CA2183858A1 - Emulsifier compositions - Google Patents

Abstract

Emulsifier 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.A.1.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 other surfactant are effective in emulsifying materials such as agrochemicals to give stable emulsions. The emulsifier can also be formed as a concentrate that can contain a specifically effective chemical and typically an organic liquid or solvent so that the concentrate forms an emulsion directly on dilution with water.

Description

~ W0 95122897 2 ~ o 3 ~ 5 8 ~ . ,u E'"ll ~IFIER COMPOSITIONS
This invention relates to emulsifier w" ,,uu ,iliu, l~, and in particular to , " ,~, which contain a plurality of surfactants; to emulsifiable Wll~lltlc~d~, which are readily emulsifisble into water, 5 comprising the emulsifier composrtion, in particular w"~"~, dt~ with a high loading of a chemical aûent with activity specific to the intended use of the w, ",~ ,ct~" to diluted fommulations comprising the concentrate; and to processes for preparing or using the emulsmer , ' Ia, the w, ,~, ,t,ct~,:,, and the diluted formulations comprising the oomposition.
10 Emuisifier , " ,~ with a plurality of surfactants are known in general in the cu,u~
industry; these may be used to fomm w, ~.UI ,~, cLels comprising a chemical agent with activity specific to the intended use of the concentrate, and such cUIl~l~lldl~ are readily emulsifiable on conversion to a diluted formulation. However, the efficacy of such emulsrfier , " ,~ as an emulsifier and the extent to ~vhich the resultant w" ,uu~ ":, are readily emulsifiable into water to 15 a diluted fommulation is usually limited to a specific combination of a dispersed chemical a3ent and readily emulsifiable surfactant w,, ,,uu, ,~"t~.
We have developed a class of vic-dicarboxylic acid r l~ OAy half ester derivatives as described in published PCT Application No WO 94/û0508 A (PCT/GB 93/û1335). This invention 20 relates to applications of compounds of this general type of the fommula (I) or (Il) below Y.A'.OC.(HR)C.C(HRI).CO.A(CmH2mO)n.R2 (1) where one of R and R~ is C~ to C22 alkenyl or alkyl and the other is hydro3en;
A is -O- or -NR~-; where R~ is hydrogen or C, to C~ alkyl, particulariy methyl or ethyl;
25 n is 2 to 100 (and as it is an average it may be non-integral);
m is 2 or 3 (and may vary along the U-2~UA/ . ", lcne chain);
R2 is hydrogen or C1 to C,~, particularly C, to C~ alkyl;
A' is -O-, -O or -NR4- where R~ is hydrogen or C, to C~ alkyl, particularly methyl or ethyl;
such that when A' is -0: Y is a cation, particularly H, and alkali metal cation especially a 30 sodium or potassium cation. or an ammonium ion (especially NH4~, an amine ammonium or an " lùlc" ,i, le~ ammonium ion); and when A' is -O- or -NR4-: Y is a C1 to C~ alkyl group (R3) or a group of the fommula (CmH2mO)n.R2 where m, n and R2 are i~ u~"~ , as defined above;
or 35 Y.A1.0C.(HR)C.C(HR').CO.A(CnH2mO)n.CpH2p.A.CO.(HR')C.C(HR)CO.A'.Y (Il) where: n, m and each R, R~, A, A' and Y are inde~u~:"~"~ly as defined above; and p is 2 or 3.

Wo95122897 2 1 838 ~8 2 - ~ lu As descnbed in WO 94/00508 A, the free acid fonms of compounds of the fommulae (I) and (Il) in are defined with Y as 8 Ht cation including both the ionised and non-ionised fomm of the free acids.
Compounds of the fomnulae (ll or (Il) are typically miAtures of isomers Wll~.lUll~.iillU to the two senses of the snhydnde ring opening reaction typically used in their synthesis- The alk(enhl 5 chain seems to have a minor steric effect on the isomer ratio (typically about 60:40), the major isomer arising from nucleophilic attack at the anhydride carbonyl group remote from the alk(en)yl group. Thus in particular the compounds of the fommulae (I) and (Il) include those of the fonmulae (la) and (lla):
R' - CH(CO.AY) - CHz CO.AZ (la) 10 in which Z is a group of fonmula (CmH2mO)nR2 in which n, m and R2 are as defined for Fommula (I) aboYe with n preferably being 3 to 50;
R2 j5 hydro~en or an alkyl group having 1 to 16 and preferably1 to 6 carbon atoms;
A and A' are each i"d~y~ -O-, -O- or -NH- groups, 5 when A or A' is -O- the respective Y is a cation for example H+ or an alkali metal ion, when A or A' is -O- 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, or of fommula (lla):
20 R' - CH(COA'Y) - CH2-CO.A - D - A.OC - CH2 - CH(COA'Y) - R' (lla) in which D is a group of fommula (CmH2mO)n CDH2p -in which p is 2 or 3; and R', A, A', m and n are as defined above for formula (la).
25 Various uses of compounds of this general type are described in WO 94/0û~û8 A, including as emulsifying agents for acrylamide invert ,uu'~ , i " systems and as wool scouring agents. We haveno~vfoundthatsuchcompoundsareusefulinemulsifierw,,,, ' ,:,withapluralityof surfactants, which may be used to form w,~"~ . comprising a chemical agent with activity specific to the intended use of the concentrate, and which w, ~ , are readily emulsifiable 30 into water. These emulsions are useful in general in the a_l uul I ' ' industry, such as in fommulations which comprise a chemical agent which is known in the au, u-J I ' industry to have an activity appropriate for use in weed, fungus or insect control.
According to a first aspect of the invention there is provided a composition which comprises 35 (a) at least one surfactant vic dicarboAylic acid l: 'y. "~ ùAy half ester denvative of the formula (I) or (Il) as defined above; and (b) at least one other surfactant.

