WO2016086726A1

WO2016086726A1 - An agrochemical composition, a method of preparing the same and the use thereof

Info

Publication number: WO2016086726A1
Application number: PCT/CN2015/092256
Authority: WO
Inventors: James Timothy Bristow
Original assignee: Rotam Agrochem International Company Limited
Priority date: 2014-12-02
Filing date: 2015-10-20
Publication date: 2016-06-09
Also published as: GB201421408D0; GB2533083A; CN105638656A; AR102564A1; TWI688338B; GB2533083B; CN105638656B; BR102015030210A2; TW201628496A; BR102015030210B1

Abstract

An agrochemical composition is provided, the composition comprising at least one dipropylene/diethylene glycol dibenzoate, at least one active ingredient and at least one emulsifier. The presence of the dipropylene/diethylene glycol dibenzoate reduces the irritancy of the composition especially reducing the eye irritation caused by the active ingredient and the emulsifier. The composition is preferably a liquid concentrate, in particular an emulsion concentrate (EC) formulation.

Description

AN AGROCHEMCIAL COMPOSITION, A METHOD OF PREPARING THE SAME AND THE USE THEREOF

The present invention relates to an agrochemical composition. The present invention further relates to a method of preparing the aforementioned composition and its use in crop protection. The present invention is also related to the reduction of eye irritation caused by the agrochemical composition, in particular a liquid concentrate formulation of the composition.

Emulsifiable concentrate (EC) formulations are a very popular formulation type for the preparation and use of compositions comprising agrochemically active components. However, such formulations require substantial quantities of organic solvents, such as aromatic hydrocarbons, chlorinated hydrocarbons, and the like, together with anionic and non-ionic emulsifiers to stabilize the active ingredients in the formulations. With this combination of components, the formulated products are of a good quality and generally perform well in field applications. However, most of the products formulated in this manner cause severe eye irritation to users. As a result, such formulations are often classed as being hazardous. For example, emulsifiable concentrates are classified as Toxicity Category I (Cat I) in Brazil. Knowing that formulations labeled with “Toxicity Category I” may cause eye irritation, farmers and other end users are reluctant to purchase and use such products.

The prior art does not offer a solution for the problems of using solvents and emulsifiers in emulsion concentrate (EC) formulations. At present, commercial emulsion concentrate formulations cause severe eye irritation. As a result, attempts have been made to avoid the use organic solvents such as aromatic or chlorinated hydrocarbons, and instead use alternative solvents having reduced toxic effects. Examples of such alternative solvents are aliphatic hydrocarbons, alcohols, glycols, polyglycols, glycol ethers, ketones, as well as polar solvents with a high solvent power, such as gamma-butyrolactone, N-methyl pyrrolidone, and the like.

However, eye irritation is caused not only by the solvents, but can also be caused by active ingredients and emulsifiers present in the formulation. The emulsifiers, for example anionic emulsifiers, are important to increase spontaneous dispersibility of the formulation in water and stability of the diluted formulation. Calcium alkylbenzene sulfonate is one type of anionic emulsifier frequently used in emulsion concentrate formulations. However, these kind of anionic emulsifiers cause severe eye irritation. Consequently, even if the composition is formulated with solvents that are non-irritant to the eyes, the formulation may still cause severe eye irritation because of the presence of active ingredients and emulsifiers.

WO 02/045507 describes a microemulsifiable concentrate comprising a hydrophobic active ingredient and at least one surfactant dissolved in a solvent system comprising a hydrophobic water-insoluble alkyl alkanolate, as a first solvent, and a polyhydric alcohol or a condensate of polyhydric alcohols and mixtures thereof, as a second solvent. The formulations are reported to exhibit reduced eye irritation.

WO 2006/002984 discloses a liquid concentrate composition comprising a water-insoluble active ingredient, at least one organic solvent having a water solubility of at least 10 g/L, and at least one non-ionic block copolymer comprising at least one polyethylene oxide moiety and at least one hydrophobic polyether moiety. The organic solvent is capable of dissolving the active ingredient. The problem of eye irritation is not discussed or otherwise addressed in WO 2006/002984.

There is an ongoing need to find safe, preferably substantially inert, components for formulating liquid concentrates, with a view to providing a formulation which will not irritate the eyes. It would be advantageous if the formulation components could also reduce the irritancy of the active ingredients and emulsifiers to the eyes of users.

It has now been surprisingly found that certain dipropylene/diethylene glycol dibenzoates are not only non-irritant to the eyes, but also reduce the eye irritation caused by the active ingredients and emulsifiers present in the formulation.

Accordingly, in a first aspect, the present invention provides an agrochemical composition comprising at least one dipropylene/diethylene glycol dibenzoate, at least one active ingredient and at least one emulsifier.

Dipropylene/diethylene glycol dibenzoates are themselves not irritants. It has been found that the presence of the dipropylene/diethylene glycol dibenzoate in the agrochemical composition significantly reduces the toxicity of the formulation, in particular reducing the irritancy of the formulation to the eyes. In particular, it appears that the dipropylene/diethylene glycol dibenzoate reduces or substantially negates the irritancy of the active ingredients and emulsifiers to the eyes.

As described in more detail below, it has been found that dipropylene/diethylene glycol dibenzoate is effective in reducing the irritancy of liquid concentrate formuilations. Thus, the inclusion of dipropylene/diethylene glycol dibenzoate in liquid concentrates reduces the eye irritancy of the formulation. In addition, it has been found that the use of dipropylene/diethylene glycol dibenzoate in liquid concentrate pesticidal formulations is environmentally friendly.

