WO1999055645A1

WO1999055645A1 - Agricultural adjuvant

Info

Publication number: WO1999055645A1
Application number: PCT/US1999/006553
Authority: WO
Inventors: Frank J. Lachut; David R. Clark; Roger H. Garst; Rudolph F. Klima
Original assignee: Henkel Corp; Cognis Corp
Current assignee: Henkel Corp; Cognis Corp
Priority date: 1998-04-29
Filing date: 1999-04-29
Publication date: 1999-11-04
Anticipated expiration: 2000-10-29
Also published as: AU3740499A

Abstract

An adjuvant composition containing: (a) an oil component; (b) a nonionic surfactant component; (c) an anionic surfactant and (d) a fertilizer component.

Description

TITLE OF THE INVENTION

Agricultural Adjuvant

BACKGROUND OF THE INVENTION The present invention generally relates to adjuvants used to formulate agricultural compositions. More particularly, the invention relates to a novel adjuvant composition which, when used in combination with a biologically active ingredient, significantly potentiates the performance of the product. It is known that various agricultural materials such as insecticides, insect repellents, fungicides, bactericides, herbicides, and plant growth regulators may be formulated into various products for use on crops and ornamental plants, for controlling weeds, insects and the like. These products may be applied in the form of a liquid or a semi-solid dispersion. Regardless of the method of application, it is advantageous to include within the product an adjuvant in order to enhance the effectiveness and performance of the agricultural product's active ingredient, thereby requiring less actives to be used to perform a certain function.

While the use and application of individual adjuvants in an agricultural product is generally known, the combination of multiple adjuvants into a single, yet compatibly soluble adjuvant composition poses various stability problems. Due to the chemical dissimilarities associated with the individual adjuvant compounds, it is oftentimes not possible to effectively disperse each of the individual adjuvants into a single homogeneous formulation.

BRIEF SUMMARY OF THE INVENTION The present invention is directed to an adjuvant composition containing:

(a) an oil component selected from the group consisting of a fatty acid 2 ester, a seed oil, a petroleum oil, a fatty acid, a fatty alcohol, a fatty ether, an fatty amide, a glyceride and mixtures thereof;

(b) a nonionic surfactant selected from the group consisting of sugar surfactants, alkoxylated fatty alcohols, alkoxylated fatty acids, alkoxylated fatty ethers, alkoxylated fatty amides, ethoxylated seed oils, ethoxylated mineral oils, nonylphenol ethoxylates, alkoxylated alkyl phenols, ethoxylated glycerides, castor oil ethoxylates and mixtures thereof;

(c) an anionic component; and

(d) a fertilizer component. The present invention is also directed to an agricultural composition containing:

(a) an adjuvant composition containing:

(i) an oil component selected from the group consisting of a fatty acid ester, a seed oil, a petroleum oil, a fatty acid, a fatty alcohol, a fatty ether, a fatty amide, a glyceride and mixtures thereof;

(ii) a nonionic surfactant selected from the group consisting of sugar surfactants, alkoxylated fatty alcohols, alkoxylated fatty acids, alkoxylated fatty ethers, alkoxylated fatty amides, ethoxylated seed oils, ethoxylated mineral oils, nonylphenol ethoxylates, alkoxylated alkyl phenols, ethoxylated glycerides, castor oil ethoxylates and mixtures thereof;

(iii) an anionic component; and

(iv) a fertilizer component; and

(b) a biologically active ingredient.

The present invention is also directed to a process for treating an agricultural substrate involving contacting the substrate with the above- disclosed agricultural composition.

DETAILED DESCRIPTION OF THE INVENTION Other than in the claims and in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients or reaction conditions used herein are to be understood as modified in all instances by the term "about". 3

The term "agricultural substrate", as used herein, means a plant. The adjuvant composition of the present invention is a combination of at least three adjuvant components, namely, an oil component, certain nonionic surfactants, an anionic component and a fertilizer component. Suitable oil components include those selected from the group consisting of a fatty acid ester, a seed oil, a petroleum oil, a fatty acid, a fatty alcohol, a fatty ether, a fatty amide, a glyceride and mixtures thereof.

These oily compounds tend to soften the outer waxy layer of the plant substrate being treated, thereby enabling the biologically active substance to better penetrate into the plant.

Fatty acid esters which may be used are those having the general formula:

R₂COOC_nH_2n+1 wherein R₂ is an alkyl radical having from about 4 to about 22 carbon atoms, and n is a number from 1-4. They are derived by the esterification of a fatty acid with an alkanol. Preferred fatty acid esters are methyl and ethyl esters derived from the esterification of unsaturated fatty acids having from about 18 to about 22 carbon atoms. Particularly preferred methyl esters include methyl oleate, methyl laurate and methyl soyate. Preferred ethyl esters include ethyl oleate and ethyl canolate. Suitable fatty acids from which the fatty acid esters may be derived include, but are not limited to, coconut and other vegetable oils, tallow, etc.

Alkoxylated fatty acid esters may also be employed. These include fatty acid esters such as those listed above which are alkoxylated with ethylene oxide, propylene oxide and combinations thereof.

Fatty alcohols which may be employed in the present invention are saturated or unsaturated, branched or linear C₈-C₂₀ alcohols. High molecular weight alcohols may be produced synthetically by the Oxo and Ziegler processes. Those having from 8 to 11 carbon atoms are generally oily liquids. On the other hand, those having greater than 11 carbon atoms are generally solids. Other methods of production are (1) reduction of vegetable seed oils and their fatty acids with sodium, (2) catalytic hydrogenation at 4 elevated temperatures and pressures, and (3) hydrolysis of spermaceti and sperm oil by saponification and vacuum fractional distillation.

The more important commercial saturated alcohols are octyl, decyl, lauryl, myristyl, cetyl and stearyl. The commercially important unsaturated alcohols include oleyl, linoleyl and linolenyl. Guerbet alcohol ethoxylates may also be employed as a carrier component.

The fatty acids which may be employed in the present invention are those composed of a chain of alkyl groups containing from 4 to 22 carbon atoms and characterized by a terminal carboxyl group. The fatty acids may be saturated such as, for example, butyric, lauric, palmitic and stearic or unsaturated such as, for example, oleic, linoleic and linolenic.