~ W095122897 2 1 ~3858 ~ u Particularly suitable emulsiher ~ of this first aspect are those uomprisin~q (a) at least one compound of the fommula (I) or (Il) above, present as 5 to 90 wt.% of the total composition, preferably as 10 to 75 wt.~6; and (b) at least one other surfactant, present as 10 to 90 wt.% of the total, preferably as 10 to 70 5 wt.%.
The balanue of the uomposition may be a water miscible liquid and/or water imiscible, e.g. orsanic, liquid. This may be desirable if the viscosity of the uomposition would othenwise be i"w".
hi5h. The uomponents and their proportions are preferably chosen such that where any 10 components are readily available only as aqueous solutions the composition provided by mixing the composition uu~ uu, ~t:"~a iS stable, l l ' la~al Idil l~ the water which is thereby introduued.
The uomposition often employs a half-ester derivative containing anionic groups and/or in particular sroups ionisable to anion. Preferred such ester derivatives are generally as set out in 15 WO 94/00508 A, but preferred surfactants of this type include mono- and di-ester derivatives within fommula (I) or (Il) respectively in which the alk(en)yl substituent on the succinic moiety preferably has 8 to 20 carbon atoms. This is particularly the case in the dUI U~l I ' ' industry when used to form an emulsrFiable concentrate comprising a chemical agent with activity specific to the intended use of the concentrate. Particuiar ester derivatives of this type include those in 20 which the alk(en)yl substituent has 10 to 17, preferably 12 to 14 carbon atoms, and especially where it is an alkenyl ~qroup. Prefenred such vic-dicarboxylic acid uu~j 'h~"aoA~ half ester derivatives also include those in which Z (in fommula (la)) is an alkylene oxide (block) (co-)polymer of fommula (CmH2mO)nR2 as def ned in which n is preferably 7 to 13 and m is 2 andlor 3. As desuibed in WO 94/00508 A, the alk(en)yl groups in the surfactants of the fonmula (I) or (Il) used 25 in this invention are desirably linear alk(en)yl groups.
The other surfactant(s) may be any which on usin~ the emulsifier composition in the fommulation of a concentrate comprising a chemical agent with activity specr~ic to the intended use of the uoncentrate, will sive a concentrate which:
30 (a) is stable and I ,u" luue"eu.ls for at least 24 hr. after makin~ up; and (b) remains homooenous on dilution with water to a diluted fommulation.
The other surfactants which are suitable for such stability in use and storage of the concentrate may be anionic, cationic, amphoteric or non-ionic surfactants, or mixtures thereof. Suitable 35 anionic surfactants include members of the alkarene sulphonate salt group, such as alkyl benzene sulphonate salts having 6 to 16 carbon atoms in its straisht chain or branched chain alkyl group, e.s. wherein the alkyl is lauryl (dodecyl), or mixtures thereof; members of the poly(arylaryl-WO 95/22897 . ~,1,. ' Iu

2 1 ~3858 ~ --alkoxylate) phosphate or sulphate salt group; members of the alkaryl phosphate or sulphate salt group; members of the straight chain or branched alkyl- and alkoxylated alkyl phosphate or sulphate salt group; and membens of the fatty aàd salt group, having 8 to 24, preferably 12 to 18, carbon atoms, e g. Iaurate, I lelJ~elde~l lud~e, l~e,u~ud~l enuaLe, stearate and oleate; and members 5 of the ~roup of salts of alkoxylated w, bUA~ !_W alkaryl and fatty alaohols, the latter including e.g.
.Yk,. ~e OXide)C12 b ~5 aIaOhOI IrIe~ UA~ Examples of suitable salts include those with an alkali metal cation e.g. sodium or potassium; an alkaline earth metal, e.L3. calcium; and ammonium, aliphatic ammonium " ,u'.~. "- "u"iu" . cation, wherein the aliphatic or alkanol moieties are e.g. straight chain or branched alkyl having 1 to 4 carbon atoms; and mixtures 1 û thereof.
Inparticularwhentheaompositionisusedintheay,u~l,t,,,,iwlindustrytofommanemulsifiable conoentrate comprising an ~u, u~ el "iwl agent with activity specLfic to the intended use of the concentrate, prefen ed component (b) anionic surfactants include ~ el l~el ,t, sulphonate salts 15 having 6 to 16 carbon atoms in their strai~ht chain or branched alkyl group, e.g. wherein the alkyl is lauryl. Preferred salts include the calcium salt.
Suitable cationic surfactants include alkoxylated fatty amine salts having 8 to 24, preferably containing more than 12 carbon atoms, and in partiaular 12 to 18 carbon atoms, the latter 2û including e.g. poly(ethylene oxide) C,zb,5 amine salts, e.~. chloride salts.
Non-ionic surfactants are particularly useful in Wl l~ lLl d~ which are readily emulsihable in particularinau,u-,l,t,,,,i-,dlw,,~e,,~,dL~. Theseincludenon-ionicsurfactantsusedinthe ~u~ uul ,~",i~al industry to fomm emulsifiables, in particular those of the formulae:
R2l.0(X)RZ' andlor R2'- N (-XH)2 in vJhich R2' is an alkyl group or alkenyl group which suitably contains up to 24, preferably 6 to 21, and especially 9 to 18 carbon atoms, an alkyl phenol group having 6 to 12 carbon atoms in its alkyl group, a sorbitan group or a group of formula R"C0 in which R2' is an alkyl group 3û haviny 11 to 22 carbon atoms;
Rn is hydnogen or an alkyl group, a w, UUA; "<~,1 group, e.g. Udl L , _"<~,l having 2 to 4 carbon atoms, or a fatty acid residue having 10 to 22 carbon atoms;
X is a r 1~ !k, ' ,~ oxide group containin3 an average of 2 to 40, preferably from 2 to 13, and especially from 2 to 10 alkylene oxide groups or mixed alkylene oxide groups; and 35 R2' is an alkyl or alkenyl group having 10 to 22 carbon atoms.

