Note: Descriptions are shown in the official language in which they were submitted.
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SURFACTANTS PROVIDING ENHANCED EFFICACY AND/OR RAlNFASlNESS TO 1~ IV~
FORMUI~nONS
This invention co~ lises a new method of use of leldli~ ely low-cost, a ric~lltllrally
acceptable s~11rf~-tAntc to f~nhAnre the e~icacy or pinf~n~ss offoliar-applied pestic~
and plant growth modifying agents. This invention further co...~ FS new and useful
S colllpG~ilions of such agents, in particular the herbicide N-phGsph'~nn~ hylglycine or its
salts or mL~lures thereof, co.~ ..;ng such efficacy- or 1~;n~ e55 f nh~ in~ SUrfAr,t~ntS
BACKGROI~ND OF T~ INVI~TION
Foliar-applied pestiridA1 and plant growth modifying chemicals are widely used in
agricultural, ;~ ;A1~ recreAtion~1 and residenti~1 areas worldwide. These rh~mic~A1
10 agents illusllalivèly include ;-.~ecl;~ :dec fungicides, herbicides, plant growth re~11Ators
and plant .- -1 ~ ;P-~1 c among other c1~ ..ic~1c Such ch~n1 cA1c are typically applied by
Spl~illg on the foliage of vr~ )n to be protected, controlled, killed or modified, but
other m~thn~C such as rope-wick app1ic~ are known. Some ofthese agents show
contact action, l~lling, controlling or .llodir~.llg the growth oftarget ol~,~n;~-..s at the site
15 of depos;~inn Other chemicals are ~y: ~, translocating within the plant to a site of
action remote from the site of depo3;lion Still other ~h~..ic~lc show both contact and
~temic action.
A common concç~-- with several such chemicals is that efficacy can be reduced ifrain falls shortly after spraying or other mode of applic~tion This concelll is more
20 pronounced with ch~mic~lc that have moderate to high solubility in water. Many methods
of overcollling the problem of reduced efficacy due to rain have been ~lic~1ose(1 Such
m.otho~s are said to have the aim of e ~hA~ "r~inf~ctnçcs" offoliar-applied agents.
Methods to çnh~nt-e l~ ess include addition to the spray solution of oils or
other lipophilic sV1,st~nces, polymers and other m~t~ri~1C which are alleged to enh~n~e
25 spreading and cticl~i~ ofthe applied formulation to leaves, and ~d-lition of various
s~rf~ct~ntc Among s-vrf~t~ntc which have been disclosed for r~inf~ctn~cc çnhAncc...
are olg~los;licone copolymers, for ~ ,1e the cllluAyldled ciloY~ne Silwet L-77 of
Union Carbide Corporation. Such sl1rf~ct~nt~ as well as other spray additives used to
enh~nce l~in~ ..Fcs, tend to be 1~ lalively ~ ,ens;ve and many have other drawbacks.
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1Y, a l~;"r~ S rnh~u~ p ms~risl may be provided by the
msmlf~urer or s.lppliel ofthe foliar-applied p~ir;d-sl or plant grorvth modifying agent
as an ingred;~ll in the ro~ n of said agent.
An eYsrnp'e of a foliar-applied agent whose ~Irica~ is se -s;live to the oc~ u~ ce
S of rain shortly a~er arp1ic~stinn is the herbicide N-phosphnn~l~ h~ rchle, also known
by its co...---o~ name ~hos~e
Gly~hn~e is a highly e~live and co..~...e~c;ally i1~1PO1l~1l herbicide useful for
co...l~t~; .e the p,~scnce of a wide variety of ul~anled Vqet~ 7;nC~ ;ng~;C~ U
weeds. GIYI,hGS~e is applied as a fi~ ed product to the foliage of annual and
10 pe[em~ial grasses and bl~a~l4-s-fplants and the like, and is taken up over a period oftime
into the leave v~l~c~lce it translocates thro~lghnut the plant.
Gly~hn~.le in ionic form has 1~ laliv~ly high water sslllbility~ P, .~el :~lly when
formlllsted as a salt, and during the uptake period ;..,".Fdi~lel~, after app~ s~;on
gly~,h( sa~e is vuln~able to being washed offthe foliage by rain or by o~.;.l.ead ~.a~ g
15 or i-ngrtion As glyrhr-ste has practically no he~l,icidal activity in the soil, its efflcacy is
u:~ly reduced by such ~.~sh;ng.
The length oftime during which glyyhos~le is sGm~ at vllLel~le to ra n
depe~ s on many e..~Q~ l and plant factors, and on the duration and .,.lensi~ ofraul, but can be as short as thirty n~;n~eS or as long as twelve hours or more after
20 app1;r~tinn In the great majority of cases rain falling six or more hours after appli~ ~tir~n
does not seriously affect p5' IU~ re of the herbicide.
Usually, gl~,uhGsate is fo.. .l~ed in commercial colllyos;l;onc in the form of a
water-soluble salt. Salts in co.. ~ cial use include alkylamine salts, such as the
isoplûy~l&~e salt, alkali metal salts, such as the sodium salt, the allllllOl~lUlll salt and the
25 t~ elLyl~ lf~ salt. However, form~ tion~ of glyphosate in its acid form are also
used. Typical glyphosate salt forrnulations include aqueous Collce~lllales~ lt~lUilillg simple
dilution in water for applic~l;on by the end-user, and water-soluble or water-di~el~ le
dry form~ tionc, especially granules, requiring l1issoll~tion or dispersion in water prior to
dppli~ n Most fo~ ;Qns~ whether liquid or dry, also contain one or more
30 ~llrfir~t~nts Even with such surfrct~nts in the form~ tion there re,nail~s a need for
f nh~nced ~ r;~ f cs of gl~l,hos~le in many shl~tin~l~
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The ~lLw~ aled s;l~Y~Ane ~ctAnt Silwet L-77 I cr~ d to above has been the
subject of much p~l ~!;ch~ se~l,h into ~ ..e~c çnhA l~r~ 1 for gl~hosale sa~t
rO.. - ~alion~ Its main active ~grcdlcnl is 1,1,1,3,5,5,5-hepk~ ;lo~ lplop~l-
omega-l~lel~ )oly (ell-jlel~ oxide) where the average i~wllber of ethylene oxide units is
5 ap~lu~ Fly seven. Other siloYAnPs of related comrosition are also desclil,ed in the art.
In rdditi~n to the high cost of Silwet L-77, co...n on to all s:k,~ a l,. ,.lber of
disadvantages have been de~ l,e~l notably its ten~lPn~y to antagol~c the activity of
glyyhosa~e on some species in the absPnce of rain. A technical sol~ltion to this pro~lc.ll is
provided in Allstralian Patent No. 609,628, wl~clei l a k~ ec~ ll such as gl~ added
10 to the spray sa1-~tion uvercol~les the ~nt~oni~m huw~;vcr cost still lc.l~ns a major
det~le.l~ in most ~ gti~nc
A major advance in cost-effective r~infa~tnPcc enh~l~cr~ for gl~hosdle was
provided in U.S. Patent No. 5,258,354, wllel~l acetylenic diol ~lrfi~nts~ ~PmplifiPll by
cthù~lales of 2~4~7~9-tctl~llelh~l-5-de~rllc q, 7-diol, are shown to give l~ rhCl~esc at
15 least equal to Silwet L-77 when used in the pl es_ncc; of certain other ~ ~ . rh et h . " ~, but
~ithoul the oc~wl~nce of ~rtagonism in the ~3ence of rain. Concenllale fi . ..-~ l;ol-~ of
hGsale with such acetylenic diol surf~ct~nt~ are tli~closed which are both ch .~ lly
and ph~i,;cally stable over a wide range of co nditinm
While acetylenic diol s~1rf~antc are ob ~ble at much lower cost than e~i~e
20 ol~s:licone surfactants, they could still be too costly for m~ny applir,?ti~-m In most
cases the end-user wishes some degree of ill~ ce against the pGS;~;I)il;ly of rain washing
the herbicide offthe foliage before it has had time to penetlale into the leaves. The end-
user seldom knows that it will certainly rain. For such L~ ce pul~oses, economics
dictate a still lower-cost adjuvant or formulation ingredient. Various low-cûst s -rf~t~nts
25 have from time to time been claimed to give r~inf~tnPss enh~l-ce...~ , inclllrlin~
ethoxylated alk~ll.he~-ol~ such as octylphenol and nûn~lphellol ethoA~la~es. These are
among the most widely used general ~ull~ose adjuvants for glyphosate in many r..~.krlx,
and are not conr;t~ed by most users to provide reliable r~inf~tne~s enh~-c~
E.H. Br~-mb~lgh (Third Tntern~tion~l Symposium on Adjuvants for
AgrorhPm~ , Cambridge, U.K., August 1992) showed that ~rlition of APSA-80, a
product said to contain 80% of a nonionic s~f~ nt based on nonoxynol-9 (nonylphenol
elho~yl~le with an average of 9 moles ethylene oxide per mole of nonlphenol), enhanced
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r~irlf~ctnpcc of gly~ G.~?~e" app]ied as Ro~ d~) herbicide in an ultra-low volume of
water (30.6 1/ha). The adjuvant was used at con~e~ lions ~ g from 0.1% to 0.5%ofthe spray sol lti~n l~inf~tn~ss il.~plov~ln~ll was not evident on atl species.There is provided herein a new method of use of alcohol alk~ lale surfnct~nt~ of5 mol~c~ r structure defined more particularly below for P~ An~ p the ~ rz~l"rse Of
foliar-applied pesticiA~1 and plant growth modifying agents.
