WO2023017809A1 - 樹脂製農薬容器の変形防止方法 - Google Patents
樹脂製農薬容器の変形防止方法 Download PDFInfo
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- WO2023017809A1 WO2023017809A1 PCT/JP2022/030312 JP2022030312W WO2023017809A1 WO 2023017809 A1 WO2023017809 A1 WO 2023017809A1 JP 2022030312 W JP2022030312 W JP 2022030312W WO 2023017809 A1 WO2023017809 A1 WO 2023017809A1
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- agricultural chemical
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Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/34—Nitriles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
- A01N43/68—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms with two or three nitrogen atoms directly attached to ring carbon atoms
- A01N43/70—Diamino—1,3,5—triazines with only one oxygen, sulfur or halogen atom or only one cyano, thiocyano (—SCN), cyanato (—OCN) or azido (—N3) group directly attached to a ring carbon atom
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
- A01N47/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P13/00—Herbicides; Algicides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D77/00—Packages formed by enclosing articles or materials in preformed containers, e.g. boxes, cartons, sacks or bags
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
- B65D85/70—Containers, packaging elements or packages, specially adapted for particular articles or materials for materials not otherwise provided for
- B65D85/82—Containers, packaging elements or packages, specially adapted for particular articles or materials for materials not otherwise provided for for poisons
Definitions
- the present invention relates to a method for preventing deformation of a plastic agricultural chemical container filled with an agricultural chemical oil-based suspension agent and the agricultural chemical oil-based suspension agent used in the method.
- liquid pesticide formulations resin containers are commonly used due to their ease of processing, lightness, gas barrier properties, and not being easily broken like glass bottles.
- oil-based suspensions are formulations in which the active ingredient of an agrochemical is dispersed in an oily component. As a result, the addition of a spreading agent to the spray liquid becomes unnecessary, and it is often used among liquid pesticide formulations.
- Patent Document 1 describes a formaldehyde donor compound and a fungicidal composition containing an antioxidant selected from gallic acid esters, phenol derivatives, L-ascorbic acid and salts and derivatives thereof, and tocopherol and derivatives thereof. Use is described to reduce the problem of neck-in effects during storage and transportation of industrial products such as fuels and lubricants.
- Patent Document 1 does not describe a resin container filled with an agricultural chemical oil-based suspension agent.
- Patent Literature 2 describes a method for preventing deformation of a plastic container when a liquid drug is packed and stored in a plastic container by reducing the dissolved oxygen concentration of the liquid drug to 30 ppm or less.
- a method of blowing an inert gas such as nitrogen gas into the chemical liquid, a method of heating in an inert gas atmosphere, and a method of reducing the pressure and then returning to normal pressure with an inert gas are described.
- Patent Document 3 after preparing a liquid drug containing an organic solvent, deaeration treatment is performed, and the gas is redissolved in the liquid drug by standing still or stirring under normal pressure or under pressure, and the amount of gas in the liquid drug is A method for preventing deformation of the container by adjusting the amount of gas dissolved in the liquid medicine by returning the pressure to a certain level or higher is described.
- Patent Document 4 describes that dibutylhydroxytoluene, butylhydroxyanisole, t-butylhydroquinone, and propyl gallate can be added as antioxidants to the pesticide oil-based suspension. It is stated that toluene, butylhydroxyanisole and epichlorohydrin can be added. However, Patent Document 4 and Patent Document 5 do not describe a resin container filled with an agricultural chemical oil-based suspension agent.
- the pesticide oil-based suspension is a formulation form that is often used among liquid pesticide formulations. and damage may occur, and prevention of this is an issue.
- the present inventors have found that the oily component in the pesticide oily suspension is oxidized by the action of oxygen, moisture, heat, light, metal ions, microorganisms, etc. in the air.
- the oxygen present in the space inside the container may be separated from the oily component.
- the inventors have come to the idea that the reaction consumes oxygen, resulting in a decompressed state in the container, which may cause deformation or breakage of the container.