~ W095/22897 2 1 8 3 ~ ~ 8 ~ u r Aamples of suitabie ~roups R2' include e.s. sorbitan and :auryl, heptadecyl, I~ J~ad~:l.,~l, h-~ , stearyl and oleyl. -xamples of suitable sroups R22 include e.3. carboxy-rnethyl, ~thyl or -propyl, or a salt thereof; and laurate, I ,~:,u~c,d~ c"u~ ,uic.~ u.. ~., luc~el, stearate or oleate. i xamples of suitable X include, '~ ~l "<y!~.. ,e or5 mixed alkylene oxide) groups, wherein the alkylene ~roups each have 2 to 8, preferably 2 to 4, e.g. 2 or 3 carbon atoms, and, when R2' is sorbitan, and R22 is fatty acid residue havin3 1û to 22 carbon atoms, a direct bond.
r~xamples of suitable non-ionic surfactants thus include i~û'y~ ,1) fatty acids and alcohols 10 having 8 to 24, preferably 12 to 18 carbon atoms in their fatty acid or alcohol Sroups;
') alkaryl alcohols havins 8 to 24, preferably 12 to 18 carbon atoms;
') ~ " , !L'~,~) sorbitan and sorbitol esters; poly(; " , '_:~.1) tri~lycerides, including e.g.
'~ I) vegetable oils, such as poly(ethoxylated) linseed oil, mustard oil, neem oil, niger seed oil, oiticica oil, palm oil, palm kernel oil, peanut oil, perilla oil, poppy seed oil, safllower oil, 15 sesame oil, or (especially) soybean oil; poly(alkoxylated) allyl alcohols; poly(alkoxylated) poly(arylaryl alcohols); and poly(~ ,"~, oxides) including (block) (co-)polymers; in particular those wherein the alkylene ~roups each have 2 to 4 carbon atoms; and sorbitan esters with up to 3û carbon atoms, such as sorbitan monooleate.
2û Within prefenred emulsifier w, I, ~s of the first aspect of the present invention, especially when used for fonmulations for application in the au,u,.i ' industry, the component (b) (at least one other surfactant) is at least one non-ionic surfactant, and optionally ii at least one anionic surfactant.
Prefenred component (b) non-ionic surfactants then include those of the formula: R210(X)R22 and/or R2' - N (-XH)2 as defined above which are indicated as prefenred non-ionic surfactants l ~ ru~ts.
3û Prefen-ed component (b) anionic surfactants then include ~ sulphonate salts having 6 to 16 carbon atoms in their straight chain or branched alkyl oroup, e.g. wherein the alkyl is lauryl.
Preferred salts include the calcium salt.
Preferred emulsiher wlll,uuai~iul ,:, of this first aspect are those comprisin~
35 a at least one vic-dicarboxylic acid I ') . 'ky~,, leOAy half ester derivative, present as S to 9û
wt.% of the total concentrate, preferably as 1û to 75 wt.%; and WO 95/22897 2 1 8 3 8 5 8 ~ u b i at least one non-ionic surfadant, present as 10 to 90 v~t.% of the total, preferably as 10 to 50 wt.%, e.g. 10 to 40 wt.%, in particular 10 to 35 wt.%; and ii optionally at least one anionic surfactant present as 0 to 60 wt.% of the total composition, preferably as 0 to 40 wt.%, e.g. 15 to 40 wt.%, in particular as 25 to 40 wt % of the total.
One class of such emulsifier , ' ,~ is of those compnsing 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. Examples of suitable water miscible liquids which may 10 fomm the balance of the composition and which may be desirable if the viscosity of the composition would otherwise be i,,.,u,,~. Iiel1, high include alcohols, including glycols, e.g. with straight chain or branched alkyl having 1 to 8 carbon atom, such as isobutanol and propylene glycol. Such liquid may often contain water, which is thereby introduced into the composition, and may be present as up to 3 wt.% of the total.
Examples of suitabie water imiscible liquids which may form part of the balance of the composition and which may be desirable if the viscosity of the composition would other~vise be i,~cul, . _. Iiel 1;'~' high include 1 ,~l u~.al L~ul 1~, preferably those having 5 to 18 carbon atoms, including aromatic l.,llu-,a,L,u,,:,,straightchainorbranchedalcohols;optionallyl,~d,vut:,,dtedvegetableoils,such 20 as an optionally ~.ydl uuel laLed cotton seed oil, linseed oil, mustard oil, neem oil, niger seed oil, oiticica oil, olive oil, palm oil, palm kernel oil, peanut oil, perilla oil, poppy seed oil, rape seed oil, saf~lower oil, sesama oil, or soybean oil; esters (especially a C1-6 ester) of a C8-Z fa~ty acid, especially a C12-18 fatty acid, e.g. members of the group comprising methyl laurate, uLadaCal lua~e, l~euLa~e~,el lUa~ . IUC~, stearate or oleate, in particular methyl 25 laurate and oleate; N-l1 le~l 1) 'IJ, .1 l " ' le, and iSuual a~ril la, or a mixture thereof. Preferred such liquidmaterialswhichmaybeusedincludexylene,anymixtureofaromaticll,~, u~alLu~1:,, and N~ U1~ a~
According to a second aspect of the invention there is provided an emulsinable concentrate 30 compnsins the emulsifier composition of the first sspect; snd (c) st least one chemical agent with activity specific to the intended use of the concentrate.
Such chemical agent specific to the intended use of the concentrate may be for example an a~lul,l I ' or a metal corrosion inhibitor.
35Ifan a~lu~91elllil.àlis presentitistypicallyoneormore~ la~2;a~ forexsmplegrowth re~ulators or herbicides, snd/or pesticides, for exsmple insecticides, fungicides or scaricides.
Such Gul luel ILI a~eS may comprise a second chemical sgent vihich will give 8 concentrate in which wo ssn2ss7 ~ . /U

