Method for preventing deformation of resin pesticide containers

Abstract

Agrochemical oil-based suspensions are often-used formulations among liquid agrochemical pharmaceutical products, but when a plastic agrochemical container is employed as a container to be filled with such a suspension, the container may be deformed or damaged during storage or transport.　With focus on the use of a specific antioxidant, the present invention provides a method for minimizing oxidation of an oil-based component of an agrochemical oil-based suspension to thereby prepare a chemically stable oil-based suspension, and filling a plastic agrochemical container with the suspension, thereby preventing deformation of the container.

Description

Technical Field

[0001] The present invention relates to a method for preventing deformation of a resin pesticide container filled with an oily pesticide suspension and to an oily pesticide suspension used in that method.

Background Art

[0002] For containers of liquid pesticide preparations, resin containers are often adopted, which are excellent in convenience such as ease of processing, light weight, gas barrier properties, and not easily broken like glass bottles. On the other hand, among liquid pesticide preparations, oily suspensions are preparations in which the active ingredient of the pesticide is dispersed in an oily component, and due to the action of a surfactant added for the purpose of uniformly dispersing the oily component in the spraying liquid, the adhesiveness and penetrability to crops are excellent, so the addition of a spreading agent to the spraying liquid is not required, and it is widely used among liquid pesticide preparations.

[0003] Patent Document 1 describes a method for reducing the problem of the neck-in effect during storage and transportation of industrial products such as fuels and lubricants by using a bactericidal composition containing an aldehyde donor compound and an antioxidant selected from gallic acid esters, phenol derivatives, L-ascorbic acid and its salts and derivatives, and tocopherols and their derivatives. However, Patent Document 1 does not describe resin containers filled with oily pesticide suspensions.

[0004] Patent Document 2 describes that, as a method for preventing deformation of a plastic container when storing a liquid medicine in the plastic container, the dissolved oxygen concentration of the liquid medicine should be 30 ppm or less. Specific methods for reducing the dissolved oxygen concentration include a method of blowing an inert gas such as nitrogen gas into the medicine liquid, a method of heating in an inert gas atmosphere, and a method of returning to normal pressure with an inert gas after depressurization.

[0005] Patent Document 3 describes a method for preventing container deformation by preparing a liquid agent containing an organic solvent, performing a degassing treatment, and then allowing the liquid agent to stand or be stirred under normal or pressurized pressure to redissolve the gas in the liquid agent, thereby returning the amount of gas in the liquid agent to a certain level or higher and adjusting the amount of dissolved gas in the liquid agent.

[0006] Patent Document 4 describes that dibutylhydroxytoluene, butylhydroxyanisole, t-butylhydroquinone, and propyl gallate can be added as antioxidants to the oily suspension of pesticides, and cited document 5 describes that dibutylhydroxytoluene, butylhydroxyanisole, and epichlorohydrin can be added as stabilizers. However, neither Patent Document 4 nor Patent Document 5 describes resin containers filled with the oily suspension of pesticides. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2005-82595 [Patent Document 2] Japanese Patent Publication No. 2002-97103 [Patent Document 3] Japanese Patent Publication No. 2017-114506 [Patent Document 4] Chinese Patent Application Publication No. 101785455 [Patent Document 5] Chinese Patent Application Publication No. 107439578 [Overview of the project] [Problems that the invention aims to solve]

[0008] As mentioned above, oily suspensions of pesticides are a commonly used formulation among liquid pesticide preparations. However, when resin containers are used to fill them, deformation or damage to the containers can occur during storage or transportation, and preventing this is a challenge. [Means for solving the problem]

[0009] The inventors, in order to solve the aforementioned problems, conducted research and found that the oily components in pesticide oily suspensions are susceptible to oxidation by the action of oxygen in the air, moisture, heat, light, metal ions, microorganisms, etc., and that oxidation is particularly accelerated by light and heat. They concluded that, depending on the storage conditions of a resin container filled with pesticide oily suspension, the oxygen present in the space inside the container may react with the oily components, consuming the oxygen and creating a reduced pressure inside the container, which could lead to deformation or damage to the container. As a means of solving this problem, they focused on using a specific antioxidant and found that by suppressing the oxidation of the oily components of the pesticide oily suspension, a chemically stable oily suspension can be prepared, and by filling a resin container with this, deformation of the container can be prevented. This led to the completion of the present invention. [Effects of the Invention]

