The present application is a continuation-in-part of U.S. patent application no. 07/957,307 filed September 16, 1992 and of U.S. patent application no. 08/047,535 filed on April 19, 1993.

The present invention relates to a disinfectant substance comprising an iodine (impregnated) resin and to a process for the preparation thereof. The iodine/resin disinfectant may be used to sterilize a fluid such as, for example, water, air, as well as fluid exudate secreted at body lesions or traumas such as at cuts, burns , etc.; thus, the disinfectant may be used to devitalize microorganisms (e.g. bacteria, viruses, etc..) which may be present in the fluid (e.g. water, air, pus and the like) . The treatment of fluid, such as water or air, with an iodine/resin disinfectant of the present invention may leave behind non-detectable (or acceptable) residual diatomic iodine in the fluid (e.g. water or air) . The present invention in particular relates to a demand type broad spectrum resin-polyiodide (e.g. water, air, wound) disinfectant.

Diatomic halogen (such as I ₂ , Cl ₂ , Br ₂ , etc..) has

SUBSTITUTESHEET

traditionally been used to disinfect water. Diatomic chlorine, for example, is a widely exploited disinfectant for controlling or eliminating micro-organisms which may be present in water. A disadvantage of a sterilization regime which exploits diatomic halogen is that the regime may leave behind unacceptable (residual) levels of halogen in the water once sterilization is complete.

An iodine/resin product has, however, been proposed for use as a demand disinfectant, namely a disinfectant wherein iodine is released almost entirely on a demand-action basis. United States patent nos. 3,817,860, 3,923,665, 4,238,477 and 4,420,590 teach such a demand disinfectant wherein iodine is the active disinfectant agent; the entire contents of each of these patents is incorporated herein by reference. In accordance with the teachings of these patents the resin product may be used without fear of introducing unacceptable concentrations of diatomic iodine into the water to be sterilized.

U.S. patent nos. 3,817,860 and 3,923,665 teach an iodine/resin demand disinfectant which is the reaction product obtained by contacting a strong base anion exchange resin with a suitable source of triiodide ions. The reaction product is taught as being very stable in the sense that the amount of iodine (e.g. I ₂ ) released into water from the reaction product is sufficiently low that the water disinfected thereby is immediately ready for use, ie. as

drinking water.

In accordance with the teachings of U.S. patent nos. 3,817,860 and 3,923,665 the procedure for preparing the iodine/resin comprises forming a triiodide ion (solution or sludge) by dissolving diatomic iodine in a water solution of a suitable alkali metal halide (e.g. KI, Nal,....). The triiodide solution is in particular taught as being made with a minimal (i.e. minor) water content just sufficient to avoid causing the I ₂ to crystallize out; see example 1 of U.S. patent no. 3,923,665. The resulting (solution) containing the triiodide ion is then contacted with the starting resin (under ambient conditions with respect to temperature (i.e. 25 to 30° C) and pressure) , the triiodide ions exchanging with the anion of the resin (e.g. exchange with chlorine, sulfate, etc., ..). The starting resin is taught as being a porous granular strong base anion exchange resin having strongly basic groups in a salt form wherein the anion thereof is exchangeable with triiodide ions. In accordance with the teachings of the above prior art references contacting is continued until the desired amount of triiodide has reacted with the strongly basic groups such that bacterially contaminated water is disinfected when passed through a bed of the obtained resin. After a suitable contact time the iodine/resin is (water) washed to remove water-elutable iodine from the resin product.

However, as indicated in U.S. patent no. 4,238,477, it is

difficult to use the procedures outlined in the two previously mentioned U.S. patents so as to obtain a homogeneous iodine/resin product containing only triiodide anions and wherein all of the active sites of the resin have been converted to triiodide ions.

Accordingly, U.S. patent no. 4,238,477 teaches an alternate process whereby the iodine/resin may be produced. In accordance with this alternate impregnation/contact process, a suitable resin in the iodide form (I ^" ) is contacted with water comprising diatomic iodine (I ₂ ) in solution, the water being recycled between a source of a predetermined amount of diatomic iodine and the resin. The process as taught by this latter patent, however, is a relatively complicated system of pumps, vessels, heaters, etc.; by exploiting a fluidized bed, it in particular may lead to a significant degree of resin bead attrition, i.e. particle breakup.

The processes as taught in U.S. patent nos. 3,817,860 and 3,923,665 are carried out at ambient temperature and ambient pressure conditions. The U.S. patent 4,238,477 teaches that the contact may occur at a higher temperature such as 60 to 95° C but that the temperature must be a non-boiling temperature (with respect to water) ; see column 3 lines 55 to 66.

The above referred to U.S. patents teach the use of the demand disinfectant iodinated resins for treating water; see

also U.S. patent nos. 4,298,475 and 4,995,976 which teach water purification devices or systems which exploit iodinated resins. None of these patents teaches the use of the iodinated resins for the purpose of sterilizing air.

It is also known to use iodine tincture for sterilising wounds. The sterilisation effect of iodine tincture is short lived; this means that the tincture must be reapplied on a regular basis to maintain the sterilisation effect. However, such solutions may also damage or destroy the tissue around the wound if applied too liberally and too often. Additionally, the direct application of such solutions to a lesion or wound is usually accompanied by a painful sensation.

Accordingly it would be advantageous to have a iodine/resin product which has improved characteristics over known or commercially available iodine/resin disinfectant products.

It would also be advantageous to have an alternate process for the preparation of a iodine/resin product (which has improved characteristics over the previously known iodine/resin) .

It would be advantageous to have an alternative effective demand disinfectant (e.g. bactericidal) resin and an effective technique for the manufacture thereof. It would, in particular, be advantageous to have an iodine/resin demand

disinfectant having a relatively low level of iodine bleed into a fluid (such as water or air) being treated as well as an iodine impregnation process for obtaining such iodinated resin.

It would also be advantageous to have a means whereby lesions, such as for example wounds or burns, may be treated in order to facilitate healing by devitalising microorganisms which may already be in the area of the lesion and further to prevent microorganisms from having access, to such lesion (i.e. a dressing), i.e. to inhibit access from any outside biovectors such as for example airborne, waterborne, spital borne, blood borne, particulate borne microorganisms and the like.

It would additionally be advantageous to have a means for inhibiting or preventing microorganisms from contacting predetermined areas of the body such as the skin (e.g. a protective textile for making protective clothing) .

In accordance with a general aspect, the present invention provides a process for preparing a demand disinfectant resin, said disinfectant resin being an iodinated strong base anion exchange resin, (i.e. a demand disinfectant-resin comprising polyiodide ions, having a valence of -1, the ions being absorbed or impregnated into the resin as herein described) ,

the process comprising a conversion step, the conversion

step comprising contacting a porous strong base anion exchange resin in a salt form with a sufficient amount of an iodine-substance absorbable by the anion exchange resin such that the anion exchange resin absorbs said iodine-substance so as to convert the anion exchange resin to the disinfectant-resin, said iodine-substance being selected from the group comprising I ₂ (i.e. diatomic iodine) and polyiodide ions having a valence of

characterized in that for the conversion step at least a portion of the absorption of iodine-substance is effected at elevated temperature and at elevated pressure, said elevated temperature being 100° C or higher (e.g. a temperature higher than 100° C such as, for example, 102° C, 103° C, 104° C, 105° C, 110° C, 115° C, 150° C, etc.), said elevated pressure being greater than atmospheric pressure (e.g. a pressure greater than barometric pressure such as for example 2 psig, 3 psig, 4 psig, 5 psig, 15 psig, 25 psig, 35 psig, 100 psig, etc.).

In accordance with the present invention the disinfectant- resin may be one in which diatomic iodine is incorporated. The disinfectant polyiodide-resin may in particular be triiodide-resin. Thus, for example, the iodine-substance may comprise triiodide ion of formula I ₃ ^" , i.e. so as to form a disinfectant-resin which comprises (absorbed) triiodide ions of formula I ₃ ^~ .

The terms "triiodide", "triiodide ion" and the like, as used

in the context herein, refer to or characterize a substance or a complex as containing three iodine atoms and which has a valence of -1. The triiodide ion herein therefore is a complex ion which may be considered as comprising molecular iodine (i.e. iodine as I ₂ ) and an iodine ion (i.e. I ^" ). Similarly the terms "polyiodide". "polyiodide ions" and the like, refer to or characterize a substance or a complex as having three or more iodine atoms and which may be formed if more of the molecular iodine combines with the monovalent triiodide ion. These terms are more particularly described in the above referred to U.S. patents.

In accordance with a further aspect, the present invention provides a process for preparing a demand disinfectant resin, said disinfectant resin being an iodinated strong base anion exchange resin, (i.e. a demand disinfectant-resin comprising polyiodide ions, having a valence of -1, the ions being absorbed or impregnated into the resin as herein described) , the process comprising a conversion step, the conversion step comprising contacting a porous strong base anion exchange resin in a salt form other than the iodide form I ^" , with a sufficient amount of an iodine-substance absorbable by the anion exchange resin such that the anion exchange resin absorbs said iodine-substance so as to convert the anion exchange resin to the disinfectant- resin, said iodine-substance being selected from the group comprising polyiodide ions having a valence of -1, characterized in that for the conversion step at least a

portion of the absorption of iodine-substance is effected at elevated temperature and at elevated pressure, said elevated temperature being 100° C or higher (e.g. a temperature higher than 100° C) , said elevated pressure being greater than atmospheric pressure (e.g. a pressure greater than barometric pressure) .

The strong base anion exchange resin may be in a salt form such as for example a chloride or hydroxyl form.

The conversion in accordance with the present invention may essentially or at least partially be effected at said elevated temperature and elevated pressure. The conversion, in accordance with the present invention, may, thus for example, be effected in one, two or more stages. For example, the elevated pressure/temperature conditions may be divided between two different pairs of elevated pressure/temperature conditions, e.g. an initial pressure of 15 psig and a temperature of 121° C and a subsequent pressure of 5 psig and a temperature of 115° C.

If the conversion is to be carried out in two stages, it may for example, comprise a first stage followed by a second stage. The first stage may, for example, be effected at low temperature conditions (e.g. at ambient temperature and ambient pressure conditions) whereas the second stage may be effected at elevated conditions such as described herein.

Thus, the present invention, in accordance with another aspect provides a process for preparing a demand disinfectant resin, said disinfectant resin being an iodinated strong base anion exchange resin, (i.e. a demand disinfectant-resin comprising polyiodide ions, having a valence of -1, the ions being absorbed or impregnated into the resin as herein described) , the process comprising a conversion step, the conversion step comprising contacting a porous strong base anion exchange resin in a salt form with a sufficient amount of an iodine-substance absorbable by the anion exchange resin such that the anion exchange resin absorbs said iodine-substance so as to convert the anion exchange resin to the demand disinfectant resin, said iodine- substance being selected from the group comprising I ₂ and polyiodide ions having a valence of -1, characterized in that said conversion step comprises an initial conversion stage followed by a second conversion stage, in that said initial conversion stage comprises contacting the anion exchange resin with the iodine-substance at a temperature of 100° C or lower so as to obtain an intermediate composition, said intermediate composition comprising residual absorbable iodine-substance and an intermediate iodinated resin, (i.e. a resin comprising absorbed polyiodide ions having a valence of -1) , and in that said second conversion stage comprises subjecting the

intermediate composition to elevated temperature and elevated pressure, said elevated temperature being 100° C or higher (e.g. a temperature higher than 100° C) , said elevated pressure being greater than atmospheric pressure.

In accordance with a further particular aspect, the present invention provides a process for preparing a demand disinfectant resin, said disinfectant resin being an iodinated strong base anion exchange resin, (i.e. a demand disinfectant-resin comprising polyiodide ions, having a valence of -1, the ions being absorbed or impregnated into the resin as herein described) , the process comprising a conversion step, the conversion step comprising contacting a porous strong base anion exchange resin in a salt form other than the iodide form

I ^" with a sufficient amount of an iodine-substance absorbable by the anion exchange resin such that the anion exchange resin absorbs said iodine-substance so as to convert the anion exchange resin to the disinfectant- resin, said iodine-substance being selected from the group comprising polyiodide ions having a valence of -1, characterized in that said conversion step comprises an initial conversion stage followed by a second conversion stage, in that said initial conversion stage comprises contacting the anion exchange resin with the iodine-substance at a temperature of 100° C or lower so as to obtain an intermediate composition, said intermediate composition

comprising residual absorbable iodine-substance and an intermediate iodinated resin (i.e. a resin comprising absorbed polyiodide ions having a valence of -1) , and in that said second conversion stage comprises subjecting the intermediate composition to elevated temperature and elevated pressure, said elevated temperature being 100° C or higher (e.g. a temperature higher than 100° C) , said elevated pressure being greater than atmospheric pressure.

