Patent Application
20250176545
The present invention relates to a liquid pesticidal composition.
U.S. Pat. No. 9,743,664 (Patent Document 1) mentions that volatilization of an auxin herbicide can be inhibited by adding a monocarboxylic acid or a salt thereof and a base such as potassium hydroxide to a pesticidal composition comprising an auxin herbicide or a salt thereof.
When the above prior art is applied to a pesticidal composition comprising, in addition to an auxin herbicide, another specific pesticidal active compound, volatilization of the auxin herbicide can be inhibited, but there is a problem that the specific pesticidal active compound is decomposed.
An object of the present invention is to provide a pesticidal composition comprising an auxin herbicide, particularly a dicamba amine salt, and another specific pesticidal active compound, which is capable of inhibiting volatilization of the auxin herbicide and inhibiting decomposition of the specific pesticidal active compound.
The present invention provides the following liquid pesticidal compositions.
—C(═O)—X— (I)
It is possible to provide a pesticidal composition comprising an auxin herbicide, particularly a dicamba amine salt, and another specific pesticidal active compound, which is capable of inhibiting volatilization of the auxin herbicide and inhibiting decomposition of the specific pesticidal active compound.
The liquid pesticidal composition according to the present invention (hereinafter also simply referred to as “pesticidal composition”) comprises an auxin herbicide, a pesticidal active compound having a partial structure represented by formula (I) (hereinafter also referred to as “compound (I)”), and at least one selected from the group consisting of a polycarboxylic acid and a salt thereof. The pesticidal composition is usually a pesticidal formulation, and its form is not particularly limited as long as it is in a liquid. “Liquid” means that it exhibits fluidity at 25° C. The pesticidal composition may contain an aqueous phase, and preferably contains an aqueous phase and an oil phase.
A detailed description of ingredients that the pesticidal composition comprises or may comprise will now be given.
Examples of the auxin herbicides include benzoic acid herbicides and phenoxy herbicides.
Examples of the benzoic acid herbicides include dicamba and an agriculturally acceptable salt or ester thereof. In a preferred embodiment, the pesticidal composition comprises a dicamba amine salt. Examples of the dicamba amine salt include a dicamba diglycolamine salt, a dicamba monoethanolamine salt, a dicamba tetrabutylamine salt, a dicamba tetrabutylphosphonium salt, a dicamba N,N-bis(3-aminopropyl)methylamine (BAPMA) salt and a dicamba choline salt. The dicamba amine salt preferably includes at least one dicamba amine salt selected from a dicamba diglycolamine salt and a dicamba monoethanolamine salt, and more preferably includes a dicamba diglycolamine salt. In one embodiment, the pesticidal composition comprises a dicamba amine salt alone or two or more thereof. Some dicamba amine salts can exist in a neutral state in the pesticidal composition. That is, a carboxylate group (—COO− group) possessed by the dicamba amine salt may exist in equilibrium with a carboxy group (—COOH group). In the pesticidal composition, the dicamba amine salt is usually dissolved in the above aqueous phase.
When the total amount of the pesticidal composition is 100% by mass, the content of the dicamba amine salt in the pesticidal composition is preferably 0.1% by mass or more and 80% by mass or less, more preferably 0.5% by mass or more and 70% by mass or less, still more preferably 1% by mass or more and 60% by mass or less, yet more preferably 2% by mass or more and 50% by mass or less, and particularly preferably 5% by mass or more and 30% by mass or less. The content of the dicamba amine salt as used herein is the content of dicamba acid.
When the pesticidal composition comprises two or more dicamba amine salts, the content of the above-mentioned dicamba amine salt is the total content of two or more dicamba amine salts. The same applies to other ingredients that the pesticidal composition comprises or may comprise, and when comprising two or more ingredients, the content and concentration of the ingredients are the total content and total concentration thereof, unless otherwise specified.
The concentration of the dicamba amine salt in the pesticidal composition is usually 0.1 mol/L or more and 5 mol/L or less, preferably 0.2 mol/L or more and 4.5 mol/L or less, more preferably 0.3 mol/L or more and 4 mol/L or less, still more preferably 0.4 mol/L or more and 3.5 mol/L or less, and yet more preferably 0.5 mol/L or more and 3 mol/L or less. The concentration of the dicamba amine salt in the pesticidal composition is the value obtained by dividing the number of mols (mol), which is obtained by dividing the weight of the dicamba amine salt included in the pesticidal composition by the molecular weight, by the volume (L) of the pesticidal composition (mol/L).
Examples of the phenoxy herbicides include 2,4-D and an agriculturally acceptable salt or ester thereof. In a preferred embodiment, the pesticidal composition comprises a 2,4-D amine salt. Examples of the 2,4-D amine salt include a 2,4-D ammonium salt, a 2,4-D diethylammonium salt, a 2,4-D dimethylammonium salt, a 2,4-D diolamine salt, a 2,4-D dodecylammonium salt, a 2,4-D heptylammonium salt, a 2,4-D isopropylammonium salt, a 2,4-D tetradecylammonium salt, a 2,4-D triethylammonium salt, a 2,4-D tris(2-hydroxypropyl)ammonium salt, a 2,4-D trolamine salt and a 2,4-D choline salt. In one embodiment, the pesticidal composition comprises a 2,4-D amine salt alone, or two or more thereof. Some 2,4-D amine salts can exist in a neutral state in the pesticidal composition. That is, a carboxylate group (—COO− group) of the 2,4-D amine salt may exist in equilibrium with a carboxy group (—COOH group). In the pesticidal composition, the 2,4-D amine salt is usually dissolved in the above aqueous phase. The content of the 2,4-D amine salt in the pesticidal composition and the concentration of the 2,4-D amine salt in the pesticidal composition are equivalent to the content and concentration of the dicamba amine salt.
The compound (I) is a compound having a partial structure represented by formula (I).
—C(═O)—X— (I)
In the pesticidal composition, the compound (I) may be contained in the above aqueous phase, the above oil phase, or both the aqueous and oil phases when the pesticidal composition comprises two or more compounds (I).
In formula (I), X represents at least one selected from the group consisting of an oxygen atom and NR1, and R1 represents a monovalent group. That is, the compound (I) is a compound having one or more structures selected from the group consisting of an ester structure and an amide structure. The compound (I) may have two or more ester structures, two or more amide structures, or one or more ester structures and one or more amide structures. The pesticidal composition may also comprise two or more compounds (I).
The monovalent group represented by R1 is, for example, a hydrogen atom, a monovalent aliphatic group (including an alicyclic group, the same applies hereinafter), a monovalent aromatic group, and a monovalent group comprising a combination of an aliphatic structure and an aromatic structure, more preferably a monovalent aliphatic group, a monovalent aromatic group, and a monovalent group comprising a combination of an aliphatic structure and an aromatic structure, and still more preferably a monovalent aromatic group, and a monovalent group comprising a combination of an aliphatic structure and an aromatic structure. Each of the monovalent aliphatic group, the monovalent aromatic group, and the monovalent group comprising a combination of an aliphatic structure and an aromatic structure may have one or more substituents, and may also contain one or more heteroatoms. For example, one or more —CH2-(s) included in these monovalent groups may be substituted with —O—, —S—, —C(═O)—, —C(═S)—, or —N(R)— [R represents a hydrogen atom or a monovalent group].
