Use of carbonyl stabilizers for 3-isothiazolones

Abstract

Disclosed herein are compositions comprisinga) at least one 3-isothiazolone of the formula (I) ##STR1## wherein Y is an unsubstituted or substituted (C.sub.1 -C.sub.18) alkyl, an unsubstituted or substituted (C.sub.3 -C.sub.12) cycloalkyl, an unsubstituted or halogen-substituted (C.sub.2 -C.sub.8) alkenyl or alkynyl, an unsubstituted or substituted (C.sub.7 -C.sub.10) aralkyl, or an unsubstituted or substituted aryl; andR and R.sup.1 is each independently H, halogen or (C.sub.1 -C.sub.4) alkyl; andb) a carbonyl compound selected from the group consisting of (C.sub.2 -C.sub.6) aldehydes, (C.sub.7 -C.sub.10) aromatic aldehydes or acids, (C.sub.2 -C.sub.4) dialdehydes, (C.sub.1 -C.sub.12) acids, (C.sub.2 -C.sub.8) diacids, triacids or tetracids, (C.sub.3 -C.sub.10) .alpha.,.beta. unsaturated carbonyls, (C.sub.1 -C.sub.6) haloamides of the formula ##STR2## where R.sub.1 =phenyl or (C.sub.1 -C.sub.4)alkyl, substituted phenyl,R.sub.2 =(C.sub.1 -C.sub.7)alkyl, (C.sub.1 -C.sub.7)alkoxylalkyl, or (C.sub.1 -C.sub.7)carbalkoxyalkyl;X.sub.1,X.sub.2,X.sub.3 =H or halogen wherein at least one X is halogen; furfural, dibutylene furfural and maleimides of the formula ##STR3## where R" is H, (C.sub.1 -C.sub.4) alkyl or aryl; provided that when (b) is selected from the group consisting of aldehydes and dialdehydes the ratio (b):(a) is less than 10:1.

Description

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention concerns the stabilization of 3-isothiazolone compounds by the incorporation with those compounds of certain carbonyl compounds.

2. Description of the Prior Art

Isothiazolones have generated high commercial interest as microbicides to prevent spoilage of certain aqueous and non-aqueous products caused by microorganisms. Isothiazolones are highly effective microbicides (as used herein, "microbicides" includes bactericides, fungicides and algicides and microbicidal activity is intended to include both the elimination of and the inhibition or prevention of growth of microbial organisms such as bacteria, fungi and algae); by suitable choice of functional groups, they are useful in a broad range of applications. However, it has been long recognized that either in storage prior to addition to the substrate to be treated or after addition, their efficacy may be decreased because they are not stable under practical conditions of long-term storage. Means have thus been sought for some time to improve the stability of isothiazolones.

U.S. Pat. Nos. 3,870,795 and 4,067,878 teach the stabilization of isothiazolones against chemical decomposition by addition of a metal nitrite or metal nitrate, but teach that other common metal salts, including carbonates, sulfates, chlorates, perchlorates, and chlorides are ineffective in stabilizing solutions of isothiazolones, such solutions usually being in water or in an hydroxylic solvent.

U.S. Pat. Nos. 4,150,026 and 4,241,214 teach that metal salt complexes of isothiazolones are useful because they have enhanced thermal stability, while retaining biological activity.

It is known to use certain organic stabilizers for isothiazolones, generally for use situations where metal salts may create problems, such as corrosion, coagulation of latices, insolubility in non-aqueous media, interaction with the substrate to be stabilized, and the like. Formaldehyde or formaldehyde-releasing chemicals are known as stabilizers, (see U.S. Pat. Nos. 4,165,318 and 4,129,448), as are certain organic chemicals such as orthoesters (U.S. application Ser. No. 118,366) and epoxides (U.S. application Ser. No. 194,234).

Grove, U.S. Pat. No. 4,783,221 teaches blends of isothiazolones with at least one metal salt of an organic carboxylic acid having at least six carbon atoms, wherein the metal is a transition metal, zinc, mercury, antimony, or lead; and also with a solvent diluent.

In certain applications, however, it is desirable to avoid addition of organic stabilizers by virtue of their volatility, decomposition under high heat, higher cost, difficulty in handling, potential toxicity, and the like. Formaldehyde is a suspected carcinogen, and it is desirable not to use formaldehyde in applications where contact with human skin or lungs may occur.

In actual use, copper salts, such as copper sulfate, have proved efficacious in the stabilization of isothiazolones. However, copper salts may be undesirable in effluent streams in such operations as in the manufacture of stabilized isothiazolones or in their blending into a product or the use of that product. Copper salts, especially the chlorides, may contribute to possible corrosion, or in the presence of polymers in aqueous dispersion may lead to coagulation of the dispersion.

German patent application No. 3144137A discloses the use of isothiazolone derivatives to provide bacteriostatic activity in disinfectant compositions containing aldehydes. The minimum ratio of aldehyde to isothiazolone disclosed is 10:1, and there is nothing in the disclosure relating to the stability or otherwise of the isothiazolone.

