CA2183857A1 - Adjuvant compositions - Google Patents

Abstract

Surfactant containing adjuvant compositions include surfactant vic-dicarboxylic acid polyalkyleneoxy half ester derivative of the formula (I) Y.A1.OC.(HR)C.C(HR1).CO.A.(CmH2mO)n.R2 or (II) Y.A1.OC.(HR)C.C(HR1).CO.A.(CmH2mO)n.CpH2p.A.CO.(HR1)C.C(HR)CO.A1.Y, where the substituents have defined meanings, and at least one of: (b) at least one other surfactant, (c) at least one oil component, and (d) at least one organic solvent. The adjuvant compositions can be used in agrochemical formulations, particularly compositions containing growth regulators, herbicides and/or pesticides or in metal working compositions in which they typically contain a metal corrosion inhibitor.

Description

~ WO 95/22896 l ~

Adiuvant Comr ositions ~
This invention relates to adjuvant cu.. I~JOa;~iUI la, and in particular to , " la which contains at least two surfactants and/or at least one oil, to dispersible -,u"~"t, aks, which are readily 5 dispersible andlor soluble in water, in particular to uu~ ,-,c:"L, ~ a with a high dispersed phase loading, uomprising such an adjuvant composiUon, to diluted fnrml 1' " ID uomprising the concentrate, and to prooesses for preparin6 or using the adjuvant , ' ' la, the, u, ,~,~"l, c~t~a, and the diluted fommulations.
CI, ~' ,awithatleastonesurfactantareknowningeneralintheau,u.,l,~,,,k,alindustryfor use as ~,u,, ,uu, lel l~a of uu, ~ "l~ dt~D comprising an ayl uul ' or of a UUI, aDuul Idil ,~ diluted fommulation comprising the concentrate such that the ay,l u~.l Itll I liual is readily dispersible andlor soluble in the concentrate or diluted formulation. Such known ~ul " lD and such known uul~c~lltla~S uomprising an active chemical a~ent may also comprise at least one oil uomponent.

There is also a demand for example in the aul u~ ,k,al industry for adjuvant ~u,, ,~,uaiLiu, la which enhanoe the activity of any chemiual agent (e.~. an ayl uu~ " ,;~al) or other materials which are present in the conoentrate or cu" ~a~ul Idil ~u dilute formulation. In some intended uses of such cu, ,~,~, ,l, al~a, e.g. in methods of applying r,u,, ~sD,uu, ,li, ,y fommulations of some c~
20 such as insecticides, herbicides, fungicides or auaricides, it is preferred Uhat not only will the l,ul I ~_~JUI ,.lil Iy diluted fommulation comprisin3 the composition have a si3nificantly enhanoed activity, but that the processes for preparing the formulation is no more than simple mixing.
However, (a) the efficacy o~ known adjuvant ~,ùllluuai~iùl ID as adjuvants and 25 (b) the extent to which the resultant uu, l,,e~ , a~s are readily dispersible and/or soluble into water is usually limited to a specific ~.u,,,ui, la~iùl~ of a dispersed chemiual agent and readily dispersible and/or soluble surfactant 1UI I I,UUI n~ D.
This invention seeks to provide a class of materials of this adjuvant nature, which give 3owll~lltla~a9whicharereadilydispersibleandlorsolubleintowaterland~ulll:au~ illydilute fommulations with significantly enhanced activity, whlch are useful in general in the auluul industry.
We have developed a class of vic-diuarboxylic acid polS. 'k~ U~y half ester derivatives as 35 desuibed in published PCT Application No WO 94/û0508 A (PCTIGB 93/û1335). This invention relates to applications of compounds of this general type of the formula (I) or (Il) below:

WO 9~i/22896 1'.~ J9 21838~7 . . - 2 --Y.A'.OC.(HR)C.C(HR').CO.A.(CmH2mO)n.R2 (1) where one of R and R1 is Cs to C22 alkenyl or alkyl and the other is hydrogen;
A is -0- or -NR'-; where R~ is hydrogen or C, to C~ alkyi, particularly methyl or ethyl;
5 n is 2 to 100 (and as it is an avera3e it may be non-intesral);
m is 2 or 3 (and may vary along the ,c Ul~UAf 'hfl~,"~ chain);
R2 is hydrogen or C, to C,~, particularly C, to C~ alkyl;
A' is -0-, -0 or -NR~- where R4 is hydrogen or C, to C, alkyl, particularly methyl or ethyl;
such that 10 when A1 is -0~: Y is a cation, particularly H~, and alkali metal cation especially a sodium or potessium cation, or an ammonium ion (especially NH~, an amine ammonium or an ' ,uld,,,i,,vammoniumion); and when A' is -0- or -NR~-: Y is a C, to C~ alkyl group (R3) or a group of the fonmula (CmH2mO)n.R2 where m, n and R2 are i, ,dv~ JVI ILly as defined above;
~ 150r Y.A'.OC.(HR)C.C(HR').CO.A.(CmH2mO)n.CpH2p.A.CO.(HR')C.C(HR)CO.A'.Y (Il)where: n, m and each R, R', A, A' and Y are i,)de,uv, ~dv~ I ~) as defined above; and p is 2 or 3.
20 As described in W0 94/00508 A, the free acid fomms of compounds of the fonmulae (I) and (Il) in are defined with Y as a H~ cation includinL~ both the ionised and non-ionised fomm of the free acids.
Compounds of the fommulae (l) or (ll) are typically miAtures of isomers w" v 2uu"~i"~ to the two senses of the anhydride ring openin3 reaction typically used in their synthesis The alk(en)yl chain seems to have a minor steric effect on the isomer ratio (typically about 6û:40), the major 25 isomer arising from nucleophilic attack at the anhydride carbonyl group remote from the alk(en)yl gnoup. Thus in particular the compounds of the formulae (I) and (Il) include those of the formulae (la) and (lla):
R' - CH(CO.AY) - CH2 CO.AZ (la) in which 30 z is a group of fommula (CmH2mO)nR2 in which n, m and R2 are as def ned for Fommula (I) above with n preferably being 3 to 5û;
R2 is hydnoL~en or an alkyl group having 1 to 16 and preferably 1 to 6 cr~rbon atoms;
A and A' are each il Idv~uvl ,dv, ILly -0-, -0 or -NH- groups, when A or A' is -0 the respective Y is a cation for eAample H~ or an alkali metal ion, when A or A' is -0- or -NH- the respective Y is a group R2 or (CmH2mO)nR2 where m and R2 are as dehned above and may be the same or different to the group Z, R' is an alkyl or alkenyl group having 6 to 22 and preferably 13 to 20 carbon atoms, , ~ Wo ss/22896 à ~ 9 or of ~ommula (lla):
R' - CH(COA'Y) - CHi-CO.A - D - A.OC - CH2 - CH(COA'Y) - R' (lla) in which D is a group of fommula (CmH2mO)n C5H2p -in which p is 2 or 3, and 5 R', A, A', m and n are as def ned above for fommula (1 a).
Various uses of compounds of this general type are described in WO 94100508 A, includin3 as emulsifying agents for acrylamide invert pu'~ ."~" ' " , systems and as wool scouring aaents. We have now found that such compounds are useful in adjuvant ,,u, I r "' la together with at least 10 one of:
(i) at least one other surfactant, (ii) at least one oil component, and (iii) at least one organic solvent.
These may be used to fomm Wl l~.el ILI dLea comprising a chemical agent with activity specific to the 15 intended use of the ,,u"~:, Itl dl~S and fommulations comprising the l..UI l~.el ILI dles such that the dUlU~,llt:lll;.,dl therein is readily dispersible and/or soluble into water. Such ~,ulll,e"~ldLea and fonmulations comprising the w"~, dldLss (unlike the above, , " la, which may be used as a component of cu, ,~"L, dl~s) need not comprise at least one other surfactant, at least one oil component or at least one organic solvent, although they may of course do so. The fommulations 20areusefulforapplyinginthec,u,u.,l,e,,,; dlindustry,e.g.forau,u~,llt,,,li~l~,suchasherbicides, fungicides or acaricides.
According to a first aspect of the invention there is provided a composition which comprises:
(a) at least one surfactant vic-dicarboxylic acid pol~ 'ky'~ UA; half ester derivative of the 25 fon~ula (1) or (Il) as defined above; and at least one of (b) at least one other surfactant, (c) at least one oil component, and (d) at least one organic solvent.
30 Suitable adjuvant ~u, " " la of this first aspect are those comprising (a) at least one vic-dicarboxylic acid pu:~ ,,euA~ half ester derivative, present as 1 to 90 wt.% of the total composition, preferably as 5 to 75 wt.%; and at least one of:
(b) at least one other surfactant, present as 0 to 90 wt.% of the total, preferably as 0 to 70 wt.%
of the totaH,u~ luùa;liul ,, 35 (c) at least one oil component, present as 0 to 99, and in particular as 0 to 97 wt,% of the total wllluuaiLi~l ,, andlor