In accordance with the present invention, for the first stage, the low temperature may, for example, be a non-boiling temperature of not more than 95° C; e.g. 15 to 60° C; e.g. ambient temperature or room temperature such as a temperature of from about 15° C to about 40° C, e.g. 20 to 30° C. The pressure associated with the low temperature condition of the first stage may, for example, be a pressure of from 0 (zero) to less than 2 psig; the pressure may in particular be essentially ambient pressure (i.e. a pressure of less than 1 psig to 0 (zero) psig; 0 psig reflecting barometric or atmospheric pressure) .

In accordance with the present invention, for the second stage, the elevated temperature may, for example, be: a temperature of 102° C or higher; e.g. 105° C or higher; e.g. 110° C or higher; e.g. 115° C or higher; e.g. up to 150° C to 210° C; e.g. 115° C to 135° C. The elevated pressure associated with the elevated temperature condition of the

second stage may, for example, be: a pressure of 2 psig or greater; e.g. 5 psig or greater; e.g. 15 psig to 35 psig; e.g. up to 100 psig.

The present invention further relates to any demand disinfectant resin, the disinfectant resin being an iodinated strong base anion exchange resin which is the same as an iodinated strong base anion exchange resin prepared in accordance with a process as defined herein; an iodinated resin the same as a resin prepared in accordance with the (particular) process described herein iε one which has the same low iodine bleed characteristic, i.e. the iodine is (more) tenaciously associated with the resin than for previously known iodinated resins. It in particular relates to a demand disinfectant resin, the disinfectant resin being an iodinated strong base anion exchange resin whenever prepared in accordance with a process as defined herein.

The present invention also relates to the use of iodinated resins to disinfect fluids containing microorganisms, such fluids including air, water, pus, and the like. The iodinated resin may for example be a known resin such as discussed herein, a resin in accordance with the present invention, nylon based resin beads impregnated with iodine (such as MCV resin from MCV Tech. Intn'l Inc.) , and the like.

Thus the present invention also provides a method for disinfecting air containing airborne microorganisms, said

method comprising passing said air over a disinfectant resin such that airborne microorganisms contact said resin and are devitalized thereby, said disinfectant resin comprising an iodinated resin. The disinfectant resin may, for example, be a demand disinfectant resin. The disinfectant resin may, for example, comprise an iodinated strong base anion exchange resin.

The present invention further provides a system for disinfecting air containing airborne microorganisms, said system comprising means for providing an air path for the movement of air therethrough, and a disinfectant resin disposed in said air path such that airborne microorganisms in air passing through said air path are able to be brought into contact with said resin and be devitalized thereby, said disinfectant resin comprising an iodinated resin. The disinfectant resin may, for example, be a demand disinfectant resin. The disinfectant resin may, for example, comprise an iodinated strong base anion exchange resin.

The present invention additionally provides a combination comprising a disinfectant component and a carrier component,

said disinfectant component comprising particles of an iodinated resin, said particles of said disinfectant component being held (e.g. fixed) to said carrier component. The disinfectant component may, for example, be a demand disinfectant component. The disinfectant resin may, for example, comprise an iodinated strong base anion exchange resin. The combination may be used as a means for providing a barrier or shield for the body against microorganisms. The combination may thus, for example, be incorporated into a textile or other wearing apparel starting material in the form of a layer (e.g. a liner layer) . The obtained raw wearing apparel material may then be used to make a protective garment, glove, sock, footwear (e.g. shoe) , helmet, face mask and the like; the obtained wearing apparel may be worn in hazardous environments to protect the wearer from contact with viable microorganisms. The combination as desired or as necessary may flexible or stiff; depending on the nature of the carrier component and also on the form of the resin (e.g. plate, particle, etc.).

The present invention in a more particular aspect provides a sterilisation dressing, for being applied to a lesion, (such as a sore, a wound (e.g. cut) , an ulcer, a boil, an abrasion, a burn or other lesion of the skin or internal organ) , said dressing comprising a disinfectant component and

a carrier component, said disinfectant component comprising particles of an iodinated strong base anion exchange resin, said carrier component being configured so as to hold onto particles of said disinfectant component such that microorganisms are able to be brought into contact with said particles and be devitalised thereby, said carrier component being of a pharmaceutically acceptable material. The disinfectant component may, for example, be a demand disinfectant. The disinfectant resin may, for example, comprise an iodinated strong base anion exchange resin. The carrier component may be stiff or it may be flexible as desired. The (sterilization) dressing may, for example, be applied over a wound or burn and be held in place over the time period needed for the body to repair the damaged area; the dressing during this time will act not only as a barrier or shield to prevent infectious microorganisms from contacting the lesion but also to sterilize the immediate area around the lesion including sterilising any fluid exudate such as pus which may exude from the lesion. Surprisingly, it has, for example, been found that even with relatively prolonged exposure of (guinea pig) skin to the active element of the dressing (i.e. the demand disinfectant) no irritation or inflammation was noted. It has also surprisingly been found that the dressing may effect infectious agents deep beneath the skin or dressing. The healing process may thus be hastened by the application of a (sterilization) dressing in accordance with the present

invention.

The demand disinfectant for the above mentioned method and system for treating air as well as for the combination and the dressing may be an iodinated resin produced in accordance with the present invention or it may be a known demand disinfectant iodinated resin such as for example as mentioned herein.

The demand disinfectant depending on the intended use may take on any desired form; it may be bulk form; it may be in sheet form; it may be in particulate or granular form (e.g. particles of resin of from 0.2 mm to 1 cm in size), etc..

It is to be understood herein, that if a "range" or "group of substances" is mentioned with respect to a particular characteristic (e.g. temperature, presssure, time and the like) of the present invention, the present invention relates to and explicitly incorporates herein each and every specific member and combination of sub-ranges or sub-groups therein whatsoever. Thus, any specified range or group is to be understood as a shorthand way of referring to each and every member of a range or group individually as well as each and every possible sub-ranges or sub-groups encompassed therein; and similarly with respect to any sub-ranges or sub-groups therein. Thus, for example,

- with respect to a pressure greater than atmospheric, this is to be understood as specifically incorporating

herein each and every individual pressure state, as well as sub-range, above atmospheric, such as for example 2 psig, 5 psig, 20 psig, 35.5 psig, 5 to 8 psig, 5 to 35, psig 10 to 25 psig, 20 to 40 psig, 35 to 50 psig, 2 to 100 psig, etc.. ;

- with respect to a temperature greater than 100° C, this is to be understood as specifically incorporating herein each and every individual temperature state, as well as sub-range, above 100° C, such as for example 101° C, 105° C and up, 110° C and up, 115° C and up, 110 to 135° C, 115° c to 135° C, 102° C to 150° C, up to 210°

- with respect to a temperature lower than 100° C, this is to be understood as specifically incorporating herein each and every individual temperature state, as well as sub-range, below 100° C, such as for example 15° C and up, 15° C to 40° C, 65° C to 95° C, 95° C and lower, etc.;

- with respect to residence or reaction time, a time of 1 minute or more is to be understood as specifically incorporating herein each and every individual time, as well as sub-range, above 1 minute, such as for example 1 minute, 3 to 15 minutes, 1 minute to 20 hours, 1 to 3 hours, 16 hours, 3 hours to 20 hours etc.;

- and similarly with respect to other parameters such as low pressures, concentrations, elements, etc...

It is also to be understood herein that "g" or "girt" is a reference to the gram weight unit; that "C" is a reference to the celsius temperature unit; and "psig" is a reference to

"pounds per square inch guage".

In drawings which illustrate example embodiments of the present invention: Figure 1 is a graph of showing the ppm of Iodine in the effluent versus the total volume of water contacted with a disinfectant-resin bed of the prior art and an example disinfectant resin of the present invention; Figure 2 iε a graph of the number of microorganisms in effluent versus the total volume of contaminated water contacted with a disinfectant reεin of the prior art and an example diεinfectant reεin of the present invention; Figure 3 iε a perεpective view of a cartridge which may be used to house an iodinated resin aε described herein for use for example in a gaε mask; Figure 4 is a crosε εectional view 4-4 of the cartridge of figure 1; Figure 5 iε a εchematic illustration of a system for testing a cartridge containing an iodinated reεin; Figure 6 iε a εchematic illuεtration of another type of εyεtem for teεting a cartridge containing an iodinated reεin; Figure 7 iε a partially cut away perεpective view of a εteriliεation dreεεing of tea-bag type conεtruction wherein the iodinated resin particles are free flowing but are held together by being

enveloped by a fluid (e.g. air-liquid) permeable envelope of paper, gauze, plaεticε material, etc.;

Figure 8 is a perspective view of a band-aid type sterlization dressing, wherein the iodinated resin particles are fixed to a central portion of an outer εurface of a flexible band-aid carrier;

Figure 9 iε a perεpective partially cut away view of a εteriliεation foam or εponge type dreεεing compriεing a flexible foam matrix having iodinated reεin particleε diεperεed therein, the foam matrix having a relatively small pore size structure;

Figure 10 is a perspective partially cut away view of a steriliεation foam or εponge type dreεεing compriεing a flexible foam matrix having iodinated reεin particles disperεed therein, the foam matrix having a relatively large pore size structure; and

Figure 11 is a croεε εectional view of a εandwich type of textile material for uεe in the preparation of protective clothing, the textile including a layer of a flexible foam matrix εuch aε is shown in figure 10.

In accordance with the present invention, the elevated temperature may aε mentioned above, for example, be in the range of from 105° C to 150° C; the elevated pressure may be 5 psig and up.

In accordance with the process of the present invention the

anion exchange reεin may, for example, as described below, be a quaternary ammonium anion exchange resin; the anion exchange resin may be in the chloride form Cl ^" , in the hydroxyl form OH ^" ; etc....

In accordance with the present invention the obtained iodide- resin may be treated prior to use to remove any water- elutable iodine from the iodide-resin. The treatment (e.g. washing) may be continued until no detectable iodine is found in wash water (the wash water initially being ion free water) . Any suitable (known) iodine teεt procedure may be uεed for iodine detection purpoεeε (εee for example the above mentioned U.S. patentε.

In accordance with the preεent invention, the abεorbable iodine εubεtance may, for example, be provided by a compoεition conεiεting of mixture of KI, I ₂ and a minor amount of water, the mole ratio of KI to I ₂ initially being about 1; the expreεεion "minor amount of water" aε uεed herein εhall be underεtood aε characterizing the amount of water aε being sufficient to avoid I ₂ crystallization.

The preεent invention in a further aspect provides an enhanced iodine/resin demand diεinfectant product in which more iodine may be distributed throughout and be more tenaciously asεociated with the reεin (e.g. beadε) than with the previouεly known or commercially available techniques, the disinfectant being produced by a procesε aε described

herein. The invention more particularly provides an enhanced triiodide-resin disinfectant.

The present invention can be practised with any (known) εtrong baεe anion exchange reεin (for example, with those such as are described in more detail in the above-mentioned United States patents such as United States patent no 3,923,665) . A quaternary ammonium anion exchange resin is, however, preferred. As used herein, it is to be understood that the expresεion "strong base anion exchange reεin" deεignateε a claεε of reεinε which either contain strongly basic "cationic" groups, such as quaternary ammonium groups or which have strongly baεic propertieε which are εubstantially equivalent to quaternary ammonium exchange resinε. United Stateε patent noε. 3,923,665 and 3,817,860 identify a number of commercially available quaternary ammonium reεinε, aε well aε other εtrong base resinε including tertiary εulphoniu reεinε, quaternary phosphonium resins, alkyl pyridinium resinε and the like.

Commercially available quaternary ammonium anion exchange resins which can be used in accordance with the present invention include in particular, Amberlite IRA-401 S, Amberlite IR-400 (Cl ^" ) , Amberlite IR-400 (OH ^" ), Amberlite IR- 402 (Cl ^" ) , etc., (from Rohm & Hass) which may be obtained in granular form. These resins may for example, contain quaternary ammonium exchange groups which are bonded to styrene-divinyl benzene polymer chains.

The resinε which may be uεed herein may be in a hydroxyl form, a chloride form or in another salt (e.g. sulphate) form provided that the anion is exchangeable with the iodine member (e.g. with triiodide ion) .

The starting resin may, for example, be granular (i.e. comprise a plurality of particles) εuch that the final product will likewise have a granular or particulate character; the granular form is advantageous due to the high surface area provided for contact with microorganisms. The starting resin may, for example, comprise granuleε having a size in the range of from 0.2 mm to 0.8 cm (e.g. of from 0.35 mm to 56 mm) .

Commercially available resins εuch as those mentioned above are available in the salt form (e.g. as the chloride) and in the form of porous granular beads of various meεh sizes; the resin may of course be used in a bulk or massive form such aε a plate, εheet, etc..

In accordance with the present invention, for example, a resin may be converted from a non-iodide form (e.g. a chloride form, a εulphate form) to the I ₃ ^" form. Suitable halide εaltε include alkali metal halides (such as KI, Nal,...); potassium iodide is preferred. Alternatively, an iodide form of the resin may be uεed and the resin contacted with a source of diatomic iodine.