the activity of the first chemiQI agent is made more specific to or selective in the intended use of the concentrate or w" ea,uul Idil ~y dilute formulation. Such W~WI Itl ate ~ typiQlly include e.g.
w, ,u:, Itl dtaa in which the first chemical a~ent is an ayl u~,l ' which is one or more ~JI 1, . , for example ~rowth regulators or herbicides, and/or pesticides, for example 5 insecticides, funsicides or aQricides, and the second is a ~JI i,: ' ~ inhibitor to regulate any , for example growth regulation or herbicidal actiYity of the conoentrate or w~ u~ ,.li, Iy dilute fonmulation, or e.3. Safener inhibitor to make it more selective, e.g. as between graminious and broad leaved species. Such a second chemiQI asent may be present as up to 15 wt.% of the total conoentrate.
Preferred w, I~.el ~ aiaa are those with a high loading of the chemiQI agent with activity specific and appnopriate for the intended use of the composition. These exhibit dispersion even of specihc chemical agents, such as ~icetochlor and Alachlor herbicides but also pesticides, such as insecticides, funsicides or acaricides, which are known in the ~u' u..~ ,cll industry as not usually 15 readily emulsified.
Prefenred emulsifiable w, luel Itl d~e:~ of this hrst aspect are those comprising (a) at least one vic-diQrboxylic acid ~ ') 'h, ~ UA; half ester derivative, present as 0.1 to 15 wt.% of the total conoentrate, preferably as 0.15 to 10 wt.%;
20 (b) at least one other surfactant, present as 1 to 25 wt.% of the total; and (c) at least one chemical agent with activity specific to the intended use of the concentrate, present as 2.5 to 95 wt.% of the total, preferably as 10 to 50 wt.%.
The greater part of the balance of the concentnate may be a water miscible liquid and/or water 25 insoluble organic solvent, to aid the dissolution of the chemiQI agent with activity specific to the intended use of the concentrate om,ul, a:,~uul Idil 1 ~ dilute fonmulation. It may also be desirable U the viscosity of the conoentrate would otherwise be i"..u" :,,, liel IIIy high. The conoentrate, in particular when used in fommulations for appliQtion in the ayl uul, ' industry, may comprise one or more such liquid and/or solvent w,,,~,u, lel ,t~ as 0 to 97, and in partlcular as 5 to 90 wt.% of the total 30 concentrate. In some intended uses of the w, ,~"~, clIe~, e.g. in methods of applyin3 tu, . ~' " ;D
of some srowth regulators, herbicides, insecticides, tungicides or aQricides, it is prefenred that the concentrate has a significant water content, e.g. over 25 wt.% of the total. Such w, I~,el ,~ dL~a are in fact w, ,vc, ,~, d~e l emulsions which are further emulsifiable on being diluted with water to give fommulations for applyiny e.y over crops. The w~ u~ lel ,~, and their proportions are preferably 35 chosen such that the concentrate provided by mixiny the concentrate components is stable, r ' ::: lalal Idil Iy the water which is thereby introduced. When the concentnate is a w~ ",~:"I~ a id.l emulsion intended e.g. for use in the aul u~,l I ' ' industry to give fommulations for applying over WO 95/22897 2 1 8 3 8 5 8 r ~ u ~

crops, certain emulsrFlable "u, ,u~ LI dt~ 2re those in which the components and their proportions are:
(a) at lesst one vic-dicarboxylic acid I ') ", ~,"euA~ half ester derivative, present as û.1 to 15 wt.% of the total concentrate, preferably as û.2 to 10 wt.%;
5 (b) at least one non-ionic surfactant component as 1 to 25 wt.% of the total emulsiflable concentrate; and (c) no anionic surfactant.
Each of the present .,u, ,~"~, dttà
1û a exhibits dispersion even of specific chemical a3ents, such as Acetochlor and Alachlor herbicides but also pesticides, such as insecticides, fungiades or acariddes, which are knowninthe~u,u.,l,u,,,i,,dlindustryasnotusuallyreadilyemulsifiedbyknownsurfactants, b remains a homosenous concentrate on dilution with water to make the concentrate into a diluted fommulation of the present invention for application of the component (c) of the 15 concentrate, without the need for the addition of any further materials to disperse the phase and prevent settling of the phase from the diluted ~,u, ,-,~" ,t~ d~e, c exhibit excellent wetting properties in relation to the dispersed chemical agent in the concentrate herein described, and in particular in relation to treated substrates.
2û Preferred , " la of the present invention, especially when used for cu, ",~"t, elLda and fommulations Of clUI ud " ~ ,dla, enable a hi~3h loadin3 even of the agents referred to in (a) above, for example herbicides such as Acetochlor and Alachlor Suitable and preferred vic-dicarboxylic acid p~l~ lky,c.l~uA~ half~ster derivatives and other surfactants in the concentrate are generally those so described l~ lL,~u, ~: with regard to the emulsiher -,u" ,uu:.;Liu"a of the first aspect of 25 the invention.
Examples of suitable water miscible liquids include alcohols, includin~ ûlycols, e e.g. with straight dhain or branched alkyl having 1 to 8 carbon atoms. Preferred examples include isobutanol and propylene glycol. Such liquid may often contain water.
3û
EAamples of suitable water insoluble organic solvents which may fomm part of the balance of the concentrate include l ', ~ UUdl ùu, la, preferably those having 5 to 18 carbon atoms, includin6 aromatic h~ ~, u~, L,u, la, straight chain or brandhed alcohols; optionally ~ u~ eJ vegetable oils, such as an optionally h~ ~l u~ dL~ld cotton seed oil, linseed oil, mustard oil, neem oil, niger 35 seed oil, oiticica oil, olive oil, palm oil, palm kemel oil, peanut oil, perilla oil, poppy seed oil, rape seed oil, safflower oil, sesame oil, or soybean oil; esters (especially a Cl ,0, ester) of a C~,022 fatty acid,especiallyaC,2,0,~fattyacid,e.g.membersofthegroupcomprisingmethyllaurate, ~W09~122897 21 83=858 ~ u g -~, I,e~"a.le.,enu~t~ ud~e, stearateoroieate, inparticularmethyl laurate and oleate; N-n ,e~ "~ , and i;,u,uc", ~~ ,a, or a mixture thereof. Prefenred such solventmaterialswhichmaybeusedincludexylene,anymixtureofaromaticl,~lu~,L,u"~,and An anti-foam agent may be present. A sufficient quantity to provide an anti-foamin3 eflect for the intended use of the concentrate without separatins out is desinable. Nommally û.05 to 10% and prefenably 0.2 to 6% by weight of the total is suitable. Any compounds may be used which are w,,. ., 'iy useful as anti-foam agents in aqueous fonmulations with a hi3h dispersed phase 10 content. The antifoamin3 a3ent(s) is/are preferably one or more u.,'~ ' ,es, especially of the type havin3 hydrophilic 3roups. It is preferably of fommula R~3 SiO [SiO R' R~lnSi R~3 in which the 3roups R~ are individually alkyl groups, preferably havin3 1 to 3 carbons atoms and are 15 preferably methyl 3roups, one or more of the qroups R may be residues of polyalkylene 31ycols and the others are as defined for R~.
The groups R~ preferably have a molecular wei~ht in the range 1000 tû 20000 and especially 5000 to 15000. Examples of suitable, '~ ' ,e antifoams are disclosed in British Patents 1533610 and 1 554736.
Other possible additives in the emulsifiable w, ,w, ", ~te:~ to which this invention relates include non-surfactant materials which are ,,u, . .~. ,Liu, ,~''y useful in surfactant fommulations as viscosity modifiers, stabilisers, and anti-microbials. One class of known viscosity modifier materials of this type includes one or more uullllllel-,i~:'y available water soluble or miscible materials such as 25 sums, e.3. xanthan gums, and cellulosics, e.g. carboxy-methyl, ethyl or propylcellulose. These are oftenpresent,whenusede.g. in~,,u-,l,c,,,iudlfommulationsinparticularas001 to1 v~t.%ofthe total w~ I~,el ,L, The present emulsifier concentnate may have a pH value within a range of for example 5 (acid) to 30 9 (alkaline), for example 6 to 8.
The emulsi~lable ~, ,~,c, ,~, clLea to which this invention relates may be produced by Wl l .'~,. l'' ~CI
mixin3ofthew,,,,uu,,_.,tainanyorderusedcu,,~.,~
.

