United States Patent [19J
`Ramachandran et al.
`
`[54] SCALP CARE PRODUCTS CONTAINING
`ANTI ITCHING /ANTI IRRITANT AGENTS
`
`[75]
`
`Inventors: Pallassana Narayanier
`Ramachandran, Robbinsville;
`Clarence Ralph Robbins, Martinsville;
`Amrit Manila) Patel, Dayton, all of
`N.J.
`
`[73] Assignee: Colgate-Palmolive Company, New
`York, N.Y.
`
`[21] Appl. No.: 08/668,803
`
`[22]
`
`Filed:
`
`Jun. 24, 1996
`
`Related U.S. Application Data
`
`[63]
`
`[51]
`
`[52]
`
`[58]
`
`Continuation of application No. 08/411,884, Mar. 31, 1995,
`abandoned.
`Int. Cl.6
`................................ CUD l/02; CllD 1!94;
`CllD 3/28
`U.S. Cl. .......................... 510/124; 510/122; 510/125;
`510/127; 510/131; 510/137; 510/138; 510/159;
`510/386; 510/500; 510/501; 510/504; 424/70.19;
`424/70.21; 424/70.24; 424/70.27; 514/852;
`514/385; 514/396
`Field of Search ..................................... 510/122, 124,
`510/125, 127, 131, 137, 138, 159, 386,
`500, 501, 504; 424/70.19, 70.21, 70.24,
`70.27; 514/852, 385, 396
`
`[56]
`
`References Cited
`
`U.S. PATENT DOCUMENTS
`
`111111
`
`1111111111111111111111111111111111111111111111111111111111111
`US005900393A
`[11] Patent Number:
`[45] Date of Patent:
`
`5,900,393
`May 4,1999
`
`3,903,287
`4,329,334
`4,329,335
`4,329,336
`4,835,148
`4,867,971
`5,106,613
`5,151,209
`5,384,114
`
`9/1975 Meiser et a!. ........................... 424/273
`5/1982 Su et a!. .................................... 424/70
`5/1982 Su et a!. .................................... 424/70
`5/1982 Su et a!. .................................... 424/70
`5/1989 Barford et a!.
`... ... .... ... ... ... ... ... 514/179
`9/1989 Ryan et a!.
`............................... 424/81
`4/1992 Hartnett et a!. ........................... 424/71
`9/1992 McCall eta!. ..................... 252/174.15
`1!1995 Dowell et a!. ......................... 424/70.1
`
`FOREIGN PATENT DOCUMENTS
`
`136914
`312234
`
`4/1985 European Pat. Off ..
`4/1989 European Pat. Off ..
`
`Primary Examiner-Douglas 1. McGinty
`Assistant Examiner-Gregory R. Delcotto
`Attorney, Agent, or Firm-Richard 1. Ancel; Rosemary M.
`Miano; Richard N. Miller
`
`[57]
`
`ABSTRACT
`
`Mild aqueous detergent, e.g., shampoo, compositions are
`disclosed based on a mixture comprising anionic surfactant
`and amphoteric surfactant, such as betaines, present in the
`composition at a level of from about 0.75 to 1.25 parts by
`weight per part by weight of anionic surfactant. The com(cid:173)
`positions also contain one or a mixture of therapeutic agents
`such as climbazole or a mixture of climbazole and one or
`more co-therapeutics such as salicylic acid. The combina(cid:173)
`tion of mild surfactant system and therapeutic agent serve to
`prevent or treat mild skin disorders such as scalp itch and
`scalp irritation when applied to the scalp as a shampoo.
`Shampoo compositions also preferably contain one or more
`conditioning agents and suitable suspending agents.
`
`3,812,142
`
`5/1974 Meiser eta!. ........................... 260/309
`
`18 Claims, No Drawings
`
`1
`
`

`

`5,900,393
`
`1
`SCALP CARE PRODUCTS CONTAINING
`ANTI ITCHING /ANTI IRRITANT AGENTS
`
`this is a continuation of pending prior application Ser.
`No. 08/411,884 filed Mar. 31, 1995, now abandoned.
`
`BACKGROUND OF THE INVENTION
`
`5
`
`2
`3- dio x o 1 an- 4- yl) me tho xy )phenyl) -piperazine
`(Ke toconazole); 1-hydroxy -4-me thyl- 6 -(2,4,4-
`trimethylpentyl)-2-pyridone monoethonolamine salt
`(picrotone olamine ); selenium sulfide; zinc pyrithione; coal
`tar; sulfur; 2-( 4'-isobutylphenyl) propionic acid (ibuprofen);
`and mixtures thereof.
