WO1995022896A1

WO1995022896A1 - Adjuvant compositions

Info

Publication number: WO1995022896A1
Application number: PCT/GB1995/000369
Authority: WO
Inventors: Dirk Hoorne; Ludewijk Maria Rogiers
Original assignee: Imperial Chemical Industries Plc
Priority date: 1994-02-24
Filing date: 1995-02-22
Publication date: 1995-08-31
Also published as: PL316034A1; CZ248596A3; WO1995022897A1; HU9602318D0; SK109096A3; HU9602319D0; KR970701000A; CA2183858A1; CZ248496A3; SK109196A3; EP0746201A1; JPH09509660A; ZA951475B; PL316035A1; HUT74607A; AU1713495A; EP0746200A1; JPH09509362A; BR9506873A; CA2183857A1

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.(C¿m?H2mO)n.R?2¿ or (II) Y.A1.OC.(HR)C.C(HR1).CO.A.(C¿m?H2mO)n.CpH2p.A.CO.(HR?1¿)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

Adjuvant Compositions

This invention relates to adjuvant compositions, and in particular to compositions which contains at least two surfactants and/or at least one oil, to dispersible concentrates, which are readily dispersible and/or soluble in water, in particular to concentrates with a high dispersed phase loading, comprising such an adjuvant composition, to diluted formulations comprising the concentrate, and to processes for preparing or using the adjuvant compositions, the concentrates, and the diluted formulations.

Compositions with at least one surfactant are known in general in the agrochemical industry for use as components of concentrates comprising an agrochemical or of a corresponding diluted formulation comprising the concentrate such that the agrochemical is readily dispersible and/or soluble in the concentrate or diluted formulation. Such known compositions and such known concentrates comprising an active chemical agent may also comprise at least one oil component. 5

There is also a demand for example in the agrochemical industry for adjuvant compositions which enhance the activity of any chemical agent (e.g. an agrochemical) or other materials which are present in the concentrate or corresponding dilute formulation. In some intended uses of such concentrates, e.g. in methods of applying corresponding formulations of some agrochemicals, ° such as insecticides, herbicides, fungicides or acaricides, it is preferred that not only will the corresponding diluted formulation comprising the composition have a significantly enhanced activity, but that the processes for preparing the formulation is no more than simple mixing. However, (a) the efficacy of known adjuvant compositions as adjuvants and 5 (b) the extent to which the resultant concentrates are readily dispersible and/or soluble into water is usually limited to a specific combination of a dispersed chemical agent and readily dispersible and/or soluble surfactant components.

This invention seeks to provide a class of materials of this adjuvant nature, which give 0 concentrates which are readily dispersible and/or soluble into water, and corresponding dilute formulations with significantly enhanced activity, which are useful in general in the agrochemical industry.

We have developed a class of vic-dicarboxylic acid polyalkyleneoxy half ester derivatives as ⁵ described in published PCT Application No WO 94/00508 A (PCT/GB 93/01335). This invention . relates to applications of compounds of this general type of the formula (I) or (II) below: Y.A¹.OC.(HR)C.C(HR¹).CO.A.(C_mH_2mO)_π.R² (I) where one of R and R¹ is C₆ to C^ alkenyl or alkyl and the other is hydrogen;

A is -0- or -NR⁴-; where R⁴ is hydrogen or C, to C_β alkyl, particularly methyl or ethyl; 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 C, to C₁₆ , particularly C₁ to C₆ alkyl;

A¹ is -0-, -O^" or -NR⁴- where R⁴ is hydrogen or C, to C₆ alkyl, particularly methyl or ethyl; such that when A¹ is -0^": Y is a cation, particularly H⁺, and alkali metal cation especially a sodium or potassium cation, or an ammonium ion (especially NH₄ ⁺, an amine ammonium or an alkanolamine ammonium ion); and when A¹ is -0- or -NR⁴-: Y is a C, to C₆ alkyl group (R³) or a group of the formula

(C-.H_2mO)_n.R² where m, n and R² are independently as defined above; or

Y.A¹.OC.(HR)C.C(HR¹).CO.A.(C_mH-_n-0)_n.C_pH_2p.A.CO.(HR¹)C.C(HR)CO.A¹.Y (II) where: n, m and each R, R\ A, A¹ and Y are independently as defined above; and p is 2 or 3.

As described in WO 94/00508 A, the free acid forms of compounds of the formulae (I) and (II) in are defined with Y as a H⁺ cation including both the ionised and non-ionised form of the free acids. Compounds of the formulae (I) or (II) are typically mixtures of isomers corresponding to the two senses of the anhydride ring opening reaction typically used in their synthesis. The alk(en)yl 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 formulae (I) and (II) include those of the formulae (la) and (Ha):

R¹ - CH(CO.AY) - CH₂ CO.AZ (la) in which z is a group of formula (C_mH_2mO)_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 and preferably 1 to 6 carbon atoms; A and A¹ are each independently -0-, -0^" 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 (C_mH_2mO)_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 (Ha):

R¹ - CH(COA¹Y) - CH₂-CO.A - D - A.OC - CH₂ - CH(COAΥ) - R¹ (lla) in which D is a group of formula (C_rnH_2n10)_n C_pH_2p - in which p is 2 or 3; and R¹, A, A¹, m and n are as defined above for formula (1a).

