CA2211996A1 - Pesticidal granules containing fertilizer and surfactant - Google Patents

Abstract

A method for producing a dry bonded pesticidal granular surfactant/fertilizer delivery system comprising spray-coating from about 1 to about 99 weight percent dry water-soluble, nitrogen-containing fertilizer particles, preferably diammonium sulfate with the surfactant composition, admixing pesticide; and granulating the final delivery system; and the granules produced thereby.

Description

-WO 96/23408 PCI'IUS96/01233 PESTICIDAL GR~I'IULES CONTAINING FERTILIZER AND SURFACTANT

Field of the Invention The present invention relates to pesticidal granules containing rapidly dissolutioning or dispersing fertilizer and surfactant compositions. More particularly, the fertilizers are water-soluble nitrogen-containing and the surfactant compositions comprise solid, nonionic surfactants.

Backqround of the Invention It is well recognized by the agricultural industry that it is advantageous to the end-user to be able to formulate active pesticides as water dissolutioning or dispersible compositions which can be easily mixed with water and applied by means of a spraying apparatus to a locus to be protected.
Additionally, many pesticides, for example, fungicides, plant growth regulators, herbicides and systemic insecticides or, in fact, any pesticide needing rain fastness or attendant soil or surface wetting/penetration require the presence of surfactant adjuvants for effective end-use applications. This is especially tr1i~e for herbicides which realize greatly enhanced post-emergence weed control when applied with certain nonionic surfactants. For example, studies such as "Surfactant Struc:ture and Concentration Strongly Affect Rimsulfuron Activity" Green et al., Weed Technology Vol.
7:633-640, 1993 have indicated that sulfonyl urea herbicidal W O 96123408 PCTrUSg6/01233 activity can be increased ten-fold with selection o~
appropriate nonionic surfactant adjuvants. The art has also recognized the particular importance of two of the adjuvant properties. They are ~lrst, the hydrophilic - hydrophobic balance (HLB) and secondly, the physical form of the initial surface deposit, ideally a moist gel. It has been theorized that with surfactants in the appropriate HLB range, the sur~actant is hydrophilic enough to solubilize the herbicide in water and lipophilic enough to penetrate the cuticle of a lea~. In moist gels, the surfactants are hypothesized to ~orm monolayers on the leaf surfaces with the lipophilic portion along the waxes and the hydrophilic portion forming "hydrophilic channels" through surface imperfections such as cracks, punctures, and pores. These channels absorb water and slightly swell to allow herbicides to diffuse through the cuticle into the cell walls.
The surfactants preferred by the art and which can realize the above-described properties when admixed with pesticides in aqueous medium, are the nonionics. Most preferably, the solid, nonionic sùrfactants are desired by the end-user, usually a farmer, ~or ease of handling such as when preparing a pesticidal spray tank mix. The solid nonionics are also preferred to eliminate the need for triple rinsing of the liquid surfactant containers, e.g., the 2.5 gallon jugs, usually used to deliver liquid surfactant concentrates to farmers and to a~oid the attendant jug disposal pro~lem.

