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CN113749092B - Unsaturated fatty acid ester application, agrochemical composition, low-eye-prick pesticide preparation and application thereof - Google Patents

Unsaturated fatty acid ester application, agrochemical composition, low-eye-prick pesticide preparation and application thereof Download PDF

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Publication number
CN113749092B
CN113749092B CN202010493341.2A CN202010493341A CN113749092B CN 113749092 B CN113749092 B CN 113749092B CN 202010493341 A CN202010493341 A CN 202010493341A CN 113749092 B CN113749092 B CN 113749092B
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fatty acid
acid ester
unsaturated fatty
pesticide
agrochemical composition
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CN113749092A (en
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许仙波
陈邦池
章金龙
穆海萍
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MAX (RUDONG) CHEMICALS CO LTD
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MAX (RUDONG) CHEMICALS CO LTD
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Priority to CN202010493341.2A priority Critical patent/CN113749092B/en
Priority to PCT/CN2021/095590 priority patent/WO2021244347A1/en
Priority to BR112022024744A priority patent/BR112022024744A2/en
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • A01N25/02Biocides, 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
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • A01N25/32Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647Triazoles; Hydrogenated triazoles
    • A01N43/6531,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01PBIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P13/00Herbicides; Algicides
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01PBIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00Fungicides
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01PBIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00Arthropodicides
    • A01P7/04Insecticides

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  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Zoology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Environmental Sciences (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Toxicology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mycology (AREA)
  • Microbiology (AREA)
  • Insects & Arthropods (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Medicinal Preparation (AREA)

Abstract

The invention provides an application of an unsaturated fatty acid ester, an agrochemical composition, a low-eye-prick pesticide preparation and application thereof, and relates to the technical field of pesticides. The agrochemical composition provided by the invention is more easy to emulsify the hydrophobic pesticide into small liquid drops through the unsaturated fatty acid ester and the hydrophobic pesticide to be discharged out of eyes along with tears through the mutual synergy of the unsaturated fatty acid ester and the hydrophobic pesticide, and the contact time of the hydrophobic pesticide and eyes or epidermis is reduced, so that the irritation of the pesticide preparation to eyes is reduced. In addition, the unsaturated fatty acid ester can form a barrier on the outer layer of the cornea of the eye, so that the contact and damage of the pesticide preparation to the eye are reduced, and meanwhile, the unsaturated fatty acid ester also has a certain moisture retention property, and is beneficial to helping the recovery of the eye.

Description

Unsaturated fatty acid ester application, agrochemical composition, low-eye-prick pesticide preparation and application thereof
Technical Field
The invention relates to the technical field of pesticides, in particular to application of unsaturated fatty acid ester, an agrochemical composition, a low-eyestrain pesticide preparation and application thereof.
Background
Most of the active components in the agrochemical preparation are hydrophobic pesticides, organic solvents such as aromatic hydrocarbon, alcohol ether and pyrrolidone are required to be dissolved and then prepared into liquid preparations such as emulsifiable concentrates or aqueous emulsion, but the organic solvents are easy to cause ecological toxicology problems. When the agrochemical liquid preparations are sprayed, if the agrochemical liquid preparations are accidentally sputtered or enter eyes of operators during spraying, the eyes are irritated or damaged, and the health of the operators is affected. After application, the eye of the wild animal is also damaged, which causes the survival crisis and destroys the ecological balance. There are now many countries in which there are restrictions on the toxicity and irritation of agrochemical liquid formulations, such as Brazil, which limits the use of class I toxicity-irritating emulsifiable concentrates in the market, germany requires that such agrochemical formulations be sold with eco-toxic tags, and operators themselves are not willing to purchase and use agrochemical products with a high toxicity irritation.
At present, a technical scheme for well reducing the irritation of an agrochemical liquid preparation containing an organic solvent is not available, some commercial preparations attempt to reduce the ecological toxicology problem of agrochemical products by using solvents with low toxicity and low eye irritation such as aliphatic hydrocarbon, paraffin oil and the like, but the substances have small dissolving capacity to active ingredients in the agrochemical preparations and narrow application range, and are difficult to meet the requirements of various agrochemical hydrophobic pesticides.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide an application of an unsaturated fatty acid ester in preparing a pesticide preparation for reducing eye irritation, so as to solve the technical problems that the solubility of a hydrophobic pesticide in the existing various pesticide preparations is limited and the ecological toxicity is high.
The second purpose of the invention is to provide an agrochemical composition to solve the technical problems that the existing agrochemical liquid preparation has large ecological toxicity and is easy to cause harm to the health of operators.
It is a further object of the present invention to provide the use of the agrochemical composition as described above for the preparation of a pesticide formulation which reduces eye irritation.
The invention aims at providing a pesticide preparation with low eyestrain so as to solve the technical problems that the existing agrochemical liquid preparation is high in ecological toxicity, easy to cause eye irritation of operators and endanger the health of the operators.
