Method for preventing deformation of agrochemical container made of resin

Abstract

FIELD: agriculture.SUBSTANCE: invention relates to agrochemical plant protection products. The agrochemical product is an agrochemical container made of resin, obtained from a material selected from low-density polyethylene, high-density polyethylene, polyvinyl chloride, polypropylene, polyamide, polyethylene terephthalate, polyvinylidene chloride, ytrile resin, polycarbonate, polyacrylate, polymethylpentene, polyethylene vinyl alcohol resin or perfluoroalkoxyfluoride resin, filled with an oil-based agrochemical suspension comprising from 0.5 to 50 parts by weight, at least one component selected from the group consisting of nicosulfuron, flazasulfuron, tolpiralate, thiafenacil, mesotrione, atrazine, bromoxynil, terbuthylazine, acetochlor, metolachlor, chlorfluazuron, fosthiazate, flonicamid, cyclaniliprol, isofetamide, cyazofamid, pyriophenone or fluazinam, from 5 to 95 parts by weight of an oil component that is a lipophilic antioxidant comprising an unsaturated hydrocarbon, and from 0.001 to 10 parts by weight at least one antioxidant selected from the group consisting of: a phenol derivative, a gallic acid ester and ethoxyquin, wherein the phenol derivative is at least one member 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, wherein the weight ratio of the antioxidant to the weight of the oil component is from 0.01:99.99 to 15:85.EFFECT: proposed agrochemical product suppresses the oxidation of the oil component that occurs in an agrochemical container made of resin filled with an oil-based agrochemical suspension, and prevents deformation of the agrochemical container.11 cl, 9 tbl, 4 ex

Description

FIELD OF TECHNOLOGY TO WHICH THE INVENTION RELATES

[0001] The present invention relates to a method for preventing deformation of a resin-made agrochemical container filled with an oil-based agrochemical suspension, and to an oil-based agrochemical suspension used in the method.BACKGROUND

[0002] Resin containers are commonly used as containers for liquid agrochemical products. They are easy to recycle, lightweight, have low gas permeability, and are not easily destroyed, unlike glass bottles. Among liquid agrochemical products, oil-based suspensions are products containing an agrochemically active ingredient dispersed in an oil component. Because they have excellent adhesion to crops and are easily penetrated, they are assisted by a surfactant added to uniformly disperse the oil component in the spray liquid. This eliminates the need for a spreading agent in the spray liquid. They are commonly used alongside other liquid agrochemical products. Patent Document 1 describes a method for reducing the difficulty of thickening during storage and transportation of industrial products such as fuel and lubricant by using a fungicidal composition containing a formaldehyde donor compound and an antioxidant selected from the group consisting of gallic acid ester, a phenol derivative, L-ascorbic acid and its salt and derivative, and tocopherol and its derivative. However, Patent Document 1 does not describe a resin container filled with an oil-based agrochemical suspension.

[0004] Patent Document 2 describes a method for preventing deformation of a plastic container when stored filled with a liquid product by maintaining the dissolved oxygen concentration of the liquid product at 30 ppm or less, and, as a specific method for reducing the dissolved oxygen concentration, describes a method for purging the liquid product with an inert gas such as nitrogen, a method for heating the liquid product in an inert gas atmosphere, and a method for reducing the pressure and then restoring the normal pressure with the inert gas.

[0005] Patent Document 3 discloses a method for preventing deformation of a container, which includes deaerating a liquid product after preparing one containing an organic solvent and maintaining or stirring it under normal or elevated pressure, so that a gas is re-dissolved in the liquid product and the amount of gas dissolved in the liquid product returns to a certain level or greater, to control the amount of dissolved gas in the liquid product.

[0006] Patent Document 4 discloses that dibutylhydroxytoluene, butylhydroxyanisole, tert-butylhydroquinone, or propyl gallate can be added as an oxidizing agent to an oil-based agrochemical suspension, and Patent Document 5 discloses that dibutylhydroxytoluene, butylhydroxyanisole, or epichlorohydrin can be added as a stabilizer. However, Patent Document 4 and Patent Document 5 do not disclose a resin container filled with an oil-based agrochemical suspension.PRIOR ART DOCUMENTS

[0007] Patent Document 1: JP-A-2005-82595Patent Document 2: JP-A-2002-97103Patent Document 3: JP-A-2017-114506Patent Document 4: CN 101785455Patent Document 5: CN 107439578. DISCLOSURE OF INVENTIONTECHNICAL PROBLEM

[0008] The oil-based agrochemical suspension is, as described above, a product that is widely used along with other liquid agrochemical products, and if a container made of resin is used as a container in which the oil-based agrochemical suspension is to be placed, the container may be deformed or destroyed during storage or transportation, and preventing this is a problem that needs to be solved. SOLUTION TO THE PROBLEM

[0009] The inventor of the present invention has conducted extensive research to solve the above problem and, as a result, focused on the fact that the oil component in an oil-based agrochemical suspension is oxidized in air under the influence of oxygen, humidity, heat, light, metal ions, microorganisms, etc., and that the oxidation is accelerated, in particular, by exposure to light and heat. He arrived at the following conclusion: Depending on the storage conditions of a resin container filled with an oil-based agrochemical suspension, the oxygen contained in the space within the container interacts with the oil component and is consumed, resulting in a decrease in the pressure inside the container, leading to deformation or destruction of the container.To address these challenges, he focused on the use of a specific antioxidant and discovered that a more chemically stable oil-based suspension can be produced by suppressing the oxidation of the oil component in an agrochemical oil-based suspension, and that deformation of a resin container can be prevented when filling the container with the oil-based suspension. The present invention was completed based on this finding. ADVANTAGEOUS EFFECTS OF THE INVENTION.

