Microbicidal microemulsion

Abstract: Dilution stable oil-in-water microemulsions of microbicidal isothiazolones of low water solubility can be formed by using certain polyoxyethylene/polyoxypropylene block copolymers together with anionic surfactant and specified cosurfactant.

Description: This invention is concerned with microemulsions of isothiazolones of low water solubility. The microemulsions of the inventions upon dilution with water, remain as microemulsion, These microemulsions are useful in many applications, such as fungicides, slimicides, algaecides or bactericides in any locus. Microemulsions are dispersions of one liquid phase in a second immiscible phase. They can be water continuous (o/w) or oil continuous (w/o) where "oil" denotes an organic liquid (or liquids) of low water solubility. An unique property of microemulsions is that the interfacial tension between the two phases is very low; much lower than can be measured with conventional instruments such as a DuNouy Tensiometer. This low interfacial tension results from very specific combinations of "oil" (water immiscible organic liquid) and surfactants and water and is manifested in that the particle size of the dispersed phase is extremely small, usually less than 1000Å. Since this is small in relation to the wave length of visible light, microemulsions appear opalescent or optically clear. Microemulsions are stable toward phase separation for periods measured in years. This contrasts with the normal macroemulsion, where milky appearance results from emulsion particles being in the 1-20 range, and where phase separation will typically occur within hours to weeks after the emulsion is prepared. Optimum solubilization of an oil to give an o/w microemulsion can occur within a narrow composition range of oil and surfactant and cosurfactant and water. A typical example is given in Microemulsion Theory and Practice, Ed. L.M. Prince, Academic Press (1977) describing the system p -xylene and sodium lauryl sulfate and pentanol and water. When the composition is outside the microemulsion range defined by a phase diagram, multiphase regions exist. The consequence is that dilution of a microemulsion composition with water usually leads to a macroemulsion or multiphase, which are unstable systems. In a practical sense it is desirable to define a microemulsion composition that will remain clear and not phase separate when further diluted in water. An o/w micellar solution can result when a small amount of "oil" is added to an aqueous solution of surfactant and water. If the amount of surfactant is great in relation to the "oil" (say >5:1) the oil can migrate to the interior of the surfactant micelle without greatly disturbing it. This solubilizing of the oil can result in a clear micellar solution and will very often retain clarity when further diluted in water. Because of large excesses of surfactant, compositions to give solubilized solutions are not as critical as with microemulsions. A microemulsion represents a much more efficient way of solubilizing an oil. US-A-4,567,161 discloses transparent microemulsions with active ingredients (e.g. pesticides, herbicides, pharmaceuticals) together with a phospholipid and a coemulsifier (glycerin ester). US-A-4,568,480 discloses preparing microemulsions using alkoxylated phenols where the phenol hydrophobe is a multi-ring system connected by alkylinden groups and the ethoxylated alcohol contains an ester group. These are generally useful with or without any additional phosphate ester alkali metal salt surfactant to prepare microemulsions of cosmetics, toiletries and drugs. EP-A-55,401 discloses the preparation of microemulsions of insecticides and acaricides using an ethoxylated phenol prepared by alkylating tolylethylphenol and phenol with p -methylstyrene. DE-3,235,612-AI discloses cold stable aqueous microemulsions of agrochemical pesticides, household pest control agents and pharmaceuticals using an emulsifier which is a mixture of alkylaryl polyglycol and an alkylarylsulfonate salt. EP-A-092,457 discloses wood preservation concentrates containing a preservative and insecticides and fungicides formulated with an anionic emulsifier and a coemulsifier such as butoxy ethanol or diethylene glycol monobutyl ether. When further diluted these microemulsions form translucent to opaque dilutions. US-A-4,146,499 discloses a method for preparing microemulsion. Japanese Patent Application 52,122-628 discloses oil-in-water microemulsions where insecticides are emulsified with a nonionic surfactant. EP-A-160,182 discloses microemulsions of a synthetic pyrethroid insecticide with a sulfonate anionic surfactant and multi-ring phenol ethoxylates. US-A-3,683,078 discloses transparent solutions of various pesticides using relatively high levels of various anionic and ethoxylated or propoxylated phenols. DE 2328192 discloses a microemulsion of <5% of a water insoluble herbicide with an emulsifier and a hydrotrope. We have now found oil-in-water microemulsions of certain isothiazolones of low water solubility which are useful as biocides. By "low water solubility" is meant that the material is soluble in water at less than 1% by weight (at normal temperature and pressure). The microemulsions of the invention are prepared by combining specifically defined amounts of isothiazolone, anionic surfactant, cosurfactant, polyoxyethylene/polyoxypropylene block copolymer, and water. Isothiazolones of low water solubility are often prepared as a solution of isothiazolone in a water-miscible organic solvent such as propylene glycol. These concentrates are further diluted by the user in water or various aqueous based media to control growth of microorganisms. This approach sometimes has the disadvantage of poor homogeneity of the isothiazolone in the dilution when the solubility of the isothiazolone is exceeded. Often it is desirable to market the isothiazolone at active ingredient levels (AI) of only several percent in the concentrate to be diluted. This requires a large amount of organic solvent per AI unit. A water based concentrate would have substantial cost advantage and environmental advantages by replacing all or most of the organic solvent with water. A microemulsion form of the isothiazolone which would remain a microemulsion upon dilution would overcome these drawbacks. The presence of such amounts of such water miscible solvent as is necessary or convenient to dissolve the isothiazolone is not generally detrimental to the dilution performance of the microemulsions of the invention so that the invention extends to the presence of such optional further ingredient but not to the presence of other unspecified ingredients in such potentially large amounts. The isothiazolones which may be employed in this invention include those having a water solubility of less than 1% by weight of the formula: wherein Y is an unsubstituted alkyl group of 2 to 18 carbon atoms, a substituted alkyl group of 2 to 18 carbon atoms having at least one hydrogen atom replaced by hydroxy, halo, cyano, alkylamino, dialkylamino, phenylamino, halophenylamino, carboxy, carbalkoxy, alkoxy, aryloxy, morpholino, piperidino, pyrrolidonyl, carbamoxy, or isothiazolonyl, wherein the total number of carbon atoms in the substituted alkyl group does not exceed 18, an unsubstituted or halo-substituted alkenyl group of 4 to 18 carbon atoms, unsubstituted or halo-substituted alkynyl group of 4 to 18 carbon atoms, an unsubstituted or alkyl-substituted cycloalkyl group having a four to six carbon atom ring and up to 12 carbon atoms, an unsubstituted or a halo-, lower alkyl-, or lower alkoxy-substituted aralkyl group wherein the total number of carbon atoms in the aralkyl group does not exceed 10; or an unsubstituted or a halo-, nitro-, lower alkyl-, or lower carbalkoxly-, substituted aryl group wherein the total number of carbon atoms in the aryl group does not exceed 10; and R and R¹ are the same or different substituent selected from hydrogen, halogen, or a (C₁-C₄)alkyl group. It will be apparent to the skilled person that the water solubility of the isothiazolones depends on the type of substituent (i.e. R,R¹ and Y). For example, the carbon content of the alkyl group required for low solubility will vary depending on the R or R¹ or both the R and R¹ substituents. For example, when R=R¹=halo, the alkyl group can be as low as two carbon atoms for the water solubility to be less than 1%. However when only one of the R or R¹ is halo and the other is hydrogen, the alkyl group will need to contain at least four carbon atoms. When both R and R¹ are hydrogen then the alkyl group will be found to require at least six carbon atoms for low solubility. In 100 parts by weight (p.b.w.) of the compositions of the invention, these isothiazolones are used in an amount of 0.1 to 50 p.b.w, in combination with 0.1 to 25 p.b.w. of anionic surfactant, 0.1 to 25 p.b.w. of specified cosurfactant, 0.5 to 50 p.b.w. of specified polyoxyethylene/polyoxypropylene block copolymer, 10 to 99 p.b.w. water and 0 to 30 p.b.w. of adjuvant(s). Anionic surfactants which may be employed include alkylaryl sulfonate salts containing from 6 to 20 carbon atoms in the alkyl group, such as nonyl benzene sulfonate salts, dodecyl benzene sulfonate salts and tridecylbenzene sulfonate salts; salts of (C₈ to C₂₀ alkyl sulfates; salts of (C₁₀ to C₂₀) fatty alcohol ethoxylate sulfates containing from 2 to 15 moles of ethylene oxide, such as decyl alcohol sulfate salts [C₁₀H₂₃O(CH₂CH₂O)₂SO₃⁻], dodecyl EO₁₂ sulfate salts, and tridecyl EO₁₅ sulfate salts; mono or dialkyl (C₄ to C₁₃) sulfosuccinate salts, such as dioctyl sulfosuccinate salts and ditridecyl sulfosuccinate salts; and sulfated oils such as sulfated castor oil and sulfated neets foot oil. The counter ion of the sulfonate and sulfate salts described above may be the alkali metal or alkaline earth metal