In accordance with the present invention any material or substance capable of donating an iodine-member absorbable by the anion exchange resin so as to convert the anion exchange resin to the desired polyiodide-resin may be used, as long as the denotable iodine-member thereof is a polyiodide ion having a valence of -1 and/or diatomic iodine. Examples of such materials in relation to iodine are shown in the above mentioned U.S. patents; e.g. compositions comprising iodine (I ₂ ) and alkali metal halide (KI, Nal, etc., KI being preferred) in aεεociation with water. Alternatively, if the reεin is in an iodide εalt form (I ^'1 ) , the material may compriεe the correεponding iodine in gaεeous form.

Thus, for example, if a triiodide-resin iε deεired the reεin may be contacted with an alkali metal iodide/I ₂ mix wherein the iodide and the diatomic iodine are present in more or less stoichiometric amountε (i.e. a mole ratio of 1) ; see the previously mentioned U.S. patents. By applying stoichiometric amounts of the iodine ion and iodine molecule (i.e. one mole of I ₂ per mole of I ^"1 ) , the iodide sludge will compriεe εubεtantially only the triiodide ions. If stoichiometric excesε quantities of I ₂ are used some of the higher polyiodide ionε may be formed. Preferably, no more than the εtoichiometric proportionε of I ^" and I ₂ are uεed in the initial aqueouε εtarting sludge so that subεtantially only triiodided attacheε to the reεin.

For example iodine may be combined with sodium, potaεεium or

ammonium iodide and some water. The composition will contain monovalent iodine ion which will combine with diatomic iodine (I ₂ ) to form polyiodide ion. The molar ratio of iodine ion to diatomic iodine will dictate the nature of the polyiodide ion present , i.e. triiodide ion, mixtures of triiodide ion and other higher polyiodides ionε, pentaiodide ion, etc.... Uεing about 1 mole of iodine ion per mole of diatomic iodine the formation of triiodide ion will be favoured. If stiochiometric exceεε of diatomic iodine iε used this will favour the formation of higher polyiodides.

The determination of the (total) amount of iodine to be contacted with the resin, reεidence timeε etc., will depend upon such factors as the nature of the polyiodide it is desired to introduce into the structure of a resin; the nature of the εtarting reεin (i.e. porosity, grain εize, equivalent exchange capacity of the reεin, etc.), etc.. Thuε, for example, to determine the amount of iodine required to prepare a polyiodide resin, the equivalent exchange capacity of the resin needs to be known. If necessary, this can be readily determined for example by the procedure deεcribed in U.S. patent no. 3,817,860 (column 9, lines 15 to 28) . The components of the proceεε may be choεen εuch that the obtained iodinated εtrong baεe anion exchange resin may comprise a εtrong base anion exchange resin component which repreεents from 25 to 90 (preferably 45 to 65) percent by weight of the total weight of the obtained iodinated resin.

The converεion at elevated conditionε, in accordance with the present invention, may be effected in a reactor which is pressure sealable during conversion but which may be opened for recovery of the reεin product after a predetermined reaction time. The proceεε may thuε be a batch proceεs wherein conversion at elevated temperature and presεure iε effected once the reactor iε εealed. In accordance with the preεent invention the reactor may be εized and the amount of reactantε determined εo aε to provide a void space in the reactor during reaction. In the case, for example, wherein the material having the denotable iodine-member is a εludge of alkali metal/I ₂ and water, the weight ratio of sludge to resin may be 1:1 or higher, eg. 1:1 to 5:1; a weight ratio of 1:1 (if Amberlite 401-S iε uεed aε the reεin) iε preferred so aε to minimize the amount of unabεorbed iodine which muεt be waεhed from the iodine/reεin product.

The high temperature/preεsure contact conditions may aε mentioned above be choεen with a view to maximizing the iodine content of the obtained iodine (e.g. iodine) demand resin.

In accordance with the present invention conversion of the resin to a polyhalide (e.g. I ₃ ^" ) form may be effected at elevated temperature greater than 100° C, for example in the range of 105° C to 150° C (e.g. 110-115° C to 150° C) ; the upper limit of the temperature used will, for example, depend on the characteriεtics of the resin being used, i.e. the

temperature should not be so high aε to degrade the reεin.

Aε mentioned in order to effect the converεion at elevated preεsure, the conversion may take place in a cloεed vessel or reactor. The presεure in εuch caεe may be a function of the temperature such that the presεure may vary with the temperature approximately in accordance with the well known gas equation PV = nRT, wherein V = the constant (free) volume of the reactor, n = moles of material in the reactor, R is the universal gaε conεtant, T is the temperature and P is the pressure. In a closed vessel, the temperature of the system may therefore be used as a means of achieving or controlling the (desired) presεure in the vessel depending upon the makeup of the Iodine mix in the reactor. Thus in accordance with the present invention, a reaction mix diεpoεed in a preεεure εealed reactor may be, for example, εubjected to a temperature of 105° C and a pressure of 200 mmHg, the presεure being induced by steam.

Alternatively, a relatively inert gas may be used to induce and\or augment the pressure in the reactor. Thus, a presεurized relatively inert gaε may be injected into a sealed reactor. The chosen gaε muεt not unduly interfer with the production of a εuitable iodinated reεin. The high temperature/pressure treatment may be conducted in a cloεed reactor in the preεence of (trapped air) , a non-interfering gaε εuch aε iodine itεelf or of εome other relatively inert (noble) gaε; the pressure as mentioned above may be augmented

by the presεuring gas. Air, carbon dioxide, nitrogen or the like may also be uεed as a presεuring gaε, if deεired, keeping in mind, however, that the uεe thereof must not unduly interfer with the production of a suitable iodinated resin. If pressure is to be induced by steam then as mentioned below εteps should be taken to isolate the reaction mix from (exceεs) water.

In accordance with the present invention, the elevated pressure is any preεεure above ambient. The preεsure may, for example, be 1 psig or higher, e.g in the range from 5 to 50 psig; the upper limit of the presεure uεed will also, for example, depend on the characteristics of the resin being used, i.e. the presεure εhould not be εo high aε to degrade the reεin.

The residence or contact time at the elevated conditions is variable depending upon the starting materials, contact conditions and amount of (tenaciouεly held) iodine it iε deεired to be abεorbed by the anion exchange reεin. The contact time may thuε take on any value; uεually, however, it iε to be expected that it will be desired that the contact time (under the conditions used) be sufficient to maximize the amount of (tenaciously held) iodine absorbed from the material containing the absorbable iodine moiety. The reεidence time may for example be aε little aε 5 to 15 minuteε (in the caεe where a preimpregnation εtep iε uεed aε εhall be described below) or several hourε or more ( up to 8

or 9 hours or more) . The residence time exploited for elevated the conditions, in any event, will aε mentioned above depend on the εtarting material, temperature and preεεure conditions, etc... ; it may vary from several minutes to 8 or 9 hours or more; the upper time limit will in any event also, for example, depend on the characteristics of the resin being used, i.e. the residence time should not be so high as to degrade the resin.

Preferably, the contact at high temperature/presεure iε preceded by an initial impregnation or absorption step (first stage) . Such first stage may be carried out for only a few minutes (e.g. for from 1 to 10 minutes or more) or for up to 24 hourε or more (e.g. for from one hour or more i.e. for from three to twenty-four hourε) . The time period of the initial stage may be relatively short. The time period, for example, may be a few minutes or εo and may correpond to the time necessary to just mix the reactantε together; in thiε caεe the converεion may be considered to be essentially carried out in a single stage at elevated conditions. The residence time of the first stage will also be predetermined with a view to the end product resin desired. For example, a water containing sludge of triiodide ions can be contacted with a salt form of the starting resin at ambient (i.e. room) temperature and pressure conditions to obtain an intermediate iodide-reεin reaction product including residual iodine- substance. This step is preferably carried out in a batch reactor; the obtained intermediate compoεition comprising an

intermediate iodide-reεin may then be εubjected to the higher temperature and preεεure in accordance with the present invention in batch fashion as well. Such a first stage may be used to initiate buildup of iodine within the resin matrix.

In accordance with the present invention an iodide-resin demand disinfectant may, for example, be obtained by a) bringing a porouε, granular, εtarting reεin into contact with an aqueous sludge of iodine and potasεium iodide εo aε to obtain a paεte mixture, iodine being preεent in the εludge eεεentially as triiodide ions, εaid εtarting resin being a strong base anion exchange resin having strongly basic groups thereof in a salt form the anion of which is exchangeable with triiodide ions, b) subjecting the paste mixture to elevated temperature and pressure conditions in an enclosed container or reactor (e.g. autoclave) for a predetermined impregnating duration of time, a void space being provided in the reactor such that contact occurε under an (eεεentially) iodine (rich) atmoεphere, and c) washing the obtained iodide-resin product (with a suitable (i.e. purity) washing liquid, (e.g. deioniεed water, R/O water (at 45° C) , etc.) to remove water elutable iodine εuch aε KI from the surface of the resin so that on drying no iodine (KI) crystalε will form on

the surface of the iodine/resin; R/O water, is water obtained using double reverεe oεmoεiε. R/O water is defined below.

More particularly an iodide/resin demand diεinfectant may be obtained using the following sequence of stepε:

1. The reεin iε purified by triple passage of water and then dispoεed in ethanol in an electroεonic bath and flushed with water and drip dried; 2. (Esεentially) εtoichiometric amounts of I ₂ and potassium iodide are admixed with a minimum amount of water which is just sufficient to obtain an I ₃ - slurry or sludge (with, if desired, very low heating) ;

3. The resin is admixed with the above-minimal water slurry in small aliquats so as to obtain a predetermined weight ratio of slurry to reεin (e.g. a 50:50 weight ratio) ;

4. The reεin-slurry mixture is then placed in a εhaking bath at atmoεpheric pressure in a closed, air- tight container (if neceεεary the container being provided with a εmall preεεure releaεe valve or opening the purpoεe of which will be hereinafter explained) for a predetermined time period (e.g. for up to, for example, εixteen to twenty-four hourε or more [e.g. a week if deεired]) to form an intermediate reεin compoεition;

5. The container containing the reaction mixture iε then diεpoεed in a (εteam) autoclave and heated at high

temperature, (e.g. 120° C) to provide a εuper atmoεpheric preεεure therein (with the ε all valve open if the container walls would not be able to resist the pressure to be exerted within the autoclave) for a predetermined residence time (e.g. a residence time of about fifteen minuteε) calculated from the time the mixture reacheε the predetermined high temperature (e.g. 120° C) .

6. The autoclave iε removed from the heat and aε εoon aε the preεsure is equalized to atmospheric, the internal container is removed and the resin product is washed (e.g. six times) with R/O water until the wash water comes out with a total iodine content of less than 0.1 parts per million.

A small hole is necesεary when a container such as a glass flask is used in order to avoid a too great preεsure difference being built up between the interior of the flask and the interior of the autoclave which might cause the flask to collapse. The hole in any event is juεt large enough to more or leεε allow for the equalization of preεεure and to maintain a poεitive presεure in the flask relative to the interior of the autoclave such that any foreign material such aε water vapour is inhibited from flowing into the flask. A more εturdy preεεure reεistant container could of course be used such that, depending on the construction of the container and the temperature/preεεure conditionε prevailing in the autoclave, the hole may be avoided. Alternatively,

instead of using a separate container to hold the reaction mix and placing it in a separate autoclave, a single autoclave/container may be uεed serving to hold and heat the reaction mix under presεure; such a container muεt of course be constructed so as to be able to resist the predetermined reaction conditions.

The iodide-resin compound formed as described herein can be used as a demand disinfectant to diεinfect water by batch contacting the contaminated water with the reεin; continuouε proceεεing as mentioned in United States patent no 3,923,665 is also possible. Thus water containing viable bacteria (to be killed) may be paεεed through a fixed bed of porous granular iodine/resin material. The maximum permisεible flow rateε for total bacterial εterilization may vary with the concentration of the polyiodide (e.g. triiodide) groupε in the resin, bed depth, bacterial count, etc... The disinfection process may be monitored by taking sampleε of water after paεsage through the bed. Potable innocuous water may thus be readily produced in accordance with the present invention without the incorporation of objectionable amountε of free iodine therein as a result. The resin may be used with any (known) water treating devices such as for example those shown in U.S. patent nos. 4,749,484 and 4,978,449.

In accordance with a further aspect, however, as mentioned above, the present invention also provideε a method for disinfecting air containing airborne microorganismε. The

method may comprise pasεing the air over a demand diεinfectant resin such that airborne microorganisms contact said resin and are devitalized thereby, the demand disinfectant reεin comprising an iodinated strong baεe anion exchange reεin. The method may, for example, include passing the air through a bed of granules of iodinated resin so that the air courseε over the granules (in a serpentine manner) aε the air makeε itε way through the bed. The maximum permissible flow rates for total bacterial sterilization may vary with the concentration of the polyiodide groups in the resin, bed depth, bacterial count, etc... The iodinated strong base anion exchange resin may comprise a strong baεe anion exchange reεin component which repreεents from 25 to 90 (preferably 45 to 65) percent by weight of the total weight of the iodinated resin.

