NO834008L - PLANT GROWTH-STIMULATING MIXTURE - Google Patents

Description

Plant growth stimulators comprising metal ions and long chain alkyl carboxylic acids and their salts and derivatives Related applications

This application is a partial continuation (CIP) of

US Serial No. 403,528 filed July 30, 1982 which again is

a CIP of US Serial No. 354,301 filed March 3, 1982.

Technical area

The present invention relates to chemical mixtures which, when added to growing plant life or seeds thereof, are effective for the growth of said plant life. More particularly, the invention relates to chemical mixtures containing long-chain carboxylic acids and salts and derivatives thereof in combination with metal ions which are useful for stimulating plant growth.

Prior art

In recent years, long-chain carboxylic acids and their derivatives have become known as plant growth-regulating agents, but the practical applicability of these compounds has however been limited to herbicidal agents or chemical agents that otherwise inhibit plant growth.

US Patent No. 3,180,750 to Davidson et al.

describes partially esterified carboxylic acids with at least 2 carbon atoms that exhibit herbicidal activity to

kill or seriously damage plant life. US Patent No. 3,619,165 to Covey et al. outlines the use of alkynyl carboxylates to kill meristem buds, the alkynyl carboxylates having alkyl groups containing 5 to 16 carbon atoms. US Patent No. 3,619,168

to Mecklenborg describes the herbicidal applicability of long-chain acids and esters with chain lengths between 4 and 22 carbon atoms. US Patent No. 3,620,712 to Conklin also describes carboxylic acids with chain lengths

between 6 and 12 carbon atoms as herbicidal agents. Others have described other long chain acids and esters for similar herbicidal use, such as Darlington in US Patent No. 2,117,856 and Stewart et al. in US Patent No. 2,603,560, the former describing compounds with carbon chain lengths of 12 or less, and the latter chain lengths of 1 to 14 carbon atoms. No reference to long chain carboxylic acids or salts or derivatives thereof showing practical utility as plant growth regulators was found in the literature with respect to chain lengths greater than 22 carbon atoms. Nor were references found regarding plant growth-stimulating effects of the aforementioned compounds.

Long-chain alcohols have become known as useful plant growth-regulating compounds, such as n-dodecanol for the removal of root shoots from tobacco. However, only one long-chain alcohol has been found to stimulate the growth of plant life, namely 1-triacontanol, which is a straight-chain alcohol with 30 carbon atoms, as described by Ries et al.

in US Patent No. 4,150,970 and Welebir in US Patent No. 4,333,758. The initial inconsistency of results described by Ries et al. led to investigations of alternative compositions of 1-triacontanol, and US Patent No. 4,333,758 teaches that the use of metal ions in the mixtures shows a synergistic effect on the activity of the alcohol and increases its reliability in promoting plant growth.

Long-chain carboxylic acids, such as 1-triacontanoic acid, have been investigated together with derivatives thereof, as possible plant growth regulators, but all results have so far been negative. E.g. have Jones et al. reported that both 1-triacontanoic acid and methyl octacosanoate are both ineffective as plant growth regulators

(Planta, 144: 277 (1979)), and 1-triacontanoic acid and other similar compounds were found ineffective in altering the growth of wheat (Charlton et al., Can. J. Plant Sei. 60: 795 (1980)).

Explanation of the invention

The realization that underlies the invention is the surprising fact that when combining long-chain carboxylic acids with approximately 12 or more carbon atoms and metal ions with a valence of +2 or more, or salts, esters or other derivatives of the aforementioned carboxylic acids with the aforementioned metal -ions, produce mixtures which are remarkably effective in stimulating plant growth and decidedly superior to the effects observed with 1-triacontanol mixtures containing metal ions, as previously described in US patent document no. 4,333,758..1 most cases are also found carboxylic acids, or salts, esters or other derivatives thereof with somewhat less than 30 carbon atoms, and have a superior effect in relation to 1-triacontanoic acid. The compounds used in the invention can further be combined with other plant growth substances to change their effects on plant life, or can be used simultaneously with herbicides or fertilizers to reduce the costs of individual application of each.

Previous teaching has shown that 1-triacontanol mixtures are effective at alkaline pH and are affected by iodizing agents and temperature. When using the compositions according to the present invention, however, these are of little importance and improved results are obtained at different optimum temperatures than those which are optimum when 1-triacontanol is added, and results in the presence of certain fertilizers have also been found to be different from those which found using triacontanol mixtures. Due to these and other circumstances which will be clarified in the following detailed description of the invention, the mechanism by which mixtures in accordance with the invention can exert their effect seems to be completely different from that by which triacontanol exerts its effects on plant life. Furthermore, natural products containing the long-chain compounds in accordance with the invention can be used. While some of these are also found to contain a relatively small amount of triacontanol, a compound found everywhere in nature, the effects of the naturally occurring compounds in the mixtures in accordance with the invention have been shown to be due to compounds in accordance with the invention and not triacontanol.

It is therefore an object of the present invention to provide a cheap and effective means of stimulating the growth of plants and increasing the yield of crops in the field.

It is another object of the invention to provide new mixtures of carboxylic acids and their salts and derivatives, and metal ions which are very effective in stimulating plant growth and increasing crop yields.

It is a third purpose of the invention to provide a method for adding compounds in accordance with the invention to areas where plants grow.

It is a fourth object of the invention to provide environmentally safe means for stimulating plant growth and crop yields.

It is a fifth object of the invention to provide an advantageous method for stimulating plant growth and crop yields.

In accordance with the invention, the above-mentioned difficulties are mainly overcome by providing simple, cheap and safe methods and mixtures of long-chain carboxylic acid, esters and salts and derivatives thereof with metal ions, which are useful for stimulating the growth of plant life and increasing the yield of crops in the field.

The mixtures according to the invention include at least one compound of formula:

or a salt thereof or a derivative thereof in which R is a straight-chain or branched, substituted or unsubstituted alkyl group with at least 12 carbon atoms, preferably between 15 and 47 carbon atoms and more preferably between 17 and 35 carbon atoms, R' is hydrogen or a straight-chain or branched, substituted or unsubstituted alkyl group with between 1 and 36 carbon atoms, preferably 1 to 30 carbon atoms, and more preferably 1 to 24 carbon atoms, as well as a metal salt in which the metal ion in the salt in an aqueous solution has a valence of +2 or + 3, the metal salt being present in the mixture in an amount effective to

help the compound in stimulating plant growth.

While straight-chain saturated carboxylic acids and esters thereof are preferred, unsaturated acids and esters are also very useful, practical utility decreasing with the number of carbon-carbon double bonds in the straight chain. If R or R' is unsaturated, it is desirable that there be 1 to 6 double bonds, preferably 1 to 3 double bonds and most preferably only 1 double bond. It is preferred that R and R' are both straight-chain alkyl groups, but compounds in which R and/or R' are branched are also useful in the invention. If the compound (I) is a carboxylic acid, monobasic carboxylic acids are preferred. However, dibasic and polybasic acids show comparable activity compared to monobasic acids and the number of carboxyl groups attached to the hydrocarbon chain affects the activity to a lesser extent than the number of carbon-carbon double bonds in the straight chain of the carboxylic acid.

Compounds in accordance with the invention are preferred

of formula:

or a salt thereof wherein R is a saturated long-chain alkyl group of 15 to 47 carbon atoms and R' is hydrogen or a saturated alkyl group of between 1 and 36 carbon atoms.

While R' can have a length of more than 36 carbon atoms, these compounds are considerably more expensive to produce than the shorter chain analogues. Thus, 1-teiracosanyl tetracosanoate exhibits superior effects to tetracosanoic acid and is also superior to 1-methyl-tetracosanoate. Although one does not consider oneself bound to the mechanism by which the invention achieves the remarkable results, it seems that the longer the chain contributed by the R'r group, the better the hydrophobic binding to a "plant receptor" be. Other derivatives of carboxylic acids are useful in carrying out the invention, such as anhydrides, carbohydrate esters and the like, thiocarboxylic acids and esters and salts thereof, cholesteryl esters and other steroid esters, amides, triglycerides and other related compounds. Any compounds which can release the free carboxylic acid, or salts or derivatives thereof, in aqueous solution by the action of acids or bases or other agents are also intended to be used in the invention. Salts of carboxylic acids in accordance with the invention are also very useful, and show a higher solubility in aqueous solution than the free acids or esters.

Specific examples of saturated acids of formula (I) include CH3(CH2)16COOH (stearic acid), CH3(CH2)lgCOOH (eicosanoic acid), CH^(CH2)2<qC>00H(docosanic acid), CH3(CH2)22COOH (tetracosanoic acid ), CH3(CH2)24<C>OOH (hexacosanoic acid), CH3(CH2)26COOH (octacosanoic acid), and CH3(CH2)2qCOOH (triacontanoic acid). Of these connections

eicosanoic acid, tetracosanoic acid and triacontanoic acid are preferred.

Specific examples of saturated esters of formula (I) include CH3(CH2)2gCOOCH3 (methyl triacontanoate), <CH>3(CH2)34COOCH3 (methyl hexathriacontanoate), CH3(CH2)4QCOOCH3 (methyl dotetracontanoate), CH3(CH2 )46COOCH3 (methyl octatetracontanoate), CH3(CH2)22CO°(CH2)23CH3

(tetra-cosanyl-tetracosanoate), and CH3(CH2)22C00^CH2^29CH3(triacontanyl-tetracosanoate). Of the above-mentioned compounds, methyl triacontanoate, tetracosanyl tetracosanoate and tricontanyl tetracosanoate are preferred.

Examples of unsaturated esters of formula (I) include C<H>3(CH2)1QCH=CH(CH2)4COOCH3 and CH^(CH2)22COO(CH2)CH=CH2.

Examples of unsaturated carboxylic acids of formula (I) include CH3(CH2)7CH=CH(CH2)7COOH (oleic acid) and C<H>3(CH2)12CH=(CH2)gCOOH (nervonic acid).

Examples of polybasic carboxylic acids include HOOC (CH2) 16COOH (1,18-octadecanedioic acid), HOOC (CH2).2QCOOH (1,22-docosandiic acid), HOOC(CH2)22<C>OOH (1,24-tetracosanedioic acid) and HOOC(CH2)1QCH(CH2)1Q<C>OOH

COOH

(1,12,2 4-tetracosanitric acid).

Examples of salts of compounds of formula (I) include, but are not limited to salts of formula

+ + +7 +"} +7 +2 + in which X is Ca+2, Na+, K+, Mg+2, La+3, Mn+2, Zn+2, NhJ , anilinium, octadecyl-ammonium etc. in which n is the valence of the cation.

According to the invention, the compounds according to the invention are solubilized in an aqueous solution containing at least one metal ion with a valence of +2

or more. The compounds can be dispersed in aqueous solution using any method practiced in the field, including simple solubilization of the compound in the aqueous solution by stirring, heating and the like, or can first be dissolved in an organic solvent which is then dissolved in a relatively large amount water, with or without the aid of a surfactant, and preferably in a surfactant

free medium. The most preferred method for solubilizing the compounds of the invention in aqueous solution comprises coating the carboxylic acids or salts or derivatives thereof, or combinations thereof, on the dry salts of the metal ions by means of a solvent in which any of the compounds used to coating the metal ion salts is soluble.

