JPH07165515A - Solid agrochemical composition - Google Patents

Abstract

PURPOSE:To obtain a solid agrochemical composition stable over a long period by mixing a crystallization preventing assistant such as an alkylene glycol rosin ester to a specific agricultural herbicide having excellent herbicidal activity, melting the mixture and supporting the mixture on a solid carrier. CONSTITUTION:This solid agrochemical composition is produced by mixing a compound of formula I [W is A-R (A is O or S; R is an alkyl, an alkenyl, an alkynyl, etc.); X is a halogen or together with W forms O-CHR<5>-CO-NR<6> (R<5> is H or an alkyl; R<6> is an alkyl, an alkenyl, etc.); Y is H or a halogen; Z is group of formula II formula III (U is O or S), formula IV or formula VI with an assistant exhibiting the action to prevent the crystallization of the compound of formula I and selected from alkylene glycol rosin esters and polyalkylene oxide rosin esters, melting the obtained mixture and supporting the mixture on a solid carrier. The composition can stably hold the agrochemical effect of the compound of formula I (e.g. the compound of formula VI) over a long period and gives slight phytotoxicity to crops.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a solid agricultural chemical composition which is stable for a long period of time. More specifically, the solid pesticide composition according to the present invention is an effect (herbicidal activity) of the pesticide active ingredient as a pesticide.
Has a characteristic that it can be stably maintained at a high level for a long period of time, and that the phytotoxicity to crops is extremely slight, and it has extremely advantageous properties in practical use as an agricultural chemical (herbicide).

[0002]

BACKGROUND OF THE INVENTION The group of compounds represented by the general formula (I) is an agricultural herbicide having an excellent weed-controlling effect, such as a wettable powder, an emulsion or a flowable agent. It is already known that it can be used as a pharmaceutical preparation (for example, JP-A-5-208975, JP-A-1-250388, JP-A-63-264489).
Gazette and European Patent Application Publication No. 170191 gazette). However, according to the studies by the present inventors,
The compound group represented by the general formula (I) has a remarkable difference in biological activity (herbicidal activity) and phytotoxicity to crops due to difference in formulation or physical properties (crystallization state) of active ingredients in the formulation. It was found that That is, among various preparations of the compound group represented by the general formula (I),
In the case of emulsions, the herbicidal activity is high, but the phytotoxicity is stronger than that of other preparations. Also, although the phytotoxicity of wettable powders is slight, it is amorphous when the pesticide active ingredient in the preparation exists in a crystalline state. It was found that the biological activity (herbicidal activity) was extremely inferior to that in the existing state.

On the other hand, a flowable agent is a preparation which can be applied to a pesticidal active ingredient in a crystalline state, and although the phytotoxicity is slight, its biological activity (herbicidal activity) is an emulsion or a hydrate containing an agrochemical active ingredient. It is extremely inferior to the agent and no improvement in biological activity was observed even by the commonly used method of finely pulverizing crystal particles. From the above, in consideration of both phytotoxicity against crops and biological activity (herbicidal activity), it is most preferable to formulate a solid formulation such as a wettable powder using an agrochemical active ingredient that has been amorphized. it is conceivable that. But,
In the case of a wettable powder, when the agrochemical active ingredient is amorphized by heat-melting treatment or treatment by dissolving with an organic solvent and then distilling off the solvent, the active ingredient gradually crystallizes over time. It has been found that it is extremely difficult to change to the state and keep the amorphous state stable in the preparation, that is, to keep the biological activity (herbicidal activity) stably high.

Regarding the amorphization of crystalline compounds, a method using alkylene glycols is generally known. For example, JP-A-1-308203 discloses that
For compounds having an amino group or an amide group in the molecule, a method of using an alkylene glycol derivative such as polyethylene glycol, polyoxyethylene nonylphenyl ether or polyoxyethylene sorbitan monooleate is described. is there. However, there is no report on the stability of the amorphous state with time when these derivatives are used, and in fact,
When the above alkylene glycol derivatives were used for the agrochemical active ingredient in the present invention, it was found that they were insufficient to maintain the amorphous state. As described above, in the formulation of the compound group represented by the general formula (I), it has hitherto been discovered that both biological activity (herbicidal activity) and phytotoxicity to crops can be practically satisfied at the same time. Didn't.

