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An improved article of a membrane permeable to water and impermeable to microbiocidal compounds containing therein a solid particulate microbiocidal composition which is useful in aqueous systems, wherein the composition is produced from aqueous solutions of a water-soluble microbiocidal compound ab

An improved article of a membrane permeable to water and impermeable to microbiocidal compounds containing therein a solid particulate microbiocidal composition which is useful in aqueous systems, wherein the composition is produced from aqueous solutions of a water-soluble microbiocidal compound absorbed in an inert, finely-divided water-insoluble solid carrier. Especially useful are microbiocidal 3-isothiazolones and 2-substituted-1,2-benzisothiazolones, and metal salt stabilized derivatives thereof, absorbed into a silicaceous diatomaceous earth in a sealed, perforated membrane, for example, a perforated bag, produced from polyethylene. These articles afford a form, which is safer for handling.

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1. A microbiocidal article useful for controlling living microorganisms in an aqueous system comprising: (a) a porous membrane having a film thickness of from 0.5 mil to about 10 mils and having a pore size smaller than the particle size of the microbiocidal to be employed containing sealed there

1. A microbiocidal article useful for controlling living microorganisms in an aqueous system comprising: (a) a porous membrane having a film thickness of from 0.5 mil to about 10 mils and having a pore size smaller than the particle size of the microbiocidal to be employed containing sealed therein: (b) a particulate, solid isothiazolone microbiocidal composition comprising: (i) an aqueous solution containing from about 0.1 to about 70 weight %, based on total weight of said composition, of at least one water-soluble isothiazolone microbiocidal, whose water solubility is greater than 1000 ppm, blended with and absorbed in; (ii) from about 99.9 to about 30 weight %, based on total weight of said composition, of an inert finely-divided water-insoluble solid carrier material selected from silicaceous diatomaceous earth, high water absorption capacity calcium silicate granular material, silicas, clays, charcoal, vermiculite, corn cobs, wood, or polymeric matrices; wherein the film-forming material is selected from a hydrophobic film-forming material having a solubility parameter of less than about 12.5. 2. The article according to claim 1 wherein said porous membrane is selected from polyester, polyfluoroolefins, polyamides, polyvinyl chloride, polyethylene, polypropylene, spunbonded polyethylene or spunbonded polypropylene, polyethylene terephthalate, or polycarbonate. 3. The article according to claim 2 wherein said membrane is selected from spunbonded polyethylene or spunbonded polypropylene. 4. The article according to claim 2 wherein said composition comprises, (i), at least one water-soluble microbiocidally-effective isothiazolone, having a water solubility of greater than 1000 ppm, represented by the formula: ##STR## wherein Y is an unsubstituted or substituted C 1 -C 18 alkyl group, an unsubstituted or substituted C 2 -C 18 alkenyl or alkynyl group, an unsubstituted or substituted C 3 -C 12 cycloalkyl group, an unsubstituted or substituted aralkyl group of 6-10 carbon atoms, or an unsubstituted or substituted aryl group of 6-10 carbon atoms; R is hydrogen, halogen or a C 1 -C 4 alkyl group; R' is hydrogen, halogen or a C 1 -C 4 alkyl group; or R and R' can be taken together with the C=C bond of the isothiazolone ring to form a substituted or unsubstituted benzene ring; or at least one of said isothiazolones stabilized with at least one metal salt used in an amount of about 1 to 60 weight %, based on weight of 3-isothiazolone and metal salt, said metal salt being represented by the formula: ##EQU##(MX n ) wherein M is a cation of a metal selected from sodium, potassium, calcium, magnesium, copper, iron, zinc, barium, manganese, silver, cobalt or nickel, X is an anion selected from chloride, bromide, iodide, sulfate, nitrate, nitrite, acetate, chlorate, perchlorate, bisulfate, bicarbonate, oxalate, maleate, p-toluene-sulfonate, carbonate, or phosphate; and n is an integer for which the anion X satisfies the valence of the cation M, and, an inert, finely-divided water-insoluble solid material selected from silicaceous diatomaceous earth, high water absorption capacity calcium silicate granular material, silicas, clays, charcoal, vermiculite, corn cobs, wood, or polymeric matrices. 