The fifth purpose of the invention is to provide the application of the low-eyespot pesticide preparation in weeding, sterilizing or pest killing and plant growth regulating.
One of the objects of the present invention is the use of an unsaturated fatty acid ester in the preparation of a pesticide formulation for reducing eye irritation, said unsaturated fatty acid ester having the general formula:
wherein a=0-18, n=1-4, b=0-8,c =0-18, d=0-4, and a, b, and c are not 0 at the same time.
Further, the number of carbon-carbon double bonds in the unsaturated fatty acid ester is 1 to 8, preferably 1 to 3;
Preferably, in the unsaturated fatty acid ester, the number of carbon atoms of the fatty chain is 6 to 24;
Preferably, the unsaturated fatty acid ester is an unsaturated fatty acid methyl ester.
Another object of the present invention is to provide an agrochemical composition comprising an unsaturated fatty acid ester and a hydrophobic pesticide in the use according to the invention;
further, the hydrophobic pesticide comprises at least one of acetochlor, permethrin, bifenthrin, carfentrazone-ethyl, trinexapac-ethyl, triclopyr derivatives, clomazone, metolachlor, 2,4-D ester, chlorpyrifos, pendimethalin, tebuconazole, difenoconazole, pinoxaden, avermectin and trifluralin.
The triclopyr derivative comprises triclopyr an agriculturally acceptable ester of triclopyr and an agriculturally acceptable salt of triclopyr, such as butoxyethyl triclopyr, and triethylamine triclopyr salts.
Further, the agrochemical composition further comprises an emulsifier;
Preferably, the emulsifier comprises at least one of alkylbenzene sulfonate, alkyl sulfonate, carboxylate, alcohol alkoxylate, alkylphenol ethoxylate, castor oil ethoxylate, amine ethoxylate, sorbitan ester, alkyl glycoside, ethylene oxide-propylene oxide copolymer, ethoxylated phenol phosphate, tristyrylphenol phosphate, fatty alcohol polyoxyethylene ether, and fatty acid polyoxyethylene ester.
Further, the mass ratio of the unsaturated fatty acid ester in the agrochemical composition is 15-95%, preferably 20-60%;
The mass ratio of the hydrophobic pesticide in the agrochemical composition is 5-85%; preferably 5 to 50%.
It is a further object of the present invention to provide the use of said agrochemical composition for the preparation of a pesticide formulation with reduced eye irritation.
It is a fourth object of the present invention to provide a low-eyepuncture pesticide formulation comprising an unsaturated fatty acid ester for use in accordance with the present invention or an agrochemical composition in accordance with the present invention.
Further, the low-eye-prick pesticide preparation is a liquid preparation;
preferably, the low-eyepoint pesticide formulation is an emulsifiable concentrate formulation.
The fifth object of the present invention is to provide the use of the above-mentioned low-eyepoint pesticide formulation in weeding, sterilizing, insecticidal or plant growth regulating.
The unsaturated fatty acid ester provided by the invention has no irritation to eyes, is low in toxicity, and is easy to emulsify hydrophobic pesticides and other auxiliary agents in pesticide preparations into small liquid drops to be discharged out of eyes along with tears, so that the contact time of the hydrophobic pesticides and other auxiliary agents with eyes or epidermis is reduced, and the irritation of the pesticide preparations to eyes is reduced. In addition, the unsaturated fatty acid ester provided by the invention can also form a barrier on the outer layer of the cornea of the eye, so that the contact and damage of hydrophobic pesticides and other auxiliary agents to the eye are reduced, and meanwhile, the unsaturated fatty acid ester has a certain moisture retention property, and is beneficial to helping the recovery of the eye.
The agrochemical composition provided by the invention is more easy to emulsify the hydrophobic pesticide into small liquid drops through the unsaturated fatty acid ester and the hydrophobic pesticide to be discharged out of eyes along with tears through the mutual synergy of the unsaturated fatty acid ester and the hydrophobic pesticide, and the contact time of the hydrophobic pesticide and eyes or epidermis is reduced, so that the irritation of the hydrophobic pesticide to eyes is reduced. In addition, the unsaturated fatty acid ester can form a barrier on the outer layer of the cornea of the eye, so that the contact and damage of the hydrophobic pesticide to the eye are reduced, and meanwhile, the unsaturated fatty acid ester also has a certain moisture retention property, and is beneficial to helping the recovery of the eye.
According to the low-eye-prick pesticide preparation, the unsaturated fatty acid ester is added, so that the contact time of the hydrophobic pesticide with eyes or epidermis can be reduced, the irritation of the hydrophobic pesticide to the eyes can be reduced, a barrier can be formed on the outer layer of cornea of the eyes, the contact and damage of the hydrophobic pesticide to the eyes can be reduced, the recovery of the eyes can be facilitated, and the safety and health of operators can be facilitated. In addition, the agrochemical composition preparation provided by the invention can reduce the injury of pesticides to eyes of wild animals, reduce ecological crisis and facilitate ecological system balance through mutual cooperation of the unsaturated fatty acid ester and the hydrophobic pesticides.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
According to one aspect of the present invention there is provided the use of an unsaturated fatty acid ester in a pesticide formulation for reducing eye irritation, the unsaturated fatty acid ester having the formula:
wherein a=0-18, n=1-4, b=0-8,c =0-18, d=0-4, and a, b, and c are not 0 at the same time.