However, solid non:ionic surfactants tend to dissolve rather slowly; therefore, end-users must be especially careful to ensure complete dissolution of the sur~actant so that proper pesticide to surfactant ratios are delivered to the locus and/or that entrained undissolved particles do not interl~pt the delivery process, e.g., by plugging spray nozzles.
Often dry wat:er-soluble nitrogen fertilizers such as urea, ethylurea, rnono and diammonium phosphate; mono and diammonium sulfate, and mixtures thereof can ~nh~nce the o ef~icacy of pesticides, especially the herbicides. This significant increase in herbicide phytotoxicity in the presence of nitrogen fertilizers has been especially observed with the u~e of diammonium sulfate adjuvant. Large increases in herbicidal eff:icacy have been reported (Adjuvants and Agrochemicals, Vol. II, Chapter 34) when di~mmn~ium sul~ate was used as an adjuvant in combination with methylated seed oil, a known cu~icle "softener". Glyphosate, one of the most frequently used herbicides worldwide, usually has diammonium sulfate added to its spray tank solution to enhance its herbicidal efficacy. As an aside, ~;~m~onium sulfate appears to have at least two modes of action when coupled to glyphosates: first:Ly, by directly increasing the glyphosates phytotoxicity and secondly, by overcoming antagonism from certain cations. It has been theorized that the sulfate ions precipitate calcium and sodium ions by forming calcium and sodium sulfates which have low water solubility. The ammonium WO 96/23408 PCI~/US96101233 ions form the more toxic glyphosate-ammonium complex and prevent formation of the less phytotoxic glyphosate - sodium complex durlng droplet drying.
However, the delivery of a pesticide, the aforedescribed solid, nonionic surfactant composition and the dry water-soluble fertilizer components individually to the customer for on-site blending or tank mixing ofttimes results in an undesirable situation for the customer for he has to ensure that the amounts of the pesticide, surfactant composition and 0 fertilizer inserted into the spray tank are correct; the materials are compatible and properly dispersed; proper safety precautions are followed, for example, if one or more of the components dust; and that necessary additional adjuvants are immediately available if, through incompatibility or otherwise, for example, problems with excessive foaming or precipitation were to occur. Even though all of the components are delivered as solids, a spill of a component delivered as a powder can also be exceedingly difficult to clean up.
In view of the above, suppliers to the agricultural market have attempted to pre-blend individual fertilizer, surfactant and other adjuvant components as an aid to the end-user farmer. However, significant differences in particle sizes among the individual components can result in separation during shipping and/or storage. Furthermore, inherent tackiness or particle fines generated through attrition can , CA 02211996 1997-07-30 W O 96/23408 PCTnUS96/01233 result in compaction and/or cakiny before the customer can use the product blend. In view of the slow aqueous dissolution rate exhibited by many of the solid nonionics, it would also be desirable to increase the rate at which the solid surfactant dissolves in the end-user's final liquid medium.
Heretofore, attempts to control the times of solid surfactant solubilization have taken various ~orms, such as using incorporated ~inders, extrusion granulation, membrane encapsulation, or tableting, i.e., compression of the surfactant-containing compositions all of which possess attendant disadvantages. For example, encapsulation is highly dependent upon t:he quality of the encapsulating material and may release the compositions in discrete packages. The compaction process is an extremely difficult way to control the release of surfactant material for slight variations in composition properties, e.g., tackiness, particle size, etc.
can have dramatic impact on the dissolution rate even under fixed, uniform compacting pressure.
Extrusion processing to prepare melt-admixed granules, such as is taught in EP 501,798A1, wherein pesticides, binders and diluents are extruded together, has the disadvantage of always intimately admixing all of the components thus inherently plac:Lng a restriction on the individual components that can be utilized in such a process. For example, in many ~ 2s situations, the individual components sought to be used are incompatible in intimate contact. Furthermore, in extruded WO 96123408 ~ 01233 granules, all of the material components will be exposed to the aqueous medium simultaneously, i.e., one cannot program for differing dissolltion rates.
As noted above, however, granule-type products, i.e., multi-component par~icles are desirable in many end-use applications such as when they are to be used in pesticidal tank mixes for they are more stable during storage and transport than mere physical mixtures of the dry individual components and provide ease of handling.
0 It would be advantageous if a process means relatively insensitive to minor process or product variations were available to avoid the above-identified problems of the prior art; to provide a single particle pesticide-fertilizer-nonionic surfactant carrier; and to perhaps not only increase the rate at which nonionic solid surfactants dissolve in ac~ueous medium, but also permit i) incompatible components to be incorporated into a single particle and ii) preferential or sec~uential exposure of selected components to the aqueous media.
For all of the above reasons, it would be highly desirable to be able to provide a dry solia gramllated product comprising a water-dispersible pesticide, water-soluble solid fertilizer and solid, nonionic surfactant composition, which does not exhibit the undesirable traits associates with heretofore prior art blend attempts as detaileci above.

Summarv of the Invention It is an object of the present in~ention to realize a process for preparing pesticidal granules comprising a dry water-soluble n:itrogen fertilizer coated by solid nonionic surfactant compositions and granulated with pestlcide adhered to the granule, and the resulting granule. This is accomplished by spray-coating the molten surfactant composition ontc~ from about 1 to about 99 weight percent dry water-soluble, nitrogen-containing fertilizer, preferably 0 diammonium sulfate crystals, said percent based on the final weight of the dry bonded adjuvant granule, and granulating the composition in t:he presence of pesticide to incorporate same into the granule.

S Detailed Descri~tion of the Invention It has been discovered that dry water-soluble nitrogen-containing ~ert:ilizers, preferably diammonium sulfate can provide excellent substrates for certain solid nonionic surfactants when the surfactant composition is dry bonded onto from about 1 to abou~ 99 weight percent (based on the total dry bonded parti.cle weight) of the fertilizer by spray-coating the fertilizer with the molten surfactant and these particles provide excellent carrier systems for pesticides. The time for complete dissolution in water of the solid, nonionic surfactant compositions can ofttimes be significantly reduced.
These coated pes,ticide-fertilizer carrier systems also realize WO 96123408 ]~CTIUS96/01233 many additional advantages over similar blends of these materials in the prior art. At the outset, being a hard coated, granular type product, the instant pesticide-fertilizer carrier systems are exceptionally stable and relatively unaffected by attrition during storage and shipping. These unique delivery systems permit components, normally incompatible with the pesticide andJor nitrogen-containing fertilizer to be physically incorporated in the granule. For example, if an adjuvant is incompatible wi~h the lo fertilizer, it can be adhered to the granule; if incompatible with the pesticide, it can be added prior to the spray coating, i.e., made part of the substrate. If it is desired to have adju~ants that require a longer exposure time to a given aqueous medium for optimum efficiency as an inherent part of the granule, for example, guar particles that require additional hydration time; pH buffers, etc., they can be preferentially or sequentially released by not having the adjuvant incorporated uniformly throughout the particle as would occur using the processing of the prior art, but rather having the adjuvant adhered to the outer surfactant coating of the granule.
By "spray-coated" is meant that the solid surfactant is melted and coated upon a substrate comprising the fertilizer while still in the molten state. This is done by spraying the molten surfactant onto the substrate, most preferably the diammonium sulfate particles in a coating blender. Complete coating of the substrate particles is not always necessary but, rather, the degree of completeness of the coating is often determined by specific requirements such as the need to isolate the fe.rt~lizer from other added incompatible adju~ants. The sprayed material, while still-in a sticky state is then continuously tumbled to partially agglomerate or granulate the i.ndividual particles while preferably the pesticide is added and bonded so as to yield dry bonded flowable granules.
o The solid, :nonionic surfactants that can be used in the process of this i.nvention are those known in the art which are solid or of a hard, nontacky wax consistency at room temperature.
Among the preferred nonionics are the following:
A) Amides such as:
i) Alkanolamides of the formula -o !l R~
R C N-~ R"
wherein R' and R" each can be -H, -CH2CH2OH, or -CH2 - CH-OH;

