Source: https://patents.google.com/patent/EP1175202B1
Timestamp: 2018-02-23 17:58:16
Document Index: 501892415

Matched Legal Cases: ['Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 60']

EP1175202B1 - Anti-dandruff and conditioning shampoos containing polyalkylene glycols and cationic polymers - Google Patents
EP1175202B1
EP1175202B1 EP20000928694 EP00928694A EP1175202B1 EP 1175202 B1 EP1175202 B1 EP 1175202B1 EP 20000928694 EP20000928694 EP 20000928694 EP 00928694 A EP00928694 A EP 00928694A EP 1175202 B1 EP1175202 B1 EP 1175202B1
EP20000928694
EP1175202A1 (en )
EP1175202B3 (en )
Shampoo compositions comprising various combinations of detersive surfactants and conditioning agents, especially silicone conditioning agents, are known in the art and are commercially available. Many of these compositions have been found to provide excellent hair cleansing and conditioning performance. For example, Pantene® Shampoo Plus Pro-Vitamin Conditioner-in-One formulas which contain anionic surfactants, a cationic polymer and silicone conditioning agents provide excellent cleaning, conditioning and hair feel benefits upon application to hair.
Anti-dandruff shampoos which also provide conditioning benefits are likewise known in the art. For example, U.S. Pat. No. 5,624,666 exemplifies and claims shampoo compositions which contain anionic surfactants, cationic polymers and zinc pyridinethione as an anti-dandruff agent. U.S. Pat. No. 5,624,666 teaches that conditioning agents such as silicone fluids can optionally be incorporated into the compositions therein. Head & Shoulders® Dandruff Shampoo Plus Conditioner is an example of a marketed product which provides both anti-dandruff and conditioning benefits upon application of the shampoo to hair.
Applicants have now discovered, however, that, surprisingly, bioavailability and coverage of the anti-dandruff active are much more predictive of efficacy than deposition of the active on the haire of scalp. In fact, Applicants have found that, in some cases, even when an anti-dandruff active deposited very well on the hair and scalp. acceptable anti-dandruff efficacy was not achieved. Conversely, good anti-dandruff efficacy could be achieved in situations where the anti-dandruff active had good coverage and was highly bioavailable, but did not deposit superiorly to the hair or scalp. Thus, in order for a shampoo composition to provide a superior combination of anti-dandruff efficacy and conditioning compared to known shampoo compositions, it must meet certain criteria with respect to bioavailability and coverage, but it does not necessarily have to have the ability to deposit the anti-dandruff active superiorly on the hair or scalp.
The present invention relates to shampoo compositions which provide a superior combination of anti-dandruff efficacy and conditioning. These shampoo compositions comprise: (A) from about 5% to about 50%, by weight, of an anionic surfactant; (B) from about 0.01% to about 10%, by weight, of a non-volatile conditioning agent; (C) from about 0.1% to about 4%, by weight, of an anti-dandruff particulate; (D) from about 0.02% to about 5%, by weight of the composition, of at least one cationic polymer; (E) from 0.005% to about 1.5%, by weight, of a polyalkylene glycol; and (F) water. The polyalkylene glycol corresponds to the formula H(O-CH2-CHR)n-OH, wherein R is hydrogen, methyl or mixtures thereof, and n is an integer having an average value from about 1,500 to about 120,000.
The anionic detersive surfactant component can comprise an anionic detersive surfactant, a zwitterionic or an amphoteric detersive surfactant having an attached moiety that is anionic at the pH of the composition, or a combination thereof; preferably an anionic detersive surfactant. Such surfactants should be physically and chemically compatible with the essential components described herein, and should not otherwise unduly impair product stability, aesthetics or performance. Examples of anionic detersive surfactants which may be suitably employed in the shampoo compositions herein include, but are not limited to: sulfates, sulfonates, sarcosinates and sarcosine derivatives.
Non-limiting examples of alkyl ether sulfates which may be used in the shampoo compositions of the present invention include sodium and ammonium salts of coconut alkyl triethylene glycol ether sulfate, tallow alkyl triethylene glycol ether sulfate, and tallow alkyl hexaoxyethylene sulfate. Preferred alkyl ether sulfates are those comprising a mixture of individual compounds, wherein the compounds in the mixture have an average alkyl chain length from about C10 to about C16 and an average degree of ethoxylation of from about 1 to about 4 moles of ethylene oxide.
Also suitable for use in the anti-dandruff and conditioning shampoos of the present invention are those anionic detersive surfactants known as olefin sulfonates. As used herein, the term "olefin sulfonates" refers to compounds which can be produced by the sulfonation of α-olefins by means of uncomplexed sulfur trioxide, followed by neutralization of the acid reaction mixture in conditions such that any sulfones which have been formed in the reaction are hydrolyzed to give the corresponding hydroxy-alkanesulfonates. The sulfur trioxide can be liquid or gaseous, and is usually, but not necessarily, diluted by inert diluents, for example by liquid SO2, chlorinated hydrocarbons, and the like, when used in the liquid form, or by air, nitrogen, gaseous SO2, and the like, when used in the gaseous form. The α-olefins from which the olefin sulfonates are derived are mono-olefins which are from about C10 to about C24, preferably from about C12 to about C16. Preferably, they are straight chain olefins. In addition to the true alkene sulfonates and a proportion of hydroxy-alkanesulfonates, the olefin sulfonates can contain minor amounts of other materials, such as alkene disulfonates depending upon the reaction conditions, proportion of reactants, the nature of the starting olefins and impurities in the olefin stock and side reactions during the sulfonation process. A non-limiting example of such an α-olefin sulfonate mixture is described in U.S. Pat. No. 3,332,880, which description is incorporated herein by reference.
Another class of sulfonates suitable for use in the anti-dandruff and conditioning shampoo compositions of the present invention are those anionic detersive surfactants known as β-alkyloxy alkane sulfonates. These surfactants conform to the general Formula (I):
where R 1 is a straight chain alkyl group from about C6 to about C20, R 2 is a lower alkyl group from about C1 to about C3, preferably C1, and M is a water-soluble cation, as described above.
Other suitable sulfonates for use in the anti-dandruff and conditioning shampoos of the present invention are the water-soluble salts of organic, sulfuric acid reaction products conforming to the formula [ R1-SO3-M ] where R 1 is a straight or branched chain, saturated, aliphatic hydrocarbon radical from about C8 to about C24, preferably about C10 to about C18; and M is a cation described above. Non-limiting examples of such anionic detersive surfactants are the salts of an organic sulfuric acid reaction product of a hydrocarbon of the methane series, including iso-, neo-, and n-paraffins, and a sulfonating agent, e.g., SO3, H2SO4, obtained according to known sulfonation methods. The sulfonation methods may include bleaching and hydrolysis. The salts are preferably from about C8 to about C24; more preferably from about C12 to about C18. Preferred are alkali metal and ammonium sulfonated C10 to C18 n-paraffins.
Still other suitable sulfonates for use in the anti-dandruff and conditioning shampoo compositions of the present invention are the reaction products of fatty acids, which are esterified with isethionic acid, and then neutralized with sodium hydroxide. Preferred fatty acids are those derived from coconut oil or palm kernel oil. Also suitable are the sodium or potassium salts of fatty acid amides of methyl tauride in which the fatty acids are derived from coconut oil or palm kernel oil. Other similar anionic surfactants are described in U.S. Pat. No. 2,486,921; U.S. Pat. No. 2,486,922; and U.S. Pat. No. 2,396,278, which descriptions are incorporated herein by reference.