35 In a third aspect the present invention thus provides a process of makin3 the concentrate by mixin3 the 1UII IUUI lel ILa together. This may be effected for example by addin~ the components (a), wo g5/22897 2 1 8 3 8 ~ 8 (b) and (c), and any other components e.g. solvents and/or any other additives, and stirrin6 until the product is llul--vuelleOUs.
For emulsifiable w, I~,el ,t, aLas to which this invention relates which are w, 11~1 ,L, d~a~ emulsions, 5 mixing the components in a speciflc order may be necessary. Such emuisifiable ~,u, I~,el ,L, dlea may have to be produced by separate cu~ . " lal mixins of a the components of the vehicle liquid, and b the components (a), (b) and (c) and any other components, respectively, to sive two separate liquid phases, with stirrins until each product is homoseneous.
10 The concentrate is made by careful dispersion of the phase containin3 the components (a), (b) and (c) in to the other phase. It is may be desirable that this is effected for example by addin~ the phases at moderately elevated temperatures with high shear mixing to deal with the il ,w, 1. ~, liel ,t'~
hish viscosity of the concentrate which is thereby introduced. The product w"~ "LI aled emulsion is subsequently left to cool to ambient temperature.
In most applications, the surfactant l,u, 1~1~1~ cl1ea of the second aspect present of the invention will suitably be supplied in a their (more ,u, I~l ~11 dL~ ) fomm and converted to a more dilute fonm at the pointofuseinsuchapplications. Goodstabilityinstora3eofthemore.,v,,~,e,,L.dLedfommas supplied before beins converted to a more dilute fomm at the point of use is still required. In a 2û fourth aspect the present invention provides a formulation which is a mixture of the components (a), (b) and (c) of the concentrate accordins to the second aspect of the present invention with 1 û
to 1 û,ûOO times the total weisht of the , . Iel l~a (a), (b) and (c) of water, e.g. with 30 to 1,000 times the total weight of the components. This formulation accordin~ to the fourth aspect of the invention may of course comprise othem,ullluull~llLa and additives. Suitable and preferred such 25componentsandadditivesareassodescribedl~elc:i,l'vetu,ewithre3ardtothe, 1 '' la,e.g.
solvents and anti-foam sgents, which may be desi~nated as components (d).
The fommulation may be made up in various ways, by for example (i) mixing the components (a), (b) and (c) and (d) to form the concentrate and then diluting the 30 concentrate by mixing it with water to fomm the formulation; or (ii) mixing components (a), (b) and (c) to fomm a concentrate and dilutins the concentrate with water to fonm a fommulation, as appropriate mixins the components (d) and dilutin3 the mixture of these components with water to form a second mixture, and mixin3 the nrSt fommulation and the seoond mixture to fomm the desired fommulation according to a fourth 35 aspect of the present invention.
Such a process for preparin5 the formulation accordins to the fourth aspect of the present invention fomms a fiRh aspect of the invention.

~ WO 95/22897 2 1 ~ 8 r ~
In all such processes for preparing the fommulation accordin3 to the invention, the ratio of the weight of water used to the total wei3ht of the w" ,uu~,~"~ . (a), (b) and (c) of the fommulations of the second aspect will of xurse be adjusted as appropriate to give a final fommulation of the components (a), (b) snd (c) with in the definition above.