In accordance with an additional aspect, the preεent invention provideε a system for disinfecting air containing airborne microorganisms, said εyεtem, for example, comprising means for providing an air path for the movement of air therethrough, and a demand diεinfectant reεin diεpoεed in εaid air path εuch that airborne microorganiεms in air passing through said air path are able to be brought into contact with εaid resin and be devitalized thereby, said demand disinfectant comprising an iodinated strong baεe anion exchange reεin.

An air path means may define an air inlet and an air outlet. The resin may be dispoεed between said inlet and outlet or be dispoεed at the inlet or outlet. The air path meanε may take any form. It may take the form of ductwork in a forced air ventilation system with the demand disinfectant comprising a bed of reεin granuleε through which the air iε made to paεε, the bed otherwiεe blocking off the air path. Alternatively the air path meanε may be defined by a cartridge uεed for a gas mask, the cartridge having an inlet and an outlet for air; the iodinated reεin for the cartridge may, if deεired, be preεent aε a bed of granuleε, granuleε incorporated into a (fluid) porouε carrier (e.g. tissue, polyurethane foam, etc.) or alternatively take a more masεive form such as a plate(ε), a tube(s), a block(s), etc.. Cartridge type gas maskε are known; εuch gaε maεkε may be obtained for example from Eastern Safety Equipment Co., Mosport, New York, USA.

The C-50 cartridge from a gas mask (from Glendale Protecting Technologieε Inc. oodbury , New York, USA) may for example be adapted to hold a bed of reεin of granules of the present invention. Referring to figure 3, the cartridge 1 compriεeε an a hollow, open ended, thi-walled, tubular body of circular croεε εection. The wall 2 may for example be of nylon. The open endε of the cartridge are each blocked off by some suitable meεh like support material 3 (e.g. 10 micron polypropylene mesh) which is held in place in any suitable known manner such aε by glues, spring clip, etc. Referring to figure 4, the iodinated granular resin bed 4 occupies the

entire space between the meεh supports 3 and 3 * ; although the granular resin is more or less tightly packed between the mesh εupportε 3 and 3 ' , there are εtill air spaces between the granules for the passage of air through the granular bed. The mesh supportε each have openingε εmall enough to retain the iodinated resin in place while allowing air to pass therethrough into the and through the supported resin bed 4. The cartridge as shown in figure 4 may include a downstream bed 5 of granules of activated carbon, catalyst, or iodine absorbent resins, to scavenge any iodine liberated from the iodinated resin 4. The activated carbon bed 5 iε held in place by a meεh support 3' and an additional mesh 6. The bed depth of the resin and carbon is shown as about 2.5 cm; wheras the bed diameter is about 8 cm. If the iodinated resin made in accordance with the procesε of the present invention is uεed the carbon bed may be omitted, i.e. only the iodinated resin bed 4 may be present in the cartridge as the active component (in the examples below, unless the contrary is indicated, the cartridgeε do not include any carbon bed) ; in thiε caεe the bed depth may, for example, be leεs 2.5 cm, e.g. 0.1 cm, 0.25 cm, 0.5 cm, 0.85 cm, 1.15 cm, etc.. Such a cartridge may be disposed in an air path as shown for example in figureε 5 and 6 which will be diεcuεεed below.

The reεin diεposed in the air path could of course take on any form other than granuleε εuch as blocks, plates, tubes etc..

The iodinated demand disinfectant resin for air treatment may be any (known) iodinated resin so long as the iodinated reεin iε capable of devitalizing airborne microorganisms (i.e. microorganismε tranεported by air) coming into contact therewith. It may, for example, be a reεin as proposed in U.S. patent nos. 3,923,665 and 4,238,477; in thiε caεe, however, it may be necessary to use the resin in conjunction with an iodine εcavenging material if the reεin gives up too much iodine to the air. The iodine scavenging material may be an activated carbon material or an un-iodinated strong baεe anion exchange reεin aε deεcribed herein.

Alternatively, as mentioned above, iodinated resin may advantageously be a resin made in accordance with the preεent invention; in thiε caεe the reεin need not be uεed in conjunction with an iodine εcavenging material εuch as a (known) exchange resin, activated carbon, catalyst, etc. , since an iodinated resin made in accordance with the procesε of the preεent invention may liberate iodine into the air in an amount below acceptable threεhold limits for breathing by human beings.

If desired the iodinated reεin for the treatment of air or water may be εome type of mixture of iodinated reεinε, e.g. a mixture of a known iodinated reεin and an iodinated reεin prepared in accordance herewith.

Aε mentioned above, the preεent invention in a further aεpect

provides a combination which may act as a sterilization barrier with respect to microorganiεms. The sterilization combination may, for example, be incorporated into protective wearing apparel or be configured aε a εterilization dreεεing for leεions such as for example, wounds and burns; the εterilisation barrier combination can be configured to be or not to be air breathable.

A sterilization dressing of the present invention advantageously may take the form of a flexible porouε cellular polymeric foam εheet having a spongy aspect and having dispersed within the polymeric matrix thereof particles of a demand disinfectant comprising a (known) iodinated reεin or an iodinated resin as deεcribed herein. The εterilization εheet may be placed over a burn area to maintain the burn area in a εterilized εtate during the healing proceεε. The diεinfectant particleε are diεtributed throughout the polymeric matrix and have εurfaceε projecting into the open poreε of the εpongy matrix; the εpongy matrix acts as a sponge so that on the body side thereof it can soak up fluid εuch aε puε which exude from the burn leεion. Once within the body of the matrix any microorganisms in the fluid or pus can contact the diεinfectant reεin particleε and become devitalized aε a reεult. On the other hand, any microorganiεms on the opposite side of the sterilization barrier which attempt to pass through the barrier are also subject to being contacted with the diεinfectant and are also devitalised.

A (flexible) phamaceutically acceptable hydrophilic foam matrix may be obtained by reacting water with HYPOL foamable hydrophilic polyurethane polymer; the HYPOL polymer starting material may be obtained from .R. Grace & Co. Lexintington Mass. U.S.A.. Water reacts to cross link the HYPOL polymer; if water is added quickly or at relatively high temperature foaming occurs and a foam product is obtained.

The carrier component may, as necessary, also be oil or fat loving, e.g. for dealing with individuals with high cholesterol levels.

If desired the iodinated resin for the steriliεation combination may be some type known iodinated resin, a resin prepared in accordance herewith, or a mixture of iodinated resins, e.g. a mixture of a known iodinated resin and an iodinated reεin prepared in accordance herewith.

Figureε 7 to 11 which illuεtrate a number of example embodiements of steriliεation barrier combinationε of the present invention will be discussed below; these combinations are also described in example 15 below.

Turning back to the procesε of the preεent invention, if commercially available materials are to be used to make the iodine/resin then, depending on the purity thereof, the εtarting materials may have to be treated to remove components which may interfer with the absorption of the

halide into the resin. Water if present in the initial reaction mix should be free of interfering elements such as interfering ions. Distilled or ion free water is preferably used for washing.

The following materials may be used to prepare a triiodide reεin in accordance with the preεent invention:

a) Amberlite 401-S (from Rohm & Haεε) a strong base anion exchange reεin in granular form, having the following characteriεtics: support matrix - styrene/divinyl benzene polymer anion - chlorine denεity - 1.06 effective εize (diameter) - 0.52 mm total exchange capacity - 0.8 meq/ml working Ph range - 0 to 11 moisture content - 62% working temperature - 170° F or less

b) I ₂ (solid) - U.S.P. grade (from Fiεher Scientific)

c) Potaεεium iodide (KI) - U.S.P. grade (from Fiεher Scientific)

d) Water - ultra pure: obtained using double reverεe oεmoεiε (i.e. herein sometimes referred to simply aε R/O water)

e) Ethanol - U.S.P. grade (from Fisher Scientific)

Uεing the above εubstances a resin cramed with triiodide (i.e. a triiodide jam-backed reεin) may be obtained as indicated in the following examples.

For the following exampleε, the following procedure for the evaluation of iodine (I ² ) and Iodide (I ^" ) , waε conducted according to "εtandard methodε for the examination of water and wastewater 17e Ed.":

Iodine method: mercuric chloride added to aqueous elemental iodine εolutions causes complete hydrolysis of iodine and the stoichiometric production of hypoiodouε acid. The compound 4, 4', 4" methylidynetriε (leuco crystal violet) reacts with the hypoiodous acid to form cryεtal violet dye. The maximum absorbance of the crystal violet dye εolution iε produced in the Ph range 3.5-4.0 and meaεured at a wavelength of 592 nm. The abεorbance follows beers' law over a wide range of iodine concentration. Iodine can be meaεured in the preεence of max. 50 PPM iodide ionε without interference.

Iodide method: iodide is selectively oxidized to iodine by the addition of potasεium peroxymonoεulfate. The iodine produced reactε inεtantaneously with the indicator reagent leuco crystal violet over the same

conditions described previously for iodine methods. Total iodine + iodide results from this procedure and iodide is calculated from substraction of iodine concentration.

Readings were performed on a lkb spectrophotometer with a lightpath of 1 cm and selected at 592 nm.

EXAMPLE 1: STARTING MATERIALS PRETREATMENT:

i) Resin:

The resin is water waεhed to remove undeεirable elementε such as material in ionic form. Thuε, 100.00 grams of Amberlite 401 S and 200 ml of R/O water are placed in an erlenmyer of 1000 ml. The mixture is shaken for about 3 minuteε and the water iε then εeparated from the reεin by drip filtration uεing a wathman filter paper and funnel. The reεin iε water waεhed in the εame faεhion two more timeε. After the laεt water waεh the resin is drip dried (i.e. again using a wathman filter paper and funnel) for 15 minutes.

The εo recovered water washed resin is subjected to an alcohol wash to disεolve undeεirable organic material which may be stuck on the resin. Thuε, the water washed resin is immersed in 300.00 ml of ethanol. The reεin alcohol mixture iε εhaken in an ultrasonic bath (Crest ultrasonic:1000 Watts - 20 liter capacity) for 5 minuteε. The alcohol washed resin is drip dried, again

using a wathman filter paper and funnel. The "fiεh" smell iε removed from the alcohol waεhed resin by a final water washing stage wherein the wash R/O water is preheated to 40 degreeε celεius. The alcohol washed resin is placed in an erlenmyer flaεk (1000 ml) and 250 ml of R/O water at 40 degreeε celεius is added thereto. The water-resin mixture is shaken in a shaking bath (Yamata shaking bath - 1 impulse per εecond/water at 32 degrees celsius) for 5 minutes; the water is then removed from the resin by drip drying aε mentioned above. The water wash is repeated once more and the resin is drip dried (for 1 hour) as mentioned above. The washed reεin iε now ready for use in example 2 hereinbelow.

ii) Iodine sludge containing water:

A mixture of iodine (I ₂ ) and potaεsium iodide (KI) iε prepared by mixing together, in an erlenmyer flaεk, 60.00 grams of iodine and 40.00 grams of potassium iodide (in both caseε on a dry weight baεiε) . Thereafter R/O water is admixed slowly drop by drop with the mixture until a metallic looking sludge iε obtained (e.g. with the addition of about 5.00 grams of water). The obtained iodine/potassium iodide sludge iε then ready for use in example 2 hereinbelow.

EXAMPLE 2: LOW TEMPERATURE/PRESSURE PREIMPREGNATION OF

RESIN WITH IODINE

The aqueous iodine sludge, as obtained above, is placed in a 500.00 ml Erlenmyer flask and is slowly heated to, and maintained at 40 degrees celsius for a few minuteε. Once the temperature of the sludge reaches 40° C, the washed resin, obtained aε above, iε slowly admixed with the iodine sludge in 10.00 gram portions every 8 minutes until all of the washed resin is within the erlenmyer flask. The 500 ml Erlenmyer flask, containing the obtained starting mix (comprising the I ₂ /KI mixture and the washed reεin - approximately 100 gramε of each of the starting materials) , is then sealed with a cork and is placed in a shaking water bath (Yamato BT:-25) for a period of 16 hourε. The temperature of the water in the shaking bath is maintained at about 20 degrees celsiuε during thiε time period. At the end of the time period, the Erlenmyer flaεk iε removed from the εhaking bath; at thiε point the removed flask contains an preimpregnation mix compriεing impregnated reεin and remaining I ₂ /KI. The Erlenmyer flask is εized εuch that at the end of this (initial) impregnation step, it is only 50% filled with the in procesε resin, etc, i.e. there is a void volume above the impregnation mix.

NOTE: If procesεing of the treated reεin iε εtopped at thiε point and the obtained reεin iε suitably washed, a resin is obtained in accordance with the prior art i.e. U.S. patent no. 3,923,665.