Subsequent dilution in water gives a very useful solution of the compounds according to the invention together with metal ions.

When the mixtures according to the invention are in dry form, the weight ratio between the compound and the metal salt is in the range 1:1 to 1:5,000,000,000, preferably 1:5 to 1:500,000,000, more preferably 1:100 to 1:50,000,000 and most preferably 1:1,000 to 1:20,000,000. Optimum weight ratios will vary somewhat depending on the particular compounds of formula (I) and metal salts used. The optimal weight ratio will also vary somewhat depending on the type of plants to be treated with it.

Mixtures in accordance with the invention contain the compound of formula (I) and the metal salt in an amount effective to stimulate plant growth. When the mixture is in dry form, the ordinary rice will contain the metal salt in an amount of 50 g to 1,000 g per kg, preferably 250 g to 1,000 g per kg, most preferably 500 g to 1,000 g per kg of the mixture. The compound of formula (I) will preferably be contained in an amount of 0.1 microgram to 10 g per kg, preferably 50 micrograms to 5 g per kg, most preferably .1 microgram to 1 g per kg of the mixture. As discussed in the following, the mixture may contain further active ingredients which improve or do not significantly inhibit the plant growth-stimulating effects of mixtures in accordance with the invention. The mixtures may also contain different inert ingredients (liquid or solid) which are incorporated into the mixture in different amounts

amounts depending on the method of application to plant life.

Typically, one part by weight of a compound according to the invention, or mixtures of more than one compound, is diluted to a final solution with up to about 5,000,000,000 parts of water (weight basis), preferably diluted with between about 4,000 to 2,000,000,000

parts of water, and more preferably with between about 40,000 and 200,000,000 parts of water. The effective range of concentrations of the compounds according to the invention in solution with metal ions can thus vary within wide limits while achieving similar results in stimulating plant growth and yield of crops in the field.

If an organic solvent is used to form a concentrate of the carboxylic acids or derivatives thereof, the compound is first dissolved in the organic solvent, with or without the application of heat. The resulting solution is then added to water which may contain the metal ions in accordance with the invention, or the metal ions may be added after the addition of the concentrate. Typically, one part (weight basis) of one or more of the carboxylic acids or derivatives thereof is dissolved in accordance with the invention in between about one and 5,000,000 parts of polar organic solvent (if no surfactant is to be added, or relatively non-polar solvent if a surfactant must be added), and preferably one or more of the compounds according to the invention are added in between about 10,000 and 500,000 parts of polar solvent (weight basis) and more preferably 10,000 parts to about 160,000 parts of solvent can be used, and most preferably between about 10,000 and 80,000 parts solvent can be used. If a non-polar solvent is used, a part of one or more compounds according to the invention (carboxylic acids, salts, esters or other derivatives thereof), on a weight basis, can be dissolved in between about one and 10,000 parts of non-polar solvent, preferably between about 10 and 1,000 parts non-polar solvent, and more preferably between about 100 and 1,000 parts non-polar solvent (by weight). The resulting solution is then dissolved in water as previously described,

with or without the use of a surface-active additive, depending on the solubility of the solvent which would be necessary in water to achieve the desired concentration of the compounds in accordance with the invention.

Polar organic solvents useful in the practice of the invention to promote the solubility of the long-chain compounds of the invention include, but are not limited to, ketones, alcohols, water-soluble ethers, glycols, sulfoxides, relatively low molecular weight organic carboxylic acids, amines, di -polar aprotic solvents such as DMSO (dimethyl sulfoxide), DMF (dimethyl formamide) and HMPA (hexamethyl phosphoramide) and the like. Typical polar and organic solvents include acetone, methyl ethyl ketone, diethyl ketone, cyclohexanone, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, sec-butanol, ethylene glycol, propylene glycol, diethylene- glycol, glyme, diglyme, dioxane, tetrahydrofuran, acetic acid, formic acid, propionic acid, lower aliphatic amines and other similar solvents which show a solubility in water and in which the compounds according to the invention are also soluble at concentrations where the resulting concentrate is useful for stimulating plant growth and crop yields after dilution to a final volume in water.

Non-polar organic solvents which may be used to promote the dispersion of the compounds of the invention with or without the use of a surfactant include, but are not limited to, hydrocarbons, higher alcohols, aromatic hydrocarbons, water-soluble ethers, esters, amines, halogenated hydrocarbons and the like. Typical non-polar solvents include chloroform, methylene chloride, carbon tetrachloride, freons, benzene, toluene, xylenes, aniline, pentanols, hexanols, heptanols, octanols, other long chain alcohols, pentane, hexane, heptane, other hydrocarbon solvents, both aliphatic and aromatic,

alkenes, alkynes, higher aliphatic amines, ethyl acetate, amyl acetate, other lower esters and other non-polar compounds in which the compounds according to the invention are soluble, and which can further be dispersed in water containing metal ions, or before the aforementioned metal ions are added to the solution, either with or without the help of surface-active additives.

Surfactants useful in the dispersion of the compounds of the invention in aqueous media include, but are not limited to "Tweens", long chain alkyl sulfonates, "Zonyl" surfactants, alkyl sulfates, nonionic surfactants, anionic surfactants, cationic surfactants and other surfactants known in the art which are useful for dispersing substantially non-polar solvents or compounds in aqueous media. If surfactants are not used, they can be added either before or after the addition of metal ions to the aqueous solution, or before or after the addition of the solution of the compounds according to the invention in an organic solvent to the aqueous part of the mixture. The amount of surfactant used is preferably kept to a minimum as complex formation or precipitation of the metal ions may occur, as this reduces the weight-promoting effect, or necessitates that additional metal ions must be added. Surfactants are typically used up to a concentration (volume/volume) of approximately 5%, with a . concentration of between about 0.1 and 3% preferred, and a concentration of between about 0.1 and 1% most preferred.

Metal ions in accordance with the invention, such as i

combination with the long-chain carboxylic acids, and salts and

derivatives thereof, they produce remarkable growth-stimulating effects, include any cation with a valence of +2 or more. While metal ions with lower valence produce a small effect, a higher valence is required for the full growth-stimulating effect. Typical metal ions useful in the practice of the present invention include but

., ... t _ +2 „ +2 T +3 „,+2 _+2 „ +2

is not limited to Ca ,Ba La Cd ,Pb , CQ , +2 +4 +2 +2 „ +2 +3 +2 „.+2

Mn, Ce, Mg, Zn Cu Fe, Fe, Ni, and the like, but only a limited number of metal ions are preferred because of their superior action and relatively low toxicity. Metal ions with higher toxicity such as Pb and Cd are very useful and can be used for plant life that is not used for nutritional purposes. Second

+2

metal ions such as Sr are particularly useful, however the most preferred metal ions are Ca, La, Mg and Mn due to their low toxicity. Furthermore, Ca is cheap and useful salts are exempt from the tolerance requirements of the US Environmental Protection Agency. While some of these metal ions are known to affect the reaction of plants to the known plant growth substances, these belong to the well-known Hofmeister series and include Ca , La , Mg and Mn . The activity observed with other polyvalent metal ions indicates, however, that the biological activity of these cations in mixtures in accordance with the invention does not seem to be related to the known effects of the cations from the Hofmeister series. While the exact mechanism remains unclear, metal ions of the invention, along with the compounds of the invention, were found to be inactive when administered separately - not in combination - under identical application conditions.

In the preferred embodiment of the invention, either the compounds according to the invention are (1) added to a solution of metal ions in water in a polar organic solvent, or (2) coated on the dry salts of the metal ions according to the invention in use of a suitable solvent which is then allowed to evaporate, with or without the action of heat. The latter method is the most preferred as it allows a product to require only a simple container without the need for a separate package containing a solution of the long chain compounds. As the long-chain compounds can be used at a very low concentration, the solubility usually does not pose a problem when the dry product is added to water.

Preferred metal ion concentrations in the final aqueous mixture applied to plant life are between 0.1 and 50 mM, with concentrations of between about 1 and 30 mM being preferred. If a surfactant is part of the final mixture, higher metal ion concentrations may be necessary and may amount up to 1 molar.

In accordance with another aspect of the invention, other plant growth substances appear to alter the effects of the compounds of the invention, such as e.g. auxins, gibberellins, cytokinins, abscisic acid, ethylene, together with salts and synthetic analogues thereof. Auxins are particularly capable* of extending the useful range of metal ion concentrations which stimulate plant growth in compositions according to the invention. This is of practical use for crops that react to relatively low metal ion concentrations, such as e.g. maize for animal feed, where hard water used for spraying can contain large amounts of metal ions. Auxins include all natural and synthetic auxins, with auxins such as indole-3-acetic acid (IAA) and naphthalene-acetic acid (NAA) being among the preferred auxins. These can be added to the solutions of the compounds in accordance with the invention, or to the aqueous solutions which may contain the metal ions in accordance with the invention, with or without the addition of the compounds in accordance with the invention. Alternatively, they can be coated on salts of the metal ions by any method used in the field. Water-soluble salts of the auxins, gibberlins (such as gibberlic acid and the like) and cytokinins (such as kinetin, benzyladenine and the like) are particularly useful.

When applying the long-chain carboxylic acids, esters, salts or derivatives thereof, alone or in combination, to the areas where the plants are grown, it is desirable to add at least 0.0025 mg of the compounds per target land, with a supply of approximately 0.0075 mg of the compounds per goal. Up to several grams of the compounds can be applied per target land, but this is usually not necessary, and a limited benefit from increasing the supply quantity is observed as will be seen

of the following examples of embodiments of the invention. The preferred method of application of the compounds according to the invention in solution with polyvalent metal ions is foliar spraying of the mixtures as a fine mist on the leaves of plant life. However, effects have been observed using other application methods, such as e.g. seed impregnation and field impregnation. Seed impregnation has the advantage of requiring a small volume of the mixtures in accordance with the invention, while field impregnation requires considerably larger quantities. For seed impregnation, the preferred ratio between seed and solution of compounds according to the invention including metal ions in solution is at least two parts of solution for every one part of seed (volume/volume) and similar results are obtained with higher ratios between solution and seed, up to about 25 to 1 or more. Soil impregnation requires a considerable amount of solution, amounting to between 1 ml per plant to 10 liters per plant, with 1 ml to 1 liter per plant is preferred and 1 ml to 1 liter per plant is preferred more. Of course, larger plants require a greater volume of solution than smaller plants and plants with deeper root systems likewise require more solution applied to the soil in which they grow. Combinations of ground impregnations, seed impregnations and foliar application are also useful, and other application variations, such as the formation of colloidal suspensions of the compounds according to the invention and the like, applied as

inoculants, use of mixtures such as fertilisers, additives or the like, are not considered to lie outside the scope of the invention.

