a2) United States Patent
`US 11,497,706 B2
`(0) Patent No.:
`Sturgis et al.
`*Nov. 15, 2022
`(45) Date of Patent:
`
`US011497706B2
`
`ANTIPERSPIRANT AND DEODORANT
`COMPOSITIONS
`
`(58) Field of Classification Search
`None
`
`(54)
`
`(71)
`
`(72)
`
`Applicant: The Procter & Gamble Company,
`Cincinnati, OH (US)
`
`Inventors: David Arthur Sturgis, Montgomery,
`OH (US); Lindsey Michelle Britt, West
`Chester, OH (US)
`
`(73)
`
`Assignee: The Procter & Gamble Company,
`Cincinnati, OH (US)
`
`See application file for complete search history.
`
`(56)
`
`References Cited
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`
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`(Continued)
`
`FOREIGN PATENT DOCUMENTS
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`
`Notice:
`
`Subject to any disclaimer, the term ofthis
`patent is extended or adjusted under 35
`US.C. 154(b) by 0 days.
`
`BE
`GB
`
`This patent is subject to a terminal dis-
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`Prior Publication Data
`
`US 2021/0100735 Al
`
`Apr. 8, 2021
`
`Related U.S. Application Data
`
`Continuation of application No. 16/021,931, filed on
`Jun. 28, 2018, now Pat. No. 10,905,647.
`(Continued)
`
`(51)
`
`Int. Cl.
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`AGIK 8/92
`AGIK 8/02
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`(52)
`
`USS. Cl.
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`(2006.01)
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`CPC wee AGIK 8/92 (2013.01); A61K 8/0229
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`15150 PCT Search Report and Written Opinion for PCT/US2019/
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`(Continued)
`
`Primary Examiner — Melissa S Mercier
`(74) Attorney, Agent, or Firm — Kathleen Y Carter
`
`(57)
`
`ABSTRACT
`
`A deodorantstick comprising at least 25% by weight liquid
`triglyceride; a primary antimicrobial having a water solu-
`bility of at most about 90 g/L at 25° C.; a fragrance
`composition comprising at least about 50% natural oils,
`essential oils, or a combination thereof; and a primary
`structurant with a melting point of at least 50° C.; said
`deodorant stick being free of an aluminumsalt; and said
`deodorant stick having a hardness from about 70 mm*10 to
`about 140 mm*10, as measured by penetration with ASTM
`D-1321 needle.
`
`(Continued)
`
`23 Claims, 3 Drawing Sheets
`
`oN
`
`
`
`Petitioner Dr. Squatch
`Ex. 1045
`
`Petitioner Dr. Squatch
` Ex. 1045
`
`

`

`US 11,497,706 B2
`
`Page 2
`
`Related U.S. Application Data
`oe
`..
`(60) Provisional application No. 62/647,111, filed on Mar.
`23, 2018, provisional application No. 62/527,180,
`filed on Jun. 30. 2017.
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`2016 (Jun. 1, 2016), XP002768345, the whole document, 3 pgs.
`Kontoghiorghes, George J.,
`“2-Hydroxypyridine-N-Oxides: Effec-
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`All Office Actions: U.S. Appl. No. 16/021,931.
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`
`
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`
`(2006.01)
`(2006.01)
`(2006.01)
`(2006.01)
`(2006.01)
`(2006.01)
`
`51
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`AG6IK 8/37
`A6IK 8/49
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`
`

`

`U.S. Patent
`
`Nov.15, 2022
`
`Sheet 1 of 3
`
`US 11,497,706 B2
`
`
`
`

`

`U.S. Patent
`
`Nov.15, 2022
`
`Sheet 2 of 3
`
`US 11,497,706 B2
`
`
`
`Fig. 2
`
`

`

`U.S. Patent
`
`Nov.15, 2022
`
`Sheet 3 of 3
`
`US 11,497,706 B2
`
`Water Gainf/Loss During Humidity Ramping
`
`PercentageofOriginalMass(4)
`
`2
`
`OD
`
`400
`
`BOG
`
`BOD
`
`Time (minutes)
`
`Fig. 3
`
`

