CA2224364A1 - Surfactants providing enhanced efficacy and/or rainfastness to pesticide formulations - Google Patents
Surfactants providing enhanced efficacy and/or rainfastness to pesticide formulations Download PDFInfo
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- CA2224364A1 CA2224364A1 CA002224364A CA2224364A CA2224364A1 CA 2224364 A1 CA2224364 A1 CA 2224364A1 CA 002224364 A CA002224364 A CA 002224364A CA 2224364 A CA2224364 A CA 2224364A CA 2224364 A1 CA2224364 A1 CA 2224364A1
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
- A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
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Abstract
Alcohol surfactants such as ethoxylated Guerbet alcohol, are added to composition containing other surfactants to enhance the efficacy and/or rainfastness of herbicidal compositions containing glyphosate or its salts. The compositions of the invention may be in the form of concentrated compositions that are storage stable and water soluble or diluted solutions that can be directly applied to foliage.
Description
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.
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~
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 W O 97tO0010 PCT~US96/10467 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 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 (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.
-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 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 WO 97tOOO10 PCT/US96/10467 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:
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 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 CA 02224364 1997-12-lO
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 ~ 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.).
CA 02224364 l997-l2-lO
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 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
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.
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~
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 W O 97tO0010 PCT~US96/10467 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 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 (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.
-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 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 WO 97tOOO10 PCT/US96/10467 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:
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 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 CA 02224364 1997-12-lO
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 ~ 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.).
CA 02224364 l997-l2-lO
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 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.
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 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.
,, ~ 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 ~I ~ ~ 8 ~ o~ ~ o ~ o ~ oo ml '~ ~ 8 l' 8 0 o~
~ ~~ '' ~ ~ 2 ~ ~ ~ ~~
o ~ o ~ o ~ o ~ o ~ ~ Zo --D
~ o c ~= o ~ g 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 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 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.
W O 97/00010 PCT~US96/10467 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
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.
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 0.05 149 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%.
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 0.016 124 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 W O 97/00010 PCTrUS96/10467 ~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 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 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 (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 % Il~hibition (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.
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 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.
,, ~ 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 ~I ~ ~ 8 ~ o~ ~ o ~ o ~ oo ml '~ ~ 8 l' 8 0 o~
~ ~~ '' ~ ~ 2 ~ ~ ~ ~~
o ~ o ~ o ~ o ~ o ~ ~ Zo --D
~ o c ~= o ~ g 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 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 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.
W O 97/00010 PCT~US96/10467 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
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.
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 0.05 149 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%.
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 0.016 124 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 W O 97/00010 PCTrUS96/10467 ~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 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 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 (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 % Il~hibition (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.
Claims (26)
1. A storage-stable, liquid or water soluble dry concentrate agriculturally acceptable water soluble composition comprising:
(a) glyphosate or one or more of its salts or mixtures thereof, (b) one or more alcohol surfactants having the following chemical structure wherein R1 and R2 are independently straight or branched chain C1 to about C28 alkyl, aryl or alkylaryl groups and the total number of carbon atoms in R1 and R2 is about 7 to about 30, R3 is hydrogen, R4groups are independently C1 to C4alkylene groups and n is an average number from about 3 to about 30; and (c) one or more other surfactants.
(a) glyphosate or one or more of its salts or mixtures thereof, (b) one or more alcohol surfactants having the following chemical structure wherein R1 and R2 are independently straight or branched chain C1 to about C28 alkyl, aryl or alkylaryl groups and the total number of carbon atoms in R1 and R2 is about 7 to about 30, R3 is hydrogen, R4groups are independently C1 to C4alkylene groups and n is an average number from about 3 to about 30; and (c) one or more other surfactants.
2. The composition of Claim 1 wherein, in the structure of said alcohol surfactant, R1 and R2 are both straight chain alkyl groups with a total of about 7 to about 30 carbon atoms, R3 is hydrogen and R4 groups are ethylene.
3. The composition of Claim 2 wherein, in the structure of said alcohol surfactant, n is an average number from about 7 to about 14.
4. The composition of Claim 1 wherein said alcohol surfactant is an ethoxylated Guerbet alcohol having an alkyl moiety of about 12 to about 16 carbon atoms, and n is anaverage number from about 7 to about 14.
5. The composition of Claim 1 wherein one or more other surfactant(s) are selected from the group consisting of alkyl monoglycosides, alkyl polyglycosides, sucrosealkylesters, tertiary and quaternary alkylamine alkoxylates, non-alkoxylated tertiary and quaternary alkylamines, alkylamine oxides and alkylbetaines.
6. The composition of Claim 4 wherein said other surfactant comprises a tertiary alkylamine surfactant with about 2 to about 10 moles of ethylene oxide per mole of amine.
7. The composition of Claim 6 wherein said tertiary alkylamine surfactant is a cocoamine or tallowamine with about 2 to about 5 moles of ethylene oxide per mole of amine.
