are incorporated herein by reference in their entireties as to descriptions of such silicone materials. 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 poryorganosiloxane materials having a viscosity at 25 degrees C of greater than or equal to 1,000,000 centistokes. Silicone gums are described in U.S. Patent Number 4,152,416, Spitzer et al; and in Noll, Walter, Chemistry and 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. All of these described references are incorporated herein by reference. The "silicone gums" will typically have a mass molecular weight in excess of about 200,000, generally between about 200,000 and about 1,000,000. Specific examples include polydimethylsiloxane, (polydimethyl siloxane) (methylvinylsiloxane) copolymer, poly(dimethyl siloxane) (diphenyl siloxane)(metliylvinylsiloxane) copolymer and mixtures thereof. Another optional ingredient that can be included in the shampoo is silicone resin. Silicone resins are highly crosslinked polymeric siloxane systems. The crosslinkJng is introduced through the incorporation of trifunctional and tetrafunctional silanes with monofunctional or difunctional, or both, silanes during manufacture of the silicone resin. As is well understood in the art, the degree of crosslinkJng that is required in order to result in a silicone resin will vary according to the specific silane units incorporated into the silicone resin. The ratio of oxygen atoms to silicon atoms is indicative of the level of crosslinking in a particular silicone material. Silanes used in the manufacture of silicone resins include monomethyl-, dimethyl-, trimethyl-, monophenyl-, diphenyl-, methylphenyi-, monovinyl-, and rnethylvinyl-chlorosilanes, and tetrachlorosilane, with the methyl-substituted silanes being most commonly utilized. Preferred resins are offered by General Electric as GE SR399, SS4230 and SS4267. Commercially available silicone resins may be supplied in a dissolved form in a low viscosity volatile or nonvolatile silicone fluid. 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, pages 294-308, 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 (CH^s SiOo.s; D denotes the difunctional unit (CH3)2 SiO, T denotes the trifunctional unit (CH3)SiOu; and Q denotes the quadri- or tetra-functional unit SiCh- Primes of the unit symbols, 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. (Figure Removed)here n is a number from 1-20 and the -(CH2)- chain may optionally contain 1 or 2 unsaturations; u and v are integers each independently selected from 0-20, provided that u +v > 1; R15 is selected from C1-C20 alkyl; and R16 is selected from the group consisting of H, -CH3 and -C(O)CH3); and (e) C1-C24 branched and unbranched hydrocarbons optionally substituted by a halogen substituted C1-C3 hydrocarbon radical, with a particular value being C1-C24 alkyl, especially methyl; and wherein (x + y)/z is a number in the range of 0.5 and 1.5, liquid having a viscosity of 1.0 x 10^ - 1 x 10 centipoise, such as 1.5 x 10 -1 x 10 centipoise. A very particular type of MQ resin is described in U.S. Patent Number 6,294,159 assigned to the same owner as this invention. In this very particular type of MQ resin, the MQ Resin structure is of Formula IA when x and y are the same may be described for M and M ; and x'/z' is a value between 0.5 and 1.5. An even more particular MQ useful in the invention is a liquid trimethylsiloxysilicate polymer, especially with an M:Q ratio of 1 (for example, a resin obtained from General Electric Company, Waterfbrd, New York as SR 399). Examples of particular insoluble silicones include, dimetbicone, cyclomemicone, trimethyl silyl amodimethicone, phenyl trimethicone, trimethyl siloxy silicate, polyorganosiloxane, polyalkylsiloxane, polyarylsiloxane, polyalkylarylsiloxane, and polyestersiloxane copolymers. If insoluble silicones are used a suitable amount of a stabilizing agent must also be included so as to stabilize the insoluble silicone. Examples of such stabilizers include one or more members selected from the group consisting of the following members which are selected so that the final amount of stabilizer added is in the range of 0.1-10.0 weight%: (a) long chain fatty alcohols with greater than 14 carbons, for example C20-40, and mixtures of such long chain fatty alcohols (for example, a O14 alcohol and ethene homopolymer PETROLTTE C-7138 fromPetrolite Corporation, St. Louis, Mo.). (b) acrylates/stearem-20 methacrylate copolymer (for example, ACULYN® 22, from Rohm & Haas, Philadelphia, Pa.); and acrylates copolymer (for example, acrylates copolymer (ACULYN® 33); ACUSOL®-445, -810, and -830; ACRYSOL® ASE 75 from Rohm & Haas; AQUA SF-1 Carbopol® from Noveon); and acrylates/C10-30 alkyl acrylate crosspolymer (PEMULEN™ polymeric emulsifiers from BF Goodrich Company, Brecksville, Ohio, particularly products designated as TR-1 and TR-2). (For the acrylates copolymer (ACULYN® 33) product (having a pH in the range of 2.1-3.5), a neutralization step is performed with sodium phosphate (such as disodium phosphate), sodium hydroxide or a cosmetically acceptable organic amine to increase the pH to approximately 6.5.); (c) agents described in U.S. Patent Number 5,015,415 (incorporated by reference herein as to a description of the agents) especially NJN-disubstituted phthalamic acids and their ammonium salts selected from the group consisting of Formula HI: (Figure Removed)here R20 and R21 may be the same or different and are each selected from the group consisting of C10-C40 straight and branched chain alkyl groups, and C10-C40 straight and branched arylaJkyl groups (for example, where R20 and R21 are the same and are each selected from the group consisting of stearyl and hydrogenated tallow such as STEFAN SAB-2 and STEPAN TAB®-2 from Stepan (Company, Northfield, Dl). The stabilizing agents should be of a grade and purity acceptable for cosmetic use or purified as needed to be cosmetically acceptable. A further discussion of some of these agents may be found in U.S. Patent Number 5,015,415 to Croze et al and U.S. Patent Number 6,287,546 to Reich, et al. hi general, the compositions of this invention which contain only the soluble silicones as the only conditioning silicone component will be clear or translucent unless an opacifying agent is added. Other optional ingredients may be included, such as insoluble silicones, stabilizers and/or pearlizers, which may opacify the shampoo formulation. Selected general formulations of the invention included can be made following the methods that are described in the Example section of this document. Examples A-D are of shampoo compositions having only the soluble silicone material and include: Examples E-F are of shampoo compositions having a combination of soluble and insoluble silicones and include: Examples G-I are of shampoo compositions having a combination of soluble and MQ resins and include(Table Removed) The following Examples are offered as illustrative of the invention and are not to be construed as limitations thereon, m the Examples and elsewhere in the description of the invention, chemical symbols and terminology have their usual and customary meanings. la the Examples as elsewhere hi this application values for n, m, etc. in formulas, molecular weights and degree of ethoxylation or propoxylation are averages. Temperatures are in degrees C unless otherwise indicated The amounts of the components are in weight percents based on the standard described; if no other standard is described then the total weight of the composition is to be inferred. Various names of chemical components include (hose listed in the mi*A Tnternatir^nal Cosmetic Ingredient Dictionary (Cosmetics, Toiletry and Fragrance Association, Inc., 7th ed. 1997). Examples 1-9; Translucent Shampoos with Soluble Sflicones Example 1 was made by the following procedure. la a suitable mixing vessel, water, sodium phosphate monobasic and EDTA were combined and mixed until salts were dissolved. Polquatemium-7 was added to the vessel next and mixed for 15 minutes. The sodium lauryl ether sulfate was added to the vessel and mixed for 10 minutes. Cocoamidopropyl betaine was added to the mixing vessel and mixed for 15 minutes. DC5324 was added to the vessel and mixed for 5-10 minutes, followed by the addition of the preservative to the mixing vessel. Fragrance was added to the vessel last and mixed for 10 minutes. Examples 2-8 can be made by the same procedure as listed above for Example 1 with only varying the levels of ingredients. When used, the cocodiethanolamide can be added in place of the cocoamidopropyl betaine. Example 9 can be made by the same procedure as listed above for Example 1 except for using DC 193 to replace DC 5324. Examoles 10-17: Ooaaue Shamooos with Soluble Silicones Formula 10-17 are made based on the following procedure. Water is first added into a suitable main vessel, and stirred at 200 rpm with an overhead mixer. Ingredients in Part II is premixed with 4% water hi a side vessel until uniformity achieved. Part n ingredients are added into the main vessel with continuous agitation. Start to heat the batch to 85°C. Part in ingredients are added into the main vessel one after the other, and agitation is continued for 30 minutes or until a clear solution is obtained. Meanwhile, Part IV ingredients are added into another side vessel, and heated to 85°C to melt the ingredients. When both vessels reach 85°C, transfer Part IV from the side vessel into the main vessel and increase agitation to 400 rpm. Stir the mixture at 85°C for 20 minutes, and men remove the heat. When the main vessel is at or below 38°C, the ingredients in Part V are added. Examples 18-20; Shampoo with both Soluble and Insoluble Silicones Formula 18-20 are made based on the following procedure. Water is first added into a suitable main vessel, and stirred at 200 rpm with an overhead mixer. .Ingredients in Part n is premixed with 4% water hi a side vessel until uniformity achieved. Add Part n into the main vessel with continuous agitation. Start to heat the batch to 85°C. Add ingredients in Part in into the main vessel one after the other, and keep agitating for 30 minutes or until clear solution is obtained. Meanwhile, add ingredients hi Part IV into another side vessel, and heat them to 85°C to melt the ingredients. When both vessels reach 85°C, transfer Part IV from the side vessel into the main vessel and increase agitation to 400 rpm. Stir the mixture at 8S°C for 20 minutes, and then remove the heat. Premix the ingredients in Part V. When the temperature of the main vessel drops to 70°C, add Part V into it with continuous agitation. When the main vessel is at or below 38°C, the ingredients in Part VI are added.Examples 21-26; Shampoos with Soluble SUicone and MO Resin Example 21 was made by the following procedure. In a suitable making vessel, the water, sodium phosphate monobasic and EDTA was added and mixed until dissolved. The batch was heated to 65°C and maintained at the temperature. The Aculyn 22 and Aqua SF-1 were added the vessel and mixed for 5 minutes. Sodium Lauryl Ether Sulfate