WO2023157929A1 - Inhibitor against crop injury due to agricultural material - Google Patents

Inhibitor against crop injury due to agricultural material Download PDF

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WO2023157929A1
WO2023157929A1 PCT/JP2023/005504 JP2023005504W WO2023157929A1 WO 2023157929 A1 WO2023157929 A1 WO 2023157929A1 JP 2023005504 W JP2023005504 W JP 2023005504W WO 2023157929 A1 WO2023157929 A1 WO 2023157929A1
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Prior art keywords
humic acid
agricultural materials
inhibitor
agricultural
phytotoxicity
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PCT/JP2023/005504
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French (fr)
Japanese (ja)
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峻 大川
藤樹 飯野
義弘 鳴坂
真理 鳴坂
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デンカ株式会社
岡山県
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Publication of WO2023157929A1 publication Critical patent/WO2023157929A1/en

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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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper
    • 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
    • A01N61/00—Biocides, pest repellants or attractants, or plant growth regulators containing substances of unknown or undetermined composition, e.g. substances characterised only by the mode of action
    • 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
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures 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
    • A01P3/00—Fungicides

Definitions

  • the present invention relates to an inhibitor of phytotoxicity caused by agricultural materials.
  • Patent Document 1 discloses a plant pathogen control agent containing a metal chelate or salt as an active ingredient.
  • Patent Document 2 discloses a plant virus disease control agent containing at least one of zinc gluconate and copper gluconate as an active ingredient.
  • JP 2020-132552 A Japanese Patent No. 6634325
  • Agricultural materials such as metal salts may cause phytotoxicity when used on crop bodies.
  • the present invention has been made in view of such circumstances, and an object of the present invention is to provide an agent for suppressing phytotoxicity caused by agricultural materials.
  • the present invention relates to the following inventions.
  • An agent for suppressing phytotoxicity caused by agricultural materials containing humic acid as an active ingredient.
  • the inhibitor of phytotoxicity caused by agricultural materials according to [1] which has a melanic index of 2.0 or more.
  • the active ingredient is a humic acid extract, and the total organic carbon concentration of the humic acid extract is 15,000 mg/L or more. inhibitor.
  • a numerical range indicated using “to” indicates a range including the numerical values before and after “to” as the minimum and maximum values, respectively. Unless otherwise specified, the units of numerical values before and after "-" are the same.
  • the upper limit value or lower limit value of the numerical range at one step may be replaced with the upper limit value or lower limit value of the numerical range at another step.
  • the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples. The upper and lower limits described individually can be combined arbitrarily.
  • the inhibitor of phytotoxicity caused by agricultural materials according to the present embodiment contains humic acid as an active ingredient.
  • the inhibitor of phytotoxicity caused by agricultural materials according to the present embodiment can suppress the occurrence of phytotoxicity caused by agricultural materials as compared with the case where it is not used.
  • Agricultural materials may be, for example, pesticides.
  • Agrochemicals are agricultural chemicals that fall under the category of "agrochemicals" under the Agricultural Chemicals Regulation Act of Japan (Act No. 82 of 1948, last revision: enforced on December 1, 2020). can be used.
  • pesticides are fungi, nematodes, mites, insects, rats, grasses, other animals and plants, or viruses (hereinafter referred to as “pests”) that damage crops (including trees and agricultural and forestry products; hereinafter referred to as “crops, etc.” ) used to control fungicides, insecticides, herbicides and other agents, growth promoters, germination inhibitors and other agents used to enhance or suppress the physiological functions of agricultural crops Law Concerning Securing, etc. (Law No. 127 of 1950), excluding fertilizers prescribed in Article 2, Paragraph 1).
  • the pesticide may be, for example, a metal salt.
  • Metals in the metal salts include, for example, copper, zinc, and iron.
  • the salt in the metal salt may be an organic acid salt or an inorganic acid salt. Salts in metal salts may be sulfates or acetates.
  • the metal salt may be at least one selected from the group consisting of copper salts, zinc salts and iron salts, and at least one selected from the group consisting of copper sulfate, copper acetate, zinc sulfate and zinc acetate.
  • the metal salt may be either an anhydride or a hydrate.
  • Vegetables are examples of crop bodies to which inhibitors of chemical damage caused by agricultural materials are applied. Vegetables may be leafy vegetables such as Chinese cabbage, Japanese mustard spinach, spinach and lettuce, and solanaceous fruit vegetables such as tomatoes, eggplants, green peppers and hot peppers.
  • phytotoxicity caused by agricultural materials refers to damage to the appearance, function, quality, etc. of crops caused by agricultural materials.
  • the phytotoxicity caused by agricultural materials includes, for example, inhibition of growth, whitening of part or all of the tissue of the crop body, white spots, brown spots, etc. on the crop body. (etiolation), necrosis (death of tissues, cells, etc.), defoliation, and deformed leaves.
  • Human acid as used herein includes humic acid and fulvic acid.
  • Humic acid includes one or more selected from the group consisting of humic acid and humic acid salts.
  • Humic acid has agricultural advantages such as promoting the growth of crop bodies and making it less susceptible to environmental stress (for example, the effects of global warming). For example, it is possible to obtain effects such as promoting the growth of crop bodies and making them less susceptible to environmental stress (for example, the effects of global warming) while suppressing chemical damage caused by agricultural materials.
  • humic acid examples include natural humic acid produced naturally in peat and weathered coal, artificial humic acid artificially produced by nitric acid oxidation of lignite, and natural humic acid or artificial humic acid containing sodium, potassium, Examples include humic acid salts neutralized with alkaline substances such as ammonia, calcium and magnesium.
  • Humic acids include fulvic acid, humic acid, nitrohumic acid, ammonium humate, calcium humate, magnesium humate, ammonium nitrohumate, calcium nitrohumate and magnesium nitrohumate, potassium humate, potassium nitrohumate and the like.
  • the active ingredient may be a humic acid extract.
  • the humic acid extract is an extract obtained by extracting nitric oxide from young coal with an extraction solvent containing water and, if necessary, alkali.
  • Young coal is coal that has a lower carbon content than bituminous coal, etc., and is defined as having a carbon content of 83% by mass or less. Young coal includes, for example, peat, lignite, lignite, sub-bituminous coal, and the like. Young coal may be used singly or in combination of two or more. Humic acid may be derived from brown coal from the viewpoint of the effect of suppressing phytotoxicity caused by agricultural materials.
  • Nitric oxide of young coal is obtained by oxidative decomposition of young coal with nitric acid.
  • Concentrated nitric acid is preferred as the nitric acid. From the viewpoint of safety and reactivity, it is preferable to use nitric acid with a concentration of 40 to 60% by mass.
  • the amount of nitric acid (HNO 3 ) used in the oxidative decomposition may be 10 parts by mass or more, or 20 parts by mass or more with respect to 20 parts by mass of young coal, and may be 300 parts by mass or less, 250 parts by mass or less, 200 parts by mass or less. It may be no more than 150 parts by mass, no more than 100 parts by mass, no more than 50 parts by mass, no more than 36 parts by mass, or no more than 20 parts by mass.
  • the amount of nitric acid (HNO 3 ) used may be 10 to 20 parts by mass, and may be 20 to 36 parts by mass, with respect to 20 parts by mass of young coal.
  • the amount of nitric acid used is a value converted to 100% nitric acid (100% HNO 3 ).
  • the temperature during oxidative decomposition may be, for example, 70 to 95°C.
  • heating to 70 to 95° C. in a hot water bath or the like facilitates rapid progress of the oxidation reaction.
  • the reaction time may be, for example, 20 minutes or more, 0.5 hours or more, or 1 hour or more, and may be 6 hours or less, 4 hours or less, or 1 hour or less.
  • the humic acid extract is prepared as a liquid by, for example, stirring nitric oxide of young coal (hereinafter referred to as crude humic acid) and an extraction solvent containing water and alkali, and then performing a solid-liquid separation step. can get.
  • the alkali includes hydroxide, ammonia, and the like.
  • Hydroxides include alkali metal hydroxides, ammonium hydroxide and the like.
  • an alkali metal hydroxide is preferable.
  • alkali metal hydroxides include potassium hydroxide and sodium hydroxide.
  • the hydroxide one or more of potassium hydroxide, sodium hydroxide, and ammonium hydroxide (ammonia water) are preferable.
  • the pH of the extraction solvent may be 0.5-7.0, 0.5-4.0 or 1.0-3.0.
  • the temperature (extraction temperature) at which the humic acid crude product is extracted with an extraction solvent may be, for example, 40 to 90°C from the viewpoint of further suppressing freezing and quality deterioration of the extract.
  • the time for extracting the humic acid crude product with the extraction solvent may be, for example, 0.5 hours or longer, 24 hours or shorter, or 1 hour or shorter.