ii) ethoxylated alkanolamides of the formula -~ ( CH2 - CH2 - O ) xH
R - C - N
~~(CH2~CH2~O~yH; and WO 96/23408 rCT/US96/01233 iii) ethylene bisamides of the formula -!1 R - C~ H
N-CH7-CH2-N ~
H ~ C-~;
il B) Esters such as:
~
i) fatty acid esters of the formula -o R - C - O - R
~0 ii) glycerol esters of the formula -o R - C - O - CH2 - CH - CH2 - O - R~
OH;

.
iii) ethoxylated fatty acid glycol and polyethylene glycol esters of the formula -o R - C - O (CH2CH20) X-R, i iv) sorbitan esters of the formula -HO OH
O
~ CH - CH2 - O - C - R; and OH

CA 02211996 1997-07~30 WO 96/23408 PCI'/US96/01233 v) el:hoxylated sorbitan esters of the formula -H-(OCH2CH2)n-O , ~ o-(CH2CH2O)x-H

"O' '~ O

O- ( CH2CH20 ) y C) Ethoxy.lates such as:

~5 i) alky.lphenol ethoxylates of the formula -R - , - ( OcH2cH2 ) nOH;

R~

ii) alcohol ethoxylates o~ the formula -R - O - ~CH2CH2O) nH;

iii) tristyrylphenol ethoxylates of the formula -( O CH2 CH2 ) nOH
~- CH ~ CH _ CH3 CH3 ; and "C~'~
iv) mercaptan ethoxylates of the fcrmula -R - S - ( CH2CH20 ) nH;

D) End-ca.pped and EO/PO block copolymers such as -WO 96/23408 PCI~/US96101233 i) alcohol alkoxylates of the formula -fH3 R-(OCH7CH2)X - (O - CH - CH2) m ~ OH;

ii) ethylene oxide/propylene oxide block copolymers of the formula -HO - (CH2cH20)x (CH2-CH-O) m ~ (CH2CH2o) y - H;

iii) reverse copolymers of the formula -HO (CH-CH20) m~ (CHzCH2O) x~ (CH2-CH ~) 1 H;
~0 iv) chlorine capped ethoxylates of the formula -R - (OCH2CH2)xCl; and v) tetra-functional block copolymers of the ~ormula -CH, CH~
3 0 H ( O CH CHz ) " - ( OCH CH2 ) ", ( CH2 CH O ) m ~ ~ ( CH2 CH20 ) ~, H

H (OCH2CH2)y - (OICH CH2)l (CH2CHO)t~ - (CH2CH20)y~H
CH~ CH~
or 4 0 CH~ CH, H (OCH CH2)", - (5CH2 CH2)~C (CH CH20),~. - (CH~ CHO), NCHzCH N
H ( OCH CH2 ) ~ - ( OCH2 CH2 ) y ( CH2CH20 ) .;. - ( CH2CHO ) ~ .
CH~ CH3 wherein R is a fatty alkyl group, preferably a C6 - C22 fatty alkyl group, most preferably a C8 - Cl8 fatty alkyl group;
Rl is -H or a fatty alkyl group, preferably -H
or a C5 - C22 fatty alkyl group, most preferably -H or a C9 - C18 fatty alkyl group;
x, x', y, y' and n are each independently mole,s of ethylene oxide preferably 1 to 300; most preferably 1 to 150; and ~, m', 1 and l~ are each independently moles of propylene oxide, preferably 1 to 300; most preferably 1 to 150;
with the proviso that the fatty alkyl group and/or the number or arrangement of the ethylene oxide and/or propylene oxide units are such that the surfactant composition is a solid at room temperature (24-C), preferably a solid at 50-C.
Mixtures of the above surfactants are acceptable and, in fact, mixtures o~ the above surfactants with other nonionics that alone are liquid even at room temperature may be acceptable provided that the amount or nature of the liquid surfactant is such that the final particulate product does not exhibit tackiness at room temperature. Preferably, tackiness is not exhibited even at 50 C.
2S The more preferred solid nonionic surfactants are the aforedescribed alkyl alcohol ethoxylates and alkylphenol =