[0010] The present invention relates to a method for preventing deformation of a resin-made agrochemical container filled with an oil-based agrochemical suspension. DESCRIPTION OF EMBODIMENTS

[0011] The present invention relates to a method for preventing deformation of a resin-made agrochemical container filled with an oil-based agrochemical suspension, wherein the oil-based agrochemical suspension filled into the resin-made agrochemical container contains (1) an agrochemically active ingredient, (2) an oil component, and (3) at least one antioxidant selected from the group consisting of a phenol derivative, a gallic acid ester, and ethoxyquin.

[0012] The present invention also relates to an oil-based agrochemical suspension for preventing deformation of an agrochemical container made of resin, comprising (1) an agrochemically active ingredient, (2) an oil component and (3) at least one antioxidant selected from the group consisting of a phenol derivative, a gallic acid ester and ethoxyquin, and which suppresses oxidation of the oil component that occurs in an agrochemical container made of resin filled with the oil-based agrochemical suspension.

[0013] In the present invention, the deformation of the resin agrochemical container means irreparable flattening, compression, deformation, distortion, cracking, etc. compared with the shape of the container when the oil-based agrochemical slurry is poured.

[0014] The agrochemically active ingredient provided in the present invention is not particularly limited as long as it can be incorporated into an oil-based suspension, and may be, for example, nicosulfuron, flazasulfuron, tolpiralate, thiafenacil, mesotrione, atrazine, bromoxynil, terbuthylazine, acetochlor, metolachlor, chlorfluazuron, fosthiazate, flonicamid, cyclaniliprol, isofetamide, cyazofamid, pyriofenone or fluazinam. Of these, nicosulfuron, flazasulfuron, tolpiralate, flonicamid, isofetamide, cyazofamid, pyriofenone and fluazinam are preferred, and nicosulfuron and tolpiralate are more preferred.

[0015] The oil component proposed in the present invention is not particularly limited if it contains an unsaturated hydrocarbon as a moiety for reacting with oxygen in an agrochemical container made of a resin after the oil-based agrochemical suspension is poured into the container, and it may be, for example, a vegetable oil, an alkyl ester of a vegetable oil, a mineral oil or an aromatic oil, or a mixture thereof.

[0016] The vegetable oil or vegetable oil alkyl ester may be, for example, soybean oil, rapeseed oil, tall oil, olive oil, castor oil, papaya oil, camellia oil, coconut oil, palm oil, sesame oil, corn oil, rice bran oil, peanut oil, cottonseed oil, linseed oil, sunflower oil, neem oil or safflower oil, or an alkyl ester thereof, and preferably rapeseed oil, corn oil or soybean oil, or a methyl ester thereof. In addition, a fatty acid glyceride can be used as the oil component. The fatty acid glyceride can be obtained from, for example, vegetable oil. The amount of fatty acid substituents may vary and may include monoglyceride, diglyceride or triglyceride.The diglyceride or triglyceride may be substituted with the same or different fatty acids at any position, and if substituted with different fatty acids, they may be an unsaturated fatty acid or a saturated fatty acid. Two or more types of fatty acid glycerides may be used in combination. The fatty acid may be, for example, 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, or ricinoleic acid, and preferably linoleic acid, oleic acid, palmitic acid, stearic acid, or erucic acid.In addition, a fatty acid glyceride alkyl ester containing a fatty acid alkyl ester moiety is preferable, and a methylated fatty acid glyceride is particularly preferable.

[0017] The mineral oil may be machine oil, paraffin oil, or naphthenic oil, and is preferably paraffin oil. The mineral oil may contain a saturated hydrocarbon, but may also include an unsaturated hydrocarbon, and such mineral oil is within the scope of the present invention.

[0018] The aromatic oil may be solvent naphtha or xylene, and is preferably solvent naphtha.

[0019] The antioxidant provided in the present invention may be, for example, a phenol derivative, a gallic acid ester, or ethoxyquin.

[0020] An antioxidant that has a desired effect when added to a product is preferably dissolved in the product, and since the oil-based agrochemical suspension proposed in the present invention is an oil-based agrochemical product, a lipophilic antioxidant is particularly preferable.

[0021] The phenol derivative may be, for example, 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) or bis(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfide, and preferably dibutylhydroxytoluene.