salts such as sodium, potassium, calcium and magnesium; ammonium salts; mono-, di- or tri-alkyl ammonium salts from amines, such as methylamine, dimethylamine and triethylamine; mono-, di- or tri-hydroxyalkylammonium salts from amines such as ethanolamine, diethanolamine and triethanolamine. Especially preferred are the sodium salts. Suitable cosurfactants include alkyl alcohols such as (C₄-C₁₀)alkyl alcohols and, preferably (C₆ to C₈) alcohols; other suitable cosurfactants include alkyl alkyoxylated alcohols of the formula CH₃(CH₂) n (OC₂H₄) m OH or CH₃(CH₂) n (OC₃H₆) m OH wherein n is 0 or an integer up to 7 and preferably 3 to 5 and m is an integer of 1 to 4 and preferably 1 to 2. Important to this invention is the use of one or more polyoxyethylene and polyoxypropylene block copolymers of the formula: wherein R³ is (C₁-C₆)alkoxy or a radical of the formula HO(CH₂CH₂O) n ¹ - where m¹ is an integer greater than 15 and preferably greater than 20 and n¹ is an integer greater than 10 and preferably greater than 20; having a weight average molecular weight above 1750 and preferably above 3000 containing 10 to 80% by weight of ethylene oxide units. The presence of this copolymer enables the dilution of the microemulsion while still retaining the characteristics of a microemulsion. In addition, it may be necessary in the use of the microemulsions or in the preparation of the microemulsion, to use various adjuvants, for example antifoam agents (such as the commerically available silicone antifoam emulsions) antifreeze agents (such as propylene glycol and urea) water soluble inorganic salts (such as sodium chloride and magnesium sulfate) which are used to optimize the action of the surfactant by increasing the concentration of the surfactant at the interface of the microemulsion. For ease in preparing microemulsions of crystalline isothiazolones, such as 4,5 - dichloro- n -octyl isothiazolone, those isothiazolones may be dissolved in water-immiscible organic solvents such as aromatic and nonaromatic hydrocarbons, esters, amides, kerosene, dioctylphthalate, dimethyl alkyl (C₆-C₁₈) amides or kylene, before combining with other ingredients to make the microemulsion. The ratios of components are as follows: (All parts by weight. General Preferred Most Preferred Isothiazolone 0.1-50 1-30 1-12.5 Anionic Surfactant 0.1-25 1-15 1-4 Cosurfactant 0.1-25 1-20 1-6 Polyoxyethylene/polyoxypropylene copolymer 0.5-50 1-40 1-10 Adjuvants 0-30 0-20 0-16 Maximum total of above components 90 80 50 plus water to make a total of 100 parts by weight. As specifed above, the compositions may additionally contain such amounts of water-miscible solvent as is necessary or convenient to dissolve the isothiazolone. The ratio of total surfactant to emulsified oil is important. The amount of surfactant required to emulsify an oil will depend on the amount of oil in the emulsion, more specifically the interfacial surface area which is proportional to the amount of emulsified oil at a constant particle size and can be determined in any individual case by simple trial and error. The microemulsions described here have relatively low surfactant to oil ratios, about 1:1. Thus the total surfactant (anionic surfactant and cosurfactant and EO/PO copolymer) required to make a 1% oil emulsion, (1%AI if no solvents are present) is about 1%. Ten percent surfactant would be required to prepare an equivalent 10% AI microemulsion. If the ratio of surfactant to oil increases to deviate significantly from 1:1 (say >5:1) the compositions are better described as solubilized emulsions or micellar solutions. The compositions required to prepare microemulsions are usually very specific while the exact composition requirements to make a micellar solution are less exacting because of the much greater amount of surfactant used. These biocidal microemulsions are useful in many areas of preservation including disinfectants, sanitizers, cleaners, deodorizers, liquid and powder soaps, skin removers, oil and grease removers, food processing chemicals, dairy chemicals, food preservatives, animal food preservatives, wood preservation, polymer latices, paint, lazures, stains, mildewicides, hospital and medical antiseptics, medical devices, metal working fluids, cooling water, air washers, petroleum production, paper treatment, pulp and paper slurries, paper mill slimicides, petroleum products, adhesives, textiles, pigment slurries, latexes, leather and hide treatments, petroleum fuel, jet fuel, laundry sanitizers, agricultural formulations, inks, mining, nonwoven fabrics, petroleum storage, rubber, sugar processing, tobacco, swimming pools, photographic rinses, cosmetics, toiletries, pharmaceuticals, chemical toilets, household laundry products, diesel fuel additives, waxes and polishes, oil field applications, and many other applications where water and organic materials come in contact under conditions which allow the growth of undesired