EXAMPLE 3: ELEVATED PRESSURE/TEMPERATURE TREATMENT

The cork of the Erlenmyer flaεk of EXAMPLE 2 removed from the εhaking bath and including the obtained impregnation mix comprising impregnated resin and remaining I ₂ /KI, is changed for a cork having a εmall diameter perforation passing therethrough (i.e. of about 3 mm in diameter) . With the perforated cork in place, the Erlenmyer flask iε disposed within a (steam pressure) autoclave along with a suitable amount of water. With the autoclave (preεεure) εealed about the flaεk, the autoclave iε heated. Heating proceedε until an internal temperature and preεεure of 115 degreeε Celεiuε and 5 pεig reεpectively iε reached. Once thoεe parameterε have been reached, they are maintained for 15 minutes of processing time. Thereafter the autoclave is allowed to slowly cool for 50 minutes of cooling time

(until the internal pressure is equal to ambient preεεure) before removing the Erlenmyer flaεk containing a (raw) product reεin demand disinfectant in accordance with the present invention.

EXAMPLE 4: WASHING OF RAW PRODUCT RESIN

The (raw) disinfectant of Example 3 is removed from the autoclave Erlenmyer flask and placed in another 2000 ml Erlenmyer flaεk. 1400 ml of R/O water at 20 degreeε Celεius is admixed with the resin in the flask and the slurry is shaken manually for 3 minutes. The wash water

is thereafter removed from the flask by decantation. This wash step is repeated 7 more timeε. The entire waεh cycle iε repeated twice (i.e. eight water washes per cycle) but using water at 45 degrees Celεius for the next wash cycle and then with water at 20 degrees Celsiuε for the last wash cycle. The washed iodine- resin iε then ready to use.

EXAMPLE 5: COMPARATIVE PHYSICAL DATA: The following resinε were examined with respect to certain physical characteristics:

Resin I-A :

Iodinated resin manufactured in accordance with the present invention i.e. as obtained from example 4 above.

Resin I-B :

Iodinated resin manufactured in accordance with teachings of the prior art (i.e. U.S. patent no. 3,923,665), namely as obtained from example 2 above after suitable washing to remove elutable iodine.

Resin I-C :

Iodinated resin manufactured by Water Technology Corporation in Minneapolis (a triiodide based disinfectant resin) .

Resin I-D :

Iodinated resin manufactured by Water Technology Corporation in Minneapolis, sold under the Trademark: Pentapure.

In the exampleε which follow the above reεinε will be referred to uεing the above deεignations, i.e. I-D, Resin I- A, etc.

EXAMPLE 5.1: COMPARATIVE WET TAP DENSITY:

The reεinε were examined in a drip dried εtate, i.e. the reεinε were uεed after being drip dried uεing wathman filter paper and a funnel (for a 5 minute dry period) .

25 ml and 100 ml flaεkε were used for the study. The flaεkeε were weighed empty. The flaεkε were then filled with reεin and were then εubjected to a manual vibration εequence (approximately 2 impulεeε per εecond for two minuteε) in order to εettle the reεin, the volume of the settled resin was then noted. The density was obtained by weighing a filled flask and subtracting the weight of the empty flask so as to obtain the weight (gramε) per unit volume (ml) of the reεin. The reεults are shown in Table 1 below.

Table 1 Resin density

I-A 1.720 gm/ml

I-B 1.480 gm/ml

I-D 1.600 gm/ml

EXAMPLE 5.2: COMPARATIVE DRY TAP DENSITY:

The same procedure aε deεcribed above for example 5.1 waε uεed except that the initial reεin materialε were dried εimultaneouεly for 12 hourε at 55 degreeε Celεius, and placed in desiccant for 2 hourε during cooling. The reεultε are εhown in Table 2 below.

EXAMPLE 5.3: IODINE CONTENT:

1.0 g of each of the different resins was boiled in 20 ml of water with a concentration of 5% by weight of εodium thioεulphate. Boiling waε conducted for 20 minuteε whereafter the water mixture waε set aside to air cool for 12 hours. The resin was then recovered and washed with 50 ml of a boiling water solution of εodium thioεulphate. Thereafter the reεin was dried in an oven for 12 hours at 105 degreeε. The iodine deεorbed reεin waε weighed in each caεe and the weight difference waε uεed to calculate the % by weight of the initial reεin

repreεented by the active iodine removed. The reεultε are shown in Table 3 below.

NOTE: As may be seen from Table 3, the resin in accordance with the present invention (i.e resin I-A) has a εubεtantially higher iodine content than the commercially available resins or the resin prepared in accordance with the prior art

(i.e. resin I-B) .

EXAMPLE 5.4: COMPARATIVE IODINE CONTENT IN WATER DURING

STAGNATION: 100.00 gm of each reεin waε mixed with 125 ml of water in Erlenmyer flaεk which waε εealed airtight. The water mixture waε allowed to εtand 20 degreeε Celsius for 7 days. A water sample was then taken from each water mixture and subjected to a standard method for testing water for the presence of Iodine using the Leuco Cryεtal Violet lodometric Spectrophotometer Technique εo aε to obtain the "ppm" concentration of iodine in the water. The reεultε are εhown in Table 4 below.

Table 4

Resin bleed iodine concentration (ppm)

I-A 1.7 ppm

I-D 2.5 ppm

NOTE: As may be seen from table 4, the resin of the present invention (reεin I-A) haε a εignificantly lower iodine bleed lose into water than the commercial product (resin I-D) .

EXAMPLE 5.5: RESIN SIZE STUDY:

Two grams of dry reεin waε examined with a microscope having a micrometer scale system and sized by eye. The reεultε are εhown in Table 5 below.

Table 5

Reεin Size (ie. approximate effective diameter size) - lowest to highest

AMBERLITE I 401 S 0.35 mm to 0.52 mm

I-A 0.60 mm to 1.20 mm

I-B 0.40 mm to 1.00 mm

EXAMPLE 6

Simultaneous teεtε were conducted to compare the antimicrobial activity of a diεinfectant reεin in accordance with the preεent invention (reεin I-A, above) and a prior art diεinfectant reεin (reεin I-D, above) . A series of batch solutionε waε prepared; each batch εolution contained a

different microorganiεm. A batch εolution waε divided into test portions so that the comparative tests could be carried out against each of the resinε at the εame uεing a reεpective teεt portion of the batch εolution; the volume of the teεt portionε waε 150 literε. The same amount of each of the reεins was supported in a reεpective fixed bed configuration

(i.e. the reεinε were diεpoεed in a cylinder 1 cm high having an internal diameter of 3 cm) . The reεpective test solutionε were allowed to paεε downwardly through each of the resins in the same fashion and at the εame flow rate (i.e. the teεt conditionε were the same for each resin) . The testε were carried out at ambient conditionε of temperature and preεεure. The microorganiεmε and teεt reεultε were aε followε: a) A lyophilized εtrain of KLEBSIELLA TERRIGENA

(A.T.C.C. 33257) waε rehydrated in phoεphate-buffered εaline (PBS) and waε εubcultivated in order to obtain a broth with a bacterial denεity of 10° cfu/ml (cfu = colony forming unitε) . The broth waε treated to obtain media free monodiεperεed bacterial cells. The bacterial solution was then diluted in water to provide the teεt batch solution at an initial concentration of 4.8 X 10 ⁷ cfu per 100 ml.

Microbiological monitoring of the test water was done throughout the experiment. Sampling of the filtered water was done at intervals prescribed by the: U.S.E.P.A. (protocol section 3.5.1 d 1(b)) with the

membrane-filter technique for KLEBSIELLA deεcribed in: 17th edition of Standard Methodε for the examination of water and wastewater, pp. 9-97 to 9-99.

A test solution containing KLEBSIELLA TERRIGENA (A.T.C.C. 33257) at an initial concentration of 4.8 X 10 ⁷ per 100 ml was pasεed through the fixed bed of each reεin at a flow rate of 125 ml/min to 200 ml/min. The treated volume of solution for each resin was 150 liters in total. Sampling of the effluent or treated εolution waε effected at intervalε correεponding with a predetermined percentage of the teεt portionε having paεεed through the reεinε. The reεults are shown in Table 6a below:

Table 6a

Total % of teεt Microorganiεm concentration in test solution pasεed effluent for each resin type (cfu/ml) through the reεin

Reεin I-D Reεin I-A

0%. ,0/0/0 .0/0/0 25% 0/0/0 0/0/0 50% 0/0/0 0/0/0 60% 0/0/0 0/0/0 75% .07070- 0/0/0 90% 0/0/0 0/0/0 100^ 0/0/0 0/0/0

As may be seen from table 6a the destruction of the bacteria was total in the case of each resin.

b) Polioviruε 1 (A.T.C.C VR-59) waε obtained as a lypholized pellet, rehydrated in PBS, and grown on buffalo green monkey (BGM) kidney cells from the Armand Frappier Institute (IAF) in Laval Quebec. Standard cell culture and virological procedures were used to obtain a concentration of 3 x 10 ⁷ of monodisperεed virion particleε per ml. Enough virus was added to a holding tank to obtain a concentration of about 1 X 10 ⁷ pfu per liter for the test batch solution (pfu = plaque-forming units) .

The assay technique consiεted of inoculating healthy BGM cellε with a εmall amount of filtered water at regular intervalε. If a viruε particle were preεent, a plaque would be observed on the cellular bed thru the gellified maintenance media which contained a vital stain.

A test solution containing Poliovirus l (A.T.C.C VR-59) at an initial concentration of 1 X 10 ⁷ pfu per liter waε paεεed through the fixed bed of each reεin at a flow rate of 125 ml/min to 200 ml/min. The treated volume of εolution for each reεin waε 150 literε in total. Sampling of the effluent or treated solution was effected at intervals corresponding with a predetermined percentage of the teεt portionε having passed through the resinε. The reεultε are εhown in Table 6b below:

Table 6b

Total % of teεt Virus concentration in test effluent εolution paεεed for each resin type (pfu/1) through the reεin

Resin I-D Resin I-A

0% 0/0/0 0/0/0

25% 0/0/0 0/0/0

50% 0/0/0 0/0/0

60% 0/0/0 .0/0/0

75% 0/0/0 0/0/0

90% 0/0/0 0/0/0

100% 0/0/0 0/0/0

As may be εeen from table 6b the destruction of the Poliovirus waε total in the caεe of each resin.

c) Rotavirus (A.T.C.C VR-899) waε obtained , rehydrated in PBS, and grown on A-104 cellε obtained from IAF. The method uεed to obtain the diluted polioviruε above waε used with respect to the rotavirus. The yield for rotaviruε grown on MA-104 cellε waε 2xl0 ⁶ pfu/ml. After dilution in the holding tank the concentration of the viruε waε 1 X 10 ⁷ pfu per liter.

The aεεay techniqueε were εimilar to thoεe uεed for polioviruε, only the cell type and vital εtain changed εince they are εpecific for each type of virus. The same sampling strategy was applied.

A test solution containing Rotavirus (A.T.C.C VR-59) at an initial concentration of 1 X 10 ⁷ per 100 ml was passed through the fixed bed of each resin at a flow

rate of 125 ml/min to 200 ml/min. The treated volume of solution for each resin was 150 literε in total. Sampling of the effluent or treated εolution waε effected at intervalε correεponding with a predetermined percentage of the teεt portions having passed through the resins. The results are shown in Table 6c below:

Table 6c

Total % of test Viruε concentration in test effluent solution pasεed for each resin type (cfu/ml) through the reεin

Resin I-D Reεin I-A

0%. ,0/0/0 0/0/0 25% ,0/0/0 0/0/0 50% 0/0/0 0/0/0 60% 0/0/0 0/0/0 75% 0/0/0 0/0/0 90% 0/0/0 0/0/0 100 0/0/0 0/0/0

As may be seen from table 6c the destruction of the Rotavirus was total in the caεe of each reεin.

EXAMPLE 7

An iodine bleed teεt waε conducted on the Reεin I-A and Reεin I-D mentioned above. The tests were conducted as follows: A pressure syringe was filled with 20 gramε of resin (inner chamber of 3 cm x 13 cm) . Using a peristaltic pump 750 ml/min of R/O water (sterilized) waε pumped through the syringe; the resin being maintained in the syringe by suitable mesh means. The total water passed

through the reεin waε 5 literε. The reεultε of the teεts are given in the graph shown in figure 1; i.e. ppm iodine in effluent vs total volume water pasεed through reεin. The bleed teεt reεultε aε εhown in the graph compareε iodine (I ₂ ) and iodide (I ^" ) in effluent of treated water after pasεing through each of the resins.

EXAMPLE 8

The bacteriocidal longevity of the Resin I-A and Resin I-D were determined for purposeε of compariεon. Two fixed resin bed devices were provided, one device loaded with one of the resins and the other device loaded with the other resin; each device was loaded with 75.00 grams of a respective resin. The tests for each resin bed were conducted simultaneously. For each resin bed, the εolution to be treated was passed therethrough at a flow rate of 2.0 litres per minute, with an initial concentration of Klebεiella Terrigena 1 X 10 ⁷ cfu/100 ml. The effluent waε teεted at intervalε for the preεence of viable bacteria. As may be seen in the graph of figure 2, the volume of contaminated solution at which bacteria start to pasε through the prior art reεin (i.e. Reεin I-D) iε significantly less than the breakthrough volume for the resin of the preεent invention (i.e. Resin I-A) . From figure 2 it may be seen that the bacteriocidal activity of the disinfectant resin of the present invention (Reεin I-A) is superior to that of the known resin (Resin I-D), i.e. the Resin I-A has about a 16% εuperior antimicrobial activity in relation to the amount of water treatable by a given amount

of disinfectant resin.