Various uses of compounds of this general type are described in WO 94/00508 A, including as emulsifying agents for acrylamide invert polymerisation systems and as wool scouring agents. We have now found that such compounds are useful in adjuvant compositions together with at least 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 form concentrates comprising a chemical agent with activity specific to the intended use of the concentrates and formulations comprising the concentrates such that the agrochemical therein is readily dispersible and/or soluble into water. Such concentrates and formulations comprising the concentrates (unlike the above compositions, which may be used as a component of concentrates) 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 formulations are useful for applying in the agrochemical industry, e.g. for agrochemicals, such as herbicides, 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 polyalkyleneoxy half ester derivative of the formula (I) or (II) 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.

Suitable adjuvant compositions of this first aspect are those comprising

(a) at least one vic-dicarboxylic acid polyalkyleneoxy 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 total composition; (c) at least one oil component, present as 0 to 99, and in particular as 0 to 97 wt.% of the total composition; and/or (d) at least one organic solvent, present as 0 to 90 wt.%, and in particular as 0 to 75 wt.% of the total composition.

The components and their proportions are preferably chosen such that where any components are readily available only as aqueous solutions the composition provided by mixing the composition components is stable, notwithstanding the water which is thereby introduced.

The composition often employs a half-ester derivative containing anionic groups and/or in particular groups ionisable to anion. Preferred such ester derivatives are generally as set out in our co-pending application, but preferred vic-dicarboxylic acid polyalkyleneoxy half ester derivative surfactants of this type include mono- and di-ester derivatives of formula (I) or (II) respectively in which R/R¹ as defined preferably has 8 to 20 carbon atoms. This is particularly the case in the agrochemical industry when used to form a dispersible and/or soluble concentrate or corresponding dilute formulation comprising a chemical agent with activity specific to the intended use of the concentrate or corresponding dilute formulation. Particular ester derivatives of this type include those in which R/R¹ has 10 to 17, preferably 12 to 14 carbon atoms, and in particular where it is an alkenyl group. Preferred such vic-dicarboxylic acid polyalkyleneoxy half ester derivatives also include those of formula (I) in which the group (C_mH_2mO)_nR² as defined above or the formula (la) in which Z is an alkylene oxide (block) (co-)polymer of formula (C_mH_2mO)_nR² as defined above, in which n is preferably 7 to 13 and m is 2 and/or 3.

The other surfactant(s), if present, may be any which on using the adjuvant composition in the formulation of a concentrate or diluted formulation comprising a chemical agent with activity specific to the intended use of the concentrate or corresponding dilute formulation, 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 corresponding diluted formulation include anionic, cationic, amphoteric or non-ionic surfactants, or mixtures thereof.

Suitable anionic surfactants include members of the alkarene sulphonate salt group, such as an alkyl benzene sulphonate salt having 6 to 16 carbon atoms in its straight chain or branched alkyl group, e.g. wherein the alkyl is lauryl (dodecyl), or mixtures thereof; members of the poly(arylaryl- 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 members of the fatty acid salt group, having 8 to 24, preferably 12 to 18, carbon atoms, e.g. laurate, heptadecanoate, heptadecenoate, stearate and oleate; and/or members of the group of salts of alkoxylated carboxylated alkaryl and fatty alcohols, the latter including e.g. poly(ethylene oxide)C₁₂.₁₅ alcohol methylcarboxylates.

Examples of suitable salts include those with a cation which is an alkali metal e.g. sodium or potassium; an alkaline earth metal, e.g. calcium; and/or ammonium, aliphatic ammonium alkanolammonium cation, wherein the aliphatic or alkanol moieties are e.g. straight-chain or branched alkyl having 1 to 4 carbon atoms; and mixtures thereof.

In particular when the composition is used in the agrochemical industry to form a dispersible and/or soluble concentrate or corresponding dilute formulation comprising an agrochemical agent with activity specific to the intended use of the concentrate or corresponding dilute formulation, preferred component (b) anionic surfactants include alkylbenzene sulphonate salts having 6 to 16 carbon atoms in their straight-chain or branched alkyl group, e.g. wherein the alkyl is lauryl. 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) C_{12to l5} amine salts, e.g. chloride salts.

Non-ionic surfactants are particularly useful in concentrates which are readily emulsifiable in particular in agrochemical concentrates. These include non-ionic surfactants used in the agrochemical industry to form emulsifiables, in particular those of the formulae: R² .0(X)R²² and/or R²⁵OR²⁶ and/or R ³ - N (-XH)₂ in which

R²¹ 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^CO in which R²³ is an alkyl group having 11 to 22 carbon atoms; R²² is hydrogen or an alkyl group, a carboxyalkyi group, e.g. carboxyalkyi having 2 to 4 carbon atoms, or a fatty acid residue having 10 to 22 carbon atoms; X is a polyalkylene oxide group containing 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; R²³ is an alkyl or alkenyl group having 10 to 22 carbon atoms; R²⁴ is a sorbitan group;

R²⁵ is a fatty acid residue having 10 to 22 carbon atoms; and R²⁶ is an alkyl or alkenyl group having 10 to 22 carbon atoms. Examples of suitable groups R²¹ include e.g. iauryl, heptadecyl, heptadecenyl, heptadecadienyl, stearyl or oleyl moieties. Examples of suitable groups R²² include e.g. carboxy-methyl, ethyl or propyi, or a salt thereof; and lauroyl, heptadecanoyi, heptadecenoyi, heptadecadienoyi, stearoyi or oleoyl. Suitable possibilities for X include those wherein the alkylene groups each have 2 to 8, preferably 2 or 3 carbon atoms. Examples of suitable groups R^2S include e.g. lauroyl, heptadecanoyi, heptadecenoyi, heptadecadienoyi, stearoyi or oleoyl.