[0022] The gallic acid ester may be, for example, methyl gallate, ethyl gallate, 2-hydroxyethyl gallate, propyl gallate, isopropyl gallate or butyl gallate, and is preferably propyl gallate.

[0023] Dibutylhydroxytoluene is a particularly preferred antioxidant.

[0024] The antioxidant provided in the present invention has a desirable effect even when added in a very small amount, and to suppress the deformation of an agrochemical container made of resin for a long period of time, the mass ratio of the antioxidant to the mass of the oil component is generally from 0.0001:99.9999 to 30:70, preferably from 0.001:99.999 to 20:80, more preferably from 0.01:99.99 to 15:85.

[0025] In the present invention, the agrochemical container made of resin in which the oil-based agrochemical suspension is to be placed is not particularly limited, and it is preferably an agrochemical container made of resin industrially obtained by direct blow molding or stretch blow molding from a material 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 or perfluoroalkoxyfluoride resin. There are no special restrictions on the capacity and it may be, for example, 100 ml, 500 ml, 1 l, 5 l, 10 l, 20 l, 200 l or 1000 l, and preferably 500 ml, 1 l or 5 l.

[0026] The mixing ratio of the agrochemical active ingredient, the oil component and the antioxidant in the oil-based agrochemical suspension according to the present invention cannot usually be determined because it varies depending on the types of ingredients, characteristics, etc., and may be, for example, as follows. The content of the agrochemical active ingredient is from 0.1 to 80 parts by weight, preferably from 0.5 to 50 parts by weight, more preferably from 2 to 35 parts by weight. The content of the oil component is from 1 to 99 parts by weight, preferably from 5 to 95 parts by weight, more preferably from 15 to 75 parts by weight. The content of the antioxidant is from 0.001 to 10 parts by weight, preferably from 0.01 to 10 parts by weight, more preferably from 0.1 to 3 parts by weight.

[0027] The oil-based agrochemical suspension provided in the present invention may contain a composition auxiliary such as a surfactant, an antifreeze agent, an anti-settling agent, a foam suppressant, or a solvent according to the requirements of the specific case.

[0028] The surfactant may be, for example, an anionic surfactant such as fatty acid salt, benzoate, alkyl sulfosuccinate, dialkyl sulfosuccinate, alkyl sulfuric acid ester salt, alkyl sulfate, alkyl ether sulfate of diglycol, alcohol ether salt of sulfuric acid, alkyl sulfonate, alkyl aryl sulfonate, alkyl diphenyl ether disulfonate, polystyrene sulfonate, alkyl phosphoric acid ester salt, alkyl aryl phosphate, styryl aryl phosphate, polyoxyethylene alkyl ether sulfuric acid salt, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene styryl aryl ether sulfate, polyoxyethylene styryl aryl ether sulfuric acid ammonium salt, polyoxyethylene alkyl aryl ether sulfuric acid salt, polyoxyethylene alkyl ether phosphate, salt polyoxyethylene alkyl aryl ether phosphoric acid, polyoxyethylene styryl aryl ether phosphate or a salt thereof;a nonionic surfactant such as sorbitan fatty acid ester, glycerol fatty acid ester, polyglyceride fatty acid, polyglycol alcohol fatty acid ester, acetylene glycol, acetylene alcohol, oxyalkylene block polymer, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene styryl aryl ether, polyoxyethylene polyoxyethylene allyl phenyl ether, polyoxyethylene glycol alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene glycerol fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyethylene castor oil, polyoxypropylene fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene alkyl ether phosphate or polyoxyethylene methylpolysiloxane; or a cationic surfactant such as an alkoxylated fatty acid amine;and two or more of them can be used as a mixture according to the requirements of a particular case. The content of the surfactant is from 0 to 80 parts by weight, preferably from 5 to 70 parts by weight;

[0029] The antifreeze agent is preferably a dihydric alcohol, in particular an alkylene glycol such as ethylene glycol or propylene glycol, and preferably propylene glycol. In addition to its antifreeze effect, the dihydric alcohol also acts as a viscosity-lowering agent and reduces the viscosity of the oil-based agrochemical suspension and, in some cases, improves fluidity. The antifreeze agent content is generally 2 to 30 parts by weight, preferably 5 to 10 parts by weight.

[0030] The anti-settling agent may be, for example, a natural polysaccharide such as xanthan gum, ramsan gum, locust bean gum, carrageenan or wellan gum; a synthetic polymer such as sodium polyacrylate; a semi-synthetic polysaccharide such as carboxymethyl cellulose; a fine mineral powder such as magnesium aluminum silicate, smectite, bentonite, hectorite, fumed silica, organic bentonite or organic hectorite, or alumina sol, and two or more of them can be used as a mixture according to the requirements of the specific occasion. The content of the anti-settling agent is usually from 0.01 to 10.0 parts by weight, preferably from 0.1 to 5.0 parts by weight.