Typically, but not limited to, a, c are each independently 0, 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18; n is 1,2, 3 or 4; b is 0, 1,2, 3, 4, 5, 6, 7 or 8; d is 0, 1,2, 3 or 4, and a, b and c cannot be simultaneously 0.
Unsaturated fatty acid has fat solubility, is an important component of retina, has the function of promoting cell repair, and has better compatibility with hydrophobic pesticides. The unsaturated fatty acid ester also has moisture keeping and antioxidant effects in cosmetics.
The unsaturated fatty acid ester provided by the invention has no irritation to eyes, is low in toxicity, and is easy to emulsify hydrophobic pesticides and other auxiliary agents in pesticide preparations into small liquid drops to be discharged out of eyes along with tears, so that the contact time of the hydrophobic pesticides and other auxiliary agents with eyes or epidermis is reduced, and the irritation of the pesticide preparations to eyes is reduced. In addition, the unsaturated fatty acid ester provided by the invention can also form a barrier on the outer layer of the cornea of the eye, so that the contact and damage of hydrophobic pesticides and other assistants to the eye are reduced, and meanwhile, the unsaturated fatty acid ester also has a certain moisture retention property, and is beneficial to helping the recovery of the eye.
In a preferred embodiment of the present invention, the number of carbon-carbon double bonds in the unsaturated fatty acid ester is 1 to 8, so that the unsaturated fatty acid ester has relatively excellent performance, and can be better mutually dissolved with the hydrophobic pesticide in the pesticide preparation, so that the contact time of the hydrophobic pesticide and other auxiliary agents with eyes or epidermis can be better reduced, and especially when the number of carbon-carbon double bonds in the unsaturated fatty acid ester is 1 to 3, the performance of the unsaturated fatty acid ester is relatively excellent, the mutual solubility of the unsaturated fatty acid ester with the hydrophobic pesticide in the pesticide preparation is relatively better, the contact time of the hydrophobic pesticide and other auxiliary agents with eyes or epidermis can be further shortened, the irritation of the pesticide preparation to eyes can be reduced, and the safety and health of operators can be protected.
In a preferred embodiment of the invention, the unsaturated fatty acid ester has 6-24 fatty chain carbon atoms, so that the unsaturated fatty acid ester has better intersolubility with the hydrophobic pesticide in the pesticide preparation, thereby being more beneficial to effectively reducing the irritation of the pesticide preparation to eyes and better ensuring the safety and health of operators.
In a preferred embodiment of the present invention, i.e. when the unsaturated fatty acid ester is unsaturated fatty acid methyl ester, the compatibility with hydrophobic pesticides is better, the irritation of the pesticide preparation to eyes is easier to reduce, and the safety and health of operators are better protected. The unsaturated fatty acid ester is safe and nontoxic, has good intersolubility with the hydrophobic pesticide in the pesticide preparation, is more favorable for forming a stable dispersion system with the hydrophobic pesticide, reduces the irritation of the hydrophobic pesticide and other auxiliary agents to eyes, helps the eyes to recover, and protects the safety and health of operators.
According to a second aspect of the present invention there is provided an agrochemical composition comprising an unsaturated fatty acid ester and a hydrophobic pesticide as provided in the use of the present invention.
In the present invention, the hydrophobic pesticide includes a substance which is slightly soluble in water and/or hardly soluble in water (i.e., the hydrophobic pesticide may be a substance which is slightly soluble in water, a substance which is hardly soluble in water, or a mixture of a substance which is slightly soluble in water and a substance which is hardly soluble in water); the hydrophobic pesticide can be used as an active ingredient for herbicides, insecticides, pest repellents, plant growth regulators, synergists, plant safeners and preservatives.
In the present invention, the hydrophobic pesticide means that the pesticide has a solubility in 100g of water having a pH of 7 of less than 10g, preferably less than 1g, more preferably less than 0.1g at 20℃under standard pressure.
In the present invention, the hydrophobic pesticide may be an active ingredient known in THE PESTICIDE Manual (2018, 18 th edition, british Crop Production Council). Using simple preliminary experiments, the person skilled in the art can select a suitable hydrophobic pesticide from the pesticides of the prior art.