  • the solid-liquid ratio is defined as the amount of extraction solvent relative to the amount of raw young coal used to prepare the humic acid crude product. For example, when 100 g (100 mL) of extraction solvent (water) is added to crude humic acid prepared from 20 g of young coal, the solid-liquid ratio (extraction solvent/young coal) is 5.
  • the solid-liquid ratio may be 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, 9 or more, or 10 or more, and 15 or less, 13 or less, 11 or less, 9 or less, 7 or less, or 6 or less.
  • the solid-liquid ratio can be adjusted by adding water.
  • the solid-liquid ratio may be adjusted so as to achieve the desired solid-liquid ratio after adjusting the pH.
  • the solid-liquid separation method may be centrifugation, filter press, or the like.
  • the total organic carbon concentration (TOC) of the humic acid extract is 15,000 mg/L or more, 15,300 mg/L or more, 15,500 mg/L or more, 16,000 mg/L or more, 16,500 mg/L or more, 17, 000 mg/L or more, 17,500 mg/L or more, 18,000 mg/L or more, 18,500 mg/L or more, 19,000 mg/L or more, 19,500 mg/L or more, 20,000 mg/L or more, or 20, It may be 500 mg/L or more.
  • the TOC of the humic acid extract is 75,000 mg/L or less, 70,000 mg/L or less, 65,000 mg/L or less, 60,000 mg/L or less, 55,000 mg/L or less, 50,000 mg/L or less, 45,000 mg/L or less, 40,000 mg/L or less, 35,000 mg/L or less, 30,000 mg/L or less, 25,000 mg/L or less, 24,000 mg/L or less, 23,000 mg/L or less, or It may be 22,000 mg/L or less.
  • the method of measuring the TOC of the humic acid extract is defined as follows.
  • the humic acid extract was centrifuged at 3,000 ⁇ g, and the supernatant was measured using a total organic carbon meter (TOC-L manufactured by Shimadzu Corporation) by combustion catalytic oxidation.
  • TOC-L total organic carbon meter
  • the above (humic acid fraction and fulvic acid fraction) are separated according to the International Humic Substances Society method (Fujitake, Humic Substances Research Vol3, P1-9). and measure the TOC of the humic acid extract.
  • the melanic index (MI) of humic acid may be, for example, 1.5 or higher, 2.0 or higher, 2.2 or higher, 2.5 or higher, 3.0 or higher, or 3.5 or higher.
  • the MI of humic acid may be 6.5 or less, 6.0 or less, 5.5 or less, 5.0 or less, 4.5 or less, 4.0 or less, 3.5 or less, or 3.0 or less .
  • MI is an index used to classify humic acid, and is the ratio (A 450 / A 520 ). (Ky ⁇ ichi Kumada, Soil Organic Matter Chemistry, 2nd Edition, Gakkai Shuppan Center (1981), Japan Journal of Soil and Fertilizer Science, No. 71, No. 1, pp. 82-85 (2000)).
  • MI is calculated by the following method.
  • the sample is ground to a 250 ⁇ m sieve using a mortar and 250 ⁇ m sieve. About 10 g of it is placed in a weighing bottle with a known mass and accurately weighed. This weighing bottle is left in a dryer maintained at a temperature of 105° C. for about 12 hours, then returned to room temperature of 20° C. in a desiccator, and then accurately weighed again.
  • the moisture content of the sample is determined by considering the weight loss as moisture.
  • the absorbance at 450 nm shows 1.0 or more
  • add 0.1 mol/L sodium hydroxide aqueous solution to adjust the absorbance to 0.8 or more and less than 1.0, then measure the absorbance at 520 nm. do.
  • the ratio of absorbance at 450 nm to absorbance at 520 nm is calculated as MI.
  • the mass average molecular weight of humic acid may be 100-6,000.
  • the lower limit of the mass average molecular weight of humic acid may be, for example, 200 or more, 300 or more, 400 or more, 500 or more, 600 or more, 700 or more, 800 or more, 900 or more, or 1000 or more.
  • the upper limit of the mass average molecular weight of humic acid is, for example, 5,500 or less, 5,000 or less, 4,500 or less, 4,000 or less, 3,500 or less, 3,000 or less, 2,500 or less, 2,000 1,500 or less, 1,2000 or less, or 1,000 or less.
  • the mass average molecular weight of humic acid is measured by the HPSEC method (GPC method) using Alliance HPLC System manufactured by Waters.
  • the column is SB-803HQ manufactured by Showa Denko KK, the standard sample is sodium polystyrene sulfonate, and the detection wavelength is 260 nm.
  • the mobile phase is 10 mmol/L sodium phosphate buffer containing 25% by mass of acetonitrile, the flow rate is 0.8 ml/min, and the column temperature is 40° C. (column oven setting).
  • the dosage form of the inhibitor of phytotoxicity caused by agricultural materials may be, for example, a liquid formulation or a powder formulation. Powders can be obtained as redissolvable powders by, for example, drying up a liquid agent for suppressing phytotoxicity caused by agricultural materials by freeze-drying or the like.
  • the inhibitor of phytotoxicity caused by agricultural materials may consist of only humic acid, or may contain other ingredients than humic acid.
  • the content of humic acid in the inhibitor of phytotoxicity caused by agricultural materials is, for example, 5% by mass or more, 10% by mass or more, 20% by mass or more, or 30% by mass, based on the total mass of the inhibitor of phytotoxicity caused by agricultural materials.
  • the inhibitor of chemical damage caused by agricultural materials can be used in combination with agricultural materials.
  • an agricultural chemical when used as an agricultural material, by applying a chemical agent containing the agricultural chemical and humic acid to the target, it is possible to obtain the control effect of the agricultural chemical and suppress the occurrence of phytotoxicity caused by the agricultural chemical.
  • the method of suppressing phytotoxicity of crops caused by agricultural materials according to the present embodiment includes applying humic acid to crops.
  • Methods of applying humic acid to crop bodies include methods of spraying or coating crop bodies, and methods of soil irrigation or soil mixing.
  • the amount and period of application of humic acid are not particularly limited.
  • the total organic carbon concentration is 0.1 to 5,000 mg / L 1 to 12 times a month, and in the case of hydroponics, the total organic carbon concentration. as 0.1 to 5,000 mg/L 1 to 12 times a month, and in the case of foliar application, the total organic carbon concentration can be 0.1 to 5,000 mg/L and 1 to 12 times a month. .
  • the portion of the crop body to which humic acid is applied is the whole or a part of the crop body, and can be appropriately selected according to the type of the crop body, the type of agricultural material, and the like.
  • the part of the crop body to which humic acid is applied may be the leaves of the crop body.
  • the timing of applying humic acid is not particularly limited, and can be appropriately selected according to the type of crop body, the type of agricultural material to be applied, and the like.
  • humic acid may be applied to the crop body to which the agricultural material has been applied, may be applied to the crop body before applying the agricultural material, or may be applied to the crop body at the same time as the application of the agricultural material. good.
  • the above-mentioned present invention can also be regarded as the use of humic acid to suppress phytotoxicity caused by agricultural materials.
  • the present invention described above can also be regarded as humic acid for use in suppressing phytotoxicity caused by agricultural materials.
  • the present invention described above can also be regarded as the use (application) of humic acid for the production of an inhibitor of chemical damage caused by agricultural materials.
  • the MI of humic acid in humic acid extract A was 4.8.
  • the total organic carbon concentration (TOC) of humic acid extract A was 22,000 mg/L.
  • the mass average molecular weight of humic acid in the humic acid extract A was 530.
  • the mass average molecular weight of humic acid was measured by HPSEC method (GPC method) using Alliance HPLC System manufactured by Waters.
  • the column was SB-803HQ manufactured by Showa Denko KK, the standard sample was sodium polystyrene sulfonate, and the detection wavelength was 260 nm.
  • the mobile phase was 10 mmol/L sodium phosphate buffer containing 25 mass % acetonitrile, the flow rate was 0.8 ml/min, and the column temperature was 40° C. (column oven setting).
  • TOC Total organic carbon concentration
  • MI Melt Index
  • the sample was ground to a 250 ⁇ m sieve product using a mortar and 250 ⁇ m sieve. About 10 g of it was placed in a weighing bottle with a known mass and accurately weighed. This weighing bottle was allowed to stand for about 12 hours in a dryer maintained at a temperature of 105° C., then returned to room temperature of 20° C. in a desiccator, and then accurately weighed again. The moisture content of the sample was determined by considering the mass decrease as moisture.
  • Test Example 1 Pathogen inoculation test 1 to tomato
  • Control group test group 1 (humic acid extract A 40 ppm)
  • test group 2 0.4 mM CuSO 4 5H 2 O
  • test group 3 0.4 mM CuSO 4.5H 2 O
  • Tomatoes (cultivar Regina) (2 strains/pot, 19 days old after seeding, 2.5 true leaves) were sprayed with each agent and allowed to stand in an incubator (24 ° C., 16 hours (light) / 8 hours (dark) light/dark cycle, 50% humidity). Three days after treatment, the plants were spray inoculated with Pseudomonas syringae (5 ⁇ 10 6 cfu/ml) (4-5 sprays per plant). The above plants were cultured in a moist room (24°C, 16 hours (light)/8 hours (dark) light/dark cycle), and disease symptoms were examined 5 days after inoculation.
  • the disease incidence was investigated by classifying the severity of disease into the following five categories. 0: no symptoms, 1: fine spots, 2: lesions are observed in less than 25% area of the leaves, 3: lesions are observed in 25% or more and less than 50% area of the leaves, 4: leaf Lesions are observed in 50% or more of the area. 5: defoliation or death n1 to n5 indicate the number of individuals.
  • FIG. 3 is a photograph showing the observation results of Chinese cabbage seedlings treated with each drug 5 days after inoculation with the pathogen. Even when Chinese cabbage was used, the result of reduction of phytotoxicity was obtained similarly to that of tomato. Since Chinese cabbage is prone to phytotoxicity, when copper sulfate was used alone, phytotoxicity (white spots, brown spots, etc.) occurred to the extent that it could not be tested. On the other hand, when the humic acid extract A and copper sulfate were used in combination, phytotoxicity was suppressed.