WO 96t23408 PCI/US96tO1233 ethoxylates.
The solid, nonionic surfactant composition of the instant granules should be ~rom about l to about 99 weiyht percent, preferably from about 3 to about 95 weight percent based on the total granule formulation weight.
The ~ost preferred solid nonionic surfactant is dinonylphenol ethoxylate () 100 E0) for it has been discovered that this compound possesses the ability to provide excellent wetting characteristics together with a high melting point.
0 Furthermore, the material exhibits an ability to dissolve in aqueous medium without formation of a gel phase.
The amount of the dry water-soluble nitrogen-cont~;n~ng fertilizer to be spray-coated by the solid nonionic composition can be ~rom about 1 to about 99 weight percent, preferably from about 1 to about 95 weight percent based on the total weight of the final spray-coated composition.
The pesticides contemplated for use in the granules of this invention are those active ingredients well. known to be of value to agriculture and are normally distributed to loci via aqueous spray means such as herbicides, fungicides, bactericides, insecticides, insect antifeedants, acaricides, miticides, nematocides, and plant growth regulants. Preferred pesticides are the herbicides selected from the group consisting of the herbicidal sulfonyl ureas, imidazolines, and glyphosates. The active ingredients should be present in the granules in pesticidally e~fective amounts, preferably from WO 96/23408 ~ us~/ol233 about 0.01 to about 90 weight percent, most preferably from about 0.03 to about 80 weight percent based on the total granule ~ormulation weight.
The essence of the pre~erred embodiment of the instant invention lies in the discovery that if solid nonionic surfactant compor,itions are spray-coated upon dry, water-soluble nitrogen-containing fertilizers such as diammonium sulfate, the dissolution rate of the dry surfactant particulate composition in aqueous solution can be greatly lo enhanced. It is also hypothesized that in addition to the action of the fertili7er per se upon the dissolution rate of the solid, nonionic surfactant composition, the coating/granulation process tends to entrap air within the coated granules thereby increasing the surface area ultimately exposed to the aqueous medium which increases the dissolution rate (as opposed to compaction and extrusion processes which tend to compress air out of the particles). Also, the pockets of entrapped air function as flotation aids which assist in keeping the coated granules from settling.
The prefer:red process of the instant spray-coating invention comprises the steps of:
a) addi.ng the dry water-soluble nitrogen-containing fert:ilizer, preferably diammonium sulfate to a blender chamber;
b) mix:Lng said fertilizer to ensure uniform dislribution;

WO 96123408 PCI'/US96/01233 c) melting the initially solid nonionic surfactant composition, preferably at a temperature of from about 65' to about 95 C. (149 - 203-F);
d) spraying the molten surfactant composition onto the fert-lizer particles in said blender chamber;
e) blending continuously to effect a uniform coa~ing and granulation of the fertilizer particles;
f) ~mi~ing pesticide particles while the surfactant composition is still tacky; and g) cooling the pesticide-containing granules, preferably to less than 50-C (122-F).
Preferably, the fertilizer particles are initially blended for at least 10 minutes before the spraying step to ensure that the initial crystal or particle sizes are uniformly distributed throughout the batch. The preferred spray blender-mixers are those of the Mark VI design manufactured by Continental Rollo or an equivalent.
Also preferably, to aid in providing a uniform granulation, the mixture should continue to be blended for at least three additional minutes after the spraying has ceased.
If it is desired to have any additional components adhere to the surface of the coated granules, e.g., if an additional additive is a fine powder and one desires to reduce dusting in the final product, the material can also be added while the coated granules are still tacky to obtain adherence, i.e., the material can be added before the granules are completely WO 96/23408 PCIrUS96/01233 cooled. Examples of such optional additional components include anti-foam agents, flow agents, anti-caking agents, stabilizers, inert fillers, gas-generating agents, dyes, and/or any adjuvants particular to the speci~ic end-use appiication of the resulting product. Optional adjuvants can be added from abou~ 0 to about 20 weight percent of the granular composi~ion. Inert ingredients can be added up to about 80 weight percenc.
Aside from being able to deliver to the end-user a complete accuralely measured, optimized and compatible pesticidal formulation in a single granule, one of the distinct advantaqes of the instant spray-coated, i.e., multi-layered particle is that it frees the preparer from many of the restrictions normally imposed upon multi-component systems manufacturers. For example, additional adjuvant components which normally would be incompati~le with the fertilizer, specifically the diammonium sulfate can be made a part of the coated granule by introducing the component after the pesticide granulation process is essentially completed, but while the multi-layered material is still tacky so that the adju~ant can be adhered to the outer surface, i.e., the component would only be in contact with the pesticide and the nonionic composition layer.
Another advantage realized by this adherence contact 2S procedure is that in addition to the pesticide, it allows other material to be placed on the outside of the spray-coated WO 96/23408 PCI~/US96/01233 granule, thus giving the adhered material preferential or advanced exposure to the aqueous media. Thus, one can also selectively sequence the exposure times of certain components of the granule.
The fertilizer of the instant process preferably should be of a coarse grade; most preferably 95 weight percent of the materlal should have an average particle size diameter of from about 200 to about 600 microns, i.e., 95 weight percent should pass through a 30 mesh (U. S. Standard) screen and not pass 0 through a 70 mesh (U. S. Standard) screen. Elimination of fines is Freferred to mi n; ml ze compaction or agglomeration of the fertilizer particles during the coating process.
The granules may be used as is or, if preferred, screened to a desired particle size.
The following specific examples are further illustrative of the present invention, but it is understood that the invention is not limited thereto. All amounts of various ingredients are by weight or weight percent unless otherwise specified.
In all of the following Examples, the dissolution rates were determined as follows:
A calculated amount of product such that t:he surfactant weight remained at 2.0 grams is added into a 250 ml beaker filled with 98 ml of deionized water at room temperature while stirring with a magnetic stirrer set to a speed of about 30-50~ full scaie and a stopwatch WO 96/23408 ~ r 101233 started. When complete dissolution is observed, i.e., the solution becomes completely clear, the time is recorded.