microorganisms. It is well known in the art that the performance of biocides is frequently enhanced by combining one or more biocides. In fact, there have been numerous examples of synergistic combinations of biocides. Thus, other known biocides may be combined advantageously with the microemulsions of this invention. When the concentrate microemulsions (0.1-50% AI) are diluted in water, the microemulsion remains. This is due to the presence of the EO/PO block copolymers. While the use of the anionic surfactant and cosurfactant by themselves at the proper level will form a microemulsion in the concentrate, when diluted, macroemulsions form which phase separate, and sometimes quite rapidly. In contrast, the dilutions described here are stable toward phase separation for months. Microemulsions, especially those containing nonionic surfactants (EO/PO types here) tend to exhibit phase changes when stored hot or cold. These phase changes are undesirable because ultimately layers may separate. The microemulsions of this invention may be formulated to remain microemulsions at anticipated storage temperatures (0°C to 54°C). The microemulsions of this invention may be formulated to remain microemulsions even when diluted in either soft (e.g. deionized) water or hard (e.g. Army Hard 342 ppm) water. Examples In the Examples which follow, which are given for the purposes of illustration only, the following procedures and abbreviations are used. All parts and percentages are by weight unless otherwise specified. A. Testing Microemulsions (1) The concentrate appearance (a) initial observation at ambient temperature C = clear appearance microemulsion SO = slightly opalescent microemulsion O = opalescent microemulsion CL = cloudy appearance macroemulsion P = phase separation - layer(s) formed - unstable macroemulsion (b) observation, hot (54°C) and cold (0°C) (same evaluation symbols) The microemulsion concentrate is prepared and a portion placed in an oven at 54°C and another portion in a refrigerator at 0°C. An observation is made after temperature equilibration (usually about 2 hours). Another observation is made at a later time (1 to 2 weeks). (2) Aqueous dilutions Dilutions are made with 1 part microemulsion and 25 parts water. Initially tap water is used (200 ppm hardness). In later stages a variety of dilutions using water of various hardness levels were evaluated (0, 50, 200, 342 ppm). A rating scale of 0-5 is used to evaluate the clarity of the dilutions. The sample is evaluated immediately after the dilution. Because there can be a tendency for coalescence of emulsified particles with time to give large particles and a corresponding increase in opacity, a second reading is taken at two hours and in the final compositions, at 24 hours. The scale is defined as follows: 0 = perfectly clear; 1 = clear, very slight opalescence; 2 = opalescent; 3 = opalescent, slightly cloudy; 4 = cloudy (macroemulsion); and 5 = phase separation. (+ is used to denote a slightly lower reading) (- is used to denote a slightly higher reading) A rating in the range of 0 to 3 indicate the material is a microemulsion with the rating 3 indicating borderline micro/macro. A rating of 4 indicates a macroemulsion. A rating of 5 indicates unstable macroemulsion with a tendency toward phase separation. Another rating is the ease with which the microemulsion mixed with water. (Self emulsification SE) VG = spontaneous mixing, little agitation needed G = some agitation needed F = substantial agitation needed Example 1 - Illustrates that dilution of microemulsion forms macroemulsion Microemulsions could be formed at 12.5% AI by using sodium dodecylbenzenesulfonate as the surfactant and butoxyethanol as the cosurfactant with either the 99% technical or 45% propylene glycol solution of technical isothiazolone. Example 2 - Illustrates use of different cosurfactants Butoxyethanol and hexoxyethanol are preferred cosurfactants. A phase change is seen between ambient temperature and 0°C with n -hexanol and between ambient temperature and 54°C with the C₈-C₁₀ alcohol mixture. Example 3 An experiment to determine the effects of varying three surfactants and the effect of EO/PO on dilution. Conclusions : EO/PO surfactant containing formulations 3A through 3I gave transparent microemulsion dilutions unlike Example 1. The concentrate is clearer with a high sulfonate level at 54°. At 0° the low sulfonate-low EO/PO surfactant gives a cloudy emulsion. The stabilization of the dilution is increased by high sulfonate and high EO/PO surfactant level. Butoxyethanol has little effect within the range studied. Example 4 - Evaluation of various hydrophile/-lipophile balance polyoxyethylene/polyoxypropylene block copolymers R(PO) m (EO) n H Example 5 An experiment was run to optimize the microemulsion containing HOEO₂₁PO₆₇EO₂₁OH surfactant. (These formulations contain a small amount of a 31% silicone emulsion - to eliminate foaming.) The dilution