The mixtures according to the invention are usable on plant life at all stages of development, with some plants reacting better at relatively earlier stages in comparison with other plants. The preferred developmental stage is the stage where the plant bears between about 2 and 7 leaves (or sets of two leaves in the case of dicots, or up to the fifth trifoliate stage for beans and soybeans) with the preferred stage being between 3 and 6 leaves . For grass species, such as wheat, maize, sorghum and the like, later growth stages have shown some advantage. Maize can be treated in a stage before or after shoot initiation in the plant. Wheat is best treated in the spring rather than shortly after germination in the autumn. Perennial plant life can be treated depending on the season, as treatments in early spring are preferred. Several sprayings on growing plants have also indicated that improved results can be obtained in this way, especially for soybeans, tomatoes and the like.

While the pH of the final mixture is not of importance, best results are obtained when the acidity or alkalinity is not very strong, preferably pH between 4 and 12 and more preferably pH between 5 and 10. Due to the tolerance of the metal ion concentrations in most plants, hard water (or well water) can usually be used without concern for the metal ion concentration in the water. Heavily polluted water, or water known to contain large concentrations of hydrocarbons or other long-chain compounds (eg water on which oil has deposited on the surface) should be avoided.

Plants are best fertilized using normal agricultural practices, without unusual or extra equipment, and results are observed even with suboptimal amounts of fertilizer. In greenhouse experiments, however, the use of concentrated water-soluble fertilizers affects the results to some extent and some guidelines for greenhouse experiments are given in the following examples of the invention. Improved results have also been observed with the inclusion of foliar fertilizers in mixtures in accordance with the invention. These include water-soluble salts that supply the plants with essential nutrients, micronutrients (including metal ions in accordance with the invention), nitrogen-containing compounds such as urea, ammonium nitrate and the like, potassium, and other compounds or combinations thereof known in the field. Compounds which complex or precipitate the metal ions used in accordance with the invention produce smaller increases when combined in solution with the compounds and metal ions in accordance with the invention and therefore show somewhat more limited practical utility.

The metal ions in accordance with the invention are any metal ions with a valence of +2 or more and those released from inorganic metal salts are preferred, but any organic or inorganic salts or compounds capable of releasing an effective concentration of the desired metal ions in aqueous solution can be used. Counter-ions, such as Gl-, NO^<->, acetate and the like are of minimal importance, as they do not appear to affect the activity of the cations in accordance with the invention. Somewhat complexed metal ions can also be useful, as well as hydrated metal ions.

Salts of carboxylic acids in accordance with the invention are very useful when carrying out the methods for plant growth stimulation during the practice of the invention and show improved solubility in comparison with the free acids in accordance with the invention. These salts can be any known in the field which show a solubility in the concentration range useful for the carboxylic acids according to the invention. The salts of alkali metals show preferred water solubility, but since the compounds in accordance with the invention show solubility at the low concentrations that are useful, described further in the following, other metal salts can also be of valuable use, such as salts of metal ions in accordance with the invention. These polyvalent ions show a limited solubility at certain concentrations in combination with long chain carboxylic acids, but it is important to note that the concentrations of the carboxylic acids according to the invention which show effective results may be low enough to show no solubility in aqueous solutions prepared therefrom . Salts of carboxylic acids or derivatives thereof may include a plurality of metal ions, and metal ions useful in carrying out the invention may be in the form of salts of a plurality of long-chain compounds in accordance with the invention.

It has further been found that different species of plant life react optimally to somewhat different concentrations of metal ions, while the concentration of the long-chain compounds in accordance with the invention remains within a much wider range. E.g. soybeans, sweet corn, and a wide variety of vegetables respond to metal ion concentrations over a wide range of between about 5 mM and 15 mM or more. In some cases, positive results are seen at lower metal ion concentrations. Maize for animal feed seems to respond well to a relatively low concentration of metal ions, i.e. between approximately 1 mM and 4 mM, with approximately between 2 mM and 3 mM being preferred. Depending on the cultivation method used, this range can be somewhat wider. The invention is further seen differently in relation to the results observed previously (e.g.

US Patent No. 4,333,758) as the use of mixtures containing metal ions and 1-triacontanol is very limited for use in maize for animal feed, as reactions are only observed in a small number of cultivation methods at a low, narrow range of metal ion concentrations , respectively between about 1.00 and 1.25 mM. Mixtures in accordance with the invention show positive results for all cultivation methods for corn for animal feed tested with a similar mixture containing metal ions in the above

described concentrations.

Other crops, such as peas and the like, react to mixtures of compounds according to the invention containing higher metal ion concentrations. These crops are seen to respond well to metal ion concentrations in the range of up to 20 mM or more, while wheat responds well to concentrations above about 15 mM to 20 mM. From the detailed description given below, optimal concentrations of metal ions, together with concentrations of compounds according to the invention which increase the growth of many crops and other plants will be apparent.

Compositions according to the invention are useful for a wide variety of plants and can be applied in a variety of ways. Crops that respond favorably are included in the group but not limited to corn for animal feed, corn, sweet corn, milo, sorghum, wheat, barley, oats, rice, rye, apples, pears, quince, avocado, papaya, blackberry, rubus blackberry , hybrid blackberries, raspberries, blueberries,

currants, gooseberries, American blueberries, cherries, plums, prunes^, oranges, lemons, grapefruit, limes, tangerines, mangoes, apricots, nectarines, beans, peas, soybeans, broccoli, lettuce, cauliflower, kohlrabi, melons, watermelons, carrots, turnips, sugar beets., horseradish, radishes, turnips, celery root, snake cucumber; Endive lettuce, Chinese cabbage, onions, garlic, potatoes, Jerusalem artichokes, sweet potatoes, yams, spinach, mustard greens, sunflowers, tomatoes, peppers, pimientos, almonds, Brazil nuts, filbert nuts, hazelnuts, hickory nuts, walnuts, alfalfa, Bermuda grass, bluegrass, clover, lespedeza, lupins, garden grass, peanut hay and peanuts, cashews, ryegrass, soybean grass, sudan grass, timothy, corngrass, sorghum grass, sugar cane, cane sorghum, bananas, pineapples, grass and grains used for feeding livestock, crops used to feed poultry, fish and other wildlife, pawpaws and other raw agricultural crops.

The compositions according to the invention may also be useful in increasing the growth and quality of trees, such as loblolly pine, Australian pine, Douglas pine, pines, oaks and other trees. The mixtures according to the invention are likewise useful for use on ornamental plants, including any plants used indoors and outdoors for ornamental purposes and which can be expected to show the effect of fungal growth under suitable conditions. The compounds according to the invention also show effects on mammals and other effects on living forms can be expected to show improved activity when combined with the metal ions in accordance with the invention.

In accordance with a further aspect of the invention, naturally occurring products containing active amounts of the compounds of the invention are very useful when combined in the mixtures with metal ions. In particular, these include naturally occurring waxes and oils and the like, then include compounds according to the invention, or mixtures thereof, which can be obtained from natural sources. These generally include useful compounds such as long chain carboxylic acids according to the invention, esters thereof, hydroxy acids and the like and include both saturated and unsaturated compounds. The compounds can also be present as esters of other naturally occurring compounds containing carboxyl groups or hydroxyl groups, such as auxins, gibberlins, sugars, etc.

Useful naturally occurring compounds include,

but is not limited to candelilla wax, carnauba wax, Chinese insect wax, esparto wax, ghedda wax, Japan wax, peanut oil, olive oil, rice husk oil, shellac, sisal wax, soybean oil, beeswax, etc. The preferred substances of these include any naturally occurring wax, oil, etc., containing the compounds according to the invention, or mixtures thereof, such as beeswax, esparto wax, etc.

In a preferred embodiment of the invention

such naturally occurring waxes are used in the mixtures in accordance with the invention, and can be used in any way that the pure compounds in accordance with the invention are utilized. Particularly useful are concentrated forms of the mixtures, prepared by coating a relatively small amount of the naturally occurring wax, oil, etc., or mixtures thereof, directly onto a metal salt of the metal ions in accordance with the invention, by means of a suitable solvent or by using other measures, as described in the preceding description.

While naturally occurring compounds may contain an additional active ingredient, such as 1-triacontanol, the following examples of the best embodiment of the invention illustrate that this compound is inactive in compositions as described herein. Many compounds and other substances are used in practical agriculture, also containing 1-triacontanol, but 1-triacontanol is assumed to be mainly inactive. Such substances include straw-containing manure, cow manure, paper, peat and peat litter, compost etc.

Substances such as these have been in use in agriculture since the beginning of agriculture itself and do not form any part of the present invention as methods of increasing crop yield and plant growth, unlike specific mixtures of ingredients contained herein which are very useful for promoting plant growth, as described in US Patent No. 4,150,970 and US Patent No. 4,333,758. Mixtures of more purified forms of the compounds according to the invention, such as those contained in naturally occurring plant products etc.,

in combination with specific concentration ranges of added metal ions in aqueous solution, however, offers superior improvements and results over prior art. The surprising results obtained by using mixtures in accordance with the invention will appear

for the person skilled in the art from the subsequent description of the invention.

In accordance with a further aspect of the invention, seeds obtained from crops sprayed with compositions in accordance with the invention show improved quality and can be expected to show increases in crop yield and obtained by planting said seeds with or without further application of the compositions and further increases can actually be observed from growing season to growing season. Improved germination has been observed in seeds from crops that require a longer germination time and grow slowly after germination, such as tomatoes, pepper, celery, lettuce, tobacco etc.

Having described the invention in this way, other objectives and further frameworks for the invention will appear from the subsequent detailed description. It should be noted, however, that the detailed description and specific examples, indicating preferred embodiments of the invention, are given only as . illustration in that various changes and modifications within the idea and framework of the invention will be apparent to the person skilled in the art from this detailed description.

BRIEF DESCRIPTION OF THE DRAWINGS

Fig. 1 is a graphical representation showing a typical dose-response curve for the compounds of the invention, illustrated for the response of corn for animal feed (type "Pioneer 3780") for mixtures of the invention containing 3 mm CaC^ and various concentrations of 1 -triacontanoic acid. Fig. 2 is a graphical representation showing the optimal hydrocarbon chain lengths of compounds according to the invention for use in tomatoes (CaC^ = 10 mm) and corn for animal feed (CaC^ = 2 mm). Fig. 3 is a graphical representation showing the reaction of sprouts of corn for animal feed (type "Pioneer 3535") to mixtures in accordance with the invention containing beeswax (10 ug/liter) and Ca + 2 (2 m») at different stages of development.

BEST PRACTICE EXAMPLES

The following examples are given here as examples of the present invention and should therefore not be considered in any way as limiting the scope of the invention.

In the preferred embodiment of the invention, compounds of formula are considered

wherein R is a long-chain alkyl group containing 15 to 47 carbon atoms and which may contain between about 0 and

6 carbon-carbon double bonds, and which may be replaced by about 0 to 4 carboxyl groups or derivatives thereof, and

R' is a long-chain alkyl group of about 1 to 36 carbon atoms and which may contain between about 0 and 6 carbon-carbon double bonds and may be substituted with about 0 to 4 carboxyl groups, or derivatives thereof, or is hydrogen, which the most preferred representatives of the classes of compounds discussed in the foregoing description. These are used to stimulate plant growth 1 mixtures given in the following examples in combination with metal ions with a valence of +2 to +3. The compounds in accordance with the invention can also be contained in naturally occurring oils, waxes etc., as described in the subsequent description of the preferred embodiments of the invention. Also, compounds that are hydrolyzed in situ to compounds in accordance with the invention in the mixtures are not considered to lie outside the scope of the present invention.

