WO1995022897A1

WO1995022897A1 - Emulsifier compositions

Info

Publication number: WO1995022897A1
Application number: PCT/GB1995/000370
Authority: WO
Inventors: Dirk Hoorne; Lodewijk 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: AU1713595A; HUT74607A; CA2183858A1; EP0746201A1; SK109196A3; CA2183857A1; WO1995022896A1; SK109096A3; ZA951475B; JPH09509362A; AU1713495A; HU9602319D0; HUT74772A; BR9506873A; CZ248596A3; KR970701001A; HU9602318D0; EP0746200A1; BR9506879A; KR970701000A

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.(C¿m?H2mO)n.R?2¿ or (II) Y.A.1.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 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

EMULSIFIER COMPOSITIONS

This invention relates to emulsifier compositions, and in particular to compositions which contain a plurality of surfactants; to emulsifiable concentrates, which are readily emulsifiable into water, comprising the emulsifier composition, in particular concentrates with a high loading of a chemical agent with activity specific to the intended use of the concentrates; to diluted formulations comprising the concentrate; and to processes for preparing or using the emulsifier compositions, the concentrates, and the diluted formulations comprising the composition.

Emulsifier compositions with a plurality of surfactants are known in general in the agrochemical industry; these may be used to form concentrates comprising a chemical agent with activity specific to the intended use of the concentrate, and such concentrates are readily emulsifiable on conversion to a diluted formulation. However, the efficacy of such emulsifier compositions as an emulsifier and the extent to which the resultant compositions are readily emulsifiable into water to a diluted formulation is usually limited to a specific combination of a dispersed chemical agent and readily emulsifiable surfactant components.

We have developed a class of vic-dicarboxylic acid polyalkyleneoxy half ester derivatives as 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(HR ).CO.A.(C_mH_2mO)_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 C. to C₆ 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 C_1β , particularly C, 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 -O- or -NR⁴-: Y is a C_n to C₆ alkyl group (R³) or a group of the formula (C_mH_2rnO)_n.R² where m, n and R² are independently as defined above; or Y.A¹.OC.(HR)C.C(HR¹).CO.A.(C_mH_2mO)_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 preferablyl to 6 carbon atoms; 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_rnH_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(COAΥ) - CH₂-CO.A - D - A.OC - CH₂ - CH(COA¹Y) - 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 R¹, A, A¹, m and n are as defined above for formula (la).

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 emulsifier compositions with a plurality of surfactants, which may be used to form concentrates comprising a chemical agent with activity specific to the intended use of the concentrate, and which concentrates are readily emulsifiable into water. These emulsions are useful in general in the agrochemical industry, such as in formulations which comprise a chemical agent which is known in the agrochemical 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 (a) at least one surfactant vic-dicarboxylic acid polyalkyleneoxy half ester derivative of the formula (I) or (II) as defined above; and (b) at least one other surfactant. Particularly suitable emulsifier compositions of this first aspect are those comprising

(a) at least one compound of the formula (I) or (II) above, present as 5 to 90 wt.% of the total composition, preferably as 10 to 75 wt.%; and

(b) at least one other surfactant, present as 10 to 90 wt.% of the total, preferably as 10 to 70 wt.%.

The balance of the composition may be a water miscible liquid and/or water imiscible, e.g. organic, liquid. This may be desirable if the viscosity of the composition would otherwise be inconveniently high. 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 WO 94/00508 A, but preferred surfactants of this type include mono- and di-ester derivatives within formula (I) or (II) 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 agrochemical industry when used to form an emulsifiable concentrate comprising a chemical agent with activity specific to the intended use of the concentrate. Particular ester derivatives of this type include those in which the alk(en)yl substituent has 10 to 17, preferably 12 to 14 carbon atoms, and especially where it is an alkenyl group. Preferred such vic-dicarboxyiic acid polyalkyleneoxy half ester derivatives also include those in which Z (in formula (la)) is an alkylene oxide (block) (co-)polymer of formula (C_rnH_2rnO)_nR² as defined in which n is preferably 7 to 13 and m is 2 and/or 3 As described in WO 94/00508 A, the alk(en)yl groups in the surfactants of the formula (I) or (II) used in this invention are desirably linear alk(en)yl groups.