[0031] The foam suppressant may be, for example, a silicone foam suppressant containing polydimethylsiloxane as an active ingredient, or silicon dioxide. Specifically, for example, commercially available products under the trade names SILCOLAPSE 432 (manufactured by Bluestar silicones), SILFOAM SC 120 (manufactured by Wacker Asahikasei Silicone Co., Ltd.) and SAG 47, SAG 1538, SAG 1572 (manufactured by Momentive) can be mentioned, and they can be used in the form of a mixture with silicon dioxide according to the requirements of the specific case. The content of the foam suppressant is usually 0.01 to 10 parts by weight, preferably 0.1 to 2.0 parts by weight.

[0032] The solvent may be, for example, 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 or alkylnaphthalene, and two or more of them can be used as a mixture according to the requirements of the specific occasion. The content of the solvent is usually 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight.

[0033] The oil-based agrochemical suspension according to the present invention can be produced by a conventional technique in the art, and for example, mention may be made of a technique in which a surfactant and an anti-settling agent or a stabilizer are added to an oil component and mixed, and then an agrochemically active ingredient is added and another auxiliary substance is added according to the requirements of the specific case, the mixture is preliminarily ground, for example, with a homogenizer, and wet ground to obtain particles of a predetermined size with a fine mill, for example, using zircon balls, and an additive such as a thickener is added, then mixed, and a technique in which an agrochemically active ingredient, dry ground together with an additive such as a surfactant, is added to an oil component in which the surfactant is dissolved,An anti-settling agent and other excipients are then pre-milled, for example, using a homogenizer, and wet-milled to a desired particle size using a fine grinding mill, for example, using glass beads. An excipient such as a thickener or stabilizer is added according to the specific requirements of the application, and then mixed. The agrochemically active ingredient is typically milled to obtain a particle size of 0.1 to 5 μm, and the particle size is preferably varied depending on the physical characteristics of the agrochemically active ingredient.

[0034] As a fine mill that can be used to produce the oil-based agrochemical suspension proposed in the present invention, mention may be made of a wet fine mill such as a ball mill, a vibration mill or a planetary mill, and, for example, Paint Shaker (manufactured by Toyo Seiki Seisaku-sho, Ltd.), Nanotaro (Nano Pulverizer) NP-100 (manufactured by THINKY CORPORATION), DYNO-MILL KD (manufactured by WAB), Ready Mill Model RMH (manufactured by AIMEX CO., LTD.) and the like can be used. The balls may be, for example, glass balls, zirconium oxide balls, zircon balls and the like. The balls are preferably those that can produce particles with a size in the range of 0.01 to 1.5 mm, more preferably from 0.5 to 1.0 mm.By using balls that produce small particle sizes, it is possible to obtain an oil-based agrochemical suspension with small to medium sized particles.

[0035] The average particle size of an agrochemically active ingredient can be measured, for example, using a laser diffraction particle size distribution device 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 using a sample dispersed in an organic solvent such as n-hexane.

[0036] The viscosity of the oil-based agrochemical suspension proposed in the present invention can be measured, for example, using a TVB-10 viscometer (manufactured by Toki Sangyo Co., Ltd.) or a BrookField viscometer (manufactured by BrookField). When using the TVB-10 viscometer, the measurement can be performed on a liquid sample at a temperature of 20°C, at a speed of 60 rpm, using an M2 or M3 rotor.

[0037] In the present invention, after an oil-based agrochemical suspension is poured into an agrochemical container made of resin, the air in the container can be replaced with nitrogen by supplying nitrogen to the container from a device such as a nitrogen cylinder (manufactured by NaRiKa Corporation). The nitrogen container can be sealed using a device such as a sealing gasket (model DGF-500, manufactured by LANDS WORK Corporation).

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

[0039]

[0001] A method for preventing deformation of a resin-made agrochemical container filled with an oil-based agrochemical suspension, wherein the oil-based agrochemical suspension filled into the resin-made agrochemical container contains (1) an agrochemically active ingredient, (2) an oil component, and (3) at least one antioxidant selected from the group consisting of a phenol derivative, a gallic acid ester, and ethoxyquin.

[0002] The method according to paragraph [1], wherein the antioxidant is at least one element selected from the group consisting of a phenol derivative and a gallic acid ester.

[0003] The method according to paragraph [1] or [2], wherein the phenol derivative is at least one member 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.

[0004] The method according to paragraph [1] or [2], wherein the gallic acid ester is at least one member selected from the group consisting of methyl gallate, ethyl gallate, 2-hydroxyethyl gallate, propyl gallate, isopropyl gallate, and butyl gallate.

[0005] The method according to any one of paragraphs [1] to [4], wherein the oil component is at least one member selected from the group consisting of a vegetable oil, an alkyl ester of a vegetable oil, a mineral oil, and an aromatic oil.

[0006] The method according to paragraph [5], wherein the vegetable oil or alkyl ester of vegetable oil is at least one member 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 bran oil, peanut oil, cottonseed oil, linseed oil, sunflower oil, neem oil and safflower oil, and an alkyl ester thereof.