In a sixth aspect the present invention also pnovides a method of applying the fonmulation according to the fourth aspect of ths present invention to a substrate ,1~ of this method include a a method of treating vegetation by applying to plants and/or soil such a formulation 1 û according to the invention which fommulation compnses a speciflc chemical agent which is an aul ul,l lt:llli~,dl b a method of working metal which compnses applying a fommulation according to the invention to the metai which fonmulation optionally comprises a specific chemical a3ent which is a metal corrosion inhibitor 15 In ~ ' " ,L a the dUI Ul.l I ' ' may be one or more ul l,h , for example growth regulators and/or herbicides, and/or pestiades, for example insecticides, fungicides or acaricides This ~:",~uù" "~ of the method of applyin3 the fommulation accordin3 to the fourth aspect of the present invention thus includes in tunn (i) a method of killing or inhibiting ve3etation by applying the fommulation which comprises a 2û specific chemical agent which is one or more ,ul ,, ~ , for example gnowth regulators and/or herbicides, and (ii) a method of killing or inhibiting plant pests by applying the formulation which comprises a specific chemical a~ent which is one or more pesticides, for exampie insecticides, fungicides or acaricides.
251n~,,,L,ud,,,,~,,l(i),theeffectoftheauru~ ,,,i~l,whetheroneormore,ul,y~ut..,~;Jcs,forexample growth re~ulators and/or herbicides, and/or pesticides, for example insedicides, fungicides or acaricides, may be potentiated by the surfactants. In: ' ' ,L (ii) the workin~ of the metal may include for example cutting or abrasion 3û Within w"~"~,dt~ and fonmulations of the present invention which comprise as component (c) an aul u-.l, 31, this is typically one or more ,ul If ~U..~'i . _s" for example growth regulators andlor herbicides, or pesticides, for example insecticides, fungicides or acancides i~xamples of such ~u~ r,~ " ~ appropriate for the intended use of the composition include an ~u~ uul, ' which is one or more pl ., !uc~ D, for example herbicides such as Acetochlor, Alachlor and Trifluralin, 35 and also pesticides, for example insecticides such Propar~ite and Fenitrothion, and fungicides such as r, uuiw, l~ult WO9~/22897 21 83858 r~ u Within cu, ~,O~ ~8 d~oS and fommulations of thô presOnt invention which comprisO as component (c) an clu~ u~,l lolll;~,dl, somO comprisO a potentiator or inhibitor of thô working of the au" ' ' U
an ~Iu.,l loll ,;~l which is one or more ~ul Iyt ' , for OAample growth resulators or herbicidOs, is present, and an inhibitor dU~ u~.h ' is also present, it may typically be a ~UI ~ U~UA;~ Y
S inhibitor~ Examples of suitable such materials include Safener.
Within w, ,~, IL dtoa and fonmulations of the present invention, some comprise a conrosion inhibitor as componOnt (c). These may be used in a method of worhng metal which comprises applyin3 a fommulation according to the invention to the metal which compnsOs such a chemical agent. One 1 û class of known corrosion inhibitors, suitable for practically all the relevant substrate matOnals which may be trOated, includes straight chain or branched alkanO carboAylic acids and water soluble salts thereof e.g. with an alkali metdl cation e.3. sodium or potassium, or an " ,.,ld,l,-"u,liumcation. Materialsofthistypeincludeinparticularwatersoluble ul~ "" ,u/ ~;um salts of straight chain or branched alkanO carboxylic acids which acicts 15 comprise 8 to 11 carbon atoms.
2û

3û

~ wogs/22897 21 83858 1~11. ,~, The present inYention is illustrated by the following Examples. All parts and pe,~"ta~ . are by weight unless otherwise stated. Example references suffixed by 'c' are for comparison purposes.
E~AMPLE 1 J 5 Preparation of Emulsifier Cl Ia The emulsifier la shown in Table 1 were made by addino the components in the stated amounts in a simple mixin~ process with stimng as appropriate. The components in Table 1 are as follows:
H1 Half Ester Derivative of the fommula:
Y.O2C.(HR)C.C(HR').CO,(CmH2mO)~.R2 where Y is H one of R and R1 is C1~H,5 and the other is hydro3en m is 2 n is about 23 alJùl Idil l~ to PEG 1000) and R2 is H.
A Anionic Surfactant calciumd~ "~t"esulphonate N Non-lonic Surfactant Atlas G-5000 surfactant (lCl) 15 W Water Miâcibie Liquid isobutanol S Solvent Solvesso 100, aromatic l ,~ dl u~, Lul~ solvent mixture (Exxon Chemicals) Table 1 Comp % w/w of Components No H1 A ~ S W
~ ~,o O 30.8 ~.o 13.0 13.2 '' 0.0 ''~.0 ~, .0 1 ~.0 1 ~-,0

3 50 0,3.G i~.0 1~.0 1~.4 , ~o o .9 ~ o ~.O fi.c.
. 0.0 3-u ~0 Y.0 ~
ii 0.0 .,6.~ -~1.0 q.O ' .fi c - 3O.~ ~3 0 3.0 .,.
" c - ' R.u ~.,.n .n ~ -.o 3û c - 3. , I " ~, ~ C - 1!1, .0 ,U ' ~
. ' C - ~ q.U ~l Q fi c ~,~ ~q,~ ,o .

wo g5n28~7 2 1 83 8 C; ~ u F~AMPLE 2 Preparation of Emulsifiable Concentrate and Diluted Fommulation; Testing of Fommulation The above emulsifier ~ E1 to 6 and E21 c to E61 c were fommulated into w" aauul l-lil "~ -wl)Cal Itl ~Las shown in Tables 2, 4, 6 and 8 by addins the components in the stated amounts in a 5 simple mixin3 process with stirring as appropriate.
The above w, l~al l~la~a:~ were fommulated into w" a~ ul ~di"-J diluted fommulations by adding the w, ,~. ,tl u~a~ to water with the following parameters described above the relevant Table in each case as appropriate: to the given % wt.lvol. dilution rate (suitable for the given desired use of the 10 given (diluted) concentrate), at the given temperature at the given WHO standard hardnesses of 342 and 50û ppm, and with the formulations being left to stand for the ~iven length of time.
The efflcacy of each emulsifier composition used in the w, Ical ,~, d~à~ shown in Tables 2, 4, 6 and 8intheformulations,.ul,a.,uu"-li"~u,tothe.ù"~ ,dlc,~sisshovJninTables3,5,7and9 15 respectively, in which the numbering of each formulation w, ~ ul l-l~ respectively to the numbering of each concentrate, and the ~Igures are the volume of the disperse phase of the concentrate (which contains the components (a), ~b) and (c)) which separates from the other phas~.
Table 2 2ûConcentrate C1 ¦ C11 Component wt./vol. of Components Alachlor ~herbicide) 480 9 480 9 E 40g E - 40~
xyene to 11 to 11 Table 3 2 % wt./vol. dilution at25C - Standard Water Hardness 342 and 500 ppm Formulation F1 ¦ F11 Haroness cream separation ~ml) 30 342 ppm NS ¦ 3.5 C
500 ppm NS ¦ 3.5 C
NS = no separation of the emulsion ~ WO 95/22897 2 1 8 3 8 ~ 8 Table 4 Concentrate C2 ¦ ,3 ¦ C2c ¦ C3c Component w.ho . of Cnmponen s Acetochlor(herbicide) 94%active 520g 5~06 920g 530g 5 - fener (,ul ,, ' ' ~; inhibitor) - ~0g - 70 -80g ' 1c - - 80g 11 c ' ~ ~ 809 ~olvesso 100 - 320g - 320g Table 5 5 % wUYol dilution 30C - Standard Water Hardness 342 ppm Fonmulation F2 ¦ F3 ¦ F2c ¦ F3c Standing Time (hr) cream sepsration (m ) 15 0.5 TC ¦ TC ¦ 0.25C 6C
1.0 0.25C ¦ 0.25C ¦ 0.5C 6C
TC = trace (~ 0.05%) separation of the emulsion Table 6 Concentrate C4 ¦ C4c .omponent Compnnents enitrothion (insecticide) 520g 520g ~31 c - 1 00g 25 .olvesso 150 to 11 to 11 Solvesso 150 = aromatic hydrocarbon solvent mixture, (E)o~on Chemicals) Table 7 5 % wt.lvol. dilution 30C Standard Water Hardness 20 and 500 ppm ormulation F4 ¦ F4c ardness (ppm) 20 ¦ 500 ¦ 20 ¦ 500 . '~tanding Time (hr) -eparat on (ml) 0.5 1~ ~ ~ 9 OC 9 OC
2 1~ . 9C+TOC 5Cf30C
24 1~ 1 C+7O 8C
35 NS = no separation of the emulsion OC = oily cream separation of the emulsion _ _ , _ . _ _ . _ _ _ _ . ... ... ....... .....

