CA1111858A - Antiperspirants - Google Patents
AntiperspirantsInfo
- Publication number
- CA1111858A CA1111858A CA301,861A CA301861A CA1111858A CA 1111858 A CA1111858 A CA 1111858A CA 301861 A CA301861 A CA 301861A CA 1111858 A CA1111858 A CA 1111858A
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- Prior art keywords
- aluminium
- weight
- amino acid
- solution
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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
-
- 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
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Cosmetics (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Gelation of aqueous solutions and especially aqueous alcoholic solutions of the more active antiperspirant active compounds described in copending Canadian application No. 269,656 and comprising a basic aluminium chloride, bromide, iodide or nitrate having an aluminium to chloride, bromide, iodide or nitrate molar ratio of from 6.5 to 1.3:1 and which compound forms in water a solutions containing polymeric species of a size greater than 100 Angstroms within which species there is contained from 2 to 80% by weight or the total aluminium are inhibited by including in the solution a neutral amino acid.
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Gelation of aqueous solutions and especially aqueous alcoholic solutions of the more active antiperspirant active compounds described in copending Canadian application No. 269,656 and comprising a basic aluminium chloride, bromide, iodide or nitrate having an aluminium to chloride, bromide, iodide or nitrate molar ratio of from 6.5 to 1.3:1 and which compound forms in water a solutions containing polymeric species of a size greater than 100 Angstroms within which species there is contained from 2 to 80% by weight or the total aluminium are inhibited by including in the solution a neutral amino acid.
- 1 - /...
Description
This invention relates to antiperspirant active agents.
For inhibiting perspiration, the application to the ski~
of many different antiperspirant active compounds has been described in the literature. ~owever, those compounds most o widely used in commercial products at the present time are basic aluminium halides, especially aluminium chlorhydrate, which has an Al/Cl molar ratio of about 2. These active compounds are applied to the s~in ~rom a variety of applicator types including aerosol sprays, pump sprays, squeeze packs~ roll-on~ and stick.
applicators. Thus aluminium chlorhydrate~ ior e~ample, i9 employed as the active ingredient of various liquid, cream, stick or dry powder antiperspirant compositions. ~owever, in spite of tbe popularity of aluminium chlorhydrate the presently available products are capable of producing only limited reduction in perspiration.
In copending Canadian application No, 269,656 there is described an improved antiperspirsnt active compou~d whieb comprises a basic aluminium chloride, bromide, io~i~e and nitrate having an aluminium to chloride, bromide, iod,de or nitrate molar ratio of from 6.5 to 1.3:1, and which compou~d iorms in water a solution containing polymeric species of a size greater than 100 Angstroms within which specie~
there is containea at least 2% by ~eig~t of tbe total aluminium.
Since in aqueous solutions of the basic aluminium compounds the halide or nitrate i9 in ionic form the polymeric species present are hydroxy-aluminium species. ~he antiperspirant active compound may be employed in the form of an aqueous solution or _ 2 ~
~ 858 J ~3 the solution may be spray dried to give a hydrated compound of the empirical formula A12(0H)6_aXa'nH2 where X is Cl, Br9 I or N03 a is from about ~.3 to 1.5 n is from about 0.5 to 8.
As described in said copending application these special forms of basic aluminium compounds ~hich in aqueous solution contain polymeric species having a size greater than 100 Angstroms within which at least 2% by weight of the total aluminium is contained, may be prepared by hea,ting aqueous solutions of basic aluminium compounds at elevated temperature. The production of the desired species depends on the appropriate choice of the reaction conditions which are interrelat,ed. I+ is preferred -l,o use temperatures of from 80C to 140C. The period of heating may be shorter as higher temperatures are used, ranging for example from 0.5 hour to 30 days. Of importance is the concentration of the basic aluminium compound starting material.
The rate of production of the higher polymeric species of the basic aluminium compound decreases as the concentration of the solution is increased and at the above temperatures the concentration should be no more than al~out 35% by weight.
The present invention relates to an improvement in the antiperspirant agents described in the said copending application.
~111858 J ~93 According to the present invention there is provided an antiperspirant active agent comprising an aqueous solution of a basic aluminium chloride, bromide, iodide or nitrate having an aluminium to chloride, bromide, iodide or nitrate molar ratio of from 6.5 to 1.3:1 which solution contains species produced by said compound of a size greater than 100 Angstroms and within which species there is contained 2 to 80,~ by weight of the total aluminium, and which solution also contains a neutral-amino acid.
By a neutral amino ac1d is- meant an amino acid containing an equal number of unneutralised amino and acidic groups.
Preferred amino acids contain 2 to 1~ carbon atoms examples of which are glycine, sarcosine, alanine, phenylalanine, valine, leucine, methionine, taurine, ornithine monohydrochloride and glutamic acid monomethyl ester. By the addition of a neutral amino acid reduction of solu'ion viscosity may be effected and gelling inhibited. The arnino acid can also be used to increase the pH of the solution reducing any tendency of the solution to cause irritation of the skin or corrosior~ of metal containers in which it might be contained. In the case of powders ~0 obtained from these solutions the amino acid may act to inhibit corrosion of metal containers.
The amount of the amino acid is preferably such that the aluminium to amino acid molar ratio is from 20:1 to 1:1.
The basic aluminium compound preferahly has an aluminium to chloride, bromide, iodide or nitrate molar ratio of from -~to 1.3:1, more particularly 2.~ to 1.6:1.
~111858 J.~g3 The weight of the aluminium in the species having an effective diameter above 100 Angstroms is preferably 5 to 60Q/o of the total aluminium.