[0005]

Means for Solving the Problems The present inventors have conducted extensive studies to solve the above problems, found that a solid agricultural chemical composition having a specific composition is stable for a long period of time, and completed the present invention. I arrived.

That is, the gist of the present invention is (i) the following general formula (I)

[Chemical 13]

[In the above formula, W is a group represented by -A-R.
Indicates. A represents an oxygen atom or a sulfur atom. R
Is C₁-C₆Alkyl group of C₂-C₆Alkenyl
Base, C₂-C₆An alkynyl group of C₃-C₆Cycloa
Rukyiru group, or -CR¹R²-CO-OR ³Represented by
Represents a group. R¹And R²Is a hydrogen atom or C₁
-C_FourIs an alkyl group. R³Is a hydrogen atom, C₁−
C₆Alkyl group of C₂-C₆Alkenyl group of C ₂−
C₆An alkynyl group of C₃-C₆A cycloalkyl group of
C₁-C₆A haloalkyl group of, or

[0008]

[Chemical 14]

A group represented by the formula (R ⁴ represents a C ₁ -C ₄ alkyl group) is shown. X represents a halogen atom. X
^May form —O—CHR ⁵ —CO—NR ⁶ — together with W. R ⁵ represents a hydrogen atom or a C ₁ -C ₄ alkyl group. R ⁶ is a C ₁ -C ₆ alkyl group,
Alkenyl C ₂ -C _6, alkynyl group C ₂ -C ₆ or a cycloalkyl group of C ₃ -C _6,. Y
Represents a hydrogen atom or a halogen atom. Z represents a group represented by any of the following.

[0010]

[Chemical 15]

(U in the above formula represents an oxygen atom or a sulfur atom.)], And (ii) alkylene glycol rosin esters and polyalkylene oxide rosin esters. A solid agrochemical composition characterized in that it contains a mixture of at least one auxiliary agent having an action of preventing crystallization of the agrochemical active ingredient selected from the following, which is melted and supported on a solid carrier.

The present invention will be described in detail below. In the present invention
The applied agricultural chemical active ingredient is represented by the above general formula (I).
It Such compounds are disclosed, for example, in JP-A-5-208975.
Japanese Patent Laid-Open No. 1-250388, Japanese Patent Laid-Open No. 63-2
No. 64489 or European Patent Application Publication No. 17
No. 0191, etc. Particularly in the present invention,
Solid and sparingly soluble in water (water solubility is about 100ppm at room temperature)
The effect is great for the following compounds. The present invention is suitable
Preferred compounds to be used are those represented by the above general formula (I)
Where W is a group represented by -AR (where A is oxygen
Atom or sulfur atom, R is C ₂-C₆The alkini
Radical or -CR¹R²-CO-OR³The group represented by
Show, R¹And R²Represents a hydrogen atom, R³Is C₁−
C₆Alkyl group of, or

[0013]

[Chemical 16]

## STR3 ## wherein X is a halogen atom or W together with

[0015]

[Chemical 17]

The groups represented by are mentioned below. In addition, Z represents a group represented by any of the following.