The other surfactant(s) may be any which on using the emulsifier composition in the formulation of a concentrate comprising a chemical agent with activity specific to the intended use of the concentrate, will give a concentrate which: (a) is stable and homogeneous for at least 24 hr. after making up; and (b) remains homogenous on dilution with water to a diluted formulation.

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 anionic surfactants include members of the alkarene sulphonate salt group, such as alkyl benzene sulphonate salts having 6 to 16 carbon atoms in its straight chain or branched chain alkyl group, e.g. wherein the alkyl is lauryl (dodecyl), or mixtures thereof; members of the poly(aryiaryl- 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 members of the group of salts of alkoxylated carboxylated alkaryl and fatty alcohols, the latter including e.g. poly(ethylene oxide)C_{12to 15} alcohol methylcarboxylates. Examples of suitable salts include those with an alkali metal cation e.g. sodium or potassium; an alkaline earth metal, e.g. calcium; and 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 an emulsifiable concentrate comprising an agrochemical agent with activity specific to the intended use of the concentrate, 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.

Suitable cationic surfactants 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 15} 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: R²¹.0(X)R²² and/or R²³ - 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 R² C0 in which R²⁴ is an alkyl group having 11 to 22 carbon atoms;

R²² is hydrogen or an alkyl group, a carboxyalkyl group, e.g. carboxyalkyl 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; and R²³ is an alkyl or alkenyl group having 10 to 22 carbon atoms. Examples of suitable groups R²¹ include e.g. sorbitan and lauryl, heptadecyl, heptadecenyl, heptadecadienyl, stearyl and oleyl. Examples of suitable groups R²² include e.g. carboxy-methyl, -ethyl or -propyl, or a salt thereof; and laurate, heptadecanoate, heptadecenoate, heptadecadienoate, stearate or oleate. Examples of suitable X include poly(homoalkylene or mixed alkylene oxide) groups, wherein the alkylene groups each have 2 to 8, preferably 2 to 4, e.g. 2 or 3 carbon atoms, and, when R²¹ is sorbitan, and R²² is fatty acid residue having 10 to 22 carbon atoms, a direct bond.

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; poly(alkoxylated) sorbitan and sorbitol esters; poly(alkoxylated) triglycerides, including e.g. poly(aikoxylated) 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, safflower oil, sesame oil, or (especially) soybean oil; poly(alkoxylated) allyl alcohols; poly(alkoxylated) poly(arylaryl alcohols); and poly(alkylene oxides) including (block) (co-)polymers; in particular those wherein the alkylene groups each have 2 to 4 carbon atoms; and sorbitan esters with up to

30 carbon atoms, such as sorbitan monooleate.

Within preferred emulsifier compositions of the first aspect of the present invention, especially when used for formulations for application in the agrochemical industry, the component (b) (at least one other surfactant) is i at least one non-ionic surfactant, and optionally ii at least one anionic surfactant.

Preferred component (b) non-ionic surfactants then include those of the formula: R²¹0(X)R²² and/or R²³ - N (-XH)₂ as defined above which are indicated as preferred non-ionic surfactants hereinbefore.

Preferred component (b) anionic surfactants then 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.