8. The composition of Claim 1 which is an aqueous concentrate formulation with aglyphosate acid equivalent loading in the range from about 5 to about 40 per cent by weight.
9. The composition of Claim 1 wherein which is a dry concentrate composition with glyphosate acid equivalent loading in the range from about 10 to about 75 percent by weight.
10. The composition of Claim 1 which is a water-soluble granular formulation with a glyphosate acid equivalent loading in the range from about 40 to about 70 per cent by weight.
11. The composition of Claim 7 wherein the weight ratio of said alcohol surfactant to glyphosate acid equivalent is in the range of about 1:20 to about 1:1.
12. The composition of Claim 11 wherein the weight ratio of said alcohol surfactant to glyphosate acid equivalent is in the range from about 1:12 to 1:2.
13. The composition of Claim 12 wherein the weight ratio of said alcohol surfactant to glyphosate acid equivalent is in the range from about 1:6 to about 1:3.
14. The composition of Claim 7 wherein the weight ratio of said alcohol surfactant to said tertiary alkylamine surfactant is in the range from about 1:20 to about 5:1.
15. The composition of Claim 14 wherein the ratio is about 1:10 to about 2:1.
16. The composition of Claim 14 wherein the ratio is about 1:5 to about 1:1.
17. An aqueous herbicidal spray solution comprising:
(a) glyphosate or one or more of its salts or mixtures thereof;
(b) one or more alcohol surfactants having the following chemical structure wherein R1 and R2 are independently straight or branched chain C1 to about C28 alky, aryl or alkylaryl groups and the total number of carbon atoms in R1 and R2 is about 7 to about 30, R3 is hydrogen, R4 groups are independently C1 to C4 alkylene groups and n is an average number from about 3 to about 30; and (c) one or more other surfactants; and (d) water.
(a) glyphosate or one or more of its salts or mixtures thereof;
(b) one or more alcohol surfactants having the following chemical structure wherein R1 and R2 are independently straight or branched chain C1 to about C28 alky, aryl or alkylaryl groups and the total number of carbon atoms in R1 and R2 is about 7 to about 30, R3 is hydrogen, R4 groups are independently C1 to C4 alkylene groups and n is an average number from about 3 to about 30; and (c) one or more other surfactants; and (d) water.
18. The composition of Claim 17 wherein, in the structure of said alcohol surfactant, R1 and R2 are both straight chain alkyl groups with a total of about 7 to about 30 carbon atoms, R3 is hydrogen and R4 groups are ethylene.
19. The composition of Claim 18 wherein, in the structure of said alcohol surfactant, n is an average number from about 7 to about 14.
20. The composition of Claim 17 wherein said alcohol surfactant is an ethoxylated Guerbet alcohol having an alkyl moiety of about 12 to about 16 carbon atoms, and n is an average number from about 7 to about 14.
21. The composition of Claim 17 wherein one or more other surfactant(s) are selected from the group consisting of alkyl monoglycosides, alkyl polyglycosides, sucrosealkylesters, tertiary and quaternary alkylamine alkoxylates, non-alkoxylated tertiary and quaternary alkylamine, alkylamine oxides and alkylbetaines.
22. The composition of Claim 21 wherein said other surfactant comprises a tertiary alkylamine surfactant with about 2 to about 10 moles of ethylene oxide per mole of amine.
23. The composition of Claim 17 wherein said tertiary alkylamine surfactant is acocoamine or tallowamine with about 2 to about 5 moles of ethylene oxide per mole of amine.
24. The composition of Claim 23 wherein the weight ratio of said alcohol surfactant to glyphosate acid equivalent is in the range of about 1:20 to about 1:1.
25. The composition of Claim 23 wherein the weight ratio of said alcohol surfactant to glyphosate acid equivalent is in the range from about 1:12 to 1:2.