EXAMPLE 9: Preparation of Reεin I-A ¹ of the preεent invention

An iodinated reεin (Resin I-A') waε prepared following the procedureε of examples 1 to 4 except that for the resin, Amberlite IR-400 (OH ^" ) (waε uεed and for the procedure of example 3 the elevated temperature and preεεure conditionε were εet at 121° C and 15 pεig reεpectively. Reεin I-A ¹ waε uεed in the following exampleε.

EXAMPLE 10: COMPARATIVE IODINE CONTENT IN EFFLUENT AIR

Two cartridgeε aε illuεtrated in figures 3 and 4 were prepared. Each cartridge contained 50.0 grammes of dry (granular) resin (i.e. and no activated carbon bed) . One cartridge contained Resin I-A' and the other contained Reεin I-D.

The cartridgeε were each disposed in a syεtem as illustrated in figure 5 but which did not contain any atomizer indicated generally by the reference number 7. The system included a housing 8 for defining an air path and had an air inlet 9. The resin cartridge 1 waε disposed at the outlet of the air path. The air leaving the cartridge 1 was directed by appropriate tubing to a collector station 10. The syεtem included a vacuum pump 11 (but not the air sterilizer syεtem 12) for drawing air from inlet 9 through the εyεtem.

In operation a cartridge 1 waε releasably placed in position

(e.g. snap fit, etc.) and the vacuum pump activated so as to draw outεide air (indicated by the arrow 13) into the houεing

8. The air paεεed through the cartridge 1 aε εhown by the arrowε 14. The air leaving the cartridge 1 waε then directed to the collector εtation 10. The air entering the collector εtation 10 impinged upon a iodine collector solution 15 (comprising double reverεe oεmoεiε water, i.e.

R/O water) in the collector εtation 10. Air leaving the collector station 10 thereafter pasεed through the pump 11 and waε exhauεted to the outside air.

Using the above described syεtem, each, cartridge was εubmitted to an air velocity therethrough of 0.7 Liter/per minute for a period of 50 minuteε. The collector εtation 10 included 50 ml purified R/O water (the water was then subjected to standard optical coloration techniqueε (i.e. the Leuco violet technique aε referred to in example 5.4 above), to determine the total iodine content) .

The reεults of the testε are εhown in table lOa:

Table 10a Reεin type total iodine (I ₂ )

Resin I-A ¹ 0.4 ppm Resin I-D 1.1 ppm

The reεults of the tests as εhown in table 9a meanε that each gramme of both of the reεin typeε will add a definite amount

of iodine to the effluent air, namely aε indicated in table 10b.

Table 10b Resin type iodine (I ₂ ) release per gram resin

Resin I-A' 0.014 Mg/m ³ /gr

Reεin I-D 0.031 Mg/m ³ /gr

Thuε, for example, if a gas mask cartridge as discusεed above contained 50.0 gm of iodinated resin, the resinε would emit the level of iodine εet out in table 10c below

Table 10c Reεin type iodine (I ₂ ) release Resin I-A ¹ 0.7 Mg/m ³ (= 50 gr x 0.014 mg/m ³ /gr)

Reεin I-D 1.5 Mg/m ³ (= 50 gr x 0.031 mg/m ³ /gr)

The "Committee of the American conference of governmental induεtrial hygieniεt." emitε the "threshold limit value" or T.L.V. for common chemicals. The iodine T.L.V. is 1.0 Mg/m ³ for air analysis for human breathing during a period of 8 hrs.

Thuε, while the Resin I-D releaseε 50% more iodine than the maximum T.L.V. indicated above, the Reεin I-A' (of the preεent invention) releaεeε iodine at a level well below the T.L.V. The Resin I-A ¹ could thus be used without an iodine scavenger; thiε would, for example, simplify the construction of a gaε maεk cartridge. The known Reεin I-D on the other

hand could also be used but it would require some sort of iodine scavenger (e.g. activated carbon) to obtain the necessary iodine T.V.L. level.

EXAMPLE 11: The Resin I-A ¹ was tested with different micro-organisms under different conditions for the sterilization of air.

EXAMPLE 11.1: Direct contact sterilization study

Reεin I-A' waε evaluated for itε biocidal capacity on direct contact with Klebεiella Terrigena in relation to a time reference and a humidity content variation; namely water content variationε of 110%, 50% & 0% (relative to the weight of dry reεin) and time variations of 2, 5, 10, and 15 secondε.

After preparing the three reεinε with their respective humidity content 25 glasε rodε were εterilized. A vial containing 25 ml of the inoculum (Klebεiella Terrigena: 10° x ml) waε alεo prepared.

The testing proceeded as follows with respect to the dry reεin. A glaεε rod waε immerεed in the inoculum and then immerεed in the dry reεin for 2 εeconds. The glasε rod was then washed in 100 ml phosphate buffer to wash out the microorganisms. Following the standard method for evaluation of water, the collected εample waε then plated and incubated.

Thiε procedure waε then repeated for 5, 10 and 15 seconds.

The procedure was alεo repeated for the two other different humidity content batcheε of Reεin I-A ¹ . The reεultε of the teεt are shown in table 11a.

Table 11a number of viable microorganisms per time period

2 sec. 5 sec. 10 sec. 15 sec % humidity

110% 16 0 0 0

50 % 23 1 0 0

0 % 67 15 0 0

As may be seen from table 11a, the Reεin I-A ¹ whether wet, humid or dry deεtroyε large quantitieε of reεiεtant bacteria in direct contact, and thiε deεtruction occurs on a relatively rapid time base as demonstrated above.

EXAMPLE 11.2: KLEBSIELLA TERRIGENA ERADICATION STUDY: AIR FLOW.

A study waε done to evaluate the biocidal effectiveness of dry Resin I-A ¹ versus Klebsiella Terrigena.

The system used was the εyεtem illustrated in figure 5. The system included an atomizer 7 (of known construction)

diεpoεed in a houεing 8 provided with an air opening 9. The εystem had a vacuum pump 11 for the displacement of air through the system. The system included an air sterilizer 12 comprising a hollow houεing 10 inches high by about 2.5 inches in inner diameter and filled with about 1.5 kilograms of Resin I-A'; the sterilizer has an air inlet and outlet. The air path through the cartridge 1 is designated by teh arrows 14. The atomizer 7 contained an inoculum 16 (Klebεiella Terrigena: 10 ⁷ x 100 ml) . For the teεt, the air flow at arrow 13 waε εet at 30 liters per minute and the air inflow at arrow 17 for the atomizer was set at 8 liters per minute; the atomizer 7 injected miεt or εpray 18 of inoculum into the air in the air path and the inoculated air then paεεed through cartridge 1 aε εhown by the arrows 14.

A cartridge 1 as illustrated in figures 3 and 4 was prepared using dry Resin I-A' (65.0 gm giving a bed depth of 1.15 cm) . The cartridge 1 was submitted to an injection of a total of 10 ml of inoculum over a time period of 15 minute. Sampling was done at 0 minutes, 7.5 minutes and at 15 minutes. The samples were collected in a standard impinger aε εhown in figure 5. After, proceεεing 100 ml of the water from the impinger on microbiological paper filter and incubation, the reεultε εhow total eradication of Klebεiella Terrigena.

EXAMPLE 11.3: BACILLUS PUMILUS ERADICATION: AIR CONTACT.

A εtudy waε carried out uεing the εyεtem εhown in figure 6.

To the extent that members of the syεtem are the εame as those used in the system illustrated in figure 5, the same reference numerals are uεed to identify the same parts. The main difference between the syεtem of figure 5 and that of figure 6 iε that the εyεtem of figure 6 uεeε a microbiological filter paper 19 to collect the microorganiεmε leaving the cartridge 1; the filter paper iε maintained in place in any (known) εuitable faεhion.

An inoculum 20 of the thermophilic bacteria Bacillus Pumilus was prepared and injected at a concentration of 10 ³ /litre of influent air. A cartridge mask containing 65.00 gm of Reεin I-A ¹ waε prepared aε for the previouε example. The teεt ran for 30 minuteε.

All effluent (velocity at arrow 13 being 30 litreε per minute) waε collected on the microbiological filter paper 19 (from millepore) , then lain in a T.S.A. (trypticase Soy Agar) and incubated. the resultε εhowed total eradication of Bacilluε Pumiluε.

EXAMPLE 11.4: BACILLUS SUBTILIS STERILIZATION IN AIR FLOW.

This test was performed with Bacillus Subtilis in a mixture of 40% active bacteria / 60% sporeε. The εyεtem εhown in figure 6 was used with the cartridge comprising 50 grams of Resin I-A ¹ (giving a bed depth of .85 cm). The controlled concentration of processed air was 55 bacteriological units

per litre. The air velocity was 23 litre per minute for 80 minutes.

Once the 80 minuteε ended, the millepore filter paper waε collected, lain on T.S.A. (after neutraliεation of potential iodine with εodium thioεulfate 5%) and incubated for 48 hours at 37 degree celsius. The resultε εhow a total eradication of micro-organiεmε.

EXAMPLE 11.5: BACILLUS SUBTILIS: Reεin I-A" versus glasε beadε in air flow.

In order to assess the retention factor of micro-organisms on inert materials thiε test was performed. Alεo, to evaluate the migration factor of the biological vector, a εequential incubation waε performed.

Two gaε cartridges were built in accordance with figures 3 and 4, namely:

a) Resin I-A' cartridge : 10 micron polypropylene upstream mesh (filter) ;

: 50.00 gm of Reεin I-A' giving a bed depth of .85 cm; : 10 Micron polypropylene downεtream mesh (filter) .

b) Glasε bead cartridge : 10 micron polypropylene upεtream

mesh ( filter) ;

: 50.0 gm εterile glaεε beadε (from

Fiεher Scientific and having the εame εize aε the beads of Resin I- A ¹ ) giving a bed depth of .85 cm; and

: 10 Micron polypropylene downstream meεh (filter) .

The εyεtem aε εhown in figure 6 waε uεed for the teεts.

Simultaneously, the two cartridges were, once inεerted in their reεpective testing chamber, submitted to a velocity of 23 litre per minuteε for 40 minuteε with a microbiological load of 40 bacteria per litre in the influent.

Once the teεt period completed, the two cartridges were disεected in εterile conditions and the microbiological filter paper recovered. Each materials composing the masks were individually as well as the filter paper were incubated in T.S.A. for 48 hourε at 37 degree celεiuε. The results are shown in table lib.

Table lib

Resin I-A ¹ Glass beads

upstream mesh: 2 cfu tnc ^* cfu

Resin\beads: 0 cfu tnc cfu

downεtream meεh: 0 cfu 220 cfu

microbiological filter paper: 0 cfu 86 cfu

tnc = microorganisms too numerous to count

As may be seen from table lib the Resin I-A' eradicated all bacteria and no living micro-organism can live in the resin bed.

The Glass beads on the other hand have a mechanical filtering capacity in regards to the biological vector but migration occurs rapidly thus obtaining "tnc" results (too numerous to count) on the upstream mesh and the beads themselves. The migration keeps on going through the filter until it reaches the microbiological paper filter in large number. Also, the glasε beads filter becomeε εeverely contaminated, cauεing a disposal problem.

EXAMPLE 11.6: BACILLUS SUBTILIS: Resin bed depth comparison This test was performed to establish the biocidal effectiveness of the Resin I-A' in regards to the microbiological eradication of Bacillus Subtiliε. The εyεtem of figure 6 waε used.

Two cartridgeε aε illustrated in figures 3 and 4 containing

respectively 30.00 gm (giving a bed depth of 0.5 cm) and 50.00 Gr (giving a bed depth of 0.85 cm) of Resin I-A were submitted to 60 minutes of air pumping at a velocity of 27 litre per minutes. A total of 23 ml of inoculum at a concentration of 10 ⁷ per ml were injected into the system.

A positive control yielded a concentration of 275 cfu/litre of air at the microbiological sampling site.

The results show total eradication for both cartridgeε.

EXAMPLE 11.7: BACILLUS SUBTILIS: LONGEVITY STUDY IN AIR

FLOW.

A cartridge of figure 3 and 4 containing 30.00 gr (bed depth: 0.5 cm) of Reεin I-A' waε εubmitted to an air flow velocity of 25 litre/ minute containing a concentration of Bacilluε Subtiliε of 112 cpu/litre (poεitive control for correlation) for a period of 3 hrs.

