Note: Descriptions are shown in the official language in which they were submitted.
~w~
04/05~3 16:12 ~416 823 0044 ICI SllE~IDA~i PRK ~1005
2093377
~ ICIAM 37512
Be)LID a5RICTI~I!I~ AW~AJ77rlt
~$-1~ of th- S~v-nt~on
The pre--nt lnventlon rel~te~ to eol~d, free-
flowing ~d~uvant-, p~rticularly for u~e w1th
~gr~cultural chemie~l~, auch ~B pe~tlCid~L, in dry form.
Baokgroun~ oX th- ~v-ntlon
Agricultural ad~uvant6 ~rQ mat~rial~ which aid
or ~odi~y the pQrfor~ance o~ nn agrlch~micnl. Ad~uvants
may al~o improve the phy~ical properties of an
agricultural for~ul~tion. ~or ~xample, an actlvator
adjuvant incr~a~e~ t~e b~olog~cal e~lcacy o~ a
pHsticido (e.g., lnc~otlc~de, her~loi~e, ~ungicld-). A
compatibility ~g-nt pr-vente th~ ohæmlcal lnteractlon of
two or ~or~ ~griche~ic~l formulatlons in a tank ~ix or
lmprove~ th~ ho~ogeneity Or llqui~ ~rtillzer with other
~grlcho~cal~ in ouc~ ~ixturo~. A wettlng ag~nt or
Epreadlng agent incr~a~es th~ eur~ace are~ covered by a
glvsn volune of ~pr~y ~ixture. Fertilizer~ l~kQ urea or
~la~onlu~ pho~phato ar~ fr-qu~ntly u~ed a~ ad~uvant~ or
Wlth other ~djuv~nt6 to i~prov~ ef~io~cy of pe~ticlde
formulatlons. Follar fortillzatlon c~n be u~ed to
~upply uroa nitrogen ~nd other nutri~nt~ to crop~.
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04/05/~3 16:13 ~416 8~3 0044 ICI SHERIl)A:`I PRK 1~006
- 2 - 2~93377
The ~djuvant systems commonly use non-ionic
~urraatant6, but ~Q~t o~ these ~urfactant~ ~re liguid6
or wnxy ~ . Hence, thoy ~re difficult to include in
a dry ~ormul~ unless ~d~orbent~, 6UC~ A~ ~lay~ or
n11icas, are employed a~ solid carrier~. How~ver, the~Q
~olld carrier~ are not 60luble ~n w~ter, not
biologlcally ~ctive, may clog ~pray l$n~ and nozzl~ or
$ncreaae nozzle wear. Example~ o~ ~uch granulated
pe~tlcide ~aterials which may include an ndsorbent
carrier are described, for example, in Canadlan P~tent
,20g,363 o~ BASF Wyandotte Corporation.
Tt h~o al~o ~en known to ~orm ~olid
agrl~ultura~ formulations in which the dgric~ltural
chemical 18 lncorporated directly in the powd~r
particle~ oS the rormulaticn. An ~x~mple of ~uch a
ey~tem i~ di~clooed ~n ~.S. P~t~nt 4,283,525 i~sued to
Amerlc~n cyanamld Co., wherein a pyrazolium salt (an
herbicide), urea, and a li~uid, non-ionic ~ur~actunt ~re
~ixed and heate~ togsther to ~orm ~ ~olten mlxtur~ w~ich
i~ th~n solidir~ed lnto granulss, bsad~, prillc, fl~ke~,
or th2 like.
~ owever, ouch co~po~it~ons lack th~
versatility of sy~t~3 in which ho ~d~uvant may ~e
manufactured, ~hipped and stored Geparately from the
agricultural chemic~ls and ~ixed at the tlme and site of
appllcation of the pe~tic~de. E~pecially important is
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04~'Q5/93 16 :14 g5~41ff 823 0~44 ICI SHERIDA~I PRK ~1007
2093377
1 --
tha fact th~t ~ eront level~ of ad~uvant are use~ with
given level o~ pe6ticide for dlr~ersnt crop
appl~c~t~on~, v~rious ~t~ge~ of crop growth or dif~erent
woath~r or cli~ate. With her~icide~, fid~uv~nt
requiroment~ ~ay al~o dep~n~ on target wo~d 3~p~cle~.
Al~o known ~rom USSR Patent 242,59z o~ Simoncv
~t al. ~All-Un~on ~ientific-Research In6tltut2 of
Chemical~ for Pl~t Protection) ~re peeticidal
lubricating powder~, containing et~ylene oxide or
~lo poly~thy~en~ ~lyccl ~ur~act~nt~ wi~h urea co~pounds.