`The invention also provides for a method of treating scalp
`disorders such as scalp irritation and/or itching comprising
`applying to the hair and scalp compositions of the invention
`10 as a shampoo and rinsing the shampoo from the hair after
`shampooing.
`Therapeutic testing of individuals living in tropical eli(cid:173)
`mates has demonstrated that the detergent compositions of
`the invention, particularly in the form of shampoos, serve
`15 both to prevent the onset of minor scalp disorders in indi(cid:173)
`viduals previously free of disorder and to provide therapeu(cid:173)
`tic healing of such disorders in individuals presented with
`such disorders.
`
`1. Field of the Invention
`The invention relates to skin care compositions which
`exhibit a therapeutic effect in the treatment of skin disorders
`such as itching, irritation and skin dryness.
`2. Description of Related Art
`There are a number of shampoo products on the market
`today which are specifically formulated as anti-dandruff
`shampoos. These products generally contain one or a mix(cid:173)
`ture of surfactants, with the primary surfactant being an
`anionic surfactant such as an alkyl or aryl sulfate or sul(cid:173)
`fonate. One hypothesis is that dandruff problems are
`believed to be linked to the presence of a yeast-like fungus 20
`on the skin and an acceleration of the normal process of skin
`production. Conventional anti-dandruff shampoos generally
`contain effective amounts of an active agent which inhibits
`fungal growth and/or slows cell growth on the scalp.
`Examples of these agents include zinc pyrithione, selenium 25
`sulfide, salicylic acid, coal tar, sulfur, ketoconozole and
`climbazole. Examples of typical anti-dandruff shampoo for(cid:173)
`mulations are disclosed in U.S. Pat. Nos. 4,089,945; 4,329,
`334; 4,329,335; 4,329,336 and 4,835,148.
`However, experience has shown that excessive dandruff is
`largely a problem associated with cold, dry climates and it
`generally does not occur until after puberty. In more humid,
`tropical regions dandruff is a much less common disorder.
`However, inhabitants of these regions are generally more
`susceptible to mild forms of scalp dermatitis with such 35
`symptoms as excessive scalp itching, scalp irritation,
`inflammation, scalp dryness and scalp redness. These symp(cid:173)
`toms can also occur during the warm summer months in
`non-tropical regions. Although many of these symptoms
`ought to be relieved by the use of the anti-fungal agents 40
`present in some anti-dandruff shampoos, e.g., climbazole,
`zinc pyrithione or selenium sulfide, experience has demon(cid:173)
`strated that these symptoms are not relieved and, in fact, are
`even worsened by regular use of many commercial anti-
`dandruff hair shampoos.
`Accordingly it is a primary object of this invention to
`provide a mild, aqueous, skin care detergent composition,
`e.g., a scalp care shampoo or a shower cleansing
`composition, which exhibits a therapeutic effect on skin
`disorders, particularly, scalp disorders, particularly as
`encountered in warm weather and in tropical regions.
`
`DETAILED DESCRIPTION OF THE
`INVENTION
`
`Anionic surfactants normally present in mild detergent
`compositions, especially shampoo formulations are used not
`only for detersive or cleansing performance, but because
`they impart a high degree of foaming characteristics to the
`detergent composition or shampoo, which enhances con(cid:173)
`sumer appeal. However, the anionics are generally much
`more irritating to the skin than are the amphoteric or
`30 non-ionic surfactants. On the other hand, these latter sur(cid:173)
`factant types are considerably less foaming than the anionics
`and are thus less appealing when used as a major or sole
`surfactant component in a detergent composition or a sham(cid:173)
`poo.
`The present invention is grounded on the discovery that
`use of a specific combination of anionic and amphoteric
`surfactants provides a mild surfactant base for a therapeutic
`aqueous, body cleansing composition, particularly in the
`form of a shampoo, such that the surfactant system does not
`tend to counteract or negate the therapeutic benefits afforded
`by the therapeutic agents present in the body cleansing
`composition or shampoo.