- 2-1~3857 .~ ,5.'~ 59 (d) at least one organic solvent, present as 0 to 90 wt.%, and in particular as 0 to 75 wt.% of the totsl composition.
The componenh and their proportions are preferebly chosen such that where any Cull luùl lel l~a are 5 readily avsilable only as aqueous solutions the , " ~ provided by mixing the composition components is stsble, l l ' "' lalal l iil Iy the water which is thereby introduced.
The composition often employs a half-ester derivative containing anionic groups and/or in p2rticular sroups ionisable to anion. Preferred such ester derivatives are generally as set out in 10 our co-pending application, but preferred vic-dicarboxylic acid uu.y. ", k.. IeOXy half ester derivative surfactants of this type include mono- and di-ester derivatives of formula (i) or (Il~
respectively in which RIR' as def ned preferably has 8 to 20 carbon atoms. This is particularly the caseinthedu,u.,l,e,,,i.,alindustrywhenusedtoformadispersibleand~orsolubleconcentrateor U UI I ~aUUI l~iil IU dilute formulation comprising a chemical agent with activity specific to the intended 15 use of the concentrate om,u" cauul l~iil IU dilute fomnulation. Particular ester derivatives of this type include those in which R~R' has 1 û to 17, preferably 12 to 14 carbon atoms, and in particular where it is an alkenyl group. Prefenred such vic-dicarboxylic acid ,uu'~ "euA~ half ester derivatives also include those of fommula (I) in which the group (CmH2mO)nR2 as defined above or the fommula (la) in which Z is an alkylene oxide (block) (co-)polymer of fommula (CmH2mO)nR2 as 20 defined above, in which n is preferably 7 to 13 and m is 2 andlor 3.
The other surfactant(s), if present, may be any which on using the adjuvant composition in the fommulation of a concentrate or diluted fommulation comprising a chemical agent with activity specifctotheintendeduseoftheconcentrateom,u,,e~uu,,~ii,,gdiluteformulation, 25 a will give a concentrate or diluted formulation which is stable and homogeneous for at least 24 hr. after making up, and b in the case of a concentrate, remains homogenous on dilution with water to a formulation.
Subject to this proviso, the other surfactants which are suitable for use in the concentrate or UUI ! eauul ~ 9 diluted formulation include anionic, cationic, amphoteric or non-ionic âurfactants, or 30 mixtures thereof.
Suitable anionic surfactants include members of the alkarene sulphonate salt ~qroup, such as an alkyl benzene sulphonate salt having 6 to 16 carbon atoms in its straight chain or branched alkyl group, e.~q. wherein the alkyl is lauryl (dodecyl), or mixtures thereof; members of the poly(arylaryl-35 alkoxylate) phosphate or sulphate salt group; members of the alkaryl phosphate or sulphate saltgroup; members of the straight chain or branched alkyl- and alkoxylated alkyl phosphate or sulphate salt group; and members of the fatty acid salt group, having 8 to 24, preferably 12 to 18, WO 9S/22896 ~ ~ i 21 8 3 8 5 7 r~l ~h ~ ~ sg carbon atoms, e.s. iaurate~ ,U~ddtlWI IUdb, ~ u~ad~ uaLc, stearate and oleate; and/or members of the 6roup of salts of alkoxylated w~ ~uAylal~d alkaryl and fatty alcohols, the latter includins e.g. poly~ethylene oxide)C,2 ,s alcohol m~ d,~ùA~
5 Examples of suitable salts include those with a cation which is an alkali metal e.s. sodium or potassium; an alkaline earth metal, e.g. alcium; andlor ammonium, aliphatic ammonium ~uk.. I~UI ,ium cation, wherein the aliphatic or alkanol moieties are e.g. straight-chain or brânched alkyl havin3 1 to 4 carbon atoms; and miAtures thereof.
10 In particular when the composition is used in the au~,u~l, ' industry to form a dispersible and/orsolubleconcentrateoruu,lu~uu,,di,,_dilutefommulationcomprisinganau,u~ ,,,i.,dlagent with activity specihc to the iniended use of the concentrate or ..u, 1~2 2UUI Idil Iy dilute fommulation, preferred component (b) anionic surfactants include ", ;i t~ "e sulphonate salts having 6 to 16 carbon atoms in their straisht-chain or branched alkyl sroup, e.s. wherein the alkyl is lauryl.
15 Preferred salts include the calcium salt.
Cationic surfactants which are suitable for such stability include alkoxylated fatty amine salts having 8 to 24, preferably containing more than 12 carbon atoms, and in particular 12 to 18 carbon atoms, the latter including e.g. poly(ethylene oxide) Cl2,0,5 amine salts, e.g. chloride salts.
Non-ionic surfactants âre particularly useful in .,u, ,~"I, dlt:S which are readily emulsifiable in pariicularinau,u~l,,:,,,i-,aluu,~ dt~s. Theseincludenon-ionicsurfactantsusedinthe a~l u~ l8.dl industry to fonn ~ pc~ in panticular those of the formulae R21.0(X)R22 and/or R2sOR2a andlor R23- N (-XH)2 25 in which R2' is an alkyl sroup or alkenyl group which suitably contains uo to 24, preferably 6 to 21, and especially 9 to 18 carbon atoms, an alkyl phenol group havins 6 to 12 carbon atoms in its alkyl group, a sorbitan group or a group of fommula R23Co in which R23 is an alkyl group having 11 to 22 carbon atoms;
30 R22 is hydrogen or an alkyl group, a carboAyalkyl gnoup, e.g. w, bUA~ -1 having 2 to 4 carbon atoms, or a fatty acid residue having 10 to 22 carbon atoms;
X is a, '~ . ,e oxide group containing an average of 2 to 4û, preferably from 2 to 13, and especially from 2 to 10 alkylene oxide sroups or mixed alkylene oxide groups, R23 j5 an alkyl or alkenyl group having 10 to 22 carbon atoms;
35 R2~ j5 a sorbitan group;
R2s is a fatty acid residue hâving 10 to 22 carbon atoms; and R26 is an alkyl or alkenyl group having 10 to 22 carbon atoms.