stability of Example 5C and Example 5G was very good (essentially equivalent) with the formulation of Example 5G having a less noticable phase change when heated above 54°C. Cold stability at -10°C is good with all samples. Example 6 An experiment to compare 2 different methods of preparation of the formulation of Example 5C. A - Experiment 5C was repeated by mixing all ingredients except n -octyl isothiazolone and heating the mixture to 50°C with agitation to form a clear solution. n -Octyl isothiazolone was then added at ambient temperature and a clear microemulsion formed upon agitation. B - Experiment 5C was repeated except solution of the HOEO₂₁PO₆₇EO₂₁OH in butoxyethanol was not initially added. A macroemulsion formed when all ingredients except this solution were mixed. When this butoxyethanol solution was added to the macroemulsion a clear microemulsion is formed. The properties of these two microemulsions were evaluated. Conclusion - These two methods of preparation afford equivalent microemulsions. Example 7 - Use of 99% technical n -octylisothiazolone. Conclusion: A slightly higher sulfonate level gives a clear concentrate which does not phase separate at hot or cold temperature. The preferred formulation using 99% technical is Example 7D because of dilution stability and lack of concentrate phase changes at 0°C and 54°C. Example 8 Microemulsion of a Solid Isothiazolone The solid, 4,5-dichloro- n -octyl-isothiazolone, is dissolved in xylene to form the "oil" to be microemulsified. The following ingredients are mixed together. Wt % 4,5-dichloro- n -octyl isothiazolone 10.00 Xylene 5.00 C₁₂H₂₅EO₁₂SO₄Na+(60% aq) 8.00 HOEO₂₁PO₆₇EO₂₁OH 4.00 Butoxyethanol 25.00 Antifoam 0.05 2% aqueous NaCl 47.95 Total 100.00 Appearance concentrate C Appearance dilution (1:25) 3 Example 9 - Microemulsion of 4,5-Dichloro n -octyl isothiazolone A solution of solid 4,5 dichloro n -octyl isothiazolone in pentyl alcohol was prepared by mild heating. This was added to a mixture of the remaining ingredients and this mixture heated to 50°-60°C until a clear microemulsion formed. Ingredients Parts by Wt. 4,5 Dichloro n -octyl isothiazolone 10.00 Pentyl alcohol 5.00 HOEO₂₁PO₆₇EO₂₁OH 8.00 C₁₂H₂₅EO₁₂SO₄Na (60% aqueous) 16.00 Butoxyethanol 25.00 Antifoam emulsion 0.05 2% Aqueous NaCl 35.95 100.00 Appearance concentrate C Appearance dilution 1 Example 10 - Variation of the cation of dodecylbenzenesulfonic acid. 10% Aqueous dodecylbenzene sulfonic acid was neutralized with potassium hydroxide, ammonium hydroxide, dimethyl amine and diethanol amine. The following formulation was prepared with each of the 4 DBSA solutions. n -Octyl isothiazolone (45% in propylene glycol) 28.0 10% DBSA salt solution 16.0 Butoxyethanol 4.0 HOEO₂₁PO₆₇EO₂₁OH 8.0 Water 44.0 100.0 Conclusion All of the above DBSA salts are effective in forming microemulsions. Dimethyl amine is least effective of these four. Example 11 - Latex paints containing isothiazolone microemulsion. Dried exterior latex paint films are susceptible to disfiguring mildew growth. To prevent this an isothiazolone microemulsion is added to the paint. A typical exterior latex paint would contain: parts by wt. Natrosol 250 MHR 3.0 Ethylene glycol 25.0 Water 120.0 Tamol® 960 7.1 Potassium tripolyphosphate 1.5 Triton® CF-10 2.5 Colloid 643 1.0 Propylene glycol 34.0 Ti-Pure R902 (titaniumdioxide) 225.0 Zinc oxide 25.0 Minex 4 147.3 Icecap K 50.0 Attagel 50 5.0 The above materials are ground for 10-15 minutes on Cowles Dissolver at 3800-4500 rpm. The speed is reduced and the following is added: Rhoplex® AC 64 305.9 Colloid 643 3.0 Texanol 9.3 Microemulsion Example 5C 7.2 Water 84.8 2.5% Natrosol 250 MHR 118.2 1176.8 A 1176.8 batch represents 100 gallons of paint. The inclusion of the isothiazolone will prevent mildew growth on the paint film under conditions where a paint with no biocide will support mildew growth. Example 12 - Use of Isothiazolone Microemulsion in a water cooling tower. Evaporative cooling is widely used for dissipation of heat. This is accomplished with a cooling tower in which a large surface area is exposed by running water down a series of slats. Air is moved over the water surface by fans resulting in evaporation. The cooled water is the heat exchange medium. Fungal growth can occur in the water and on the tower surfaces. This growth can cause several operational problems such as fouling, plugging and wood rot, generally leading to loss of cooling efficiency and biodeterioration of the cooling tower itself. To control fungal growth 5-10 ppm active ingredient of the isothiazolone microemulsion prepared in Example 5G can be added directly to the bulk water in the cooling tower weekly. Example 13 - Using Isothiazolone Microemulsions to prevent fungal growth in metal working fluids. In the machining of metal parts a metal working fluid is used. This fluid serves to cool, lubricate, and prevent corrosion on the surface being worked. The fluid itself