Examples of suitable non-ionic surfactants thus include poly(alkoxylated) fatty acids and alcohols having 8 to 24, preferably 12 to 18 carbon atoms in their fatty acid or alcohol groups; poly(alkoxylated) alkaryl alcohols having 8 to 24, preferably 12 to 18 carbon atoms, and phosphate and sulphate esters thereof; poiy(alkoxyiated) sorbitan and sorbitol esters; poly(alkoxylated) mono-, di- and triglycerides, including poly(alkoxyiated) vegetable oils, such as poly(ethoxylated) mustard oil, neem oil, niger seed oil, oiticica oil, palm oil, palm kernel oil, peanut oil, safflower oil, sesame oil, soybean oil, and especially castor oil; poly(alkoxylated) allyl alcohols, and phosphate and sulphate esters thereof; poly(alkoxylated) poly(arylaryl alcohols); sorbitan mono-esters in which the acyl group has 11 to 22 carbon atoms; and poly(alkylene oxides) including (block) (co-)polymers.

Within one class of adjuvant compositions of the first aspect of the present invention, especially when used for formulations for application in the agrochemical industry, the component (b) (another surfactant) is

(i) at least one non-ionic surfactant, and/or (ii) at least one anionic surfactant.

Preferred component (b) non-ionic surfactants then include those of the formula R ¹.0(X)R²² and/or R² .OR²⁵ and/or R²⁶ - N (-XH)₂ as defined above which are indicated as preferred non-ionic surfactants above.

Preferred component (b) anionic surfactants include alkylbenzene sulphonate salts having 6 to 16 carbon atoms in their straight-chain or branched alkyl group, e.g. wherein the alkyl is Iauryl. Preferred salts include the calcium salt.

The oil component typically has a boiling point of over 200°C at atmospheric pressure and a melting point not higher than 60^βC. It may comprise for example a mineral oil, an optionally hydrogenated vegetable oil, such as an optionally hydrogenated 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, safflower oil, sesame oil, or soybean oil, an ester (especially a C_{1 to6} ester) of a C_81o22 fatty acid, especially a C_{12to 18} fatty acid, or a mixture thereof.

In the composition any oil soluble surfactant present may of course be partitioned between an oil phase and an aqueous phase.

Preferred adjuvant compositions of this first aspect are those comprising (a) at least one vic-dicarboxylic acid polyalkyleneoxy half ester derivative, present as 5 to 90 wt.% of the total composition, preferably as 10 to 75 wt.%; and (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 60 wt.% of the total, preferably as 0 to 40 wt.%, e.g. 15 to 40 wt.%, in particular as 25 to 40 wt.% of the total; and/or (c) at least one oil component, present as 0 to 97, e.g. 0 to 85, wt.% of the total.

One class of such adjuvant compositions 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 comprising no anionic surfactant.

The organic solvent in particular when used in formulations for application in the agrochemical industry, may be one or more water-miscible and/or soluble liquids and/or water-insoluble organic solvents. This is desirable if the viscosity of the composition would otherwise be inconveniently high. Examples of suitable water-miscible and/or soluble liquids include alcohols, including glycols, e.g. with straight-chain or branched alkyl having 1 to 18 carbon atoms. For applications in the agrochemical 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 hydrocarbons, preferably those having 5 to 18 carbon atoms, including aromatic hydrocarbons, and/or straight chain or branched fatty alcohols, and isoparaffins, and mixtures thereof.

The composition 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 conventional mixing of the components in any order used conventionally in the formulation of such compositions for use in concentrates or corresponding dilute formulations for application in the agrochemical industry. In a second aspect the present invention thus provides a process of making the composition by mixing the components together.

According to a third aspect of the invention there is provided a dispersible and/or soluble concentrate comprising (a) at least one surfactant vic-dicarboxylic acid polyalkyleneoxy half ester derivative of the type hereinbefore described; and (e) at least one chemical agent with activity specific to the intended use of the concentrate or corresponding dilute formulation.

Such chemical agent specific to the intended use of the concentrate or corresponding dilute formulation may be for example an agrochemical or a metal corrosion inhibitor.

If an agrochemical is present it is typically one or more phytoactives, for example growth regulators or herbicides, and/or pesticides, for example insecticides, fungicides or acaricides.

Such concentrates may comprise a second chemical agent which will give a concentrate in which the activity of the first chemical agent is made more specific to or selective in the intended use of the concentrate or corresponding dilute formulation.