- the present invention is a method for preventing deformation of a resin agricultural chemical container filled with an agricultural chemical oil suspension, wherein the agricultural chemical oil suspension to be filled in the resin agricultural chemical container comprises (1) an agricultural chemical active ingredient, (2)
- the present invention relates to a method for preventing deformation of the plastic agricultural chemical container, which contains an oily component and (3) at least one antioxidant selected from the group consisting of phenol derivatives, gallic acid esters and ethoxyquin.
- the present invention also provides an agricultural chemical oil-based suspension containing (1) an agricultural chemical active ingredient, (2) an oily ingredient, and (3) at least one antioxidant selected from the group consisting of phenol derivatives, gallic acid esters and ethoxyquin.
- the present invention relates to an agricultural chemical oil-based suspension agent for preventing deformation of a resin-made agricultural chemical container, which suppresses oxidation of the oily component generated in the container after being filled in the resin-made agricultural chemical container.
- the deformation of a resin agricultural chemical container refers to a state in which the shape of the container is dented, shrunk, distorted, broken, cracked, etc. from the state at the time of filling with the agricultural chemical oil-based suspension agent, and cannot be restored.
- the active ingredient of agricultural chemicals in the present invention is not particularly limited as long as it can be prepared into an oily suspension.
- nicosulfuron, flazasulfuron, tolpiralate, flonicamid, isofetamide, cyazofamid, pyriophenone or fluazinam are preferred, and nicosulfuron or tolpiralate is more preferred.
- 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 pesticidal oily suspension is filled in the resin pesticide container.
- alkyl-esterified vegetable oils, mineral oils, and aromatic oils may be mixed and used.
- 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, and cottonseed oil. , linseed oil, sunflower oil, neem oil, safflower oil and their alkyl ester oils, of which rapeseed oil, corn oil, soybean oil and their methyl ester oils are preferred. Moreover, fatty acid glyceride can be used as an oil component. Fatty acid glycerides can be obtained, for example, from vegetable oils.
- the number of fatty acid substitutions is arbitrary, and examples include monoglyceride, diglyceride, and triglyceride.
- diglycerides or triglycerides the same or different fatty acids may be substituted at any position, and when different fatty acids are substituted, they may be unsaturated or saturated fatty acids.
- two or more types of fatty acid glycerides can be used in combination.
- fatty acids examples include ⁇ -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, and lignoserine. acid, erucic acid, ricinoleic acid, etc., among which linoleic acid, oleic acid, palmitic acid, stearic acid, and erucic acid are preferred. Also, alkyl-esterified fatty acid glycerides in which the fatty acid moiety is alkyl-esterified are preferred, and methylated fatty acid glycerides are particularly preferred.
- Mineral oils include machine oil, paraffin oil and naphthenic oil, among which paraffin oil is preferred.
- Mineral oil which mainly contains saturated hydrocarbons, may contain unsaturated hydrocarbons and is the subject of the present invention.
- Aromatic oils include solvent naphtha and xylene, among which solvent naphtha is preferred.
- antioxidants in the present invention include phenol derivatives, gallic acid esters and ethoxyquin.
- the desired effect can be obtained by adding the antioxidant to the formulation, but it is preferable that the antioxidant is dissolved in the formulation. For this reason, lipophilic antioxidants are particularly preferred.
- phenol derivatives 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), bis(5-tert-butyl-4-hydroxy-2-methylphenyl) sulfide, among which dibutylhydroxytoluene is preferred.
- gallic acid esters examples include methyl gallate, ethyl gallate, 2-hydroxyethyl gallate, propyl gallate, isopropyl gallate, and butyl gallate, with propyl gallate being preferred.
- Dibutylhydroxytoluene is particularly preferred as the antioxidant.
- the antioxidant in the present invention can achieve the desired effect even when added in a very small amount. .0001:99.9999 to 30:70, preferably 0.001:99.999 to 20:80, more preferably 0.01:99.99 to 15:85.
- the resin agricultural chemical container to be filled with an agricultural chemical oil-based suspension agent is not particularly limited, but examples include low density polyethylene, high density polyethylene, polyvinyl chloride, polypropylene, polyamide, polyethylene terephthalate, polyvinylidene chloride, and nitrile resin , polycarbonate, polyacrylate, polymethylpentene, polyethylene vinyl alcohol resin, perfluoroalkoxy fluororesin, etc., and is industrially produced by a direct blow molding method or a stretch blow molding method.
