CA1158157A - Antimicrobial compositions - Google Patents

Abstract

Abstract of the Disclosure This invention relates to antimicrobial compositions comprising a combination of (1) a multi-substituted aryl compound wherein one or more of the substituents is oleophilic (such as an alkyl group with a chain length of C4 to C24) and the other is hydrophilic (such as a sulfo group); (2) a metal-oxine; (3) a metal salt of a hydroxy arene carboxylic acid; and where required, (4) a solvent to convert the composition into a readily handleable liquid for dilution and application. In some instances, as described herein, an hydroxyl group may be substituted for the sulfo group in the multi-sub-stituted aryl compound.

Description

11581~7 The present invention relates to an antimicrobial and pesticidal composition which includes ~a) a multi-substituted aryl compound wherein one substituent is oleophilic and another substituent is hydrophilic, (b) a metal complex of oxine, and ~c) a metal salt of a hydroxy substituted arene carboxylic acid, wherein the weight ratio of oxine to hydroxy substituted arene carboxylic acid is within the range of 1:4 to 9:1, and wherein the weight ratio of (a) to (b) plus ~c) is between 4:1 and 70:1.
This invention also relates to a method for controlling the growth of microorganisms which comprises applying to the locus of said organisms an antimicrobially effective amount of a composition that comprises ~a) a multi-substituted aryl compound wherein one substituent is oleophilic and an-other substituent is hydrophilic, ~b) a metal complex of oxine, and (c) a metal salt of a hydroxy substituted arene carboxylic acid, wherein the weight ratio of oxine to hydroxy substituted arene carboxylic acid is within the range of 1:4 to 9:1, and wherein the weight ratio of (a) to (b) plus (c) is between 4:1 and 70:1.
The antimicrobial compositions of this invention differ from those disclosed in South African Patent 76-6268 of West et al issued on August 1977 in the substitution of component (3) above for varying and replacing substan-tial portions of component (2) above. It is found that such replacementyields totally ~mexpected advantages over the previously described compositions, including:
1. High antimicrobial efficacy -- the high, broad spectrum efficacy noted in the aforesaid compositions are retained generally in the compositions of the present invention. In many instances performance is equal; in others an actual improvement is noted; in still other cases, efficacy loss is minor or unexpectedly low. This unanticipated discovery is contrary to accepted "~
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state-of-the-art theory as reco~nized by those skilled in the art since the aforementioned hydroxy arene carboxylic acids, and metal salts thereof, pro-vide a very low order of efficacy compared to that of the metal oxines pre-pared with the same metal.

2. Cost eff cacy -- the metal salts of the arene acids generally are much less expensive than the metal oxines produced with the same metal, and this is especially so with the preferred arene acid -- salicylic acid. Since the hydroxy arene acid modified compositions of the present invention exhibit the same general order-of-magnitude of antimicrobial efficacy, the all-important cost-performance of present invention compositions is considerably improved over that of the aforesaid compositions. The improvement in cost-efficacy afforded by this invention will vary depending upon the antimicrobial plus handling and use requirements for any given application. For example, for a particular end use, the optimum replacement of oxine for hydroxy arene acid, antimicrobially, may be ~0%, while for another, it may be 40%. For one application, maintenance of low viscosity of the composition in liquid con-centrate form at low temperatures may be essential, in which case the fact that lower cost solvents may be used for composition concentrates of this invention compared to those of the aforesaid compositions is a significant monetary advantage, as discussed below. The composition concentrates of this invention generally allow higher active ingredient contents than the aforesaid compositions, and, consequently lower manufacturing, container and shipping costs, all of which involve an energy saving.