`

`US 11,497,706 B2
`
`1
`ANTIPERSPIRANT AND DEODORANT
`COMPOSITIONS
`
`CROSS REFERENCE TO RELATED
`APPLICATIONS
`
`‘This application is a continuation of U.S. patent applica-
`tion Ser. No. 16/021,931, filed Jun. 28, 2018, which claims
`the benefit of U.S. Provisional Application No. 62/527,180,
`filed Jun. 30, 2017, and of U.S. Provisional Application No.
`62/647,111, filed Mar. 23, 2018, the substances of which are
`incorporated herein by reference.
`
`FIELD OF THE INVENTION
`
`The present disclosure relates to antiperspirant and
`deodorant compositions and methodsrelating thereto.
`
`BACKGROUNDOF THE INVENTION
`
`Many antiperspirant and deodorants use actives that are
`astringent metallic salts, or in particular, aluminum salts.
`While aluminum is highly effective as an active, there is
`consumerinterest in antiperspirants and deodorants that do
`not contain aluminum.
`Consumers are also seeking more natural products com-
`plete with fragrances that are mostly natural or essential oil
`based. They are further seeking products with lowerirrita-
`tion than they have experienced with baking soda based
`products. The challenge with formulating with the natural
`and essential oil fragrances is that they can beless stable in
`the presence of heat and extreme pH (either high or low).
`And products formulated with baking soda, which has a
`relatively high pH and high water solubility, can increase
`irritation, even for consumers with moderate sweat rates.
`Highly water soluble alkaline powders contribute negatively
`towards naturalor essential oil stability as well, especially in
`a hot process needed to melt waxes. And high water solu-
`bility powders can also lead to gritty products, as the water
`soluble powders can agglomerate when exposed to moisture
`released from powders during the hot batch process.
`Thus,
`there is a continuing challenge to formulate a
`non-aluminum, natural fragrance deodorant that provides
`low irritation while maintaining sufficient odor protection.
`Piroctone olamine is an anti-dandruff active used in
`
`shampoos, conditioners, and other treatments. Piroctone
`olamine can be an effective antimicrobial, but used alone as
`an active,
`it may not deliver the hoped for consumer
`performance. The inventors of the present invention have
`found,
`surprisingly,
`that
`the combination of piroctone
`olamine and other antimicrobials can provide significant
`antimicrobial activity against two of the most common
`underarm odor bacteria C. mucofaciens and S. epidermidis,
`which results in consumer odorprotection on par or greater
`than some of the commonly used commercial deodorants
`available today.
`Also to consider is that impurities can reducethe efficacy
`of piroctone olamine Therefore, there is a need to develop
`products that mitigate this phenomenon and provide higher
`efficacy. The inventors of the present invention have found
`that select combinations of chelators and piroctone olamine,
`such as in an anhydrous formulation or in particularratios,
`can provide significantly higher levels of anti-fungalactivity
`than either material alone.
`
`Furthermore, while antimicrobials in antiperspirants and
`deodorants are known to be able to reduce the microbes on
`
`the skin, microbes within hair follicles may still remain and
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`40
`
`45
`
`50
`
`55
`
`60
`
`65
`
`2
`contribute to malodor. The inventors of the present invention
`have found that piroctone olamine and other antimicrobial
`powders, if used at a size that can fit into a hair follicle, can
`deliver surprisingly superior antimicrobial activity.
`By utilizing piroctone olamine in combination with
`appropriate antimicrobials, chelators, and/or at particular
`particle sizes, the present invention delivers compositions
`and products with superior antimicrobial performance.
`
`SUMMARY OF THE INVENTION
`
`A deodorant stick comprising at least 25% of a liquid
`triglyceride; a primary antimicrobial having a water solu-
`bility of at most about 90 g/L at 25° C.; a fragrance
`composition comprising at least about 50% natural oils,
`essential oils, or a combination thereof; and a primary
`structurant with a melting point of at least 50° C.; said
`deodorant stick being free of an aluminumsalt; and said
`deodorant stick having a hardness from about 70 mm*10 to
`about 140 mm*10, as measured by penetration with ASTM
`D-1321 needle.
`
`BRIEF DESCRIPTION OF THE DRAWINGS
`
`FIG. 1 is an illustration of a hair and hair follicle along
`with larger antimicrobial particles.
`FIG. 2 is an illustration of a hair and hair follicle along
`with smaller antimicrobial particles.
`FIG.3 is a graph of the water gain/loss of two deodorant
`products.
`
`DETAILED DESCRIPTION OF THE
`INVENTION
`
`While the specification concludes with claims that par-
`ticularly point out and distinctly claim the invention,it is
`believed the present invention will be better understood
`from the following description.
`The present invention can comprise, consist of, or consist
`essentially of the essential elements and limitations of the
`invention described herein, as well any of the additional or
`optional ingredients, components, or limitations described
`herein.
`
`All percentages, parts and ratios are based upon the total
`weight of the compositions of the present invention, unless
`otherwise specified. All such weights as they pertain to listed
`ingredients are based on the active level and, therefore do
`not include carriers or by-products that may be included in
`commercially available materials.
`The components and/or steps, including those which may
`optionally be added, of the various embodiments of the
`present invention, are described in detail below.
`All documents cited are, in relevant part, incorporated
`herein by reference; the citation of any documentis not to be
`construed as an admission thatit is prior art with respect to
`the present invention.
`All ratios are weight ratios unless specifically stated
`otherwise.
`
`All temperatures are in degrees Celsius, unless specifi-
`cally stated otherwise.
`Except as otherwise noted, all amounts including quan-
`tities, percentages, portions, and proportions, are understood
`to be modified by the word “about”, and amounts are not
`669?
`66
`intended to indicate significant digits.
`a,
`Except as otherwise noted, the articles
`“the” mean “one or more”.
`
`an’, and
`
`