Such concentrates typically include e.g. concentrates in which

(a) the first chemical agent is an agrochemical which is one or more phytoactives, for example growth regulators or herbicides, and/or pesticides, for example insecticides, fungicides or acaricides. and (b) the second is a phytotoxicity inhibitor to regulate any phytoactivity, for example growth regulation or herbicidal activity of the concentrate or corresponding dilute formulation, or e.g. Safener inhibitor to make it more selective, e.g. as between graminious and broad leaved species. Such a second chemical agent may be present as up to 15 wt.% of the total concentrate.

Preferred concentrates are those with a high loading of the dispersed phase appropriate for the intended use of the concentrate or corresponding dilute formulation.

These exhibit dispersion even of specific chemical agents which are known in the agrochemical industry as not usually readily dispersed.

One class of such concentrates is that of concentrates comprising at least one of (b) at least one other surfactant,

(c) at least one oil component, and

(d) at least one organic solvent.

(e) at least one chemical agent with activity specific to the intended use of the concentrate or corresponding dilute formulation.

Component (d) (optionally, at least one organic solvent), if present as a component of the above concentrate, will often a be the same as, or b comprise, the water miscible and/or soluble liquid(s) and/or water insoluble organic solvent(s) which are present in the corresponding adjuvant composition, which in such case thus forms a component of the concentrate and corresponding dilute formulations. Again, including (d) to form a component of such concentrates may be desirable if the viscosity of the concentrate would otherwise be inconveniently high, especially when used in concentrates for formulations for application in the agrochemical industry.

Each of the present concentrates when present with say, 10 to 10,000 times the total weight of the components (a) and (d) of water in a corresponding diluted formulation of the present invention for 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 concentrate; and

(b) produces formulations with significantly enhanced activity of the chemical agent specific to the intended use of the formulation, without the need for the addition of any further adjuvant materials for enhanced activity.

(c) exhibits good wetting properties in relation to the dispersed chemical agent in the concentrate herein described, and in particular in relation to treated substrates.

Suitable and preferred vic-dicarboxylic acid polyalkyleneoxy half-ester derivative components are those so described hereinbefore with regard to the same materials which form components of the adjuvant compositions of the first aspect of the invention.

Suitable and preferred optional components of such concentrates, i.e. components such as other surfactant(s), oil component(s) and organic solvent(s), if present in the concentrate, are generally those so described hereinbefore with regard to the same materials which form components of the adjuvant compositions of the first aspect of the invention. An anti-foam agent may be present. A sufficient quantity to provide an anti-foaming effect for the intended use of the concentrate or corresponding dilute formulation without separating out is desirable. Normally 0.05 to 10% and preferably 0.2 to 6% by weight of the total is suitable. Any compounds may be used which are conventionally useful as anti-foam agents in aqueous surfactant formulated with a high dispersed phase content. The antifoaming agent(s) is preferably one or more polysiloxanes, especially of the type having hydrophilic groups. It is preferably of formula:

R% SiO [SiO R* R^**]_nSi R^* ₃ in which the groups R^* are individually alkyl groups, preferably having 1 to 3 carbons atoms and are preferably methyl groups, one or more of the groups R** may be residues of polyalkylene glycols and the others are as defined for R*. The groups R* preferably have a molecular weight in the range 1000 to 20000 and especially 5000 to 15000. Examples of suitable polysiloxane antifoams are disclosed in British Patents 1533610 and 1554736.

Other possible additives in the dispersible and/or soluble concentrate to which this invention relates include non-surfactant materials which are conventionally useful in surfactant formulations, such as viscosity modifiers, stabilisers, and anti-microbials.

One class of known viscosity modifier materials of this type includes one or more commercially available water-soluble or -miscible materials such as gums, e.g. xanthan gums, and/or cellulosics, e.g. carboxy-methyl, ethyl or propylcellulose. These are often present, when used e.g. in agrochemical formulations in particular as 0.01 to 5 wt.% 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.

The dispersible and/or soluble concentrates to which this invention relates may be produced by conventional mixing of the components in any order used conventionally. 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 components (a) and (e), and any optional other additives, and stirring until the product is homogeneous.

For some dispersible and/or soluble concentrates 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 composition would otherwise be inconveniently high. Such dispersible and/or soluble concentrates may have to be produced by separate conventional mixing of the components of the organic solvent (d), e.g. water-miscible and/or soluble liquids and/or water-insoluble organic solvents, optionally, with at least one oil component to form a first liquid phase, and dispersion of the specific chemical agent(s) (e) for the intended use of the concentrate or corresponding formulations together with the remaining components, e.g. another surfactant (b) to give a second separate liquid phase. This is effected with stirring until each phase is homogeneous. The concentrate is made by careful dispersion of the second phase into the first phase.

It may be desirable that this is effected for example by adding the phases at moderately elevated temperatures with high shear mixing to deal with the inconveniently high viscosity of the concentrate which is thereby introduced. The product concentrated dispersion is subsequently left to cool to ambient temperature.

Some dispersible and/or soluble concentrates may have to be produced by separate spraying of one or more solid components of the concentrate, e.g. the specific chemical agent(s) (e) onto a carrier to give a solid phase, followed by dispersion of the carrier together with the remaining components. This latter may be effected for example by stirring until the product is homogeneous. This variant may be necessary if the solid component(s) are those generally described in the art as not usually readily dispersed in concentrates of the present class for application in the agrochemical industry.

