HK1018383A - Solid biocidal compositions - Google Patents

Description

Solid biocidal compositions

Generally, the present invention relates to solid compositions of biocidal compounds. In particular, the present invention provides solid compositions capable of controlled release of biocidal compounds.

The ability to control the release of biocidal compounds to the locus to be protected is important in the field of biocidal compounds, particularly in the field of microbicides and marine antifouling agents. Generally, when a biocidal compound is added to the locus to be protected, the compound is released rapidly, whether or not it is needed. Controlled release compositions are capable of delivering biocidal compounds in response to the need for the compound. According to this method, only the desired amount of biocidal compound is released to the site to be protected. Controlled release has the advantages of reduced cost, reduced toxicity, and increased efficiency.

Solid formulations of biocidal compounds are a useful method of delivering biocidal compounds to the site to be protected. Solid formulations also ensure the safety of such biocidal compounds by reducing the likelihood of human contact. For example, solid compositions can reduce the risk of spillage that is typically present with liquid compositions.

Various solid compositions of biocidal compounds are known. Such methods include encapsulation of the biocidal compound, adsorption of the biocidal compound on an inert carrier (e.g., silica gel), and inclusion of the biocidal compound.

However, such solid compositions do not provide controlled release of biocidal compounds. For example, solid compositions in which a biocidal compound is adsorbed on an inert solid support are generally not capable of controlling the release of the biocidal compound. Generally, the biocidal compound is released rapidly once the solid composition is applied to the locus to be protected. Thus, once such a composition is added to the locus to be protected, any safety of the biocidal compound provided by the solid composition will not exist.

For example, EP 106563A (Melamed) discloses compositions having water-soluble microbicides in admixture with inert, finely divided, water-insoluble solid carriers such as clays, inorganic silicates and silica. These compositions do not provide controlled release of biocidal compounds. Such compounds are released to the site to be protected by dissolution and their release is therefore controlled by the dissolution rate of the particular biocidal compound. This application does not disclose zirconium hydroxide.

Hydroxides of certain metals such as zirconium, titanium, iron, vanadium and tin have been disclosed as chelating antibiotics (Kennedy et al chemotherapy 9, 766-770(1976)) for antimicrobial agents. The center here is on the immobilization of antibiotics. While Kennedy et al disclose that the metal hydroxides tested slowly released antibiotics, Kennedy et al did not recognize the specific ability of zirconium hydroxide to control the release of biocidal compounds. Other metal hydroxides such as titanium hydroxide, as described by Kennedy et al, do not control the release of biocidal compounds. No discussion is made of microbicidal compounds or marine antifouling agents.

The problem addressed by the present invention is to provide a solid composition of a biocidal compound which, once added to the locus to be protected, is safer to handle and provides controlled release of the biocidal compound.

Summary of The Invention

The present invention provides solid compositions comprising a biocidal compound and zirconium hydroxide, which compositions enable the controlled release of the biocidal compound.

It is another object of the present invention to provide a method of controlling or inhibiting the growth of microorganisms at a specific locus which comprises introducing into or onto the locus to be protected an effective amount of a composition as described above.

It is another object of the present invention to provide a method of removing or inhibiting the growth of marine organisms on a structure which comprises introducing into or onto the structure to be protected an effective amount of the above composition. Detailed description of the invention

The terms used in this specification have the following meanings unless clearly stated otherwise herein.

The term "biocidal compound" refers to both microbicides and marine antifouling agents. "microbicide" refers to a compound capable of inhibiting or controlling the growth of microorganisms at a particular locus. The term "site" does not include pharmaceutical or veterinary applications. The term "microorganism" includes, but is not limited to, fungi, bacteria, algae.

"Marine antifouling agents" include algicides and molluscicides. "Marine antifouling activity" includes the elimination and inhibition of marine growth. Marine organisms controlled by marine antifouling agents suitable for use in the present invention include hard and soft fouling organisms. Generally, the term "soft fouling organisms" refers to plants and invertebrates (such as slime organisms, algae, macroalgae, soft corals, tunicates, hydroids, sponges and anemones), and the term "hard fouling organisms" refers to invertebrates (such as barnacles, tubificans and mollusks) having a specific hard shell shape.

All amounts are in weight percent ("% wt") (unless otherwise specified) and include all% wt ranges. The following abbreviations are used herein: g is gram; ml is equal to milliliter; l is liter; c is centigrade degree; min is minutes; ppm to parts per million; rpm is the rotation speed per minute; cm is equal to centimeter.