WO 95122897 1 ~,1,. lu 2~83~58 C = cream separation of the emulsion TOC = trace (~ 0.05%) oily cream separation of the emulsion O = oil separation of the emulsion 5 I ble8 Concentrate C5 ¦ C6 C7 ¦ C51c ¦ C61c ¦ C71c ~;omponent ~. of Com onents ( ) 'ropargite (insecticide) 635 635 635 635 635 635 c - - - 80 ! C - - - - 80 fi C - - - - - 80 . ylene 322 322 322 322 322 322 Table 9 1 % wt./vol. dilution 30~C Standard Water Hardness 342 ppm Fommulation F5 ¦ F6 ¦ F7 ¦ F51c ¦ F61c ¦ F71c Standing Time (hr) separation (ml) 200.5NS NS NS 0.5C + 0.5 C 1 C +
TO + TO TO
NSNS NS 0.5 C TC + TC +
0.50 1 0 1.20 2NSNS NS 0.5C TC+ TC+
0.50 l 0 1 0 4NSNS NS O.5C+ TC + TC +
0.50 10 10 24NS NS NS TC NS 0.5C +
0.70 NS = no separation of the emu~sion TC = trace (< 0.05%) oily cream separation of the emulsion 30 C = cream sepanation of the emulsion TO = trace (< 0.05%) oil separation of the emulsion O = oil separation of the emulsion ~ WO 95/22897 2 1 ~ 3 ~ :~ 8 EXAMPl F 3 Prepatation of Emulsifer C , ' ,a The emulsifier ,~ a shown in Table 10 were made by adding the components in the stated amounts in a simple mixing process with stirtins as appropnate. The half ester derivative 5 component H2 in Table 10 is of the fommula:
Y.02C.(HR)C.C(HR').CO2(CmH2mO),.R2 where Y is H, one of R and R1 is C"H27 and the other is hydrogen, m is 2, n is about 14 (wllc7~,uulldill~to PEG6ûO)and R2 is H.
1 û Table 10 ~ ~ , I 7 ¦ E8 ¦ E9 Component c; w/w of Components ~2 ~5 1 50 1 -Atlas G-5ûO0 5 ¦ 5û ¦ 1ûO

Preparation of Emulsifable Concentrate (Concentrated Emulsion) and Diluted Formulation;
Testing of Fonmulation Theaboveemulsiflerw,,,uu:.iLiu,,aE7toE9wereformulatedintow,,a:,,uu,,~i,,ucu,l,,e,,lld~a 20 shown in Table 11 by adding the components in the stated amounts In the following mixing process The Acetochlor active material, the Safener, the poly(ethoxylated) soybean oil and the respective emulsifier composition E7, E8 or E9 components on the one hand, and the propylene glycol and the water on the other were mixed separately at 50C with stirring until 25 each product was l~ul~luue~ UUS, to give two separate liquid phases, ('phase B' and 'phase A' tespectively).
Phase B was then carefully dispetsed in Phase A by adding it slowly to Phase A with oonstant stinting and keeping the temperature at 50C. The resultant mixture of phase B
and phase A was then I IUI "Uy~:l ,;sed with hish shear mixing, and the tesultant w"~"l, .,'~,J
30 emulsion was allowed to cool to ambient temperature under low energy mixing.
The viscosity modifier was then dispetsed in the emulsion under high shear mixing to give a thickened emulsion.
The above emulsifier ,,u" luuail;ul la E7 to E9 were also fommulated into ~,u,, L_,JUI ~i;l lu Wl l~ .t~
shown in Tables 14 and 17 by mixing the wllluullellll~ in the stated amounts in the above mixing 35 process. The efficacy of each emulsifier composition used in the r,u, ,~"~, d~tla is shown in Tables 12,15 and 18 respectively.