Preferred emulsifier compositions of this first aspect are those comprising a at least one vic-dicarboxyiic acid polyalkyleneoxy half ester derivative, present as 5 to 90 wt.% of the total concentrate, preferably as 10 to 75 wt.%; and b i at least one non-ionic surfactant, present as 10 to 90 wt. % 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 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. Examples of suitable water miscible liquids which may form the balance of the composition and which may be desirable if the viscosity of the composition would otherwise be inconveniently high include alcohols, including glycois, 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 suitable 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 otherwise be inconveniently high include hydrocarbons, preferably those having 5 to 18 carbon atoms, including aromatic hydrocarbons, straight chain or branched alcohols; optionally hydrogenated vegetable oils, 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; esters (especially a C1-6 ester) of a C8-22 fatty acid, especially a C12-18 fatty acid, e.g. members of the group comprising methyl laurate, heptadecanoate, heptadecenoate, heptadecadienoate, stearate or oleate, in particular methyl laurate and oleate; N-methylpyrrolidone; and isoparaffins; or a mixture thereof. Preferred such liquid materials which may be used include xylene, any mixture of aromatic hydrocarbons, and N-methylpyrrolidone.

According to a second aspect of the invention there is provided an emulsifiable concentrate comprising the emulsifier composition of the first aspect; and

(c) at 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 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 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 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 chemical agent with activity specific and appropriate for the intended use of the composition. These exhibit dispersion even of specific chemical agents, such as Acetochlor and Alachlor herbicides but also pesticides, such as insecticides, fungicides or acaricides, which are known in the agrochemical industry as not usually readily emulsified.

Preferred emulsifiable concentrates of this first aspect are those comprising (a) at least one vic-dicarboxyiic acid polyalkyleneoxy half ester derivative, present as 0.1 to 15 wt.% of the total concentrate, preferably as 0.15 to 10 wt.%; (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 concentrate may be a water miscible liquid and/or water insoluble organic solvent, to aid the dissolution of the chemical agent with activity specific to the intended use of the concentrate or corresponding dilute formulation. It may also be desirable if the viscosity of the concentrate would otherwise be inconveniently high. The concentrate, in particular when used in formulations for application in the agrochemical industry, may comprise one or more such liquid and/or solvent components as 0 to 97, and in particular as 5 to 90 wt.% of the total concentrate. In some intended uses of the concentrates, e.g. in methods of applying formulations of some growth regulators, herbicides, insecticides, fungicides or acaricides, it is preferred that the concentrate has a significant water content, e.g. over 25 wt.% of the total. Such concentrates are in fact concentrated emulsions which are further emulsifiable on being diluted with water to give formulations for applying e.g. over crops. The components and their proportions are preferably chosen such that the concentrate provided by mixing the concentrate components is stable, notwithstanding the water which is thereby introduced. When the concentrate is a concentrated emulsion intended e.g. for use in the agrochemical industry to give formulations for applying over crops, certain emulsifiable concentrates are those in which the components and their proportions are:

(a) at least one vic-dicarboxyiic acid polyalkyleneoxy half ester derivative, present as 0.1 to 15 wt.% of the total concentrate, preferably as 0.2 to 10 wt.%; (b) at least one non-ionic surfactant component as 1 to 25 wt.% of the total emulsifiable concentrate; and (c) no anionic surfactant.

Each of the present concentrates a exhibits dispersion even of specific chemical agents, such as Acetochlor and Alachlor herbicides but also pesticides, such as insecticides, fungicides or acaricides, which are known in the agrochemical industry as not usually readily emulsified by known surfactants, b remains a homogenous concentrate on dilution with water to make the concentrate into a diluted formulation of the present invention for application of the component (c) of the concentrate, without the need for the addition of any further materials to disperse the phase and prevent settling of the phase from the diluted concentrate; 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.

Preferred compositions of the present invention, especially when used for concentrates and formulations of agrochemicals, enable a high loading even of the agents referred to in (a) above, for example herbicides such as Acetochlor and Alachlor. Suitable and preferred vic-dicarboxyiic acid polyalkyleneoxy half-ester derivatives and other surfactants in the concentrate are generally those so described hereinbefore with regard to the emulsifier compositions of the first aspect of the invention.

Examples of suitable water miscible liquids include alcohols, including glycois, e e.g. with straight chain or branched alkyl having 1 to 8 carbon atoms. Preferred examples include isobutanol and propylene glycol. Such liquid may often contain water.

