TW201628496A - An agrochemcial composition, a method of preparing the same and the use thereof - Google Patents

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

Agrochemical composition, method for preparing the same, and use thereof

The present invention relates to an agrochemical composition. The invention further relates to a process for the preparation of the above compositions and to their use in crop protection. The invention further relates to reducing ocular irritation caused by agrochemical compositions, especially liquid concentrate formulations of the compositions.

Emulsion (EC) formulations are a very conventional type of formulation for the preparation and application of compositions comprising agrochemically active ingredients. However, such formulations require large amounts of organic solvents, such as aromatic hydrocarbons, chlorinated hydrocarbons, and the like, while requiring both anionic and nonionic emulsifiers to stabilize the active ingredients in the formulation. By combining the components, the formulated product is of good quality and generally performs well in field applications. However, most products formulated in this manner can cause severe eye irritation to the user. Therefore, such formulations are often classified as dangerous. For example, emulsions are classified as Class I toxicity (Cat I) in Brazil. Farmers and other end users are reluctant to purchase and use such products because the formulation labeled "Class I toxicity" can cause eye irritation.

The prior art does not provide a solution to the problem of using solvents and emulsifiers in emulsion (EC) formulations. Currently, commercially available emulsion formulations can cause severe eye irritation. Therefore, attempts have been made to avoid the use of organic solvents such as aromatic hydrocarbons or chlorinated hydrocarbons, and to substitute alternative solvents which are less toxic. Examples of such alternative solvents are aliphatic hydrocarbons, alcohols, ethylene glycol, polyethylene glycols, glycol ethers, ketones, and polar solvents such as gamma-butyrolactone, N-methyl having high solubility. Pyrrolidone and the like.

However, eye irritation is not only caused by solvents, but also by the active ingredients and emulsifiers present in the formulation. Emulsifiers, such as anionic emulsifiers, are important to increase the spontaneous dispersibility of the formulation in water and the stability of the diluted formulation. Calcium alkylbenzene sulfonate is one of the anionic emulsifiers commonly used in emulsion formulations. However, these anionic emulsifiers can cause severe eye irritation. Therefore, even if the composition is formulated with a solvent which is non-irritating to the eye, the formulation may still cause severe eye irritation due to the presence of the active ingredient and the emulsifier.

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 solvent as a first solvent An alkyl alkanolate, and a condensate of a polyol or a polyol as a second solvent and a mixture thereof. The formulation was 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 comprising at least one polyethylene oxide moiety and at least one hydrophobic A nonionic block copolymer of a polyether moiety. The organic solvent is capable of dissolving the active ingredient. The eye irritation problem is not discussed or mentioned in WO 2006/002984.

In order to provide a formulation that does not irritate the eye, there is an ongoing need to find safe, preferably substantially inert, components for formulating liquid concentrates. It would be advantageous if the formulation component also reduced the irritation of the active ingredient and emulsifier to the eye of the user.

At present, it has surprisingly been found that dipropylene glycol/diethylene glycol dibenzoate not only does not irritate the eye, but also reduces the irritations 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 glycol / diethylene glycol dibenzoate, at least one active ingredient, and at least one emulsifier.

Dipropylene glycol / diethylene glycol dibenzoate itself is not a irritant. The presence of dipropylene glycol/diethylene glycol dibenzoate in agrochemical compositions has been found to significantly reduce the toxicity of the formulation, particularly to reduce the irritation of the formulation to the eye. In particular, it has been shown that dipropylene glycol/diethylene glycol dibenzoate reduces or substantially eliminates irritation of the active ingredient and emulsifier to the eye.

As described in more detail below, dipropylene glycol/diethylene glycol dibenzoate has been found to be effective in reducing the irritation of liquid concentrate formulations. Therefore, the inclusion of dipropylene glycol/diethylene glycol dibenzoate in the liquid concentrate reduces the eye irritation of the formulation. In addition, the use of dipropylene glycol/diethylene glycol dibenzoate in liquid concentrate pesticide formulations has been found to be environmentally friendly.

The dipropylene glycol/diethylene glycol dibenzoate in the composition of the invention is present in an amount sufficient to reduce the irritation of the other components of the composition, especially to reduce the irritations of the active ingredients and emulsifiers present. The amount of dipropylene glycol/diethylene glycol dibenzoate required will depend on the particular active ingredient and emulsifier used in the composition and their amount. The amount of dipropylene glycol/diethylene glycol dibenzoate required to reduce or eliminate irritation to the eye of the formulation can be determined by trial and error without undue experimentation by a skilled person.