Also suitable for use in the anti-dandruff and conditioning shampoos of the present invention are those anionic detersive surfactants known as sarcosinates and sarcosine derivatives. Sarcosinates are the derivatives of sarcosine and N-methyl glycine, acylated with a fatty acid chloride. They conform to the general Formula (II):
wherein RCO- is a fatty acid radical and wherein X is either hydrogen (acid form) or a cationic species, such as Na+ or TEA+ (salt form). Non-limiting examples of sarcosinates and sarcosine derivatives include: sodium lauryl sarcosinate, lauryl sarcosine, cocoyl sarcosine, and mixtures thereof. A preferred sarcosinate is sodium lauryl sarcosinate.
The conditioning agent of the anti-dandruff and conditioning shampoo compositions of the present invention is preferably an insoluble siiicone conditioning agent. The silicone conditioning agent particles may comprise volatile silicone, non-volatile silicone, or combinations thereof. Preferred are non-volatile silicone conditioning agents. If volatile silicones are present, it will typically be incidental to their use as a solvent or carrier for commercially available forms of non-volatile silicone materials ingredients, such as silicone gums and resins. The silicone conditioning agent particles may comprise a silicone fluid conditioning agent and may also comprise other ingredients, such as a silicone resin to improve silicone fluid deposition efficiency or enhance glossiness of the hair (especially when high refractive index (e.g. above about 1.46) silicone conditioning agents are used (e.g. highly phenylated silicones).
The concentration of the silicone conditioning agent typical!y ranges from about 0.01% to about 10%, by weight of the composition, preferably from about 0.1% to about 8%, more preferably from about 0.1% to about 5%, most preferably from about 0.2% to about 3%. Non-limiting examples of suitable silicone conditioning agents, and optional suspending agents for the silicone, are described in U.S. Reissue Pat. No. 34,584, U.S. Pat. No. 5,104,646, and U.S. Pat. No. 5,106,609, which descriptions are incorporated herein by reference. The silicone conditioning agents for use in the anti-dandruff and conditioning shampoo compositions of the present invention preferably have a viscosity, as measured at 25°C, from about 20 to about 2,000,000 centistokes ("csk"), more preferably from about 1,000 to about 1,800,000 csk, even more preferably from about 50,000 to about 1,500,000 csk, most preferably from about 100,000 to about 1,500,000 csk.
The dispersed, silicone conditioning agent particles typically have a number average particle diameter ranging from about 0.01µm to about 50µm. For small particle application to hair, the number average particle diameters typically range from about 0.01µm to about 4µm, preferably from about 0.01µm to about 2µm, more preferably from about 0.01µm to about 0.5µm. For larger particle application to hair, the number average particle diameters typically range from about 4µm to about 50µm, preferably from about 6µm to about 30µm, more preferably from about 9µm to about 20µm, most preferably from about 12µm to about 18µm. Conditioning agents having an average particle size of less than about 5µm may deposit more efficiently on the hair. It is believed that small size particles of conditioning agent are contained within the coacervate that is formed between the anionic surfactant component (described above) and the cationic polymer component (described below), upon dilution of the shampoo.
Silicone fluids include silicone oils, which are flowable silicone materials having a viscosity, as measured at 25°C, less than 1,000,000 csk, preferably from about 5 csk to about 1,000,000 csk, more preferably from about 10 csk to about 100,000 csk. Suitable silicone oils for use in the anti-dandruff and conditioning shampoo compositions of the present invention include polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, polyether siloxane copolymers, and mixtures thereof. Other insoluble, non-volatile silicone fluids having hair conditioning properties may also be used.
wherein R is aliphatic, preferably alkyl or alkenyl, or aryl, R can be substituted or unsubstituted, and x is an integer from 1 to about 8,000. Suitable unsubstituted R groups for use in the anti-dandruff and conditioning shampoo compositions of the present invention include, but are not limited to: alkoxy, aryloxy, alkaryl, arylalkyl, arylalkenyl, alkamino, and ether-substituted, hydroxyl-substituted, and halogen-substituted aliphatic and aryl groups. Suitable R groups also include cationic amines and quaternary ammonium groups.
Preferred alkyl and alkenyl substituents are C1 to C5 alkyls and alkenyls, more preferably from C1 to C4, most preferably from C1 to C2. The aliphatic portions of other alkyl-, alkenyl-, or alkynyl-containing groups (such as alkoxy, alkaryl, and alkamino) can be straight or branched chains, and are preferably from C1 to C5, more preferably from C1 to C4, even more preferably from C1 to C3, most preferably from C1 to C2. As discussed above, the R substituents can also contain amino functionalities (e.g. alkamino groups), which can be primary, secondary or tertiary amines or quaternary ammonium. These include mono-, di- and tri-alkylamino and alkoxyamino groups, wherein the aliphatic portion chain length is preferably as described above. The R substituents may also be substituted with other groups, such as halogens (e.g. chloride, fluoride, and bromide), halogenated aliphatic or aryl groups, hydroxy (e.g. hydroxy substituted aliphatic groups), and mixtures thereof. Suitable halogenated R groups could include, for example, tri-halogenated (preferably tri-fluoro) alkyl groups such as -R1CF3, wherein R 1 is a C1 - C3 alkyl. An example of such a polysiloxane includes, but is not limited to, polymethyl 3,3,3-trifluoropropylsiloxane.
Non-volatile polyalkylsiloxane fluids that may be used include, for example, low molecular weight polydimethylsiloxanes. These siloxanes are available, for example, from the General Electric Company in their Viscasil R and SF 96 series, and from Dow Coming in their Dow Coming 200 series. Polyalkylaryl siloxane fluids that may be used, also include. for example, polymethylphenylsiloxanes. 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. Polyether siloxane copolymers that may be used include, for example, a polypropylene oxide modified polydimethylsiloxane (e.g., 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 concentrations must be sufficiently low to prevent solubility in water and the composition described herein.
Alkylamino substituted silicones suitable for use in the anti-dandruff and conditioning shampoo compositions of the present invention include, but are not limited to, those which conform to the following general Formula (IV):
wherein x and y are integers. This polymer is also known as "amodimethicone."
Cationic silicone fluids suitable for use in the anti-dandruff and conditioning shampoo compositions of the present invention include, but are not limited to, those which conform to the general formula (V): (R1)aG3-a-Si-(-OSiG2)n-(-OSiGb(R1)2-b)m-O-SiG3-a(R1)a wherein G is hydrogen, phenyl, hydroxy, or C1-C8 alkyl, preferably methyl; a is 0 or an integer having a value from 1 to 3, preferably 0; b is 0 or 1, preferably 1; n is a number from 0 to 1,999, preferably from 49 to 149; m is an integer from 1 to 2,000, preferably from 1 to 10; the sum of n and m is a number from 1 to 2,000, preferably from 50 to 150; R 1 is a monovalent radical conforming to the general formula CqH2qL, wherein q is an integer having a value from 2 to 8 and L is selected from the following groups: - N(R2)CH2-CH2-N(R2)2 - N(R2)2 -N(R2)3A- - N(R2)CH2-CH2-NR2H2A- wherein R2 is hydrogen, phenyl, benzyl, or a saturated hydrocarbon radical, preferably an alkyl radical from about C1 to about C20, and A - is a halide ion.
Other silicone cationic polymers which may be used in the anti-dandruff and conditioning shampoo compositions of the present invention are represented by the general formula (VII):
wherein R3 is a monovalent hydrocarbon radical from C1 to C18, preferably an alkyl or alkenyl radical, such as methyl; R4 is a hydrocarbon radical, preferably a C1 to C18 alkylene radical or a C10 to C18 alkyleneoxy radical, more preferably a C1 to C8 alkyleneoxy radical; Q- is a halide ion, preferably chloride; r is an average statistical value from 2 to 20, preferably from 2 to 8; s is an average statistical value from 20 to 200, preferably from 20 to 50. A preferred polymer of this class is known as UCARE SILICONE ALE 56™, available from Union Carbide.