The fatty ethers which may be employed are those generally derived from fatty alcohols, such as those listed above, by the elimination of water. They are generally characterized by the formula ROR wherein R is an alkyl group containing from 4 to 22 carbon atoms.

Similarly, the fatty amides which may also be employed are those characterized by the general formula R=CONH₂ wherein R is an alkyl group having from 4 to 22 carbon atoms.

Suitable seed oils are those derived from seeds and nuts and include, but are not limited to, castor, coconut, soybean, and the like. Preferred seed oils include soybean oil.

Useful petroleum oils include, but are not limited to, petroleum and petroleum-derived oils. Preferred petroleum oils include mineral oils.

Suitable glycerides include those derived from glycerol and a C^ fatty acid. Preferred glycerides include glycerol mono/di oleate.

Suitable nonionic surfactants for use in the present invention include sugar surfactants, alkoxylated fatty alcohols, alkoxylated fatty acids, alkoxylated fatty ethers, alkoxylated fatty amides, ethoxylated seed oils, ethoxylated mineral oils, nonylphenol ethoxylates, alkoxylated alkyl phenols, ethoxylated glycerides, castor oil ethoxylates, and mixtures thereof.

Suitable sugar surfactants include those selected from the group consisting of an alkyl polyglycoside, an alkyl glucose ester, an aldobionamide, 5 a gluconamide, a glyceramide, a glyceroglycolipid, a polyhydroxy fatty acid amide and mixtures thereof.

The alkyl polyglycosides which may be employed in the present invention are those corresponding to the formula: R₁0(Z)_a wherein R_t is a monovalent organic radical having from about 6 to about 30 carbon atoms; Z is saccharide residue having 5 or 6 carbon atoms; a is a number having a value from 1 to about 6. The alkyl polyglucosides which can be used in the compositions and processes according to the invention are commercially available, for example, as APG® surfactants, GLUCOPON® surfactants, AGRIMUL® surfactants, or PLANTAREN® surfactants from Henkel Corporation, Ambler, PA, 19002. Examples of such surfactants include but are not limited to:

1. AGRIMUL® PG 2067 Surfactant - an alkylpolyglycoside in which the alkyl group contains 8 to 10 carbon atoms and having an average degree of polymerization of 1.7.

2. AGRIMUL® 2072 Surfactant - an alkyl polyglycoside in which the alkyl group contains 8 to 16 carbon atoms and having an average degree of polymerization of 1.6. 3. AGRIMUL® 2065 Surfactant - an alkyl polyglycoside in which the alkyl group contains 12 to 16 carbon atoms and having an average degree of polymerization of 1.6.

4. APG® 300 Surfactant - an alkyl polyglycoside substantially the same as AGRIMUL® 2069 Surfactant but having an average degree of polymerization of 1.4.

5. AGRIMUL® PG 2069 Surfactant - an alkyl polyglycoside in which the alkyl group contains 9 to 11 carbon atoms and having an average degree of polymerization of 1.6.

6. AGRIMUL® 2062 Surfactant - an alkyl polyglycoside in which the alkyl group contains 12 to 16 carbon atoms and having an average degree of polymerization of 1.4.

7. PLANTAREN® 2000 Surfactant - a C_8-16 alkyl polyglycoside in which the 6 alkyl group contains 8 to 16 carbon atoms and having an average degree of polymerization of 1.4.

8. PLANTAREN® 1300 Surfactant - a C₁₂.₁₆ alkyl polyglycoside in which the alkyl group contains 12 to 16 carbon atoms and having an average degree of polymerization of 1.6.

Other examples include alkyl polyglycoside surfactant compositions which are comprised of mixtures of compounds of formula I wherein Z represents a moiety derived from a reducing saccharide containing 5 or 6 carbon atoms; a is zero; and R₁ is an alkyl radical having from 8 to 20 carbon atoms. The composition is characterized in that it has increased surfactant properties and an HLB in the range of about 10 to about 16 and a non-Flory distribution of glycosides, which is comprised of a mixture of an alkyl monoglycoside and a mixture of alkyl polyglycosides having varying degrees of polymerization of 2 and higher in progressively decreasing amounts, in which the amount by weight of polyglycoside having a degree of polymerization of 2, or mixtures thereof with the polyglycoside having a degree of polymerization of 3, predominate in relation to the amount of monoglycoside, said composition having an average degree of polymerization of about 1.8 to about 3. Such compositions, also known as peaked alkyl polyglucosides, can be prepared by separation of the monoglycoside from the original reaction mixture of alkyl monoglycoside and alkyl polyglycosides after removal of the alcohol. This separation may be carried out by molecular distillation and normally results in the removal of about 70-95% by weight of the alkyl monoglycosides. After removal of the alkyl monoglycosides, the relative distribution of the various components, mono- and poly-glycosides, in the resulting product changes and the concentration in the product of the polyglycosides relative to the monoglycoside increases as well as the concentration of individual polyglycosides to the total, i.e., DP2 and DP3 fractions in relation to the sum of all DP fractions. Such compositions are disclosed in U.S. Patent No. 5,266,690, the entire contents of which are incorporated herein by reference.

Preferred alkyl polyglycosides are those in which the alkyl group 7 contains from 8 to 12 carbon atoms and having an average degree of polymerization of 1.6 to 1.7. The most preferred alkyl polyglycosides are those which have alkyl groups containing 8 to 10 carbon atoms and having an average degree of polymerization of 1.7 and those which have alkyl groups containing 9 to 11 carbon atoms and having an average degree of polymerization of 1.6.

The alkyl glucose ester sugar cosurfactants are generally disclosed in U.S. Patent Nos. 5,109,127 and 5,190,747, the entire contents of both being incorporated herein by reference. These sugar cosurfactants have the general formula:

RC(θ)qϊ₂ H O

H OH

HO

H OH wherein R represents a fatty acid residue of 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms and R¹ represents an alkyl group having 2 to 6 carbon atoms. Representative examples of such alkyl glucose esters are 1 -ethyl-6- caprylglucoside, 1-ethyl-6-laurylglucoside, 1-butyl-6-caprylglucoside, 1-ethyl- 6-palmitylglucoside and 1-ethyl-6-oleylglucoside.

