WO2011157102A1 - Pesticidal composition - Google Patents

Pesticidal composition Download PDF

Info

Publication number
WO2011157102A1
WO2011157102A1 PCT/CN2011/074623 CN2011074623W WO2011157102A1 WO 2011157102 A1 WO2011157102 A1 WO 2011157102A1 CN 2011074623 W CN2011074623 W CN 2011074623W WO 2011157102 A1 WO2011157102 A1 WO 2011157102A1
Authority
WO
WIPO (PCT)
Prior art keywords
ether
glycol
mono
formulation
dialkylene
Prior art date
Application number
PCT/CN2011/074623
Other languages
French (fr)
Inventor
James Timothy Bristow
Original Assignee
Rotam Agrochem International Co.,Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=45347660&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2011157102(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Rotam Agrochem International Co.,Ltd filed Critical Rotam Agrochem International Co.,Ltd
Priority to MYPI2012005443A priority Critical patent/MY172609A/en
Priority to CN201180029390.XA priority patent/CN103037686B/en
Priority to AP2013006677A priority patent/AP3618A/en
Publication of WO2011157102A1 publication Critical patent/WO2011157102A1/en

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels

Definitions

  • the present invention relates to an agrochemical composition.
  • the present invention is especially concerned with a stable and environmental-friendly emulsion in water (EW) pesticidal formulation comprising benzoylphenyl urea compounds active as an insecticides and an ether as the solvent.
  • EW emulsion in water
  • the present invention further relates to a method of preparing the aforementioned composition and their use in crop protection.
  • the present invention is particularly concerned with the prevention of the crystallization of insecticidal benzoylphenyl urea derivatives and with the reduction of the phytotoxicity of EW emulsion formulations.
  • Insect growth regulators known for use in controlling insects include benzoylphenyl urea (BPU) compounds, examples of which may be selected from among the commercially available compounds novaluron, lufenuron, hexaflumuron, triflumuron, diflubenzuron, chlorfluazuron, flufenoxuron, noviflumuron and teflubenzuron.
  • BPU benzoylphenyl urea
  • Benzoyphenyl urea compounds are generally commercialized in emulsion concentrate formulations. However, such formulations require substantial quantities of organic solvents such as aromatic hydrocarbons, chlorinated hydrocarbons, etc. which are known for their toxicological and ecotoxicological properties. The solvent-based formulation brings toxicity, environmental and odor problems. As a result, there is an ongoing need to develop an environmentally-friendly formulation for benzoylphenyl urea compounds.
  • Emulsion in Water (EW) is an environmentally-friendly formulation. Examples of Emulsion in Water
  • CN10137996 describes an Emulsion in Water (EW) formulation comprising 1-50% Lufenuron as active ingredient, a solvent in an amount of 1 %-10%, an antifreeze agent in an amount of 0.5%-5%, an antifoam agent in an amount of 0.1 %-1 %, an emulsifier in an amount of 1 %-10%, a thickener in an amount of 0.1 %-5% and water.
  • EW Emulsion in Water
  • this formulation is more environmentally acceptable than solvent-based Emulsion Concentrate formulations for the same active ingredient, the solvent used in the formulation is xylene or toluene, both of which can be very damaging to the environment.
  • Aliphatic hydrocarbons suffer from their generally low solvent power to solid pesticides.
  • the other solvents listed above, while suitable to solubilize the pesticide, are themselves soluble in water. Such a solubility in water causes the phenomenon of crystallization of the pesticide. Such crystallization makes the formulation unsuitable for spraying.
  • the present invention provides a stable and environmentally-friendly Emulsion in Water (EW) pesticidal formulation.
  • EW Emulsion in Water
  • this invention relates to a use of certain C 2 -C 4 dialkylene glycol di-/mono- C C 4 alkyl ethers as the solvent in an EW composition comprising one or more benzoylphenyl ureas as active agrochemical ingredients.
  • These ethers when used as solvents, are not only environmental friendly, but also advantageously reduce or prevent the crystallization of benzoylphenyl urea in the final formulation.
  • the present invention provides an agrochemical composition
  • a benzoylphenyl urea active ingredient and a C 2 -C 4 dialkylene glycol di-/mono- C-
  • the present invention provides an agrochemical composition consisting essentially of:
  • the C 2 -C 4 dialkylene glycol di-/mono- C C 4 alkyl ether is one or more ethers selected from diethylene glycol dimethyl ether, diethylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether, dibutylene glycol dimethyl ether, dibutylene glycol methyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl ether, dibutylene glycol diethyl ether, dibutylene glycol ethyl ether, diethylene glycol dipropyl ether, diethylene glycol propyl ether, diprop
  • the benzoylphenyl urea active ingredient is at least one compound selected from novaluron, lufenuron, hexaflumuron, triflumuron, diflubenzuron, chlorfluazuron, flufenoxuron, noviflumuron and teflubenzuron and mixtures thereof.
  • Another aspect of the present invention provides a practical method for preparing an agriculturally acceptable stable emulsion in water formulation of a benzoylphenyl urea as active ingredient in which a solvent selected from one or more C 2 -C 4 dialkylene glycol di-/mono- C-
  • the present invention provides a method for preparing an agrochemical formulation, which method comprises the steps of :
  • EW Water
  • the concentrated water emulsions of the present invention exhibit both a high degree of physical and chemical stability, in particular in a temperature range from -15°C to 55°C, in which no crystallization phenomena are observed during storage.
  • the formulations also exhibit improved environmental friendliness.
  • Benzoylphenyl ureas are water insoluble compounds. These compounds are commercially formulated into Emulsion Concentrate (EC) products. Substantive quantities of organic solvents such as xylene or toluene in Emulsion Concentrate formulations are problematic, in particular giving rise to pollution to the environment when the formulations are finally applied in use. Accordingly, there is an ongoing need to develop environmentally friendly formulations for benzoylphenyl urea compounds. Emulsion in Water formulation is one formulation that has the potential for reduced environmental impact. However, the solvents used in the EW formulation of benzoylphenyl ureas as active ingredient are similar with those used in EC formulation. As a result, the problem of environmental pollution remains present.
  • C 2 -C 4 dialkylene glycol di-/mono- C C 4 alkyl ethers when used as solvents in EW formulations, not only exhibit reduced environmental impact, but can also prevent the crystallization of benzoylphenyl urea active ingredient in the final formulation.
  • the C 2 -C 4 dialkylene glycol di-/mono- C C 4 alkyl ether is present in the composition in an amount sufficient to reduce the crystallization of the benzoylphenyl urea active ingredient.
  • C 2 -C 4 dialkylene glycol di-/mono- C C 4 alkyl ethers are effective in reducing the crystallization of the benzoylphenyl urea active ingredient compounds in EW formulations.
  • the inclusion of one or more C 2 -C 4 dialkylene glycol di-/mono- C C 4 alkyl ethers in the liquid concentrates reduces the crystallization of the active ingredient.
  • the use of C 2 -C 4 dialkylene glycol di-/mono- C C 4 alkyl ethers in the liquid concentrates is more environmentally friendly than known formulations.
  • C 2 -C 4 dialkylene glycol di-/mono- C C 4 alkyl ethers are suitable for preparing Emulsion in Water (EW) formulations of sparingly water-soluble or even water-insoluble organic pesticide compounds, in particular benzoylphenyl ureas. Further, the C 2 -C 4 dialkylene glycol di-/mono- C C 4 alkyl ethers are active in reducing the crystallization of benzoylphenyl ureas in the formulation during storage.
  • the C 2 -C 4 dialkylene glycol di-/mono- C C 4 alkyl ethers are present in an amount sufficient to reduce the crystallization of the benzoylphenyl urea compounds.
  • the amount of the C 2 -C 4 dialkylene glycol di-/mono- C C 4 alkyl ether present in the composition will depend, in part, on the concentration of the benzoylphenyl urea active ingredient and may be determined without undue experimentation.
  • the C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether is preferably present in an amount such as to give a weight ratio of the benzoylphenyl urea active ingredient to the C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether of from 1 :0.1 to 1 :7.5, more preferably from 1 :0.3 to 1 :6, still more preferably from 1 :0.5 to 1 ;5.
  • the composition may comprise a single C 2 -C 4 dialkylene glycol di-/mono- (- C 4 alkyl ether or a combination of two or more C 2 -C 4 dialkylene glycol di-/mono- (- C 4 alkyl ethers.
  • the C2-C4 dialkylene glycol di-/mono- (- C 4 alkyl ether may be any suitable such ether.
  • the C 2 -C 4 dialkylene glycol di-/mono- (- C 4 alkyl ether is preferably at least one member selected from diethylene glycol dimethyl ether, diethylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether, dibutylene glycol dimethyl ether, dibutylene glycol methyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl ether, dibutylene glycol diethyl ether, dibutylene glycol ethyl ether, diethylene glycol dipropyl ether, diethylene glycol propyl ether, dipropylene glycol dipropyl ether, dipropylene glycol propyl