was added to the vessel next and mixed for 10 minutes. The pH was adjusted to between 6.5 and 7.0 with a 50% Sodium hydroxide solution. The batch was mixed for 15 minutes. The Polyquaternium-7 was pre-mixed in a side vessel with 4% water until uniform, added to the main vessel and mixed for 15 minutes. The ethylene glycol distearate was pre-melted in a side vessel with 1% SLBS and heated to 65°C. When the side vessel and main vessel were both at 65°C, the side vessel mat contained the BGDS was added to the main vessel and mixed for 10 minutes. The main vessel was then allowed to cool. The trimethylsiloxysilicate and DC5324 were added to the main vessel one at a time and mixed for 10 minutes. The cocamidopropyl betaine was added to the main vessel and mixed for 10 minutes. When the main vessel was at or below 38°C, the preservative and fragrance were added. Example 22 was made by the following procedure. In a suitable making vessel, the water, sodium phosphate monobasic and EDTA was added and mixed until dissolved. The batch was heated to 80°C and maintained at the temperature. The ACULYN-22 and AQUA SF-1 were added the vessel and mixed for 5 minutes. Ammonium lauryl sulfate was added to the vessel next and mixed for 10 minutes. The pH was adjusted to between 6.5 and 7.0 with a 50% sodium hydroxide solution. The batch was mixed for 15 minutes. The Polyquaternium-7 was pre-mixed in a side vessel with 4% water until uniform, added to the main vessel and mixed for 15 minutes. The ethylene glycol distearate and cocomonoethanolamide were pre-melted La a side vessel and heated to 80°C. When the side vessel and main vessel were both at 80°C, the side vessel that contained the EGDS was added to the main vessel and mixed for 10 minutes. The main vessel was men allowed to cool. The trimethylsiloxysilicate and DC5324 materials were added to the main vessel one at a time and mixed for 10 minutes. When the main vessel was at or below 38°C, the preservative and fragrance were added. Example 23 can be made by the same procedure as Example 21, except the Polyquaternium-10 is added in place of the Polyquaternium-7, the ACULYN-33 is added in place of the AQUA SF-1 and the TAB-2 is added in place of the EGDS. Example 24 can be made by the same procedure as Example 21, except the Polyquatemium-10 is added in place of the Polyquaternium-7, the ACULYN-33 is added in place of the ACULYN-22 and the TAB-2 is added in place of the EGDS. Example 25 can be made by the same procedure as Example 22, except the TAB-2 is added in place of the EGDS and the cocoamidopropyl betaine is added in place of the cocomonoemanolamide. Example 26 can be made by the same procedure as Example 21, except without heating and omitting the EGDS premix phase. (Table Removed) CLAIMS What is claimed is: 1. A conditioning shampoo comprising: (a) 4-25 weight % of an anionic surfactant or mixtures of two or more anionic surfactants; (b) 0.025-3 weight % of a cationic deposition polymer; (c) 0.1-5 weight % of a detergent soluble silicone having a molecular weight less than 100,000 daltons; and (d) water; wherein all amounts are based on the weight of the entire shampoo. 2. A conditioning shampoo according to Claim 1 additionally comprising one or more ingredients selected from the group consisting of: (e) 0-10 weight % of a co-surfactant selected from the group consisting of amphoteric, nonionic, zwitterionic surfactants, and mixtures of two or more of the foregoing; (f) 0-5 weight % of a pearlizer; (g) 0-5 weight % of a salt; (h) 0-0.5 weight % of a chelating agent; (i) 0-1 weight % of a buffering agent; (j) 0-5.0 weight % fragrance; (k) 0-1 weight % of a pH adjuster, (1) 0-5 weight % of a coloring agent; (m) 0-5 weight % of an insoluble silicone; (n) 0-5 weight % of a silicone resin; (o) 0-10 weight % of a stabilizing agent for the insoluble silicone and/or the silicone resin; and (p) 0-2 weight % of a preservative. 3. A conditioning shampoo according to Claim 1 wherein the molecular weight of the detergent soluble silicone is in the range of 1,000-10,000 daltons. 4. A conditioning shampoo according to Claim 1 wherein the water content is in the range of 57-90 weight %. 5. A conditioning shampoo according to Claim 1 comprising about 5 to about 20 weight % of the anionic surfactant. 6. A conditioning shampoo according to Claim 1 wherein the anionic surfactant is selected from the group consisting of alkyl and alkyl ether sulfates having from 7-25 carbons; alkyl sulfuric acid salts having about 8 to about 24 carbon atoms; olefin sulfonates; beta-alkyloxy alkane sulfonates; reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide; and succinamates selected from the group consisting of disodium N-octadecyl sulfofosuccinamate; tetrasodium N- (l,2-dicarboxyethyl)-N-octadecylsulfosuccinamate; diamyl eater of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; and dioctyl esters of sodium sulfosuccinic acid; and mixtures of two or more of the foregoing. 7. A conditioning shampoo according to Claim 1 comprising an anionic surfactant wherein the anionic surfactant is selected from the group consisting of 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, ammonium cocoyl sulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate, sodium lauroyl sulfate, potassium cocoyl sulfate, potassium lauryl sulfate, triethanolamine lauryl sulfate, monoethanolamine cocoyl sulfate, monoethanolamine lauryl sulfate, sodium tridecyl benzene sulfonate, sodium dodecyl benzene sulfonate, and mixtures of two or more of the foregoing. 8. A conditioning shampoo according to Claim 1 comprising an anionic surfactant wherein the anionic surfactant is selected from the group consisting of: (i) polyethylene oxide condensates of alkyl phenols wherein the alkyl portion of the alkyl phenol has 6-12 carbons and may be straight chain or branched and the ethylene oxide portion is present in an amount of 10-60 moles of ethylene oxide per mole of alkyl phenol; (ii) condensation products of ethylene oxide with a product resulting from the reaction of propylene oxide and ethylene diamine; (iii) condensation products of C8-18 straight or branched chain aliphatic alcohols with ethylene oxide; (iv) long chain tertiary amine oxides of formula (R^XR2) 3)—N -O, wherein R1 is an C8-18 alkyl, alkenyl or monohydroxy alkyls; which has from 0-10 ethylene moieties and from 0-1 glyceryl moiety; and R2 and R3 may be the same or different and are each independently selected from the group consisting of Cl-3 alkyls with 0-1 hydroxy group; (v) long chain tertiary phosphine oxides of Formula: R4 R5 R6 P-O where R4 contains a C8-18 alkyl, alkenyl or monohydroxyalkyl radical; 0-10 ethylene oxide moieties and 0-1 glyceryl moiety, and R5 and R6 are each independently Cl-3 alkyl or monohydroxyalkyl; (vi) long chain dialkyl sulfoxides containing one short chain alkyl or hydroxy alkyl radical of 1-? carbons and one long hydrophobic chain having a C8-20 alkyl, alkenyl, hydroxy alkyl or keto alkyl group, with 0-10 ethylene oxide moieties and 0-1 glyceryl moiety, and (vii) mixtures of two or more of the foregoing. 9. A conditioning shampoo according to Claim 2 comprising a co-surfactant 10. A conditioning shampoo according to Claim 9 wherein the co-surfactant comprises a nonionic surfactant wherein the nonionic surfactant is selected from the group consisting of esters of polyols or sugars; fatty acid alkanolamides having 7-25 carbons; pyrrolidones; and the condensation products of ethylene oxide and C7-C25 long chain amides; and mixtures thereof. 11. A conditioning shampoo according to Claim 10 in which the alkanolamide is selected from the group consisting of cocamide MBA, cocamide DBA, soyamide DEA, lauramide DEA, oleamide MDPA, stearamide MEA, myristamide MEA, lauramide MEA, capramide DEA, ricinoleamide DEA, myristamide DEA, stearamide DEA, oleylamide DEA, tallowamide DEA, lauramide MEA, tallowamide MEA, isostearamide DEA, isostearamide MEA, and combinations thereof where DEA means diethauolamide; MEA means monoethanolamide; and MIPA means monoisopropy! amide. 12. A conditioning shampoo according to Claim 9 comprising an amphoteric surfactant wherein the amphoteric surfactant is selected from the group consisting of aliphatic secondary and tertiary amines in which the aliphatic substituent contains from about 8 to 18 carbon atoms and contains an anionic water solubilizing group selected from the group consisting of carboxy, sulfonate, sulfate, phosphate, and phosphonate. 13. A conditioning shampoo according to Claim 12 wherein the amphoteric surfactant is selected from the group consisting of sodium 3-dodecyl-aminopropionate, sodium 3-dodecylaminopropane sulfonate, sodium lauryl sarcosinate, N-alkyltaurines, N-higher alkyl aspartic acids, and mixtures thereof. 14. A conditioning shampoo according to Claim 2 comprising a zwitterionic surfactant wherein the zwitterionic surfactant is selected from the group consisting of cocodimethyl 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; lauryl bis-(2- hydroxypropyi)alpha-carboxyethyl betaine; sulfobetaines selected from the group consisting of cocodimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, lauryl bis-(2-hydroxyethyl) sulfopropyl betaine; amidobetaines and amidosulfobetaines, wherein the RCONH(CH2)3 radical is attached to the nitrogen atom of the betaine; and mixtures of two of more of the foregoing. 15. A conditioning shampoo according to Claim 1 wherein the cationic deposition polymer is selected from the group of cationic polymers containing quaternary ammonium or cationic protonated amino moieties selected from the group consisting of cationic protonated primary, secondary, and tertiary amines. 16. A conditioning shampoo according to Claim 1 wherein the cationic deposition polymer has an average molecular weight between about 5,000 and 10 million daltons. 17. A conditioning shampoo according to Claim 16 wherein the cationic deposition polymer has an average molecular weight hi the range of about 200,000 to about 2 million daltons. 18. A conditioning shampoo according to Claim 1 wherein the cationic deposition polymer has a cationic charge density ranging from about 0.2 meq/gm to about 7 meq/gm at the pH of the shampoo. 19. A conditioning shampoo according to Claim 1 wherein the detergent soluble silicone is selected from the group consisting of: a) water soluble siticones and b) water dispersible, detergent soluble but not water soluble silicones. 20. A conditioning shampoo according to Claim 19 wherein the detergent soluble silicone is selected from the group consisting of: dimethicone copolyols having a molecular weight less than 100,000 daltons. 21. A conditioning shampoo according to any one of Claims 1-20 wherein the conditioning shampoo is free of insoluble silicones. 22. A conditioning shampoo according to any one of Claims 1 -20 wherein the conditioning shampoo comprises a combination of soluble silicone and insoluble silicone. 23. A conditioning shampoo according to Claim 2 wherein the salt is NaCl. 24. A conditioning shampoo according to Claim 1 further comprising an MQ resin.