5. The article according to claim 4 wherein said composition comprises from about 1 to 35 weight %, based on total weight of said composition, of an isothiazolone wherein Y is an unsubstituted or substituted C 1 -C 18 alkyl group or C 3 -C 12 cycloalkyl group; R is hydrogen or halogen; R' is hydrogen or halogen; or R and R' are taken together with the C=C bond of the 3-isothiazolone ring to form a substituted or unsubstituted benzene ring; or said isothiazolone stabilized with said metal salt; and from about 99 to 65 weight %, based on total weight of said composition, of a solid carrier material selected from silicaceous diatomaceous earth, high water absorption capacity calcium silicate granular material, or clays. 6. The article according to claim 5 wherein said composition comprises from about 2 to 25 weight %, based on total weight of said composition, of an isothiazolone wherein Y is methyl, R is hydrogen, and R' is chlorine or said isothiazolone is stabilized with Mg(NO 3 ) 2 or a mixture of Mg(NO 3 ) 2 and MgCl 2 ; and from about 98 to 75 weight %, based on total weight of said composition, of silicaceous diatomaceous earth. 7. The article according to claim 6 wherein said composition comprises, in combination with said water-soluble isothiazolone, an isothiazolone having a water solubility of about 500 ppm wherein Y is n-octyl or t-octyl and R and R' are each hydrogen, or an aqueous solution of said combination of isothiazolones stabilized with said metal salt wherein said metal salt is Mg(NO 3 ) 2 or a mixture of Mg(NO 3 ) 2 and MgCl 2, the combination comprising about 2 to 25 weight %, based on total weight of said composition; and from about 98 to 75 weight %, based on total weight of said composition, of silicaceous diatomaceous earth. 8. The article of claim 7 wherein the membrane has a pore diameter equal to or less than 6 mils. 9. The article of claim 8 wherein the membrane has a pore diameter of about 5 mils. 10. The article according to claim 9 wherein said composition comprises from about 2 to 25 weight %, based on total weight of said composition, of a mixture of an isothiazolone in an aqueous solution wherein Y is methyl, R is hydrogen and R' is chlorine or Y is methyl, R is hydrogen and R' is hydrogen, or an aqueous solution of said mixture of isothiazolones stabilized with Mg(NO 3 ) 2 or a mixture of Mg(NO 3 ) 2 and MgCl 2 ; and from about 98 to 75 weight %, based on total weight of said composition, of silicaceous diatomaceous earth. 11. A method for controlling living microorganisms in an aqueous system which comprises incorporating into the aqueous system the article of claim 1. 12. A method for controlling living microorganisms in an aqueous system which comprises incorporating into the aqueous system the article of claim 2. 13. A method for controlling living microorganisms in an aqueous system which comprises incorporating into the aqueous system the article of claim 3. 14. A method for controlling living microorganisms in an aqueous system which comprises incorporating into the aqueous system the article of claim 4. 15. A method for controlling living microorganisms in an aqueous system which comprises incorporating into the aqueous system the article of claim 5. 16. A method for controlling living microorganisms in an aqueous system which comprises incorporating into the aqueous system the article of claim 6. 17. A method for controlling living microorganisms in an aqueous system which comprises incorporating into the aqueous system the article of claim 7. 18. A method for controlling living microorganisms in an aqueous system which comprises incorporating into the aqueous system the article of claim 8. 19. A method for controlling living microorganisms in an aqueous system which comprises incorporating into the aqueous system the article of claim 9. 20. A method for controlling living microorganisms in an aqueous system which comprises incorporating into the aqueous system the article of claim 10. 21. A method according to claim 10 wherein the aqueous system is selected from metal-working fluids, water cooling tower waters, toilet bowls, swimming pools, or washing machines.