`

`US 11,497,706 B2
`
`3
`Herein, “comprising” means that other steps and other
`ingredients which do not affect the end result can be added.
`This term encompassesthe terms “consisting of’ and “con-
`sisting essentially of’. The compositions and methods/pro-
`cesses of the present invention can comprise, consist of, and
`consist essentially of the essential elements and limitations
`of the invention described herein, as well as any of the
`additional or optional
`ingredients, components, steps, or
`limitations described herein.
`
`Herein, “effective” means an amount of a subject active
`high enough to provide a significant positive modification of
`the condition to be treated. An effective amount of the
`subject active will vary with the particular condition being
`treated, the severity of the condition, the duration of the
`treatment,
`the nature of concurrent
`treatment, and like
`factors.
`
`The term “anhydrous”as used herein means substantially
`free of added or free water. From a formulation standpoint,
`this means that the anhydrous antiperspirant or deodorant
`stick compositions of the present invention contain less than
`about 1%, and more specifically zero percent, by weight of
`free or added water, other than the water of hydration
`typically associated with the particulate antiperspirant or
`deodorant active prior to formulation.
`The term “ambient conditions” as used herein refers to
`
`surrounding conditions under about one atmosphere ofpres-
`sure, at about 50% relative humidity, and at about 25° C.,
`unless otherwise specified. All values, amounts, and mea-
`surements described herein are obtained under ambient
`conditions unless otherwise specified.
`The term “majority” refers to greater than about 51% of
`the stated component or parameter.
`The term “polarity” as used herein is defined by the
`Hansen Solubility Parameter for solubility.
`“Substantially free of’ refers to about 2% or less, about
`1% orless, or about 0.1% orless ofa stated ingredient. “Free
`of”refers to no detectable amountofthe stated ingredient or
`thing.
`The term “volatile” as used herein refers to those mate-
`
`rials that have a measurable vapor pressure at 25° C. Such
`vapor pressures typically range from about 0.01 millimeters
`of Mercury (mm Hg) to about 6 mmHg, moretypically from
`about 0.02 mmHgto about 1.5 mmHg; and have an average
`boiling point at one (1) atmosphere ofpressure of less than
`about 250° C., more typically less than about 235° C.
`Conversely, the term “non-volatile” refers to those materials
`that are not “volatile” as defined herein.
`A. 2-Pyridinol-N-Oxide Materials
`2-Pyridinol-N-oxide materials suitable for use in this
`invention include a substituted or unsubstituted 2-pyridinol-
`N-oxide material or a salt thereof. Included within the scope
`of this invention are tautomers of this material, e.g., 1-hy-
`droxy-2(1H)-pyridinone. The substituted or unsubstituted
`2-pyridinol-N-oxide material and its corresponding tauto-
`meric form, 1-hydroxy-2(1H)-pyridinone, are shown below:
`
`1
`N.
`
`Rt
`
`OH Rt
`
`1
`N
`
`0
`
`R3 Api i Ap
`R?
`R?
`
`4
`where R', R*, R®, R* groups are independently selected
`from the group consisting of H, Cl, Br, I, F, NO, NO,, and