The aqueous solution of the active antiperspirant agent comprising the higher polymeric species as defined, may, if desired, be evaporated to concentrate the solution or it may be dried to give a solid hydrated material. ~s with ordinary aluminium chlorhydrate, for example, drying conditions which lead to both the loss of water of condensation and hydrochloric acid should be avoided as these may lead to irreversible degradation of the basic aluminium compound. Any suitable method of drying may be used, spray drying being a particularly useful method. The spray drying method described in US Patent No.3,887,692 may be employed. The solid material may be ground or milled as required, more particu]arly to a particle size below 100 microns such that the particulate compound is suitable for use in an aerosol powder spray product. Drying should be effected in such manner as to give a product having a water content consistent with the following e~pirical formula ~l2(OH)6 aXa.nH20.(Amino acid)m where X is Cl, ~r, I or ~-03, a is fron about 0.3 to 1.5, n is from about 0.5 to 8, preferably ~..5 to ~, and m indicates the amount of amino acid and is preferably about ~.1 to 2.
The invention in another aspect also relates to these no~el solid antiperspirant acti~e complex materials.
T~e powdered complex obtained on drying has superior characteristics, not possessed when the components are dried ~ 58 J-~93 separately and combined in the dried state by simple physical mi,Yi ng .
The compositions of the invention may be made by dissolving the amino aeid in the solution of the basic aluminium compound eontaining the polymerie speeies greater than 10~ Angst,roms prepared as described in the above copendin.g application.
Alt,ernat,ively t,he amino aeid may be included in a solution made up ~rom the powder obtained by drying the solution prepared .aecording to t~e~above copending application. The anti-perspirant acf,ive agent,s of t,his invention may also be produced r1~ Uo. ~0/~
` by the process of our concurrently filed~application~entitled "Antiperspirants" (J.l~). This latter applieation relat,es to a proeess for producing an æntiperspir~n-t active material comprising heating an aqueous solution of a mixture of a basic 1~ aluminium chloric,3e, bromide, iodide or nitrate having an aluminium to chloride, bromide, iodide or nitrate molar ratio o~
6.5 to 1.3:1 and an amino acid, the concentration of the basic aluminium compouncd in such solution and the temperature and time of heat,ing the solution being such tha-~ t,here i9 produced. in the solution polymeric species havin~ a size great,er than 10~
Angstroms 9 s~id species being produced in such amount, that from
For inhibiting perspiration, the application to the ski~
of many different antiperspirant active compounds has been described in the literature. ~owever, those compounds most o widely used in commercial products at the present time are basic aluminium halides, especially aluminium chlorhydrate, which has an Al/Cl molar ratio of about 2. These active compounds are applied to the s~in ~rom a variety of applicator types including aerosol sprays, pump sprays, squeeze packs~ roll-on~ and stick.
applicators. Thus aluminium chlorhydrate~ ior e~ample, i9 employed as the active ingredient of various liquid, cream, stick or dry powder antiperspirant compositions. ~owever, in spite of tbe popularity of aluminium chlorhydrate the presently available products are capable of producing only limited reduction in perspiration.
In copending Canadian application No, 269,656 there is described an improved antiperspirsnt active compou~d whieb comprises a basic aluminium chloride, bromide, io~i~e and nitrate having an aluminium to chloride, bromide, iod,de or nitrate molar ratio of from 6.5 to 1.3:1, and which compou~d iorms in water a solution containing polymeric species of a size greater than 100 Angstroms within which specie~
there is containea at least 2% by ~eig~t of tbe total aluminium.
Since in aqueous solutions of the basic aluminium compounds the halide or nitrate i9 in ionic form the polymeric species present are hydroxy-aluminium species. ~he antiperspirant active compound may be employed in the form of an aqueous solution or _ 2 ~
~ 858 J ~3 the solution may be spray dried to give a hydrated compound of the empirical formula A12(0H)6_aXa'nH2 where X is Cl, Br9 I or N03 a is from about ~.3 to 1.5 n is from about 0.5 to 8.
As described in said copending application these special forms of basic aluminium compounds ~hich in aqueous solution contain polymeric species having a size greater than 100 Angstroms within which at least 2% by weight of the total aluminium is contained, may be prepared by hea,ting aqueous solutions of basic aluminium compounds at elevated temperature. The production of the desired species depends on the appropriate choice of the reaction conditions which are interrelat,ed. I+ is preferred -l,o use temperatures of from 80C to 140C. The period of heating may be shorter as higher temperatures are used, ranging for example from 0.5 hour to 30 days. Of importance is the concentration of the basic aluminium compound starting material.
The rate of production of the higher polymeric species of the basic aluminium compound decreases as the concentration of the solution is increased and at the above temperatures the concentration should be no more than al~out 35% by weight.
The present invention relates to an improvement in the antiperspirant agents described in the said copending application.
~111858 J ~93 According to the present invention there is provided an antiperspirant active agent comprising an aqueous solution of a basic aluminium chloride, bromide, iodide or nitrate having an aluminium to chloride, bromide, iodide or nitrate molar ratio of from 6.5 to 1.3:1 which solution contains species produced by said compound of a size greater than 100 Angstroms and within which species there is contained 2 to 80,~ by weight of the total aluminium, and which solution also contains a neutral-amino acid.
By a neutral amino ac1d is- meant an amino acid containing an equal number of unneutralised amino and acidic groups.
Preferred amino acids contain 2 to 1~ carbon atoms examples of which are glycine, sarcosine, alanine, phenylalanine, valine, leucine, methionine, taurine, ornithine monohydrochloride and glutamic acid monomethyl ester. By the addition of a neutral amino acid reduction of solu'ion viscosity may be effected and gelling inhibited. The arnino acid can also be used to increase the pH of the solution reducing any tendency of the solution to cause irritation of the skin or corrosior~ of metal containers in which it might be contained. In the case of powders ~0 obtained from these solutions the amino acid may act to inhibit corrosion of metal containers.