Other silicone fluids suitable for use in the anti-dandruff and conditioning shampoo compositions of the present invention are the insoluble silicone gums. These gums are polyorganosiloxane materials having a viscosity, as measured at 25°C, of greater than or equal to 1,000,000 csk. Silicone gums are described in U.S. Pat. No. 4,152,416; Noll and Walter, Chemistry and Technology of Silicones, New York: Academic Press (1968); and in General Electric Silicone Rubber Product Data Sheets SE 30, SE 33, SE 54 and SE 76, all of which are incorporated herein by reference. The silicone gums will typically have a weight average molecular weight in excess of about 200,000, preferably from about 200,000 to about 1,000,000. Specific non-limiting examples of silicone gums for use in the anti-dandruff and conditioning shampoo compositions of the present invention include polydimethylsiloxane, (polydimethylsiloxane) (methylvinylsiloxane) copolymer, poly(dimethylsiloxane) (diphenyl siloxane)(methylvinylsiloxane) copolymer and mixtures thereof.
Other non-volatile, insoluble silicone fluid conditioning agents that are suitable for use in the anti-dandruff and conditioning shampoo compositions of the present invention are those known as "high refractive index silicones," having a refractive index of at least about 1.46, preferably at least about 1.48, more preferably at least about 1.52, most preferably at least about 1.55. The refractive index of the polysiloxane fluid will generally be less than about 1.70, typically less than about 1.60. In this context, polysiloxane "fluid" includes oils as well as gums.
The high refractive index polysiloxane fluids are also characterized by relatively high surface tensions as a result of their aryl substitution. Generally, the polysiloxane fluids will have a surface tension of at least about 2.4 Pa, typically at least about 2.7 Pa. Surface tension, for purposes hereof, is measured by a de Nouy ring tensiometer according to Dow Corning Corporate Test Method CTM 0461 (23 November, 1971). Changes in surface tension can be measured according to the above test method or according to ASTM Method D 1331.
Preferred high refractive index polysiloxane fluids have a combination of phenyl or phenyl derivative substituents (most preferably phenyl), with alkyl substituents, preferably C1-C4 alkyl (most preferably methyl), hydroxy, or C1-C4 alkylamino (especially -R1NHR2NH2 wherein each R 1 and R 2 independently is a C1-C3 alkyl, alkenyl, and/or alkoxy). High refractive index polysiloxanes are available from Dow Corning, Huls America, and General Electric.
Also, the spreading agent will preferably reduce the surface tension by at least about 0.2 Pa, preferably at least about 0.3 Pa, even more preferably at least about 0.4 Pa, most preferably at least about 0.5 Pa.
The surface tension of the mixture of the polysiloxane fluid and the spreading agent, at the proportions present in the final product, is preferably less than or equal to about 3 Pa, more preferably less than or equal to about 2.8 Pa, most preferably less than or equal to about 2.5 Pa. Typically, the surface tension will be in the range from about 1.5 Pa to about 3 Pa, more typically from about 1.8 Pa to about 2.8 Pa, and most generally from about 2 Pa to about 2.5 Pa.
Silicone fluids suitable for use in the anti-dandruff and conditioning shampoo compositions of the present invention are disclosed in U.S. Pat. No. 2,826,551, U.S. Pat. No. 3,964,500, U.S. Pat. No. 4,364,837, British Pat. No. 849,433, and Silicon Compounds. Petrarch Systems, Inc. (1984), all of which are incorporated herein by reference.
Silicone resins may be included in the silicone conditioning agent of the anti-dandruff and conditioning shampoo compositions of the present invention. These resins are highly cross-linked polymeric siloxane systems. The cross-linking 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 apparent to one of ordinary skill in the art, the degree of cross-linking that is required in order to result in a silicone resin will vary according to the specific silane units incorporated into the silicone resin. Generally, silicone materials which have a sufficient level of trifunctional and tetrafunctional siloxane monomer units (and hence, a sufficient level of cross-linking) such that they dry down to a rigid, or hard, film are considered to be silicone resins. The ratio of oxygen atoms to silicon atoms is indicative of the level of cross-linking in a particular silicone material. Silicone resins suitable for use in the anti-dandruff and conditioning shampoo compositions of the present invention generally have at least about 1.1 oxygen atoms per silicon atom. Preferably. the ratio of oxygen to silicon atoms is at least about 1.2:1.0. Silanes used in the manufacture of silicone resins include, but are not limited to: monomethyl-, dimethyl-, trimethyl-, monophenyl-, diphenyl-, methylphenyl-, monovinyl-, and methylvinyl-chlorosilanes, and tetrachlorosilane, with the methyl-substituted silanes being most commonly utilized. Preferred resins are available from General Electric as GE SS4230 and GE SS4267. Commercially available silicone resins are generally supplied in a dissolved form in a low viscosity volatile or non-volatile silicone fluid. The silicone resins for use herein should be supplied and incorporated into the present compositions in such dissolved form, as will be readily apparent to one of ordinary skill in the art.
Silicone materials and silicone resins in particular, can conveniently be identified according to a shorthand nomenclature system known to those of ordinary skill in the art as "MDTQ" nomenclature. Under this system, the silicone is described according to presence of various siloxane monomer units which make up the silicone. Briefly, the symbol M denotes the monofunctional unit (CH3)3SiO0.5; D denotes the difunctional unit (CH3)2SiO; T denotes the trifunctional unit (CH3)SiO1.5; and Q denotes the quadra- or tetra-functional unit SiO2. Primes of the unit symbols (e.g. M', D', T', and Q') denote substituents other than methyl, and must be specifically defined for each occurrence. Typical alternate substituents include, but are not limited to, groups such as vinyl, phenyls, amines, hydroxyls, and the like. The molar ratios of the various units, either in terms of subscripts to the symbols indicating the total number of each type of unit in the silicone (or an average thereof) or as specifically indicated ratios in combination with molecular weight complete the description of the silicone material under the MDTQ system. Higher relative molar amounts of T, Q, T' and/or Q' to D, D', M and/or M' in a silicone resin indicates higher levels of cross-linking. As discussed above, however, the overall level of cross-linking can also be indicated by the oxygen to silicon ratio.
The organic conditioning oils suitable for use as the conditioning agent herein are preferably low viscosity, water insoluble, liquids selected from the hydrocarbon oils, polyolefins, fatty esters, and mixtures thereof. The viscosity, as measured at 40°C, of such organic conditioning oils is preferably from about 1 centipoise to about 200 centipoise, more preferably from about 1 centipoise to about 100 centipoise, most preferably from about 2 centipoise to about 50 centipoise.
Organic conditioning oils for use in the anti-dandruff and conditioning shampoo compositions of the present invention can also include liquid polyolefins, more preferably liquid poly-α-olefins, most preferably hydrogenated liquid poly-α-olefins. Polyolefms for use herein are prepared by polymerization of C4 to about C14 olefenic monomers, preferably from about C6 to about C12.
Other fatty esters suitable for use in the anti-dandruff and conditioning shampoo compositions of the present invention are mono-carboxylic acid esters of the general formula R'COOR, wherein R' and R are alkyl or alkenyl radicals, and the sum of carbon atoms in R' and R is at least 10, preferably at least 20. The mono-carboxylic acid ester need not necessarily contain at least one chain with at least 10 carbon atoms; rather the total number of aliphatic chain carbon atoms must be least 10. Specific non-limiting examples of mono-carboxylic acid esters include: isopropyl myristate, glycol stearate, and isopropyl laurate.
Still other fatty esters suitable for use in the anti-dandruff and conditioning shampoo compositions of the present invention are di- and tri-alkyl and alkenyl esters of carboxylic acids, such as esters of C4 to C8 dicarboxylic acids (e.g. C1 to C22 esters, preferably C1 to C6, of succinic acid, glutaric acid, adipic acid, hexanoic acid, heptanoic acid, and octanoic acid). Specific non-limiting examples of di- and tri- alkyl and alkenyl esters of carboxylic acids include isocetyl stearyol stearate, diisopropyl adipate, and tristearyl citrate.