`Suitable anionic surfactants which may be used include
`the water-soluble alkali metal or ammonium salts having
`alkyl radicals containing from about 8 to about 22 carbon
`atoms, the term alkyl being sued to include the alkyl portion
`of higher acyl radicals. Examples of suitable synthetic
`anionic surfactants are sodium or ammonium alkyl
`sulphates, especially those obtained by sulphating higher
`50 (C8-C18) alcohols produced, for example, from tallow or
`coconut oil; alkyl (C9-C20) benzene sulfonates, particularly
`sodium linear secondary alkyl (C10-C15) benzene sul(cid:173)
`fonates; alkyl glyceryl ether sulfates, especially those ethers
`of the higher alcohols derived from tallow or coconut oil and
`55 synthetic alcohols derived from petroleum; coconut oil fatty
`monoglyceride sulfates and sulfonates; salts of sulfuric acid
`esters of higher (C8-C18) fatty alcohol-alkylene oxide, par(cid:173)
`ticularly ethylene oxide reaction products; the reaction prod(cid:173)
`ucts of fatty acids such as coconut fatty acids esterified with
`60 isethionic acid and neutralized with sodium hydroxide;
`sodium and potassium salts of fatty acid amides of methyl
`taurine; alkane monosulfonates such as those derived from
`reacting alpha-olefins (C8-C20) with sodium bisulfite and
`those derived from reacting paraffins with S02 and Cl2 and
`65 then hydrolyzing with a base to produce a random sulfonate;
`and olefin sulfonates which term is used to describe the
`material made by reacting olefins, particularly C10-C20
`
`45
`
`SUMMARY OF THE INVENTION
`
`The present invention provides a mild aqueous, detergent
`composition, e.g., a shampoo composition, having a thera(cid:173)
`peutic effect on skin and scalp disorders comprising an
`aqueous dispersion of: (a) from about 5 to about 12% by
`weight of anionic surfactant; (b) amphoteric surfactant
`present in said composition at a level of at least about 0.75
`parts by weight per part by weight of said anionic surfactant;
`and (c) from about 0.10 to about 4% by weight of a
`therapeutic agent selected from the group consisting of
`1-imidazoly 1-1-( 4-chlorophenoxy)-3,3-dimethy lbutan-2-
`one, ( climbazole) acetylsalicylic acid, salicylic acid, 2,4,4,
`'-trichloro-2'-hydroxy diphenyl ether (triclosan); 1-acetyl-4-
`( 4-( (2-(2,4-dichlorophenyl)-2-(lH -imidazolyl-1-methyl)-1,
`
`2
`
`

`

`5,900,393
`
`15
`
`3
`alpha-olefins, with So3 and then neutralizing and hydrolyz(cid:173)
`ing the reaction product. The preferred anionic surfactants
`are sodium or ammonium (C10-C18) alkyl sulfates and
`(C10-C18) alkyl polyethoxy (1-11 Eo) sulfates and mixtures
`thereof having differing water solubilities.
`Particularly preferred anionic surfactant comprises a mix(cid:173)
`ture of a C10 to C18 alkyl sodium or ammonium sulfate or
`sulfonate or a C14-C18 alpha-olefin sodium or ammonium
`sulfonate (AOS) and a C8 to C12 alkyl polyethoxy (2-4 EO)
`sodium or ammonium sulfate. Mixtures containing a major 10
`amount of the alkyl sulfates, olefin sulfonates or alkyl
`alkoxy sulfates with aryl sulfonates such as sodium cumene
`sulfonate, sodium xylene sulfonate and sodium benzene
`sulfonate are also preferred.
`The amount of anionic surfactant present in the campo-
`sition will generally range from about 4 to 12% by weight
`(active ingredient), more preferably from about 6 to 10% by
`weight.
`The second essential component of the formulation is an
`amphoteric surfactant, present at a level of at least about
`0.75 parts by weight per 1 part by weight of the content of
`anionic surfactant present in the composition. The preferred
`level of amphoteric surfactant is in the range of from about
`0.75 to 1.25 parts by weight, more preferably from about 0.9
`to 1.1. parts by weight per 1 part by weight of anionic
`surfactant. It has been found that the presence of one or more
`amphoteric surfactants at these levels tends to cancel out the
`tendency of most anionic surfactants to cause irritation when
`contacted with the skin or scalp.
`Examples of amphoteric surfactants which may be used in 30
`the compositions of the invention include betaines and
`compounds which can be broadly described as derivatives of
`aliphatic secondary and tertiary amines in which the ali(cid:173)
`phatic radical can be straight chain or branched and wherein
`one of the aliphatic substituents contains from about 8 to 35
`about 18 carbon atoms and one contains an anionic water
`solubilizing group, e.g., carboxy, sulfonate, sulfate,
`phosphate, or phosphonate. Examples of compounds falling
`within
`this
`definition
`are
`sodium
`3-dodecylaminopropionate,
`sodium 40
`3-dodecylaminopropane sulfonate, N-alkyltaurines, such as
`prepared by reacting dodecylamine with sodium isethionate,
`N-higher alkyl aspartic acids and the products sold under the
`trade name "Miranol".
`Examples of betaines useful herein include the high alkyl 45
`betaines such as coco dimethyl carboxymethyl betaine,
`lauryl dimethyl carboxymethyl betaine, lauryl dimethyl
`alpha-carboxymethyl betaine, cetyl dimethyl carboxymethyl
`betaine, lauryl bis(2-hydroxypropyl) carboxymethyl
`betaine, oleyl dimethyl gamma-carboxypropyl betaine, lau- 50
`ryl bis-(2-hydroxypropyl) alpha-carboxymethyl betaine and
`the like.
`Other suitable sulfobetaines include 1-(lauryl,
`dimethylammonio) acetate-1-(myristyl dimethylammonio)
`propane-3-sulfonate and 1-(myristyl dimethylamino )-2- 55
`hydroxypropane-3-sulfonate.
`Particularly preferred betaines are those having the fol(cid:173)
`lowing general formula:
`
`wherein R1 is an alkyl group having from about 10 to 20 65
`carbon atoms, preferably 12 to 16 carbon atoms or the amino
`radical:
`
`20
`
`25
`
`4
`R---C-(O)-N(H)-(CH2)n-
`wherein R is an alkyl group having about 10 to 20 carbon
`atoms and n is the integer 1 to 4; R2 and R3 are each alkyl
`groups having 1 to 3 carbons and preferably 1 carbon; R4 is
`5 an alkylene or hydroxyalkylene group having from 1 to 4
`carbon atoms and, optionally, one hydroxyl group; and X is
`an anion selected from the group consisting of S03=and
`COO=. Typical alkyl-dimethyl betaines include decyl dim-
`ethyl betaine or 2-(N-decyl-N,N-dimethylammonio) acetate,
`coco dimethyl betaine or 2-(N-coco-N,N-dimethyl(cid:173)
`ammonio) acetate, myristyl dimethyl betaine, cetyl dimethyl
`betaine, stearyl dimethyl betaine, etc. Typical sulfobetaines
`or sultaines similarly include coco dimethyl sulfobetaine, or
`3-(N -coco-N,N -dimethyl ammonia) propane-1 sulfonate,
`myristyl dimethyl sulfobetaine, or 3-(N-coco-N,N-dimethyl
`ammonia) propane-1 sulfonate, myristyl dimethyl
`sulfobetaine, palmityl dimethyl sulfobetaine, lauryl dim(cid:173)
`ethyl sulfobetaine, etc. The amidobetaine and amidosulfo(cid:173)
`betaines similarly include cocoamidoethyl betaine,
`coco amidoeth y lsulfo betaine, cocoamidopropy 1 betaine,
`cocomidopropylsulfobetaine and like materials.
`Shampoo formulations containing a combination of
`anionic and amphoteric surfactants such as betaines present
`at a level of at least about 0.75 parts by weight betaine per
`part by weight of anionic surfactant are disclosed in copend(cid:173)
`ing U.S. patent application Ser. No. 08/155,251, the com-
`plete disclosure of which is incorporated herein by refer(cid:173)
`ence.
`The composition may also contain one or more non-ionic
`surfactants which assist in the formation of more stable
`aqueous compositions, which compositions may be in the
`form of solutions or dispersions, particularly suspensions or
`emulsions. The non-ionics, where used, are generally
`present as a surfactant minor, generally at levels below 10%
`by weight, more preferably below 5% by weight of the
`composition.
`Suitable nonionic surfactants include, in particular, the
`reaction products of compounds having a hydrophobic
`group and a reactive hydrogen atom, for example aliphatic
`alcohols, acids, amides and alkyl phenols with alkylene
`oxides, especially ethylene oxide, either alone or with pro-
`pylene oxide. Specific nonionic surfactant compounds are
`alkyl (C 6-C18) primary or secondary linear or branched
`alcohols condensed with ethylene oxide, and products made
`by condensation of ethylene oxide with the reaction products
`of propylene oxide and ethylenediamine. Other so-called
`nonionic surfactant compounds include long chain tertiary
`amine oxides, long-chain tertiary phosphine oxides, dialkyl
`sulfoxides, fatty (C8-C18) esters of glycerol. sorbitan and the
`like, alkyl polyglycosides, ethoxylated glycerol esters, ethy(cid:173)
`oxylated sorbitans and ethoxylated phosphate esters.