The amount of the amino acid is preferably such that the aluminium to amino acid molar ratio is from 20:1 to 1:1.
The basic aluminium compound preferahly has an aluminium to chloride, bromide, iodide or nitrate molar ratio of from -~to 1.3:1, more particularly 2.~ to 1.6:1.
~111858 J.~g3 The weight of the aluminium in the species having an effective diameter above 100 Angstroms is preferably 5 to 60Q/o of the total aluminium.
The aqueous solution of the active antiperspirant agent comprising the higher polymeric species as defined, may, if desired, be evaporated to concentrate the solution or it may be dried to give a solid hydrated material. ~s with ordinary aluminium chlorhydrate, for example, drying conditions which lead to both the loss of water of condensation and hydrochloric acid should be avoided as these may lead to irreversible degradation of the basic aluminium compound. Any suitable method of drying may be used, spray drying being a particularly useful method. The spray drying method described in US Patent No.3,887,692 may be employed. The solid material may be ground or milled as required, more particu]arly to a particle size below 100 microns such that the particulate compound is suitable for use in an aerosol powder spray product. Drying should be effected in such manner as to give a product having a water content consistent with the following e~pirical formula ~l2(OH)6 aXa.nH20.(Amino acid)m where X is Cl, ~r, I or ~-03, a is fron about 0.3 to 1.5, n is from about 0.5 to 8, preferably ~..5 to ~, and m indicates the amount of amino acid and is preferably about ~.1 to 2.
The invention in another aspect also relates to these no~el solid antiperspirant acti~e complex materials.
T~e powdered complex obtained on drying has superior characteristics, not possessed when the components are dried ~ 58 J-~93 separately and combined in the dried state by simple physical mi,Yi ng .
The compositions of the invention may be made by dissolving the amino aeid in the solution of the basic aluminium compound eontaining the polymerie speeies greater than 10~ Angst,roms prepared as described in the above copendin.g application.
Alt,ernat,ively t,he amino aeid may be included in a solution made up ~rom the powder obtained by drying the solution prepared .aecording to t~e~above copending application. The anti-perspirant acf,ive agent,s of t,his invention may also be produced r1~ Uo. ~0/~
` by the process of our concurrently filed~application~entitled "Antiperspirants" (J.l~). This latter applieation relat,es to a proeess for producing an æntiperspir~n-t active material comprising heating an aqueous solution of a mixture of a basic 1~ aluminium chloric,3e, bromide, iodide or nitrate having an aluminium to chloride, bromide, iodide or nitrate molar ratio o~
6.5 to 1.3:1 and an amino acid, the concentration of the basic aluminium compouncd in such solution and the temperature and time of heat,ing the solution being such tha-~ t,here i9 produced. in the solution polymeric species havin~ a size great,er than 10~
Angstroms 9 s~id species being produced in such amount, that from
2 to ~ by ~;eight of the total aluminium is contained within such species.
~he anti.perspirant agent of t,he invent,ion may he employecl 2a directly as an antiperspirant composition ~n the form o. the solution, or it may he used in ~nti.perspir~nt composit,ions in the form of a po~der ohtained from suoh so3.ution, or again as a ~111858 J.493 solution obtained from such powder. Various examples of suitable antiperspirant compositions are described in the copending application referred to above.
Thus in accordance with one aspect of the invention there is provided an antiperspirant composition comprising an aqueous solution of the basic aluminium compound and ~lino acid according to the invention in combination with an adjunct which is a perfume, thickener, alcohol or propellant. The anti-perspirant composition may be in the form of a lotion comprising an aqueous or aqueous alcoholic solution of the basic aluminium compound in a concentration of from 1 to 30C,io by ~eight and 0.1 to 5~o by ~eight of a thickening agent. Suitable thickening agents for antiperspirant lotions are well known to those skilled in tlle art, and include for example, magnesiuln aluminium silicates. Thickening may also be effected by emu]sifying an oil or the like in the composition. Furthermore, the composition may comprise an aqueous or aqueou.s alcoholic solution of the basic aluminium compoun~l in a concentration of from 1 to 30C/c by weight, the amino acid an~ from 0.3 to 2% hy weight of perfume.
The composition may comprise an aqueous alcoholic solution of the basic aluminium compound and neutral amino acid containing up to 75% by weight of a Cl-C3 aliphatic alcohol. These aqueous alcoholic connpositions preferably contain ethanol, propanol, isopropanol or a mixture thereof as the alcohol.
The amino acid is particularly useful ~-ith ayueous a]coholic solutions of the basic aluminiu~n compound since such solutiolls _ 7 ~
~1~18S8 ~ 493 have a greater propensity to gel than simple aqueous solutions.
Antiperspirant compositions comprising an aqueous solution of the basic aluminium compound and the amino acid may contain from about 1 to 80% by l~eight of a propellant.
The antiperspirant composition may also comprise in combination a powdered antiperspirant active material obtained by drying the antiperspirant active solution of the invention and a powdered inert solid diluent or organic liquid carrier.
The composition may be in the form of a powder aerosol composition comprising a suspension of the powdered basic aluminium compound/amino acicl complex in a liquid carrierj said composition also comprising a propellant. In particular the composition may be in the form of a powder aerosol composition comprising A. from about 1% to about 12% by weight of said basic aluminium compound/amino acid ma-terial in powder form;
B. from about ~.1% to about 5~b by weight of a suspending agent;
C. from about 1% to about 15~o by weight of a carrier liquid; and D. from about 70,~o to about 9~Ço by weight of a propellant.