U.S. Pat. No. 4,539,071 discloses a combination of an isothiazolone and glutaraldehyde as a biocide, but there is no discussion in this disclosure relating to the stability of the composition. Commercial formulations of isothiazolones and N,N-methylolchloroacetamide are also known, being sold under the trademark Parmetol, but the carbonyl compound is not being employed as a stabilizer.

SUMMARY OF THE INVENTION

It is an object of the invention to provide a stabilization system for isothiazolones which overcomes some or all of the disadvantages of prior art systems. It is also an object to provide an isothiazolone stabilized by only low levels of stabilizer so as to avoid interference with other components in systems in which isothiazolones are used as microbicides.

These objects, and others which will become apparent from the following disclosure, are achieved by the present invention. It has been surprisingly found that isothiazolones may be stabilized against decomposition by the addition of a carbonyl compound to the composition containing the isothiazolone. Accordingly the invention provides in one aspect a composition comprising:

a) at least one 3-isothiazolone of the formula (I) ##STR4## wherein Y is an unsubstituted or substituted (C.sub.1 -C.sub.18) alkyl, an unsubstituted or substituted (C.sub.3 -C.sub.12) cycloalkyl, an unsubstituted or halogen-substituted (C.sub.2 -C.sub.8) alkenyl or alkynyl, an unsubstituted or substituted (C.sub.7 -C.sub.10) aralkyl, or an unsubstituted or substituted aryl; and R and R.sup.1 is each independently H, halogen or (C.sub.1 -C.sub.4) alkyl; and b) a carbonyl compound selected from the group consisting of (C.sub.2 -C.sub.6) aldehydes, (C.sub.7 -C.sub.10) aromatic aldehydes and acids, (C.sub.2 -C.sub.4) dialdehydes, (C.sub.1 -C.sub.12) acids, (C.sub.2 -C.sub.8) diacids, triacids and tetracids, (C.sub.3 -C.sub.10).alpha.,.beta. unsaturated carbonyls, otherwise unsubstituted (C.sub.1 -C.sub.6) haloamides of the formula ##STR5## where R.sub.1 =phenyl or (C.sub.1 -C.sub.4)alkyl-substituted phenyl, R.sub.2 =(C.sub.1 -C.sub.7)alkyl, (C.sub.1 -C.sub.7)alkoxylalkyl, or (C.sub.1 -C.sub.7)carbalkoxyalkyl; X.sub.1,X.sub.2,X.sub.3 =H or halogen wherein at least one X is halogen; furfural, dibutylene furfural and maleimides of the formula ##STR6## where R" is H, (C.sub.1 -C.sub.4) alkyl or aryl; provided that when (b) is selected from the group consisting of aldehydes and dialdehydes the ratio (b):(a) is less than 10:1.

In another aspect, the invention comprises a method for inhibiting or preventing the growth of bacteria, fungi, yeast or algae in a locus subject or susceptible to contamination by bacteria, fungi, yeast or algae, which comprises incorporating onto or into the locus, in an amount which is effective to adversely affect the growth of bacteria, fungi, yeast, or algae, the aforementioned composition.

DETAILED DESCRIPTION OF THE INVENTION AND THE PREFERRED EMBODIMENTS

The isothiazolones which are stabilized include those disclosed in U.S. Pat. Nos. 3,523,121 and 3,761,488 and represented by the formula ##STR7## as defined above. In particular, Y may be a (C.sub.1 -C.sub.18)alkyl or (C.sub.3 -C.sub.12)cycloalkyl each optionally substituted with one or more of hydroxy, halo, cyano, alkylamino, dialkylamine, arylamino, carboxy, carbalkoxy, alkoxy, aryloxy, alkylthio, arylthio, haloalkoxy, cycloalkylamino, carbamoxy, or isothiazolonyl; and unsubstituted or halo-substituted (C.sub.2 -C.sub.8) alkenyl or alkynyl; a (C.sub.7 -C.sub.10)aralkyl optionally substituted with one or more of halogen, (C.sub.1 -C.sub.4)alkyl or (C.sub.1 -C.sub.4)alkoxy; and an aryl optionally substituted with one or more of halogen, nitro, (C.sub.1 -C.sub.4)alkyl, (C.sub.1 -C.sub.4)alkyl-acylamino, carb(C.sub.1 -C.sub.4)alkoxy or sulfamyl.

Preferred substituents for Y are substituted or unsubstituted (C.sub.1 -C.sub.18) alkyl or (C.sub.3 -C.sub.12) cycloalkyl; R is preferred to be H, Me or Cl; and R.sup.1 is preferred to be H or Cl. Representative of such preferred Y substituents are methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, cyclohexyl, benzyl, 3,4-dichlorobenzyl, 4-methoxybenzyl, 4-chlorobenzyl, 3,4-dichlorophenyl, 4-methoxyphenyl, hydroxymethyl, chloromethyl, chloropropyl, hydrogen, and the like.