According to the liquid pesticidal compositions of the present invention, when comprising a dicamba amine salt as an auxin herbicide, it is possible to inhibit volatilization of dicamba and to inhibit decomposition of the compound (I).
The decomposition of the compound (I) is typically accompanied by cleavage of a C—X bond in the above formula (I). The decomposition of the compound (I) is usually involved in a dicamba amine salt coexisting in the pesticidal composition. The decomposition of the compound (I) means the cleavage of at least one bond existing in the compound (I), and also includes the addition of other atoms or molecules to the cleaved site.
The compound (I) is preferably a herbicidal active compound. Examples of the herbicidal active compound include protoporphyrinogen oxidase (PPO) inhibitors, acetyl CoA carboxylase (ACCase) inhibitors, acetolactate synthase (ALS) inhibitors, acetohydroxyacid synthase (AHAS) inhibitors, photosystem I inhibitors, photosystem II inhibitors, carotenoid biosynthesis inhibitors, enolpyruvyl shikimate 3-phosphate (EPSP) synthase inhibitors, glutamine synthetase inhibitors, dihydropteroate synthase inhibitors, mitosis inhibitors, nucleic acid inhibitors and the like. Particularly, the compound (I) preferably comprises PPO inhibitors, and more preferably consists of PPO inhibitors.
Examples of the compound (I) include a compound represented by the following formula (I-1):
(hereinafter also referred to as “compound (I-1)”).
In formula (I-1), X is as defined above. R2 represents a monovalent group. R3 represents a monovalent group when X is an oxygen atom, and C(═O)—R4 when X is NR1. R4 represents a monovalent group, and R2 and R4 may form a ring together with the carbon atom to which R2 is bonded, X and the carbon atom to which R4 is bonded.
The monovalent group represented by R2, R3, and R4 each independently include, for example, a monovalent aliphatic group, a monovalent aromatic group, and a monovalent group comprising a combination of an aliphatic structure and an aromatic structure. Each of the monovalent aliphatic group, the monovalent aromatic group, and the monovalent group comprising a combination of an aliphatic structure and an aromatic structure may have one or more substituents, and may also contain one or more heteroatoms. The monovalent group represented by R2 is preferably a monovalent group comprising a combination of an aliphatic structure and an aromatic structure. When X is an oxygen atom, the monovalent group represented by R3 is preferably a monovalent aliphatic group, more preferably an alkyl group, still more preferably an alkyl group having 1 to 6 carbon atoms, and yet more preferably an alkyl group having 1 to 4 carbon atoms. The monovalent group represented by R4 is preferably a monovalent aliphatic group, or a monovalent group comprising a combination of an aliphatic structure and an aromatic structure.
Each of the monovalent aliphatic group, the monovalent aromatic group, and the monovalent group comprising a combination of an aliphatic structure and an aromatic structure may have one or more substituents, and may also contain one or more heteroatoms. For example, one or more —CH2-(s) included in these monovalent groups may be substituted with —O—, —S—, —C(═O)—, —C(═S)—, or —N(R)— [R represents a hydrogen atom or a monovalent group].
The compound (I-1) in which X is an oxygen atom and R3 is a monovalent group is a compound having an ester structure. The compound (I-1) in which X is NR1 and R3 is C(═O)—R4 is a compound having an imide structure. The compound having an imide structure may be a compound having a uracil ring structure. The uracil ring structure includes an imide structure. The compound having a uracil ring structure is a compound in which R2 and R4 may form a ring together with the carbon atom to which R2 is bonded, X and the carbon atom to which R4 is bonded in formula (I-1), and R2 and R4 are taken together to form —N(Ra)—C(Rb)═C(Rc)—. Ra, Rb, and Rc are each independently a hydrogen atom or a monovalent group.
Examples of the compound (I-1) having an imide structure include a compound represented by the following formula (I-1a):
(hereinafter also referred to as “compound (I-1a)”).
In formula (I-1a), R1, R2 and R4 are as defined above. R1 is preferably an aryl group or heteroaryl group which may have one or more substituents, more preferably a phenyl group or pyridyl group which may have one or more substituents, and still more preferably a phenyl group or 2-pyridyl group which may have one or more substituents. Examples of the substituent include a monovalent group which may contain one or more heteroatoms, a halogen atom and the like. The halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and preferably a fluorine atom or a chlorine atom.
The monovalent group represented by R2 and R4 each independently include, for example, a monovalent aliphatic group, a monovalent aromatic group, and a monovalent group comprising a combination of an aliphatic structure and an aromatic structure. Each of the monovalent aliphatic group, the monovalent aromatic group, and the monovalent group comprising a combination of an aliphatic structure and an aromatic structure may have one or more substituents, and may also contain one or more heteroatoms. The monovalent group represented by R2 is preferably a monovalent group comprising a combination of an aliphatic structure and an aromatic structure. The monovalent group represented by R4 is preferably a monovalent aliphatic group, or a monovalent group comprising a combination of an aliphatic structure and an aromatic structure.
R2 and R4 may form a ring together with the carbon atom to which R2 is bonded, an N atom and the carbon atom to which R4 is bonded.
Each of the monovalent aliphatic group, the monovalent aromatic group, and the monovalent group comprising a combination of an aliphatic structure and an aromatic structure may have one or more substituents, and may also contain one or more heteroatoms. For example, one or more —CH2-(s) included in these monovalent groups may be substituted with —O—, —S—, —C(═O)—, —C(═S)—, or —N(R)— [R represents a hydrogen atom or a monovalent group].
In one preferred embodiment, the compound (I-1a) is a compound represented by the following formula (I-1aa):
(hereinafter also referred to as “compound (I-1aa)”).
In formula (I-1aa), R2 and R4 are as defined above. R2 and R4 may form a ring together with the carbon atom to which R2 is bonded, an N atom and the carbon atom to which R4 is bonded.
Rd represents a fluorine atom or a hydrogen atom. Re represents monovalent group which may contain one or more heteroatoms. Rf represents a monovalent group or halogen atom which may contain one or more heteroatoms. Rf and RP may be taken together to form a ring. Z represents C—H or N (nitrogen atom). The above halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and preferably a chlorine atom.
A preferred example of the monovalent group which may contain one or more heteroatoms as for Re is —Y—Rg. Y represents an oxygen atom or a sulfur atom, and Rg represents a pyridyl group which may have one or more substituents.
In another preferred embodiment, the compound (I-1a) is a compound having a uracil ring structure. The uracil ring structure includes an imide structure. The compound (I-1a) having a uracil ring structure includes, for example, a compound represented by the following formula (I-1ab):
(hereinafter also referred to as “compound (I-1ab)”).
In formula (I-1ab), R1, Ra, Rb and Rc are as defined above. R1 is preferably an aryl group or heteroaryl group which may have one or more substituents, more preferably a phenyl group or pyridyl group which may have one or more substituents, still more preferably a phenyl group or 2-pyridyl group which may have one or more substituents. Examples of the substituent include a monovalent group which may contain one or more heteroatoms, a halogen atom and the like. The halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and preferably a fluorine atom or a chlorine atom.
Ra and Rb are preferably a monovalent group, more preferably an alkyl group or amino group which may be substituted with a halogen atom, still more preferably an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom, yet more preferably an alkyl group having 1 or 2 carbon atoms which may be substituted with a halogen atom, and particularly preferably a methyl group which may be substituted with a halogen atom. The halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and preferably a fluorine atom. In one embodiment, Ra is an alkyl group which is not substituted with a halogen atom, and Rb is a perfluoroalkyl group. Each of the number of carbon atoms of the alkyl group and the perfluoroalkyl group is preferably 1 to 4, more preferably 1 or 2, and still more preferably 1.
Rc is a hydrogen atom or an alkyl group, and preferably a hydrogen atom.
A preferred example of the compound (I-1ab) is preferably a compound in which R1 is a phenyl group or pyridyl group which may have one or more substituents, Rc is a methyl group, and R1 is a trifluoromethyl group.
The compound (I-1ab) includes, for example, a compound represented by the following formula (I-1ab′) (hereinafter referred to as “compound (I-1ab′)”).
In formula (I-1ab′), Rd, Re and Rf are the same as defined above. Specifically, Rd represents a fluorine atom or a hydrogen atom. Re represents a monovalent group which may contain one or more heteroatoms. Rf represents a monovalent group which may contain one or more heteroatoms, or a halogen atom. Rf and Re may be taken together to form a ring. Z represents C—H or N (nitrogen atom). The above halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and preferably a fluorine atom or a chlorine atom.
A preferred example of the monovalent group which may contain one or more heteroatoms as for Re is —Y—Rg. Y represents an oxygen atom or a sulfur atom, and RU represents a pyridyl group which may have one or more substituents.
Specific example of the compound (I-1ab′) is a compound represented by the following formula (I-A) (hereinafter also referred to as “compound (I-A)”), and the compound is a PPO inhibitor.
Examples of the compound (I-1aa) other than the compound having a uracil ring structure include a compound represented by the following formula (I-1aa′) (hereinafter also referred to as “compound (I-1aa′)”).
In formula (I-1aa′), a ring comprising an N atom represents a cyclic imide structure. Rd, Re and Rf are as defined above. Specifically, Rd represents a fluorine atom or a hydrogen atom. Re represents a monovalent group which may contain one or more heteroatoms. Rf represents a monovalent group which may contain one or more heteroatoms, or a halogen atom. Rf and Re may be taken together to form a ring. Z represents C—H or N (nitrogen atom). The above halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and preferably a chlorine atom.
Examples of the cyclic imide structure include a succinimide structure, a glutalimide structure, a phthalimide structure, a tetrahydrophthalimide structure and the like.
A preferred example of the monovalent group which may contain one or more heteroatoms as for Re is —Y—Rg. Y represents an oxygen atom or a sulfur atom, and Rg represents a pyridyl group which may have one or more substituents.
Specific examples of the compound (I-1aa′) are compounds represented by the following formulas (I-B) and (I-C) (hereinafter also referred to as “compounds (I-B) and (I-C)”, respectively), and these are both PPO inhibitors.
The compound having an ester structure (I-1) is a compound represented by the following formula (I-1b) (hereinafter also referred to as “compound (I-1b)”).
In formula (I-1b), R2 and R3 are as defined above. The monovalent group represented by R2 and R3 each independently include, for example, a monovalent aliphatic group, a monovalent aromatic group, a monovalent group comprising a combination of an aliphatic structure and an aromatic structure. Each of the monovalent aliphatic group, the monovalent aromatic group, and the monovalent group comprising a combination of an aliphatic structure and an aromatic structure may have one or more substituents, and may also contain one or more heteroatoms. The monovalent group represented by R2 is preferably a monovalent group comprising a combination of an aliphatic structure and an aromatic structure. The monovalent group represented by R3 is preferably a monovalent aliphatic group, more preferably an alkyl group, still more preferably an alkyl group having 1 to 6 carbon atoms, and yet more preferably an alkyl group having 1 to 4 carbon atoms.
Each of the monovalent aliphatic group, the monovalent aromatic group, and the monovalent group comprising a combination of an aliphatic structure and an aromatic structure may have one or more substituents, or may also contain one or more heteroatoms. For example, one or more —CH2-(s) included in these monovalent groups may be substituted with —O—, —S—, —C(═O)—, —C(═S)—, or —N(R)— [R represents a hydrogen atom or a monovalent group].
The compound (I-1b) includes, for example, a compound represented by the following formula (I-1ba) (hereinafter referred to as “compound (I-1ba)”).
In formula (I-1ba), Rh represents an alkyl group. Rh is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably an alkyl group having 1 or 2 carbon atoms. A plurality of Ri(s) may be the same or different from each other, and each independently represent a hydrogen atom, a halogen atom, or a monovalent group which may contain one or more heteroatoms. L represents an alkylene group which may have a substituent. One or more —CH2-(s) included in the alkylene group may be substituted with —O—, —S—, —C(═O)—, —C(═S)—, or —N(R)— [R represents a hydrogen atom or a monovalent group]. The number of carbon atoms of the alkylene group is, for example, 2 to 6, and preferably 2 or 3. Examples of the substituent, which may be possessed by the alkylene group, include a halogen atom. Z represents C—H or N (nitrogen atom).
A preferred example of the compound (I-1ba) is a compound represented by the following formula (I-1ba′) (hereinafter also referred to as “compound (I-1ba′)”).
In formula (I-1ba′), Rh and Z are as defined above. Rj represents a monovalent group which may contain one or more heteroatoms.
Specific examples of the compound (I-1ba′) are the above-mentioned compound (I-A) and compound (I-C), and these are both PPO inhibitors.
When the total amount of the pesticidal composition is 100% by mass, the content of the compound (I) in the pesticidal composition is preferably 0.01% by mass or more and 25% by mass or less, more preferably 0.05% by mass or more and 20% by mass or less, still more preferably 0.1% by mass or more and 15% by mass or less, and yet more preferably 0.2% by mass or more and 10% by mass or less, in order to improve the storage stability of the pesticidal composition while appropriately increasing the content.
The pesticidal composition may comprise one or more pesticidal active compounds other than the auxin herbicide and the compound (I). Examples of the pesticidal active compounds other than the auxin herbicide and the compound (I) include, but are not particularly limited to, an insecticidal active ingredient, a fungicidal active ingredient, a herbicidal active ingredient, a plant growth regulation active ingredient and a phytotoxicity reduction active ingredient, of which a herbicidal active ingredient is preferable.
Examples of the herbicidal active compounds include protoporphyrinogen oxidase (PPO) inhibitors, acetyl CoA carboxylase (ACCase) inhibitors, acetolactate synthase (ALS) inhibitors, acetohydroxyacid synthase (AHAS) inhibitors, photosystem I inhibitors, photosystem II inhibitors, carotenoid biosynthesis inhibitors, enolpyruvyl shikimate 3-phosphate (EPSP) synthase inhibitors, glutamine synthetase inhibitors, dihydropteroate synthase inhibitors, mitosis inhibitors, nucleic acid inhibitors and the like.
When the total amount of the pesticidal active compound included in the pesticidal composition is 100% by mass, the total content of the auxin herbicide and the compound (I) in all the pesticidal active compounds included in the composition is, for example, 50% by mass or more and 100% by mass or less. The content is preferably 60% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, still more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less.
The pesticidal composition comprises at least one selected from the group consisting of a polycarboxylic acid and a salt thereof. As used herein, “polycarboxylic acid” means a compound having two or more carboxy groups in one molecule. Hereinafter, polycarboxylic acid and polycarboxylate are also collectively referred to as “polycarboxylic acids”. According to the pesticidal composition comprising polycarboxylic acids, it is possible to inhibit volatilization of the auxin herbicide and to inhibit decomposition of the compound (I). Meanwhile, when using a monocarboxylic acid or a salt thereof instead of polycarboxylic acids, it is possible to inhibit volatilization of the auxin herbicide, but it is impossible to inhibit decomposition of the compound (I). The pesticidal composition may comprise two or more polycarboxylic acids, two or more polycarboxylates, one or more polycarboxylic acids, and one or more polycarboxylates.
All carboxy groups of the polycarboxylate may be in a salt form, or some carboxy groups of the plurality of carboxy groups may be in a salt form. The salt form of the carboxy group is represented by the formula: —COO-M|, where M| is a cation. Examples of the polycarboxylate include alkali metal salts such as a sodium salt and a potassium salt, alkaline earth metal salts such as a magnesium salt and a calcium salt, and an amine salt.
The polycarboxylic acid and the polycarboxylate are preferably a polymer (including an oligomer). The polymer means a polymer of a monomer having one or more carboxy groups or —COO-M+ groups. Hereinafter, the polycarboxylic acid, which is a polymer, is also referred to as “polycarboxylic acid polymer”, and the polycarboxylate, which is a polymer, is also referred to as “polycarboxylate polymer”. The polycarboxylic acid polymer and the polycarboxylate polymer have two or more carboxy groups and/or —COO-M+ groups, and preferably ten or more groups. The number of carboxy groups and —COO-M+ groups possessed by the polycarboxylic acid polymer and the polycarboxylate polymer depends on the molecular weight (degree of polymerization) of the polymer.
The polycarboxylic acid polymer and the polycarboxylate polymer may be either a homopolymer of a monomer having carboxy groups or —COO-M+ groups, or a copolymer of a monomer having carboxy groups or —COO−M+ groups and other monomers copolymerizable with the monomer. The polycarboxylic acid polymer and the polycarboxylate polymer are preferably water soluble.
Examples of the monomer having carboxy groups or —COO−M| groups include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and o-, m- and p-vinylbenzoic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid; and salts thereof. The polycarboxylic acid polymer and the polycarboxylate polymer can include two or more constituent units derived from a monomer having carboxy groups or —COO-M+ groups.
Examples of other monomers mentioned above include acrylic acid ester, methacrylic acid ester, vinyl alcohol, acrylamide and the like. The polycarboxylic acid polymer and the polycarboxylate polymer can include two or more constituent units derived from other monomers.
Examples of the polycarboxylic acid polymer and the polycarboxylate polymer include polyacrylic acid, polymethacrylic acid, alkali metal salts (sodium salt, potassium salt, etc.) of polyacrylic acid or polymethacrylic acid, acrylic acid-maleic acid copolymer, methacrylic acid-maleic acid copolymer, acrylic acid-maleic acid copolymer or alkali metal salts (sodium salt, potassium salt, etc.) of acrylic acid-maleic acid copolymer and the like.
The molecular weight (Mw) of the polycarboxylic acid polymer and the polycarboxylate polymer is preferably 200 or more, more preferably 500 or more, still more preferably 1,000 or more, yet more preferably 1,200 or more, further preferably 1,500 or more, still further preferably 2,000 or more, particularly preferably 2,500 or more, and most preferably 4,000 or more. When Mw is within the above range, it is possible to effectively inhibit decomposition of the compound (I). Mw is preferably 250,000 or less, more preferably 200,000 or less, still more preferably 150,000 or less, yet more preferably 100,000 or less, further preferably 75,000 or less, still further preferably 50,000 or less, particularly 30,000 or less, and most preferably 25,000 or less. When Mw is within the above range, the polycarboxylic acid polymer and the polycarboxylate polymer easily become water soluble, and as a result, it becomes easier to prepare a formulation.
When the auxin herbicide included in the pesticidal composition is a dicamba amine salt, the content of polycarboxylic acids in the pesticidal composition is preferably 0.1 mol or more and 10 mol or less, more preferably 0.2 mol or more and 8 mol or less, still more preferably 0.3 mol or more and 6 mol or less, yet more preferably 0.4 mol or more and 4 mol or less, and particularly preferably 0.5 mol or more and 2 mol or less, based on 1 mol of dicamba acid, when the amount of the dicamba amine salt is expressed by the amount of dicamba acid constituting the dicamba amine salt, and the amount of the polycarboxylic acids is expressed as the amount of one molecule of monocarboxylic acid constituting the polycarboxylic acids. When the content of polycarboxylic acids is within the above range, it is possible to effectively inhibit decomposition of the compound (I) while moderately inhibiting the volatility of dicamba.
The pesticidal composition may further comprise a basic component. The basic component can function as a pH adjuster to adjust the pH of the pesticidal composition. The basic component is preferably water soluble. The pesticidal composition may comprise two or more basic components. The basic component as used herein does not include the above-mentioned polycarboxylates which exhibit the basicity.
Examples of the basic components include organic bases such as diglycolamine, monoethanolamine and polyethyleneimine; and inorganic bases. The basic component is preferably an inorganic base, and more preferably an alkali metal salt. Examples of the alkali metal salts include alkali metal hydroxides, alkali metal carbonates and alkali metal bicarbonates. Of these, the basic component is preferably an alkali metal hydroxide. Examples of the alkali metal hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide and the like, of which and sodium hydroxide and potassium hydroxide are preferable. When the pesticidal composition further comprises a basic component, it is preferred that the pesticidal composition comprises at least one alkali metal hydroxide selected from the group consisting of potassium hydroxide and sodium hydroxide.
The content of the basic component in the pesticidal composition is preferably adjusted in consideration of the pH value of the pesticidal composition. The pH value at 25° C. of the pesticidal composition is preferably 4.0 or more and 9.0 or less, more preferably 4.2 or more and 8.5 or less, still more preferably 4.4 or more and 8.0 or less, yet more preferably 4.6 or more and 7.5 or less, further preferably 4.7 or more and 7.0 or less, still further preferably 4.8 or more and 6.5 or less, still more further preferably 4.9 or more and 6.0 or less, and most preferably 5.0 or more and 5.8 or less. When the pH value at 25° C. of the pesticidal composition is within the above range, it is possible to more effectively inhibit decomposition of the compound (I). The pH value of the pesticidal composition can be measured by charging the pesticidal composition in a glass container, shaking the glass container by hand, and dipping an electrode of a pH meter in the pesticidal composition.
The content of the basic component in the pesticidal composition is preferably the amount such that the pH value at 25° C. of the pesticidal composition is within the above range. The concentration of the basic component in the pesticidal composition is, for example, 0.0001 mol/L or more and 0.050 mol/L or less, preferably 0.0005 mol/L or more and 0.040 mol/L or less, more preferably 0.00075 mol/L or more and 0.030 mol/L or less, still more preferably 0.001 mol/L or more and 0.025 mol/L or less, and yet more preferably 0.002 mol/L or more and 0.020 mol/L or less.
The pesticidal composition may comprise no basic component. An example of the pesticidal composition comprising no basic component is a pesticidal composition in which the pH value at 25° C. of the pesticidal composition is adjusted within the above range by the inclusion of polycarboxylic acids. For example, use of polycarboxylic acid and polycarboxylate in combination as polycarboxylic acids enables adjustment of the pH value at 25° C. of the pesticidal composition within the above range without further inclusion of the basic component.
The pesticidal composition can comprise an organic solvent. The organic solvent constitutes the above oil phase. The organic solvent is preferably an organic solvent capable of dissolving the compound (I). The pesticidal composition can comprise one or more organic solvents.
The organic solvent preferably has water solubility at 25° C. of 10% by mass or less. The water solubility may be 8% by mass or less, 5% by mass or less, 3% by mass or less, or 1% by mass or less. It is preferable for the pesticidal composition to comprise an organic solvent having water solubility within the above range because the storage stability of the pesticidal composition is improved. The water solubility at 25° C. of the organic solvent is usually 0% by mass or more, and may be 10-5% by mass or more.
As used herein, the water solubility at 25° C. refers to the solubility in water at a temperature of 25° C. and a pH of 7. For example, the solubility of 10% by mass in water at 25° C. means the solubility of 1×10−1 g in 1 g of water at a temperature of 25° C. and a pH of 7.
It is possible to adopt, as the water solubility of the organic solvent, the numerical value listed in the database (Solubility Database) of the International Union of Pure and Applied Chemistry (IUPAC) or the National Institute of Standards and Technology (NIST) of the United States. If not listed in the database, the water solubility of the organic solvent can be measured by quantifying the saturated solubility in water at a temperature of 25° C. and a pH of 7 using high-performance liquid chromatography.
Examples of the organic solvent capable of dissolving the compound (I) include:
From the viewpoint of the solubility of the compound (I) and the storage stability of the pesticidal composition, the organic solvent preferably includes one or more types selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, ketones, esters, ethers, amides, amines and alcohols, and more preferably aromatic hydrocarbons. The aromatic hydrocarbon preferably includes one or more types selected from the group consisting of alkylbenzenes (for example, toluene, xylene, ethylbenzene, octadecylbenzene, dialkylbenzene and trialkylbenzene), alkylnaphthalenes (for example, methylnaphthalene, dimethylnaphthalene, dodecylnaphthalene and tridecylnaphthalene), phenyl xylyl ethane and 1-phenyl-1-ethylphenylethane, more preferably one or more types selected from the group consisting of alkylbenzenes and alkylnaphthalenes, and still more preferably one or more types selected from the group consisting of C9-C12 alkylbenzenes and C10-C15 alkylnaphthalenes. The organic solvent may be composed of an aromatic hydrocarbon.
When the total amount of the pesticidal composition is 100% by mass, the content of the organic solvent in the pesticidal composition is preferably 0.1% by mass or more and 45% by mass or less, more preferably 0.5% by mass or more and 40% by mass or less, still more preferably 1% by mass or more and 35% by mass or less, and yet more preferably 3% by mass or more and 30% by mass or less. It is preferable for the pesticidal composition to comprise the organic solvent in the content within the above range from the viewpoint of improving the storage stability of the pesticidal composition while moderately increasing the content of the compound (I).
The content of the organic solvent is usually 1 mass times or more and 50 mass times or less, preferably 2 mass times or more and 40 mass times or less, more preferably 3 mass times or more and 30 mass times or less, still more preferably 4 mass times or more and 25 mass times or less, yet more preferably 5 mass times or more and 20 mass times or less, further preferably 6 mass times or more and 20 mass times or less, still further preferably 7 mass times or more and 20 mass times or less, and particularly preferably 8 mass times or more and 20 mass times or less, the content of the compound (I). It is preferable to adjust the ratio (mass ratio) of the content of the organic solvent to the content of the compound (I) within the above range from the viewpoint of improving the storage stability of the pesticidal composition while moderately increasing the content of the compound (I).
The pesticidal composition can comprise water. Examples of water include ion-exchanged water, tap water and underground water. Water constitutes the above aqueous phase of the pesticidal composition.
When the total amount of the pesticidal composition is 100% by mass, the content of water in the pesticidal composition is preferably 30% by mass or more and 95% by mass or less, more preferably 35% by mass or more and 90% by mass or less, still more preferably 40% by mass or more and 80% by mass or less, and yet more preferably 45% by mass or more and 75% by mass or less. It is preferable for the pesticidal composition to comprise water in the content within the above range from the viewpoint of improving the suspended or emulsified state of the pesticidal composition.
The pesticidal composition may comprise an auxiliary agent for formulation. Examples of the auxiliary agents for formulation include surfactants, thickeners, defoamers, anti-freezing agents, preservatives and the like.
Examples of the surfactants include nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants. The pesticidal composition can comprise one or more surfactants selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants.
Examples of the nonionic surfactants include:
Examples of the anionic surfactants include:
Examples of salts in the above sulfonates, sulfates, carboxylates and phosphates include sodium salts, potassium salts, calcium salts, ammonium salts, isopropylamine salts, triethanolamine salts and the like.
Examples of the cationic surfactants include:
Examples of the amphoteric surfactants include N-laurylalanine, N,N,N-trimethylaminopropionic acid, N,N,N-trihydroxyethylaminopropionic acid, N-hexyl-N,N-dimethylaminoacetic acid, betaine, alkyl betaines (for example, 1-(2-carboxyethyl)pyrimidinium betaine), imidazoline, taurine, alkyl taurine and lecithin.
From the viewpoint of improving the suspended or emulsified state of the pesticidal composition, when the total amount of the pesticidal composition is 100% by mass, the content of the surfactant in the pesticidal composition is preferably 0.5% by mass or more and 30% by mass or less, more preferably 0.7% by mass or more and 25% by mass or less, still more preferably 0.8% by mass or more and 20% by mass or less, yet more preferably 1% by mass or more and 15% by mass or less, and particularly preferably 1.5% by mass or more and 10% by mass or less.
The content of the surfactant is preferably 0.05 mass times or more and 30 mass times or less, more preferably 0.07 mass times or more and 25 mass times or less, still more preferably 0.1 mass times or more and 20 mass times or less, and particularly preferably 0.1 mass times or more and 15 mass times or less, the content of the pesticidal active compound.
Examples of the thickeners include polysaccharides such as xanthan gum, guar gum, Welan gum, Diutan gum and cellulose nanofiber, clay, silicates and the like. When the total amount of the pesticidal composition is 100% by mass, the content of the thickener in the pesticidal composition is usually 0.01% by mass or more and may be 0.05% by mass or more or 0.1% by mass or more, and is usually 5% or less and may be 3% by mass or less.
Examples of the defoamers include silicone-based defoamers. When the total amount of the pesticidal composition is 100% by mass, the content of the defoamer in the pesticidal composition is usually 0.01% by mass or more and may be 0.05% by mass or more or 0.1% by mass or more, and is usually 1% by mass or less and may be 0.5% by mass or less.
Examples of the anti-freezing agents include ethylene glycol, propylene glycol, urea, glycerin and the like. When the total amount of the pesticidal composition is 100% by mass, the content of the anti-freezing agent in the pesticidal composition is usually 1% by mass or more and may be 2% by mass or more, and is usually 10% by mass or less or may be 8% by mass or less.
Examples of the preservatives include isothiazolinone preservatives. When the total amount of the pesticidal composition is 100% by mass, the content of the preservative in the pesticidal composition is usually 0.05% by mass or more and may be 0.1% by mass or more, and is usually 0.5% by mass or less and may be 0.3% by mass or less.
It is possible to prepare a pesticidal composition in which a dicamba amine salt is contained in an aqueous phase and the compound (I) is suspended in an aqueous phase, for example, in the following manner. The dicamba amine salt, the compound (I), water, a surfactant and, if necessary, an auxiliary agent for formulation are ground and suspended by a wet grinding method using media such as glass beads or zirconia to obtain a suspension. The suspension does not have to contain the dicamba amine salt. If not, the resulting suspension is mixed with the dicamba amine salt to obtain a mixture. The suspension or mixture is mixed with polycarboxylic acids and, if necessary, the auxiliary agent for formulation, such as a thickener, a preservative or a defoamer to obtain a pesticidal composition.
It is possible to prepare a pesticidal composition which is an oil-in-water emulsion containing a dicamba amine salt in an aqueous phase and the compound (I) in an oil phase, for example, in the following manner. The compound (I), an organic solvent and, if necessary, a surfactant are mixed to prepare an oil phase. Meanwhile, the dicamba amine salt, an auxiliary agent for formulation, water and, if necessary, a surfactant are added to prepare an aqueous phase. The surfactant may be added to the organic solvent or water, or may be added to both. The oil phase is added to the aqueous phase, followed by emulsification with a stirrer such as a homogenizer to obtain an emulsion. The emulsion is mixed with polycarboxylic acids and, if necessary, a basic component and an auxiliary agent for formulation, such as a thickener, a preservative or a defoamer to obtain a pesticidal composition.
It is possible to prepare a pesticidal composition which is an oil-in-water emulsion containing a dicamba amine salt in an aqueous phase, the compound (I) (first compound (I)) suspended in an aqueous phase and the other compound (I) (second compound (I)) in an oil phase, for example, in the following manner. The second compound (I), an organic solvent and, if necessary, a surfactant are mixed to prepare an oil phase. Meanwhile, the dicamba amine salt, an auxiliary agent for formulation, water and, if necessary, a surfactant are added to prepare an aqueous phase. The surfactant may be added to the organic solvent or water, or may be added to both. Further, the first compound (I), water, a surfactant, and, if necessary, other auxiliary agent for formulation are ground and suspended by a wet grinding method using media such as glass beads or zirconia to obtain a suspension. The oil phase is added to the aqueous phase, followed by emulsification with a stirrer such as a homogenizer to obtain an emulsion. The emulsion is mixed with the suspension, polycarboxylic acids and, if necessary, a basic component and an auxiliary agent for formulation, such as a thickener, a preservative or a defoamer to obtain a pesticidal composition.
It is possible to suitably use the pesticidal composition as a liquid pesticidal formulation called suspension concentrate (SC), emulsifiable concentrate (EC), emulsion oil in water (EW), suspoemulsion (SE), microemulsion (ME), microcapsule (MC) or soluble concentrate (SL) in the field of pesticides.
The pesticidal composition is capable of controlling weeds by use in agricultural lands such as fields, orchards, pastures, lawns and forestry lands; and non-crop areas such as bank slopes, riverbeds, road shoulders and slopes, railroad beds, parks, grounds, parking lots, airports, industrial sites such as factories and storage facilities, fallow lands and idle lands in urban areas.
The user usually mixes the pesticidal composition with water to prepare a suspension or emulsion, which is then sprayed with a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. The spray volume varies depending on the climatic conditions, treatment time, soil conditions, target crops, target weeds and the like, but is usually 10 L or more and 2,000 L or less, and preferably 50 L or more and 400 L or less, per hectare. The suspension or emulsion is prepared by mixing the suspension or emulsion with water, which is usually 2 to 10,000 times, preferably 10 to 8,000 times, and more preferably 15 to 6,000 times, the volume of the suspension or emulsion, respectively.
When the suspension or emulsion is applied, an adjuvant may be used in combination. Although there is no particular limitation on type of the adjuvant, in the case of oil-based adjuvants such as Agri-Dex and MSO (mineral oils such as paraffinic hydrocarbons, naphthenic hydrocarbons, aromatic hydrocarbons, or Methylated Seed Oil obtained by esterifying vegetable oils (soybean oil or rapeseed oil)), 0.25%, 0.5%, 1%, 2%, 3%, 4%, 5% or 6% (volume/volume) of the adjuvants are preferably mixed in the spray liquid. In the case of nonionic adjuvants such as Induce (polyoxyalkylene alkyl ethers, polyoxyalkylene fatty acid esters, alkyl aryl alkoxylates or alkyl aryl polyoxyalkylene glycols), 0.05%, 0.1%, 0.25% or 0.5% (volume/volume) of the adjuvants are preferably mixed in the spray liquid. It is possible to exemplify anionic adjuvants (substituted sulfonates) such as Gramine S, cationic adjuvants (polyoxyethylene amines) such as Genamin T 200BM, and organosilicone-based adjuvants such as Silwet L77. It is also possible to mix drift reducers such as Intact (polyethylene glycol), and/or volatilization reducers such as Vapex and a VaporGrip Xtra Agent (mixture of potassium hydroxide and acetic acid). There is no particular limitation on pH and hardness of the above spray liquid.
Hereinafter, the present invention will be described in more detail by way of Examples, Comparative Examples and the like, but the present invention is not limited by these Examples.
Ingredients used in the preparation of the liquid pesticidal compositions are shown below.
0.53 Part by mass of the compound (I-A) and 1.00 parts by mass of Pluronic P-104 were mixed with 5.25 parts by mass of Solvesso 200ND to prepare 6.775 parts by mass of an oil phase. To a mixed solution of 37.21 parts by mass of an aqueous Dicamba DGA solution (concentration of dicamba acid: 39.5% by mass) and 0.067 part by mass of XIAMETER ACP-1500, the above oil phase was added, and then the mixture was emulsified by stirring using a Polytron homogenizer (manufactured by KINEMATICA AG) to obtain 44.06 parts by mass of an emulsion (A1) of a pesticidal active compound.
<Preparation of Emulsion (A2) of Pesticidal Active Compound containing Dicamba MEA>
0.53 Part by mass of the compound (I-A) and 1.00 parts by mass of Pluronic P-104 were mixed with 5.25 parts by mass of Solvesso 200ND to prepare 6.775 parts by mass of an oil phase. To a mixed solution of 26.25 parts by mass of an aqueous Dicamba MEA solution (concentration of dicamba acid: 56.0% by mass) and 0.067 part by mass of XIAMETER ACP-1500, the above oil phase was added, and then the mixture was emulsified by stirring using a Polytron homogenizer (manufactured by KINEMATICA AG) to obtain 33.10 parts by mass of an emulsion (A2) of a pesticidal active compound.