- the volume is not particularly limited, but includes, for example, 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.
- the blending ratio of the agricultural chemical active ingredient, the oil-based ingredient and the antioxidant in the agricultural chemical oil-based suspension of the present invention may be appropriately changed depending on the type and properties of each component, and cannot be defined unconditionally. Street.
- the agricultural chemical active ingredient is 0.1 to 80 parts by weight, preferably 0.5 to 50 parts by weight, more preferably 2 to 35 parts by weight.
- the oil component is 1 to 99 parts by weight, preferably 5 to 95 parts by weight, more preferably 15 to 75 parts by weight.
- the antioxidant is 0.001 to 10 parts by weight, preferably 0.01 to 10 parts by weight, more preferably 0.1 to 3 parts by weight.
- the pesticide oil-based suspension of the present invention can be appropriately added with formulation aids such as surfactants, antifreeze agents, anti-settling agents, antifoaming agents, and solvents, if necessary.
- surfactant examples include fatty acid salts, benzoates, alkyl sulfosuccinates, dialkyl sulfosuccinates, alkyl sulfates, alkyl sulfates, alkyl diglycol ether sulfates, alcohol sulfates, and alkyl sulfonates.
- alkyl aryl sulfonate alkyl diphenyl ether disulfonate, polystyrene sulfonate, alkyl phosphate, alkyl aryl phosphate, styrylaryl phosphate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl Ether sulfate, polyoxyethylene styryl aryl ether sulfate, polyoxyethylene styryl aryl ether ammonium sulfate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl aryl phosphate , anionic surfactants such as polyoxyethylene styryl aryl ether phosphate or salts thereof; sorbitan fatty acid ester, glycerin fatty acid ester, fatty acid polyglyceride, fatty acid alcohol polyglycol ether,
- a dihydric alcohol is preferred, and specific examples include alkylene glycols such as ethylene glycol and propylene glycol, among which propylene glycol is preferred.
- the dihydric alcohol also acts as a viscosity-reducing agent, and in addition to the antifreeze effect, it reduces the viscosity of the agricultural chemical oil-based suspension and may improve the fluidity.
- the amount of the antifreeze agent is usually 2 to 30 parts by weight, preferably 5 to 10 parts by weight.
- the anti-settling agent examples include natural polysaccharides such as xanthan gum, rhamsan gum, locust bean gum, carrageenan and welan gum; synthetic polymers such as sodium polyacrylate; semi-synthetic polysaccharides such as carboxymethyl cellulose; aluminum magnesium silicate; Mineral fine powders such as smectite, bentonite, hectorite, dry silica, organic bentonite, organic hectorite, etc., alumina sol, etc., may be mentioned, and if necessary, two or more of these may be used in combination.
- the blending ratio of the anti-settling agent is usually 0.01-10.0 parts by weight, preferably 0.1-5.0 parts by weight.
- Antifoaming agents include, for example, silicone-based antifoaming agents containing polydimethylsiloxane as an active ingredient, silica, and the like.
- silicone-based antifoaming agents containing polydimethylsiloxane as an active ingredient, silica, and the like.
- trade name SILCOLAPSE 432 manufactured by Bluestar Silicones
- trade name SILFOAM SC 120 manufactured by Asahi Kasei Wacker Silicone Co., Ltd.
- trade names SAG 47, SAG 1538, SAG 1572 manufactured by Momentive
- silica may be mixed.
- the blending ratio of the antifoaming agent is usually 0.01 to 10 parts by weight, preferably 0.1 to 2.0 parts by weight.
- solvents examples include water, dioxane, acetone, isophorone, methylisobutylketone, chlorobenzene, cyclohexane, dimethylsulfoxide, dimethylformamide, dimethylacetamide, dimethyl C8-C12amide, N-methyl-2-pyrrolidone, 2-ethylhexanol, ⁇ -butyrolactone, alcohol, acetic acid, butyric acid, lactic acid, isopropyl acetate, butyl acetate, dimethyl lactate, benzene, alkylbenzene, alkylnaphthalene, etc., and if necessary, two or more of these may be used in combination.