The known pesticides can be classified according to structure and comprise organophosphorus (chlorpyrifos, dimethoate, phoxim, dichlorvos), carbamate (carbofuran), pyrethroid (permethrin, bifenthrin), organic sulfide (mancozeb, thiram), amide (alachlor, acetochlor, metolachlor, isoprothiolane, butachlor), urea compound (chlormequat), ether compound (herbicidal ether, clomazone), phenol compound (sodium pentachlorophenate), phenoxycarboxylic acid (2, 4-D butyl, triclopyr derivative, methoxam), triazobenzene (prometryne, atrazine), benzoic acid (dicamba), amidines (amitraz), triazolinones (carfentrazone), triazoles (difenoxazole, triadimefon), phenylpyrazoline (pinoxaden), cyclohexanecarboxylic acid (trinexade), aniline (pendimethalin), trifluralin (oxaprozin), avermectin, and the like.
The agrochemical composition provided by the invention is more easy to emulsify the hydrophobic pesticide into small liquid drops through the unsaturated fatty acid ester and the hydrophobic pesticide to be discharged out of eyes along with tears through the mutual synergy of the unsaturated fatty acid ester and the hydrophobic pesticide, and the contact time of the hydrophobic pesticide and eyes or epidermis is reduced, so that the irritation of the pesticide preparation to eyes is reduced. In addition, the unsaturated fatty acid ester can form a barrier on the outer layer of the cornea of the eye, so that the contact and damage of the hydrophobic pesticide to the eye are reduced, and meanwhile, the unsaturated fatty acid ester also has a certain moisture retention property, and is beneficial to helping the recovery of the eye.
In a preferred embodiment of the present invention, the hydrophobic pesticide includes, but is not limited to, a hydrophobic pesticide including at least one of acetochlor, permethrin, bifenthrin, carfentrazone, trinexapac-ethyl, triclopyr derivatives, clomazone, metolachlor, 2,4-D ester, chlorpyrifos, pendimethalin, tebuconazole, difenoconazole, pinoxaden, avermectin, and trifluralin.
The above-mentioned "triclopyr derivative" includes triclopyr, an agriculturally acceptable ester of triclopyr (e.g., butoxyethyl triclopyr) and an agriculturally acceptable salt of triclopyr (e.g., triethylamine salt of triclopyr).
The above-mentioned "at least one kind" means that the hydrophobic pesticide of the hydrophobic pesticide includes two or more kinds of substances selected from acetochlor, permethrin, bifenthrin, carfentrazone-ethyl, trinexapac-ethyl, triclopyr derivatives, clomazone, metolachlor, 2,4-D ester, chlorpyrifos, pendimethalin, tebuconazole, difenoconazole, pinoxaden, avermectin or trifluralin.
In a preferred embodiment of the invention, the agrochemical composition further comprises an emulsifier. By adding the emulsifying agent into the agrochemical composition, the unsaturated fatty acid ester and the hydrophobic pesticide are mutually dissolved, and are easier to emulsify into small liquid drops under the action of the emulsifying agent, so that the irritation of the agrochemical composition to eyes is reduced, and the safety and the health of operators are protected.
In a preferred embodiment of the present invention, the emulsifier comprises an ionic emulsifier and/or a nonionic emulsifier.
Emulsifiers are used for emulsifying, wetting, dispersing, suspending or other purposes. The agrochemical composition is applied in the form of a pesticide liquid preparation, and the pesticide liquid preparation needs a certain emulsifier (ionic, nonionic, etc.) to stabilize active ingredients in the preparation, so that good emulsifying dispersibility and emulsifying stability are ensured when the agrochemical composition is diluted by adding water for use, which is the basis of normal use of the product. However, these emulsifiers are also responsible for the severe eye irritation, especially some anionic emulsifiers, which are severe to the eye.
The unsaturated fatty acid ester is added into the agrochemical composition, so that the irritation of hydrophobic pesticides, emulsifying agents and other optional auxiliary agents to eyes can be effectively reduced, and the safety and the health of operators are protected.
The above "and/or" means that the emulsifier may include an ionic emulsifier or a nonionic emulsifier, and may also include a mixture of an ionic emulsifier and a nonionic emulsifier.
In a preferred embodiment of the present invention, the emulsifier comprises at least one of alkylbenzene sulfonate, alkylbenzenesulfonate, alkylsulfonate, carboxylate, alcohol alkoxylate, alkylphenol ethoxylate, castor oil ethoxylate, amine ethoxylate, sorbitan ester, alkyl glycoside, ethylene oxide-propylene oxide copolymer, ethoxylated phenol phosphate, tristyrylphenol phosphate, fatty alcohol polyoxyethylene ether, and fatty acid polyoxyethylene ester.