The dipropylene/diethylene glycol dibenzoate is present in the composition of the present invention in an amount sufficient to reduce the irritancy of the other components in the composition, in particular the eye irritation of the active ingredients and emulsifiers present. The amount of dipropylene/diethylene glycol dibenzoate required will be determined by the particular active ingredients and emulsifiers employed in the composition and their amounts. The amount of the dipropylene/diethylene glycol dibenzoate required to reduce or eliminate the irritancy to the eyes of the formulation may be determined without undue experimentation by the skilled person, for example by trial and error.

The dipropylene/diethylene glycol dibenzoate is effective to reduce the eye irritancy of the active ingredient when present in a wide range of weight ratios to the active ingredient. The dipropylene/diethylene glycol dibenzoate is preferably present in an amount at least equal to or, more preferably in excess of the amount of the active ingredient. The weight ratio of the dipropylene/diethylene glycol dibenzoate to the active ingredient is preferably at least 1∶1, in some preferred embodiments at least 1∶2, in other preferred embodiments at least 1∶3. In particular, the dipropylene/diethylene glycol dibenzoate is preferably present in an amount to provide a weight ratio of the active ingredient to the dipropylene/diethylene glycol dibenzoate from 1∶1 to 1∶100, preferably from 1∶1 to 1∶90, more preferably from 1∶2 to 1∶20, still more preferably from 1∶3 to 1∶15.

The dipropylene/diethylene glycol dibenzoate is effective in reducing the eye irritancy of emulsifiers in a wide range of weight ratios. In many embodiments, the dipropylene/diethylene glycol dibenzoate is present in the composition in an amount at least equal to, more preferably in excess, of the total amount of the emulsifier present. The weight ratio of the dipropylene/diethylene glycol dibenzoate to the total emulsifier content of the composition is preferably at least 0.1, more preferably at least 0.2. The weight ratio of the dipropylene/diethylene glycol dibenzoate to the total emulsifier content of the composition may be from 0.1 to 60, preferably from 0.2 to 60. In a number of embodiments, a weight ratio of from 0.3 to 10, more particularly from 0.4 to 8 has been found to be effective. Higher amounts of the dipropylene/diethylene glycol dibenzoate may be employed, for example in weight ratios to the emulsifier content of from 10 to 50. In many embodiments, a weight ratio of dipropylene/diethylene glycol dibenzoate to the emulsifier content of less than 15, more preferably less than 10 is effective.

The dipropylene/diethylene glycol dibenzoate may be present in the composition in an amount of at least 2％by weight, preferably from 10％by weight, more preferably from 20％by weight. In preferred embodiments, the dipropylene/diethylene glycol dibenzoate is present in the composition in an amount of from 2 to 90％by weight, preferably from 10 to 80％be weight, more preferably from 20 to 70％by weight of the composition.

The composition may comprise dipropylene glycol dibenzoate, diethylene glycol dibenzoate or a combination of dipropylene glycol dibenzoate and diethylene glycol dibenzoate.

As mentioned above, the present invention provides an agrochemical composition comprising at least one agrochemically active ingredient. It has been found that the presence of one or more dipropylene/diethylene glycol dibenzoates is effective in reducing the irritancy of a range of active ingredients. Suitable active ingredients for use in the composition of the present invention are well known in the art and are commercially available.

As noted above, the dipropylene/diethylene glycol dibenzoates have been found to be effective in reducing the toxicity, in particular the irritancy to eyes, of a range of active ingredients. In one embodiment, the composition of the present invention comprises, as an active ingredient clomazone (2- (2-chlorobenzyl) -4, 4-dimethyl-1, 2-oxazolidin-3-one) .

It has also been found that the dipropylene/diethylene glycol dibenzoates are effective in reducing the toxicity, in particular the irritancy to eyes, of pyrethroid ester acaricides and insecticides. Such pyrethroids are known in the art and include, for example, cyhalothrin ( (RS) -α-cyano-3-phenoxybenzyl (Z) - (1RS, 3RS) -3- (2-chloro-3, 3, 3-trifluoroprop-1-enyl) -2, 2-dimethylcyclopropanecarboxylate) , cypermethrin ( (RS) -α-cyano-3-phenoxybenzyl (1RS, 3RS； 1RS, 3SR) -3- (2, 2-dichlorovinyl) -2, 2-dimethyl cyclopropanecarboxylate) , deltamethrin ( (S) -α-cyano-3-phenoxybenzyl (1R, 3R) -3- (2, 2-dibromovinyl) -2, 2-dimethylcyclopropanecarboxylate) , lambda-cyhalothrin ( (S) -α-cyano-3-phenoxybenzyl (Z) - (1R, 3R) -3- (2-chloro-3, 3, 3-trifluoroprop-1-enyl) -2, 2-dimethylcyclopropanecarboxylate and (R) --cyano-3-phenoxybenzyl (Z) - (1S, 3S) -3- (2-chloro-3, 3, 3-trifluoroprop-1-enyl) -2, 2-dimethylcyclopropane carboxylate) . A particularly suitable pyrethroid is bifenthrin.

In one embodiment, the composition of the present invention comprises, as an active ingredient pyriproxyfen (4-phenoxyphenyl (RS) -2- (2-pyridyloxy) propyl ether) .