MIXTURE 1

A 5 mg amount of 1-triacontanoic acid was dissolved with heating in 50 ml of acetone. The concentrate was then added to a solution of metal ions in water and applied as a foliar spray to plant life.

MIXTURE 2

A 5 mg amount of 1-tetracosanoic acid or other long-chain acid was added to 50 ml of acetone, optionally heated to dissolve the compound. The solution was added to a solution of metal ions and applied as described for mixture 1.

MIXTURE 3

A 5 mg amount of a long chain ester was dissolved in 5 ml of a ketone or alcohol solvent, with or without the application of heat. The solution was applied to an aqueous solution of metal ions and applied to plant life, or used for a seed impregnation or soil impregnation.

MIXTURE 4

A 5 mg amount of a long-chain, unsaturated carboxylic acid, with at least one carbon-carbon double bond, was dissolved in acetone or other suitable solvent. The solution was then added to a larger volume of water containing metal ions and applied to plant life.

MIXTURE 5

A 150 mg amount of a long-chain ester or fatty acid ester was dissolved in 100 ml of trichlorethylene with or without the application of heat. A quantity of the resulting solution was added to a solution of metal ions, with or without the aid of a surfactant additive, and sprayed onto the leaves of growing plant life.

MIXTURE 6

A 50 mg amount of a tetracosanoic acid (or other long-chain acid or ester) was dissolved in 50 ml of acetone or other solvent in which the compound was soluble, with or without the application of heat. The concentrate was then used to coat the salt with a metal ion in accordance with the invention, allowed to dry, and the salt then dissolved in water and added to plant life, or used as a seed impregnation or soil impregnation. Weight ratio (compound: salt) is <1:100.

MIXTURE 7

A 150 mg amount of naturally occurring wax was solubilized in 100 ml of trichlorethylene, with or without the addition of heat. The solution was then used to coat salts of metal ions in accordance with the invention which were then dissolved in water to form a mixture with the desired concentration of both components. The solution was then added as described under mixture 6 above.

MIXTURE 8

A 150 mg amount of naturally occurring wax or oil was dissolved in 100 ml of a non-polar solvent such as trichloroethylene, chloroform, benzene, etc., and the resulting solution was further dissolved to allow a sufficient volume resulting therefrom to coat an amount of a metal ion salt, or combination thereof, relatively greater than that described under the preceding mixture 7. The solvent used for further dilution of the concentrated solution may be selected from groups of solvents which are either polar or non-polar in nature. The resulting treated gaps of metal ions in accordance with the invention are then diluted in water after evaporation of the solvent.

DETAILED EXAMPLES

EXAMPLE I

A 0.1 ml amount of mixture 1 was added to a solution of MgCl 2 / or other metal salt, with a metal ion concentration of 3 mm in water, stirred and sprayed on the leaves of sprouts of maize for animal feed.

EXAMPLE II

A 1.0 ml amount of mixture 1 was added to a

+ 2

solution of CaC^ or another Ca salt, in water at a concentration of 10 mm (200 ml total volume). The solution was shaken and sprayed on the leaves of soybean sprouts (1-triacontanoic acid concentration 0.1 mg/l).

EXAMPLE III

A 0.01 ml quantity of mixture 2, containing stearic acid

+2 +3

was added to a solution of Ca or La salts with a metal ion concentration of 10 mm. After stirring, the solution was applied to the leaves of tornat plant sprouts.

EXAMPLE IV

A 1.0 ml sample of a tetracosanyl tetracosanoate in acetone solution was dissolved in 2 liters of water containing a 15 mm metal salt. The resulting solution was sprayed on the leaves of pea sprouts.

EXAMPLE V

A 0.1 ml amount of erucic acid was dissolved in a suitable solvent and added to 200 ml of water containing metal ions with a concentration of between about 10 mm and 15 mm. The resulting solution was then applied to the leaves of tomato plant sprouts, or can be used as a seed impregnation for tomato seeds.

EXAMPLE VI

A 40 ml sample of hexacosanoic acid, or salt or suitable derivative thereof, in solution according to mixture 2 or 3, was added to 37.85 L of water containing metal ions at a concentration of 3 mm. The final solution was applied as a mist to approximately 4 acres of corn for animal feed.

EXAMPLE VII

A 0.5 mg amount of 1-tetracosanoic acid was added

109 g of anhydrous CaCl2 and the mixture was allowed to dry. The granulated product was dissolved in 378 L of water and applied to about 40 acres of corn for animal feed as a fine foliar shower, the water having a metal ion concentration of between about 2 and 3 mm.

EXAMPLE VIII

Beeswax or esparto wax was dissolved in a non-polar solvent such as trichlorethylene or the like, in accordance with mixture 7. The solution was then uniformly applied to about 80 kg of anhydrous CaCl 2 and allowed to dry. Dilution of the final product in water to 2 mm Ca + 2 concentration provided sufficient solution to cover approximately 3,800 acres of animal form ice.

EXAMPLE IX

A 0.33 ml sample of the solution described in mixture 7 was added to 109 g of technical grade CaCl 2 (77%) and the mixture was dried. After dissolving the granulated product in about 37.85 L of water, the solution was sprayed at a rate of about 19 L/acre on about 2 acres in two applications.

EXAMPLE X

A 0.67 ml sample of the solution according to mixture 8 was added to 50 ml of acetone (or other solvent) and to the solvent was added 1.090 g of technical grade CaCl 2 . After the product had dried, it was dissolved in approximately 757 L of water and applied to approximately 40 acres of a vegetable crop at a rate of approximately 19 L/acre.

While the preceding examples only partially briefly illustrate the preferred embodiments of the invention, they are in no way intended to limit the scope of possible combinations of compositions and methods in accordance with the invention. The mixtures according to the invention are applied, preferably to the leaves of growing plant life, and are also useful as seed impregnation, field impregnation, etc. The methods used to assess the effect in the preceding examples in accordance with the invention are outlined in the following description of the methods used in practicing the invention.

METHODS

The compounds of the invention were obtained from the following sources: straight chain saturated and unsaturated carboxylic acids of up to 30 carbon atoms were obtained from Sigma Chemical Co., St. Louis, Mo. Long-chain esters were synthesized either by esterification with an ether solution of diazomethane, or by reaction between the acid chloride and an alcohol. Amides were produced by reaction between acid chlorides and aqueous ammonia. Carboxylic acids and esters with a carbon chain of more than 30 carbon atoms were prepared in accordance with the methods disclosed in either US Patent No. 4,167,641 or the methods described in Ph. D. Thesis by Andrew J. Welebir entitled "The Synthesis of Long-Chain Carboxylic Acids Containing Up to Forty-Eight Carbon Atoms and Use of Their Potassium Carboxylates as New Surfactants", The American University, Washington, D.C., May 1978.

To illustrate the action of compositions according to the invention, two primary methods of forming the compositions were used: (a) solubilization of the compounds according to the invention in a suitable solvent, polar solvents being preferred over non-polar solvents, with or without the use of surface-active additives, and dissolving the thus obtained concentrate in water, optionally containing a surface-active agent; and (b) adding the solution of

the compound according to the invention described above to salts of metal ions according to the invention, followed by evaporation of the solvent.

The resulting granulated product was then dissolved in a desired amount of water to achieve the desired concentration

of metal ions in solution. In those cases where the pH of the solution was adjusted, this was done by adding an alkali, such as sodium hydroxide, to the water before dissolving the concentrated form of the compounds in accordance with the invention.

In greenhouse experiments, plants were sown in pots with a diameter

10 to 15 cm containing peat litter. The double number of seeds per trials were sown than the relevant number of plants used in the different treatments, the plants being thinned to a corresponding size before application of the mixtures in accordance with the invention. In general, the mixtures were fertilized at germination with a water-soluble 15-30-15 fertilizer and again the following day with (15-30-15 fertilizer in the case of dicot, and 30-10-10 fertilizer for monocot). Each group received approximately 50 ml of fertilizer with a concentration of 2.5 g/l.

In field trials, seeds were sown using standard agricultural methods or as otherwise indicated. Small pieces were generally used and were carefully selected to minimize variation in plant size within each group. In all experiments carried out (greenhouse and field experiments), the treatments were randomly carried out within each group using standard methods carried out in the area. The plants were size-blocked in the greenhouse experiments to reduce the variations due to plant size to a minimum.

The results obtained were found to be similar regardless of whether the plants were grown under natural or artificial lighting (about 750 to 1,000 ft-can) for many of the plants tested. When the plants were grown under artificial lighting, 26°C daytime temperatures were maintained with nighttime temperatures of approximately 17°C. Plants grown under natural lighting were grown at the same time of year as normal for the plant in question when grown in the field. For applications at varying temperatures, the indoor temperatures were regulated accordingly and plants grown outdoors were sprayed at varying times of the day when the desired temperatures were reached.

Plants were sprayed at different stages of development with mixtures in accordance with the invention as described in the examples that follow. In all cases, randomized complete group designs were used, with each treatment repeated between approximately 4 and 6 times. In greenhouse experiments, the plants were generally harvested at least 4 days after treatment, including the roots, and the soil was removed from there by washing with water. Fresh weights were obtained for each group and the plants were dried to constant weight in an oven at a temperature below 100°C. Water content values were obtained by subtracting the dry weights from the fresh weights, but dry weights were used as a true indicator of growth increases for treated groups relative to control groups.

During field trials, increases in salable yield were determined and observations were recorded with regard to increases in the number of fruits, grain sizes, etc. All data were analyzed statistically using standard analysis of variance methods frequently used in the field and using Duncan's Multiple Range Test (Biometrics, 11: 1 (1955)). Increases in the dry weights of seedlings found in greenhouse trials were found to be particularly useful in predicting the yields of crops in field trials and in general dry weights obtained in this way can be expected to be lower than the actual yields found in field trials.

The experiments included determining optimal stages of plant development for spraying or other application of the compounds of the invention, optimal application rates, optimal temperatures, and other conditions useful in applying compositions of the invention to plant life in the field, greenhouse or other environments .

Compounds according to the invention were tested in solution with metal ions according to the invention, either individually or in combination with other compounds or metal salts according to the invention. The preferred mixture of compounds used was

purified beeswax, which is known to contain esters of straight-chain monohydric alcohols with the same number of carbon chains from C 2/j to C^g esterified with straight-chain acids which also have the same number of carbon atoms up to C36 (some C^g hydroxy acids). Hydrocarbons with straight carbon chains from C0 1 to C 1 (inert) as described in Merck Index, 9: 1027 (1976) are also included. The long-chain esters are also found to be superior to carboxylic acids and the small amount of 1-triacontanol component in the wax is also shown by the subsequent detailed description to be inert in the mixtures according to the invention containing beeswax. Other naturally occurring oils, waxes etc. are also useful, including those obtained from both plant and animal sources, as described in the foregoing description of the invention.