Full Text

CONDITIONING SHAMPOOS WITH DETERGENT SOLUBLE SILICONES
Field of the Invention
This invention relates to improved conditioning shampoos that maybe made without stabilizing agents for silicones.
Background of the Invention
A variety of conditioning shampoos (also called "2-in-l shampoos") have been sold and/or described in the patent literature. These products characteristically include an insoluble silicone such as dimethicone in combination with some type of stabilizing agent. The stabilizing agents that have been used have included, for example, ethylene glycol distearate (which is also a pearlizing agent), long chain alcohols such as those having C20-40 carbons (commonly referred to as "Unilin" technology), behenyi alcohol, selected acrylates such as ACULYN-33, and other systems such as cetearyl alcohol mixtures. Some of the stabilizers require heat in the manufacturing processes and others made be made at room temperature.
U.S. Patent Number 5,945,093 describes an improved stable conditioning shampoo imparts improved physical and cosmetic properties to the hair such as wet and dry comb, wet and dry feel, gloss, static control and manageability, yet does not cause build-up and does not contain any polyhydric compounds. The shampoo includes an anionic surfactant, a water soluble cationic surfactant, a water-insoluble conditioning agent, and a suspending agent where the suspending agent is a mixture of a cellulose derivative and a PVM/MA .decadiene cross polymer. The conditioning shampoo is stable for extended periods.
U.S. Patent Number 5,932,203 describes conditioning shampoo compositions which comprise (A) an anionic surfactant component selected from the group consisting of anionic surfactants, zwitterionic or amphoteric surfactants having an attached group that is anionic at (he pH of the composition (B) an organic, cationic, hair conditioning polymer, (C) a selected water insoluble, synthetic ester; and (D) water.
U.S. Patent Number 6,287,546 describes improved stabilized shampoo compositions containing siloxysilicate materials commonly referred to as MQ resins, wherein the stabilizers are selected from (i) long chain fatty alcohols with greater than 14 carbons; (ii) acrylates/steareth-20 methacrylate copolymer, acrylates copolymer; and acrylates/C10-30 alkyl acryiate cross polymer; and (iii) selected N,N-disubstituted phthalamic acids and their ammonium salts.

Of course the use of soluble silicones can be complex if a product is to be obtained that does not rinse the soluble silicone down the drain during shampooing. Thus, there remains a need for conditioning shampoos that can deliver a higher degree of conditioning. There is also a need for conditioning shampoos that can be made in part or in whole without the need for stabilizing agents required for insoluble silicone materials. Yet another object is to create conditioning shampoos that can use soluble silicones and still achieve good conditioning.
Brief Summary of the Invention
The conditioning shampoos of this invention comprise:
(a) 4-25 weight % of an anionic surfactant or mixtures of more than one such
surfactant;
(b) 0.025-3 weight % of a canonic deposition polymer;
(c) 0.1-5 weight % of a detergent soluble silicone having a molecular weight less
than 100,000 daltons, particularly in the range of 1,000-10,000 and, more particularly,
in the range of 2,000-4,000; and
(d) water (including water that comes in with the ingredients) for example in a
range of 57-90 weight %.
In addition to these ingredients, one or more optional ingredients selected fiom the group consisting of the following list maybe included:
(e) 0-10 weight % (particularly 0.5-10 weight %) of a co-surfectant or mixtures of
more than one co-surfactant selected fiom the group consisting of amphoteric, nonionic
and zwitterionic surfactants and mixtures thereof;
(f) 0-5 weight % of a pearlizer (including ethylene glycol distearate);
(g) 0-5 weight % of a salt such as NaCl as a viscosity modifier;
(h) 0-0.5 weight % of a dictating agent such as EDTA;
(i) 0-1 weight % of a buffering agent (which may also have some chelating
properties) such as sodium dihydrogen phosphate monohydrate;
(j) 0-5.0 weight % fragrance (particularly 0.2-2.0%);
(k) 0-1 weight % of a pH adjuster (such as citric acid);
(1) 0-5 weight % of a coloring agent;
(m) 0-8 weight % of an insoluble silicone;
(n) 0-5 weight % of a silicone resin;
(o) 0-10 weight % of a stabilizing agent for the insoluble silicone and/or the
silicone resin (particularly 0-5.0%); and
(p) 0-2 weight % of a preservative.