Dipropylene glycol/diethylene glycol dibenzoate is effective in reducing the eye irritation of the active ingredient when present in a wide range of weight ratios to the active ingredient. The dipropylene glycol/diethylene glycol dibenzoate is preferably present in an amount at least in the same amount as the active ingredient, more preferably in an amount exceeding the active ingredient. The weight ratio of dipropylene glycol/diethylene glycol dibenzoate to the active ingredient is preferably at least 1:1, in certain preferred embodiments at least 1:2, and in other preferred embodiments at least 1:3. . especially Preferably, the dipropylene glycol/diethylene glycol dibenzoate is provided in a weight ratio of the active ingredient to the dipropylene glycol/diethylene glycol dibenzoate of from 1:1 to 1:100, preferably from 1:1 to 1 : 90, more preferably 1:2 to 1:20, further preferably in an amount of 1:3 to 1:15.

Dipropylene glycol/diethylene glycol dibenzoate is effective in reducing the eye irritation of the emulsifier in a wide weight ratio range. In many embodiments, the dipropylene glycol/diethylene glycol dibenzoate is present in the composition in an amount that is at least the same, more preferably more than the total amount of emulsifier present. The weight ratio of the total content of dipropylene glycol / diethylene glycol dibenzoate to the emulsifier in the composition is preferably at least 0.1, more preferably at least 0.2. The weight ratio of the dipropylene glycol / diethylene glycol dibenzoate to the total content of the emulsifier in the composition may be from 0.1 to 60, preferably from 0.2 to 60. In some embodiments, it has been found that a weight ratio of 0.3 to 10, more specifically 0.4 to 8, is effective. Dipropylene glycol / diethylene glycol dibenzoate can be used in higher amounts, for example, from 10 to 50 by weight to the emulsifier content. In many embodiments, it is effective that the weight ratio of dipropylene glycol / diethylene glycol dibenzoate to emulsifier content is less than 15, more preferably less than 10.

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

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

As described above, the present invention provides an agrochemical composition comprising at least one agrochemical active ingredient. The presence of one or more dipropylene glycol/diethylene glycol dibenzoate has been found to be effective in reducing the irritation of a range of active ingredients. Suitable active ingredients for use in the compositions of the present invention are well known in the art and are commercially available.

As mentioned above, dipropylene glycol / diethylene glycol dibenzoate has been found to be effective Low toxicity, especially a range of active ingredients on the eye. In one embodiment, the composition of the present invention comprises ascorbic acid (2-(2-chlorobenzyl)-4,4-dimethyl-1,2-oxazolidin-3-one) as an active ingredient .

Dipropylene glycol/diethylene glycol dibenzoate has also been found to be effective in reducing the toxicity of pyrethroid acaricides and insecticides, especially to the eye. Such pyrethroids are well known in the art and include, for example, cyhalothrin (( RS )-α-cyano-3-phenoxybenzyl ( Z )-(1 RS , 3 RS )-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarboxylate), cypermethrin (( RS )-α- Cyano-3-phenoxybenzyl (1 RS, 3 RS ; 1 RS, 3 SR )-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate) , deltamethrin (( S )-α-cyano-3-phenoxybenzyl (1 R , 3 R )-3-(2,2-dibromovinyl)-2,2- Dimethylcyclopropanecarboxylate), lambda-cyhalothrin (( S )-α-cyano-3-phenoxybenzyl ( Z )-(1 R, 3 R ) -3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarboxylate and ( R )-cyano-3-phenoxybenzyl ( Z )-(1 S, 3 S )-3-(2-Chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarboxylate). A particularly preferred pyrethroid is bifenthrin.

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

Dipropylene glycol/diethylene glycol dibenzoate has also been found to be effective in reducing the toxicity of cyclohexene oxime herbicides, especially to the eye, including alloxydim (1RS). -3-[(E)-1-(Allyloxyimino)butyl]-4-hydroxy-6,6-dimethyl-2-oxocyclohex-3-enecarboxylic acid methyl ester) Butyroxydim ((5RS)-5-(3-butylindolyl-2,4,6-trimethylphenyl)-2-[(EZ)-1-(ethoxyimino)) Propyl]-3-hydroxycyclohex-2-en-1-one), clethodim ((5RS)-2-{(1EZ)-1-[(2E)-3-chloropropeneoxy) Iminoamino]propyl}-5-[(2RS)-2-(ethylthio)propyl]-3-hydroxycyclohex-2-en-1-one), cyclohexenone (cloproxydim) (5RS)-2-{(EZ)-1-[(2EZ)-3-chloroallyloxyimino] }}-5-[(2RS)-2-(ethylthio)propyl]-3-hydroxycyclohex-2-en-1-one), cycloxydim ((5RS)-2-[ (EZ)-1-(ethoxyimino)butyl]-3-hydroxy-5-[(3RS)-thialan-3-yl]cyclohex-2-en-1-one) , cyprofen (profoxydim) ((5RS)-2-{(EZ)-1-[(2RS)-2-(4-chlorophenoxy)propoxyimino]butyl}-3 -hydroxy-5-[(3RS)-thialan-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), pyran Ketone (tepraloxydim)((5RS)-2-{(EZ)-1-[(2E)-3-chloroallyloxyimino]propyl}-3-hydroxy-5-perhydropyran-4 -cyclohex-2-en-1-one), and tralkoxydim ((RS)-2-[(EZ)-1-(ethoxyimino)propyl]-3- Hydroxy-5-2,4,6-trimethylcyclocyclo-2-ene-1-one). Dipropylene glycol/diethylene glycol dibenzoate is particularly effective in reducing the irritation of ketene.