WO 9~i/22896 . 218 ~ $ ~ 7 r~ 9 ~

Examples of suitable ~roups R2' include e.3. 1auryl, heptadecyl, 1 ,c,u~adc:~,,J~
stearyl or oleyl moieties. Examples of suitable groups R22 include e.g. carboxy-methyl, ethyl or propyl, or a salt thereof; and lauroyl, I leu~a(ieual lùjl, I~:,uLa~ u~:l lo;l, 1~ Io~l, stearoyl or oleoyl. Suitable possibilities for X include those wherein the alkylene ~roups each have 2 to 8, 5 preferably 2 or 3 carbon atoms. Examples of suitable groups R2' include e.g. Iauroyl, ad~,al~ojl, Ile,uLadtl~ lujl, 1~ lujl, steanoyl oroleoyl.
Examples of suitable non-ionic surfactants thus include poly(~ ,d) fatty acids and alcohols havin~ 8 to 24, preferably 12 to 18 carbon atoms in their fatty acid or alcohol groups;
10 poly(alkoxylated) alkaryl alcohols havin~ 8 to 24, preferably 12 to 18 carbon atoms, and phosphate and sulphate esters thereof; poly(alkoxylated) sorbitan and sorbitol esters;
poly( " , I_'~I) mono-, di- and L, i~ .,él kJ~:" including poly(alkoxylated) vegetable oils, such as poly(ethoxylated) mustard oil, neem oil, niser seed oil, oiticica oil, palm oil, palm kennel oil, peanut oil, safllower oil, sesame oil, soybean oil, and especially castor oil poly(alkoxylated) allyl alcohols, 15 and phosphate and sulphate esters thereof; poly(~ .8.l) poly(anylanyl alcohols); sorbitan mono~sters in which the acyl ~roup has 11 to 22 carbon atoms; and poly(alkylene oxides) includin~ (block) (co-)polymers.
Within one class of adjuvant ~Ill,uu~iLiu,la of the hrst aspect of the present invention, especially 2û when used for fonmulations for application in the a~l uul 1~l l Ik,al industry, the component (b) (another surfactant) is (i) at least one non-ionic surfactant, and/or (ii) at least one anionic surfactant.
25 Prefenred component (b) non-ionic surfactants then include those of the fonmula R .O(X)R and/or R2~.OR2s and/or R - N (-XH)2 as defined above which are indicated as preferred non-ionic surfactants above Preferred component (b) anionic surfactants include 'hy;. t2"~:"e sulphonate salts having 6 to 16 30 carbon atoms in their straight-chain or branched alkyl group, e.3. wherein the alkyl is lauryl.
Preferned salts include the calcium salt.
The oil component typically has a boilina point of over 20û'C at _`l l lual~ l L. pressure and a melting point not higher than 6ûC. It may comprise for example a mineral oil, an optionally 35 hjd, uy~:, Idt_sl vegetable oil, such as an optionally ~.; .i~ U~e:l laLw::l cotton seed oil, linseed oil, mustard oil, neem oll, ni~er seed oil, oiticica oil, olive oil, palm oil, palm kernel oil, peanut oil, W0 95~22896 ' . =' ~ 1 8 3 8 ~ 7 r ~ 9 , .. . .

perilla oil, poppy seed oil, rape seed oil, safflower oil, sesame oil, or soybean oil, an ester (especiallyaC1,cbester)ofaC~,,22fattyacid,especiallyaC,2,0,Dfattyacid,oramixturethereof.
In the composition any oil soluble surfactant present may of course be partitioned between an oil 5 phase and an aqueous phase.
Preferred adjuvant ,u, Il,uu:,iliu, ,:, of this flrst aspect are those comprisin~o (a) at least one vic-dicarboxylic acid ~u!~ UA~ half ester derivative, pnesent as 5 to 9û
wt.% of the total composition, preferably as 1 û to 75 wt.%; and û (b) (i) at least one non-ionic surfactant, present as 0 to 90 wt.% of the total, preferably as 0 to 50 wt.%, e.g. 0 to 40 wt.%, in particular 0 to 35 wt.%; and/or (ii) at least one anionic surfactant present as 0 to 6û wt.% of the total, pneferably as û to 40wt.%,e.g.15to40wt.%,inparticularas25to40wt.%ofthetotal;and/or (c) at least one oil component, present as 0 to 97, e.s. 0 to 85, wt.% of the total.
One class of such adjuvant . .. I " .~ is of those comprising at least one anionic surfactant as 15 to 40 wt.%, in particular as 25 to 40 wt.% of the composition. Another class of composition is of those comprisin3 no anionic surfactant.
20 The organic solvent in particular when used in fommulations for appiication in the dUI u~h_.. .;~l industry, may be one or more water-miscible andlor soluble liquids and/or water-insoluble organic solvents. This is desirable if the viscosity of the composition would otherwise be il)l,UI .. _. Ii~l l ly hioh. Examples of suitable water-miscible and/or soluble liquids include alcohols, including 31ycols, e.g. with straight-chain or branched alkyl having 1 to 18 carbon atoms. For applications in 25 the aul u~ ll liwl industry, preferred examples include isobutanol, n-butanol, isoheptyl alcohol, n-and iso-octanol; and propylene and ethylene glycols, and mixtures thereof. Such liquid may often contain water.
Examples of suitable water insoluble organic solvents include i^.~ dlu~ i,u, la, preferably those 30 havino 5 to 18 carbon atoms, including aromatic h~ ll uw, i u, Ial andlor straight chain or bnanched fatty alcohols, and isopanafflns, and mixtures thereof.
The oomposition may be used without any specific chemical agent, e.g. as a precursor for dilution with water for metal cutting fluids.
The adjuvant composition to which the first aspect of this invention relates may be produced by ~o~ ;J~Il mixing of the components in any onder used uu~ iu~ "y in the formulation of such W09s/22896 ' 2 1 83 3S7 ~, ' ,aforuseincunce,,lldLesom,ul,eauu,,-lilludilutefonmulationsforapplicationinthe d~U,I u~,l lell liWI industry. In a sewnd aspect the present invention thus proYides a process of makin3 the wmposition by mixing the wll,,uu"ell~ to3ether.
5 Accordin3 to a third aspect of the invention there is provided a dispersible and/or soluble concentrate comprisin3 (a) at least one surfactant vic-dicarboxylic acid ~ '~ ", ' ,e.,A~ half ester derivative of the type I lél eil IborUl e described; and (e) at least one chemical a3ent with activity specific to the intended use of the concentrate or 10 w"eauu"di"ydilutefonmulation.
Such chemicai agent specihc to the intended use of the concentrate or "u" e:~,uul Idil ~v dilute fonmulation may be for example an dulu-l le",i~,dl or a metal wnrosion inhibitor.
If an dUI Ul~h~n'.;_dl is present it is typically one or more IJI ,, 'Udl.~i /US, for example 3rowth 15 re3ulators or herbicides, andlor pesticides, for example insecticides, fungicides or acaricides.
Suchw,,~,e,,L,dtesmaycompriseasecondchemicalagentwhichwill3iveaconcentrateinwhich the activity of the first chemical a3ent is made more specific to or selective in the intended use of the concentrate Om,ul ~ ea,uul l~ y dilute fonmulation.
2û
Such wl luel ILI dlea typically include e.g. uul)uel ,~, d~es in which (a) the first chemical agent is an dUI uul lel I liWI which is one or more phytoactives, for example 3rovlth regulators or herbicides, and/or pesticides, for example insecticides, fungicides or acancides, and 25 (b) the second is a phytotoxicity inhibitor to re3ulate any ,ul l~ua~ ;`y, for example 3rowth re3ulation or herbicidal acbvity of the concentrate or w, I ecluul ~dil l_ dilute formulation, or e.g. Safener inhibitor to make it more selective, e.g. as between 3raminious and broad leaved species.
Such a second chemical a3ent may be present as up to 15 wt.% of the total concentrate.
Preferred w, I-,el lll dlas are those with a hi3h loading of the dispersed phase appropriate for the intendaduseofthecwncentrateor,,ul,ea,uu,,dillgdiluteformulation.
These exhibit dispersion even of specific chemical agents which are known in the au, u~l lel l~k 35 industry as not usually readily dispersed.
One class of such ,u, ,-,~, IL, c~ea is that of ~u, ,cs, ILI ~Les comprising at least one of ~ W0 95~12896 ~ 3 8 ~ 7 r~ g (b) zt least one other surfactant, (c) at least one oil component, and (d) at least one or~anic solvent.
(e) at least one chemical agent with activity specific to the intended use of the concentrate or 5 wl I ea,uul Idil lg dilute formulation.
Component (d) (optionally, at least one oroanic solvent), if present as a component of the above ooncentrate, will often a be the same as, or 10 b comprise, the water miscible andlor soluble liquid(s) and/or water insoluble organic solvent(s) which are present in the Cwl, ~ u, l~ rJ adjuvant composition, which in such case thus fomms a component of the concentrate and ,,u" Ua~JUI Idi, ,u dilute fommulations. A~ain, includin~o (d) to fomm a component of such w"Oe:l ,l, a~ea may be desirable if the viscosity of the concentrate would otherwise be 15i"w".~,.,ie"Llyhish,especiallywhenusedinuu"~,e"l,a~forformulationsforapplicationinthe aul uul l ' industry.
Each of the present wl)uel 1ll aLu:~ when present with say, 10 to 10,000 times the total weiaht of the w...~,u,,~ ,(a)and(d~ofwaterinaw,,~,uu,,di,,udilutedfonmulationofthepresentinventionfor 20 application of the component (d) of the concentrate, (a) remains stable and homogenous without the need for the addition of any further materials to disperse the relevant phase and prevent settling of the dispersed phase from the diluted Cwll~,éllLlaLe, and ~b) produces formulations with siqnificantly enhanced activity of the chemical agent specific to 25 the intended use of the fonmulation, without the need for the addition of any further adjuvant materials for enhanced activity.
(c) exhibits sood wettin3 properties in relation to the dispersed chemical a8ent in the concentrate herein described, and in particular in relation to treated substrates.
30 Suitable and prefenred vic-dicarboxylic acid pol~ 'hylu. 113UAy half-ester derivative ,o, l luullel Ib are those so described l~leil IL-~rul: with re3ard to the same materials which form .,u, , ,,uu, ,~:"~, of the adjuvant cu, I IIJùaiLiul la of the first aspect of the invention.
Suitable and preferred optional components of such uo,)~,el"L, aL~s, i.e. cu"~,uu~ k, such as other 35 surfactant(s), oil component(s) and oroanic solvent(s), if present in the concentrate, are generally thosesodescribedl~u,ei,,~erul~withreoardtothesamematerialâwhichform~.u,l,uu,~e,,Laofthe adjuvant ~u,,I,uuaiLiul~s of the hrst aspect of the invention.