0.53 Part by mass of the compound (I-A) was mixed with 5.25 parts by mass of Solvesso 200ND to prepare 5.775 parts by mass of an oil phase. To a mixed solution of 37.21 parts by mass of an aqueous Dicamba DGA solution (concentration of dicamba acid: 39.5% by mass), 0.067 part by mass of XIAMETER ACP-1500 and 3.89 parts by mass of an aqueous Selvol 523 solution (concentration of Selvol 523: 9% by mass), the above oil phase was added, and then the mixture was emulsified by stirring using a Polytron homogenizer (manufactured by KINEMATICA AG) to obtain 46.95 parts by mass of an emulsion (A3) of a pesticidal active compound.
To 14.72 parts by mass of ion-exchanged water, 0.40 part by mass of Veegum R, 0.067 part by mass of XIAMETER ACP-1500, 4.00 parts by mass of Reax910, 0.50 part by mass of Synperonic PE/F 127 and 2.28 parts by mass of the compound (I-B) were added, and after stirring and mixing, the mixture was wet-ground using a bead mill (product name: DYNO-MILL, manufactured by SHINMARU ENTERPRISES CORPORATION, glass bead diameter: 1.0 mm, filling rate: 80%, peripheral speed: 10 m/s) to obtain 21.97 parts by mass of a suspension (B1) of a pesticidal active compound.
To 14.72 parts by mass of ion-exchanged water, 0.40 part by mass of Veegum R, 0.067 part by mass of XIAMETER ACP-1500, 4.00 parts by mass of Reax910, 0.50 part by mass of Synperonic PE/F 127 and 2.28 parts by mass of the compound (I-C) were added, and after stirring and mixing, the mixture was wet-ground using a bead mill (product name: Awatori Neritaro ARE-310, manufactured by THINKY CORPORATION) to obtain 21.97 parts by mass of a suspension (B2) of a pesticidal active compound.
0.20 part by mass of Kelzan AP-AS, 0.20 part by mass of Proxel GXL and 20.00 parts by mass of ion-exchanged water were mixed to obtain 20.40 parts by mass of a thickener-containing liquid (C1).
20.40 Parts by mass of the thickener-containing liquid (C1) was obtained according to the above manner. To 20.40 parts by mass of the thickener-containing liquid (C1) thus obtained, 4.15 parts by mass of sodium chloride was added and then dissolved by stirring and mixing to obtain 24.55 parts by mass of a thickener-containing liquid (C2).
44.06 Parts by mass of the emulsion (A1) of the pesticidal active compound, 21.97 parts by mass of the suspension (B1) of the pesticidal active compound, 20.40 parts by mass of the thickener-containing liquid (C1) and 0.067 parts by mass of XIAMETER ACP-1500 were stirred and mixed to obtain 86.50 parts by mass of a premixture (D1).
44.06 Parts by mass of the emulsion (A1) of the pesticidal active compound, 21.97 parts by mass of the suspension (B1) of the pesticidal active compound, 24.55 parts by mass of the thickener-containing liquid (C2) and 0.067 parts by mass of XIAMETER ACP-1500 were stirred and mixed to obtain 90.65 parts by mass of a premixture (D2).
33.10 Parts by mass of the emulsion (A2) of the pesticidal active compound, 21.97 parts by mass of the suspension (B1) of the pesticidal active compound, 20.40 parts by mass of the thickener-containing liquid (C1) and 0.067 parts by mass of XIAMETER ACP-1500 were stirred and mixed to obtain 75.54 parts by mass of a premixture (D3).
37.21 Parts by mass of an aqueous Dicamba DGA solution (concentration of dicamba acid: 39.5% by mass), 21.97 parts by mass of the suspension (B2) of the pesticidal active compound, 20.40 parts by mass of the thickener-containing liquid (C1) and 0.13 part by mass of XIAMETER ACP-1500 were stirred and mixed to obtain 79.71 parts by mass of a premixture (D4).
44.06 Parts by mass of the emulsion (A1) of the pesticidal active compound, 20.40 parts by mass of the thickener-containing liquid (C1) and 0.13 part by mass of XIAMETER ACP-1500 were stirred and mixed to obtain 64.53 parts by mass of a premixture (D5).
37.21 Parts by mass of an aqueous Dicamba DGA solution (concentration of dicamba acid: 39.5% by mass), 21.97 parts by mass of the suspension (B1) of the pesticidal active compound, 20.40 parts by mass of the thickener-containing liquid (C1) and 0.13 part by mass of XIAMETER ACP-1500 were stirred and mixed to obtain 79.71 parts by mass of a premixture (D6).
46.95 Parts by mass of the emulsion (A3) of the pesticidal active compound, 21.97 parts by mass of the suspension (B1) of the pesticidal active compound, 20.40 parts by mass of the thickener-containing liquid (C1) and 0.067 part by mass of XIAMETER ACP-1500 were stirred and mixed to obtain 89.39 parts by mass of a premixture (D7).
To 86.50 parts by mass of the premixture (D1), a solution obtained by mixing 9.26 parts by mass of ion-exchanged water, 3.00 parts by mass of acetic acid and 1.24 parts by mass of potassium hydroxide was added, followed by stirring and mixing to obtain a comparative pesticidal composition (Y1).
To 86.50 parts by mass of the premixture (D1), a solution obtained by mixing 8.75 parts by mass of ion-exchanged water, 3.69 parts by mass of propionic acid and 1.06 parts by mass of potassium hydroxide was added, followed by stirring and mixing to obtain a comparative pesticidal composition (Y2).
To 86.50 parts by mass of the premixture (D1), a solution obtained by mixing 8.67 parts by mass of ion-exchanged water, 3.59 parts by mass of polyacrylic acid 5,000 and 1.24 parts by mass of potassium hydroxide was added, followed by stirring and mixing to obtain a present pesticidal composition (X1).
To 90.65 parts by mass of the premixture (D2), a solution obtained by mixing 4.00 parts by mass of ion-exchanged water, 3.59 parts by mass of polyacrylic acid 5,000 and 1.76 parts by mass of potassium hydroxide was added, followed by stirring and mixing to obtain a present pesticidal composition (X2).
To 86.50 parts by mass of the premixture (D1), a solution obtained by mixing 7.92 parts by mass of ion-exchanged water, 3.38 parts by mass of AQUALIC TL-37 and 2.20 parts by mass of polyacrylic acid 5,000 was added, followed by stirring and mixing to obtain a present pesticidal composition (X3).
To 86.50 parts by mass of the premixture (D1), a solution obtained by mixing 8.67 parts by mass of ion-exchanged water, 3.59 parts by mass of polyacrylic acid 25,000 and 1.24 parts by mass of potassium hydroxide was added, followed by stirring and mixing to obtain a present pesticidal composition (X4).
To 86.50 parts by mass of the premixture (D1), a solution obtained by mixing 8.83 parts by mass of ion-exchanged water, 3.59 parts by mass of polyacrylic acid 5,000 and 1.08 parts by mass of sodium hydroxide was added, followed by stirring and mixing to obtain a present pesticidal composition (X5).
To 75.54 parts by mass of the premixture (D3), a solution obtained by mixing 11.43 parts by mass of ion-exchanged water, 7.99 parts by mass of acetic acid and 5.04 parts by mass of potassium hydroxide was added, followed by stirring and mixing to obtain a comparative pesticidal composition (Y3).
To 75.54 parts by mass of the premixture (D3), a solution obtained by mixing 9.85 parts by mass of ion-exchanged water, 9.57 parts by mass of polyacrylic acid 5,000 and 5.04 parts by mass of potassium hydroxide was added, followed by stirring and mixing to obtain a present pesticidal composition (X6).