  • the composition of the present invention is a liquid concentrate.
  • the one or more C2-C4 dialkylene glycol di-/mono- (- C 4 alkyl ethers are preferably present in an amount of at least 5% by weight, more preferably at least 10% by weight.
  • the C 2 -C 4 dialkylene glycol di-/mono- C1-C4 alkyl ether may be present in an amount of from 5% to 75% by weight, more preferably from 5 to 60% by weight, still more preferably from 10 to 50% by weight.
  • C 2 -C 4 dialkylene glycol di-/mono- C C 4 alkyl ethers are effective in reducing the crystallization of certain benzoylphenyl urea derivatives active as agrochemicals, in particular active as insecticides.
  • Suitable benzoylphenyl ureas for inclusion in the composition are known in the art and many are commercially available.
  • the composition may comprise one or more
  • the formulation contains one or more benzoylphenyl ureas as active ingredient selected from the group consisting of novaluron, lufenuron, hexaflumuron, triflumuron, diflubenzuron, chlorfluazuron, flufenoxuron, noviflumuron, teflubenzuron and mixtures thereof.
  • the benzoylphenyl urea may be present in any suitable amount to provide the required pesticidal activity of the formulation.
  • the benzoylphenul urea may be present in an amount of at least 1 % by weight, preferably at least 2% by weight, more preferably at least 3% by weight.
  • the benzoylphenyl urea may be present in the formulation in an amount in the range of from 1 to 70% by weight, preferably from 2 to 60%, more preferably from 3 to 50% by weight. A preferred range is from 5 to 40% by weight.
  • the formulations of the present invention may comprise one or more surface active agents.
  • a surfactant in which the lipophillic part is derived from a safe natural product.
  • Such surfactants are usually found in use in food and cosmetic industries.
  • the preferred surfactants for use in the formulations of the present invention are those with an H.L.B range of from 7 to 17.
  • suitable surface-active compounds are nonionic, cationic and/or anionic surfactants or a mixture of surfactants having good emulsifying, dispersing and wetting capabilities.
  • Nonionic surfactants are preferably one or more selected from the group consisting of polyethoxylated castor oil, polyadducts of polypropylene and polyethylene oxide, tributylphenol polyethoxylate, polyethylene glycol and octylphenol polyethoxylate.
  • Fatty acid esters of polyoxyethylene sorbitan e.g. polyoxyethylene sorbitan trioleate, are also suitable nonionic surfactants.
  • Cationic surfactants are preferably quaternary ammonium salts carrying, as N-substituent, at least one C 8 -C 22 alkyl radical and, as a further substituent, unsubstituted or halogenated lower alkyl, benzyl or hydroxyl- lower alkyl radicals.
  • the salts are preferably in the form of halide, methyl sulfate or ethyl sulfate. Examples are stearyltrimethylammonium chloride and benzyl bis(2-chloroethyl)ethylammonium bromide.
  • Suitable anionic surfactants may be water-soluble soaps as well as water-soluble synthetic surface-active compounds.
  • alkylarylsulfonates are sodium, calcium or triethanolammonium salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or a condensate of naphthalenesulfonic acid and formaldehyde.
  • Corresponding phosphates e.g. salts of phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 mol of ethylene oxide, or phospholipids, are also suitable.
  • the surfactants may be present in any suitable amount to provide the required dispersion and stability of the liquid concentrate formulation.
  • the one or more surfactants may be present in an amount of at least 5%, preferably at least 10%, more preferably at least 15% by weight.
  • the total surfactant concentration is in the range of from 5 to 50% by weight, more preferably from 10 to 40%) by weight.
  • a surfactant concentration in the range of from 15 to 25% by weight has been found to be suitable in many embodiments.
  • compositions for inclusion in the composition are well known in the art and include, for example antifreeze agents, antifoam agents and thickeners. Such components are commercially available and their use will be recognized and understood by the person skilled in the art. Such additional components may be present in any effective amount, typically from 0.1 to 1 % by weight, more preferably from 0.2 to 0.75% by weight. A concentration of 0.5% by weight of each of the aforementioned components is suitable in many embodiments.
  • This invention also provides a method for preparing an enhanced agriculturally acceptable stable emulsion in water formulation of benzoylphenyl urea as active ingredient in which a C 2 -C 4 dialkylene glycol di-/mono- C C 4 alkyl ether as solvent, is formulated therewith.
  • the present invention provides a method for preparing a liquid concentrate formulation of a benzoylphenyl urea, which method comprises the steps of: 1 . Mixing one or more pesticidally active benzoylphenyl ureas with one or more
  • the present invention provides the use of a C 2 -C 4 dialkylene glycol di-/mono- C C 4 alkyl ether to reduce the crystallization of a benzoylphenyl urea active ingredient in a liquid concentrate formulation.
  • the present invention provides a method for controlling pests at a locus, in particular insects, the method comprising applying to the locus an effective amount of a formulation as hereinbefore described.
  • the invention also provides the use of a concentrate formulation as hereinbefore described in the control of pests at a locus.
  • These concentrated water emulsions of the present invention exhibit improved physical and chemical stability across a wide range of conditions, in particular across a temperature range from -15°C to 55°C, where little or no crystallization phenomena are observed during storage.
  • the formulationsy are also environmentally friendly.
  • the advantage of the formulations of the present invention is that commercially viable concentrations of stable EW formulations of the pesticide may be used without any substantial or detrimental formation of crystals.
  • the formulations of the present invention exhibit a low degree of phytotoxicity compared to the commercial E.C. equivalents.
  • the EW formulations of the present invention have further advantages of being non-flammable and of being of low dermal toxicity and low skin irritancy.
  • EW formulations of the present invention can be considered ecotoxicologically safe, since they are prepared from safe and substantially inert ingredients.
  • the result is not only useful formulations, but also formulations which can meet stringent requirements of the EPA in the United States and the standards of European control of volatile organic compounds.
  • Preparation of water phase Mix one or more additives selected from the group consisting of a surface-active agent, a thickener, an antifoam agent, and an antifreeze agent with water in another blending tank.
  • the samples were tested for low temperature stability and heat storage stability.
  • Low temperature stability was tested in a low temperature apparatus at -14°C for 30 days.
  • Heat storage stability was tested in an oven at 54°C for 14 days.
  • the formulation was filtered through a 342 mesh sieve, and the flowability of the formulation and the formation of crystals observed.
  • the performance of the formulation upon dilution was also determined.
  • the dilution stability in a ratio of 5% v/v in CIPAC D stand water was tested at 30°C for 24 hour, the formation of crystals determined and the separation status observed.
  • test samples are categorized as follows:
  • the liquid formulation described in Table 1 was prepared containing the indicated C 2 -C 4 dialkylene glycol di-/mono- C1-C4 alkyl ether and lufenuron as active ingredient, wherein the ratio of lufenuron and C 2 -C 4 dialkylene glycol di-/mono- C1-C4 alkyl ether was approximately 1 :5.
  • the formulation of Example 1 contained the C 2 -C 4 dialkylene glycol di-/mono- C1-C4 alkyl ether in an amount of 25%wt.
  • the liquid formulation described in Table 2 was prepared containing the indicated C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether and novaluron as the active ingredient, wherein the ratio of novaluron and C 2 -C 4 dialkylene glycol di-/mono- C C4 alkyl ether was approximately 1 :4.
  • the formulation of Example 2 contained the C 2 -C 4 dialkylene glycol di-/mono- C1-C4 alkyl ether in an amount of 40%wt. Table 2
  • the liquid formulation described in Table 3 was prepared containing the indicated C 2 -C 4 dialkylene glycol di-/mono- (- C 4 alkyl ether and hexafluron as the active ingredient, wherein the ratio of hexaflumuron and C 2 -C 4 dialkylene glycol di-/mono- C1-C4 alkyl ether was approximately 1 :3.
  • the formulation of Example 3 contained the C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether in an amount of 24%wt.
  • the liquid formulation described in Table 4 was prepared containing the indicated C 2 -C 4 dialkylene glycol di-/mono- (- C 4 alkyl ether and triflumuron as the active ingredient, wherein the ratio of triflumuron and C 2 -C 4 dialkylene glycol di-/mono- (- C 4 alkyl ether was approximately 1 :2.
  • the formulation of Example 4 contained the C2-C4 dialkylene glycol di-/mono- (- C 4 alkyl ether in an amount of 10%wt.
  • Example 5 The liquid formulation described in Table 5 was prepared containing the indicated C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether and diflubenzuron as the active ingredient, wherein the ratio of diflubenzuron and C 2 -C 4 dialkylene glycol di-/mono- C1-C4 alkyl ether was approximately 1 :5.