wo ss/22896 r~
--: 21838~7 , .

An anti-foam agent may be present. A sufficient quantity to provide an anti-foaming effect for the intended use of the concentrate or ,,u" ~uu, l~ u dilute fomnulation without separating out is desirable. Nommally 0.05 to 10% and preferably 0.2 to 6% by weight of the total is suitable. Any compounds may be used which are c u".~ ,/ useful as anti-foam agents in aqueous 5 surfactant fonmulated with a high dispersed phase content. The antifoaming agent(s) is preferably one or more, ') ' ,us, especially of the type havin,o, hydrophilic groups. It is preferably of fommula:
R~3 SiO ~rsio R~ R~nSi R;
in which 1û the groups R~ are individually alkyl groups, preferably having 1 to 3 carbons atoms and are preferably methyl groups, one or more of the 6roups R~ may be residues of pu~ . ,e glycols and the others are as denned for R~.
The groups R~ preferably have a molecular weight in the nange 1000 to 20000 and especially 5000 15 to 15000. Examples of suitable ,. 'y ' ,e antifoams are disclosed in British Patents 1533610 and 1 554736.
Other possible additives in the dispersible and/or soluble concentrate to which this invention relates include non-surfactant materials which are cu,, . _. " ,_::~ useful in surfactant fommulations, 20 such as viscosity modifiers, stabilisers, and anti-microbials One class of known viscosity modifier materials of this type includes one or more cu"""c~
aYailable water-soluble or -miscible materials such as gums, e.g. xanthan sums, and~or cellulosics, e.g. carboxy-methyl, ethyl or propylcellulose. These are often present, when used e.g. in 25 a~,u~ "1iual fommulations in particular as O.01 to 5 vlt.% of the total concentrate.
The present concentrate may have a pH value within a range of for example 3 (acid) to 10 (alkaline), for example 6 to 8.
30 The dispersible andlor soluble ~u, " ~"~, .,L~ to which this invention relates may be produced by .u, . . e,. ,Liu, It.l mixing of the ,u" IUUI 1~ in any order used cul, . _. I" I_:'; . In a fourth aspect the present invention thus provides a process of making the concentrate by mixing the components together. This may be effected for example by adding the l,UI IIUUI 1~ .. (a) snd (e), and any optional other additives, and stirring until the product is l)u,,,u9u,)eous.
For some dispersible andlorsoluble cuilu~llll~L~s to which this invention relates, mixing the components in a specific order may be necessary or e.g. may be desirable if the viscosity of the .... _ ... _ . _ . . _ _ .. .. ..... .. ..... ...... .... ... ... .. .. . ...... .... . _ _ _ . . .. ... _ .. _ W095122896 21838~7 r~ cl~ ~
composition would otherwise be i"w" . ~ !) high. Such dispersible and/or soluble~,u",,~"L, dl~ may have to be produced by separate w, . ~"' ,~l mixing of the w" ,~,u"~"~, of the orgsnic solvent (d), e.g. water-miscible snd/or soluble liquids andlor water-insoluble organic soivents, optionally, with at least one oil uomponent to fomm a first liquid phase, and dispersion of S the specific chemical a9ent(s) (e) for the intended use of the concentrate or w~ u~ u fommulations together with the remainin3 cu",,uul l~ , e.g. another surfactant (b) to aive a seuond ssparate liquid phase. This is effected with stirring until each phase is homo3eneous. The concentrate is made by careful dispersion of the second phase into the first phase.
10 It may be desirable that this is effected for example by adding the phases at moderately elevated temperatures with high shear mixin6 to deal with the i"-,u". _. ,u:, I:!y high viscosity of the uoncentrate which is thereby introduced. The product cù"..~"L~ IL~d dispersion is subsequently left to cool to ambient temperature.
15 Some dispersible and/or soluble w, ,u~, ,L, c,L_~ may have to be produced by separate spraying of one or more solid uo" "-U"t" ,~ of the conuentrate, e.~. the speciflc chemical agent(s) (e) onto a c2rrier to 6ive a solid phase, followed by dispersion of the carrier tosether with the remainins uomponents. This latter may be effected for example by stirrins until the product is l~u,, luue~ ous.
This variant may be necessary if the solid uomponent(s) are those senerally desuibed in the art û as not usually readily dispersed in ,u~ t~clL~:s of the present class for application in t he industry.
In some applications, the ,u, ,..~"L, c~Lt:~ of the third aspect of the invention will suitably be supplied to the customer as such and converted to a more dilute fomm at the point of use in such 25 applications.
In other applications, the relevant chemical agent is supplied to the customer, optionally with at laast one organic solvent or oil but separate from the remaining components of the concentrate in a seuond separate phase, and conversion to a dilute formulation, e.g. for application in the 3û .luluulltl~iwl industry, is effected by dilution of the two sets of materials, with stirring, followed by mixing of the w"~u, Idil IU diluted materials to effect dispersion of the agent in the formulations for appliuation.
Good stability in stora5e of the uu, ",~"L~ ~L~ :J materials in either form as supplied before being 35 converted to a more dilute form at the point of use is required.