Suitable microbiocides useful in the present invention include, but are not limited to: methylenebis (thiocyanate), isothiazolone (isothiazolone) (e.g., 2-N-octyl-4-isothiazolin-3-one), 4, 5-dichloro-2-N-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 1, 2-benzisothiazolin-3-one, and 2-methyl-4, 5-trimethylene-4-isothiazolin-3-one, carbamates (e.g., 3-iodopropargyl-N-butylcarbamate), methyl benzimidazol-2-ylcarbamate, methyl esters of these, and mixtures thereof, Imidazolidinyl urea, diazolidinyl urea, N' - [3, 4-dichlorophenyl group]N, N-dimethylurea, 3, 4, 4 '-trichlorocarbanilide, dimethyldithiocarbamate, and disodium ethylenebisdithiocarbamate, heterocyclic compounds (e.g., 2-pyridylthio-1-zinc oxide, 2-pyridylthio-1-sodium oxide, 10' -oxydiphenoxyarsine, N-trichloromethylthiophthalimide, 5-oxo-3, 4-dichloro-1, 2-dithiol, 3-bromo-1-chloro-5, 5-dimethylhydantoin, 4, 4-dimethyl-1, 3-dimethylolhydantoin, 2- (thiocyanatomethylthio) benzothiazole, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine, sodium dithiocarbanilide, bis-N-trichloroiminobis-thiocarbamate, bis-phenylthiocarbamate, bis-N-trichloromethyl-1-pyridineimide, 5-oxo-3, 4-dichloro-1, 2, 3, 5-twomethyl-1H-pyrazole-1-methanol, 1- (2-hydroxyethyl) -2-octadecylimidazoline; 4- (2-nitrobutyl) morpholine, triazine, N '-methylenebis (5-methyl-1, 3-oxazolidine), 2' -oxybis (4, 4, 6-trimethyl-1, 3, 2-dioxaborolane), 2 '- (1-methyltrimethylenedioxy) bis (4-ethyl-1, 3, 2-dioxaborolane), hexahydro-1, 3, 5-tris (2-hydroxyethyl) -s-triazine, 4, 4-dimethyloxazolidine, 3, 4, 4-trimethyloxazolidine, 4, 4' - (2-ethyl-nitrotrimethylene) dimorpholine, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine, 2, 3, 5, 6-tetrachloro-4- (methylsulfonyl) pyridine, alpha- [2- (4-chlorophenyl) ethyl]- α - (1, 1-dimethylethyl) -1H-1, 2, 4-triazolyl- (1) -ethanol, 1- [ (2- (2 ', 4' -dichlorophenyl) -4-propyl-1, 3-dioxolan-2-yl-methyl]-1H-1, 2, 4-triazole, didecyldimethylammonium chloride, copper-8-hydroxyquinoline, 1- [2- (2, 4-dichlorophenyl) -1, 3-dioxolan-2-yl-methyl]-1H-1, 2, 4-triazole, 2- (4-thiazolyl) -benzimidazole, 3, 5-dimethyl-1, 3, 5-thiadiazine-2-thione, 2-chloro-4, 6-bis (ethylamino) -1, 3, 5-triazine, 2-chloro-4-ethylamino-6-tert-butylamino-1, 3, 5-triazine, 1- (3-chloroallyl) -3, 5, 7-triaza-1-azoniaadamantane chloride, copper naphthenate, 5-hydroxymethyloxymethyl-1-aza-3, 7-dioxabicyclo [3.3.0]Octane, 5-hydroxymethyl-1-aza-3, 7-dioxabicyclo [3.3.0]Octane, 7-ethyl-1, 5-dioxa-3-azabicyclooctane, cetylpyridinium nitride, 3-bromo-1-chloro-5-dimethyl-5-ethylhydantoin dodecyl-bis (aminoethyl) -glycine, 5-hydroxypoly- [ methyleneoxyethyl group]Methyl-1-aza-3, 7-dioxabicyclo [3.3.0]Octane, carboxylic acids and their derivatives (e.g. (E, E) -2, 4-hexadienoic acid, benzoic acid, sodium or calcium propionate, disodium ethylenediaminetetraacetate, sodium hydroxymethylglycinate, benzyl ester of 4-hydroxybenzoic acid, (C) of 4-hydroxybenzoic acid₁-C₄) (C) of alkyl ester, sodium salt of 4-hydroxybenzoic acid₁-C₄) Alkyl esters, tallow fatty acid dimethylamide, 2-dibromo-3-nitrilopropionamide, alcohols and amines (e.g., 1- (alkylamino) -3-amino-propane, 2-bromo-2-nitro-1, 3-propanediol, phenoxyethanol, benzyl alcohol, 2-hydroxymethylaminoethanol, n-2-hydroxypropylaminomethanol, 2-hydroxyaminomethanolPropylmethane thiosulfonate, p-nitrophenol, 4-chloro-3, 5-dimethylphenol, ammonium and phosphonium salts (e.g., n-alkyldimethylbenzylammonium chloride, cetyltrimethylammonium chloride, didecyldimethylammonium chloride, poly (hexamethylene biguanide) hydrochloride, poly [ oxyethylene (dimethylimino) ethylene dichloride]Alkyl dimethyl benzyl chloride ammonium chloride, dodecyl guanidine hydrochloride, 2- (decylthio) ethylenediamine hydrochloride, quaternary ammonium compounds, tetrakis (hydroxymethyl) phosphonium hydrochloride, tetrakis (hydroxymethyl) phosphonium sulfate, aldehydes, ketones, and formaldehyde-releasing agents (e.g., pentane-1, 5-dialdehyde, 1, 2-benzenedicarboxaldehyde), formaldehyde, 2-bromo-4 '-hydroxyacetophenone, tris (hydroxymethyl) nitromethane, and 5-bromo-5-nitro-1, 3-dioxane, halogenated aromatic compounds (e.g., 2, 4, 5, 6-tetrachloroisophthalonitrile, 2, 4, 4' -trichloro-2 '-hydroxydiphenyl ether, 2' -dihydroxy-5, 5 '-dichloro-diphenylmethane, and 1, 6-bis- (4' -chlorophenyl) -biguanide, bis (4 '-chloro-5, 5' -dichloro-diphenylmethane), bis (2 '-chloro-4' -phenyl) -biguanide, bis (hydroxymethyl) phosphonium chloride, and bis (hydroxymethyl) phosphonium chloride, Halogenated aliphatic compounds (e.g., 1, 2-dibromo-2, 4-dicyanobutane, diiodomethyl-p-tolylsulfone, dibromonitroethane, hexachlorodimethylsulfone, olefins (e.g., β -bromo- β -nitrostyrene, 1, 4-bis (bromoacetoxy) -2-butene, terpenes, limonene, enzymes (e.g., cellulase, α -amylase, protease, polysaccharidase, fructofuranosylhydrolase), surfactants (e.g., alkylaryl esters, polyethoxylated alcohols, polyethoxylated ethers, phosphate esters, sulfonate esters, sulfonated fatty substances, sulfosuccinates, and dodecylbenzene sulfonic acid).

Suitable marine antifouling agents useful in the present invention include, but are not limited to: manganese ethylenebisdithiocarbamates, zinc dimethyldithiocarbamates, 2-methylthio-4-tert-butylamino-6-cyclopropylaminotriazine, 2, 4, 5, 6-tetrachloroisophthalonitrile, 3- (3, 4-dichlorophenyl) -1, 1-dimethylurea, zinc ethylenebisdithiocarbamates, copper thiocyanates, 4, 5-dichloro-2-N-octyl-3-isothiazolone, N- (fluorodichloromethylthio) -phthalimide, N-dimethyl-N '-phenyl-N' -fluorodichloromethylthio-sulfamide, 2-pyridylthio-1-zinc oxide, tetramethylthiuram disulfide, 2, 4, 6-trichlorophenylmaleimide, 2-dimethyldichloromaleimide, 2-dimethyldithiocarbazide, sodium dithiocarbazide, sodium carbazide, sodium, 2, 3, 5, 6-tetrachloro-4- (methylsulfonyl) -pyridine, 3-iodo-2-propynylbutylcarbamate, diiodomethyl-p-tolylsulfone, bisdimethyldithiocarbamylzinc ethylenebisdithiocarbamate, phenyl (bispyridyl) bismuth dichloride, 2- (4-thiazolyl) -benzimidazole, pyridine triphenylborane, phenylamide, halopropargyl compounds or 2-haloalkoxyaryl-3-isothiazolone. Suitable 2-haloalkoxyaryl-3-isothiazolones include, but are not limited to: 2- (4-trifluoromethoxyphenyl) -3-isothiazolone, 2- (4-trifluoromethoxyphenyl) -5-chloro-3-isothiazolone and 2- (4-trifluoromethoxyphenyl) -4, 5-dichloro-3-isothiazolone.