In some applications, the concentrates of the third aspect of the invention will suitably be supplied to the customer as such and converted to a more dilute form at the point of use in such applications.

In other applications, the relevant chemical agent is supplied to the customer, optionally with at least one organic solvent or oil but separate from the remaining components of the concentrate in a second separate phase, and conversion to a dilute formulation, e.g. for application in the agrochemical industry, is effected by dilution of the two sets of materials, with stirring, followed by mixing of the corresponding diluted materials to effect dispersion of the agent in the formulations for application.

Good stability in storage of the concentrated materials in either form as supplied before being converted to a more dilute form at the point of use is required. In a fifth aspect the present invention provides a formulation which is a mixture of the components (a) and (e) and optionally (b), (c) and (d) of the concentrate according to the third aspect of the present invention with 10 to 10,000 times the total weight of the components (a) and (e) of water, e.g. with 30 to 1 ,000 times the total weight of the components.

This formulation according to the fifth aspect of the invention may of course comprise other components and additives. Suitable and preferred such components and additives are as so described hereinbefore with regard to the compositions, e.g. miscible materials such as solvents, anti-foam agents, stabilisers, and anti-microbials, which may be designated as components (f).

As noted above, the formulation may be made up in various ways, by for example

(i) mixing the components (a) to (f) as appropriate to form the concentrate and then diluting the concentrate by mixing it with water to form the formulation; or (ii) mixing component (a) with an optional selection of materials from (b), (c), (d) and (f) to form a concentrate and diluting the concentrate with water to form a corresponding first dilute mixture, as appropriate mixing the component(s) (e) and diluting the mixture of these components with water to form a second dilute mixture, and/or mixing the first and second dilute mixtures to form the desired formulation according to a fifth aspect of the present invention.

Such a process for preparing the formulation according to the fifth aspect of the present invention forms a sixth aspect of the invention.

According to a seventh aspect of the invention there is provided a dilute formulation comprising a composition of the first aspect of the present invention with 10 to 10,000 times the total weight of its components of water, e.g. with 30 to 1 ,000 times the total weight of the components of water. This formulation according to the seventh aspect of the present invention may be used e.g. for metal cutting fluids.

In an eighth aspect the present invention also provides a process of making the dilute formulation according 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 stirring until the product is homogeneous.

In a ninth aspect the present invention also provides a method of applying the formulation according to the fifth aspect of the present invention to a substrate. Embodiments of this method include a a method of treating vegetation by applying to plants and/or soil such a formulation according to the invention which formulation comprises a specific chemical agent which is an agrochemical and/or b a method of working metal which comprises applying a formulation according to the invention to the metal which formulation optionally comprises a specific chemical agent which is a metal corrosion inhibitor.

In embodiment a the agrochemical may be one or more phytoactives, for example growth regulators and/or herbicides, and/or pesticides, for example insecticides, fungicides or acaricides. This embodiment of the method of applying the formulation according to the fourth aspect of the present invention thus includes in turn (i) a method of killing or inhibiting vegetation by applying the formulation which comprises a specific chemical agent which is one or more phytoactives, for example growth regulators and/or herbicides, and (ii) a method of killing or inhibiting plant pests by applying the formulation which comprises a specific chemical agent which is one or more pesticides, for example insecticides, fungicides or acaricides. In embodiment b the working of the metal may include for example cutting or abrasion.

Examples of agrochemicals which are phytoactives, for example growth regulators and/or herbicides, or pesticides, for example insecticides, fungicides or acaricides. Examples of such agrochemicals appropriate for the intended use of the composition include an agrochemical which is one or more phytoactives, for example herbicides such as Acetochlor, Alachlor, Nicosulfuron, Primisulfuron, Prosulfocarb, Sulfosate and Trifluralin, and also pesticides, for example insecticides such as Fenitrothion and Propargite, fungicides such as Iprodione and Propiconazole, and agrochemicals of the formula

R³⁰ . C(O) . CH₂ . N(Z¹¹) . CH₂ . P(O) . (R³⁰), (a PMCM compound) in which each R³⁰ is selected from halogen, -NHOH, -N(R³¹)₂, -OR³²-, -SR³²- and -OM, where:

R³¹ is independently 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 independently selected from hydrogen, alkyl, hydroxyalkyl or chloroalkyl, preferably 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; M is selected from hydrogen and agriculturally acceptable salt forming moieties such as alkali metal, alkaline earth metal, stannic, ammonium, organic ammonium, alkyl sulfonium, alkyl sulfoxonium, alkyl phosphonium moieties or combinations thereof; and Z¹ is hydrogen, an organic moiety or an inorganic moiety.