[0007] The method according to paragraph [5], wherein the mineral oil is at least one member selected from the group consisting of machine oil, paraffin oil, and naphthenic oil.

[0008] The method according to paragraph [5], wherein the aromatic oil is at least one element selected from the group consisting of the following: a naphtha solvent and xylene.

[0009] The method according to any one of paragraphs [1] to [4], wherein the oil component is a fatty acid glyceride.

[0010] The method according to paragraph [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.

[0011] The method according to paragraph [9] or

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

[0012] The method according to any one of paragraphs [1] to

[11] , wherein the ratio of the mass of the antioxidant to the mass of the oil component is from 0.01:99.99 to 15:85.

[0013] The method according to any one of paragraphs [1] to

[12] , wherein after the oil-based agrochemical suspension is poured into the agrochemical container made of resin, the gas in the container is replaced with nitrogen.

[0014] The method according to any one of paragraphs [1] to

[13] , wherein the agrochemically active ingredient is nicosulfuron, flazasulfuron, tolpyralate, thiafenacil, mesotrione, atrazine, bromoxynil, terbuthylazine, acetochlor, metolachlor, chlorfluazuron, fosthiazate, flonicamid, cyclaniliprol, isofetamide, cyazofamid, pyriophenone or fluazinam.

[0015] The method according to any one of paragraphs [1] to

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

[0016] An oil-based agrochemical suspension for preventing deformation of a resin-made agrochemical container as defined in any one of paragraphs [1] to

[15] .

[0017] A method for preventing deformation of an agrochemical container made of resin, which comprises obtaining an oil-based agrochemical suspension by mixing (1) an agrochemical active ingredient, (2) an oil component and (3) at least one antioxidant selected from the group consisting of a phenol derivative, a gallic acid ester and ethoxyquin, and pouring the oil-based agrochemical suspension into the agrochemical container made of resin, to suppress a decrease in pressure in the agrochemical container made of resin caused by oxygen consumption in the agrochemical container made of resin filled with the oil-based agrochemical suspension.

[0018] The method according to paragraph

[17] , wherein the antioxidant is at least one element selected from the group consisting of a phenol derivative and a gallic acid ester.EXAMPLES

[0040] The present invention is described in detail below with reference to examples, but it should be understood that the present invention is not limited thereto. First, production examples are described.

[0041] Examples of preparationThe components in the quantities indicated in the following Table A are mixed and ground using an ULTRA-TURRAX T25basic homogenizer (manufactured by IKA) to obtain an oil-based suspension. The numerical values ​​​​are given in Table A in parts by weight. The surfactants (c1) to (c7) listed as component (c) in Table A are described in Table B, and the commercially available products listed in Table A are as follows. "SAG47", a trade name, a silicone foam suppressant (manufactured by Momentive); "Agnique ME 18RD-F", a trade name, a methyl ester of C16-18 saturated fatty acid and C18 unsaturated fatty acid (manufactured by BASF); "Corn Salad Oil", a trade name, triacylglycerol (manufactured by Boso oil and fat Co., Ltd.).

[0042] Table A Component Examples of receipt 1 2 3 4 (a) Tolpiralat 12,0 3,0 - 10,0 (b) Nicosulfuron 12,0 3,0 6,0 - (c) (c)-1 10,5 12,0 10,0 3,0 (c) (c)-2 1,2 - 1,0 - (c) (c)-3 - 5,0 - - (c) (c)-4 - - 15,0 - (c) (c)-5 3,0 - - 10,0 (c) (c)-6 3,3 - 2,0 - (c) (c)-7 1,0 - 2,0 (d) Finely dispersed silicon dioxide 3,0 - - - (e) Organic bentonite 1,5 1,0 1,0 1,0 (f) SAG47 - 0,5 - - (g) 2-ethylhexanol - - 7,2 - (h) Agnique ME 18RD-F 54,7 - 65,4 72,0 (h) Corn Salad Oil - 70,5 - -

[0043] Table A (continued) Component Examples of receipt Comparative example 5 6 7 1 (a)-2 Flonicamid 24,0 - - - (a)-3 Atrazine - 24,0 - - (a)-4 Bromoxynil - - 24,0 - (a)-5 Glyphosate - - - 24,0 (c) (c)-1 - - - - (c) (c)-2 1,2 1,2 1,2 1,2 (c) (c)-3 - - - - (c) (c)-4 - - - - (c) (c)-5 3,0 3,0 3,0 3,0 (c) (c)-6 3,3 3,3 3,3 3,3 (c) (c)-7 - - - - (d) Finely dispersed silicon dioxide 3,0 3,0 3,0 3,0 (e) Organic bentonite 1,5 1,5 1,5 1,5 (f) SAG47 - - - - (g) 2-Ethylhexanol - - - - (h) Agnique ME 18RD-F 54,7 54,7 54,7 54,7 (h) Corn Salad Oil - - - -