Exam~les I-II
A flaked dinonylphenol ethoxylate ()100 E0) (sold under the Rhone-Poulenc trademark Igepal DM-970 FLK) is blended with a sufficient amount of. a liquid isodecyl alcohol ethoxylate (4 E0) (sold under the Rhone-Poulenc trademark Rhodasurf DA-530) to produce a non-tacky, solid mixture with a 85:15 respectively weight ratio surfactant Composition A (said blend also sold by Rhone-Poulenc under the trademar~ AgRHô DS 420).
Although the isodecyl alcohol ethoxylate has an adverse effect on the melting point of the solid dinonylphenol ethoxylated surfactant, its presence is useful for the improved wetting characteristic it provides, i.e., the lower surface tension realized in the final aqueous solution as a result of its incorporation.
At room temperature, dry diammonium sulfate is added to the dry Composition A prepared above in a Sigma Blade Mixer in a weight ratio of. approximately 85:15 weight percent sulfate to surfactant. ~lending is unable to be accomplished because the materials compress together and cake.
The test is run again utilizing solely the flaked dinonylphenol ethoxylate ()100 E0), i.e., Igepal DM-970 FLK in lieu of Composit,on A. Again, the blending is unsuccessful because, even at room temperat:ure, the surfactant and diammonium sulfate compact to form cakes.

Exam~le III
r Diammonium sulfate is charged into a Continental Rollo mixer Mark VI blender. The sulfate is rotationally blended for about lO minutes. A solid nonionic surfactant composition comprising an 85:15 weight ratio of dinonylphenol ethoxylate () lO0 EO) (Igepal DM 970) and isodecyl alcohol ethoxylate (4 0 EO) (Igepal DA 530) respectively, (said nonioni.c surfactant composition blend sold under the Rhone-Poulenc trademark AgRHô
DS 420) is heated at a temperature of about 85- C until the surfactant composition is melted. The molten surfactant is then sprayed onto the rotating diammonium sulfate through fine sized 8008E spray tips. The mixture is blended continuously for three additional minutes to ensure uniform granulation.
The mixture is then cooled to about 45- C at which time an antifoam agent is blended into the mixture (and where indicated, this is followed by citric acid and a flow aid) for three minutes. The coated granular product is collected through a #8 (U. S. Standard) mesh screen. In ~hese and the following examples, the weight percentages as indicated are based on the total weight of the final granule ~ormulation.

, CA 022ll996 l997-07-30 W O 96/23408 PC~rrUS96/~1233 Table I
Di~onylpherlol Isodecyi Alcohol Ethoxylate () lO0 EO) Ethoxylate (4 EO) Ammonium Antifoam Dissolution sa~le Flaked Liouid Sulfate Aqe~t~ ~i~e (Min.) Control 85.00~ 15.00~ - - 4:25 l 81.00~ 13.00~ 5.00~ l.00~ 2:50 2 79.00~ lO.O0~ 10.00~ l O0~ 2:40 3 75.00~ 9.00~ 15.00~ l.OO~ 2:35 O ~ 20.77~ 3.60~ 74.00~ 0.07~ 1:70 a polyorganosiloxane sold under the Rhone-Poulenc trademark Rhodorsil Silicone EP 6703 ~ 1.30~ citric acid and 0.26~ flow aid (an amorphous precipitated silica sold under the Rhone-Poulenc Trademark Tixosil 38 AB) are added.
The resulting dissolution time of the solid nonionic surfactant composition indicates the significantly enhanced dissolution rates that can be unexpectedly realized by this invention, i.e., by the spray-coating of ~;~onium sulfate with the molten nonionic surfactant composition.

ExamPle IV
84.05 weight: percent diammonium sulfate is charged into a Continental Rollo mixer Mark VI blender. The sulfate is rotationally blended for about 10 minutes. 15 weight percent of a solid nonionic surfactant composition comprising a 85:15 weight ratio of dinonylphenol ethoxylate () 100 E0) (Igepal DM
970) to isodecyl alcohol ethoxylate (4 E0) (Igepal DA 530) respectively, (said nonionic surfactant composition blend sold under the Rhone-eoulenc trademar~ AgRHô DS 420) is heated at a temperature of about 85 C until the surfactant composition is melted. The molten surfactant is then sprayed onto the rotating ammoniurn sulfate through five sized 8008E spray tips.
The mixture is blended continuously for three additional WO 96/23408 ~CT/US96/01233 minutes to ensure uniform granulation. The mixture is then cooled to about 45- C at which time 0.2 weight percent of antifoam Rhodorsil Silicone EP 6703 is blended into the mixture for three minutes. Bastly, 0.75 weight percent of an anti-caking or free -low aid (Tixosil 38AB) is b].ended in for a few minutes. The coated granular product is collected through a #8 mesh sieve.
The dissolution times of the resulting coated granules are less than half that of the solid nonionic sur~actant composition alone.