is prepared by adding a metal working concentrate to water. Three gallons Cimcool 5 star 40, a concentrate, is added to 100 gallons of water. This is stored in a sump and pumped to the various machining operations. Spent fluid is returned to the sump for reuse. Over time this fluid can become contaminated with mircoorganism and support fungal growth. This fungal growth can interfere with normal operation by clogging filters in these systems. Addition of 25-50 ppm active ingredient of the isothiazolone microemulsion prepared in Example 4F will control fungal growth. Example 14 - Use of Isothiazolone Microemulsion as an antisapstain control on wood. When green lumber is stored in a wet or humid condition, various surface fungal growth can occur which discolors the surface, lowering the value of the lumber. To eliminate this growth an isothiazolone microemulsion is applied to the lumber surface. An aqueous dilution of the microemulsion prepared in Example 4B is prepared at 350 to 1000 ppm of isothiazolone active ingredient. Freshly sawn timber is dipped in the solution for 30 seconds. The lumber is withdrawn from the solution and allowed to dry. The residual isothiazolone on the wood surface prevents staining due to fungal growth. Example 15 - Use of Isothiazolone Microemulsion as a laundry mildewcide. A laboratory test was done using the microemulsion defined in Example 5C to determine its effectiveness as a laundry mildewcide. Pieces of fabric were washed in a commercial washing machine and treated with the composition of 5C diluted to the proper concentration in water. The fabric is exposed to the biocide for a 3 minute "rinse cycle". The fabric is air dried overnight then sprayed with Sabround Detrose Broth, a nitrogen source for the fungus ( A.niger ). After air drying the fabric is sprayed with a spore suspension of A.Niger in a 50 ppm solution of surfactant (octyl phenoxy polyethoxy (8) ethanol). Each piece of fabric is hung on a hook in a chamber in which the relative humidity is maintained at 94% and the temperature at 30°C. After 4 weeks storage the fabric is evaluated for percent fungal coverage. Growth of A.niger on 100% cotton fabric treated with Isothiazolone Microemulsion 5C. Concentration of Active Ingredient in Fabric Treatment Solution Percent Growth of A.Niger on 100% Cotton Fabric (ppm) Test 1 Test 2 10 20 10 20 20 20 30 20 90 40 NG T 50 NG NG untreated control 100 100 This mildewcide treatment controlled the fungal growth at 40 ppm active ingredient or above. In another aspect the invention comprises a mechanical process for improving the commercial value effectiveness and/or profitability of compositions or liquid loci which are, or may be, subject to contamination by bacteria fungi or algae which comprises (1) charging to a container, dosing or other dissemination device a dilution-stable microemulsion comprising isothiazolone of low water solubility, anionic surfactant, cosurfactant and water, wherein the microemulsion contains polyoxyethylene/polyoxypropylene block copolymer of the formula: wherein R³ is (C₁-C₆)alkoxy or a radical of the formula where m¹ is an integer greater than 15 and n¹ is an integer greater than 10; (2) using the container, dosing or other dissemination device to apply the microemulsion to the locus or composition; (3) controlling the dose of isothiazolone during this application step so that the dosage of active ingredient is sufficient to combat the bacteria, fungus or algae but insufficient to cause any adverse effect on the composition or locus or any thing or person with which or may come into contact.

Claims: Claims for the following Contracting States : AT, BE, CH, DE, FR, GB, GR, IT, LI, LU, NL, SE A dilution-stable microemulsion comprising isothiazolone of low water solubility, anionic surfactant, cosurfactant and water, characterised in that the microemulsion contains polyoxyethylene/polyoxypropylene block copolymer of the formula: wherein R³ is (C₁-C₆)alkoxy or a radical of the formula where m¹ is an integer greater than 15 and n¹ is an integer greater than 10; A microemulsion comprising components in the folowing ratios: (A) from 0.1-50 parts by weight of isothiazolone, having a water solubility of less than 1% by weight, of the formula: wherein Y is an unsubstituted alkyl group of 2 to 18 carbon atoms, a substituted alkyl group of 2 to 18 carbon atoms having at least one hydrogen atom replaced by an hydroxy, halo, cyano, alkylamino, dialkylamino, phenylamino, halophenylamino, carboxy, carbalkoxy, alkoxy, aryloxy, morpholino, piperidino, pyrrolidonyl, carbamoxy, or isothiazolonyl group, wherein the total number of carbon atoms in the substituted alkyl group does not exceed 18, an unsubstituted or halo-substituted alkenyl group of 4 to 18 carbon atoms, an unsubstituted or halo-substituted alkynyl group of 4 to 18 carbon atoms, an unsubstituted or alkyl-substituted cycloalkyl group having a four to six carbon atom ring