[0017]

[Chemical 18]

Further, among the above compounds, (i) W is -A
A group represented by -R (A represents a sulfur atom, R represents -CH ₂
Represents a group represented by COOR ³ , wherein R ³ is a C ₁ -C ₄ alkyl group or

[0019]

[Chemical 19]

X is a halogen atom, Z is a group represented by any of the following,

[0021]

[Chemical 20]

[0022] (ii) W is a group represented by -A-R (A represents an oxygen atom, R represents shows the alkynyl group of C ₂ -C ₄₎
And X represents a halogen atom or together with W

[0023]

[Chemical 21]

Forming a group represented by: Y is a halogen atom, and Z is

[0025]

[Chemical formula 22]

Those having a group represented by are preferred. Specific examples of the agricultural chemical active ingredient to which the present invention is applied include the compounds shown in Table 1 below. Particularly preferred are compound B and compound C in Table 1. Further, as auxiliary agents used for preventing crystallization of the above compound group, alkylene glycol-rosin ester or polyalkylene oxide rosin ester, preferably ethylene glycol-rosin ester or propylene glycol-rosin ester And the like, the number of added moles of alkylene glycol-rosin ester such as ethylene oxide or ethylene oxide is 2 to 20, preferably 5 to 18
Examples of polyalkylene oxide rosin esters such as polyoxyethylene rosin ester or polypropylene oxide rosin ester having an addition mole number of propylene oxide of 2 to 20.

The alkylene glycol-rosin ester or polyalkylene oxide rosin ether referred to herein is an ester of rosin obtained from pine resin with alkylene glycol or polyalkylene glycol, the main component of which is the following structure. It is shown by the formula.

[0028]

[Chemical formula 23]

(In the above formula, R ⁷ and R ⁸ represent a hydrogen atom or a methyl group, and n represents an integer of 1 to 20). When a weight ratio of the compound represented by I) is 0.1 times or more, the effect of preventing crystallization is observed, but in practical use, it is in the range of 0.1 to 10 times, more preferably 0.1 times. ~
It is better to use it in the range of 5 times.

Solid agricultural chemicals containing a molten mixture of the agricultural chemical active ingredient represented by the above general formula (I) and auxiliary agents having an anti-crystallization effect such as alkylene glycol-rosin esters or polyalkylene oxide rosin esters. As a method for producing the composition, the following method can be usually adopted. That is, after the mixture is heated and melted and supported on a solid carrier, it is crushed by cooling, or after the mixture is dissolved in an organic solvent and supported on a solid carrier, as it is or after the organic solvent is removed by evaporation. , Crush.

Examples of the organic solvent used include halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride, alcohols such as methanol, ethanol and isopropanol, esters such as ethyl acetate and butyl acetate, benzene, and the like. Examples thereof include aromatic hydrocarbons such as toluene and xylene, nitrogen-containing polar solvents such as acetonitrile, N-methylpyrrolidone and pyridine, and chain or cyclic ethers such as diethyl ether, tetrahydrofuran and dioxane.

As the solid carrier, diatomaceous earth, clay,
Mineral simple substance such as talc, kaolin or bentonite,
A synthetic simple substance such as hydrous silicon dioxide and calcium carbonate or a solid simple substance usually used for agricultural preparations such as starch and a vegetable carrier such as cellulose can be used. Although the amount of the solid simple substance used is not particularly limited, it is usually a mixture 1 of the agrochemical active ingredient and (poly) alkylene glycol.
It is preferable to use 0.5 to 10 parts by weight based on parts by weight. Further, in order to improve the dispersibility of the preparation or the like, these solid carriers may be preliminarily loaded with a surfactant such as various anionic surfactants or nonionic surfactants generally used, and the above mixture After supporting
You may add.

The surfactant to be used is not particularly limited as long as it is usually used in pesticide formulations, and examples thereof include non-oxidizing agents such as polyoxyethylene alkyl allyl ether and polyoxyethylene sorbitan monolaurate. Ionic surfactants, cationic surfactants such as alkyldimethylbenzylammonium chloride and alkylpyridinium chloride, anionic surfactants such as alkylbenzene sulfonates, lignin sulfonates and higher alcohol sulfates, alkyldimethyl betaines, dodecyl Examples include amphoteric surfactants such as aminoethylglycine.