Representative patents disclosing at least some of such compounds include US Patents 3799758, 4397676, 4140513, 4315765, 3868407, 4405531, 4481026, 4414158, 4120689, 4472189, 4341549 and 3948975. Representative patents disclosing PMCM compounds wherein Z is other than hydrogen include US Patents 3888915, 3933946, 4062699, 4119430, 4322239 and 4084954. In preferred PMCM compounds, Z ¹ is hydrogen or an organic substituent, and/or R³² is independently selected from hydrogen, alkyl, hydroxyalkyl or chloroalkyl, preferably 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; M is selected from hydrogen and agriculturally acceptable salt forming moieties alkali metal, phosphonium moieties or combinations thereof. Representative patents disclosing at least some of such compounds include US Patents 3799758, 4397676, 4140513, 4315765, 3868407, 4405531, 4481026, 4414158, 4120689, 4472189, 4341549 and 3948975. Representative patents disclosing PMCM compounds wherein Z¹¹ is other than hydrogen include US Patents 3888915, 3933946, 4062699, 4119430, 4322239 and 4084954. In preferred PMCM compounds, Z¹¹ is hydrogen or an organic substituent. Representative organic substituents include methylene carboxylic; methylene phosphonic; and methylene cyano. Representative organic substituents also include carboxyl, such as formyl, acetyl, benzoyl, perfluoroacyl and thiocarbonyl; ethylene, such as cyano, carbamoyl or carboxy substituted ethyl; and benzene sulphonyl substituents. Representative patents disclosing compounds where the nitrogen contains three organic substituents include US Patents 3455675, 3556762, 3853530, 3970695, 3988142, 3991095, 3996040, 4047927, 4180394, 4203756, 4261727 and 4312662. A preferred tertiary nitrogen substituted PMCM compound is N,N-bis(phosphonomethyl)glycine. Those PMCM compounds wherein Z¹¹ is hydrogen are most preferred when the phytoactivity desired is herbicidal activity. The above patents are herein incorporated by reference.

Illustrative of agriculturally acceptable salt-forming 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 weights of from 24 through 88 inclusive, such as magnesium or calcium; ammonium and aliphatic ammonium, wherein the aliphatic is primary, secondary, tertiary or quaternary and preferably wherein the total number of carbon atoms does not exceed more than about twelve; phenylammonium; trialkylsulphonium, preferably wherein the total number of carbons in the three alkyl substituents does not exceed more than about six, such as trimethylsulphonium, ethyl dimethylsulphonium, propyi dimethylsulphonium and the like; trialkylsulphoxonium, preferably wherein the total number of carbon atoms in the three alkyl substituent does not exceed more than about six, such as trimethylsulphoxonium, ethyl dimethylsulphoxonium, propyi dimethylsulfoxonium and the like; tetraalkylphosphonium, such as tetramethylphosphonium, ethyl trimethylphosphonium, propyi trimethylphosphonium and the like.

In preferred compounds, M is independently selected from the above-described agriculturally acceptable salt-forming moieties and hydrogen. In more preferred compounds, M is an alkali metal, ammonium, monoalkyi ammonium or trialkylsulphonium moiety. In most preferred compounds, only one M is an alkali metal, ammonium, monoalkyi ammonium, or trialkylsulphonium moiety, while the two M's are hydrogen. Representative most preferred compounds include isopropylamine N-phosphonomethylglycine, trimethylsulphonium N-phosphonomethylglycine and sodium sesqui-N-phosphono-methylglycine. Combinations of two or more PMCM compounds can be employed in the concentrate and processes of the present invention.

Within concentrates and formulations of the present invention which comprise as component (c) an agrochemical, some comprise a potentiator or inhibitor of the working of the agrochemical. If an agrochemical which is one or more phytoactives, for example growth regulators or herbicides, is present, and an inhibitor agrochemical is also present, it may typically be a phytotoxicity inhibitor. Examples of suitable such materials include Safener.

Within concentrates and formulations of the present invention, some comprise a corrosion inhibitor as component (c). These may be used in a method of working metal which comprises applying a formulation according to the invention to the metal which comprises such a chemical agent. One class of known corrosion inhibitors, suitable for practically all the relevant substrate materials which may be treated, includes straight chain or branched chain alkane carboxylic acids and water soluble salts thereof e.g. with an alkali metal cation e.g. sodium or potassium, or an alkanolammonium cation. Materials of this type include in particular water soluble alkanolammonium salts of straight chain or branched chain alkane carboxylic acids which acids comprise 8 to 11 carbon atoms. The present invention is illustrated by the following Examples. All parts and percentages are by weight unless otherwise stated.

EXAMPLE 1 Preparation of Adjuvant Compositions The adjuvant compositions shown in Tables 1 and 2 were made by adding the components in the stated amounts in a simple mixing process with stirring as appropriate. The vic-dicarboxylic polyalkyleneoxy half ester derivative components in the compositions in Tables 1 and 2 are of formula (lb): Y.0₂C.(HR)C.C(HR¹).C0₂.(C_mH_2mO)_n.R² (I) in which:

H1 one of R and R¹ is C_1β straight chain alkenyl and the other is hydrogen, m = 2, n = ca 4 (equivalent to a PEG 180 chain), and R² is methyl; H2 one of R and R¹ is C_1S straight chain alkenyl and the other is hydrogen, m = 2, n = ca 11 (equivalent to a PEG 500 chain), and R² is methyl; H3 one of R and R¹ is C₁₈ straight chain alkenyl and the other is hydrogen, m = 2, n = ca 14 (equivalent to a PEG 600 chain), and R² is hydrogen; H4 one of R and R¹ is C¹⁴ straight chain alkenyl and the other is hydrogen, m = 2, n = ca 14 (equivalent to a PEG 600 chain), and R² is hydrogen; H5 one of R and R¹ 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 A1 A2 A3