  • the formulation of Example 5 contained the C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether in an amount of 50%wt. Table 5
  • the liquid formulation described in Table 6 was prepared containing the indicated C 2 -C 4 dialkylene glycol di-/mono- (- C 4 alkyl ether and chlorfluazuron as the active ingredient, wherein the ratio of chlorfluazuron and C 2 -C 4 dialkylene glycol di-/mono- C1-C4 alkyl ether was approximately 1 :0.5.
  • the formulation of Example 6 contained the C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether in an amount of 10%wt.
  • the liquid formulation described in Table 7 was prepared containing the indicated C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether and flufenoxuron as the active ingredient, wherein the ratio of flufenoxuron and C 2 -C 4 dialkylene glycol di-/mono- C C4 alkyl ether was approximately 1 : 1 .
  • the formulation of Example 7 contained the C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether in an amount of 25%wt. Table 7
  • the liquid formulation described in Table 8 was prepared containing the indicated C 2 -C 4 dialkylene glycol di-/mono- (- C 4 alkyl ether and noviflumuron as the active ingredient, wherein the ratio of noviflumuron and C 2 -C 4 dialkylene glycol di-/mono- C1-C4 alkyl ether was approximately 1 :5.
  • the formulation of Example 8 contained the C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether in an amount of 25%wt.
  • the liquid formulation described in Table 9 was prepared containing the indicated C 2 -C 4 dialkylene glycol di-/mono- (- C 4 alkyl ether and teflubenuron as the active ingredient, wherein the ratio of teflubenuron and C 2 -C 4 dialkylene glycol di-/mono- ( C 4 alkyl ether was approximately 1 :5.
  • the formulation of Example 9 contained the C2-C4 dialkylene glycol di-/mono- (- C 4 alkyl ether in an amount of 20%wt.
  • the liquid formulation described in Table 10 was prepared containing the indicated C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether and a combination of novaluron and lufenuron as active ingredients, wherein the ratio of novaluron plus lufenuron and C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether was approximately 1 :3.
  • the formulation of Example 10 contained the C 2 -C 4 dialkylene glycol di-/mono- C1-C4 alkyl ether in an amount of 30%wt.
  • the liquid formulation described in Table 1 1 was prepared containing the indicated C 2 -C 4 dialkylene glycol di-/mono- C1-C4 alkyl ether and a combination of triflumuron and hexaflumuron as active ingredients, wherein the ratio of triflumuron plus hexaflumuron and C 2 -C 4 dialkylene glycol di-/mono- C1-C4 alkyl ether was
  • Example 1 1 contained the C 2 -C 4 dialkylene glycol di-/mono- C1-C4 alkyl ether in an amount of 30%wt.
  • the liquid formulation described in Table 12 was prepared containing the indicated C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether and a combination of diflubenzuron and chlorfuazuron as active ingredients, wherein the ratio of diflubenzuron plus chlorfluazuron and C 2 -C 4 dialkylene glycol di-/mono- C C 4 alkyl ether was approximately 1 :2.
  • the formulation of Example 12 contained the C 2 -C 4 dialkylene glycol di-/mono- C C 4 alkyl ether in an amount of 30%wt. Table 12
  • the liquid formulation described in Table 13 was prepared containing the indicated C 2 -C 4 dialkylene glycol di-/mono- C C 4 alkyl ether and a combination of flufenoxuron and noviflumuron as active ingredients, wherein the ratio of flufenoxuron plus noviflumuron and C 2 -C 4 dialkylene glycol di-/mono- C C 4 alkyl ether was
  • Example 13 contained the C 2 -C 4 dialkylene glycol di-/mono- C C 4 alkyl ether in an amount of 35%wt. Table 13
  • the liquid formulation described in Table 1 was prepared containing the indicated C 2 -C 4 dialkylene glycol di-/mono- (- C 4 alkyl ether and a combination of noviflumuron and teflubenzuron as active ingredients, wherein the ratio of noviflumuron plus teflubenzuron and C 2 -C 4 dialkylene glycol di-/mono- C1-C4 alkyl ether was approximately 1 : 1.3.
  • the formulation of Example 14 contained C 2 -C 4 dialkylene glycol di-/mono- C1-C4 alkyl ether in an amount of 40%wt.
  • the liquid formulation described in Table 15 was prepared containing the indicated C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether and a combination of novaluron and hexaflumuron as active ingredients, wherein the ratio of novaluron plus hexaflumuron and C 2 -C 4 dialkylene glycol di-/mono- C C 4 alkyl ether was
  • Example 15 contained the C 2 -C 4 dialkylene glycol di-/mono- C C 4 alkyl ether in an amount of 50%wt.
  • the liquid formulation described in Table 16 was prepared containing the indicated C 2 -C 4 dialkylene glycol di-/mono- C C 4 alkyl ether and a combination of lufenuron and triflumuron as active ingredients, wherein the ratio of lufenuron plus triflumuron and C 2 -C 4 dialkylene glycol di-/mono- C C 4 alkyl ether was approximately 1 :2.
  • the formulation of Example 16 contained the C 2 -C 4 dialkylene glycol di-/mono- C C 4 alkyl ether in an amount of 36%wt.
  • the liquid formulation described in Table 17 was prepared containing the indicated C 2 -C 4 dialkylene glycol di-/mono- (- C 4 alkyl ether and a combination of lufenuron and diflubenzuron as active ingredients, wherein the ratio of lufenuron plus diflubenzuron and C2-C4 dialkylene glycol di-/mono- (- C 4 alkyl ether was approximately 1 : 1 .8.
  • the formulation of Example 17 contained C 2 -C 4 dialkylene glycol di-/mono- (- C 4 alkyl ether in an amount of 45%wt.
  • the liquid formulation described in Table 18 was prepared containing the indicated C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether and a combination of lufenuron and chlorfluazuron as active ingredients, wherein the ratio of lufenuron plus chlorfluazuron and C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether was approximately 1 : 1 .4.
  • the formulation of Example 18 contained the C 2 -C 4 dialkylene glycol di-/mono- C C 4 alkyl ether in an amount of 35%wt.
  • the liquid formulation described in Table 19 was prepared containing the indicated C 2 -C 4 dialkylene glycol di-/mono- C C 4 alkyl ether and a combination of lufenuron and flufenoxuron as active ingredients, wherein the ratio of lufenuron plus flufenoxuron and C 2 -C 4 dialkylene glycol di-/mono- C C 4 alkyl ether was approximately 1 :5.
  • the formulation of Example 19 contained the C 2 -C 4 dialkylene glycol di-/mono- C C 4 alkyl ether in an amount of 50%wt.
  • the liquid formulation described in Table 20 was prepared containing the indicated C 2 -C 4 dialkylene glycol di-/mono- (- C 4 alkyl ether and a combination of lufenuron and noviflumuron as active ingredients, wherein the ratio of lufenuron plus noviflumuron and C2-C4 dialkylene glycol di-/mono- (- C 4 alkyl ether was approximately 1 : 1 .
  • the formulation of Example 20 contained the C 2 -C 4 dialkylene glycol di-/mono- (- C 4 alkyl ether in an amount of 35%wt.
  • the liquid formulation described in Table 21 was prepared containing the indicated C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether and a combination of lufenuron and teflubenzuron as active ingredients, wherein the ratio of lufenuron plus teflubenzuron and C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether was approximately 1 :2.
  • the formulation of Example 1 contained the C 2 -C 4 dialkylene glycol di-/mono- C C 4 alkyl ether in an amount of 20%wt.
  • dipropylene glycol butyl ether 100kg dipropylene glycol dibutyl ether 100kg
  • the liquid formulation described in Table 22 was prepared containing the indicated C 2 -C 4 dialkylene glycol di-/mono- C-
  • the formulation of Example 22 contained the C 2 -C 4 dialkylene glycol di-/mono- C C 4 alkyl ether in an amount of 40%wt.
  • the liquid formulation described in Table 23 was prepared containing the indicated C 2 -C 4 dialkylene glycol di-/mono- C1-C4 alkyl ether and a combination of triflumuron and noviflumuron as active ingredients, wherein the ratio of triflumuron plus noviflumuron and C 2 -C 4 dialkylene glycol di-/mono- C1-C4 alkyl ether was
  • Example 23 contained the C 2 -C 4 dialkylene glycol di-/mono- C1-C4 alkyl ether in an amount of 50%wt.
  • Example 1 -23 The samples from Example 1 -23 were tested for low temperature stability at -14°C for 30 days and for heat storage stability at 54°C for 14 days. The dilution stability in a ratio of 5% v/v in CIPAC D stand water was also tested at 30°C for 24hour.
  • the trials to check relative phytotoxicity were carried out with the following samples according to the present invention and comparative trial based on a commercial Lufenuon 50 EC product. In terms of the severity of the phytotoxic symptoms, the test samples were categorized as follows: Cat 0: no phytotoxicity
  • the EW formulation according to this present invention has good flowability and storage stability at both low temperatures and high temperatures. Further, the phytotoxicity exhibited by the formulations of this invention is siginficantly less than the equivalent commercial EC formulation.
  • the C 2 -C 4 dialkylene glycol di-/mono- C C 4 alkyl ether present in the formulation exhibits significant performance in preventing the crystallization of the insecticidally active benzoylphenyl urea derivatives, while also contributing to a significant reduction in the adverse environmental impacts of the formulations when in use.