`(CH,),,G, where each G is independently selected from the
`group consisting of (O),,SO,M°, (O),,CO,M®, (O),,C(O)
`(R°), (O),,C(OYN(RPR®), (O),,CN, (O),,(R°), and N(R®R®),
`where m is 0 or 1, n is an integer from 0 to 4, R® and R® are
`independently selected fromthe group consisting of H and
`a substituted or unsubstituted C,-C, 5, organic group, and M*
`is selected from the group consisting of H, a substituted or
`unsubstituted C,-C,,, organic group, *N(R’R*R?R"°), and
`1/q M' %* where M'is selected from the group consisting of
`an alkali metal of charge q and an alkaline earth metal of
`charge gq, where R7, R8, R9, and R10 are independently
`selected from the group consisting of H and a substituted or
`unsubstituted C,-C,>5, organic group, and where any pair of
`vicinal groups, R' and R?, R? and R°, R® and R* may be
`taken together to form another five- or six-membered aro-
`matic or aliphatic ring optionally substituted with one or
`more groups selected from the group consisting of Cl, Br, I,
`F, NO, NO,, CN, (CH,),,G, and mixtures thereof. Suitable
`organic groups include (C,-C,,)alkyl, (C.-C, ,)alkenyl, and
`(C,-C,,)alkynyl. The organic group mayoptionally be sub-
`stituted and suitable substituent groups include a hydroxyl
`group, a carboxyl group, and an amino group. 2-pyridinol-
`N-oxide is also known, for example, as 2-hydroxypyridine-
`N-oxide, 2-pyridinol-1-oxide, or 2-hydroxypyridine-1-ox-
`ide.
`In certain aspects, the 2-pyridinol-N-oxide material is a
`2-pyridinol-N-oxide material or tautomer thereof according
`to the formula(s) above, where R', R?, R*, R* are indepen-
`dently selected from the group consisting of H, Cl, and
`(CH,),,G, where G is independently selected from the group
`consisting of (O),,SO;M?,
`(O),,CO,M?,
`(O),,C(O\R),
`(O),,CN, and (O),,(R°), where m is 0 or 1. In other aspects,
`the 2-pyridinol-N-oxide material is a 2-pyridinol-N-oxide
`material according to the formula above, where R', R’, R’,
`R* are independently selected from the group consisting of
`H, SO,M°, and CO,M°. In still other aspects, R’, R?, R®, R*
`are independently selected from the group consisting of H,
`SO,M°, and CO,M®, where no more than one R*, R?, R*, R*
`is SO,;M? or CO,M?.
`In certain aspects, the 2-pyridinol-N-oxide material is the
`salt of a substituted or unsubstituted 2-pyridinol-N-oxide
`material. In these aspects, the hydrogen of the hydroxyl
`group of the 2-pyridinol-N-oxide material may be substi-
`tuted with a suitable charge-balancing cation.
`In these
`aspects, non-limiting examples of the hydrogen-substituting
`cation include Na‘, Lit, K*, 4 Mg**,or 4 Ca",substituted
`ammonium, such as C,-C, alkanolammnonium, mono-etha-
`nolamine (MEA), tri-ethanolamine (TEA), di-ethanolamine
`(DEA), or any mixture thereof. In some aspects, in solution,
`the cation may be dissociated from the 2-pyridinol-N-oxide
`or the 1-hydroxy-2(1H)-pyridinone anion.
`In certain aspects, the 2-pyridinol-N-oxide material is of
`a substituted or unsubstituted 2-pyridinol-N-oxide material.
`Salts for use herein include those formed from the polyva-
`lent metals barium, bismuth, strontium, copper, zinc, cad-
`mium, zirconium and mixtures thereof.
`is
`In some aspects,
`the 2-pyridinol-N-oxide material
`selected from the group consisting of: 6-hydroxy-3-pyri-
`dinesulfonic acid, 1-oxide (CAS 191672-18-1); 2-hydroxy-
`pyridine-1-oxide (CAS 13161-30-3); 2-hydroxy-4-pyridin-
`ecarboxylic acid, 1-oxide (CAS 13602-64-7); 5-ethoxy-2-
`pyridinol, 2-acetate,
`l-oxide (CAS 51984-49-7);
`1-@G-
`hydroxy-2-oxido-4-isoquinolinyl)-ethanone (CAS 65417-
`65-4); 6-hydroxy-3-pyridinecarboxylic acid, 1-oxide (CAS
`90037-89-1); 2-methoxy-4-quinolinecarbonitrile, 1-oxide
`
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`US 11,497,706 B2
`
`5
`(CAS 379722-76-6); 2-pyridinecarboxylic acid, 6-hydroxy-,
`l-oxide (CAS 1094194-45-2); 3-pyridinecarboxylic acid,
`2-hydroxy-, 1-oxide (CAS 408538-43-2); 2-pyridinol, 3-ni-
`tro-, 1-oxide (CAS 282102-08-3); 3-pyridinepropanenitrile,
`2-hydroxy-,
`1-oxide
`(193605-60-6);
`3-pyridineethanol,
`2-hydroxy-, 3-acetate, 1-oxide (CAS 193605-56-0); 2-pyri-
`dinol, 4-bromo-, 1-oxide (CAS 170875-41-9); 2-pyridinol,
`4,6-dibromo-, 2-acetate,
`1-oxide
`(CAS 170875-40-8);
`2-pyridinol, 4,6-dibromo,
`1l-oxide (CAS 170875-38-4);
`2-pyridinol, 4-(2-aminoethyl)-,
`l-oxide (CAS 154403-93-
`7); 2-pyridinol, 5-(2-aminoethyl)-, 1-oxide (CAS 154403-
`92-6);
`3-pyridinepropanoic
`acid,
`a-amino-6-hydroxy-,
`l-oxide (CAS 134419-61-7); 2-pyridinol, 3,5-dimethyl,
`l-oxide (CAS 102074-62-4); 2-pyridinol, 3-methyl-, 1-ox-
`ide (CAS 99969-07-0); 2-pyridinol, 3,5-dinitro, 1-oxide
`(CAS 98136-47-1); 2-pyridinol, 3,5-dibromo-, 1-oxide
`(CAS 98136-29-9); 2-pyridinol, 4-methyl-6-(2-methylpro-
`pyl)-, 1-oxide (CAS 91408-77-4); 2-pyridinol, 3-bromo-4,
`6-dimethyl-, 1-oxide (CAS 91408-76-3); 2-pyridinol, 4,5,6-
`trimethyl-,
`l-oxide
`(CAS
`91408-75-2);
`2-pyridinol,
`6-heptyl-4-methyl-, 1-oxide (CAS 91408-73-0); 2-pyridi-
`nol, 6-(cyclohexylmethyl)-4-methyl-, 1-oxide (CAS 91408-
`72-9); 2-pyridinol, 6-bromo-, 1-oxide (CAS 89284-00-4);
`2-pyridinol, 5-bromo-, 1-oxide (CAS 89283-99-8); 2-pyri-
`dinol, 3,5-dichloro-4,6-difluoro-, 1-oxide (CAS 33693-37-
`7); 2-pyridinol, 3,4,5,6-tetrachloro-,
`l1-oxide (CAS 32835-
`63-5); 2-pyridinol, 6-methyl-, 1-oxide (CAS 14420-62-3);
`2-pyridinol, 5-nitro-, 1-oxide (CAS 14396-03-3); 2-pyridi-
`nol, 4-methyl-5-nitro-, 1-oxide (CAS 13602-77-2); 2-pyri-
`dinol, 4-chloro-5-nitro-, 1-oxide (CAS 13602-73-8); 2-pyri-
`dinol, 4-chloro-,
`l-oxide (CAS 13602-65-8); 2-pyridinol,
`4-nitro-,
`1l-oxide
`(CAS 13602-63-6); and 2-pyridinol,
`4-methyl-, 1-oxide (CAS 1952-64-3), and mixtures thereof.
`These materials are commercially available from,
`for
`example, Sigma-Aldrich (St. Louis, Mo.) and/or Aces
`Pharma (Branford, Conn.).
`In certain aspects, the 2-pyridinol-N-oxide material is a
`2-pyridinol-N-oxide material selected from the group con-
`sisting of: 2-hydroxypyridine-1-oxide; 3-pyridinecarboxylic
`acid, 2-hydroxy-, 1-oxide; 6-hydroxy-3-pyridinecarboxylic
`acid, 1-oxide; 2-hydroxy-4-pyridinecarboxylic acid, 1-ox-
`ide; 2-pyridinecarboxylic acid, 6-hydroxy-, 1-oxide; 6-hy-
`droxy-3-pyridinesulfonic
`acid,
`1-oxide;
`and mixtures
`thereof.
`
`In certain aspects, the 2-pyridinol-N-oxide material is a
`1-Hydroxy-2(1H)-pyridinone material selected from the
`group consisting of: 1-Hydroxy-2(1H)-pyridinone (CAS
`822-89-9); 1,6-dihydro-1 -hydroxy-6-oxo-3-Pyridinecarbox-
`ylic acid (CAS 677763-18-7); 1,2-dihydro-1-hydroxy-2-