The aldobionamide sugar cosurfactants are generally disclosed in U.S. Patent No. 5,310,542 and in published European Patent Application No. 550,281 , both of which are incorporated herein by reference. An Aldobionamide is generally defined as the amide of an aldobionic acid or aldobionolactone and an aldobionic acid in turn is defined as a sugar substance (e.g., any cyclic sugar) in which the aldehyde group has been replaced by a carboxylic acid which upon drying is capable of cyclizing to form an aldonolactone. The aldobionamides can be based on compounds comprising two saccharide units, e.g., lactobionamides, maltobionamides, cellobionamides, melibionamides, or gentiobionamides, or they can be based 8 on compounds comprising more than two saccharide units provided that the polysaccharide has a terminal sugar unit with an aldehyde group available.

The preferred aldobionamides of the present invention are lactobionamides of the formula:

NR1R2

wher ein R¹ and R² are the same or different and are selected from hydrogen and an aliphatic hydrocarbon radical containing up to about 36 carbon atoms (e.g., alkyl groups and alkenyl groups, which groups may also include a heteroatom such as N, O, S, present, for instance, as an amide, carboxy, ether and/or saccharide moiety) except that R and R² cannot simultaneously be hydrogen. The aliphatic hydrocarbon radical preferably contains up to 24 carbon atoms, most preferably from 8 to 18 carbon atoms. Representative examples of such lactobionamides are N-propyl lactobionamide, N-pentyl lactobionamide, N-decyl lactobionamide, N-hexadecyl lactobionamide, N- oleyl lactobionamide, N-dodecyl-N-methyl lactobionamide, and N- dodecyloxypropyl lactobionamide.

The gluconamide sugar cosurfactants are generally disclosed in U.S. Patent 5,352,386, the entire contents of which are incorporated herein by reference. These cosurfactants have the general formula: HOCH₂-(CHOH)_m-C(0)-NHR wherein m is an integer from 2 to 5; and R is a straight or branched, saturated or unsaturated aliphatic hydrocarbon having 4 to about 24 carbon atoms, preferably 8 to 24 carbon atoms, which R group can also contain a heteroatom selected from the group consisting of oxygen, nitrogen and sulfur. Representative examples of such cosurfactants are N-octylerythronamide, N- 9 decylerythronamide, N-dodecylerythronamide, N-tetradecylerythronamide, N- decylxylonamide and N-dodecylxylonamide.

The glyceramide sugar cosurfactants are generally disclosed in U.S. Patent 5,352,387, the entire contents of which are incorporated herein by reference. These cosurfactants have the general formula:

HOCH₂CH(OH)C(0)NHR wherein R is a C₈ to C₂₄ straight or branched chained, saturated or unsaturated aliphatic hydrocarbon in which the R group may also be substituted by a heteroatom selected from oxygen, nitrogen and sulfur. Representative examples of such cosurfactants are N-octylglyceramide, N- decylglyceramide and N-hexadecylglyceramide.

The glyceroglycolipid sugar cosurfactants are generally disclosed in U.S. Patent 5,358,656 and published European Patent Application No. 550,279, the disclosure of each of which is incorporated herein by reference. The glyceroglycolipids can be of the formula:

A¹-0-CH₂-CH(B)-CH₂NRR₁ wherein A¹ is a saccharide, preferably having one or more saccharide units, more preferably a mono or disaccharide and most preferably a monosaccharide such as glucose or galactose; R and R are the same or different and are hydrogen, a branched or unbranched hydrocarbon radical having from 1 to about 24, preferably from about 6 to about 18 carbon atoms; B is OH or a NR²R³ group, wherein R² and R³ may be the same or different and are hydrogen, a branched or unbranched hydrocarbon radical having 1 to 24, preferably from 6 to 18 carbon atoms, and NRR and B are positionally interchangeable. Representative examples of such cosurfactants are 3- (butylamino)-2-hydroxypropyl-β-D-galactopyranoside, 3-(octylamino)-2- hydroxypropyl-β-D-galactopyranoside, 3-(eicosylamino)-2-hydroxypropyl-β-D- galactopyranoside, 3-(butylamino)-2-hydroxypropyl-β-D-glucopyranoside, and 3-(pentylamino)-2-hydroxypropyl-β-D-mannopyranoside. Other glyceroglycolipid cosurfactants are disclosed in published

European Patent Application No. 550,280, which is incorporated herein by 10 reference. These cosurfactants are of the formula:

A'-O-CH^CH RO-C^OR wherein A¹ is from 1 to 4 saccharide units and more preferably represents a mono or disaccharide, and most preferably a monosaccharide, for example, glucose or galactose; R and R, are the same or different and are hydrogen, or a branched or unbranched, saturated or unsaturated, hydrocarbon radical having from 1 to 24 carbon atoms, preferably from 6 to 18 carbon atoms. Representative examples of such cosurfactants are 3-(butyloxy)-2- hydroxypropyl-β-D-galactopyranoside, 3-(eicosyloxy)-2-hydroxypropyl-β-D- galactopyranoside, 3-(decyloxy)-2-hydroxypropyl-β-D-galactopyranoside, 3- (butyloxy)-2-hydroxypropyl-β-D-glucopyranoside, 3-(octyloxy)-2- hydroxypropyl-β-D-mannopyranoside, 3-(tetradecyloxy)-2-hydroxypropyl-β-D- lactoside, 3-(octadecyloxy)-2-hydroxypropyl-β-D-maltoside, 3-(octyloxy)-2- hydroxypropyl-β-D-galactotrioside, and 3-(dodecyloxy)-2-hydroxypropyl-β-D- cellotrioside.