Abstract

An agrochemical composition is provided, the composition comprising at least one benzoylphenyl urea active ingredient, a solvent comprising a C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether; and optionally at least one component selected from the group consisting of a surface-active agent, a thickener, an antifoam agent, an antifreeze agent and water. The presence of the C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether reduces the crystallization of the benzoylphenyl urea active ingredient during storage and use, while also reducing the phytotoxicity of the formulation. A method of preparing the formulation, in particular an EW formulation comprises (1) mixing one or more pesticidally active benzoylphenyl ureas with one or more C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ethers to form a homogeneous oil phase; (2) mixing one or more additives selected from a surface-active agent, a thickener, an antifoam agent, an antifreeze agent and water; and (3) combining the water phase and the oil phase to form a dispersible EW emulsion formulation.

Description

PESTICIDAL COMPOSITION
FIELD OF THE INVENTION
The present invention relates to an agrochemical composition. The present invention is especially concerned with a stable and environmental-friendly emulsion in water (EW) pesticidal formulation comprising benzoylphenyl urea compounds active as an insecticides and an ether as the solvent. The present invention further relates to a method of preparing the aforementioned composition and their use in crop protection. The present invention is particularly concerned with the prevention of the crystallization of insecticidal benzoylphenyl urea derivatives and with the reduction of the phytotoxicity of EW emulsion formulations.
BACKGROUIND OF THE INVENTION
Insect growth regulators known for use in controlling insects include benzoylphenyl urea (BPU) compounds, examples of which may be selected from among the commercially available compounds novaluron, lufenuron, hexaflumuron, triflumuron, diflubenzuron, chlorfluazuron, flufenoxuron, noviflumuron and teflubenzuron. Benzoyphenyl urea compounds are generally commercialized in emulsion concentrate formulations. However, such formulations require substantial quantities of organic solvents such as aromatic hydrocarbons, chlorinated hydrocarbons, etc. which are known for their toxicological and ecotoxicological properties. The solvent-based formulation brings toxicity, environmental and odor problems. As a result, there is an ongoing need to develop an environmentally-friendly formulation for benzoylphenyl urea compounds. Emulsion in Water (EW) is an environmentally-friendly formulation. Examples of Emulsion in Water formulations are known in the art.
CN10137996 describes an Emulsion in Water (EW) formulation comprising 1-50% Lufenuron as active ingredient, a solvent in an amount of 1 %-10%, an antifreeze agent in an amount of 0.5%-5%, an antifoam agent in an amount of 0.1 %-1 %, an emulsifier in an amount of 1 %-10%, a thickener in an amount of 0.1 %-5% and water. Although this formulation is more environmentally acceptable than solvent-based Emulsion Concentrate formulations for the same active ingredient, the solvent used in the formulation is xylene or toluene, both of which can be very damaging to the environment.
There is a need to improve the prior art by the selection of solvents which are environmentally-friendly. It would also be most advantageous if the selected solvents could impart other benefits to the formulation, in particular to improve the shelf-life.
The United States Environmental Protection Agency has conducted a review of ingredients in pesticidal formulations other than active ingredient. In Europe, the E.E.C. Council is at an advanced stage of introducing legislation regulating the use of volatile organic compounds (VOC) and to require the eco-labelling of formulations which contain such VOC's. Indeed, Canada and Germany already have a system of ecotoxic labelling.
Under these circumstances, it has been desired to quickly develop alternatives to conventional agricultural chemicals having the above-described problems, and to supply to the market agricultural chemicals which are human- and environmentally-friendly and which are also practical to use in commercial agriculture. A number of alternative solvents have been tried or used in the past. Examples of such alternative solvents are aliphatic hydrocarbons, alcohols, glycols, polyglycols, glycol ethers, ketones and polar solvents with high solvent power, such as gamma-butyrolactone, N-methyl pyrrolidone and the like.
Aliphatic hydrocarbons suffer from their generally low solvent power to solid pesticides. The other solvents listed above, while suitable to solubilize the pesticide, are themselves soluble in water. Such a solubility in water causes the phenomenon of crystallization of the pesticide. Such crystallization makes the formulation unsuitable for spraying.
In the present invention it has been surprisingly found that certain C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether solvents can not only prevent the crystallization of benzoylphenyl urea derivative in Emulsion in Water ( EW) formulations during storage, but also that these solvents are significantly more environmentally friendly than other solvents hitherto used in agrochemical formulations. SUMMARY OF THE INVENTION
The present invention provides a stable and environmentally-friendly Emulsion in Water (EW) pesticidal formulation. In particular, this invention relates to a use of certain C2-C4 dialkylene glycol di-/mono- C C4 alkyl ethers as the solvent in an EW composition comprising one or more benzoylphenyl ureas as active agrochemical ingredients. These ethers, when used as solvents, are not only environmental friendly, but also advantageously reduce or prevent the crystallization of benzoylphenyl urea in the final formulation.
Accordingly, in a first aspect, the present invention provides an agrochemical composition comprising a benzoylphenyl urea active ingredient and a C2-C4 dialkylene glycol di-/mono- C-|-C4 alkyl ether.
In a further aspect, the present invention provides an agrochemical composition consisting essentially of:
(a) 1 %-50% benzoylphenyl urea active ingredient; (b) 5%-50% of a C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether as a solvent; and
(c) optionally one or more additives selected from the group consisting of a surface-active agent, a thickener, an antifoam agent, an antifreeze agent and water, the sum of all ingredients totaling 100%. In one embodiment, the C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether is one or more ethers selected from diethylene glycol dimethyl ether, diethylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether, dibutylene glycol dimethyl ether, dibutylene glycol methyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl ether, dibutylene glycol diethyl ether, dibutylene glycol ethyl ether, diethylene glycol dipropyl ether, diethylene glycol propyl ether, dipropylene glycol dipropyl ether, dipropylene glycol propyl ether, dibutylene glycol dipropyl ether, dibutylene glycol propyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl ether, dipropylene glycol dibutyl ether, dipropylene glycol butyl ether, dibutylene glycol dibutyl ether, dibutylene glycol butyl ether and mixtures thereof.
In preferred embodiments, the benzoylphenyl urea active ingredient is at least one compound selected from novaluron, lufenuron, hexaflumuron, triflumuron, diflubenzuron, chlorfluazuron, flufenoxuron, noviflumuron and teflubenzuron and mixtures thereof.
Another aspect of the present invention provides a practical method for preparing an agriculturally acceptable stable emulsion in water formulation of a benzoylphenyl urea as active ingredient in which a solvent selected from one or more C2-C4 dialkylene glycol di-/mono- C-|-C4 alkyl ethers, is formulated therewith. In particular, the present invention provides a method for preparing an agrochemical formulation, which method comprises the steps of :
1. Mixing one or more pesticidally active benzoylphenyl ureas with one or more
C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether to get a homogeneous oil phase;
2. Mixing at least one additives selected from the group consisting of a surface-active agent, a thickener, an antifoam agent, an antifreeze agent and water, the sum of all ingredients totaling 100% to get a homogeneous water phase; 3. Combining the water phase and the oil phase to get a dispersible Emulsion in
Water (EW) formulation with mixing, for example with the aid of an apparatus such as a high-shear mixer, a high pressure orifice homogenizer and the like.
The concentrated water emulsions of the present invention exhibit both a high degree of physical and chemical stability, in particular in a temperature range from -15°C to 55°C, in which no crystallization phenomena are observed during storage. The formulations also exhibit improved environmental friendliness.
DETAILED DESCRIPTION OF THE INVENTION
Benzoylphenyl ureas are water insoluble compounds. These compounds are commercially formulated into Emulsion Concentrate (EC) products. Substantive quantities of organic solvents such as xylene or toluene in Emulsion Concentrate formulations are problematic, in particular giving rise to pollution to the environment when the formulations are finally applied in use. Accordingly, there is an ongoing need to develop environmentally friendly formulations for benzoylphenyl urea compounds. Emulsion in Water formulation is one formulation that has the potential for reduced environmental impact. However, the solvents used in the EW formulation of benzoylphenyl ureas as active ingredient are similar with those used in EC formulation. As a result, the problem of environmental pollution remains present. There is a need to find a solvent for use in the EW formulation of benzoylphenyl ureas as active ingredient that offers reduced environmental impact. Water-soluble solvents having a high solubility for the pesticide, in particular the benzoylphenyl ureas, are known. However, such a solubility in water causes the phenomenon of crystallization of the pesticide. Such crystallization renders the formulation unsuitable for spraying. Accordingly, it would be an advantage if the solvents selected in the EW composition are not only environmentally friendly, but also can prevent the crystallization of benzoylphenyl ureas in the formulation during storage. In the present invention, it has been surprisingly found that certain C2-C4 dialkylene glycol di-/mono- C C4 alkyl ethers, when used as solvents in EW formulations, not only exhibit reduced environmental impact, but can also prevent the crystallization of benzoylphenyl urea active ingredient in the final formulation. The C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether is present in the composition in an amount sufficient to reduce the crystallization of the benzoylphenyl urea active ingredient.