[0010] According to the present invention, a method can be provided to prevent deformation of a resin pesticide container filled with an oily pesticide suspension. [Modes for carrying out the invention]

[0011] The present invention relates to a method for preventing deformation of a resin pesticide container filled with an oily pesticide suspension, wherein the oily pesticide suspension filled into the resin pesticide container contains (1) an active pesticide component, (2) an oily component, and (3) at least one antioxidant selected from the group consisting of phenol derivatives, gallic acid esters, and ethoxyquin.

[0012] The present invention also relates to an oily pesticide suspension containing (1) an active pesticide ingredient, (2) an oily component, and (3) at least one antioxidant selected from the group consisting of phenol derivatives, gallic acid esters, and ethoxyquin, wherein the oxidation of the oily component generated in the container after filling the resin pesticide container is suppressed, and the oily pesticide suspension is for preventing deformation of resin pesticide containers.

[0013] In this invention, deformation of a resin pesticide container refers to a state in which the shape of the container deteriorates from its state at the time the pesticide oil suspension was filled, resulting in dents, shrinkage, distortion, damage, cracks, etc., and which cannot be restored to its original shape.

[0014] The active pesticide ingredient in the present invention is not particularly limited as long as it can be prepared as an oily suspension, but examples include nicosulfuron, flazasulfuron, tolpyralate, thiafenacil, mesotrione, atrazine, bromoxynil, terbutyrazine, acetochlor, metrachlor, chlorfluazuron, fostiazate, flonicamide, cyclaniliprole, isofetamide, cyazofamide, pyriophenone, fluazinam, and the like. Among these, nicosulfuron, flazasulfuron, tolpyralate, flonicamide, isofetamide, cyazofamide, pyriophenone, or fluazinam are preferred, with nicosulfuron or tolpyralate being more preferred.

[0015] The oily component in the present invention is not particularly limited as long as it contains an unsaturated hydrocarbon as a site that reacts with oxygen in the container after the pesticide oily suspension is filled into a resin pesticide container. Examples include vegetable oil, alkyl esterified vegetable oil, mineral oil, and aromatic oil, and these may be used in mixture form.

[0016] Examples of vegetable oils or alkyl esterified vegetable oils include soybean oil, rapeseed oil, tall oil, olive oil, castor oil, papaya oil, camellia oil, coconut oil, palm oil, sesame oil, corn oil, rice oil, peanut oil, cottonseed oil, linseed oil, sunflower oil, neem oil, safflower oil, and their alkyl ester oils, with rapeseed oil, corn oil, soybean oil, and their methyl ester oils being preferred. Also, as the oily component, fatty acid glycerides can be used. Fatty acid glycerides can be obtained, for example, from vegetable oils. The number of substitutions of fatty acids is arbitrary, and examples include monoglycerides, diglycerides or triglycerides. In the case of diglycerides or triglycerides, the same or different fatty acids may be substituted at any position. When different fatty acids are substituted, they may be either unsaturated fatty acids or saturated fatty acids. Also, two or more types of fatty acid glycerides can be mixed and used. Examples of the fatty acids include α-linolenic acid, linoleic acid, oleic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, arachidic acid, eicosenoic acid, behenic acid, erucic acid, lignoceric acid, erucic acid, ricinoleic acid, etc. Among them, linoleic acid, oleic acid, palmitic acid, stearic acid, and erucic acid are preferable. Also, alkyl esterified fatty acid glycerides in which the fatty acid moiety is alkyl esterified are preferable, and methylated fatty acid glycerides are particularly preferable.

[0017] Examples of the mineral oil include machine oil, paraffin oil, and naphthenic oil. Among them, paraffin oil is preferable. Mineral oil mainly contains saturated hydrocarbons, but may contain unsaturated hydrocarbons mixed therein, which are the subject of the present invention.

[0018] Examples of the aromatic oil include solvent naphtha and xylene. Among them, solvent naphtha is preferable.

[0019] Examples of the antioxidant in the present invention include, for example, phenol derivatives, gallic acid esters, and ethoxyquin.

[0020] The antioxidant can obtain the desired effect by adding it to the formulation, but a state in which the antioxidant is dissolved in the formulation is preferable. Since the agrochemical oily suspension formulation of the present invention is an agrochemical formulation based on oil, a lipophilic antioxidant is particularly preferable.

[0021] Examples of the phenolic derivative include dibutylhydroxytoluene, butylhydroxyanisole, 2,5-di-tert-amylhydroquinone, 2,5-di-tert-butylhydroquinone, 4,4'-butylidenebis(6-tert-butyl-m-cresol), 4,4'-thiobis(6-tert-butyl-m-cresol), and bis(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfide. Among them, dibutylhydroxytoluene is preferred.

[0022] Examples of the gallic acid ester include methyl gallate, ethyl gallate, 2-hydroxyethyl gallate, propyl gallate, isopropyl gallate, and butyl gallate. Among them, propyl gallate is preferred.

[0023] As the antioxidant, dibutylhydroxytoluene is particularly preferred.

[0024] In the present invention, even if the addition amount of the antioxidant is very small, the desired effect can be obtained. However, for suppressing the deformation of the resin pesticide container over a long period, the weight ratio of the antioxidant to the oily component is usually 0.0001:99.9999 to 30:70, preferably 0.001:99.999 to 20:80, and more preferably 0.01:99.99 to 15:85.

[0025] The resin pesticide container for filling the pesticide oil-based suspension in the present invention is not particularly limited. For example, resin pesticide containers industrially produced by a direct blow molding method or a stretch blow molding method from materials such as low-density polyethylene, high-density polyethylene, polyvinyl chloride, polypropylene, polyamide, polyethylene terephthalate, polyvinylidene chloride, nitrile resin, polycarbonate, polyacrylate, polymethylpentene, polyethylene vinyl alcohol resin, and perfluoroalkoxy fluororesin are preferred. The capacity is not particularly limited, and examples thereof include 100 mL, 500 mL, 1 L, 5 L, 10 L, 20 L, 200 L, and 1000 L, with 500 mL, 1 L, and 5 L being preferred.

[0026] The proportions of the active pesticide, oily component, and antioxidant in the pesticide oily suspension of the present invention may be changed as appropriate depending on the type and properties of each component, and cannot be specified in general terms, but for example they are as follows. The amount of the active ingredient in the pesticide is 0.1 to 80 parts by weight, preferably 0.5 to 50 parts by weight, and more preferably 2 to 35 parts by weight. The oily component is 1 to 99 parts by weight, preferably 5 to 95 parts by weight, and more preferably 15 to 75 parts by weight. The antioxidant is present in an amount of 0.001 to 10 parts by weight, preferably 0.01 to 10 parts by weight, and more preferably 0.1 to 3 parts by weight.

[0027] The oily suspension of agricultural chemicals of the present invention may contain formulation aids such as surfactants, antifreezes, anti-settling agents, defoaming agents, and solvents, as needed.