:S~c al~o V. D. Slmonov t al., "U~Q 0~ Cl~thrate
Co~pound~ of ~rea with Surfact~nts ~n the Production of
Pesticid~l Preparation~," po~l. Neftekhim. Sekts.
Ba~hkir. Respub. Pravl._V6es. Xhi~. Obs~chQst. 6:32~-9
15 ~1971) and USSR Patent 523,895 Of E~e19YanOV t a1.,
~Perhydrates of urea Clathrat~ ~ith 6UrfaCtant~ . "
However, ln USSR Patent 2~2, 592, the princ~pal
ChemiCa1 fUnCt~ on i~ one of pr~vention o~ c~Xing o~ the
POWder ~OrmU1~t~0n rllthe~ thlln biO10g1Ca1 ~CtiV~t10n 0
the ~ctlvo pesticide componQnt. Other ~mportant
~d~uvant ~ctivity whish is not dl~clo~ed or clai~ad ~n
thi~ patent ~ncludes enbanc~d biol~gicsl e~f~c~cy,
~mproved spray tahk co~patibility, better wetting or
sticklng properties.
~s~
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04~05/~3 16:14 ~41R 823 0044 ICI SHERIDA.~ PRK 1~008
- 4 - 2093377
3u~ry of tho S~v-~tlou
According to the pre~nt inv~n~ion aolid,
~r~e-flowing ~djuvants, whlch di~solve oo~plfftely and
r~pidly ~n wat~r, ~re provifled ~n th~ Sor~ of ~ow~er~d
adducts of urea and at lea8t on0 surfact~nt, pr~erably
non-ionic, in ~hich the sur~actant i~ G~lecte~ ~rom an
ethoxy~at~d linear or branch~d chain aliphat1c nlcohol
or acl~ containing at least 10 mol~c of ethylene oxide
per mole of acid or alcohol ~nd 8 to 24 oarbon atoms ln
the alipha~ic cbaln; ~lock or rando~ copolymer~ of
ethylene oxidz and propylene oxide: an~ block or random
copoly~er~ of ethylRne oxide ~nd prspylen~ oxide ba~ed
on ~liphatic alcohol~ h~ving 4 to 18 carbon atomc.
Additional acldifying surfActants may include anionic
phosp~ate e~ters of th~ ~ormula ROP(O)(OH)2 wherein R is
alkyl, alkylaryl, alkoxylatod alkyl, or ~lkoxylat~d
alkyl~ryl. The ~dduct~ of the ~v0ntion ~ay furt~er
include additional f~rtilizer component~ ~uch hS
diam~onium pho~phat~, ~nd/or ~tlckl~g agent~, ~u~h a~
~atty ~cid~ ~aving 12 to 24 earbon~ in the aliphatic
chain or ~lkoxylat~d novolac re-in#.
The ad~uvant~ of t~e ~nvent~on ~ay be ~ormed
by m~xing and hQating tha urea, ~urSactnnts a~d ot~er
componsnt~ to form a uniform liquid melt, and then
8praying the liquid ~elt ~nto a cool~ng tower to produce
a free-flowlng powder. The~a ~dducts can then ~e built
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04~'05/93 16:15 ~416 823 00~4 ICI SIIERID.~N PX~ 12100~
_ 5 _ 2093377
into ~ dry pesticid~ for~ulation to lmprove wetting,
comp~tlblllty, buffering, disper3ibility and~or provide
ad~uvancy. Alternatively, t~e adducte can be added
directly to the spray t~nk like ~ny other t~nk-mix
ad~uvant. Reg~rdle~s of the ~etho~ o~ u~e, the
ad~uvant~ o~ the invention will activate pe~ticlde~
biologic~lly a~ well a~ functioning as wetting agents,
co~patibllity agent6 or fertilizer-nutrient. Enhanced
actl~ity, b~ologically o~ otherwi6e, achieves the
~o de~ired pe~tlcidal effact with lower level~ of the more
~xpen~iv~ pesticide6.
D~t~ Do~or~ptio~ of Pse f erro~ E~ i~e~ts
Urea ~nd diammoniu~ pho#phate ~re commonly
used as ~ertilizer~. According to the pre~ent
lS inventlon, it h~s been found that urea, wlth or without
dia~monium phosphatQ or oth~r ~ertilizer6, ~orm~ ~ ~olid
adduct with certain non-ionlc surfwtant~. This ~dduct
or complex ~ largely a type o~ phy~ical "lnclusi~n
compound" or "clathrate.~ While tha ex~ct structur~ i5
not known, it i~ believ~ that at l~ast a phy~lcal
combi~tion exists, which will be roferred to herein a~
an ~dduct.