It has been found that C2-C4 dialkylene glycol di-/mono- C C4 alkyl ethers are effective in reducing the crystallization of the benzoylphenyl urea active ingredient compounds in EW formulations. Thus, the inclusion of one or more C2-C4 dialkylene glycol di-/mono- C C4 alkyl ethers in the liquid concentrates reduces the crystallization of the active ingredient. In addition, it has been found that the use of C2-C4 dialkylene glycol di-/mono- C C4 alkyl ethers in the liquid concentrates is more environmentally friendly than known formulations.
C2-C4 dialkylene glycol di-/mono- C C4 alkyl ethers are suitable for preparing Emulsion in Water (EW) formulations of sparingly water-soluble or even water-insoluble organic pesticide compounds, in particular benzoylphenyl ureas. Further, the C2-C4 dialkylene glycol di-/mono- C C4 alkyl ethers are active in reducing the crystallization of benzoylphenyl ureas in the formulation during storage.
In the formulations of the present invention, the C2-C4 dialkylene glycol di-/mono- C C4 alkyl ethers are present in an amount sufficient to reduce the crystallization of the benzoylphenyl urea compounds. The amount of the C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether present in the composition will depend, in part, on the concentration of the benzoylphenyl urea active ingredient and may be determined without undue experimentation. The C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether is preferably present in an amount such as to give a weight ratio of the benzoylphenyl urea active ingredient to the C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether of from 1 :0.1 to 1 :7.5, more preferably from 1 :0.3 to 1 :6, still more preferably from 1 :0.5 to 1 ;5. The composition may comprise a single C2-C4 dialkylene glycol di-/mono- (- C4 alkyl ether or a combination of two or more C2-C4 dialkylene glycol di-/mono- (- C4 alkyl ethers.
The C2-C4 dialkylene glycol di-/mono- (- C4 alkyl ether may be any suitable such ether. The C2-C4 dialkylene glycol di-/mono- (- C4 alkyl ether is preferably at least one member selected from diethylene glycol dimethyl ether, diethylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether, dibutylene glycol dimethyl ether, dibutylene glycol methyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl ether, dibutylene glycol diethyl ether, dibutylene glycol ethyl ether, diethylene glycol dipropyl ether, diethylene glycol propyl ether, dipropylene glycol dipropyl ether, dipropylene glycol propyl ether, dibutylene glycol dipropyl ether, dibutylene glycol propyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl ether, dipropylene glycol dibutyl ether, dipropylene glycol butyl ether, dibutylene glycol dibutyl ether, dibutylene glycol butyl ether and mixtures thereof. Suitable C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ethers are known in the art and are commercially available.
The composition of the present invention is a liquid concentrate. The one or more C2-C4 dialkylene glycol di-/mono- (- C4 alkyl ethers are preferably present in an amount of at least 5% by weight, more preferably at least 10% by weight. The C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether may be present in an amount of from 5% to 75% by weight, more preferably from 5 to 60% by weight, still more preferably from 10 to 50% by weight.
As noted above, it has been found that C2-C4 dialkylene glycol di-/mono- C C4 alkyl ethers are effective in reducing the crystallization of certain benzoylphenyl urea derivatives active as agrochemicals, in particular active as insecticides. Suitable benzoylphenyl ureas for inclusion in the composition are known in the art and many are commercially available. The composition may comprise one or more
benzoylphenyl urea derivative active ingredients.
In one embodiment, the formulation contains one or more benzoylphenyl ureas as active ingredient selected from the group consisting of novaluron, lufenuron, hexaflumuron, triflumuron, diflubenzuron, chlorfluazuron, flufenoxuron, noviflumuron, teflubenzuron and mixtures thereof.
The benzoylphenyl urea may be present in any suitable amount to provide the required pesticidal activity of the formulation. In particular, the benzoylphenul urea may be present in an amount of at least 1 % by weight, preferably at least 2% by weight, more preferably at least 3% by weight. The benzoylphenyl urea may be present in the formulation in an amount in the range of from 1 to 70% by weight, preferably from 2 to 60%, more preferably from 3 to 50% by weight. A preferred range is from 5 to 40% by weight.
The formulations of the present invention may comprise one or more surface active agents. In order that the formulations of the present invention exhibit advantageous ecological acceptablility, it is preferable to use a surfactant in which the lipophillic part is derived from a safe natural product. Such surfactants are usually found in use in food and cosmetic industries. The preferred surfactants for use in the formulations of the present invention are those with an H.L.B range of from 7 to 17.
Depending on the nature of the active compound to be formulated, suitable surface-active compounds are nonionic, cationic and/or anionic surfactants or a mixture of surfactants having good emulsifying, dispersing and wetting capabilities. Nonionic surfactants are preferably one or more selected from the group consisting of polyethoxylated castor oil, polyadducts of polypropylene and polyethylene oxide, tributylphenol polyethoxylate, polyethylene glycol and octylphenol polyethoxylate. Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable nonionic surfactants. Cationic surfactants are preferably quaternary ammonium salts carrying, as N-substituent, at least one C8-C22 alkyl radical and, as a further substituent, unsubstituted or halogenated lower alkyl, benzyl or hydroxyl- lower alkyl radicals. The salts are preferably in the form of halide, methyl sulfate or ethyl sulfate. Examples are stearyltrimethylammonium chloride and benzyl bis(2-chloroethyl)ethylammonium bromide.
Suitable anionic surfactants may be water-soluble soaps as well as water-soluble synthetic surface-active compounds. Typical examples of alkylarylsulfonates are sodium, calcium or triethanolammonium salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or a condensate of naphthalenesulfonic acid and formaldehyde. Corresponding phosphates, e.g. salts of phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 mol of ethylene oxide, or phospholipids, are also suitable. The surfactants may be present in any suitable amount to provide the required dispersion and stability of the liquid concentrate formulation. In particular, the one or more surfactants may be present in an amount of at least 5%, preferably at least 10%, more preferably at least 15% by weight. Preferably, the total surfactant concentration is in the range of from 5 to 50% by weight, more preferably from 10 to 40%) by weight. A surfactant concentration in the range of from 15 to 25% by weight has been found to be suitable in many embodiments.
Further components for inclusion in the composition are well known in the art and include, for example antifreeze agents, antifoam agents and thickeners. Such components are commercially available and their use will be recognized and understood by the person skilled in the art. Such additional components may be present in any effective amount, typically from 0.1 to 1 % by weight, more preferably from 0.2 to 0.75% by weight. A concentration of 0.5% by weight of each of the aforementioned components is suitable in many embodiments.
This invention also provides a method for preparing an enhanced agriculturally acceptable stable emulsion in water formulation of benzoylphenyl urea as active ingredient in which a C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether as solvent, is formulated therewith. In particular, the present invention provides a method for preparing a liquid concentrate formulation of a benzoylphenyl urea, which method comprises the steps of: 1 . Mixing one or more pesticidally active benzoylphenyl ureas with one or more
C2-C4 dialkylene glycol di-/mono- C C4 alkyl ethers to obtain a homogeneous oil phase;
2. Mixing one or more additives selected from the group consisting of a surface-active agent, a thickener, an antifoam agent, an antifreeze agent and water, to obtain a homogeneous water phase; and
3. Adding the water phase to the oil phase to obtain a dispersible EW emulsion formulation with mixing, for example with the aid of an apparatus such as a high-shear mixer, a high pressure orifice homogenizer and the like. ln a further aspect, the present invention provides the use of a C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether to reduce the crystallization of a benzoylphenyl urea active ingredient in a liquid concentrate formulation.
Still further, the present invention provides a method for controlling pests at a locus, in particular insects, the method comprising applying to the locus an effective amount of a formulation as hereinbefore described.
Further, the invention also provides the use of a concentrate formulation as hereinbefore described in the control of pests at a locus.
These concentrated water emulsions of the present invention exhibit improved physical and chemical stability across a wide range of conditions, in particular across a temperature range from -15°C to 55°C, where little or no crystallization phenomena are observed during storage. The formulationsy are also environmentally friendly.
The advantage of the formulations of the present invention is that commercially viable concentrations of stable EW formulations of the pesticide may be used without any substantial or detrimental formation of crystals.
The formulations of the present invention exhibit a low degree of phytotoxicity compared to the commercial E.C. equivalents.
The EW formulations of the present invention have further advantages of being non-flammable and of being of low dermal toxicity and low skin irritancy.
Finally, the EW formulations of the present invention can be considered ecotoxicologically safe, since they are prepared from safe and substantially inert ingredients. The result is not only useful formulations, but also formulations which can meet stringent requirements of the EPA in the United States and the standards of European control of volatile organic compounds.
While the invention will now be described in connection with certain preferred embodiments in the following examples, it will be understood that it is not intended to limit the invention to these particular embodiments. On the contrary, it is intended to cover all alternatives, modifications and equivalents as may be included within the scope of the invention as defined by the appended claims. Thus, the following examples, which include preferred embodiments, will serve to illustrate the practice of this invention, it being understood that the particulars shown are by way of example and for purposes of illustrative discussion of preferred embodiments of the present invention only and are presented in the cause of providing what is believed to be the most useful and readily understood description of procedures as well as of the principles and conceptual aspects of the invention. EXAMPLES
In each of the following examples, a composition was prepared according to the following general methodology:
1. Preparation of oil phase:
Charge the specified amount of one or more C2-C4 dialkylene glycol di-/mono- C C4 alkyl ethers to a blending tank; agitate the solvent; add the specified amount of one or more benzoylphenyl urea active ingredients to the blending tank; continue agitating for 30 minutes until all benzoylphenyl urea active ingredients are dissolved completely to form a homogeneous solution;
2. Preparation of water phase: Mix one or more additives selected from the group consisting of a surface-active agent, a thickener, an antifoam agent, and an antifreeze agent with water in another blending tank.
3. High-shear mixing
Add the water phase to the oil phase with high shear mixing to obtain a dispersible EW emulsion formulation. The mixture was prepared with the aid of an apparatus such as a high-shear mixer, a high pressure orifice homogenizer and the like.
The samples were tested for low temperature stability and heat storage stability. Low temperature stability was tested in a low temperature apparatus at -14°C for 30 days. Heat storage stability was tested in an oven at 54°C for 14 days. After finishing the test, the formulation was filtered through a 342 mesh sieve, and the flowability of the formulation and the formation of crystals observed.
The performance of the formulation upon dilution was also determined. In particular, the dilution stability in a ratio of 5% v/v in CIPAC D stand water was tested at 30°C for 24 hour, the formation of crystals determined and the separation status observed.
The trials to check relative phytotoxicity were carried out with the following samples according to the present invention and a comparative trial based on a commercial Lufenuron 50 EC product. In terms of the severity of the symptoms, the test samples are categorized as follows:
Cat 0: no phytotoxicity Cat 1 : slight phytotoxicity
Cat 2: strong phytotoxicity
Example 1
The liquid formulation described in Table 1 was prepared containing the indicated C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether and lufenuron as active ingredient, wherein the ratio of lufenuron and C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether was approximately 1 :5. The formulation of Example 1 contained the C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether in an amount of 25%wt.
Table 1
Figure imgf000012_0001
Example 2
The liquid formulation described in Table 2 was prepared containing the indicated C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether and novaluron as the active ingredient, wherein the ratio of novaluron and C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether was approximately 1 :4. The formulation of Example 2 contained the C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether in an amount of 40%wt. Table 2
EXAMPLE 2: novaluron EW
Component Composition novaluron tech 100kg( as pure)
Sodium dodecylphenylsulfonate 100kg
TWEEN 80 100kg Sorbitan monooleate ethoxylate
Diethyl glycol methyl ether 400kg
Xantam gum 5kg
Propylene glycol 5kg
WATER 290kg
Total 1000kg
Example 3
The liquid formulation described in Table 3 was prepared containing the indicated C2-C4 dialkylene glycol di-/mono- (- C4 alkyl ether and hexafluron as the active ingredient, wherein the ratio of hexaflumuron and C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether was approximately 1 :3. The formulation of Example 3 contained the C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether in an amount of 24%wt.
Table 3
EXAMPLE 3: hexaflumuron EW
Component Composition hexaflumuron tech 80kg( as pure)
Sodium dodecylphenylsulfonate 100kg
TWEEN 80 100kg
Sorbitan monooleate ethoxylate
Dipropylene glycol dimethyl ether 240kg
Xantam gum 5kg
Propylene glycol 5kg
WATER 470kg
Total 1000kg Example 4
The liquid formulation described in Table 4 was prepared containing the indicated C2-C4 dialkylene glycol di-/mono- (- C4 alkyl ether and triflumuron as the active ingredient, wherein the ratio of triflumuron and C2-C4 dialkylene glycol di-/mono- (- C4 alkyl ether was approximately 1 :2. The formulation of Example 4 contained the C2-C4 dialkylene glycol di-/mono- (- C4 alkyl ether in an amount of 10%wt.
Table 4
Figure imgf000014_0001
Example 5 The liquid formulation described in Table 5 was prepared containing the indicated C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether and diflubenzuron as the active ingredient, wherein the ratio of diflubenzuron and C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether was approximately 1 :5. The formulation of Example 5 contained the C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether in an amount of 50%wt. Table 5
EXAMPLE 5: diflubenzuron EW
Component Composition diflubenzuron tech 100kg( as pure)
Sodium dodecylphenylsulfonate 100kg
TWEEN 80 100kg
Sorbitan monooleate ethoxylate dipropylene glycol methyl ether 500kg
Xantam gum 5kg
Propylene glycol 5kg
Water 190kg
Total 1000kg
Example 6
The liquid formulation described in Table 6 was prepared containing the indicated C2-C4 dialkylene glycol di-/mono- (- C4 alkyl ether and chlorfluazuron as the active ingredient, wherein the ratio of chlorfluazuron and C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether was approximately 1 :0.5. The formulation of Example 6 contained the C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether in an amount of 10%wt.
Table 6
Figure imgf000015_0001
Example 7
The liquid formulation described in Table 7 was prepared containing the indicated C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether and flufenoxuron as the active ingredient, wherein the ratio of flufenoxuron and C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether was approximately 1 : 1 . The formulation of Example 7 contained the C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether in an amount of 25%wt. Table 7
EXAMPLE 7: flufenoxuron EW
Component Composition flufenoxuron tech 250kg( as pure)
Sodium dodecylphenylsulfonate 100kg
TWEEN 80 100kg
Sorbitan monooleate ethoxylate
diethylene glycol ethyl ether 250kg
Xantam gum 5kg
Propylene glycol 5kg
Water 290kg
Total 1000kg
Example 8
The liquid formulation described in Table 8 was prepared containing the indicated C2-C4 dialkylene glycol di-/mono- (- C4 alkyl ether and noviflumuron as the active ingredient, wherein the ratio of noviflumuron and C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether was approximately 1 :5. The formulation of Example 8 contained the C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether in an amount of 25%wt.
Table 8
EXAMPLE 8: novaluron EW
Component Composition
Noviflumuron tech 50kg( as pure)
Sodium dodecylphenylsulfonate 100kg
TWEEN 80 150kg
Sorbitan monooleate ethoxylate
dipropylene glycol diethyl ether, 250kg
Xantam gum 5kg
Propylene glycol 5kg
Water 440kg
Total 1000kg Example 9
The liquid formulation described in Table 9 was prepared containing the indicated C2-C4 dialkylene glycol di-/mono- (- C4 alkyl ether and teflubenuron as the active ingredient, wherein the ratio of teflubenuron and C2-C4 dialkylene glycol di-/mono- ( C4 alkyl ether was approximately 1 :5. The formulation of Example 9 contained the C2-C4 dialkylene glycol di-/mono- (- C4 alkyl ether in an amount of 20%wt.
Table 9
EXAMPLE 9: teflubenuron EW
Component Composition teflubenuron tech 40kg( as pure)
Sodium dodecylphenylsulfonate 100kg
TWEEN 80 160kg
Sorbitan monooleate ethoxylate
dipropylene glycol ethyl ether 200kg
Xantam gum 5kg
Propylene glycol 5kg
Water 490kg
Total 1000kg
Example 10
The liquid formulation described in Table 10 was prepared containing the indicated C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether and a combination of novaluron and lufenuron as active ingredients, wherein the ratio of novaluron plus lufenuron and C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether was approximately 1 :3. The formulation of Example 10 contained the C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether in an amount of 30%wt.
Table 10
EXAMPLE 10: novaluron+lufenuron EW
Component Composition novaluron tech 50kg( as pure)
Lufenuron tech 50kg( as pure)
Sodium dodecylphenylsulfonate 100kg TWEEN 80 100kg
Sorbitan monooleate ethoxylate
Dibutylene glycol diethyl ether 300kg
Xantam gum 5kg
Propylene glycol 5kg
Water 290kg
Total 1000kg
Example 11
The liquid formulation described in Table 1 1 was prepared containing the indicated C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether and a combination of triflumuron and hexaflumuron as active ingredients, wherein the ratio of triflumuron plus hexaflumuron and C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether was
approximately 1 : 1.5. The formulation of Example 1 1 contained the C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether in an amount of 30%wt.
Table 1 1
EXAMPLE 11 : hexaflumuron+triflumuron EW
Component Composition hexaflumuron tech 100kg( as pure)
Triflumuron tech 100kg( as pure)
Sodium dodecylphenylsulfonate 100kg
TWEEN 80 100kg
Sorbitan monooleate ethoxylate
dibutylene glycol ethyl ether 300kg
Xantam gum 5kg
Propylene glycol 5kg
Water 290kg
Total 1000kg
Example 12
The liquid formulation described in Table 12 was prepared containing the indicated C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether and a combination of diflubenzuron and chlorfuazuron as active ingredients, wherein the ratio of diflubenzuron plus chlorfluazuron and C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether was approximately 1 :2. The formulation of Example 12 contained the C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether in an amount of 30%wt. Table 12
Figure imgf000019_0001
Example 13
The liquid formulation described in Table 13 was prepared containing the indicated C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether and a combination of flufenoxuron and noviflumuron as active ingredients, wherein the ratio of flufenoxuron plus noviflumuron and C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether was
approximately 1 : 1 .4. The formulation of Example 13 contained the C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether in an amount of 35%wt. Table 13
EXAMPLE 13: flufenoxuron+noviflumuron EW
Component Composition flufenoxuron tech 200kg( as pure)
Noviflumuron tech 50kg( as pure)
Sodium dodecylphenylsulfonate 100kg TWEEN 80 100kg
Sorbitan monooleate ethoxylate
diethylene glycol propyl ether, 350kg
Xantam gum 5kg
Propylene glycol 5kg
Water 190kg
Total 1000kg
Example 14
The liquid formulation described in Table 1 was prepared containing the indicated C2-C4 dialkylene glycol di-/mono- (- C4 alkyl ether and a combination of noviflumuron and teflubenzuron as active ingredients, wherein the ratio of noviflumuron plus teflubenzuron and C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether was approximately 1 : 1.3. The formulation of Example 14 contained C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether in an amount of 40%wt.
Table 14
EXAMPLE 14: novaluron EW
Component Composition noviflumuron tech 100kg( as pure)
Teflubenzuron 200kg( as pure)
Sodium dodecylphenylsulfonate 100kg
TWEEN 80 100kg
Sorbitan monooleate ethoxylate
dipropylene glycol dipropyl ether 400kg
Xantam gum 5kg
Propylene glycol 5kg
Water 90kg
Total 1000kg
Example 15
The liquid formulation described in Table 15 was prepared containing the indicated C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether and a combination of novaluron and hexaflumuron as active ingredients, wherein the ratio of novaluron plus hexaflumuron and C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether was