Components wt. of Components (g)

Mineral oil (ex Q8) 830 - 965

Refined Rape Seed Oil - 830 -

H1 119 85 17.5

Calcium dodecylbenzenesulphonate 36 - -

Isoheptyl alcohol 15 - -

Sorbitan monooleate - - 3.5 n-Butanol - - 14

Poly(ethoxylated) (5) Castor oil - 85 - Table 2

Composition Number A4 A5 A6 A7

Components wt. of Components (g)

H2 70 - - -

H3 - 70 - -

H4 - - 100 -

H5 - - - 100

Propylene Glycol 30 30 - -

EXAMPLE 2 ^'

Preparation of Diluted Formulation; Testing of Formulation

The above adjuvant compositions were formulated into corresponding diluted formulations by adding them to an aqueous dispersion and/or solution of a chemical agent with activity specific to the intended use of the corresponding dilute formulation, optionally with water and any other additives, and stirring to emulsify and give a homogenous formulation. This was effected with the parameters described above the relevant Table in each case. The method of applying and testing the formulations varied and is detailed in each case in the relevant following sub-Examples 2.

Such formulations for application in the agrochemical industry which comprise the present adjuvant compositions have significantly enhanced activity compared with corresponding formulations of which the present adjuvant composition do not form a component.

SUB-EXAMPLE 2.1

Preparation of Diluted Formulation of Fungicide Iprodione; Testing of Formulation

The following Formulations F1 to F6 were made up as described above, by mixing the components:

(a) dispersed chemical agent, solution in water of Rovral FLO fungicide, (50% w/v Iprodione. Rhόne-Poulenc) 3 parts per 250 parts v/v, and

(b) adjuvant compositions A1 and A2, in water as set out in Table 3 below

Table 3

Formulation No F1 F2 F3 F4 F5 F6

Component wt.% of Components

Rovral FLO * (fungicide) 0.05 0.05 0.05 0.05 0.05 0.05

A1 0.05 0.1 0.2 - - -

A2 - - - 0.05 0.1 0.2 TEST METHOD

An in vitro test method was used, consisting of inoculating a bean leaf on agar with Botrytis cinerea fungus, followed by applying the relevant formulation. The latter step is effected by drenching a filter paper with the formulation, and then placing the paper on the leaf. The efficacy of the formulation is assessed by measuring 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 the controls of distilled water and a corresponding dilute formulation containing 0.1 wt.% adjuvant composition, where the zone diameter was 0 (not shown in Table 4). Testing was also carried out against a control of a corresponding dilute formulation containing 0.1 wt.% of the chemical agent (included in Table 4).

Table 4

Formulation IAD (mm)

Rovral FLO alone 13.00

F1 23.00

F2 31.75

F3 41.00

F4 24

F5 33.25

F6 42.5

SUB-EXAMPLE 2.2

Preparation of Diluted Formulation of Herbicide Prosulfocarb; Testing of Formulation

The following Formulations F7 and F8 were made up as described above, by mixing the components:

(a) dispersed chemical agent, solution in water of Defi herbicide, (80% w/v Prosulfocarb EC, Zeneca Agrochem), 3 parts per 250 parts v/v, and

(b) adjuvant compositions A7 and A4, in the proportions set out in Table 5 below.

Table 5

Formulation F7 F8

Component w/v % of Component

A7 0.5 -

A4 - 0.5 TEST METHOD

The formulations shown in Table 5 were sprayed in a field trial at 250 l/ha onto wheat (variety Minaret) at the 2-leaf stage infected with Echinocloa crus-galli. Visual evaluation of the weed control is performed in accordance with the EWRC scale (1 = no damage to 9 = 100% damage). Testing was carried out against an untreated control. Testing was also carried out against a control of a corresponding formulation containing only the chemical agent (shown in the Table). The results are set out in Table 6 as the means of 4 replicates.

Table 6

Formulation Rating (EWRC scale)

Prosulfocarb alone 5

F7 6-7

F8 6

Control 1

No phytotoxicity was observed on the wheat.

SUB-EXAMPLE 2.3

Preparation of Diluted Formulation of Herbicide Primisulfuron, Testing of Formulation

The following Formulations F9 and F10 were made up as described above, by mixing the components:

(a) dispersed chemical agent, solution in water of Tell 75 WG herbicide, (75% w/v Primisulfuron, Ciba) 0.1 g/l, and

(b) adjuvant compositions A5 and A6.

Table 7

Formulation F9 F10

Component v/v % of Component

A5 0.1 -

A6 - 0.1

TEST METHOD The formulations shown in Table 7 were sprayed in a greenhouse trial (temperature 16 - 32°C and relative humidity 65 - 95%, at 400 l/ha onto Sorghum halepense (SORHA) and Amaranthus retroflexus (AMARE). Testing was carried out against an untreated control. Testing was also carried out against a control of a corresponding formulation containing only the chemical agent. Visual evaluation of the weed control is performed 7, 14 and 28 days after treatment. Weed control was evaluated as the percentage of dead plants as compared with an untreated control. The results are set out in Table 8 as the means of 6 replicates. Table 8

Formulation Assessment % Control (days) SOHRA AMARE

Primisulfuron alone 7 0 0

14 10 29

28 26 79

F9 7 0 0

14 15 45

28 50 95

F10 7 0 0

14 15 49

28 40- 85

SUB-EXAMPLE 2.4

Preparation of Diluted Formulation of Herbicide Nicosulfuron, Testing of Formulation

The following Formulations F11 to F13 were made up as described above, by mixing the components:

(a) dispersed chemical agent, solution in water of Nicosulforon SC herbicide, (10% w/v Nicosulfuron SC, Zeneca Agrochemicals) 0.125 %v/v, and

(b) adjuvant compositions A5, A6 and A7, in the proportions set out in Table 9 below.