111~858 PJ ~93 The carrier liquid may for example be a non-volatile non-hygroscopic liquid as suggested in US Patent No.3,964,203.
Especially useful are carrier liquids which have emollient properties and a number of these are referred to in British Patent Specification No 1,393,860. Especially preferred are fatty acid esters such as isopropyl myristate and those esters referred to in British Patent Specification No.193539914 such as dibutyl phthalate and diisopropyl adipate.
Various other carrier liquids for po~der suspension aerosols are suggested in US Patent Specifications ~os.
39833~721~ 3,8339720~ 39920,807~ 3,949,066 and 3,~74,270 and in British Patent Specifications Nos.1,341,7~8, 1,3~0,26~, 1,369,872 and 19411,547. Volatile carrier liquids may also be used such as ethanol or a volatile silicone as described in South African and British Patent Specifications ~os.75/3576 and 1,467,676, respectively.
The ratio of total solids in the compositions to the carrier liquid may vary over a wide range, for example from 0.1 to 3 parts of the powder per part by weight of the carrier liquid.
The propellant can he a liquefied hydrocarbon9 halogenated hydrocarbon or a mixture thereof. Examples of materials that are suitable for use as propellants are given in the above-mentioned patents and include trichloro~luoromethane, dichloro-difluoromethane, dichlorotetrafluoroethane, monochlorodifluoro-methane, trichlorotrifluoroethane, propane, butane, 1,1-di~:luoro-ethane, 191-difluoro-1-chloroethane, dichloromonofluoromethane, methyle~e chloride, isopentane and isobutane, used singly or g 1111858 PJ.493 admixed. Trichlorofluoromethane, dichlorodifluoromethane, dichlorotetrafluoroethane, and isobutane, used singly or admixed, are preferred.
E~amples of materials that are suitable for use as permanent gas propellants are nitrogen, carbon dioxide and nitrous oxide.
It is common practice to include in aerosol powder-spray compositions a material to assist in the suspending of the powder in the liquid vehicle. The materials prevent compacting of the powder and they may also act as thickening or gelling agents for the liquid vehicle. ~specially preferred are hydrophobic clays and colloidal silicas. Hydrophobic clays are available under the trade name Bentone, eg Bentone 34 or Bentone 38, and their use as suspending agents are described in a n.umber o~ patent specifications including US Patent Specification No.397739683. Sui.table colloidal silicas sB include Aerosil~200 and ab-0-Sil M-5 as well as other gradea.
The antiperspirant composition may simply comprise from 5 to 40~ by weight of the ami.no acid-containing aluminium compouncl in powder ~orm~ the remainder consisting essenti.ally of an inert powder material, such as talc or starch, for example.
The invention also relates to packages consisting of the comhination o~ an antiperspirant co~position co~prising an antiperspirant active agent according to -the i~vention and an applicator for applying the antiperspirant compcsi~ion to the skin. The pac~age may ~e one in ~.hich ~he applicator is a container fitted with a valve for dis~ensing liquid in aerosol ~t~s t~e~r~
-- 1 0 -- ~
1~1858 form and the antiperspirant composition comprises a suspension of the antiperspirant active agent in particulate form in a liquid carrier which may be in admixture with a propellant.
Furthermore, the package may be one wherein the applicator is a container ~itted with a valve for dispensing liquid in aerosol form and the antiperspirant comp~sition comprises an aqueous or aqueous alcoholic solution of the hasic aluminium compound and amino acid. In this case the aqueous solution may be discharged by a propellant gas or by a finger-operated pump mechanism or by containing the composition within a container of pliable material ~hereby by squeezing the container the composition is expelled through the spray valve. Another form of package is one in which the applicator is a roll-on applicator and the antiperspirant composition comprises an aqueous or aqueous alcoholic solution of the antiperspirant active material and amino acid. Furthermore9 the package may be one wherein the applicator is an applicator for dispensing a powdered material and the antiperspirant composition is a powdered compos ition including the basic aluminium compollnd/
amino acid complex in powder form. The applicator may also be a stick applicator for holding an antiperspirant composition in the form of a stick or it may be tissue or cloth which is impregnated with the antiperspirant active material.
The invention also relates to a method o~ inhibiting the exudation of perspiration comprising applying the amino aci~
containing polymeric aluminium antiperspirant active material to the skln.
~111858 pJ ~93 Determination of Percentage Aluminium in Polymeric Species havin~ a size ~reater than 100 An stroms The heat treated basic aluminium compounds described herein were defined by molecular sieve chro~atography. For this purpose there was used a 1.2 m x 6.0 mm column packed with spherical porous silica beads of particle size 75-125 microns, and of surface area 350-5~ m /g, and having a maximum pore size of 100 Angstroms. The silica employed, available D ~
; commercially as Porasil AX~.had been deactivated to eliminate adsorption in ~olecular size separations. The use of Porasil silica beads as a column packing in chromatography is referred to in "Gel Permeation Chromatography" by K.H. Altgelt and L. Segan, 1971, pages 16 to 18. The silica was conditioned before use by passage of a single large sample (eg 0.5 ml of a 2/o W/w solution) of a heat frea~ed aluminium chlorhydra+e.