It has also been found that the dipropylene/diethylene glycol dibenzoates are effective in reducing the toxicity, in particular the irritancy to eyes, of cyclohexime oxime herbicides, including alloxydim (methyl (1RS) -3- [ (E) -1 - (allyloxyimino) butyl] -4-hydroxy-6, 6-dimethyl-2-oxocyclohex-3-enecarboxylate) , butroxydim ( (5RS) -5- (3-butyryl-2, 4, 6-trimethylphenyl) -2- [ (EZ) -1- (ethoxyimino) propyl] -3-hydroxycyclohex-2-en-1-one) , clethodim ( (5RS) -2- { (1EZ) -1- [ (2E) -3-chloroallyloxy imino] propyl} -5- [ (2RS) -2- (ethylthio) propyl] -3-hydroxycyclohex-2-en-1-one) , cloproxydim ( (5RS) -2- { (EZ) -1- [ (2EZ) -3-chloroallyloxyimino] butyl} -5- [ (2RS) -2- (ethyl thio) propyl] -3-hydroxycyclohex-2-en-1-one) , cycloxydim ( (5RS) -2- [ (EZ) -1- (ethoxy imino) butyl] -3-hydroxy-5- [ (3RS) -thian-3-yl] cyclohex-2-en-1-one) , profoxydim ( (5RS) -2- { (EZ) -1- [ (2RS) -2- (4-chlorophenoxy) propoxyimino] butyl} -3-hydroxy-5- [ (3RS) -thian-3-yl] cyclohex-2-en-1-one) , sethoxydim ( (5RS) -2- [ (EZ) -1- (ethoxyimino) butyl] -5- [ (2RS) -2- (ethylthio) propyl] -3-hydroxycyclohex-2-en-1-one) , tepraloxydim ( (5RS) -2- { (EZ) -1- [ (2E) -3-chloroallyloxyimino] propyl} -3-hydroxy-5-perhydropyran-4-ylcyclohex-2 -en-1-one) , and tralkoxydim ( (RS) -2- [ (EZ) -1- (ethoxyimino) propyl] -3-hydroxy-5-mesitylcyclohex-2-en-1-one) . The dipropylene/diethylene glycol dibenzoates are particularly effective in reducing the irritancy of clethodim.

It has further been found that the dipropylene/diethylene glycol dibenzoates are effective in reducing the toxicity, in particular the irritancy to eyes, of benzoylphenylurea chitin synthesis inhibitors , including bistrifluron (1- [2-chloro-3, 5-bis (trifluoromethyl) phenyl] -3- (2, 6-difluorobenzoyl) urea) , chlorbenzuron (1- (2-chlorobenzoyl) -3- (4-chlorophenyl) urea) , chlorfluazuron (1- [3, 5 -dichloro-4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenyl] -3- (2, 6-difluorobenzoyl) urea) , dichlorbenzuron (1- (4-chlorophenyl) -3- (2, 6-dichlorobenzoyl) urea) , diflubenzuron (1- (4-chlorophenyl) -3- (2, 6-difluorobenzoyl) urea) , flucycloxuron (1- {α- [ (EZ) -4-chloro-α-cyclopropylbenzylideneaminooxy] -p-tolyl} -3- (2, 6-difluoro benzoyl) urea (ratio 50–80％ (E) -and 50–20％ (Z) -isomers) , flufenoxuron (1- [4- (2-chloro-α, α, α-trifluoro-p-tolyloxy) -2-fluorophenyl] -3- (2, 6-difluoro benzoyl) urea) , hexaflumuron (1- [3, 5-dichloro-4- (1, 1, 2, 2-tetrafluoroethoxy) phenyl] -3- (2, 6-difluorobenzoyl) urea) , lufenuron ( (RS) -1- [2, 5-dichloro-4- (1, 1, 2, 3, 3, 3-hexa fluoropropoxy) phenyl] -3- (2, 6-difluorobenzoyl) urea) , novaluron ( (RS) -1- [3-chloro-4- (1, 1, 2-trifluoro-2-trifluoromethoxyethoxy) phenyl] -3- (2, 6-difluorobenzoyl) urea) , noviflumuron (1- {3, 5-dichloro-2-fluoro-4- [ (RS) -1, 1, 2, 3, 3, 3-hexafluoropropoxy] phenyl} -3- (2, 6-difluorobenzoyl) urea) , penfluron (1- (2, 6-difluorobenzoyl) -3- (α, α, α-trifluoro-p-tolyl) urea) , teflubenzuron (1- (3, 5-dichloro-2, 4-difluorophenyl) -3- (2, 6-difluorobenzoyl) urea) , and triflumuron (1- (2-chlorobenzoyl) -3- (4-trifluoromethoxyphenyl) urea) . The dipropylene/diethylene glycol dibenzoates are particularly effective in reducing the irritancy of lufenuron.