Particularly preferred isothiazolones are 5-chloro-2-methyl-3-isothiazolone, 2-methyl-3-isothiazolone, 2-n-octyl-3-isothiazolone, 4,5-dichloro-2-cyclohexyl-3-isothiazolone and 4,5-dichloro-2-octyl-3-isothiazolone.

Most preferred is 5-chloro-2-methyl-3-isothiazolone, either as a sole compound or in admixture with 2-methyl-3-isothiazolone. When in admixture, the preferred ratio of monochlorinated/unchlorinated isothiazolone is from about 70:30 to about 85:15, and an especially preferred ratio is from about 70:30 to about 80:20. A second especially preferred isothiazolone is 2-methyl-3-isothiazolone in combination with low levels of 5-chloro-2-methyl-3-isothiazolone, a preferred ratio being from about 98:2 to about 96:4, and an especially preferred ratio being about 97:3.

The carbonyl compounds may possess other functionality such as a halogen substituent in addition to the carbonyl group: in particular, aromatic aldehydes may have other substituents on the aromatic ring. It will also be appreciated that carbonyl compounds may exist in the form of salts which can be equally active as stabilizers, and accordingly the present invention is intended to cover the claimed compounds when they exist as salts. Preferred carbonyl compounds are (C.sub.2 -C.sub.4) aldehydes, (C.sub.4 -C.sub.6) acids, (C.sub.3 -C.sub.5) .alpha.,.beta.-unsaturated carbonyls, (C.sub.2 -C.sub.4) dialdehydes, (C.sub.2 -C.sub.4) diacids, and maleimides. Particularly preferred specific compounds include crotonaldehyde, glyoxal, maleic acid, succinic acid, fumaric acid, maleimide, (methyl-1-naphthyl) maleimide, N-ethyl maleimide, N-phenylmaleimide, malonic acid, glutaric acid and cinnamaldehyde. Additional preferred compounds include acetaldehyde, benzaldehyde, citral, and vanillin.

Some carbonyl compounds are known to have microbicidal activity, although their efficacy as stabilizers of isothiazolones has not previously been appreciated. Such compounds will be particularly desirable to use as stabilizers; examples are acrolein, benzoic acid, sorbic acid, dehydroacetic acid, glycolic acid and citric acid.

The composition may contain from about 0.01 to about 99.9999 parts of the one or more isothiazolones, and from about 0.0001 to about 99.9 parts of the carbonyl compound.

Generally, the composition of the invention will be in the form of a solution. Typical formulation ranges are illustrated in the following Table (all percentages are parts by weight) for both a concentrated solution of the isothiazolone and a dilute solution. For certain uses, such as shipping of large quantities, more concentrated solutions may also be utilized.

______________________________________FORMULATIONS TABLEIsothiazolone Carbonyl Compound Solvent______________________________________(I, Supra) 0.0001-99.9% 0-99.9899%0.01-99.9999%Preferred 0.01-20% 30-99.89%0.1-50%______________________________________

Solvents may be used to dissolve the isothiazolones and may be any organic solvent which dissolves the isothiazolones, is compatible with the proposed end use, does not destabilize the isothiazolone, and does not react with the carbonyl compound to eliminate its stabilizing action.

Hydroxylic solvents, for example, polyols, such as glycols, alcohols and the like, may be used. Under conditions of high dilution and high ratios of stabilizer to isothiazolone, glycols may be successfully used. In certain formulations, hydrocarbons, either aliphatic or aromatic, are useful solvents.

Preferred solvents are capped polyols, wherein the free hydroxyl group is replaced with an ether or ester function. Especially preferred are 2,5,8,11-tetraoxadodecane, commonly known as triethylene glycol dimethyl ether, and 4,7-dioxaundecanol-1 acetate, commonly known as diethylene glycol butyl ether acetate.

Water is a solvent for certain of the preferred isothiazolones and the carbonyl compound may be employed in aqueous formulations.

The amounts of carbonyl compound employed will vary depending on use conditions and concentrations of the isothiazolone in the mixture: effective amounts of carbonyl compounds based on isothiazolone may be ratios in the range of from about 1:100 to about 1000:1 stabilizer to isothiazolone. In concentrated solutions, ratios are generally from about 1:50 to about 50:1. Obviously higher amounts may be used, but at additional cost. At high levels of dilution of the isothiazolone (such as from 1 to 10,000 ppm isothiazolone in the solvent), the ratio of stabilizer to isothiazolone can range from about 1:10 to about 20:1. The preferred range is from 1:1 to 20:1.

The stabilization advantages of the carbonyl compounds of the present invention are noted even when the isothiazolone contains other salt stabilizers recorded in U.S. Pat. Nos. 3,870,795, 4,067,878, 4,150,026 and 4,241,214.

Uses of these new organically stabilized microbicides are typically at any locus subject to contamination by bacteria, fungi, yeast or algae. Typically loci are in aqueous systems such as water cooling, laundry wash water, oil systems such as cutting oils, oil fields and the like where microorganisms need to be killed or where their growth needs to be controlled. However these stabilized microbicides may also be used in all applications for which known microbicidal compositions are useful; preferred utilities of the compositions are to protect wood paint, adhesive, glue, paper, textile, leather, plastics, cardboard, lubricants, cosmetics, food, caulking, feed and industrial cooling water from microorganisms.

The following lists typical industries and applications of compositions:

______________________________________Industry Application______________________________________Adhesives, Sealants adhesives caulks sealantsAgriculture/food chain adjuvant preservation agricultural active ingredient agricultural chemical preservative agricultural formulations preservation animal feed preservation dairy chemicals fertilizer preservation food preservation food processing chemicals grain preservation post-harvest produce protection sugar processing tobaccoConstruction products asphalt/concrete cement modifiers construction products roof mastics synthetic stucco wall mastics joint cementCosmetics and toiletries cosmetics raw materials for cosmetics, toiletries toiletriesDisinfectants, antiseptics antiseptic disinfectantEmulsions, dispersions aqueous dispersions dispersed pigments latex photographic emulsions pigment slurries polymer laticesFormulated household fabric softenersproducts polishes waxes hand dish detergents raw materials liquid detergents hand soapsIndustrial processing, misc electrodeposition paint, baths, rinses. electrodeposition pretreatment, post rinses industrial fluids preservation pasteurization baths process aid preservationIndustrial water treatment air washers cooling towers cooling water water cooling preservation/treatment of wooden cooling tower slats and structural members can warmers brewery pasteurization closed loop water cooling systemsLaundry household laundry products laundered goods laundry wash water sanitizers-laundryLeather, leather products leather and hide leather and hide productsLubricants, hydraulic aids automotive lubricants and fluids conveyor lubricants greases hydraulic fluids lubricantsMedical devices diagnostic enzymes diagnostic kits medical devicesMetalworking & related cutting fluidsapp's metal cleaning metalworking fluidsOdor control air conditioning(active ingredient) animal bedding cat litter chemical toilet prep'ns deodorizers humidifiers industrial deodorants sanitary formulations toilet bowlsPaints and coatings emulsions paintsPaper and wood pulp, absorbant materials of paper andtheir products wood pulp packaging materials of paper and wood pulp paper paper products paper treatment soap wrap wood pulp wood pulp productsPaper mill paper mill slimicides pulp and paper slurriesPetroleum refining, fuels aviation fuels (jet fuel, aviation gas) crude oils burner, diesel and turbine fuel oils coal slurries diesel fuel additives diesel fuels fuels gasoline heating oils hydrocarbons kerosene liquefied petroleum gas petrochemical feedstocks petroleum products, storage, transportation and production recycled petroleum products residual fuel oils turbine oilsPhotographic Chemicals photographic processing - washand process water, rinses photoprocessing photoplate processing chemicals (developers, stabilizers etc)Printing fountain solutions (printing) ink components (pigments, resins, solvents, etc) inksSanitizers (active) sanitizers sanitizers-dairy sanitizers-dental sanitizers-fermentation sanitizers-food preparation sanitizers-food processing sanitizers-medical sanitizers-rendering sanitizers-veterinarySoaps, detergents, cleaners cleaners detergents household cleaners industrial cleaners liquid soaps oil and grease remover powdered soaps raw materials for cleaning products soaps surfactantsTextiles, textile products bonded fabrics burlap canvas canvas goods carpet backing carpets clothing coated fabrics curtains draperies engineering textiles fibers geotextiles goods made of textiles knitted fabrics nets nonwoven fabrics rope rugs textile accessories textile products textiles upholstery woven fabrics yarnTextile processing dye fixatives dyes fiber lubricants hand modifiers sizes textile processing fluidsTherapeutic (active or animal health/veterinarypreservative) aquaculture dental human health pharmaceutical/therapeuticWater purification charcoal beds deionization resins filters membranes reverse osmosis membranes ultrafilters water purification water purification pipes, tubingWood applications lazures (wood stains) wood wood productsMiscellaneous alcohols bedding incorporating water or gels ceramic contact lens cases-leaching electronic circuitry electronics chemicals enzymes-food production enzymes enzymes-industrial gel cushions marine antifoulants mildewcides wood plastics laundry mining natural rubber latex oil field injection waters including enhanced recover injection fluids, drilling, fracturing and completion fluids pipes plastics polymer systems polymers and resins (synthetic and natural) reagent preservation rubber rubber products skin remover solid protective/decorative films stains swimming pools waste treatment water beds______________________________________

Because isothiazolones are so active as microbicides and only low levels of carbonyl compounds are required to achieve stabilization, the amount of carbonyl compound in systems being treated will be very small, and therefore it is not likely to interfere with other components in systems requiring protection or with systems to which the protected systems will be applied. Potential areas of general application include metal-working fluids, cooling water, and air washers.