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Abstract

One aspect of the present invention relates to an inhibitor against crop injury due to agricultural material, the inhibitor containing humic acid as an active ingredient.

Description

農業資材による薬害の抑制剤Suppressant for phytotoxicity caused by agricultural materials
　本発明は、農業資材による薬害の抑制剤に関する。 The present invention relates to an inhibitor of phytotoxicity caused by agricultural materials.
　植物を病原菌及びウイルス等から保護するために、金属塩等の農業資材が用いられる場合がある。例えば、特許文献１には、金属のキレート又は塩を有効成分とする、植物病原菌の防除剤が開示されている。例えば、特許文献２には、グルコン酸亜鉛及びグルコン酸銅の少なくとも１つを有効成分とする、植物ウイルス病の防除剤が開示されている。 Agricultural materials such as metal salts are sometimes used to protect plants from pathogenic bacteria and viruses. For example, Patent Document 1 discloses a plant pathogen control agent containing a metal chelate or salt as an active ingredient. For example, Patent Document 2 discloses a plant virus disease control agent containing at least one of zinc gluconate and copper gluconate as an active ingredient.
特開２０２０－１３２５５２号公報JP 2020-132552 A 特許第６６３４３２５号公報Japanese Patent No. 6634325
　金属塩等の農業資材は、作物体に用いた際に薬害を引き起こす場合がある。本発明は、このような事情に鑑みてなされたものであり、農業資材による薬害の抑制剤を提供することを目的とする。 Agricultural materials such as metal salts may cause phytotoxicity when used on crop bodies. The present invention has been made in view of such circumstances, and an object of the present invention is to provide an agent for suppressing phytotoxicity caused by agricultural materials.
　本発明は、以下の各発明に関する。
［１］腐植酸を有効成分として含有する、農業資材による薬害の抑制剤。
［２］メラニックインデックスが２．０以上である、［１］に記載の農業資材による薬害の抑制剤。
［３］腐植酸の質量平均分子量が１００～６，０００である、［１］又は［２］に記載の農業資材による薬害の抑制剤。
［４］有効成分が腐植酸抽出液であり、腐植酸抽出液の全有機炭素濃度が１５，０００ｍｇ／Ｌ以上である、［１］～［３］のいずれかに記載の農業資材による薬害の抑制剤。
［５］腐植酸の質量平均分子量が１００～１，２００であり、腐植酸抽出液の全有機炭素濃度が１５，０００～２５，０００ｍｇ／Ｌである、［４］に記載の農業資材による薬害の抑制剤。
［６］褐炭由来である、［１］～［５］のいずれかに記載の農業資材による薬害の抑制剤。
［７］農業資材が農薬である、［１］～［６］のいずれかに記載の農業資材による薬害の抑制剤。
［８］農薬が金属塩である、［７］に記載の農業資材による薬害の抑制剤。
［９］農薬が銅塩、亜鉛塩、及び鉄塩からなる群より選択される少なくとも１種の金属塩である、［７］又は［８］に記載の農業資材による薬害の抑制剤。
［１０］作物体の農業資材による薬害を抑制する方法であって、作物体に腐植酸を施用することを含む、方法。 The present invention relates to the following inventions.
[1] An agent for suppressing phytotoxicity caused by agricultural materials, containing humic acid as an active ingredient.
[2] The inhibitor of phytotoxicity caused by agricultural materials according to [1], which has a melanic index of 2.0 or more.
[3] The inhibitor of phytotoxicity caused by agricultural materials according to [1] or [2], wherein the humic acid has a mass average molecular weight of 100 to 6,000.
[4] The active ingredient is a humic acid extract, and the total organic carbon concentration of the humic acid extract is 15,000 mg/L or more. inhibitor.
[5] Chemical damage due to agricultural materials according to [4], wherein the mass average molecular weight of humic acid is 100 to 1,200, and the total organic carbon concentration of the humic acid extract is 15,000 to 25,000 mg/L. inhibitor.
[6] The inhibitor of phytotoxicity caused by agricultural materials according to any one of [1] to [5], which is derived from lignite.
[7] The inhibitor of phytotoxicity caused by agricultural materials according to any one of [1] to [6], wherein the agricultural materials are agricultural chemicals.
[8] The inhibitor of phytotoxicity caused by agricultural materials according to [7], wherein the agricultural chemical is a metal salt.
[9] The inhibitor of phytotoxicity caused by agricultural materials according to [7] or [8], wherein the pesticide is at least one metal salt selected from the group consisting of copper salts, zinc salts and iron salts.
[10] A method for suppressing phytotoxicity of crop bodies by agricultural materials, comprising applying humic acid to the crop bodies.
　本発明によれば、農業資材による薬害の抑制剤を提供することができる。 According to the present invention, it is possible to provide an inhibitor of phytotoxicity caused by agricultural materials.
病原菌を接種したトマトの発病度の算出結果を示すグラフである。It is a graph which shows the calculation result of the severity of the disease of the tomato inoculated with pathogenic bacteria. 病原菌を接種したハクサイの発病度の算出結果を示すグラフである。It is a graph which shows the calculation result of the degree of disease of the Chinese cabbage inoculated with pathogenic bacteria. 病原菌を接種したハクサイの薬害の観察結果を示す写真である。It is a photograph showing the observation results of phytotoxicity of Chinese cabbage inoculated with pathogenic bacteria.
　以下、本発明を実施するための形態について詳細に説明する。ただし、本発明は以下の実施形態に限定されるものではない。本明細書中、「～」を用いて示された数値範囲は、「～」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。具体的に明示する場合を除き、「～」の前後に記載される数値の単位は同じである。本明細書中に段階的に記載されている数値範囲において、ある段階の数値範囲の上限値又は下限値は、他の段階の数値範囲の上限値又は下限値に置き換えてもよい。本明細書中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。個別に記載した上限値及び下限値は任意に組み合わせ可能である。 Hereinafter, the embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In this specification, a numerical range indicated using "to" indicates a range including the numerical values before and after "to" as the minimum and maximum values, respectively. Unless otherwise specified, the units of numerical values before and after "-" are the same. In the numerical ranges described stepwise in this specification, the upper limit value or lower limit value of the numerical range at one step may be replaced with the upper limit value or lower limit value of the numerical range at another step. In the numerical ranges described herein, the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples. The upper and lower limits described individually can be combined arbitrarily.
〔農業資材による薬害の抑制剤〕
　本実施形態に係る農業資材による薬害の抑制剤は、腐植酸を有効成分として含有する。本実施形態に係る農業資材による薬害の抑制剤は、これを使用しない場合と比べて、農業資材に起因する薬害の発生を抑制することができる。 [Inhibitor for phytotoxicity caused by agricultural materials]
The inhibitor of phytotoxicity caused by agricultural materials according to the present embodiment contains humic acid as an active ingredient. The inhibitor of phytotoxicity caused by agricultural materials according to the present embodiment can suppress the occurrence of phytotoxicity caused by agricultural materials as compared with the case where it is not used.
＜農業資材＞
　農業資材は、例えば、農薬であってよい。農薬は、農業用の薬剤であり、日本国農薬取締法（昭和二十三年法律第八十二号、最終改正：令和２年１２月１日施行）上の「農薬」に該当する薬剤を用いることができる。具体的には、農薬は、農作物（樹木及び農林産物を含む。以下「農作物等」という。）を害する菌、線虫、だに、昆虫、ねずみ、草その他の動植物又はウイルス（以下「病害虫」と総称する。）の防除に用いられる殺菌剤、殺虫剤、除草剤その他の薬剤等、農作物等の生理機能の増進又は抑制に用いられる成長促進剤、発芽抑制剤その他の薬剤（肥料の品質の確保等に関する法律（昭和二十五年法律第百二十七号）第二条第一項に規定する肥料を除く。）等であってよい。 <Agricultural materials>
Agricultural materials may be, for example, pesticides. Agrochemicals are agricultural chemicals that fall under the category of "agrochemicals" under the Agricultural Chemicals Regulation Act of Japan (Act No. 82 of 1948, last revision: enforced on December 1, 2020). can be used. Specifically, pesticides are fungi, nematodes, mites, insects, rats, grasses, other animals and plants, or viruses (hereinafter referred to as “pests”) that damage crops (including trees and agricultural and forestry products; hereinafter referred to as “crops, etc.” ) used to control fungicides, insecticides, herbicides and other agents, growth promoters, germination inhibitors and other agents used to enhance or suppress the physiological functions of agricultural crops Law Concerning Securing, etc. (Law No. 127 of 1950), excluding fertilizers prescribed in Article 2, Paragraph 1).