It has further been found that the dipropylene/diethylene glycol dibenzoates are effective in reducing the toxicity, in particular the irritancy to eyes, of avermectin insecticides, acaracides and nematacides, including abamectin (mixture of ≥ 80％ (10E, 14E, 16E) - (1R, 4S, 5′S, 6S, 6′R, 8R, 12S, 13S, 20R, 21R, 24S) -6′- [ (S) -sec-butyl] -21, 24 -dihydroxy-5′, 11, 13, 22-tetramethyl-2-oxo- (3, 7, 19-trioxatetracyclo [15.6.1.1^4, 8.0^20, 24] pentacosa-10, 14, 16, 22-tetraene) -6-spiro-2′- (5′, 6′-dihydro-2′H-pyran) -12-yl 2, 6-dideoxy-4-O- (2, 6-dideoxy-3-O-methyl-α-L-arabino-hexopyranosyl) -3-O-methyl-α-L-arabino-hexopyranoside and ≤ 20％ (10E, 14E, 16E) - (1R, 4S, 5′S, 6S, 6′R, 8R, 12S, 13S, 20R, 21R, 24S) -21, 24-dihydroxy-6′-isopropyl-5′, 11, 13, 22-tetramethyl-2-oxo- (3, 7, 19-trioxatetracyclo [15.6.1.1^4, 8.0^20, 24] pentacosa-10, 14, 16, 22-tetraene) -6-spiro-2′- (5′, 6′-dihydro-2′H-pyran) -12-yl 2, 6-dideoxy-4-O- (2, 6-dideoxy-3-O-methyl-α-L-arabino-hexopyranosyl) -3-O-methyl-α-L-arabino-hexopyranoside) , doramectin ( (10E, 14E, 16E) - (1R, 4S, 5′S, 6S, 6′R, 8R, 12S, 13S, 20R, 21R, 24S) -6′-cyclohexyl-21, 24-dihydroxy-5′, 11, 13, 22-tetramethyl-2-oxo- (3, 7, 19-trioxatetracyclo [15.6.1.1^4, 8.0^20, 24] pentacosa-10, 14, 16, 22-tetraene) -6-spiro-2′- (5′, 6′-dihydro-2′H-pyran) -12-yl 2, 6-dideoxy-4-O- (2, 6-dideoxy-3-O-methyl-α-L-arabino-hexopyranosyl) -3-O-methyl-α-L-arabino-hexopyranoside) , emamectin (mixture of ≥ 90％ (10E, 14E, 16E) - (1R, 4S, 5′S, 6S, 6′R, 8R, 12S, 13S, 20R, 21R, 24S) -6′- [ (S) -sec-butyl] -21, 24 -dihydroxy-5′, 11, 13, 22-tetramethyl-2-oxo- (3, 7, 19-trioxatetracyclo [15.6.1.1^4, 8.0^20, 24] pen tacosa-10, 14, 16, 22-tetraene) -6-spiro-2′- (5′, 6′-dihydro-2′H-pyran) -12-yl 2, 6-dideoxy-3-O-methyl-4-O- (2, 4, 6-trideoxy-3-O-methyl-4-methylamino-α-L-lyxo-hexapyranosyl) -α -L-arabino-hexapyranoside and ≤ 10％ (10E, 14E, 16E) - (1R, 4S, 5′S, 6S, 6′R, 8R, 12S, 13S, 20R, 21R, 24S) -21, 24-dihydroxy-6′-isopropyl-5′, 11, 13, 22-tetramethyl-2-oxo- (3, 7, 19-trioxatetracyclo [15.6.1.1^4, ⁸.0^20, ²⁴] pentacosa-10, 14, 16, 22-tetraene) -6-spiro-2′- (5′, 6′-dihydro-2′H-pyran) -12-yl 2, 6-dideoxy-3-O-methyl-4-O- (2, 4, 6-trideoxy-3-O-methyl-4-methylamino-α-L-lyxo-hexapyranosyl) -α-L-arabino-hexa pyranoside) , eprinomection (mixture of (10E, 14E, 16E) - (1R, 4S, 5′S, 6S, 6′R, 8R, 12S, 13S, 20R, 21R, 24S) -6′- [ (S) -sec-butyl] -21, 24-dihydroxy-5′, 11, 13, 22-tetramethyl-2-o xo- (3, 7, 19-trioxatetracyclo [15.6.1.1^4, 8.0^20, 24] pentacosa-10, 14, 16, 22-tetraene) -6-spiro-2′- (5′, 6′-dihydro-2′H-pyran) -12-yl 4-O- (4-acetamido-2, 4, 6-trideoxy-3-O-methyl-α-L-lyxo-hexopyranosyl) -2, 6-dideoxy-3-O-methyl-α-L-arabino-hexopyranoside (major component) and (10E, 14E, 16E) - (1R, 4S, 5′S, 6S, 6′R, 8R, 12S, 13S, 20R, 21R, 24S) -21, 24-dihydroxy-6′-isopropyl-5′, 11, 13, 22-tetramethyl-2-oxo- (3, 7, 19-trioxatet racyclo [15.6.1.1^4, 8.0^20, 24] pentacosa-10, 14, 16, 22-tetraene) -6-spiro-2′- (5′, 6′-dihydro-2′H -pyran) -12-yl 4-O- (4-acetamido-2, 4, 6-trideoxy-3-O-methyl-α-L-lyxo-hexopyranosyl) -2, 6-dideoxy-3-O-methyl-α-L-arabino-hexopyranoside (minor component) ) , ivermectin (mixture of (10E, 14E, 16E) - (1R, 4S, 5′S, 6R, 6′R, 8R, 12S, 13S, 20R, 21R, 24S) -6′- [ (S) -sec-butyl] -21, 24-dihydroxy-5′, 11, 13, 22-tetramethyl-2-oxo- (3, 7, 19-trioxatetracyclo [15.6.1.1^4, 8.0^20, 24] pentacosa-10, 14, 16, 22-tetraene) -6-spiro-2′- (t etrahydropyran) -12-yl 2, 6-dideoxy-4-O- (2, 6-dideoxy-3-O-methyl-α-L-arabino-hexopyranosyl) -3-O-methyl-α-L-arabino-hexopyranoside and (10E, 14E, 16E) - (1R, 4S, 5′S, 6R, 6′R, 8R, 12S, 13S, 20R, 21R, 24S) -21, 24-dihydroxy-6′-isopropyl-5′, 11, 13, 22-tetra methyl-2-oxo- (3, 7, 19-trioxatetracyclo [15.6.1.1^4, 8.0^20, 24] pentacosa-10, 14, 16, 22-tetraen e) -6-spiro-2′- (tetrahydropyran) -12-yl 2, 6-dideoxy-4-O- (2, 6-dideoxy-3-O-methyl-α-L-arabino-hexopyranosyl) -3-O-methyl-α-L-arabino-hexopyranoside) , and selamectin ( (10E, 14E, 16E, 21Z) - (1R, 4S, 5′S, 6R, 6′S, 8R, 12S, 13S, 20R, 21R, 24S) -6′-cyclohexyl-24-hydroxy-21-hydroxyimino-5′, 11, 13, 22-tetramethyl-2-oxo- (3, 7, 19-trioxatetracyclo [15.6.1.1^4, 8.0^20, 24] pentacosa-10, 14, 16, 22-tetraene) -6-spiro-2′- (tetrahydropyran) -12-yl 2, 6-dideoxy-3-O-methyl-α-L-arabino-hexopyranoside) . The dipropylene/diethylene glycol dibenzoates are particularly effective in reducing the irritancy of abamectin.

