the present invention provides compositions and methods for creating disinfecting and deodorizing chlorous acid hclo 2 ! and chlorous - acid derived oxychlorine species from metal chlorite salts without utilizing proton - donating acids . the chlorous acid in aqueous solutions provides its oxidative disinfecting and deodorizing action through a series of transient and stable oxychlorine degradation species . these include hypochlorous acid hocl !, dichlorine dioxide cl 2 o 2 !, and chlorine dioxide clo 2 !. the chlorine dioxide / chlorite complex anion cl 2 o 4 ! - is also believed to provided antimicrobial and deodorizing properties . the formation of aqueous acidic environments can be brought about by the interaction of selected metal salts and water . for example , certain hydrated metal salts , such as iron , aluminum and gadolinium chlorides , will replace a bound water with an hydroxyl radical oh ! - from the water mediums which essentially liberates a free proton into the aqueous environment . the following representative reactions of the respective hydrated cations illustrate these mechanisms . the effective pk a &# 39 ; s of these reactions , which indicate the degree of acidity created by dissolution of these salts , are given after each reaction . 2 fe ( h . sub . 2 o ). sub . 6 !. sup . 3 + ←→ fe ( h . sub . 2 o ). sub . 4 ( oh ). sub . 2 fe ( h . sub . 20 , 4 !. sup . 4 + + 2h . sup .+ pk . sub . a = 2 . 91 the vanadyl cation , derived from the metal vanadium , also has a tendency to create an acidic aqueous environment , based on the tendency for the vanadyl species to polymerize , i . e . another metallic salt , zirconium oxychloride zrocl 2 ! is known to create very acidic conditions upon dissolution in water . the merck index states that the ph created by this salt is the same as for an equimolar amount of hydrochloric acid . for example , to achieve a ph of 3 , one could use either 0 . 001n hcl or a solution of 0 . 0178 % zirconium oxychloride . it is also well known that the soluble salts of such metals as zinc , cadmium and magnesium create acidic conditions in aqueous media . such salts would include , but not be limited to the following anions : chloride , nitrate , sulfate , perchlorate , acetate , citrate , and lactate . representative acidities of aluminum salt solutions are as follows : aluminum acetate -- 1 : 20 ph 4 . 2 ; aluminum ammonium sulfate -- 0 . 05m ( 1 . 18 %) ph 4 . 6 ; aluminum chlorhydroxide -- 15 % solution ph 4 . 3 . the latter salt is used extensively in underarm antiperspirants ; and the inclusion of an encapsulated metal chlorite salt in an aluminum chlorhydroxide matrix , for release through application of pressure or body heat , will create an effective underarm deodorant in the acidic antiperspirant environment . illustrative of the acidities of current commercial solid antiperspirant products are the following ph figures for 1 % aqueous dispersions of these materials : sure : 4 . 03 ultra ban : 4 . 14 arrid : 4 . 54 brut : 4 . 55 pierre cardin : 4 . 59 all of these products predominate in aluminum chlorhydroxide as the active agent , with a concentration generally of about 20 % ( w / w ). in many underarm antiperspirants the aluminum chlorhydroxide is often present in a stable water - soluble complex in combination with propylene glycol , this complex being termed rehydrol . other aluminum salts , and their levels of use , are the sulfate ( 8 %- 20 % in lotions and creams ), the chloride ( about 5 % in creams and lotions ), and the phenolsulfonate ( about 10 %- 20 %). all of these aluminum salts will induce acidic environments in aqueous media sufficient to form chlorous acid when a metal chlorite is introduced . zirconium salts are also effective antiperspirants , and are often used in combination with aluminum salts in underarm products . in addition to zirconium oxychloride , zirconium lactate and sodium zirconium lactate are effective antiperspirants . their ordinary use levels are about 3 % to 12 %, which are also appropriate concentrations to create antimicrobially - effective amounts of chlorous acid . it is not necessary , however , to use these metal salts in high enough amounts to create effective antiperspirancy , in order to have sufficient acidity to form effective deodorants . in facts , while many people are irritated by the acidity of antiperspirant formulations , they may not be so affected by the lower levels of metal salts needed to create chlorous acid antimicrobial action . in general , the use levels of these acid - inducing salts , for underarm deodorancy , range from about 1 % to about 30 %, depending on the nature , the molecular weight and the degree of hydration of the product . in preferred embodiments , the concentration , of the aluminum salts and the zirconium salts , individually or in combinations range from about 3 % to about 20 %. the concentration of the metal chlorite , upon combination with the acid - inducing metal salt , is generally about 0 . 