3. Lower cost, improved handling concentrate solvent systems -- the preferred embodiment of the invention generally involves preparation of thé
compositions in as high a concentTation of active ingredients as possible, consistent with other practical requirements, which vary from one end use to L 1581~7 the next, including sufficiently low viscosity (generally below 2000 cps at 70F) to allow rapid formation of the homogeneous solution when the concen-trate is use-diluted, usually with water, for application; retention of con-centrate viscosity at 40F below about 1000 cps allows for metering via an automatic proportioning pump with the required amount of water for use at low operating temperatures.
Generally the compositions of the present invention allow higher active ingredient content concentrates that meet the foregoing requirements and with lower cost solvent systems than do the compositions of the previous-ly disclosed compositions. This is particularly true of the preferred hydroxyarene carboxylic acid -- salicylic acid.
The reason why metal hydroxy arene carboxylic acids can be substitut-ed, as adjuvants, for metal oxine in substantial and widely varying amounts in the aforesaid compositions is not known with certainty. It is conjectured that such hydroxy acids improve the solubility of the metal oxine in the liquid carrier by reducing the micelle size, thereby gaining more intimate contact between the composition of the invention and the target organism. One of the more inexplicable facets of the invention is the fact that, as illus-trated in many of the examples to follow, antimicrobial efficacy remains essentially constant while the active ingredient content -- metal oxine -- is progressively reduced over a broad range. I am not aware of any conventional theory that offers a completely satisfactory explanation, especially in view of invention operability over such a broad range of antimicrobial content.
The multi-substituted aryl compound functions predominantly as a solubilizing agent for the metal complex of oxine. The multi-substituted aryl compounds are preferably benzene compounds although naphthalene compounds may be used. Although the aryl compound may contain substituents other than the oleophilic and hydrophilic ones ~e.g. it may be substituted with -N02, -CN or -CH0 groups), it is preferred that the aryl group is substituted with only one oleophilic and one hydrophilic group. The most effective and the most easily accessible hydrophilic groups are the sulfo and the hydroxyl groups.
The oleophilic substituent of the aryl compound is suitably a straight or branched aliphatic hydrocarbon group having from about 6 to about 24 carbon atoms. The ~leophilic group may contain substituents which do not substantially decrease its oleophilic character, such as chlorine, but is preferably unsubstituted and is preferably an essentially straight alkyl or alkenyl group. Most preferred are alkyl and alkenyl groups having 6 to 18 carbon atoms, and among them especially the alkyl groups. Preferably the oleophilic substituent is present in para position to the hydrophilic sub-stituent.
In the practice of the invention, the preferred multi-substituted aryl compounds are alkyl benzene sulfonic acids with an alkyl side chain group(s) of C10, C12, or C13, commonly known as decyl-, dodecyl- and tridecyl benzene sulfonic acid respectively; and alkyl phenols with an alkyl side chain group(s) of C8, Cg, C10, and C12, commonly known as octyl-, nonyl-, decyl-and dodecyl phenol respectively. A primary reason for these preferences iscost. These compounds, all intermediates in the manufacture of detergents and surfactants, are readily availabe in large quantity at low cost compared to other multi-substituted aryl compounds suitable for the practice of this invention. Especially suitable is dodecylbenzene sulphonic acid.
Further in the practice of this invention, an anomaly should be noted in regard to use of the multi-substituted aryl compounds described above.
The use of the common names for these compounds involves a misnomer. These compounds are mixtures wherein alkyl side groups vary in carbon chain length, in number and in position on the aryl ring structure. In the parlance employed for these compounds in the major industry of use, detergents, the term, for example, dodecylbenzene sulfonic acid actually means that the total number of carbons on the total number of alkyl side chains on the aryl ring structure averages twelve, or close thereto -- such as 11.9 or 12.2.
The metal-oxine functions as an antimicrobial component. Oxine is also referred to as 8-hydroxyquinoline or 8-quinolinol. The oxine may be substituted with one or two halogens, preferably chlorine, or with other groups. The oxine is, however, preferably unsubstituted. The metal may be any of the following: mercury, copper, cadmium, nickel, lead, cobalt, zinc, iron, calcium, aluminum and tin. Copper usually is preferred because of its desirable combination of broad spectrum, high activity against target orga-nisms; minimal safety and environmental hazard; and low cost. The metal suitably is present in amounts from about 20% to about 500% of the amount stoichiometrically required to form the full chelate with the oxine; in most instances, however 100% is preferred.
In the practice of the invention, the usually preferred hydroxy arene carboxylic acid is salicylic acid, for reasons of economy; 3-hydroxy-2-naphthoic acid and 1-hydroxy-2-naphthoic acid also perform satisfactorily but at higher cost than salicylic acid; other hydroxy arene carboxylic acids include mono or polycylic compounds, the latter including fused or bridged rings, and substituents other than hydroxyl and carboxylic groups may be present on the ring(s), such as halogens; multiple hydroxyl and carboxylic groups may be present, such as methylene disalicylic acid; meta-hydroxy benzoic acid and para-hydroxy benzoic acid.
In the practice of this invention, copper generally is the preferred :
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chelating metal for the oxine, and also for preparing the salt of the hydroxy arene carboxylic acid, in that it usually provides the optimum balance of desired properties including cost-efficacy, mammallian and phytotoxicity, color and handling properties. Other of the aforesaid metals may be employed, however. Usually only a single metal is employed, but two or more generally are feasible in any proportions, so that the composition of this invention may include a mixture of two or more metal oxine chelates and more than one metal salt of the hydroxy arene carboxylic acid.
For economic reasons the metal oxine and metal salt of said hydroxy acid usually are prepared in situ in the compositions of the invention, although the prepared oxine chelate and metal salt of said hydroxy acid may be used. The source of the desired metals may be a wide range of compounds of such metals which (1) allow reaction to take place and (2) produce a by-product which does not yield undesirable side effects in the use of the composition.
For example, copper sulfate produces sulfuric acid as the by-product and therefore generally is not desirable; copper hydroxide produces water which usually is satisfactory; copper naphthenate yields napthenic acids which are satisfactory in certain instances. In some cases, the desired metal itself may be used for the in situ reaction but generally the reaction rate is too slow to be practical and reaction conditions are severe.
Normally, for most uses, a stoichiometric ratio or small excess of metal to oxine plus hydroxy arene carboxylic acid is preferred. It also is practical to prepare compositions wherein a less than stoichiometric amount of metal is smployed for the total of the oxine plus hydroxy acid in the compo-sition, but a less than stoichiometric amount of metal for the oxine alone rarely is desirable. In certain instances, a stoichiometric excess of metal in the composition is preferred, for special antimicrobial purposes, especial-1 1S81~7 ly i in a form that is soluble in the carrier.
As indicated earlier, in my compositions part of the oxine in theaoresaid known composition can be considered as being replaced by a hydroxy arene carboxylic acid and the weight ratio o oxine to acid is suitably with-in the range of 1:4 to 9:1 and preferably within the range 1:3 to 3:1. This replacement permits substantial reductions in the oxine component while re-taining high antimicrobial (antibacterial, antifungal, antiviral and antipro-tozoan) and insecticidal activity; it is ound that up to about 90% replace-ment of metal oxine with metal hydroxy acid salt yields from equal or better to substantial retention of properties of the previously disclosed compositions without the metal hydroxy acid salt. The degree of substitution of metal hydroxy acid salt for metal oxine will vary with the detailed efficacy and auxiliary requirements of the intended type of end use. In general, the optimum degree of substitution ranges from 10 to 80%, preferably 20 - 75% in terms of cost-efficacy, ease of use-dilution with water or other solvent carrier, concentrate activè ingredient content, concentrate viscosity at low temperature, resistance to removal of active ingredient from the applied substrate by water leaching and the like.
In my compositions there should generally be a weight excess of the multi-substituted aryl compound with respect to the metal-oxine-hydroxy acid component and suitably of at least 4 parts per part of the latter.
Preferably 4 to 70 parts by weight of the multi-substituted aryl compound is included for each part of the metal-oxine-hydroxy acid component. The actual maximum ratio, usually desired for economic reasons, will change with a number of variables including the solvent system, the ratio of metal oxine to metal hydroxy acid, the shelf stability of the concentrated composition, the degree of use dilution with water, organic solvents, or mixtures thereof 11581~7 and the impurities in the water (including hardness).
The compositions of the invention generally are prepared as liquid concentrates for subsequent dilution at the site of use with a suitable carrier, which usually is water for most end uses, but also may be an organic solvent for some applications. Suitable organic solvents for the sulfonic acid type compositions include a substantial variety of both polar and non-polar compounds; including, in the former category, methanol, ethanol, iso-propanol, ethylene glycol, propylene glycol, n-butanol, a number of glycol ethers, ketones, dimethylformamide, N-methyl-2-pyrrolidone and combinations of water with water-soluble organic solvents; in the latter category are included a variety of aliphatic or aromatic hydrocarbons such as mineral spirits, kerosene, fuel oil, diesel fuel and xylol. Liquid ethoxylated alkyl phenols may also be used as solvents or reaction media. A metal in the form of a hydrate or a salt such as acetate, can be mixed with the sol-vent and the multi-substituted aryl compound and then the oxine and the hydroxy acid added in the dèsired quantites. It is often suitable to use about 20% by weight or more of a solvent based on the total weight of the composition. Concentrates preferably contain from 2 to 10 parts by weight of metal-oxine-hydroxy acid component, 25 to 83 parts by weight of disubstituted aryl compound and 15 to 38 parts by weight of water or a polar solvent.
It is within the scope of this invention to incorporate a broad range of additives in both large and small amounts in the compositions, both in concentrate and ready-to-use form to meet a variety of secondary require-ments for a wide range of end uses, including coloring agents (pigments and dyes), defoamers, anionic, non-ionic and amphoteric detergents; odorants, emollients, slip agents, dry carriers, gellants, resins and polymers, other antimicrobials, insecticides, fire retardants and the like to produce granules, liquids and ointments. A number of insecticides, normally suspensions in a water carrier, form true solutions when incorporated in suitable amount.
Those skilled in the art can readily determine the suitability or lack there-of of any such additive for the desired purpose in terms of compatability, efficacy and desired auxiliary characteristics.
The compositions of the invention exhibit utility in a broad range of different end uses, including preservation of materials subject to biological degradation including wood, leather, paints, paper, wool, cotton and stone;
control of microbial growth on wood, metals, glass, ceramics, plastics, con-crete and other environmental surfaces; control of fungal and bacterialpathogens via topical application to human, animal and plant life; slime (fungal and bacterial) control in water; foodstuff and animal feed preserva-tion; insect control.
The compositions of this invention are especially useful in protect-ing wood and wood-based materials which are susceptible to attack by wood destroying fungi. Pine, spruce and birch in the form of poles, piles and beams and all kinds of wood and timber for constructional purposes and wood based materials such as plywood and chipboard can for example be protected by treatment with the wood preservatives. In the treatment, effective amounts of the compositions are applied by conventional methods such as dipping, impregnation, spraying and coating. The treatment gives a good effect against attack of and growth of wood destroying fungi such as mould, rot, and fungi causing stains.
The compositions of a disubstituted aryl compound and metal-oxine-hydroxy acid component can form part of formulations with solvents and/or diluents known per se and other additives such as binders for improving their retention to the wood material as well as water-repelling agents. The 1~581~7 formulation may further contain other fungicides~ In formulations for thc treatment of wood and wood based materials the amount of aryl compound and metal-oxine-hydroxy acid component is suitably from 0.1 to 10 percent by weight The concentration is, however, not critical but is adapted with respect to the desired protection and the kind of wood.
Concentrates of the compositions in solvents are usually diluted prior to use. Preferably water is used for the dilution although other diluents such as aliphatic and aromatic solvents can be used if desired. It is an advantage of the present compositions that they can be diluted with water to very low concentrations of active ingredients without precipitation of active ingredients. Those skilled in the art can readily determine the concentration for a given end use, wherein use dilution of the concentrate will vary from zero (the concentrate itself may be applied to a substrate) to 1:200,000 (for control of bacterial count in water). The commonly employed range of use dilutions, however, is about 1:600 to 1:10.
In summary then, an important aspect of this invention is that relatively expensive oxine is in effect replaced by relatively inexpensive hydroxy substituted arene carboxylic acid. Also, the use of hydroxy acids allows higher concentrations of the compositions to be prepared in lower cost solvents. Another positive effect of such substitution is that when my compositions are made into formulations by dilution with water, the degree of dilution with water can be increased without the precipitation of the active ingredients (as compared with the case where no hydroxy acids are used).
This is advantageous in those uses where high dilutions are desirable and also as it makes it possible to avoid over-dosage, which is always desirable rom an environmental point of view, even when dealing with substances that are not toxic.