It has been found that the composition of the present invention is particularly effective when the active ingredient is selected from clomazone, bifenthrin, pyriproxyfen, clethodim, lufenuron, abamectin and mixtures thereof.

The present invention provides an agrochemical composition further comprising at least one emulsifier. Suitable emulsifiers for use in the composition are well known in the art and are commercially available. The emulsifier or emulsifier mixture is selected to have good emulsifying, dispersing and wetting abilities in the formulation employed. The emulsifier may be selected from non-ionic emulsifiers, ionic emulsifiers, cationic emulsifiers and mixtures thereof.

Preferred non-ionic emulsifiers are those selected from alcohol alkoxylates, alkylphenol ethoxylates, alkylpolysaccharides, amine ethoxylates, castor oil ethoxylates, sorbitan fatty acid ester ethoxylates, and polyoxyethylene fatty acids.

Preferred anionic emulsifiers are water-soluble soaps as well as water-soluble synthetic emulsifiers. Typical examples of anionic emulsifiers are selected from amine alkylbenzenesulfonate, ammonium dodecylbenzene sulfonate, calcium alkylsulphonate, and calcium alkylbenzenesulfonate.

Preferred cationic emulsifiers in the composition of the present invention may be quaternary ammonium salts having the following general formula:

in which R₁, R₂, R₃ or R₄ each represents at least one C₈ to C₂₂ alkyl radical, or R₁, R₂, R₃ or R₄ each represents an unsubstituted or halogenated lower alkyl, benzyl, or hydroxyl-lower alkyl radicals； and X represents a halide, for example a chlorine ion, methyl sulfate or ethyl sulfate. Examples of preferred cationic emulsifiers are polyoxyethylene quaternary and polyoxyethylene tallow ethylmonium ethosulfate, stearyltrimethylammonium chloride, benzyl bis (2-chloroethyl) ethylammonium bromide.

The emulsifier or emulsifier mixture may be present in the composition in any suitable amount. Preferably, the emulsifier is present in the composition in an amount of at least 5％by weight, more preferably at least 10％by weight, still more preferably at least 15％by weight. Preferably, the one or more emulsifiers are present in an amount in the range of from 5 to 40％by weight, more preferably from 5 to 35％by weight, still more preferably from 10 to 30％by weight of the composition. An amount of one or more emulsifiers of from 20 to 30％by weight of the composition has been found to be particularly suitable in many embodiments.

In addition to dipropylene/diethylene glycol dibenzoate, at least one active ingredient and at least one emulsifier, the compositions of the present invention may also comprise other components as is known in the art, depending upon the type of formulation being employed.

For example, the composition may comprise one or more solvents, in particular one or more polar or non-polar organic solvents. Suitable solvents are known in the art and are commercially available. Suitable polar or non-polar organic solvents include alcohols, such as benzyl alcohol, alkyl pyrrolidones, such as N-methylprrolidone, N-octylpyrrolidone, or one or more lactones, such as γ-butyrolactone； aromatic hydrocarbons and mixtures thereof, such as the commercially available solvent compositions SOLVESSO^TM 100 and SOLVESSO^TM 200, and dimethyl sulfoxide.

Further components that may be included in the composition are well known in the art and include one or more stabilizers, one or more thickeners, and the like. Such components are commercially available and their uses in formulating the agrochemical compositions are recognized and understood by the person skilled in the art.

The composition of the present invention may be prepared in any suitable form. The composition of the present invention is preferably a liquid concentrate, in particular an emulsifiable concentrate (EC) formulation. The liquid concentrate formulations may comprise active ingredients that are sparingly water-soluble or water-insoluble. The liquid concentrate formulations are preferably those for dispersion in water, prior to use.

In a further aspect, the present invention provides a liquid concentrate composition comprising at least one dipropylene/diethylene glycol dibenzoate, at least one active ingredient and at least one emulsifier.

The present invention also provides, in a further aspect, a method for preparing an agrochemical composition, the method comprising combining at least one dipropylene/diethylene glycol dibenzoate with at least one active ingredient and at least one emulsifier.