05 % to about 5 %. since the chlorite cannot be directly introduced into the aqueous metal salt environment without immediate formation of unstable chlorous acid , it must be included in the matrix in an encapsulated form , for subsequent release upon the skin . this may be immediately upon application to the body or some time afterwards . the capsule can contain a liquid concentrate or a metal chlorite powder , and be constructed of an impervious composition . in one embodiment , the capsule may be fabricated of a frangible material , such as a polyethylene wax , a natural material such as beeswax , a synthetic material such as epolene or acrawax , or a combination of these materials . additional materials , such as titanium dioxide powder , may be included in the capsule walls to enhance frangibility . upon application to the skin , the capsules are broken by the pressure of the application , and they release their contents to the acidic environment created by the aqueous metal salts . in another embodiment , the capsule walls are comprised of meltable , water - insoluble polymers , with melting points approximately the same as body temperature . after application to the skin in a gelled metal salt matrix , the capsules are warmed by the body , and melt . this process releases the capsules &# 39 ; metal chlorite solution or powder contents to the acidic environment . typical compositions of these meltable capsules include the following materials , generally as mixtures , formulated to achieve the appropriate melting temperature and other necessary physical parameters : microcrystalline wax , cocoa butter , myristyl myristate , hydrogenated castor oil , beeswax and beeswax substitutes , behenamide monoethylamine , hydrogenated castor oil , and mixtures of long chain fatty acids and glycerides . the metal chlorite is typically enveloped by these polymers by a coacervation process . zinc salts have found application in the oral care field , as effective antiplaque and anticalculus agents . they have also shown efficacy in reducing oral malodor . zinc chloride and zinc citrate are the primary zinc salts that have been used in dentifrices and mouthwashes . zinc chloride , for example , at a concentration of 0 . 25 %, has a ph of about 4 . other zinc salts which induce acidic environments include zinc nitrate ( where a 5 % solution has a ph of about 5 . 1 ) and zinc sulfate ( where a saturated solution has a ph of about 4 . 5 ). the aqueous combination of a zinc salt , such as zinc chloride , and a metal chlorite salt , such as sodium chlorite , is an effective treatment for oral malodor , as well as being helpful in reducing dental plaque , calculus formation , and inflamed oral surfaces . in general these combinations of metal chlorite and acid - inducing metal salt must be prepared shortly before use , to prevent undue degradation of the chlorous acid that is immediately formed . the mixed solution is generally comprised of zinc salts in the range from about 0 . 05 % to about 0 . 5 %, preferably from about 0 . 15 % to about 0 . 35 %, and most preferably from about 0 . 2 % to about 0 . 3 %. the metal chlorite , in a preferred embodiment , is sodium chlorite , at a concentration range of about 0 . 05 % to about 0 . 35 %, and most preferably from about 0 . 1 % to about 0 . 2 %. additional components such as flavor , bodying agents , colors and sweeteners may be included in one or both of the premixed metal salt and metal chlorite solutions , in order to provide appropriate consumer acceptability . another application in which it is difficult to use proton - donating acids to activate a chlorite to chlorous acid is in packaging materials . the acid , or even precursor acid anhydride , causes rapid chlorite decomposition . in this invention a metal chlorite salt , instead of a proton - donating material , is incorporated into a dry polymer or oligomer film in combination with a selected anhydrous metal salt . an anhydrous deliquescent salt may be optionally included into the matrix . upon exposure to a moist environment , the film will absorb moisture into itself , and the metal salt will induce an acidic environment by preferentially attracting oh ! - radicals into its immediate structure . the chlorous acid , thus formed , will partially degrade to chlorine dioxide , the vapors of which can act as a microbiocide and deodorant . the packaging film can be so constructed that the outer portion will have a low permeability to chlorine dioxide gas , such as from a polyvinylidene chloride or polyester film , so that the gas generated will preferentially diffuse inwards to the packaged contents . the metal chlorite may be contained in films such as described by wellinghoff ( u . s . pat . no . 5 , 360 , 609 ) which is incorporated herein by reference . in that patent , the metal chlorite is suspended in a hydrogen bonded matrix , such as a mixture of formamide , acrylamide and isopropylacrylamide . in the wellinghoff patent , that phase is mixed with a phase containing a hydrolyzable acid anhydride , from which mixture a sustained release of chlorine dioxide is observed within five minutes . in contrast , in the present patent , a similar hydrogen bonded phase is mixed with a phase containing a specific anydrous metal salt dispersed in an organic solvent solution of a polymer from this mixture no chlorine dioxide will evolve , even when the solvent mixture is deposited by evaporation onto a barrier film surface . the concentration of metal chlorite salt in the hydrogen bonded matrix is preferably in the concentration range of about 1 % to 14 wt %, and the total dissolved polymer is preferably in the range of about 50 % to about 80 %. this phase may be preferably combined with the metal chlorite phase in a ratio of about 1 : 2 to about 2 : 1 . the metal salt in the anhydrous , apolar phase is preferably in the concentration range of about 0 . 