[0028] Examples of the aforementioned surfactants include anionic surfactants such as fatty acid salts, benzoates, alkyl sulfosuccinates, dialkyl sulfosuccinates, alkyl sulfate esters, alkyl sulfates, alkyl diglycol ether sulfates, alcohol sulfate esters, alkyl sulfonates, alkylaryl sulfonates, alkyl diphenyl ether disulfonates, polystyrene sulfonates, alkyl phosphate esters, alkylaryl phosphates, styrylaryl phosphates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylaryl ether sulfates, polyoxyethylene styrylaryl ether sulfates, polyoxyethylene styrylaryl ether sulfates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylaryl phosphates, polyoxyethylene styrylaryl ether phosphates, or salts thereof; sorbitan fatty acid esters, glycerin Examples of nonionic surfactants include fatty acid esters, fatty acid polyglycerides, fatty acid alcohol polyglycol ethers, acetylene glycol, acetylene alcohol, oxyalkylene block polymers, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene styrylaryl ethers, polyoxyethylene allylphenyl ethers, polyoxyethylene glycol alkyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxyethylene castor oil, polyoxypropylene fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene alkyl ether phosphate esters, and polyoxyethylene methylpolysiloxane; cationic surfactants such as alkoxylated aliphatic amines; and two or more of these may be mixed as needed. The blending ratio of the surfactant is 0 to 80 parts by weight, preferably 5 to 70 parts by weight.

[0029] The aforementioned antifreeze agent is preferably a dihydric alcohol, specifically an alkylene glycol such as ethylene glycol or propylene glycol, with propylene glycol being the most preferred. The dihydric alcohol also acts as a viscosity reducer, and in addition to its antifreeze effect, it may reduce the viscosity of the pesticide oily suspension and improve its fluidity. The proportion of the antifreeze agent is usually 2 to 30 parts by weight, preferably 5 to 10 parts by weight.

[0030] Examples of the aforementioned settling inhibitors include natural polysaccharides such as xanthan gum, ramzan gum, locust bean gum, carrageenan, and welan gum; synthetic polymers such as sodium polyacrylate; semi-synthetic polysaccharides such as carboxymethylcellulose; mineral fine powders such as aluminum magnesium silicate, smectite, bentonite, hectorite, dry silica, organic bentonite, and organic hectorite, as well as alumina sol. Two or more of these may be mixed as needed. The blending ratio of the settling inhibitor is usually 0.01 to 10.0 parts by weight, preferably 0.1 to 5.0 parts by weight.

[0031] Examples of defoaming agents include silicone-based defoaming agents containing polydimethylsiloxane as an active ingredient, silica, etc. Specifically, examples include trade names SILCOLAPSE 432 (manufactured by Bluestar Silicones), SILFOAM SC 120 (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), SAG 47, SAG 1538, SAG 1572 (manufactured by Momentive), etc. Silica may be mixed in as needed. The blending ratio of the defoaming agent is usually 0.01 to 10 parts by weight, preferably 0.1 to 2.0 parts by weight.

[0032] Examples of solvents include water, dioxane, acetone, isophorone, methyl isobutyl ketone, chlorobenzene, cyclohexane, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, dimethyl C8-C12 amide, N-methyl-2-pyrrolidone, 2-ethylhexanol, γ-butyrolactone, alcohol, acetic acid, butyric acid, lactic acid, isopropyl acetate, butyl acetate, dimethyl lactate, benzene, alkylbenzene, and alkylnaphthalene. Two or more of these may be mixed as needed. The solvent blending ratio is usually 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight.

[0033] The present invention can be used to produce an oily suspension of pesticides in accordance with conventional methods in the art. For example, one method involves adding a surfactant, an anti-settling agent, and a stabilizer to an oily component and mixing them, then adding the active pesticide component, and if necessary, adding other auxiliary agents. After pre-pulverizing with a homogenizer or the like, the mixture is finely pulverized to a predetermined particle size using a wet grinder with zircon beads or the like, and then adding and mixing auxiliary agents such as thickeners. Another method involves dry-pulverizing the active pesticide component together with auxiliary agents such as a surfactant, adding the dry-pulverized mixture to an oily component in which the surfactant, anti-settling agent, and other auxiliary agents are dissolved, pre-pulverizing with a homogenizer or the like, finely pulverizing to a predetermined particle size using a wet grinder with glass beads or the like, and then adding and mixing auxiliary agents such as thickeners and stabilizers as necessary. The particle size of the active pesticide component is usually preferably pulverized to around 0.1 to 5 μm, and it is desirable to change the particle size according to the physical properties of the active pesticide component.

[0034] Examples of grinders that can be used when manufacturing the pesticide oily suspension of the present invention include wet grinders such as bead mills, vibratory mills, and planetary mills, but examples of which can be used include Paint Shaker (manufactured by Toyo Seiki Seisakusho), Grinding Nano Taro NP-100 (manufactured by THINKY), Dyno Mill KD type (manufactured by WAB), and Lady Mill RMH type (manufactured by AIMEX). Examples of beads that can be used include glass beads, zirconia beads, and zircon beads. It is preferable to use beads with a particle size in the range of 0.01 to 1.5 mm, and more preferably in the range of 0.5 to 1.0 mm. By using beads with a small particle size, it is possible to manufacture a pesticide oily suspension with a small average particle size.

[0035] The average particle size of the active ingredient in pesticides can be measured using laser diffraction particle size analyzers such as the Microtrac MT3300-EXII (manufactured by Nikkiso Co., Ltd.) or the Mastersizer 3000 (manufactured by Malvern). When using the Microtrac MT3300-EXII, the measurement can be performed by dispersing the sample in an organic solvent such as n-hexane.

[0036] The viscosity of the pesticide oily suspension of the present invention can be measured, for example, using a TVB-10 viscometer (manufactured by Toki Sangyo Co., Ltd.) or a Brook Field viscometer (manufactured by Brook Field). When using a TVB-10 viscometer, the measurement can be performed with a sample liquid temperature of 20°C, a rotation speed of 60 rpm, and rotor M2 or M3.

[0037] In this invention, after filling a resin pesticide container with an oily pesticide suspension, nitrogen gas can be supplied to the empty space inside the container from a device such as a cartridge-type nitrogen cylinder (manufactured by Narika Co., Ltd.), thereby replacing the empty space inside the container with nitrogen. The nitrogen-purged container can then be sealed using a device such as an induction liner (DGF-500 model, manufactured by Landsworks Co., Ltd.).

[0038] Preferred embodiments of the present invention are described below.

[0039] [1] A method for preventing deformation of a resin pesticide container filled with an oily pesticide suspension, wherein the oily pesticide suspension filled in the resin pesticide container contains (1) an active pesticide component, (2) an oily component, and (3) at least one antioxidant selected from the group consisting of phenol derivatives, gallic acid esters, and ethoxyquin. [2] The method according to [1], wherein the antioxidant is at least one selected from the group consisting of phenol derivatives and gallic acid esters. [3] The method according to [1] or [2], wherein the phenol derivative is at least one selected from the group consisting of dibutylhydroxytoluene, butylhydroxyanisole, 2,5-di-tert-amylhydroquinone, 2,5-di-tert-butylhydroquinone, 4,4'-butylidenebis(6-tert-butyl-m-cresol), 4,4'-thiobis(6-tert-butyl-m-cresol), and bis(5-tert-butyl-4-hydroxy-2-methylphenyl) sulfide. [4] The method according to [1] or [2], wherein the gallic acid ester is at least one selected from the group consisting of methyl gallate, ethyl gallate, 2-hydroxyethyl gallate, propyl gallate, isopropyl gallate, and butyl gallate. [5] The method according to [1] to [4], wherein the oily component is at least one selected from the group consisting of vegetable oil, alkyl esterified vegetable oil, mineral oil and aromatic oil. [6] The method according to [5], wherein the vegetable oil or alkyl esterified vegetable oil is selected from the group consisting of soybean oil, rapeseed oil, tall oil, olive oil, castor oil, papaya oil, camellia oil, coconut oil, palm oil, sesame oil, corn oil, rice oil, peanut oil, cottonseed oil, linseed oil, sunflower oil, neem oil, safflower oil, and alkyl ester oils thereof. [7] The method according to [5], wherein the mineral oil is at least one selected from the group consisting of machine oil, paraffin oil and naphthenic oil. [8] The method according to [5], wherein the aromatic oil is at least one selected from the group consisting of solvent naphtha and xylene. [9] The method according to [1] to [4], wherein the oily component is a fatty acid glyceride.

[10] The method according to [9], wherein the fatty acid glyceride is a glyceride of at least one fatty acid selected from the group consisting of α-linolenic acid, linoleic acid, oleic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, arachidic acid, eicosenoic acid, behenic acid, erucic acid, lignoceric acid, erucic acid, and ricinoleic acid.

[11] The method according to [9] or

[10] , wherein the fatty acid glyceride is a monoglyceride, a diglyceride, a triglyceride, or a mixture thereof.

[12] The method according to [1] to

[11] , wherein the weight ratio of the antioxidant to the oily component is 0.01:99.99 to 15:85.

[13] The method according to [1] to

[12] , wherein after filling the oily pesticide suspension into a resin pesticide container, the gas in the space inside the container is further replaced with nitrogen gas.

[14] The method according to [1] to

[13] , wherein the active ingredient of the pesticide is nicosulfuron, flazasulfuron, tolpyralate, thiafenacil, mesotrione, atrazine, bromoxynil, terbutyrazine, acetochlor, metrachlor, chlorfluazuron, fostiazate, flonicamide, cyclaniliprole, isofetamide, cyazofamide, pyriophenone, or fluazinam.

[15] The method according to [1] to

[13] , wherein the active ingredient of the pesticide is at least one selected from the group consisting of nicosulfuron and tolpyralate.

[16] An oily pesticide suspension for preventing deformation of resin pesticide containers, as described in [1] to

[15] above.

[17] A method for preventing deformation of a resin pesticide container, comprising: (1) an active pesticide component, (2) an oily component, and (3) at least one antioxidant selected from the group consisting of phenol derivatives, gallic acid esters, and ethoxyquin to prepare an oily pesticide suspension; Next, the oily suspension of the pesticide is filled into a resin pesticide container. A method for suppressing the pressure reduction inside a resin pesticide container caused by the consumption of oxygen inside the container after filling.

[18] The method according to

[17] , wherein the antioxidant is at least one selected from the group consisting of phenol derivatives and gallic acid esters. [Examples]

[0040] The following describes examples relating to the present invention, but these are not intended to limit the present invention. First, examples of formulations are described.

[0041] Examples of formulations The oily suspension is prepared by mixing and grinding the amounts of each component shown in Table A below using a homogenizer ULTRA-TURRAX T25basic (manufactured by IKA). The numbers in Table A represent parts by weight. The surfactants (C1) to (C7), which are component (C) in Table A, are shown in Table B, and the components of the products listed in Table A are as follows. • Product name "SAG47": Silicone-based defoaming agent (manufactured by Momentive) • Product name "Agnique ME 18RD-F": Methyl ester of C16-18 saturated fatty acids and C18 unsaturated fatty acids (manufactured by BASF) • Product name "Corn Salad Oil": Triacylglycerol (manufactured by Boso Oil & Fat Co., Ltd.)

[0042] [Table 1]

[0043] [Table 2]

[0044] [Table 3]

[0045] Next, we will describe an example test. Test Example 1 As described below, oily suspensions containing the active ingredient of the pesticide and oily suspensions without the active ingredient of the pesticide were prepared. [Contains active pesticide ingredients] A mixture of the active pesticide ingredients (12.0 parts by weight of tolpyrate and 12.0 parts by weight of nicosulfuron), 10.5 parts by weight of polyoxyethylene sorbitan fatty acid ester, 1.2 parts by weight of polyoxyethylene castor oil, 3.3 parts by weight of alkylbenzene sulfonate calcium, 1.5 parts by weight of organic bentonite, 3.0 parts by weight of polyoxyethylene monoalkyl ether, and 3.0 parts by weight of dry-process silica was prepared by mixing these ingredients and adding 54.7 parts by weight of Agnique ME18RD-F (trade name: methyl ester of C16-18 saturated fatty acids and C18 unsaturated fatty acids, manufactured by BASF) to make a total volume of 1 L. The mixture was then mixed and ground using a homogenizer ULTRA-TURRAX T25basic (manufactured by IKA), and further ground using a bead mill to obtain an oily suspension agent with a particle size of 5 μm or less for the active pesticide ingredients.

[0046] [No active ingredients in pesticides] 6.2 parts by weight of polyoxyethylene sorbitan fatty acid ester, 0.7 parts by weight of polyoxyethylene castor oil, 1.9 parts by weight of alkylbenzene sulfonate calcium, and 79.2 parts by weight of Agnique ME18RD-F (trade name: methyl ester of C16-18 saturated fatty acids and C18 unsaturated fatty acids, manufactured by BASF) were added to prepare a total volume of 1 L, and then the mixture was mixed and ground using a homogenizer ULTRA-TURRAX T25basic (manufactured by IKA) to obtain an oily suspension.

[0047] Test samples were prepared by adding and mixing the antioxidants (dibutylhydroxytoluene or ascorbic acid) shown in Table 1 to each oily suspension, and then filling 200 ml of each sample into 500 ml polyethylene bottles (model number: NSW-500-2(M) bottle, manufactured by Toto Seikei Co., Ltd.). Before sealing the bottles with induction liners, an oxygen concentration measuring tip was inserted into the empty space. For some samples, the gas in the empty space of the bottle was replaced with nitrogen gas (cartridge-type experimental gas (manufacturer: Narika Co., Ltd.)), and the bottles were sealed with induction liners (model DGF-500, manufactured by Landsworks Co., Ltd.) and stored at room temperature for 863 days. After storage, the appearance of the bottles was inspected according to the following criteria, and the oxygen concentration inside the bottles was also measured. The results are shown in Table 1. Bottle container appearance: ○: No change or very slight change, ×: Large dent on the body.

[0048] [Table 4]

[0049] The results of Test Example 1 showed that under long-term storage conditions, the deformation of the bottle container was suppressed by including 0.2 parts by weight of the antioxidant of the present invention. Furthermore, the deformation of the bottle container was also suppressed by including 0.02 parts by weight of the antioxidant and replacing the air inside the bottle container with nitrogen. In addition, the oxygen concentration was slightly higher when the formulation contained the active ingredient of the pesticide.

[0050] Test Example 2 An oily suspension was prepared using the same method as in Test Example 1. 0.01 to 3.0 parts by weight of the antioxidants shown in Table 2 were added and mixed. The appearance of the bottle container and the oxygen concentration inside the bottle container were then measured. The results are shown in Table 2.

[0051] [Table 5]

[0052] The results of Test Example 2 showed that under long-term storage conditions (140 days), adding 0.01 to 3.0 parts by weight of dibutylhydroxytoluene, the antioxidant of the present invention, and 0.2 parts by weight of propyl gallate or 0.2 parts by weight of ethoxyquin suppressed deformation of the bottle container. However, lipophilic antioxidants showed a higher inhibitory effect than hydrophilic antioxidants such as ascorbic acid. Furthermore, replacing the air inside the bottle container with nitrogen also suppressed deformation of the bottle container. In addition, formulations containing the active pesticide ingredient resulted in a higher oxygen concentration and a greater effect in preventing bottle container deformation.

[0053] Test Example 3 70 g of the oily suspension prepared in Test Example 2 was measured into a 100 ml glass bottle and placed in an aluminum packaging container (Yanagi Co., Ltd., model 0401, 12 x 22 cm). The amount of air inside was adjusted so that the volume of the aluminum laminate was 400-430 ml, and the container was sealed using a heat sealer (Fuji Impulse Co., Ltd., model PS-310E). It was stored at room temperature for 130 days. The change in the volume of the aluminum laminate container was investigated by measuring the volume of water when the aluminum laminate container was submerged in a 2 L graduated cylinder pre-filled with 1.5 L of water. The results are shown in Table 3.

[0054] [Table 6]

[0055] The results of Test Example 3 showed that under long-term storage conditions (130 days at room temperature), the deformation of the aluminum laminate container was suppressed by adding 0.01 to 3.0 parts by weight of dibutylhydroxytoluene, 0.2 to 3.0 parts by weight of propyl gallate, or 0.1 to 3.0 parts by weight of ethoxyquin. On the other hand, the effect of preventing container deformation was low when hydrophilic antioxidants such as ascorbic acid and D-isoascorbic acid, or tocopherol were added. Furthermore, the deformation of the aluminum laminate container was also suppressed by purging the air inside the bottle container with nitrogen. In addition, the effect of preventing deformation of the aluminum laminate container was higher when the formulation contained the active ingredient of the pesticide.

[0056] Test Example 4 Using the active ingredients of the pesticides shown in Table 4, an oily suspension was prepared in the same manner as in Test Example 1. 0.01 to 0.2 parts by weight of dibutylhydroxytoluene were added and mixed, and the suspension was stored at 40°C for 28 days. To investigate the condition of the bottle container, the outer diameter (center and bottom, 2 cm from the bottom) was measured, and the rate of change (CV) of the outer diameter was calculated using the following formula. A smaller CV value indicates less deformation of the container and a higher deformation prevention effect. The results are shown in Table 4. CV value = Standard deviation of container outer diameter ÷ Mean value of container outer diameter × 100

[0057] [Table 7]

[0058] The results of Test Example 4 showed that for each formulation containing pesticide active ingredients other than glyphosate, the deformation of the bottle container was suppressed by adding 0.1 parts by weight or more of dibutylhydroxytoluene per 100 mL of sample. Furthermore, the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2021-131666, filed on August 12, 2021, are incorporated herein by reference as disclosure of the specification of the present invention.

Claims

1. A method for preventing deformation of a resin pesticide container filled with an oily pesticide suspension, wherein the oily pesticide suspension filled into the resin pesticide container contains (1) an active pesticide component, (2) an oily component including an unsaturated hydrocarbon, and (3) at least one lipophilic antioxidant selected from phenol derivatives, and the content of the lipophilic antioxidant in the oily pesticide suspension is 0.1 parts by weight or more.

2. The method according to claim 1, wherein the phenol derivative is at least one selected from the group consisting of dibutylhydroxytoluene, butylhydroxyanisole, 2,5-di-tert-amylhydroquinone, 2,5-di-tert-butylhydroquinone, 4,4'-butylidenebis(6-tert-butyl-m-cresol), 4,4'-thiobis(6-tert-butyl-m-cresol), and bis(5-tert-butyl-4-hydroxy-2-methylphenyl) sulfide.

3. The method according to claim 1 or 2, wherein the oily component is at least one selected from the group consisting of vegetable oil, alkyl esterified vegetable oil, mineral oil, and aromatic oil.

4. The method according to claim 1 or 2, wherein the oily component is a fatty acid glyceride.

5. The method according to claim 4, wherein the fatty acid glyceride is a glyceride of at least one fatty acid selected from the group consisting of α-linolenic acid, linoleic acid, oleic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, arachidic acid, eicosenoic acid, behenic acid, erucic acid, lignoceric acid, erucic acid, and ricinoleic acid.

6. The method according to claim 4, wherein the fatty acid glyceride is a monoglyceride, a diglyceride, a triglyceride, or a mixture thereof.

7. The method according to claim 1 or 2, wherein the weight ratio of the lipophilic antioxidant to the oily component is 0.01:99.99 to 15:

85.

8. The method according to claim 1 or 2, wherein after filling the resin pesticide container with the aforementioned oily pesticide suspension, the gas in the space inside the container is further replaced with nitrogen gas.

9. A method for preventing deformation of resin pesticide containers, (1) an active ingredient in the pesticide, (2) an oily component containing an unsaturated hydrocarbon, and (3) at least one lipophilic antioxidant selected from phenol derivatives are mixed so that the content of the lipophilic antioxidant is 0.1 parts by weight or more to prepare an oily suspension for the pesticide. Next, the oily suspension of the pesticide is filled into a resin pesticide container. A method for suppressing the pressure reduction inside a resin pesticide container caused by the consumption of oxygen inside the container after filling.

10. The method according to claim 9, wherein nitrogen gas is supplied to the empty space of the resin pesticide container after filling it with the aforementioned oily pesticide suspension.

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