There are also provided herein new, storage-stable, liquid or dry co.~ce~ ale
co~ as;ti~ nC co.. ~p~ ;C ~e gl~hGsale or one or more of its salts, an alcohol alku,-~late
sllrf~ct~nt of ~-~'e~ structure defined below and one or more other s~lrf~ct~nt~, said
10 co..~l)Gsi~ n~ shov~-l,g ~ -ced l~ r~ F ,5 by co...rP-- ;con with similar compositions not
co.~ n;n~ said alcohol ~o~ ldle s~lrf~ct~nt and sh~,wing at least equal l~ r~ ess by
co...i.a- ;co~ with much higher-cost COIl~pO lions of the prior art based on etho~yldled
s~loY~ne or acetylenic diol sllrfact~nt~ Not all alcohol alku~lale surf~nt~ provide the
desired degree of,-:-.r~ ss Pnh~ ~c~..."l~l Alcohol alkox~ldtes of --'e.~llP/r structure
15 defined below, when used in acco.dance with the present i,.~.,lion, give ;,..I,c.ior
.r~ css by co..~?~--; OI- with, for e~ ,k, p,h"a.~ linear alcohol alkoxylates oralkylphenol alko~lales of the prior art.
Also provided herein are new, storagc-st~le liquid or dry con~ ale
col''i!o~;l;nn~ co.~.p.;~;~.g glyphosate or one or more of its salts, an alcohol alku~lale
20 slllfr :t~nt of moleculs~ ~L~. lu-c defined below and one or more other s~ ct~nts, said
compositions showing P~h~ced herbicidal efficacy by co,..pa. ison with glyphosate
comroYtir~nc known in the art, whether rain occurs shortly a~er ap~lic~s~tion or not.
Among the s~ t~nts used in co,nbinalion with alcohol alkoxylates in
compositions ofthe present invention are etho~ylaled tertiary and 4v~ y alkyl~ es
and aL~la,n.ne oxides.
It is known in the art that ethoxylated alkylamine or alkylamine oxide sll~fs-ctsnt~
having sn average allyl chain length in the range from 10 to 20 carbon atoms and having
an average of from 2 to 20 moles of ethylene oxide (EO) per mole of amine, are e~e~;~ive
in pote~ P the hc~ cidal activity of glyphosate compositions. Eu~upeall Patent No. 0
290 416, for example, ~~ 03~S glyphosate compositions cor.l;~ tertiary alkylamine
~llrfg~ntS within the range P-1~co--~,s~sed by the above description, and notes that such
con,po~;l;on~ particularly those with EO levels in the lower part ofthe range mentioned
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ahove, have high herbicidal unit activity. Eur~peall Patent No. 0 274 369 tlicrlosec highly
efficacious gly~ht s ~te CO~ Or- I ;onC co~ 4.J~tf .-~-y aL~yla,~e ~-- r, ~0..-~ within
the range ,~-r~...pq~sed by the above des~ t;on. ~ both cases it is disclosed that for best
pc- r.,. m~n~ e the cGll~posiliol~ should also contain a si~ifis~nt amount of an inol~a~c
5 ammonium salt such as A."~ n;"'~ sulfate.
US Patent No. 5,118,444 ~iSCloSes clhoAylaled all~yl~l"ne oxide s~lrf~ct~ntc
within the range enctj..-p~csed by the above dest;, ;llt;on, and in-~ic~tçs their !.S~ r l ,F ~, as
comronPnts of glyl.hos~le form~ tic~nc
~.. -- 1.;.. sulfate is bulky and can only be accol,--.. odated in a co~c~ ale
10 form~ ti~n at an effective level by greatly lowe~hlg the content of active ingredient, in
this case gly~hoQ~e A ci~.;r.c --d advance in the art offt)nnlll~ti~ glylJhosatecon~ ~ ales would result from id~ntifir~tion of a m~tt~ri~l which further enh~-rPs the
efficacy of Con~i)os;l;t~nc c~ ~ elhoA~laled alh~l&.,ine surf~rt~ntc~ but which is
i./e at a lower COl ce nllalion than is required in the case of a------- ni~lm sulfate. That
1~ m~tçri~l could be inco~lJo~aled in a conc~ ale formlll?tion will.oul ~ P~certable dilution
ofthe glyphosate active h~g~ienl. The present i~ 1iol provides just such an adva- ce
in the art.
SUr.1MARY OF THE INVENTION
There is provided a new method, for çnh~n~ing the efficacy or r~inf~tnPc~ of
20 foliar-applied pe~ 1A1 and plant growth modifying agents, using alcohol alkoxylate
sllrfAetAnt~ such as those having the rep~esenl~live ch~Pm~ l structure
lR2
R I--C--R 3
(CH2)m--o--(R4--~)n--H
wherein Rl and R2 are independently straight or branched chain Cl to about C 28
alkyl, aryl or alkylaryl groups and the total number of carbon atoms in Rl and R2 is about
25 7 to about 30, R3 is hydrogen, R4 groups are indepen~lPntly Cl to C4 alkylene groups, m is
a po~ e integer from 1 to 3 and n is an average number from about 3 to about 30.
-
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There are also provided new, ~lol~ge- b'~, liquid or dry conc~ ale
co~ )o~ lions CO~ ;Q ~P (a) gly~hosale or one of its ~culturally a~e~t~ble salts, (b)
one or more alcohol surfactants such as those having the r~pl ~ 3c~ltali~e chemical
structure
1 2
Rl--C--R3
(CH2)m--O--(R4--~)n~ H
~ Lclcill Rl and R2 are in~ de. lly straight or blallcl~d chain Cl to about C28
alkyl, aryl or alkylaryl groups and the total n~.-.bcr of carbon atoms in Rl and R2 is about
7 to about 30, R3 is h~dr~,~cn, R4 groups are in-l~f n~l~nlly C~ to C,. alkylene groups, m is
a positive integer from 1 to 3 and n is an average ll~lllber from about 3 to about 30, and
10 (c) one or more other s~,- r, ~, ~1s In pr~fe.-ed co, ~l~Gs;~;onQ~ R3in the structure ofthe
alcohol surfactant is h~en and R4is ell.jl~.e.
Co .~ros ~ c ofthe il.~e.llioll possess at least one ofthe following ~n~ils overcomposi~ionc known in the art (1) They may show enh~nGed ~ cs by CC....p8.;~
with similar collll)os lions not co..~ said alcohol surf~ ntQ., and at least ~ ially
15 equal r~infActness by CG~pd-;~OI~ with much higher-cost compositions of the prior art
based on etll~ laled ~ y~ne or acetylenic diol c~lrfact~ntc (2) They may show
enh~l-eed h~,.l,;cidal efficacy, even in the ~hs~nce of rain, by co..~ ;con with siTnilar
co~ osilion3 not co ~1A;~ g said alcohol s,~lr~ nlc
A method of use of such compos;liol~s to provide acceptable control of weeds and20 other ullv~lled ~,egelâlion whether or not rain falls shortly after applicntion is also
provided
DETAILED DESCRIPTION OF THE INVENl~ON
In the most widely used CQ-~ Cial glyphosate composition~ the herbicide
glyphosate is forrn~ ted as its isopro~ lille salt Fx~ellçnt control of most plant
25 species can normally be obtaillcd at rates of 0 1 to 10 kg/ha of glyphos~te-isopro~larnine~
It is generally pl~ f~lled to refer to the amount of glyphosate applied in terms of
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gly~hn~te acid equivalent, co~ ;on~lly abb.~,;aled as "ae.". .Ar~lic1Ation to plants is
most co....nnly done by sl"~",g a soll~tion ofthe glyphos-A,te herbicide in water.