Note that for ingredients (a) and (b), these ingredients may be added as aqueous solutions (for example, having 8-90% of the active ingredient). For optional ingredients (e) and (f), they may be added as a pre-formed aqueous solution or suspension. For optional ingredients (g), (h), (i), (k), (1), (o) and (p) these ingredients may be added as aqueous solutions. For optional ingredients (m) and (n), these ingredients may be added as pre-formed stabilized emulsions.
Detailed Description of the Invention
The shampoos of this invention may be made as clear, translucent or opaque products which are colored or colorless. In addition, the compositions of this invention may be made with soluble silicones only and without the need for any stabilizers for the silicones, or they may be made by supplementing the system with a portion of insoluble silicone with a conventional stabilizing system for those silicones.
Additionally, in a special embodiment, an MQ resin is used hi the formulation to form a 3-in-l product with special styling capabilities.
The anionic surfactants useful in the compositions of the invention include those familiar to skilled practioners. The anionic surfactant of component (a) will generally be present at a level from about 4 weight % to about 25%, particularly from about 6 weight % to about 19 weight %, with an amount of about 7-17 weight % being of particular interest.
Anionic detersive surfactants useful herein include those that are disclosed in U.S. Patent Number 5,573,709, the disclosure of which is incorporated herein by reference in its entirety as to the description of such surfactants. Examples of the anionic surfactants useful in mis invention include alkyl and alkyl ether sulfates, particularly those having from 7-25 carbons. Specific examples of alkyl ether sulfates which may be used in the present invention are sodium and ammonium salts of lauryl sulfate, lauryl ether sulfate, coconut alkyl triethylene glycol ether sulfate; tallow alkyl triethylene glycol ether sulfate, and tallow alkyl hexaoxyethylene sulfate. A particular group of anionic surfactants includes alkyl ether sulfates comprising a mixture of individual compounds, said mixture having an average alkyl chain length of from about 12 to about 16 carbon atoms and an average degree of ethoxylation of from about 1 to about 6 moles of ethylene oxide.
Another suitable class of anionic detersive surfactants are the alkyl sulfuric acid salts. 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, for example, SCb, H2SO4, oleum (fuming sulfuric acid) obtained

according to known sulfonation methods, including bleaching and hydrolysis. Preferred are alkali metal and ammonium sulfated Cn n-para£6ns.
Additional examples of synthetic anionic detersive surfactants which come within the terms of the present invention are the olefin sulfonates, the beta-alkyloxy alkane sulfonates, and the reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide, as well as succinamates. Specific examples of succinamates include disodium N-octadecyl sulfofosuccinamate; tetrasodium N-(l,2-dicarboxyethyl)-N-octadecylsulfosuccinamate; diamyl eater of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; and dioctyl esters of sodium sulfosuccinic acid.
Many additional synthetic anionic surfactants are described in McCutcheon's Emulsifiers and Detergents, 1989 Annual, published by M. C. Publishing Co., which descriptions are incorporated herein by reference in their entirety as to the listing of such surfactants. Finally, U.S. Patent Number 3,929,678, Laughlin et al., discloses many other anionic as well as other surfactant types and is incorporated herein by reference in its entirety as to descriptions of such surfactants.
A particular group of anionic detersive surfactants for use in the present shampoo compositions include one or more members selected from the group consisting of ammonium lauryi 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, ammonium cocoyl sulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate, sodium lauroyl sulfate, potassium cocoyl sulfate, potassium lauryl sulfate, triethanolamine lauryi sulfate, monoethanolamine cocoyl sulfate, monoethanolamine lauryl sulfate, sodium tridecyl benzene sulfbnate, sodium dodecyi benzene sulfbnate, and mixtures of two or more of the foregoing.
A particular anionic component is a combination of 5-20 weight % of ammonium lauryl sulfate and 5-20 weight % of ammonium lauryl ether sulfate.
The shampoo compositions of the present invention comprise a cationic polymer particularly an organic polymer, as a deposition aid polymer. Such cationic polymers should also be physically and chemically compatible with the essential components described herein, or should not otherwise unduly impair product stability, aesthetics or performance.

The concentration of the organic, cationic, conditioning polymer of the shampoo composition should be generally in the range from about 0.025% to about 3%, preferably from about 0.05% to about 2%, more preferably from about 0.1% to about 1%, by weight of the shampoo composition.
The cationic deposition polymer contains cationic nitrogen-containing moieties such as quaternary ammonium or cationic protonated amino moieties. The cationic protonated amines can be primary, secondary, or tertiary amines (preferably secondary or tertiary), depending upon the particular species and the selected pH of the shampoo composition. The average molecular weight of the cationic conditioning polymers is between about 10 million and about 5,000, preferably at least about 100,000, more preferably at least about 200,000, but preferably not more than about 2 million, preferably not more than about 1.5 million. The polymers also have a cationic charge density ranging from about 0.2 meq/gm to about 7 meq/gm, preferably at least about 0.4meq/gm, more preferably at least about 0.6meq/gm, but also preferably less than about 5meq/gm, more preferably less than about 2 meq/gm, at the pH of intended use of the shampoo composition, which pH will generally range from about pH 3 to about pH 9, preferably between about pH 4 and about pH7.
Any anionic counterions can be used in association with the cationic deposition polymers so long as the polymers remain soluble hi water, in the shampoo composition, or in a coacervate phase of the shampoo composition, and so long as the counterions are physically and chemically compatible with the essential components of the shampoo composition or do not otherwise unduly impair product performance, stability or aesthetics. Non-limiting examples of such counterions include halides (for example, chlorine, fluorine, bromine, iodine), sulfate and methylsulfate).
The cationic nitrogen-containing moiety of the cationic polymer is generally present as a substituent on all, or more typically on some, of the monomer units thereof. Thus, the cationic polymer for use in the shampoo composition includes homopolymers, copolymers, terpolymers, and so forth, of quaternary ammonium or cationic amine-substimted monomer units, optionally in combination with non-cationic monomers referred to herein as spacer monomers. Non-limiting examples of such polymers are described in the CTFA Cosmetic Ingredient Dictionary, 3rd edition, edited by Estrin, Crosley, and Haynes (The Cosmetic, Toiletry, and Fragrance Association, Inc., Washington, D.C. (1982)), which description is incorporated herein by reference as to the description of these polymers.
Non-limiting examples of suitable cationic polymers include copolymers of vinyl monomers having cationic protonated amine or quaternary ammonium functionalities with water soluble spacer monomers such as acrylamide,

methacrylamide, alkyl and dialkyl acrylamides, alkyl and dialkyl methacrylamides, alkyl acrylate, allyl methacrylate, vinyl caprolactone or vinyl pyrrolidone. The alkyl and dialkyl substituted monomers preferably have from Q to C? alkyl groups, more preferably from Ci to Cs alkyl groups. Other suitable spacer monomers include vinyl esters, vinyl alcohol (made by hydrolysis of polyvinyl acetate), maleic anhydride, propylene glycol, and ethylene glycol.
Suitable cationic protonated amino and quaternary ammonium monomers, for inclusion in the cationic polymers of the shampoo composition herein, include vinyl compounds substituted with dialkyiaminoalkyl acrylate, dialkylaminoalkyl methacrylate, monoalaylaminoalkyl acrylate, monoalkylaminoalkyl methacrylate, trialkyl methacryloxyalkyl ammonium salt, trialkyl acryloyalyl ammonium salt, diallyi quaternary ammonium salts, and vinyl quaternary ammonium monomers having cyclic cationic nitrogen-containing rings such as pyridinium, imidazolium, and quatemized pyrrolidone, e.g., alkyl vinyl imidazolium, alkyl vinyl pyridinium, alkyl vinyl pyrrolidone salts. The alkyl portions of these monomers are preferably lower alkyls such as Ci, €2 or €3 alkyls.
Suitable amine-substituted vinyl monomers for use herein include dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, dialkylaminoalkyl acrylamide, and dialkylaminoalkyl methacrylamide, wherein the alkyl groups are preferably d -C? hydrocarbyls, more preferably Cj -Ca, alkyls.
Other suitable cationic polymers for use in the shampoo composition include copolymers of 1 -vinyl-2-pvnolidone and 1 -vinyl-3-methylimidazolium salt (for example, chloride salt) (referred to in the industry by the Cosmetic, Toiletry, and Fragrance Association, "CTFA", as Polyquatemium-16), such as those commercially available from BASF Wyandotte Corp. (Parsippany, NJ.) under the LUVIQUAT trade name (for example, LUVIQUAT FC 370); copolymers of l-vinyl-2-pyrrolidone and dimethylaminoethyl methacrylate (referred to in the industry by CTFA as Polyquaternium-11) such as those commercially available from ISP Corporation (Wayne, NJ.) under the GAFQUAT trade name (for example, GAFQUAT 755N); cationic diallyi quaternary ammonium-containing polymers, including, for example, dimethyldiallylammonium chloride homopolymer and copolymers of acrylamide and dimethyldiallylammonium chloride, referred to in the industry (CTFA) as Polyquaternium-6 and Polyquatemium-7, respectively; and mineral acid salts of amino-alkyl esters of homopolymers and copolymers of unsaturated carboxylic acids having from 3 to 5 carbon atoms, as described in U.S. Patent Number 4,009,256, which description is incorporated herein by reference as to the description of these polymers.

