Agrochemical composition of low eye irritation and method for preparation of an agrochemical composition of low eye irritation
Patent Information
- Application Number
- BR112022024744
- Authority / Receiving Office
- BR · BR
- Patent Type
- Patents
- Current Assignee / Owner
- Publication Date
- 2026-08-11
Abstract
Description
Agrochemical composition with low eye irritation and method for preparing an agrochemical composition with low eye irritation. CROSS-REFERENCE TO RELATED REQUESTS
[001] This application claims the benefit of priority from Patent Application No. CN 202010493341.2, filed on June 3, 2020, and entitled “APPLICATION OF UNSATURATED FATTY ACID ESTER, AGROCHEMICAL COMPOSITION, LOW EYE IRRITATION PESTICIDE FORMULATION AND APPLICATION THEREOF”. The content of the aforementioned application, including any intervening amendments thereto, is incorporated herein by reference in its entirety. FIELD OF TECHNIQUE
[002] This application relates to pesticides, and more particularly to an application of an unsaturated fatty acid ester, an agrochemical composition and a low eye irritation pesticide formulation, as well as an application thereof. BACKGROUND
[003] Considering that the active ingredients in an agrochemical formulation are dominated by hydrophobic pesticides, it is necessary to dissolve the agrochemical formulation with an organic solvent, such as aromatic hydrocarbon, alcoholic ether, and pyrrolidone, to prepare a liquid formulation for practical application, such as emulsifiable concentrates (ECs) and aqueous emulsions. However, these organic solvents will lead to ecotoxicological problems. Furthermore, these liquid agrochemical formulations can cause eye irritation or injury and threaten the health of operators after accidental spraying into their eyes. These agrochemical formulations can also damage the eyes of wildlife, threatening their survival and disrupting the ecological balance. In this case, the toxicity and irritation of liquid agrochemical formulations have been strictly restricted in many Petition 870250116788, dated 12 / 18 / 2025, page 13 / 26 2 / 24 countries. For example, the commercial application of Class I EC formulations (toxic and irritating) has been restricted in Brazil; and as published by Germany, agrochemical formulations must have an ecotoxicity label before being placed on the market. Operators themselves are less likely to choose and use agrochemicals with high toxicity and strong irritation.
[004] There is a lack of a satisfactory technical scheme to effectively mitigate irritation from liquid agrochemical formulations containing an organic solvent. Efforts have been made to alleviate the ecotoxicological problems associated with agrochemicals by adopting a low-toxicity, low-eye-irritation solvent such as aliphatic hydrocarbons and paraffin oil. However, these solvents struggle with low dissolution capacity of active ingredients in agrochemicals and a limited application range, and therefore cannot meet the requirements of existing agrochemicals containing various hydrophobic pesticides. SUMMARY
[005] A primary objective of this application is to provide an application of an unsaturated fatty acid ester in the preparation of a low eye irritation pesticide formulation to address problems in existing agrochemical formulations such as poor dissolution ability for hydrophobic pesticides and high ecotoxicity.
[006] A second objective of this application is to provide an agrochemical composition to alleviate the problem that existing liquid agrochemical formulations have high ecotoxicity and will seriously threaten human health.
[007] A third objective of this application is to provide an application of the agrochemical composition in the preparation of a low eye irritation pesticide formulation.
[008] A fourth objective of this application is to provide a low eye irritation pesticide formulation to overcome the problem that the formulations Petition 870220112460, dated 02 / 12 / 2022, page 8 / 88 3 / 24 Existing liquid agrochemicals have high ecotoxicity and cause severe eye irritation, posing a serious threat to human health.
[009] A fifth objective of this application is to provide an application of the low eye irritation pesticide formulation in weeding, sterilization, disinsection and plant growth regulation.
[010] Technical solutions for this application are described as follows.
[011] In a first aspect, this application provides an application of an unsaturated fatty acid ester in the preparation of a low eye irritation pesticide formulation, wherein the unsaturated fatty acid ester is shown in the following formula: O ( H2 \ í H H2n H \ ( H2 \ II í H2 \ H3C4— C—hC=FC—Cs--C=^CH—C—EC--O4—C—FCH33\ / aH\nTbH \ Λ \ / d 3· ;
[012] where a = 0-18; n = 1-4; b = 0-8; c = 0-18; d = 0-4; and a, b and c are not simultaneously equal to 0.
[013] In one embodiment, the unsaturated fatty acid ester has 1-8, preferably 1-3, carbon-carbon double bonds.
[014] In one embodiment, an aliphatic chain of the unsaturated fatty acid ester has 6-24 carbon atoms.
[015] In one embodiment, the unsaturated fatty acid ester is an unsaturated fatty acid methyl ester.
[016] In a second aspect, this application provides an agrochemical composition comprising:
[017] the unsaturated fatty acid ester mentioned in the application above; and a hydrophobic pesticide.
[018] In one embodiment, the hydrophobic pesticide is selected from the group consisting of acetochlor, permethrin, bifenthrin, carfentrazone-ethyl, trinexapac-ethyl, triclopyr, triclopyr derivative, clomazone, metolachlor, (S)metolachlor, 2,4-D ester, chlorpyrifos, pendimethalin, tebuconazole, difenoconazole, pinoxaden, avermectin, trifluralin and a combination thereof. Petition 870220112460, dated 02 / 12 / 2022, p. 9 / 88 4 / 24
[019] In one embodiment, the triclopyr derivative comprises triclopyr, agriculturally acceptable triclopyr ester (as 2-butoxyethyl triclopyr ester) and agriculturally acceptable triclopyr salt (as triethylamine triclopyr salt).
[020] In one embodiment, the agrochemical composition additionally comprises an emulsifier.
[021] In one embodiment, the emulsifier is selected from the group consisting of alkylbenzene sulfonate salt, alkylbenzene sulfonate ester, alkyl sulfonate salt, alkyl sulfonate ester, carboxylate, carboxylic acid ester, alcohol alkoxylate, alkylphenol ethoxylate, ethoxylated castor oil, amine ethoxylate, sorbitan fatty acid ester, alkyl polyglycoside, ethylene oxide-propylene oxide copolymer, ethoxylated phenol phosphate, triestyrylphenol phosphate, polyoxyethylene fatty alcohol ether, polyoxyethylene fatty acid ester and a combination thereof.
[022] In one embodiment, the agrochemical composition comprises 15-95%, preferably 20-60%, by weight of unsaturated fatty acid ester.
[023] In one embodiment, the agrochemical composition comprises 5-85%, preferably 5-50%, by weight of the hydrophobic pesticide.
[024] In a third aspect, this application provides an application of the above agrochemical composition in the preparation of a low eye irritation pesticide formulation.
[025] In a fourth aspect, this application provides a low eye irritation pesticide formulation comprising:
[026] the unsaturated fatty acid ester mentioned in the above application or the agrochemical composition mentioned above.
[027] In one embodiment, the low eye irritation pesticide formulation is a liquid formulation.
[028] In one embodiment, the low eye irritation pesticide formulation is an emulsifiable concentrate (EC) formulation.
[029] In a fifth aspect, this application provides an application of the aforementioned low eye irritation pesticide formulation in weeding, Petition 870220112460, dated 02 / 12 / 2022, page 10 / 88 5 / 24 sterilization, pest control and plant growth regulation.
[030] Compared to the previous technique, this application has the following beneficial effects.
[031] On the one hand, the unsaturated fatty acid ester provided in this document is not irritating to human eyes and has low toxicity and, on the other hand, it can emulsify the hydrophobic pesticide and other adjuvants into droplets to leave the eyes tear-inducing, shortening the contact between the hydrophobic pesticide and the eyes or epidermis and relieving irritation from the pesticide formulation to the eyes. Additionally, the unsaturated fatty acid ester provided in this document can form a barrier on the ectocornea, so as not only to reduce damage from the hydrophobic pesticide and other adjuvants to the eyes, but also to play a certain role in moisturizing the eyes, facilitating eye protection and recovery.
[032] The synergistic effect of the unsaturated fatty acid ester and hydrophobic pesticide is enabled in the agrochemical composition provided in this document. Specifically, the unsaturated fatty acid ester can easily emulsify the hydrophobic pesticide into droplets to leave the eyes tear-inducing, so that the exposure of the eyes or epidermis to the hydrophobic pesticide is shortened, attenuating the irritation of the hydrophobic pesticide to the eyes. Additionally, the unsaturated fatty acid ester can form a barrier on the ectocornea, which can not only reduce damage from the hydrophobic pesticide to the eyes, but also play a certain role in moisturizing the eyes, facilitating eye protection and recovery.
[033] Regarding the low eye irritation pesticide formulation containing the unsaturated fatty acid ester, the contact time between the hydrophobic pesticide and the eyes or epidermis is shortened to alleviate the irritation of the hydrophobic pesticide to the eyes. Furthermore, the unsaturated fatty acid ester can form a barrier on the ectocornea to protect the eyes from being damaged by the hydrophobic pesticide, effectively enhancing safety. Additionally, based on the synergistic effect between the unsaturated fatty acid ester and the pesticide Petition 870220112460, dated 02 / 12 / 2022, page 11 / 88 6 / 24 hydrophobic, the low eye irritation pesticide formulation provided in this document may reduce pesticide damage to the eyes of wildlife, alleviate the ecological crisis and contribute to ecological balance. DETAILED DESCRIPTION OF THE MODALITIES
[034] This application will be clearly and completely described with reference to the following embodiments. Obviously, some embodiments of this application are merely described below and are not intended to limit this application. It should be understood that any other embodiments obtained by persons skilled in the art based on the content disclosed herein without paying creative effort shall fall within the scope of this application.
[035] In a first aspect, this application provides an application of an unsaturated fatty acid ester in the preparation of a low eye irritation pesticide formulation, wherein the unsaturated fatty acid ester is shown in the following formula: THE I H2 \ J_a H2 H\ / H2 X II H H2 \ '': < / <<',<< / <''' / ;
[036] Where a = 0-18; n = 1-4; b = 0-8; c = 0-18; d = 0-4; and a, b and c are not simultaneously equal to 0.
[037] In one embodiment, a and 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 are not simultaneously equal to 0.
[038] As an important component of the retina, unsaturated fatty acids are fat-soluble and can promote cell repair. Unsaturated fatty acid esters have good compatibility with hydrophobic pesticides. Unsaturated fatty acid esters also have a moisturizing and antioxidant effect in cosmetics.
[039] On the one hand, the unsaturated fatty acid ester provided in this document is not irritating to human eyes and has low toxicity and, on the other hand Petition 870220112460, dated 02 / 12 / 2022, p. 12 / 88 7 / 24 side, the same can emulsify the hydrophobic pesticide and other adjuvants into droplets to leave the eyes with tears, shortening the contact between the hydrophobic pesticide and the eyes or epidermis and relieving irritation from the pesticide formulation to the eyes. Additionally, the unsaturated fatty acid ester provided in this document can form a barrier on the ectocornea, so as not only to reduce damage from the hydrophobic pesticide and other adjuvants to the eyes, but also to play a certain role in moisturizing the eyes, facilitating eye protection and recovery.
[040] In one embodiment, the unsaturated fatty acid ester has 1-8 carbon-carbon double bonds, so that the unsaturated fatty acid ester has excellent compatibility with hydrophobic pesticides in the pesticide formulation, effectively shortening the contact time between the hydrophobic pesticides and the eyes or epidermis. Especially when there are 1-3 carbon-carbon double bonds, the unsaturated fatty acid ester has even more excellent compatibility with hydrophobic pesticides in the pesticide formulation, so that the contact time between the hydrophobic pesticides and other adjuvants and the eyes or epidermis is further shortened, facilitating the attenuation of irritation from the pesticide formulation to the eyes and protecting operators.
[041] In one embodiment, when an aliphatic chain in the unsaturated fatty acid ester has 6-24 carbon atoms, the unsaturated fatty acid ester has better dissolution ability for hydrophobic pesticides in the pesticide formulation, which facilitates mitigating irritation of the pesticide formulation to the eyes and effectively enhances safety.
[042] In one embodiment, when the unsaturated fatty acid ester is an unsaturated fatty acid methyl ester, the unsaturated fatty acid methyl ester has better dissolving ability for hydrophobic pesticide, making it easier to mitigate irritation of the pesticide formulation to the eyes and effectively protect operators. The unsaturated fatty acid ester has no toxicity and better dissolving ability for the hydrophobic pesticide in the formulation of Petition 870220112460, dated 02 / 12 / 2022, p. 13 / 88 8 / 24 pesticide, which is more likely to form a stable dispersion system with hydrophobic pesticide, thereby attenuating the irritation of hydrophobic pesticide and other adjuvants to the eyes, facilitating eye protection and recovery and protecting operators.
[043] In a second aspect, this application provides an agrochemical composition, which includes the unsaturated fatty acid ester mentioned in the first aspect and a hydrophobic pesticide.
[044] In this application, the hydrophobic pesticide includes a slightly water-soluble substance and / or a water-insoluble substance (namely, the hydrophobic pesticide may be a slightly water-soluble substance, a water-insoluble substance or a mixture thereof). The hydrophobic pesticide may be used as an active ingredient in herbicides, insecticides, pest repellents, plant growth regulators, synergists, protectants and preservatives.
[045] As used in this document, hydrophobic pesticide refers to a pesticide that has a solubility of less than 10 g (such as less than 1 g and less than 0.1 g) in 100 g of water (pH 7) under standard atmospheric pressure at 20 °C.
[046] In this application, the hydrophobic pesticide may be an active ingredient published in “The Pesticide Manual” (Worthing C R. The Pesticide manual [M]. Version 18. British Crop Protection Council, 2018). Persons skilled in the art may select a suitable hydrophobic pesticide from the prior art through simple preliminary tests.
[047] Known pesticides can be structurally classified into organophosphates (chlorpyrifos, dimethoate, phoxim and dichlorvos), carbamates (carbofuran), pyrethroids (permethrin, bifenthrin), organic sulfides (mancozeb, thiram), amide compounds (alachlor, acetochlor, (S)-metolachlor, fine (S)-metolachlor, butachlor), urea compounds (chlorotoluron), ether compounds (nitrophene, lactophene), phenolic compounds (sodium pentachlorophenolate), phenoxycarboxylic acids (2,4-D-butyl ester, triclopyr, triclopyr derivative, tetrachlor Petition 870220112460, dated 02 / 12 / 2022, page 14 / 88 9 / 24 dimethyl), triazines (promethazine, atrazine), benzoic acid (dicamba), amidines (chlordimeform), triazolinones (carfentrazone-ethyl), triazoles (difenoconazole, triadimephone, tebuconazole), phenylpyrazolines (pinoxadene), cyclohexanecarboxylic acids (trinexapac-ethyl), anilines (pendimethalin, trifluralin), heterocyclic compounds (clomazone, carbendazim, himexazole) and abamectin.
[048] The synergistic effect of the unsaturated fatty acid ester and hydrophobic pesticide is enabled in the agrochemical composition provided in this document. Specifically, the unsaturated fatty acid ester can easily emulsify the hydrophobic pesticide into droplets that cause the eyes to tear, thus shortening the exposure of the eyes or epidermis to the hydrophobic pesticide and mitigating the irritation caused by the hydrophobic pesticide to the eyes.Additionally, the unsaturated fatty acid ester can form a barrier on the ectocornea, which may not only reduce damage from hydrophobic pesticides to the eyes, but also play a role in moisturizing the eyes, facilitating eye protection and recovery.
[049] In one embodiment, the hydrophobic pesticide includes at least one of acetochlor, permethrin, bifenthrin, carfentrazone-ethyl, trinexapac-ethyl, triclopyr, triclopyr derivative, clomazone, (S)-metolachlor, 2,4-D ester, chlorpyrifos, pendimethalin, tebuconazole, difenoconazole, pinoxaden, avermectin, and trifluralin.
[050] The triclopyr derivative mentioned above includes triclopyr, agriculturally acceptable esters of triclopyr (such as 2-butoxyethyl triclopyr ester), and agriculturally acceptable salts of triclopyr (such as triethylamine triclopyr salt).
[051] “At least one” means that the hydrophobic pesticide includes two or more of the following: acetochlor, permethrin, bifenthrin, carfentrazone-ethyl, trinexapac-ethyl, triclopyr, triclopyr derivative, clomazone, (S)-metolachlor, 2,4-D ester, chlorpyrifos, pendimethalin, tebuconazole, difenoconazole, pinoxaden, avermectin, and trifluralin.
[052] In one embodiment, the agrochemical composition additionally includes an emulsifier. The emulsifier may enhance the mutual solubility between the unsaturated fatty acid ester and the hydrophobic pesticide, which may promote the formation of small droplets, so as to mitigate irritation from the composition. Petition 870220112460, dated 02 / 12 / 2022, page 15 / 88 10 / 24 agrochemicals to the eye and improve safety.
[053] In one embodiment, the emulsifier includes an ionic emulsifier and / or a non-ionic emulsifier.
[054] The emulsifier is used for emulsification, wetting, dispersion, suspension, etc. The agrochemical composition is mainly applied in a liquid formulation form. It is necessary to introduce an appropriate emulsifier (such as ionic and non-ionic emulsifiers) into the liquid pesticide formulation to stabilize the active ingredients and achieve satisfactory dispersion and stability after dilution, facilitating normal use. However, these emulsifiers, especially some anionic emulsifiers, can also cause severe eye irritation.
[055] Unsaturated fatty acid ester can effectively mitigate irritation from hydrophobic pesticides, emulsifiers and other adjuvants to the eyes, providing enhanced application safety.
[056] The “and / or” means that the emulsifier may include an ionic emulsifier, a non-ionic emulsifier, or a mixture thereof.
[057] In one embodiment, the emulsifier includes at least one of alkylbenzene sulfonate salt, alkylbenzene sulfonate ester, alkyl sulfonate salt, alkyl sulfonate ester, carboxylate, carboxylic acid ester, alcohol alkoxylate, alkylphenol ethoxylate, ethoxylated castor oil, amine ethoxylate, sorbitan fatty acid ester, alkyl polyglycoside, ethylene oxide-propylene oxide copolymer, ethoxylated phenol phosphate, triestyrylphenol phosphate, polyoxyethylene fatty alcohol ether and polyoxyethylene fatty acid ester.
[058] “At least one” means that the emulsifier may include one or more of the following: alkyl benzene sulfonate, alkyl benzene sulfonate ester, alkyl sulfonate, alkyl sulfonate ester, carboxylate, carboxylic acid ester, alcohol alkoxylate, alkylphenol ethoxylate, ethoxylated castor oil, amine ethoxylate, sorbitan fatty acid ester, alkyl polyglycoside, ethylene oxide-propylene oxide copolymer, ethoxylated phenol phosphate, Petition 870220112460, dated 02 / 12 / 2022, page 16 / 88 11 / 24 triestyrylphenol phosphate, polyoxyethylene fatty alcohol ether and polyoxyethylene fatty acid ester.
[059] In one embodiment, the agrochemical composition includes 15-95%, preferably 20-60%, by weight of unsaturated fatty acid ester.
[060] In one embodiment, a weight percentage of the unsaturated fatty acid ester in the agrochemical composition is 15%, 25%, 30%, 60%, 75%, 85% or 95%.
[061] In one embodiment, the agrochemical composition includes 5-85%, preferably 5-50%, by weight of the hydrophobic pesticide. The percentage by weight of the hydrophobic pesticide in the agrochemical composition is controlled to achieve the corresponding effect.
[062] In one embodiment, a percentage by weight of hydrophobic pesticide in the agrochemical composition is 15%, 25%, 40%, 50%, 60%, 75%, 80% or 85%.
[063] In one embodiment, the preparation of the agrochemical composition is carried out through the following steps.
[064] The unsaturated fatty acid ester, the hydrophobic pesticide, and a solvent were mixed uniformly to obtain a mixture. After the hydrophobic pesticide had dissolved, an emulsifier and adjuvants were added to the mixture, followed by uniform mixing to obtain the agrochemical composition.
[065] As a concentrated pesticide formulation, the agrochemical composition is diluted with water and then applied by irrigation, spraying or other conventional methods known to those skilled in the art.
[066] In a third aspect, an application of the aforementioned agrochemical composition in the preparation of a low eye irritation pesticide formulation is provided in this document.
[067] In a fourth aspect, a low eye irritation pesticide formulation is provided in this document, which includes an acid ester. Petition 870220112460, dated 02 / 12 / 2022, page 17 / 88 12 / 24 unsaturated fat mentioned above or the agrochemical composition mentioned above.
[068] “Low eye irritation” means low eye irritation, which is defined according to the classification standards provided by the Organisation for Economic Co-operation and Development (OECD) (2000) or the Globally Harmonised System of Classification and Identification of Chemicals (GHS) (2007) classification standards. The eye irritation level is Category 2B or lower, i.e., for 2 / 3 of the test animals, the mean values of the animal irritation response scores meet the following criteria: corneal opacity < 1, iritis < 1, conjunctival hyperemia < 2; and conjunctival edema < 2.
[069] The low eye irritation pesticide formulation provided in this document is supplemented with an unsaturated fatty acid ester, which can not only shorten the contact between hydrophobic pesticide and eyes or epidermis to mitigate hydrophobic pesticide eye irritation, but also form a barrier on the ectocornea to reduce eye damage from the hydrophobic pesticide, facilitating eye protection and recovery and protecting the operator's health.
[070] In one embodiment, the low eye irritation pesticide formulation provided herein is a liquid formulation, more preferably an emulsifiable concentrate (EC) formulation.
[071] In one embodiment, the agrochemical composition or low eye irritation pesticide formulation is diluted in water to make it easier to apply to agricultural land by spraying or irrigation.
[072] In a fifth aspect, an application of the aforementioned low eye irritation pesticide formulation is provided in this document for weeding, sterilization or disinsection, or plant growth regulation.
[073] The technical solutions for this application will be further described below with reference to examples and comparative examples. Petition 870220112460, dated 02 / 12 / 2022, p. 18 / 88 13 / 24 EXAMPLE 1-1
[074] An agrochemical composition has been provided in this document, comprising 50% by weight of an unsaturated fatty acid ester, 10% by weight of an emulsifier and 40% by weight of a hydrophobic pesticide, wherein the unsaturated fatty acid ester has been shown in the following formula: O / H2 \ J_H H2n H \ HH, \ II H H2\tu (|;C; i CCtHfHC-OVACH ;
[075] wherein a=4, b=1, c=7, d=0 and n=1; the hydrophobic pesticide was carfentrazone-ethyl; the emulsifier included calcium dodecylbenzene sulfonate (emulsifier CAL, purchased from Clariant Company) and ethylene oxide-propylene oxide copolymer (polyether block EO-PO) (emulsifier Etilane NS500LQ, purchased from Akzo Nobel Company), and a weight percentage of each of calcium dodecylbenzene sulfonate and ethylene oxide-propylene oxide copolymer in the agrochemical composition was 5%. EXAMPLE 1-2
[076] An agrochemical composition has been provided herein, comprising 25% by weight of an unsaturated fatty acid ester, 25% by weight of a solvent, 10% by weight of an emulsifier and 40% by weight of a hydrophobic pesticide, wherein the unsaturated fatty acid ester, the hydrophobic pesticide and the emulsifier used herein were, respectively, the same as those in Example 1-1, and the solvent used herein was the aromatic solvent (Solvesso 150, purchased from Mobil Corporation). EXAMPLE 1-3
[077] An agrochemical composition has been provided in this document, comprising 15% by weight of an unsaturated fatty acid ester, 35% by weight of a solvent, 10% by weight of an emulsifier and 40% by weight of a hydrophobic pesticide, wherein the unsaturated fatty acid ester, the hydrophobic pesticide, the emulsifier and the solvent used in this document were, respectively, the same as those in Example 1-2. Petition 870220112460, dated 02 / 12 / 2022, p. 19 / 88 14 / 24 EXAMPLE 1-4
[078] An agrochemical composition was provided in this document, which differed from that in Example 1-1 in that the formula for the unsaturated fatty acid ester was: O / H2 \ / H H2n H\ / H2 \ || / H2 \h'cVc1h4c-c— CtHTClC-OVACH,a=4, b=2, c=4, d=1 and n=1. EXAMPLE 1-5
[079] An agrochemical composition was provided in this document, which differed from that in Example 1-1 where the formula for the unsaturated fatty acid ester was: THE I H2 \ _HH H2n H \ H H2 \ II ! H2\ H'CfClHTC-C— CtHfHC-OVACH,a=1, b=2, c=7, d=1 and n=1. EXAMPLE 1-6
[080] An agrochemical composition was provided in this document, which differed from that in Example 1-1 where the formula for the unsaturated fatty acid ester was: THE I H2 \ _H H H2n H \ H H2 \ II ! H2 \,u 3.([C;i 1CtHfHC-OVACH,a=4, b=3, c=3, d=0 and n=1. EXAMPLE 1-7
[081] An agrochemical composition was provided in this document, which differed from that in Example 1-1 where the formula for the unsaturated fatty acid ester was: Petition 870220112460, dated 02 / 12 / 2022, p. 20 / 88 15 / 24 O / H2 \ / H H2n H\ / H2 \ || / H2 \h'cVc1h4c-c— ':?;(·>7o- / 7h, a=0, b=4, c=3, d=0 and n=1. COMPARATIVE EXAMPLE 1-1
[082] An agrochemical composition comprising 10% by weight of an emulsifier, 40% by weight of a hydrophobic pesticide and 50% by weight of a solvent has been provided in this document, wherein the emulsifier, the hydrophobic pesticide and the solvent used in this document were, respectively, the same as those in Example 1-2. COMPARATIVE EXAMPLE 1-2
[083] An agrochemical composition comprising 10% by weight of an emulsifier, 40% by weight of a hydrophobic pesticide, 25% by weight of a solvent and 25% by weight of water has been provided in this document, wherein the emulsifier, the hydrophobic pesticide and the solvent used in this document were, respectively, the same as those in Example 1-2, and the water was deionized. EXPERIMENTAL EXAMPLE 1
[084] The agrochemical compositions provided in Examples 1-1~1-7 and the agrochemical compositions provided in Comparative Examples 1-1~1-2 were, respectively, administered to New Zealand white rabbits at a dosage of 0.1 ml. Three replicates were conducted for each agrochemical composition (namely, the same agrochemical composition was administered to three rabbits) to determine the level of eye irritation caused by the agrochemical composition to the New Zealand white rabbits.
[085] During the experiments, the agrochemical composition was merely administered to the conjunctival sac of one eye of each rabbit, and the other eye served as a control. 24 h after administration, the cornea, iris and conjunctiva of the eye were observed to assess irritation, and the results are shown in Table 1. Petition 870220112460, dated 02 / 12 / 2022, page 21 / 88 16 / 24
[086] The agrochemical compositions in Comparative Examples 1-1~1-2 resulted in severe corneal opacity (score 3), conjunctival hyperemia, and conjunctival edema (score 2); the agrochemical composition in Example 1-1 did not exhibit corneal, iritis, or conjunctival irritation (score 0); the agrochemical compositions in Examples 1-2~1-7 caused slight conjunctival edema or conjunctival hyperemia (score 0 or 1). Compared to Comparative Examples 1-1~1-2, Examples 1-1~1-7 had less irritation. It can be concluded that the unsaturated fatty acid ester can effectively mitigate eye irritation caused by the pesticide formulation and reduce eye irritation from the carfentrazone-ethyl EC formulation. TABLE 1 EYE DAMAGE AND SCORING TABLE Scoring (24 h) Corneal opacity Iritis Conjunctival hyperemia Conjunctival edema Example 11 0 0 0 0 Example 12 0 0 1 1 Example 13 1 0 1 1 Example 14 0 0 1 0 Example 15 0 0 1 1 Example 16 0 0 1 0 Example 17 0 0 1 1 Example Comparative 1-1 3 1 2 2 Example Comparative 1-2 3 0 1 2 Petition 870220112460, dated 02 / 12 / 2022, page 22 / 88 17 / 24 Notes: The scoring criteria above were defined with reference to the OECD, and the test was conducted in accordance with 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 on 2 October 2012; (3) UNITED STATES. ENVIRONMENTAL PROTECTION AGENCY Health Effects Test Guidelines. OPPTS 870.2400,1998; and (4) Globally Harmonized System of Classification and Labeling of Chemicals (GHS), United Nations Economic Commission for Europe, 2007, retrieved July 13, 2007.
[087] The scoring criteria were shown as follows: Irritation Score Observation Corneal opacity (Densest part) 0-4 Highest irritation score is 4 Iritis 0-2 Highest irritation score is 2 Conjunctival hyperemia 0-3 Highest irritation score is 3 Conjunctival edema (containing eyelid and nictitating membrane) 0-4 Highest irritation score is 4 EXPERIMENTAL EXAMPLE 2
[088] The efficacy trials of individual agrochemical compositions of Examples 1-1~1-7 and Comparative Example 1-1~1-2 were conducted in a wheat field, where the main weeds were Galium spurium and Chenopodium glaucum (3-5 leaf stage), and the wheat was in the stage of Petition 870220112460, dated 02 / 12 / 2022, page 23 / 88 18 / 24 tillering. Each example was used to treat an area of 1 mu, and different treatment areas are separated by a protective row. The agrochemical compositions provided in Examples 1-1~1-7 and Comparative Examples 1-1~1-2 were diluted with water and sprayed on the stems and leaves, respectively, where the dosage was set so that an amount of the effective ingredient was 1.5 g / mu, and the spray volume was 40 l / mu. The blank control group was sprayed with the same amount of water. 15 days after administration, the fresh weight of weeds was investigated, and the wheat growth inhibition rate (%) was visually observed, which are shown in Table 2.
[089] The agrochemical compositions in Examples 1-1~1-7 and Comparative Examples 1-1~1-2 all exhibited significant inhibitory effects on broadleaf weeds in the wheat field. Compared with the Comparative Examples, the agrochemical compositions in the Examples had better efficacy. Under the same dosage, all Examples and Comparative Examples had no phytotoxicity to wheat. TABLE 2 FIELD CONTROL EFFECT OF AGROCHEMICAL COMPOSITIONS ON BROADLEAF WEEDS IN THE FIELD OF WHEAT Group Fresh weight of Galium spurium (%) Fresh weight of Chenopodium glaucum (%) Broadleaf weed Total fresh weight of weed (%) Wheat phytotoxicity (Growth inhibition rate) (%) Example 1-1 87.8 86.5 86.9 0.0 Example 1-2 88.9 84.3 85.8 0.0 Example 1-3 85.6 84.5 85.0 0.0 Example 1-4 90.3 87.1 88.1 0.0 Example 1-5 88.5 86.2 86.1 0.0 Petition 870220112460, dated 02 / 12 / 2022, page 24 / 88 19 / 24 Example 1-6 87.6 81.8 83.4 0.0 Example 1-7 88.3 85.9 85.5 0.0 Comparative Example 11 82.5 81.7 82.2 0.0 Comparative Example 12 79.6 77.9 78.0 0.0 Blank control group 0.0 0.0 0.0 / EXAMPLE 2-1
[090] An agrochemical composition has been provided in this document, comprising 57% by weight of an unsaturated fatty acid ester, 18% by weight of an emulsifier, 25% by weight of a hydrophobic pesticide, wherein the unsaturated fatty acid ester has been shown in the following formula: O / H2 \ / H H2n H\ / H2 \ || / H2 \h'cVc1h4c-c— ':?;(·>7o- / 7h· ; where a=4, b=1, c=7, d=0, n=1; the hydrophobic pesticide was trinexapac-ethyl; the emulsifier includes polyoxyethylene fatty alcohol ether (emulsifier Genapol X 060, purchased from Clariant Company) and polyoxyethylene sorbitan ester (emulsifier Tween-80, purchased from Croda Sipo Co., Ltd.), and a weight percentage of polyoxyethylene fatty alcohol ether in the agrochemical composition was 10%; and a weight percentage of polyoxyethylene sorbitan ester in the agrochemical composition was 8%. EXAMPLE 2-2
[091] An agrochemical composition has been provided in this document, comprising 40% by weight of an unsaturated fatty acid ester, 18% by weight of an emulsifier, 25% by weight of a hydrophobic pesticide and 17% by weight of water, wherein the unsaturated fatty acid ester, the hydrophobic pesticide and the Petition 870220112460, dated 02 / 12 / 2022, page 25 / 88 20 / 24 emulsifiers used in this document were, respectively, the same as those in Example 2-1. EXAMPLE 2-3 An agrochemical composition has been provided in this document, which includes 30% by weight of an unsaturated fatty acid ester, 25% by weight of an emulsifier, and 45% by weight of a hydrophobic pesticide, wherein the unsaturated fatty acid ester, the hydrophobic pesticide, and the emulsifier used in this document were, respectively, the same as those in Example 21; a weight percentage of the polyoxyethylene fatty alcohol ether emulsifier in the agrochemical composition was 10%, and a weight percentage of the polyoxyethylene sorbitan ester in the agrochemical composition was 15%. EXAMPLE 2-4
[092] An agrochemical composition was provided in this document, which differed from that in Example 2-1 in that the formula for the unsaturated fatty acid ester was: O / H2 \ J_ H H2n H\ H H2 \ II I H2 \H'CfClH4C-C—CtHTClC-OVHdCH',a=4, b=2, c=4, d=1, en=1. EXAMPLE 2-5
[093] An agrochemical composition was provided in this document, which differed from that in Example 2-1 where the formula for the unsaturated fatty acid ester was: O / H2 \ J_ HH2n H\ H H2 \ II I H2 \ ·<'-'''-- °· - 7H,a=0, b=4, c=3, d=1, en=1. EXAMPLE 2-6
[094] An agrochemical composition was provided in this document, which was different from that in Example 2-1 where in the fatty acid ester formula Petition 870220112460, dated 02 / 12 / 2022, p. 26 / 88 21 / 24 unsaturated: O / H2 \ J_H H2n H \ HH, \ II H H2\ H'CVlHT-C-— CtHfHC-OVACH , a=1, b=2, c=7, d=0, en=1. COMPARATIVE EXAMPLE 2-1
[095] An agrochemical composition has been provided herein, comprising 18% by weight of an emulsifier, 25% by weight of a hydrophobic pesticide and 57% by weight of a solvent, wherein the emulsifier and hydrophobic pesticide used herein were, respectively, the same as those in Example 2-1, and the solvent was methyl caprylate. COMPARATIVE EXAMPLE 2-2
[096] An agrochemical composition has been provided in this document, comprising 18% by weight of an emulsifier, 25% by weight of a hydrophobic pesticide, 40% by weight of a solvent and 17% by weight of water, wherein the emulsifier, the hydrophobic pesticide and the solvent used in this document were, respectively, the same as those in Comparative Example 2-1, and the water was deionized. COMPARATIVE EXAMPLE 2-3
[097] An agrochemical composition has been provided in this document, comprising 18% by weight of an emulsifier, 25% by weight of a hydrophobic pesticide and 57% by weight of a solvent, wherein the emulsifier and hydrophobic pesticide used in this document were, respectively, the same as those in Comparative Example 2-1, and the solvent was tetrahydrofurfuryl alcohol. EXPERIMENTAL EXAMPLE 3
[098] 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, respectively, administered to New Zealand white rabbits at a dosage of 0.1 ml. Three replicates were conducted for each composition. Petition 870220112460, dated 02 / 12 / 2022, page 27 / 88 22 / 24 agrochemical (namely, the same agrochemical composition was administered to three rabbits) to determine the level of eye irritation caused by the agrochemical composition to New Zealand white rabbits.
[099] During the experiments, the agrochemical compositions were merely administered to the conjunctival sac of one eye of each rabbit, and the other eye served as a control. 24 h after administration, the cornea, iris and conjunctiva of the eye were observed to assess irritation, and the results are shown in Table 3. TABLE 3 EYE DAMAGE AND SCORING TABLE Scores (24 h) Corneal opacity Iritis Conjunctival hyperemia Conjunctival edema Example 2-1 0 0 1 0 Example 2-2 0 0 1 0 Example 2-3 0 0 1 1 Example 2-4 0 0 1 0 Example 2-5 0 0 1 1 Example 2-6 0 0 1 1 Comparative Example 2-1 2 0 2 3 Comparative Example 2-2 2 0 2 2 Petition 870220112460, dated 02 / 12 / 2022, page 28 / 88 23 / 24 Comparative Example 2-3 3 1 3 3 Notes: The scoring criteria above are the same as those in Table 1 and are not repeated in this document. EXPERIMENTAL EXAMPLE 4
[100] Efficacy trials of individual agrochemical compositions from Examples 2-1~2-6 and Comparative Example 2-1~2-3 were conducted in a wheat field, where the wheat was Yangmai 20 at the tillering stage. Each example was used to treat an area of 1 mu, and different treatment areas are separated by a protective row. The agrochemical compositions provided in Examples 2-1~2-6 and the agrochemical compositions provided in Comparative Examples 2-1~2-3 were diluted with water and sprayed onto the stems and leaves, respectively, where the dosage was set so that an amount of the effective ingredient was 7 g / mu, and the spray volume was 40 l / mu. The blank control group was sprayed with the same amount of water.Wheat stem lengths at 14, 28, and 55 days after administration were investigated and compared with wheat stem lengths from the blank control plant to calculate the growth inhibition rate, which are shown in Figure 4. The agrochemical compositions in Examples 2-1~2-6 and Comparative Examples 2-1~2-3 have a significant inhibitory effect on wheat plant growth and noticeably enhance wheat stem strength, thus effectively regulating wheat growth and preventing lodging. TABLE 4 FIELD TEST RESULTS OF AGROCHEMICAL COMPOSITIONS ON THE WHEAT GROWTH REGULATORY EFFECT. Petition 870220112460, dated 02 / 12 / 2022, page 29 / 88 24 / 24 Group Stem Length Growth Inhibition Rate (GIR) (%) Stem Resistivity Growth Stimulation Rate (GSR) (%) Day 14 Day 28 Day 55 Day 55 Example 2-1 4.2 12.0 10.8 19.7 Example 2-2 4.9 11.9 9.6 18.2 Example 2-3 4.4 12.6 8.6 15.1 Example 2-4 6.5 11.1 10.2 18.0 Example 2-5 4.3 10.4 8.3 19.5 Example 2-6 4.6 11.1 8.8 15.1 Comparative Example 2-1 5.9 10.7 10.1 15.0 Comparative Example 2-2 4.6 10.4 9.4 13.3 Comparative Example 2-3 4.4 10.9 8.1 14.3 Blank control group / / / /
[101] It should be noted that the embodiments mentioned above are merely illustrative of the technical solutions of this application and are not intended to limit the scope of this application. Although this application has been described in detail with reference to the embodiments above, it should be understood that various modifications, variations and substitutions may still be made by persons skilled in the art. Such modifications, variations and substitutions made by persons skilled in the art based on the content disclosed herein without departing from the spirit of this application must be within the scope of this application as defined by the appended claims.
Claims
1. LOW EYE IRRITATION AGROCHEMICAL COMPOSITION, characterized by: an unsaturated fatty acid ester; and an agrochemical; wherein the agrochemical is selected from the group consisting of carfentrazone-ethyl, trinexapac-ethyl or a combination thereof; and the unsaturated fatty acid ester is shown in the following formula: O / h2\ / h h2 h\_ / H2\ II H h2\ H'CtClírVC-C~ C7bHVC7hC-OVCTdCH3. ; wherein a=4, b=1, c=7, d=0, and n=1; a=4, b=2, c=4, d=1, and n=1; a=1, b=2, c=7, d=1, and n=1; a=4, b=3, c=3, d=0, and n=1; a=0, b=4, c=3, d=0, and n=1; a=0, b=4, c=3, d=1, and n=1; or a=1, b=2, c=7, d=0, and n=1.
2. LOW EYE IRRITATION AGROCHEMICAL COMPOSITION, according to claim 1, characterized in that it comprises 20-60% by weight of unsaturated fatty acid ester and 5 to 50% by weight of the agrochemical; and the low eye irritation agrochemical composition is an emulsifiable concentrate (EC) formulation.
3. LOW EYE IRRITATION AGROCHEMICAL COMPOSITION, according to claim 1, characterized by comprising: an emulsifier; wherein the emulsifier is selected from the group consisting of alkyl benzene sulfonate salt, alkyl benzene sulfonate ester, alkyl sulfonate salt, alkyl sulfonate ester, carboxylate, carboxylic acid ester, alcohol alkoxylate, alkylphenol ethoxylate, castor oil ethoxylate, Petition 870260061751, dated 06 / 24 / 2026, p. 10 / 17 2 / 2 amine ethoxylate, sorbitan fatty acid ester, alkyl polyglycoside, ethylene oxide-propylene oxide copolymer, ethoxylated phenol phosphate, tristeyrylphenol phosphate, fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester and a combination thereof.