For most ~p~ ;nl~s~ the efficacy of glyphosate is S;~ Ai~11y i~ roved by the
p,esc.lce of a s~rfAAt~ t However, not aU surf cti nt~ are equally effective in illlploving
5 the herbicidal activity of gl~.hGs~e, and some s~l-f~ctnnt~ are quite ine~ecliv~; or may
even reduce ~)hosale activity. Among the most eII~clive prior art sl- f ctnnt~ for
""pro~ g gl~,hosd1e activity are alkoxylated alkylamine sll~f-ActnntA, incl~ ing both
tertiary and ~ ale~ ~ ~ y amine types. Nonionic s - factnntc differ widely and to a large
extent unpre~ictnbly in their ability to ~.h~nce glyl~hosale activity. The alcohol
10 alkuA~lales ofthe present Ill~ iOn are rl l~lively weak in this regard, when used as the
sole surfactant.
Most co........ ~ ial gly~hGsale salt forrn~.lntiorl~ already contain one or more
surfactants, most cc - ~-nl nl~ of the tertiary or q~lat~n~ry alkylamine allw~lale class
mPntionPd above. For PY~mple, P~o~n(l.~ 3 herbicide of Mnnc~nto Co~pa~y is an
15 aqueous con~ ale for-nlllation ofthe isopr~la",ine salt of gl~pho~le In ar~ tion to
gl~ho~dte in the amount of 360 grams a.e./liter, Rnun~lp herbicide as sold, for PYQmr'e,
in Canada con~ c a su~-fQctQnt based on ethoxylated tallov~ e having an avelage of
about 15 moles EO per mole of amine.
The end-user may add more surfactant to a glyphos~Qte spray solutiQn; _s well as20 amines, low-cost I~OI~iQl~;C su~ctQntc ofthe ethoA~laled p,--"a-y linear alcohol,
al~lphel~ol or fatty acid dasses are especially widely used in this way. However, because
of the wide van~tion in efficacy of such sllrfQctQntc it is generally pl ê~wl èd to include an
e~eclive s~ ri-cl~ in the concçl~l~aLe formulation. In addition to the relatively poor
efficacy of alcohol alkoxylates when used as the sole sl~ctQntC with glyphosQte, these
25 alcohol surfactants suffer the further dl~a~ that they cannot be fonn--lQted with
glyl.hos~le salts in agriculturally useful arnountc in aqueous conce"L~ales~ except in the
presence of cQ~"p~ i7i~ agents. Such agents include a wide variety of tertiary and
uatel~ y an~ine surfQctQntc, allyl poly~ly-~osides and other mQt~riQlc
There is now provided a new metho~ for enhQn~ing the efficacy or MinfQctnPcc of
30 foliar-applied pesti~ and plant growth modifying agents, using alcohol alkoxylate
s~rfQctQnts such as those having the .e~lwc~,~aliv~ chemical structure:
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Rl--C--R3
(CH2)m--O--(R4--~)n~ H
~ lle.ein Rl and R2 are ;-ulep~ ntly straight or bl~lclled chain Cl to about C28
alkyl, aryl or alkylaryl groups and the total llulllllc. of carbon atoms in Rl and R2 is about
7 to about 30, R3 is L,~ lUg~,n, R4 groups are in~epenrl~ntly Cl to C4 allylene groups, m is
S pos.livt; integer from 1 to 3 and n is an average ~ el from about 3 to about 30,
plcrel~ly from about 7 to about 14, and most preferably from about 9 to about 12. R
and R2 are preferably straight-chain alkyl groups with a total of about 10 to about 20
carbon atoms, R3 is preferably hydrogen, R4 is ~.~,f~,.dbly ethylene and m is p.~rt;lably 1.
There are also provided new, storage-stable, liquid or dry col~cenl ~ dte
10 compositions co,~ g (a) gly~ho~te or one of its ~ ;c-u~ lly nc cepta1 le salts, (b)
one or more alcohol surfactants such as those having the r~lei.ent~livt; c
structure:
lR2
Rl--C--R3
(CH2)m--O--(R4~~)n~ H
~l.e,~il Rl and R2 are indepPnd~ntly straight or bl~lched chain Cl to about C28
15 alkyl, aryl or alkylaryl groups and the total number of carbon atoms in Rl and R2 is about
7 to about 30, R3 is hydlogen, R4 groups are indepen~lently Cl to C4 alkylene groups, m is
positive integer from 1 to 3 and n is an av~,~.ge number from about 3 to about 30, and (c)
one or more other s~lrf ct~nt~ said compositions showlllg e .h~n~.ed e~icac~ and/or
l~i..l~cln~5~ by co..~p~ ;cQn with similar compositions not c~..lA;ni~p said alcohol
20 s~lrf~ct~ntc and sl-~,wing at least ~ubsl~lially equal Minf~tn~ss by co---p~- ;con with much
higher-cost compositions ofthe prior art based on ethoxylated cilolr~ne or acetylenic diol
sl~rf~Gpntc
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A method of use of such compositions to pr~.,ide as~:pt~b~e control of weeds and
other u~ ed vegel~ n wl~ether or not rain falls shortly a~er appli~ ~iQn iS also
~ro~ided.
A particular eml~odimpnt of this invention is a surfactant co~ )osilion co. r ;~5 (a) an alcohol surfactant in which R3 is hydrogen, Rl and R2 are straight chain alkyl
groups with a total of about 10 to about 20 carbon atoms, R4 is ethylene, m is l and n is
an a~el~ge number in the range from about 7 to about 14, most pler~l~l" from about 9
to about 12; and (b) an ethoA~laled tertiary or ql!~t~ ~.A y all~ e or aU~yla.nille oAide
surfactant having an average of from about 2 to about 20 moles of ethylene oxide per
10 mole of amine. Said s~ nt con~pGs l;on may be corc....~ A~ed with a gly~hosdle
herbicide in an aqueo~ls or dry co~ce~ ale fo------l-l;c n ~ iV~ly~ said surfactant
c~n~os'l;on may be provided to the end user sepa,dtel~ from the gl~l,hGs~le herbicide,
for tank mi~ng by him ;~ eJ;~te1y prior to app~ "
Typically in co~.,..., -,;al prepalalions of sec~ A~y alcohol ~ -- r ~ the
15 e~oAylaled alcohol group can be located ~Iy~L~l~ on the alkyl chain except at the ends,
and such p~ep~alions are ll~erul~ ll~lules of alcQhol~i. The alkyl chain length also
normallyvarieswithincc~ e~,;alpr~ dlions.
In the examples that follow, one such prepalalioll is l~f~lled to as "C 11-15
s~cqlld~y alcohol 9 EO". This product has a total of about 11 to about 15 carbon atoms
20 in the allyl chain and an average of about 9 moles ethylene oxide per mole of alcohol
(n=9). C ~ secon y alcohol clLo~ylàles such as this are co.. l,~;ally available from
Union Carbide Co-~olalion as the Tergitol 15-S series.
An c~ le of prer~ d s~ ct~nt which has been found useful accGrding to the
present i,.vw.lion has the repres~llt~live ch~...icdl structure:
lR2
R 1--f--R3
(CH 2)m--O--(R4 ~~)n~ H
whcreill Rl and R2 are straight chain alkyl groups with a total of about 10 to about 20
carbon atoms, R3 is 1Iy~lloge4 R4 is ethylene, m is 1 and n is an average number in the
range from about 7 to about 14. Such surf~ct~ntc may be produced by reacting ethylene
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oxide, according to mçthntl~ known in the art, with ql~hols known in the art as "Guerbet
vqlr,Qhnl~
To provide the desired rinfq~tn~ el-h~l1c~ of a foliar applied pesti~ ql or
plant growth modifying agent, alcohol alkoxylates ofthe ~ . nl;on may be used at5 c~r~ alions in the spray solution in the range from about 0.05 to about 2 per cent by
volurne, p~r~l. bly from about 0.1 to about 1 per cent by volume, ~lthOU~h in certain
~;u~ ces greater or lesser collc.,llt,~lions may be used.
In conce~ le or ready-to-use gl~hosdle rc.. 1~ , the alcohol alku~ylate
sllrf~-t~nt may usefully be inrl~lded at weight/weight ratios of said sU~ct~nt to
10 glyphosate a.e. from about 1:20 to about 1:1, p.~fel~bly from about 1:12 to about 1:2 and
most preferably from about 1:6 to about 1:3.
In ready-to-use formlll?tions, gl~hos~e is typically present at about 0.5 to about
2 per cent a.e. by weight. ~queous concent,~te formlll-qtion~ ofthe invention may contain
about S to about 40 per cent glyyhos~te a.e. by weight.
Dry conce ~1~ale ful~ rl;nn~ ofthe ill~e~lt;oll may contain about 10 to about 75per cent glyphosqte a.e. by weight. Pl~rt"~d dry col-ce~ le fo.... ~I~I;on~ are water-
soluble granules co~ P about 40 to about 70 per cent gl~hosate a.e. by weight.