5 % to about 10 % and the polymer component of that phase is preferably in the concentration range of about 50 % to about 75 %. after deposition of that phase onto a carrier film , no evolution of chlorine dioxide is observed to occur through degradation of chlorous acid until the barrier film is exposed to an environment from which moisture in the air can induce an acidic environment brought about by the dissolution of the metal salts in the film . the metal salts may comprise , but not be limited to , one or a combination of the water soluble metal salts of such cations as aluminum , ferric , ferrous , cadmium , gallium , zirconyl , vanadyl , stannous , stannic , and zinc , in combination with appropriate anions . it should be noted that the use of such metal salts as sole activators of metal chlorites to form disinfecting chlorous acid , as well as chlorine dioxide under some circumstances , differs substantially from the use of transition metals and metal oxides to enhance the catalytic generation of chlorine dioxide from sodium chlorite , as taught in ringo , u . s . pat . no . 5 , 008 , 096 in 1991 . in that patent , certain metals were to used to stimulate higher levels of chlorine dioxide generation when they were included in well - known oxidation or acidification reactions by which chlorine dioxide is formed from sodium chlorite . the present invention is illustrated by the following examples . unless otherwise noted , all parts and percentages in the examples as well as the specification and claims are by weight . this example illustrates the use of a representative deodorant stick , in which microencapsulated sodium chlorite solution is suspended in a gelled composition containing aluminum chlorhydroxide at a level below that which provides adequate antiperspirancy , but sufficient to induce the formation of chlorous acid from chlorite . upon application of the stick to the underarm , the frangible capsules containing the chlorite solution are broken , releasing the capsule contents into the acidic aluminum salt medium . ______________________________________part aaluminum chlorhydroxide , 15 % 10 . 00 gmsolutionethyl alcohol 12 . 00 mlpropylene glycol 3 . 00 gmsodium hydroxide 0 . 75 gmstearic acid 5 . 25 gmwater 42 . 00 gmpart bmicrocapsules with the followingcharacteristicsshell : 80 % boler paraffin wax 1426 20 % epolene c - 16 polyethylenefill : 35 % aqueous sodium chloritepayload : 40 % size 500 μmdensity : 1 . 07 gm / mlburst strength : 30 - 50 gm______________________________________ the stearic acid is dissolved in the glycol / alcohol mixture . in another container the sodum hydroxide is dissolved in the water and combined with the aluminum chlorhydroxide solution , which mixture is then heated to 65 ° c . the alcohol solution is heated in a separate container to the same temperature and added to the aqueous solution with stirring . the soap forms rapidly . when the reaction is complete , the mixture is cooled slowly until it begins to thicken , at which point 5 gm of the sodium chlorite microcapsules are stirred in carefully to a uniform dispersion . the product is then poured into a mold to further cool . this example illustrates the use of a representative deodorant cream , in which microencapsulated sodium chlorite solution is suspended in an oil water cream base containing a mixture of metal salts which induce formation of chlorous acid . upon application of the cream to the underarm , the applied pressure releases the chlorite from the capsules , and the acid environment induces the creation of chlorous acid . a cream base is prepared by mixing the following ingredients in the order listed , at 45 °- 50 ° c . : ______________________________________glycerol 10 gmsorbitan monostearate , polyoxyethylene derivative 3 gmglyceryl monostearate 13 gmtriethanolamine salt of dodecylbenzene sulfonate 10 gmspermaceti wax 3 gmpetrolatum 1 gmwater 52 gmtitanium dioxide 1 gmsodium zirconium lactate 5 gmaluminum chloride 2 gm______________________________________ when the mixture is uniform , it is cooled slowly until it begins to thicken , at which point 6 gm of the sodium chlorite microcapsules from example 1 are stirred in carefully , to form a uniform dispersion . the product is then poured into jars to cool , and capped . this example illustrate the use of a concentric deodorant stick , where the underarm application and abrasion of two separated solid phases , containing a specific metal salt in one phase and a metal chlorite salt in the other , causes the two phases to mix on the skin and create an antimicrobial and deodorizing chlorous acid matrix . the aluminum chlorhydroxide stick in example 1 is prepared without the inclusion of the sodium