Data in the following tables and examples of the invention are intended to exemplify the results that can be expected from the application of compositions in accordance with the invention to plant life using the methods outlined herein, but the specific compounds, compositions and methods used in the examples should not be considered in any way way to limit the inventive idea and scope of the invention as fully described herein.

TABLE 1 Increases in dry weight of animal form ice seedlings (cv. "Pioneer 3780") treated 7 days after germination with and without 1-triacontanoic acid (0.1 mg/l, mixture 1) and naphthalene-acetic acid, and with different concentrations of CaCl^

(ph = 9, spray temperature = 25 C). The seedlings were harvested 4 days after spraying.

The weights are the sum of four plants per group (average) repeated 5 times. Smaller variation due to plant size in trial 2 is the reason for the greater level of significance for the results compared to trial 1.

TABLE 2 Increases in dry weight of dyref orrnais seedlings sprayed 6 days after germination with mixtures of 1-triacontanoic acid (0.1 mg/l) and various metal ions (3 mm) at

temperature 26°C and pH 9.3. The plants were harvested 4 days after spraying (cv "Pioneer 3780").

TABLE 3 Increases in dry weight of animal forage maize seedlings (cv. "Pineer 3780") treated 7 days after germination with and without a variety of different long-chain alkyl carboxylic acids and esters of formula R-COOR' (mixtures 1, 2, & 3) and CaC^, harvested 4 days after spraying. TABLE 4 Increases in dry weight of animal forage corn germ plants sprayed with mixtures according to the invention (mixtures 6&7) on the 7th day after germination and harvested 4 days later (cv. "Pioneer 3320").

TABLE 5 Increases in dry weight of animal form ice seedlings sprayed with compositions according to the invention (compositions 6 & 7) on the 6th day after germination* and harvested 5 days

then (cv. "Pioneer 3382").

TABLE 6 Increases in dry weight of animal form ice seedlings (cv. "Pioneer 3572") sprayed with different mixtures according to the invention in (mixtures 6 & 7), using well water3 at pH 7.7 and sprayed in an amount of 9 .5 l/measure at two different temperatures. TABLE 7 Increases in dry weight of animal pre-maize seedlings sprayed with different mixtures according to the invention (mixtures 6 & 7) on the 7th day after germination using well water (pH 7.7) and CaCl2 of technical purity (sprayed at 19 C ). TABLE 8 Increases in dry weight of animal form ice seedlings (cv. "Pioneer 3535") sprayed with mixtures according to the invention containing beeswax (10 ug/l) and CaC^ (2 mm) at different stages of development (pH 7.4, temperature 21 .2°C, equivalent supply quantity 9.5 litres/measure.

TABLE 9 Increases in dry weights of animal form ice seedlings (cv. "Beck 65X") sprayed with compositions 6 and 7 according to the invention on the 8th day after germination at 19°C

(supply quantity equivalent to 9.5 l/measure)

and harvested on the 12th day after germination (5 replicates, 4 plants per group).

TABLE 10 Increases in dry weight of animal form ice seedlings (cv. "DeKalb XL-61") sprayed with various compositions according to the invention on the 7th day after germination with two application rates and harvested 4 days later (sprayed at 19°C). TABLE 11 Increases in dry weight of animal form ice seedlings (cv. "Trojan T-1000") sprayed with mixtures according to the invention (mixtures 3, 6 & 7) at pH 7.5 and 19.5°C on the 12th day after germination and harvested 17 days thereafter. TABLE 12 Increases in dry weight of animal form ice seedlings (cv. "Trojan T-950") sprayed with mixtures according to the invention 8 days after germination (tap water, pH 7.3, 9.5 l/measure equivalent supply amount) and harvest 4 days thereafter (mixtures 6 & 7). TABLE 13 Increases in dry weight of animal form ice seedlings (cv. "Trojan T-1100<1>) sprayed with mixtures according to the invention (mixture 6) 12 days after germination (9.5 l/measure equivalent), and harvested 4 days thereafter. l, previously known technique) 11 days after germination and with an equivalent supply quantity of 9.5 l/measurement. Plants were harvested 4 days after spraying (4 plants/group, 5 repetitions). TABLE 15 Increase in marketable yield from animal form ice treated with mixtures in accordance with the invention containing 10Jig/1 beeswax and 2 mm CaCl2 under different spraying conditions a. TABLE 16 Increases in dry weight of soybean seedlings (cv. "Williams") sprayed with mixtures in accordance with the invention (mixtures 1, 2 & 6) 16th day at pH 9.0 and 26°C (trial 1) and 16th day at pH 9.5 and 27°C (f trial 2) and harvested 6 days (trial 1) and 4 days (trial 2) thereafter.

TABLE 17 Increases in dry weight of broad bean seedlings (cv. "Williams") sprayed with compositions according to the invention containing compounds of structure R-COOR'

(mixtures 3, 4, 6 & 8 with 10 ug/l) and

+ 2

About (10 mm) at different developmental stages temperatures (pH 7.4 to 7.6).

TABLE 18 Increases in marketable yield of soybeans (cv. "Williams") sprayed with mixtures according to the invention at the three-leaf stage at 30°C and pH 7.6a (mixtures 6 & () . TABLE 19 Increase in dry weight of pea -seedlings (cv. "Early Alaska") sprayed with mixtures according to the invention (mixture 6 & 8) 8 days after germination at pH 9.3 and 26°C and harvested 4 days later TABLE 20 Increases in dry weight of pea -seedlings (cv. "Sugar Snap") sprayed with mixtures in accordance with the invention (mixture 6 & 8) 7 days after germination at pH 9.0 and 26°C and harvested 7 days later.

TABLE 21 Increases in salable yield of peas

(cv. "Early Alaska" and "Sugar Snap")

which results from the addition of mixtures according to the invention (mixture 8) at 22°C and pH 7.3 when the plants were 15 to 20 cm high (supply amount equivalent to 19 l/measure) 4 repetitions.

TABLE 22 Increases in dry weight of tomato seedlings sprayed with mixtures in accordance with the invention (mixtures 1,2, 6 & 8) when the plants had 3 pairs of distinct leaves, harvest 4 days later. TABLE 23 Increases in marketable yield of tomatoes sprayed with mixtures 6 and 6 in accordance with the invention when the seedlings had 4 sets of distinct leaves (pH 7.4, temp. = 30°C, cv. "Better Boy"). TABLE 24 Increases in dry weight of wheat seedlings (cv. "Potomac") sprayed with mixtures according to the invention (mixtures 6 & 8) when the seedlings had 3 to 4 distinct leaves (pH 7.5) and harvested 8 days later. TABLE 25 Increases in dry weight of wheat seedlings sprayed with compositions according to the invention (mixture 7) at 20°C and pH 7.5 after the seedlings had about 4 distinct leaves, harvested 5 days thereafter. The plants were subjected to drying conditions (air circulation 6 hours/day at 36.5°C and 52% relative humidity). Added quantity 9.5 l/measure equivalent.

Note: When the plants were not subjected to drought conditions, increases in water content in the area were normal

7 to 10%.

TABLE 26 Increases in dry weight of sweetcorn seedlings (cv. "Silver Queen") sprayed with mixture 7 in accordance with the invention 9 days after germination and harvested 5 days later (sprayed at 25°C and pH 6.8).

TABLE 27 Increases in salable yield of sweet corn (cv. "Golden X Bantam") sprayed with mixtures 6 & 8 in accordance with the invention when the seedlings had 4 distinct leaves (28°C, pH 7.3, 9.5 l/measure equivalent supply quantity)<*>. TABLE 28 Increases in dry weight of tdbaks seedlings (cv. "Broad Leaf Hicks") sprayed with mixtures according to the invention (mixtures 6 & 8) 52 days after germination (22°C, pH 7.4) and harvested 4 days thereafter. TABLE 29 Increases in dry weight of cotton seedlings (cv. "McNair 235") sprayed with mixtures (3', 6 & 8 according to the invention 50 days after germination (3rd to 4th set of distinct leaves) at pH 7 ,6 and 24°C (19 l/measure equivalent supply amount).TABLE 30 Increases in dry weight of pepper seedlings sprayed with compounds according to the invention of the formula R-COOH (1fig/l) 32 days after germination and harvested 4 days then (6 plants per group, 5 replicates) TABLE 31 Increases in marketable yield of pepper (cv. "Red Chili") sprayed with mixtures 6 according to the invention at 22°C and pH 7.2 when the plants had 4 to 5 sets of distinct leaves. TABLE 32 Increases in marketable yield of lettuce (cv. "Buttercrunch") sprayed with Mixture 7 at pH 7.5 and 25°C and 76% relative humidity. The plants had 4 to 5 sets of distinct leaves and were harvested 1 month after spraying TABLE 33 Increases in growth of potatoes<*>(cv. "Irish Cobler") sprayed with mixtures of different compounds in sam answer with the invention (mixture 7) 24 days after planting and harvested 6 days after spraying (pH 7.6, 5 repetitions).

TABLE 34 Increases in marketable yield of radishes (cv. "Champion") sprayed with different mixtures according to the invention (mixtures 6 & 8) at 27°C when the plants had 3 pairs of distinct leaves (pH 6.9). The scales

is for 5 plants per group, repeated 5

times.

TABLE 35 Increases in growth of Kentucky Bluegrass (mixture) treated with Mixture 8 in accordance with the invention at various developmental stages with a feed rate equivalent to 19 L/measure (29°C, pH 7.5, repeated 5 times). TABLE 36 Increases in the number of harvestable fruits of certain crops sprayed with mixtures according to the invention (mixtures 2, 3, 6 & 7) observed in the middle of the growing season (compared to control groups). TABLE 37 Increases in the dry weights of other seedlings sprayed with compositions according to the invention (mixture 1) at pH 9 to 9.5 and 22 to 26°C, harvest 4 to 7 days thereafter.

TABLE 38 Increases in the yield of alfalfa (cv. "Kansas") sprayed with mixtures according to the invention containing 10 ug/l beeswax and 10 mm CaCl2 with pH 7.4.

After the plants were 15 to 20 cm tall. The plants were harvested on two occasions when they were 30 cm tall. TABLE 39 Increases in salable yield of beans (cv. "Blue Lakes") and snake cucumbers (cv. "Straight 8") treated with mixture 8 in accordance with the invention (Beeswax = 10 jig/l, CaCl2 = 10 mm) applied in a quantity of 10 l/measure.

EXAMPLE XI: ANIMAL FORMS - MAIZE

A thorough examination of the effects of the mixtures according to the invention was carried out using different animal form corn cultivars, as animal form corn is the major agricultural specialty in the United States. Table 1 shows the results obtained by promoting the growth of animal form ice seedlings (cv. "Pioneer 3780") using different mixtures in accordance with the invention, and further shows how additional plant growth substances can be used to increase the effective area of metal- ion concentrations effective in the mixtures for stimulating corn growth. Generally, the addition of such substances is not necessary in the compositions because of the wide range of effective concentrations of metal ions for animal feed corn (between about 1.5 and 4 mm is preferred). Fig. 1 further shows the extremely low concentrations of a compound, namely 1-triacontanoic acid, which are effective for stimulating plant growth, and also the wide range of concentrations which can be used while maintaining a high level of growth stimulating action in maize seedlings.