- the blending ratio of the solvent is usually 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight.
- the method for producing the pesticidal oil-based suspension of the present invention can be carried out according to the usual method in the relevant technical field. After mixing, the active ingredient of agricultural chemicals is added, and if necessary, other adjuvants are added, and after preliminary pulverization with a homogenizer or the like, using zircon beads or the like, finely pulverized to a predetermined particle size with a wet pulverizer, A method of adding and mixing auxiliary agents such as thickeners, and a method of dry pulverizing the active ingredients of agricultural chemicals with auxiliary agents such as surfactants and dissolving surfactants, anti-settling agents and other auxiliary agents.
- auxiliary agents such as thickeners
- auxiliary agents such as surfactants and dissolving surfactants, anti-settling agents and other auxiliary agents.
- the particle size of the active ingredient of agricultural chemicals is preferably pulverized to approximately 0.1 to 5 ⁇ m, and it is desirable to change the particle size according to the physical properties of the active ingredient of agricultural chemicals.
- Pulverizers that can be used for producing the pesticide oil-based suspension of the present invention include wet pulverizers such as bead mills, vibration mills, and planetary mills.
- NP-100 manufactured by THINKY Co.
- Dyno Mill KD type manufactured by WAB Co.
- Ready Mill RMH type manufactured by Imex Co.
- Usable beads include glass beads, zirconia beads, zircon beads and the like.
- the bead particle size to be used is preferably in the range of 0.01 to 1.5 mm, more preferably in the range of 0.5 to 1.0 mm. By using beads with a small particle size, an agrochemical oil suspension with a small average particle size can be produced.
- the average particle size of the pesticide active ingredient can be measured with a laser diffraction particle size distribution analyzer such as Microtrac MT3300-EXII (manufactured by Nikkiso Co., Ltd.) and Mastersizer 3000 (manufactured by Malvern).
- a laser diffraction particle size distribution analyzer such as Microtrac MT3300-EXII (manufactured by Nikkiso Co., Ltd.) and Mastersizer 3000 (manufactured by Malvern).
- the measurement can be performed by dispersing the sample in an organic solvent such as n-hexane.
- the viscosity of the pesticide oil-based suspension of the present invention can be measured, for example, with a TVB-10 viscometer (manufactured by Toki Sangyo Co., Ltd.) or a Brook Field viscometer (manufactured by Brook Field Co.).
- a TVB-10 type viscometer the measurement can be performed using a sample liquid temperature of 20° C., a rotation speed of 60 rpm, and a rotor M2 or M3.
- nitrogen gas is supplied to the space of the container from a device such as a cartridge type nitrogen cylinder (manufactured by Narika Co., Ltd.) to fill the space of the container. Part can be replaced with nitrogen.
- the nitrogen-purged container can be sealed with a device such as an induction liner (type DGF-500, manufactured by Landswork).
- a method for preventing deformation of a resin agricultural chemical container filled with an agricultural chemical oil-based suspension agent wherein the agricultural chemical oil-based suspension agent filled in the resin agricultural chemical container contains (1) an agricultural chemical active ingredient, (2) an oily and (3) at least one antioxidant selected from the group consisting of phenol derivatives, gallic acid esters and ethoxyquin.
- the antioxidant is at least one selected from the group consisting of phenol derivatives and gallic acid esters.
- the phenol derivative is 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 at least selected from the group consisting of bis(5-tert-butyl-4-hydroxy-2-methylphenyl) sulfide
- the gallate is at least one selected from the group consisting of methyl gallate, ethyl gallate, 2-hydroxyethyl gallate, propyl gallate, isopropyl gallate and butyl gallate; [1 ] or [2].
- the oily component is at least one selected from the group consisting of vegetable oils, alkyl-esterified vegetable oils, mineral oils and aromatic oils.
- the vegetable oil or alkyl-esterified vegetable oil is 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, The method according to [5], wherein the oil is selected from the group consisting of cottonseed oil, linseed oil, sunflower oil, neem oil, safflower oil and alkyl ester oils thereof.