One significant area of application for the compositions of the invention is as microbicides in metal working fluids. Metal working fluids are proprietary combinations of chemicals, which may contain, inter alia, ingredients such as alkanolamines, petroleum sulfonate surfactants, oils (naphthenic, paraffinic, etc.), chlorinated paraffins and fatty esters, sulfurized fatty compounds, phosphate esters, fatty acids and their amine salts, glycols, polyglycols, boric acid esters and amides. They are utilized in the milling, machining, drilling, and other processing technologies for fabricating metal for the purposes of lubricating, cooling, preventing surface corrosion, and the like. They are sold in the form of active metal working fluid (MWF) concentrates, and are diluted in use to 1-10% active ingredients in water.

Because metal working fluids are recycled and stored, the growth of microorganisms is favored. Isothiazolones have been found effective in preventing the growth of such organisms. Certain of the components in the metal working fluids will tend to destroy the isothiazolone and so remove its microbicidal protective activity, so that stabilizers for the isothiazolone against such degradation are desirable.

It is known in the art that the performance of microbicides may be enhanced by combination with one or more other microbicides. Thus, other known microbicides may be combined advantageously with the composition of this invention.

The following examples are intended to illustrate the present invention and not to limit it except as it is limited by the claims. All percentages are by weight unless otherwise specified, and all reagents are of good commercial quality unless otherwise specified. Methods for quantitative determination of the isothiazolones in the following examples in metal-working fluids are described in detail in "Kathon.RTM. 886 MW Microbicide and Kathon.RTM. 893 MW Fungicide: Analysis in Metalworking Fluids by High-Performance Liquid Chromatography", 1988, Rohm and Haas Company.

EXAMPLES

EXAMPLES 1 TO 4

These examples demonstrate the stabilizing effect of carbonyl compounds for isothiazolones added to several different metal working fluids (MWF). MWF concentrates A and B were "semisynthetic" types having about 10 to 15 percent naphthenic/paraffinic oil, about 50 percent water, emulsifying agents, pH adjusting amines, anticorrosive agents, and EP (extreme pressure) agents.

Into a glass vial in the following order were placed: a) 5 parts by weight of the MWF concentrate solution, b) 5 parts of the stabilizer in solution or dispersion, c) 5 parts water, d) 5 parts of an aqueous solution containing 80 ppm active ingredient (AI), prepared by dilution of a 14.4% aqueous solution of an approximately 75/25 mixture of 5-chloro-2-methyl-3-isothiazolone and 2-methyl-3-isothiazolone, the former being considered the active ingredient for these purposes; also present was 9.2% magnesium chloride and 15.7% magnesium nitrate. Thus the final mixture contained 3-5% of the MWF concentrate, 15 ppm active ingredient of the isothiazolone, and 0 (control) to 1,000 ppm of the stabilizer.

The vials were then capped, stored at ambient room temperature in a closed cabinet for a designated time, filtered through a 0.45 micron filter into another vial and analyzed the same day. The relative concentration of the active ingredient was determined by reverse phase high pressure liquid chromatography, utilizing a Varian model 5500 chromatograph and an ultraviolet detector.

TABLE 1______________________________________STABILIZATION OF 5-CHLORO-2-METHYL-3-ISOTHIAZOLONE IN MWF CONCENTRATE AAFTER FIVE DAYSOriginal system contained 15 ppm 5-chloro-2-methyl-3-(AI) with 3% MWF Concentrate A in water.All stabilizers were added at 1000 ppmStabilizer % AI remaining______________________________________None, (comparative) 3crotonic acid 87trans-cinnamic acid 56fumaric acid 100maleic acid 100N-phenylmaleimide 354-acetylbutyric acid 732-oxoadipic acid 653-oxoadipic acid 383-oxoglutaric acid 374-ketopimelic acid 66succinic acid 1003-bromopropionic acid 914-hydrazinobenzoic acid 34Comparativebenzalacetophenone 112-oxooctanenitrile 0pyruvonitrile 02,4-hexanedione 0acetoacetanilide 04-chlorocinnamonitrile 52-acetoxy-3-butene nitrile 0N-(2-hydroxyethyl)acetoacetamide 1______________________________________

EXAMPLE 2

This example demonstrates the stabilizing effect of several carbonyl compounds on a commercial MWF after 4 days at room temperature. Testing was as in Example 1. In the absence of the MWF, the relative concentration of the AI remained at 100%.