Preferred microbicidal compounds are 2-N-octyl-4-isothiazolin-3-one, 4, 5-dichloro-2-N-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 1, 2-benzisothiazolin-3-one, 2-methyl-4, 5-trimethylene-4-isothiazolin-3-one, 3-iodopropargyl-N-butylcarbamate, 2-pyridylthio-1-zinc oxide, 8-pyridylthio-1-sodium oxide, sodium, 3, 4, 4' -trichlorocarbanilide, 2-bromo-2-nitro-1, 3-propanediol, 1, 2-dibromo-2, 4-dicyanobutane, methylenebis (thiocyanate), 3-bromo-1-chloro-5, 5-dimethylhydantoin, 2-dibromo-3-nitropropionamide, 2, 4, 5, 6-tetrachloroisophthalonitrile, 2- (thiocyanatomethylthio) benzothiazole and 5-chloro-2- (2, 4-dichlorophenoxy) phenol.

Generally, the biocidal compounds useful in the present invention are commercially available. Zirconium hydroxide (also known as hydrous zirconium oxide) is commercially available from Magnesium Elektron corporation (Flemington, NJ). Zirconium hydroxide may be used without further purification. Zirconium hydroxide may also be used in hydrated form, such as a paste.

When the biocidal compound is a solid, the composition of the present invention can be prepared by mixing the biocidal compound (either in molten form or in solution) with zirconium hydroxide. When the biocidal compound is a liquid, the biocidal compound can be mixed with the zirconium hydroxide as such, or as a solution. Suitable solvents for said biocidal compounds are any solvents which dissolve the biocidal compoundsA compound, but not a solvent which makes it unstable and non-reactive with zirconium hydroxide. Suitable solvents include alcohols (such as methanol, ethanol, and propanol); esters (e.g., ethyl acetate and butyl acetate); ketones (such as acetone and methyl isobutyl ketone); cyanogen (e.g., acetonitrile), and the like. A preferred solvent is (C)₁-C₄) An alcohol.

The total amount of biocidal compound in the composition is from 0.1% wt to 95% wt based on the weight of zirconium hydroxide. . Preferably, the total amount of biocidal compounds is 0.1-30% wt. Thus, the weight ratio of biocidal compound to zirconium hydroxide in the composition is generally from 0.1: 99.9 to 95: 5, preferably from 0.1: 99.9 to 30: 70.

For compositions of the present invention containing certain biocidal compounds, a portion of the biocidal compound may be rapidly released to a site, while the remaining portion of the biocidal compound is released in a controlled manner. In this case, generally up to 25% (mol) of the biocidal compound can be released in a controlled manner, while an excess of more than 25% (mol) is released rapidly. The amount released in a controlled manner depends on the particular biocidal compound used. For example, typically when the compositions of the present invention contain more than 16% wt (about 9% (mole)) of 4, 5-dichloro-2-n-octyl-3-isothiazolone, the amount of 4, 5-dichloro-2-n-octyl-3-isothiazolone of more than 16% wt is rapidly released to a site, while the remaining 16% wt is released to a site in a controlled manner. Generally, when more than 25 mole percent of the biocidal compound is added to the compositions of the present invention, the rapidly released biocidal compound can be used for initial microbial control, with the remainder of the biocidal compound released in a controlled manner being used to control subsequent microorganisms. Compositions containing more than 25 mole percent biocidal compound are preferably used at sites where both initial and subsequent control is desired.

More than one biocidal compound may be used in the compositions of the present invention, provided that the compounds do not react with and destroy each other, and that they are compatible with zirconium hydroxide. The advantage of such multiple biocidal compounds over the use of a single compound is that more extensive control can be achieved. In addition, this can reduce processing costs when multiple biocidal compounds must be used.

The compositions of the present invention may be used in any case where the biocidal compounds are used. When the biocidal compound is a microbicide, the compositions of the present invention may be used to control or inhibit the growth of microorganisms (such as bacteria, fungi, and algae) at a locus. The compositions of the present invention are suitable for use in any location where protection from microbial attack is desired. Suitable sites include, but are not limited to: a cooling tower; an air scrubber; mineral slurry; pulp and paper processing liquids; coating paper; a swimming pool; a hot spring field; a binder; a filler; olibanum; a sealant; agricultural auxiliary preservatives; a building product; cosmetics and toiletries; shampoos; disinfectants and preservatives; manufacturing industrial and consumer products; a soap; laundry room cleaning water; leather and leather products; wood (including lumber, trees, fiberboard, plywood, and composite wood materials); plastic; a lubricant; a hydraulic fluid; a medical device; metalworking fluids, emulsions and dispersions; paints (including marine paints); varnishes (including marine varnishes); a latex; an odor control liquid; coatings (including marine coatings); a petroleum processing liquid; a fuel; an oilfield fluid; chemicals for photography; printing a liquid; a sanitizer; a detergent; a textile; textile products.