- the mineral oil is at least one selected from the group consisting of machine oil, paraffin oil and naphthenic oil.
- the fatty acid glyceride is ⁇ -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, erucine
- the active ingredient of the agricultural chemical is nicosulfuron, flazasulfuron, tolpiralate, thiaphenacil, mesotrione, atrazine, bromoxynil, turbthylazine, acetochlor, metolachlor, chlorfluazuron, fosthiazate, flonicamid, cyclaniliprole, isofetamide , cyazofamid, pyriophenone or fluazinam [1] to [13].
- the agricultural chemical active ingredient is at least one selected from the group consisting of nicosulfuron and tolpiralate.
- a method for preventing deformation of a plastic agricultural chemical container comprising (1) an agricultural chemical active ingredient, (2) an oily ingredient, and (3) at least one selected from the group consisting of phenol derivatives, gallic acid esters and ethoxyquin
- a pesticide oil-based suspension is prepared by mixing a seed antioxidant, Then, the pesticide oil-based suspension is filled in a resin pesticide container, A method for suppressing decompression in a resin agricultural chemical container due to consumption of oxygen inside the resin agricultural chemical container after filling.
- the antioxidant is at least one selected from the group consisting of phenol derivatives and gallic acid esters.
- Test example 1 As described below, an oily suspension containing an agricultural chemical active ingredient and an oily suspension containing no agricultural chemical active ingredient were prepared. [Contains pesticide active ingredients] Agrochemical active ingredients (tolpiralate 12.0 parts by weight, nicosulfuron 12.0 parts by weight), polyoxyethylene sorbitan fatty acid ester 10.5 parts by weight, polyoxyethylene castor oil 1.2 parts by weight, calcium alkylbenzene sulfonate3.
- Test example 2 An oily suspension was prepared in the same manner as in Test Example 1, and after adding and mixing 0.01 to 3.0 parts by weight of the antioxidant shown in Table 2, the appearance of the bottle container and the oxygen concentration in the bottle container were measured. It was measured. The survey results are shown in Table 2.