TABLE 2______________________________________MWF A STABILIZED WITH CARBONYL COMPOUNDSAGED 4 DAYSOriginal system contained 15 ppm 5-chloro-2-methyl-3-isothiazolone (AI) with 3% MWF concentrate A in water.All stabilizers were added at 1000 ppm.Stabilizer % AI remaining______________________________________None 3acrylic acid 79propiolic acid 88crotonic acid 70trans-2-pentenoic acid 65trans-2-hexenoic acid 39butyric acid 72vinyl acetic acid 59crotonaldehyde 63succinic acid 78phthalic acid 22maleic acid 91fumaric acid 68maleimide 67isophthalic acid 67malonic acid 91succinic acid 79glutaric acid 733-oxoglutaric acid 28Comparativemethyl crotonate 9crotononitrile 63-penten-2-one 4succinamide 6succinonitrile 4______________________________________

EXAMPLE 3

This example demonstrates the stabilizing effect of further carbonyl compounds on a commercial MWF after 3 days at room temperature.

The original system contained 15 ppm of 5-chloro-2-methyl-3-isothiazone (AI) with 3% MWF concentrate A in water. All stabilizers were added at 1000 ppm.

TABLE 3______________________________________Stabilizer % AI remaining______________________________________None 19adipic acid 55citric acid 79tactic acid 43(D)(L) malic acid 69(D)(L) mandelic acid 37oxalic acid 76propionic acid 63sorbic acid 52tartaric acid 65______________________________________

EXAMPLE 4

In this experiment, further results are shown for a variety of carbonyl compounds in two different MWFs. The carbonyl compounds tested were readily soluble in the test system; there was no color development with the systems on mixing.

TABLE 4______________________________________COMPARISON OF SEVERAL CARBONYL COMPOUNDSIN TWO MWF SYSTEMS AFTER 11 DAYSOriginal system contained 15 ppm 5-chloro-2-methyl-3-isothiazolone (AI) with 3% MWF concentrate A in water.All stabilizers were added at 1000 ppm. Stabilizer MWF Conc. A MWF Conc. B level % AI % AIStabilizer (ppm) Remaining Remaining______________________________________None, 0 43 3(comparative)N-ethylmaleimide 1000 77 3N-phenylmaleimide 1000 72 19t-cinnamaldehyde 1000 61 50iodoacetamide 1000 83 31______________________________________

EXAMPLE 5

This example illustrates the ability of carbonyl compounds to stabilize isothiazolone in the presence of typical formulations used for water treatment in cooling towers.

A synthetic cooling tower water was prepared by adding 466.4 mg sodium carbonate into a liter of deionized water. The pH was adjusted to 9.0 using concentrated hydrochloric acid. Into the solution was added 10.7 ml scale/corrosion inhibitor stock solution (Acrysol QR 1086, Bahibit AM, and Cobratec TT-50-S), then 160 mg CaCl.sub.2.2H.sub.2 O and 122 mg MgCl.sub.2.6H.sub.2 O. The final solution was adjusted to pH 9.0 with hydrochloric acid.

The synthetic water contained 170 ppm hardness as CaCO.sub.3, 440 ppm alkalinity as CaCO.sub.3, 5 ppm Acrysol.RTM. QR 1086, 5 ppm Bahibit.TM. AM (Phosphonate), and 2 ppm Cobratec.RTM. TT-50-S (Tolyltriazole). The hardness was 160 ppm CaCl.sub.2.2H.sub.2 O and 122 ppm MgCl.sub.2.6H.sub.2 O.

Isothiazolone was added at 5 ppm AI and incubated for 10 days at room temperature. AI analysis was done as described in Example 1. Results are given in Table 5.

TABLE 5______________________________________COMPARISON OF CARBONYL STABILIZERS INCOOLING TOWER WATER AFTER 10 DAYSAT ROOM TEMPERATUREStabilizer Stabilizer Level (ppm) % AI Remaining______________________________________None 0 40crotonaldehyde 50 40crotonaldehyde 25 40glyoxal 50 74glyoxal 25 60maleimide 50 71maleimide 25 57t-cinnamaldehyde 50 43t-cinnamaldehyde 25 40______________________________________

EXAMPLES 6-9

These examples illustrate the stabilizing effect of carbonyl compounds for isothiazolones in metalworking fluids. Tests were run as described for Examples 1-4. Results are given in Tables 6-10.

TABLE 6______________________________________11.25 ppm AI, 300 ppm stabilizer, 2 days at room temperature,a synthetic metalworking fluid (MWF-A)Stabilizer % AI remaining______________________________________None 50Benzaldehyde 56Salicylaldehyde 66Acetaldehyde 67Methacrolein 69______________________________________ TABLE 7______________________________________15 ppm AI, 1000 ppm stabilizer, 3 days at room temperature,MWF-AStabilizer % AI remaining______________________________________None 23Furfuraldehyde 554-Methoxysalicylaldehyde 66Methyl glyoxal 77Glycollic acid 77______________________________________ TABLE 8______________________________________15 ppm AI, 2000 ppm stabilizer, 3 days at room temperature,MWF-AStabilizer % AI remaining______________________________________None 14Acrolein 67______________________________________ TABLE 9______________________________________11.25 ppm AI, 300 ppm stabilizer, 2 days at room temperature,a synthetic metalworking fluid (MWF-A).Stabilizer % AI remaining______________________________________None 32Metolachlor 44Diethatyl Ethyl 72Alachlor 46Butachlor 42______________________________________

The four stabilizers were added as the commercially available emulsifable concentrates (stabilizer in an aromatic or aliphatic solvent plus a mixture of nonionic and anionic emulsifiers). The products and suppliers were metolachlor (Dual EC-Ciba-Geigy); diethatyl ethyl (Antor EC-BFC Chemicals); alachlor (Lasso EC-Monsanto); and butachlor (Machete EC-Monsanto).