Plerel~d glyphnsqte salts for use in a~lueous or dry formlll,q,tion~ ofthe .l,~elltion
include an~nonium, alk~la""ne, for example isopropylamine, alkyl~ fnnillm for example
20 l"..lcll.~lc-~lfon; lm, and allcali metal salts. Most commonly these salts have a molar ratio
of actions to glyphl)s-qte anions in the range from about 1:1 to about 2:1.
Long-term shelf stability is an i."~,o,la"l CQ~ .;;al ~11- ihule of Con~ ale
f~" ",. ~1~1 ionc of pe ,~ d~l and plant growth modifying agents. In the case of aqueous
con~ le forrrlll~tion~ such as those of glyphosqvte, it is particularly important that
25 s~ cpntc in the rO. l~ -I;On do not i~p~ale from the other ingredi~lls as a distinct
phase. Many such nqueoll~ conc~ Les show a tendency for phase s~a,~lion at high
t~ )elalul~s. The "--l-;---~-, te.llpe~dLu,e at which such phase separation occurs is known
as the "cloud point" of the rO. - Ildl ;on. It is well known to those of skill in the art that
most nonionic sllrf~ct~nts, etho~ylated alcohols being a good example, have rather poor
30 co..~r~ y with high ionic ~L~ glh sol~ltion~ such as aqueous concenl,~,le formlllati~n~
of glyphosate salts. This poor co~p~ )ility is ...~-;rr~Led as a low cloud point, leading to
n~cceptably poor shelf stability of the formlll~ti-)n
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~ n accordance with the present invention alcohol alkoA~lal~s are i.~ ol~ted at
useful levels in an aqueous co-lc~ n . ate fo~ ion of glyphns?te salt by further inrl~
in the rO~ ;Ol~ aCfO~ rtg agent which raises the cloud point of the fnrm111 ,stion
to an a~cq~table level, for eYq-mr'e 50 C or higher.
In both aqueous and dly conc~ ale gln~hn~le rO- "~ n.c where ~ .
Pl~h~ncç~f ~-l is desired, additinnsl s~1~cti~nt(s) should be in~ ded in an amount ;~ ~f r
to provide ilcce~t~ble herbicidal efflcacy in the 3!~sf n~e of rain, and to allow the alcohol
alk~late to exhibit the desired level of ~ rAc~ness f r h~nc~...f nl
The amount of such ad~lhionq-1 su~r~vqnt other than alcohol all~o~lale to be
10 in~ ded d~pf ~-dC greatly on the chemical composition ofthat s~rfq-cti~nt on the plant
species l~ ed and on f.lvirol-~..f ~ 1 factors. Normally, hu~ er, the weight/weight
ratio of alcohol alk~ t~ to the total of other Sl~ ri~-li --l'j iS in the range from about 1:20
to about 5: l, prer~lably from about l: lO to about 2:1 and most plerw ~Iy from about 1:5
to about 1~1.
The surfactant(s) ~diti'~nql to alcohol alkoxylates in glyphosate compositions of
the ill~_.lliull may be sç1ected from alkyl monoglyco ides7 alkyl poly~cosidçs, sucrose
all~yle ~ seCon~a ~, tertiary, orqualell.alyall~ lùnealku,~lales, non-allw~laledtertiary or ~ y alhyl~ .es, alkylamine oxides, alkylbetaines and the like. Good
results may be o~ d for ey~mple~ with coco~ ~;ne 2 EO and ~ EO (e.g. Fthnm.oçn
C/12 and C/15, Akzo Ch~mic~lc Inc.), N-lllet}lrllallow~ulul,onium chloride 5 EO, 10 EO
and lS EO, N-methyloct~dec~ ..,..oni~lm thlonde 15 EO (e.g. Fthoql-~d 18/25, Akzo
Chc,~ Inc.)., N-methylcoco~mmonium chloride 2 EO (form~ ted at 35%
conc~ltlalion in water as Ethoquad C/12W, Alczo Chemicals Inc.), N-
methylcoco~ ol~ n chloride 15 EO (e.g. Ethoquad C/25, Akzo Ch~mic~ls Inc.), N, N-
diethyl-N-methy~ ,o~ n chloride 1 EO + 7PO (Emcol CC-9, Witco Corporation), N,
N-dilll~l~ldode~iyl~lulle (ArmeenDM12D, Akzo Chçm:~al~ Inc.), N,N,N-
tllylcoco~mmonium chloride (form--l~ted at 33% col~ce~ alion in water as Arquad
C-33W, Akzo Chemic~l~ Inc.), N,N,N-trimethyltall~w~ .oni-lm chloride (forml~l~ted at
27% conc~l~t~alion in water as Arquad T-27W, Akzo Chemi~ls Inc.), potassium
la~ ll,et~le, allyl poly~ll.cosjdes (Agrimul PG 2067 and Agrimul PG 2069, HenkelCol~Glalion), Cs 1o allyl mono~ cocide, and sucrose cocoate (Crodesta SL-40, Croda
Lnc.).
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Several of the FY~mp~q s herein utilize N~ lcoco~ ..onium chloride with 2
moles ethylene oxide ("coco~ e quat 2 EO") as the ad~litinnAl sllrfAGt~nt Other
Examples herein utilize tertiary COCOA ..;~e or tallc~w~l~ne with 5 moles ethylene oxide
("cocoamine S EO" or "tallu~ li,.c 5 EO" res~e~ti~,ly) as the ~ddition~l surfactant.
S In addition to glyl.h-~,s~le or its salts, the alcohol aLI~oxylate and the ;l~r1itinn~1
~lrfiA~nt(s), any of a variety offurther ingledic,ltP, or adjuv~lts may be inrl~lded in
fQrm~ tjnnc ofthe present invention as long as such added m~teriAlc are not cigrlifir.~ntly
~nta~nnictic to the gl~ hosale herbicidal activity and/or to the alcohol alkoxylate efficacy
or l~ s,g ~nh~.lr .~g activity. Mixtures of gl~hot~te with other herbicides are also
within the scope ofthe present il-~e-ltion. Examples of such other herbiddes include
biql~phoS,~ 5'~ e, 2,4-D,MCPA, ~lic~mhA di~h~ lethers, jmid~o~ onesand
SUIrv~ 1~5.
~r~thnrl.~A of use of some gly~hG~sale ro~ ;Qnc are well known to those of ski
in the art. Aqueous cQnr~ ale fol.. l~1;QnA~ ofthe invention are diluted in an
15 dppropliàle volume of water and applied, for ~ ~ ..ple by s~Jlayillg, to the weeds or other
Wl~ A lted ~.~e~AI;c n to be killed or controlled. Dry cQnre~ ale form~ tiom ofthe
invention are dissolved or d;~c ~d in an appropliale volume of water and applied in the
same way.
The present invention is illustrated by but not limited to the following Examples.
20 Indec-~;b;~ CQnCCn1 ~dtecoll~pGslions oftheExamples,pe~enl~esaregivenbyweightunless ollle-w;se in~i~qted In ~e~ g C~ont~ 1- aLiOnS of sll~A,tAnts in spray sQl~ltinnc~
pe~ ges are given by volume.
EXAMPLES
Co~pq ali~te herbicidal activity with and without simlllAted rain was determined in
25 grePnhsu~e and field tests. For gl~ .ho ce tests, seeds or plopa~ules of s~PIPcted species
were planted in 10.2 cm square pots of soil with added fertilizer. Tc.llpelalule and
relative humidity were allowed to fl~l~Ahl~q~fe within limits defined for each test d~scnbed in
the following FYAm1 1~S. Plants were allowed to grow until the desired growth stage or
size (defined for each test) for s~ayil~g. Pots were sele~led for ~ ....;ly before
30 ~ Inf~II and three replicate pots were acsiened to each lrrA~ Spray so~utionc were
pl~part;d by dilution or t~ ol~ltio~ of conce"ll~le herbicide ~r...~ mc in water. U7hen
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desired to test "tank mix" applic~sJion of surfactant CGI"~G~ l;onC these were added to
other spray sn1lltion at the r~ ed CQI~ alion. Spraying was Pf~ ~ ~--ed with a device
which c~ s a~;~ u~ 1 field ~l~g e.~ p-~n~ deL~ g a fine spray at a ples~e
of about 207 l~i1Opacrs1s Speed oftravel ofthe spray device over the plants was aclj~1st~d
5 to give the desired spray volume (defined for each test). For lo~ics1 reasons, all three
rep1ics~es of each IIC~ were sprayed together. "Rain" l~ nlS were applied by
repeated paCc~e of a coarse spray of water over the plants at some desired period oftime
after he.l,icide s~,.~n-g. The amount and duration of"rain" were noted. A~er spla~.g
and "rain" I~,~..e~1 the pl. nts were ,~lullled to the gre~1-ho!.~. Herbicidal efficacy was
10 evaluated by visual A~se~--.F ~1 at one or more s~le~!led time periods a~er l.~l...f..l and
recorded as "~el~e~t contror' on an ~lJ;llalr scale by co...p~ Qn with u~ ,aled plants.