When the compositions of the present invention contain microbicides, they may be added directly to the locus to be protected or as a composition which also contains a suitable carrier. Carriers suitable for use in the microbicide include, but are not limited to: water; an organic solvent such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, xylene, toluene, acetone, methyl isobutyl ketone, or an ester; or mixtures thereof. Said compositions may be formulated as microemulsions, micro-emulsifiable concentrates, emulsions, emulsifiable concentrates and pastes, or encapsulated. The particular formulation will depend on the site to be protected and the particular biocide used. Preparation of these formulations can be accomplished by well-known standard methods.

When the composition contains a microbicide, the amount of the composition of the invention required to control or inhibit the growth of microorganisms depends on the locus to be protected, but is generally sufficient if from 0.1 to 5000ppm of the microbicide is provided at the locus to be protected. Typically the microbicide will require further dilution when applied to the desired locus. For example, the compositions of the present invention may be added to metalworking liquid concentrates that also require dilution. Generally, if 5 to 50ppm of the microbicide is present in the final metalworking fluid dilution, the amount of the composition of the present invention necessary to control the growth of microorganisms in the final dilution is sufficient. On sites that cannot be further diluted (e.g. paints), generally, if 500-5000ppm of the microbicide is provided, the amount of the composition of the present invention necessary to control the growth of microorganisms is sufficient.

When the biocidal compound of the present invention is a marine antifouling agent, the composition of the present invention can be used to inhibit the growth of marine organisms by applying the composition to marine structures. Depending on the particular marine structure to be protected, the compositions of the present invention may be incorporated directly onto the marine structure, or into a coating that is subsequently applied to the marine structure.

Suitable configurations include, but are not limited to: boats, ships, oil trestles, piers, pile foundations, docks, elastic rubber and fishnets. Typically, the compositions of the present invention may be incorporated directly into a structure such as an elastomeric rubber or a fishing net fiber during manufacture. Generally, the composition of the present invention is directly applied to structures such as a fishing net or a stake. The compositions of the invention may also be incorporated into a conventional marine coating (such as a conventional marine paint or varnish).

When the composition of the invention contains a marine antifouling agent, it is generally sufficient if 0.1-30% by weight (based on the weight of the structure to be protected or on the weight of the coating used) of marine antifouling agent is provided, the amount of the composition of the invention required to inhibit or prevent the growth of marine organisms. When the composition of the invention is incorporated directly into or applied directly to a structure, it is generally sufficient if 0.1 to 30% by weight (based on the weight of said structure) of a marine antifouling agent can be provided, the amount of composition required to inhibit the growth of marine organisms. Preferably, the amount of the composition of the present invention is sufficient to provide 0.5 to 20% wt of marine antifouling agent; more preferably, 1-15% wt of marine antifoulant is provided. When the composition of the invention is incorporated into a coating, it will generally be sufficient if it is capable of providing from 0.1 to 30% by weight (based on the weight of said coating) of a marine antifouling agent, an amount of the composition of the invention suitable for inhibiting the growth of marine organisms. Preferably the composition of the invention is in an amount to provide from 0.5 to 15% wt of a marine antifouling agent; more preferably, 1-10% wt of marine antifouling agent is provided.

Generally, the compositions of the present invention containing a marine antifouling agent are mixed with a carrier, such as water; organic solvents (such as xylene, methyl isobutyl ketone, and methyl isoamyl ketone); or mixtures thereof.

The compositions of the present invention may be applied directly by any conventional means, such as dipping, spraying or coating. For example, the net may be protected by soaking the net in a composition comprising the composition of the invention and a carrier, or spraying the net with said composition.

Constructions such as stakes and fishnets may be protected by incorporating the composition of the invention directly into said construction. The composition of the invention, which also contains a carrier, can be applied to wood for pile foundations, for example, by pressure treatment or vacuum impregnation. These compositions may also be added to the fish net during the manufacturing process.

The general paint contains a binder and a solvent, and may or may not contain other components. The solvent may be an organic solvent or water. The compositions of the present invention are suitable for use in solvent and water based coatings. Solvent-based marine coatings are preferred.

Any conventional binder may be used in the marine antifouling paint mixed with the composition of the present invention. Suitable binders include, but are not limited to: polyvinyl chloride in a solvent-based system; chlorinated rubber in solvent-based systems; acrylic resins in solvent-based or aqueous systems; vinyl chloride-vinyl acetate copolymer systems as aqueous dispersions or solvent-based systems; butadiene-styrene rubber; butadiene-acrylonitrile rubber; butadiene-styrene-acrylonitrile rubber; drying oils (such as linseed oil); asphalt; an epoxide; siloxanes, and the like.

