WO2013077832A2 - Compositions d'aluminium à efficacité améliorée présentant des bandes iii et iv de clhr élevées - Google Patents

Compositions d'aluminium à efficacité améliorée présentant des bandes iii et iv de clhr élevées Download PDF

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Publication number
WO2013077832A2
WO2013077832A2 PCT/US2007/070374 US2007070374W WO2013077832A2 WO 2013077832 A2 WO2013077832 A2 WO 2013077832A2 US 2007070374 W US2007070374 W US 2007070374W WO 2013077832 A2 WO2013077832 A2 WO 2013077832A2
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WIPO (PCT)
Prior art keywords
band
aluminum
solution
ratio
area
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Ceased
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PCT/US2007/070374
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English (en)
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WO2013077832A3 (fr
Inventor
Zijun Li
Mark Rerek
Kevin Janak
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Reheis Co Inc
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Reheis Co Inc
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Priority to PCT/US2007/070374 priority Critical patent/WO2013077832A2/fr
Anticipated expiration legal-status Critical
Publication of WO2013077832A2 publication Critical patent/WO2013077832A2/fr
Publication of WO2013077832A3 publication Critical patent/WO2013077832A3/fr
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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q15/00—Anti-perspirants or body deodorants
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/26—Aluminium; Compounds thereof