The above-mentioned "at least one" means that the emulsifier may include any one of alkylbenzene sulfonate, alkylbenzenesulfonate, alkylsulfonate, carboxylate, alcohol alkoxylate, alkylphenol ethoxylate, castor oil ethoxylate, amine ethoxylate, sorbitan ester, alkyl glycoside, ethylene oxide-propylene oxide copolymer, ethoxylated phenol phosphate, tristyrylphenol phosphate, fatty alcohol polyoxyethylene ether and fatty acid polyoxyethylene ester, and may also include any two or more of alkylbenzene sulfonate, alkylbenzenesulfonate, alkylsulfonate, carboxylate, alcohol alkoxylate, alkylphenol ethoxylate, castor oil ethoxylate, amine ethoxylate, sorbitan ester, alkyl glycoside, ethylene oxide-propylene oxide copolymer, ethoxylated phenol phosphate, tristyrylphenol phosphate, fatty alcohol polyoxyethylene ether, and fatty acid polyoxyethylene ester.
In a preferred embodiment of the invention, the mass fraction of unsaturated fatty acid ester in the agrochemical composition is from 15 to 95%, preferably from 20 to 60%.
Typically, but not by way of limitation, the unsaturated fatty acid ester comprises, for example, 15%, 25%, 30%, 60%, 75%, 85% or 95% by mass of the agrochemical composition.
In a preferred embodiment of the invention, the hydrophobic pesticide is present in the agrochemical composition in a mass ratio of from 5 to 85%, preferably from 5 to 50%. The pesticide composition has corresponding pesticide effect by controlling the mass ratio of the hydrophobic pesticide in the pesticide composition.
Typically, but not by way of limitation, the hydrophobic pesticide comprises, for example, 15%, 25%, 40%, 50%, 60%, 75%,80% or 85% by mass of the agrochemical composition.
In a preferred embodiment of the invention, the process for preparing an agrochemical composition comprises the steps of:
And uniformly mixing the unsaturated fatty acid ester, the hydrophobic pesticide and an optional solvent, adding an emulsifying agent and optional other auxiliary agents after the hydrophobic pesticide is dissolved, and uniformly mixing to obtain the agrochemical composition.
The agrochemical composition is a concentrate of the pesticide formulation which, upon dilution in water, can be applied by irrigation, spraying or other conventional methods known to those skilled in the art.
According to a third aspect of the present invention there is provided the use of an agrochemical composition as described above in the preparation of a pesticide formulation which reduces eye irritation.
According to a fourth aspect of the present invention there is provided a low eyepoint pesticide formulation comprising an unsaturated fatty acid ester for use in accordance with the present invention or an agrochemical composition provided in accordance with the present invention.
The "low eye irritation" as used herein refers to low eye irritation, and refers to OECD (2000) or GHS (2007) classification standards, wherein the eye irritation level is Category 2B or lower, i.e., the integral mean of the stimulus response of 2/3 animals: the corneal opacity is less than or equal to 1, the iris is less than or equal to 1, conjunctival congestion is less than or equal to 2, conjunctival edema is less than or equal to 2.
According to the low-eye-prick pesticide preparation, the unsaturated fatty acid ester is added, so that the contact time of the hydrophobic pesticide with eyes or epidermis can be reduced, the irritation of the hydrophobic pesticide to the eyes can be reduced, a barrier can be formed on the outer layer of cornea of the eyes, the contact and damage of the hydrophobic pesticide to the eyes can be reduced, the recovery of the eyes can be facilitated, and the safety and health of operators can be facilitated.
In a preferred embodiment of the present invention, the low-eyepuncture pesticide formulation provided by the present invention is a liquid formulation, more preferably an emulsifiable concentrate formulation.
In a preferred embodiment of the invention, the agrochemical composition or the low eye-prick pesticide formulation is diluted in water to facilitate application in the field and also to facilitate addition to the field by spraying or irrigation.
According to a fifth aspect of the present invention there is provided the use of a low eyepoint pesticide formulation as described above for weeding, sterilizing, pest killing or plant growth regulation.
The technical scheme provided by the invention is further described below by combining examples and comparative examples.
Example 1-1
The present example provides an agrochemical composition comprising the following components in mass fraction: 50% of unsaturated fatty acid ester, 10% of emulsifying agent and 40% of hydrophobic pesticide; the molecular structural formula of the unsaturated fatty acid ester is shown as follows:
Wherein a=4, b=1, c= 7,d =0, n=1; the hydrophobic pesticide is carfentrazone-ethyl; the emulsifiers included calcium dodecylbenzenesulfonate (emulsifier CAL, available from clariant corporation) and EO-PO block polyether (emulsifier ETHYLAN NS-500LQ, available from aku nobel corporation), and the mass ratio of both emulsifiers in the agrochemical composition was 5%.
Examples 1 to 2
The present example provides an agrochemical composition comprising the following components in mass fraction: 25% of unsaturated fatty acid ester, 25% of solvent, 10% of emulsifier and 40% of hydrophobic pesticide; wherein the unsaturated fatty acid ester, the hydrophobic pesticide and the emulsifier are the same as in example 1-1; the solvent is aromatic hydrocarbon solvent Solvesso 150, purchased from Mobil company.