WO 95/22896 Pt~T~GB95/00369 2183,,3,~7 In a fifh aspect the present invention provides a fommulation which is a mixture of the -,u",uv"~ D
(a) snd ~e) and optionally (b), (c) and (d) of the concentrate according to the third aspect of the presentinventionwith 10to 10,00ûtimesthetotalweightofthecu,,,,uu,,c~ D(a)and(e)ofwater, e.~. with 30 to 1 ,00û times the total wei3ht of the cu" ,uu"~ D.
s This formulation accordin3 to the flflh aspect of the invention may of course comprise other components and additives. Suitable and prefenred such uu~ ,uu, lal llD and additivâs are as so described l l~ "barul e with re5ard to the _u" ~uuDiliul ID, e.a. miscible materials such as solvents, anti-foam agents, stabilisers, and anti-microbials, which may be designated as components (fl.
' 10 As noted above, the fommulation may be made up in various ways, by for example (i) mixing the w" l,uu, lel ,~D (a) to (fl as appropriate to fonm the concentrate and then diluting the concentnate by mixing it with water to fomm the formulation; or (ii) mixing component (a) with an optional selection of materials from (b), (c), (d) and (fl to fomm 15 aconcentrateanddilutingtheooncentratewithwatertoformaw,,eD~ulldil,~firstdilute mixture, as appropriate mixing the Wlll,UUlltllll(S) (e) and diluting the mixture of these components with water to fomm a second dilute mixture, and/or mixing the first and second dilute mixtures to form the desired fommulation according to a 2û ffth aspect of the present invention.
Such a process for preparing the fommulation according to the fifth aspect of the present invention fomms a sixth aspect of the invention.
Accordina to a seventh aspect of the invention there is provided a dilute formulation comprising a 25 composition of the hrst aspect of the present invention with 10 to 10,ûOû times the total weight of its components of water, e.g. with 30 to 1 ,ûOO times the total wei3ht of the components of water.
This fommulation according to the seventh aspect of the present invention may be used e.g. for metal cutting fluids.
30 In an eighth aspect the present invention also provides a process of making the dilute formulation aocording to a seventh aspect of the invention. This may be effected for example by adding the components (a) and at least one of the optional other additives (b) to (d), followed by dilution with water and stirrin3 until the product is l~l l ,U~t~l ,ou~ts.
35 In a ninth aspect the present invention also provides a method of applying the formulation according to the ftf h aspect of the present invention to a substrate. CmL,ùdi, I lel Ib of this method include _ . _ _ _ _ W0 9sl2289(i r~ 5~
, . t 21~38~7 a a method of treating vegetation by applying to plants andlor soil such a formulation accordin3 ~o the invention which fommulation comprises a specific chemical agent which is an ~u, u-,i, ' ' andlor b a method of working metai which comprises applying a fommulation accordins to the 5 invention to the metal which formulation optionally comprises a specific chemical agent which is a metal corrosion inhibitor.
In~",l,o ii",u"~athe~y,uul, ' 'maybeoneormore,ul.,' ".~ ,forexamplegrovtth regulators andlor herbicides, andlor pesticides, for example insecticides, fungicides or acaricides.
10 This ~.. ,1 ,~,. l;. . -"1 of the method of applying the fonmulation according to the fourth aspect of the present invention thus includes in tum (i) a method of killing or inhibiting vegetation by applying the fommulation which comprises a specific chemical agent which is one or more phytoactives, for example grovtth regulators andlor herbicides, and 15 (ii) a method of killing or inhibiting plant pests by applying the fommulation which comprises a specific chemical agent vlhich is one or more pestiades, for example insecticides, fungicides or acancides.
In t" ,~u ii" ,~:"l b the working of the metal may include for example cutting or abrasion.
2û Examples of aulu~,lltlllli,,dl~which are t,lly~tua~ , forexample growth regulators and~or herbicides, or pesticides, for example insecticides, fungicides or acaricides. Examples of such d,u,,u.,i,~",k,dlaappropriatefortheintendeduseofthecompositionincludeana~u,lu~ ",i._dlwhich is one or more ul ,~ `Ud~.`. .'~..~, for example herbicides such as Acetochlor, Alachlor, Nicosulfuron, Primisulfuron, Prosuifocarb, Sulfosate and Trifiuralin, and also pesticides, for example insecticides 25 such as Fenitrothion and Propargite, fungicides such as Iprodione and r, U,Ui1UI Id~U'~, and i:lul u~ dl:> of the fommula R30, C(O) . CH2 . N(Z") . CH2 . P(O) . (R~)2 (a PMCM compound) in which each R30 jS selected from halogen, -NHOH, -N(R31)2, -oR32-, -SR2- and -OM, 30 where:
R3' is il~ iup~ iUI Illy selected from hydrogen, alkyl or hydroxyalkyl, preferably containing less than about 5 carbon atoms, alkenyl, preferably containing less than about 5 carbon atoms or phenyl moieties;
R32 is i" i~u~" i~ selected from hydrogen, alkyl, hydrûxyalkyl or chloroalkyl, preferably 35 containing less than about 5 carbon atoms, alkoxy, preferably containing less than about 5 carbon atoms, alkylene amine, preferably containing less than about 12 carbon atoms, phenyl or benzyl moieties;

WO 95/22896 ~ P~ ,;b95.'C J9 83~7 M is selected from hydrooen and asriculturally acceptabie salt formins moieties such as alkali metal, alkaline earth metal, stannic, ammonium, organic ammonium, alkyl sulfonium, alkyl sulfoxonium, alkyl phosphonium moieties or w, ~ , ' ID thereof; and Z" is hydrogen, an oriaanic moiety or an inoriaanic moiety.