　農薬は、例えば、金属塩であってよい。金属塩における金属としては、例えば、銅、亜鉛、及び、鉄が挙げられる。金属塩における塩は、有機酸塩であってよく、無機酸塩であってもよい。金属塩における塩は、硫酸塩、又は酢酸塩であってよい。金属塩は、銅塩、亜鉛塩及び鉄塩からなる群より選択される少なくとも１種であってよく、硫酸銅、酢酸銅、硫酸亜鉛、及び酢酸亜鉛からなる群より選択される少なくとも１種であることが好ましい。金属塩は、無水物であってもよく、水和物であってもよい。 The pesticide may be, for example, a metal salt. Metals in the metal salts include, for example, copper, zinc, and iron. The salt in the metal salt may be an organic acid salt or an inorganic acid salt. Salts in metal salts may be sulfates or acetates. The metal salt may be at least one selected from the group consisting of copper salts, zinc salts and iron salts, and at least one selected from the group consisting of copper sulfate, copper acetate, zinc sulfate and zinc acetate. Preferably. The metal salt may be either an anhydride or a hydrate.
＜作物体＞
　農業資材による薬害の抑制剤の対象となる作物体としては、野菜類が挙げられる。野菜類は、ハクサイ、コマツナ、ホウレンソウ、レタス等の葉菜類であってよく、トマト、ナス、ピーマン、トウガラシ等のナス科果菜類が挙げられる。 <Crop body>
Vegetables are examples of crop bodies to which inhibitors of chemical damage caused by agricultural materials are applied. Vegetables may be leafy vegetables such as Chinese cabbage, Japanese mustard spinach, spinach and lettuce, and solanaceous fruit vegetables such as tomatoes, eggplants, green peppers and hot peppers.
＜薬害＞
　「農業資材による薬害」は、農業資材によって作物の外観、機能、及び品質等に障害を受けることをいう。農業資材による薬害には、例えば、生育が阻害される、作物体の組織の一部又は全部が白くなる、作物体に白抜きの斑点、褐色斑点等が生じる、茎葉に現れる症状としては、クロロシス（黄化）、ネクロシス（組織、細胞等が死ぬ）、落葉、奇形葉を生じる等が含まれる。 <Phytotoxicity>
"Phytotoxicity caused by agricultural materials" refers to damage to the appearance, function, quality, etc. of crops caused by agricultural materials. The phytotoxicity caused by agricultural materials includes, for example, inhibition of growth, whitening of part or all of the tissue of the crop body, white spots, brown spots, etc. on the crop body. (etiolation), necrosis (death of tissues, cells, etc.), defoliation, and deformed leaves.
＜腐植酸＞
　本明細書における「腐植酸」には、フミン酸及びフルボ酸が含まれる。腐植酸は、腐植酸及び腐植酸塩からなる群より選択される１種以上を含む。腐植酸は、作物体の生育を促進する、環境ストレス（例えば、温暖化の影響）を受けにくくなる等の農業上の利点を有するため、本実施形態に係る農業資材による薬害の抑制剤によれば、農業資材による薬害を抑制しながら、作物体の生育を促進する、及び、環境ストレス（例えば、温暖化の影響）を受けにくくなる等の効果を得ることができる。 <humic acid>
"Humic acid" as used herein includes humic acid and fulvic acid. Humic acid includes one or more selected from the group consisting of humic acid and humic acid salts. Humic acid has agricultural advantages such as promoting the growth of crop bodies and making it less susceptible to environmental stress (for example, the effects of global warming). For example, it is possible to obtain effects such as promoting the growth of crop bodies and making them less susceptible to environmental stress (for example, the effects of global warming) while suppressing chemical damage caused by agricultural materials.
　腐植酸としては、泥炭及び風化炭等の天然に産出される天然腐植酸、褐炭の硝酸酸化等により人工的に製造される人工腐植酸、及び、天然腐植酸又は人工腐植酸をナトリウム、カリウム、アンモニア、カルシウム及びマグネシウム等のアルカリ物質で中和した腐植酸塩等が挙げられる。腐植酸としては、フルボ酸、フミン酸、ニトロフミン酸、フミン酸アンモニウム、フミン酸カルシウム、フミン酸マグネシウム、ニトロフミン酸アンモニウム、ニトロフミン酸カルシウム及びニトロフミン酸マグネシウム、フミン酸カリウム、ニトロフミン酸カリウム等が挙げられる。 Examples of humic acid include natural humic acid produced naturally in peat and weathered coal, artificial humic acid artificially produced by nitric acid oxidation of lignite, and natural humic acid or artificial humic acid containing sodium, potassium, Examples include humic acid salts neutralized with alkaline substances such as ammonia, calcium and magnesium. Humic acids include fulvic acid, humic acid, nitrohumic acid, ammonium humate, calcium humate, magnesium humate, ammonium nitrohumate, calcium nitrohumate and magnesium nitrohumate, potassium humate, potassium nitrohumate and the like.
　有効成分は、腐植酸抽出液であってよい。腐植酸抽出液は、若年炭の硝酸酸化物を、水と必要によりアルカリとを含む抽出溶媒により抽出した抽出物である。 The active ingredient may be a humic acid extract. The humic acid extract is an extract obtained by extracting nitric oxide from young coal with an extraction solvent containing water and, if necessary, alkali.
　若年炭とは、瀝青炭等に比べ炭素含有量の少ない石炭であり、炭素含有率が８３質量％以下であるものと定義される。若年炭としては、例えば、泥炭、亜炭、褐炭、亜瀝青炭等が挙げられる。若年炭は、１種を単独で、又は２種以上を組み合わせて使用してよい。腐植酸は、農業資材による薬害の抑制効果の点から、褐炭由来であってよい。 Young coal is coal that has a lower carbon content than bituminous coal, etc., and is defined as having a carbon content of 83% by mass or less. Young coal includes, for example, peat, lignite, lignite, sub-bituminous coal, and the like. Young coal may be used singly or in combination of two or more. Humic acid may be derived from brown coal from the viewpoint of the effect of suppressing phytotoxicity caused by agricultural materials.
　若年炭の硝酸酸化物は、若年炭を硝酸で酸化分解させて得られる。硝酸としては濃硝酸が好ましい。安全性と反応性の点で、濃度４０～６０質量％の硝酸を用いることが好ましい。酸化分解の際の硝酸（ＨＮＯ３）の使用量は、若年炭２０質量部に対して、１０質量部以上、又は２０質量部以上であってよく、３００質量部以下、２５０質量部以下、２００質量部以下、１５０質量部以下、１００質量部以下、５０質量部以下、３６質量部以下、又は２０質量部以下であってよい。硝酸（ＨＮＯ３）の使用量は、若年炭２０質量部に対して、１０～２０質量部であってよく、２０～３６質量部であってよい。ここで、硝酸の使用量は１００％硝酸（１００％ＨＮＯ３）に換算した値である。 Nitric oxide of young coal is obtained by oxidative decomposition of young coal with nitric acid. Concentrated nitric acid is preferred as the nitric acid. From the viewpoint of safety and reactivity, it is preferable to use nitric acid with a concentration of 40 to 60% by mass. The amount of nitric acid (HNO 3 ) used in the oxidative decomposition may be 10 parts by mass or more, or 20 parts by mass or more with respect to 20 parts by mass of young coal, and may be 300 parts by mass or less, 250 parts by mass or less, 200 parts by mass or less. It may be no more than 150 parts by mass, no more than 100 parts by mass, no more than 50 parts by mass, no more than 36 parts by mass, or no more than 20 parts by mass. The amount of nitric acid (HNO 3 ) used may be 10 to 20 parts by mass, and may be 20 to 36 parts by mass, with respect to 20 parts by mass of young coal. Here, the amount of nitric acid used is a value converted to 100% nitric acid (100% HNO 3 ).
　酸化分解の際の温度は、例えば、７０～９５℃であってよい。酸化反応のスターターとして、湯浴等で７０～９５℃に加温すると酸化反応が速やかに進行しやすい。反応時間は、例えば、２０分間以上、０．５時間以上、又は１時間以上であってよく、６時間以下、４時間以下、又は１時間以下であってよい。 The temperature during oxidative decomposition may be, for example, 70 to 95°C. As a starter for the oxidation reaction, heating to 70 to 95° C. in a hot water bath or the like facilitates rapid progress of the oxidation reaction. The reaction time may be, for example, 20 minutes or more, 0.5 hours or more, or 1 hour or more, and may be 6 hours or less, 4 hours or less, or 1 hour or less.
　腐植酸抽出液は、例えば、若年炭の硝酸酸化物（以下、腐植酸粗製物という）と、水及びアルカリを含む抽出溶媒とを攪拌した後、固液分離工程を行うことにより、液状物として得られる。 The humic acid extract is prepared as a liquid by, for example, stirring nitric oxide of young coal (hereinafter referred to as crude humic acid) and an extraction solvent containing water and alkali, and then performing a solid-liquid separation step. can get.