11~8~ 57 The following, non-limiting examples illustrate the practice and the scope of this invention. The method of preparation, herein described, is employed for all of the following examples; the method is non-limiting in that other types of equipment and other orders of additions of components to the reaction vessel may be employed by those skilled in the art.
Apparatus to prepare compositions of the invention consists of a stainless steel, jacketed, closed reactor equipped with a source of applied heat (steam), a reflux take-off condenser, a charge port for introduction of ingredients, a discharge opening, a means for measuring temperature of the composition and a power driven agitator. The solvent and the alkyl aryl sulfo or hydroxy compound are charged to the reactor first and the agitator is turned on. The compound providing the metal to form the metal oxine and the metal hydroxy acid is added, followed by the oxine and the hydroxy carboxylic acid. The reaction generates an exotherm. The reactants are maintained at 140 F or thereabouts, with outside heat if necessary, for sufficient time for a clear, homogeneous solution to form; generally 30 minutes or less. The composition prior to discharge from the reaction vessel is allowed to cool to a temperature well below that wherein solvent may be easily evaporated from the composition.
In all of the following examples, the quantity of ingredients is expressed in parts by weight.
Examples 1 through 5 .
These compositions were prepared:
Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Oxine 4.1 3.1 2.1 1.0 Salicylic acid - 1.0 2.0 3.1 14.0 Copper hydrate 1.5 1.5 1.5 1.5 5.0 Dodecylbenzene sulfonic acid 64.0 64.0 64.0 64.0 51.0 Methanol 30.4 30.4 30 4 30 4 30.0 l 1~8157 The compositions of the five examples are liquid concentrates which are water diluted for use. Fresh-~cut~ rough sawn, green southern yellow pine board (5 replicates of each) are dip immersed for 10 seconds in each use solution at each indicated use dilution, immediately close stacked, five boards high and covered with plastic film, in a controlled atmosphere chamber at 80 F. and 75% R.H.. At the same time, control boards dipped in water and control boards dip treated with an industry standard anti-fungal were placed in the chamber. After 21 days in this severe exposure environment, the test boards were rated for sapstain and mold growth on the surface of the boards, expressed as a percentage of the total surface area of the five replicate boards.

Use Dilution Fungal Growth Composition _ in Water Sapstain (%)_ Molds(%) Example 1 1:100 1 0 " 1:200 2 Example 2 1:100 1 0 " 1:200 3 Example 3 1:100 0 0 " 1:200 2 2 Example 4 1:100 1 0 " 1:200 3 Example 5 1:100 9 2 " 1:200 14 4 Untreated control -- 90 6 Treated control* 1:50 3 0 1:1~0 4 0 * A concentrate containing 29% sodium tetrachlorophenate active ingredient It is evident from these results that the test method is severe since the water dipped control boards are almost completely covered with sapstain and mold. It also is evident that the oxine-salicylic acid combin-ations are essentially equal to each other and to the oxine-only composition, and to the standard antifungal control despite the fact that the diluted-for-use solutions of the standard antifungal contain a much higher concentration of active ingredient. Lastly, it is evident that the copper salicylate alone ~Example 5) yields antifungal control significantly inferior to Examples 1, 2, 3 and 4 despite an active ingredient content almost four times higher.
Examples 6 and 7 The following compositions were prepared:
Ex 6 Ex.7 Oxine 4.1 2.0 Salicylic acid - 2.1 Tetrachlorophenol 22.0 22.0 Copper hydrate 1.5 1.5 Dodecylbenzene sulfonic acid 47.0 47.0 Methanol 25.4 25.4 These examples illustrate the introduction of an additional anti-microbial, tetrachlorophenol, to a composition of the invention (Example 7) and comparing it by test, below, to a control composition containing metal oxine without the presence of metal hydroxy carboxylic acid (Example 6).