Other suitable cationic polymers for use in the shampoo composition include polysaccharide polymers, such as cationic cellulose derivatives and cationic staich derivatives. Suitable cationic polysaccharide polymers include those which conform toccc
wherein A is an anhydroglucose residual group, such as a starch or cellulose anhydroglucose residual; R7 is an alkylene oxyalkylene, polyoxyalkylene, or hydroxyalkylene group, or combination thereof, R8, R9, and R10 independently are alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl, or alkoxyaryl groups, each group containing up to about 18 carbon atoms, and the total number of carbon atoms for each cationic moiety (i.e., the sum of carbon atoms in R8, R9 and R10) preferably being about 20 or less; and X is an anionic counterion as described in hereinbefore.
Preferred cationic cellulose polymers are those polymers available from Amerchol Corp. (Edison, N.J.,) in their Polymer JR and LR series of polymers, as salts of hydroxyethyl cellulose reacted with trimethyl ammonium substituted epoxide, referred to in the industry (CTFA) as Polyquaternium-10. Another type of preferred, cationic cellulose includes the polymeric quaternary ammonium salts of acrylamide and dimethyl diallyl ammonium chloride monomers, referred to in the industry (CTFA) as Polyquatemium-7. These materials are available from Nalco Company (Naperville, IL) under the trade name Merquat 550.
Other suitable cationic polymers include cationic guar gum derivatives, such as guar hydroxypropyltrimonium chloride, specific examples of which include the Jaguar series commercially available from Celanese Corporation. Other suitable cationic polymers include quaternary nitrogen-containing cellulose ethers, some examples of which are described in U.S. Patent Number 3,962,418, which description is incorporated herein by reference herein as to these polymers. Other suitable cationic polymers include copolymers of ethcrified cellulose, guar and starch, some examples of which are described in U.S. Patent Number 3,958,581, which description is incorporated herein by reference.
The detergent soluble silicones include the following categories: (a) water soluble, and (b) detergent soluble, water dispersible, but not water soluble. With regard to the soluble silicones used in the compositions of this invention, the silicones are soluble hi the aqueous surfactant-containing systems described above and are generally
classified as dimethicone copolyols having a molecular weight less than 100,000 daltons, particularly in the range of 1,000-10,000 daltons and, more particularly, hi the range of 2,000-4,000 daltons. Examples of suitable materials include PEG-12 Dimethicone (silicone glycol copolymer- water soluble) (sold as DC-193 by Dow Corning Corp., Midland, Michigan) and PEG-12 dimethicone (a detergent soluble, water dispersible silicone copolyol with a molecular weight of about 2300 and sold as DC-5324 by Dow Coming).
The compositions of Ibis invention may be made using the detergent soluble silicone as the only silicone conditioning component Alternatively, the compositions of this invention may be made with a portion of the silicone component for conditioning contributed by insoluble silicones.
A particular embodiment of interest is one that further comprises a co-surfactant, for example, 0-10 weight % (particularly 0.5-10 weight %) of a co-surfactant or mixtures of more man one co-surfactant selected from the group consisting of amphoteric, nonionic and zwitterionic surfactants and mixtures thereof. Nonionic detersive surfactants which can be used in the invention include those selected from the group described in U.S. Patent No. 4,741,855 to Grote et al and incorporated by reference herein including:
(i) polyethylene oxide condensates of alkyl phenols wherein the alkyl portion of the alkyl phenol has 6-12 carbons and may be straight chain or branched and the ethylene oxide portion is present in an amount of 10-60 moles of ethylene oxide per mole of alkyl phenol;
(ii) condensation products of ethylene oxide with a product resulting from the reaction of propylene oxide and ethylene diamine varied according to the hydrophobic/hydrophilic balance desired (for example, compounds containing from 40-80% polyoxyethylene by weight and having a molecular weight of ftom 5,000-11,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product of ethylene diamine and excess propylene oxide, wherein the base has a molecular weight of 2500-3,000);
(iii) condensation products of C8-18 straight or branched chain aliphatic alcohols with ethylene oxide (for example, coconut alcohol ethylene oxide condensate with 10-30 moles of ethylene oxide per mole of coconut alcohol wherein the coconut fraction has 10-14 carbon atoms);
(iv) long chain tertiary amine oxides of formula (R^XR'XR3)—N ->O, wherein R1 is an C8-18 alkyl, alkenyl or monohydroxy alkyls; which has from 0-10 ethylene moieties and from 0-1 glyceryl moiety; and R2 and R3 may be the same or different and are each independently selected from the group consisting of Cl-3 alkyls with 0-1hydroxy group; the atrow in the structure is a conventional representation of a semi-polar bond (examples of suitable long chain tertiary amine oxides including cocamidopropylamine oxide and lauramine oxide);
(v) long chain tertiary phosphine oxides of Formula: R4 R5 R6 P-^O where R4 contains a C8-18 alkyl, alkenyl or monohydroxyalkyl radical; 0-10 ethylene oxide moieties and 0-1 glyceryl moiety, and R5 and R6 are each independently Cl-3 alkyl or monohydroxyalkyl with the arrow in the formula being a conventional representation of a semi-polar bond; and
(vi) long chain dialkyi sulfoxides containing one short chain alkyl or hydroxy alkyl radical of 1-3 carbons (particularly methyl) and one long hydrophobic chain having a C8-20 alkyl, alkenyl, hydroxy alkyl or keto alkyl group, with 0-10 ethylene oxide moieties and 0-1 glyceryl moiety.
Other representative nonionic surfactants include esters of polyols or sugars; fatty acid alkanolamides having 7-25 carbons; pyrrolidones; and the condensation products of ethylene oxide and C7-C25 long chain amides. These nonionic surfactants, as well as numerous others not cited herein, are well known in the art .and are fully described in the literature, such as McCutcheon's Detergents and Emulsifiers. which is incorporated herein by reference as to a description of these nonionic surfactants.
hi particular, a nonionic alkanolamide can be included in the composition to provide foam stability. The alkanolamide can be included in an amount of 0% to about 5% by weight of the composition. Accordingly, suitable alkanolamides include, but are not limited to, those known in the art of hair care formulations, such as cocamide MEA, cocamide DBA, soyamide DBA, lauramide DBA, oleamide MIP A, stearamide MEA, myristamide MEA, lauramide MEA, capramide DEA, ricinoleamide DBA, myristamide DBA, stearamide DEA, oleylamide DEA, tallowamide DEA, lauramide MEA, tallowamide MEA, isostearamide DEA, isostearamide MEA, and combinations thereof where DEA means diethanolamide; MEA means monoethanolamide; and MIP A means monoisopropyl amide.
la the compositions of the present invention, amphoteric surfactants may also be included. 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 substituent contains from about 8 to 18 carbon atoms and contains an anionic water solubilizing group, for example, 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 U.S. Patent Number. 2,658,072, N-higher alkyi aspartic acids such as those produced according to the teaching of U.S. Patent Number 2,438,091, and the products sold under the trade name "MIRANOL" as described in U.S. Patent Number 2,528,378.
la the present invention, zwitterionics such* as betaines can also useful. Examples of suitable betaines include the high alkyl betaines, such as cocodimethyl carboxymethyl betaine, cocoamidopropyi betaine, cocobetaine, lauryl amidopropyl betaine, oleyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alphacarboxvethyl betaine, cetji 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 maybe represented by cocodimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyi 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.
A specific betaine of interest is 0-5 weight % of cocoamidopropyi betaine.
With regard to insoluble silicones, such insoluble silicones are characteristically a nonvolatile, nonionic silicone hair conditioning agent which is insoluble hi the shampoo compositions hereof. The silicone hair conditioning agent is intermixed in the shampoo composition so as to be in the form of dispersed, insoluble particles, or droplets. The silicone hair conditioning agent comprises 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 other ingredients, such as a silicone resin to enhance deposition efficiency. These insoluble silicones have particular viscosities of from about 200 to about 2,000,000 centistokes at 25 degrees C., more particularly from about 1,000 to about 1,800,000, even more particularly from about 10,000 to about 1,500,000 cst The viscosity can be measured by means of a glass capillary viscometer as set forth in Dow Coming Corporate test method CTM0004, July 20,1970.
The insoluble silicone hair conditioning agent may be used in the shampoo compositions hereof at levels of from about 0 weight % to about 8 weight % based on the weight of the composition, particularly from about 0.5 weight % to about 4 weight%.
Suitable insoluble, nonvolatile silicone fluids include polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, polyether siloxane copolymers, and mixtures thereof. Other insoluble, nonvolatile silicones fluids having hair conditioning
properties can also 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 understood by those in the art The term "silicone fluid" shall mean flowabJe silicone materials having a viscosity of less than 1,000,000 centistokes at 25 degrees C. Generally, the viscosity of the fluid will be between about 5 and 1,000,000 centistokes at 25 degrees C., preferably between about 10 and about 100,000 centistokes.
The nonvolatile polyalkylsiloxane fluids that maybe used include, for example, polydimethyl siloxanes. These siloxanes are available, for example, from the General Electric Company in their Viscasil® and SF 96 series, and from Dow Coming in their Dow Coming 200 series.
The polyalkylaryl siloxane fluids that may be used, also include, for example, polvmethylphenylsiloxanes. These siloxanes are available, for example, from the General Electric Company as SF 1075 methyl phenyl fluid or from Dow Coming as 556 Cosmetic Grade Fluid.
The polyether siloxane copolymers that may be used include, for example, a polypropylene oxide modified polydimethylsiloxane (for example, Dow Corning DC-1248) although ethylene oxide or mixtures of ethylene oxide and propylene oxide may also be used. The ethylene oxide and polypropylene oxide level must be sufficiently low to prevent solubility in water and the composition hereof.
References disclosing suitable silicone fluids include U.S. Patent Number 2,826,551, Geen; U.S. Patent Number 3,964,500, Drakoff; U.S. Patent Number 4,364,837, Pader; U.S. Patent Number 5,573,709, Wells; British Patent 849,433, Woolston; and PCT Patent Application WO 93/08787. All of these patents are incorporated herein by reference in their entireties as to descriptions of such silicone materials.
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 poryorganosiloxane materials having a viscosity at 25 degrees C of greater than or equal to 1,000,000 centistokes. Silicone gums are described in U.S. Patent Number 4,152,416, Spitzer et al; and in Noll, Walter, Chemistry and
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. All of these described references are incorporated herein by reference. The "silicone gums" will typically have a mass molecular weight in excess of about 200,000, generally between
about 200,000 and about 1,000,000. Specific examples include polydimethylsiloxane, (polydimethyl siloxane) (methylvinylsiloxane) copolymer, poly(dimethyl siloxane) (diphenyl siloxane)(metliylvinylsiloxane) copolymer and mixtures thereof.
Another optional ingredient that can be included in the shampoo is silicone resin. Silicone resins are highly crosslinked polymeric siloxane systems. The crosslinkJng is introduced through the incorporation of trifunctional and tetrafunctional silanes with monofunctional or difunctional, or both, silanes during manufacture of the silicone resin. As is well understood in the art, the degree of crosslinkJng that is required in order to result in a silicone resin will vary according to the specific silane units incorporated into the silicone resin. The ratio of oxygen atoms to silicon atoms is indicative of the level of crosslinking in a particular silicone material. Silanes used in the manufacture of silicone resins include monomethyl-, dimethyl-, trimethyl-, monophenyl-, diphenyl-, methylphenyi-, monovinyl-, and rnethylvinyl-chlorosilanes, and tetrachlorosilane, with the methyl-substituted silanes being most commonly utilized. Preferred resins are offered by General Electric as GE SR399, SS4230 and SS4267. Commercially available silicone resins may be supplied in a dissolved form in a low viscosity volatile or nonvolatile silicone fluid.
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, pages 294-308, 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 (CH^s SiOo.s; D denotes the difunctional unit (CH3)2 SiO, T denotes the trifunctional unit (CH3)SiOu; and Q denotes the quadri- or tetra-functional unit SiCh- Primes of the unit symbols, 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.