- Test example 3 70 g of the oily suspension prepared in Test Example 2 was weighed into a 100 ml glass bottle, placed in an aluminum packaging container (manufactured by Yanagi Co., model number 0401, 12 x 22 cm), and the volume of the aluminum laminate was 400 to 430 ml. After adjusting the amount of air in the container, the container was sealed with a heat sealer (manufactured by Fuji Impulse Co., Model No. PS-310E) and stored at room temperature for 130 days. The change in 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 filled with 1.5 L of water in advance. The survey results are shown in Table 3.
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Abstract
Description
中でも、ニコスルフロン、フラザスルフロン、トルピラレート、フロニカミド、イソフェタミド、シアゾファミド、ピリオフェノンまたはフルアジナムが好ましく、ニコスルフロンまたはトルピラレートがより好ましい。
また、油性成分として、脂肪酸グリセライドを用いることができる。脂肪酸グリセライドは、例えば植物油から得ることが可能である。脂肪酸の置換数は任意であり、モノグリセライド、ジグリセライド又はトリグリセライドが挙げられる。ジグリセライド又はトリグリセライドである場合、同一又は異なる脂肪酸が、任意の位置に置換したものであってよく、異なる脂肪酸が置換する場合、それらは不飽和脂肪酸と飽和脂肪酸のいずれでもよい。また、2種類以上の脂肪酸グリセライドを混用することもできる。
前記脂肪酸としては、α-リノレン酸、リノール酸、オレイン酸、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、パルミトレイン酸、ステアリン酸、アラキジン酸、エイコセン酸、ベヘン酸、エルシン酸、リグノセリン酸、エルカ酸、リシノール酸などが挙げられ、中でもリノール酸、オレイン酸、パルミチン酸、ステアリン酸、エルカ酸が好ましい。また、脂肪酸部分がアルキルエステル化されたアルキルエステル化脂肪酸グリセライドが好ましく、メチル化脂肪酸グリセライドが特に好ましい。
農薬有効成分は、0.1~80重量部であり、好ましくは0.5~50重量部であり、さらに好ましくは2~35重量部である。
油性成分は、1~99重量部であり、好ましくは5~95重量部であり、より好ましくは15~75重量部である。
酸化防止剤は、0.001~10重量部であり、好ましくは0.01~10重量部であり、より好ましくは0.1~3重量部である。
〔2〕前記酸化防止剤が、フェノール誘導体及び没食子酸エステルからなる群から選択される少なくとも1種である、〔1〕に記載の方法。
〔3〕前記フェノール誘導体が、ジブチルヒドロキシトルエン、ブチルヒドロキシアニソール、2,5-ジ-tert-アミルヒドロキノン、2,5-ジ-tert-ブチルヒドロキノン、4,4’-ブチリデンビス(6-tert-ブチル-m-クレゾール)、4,4’-チオビス(6-tert-ブチル-m-クレゾール)及びビス(5-tert-ブチル-4-ヒドロキシ-2-メチルフェニル)スルフィドからなる群から選択される少なくとも1種である、〔1〕又は〔2〕に記載の方法。
〔4〕前記没食子酸エステルが、没食子酸メチル、没食子酸エチル、没食子酸2-ヒドロキシエチル、没食子酸プロピル、没食子酸イソプロピル及び没食子酸ブチルからなる群から選択される少なくとも1種である、〔1〕又は〔2〕に記載の方法。
〔5〕前記油性成分が、植物油、アルキルエステル化された植物油、鉱物油及び芳香族油からなる群から選択される少なくとも1種である、〔1〕~〔4〕に記載の方法。
〔6〕前記植物油又はアルキルエステル化された植物油が、ダイズ油、ナタネ油、トール油、オリーブ油、ヒマシ油、パパイヤ油、椿油、ヤシ油、パーム油、ゴマ油、トウモロコシ油、米油、ピーナッツ油、棉実油、アマニ油、ヒマワリ油、ニーム油、紅花油及びそれらのアルキルエステル油からなる群から選択される、〔5〕に記載の方法。