Dipropylene glycol/diethylene glycol dibenzoate has been further found to be effective in reducing the toxicity of benzamidine benzourea chitin synthesis inhibitors, especially to the eye, including bistrifluron (1-[2-Chloro-3,5-bis(trifluoromethyl)phenyl]-3-(2,6-difluorobenzhydryl)urea), chlorbenzuron (1-( 2-chlorobenzhydryl)-3-(4-chlorophenyl)urea, chlorfluazuron (1-[3,5-dichloro-4-(3-chloro-5-trifluoromethyl) Di-2-benzyloxy)phenyl]-3-(2,6-difluorobenzhydryl)urea, in addition to dichlorbenzuron (1-(4-chlorophenyl)-3-( 2,6-dichlorobenzhydryl)urea, diflubenzuron (1-(4-chlorophenyl)-3-(2,6-difluorobenzhydryl)urea), fluorocyclic Flucycloxuron (1-{α-[( EZ )-4-chloro-α-cyclopropylbenzylideneamino]-p-tolyl}-3-(2,6-difluorobenzhydrazide) Urea) (50-80% ( E )- and 50-20% ( Z )-isomers), flufenoxuron (1-[4-(2-chloro-α,α,α-) Trifluoro-p-tolyloxy)-2-fluorophenyl]-3-(2,6-difluorobenzhydryl)urea, hexaflumuron (1-[3,5-dichloro- 4-(1,1,2,2-tetrafluoroethoxy)phenyl]-3-(2,6-difluorobenzhydryl)urea), hydrazine Lufenuron (( RS )-1-[2,5-dichloro-4-(1,1,2,3,3,3-hexafluoropropoxy)phenyl]-3-(2, 6-difluorobenzhydryl)urea, novaluron (( RS )-1-[3-chloro-4-(1,1,2-trifluoro-2-trifluoromethoxy) Oxy)phenyl]-3-(2,6-difluorobenzimidyl)urea, polyfluorourea (noviflumuron) (1-{3,5-dichloro-2-fluoro-4-[( RS) )-1,1,2,3,3,3-hexafluoropropoxy]phenyl}-3-(2,6-difluorobenzhydryl)urea, penfluron (penfluron) (1- (2,6-difluorobenzhydryl)-3-(α,α,α-trifluoro-p-tolyl)urea, fluorophenylurea (teflubenzuron) (1-(3,5-dichloro-2) , 4-difluorophenyl)-3-(2,6-difluorobenzhydryl)urea) and triilumuron (1-(2-chlorobenzhydryl)-3-(4- Trifluoromethoxyphenyl)urea) Dipropylene glycol/diethylene glycol dibenzoate is particularly effective in reducing the irritation of guanidine.