Examples 1 to 3
The present example provides an agrochemical composition comprising the following components in mass fraction: 15% of unsaturated fatty acid ester, 35% of solvent, 10% of emulsifier and 40% of hydrophobic pesticide; wherein the unsaturated fatty acid ester, the hydrophobic pesticide, the emulsifier and the solvent are the same as in examples 1-2.
Examples 1 to 4
This example provides an agrochemical composition which differs from example 1-1 in that the unsaturated fatty acid ester is as follows:
a=4,b=2,c=4,d=1,n=1。
examples 1 to 5
This example provides an agrochemical composition which differs from example 1-1 in that the unsaturated fatty acid ester is as follows:
a=1,b=2,c=7,d=1,n=1。
Examples 1 to 6
This example provides an agrochemical composition which differs from example 1-1 in that the unsaturated fatty acid ester is as follows:
a=4,b=3,c=3,d=0,n=1。
examples 1 to 7
This example provides an agrochemical composition which differs from example 1-1 in that the unsaturated fatty acid ester is as follows:
a=0,b=4,c=3,d=0,n=1。
Comparative examples 1 to 1
The present comparative example provides an agrochemical composition comprising the following components in mass fraction: 10% of an emulsifying agent, 40% of a hydrophobic pesticide and 50% of a solvent; wherein the emulsifier, the hydrophobic pesticide and the solvent are the same as in examples 1-2.
Comparative examples 1 to 2
The present comparative example provides an agrochemical composition comprising the following components in mass fraction: 10% of an emulsifying agent, 40% of a hydrophobic pesticide, 25% of a solvent and 25% of water; wherein the emulsifier, the hydrophobic pesticide and the solvent are the same as in examples 1-2, and the water is deionized water.
Test example 1
The agrochemical compositions provided in examples 1-1 to 1-7 and the agrochemical compositions provided in comparative examples 1-1 to 1-2 were administered to New Zealand white rabbits, respectively, at a dose of 0.1mL each; repeated experiments were performed using 3 New Zealand white rabbits per agrochemical composition to determine the extent to which the agrochemical composition produced eye irritation to the eyes of the white rabbits.
During the test, the drug was applied to conjunctival sac of one eye of each white rabbit, and the other eye was not applied with the drug and used as a blank, and the cornea, iris and conjunctiva of the eye were evaluated for irritation at 24 hours after the administration, and the evaluation results are shown in table 1.
Comparative examples 1-1 to 1-2 showed more severe corneal haze (score 3), conjunctival congestion, conjunctival edema (score 2); the cornea, iris and conjunctiva showed no irritation (score of 0) after administration of example 1-1, and slight conjunctival edema or congestion (score of 0 or 1) after administration of examples 1-2 to 1-7 showed significant improvement over comparative examples 1-1 to 1-2. The unsaturated fatty acid ester can effectively reduce the eye irritation of pesticide preparations and reduce the eye irritation of carfentrazone-ethyl emulsifiable concentrate preparations.
Table 1 eye injury and scoring table
Remarks: the scoring criteria described above were performed with reference to the OECD standard, according to the guidelines test requirements specified in the following documents:
(1)OECD(2000).Guidance Document on the Recognition,Assessment and Use of Clinical Signs as Humane Endpoints for Experimental Animals Used in Safety Evaluation.Environmental Health and Safety Monograph Series on Testing and Assessment No 19.
(2)OECD GUIDELINE FOR THE TESTING OF CHEMICALS.Section 4:Health Effects,No 405:Acute Eye Irritation/Corrosion.OECD,Paris,adopted 02nd October 2012.
(3)UNITED STATES.ENVIRONMENTAL PROTECTION AGENCY.Health Effects Test Guidelines.OPPTS 870.2400,1998.
(4)Globally Harmonized System of Classification and Labelling of Chemicals(GHS),United Nations Economic Commission for Europe,2007,retrieved July 13,2007.
the scoring criteria are as follows:
Stimulus response Score value Remarks
Corneal haze (based on the most dense part) 0-4 Min Maximum stimulation score of 4
Iris 0-2 Min Maximum stimulation score of 2
Conjunctival congestion 0-3 Min Maximum stimulation score of 3
Conjunctival edema (comprising eyelid and third eyelid) 0-4 Min Maximum stimulation score of 4
Test example 2
In each example, a field efficacy test of wheat is carried out, the main weeds in the test field are cleavers and chenopodium album, the grass age is about 3-5 leaves, and the wheat is in the tillering stage. Each example treated a large area with a treatment area of 1 mu, with line separation between different treatments. The agrochemical compositions provided in examples 1-1 to 1-7 and the agrochemical compositions provided in comparative examples 1-1 to 1-2 were sprayed with water, respectively, in an amount of 1.5 g/mu of the active ingredient and 40L/mu of the spray. The control group was sprayed with an equal amount of clear water, the fresh weight control effect of weeds was investigated 15 days after the application of the chemical, and the growth inhibition rate (%) of wheat was visually examined, and the results are shown in table 2.