　アルカリとしては、水酸化物、アンモニア等が挙げられる。水酸化物としては、アルカリ金属の水酸化物、水酸化アンモニウム等が挙げられる。水酸化物としては、アルカリ金属の水酸化物が好ましい。アルカリ金属の水酸化物としては、水酸化カリウム、水酸化ナトリウム等が挙げられる。水酸化物としては、水酸化カリウム、水酸化ナトリウム、及び水酸化アンモニウム（アンモニア水）のうちの１種以上が好ましい。抽出溶媒のｐＨは、０．５～７．０、０．５～４．０又は１．０～３．０であってよい。 　The alkali includes hydroxide, ammonia, and the like. Hydroxides include alkali metal hydroxides, ammonium hydroxide and the like. As the hydroxide, an alkali metal hydroxide is preferable. Examples of alkali metal hydroxides include potassium hydroxide and sodium hydroxide. As the hydroxide, one or more of potassium hydroxide, sodium hydroxide, and ammonium hydroxide (ammonia water) are preferable. The pH of the extraction solvent may be 0.5-7.0, 0.5-4.0 or 1.0-3.0.
　腐植酸粗製物を抽出溶媒で抽出する際の温度（抽出温度）は、抽出液の凍結及び品質低下を更に抑制する観点から、例えば、４０～９０℃であってよい。腐植酸粗製物を抽出溶媒で抽出する時間（抽出時間）は、例えば、０．５時間以上であってよく、２４時間以下であってよく、１時間以下であってもよい。 The temperature (extraction temperature) at which the humic acid crude product is extracted with an extraction solvent may be, for example, 40 to 90°C from the viewpoint of further suppressing freezing and quality deterioration of the extract. The time for extracting the humic acid crude product with the extraction solvent (extraction time) may be, for example, 0.5 hours or longer, 24 hours or shorter, or 1 hour or shorter.
　腐植酸粗製物を調製するために用いた原料の若年炭の量に対する抽出溶媒の量を、固液比と定義する。例えば、若年炭２０ｇから調製された腐植酸粗製物に抽出溶媒（水）１００ｇ（１００ｍＬ）を添加した場合、固液比（抽出溶媒／若年炭）は５となる。固液比は３以上、４以上、５以上、６以上、７以上、８以上、９以上又は１０以上であってよく、１５以下、１３以下、１１以下、９以下、７以下、又は６以下であってよい。固液比は、水の添加によって調整することができる。固液比は、ｐＨを調整後に目的の固液比となるように調整されてよい。固液分離する方法は、遠心分離、フィルタープレス等であってよい。 The solid-liquid ratio is defined as the amount of extraction solvent relative to the amount of raw young coal used to prepare the humic acid crude product. For example, when 100 g (100 mL) of extraction solvent (water) is added to crude humic acid prepared from 20 g of young coal, the solid-liquid ratio (extraction solvent/young coal) is 5. The solid-liquid ratio may be 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, 9 or more, or 10 or more, and 15 or less, 13 or less, 11 or less, 9 or less, 7 or less, or 6 or less. can be The solid-liquid ratio can be adjusted by adding water. The solid-liquid ratio may be adjusted so as to achieve the desired solid-liquid ratio after adjusting the pH. The solid-liquid separation method may be centrifugation, filter press, or the like.
　腐植酸抽出液の全有機炭素濃度（ＴＯＣ）は１５，０００ｍｇ／Ｌ以上、１５，３００ｍｇ／Ｌ以上、１５，５００ｍｇ／Ｌ以上、１６，０００ｍｇ／Ｌ以上、１６，５００ｍｇ／Ｌ以上、１７，０００ｍｇ／Ｌ以上、１７，５００ｍｇ／Ｌ以上、１８，０００ｍｇ／Ｌ以上、１８，５００ｍｇ／Ｌ以上、１９，０００ｍｇ／Ｌ以上、１９，５００ｍｇ／Ｌ以上、２０，０００ｍｇ／Ｌ以上、又は２０，５００ｍｇ／Ｌ以上であってよい。腐植酸抽出液のＴＯＣは、７５，０００ｍｇ／Ｌ以下、７０，０００ｍｇ／Ｌ以下、６５，０００ｍｇ／Ｌ以下、６０，０００ｍｇ／Ｌ以下、５５，０００ｍｇ／Ｌ以下、５０，０００ｍｇ／Ｌ以下、４５，０００ｍｇ／Ｌ以下、４０，０００ｍｇ／Ｌ以下、３５，０００ｍｇ／Ｌ以下、３０，０００ｍｇ／Ｌ以下、２５，０００ｍｇ／Ｌ以下、２４，０００ｍｇ／Ｌ以下、２３，０００ｍｇ／Ｌ以下、又は２２，０００ｍｇ／Ｌ以下であってよい。 The total organic carbon concentration (TOC) of the humic acid extract is 15,000 mg/L or more, 15,300 mg/L or more, 15,500 mg/L or more, 16,000 mg/L or more, 16,500 mg/L or more, 17, 000 mg/L or more, 17,500 mg/L or more, 18,000 mg/L or more, 18,500 mg/L or more, 19,000 mg/L or more, 19,500 mg/L or more, 20,000 mg/L or more, or 20, It may be 500 mg/L or more. The TOC of the humic acid extract is 75,000 mg/L or less, 70,000 mg/L or less, 65,000 mg/L or less, 60,000 mg/L or less, 55,000 mg/L or less, 50,000 mg/L or less, 45,000 mg/L or less, 40,000 mg/L or less, 35,000 mg/L or less, 30,000 mg/L or less, 25,000 mg/L or less, 24,000 mg/L or less, 23,000 mg/L or less, or It may be 22,000 mg/L or less.
　腐植酸抽出液のＴＯＣの測定方法は、次のように定義される。腐植酸抽出液を、３，０００×ｇで遠心分離した上澄み液を、全有機体炭素計（島津製作所製ＴＯＣ－Ｌ）を用いて燃焼触媒酸化方式で測定した値である。肥料成分である尿素等の非腐植物質を含む場合は、国際腐植物質学会法（藤嶽、ＨｕｍｉｃＳｕｂｓｔａｎｃｅｓ　Ｒｅｓｅａｒｃｈ　Ｖｏｌ３、Ｐ１－９）に準じて分別したもの（フミン酸画分及びフルボ酸画分）を上記の手法にて定量し、腐植酸抽出液のＴＯＣを測定する。 The method of measuring the TOC of the humic acid extract is defined as follows. The humic acid extract was centrifuged at 3,000×g, and the supernatant was measured using a total organic carbon meter (TOC-L manufactured by Shimadzu Corporation) by combustion catalytic oxidation. When non-humic substances such as urea, which is a fertilizer component, are included, the above (humic acid fraction and fulvic acid fraction) are separated according to the International Humic Substances Society method (Fujitake, Humic Substances Research Vol3, P1-9). and measure the TOC of the humic acid extract.
　腐植酸のメラニックインデックス（ＭＩ）は、例えば、１．５以上、２．０以上、２．２以上、２．５以上、３．０以上、又は３．５以上であってよい。腐植酸のＭＩは、６．５以下、６．０以下、５．５以下、５．０以下、４．５以下、４．０以下、３．５以下、又は３．０以下であってよい。 The melanic index (MI) of humic acid may be, for example, 1.5 or higher, 2.0 or higher, 2.2 or higher, 2.5 or higher, 3.0 or higher, or 3.5 or higher. The MI of humic acid may be 6.5 or less, 6.0 or less, 5.5 or less, 5.0 or less, 4.5 or less, 4.0 or less, 3.5 or less, or 3.0 or less .
　ＭＩとは、腐植酸の分類に用いられている指標であり、水酸化ナトリウム抽出液の吸収スペクトルの波長４５０ｎｍにおける吸光度（Ａ４５０）と５２０ｎｍにおける吸光度（Ａ５２０）との比（Ａ４５０／Ａ５２０）である。（熊田恭一著、土壌有機物の化学第２版　学会出版センター（１９８１）、日本土壌肥料学雑誌　第７１号　第１号　ｐ．８２～８５（２０００））。 MI is an index used to classify humic acid, and is the ratio (A 450 / A 520 ). (Kyōichi Kumada, Soil Organic Matter Chemistry, 2nd Edition, Gakkai Shuppan Center (1981), Japan Journal of Soil and Fertilizer Science, No. 71, No. 1, pp. 82-85 (2000)).
　より具体的には、ＭＩとは、次の方法によって算出されるものである。試料を乳鉢と２５０μｍ篩を用い２５０μｍ篩下品に粉砕する。その約１０ｇを、質量が既知の秤量ビンに取り精秤する。この秤量ビンを温度１０５℃に保持した乾燥機で約１２時間放置し、その後、デシケーター中で室温２０℃に戻してから再度精秤する。その質量減少分を水分とみなして試料の含水率を求める。次に、５０ｍｌ遠沈管に、上記２５０μｍ篩下品を乾燥質量相当量で０．１０ｇと、０．５ｍｏｌ／Ｌ水酸化ナトリウム水溶液４５ｍｌとを入れ、室温２０℃で約１時間、２５０ｒｐｍの速度で振とうした後、３，０００×ｇ、約１０分間の遠心分離を実施し、その上澄み液をアドバンテック社製Ｎｏ．５Ｃの濾紙で濾過する。濾液の４５０ｎｍの吸光度と５２０ｎｍの吸光度を、蒸留水をブランクとして測定する。この場合、４５０ｎｍの吸光度が１．０以上を示したならば、０．１ｍｏｌ／Ｌ水酸化ナトリウム水溶液を添加し吸光度が０．８以上１．０未満に調整してから、５２０ｎｍの吸光度を測定する。５２０ｎｍでの吸光度に対する４５０ｎｍでの吸光度の比（４５０ｎｍでの吸光度／５２０ｎｍでの吸光度）を算出し、ＭＩとする。 More specifically, MI is calculated by the following method. The sample is ground to a 250 μm sieve using a mortar and 250 μm sieve. About 10 g of it is placed in a weighing bottle with a known mass and accurately weighed. This weighing bottle is left in a dryer maintained at a temperature of 105° C. for about 12 hours, then returned to room temperature of 20° C. in a desiccator, and then accurately weighed again. The moisture content of the sample is determined by considering the weight loss as moisture. Next, in a 50 ml centrifuge tube, 0.10 g of the above 250 μm sieve product (dry mass equivalent) and 45 ml of 0.5 mol/L sodium hydroxide aqueous solution were placed, and the mixture was shaken at room temperature of 20° C. for about 1 hour at a speed of 250 rpm. After centrifugation, centrifugation was carried out at 3,000×g for about 10 minutes, and the supernatant was centrifuged in Advantech No. Filter through 5C filter paper. The absorbance at 450 nm and 520 nm of the filtrate is measured using distilled water as a blank. In this case, if the absorbance at 450 nm shows 1.0 or more, add 0.1 mol/L sodium hydroxide aqueous solution to adjust the absorbance to 0.8 or more and less than 1.0, then measure the absorbance at 520 nm. do. The ratio of absorbance at 450 nm to absorbance at 520 nm (absorbance at 450 nm/absorbance at 520 nm) is calculated as MI.