On ~his scale 0 means no visible effect and l00 means death of all plants. In the
Examples, percent control values given are the means ofthree reF1icatçs
In field tests, l~ol~ were applied post-e.n~g~ce to plants which had grown
15 naturally or from seeds planted ...e~ -ic ~1ly in rows. A r~ndQmi7~d block design with
three rer1icatçs was used, with plot size depcnding on local cilc~ .,t~ncçs A bae1rr~r1~
sprayer with multiple nozzles giving an o~,lapping spray pattern was used to ...~ e
~- . rO....;l~ of apl.1ic~l;Qn "Rain" was cim~ ted by means of O~ d irri~tion
eq.~ tested for ..,.;rO. ~";1y Of deposilion of water. Percent control was evaluated in
similar fashion to that des~rihed above for gre~nho1.~e tests.
EA~IIF1e 1
The following s~1rf~et~nt adjuvants were tested for li.;.,rA~ P~c enh~ncemen~ ofglyphosate in a field.
Prior Art
l. Triton AG-98
2. 2, 4, 7, 9-tetrarnethyl-5-decyne-4, 7-diol l0 EO
Invention
3. C~ s secon~ry alcohol 9 EO
4. Adjuvant 3 + coco~ - quat 2 EO ( l: l ratio)
In this and other F.Y~nnp1ec a number followed by "EO" refers to the average moles of
ethylene oxide per mole of surfactant.
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Glyphosate was applied as the isoplop.~l&l~ne salt, either without s-~- r~ l (the
glyphosate fo.""-1A~;O~ sold as Accord~ herbicide by ~n~ 1O Colll~ ) or with a
tAnt based on tallov~ e ethoxylate (the glypho~le forrnlllAtion sold as Roundup~herbicide by M(~nCAnto Colll?~). Triton AG-98 (Union Carbide Col~olal;on) is a
5 widely used low foam ~ 'f~ &~ UI~l adjuvant, 80% of which is o.;l~lphenol
ethoxylate.
A total of 11 grass and broadleaf species were planted in rows:
A. Panicum di~ tc~ ;norum (fall panicum, PANDI)
B. Lolium sp. (annual l.~ ~S, LOLSS)
C. Bromus lf~lol~ln (downy brome, BROTE)
~ D. Sorgnum vulgare. (grain solgLulll CV. Rox Orange, SORGR)
E. Fr.hino~loa crus-galli var. r~ enlae (Jap~--ese millet, ECHCF)
F. Fr,hi~lorhloa crus-galli (b&ll~d~ass~ ECHCG)
G. Set~aria faberi (giant foxtail, SETFA)
H. ~hlltilQn ll~op}~ti (velvetleaf, ABIll~
I. Chel opodiuln album (common lambsquarters, (CHEAL).
J. Kochia scopalia (kochia, KCHSC)
K. Salsola kali (Russian thistle, (SASKR)
All app~ were made at a spray volume of 10 gallons/acre (93.5 l/~a). To
20 .~ e variation in rain-free period, all plots were sprayed within 15 ...;~J~es Rain was
~imlllated by o.~e~llcad irri~tiQn using an array offixed spnnl-lprs~ which were turned on
60 ...;~.-Jles a~er the midpoint ofthe 15-minute glyphosate application period. The
sprinl~lers were left on for 60 Inin~te~ talgcling a "rainfall" of at least 0.5 inch (12 mm).
Gauges located throughout the expelimental area showed that the actual amount of "rain"
delivered varied from 11 to 18 mrn, with a mean of 14.5 mm.
Data in Table 1 show percent inhibition as recolded 15 days after l.e~
(I)AT) with gly~JhGsdle at the rate of 0.25 lb. a.e./acre (0.28 kg a.e.nla), without and with
"rain" des~- il-ed above. For all "rain" ll~a~ s the adju~ ls were applied at a
concc"ll~lion of 0.25% in the spray solution. For the "no rain" t- e~ , adjuvant 4
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was applied at 0.25%, but the other adju~ were applîed, l~uOugll Op~,alor error, at
0.125%. This error does not affect any ofthe con~luC;on~ drawn below from this test.
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,, ~ o ~ ~ o 1~ oo oo
o t~ oo o r-- o o
_, o o ~ oo ~- oo
oo ~ o ~7 oo o o~ oo
~1 o ~ o ~ o ~ o '~ o~
o
07
~I ~ ~ 8 ~ o~ ~ o ~ o ~ oo
ml '~ ~ 8 l' 8 0 o~
~ ~~ '' ~ ~ 2 ~ ~ ~ ~~
o ~ o ~ o ~ o ~ o
~ ~ Zo --
D
~ o
c ~= o ~ g
16
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The results of this test show Adjuvant 3 (co~ a secc~n~ alcohol
ethc~ldle) to provide 5;~ ri~cl-~es': ~nh~nef..~.f.~l of Rolm~1up. While not giving
complete ~ rACl ~ess under the severe cQr.dil ;oI-s of this test, the use of Adjuvant 3
I~l},eless gave greater e ~h~n~n~f n1 of r~inf~ctness than the Triton AG-98 (Adjuvant 1
ofthe prior art) and was at least as effective overall as 2, 4, 7, 9-te~ L~rl-5-decyne 4,
7-diol 10 EO (Adjuvant 2 ofthe prior art) which is a much higher-cost m~trri~l
Adjuvant 4 provided a similar degree of r~inf~stn~cs e ~h~nc~ 1 to Adjuvant 3, and
when added to the surf~ ntlecc product Accord gave similar pe~ ce with "rain" aswhen added to the surfactant-c~ -p product Roun~lllp.
Example 2
~ lueouc conc~..l ~ ale form~ tions of the isopr(,l"~lamine salt of gly~hosale were
prepared at a gly~hosdte a.e. Ioading of 18.4% (equivalent to about 200 g a.e./liter). All
c0 ~1A;-.~-d 7% cocoO~ e quat 2 EO and 10.2% nonionic sulf~rt~t The noninn;-
surfictant was s~le~led from several secol-d ~~y alcohol e~Lo~ldtes, Silwet L-77, 2, 4, 7,
9-t~,t~r.~ 1-5-dec~.. e q, 7-diol 10 EO, nonylphenol 8 EO, 10 EO and 12 EO and C12-15
l&y alcohd 7 EO, 9 E0 and 12 EO. These forrn~ tions were tested for l~ A~ sc
in a gl~ nh~ice test.
The test species was ~ ~lm .. ~;.. " (~lin~grass, PANMA). All glyphosate
fonn~llqtisn~ were applied at 1.5 Ib a.e./acre (1.68 kg a.e.lha) in a spray volume of 20
20 gallons/acre (185 ltha). CGIIU~ C;aI pnundup herbicide was inrl~lded as a ;.l~ldard.
.S;~ ed rain was applied in the amount of 6 mmover a period of 15 ~ IÇ5, bePi~
1 hour after ~Inhosdle tl~ n~ Data on percent inhibition without and with "rain" are
presented in TaUe 2.
Table 2: Percent inhil-ition of ~line~rass 15 DAT without and with sir~ ted rain (means of 3 replic~tes).