`A more detailed illustration of the various surfactants and
`classes of surfactants mentioned may be found in the text
`Surface Active Agents, Vol. II, by Schwartz, Perry and Berch
`(Interscience Publishers, 1958), in a series of annual publi(cid:173)
`cations entitled McCutcheon's Detergents and Emulsifiers,
`issued in 1969, or in Tenside-Taschenbuch, H. Stache, 2nd
`Ed. Carl Hanser Verlag, Munich and Vienaa, 1981.
`The therapeutic agent present in the composition is
`60 selected from the group consisting of climbazole, acetylsali(cid:173)
`cylic acid, salicylic acid, triclosan, ketoconazole, piroctone
`olamine, selenium sulfide, zinc pyrithione, coal tar, sulfur,
`ibuprofen and mixtures thereof, present at a level of from
`about 0.10 to about 4% by weight.
`The therapeutic agent preferably present in the composi(cid:173)
`tion of the invention is climbazole which is known chemi(cid:173)
`cally as 1-imidazolyl-1-( 4-chlorophenoxy)-3,3-
`
`3
`
`

`

`5,900,393
`
`5
`dimethylbutane-2-one or equivalent imidazolyl compounds.
`This agent may be prepared by reacting 1-bromo-1-(4-
`chlorophenoxy)-3-dimethylbutan-2-one with imidazole dis(cid:173)
`solved in acetonitrile as disclosed in U.S. Pat. Nos. 3,812,
`142 and 3,903,287. This imidazolyl ketone is a water
`insoluble crystalline powder having a melting point of
`94.5°-97.8° C., and may be obtained from the Bayer Com(cid:173)
`pany.
`Climbazole has proven a more effective therapeutic in
`compositions having a pH on the acid side, e.g. from about
`4.0 to about 6.9, more preferably from about 4.5 to 6.5.
`Adjustment of the pH of the shampoo formulation with a
`suitable acid, e.g. citric acid, may be necessary. Suitable acid
`buffers such as boric acid and phosphoric acid may also be
`used.
`A combination of climbazole with one or more keratolytic
`or anti-inflammatory agents such as acetylsalicylic acid
`(aspirin), salicylic acid, 2,4,4'-trichloro-2'-hydroxy diphenyl
`ether (triclosan); 2-( 4'-isobutylphenyl) propionic acid
`(ibuprofen); 1-acetyl-4-( 4-( (2-(2,4-dichlorophenyl)-2-(lH(cid:173)
`imidazolyl-1-methyl)-1,3-dioxolan-4-yl)methoxy)phenyl)(cid:173)
`piperazine (Ketoconazole ); 1-hydroxy-4-methyl-6-(2,4,4-
`trimethylpentyl)-2-pyridone monoethonolamine salt
`(piroctone olamine ); coal tar; selenium sulfide; sulfur or zinc
`pyrithione is also within the scope of the invention. Addition
`of one or more of these therapeutics serves the dual roles of
`pH adjustment (where the additive is acid) as described
`above, and as a co-therapeutic along with the climbazole.
`Use of the combination can also impart improved hair
`conditioning effects to the shampoo as will be hereinafter
`described. The climbazole is normally present in the sham(cid:173)
`poo at a level effective to provide therapeutic relief of the
`scalp disorders described herein. Preferred levels are in the
`range of about 0.1 to about 4% by weight, more preferably
`from about 0.25 to 2.5% by weight and most preferably from
`about 0.5 to 1.5% by weight. When used with a
`co-therapeutic, e.g. salicylic acid, the co-therapeutic may be
`present at a level of from about 0.1 to about 10% by weight,
`more preferably from about 0.25 to about 4% by weight and
`most preferably from about 0.25 to 2.5% by weight.
`The body cleansing composition of the present invention
`may also be formulated as a hair conditioning shampoo and
`therefore may contain one or more hair conditioning agents
`and suspending agents.
`Suitable hair conditioning agents include organosilicon
`compounds, e.g., non-volatile silicones and aminosilicones
`such as dimethicone. The conditioner may also comprise
`water insoluble polyethylenes; paraffins; petrolatums;
`microcrystalline waxes; C18-C36 mixed fatty acids and
`corresponding triglycerides; stearyl stearate and like known
`conditioners.
`Conditioners may also include various cationic quater(cid:173)
`nary ammonium salts or polymers. Preferred quaternary
`ammonium salts include materials such as tricetyl methyl
`ammonium chloride, dicetyl dimethyl ammonium chloride,
`distearyl dimethyl ammonium chloride, tristearyl methyl
`ammonium chloride and other quaternaries such as: guar
`hydroxypropyl trimethylammonium chloride (Cosmedia
`GUAR-C261, available from Hoechst Celanese Corp.);
`polyethylene glycol (PEG 15) coco-polyamine (Polyquat®
`H81, available from Henkel G.m.b.H.); quaternized
`hydroxyethyl cellulose, available from Amerchol as Poly(cid:173)
`mers JR and LR; polymers of dimethyldiallyl ammonium
`chloride or copolymers thereof with acrylamide, available as
`Merquats 100 and 550 (also known as polyquaternium 10
`and 7 respectively); vinyl imidazole vinyl pyrrolidone
`copolymers, available as Luviquats from BASF Corp.; poly-
`
`6
`vinyl pyrrxolidone-dimethylaminoethyl methacrylate
`copolymers, available as GAFQUATS from GAF Corp.; and
`like materials. The quaternary conditioners are normally
`present in the composition at levels of from about 0.2 to
`5 about 5% by weight.
`Hair conditioning shampoos also contain one or more
`suspending agents or lipids which assist in maintaining a
`stable dispersion of non-water soluble ingredients and also
`impart improved hair conditioning effects, generally present
`10 at a level of from about 1 to 15% by weight. Suitable of such
`agents include long chain acyl derivatives such as C16 to C50
`fatty acid esters of polyols such as glycerol, ethylene glycol
`or sorbitol. Preferred agents of this class include glycerol
`distearate and isosteareth (2 or 10), as well as long chain
`15 alkanolamides such as stearamide DEAdistearate. Suspend(cid:173)
`ing agents of this type are normally present in the compo(cid:173)
`sition at a level of from about 0.5 to about 5% by weight of
`the composition.
`Other useful suspension stabilizers are long chain primary
`20 alcohols or ethoxylated alcohols averaging about 26 to 40
`carbon atoms in the chain. These alcohols are mixed alco(cid:173)
`hols wherein at least about 80% of the chain lengths are of
`18-44 carbon atoms for alcohols averaging 30 carbon atoms
`and at least 80% of the chain lengths are 30-54 carbon atoms
`25 for alcohols averaging 40 carbon atoms. These materials are
`available from Petrolite Corporation under the trade name
`UNILIN™ alcohols. Preferred materials are Unilin™ 425
`alcohol (30 carbon chain average), Unilin™ 550 alcohol ( 40
`carbon chain average) and Unilin™ 350 (26 carbon chain
`30 average). A suitable derivative is Unithox™-550 which is an
`ethoxylated (13 EO) alcohol averaging 40 carbon atoms in
`the alkyl chain. These alcohols are normally present in the
`composition at levels of from about 1 to about 7% by weight.
`The shampoo composition also contains water, preferably
`35 deionized or irradiated water. The amount of water present
`in the composition as added water plus water present in the
`ingredients used in the formula will generally range from
`about 50 to about 85% by weight, more preferably from
`about 60 to about 80% by weight.
`In addition to the previously mentioned constituents of the
`liquid shampoo, normal and conventional adjuvants may be
`present, provided they do not adversely affect the properties
`of the shampoo. Thus, there may be used various coloring
`agents and perfumes, ultraviolet light absorbers such as the
`45 Uvinuls, which are products of GAF Corporation, preser(cid:173)
`vatives such as formaldehyde or hydrogen peroxide; pearl(cid:173)
`escing agents and opacifiers, solvents, such as ethanol,
`glycerin and glycols (ethylene glycol is useful as a clarifying
`agent, to prevent high and low temperature clouding of
`50 desirably clear shampoos); lubricants, such as mineral oil
`and higher fatty alcohols, e.g. cetyl alcohol, stearyl alcohol;
`sequestering agents such as EDTA tetrasodium salt, thick(cid:173)
`ening agents such as hydroxypropyl methyl cellulose
`(Methocel 34M) and salts such as sodium chloride, etc. The
`55 proportion of such adjuvant material, in total, will normally
`not exceed 5% of the shampoo.