The solid agricultural chemical composition thus obtained can be used as it is by diluting it with water as a wettable powder for agriculture, but if necessary, other solid carrier,
It is also possible to use a surfactant, a binder, water and the like to formulate into granules or granule wettable powders. Further, the solid agricultural chemical composition is mixed into a solid preparation containing other agricultural chemical active ingredient, or the other agricultural chemical active ingredient is mixed into the solid agricultural chemical composition, and the mixture is formulated as a mixture. It is also possible to do so. The alkylene glycol-rosin ester or the polyalkylene oxide rosin ester used in the present invention can maintain the amorphous state of the compound group represented by the general formula (I) in the preparation for a long period of time, It has an excellent effect that conventional alkylene glycols do not have, and is extremely effective in stably maintaining a high biological activity (herbicidal activity) of the compound group.

[0035]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
The compound of the general formula (I) used in the examples is
As shown in Table 1 below.

[0036]

[Table 1]

Example 1 20 parts of propylene glycol rosin ester was added to 20 parts of compound B in the crystalline state, and the mixture was heated to about 80 ° C. and melted. To this was added a solid carrier consisting of a mixture of 20 parts of white carbon, 35 parts of diatomaceous earth, 2 parts of alkylallyl sulfonate and 3 parts of sodium lignin sulfonate, and the above melted mixture was uniformly adsorbed. After cooling, the adsorbed solid was crushed with a hammer mill to obtain the wettable powder of the present invention.

Example 2 20 parts of propylene glycol rosin ester was added to 20 parts of crystalline compound C, and the mixture was heated to about 80 ° C. and melted. To this was added a solid carrier consisting of a mixture of 20 parts of white carbon, 35 parts of diatomaceous earth, 2 parts of alkylallyl sulfonate and 3 parts of sodium lignin sulfonate, and the above melted mixture was uniformly adsorbed. After cooling, the adsorbed solid was crushed with a hammer mill to obtain the wettable powder of the present invention.

Example 3 20 parts of propylene glycol rosin ester was added to 20 parts of crystalline compound D, and the mixture was heated to about 80 ° C. and melted. To this was added a solid carrier consisting of a mixture of 20 parts of white carbon, 35 parts of diatomaceous earth, 2 parts of alkylallyl sulfonate and 3 parts of sodium lignin sulfonate, and the above melted mixture was uniformly adsorbed. After cooling, the adsorbed solid was crushed with a hammer mill to obtain the wettable powder of the present invention.

Example 4 To 20 parts of crystalline compound B, 5 parts of polyoxyethylene rosin ester (number of moles of ethylene oxide added: 15) was added and heated to about 80 ° C. to melt. To this was added a solid carrier consisting of a mixture of 20 parts of white carbon, 50 parts of diatomaceous earth, 2 parts of alkylallyl sulfonate and 3 parts of sodium lignin sulfonate, and the molten mixture was uniformly adsorbed. After cooling, the adsorbed solid was crushed with a hammer mill to obtain the wettable powder of the present invention.

Example 5 20 parts of propylene glycol rosin ester was added to 20 parts of crystalline compound E, and the mixture was heated to about 80 ° C. and dissolved. To this was added a solid carrier consisting of a mixture of 20 parts of white carbon, 35 parts of diatomaceous earth, 2 parts of alkylallyl sulfonate and 3 parts of sodium lignin sulfonate, and the above molten mixture was uniformly adsorbed. After cooling, the adsorbed solid was crushed with a hammer mill to obtain the wettable powder of the present invention.

Example 6 To 20 parts of crystalline compound F, 20 parts of propylene glycol rosin ester was added and heated to about 80 ° C. to dissolve. To this was added a solid carrier consisting of a mixture of 20 parts of white carbon, 35 parts of diatomaceous earth, 2 parts of alkylallyl sulfonate and 3 parts of sodium lignin sulfonate, and the above molten mixture was uniformly adsorbed. After cooling, the adsorbed solid was crushed with a hammer mill to obtain the wettable powder of the present invention.