Samples to be tested were dissolved in deionized water to approximately ~.2 ~l aluminium and thoroughly dispersed by treatment (4 minutes) with a sonic probe. About 0.1 ml samples of approximately 0.2 M aluminium solutions were applied to the column by a sample loop system and eluted ~iith 1~ l'l aqueous hydrochloric acid solution using a peristaltic pump. A
differential refractive index monitor linked to a pen recorder was used to detect fractions as they were eluted. These ~ractions were collected and analysed for aluminium by atomic absorption. Complete elution of all aluminium applied in each sample was checked by direct analysis of another sample of the same volume. The perc~ntage of the total aluminium s~hich appeared in the fraction eluted at the void volume of the column ~e~es ~~-v~e ~
- 12 _ ~111858 pJ,493 was considered as that deriving from polymeric material of a size greater than 100 Angstroms in effective diameter. None of this polymeric material was found in any untreated aluminium chlorhydrate solutions.
Determination of Water Content of Powdered Materials __ __ _ _._ The water content of powdered materials was estimated by thermogravimetric analysis (TGA). On heating to 1,000C, aluminium chlorhydrate undergoes the following reaction:
A12(0H)5cl(H2o)x Al23 + HC1~ + (x + 2~H2o~
From a knowledge of Al/Cl ratio of the material (and hence the empirical weight of the anhydrous Al2(0H)6_aCla) it is poss to calculate the number of moles of water (x) associated with each anhydrous unit from an accurate determination of the weight loss on heating a kno~-n weight of samp]e to 1,000C.
The following equation shows the method of calculation:
Wei~llt of solid before heati_~ 102~ Empirical weight x ~ Weight of solid after heating x J of anhydrous ~Al2(OH)6 aCla~
The percentage of water is given by 1080~x Empirical weight of anhydrous A12(H)6-aCla + 1~
~he following Examples illustrate the invention. Percentages are by ~ieight.
_xample 1_ A ~atch of aluminium chlorhydrate ha~in~ an Al/Cl molar - ratio of 2.~4 and a water content of 1~.5,' was dissolved in deionized water to give a 10,b solution. This solution was 30 heated in 1 litre screw cap glass bot-tles to 9~-100C over 10 11~1858 J 493 hours and then held at this temperature for a further 38 hours.
The resulting solution was cooled to room temperature and found to con-tain 23. 9/0 of the total aluminium as polymers exceeding 10~ Angstroms in effective diameter. This solution was then spray dried and the powder sieved to obtain the fraction between 30-50 microns9 with a water content of 14.3%. A
solution possessing antiperspirant properties was formulated - containing 17.5% of the spray dried powder described above~ and 5% glycine, the total being made up with deionized water. The glycine prevented gelation of the solution.
Ex_mples 2 to 19 A number of aqueous alcoholic solutions of a neutral amino acid and the powder obtained as described in Example 1 were made up. They were prepared by mixing ethanol ( 30%) with the 15 powder (15%) -to form a slurry to which was added the neutral amino acid (5%) followed by the water which made up the balance of the composition. The neutral amino acids e~lployed are given below.
~111858 J.4g3 Example Neutral Amino Acid 2 Glycine
~he anti.perspirant agent of t,he invent,ion may he employecl 2a directly as an antiperspirant composition ~n the form o. the solution, or it may he used in ~nti.perspir~nt composit,ions in the form of a po~der ohtained from suoh so3.ution, or again as a ~111858 J.493 solution obtained from such powder. Various examples of suitable antiperspirant compositions are described in the copending application referred to above.
Thus in accordance with one aspect of the invention there is provided an antiperspirant composition comprising an aqueous solution of the basic aluminium compound and ~lino acid according to the invention in combination with an adjunct which is a perfume, thickener, alcohol or propellant. The anti-perspirant composition may be in the form of a lotion comprising an aqueous or aqueous alcoholic solution of the basic aluminium compound in a concentration of from 1 to 30C,io by ~eight and 0.1 to 5~o by ~eight of a thickening agent. Suitable thickening agents for antiperspirant lotions are well known to those skilled in tlle art, and include for example, magnesiuln aluminium silicates. Thickening may also be effected by emu]sifying an oil or the like in the composition. Furthermore, the composition may comprise an aqueous or aqueou.s alcoholic solution of the basic aluminium compoun~l in a concentration of from 1 to 30C/c by weight, the amino acid an~ from 0.3 to 2% hy weight of perfume.
The composition may comprise an aqueous alcoholic solution of the basic aluminium compound and neutral amino acid containing up to 75% by weight of a Cl-C3 aliphatic alcohol. These aqueous alcoholic connpositions preferably contain ethanol, propanol, isopropanol or a mixture thereof as the alcohol.
The amino acid is particularly useful ~-ith ayueous a]coholic solutions of the basic aluminiu~n compound since such solutiolls _ 7 ~
~1~18S8 ~ 493 have a greater propensity to gel than simple aqueous solutions.
Antiperspirant compositions comprising an aqueous solution of the basic aluminium compound and the amino acid may contain from about 1 to 80% by l~eight of a propellant.
The antiperspirant composition may also comprise in combination a powdered antiperspirant active material obtained by drying the antiperspirant active solution of the invention and a powdered inert solid diluent or organic liquid carrier.
The composition may be in the form of a powder aerosol composition comprising a suspension of the powdered basic aluminium compound/amino acicl complex in a liquid carrierj said composition also comprising a propellant. In particular the composition may be in the form of a powder aerosol composition comprising A. from about 1% to about 12% by weight of said basic aluminium compound/amino acid ma-terial in powder form;
B. from about ~.1% to about 5~b by weight of a suspending agent;
C. from about 1% to about 15~o by weight of a carrier liquid; and D. from about 70,~o to about 9~Ço by weight of a propellant.
111~858 PJ ~93 The carrier liquid may for example be a non-volatile non-hygroscopic liquid as suggested in US Patent No.3,964,203.