R~,ul ~ e patents disclosing at least some of such compounds indude US Patents 3799758, 4397676, 4140513, 4315765, 3868407, 4405531, 4481026, 4414158, 4120689, 4472189,4341549 and 3948975. Re,Jlt a~7l 1 . 3 patents disclosin~ PMCM compounds wherein Z is other than hydrogen include US Patents 3888915, 3933946, 4062699, 4119430, 4322239 and 4084954.
10 In preferred PMCM compounds, Z" is hydrogen or an or5anic substituent, and/or R~ is i"d~,u~ ";iy selected from hydroi3en, alkyl, hydroxyalkyl or chloroalkyl, preferably Containinia less than about 5 carbon atoms, alkoxy, preferably containins less than about 5 carbon atoms, alkylene amine, preferably containing less than about 12 carbon atoms, phenyl or benzyl moieties;
M is selected from hydrogen snd agriculturally acceptable salt fonmin~q moieties alkali metal, 15 phosphonium moieties or w" liJil I ' ' thereof. R~u, tl~ patents disclosing at least some of such compounds include US Patents 3799758, 4397676, 4140513, 4315765, 3868407, 4405531, 4481026, 4414158, 4120689, 4472189, 4341549 and 3948975. i~,u,~ e patents disclosing PMCM compounds wherein Z" is other than hydnoiaen include US Patents 3888915, 3933946, 4062699, 4119430, 4322239 and 4084954. In preferred PMCM compounds, Z" is 20 hydroaen or an orraanic substituent. R~ .t; ~_ ori3anic substituents include methylene carboxylic; methyiene phosphonic; and methylene cyano. Rc:,ult~ aLi._ organic substituents also include carboxyl, such as fommyl, acetyl, benzoyl, perfiuoroacyl and ~l liu-,al iJUI)jl; ethylene, such as cyano, carbamoyl or carboxy substituted ethyl; and benzene sulphonyl substituents.
R~,ulù~elllaLi~c patentsdisclosinocompoundswherethenitrogencontainsthreeor~anic 25 substituents inciude US Patents 3455675, 3556762, 385353û, 3970695, 3988142, 3991095, 399604û, 4047927, 4180394, 4203756, 4261727 and 4312662. A preferred tertiary nitro3en substitutedPMCMcompound isN,N-i,i~(i l,u~,l,u,,ul,,~l,Jl)~lycine. ThosePMCMcompounds wherein Z" is hydro~qen are most preferre~ when the ,ull,' " ;'~ desired is herbicidal activity.
The above patents are herein i, ,~,u, uu, d~rJ by reference.
Illustrative of agriculturally acceptable salt-fommin3 moieties represented by M, as in OM, are the alkali metals having atomic weights of from 22 through 133, inclusive, such as sodium, potassium, or rubidium; the alkaline earth metals having atomic wei~hts of from 24 throu~h 88 inclusive, such as ma~nesium or calcium; ammonium and aliphatic ammonium, wherein the aliphatic is primary, 35 secondary, tertiary or quaternary and preferably wherein the total number of carbon atoms does not exceed more than about twelve; ~JI n~ l llùl ,kJm; trialkylsulphonium, preferably wherein the total number of carbons in the three alkyl substituents does not exceed more than about six, such W0 95122896 ~ r~ 7v.~ ~9 ' - 2183857 as trimethylsulphonium, ethyl dimethylsulphonium, propyl d~methylsulphonium and the like;
trialkylsulphoxonium, preferably wherein the total number of arbon atoms in the thnee alkyl substituent does not exceed more than about six, such as trimethylsulphoxonium, ethyl dimethylsuiphoxonium, propyl dimethylsulfoxonium and the like; I~I, ", `IJI luaul ,u"i!vm~ such as S ~c~allldll~ lua~ullullium~ ethyl llillleIl,,~vl,ua,ul,u,,i~m, propyl I,i,,,~U,~I~,I,uaui,u,,ium and the like.
In prefenred compounds, M is i, IJe,ue~ vtll ILly selected from the above-described aanculturally acceptable salt-fomming moieties and hydrogen. In more prefenred compounds, M is an alkali metal, ammonium, monoalkyl ammonium or trialkylsulphonium moiety. In most preferred 10 compounds, only one M is an alkali metal, ammonium, monoalkyl ammonium, or trialkylsulphonium moiety, while the two M's are hydrogen. F~t:,ul_ael.'~ most prefenred compounds include is~vulu,u,~ lille N-,ulluaullul,u",eU,J',u,,y.,i"e, trimethylsulphonium N-ulluaullul,u",e,Il,J's'~_i"t-and sodium sesqui-N-phosphono-rr,~II l, 'sl~ ,e. Cu, ,llvil ,cLiu, la of two or more PMCM compounds an be employed in the concentrate and processes of the present invention.
Within w, ,~:"~, aL~a and fommulations of the present invention which comprise as component (c) 2n ~yl u.,l ,~"~i~,cl, some comprise a potentiator or inhibitor of the workin3 of the ayl u-,l le:l I ,k,dl. If an aylu~.;lelllil,cl which is one or more ,ull,tvu~ v, for example arowth re3ulators or herbicides, is present, and an inhibitor aulu~l lellliwl is also present, it may typially be a phytotoxicity 20 inhibitor. Examples of suitable such materials include Safener.
Within w, ,~"l, .l~ea and fommulations of the present invention, some comprise a con osion inhibitor as component (c). Theâe may be used in a method of working metal which comprises applying a fommulation according to the invention to the metai which oomprises such a chemial agent. One 25 class of known corroâion inhibitors, suitable for practically all the relevant substrate materials which may be treated, includes straight chain or branched chain alkane arboxylic acids and water soluble salts thereof e.a. with an alkali metal cation e.g. sodium or potassium, or an " ,ulc,,,,,,u,,ivm ation. Materials of this type include in particularwater soluble ~ùlc~ IIJI ,ium salts of straight chain or bnanched chain alkane arboxylic acids which acids 30 comprise 8 to 11 arbon atoms.

r',, ~
WO9S/22896 2183857 r~l .. scl.~s The present invention is illustrated by the following Examples. All parts and percentages are by weight unless otherwise stated.
E~AMPl F 1 5 Preparation of Adjuvant C , " Ia The adjuvant r "' 1:1 shown in Tables 1 and 2 were made by adding the components in the stated amounts in a simple mixina process with stirring as appropriate. The vic-dicarboxylic 1` ~y. ", '~, ~eu~ half ester derivatiYe components in the cu"",u -i~iul l~ in Tables 1 and 2 are of fonmula (Ib): Y.O2C.(HR)C.C(HR').CO2.(CmH2mO)~.R2 (I) 10 in which:
H1 one of R and R' is C,~ strai3ht chain alkenyl and the other is hydroaen, m = 2, n = c8 4 (equivalent to a PEG 1 8û chain), and R2 jS methyl;
H2 one of R and R' is C,~ straight chain alkenyl and the other is hydrogen, m = 2, n = ca 11 (equivalent to a PEG 5ûû chain), and R2 jS methyl;
15 H3 one of R and Rl js C,~ straiaht chain alkenyl and the other is hydrogen, m = 2, n = ca 14 (equivalent to a PEG 600 chain), and R2 jS hydrogen;
H4 one of R and R' is C14 straiaht chain alkenyl and the other is hydrogen, m = 2, n = ca 14 (equivalent to a PEG 600 chain), and R2 jS hydrogen;
H5 one of R and R' is C12 straight chain alkenyl and the other is hydrogen, m = 2, n = ca 14 (equivalent to a PEG 600 chain), and R2 is hydrogen.
Table 1 Composition Number AS ¦ A2 ¦ A~.
Components wt. of Componelts (g 25Mineral oil (ex Q8) 830 - 96 Refined Rape Seed Oil - 830 H1 119 85 17.5 Calcium dude~J be~ .,esulphonate 36 Isoheptyl alcohol 15 Sorbitan monooleate - - 3.5 30n-Butanol - - 14 POIy(e~l lù~.~ ) (5) Castor oil - 85 wo gsl22896 P~ J, ~ ~
-` 218~8~7 ~able 2 Composition Number A4 ¦ A5 ¦ A6 ¦ A7 Components wt. of Com )onents ( -) ~ropylene Glycol 30 30 Preparation of Diluted Formulation; Testing of Formulation Theaboveadjuvant-,u,,,uu,iliu,,awereformulatedinto~u,,~auu,,dl,,ydilutedfommulationsby adding them to an aqueous dispersion andlor solution of a chemical agent with activity specific to the intended use of th0 w"~:~,uu, Idi"y dilute formulation, optionally with water and any other additives, and stinring to emulsify and give a homogenous fonmulation. This was effected with the parameters described above the relevant Table in each case. The method of applying and testin3 the fommulations vsried and is detailed in each case in ths relevant followin~ sub-Examples 2.
Suchfommulationsforapplicationintheuy,u-,l,~,,,-cdlindustrywhichcomprisethepresent adjuvant 1UI I IpU~ ;UI l~i have si3nificantly enhanced activity compared with ~:u" ~.uu, fommulations of which the present adjuvant composition do not form a component.
SUB-EXAMPLE 2.1 Preparation of Diluted Formulation of Fun3icide Iprodione: Testin3 of Fommulation The following Formulations F1 to F6 were made up as described above, by mixing the ~uIIluulle~
(a) dispersed chemical agent, solution in water of Rovral FLO fun3icide, (50% w/v Iprodione.
Rhone-Poulenc) 3 parts per 250 parts v~v, and (b) adjuvant~ A1 andA2, in water as set out in Table 3 below Ta ~le 3 Formulation No F1 ¦ F2 ¦ F3 ¦ F4 ¦ F5 ¦ F6 Component ~1~t.% of Cnmponent-, Rovn31 FL0 ~ ffungicide) 0.05 0.05 0.05 û.05 û.05 0.05 A1 0.05 û.1 0.2 35 A2 - - - 0.05 0.1 0.2 wo 95/22896 ~ ,5.'~ 59 21838~7 ;, ~ - 1 i3 -TEST METHOD
An in vitfo test method was used, consistina of inoculating a bean leaf on agar with Botrytis cmerea fungus, followed by applying the relevant fonmuiation. The latter step is effected by drenching a filter paper with the formulation, and then placing the paper on the leaf. The efficacy cf the 5 fonmulation is assessed by measurini~ the diameter of the fungus free zone (the Inhibition Area Diameter iAD in MM) 10 days after application of the filter paper. The test results (the means of 4 replicates) are set out in Table 4 below. Testing was carried out against ti1e controls of distilled waterandacu,,~:a,uu,,Ji,,!adilutefonnulationcontainingO.1 wt.%adjuvantcomposition,wherethe zone diameter was 0 (not shown in Table 4). Testing was also carried out against a control of a 1 û I~UI, ~alJul ,J~ dilute formulation containing o 1 wt % of the chemical sgent (included in Table 4) Formulation IAD (mm) vral FLO alone 13.00 23.00 31.75