Examples of suitable water insoluble organic solvents which may form part of the balance of the concentrate include hydrocarbons, preferably those having 5 to 18 carbon atoms, including aromatic hydrocarbons, straight chain or branched alcohols; optionally hydrogenated vegetable oils, 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; esters (especially a C, ,_o6 ester) of a C_8lo22 fatty acid, especially a C_{12 to 18} fatty acid, e.g. members of the group comprising methyl laurate, heptadecanoate, heptadecenoate, heptadecadienoate, stearate or oleate, in particular methyl laurate and oleate; N-methylpyrrolidone; and isoparaffins; or a mixture thereof. Preferred such solvent materials which may be used include xylene, any mixture of aromatic hydrocarbons, and N-methylpyrrolidone.

An anti-foam agent may be present. A sufficient quantity to provide an anti-foaming effect for the intended use of the concentrate 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 formulations with a high dispersed phase content. The antifoaming agent(s) is/are preferably one or more polysiloxanes, especially of the type having hydrophilic groups. It is preferably of formula

R*₃ SiO [SiO R* R^**]„Si 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 glycois 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 emulsifiable concentrates to which this invention relates include non-surfactant materials which are conventionally useful in surfactant formulations 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 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 1 wt.% of the total concentrate.

The present emulsifier concentrate may have a pH value within a range of for example 5 (acid) to 9 (alkaline), for example 6 to 8.

The emulsifiable concentrates to which this invention relates may be produced by conventional mixing of the components in any order used conventionally.

In a third 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), (b) and (c), and any other components e.g. solvents and/or any other additives, and stirring until tthhee p prroodduucctt iiss hhoommooggeenneeoouuss.

For emulsifiable concentrates to which this invention relates which are concentrated emulsions, mixing the components in a specific order may be necessary. Such emulsifiable concentrates may have to be produced by separate conventional mixing of a the components of the vehicle liquid, and b the components (a), (b) and (c) and any other components, respectively, to give two separate liquid phases, with stirring until each product is homogeneous. The concentrate is made by careful dispersion of the phase containing the components (a), (b) and (c) in to the other phase. It is 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 emulsion is subsequently left to cool to ambient temperature.

In most applications, the surfactant concentrates of the second aspect present of the invention will suitably be supplied in a their (more concentrated) form and converted to a more dilute form at the point of use in such applications. Good stability in storage of the more concentrated form as supplied before being converted to a more dilute form at the point of use is still required. In a fourth aspect the present invention provides a formulation which is a mixture of the components (a), (b) and (c) of the concentrate according to the second aspect of the present invention with 10 to 10,000 times the total weight of the components (a), (b) and (c) of water, e.g. with 30 to 1 ,000 times the total weight of the components. This formulation according to the fourth 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. solvents and anti-foam agents, which may be designated as components (d).

The formulation 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 concentrate by mixing it with water to form the formulation; or

(ii) mixing components (a), (b) and (c) to form a concentrate and diluting the concentrate with water to form a formulation, as appropriate mixing the components (d) and diluting the mixture of these components with water to form a second mixture, and mixing the first formulation and the second mixture to form the desired formulation according to a fourth aspect of the present invention.

Such a process for preparing the formulation according to the fourth aspect of the present invention forms a fifth aspect of the invention. In all such processes for preparing the formulation according to the invention, the ratio of the weight of water used to the total weight of the components (a), (b) and (c) of the formulations of the second aspect will of course be adjusted as appropriate to give a final formulation of the components (a), (b) and (c) with in the definition above.

In a sixth aspect the present invention also provides a method of applying the formulation according to the fourth 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. 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 (i), the effect of the agrochemical, whether one or more phytoactives, for example growth regulators and/or herbicides, and/or pesticides, for example insecticides, fungicides or acaricides, may be potentiated by the surfactants. In embodiment (ii) the working of the metal may include for example cutting or abrasion.