〔7〕前記鉱物油が、マシン油、パラフィンオイル及びナフテンオイルからなる群から選択される少なくとも1種である、〔5〕に記載の方法。
〔8〕前記芳香族油が、ソルベントナフサ及びキシレンからなる群から選択される少なくとも1種である、〔5〕に記載の方法。
〔9〕前記油性成分が、脂肪酸グリセライドである、〔1〕~〔4〕に記載の方法。
〔10〕前記脂肪酸グリセライドが、α-リノレン酸、リノール酸、オレイン酸、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、パルミトレイン酸、ステアリン酸、アラキジン酸、エイコセン酸、ベヘン酸、エルシン酸、リグノセリン酸、エルカ酸及びリシノール酸からなる群から選択される少なくとも1種の脂肪酸のグリセライドである、〔9〕に記載の方法。
〔11〕前記脂肪酸グリセライドが、モノグリセライド、ジグリセライド、トリグリセライド又はそれらの混合物である、〔9〕又は〔10〕に記載の方法。
〔12〕前記酸化防止剤と前記油性成分との重量比が0.01:99.99~15:85である、〔1〕~〔11〕に記載の方法。
〔13〕前記農薬油性懸濁剤を樹脂製農薬容器に充填した後、さらに、容器内の空間部のガスを窒素ガスへ置換する、〔1〕~〔12〕に記載の方法。
〔14〕前記農薬有効成分が、ニコスルフロン、フラザスルフロン、トルピラレート、チアフェナシル、メソトリオン、アトラジン、ブロモキシニル、ターブチラジン、アセトクロール、メトラクロール、クロルフルアズロン、ホスチアゼート、フロニカミド、シクラニリプロール、イソフェタミド、シアゾファミド、ピリオフェノン又はフルアジナムである〔1〕~〔13〕に記載の方法。
〔15〕前記農薬有効成分が、ニコスルフロン及びトルピラレートからなる群から選択される少なくとも1種である〔1〕~〔13〕に記載の方法。
〔16〕前記〔1〕~〔15〕に記載された、樹脂製農薬容器変形防止用の、農薬油性懸濁剤。
〔17〕樹脂製農薬容器の変形を防止する方法であって、(1)農薬有効成分、(2)油性成分並びに(3)フェノール誘導体、没食子酸エステル及びエトキシキンからなる群から選択される少なくとも1種の酸化防止剤を混合して農薬油性懸濁剤を調製し、
次いで当該農薬油性懸濁剤を樹脂製農薬容器に充填し、
充填後に樹脂製農薬容器内部の酸素が消費されることによる当該樹脂製農薬容器内の減圧を抑える、方法。
〔18〕前記酸化防止剤が、フェノール誘導体及び没食子酸エステルからなる群から選択される少なくとも1種である、〔17〕に記載の方法。
下記表Aに示す量の各成分を、ホモジナイザーULTRA-TURRAX T25basic(IKA社製)にて混合粉砕して、油性懸濁剤を調製する。表A中の数字は重量部を表す。表A中の(C)成分である界面活性剤(C1)~(C7)は、各々表Bに示したものであり、また、表A中に記載した商品の成分は、各々以下のものである。
・商品名「SAG47」:シリコーン系消泡剤(モメンティブ社製)
・商品名「Agnique ME 18RD-F」:C16-18飽和脂肪酸とC18不飽和脂肪酸のメチルエステル(BASF社製)
・商品名「コーンサラダ油」:トリアシルグリセロール(ボーソー油脂社製)
試験例1
以下の通り、農薬有効成分有りの油性懸濁剤と、農薬有効成分無しの油性懸濁剤を調製した。
[農薬有効成分有り]
農薬有効成分(トルピラレート12.0重量部、ニコスルフロン12.0重量部)、ポリオキシエチレンソルビタン脂肪酸エステル10.5重量部、ポリオキシエチレンヒマシ油1.2重量部、アルキルベンゼンスルホン酸カルシウム3.3重量部、有機ベントナイト1.5重量部、ポリオキシエチレンモノアルキルエーテル3.0重量部、乾式法シリカ3.0重量部を混合し、Agnique ME18RD-F(商品名:C16-18飽和脂肪酸とC18不飽和脂肪酸のメチルエステル、BASF社製)を54.7重量部加えて1Lとなるように調製した。その後、ホモジナイザーULTRA-TURRAX T25basic(IKA社製)により混合粉砕し、農薬有効成分の粒子径が5μm以下となるようにビーズミルでさらに粉砕して油性懸濁剤を得た。
ポリオキシエチレンソルビタン脂肪酸エステル6.2重量部、ポリオキシエチレンヒマシ油0.7重量部、アルキルベンゼンスルホン酸カルシウム1.9重量部、Agnique ME18RD-F(商品名:C16-18飽和脂肪酸とC18不飽和脂肪酸のメチルエステル、BASF社製)を79.2重量部加えて1Lとなるように調製してから、ホモジナイザーULTRA-TURRAX T25basic(IKA社製)により混合粉砕して油性懸濁剤を得た。
ボトル容器の外観 〇:変化がないか極わずか、×:胴体部分に大きな凹み有
試験例1と同じ方法で油性懸濁剤を調製し、第2表に示した酸化防止剤0.01重量部~3.0重量部を添加、混合した後、ボトル容器の外観及びボトル容器内の酸素濃度を測定した。調査結果は第2表に示した。