The ~pecific sur~actante ~urface actlve
~gents) which have been found to complax with urea
include the ethoxy~ated aliphatic alcohol~ or acids
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_ _04/05/03 _ ~16:15 SE~416 82S 00~4 ICI SHEI'~IDA~I PRK ~0~0
.
2093377
- 6 - :
having B to ~4 carbon ~toms in the ~lcohol or aci~ chaln
an~ containlng ~t lea~t 10 and prefer~bly 10 to 50 mole~
of ~thylono oxide per mole o~ ~cid or alcohol. Wh$lR
ethylene oxl~e i8 prererred, it will be understoo~ that
other ~lkylene oxides, particularly propylene ox~ ay
be 6ub~tituted.
Yreferred surractznts of this type ~or U6~ in
the pre~ent invent~on includ2 othoxylated C13 to C15
aliphatic alcohol~ Yhera the degree o~ othoxylat~on
rangee from ll to 20 ~0108, which ~re commercially
av~ilabl~ from ICI Americas Inc. under the trademark
5YNPERONIC~ A-ll through A-~O, and ~thoxyl~ted tridecyl
(C13) alcohols where the ~egree of etboxylation range~
from 12 to 15 mole~, ~hich are commercially ~v~llable
1~ from ICI Am~ricac Inc. under the tr~dem~rks RENEX~ 30
and 31. Al~o sultable ~r~ the ethoxylated for~o of C8
to C24 fatty ~ci~, prderably othoxyl~ted C14 to C18
f~tty acidc, w~ere the degree of ethoxyl~tion ~ B at
leagt 10 ~018~, pref-rably 20 to 4~ ~oleo, per mole of
20 acid. ~or xampla, polyoxyethylene ~40) st~ar~c ~ci~,
co~m~rci~lly ovaila~le from ICI Americ~s, Inc. a~ ~Y~g
52, i~ ~ preferred example.
Al~o suitabl- for complexing with ure~
nccording to the precent lnvention are ethoxylDted Cl2
to C~8 alcohole teaturated or unsaturated~ having 15 to
30 moles of ethylene ox$de per mole o~ alcohol, 6uch ~s
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_ _ 04/05~3 16:16 2~416 823 0044 ICI S~ERIDI~i PRK ~011
2093377
polyoxyethylenQ (20~ cetyl alcohol an~ polyoxyethylene
(20) oleyl alcohol. The number ~n parenthesi~ in~icate~
the degree of ethoxyl~tion.
Anoth~r ~it~le cla~s o~ non-ionic
our~act~nt~ for ~o~plexing w~th uro~ ~ra variou~ random
~nd/or block ~opoly~er~ of Qthylene oxide ana propylene
ox;de, or r~ndom and~cr blo~k copolym~r~ Or ethylene
oxld2 ~nd propylene oxide ba~ed on ~liphatic alcohol~
having 4 to 18 carbon atoms, pre~erably having a
molecular weight ln the r~nge Or 500 to 8000. Preferred
examples o~ the form~r are com~erclally avail~ble from
ICI Americ~6 Inc. such a~ SYNPERONIC ~tP103. The
l~tter ~re copolymsr~ in wh. ~h the molecular welgnt i~
built up w~th ~thylQne oxide ~nd propylene oxide unlts,
an exa~ple being polyoxyethylene l45) polyoxypropylene
(38) butyl carbitol.
It ~hould be under~too~ th~t m~ny ~urfactants,
includin~ many polyoxyethylen~ (PO~B) have been tried,
but ~any nre not compatlb~e with urea and/or do not
produce complexes wi~h urea or do not for~ 6atisfactory
solid adduct~ ~or use in tho pre~ent in~ention.
~ he uroa 1~ proferably present in the adducts
of tbu ~nvention ln an a~ount o~ about 40 to 75 weight
percent of the complex, and the nonionic ~nd~or anionic
sur~actants are preferably pre~ent in an amount of about
25 to 60 welght percent of th~ complex. However, the
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__04/05~3 16:17 2P41~ 823 0044 ICI SI~ERIDAN PRR 1~012
377
- 8 -
complox~ of the invention may al60 lnclude ether
fartiliz~rs in amount~ up to about 30 we~gbt perc~nt,
suoh a6 ~lammoniu~ pho~phat~ or a~onlum nitrate. Where
the eo~plax inelude~ another fert~lizRr beslde urea, a
typleal forDulat~on aay lnelude, for example, about 40%
urea, about 40% surfactant and about 20% of diammoniu~
pho~phate or other fert~lizer.
