O
`Unlted States Patent
`
`1191
`
`[11] Patent Number:
`
`4,470,982
`
`
`Winkler
`[45] Date of Patent:
`Sep. 11, 1984
`
`[54] SHAMPOO COMPOSITIONS
`,
`_
`_
`_
`_
`.
`Inventor: William Mkaler, Cmcmnatl,
`. 0th
`
`{75]
`
`.
`.
`[73] Ass‘gnee'
`
`T1.” mm." 8‘93“” “”3“”
`Cmcmnath Oh‘O
`.
`[21] Appl. No.. 367,204
`[22] Filed:
`Apr- 12, 1932
`
`Related U.S. Application Data
`.
`
`.
`
`[631
`
`[51]
`
`119,283, Feb. 7, 1980, abandoned.
`Int. Cl.3 ................... A61K 31/555; A61K 33/04;
`A61K 31/615; A61K 31/61
`[52] US. Cl. .................................... 424/245; 424/ 164;
`424 233; 424 234; 424 263
`[58] Field of Search
`/
`'
`./'
`4241245
`.......................................
`[56]
`References Cited
`
`U.S. PATENT DOCUMENTS
`_
`260/294.8
`2,786,847
`3/1957 Cislak ............
`
`
`260/270
` .
`2,809,971 10/1957 ‘ Bernstein at al.
`
`3,476,489 11/1969 Mees ct al.
`424/164
`1/1970 Parran .............. 252/106
`3,489,686
`
`3,583,999
`6/1971 Damico
`260/294.8 G
`6/1971 Damico ............................... 260/290
`3,590,035
`
`3,773,770 11/1973 Damico ........................... 260/290R
`
`1/1974 Grand .............
`3,785,985
`252/106
`
`3,917,81711/1975 Vanlerberghe.
`...... 424/70
`
`7/1977 Gerstein ............... 252/106
`4,033,895
`
`4,041,033
`8/1977 Douglass ........
`260/250A
`5/1978 Brinkman et a1.
`..... 252/164
`4,089,945
`
`4,161,526
`7/1979 Gorman ......
`. 424/245
`
`4,323,683 4/1982 Bolich et a1. ............................ 546/6
`
`FOREIGN PATENT DOCUMENTS
`2060810
`5/1977 Japan.
`1051268 12/1966 United Kingdom .
`1280671
`7/1972 United Kingdom.
`
`1390078 “1975 UN“ ngd"’“'
`OTHER PUBLICATIONS
`Inorganic Chemistry 16, 1834, (1977), Suave® An-
`tidandruff Shampoo,
`,
`_
`.
`'
`Primary Exammer—Fredenck E. Waddell
`Attorney, Agent, or Firm_Richard c. Witte; John V.
`Gorman; Douglas C. Mohl
`ABSTRACT
`
`[57]
`
`Antidandruff, lotion shampoo compositions which con-
`tain critical amounts of an anionic surfactant, a suspend-
`ing agent and an alkanol amide.
`
`8 Claims, No Drawings
`
`
`
` —% T 1054
` UN T. diniR 41X -1
`
`
`
`
`
`
`
`
` 4 I
`
`
`
`
`T.d'.V4'.R VS. PKOCTOK & GAD/HT.
`
`II'?R20l3-OO509
`
`
`
`UN
`
`000001
`
`000001
`
`UNILEVER EXHIBIT 1054
`UNILEVER VS. PROCTOR & GAMBLE
`IPR2013-00509
`
`

`

`1
`
`SHAMPOO COMPOSITIONS
`
`CROSS-REFERENCE TO RELATED
`APPLICATION
`
`4,470,982
`
`2
`tain several optional components. Each of the compo-
`nents is discussed in detail below.
`
`Anionic Surfactant
`
`This is aéontinuation of application Ser. No. 219,281,
`filed Dec. 22, 1980 now abandoned, which is a continua-
`tion-in-part application of application Ser. No. 119,283,
`filed Feb. 7, 1980, now abandoned.
`
`TECHNICAL FIELD
`
`The present invention is related to antidandruff lotion
`shampoo compositions which possess good lotion vis-
`cosity while also being quite stable with respect to sepa-
`ration.
`
`Lotion compositions, particularly those containing
`particulate materials,
`traditionally suffer from liquid
`separating. If an attempt is made to avoid such separa-
`tion the compositions become too viscous for satisfac-
`tory pouring. A totally acceptable product requires that
`both stability and viscosity be optimized.