Comparative Example 1 White carbon 20 was added to 20 parts of compound B in a crystalline state.
Part, diatomaceous earth 55 parts, alkyl allyl sulfonate 2 parts,
3 parts of sodium lignin sulfonate was added and mixed uniformly, and then ground with a hammer mill to obtain a comparative wettable powder. Comparative Example 2 20 parts of compound C in a crystalline state was mixed with 20 parts of white carbon.
Part, diatomaceous earth 55 parts, alkyl allyl sulfonate 2 parts,
3 parts of sodium lignin sulfonate was added and mixed uniformly, and then ground with a hammer mill to obtain a comparative wettable powder.

Comparative Example 3 White carbon 20 was added to 20 parts of compound D in the crystalline state.
Part, diatomaceous earth 55 parts, alkyl allyl sulfonate 2 parts,
3 parts of sodium lignin sulfonate was added and mixed uniformly, and then ground with a hammer mill to obtain a comparative wettable powder. Comparative Example 4 To 20 parts of Compound B, 70 parts of Solvesso 200 (an alkylnaphthalene-based solvent manufactured by Exxon Chemical Co., Ltd.) and 10 parts of polyoxyethylene styryl phenyl ether were added, and the whole was uniformly dissolved to obtain a comparative emulsion.

Comparative Example 5 70 parts of Solvesso 200 and 10 parts of polyoxyethylene styryl phenyl ether were added to 20 parts of compound C, and the whole was uniformly dissolved to obtain a comparative emulsion. Comparative Example 6 70 parts of Solvesso 200 and 10 parts of polyoxyethylene styryl phenyl ether were added to 20 parts of Compound D, and the whole was uniformly dissolved to obtain a comparative emulsion.

Comparative Example 7 To 20 parts of compound B in a crystalline state, 20 parts of polyoxyethylene sorbitan monooleate and 50 parts of water were added, and the mixture was pulverized with a wet pulverizer to a particle size of 0.4 μm or less. % Aqueous solution was added and uniformly mixed to obtain a comparative flowable agent.

Comparative Example 8 After dissolving 20 parts of compound B in crystalline form in dichloromethane, the dichloromethane was distilled off with a rotary evaporator. The obtained amorphous compound B was heated to 80 ° C. and kept. 20 parts white carbon, 55 diatomaceous earth
Parts, 2 parts of alkylallyl sulfonate and 3 parts of sodium lignin sulfonate were added as a solid carrier to uniformly adsorb the molten compound. After cooling, the adsorbed solid was crushed with a hammer mill to give a comparative wettable powder.

Comparative Example 9 White carbon 20 was added to 20 parts of compound E in a crystalline state.
Part, diatomaceous earth 55 parts, alkyl allyl sulfonate 2 parts,
3 parts of sodium lignin sulfonate was added and mixed uniformly, and then pulverized with a hammer mill to obtain a comparative wettable powder. Comparative Example 10 White carbon 20 was added to 20 parts of compound F in a crystalline state.
Part, diatomaceous earth 55 parts, alkyl allyl sulfonate 2 parts,
3 parts of sodium lignin sulfonate was added and mixed uniformly, and then pulverized with a hammer mill to obtain a comparative wettable powder.

Test Example 1 Amorphous Stability Evaluation Test To 1 part of Compounds A to F, 1 part of various auxiliaries for the purpose of preventing crystallization was added, and the mixture was heated to about 80 ° C. and dissolved. After that, the sample was placed under room temperature and humidity of 90%, and after 1 week, the presence or absence of crystal precipitation was examined. The obtained results are shown in Table 2 below.