[0044] Table B Component (c)-1 Polyoxyethylene sorbitan fatty acid ester (c)-2 Polyoxyethylene - castor oil (c)-3 Polyoxyethylene allylphenyl ether (c)-4 Polyoxyethylenealkylamine (c)-5 Polyoxyethylene alkyl ether (c)-6 Calcium alkylbenzenesulfonate (c)-7 Sodium alkylbenzenesulfonate

[0045] The following are the research examples. Research Example 1 Oil-based suspensions containing an agrochemically active ingredient and oil-based suspensions not containing an agrochemically active ingredient were prepared as follows. [Containing an agrochemically active ingredient] An agrochemically active ingredient (tolpyralate: 12.0 parts by weight, nicosulfuron: 12.0 parts by weight), 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 calcium alkyl benzene sulfonate, 1.5 parts by weight of organic bentonite, 3.0 parts by weight of polyoxyethylene monoalkyl ether and 3.0 parts by weight of finely divided silica were mixed and 54.7 parts by weight Agnique ME18RD-F (trade name; methyl ester of C16-18 saturated fatty acid and C18 unsaturated fatty acid, manufactured by BASF) was added to a volume of 1 L.The mixture was mixed and ground using an ULTRA-TURRAX T25basic homogenizer (manufactured by IKA) and further ground using a ball mill to obtain particles of the agrochemically active ingredient of 5 μm or less in size, and an oil-based suspension was obtained.

[0046] [Not containing agrochemically active ingredient] 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 calcium alkylbenzenesulfonate and 79.2 parts by weight of Agnique ME18RD-F (trade name; methyl ester of C16-18 saturated fatty acid and C18 unsaturated fatty acid, manufactured by BASF) were mixed to make the volume of 1 L, and the mixture was stirred and ground with an ULTRA-TURRAX T25 basic homogenizer (manufactured by IKA) to obtain an oil-based suspension.

[0047] An antioxidant (dibutylhydroxytoluene or ascorbic acid) listed in Table 1 was added to each oil-based suspension and mixed to obtain a test sample, and 200 mL of each was placed in a 500 mL polyethylene bottle container (model: NSW-500-2(M) bottle, manufactured by TOHTO MOLDING CO., LTD). Before sealing the bottle container with a closure gasket, an oxygen concentration sensor was placed in the bottle container, and for some samples, the gas in the bottle container was replaced with nitrogen (laboratory gas cylinder (manufactured by NaRiKa Corporation)). Each bottle container was sealed with a closure gasket (model: DGF-500, manufactured by LANDS WORK corporation) and stored at room temperature for 863 days. After storage, the bottle container's appearance was examined according to the standards specified below, and the oxygen concentration in the bottle container was measured. The results are presented in Table 1.Appearance of the bottle container *: no change or very little change is observed, ×: a large dent is observed on the body.

[0048] Table 1 Agrochemically active ingredient Antioxidant Added quantity (mass fraction) Appearance Oxygen concentration after storage for 863 days Contains Dibutylhydroxytoluene (BHT) 0,2 * 15,4% BHT+nitrogen for replacement 0,02 * 0,7% Ascorbic acid 0,02 × 0,8% Absent Dibutylhydroxytoluene (BHT) 0,2 * 13,2% 0,02 × 1,5% Contains Didn't add - × 1,2%

[0049] Based on the results obtained in Study Example 1, it was found that, during long-term storage, the addition of 0.2 parts by weight of the antioxidant proposed in the present invention suppressed the deformation of the bottle container. Bottle container deformation was also suppressed by replacing the air in the bottle container with nitrogen, in addition to the addition of 0.02 parts by weight of the antioxidant. Furthermore, the oxygen concentration was slightly lower when the agrochemically active ingredient was present in the product.

[0050] Study Example 2: An oil-based suspension was prepared in the same manner as Study Example 1. The antioxidant listed in Table 2 was added in amounts ranging from 0.01 to 3.0 parts by weight, then stirred, the bottle container's appearance was examined, and the oxygen concentration in the bottle container was measured. The results are shown in Table 2.

[0051] Table 2 Agrochemically active ingredient Antioxidant Added quantity (mass fraction) Appearance Oxygen concentration after storage for 140 days Contains Dibutylhydroxytoluene (BHT) 3,0 * 14,7% 0,2 * 13,2% 0,1 * 13,9% 0,01 * 10,3% Ascorbic acid 3,0 * 7,2% 0,2 × 0,16% 0,1 × 0,23% 0,01 × 0,14% Propyl gallate 0,2 * 9,4% Ethoxyquin 0,2 * 12,0% Nitrogen for replacement ― * 0,19% Didn't add ― × 0,72% Absent Dibutylhydroxytoluene (BHT) 3,0 * 9,4% 0,2 * 7,7% 0,1 * 5,2% 0,01 × ― Ascorbic acid 3,0 × 0,29% 0,2 × 0,28% 0,1 × 0,23% 0,01 × ― Nitrogen for replacement ― * 0,25% Didn't add ― × 0,77%

[0052] Based on the results obtained in Test Example 2, it was found that, upon long-term storage (140 days), with the addition of 0.01 to 3.0 parts by weight of dibutylhydroxytoluene, 0.2 parts by weight of propyl gallate, or 0.2 parts by weight of ethoxyquin as the antioxidant proposed in the present invention, the deformation of the bottle container was suppressed, and the lipophilic antioxidant had a greater suppressive effect than a hydrophilic antioxidant such as ascorbic acid. The deformation of the bottle container was also suppressed by replacing the air in the bottle container with nitrogen. In addition, when the product contained an agrochemically active ingredient, the oxygen concentration was higher, and a more significant effect on suppressing the deformation of the bottle container was observed.