The compositions of the present invention may be prepared using techniques known in the art. A particularly preferred method for preparing the liquid concentrate composition is as follows:

Each component is provided according to the weight fraction required in the final composition. First, a solvent and dipropylene/diethylene glycol dibenzoate are added to a suitable mixing vessel, for example a blending tank, and mixed to form a mixture. The active ingredient is then added to the mixture and mixed continuously (typically for about 30 minutes) until the active ingredient dissolves completely in the solvent. Thereafter, the one or more emulsifiers and the further components, if present, are added to the mixture and mixed (typically for about an hour) to ensure homogeneity.

In a further aspect, the present invention provides the use of at least one dipropylene/diethylene glycol dibenzoate to reduce the eye irritancy of an active ingredient and an emulsifier in an agrochemical formulation.

In a further aspect, the present invention provides a method for reducing the eye irritation of liquid formulations caused by the active ingredients and emulsifiers, the method comprising adding at least one dipropylene/diethylene glycol dibenzoate to the formulation in an amount sufficient to reduce the eye irritancy of the formulation.

In a still further aspect, the present invention provides a method for treating pests at a locus comprising applying to the locus a composition as hereinbefore described.

Embodiments of the present invention will now be described, for illustration purposes only, by way of the following examples.

EXAMPLES

In each of the following examples, a composition was prepared according to the following general methodology:

In general, each component was added to a vessel in an amount based upon the particular composition recipe indicate. More particularly, first, the solvent and dipropylene/diethylene glycol dibenzoate were added to a blending tank in the specified amounts and mixed to form a mixture. At least one active ingredient was added to the mixture and mixed continuously for about 30 minutes until the active ingredient was dissolved completely. Thereafter, the emulsifier was added to the blending tank and the resulting mixture mixed continuously for about an hour until the mixture was uniform, after which mixing was stopped. Finally, the mixture was discharged from the blending tank.

The eye irritation potential of each formulation was determined according to the method described by N. P. Luepke: ‘Hen's Egg Chorio Allantoic Membrane Test for Irritation Potential’ , Fd. Chem. Toxic. 23 (1985) , pp 287-291, (hereafter the ‘HET-CAM Test’ ) , which was modified according to the method of H. Spielmann (H. Spielmann: Methods in Molecular Biology 43 (1995) pp. 199-204, and H. Spielmann et al. ATLA 24 (1996) , pp. 741-858) .

In the HET-CAM Test, a chorioallantoic membrane (CAM) was treated with samples of each composition. The chorioallantoic membrane was then observed for 5 minutes. The severity of haemorrhage, lysis and coagulation were examined. The samples were categorized as follows:

Category 0 (Cat 0) : strongly irritant

Category I (Cat I) : irritant

Category II (Cat II) : moderate irritant

Category III (Cat III) : non-irritant

Samples and controls were prepared for each formulation. The eye irritation potential of the samples and controls were examined as mentioned above. In each example, the control composition is identical to the sample composition, with the exception that dipropylene/diethylene glycol dibenzoate was omitted.

Example 1

Emulsion concentrate compositions Sample 1 and Control 1 were prepared according to the recipe specified in Table 1 below. The ratio of bifenthrin and dipropylene glycol dibenzoate of Sample 1 was approximately 1∶13. The eye irritancy of Sample 1 was compared with that of Control 1 (that is the composition of Sample 1 without the addition of dipropylene glycol dibenzoate) .

Table 1

Example 2

Emulsion concentrate compositions Sample 2 and Control 2 were prepared according to the recipe set out in Table 2 below. The ratio of bifenthrin and diethylene glycol dibenzoate of Sample 2 was approximately 1∶1. The eye irritation of Sample 2 was compared with that of Control 2 (without the addition of diethylene glycol dibenzoate) .

Table 2

Example 3

Emulsion concentrate compositions Sample 3 and Control 3 were prepared with components according to Table 3 below. The ratio of bifenthrin and dipropylene glycol dibenzoate of Sample 3 was approximately 1∶2. The eye irritation of Sample 3 was compared with that Control 3 (without the addition of dipropylene glycol dibenzoate) .

Table 3

Example 4

Emulsion concentrate compositions Sample 4 and Control 4 were prepared with components as set out in Table 4 below. The ratio of clethodim and diethylene glycol dibenzoate of Sample 4 was approximately 1∶3. The eye irritation of Sample 4 was compared with that of Control 4 (without the addition of diethylene glycol dibenzoate) .

Table 4

Example 5

Emulsion concentrate compositions Sample 5 and Control 5 were prepared with components according to Table 5. The ratio of clomazone and dipropylene glycol dibenzoate of Sample 5 was approximately 1∶6. The eye irritation of Sample 5 was compared with that of Control 5 (without the addition of dipropylene glycol dibenzoate) .

Table 5

Example 6

Emulsion concentrate compositions Sample 6 and Control 6 were prepared with components according to Table 6 below. The ratio of pyriproxyfen and dipropylene glycol dibenzoate of Sample 6 was approximately 1∶5. The eye irritation of Sample 6 was compared with that of Control 6 (without the addition of dipropylene glycol dibenzoate) .

Table 6

Example 7

Emulsion concentrate compositions Sample 7 and Control 7 were prepared with components as set out in Table 7 below. The ratio of pyriproxyfen and diethylene glycol dibenzoate of Sample 7 was approximately 1∶10. The eye irritation of Sample 7 was compared with that of Control 7 (without the addition of diethylene glycol dibenzoate) .

Table 7

Example 8

Emulsion concentrate compositions Sample 8 and Control 8 were prepared with components according to Table 8 below. The ratio of pyriproxyfen and dipropylene glycol dibenzoate of Sample 7 was approximately 1∶16. The eye irritation of Sample 8 was compared with that of Control 8 (without the addition of dipropylene glycol dibenzoate) .