The polyhydroxy fatty acid amide sugar cosurfactants are generally disclosed in U.S. Patent Nos. 5,174,927, 5,223,179 and 5,332,528, the entire disclosure of each of which is incorporated herein by reference. The polyhydroxy fatty acid amide surfactant component of the present invention comprises compounds of the structural formula:

R²C(0)N(R¹)Z wherein: R¹ is H, ^-0₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, preferably ( C₄ alkyl, more preferably C, or C₂ alkyl, most preferably C alkyl (i.e., methyl); and R² is a C₅-C₃₁ hydrocarbyl, preferably straight chain C₇-C₁₉ alkyl or alkenyl, more preferably straight chain C₉-C₁₇ alkyl or alkenyl, most preferably straight chain C^-C^ alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxy hydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. As raw 11 materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials. Z preferably will be selected from the group consisting of -CH₂-(CHOH)n-CH₂OH, -CH(CH₂OH)-(CHOH)_n. CH₂OH, -CH₂-(CHOH)₂(CHOR')(CHOH)-CH₂OH, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosaccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly -CH₂-(CHOH)₄-CH₂OH.

In the above formula R¹ can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl. R²C(0)N< can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc. Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl,

1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl, etc.

Representative examples of such cosurfactants are N-methyl-N-1- deoxyglucityl cocoamide and N-methyl-N-1 -deoxyglucityl tallowamide.

Other suitable polyhydroxy fatty acid amide cosurfactants (see U.S. Patent Nos. 5,223,179 and 5,338,491 , the entire contents of each of which are incorporated herein by reference) are those of the formula:

RC(0)N(R¹)CH₂CH(OH)CH₂OH wherein R is a C₇-C₂₁ hydrocarbyl species, i.e., coconut, tallow, palm fatty alkyl and oleyl, and R¹ is a C to C₆ hydrocarbyl or substituted hydrocarbyl species, i.e., N-alkyl-N-(1 ,2-propanediol) and N-hydroxyalkyl-N-1 ,2-propane diol fatty acid amides. Representative examples of such cosurfactants are the tallow amide of 3-[2-(hydroxyethyl)amino]-1 ,2-propanediol (HEAPD), the palmitate amide of 3-methylamino-1 ,2-propanediol (MAPD) and the lauramide of MAPD. Alkoxylated fatty alcohols include fatty alcohols such as those listed above which are alkoxylated with ethylene oxide, propylene oxide and combinations thereof. 12

Alkoxylated fatty acids include fatty acids such as those listed above which are alkoxylated with ethylene oxide, propylene oxide and combinations thereof.

Alkoxylated fatty ethers include fatty ethers such as those listed above which are alkoxylated with ethylene oxide, propylene oxide and combinations thereof.

Alkoxylated fatty amides include fatty amides such as those listed above which are alkoxylated with ethylene oxide, propylene oxide and combinations thereof. Suitable alcohol ethoxylates include C8-18 alcohols ethoxylated with from about 2 to about 30 moles of ethylene oxide.

Suitable ethoxylated seed oils include those containing from about 1 to about 200 moles of ethylene oxide.

Similarly, examples of ethoxylated mineral oils include those containing from about 1 to about 200 moles of ethylene oxide.

Suitable nonylphenol ethoxylates include those ethoxylated with from about 4 to about 70 moles of ethylene oxide. A particularly preferred nonylphenol ethoxylate is a combination of an NP-9 with an NP-6.

Alkoxylated alkyl phenols include alkyl phenols such as those listed above which are alkoxylated with ethylene oxide, propylene oxide and combinations thereof.

Ethoxylated glycerides which may be employed in the adjuvant composition of the present invention include those based on C^^ fatty acids containing from about 1 to about 200 moles of ethylene oxide. Suitable castor oil ethoxylates include those containing from about 1 to about 200 moles of ethylene oxide.

Particularly preferred nonionic surfactants for use in the adjuvant composition of the present invention include a mixture of an alkyl polyglycoside and a castor oil containing from about 5 to about 54 moles of ethylene oxide in a ratio by weight of 1 :2 to about 1 :20.

The anionic surfactants that can be used in the compositions according to the invention are selected from the group consisting of an 13 ethoxylated partial phosphate ester, an alkyl sulfate and, an alkyl ether sulfate, a branched alkyl benzene sulfonate, a linear alkyl benzene sulfonate and an alpha olefin sulfonate. The preferred anionic surfactant is an ethoxylated partial phosphate ester. The ethoxylated partial phosphate esters are partial phosphate esters of polyoxyalkylene ethers. These partial esters are prepared by methods well known to those skilled in the art such as, for example, by reaction of a monofunctional polyoxyalkylene ether with phosphoric acid, diphosphorus pentoxide, polyphosphoric acid, or phosphorus oxytrichloride. These partial phosphate esters are described in U.S. patent 4,966,728 at column 3, lines 14-33, the contents of which are incorporated herein by reference. A preferred ethoxylated partial phosphate ester is phosphoric acid partially esterified with nonyl phenol (EO)-9, (nonyl phenol ethoxylated with 9 moles of ethylene oxide).

The alkyl sulfates that can be used in the compositions according to the invention are those wherein the alkyl group has from about 6 to about 22 carbon atoms. The alkyl ether sulfates that can be used in the compositions according to the invention are those wherein the alkyl group has from about 6 to about 22 carbon atoms. The branched alkyl benzene sulfonates that can be used in the compositions according to the invention are those wherein the alkyl group can be branched and has from about 6 to about 22 carbon atoms. The linear alkyl benzene sulfonates that can be used in the compositions according to the invention are those wherein the alkyl group is an essentially unbranched alkyl group having from about 6 to about 22 carbon atoms. The alpha olefin sulfonates that can be used in the compositions according to the invention are those wherein the alkyl group has from about 6 to about 22 carbon atoms.

Suitable fertilizer components include, but are not limited to, nitrogenous fertilizers such as urea ammonium nitrate, as well as those of the sulfate type such as liquid ammonium sulfate. It should be noted, however, that any fertilizer suitable for application onto an agricultural substrate, may be utilized, without departing from the spirit of the invention.

According to one embodiment of the present invention, there is 14 provided an adjuvant composition containing: (a) from about .5 to about 95% by weight, preferably from about 5 to about 90% by weight, and most preferably from about 10 to about 80% by weight, of an oil component; (b) from about .5 to about 35% by weight, preferably from about 1 to about 25% by weight, and most preferably from about 5 to about 20% by weight, of a nonionic surfactant; (c) from about .1 to about 25% by weight, preferably from about .5 to about 15% by weight, and most preferably from about 1 to about 10% by weight, of an anionic component; and (d) from about .1 to about 70% by weight, preferably from about .5 to about 60% by weight, and most preferably from about 1 to about 50% by weight, of a fertilizer, preferably a nitrogenous fertilizer.