No rain Rain
Rmln-lllp~ herbicide (standard) 100 65
Nonionic in formlll~tion
Silwet L-77 100 70
2, 4, 7, 9-tet~ yl-5-decyne-47 7-diol 10 EO 98 94
nonylphenol 8 EO 100 97
noI.~rll)hcnol lOE0 100 81
nonylphenol 12EO 100 63
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No rain Rain
Roundl~ herbicide (~hndald) lO0 65
Nonionicin rc.. ~ ;nn
Cl2-ls plUll~ r alcohol 7 EO 99 go
Cl2.l5plu~y alcohol9 EO 98 81
Cl2 1~ p~u~ r alcohol 12 EO 99 68
Cll-ls se~l-A~ alcohol 7 EO l00 89
Cll-ls se~Q~A~- ~ alcohol 9 EO l00 99
Cll-ls seco~ y alcohol 12 EO l00 86
Cll-ls se~cntl~q~y alcohol 15 EO 99 80
Cl2 b,~r1chet se~~n~qfy alcohol 6 EO 100 66
Cl2bl~ cl~dsec~n~~~yalcohollO EO 100 98
In this test, acceptable pr ro~ al~ce(>85% inh;l~iti~n) with rain was o~ d with
2, 4, 7, 9-tell~llelll~l-5-de~le ~, 7-diol l0 EO ofthe prior art, and with two lower cost
~ .;q1c,l~oll~1ph~l~ol8 EO and Cl2-ls plu1~ alcohol 7 EO, ~kewise outside the scope
5 ofthe present ul~llion. It will be noted that even a slight u1clease in the EO level on
either the no11~ henol or the p1u1~y alcohol ~i~ifi~qr~tly reduced the ~;~r~ C~ ofthe
fofm~ tion; at the 12 EO level no ~ .ri cl..cs5 advantage at all was obt~ pd with either
ofthese surfactant types. By C~11tlaCI, Cll-ls secQ~ alcohol S-- r~ gave el-hal~ce~
1i.;..rA~ cc over a wide range of EO levels. Ofthe Cl2 b1~cl1ed seco~d~y alcohol10 sllrf-ctq-ntc tested, the l0 EO example gave ~-eellp ~ ;.,f; ~ cc while the 6 EO example
did not give s;~ c~ r~c~ cs ~..k~l~cç~..e~l in this test.
Ex~unple 3
~ lueollC conc~ ale rc - I~ ;onc ofthe isopropylamine salt of gl~1.hos~le were
pl~p~ed at a gl~l,hGsale a.e. loading of 31% (equivalent to about 360 g a.e./liter). All
co~ d 7.5% coco~-.. ;~-e quat 2 EO and 8.6% nonionic surfactant. Fo.. l~ nc
cG~ d as the nonion:C C11-15 secondary alcohol 9 EO or Cl2 b~-ched scconda-y
alcohol l0 EO; for co-~p~ ;con, other form~ tione were made CG~ g nonionic
dicc1osed as 1~i~.r~c~... ss aids in the prior art such as 2, 4, 7, 9-tetl~llelhyl-5-decyne-4~ 7-
diol l0 EO or non~lph. nol 8 EO. These fo1111ulalions were tested for r~inf~ctness in a
20 grePnho..ce test.
The test species was Elymus repens (qu~ ss, AGRRE). All gl~l,hGsdle
form~ tion.c were applied at both 0.75 and 1.5 Ib. a.e./acre (0.84 and 1.68 kg a.e./ha) in a
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spray volume of 20 gallons/acre (187 l/ha). Co.~ .al Rmm~ herbicide wa5
inrlllded as a s~lddrd. ~ ed rain was applied in the amount of 6 rnm over a period
of 15 ...~ s, bFei~ P. 1 hour after glyphosate ~ F,.~ Data on percent inhibitionwithout and with "rain" are pre3c~lted in Table 3.
5 Table 3: Percent i.~h~ on of q~ ~ass 28 DAT without c;~ led rain (means of 3
1 ~liCI~ I F 5)
A~-p~ tion rate lb/a (kg/h) 0.75 (0.84) 1.5 (1.68)
No ~ain Rain No Rain Rain
Rotmdup (st~d) 73 30 92 72
Nlonionic in ru~ ;on
2,4,7,9-t~yl-5 decyne-4,7 diol lo EO 94 78 98 94
~u~ll~ol 8 EO 97 83 9~ 79
Cll 15 ~ y alcohol 9 EO 93 96 100 98
C,21,-t ~h~l~ yalcohol lOEO 94 84 100 88
At the lower gl~fphGsdle rate, both fo.. ~ nc C0.~ g seco~ Qhnlc
10 gave better l~ ct~.~ss than the fo~ AI;on ofthe prior art co.~1A~ning 2, 4, 7, 9-
tell~llelL~l-s-de~lle ~, 7-diol 10 EO, and the forrn~ tion ofthe ill~el~lion c~r.l~in;l~p
Cll-ls seco~ r alcohol 9 EO gave better r~inf~ctness than either ofthe prior artf~ .. l?li~nc At the higher glyphosate rate, both formulations ofthe present i,~ lion
gave better l~;~-r~ -ess than the formlll~tion ofthe prior art co--~ ;~ nonylphenol 8 EO,
15 and gave COlllp.u ble ~ r~ .e,~ to the much higher cost form~ tion co,-1;~;..;l-~ 2, 4, 7,
9-lc:ll~lle~ l-5-decyne~7diol 10 EO.
Considering F~;- ..ple5 2 and 3 together, it is clear that Cll-ls secollda.y alcohol
9 EO and Cl2 ~,~nched secondary alcohol 10 EO ofthe present invention are more
CQnciQt~nt in their ~ .r~c1-~Qc ~nh~n~.i~ perforrnance than noll~lphenol ethoxylates ofthe
prior art.
FY~ PIe 4
The following glyphosate forrn~ tion.c were tested for herbicidal activity and
~;~;nr~ esc by coll,l a ison with Roundup~ herbicide in a field trial;
For nulation A: 31% glyphosate a.e. as the isoplollylamine salt, 7.5% coco~mine quat
2 EO, 8.6% non~lphc~.ol 8 EO.
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F~ ;QI~ B: 31% gl~hcs~te a.e. as the isoploy~l&~le salt, 7.5% COCr~ nÇ quat
2 EO, 8.6% Cn-ls seCQn~A ~ alcohol 9 EO.
A total of 7 grass and br~ ar~ f species were planted in rows:
L. Digitaria ciliaris (svulhe.~l crabgrass, DIGSP)
S M. B~ plal~h~lld(brc~ fsignalgrass,BRAPP)
N. Sor~ ,h~lçpçn~e~ohl-~ol-~ aS;~ SORHA)
O. Fr~ ~loa crus-galli (b~a~ ECHCG)
P. Sida spinosa (pricldy sida, SlDSP)
Q. Echinochloa crus-galli var. ~ e (JApAIlçse millet, ECHCF)
R Se~b~n:~ ~YAItattl (hemp sF,lJ~ SEBEX)
All app1ic~,l ;OllR were made at a spray volume of 10 gallons/acre (93 .5 1AIa). To
A~ ;0l- in rain-free period, all plots were ~l~ed within 15 ...;..~ Rain was
Q;rnllhted by ~ head irrigation using a lateral move irri~inn system, which was turned
on 60 .l.: ..,~çs after the midpoint ofthe 15-minute gl~}i9SA~Ç applic2l;0l- period to give a
"rainfilll" of ap~ ,u~ y 0.5 inch (12 mm).
Data in Table 4 show percent il-k b;l;QI- as ~col~led 21 days a~er llca~
~I)AT) with gl~l,ho~dte at the rate of 0.75 lb. a.e./acre (0.~4 kg a.e./ha), without and with
"rain" as described above.
Table 4: Percent ;~ ;1;91~ 21 DAT wil}~ùul and with c;---~ ed rain (means of 3
replic~tçs). Form~ tiollc A and B and species L-R as defined in text.
Formulation in Species
L M N Q P Q B
R~lndllr (sl~lda~d) no 98 95 99 86 75 90 77
yes 65 57 86 52 65 78 68
A no 100 93 99 87 77 89 69
yes 79 70 93 62 68 82 75
B no 100 92 95 79 73 89 72
yes 87 75 96 68 77 84 82
E~.,lplcs 5-7
In Examples 5-7, a short-term whole plant assay was used to evaluate relative
25 efficacy of aqueous glyphosate compositions co.~ tallov~à-"ll,e 5 EO and either C
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WO 97/00010 PcrluS96/10467
15 secc -- ~s~y alcohol 9 EO or a Guerbet alcohol in di~cltilt conrç~ alions andplo~ollions relative to one another.
The following procedures were used for testing in Examples 5-7. This test is
dFsi~ed to give an ;I~3;CAI;~ of relative r~inf~tnPcs of difrere.li gly~ho3~1e
5 CO~ OS l;nn~ Equal volumes of ~-~.;rO. .--ly sized seeds (20-25 in l~ulll~er) of barley cv.
Pennco were sown in a glow-ng ~~eJ;~ con-~:~l ;-.g of a 3 :2: 1 sand/soiUpeat Inl~lUIt; in 4
inch square plastic pots. Pots were placed in a controlled e.lvi.urs~ l growth c1-~-.-ke~
providing a 14 hour pholop~. ;o-l day and night tel~lpelal~lres of 78~F and 66~
I~s~ ely~ and a relative humidity in the range from 30% to 50%. Light was p,ov;ded
10 by a cC~ hi~Al ;on of metal halide and sodium vapor lamps. All pots were bottom ~. alel~ d
at 1200 hr on the first day, resl~ltin~ in rapid salulaliOll ofthe g~win~ eJiu~ .See
c.ll~,.gw~ce oc-,ulled on the third and fourth days. On the seventh day, all pots were
fertilized by bottom ~aleling with a Peters 20-20-20 fertilizer cor.lh;~ ing 475 ppm soluble
r~
On the eighth day, pots were sorted into 6 replicate blocks acco,-lillg to plant size.