Th~ ~dduet~ of the lnvention may al~o include ~:
an anion~e ~urfAetant nc aeidify~ng agent, ~uch a~ nn
lo organlc pho~ph~te e~ter derivod f~om aleohol6 or
~thoxylat~d alcohol~ . ~h~ ae1difying agent m~y be
pr~ent in an amount up to about ~0 weight percent.
Aeldl~ying agent~ are u3ed to lower the p~ o~ pe~ticide
~pray mixturo~. Some pe~tieido betives are more
effeetlvQ or ~table ~n the aeid form. Pho~phate esters
may aloo ~unction ~s aetivator ad~uvants, wetting
~g~nts, dlsper~nte or oompatibillty ag~nt~. An exa~ple
of a ~u~tablo pho~ph~te e~ter ~nionie curfaetant is
polyoxyet~yleno (12) tr$decyl alGohol phosphate,
av~ilablQ ~rom ICI am-riea6 Ine. a~ ATPHOS- 3232.
The ~dduet~ of the invention ~ay further
lnelud- stleklng ag~nt~, wbieh ara e~cntiAlly known to
i~prove raln-~a~tn~ of the pestieid- Sormul~tlon.
Such ~ticking agent~ $nclude aliph~tie fatty aeids
having 12 to 24 c~rbon ~to~ ~nd ~r~ ~nown a~ anlonic
~urf~ctants. Other su$t~ble ~ticking agents include
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___04/05/~3 16:17 ~416 823 0044 ICI SHERID~?~ PRK 1~013
2093377
g
alkoxylated novol~c re~ln~ whlch ~re non-ionic
~ur~actants which may b~ de~cr~ed g-nerlcally a8
poly~metbylen~-p-alkylphenoxy~-poly~oxyalkylene) ~thanol
havinq ~ to 12 mole~ o~ alkoxylatlon (i.e., oxyethylene
or oxypropyl~ne). The ~cking agqntfi mAy be pr~sent ln
the adducts o~ the ~nvention up to about 20 weight
percont, ~nd prefer~bly ~ to 20 w~$ght percent of the
adduct.
In addition to the a~ove components, the
complexQs o~ the ~boYe ~nvention ~ay al~o ln¢lude up to
about 6 weight percent water and an ~rfcctlve amount of
an ~nti-foa~ing agent.
The co~plexes oP the invontio~ ~re ~ormed by
mixing and heating all of the compon~nts together at
about 90-130C and ~tirring the mlxture unt~l a uniform
melt 1~ forced. ~h~ re~ulting melt i~ then cooled and
~ormed into ~ powde~, prefor~bly by ~prAying the liquid
m~lt in a conventional ~prny coollng tower u~ing
comention~l ~pray nozzl~ and oper~tlng conditions
which w~ll be readily ~pparent to those s~illed in the
art. In tho cooling tower the ~prayed mixture
solidiSie6 in the ~orm o~ ~ prilled powd~r resembl$ng
eoap powder. Thic powder will typically pa~s through ~
20 me~h ccreen. ~ho~ skilled in the art will recognize
that oth~r ~ethod~ of cooling the molten mlxture ~na
7~
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04/05/~3 lB:18 2~416 823 0044 ICI SHERIDA.~i PRK 1~014
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Pormlng the powder ~ay be u~ed, ~uch A~ pouring th~ melt
on ~ cold surf~c~ and then gri~ding the solidified
product ln a micropulverlzer or the like.
~he ~Qsulting powdered complex may be
for~ulated lnto a variety o~ ~olld agrlcultural
che~lcal~ or formul~tions, ~uch as p~sticlde~,
hor~icldes, growth-promotion agHnta, funglc~de~,
f~rtillzers~ otc. Such pest$cldQ ~ormulation typss
includQ water-d~spersibl~ gr~nul~ ~WDG1, wetta~le
10 powder~ (WP) or ~imple granules. The composltlons of
the invention ~ay exhibit one or moro of the following
adjuvant ~unctio~alitle~ depending on its specif ic
composition, th~ use level and the way it is ueed
~tank-mlx or built-in3: wetting or ~ticking ngent,
dlsper~ant, ~u~fer, co~patibility agent, biological
p-st~clde activator or fertilizar.
For ~xa~ple, a rel~t$v~1y c~all amount o~ the
SUb~QCt compocitlon i~ needed to proviae wett$ng or
di-persant ~unot~onality ~or a WDG or WP ~orm of
ZO pecticid~. Howov-r, h~gher l~vel~ ~ay b~ requlred to
~nh~nce t~e b~ological act~vity of a p~st~cide. Be~ldes
being built lnto pe~ticid~ ~or~ulstions, She oomplexes
can be dry blended with gr~nulated po~ticide products.