Examples 1-1 to 1-7 and comparative examples 1-1 to 1-2 have remarkable control effects on broadleaf weeds in wheat fields, and the examples have certain advantages in efficacy over the comparative examples, and all the agents do not show phytotoxicity to wheat at the same dosage.
The composition of Table 2 has the effect of controlling broad-leaved weeds in wheat fields in fields
Example 2-1
The present example provides an agrochemical composition comprising the following components in mass fraction: 57% of unsaturated fatty acid ester, 18% of emulsifying agent and 25% of hydrophobic pesticide; the molecular structural formula of the unsaturated fatty acid ester is shown as the following formula:
Wherein a=4, b=1, c= 7,d =0, n=1; the hydrophobic pesticide is trinexapac-ethyl; the emulsifier included fatty alcohol polyoxyethylene ether (emulsifier Genapol X060, available from clahn company) and polyoxyethylene sorbitan monooleate (emulsifier Tween80, available from hengeipu chemical company), and the mass ratio of fatty alcohol polyoxyethylene ether in the agrochemical composition was 10%, and the mass ratio of polyoxyethylene sorbitan monooleate in the agrochemical composition was 8%.
Example 2-2
The present example provides an agrochemical composition comprising the following components in mass fraction: 40% of unsaturated fatty acid ester, 18% of emulsifying agent, 25% of hydrophobic pesticide and 17% of water; wherein the unsaturated fatty acid ester, the hydrophobic pesticide and the emulsifier are the same as in example 2-1.
Examples 2 to 3
The present example provides an agrochemical composition comprising the following components in mass fraction: 30% of unsaturated fatty acid ester, 25% of emulsifying agent and 45% of hydrophobic pesticide; wherein the unsaturated fatty acid ester, the hydrophobic pesticide and the emulsifier are the same as in example 2-1; the mass ratio of the emulsifier fatty alcohol polyoxyethylene ether in the agrochemical composition is 10%, and the mass ratio of the polyoxyethylene sorbitan monooleate in the agrochemical composition is 15%.
Examples 2 to 4
This example provides an agrochemical composition which differs from example 2-1 in that the unsaturated fatty acid ester is as follows:
a=4,b=2,c=4,d=1,n=1。
Examples 2 to 5
This example provides an agrochemical composition which differs from example 2-1 in that the unsaturated fatty acid ester is as follows:
a=0,b=4,c=3,d=1,n=1。
examples 2 to 6
This example provides an agrochemical composition which differs from example 2-1 in that the unsaturated fatty acid ester is as follows:
a=1,b=2,c=7,d=0,n=1。
comparative example 2-1
The present comparative example provides an agrochemical composition comprising the following components in mass fraction: 18% of emulsifying agent, 25% of hydrophobic pesticide and 57% of solvent; wherein, the emulsifier and the hydrophobic pesticide are the same as in the embodiment 2-1, and the solvent is methyl octanoate.
Comparative examples 2 to 2
The present comparative example provides an agrochemical composition comprising the following components in mass fraction: 18% of an emulsifying agent, 25% of a hydrophobic pesticide, 40% of a solvent and 17% of water; wherein, the emulsifier, the hydrophobic pesticide and the solvent are the same as those in comparative example 2-1, and the water is deionized water.
Comparative examples 2 to 3
The present comparative example provides an agrochemical composition comprising the following components in mass fraction: 18% of emulsifying agent, 25% of hydrophobic pesticide and 57% of solvent; wherein, the emulsifier and the hydrophobic pesticide are the same as those in comparative example 2-1, and the solvent is tetrahydrofurfuryl alcohol.
Test example 3
The agrochemical compositions provided in examples 2-1 to 2-6 and the agrochemical compositions provided in comparative examples 2-1 to 2-2 were administered to New Zealand white rabbits, respectively, at a dose of 0.1mL each; repeated experiments were performed using 3 New Zealand white rabbits per agrochemical composition to determine the extent to which the agrochemical composition produced eye irritation to the eyes of the white rabbits.
During the test, the drug was applied to conjunctival sac of one eye of each white rabbit, and the other eye was not applied with the drug and used as a blank, and the cornea, iris and conjunctiva of the eye were subjected to irritation evaluation 24 hours after the administration, and the evaluation results are shown in table 3.
TABLE 3 eye injury and scoring table
Remarks: the evaluation criteria are the same as those of test example 1, and will not be described in detail here.