Definitions

  • This invention relates to novel aluminum aniiperspirant compositions of enhanced efficacy thai are activated by both heat and acid and have a high HPLC Band IB as well as a high HPLC Band IV and to the processes for the preparation of the compositions.
  • the processes of the present invention include the addition of an acid such as A.1CL to the aluminum solutions having high HPLC Band HI prepared by both direct and indirect processes, as well as the preparation of aluminum sesquichlorohydrate solutions directly through the reaction o f Al powder with aqueous aluminum chloride solutions.
  • the aluminum sal solutions derived from the processes of the invention are dried to powders and are conveniently adaptable for use in consumer-acceptable aniiperspirant- formulaied products incl uding aerosols, sticks, creams and soft solids.
  • Enhanced efficacy aluminum annperspirani salts are known and generally related to the aluminum species that are activated by either heat, as indicated by having high SEC (size exclusion cliromatography)-HPLC (high performance liquid chromatography) Band III content or by acid as having high Band ⁇ content at lower Al Cl ratio. These compositions are typically different from conventional aniiperspirant salts that have low quantities of Band III, with Band III/II area ratio of less than 0.1 or 0.2, as well as low Band IV of less than 20%. In the evaluation of "Bands" and "peaks”, as applied in the characterization for aniiperspirant properties, typically i n the Band reference. Bands I, II.
  • Enhanced efficacy aluminum aniiperspirant salts have an HPLC Band LII/11 area ratio of 0.5 or higher with at least 70% and preferably at least 80% of aluminum contained in Bands II and III.
  • Enhanced aniiperspirant salts typically have a Band III content of at least 20%, and usually at least 30%, of the total aluminum contained in all the peaks as measured by peak area.
  • the enhanced aluminum salts activated by heat that are characterized by the presence of high HPLC Band III or high Band III/II ratio, are prepared by the dilution and heat treatment of 50% ACH (aluminum chlorohydraicj solution and quickly drying the solutions to powders because of the rapid reverting bacl; of Band Iff to Band II whe such are in aqueous solutions, particularly at concentrations of greater than 20%.
  • 50% ACH aluminum chlorohydraicj solution and quickly drying the solutions to powders because of the rapid reverting bacl; of Band Iff to Band II whe such are in aqueous solutions, particularly at concentrations of greater than 20%.
  • Prior an patents describing the enhanced aluminum salts include British Patent G.B 2,048,229; U.S. Patent No. 4,359,456; U.S. Patent ' No. 4,775,528; U.S. Patent No. 4,81 8,512; U.S. Patent No. 4,859,446; U.S. Patent No. 4,871 ,525; U.S. Patent No. 4.900,534: U.S. Patent No. 4.944,933; U.S. Patent No. 5,356.609; U.S. Patent No. 5,358,694; U.S. Patent No.5,595 729 and U.S. Patent No. 5.626,827.
  • Aluminum antiperspirant salts of enhanced efficacy can also be prepared through acid activation at lower Al/Cl ratio, such as ratios of less than 1 .5 as described, for example, in U.S. Patent Nos. 5.71 8, 876 and 6,024,945. where the basic aluminum chloride solutions with 28% to 42% solid concentration have at least 50% HPLC Band II and less than 20% Band 111.
  • U.S. Pat. No. 6,902,724 describes a basic aluminum chloride (BAG) composition having a Band I relative area value of less than 5%, a Band II of 20% to 60%, a Band ID of 1 0% to 35% and a Band IV of 15% to 50% at Al/Cl ratio of 1.2 to 1 .5 comprising 30% to 42% anhydrous solid.
  • BAG basic aluminum chloride
  • the BAC solution is prepared by reacting aluminum powder with aluminum chloride aqueous solution at a temperature greater than 85 C.
  • the freshly prepared BAC solutions always have Band HI of less than 20% and. in any event, no BAC solution in that patent reference appears as having a Band III area greater than 25%.
  • the HPLC figure in that patent focuses on a BAC solution having high Bands II and TV.
  • aluminum antiperspirant compositions of enhanced efficacy that are activated by both heat and acid with high HPLC Band III and high HPLC Band IV is unknown. Accordingly, the production of aluminum antiperspirant compositions of enhanced efficacy that are activated by both heat and acid and that have both a high HPLC Band HI and a high Band IV is highly desirable.
  • the aluminum-sesquichlorohydrate solutions prepared by die direct process of the invention have higher concentration and are stable in aqueous solution for several days before being spray dried compared to solutions solely prepared by dilution and beat activation that must be spray dried immediately.
  • the aluminum powders prepared according to the invention can be used in various finished formulations, such as aerosols, sticks, soft solids and the like.
  • novel aluminum compositions of enhanced antiperspirant efficacy thai are activated by both heat and acid and are characterized by having high HPLC Band ill and high HPLC Band IV. are prepared by processes (referred to for convenience as Processes " A” and “B"), by the addition of an acid such as A.IQ3 to the alum inum salt solutions having high HPLC Band ill prepared either directly or indirectly.
  • these novel aluminum salt solutions may be prepared by an alternative process referred as Process "C,” involving the direct reaction of Al powder with the aqueous A.IC I3 solutions at elevated temperatures at Al/Cl ratios of less than 1.8.
  • the aluminum salt .solutions prepared according to the invention, from each of the Processes of A, B and C are dried to powders and are characterized by having: an HPLC Band 1 of less than 1 0%, preferably less than 5%; a Band III of at least 20%, preferably at least 30%: a Band IU/Il ratio of at least about 0.7, preferably at least about 0.9: and a Band IV of at least 20%, preferably ai least 25% and have an Al/Cl ratio of below l .S.
  • the powders containing activated aluminum salts derived in accordance with the invention may be utilized, in fonnulating aerosol, soft solid, cream and stick products, as appropriate.
  • ii is an object of the present invention to provide novel basic aluminum, haiic!e ainiperspiram salt powder compositions of enhanced efficacy activated by both heat and acid.
  • Fig. 1 is the 2 Al NMR of an aluminum salt composition with an Al/Cl ratio of 1 .47 prepared according io Process A of the invention.