ExamPle V
The process of Example IV is followed utilizing the following weight percentages: ammonium sulfate - 93.15~; AgRHo 15 DS 420 - 6.0~; Rhodorsil EP 6703 - 0.1~; and Tixosil 38 AB -0.75~.
As in Example IV, the dissolution times of the resulting coated granules are again less than half that of the solid nonionic surfactant compositions alone.
In addition to the above-identified advantages of potentially increased surfactant dissolution rates and the avoidance of compaction problems associated with attempts to intimately admix diammonium sulfate with the solid surfactants of the instant invention, the spray-admixed compositions of this invention do no~ suffer from par~icle separatlon that can occur with simple solid blends of the same materials.

WO 96/23408 PCI'/US96/01233 In addition to the aforementioned enhanced dissolution;
incompatibility avoidance; and preferential dissolution advantages, the coated products of this invention also realize a very uniform granuie size together with excellent attrition resistance. Serendipitously, the process is significantly less energy intensive and more capital cost e~fective than other melt-admixing processes, e.g., the extrusion processes of the prior art.

Exam~les VI - XV
Twenty five pounds of Adjuvant A is prepared by charging 93.15 weight percent diammonium sulfate into a Continental ~ Rollo Mixer Mark VI Blender. The sulfate is rotationally blended for about 10 minutes. 6.0 weight percent of a solid nonionic surfactant composition comprising an 85:15 weight ratio of dinonylphenol ethoxylate () 100 EO) (Igepal DM 970) to isodecyl alcohol ethoxylate (4 EO) (Igepal DA 530) respectively, (said nonionic surfactant composition blend sold under the Rhone-Poulenc trademark AgRHô DS 420) is heated at a temperature of about 85- C until the surfactant composition is melted. The molten surfactant is then sprayed onto the rotating diammonium sulfate through five sized 8008E spray tips. The mixture is blended continuously for two additional minutes to ensure uniform granulating, at which time herbicides ~e identified and, in the amounts listed below, are added. The material is tumble blended an additional three minutes to adhere the particulate pesticide to and incorporate them in the granules. The mixture is then cooled to about 45-C, at which time 0.8 oz. of antifoam Rhodorsil Silicone EP
6703 is blended into the mixture for three minutes. Lastly, 6.0 oz. of an anti-caking or free flow aid (Tixosil 38 AB) is blended in for a few minutes. The pesticide-adhered granules o are cooled and collected through a sieve.
The following table illustrates the enhanced phytotoxicity realized by the use of the dry bonded pesticidal-adjuvant systems of the instant invention prepared as above described compared to that realized by standard liquid adjuvant-pesticide blends. The carrier for the compositions listed in Table II is water at ten gallons per acre.
Kinetic (a trademark of Helena Chemical Co.) is a proprietary liquid surfactant adjuvant system comprising a polyorganosilicone and an ethyleneoxide/propyleneoxide block copolymer. Dynamic (a trademark of Helena Chemical Co.) is a proprietary liquid adjuvant system comprising methylated seed oil (MSO) and a polyorganosilicone. C.O.C. is a crop oil concentrate usually about 83 weight percent paraffinic crop oil and 17 weight percent emulsifier.

W O 96/23408 P ~ rUS96/01233 - Table II
Rate per ~ Control Days before Cro~ Com~ounds Acre (22 davs) Visual ActiVity Corn Dry 8Onded2.'~0 lbs.lO0 5 Fert/Adjuvan~
Beacon .78 oz.
Accent .78 oz.

Corn Kinetic ~.60 oz. 95 lO
Beacon .78 oz.
Accen~ .78 oz.
SoybeansDry Bonded 2.50 lbs. lO0 2 Fert/Adjuv.an~
Pursuit 4.00 oz.
Soybeans Dynamic 6.~0 oz. 95 lO
Pursuit 4.00 oz.
Soybeans Dry Bonded 2.S0 lbs. lO0 3 Fert/Adjuvan~
Classic .33 oz.
Pinnacle .2S oz.
Soybeans Kinetic l.60 oz. 95 5 Classic .66 oz.
Pinnacle .66 oz.
Soybeans Dry Bonded 2.50 lbs. lO0 2.5 Fert/Adjuv.an~
Poast Plus 18.00 oz.
Soybeans C.O.C. 2.00 pts. 95 14 Poast Plus 18.00 oz.
Soybeans Dry Bonded 2.50 lbs. lO0 3 Fert/Adjuvan~
Pursuit 4.00 oz.
Butyrac 2003~00 oz.
3eacon is a trademark of Ciba Gei~y for a sulfonyl urea formulation.
4S Accent, Classic and Pinnacie are trademarks of DuPont for sulfonyl urea formulations.
Pursuit is a trademarlc of American Cyanamid for an imidazoline fo~nulation.
Poast Plus is a traLdemark of BASF for a proprietary cycl~h~ ne~ione formulation.
Butyrac 200 is a trademark ror a 2,4 DB formulation sold by Rhone-Poulenc Inc.
The abo~e -esults illustrate the significantly enhanced herbicid~l activity that can ~e realized vla the use of the dry bonded pes~icidal-adjuvant granules of the instant invention over the activity levels when standard liquid adjuvant systems are used.

