CN113749092A - Unsaturated fatty acid esterified product application, agrochemical composition, low-irritation pesticide preparation and application thereof - Google Patents
Unsaturated fatty acid esterified product application, agrochemical composition, low-irritation pesticide preparation and application thereof Download PDFInfo
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- CN113749092A CN113749092A CN202010493341.2A CN202010493341A CN113749092A CN 113749092 A CN113749092 A CN 113749092A CN 202010493341 A CN202010493341 A CN 202010493341A CN 113749092 A CN113749092 A CN 113749092A
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- Prior art keywords
- fatty acid
- unsaturated fatty
- pesticide
- agrochemical composition
- irritation
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- 238000010998 test method Methods 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical group OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- BAZVSMNPJJMILC-UHFFFAOYSA-N triadimenol Chemical compound C1=NC=NN1C(C(O)C(C)(C)C)OC1=CC=C(Cl)C=C1 BAZVSMNPJJMILC-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- AMFGTOFWMRQMEM-UHFFFAOYSA-N triazophos Chemical compound N1=C(OP(=S)(OCC)OCC)N=CN1C1=CC=CC=C1 AMFGTOFWMRQMEM-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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
-
- 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
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P13/00—Herbicides; Algicides
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P3/00—Fungicides
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P7/00—Arthropodicides
- A01P7/04—Insecticides
Abstract
The invention provides an application of an unsaturated fatty acid esterified substance, an agrochemical composition, a low-irritation pesticide preparation and an application thereof, and relates to the technical field of pesticides. The agrochemical composition provided by the invention is mutually cooperated with the hydrophobic pesticide through the unsaturated fatty acid ester compound, so that the hydrophobic pesticide is more easily emulsified into small droplets through the unsaturated fatty acid ester compound and is discharged out of eyes along with tears, and the contact time of the hydrophobic pesticide and the eyes or the epidermis is reduced, thereby reducing the irritation of the pesticide preparation to the eyes. In addition, the unsaturated fatty acid ester compound can form a barrier on the outer layer of the cornea of the eye, so that the contact and the damage of the pesticide preparation to the eye are reduced, and meanwhile, the unsaturated fatty acid ester compound also has certain moisture retention property and is beneficial to helping the eye to recover.
Description
Technical Field
The invention relates to the technical field of pesticides, in particular to application of unsaturated fatty acid esterified substance, an agrochemical composition, a low-irritation pesticide preparation and application thereof.
Background
Most active components in the agricultural chemical preparation are hydrophobic pesticides, and are dissolved by organic solvents such as aromatic hydrocarbon, alcohol ether, pyrrolidone and the like to prepare liquid preparations such as missible oil or aqueous emulsion and the like, but the organic solvents easily cause the problem of ecotoxicology. When the agricultural chemical liquid preparation is used in spraying, if the agricultural chemical liquid preparation is accidentally splashed or enters the eyes of an operator in spraying, the agricultural chemical liquid preparation can cause irritation or damage to the eyes and affect the health of the operator. After the pesticide is applied, the pesticide can also cause harm to eyes of wild animals, so that the survival crisis of the wild animals is caused, and the ecological balance is destroyed. The toxicity and irritation of agrochemical liquid preparations are now limited in many countries, for example, brazil limits the use of emulsifiable concentrate preparations with type i toxicity irritation in the market, germany requires that such agrochemical preparations be sold with ecotoxicity labels, and workers themselves are not willing to buy and use agrochemical products with high toxicity irritation.
At present, no technical scheme for well reducing the irritation of an agrochemical liquid preparation containing an organic solvent exists, and some commercial preparations try to reduce the ecotoxicological problem of agrochemical products by using low-toxicity and low-eye-irritation solvents such as aliphatic hydrocarbon, paraffin oil and the like, but the substances have small dissolving capacity for active ingredients in the agrochemical preparations and narrow application range, and are difficult to meet the requirements of various existing agrochemical hydrophobic pesticides.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide an application of an unsaturated fatty acid ester compound in preparation of a pesticide preparation for reducing eye irritation so as to meet the technical problems of limited solubility and high ecological toxicity of hydrophobic pesticides in various existing agricultural chemical preparations.
The invention also aims to provide an agrochemical composition to solve the technical problems that the existing agrochemical liquid preparation has high ecological toxicity and is easy to cause harm to the health of operating personnel.
The invention also aims to provide the application of the agrochemical composition in preparing the pesticide preparation for reducing eye irritation.
The invention also aims to provide a low-eye-irritation pesticide preparation to solve the technical problems that the existing agrochemical liquid preparation has high ecological toxicity, is easy to cause eye irritation to operators and is harmful to the body health of the operators.
The fifth purpose of the invention is to provide the application of the low-glare pesticide preparation in weeding, sterilization or disinsection and plant growth regulation.
One of the objects of the present invention is to provide the use of an unsaturated fatty acid esterified substance having the general formula:
wherein a is 0-18, n is 1-4, b is 0-8, c is 0-18, d is 0-4, and a, b and c are not simultaneously 0.
Further, the number of carbon-carbon double bonds in the unsaturated fatty acid ester is 1-8, preferably 1-3;
preferably, in the unsaturated fatty acid esterified product, the number of aliphatic chain carbon atoms is 6 to 24;
preferably, the unsaturated fatty acid ester is an unsaturated fatty acid methyl ester.
The second object of the invention is to provide an agrochemical composition comprising an unsaturated fatty acid esterified product and a hydrophobic pesticide in the application of 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, abamectin and trifluralin.
The triclopyr derivatives include triclopyr, an agriculturally acceptable ester of triclopyr and an agriculturally acceptable salt of triclopyr, such as butoxyethyl triclopyr and triclopyr triethylamine salt.
Further, the agrochemical composition further comprises an emulsifier;
preferably, the emulsifier comprises at least one of an alkylbenzene sulfonate, an alkyl sulfonate, a carboxylate, an alcohol alkoxylate, an alkylphenol ethoxylate, a castor oil ethoxylate, an amine ethoxylate, a sorbitan ester, an alkyl glycoside, an ethylene oxide-propylene oxide copolymer, an ethoxylated phenol phosphate, a tristyrylphenol phosphate, a fatty alcohol polyoxyethylene ether, and a fatty acid polyoxyethylene ester.
Further, the mass ratio of the unsaturated fatty acid ester compound 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%.
The invention also aims to provide the application of the agrochemical composition in preparing the pesticide preparation for reducing eye irritation.
The fourth purpose of the invention is to provide a low-eye-irritation pesticide preparation, which comprises the unsaturated fatty acid esterified product in the application or the agrochemical composition.
Further, the low-glare pesticide preparation is a liquid preparation;
preferably, the low-glare pesticide formulation is an emulsifiable concentrate formulation.
The fifth purpose of the invention is to provide the application of the low-glare pesticide preparation in weeding, sterilization, disinsection or plant growth regulation.
The unsaturated fatty acid esterified product provided by the invention has no irritation to eyes and low toxicity, and on the other hand, the hydrophobic pesticide and other auxiliaries in the pesticide preparation are easily emulsified into small droplets to be discharged out of eyes along with tears, so that the contact time between the hydrophobic pesticide and other auxiliaries and eyes or epidermis is reduced, and the irritation to eyes by the pesticide preparation is reduced. In addition, the unsaturated fatty acid ester compound provided by the invention can form a barrier on the outer layer of the cornea of the eye, reduce the contact and damage of hydrophobic pesticide and other auxiliary agents to the eye, and simultaneously has certain moisture retention property, thereby being beneficial to the recovery of the eye.
The agrochemical composition provided by the invention is mutually cooperated with the hydrophobic pesticide through the unsaturated fatty acid ester compound, so that the hydrophobic pesticide is more easily emulsified into small droplets through the unsaturated fatty acid ester compound and is discharged out of eyes along with tears, and the contact time of the hydrophobic pesticide and the eyes or the epidermis is reduced, thereby reducing the irritation of the hydrophobic pesticide to the eyes. In addition, the unsaturated fatty acid ester compound can form a barrier on the outer layer of the cornea of the eye, so that the contact and damage of hydrophobic pesticide to the eye are reduced, and meanwhile, the unsaturated fatty acid ester compound also has certain moisture retention property and is beneficial to helping the eye to recover.
According to the low-eye-irritation pesticide preparation provided by the invention, the unsaturated fatty acid ester compound is added, so that the contact time of the hydrophobic pesticide and eyes or epidermis can be reduced, the irritation of the hydrophobic pesticide to the eyes is reduced, a barrier can be formed on the outer layer of the cornea of the eyes, the contact and damage of the hydrophobic pesticide to the eyes are reduced, the eye recovery is facilitated, and the safety and health of operators are facilitated. In addition, the agrochemical composition preparation provided by the invention can reduce the damage of the pesticide to the eyes of wild animals, reduce the ecological crisis and contribute to ecological system balance through the mutual synergy of the unsaturated fatty acid esterified substance and the hydrophobic pesticide.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
According to one aspect of the present invention there is provided the use of an unsaturated fatty acid esterified substance in a formulation for a pesticide for reducing eye irritation, the unsaturated fatty acid esterified substance having the general formula:
wherein a is 0-18, n is 1-4, b is 0-8, c is 0-18, d is 0-4, and a, b and c are not simultaneously 0.
Typically, but not by way of limitation, 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 0 at the same time.
The unsaturated fatty acid is fat-soluble, is an important component of retina, has the function of promoting cell repair, and the esterified product has better compatibility with hydrophobic pesticide. The unsaturated fatty acid ester also has moisturizing and antioxidant effects in cosmetics.
The unsaturated fatty acid esterified product provided by the invention has no irritation to eyes and low toxicity, and on the other hand, the hydrophobic pesticide and other auxiliaries in the pesticide preparation are easily emulsified into small droplets to be discharged out of eyes along with tears, so that the contact time between the hydrophobic pesticide and other auxiliaries and eyes or epidermis is reduced, and the irritation to eyes by the pesticide preparation is reduced. In addition, the unsaturated fatty acid ester compound provided by the invention can form a barrier on the outer layer of the cornea of the eye, reduce the contact and damage of hydrophobic pesticide and other auxiliary agents to the eye, and simultaneously has certain moisture retention property, thereby being beneficial to the recovery of the eye.
In a preferred embodiment of the invention, the number of the carbon-carbon double bonds in the unsaturated fatty acid ester compound is 1 to 8, so that the unsaturated fatty acid ester compound has excellent performance, and the unsaturated fatty acid ester compound can be well dissolved with the hydrophobic pesticide in the pesticide preparation, so that the contact time of the hydrophobic pesticide and other additives with eyes or the epidermis can be better reduced, especially when the number of the carbon-carbon double bonds in the unsaturated fatty acid ester compound is 1 to 3, the unsaturated fatty acid ester compound has more excellent performance, the mutual dissolution performance of the unsaturated fatty acid ester compound with the hydrophobic pesticide in the pesticide preparation is better, the contact time of the hydrophobic pesticide and other additives with the eyes or the epidermis can be further shortened, the irritation of the pesticide preparation to the eyes can be more favorably reduced, and the safety and health of operators can be protected.
In a preferred embodiment of the invention, in the unsaturated fatty acid ester compound, the number of carbon atoms in the fatty chain is 6-24, so that the unsaturated fatty acid ester compound and the hydrophobic pesticide in the pesticide preparation have more excellent intersolubility, and thus, the irritation of the pesticide preparation to eyes can be more effectively reduced, and the safety and health of operators can be better ensured.
In a preferred embodiment of the invention, when the unsaturated fatty acid esterified product is unsaturated fatty acid methyl ester, the unsaturated fatty acid esterified product has better intersolubility with hydrophobic pesticide, is easier to reduce the irritation of the pesticide preparation to eyes, and better protects the safety and health of operators. The unsaturated fatty acid esterified substance is safe and nontoxic, has good intersolubility with hydrophobic pesticides in pesticide preparations, is more beneficial to forming a stable dispersion system with the hydrophobic pesticides, reduces the irritation of the hydrophobic pesticides and other auxiliaries to eyes, helps the eyes to recover, and protects the safety and health of operators.
According to a second aspect of the invention there is provided an agrochemical composition comprising an unsaturated fatty acid ester and a hydrophobic pesticide as provided in the use of the invention.
In the present invention, the hydrophobic agricultural chemical includes a slightly water-soluble and/or poorly water-soluble substance (that is, the hydrophobic agricultural chemical may be either a slightly water-soluble substance or a poorly water-soluble substance, or a mixture of a slightly water-soluble substance and a poorly water-soluble substance); the hydrophobic pesticide can be used as an active ingredient for herbicides, insecticides, pest repellants, plant growth regulators, synergists, plant safeners and preservatives.
In the present invention, the hydrophobic pesticide means that the pesticide has a solubility of less than 10g, preferably less than 1g, more preferably less than 0.1g in 100g of water having a pH of 7 at 20 ℃ under standard gas 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 tests, the person skilled in the art can select suitable hydrophobic pesticides from the prior art pesticides.
Known pesticides may include organophosphorus (chlorpyrifos, dimethoate, phoxim, dichlorvos), carbamate (carbofuran), pyrethroid (permethrin, bifenthrin), organosulfide (mancozeb, thiram), amide (alachlor, acetochlor, metolachlor, s-metolachlor, butachlor, urea compounds (chlortoluron), ether compounds (aclor, clorflat), phenolic compounds (sodium pentachlorophenate), phenoxycarboxylic acids (2,4-D butyl ester, triclopyr derivatives, methoxone), triazobenzenes (prometryn, atrazine), benzoic acids (dicamba), amidines (chlordimeform), triazolinones (carfentrazone), triazoles (difenoconazole, triadimenol), phenylpyrazoline (pinoxaden), Cyclohexane carboxylic acids (trinexapac-ethyl), anilines (pendimethalin and trifluralin), heterocycles (clomazone, carbendazim and hymexazol), abamectin and the like.
The agrochemical composition provided by the invention is mutually cooperated with the hydrophobic pesticide through the unsaturated fatty acid ester compound, so that the hydrophobic pesticide is more easily emulsified into small droplets through the unsaturated fatty acid ester compound and is discharged out of eyes along with tears, and the contact time of the hydrophobic pesticide and the eyes or the epidermis is reduced, thereby reducing the irritation of the pesticide preparation to the eyes. In addition, the unsaturated fatty acid ester compound can form a barrier on the outer layer of the cornea of the eye, so that the contact and damage of hydrophobic pesticide to the eye are reduced, and meanwhile, the unsaturated fatty acid ester compound also has certain moisture retention property and is beneficial to helping the eye to recover.
In a preferred embodiment of the invention, the hydrophobic pesticide includes, but is not limited to, at least one of acetochlor, permethrin, bifenthrin, carfentrazone-ethyl, trinexapac-ethyl, triclopyr derivatives, clomazone, metolachlor, s-metolachlor, 2,4-D ester, chlorpyrifos, pendimethalin, tebuconazole, difenoconazole, pinoxaden, abamectin and trifluralin.
The above-mentioned "triclopyr derivatives" include triclopyr, an agriculturally acceptable ester of triclopyr (such as butoxyethyl triclopyr), and an agriculturally acceptable salt of triclopyr (such as the triethylamine salt of triclopyr).
The term "at least one of" refers to that the hydrophobic pesticide comprises a mixture of two or more of acetochlor, permethrin, bifenthrin, carfentrazone-ethyl, trinexapac-ethyl, triclopyr derivatives, clomazone, metolachlor, 2,4-D ester, chlorpyrifos, pendimethalin, tebuconazole, difenoconazole, pinoxaden, abamectin or trifluralin.
In a preferred embodiment of the invention, the agrochemical composition further comprises an emulsifier. By adding the emulsifier into the agrochemical composition, after the unsaturated fatty acid ester compound and the hydrophobic pesticide are mutually dissolved, the unsaturated fatty acid ester compound and the hydrophobic pesticide are more easily emulsified into small droplets under the action of the emulsifier, so that the irritation of the agrochemical composition to eyes is reduced, and the safety and health of operators are protected.
In a preferred embodiment of the invention, the emulsifier comprises an ionic emulsifier and/or a non-ionic emulsifier.
Emulsifiers are used for emulsifying, wetting, dispersing, suspending or other purposes. The agrochemical composition is mostly applied in the form of pesticide liquid preparation, the pesticide liquid preparation needs a certain amount of emulsifier (ionic type, non-ionic type and the like) to stabilize active ingredients in the preparation, and good emulsifying dispersibility and emulsifying stability are ensured when the pesticide liquid preparation is diluted by adding water for use, which is the basis of normal use of the product. However, these emulsifiers are also responsible for severe eye irritation, especially some anionic emulsifiers, which are very irritating to the eye.
According to the invention, the unsaturated fatty acid ester compound is added into the agrochemical composition, so that the irritation of the hydrophobic pesticide, the emulsifier and other optional auxiliary agents to eyes can be effectively reduced, and the safety and health of operators are protected.
The above "and/or" means that the emulsifier may comprise ionic emulsifiers or non-ionic emulsifiers, and may also comprise a mixture of ionic emulsifiers and non-ionic emulsifiers.
In a preferred embodiment of the present invention, the emulsifier comprises at least one of alkyl benzene 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.
The above-mentioned "at least one" means that the emulsifier may include any 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, and may include alkylbenzene sulfonate, alkyl sulfonate, carboxylate, alcohol alkoxylate, alkyl phenol ethoxylate, castor oil ethoxylate, amine ethoxylate, sorbitan ester, alkyl glycoside, ethylene oxide-propylene oxide copolymer, ethoxylated phenol phosphate, ethoxylated sorbitan ester, alcohol ethoxylate, phenol phosphate, alcohol ethoxylate, phenol phosphate, and alcohol ethoxylate, The mixture of any two or more of tristyrylphenol phosphate, fatty alcohol-polyoxyethylene ether and fatty acid-polyoxyethylene ester.
In a preferred embodiment of the invention, the proportion by mass of the unsaturated fatty acid ester compound 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 constitutes, for example, 15%, 25%, 30%, 60%, 75%, 85% or 95% by weight of the agrochemical composition.
In a preferred embodiment of the invention, the mass proportion of the hydrophobic pesticide in the agrochemical composition is 5 to 85%, preferably 5 to 50%. The mass ratio of the hydrophobic pesticide in the agrochemical composition is controlled so that the agrochemical composition has corresponding pesticide effect.
Typically, but not limitatively, the hydrophobic pesticide constitutes 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 agrochemical composition is prepared by a process comprising the steps of:
the unsaturated fatty acid esterified product, the hydrophobic pesticide and the optional solvent are uniformly mixed, and after the hydrophobic pesticide is dissolved, the emulsifier and the optional other auxiliary agents are added and uniformly mixed, so that the agricultural chemical composition is obtained.
The agrochemical composition is a concentrate of a 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 manufacture of a pesticide formulation for reducing eye irritation.
According to a fourth aspect of the invention, there is provided a low eye irritation pesticide formulation comprising an unsaturated fatty acid esterified product for use according to the invention or an agrochemical composition according to the invention.
The term "low eye irritation" as used herein refers to low eye irritation, and refers to OECD (2000) or GHS (2007) classification standard, and the eye irritation level is a Category 2B or lower irritation level, i.e. the mean of the stimulation response integrals of 2/3 animals: the corneal opacity is less than or equal to 1, the iris is less than or equal to 1, the conjunctival congestion is less than or equal to 2, and the conjunctival edema is less than or equal to 2.
According to the low-eye-irritation pesticide preparation provided by the invention, the unsaturated fatty acid ester compound is added, so that the contact time of the hydrophobic pesticide and eyes or epidermis can be reduced, the irritation of the hydrophobic pesticide to the eyes is reduced, a barrier can be formed on the outer layer of the cornea of the eyes, the contact and damage of the hydrophobic pesticide to the eyes are reduced, the eye recovery is facilitated, and the safety and health of operators are facilitated.
In a preferred embodiment of the present invention, the low-glare 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 low-glare pesticide formulation is diluted by addition to water to facilitate application to 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-glare pesticide formulation as described above for weeding, combating bacteria, combating insects or regulating plant growth.
The technical scheme provided by the invention is further explained by combining the embodiment and the comparative example.
Examples 1 to 1
The embodiment provides an agrochemical composition, which comprises the following components in parts by mass: 50% of unsaturated fatty acid esterified substance, 10% of emulsifier and 40% of hydrophobic pesticide; the molecular structural formula of the unsaturated fatty acid esterified compound is shown as follows:
wherein a is 4, b is 1, c is 7, d is 0, and n is 1; the hydrophobic pesticide is carfentrazone-ethyl; the emulsifiers included calcium dodecylbenzenesulfonate (emulsifier CAL, available from clariant) and EO-PO block polyether (emulsifier ethyl lan NS-500LQ, available from aksunobel), and both emulsifiers accounted for 5% by weight of the agrochemical composition.
Examples 1 to 2
The embodiment provides an agrochemical composition, which comprises the following components in parts by mass: 25% of unsaturated fatty acid ester compound, 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, which is purchased from Mobil corporation.
Examples 1 to 3
The embodiment provides an agrochemical composition, which comprises the following components in parts by mass: 15% of unsaturated fatty acid esterified substance, 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 esterified compound 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 esterified compound 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 esterified compound 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 esterified compound is as follows:
a=0,b=4,c=3,d=0,n=1。
comparative examples 1 to 1
The comparative example provides an agrochemical composition, and comprises the following components in parts by mass: 10% of emulsifier, 40% of hydrophobic pesticide and 50% of solvent; wherein the emulsifier, the hydrophobic pesticide and the solvent are the same as in examples 1-2.
Comparative examples 1 to 2
The comparative example provides an agrochemical composition, and comprises the following components in parts by mass: 10% of emulsifier, 40% of hydrophobic pesticide, 25% of 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 are respectively administered to New Zealand white rabbits at an administration dosage of 0.1 mL; each agrochemical composition was tested in duplicate using 3 new zealand white rabbits to determine the degree of eye irritation that the agrochemical composition would have on the eyes of the white rabbits.
In the test procedure, the agent was applied to the conjunctival sac of one eye of each white rabbit, the other eye was not applied with the agent and served as a blank control, and the cornea, iris and conjunctiva of the eyes were evaluated for irritation at 24h after the administration, and the evaluation results are shown in table 1.
Comparative examples 1-1 to 1-2 had severe corneal haze (score 3), and conjunctival congestion and conjunctival edema (score 2) after administration; the cornea, iris and conjunctiva showed no irritation (score 0) after the administration of example 1-1, and the conjunctiva edema or hyperemia (score 0 or 1) was slight after the administration of examples 1-2 to 1-7, which was significantly improved as compared with comparative examples 1-1 to 1-2. The unsaturated fatty acid esterified product can effectively reduce the eye irritation of the pesticide preparation and reduce the eye irritation of the carfentrazone-ethyl missible oil preparation.
TABLE 1 Ocular injury and scoring sheet
Remarking: the above scoring criteria were performed with reference to the OECD standard, according to the guidelines set out 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 were as follows:
stimulation response | Score value | Remarks for note |
Corneal opacity (based on the densest part) | 0 to 4 minutes | Maximum stimulation score of 4 |
Iris (iris) | 0 to 2 points | Maximum stimulation score of 2 |
Conjunctival congestion | 0 to 3 points | Maximum stimulation score of 3 |
Conjunctival edema (including eyelid and third eyelid) | 0 to 4 minutes | Maximum stimulation score of 4 |
Test example 2
The embodiments develop the drug effect test in wheat field, the main weeds in the test field are cleavers and chenopodium album, the age of the grass is about 3-5 leaves, and the wheat is in tillering stage. Each example treated a large area, with a treatment area of 1 mu, with guard lines separating 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 mixed with water, stems and leaves, respectively, and were subjected to spray treatment, wherein the application dose was 1.5 g/mu of the effective component, and the spray volume was 40L/mu. The blank control group was sprayed with an equal amount of clear water, and 15 days after the application of the agent, the weed fresh weight control effect was investigated, and the wheat growth inhibition rate (%) was visually observed, with the results shown in table 2.
The examples 1-1 to 1-7 and the comparative examples 1-1 to 1-2 have obvious control effect on broadleaf weeds in wheat fields, the examples have certain advantages in pesticide effect compared with the comparative examples, and all the pesticides do not show phytotoxicity on wheat under the same using dose.
TABLE 2 field control effect of the compositions on broadleaf weeds in wheat fields
Example 2-1
The embodiment provides an agrochemical composition, which comprises the following components in parts by mass: 57% of unsaturated fatty acid ester compound, 18% of emulsifier and 25% of hydrophobic pesticide; the molecular structural formula of the unsaturated fatty acid esterified compound is shown as the following formula:
wherein a is 4, b is 1, c is 7, d is 0, and n is 1; the hydrophobic pesticide is trinexapac-ethyl; the emulsifier comprises fatty alcohol-polyoxyethylene ether (emulsifier Genapol X060, available from Clariant) and polyoxyethylene sorbitan monooleate (emulsifier Tween80, available from Dasipo chemical Co., Ltd.), wherein the mass proportion of the fatty alcohol-polyoxyethylene ether in the agrochemical composition is 10%, and the mass proportion of the polyoxyethylene sorbitan monooleate in the agrochemical composition is 8%.
Examples 2 to 2
The embodiment provides an agrochemical composition, which comprises the following components in parts by mass: 40% of unsaturated fatty acid esterified substance, 18% of emulsifier, 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 embodiment provides an agrochemical composition, which comprises the following components in parts by mass: 30% of unsaturated fatty acid ester compound, 25% of emulsifier 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 emulsifier fatty alcohol-polyoxyethylene ether accounts for 10% of the agrochemical composition, and the polyoxyethylene sorbitan monooleate accounts for 15% of the agrochemical composition.
Examples 2 to 4
This example provides an agrochemical composition which differs from example 2-1 in that the unsaturated fatty acid esterified compound 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 esterified compound 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 esterified compound is as follows:
a=1,b=2,c=7,d=0,n=1。
comparative example 2-1
The comparative example provides an agrochemical composition, and comprises the following components in parts by mass: 18% of emulsifier, 25% of hydrophobic pesticide and 57% of solvent; wherein the emulsifier and the hydrophobic pesticide are the same as in example 2-1, and the solvent is methyl caprylate.
Comparative examples 2 to 2
The comparative example provides an agrochemical composition, and comprises the following components in parts by mass: 18% of emulsifier, 25% of hydrophobic pesticide, 40% of solvent and 17% of water; wherein the emulsifier, the hydrophobic pesticide and the solvent are the same as in comparative example 2-1, and the water is deionized water.
Comparative examples 2 to 3
The comparative example provides an agrochemical composition, and comprises the following components in parts by mass: 18% of emulsifier, 25% of hydrophobic pesticide and 57% of solvent; wherein the emulsifier and the hydrophobic pesticide are the same as in comparative example 2-1, and the solvent is tetrahydrofurfuryl alcohol.
Test example 3
The agrochemical compositions provided in the examples 2-1 to 2-6 and the agrochemical compositions provided in the comparative examples 2-1 to 2-2 were respectively administered to New Zealand white rabbits at an administration dose of 0.1 mL; each agrochemical composition was tested in duplicate using 3 new zealand white rabbits to determine the degree of eye irritation that the agrochemical composition would have on the eyes of the white rabbits.
During the test, the agent was applied to the conjunctival sac of one eye of each white rabbit, the other eye was not applied with the agent and served as a blank control, and the cornea, iris and conjunctiva of the eyes were evaluated for irritation at 24h after the administration, and the evaluation results are shown in table 3.
TABLE 3 eye injury and scoring table
Remarking: the evaluation criteria were the same as in test example 1 and are not described in detail herein.
Test example 4
In each example, a field efficacy test of wheat growth regulation is carried out, wherein the wheat in the test field is at the final stage of tillering, and the wheat variety is poplar wheat 20. Each example treated a large area, with a treatment area of 1 mu, with guard lines separating 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 mixed with water, stems and leaves respectively for spray treatment, and the application doses were 7 g/mu of active ingredient and 40L/mu of liquid spray. The blank control group was sprayed with equal amount of clear water, wheat plant heights were investigated 14 days, 28 days, and 55 days after the application of the chemical, the plant height inhibition rate was calculated by comparing with the blank control plant height, the stalk strength was measured simultaneously 55 days after the application, the stalk strength promotion rate was calculated by comparing with the blank control, and the results are shown in table 4. The examples 2-1 to 2-6 and the comparative examples 2-1 to 2-3 have obvious inhibition effect on the plant height of wheat, have obvious promotion effect on the stalk strength of wheat, effectively regulate the growth of wheat and prevent the lodging of wheat.
TABLE 4 field test results of the effect of the compositions on wheat growth regulation
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. Use of an unsaturated fatty acid esterified product for the preparation of a pesticide formulation for reducing eye irritation, wherein the unsaturated fatty acid esterified product has the general formula:
wherein a is 0-18, n is 1-4, b is 0-8, c is 0-18, d is 0-4, and a, b and c are not simultaneously 0.
2. Use according to claim 1, wherein the number of carbon-carbon double bonds in the unsaturated fatty acid ester is from 1 to 8, preferably from 1 to 3;
preferably, in the unsaturated fatty acid esterified product, the number of aliphatic chain carbon atoms is 6 to 24;
preferably, the unsaturated fatty acid ester is an unsaturated fatty acid methyl ester.
3. An agrochemical composition comprising an unsaturated fatty acid esterified substance for use according to claim 1 or 2 and a hydrophobic pesticide.
4. The agrochemical composition according to claim 3, wherein the hydrophobic pesticide includes at least one of acetochlor, permethrin, bifenthrin, carfentrazone-ethyl, trinexapac-ethyl, triclopyr derivatives, clomazone, metolachlor, s-metolachlor, 2,4-D esters, chlorpyrifos, pendimethalin, tebuconazole, difenoconazole, pinoxaden, abamectin and trifluralin.
5. The agrochemical composition according to claim 3 or 4, characterised in that it further comprises an emulsifier;
preferably, the emulsifier comprises an ionic emulsifier and/or a non-ionic emulsifier;
preferably, the emulsifier comprises at least one of alkyl benzene sulfonate, alkyl sulfonate, carboxylate, alcohol alkoxylate, alkyl phenol 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.
6. Agrochemical composition according to claim 5, characterised in that the proportion by mass of the unsaturated fatty acid esterified substance in the agrochemical composition is 15-95%, preferably 20-60%;
preferably, the mass proportion of the hydrophobic pesticide in the agrochemical composition is 5-85%, preferably 5-50%.
7. Use of the agrochemical composition according to any one of claims 3 to 6 in the preparation of a pesticide formulation with reduced eye irritation.
8. A low-irritation agrochemical formulation comprising an unsaturated fatty acid esterified product for use according to claim 1 or 2 or an agrochemical composition according to any one of claims 3 to 6.
9. The low-glare pesticide formulation of claim 8, wherein the low-glare pesticide formulation is a liquid formulation;
preferably, the low-glare pesticide formulation is an emulsifiable concentrate formulation.
10. Use of a low-glare pesticide formulation according to claim 8 or 9 for weeding, killing bacteria, killing insects, or regulating plant growth.
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PCT/CN2021/095590 WO2021244347A1 (en) | 2020-06-03 | 2021-05-24 | Use of esterified product of unsaturated fatty acid, and agrochemical composition and low eye irritancy pesticide preparation and use thereof |
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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