The marine coating of the present invention may or may not contain one or more of the following: inorganic pigments, organic pigments, or dyes and natural resins (such as rosin). The water-based coating may or may not contain: coalescing agents, dispersants, surfactants, rheology modifiers, or adhesion promoters. The solvent-based coating may or may not contain: extenders, plasticizers or rheology modifiers.

A typical marine coating contains 2-20% by weight of binder, up to 15% by weight of rosin/modified rosin, 0.5-5% by weight of plasticizer, 0.1-2% by weight of anti-settling agent, 5-60% by weight of solvent/diluent, up to 70% by weight of cuprous oxide, up to 30% by weight of pigment (other than cuprous oxide), and up to 15% by weight of marine antifouling agent.

Marine coatings containing the compositions of the present invention can be applied to the structure to be protected by any of a number of conventional means. Suitable means of application include, but are not limited to: spraying; rolling; brushing; or soaking.

The following examples are presented to further illustrate the invention specifically and are not intended to limit the scope of the invention in any respect.

Example 1 preparation of the composition of the invention

The compositions of the present invention are prepared by the following general methods.

To 1.0g of zirconium hydroxide in a flask was added 0.7g of 4, 5-dichloro-2-n-octyl-3-isothiazolone in 20% by weight methanol. The resulting slurry was then dried at 55 ℃ under reduced pressure to give 1.1g of a yellow powder. This composition, labeled sample 1, contained 14 wt% 4, 5-dichloro-2-n-octyl-3-isothiazolone based on the total weight of zirconium hydroxide. These data are presented in table 1.

Table 1 shows other compositions prepared according to the general method described above (only the isothiazolone was changed, or the amount of isothiazolone solution added was changed).

Table 1: composition samples of the invention isothiazolone% Wt 14, 5-dichloro-2-n-octyl-3-isothiazolone 1424, 5-dichloro-2-n-octyl-3-isothiazolone 1634, 5-dichloro-2-n-octyl-3-isothiazolone 2842-n-octyl-3-isothiazolone 1452-n-octyl-3-isothiazolone 2865-chloro-2-methyl-3-isothiazolone and 2-methyl-3-iso 15

3: 1 mixture of thiazolones 73, 4, 4' -trichlorocarbanilide 33

EXAMPLE 2 Release of bioactive Compounds

Sample 1 and the comparative samples were evaluated for the release of biocidal compounds.

Comparative sample 1 ("C-1") was prepared according to the general method of example 1, except that silica gel was used instead of zirconium hydroxide. Sample C-1 contained 14% wt 4, 5-dichloro-2-n-octyl-3-isothiazolone.

The amount of biocidal compound released from each sample was determined according to the following general method. The weighed sample was placed in a 100ml sample jar. To the jar was added 100ml of an aqueous solution containing 0.3% wt sodium diethylhexyl sulfosuccinate. This solution was then gently stirred to ensure that no foam was formed. Samples (0.5ml aliquots) were taken at various time points and transferred to microcentrifuge tubes. Each aliquot was then centrifuged at 14,000rpm for 3 minutes. The supernatant was decanted and analyzed by HPLC for the amount of biocidal compound. The microcentrifuge tube was then washed with 0.5ml of an aqueous solution containing 0.3% sodium diethylhexylsulfosuccinate, and the wash liquid was added to the sample jar. This ensures that any particles that are poured from the sample are not lost and the amount in the jar remains the same. The cumulative percentage of 4, 5-dichloro-2-n-octyl-3-isothiazolone released is shown in Table 2.

Table 2: percentage of 4, 5-dichloro-2-n-octyl-3-isothiazolone released

Sample (I)	20 minutes	40 minutes	60 minutes	120 minutes	180 minutes
						1	1.5	1.5	1.5	1.5	2.5
C-1	50.5	53.5	75	77	72

The above data clearly show that the compositions of the present invention provide superior control of the release of 4, 5-dichloro-2-n-octyl-3-isothiazolone compared to other known solid compositions.

Example 3 comparative sample

Comparative solid compositions of biocidal compounds containing titanium (IV) hydroxide were prepared and evaluated.