[0053] Study Example 2: 370g of the oil-based suspension obtained in Study Example 2 was weighed into a 100ml glass bottle and placed in an aluminum-laminated bag (manufactured by YANAGI, Model No. 0401, 12×22cm), the amount of air in the bag was adjusted so that the volume of the aluminum-laminated bag was 400 to 430ml, and the bag was sealed with a heat sealer (manufactured by FUJIIMPULSE CO., LTD. Model No. PS-310E) and stored at room temperature for 130 days. The change in volume of the aluminum-laminated bag was determined by measuring the volume of water after placing the aluminum-laminated bag in a 2L graduated cylinder into which 1.5L of water was added. The results are shown in Table 3.

[0054] Table 3 Agrochemically active ingredient Antioxidant Added quantity (mass fraction) Decrease (ml) Contains Dibutylhydroxytoluene (BHT) 3,0 0 0,2 5 0,1 5 0,01 10 Ascorbic acid 3,0 15 0,2 60 0,1 55 0,01 60 D-isoascorbic acid 3,0 10 0,2 70 0,1 50 DL-α-tocopherol 3,0 55 0,2 40 0,1 30 Propyl gallate 3,0 10 0,2 10 0,1 20 Ethoxyquin 3,0 5 0,2 5 0,1 5 Nitrogen for replacement ― 0 Didn't add ― 60 Absent Dibutylhydroxytoluene (BHT) 3,0 15 0,2 15 0,1 20 0,01 60 Ascorbic acid 3,0 60 0,2 60 0,1 55 0,01 55 Nitrogen for replacement ― -5 Didn't add ― 60

[0055] Based on the results obtained in Study Example 3, it was found that, during long-term storage (130 days at room temperature), the addition of 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 suppressed the deformation of the aluminum-laminated bag. On the other hand, when ascorbic acid or D-isoascorbic acid, which are hydrophilic antioxidants, or tocopherol were added, the deformation suppression effect of the container was weak. The deformation of the aluminum-laminated bag was also suppressed when the air in the bag was replaced with nitrogen. In addition, when the product contained an agrochemically active ingredient, the oxygen concentration was higher, and a more significant deformation suppression effect of the aluminum-laminated bag was observed.

[0056] Study Example 4 In the same manner as in Study Example 1, oil-based suspensions were prepared by using the agrochemically active ingredient listed in Table 4, adding 0.01 parts by weight to 0.2 parts by weight of dibutyl hydroxytoluene, then stirring, and the bottle container was stored at 40°C for 28 days. To study the condition of the bottle container, the outer diameter (the center part and the bottom part at a distance of 2 cm from the bottom) of the bottle container was measured, and the change in the outer diameter, the CV value, was calculated according to the following formula. The smaller the CV value, the smaller the deformation of the container and the more significant the deformation prevention effect. The results are shown in Table 4. CV value = (standard deviation of the container outer diameter / average value of the container outer diameter) × 100

[0057] Table 4 Agrochemically active ingredient Added amount of BHT (mass fraction) Outside diameter CV value Central part Bottom part Tolpyralate 120 g / l+Nicosulfuron 120 g / l 0,2 0,32 0,57 0,1 0,51 0,44 0,01 0,65 0,57 Didn't add 2,26 3,25 Flonicamid 240 g / l 0,2 0,39 0,17 0,1 0,31 0,30 0,01 0,73 2,78 Didn't add 1,16 3,09 Atrazine 240 g / l 0,2 0,33 0,45 0,1 0,27 0,30 0,01 3,18 5,42 Didn't add 4,04 5,83 Bromoxynil-240 g / l 0,2 0,20 0,22 0,1 0,62 0,49 0,01 1,24 1,84 Didn't add 1,38 3,10 Glyphosate 240 g / l 0,2 1,57 0,90 0,1 2,25 4,51 0,01 0,63 4,79 Didn't add 0,46 1,15 Absent 0,2 0,50 0,56 0,1 0,43 0,47 0,01 2,33 2,83 Didn't add 2,06 2,92

[0058] Based on the results obtained in Test Example 4, it was found that, when using products containing an agrochemically active ingredient other than glyphosate, the deformation of the bottle container was suppressed when dibutyl hydroxytoluene was added in an amount of 0.1 parts by weight or more per 100 ml of the sample. The entire disclosure of Japanese Patent Application No. 2021-131666, filed on August 12, 2021, including the description, claims, and abstract, is incorporated herein by reference in its entirety.