chlorite microcapsules . the stick is cooled to about 10 ° c . and a 2 - cm central cylinder is removed with a cork borer . into the hole that is formed is poured a melted paraffin wax , at about 40 ° c ., which is then poured out after about 2 minutes . this leaves a thin wax coating over the inner surface of the hollow cylinder . into this cavity is poured , up to the top surface of the stick , a composition of the following percent composition , preheated to 40 ° c . : ______________________________________stearyl alcohol 10 gmcyclomethicone 20 gmisopropyl alcohol 50 gmsodium stearate 8 gmsodium chlorite ( pure basis ) 1 gmsodium hydroxide , 1n 2 gmwater 9 gm______________________________________ the combination is cooled to 15 °- 20 ° c ., to set the inner phase . this example illustrates the use of a mixed metal salt to create an astringent , deodorizing and antimicrobial oral rinse . the rinse is prepared by combining equal volumes of the following two liquid phases directly before use : ______________________________________phase azinc chloride 0 . 10 % aluminum potassium sulfate 0 . 10 % glycerin 20 . 00 % ethyl alcohol 10 . 00 % cinammon oil 0 . 010 % menthol 0 . 050 % fd & amp ; c red no . 40 0 . 002 % water 69 . 708 % phase bsodium chlorite ( pure basis ) 0 . 25 % water , q . s . after adding sodium hydroxide , to → 100 . 00 % sodium hydroxide 1n , q . s . to achieve solution ph = 10______________________________________ this example illustrates the use of comixed , solvent - dispersed phases of a ) metal chlorite salt + monomer , and b ) acid - inducing metal salt + polymer , as a deposit on a packaging film , such that the resulting cured film creates chlorine dioxide from the chlorous acid precursor that is formed upon absorption of moisture from the package environment . the composition is prepared in two parts by mixing the following ingredients , and maintaining each at 0 °- 5 ° c . until mixing and depositing : ______________________________________part asodium chlorite 7 . 00 % formamide ( anhydrous ) 31 . 00 % acrylamide ( anhydrous , stabilized ) 31 . 00 % isopropylacrylamide 31 . 00 % part bpolystyrene 60 . 00 % ethylbenzene 40 . 00 % ______________________________________ the composition is sprayed onto the surface of a 2 - mil thick polyvinylidene chloride ( saran ) film , and cures as the solvent evaporates in use , the low gas - permeable saran substrate is on the outer surface of the packaging composition , and only moisture from the packaged contents will induce the reaction , and the resulting chlorine dioxide so formed will preferentially diffuse inwards . this example illustrates the use of a stable , single phase of comixed powders of a metal salt and a metal chlorite which , upon the addition of water , forms a disinfecting and deodorizing chlorous acid system . the mixture is stored in a moisture - barrier package to prevent premature activation . ______________________________________sodium aluminum sulfate , anhydrous powder 0 . 71 gmsodium chlorite , technical grade , anhydrous powder 0 . 71 gm______________________________________ the powders are physically intermixed , in a dry environment , and enclosed in a saran package . upon opening , the powder is added to ounce of tap water and the mixture is stirred for 10 seconds to dissolve . the resulting solution which has a ph of 3 . 77 , and develops the distinctive odor and color of chlorine dioxide , can be used as a disinfectant for inanimate and animate surfaces , such as on medical equipment or as a teat dip , respectively . this example illustrates the use of the stable , single - phase mixture shown in example 6 as an area deodorant , disinfectant or fumigant . the powdered contents of the package are transferred to a glass dish , which is then placed in an area which requires disinfection or deodorization . moisture from the environment is absorbed into the powder , which undergoes the production of gaseous chlorine dioxide . the rate of moisture uptake and onset of action may be enhanced by inclusion of a deliquescent salt , such as anhydrous calcium chloride , in the powdered mixture . it is clear that the present invention is well adapted to carry out the objects and achieve the ends and advantages mentioned therein . while currently preferred embodiments of the invention have been described for purposes of this disclosure , numerous changes may be made which will readily suggest themselves to those skilled in the art , and which are encompassed within the spirit of the invention disclosed , and as defined in the appended claims .
an antimicrobial and deodorizing composition is disclosed , which includes an aqueous solution having at least one acid - inducing metal salt and a metal chlorite and no protic acid . the aqueous solution has a ph less than about 7 . the acidity - inducing metal salt , preferably , includes a iron cation , an aluminum cation , a gadolinium cation , a vanadium cation , a zirconium cation or a zinc cation , and anions sufficient for rendering said metal salt electrically neutral and water - soluble . the metal chlorite may , preferably , be sodium chlorite . various methods for use of the composition are also disclosed .