PESTICIDAL GRANULES CONTAINING FERTILIZER AND SURFACTANT

GRANULES PESTICIDES CONTENANT UN FERTILISANT ET UN AGENT TENSIOACTIF

English 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.

French Abstract

L'invention concerne un procédé de production d'un système pesticide granulaire et lié à sec, de libération d'agent tensioactif/fertilisant, qui consiste à enduire par projection environ 1 à 99 % des particules de fertilisant sèches, hydosolubles et contenant de l'azote, de préférence du sulfate de diammonium, d'une composition tensioactive, à mélanger le pesticide et à granuler le système de libération final. L'invention porte également sur les granulés ainsi produits.

Claims

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:
28

i) alkanolamides of the formula
<IMG>
wherein R' and R" each can be -H7 -CH2 CH2 OH,
or -CH2
<IMG>;
ii) ethoxylated alkanolamides of the formula
<IMG>;
iii) ethylene bisamides of the formula
<IMG>;
iv) fatty acid esters of the formula
<IMG>;
v) glycerol esters of the formula
<IMG>;
vi) ethoxylated fatty acid glycol and polyethylene
glycol esters of the formula
<IMG>;
29

vii) sorbitan esters of the formula
<IMG>;
viii) ethoxylated sorbitan esters of the formula
<IMG>;
ix) alkylphenol ethoxylates of the formula
<IMG>;
x) alcohol ethoxylates of the formula
R - O - (CH2CH2O)nH;
xi) tristyrylphenol ethoxylates of the formula
<IMG>;
xii) mercaptan ethoxylates of the formula
R - S - (CH2CH2O)nH;

xiii) alcohol alkoxylates of the formula
<IMG>;
xiv) ethyleneoxide/propyleneoxide block copolymers
of the formula
<IMG>;
xv) reverse copolymers of the formula
<IMG>;
xvi) chlorine capped ethoxylates of the formula
R - (OCH2CH2)xCl;
xvii) tetra-functional block copolymers of the
formula
<IMG>;
or
<IMG>; and
xviii) mixtures thereof
wherein
R is a fatty alkyl group;
31

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.
32

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
33

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
<IMG>
wherein R' and R" each can be -H, -CH2 CH2 OH, or
-CH2 - CH-OH;
¦
CH3
ii) ethoxylated alkanolamides of the formula
<IMG>;
iii) ethylene bisamides of the formula
<IMG>;
iv) fatty acid esters of the formula
<IMG>;
34

v) glycerol esters of the formula
<IMG>;
vi) ethoxylated fatty acid glycol and polyethylene
glycol esters of the formula
<IMG>;
vii) sorbitan esters of the formula
<IMG>;
viii) ethoxylated sorbitan esters of the formula
<IMG>;
ix) alkylphenol ethoxylates of the formula
<IMG>;
x) alcohol ethoxylates of the formula
R - O - (CH2CH2O)nH;

xi) tristyrylphenol ethoxylates of the formula
<IMG>;
xii) mercaptan ethoxylates of the formula
R - S - (CH2CH2O)nH;
xiii) alcohol alkoxylates of the formula
<IMG>;
xiv) ethyleneoxide/propyleneoxide block copolymers
of the formula
<IMG>;
xv) reverse copolymers of the formula
<IMG>;
xvi) chlorine capped ethoxylates of the formula
R - (OCH2CH2)xCl;
36

xvii) tetra-functional block copolymers of the
formula
<IMG>
or
<IMG>; 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
37

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
38

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.
39

Description

-
CA 02211996 1997-07-30
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

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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.

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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

CA 02211996 1997-07-30
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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

CA 02211996 1997-07-30
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.

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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

CA 02211996 1997-07-30
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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

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WO 96/23408 PCTIUS96/01233
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;
CH3
ii) ethoxylated alkanolamides of the formula -
~ ( CH2 - CH2 - O ) xH
R - C - N
~~(CH2~CH2~O~yH; and

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WO 96/23408 rCT/US96/01233
iii) ethylene bisamides of the formula -
!1
R - C~ H
N-CH7-CH2-N ~
H ~ C-~;
il
0 0
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

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WO 96/23408 PCI'/US96/01233
v) el:hoxylated sorbitan esters of the formula -
H-(OCH2CH2)n-O , ~ o-(CH2CH2O)x-H
"O' '~ O
CH-CH2-G-C-R
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
CH3 - C
"C~'~
iv) mercaptan ethoxylates of the fcrmula -
R - S - ( CH2CH20 ) nH;
D) End-ca.pped and EO/PO block copolymers such as -
11

CA 02211996 1997-07-30
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 -
CIH3
HO - (CH2cH20)x (CH2-CH-O) m ~ (CH2CH2o) y - H;
iii) reverse copolymers of the formula -
CH3 ICH3
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
NCH2 CH2N
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

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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

=
CA 02211996 1997-07-30
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

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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;

CA 02211996 1997-07-30
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

CA 02211996 1997-07-30
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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

CA 02211996 1997-07-30
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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

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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
19

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WO 96/23408 PCT/US96/01233
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

CA 02211996 1997-07-30
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.

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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

CA 02211996 1997-07-30
WO 96/23408 PCIIUS96/01233
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.
24

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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.
0
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.
2S

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,

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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: