JP2006199630A - Sustained-release agricultural chemical composition and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sustained-release agricultural chemical composition exhibiting the effect of an active component of the agricultural chemical for a long period of time and its production method. <P>SOLUTION: The sustained-release agricultural chemical composition comprises a water-soluble high molecular compound, an organic/inorganic complex formed from a compound expressed by formula (I): R<SP>1</SP><SB>n</SB>M<SP>1</SP>X<SB>m-n</SB>and an agricultural-chemically active component. Wherein, R<SP>1</SP>represents a 1-10C alkyl group optionally having a substituent, a 2-10C alkenyl group optionally having a substituent, a 3-8C cycloalkyl group optionally having a substituent or an aryl group optionally having a substituent; M<SP>1</SP>represents a metal atom; X represents a hydroxyl group or a hydrolyzable group; m represents the valence of M<SP>1</SP>; and n represents an integer of 0 to (m-2). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an organic / inorganic composite formed from an organic metal compound such as a metal alkoxide and a water-soluble polymer compound such as hydroxypropyl cellulose, and a sustained-release agrochemical composition containing an agrochemical active ingredient, and the agrochemical. The present invention relates to a method for producing a composition.

Conventionally, sustained-release compositions for the purpose of controlling dissolution of various active ingredients in water and controlling volatilization in air are known.
For example, Patent Document 1 describes an antifogging film-forming substrate formed by coating a substrate surface with a water-absorbing organic-inorganic composite coating composed of a water-absorbing organic polymer, a metal oxide, and a fragrance. According to this base material, volatilization of the fragrance into the air can be controlled.
Patent Document 2 describes a composition for a biodegradable molded article that is composed of a polysaccharide, a metal compound, a solvent, and the like and is gradually degraded in nature.
Patent Document 3 provides sustained release by inclusion of an antibacterial agent such as 5-chloro-2-methyl-4-isothiazolin-3-one with a multimolecular host compound such as tetrakisphenols. Non-bleached powder-based slime control agents are described.

  Various agrochemical formulations have been developed for the safe and efficient application of active ingredients such as pesticides. Examples of such agricultural chemical formulations include powders, granules, wettable powders, wettable powders, aqueous solvents, aqueous solutions, emulsions, sols, and the like. Agrochemical active ingredients with high water solubility such as acetamiprid are usually It is used as an aqueous solvent, granule, wettable powder and the like.

  However, especially when using an agrochemical active ingredient with high water solubility, there are cases where the use situation is limited or the residual effect is inferior for reasons such as insufficient solubility control in water, etc. There is a demand for the development of an agrochemical formulation with better sustained release.

JP 2001-172053 A JP-A-7-309972 JP 2000-327509 A

  This invention is made | formed in view of such a situation, and makes it a subject to provide the sustained-release agrochemical composition in which the efficacy of an agrochemical active ingredient is exhibited over a long period of time, and its manufacturing method.

  As a result of diligent research to solve the above-mentioned problems, the present inventors have added a mixture of hydroxypropylcellulose, tetraethoxysilane, acetamiprid, and water to a mixture of dilute hydrochloric acid as a condensation catalyst and agitated. The inventors have found that a sustained-release agrochemical composition in which elution of the component acetamiprid into water is controlled can be efficiently obtained, and the present invention has been completed.

  Thus, according to the first aspect of the present invention, a water-soluble polymer compound and the formula (I)

(In the formula, R ¹ is a C1-C10 alkyl group which may have a substituent, a C2-C10 alkenyl group which may have a substituent, and C3-C8 which may have a substituent. A cycloalkyl group, an aryl group which may have a substituent, M ¹ represents a metal atom, X represents a hydroxyl group or a hydrolyzable group, m represents a valence of M ¹ , and n represents 0 To (m-2 represents an integer). An organic / inorganic complex formed from the compound represented by (2) and a pesticidal active ingredient is provided. .

In the sustained-release agricultural chemical composition of the present invention, the agricultural chemical active ingredient is preferably a compound having a saturated solubility in water of 25 ° C. of 500 ppm or more.
In the sustained-release agrochemical composition of the present invention, the agrochemical active ingredient is preferably a neonicotinoid compound, and the neonicotinoid compound is nitenpyram, imidacloprid, acetamiprid, thiamethoxam, clothianidin, thiacloprid and dinotefuran. It is preferably at least one selected from the group consisting of

  According to a second of the present invention, a water-soluble polymer compound of formula (I)

(In the formula, R ¹ is a C1-C10 alkyl group which may have a substituent, a C2-C10 alkenyl group which may have a substituent, and C3-C8 which may have a substituent. A cycloalkyl group, an aryl group which may have a substituent, M ¹ represents a metal atom, X represents a hydroxyl group or a hydrolyzable group, m represents a valence of M ¹ , and n represents 0 To (m-2) represents the integer of (m-2)), and a step of adding a condensation catalyst to the mixture containing the compound represented by the pesticidal active ingredient and water, and a method for producing a sustained-release agrochemical composition Is provided.

The sustained-release agrochemical composition of the present invention is an agrochemical formulation excellent in sustained-release, in which the effectiveness of the agrochemical is exhibited over a long period of time. That is, the sustained-release agrochemical composition of the present invention enhances safety to the human body and the environment, saves labor, expands usage scenes, and exhibits excellent pesticide efficacy over a long period of time.
According to the method for producing a sustained-release agrochemical composition of the present invention, the sustained-release agrochemical composition of the present invention can be produced simply and efficiently.

Hereinafter, the present invention will be described in detail.
1) Sustained release agrochemical composition The sustained release agrochemical composition of the present invention comprises an organic / inorganic complex formed from a water-soluble polymer compound and the compound represented by the formula (I), and an agrochemical active ingredient. It is characterized by containing.

(1) Organic / inorganic composite The organic / inorganic composite contained in the sustained-release agricultural chemical composition of the present invention is formed from the compound represented by the formula (I) and a water-soluble polymer compound. This organic / inorganic composite is a high-performance product formed by hybridizing (compositing) an inorganic polymer that is a polycondensate of the compound represented by formula (I) with a water-soluble polymer that is an organic compound. It is a composite material. Such an organic / inorganic composite has both characteristics such as hardness, uniformity and transparency derived from a network structure of an inorganic substance, and properties such as flexibility and moldability derived from an organic component. Yes.

  The organic / inorganic composite has a network structure. The agrochemical composition of the present invention is considered to have a structure in which an agrochemical active ingredient is incorporated in the internal space formed by the network structure of the organic / inorganic composite. That is, the sustained-release agrochemical composition of the present invention is such that molecules of an agrochemical active ingredient are confined in a network-like matrix of an organic / inorganic composite, and this is placed in water. It is considered that the elution of the pesticidal active ingredient into water is controlled to a constant amount, and excellent sustained release is exhibited.

In the compound represented by the formula (I) used for the formation of the organic-inorganic composite, in the formula (I), R ¹ has a C1-C10 alkyl group which may have a substituent, and a substituent. Represents an optionally substituted C2-C10 alkenyl group, an optionally substituted C3-C8 cycloalkyl group, or an optionally substituted aryl group.

Examples of the alkyl group of the C1-C10 alkyl group that may have a substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. A butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-decyl group and the like can be mentioned.
Examples of the alkenyl group of the C2-C10 alkenyl group which may have a substituent include a vinyl group, a propenyl group, a butenyl group, and a pentenyl group.
Examples of the cycloalkyl group of the C3 to C8 cycloalkyl group which may have a substituent include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
Examples of the aryl group of the aryl group which may have a substituent include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

  Examples of the substituent which may have the above-described substituent (C1-C10 alkyl group, C2-C10 alkenyl group, C3-C8 cycloalkyl group) include halogen such as fluorine atom, chlorine atom, bromine atom and iodine atom. Atom; aryl group such as phenyl group; carboxyl group; amide group; imide group; alkoxycarbonyl group such as methoxycarbonyl group; alkoxyl group such as methoxy group and ethoxy group;

  Examples of the substituent of the aryl group which may have the substituent include alkyl groups such as methyl group, ethyl group and isopropyl group; halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; carboxyl group; Amido group; Imido group; Alkoxycarbonyl group such as methoxycarbonyl group; Alkoxyl group such as methoxy group and ethoxy group;

Among these, R ¹ is preferably a C1 to C10 alkyl group or a C1 to C10 fluorinated alkyl group from the viewpoints of availability, matrix formation ease, and the like.

M ¹ represents a metal atom, and from the viewpoints of availability, matrix formation, and the like, a silicon atom, a titanium atom, and a zirconium atom are more preferable, and a silicon atom and a titanium atom are particularly preferable.

  X represents a hydroxyl group or a hydrolyzable group. The hydrolyzable group is not particularly limited as long as it is a group that reacts with water and decomposes to produce a hydroxyl group. For example, an alkoxyl group having 1 to 6 carbon atoms which may have a substituent; an acyloxy group which may have a substituent; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an isocyanate group Cyano group; amino group; or amide group.

  Examples of the alkoxyl group having 1 to 6 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, n-pentyloxy group, and n-to. A xyloxy group etc. are mentioned. Examples of the acyloxy group include an acetoxy group, a propionyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, and an n-butylcarbonyloxy group. Examples of these substituents include a carboxyl group, an amide group, an imide group, an ester group, and a hydroxyl group.

  In the present invention, X is preferably an alkoxyl group having 1 to 6 carbon atoms, an acyloxy group, or an isocyanate group, and more preferably an alkoxyl group having 1 to 4 carbon atoms or an acyloxy group.

m represents the valence of the metal atom ^{M 1.}
n represents any integer from 0 to (m−2). When n is 2 or more, R ¹ may be the same or different, and when (mn) is 2 or more, X may be the same or different. .

  In the present invention, the compound represented by the formula (I) is preferably a metal alkoxide represented by the following formula (II).

In the formula (II), M ² is a titanium atom, a silicon atom, a sodium atom, a calcium atom, a barium atom, a copper atom, an aluminum atom, a germanium atom, a vanadium atom, a tungsten atom, a yttrium atom, a zinc atom, a lead atom, or a zirconium atom. Represents a lanthanide atom, and is particularly preferably a titanium atom or a silicon atom.

R ² represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms. Examples of the linear or branched alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and t-butyl. Groups.
q represents the valence of M ² . For example, when M ² is a titanium atom or a silicon atom, q = 4.

  Preferred examples of the metal alkoxide represented by the formula (II) include tetraalkylsilanes such as tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, and tetra n-butoxysilane; tetramethoxy And tetraalkyl titanium such as titanium, tetraethoxy titanium, tetra n-propoxy titanium, tetraisopropoxy titanium and tetra n-butoxy titanium.

  In the present invention, the compounds represented by the formula (I) can be used singly or in combination of two or more.

  In the present invention, an inorganic polymer or an inorganic polymer monomer or oligomer that has been polymerized in advance can also be used from the compound represented by the formula (I) as a raw material.

  The water-soluble polymer compound used in the present invention is a water-soluble polymer that is combined with an inorganic polymer that is a polycondensate of the compound represented by the formula (I) to form an organic / inorganic composite. If it forms, it will not be restrict | limited in particular.

  Specific examples of the water-soluble polymer compound include polyvinyl alcohol, polyvinyl acetal, polyvinyl pyrrolidone, polyvinyl acetate, polysaccharide polymers, and the like, and polysaccharide polymers are preferable.

Examples of polysaccharide polymers include hydroxyalkyl polysaccharides and hydroxyalkyl polysaccharide derivatives.
A hydroxyalkyl polysaccharide is a compound in which a hydroxyalkyl group is introduced into the hydroxyl group of the polysaccharide.
Examples of the polysaccharide include cellulose, starch, amylose, amylopectin, pullulan, curdlan, mannan, glucomannan, arabinan, chitin, chitosan, alginic acid, carrageenan, dextran and derivatives thereof.

  Examples of hydroxyalkyl polysaccharides include hydroxyethyl polysaccharides obtained by reacting polysaccharides with ethylene oxide; hydroxypropyl polysaccharides obtained by reacting polysaccharides with propylene oxide; polysaccharides with glycidol or Dihydroxypropyl polysaccharides obtained by reacting 3-chloro-1,2-propanediol; hydroxypropyl polysaccharides obtained by reacting both propylene oxide and glycidol with polysaccharides, dihydroxypropyl polysaccharides Examples thereof include polysaccharides having two or more kinds of hydroxyalkyl groups;

  Examples of the hydroxyalkyl polysaccharide derivative include polysaccharide derivatives having a structure in which part or all of the hydroxyl groups in the molecule of the hydroxyalkyl polysaccharide are blocked with a substituent via an ester bond or an ether bond.

  In the present invention, these water-soluble polymer compounds can be used singly or in combination of two or more.

  In the present invention, among these, hydroxyalkyl polysaccharides are preferred, hydroxyalkylcelluloses are more preferred, and hydroxypropylcellulose (HPC) is preferred because of easy hybridization with inorganic polymers and availability. Particularly preferred.

  The content of the water-soluble polymer compound in the agricultural chemical composition of the present invention is not particularly limited, but in obtaining an agricultural chemical composition excellent in sustained release properties, the weight ratio with the compound represented by the formula (I). The amount of water-soluble polymer compound: the compound represented by formula (I) (weight in terms of metal oxide) = 10: 1 to 1:10 is preferred, and the water-soluble polymer compound: represented by formula (I) More preferably, the amount of the compound is 5: 1 to 1: 5.

(2) Agrochemical active ingredient The agrochemical active ingredient used in the present invention is used as an agricultural chemical active ingredient such as agricultural and horticultural insecticide, agricultural and horticultural fungicide, agricultural and horticultural herbicide, agricultural and horticultural acaricide. If so, there are no particular restrictions. Especially, in this invention, it is preferable to use the pesticidal active ingredient whose saturated solubility with respect to 25 degreeC water is 500 ppm or more.

  Examples of such agrochemical active ingredients include (E) -N- (6-chloro-3-pyridylmethyl) -N-ethyl-N′-methyl-2-nitrovinylidenediamine [generic name: nitenpyram, water solubility] : About 2000 ppm], (E) -N1-[(6-chloro-3-pyridyl) methyl] -N2-cyano-N1-methylacetamidine [generic name: acetamiprid, water solubility: 4200 ppm (25 ° C.)], 1- (6-Chloro-3-pyridylmethyl) -N-nitroimidazolidin-2-ylideneamine [generic name: imidacloprid, water solubility: 510 ppm (20 ° C.)], 3- (2-chloro-1,3-thiazole-5 -Methyl-1,3,5-oxadiazinan-4-ylidene [generic name: thiamethoxam, water solubility: 4100 ppm (25 ° C)], (E) -1 (2-chloro-1,3-thiazol-5-ylmethyl-3-methyl-2-nitroguanidine [generic name: clothianidin, water solubility: 0.327 g / L (20 ° C.)], 3- (6-chloro- 3-pyridylmethyl) -1,3-thiazolidine-2-ylidenecyanamide (generic name: thiacloprid), (RS) -1-methyl-2-nitro-3- (tetrahydro-3-furylmethyl) guanidine (generic name) : Dinotefuran) and other neonicotinoid compounds;

O, S-dimethyl-N-acetylphosphoramidothioate [generic name: acephate, about 650000 ppm], N2- (4-chloro-o-toluyl) -N1, N1-dimethylformamide [water solubility: 250 ppm (20 ° C)], 2,2-dichlorovinyldimethylphosphate [generic name: DDVP, water solubility: about 1000 ppm (room temperature)]; 2,2-dimethyl-1,3-benzodioxole-4 -Il-methylcarbamate / hydrochloride [generic name: bendiocarb, water solubility: 26000 ppm (25 ° C.)], S, S′-2-dimethylaminotrimethylene-bis (thiocarbamate) [generic name: cartap, water Solubility: 200000 ppm (25 ° C.)], 2-ethylthiomethylphenylmethylcarbamate [generic name : Ethiophene carb, water solubility: 1800 ppm (20 ° C.)] and the like; S-methyl-N, N-dimethyl-N-methylcarbamoyloxy-1-thiooxamimidate [generic name: oxamyl, water solubility: 280000 ppm], S-methyl-N- (methylcarbamoyloxy) thioacetimidate [generic name: mesomil, water solubility: 58000 ppm], 1,3-dichloropropene [generic name: DD, water solubility: 2000 ppm], etc. Other insecticidal compounds; and the like.
These agrochemical active ingredients can be used singly or in combination of two or more at any ratio.

  Among these, in the present invention, the pesticidal active ingredient is more preferably a neonicotinoid compound, and the neonicotinoid compound is composed of nitenpyram, imidacloprid, acetamiprid, thiamethoxam, clothianidin, thiacloprid and dinotefuran. It is preferably at least one selected from the group.

  The content of the pesticidal active ingredient in the pesticidal composition of the present invention is not particularly limited and varies depending on the type of the pesticidal active ingredient, but from the viewpoint of obtaining a preferable sustained release property of the pesticidal active ingredient, On the other hand, it is usually 0.1 to 50% by weight, preferably 1 to 35% by weight.

To the agrochemical composition of the present invention, other agrochemical active ingredients, and various surfactants, mineral substances, antifreeze agents, thickeners, fixing agents, solvents and the like added to the agrochemical formulation are added. can do.
The shape of the agrochemical composition of the present invention is not particularly limited, and may have any shape such as a granular shape, a film shape, or a sheet shape.

  The agrochemical composition of the present invention can continue to elute the agrochemical active ingredient slowly at a constant speed regardless of the solubility of the agrochemical active ingredient used in various solvents and the external environment. It can be used as an agrochemical formulation that can exert its efficacy.

  When the agrochemical composition of the present invention contains a water-soluble agrochemical active ingredient, the dissolution rate of the water-soluble agrochemical active ingredient in water even when the agrochemical composition of the present invention is placed in water Can be controlled at a constant speed. Therefore, it is possible to use the agrochemical composition of the present invention as an agrochemical formulation that can exhibit the efficacy of agrochemicals over a long period of time, even in use situations where it has been difficult to use with agrochemical formulations that contain water-soluble pesticide active ingredients. It becomes.

2) Method for producing sustained-release agrochemical composition The sustained-release agrochemical composition of the present invention comprises (A) at least one of the water-soluble polymer compounds, at least one compound represented by formula (I), and agrochemical activity. A method of adding a condensation catalyst to a mixture containing at least one component and water, and stirring the whole volume, or (B) at least one water-soluble polymer compound, at least one compound represented by the formula (I), In addition, an organic / inorganic composite material can be prepared in advance by adding a condensation catalyst to a mixture containing water and stirring, and can be produced by a method of mixing this with at least one agrochemical active ingredient. In the present invention, the method (A) is preferable because the sustained-release agricultural chemical composition of the present invention can be obtained simply and efficiently.

  More specifically, the method (A) includes a water-soluble polymer compound, a compound represented by the formula (I), and an agrochemical active ingredient in water in the presence or absence of an organic solvent and a condensation catalyst. And mixing and stirring together.

  The condensation catalyst to be used is represented by the formula (I) by interacting with the metal part or hydrolyzable group part of the compound represented by the formula (I) via a coordination bond or a hydrogen bond. If it is a catalyst which has the effect | action which accelerates | stimulates condensation with the compound and water-soluble high molecular compound, it will not restrict | limit in particular. Among these, at least one compound selected from the group consisting of metal oxides, metal alkoxides, metal alkoxide partial hydrolysis products, silanol condensation catalysts, and acid catalysts is preferable, and silanol condensation catalysts and acid catalysts are more preferable.

  Examples of the silanol condensation catalyst include carboxylic acid metal salts, carboxylic acid ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanate esters, and titanate ester chelates.

  Specifically, stannous acetate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, stannous dioctanoate, lead naphthenate, cobalt naphthenate , Iron 2-ethylhexenoate, dioctyltin bisoctylthioglycolate, dioctyltin maleate, dibutyltin maleate polymer, dimethyltin mercaptopropionate polymer, dibutyltin bisacetylacetate, dioctyltin bisacetyllaurate , Titanium tetraethoxide, titanium tetrabutoxide, titanium tetraisopropoxide, titanium bis (acetylacetonyl) dipropoxide, etc. .

  Examples of the acid catalyst include mineral acids such as hydrochloric acid, nitric acid, boric acid, and borohydrofluoric acid, organic acids such as acetic acid, formic acid, oxalic acid, carbonic acid, trifluoroacetic acid, p-toluenesulfonic acid, and methanesulfonic acid. In addition, a photoacid generator that generates an acid by light irradiation, specifically, diphenyliodonium hexafluorophosphate, triphenylphosphonium hexafluorophosphate, and the like can be exemplified.

  The amount of the condensation catalyst used is not particularly limited as long as the pesticidal active ingredient can be stably present and does not affect the sustained-release pesticidal composition, but with respect to 1 mol of the compound represented by the formula (I). The number of moles in terms of oxide is usually 0.001 to 1 times mol, preferably 0.001 to 0.2 times mol.

The water used in the method (A) has a role of reacting with the hydrolyzable group of the compound represented by the formula (I) and polycondensing the compound represented by the formula (I).
The amount of water added is 0.01 to 10 times mol, preferably 0.05 to 5 times mol for 1 mol of the compound represented by formula (I).
Moreover, water may be used as a solvent, and when an acid catalyst is used as a catalyst, it is not necessary to add water as long as the acid catalyst contains water.

  The organic solvent used in the method (A) is not particularly limited. Specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, benzyl alcohol, methylcyclohexanol, ethane Alcohols such as diol, propanediol, butanediol, pentanediol, hexylene glycol, octylene glycol, hexanetriol, 3,5,5-trimethyl-1-hexanol; butyl formate, pentyl formate, methyl acetate, ethyl acetate, Propyl acetate, butyl acetate, pentyl acetate, hexyl acetate, benzyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, methyl propionate, ethyl propionate , Esters such as butyl propionate and pentyl propionate; ketones such as dimethyl ketone, methyl ethyl ketone, pentanone, hexanone, methyl isobutyl ketone, heptanone, diisobutyl ketone; nitriles such as acetonitrile; diethyl ether, dipropyl ether, diisopropyl ether , Ethers such as dibutyl ether, dihexyl ether, anisole, tetrahydrofuran, tetrahydropyran, dimethoxyethane, diethoxyethane, dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether; acetals such as methylal; pentane, hexane, Aliphatic hydrocarbons such as heptane, octane, nonane, decane, dodecane; Aromatic hydrocarbons such as ruene, xylene, ethylbenzene, cumene, micitylene, tetralin, butylbenzene, cymene, diethylbenzene, pentylbenzene, dipentylbenzene; cycloaliphatic carbonization such as cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, decalin Hydrogen; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, chlorobenzene, dichlorobenzene, bromobenzene, and the like. These organic solvents can be used singly or in combination of two or more.

Among these, alcohols and esters having high water solubility are preferable, and alcohols are more preferable.
Although the usage-amount of an organic solvent is not restrict | limited in particular, it is 1-100g normally with respect to 1g of water-soluble high molecular compounds, Preferably it is 5-50g.

  In the method (A), the amount of the agrochemical active ingredient used is not particularly limited, but from the viewpoint of obtaining an agrochemical composition excellent in sustained release of the agrochemical active ingredient, the compound represented by the formula (I) Of the pesticidal active ingredient: the compound represented by the formula (I) = 1: 20 to 10: 1, and the pesticidal active ingredient: the compound represented by the formula (I) = 1: 10. More preferably, it is ˜1: 1.

  In the method (A), the amount of the water-soluble polymer compound used is not particularly limited, but in order to obtain an agrochemical composition excellent in sustained release properties, the weight ratio with the compound represented by the formula (I). The amount of water-soluble polymer compound: the compound represented by formula (I) (weight in terms of metal oxide) = 10: 1 to 1:10 is preferred, and the water-soluble polymer compound: represented by formula (I) More preferably, the amount of the compound is 5: 1 to 1: 5.

  In the method (A), the temperature for mixing and stirring the whole volume is usually 0 to 60 ° C., preferably room temperature. The mixing / stirring time is several tens of minutes to several hours as a whole, although it depends on the type and amount of raw materials used.

  More specifically, in the method (B), the water-soluble polymer compound and the compound represented by the formula (I) are mixed and stirred together with water and a condensation catalyst in the presence or absence of an organic solvent. Thus, after obtaining an organic / inorganic composite, this can be mixed with an agrochemical active ingredient at a predetermined ratio.

  In the method (B), as the condensation catalyst and organic solvent to be used, the same ones listed as those that can be used in the method (A) can be used. The amount of water added, the stirring temperature, etc. are the same as in the method (A).

  In the method (B), the amount of the pesticidal active ingredient to be blended with the organic / inorganic composite is not particularly limited, but is generally 0.1 to 50% by weight, preferably 1 to 35% by weight.

  In any case, after mixing and stirring, a desired sustained-release composition can be obtained by forming a film as desired and drying.

  For example, the mixed and stirred mixture obtained by the method (A) above is cast into a polytetrafluoroethylene petri dish, dried at room temperature for 2 weeks, and then vacuum-dried at 80 ° C. for one day to form a thin film. The sustained-release agrochemical composition of the present invention can be obtained.

  The sustained-release agricultural chemical composition of the present invention may contain silicon oxide or calcium silicate. Specific examples of silicon oxide or calcium silicate include white carbon, and more specific examples include normal white carbon, calcined white carbon, and hydrophobic white carbon.

Ordinary white carbon is a general term for amorphous silicon dioxide made of SiO ₂ and calcium silicate, and is classified into precipitated silica and fumed silica depending on the production method.
Firing white carbon is white carbon in which silanol groups on the surface are hydrophobized by treating normal white carbon at a high temperature. Hydrophobic white carbon is hydrophilic silanol on the surface of silicon oxide or calcium silicate. A group (Si-OH) that has been subjected to a hydrophobic treatment by chemical modification, heat treatment or the like is shown.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, the scope of the present invention is not limited at all by the following examples.

(Example 1) Production of agricultural chemical composition Hydroxypropylcellulose (product name: HPC-SL, manufactured by Nippon Soda Co., Ltd.) (4.0 g) was dissolved in ethanol (36 g), and tetraethoxysilane (13.85 g) was added thereto for 30 minutes. Further, 2 g of acetamiprid (agrochemical active ingredient) was added and stirred for 30 minutes. Thereafter, 0.66 ml of 1N hydrochloric acid (0.01 equivalent of hydrochloric acid with respect to tetraethoxysilane) was added to this mixture, and the mixture was stirred for 3 hours and cast into a petri dish made of polytetrafluoroethylene. After drying at room temperature for 2 weeks, it was vacuum-dried at 80 ° C. for one day to obtain a transparent film of the agricultural chemical composition.

Pesticide active ingredient elution test 0.15 g of the agricultural chemical composition obtained above (acetamipride content 0.03 g) was weighed into a volumetric flask, filled with 300 ml of distilled water at 25 ° C., then stoppered and inverted 5 times. And left in a thermostatic bath at 25 ° C. Sampling was performed 1 hour, 3 hours, 24 hours, and 48 hours after 5 inversions over time. The concentration of acetamiprid in the solution (dissolution rate%) was measured under the following conditions by an external standard method using high performance liquid chromatography.

<Measurement conditions>
Column: CrestPak C18S 4.6 × 150 nm (manufactured by JASCO Corporation)
Column oven temperature: 35 ° C
Measurement wavelength: 244 nm
Moving bed: acetonitrile / purified water = 3/7 (volume ratio)
Flow rate: 1.0 ml / min
Sample injection volume: 10 μl

(Comparative Example 1)
In place of 0.15 g of the agrochemical composition of Example 1, 0.03 g of acetamiprid drug substance was used, and an elution test was conducted in the same manner as in Example 1.

  The measurement results of the dissolution test of the agricultural chemical composition of Example 1 and the dissolution test of the acetamiprid drug substance of Comparative Example 1 are shown in Table 1 and FIG. In FIG. 1, the vertical axis represents elution rate (%), and the horizontal axis represents elapsed time (hour).

  From the dissolution rate graphs in Table 1 and FIG. 1, in Comparative Example 1, most of the acetamiprid was eluted within the first hour, whereas in Example 1, the acetamiprid was gradually eluted over the measured 48 hours. You can see that The agrochemical composition of Example 1 is an agrochemical composition excellent in sustained release properties.

FIG. 1 is a diagram showing measurement results of dissolution tests of Example 1 and Comparative Example 1.

Claims (5)

Water-soluble polymer compound and formula (I)

(In the formula, R ¹ is a C1-C10 alkyl group which may have a substituent, a C2-C10 alkenyl group which may have a substituent, and C3-C8 which may have a substituent. A cycloalkyl group, an aryl group which may have a substituent, M ¹ represents a metal atom, X represents a hydroxyl group or a hydrolyzable group, m represents a valence of M ¹ , and n represents 0 To (m-2), an organic / inorganic composite formed from the compound represented by (2), and a pesticidal active ingredient.   The sustained-release agrochemical composition according to claim 1, wherein the agrochemical active ingredient is a compound having a saturated solubility in water of 25 ° C of 500 ppm or more.   The sustained-release agrochemical composition according to claim 1 or 2, wherein the agrochemical active ingredient is a neonicotinoid compound.   The sustained-release agricultural chemical composition according to claim 3, wherein the neonicotinoid compound is at least one selected from the group consisting of nitenpyram, imidacloprid, acetamiprid, thiamethoxam, clothianidin, thiacloprid and dinotefuran. Water-soluble polymer compound, formula (I)

(In the formula, R ¹ is a C1-C10 alkyl group which may have a substituent, a C2-C10 alkenyl group which may have a substituent, and C3-C8 which may have a substituent. A cycloalkyl group, an aryl group which may have a substituent, M ¹ represents a metal atom, X represents a hydroxyl group or a hydrolyzable group, m represents a valence of M ¹ , and n represents 0 To (m-2) represents the integer of (m-2)), and a step of adding a condensation catalyst to the mixture containing the compound represented by the pesticidal active ingredient and water, and a method for producing a sustained-release agrochemical composition .

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