[0050]

[Table 2] 1) The value in () indicates the number of moles of ethylene oxide added. 2) After dissolving each compound of A, B, C, D, E, and F in dichloromethane, dichloromethane was distilled off by a rotary evaporator to make it amorphous. Evaluation: ○: Amorphous state is stable for 1 week or more Δ: Amorphous state is stable for 1 day or more, crystals are deposited within 1 week × ... Crystals are deposited within 1 day

Test Example 2 Herbicidal Effect Test A pot of 180 cm ² in unglazed clay was filled with upland volcanic ash soil, and after fertilization, various larvae of Abutilon chinensis, Onamomi and Noasaagao were sown in each pot. When cultivation management was continued in a greenhouse and the growth leaf age of the test plant reached the 3-5 leaf stage of velveteen, the 3-5 leaf stage of Onami fir, and the 2-2.5 leaf stage of Noosa morning glory, Examples and The amount of each active ingredient of Comparative Examples was 0.006, 0.013, 0.0 per hectare.
Spreading agent (X-77; 0.125% to be 25 kg)
v / v) was added to adjust the dilution, and the foliage of each plant was treated with a small power pressure sprayer at an amount of 250 liters equivalent to the amount of treatment liquid per hectare. Then, cultivation control was continued in the greenhouse, and the herbicidal effect was investigated 21 days after the chemical treatment. The evaluation of the herbicidal effect was carried out by visual observation according to the following criteria.

[0052]

[Table 3] Judgment criteria: The obtained results are shown in Tables 3 and 4.

[0053]

[Table 4]

[0054]

[Table 5]

Test Example 3 Chemical Injury Test on Crops A biscuit pot with an area of 180 cm ² was filled with upland volcanic ash soil, and after fertilization, soybean, corn and various wheat seeds were sown in each pot. When cultivation control is continued in a greenhouse and the growing leaf age of the test plant reaches soybean 1 to 1.5 leaf stage, corn 3 to 3.5 leaf stage, and wheat 2.5 to 3 leaf stage, Each preparation of Examples and Comparative Examples was treated with 0.025, 0.05
Spreading agent (X-77; 0.125
% V / v) and diluted to 250 liters as the amount of treatment liquid per hectare to treat the foliage of each crop with a small power pressurizer. After that, cultivation control was continued in a greenhouse, and 14 days after the chemical treatment, phytotoxicity was investigated. The evaluation of drug damage was carried out by visual observation according to the following criteria.

[0056]

[Table 6] Criteria: The obtained results are shown in Tables 5 and 6.

[0057]

[Table 7]

[0058]

[Table 8]

Test Example 4 Herbicidal Effect over Time A bisque-fired pot having an area of 180 cm ² was filled with upland volcanic ash soil, and after fertilization, various offspring of Onami fir and No. morning glory were sown in each pot. Cultivation management is continued in the greenhouse, and the leaf age of the test plant is the 4th leaf stage of Onamomi, Noasaagao 2-3
When the leaf age stage was reached, 0.013,0.00% per hectare of each of the formulations of Examples and Comparative Examples was used as the active ingredient amount.
Spreading agent (X-77;
Diluting with water containing 0.125% v / v), the foliage of each plant was treated with a small power pressurizer at a volume equivalent to 250 liters as a treatment liquid volume per hectare. Then, cultivation control was continued in the greenhouse, and the herbicidal effect was investigated 21 days after the chemical treatment. Further, the herbicidal effect was examined by performing the same treatment using the formulation after storage for 3 months. The evaluation of the herbicidal effect was the same as in Test Example 2. The obtained results are shown in Tables 7 and 8.

[0060]

[Table 9]

[0061]

[Table 10]

Example 5 Herbicidal Effect Test A pot of 180 cm ² in unglazed pottery was filled with upland volcanic ash soil, and after fertilization, various larvae of Abutilon chinensis, Onami fir and No. morning glory were sown in each pot. When cultivation management is continued in the greenhouse and the growth leaf age of the test plant reaches the velvet leaf stage of 4.5 to 5 leaf stage, the onion tree of 5 to 5.5 leaf stage, and the morning glory of 3 to 4.5 leaf stage, Each formulation of Examples and Comparative Examples was treated with 0.013, 0.025
Spreading agent (X-77; 0.12
Diluting and adjusting with water containing 5% v / v), the foliage of each plant was treated with a small power pressure sprayer at a volume equivalent to 250 liters as a treatment liquid volume per hectare. Then, cultivation control was continued in the greenhouse, and the herbicidal effect was investigated 21 days after the chemical treatment. The evaluation of the herbicidal effect was the same as in Test Example 2. The results obtained are shown in Table 9.