(Figure Removed)here n is a number from 1-20 and the -(CH2)- chain may optionally contain 1 or 2 unsaturations; u and v are integers each independently selected from 0-20, provided that
u +v > 1; R15 is selected from C1-C20 alkyl; and R16 is selected from the group consisting of H, -CH3 and -C(O)CH3); and
(e) C1-C24 branched and unbranched hydrocarbons optionally substituted by a halogen substituted C1-C3 hydrocarbon radical, with a particular value being C1-C24 alkyl, especially methyl; and wherein (x + y)/z is a number in the range of 0.5 and 1.5,
liquid having a viscosity of 1.0 x 10^ - 1 x 10
centipoise, such as 1.5 x 10 -1 x 10 centipoise.
A very particular type of MQ resin is described in U.S. Patent Number 6,294,159 assigned to the same owner as this invention. In this very particular type of MQ resin, the MQ Resin structure is of Formula IA when x and y are the same may be
described for M and M ; and x'/z' is a value between 0.5 and 1.5.
An even more particular MQ useful in the invention is a liquid trimethylsiloxysilicate polymer, especially with an M:Q ratio of 1 (for example, a resin obtained from General Electric Company, Waterfbrd, New York as SR 399).
Examples of particular insoluble silicones include, dimetbicone, cyclomemicone, trimethyl silyl amodimethicone, phenyl trimethicone, trimethyl siloxy silicate, polyorganosiloxane, polyalkylsiloxane, polyarylsiloxane, polyalkylarylsiloxane, and polyestersiloxane copolymers.
If insoluble silicones are used a suitable amount of a stabilizing agent must also be included so as to stabilize the insoluble silicone. Examples of such stabilizers include one or more members selected from the group consisting of the following members which are selected so that the final amount of stabilizer added is in the range of 0.1-10.0 weight%:
(a) long chain fatty alcohols with greater than 14 carbons, for example C20-40,
and mixtures of such long chain fatty alcohols (for example, a O14 alcohol and ethene
homopolymer PETROLTTE C-7138 fromPetrolite Corporation, St. Louis, Mo.).
(b) acrylates/stearem-20 methacrylate copolymer (for example, ACULYN® 22,
from Rohm & Haas, Philadelphia, Pa.); and acrylates copolymer (for example, acrylates
copolymer (ACULYN® 33); ACUSOL®-445, -810, and -830; ACRYSOL® ASE 75
from Rohm & Haas; AQUA SF-1 Carbopol® from Noveon); and acrylates/C10-30
alkyl acrylate crosspolymer (PEMULEN™ polymeric emulsifiers from BF Goodrich
Company, Brecksville, Ohio, particularly products designated as TR-1 and TR-2). (For
the acrylates copolymer (ACULYN® 33) product (having a pH in the range of 2.1-3.5),
a neutralization step is performed with sodium phosphate (such as disodium
phosphate), sodium hydroxide or a cosmetically acceptable organic amine to increase
the pH to approximately 6.5.);
(c) agents described in U.S. Patent Number 5,015,415 (incorporated by
reference herein as to a description of the agents) especially NJN-disubstituted
phthalamic acids and their ammonium salts selected from the group consisting of
Formula HI:

(Figure Removed)here R20 and R21 may be the same or different and are each selected from the group consisting of C10-C40 straight and branched chain alkyl groups, and C10-C40 straight and branched arylaJkyl groups (for example, where R20 and R21 are the same and are each selected from the group consisting of stearyl and hydrogenated tallow such as STEFAN SAB-2 and STEPAN TAB®-2 from Stepan (Company, Northfield, Dl). The stabilizing agents should be of a grade and purity acceptable for cosmetic use or purified as needed to be cosmetically acceptable. A further discussion of some of these agents may be found in U.S. Patent Number 5,015,415 to Croze et al and U.S. Patent Number 6,287,546 to Reich, et al.
hi general, the compositions of this invention which contain only the soluble silicones as the only conditioning silicone component will be clear or translucent unless an opacifying agent is added. Other optional ingredients may be included, such as insoluble silicones, stabilizers and/or pearlizers, which may opacify the shampoo formulation.
Selected general formulations of the invention included can be made following the methods that are described in the Example section of this document.
Examples A-D are of shampoo compositions having only the soluble silicone material and include:
Examples E-F are of shampoo compositions having a combination of soluble
and insoluble silicones and include:
Examples G-I are of shampoo compositions having a combination of soluble and MQ resins and include(Table Removed)

