United States Patent (19)
`Esnau
`
`63
`
`(54) ANTIPERSPIRANT STICK
`75) Inventor: Walter Hugh Elsnau, Cincinnati,
`Ohio
`(73) Assignee:
`The Procter & Gamble Company,
`Cincinnati, Ohio
`(21) Appl. No.: 632,128
`(22
`Filed:
`Nov. 14, 1975
`Related U.S. Application Data
`Continuation of Ser. No. 373,820, June 26, 1973,
`abandoned.
`51) Int. Cl’................................................ A61K 7/34
`52 U.S. C. ............................... 424/66; 424/DIG. 5;
`424/68
`58) Field of Search ...................... 424/66, DIG. 5, 68
`(56)
`References Cited
`U.S. PATENT DOCUMENTS
`1,984,669 12/1934 Taub ...................................... 424/65
`2,087,161
`7/1937 Moore.....
`... 424/68 X
`2,566,722 9/1951
`Friedberg ...
`... 424/DIG. 5
`2,865,859 12/1958 Lubowe ......
`... 424/66 X
`2,889,253
`6/1959 Berger et al............
`. 424/170X
`2,890,152
`6/1959 Babcock, Jr. et al. ............ 424/68 X
`2,893,918
`7/1959 Abramson ..................... 424/OIG, 5
`3,098,795
`7/1964 Kreps............................. 424/OG. S
`
`(11)
`45)
`
`4,049,792
`Sept. 20, 1977
`
`
`
`3,194,736
`3,255,082
`3,259,545
`3,325,367
`
`7/1965 Braun et al. ................... 424/DIG. 5
`7/1966 Barton ........................... 424/DIG. 5
`7/1966. Teller ..................................... 424/66
`6/1967 Wiechowski .......................... 424/66
`OTHER PUBLICATIONS
`American Perfumer & Cosmetics, 1963, vol. 78 p. 50.
`Drug & Cosmetic Industry, Nov. 1968, p. 80
`Drug & Cosmetic Industry, Nov. 1950, vol. 67, No. 5 p.
`687.
`Household & Personal Products Formulary, Sept. 1972.
`Primary Examiner-Dale R. Ore
`Attorney, Agent, or Firm-Ronald L. Hofer; George W.
`Allen; Douglas C. Mohl
`57
`ABSTRACT
`A very effective antiperspirant composition in the form
`of a stick comprising from abouyt 1% to about 20% of
`a water-insoluble wax, from about 20% to about 50% of
`an essentially water-insoluble, but water-dispersible,
`liquid emollient, and from about 30% to about 60% of
`an activealuminum or zirconium astringent antiperspi
`rant salt in the form of finely divided particles, said
`composition being essentially water-insoluble with the
`exception of the active particles.
`
`7 Claims, No Drawings
`
`Petitioner Dr. Squatch
` Ex. 1041
`
`

`

`1.
`
`5
`
`O
`
`35
`
`ANTPERSPIRANT STICK
`CROSS REFERENCE TO RELATED
`APPLICATION
`This application is a continuation of the copending
`application of Walter Hugh Elsnau having Ser. No.
`373,820, filed June 26, 1973, now abandoned.
`BACKGROUND OF THE INVENTION
`1. Field of the Invention
`This invention relates to antiperspirant compositions
`in the form of a stick.
`2. Prior Art
`The use of stick antiperspirant compositions is well
`15
`known. However, most of the stick antiperspirant com
`positions known heretofore have included a relatively
`insoluble soap, see for example, Taub; U.S. Pat. No.
`1984,669; issued Dec. 18, 1934 and more typically, a
`soap gel, see for example, Teller; U.S. Pat. No.
`20
`2,732,327; issued Jan. 24, 1956. Almost all of the prior
`art stick antiperspirant compositions contain either
`water or large amounts of water-soluble materials. For
`example, Moore; U.S. Pat. No. 2,087,162; issued July 13,
`1937 discloses a composition containing large amounts
`25
`of isopropyl alcohol. Most prior art antiperspirant stick
`compositions also fail to have sufficient active present,
`for example, the formulas shown in the Formulary sec
`tion of Household and Personal Products Industry, Sep
`tember 1972.