Other fatty esters suitable for use in the anti-dandruff and conditioning shampoo compositions of the present invention are water insoluble synthetic fatty esters. Some preferred synthetic esters conform to the general Formula (IX):
wherein R 1 is a C7 to C9 alkyl, alkenyl, hydroxyalkyl or hydroxyalkenyl group, preferably a saturated alkyl group, more preferably a saturated, linear, alkyl group; n is a positive integer having a value from 2 to 4, preferably 3; and Y is an alkyl, alkenyl, hydroxy or carboxy substituted alkyl or alkenyl, having from about 2 to about 20 carbon atoms, preferably from about 3 to about 14 carbon atoms. Other preferred synthetic esters conform to the general Formula (X):
3. Other conditionine agents
Also suitable for use in the compositions herein are the conditioning agents described by the Procter & Gamble Company in U.S. Pat. Nos. 5.674,478, and 5,750,122, both of which are incorporated herein in their entirety by reference. Also suitable for use herein are those conditioniag agents described in U.S. Pat. Nos. 4,529,586 (Clairol), 4,507,280 (Clairol), 4,663,158 (Clairol), 4,197,865 (L'Oreal), 4,217, 914 (L'Oreal), 4,381,919 (L'Oreal), and 4,422, 853 (L'Orea)), all of which descriptions are incorporated herein by reference.
Some other preferred silicone conditioning agents for use in the compositions of the present invention include: Abil® S 201 (dimethicone/sodium PG-propyldimethicone thiosulfate copolymer), available from Goldschmidt; DC Q2-8220 (trimethylsilyl amodimethicone) available from Dow Corning; DC 949 (amodimethicone, cetrimonium chloride, and Trideceth-12), available from Dow Corning; DC 749 (cyclomethicone and trimethylsiloxysilicate), available from Dow Corning; DC2502 (cetyl dimethicone), available from Dow Corning; BC97/004 and BC 99/088 (amino functionalized silicone microemulsions), available from Basildon Chemicals; GE SME253 and SM2115-D2_and SM2658 and SF1708 (amino functionalized silicone microemulsions), available from General Electric; siliconized meadowfoam seed oil, available from Croda; and those silicone conditioning agents described by GAF Corp. in U.S. Pat. No. 4,834,767 (quaternized amino lactam), by Biosil Technologies in U.S. Pat. No. 5,854,319 (reactive silicone emulsions containing amino acids), and by Dow Coming in U.S. Pat. No. 4,898,585 (polysiloxanes), all of which descriptions are incorporated herein by reference.
Pyridinethione anti-dandruff particulates, especially 1-hydroxy-2-pyridinethione salts, are highly preferred particulate anti-dandruff agents for use in the anti-dandruff and conditioning shampoo compositions of the present invention. The concentration of pyridinethione anti-dandruff particulate typically ranges from about 0.1% to about 4%, by weight of the composition, preferably from about 0.1% to about 3%, most preferably from about 0.3% to about 2%. Preferred pyridinethione salts include those formed from heavy metals such as zinc, tin, cadmium, magnesium, aluminum and zirconium, preferably zinc, more preferably the zinc salt of 1-hydroxy-2-pyridinethione (known as "zinc pyridinethione" or "ZPT"), most preferably 1-hydroxy-2-pyridinethione salts in platelet particle form, wherein the particles have an average size of up to about 20µ, preferably up to about 5µ, most preferably up to about 2.5µ. Salts formed from other cations, such as sodium, may also be suitable. Pyridinethione anti-dandruff agents are described, for example, in U.S. Pat. No. 2,809,971; U.S. Pat. No. 3,236,733; U.S. Pat. No. 3,753,196; U.S. Pat. No. 3,761,418; U.S. Pat. No. 4,345,080; U.S. Pat. No. 4,323,683; U.S. Pat. No. 4,379,753; and U.S. Pat. No. 4,470,982, all of which are incorporated herein by reference. It is contemplated that when ZPT is used as the anti-dandruff particulate in the shampoo compositions herein, that the growth or re-growth of hair may be stimulated or regulated, or both, or that hair loss may be reduced or inhibited, or that hair may appear thicker or fuller.
Selenium sulfide is a particulate anti-dandruff agent suitable for use in the anti-dandruff and conditioning shampoo compositions of the present invention, effective concentrations of which range from about 0.1% to about 4%, by weight of the composition, preferably from about 0.3% to about 2.5%, more preferably from about 0.5% to about 1.5%. Selenium sulfide is generally regarded as a compound having one mole of selenium and two moles of sulfur, although it may also be a cyclic structure that conforms to the general formula SexSy, wherein x + y = 8. Average particle diameters for the selenium sulfide are typically less than 15µm, as measured by forward laser light scattering device (e.g. Malvern 3600 instrument), preferably less than 10 µm. Selenium sulfide compounds are described, for example, in U.S. Pat. No. 2,694,668; U.S. Pat. No. 3,152,046; U.S. Pat. No. 4,089,945; and U.S. Pat. No. 4,885,107, all of which descriptions are incorporated herein by reference.
Sulfur may also be used as the particulate anti-dandruff agent in the anti-dandruff and conditioning shampoo compositions of the present invention. Effective concentrations of the particulate sulfur are typically from about 1% to about 4%, by weight of the composition, preferably from about 2% to about 4%.
A coacervate is formed, upon dilution of the shampoo composition, between the cationic polymer and the anionic detersive surfactant component (described above) of the present invention. It is believed that the cationic moiety of the polymer binds with the anionic moiety of the surfactant to form an insoluble complex that precipitates, upon dilution (the coacervate). Complex coacervates of the cationic polymer can also be formed with other optional anionic components of the shampoo composition (described below). Coacervate formation is dependent upon a variety of criteria, such as molecular weight, component concentration, and ratio of interacting ionic components, ionic strength (including modification of ionic strength, for example, by addition of salts), charge density of the cationic and anionic components, pH, and temperature. Coacervate systems and the effect of these parameters have been described, for example, in J. Caelles, et al., "Anionic and Cationic Compounds in Mixed Systems", Cosmetics & Toiletries, vol. 106, (April 1991), pp 49-54; C. J. van Oss, "Coacervation, Complex-Coacervation and Flocculation", J. Dispersion Science and Tech., vol. 9 (5,6), (1988-89), pp 561-73; and in D. J. Burgess, "Practical Analysis of Complex Coacervate Systems", J. of Colloid and Interface Science, vol. 140, no. 1, (November 1990), pp 227-38; all of which descriptions are incorporated herein by reference. The shampoo compositions described herein, typically have a ratio of anionic detersive surfactant component to cationic polymer component from about 25 : 0.02 to about 1 : 5, preferably from about 20 : 0.1 to about 12 : 1.
The average molecular weight of cationic conditioning polymers suitable for use herein is typically from about 5,000 to about 10,000,000. preferably from about 100,000 to about 2,000,000, more preferably from about 200,000 to about 1,500,000, more preferably from about 250,000 to about 850,000, more preferably from about 350.000 to about 850,000, most preferably from about 350,000 to about 500,000. The polymers have a cationic charge density typically from about 0.2 meq/g to about 7 meq/g, as measured at the pH of intended use of the shampoo composition, preferably from about 0.4meq/gm to about 5 meq/g, more preferably from about 0.6meq/g to about 2 meq/g, more preferably from about 0.5 meq/g to about 0.1 meq/g, more preferably from about 0.5 meq/g to about 0.9 meq/g. The pH of intended use of the shampoo composition typically ranges from about pH 3 to about pH 9, preferably from about pH 4 to about pH 7.