[0063]

[Table 11]

[0064]

INDUSTRIAL APPLICABILITY In the solid agricultural chemical composition of the present invention, the agricultural chemical active ingredient is stably maintained in the amorphous state for a long period of time. As a result, the pesticidal composition of the present invention exhibits a high herbicidal activity for a long period of time, and has a minimal phytotoxicity to crops.

Claims (9)

[Claims] (I) The following general formula (I):[In the above formula, W represents a group represented by -A-R. A is an oxygen atom,
Or represents a sulfur atom. R is C₁-C₆The alkyl
Base, C₂-C₆Alkenyl group of C₂-C₆The alkini
Lu group, C₃-C₆Cycloalkyl group, or -CR¹
R²-CO-OR ³Represents a group represented by. R¹And R
²Is a hydrogen atom or C₁-C_FourShows the alkyl group of
You R³Is a hydrogen atom, C₁-C₆Alkyl group of C₂
-C₆Alkenyl group of C ₂-C₆An alkynyl group of C
₃-C₆Cycloalkyl group, C₁-C₆The halo archi
Group, orA group represented by (R^FourIs C₁-C_FourShows the alkyl group of
Is shown). X represents a halogen atom. X is with W
On -O-CHR^Five-CO-NR⁶-May be formed
Yes. R^FiveIs a hydrogen atom or C₁-C_FourAlkyl group of
Indicates. R⁶Is C₁-C₆Alkyl group of C₂-C₆
Alkenyl group of C₂-C₆An alkynyl group of, or C
₃-C₆Represents a cycloalkyl group. Y is a hydrogen atom,
Alternatively, it represents a halogen atom. Z is one of the following
Is shown as a group. [Chemical 3](U in the above formula represents an oxygen atom or a sulfur atom.
You )] At least one of the pesticide active ingredients represented by
Seeds, and (ii) alkylene glycol rosin ester
And polyalkylene oxide rosin esters
A supplement having an action of preventing crystallization of the agrochemical active ingredient selected from
At least one of the auxiliaries is mixed and melted to form a solid
Solid agriculture characterized by containing what is carried by the body
Medicinal composition. 2. In the general formula (I), an alkynyl group, or -CR ¹ R ² -C R's C ₂ -C ₆
A group represented by O-OR ³ (R ¹ and R ² represent a hydrogen atom, R ³ is a C ₁ -C ₆ alkyl group, or And X represents a halogen atom or W together with And Y represents a halogen atom, and Z represents a group represented by any of the following. [Chemical 6] 3. In the general formula (I), A represents a sulfur atom and R represents —CH.₂COOR³Represented by
Group (R³Is C₁-C _FourAn alkyl group of orWherein X and Y represent a halogen atom, and Z represents a group represented by any of the following:
Solid pesticide composition. [Chemical 8] 4. In the general formula (I), A represents an oxygen atom, R represents a C ₂ -C ₄ alkynyl group, X represents a halogen atom, or together with W, And Y represents a halogen atom and Z represents The solid agricultural chemical composition according to claim 1, which represents a group represented by: 5. The pesticide active ingredient is represented by the following formula: Or the following formula The agrochemical composition according to claim 1, which is represented by: 6. The solid pesticide composition according to claim 1, wherein the weight ratio of the auxiliary agent having an anti-crystallization effect to the pesticidal active ingredient is 0.1 to 10 times. 7. The solid agricultural chemical composition according to claim 1, wherein the weight ratio of the auxiliaries having an anti-crystallization effect to the agricultural chemical active ingredient is 0.1 to 5 times. 8. The solid pesticide composition according to claim 1, wherein the auxiliary agent having an anti-crystallization effect is a polyoxyethylene rosin ester having an ethylene oxide addition mole number of 5 to 18. 9. An anionic or nonionic surfactant is further added. The solid agricultural chemical composition according to claim 1.