WO95/22897 2 1 838~8 ~ .scl ~u Table 1 1 Concentnate CE1 ¦ CE2 ¦ CE3 Component .~t./vol of Components Acetochlor(heroicide) 93%active 5889 5389 5389 Ssfener(~l.,' ' ~inhibitor) ~ 9 529 529 UAY~.,hl) soybean oil 9 159 159 , [~9 propylene glycol 5û9 509 509 10 Rhodopol23(visoositymodifler) 19 19 19 water to 11 to 11 to 11 Table 1 Formulation CE1 ¦ CE2 ¦ CE3 15 Temp.(C) Time(wk) sep2r~tior O ~'~ N--22 4 ~ N.. i~
40 4 ~ ~` N~; ~ S
NS = no separation of the emulsion 20 The above wllwl~lal~ were fommulated into wll~auulldillU diluted fonmulations by adding the ~.UI IC~ 1 a~e:a to water with following parameters described above the relevant Tabie in each case as appropriate: to the given % wt./vol. dilution rate (suitable for the given desired use of the given (diluted) concentrate), at the given temperature at the given WHO standard hardness of 342 ppm, and with the formulations being left to stand for the giYen iength of time.
The efiicacy of each emulsifier composition used in the ~UI lWI Ill al~ shown in Tables 11, 14 and 17inthefonmulationsw,,c,auu,,Jil,,u,tothe~u,l-,e,llilc~l,,~isshowninTables13, 16and19 respectively, in which the numbering of each formulation Wl I ~a,UUI I~S respectively to the numbering of each concentnate, and the figures are the volume of the dispense phase of the 30 concentrate (which oontains the cu" -,uul l~ (a), (b) and (c)) which sepanates from the other ph~_ ~ W0 95/22897 2 1 8 3 8 ~ 8 1~1 ,9 ',able 13 2 % wt./vol, dilution 22C Standard Water H2rdness 342 ppm Fommulation CF1 ¦ CF2 ¦ CF3 Temp (C) Time (wk) sc ~aratinn (ml) 0 N~ 0.15 22 ~ Tr ~r~ 0.1 l:
40 ~ TC ~(, 0.1 r-TC = trace (~ 0.05%) cream separation of the emulsion C = cream separation of the emu~sion Table 14 Concentrate CE4 ¦ CE5 ¦ CE6 omponent wt./vol of Compnnents ' r`lfluralin ~heroicide) 96~ active 5005 5009 5009 a - 509 _~ , 509 propylene alycol 209 205 209 xylene 2059 2059 2059 water to 11 to 11 to 11 Table 15 Fommulation CE4 ¦CE5 ¦CE6 Temp ('C) Tlme ~wk) ~i~DaratiDn 0 \` ~.. NS

NS = no separation of the emulsion 1~
30 2 % wt IYOI~ dilution 22C Standard Water Hardness 342 ppm Fommulation CF4 ¦CF5 ¦CF6 Temp (G) Tme (wk) ! epqratiol ~ml) 0.2 - 0.~5C 0.6C
22 4 o.2 C O.fi C
40 4 0.3.'~C 0. ~ C

35 C = cream separation o~ the emulsion oncentrate CE7 ¦ CE8 ¦ C 9 r.omponent v,t./vol of Comp~nen 'u~uiw,,i~ule(fungicide)60%active 4179 4173 4~ g r~ - 100g g ~ 009 propylene glycol 1009 1009 ~ ûug xylene 1839 1833 ~.,9 ~vater to 11 to I to I

rable 1 Formulation CE7 ¦ CE8 ¦ CE9 Temp (C) Time (wk) sep~-~tior 0 ~ N~
15 22 4 ~ ~ N-40 4 '~ ` N~
NS = no separation of the emulsiûn 20 2 % wt./vol. dilution 22C Standard Water Hardness 342 ppm Fommulation CF1 ¦ CF2 ¦ CF3 Temp (C) Time (wk) se~ara ion (ml) û ~ 2 C

40 4 ~ TC 1 C
C = cream soparation o~ the emulsion I = impossible to emulsify

Claims (8)

Claims:

1 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 C6 to 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 average it may be non-integral);
m is 2 or 3 (and may vary along the polyoxyalkylene chain);
R2 is hydrogen or C1 to C16;
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 (b) at least one other surfactant.

2 A composition as claimed in claim 1 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.

3 A composition as claimed in either claim 1 or claim 2 which comprises:
(a) at least one compound of the formula (?) or (??) as defined in either claim 1 or claim 2, present as 5 to 90 wt.% of the total composition; and (b) at least one other surfactant, present as 10 to 90 wt % of the total composition.

4 A composition as claimed in any one of claims 1 to 3 which comprises:
a at least one compound of the formula (?) or (??) as defined in either claim 1 or claim 2, present as 5 to 90 wt.% of the total concentrate; and b i at least one non-ionic surfactant, present as 10 to 90 wt.% of the total; and ii optionally at least one anionic surfactant present as 0 to 60 wt.% of the total composition.

A composition as claimed in any one of claims 1 to 4 in which the other surfactant is or includes at least one of:
an anionic surfactant selected from the alkarene sulphonate salt group; the poly(arylaryl-alkoxylate) 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 members of 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 alkanolammonium, wherein the aliphatic or alkanol moieties are alkyl having 1 to 4 carbon atoms; and mixtures thereof;
a cationic surfactant selected from alkoxylated fatty amine salts having 8 to 24; and/or a non-ionic surfactant selected from those of the formulae:
R21.O(X)R22 and/or R23-N(-XH)2 in which R21 is an alkyl group or alkenyl group which contains up to 24, an alkyl phenol group having 6 to 12 carbon atoms in its alkyl group, a sorbitan group or a group of the formula R24CO in which R24 is an alkyl group having 11 to 22 carbon atoms;
R22 is hydrogen or an alkyl group, a carboxyalkyl group, or a fatty acid residue having 10 to 22 carbon atoms;
X is a polyalkylene oxide group containing an average of 2 to 40 alkylene oxide groups or mixed alkylene oxide groups; and R23 is an alkyl or alkenyl group having 10 to 22 carbon atoms.

6 An emulsifyable concentrate 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 0.1 to 15 wt.% of the total concentrate;
(b) at least one other surfactant, present as 1 to 25 wt.% of the total concentrate; and (c) at least one chemical agent with activity specific to the intended use of the concentrate, present as 2.5 to 95 wt.% of the total concentrate.

7 A concentrate as claimed in claim 6 in which the chemical agent with activity specific to the intended use is or includes one or more herbicide or pesticide.

8 A concentrate as claimed in either claim 6 or claim 7 in which the balance of the concentrate is made up of one or more water miscible organic liquids selected from alcohols and glycols;
and/or one or more water imiscible liquid selected from hydrocarbons; straight chain or branched alcohols; optionally hydrogenated vegetable oils; C1 to 5 esters of C8 to 22 fatty acids;
N-methylpyrrolidone; and isoparaffins; or a mixture thereof.