Suitable polysaccharide cationic polymers for use in the anti-dandruff and conditioning shampoo compositions of the present invention are the cationic cellulose derivatives and cationic starch derivatives. Such cationic polymers include those which conform to the general Formula (XI):
wherein A is an anhydroglucose residual group (e.g. a starch or cellulose anhydroglucose residual); R is an alkylene oxyalkylene, polyoxyalkylene, or hydroxyalkylene group, or combination thereof; R1, R2, and R 3 are independently 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 R1, R2, and R3) preferably being about 20 or less; and X is an anionic counterion as described above.
Preferred cationic cellulose polymers include, but are not limited to, those polymers available from Amerchol Corporation, in their Polymer JR and LR series of polymers, as salts of hydroxyethyl cellulose reacted with trimethyl ammonium substituted epoxide, known in the industry (CTFA) as Polyquaternium 10 (e.g. JR 30M®, available from Amerchol Corporation). Preferred Polyquaternium 10 polymers for use herein, typically have a charge density from about 0.3 meq/g to about 3 meq/g and a molecular weight from about 200,000 to about 1,500,00. Another non-limiting of a preferred type of cationic cellulose includes the polymeric quaternary ammonium salt of hydroxyethyl cellulose reacted with lauryl dimethyl ammonium-substituted epoxide, known in the industry (CTFA) as Polyquaternium 24, (e.g. Polymer LM 200®, available from Amerchol Corporation).
Also suitable for use herein are those quaternary nitrogen-containing cellulose copolymers of hydroxyethylcellulose reacted with diallyldimethyl ammonium chloride, known in the industry (CTFA) as Polyquatemium 4 (e.g. Celquat® H-100, available from National Starch Corporation). Quaternary nitrogen-containing cellulose ethers suitable for use herein are described in U.S. Pat. No. 3,962,418, and still other copolymers of etherified cellulose and starch suitable for use herein are described in U.S. Pat. No. 3,958,581, both of which descriptions are incorporated herein by reference.
wherein R5 is a C1 to C3 alkylene; X is chlorine or bromine, and Z is an anion such as Cl-, Br-, I- or HSO4 -.
wherein R is guar gum. Preferably, the cationic guar polymer is guar hydroxypropyltrimethylammonium chloride, which can be more specifically represented by the general Formula (XVI):
Specific non-limiting examples of cationic guar polymers which conform to Formula XVI include: Jaguar® C 13S, having a cationic charge density of 0.8meq/g (available from Rhodia Company) and Jaguar® C 17, having a cationic charge density of 1.6meq/g (available from Rhodia Company). Other suitable cationic guar polymers include hydroxypropylated cationic guar derivatives. Still other suitable cationic polymers include copolymers of etherified guar, some examples of which are described in U.S. Pat. No. 3,958,581, which description is incorporated herein by reference.
Other suitable cationic polymers for use in the anti-dandruff and conditioning shampoo compositions of the present invention are copolymers of vinyl monomers, having cationic protonated amine or quaternary ammonium functionalities, reacted with water soluble monomers. Non-limiting examples of such monomers include: acrylamide, methacrylamide, alkyl and dialkyl acrylamides, alkyl and dialkyl methacrylamides, alkyl acrylate, alkyl methacrylate, vinyl caprolactone , vinyl pyrrolidone, and mixtures thereof. The alkyl and dialkyl substituted monomers preferably have from C1 to C7 alkyl groups, more preferably from C1 to C3 alkyl groups. Other suitable monomers include vinyl esters, vinyl alcohol (made by hydrolysis of poly vinyl acetate), maleic anhydride, propylene glycol, ethylene glycol, and mixtures thereof.
Suitable cationic protonated amino and quaternary ammonium monomers, for inclusion in the cationic polymers of the shampoo composition herein, include vinyl compounds substituted with dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, monoalkylaminoalkyl acrylate, monoalkylaminoalkyl methacrylate, trialkyl methacryloxyalkyl ammonium salt, trialkyl acryloxyalkyl ammonium salt, diallyl quaternary ammonium salts; and vinyl quaternary ammonium monomers having cyclic cationic nitrogen-containing rings such as pyridinium, imidazolium, and quaternized pyrrolidones, such as alkyl vinyl imidazolium, alkyl vinyl pyridinium, and alkyl vinyl pyrrolidone salts. The alkyl portions of these monomers are preferably lower alkyls such as the C1 - C3 alkyls.
Other suitable cationic polymers for use in the anti-dandruff and conditioning shampoo compositions of the present invention include: copolymers of 1-vinyl-2-pyrrolidone and 1-vinyl-3-methylimidazolium salt (e.g., chloride salt), known in the industry (CTFA) as Polyquaternium 16 (e.g. Luviquat® FC 370, available from BASF Wyandotte Corporation); copolymers of 1-vinyl-2-pytrolidone and dimethylaminoethyl methacrylate, known in the industry (CTFA) as Polyquaternium 11 (e.g. Gafquat® 755N, available from ISP Corporation); cationic diallyl quaternary ammonium-containing polymers, including, for example, dimethyldiallylammonium chloride homopolymer, known in the industry (CTFA) as Polyquatemium 6; copolymers of acrylamide and dimethyldiallylammonium chloride, known in the industry (CTFA) as Polyquatemium 7; and mineral acid salts of amino-alkyl esters of homopolymers and copolymers of unsaturated C3 to C5 carboxylic acids, such as those described in U.S. Pat. No. 4,009,256, which description is incorporated herein by reference.
Still other cationic polymers for use in the anti-dandruff and conditioning shampoo compositions of the present invention are cationic modified proteins, such as lauryldimonium hydroxypropyl collagen (e.g. Croquat® L, available from Croda Corporation), or cocodimonium hydroxypropyl hydrolized hair keratin (e.g. Croquat® HH, available from Croda Corporation). Other cationic polymers include the polymeric quaternary salt prepared the reaction of adipic acid and dimethylaminopropylamine, reacted with dichloroethyl ether, known in the industry (CTFA) as Polyquaternium 2 (e.g. Mirapol® AD-1, available from Rhodia), and the polymeric quaternary salt prepared by the reaction of azelaic acid and dimethylaminopropylether, known in the industry (CTFA) as Polyquatemium 18 (e.g. Mirapol® AZ-1, available from Rhodia Corporation).
Yet other cationic polymers suitable for use herein are the Arquad® series of quaternary ammonium salts, available from Akzo Nobel. Other preferred cationic polymers for use herein include: Polymer KG30M (polyquaternium 10 and quaternized cellulose), Incroquat® behenyl trimonium methosulfate (cetearyl alcohol and behentrimonium methosulfate), available from Croda; Merquat® 5 (quaternary ammonium resin), available from Calgon; Gafquat® series 440 (cationic quatemized copolymers), available from ISP; Akypoquat® 131, available from Kao; Salcare® SC 60 (quaternary ammonium resin), or Salcare® SC95 or SC96 (cationic liquid dispersion thickeners), all available from Ciba; and Meadowquat® HG (PEG-2-dimeadowfoamamido-ethylmonium methosulfate), available from Fanning.
The polyalkylene glycols suitable for use in the shampoo compositions herein are characterized by the general Formula (XVII):
wherein R is hydrogen, methyl, or mixtures thereof, preferably hydrogen, and n is an integer having an average value from about 1,500 to about 120,000, preferably from about 1,500 to about 50,000, more preferably from about 2,500 to about 25,000, and most preferably from about 3,500 to about 15,000. When R is hydrogen, these materials are polymers of ethylene oxide, which are also known as polyethylene glycols. When R is methyl, these materials are polymers of propylene oxide, which are also known as polypropylene glycols. When R is methyl, it is also understood that various positional isomers of the resulting polymers can exist. Preferred for use herein are polyethylene glycols, polypropylene glycols, and mixtures thereof.