The test was done using the impinger technique (of figure 5) , with 300 ml of εterile water. Once the 3 hours completed the water from the impinger was filtered on a microbiological membrane as referred in standard method for analysis of water and waste water 17 th edition, pp.9-97 To 9-99. The growth media waε trypticaεe soy agar. The results after incubation for 48 hours at 37.5 degree celεiuε was total eradication.

EXAMPLE 12: Studies of the fixation of iodine at different iodine concentrations

Reεin I-A ¹ , Reεin I-B ¹ , Reεin I-B" and Reεin I-A" were prepared aε followε:

Reεin I-A' waε prepared as described in example 9. Resin I-B' was prepared following the procedures of examples 1 and 2 except that for the resin, Amberlite IR-400 (OH ^" ) (from Rohm & Hasε) waε used. Reεin I-B" was prepared following the procedureε of exampleε 1 and 2 (uεing Amberlite 401-S) except that the amount of the I ₂ /KI mixture waε adjuεted εo aε to provide a reεin compriεing about 30 percent iodine at the end of the procedure in example 2; the mixture obtained at the end of the procedure of example 2 waε divided into two equal partε and one part waε subjected to a wash to provide the iodinated resin obtained as at the end of the procedure in example 2; and Resin I-A" waε prepared by taking the remaining one half part of the intermediate mixture obtained in the preparation of Reεin I-B" (mentioned above) and εubjecting the mixture to the procedure of example 3 except that the elevated temperature and preεsure conditions were set at 121° C and 15 psig respectively.

The iodine content of the above iodinated reεinε was determined in accordance with the procedure outlined in example 5.3. The resinε were also subjected to an iodine

bleed teεt aε outlined in example 7. The reεultε are εhown in table 12 below:

Table 12

Iodine leach

0.15 ppm 0.05 ppm

Resin I-B" 30.5 0.3 ppm

Resin I-A" 29.0 0.05 ppm

Aε may be εeen from table 12, εubjecting the reεin to a high temperature/preεεure treatment reεults in the iodine being more tenaciously fixed to the resin at different iodine concentrationε.

EXAMPLE 13: Air εtudy with I-B"

The procedure of example 11.6 waε followed uεing 30 grams of Resin I-B" and Bacillus Subtilis at a concentration of 275000 cfu per cubic meter. It was found that the Reεin I-B" eradicated only 7 to 10 % of the microorganiεmε. The reεultε of the teεt εhow that the Reεin I-B" iε not aε effective at eradicating microorganiεmε from air aε iε the Reεin I-A' ; it would be neceεεary to have εubεtantially more of Reεin I-B" in order to totally εterilize air aε compared with the Resin I-A' .

EXAMPLE 14: Studieε of the fixation of iodine at different temperatures as well as at atmospheric and elevated pressureε

Reεin IA, Reεin 2B, Reεin 3A and Reεin 4B were prepared aε follows:

The starting resin waε Amberlite 402 (OH ^" ) from Rohm & Haεε. 1000 gramε of thiε reεin waε pretreated following the procedure outlined in example l(i). The obtained waεhed reεin waε divided into four 200 gram portionε. An iodine εludge (four portionε, one for each of the above mentioned 200 gm portionε of reεin) waε prepared aε outlined in example l(ii) but uεing twice the amount of materialε εuch aε the iodine and the potaεεium iodide. The 200 gm reεin portionε were each iodinated using a respective iodine sludge as follows:

Resin IA was prepared, using an above mentioned 200 gm resin portion and a respective iodine εludge, following the procedureε of exampleε 2 to 4 except that for the procedure of example 3 the elevated temperature and preεεure conditionε were set at 121° C and 15 psig respectively (while the reaction time at the elevated conditions remained at 15 minutes) ;

Resin 2B was prepared, using an above mentioned 200 gm resin portion and a respective iodine sludge, following the procedure of example 2 except that the temperature

of the εhaking bath waε maintained at 40° C; Reεin 3A waε prepared, uεing an above mentioned 200 gm resin portion and a respective iodine sludge, following the procedures of examples 2 to 4 except that for the procedure of example 3 the elevated temperature and presεure conditionε were set at 121° C and 15 psig respectively while the reaction time at these elevated conditions waε set at 1.5 hours rather than at 15 minutes; and Reεin 4B waε prepared, uεing an above mentioned 200 gm reεin portion and a reεpective iodine εludge, following the procedure of example 2 except that the reaction mixture waε placed into a container having a looεe fitting cover; the container containing the reaction mixture waε placed into a heated water bath; the temperature of the reaction mixture was brought up to a boiling temperature of 100° C to 105° C over a period of 20 minutes and waε maintained at the boiling temperature og 100° C to 105° C for a period of 15 minutes; and thereafter the mixture was allowed to cool to room temperature over a period of about 1 hour (the reactor was not a preεεure εealed reactor but one wherein the loose fitting cover allowed gas\vapour to eεcape such that the reaction was carried out (eεεentially) at atmoεpheric preεεure - extra safety precautions had to be taken due to the violent sputtering of the reaction mixture and to the toxicity of the releaεed gaε\vapour) .

The denεity of each of the obtained iodinated reεinε waε determined in accordance with the procedure outlined in example 5.1. The iodine content of the above iodinated reεinε waε determined in accordance with the procedure outlined in example 5.3. The reεinε were alεo subjected to an iodine bleed test as outlined in example 7. The resultε are shown in table 14 below:

Iodine leach Density

0.5 ppm 1.616 gm\ml 1.5 ppm 1.694 gm\ml 0.5 ppm 1.661 gm\ml 1.0 ppm 1.595 gm\ml

As may be seen from table 14, subjecting the starting iodine\resin mixture to a treatment at essentially atmospheric presεure and a temperature of 100° C to 105° C or lower (reεin 2B and 4B) doeε not reεult in the iodine being as tenaciouεly fixed to the reεin aε when uεing both a temperature above 100° C and a preεεure above atmospheric preεεure (reεinε IA and 3A) .

EXAMPLE 15: Steriliεation barrier combinationε for uεe aε wound (εteriliεation) dreεεingε

EXAMPLE 15.1 Preparation of εterilisation foam dressing

The following εtarting materialε were uεed to prepare a sterilisation foam dresεing:

- a particulate iodinated reεin prepared in accordance with example 9 above; the reεin compriεing particleε or beadε of about 0.3 mm to about 0.7 mm;

- R/O water; and aε foam precurεor, HYPOL foamable hydrophilic polyurethane polymer, (code : # FHP2002) from W.R. Grace & Co. , Organic Chemicals Division, Lexington, Massachuεettε 02173.

The εteriliεation foam barrier waε prepared aε followε:

150 ml of R/O water was placed into a 300 ml beaker. The water was heated to 50° C. 10 cc of the HYPOL and 10 gm of the iodinated reεin were εimultaneouεly admixed with the heated water; mixing waε accompliεhed with a magnetic εtirring rod and waε carried out before and after the addition of the HYPOL and the reεin for the purpoεe of diεperεing the reεin particleε as homogeneously aε poεεible throughout the mixture. The obtained foam was set or cured in about 7 minutes; the resin particles were disperεed throughout the matrix of the foam which waε of porouε cellular εtructure (i.e. sponge like) . Once set the obtained flexible foam had a semi-sphere like form (see for example figure 9) ; εliceε of thiε foam material were taken so as to provide a foam dresεing having an eεεentially flat face for being applied against a wound. The obtained

steriliεation foam waε flexible and sponge like in that it could absorb liquids εuch aε water, puε and the like.

EXAMPLE 15.2 Preparation of a band-aid like sterilisation dresεing

The following εtarting materialε were uεed to prepare a band- aid sterilisation dressing:

- a particulate iodinated resin prepared in accordance with example 4 above; the reεin compriεing particleε or beadε of about 0.3 mm to about 0.7 mm; and

- a strip of polymeric material having an adheεive on one face thereof (the εtrip waε Compeed) .

The εteriliεation strip barrier was prepared as follows:

An open ended ring funnel was dispoεed over a central area of the εtrip on the adhesive face thereof. Resin beadε were placed in the stem of the ring funnel εo aε to eεεentialy cover the central portion of the adheεive face defined by the ring; a plunger waε εhoved into the ring and a mild preεεure was applied to the resin beadε therein. The ring waε removed along with exceεε resin beads εo aε to leave behind a εingle layer of reεin beadε fixed to the adheεive face of the εtrip; the reεin beadε in the layer eεεentialy abutted each other. The εtrip barrier had a form as εhown in figure 8; if deεired the beads do not have to abut but could be spaced apart.

EXAMPLE 15.3 Animal infection study: cutε

The foam type εteriliεation dreεεing obtained from example 15.1 waε teεted aε followε:

Eight male guinea pigs were shaved so as to expoεe eεsentially the same εkin area. The guinea pigε each weighed about 500 to 550 gm and were obtained from Charleε River, Quebec, Canada, a εub-diviεion of Bausch & Lomb the guinea pigs were quarantined for a period of 48 hours before being prepared for and subjected to the teεtε.

The guinea pigs were prepared for the tests aε follows:

Esεentially the same area of skin of each of the guinea pigε waε aneεthetiεed uεing Carbocaine-V

(chlorhydrate of Mepivacaine USP 2%) ; thiε aneεthetic haε no known εterilisation qualities.

An inoculum compriεing a mixture of Staphillococuε

Aureus and Pseudomonaε Aeriginoεa waε prepared at

10° cfu/ml; the ratio of Staphillococuε Aureus to

Pεeudomonaε Aeriginoεa waε 1:1. 0.2 ml of the inoculum waε injected under the aneεthetiεed skin of each animal. A cruciform structured scalpel cut (#) waε made above the inoculum injection area of each of the animalε; i.e. the cuts were 1.0 to 4.0 cm long and 1.0 to 4.0 mm deep. Additional inoculum was dabbed onto the εurface cutε.

The animalε were divided into two groups of four animals each, one group to be used aε a control group and the

other group aε a teεt group. A foam εteriliεation dressing was applied over the wound for each of the animals of the test group, i.e. the foam dresεing was placed in contact with the wounded skin area and maintained in place during the period of the test. The foam dreεεingε were maintained in place over the wound area by meanε of an adheεive εtrip which waε provided with an opening or window by meanε of which a portion of the foam dreεεing waε left uncovered and exposed to the air. No dresεing or εteriliεation material waε applied to the woundε of the animalε of the control group.

The four animals of the teεt group with dreεεingε developed no infection and the scaring process was initiated after 16 hourε. On the other hand the four control animalε developed infection and the infection waε εtill εpreading after 72 hourε.

The εtrip type εterilisation dressing obtained from example 15.2 was tested exactly as above for the foam dreεεing with exactly the εame reεultε.

EXAMPLE 15.4 Animal infection study: burns The same εtudieε aε deεcribed in example 15.3 were carried out except that the leεion waε a burn created with a 1.0 cm red hot rod; the hot rod waε firmly held againεt the εkin for about 3 to 4 seconds. The same Inoculum as in example 15.3 was injected beneath the burn area and alεo dabbed onto the

εurface of the burned εkin. Exactly the same resultε were obtained for the two typeε of dreεsings as were obtained for the teεtε of example 15.3.

EXAMPLE 15.5 Animal infection εtudy: cutε with continual contact with infectiouε liquid The foam type εteriliεation dreεsing obtained from example 15.1 was teεted aε followε:

Four male guinea pigε were εhaved εo aε to expoεe eεεentially the εame εkin area. The guinea pigε each weighed about 500 to 550 gm and were obtained from Charleε River, Quebc, Canada; the guinea pigε were quarantined for a period of 48 hourε before being prepared for and εubjected to the teεtε.

The guinea pigε were prepared for the teεtε aε followε:

Essentially the same area of skin of each of the guinea pigε waε aneεthetiεed uεing Carbocaine-V

(chlorhydrate of Mepivacaine USP 2%) ; the area waε alεo εteriliεed uεing 70% isopropyl alcohol. A cruciform structured scalpel cut (#) was then made in the steriliεed area; i.e. the cutε were 1.0 to

4.0 cm long and 1.0 to 4.0 mm deep.

The animalε were divided into two groupε of two animalε each, one group to be uεed aε a control group and the other group aε a teεt group. A foam εterilisation dressing was applied over the wound for each of the animalε of the teεt group, i.e. the foam dreεεing waε

placed in contact with the wounded skin area and maintained in place during the period of the test. The foam dreεsings were maintained in place over the wound area by meanε of an adhesive strip which was provided with an opening or window by means of which a portion of the foam dreεεing was left uncovered and exposed. No dresεing or εteriliεation material was applied to the wounds of the animalε of the control group.

An inoculum compriεing a mixture of Staphillococus Aureus and Pseudomonaε Aeriginoεa waε prepared at 10 ⁷ cfu/ 100ml; the ratio of Staphillococuε Aureus to Pseudomonas Aeriginosa was 1:1. Sufficient inoculum waε prepared such that each of the animals of the test and control group could be bathed in the inoculum such that the bath liquid was in continual contact with the wound area, i.e. the bath liquid covered the dressingε. The animals of each group were kept in the bath inoculum for a period of 72 hours.