`Similar compositions which do not contain water-sol
`uble compounds in large amounts have been disclosed,
`but these have not been antiperspirant compositions.
`See, e.g., Mohrlok; U.S. Pat. No. 3,641,239; issued Feb.
`8, 1972, which relates to a lipstick, rouge, mascara or
`styptic crayon containing a silicone wax.
`The stick antiperspirant prior art compositions, al
`though effective, do not suggest the compositions of
`this invention which are surprisingly more effective
`than the compositions of the prior art. Further, the
`40
`compositions of the present invention are more cosmeti
`cally appealing than prior art compositions. Even fur
`ther, the efficacy of compositions of the present inven
`tion is longer-lasting than that of prior art compositions.
`Still further, the stick antiperspirant compositions of the
`45
`present invention are stable, offer safety advantages
`over aerosol antiperspirant products, are substantially
`non-irritating to the skin, and do not require a compli
`cated package for dispensing and preventing "dry-out',
`giving the present compositions advantages over other
`antiperspirant compositions.
`Unless indicated otherwise, all percentages hereinaf
`ter are percentages by weight.
`SUMMARY OF THE INVENTION
`This invention relates to a very effective antiperspi
`rant stick composition comprising from about 1% to
`about 20% of a water-insoluble wax having a melting
`point of from about 150 F. to about 215 F.; from about
`20% to about 50% of an essentially water-insoluble, but
`60
`water-dispersible, liquid emollient; and from about 30%
`to about 60% of a relatively water-soluble aluminum or
`Zirconium astringent antiperspirant salt in finely divided
`particulate form dispersed in said composition. The ,
`composition may optionally contain from 0% to about
`65
`25% of a relatively water-insoluble waxy material hav
`ing a melting point of from about 100 F. to about 150
`F., such as a fatty acid or a fatty alcohol and from 0%
`
`4,049,792
`2
`to about 10% of a water-insoluble, inert filler material in
`the form of finely divided particles dispersed in said
`composition.
`DESCRIPTION OF THE INVENTION
`Applicant has surprisingly discovered a very effec
`tive, non-irritating, cosmetically attractive antiperspi
`rant composition in the form of a stick comprising a
`wax, a liquid emollient, and an astringent aluminum or
`zirconium salt, Optionally, the present compositions
`may contain a waxy material having a melting point of
`from about 100 F. to about 150 F. and/or an inert filler
`material. These ingredients are more specifically de
`scribed below.
`While applicant does not wish to be bound by any
`theory, it is believed that the structure of a composition
`of the present invention is highly important in determin
`ing both the cosmetic attractiveness and antiperspirant
`efficacy of the stick antiperspirant. A stick antiperspi
`rant composition of the present invention is essentially
`anhydrous, containing no volatile ingredients. Thus, a
`composition of the present invention does not impart a
`wet impression to the user. Further, the antiperspirant
`active ingredient is dispersed throughout the product at
`a highly effective concentration. When the composition
`is applied to the skin, the other required ingredients of
`the composition hold the active to the skin. It has been
`surprisingly discovered that the level of antiperspirant
`active in the composition is critical to improved effi
`cacy as an antiperspirant. It was surprisingly discovered
`that merely adding more of a composition containing a
`lower concentration of antiperspirant active does not
`give equivalent performance to a composition of the
`present invention which employs the active at a higher
`concentration.
`It is further believed that the present compositions
`comprising essentially water-insoluble materials and a
`water-soluble aluminum or zirconium salt form an insol
`uble film on the skin while holding a soluble active
`ingredient against the skin to help prevent perspiration
`resulting in an antiperspirant product which resists
`washing away by sweat but is easily washed away by a
`soap solution. Thus, the present compositions are effec
`tive for long periods of time.