`BACKGROUND ART
`
`The separate use of the components of the present
`invention in shampoos is known'in the shampoo art.
`US. Pat. No. 3,917,817, Nov. 5, 1975 to Vanler-
`berghe et a1 discloses a shampoo composition contain-
`ing a piperazine based cationic polymer, 10% sodium
`alkyl sulfate, 4% lauryl monoethanolamide and 3%
`glycol distearate. US. Pat. No. 4,013,787, Mar. 22, 1977
`to Vanlerberghe et a1 discloses a similar composition.
`Japanese Application, with Open for Public Inspection
`No. 60810, May 19, 1977 (Lion Fat & Oil), discloses
`shampoos containing 5% to 50% of an anionic surfac-
`tant, 1% to 10% of a fatty acid diethanol amide, 0.1% to
`10% of an insoluble fine powder, and 1% to 10% of an
`ethyleneglycol ester.
`While these references disclose compositions which
`contain components of the type present in the composi-
`tions of the present invention, they do not suggest com-
`bining the components in the amounts found critical by
`the present inventor.
`It is an object of the present invention, therefore, to
`provide shampoos containing certain critical levels of
`surfactant, amide and a suspending agent as well as
`containing a particulate antidandruff agent.
`It is a further object of the present invention to pro-
`vide shampoos which have optimal viscosity and liquid
`separation.
`These and other objectives will become readily ap-
`parent from the detailed description which follows.
`DISCLOSURE OF THE INVENTION
`
`The present invention relates to antidandruff sham-
`poo compositions comprising from about 11% to about
`20% of an anionic surfactant, from about 4% to about
`6% of a suspending agent, from about 2% to about 4%
`of an alkanol amide, a particulate antidandruff agent and
`water. The compositions exhibit very little liquid sepa-
`ration and preferably have a viscosity at 25° C. of from
`about 2500 cps to about 6000 cps.
`DETAILED DESCRIPTION OF THE
`INVENTION
`
`The compositions of the present invention comprise
`certain essential components and may additionally con-
`
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`
`The surfactant in the shampoos of this invention is
`anionic and is present at a level of from about 11% to
`about 20%, preferably about 14% to about 18%. Specif-
`ically, the surfactant is an alkyl sulfate, an ethoxylated
`alkyl sulfate or mixtures thereof. The alkyl sulfates
`found useful are the sodium, ammonium and triethanol-
`amine alkyl sulfates having from about 8 to about 22
`carbon atoms in the alkyl chain. Preferred are those
`sulfates obtained by sulfating the higher alcohols, those
`having from about 8 to about 18 carbon atoms.
`The ethoxylated alkyl sulfates have alkyl chains of
`the type used with the alkyl sulfates but have from
`about 1 to 6, preferably 3, ethoxy groups per molecule.
`The most preferred surfactant is sodium alkyl sulfate.
`With this surfactant, as well as others, the viscosity may
`be controlled in the desired range by the total amount of
`buffering agent which may be present.
`
`Suspending Agent
`
`The suspending agent useful in the present composi—
`tions can be any of several materials. Included are ethyl-
`ene glycol esters of fatty acids having from about 16 to
`about 22 carbon atoms. Preferred are the ethylene gly-
`col stearates, both mono and distearate. Other suspend-
`ing agents found useful are alkanol amides of fatty acids,
`having from about 16 to about 22 carbon atoms, prefera-
`bly about 16 to 18 carbon atoms. Preferred alkanol
`amides are stearic monoethanolamide, stearic diethanol-
`amide,
`stearic monoisopropanolamide
`and stearic
`monoethanolamide stearate.
`
`Still other suitable suspending agents are alkyl (C16-
`22) dimethyl amine oxides such as stearyl dimethyl
`amine oxide. Mixtures of these materials are also accept-
`able.
`
`The suspending agent is present at a level of from
`about 4% to about 6%. The suspending agent serves to
`assist in suspending the antidandruff active and may
`give pearlescence to the product.
`Amide
`
`The amide used in the present compositions can be
`any of the alkanolamides of fatty acids known for use in
`shampoos. These are generally mono- and diethanola-
`mides of fatty acids having from about 8 to about 14
`carbon atoms. Preferred are coconut monoethanolam-
`ide, lauric diethanolamide and mixtures thereof.