While the invention has been described with reference to specific examples and applications, other modifications and uses for the invention will be apparent to those skilled in the art without departing from the spirit and scope of the invention defined in the appended claims.

Claims

1. Composition comprising

a) at least one 3-isothiazolone of the formula (I) ##STR8## wherein Y is an unsubstituted or substituted (C.sub.1 -C.sub.18) alkyl, an unsubstituted or substituted (C.sub.3 -C.sub.12) cycloalkyl, an unsubstituted or halogen-substituted (C.sub.2 -C.sub.8) alkenyl or alkynyl, an unsubstituted or substituted (C.sub.7 -C.sub.10) aralkyl, or an unsubstituted or substituted aryl; and

R and R.sup.1 is each independently H, halogen or (C.sub.1 -C.sub.4) alkyl; and

b) a carbonyl compound selected from the group consisting of (C.sub.2 -C.sub.6) aldehydes, (C.sub.7 -C.sub.10) aromatic aldehydes or acids, (C.sub.2 -C.sub.4) dialdehydes, (C.sub.1 -C.sub.12) acids, (C.sub.2 -C.sub.8) diacids, triacids or tetracids, (C.sub.3 -C.sub.10) .alpha.,.beta. unsaturated carbonyls, (C.sub.1 -C.sub.6) haloamides of the formula ##STR9## where R.sub.1 =phenyl or (C.sub.1 -C.sub.4)alkyl-substituted phenyl,

R.sub.2 =(C.sub.1 -C.sub.7)alkyl, (C.sub.1 -C.sub.7)alkoxylalkyl, or (C.sub.1 -C.sub.7)Carbalkoxyalkyl;

X.sub.1,X.sub.2,X.sub.3 =H or halogen wherein at least one X is halogen; furfural, dibutylene furfural and maleimides of the formula ##STR10## where R" is H, (C.sub.1 -C.sub.4) alkyl or aryl; the amount of b) being sufficient to stabilize a), provided that when (b) is selected from the group consisting of aldehydes and dialdehydes the ratio (b):(a) is less than 10:1.

2. Composition according to claim 1 wherein the carbonyl compound is selected from (C.sub.2 -C.sub.4)aldehydes, (C.sub.2 -C.sub.4)dialdehydes, (C.sub.4 -C.sub.6)acids, (C.sub.2 -C.sub.4)diacids, (C.sub.3 -C.sub.5).alpha.,.beta.-unsaturated carbonyls, and maleimides.

3. Composition according to claim 1 wherein the carbonyl compound is selected from crotonaldehyde, glyoxal, maleic acid, succinic acid, fumaric acid, maleimide, (methyl-1-naphthyl) maleimide, N-ethyl maleimide, N-phenylmaleimide, malonic acid, glutaric acid, cinnamaldehyde, crotonic acid, iodoacetamide, benzaldehyde, acetaldehyde, salicylaldehyde, methacrolein, and acrolein.

4. Composition according to claim 1 wherein said carbonyl compound is (C.sub.1 -C.sub.6) haloamide selected from the group consisting of alachlor, butachlor, diethatyl ethyl, and metolachlor.

5. Composition according to claim 1 wherein Y is selected from: (C.sub.1 -C.sub.18)alkyl or (C.sub.3 -C.sub.12)cycloalkyl each optionally substituted with one or more of hydroxy, halo, cyano, alkylamino, dialkylamine, arylamino, carboxy, carbalkoxy, alkoxy, aryloxy, alkylthio, arylthio, haloalkoxy, cycloalkylamino, carbamoxy, or isothiazolonyl; an unsubstituted or halo-substituted (C.sub.2 -C.sub.8) alkenyl or alkynyl; a (C.sub.7 -C.sub.10)aralkyl optionally substituted with one or more of halogen, (C.sub.1 -C.sub.4) alkyl or (C.sub.1 -C.sub.4)alkoxy; and an aryl optionally substituted with one or more of halogen, nitro, (C.sub.1 -C.sub.4)alkyl, (C.sub.1 -C.sub.4)alkyl-acylamino, carb(C.sub.1 -C.sub.4) alkoxy or sulfamyl.