　腐植酸の質量平均分子量は、１００～６，０００であってよい。腐植酸の質量平均分子量の下限は、例えば、２００以上、３００以上、４００以上、５００以上、６００以上、７００以上、８００以上、９００以上、又は１０００以上であってよい。腐植酸の質量平均分子量の上限は、例えば、５，５００以下、５，０００以下、４，５００以下、４，０００以下、３，５００以下、３，０００以下、２，５００以下、２，０００以下、１，５００以下、１，２０００以下、又は１，０００以下であってよい。 The mass average molecular weight of humic acid may be 100-6,000. The lower limit of the mass average molecular weight of humic acid may be, for example, 200 or more, 300 or more, 400 or more, 500 or more, 600 or more, 700 or more, 800 or more, 900 or more, or 1000 or more. The upper limit of the mass average molecular weight of humic acid is, for example, 5,500 or less, 5,000 or less, 4,500 or less, 4,000 or less, 3,500 or less, 3,000 or less, 2,500 or less, 2,000 1,500 or less, 1,2000 or less, or 1,000 or less.
　腐植酸の質量平均分子量は、Ｗａｔｅｒｓ社製Ａｌｌｉａｎｃｅ　ＨＰＬＣ　Ｓｙｓｔｅｍを用い、ＨＰＳＥＣ法（ＧＰＣ法）により測定される。カラムは昭和電工株式会社製ＳＢ－８０３ＨＱ、標準試料はポリスチレンスルホン酸ナトリウムを用い、検出波長は２６０ｎｍとする。移動相は２５質量％アセトニトリル含有の１０ｍｍｏｌ／Ｌリン酸ナトリウム緩衝液とし、流速は０．８ｍｌ／分とし、カラムの温度は４０℃（カラムオーブンの設定値）とする。 The mass average molecular weight of humic acid is measured by the HPSEC method (GPC method) using Alliance HPLC System manufactured by Waters. The column is SB-803HQ manufactured by Showa Denko KK, the standard sample is sodium polystyrene sulfonate, and the detection wavelength is 260 nm. The mobile phase is 10 mmol/L sodium phosphate buffer containing 25% by mass of acetonitrile, the flow rate is 0.8 ml/min, and the column temperature is 40° C. (column oven setting).
　農業資材による薬害の抑制剤の剤型は、例えば、液剤又は粉剤であってよい。粉剤は、例えば、液剤である農業資材による薬害の抑制剤を凍結乾燥等によってドライアップすることにより、再溶解可能な粉剤として得ることができる。
　農業資材による薬害の抑制剤は、腐植酸のみからなっていてよく、腐植酸以外の他の成分を含んでいてよい。農業資材による薬害の抑制剤中の腐植酸の含有量は、農業資材による薬害の抑制剤の全質量を基準として、例えば、５質量％以上、１０質量％以上、２０質量％以上、３０質量％以上、４０質量％以上、５０質量％以上、６０質量％以上、７０質量％以上、８０質量％以上、９０質量％以上、又は９５質量％以上であってよく、１００質量％以下、９９質量％以下、又は９５質量％以下であってよい。 The dosage form of the inhibitor of phytotoxicity caused by agricultural materials may be, for example, a liquid formulation or a powder formulation. Powders can be obtained as redissolvable powders by, for example, drying up a liquid agent for suppressing phytotoxicity caused by agricultural materials by freeze-drying or the like.
The inhibitor of phytotoxicity caused by agricultural materials may consist of only humic acid, or may contain other ingredients than humic acid. The content of humic acid in the inhibitor of phytotoxicity caused by agricultural materials is, for example, 5% by mass or more, 10% by mass or more, 20% by mass or more, or 30% by mass, based on the total mass of the inhibitor of phytotoxicity caused by agricultural materials. 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more, 100% by mass or more, 99% by mass or more or less, or 95% by mass or less.
　農業資材による薬害の抑制剤は、農業資材と併用して用いることができる。例えば、農業資材として農薬を用いる場合、農薬と、腐植酸とを含む薬剤を対象に施用することによって、農薬による防除効果等を得ながら、農薬による薬害の発生を抑制することができる。 The inhibitor of chemical damage caused by agricultural materials can be used in combination with agricultural materials. For example, when an agricultural chemical is used as an agricultural material, by applying a chemical agent containing the agricultural chemical and humic acid to the target, it is possible to obtain the control effect of the agricultural chemical and suppress the occurrence of phytotoxicity caused by the agricultural chemical.
　本実施形態に係る作物体の農業資材による薬害を抑制する方法は、作物体に腐植酸を施用することを含む。 The method of suppressing phytotoxicity of crops caused by agricultural materials according to the present embodiment includes applying humic acid to crops.
　作物体に腐植酸を施用する方法として、作物体に対して散布、塗付等を行う方法、土壌潅注又は土壌混和等を行う方法が挙げられる。 Methods of applying humic acid to crop bodies include methods of spraying or coating crop bodies, and methods of soil irrigation or soil mixing.
　腐植酸の施用量及び施用期間は特に限られず、土壌施用の場合は全有機炭素濃度として０．１～５，０００ｍｇ／Ｌを月に１～１２回、水耕栽培の場合は全有機炭素濃度として０．１～５，０００ｍｇ／Ｌを月に１～１２回、葉面施用の場合は全有機炭素濃度として０．１～５，０００ｍｇ／Ｌで月に１～１２回とすることができる。 The amount and period of application of humic acid are not particularly limited. In the case of soil application, the total organic carbon concentration is 0.1 to 5,000 mg / L 1 to 12 times a month, and in the case of hydroponics, the total organic carbon concentration. as 0.1 to 5,000 mg/L 1 to 12 times a month, and in the case of foliar application, the total organic carbon concentration can be 0.1 to 5,000 mg/L and 1 to 12 times a month. .
　腐植酸を施用する作物体の部位は、作物体の全体又一部であり、作物体の種類、農業資材の種類等に応じて、適宜選択することができる。例えば、腐植酸を施用する作物体の部位は、作物体の葉等であってよい。
　腐植酸を施用するタイミングは、特に制限されず、作物体の種類、施用する農業資材の種類等に応じて適宜選択することができる。例えば、腐植酸は、農業資材が施用された作物体に施用してもよく、農業資材を施用する前の作物体に施用してもよく、農業資材の施用と同時に作物体に施用してもよい。 The portion of the crop body to which humic acid is applied is the whole or a part of the crop body, and can be appropriately selected according to the type of the crop body, the type of agricultural material, and the like. For example, the part of the crop body to which humic acid is applied may be the leaves of the crop body.
The timing of applying humic acid is not particularly limited, and can be appropriately selected according to the type of crop body, the type of agricultural material to be applied, and the like. For example, humic acid may be applied to the crop body to which the agricultural material has been applied, may be applied to the crop body before applying the agricultural material, or may be applied to the crop body at the same time as the application of the agricultural material. good.
　上述した本発明は、農業資材による薬害を抑制するための腐植酸の使用と捉えることもできる。上述した本発明は、農業資材による薬害の抑制に使用するための腐植酸と捉えることもできる。上述した本発明は、農業資材による薬害の抑制剤の製造のための腐植酸の使用（応用）と捉えることもできる。 The above-mentioned present invention can also be regarded as the use of humic acid to suppress phytotoxicity caused by agricultural materials. The present invention described above can also be regarded as humic acid for use in suppressing phytotoxicity caused by agricultural materials. The present invention described above can also be regarded as the use (application) of humic acid for the production of an inhibitor of chemical damage caused by agricultural materials.
　以下、実施例に基づいて本発明をより具体的に説明する。但し、本発明は、以下の実施例により限定されるものではない。 The present invention will be described more specifically below based on examples. However, the present invention is not limited by the following examples.
［腐植酸抽出液Ａの準備］
　ドラフト中で、炭素含有率が７７質量％の褐炭５００ｇを１,０００ｍｌのビーカーに入れて、濃度４８質量％の硝酸１５６２．５ｇ（若年炭１００質量部に対して１００％硝酸１５０質量部）を添加した。８０℃の水浴中で３時間酸化反応を行った。この操作で得た腐植酸を含む粗製物を以下の抽出操作に供した。
　この粗製物１００ｇに０．５ｍｏｌ／Ｌの水酸化カリウム水溶液を約４５０ｍＬ加え、ｐＨ計でモニタしながら１.０ｍｏｌ／Ｌの水酸化カリウム水溶液を適宜加えｐＨ２．０とした。固液比（抽出溶媒／若年炭）５：１となるように水を加え、８０℃で１時間抽出した。この抽出液を、３，０００×ｇで遠心分離し、得られた上澄み液は適宜希釈し、質量平均分子量、全有機炭素濃度（ＴＯＣ）及びメラニックインデックス（ＭＩ）を測定した。 [Preparation of humic acid extract A]
In a fume hood, 500 g of brown coal with a carbon content of 77% by mass is placed in a 1,000 ml beaker, and 1562.5 g of nitric acid with a concentration of 48% by mass (150 parts by mass of 100% nitric acid for 100 parts by mass of young coal) is added. added. An oxidation reaction was carried out in a water bath at 80°C for 3 hours. The crude product containing humic acid obtained by this operation was subjected to the following extraction operation.