Within concentrates and formulations of the present invention which comprise as component (c) an agrochemical, this is typically one or more 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 and Trifluralin, and also pesticides, for example insecticides such Propargite and Fenitrothion, and fungicides such as Propiconazole. 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 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 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 references suffixed by 'c' are for comparison purposes.

EXAMPLE 1 Preparation of Emulsifier Compositions The emulsifier compositions shown in Table 1 were made by adding the components in the stated amounts in a simple mixing process with stirring as appropriate. The components in Table 1 are as follows: H1 Half Ester Derivative of the formula:

Y.0₂C.(HR)C.C(HR¹).C0₂(C_mH_2mO)_n.R² where Y is H, one of R and R1 is C^H^ and the other is hydrogen, m is 2, n is about 23 (corresponding to PEG 1000) and R² is H.

A Anionic Surfactant calcium dodecy I benzene sulphonate N Non-Ionic Surfactant Atlas G-5000 surfactant (ICI) W Water Miscible Liquid isobutanol S Solvent Solvesso 100, aromatic hydrocarbon solvent mixture, (Exxon Chemicals)

Table 1

Comp %w/wofComponents No

H1 A N S W

E1 30.0 30.8 13.0 13.0 13.2

E2 10.0 28.0 35.0 15.0 12.0

E3 25.0 33.6 16.0 11.0 14.4

E4 10.0 39.2 27.0 7.0 16.8

E5 10.0 37.8 28.0 8.0 16.2

E6 10.0 36.4 29.0 9.0 15.6

E11c - 30.8 43.0 13.0 13.2

E21c - 28.0 45.0 15.0 12.0

E31c - 33.6 41.0 11.0 14.4

E41c - 39.2 37.0 7.0 16.8

E51c - 37.8 38.0 8.0 16.2

E61c 36.4 39.0 9.0 15.6 EXAMPLE 2 Preparation of Emulsifiable Concentrate and Diluted Formulation; Testing of Formulation The above emulsifier compositions E1 to 6 and E21 c to E61 c were formulated into corresponding concentrates shown in Tables 2, 4, 6 and 8 by adding the components in the stated amounts in a simple mixing process with stirring as appropriate.

The above concentrates were formulated into corresponding diluted formulations by adding the concentrates to water with the following parameters described above the relevant Table in each case as appropriate: to the given % wtivol. dilution rate (suitable for the given desired use of the given (diluted) concentrate), at the given temperature at the given WHO standard hardnesses of 342 and 500 ppm, and with the formulations being left to stand for the given length of time.

The efficacy of each emulsifier composition used in the concentrates shown in Tables 2, 4, 6 and 8 in the formulations corresponding to the concentrates is shown in Tables 3, 5, 7 and 9 respectively, in which the numbering of each formulation corresponds respectively to the numbering of each concentrate, and the figures are the volume of the disperse phase of the concentrate (which contains the components (a), (b) and (c)) which separates from the other phase.

Table 2 ' Concentrate C1 C11

Component wt./vol. of Components

Alachlor (herbicide) 480 g 480 g

E1 40 g

E2 - 40 g xylene to l l to l l

Table 3 2 % wt./vol. dilution at25°C - Standard Water Hardness 342 and 500 ppm

Formulation F1 F11

Hardness cream separation (ml)

342 ppm NS 3.5 C

500 ppm NS 3.5 C

NS = no separation of the emulsion Table 4

Concentrate C2 C3 C2c C3c

Component wt/vol. of Components

Acetochlor (herbicide) 94% active 920g 530g 920g 530g

Safener (phytotoxicity inhibitor) - 70g - 70g

E2 80g - - -

E3 - 80g - -

E21c - - 80g -

E31c - - - 80g

Solvesso 100 - 320g - 320g

Table 5

5 % wt/vol dilution 30°C Standard Water Hardness 342 ppm

Formulation F2 F3 F2c F3c

Standing Time (hr) cream separation (ml)