3 4~.00 3.'5 6 4.
20 SuB-ExAMpLE 2 ~ -Preparation of Diluted Formulation of Herbicide Prosulfocarb; Testing of Formulation The following Fon~ulations F7 and F8 were made up as described above, by mixing the .U~ IUI 11:1 Ita.
(a) dispersed chemical agent, solution in water of Defi herbicide, (8û% wlv Prosulfocarb EC, 25 Zeneca Aorochem), 3 parts per 250 parts v/v, and (b) adjuvant , '.i la A7 and A4, in the proportions set out in Table 5 below.
Table 5 Formulation F7 ¦ F8 Component wlv % of Component A7 0.5 ¦ -A4 - ¦ 0.5 WO 95/22896 ~ 9 ,9 TEST METHOD
The fommulations shown in Table 5 were sprayed in a f eld trial at 250 Uha onto wheat (variety Minaret) at the 2-leaf stage infected with Echmocloa crus~alL Visual evaiuation of the weed control is performed in accordance with the EWRC scale (1 = no dama3e to 9 = 100% dama3e).
5 Testing was crmried out against an untreated control. Testing was also canried out a3ainst a control of a w" t~a~ul ~di"y fommulation containin3 only the chemical a3ent (shown in the Table).
The results are set out in Table 6 as the means of 4 replicates.
~Q~
Fonmulation Ratins (EWRC scale) 'rosulfocarb alone 5 Control No phytotoxicity was observed on the wheat.

SUB-E)~AMPLE 2.3 Preparation of Diluted Fonmulation of Herbicide Primisulfuron, Testin3 of Formulation The followins Formulations F9 and F10 were made up as described above, by mixin5 the wl I luu~ a.
20 (a) dispersed chemical a3ent, solution in water of Tell 75 WG herbicide, (75% w~v Primisulfuron, Ciba) 0.1a/l, and (b) adjuvant ., " la A5 and A6.
Ta~le 7 Fonmulation F9 ¦ F10 Component v~v % of Component A5 o1 A6 - ¦ 0.1 TEST METHOD
30 The formuiations shown in Table 7 were sprayed in a 3reenhouse trial (temperature 16 - 32C and relative humidity 65 - 95q~, at 40û l/ha onto Sorghum halepense (SORHA) and Amaranthus re~roflexus (AMARE). Testin3 was carried out a3ainst an untreated control. Testing was also canried out against a oontrol of a cu"t~auul ~di"y fonmulation containin3 only the chemical ayent.
Visual evaluation of the weed control is performed 7, 14 and 28 days after treatment. Weed 35 control was evaluated as the percenta3e of dead plants as compared with an untreated control.
The results are set out in Table 8 as the means of 6 replir;ates.

WO 9S/2289G 2 1 8 3 8 5 7 r~ ~

Formulation A ,l % C ntrol (days) SO lRA AM ~RE
Primisulfuron alone 7 14 ' 2 10 SUB EXAMPLE 2.4 - -Preparation of Diluted Fonmulation of Herbicide Nicosulfuron, Testing of Formulation The followins Fonmulations F11 to F13 were made up as described above, by mixing the wl I luul ~ a.
(a) dispersed chemical agent, solution in water of Nicosulforon SC herbicide, (10% w/v Nicosulfuron SC, Zeneca A~, u.,l ,t", I;..dl~) 0.125 %v/v, and (b) adjuvant w,- ,uusiliu, la A5, A6 and A7, in the proportions set out in Table 9 below.
Table 9 Fommulation F11 ¦ F12 ¦ F13 Component vlv%of Compnnent A 0.1 Afi - 0.1 A- - - 0.1 The formulations shown in Table 9 were sprayed in a ~reenhouse trial (temperature 16 - 32C and relative humidity 65 - 95~, at 400 I/ha onto Sorghum hale,oensQ (SORHA) and Amaranthus ret~tle~us (AMARE). Testing was carried out a3ainst an untreated control. Testing was also carried out against a control of a w, ,t:~uu"~li, ,u formulation containing only the chemica' a~ent.
30 Visual evaluation of the weed r,ontrol is perfonmed 7, 14 and 28 days after treatmenS and the weed control (% control) is assessed as the percentage dead plants compared with an untreated control.
The results are set out in Table 10 as the means of 6 replicates.

Wo 95/22896 21838~7 Table 10 Fommulation A. sr,~ . ,L % Cnntrol (days) SOHRA AMARE
Nicosulfuron alone 7 0 0

4 10 20 -'8 1 5 70 F11 t O O

1~ 20 30 2~ 25 75 F13 '' 0 0 SUB-EXAMPLE 2.5 Preparation of Diluted Fommulation of Herbicide Trimethylsulphonium Glyphosate, Testin3 of Formulation The following Fomnulations F14 to F17 were mede up as described above, by mixin3 the 20 Cu~ Jul l~l lLa (a) dispersed chemical agent, solution in water of Sulfosate herbicide, (70% wlw Trimethylsulphonium Glyphosate~) 0.5 %v/v, and (b) adjuvant ~;u"~u~ u":. A4, A5, A6, and A7.
Table 1 1 Fommulation F14 ¦ F15 ¦ F16 ¦ F17 Component vlv % of Component A4 0.15 A5 - 0.15 A6 - - 0.15 30A7 - - - 0.15 .
TEST METHOD
The formulations shown in Table 11 were sprayed in a 3reenhouse trial (temperature 16 - 32C
and relative humidity 65 - 95%, at 400 llha onto Agropyron nepens (AGRRE), Poa annua (POAAN) 35 and Amananthus retrr~flexus (AMARE). Testin3 was carried out against an untreated control.
Testing was also carried out aoainst a control of a uu~ uul .d;l ~u fommulation containing only the ... .