About 450 mL of a 0.5 mol/L potassium hydroxide aqueous solution was added to 100 g of this crude product, and the pH was adjusted to 2.0 by adding a 1.0 mol/L potassium hydroxide aqueous solution appropriately while monitoring with a pH meter. Water was added so that the solid-liquid ratio (extraction solvent/juvenile charcoal) was 5:1, and extraction was carried out at 80° C. for 1 hour. This extract was centrifuged at 3,000×g, the obtained supernatant was diluted appropriately, and the weight average molecular weight, total organic carbon concentration (TOC) and melanic index (MI) were measured.
　腐植酸抽出液Ａ中の腐植酸のＭＩは４．８であった。腐植酸抽出液Ａの全有機炭素濃度（ＴＯＣ）は、２２，０００ｍｇ／Ｌであった。腐植酸抽出液Ａ中の腐植酸の質量平均分子量は５３０であった。 The MI of humic acid in humic acid extract A was 4.8. The total organic carbon concentration (TOC) of humic acid extract A was 22,000 mg/L. The mass average molecular weight of humic acid in the humic acid extract A was 530.
［質量平均分子量］
　腐植酸の質量平均分子量は、Ｗａｔｅｒｓ社製Ａｌｌｉａｎｃｅ ＨＰＬＣ Ｓｙｓｔｅｍを用い、ＨＰＳＥＣ法（ＧＰＣ法）により測定した。カラムは昭和電工株式会社製ＳＢ－８０３ＨＱ、標準試料はポリスチレンスルホン酸ナトリウムを用い、検出波長は２６０ｎｍとした。移動相は２５質量％アセトニトリル含有の１０ｍｍｏｌ／Ｌリン酸ナトリウム緩衝液とし、流速は０．８ｍｌ／分とし、カラムの温度は４０℃（カラムオーブンの設定値）とした。 [Mass average molecular weight]
The mass average molecular weight of humic acid was measured by HPSEC method (GPC method) using Alliance HPLC System manufactured by Waters. The column was SB-803HQ manufactured by Showa Denko KK, the standard sample was sodium polystyrene sulfonate, and the detection wavelength was 260 nm. The mobile phase was 10 mmol/L sodium phosphate buffer containing 25 mass % acetonitrile, the flow rate was 0.8 ml/min, and the column temperature was 40° C. (column oven setting).
［全有機炭素濃度（ＴＯＣ）］
　腐植酸抽出液ＡのＴＯＣは、全有機体炭素計（株式会社島津製作所製ＴＯＣ－Ｌ）を用い、燃焼触媒酸化方式で測定した。 [Total organic carbon concentration (TOC)]
The TOC of the humic acid extract A was measured by a combustion catalytic oxidation method using a total organic carbon meter (TOC-L manufactured by Shimadzu Corporation).
［メラニックインデックス（ＭＩ）］
　試料を乳鉢と２５０μｍ篩を用い２５０μｍ篩下品に粉砕した。その約１０ｇを、質量が既知の秤量ビンに取り精秤した。この秤量ビンを温度１０５℃に保持した乾燥機で約１２時間放置し、その後、デシケーター中で室温２０℃に戻してから再度精秤した。その質量減少分を水分とみなして試料の含水率を求めた。次に、５０ｍｌ遠沈管に、上記２５０μｍ篩下品を乾燥質量相当量で０．１０ｇと、０．５ｍｏｌ／Ｌ水酸化ナトリウム水溶液４５ｍｌとを入れ、室温２０℃で約１時間、２５０ｒｐｍの速度で振とうした後、３，０００×ｇ、約１０分間の遠心分離を実施し、その上澄み液をアドバンテック社製Ｎｏ．５Ｃの濾紙で濾過した。濾液の４５０ｎｍの吸光度と５２０ｎｍの吸光度を、蒸留水をブランクとして測定した。この場合、４５０ｎｍの吸光度が１．０以上を示したならば、０．１ｍｏｌ／Ｌ水酸化ナトリウム水溶液を添加し吸光度が０．８以上１．０未満に調整してから、５２０ｎｍの吸光度を測定した。５２０ｎｍでの吸光度に対する４５０ｎｍでの吸光度の比（４５０ｎｍでの吸光度／５２０ｎｍでの吸光度）を算出し、ＭＩとした。 [Melanic Index (MI)]
The sample was ground to a 250 μm sieve product using a mortar and 250 μm sieve. About 10 g of it was placed in a weighing bottle with a known mass and accurately weighed. This weighing bottle was allowed to stand for about 12 hours in a dryer maintained at a temperature of 105° C., then returned to room temperature of 20° C. in a desiccator, and then accurately weighed again. The moisture content of the sample was determined by considering the mass decrease as moisture. Next, in a 50 ml centrifuge tube, 0.10 g of the above 250 μm sieve product (dry mass equivalent) and 45 ml of 0.5 mol/L sodium hydroxide aqueous solution were placed, and the mixture was shaken at room temperature of 20° C. for about 1 hour at a speed of 250 rpm. After centrifugation, centrifugation was carried out at 3,000×g for about 10 minutes, and the supernatant was centrifuged in Advantech No. It was filtered through a 5C filter paper. Absorbance at 450 nm and 520 nm of the filtrate was measured using distilled water as a blank. In this case, if the absorbance at 450 nm shows 1.0 or more, add 0.1 mol/L sodium hydroxide aqueous solution to adjust the absorbance to 0.8 or more and less than 1.0, then measure the absorbance at 520 nm. did. The ratio of absorbance at 450 nm to absorbance at 520 nm (absorbance at 450 nm/absorbance at 520 nm) was calculated and designated as MI.
［試験例１：トマトへの病原菌接種試験１］
　以下の方法で対照区、試験区１（腐植酸抽出液Ａ　４０ｐｐｍ）、試験区２（０．４ｍＭ　ＣｕＳＯ４・５Ｈ２Ｏ）及び試験区３（腐植酸抽出液Ａ（４０ｐｐｍ）＋０．４ｍＭ　ＣｕＳＯ４・５Ｈ２Ｏ）の薬剤を準備した。 [Test Example 1: Pathogen inoculation test 1 to tomato]
Control group, test group 1 (humic acid extract A 40 ppm), test group 2 (0.4 mM CuSO 4 5H 2 O) and test group 3 (humic acid extract A (40 ppm) + 0.4 mM CuSO 4.5H 2 O) was prepared.
　トマト（品種レジナ）（２株／ポット、播種後、１９日齢、本葉２．５枚）に、各剤を噴霧処理し、培養庫に静置した（２４℃、１６時間（明）／８時間（暗）の明暗サイクル、湿度５０％）。処理３日後に、トマト斑葉細菌病菌Ｐｓｅｕｄｏｍｏｎａｓ　ｓｙｒｉｎｇａｅ（５×１０６ｃｆｕ／ｍｌ）を噴霧接種した（個体ごとに４～５回噴霧）。以上について、湿室下（２４℃、１６時間（明）／８時間（暗）の明暗サイクル）にて培養し、接種５日後に病徴を検定した。 Tomatoes (cultivar Regina) (2 strains/pot, 19 days old after seeding, 2.5 true leaves) were sprayed with each agent and allowed to stand in an incubator (24 ° C., 16 hours (light) / 8 hours (dark) light/dark cycle, 50% humidity). Three days after treatment, the plants were spray inoculated with Pseudomonas syringae (5×10 6 cfu/ml) (4-5 sprays per plant). The above plants were cultured in a moist room (24°C, 16 hours (light)/8 hours (dark) light/dark cycle), and disease symptoms were examined 5 days after inoculation.
　発病度は、次に示す方法によって算出した。結果を図１に示す。
　発病度は以下の式で表される。
発病度＝｛（１ｎ１＋２ｎ２＋３ｎ３＋４ｎ４＋５ｎ５）／（５×調査数）｝×１００
　発病調査は発病度を以下の５つに区分して調査した。
０：病徴なし、１：微小斑点、２：葉の２５％未満の面積に病斑が認められる、３：葉の２５％以上５０％未満の面積に病斑が認められる、４：葉の５０％以上の面積に病斑が認められる、５：落葉又は枯死
ｎ１からｎ５は個体数を示す。 The severity of disease was calculated by the method shown below. The results are shown in FIG.
The disease severity is expressed by the following formula.
Disease severity = {(1n1 + 2n2 + 3n3 + 4n4 + 5n5) / (5 x number of investigations)} x 100
The disease incidence was investigated by classifying the severity of disease into the following five categories.
0: no symptoms, 1: fine spots, 2: lesions are observed in less than 25% area of the leaves, 3: lesions are observed in 25% or more and less than 50% area of the leaves, 4: leaf Lesions are observed in 50% or more of the area. 5: defoliation or death n1 to n5 indicate the number of individuals.
　トマトに硫酸銅を単独で噴霧した場合、接種後に葉先が少しクロロシスになった。腐植酸抽出液Ａと、硫酸銅とを併せて噴霧した場合、薬害が抑えられる結果を得た。 When tomatoes were sprayed with copper sulfate alone, the tips of the leaves became a little chlorosis after inoculation. When the humic acid extract A and copper sulfate were sprayed together, a result was obtained in which phytotoxicity was suppressed.
［試験例２：ハクサイへの病原菌接種試験］
　ハクサイ苗（黄ごころ８５）（３株／ポット、１４日齢、展開葉２枚及び未展開葉２枚）に各薬剤を噴霧処理した。処理した株は、２４℃、１６時間（明）／８時間（暗）の明暗下で静置した。処理２日後にアブラナ科野菜黒斑細菌病菌Ｐｓｅｕｄｏｍｏｎａｓ　ｃａｎｎａｂｉｎａ　ｐｖ．　ａｌｉｓａｌｅｎｓｉｓ（５×１０６ｃｆｕ／ｍｌ）を噴霧接種した（個体ごとに４～５回噴霧）。接種後は湿室下（２４℃、１６時間（明）／８時間（暗）の明暗サイクル）に静置し、接種５日後に試験例１と同様の方法によって発病度を検定した。結果を図２に示す。 [Test Example 2: Pathogen inoculation test to Chinese cabbage]
Chinese cabbage seedlings (Yellow Gokoro 85) (3 strains/pot, 14 days old, 2 expanded leaves and 2 undeveloped leaves) were sprayed with each drug. The treated strains were allowed to stand at 24° C. under 16 hours (light)/8 hours (dark) of light and darkness. Two days after treatment, cruciferous vegetable black spot bacteria Pseudomonas cannabina pv. alisalensis (5×10 6 cfu/ml) was spray inoculated (4-5 sprays per animal). After inoculation, the plants were allowed to stand in a moist room (24° C., 16 hours (light)/8 hours (dark) light-dark cycle), and 5 days after inoculation, the disease severity was examined by the same method as in Test Example 1. The results are shown in FIG.
　図３は、病原菌接種５日後の各薬剤で処理したハクサイ苗の観察結果を示す写真である。
ハクサイを用いた場合でも、トマトと同様に薬害軽減の結果を得た。ハクサイは薬害がでやすいため、硫酸銅を単独で用いた場合には検定できないほどの薬害（白抜きの斑点、褐色斑点等）が出た。一方、腐植酸抽出液Ａと硫酸銅とを併用した場合には、薬害が抑えられていた。