While Ca is the preferred metal ion in accordance with the invention due to low cost and other factors described above, Table 2 shows the effectiveness of a large number of metal ions with a valence of +2 or more in mixtures in accordance with the invention. The given data clearly indicate that all polyvalent metal ions are useful in the mixtures for stimulating plant-+2

the growth. While some metal ions, such as Cd, are somewhat more effective than others, their use can be expected to be more limited due to the relatively high toxicity, and the use of these metal ions can best be limited to plant life that is not used for food purposes, etc.

Table 3 shows the effectiveness of a wide range of compounds according to the invention in combination with Ca + 2 on animal form ice (cv. "Pioneer 3780") with from 24 to 48 carbon atoms in the chain of the carboxylic acids or their esters. The pH of the solutions applied to the maize seedlings also did not appear to have any effect on the results obtained, with similar increases in dry weight observed for mixtures at pH 9.3 and 5.2.

Tables 4 and 5 show additional data for animal form ice (cvs. "Pioneer 3320" and "- 3382", respectively), and

includes the mixture of esters contained in beeswax. In these and other examples it was found that the use of technical grade CaCl^ did not affect the results obtained with the mixtures, nor did the use of hard water. This indicates that the mixtures 6&7 in accordance with the invention are very economical due to the low price for both beeswax and CaC3 of technical purity. The CaC₂ used is further known to contain approximately 11% CaC₂, the rest being either other metal ion salts, some of which are in accordance with the invention.

Table 6 shows the effect of temperature on cv. "Pioneer 3572" when treated with different mixtures and surprisingly indicates that lower application temperatures for animal form ice cultivars may be preferred. Since animal form ice is usually sprayed with the compositions according to the invention at an early stage and since spraying is usually carried out by the growers either early in the morning or in the evening when the temperatures are lower, this appears to be advantageous.

Table 7 compares the application quantities of mixtures in accordance with the invention on cultivars respectively. "Pioneer 3744" and "Pioneer 3535". The data indicate that smaller application amounts may be preferred over larger ones so that application of compositions according to the invention becomes even more profitable. "Pioneer 3535" reacts relatively poorly compared to other tested cultivars and this may be due to the high growth rate observed with this cultivar. However, Table 8 shows that the stage at which the cultivar is sprayed affects the results and other cultivars can be expected to respond to a higher degree when sprayed at different stages.

Table 9 shows the effects of the mixtures on cv.

"Beck 65X" and further shows that no further effect was observed with further sprayings. However, it has been observed that maize plants sprayed on the field with several sprays show the appearance of an additional skein per plant that is not observed in control plants. While this effect may depend on the variety of maize used, it has been observed with single sprays on cv. "Trojan TXS-94", but not by cv. "Pioneer 3535".

Tables 10 and 11 show additional data obtained with

cvs. "DeKalb XL-61" and "Trojan T-1000". Further support is given in Table 10 for the use of smaller feed amounts, and Table 11 shows the effectiveness of long chain esters of formula R-COOR' in which R = 24 carbon atoms and R' = 24 to 30 carbon atoms. A reduced effect is observed as R' increases in length for this variety of animal form ice, and in general the use of the wax esters shows improved results over the use of the free acids.

Also nervonic acid, a 24 carbon unsaturated acid (cis-15-tetracosenoic acid) shows some effect similar to that observed under the same conditions when beeswax was added to the compositions according to the invention. It is interesting to note that this cultivar ("T-1000") and other later maturing cultivars react better at a relatively higher temperature than the cultivars mentioned so far. As these cultivars require a longer time to reach a stage where spraying should be carried out, this can be advantageous as the temperatures at which the cultivars should be sprayed will be higher at this point in the growing season and further benefit can be offered thereby.

Tables 12 and 13 show that the mixtures in accordance with the invention show compatibility with fertilizers and herbicides for cultivars respectively. "Trojan T-950" and "Trojan T-1100". While fertilizers with a high phosphate content can precipitate the metal ions in accordance with the invention in aqueous solution, the effects of increasing the growth of maize seedlings are nevertheless noticeable. While cultivar "T-1100" requires a high temperature for activity when sprayed with the mixtures compared to other tested cultivars, an improved result, showing statistical significance, is observed with the inclusion of a urea/Zn<+2>foliar fertilizer in the mixture even at the lower temperature. Addition of the herbicide "Banvel D" also shows a slightly improved result, but this was not found to be statistically significant. This indicates that the mixtures in accordance with the invention are useful when combined with agricultural products in common use, thereby reducing further labor costs that would be incurred by a separate, additional spraying of the mixtures.

Table 14 compares the results observed using the mixtures according to the invention containing beeswax and 1-triacontanyl tetracosanoate and the mixtures from prior art (as described in US patent document no. 4,333,758 and related applications). In the prior art, 1-triacontanol, which is also contained in beeswax in small amounts, is found to stimulate plant growth only at alkaline pH, as shown for cultivar "Pioneer 35 35". Table 14 shows that no growth stimulation is observed with metal ions alone in solution, and that the triacontanol mixture containing NAA is effective only at alkaline pH. No results are observed when triacontanol is applied to plant life using the compositions according to the invention containing a metal ion concentration of 2 mm at pH 7.3, triacontanol being present at a concentration of 0.1 mg/l, i.e. ten times as large an amount as in the beeswax present in solution in mixtures used under the same conditions.

An ester of tetracosanoic acid which is also present in beeswax, namely 1-triacontanyl tetracosanoate, is also very effective for stimulating plant growth in the mixtures used herein and this indicates that the carboxylic acid part is necessary for the activity of the compounds according to the invention so that the invention is clear different from prior art.

Field trials conducted with animal form ice showed positive results for a number of cultivars tested, two of which are shown in Table 15. The cultivar "Trojan TXS-94" showed typical results found with other cultivars, and cultivar "Pioneer 3535", a cultivar found to respond relatively poor compared to other tested cultivars, showed somewhat smaller increases. However, after examining the data for this cultivar, it was observed that the conditions used in the field trials differed from those recommended for short-term greenhouse trials (see Table 7) in that the mixtures containing beeswax were found to be more effective at a lower spraying, temperature than the temperature at which the mixtures were sprayed during field trials. Based on this observation, it can be concluded that animal form ice reacts more favorably when the plants have been developed further than the three-leaf stage, but this is not necessary for the activity. A further observation of interest is that this cultivar of animal form ice responds to mixtures in accordance with the invention up to approximately the seven-leaf stage in greenhouse experiments, the activity being observed to be reduced at this stage (Fig. 3). In field trials, however, increases in crop yield are noted even when the seedlings were sprayed at the seven-leaf stage (table 15). However, this may be due to the fact that plants treated in greenhouse-controlled environments with mixtures in accordance with the invention are grown in pots so that this causes limited volume for root growth to be a contributing factor.

It is therefore clear that positive results are obtained by applying mixtures according to the invention under a number of different conditions and stages of plant growth, but by changing the conditions under which mixtures according to the invention are added, the results observed from there can be improved.

EXAMPLE XII: SOY BEANS

As shown in Table 16, soybean seedlings respond well to compositions according to the invention at preferred metal ion concentrations between about 5 and 15 mm. When the results obtained in this manner are compared with those of compositions in accordance with the prior art, as more fully described in the preceding discussion for animal forms, the present invention differs from the prior art in that soybean seedlings have been found to respond to mixtures of triacontanol only when the land in which they are grown has a sufficiently high phosphate content. From these results, it becomes clear to the person skilled in the art that the growth-stimulating effect of the mixtures according to the invention containing beeswax cannot be attributed to traces of 1-triacontanol contained therein, or in other naturally occurring waxes (see table 17). It is further observed that the naturally occurring constituents which are compounds according to the invention, especially waxy esters, are very active in promoting the growth of soybean seedlings and unsaturated acids are also effective in mixtures according to the invention containing metal ions.

The step in which the seedlings are treated changes the reaction obtained to some extent, with a step between approximately the second and fourth trifoliate steps being preferred. The temperature at which soybeans are preferably sprayed or otherwise treated with compositions in accordance with the invention also appears to be wider than those observed in the case of animal form ice seedlings. Similar results are found using other soybean cultivars, such as cultivar "Essex" and the like.

As in the case of other crops, it is also observed that soybeans react preferentially to straight-chain carboxylic acids or salts or derivatives thereof which have a relatively longer hydrocarbon chain length than other crops such as tomatoes, peas and the like, i.e. that compounds with approximately 30 carbon atoms produce a better reaction when they are combined in the compositions of the invention than compounds of the invention having only about 24 carbon atoms or less. E.g. it turns out that animal form ice reacts to a relatively longer hydrocarbon chain length in the mixtures than tomatoes (see fig. 2).

Increases in yield of soybean crops have been observed (Table 18) using cultivar "Williams" and other cultivars. Soybeans also appear to show a rapid increase in growth in field trials, like many other crops, shortly after application of the compositions in accordance with the invention.

EXAMPLE XIII: PEAS

Peas were tested with mixtures in accordance with the invention with favorable results, both in greenhouse trials and on

the field. A comparison of greenhouse data indicated in

tables 19 and 20 with the relevant field test data obtained and shown in table 21 show that increases in the field promoted by application of the mixtures can be expected to be as large as or exceed those observed in the short-term greenhouse trials. It is therefore clear that the methods used in these greenhouse trials at an early stage of plant development provide a method that is very useful both in predicting the optimal mixtures for use in field trials and in predicting the minimum increase in crop yield that can be expected when applying the optimal mixtures.

Unlike soybeans, peas react to mixtures in accordance with the invention to a greater extent when the hydrocarbon chain length of the compounds contained therein is relatively short, i.e. 22 or 24 carbon atoms compared to approximately 30 carbon atoms. The mixtures according to the invention are also found to be superior in stimulating the growth of pea cultivars which react somewhat poorly to triacontanol mixtures, such as e.g. cultivar "Suggar Snap" (prior technique) both in the greenhouse and in the field.

In the case of peas, it may be desirable to use other more economical, naturally occurring waxes, oils, etc. which contain a lower average molecular weight hydrocarbon chain, such as peanut oil (C-^ to <C>24), jojoba oil (C20 to C22) and other such waxes and oils and the like obtained from vegetable and animal sources. Other compounds within the scope of the invention which show increases in the growth of peas and . can be expected to show increases in the growth of other plant life when used in accordance with the invention also includes, but is not limited to, erucic acid, tribehenin, dibehenoyl-phosphatidyl-choline (or other acidic phospholipids) etc., the smaller reactions being observed for compounds such as 4 , 7, 10, 13, 16, 19-docosahexaenoic acid, 2-hydroxydocosanoic acid, lecithin, etc.