`oxo-4-Pyridinecarboxylic acid (CAS 119736-22-0); 1,6-di-
`hydro-1-hydroxy-6-oxo-2-Pyridinecarboxylic
`acid (CAS
`94781-89-2);
` 1-hydroxy-4-methyl-6-(2,4,4-trimethylpen-
`tyl)-2(1H)-Pyridinone (CAS 50650-76-5); 6-(cyclohexylm-
`ethyl)-1-hydroxy-4-methyl-2(1H)-Pyridinone (CAS 29342-
`10-7);
`1-hydroxy-4,6-dimethyl-2(1H)-Pyridinone
`(CAS
`29342-02-7);
`1-Hydroxy-4-methyl-6-(2,4,4-trimethylpen-
`tyl)-2-pyridone monoethanolamine
`(CAS 68890-66-4);
`1-hydroxy-6-(octyloxy)-2(1H)-Pyridinone (CAS 162912-
`64-3);
`1-Hydroxy-4-methyl-6-cyclohexyl-2-pyridinone
`ethanolamine salt (CAS 41621-49-2); 1-Hydroxy-4-methyl-
`6-cyclohexyl-2-pyridinone (CAS 29342-05-0); 6-ethoxy-1,
`2-dihydro-1-hydroxy-2-oxo-4-Pyridinecarboxylic
`acid,
`methyl ester (CAS 36979-78-9); 1-hydroxy-5-nitro-2(1H)-
`Pyridinone (CAS 45939-70-6); and mixtures thereof. These
`materials are commercially available from, for example,
`Sigma-Aldrich (St. Louis, Mo.), Princeton Building Blocks
`(Monmouth Junction, N.J.), 3B Scientific Corporation (Lib-
`
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`20
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`6
`IIl.), SynFine Research (Richmond Hill, ON),
`ertyville,
`Ryan Scientific,
`Inc.
`(Mt. Pleasant, S.C.), and/or Aces
`Pharma (Branford, Conn.).
`In certain aspects, the 2-pyridinol-N-oxide material is a
`2-pyridinol-N-oxide material or tautomer thereof according
`to the formula(s) below:
`
`where X is an oxygenor sulfur moiety and R is a substituted
`or unsubstituted hydrocarbon group having between 1 and
`20 carbon atoms. Materials of this class can be synthesized
`following the procedure disclosed in U.S. Pat. No. 5,675,
`013.
`
`In certain aspects, the 2-pyridinol-N-oxide material is a
`2-pyridinol-N-oxide material or tautomer thereof according
`to the formula(s) below:
`
`Wherein R' and R" are independently either hydrogen or
`a substituted or unsubstituted hydrocarbon group having
`between 1 and 20 carbon atoms. Materials of this class can
`be synthesized following the procedure disclosed in U.S.
`Pat. No. 5,675,013. In certain aspects, the 2-pyridinol-N-
`oxide material
`is 1-Hydroxy-4-methy]-6-(2,4,4-trimethyl-
`pentyl)-2-pyridone monoethanolaminesalt.
`The amount of 2-pyridinol-N-oxide (which may through-
`out this disclosure sometimes be referred to as piroctone
`olamine) in antiperspirant or deodorant formulations of the
`present invention may be from about 0.04% to about 1.0%
`by weight, in some embodiments from about 0.05% to about
`0.6% by weight, and in some embodiments from about
`0.05% to about 0.5% by weight.
`B. Chelators
`
`In the present invention, iron chelators may have, but are
`not limited to, the following characteristics:
`1. An affinity for iron ions in either the ferrous (iron IT) or
`ferric (II) forms;
`2. Materials of Description 1 (above) that have a denticity of
`four or higher (denticity is the number of groups of a
`molecule that bind to the iron);
`3. Chemical descriptions that are a subset of Description 2:
`a. Either natural or synthetic materials;
`b. Materials of the following chemical classes:
`i. Aminophosphates
`ii Aminocarboxylates
`ili. Hydroxamic acids
`and molecules representing combinations of these chemi-
`cal classes.
`
`