Auxiliary components may also be added to the adjuvant composition of the present invention, in order to further enhance the properties thereof. Examples thereof include, but are not limited to, water-soluble silicone surfactants, oil-soluble silicone surfactants, cationic surfactants, amphoteric surfactants, and the like.

Suitable water-soluble silicone surfactants include, but are not limited to, EO/PO polyether-trisiloxane copolymers such as BREAKTHRU® S240, commercially available from Goldschmidt Chemical Corp. Suitable oil-soluble silicone surfactants include, but are not limited to,

EO/PO polyether-polymethylsiloxane-copolymers such as BREAKTHRU® OE 441 , commercially available from Goldschmidt ChemicaLCorp.

Anionic surfactants which may be employed include, but are not limited to, phosphate esters, an ethoxylated partial phosphate ester, an alkyl sulfate and, an alkyl ether sulfate, a branched alkyl benzene sulfonate, a linear alkyl benzene sulfonate and an alpha olefin sulfonate. The preferred anionic surfactant is an ethoxylated partial phosphate ester. The ethoxylated partial phosphate esters are partial phosphate esters of polyoxyalkylene ethers. These partial esters are prepared by methods well known to those skilled in the art such as, for example, by reaction of a monofunctional polyoxyalkylene ether with phosphoric acid, diphosphorus pentoxide, polyphosphoric acid, or phosphorus oxytrichloride. These partial phosphate esters are described in 15

U.S. patent 4,966,728 at column 3, lines 14-33, the contents of which are incorporated herein by reference. A preferred ethoxylated partial phosphate ester is phosphoric acid partially esterified with nonyl phenol (EO)-9, (nonyl phenol ethoxylated with 9 moles of ethylene oxide). Cationic surfactants which may be employed include, but are not limited to, ethoxylated amines such as ethoxylated tallow amine.

Amphoteric surfactants which may be employed include, but are not limited to, amino acids and their derivatives, amino acid salts, imidazolinium derivatives, alkyl betaines and amidopropyl analogues. In the event that such auxiliary components are employed, they will be present in the adjuvant composition of the present invention in an amount ranging from about 1 to about 25% by weight, preferably from about 4 to about 20% by weight, and most preferably from about 7 to about 18% by weight. In the event that methyl or ethyl esters of fatty acids or other pH sensitive components such as sulfonylurea pesticides are added to the composition, it may be necessary to adjust the pH to from about 3.0 to about 10.0, preferably from about 4.0 to about 9.0, and most preferably from about 5.5 to about 6.5, in order to prevent hydrolysis or breakdown of the components. The pH may be adjusted by using, for example, potassium hydroxide, ammonium hydroxide, sodium hydroxide, triethanolamine, monoethanolamine and aminoethylethanolamine.

The adjuvant composition thus formed can then be combined with a biologically active substance such as a fungicide, bactericide, bacteriostat, herbicide/plant growth regulator, and the like, to formulate an agricultural composition for use on agricultural substrates.

Suitable biologically active materials which can be used to make agricultural compositions according to the invention include, but are not limited to, fungicides such as 3,3'-ethylenebis (tetrahydro-4,6-dimethyl-2H-1 ,3,5-thiadiazine-2-thione), zinc or manganese ethylenebis(dithiocarbamate), bis-(dimethyldithiocarbamoyl)disulfide, zinc propylenebis (dithiocarbamate), bis(dimethyldithiocarbamoyl) 16 ethylenediamine; nickel dimethyldithiocarbamate, methyl-1(butylcarbamoyl)-2-benzimidazolecarbamate,

1,2-bis(3-methoxycarbonyl-2-thioureido)benzene,

1-isopropylcarbamoyl-3-(3,5-dichlorophenyl)hydantoin, potassium N-hydroxymethyl-N-methyldithiocarbamate and

5-methyl-10-butoxycarbonylamino-10, 11 -dehydrodibenzo (b,f)azepine; pyridine fungicides such as zinc bis(1-hydroxy-2(1H)pyridinethionate and 2-pyridinethiol-1 -oxide sodium salt;

O.O-diisopropyl S-benzylphosphorothioate and O-ethyl S,S-diphenyldithiophosphate; phthalimide fungicides such as

N-(2,6-p-diethylphenyl)phthalimide and

N-(2,6-diethylphenyl)-4-methylphthalimide; dicarboxyimide fungicides such as

N-trichloromethylthio 4-cyclohexene-1 ,2-dicarboxyimide and

N-tetrachloroethylthio-4-cyclohexene-1 ,2-dicarboxyimide; 5,6-dihydro-2-methyl-1 ,4-oxathine-3-carboxanilido-4,4-dioxide and

5,6-dihydro-2-methyl-1 , 4-oxathine-3-carboxanilide; naphthoquinone fungicides such as 2,3-dichloro-1 ,4-naphthoquinone, 2-oxy-3-chloro-1 ,4-naphthoquinone copper sulfate, pentachloronitrobenzene; 1 ,4-dichloro-2,5-dimethoxybenzene; 5-methyl-s-triazol-(3,4-b)benzthiazole; 2-(thiocyanomethylthio)benzothiazole;

3-hydroxy-5-methylisooxazole; N-2,3-dichlorophenyltetrachlorophthalamic acid;

5-ethoxy-3-trichloromethyl-1,2,4-thiazole;

2,4^dichloro-6-(0-chloroanilino)-1 ,3,5-triazine; 2,3-dicyano-1 ,4-dithioanthraquinone; copper 8-quinolinate; polyoxine; validamycin; cycloheximide; iron methanearsonate; diisopropyl

1 ,3-dithiolane-2-iridene malonate; 3-allyloxy-1 ,2-benzoisothiazol-1 ,1 -dioxide; kasugamycin; Blasticidin S; 4,5,6,7-tetrachlorophthalide;

3-(3,5-dichlorophenyl)5-ethenyl 5-methyloxazoline-2,4-dione; N-(3,5-dichlorophenyl)-1 ,2-dimethylcyclopropane-1 ,2-dicarboxyimide;