Specific non-limiting examples of polyethylene glycol polymers for use in the anti-dandruff and conditioning shampoo compositions of the present invention include: PEG 2M, wherein R is hydrogen and n has an average value of about 2,000 (e.g. Polyox WSR® N-10, available from Union Carbide); PEG 5M,
wherein R is hydrogen and n has an average value of about 5,000 (e.g. Polyox WSR® N-35 and Polyox WSR® N-80, both available from Union Carbide); PEG 7M, wherein R is hydrogen and n has an average value of about 7,000 (e.g. Polyox WSR® N-750, available from Union Carbide); PEG 9M, wherein R is hydrogen and n has an average value of about 9,000 (e.g. Polyox WSR® N-3333, available from Union Carbide); PEG 14 M, wherein R is hydrogen and n has an average value of about 14,000 (e.g. Polyox WSR® N-3000, available from Union Carbide); PEG 23M, wherein R is hydrogen and n has an average value of about 23,000 (e.g. Polyox WSR® N-12k, available from Union Carbide); PEG 90M, wherein R is hydrogen and n has an average value of about 90,000 (e.g. Polyox WSR® 301, available from Union Carbide); and PEG 100M, wherein R is hydrogen and n has an average value of about 100,000 (e.g. Carbowax PEG 4600™, available from Union Carbide). Preferred polyethylene glycols include PEG 7M, PEG 14M, PEG 25M, PEG 90M, and mixtures thereof.
Cationic detersive surfactants suitable for use herein include, but are not limited to, surfactants containing quaternary nitrogen moieties. Examples of suitable cationic surfactants are those corresponding to the general Formula (XVIII):
Preferred cationic detersive surfactants are those containing two long alkyl chains and two short alkyl chains or those containing one long alkyl chain and three short alkyl chains. Such long alkyl chains are preferably from C12 to C22, more preferably from C16 to C22. Such short alkyl chains are preferably from C1 to C3, more preferably from C1 to C2. Nonionic detersive surfactants suitable for use herein include, but are not limited to, those compounds produced by condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature.
Non-limiting examples of other amphoteric, zwitterionic, cationic and nonionic detersive surfactants suitable for use in the anti-dandruff and conditioning shampoo composition of the present invention are described in McCutcheon's, Emulsifiers and Detergents, (1989), published by M. C. Pub. Co., and in U.S. Pat. No. 2,438,091; U.S. Pat. No. 2,528,378; U.S. Pat. No. 2,658,072; U.S. Pat. No. 3,155,591; U.S. Pat. No. 3,929,678; U.S. Pat. No. 3,959,461; U.S. Pat. No. 4,387,090; U.S. Pat. No. 5,104,646; U.S. Pat. No. 5,106,609; and U.S. Pat. No. 5,837,661, all of which descriptions are incorporated herein by reference.
Still other suitable suspending agents for use in the anti-dandruff and conditioning shampoo compositions of the present invention include carboxyvinyl polymers. Preferred among these polymers are the copolymers of acrylic acid crosslinked with polyallylsucrose, as described in U.S. Pat. No. 2,798,053, which description is incorporated herein by reference. Examples of these polymers include Carbopol 934, 940, 941, and 956, available from B. F. Goodrich Company.
As used herein, the term "hair growth regulating" is meant to include: stimulating hair growth and/or hair thickening; preventing, reducing, arresting and/or retarding the loss of hair and/or the thinning of hair; increasing the rate of hair growth; inducing the formation of a greater number of hair strands; increasing the diameter of the hair strand; lengthening the hair strand; changing the hair follicle from vellus to terminal; converting follicles from telogen to anagen phase (thereby increasing the overall ratio of anagen phase follicles relative to telogen phase follicles); treating alopecias; and any combination thereof.
Vasodilators such as potassium channel agonists including, for example, minoxidil and minoxidil derivatives such as aminexil and such as those described in U.S. Patent 3,382,247, U.S. Patent 5,756,092, issued May 26, 1998, U.S. Patent 5,772,990, issued June 30, 1998, U.S. Patent 5,760,043, issued June 2, 1998, U.S. Patent 328,914, issued July 12, 1994, U.S. Patent 5,466,694, issued November 14, 1995, 5,438,058, issued August 1, 1995, and U.S. Patent 4,973,474, issued November 27, 1990, (all of which are herein incorporated by reference), and cromakalin and diazoxide can be used as optional hair growth regulating agents in the compositions herein.
One suitable class of optional activity enhancer for use herein are anti-androgens. Examples of suitable anti-androgens may include, but are not limited 5-α-reductase inhibitors such as finesteride and those described in U.S. Patent 5,516,779, issued May 14, 1996 (herein incorporated by reference) and in Nnane et al, Cancer Research 58, "Effects of Some Novel Inhibitors of C17,20-Lyase and 5α-Reductase in Vitro and in Vivo and Their Potential Role in the Treatment of Prostate Cancer., as well as cyproterone acetate, azelaic acid and its derivatives and those compounds described in U.S. Patent 5,480,913, issued January 2, 1996, flutamide, and those described in U.S. Patents 5,411,981, issued May 2, 1995, U.S. Patent 5,565,467, issued October 15, 1996 and U.S. Patent 4,910,226, issued March 20, 1990, all of which are herein incorporated by reference.
Another suitable class of optional hair growth regulating agents are immunosuppressants such as 1) cyclosporin and cyclosporin analogs including those described in U.S. Provisional Patent Application No. 60/122,925, Fulmer et al., "Method of Treating Hair Loss Using Non-Immunosuppressive Compounds", filed March 5, 1999, herein incorporated by reference, and 2) FK506 analogs such as those described in U.S. Provisional Patent Application No. 60/102,449, McIver et al., "Heterocyclic 2-Substituted Ketoamides", filed September 30, 1998, U.S. Provisional Patent Application No. 60/102,448, McIver et al., "2-Substituted Ketoamides", filed September 30, 1998, U:S. Provisional Patent Application No. 60/102,539, McIver et al., "2-Substituted Heterocyclic Sulfonamides", filed September 30, 1998, U.S. Provisional Patent Application No. 60/102,458, Tiesman et al., "Method of Treating Hair Loss Using Ketoamides", filed September 30, 1998, and U.S. Provisional Patent Application No. 60/102,437, McIver et al., "Method of Treating Hair Loss Using Sulfonamides", filed September 30, 1998, all of which are herein incorporated by reference.
Anti-inflammatories can also be incorporated into the compositions herein as an optional activity enhancer. Examples of suitable anti-inflammatories may include glucocorticoids such as hydrocortisone, mometasone furoate and prednisolone, nonsteroidal anti-inflammatories including cyclooxygenase or lipoxygenase inhibitors such as those described in U.S. Patent 5,756,092, and benzydamine, salicylic acid, and those compounds described in EPA 0,770,399, published May 2, 1997, WO 94/06434, published March 31, 1994 and FR 2,268,523, published November 21, 1975, all of which are herein incorporated by reference.
Another suitable class of optional hair growth regulating agents are thyroid hormones and derivatives and analogs thereof. Examples of suitable thyroid hormones for use herein may include triiodothyrionine. Examples of thyroid hormone analogs which may be suitable for use herein include those described in U.S. Provisional Patent Application No. 60/136,996, Zhang et al., "Method of Treating Hair Loss", filed June 1, 1999, U.S. Provisional Patent Application No. 60/137,024, Zhang et al., "Method of Treating Hair Loss Using Biphenyl Compounds", filed June 1, 1999, U.S. Provisional Patent Application No. 60/137,022, Zhang et al., "Method of Treating Hair Loss Using Carboxyl Derivatives", filed June 1, 1999, U.S. Provisional Patent Application No. 60/137,023, Zhang et al., "Method of Treating Hair Loss Using Sulfonyl Thyromimetic Compounds", filed June 1, 1999, U.S. Provisional Patent Application No. 60/137,052, Youngquist et al., "Biaryl Compounds", filed June 1, 1999, U.S. Provisional Patent Application No. 60/137,063, Youngquist et al., "Sulfur-Bridged Compounds", filed June 1, 1999, and U.S. Provisional Patent Application No. 60/136,958, Youngquist et al., "Substituted Biaryl Ether Compounds", filed June 1, 1999.