Dipropylene glycol/diethylene glycol dibenzoate was further found to be effective in reducing the toxicity of avermectin insecticides, acaricides and nematicides, especially to the eye, including avermectin ( Abamectfn)( 80% (10 E , 14 E , 16 E )-(1 R , 4 S , 5' S , 6 S , 6' R , 8 R , 12 S , 13 S , 20 R , 21 R , 24 S )- 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 ] twenty-five -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- arabinose -hexyranosyl)-3 - O -methyl-α-L- arabinose -hexyranoside and 20% (10 E , 14 E , 16 E )-(1 R , 4 S , 5' S , 6 S , 6' R , 8 R , 12 S , 13 S , 20 R , 21 R , 24 S )- 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 ] twenty-five -10,14,16,22-tetraene)-6-spiro-2'-(5',6'-dihydro-2' H -pyran)-12- 2,6-dideoxy-4- O- (2,6-bisdeoxy-3- O -methyl-α-L- arabinose -hexyranosyl)-3- O -methyl- a mixture of α-L-arabinose-hexyranoside), doramectin ((10 E , 14 E , 16 E )-(1 R , 4 S , 5' S , 6 S , 6' R , 8 R , 12 S , 13 S , 20 R , 21 R , 24 S )-6'-cyclohexyl-21,24-dihydroxy-5',11,13,22-tetramethyl-2-oxo Generation-(3,7,19-trioxatetracyclo[15.6.1.1 ^4,8 .0 ^20,24 ]25-10,14,16,22-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- arabinose -hexyranosyl)-3- O -methyl-α-L- arabinose -hexyranose), emamectin (ememectin) 90% (10 E , 14 E , 16 E )-(1 R , 4 S , 5' S , 6 S , 6' R , 8 R , 12 S , 13 S , 20 R , 21 R , 24 S )- 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 ] twenty-five -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- lyso-hexapyranosyl) -α-L- arabinose -hexapyranoside and 10% (10 E , 14 E , 16 E )-(1 R , 4 S , 5' S , 6 S , 6' R , 8 R , 12 S , 13 S , 20 R , 21 R , 24 S )- 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 ] twenty-five -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 - 4-methyl group to -α-L- SU - hexopyranose yl) -α-L- arabinose - pyranoside mixture was six), as acetamide avermectins (eprinomectin) ((10 E, 14 E, 16 E) - (1 R , 4 S , 5' S , 6 S , 6' R , 8 R , 12 S , 13 S , 20 R , 21 R , 24 S )-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 ] twenty-fifth -10,14,16,22-tetraene)-6-spiro-2'-(5',6'-dihydro-2' H -pyran)-12-yl 4- O- (4-acetonitrile amino-2,4,6-trideoxy -3- O - methyl -α-L- lyxo - hexopyranosyl) -2,6-dideoxy -3- O - [alpha-methyl -L- arabinose -hexyranose (main component) and (10 E , 14 E , 16 E )-(1 R , 4 S , 5' S , 6 S , 6' R , 8 R , 12 S , 13 S, 20 R, 21 R, 24 S) -21,24- dihydroxy-6' Propyl-5 ', 11,13,22- tetramethyl-2-oxo - (3,7,19- trioxa tetracyclo [15.6.1.1 ^4,8 .0 ^20,24] twenty-five - 10,14,16,22-tetraene)-6-spiro-2'-(5',6'-dihydro-2' H -pyran)-12-yl 4- O- (4-acetamide deoxy-2,4,6 -3- O - methyl -α-L- lyxo - hexopyranosyl) -2,6-dideoxy -3- O - methyl -α- a mixture of L- arabinose -hexyranose (minor component), ivermectin ((10 E , 14 E , 16 E )-(1 R , 4 S , 5' S , 6 R , 6' R , 8 R , 12 S , 13 S , 20 R , 21 R , 24 S )-6'-[( S )-sec-butyl]-21,24-dihydroxy-5',11, 13,22-tetramethyl-2-oxo-(3,7,19-trioxatetracycline [15.6.1.1 ^4,8 .0 ^20,24 ] twenty five-10,14,16,22- Tetraphenyl)-6-spiro-2'-(tetrahydropyran)-12-yl 2,6-dideoxy-4- O- (2,6-dideoxy-3- O -methyl-α -L- arabinose -hexyranosyl)-3- O -methyl-α-L- arabinose -hexyranoside and (10 E ,14 E ,16 E )-(1 R ,4 S , 5' S ,6 R ,6' R ,8 R ,12 S ,13 S ,20 R ,21 R ,24 S )-21,24-dihydroxy-6'-isopropyl-5',11,13 ,22-tetramethyl-2-oxo-(3,7,19-trioxatetracycline [15.6.1.1 ^4,8 .0 ^20,24 ] twenty five-10,14,16,22-four Alkene-6-spiro-2'-(tetrahydropyran)-12-yl 2,6-dideoxy-4- O- (2,6-bisdeoxy-3- O -methyl-α-L- arabinose -hexyranosyl)-3- O -methyl-α a mixture of -L- arabinose -hexyranose) and selamectin ((10 E , 14 E , 16 E , 21 Z )-(1 R , 4 S , 5' S , 6 R ,6' S ,8 R ,12 S ,13 S ,20 R ,21 R ,24 S )-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 ]25-10,14,16,22-tetraene)- 6-spiro-2'-(tetrahydropyran)-12-yl 2,6-dideoxy-3- O -methyl-α-L- arabinose -hexyranoside). Dipropylene glycol/diethylene glycol dibenzoate is particularly effective in reducing the irritation of avermectin.

The compositions of the present invention have been found to be particularly effective when the active ingredient is selected from the group consisting of clomazone, bifenthrin, pyripramine, clethone, guanidine, avermectin, and mixtures thereof.