S-n-butyl-5'-para-t-butylbenzyl-N-3-pyridyldithiocarbonylimidate;

4-chlorophenoxy-3,3-dimethyl-1-(1 H,1 ,3,4-triazol-1-yl)-2-butanone; 17 methyl-D,L-N-(2,6-dimethylphenyl)-N-(2'-methoxyacetyl)alaninate;

N-propyl-N-[2-(2,4,6-trichlorophenoxy)ethyl]imidazol-1-carboxamide;

N-(3,5-dichlorophenyl)succinamide; tetrachloroisophthalonitrile;

2-dimethylamino-4-methyl-5-n-butyl-6-hydroxypyrimidine; 2,6-dichloro-4-nitroaniline; 3-methyl-4-chlorobenzthiazol-2-one;

1 ,2,5,6-tetrahydro-4H-pyrrolol-[3,2,1-i,j]quinoline-2-one;

3'-isopropoxy-2-methylbenzanilide;

1 -[2-(2,4-dichlorophenyl)-4-ethyl-1 ,3-dioxorane-2-ylmethyl]-1 H,1 ,2,4-triazol;

1 ,2-benzisothiazoline-3-one; basic copper chloride; basic copper sulfate; N'-dichlorofluoromethylthio-N,N-dimethyl-N-phenyl sulfamide; ethyl-N-(3-dimethylaminopropyl)thiocarbamate hydrochloride; piomycin;

S,S-6-methylquinoxaline-2,3-diyldithiocarbonate; complex of zinc and manneb; di-zinc bis(dimethyldithiocarbamate)ethylenebis (dithiocarbamate). Plant growth regulators which may also be employed include but are not limited to N-methoxycaronyl-N'-4-methylphenylcarbamoylethylisourea and

1 -(4-chlorophenylcarbamoyl)-3-ethoxycarbonyl-2-methylisourea; another type of plant growth regulators such as sodium naphthaleneacetate,

1 ,2-dihydropyridazine-3,6-dione and gibberellins; triazine herbicides such as

2-methylthio-4,6-bisethylamino-1 ,3,5-triazine, 2-chloro-4,6-bisethylamino-1 ,3,5-triazine,

2-methoxy-4-ethylamino-6-isopropylamino-1 ,3,5-triazine,

2-chloro-4-ethylamino-6-isopropylamino-s-triazine,

2-methylthio-4,6-bis(isopropylamino)-S-triazine and

2-methylthio-4-ethylamino-6-isopropylamino-s-triazine; phenoxy herbicides such as 2,4-dichlorophenoxyacetic acid and methyl, ethyl, and butyl esters thereof.

2-chloro-4-methylphenoxyacetic acid, 4-chloro-2-methylphenoxyacetic acid and ethyl 2-methyl-4-chlorophenoxybutylate; diphenylether herbicides such as 2,4,6-trichlorophenyl-4'-nitrophenylether,2,4-dichlorophenyl-4'-nitrophenylethe r and 3,5-dimethylphenyl-4'-nitrophenylether; urea herbicides such as

3-(3,4-dichlorophenyl)-1 -methoxy-1 -methyl urea, 18

3-(3,4-dichlorophenyl)-1 ,1-dimethylurea and 3-(4-chlorophenyl)-1,1 -dimethyl urea; carbamate herbicides such as

3-methoxycarbonylaminophenyl-N-(3-methylphenyl)carbamate, isopropyl-N-(3-chlorophenyl)carbamate and methyl-N-(3,4'-dichlorophenyl)carbamate; uracil herbicides such as

5-bromo-3-sec-butyl-6-methyluracil and 1 -cyclohexyl-3,5-propyleneuracil; thiolcarbamate herbicides such as

S-(4-chlorobenzyl)-N,N-diethylthiolcarbamate,S-ethyl-N-cyclohexyl-N- ethylthiolcarbamate and S-ethyl-hexahydro-1H-azepine-1-carbothioate and S-ethyl-N,N-di-n-propyl-thiocarbamate; pyridinium herbicides such as l .l'-di-methyM^'-bispyridinium dichloride; phosphoric herbicides such as N-(phosphonomethyl)glycine; aniline herbicides such as alpha, alpha, alpha-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine, 4-(methylsulfonyl)-2,6-dinitro-N,N-dipropylaniline and N[3], N[3]-diethyl-2,4-dinitro-6 trifluoromethyl-1 ,3-phenylene diamine; acid anilide herbicides such as 2-chloro-2',6'-diethyl-N-(butoxymethyl)acetoanilide, 2-chloro-2^,,6'-diethyl-N-(methoxymethyl)acetoanilide, and 3,4-dichloropropionanilide; pyrazole herbicides such as 1 ,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-hydroxypyrazole and l,3-di-methyl-4-(2,4-dichlorobenzoyl)-5-(p-toluenesulfonyloxy)pyrazole;

5-tert-butyl-3-(2,4-dichloro-5-isopropoxyphenyl)-1 ,3,4-oxadiazoline-2-one; 2-[N-isopropyl,N-(4-chlorophenyl)carbamoyl]-4-chloro-5-methyl-4-isooxazoline -3-one; 3-isopropylbenzo-2-thia-1 ,3-diazinone-(4)-2,4-dioxide and 3-(2-methyl-phenoxy)pyridazine. The precise amount of biologically active ingredient to be combined with the adjuvant composition will ultimately depend on the end-users needs and objectives and, thus, will be known by those skilled in the art.

The agricultural compositions according to the invention may also contain, for example, dyes, additional cosurfactants, emulsifiers and solvents where required.

The present invention also provides a process for treating an agricultural substrate involving contacting the substrate with the above- disclosed agricultural composition. 19

The present invention will be better understood from the examples which follow, all of which are intended to be illustrative only and are not meant to unduly limit the scope of the invention. Unless otherwise indicated, percentages are on a weight-by-weight basis.