Prostaglandin agonists or antagonists can also be used as optional hair growth regulating agents in the compositions herein. Examples of suitable prostaglandins agonists or antagonists include latanoprost and those described in WO 98/33497, Johnstone, published August 6, 1998, WO 95/11003, Stjernschantz, published April 27, 1995, JP 97-100091, and Ueno, JP 96-134242, Nakamura.
Non-limiting examples of penetration enhancers which may be used as optional hair growth regulating agents herein include, for example, 2-methyl propan-2-ol, propan-2-ol, ethyl-2-hydroxypropanoate, hexan-2,5-diol, POE(2) ethyl ether, di(2-hydroxypropyl) ether, pentan-2,4-diol, acetone, POE(2) methyl ether, 2-hydroxypropionic acid, 2-hydroxyoctanoic acid, propan-1-ol, 1,4-dioxane, tetrahydrofuran, butan-1,4-diol, propylene glycol dipelargonate, polyoxypropylene 15 stearyl ether, octyl alcohol, POE ester of oleyl alcohol, oleyl alcohol, lauryl alcohol, dioctyl adipate, dicapryl adipate, di-isopropyl adipate, di-isopropyl sebacate, dibutyl sebacate, diethyl sebacate, dimethyl sebacate, dioctyl sebacate, dibutyl suberate, dioctyl azelate, dibenzyl sebacate, dibutyl phthalate, dibutyl azelate, ethyl myristate, dimethyl azelate, butyl myristate, dibutyl succinate, didecyl phthalate, decyl oleate, ethyl caproate, ethyl salicylate, iso-propyl palmitate, ethyl laurate, 2-ethyl-hexyl pelargonate, iso-propyl isostearate, butyl laurate, benzyl benzoate, butyl benzoate, hexyl laurate, ethyl caprate, ethyl caprylate, butyl stearate, benzyl salicylate, 2-hydroxypropanoic acid, 2-hyroxyoctanoic acid, methylsulfoxide, N,N-dimethyl acetamide, N,N-dimethyl formamide, 2-pyrrolidone, 1-methyl-2-pyrrolidone, 5-methyl-2-pyrrolidone, 1,5-dimethyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, phosphine oxides, sugar esters, tetrahydrofurfural alcohol, urea, diethyl-m-toluamide 1-dodecylazacyloheptan-2-one and those described in U.S. Patent 5,015,470, issued May 14, 1991 and U.S. Patent 5,496,827, issued July 15, 1994 (both of which are herein incorporated in its entirety by reference).
Other classes of optional hair growth regulating agents for use herein include flavinoids, ascomycin derivatives and analogs, histamine antagonists such as diphenhydramine hydrochloride, other triterpenes such as oleanolic acid and ursolic acid and those described in U.S. Patent 5,529,769, JP 10017431, WO 95/35103, U.S. Patent 5,468,888, JP 09067253, WO 92/09262, JP 62093215, U.S. Patent 5,631,282, U.S. Patent 5,679,705, JP 08193094, saponins such as those described in EP 0,558,509 to Bonte et al, published September 8, 1993 and WO 97/01346 to Bonte et al, published January 16, 1997 (both of which are herein incorporated by reference in their entirety), proeoglycanase or glycosaminoglycanase inhibitors such as those described in U.S. Patents 5,015,470, issued May 14, 1991, U.S. Patent 5,300,284, issued April 5, 1994 and U.S. Patent 5,185,325, issued February 9, 1993 (all of which are herein incorporated in their entirety by reference) estrogen agonists and antagonists, pseudoterins, cytokine and growth factor promoters, analogs or inhibitors such as interleukin1 inhibitors, interleukin-6 inhibitors, interleukin-10 promotors, and tumor necrosis factor inhibitors, vitamins such as vitamin D analogs and parathyroid hormone antagonists, Vitamin B 12 analogs and panthenol, interfuron agonists and antagonists, hydroxyacids such as those described in U.S. Patent 5,550,158, benzophenones and hydantoin anticonvulsants such as phenytoin.
Other hair growth agents are described in detail in, for example, JP 09-157,139 to Tsuji et al, published June 17, 1997; EP 0277455 A1 to Mirabeau, published August 10, 1988; WO 97/05887 to Cabo Soler et al, published February 20, 1997; WO 92/16186 to Bonte et al, published March 13, 1992; JP 62-93215 to Okazaki et al, published April 28, 1987; U.S. Patent 4,987,150 to Kurono et al, issued January 22, 1991; JP 290811 to Ohba et al, published October 15, 1992; JP 05-286,835 to Tanaka et al, published November 2, 1993, FR 2,723,313 to Greff, published August 2, 1994, U. S. Patent 5,015,470 to Gibson, issued May 14, 1991, U.S. Patent 5,559,092, issued September 24, 1996, U.S. patent 5,536,751, issued July 16, 1996, U.S. Patent 5,714,515, issued February 3, 1998, EPA 0,319,991, published June 14, 1989, EPA 0,357,630, published October 6, 1988, EPA 0,573,253, published December 8, 1993, JP 61-260010, published November 18, 1986, U.S. Patent 5,772,990, issued June 30, 1998, U.S. Patent 5,053, 410, issued October 1, 1991, and U.S. Patent 4,761,401, issued August 2, 1988, all of which are herein incorporated by reference.
Optional viscosity modifiers and thickeners may used, typically in amounts effective for the anti-dandruff and conditioning shampoo compositions of the present invention to generally have an overall viscosity from about 1,000 csk to about 20,000 csk, preferably from about 3,000 csk to about 10,000 csk. Specific non-limiting examples of such viscosity modifiers and thickeners include; sodium chloride, sodium sulfate, and mixtures thereof.
The anti-dandruff and conditioning shampoo compositions of the present invention may be prepared by any known or otherwise effective technique, suitable for providing a shampoo composition provided that the resulting composition provides the excellent hair feel benefits described herein. Methods for preparing the anti-dandruff and conditioning shampoos of the present invention include conventional formulation and mixing techniques. A method such as that described in U.S. PaL No. 5,937,661, which description is incorporated herein by reference, could be employed, wherein the anti-dandruff particulate of the present invention would typically be added in the same step as the silicone premix is added in the '661 description.
The anti-dandruff and conditioning shampoo compositions of the present invention are used in a conventional manner for cleansing and conditioning the hair or skin. They are particularly used in a conventional manner for treating the condition commonly known as dandruff. An effective amount of the composition for cleansing and conditioning the hair or skin is applied to hair, or other region of the body, that has preferably been wetted, generally with water, and then the composition is rinsed off. Effective amounts typically range from about 1g to about 50g, preferably from about 1g to about 20g. Application to the hair typically includes working the composition through the hair such that most or all of the hair is contacted with the composition.
The following are non-limiting examples of the anti-dandruff and conditioning shampoo compositions of the present invention. The examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as many variations thereof are possible without departing from the scope of the invention, which would be recognized by one of ordinary skill in the art. In the examples, all concentrations are listed as weight percent, unless otherwise specified. As used herein, "minors" refers to those optional components such as preservatives, viscosity modifiers, pH modifiers, fragrances, foam boosters, and the like. As is apparent to one of ordinary skill in the art, the selection of these minors will vary depending on the physical and chemical characteristics of the particular ingredients selected to make the present invention as described herein.