Tl~ , in~hlrling no-lle~ nl conllols, were randomly ~i~Pd within each block
onelae~ perpot.
Plants were treated with glyphos~te co.npos lions in rapid succesc o~ bel~.e~,.
0830 hr and 0900 hr on the ninth day, when average plant height was 13-15 cm and the
20 ~ second leaf was just be~ g to elongate. Compositions were applied using a calibrated
single-nozzle track sprayer del;v~..ng 187 l/ha through a Teejet 8001E nozzle at 276
kilopascals. Plants were rellluv~d from the growth ~ b~r ;~ P.I;~I~IY before ~ e~
and lelu~ned to the same growth chA-..ber ;~ ell;AI~IY after II~ Pots were
spatially ~ nged in a randomized co--l~lete block e,~.im~ al design. At 6 hours after
25 t~ .l plants in all pots were ttimmed by cutting to 20 mm above the top edge ofthe
pot. This removed appro~ ly 90% ofthe barley leaf area. Pots were bottom wateredonce daily for the re..~ der ofthe study. Data collection took place on the ~;xleelllh day,
7 days a~er ~ .,"I
Average height of barley I egl UWIll in each pot was l.R&s.lred to the nearest S mm
30 il~cr~..e.ll, from the earlier cutting height 20 mm above the edge of the pot. All plants in
each pot were then cut at 20 mm above the edge ofthe pot and total fresh weight was
recorded.
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T~.~...ple S
All comrositiQn~ in this Example conl~ned g~ hos~le as the isopr~ e salt
at a cO~C~ aliOllC~ ted to deliver 0.42 kg a.e./ha. PolyuAyell"~lene tallo~a,n...e
S EO (T/Am S) c~ c~ aliol~ was varied i--depP. ~de~~lly of Cll-ls seconA~ alcûhol 9 EO
S (S/Al 9) conrf~ aliûn as will be clear frûm the tables below. U llrealed plants had a
mean l'egl'OV~ height of 175 mm.
Mean height of l~i~uwth (mm)
T/Am 5 S/A1 9 (%wlv)
(% w/v) 0 0.15 0.3 0.45 0.6 0.75
0 148 101 112 124 120 122
0.05 149 52 39 51 55 66
0.1 64 51 49 51 60 63
0.15 65 53 50 47 46 52
0.2 58 50 45 52 54 52
0.25 57 47 45 43 47 42
Least C;~;r~c~ d~re,e ce ~P--0.05)15
10 Mean fresh weight of le~uwlh Cg)
T/Am 5 S/Al 9 (%wlv)
(% w/v) 0 0.15 0.3 0.45 0.6 0.75
0 1.92 1.24 1.34 1.46 1.43 1.45
0.05 1.80 0.70 0.54 0.61 0.77 0.90
0.1 0.83 0.75 0.68 0.69 0.80 0.80
0.15 0.78 0.68 0.72 0.65 0.61 0.67
0.2 0.73 0.61 0.62 0.71 0.68 0.66
0.25 0.76 0.56 0.56 0.59 0.68 0.61
Least si~rific~nt d~ference ~~0.05) 0.20
In this study, when S/Al 9 was the sûle surfactant, the lowest tested concP~.-l,~lion
(0.15%) was the most e~.;live in potP ~ l;.,g gl~lJhosale activity, there being a slight
15 tenden~ for pelru----~nce to deteriorate as col-c~ alion was inc-~ased above this level.
When T/Arn 5 was the sole surfactant, the lowest tested conce..l-alion (0.05%) gave little
or no i--.prov~ ~.ci.l in glyphosate efflcacy, but a concenl~alion of 0.1% gave vely
~i~nific~nt illlyluvel-el-t- No further improvement was seen as T/Am 5 connc~ alion was
~c.eased above 0.1%.
22
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W O 97/00010 PCT~US96/10467
When T/Am cQnc~ alion was 0.1% or higher, adding S/Al 9 gave little funher
nl"o~ell,eil1 in glyphosate efficacy in this study. However, at 0.05% T/Am 5, a~ ion of
S/Al 9 gave a re~ons~ far in excess of any l~sponse that could have been predicted from
the weak pr~ fiu....~-ce of S/Al 9 alone. This study l~ 'trult clearly shows a ~ crgi:~ic
5 intel~.;tiol bet~ e.l StAl 9 and T/Am S at ~.~t)ol till.al levels of T/Am 5.
F.. i..nl)le 6
A further study was con~lcted to focus greater attention on low T/Am 5
col-c~ aLions and to try to confirm a ~,.~ lic illtel~clion ~el~ T/Am 5 and S/Al 9
at such low T/Am 5 cQI~c~ ions. Glyphosate rates in this study were also lower (0.07,
10 0.14 and 0.28 kg a.e./ha). All compositions in this F~ le co..~il-ed glyphos~te as the
...nnoic~!plu~ lline salt. T/Am 5 concenl~lion was again vaned ;.ldc;pende.llly of
S/Al 9 conr~ alion as will be clear from the tables below, in which results for all three
glyphosate rates are a~ltl~ged. Unl~aled plants had a mean l~ùwlh height of 168 mm.
Mean height of l~gluwlh (mm)
T/Am 5 S/Al 9 (~/Ow/v)
(% w/v) 0 0.031 0.062 0.125 0.25 0.5
0 171 144 145 151 156 165
0.016 124 87 88 91 93 120
0.031 118 90 84 85 93 99
0.062 123 92 79 79 79 98
0.125 116 92 88 86 84 85
0.25 113 84 85 75 73 78
Least si~ific~n~ di~ ce (P=0.05) 11
Mean fresh weight of re~uwlh (g)
T/Am 5 StAl 9 (~/Ow/v)
(% w/v) 0 0.031 0.062 0.125 0.25 0.5
0 2.83 2.16 2.28 2.31 2.44 2.98
0.016 1.82 1.32 1.24 1.33 1.40 1.90
0.031 1.64 1.46 1.33 1.25 1.32 1.51
0.062 1.75 1.44 1.18 1.28 1.18 1.47
0.125 1.72 1.39 1.36 1.34 1.37 1.32
0.25 1.71 1.32 1.32 1.19 1.21 1.28
Least si~ificant di~lence (P=0.05) 0.20
As in the previous study (Example 15), when S/Al 9 was the sole surfactant, the
lowest tested con~ e~ alion~ in this case just 0.031%, was the most effective in
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~otr ~ p ~pho~le activity, thae being once again a slight t~d~ r for p~rw"~ ce
to detçriorate as Co~c~ alion was incleased above this level. When T/Am S was the
sole su~f~et~t, all concP~ alions, even as low as 0.016%, gave ~ ;rA~I il.lplo~e..,~t
in glyphosate efflcacy. No c;~ further illlprovel~cnl was seen as T/Am 5
5 ~onr,~-~1-a~iol~wasillcl~,asedaboveO.016%.
Adding S/A1 9 to T/Am S hl.pru~/cd glyphosate efficacy beyond that acl~c~able
with T/Am 5 alone. In this study, the ilnp~ cnl was seen with all co..~k;.~AI;ol~ except
for co~hi~al;onc of high S/AI 9 and T/Am 5 conc~ alion. In most cases ~1rlition to
T/Am 5 of S/A1 9 gave a ~e~olue far in excess of any res~Qn~e that could have been
10 predicted from the weak p~- r~ Ae of S/A1 9 alone. This study lh~,;e~ule CQI~ the
~1.e~iStiC interaction be~ S/A1 9 and T/Am 5.
CG~ ;con~maybedrawnbel~c~certain 1:1 co..~ AI;onsofS/A1 9and
T/Am 5 and either S/A1 9 alone or T/Am alone at the same total s~ ctAnt co~c~ n . ~lion
as shown in the following table.