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

Component Components

Fenitrothion (insecticide) 520g 520g

E3 100g -

E31c - 100g

Solvesso 150 to l l to l l

Solvesso 150 = aromatic hydrocarbon solvent mixture, (Exxon Chemicals)

Table 7 5 % wt./vol. dilution 30^βC Standard Water Hardness 20 and 500 ppm

Formulation F4 F4c

Hardness (ppm) 20 500 20 500

Standing Time (hr) separation (ml)

0.5 NS NS 9 0C 9 0C

2 NS NS 9 C + TOC 5 C +3 OC

24 NS NS 1 C +7 0 8 C NS = no separation of the emulsion

OC = oily cream separation of the emulsion C = cream separation of the emulsion

TOC = trace (< 0.05%) oily cream separation of the emulsion

0 = oil separation of the emulsion

Table 8

Concentrate C5 C6 C7 C51c C61c C71c

Component wt. of Components (g)

Propargite (insecticide) 635 635 635 635 635 635

E4 80 - - - - -

E5 - 80 - - - -

E6 - - 80 - - -

E41c - - - 80 - -

E51c - - - - 80 -

E61c - - - - - 80

Xylene 322 322 322 322 322 322

Table 9 1 % wt./vol. dilution 30°C Standard Water Hardness 342 ppm

Formulation F5 F6 F7 F51c F61c F71c

Standing Time (hr) separation (ml)

0.5 NS NS NS 0.5 C + 0.5 C 1 C + TO + TO TO

1 NS NS NS 0.5 C TC + TC + 0.5 O 1 0 1.2 0

2 NS NS NS 0.5 C TC + TC + 0.5 0 1 0 1 0

4 NS NS NS 0.5C+ TC + TC + 0.5 0 1 0 1 0

24 NS NS NS TC NS 0.5C + 0.7 0

NS = no separation of the emulsion TC = trace (< 0.05%) oily cream separation of the emulsion C = cream separation of the emulsion

TO = trace (< 0.05%) oil separation of the emulsion 0 = oil separation of the emulsion EXAMPLE 3 Preparation of Emulsifier Compositions

The emulsifier compositions shown in Table 10 were made by adding the components in the stated amounts in a simple mixing process with stirring as appropriate. The half ester derivative component H2 in Table 10 is of the formula:

Y.0₂C.(HR)C.C(HR¹).C0₂(C_mH_2n,0)_n.R² where Y is H, one of R and R1 is C₁₄H₂₇ and the other is hydrogen, m is 2, n is about 14 (corresponding to PEG 600) and R² is H.

Table 10

Composition E7 E8 E9

Component % w/w of Components

H2 75 50 -

Atlas G-5000 25 50 100 5

EXAMPLE 4

Preparation of Emulsifiable Concentrate (Concentrated Emulsion) and Diluted Formulation;

Testing of Formulation

The above emulsifier compositions E7 to E9 were formulated into corresponding concentrates o 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 50°C with stirring until 5 each product was homogeneous, to give two separate liquid phases, ('phase B' and 'phase

A respectively).

Phase B was then carefully dispersed in Phase A by adding it slowly to Phase A with constant stirring and keeping the temperature at 50^βC. The resultant mixture of phase B and phase A was then homogenised with high shear mixing, and the resultant concentrated 0 emulsion was allowed to cool to ambient temperature under low energy mixing.

The viscosity modifier was then dispersed in the emulsion under high shear mixing to give a thickened emulsion.