The following Examples are offered as illustrative of the invention and are not to be construed as limitations thereon, m the Examples and elsewhere in the description of the invention, chemical symbols and terminology have their usual and customary meanings. la the Examples as elsewhere hi this application values for n, m, etc. in formulas, molecular weights and degree of ethoxylation or propoxylation are averages. Temperatures are in degrees C unless otherwise indicated The amounts of the components are in weight percents based on the standard described; if no other standard is described then the total weight of the composition is to be inferred. Various names of chemical components include (hose listed in the mi*A Tnternatir^nal Cosmetic Ingredient Dictionary (Cosmetics, Toiletry and Fragrance Association, Inc., 7th ed. 1997).
Examples 1-9; Translucent Shampoos with Soluble Sflicones
Example 1 was made by the following procedure. la a suitable mixing vessel, water, sodium phosphate monobasic and EDTA were combined and mixed until salts were dissolved. Polquatemium-7 was added to the vessel next and mixed for 15 minutes. The sodium lauryl ether sulfate was added to the vessel and mixed for 10 minutes. Cocoamidopropyl betaine was added to the mixing vessel and mixed for 15 minutes. DC5324 was added to the vessel and mixed for 5-10 minutes, followed by the addition of the preservative to the mixing vessel. Fragrance was added to the vessel last and mixed for 10 minutes.
Examples 2-8 can be made by the same procedure as listed above for Example 1 with only varying the levels of ingredients. When used, the cocodiethanolamide can be added in place of the cocoamidopropyl betaine.
Example 9 can be made by the same procedure as listed above for Example 1 except for using DC 193 to replace DC 5324.
Examoles 10-17: Ooaaue Shamooos with Soluble Silicones
Formula 10-17 are made based on the following procedure. Water is first added into a suitable main vessel, and stirred at 200 rpm with an overhead mixer. Ingredients in Part II is premixed with 4% water hi a side vessel until uniformity achieved. Part n ingredients are added into the main vessel with continuous agitation. Start to heat the batch to 85°C. Part in ingredients are added into the main vessel one after the other, and agitation is continued for 30 minutes or until a clear solution is obtained. Meanwhile, Part IV ingredients are added into another side vessel, and heated to 85°C to melt the ingredients. When both vessels reach 85°C, transfer Part IV from the side vessel into the main vessel and increase agitation to 400 rpm. Stir the mixture at 85°C for 20 minutes, and men remove the heat. When the main vessel is at or below 38°C, the ingredients in Part V are added.

Examples 18-20; Shampoo with both Soluble and Insoluble Silicones
Formula 18-20 are made based on the following procedure. Water is first added into a suitable main vessel, and stirred at 200 rpm with an overhead mixer. .Ingredients in Part n is premixed with 4% water hi a side vessel until uniformity achieved. Add Part n into the main vessel with continuous agitation. Start to heat the batch to 85°C. Add ingredients in Part in into the main vessel one after the other, and keep agitating for 30 minutes or until clear solution is obtained. Meanwhile, add ingredients hi Part IV into another side vessel, and heat them to 85°C to melt the ingredients. When both vessels reach 85°C, transfer Part IV from the side vessel into the main vessel and increase agitation to 400 rpm. Stir the mixture at 8S°C for 20 minutes, and then remove the heat. Premix the ingredients in Part V. When the temperature of the main vessel drops to 70°C, add Part V into it with continuous agitation. When the main vessel is at or below 38°C, the ingredients in Part VI are added.Examples 21-26; Shampoos with Soluble SUicone and MO Resin
Example 21 was made by the following procedure. In a suitable making vessel, the water, sodium phosphate monobasic and EDTA was added and mixed until dissolved. The batch was heated to 65°C and maintained at the temperature. The Aculyn 22 and Aqua SF-1 were added the vessel and mixed for 5 minutes. Sodium Lauryl Ether Sulfate was added to the vessel next and mixed for 10 minutes. The pH was adjusted to between 6.5 and 7.0 with a 50% Sodium hydroxide solution. The batch was mixed for 15 minutes. The Polyquaternium-7 was pre-mixed in a side vessel with 4% water until uniform, added to the main vessel and mixed for 15 minutes. The ethylene glycol distearate was pre-melted in a side vessel with 1% SLBS and heated to 65°C. When the side vessel and main vessel were both at 65°C, the side vessel mat contained the BGDS was added to the main vessel and mixed for 10 minutes. The main vessel was then allowed to cool. The trimethylsiloxysilicate and DC5324 were added to the main vessel one at a time and mixed for 10 minutes. The cocamidopropyl betaine was added to the main vessel and mixed for 10 minutes. When the main vessel was at or below 38°C, the preservative and fragrance were added.
Example 22 was made by the following procedure. In a suitable making vessel, the water, sodium phosphate monobasic and EDTA was added and mixed until dissolved. The batch was heated to 80°C and maintained at the temperature. The ACULYN-22 and AQUA SF-1 were added the vessel and mixed for 5 minutes. Ammonium lauryl sulfate was added to the vessel next and mixed for 10 minutes. The pH was adjusted to between 6.5 and 7.0 with a 50% sodium hydroxide solution. The batch was mixed for 15 minutes. The Polyquaternium-7 was pre-mixed in a side vessel with 4% water until uniform, added to the main vessel and mixed for 15 minutes. The ethylene glycol distearate and cocomonoethanolamide were pre-melted La a side vessel and heated to 80°C. When the side vessel and main vessel were both at 80°C, the side vessel that contained the EGDS was added to the main vessel and mixed for 10 minutes. The main vessel was men allowed to cool. The trimethylsiloxysilicate and DC5324 materials were added to the main vessel one at a time and mixed for 10 minutes. When the main vessel was at or below 38°C, the preservative and fragrance were added.
Example 23 can be made by the same procedure as Example 21, except the Polyquaternium-10 is added in place of the Polyquaternium-7, the ACULYN-33 is added in place of the AQUA SF-1 and the TAB-2 is added in place of the EGDS.
Example 24 can be made by the same procedure as Example 21, except the Polyquatemium-10 is added in place of the Polyquaternium-7, the ACULYN-33 is added in place of the ACULYN-22 and the TAB-2 is added in place of the EGDS.
Example 25 can be made by the same procedure as Example 22, except the TAB-2 is added in place of the EGDS and the cocoamidopropyl betaine is added in place of the cocomonoemanolamide.
Example 26 can be made by the same procedure as Example 21, except without heating and omitting the EGDS premix phase.
(Table Removed)

CLAIMS
What is claimed is:
1. A conditioning shampoo comprising:
(a) 4-25 weight % of an anionic surfactant or mixtures of two or more anionic
surfactants;
(b) 0.025-3 weight % of a cationic deposition polymer;
(c) 0.1-5 weight % of a detergent soluble silicone having a molecular weight less
than 100,000 daltons; and
(d) water;
wherein all amounts are based on the weight of the entire shampoo.
2. A conditioning shampoo according to Claim 1 additionally comprising one or
more ingredients selected from the group consisting of:
(e) 0-10 weight % of a co-surfactant selected from the group consisting of
amphoteric, nonionic, zwitterionic surfactants, and mixtures of two or more of the
foregoing;
(f) 0-5 weight % of a pearlizer;
(g) 0-5 weight % of a salt;
(h) 0-0.5 weight % of a chelating agent;
(i) 0-1 weight % of a buffering agent;
(j) 0-5.0 weight % fragrance;
(k) 0-1 weight % of a pH adjuster,
(1) 0-5 weight % of a coloring agent;
(m) 0-5 weight % of an insoluble silicone;
(n) 0-5 weight % of a silicone resin;
(o) 0-10 weight % of a stabilizing agent for the insoluble silicone and/or the
silicone resin; and
(p) 0-2 weight % of a preservative.
3. A conditioning shampoo according to Claim 1 wherein the molecular weight of
the detergent soluble silicone is in the range of 1,000-10,000 daltons.
4. A conditioning shampoo according to Claim 1 wherein the water content is in
the range of 57-90 weight %.