approximately 1 :5. The formulation of Example 15 contained the C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether in an amount of 50%wt.
Table 15
EXAMPLE 15: novaluron+hexaflumuron EW
Component Composition novaluron tech 50kg( as pure)
Hexaflumuron tech 50kg(as pure)
Sodium dodecylphenylsulfonate 100kg
TWEEN 80 100kg
Sorbitan monooleate ethoxylate
dipropylene glycol propyl ether 500kg
Xantam gum 5kg
Propylene glycol 5kg
Water 190kg
Total 1000kg
Example 16
The liquid formulation described in Table 16 was prepared containing the indicated C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether and a combination of lufenuron and triflumuron as active ingredients, wherein the ratio of lufenuron plus triflumuron and C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether was approximately 1 :2. The formulation of Example 16 contained the C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether in an amount of 36%wt.
Table 16
EXAMPLE 16: lufenuron+triflumuron EW
Component Composition
Lufenuron tech 80kg( as pure)
Triflumuron tech 100kg( as pure)
Sodium dodecylphenylsulfonate 100kg
TWEEN 80 100kg
Sorbitan monooleate ethoxylate dibutylene glycol dipropyl ether 360kg
Xantam gum 5kg
Propylene glycol 5kg
Water 250kg
Total 1000kg
Example 17
The liquid formulation described in Table 17 was prepared containing the indicated C2-C4 dialkylene glycol di-/mono- (- C4 alkyl ether and a combination of lufenuron and diflubenzuron as active ingredients, wherein the ratio of lufenuron plus diflubenzuron and C2-C4 dialkylene glycol di-/mono- (- C4 alkyl ether was approximately 1 : 1 .8. The formulation of Example 17 contained C2-C4 dialkylene glycol di-/mono- (- C4 alkyl ether in an amount of 45%wt.
Table 17
Figure imgf000022_0001
Example 18
The liquid formulation described in Table 18 was prepared containing the indicated C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether and a combination of lufenuron and chlorfluazuron as active ingredients, wherein the ratio of lufenuron plus chlorfluazuron and C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether was approximately 1 : 1 .4. The formulation of Example 18 contained the C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether in an amount of 35%wt.
Table 18
EXAMPLE 18: lufenuron+chlorfluazuron EW
Component Composition
Lufenuron tech 50kg( as pure)
Chlorfluazuron tech 200kg( as pure)
Sodium dodecylphenylsulfonate 100kg
TWEEN 80 100kg
Sorbitan monooleate ethoxylate
diethylene glycol dibutyl ether 350kg
Xantam gum 5kg
Propylene glycol 5kg
Water 190kg
Total 1000kg
Example 19
The liquid formulation described in Table 19 was prepared containing the indicated C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether and a combination of lufenuron and flufenoxuron as active ingredients, wherein the ratio of lufenuron plus flufenoxuron and C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether was approximately 1 :5. The formulation of Example 19 contained the C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether in an amount of 50%wt.
Table 19
EXAMPLE 19: lufenuron+flufenoxuron EW
Component Composition
Lufenuron tech 50kg( as pure)
Flufenoxuron tech 50kg( as pure)
Sodium dodecylphenylsulfonate 50kg
TWEEN 80 50kg
Sorbitan monooleate ethoxylate diethylene glycol butyl ether 500kg
Xantam gum 5kg
Propylene glycol 5kg
Water 290kg
Total 1000kg
Example 20
The liquid formulation described in Table 20 was prepared containing the indicated C2-C4 dialkylene glycol di-/mono- (- C4 alkyl ether and a combination of lufenuron and noviflumuron as active ingredients, wherein the ratio of lufenuron plus noviflumuron and C2-C4 dialkylene glycol di-/mono- (- C4 alkyl ether was approximately 1 : 1 . The formulation of Example 20 contained the C2-C4 dialkylene glycol di-/mono- (- C4 alkyl ether in an amount of 35%wt.
Table 20
EXAMPLE 20: lufenuron+ noviflumuron EW
Component Composition lufenuron tech 100kg( as pure)
Noviflumuron tech 250kg(as pure)
Sodium dodecylphenylsulfonate 100kg
TWEEN 80 100kg
Sorbitan monooleate ethoxylate
dipropylene glycol dibutyl ether 350kg
Xantam gum 5kg
Propylene glycol 5kg
Water 90kg
Total 1000kg
Example 21
The liquid formulation described in Table 21 was prepared containing the indicated C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether and a combination of lufenuron and teflubenzuron as active ingredients, wherein the ratio of lufenuron plus teflubenzuron and C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether was approximately 1 :2. The formulation of Example 1 contained the C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether in an amount of 20%wt.
Table 21
EXAMPLE 21 : lufenuron+teflubenzuron EW
Component Composition lufenuron tech 50kg( as pure) teflubenzuron 50kg(as pure)
Sodium dodecylphenylsulfonate 100kg
TWEEN 80 100kg
Sorbitan monooleate ethoxylate
dipropylene glycol butyl ether 100kg dipropylene glycol dibutyl ether 100kg
Xantam gum 5kg
Propylene glycol 5kg
Water 490kg
Total 1000kg
Example 22
The liquid formulation described in Table 22 was prepared containing the indicated C2-C4 dialkylene glycol di-/mono- C-|-C4 alkyl ether and a combination of triflumuron and teflubenzuron as active ingredients, wherein the ratio of triflumuron plus teflubenzuron and C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether was approximately 1 :2. The formulation of Example 22 contained the C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether in an amount of 40%wt.
Table 22
EXAMPLE 22: triflumuron+teflubenzuron EW
Component Composition triflumuron tech 100kg( as pure)
Teflubenuron tech 100kg(as pure)
Sodium dodecylphenylsulfonate 100kg
TWEEN 80 100kg
Sorbitan monooleate ethoxylate dibutylene glycol dibutyl ether 200kg
dipropylene glycol butyl ether 200kg
Xantam gum 5kg
Propylene glycol 5kg
Water 190kg
Total 1000kg
Example 23
The liquid formulation described in Table 23 was prepared containing the indicated C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether and a combination of triflumuron and noviflumuron as active ingredients, wherein the ratio of triflumuron plus noviflumuron and C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether was
approximately 1 :3.3. The formulation of Example 23 contained the C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether in an amount of 50%wt.
Table 23
EXAMPLE 23: triflumuron+ noviflumuron EW
Component Composition triflumuron tech 100kg( as pure)
Noviflumuron tech 50kg( as pure)
Sodium dodecylphenylsulfonate 100kg
TWEEN 80 100kg
Sorbitan monooleate ethoxylate
dibutylene glycol butyl ether 500kg
Xantam gum 5kg
Propylene glycol 5kg
Water 140kg
Total 1000kg
Example 24
The samples from Example 1 -23 were tested for low temperature stability at -14°C for 30 days and for heat storage stability at 54°C for 14 days. The dilution stability in a ratio of 5% v/v in CIPAC D stand water was also tested at 30°C for 24hour. The trials to check relative phytotoxicity were carried out with the following samples according to the present invention and comparative trial based on a commercial Lufenuon 50 EC product. In terms of the severity of the phytotoxic symptoms, the test samples were categorized as follows: Cat 0: no phytotoxicity
Cat 1 : slight phytotoxicity
Cat 2: strong phytotoxicity The emulsion formulatins of the present invention had the following characteristics:
Examples Low temperature Heat storage stability The dilution (5% v/v) stability at -14oc for at 54°C for 14days stability for 24h 30days
Example 1 Good flowability, no Good flowability, no No separation, no crystal formation crystal formation crystal formation
Example 2 Good flowability, no Good flowability, no No separation, no crystal formation crystal formation crystal formation
Example 3 Good flowability, no Good flowability, no No separation, no crystal formation crystal formation crystal formation
Example 4 Good flowability, no Good flowability, no No separation, no crystal formation crystal formation crystal formation
Example 5 Good flowability, no Good flowability, no No separation, no crystal formation crystal formation crystal formation
Example 6 Good flowability, no Good flowability, no No separation, no crystal formation crystal formation crystal formation
Example 7 Good flowability, no Good flowability, no No separation, no crystal formation crystal formation crystal formation
Example 8 Good flowability, no Good flowability, no No separation, no crystal formation crystal formation crystal formation
Example Good flowability, no Good flowability, no No separation, no 10 crystal formation crystal formation crystal formation
Example Good flowability, no Good flowability, no No separation, no 1 1 crystal formation crystal formation crystal formation
Example Good flowability, no Good flowability, no No separation, no 12 crystal formation crystal formation crystal formation Example Good flowability, no Good flowability, no No separation, no 13 crystal formation crystal formation crystal formation
Example Good flowability, no Good flowability, no No separation, no 15 crystal formation crystal formation crystal formation
Example Good flowability, no Good flowability, no No separation, no 16 crystal formation crystal formation crystal formation
Example Good flowability, no Good flowability, no No separation, no 17 crystal formation crystal formation crystal formation
Example Good flowability, no Good flowability, no No separation, no 18 crystal formation crystal formation crystal formation
Example Good flowability, no Good flowability, no No separation, no 19 crystal formation crystal formation crystal formation
Example Good flowability, no Good flowability, no No separation, no 20 crystal formation crystal formation crystal formation
Example Good flowability, no Good flowability, no No separation, no 21 crystal formation crystal formation crystal formation
Example Good flowability, no Good flowability, no No separation, no 22 crystal formation crystal formation crystal formation
Example Good flowability, no Good flowability, no No separation, no 23 crystal formation crystal formation crystal formation
The trials to test phytotoxicity of the formulations showed that the formulations of Examples 1-23 all exhibited a phytoxicity of Cat 1 level. The comparative trial with the commercial Lufenuron 50EC product showed the product to exhibit Cat 2 level phytotoxicity. in summary, the EW formulation of the present invention was sigificantly less phytotoxic than the equivalent commercial EC product.
From the experimental data set out above, it can be seen that the EW formulation according to this present invention has good flowability and storage stability at both low temperatures and high temperatures. Further, the phytotoxicity exhibited by the formulations of this invention is siginficantly less than the equivalent commercial EC formulation. The C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether present in the formulation exhibits significant performance in preventing the crystallization of the insecticidally active benzoylphenyl urea derivatives, while also contributing to a significant reduction in the adverse environmental impacts of the formulations when in use.