Especially useful are carrier liquids which have emollient properties and a number of these are referred to in British Patent Specification No 1,393,860. Especially preferred are fatty acid esters such as isopropyl myristate and those esters referred to in British Patent Specification No.193539914 such as dibutyl phthalate and diisopropyl adipate.
Various other carrier liquids for po~der suspension aerosols are suggested in US Patent Specifications ~os.
39833~721~ 3,8339720~ 39920,807~ 3,949,066 and 3,~74,270 and in British Patent Specifications Nos.1,341,7~8, 1,3~0,26~, 1,369,872 and 19411,547. Volatile carrier liquids may also be used such as ethanol or a volatile silicone as described in South African and British Patent Specifications ~os.75/3576 and 1,467,676, respectively.
The ratio of total solids in the compositions to the carrier liquid may vary over a wide range, for example from 0.1 to 3 parts of the powder per part by weight of the carrier liquid.
The propellant can he a liquefied hydrocarbon9 halogenated hydrocarbon or a mixture thereof. Examples of materials that are suitable for use as propellants are given in the above-mentioned patents and include trichloro~luoromethane, dichloro-difluoromethane, dichlorotetrafluoroethane, monochlorodifluoro-methane, trichlorotrifluoroethane, propane, butane, 1,1-di~:luoro-ethane, 191-difluoro-1-chloroethane, dichloromonofluoromethane, methyle~e chloride, isopentane and isobutane, used singly or g 1111858 PJ.493 admixed. Trichlorofluoromethane, dichlorodifluoromethane, dichlorotetrafluoroethane, and isobutane, used singly or admixed, are preferred.
E~amples of materials that are suitable for use as permanent gas propellants are nitrogen, carbon dioxide and nitrous oxide.
It is common practice to include in aerosol powder-spray compositions a material to assist in the suspending of the powder in the liquid vehicle. The materials prevent compacting of the powder and they may also act as thickening or gelling agents for the liquid vehicle. ~specially preferred are hydrophobic clays and colloidal silicas. Hydrophobic clays are available under the trade name Bentone, eg Bentone 34 or Bentone 38, and their use as suspending agents are described in a n.umber o~ patent specifications including US Patent Specification No.397739683. Sui.table colloidal silicas sB include Aerosil~200 and ab-0-Sil M-5 as well as other gradea.
The antiperspirant composition may simply comprise from 5 to 40~ by weight of the ami.no acid-containing aluminium compouncl in powder ~orm~ the remainder consisting essenti.ally of an inert powder material, such as talc or starch, for example.
The invention also relates to packages consisting of the comhination o~ an antiperspirant co~position co~prising an antiperspirant active agent according to -the i~vention and an applicator for applying the antiperspirant compcsi~ion to the skin. The pac~age may ~e one in ~.hich ~he applicator is a container fitted with a valve for dis~ensing liquid in aerosol ~t~s t~e~r~
-- 1 0 -- ~
1~1858 form and the antiperspirant composition comprises a suspension of the antiperspirant active agent in particulate form in a liquid carrier which may be in admixture with a propellant.
Furthermore, the package may be one wherein the applicator is a container ~itted with a valve for dispensing liquid in aerosol form and the antiperspirant comp~sition comprises an aqueous or aqueous alcoholic solution of the hasic aluminium compound and amino acid. In this case the aqueous solution may be discharged by a propellant gas or by a finger-operated pump mechanism or by containing the composition within a container of pliable material ~hereby by squeezing the container the composition is expelled through the spray valve. Another form of package is one in which the applicator is a roll-on applicator and the antiperspirant composition comprises an aqueous or aqueous alcoholic solution of the antiperspirant active material and amino acid. Furthermore9 the package may be one wherein the applicator is an applicator for dispensing a powdered material and the antiperspirant composition is a powdered compos ition including the basic aluminium compollnd/
amino acid complex in powder form. The applicator may also be a stick applicator for holding an antiperspirant composition in the form of a stick or it may be tissue or cloth which is impregnated with the antiperspirant active material.
The invention also relates to a method o~ inhibiting the exudation of perspiration comprising applying the amino aci~
containing polymeric aluminium antiperspirant active material to the skln.
~111858 pJ ~93 Determination of Percentage Aluminium in Polymeric Species havin~ a size ~reater than 100 An stroms The heat treated basic aluminium compounds described herein were defined by molecular sieve chro~atography. For this purpose there was used a 1.2 m x 6.0 mm column packed with spherical porous silica beads of particle size 75-125 microns, and of surface area 350-5~ m /g, and having a maximum pore size of 100 Angstroms. The silica employed, available D ~
; commercially as Porasil AX~.had been deactivated to eliminate adsorption in ~olecular size separations. The use of Porasil silica beads as a column packing in chromatography is referred to in "Gel Permeation Chromatography" by K.H. Altgelt and L. Segan, 1971, pages 16 to 18. The silica was conditioned before use by passage of a single large sample (eg 0.5 ml of a 2/o W/w solution) of a heat frea~ed aluminium chlorhydra+e.
Samples to be tested were dissolved in deionized water to approximately ~.2 ~l aluminium and thoroughly dispersed by treatment (4 minutes) with a sonic probe. About 0.1 ml samples of approximately 0.2 M aluminium solutions were applied to the column by a sample loop system and eluted ~iith 1~ l'l aqueous hydrochloric acid solution using a peristaltic pump. A
differential refractive index monitor linked to a pen recorder was used to detect fractions as they were eluted. These ~ractions were collected and analysed for aluminium by atomic absorption. Complete elution of all aluminium applied in each sample was checked by direct analysis of another sample of the same volume. The perc~ntage of the total aluminium s~hich appeared in the fraction eluted at the void volume of the column ~e~es ~~-v~e ~
- 12 _ ~111858 pJ,493 was considered as that deriving from polymeric material of a size greater than 100 Angstroms in effective diameter. None of this polymeric material was found in any untreated aluminium chlorhydrate solutions.