EXAMPLES

Example 1

Component % wt

Methyl Soyate 74.0

EO/PO Polyether-polymethysiloxane-copolymer^ 3.0

POE (16) Castor Oil 7.0

EO/PO Polyether -Trisiloxane-copolymer^ 12.0

C8-10 Alkyl Polyglycoside 1.0

POE (6) Tridecyl Alcohol Phosphate, Free Acid 1.0

32% Nitrogen Fertilizer Z£>

100.0%

1) BREAKTHRU® OE 441 Goldschmidt Chemical Corporation

2) BREAKTHRU® S240 Goldschmidt Chemical Corporation

20

Example 2

Component % wt

32% Nitrogen Fertilizer 58.5

C8-10 Alkyl Polyglycoside 1.5

Water 5.6

POE (6) Tridecyl Alcohol Phosphate, Free Acid 8.2

Methyl Soyate 10.7

POE (16) Castor Oil 14.8

Amino Ethyl Ethanolamine 0.7

100.0%

Example 3

Component % wt

28% Nitrogen Fertilizer 56.5

Ethyl Canolate 27.5

POE (16) Castor Oil 4.9

C9-11 Alkyl Polyglycosides 2.4

POE(9) Nonyl Phenol Phosphate Ester, Free Acid 7.4

KOH (45%) 1,3

100.0%

The above-formulated adjuvant compositions exhibited acceptable storage stability, in view of the presence of a fertilizer component in the composition.

Claims

21 What is claimed is:

1. An adjuvant composition comprising:

(a) an oil component selected from the group consisting of a fatty acid ester, a seed oil, a petroleum oil, a fatty acid, a fatty alcohol, a fatty ether, a fatty amide, a glyceride and mixtures thereof;

(c) an anionic surfactant; and

(d) a fertilizer component.

2. The composition of claim 1 wherein the oil component is present in the composition in an amount of from about 0.5 to about 95% by weight, based on the weight of the composition.

3. The composition of claim 1 wherein the oil component is a fatty acid ester selected from the group consisting of a methyl ester, an ethyl ester, and mixtures thereof.

4. The composition of claim 3 wherein the fatty acid ester is a methyl ester selected from the group consisting of methyl oleate, methyl laurate, methyl soyate and mixtures thereof.

5. The composition of claim 1 wherein the nonionic surfactant component is present in the composition in an amount of from about 0.5 to about 35% by weight, based on the weight of the composition.

6. The composition of claim 1 wherein the nonionic surfactant component is a sugar surfactant.

7. The composition of claim 6 wherein the sugar surfactant is an alkyl polyglycoside corresponding to formula I:

RιO(Z)_a wherein R, is a monovalent organic radical having from about 6 to about 30 carbon atoms; Z is saccharide residue having 5 or 6 carbon atoms; a is a number having a value from 1 to about 6. 22

8. The composition of claim 7 wherein in formula I, R., is a monovalent organic radical having from 8 to 12 carbon atoms, and a is a number from about 1.6 to about 1.7.

9. The composition of claim 1 wherein the nonionic surfactant component is a mixture of a sugar surfactant and an ethoxylated seed oil.

10. The composition of claim 9 wherein the sugar surfactant is an alkyl polyglycoside and the ethoxylated seed oil is castor oil having from about 1 to about 200 moles of ethylene oxide.

11. The composition of claim 1 wherein the anionic surfactant is present in the composition in an amount of from about 0.1 to about 25% by weight, based on the weight of the composition.

12. The composition of claim 1 wherein the anionic surfactant is a phosphate ester.

13. The composition of claim 1 wherein the fertilizer component is present in the composition in an amount of from about 0.1 to about 70% by weight, based on the weight of the composition.

14. The composition of claim 1 wherein the fertilizer component is a nitrogenous fertilizer.

15. The composition of claim 14 wherein the nitrogenous fertilizer is urea ammonium nitrate.

16. The composition of claim 1 further comprising an auxiliary component selected from the group consisting of a cationic surfactant, an amphoteric surfactant, and mixtures thereof.

17. The composition of claim 14 wherein the auxiliary component is present in the composition in an amount of from about 1 to about 25% by weight, based on the weight of the composition.

18. The composition of claim 1 wherein the nonionic surfactant is an alkoxylated fatty alcohol.

19. The composition of claim 1 wherein the nonionic surfactant is a nonylphenol ethoxylate.

20. The composition of claim 1 wherein the nonionic surfactant is an ethoxylated mineral oil. 23

21. The composition of claim 1 wherein the nonionic surfactant is an alkoxylated fatty ether.

22. The composition of claim 1 wherein the nonionic surfactant is an alkoxylated fatty amide.

23. An adjuvant composition comprising:

(a) from about 10 to about 80% by weight of a fatty acid ester;

(b) from about 5 to about 20% by weight of a nonionic surfactant consisting of a mixture of an alkyl polyglycoside and an ethoxylated seed oil;

(c) from about 1 to about 10% by weight of a phosphate ester; and (d) from about 0.1 to about 70% by weight of a nitrogenous fertilizer component, all weights being based on the weight of the composition.

24. An agricultural composition comprising the adjuvant composition of claim 1 and an effective amount of a biologically active ingredient.

25. A process for treating an agricultural substrate comprising contacting the substrate with the agricultural composition of claim 24.

26. An adjuvant composition comprising:

(a) an oil component selected from the group consisting of a fatty acid ester, a seed oil, a petroleum oil, a fatty acid, a fatty alcohol, a fatty ether, a fatty amide, a glyceride and mixtures thereof; (b) a nonionic surfactant selected from the group consisting of sugar surfactants, alkoxylated fatty alcohols, alkoxylated fatty acids, alkoxylated fatty ethers, alkoxylated fatty amides, ethoxylated seed oils, ethoxylated mineral oils, nonylphenol ethoxylates, alkoxylated alkyl phenols, ethoxylated glycerides, castor oil ethoxylates and mixtures thereof; and (c) a fertilizer component.

27. The composition of claim 26 wherein the oil component is present in the composition in an amount of from about 0.5 to about 95% by weight, based on the weight of the composition.

28. The composition of claim 26 wherein the oil component is a fatty acid ester selected from the group consisting of a methyl ester, an ethyl ester, and mixtures thereof.

29. The composition of claim 28 wherein the fatty acid ester is a methyl ester 24 selected from the group consisting of methyl oleate, methyl laurate, methyl soyate and mixtures thereof.

30. The composition of claim 26 wherein the nonionic surfactant component is present in the composition in an amount of from about 0.5 to about 35% by weight, based on the weight of the composition.