試験例2で調製した油性懸濁剤70gを100mlのガラス瓶に量り取り、アルミ包装容器(ヤナギ社製、型番0401、12×22cm)に入れ、アルミラミネートの体積が400~430mlとなるように内部の空気量を調整して、ヒートシーラー(富士インパルス社製、型番PS-310E型)にて密閉し、室温で130日間保管した。アルミラミネート容器の体積の変化は、あらかじめ1.5Lの水を張った2Lのメスシリンダーにアルミラミネート容器を沈めた際の水の体積を量ることで調査した。調査結果は第3表に示した。
第4表に示した農薬有効成分を用い、試験例1と同じ方法で油性懸濁剤を調製し、ジブチルヒドロキシトルエン0.01重量部~0.2重量部を添加、混合した後、40℃で28日間保存した。ボトル容器の状態の調査のため、ボトル容器の外径(中央部及び下部(底から2cm)を測定し、下記式により、外径の変化率CV値を算出した。CV値が小さいほど容器の変形が小さく変形防止効果が高い。調査結果は第4表に示した。
CV値=容器外径の標準偏差÷容器外径の平均値×100
なお、2021年8月12日に出願された日本特許出願2021-131666号の明細書、特許請求の範囲、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
Claims (15)
- 農薬油性懸濁剤を充填した樹脂製農薬容器の変形を防止する方法であって、当該樹脂製農薬容器に充填する農薬油性懸濁剤が(1)農薬有効成分、(2)油性成分並びに(3)フェノール誘導体、没食子酸エステル及びエトキシキンからなる群から選択される少なくとも1種の酸化防止剤を含有するものである、前記樹脂製農薬容器の変形を防止する方法。
- 前記酸化防止剤が、フェノール誘導体及び没食子酸エステルからなる群から選択される少なくとも1種である、請求項1に記載の方法。
- 前記酸化防止剤がフェノール誘導体である、請求項1又は2に記載の方法。
- 前記フェノール誘導体が、ジブチルヒドロキシトルエン、ブチルヒドロキシアニソール、2,5-ジ-tert-アミルヒドロキノン、2,5-ジ-tert-ブチルヒドロキノン、4,4’-ブチリデンビス(6-tert-ブチル-m-クレゾール)、4,4’-チオビス(6-tert-ブチル-m-クレゾール)及びビス(5-tert-ブチル-4-ヒドロキシ-2-メチルフェニル)スルフィドからなる群から選択される少なくとも1種である、請求項1~3に記載の方法。
- 前記油性成分が植物油、アルキルエステル化された植物油、鉱物油及び芳香族油からなる群から選択される少なくとも1種である、請求項1~4に記載の方法。
- 前記油性成分が、脂肪酸グリセライドである、請求項1~5に記載の方法。
- 前記脂肪酸グリセライドが、α-リノレン酸、リノール酸、オレイン酸、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、パルミトレイン酸、ステアリン酸、アラキジン酸、エイコセン酸、ベヘン酸、エルシン酸、リグノセリン酸、エルカ酸及びリシノール酸からなる群から選択される少なくとも1種の脂肪酸のグリセライドである、請求項6に記載の方法。
- 前記脂肪酸グリセライドが、モノグリセライド、ジグリセライド、トリグリセライド又はそれらの混合物である、請求項6又は7に記載の方法。
- 前記酸化防止剤と前記油性成分との重量比が0.01:99.99~15:85である、請求項1~8に記載の方法。
- 前記農薬油性懸濁剤を前記樹脂製農薬容器に充填した後、さらに、容器内の空間部のガスを窒素ガスへ置換する、請求項1~9に記載の方法。
- (1)農薬有効成分、(2)油性成分並びに(3)フェノール誘導体、没食子酸エステル及びエトキシキンからなる群から選択される少なくとも1種の酸化防止剤を含有する農薬油性懸濁剤であって、樹脂製農薬容器に充填されたのち容器内で発生する油性成分の酸化が抑制された、樹脂製農薬容器変形防止用の、前記農薬油性懸濁剤。
- 前記酸化防止剤が、フェノール誘導体及び没食子酸エステルからなる群から選択される少なくとも1種である、請求項11に記載の農薬油性懸濁剤。
- 樹脂製農薬容器の変形を防止する方法であって、
(1)農薬有効成分、(2)油性成分並びに(3)フェノール誘導体、没食子酸エステル及びエトキシキンからなる群から選択される少なくとも1種の酸化防止剤を混合して農薬油性懸濁剤を調製し、
次いで当該農薬油性懸濁剤を樹脂製農薬容器に充填し、
充填後に樹脂製農薬容器内部の酸素が消費されることによる当該樹脂製農薬容器内の減圧を抑える、方法。 - 前記酸化防止剤が、フェノール誘導体及び没食子酸エステルからなる群から選択される少なくとも1種である、請求項13に記載の方法。
- 前記農薬油性懸濁剤を充填した後、前記樹脂製農薬容器の空間部分に窒素ガスを供給するする、請求項13または14に記載の方法。
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