Table 8

Example 9

Emulsion concentrate compositions Sample 9 and Control 9 were prepared according to the recipe of Table 9. The ratio of pyriproxyfen and dipropylene glycol dibenzoate of Sample 9 was approximately 1∶20. Eye irritation of Sample 9 was compared with that of Control 9 (without the addition of dipropylene glycol dibenzoate) .

Table 9

Example 10

Emulsion concentrate compositions Sample 10 and Control 10 were prepared according to the recipe of Table 10 below. The ratio of lufenuron and dipropylene glycol dibenzoate of Sample 10 was approximately 1∶30. The eye irritation of Sample 10 was compared with that of Control 10 (without the addition of dipropylene glycol dibenzoate) .

Table 10

Example 11

Emulsion concentrate compositions Sample 11 and Control 11 were prepared according to the recipe of Table 11. The ratio of abmectin and dipropylene glycol dibenzoate of Sample 11 was approximately 1∶90. The eye irritation of Sample 11 was compared with that of Control 11 (without the addition of dipropylene glycol dibenzoate) .

Table 11

Example 12

Emulsion concentrate compositions Sample 12 and Control 12 were prepared according to the recipe of Table 12. The ratio between bifenthrin and the combined dipropylene glycol dibenzoate and diethylene glycol dibenzoate of Sample 12 was approximately 1∶5. The eye irritation of Sample 12 was compared with that of Control 12 (without the addition of dipropylene glycol dibenzoate and diethylene glycol dibenzoate) .

Table 12

Example 13

The eye irritation potential of the compositions of the Samples and Controls of Examples 1 to 12 was determined as described above. The performance of the compositions of the Samples and Controls was categorized as follows:

Category 0 (Cat 0) : strongly irritant

Category I (Cat I) : irritant

Category II (Cat II) : moderate irritant

Category III (Cat III) : non-irritant

The results are listed in Table 13 below.

Table 13

Samples and Controls	Results
Sample 1	Cat III
Control 1	Cat 0
Sample 2	Cat III
Control 2	Cat 0
Sample 3	Cat III
Control 3	Cat 0
Sample 4	Cat III
Control 4	Cat 0
Sample 5	Cat III
Control 5	Cat 0
Sample 6	Cat III
Control 6	Cat 0
Sample 7	Cat III
Control 7	Cat 0
Sample 8	Cat III
Control 8	Cat 0
Sample 9	Cat III
Control 9	Cat 0
Sample 10	Cat III
Control 10	Cat 0
Sample 11	Cat III
Control 11	Cat 0
Sample 12	Cat III

Control 12	Cat 0
SOLVESSO^TM 100	Cat III
SOLVESSO^TM 200	Cat II
Dimethyl sulfoxide	Cat III
Benzyl alcohol	Cat II

From the results set out in Table 13, it can be seen that dipropylene glycol dibenzoate and diethylene glycol dibenzoate, whether used alone or in combination, were very effective in significantly reducing the eye irritation potential of the compositions.