`The amide is present at a level of from about 2% to
`about 4%.
`
`Antidandruff Agent
`
`Another essential element of the present composi-
`tions is a particulate antidandruff agent.
`Included
`among such agents are sulfur, selenium sulfide, salicylic
`acid, zinc pyridinethione, other l-hydroxy pyridones,
`such as those disclosed in US. Pat. No. 4,185,106, Jan.
`22, 1980 to Dittmar et al, incorporated herein by refer—
`ence and azole antimycotics disclosed in British Pat.
`No. 1,502,144, Feb. 22, 1978, incorporated herein by
`reference, among many others. The antidandruff agent
`is present at a level of from about 0.2% to about 4%.
`Zinc pyridinethione is the preferred agent, particu-
`larly where its salt crystals are predominantly flat plate-
`lets which have a mean sphericity less than about 0.65,
`preferably between about 0.20 and about 0.65, and a
`
`000002
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`000002
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`

`

`4,470,982
`
`3
`median particle diameter of at least about 211., expressed
`as the diameter of a sphere of equivalent volume. It is
`preferred that
`the median particle diameter not be
`greater than about 15p, expressed on the same basis.
`The diameter of a sphere of equivalent volume, dv, for
`a particle can be determined by a variety of sedimenta~
`tion techniques which are based onvStokes’ Law for the
`settling velocity ofa particle in a fluid. Such techniques
`are described in Stockham, J. D. and Fochtman, E. G.,
`Particle Size Analysis, Ann Arbor Science, 1978, incor-
`porated herein by reference.
`The sphericity of a particle is also described by
`Stockham and Fochtman at page 113 as
`
`4
`The following examples further describe and demon-
`strate embodiments within the scope of the present
`invention. The exammples are given solely for the pur-
`pose of illustration and are not to be construed as limita-
`tions of the present invention as many variations thereof
`are possible without departing from its spirit and scope.
`Unless otherwise indicated, all percentages herein are
`by weight.
`
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`EXAMPLE I
`
`invention
`A shampoo composition of the present
`having the following composition was prepared.
`
` Component Level
`
`Ammonium Alky] Sulfate
`55.25%
`(27% Aqueous Solution)
`0.24
`Citric Acid
`0.55
`Sodium Citrate
`3.00
`Coconut Monoethanolamide
`5.00
`Ethylene Glycol Distearate
`2.00
`Zinc Pyridinethione
`0.20
`Methyl Paraben
`0.10
`Propyl Paraben
`0.20
`Color Solution
`0.50
`Perfume
`
`Water q.s. 100.00%
`
`d,
`i=0?)
`
`2
`
`where dv is the diameter of a sphere of equivalent vol-
`ume, supra, and d; is the diameter ofa sphere of equiva-
`lent area. A technique for determining d: is the BET
`technique described by Stockham and Fochtman at
`page 122.
`Since the sphericity of interest herein is the mean
`sphericity, the mean diameters are employed.
`Water
`
`The compositions of the present invention are lotions
`with water being the major carrier. The amount of 30
`water present is generally from about 35% to about
`90%, preferably from about 60% to about 80%.
`
`Optional Components
`
`The shampoos herein can contain a variety of nones-
`sential optional ingredients suitable for rendering such
`compositions more stable and desirable. Such conven—
`tional optional
`ingredients are well known to those
`skilled in the art, e.g., preservatives such as benzyl alco-
`hol, methyl paraben, propyl paraben and imidazolidinyl
`urea; pH adjusting agents such as citric acid, sodium
`citrate, succinic acid, phosphoric acid, sodium hydrox-
`ide, sodium carbonate, etc.; and, sequestering agents
`such as disodium ethylenediamine tetraacetate.
`Minor ingredients such as perfumes, dyes and color-
`ing agents can also be added to the instant compositions
`to improve their consumer acceptability. If present,
`such agents generally comprise from about 0.1% to
`2.0% by weight of the composition.
`The shampoos of the present invention are preferably
`substantially free of suspending agents such as magnesi-
`um/aluminum silicate (present at less than about 0.1%)
`and inorganic salts such as alkali metal chlorides and
`ammonium chloride (present at less than about 0.70%).