CA 022ll996 l997-07-30 W O 96/23408 P ~ rUS96/OlZ33 Examples XVI - XVII
The following examples illustrate the enhanced phytotoxicity realized by the use of a glyphosate herbicide incorporated into the granulated products of the surfactant-fertilizer carrier systems of this invention prepared asdescribed in Examples VI - XV with the followiny changes to the pesticidal granular composition: 84.05 weight percent diammonlum sulfate; 15.0 weight percent AgRHô DS 420; 1.6 oz.
Rhodorsil Silicone EP 6703; and 6.0 oz. of Tixosil 38 AB. The 0 herbicide used is Roundup which is a trademark of Monsanto for a glyphosate herbicidal ~ormulation. Quest is a proprietary ammonia-based water conditioner of Helena Chemical Co. The carrier for the compositions is again ten gallons of water per acre.

Table III

~ Control Days ~efore Com~ounds Rate ~er Acre (22 davs) Visual Activitv 20 Dry Bonded O l~s.100 5 Fert/Adjuvant Roundup '.0 qt.

~ n~--r l.O qt.90 lO

25 Quest 3.2 oz.

~inet~c 1.6 oz.

The above results illustrate the greatly enhanced herbicidal activity achieved via the use of the dry bonded pesticidal-adjuvant granules of this invention when the pesticide is a glyphosate herbicide. The outstanding activity of these dry bonded granules are the result of the combined properties of high surfactant loadings; high ammonium ion levels; and rapid aqueous dispersement. These factors, WO 96/23408 PCI'IIJS96/01233 together with the fact that 1) the HLB is about 16, i.e., within the art-recog.,ized preferred range of 12-17 and 2) the compositions dry i.ni~-ally to a moist gel on leaf surfaces (an ideal condition as Freviously noted for increased pesticide leaf penetration) combine to make these dry bonded granules powerful products _or the pesticide end-user. The final granular product is such that it produces ~ery little foam;
low dust levels a.nd odor; is non-compacting; and spills are easily swept up. The dry bonded granular pesticide delivery 0 systems of this invention enable a rapidly dispersing, completely optimized and balanced pesticidal-adjuvant-fertilizer composition to be prepared and, there~ore, combines performance, convenience, and safety to the end-user in one granular product -- an ideal situation.
Although the present invention has been described and illustrated with reference to specific examples, it is understood that modifications and variations of composition and procedure are contemplated within the scope of the following claims:

Claims (23)

We claim:

1. A method for producing a dry bonded granular pesticide system comprising spray-coating from about 1 to about 99 weight percent dry, water-soluble nitrogen-containing fertilizer with from about 1 to about 99 weight percent of a solid, nonionic surfactant composition and admixing from about 0.01 to about 90 weight percent pesticide while the surfactant composition is still tacky; the weight percentage based on the total weight of the spray-coated composition.

2. The method of claim 1 wherein the fertilizer is present from about 1 to about 95 weight percent of the spray-coated granular composition.

3. The method of claim 1 wherein said fertilizer is diammonium sulfate.

4. The method of claim 2 wherein said fertilizer is diammonium sulfate.

5. A method for producing a dry bonded granular pesticide system comprising:
spray-coating from about 1 to about 99 weight percent dry water-soluble, nitrogen-containing fertilizer with from about 1 to about 99 weight percent of a solid, nonionic surfactant composition selected from the group consisting of:

i) alkanolamides of the formula wherein R' and R" each can be -H7 -CH2 CH2 OH, or -CH2 ;

ii) ethoxylated alkanolamides of the formula ;

iii) ethylene bisamides of the formula ;

iv) fatty acid esters of the formula ;

v) glycerol esters of the formula ;

vi) ethoxylated fatty acid glycol and polyethylene glycol esters of the formula ;

vii) sorbitan esters of the formula ;

viii) ethoxylated sorbitan esters of the formula ;

ix) alkylphenol ethoxylates of the formula ;

x) alcohol ethoxylates of the formula R - O - (CH2CH2O)nH;
xi) tristyrylphenol ethoxylates of the formula ;

xii) mercaptan ethoxylates of the formula R - S - (CH2CH2O)nH;

xiii) alcohol alkoxylates of the formula ;

xiv) ethyleneoxide/propyleneoxide block copolymers of the formula ;

xv) reverse copolymers of the formula ;

xvi) chlorine capped ethoxylates of the formula R - (OCH2CH2)xCl;
xvii) tetra-functional block copolymers of the formula ;

or ; and xviii) mixtures thereof wherein R is a fatty alkyl group;

R1 is -H or a fatty alkyl group;
x, x', y, y' and n are each independently moles of ethyleneoxide; and m, m', l and l' are each independently moles of propyleneoxide; and with the proviso that the fatty alkyl group and/or the number or arrangement of the ethyleneoxide and/or propyleneoxide units are such that the surfactant composition is solid at 24°C; and admixing from about 0.01 to about 90 weight percent pesticide while the surfactant composition is still in a tacky state; (all weight percents based on the total spray-coated granular composition weight).