To 79.71 parts by mass of the premixture (D4), a solution obtained by mixing 16.05 parts by mass of ion-exchanged water, 3.00 parts by mass of acetic acid and 1.24 parts by mass of potassium hydroxide was added, followed by stirring and mixing to obtain a comparative pesticidal composition (Y4).
To 79.71 parts by mass of the premixture (D4), a solution obtained by mixing 15.46 parts by mass of ion-exchanged water, 3.59 parts by mass of polyacrylic acid 5,000 and 1.24 parts by mass of potassium hydroxide was added, followed by stirring and mixing to obtain a present pesticidal composition (X7).
To 64.53 parts by mass of the premixture (D5), a solution obtained by mixing 31.23 parts by mass of ion-exchanged water, 3.00 parts by mass of acetic acid and 1.24 parts by mass of potassium hydroxide was added, followed by stirring and mixing to obtain a comparative pesticidal composition (Y5).
To 64.53 parts by mass of the premixture (D5), a solution obtained by mixing 30.64 parts by mass of ion-exchanged water, 3.59 parts by mass of polyacrylic acid 5,000 and 1.24 parts by mass of potassium hydroxide was added, followed by stirring and mixing to obtain a present pesticidal composition (X8).
To 79.71 parts by mass of the premixture (D6), a solution obtained by mixing 16.05 parts by mass of ion-exchanged water, 3.00 parts by mass of acetic acid and 1.24 parts by mass of potassium hydroxide was added, followed by stirring and mixing to obtain a comparative pesticidal composition (Y6).
To 79.71 parts by mass of the premixture (D6), a solution obtained by mixing 15.46 parts by mass of ion-exchanged water, 3.59 parts by mass of polyacrylic acid 5,000 and 1.24 parts by mass of potassium hydroxide was added, followed by stirring and mixing to obtain a present pesticidal composition (X9).
To 89.39 parts by mass of the premixture (D7), a solution obtained by mixing 5.85 parts by mass of ion-exchanged water, 3.00 parts by mass of acetic acid and 1.76 parts by mass of potassium hydroxide was added, followed by stirring and mixing to obtain a comparative pesticidal composition (Y7).
To 89.39 parts by mass of the premixture (D7), a solution obtained by mixing 5.26 parts by mass of ion-exchanged water, 3.59 parts by mass of polyacrylic acid 5,000 and 1.76 parts by mass of potassium hydroxide was added, followed by stirring and mixing to obtain a present pesticidal composition (X10).
Table 1 and Table 2 show each composition of the present pesticidal compositions (X1) to (X10) and the comparative pesticidal compositions (Y1) to (Y7). The unit of the content of each ingredient shown in Table 1 and Table 2 is % by mass.
Each of the present pesticidal compositions (X1) to (X10) and the comparative pesticidal compositions (Y1) to (Y7) was charged in a screw tube and then left to stand in an incubator at 54° C. for 14 days. The content of the compound (I) in each pesticidal composition after storage was then analyzed by HPLC, and then the residual ratio of the compound (I) was evaluated using the calculation formula below. The results are shown in Table 1 and Table 2. The higher the residual ratio of the compound (I), the higher the inhibitory effect on decomposition of the compound (I).
Mass spectra were measured for compositions containing the compound (I-A), the compound (I-B), a dicamba diglycolamine salt, acetic acid and potassium hydroxide, which were left to stand in an incubator at 50° C. for 8 weeks. As a result, the followings were confirmed: decomposition products a and b represented by formulas below, which are decomposition products of the compound (I-A), and a decomposition product c represented by formula below, which is a decomposition product of the compound (I-B).
The decomposition product a is obtained as a result of ring-opening of a uracil ring due to the cleavage of a C—N bond (bond between an N atom at the 3-position and a C atom at the 4-position) included in an imide structure constituting a uracil ring structure of the compound (I-A), and a bond between an N atom at the 1-position and a C atom at the 6-position. The decomposed product b is obtained as a result of the addition of diglycolamine (DGA) to the terminal ethyl ester moiety, in addition to the ring-opening of the uracil ring of the compound (I-A). The decomposition product c is obtained as a result of the cleavage of two C—N bonds included in the imide structure of the compound (I-B).
From the results of Test Example 2, it can be understood that the technology of the present invention is effective in inhibiting decomposition of compounds having an amide structure, a uracil ring structure or imide structure including the amide structure, or an ester structure.
For each of the present pesticidal compositions (X1) to (X10) and the comparative pesticidal compositions (Y1) to (Y7), 8.16 parts by mass of each pesticidal composition was mixed with 6.03 parts by mass of Roundup PowerMAX (registered trademark) (Bayer CropScience product containing 48.7% by mass of a glyphosate potassium salt) and 85.81 parts by mass of ion-exchanged water to prepare 100 parts by mass of a diluted solution of each pesticidal composition, which was used as a measurement sample.
Also, 3.01 parts by mass of Clarity (registered trademark) (BASF product containing 58.1% by mass of a dicamba diglycolamine salt) was mixed with 6.03 parts by mass of Roundup PowerMAX and 90.96 parts by mass of ion-exchanged water to prepare 100 parts by mass of a control.
A description will be made with reference to
In a state where the temperature control mat 300 is controlled at 35° C., the suction pump 600 was activated to take outside air from the notches 450, thus generating a flow of gas that flows to the suction pump 600. The gas suction rate was set at 2 L/min. The suction pump 600 was continuously operated for 24 hours. The polyurethane foam 550 was then collected, and dicamba absorbed in the polyurethane foam 550 was extracted with methanol, followed by quantitative analysis using LC-MS. The amount of dicamba extracted from the quantitative analysis corresponds to the volatilization amount of dicamba. The same test was carried out for the control.
When the volatilization amount of dicamba in the control is defined as 1, the relative value of the volatilization amount of dicamba in the diluted solutions of each pesticidal composition was calculated. The results are shown in Table 1 and Table 2.
The pH value at 25° C. of each of the present pesticidal compositions (X1) to (X10) and the comparative pesticidal compositions (Y1) to (Y7) was measured according to the following procedure. Each pesticidal composition was charged in a glass container and shaken by hand. An electrode of a pH meter (“Tabletop pH meter F-71S”, manufactured by HORIBA, Ltd.) was dipped in the pesticidal composition and then the pH value was then measured. The results are shown in Table 1 and Table 2.
The present pesticidal compositions (Z1) to (Z5) shown in Table 3 are prepared according to the method for preparing the above-mentioned present pesticidal compositions (X1) to (X10) and comparative pesticidal compositions (Y1) to (Y7). The unit of the content of each ingredient shown in Table 3 is % by mass.
For each of the present pesticidal compositions (Z1) to (Z5), the residual ratio of the compound (I) and the volatilization amount of 2,4-D are evaluated according to the above-mentioned Test Examples [1] and [3], respectively. As a result, it is confirmed that all of the present pesticidal compositions (Z1) to (Z5) are pesticidal compositions capable of inhibiting volatilization of 2,4-D and inhibiting decomposition of the compound (I).
| Number | Date | Country | Kind |
|---|---|---|---|
| 2022-085180 | May 2022 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2023/019091 | 5/23/2023 | WO |