and up to 12 carbon atoms, an unsubstituted or a halo-, (C₁-C₆)alkyl-, or (C₁-C₆)alkoxy-substituted aralkyl group wherein the total number of carbon atoms in the aralkyl group does not exceed 10; or an unsubstituted or a halo, nitro-, (C₁-C₆)alkyl-, or (C₁-C₆)carbalkoxy-, substituted aryl group wherein the total number of carbon atoms in the aryl group does not exceed 10; and R and R¹ are the same or different substituent selected from hydrogen, halogen, or a (C₁-C₄)alkyl group; and (B) from 0.1 to 25 parts by weight of anionic surfactant; (C) from 0.1 to 25 parts by weight of cosurfactant selected from alkyl alcohols and alkylalkoxylated alcohols; (D) from 0.5 to 50 parts by weight of polyoxyethylene/polyoxypropylene block copolymer of the formula: wherein R³ is (C₁-C₆)alkoxy or a radical of the formula where m¹ is an integer greater than 15 and n¹ is an integer greater than 10; (E) from 10 to 99 parts by weight of water; and (F) from 0 to 30 parts by weight of adjuvant; with the proviso that the total parts by weight of components A to F is 100. The microemulsion of Claim 2 comprising from 1 to 30 parts by weight of the isothiazolone; from 1 to 15 parts by weight of the anionic surfactant; from 1 to 20 parts by weight of the cosurfactant; from 1 to 40 parts by weight of the polyoxyethylene/polyoxypropylene copolymer; from 20 to 98 parts by weight of water and from 0 to 20 parts by weight of adjuvant per 100 parts by weight of the six specified components. The microemulsion of Claim 2 comprising from 1 to 12.5 parts by weight of the isothiazolone; from 1 to 4 parts by weight of the anionic surfactant, from 1 to 6 parts by weight of the cosurfactant; from 1 to 10 parts by weight of the copolymer; from 50 to 90 parts by weight water and from 0 to 16 parts by weight of adjuvant per total of 100 parts by weight of the six specified components. A microemulsion of any preceding claim wherein the anionic surfactant comprises an alkylaryl sulfonate salt, alkyl (C₈-C₂₀) sulfate salt; (C₁₀-C₂₀) fatty alcohol ethoxylate sulfate salt, mono- or dialkyl (C₄-C₁₃) sulfosuccinate salt and/or sulfated oil. A microemulsion of any preceding claim wherein the cosurfactant is a (C₄ to C₁₀)alkyl alcohol or an alkylalkoxylated alcohol of the formula CH₃(CH₂) n (OC₂H₄) m OH or CH₃(CH₂) n (OC₃H₆) m OH wherein n is O or an integer of 1 to 7 and m is an integer of 1 to 4. A microemulsion of any preceding claim wherein the polyoxyethylene/polyoxypropylene copolymer has a weight average molecular weight above 1750. A microemulsion of Claim 7 wherein the polyoxyethylene/polyoxypropylene copolymer has a weight average molecular weight above 3000. A microemulsion of any preceding claim wherein the isothiazolone comprises n -octyl-4-isothiazolin-3-one and/or n -octyl-4,5-dichloroisothiazolone. A method for preparing a microemulsion of any preceding claim which comprises admixing the specified components in the specified quantities. A method for inhibiting the growth of bacteria, fungi, or algae in a locus subject to contamination by bacteria, fungi, or algae, which comprises incorporating onto or into the locus an effective amount of a microemulsion of any of Claims 1 to 10. A method of Claim 11 wherein the locus is a cutting oil formulation, a water-cooling system, a solid protective or decorative film, a fabric, leather, paper, or wood, a laundry wash water, a cosmetic formulation, a fuel system, a plastics material, an emulsion, or any aqueous medium other than as specified elsewhere in this claim. The use of one or more polyoxyethylene/polyoxypropylene block copolymers of the formula where R³ is (C₁-C₆)alkoxy or a radical of the formula where m¹ is an integer greater than 15 and n¹ is an integer greater than 10, together with anionic surfactant, alkyl alcohol and/or alkylalkoxylated alcohol cosurfactant and water to form a stable microemulsion of isothiazolone of low water solubility. Claims for the following Contracting State : ES The use of one or more polyoxyethylene/polyoxypropylene block copolymers of the formula where R³ is (C₁-C₆)alkoxy or a radical of the formula where m¹ is an integer greater than 15 and n¹ is an integer greater than 10, together with anionic surfactant, alkyl alcohol and/or alkylalkoxylated alcohol cosurfactant and water to form a stable microemulsion of isothiazolone of low water solubility. A mechanical process for improving the commercial value effectiveness and/or profitability of compositions or liquid loci which are, or may be, subject to contamination by bacteria, fungi or algae which comprises (1) charging to a container, dosing or other dissemination device a dilution-stable microemulsion comprising isothiazolone of low water solubility, anionic surfactant, cosurfactant and water, wherein the microemulsion contains polyoxyethylene/polyoxypropylene block copolymer of the formula: wherein R³ is (C₁-C₆)alkoxy or a radical of the formula where m¹ is an integer greater than 