`The shampoos are readily made by simple mixing meth(cid:173)
`ods from readily available components which, on storage, do
`not adversely affect the entire composition. However, it is
`60 preferred that the imidazolyl compound be first mixed with
`a nonionic component prior to the addition of the amphoteric
`and anionic surfactants. However, in the absence of a
`nonionic surfactant, the Climbazole can also be mixed with
`an aqueous solution of the amphoteric betaine prior to the
`65 addition of the anionic surfactant. Thus, the products are
`capable of being made in desired clear form or in opaque or
`opalescent form. The viscosities are adjustable by changing
`
`40
`
`4
`
`

`

`5,900,393
`
`7
`the total percentage of active ingredients and by modifying
`the percentages of thickening agent, sodium chloride and
`other adjuvants. The viscosity of the shampoo will normally
`be about that of glycerin at room temperature, e.g., about
`1,000 centipoises, but the viscosity may be in the broader 5
`ranges of 250-1500 centipoises. Its viscosity may approxi(cid:173)
`mate those of commercially acceptable shampoos now on
`the market. Instead of measuring viscosity directly, as by a
`Brookfield LVF viscometer, one may employ standard labo(cid:173)
`ratory flow tests, in which flow times through a restriction or 10
`tube length under a reproducible head are measured in
`seconds, utilizing a Raymond tube. Viscosities may prefer(cid:173)
`ably range from 10-135 seconds and up to 300 or 400
`seconds. The shampoo itself remains stable on storage for
`lengthy periods of time, without color changes or settling out 15
`of any insoluble materials.
`The following examples are illustrative of the invention.
`
`8
`
`Ammonium lauryl sulfate
`Cocamide DEA *
`Sodium cumene sulfonate
`Na laureth -13 carboxylate
`
`19 wt.%
`4.5 wt.%
`1.4 wt.%
`2.5 wt.%
`
`*CTFA adopted name for Coconut Diethanolamide
`
`Each of the four panels were shampooed with the control
`product every other day for two weeks for a total of seven
`washes. The shampoo procedure involved the application of
`10 grams of the control directly to the wet scalp followed by
`a one minute massage into the scalp. The hair is then washed
`and rinsed free of lather and dried.
`Scalp evaluations were made by the subjects themselves
`and a dermatologist after 6, 10 and 14 days to determine the
`degree of scalp discomfort occasioned by shampooing using
`the control. Ratings of itching, irritation (redness of skin),
`dryness and flaking were made on a scale of 1 to 10, with 1
`representing no problem and 10 representing maximum
`20 problem.
`The average score for each of the four groups at the end
`of the control washing for each of the four scalp discomfort
`factors was plotted as a base line value.
`The four control groups were then subjected to seven
`25 additional shampooings using the protocol described above
`over the next two weeks using the following shampoos:
`Group A-Formula A
`Group B-Formula B.
`Group C-Commercial HEAD AND SHOULDERS™
`product obtained in Mexico (H&S)*
`* Major surfactant is anionic.
`Group D-Commercial PANTENE™ Scalp Care/Anti
`Dandruff product obtained in the Philippines.*
`* Major surfactant is anionic.
`Scalp evaluations for each group were made after the 3rd,
`5th and 7th washes, rated on a 1-10 scale as described above
`and plotted as a fitted regression line for each group vs. the
`baseline values obtained after the control washings.
`Scalp changes are shown in Table 1. The more negative
`40 the change, the better the improvement of the scalp condi(cid:173)
`tion.
`
`30
`
`35
`
`EXAMPLE 1
`
`A shampoo composition was prepared by the general
`mixing procedure described above. The formulation of this
`shampoo is as follows in weight %:
`
`COMPONENT
`
`ACTIVES
`
`AS IS
`
`%
`
`Cocoamido Propyl Betaine No. 3
`Deionized water (irradiated)
`Sodium Deceth Sulfate (3 Eo)
`Ammonium Laury! Sulfate
`Sodium Cumene Sulfonate
`c30-C40 Fatty Alcohol (UNILIN TM)
`Dimethyl Polysiloxane
`Dis teary! Methyl Ammonium Chloride
`Preservative
`Isosteareth (2 Eo)
`Perfume
`Hydroxy Ethyl Cellulose
`Climbazole
`Polyquaternium 10
`Sodium Phosphate (Di Basic)
`EDTA
`Colorant
`
`30.0
`25.0
`15.0
`12.0
`5.0
`4.0
`3.5
`1.0
`1.0
`0.8
`0.75
`0.6
`0.5
`0.35
`0.2
`0.1
`0.013
`
`9.0
`
`4.5
`3.0
`2.3
`4.0
`3.5
`1.0
`1.0
`0.8
`0.75
`0.6
`0.5
`0.35
`0.2
`0.06
`0.013
`
`This shampoo was designated as Formula A.