  FIG. 3 is a photograph showing the observation results of Chinese cabbage seedlings treated with each drug 5 days after inoculation with the pathogen.
Even when Chinese cabbage was used, the result of reduction of phytotoxicity was obtained similarly to that of tomato. Since Chinese cabbage is prone to phytotoxicity, when copper sulfate was used alone, phytotoxicity (white spots, brown spots, etc.) occurred to the extent that it could not be tested. On the other hand, when the humic acid extract A and copper sulfate were used in combination, phytotoxicity was suppressed.

Claims (10)

  1. 　腐植酸を有効成分として含有する、農業資材による薬害の抑制剤。 An inhibitor of phytotoxicity caused by agricultural materials, containing humic acid as an active ingredient.
  2. 　メラニックインデックスが２．０以上である、請求項１に記載の農業資材による薬害の抑制剤。 The inhibitor of phytotoxicity caused by agricultural materials according to claim 1, which has a melanic index of 2.0 or more.
  3. 　前記腐植酸の質量平均分子量が１００～６，０００である、請求項１又は２に記載の農業資材による薬害の抑制剤。 The inhibitor of phytotoxicity caused by agricultural materials according to claim 1 or 2, wherein the humic acid has a mass average molecular weight of 100 to 6,000.
  4. 　前記有効成分が腐植酸抽出液であり、
    　前記腐植酸抽出液の全有機炭素濃度が１５，０００ｍｇ／Ｌ以上である、請求項１又は２に記載の農業資材による薬害の抑制剤。     The active ingredient is a humic acid extract,
    3. The agent for suppressing phytotoxicity caused by agricultural materials according to claim 1 or 2, wherein the humic acid extract has a total organic carbon concentration of 15,000 mg/L or more.
  5. 　前記腐植酸の質量平均分子量が１００～１，２００であり、
    　前記腐植酸抽出液の全有機炭素濃度が１５，０００～２５，０００ｍｇ／Ｌである、請求項４に記載の農業資材による薬害の抑制剤。     The humic acid has a mass average molecular weight of 100 to 1,200,
    5. The inhibitor of phytotoxicity caused by agricultural materials according to claim 4, wherein the humic acid extract has a total organic carbon concentration of 15,000 to 25,000 mg/L.
  6. 　褐炭由来である、請求項１又は２に記載の農業資材による薬害の抑制剤。 The inhibitor of phytotoxicity caused by agricultural materials according to claim 1 or 2, which is derived from lignite.
  7. 　前記農業資材が農薬である、請求項１又は２に記載の農業資材による薬害の抑制剤。 The inhibitor of phytotoxicity caused by agricultural materials according to claim 1 or 2, wherein the agricultural materials are agricultural chemicals.
  8. 　前記農薬が金属塩である、請求項７に記載の農業資材による薬害の抑制剤。 The inhibitor of phytotoxicity caused by agricultural materials according to claim 7, wherein the agricultural chemical is a metal salt.
  9. 　前記農薬が銅塩、亜鉛塩、及び鉄塩からなる群より選択される少なくとも１種の金属塩である、請求項７に記載の農業資材による薬害の抑制剤。 The inhibitor of chemical damage caused by agricultural materials according to claim 7, wherein the agricultural chemical is at least one metal salt selected from the group consisting of copper salts, zinc salts, and iron salts.
  10. 　作物体の農業資材による薬害を抑制する方法であって、
    　前記作物体に腐植酸を施用することを含む、方法。

          A method for suppressing phytotoxicity of crop bodies by agricultural materials, comprising:
    A method comprising applying humic acid to the crop body.
PCT/JP2023/005504 2022-02-17 2023-02-16 Inhibitor against crop injury due to agricultural material WO2023157929A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1593154A (en) * 2004-07-13 2005-03-16 田忠科 Copper humate agricultural chemicals bactericide for prevention and cure of fruit tree branch disease
CN103734190A (en) * 2014-01-23 2014-04-23 青岛农业大学 Film-coating therapeutic agent containing humic acid and chemical fungicide
CN109744054A (en) * 2017-11-07 2019-05-14 袁敬伟 A method of prevention and treatment apple tree canker
KR102327187B1 (en) * 2021-05-14 2021-11-17 주식회사 삼성컴퍼니 Herbicide composition with mineral elements

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1593154A (en) * 2004-07-13 2005-03-16 田忠科 Copper humate agricultural chemicals bactericide for prevention and cure of fruit tree branch disease
CN103734190A (en) * 2014-01-23 2014-04-23 青岛农业大学 Film-coating therapeutic agent containing humic acid and chemical fungicide
CN109744054A (en) * 2017-11-07 2019-05-14 袁敬伟 A method of prevention and treatment apple tree canker
KR102327187B1 (en) * 2021-05-14 2021-11-17 주식회사 삼성컴퍼니 Herbicide composition with mineral elements

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