The two animals of the test group with dresεingε developed no infection and the εcaring proceεε waε in full process. On the other hand the two control animals each had developed infection.

EXAMPLE 15.6 Animal infection study: cuts contacted with aerosol borne infectious agents

The same procedure as for example 15.5 was used except that instead of being maintained in a bath of inoculum, the inoculum waε applied uεing an atomiεer the same aε that used for example 11.2 for artificial creation of airborne infection of a wound; the inoculum used also had 10° cfu/ml rather than 10 ⁷ cfu/100ml as in example 15.6. 4 ml of the inoculum waε sprayed directly on the wound of the control animals and on the dressing covering the wound of the test animals; the inoculum was so applied every hour for 8 hours with 72 hours of incubation. The same resultε aε in example 15.5 were obtained.

EXAMPLE 15.7 Skin reaction εtudy: iodine tincture

Three male guinea pigε were εhaved εo aε to expoεe eεεentially the same skin area. The guinea pigε each weighed about 500 to 550 gm and were obtained from Charleε River, Quebec, Canada; the guinea pigε were quarantined for a period of 48 hourε before being prepared for and εubjected to the teεtε.

The guinea pigε were prepared for the teεtε aε followε:

Eεεentially the same area of skin of each of the guinea pigε waε aneεthetiεed uεing Carbocaine-V (chlorhydrate of Mepivacaine USP 2%) ; the area waε alεo εteriliεed uεing &0& iεopropyl alcohol. A cruciform εtructured εcalpel cut (#) waε made in the εteriliεed area; i.e. the cuts were 1.0 to 4.0

cm long and 1.0 to 4.0 mm deep. An inoculum comprising a mixture of staphillococus Aureus and Pseudomonas Aeriginosa was prepared at 10 ⁹ cfu/ml; the ratio of Staphillococuε Aureuε to Pseudomonas Aeriginosa waε 1:1.

The inoculum was only dabbed onto the surface of the wounds of each of the animals (no injection of inoculum under the skin) . It waε found that a 5% iodine tincture locally applied on the woundε would neutraliεe infection provided that the iodine tincture was applied at 0.1 ml directly after infection and every 2 hours thereafter for 10 hours; the iodine tincture was from Jean Coutu, Quebec, Canada - 5% iodine, 3.3% KI and 75% ethanol. However, it was noted that the skin in the periphery of the wound waε εeriouεly devitalised becauεe of the burning effect of the tincture i.e. of the iodine.

It waε also found that the iodine tincture did not stop infection from occurring if inoculum was injected under the skin.

EXAMPLE 15.8 Skin reaction study: sterilisation dresεingε

Three male guinea pigs were shaved so as to expoεe eεεentially the εame εkin area. The guinea pigs each weighed about 500 to 550 gm and were obtained from Charles River, Quebec, Canada; the guinea pigs were

quarantined for a period of 48 hourε before being subjected to the testε.

A foam εteriliεation dressing of example 15.1 was applied over a εhave skin area of each of the animals, i.e. the foam dressing was placed in contact with the shaved εkin area and maintained in place during the period of the test. The foam dressings were maintained in place over the skin area by meanε of an adheεive εtrip which waε provided with an opening or window by meanε of which a portion of the foam dreεεing waε left uncovered and expoεed to the air. The dreεεing waε maintained in place for a period of 3 weekε. The covered skin area was examined every two dayε. No redness, rash, inflammation, or any other reaction waε noted; the covered εkin remained healthy.

The above procedure was also carried out uεing a strip sterilisation dresεing of example 15.2. However the dreεεing was maintained in place only for 7 dayε. Again, no redneεε, rash, inflammation, or any other reaction was noted; the covered εkin remained healthy.

Figureε 7 to 11 illustrate a number of example embodiements of steriliεation barrier combinationε of the preεent invention; εome of theεe combinationε are also described in example 15 above.

Figure 7 showε a partially cut away perspective view of a sterilisation barrier dressing of tea-bag type construction wherein the iodinated resin particles or beads (one of which is designated by the reference numeral 30) are free flowing but are held together by being enveloped by a fluid (e.g. air-liquid) permeable envelope 31 of (known) pharmaceutically acceptable paper or gauze (e.g. a εuitable εterile gauze from Johnεon & Johnεon, Canada) . The paper or gauze iε permeable to fluidε εuch aε air and water but is able to hold onto the particles of iodinated resin enveloped thereby εince any holeε in the paper gauze are εized to be εmaller than the particleε of resin. This type of dressing may be made relatively small or relatively large keeping in mind the εize of the leεion that it iε intended to cover. The dreεεing may be made by providing a εheet of paper or gauze, placing the desired amount of resin particleε thereon and then folding one εide edge of the paper or gauze over the reεin particleε 30 εo as to overlay and abut the opposite side; these abuting side edgeε 32 and 33 aε well aε each of the reεpective εide edges of the two pairs of adjacent side edges indicated generally at 34 and 35 may be fixed together in any known manner, for example by compreεεion, εtitching or by the use of any known phamaceutically acceptable adhesive. The fixation of the sides is εuch that they will tend to maintain their integrity in the face of water , body fluidε or body exudateε (e.g. puε) . The embodiment εhown in figure 7 iε εhown may be considered as eεεentially having a plurality of resin bead layers; it could of course have only a single εuch

layer.

Alternatively, the sterilisation barrier may take on a band- aid type aspect as shown in figure 8. The combination εhown haε a flexible carrier component 36. A central portion of one εide of the carrier component 36 haε fixed thereto a plurality of beads or particles (one of which is deεignated by the reference numeral 37) of demand disinfectant iodinated resin. The resin beadε 37 are fixed to the εurface by a εuitable adhesive which is phar acetically acceptable and which will maintain the beads on the carrier component even if exposed to water or body fluids or exudateε. The portion of the band surface 38 which surrounds the centrally dispoεed beadε 36 may alεo be provided with any (known) adhesive which may for example be able to releasably stick the combination to the skin (e.g. a latex based adheεive) . The carrier component 36 may, aε desired be permeable or impermeable to fluidε such as air, water, puε; prefereably, the carrier iε permeable to gaε such as air, water vapour, etc. at least in the region of the reεin beadε fixed thereto, i.e. thiε region iε air breathable. The carrier component 36 may be of any suitable pharmaceutically acceptable (plasticε) material (e.g. the carrier component may be a porouε hydrophobic material permeable to air and water vapour εuch aε deεcribed in U.S. patent nos. 3,953,566 and 4,194,041 - Gore-Tex) . The carrier component complete with an adheεive face may be obtained from Peco Marketing ltd. , Montreal, Quebec under the name "Compeed".

Figureε 9, 10 and 11 εhow a number of further embodimentε of the sterilisation barrier combination.

Figure 9 εhowε a flexible sterilisation foam or εponge type dreεsing 39 for wounds. The dreεεing compriεeε a flexible pharmaceutically acceptable foam matrix 40 having iodinated resin particles (one of which iε deεignated with the reference numeral 41) dispersed therein. The foam matrix 40 has a porous open cell structure such that it is permeable to fluids such aε air and water and can absorb body liquidε in the manner of a εponge (e.g. the foam is hydrophilic and/or oil loving) ; the foam barrier is air breathable. The foam matrix 40 as shown has cells of relatively small εize εo aε to facilitate the abεorption of liquids such as puε. The reεin particles 41 making up the resin disinfectant component are distributed throughout and held or fixed in place by the polymeric matrix 40 εuch that εurface portionε of the reεin particles are exposed within the cells of the matrix 40. The exposed surfaceε of the reεin are available for contact with any microorganisms which may find their way into the cells of the body of the barrier combination; contact with the reεin devitaliεes the microorganismε.

The foam εteriliεation barrier or dreεεing 39 aε shown in figure 9 has a εemi-spherical like shape. The flat surface 42 may be applied to a wound or cut. The dresεing may be held in place by any εuitable meanε εuch aε for example any suitable strapping or by adheεive tape means. Preferably, the

εterilisation foam dressing 39 is held in place such that at least a portion of it is exposed (e.g. exposed to the air) ; thus the means for holding the foam in place may be an adheεive εtrip which haε a central opening exposing at least a portion of the foam when the foam iε held in place. Once in place on the wound, the flexible foam εteriliεation barrier will εterilise the immediate area of the wound which it covers and also prevent other infectious microorganiεmε from contacting the wound from outside the body. Surpriεingly, however, it haε been found that the εterilisation barrier is also effective not only againεt microorganiεmε at the immediate εurface of a wound but also against thoεe deeper within the body in the area of a cut.

Figure 10 illuεtrateε another type of flexible foam εterilisation barrier 43. It differs from the steriliεation barrier shown in figure 9 in that the size of the cells (one of which iε deεignated with the reference numeral 44) is significantly larger than those for the foam shown in figure 9; this type of foam may be used aε a liner material for wearing apparel to provide the apparel with the ability to protect the wearer from (εkin) contact with viable microorganiεmε. The reεin beadε, εpheres or particles (one of which is deεignated with the reference numeral 45) are, aε in the caεe of the reεin spheres 41 for the foam barrier 39 of figure 9, dispersed in the foam matrix and are held or fixed in place thereby such that exposed surfaces of the resin are available for contact with any microorganiεmε which

may find their way into the cellε of the body of the barrier combination; contact with the resin devitalises the microorganisms.

The foam matrix for the steriliεation barrierε of figures 9 and 10 may be made by admixing (known) starting reactants in (known) manner to make (known) foamε which are pharmaceutically acceptable. Known polyurethane foamε may for example be uεed. In order to make the εteriliεation barrier, the diεinfectant reεin particleε may be admixed with and diεperεed (e.g. more or leεε homogeneouεly) in the εtarting reactantε at the beginning of the foam producing reaction. The foam barrier may be set in molds or else cut to the deεired εhape. The foam εteriliεation barrier may take any deεired form such as sheetε, filmε, plugε, and the like; it may, for example, be molded εo aε to conform to the εhape of portion of the body to which it iε to be applied.

Aε mentioned above a (flexible) phamaceutically acceptable hydrophilic foam matrix may be obtained uεing water and HYPOL foamable hydrophilic polyurethane polymer εtarting material from W.R. Grace & Co. Lexintington Maεε. U.S.A..

The pore or cell εize of the foam barrier may be adjuεted in known manner; for example by altering the reaction temperature. For example in the caεe of HYPOL a temperature of about 50 to 70° C may be uεed to obtain small pore sizes and a lower temperature of about 35 to 45° C may be used to

obtainer larger εized poreε.

Figure 11 εhowε a cross εectional portion of a εandwich type textile material 46 which incorporateε a flexible large cell εize sterilisation foam layer 47. The sandwich compriseε two outer flexible clothe type layerε 48 and 49 which are fixed to the central εteriliεation foam barrier 46 in any εuitable manner (e.g. by an adheεive, melt fuεion, etc.). The two outer layerε 48 and 49 may be of any desired material; they may be permeable or impermeable to fluids such aε air, water vapour, water and the like. They may for example be of cotton, polypropylene, etc.; or a Gore-tex type material mentioned above. A sheet of textile material as shown may cut into pieces of variouε εhapeε needed to form such protective wearing apparel as may be deεired, e.g. coatε, pantε, εockε, face masks (e.g. full face maskε or maεkε covering only the mouth and noεe) and the like.

The flexible foam layer 47 can be made in any known manner provided that diεinfectant resin particles are disperεed in the reaction mixture during the reaction εuch that the end product foam also has the reεin particleε diεperεed in the foam matrix and any microorganiεm able to penetrate into an interior cell of the foam may be able to contact a reεin particle expoεed into the cell and be devitalised thereby. The foam barrier as in the caεe of the foam dreεεingε mentioned may be configured to be permeable to fluids such aε air, water, etc..

The textile material 46 may be formed by first forming a sheet of the sterilisation foam; by providing sheetε of the desired outer layers; and then gluing the elements together such that the foam is sandwiched between the two other outer layerε. Alternatively, a mold may be used wherein opposed εurfaceε of the mold are provided with a reεpective outer layer; the foam εtarting materialε are introduced between the layers; and foaming activated such that the foam layer is produced in situ.

Although shown with two outer layers the combination of figure 11 may of course have only one εuch clothe like layer. Additionally if the outer layer or layers are permeable to fluids such as air, water, pus and the like, the wearing apparel made therefrom could as needed double as a kind of εteriliεation dressing; the textile may thus for example be air breathable.

Additionally although the foam sterilisation barrier has been described in relation to a flexible foam it may be a stiff foam depending upon the application; again the stiff foam matrix may be prepared in known manner.

An alternate embodiement of the εandwich type textile may be made wherein the foam matrix iε omitted; in thiε caεe the beadε may be placed between the outer layerε and the beads may be fixed in place for example by an adhesive or by melt

fusion depending on the nature of the layers (e.g. melt fusion may be considered if the layers are of thermoplastics material; the textile may of course be so made aε to preεerve the flexibility of the combination.