`
`TABLE 1
`
`EXAMPLE 2
`
`45 SHAMPOO
`
`ITCH-
`ING
`
`IRRI-
`TAT! ON
`
`DRY-
`NESS
`
`CONCLU-
`FLAKING SION
`
`A second shampoo was prepared having the formula of
`Example 1 except that the amount of climbazole was raised
`to 1.5% by weight and 1.5% by weight less water was added
`to the formulation. This formulation was designated as
`Formula B.
`The effectiveness of the shampoo formulations of the
`present invention for healing and preventing scalp disorders
`was evaluated using the following protocol. Ninety residents
`of the Dominican Republic who were free of scalp disease 55
`(as determined by a dermatologist), but who regularly com(cid:173)
`plained of scalp irritation and itching occasioned by sham(cid:173)
`poo usage were selected by questionnaire. The group was
`arbitrarily divided into six groups of 15 each.
`Four groups were used to evaluate the effectiveness of 60
`Formulas A and B above in reducing scalp discomfort
`(itchiness) for those complaining of discomfort after sham(cid:173)
`pooing with a control formulation containing a high content
`of anionic surfactant. The control formulation used was a
`formulation containing no therapeutic agent and a surfactant
`mixture high in anionic content. The surfactant combination
`(actives) in the control were:
`
`PANTENE
`
`-0.28
`
`-0.35
`
`-0.28
`
`H&S
`
`0.18
`
`-0.28
`
`1.05
`
`50 Form B
`
`-2.10
`
`-0.15
`
`-3.93
`
`FormA
`
`-1.25
`
`-1.00
`
`-1.00
`
`-1.75 marginally
`effective
`-2.05 marginally
`effective
`-5.30 most
`effective
`effective
`
`-3.72
`
`These results show that the products of the present invention
`are considerably more effective than leading commercial
`anti-dandruff shampoos (which contain anionic surfactant as
`the major surfactant component) in reducing or substantially
`eliminating scalp disorder factors occasioned by the use of
`an irritating, high anionic content shampoo.
`The remaining two groups of 15 panelists each (GroupE
`and F) were subjected to a different protocol. In this
`protocol, there were no control washings, but instead the
`hair of each panelist was washed every other day by the
`washing procedure described above (for a total of 14
`65 washings) with HEAD AND SHOULDERS™ (Group E)
`and with Formula B (Group F). The objective of this
`protocol was to determine the effectiveness of each product
`
`5
`
`

`

`5,900,393
`
`9
`to prevent the onset of scalp disorders. As above, a baseline
`evaluation of scalp disorder for each panelist prior to the 14
`washings was established by dermatological observation
`and panelist input.
`Changes in scalp characteristics after 14 washes rated on
`a 1-10 scale were plotted as above. Results are shown in
`
`5
`
`TABLE 2
`
`SHAMPOO
`
`ITCH-
`ING
`
`IRRI-
`TAT! ON
`
`CONCLU-
`DRY-
`NESS FLAKING SION
`
`HandS
`
`-2.42
`
`-0.07
`
`0.08
`
`Form B
`
`-2.69
`
`-1.49
`
`-4.93
`
`-2.98 marginally
`effective
`effective
`
`-4.84
`
`10
`
`10
`R2
`
`R1-N-R4-X
`
`R3
`
`wherein R1 is an alkyl group having from about 10 to 20
`carbon atoms or the amino radical:
`
`R---C-(O)-N(H)-(CH2)n-
`
`The results show that the product of the invention is con(cid:173)
`siderably more effective in preventing the onset of scalp
`disorder problems than a leading commercial brand. Again,
`it is believed that the major factor contributing to this
`efficacy is the mild surfactant system present in the formu(cid:173)
`lations of this invention.
`An additional feature of the invention is based on the
`discovery that mild conditioning shampoos of the invention 25
`which contain an alkyl, alkaryl or alpha olefin sulfonate as
`the main anionic surfactant and a combination of climbazole
`and salicylic acid or acetylsalicylic acid also provide
`improved conditioning effects in an acid shampoo (pH
`4.0-5.0). Two shampoo formulations containing the follow(cid:173)
`ing surfactant and therapeutic ingredient compositions were
`prepared:
`
`Example 3
`
`Example 4
`
`Climbazole
`Salicylic Acid
`Sodium AOS (40%)
`Na Cumene Sulfonate ( 43.3%)
`Cocoamidopropyl Betaine (30%)
`
`1.5
`2.0
`22.5
`7.0
`30.0
`
`22.5
`7.0
`30.0
`
`35
`
`40
`
`The remainder of each formulation was iden