  • Fig. 2 is the SEC-HPLC of an aluminum salt composition with an Al/Cl ratio of 1.49 prepared according to process B of the invention.
  • Fig. 3 is the SDC-HPLC of an aluminum sail composi tion with an Al/Cl ratio of 1.71 prepared according to process C of the invention.
  • the present invention is di rected to novel aluminum antiperspirant compositions of enhanced efficacy activated by both heat and acid which, when analyzed by SEC-iTPLC at about 10% concentration (i.e.. by 2% Al) in water, exhibit an HPLC Band 1 area of less than 10%, preferably less than 5%; a Band Hi area of at least 20%. preferably 30% or more; a Band ⁇ / ⁇ ratio of at least 0.7. preferably 0.9 or more; a Band IV area of at least 20%, preferably 25% or more; and have at least: 60% and preferably 70% or more aluminum species contained in Bands ⁇ and Band IV.
  • the basic aluminum salts of these compositions have the formula:
  • a iOH) wherein X is CI , Br , I or NOj , a is from about 1.1 to about 1.7, with basic aluminum chioride the most preferred.
  • BAG as used herein, and as indicated by the above formula, includes the iodide and bromide halogen ions in addition to chloride, and the nitrate ion NOj .
  • the preferred ratio of aluminum to chloride or other ions of the BAC solution is from 1.4 to 1.6.
  • BAC solution is first prepared by the standard method such as described in US patent 5.71 8.876 which is incorporated herein by reference.
  • the ratio of Al Cl of the BAC solution should be above J .5, with the preferred ratio being 1 .7 to 1 .9.
  • the 50% solution is diluted, so that it comprises about ) 0% to about 25% by weight solution, and heated until the desired .HPLC Band ⁇ / ⁇ ratio is obtained.
  • the solution is rsfluxed for 1 to 2 hours, which is then cooled, followed by the addition of an acid .
  • Th resultant Al salt solution is quickly dried to afford an aluminum composition having high HPLC Bands ill and TV. During the spray drying of the solution, the loss of some chloride may be expected.
  • Process B involving a direct reaction with aluminum powder, about 25% - 35% by weight BAC solution is prepared first such that, initially the solution has an Al/iuii ide ratio of about 1.75 to about 1 .95 during the direct reaction between AI powder and aqueous aluminum halicie solution is conducted at tenipei-atures above 65 C.
  • An acid, such as AlCl;; is added ⁇ provide greater activation, and the solution is then processed through a drying operation.
  • a 25% - 40% by weight B AG solution is prepared through the reaction of aluminum powder with aqueous AIG3 solution at a temperature of greater than 65 C.
  • the solution generally has a ratio of Al/CI of about 1.2 to about 1 .8, preferably about 1 .4 to 1.7 with a 30% to 35% by weight concentration.
  • This solution is found to have a room temperature stability with respect to SEC-HPLC distribution of about one week and is readily dried to produce a powder product.
  • a polyhydric alcohol such as propylene glycol
  • the double activated aluminum solutions can be dried to powders by any appropriate means, including spray drying, freeze drying and vacuum drying. Spray drying is the most preferred method. Furthermore, the solutions can be dried into different densities and different shapes, such as low and high density spherical particles to better sun the variety of formulations, such as soft solids and low residue sticks, to which the powders of the invention may be applied.
  • the aluminum antiperspirant salts of the present invention are. characterized as follows:
  • the degree of the polymerization of aluminum complexes is determined by Size Exclusion CluOmatography (SEC) operated via a High Performance Liquid Chromatograph (HPLC) instrument.
  • SEC Size Exclusion CluOmatography
  • HPLC High Performance Liquid Chromatograph
  • Band I the highest molecular weight AI species are eluted first and are designated as Band I, which is equivalent to peaks 1 and 2; Band II (equivalent to peal 3) and Band ⁇ (equivalent to peak 4) are intermediate molecular weigh! AI compounds.
  • Band TV (equivalent to peak 5) is derived from the lowest molecular weight AI complexes, including monomers and climers.
  • Band V is derived from the chloride. The relative area of one or more peaks is determined in order to characterize the distribution of polymeric species in the aluminum complexes that are formed.
  • the aluminum antiperspirant salts according to the present invention have SEC-HPLC Band III to Band II area ratio of at least 0.7. and most preferably a! least 0.9.
  • Band IV content should be at least about 20%.
  • At least. 60%. and preferably at least about 70%, of the total SEC-HPLC band content, should be contained within Band ⁇ and Band IV.
  • These enhanced salts have a Band III content of at least 20%, and preferably at least 30%, of the total aluminum contained in all the peaks as measured by peak area.
  • a C ; column (150 x 4.0mm) from YMC. Inc., & Column Engineering Ci column ( 1 00 x 4.6mm) and a Liclirosorb Silica column (250 x 4.6mni ) connected in series is used to obtain the S BC-H PLC Chromatograras.
  • Each sample is dissolved in deionized water to form a 2% by weiglv. AI solution.
  • Each sample is filtered through a 0.45 ⁇ filter and chromatographed within 15 minutes using a O.OIN nitric acid solution as the mobile phase at a flow rate of 0.75 ml/minute.
  • the invention will be further illustrated by the following Examples. In the Examples, parts are by weight unless otherwise specified.
  • the " '%A.ST is the abbreviation of anhydrous solid excluding the bonded water in antiperspirant powder.
  • BAC solutions 20% by weight BAC solutions were prepared by diluting about 50% BAC solutions with water and refluxed for one hour. The results are as followed.
  • BAC solutions were prepared by diluting a 50% BAG solution which was refluxed for two hours. After the refluxed solutions were cooled, AlCH solutions (32 Be) were added to make the double activated Al solutions with both high HPLC Bands III and IV ft! different Al/C.l ratios, arid the solutions were spray dried.
  • Table I Fig. 1 illustrates the " ' ' A! NMR of the novel Al salt composition prepared under ExDerune.nl Number 3.
  • Each of the novel At salt compositions according to the present invention have pH (i5 w/w) values above 3.5 as illustrated in Table VI, and as such, afford skin friendly anriperspirant vehicles when formulated in aerosol stick and son solid products.