To 1.06g of titanium (IV) hydroxide was added 1.03g of 4, 5-dichloro-2-n-octyl-3-isothiazolone in 20.4% by weight ethanol. The resulting slurry was homogenized in 10ml of ethanol. The treatment was carried out at room temperature under reduced pressure for 1 hour, and then at 45 ℃ for 1 hour to remove the solvent. The resulting powder, labeled C-2, contained 20% wt 4, 5-dichloro-2-n-octyl-3-isothiazolone. Sample C-2 was evaluated for its ability to release 3-isothiazolone as per the procedure of example 2. The cumulative percentage of 4, 5-dichloro-2-n-octyl-3-isothiazolone released is shown in Table 3. Table 3: percentage of 4, 5-dichloro-2-n-octyl-3-isothiazolone released

Sample (I)	30 minutes	60 minutes	120 minutes	300 minutes	1860 minutes	5760 min
							C-2	4.9	7.2	11.0	19.7	50.3	68.4

The above data clearly show that solid titanium (IV) hydroxide compositions release 4, 5-dichloro-2-n-octyl-3-isothiazolone rapidly compared to the compositions of the present invention and therefore do not provide any controlled release of 4, 5-dichloro-2-n-octyl-3-isothiazolone.

Example 4 comparative sample

Comparative solid compositions of biocidal compounds containing zirconia were prepared and evaluated.

The zirconia is prepared by calcining zirconium hydroxide at 500 ℃. To 2.0g of zirconia was added 2.86g of 4, 5-dichloro-2-n-octyl-3-isothiazolone in 10% wt methanol. The solvent was then removed under reduced pressure to give a pale yellow powder. The resulting powder labeled sample C-3 contained 14% wt 4, 5-dichloro-2-n-octyl-3-isothiazolone. Sample C-3 was evaluated for its ability to release 3-isothiazolone as per the procedure of example 2. The cumulative percentage of 4, 5-dichloro-2-n-octyl-3-isothiazolone released is shown in Table 4.

Table 4: percentage of 4, 5-dichloro-2-n-octyl-3-isothiazolone released

Sample (I)	20 minutes	40 minutes	60 minutes	130 minutes	180 minutes	300 minutes
							C-3	85	79	91	92	94	95

The above data clearly show that the zirconia solid composition releases 4, 5-dichloro-2-n-octyl-3-isothiazolone rapidly and does not provide any controlled release of 4, 5-dichloro-2-n-octyl-3-isothiazolone compared to the composition of the present invention.

Example 5 fungicidal Activity

The fungicidal activity of the compositions of the invention in paint formulations was evaluated.

The paint formulation was prepared by mixing the following ingredients in a Cowles dispolver for 10-15 minutes at 3800-.

Material g/LNatrosol 250 MHR hydroxyethylcellulose 3.6 ethylene glycol 30 water 134.4Tamol 960 (40%) Polymethacrylate 8.6Triton CF-10 surfactant 3.1 colloidal 643 defoamer 1.2 propylene glycol 40.8Ti-Pure R-902 titanium dioxide 270Minex 4 filler pigment 191.3Icecap K filler pigment 60Attagel 50 Clay 6

Once the above components have been compounded, the following components are added at low speed. Materials g/L film-forming acrylic copolymer 367.1 colloidal 643 defoamer 3.6Texanol coalescing agent 11.3 Ammonia (28%) 2.8Natrosol 250 MHR hydroxyethyl cellulose 128.4 Water 130.8

Sufficient fungicide is added to the paint formulation to provide 1000, 5000, or 30,000ppm of biocidal compound.

Paint samples were prepared using sample compositions 1, 2 and 4 of the present invention. These paints were tested for mildew resistance and compared with paints containing only zirconium hydroxide ("sample C-4"), 4, 5-dichloro-2-n-octyl-3-isothiazolone ("sample C-5") and 2-n-octyl-3-isothiazolone ("sample C-6"). The actual amounts of biocidal compounds used are shown in tables 5 and 6.

The paints were tested according to the following general method. An analytical 1.27cm (0.5 inch) piece of filter paper was dipped into the paint sample to be tested, excess paint was wiped off, and the piece was placed on a Beckman mode reservoir. The painted filter paper discs were then dried at room temperature for 24 hours.

Some dried filter paper discs were leached to simulate a moist environment. The filter paper disc dried in the reservoir was placed in a water bath with a continuous flow of water. At various time periods, the filter paper discs were removed from the water bath and dried at room temperature.

After all filter paper discs were removed and dried, these filter paper discs were placed on malt agar plates (25.4 × 25.4cm) and inoculated with a mixture of 5 fungi: aspergillus niger (Aspergillus niger), Aureobasidium pullulans (Aureobasidium pullulans), Cladophora rhodosporides, Penicillium purpurogenum (Penicillium purpurogenum), and Stachybotrys chartarum. The inoculated plates were then incubated at 30 ℃ for 1 week. After 1 week, fungal growth on the filter paper discs was visually rated on a scale of 1-10, 10 for no growth, and 1 for complete fungal overgrowth. Ratings of 9 and 10 are by. The results are shown in Table 5.