Claims

1. A method for preventing deformation of an agrochemical container made of resin, which is produced industrially from a material selected from low-density polyethylene, high-density polyethylene, polyvinyl chloride, polypropylene, polyamide, polyethylene terephthalate, polyvinylidene chloride, nitrile resin, polycarbonate, polyacrylate, polymethylpentene, polyethylene vinyl alcohol resin or perfluoroalkoxyfluoride resin, and filled with an oil-based agrochemical suspension, comprising the step of pouring an oil-based agrochemical suspension into the agrochemical container made of resin, containing (1) from 0.5 to 50 parts by weight of at least one component selected from the group consisting of nicosulfuron, flazasulfuron, tolpiralate, thiafenacil, mesotrione, atrazine, bromoxynil, terbuthylazine, acetochlor, metolachlor, chlorfluazuron, fosthiazate, flonicamid, cyclaniliprol, isofetamide, cyazofamid, pyriophenone or fluazinam, (2) from 5 to 95 parts by weight of an oil component which is a lipophilic antioxidant containing an unsaturated hydrocarbon, and (3) from 0.001 to 10 parts by weight of at least one antioxidant selected from the group consisting of a phenol derivative, a gallic acid ester, and ethoxyquin, wherein the phenol derivative is at least one member 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, where the ratio of the mass of the antioxidant to the mass of the oil component is from 0.01:99.99 to 15:

85.

2. The method according to paragraph 1, which includes: obtaining an oil-based agrochemical suspension by mixing (1) at least one component selected from the group consisting of nicosulfuron, flazasulfuron, tolpyralate, thiafenacil, mesotrione, atrazine, bromoxynil, terbuthylazine, acetochlor, metolachlor, chlorfluazuron, fosthiazate, flonicamid, cyclaniliprol, isofetamide, cyazofamid, pyriophenone or fluazinam, (2) an oil component which is a lipophilic antioxidant containing an unsaturated hydrocarbon and (3) at least one antioxidant selected from the group consisting of a phenol derivative, a gallic acid ester and ethoxyquin, wherein the weight ratio of the antioxidant to the weight of the oil component is from 0.01:99.99 to 15:85; pouring said oil-based agrochemical suspension into a resin-made agrochemical container to suppress a decrease in pressure in the resin-made agrochemical container caused by oxygen consumption in the resin-made agrochemical container filled with the oil-based agrochemical suspension.

3. The method according to claim 1 or 2, wherein the antioxidant is at least one element selected from the group consisting of the following: a phenol derivative and a gallic acid ester.

4. The method according to paragraphs 1-3, wherein the antioxidant is a phenol derivative.

5. The method according to any one of claims 1 to 4, wherein the oil component is at least one element selected from the group consisting of: vegetable oil, vegetable oil alkyl ester, mineral oil, and aromatic oil.

6. The method according to any one of claims 1-5, wherein the oil component is a fatty acid glyceride.

7. The method of claim 6, wherein the fatty acid glyceride is a glyceride of at least one fatty acid selected from the group consisting of: alpha-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.

8. The method according to claim 6 or 7, wherein the fatty acid glyceride is a monoglyceride, diglyceride, triglyceride, or a mixture thereof.

9. The method according to any one of paragraphs 1-8, wherein after the agrochemical oil-based suspension is poured into the resin container, the gas in the container is replaced with nitrogen.

10. An agrochemical product consisting of an agrochemical container made of resin, obtained industrially from a material selected from low-density polyethylene, high-density polyethylene, polyvinyl chloride, polypropylene, polyamide, polyethylene terephthalate, polyvinylidene chloride, nitrile resin, polycarbonate, polyacrylate, polymethylpentene, polyethylene vinyl alcohol resin or perfluoroalkoxyfluoride resin, and an oil-based agrochemical suspension containing: from 0.5 to 50 parts by weight of at least one component selected from the group consisting of nicosulfuron, flazasulfuron, tolpiralate, thiafenacil, mesotrione, atrazine, bromoxynil, terbuthylazine, acetochlor, metolachlor, chlorfluazuron, fosthiazate, flonicamid, cyclaniliprol, isofetamide, cyazofamid, pyriophenone or fluazinam, from 5 to 95 parts by weight of an oil component, which is a lipophilic antioxidant containing an unsaturated hydrocarbon, and from 0.001 to 10 parts by weight of at least one antioxidant selected from the group consisting of the following: a phenol derivative, a gallic acid ester and ethoxyquin, wherein the phenol derivative is at least one element selected from the group consisting of the following: 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, wherein the ratio of the weight of the antioxidant to the weight of the oil component is from 0.01:99.99 to 15:85; and in which the oxidation of the oil component is suppressed, which occurs in an agrochemical container made of resin filled with an oil-based agrochemical suspension.

11. An agrochemical product according to claim 10, wherein the antioxidant is at least one element selected from the group consisting of the following: a phenol derivative and a gallic acid ester.