Use Dilution Fungal Growth Composition in Water Sapstain(%_ hbld ~) Example 6 1:150 3 0 " 1:300 9 0 Example 7 1:150 1 0 " 1:300 6 0 ~ ~58157 Use Dilution Fungal Growth Composition in ~Yater Sapstain~%) ~old(%) _ _ ___ Treated control* 1:50 3 0 " * 1:100 6 0 Untreated control -- 92 7 * 29% sodium tetrachlorophenate active ingredient These results indicate that copper salicylate replacement of copper oxine at the 51% level (Example 7) is as least as effective as the composition without copper salicylate (Example 6) in the presence of another antifungal (tetrachlorophenol). It also illustrates the point that the 22% tetrachloro-phenol addition to both compositions adds at least as much as the overall effectiveness, in terms of active ingredient content of the use solutions, as indicated by the 29% sodium tetrachlorophenate in the treated control product.
Note: The compositions of Examples 2, 3, 4 and 7 have a definite wintergreen odor which becomes more pronounced as the percentage of salicylic acid in the compositions increases. Since this odor disappears on a treated substrate, fairly shortly after treatment, it is conjectured that, in solution, methyl salicylate is formed from methanol and salicyclic, but that when the solution is applied and the methanol evaporates, copper salicylate forms.
This oil of wintergreen odor is not formed when a non-alcohol solvent is used in preparing the composition. In the presence of ethanol solvent, a much weaker oil of wintergreen odor results. The wintergreen odor is much more pronounced in Examples 2, 3 and 4 than in Example 7 since the strong odor of tetrachlorophenol in the latter acts as an odor masking agent.
Examples 8 through 11 -Compositions very similar to those of Examples 2, 3 and 4 were prepared and tested by the previous procedure, yielding somewhat different -]4-11~8157 results since fungal inoculation is natural, not artificial, and since the test was conducted at another time with test boards from different trees.
_x. 8 Ex. 9 Ex _ 0 Ex. 11 Oxine 4.1 2.5 1.7 0.8 Salicylic acid - 1.6 2.4 3.3 Copper hydrate 1.5 1.5 1.5 1.5 Dodecylbenzene sulfonic acid 65.0 65.0 65.0 65.0 Propylene glycol methyl ether 29.4 29.4 29.4 29.4 Again the results in terms of percentage of board area covered by sapstain and mold growth are very low and approximately equal, whereas the control (water treated) boards exhibited an average stain plus mold growth of 74% when the compositions were employed at l:lOO and 1:200 use dilutions in water.
In these examples, there was no evidence of an oil of wintergreen odor as no alcohol was present to form a salicyclic acid ester.
Examples 12 and 13 These compositions were prepared:
Ex. 12 Ex. 13 Oxine 2.1 1.2 3-hydroxy-2-naphthoic acid 2.0 2.9 Copper hydrate 1.4 1.4 Dodecylbenzene sulfonic acid 65.0 65.0 Methanol 29.5 29.5 Use diluted and tested as before, at 1:100 and 1:200, both compo-sitions exhibited zero sapstain and mold growth whereas the water treated controls showed an average of 63% fungal coverage after a 15-day test period.
Examples 14 and 15 -- ~ ~

115815 '~

These compositions were prepared:
Ex. 14 Ex. 15 Oxine 1.8 1.8 Meta-hydroxy benzoic acid 2.3 Para-hydroxy benzoic acid - 2.3 Copper hydrate 1.5 1.5 Tridecylbenzene sulfonic acid 60.0 60.0 Propylene glycol 15.4 15.4 Ethanol 19.0 19.0 Tested as before, for two weeks, surface area of test boards covered with sapstain and mold was less than 5% of both compositions compared to 61%
for the water treated controls.
Examples 15 through 20 ~
These compositions were prepared:
Ex. 15 Ex. 16Ex. 17 Ex. 18Ex. 19Ex. 20 Oxine 8.2 6.1 2.1 4.1 6.1 3.0 Salicyclic acid - 2.1 6.1 4.1 l-Hydroxy-2-napthoic acid - - - - 2.1 5.2 Copper hydrate 2.9 2.9 2.9 2.9 2.9 2.9 Dodecylbenzene sulfonic acid 59.059.0 59.0 59.0 59.0 59.0 Propylene glycol 25.0 25.0 25.0 25.0 25.0 25.0 Water 5.0 5.0 5.0 5.0 5.0 5.0 The compositions, employing varying substitutions of salicyclic acid and a different hydroxy naphthoic acid than in Examples 12 and 13, were tested in accordance the American Wood Preservers' Association procedure wherein southern yellow pine sapwood blocks are impregnated to refusal, typically about 40 lbs of liquid per cubic foot of wood, with the test com-11~8157 positions appropriately use diluted with water to yield the desired, and indicated below, retentions of the test compositions as prepared. The impregnated blocks, 5 replicates of each composition at each retention, then were dried to constant weight at a temperature and relative humidity as pre-scribed by the test procedure and placed in contact with the two primary decay fungi employed for wood decay preservative evaluation for a period of three months; after which the test blocks are re-conditioned to constant weight, the loss in weight being directly equal to the amount of decay incurred. IVeight losses below about 2% are considered within experimental error inherent in the test method and are interpreted as zero weight loss attributable to attack on the wood by the decay fungi.
The following results are stated as the average retention and weight loss for the five replicates.
All retentions are expressed as pcf -- lbs per cubic food of wood.
All weight loss values are expressed as a percentage of the original condition-ed-to-constant-weight blocks.
Lenzites trabea (Mad. 617) Poria monticola ~Mad. 698) Retention ~eight Loss RetentionWeight Loss Example 15 0.13 0.38 0.300.49 " 0.23 0.39 0.500.62 Example 16 0.301.88 " 0.500.41 Example 17 0.301.48 " 0.500.44 Example 18 0.13 1.19 0.302.04 " 0.23 0.12 0.500.26 Example 19 0.13 0.05 0.301.30 " 0.23 0.25 0.500.23 Lenzitbs trabea ~Mad~ 617) Poria mon~i ola ~Mad. 698) Ret _ tion Welght Loss _tention Weight Loss Example 20 0.13 1.19 0.30 0 " 0.23 0.12 0.50 0.28 CCA-C* 0.05 (1)51.87 0.05 ~1) 29.12 " 0.10 35.04 0.10 16.88 " 0.15 11.16 0.15 4.94 " 0.20 9.64 0.20 0 " 0.25 5.08 0.25 5.55 " 0.30 1.72 0.30 0.42 Untreated controls - 49.49 - 54.07 * CCA - Type C: a major type of wood preservative in worldwide use for long term resistance to wood decay; a copper-chrome-arsenic composition as defined by the American Wood Preservers' Association specifications.
(1) All retentions expressed on an oxide basis.
All retentions of the test compositions exhibit at or above thresh-old resistance to the test fungus; the term threshold being defined as that retention which just stops all decay.
The results indicate essentially no practical difference between any of the test compositions and, if anything, a slight improvement for some of the hydroxy carboxylic acid containing compositions. The results for all test compositions ~Examples 15 through 20) also exhibit a very high order of efficacy indeedl when measured against CCA-C, the control wood preservative that is recognized worldwide as one of the best, if not the best, of the wood preservatives for long term, up to 50 years or more, ground contact service.
Example~ 21 and 22 The following compositions were prepared:

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, ~,,: --Ex. 21 Ex. 22 __ Oxine 4.1 1.8 Salicylic acid - 2.3 Zinc oxide 1.3 1.3 Decylbenzene sulfonic acid 60.0 60.0 Propylene glycol 28.0 28.0 Water 6.6 6.6 Both compositions were tested as a rice seed treatment; field trials at a number of locations involving both drill and water planting techniques, at seed application rates ranging from 2 to 12 ounces per 100 pounds of seed.
The method of application of the compositions to the seed consisted of adding 800 milliliters of water to the number of ounces of the composition to be placed on 100 pounds of seed. The water diluted solutions were then used to coat the inside walls of a container to which 100 pounds of seed were added and the container revolved for 15 minutes to allow the seed to be coated with the compositions. The seed then was planted and stand counts measured 4 to 6 weeks later and compared to stand counts of untreated control seed. Treated seed results are expressed as percentage increase (or decrease) from control.
Overall results from all test locations for the composition of Example 21 was 1.41% improvement over control per one ounce of test composi-tion whereas the composition of Example 22 was 1.47%. Another zinc based product, Kocide-Zinc SD, was 1.05%.
Examples 23 and 24 The following compositions were prepared:
Ex. 23 Ex. 24 Oxine 8.2 4.3 Salicylic acid - 3.9 Copper hydrate 2.9 2.9 Ex 23 Ex. 24 Dodecylbenzene sulfonic acid 60.0 60.0 Propylene glycol 23.0 23.0 Water 5-9 5-9 Evaluated as in the just preceding two examples as a rice seed treatment, the composition of Example 24, containing a replacement of oxine with salicylic acid, exhibits a 4.96% stand improvement over control per ounce of composition, a substantial improvement over Example 23, produced with B oxine only, which exhibits a 3.84% improvement over control. The widely used agricultural fungicide, Difolatan 4FL, tested under the same conditions, exhibited a value of 3.84% which is equal to that of Example 23 and signifi-cantly below Example 24.
Example 25 This composition was prepared:
Oxine 2.5 Salicylic acid5.6 Copper hydrate2.8 Dodecylbenzene sulfonic acid 60.0 Propylene glycol 24.0 Water 5.1 Rice seed was treated as in preceding Example and drill-planted together with untreated control seed and evaluated for plant emergence rate, with these results:

Application Rate Plant Emergence *
(grams/l _ O grams seed) (%) Test Composition 1.25 61 " 2.50 60 a~K

11581~7 Application Rate Plant Emergence *
(grams/1000 grams seed) (%) Test Ccmposition 3.75 59 " 5.00 62 " 7.50 64 Control (untreated) -- 42 * per 200 seeds planted The results with treated seed exhibit substantial improvement in emer-gence rate over control seed wherein Helminthosporium sp., Curvularia sp. and Fusarium sp. are primary examples of seed-bome fungal pathogens.
Test composition results also compare very favorably with a number of widely kncwn and used fungicides that were evaluated simultaneously over a similar range of application rates:
Plant Emergen oe (%) Triadimenol 50 2-(thiocyancmethylthio) benzothiazole 54 Zinc ion/manganese ethylene bisdithiocarbamate64 Captafol * 55 5-ethoxy-3-trichloromethyl - 1,2,4 thiadiazole 57 Carboxin 51 * Common name for cis-N-[(1,1,2,2,-tetrachloroethyl)thio]-4-cyclohexene-1,2-dicarboxamide ``'I

ll581~7 Example 26 This co~position was prepared:
Ex. 26 Oxine 2.6 Salicylic acid 1.5 Copper hydrate 1.4 Dcdecylbenzene sulfonic acid 60.0 Propylene glycol 27.5 Water 7.0 -21a-I 1581~7 and evaluated for control of the bacterial plant pathogen, Corynebacterium se~ _ icum, the casual organism of potato ring rot disease, via the following procedure.
Dip pieces of wood into a tuber slurry infected with the test bacterium and, within 5 minutes thereafter, spray the infected wood surface with the test composition that is use-diluted with water as shown below.
Then, within 5 minutes, vigorously rub healthy potato seed pieces against the prepared wood surfaces and plant directly in soil in greenhouse pots.
The results are given below and compared with control plantings of seed pieces rubbed against infected wood surfaces not sprayed with the test composition:
% of ring rot % of ring rot Use dilutioninfected plantsinfected tubers 1:19 0 1:99 Control 7 9 In this test, no phytotoxicity was noted in that tuber yield, cal-culated in lbs of tubers per acre, exhibited an 8% increase in yield of the test composition treated seed pieces compared to controls. A subsequent test yielded these results:
% plants infected Use dilution% plant emergencewith ring rot 1:20 94 0 1:100 83 3 Controls 94 29 The test results illustrate the effectiveness of the composition against an economically important Gram-positive bacterium that is pathogenic to potatoes. Corynebacterium sepedonicum is closely related to another Corynebacterium sp. that is the primary causal organism for the skin condition known as teenage acne.

Example 27 This composition was prepared:
Oxine 3-3 Salicylic acid 4,9 Copper hydrate 2.9 Dodecylbenzene sulfonic acid 60.0 Propylene glycol 23.0 Water 5.9 and evaluated against four economically important plant pathogens.
The test procedure consisted of incorporating 0, 1, 10, 100 and 1000 ppm of each test product into autoclaved and cooled Difco * PDA. Four plates per test organism per product concentration were prepared and inoculated with 5 mm diameter my oe lial plugs of three fungi:
Fusarium solani Fusarium oxysporun izoctonia sp.
and, one bacterial pathogen that attacks plant life:
E~wi ~ chrysanthemi whjch is inoculated onto plates by adding 0.1 ml of a 5 x 10 cell/ml suspension.
Diameter of my oe lial grcwth was measured in three directions at 3, 5 and 7 days after inoculation; bacterial colonies were ocunted 4 days after inoculation.
Test results obtained via these pro oe dures indicated very effective de-grees of activity against the tested organisms.
Rhizoctonia sp.

Average Diameter of Grcwth (mm) PPM 3 days 5 days7 days Test Ccmposition 1 HG HG HG
" 10 29 63 HG
* Trade mark for a potato dextrose agar ~15815'7 Average Diametér of Growth ~mm) PPM 3 days 5 days 7 days Test Composition 100 IG IG IG
" 1000 IG IG IG
Control 0 HG HG HG

usarium oxysporum Test Composition 1 31 55 75 " 10 28 50 68 " 100 IG IG IG
" 1000 IG IG IG
Control 0 31 51 70 Fusarium solani _ _ .
Test Composition 1 24 42 --" lO 11 25 40 " .100 IG IG IG
" 1000 IG IG IG
Control 0 26 46 69 Key: HG - Heavy overgrowth -- 85 mm diameter plate covered IG - insignificant growth 20Erwinia chrysanthemi -PPM Total colonies per 4 plates Test Composition 1 457 " 10 0 " 100 0 ~- 1000 Control 0 67 These results illustrate a high order of activity against both 1158~7 fungi and Erwinia sp., a somewhat ill-defined, difficult-to-control, Cram-negative bacterial genus which is pathogenic to a broad variety of plant life.
Examples 28j 29, 30 and 31 The following compositions were prepared:
Ex 28 Ex 29 Ex. 30 Ex. 31 Oxine 4.1 1.8 8.2 3.6 Salicyclic acid - 2.3 - 4.6 Copper hydrate 1.4 1.4 2.9 2.9 Dodecylbenzene sulfonic acid64.0 64.0 58.0 58.0 Propylene glycol 24.5 24.5 24.9 24.9 Water 6.0 6.0 6.0 6.0 The toxicity of these compositions was tested on amended agar plates at concentrations as shown below using 60 mm x 15 mm petri plates, using approximately 7 ml of agar-test composition per plate. Each plate containing a test composition or water control was seeded with a 7-mm agar plug contain-ing mycelium of Verticillium fungicola Preuss, a member of a widespread genus of fungus that is pathogenic to plant life; this fungus strain is sensitive to benomyl.