The present invention provides an agrochemical composition further comprising at least one emulsifier. Suitable emulsifiers for use in the compositions are well known in the art and are commercially available. The emulsifier or emulsifier mixture is selected to give good emulsifying, dispersing and wetting ability in the formulation used. The emulsifier may be selected from the group consisting of nonionic emulsifiers, ionic emulsifiers, cationic emulsifiers, and mixtures thereof.

Preferred nonionic emulsifiers are selected from the group consisting of alcohol alkoxylates, alkylphenol ethoxylates, alkyl polysaccharides, amine ethoxylates, castor oil ethoxylates, sorbitan fatty acid esters ethoxylates. A base compound, and a polyoxyethylene fatty acid.

Preferred anionic emulsifiers are water soluble soaps and water soluble synthetic emulsifiers. Typical examples of anionic emulsifiers are selected from the group consisting of alkyl benzene sulfonate, ammonium dodecyl benzene sulfonate, and alkyl groups. Calcium sulfonate, and calcium alkylbenzene sulfonate.

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

Wherein R ₁ , R ₂ , R ₃ or R ₄ each represent at least one C ₈ -C ₂₂ alkyl group, or R ₁ , R ₂ , R ₃ or R ₄ respectively represent unsubstituted or halogenated lower alkyl, benzyl Or a hydroxy-lower alkyl group; and X represents a halide such as a chloride ion, methyl sulfate or ethyl sulfate. Preferred examples of the cationic emulsifier are polyoxyethylene quaternary ammonium salt, tallow polyoxyethylene ethyl ammonium ethate, stearyl trimethyl ammonium chloride, benzyl bis(2-chloroethyl) ethyl bromide Ammonium.

The emulsifier or emulsifier mixture is present in the composition in any suitable amount. The emulsifier is preferably 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 of from 5 to 40% by weight of the composition, more preferably from 5 to 35% by weight, still more preferably from 10 to 30% by weight. It has been found that in many embodiments, one or more emulsifiers are particularly suitable in amounts of from 20 to 30% by weight of the composition.

In addition to dipropylene glycol/diethylene glycol dibenzoate, at least one active ingredient and at least one emulsifier, the compositions of the present invention may comprise other ingredients well known in the art depending on the type of formulation used.

For example, the composition may comprise one or more solvents, especially 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 pyrrolidone such as N-methylpyrrolidone, N-octylpyrrolidone; or one or more lactones such as γ-butyrolactone; aromatic hydrocarbons and mixtures thereof , such as the commercially available solvent composition SOLVESSO ^TM 100 and SOLVESSO ^TM 200, and dimethyl sulfoxide.

Other ingredients 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 ingredients are commercially available and their use in formulating agrochemical compositions is recognized and appreciated by those skilled in the art.

The compositions of the present invention can be prepared in any suitable form. The composition of the invention is preferably a liquid concentrate, in particular an emulsion (EC) formulation. Liquid concentrate formulations may contain active ingredients that are sparingly soluble or insoluble in water. The liquid concentrate formulation is preferably pre-dispersed in water prior to use.

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

In yet another aspect, the present invention also provides a method of preparing an agrochemical composition, the method comprising combining at least one dipropylene glycol / diethylene glycol dibenzoate with at least one active ingredient and at least one emulsifier.

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

The individual ingredients are provided according to the weight portion required in the final composition. First, the solvent and dipropylene glycol/diethylene glycol dibenzoate are added to a suitable mixing vessel, such as a blending tank, and mixed to form a mixture. The active ingredient is then added to the mixture and mixed continuously (typically about 30 minutes) until the active ingredient is completely dissolved in the solvent. Thereafter, one or more emulsifiers and other ingredients, if any, are added to the mixture and mixed (typically about 1 hour) to ensure uniformity.

In another aspect, the present invention provides the use of at least one dipropylene glycol/diethylene glycol dibenzoate for reducing the irritations of the active ingredients and emulsifiers in an agrochemical formulation.

In another aspect, the invention provides a method of reducing ocular irritation of a liquid formulation resulting from an active ingredient and an emulsifier, the method comprising adding at least one to the formulation in an amount sufficient to reduce ocular irritation of the formulation Dipropylene glycol / diethylene glycol dibenzoate.

In yet another aspect, the invention provides a method of treating a pest at a location, the method comprising applying a composition as described above at the location.

Embodiments of the invention are described by the following examples for exemplary purposes only.