`

`US 11,497,706 B2
`
`7
`invention, an iron
`In an embodiment of the present
`chelator may be present from the following groups:
`(1) Iron Chelators Represented by the Following Structure:
`
`8
`olamine gets into solution. This further advantage only
`exists in an anhydrous formulation, as in an aqueousfor-
`mulation, everything is fully in solution from the beginning.
`Table 1 below showsthe intrinsic water solubility inde-
`pendent of pH (LogWS,,)of piroctone olamine and EDTA as
`>
`_
`an example. The lower LogWS,ofpiroctone olamineindi-
`cates that it will get into solution more slowly than a chelant
`i
`15
`such as EDTA, and the chelant will have more of an
`BAUS™yom
`opportunity to bond with iron than the piroctone olamine
`will.
`L
`
`RB
`
`TABLE 1
`
`where R'’, R’* R'3, R™*, R* are independently selected
`from the group consisting of M'M?PO,;, CO,M’, and mix-
`tures thereof
`where M' and M?is H, a metalsalt (such as Na, K, Ca,
`Mg, Al, etc.) or ammonium salt.
`(2) Iron Chelators Represented by the Following Structure:
`
`15
`
`CAS Number
`6153824
`6153825
`
`Name
`Piroctone olamine
`EDTA
`
`LogWs,
`3.22
`-14
`
`Furthermore, the inventors of the present invention have
`foundthat the ratio of chelant to piroctone olamine may be
`
`iin a8
`N
`
`i
`OH
`
`O A
`
`é
`
`AL “Sw
`(CH) we Dan
`(CH) a ak CH A
`H
`|
`H
`OH
`
`|
`OH
`
`(CHa)
`
`where a is an integer from 2 to 7 wherein any of the CH,
`groups in this unit may be substituted with alkyl oraryl
`units that may contain heteroatoms(S, N, O, Cl, F, Br
`or I)
`where b is an integer from 1 to 7 wherein any of the CH,
`groups in this unit may be substituted with alkyl oraryl
`units that may contain heteroatoms(S, N, O, Cl, F, Br
`or I)
`where R'° is H or (CH,),, where n in an integer from 1 to
`6 or is a CH,linker unit that may be further substituted
`at any CH, group in the chain with alkyl or aryl units
`that may contain heteroatoms(S, N, O, Cl, F, Br, or I).
`Specific and/or additional chelators in the present inven-
`tion may include, but are not limited to, diethylenetriamine-
`pentaacetic acid (DTPA), diethylenetriaminepentakis (meth-
`ylenephosphonic acid)
`(DTPMP), desferrioxamine,
`their
`salts and combinations thereof, EDTA, DPTA, EDDS,
`enterobactin, desferrioxamine, HBED, and combinations
`thereof.
`
`While piroctone olamine can be an effective antimicrobial
`for an antiperspirant or deodorant, the presence of iron and
`other impurities may reduce piroctone olamine’s effective-
`ness. As such, the inventors of the present invention have
`found that
`including a chelant
`to bond with iron,
`for
`example, can reduce the occurrence of piroctone olamine
`itself bonding with theiron,essentially freeing the piroctone
`olamine to be effective against bacteria.
`This is particularly true in anhydrous formulations. In an
`aqueous formulation comprising piroctone olamine and a
`chelant, the chelant can improve piroctone olamine’s effi-
`cacy because the chelant should have more affinity for the
`iron than the piroctone olamine has affinity for the iron. In
`addition,
`in an anhydrous formulation, with little or no
`water, the water solubility of the materials comes into play
`when sweat meets the formulation. Piroctone olamine typi-
`cally has a lower water solubility than a chelant, meaning
`that in an anhydrous formulation, the chelant’s higher water
`solubility results in the chelant more quickly getting into
`solution and bonding with iron,
`ie., before the piroctone
`
`30
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`