`The Water-Insoluble Wax
`A high melting point water-insoluble wax provides
`the basic structure of the composition. Suitable waxes
`are water-insoluble waxes having a melting point of
`from about 150 F. to about 215 F. and are hereinafter
`referred to as high melting point waxes. Examples of
`suitable waxes are beeswax, spermaceti, carnauba, bay
`berry, candelilla, montan, ozokerite, ceresin, paraffin,
`synthetic waxes such as Fisher-Tropsh waxes, and mi
`crocrystalline wax. Preferred waxes are ceresin, ozoke
`rite, white beeswax and synthetic waxes. It is speculated
`that the high melting point wax provides a structure
`which can be sheared when applied to the skin, thereby
`exposing the active particles described hereinafter to
`the skin. The present compositions may contain from
`about 1% to about 20% of this wax. The preferred
`amount of high melting point wax is from about 5% to
`about 15%, most preferably from about 6% to about
`10%. Higher levels of wax lead to lower wear rates, and
`lower levels of wax tend to give higher wear rates and
`a softer, less desirable structure which feels sticky to the
`user and does not provide adequate shearing action in
`S.
`
`50
`
`55
`
`

`

`5
`
`15
`
`The Liquid Emollient
`The liquid emollient is an essential ingredient in the
`preparation of the antiperspirant stick of this invention.
`Such emollients are in liquid form at room temperature
`(about 72 F). It has been discovered that water-soluble
`emollients are not desirable components of a stick anti
`perspirant composition. However, the liquid emollients
`of this invention are water-dispersible in the presence of
`a surfactant, e.g., soap, which is desirable in that it per
`10
`mits the removal of the antiperspirant composition by
`taking a shower or a bath. Any liquid, non-toxic, non
`irritating organic material having a solubility in water
`of from about 0.0005% to about 1.0% at 72 F. can be
`used. Preferred emollients include fatty acid and fatty
`alcohol esters, e.g., isopropyl myristate, isopropyl pal
`mitate, cetyl acetate, cetyl propionate, etc. Other pre
`ferred emollients are relatively water-insoluble ethers
`and alochols such as polypropylene glycol, the conden
`sation product of one or two moles of ethylene oxide
`20
`with behenyl alcohol, etc. Especially preferred emol
`lients include ispropyl myristate, isopropyl palmitate
`and Fluid AP, a commercially available emollient com
`prising the condensation product of about fourteen
`moles of propylene oxide with one mole of butyl alco
`25
`hol.
`The present compositions may contain from about
`20% to about 50% of a liquid emollient. The preferred
`amount of liquid emollient is from about 30% to about
`50%, most preferably from about 35% to about 45%.
`The Antiperspirant Active
`The present compositions contain, as an essential
`ingredient, an antiperspirant active. Any aluminum or
`zirconium astringent antiperspirant salt in the form of
`35
`impalpable particles may be employed. Such salts are
`well known in the antiperspirant art.
`Preferred antiperspirant actives include impalpable
`aluminum chlorhydroxide and aluminum hydroxybro
`mide as well as the antiperspirant actives disclosed in
`40
`the copending application of Raymond E. Bolich, Jr.,
`having Ser. No. 59,690, filed July 30, 1970, and in U.S.
`Pat. No. 3,792,068, issued Feb. 12, 1974 to Luedders et
`al.
`This Luedders et al patent discloses a complex of
`45
`aluminium, zirconium and amino acid formed by
`A. Co-dissolving in water
`-
`1. one part Al2(OH)6-X, wherein X is an anion
`selected from the group consisting of chloride, bro
`mide and iodide and n is a number from about 0.8
`50
`to about 1.2;
`.
`.
`.
`.
`.
`-
`2. n parts Zry wherein Y is an anion selected from the
`group consisting of -O(OH)Cl and OCl, and
`where n has a value of from about 0.16 to about 1.2;
`3. p parts neutral amino acid selected from the group
`consisting of glycine, dl-tryptophane, dl-6-
`phenylalanine, dl-valine, dl-methionine and S-ala
`nine, and where p has a value of from about 0.06 to
`about 0.53;
`,
`f
`B. Co-drying the resultant mixture at a temperature of
`60
`from about 100° C. to about 230 C. to a moisture
`level of from about 0.5% to about 15% by weight;
`and
`C. Comminuting the resultant dried inorganic-organic
`antiperspirant complex into the form of and impalpa
`65
`ble powder.
`,
`,
`" :
`"
`"
`:
`The preferred aluminium, compound for preparation
`of the Luedders et al complex is aluminum chlorhy
`
`4,049,792
`4.