Table 9

Formulation F11 F12 F13

Component v/v % of Component

A5 0.1 - -

A6 - 0.1 -

A7 - - 0.1

TEST METHOD

The formulations shown in Table 9 were sprayed in a greenhouse trial (temperature 16 - 32°C and relative humidity 65 - 95%, at 400 l/ha onto Sorghum halepense (SORHA) and Amaranthus retroflexus (AMARE). Testing was carried out against an untreated control. Testing was also carried out against a control of a co esponding formulation containing only the chemical agent. Visual evaluation of the weed control is performed 7, 14 and 28 days after treatment 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. Table 10

Formulation Assessment % Control (days) SOHRA AMARE

Nicosulfuron alone 7 0 0

14 10 20

28 15 70

F11 7 0 0

1 25 28

28 30 77

F12 7 0 0

14 20 30

28 25 75

F13 7 0 0

14 25 30

28 25 80

SUB-EXAMPLE 2.5

Preparation of Diluted Formulation of Herbicide Trimethylsulphonium Glyphosate, Testing of

Formulation

The following Formulations F14 to F17 were made up as described above, by mixing the components:

(a) dispersed chemical agent, solution in water of Sulfosate herbicide, (70% w/w Trimethylsulphonium Glyphosate^*) 0.5 %v/v, and

(b) adjuvant compositions A4, A5, A6, and A7.

Table 11

Formulation F14 F15 F16 F17

Component v/v % of Component

A4 0.15 - -

A5 - 0.15 -

A6 - - 0.15 -

A7 - - - ^• 0.15

TEST METHOD

The formulations shown in Table 11 were sprayed in a greenhouse trial (temperature 16 - 32°C and relative humidity 65 - 95%, at 400 l/ha onto Agropyron repens (AGRRE), Poa annua (POAAN) and Amaranthus retroflexus (AMARE). Testing was carried out against an untreated control. Testing was also carried out against a control of a corresponding formulation containing only the chemical agent. Visual evaluation of the weed control is performed 7, 14 and 28 days after treatment. Weed control (% control) was assessed as the percentage dead plants compared with an untreated control. The results are set out in Table 12 as the means of 6 replicates.

Table 12

Formulation Assessment % Control (days) AGRRE POAAN AMARE

Sulfosateate 7 0 0 75

14 40 45 90

28 55 70 95

F14 7 0 0 85

14 70 75 99

28 100 100 100

F15 7 0 0 90

14 70 70 100

28 100 100 100

F16 7 0 0 95

14 90 95 100

28 100 100 100

F17 7 0 0 80

14 90 88 99

28 100 100 100

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.A¹.0C.(HR)C.C(HR¹).C0.A.(C_mH_2m0)_n.R² (I) where one of R and R1 is C₆ to C^ alkenyl or alkyl and the other is hydrogen; A is -O- or -NR⁴-; where R⁴ is hydrogen or C, 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 C, to C₁₆ alkyl;

A¹ is -0-, -0^" or -NR⁴- where R⁴ is hydrogen or C, to C₆ alkyl; such that when A¹ is -0^": Y is a cation; and when A¹ is -0- or -NR⁴-: Y is a C, to C₆ alkyl group (R³) or a group of the formula (C_mH_2mO)_n.R² where m, n and R² are independently as defined above; or

Y.A¹.OC.(HR)C.C(HR¹).CO.A.(C_mH_2rnO)_n.C_pH_2p.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 (la) or (lla):

(la) and (lla):

R¹ - CH(CO.AY) - CH₂ CO.AZ (la) in which Z is a group of formula (C_mH_2mO)_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 -0-, -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 (C_mH_2mO).R² 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 (lla):

R¹ - CH(COA¹Y) - CH₂-CO.A - D - A.OC - CH₂ - CH(COAΥ) - R¹ (lla) in which D is a group of formula (C_mH_2mO)_n C_pH_2p - in which p is 2 or 3; and R\ A, A¹, m and n are as defined above.

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:

R²¹.0(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 R^2βCO in which R²⁶ is an alkyl group having 11 to 22 carbon atoms; R²² is hydrogen or an alkyl group, a carboxyalkyi group having 2 to 4 carbon atoms, or a fatty acid residue having 10 to 22 carbon atoms; and }22 is hydrogen or an alkyl group, a carboxyalkyi group having 2 to 4 carbon atoms, or a fatty acid residue having 10 to 22 carbon atoms; and X is a poiyalkylene 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 R²⁶ 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 C, _to6 ester of a C_8to22 fatty acid; and mixtures thereof.

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.

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.

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.

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

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.

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.

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.