`Additionally while the pH may be in the range of from
`about 3 to about 9, the preferred pH is from about 4 to
`about 6, particularly when ammonium alkyl sulfate is
`the surfactant. The proper pH is obtained through'the
`use of an appropriate buffer such as sodium citrate/ci-
`tric acid.
`
`Method of Manufacture
`
`The shampoos of the present invention may be made
`using mixing techniques well known in the art.
`
`Industrial Applicability
`
`The shampoos of the present invention are used in a
`conventional manner.
`'
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`The composition had a viscosity of about 4000 cps
`and experienced very little separation after 2 weeks at
`120° F.
`
`EXAMPLE II
`
`The following shampoo composition was prepared.
`
` Component Level
`
`Ammonium Alkyl Sulfate
`55.25%
`(27% Aqueous Solution)
`3.0
`Coconut Monoethanolamide
`5.0
`Ethylene Glycol Distearate
`2.0
`Zinc Pyridinethione
`1.0
`Ammonium Chloride
`0.24
`Citric Acid
`. 0.55
`Sodium Citrate
`0.20
`Methyl Paraben
`0.10
`Propyl Paraben
`0.15
`Color
`0.50
`Perfume
`9.5.
`Water
`100.00
`
`This formulation, which contains a level of ammo-
`nium chloride outside the scope of the present inven-
`tion, separated unacceptably after 1 week at 100° F.
`EXAMPLE III
`
`The following composition was prepared.
`
` Component Level
`
`Ammonium Alkyl Sulfate
`55.25%
`(27% Aqueous Solution)
`2.00
`Zinc Pyridinethione
`4.64
`Coconut Monoethanolamide
`2.35
`Ethylene Glycol Distearate
`0.20
`Citric Acid
`0.20
`Methyl Paraben
`0.10
`Propyl Paraben
`0.35
`Color Solution
`0.50
`Perfume
`
`Water q.s. 100.00%
`
`‘
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`000003
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`000003
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`

`5
`This composition, outside the scope of the present
`invention, had an acceptable viscosity of 5,520 cps but
`showed unacceptable liquid separation at 100° F. after 1
`month.
`What is claimed is:
`
`4,470,982
`
`6
`sisting of ammonium alkyl sulfate, sodium alkyl sulfate,
`sodium ethoxy(3)alkyl sulfate,
`triethanolamine alkyl
`sulfate and mixtures thereof.
`3. A shampoo composition according to claim 2
`wherein the suspending agent is selected from the group
`consisting of ethylene glycol monostearate, ethylene
`glycol distearate and mixtures thereof.
`4. A shampoo composition according to claim 3
`wherein the alkanolamide of a fatty acid having from
`about 8 to about 14 carbon atoms is selected from the
`group consisting of coconut monoethanolamide, lauric
`diethanolamide and mixtures thereof.
`5. A shampoo composition according to claim 4
`wherein the surfactant is sodium alkyl sulfate wherein
`the alkyl group contains from about 8 to about 18 car-
`bon atoms and wherein the pH of said composition is
`from about 4 to about 6.
`
`6. A shampoo composition according to claim 5
`wherein the alkanolamide is coconut monoethanolam—
`ide.
`'
`
`7. A shampoo composition according to claim 6
`wherein the suspending agent is ethylene glycol distea-
`rate;
`8. A shampoo composition according to claim 7
`wherein the antidandruff agent is zinc pyridinethione,
`III
`II!
`*
`*
`*
`
`10
`
`1. A lotion shampoo composition comprising:
`(A) from about 11% to about 20% of a surfactant
`selected from the group consisting of alkyl sulfates,
`ethoxylated alkyl sulfates and mixtures thereof;
`'
`(B) from about 4% to about 6% of a suspending agent
`selected from the group consisting of ethylene
`glycol esters of fatty acids having from about 16 to
`about 22 carbon atoms, alkanol amides of fatty
`acids having from about 16 to about 22 carbon
`atoms, alkyl
`(Cm—22) dimethyl amine oxides and 15
`mixtures thereof;
`(C) from about 2% to about 4% of an alkanolamide of
`a fatty acid having from about 8 to about 14 carbon
`atoms;
`(D) from about 0.2% to about 4% of a particulate
`antidandruff agent; and
`(E) from about 35% to about 90% water,
`wherein said composition is substantially free of alkali
`metal chlorides and ammonium chloride.
`2. A shampoo composition according to claim 1
`wherein the surfactant is selected from the group con-
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