6. The method of claim 5 wherein R fatty alkyl groups are from C6 to C22;
R1 is H or the fatty alkyl groups are from C6 to C22;
x, x', y, y', and n are each independently from 1 to 300; and m, m', l, and l' are each independently from 1 to 300.

7. The method of claim 6 wherein R is C8 to C18 alkyl;
R1 is H or C8 to C18 alkyl;
x, x' y, y' and n are each independently from 1 to 200;
m, m', l, and l' are each independently from 1 to 200.

8. A method for producing a dry bonded granular pesticide system comprising a) mixing dry water-soluble nitrogen-containing fertilizer particles in a blending chamber;
b) melting a solid nonionic surfactant composition;
c) spraying the molten surfactant composition onto said fertilizer;
d) blending continuously to achieve a uniform coating and granulation of the fertilizer particles;
e) admixing pesticide particles while the surfactant composition is still tacky; and f) cooling the pesticide-containing granules wherein said fertilizer comprises from about 1 to about 99 weight percent of the granule composition; said nonionic surfactant comprises from about 1 to about 99 weight percent; and said pesticide comprises from about 0.01 to about 90 weight percent (all weight percents based on the total spray-coated granular composition weight).

9. The method of claim 8 wherein said fertilizer is present from about 1 to about 95 weight percent of the coated composition.

10. The method of claim 8 wherein said fertilizer is diammonium sulfate.

11. The method of claim 9 wherein said fertilizer is diammonium sulfate.

12. A method for producing a dry bonded granular pesticide system comprising a) mixing dry water-soluble nitrogen-containing fertilizer particles in a blending chamber;
b) melting a solid nonionic surfactant selected from the group consisting of i) alkanolamides wherein R' and R" each can be -H, -CH2 CH2 OH, or -CH2 - CH-OH;
¦

ii) ethoxylated alkanolamides of the formula ;

iii) ethylene bisamides of the formula ;

iv) fatty acid esters of the formula ;

v) glycerol esters of the formula ;

vi) ethoxylated fatty acid glycol and polyethylene glycol esters of the formula ;

vii) sorbitan esters of the formula ;

viii) ethoxylated sorbitan esters of the formula ;

ix) alkylphenol ethoxylates of the formula ;

x) alcohol ethoxylates of the formula R - O - (CH2CH2O)nH;

xi) tristyrylphenol ethoxylates of the formula ;

xii) mercaptan ethoxylates of the formula R - S - (CH2CH2O)nH;

xiii) alcohol alkoxylates of the formula ;

xiv) ethyleneoxide/propyleneoxide block copolymers of the formula ;

xv) reverse copolymers of the formula ;

xvi) chlorine capped ethoxylates of the formula R - (OCH2CH2)xCl;

xvii) tetra-functional block copolymers of the formula or ; and xviii) mixtures thereof wherein R is a fatty alkyl group;
R1 is -H or a fatty alkyl group;
x, x', y, y', and n are each independently moles of ethyleneoxide; and m, m', l, and l' are each independently moles of propyleneoxide; and with the proviso that the fatty alkyl group and/or the number or arrangement of the ethyleneoxide and/or propyleneoxide units are such that the surfactant composition is solid at 24°C.
c) spraying the molten surfactant onto the fertilizer;
d) blending continuously to achieve a uniform coating and granulation of the fertilizer particles;
e) admixing pesticide particles while the surfactant composition is still tacky; and f) cooling the pesticide-containing granules wherein said fertilizer comprises from about 1 to about 99 weight percent of the granular composition; said nonionic surfactant comprises from about 1 to about 99 weight percent; and said pesticide comprises from about 0.01 to about 90 weight percent (all weight percents based on the total spray-coated granular composition weight).

13. The method of claim 12 wherein the fertilizer is present from about 1 to about 95 weight percent based on the coated composition.

14. The method of claim 12 wherein R fatty alkyl groups are from C6 to C22 R1 is -H or the fatty alkyl groups are from C5 to C22;
x, x', y, y', and n are each independently 1 to 300;
and m, m', l, and l' are each independently 1 to 300.

15. The method of claim 14 wherein R is C9 - C18 alkyl;
R1 is -A or C8 - C18 alkyl;
x, x', y, y', and n are each independently from 1 to 200; and m, m', l, and l' are each independently from 1 to 200.

16. The method of claim 8 wherein i) the nonionic surfactant is melted at from about 65°
C to about 95° C; and ii) the pesticidal granules particles are cooled to less than about 50° C.

17. The method of claim 12 wherein i) the nonionic surfactant is melted at from about 65°
C to about 95° C; and ii) the pesticidal granules particles are cooled to less than about 50° C.

18. The dry bonded pesticide granules produced by the process of claim 1.

19. The dry bonded pesticide granules produced by the process of claim 3.

20. The dry bonded pesticide granules produced by the process of claim 5.

21. The dry bonded pesticide granules produced by the process of claim 8.

22. The dry bonded pesticide granules produced by the process of claim 10.

23. The dry bonded pesticide granules produced by the process of claim 12.