Test Dilution Colony Diameter~ ) in mm.
in Water Ex. 28 Ex. 29Ex. 30 Ex. 31 Water Control _ ~
__ 53 *

1:103 15 0 14 0 1:104 27 27 21 24 1:105 53 * 53 * 53 * 53 *

~1) - avera~e of three replicates per plate * - colony size had reached plate circumference These data, at the highest use concentration completely effective 1 1581~7 for the compositions of Examples 29 and 31 (the compositions of this invention), somewhere between a use-dilution of 1:1,000 and 1:10,000, are clearly more effective than the compositions of Examples 28 and 30 which do not contain the salicylic acid replacement for oxine. The test was repeated against a benomyl-tolerant isolate of V rticillium fun ola:

Test DilutionColony Diameter in mm.
_ in WaterEx. 28 Ex _ Ex 30 Ex. 31 Water Control __ 39 1:103 14 10 15 10 1:104 26 27 25 23 1:10 38 38 38 39 1:106 39 39 39 38 Again, the compositions of this invention (Examples 29 and 31) proved superior to those of Examples 28 and 30. While none of the compo-sitions provided complete control at the highest tested concentration (1:103), Examples 29 and 31 also were superior to those of the well-known and expen-sive benomyl which at 1:103 use dilution exhibited a 16 mm colony diameter.
The test procedure was repeated against Dactylium dendroides, a pathogenic fungus that attacks edible mushrooms (Agaricus _isp rus):

20Test DilutionColony Diameter in mm.
in Water Ex. 28Ex. 29Ex. 30Ex. 31 Water Control __ 53 1:103 16 11 15 15 1:104 27 28 16 18 1:105 53 53 53 53 In this case, the compositions of this invention (Examples 29 and 31) were essentially equal in efficacy to those of Examples 28 and 30.
The test procedure was repeated against Mycogone pernlciosa Magnus, 11581~7 a mushroon fungal pathogen:

Test Dilution Colony ~iameter-in mm.
in ~ater Ex. 28Ex. 29 Ex. 30Ex. 31 Water Control ____ ._ _ __ __ 53 1:104 18 17 12 0 1:105 53 53 53 53 In this comparative test, the compositions of the invention, Examples 29 and 31, provided the higher efficacy.
Examples 32, 33, 34 and 35 These compositions were prepared:
Ex. 32 Ex 33 Ex. 34 x. 35 Oxine 4.1 1.0 8.2 2.0 Salicylic acid - 3.1 - 6.2 Copper hydrate 1.4 1.4 2.8 2.8 Dodecylbenzene sulfonic acid62.0 62.0 62.0 62.0 Propylene glycol 26.0 26.0 21.0 21.0 Water 6.5 6.5 6.0 6.0 These compositions plus a water control were tested for efficacy against Pseudomonas tolaasii Paine, a Gram-negative bacterium which is the causal organism of mummy disease of mushrooms (Agaricus bisporus). The genus, Pseudomonas, is a difficult-to-control pathogen that affects most plant and animal life causing a wide range of diseases that are much feared human and animal pathogens because of widespread resistance to treatment with antibiotics.
The test procedure consisted of streaking a loopful of the bacterium culture onto the prepared plates containing the test concentrations of the test compositions; after two days of incubation, inspection was made for visible bacterial growth.

ll58157 Use Dilution in Water Ex. 32 Ex. 33 Ex. 34 Ex. 35 Water Control 1:10 + - +
1 104 + + ~ +
(+) -- no growth (-) -- growth (+) -- presence of a few isolated bacterial colonies These results indicate somewhat improved efficacy for the compo-sitions of the invention (Examples 33 and 35) as compared to the compositionsof Examples 32 and 34 which contain no replacement of oxine with an hydroxy carboxylic acid.
These efficacy data indicate a threshold control activity at a use dilution between 1:1,000 and 1:10,000; a high order or performance for an antibacterial chemical agent and especially since Gram-negative organisms in general, and P eudomonas sp. in particular have long been known for tolerance to chemical disinfection agents safe enough for use on mammal and plant tissues.
Examples 36 and 37 The following compositions were prepared:
_Ex. 36 Ex. 37 Oxine 8.2 4.1 Salicylic acid - 4.1 Copper hydrate 2.9 2.9 Dodecylbenzene sulfonic acid 59.0 59.0 Propylene glycol 23.7 23.7 Water 6.2 6.2 These compositions were tested on chrysanthemums against the Gram-negative bacterial pathogen, _seudomonas chichorii (P1617), via the following test procedure:
Ninety plants per composition were used per treatment with two replicates per composition. Spray application to runoff was carried out weekly until 12 days after initial inoculation of the plants with a P.
chichorii suspension~
The plants were inoculated three and four weeks after the initial application of the test compositions with P. hichorii suspension by spraying uniformly over the soil bed. The first suspension, applied after 3 weeks at 8:30 AM with dew on the plants for at least an hour after application, con-tained 2 x 106 bacteria per ml; the second suspension, applied after four weeks at 10:30 PM, contained 5 x 106 bacteria per ml. Suspensions were pre-pared by scraping bacterial growth off the surface of four Kings Media B
plates and mixing with two liters of sterile water.
Disease control was evaluated, on 25 randomly selected leaves for each composition in each replicate, by counting the number of typical disease spots and comparing spot numbers on composition treated versus control leaves.
The efficacy evaluation was made twelve days after initial inocu-lation.

Use Dilution Total Number in Water of Spots % Control Example 36 1:400 248 19 Example 37 1:400 164 47 Control _ 307 The composition of the invention (Example 37) exhibited efficacy superior to the oxine-only composition (Example 36).