Wo 95/22896 P~ , S~
21838~7 chemical a~ent. Visual evaluation of the weed r,ontrol is perforrned 7, 14 and 28 days after treatment. Weed control (% control) was assessed as the percenta~e dead plants compared with an untreated r,ontrol. The results are s2t out in Table 12 as the means of 6 replicates.
Table 1 Fommulation As~.~s~.".~,., % Contro (days) AGRRE POMN Al\/ ~RE
.S~ ~'' 7 0 o ~:~
14 ~0 45 28 ~5 70 9 14 0 75 ! 9 1~ 90 95 100 2F~ 100 100 100 ~ .
35 ~

Claims (14)

Claims

1 According to a first aspect of the invention there is provided a composition which comprises:
(a) at least one surfactant vic-dicarboxylic acid polyalkyleneoxy half ester derivative of the formula (I) or (II):
Y.A1.OC.(HR)C.C(HR1).CO.A.(CmH2mO)n.R2 (I) where one of R and R1 is C6to C22 alkenyl or alkyl and the other is hydrogen;
A is -O- or -NR4-; where R4 is hydrogen or C1 to C6 alkyl;
n is 2 to 100 (and as it is an avenage it may be non-integral);
m is 2 or 3 (and may vary along the polyoxyalkylene chain);
R2 is hydrogen or C1 to C16 alkyl;
A1 is -O-, -O? or -NR4- where R4 is hydrogen or C1 to C6 alkyl;
such that when A1 is -O?: Y is a cation; and when A1 is -O- or -NR4-: Y is a C1 to C6 alkyl group (R3) or a group of the formula (CmH2mO)n.R2 where m, n and R2 are independently as defined above;
or Y.A1.OC.(HR)C.C(HR1).CO.A.(CmH2mO)n.CpH2p.A.CO.(HR1)C.C(HR)CO.A1.Y (II) where:
n, m and each R, R1, A, A1 and Y are independently as defined above; and p is 2 or 3, and at least one of (b) at least one other surfactant, (c) at least one oil component, and (d) at least one organic solvent.

2 An adjuvant composition as claimed in claim 1 comprising (a) at least one vic-dicarboxylic acid polyalkyleneoxy half ester derivative as defined in claim 1, present as 1 to 90 wt. % of the total composition; and at least one of:(b) at least one other surfactant, present as 0 to 90 wt.% of the total of the total composition;
(c) at least one oil component, present as 0 to 99 of the total composition; and/or (d) at least one organic solvent, present as 0 to 90 wt.% of the total composition.

3 A composition as claimed in either claim 1 or claim 2 wherein the compound of the formula (I) or (II) is at least one compound of the formula (Ia) or (IIa):
(Ia) and (IIa):
R1-CH(CO.AY)-CH2CO.AZ (Ia) in which Z is a group of formula (CmH2mO)nR2 in which n, m and R2 are as defined for Formula (I) above with n preferably being 3 to 50;
R2 is hydrogen or an alkyl group having 1 to 16;
A and A1 are each independently -O-, -O? or -NH- groups, when A or A1 is -O? the respective Y is a cation for example H+ or an alkali metal ion, when A or A1 is -O- or -NH- the respective Y is a group R2 or (CmH2mO)nR2 where m and R2 are as defined above and may be the same or different to the group Z, R1 is an alkyl or alkenyl group having 6 to 22 and preferably 13 to 20 carbon atoms, or of formula (IIa):
R1-CH(COA1Y)-CH2-CO.A-D-A.OC-CH2-CH(COA1Y)-R1 (IIa) in which D is a group of formula (CmH2mO)nCpH2p-in which p is 2 or 3; and R1, A, A1, m and n are as defined above.

4 A composition as claimed in any one of claims 1 to 3 which includes at least one other surfactant which is or includes at least one of:
an anionic surfactant selected from surfactants of the alkarene sulphonate salt group; the poly(arylarylalkoxylate) phosphate or sulphate salt group; the alkaryl phosphate or sulphate salt group; the straight chain or branched alkyl- and alkoxylated alkyl phosphate or sulphate salt group; the fatty acid salt group, having 8 to 24 carbon atoms; and/or the group of salts of alkoxylated carboxylated alkaryl and fatty alcohols, in which the salt cation is an alkali metal; an alkaline earth metal; and/or ammonium, aliphatic ammonium or alkanol-ammonium cation, wherein the aliphatic or alkanol moieties are alkyl having 1 to 4 carbon atoms; or a mixture thereof;
a cationic surfactant selected from alkoxylated fatty amine salts having 8 to 24 carbon atoms, and in particular 12 to 18 carbon atoms; and/or non-ionic surfactants of the formula:
R21.O(X)R22 and/or R24OR25 and/or R26-N(-XH)2 in which:
R21 is an alkyl group or alkenyl group containing up to 24 carbon atoms, an alkyl phenol group having 6 to 12 carbon atoms in its alkyl group, a sorbitan group, or a group of formula R26CO in which R26 is an alkyl group having 11 to 22 carbon atoms;
R22 is hydrogen or an alkyl group, a carboxyalkyl group having 2 to 4 carbon atoms, or a fatty acid residue having 10 to 22 carbon atoms; and R22 is hydrogen or an alkyl group, a carboxyalkyl group having 2 to 4 carbon atoms, or a fatty acid residue having 10 to 22 carbon atoms; and X is a polyalkylene oxide group containing an average of 2 to 40 alkylene oxide groups or mixed alkylene oxide groups;
R23 is a sorbitan group;
R24 is a fatty acid residue having 10 to 22 carbon atoms; and R25 is an alkyl or alkenyl group having 10 to 22 carbon atoms.

A composition as claimed in any one of claims 1 to 4 which includes at least one oil component having a boiling point of over 200°C at atmospheric pressure and a melting point not higher than 60°C and selected from mineral oils; optionally hydrogenated vegetable oils;
a C1 to 5 ester of a C8 to 22 fatty acid; and mixtures thereof.

6 A composition as claimed in any one of claims 1 to 5 which includes at least one water soluble or miscible organic solvent selected from alcohols and glycols.

7 An adjuvant composition as claimed in any one of claims 1 to 6 comprising:
(a) at least one vic-dicarboxylic acid polyalkyleneoxy half ester derivative of the formula (I) or (II) as defined in claim 1, present as 5 to 90 wt.% of the total composition; and (b) (i) at least one non-ionic surfactant present as 0 to 90 wt.% of the total; and/or (ii) at least one anionic surfactant present as 0 to 60 wt.% of the total; and/or (c) at least one oil component present as 0 to 97 wt.% of the total.

8 A dispersible and or soluble concentrate which comprises:
(a) at least one surfactant vic-dicarboxylic acid polyalkyleneoxy half ester derivative of the formula (I) or (II); and (e) at least one chemical agent with activity specific to the intended use of the concentrate or corresponding dilute formulation.

9 A concentrate as claimed in claim 8 in which the chemical agent with activity specific to the intended use is one ore more compounds selected from growth regulators, herbicides and pesticides.

A concentrate as claimed in claim 8 in which the chemical agent is or includes one or more PMCM compounds

11 A concentrate as claimed in claim 8 in which the chemical agent with activity specific to the intended use is a metal corrosion inhibitor.

12 A dilute formulation which comprises a composition as claimed in any one of claims 1 to 7 or a concentrate as claimed in any one of claims 8 to 11 dispersed in from 10 to 10000 times the total weight of its components of water.

13 A method of treating vegetation which comprises applying to plants a concentrate as claimed in either claim 9 or claim 10 which has been dispersed in from 10 to 10000 times the total weight of its components of water.

14 A method of working metal which comprises applying to plants a concentrate as claimed in claim 11 which has been dispersed in from 10 to 10000 times the total weight of its components of water.