`droxide of the formula Al(OH)3Cl2.H2O. The pre
`ferred zirconium compound for preparation of the
`Luedders et al complex is zirconyl hydroxychloride
`having the formula ZrO(OH)Cl·3H2O. The preferred
`amino acid for preparing the Luedders et al complex is
`glycine of the formula CH(NH2)COOH. (Salts of such
`amino acids can also be employed in such antiperspirant
`complexes.)
`Other preferred actives for use in the present inven
`tion include mixtures of aluminum chloride and alumi
`num hydroxychloride.
`The present compositions may contain from about
`30% to about 60% of an antiperspirant active ingredi
`ent. The preferred amount of antiperspirant active is
`from about 30% to about 50%, preferably from about
`40% to about 50%. Higher levels tend to give a product
`which crumbles too easily and lower levels give a prod
`uct which is less effective.
`A Low Melting Point Wax
`The present compositions may also contain, as an
`optional ingredient, from 0% to about 25% of a waxy
`material having a melting point of from about 100' F. to
`about 150' F. Preferred low melting point waxes are
`fatty acids containing from about 8 to about 20 carbon
`atoms, fatty alcohols containing from about 8 to about
`20 carbon atoms, silicone waxes and glycerol monostea
`rate. Especially preferred materials of this type are the
`Cs to Czo fatty acids and Cs to Czo fatty alcohols. The
`most preferred low melting point waxes are cetyl alco
`hol, stearyl alcohol, myristyl alcohol, lauryl alcohol and
`glycerol monostearate.
`The preferred amount of the low melting point wax is
`from about 5% to about 15%, preferably from about
`8% to about 12%.
`The low melting point wax can be used as an adjunct
`to the high melting point wax to provide structure and
`as an emollient. The low melting point wax can also be
`used to adjust the feel of the stick. One skilled in the art
`will easily be able to make a product which feels more
`brittle, soft, slippery, sticky, rough, etc., by blending
`various suitable high melting point and low melting
`point waxes. The use of a silicone wax tends to cause the
`stick to feel more slippery to the user.
`Inert Filler
`In addition to the ingredients named hereinbefore, it is
`also optional to have in the compositions from 0% to
`about 10% of an inert particulate filler material such as
`a colloidal silica, e.g., Cab-O-Sil (Cabot Corp.), a pyro
`genic silica having a particulate diameter between about
`0.001 and 0.03 microns as disclosed in British Pat. No.
`987,301 and British Pat. No. 1,167,173, or finely divided
`hydrophobic clays such as a reaction product of a clay
`such as Bentonite and dimethyldistearyl ammonium
`chloride (Bentone 34 or Bentone 38, NL Industries) as
`disclosed in British Pat. No. 1,167,173, or talc.
`In addition to the above ingredients, it is desirable to
`include a perfume, stabilizing agent, pigments, coloring
`agent, antibacterial agents, etc., in small amounts. Ex
`amples of additional ingredients include TiO, (pigment),
`oil soluble dyes, and zinc phenol sulfonate (antibacterial
`agent). However, it is desirable that only small amounts
`of hydrophilic ingredients are used in addition to the
`active material. Preferably, less than about 5% of the
`composition, in addition to the active ingredients, is
`soluble in water.
`
`30
`
`55
`
`
`
`

`

`4,049,792
`5
`The stick antiperspirant compositions of the present
`invention are prepared by heating the solid waxes and
`liquid emollient, in a suitable container while gently
`stirring. When the wax or waxes are melted and mixed
`thoroughly with the emollient, the antiperspirant active
`ingredient is mixed and dispersed in the melt. The op
`tional ingredients may then be added or the melt may be
`allowed to cool to a temperature above the solidifica
`tion point before adding additional ingredients.
`The following examples are intended to illustrate but
`not to limit the present invention.