Test example 4
In each example, a field efficacy test for wheat growth regulation was carried out, wherein wheat in the test field was at the end of tillering, and the wheat variety was poplar 20. Each example treated a large area with a treatment area of 1 mu, with line separation between different treatments. The agrochemical compositions provided in examples 2-1 to 2-6 and the agrochemical compositions provided in comparative examples 2-1 to 2-3 were sprayed with water, respectively, in an amount of 7 g/mu of the active ingredient and 40L/mu of the spray. The control group was sprayed with the same amount of clear water, the wheat plant height was investigated 14 days, 28 days and 55 days after the application of the drug, the plant height inhibition rate was calculated by comparing with the control plant height, the stalk strength was measured at the same time 55 days after the drug, the stalk strength promotion rate was calculated by comparing with the control, and the results are shown in table 4. Examples 2-1 to 2-6 and comparative examples 2-1 to 2-3 have obvious inhibiting effects on the plant height of wheat, have obvious promoting effects on the stalk strength of wheat, and effectively regulate the growth of wheat and prevent lodging of wheat.
Table 4 results of field test of the effect of compositions on wheat growth regulation
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims (6)

1. Use of an agrochemical composition for the preparation of a formulation of a pesticide for reducing eye irritation, wherein the agrochemical composition is an unsaturated fatty acid ester and a hydrophobic pesticide;
the molecular structural formula of the unsaturated fatty acid ester is shown as follows:
; wherein a=4, b=1, c= 7,d =0, n=1;
or, the molecular structural formula of the unsaturated fatty acid ester is shown as follows:
; wherein a=4, b=2, c=4, d=1, n=1;
or, the molecular structural formula of the unsaturated fatty acid ester is shown as follows:
; wherein a=1, b=2, c= 7,d =1, n=1;
or, the molecular structural formula of the unsaturated fatty acid ester is shown as follows:
; wherein a=4, b=3, c=3, d=0, n=1;
or, the molecular structural formula of the unsaturated fatty acid ester is shown as follows:
; wherein a=0, b=4, c=3, d=0, n=1;
or, the molecular structural formula of the unsaturated fatty acid ester is shown as follows:
; wherein a=0, b=4, c=3, d=1, n=1;
or, the molecular structural formula of the unsaturated fatty acid ester is shown as follows:
; wherein a=1, b=2, c= 7,d =0, n=1;
The hydrophobic pesticide is carfentrazone-ethyl and trinexapac-ethyl;
The mass ratio of the unsaturated fatty acid ester compound in the agrochemical composition is 15-95%.
2. Use of an agrochemical composition according to claim 1 for the preparation of a pesticide formulation which reduces eye irritation, wherein the agrochemical composition further comprises an emulsifier comprising an ionic emulsifier and/or a non-ionic emulsifier.
3. Use of an agrochemical composition according to claim 2 in the preparation of a pesticide formulation with reduced eye irritation wherein the emulsifier comprises at least one of alkylbenzene sulfonate, alkylbenzenesulfonate, alkyl sulfonate, carboxylate, alcohol alkoxylate, alkylphenol ethoxylate, castor oil ethoxylate, amine ethoxylate, sorbitan ester, alkyl glycoside, ethylene oxide-propylene oxide copolymer, ethoxylated phenol phosphate, tristyrylphenol phosphate and fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester.
4. Use of an agrochemical composition according to claim 3 for the preparation of a pesticide formulation with reduced eye irritation, wherein the mass ratio of unsaturated fatty acid ester in the agrochemical composition is 15-95%;
The mass ratio of the hydrophobic pesticide in the agrochemical composition is 5-85%.
5. A pesticide preparation for reducing eye irritation, characterized in that the pesticide preparation for reducing eye irritation is an unsaturated fatty acid ester and a hydrophobic pesticide;
the molecular structural formula of the unsaturated fatty acid ester is shown as follows:
; wherein a=4, b=1, c= 7,d =0, n=1;
or, the molecular structural formula of the unsaturated fatty acid ester is shown as follows:
; wherein a=4, b=2, c=4, d=1, n=1;
or, the molecular structural formula of the unsaturated fatty acid ester is shown as follows:
; wherein a=1, b=2, c= 7,d =1, n=1;
or, the molecular structural formula of the unsaturated fatty acid ester is shown as follows:
; wherein a=4, b=3, c=3, d=0, n=1;
or, the molecular structural formula of the unsaturated fatty acid ester is shown as follows:
; wherein a=0, b=4, c=3, d=0, n=1;
or, the molecular structural formula of the unsaturated fatty acid ester is shown as follows:
; wherein a=0, b=4, c=3, d=1, n=1;
or, the molecular structural formula of the unsaturated fatty acid ester is shown as follows:
; wherein a=1, b=2, c= 7,d =0, n=1;
The hydrophobic pesticide is carfentrazone-ethyl and trinexapac-ethyl;
the mass ratio of the unsaturated fatty acid ester in the pesticide preparation for reducing eye irritation is 15-95%.
6. Use of a pesticide formulation for reducing eye irritation as described in claim 5 for weeding, sterilizing, pest killing or plant growth regulating.
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BR112022024744A BR112022024744A2 (en) 2020-06-03 2021-05-24 APPLICATION OF UNSATURATED FATTY ACID ESTER, AGROCHEMICAL COMPOSITION, LOW EYE IRRITATION PESTICIDE FORMULATION AND THEIR APPLICATION

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