The above emulsifier compositions E7 to E9 were also formulated into corresponding concentrates shown in Tables 14 and 17 by mixing the components in the stated amounts in the above mixing 5 process. The efficacy of each emulsifier composition used in the concentrates is shown in Tables

12, 15 and 18 respectively. Table 11

Concentrate CE1 CE2 CE3

Component wt./vol. of Components

Acetochlor (herbicide) 93% active 538g 538g 538g

Safener (phytotoxicity inhibitor) 52g 52g 52g poly(ethoxylated) soybean oil 15g 15g 15g

E7 50g - -

E8 - 50g -

E9 - - 50g propylene glycol 50g 50g 50g

Rhodopol 23 (viscosity modifier) ig 19 ig water to ll to ll to ll

Table 12

Formulation CE1 CE2 CE3

Temp. (°C) Time (wk) separation

NS NS NS

22 NS NS NS

40 NS NS NS

NS = no separation of the emulsion The above concentrates were formulated into corresponding diluted formulations by adding the concentrates to water with following parameters described above the relevant Table 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 given length of time.

The efficacy of each emulsifier composition used in the concentrates shown in Tables 11 , 14 and

17 in the formulations corresponding to the concentrates is shown in Tables 13, 16 and 19 respectively, in which the numbering of each formulation corresponds respectively to the numbering of each concentrate, and the figures are the volume of the disperse phase of the concentrate (which contains the components (a), (b) and (c)) which separates from the other phase. Table 13 2 % wt./vol. dilution 22°C Standard Water Hardness 342 ppm

Formulation CF1 CF2 CF3

Temp (°C) Time (wk) separation (ml)

0 NS TC 0.15C

22 4 TC TC 0.1 C

40 4 TC TC 0.1 C

TC = trace (< 0.05%) cream separation of the emulsion C = cream separation of the emulsion

Table 14

Concentrate CE4 CE5 CE6

Component wt/vol of Components

Trifluralin (herbicide) 96% active 500g 500g 500g

E7 50g - -

E8 - 50g -

E9 - - 50g propylene glycol 20g 20g 20g xylene 205g 205g 205g water to ll to ll to l l

Table 15

NS = no separation of the emulsion

Table 16

2 % wt./vol. dilution 22°C Standard Water Hardness 342 ppm

C = cream separation of the emulsion Table 17

Concentrate CE7 CE8 CE9

Component wt./vol. of Components

Propiconazole (fungicide) 60% active 417g 417g 417g

E7 100g - -

E8 - 100g -

E9 - - 100g propylene glycol 100g 100g 100g xylene 183g 183g 183g water to l l to ll to ll

Table 18

Formulation CE7 CE8 CE9

Temp (°C) Time (wk) separation

0 NS NS NS

22 4 NS NS NS

40 4 NS NS NS

NS = no separation of the emulsion

Table 19 2 % wt./vol. dilution 22°C Standard Water Hardness 342 ppm

Formulation CF1 CF2 CF3

Temp (°C) Time (wk) separation (ml)

0 NS NS 2 C

22 4 NS NS I

40 4 NS TC 1 C

C = cream separation of the emulsion I = impossible to emulsify

Claims

Claims:

1 A composition which comprises

(a) at least one surfactant vic-dicarboxyiic acid polyalkyleneoxy half ester derivative of the formula (I) or (II): Y.A\OC.(HR)C.C(HR¹).CO.A.(C H_2mO)_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 C_1β;

A¹ is -0-, -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 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 (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 (la) or (I la):

(la) and (Ma): R¹ - CH(CO.AY) - CH₂ CO.AZ (la) in which Z is a group of formula (C_mH_2rnO)_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)_πR² 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(COAΥ) - CH₂-CO.A - D - A.OC - CH₂ - CH(COAΥ) - R¹ (lla) in which D is a group of formula (C_mH_2n,0)_n C_pH_2p - 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 (I) or (II) 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 (I) or (II) 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.

5 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:

R²¹.0(X)R^Ω 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 R² CO 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. An emulsifyable concentrate comprising

(a) at least one vic-dicarboxyiic 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.

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.

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 glycois; and/or one or more water imiscible liquid selected from hydrocarbons; straight chain or branched alcohols; optionally hydrogenated vegetable oils; C_{1 to6} esters of C_8lo22 fatty acids; N-methylpyrroiidone; and isoparaffins; or a mixture thereof.