`EXAMPLE
`In the following example, the wax, cetyl alcohol, and
`propylene oxide condensates were combined in a steel
`vessel and heated and gently stirred until the wax and
`cetyl alcohol had melted and were well intermixed in
`each other and the propylene oxide condensates. Next,
`the aluminium chlorhydroxide was stirred into the com
`20
`position and dispersed therein. This mixture was then
`allowed to cool to just above the solidification tempera
`ture at which point the perfume was stirred into the
`mixture which was finally poured into a mold of cylin
`drical shape and allowed to solidify.
`
`5
`
`O
`
`15
`
`EXAMPLE IV
`
`Ingredient
`Carnauba wax
`Beeswax
`Stearyl alcohol
`Isopropyl myristate
`Aluminum chlorhydroxide
`Perfume
`Bentone 38
`
`EXAMPLE V
`
`Ingredient
`Beeswax
`Paraffin.
`Isopropyl myristate
`Vaseline(8)
`Aluminum chlorhydroxide
`Perfume
`Cab-O-Sil (grade M-5)
`
`Percent by Weight
`3.0
`2.0
`7.0
`44.0
`40.0
`1.0
`3.0
`100,0
`
`Percent by Weight
`4.0
`2.5
`37.0
`9.0
`3.5
`0.5
`5.5
`OOO
`
`Percent by Weight
`8.5
`8.5
`35.0
`43.5
`0.5
`4.0
`1000
`
`25
`
`EXAMPLE VI
`
`Ingredient
`Ozokerite wax
`Cetyl alcohol
`Emollient (Condensation Product of
`about 4 moles of propy
`lene oxide with one mole
`of butyl alcohol)
`Aluminum chlorhydroxide
`Perfume
`
`Percent by Weight
`8.5
`10.0
`37.7
`
`- 43.0
`0.8
`100.0
`
`30
`
`35
`
`The following examples were all prepared similarly
`to Example I. The waxy ingredients and emollient were
`first melted and intermixed at which time the antiperspi
`40
`rant active ingredient was added followed by the other
`ingredients. The mixture was then allowed to solidify.
`EXAMPLE II
`
`Ingredient
`Ozokerite wax
`Cetyl alcohol
`Fluid AP(R) (Propylene oxide/
`butyl alcohol con
`densate)
`Aluminum chlorhydroxide
`Perfume
`Cab-O-Sil (grade M-5)
`
`EXAMPLE III
`
`Ingredient
`Ozokerite wax
`Cetyl alcohol
`Isopropyl palmitate
`Zirconium hydroxychloride/
`aluminum chlorhydroxide/
`glycine complex
`Perfume
`Cab-O-Sil (grade M-5)
`
`45
`
`50
`
`55
`
`60
`
`65
`
`Percent by Weight
`4.0
`9.5
`39.5
`
`43.5
`0.5
`3.0
`000
`
`Percent by Weight
`2.5
`8.0
`400
`45.4
`
`0.5
`3.6
`100.0
`
`Ingredient
`Ozokerite wax
`Cetyl alcohol
`Isopropyl palmitate
`Aluminum chlorhydroxide
`Perfume
`Cab-O-Sil (grade M-5)
`
`What is claimed is:
`1. A stick antiperspirant composition essentially anhy
`drous and comprising essentially water-insoluble mate
`rials and a water-soluble antiperspirant salt, said compo
`sition comprising
`A. from about 1% to about 20% of a high melting
`point water-insoluble wax which has a melting
`point of from about 150 F. to about 215° F and
`which is selected from the group consisting of bees
`wax, spermaceti, carnauba, bayberry, candelilla,
`montan, ozokerite, ceresin, paraffin, synthetic wax
`and microcrystalline wax;
`B. from about 20% to about 50% of a liquid, non
`toxic, non-irritating organic emollient compound
`having a water-solubility of from about 0.0005% to
`about 1% at 72 F.; and
`C. from about 30% to about 60% of a compound
`having antiperspirant activity selected from the
`group consisting of
`i. aluminium chlorhydroxide,
`ii. aluminium hydroxybromide,
`iii. mixtures of aluminum chlorhydroxide and alu
`minium chloride, and
`iv. antiperspirant complexes formed by
`a. co-dissolving in water
`1. one part Al(OH)6-X, wherein X is an
`anion selected from the group consisting of
`chloride, bromide and iodide and m is a num
`ber from about 0.8 to about 1.2;
`2. n parts ZrY wherein Y is an anion selected
`from the group consisting of-O(OH)Cl and
`OCl, and where n has a value of from about
`0.16 to about 1.2;
`
`

`

`5
`
`4,049,792
`8
`7
`4. A stick antiperspirant composition essentially anhy
`3. p parts neutral amino acid selected from the
`group consisting of glycine, dil-tryptophane,
`drous and comprising essentially water-insoluble mate
`rials and a water-soluble antiperspirant salt, said compo
`dl-9-phenylalanine, dl-valine, dil-methionine
`sition comprising
`and g-alanine, and where p has a value of
`A. from about 1% to about 20% of a high melting
`from about 0.06 to about 0.53; and
`point water-insoluble wax which has a melting
`b. co-drying the resultant mixture at a tempera
`point of from about 150 F. to about 215 F. and
`ture of from about 100 C. to about 230 C. to
`which is selected from the group consisting of
`a moisture level of from about 0.5% to about
`white beeswax, ceresin, ozokerite and synthetic
`15% by weight; said compound being in im
`10
`waxes;
`palpable powder form.