Finally, th~ cubject complex~s can be used
alons as tank-mix a~uv~nt~ ln order to lmprove
comp~tl~ility and other above-~entio~ed ~unctionalities
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04/05/~3 lô:l~ ~416 823 0044 ICI SHERIDA:~ PRK 1j~015
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2093377
11
between v~rious pesticide formulatlon~ ~nd~or fortilizer
~olutlons. ~ol~d ad~uvant~ have Dany advantageB over
liquid a~uvants, $ncluding ~llm$nation og ~xtraneous
~olvent, reduc~d ~ol~tillSy, safcty and ~a~ of
h~ndling. A~o, the ~u~eot ~olid a~uvant~ are
~eent$~11y 100~ actlve ln that there i~ no non-
functional ~olid c~rrier such a~ cl~y or ~ilica.
Ihe invc~tlon will now be illu~trated in ~Dre
detail with reference ~o tho ~ollowing speciflc, non-
li~itlng example;
~xu~ple I
An ad~uvant according to the ~nvention wasprepared ~rom the following components:
Co~po~t ~t %
15 p~lyoxyethylene (12) tridecyl ~lcohol 50.o
uraa 48.0
w~t~r 2.0
The components were all ~eltsd tog~ther at 120~C and
stirrsd untll a uni~orm llquld ~elt ~a~ ~btained. The
l~quid melt was th-n ~prayed into ~ ~ooling tower at an
inlet t~perature o~ 90-130C and a ~axi~um pressure o~
200 p~ig. The resulting powder particle6 were in the
form o~ prill6 whlch pa~s a 20 ~sh screen.
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Oq/05/~3 1~ 416 823 0044 ICI S~lERIDA~i P~K 1~016
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` 2~93377
- 12 - -
~ u~pl- A
~ ~Q ~olid ~gricultur~l ~djuvant ~n Ex~mplo I
b enhnnce5 tb~ biologlcal ~ct~vity o~ var~ou~ herblcide~
a~ well as improv~ng phy~ical prop~rtiec cuch ns w~tting
~nd di6perslb11~ty. For ex~ple, when 0.5~ of th1~
' ad~uvant co~po~ltion i~ ~dded to ~pray dllutlon ~olut~on
$ o~ N-phosphonomethylglycinotri~ethylsulfonium 6alt
(~ul~o~ato), herbicide activlty ag~inst com~on ~Qd
I speC12S iS improv~d. Th$~ dsmonstr~tes thQ octivator
functlon~lity of thls sub~oct adjuvant.
W ~ % Control
(1~ days æ t~r treatment)
8ul~o~at- ~ulro~ amplo I
I ber~uda gra~ ~CYNDA) 37 54
1 15 quackgrase (AGRR~) 46 86
field bindwe6d (CONAR) 15 ~7
purple nutsedg~ ~CYPRO) 34 37
~u~p~- 2
~hlG ~xa~pl~ illustrate~ the u~ of an
~idl~ying agent, ~.e., polyoxy0thylen~ (12) tridocyl
~ phosph~te, bu~lt into the adduct of ~xample 1. ~he
I resultin~ uvant would ~l~o lmprove cc~patibility
betw~en variou~ p~cticide ~oroulation- ~nd~or fertill~er
~olution~. :
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_ _04/05/~3 1~:20 SE~418 823 0044 ICI SHERIDAN PRK b~ol7
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2093377
-- 13 --
Co~po~ent ~lght %
polyoxyethylon~ ~12) trl~ecyl ~lcohol 39.7
polyoxyethylonQ ~12) tridecyl hlcohol phosphate 10.0
ure~ 48.0
S w~ter 2.0
anti-fo~m 0.3
The ~etho~ o~ preparation ie the s~ma a~ in
Example 1.
g
~his example lllustrate~ that ~ertil izer
co~ponents other than urea c~n be incorporat~d into the
adduct .
Compone~t 'deight
polyoxyethylene (12) trldecyl alcohol 29.7
polyoxyethylone (12) tridecyl alcohol phosphate 10.0
urea 3B.0
dia~onium pho~phste 20.0
water 2.0
anti-~oa~ 0.3
The ~ethod of p~eparation 1~ the 3a~e as ~n
Ex~mple 1.
The precent lnvention m~y he e3bodled in other ~:
~s~ecif ic forms witl~out dep~lrting from the ~-pir1t or
~6~ntial ~ttributec thereot and, nccordingly, ~eferenc~
shoul~ be m~de to the ~ppend~d cl~lms, r~t~er th~n to
the ~or~going ~pecification ~5 indicating the ~cope of
the lnv-ntion.
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