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
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  • Epidemiology (AREA)
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Abstract

L'invention concerne la production de nouvelles compositions antitranspiration à base d'aluminium à efficacité améliorée qui sont activées par la chaleur et un acide et contiennent des sels d'aluminium basiques de formule: Al2(OH)6-aXa , X représentant CI, Br, 1, ou NO3, a étant compris entre environ 1,1 et environ 1,7, le chlorure d'aluminium basique constituant le sel préféré. Lors de leur analyse par chromatographie sur gel-CLHP à une concentration d'environ 10% (par exemple, 2% d'Al) dans l'eau, ces compositions présentent une zone de bande I de chromatographie sur gel-CLHP inférieure à 10%, une zone de bande III d'au moins 20%, avec un rapport de zone de bandes III/II d'au moins 0,7, une zone de bande IV d'au moins 20%, et elles ont au moins 60% d'espèces d'aluminium contenues dans les bandes III et la bande IV.
PCT/US2007/070374 2007-11-19 2007-11-19 Compositions d'aluminium à efficacité améliorée présentant des bandes iii et iv de clhr élevées Ceased WO2013077832A2 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3112318A1 (fr) * 2015-06-30 2017-01-04 Gulbrandsen Technologies, Inc. Aluminium sesquichlorohydrate avec haute performance actif pour aérosol

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4859446A (en) * 1986-12-18 1989-08-22 Wickhen Products, Inc. Process for preparing basic aluminum compounds having increased sweat resistant activity
JPH0356411A (ja) * 1989-06-30 1991-03-12 Dow Corning Corp 活性化発汗抑制剤塩類の製造方法
US7087220B2 (en) * 2004-05-28 2006-08-08 Reheis, Inc. High pH antiperspirant compositions of enhanced efficacy

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3112318A1 (fr) * 2015-06-30 2017-01-04 Gulbrandsen Technologies, Inc. Aluminium sesquichlorohydrate avec haute performance actif pour aérosol
US9572758B2 (en) 2015-06-30 2017-02-21 Gulbrandsen Technologies, Inc. Method of making high performance activated aluminum sesquichlorohydrate powders
US9988281B2 (en) 2015-06-30 2018-06-05 Gulbrandsen Technologies, Inc. Method of making high performance activated aluminum sesquichlorohydrate powders
US10526210B2 (en) 2015-06-30 2020-01-07 Gulbrandsen Technologies, Inc. Method of making high performance activated aluminum sesquichlorohydrate powders

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