Example

In the following examples, the compositions were prepared according to the following general methods:

Typically, each ingredient is added to the container in the amounts indicated in the particular composition formulation. More specifically, first, a solvent and dipropylene glycol/diethylene glycol dibenzoate are added to a blending tank in a specific amount, and mixed to prepare a mixture. At least one active ingredient is added to the mixture and mixed continuously for about 30 minutes until the active ingredient is completely dissolved. Thereafter, the emulsifier was added to the blending tank, and the resulting mixture was continuously mixed for about 1 hour until the mixture was homogeneous, and the mixing was stopped. Finally, the mixture is discharged from the blending tank.

The ocular irritation potential of each formulation was determined according to the method described below: NPLuepke: "Hen's Egg Chorio Allantoic Membrane Test for Irritation Potential", Fd.Chem.Toxic .23 (1985), pp. 287-291 (hereinafter referred to as "HET-CAM test"), according to H. Spielmann (H. Spielmann: Methods in Molecular Biology 43 (1995) 199-204 and H. Spielmann The method of ATLA 24 (1996), pp. 741-858) has been improved.

In the HET-CAM test, each composition sample was used for the chorioallantoic membrane (CAM). Process it. The chorioallantoic membrane was then observed for 5 minutes. The severity of bleeding, cell lysis, and coagulation is tested. Samples are classified as follows:

Category 0 (Cat 0): Intense stimulation

Category I (Cat I): Stimulus

Category II (Cat II): Gentle stimulation

Category III (Cat III): no stimulation

Samples and control groups were prepared for each formulation. As described above, the ocular irritation potential was measured for each sample and control. In each of the examples, the control composition was substantially the same as the sample composition except that dipropylene glycol/diethylene glycol dibenzoate was omitted.

Example 1

Emulsion composition sample 1 and control 1 were prepared according to the formulation shown in Table 1 below. The ratio of bifenthrin to dipropylene glycol dibenzoate of sample 1 was about 1:13. The ocular irritation of Sample 1 was compared to Control 1 (i.e., Sample 1 composition without addition of dipropylene glycol dibenzoate).

Example 2

Emulsion composition sample 2 and control 2 were prepared according to the formulation shown in Table 2 below. The ratio of bifenthrin to diethylene glycol dibenzoate in sample 2 was about 1:1. The eye irritation of Sample 2 was compared to Control 2 (without addition of diethylene glycol dibenzoate).

Example 3

Emulsion composition sample 3 and control 3 were prepared according to the ingredients of Table 3 below. The ratio of bifenthrin to dipropylene glycol dibenzoate in sample 3 was about 1:2. The eye irritation of Sample 3 was compared to Control 3 (no dipropylene glycol dibenzoate added).

Example 4

Emulsion composition sample 4 and control 4 were prepared according to the ingredients of Table 4 below. The ratio of the ketene and diethylene glycol dibenzoate of Sample 4 was about 1:3. The ocular irritation of Sample 4 was compared to Control 4 (without addition of diethylene glycol dibenzoate).

Example 5

Emulsion composition sample 5 and control 5 were prepared according to the ingredients of Table 5. The ratio of clomazone and dipropylene glycol dibenzoate in sample 5 was about 1:6. The eye irritation of sample 5 was compared to control 5 (no dipropylene glycol dibenzoate added).

Example 6

Emulsion composition sample 6 and control 6 were prepared according to the ingredients of Table 6 below. The ratio of pyriproxyfen to dipropylene glycol dibenzoate of sample 6 was about 1:5. The ocular irritation of Sample 6 was compared to Control 6 (no dipropylene glycol dibenzoate added).

Example 7

Emulsion composition sample 7 and control 7 were prepared according to the ingredients shown in Table 7 below. The ratio of pyriproxyfen to diethylene glycol dibenzoate of sample 7 was about 1:10. The ocular irritation of Sample 7 was compared to Control 7 (without addition of diethylene glycol dibenzoate).

Example 8

Emulsion composition sample 8 and control 8 were prepared according to the ingredients of Table 8 below. Sample 8 The ratio of pyriproxyfen to dipropylene glycol dibenzoate is about 1:16. The ocular irritation of Sample 8 was compared to Control 8 (without addition of dipropylene glycol dibenzoate).

Example 9

Emulsion composition sample 9 and control 9 were prepared according to the formulation of Table 9 below. The ratio of pyriproxyfen to dipropylene glycol dibenzoate of sample 9 was about 1:20. The ocular irritation of Sample 9 was compared to Control 9 (no dipropylene glycol dibenzoate added).

Example 10

According to the formulation of Table 10, emulsion composition sample 10 and control 10 were prepared. Sample 10 had a ratio of guanidinium to dipropylene glycol dibenzoate of about 1:30. The ocular irritation of Sample 10 was compared to Control 10 (no dipropylene glycol dibenzoate added).