A suitable method for preparing the anti-dandruff and conditioning shampoo compositions described in Examples I - XV (below) follows: About one-third to all of the ammonium laureth sulfate (added as 25wt% solution) is added to a jacketed mix tank and heated to about 60°C to about 80°C with slow agitation to form a surfactant solution Cocamide MEA and fatty alcohols, (where applicable), are added to the tank and allowed to disperse. Salts (e.g. sodium chloride) and pH modifiers (e.g. citric acid, sodium citrate) are added to the tank and allowed to disperse. Ethylene glycol distearate ("EGDS") is added to the mixing vessel and allowed to melt. After the EGDS is melted and dispersed, preservative is added to the surfactant solution. The resulting mixture is cooled to about 25°C to about 40°C and collected in a finishing tank. As a result of this cooling step, the EGDS crystallizes to form a crystalline network in the product. The remainder of the ammonium laureth sulfate and other components, including the silicone and anti-dandruff particulate, are added to the finishing tank with agitation to ensure a homogeneous mixture. Cationic polymer is dispersed in water as an about 0.1% to about 10% aqueous solution and then added to the final mix. Once all components have been added, additional viscosity and pH modifiers may be added, as needed, to the mixture to adjust product viscosity and pH to the extent desired.
Ammonium Laureth Sulfate 12 12 11 10 12
Guar Hydroxypropyltrimonium Chloride 0.4 0.4 0.25 0..6 0.6
PEG 23M --- --- --- --- 0.1
PEG 90M 0.1 0.05 0.025 0.01 ---
Zinc Pyrithione 1 1 1 1 1
1-decene homopolymer 0.2 0.3 0.3 0.5 0.4
Trimethylpropane Capyl Caprylate 0.2 0,1 0.1 0.0 0.1
Dimethicone 1.0 2.0 0.8 0.5 1.25
Water and minors ----------- quantity sufficient ------------
Polyquaternium-10 --- --- 0.25 0.25 0.1
Guar Hydroxypropyltrimonium Chloride --- 0.25 --- --- ---
Guar Hydroxypropyltrimonium Chloride 0.5 --- 0.25 0.35 0.4
PEG 7M 0.1 --- 0.1 0.1 0.2
PEG 90M --- 0.1 --- --- ---
1-decene homopolymer 0.2 0.4 0.4 0.5 0.5
Trimethylpropane Capyl Caprylate 0.1 --- 0.1 0.2 ---
Dimethicone 0.55 1.15 1.35 3.25 3.35
Water and minors ------------ quantity sufficient ------------
Ammonium Lauryl Sulfate 6 7 7 5 5
Polyquaternium-10 0.15 --- --- --- ---
Guar Hydroxypropyltrimonium Chloride --- --- 0.1 --- ---
Guar Hydroxypropyltrimonium Chloride --- 0.4 --- 0.1 ---
Guar Hydroxypropyltrimonium Chloride --- --- --- --- 0.5
Guar Hydroxypropyltrimonium Chloride 0.25 --- --- --- ---
PEG 90M 0.025 0. 1 0.15 0.15 0.2
1-decene homopolymer 0.6 0.2 0.4 --- 0.1
Trimethylpropane Capyl Caprylate --- --- 0.3 0.2 0.1
Dimethicone 1.35 1.45 0.75 1.1 0.85
A shampoo composition characterised in that it comprises:
a) from 5% to 50%, by weight of the composition, of an anionic surfactant;
b) from 0.01% to 10%, by weight of the composition, of a non-volatile conditioning agent;
c) from 0.1% to 4%, by weight of the composition, of an anti-dandruff particulate;
d) from 0.02% to 5%, by weight of the composition, of at least one cationic polymer;
e) from 0.005% to 1.5%, by weight of the composition, of a polyalkylene glycol corresponding to the formula:
i) wherein R is selected from the group consisting of hydrogen, methyl and mixtures thereof,
ii) wherein n is an integer having an average value from 1,500 to 120,000; and f) water.
A shampoo composition according to any Claim 1, wherein said at least one cationic polymer component is selected from the group consisting of: guar derivatives, preferably guar hydroxypropyltrimonium chloride; cellulose derivatives, preferably polyquaternium-10; and mixtures thereof.
A shampoo composition according to any preceding claim, characterised in that it comprises from 0.1% to 1%, by weight of the composition, of said at least one cationic polymer.
A shampoo composition according to any preceding claim, wherein said guar derivatives have a molecular weight from 50,000 to 700,000, and a charge density from 0.05 meq/g to 0.9 meq/g; and said cellulose derivatives have a molecular weight from 200;000 to 1,500,000, preferably from 350,000 to 500,000, and a charge density from 0.2 meq/g to 0.6 meq/g.
A shampoo composition according to any preceding claim, wherein said non-volatile conditioning agent comprises dispersed, silicone.
A shampoo composition according to any preceding claim, wherein said polyalkylene glycol has an average value of n from 1,500 to 50,000, preferably from 3,500 to 15,000.
A shampoo composition according to any preceding claim, wherein said anti-dandruff Particulate is a zinc salt of 1-hydroxy-2-pyridinethione, and preferably wherein said zinc salt of 1-hydroxy-2-pyridinethione is in platelet particle form.
A shampoo composition according to any preceding claim, wherein said composition further comprises from 0.1% to 10%, by weight of the composition, of a suspending agent, and preferably wherein said suspending agent is ethylene glycol distearate.
a) from 10% to 25%, by weight of the composition, of an anionic surfactant;
b) from 0.01 % to 10%, by weight of the composition, of an insoluble, non-volatile silicone conditioning agent;
c) from 0.3% to 2%, by weight of the composition, of a zinc salt of 1-hydroxy-2-pyridinethione;
d) from 0.1% to 0.1%, by weight of the composition, of at least one cationic polymer selected from the group consisting of guar derivatives, cellulose derivatives, and mixtures thereof;
e) from 0.025% to 1.5%, by weight of the composition, of a polyalkylene glycol corresponding to the formula:
ii) wherein n is an integer having an average value from 3,500 to 15,000; and f) water.
A method for providing anti-dandruff efficacy and conditioning hair characterised in that it comprises:
a) wetting said hair with water;
b) applying to said hair an effective amount of a shampoo composition according to any preceding claim; and
c) rinsing said shampoo composition from said hair using water.
A shampoo composition according to any claims 1-9 further characterised in that it comprises from 0.001% to 15% of a hair growth regulating agent selected from the group consisting of zinc salts of carboxylic acids, saponins, triterpenes, oleanolic acid, ursolic acid, betulinic acid, betulonic acid, crataegolic acid, celastrol, asiatic acid, inhibitors of 5-α-reductase, progesterone, 1,4-methyl-4-azasteroids, 17-β-N,N-diethylcarbamoyl-4-methyl-4-aza-5-α-androstan-3-one, androgen receptor antagonists, cyproterone acetate, minoxidil, azelaic acid and derivatives thereof, cyclosporin, triiodothyronine, diazoxide, potassium channel openers, cromakalin, phenytoin, ketoconazole, finesteride, dutasteride, coal tar, zinc gluconate, glucocortisoids, macrolides, aminexil, and mixtures thereof.
A non-therapeutic method for regulating the growth of the hair characterised in that it comprises:
b) applying to said hair an effective amount, of a shampoo composition according to claim 11; and
EP20000928694 1999-05-03 2000-05-02 Anti-dandruff and conditioning shampoos containing polyalkylene glycols and cationic polymers Active EP1175202B3 (en)
US132869P 1999-05-03
EP1175202A1 true EP1175202A1 (en) 2002-01-30
EP1175202B1 true EP1175202B1 (en) 2004-09-15
EP1175202B3 EP1175202B3 (en) 2014-03-05
EP20000928694 Active EP1175202B3 (en) 1999-05-03 2000-05-02 Anti-dandruff and conditioning shampoos containing polyalkylene glycols and cationic polymers
DE10224025A1 (en) * 2002-05-31 2003-12-11 Beiersdorf Ag Nourishing Shampoo
JP4157555B2 (en) * 2002-11-12 2008-10-01 ユニリーバー・ナームローゼ・ベンノートシヤープ Composition for cleaning and conditioning hair
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