31. The composition of claim 26 wherein the nonionic surfactant component is a sugar surfactant.

32. The composition of claim 31 wherein the sugar surfactant is an alkyl polyglycoside corresponding to formula I: R₁0(Z)_a wherein R, is a monovalent organic radical having from about 6 to about 30 carbon atoms; Z is saccharide residue having 5 or 6 carbon atoms; a is a number having a value from 1 to about 6.

33. The composition of claim 32 wherein in formula I, R₁ is a monovalent organic radical having from 8 to 12 carbon atoms, and a is a number from about

1.6 to about 1.7.

34. The composition of claim 26 wherein the nonionic surfactant component is a mixture of a sugar surfactant and an ethoxylated seed oil.

35. The composition of claim 34 wherein the sugar surfactant is an alkyl polyglycoside and the ethoxylated seed oil is castor oil having from about 1 to about 200 moles of ethylene oxide.

36. The composition of claim 26 further comprising from about 0.1 to about 25% by weight, based on the weight of the composition, of an anionic surfactant.

37. The composition of claim 36 wherein the anionic surfactant is a phosphate ester.

38. The composition of claim 26 wherein the fertilizer component is present in the composition in an amount of from about 0.1 to about 70% by weight, based on the weight of the composition.

39. The composition of claim 26 wherein the fertilizer component is a nitrogenous fertilizer.

40. The composition of claim 39 wherein the nitrogenous fertilizer is urea ammonium nitrate. 25

41. The composition of claim 26 further comprising an auxiliary component selected from the group consisting of a cationic surfactant, an amphoteric surfactant, and mixtures thereof.

42. The composition of claim 41 wherein the auxiliary component is present in the composition in an amount of from about 1 to about 25% by weight, based on the weight of the composition.

43. The composition of claim 26 wherein the nonionic surfactant is an alkoxylated fatty alcohol.

44. The composition of claim 26 wherein the nonionic surfactant is a nonylphenol ethoxylate.

45. The composition of claim 26 wherein the nonionic surfactant is an ethoxylated mineral oil.

46. The composition of claim 26 wherein the nonionic surfactant is an alkoxylated fatty ether.

47. The composition of claim 26 wherein the nonionic surfactant is an alkoxylated fatty amide.

48. An agricultural composition comprising the adjuvant composition of claim 26 and an effective amount of a biologically active ingredient.

49. A process for treating an agricultural substrate comprising contacting the substrate with the agricultural composition of claim 48.

50. An adjuvant composition comprising:

(a) an oil component selected from the group consisting of a fatty acid ester, a seed oil, a petroleum oil, a fatty acid, a fatty alcohol, a fatty ether, a fatty amide, a glyceride and mixtures thereof; (b) an anionic surfactant; and

(c) a fertilizer component.

51. The composition of claim 50 wherein the oil component is present in the composition in an amount of from about 0.5 to about 95% by weight, based on the weight of the composition.

52. The composition of claim 50 wherein the oil component is a fatty acid ester selected from the group consisting of a methyl ester, an ethyl ester, and mixtures thereof. 26

53. The composition of claim 52 wherein the fatty acid ester is a methyl ester selected from the group consisting of methyl oleate, methyl laurate, methyl soyate and mixtures thereof.

54. The composition of claim 50 further comprising from about 0.5 to about 35% by weight, based on the weight of the composition, of a nonionic surfactant selected from the group consisting of sugar surfactants, alkoxylated fatty alcohols, alkoxylated fatty acids, alkoxylated fatty ethers, alkoxylated fatty amides, ethoxylated seed oils, ethoxylated mineral oils, nonylphenol ethoxylates, alkoxylated alkyl phenols, ethoxylated glycerides, castor oil ethoxylates and mixtures thereof.

55. The composition of claim 54 wherein the nonionic surfactant component is a sugar surfactant.

56. The composition of claim 55 wherein the sugar surfactant is an alkyl polyglycoside corresponding to formula I: R₁0(Z)_a wherein R, is a monovalent organic radical having from about 6 to about 30 carbon atoms; Z is saccharide residue having 5 or 6 carbon atoms; a is a number having a value from 1 to about 6.

57. The composition of claim 56 wherein in formula I, R, is a monovalent organic radical having from 8 to 12 carbon atoms, and a is a number from about

1.6 to about 1.7.

58. The composition of claim 54 wherein the nonionic surfactant component is a mixture of a sugar surfactant and an ethoxylated seed oil.

59. The composition of claim 58 wherein the sugar surfactant is an alkyl polyglycoside and the ethoxylated seed oil is castor oil having from about 1 to about 200 moles of ethylene oxide.

60. The composition of claim 50 wherein the anionic surfactant is present in the composition in an amount of from about 0.1 to about 25% by weight, based on the weight of the composition.

61. The composition of claim 50 wherein the anionic surfactant is a phosphate ester.

62. The composition of claim 50 wherein the fertilizer component is present 27 in the composition in an amount of from about 0.1 to about 70% by weight, based on the weight of the composition.

63. The composition of claim 50 wherein the fertilizer component is a nitrogenous fertilizer.

64. The composition of claim 63 wherein the nitrogenous fertilizer is urea ammonium nitrate.

65. The composition of claim 50 further comprising an auxiliary component selected from the group consisting of a cationic surfactant, an amphoteric surfactant, and mixtures thereof.

66. The composition of claim 65 wherein the auxiliary component is present in the composition in an amount of from about 1 to about 25% by weight, based on the weight of the composition.

67. The composition of claim 54 wherein the nonionic surfactant is an alkoxylated fatty alcohol.

68. The composition of claim 54 wherein the nonionic surfactant is a nonylphenol ethoxylate.

69. The composition of claim 54 wherein the nonionic surfactant is an ethoxylated mineral oil.

70. The composition of claim 54 wherein the nonionic surfactant is an alkoxylated fatty ether.

71. The composition of claim 54 wherein the nonionic surfactant is an alkoxylated fatty amide.

72. An agricultural composition comprising the adjuvant composition of claim 50 and an effective amount of a biologically active ingredient.

73. A process for treating an agricultural substrate comprising contacting the substrate with the agricultural composition of claim 72.