Determination of Water Content of Powdered Materials __ __ _ _._ The water content of powdered materials was estimated by thermogravimetric analysis (TGA). On heating to 1,000C, aluminium chlorhydrate undergoes the following reaction:
A12(0H)5cl(H2o)x Al23 + HC1~ + (x + 2~H2o~
From a knowledge of Al/Cl ratio of the material (and hence the empirical weight of the anhydrous Al2(0H)6_aCla) it is poss to calculate the number of moles of water (x) associated with each anhydrous unit from an accurate determination of the weight loss on heating a kno~-n weight of samp]e to 1,000C.
The following equation shows the method of calculation:
Wei~llt of solid before heati_~ 102~ Empirical weight x ~ Weight of solid after heating x J of anhydrous ~Al2(OH)6 aCla~
The percentage of water is given by 1080~x Empirical weight of anhydrous A12(H)6-aCla + 1~
~he following Examples illustrate the invention. Percentages are by ~ieight.
_xample 1_ A ~atch of aluminium chlorhydrate ha~in~ an Al/Cl molar - ratio of 2.~4 and a water content of 1~.5,' was dissolved in deionized water to give a 10,b solution. This solution was 30 heated in 1 litre screw cap glass bot-tles to 9~-100C over 10 11~1858 J 493 hours and then held at this temperature for a further 38 hours.
The resulting solution was cooled to room temperature and found to con-tain 23. 9/0 of the total aluminium as polymers exceeding 10~ Angstroms in effective diameter. This solution was then spray dried and the powder sieved to obtain the fraction between 30-50 microns9 with a water content of 14.3%. A
solution possessing antiperspirant properties was formulated - containing 17.5% of the spray dried powder described above~ and 5% glycine, the total being made up with deionized water. The glycine prevented gelation of the solution.
Ex_mples 2 to 19 A number of aqueous alcoholic solutions of a neutral amino acid and the powder obtained as described in Example 1 were made up. They were prepared by mixing ethanol ( 30%) with the 15 powder (15%) -to form a slurry to which was added the neutral amino acid (5%) followed by the water which made up the balance of the composition. The neutral amino acids e~lployed are given below.
~111858 J.4g3 Example Neutral Amino Acid 2 Glycine
3 c~._Alanine
4 ~_Alanine Taurine 6 Serine 7 Sarcosine 8 Valine g Leucine Proline 11 Methionine 12 Threonine 13 Lysine monohydrochloride 14 Ornithine monohydrochloride Glutamic acid ~-methyl ester 16 CX-~mino_n-butyric acid 17 ~-Amino-n-butyric acid 18 5-Amino-caproic acid 19 ~-Amino-caprylic acid In each case the neutral amino acid prevented gelation of the solution, effectiveness being independent of the isomeric form of the acids. When the amino acid was omitted gelation occurred on standing. Amino acids other than neutral amino acids failed to prevent gelation as shown by the use at the s~le level of lysine, ar~inine, aspartic acid and glutamic acid which were ineffective.
~1~1858 J.493 Exa~les 20 to 22 The following examples illustrate the use of neutral amino acids in solutions containing higher concentrations of ethanol.
These solutions were prepared as before from ethanol, anti-
~1~1858 J.493 Exa~les 20 to 22 The following examples illustrate the use of neutral amino acids in solutions containing higher concentrations of ethanol.
These solutions were prepared as before from ethanol, anti-
5 perspirant powder (15%) a~d neutral amino acid (5%) with watermaking up the balance. The concentrations of ethanol and the neutral amino acids employed are indicated below.
Example LEthanol Ne~tral Amino Acid Ornithine monohydrochloride 2i 50 Leucine 22 60 Valine In each case the neutral amino acid prevented gelation of the solution.
Example 23 70 kg of an aluminium chlorhydrate having an Al/Cl molar ratio of l.9i and a water content of 1~.~h was dissolved in 630 kg of deionized water at 45C and stirred and heated to 120C in a stainless steel reactor over 3.75 hours. Stirring and heating at this temperature was maintained for a further 5.5 hours before cooling rapidly to 70C and more slowly to ambient temperature. The resulting solution contained 41.0%
of the total aluminium as polymers with effective diameters exceeding 100 Angstroms. To a batch ol this solution sufficient glycine was added to give a 70,b glycine solution~
with aluminium:glycine molar ratio of unity. The resultant solution was then spray dried using inlet and outlet temperatures of 250C and 95C9 respectively. A l7.50,b aqueous solution was - 16 _ /
~ 8S~ J 493 made up from this powder and it did not gel. A 17.5% solution made from powder prepared as above without the addition of the glycine did gel.
_ 17 -
Example LEthanol Ne~tral Amino Acid Ornithine monohydrochloride 2i 50 Leucine 22 60 Valine In each case the neutral amino acid prevented gelation of the solution.
Example 23 70 kg of an aluminium chlorhydrate having an Al/Cl molar ratio of l.9i and a water content of 1~.~h was dissolved in 630 kg of deionized water at 45C and stirred and heated to 120C in a stainless steel reactor over 3.75 hours. Stirring and heating at this temperature was maintained for a further 5.5 hours before cooling rapidly to 70C and more slowly to ambient temperature. The resulting solution contained 41.0%
of the total aluminium as polymers with effective diameters exceeding 100 Angstroms. To a batch ol this solution sufficient glycine was added to give a 70,b glycine solution~
with aluminium:glycine molar ratio of unity. The resultant solution was then spray dried using inlet and outlet temperatures of 250C and 95C9 respectively. A l7.50,b aqueous solution was - 16 _ /
~ 8S~ J 493 made up from this powder and it did not gel. A 17.5% solution made from powder prepared as above without the addition of the glycine did gel.