26. The composition of Claim 23 wherein the weight ratio of said alcohol surfactant to glyphosate acid equivalent is in the range from about 1:6 to about 1:3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US49146695A | 1995-06-16 | 1995-06-16 | |
| US08/491,466 | 1995-06-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2224364A1 true CA2224364A1 (en) | 1997-01-03 |
Family
ID=23952351
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002224364A Abandoned CA2224364A1 (en) | 1995-06-16 | 1996-06-17 | Surfactants providing enhanced efficacy and/or rainfastness to pesticide formulations |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0854676A4 (en) |
| JP (1) | JP3980640B2 (en) |
| AU (1) | AU696607B2 (en) |
| CA (1) | CA2224364A1 (en) |
| NZ (1) | NZ312352A (en) |
| WO (1) | WO1997000010A1 (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9703054D0 (en) * | 1997-02-14 | 1997-04-02 | Ici Plc | Agrochemical surfactant compositions |
| DK1073331T3 (en) * | 1998-04-24 | 2003-06-16 | Monsanto Technology Llc | Concentrate composition of an acid treatment plant treatment compound |
| FR2790642A1 (en) * | 1999-03-08 | 2000-09-15 | Aventis Cropscience Sa | NEW PESTICIDE AND / OR REGULATORY GROWTH COMPOSITIONS |
| ATE250857T1 (en) * | 1999-03-11 | 2003-10-15 | Ecoval Corp | HERBICIDAL COMPOSITION |
| AUPQ017599A0 (en) | 1999-05-05 | 1999-05-27 | Victorian Chemicals International Pty Ltd | Adjuvant composition for chemicals used in agriculture |
| AUPQ579800A0 (en) | 2000-02-23 | 2000-03-16 | Victorian Chemicals International Pty Ltd | Plant growth hormone compositions |
| MY158895A (en) | 2000-05-19 | 2016-11-30 | Monsanto Technology Llc | Potassium glyphosate formulations |
| WO2002032227A1 (en) | 2000-10-17 | 2002-04-25 | Victorian Chemicals International Pty Ltd | Herbicide composition |
| AU2003232505B2 (en) | 2002-04-24 | 2009-08-27 | Basf Aktiengesellschaft | Use of defined alcohol alkoxylates as adjuvants in the agrotechnical field |
| MY157730A (en) * | 2004-09-27 | 2016-07-15 | Kao Corp | Herbicide composition |
| JP2006117650A (en) | 2004-09-27 | 2006-05-11 | Kao Corp | Herbicide composition |
| BRPI0909773A2 (en) * | 2008-04-24 | 2015-10-06 | Basf Se | suspension concentrate of a plant protecting active agent, uses of the suspension concentrate and a cyclodextrin, method for treating fungicide, insecticide or herbicide of plants and their habitat, and spray mixture. |
| EP2138041A1 (en) | 2008-06-26 | 2009-12-30 | Basf Se | A method for enhancing the rainfastness of glyphosate |
| EP2138042A1 (en) | 2008-06-26 | 2009-12-30 | Basf Se | A method for enhancing the rainfastness of glyphosate |
| ES2648201T3 (en) | 2008-09-29 | 2017-12-29 | Monsanto Technology Llc | Glyphosate formulations containing almidoalkylamine surfactants |
| EP2457890A1 (en) * | 2010-11-29 | 2012-05-30 | Cognis IP Management GmbH | Biocide compositions comprising alkoxylation products of isoamyl alcohol derivatives |
| WO2017196951A1 (en) | 2016-05-11 | 2017-11-16 | Monsanto Technology Llc | Glyphosate formulations containing amidoalkylamine surfactants |
| WO2020025393A1 (en) | 2018-07-30 | 2020-02-06 | Bayer Aktiengesellschaft | Combinations containing pva and certain herbicides with improved properties |
| CA3107834A1 (en) | 2018-07-30 | 2020-02-06 | Bayer Aktiengesellschaft | Herbicide compositions with improved properties |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2589328A1 (en) * | 1985-10-31 | 1987-05-07 | Stauffer Chemical Co | Method and composition for improving the herbicidal activity of salts of N-phosphomethylglycine |
| DK191386D0 (en) * | 1986-04-24 | 1986-04-24 | Koege Kemisk Vaerk | emulsifier |
| US4990175A (en) * | 1989-06-13 | 1991-02-05 | Dow Corning Corporation | Foliar applied herbicidal compositions containing a silicone glycolsilicone alkane terpolymer adjuvant |
| AU650091B2 (en) * | 1991-02-08 | 1994-06-09 | Monsanto Europe S.A. | Glyphosate compositions and their use |
| CA2074993A1 (en) * | 1991-08-02 | 1993-02-03 | Miguel Molina Dayawon | Glyphosate-containing herbicidal compositions having enhanced effectiveness |
| US5258359A (en) * | 1991-08-02 | 1993-11-02 | Monsanto Company | Glyphosant-containing herbicidal compositions comprising acetylenic diol rainfastness enhancing agents |
| MY111437A (en) * | 1992-07-31 | 2000-05-31 | Monsanto Co | Improved glyphosate herbicide formulation. |
-
1996
- 1996-06-17 AU AU63863/96A patent/AU696607B2/en not_active Ceased
- 1996-06-17 CA CA002224364A patent/CA2224364A1/en not_active Abandoned
- 1996-06-17 NZ NZ312352A patent/NZ312352A/en unknown
- 1996-06-17 EP EP96923316A patent/EP0854676A4/en not_active Withdrawn
- 1996-06-17 JP JP50340097A patent/JP3980640B2/en not_active Expired - Lifetime
- 1996-06-17 WO PCT/US1996/010467 patent/WO1997000010A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| JP3980640B2 (en) | 2007-09-26 |
| AU696607B2 (en) | 1998-09-17 |
| EP0854676A4 (en) | 2000-03-15 |
| NZ312352A (en) | 1999-11-29 |
| EP0854676A1 (en) | 1998-07-29 |
| AU6386396A (en) | 1997-01-15 |
| WO1997000010A1 (en) | 1997-01-03 |
| JPH11507673A (en) | 1999-07-06 |
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| FZDE | Discontinued |
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