`B. from about 30% to 50% of a liquid emollient se
`2. A stick antiperspirant composition as recited in
`lected from the group consisting of isopropyl my
`claim 1 which additionally comprises
`ristate, isopropyl palmitate and the condensation
`A. from about 0% to about 25% of a low melting
`product of about 14 moles of propylene oxide with
`point waxy material which has a melting point of
`one mole of butyl alcohol;
`15
`from about 100' F. to about 150' F. and which is
`C. from about 30% to 50% of an impalpable pow
`selected from the group consisting fatty acids con
`dered antiperspirant active compound selected
`taining from about 8 to 20 carbon atoms, fatty alco
`from the group consisting of aluminium chlorhy
`hols containing from about 8 to 20 carbon atoms
`droxide, aluminum hydroxybromide, mixtures of
`and glycerol monostearate; and
`aluminium chlorhydroxide and aluminum chloride
`20
`*... and complexes formed from zirconium hydroxy--
`B. from about 0% to about 10% of an inert particulate
`chloride, aluminium chlorhydroxide and glycine;
`filler material selected from the group consisting of
`and
`colloidal silica and a reaction product of Bentonite
`D. from about 5% to 15% of a low melting point
`and dimethyldistearyl ammonium chloride.
`waxy material which has a melting point of from
`3. A stick antiperspirant composition as recited in
`about 100 F. to about 150 F. and which is selected
`claim 2 wherein:
`from the group consisting of cetyl alcohol, stearyl
`A. said high melting point wax is selected from the
`alcohol, myristyl alcohol, lauryl alcohol and glyc
`group consisting of white beeswax, ozokerite, cere
`erol monostearate.
`sin and synthetic waxes;
`m
`5. A stick antiperspirant composition according to
`30
`B. said emollient is selected from the group consisting
`claim 4 wherein the antiperspirant active comprises
`of isopropyl myristate, isopropyl palmitate, cetyl
`from about 40% to 50% of the composition and is se
`acetate and cetyl proprionate;
`lected from the group consisting of complexes formed
`C. said antiperspirant compound is selected from the
`from zirconium hydroxychloride, aluminium chlorhy
`group consisting of aluminium chlorhydroxide,
`droxide and glycine and wherein the low melting point
`35
`aluminium hydroxybromide, mixtures of aluminum
`waxy material is cetyl alcohol.
`chlorhydroxide and aluminum chloride and com
`6. A stick antiperspirant composition according to
`plexes formed from zirconium hydroxychloride,
`claim 5 wherein the emollient is isopropyl myristate.
`aluminium chlorhydroxide and glycine; and
`.
`7. A stick antiperspirant composition according to
`D. said low melting point waxy material is selected
`claim 5 wherein the emollient is the condensation prod
`from the group consisting of cetyl alcohol, stearyl
`uct of about four moles of propylene oxide with one
`alcohol, myristyl alcohol, lauryl alcohol and glyc
`mole of butyl alcohol.
`erol monostearate.
`.
`
`25
`
`45
`
`SO
`
`55
`
`65
`
`