_ 17 -
Claims (5)
1. An antiperspirant active agent comprising a 1 to 30% by weight aqueous solution of a basic aluminium chloride, bromide, iodide or nitrate having an aluminium to chloride, bromide, iodide or nitrate molar ratio of from 6.5 to 1.3:1 which solution contains polymeric species of a size greater than 100 Angstroms and within which species there is contained 2 to 80% by weight of the total aluminium, and which solution also contains a neutral amino acid containing 2 to 10 carbon atoms in such amount that the aluminium to amino acid molar ratio is from 20:1 to 1:1.
2. An antiperspirant active agent as claimed in Claim 1, wherein the amino acid is glycine, sarcosine, alanine, phenylalanine, valine, leucine, methionine, taurine, ornithine monohydrochloride or glutamic acid monomethyl ester.
3. An antiperspirant active agent as claimed in Claim 1, wherein the weight of the aluminium in the species having a size greater than 100 Angstroms is 5 to 60% of the total weight of the aluminium.
4. An antiperspirant active agent as claimed in any of the claims 1 to 3 additionally comprising up to 75% by weight of a C1-C3 aliphatic alcohol.
5. A solid antiperspirant active complex material having the empirical formula Al2(OH)6-aXa.nH2O.(Neutral amino acid)m where X is Cl, Br, I or NO3, a is from about 0.3 to 1.5, n is from about 0.5 to 8, and m is from 0.1 to 2, said solid complex on dissolving in water forming species having a size greater than 100 Angstroms within which species there is contained 2 to 80% by weight of the total aluminium.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB17344/77 | 1977-04-26 | ||
| GB1734477A GB1597497A (en) | 1977-04-26 | 1977-04-26 | Antiperspirants |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1111858A true CA1111858A (en) | 1981-11-03 |
Family
ID=10093533
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA301,861A Expired CA1111858A (en) | 1977-04-26 | 1978-04-25 | Antiperspirants |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS53136530A (en) |
| CA (1) | CA1111858A (en) |
| DE (1) | DE2818321A1 (en) |
| FR (1) | FR2388554A1 (en) |
| GB (1) | GB1597497A (en) |
| IE (1) | IE46799B1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8410403D0 (en) * | 1984-04-24 | 1984-05-31 | Unilever Plc | Antiperspirant product |
| FR2636238B1 (en) * | 1988-09-14 | 1994-01-21 | Morelle Jean | NEW ANTISUDORAL COMPOSITIONS |
| US5643559A (en) * | 1991-10-30 | 1997-07-01 | Colgate-Palmolive Company | Deodorant compositions comprising inhibitors of odor-producing axillary bacterial exoenzymes |
| JPH0546128U (en) * | 1991-11-13 | 1993-06-18 | 株式会社精工舎 | Electric field strength display |
| GB9604340D0 (en) * | 1996-02-29 | 1996-05-01 | Unilever Plc | Antiperspirant aerosol composition and method of making same |
| DE102006062433A1 (en) * | 2006-12-27 | 2008-07-03 | Henkel Kgaa | Deodorant or antiperspirant composition comprises a deodorant or antiperspirant agent and taurine in a carrier |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3876758A (en) * | 1969-12-01 | 1975-04-08 | Stewart M Beekman | Process for preparing alcohol solutions of aluminum chlorhydroxides for antiperspirant use and for other uses and compositions containing the same |
| FR2259587A1 (en) * | 1974-02-04 | 1975-08-29 | Procter & Gamble | Zirconium or hafnium oxyhalide anti-perspirant cpds - used in compsns with aluminium cpds and amino acids |
| AU8303275A (en) * | 1974-07-17 | 1977-01-20 | Armour Pharma | Aluminum-zirconium antiperspirant systems with trace amounts of alkaline earth metals |
| US3970748A (en) * | 1975-02-24 | 1976-07-20 | Schuylkill Chemical Company | Aluminum chlorhydroxy glycinate complexes |
| DE2700711A1 (en) * | 1977-01-10 | 1978-07-13 | Unilever Nv | Antiperspirants contg. basic aluminium cpds. - in the form of polymeric molecules |
| FR2377194A1 (en) * | 1977-01-14 | 1978-08-11 | Unilever Nv | Antiperspirants contg. basic aluminium cpds. - in the form of polymeric molecules |
-
1977
- 1977-04-26 GB GB1734477A patent/GB1597497A/en not_active Expired
-
1978
- 1978-04-21 IE IE78578A patent/IE46799B1/en unknown
- 1978-04-24 JP JP4860978A patent/JPS53136530A/en active Granted
- 1978-04-25 CA CA301,861A patent/CA1111858A/en not_active Expired
- 1978-04-26 DE DE19782818321 patent/DE2818321A1/en active Granted
- 1978-04-26 FR FR7812385A patent/FR2388554A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| IE780785L (en) | 1978-10-26 |
| FR2388554B1 (en) | 1983-05-20 |
| DE2818321A1 (en) | 1978-11-02 |
| FR2388554A1 (en) | 1978-11-24 |
| IE46799B1 (en) | 1983-09-21 |
| JPS53136530A (en) | 1978-11-29 |
| DE2818321C2 (en) | 1989-08-31 |
| JPS6323169B2 (en) | 1988-05-16 |
| GB1597497A (en) | 1981-09-09 |
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Legal Events
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