5. A conditioning shampoo according to Claim 1 comprising about 5 to about 20
weight % of the anionic surfactant.
6. A conditioning shampoo according to Claim 1 wherein the anionic surfactant is
selected from the group consisting of alkyl and alkyl ether sulfates having from 7-25
carbons; alkyl sulfuric acid salts having about 8 to about 24 carbon atoms; olefin
sulfonates; beta-alkyloxy alkane sulfonates; reaction products of fatty acids esterified
with isethionic acid and neutralized with sodium hydroxide; and succinamates selected
from the group consisting of disodium N-octadecyl sulfofosuccinamate; tetrasodium N-
(l,2-dicarboxyethyl)-N-octadecylsulfosuccinamate; diamyl eater of sodium
sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; and dioctyl esters of
sodium sulfosuccinic acid; and mixtures of two or more of the foregoing.
7. A conditioning shampoo according to Claim 1 comprising an anionic surfactant
wherein the anionic surfactant is selected from the group consisting of 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, ammonium cocoyl sulfate, ammonium lauroyl sulfate, sodium cocoyl
sulfate, sodium lauroyl sulfate, potassium cocoyl sulfate, potassium lauryl sulfate,
triethanolamine lauryl sulfate, monoethanolamine cocoyl sulfate, monoethanolamine
lauryl sulfate, sodium tridecyl benzene sulfonate, sodium dodecyl benzene sulfonate,
and mixtures of two or more of the foregoing.
8. A conditioning shampoo according to Claim 1 comprising an anionic surfactant
wherein the anionic surfactant is selected from the group consisting of:
(i) polyethylene oxide condensates of alkyl phenols wherein the alkyl portion of the
alkyl phenol has 6-12 carbons and may be straight chain or branched and the ethylene
oxide portion is present in an amount of 10-60 moles of ethylene oxide per mole of
alkyl phenol;
(ii) condensation products of ethylene oxide with a product resulting from the reaction
of propylene oxide and ethylene diamine;
(iii) condensation products of C8-18 straight or branched chain aliphatic alcohols with
ethylene oxide;
(iv) long chain tertiary amine oxides of formula (R^XR2) 3)—N -O, wherein R1 is an
C8-18 alkyl, alkenyl or monohydroxy alkyls; which has from 0-10 ethylene moieties
and from 0-1 glyceryl moiety; and R2 and R3 may be the same or different and are each
independently selected from the group consisting of Cl-3 alkyls with 0-1 hydroxy
group;
(v) long chain tertiary phosphine oxides of Formula: R4 R5 R6 P-O where R4 contains
a C8-18 alkyl, alkenyl or monohydroxyalkyl radical; 0-10 ethylene oxide moieties and
0-1 glyceryl moiety, and R5 and R6 are each independently Cl-3 alkyl or
monohydroxyalkyl;
(vi) long chain dialkyl sulfoxides containing one short chain alkyl or hydroxy alkyl
radical of 1-? carbons and one long hydrophobic chain having a C8-20 alkyl, alkenyl,
hydroxy alkyl or keto alkyl group, with 0-10 ethylene oxide moieties and 0-1 glyceryl
moiety, and
(vii) mixtures of two or more of the foregoing.
9. A conditioning shampoo according to Claim 2 comprising a co-surfactant
10. A conditioning shampoo according to Claim 9 wherein the co-surfactant
comprises a nonionic surfactant wherein the nonionic surfactant is selected from the
group consisting of esters of polyols or sugars; fatty acid alkanolamides having 7-25
carbons; pyrrolidones; and the condensation products of ethylene oxide and C7-C25
long chain amides; and mixtures thereof.
11. A conditioning shampoo according to Claim 10 in which the alkanolamide is
selected from the group consisting of cocamide MBA, cocamide DBA, soyamide DEA,
lauramide DEA, oleamide MDPA, stearamide MEA, myristamide MEA, lauramide
MEA, capramide DEA, ricinoleamide DEA, myristamide DEA, stearamide DEA,
oleylamide DEA, tallowamide DEA, lauramide MEA, tallowamide MEA,
isostearamide DEA, isostearamide MEA, and combinations thereof where DEA means
diethauolamide; MEA means monoethanolamide; and MIPA means monoisopropy!
amide.
12. A conditioning shampoo according to Claim 9 comprising an amphoteric
surfactant wherein the amphoteric surfactant is selected from the group consisting of
aliphatic secondary and tertiary amines in which the aliphatic substituent contains from
about 8 to 18 carbon atoms and contains an anionic water solubilizing group selected
from the group consisting of carboxy, sulfonate, sulfate, phosphate, and phosphonate.
13. A conditioning shampoo according to Claim 12 wherein the amphoteric
surfactant is selected from the group consisting of sodium 3-dodecyl-aminopropionate,
sodium 3-dodecylaminopropane sulfonate, sodium lauryl sarcosinate, N-alkyltaurines,
N-higher alkyl aspartic acids, and mixtures thereof.
14. A conditioning shampoo according to Claim 2 comprising a zwitterionic
surfactant wherein the zwitterionic surfactant is selected from the group consisting of
cocodimethyl 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; lauryl bis-(2-
hydroxypropyi)alpha-carboxyethyl betaine;
sulfobetaines selected from the group consisting of cocodimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, lauryl bis-(2-hydroxyethyl) sulfopropyl betaine; amidobetaines and amidosulfobetaines, wherein the RCONH(CH2)3 radical is attached to the nitrogen atom of the betaine; and mixtures of two of more of the foregoing.
15. A conditioning shampoo according to Claim 1 wherein the cationic deposition
polymer is selected from the group of cationic polymers containing quaternary
ammonium or cationic protonated amino moieties selected from the group consisting of
cationic protonated primary, secondary, and tertiary amines.
16. A conditioning shampoo according to Claim 1 wherein the cationic deposition
polymer has an average molecular weight between about 5,000 and 10 million daltons.
17. A conditioning shampoo according to Claim 16 wherein the cationic deposition
polymer has an average molecular weight hi the range of about 200,000 to about 2
million daltons.
18. A conditioning shampoo according to Claim 1 wherein the cationic deposition
polymer has a cationic charge density ranging from about 0.2 meq/gm to about 7
meq/gm at the pH of the shampoo.
19. A conditioning shampoo according to Claim 1 wherein the detergent soluble
silicone is selected from the group consisting of:
a) water soluble siticones and b) water dispersible, detergent soluble but not water soluble silicones.
20. A conditioning shampoo according to Claim 19 wherein the detergent soluble
silicone is selected from the group consisting of:
dimethicone copolyols having a molecular weight less than 100,000 daltons.
21. A conditioning shampoo according to any one of Claims 1-20 wherein the
conditioning shampoo is free of insoluble silicones.
22. A conditioning shampoo according to any one of Claims 1 -20 wherein the
conditioning shampoo comprises a combination of soluble silicone and insoluble
silicone.
23. A conditioning shampoo according to Claim 2 wherein the salt is NaCl.
24. A conditioning shampoo according to Claim 1 further comprising an MQ resin.

Documents:

2312-delnp-2007-Abstract-(09-04-2013).pdf

2312-delnp-2007-abstract.pdf

2312-delnp-2007-Claims-(09-04-2013).pdf

2312-delnp-2007-claims.pdf

2312-delnp-2007-Correspondence-Others-(05-11-2012).pdf

2312-delnp-2007-Correspondence-Others-(09-04-2013).pdf

2312-delnp-2007-Correspondence-Others-(27-05-2013).pdf

2312-delnp-2007-correspondence-others.pdf

2312-delnp-2007-description (complete).pdf

2312-delnp-2007-Form 3-(05-11-2012).pdf

2312-delnp-2007-form-1.pdf

2312-delnp-2007-Form-18 (10-10-2008).pdf

2312-delnp-2007-Form-2-(09-04-2013).pdf

2312-delnp-2007-form-2.pdf

2312-delnp-2007-Form-3-(27-05-2013).pdf

2312-delnp-2007-form-3.pdf

2312-delnp-2007-form-5.pdf

2312-delnp-2007-GPA-(09-04-2013).pdf

2312-delnp-2007-pct-210.pdf

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Patent Number

259113

Indian Patent Application Number

2312/DELNP/2007

PG Journal Number

09/2014

Publication Date

28-Feb-2014

Grant Date

26-Feb-2014

Date of Filing

23-Mar-2007

Name of Patentee

COLGATE-PALMOLIVE COMPANY

Applicant Address

300 PARK AVENUE, NEW YORK, NEW YORK 10022 USA

Inventors:

#	Inventor's Name	Inventor's Address
1	KOZUBAL CHERYL	6 QUAIL HOLLOW DRIVE, WESTAMPTON, NEW JERSEY 08060 USA
2	HARTNETT DONNA	128 RED OAK WAY, BELLE MEAD, NEW JERSEY 08502 USA
3	FEI LIN	91 STILLWELL ROAD, KENDALL PARK, NEW JERSEY 08824 USA
4	DUGDALE JULIA	35 PINEY BRANCH ROAD, CRANBURY, NEW JERSEY 08512 USA
5	REICH CHARLES	324 LINCOLN AVENUE, HIGHLAND PARK, NEW JERSEY 08904 USA

PCT International Classification Number

A61Q 5/02

PCT International Application Number

PCT/US2005/036313

PCT International Filing date

2005-10-11

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	10/964,255	2004-10-13	U.S.A.