EXAMPLE XIV: TOMATOES

Several cultivars of tomatoes were treated with mixtures

in accordance with the invention with similar increases in the knowledge thereby induced. Data for the two cultivars shown in Table 22 indicate that tomatoes react to mixtures in accordance with the invention containing compounds of the formula R-COOR' in which R is between 16 and 36 carbon atoms with respect to the chain length, a relatively shorter hydrocarbon chain length being preferred over the case of soybeans . The most preferred hydrocarbon chain lengths are those where R = 16 to about 24 carbon atoms, ie

20 carbon atoms are preferred (Fig. 2). As a result, many naturally occurring waxes, oils, etc. useful in mixtures in accordance with the invention, such as beeswax (C24 to <C>36), jojoba wax or oil (C2Q to C22), olive oil (C^6 to C2q), rice bran oil (C-^g to C^g), soybean oil and the like. In fact, human sebum can be expected to have an effect on plant life when combined in mixtures according to the invention and to effect growth in plant life.

Some differences between tomato cultivars appear from their reaction to mixtures according to the invention, as shown for the two cultivars in Table 22 with their reaction to mixtures containing eicosanoic acid (C^q)• While increases in plant growth are seen either with saturated or unsaturated compounds in the mixtures , a significant reduction in plant growth is observed when the hydrocarbon chain is reduced to approximately 14 carbon atoms. As the prior art teaches that such compounds are inhibitory with regard to their effects on plant growth as described more fully in the preceding background of the prior art when supplied without the addition of metal ions in accordance with the invention, including the 14 carbon analogue and right analogues , the surprising transition between growth inhibition and growth stimulation observed using compositions according to the invention containing these compounds is not clear as to the possible mechanism by which the compositions herein achieve their results. It may also be possible that compositions such as those described herein containing relatively low molecular weight compounds (eg, wherein R = 14 carbon atoms or less) known to cause growth inhibition may be superior in their growth enhancing effects of plant life when combined with metal ions in accordance with the invention.

Preliminary observations during field trials with tomatoes have shown that large increases in the number of tomatoes occur on plants sprayed with the mixtures in accordance with the invention. As a result of field trials, marketable increases in yield are found to be similar to increases in dry weight observed in greenhouse trials (see Tables 22 and 23). Other cultivars have been found to show increases in yield, e.g. cv. "Campbells 1327" gave 20 to 34% higher yields compared to controls, and cv. "Ace 55" showed increases up to 31%.

In addition to increases observed when tomato seedlings were sprayed with compositions according to the invention, increases in dry weight of seedlings grown from seeds impregnated in a mixture containing beeswax (10 ug/l)

+2

and Ca (10 mm) for 1.5 h before planting observed to be 33% above control plants grown from untreated seed

(p = 0.01) when the plants reached a stage where they had 4

set of distinct leaves. This result indicates that compositions according to the invention are very effective in improving the quality of seeds before planting and this method of application may be preferred for seeds of various crops that require long periods of time to germinate and produce seedlings of suitable size for planting in the field, such as tomatoes , tobacco, celery, lettuce, wheat, rice etc. Subsequent application of the compositions as foliar spraying, ground impregnation and the like can be expected to further improve the growth of plant life and yields of certain crops.

EXAMPLE XV: WHEAT

Winter wheat was tested with compositions in accordance with the invention under various conditions and found to respond comparably to animal form ice with regard to observed increases in dry weight. It was noted, however, that the concentrations of metal ions used in the mixtures for an optimal effect were somewhat higher than observed for most other crops and plant life and similar to that observed for peas.

Table 21 shows the range of metal ion concentrations effective in mixtures for winter wheat (cv. "Potomac") and compares them to those found useful in the prior art. It is observed that the temperatures at which a reaction is observed when the mixtures are added to wheat seedlings are significantly lower than the equivalent whereby previously known techniques show an effect in plant growth stimulation. The metal ion concentration that is effective is also lower than that required for optimal activity using previously known compositions. This offers two advantages: (1) the costs of compounding the product are reduced and (2) the temperature at which winter wheat is sprayed in the spring need not be high,

which is rarely the case in the field at this particular time of year when wheat is usually grown.

Table 22 shows that the optimum metal ion concentration in mixtures used for wheat in these examples is about 15 mm and is superior to the mixture containing 20 mm metal ions by about 47%. The prior art teaches that the preferred metal ion concentration used in triacontanol mixtures is 20 to 25 mM or more. An interesting result is noted that when the wheat seedlings are exposed to a lack of water, such as under drought conditions every day between spraying the seedlings and autumn, the water content of the seedlings rises very sharply, somewhat at the expense of an increase in dry weight. This may indicate that the mixtures according to the invention are useful in inducing drought resistance in plant life, and while drought seems to affect the observed dry weight increases to some extent, as might be expected, they are no less observed and are statistically significant. Normal increases in water content observed in the case of wheat, and many other plants tested, are of the order of between about 7 and 10% compared to 19 to 45% increases observed over control groups under the water deficit conditions described.

Concentrations of metal ions above about 20 mm in combination with the metal ions in the mixtures according to the invention show a reduction in the results obtained which amount to only about 4% increase in dry weight over controls at a Ca concentration of 25 mm.

An increase in the dry weight of wheat seedlings was also observed using a soil impregnation mixture, shown in Table 2-2, which was 7% higher than the dry weight of controls treated with an identical +2

solution containing only Ca . While this increase is only about half of that observed in the case of foliar application of the mixtures, the result can be expected to vary with the amount of solution applied to the soil. However, due to the greater amount of solution required when using ground impregnation, this method of application is not preferred, but is nevertheless effective.

Results from field trials can be expected to be as good as or exceed those observed in these short-term greenhouse trials, as described in the previous description.

EXAMPLE XVI: SWEET CORN

The mixtures according to the invention were found active in promoting the growth of sweet corn seedlings when applied in accordance with the methods according to the invention. The observed increases were found to be approximately the same as those observed for animal form ice seedlings in greenhouse experiments under the conditions used, but the concentrations of metal ions in accordance with the invention necessary for a reaction were found to be somewhat higher than those used in the case of animal formais. Concentrations of metal ions in applied mixtures that can be considered optimal are between about 3 mm and 10 mm, with between about 7.5 mm and 10 mm being preferred for sweet corn (Table 26).

About 2 weeks before the harvest, sweetcorn plants showed approximately 22% more ears per group than control plants on average, and with a clear increase in spikelet size. Plants sprayed at the 4th leaf stage produced increases in salable yield of up to 51%

(see tabe-1 27) for cv. "Golden Cross Bantam" below

+2 use of mixtures containing 10 mm Ca and compounds in accordance with the invention.

EXAMPLE XVII: TOBACCO

Tobacco seedlings were tested with mixtures according to the invention with the results shown in Table 28. Optimum concentrations of polyvalent metal ions useful on tobacco seedlings are within a wide range, similar results being observed 4 days after foliar spraying with mixtures containing between 5 mm and 15 mm Approx +2. Metal ions outside this range also produce effective plant growth stimulation. Similar activity is found with other tobacco cultivars, the preferred application stage being between about 1 to 3 weeks after the seedlings have been set out in the field. Application of the compositions according to the invention is best carried out at temperatures of about 22°C or more, preferably between about 22 and 33°C, but positive results can be observed outside this temperature range. Furthermore, tobacco seeds, which require quite a long time to germinate and reach a size suitable for planting in the field, can be impregnated in compositions according to the invention before planting in beds to help improve both germination and increase the rate of growth thereof.

EXAMPLE XVIII: COTTON

Cotton seedlings respond favorably to the described compositions according to the invention, with increases in growth found in greenhouse experiments shown in Table 29.

The leaves of cotton seedlings are readily coated with aqueous solutions of compositions according to the invention without the aid of any surface-active additives, similarly to leaves of other dicot types such as cowpeas and the like, when applied as foliar sprays, and improved reactions are observed at temperatures preferably 24° C and more. Both the carboxylic acids and their esters in accordance with the invention (or their salts) and especially waxy esters cause significant growth increases measured on the basis of dry weights and compared to control groups. However, the inclusion of esters, and especially waxy esters, shows slight differences in the observed reactions using carboxylic acids and their salts. However, the increases in the heights of the seedlings were also determined and these were found to be about 5 to 15% different compared to the controls.

EXAMPLE XIX: PEPPER

Pepper seedlings respond well to the different mixtures in accordance with the invention, as greenhouse trial results with cv. "Early California Wonder" is reproduced in Table 30. An unusual reaction to mixtures containing different metal-ion concentrations and different compounds of the invention is observed, with a somewhat different metal-ion concentration being preferred for compounds of the invention with varying hydrocarbon chain lengths. Thus, while significant increases in dry weight were observed with seedlings sprayed with mixtures containing triacontanoic acid and Ca + 2 (10 mm) or with tetracosanoic acid and Ca<+2> (5 mm), no particular increase was observed when metal ion concentration the on was raised to 10 mm or more using the mixtures containing tetracosanoic acid on cultivar. At mid-season, a large increase in the number of pepper fruits on treated plants was observed compared to the number of pepper fruits on control plants and the final yield of pepper fruits was found to be 82% compared to the controls (see Tables 30 and 36).

EXAMPLE XX: SALAD

Lettuce (cv. "Buttercrunch") was treated with two

mixtures in accordance with the invention and allowed to ripen before harvesting. Table 32 shows the increases in salable yield found using compositions according to the invention containing beeswax and various

+2

concentrations of approx. Lettuce appears to respond to metal-ion concentrations over a wide range as in the case of tobacco given above.

EXAMPLE XXI; POTATOES

Table 33 shows that mixtures according to the invention are effective for stimulating the growth of potatoes. Data contained therein also indicate that potatoes respond at a preferred temperature at the time of application below about 24°C, with a temperature of about 21°C being preferred. This finding is advantageous for the grower as potatoes are generally grown in colder climates and a relatively higher temperature at the time when mixtures in accordance with the invention can be added is less likely to occur at the time of application of the mixtures. It is important to note that root crops showing an increase in the : dry weight of the foliage obtained therefrom also show similar increases in the size and weight of the crop itself after treatment with compositions in accordance with the invention. For this reason, the dry weight of potato seedling foliage was used as an indication of growth to predict optimal compositions according to the invention useful in the field to produce increases in crop yield.

EXAMPLE XXII: RADISHES

Table 34 shows increases in marketable yield of radishes found as a result of application of compositions in accordance with the invention. It appears from investigations of the data that radishes preferentially react to the compounds in accordance with the invention which have a relatively high molecular weight. Thus, observed increases with the mixture containing beeswax (a mixture containing compounds of the formula R-COOR' in which R and R' are alkyl groups of length between 24 and 36 carbon atoms) and metal ions were found to be 35% above the controls, while application of tetracosanoic acid (C^) alone showed an increase in yield of 47% over the controls. High metal ion concentrations, i.e. 15 mm or more, are not found to produce any significant increases in crop yield beyond the controls under the conditions stated herein.