Claims

1. An agrochemical composition comprising at least one benzoylphenyl urea active ingredient, a solvent comprising a C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether; and optionally at least one component selected from the group consisting of a surface-active agent, a thickener, an antifoam agent, an antifreeze agent and water.
2. The composition according to claim 1 , wherein the ratio of benzoylphenyl urea active ingredient and the C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether is from 1 :0.1 to 1 :7.5, preferably from 1 :0.5 to 1 :5.
3. The composition according to any preceding claim, wherein two or more C2-C4 dialkylene glycol di-/mono- C C4 alkyl ethers are present.
4. The composition according to any preceding claim, wherein two or more
benzoylphenyl urea active ingredients are present.
5. The composition according to any preceding claim, wherein the C2-C4 dialkylene glycol di-/mono- C-|-C4 alkyl ether is selected from diethylene glycol dimethyl ether, diethylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether, dibutylene glycol dimethyl ether, dibutylene glycol methyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl ether, dibutylene glycol diethyl ether, dibutylene glycol ethyl ether, diethylene glycol dipropyl ether, diethylene glycol propyl ether, dipropylene glycol dipropyl ether, dipropylene glycol propyl ether, dibutylene glycol dipropyl ether, dibutylene glycol propyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl ether, dipropylene glycol dibutyl ether, dipropylene glycol butyl ether, dibutylene glycol dibutyl ether, dibutylene glycol butyl ether and mixtures thereof.
6. The composition according to any preceding claim, wherein the C2-C4 dialkylene glycol di-/mono- C C4 alkyl ether is present in an amount of from 5% to 75% by weight, preferably from 5 to 50% by weight.
7. The composition according to any preceding claim, wherein the benzoylphenyl urea derivative is selected from novaluron, lufenuron, hexaflumuron, triflumuron, diflubenzuron, chlorfluazuron, flufenoxuron, noviflumuron and teflubenzuron and mixtures thereof.
8. The composition according to any preceding claim, wherein the benzoylphenyl urea derivative is present in an amount in the range of from 1 to 70% by weight, more preferably from 5 to 40% by weight.
9. The composition according to any preceding claim, further comprising at least one member component selected from a surface-active agent, a thickener, an antifoam agent, an antifreeze agent, and water.
10. A an agrochemical composition consisting essentially of: (a) 1 %-50% benzoylphenyl urea active ingredient;
(b) 5%-50% of a C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether as a solvent; and
(c) optionally one or more additives selected from a surface-active agent, a thickener, an antifoam agent, an antifreeze agent and water
1 1 . The use of a C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether to prevent the crystallization of insecticidal benzoylphenyl urea derivatives in a liquid agrochemical formulation.
12. The use of a C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ether to reduce the phytotoxicity of an EW emulsion formulation of a benzoylphenyl urea.
13. The use according to either of claims 1 1 or 12, wherein the C2-C4 dialkylene glycol di-/mono- (- C4 alkyl ether is present in the formulation as a solvent for the active ingredient.
14. A method of preparing an EW emulsion agrochemical formulation, the method comprising: (1 ) Mixing one or more pesticidally active benzoylphenyl ureas with one or more C2-C4 dialkylene glycol di-/mono- C1-C4 alkyl ethers to form a homogeneous oil phase;
(2) Mixing one or more additives selected from a surface-active agent, a thickener, an antifoam agent, an antifreeze agent and water; (3) Combining the water phase and the oil phase to form a dispersible EW emulsion formulation.
15. The method according to claim 14, wherein the water phase and the oil phase are combined with mixing, preferably with the aid of an apparatus such as a high-shear mixer or a high pressure orifice homogenizer.
16. A method of treating pests at a locus comprising applying to the locus an
effective amount of a composition according to any of claims 1 to 10.
17. The method according to claim 16, wherein the composition is diluted with water before application to the locus.
18. The use of a composition according to any of claims 1 to 10 in the treatment of pests at a locus.
PCT/CN2011/074623 2010-06-17 2011-05-25 Pesticidal composition WO2011157102A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
MYPI2012005443A MY172609A (en) 2010-06-17 2011-05-25 Pesticidal composition
CN201180029390.XA CN103037686B (en) 2010-06-17 2011-05-25 Pesticidal Composition
AP2013006677A AP3618A (en) 2010-06-17 2011-05-25 Pesticidal composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BRPI1002288-0A BRPI1002288A2 (en) 2010-06-17 2010-06-17 AGROCHEMICAL COMPOSITION, USE OF A DI / MONO C1-C4 ALKYL ALCOHOL DIALKYLENE GLYCOL C2-C4, METHOD FOR PREPARING AN EW EMULSION FORMULATION, PEST TREATMENT METHOD AND USE OF COMPOSITION
BRPI1002288-0 2010-06-17

Publications (1)

Publication Number Publication Date
WO2011157102A1 true WO2011157102A1 (en) 2011-12-22

Family

ID=45347660

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2011/074623 WO2011157102A1 (en) 2010-06-17 2011-05-25 Pesticidal composition

Country Status (9)

Country Link
CN (1) CN103037686B (en)
AP (1) AP3618A (en)
AR (1) AR081952A1 (en)
BR (1) BRPI1002288A2 (en)
CO (1) CO6650417A2 (en)
CR (1) CR20120640A (en)
EC (1) ECSP12012340A (en)
PE (1) PE20131028A1 (en)
WO (1) WO2011157102A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016124610A1 (en) * 2015-02-03 2016-08-11 Bimeda Finance S.A.R.L. A formulation for treatment of blowfly strike

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2005100403A4 (en) * 2005-05-13 2005-06-09 Jurox Pty Ltd Parasiticide Composition
WO2005053746A1 (en) * 2003-12-04 2005-06-16 Jurox Pty Ltd Improved parasiticide composition
JP2006056810A (en) * 2004-08-19 2006-03-02 Shinto Fine Co Ltd Harmful insect-controlling composition and harmful insect-controlling method
CN101642121A (en) * 2009-06-24 2010-02-10 深圳诺普信农化股份有限公司 Complex composition containing lufenuron
CN101690475A (en) * 2009-07-07 2010-04-07 深圳诺普信农化股份有限公司 Lufenuron multiple emulsion and preparation method thereof
CN101697733A (en) * 2009-09-30 2010-04-28 深圳诺普信农化股份有限公司 Lufenuron-containing aqueous emulsion and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005053746A1 (en) * 2003-12-04 2005-06-16 Jurox Pty Ltd Improved parasiticide composition
JP2006056810A (en) * 2004-08-19 2006-03-02 Shinto Fine Co Ltd Harmful insect-controlling composition and harmful insect-controlling method
AU2005100403A4 (en) * 2005-05-13 2005-06-09 Jurox Pty Ltd Parasiticide Composition
CN101642121A (en) * 2009-06-24 2010-02-10 深圳诺普信农化股份有限公司 Complex composition containing lufenuron
CN101690475A (en) * 2009-07-07 2010-04-07 深圳诺普信农化股份有限公司 Lufenuron multiple emulsion and preparation method thereof
CN101697733A (en) * 2009-09-30 2010-04-28 深圳诺普信农化股份有限公司 Lufenuron-containing aqueous emulsion and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016124610A1 (en) * 2015-02-03 2016-08-11 Bimeda Finance S.A.R.L. A formulation for treatment of blowfly strike
GB2551451A (en) * 2015-02-03 2017-12-20 Bimeda Finance S A R L A formulation for treatment of blowfly strike
GB2551451B (en) * 2015-02-03 2020-05-27 Bimeda Finance S A R L A formulation for treatment of blowfly strike
GB2580572A (en) * 2015-02-03 2020-07-22 Bimeda Finance S A R L A formulation for treatment of blowfly strike
AU2019283896B2 (en) * 2015-02-03 2021-04-01 Bimeda Finance S.A.R.L. A formulation for treatment of blowfly strike

Also Published As

Publication number Publication date
CR20120640A (en) 2013-04-08
AP2013006677A0 (en) 2013-01-31
CN103037686B (en) 2014-07-23
AP3618A (en) 2016-02-29
CN103037686A (en) 2013-04-10
BRPI1002288A2 (en) 2012-03-13
ECSP12012340A (en) 2012-12-28
CO6650417A2 (en) 2013-04-15
PE20131028A1 (en) 2013-09-18
AR081952A1 (en) 2012-10-31

Similar Documents

Publication Publication Date Title
JP3152991B2 (en) Liquid herbicide composition
EP2819513B1 (en) Emulsifiable concentrate formulation
US10130091B2 (en) Agrochemical emulsifiable concentrate formulation
JP2001511801A (en) Pesticide surfactant composition
US7314848B1 (en) Adjuvant composition for chemicals used in agriculture
MX2009001213A (en) Defoliant composition and method.
JP5898192B2 (en) Agrochemical formulation
WO2019243927A1 (en) Stable co-formulation of benzoylurea with pyrethroids.
EP1608220B2 (en) Pesticides formulations
US6187715B1 (en) Water-based microemulsions of a lower alkyl ester of quinoxalinyl herbicide
WO2011157102A1 (en) Pesticidal composition
US6541516B1 (en) Water miscible emulsions of pyrethroid insecticides or triazole fungicides
TWI434653B (en) Use of a c2-c4 dialkylene glycol di-/mono- c1-c4 alkyl ether
WO2011157101A1 (en) Pesticidal composition
KR920003208B1 (en) Composition for selectively controlling weeds in crops of transplanted rice plants of in rice crops grown in water from seed
KR20240017815A (en) Pesticide composition containing diamide and tetramic acid compounds
US20060105007A1 (en) Stable matrix emulsion concentrates and stable aqueous and/or organic solvent compositions containing biocides
CN114144062A (en) Pesticidal formulations
WO2020049493A1 (en) Stable agrochemical composition
WO2011034444A1 (en) Herbicidal surfactant formulations
WO2020011950A1 (en) Plant growth regulator concentrate and use thereof
US20060058191A1 (en) Pesticide solvent system for reducing phytotoxicity
JP4707129B2 (en) Emulsion composition
OA20624A (en) Stable Agrochemical Composition
JPH07524B2 (en) Pyrethroid pesticide composition

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201180029390.X

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11795068

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2772/MUMNP/2012

Country of ref document: IN

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 12228116

Country of ref document: CO

Ref document number: 002441-2012

Country of ref document: PE

Ref document number: CR2012-000640

Country of ref document: CR

ENP Entry into the national phase

Ref document number: 0174113

Country of ref document: KE

ENP Entry into the national phase

Ref document number: 0175313

Country of ref document: KE

122 Ep: pct application non-entry in european phase

Ref document number: 11795068

Country of ref document: EP

Kind code of ref document: A1