Total ~ctAnt cQ~-cP~ aliol T/Am 5 alone 1:1 CG.~Ik;.~;Q~ S/A1 9 alone
0.062 1.75 1.46 2.28
0.125 1.72 1.18 2.31
0.25 1.71 1.34 2.44
In all cases the fresh weight reduction is greater w,ith the co...l-il-AI;on of
surfS~Gpnt-~ than with either surfactant alone at the same total col-cer.1. alion.
r~A~ple 7
~ lueo~l~ form~ tions of glyphosate as the isop~plydl~ e salt cG..IAi~;n~ T/Am,
20 an ethoxylated Guerbet alcohol, and a 50/50 weight % blend of these s~ ctAnts were
plc~alct. Various such etho~ylated Guerbet alcohols have been inrluded in fiormlllAtionc
of this type, having the following repl~3e.lldli.~e chPmicAI structure:
CH3--(cH2)x--fH--(CH2)y--CH3
CH 2--O--(CH 2--CH 2--~)n--H
25 They include one ex~unple Gl in which x + y is 8 and n is an ~ ge of 7.7, and another
eY~rnple G2 in which x + y is 12 and n is an average of 9Ø The f~nnlll~tiQnc of this
CA 02224364 1997-12-10
WO 97/00010 PCT/US96/10467
examplewere co..-ki~-fd with ~qIleouc solution of iso~ro~yl amine salt of glyphosate and
the Ie~ g soI ltion was further diluted with water to produce a spray solutiQn The
spray sollltion was sprayed on plants in a greenhoI)se to del~ e their herbicidal
efficacy.
CoIl.poslliol s co~ JhGs~le with tallowalll.ne, glyphos~t~ with Guerbet
alcohol surfnçt~nt, and glyph--s~te with a Guerbet alcohol ~ rt~nt/talluv~ e blend
were applied at three din'cr~ dosag~s to barley plants. The p~ ge inhil-ition was
then recorded in terms of net ;~h;l) ~;on of vertical growth (VG) and net inhibition offresh
weight ~FW). The foll~.,lg results were obl~Ied:
¦ taUowamine Guerbet blend
1. Guerbet - G2
t.~tal~r- b ~1=0.0625% VG FW VG FW VG FW
' g'yphosate 0.0625 lb/acre 18 15 10 18 "0 20
osdt~0.12' lbtacre 29 37 -5 3 ~7 44
osd~e 0.25 lb/acre 53 50 20 25 67 61
2 Guerbet. - G2
~ t.~tal surfactant= 0.'.25%
g ~ u~te o.on"5 I'a/acre 9 8 4 -1 26 2'
g'yplosate 0.1~' lb/acre 45 49 -1 5 35 42
g'y~ Osdt~, 0.2' lb/acre 65 63 25 26 61 5'
3 C-uerbet - G2
t.~ -..r~ct ,1 = o.~,5%
g ~ dte O.~6~5 1'~/acre 20 ' 6 8 13 2 30
gypqosateO5,2t Ib/acre 41 '4 -5 7 5'' 53
gly~ .u_.t~ 0.''5 Ib/acre 60 61 18 20 69 64
4 Guerbet - Gl
total s,~ IV-~1 = 0.0625%
glyp'losate 0.06' 5 Ib/acre 12 12 -2 -5 24 27
gly~)1ua~0.12' Ib/acre 37 35 7 16 54 50
osdt,0.25 b/acre 54 53 28 29 65 53
Guerbet - Gl
~ total s . ~ --t = O. ~125%
g' ~Jh~lsdt~ 0.0625 I -/acre 17 19 4 -6 19 15
g~yphuad~ 0.125 Ib/acre 10 18 1 3 47 41
g' ~hùsdt~ 0.25 Ib/acre 44 47 23 20 67 61
Guerbet - Gl
6 total s-v. ~ = 0.25%
g ~ lua~le O.l~r~25 Ib/acre 20 19 -3 -16 28 28
g y~ ~~t~ 0.',25 Ib/acre 23 21 2 13 36 32
gy~lGaateO.2' Ib/acre 41 42 14 16 59 58
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F~ e8
This eAl.e~ 1 was conducted to det~ .e g,crnho~se efficacy of Guerbet
alcohol s~ nt~ in cû.nl.~ ;ol with T/Am 5 as p ol~ o,s for ~Iy~hGs~e as the
5 isop,o~ e salt. ,s r; 1A~1COIllpGSliOnS were plcp~d by CQ...~ Y Guerbet
alcohol surfactant at 3.33% and T/Am 5 at 6.66% in aqueous sQl~ltion These sv- r~
colllpos;l;nn~ were tA~ ;A~ d with glyphosate at two glylJhos~lç~ r~ 1 ratios (2:1
and 4:1) and colllpa.~d to a ~ danl formlllqti~n and to a T/Am 5 + blend at the same
lanLi~;x ratios. The Guerbet alcohol sll~fAct~nt.s were Gl and G2 of Example 7.
The following proc~lules were followed. Velvetleafand ba.l,~aldgrass (JAP~I~FSe
millet) were planted in stand~.l 4 inch pots which co..1i.;..ed a SO% I,~lure of Metro Mix
and 50% Dupo silt loam soil. This soil mLx was ple~iOllSI~r steam s~ ed and
plefwlili~ed with Os,l,ocote (14-14-14) slow release fertilizer at a rate of 100 gm per
cubic foot. APPIVA;" -tfl~ one week after en~ nce any llnh~i~lthy or extra plants were
15 ,e."uv~d to create a ~- -;rl~- - - test pot prior to herbicide applic~ Herbicide
applir?~ir.nc were made via a track sprayer. The sl~dard fo.. l_l;on used in this test
was the co-~ c;al product l~ ndllp~ herbicide as sold in ( ~ni~d~, as de~r- ;l~ed above.
All pots were then placed in a warm ~.~pl l~mPnt~l lighted (approx. 475 microeii.st~in~)
glc~nho~ce and s.ll~; I;g~e~ to .,.~ a~eqll~te soil n~oi~ forthe duration ofthe
20 test.
% ~ io
20 DAT
(avg. 4 reps.)
Glyphosate Ratio
Lb. ae/ Gly: velvet- Ba~n-
Che TRT ~onnul~tinn Acre Surfleaf yard
~d O O o
2 Roundup 0.125 36.3 62.5
3 Roundup 0.25 57.5 78.8
4 Roundup 0.38 72.5 95.8
2 5 GIYIJI~S~ + Gl + T/Am 5 0.125 2:1 33.8 65.0
6 Cl~ s~ + Gl + T/Am 5 0.25 2:1 47.5 81.3
7 Cl~ A + Gl + T/Am 5 0.38 2:1 73.8 93.3
8 Glyplh)sdt4 + Gl + T/AM 5 0.125 4:1 10.0 42.5
g Gly~J~iu~ale + Gl + T/AM 50.25 4:1 37.5 67.5
26
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W O 97/00010 PCTAUS96/10467
% Il~hibition
20 DAT
(avg. 4 reps.)
Glyyhos~te Ratio
Lb. ae/ Gly: velvet- Barn-
Che TRT Formula~on Acre Surf leaf yard
Jlyphosate + Gl + T/AM 5 0.38 4:1 57.5 78.8
3 11 Glyphosate + G2 + T/Am 5 0.125 2:1 31.3 62.5
12 Glyphosate + G2 + T/Am 5 0.25 2:1 56.3 75.0
13 Glyphosate + G2 + T/Am 5 0.38 2:1 66.3 95.3
14 Jlyphosate + G2 + T/Am 5 0.125 4:1 26.3 47.5
Glyphosate + G2 + T/Am 5 0.25 4:1 43.8 75.0
16 Gl~ILG~ + G2 + T/Am 5 0.38 4:1 58.8 80.0
4 17 J~ hO ~ + S/Al9 + T/Am 5 0.125 2:1 32.5 51.3
18 Gly~hos~e + S/AI9 + T/Am 5 0.25 2:1 56.3 68.8
19 G1Y~ G~ + S/AI9 + T/Am 5 0.38 2:1 67.5 88.8
ZO Glyphosate + S/AI9 + T/Am 5 0.125 4:1 26.3 35.0
21 Glyphosate + S/Al9 + T/Am 5 0.25 4:1 45.0 71.3
22 Gl~,ho~+S/Al9+T/Am5 0.38 4:1 61.3 77.5
r~...ple 9
A series of c~-c~ -aled rollll.ll~l;Qn~ were p.ep~ed co..li.;.. -.g 24 percent
glyphosate as the isoplu~J~rl~lllne salt of glyphosate and a n~lure of a Guerbet alcohol
5 (G3) ofthe fc,.-..~la of F.~ e 7 with T/Am5. The ratio of G3 of T/Am5 varied from
about2:1 toabout8:1. ThecloudpointofthecG~npGs;lionswere~et~llll;r~lrltorange
from 57 degrees C to 86 degrees C. The highest cloud points were o~l~ncd with the
highest ratios of T/Am 5/G3 ratios. However, all compositions were s~ti~f~ctQry with
respect to practical utility with respect to this aspect ofthe collcc~ ale composition~
While the illu~llali~e embodim~nt~ ofthe invention have been des.;lil,ed with
particularity, it will be understood that various other morlifications will be a~p~e..l to and
can readily be made by one of skill in the art without departing from the spirit and scope
of the invention.