Example 38 The following composition was prepared:
Oxine 1.2 Salicylic acid 2.9 Copper hydrate 1.4 Dodecylbenzene sulfonic acid 64.0 Isopropanol 30.5 The composition was evaluated as a bactericide via the AOAC Use-Dilution Confirmation procedure, 10-minute kill, against the three major bacterial mammallian pathogens specified by the Environmental Protection Agency (EPA) for the most stringent use -- hospitals; and against Aerobacter aerogenes, a producer of slime in water systems. The test procedure is that specified in the 12th Edition ~1975) of the "Official Methods of Analysis of the Association of the Official Analytical Chemists".
Staphylococcus aureus Salmonella cholerasuis Number of Tubes Tested Number of Tubes Tested Use Dilution Negative PositiueNegative Positive in Water A B A B A B A B
1:1400 10 10 0 0 10 10 0 0 Psuedomonas aeruginosa ~PRD-10) Aerobacter aerogenes Number of Tubes Tested Number of Tubes Tested Use-Dilution Negative Positive Negative Positive in Water A B A B A B A B
~
1:750 10 10 0 0 10 10 0 0 A = Subculture B - Re-subculture A "Negative" reading indicates a 10-minute kill of the test bac-terium ~as achieved at the stated use-dilution of the test composition; or else regrowth of the bacterium would have occurred in one or more of the -! ~ ' ;
~.

1 1~8157 tubes, yielding one or more "Positive" values. In order to pass this test, all values must be "Negative". Since no "Positive" values resulted, it is probable the threshold use-dilution yielding all "Negative" readings is higher than that tested. But in any event, the results achieved indicate a very high order of efficacy indeed, especially in the case of P. aeruginosa (PRD-10), a notably difficult bacterium to kill with chemical agents.
Example 39 The composition of the preceding Example was tested in accordance with that specified by EPA for kill of fungal growth on environmental (inanimate) surfaces. A 10-minute maximum kill time is required against Aspergillus niger, a black fungus (mold) that is widespread in the world, very difficult to kill and which will grow on a broad range of substrates including even glass over a wide range of climatic conditions. _. niger also can cause an animal and human disease known as aspergillulosis which is difficult to cure and frequently is fatal. A. niger can damage certain sub-strates including some paint films.
The test method is the AOAC Fungicidal Test, 12th Edition (1975).
These results were achieved:
Exposure Time in Minutes Use Dilution 5 _ _ 10 _ _15 in Water A B A B A B
__ _ _ _ _ _ ~
1:250 + + 0 0 0 0 + + O O O O

+ + O O O O

A = Subculture + = Growth B = Re-subculture - = No Growth The results indicate that a kill was achieved in the required 10-minutes but not in 5 minutes. It is probable that a 10-minute kill would `:
11~8157 result at use-dilution higher than the tested 1:250.
The results exhibit a high order of efficacy for any known fungi-cide; particularly for one safe enough for human and animal use as are most of the compositions of this invention.
Example 40 _ The composition of Example 38 was tested in accordance with the AOAC
method employed in Example 39 against Trlchophyton men ro h _ s (ATCC 9533), a causal organism of the skin condition known as "Athletes' Foot", with these results:

Exposure Time in Minutes Use Dilution 5 10 15_ in l~ater A B A B A B
_ 1:700 0 0 0 0 0 0 O O O O O O
O O O O O O
The results indicate a high order of fungicidal efficacy; the results also indicate the probability that even higher use-dilutions will yield the desired kill.
Example 41 The following composition was prepared:
Oxine 1.85 Salicylic acid 1.23 Copper hydrate 1.10 Nonyl phenol 70.00 Petroleum oil ~1~ 25.82 This composition was employed immediately to prepare the following final, ready-to-use formulation, a low viscosity liquid:

Foregoing composition 10 Rosin ester of abietic acid 5 Petroleum oil 83 ~1) a mixture of paraffinic and naphthenic fractions with a boilding range of about 350 F. to 625 F.
This final formulation applied to wood was evaluated as follows:
Stake Test ~ground contact exposure) -- 3/4" x 3/4" x 18" long southern yellow pine sapwood test stakes were soak-treated to 4.0 lb per 10 cubic foot retention and buried to a depth of 9" in a test area in northern Mississippi, an area where untreated wood stakes fail from decay and termite attack in 10-15 months. In four years, the treated stakes (five replicates) remain free of biological attack.
Examples 42 and 43 These compositions were prepared:
Ex. 42 Ex. 43 Oxine 1.8 3.1 Salicylic acid 2.3 5.1 Copper hydrate 1.5 3.0 Dodecylbenzene sulfonic acid 63.0 60.0 Propylene glycol 25.0 22.6 Water 6.4 6.2 These compositions were evaluated in-vitro against three fungi that grow on animal feed causingJ when consumed, both mycoses and mycotoxicoses which, for example, inhibit growth of pcultry; and for example, can contamin-ate the milk of dairy cows that feed on moldy grain or hay, with mycotoxins.
Minimum inhibition concentration ~MIC) was determined for the test ,, ,- :~, , -ll58157 compositions against three fungi that are representative in moldy feed:
As _r _llus flavus (ATCC 168833 -- produces several aflatoxins which have extremely high acute toxicity to mammals. One of the aflatoxins is the most potent liver carcinogen known to man and is found not only in animal feeds but also in a variety of human foodstuffs. In addition, a number of _spergillus sp. are widespread plant pathogens.
Fusarium moniliforme (ATCC 10052) -- a widespread plant pathogen _ _ _ _ _ that is a casual fungus of animal mycoses, and mycotoxicoses in both animals and humans.
Candida albicans (ATCC 10231) -- in addition to adverse effect on _ livestock and poultry, this yeast-like fungus is very widespread and the causal organism of a variety of human pathogenic conditions on skin and mucaus membrane surfaces.
The test procedure was one well-known to those skilled in the art and, very generally, consists of culturing the test organisms on potato dextrose agar, preparing a cell suspension containing approximately 2 x 105 cells per ml, placing 1 ml of which into sterile petri plates and overlayering the plates with the agar containing varying amounts of the test compositions.
After a seven day incubation at 25C., growth of fungi is observed. All experiments were repeated at least three times, in duplicate for each fungus at each test concentration of each test composition. The following results were obtained from all the pooled data, and compared with a number of other, generally low toxicity, antifungals employed for a broad range of foodstuff and animal feed preservation and for general purpose antifungal applications:

Minimum Inh;bition Concentration ~ppm) A_ flavus _. Moniliforme C. Albicans Example 42 5 10 5 " 43 1 5 Acetic acid 5000 5000 5000 Propionic acid 5000 5000 5000 Benzoic acid 500 500 500 Sorbic acid 500 500 500 Sodium benzoate ~5000 ~5000 ~5000 O-Phenyl phenol 50 50 50 Boric acid >5000 ~5000 5000 Sodium EDTA ~5000 '5000 >5000 Copper sulfate 5000 5000 5000 Gentian violet 500 500 5 Both compositions of the invention provide extremely high efficacy indicating usefulness in a broad range of end uses.
Example 44 This composition was prepared:
Oxine 4.10 Salicylic acid 6.15 Copper hydrate 3.70 Dodecylbenzene sulfonic acid 63.00 Methanol 15.05 Isopropanol 8.00 The composition was evaluated in wood for control of subterranean termites ~Reticulitermes flapes) in accordance with the American Wood Preservers' Association ~AWPA) Test Method M12-72, wherein 3/4" cube southern yellow pine sapwood blocks were impregnated with the test composition in a 115815~

water solution at the desired retentions in the blocks (5 replicates at each retention), weighed and exposed to termites for a 30-day period; after which the blocks were reweighed, the loss in weight, over-and-above about 2% not considered attributable to termite attack, being a direct measure of loss of wood from termite ingestion.
The following results were obtained:
Block Retention ( ) Weight Loss (~O) 0.24 5.6 0.41 0.2 (1) lbs per cubic foot of test composition as prepared; average of 5 replicates.
These data indicate that the threshold retention for termite control, point of no attack on the wood, is between 0.24 and 0.41 lbs per cubic foot.
Example 45 This composition was prepared:
Oxine 0.72 Salicylic acid 2.56 Cupric acetate 2.39 Dodecylbenzene sulfonic acid 66.00 Methanol 28.33 Tested as an antiviral agent, an Adenovirus suspension containing 8.4 x 10 pfu per ml was treated by admixture with 0.2% of test composition.
In one hour, readings of zero pfu per ml were obtained.
Tested as an antiprotozoan agent against Tetrahymena, a ciliated protozoan obtained from pond water, the minimum inhibition concentration was found to be 120 ppm of the test composition as prepared.

.

-Example 46 This composition was prepared:
Oxine 2.0 Salicylic acid 3.9 Zinc oxide 1.8 Dodecylbenzene sulfonic acid 62.0 Propylene glycol 20.0 Ethanol 10.3 Formulated at 2% concentration in a petrolatum/water ointment and applied to the armpits of several test subjects, odor development was com-pletely inhibited for a minimum of 48 hours.
Example 47 This composition was prepared:
Oxine 0.8 Salicylic acid 4.1 Zinc oxide 1.8 Dodecylbenzene sulfonic acid 64.0 Nonylphenol ethoxylate* 29.3 * 1 mol nonyl phenol reacted with 9 mols ethylene oxide In this composition a non-ionic detergent was used as the solvent system. At a 1:10 use-dilution in water and employed to wash armpits of three test subjects, after which the cleaned areas was rinsed with water, complete inhibition of underarm odor formation w~s obtained in all test subjects for the 24-hour period of the test.
Examples 48 through 54 -The following compositions were prepared:

l 158157 Example 48~- 49 50 51 52 53 54 Oxine 0.67 2.00 1.50 2,50 Salicylic acid 1.34 2.00 2.50 1.50 2.00 2.20 2.50 Silver acetate 2.02 -- -- -- -- -- --Manganous sulfate monohydrate -- 2.33 -- -- -- -- --Cobaltous sulfate heptahydrate -- -- 3.88 -- -- -- --Mercuric chloride -- -- -- 3.73 -- -- --Nickel oxine -- -- -- -- 2.98 -- --Nickel acetate -- -- -- -- 0.96 -- --Magnesium oxine -- -- -- -- -- 2.00 --Magnesium acetate -- -- -- -- -- 0.85 --Tin oxine -- -- -- -- -- -- 3.26 Stannous sulfate -- -- -- -- -- -- 1.46 Dodecylbenzene sulfonic acid 65.00 62.76 62.72 63.00 65.00 64.00 64.00 Propylene glycol 25.50 25.00 24.4025.0025.00 25.0023.90 Water 5.47 5.91 5.00 4.27 4.10 5.95 4.88 These test compositions were checked for compatibility, stability as prepared in concentrate form, stability when water diluted for use. All proved compatible as prepared (transparent, colored solutions), and when water diluted 1:20 were sufficiently stable for practical use.

Claims (20)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. An antimicrobial and pesticidal composition which includes (a) a multi-substituted aryl compound wherein one substituent is oleo-philic and another substituent is hydrophilic, (b) a metal complex of oxine, and (c) a metal salt of a hydroxy substituted arene carboxylic acid, wherein the weight ratio of oxine to hydroxy substituted arene carboxylic acid is within the range of 1:4 to 9:1, and wherein the weight ratio of (a) to (b) plus (c) is between 4:1 and 70:1.

2. A composition according to Claim 1 wherein component (a) is benzene sulphonic acid substituted with an oleophilic group.

3. A composition according to Claim 2 wherein the oleophilic group is an alkyl or alkenyl group having 6 to 24 carbon atoms.

4. A composition according to Claim 1 wherein component (a) is phenol substituted with an oleophilic group.

5. A composition according to Claim 4 wherein the oleophilic group is an alkyl or alkenyl group having 6 to 24 carbon atoms.

6. A composition according to Claim 1 wherein the hydroxy substituted arene carboxylic acid is salicylic acid.

7. A composition according to Claim 1 wherein the hydroxy substituted arene carboxylic acid is 3-hydroxy-2-naphthoic acid.

8. A composition according to Claim 1 wherein the metal of component (b) and (c) is copper.

9. A composition according to Claim 1 wherein (a) is dodecylbenzene sulfonic acid, (b) is copper-8-quinolinolate and (c) is salicyclic acid.

10. A composition according to Claim 9 which includes 2 to 10 parts by weight of a combination of (b) plus (c), 25 to 83 parts by weight of (a) and 15 to 35 parts by weight of water or a polar solvent.

11. A method for controlling the growth of microorganisms which com-prises applying to the locus of said organisms an antimicrobially effective amount of a composition that comprises (a) a multi-substituted aryl compound wherein one substituent is oleo-philic and another substituent is hydrophilic, (b) a metal complex of oxine, and (c) a metal salt of a hydroxy substituted arene carboxylic acid, wherein the weight ratio of oxine to hydroxy substituted arene carboxylic acid is within the range of 1:4 to 9:1, and wherein the weight ratio of (a) to (b) plus (c) is between 4:1 and 70:1.

12. A method according to Claim 11 wherein component (a) is benzene sulphonic acid substituted with an oleophilic group.

13. A method according to Claim 12 wherein the oleophilic group is an alkyl or alkenyl group having 6 to 24 carbon atoms.

14. A method according to Claim 11 wherein component (a) is phenol substituted with an oleophilic group.

15. A method according to Claim 14 wherein the oleophilic group is an alkyl or alkenyl group having 6 to 24 carbon atoms.

16. A method according to Claim 11 wherein the hydroxy substituted arene carboxylic acid is salicylic acid.

17. A method according to Claim 11 wherein the hydroxy substituted arene carboxylic acid is 3-hydroxy-2-naphthoic acid.

18. A method according to Claim 11 wherein the metal of component (b) and (c) is copper.

19. A method according to Claim 11 wherein (a) is dodecylbenzene sulfonic acid, (b) is copper-8-quinolinolate and (c) is salicylic acid.

20. A method according to Claim 19 which includes 2 to 10 parts by weight of a combination of (b) plus (c), 25 to 83 parts by weight of (a) and 15 to 35 parts by weight of water or a polar solvent.