Example 11

Emulsion composition sample 11 and control 11 were prepared according to the formulation of Table 11 below. The ratio of avermectin to dipropylene glycol dibenzoate of sample 11 was about 1:90. The ocular irritation of Sample 11 was compared to Control 11 (no dipropylene glycol dibenzoate added).

Example 12

Emulsion composition sample 12 and control 12 were prepared according to the formulation of Table 12 below. The ratio of bifenthrin to dipropylene glycol dibenzoate and diethylene glycol dibenzoate in sample 12 was about 1:5. The ocular irritation of Sample 12 was compared to Control 12 (no dipropylene glycol dibenzoate and diethylene glycol dibenzoate added).

Example 13

The ocular irritation potential of the samples of Examples 1 to 12 and the control composition was determined as above. The performance of the sample and control compositions was classified as follows:

Category 0 (Cat 0): Intense stimulation

Category I (Cat I): Stimulus

Category II (Cat II): Gentle stimulation

Category III (Cat III): no stimulation

The results are shown in Table 13 below.

From the results of Table 13, it is understood that the use of dipropylene glycol dibenzoate and diethylene glycol dibenzoate alone or in combination can significantly reduce the ocular irritation potential of the composition very effectively.

Claims (50)

An agrochemical composition comprising at least one dipropylene glycol/diethylene glycol dibenzoate, at least one active ingredient, and at least one emulsifier. The composition of claim 1, wherein the dipropylene glycol / diethylene glycol dibenzoate is present in an amount of from 2% by weight to 90% by weight based on the weight of the composition. The composition of claim 2, wherein the dipropylene glycol / diethylene glycol dibenzoate is present in an amount of 10% by weight to 80% by weight based on the weight of the composition. The composition of claim 3, wherein the dipropylene glycol / diethylene glycol dibenzoate is present in an amount of from 20% by weight to 70% by weight based on the weight of the composition. The composition according to any one of the preceding claims, wherein the weight ratio of the active ingredient to dipropylene glycol / diethylene glycol dibenzoate is from 1:1 to 1:90. The composition of claim 5, wherein the weight ratio of the active ingredient to dipropylene glycol / diethylene glycol dibenzoate is from 1:1 to 1:50. The composition of claim 6, wherein the weight ratio of the active ingredient to dipropylene glycol / diethylene glycol dibenzoate is from 1:2 to 1:20. The composition of claim 7, wherein the weight ratio of the active ingredient to dipropylene glycol / diethylene glycol dibenzoate is from 1:3 to 1:15. The composition according to any of the preceding claims, wherein the active ingredient comprises a substance selected from the group consisting of clomazone, pyrethroid, cyclohexene oxime, and benzamidine A synthetic inhibitor of the substance and a compound of avermectin. The composition according to claim 9, wherein the active ingredient comprises a compound selected from the group consisting of bifenthrin, pyriproxyfen, clethodim, clomazone, avermectin and guanidinium. (lufenuron) compound. The composition of any of the preceding claims, wherein the emulsifier comprises a nonionic emulsifier. The composition according to claim 11, wherein the nonionic emulsifier is selected from the group consisting of alcohol alkoxylates, alkylphenol ethoxylates, alkylpolysaccharides, amine ethoxylates, castor oil ethoxylates, sorbitol Anhydride fatty acid ester ethoxylates and polyoxyethylene fatty acids. The composition of any of the preceding claims, wherein the emulsifier comprises an ionic emulsifier. The composition of claim 13, wherein the ionic emulsifier is selected from the group consisting of alkyl benzene sulfonate, ammonium dodecyl benzene sulfonate, calcium alkyl sulfonate, and calcium alkyl benzene sulfonate. The composition of any of the preceding claims, wherein the emulsifier comprises a cationic emulsifier. The composition of claim 15 wherein the cationic emulsifier is selected from the group consisting of polyoxyethylene quaternary ammonium salts, tallow polyoxyethylene ethyl ammonium ethate, stearic acid trimethyl ammonium chloride, and benzyl di(2-) Chloroethyl)ethylammonium bromide. The composition of any of the preceding claims, wherein the at least one dipropylene glycol / diethylene glycol dibenzoate is diethylene glycol dibenzoate or dipropylene glycol dibenzoate. The composition of any one of claims 1 to 16, wherein the at least one dipropylene glycol / diethylene glycol dibenzoate comprises diethylene glycol dibenzoate and dipropylene glycol dibenzoate mixture. The composition of any of the preceding claims, wherein the composition is a liquid concentrate. The composition of claim 19, wherein the composition is an emulsion (EC) formulation. A use of at least one