The remaining filter paper discs were subjected to high heat conditions. The remaining filter paper disc from the reservoir was placed in an oven at 50 ℃. At various time points, the filter paper discs were removed from the oven. After all the filter paper discs were removed from the oven, the filter paper discs were inoculated with the fungus mixture as described above. The results obtained are shown in Table 6.

Table 5: resistant samples of fungi after several days of leaching ppm 11000103311150001010999 control on day 0, day 6, day 8, day 11, day 13^* - 6 1 1 1 1C-4 6000 2 - - - -C-4 30,000 2 - - - -^*The control was a paint containing no biocidal compound. Table 6: resistant samples of fungi ppm 21000101064310001010864100010101010C-510001010105C-6100010101010 on day 25, day 10, day 0, day 4 after heating for several days

These data clearly show that 4, 5-dichloro-2-n-octyl-3-isothiazolone and 2-n-octyl-3-isothiazolone retain their fungicidal activity when prepared as solid compositions according to the process of the present invention. These data also indicate that zirconium hydroxide does not have any fungicidal activity.

Claims (9)

1. A solid composition comprising a biocidal compound and zirconium hydroxide, wherein said composition provides controlled release of the biocidal compound.

2. The composition of claim 1 wherein said biocidal compound is selected from the group consisting of: methylene bis (thiocyanate); isothiazolone; a carbamate; a heterocyclic compound; carboxylic acids and their derivatives; alcohols and amines; ammonium and phosphonium salts; aldehydes, ketones, and formaldehyde-releasing agents; a halogenated aromatic compound; a halogenated aliphatic compound; an olefin; an enzyme; a surfactant; copper thiocyanate; n, N-dimethyl-N '-phenyl-N' -fluorodichloromethylthiosulfamide; a benzamide; a halopropargyl compound; and 2-haloalkoxyaryl-3-isothiazolone.

3. The composition of claim 2 wherein said biocidal compound is selected from the group consisting of: 2-N-octyl-4-isothiazolin-3-one, 4, 5-dichloro-2-N-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 1, 2-benzisothiazolin-3-one, 2-methyl-4, 5-trimethylene-4-isothiazolin-3-one, 3-iodopropargyl-N-butylcarbamate, 2-pyridylthio-1-zinc oxide, 2-pyridylthio-1-sodium oxide, 3, 4, 4' -trichlorocarbanilide, sodium chloride, 2-bromo-2-nitro-1, 3-propanediol, 1, 2-dibromo-2, 4-dicyanobutane, methylenebis (thiocyanate), 3-bromo-1-chloro-5, 5-dimethylhydantoin, 2-dibromo-3-nitrilopropionamide, 2, 4, 5, 6-tetrachloroisophthalonitrile, 2- (thiocyanatomethylthio) benzothiazole, 5-chloro-2- (2, 4-dichlorophenoxy) phenol.

4. The composition of claim 1 wherein the weight ratio of said biocidal compound to zirconium hydroxide is from 0.1: 99.9 to 95: 5.

5. The composition of claim 4 wherein said weight ratio is from 0.1: 99.9 to 30: 70.

6. The composition of claim 1, further comprising a carrier selected from the group consisting of: water, acetonitrile, ethyl acetate, butyl acetate, toluene, xylene, methanol, ethanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol.

7. A method of controlling the growth of bacteria, fungi, algae and marine fouling organisms which comprises introducing into the locus to be protected a composition according to claim 1.

8. The method of claim 7, wherein said site to be protected is selected from the group consisting of: a cooling tower; an air scrubber; mineral slurry; pulp and paper processing liquids; coating paper; a swimming pool; a hot spring field; a binder; a filler; olibanum; a sealant; agricultural auxiliary preservatives; a building product; cosmetics and toiletries; shampoos; disinfectants and preservatives; manufacturing industrial and consumer products; a soap; laundry room cleaning water; leather and leather products; wood includes lumber, trees, fiberboard, plywood and composite wood materials; plastic; a lubricant; a hydraulic fluid; a medical device; metalworking fluids, emulsions and dispersions; paints (including marine paints); varnishes (including marine varnishes); a latex; an odor control liquid; coatings (including marine coatings); a petroleum processing liquid; a fuel; an oilfield fluid; photographic chemicals; printing a liquid; a sanitizer; a detergent; a textile; textile products and marine constructions.

9. The method of claim 8, wherein said marine structure is selected from the group consisting of boats, ships, oil trestles, piers, pilings, docks, elastomeric rubbers, and fishnets.