`important. In some embodiments, the improved efficacy of
`a chelant with piroctone olamine can be seen whenthe ratio
`of chelant
`to piroctone is at
`least about 4:1,
`in some
`embodimentsat least 6:1, and in some embodiments, at least
`8:1. The amountof chelant, by weight of composition, may
`be from about 0.05% to about 4%.
`C. Water Solubility
`The present
`inventors have discovered that the water
`solubilities of certain components in the solid stick antiper-
`spirant or deodorant have great importance. Some deodorant
`ingredients will bring in moisture to the batch, which can
`solvate these components to different extents when the water
`evaporates and subsequently recondenses as free water in
`the batch. Certain batch processing conditions (such as a
`closed top on the tank) could moreeffectively trap this water
`in the tank, whereit is then free to interact with components
`of the batch. For example, highly water soluble alkaline
`powders can contribute negatively towards natural and
`essential oil stability when dissolved. This is because many
`natural and essential oils contain a broad range of perfume
`chemicals, many of which can undergo degradation reac-
`tions when exposed to extreme pHor heat. This is why many
`natural and essential oils have shorter shelf lives than many
`commercial synthetic chemicals or perfumes. And certain
`antimicrobials may causeirritation due to high water solu-
`bility. Further, high water solubility can lead to grittier
`products as the more water soluble powders can agglomerate
`whenexposed to moisture released from powders during the
`heat of manufacture.
`
`To demonstrate this concept, the present inventors made
`two batches of deodorant product following the same for-
`mula, where baking soda (high water solubility) was the
`active ingredient. The fragrance contained 6-8% natural
`vanilla. Batch A was made similarly to the inventive for-
`mulas herein. Batch B had 3% water added into the batch
`during cooling to simulate moisture that could evaporate and
`recondense in a tank under certain process conditions. The
`differences in Batch B were almost immediately obvious.
`The color of the batch became a deep brown during a brief
`hold time of 15 minutes.
`
`

`

`US 11,497,706 B2
`
`9
`is believed that the water
`it
`As previously explained,
`solvates the baking soda sinceit is so highly water soluble,
`and the resulting high pH solution degrades fragrance (par-
`ticularly the more susceptible natural vanilla) The resulting
`byproducts change the color and odorof the batch.
`Color and odor were observedto be adversely affected by
`the excess water. The color difference was very visually
`obvious. The odor differences were confirmed with an odor
`
`panel, in which the comparison of Batch A (control) vs.
`Batch B failed with a grade of 2.7 (below 3 is a failure).
`Thus, embodiments of the present invention may include an
`antimicrobial with a low water solubility. An antimicrobial
`with a low water solubility may be, in some embodiments,
`an antimicrobial with a water solubility of at most 90 g/L at
`25°C., in other embodiments at most 75 g/L at 25° C., or in
`still other embodiments at most 50 g/L at 25° C.
`Materials with a water solubility above 90 g/L @25° C.
`include but are not limited to: potassium carbonate, potas-
`sium bicarbonate, sodium carbonate, sodium sesquicarbon-
`ate, triethyl citrate, and baking soda. Materials with a water
`solubility below 90 g/L @25° C. include but are not limited
`to: beryllium carbonate, magnesium carbonat