dipropylene glycol/diethylene glycol dibenzoate for reducing eye irritation caused by at least one active ingredient and/or at least one emulsifier in an agrochemical composition. According to the use of claim 21, wherein dipropylene glycol/diethylene glycol dibenzoate is combined in the composition with the active ingredient and an emulsifier. The use according to claim 21 or 22, wherein the active ingredient comprises a pyridoxal, pyrethroid, cyclohexene oxime, benzamidine benzoate chitin synthesis inhibitor and avermectin Compound. The use according to claim 23, wherein the active ingredient comprises a compound selected from the group consisting of bifenthrin, pyriproxyfen, clethethone, clomazone, avermectin and guanidinium. The use of any of claims 21-24, wherein the emulsifier comprises a nonionic emulsifier. The use according to claim 25, wherein the nonionic emulsifier is selected from the group consisting of an alcohol alkoxylate, an alkylphenol ethoxylate, an alkylpolysaccharide, an amine ethoxylate, a castor oil ethoxylate, a sorbitan Fatty acid ester ethoxylates and polyoxyethylene fatty acids. The use of any of claims 21-26, wherein the emulsifier comprises an ionic emulsifier. The use according to claim 27, wherein the ionic emulsifier is selected from the group consisting of alkyl benzene sulfonate, ammonium dodecyl benzene sulfonate, calcium alkyl sulfonate and calcium alkyl benzene sulfonate. The use of any of claims 21-26, wherein the emulsifier comprises a cationic emulsifier. The use according to claim 29, wherein the cationic emulsifier is selected from the group consisting of polyoxyethylene quaternary ammonium salts, tallow polyoxyethylene ethyl ammonium ethate, stearic acid trimethyl ammonium chloride, and benzyl bis (2-chloro) Ethyl)ethylammonium bromide. The use of any one of claims 21-30, wherein the at least one dipropylene glycol / diethylene glycol dibenzoate is diethylene glycol dibenzoate or dipropylene glycol dibenzoate. The use according to any one of claims 21 to 30, wherein the at least one dipropylene glycol / diethylene glycol dibenzoate comprises a mixture of diethylene glycol dibenzoate and dipropylene glycol dibenzoate . A method of reducing ocular irritation of a liquid composition comprising at least one active ingredient and at least one emulsifier, the method comprising at least one dipropylene glycol / diethylene glycol dibenzoate in the composition. The method according to claim 33, wherein the active ingredient comprises a compound selected from the group consisting of clomazone, pyrethroid, cyclohexene oxime, benzamidine phenylurea chitin synthesis inhibitor, and avermectin. The method of claim 34, wherein the active ingredient comprises a compound selected from the group consisting of bifenthrin, pyriproxyfen, clethethone, clomazone, avermectin, and guanidinium. The method of any of claims 33-35, wherein the emulsifier comprises a nonionic emulsifier. The method of claim 36, wherein the nonionic emulsifier is selected from the group consisting of alcohol alkoxylated alcohols, alkylphenol ethoxylates, alkyl polysaccharides, amine ethoxylates, castor oil ethoxylates, sorbitol Anhydride fatty acid ester ethoxylates and polyoxyethylene fatty acids. The method of any of claims 33-37, wherein the emulsifier comprises an ionic emulsifier. The method of claim 38, wherein the ionic emulsifier is selected from the group consisting of alkyl benzene sulfonate, ammonium dodecyl benzene sulfonate, calcium alkyl sulfonate and calcium alkyl benzene sulfonate. The method of any one of claims 33-39, wherein the emulsifier comprises cationic emulsification Agent. The method of claim 40, wherein the cationic emulsifier is selected from the group consisting of polyoxyethylene quaternary ammonium salts, tallow polyoxyethylene ethyl ammonium ethate, stearic acid trimethyl ammonium chloride, and benzyl bis (2-chloro) Ethyl)ethylammonium bromide. The method of any one of claims 33-41, wherein the at least one dipropylene glycol / diethylene glycol dibenzoate is diethylene glycol dibenzoate or dipropylene glycol dibenzoate. The method of any one of claims 33-42, wherein the at least one dipropylene glycol / diethylene glycol dibenzoate comprises a mixture of diethylene glycol dibenzoate and dipropylene glycol dibenzoate . The method of any of claims 33-43, wherein the composition is a liquid concentrate. The method of claim 44, wherein the composition is an emulsion (EC) formulation. A method of treating a pest at a location, the method comprising administering a composition according to any one of claims 1-20 at the location. A composition substantially as described above. A use of at least one dipropylene glycol / diethylene glycol dibenzoate substantially as hereinbefore described. A method of reducing eye irritation by a composition substantially as described above. A method of treating pests at a location substantially as described above.