15 and n¹ is an integer greater than 10; (2) using the container, dosing or other dissemination device to apply the microemulsion to the locus or composition; (3) controlling the dose of isothiazolone during this application step so that the dosage of active ingredient is sufficient to combat the bacteria, fungus or algae but insufficient to cause any adverse effect on the composition or locus or any thing or person with which it may come into contact. The use or process of Claim 1 or 2, wherein the microemulsion comprises components in the folowing ratios: (A) from 0.1-50 parts by weight of isothiazolone, having a water solubility of less than 1% by weight, of the formula: wherein Y is an unsubstituted alkyl group of 2 to 18 carbon atoms, a substituted alkyl group of 2 to 18 carbon atoms having at least one hydrogen atom replaced by an hydroxy, halo, cyano, alkylamino, dialkylamino, phenylamino, halophenylamino, carboxy, carbalkoxy, alkoxy, aryloxy, morpholino, piperidino, pyrrolidonyl, carbamoxy, or isothiazolonyl group, wherein the total number of carbon atoms in the substituted alkyl group does not exceed 18, an unsubstituted or halo-substituted alkenyl group of 4 to 18 carbon atoms, an unsubstituted or halo-substituted alkynyl group of 4 to 18 carbon atoms, an unsubstituted or alkyl-substituted cycloalkyl group having a four to six carbon atom ring and up to 12 carbon atoms, an unsubstituted or a halo-, (C₁-C₆)alkyl-, or (C₁-C₆)alkoxy-substituted aralkyl group wherein the total number of carbon atoms in the aralkyl group does not exceed 10; or an unsubstituted or a halo, nitro-, (C₁-C₆)alkyl-, or (C₁-C₆)carbalkoxy-, substituted aryl group wherein the total number of carbon atoms in the aryl group does not exceed 10; and R and R¹ are the same or different substituent selected from hydrogen, halogen, or a (C₁-C₄)alkyl group; and (B) from 0.1 to 25 parts by weight of anionic surfactant; (C) from 0.1 to 25 parts by weight of cosurfactant selected from alkyl alcohols and alkylalkoxylated alcohols; (D) from 0.5 to 50 parts by weight of polyoxyethylene/polyoxypropylene block copolymer of the formula: wherein R³ is (C₁-C₆)alkoxy or a radical of the formula where m¹ is an integer greater than 15 and n¹ is an integer greater than 10; (E) from 10 to 99 parts by weight of water; and (F) from 0 to 30 parts by weight of adjuvant; with the proviso that the total parts by weight of components A to F is 100. A use or process according to Claim 3, wherein the mircoremulsion comprises from 1 to 30 parts by weight of the isothiazolone; from 1 to 15 parts by weight of the anionic surfactant; from 1 to 20 parts by weight of the cosurfactant; from 1 to 40 parts by weight of the polyoxyethylene/polyoxypropylene copolymer; from 20 to 98 parts by weight of water and from 0 to 20 parts by weight of adjuvant per 100 parts by weight of the six specified components. A use or process according to Claim 3, wherein the microemulsion comprises from 1 to 12.5 parts by weight of the isothiazolone; from 1 to 4 parts by weight of the anionic surfactant, from 1 to 6 parts by weight of the cosurfactant; from 1 to 10 parts by weight of the copolymer; from 50 to 90 parts by weight water and from 0 to 16 parts by weight of adjuvant per total of 100 parts by weight of the six specified components. A use or process of any preceding claim, wherein the anionic surfactant comprises an alkylaryl sulfonate salt, alkyl (C₈-C₂₀) sulfate salt; (C₁₀-C₂₀) fatty alcohol ethoxylate sulfate salt, mono- or dialkyl (C₄-C₁₃) sulfosuccinate salt and/or sulfated oil. A use or process of any preceding claim, wherein the cosurfactant is a (C₄ to C₁₀)alkyl alcohol or an alkylalkoxylated alcohol of the formula CH₃(CH₂) n (OC₂H₄) m OH or CH₃(CH₂) n (OC₃H₆) m OH wherein n is O or an integer of 1 to 7 and m is an integer of 1 to 4. A use or process of any preceding claim, wherein the polyoxyethylene/polyoxypropylene copolymer has a weight average molecular weight above 1750. A use or process of Claim 8, wherein the polyoxyethylene/polyoxypropylene copolymer has a weight average molecular weight above 3000. A use or process of any preceding claim, wherein the isothiazolone comprises n -octyl-4-isothiazolin-3-one and/or n -octyl-4,5-dichloroisothiazolone. A method for preparing a microemulsion as described in any preceding claim, which comprises admixing the specified components in the specified quantities. A use or process of any preceding claim, wherein the locus is a cutting oil formulation, a water-cooling system, a solid protective or decorative film, a fabric, leather, paper, or wood, a laundry wash water, a cosmetic formulation, a fuel system, a plastics material, an emulsion, or any aqueous medium other than as specified elsewhere in this claim.

Inventors: MATTOX JOHN ROBERT, MATTOX, JOHN ROBERT
Applicants: ROHM & HAAS, ROHM AND HAAS COMPANY
Application year: 1988
Main classification: A01N25
IPC codes: A01N47, B01F17, A01N43, A01N25