EXAMPLE XXIII: GRASS

Grass of economic importance, such as alfalfa, bluegrass, etc. respond to compositions according to the invention as demonstrated by increases in the dry weight of the harvested grass compared to controls (Tables 35, 37 and 38). Some grasses exhibit a growth-stimulating response in a narrow range of growth stages, such as Kentucky bluegrass (Table 35), while alfalfa generally responds over a somewhat broader range of growth stages (eg, 8 to 20 cm height, Tables 37 and 38). Grass harvested for use as animal feed and the like generally responds to the application of compositions in accordance with the invention before the first cutting and increases are observed with a second harvest without further application of the compositions.

EXAMPLE XXIV: VEGETABLES AND OTHER CROPS

Other crops tested have also shown significant increases in marketable yields compared to the controls as a result of application of compositions in accordance with the invention. This and snake cucumbers showed high increases in crop yield and observations of other crops tested indicate that similar results are possible for all crops tested with mixtures in accordance with the invention (Table 39). Onions have shown an increase in size of up to about 42% after treatment with the mixtures, and carrots have shown increases of about 36%. While all data contained herein were developed using the present compositions in the eastern United States, data developed under varying conditions in other parts of the United States indicate that similar results are possible under a wide range of environmental factors.

From the foregoing description and examples of the invention, it becomes clear to the person skilled in the art that the mixtures in accordance with the invention have a wide range of potential and applicability for growth promotion of plant life and increases in crop yields. Polybasic acids are as effective as monobasic acids in the mixtures (Table 3) and esters, especially waxy esters such as those contained in a wide variety of naturally occurring waxes and oils and the like. are very useful in the compositions according to the invention and show some degree of superiority in a number of cases after inclusion in the compositions described herein.

As a result of the remarkable effectiveness of the compositions according to the invention, other effects on plant life are possible from their use, such as improved disease and cold resistance of plant life, and effects of this type have been observed. E.g. sweet corn was found to be susceptible to disease and produced no marketable yield on control plots, but was found to produce normal yields when pre-treated with compositions in accordance with the invention, and other effects similar to these are also observed when applying compositions in accordance with the invention.

Although one does not wish to be bound by any exact mechanism by which the invention achieves the remarkable results, it is possible that the long-chain compounds of the invention may act as "coating agents" in small amounts and which may then assist plant life for use in metal absorption -ions in accordance with the invention as micro-nutrients, foliar fertilizers etc. While other mechanisms are possible, the exact mechanisms have not been clarified.

The importance of using mixtures in accordance with the invention means a high potential in increasing the world's food supply, as well as an economic increase of resources derived from plant life useful as energy sources, building materials, etc. Many other applications that have not yet been realized could be realized from the use of plant life if the supply of plant life resources could become economically abundant, these applications being made possible by the use of the compositions discussed herein. Supply of the mixtures is easily done using the methods described herein and can be done by any other methods practiced in the area, such as adding the components of the mixtures to irrigation systems, supply of the components to plant life as side mixtures to be further diluted with water and is absorbed by the root system in plant life, etc.

With the invention described in this way, it is clear that it can be varied in many ways and such variations are not to be considered as going beyond the idea and scope of the invention and all such modifications that will be clear to the person skilled in the field are intended to be included within the scope of the subsequent patent claims.

Claims (41)

1. Plant growth-stimulating mixture, characterized in that it comprises: a compound of formula or a salt thereof wherein R is a saturated long-chain alkyl group of 15 to 47 carbon atoms, an unsaturated long-chain alkyl group of 15 to 47 carbon atoms, a saturated long-chain alkyl group of 15 to 47 carbon atoms substituted with 1 to 4 carboxyl -groups or an unsaturated long-chain alkyl group with 15 to 47 carbon atoms which is substituted with 1 to 4 carboxyl groups, R' is hydrogen, a saturated alkyl group of 1 to 36 carbon atoms, an unsaturated alkyl group of 1 to 36 carbon atoms, a saturated alkyl group of 1 to 36 carbon atoms substituted with 1 to 4 carboxyl groups or an unsaturated alkyl- group of 1 to 36 carbon atoms substituted with 1 to 4 carboxyl groups, and a metal salt wherein the metal ion in the salt has a valence of +2 to +3 in an aqueous solution, the metal salt being present in the mixture in an amount effective to assist the compound in stimulating plant growth. 2. Mixture as stated in claim 1, characterized in that it consists of a dry mixture comprising the said compound and the said metal salt. 3. Mixture as stated in claim 1, characterized in that the mixture is in the form of a liquid. 4. Mixture as stated in claim 1, characterized in that it is in the form of an aqueous solution or dispersion or in which the mentioned metal salts form metal ions in the solution. 5. Mixture as stated in claim 2, characterized in that the compound is coated on particles of the salt. 6. Mixture as stated in claim 1, characterized in that the compound is a compound found in a naturally occurring wax or oil. 7. Mixture as stated in claim 1, characterized in that it includes a naturally occurring wax or oil containing the said compound. 8. Mixture as stated in claim 7, characterized in that the naturally occurring wax or oil is selected from the group consisting of beeswax, esparto wax, peanut oil, jojoba oil, olive oil, soybean oil and rice-bean oil. 9. Mixture as stated in claim 7, characterized in that the mixture contains beeswax. 10. Mixture as stated in claim 1, characterized in that the compound is a compound with formula or a salt thereof wherein R is a saturated long-chain alkyl group of 15 to 47 carbon atoms and R' is hydrogen or a saturated alkyl group of between 1 and 36 carbon atoms. 11. Mixture as stated in claim 10, characterized in that R' is hydrogen. 12. Mixture as stated in claim 10, characterized in that R' is a saturated long-chain alkyl group with between 1 and 36 carbon atoms. 13. Mixture as stated in claim 4, characterized in that the metal ions are in the 4-c group w 4-« * ~ <+2> T <+3> „ <+2> „ <+2> selected from the group consisting of of Ca, La, Mg, Mn, Sr, Pb, Ba, Cd, Zn, Cu and Co 14. Mixture as stated in claim 4, characterized in that the metal ion is Ca<+2>. 15. Mixture as stated in claim 1, characterized in that the metal salt is a calcium salt. 16. Mixture as stated in claim 7, characterized in that the metal salt is a calcium salt. 17. Mixture as stated in claim 1, characterized in that the weight ratio between the compound and the metal salt is in the range from 1:5 to 1:500,000,000. 18. Mixture as stated in claim 1, characterized in that the compound of formula (I) is present in an amount of 50 pg to 5 g per kg mixture. 19. Method for stimulating plant growth, characterized by adding an effective plant growth-stimulating amount of the mixture specified in claim 1 to the area where the plants grow. 20. Method for stimulating plant growth, characterized by adding an effective plant growth-stimulating amount of the mixture as stated in claim 3 to an area where the plants grow. 21. Method for stimulating plant growth, characterized by adding an effective plant growth-stimulating amount of the mixture as stated in claim 4 to the area where the plants grow. 22. Method for stimulating plant growth, characterized by adding an effective plant growth-stimulating amount of the mixture as stated in claim 6 to the area where the plants grow. 23. Method for stimulating plant growth, characterized by adding an effective plant growth-stimulating amount of the mixture as stated in claim 8 to the area where the plants grow. 24. Method for stimulating plant growth, characterized by adding an effective plant growth-stimulating amount of the mixture as stated in claim 9 to the area where the plants grow. 25. Method for stimulating plant growth, characterized by adding an effective plant growth-stimulating amount of the mixture as stated in claim 10 to the area where the plants grow. 26. Method for stimulating plant growth, characterized by applying an effective plate growth-stimulating amount of the mixture as stated in claim 14 to the area where the plants grow. 27. Method as stated in claim 21, characterized in that the mixture is applied to the leaves of growing plants. 28. Method as stated in claim 21, characterized in that the mixture is applied when the plant life has between 2 and 7 distinct leaves. 29. Method as stated in claim 19, characterized in that the plant life is selected from the group consisting of animal form ice, soybeans, peas, tomatoes, wheat, sweet corn, tobacco, cotton, pepper, lettuce, potatoes, radishes, carrots, alfalfa, barley, beans, sorghum and snake cucumbers. 30. Method for stimulating plant growth, characterized by adding an effective amount of the mixture as stated in claim 1 to plant life selected from the group consisting of animal form ice, soybeans, peas, tomatoes, wheat, sweet corn, tobacco, pepper, cotton., lettuce, potatoes, radishes, carrots, alfalfa, barley, beans, sorghum, cucumbers, bluegrass, onions and vigna beans. 31. Plant growth-stimulating mixture, characterized in that it comprises 0.1 ug to 10 g per kg of the mixture of a compound of formula: or a salt thereof wherein R is a saturated long-chain alkyl group having 15 to 47 carbon atoms, an unsaturated long-chain alkyl group having 15 to 47 carbon atoms, a saturated long-chain alkyl group having 15 to .47 carbon atoms substituted with 1 to 4 carboxyl groups or an unsaturated long-chain alkyl group of 15 to 47 carbon atoms which is substituted with 1 to 4 carboxyl groups, R' is hydrogen, a saturated alkyl group of 1 to 36 carbon atoms, an unsaturated alkyl group of 1 to 36 carbon atoms, a saturated alkyl group with 1 to 36 carbon atoms substituted with 1 to 4 carboxyl groups or an unsaturated alkyl group with 1 to 36 carbon atoms substituted with 1 to 4 carboxyl groups, and 50 g to 1,000 g per kg of the mixture of a metal salt in which the metal ion in the salt has a valence of +2 or +3 in an aqueous solution. 32. Mixture as stated in claim 31, characterized in that the compound of formula (I) is present in an amount of 50 ug to 5 g per kg of the mixture and the metal salt is present in an amount of 250 g to 1,000 per kg of the mixture. 33. Mixture as stated in claim 31, characterized in that the compound of formula (I) is a compound found in naturally occurring waxes or oil. 34. Mixture as stated in claim 32, characterized in that the mixture includes a naturally occurring type of wax or oil selected from the group consisting of beeswax, esparto wax, peanut oil, jojoba oil, olive oil, soybean oil and rice husk oil. 35. Mixture as stated in claim 32, characterized in that the mixture contains beeswax. 36. Mixture - as stated in claim 31, characterized in that the compound is a compound with formula: or a salt thereof wherein R is a saturated long-chain alkyl group of 15 to 47 carbon atoms and R' is hydrogen or a saturated alkyl group of between 1 and 36 carbon atoms. 37. Mixture as stated in claim 31, characterized in that the metal salt is a calcium salt. 38. Mixture as stated in claim 34, characterized in that the metal salt is a calcium salt. 39. Mixture as stated in claim 35, characterized in that the metal salt is calcium chloride. 40. Mixture as stated in claim 31, characterized in that the metal ions are selected from the group consisting of Ca , La , Mg + 2 , Sr <+2> , TM+2 +2 „,+2 +2 +2 + 2 Pb, Ba, Cd, Zn, Cu and Co 41. Method for stimulating plant growth, characterized by adding an aqueous solution containing an effective plant growth-stimulating amount of the mixture as stated in claim 31 to the leaves of growing plants.