Claims

An agrochemical composition comprising at least one dipropylene/diethylene glycol dibenzoate, at least one active ingredient and at least one emulsifier.
The composition according to claim 1, wherein the dipropylene/diethylene glycol dibenzoate is present in an amount of from 2％ to 90％ by weight of the composition.
The composition according to claim 2, wherein the dipropylene/diethylene glycol dibenzoate is present in an amount of from 10％ to 80％ by weight of the composition.
The composition according to claim 3, wherein the dipropylene/diethylene glycol dibenzoate is present in an amount of from 20％ to 70％ by weight of the composition.
The composition according to any preceding claim, wherein the weight ratio of the active ingredient and dipropylene/diethylene glycol dibenzoate is from 1:1 to 1:90.
The composition according to claim 5, wherein the weight ratio of the active ingredient and dipropylene/diethylene glycol dibenzoate is from 1:1 to 1:50.
The composition according to claim 6, wherein the weight ratio of the active ingredient and dipropylene/diethylene glycol dibenzoate is from 1:2 to 1:20.
The composition according to claim 7, wherein the weight ratio of the active ingredient and dipropylene/diethylene glycol dibenzoate is from 1:3 to 1:15.
The composition according to any preceding claim, wherein the active ingredient comprises a compound selected from clomazone, a pyrethroid ester, a cyclohexime oxime, a benzoylphenylurea chitin synthesis inhibitor, and an avermectin.
The composition according to claim 9, wherein the active ingredient comprises a compound selected from bifenthrin, pyriproxyfen, clethodim, clomazone, abamectin and lufenuron.
The composition according to any preceding claim, wherein the emulsifier comprises a non-ionic emulsifier.
The composition according to claim 11, wherein the non-ionic emulsifier is selected from an alcohol alkoxylate, an alkylphenol ethoxylate, an alkylpolysaccharide, an amine ethoxylate, a castor oil ethoxylate, a sorbitan fatty acid ester ethoxylate and a polyoxyethylene fatty acid.
The composition according to any preceding claim, wherein the emulsifier comprises an ionic emulsifier.
The composition according to claim 13, wherein the ionic emulsifier is selected from an amine alkylbenzenesulfonate, an ammonium dodecylbenzene sulfonate, a calcium alkylsulphonate and a calcium alkylbenzenesulfonate.
The composition according to any preceding claim, wherein the emulsifier comprises a cationic emulsifier.
The composition according to claim 15, wherein the cationic emulsifier is selected from polyoxyethylene quaternary and polyoxyethylene tallow ethylmonium ethosulfate, stearyltrimethylammonium chloride and benzyl bis (2-chloroethyl) ethylammonium bromide.
The composition according to any preceding claim, wherein the at least one dipropylene/diethylene glycol dibenzoate is diethylene glycol dibenzoate or dipropylene glycol dibenzoate.
The composition according to any of claims 1 to 16, wherein the at least one dipropylene/diethylene glycol dibenzoate comprises a mixture of diethylene glycol dibenzoate and dipropylene glycol dibenzoate.
The composition according to any preceding claim, wherein the composition is a liquid concentrate.
The composition according to claim 19, wherein the composition is an emulsificable concentrate (EC) formulation.
The use of at least one dipropylene/diethylene glycol dibenzoate to reduce the eye irritation of an agrochemical composition caused by at least one active ingredient and/or at least one emulsifier in the composition.
The use according to claim 21, wherein the dipropylene/diethylene glycol dibenzoate is combined with the active ingredient and emulsifier in the composition.
The use according to either of claims 21 or 22, wherein the active ingredient comprises a compound selected from clomazone, a pyrethroid ester, a cyclohexime oxime, a benzoylphenylurea chitin synthesis inhibitor, and an avermectin.
The use according to claim 23, wherein the active ingredient comprises a compound selected from bifenthrin, pyriproxyfen, clethodim, clomazone, abamectin and lufenuron.
The use according to any of claims 21 to 24, wherein the emulsifier comprises a non-ionic emulsifier.
The use according to claim 25, wherein the non-ionic emulsifier is selected from an alcohol alkoxylate, an alkylphenol ethoxylate, an alkylpolysaccharide, an amine ethoxylate, a castor oil ethoxylate, a sorbitan fatty acid ester ethoxylate and a polyoxyethylene fatty acid.
The use according to any of claims 21 to 26, wherein the emulsifier comprises an ionic emulsifier.
The use according to claim 27, wherein the ionic emulsifier is selected from an amine alkylbenzenesulfonate, an ammonium dodecylbenzene sulfonate, a calcium alkylsulphonate and a calcium alkylbenzenesulfonate.
The use according to any of claims 21 to 26, wherein the emulsifier comprises a cationic emulsifier.
The use according to claim 29, wherein the cationic emulsifier is selected from polyoxyethylene quaternary and polyoxyethylene tallow ethylmonium ethosulfate, stearyltrimethylammonium chloride and benzyl bis (2-chloroethyl) ethylammonium bromide.
The use according to any of claims 21 to 30, wherein the at least one dipropylene/diethylene glycol dibenzoate is diethylene glycol dibenzoate or dipropylene glycol dibenzoate.
The use according to any of claims 21 to 30, wherein the at least one dipropylene/diethylene glycol dibenzoate comprises a mixture of diethylene glycol dibenzoate and dipropylene glycol dibenzoate.
A method of reducing eye irritation of a liquid composition comprising at least one active ingredient and at least one emulsifier, the method comprising including in the composition at least one dipropylene/diethylene glycol dibenzoate in the composition.
The method according to claim 33, wherein the active ingredient comprises a compound selected from clomazone, a pyrethroid ester, a cyclohexime oxime, a benzoylphenylurea chitin synthesis inhibitor, and an avermectin.
The method according to claim 34, wherein the active ingredient comprises a compound selected from bifenthrin, pyriproxyfen, clethodim, clomazone, abamectin and lufenuron.
The method according to any of claims 33 to 35, wherein the emulsifier comprises a non-ionic emulsifier.
The method according to claim 36, wherein the non-ionic emulsifier is selected from an alcohol alkoxylate, an alkylphenol ethoxylate, an alkylpolysaccharide, an amine ethoxylate, a castor oil ethoxylate, a sorbitan fatty acid ester ethoxylate and a polyoxyethylene fatty acid.
The method according to any of claims 33 to 37, wherein the emulsifier comprises an ionic emulsifier.
The method according to claim 38, wherein the ionic emulsifier is selected from an amine alkylbenzenesulfonate, an ammonium dodecylbenzene sulfonate, a calcium alkylsulphonate and a calcium alkylbenzenesulfonate.
The method according to any of claims 33 to 39, wherein the emulsifier comprises a cationic emulsifier.
The method according to claim 40, wherein the cationic emulsifier is selected from polyoxyethylene quaternary and polyoxyethylene tallow ethylmonium ethosulfate, stearyltrimethylammonium chloride and benzyl bis (2-chloroethyl) ethylammonium bromide.
The method according to any of claims 33 to 41, wherein the at least one dipropylene/diethylene glycol dibenzoate is diethylene glycol dibenzoate or dipropylene glycol dibenzoate.
The method according to any of claims 33 to 42, wherein the at least one dipropylene/diethylene glycol dibenzoate comprises a mixture of diethylene glycol dibenzoate and dipropylene glycol dibenzoate.
The method according to any of claims 33 to 43, wherein the composition is a liquid concentrate.
The method according to claim 44, wherein the composition is an emulsificable concentrate (EC) formulation.
A method of treating pests at a locus comprising applying to the locus a composition according to any of claims 1 to 20.
A composition substantially as hereinbefore described.
The use of at least one dipropylene/diethylene glycol dibenzoate substantially as hereinbefore described.
A method of reducing eye irritancy of a composition substantially as hereinbefore described.
A method of treating pests at a locus substantially as hereinbefore described.