6. Composition according to claim 1 wherein the 3isothiazolone is selected from 5-chloro-2-methyl-3-isothiazolone, 2-methyl-3-isothiazolone, 2-n-octyl-3-isothiazolone, 4,5-dichloro-2-cyclohexyl-3-isothiazolone, and 4,5-dichloro-2-octyl-3-isothiazolone.

7. Composition according to claim 1 comprising a carbonyl compound and a mixture of 5-chloro-2-methyl-3-isothiazolone and 2-methyl-3-isothiazolone.

8. Composition according to claim 1 wherein the total amount of 3-isothiazolone is from 0.1 to about 50% by weight, and the carbonyl compound is present in an amount from 0.01 to about 50% by weight, based on the total weight of the composition.

9. Composition according to claim 1 wherein the ratio of carbonyl compound to total 3-isothiazolone present is from about 1:50 to about 20:1, subject to the proviso of claim 1.

10. Composition according to claim 1 wherein the ratio of carbonyl compound to total 3-isothiazolone present is from about 1:1 to about 20:1, subject to the proviso of claim 1.

11. Composition according to claim 1 which additionally comprises a polyol solvent.

12. A method of stabilizing a 3-isothiazolone of the formula (I) as defined in claim 1 comprising incorporating with said 3-isothiazolone an effective amount of a carbonyl compound selected from the group consisting of (C.sub.2 -C.sub.6)aldehydes, (C.sub.7 -C.sub.10) aromatic aldehydes or acids, (C.sub.2 -C.sub.4) dialdehydes, (C.sub.1 -C.sub.12) acids, (C.sub.2 -C.sub.8) diacids, triacids or tetracids, (C.sub.3 -C.sub.10) .alpha.,.beta. unsaturated carbonyls, (C.sub.1 -C.sub.6) haloamides of the formula ##STR11## where R.sub.1 =phenyl or (C.sub.1 -C.sub.4)alkyl-substituted phenyl,

R.sub.2 =(C.sub.1 -C.sub.7)alkyl, (C.sub.1 -C.sub.7)alkoxylalkyl, or (C.sub.1 -C.sub.7)carbalkoxyalkyl;

X.sub.1, X.sub.2,X.sub.3 =H or halogen wherein at least one X is halogen; furfural, dibutylene furfural and maleimides of the formula ##STR12## where R" is H, (C.sub.1 -C.sub.4) alkyl or aryl.

13. Method according to claim 12 wherein Y is selected from: (C.sub.1 -C.sub.18)alkyl or (C.sub.3 -C.sub.12)cycloalkyl each optionally substituted with one or more of hydroxy, halo, cyano, alkylamino, dialkylamine, arylamino, carboxy, carbalkoxy, alkoxy, aryloxy, alkylthio, arylthio, haloalkoxy, cycloal cylamino, carbamoxy, or isothiazolonyl; an unsubstituted or halo-substituted (C.sub.2 -C.sub.8) alkenoyl or alkynyl; a (C.sub.7 -C.sub.10)aralkyl optionally substituted with one or more of halogen, (C.sub.1 -C.sub.4)alkyl or (C.sub.1 -C.sub.4)alkoxy; and an aryl optionally substituted with one or more of halogen, nitro, (C.sub.1 -C.sub.4)alkyl, (C.sub.1 -C.sub.4)alkyl-acylamino, carb(C.sub.1 -C.sub.4)alkoxy or sulfamyl.

14. Method according to claim 12 wherein the carbonyl compound is selected from (C.sub.2 -C.sub.4)aldehydes, (C.sub.2 -C.sub.4)dialdehydes, (C.sub.4 -C.sub.6)acids, (C.sub.2 -C.sub.4)diacids, (C.sub.3 -C.sub.5)a,b-unsaturated carbonyls, and maleimides.

15. Method according to claim 12 wherein the carbonyl compound is selected from crotonaldehyde, glyoxal, maleic acid, succinic acid, fumaric acid, maleimide, (methyl-l-naphthyl) maleimide, N-ethyl maleimide, N-phenylmaleimide, malonic acid, glutaric acid, cinnamaldehyde, crotonic acid, iodoacetamide, benzaldehyde, acetaldehyde, salicylaldehyde, methacrolein, and acrolein.

16. Method according to claim 12 wherein the ratio of incorporated carbonyl compound to 3-isothiazolone present is from about 1:100 to 1000:1.

17. Method according to claim 12 wherein the ratio of incorporated carbonyl compound to 3-isothiazolone present is from about 1:50 to 20:1.

18. Method of inhibiting or preventing the growth of bacteria, fungi or algae in a locus subject or susceptible to contamination thereby, comprising incorporating into or onto the locus a composition according to claim 1 in an amount effective to adversely affect the growth of said bacteria, fungi or algae.

19. Method according to clam 18 wherein the locus is selected from a metal-working fluid, a cutting oil, a water-cooling system, a cosmetic formulation, a paint, and a film-forming agent.