JPS59175404A - Emulsifiable powder readily soluble in water and its application - Google Patents

Abstract

PURPOSE:To obtain the titled powder capable of forming a stable solution or emulsion of an active component easily by stirring in water, by converting an agricultural or disinfective drug in the form of a stock liquid containing an emulsifier, and impregnating said liquid in a specific thermally expanded rock powder. CONSTITUTION:The active component of a drug for agricultural use (including horticultural and forestry use) or disinfection use is converted to a stock liquid containing an emulsifier, and the liquid is impregnated in powder of thermally expanded rock having an oil absorption of >=50% and a dissolved emulsion ratio of >=50%, e.g. powder of expanded perlite, pitchstone, etc. to obtain the objective powder. The preparation of the stock liquid is carried out by dissolving the active component in water or in an organic solvent and adding an emulsifier thereto when the active component is soluble in water, or by adding an emulsifier to the active component when it is water-insoluble liquid, or by dissolving the active component in a solvent and adding an emulsifier to the solution when the active component is a water-insoluble solid.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for achieving the above object economically and with improved quality when thermally expandable rock powder is selected from among inorganic silicates as carriers as disclosed in Japanese Patent Publication No. 57-45402. The present invention relates to an emulsifiable powder that is easily soluble in water, which is obtained by solidifying a liquid solution or emulsion stock solution of an agricultural or epidemic prevention agent, and a method for using the same.

Agricultural chemicals here include chemicals in a broad sense, including horticultural chemicals and forestry chemicals.

In addition, the emulsifying powder and granules that are easily soluble in water refer to "oil absorption rate" of 50% or more and "/8 emulsification rate" of 50%, which is specified in the present invention as an active ingredient liquid preparation or emulsion stock solution for agriculture or epidemic prevention. % or more, which is occluded and retained by thermally expanded rock powder, and which easily forms a stable solution or emulsion of the active ingredient when added to water and stirred. .

Agricultural or epidemic prevention drugs are sold and used as preparations containing energizing active ingredients mixed with various auxiliary agents. These preparations are classified into fJT (powders, 9 grains, 1 tablet, permanent formulations, liquid formulations, emulsion formulations, etc.) according to their dosage form.Wettable powders, liquid formulations, and emulsion concentrates are generally diluted with water at the time of use to form suspensions. It is made into an F6 liquid or an emulsion and is generally sprayed using a sprayer. Therefore, since wettable powders, liquids, or emulsion concentrates are used as a carrier and water is used as a carrier, the spraying work itself is more complicated than powders, etc., but the particle diameter of the spraying concentrate is larger than that of emulsions, etc., and there is a risk of drifting and scattering. There is also less lη staining outside of the target environment of the active ingredient. Of all the products that use Kasagi as a carrier, liquids and emulsions are better than wettable powders in water/8P! ? The emulsified active ingredient has a microscopic molecular diameter, and its biological effects are quickly and reliably expressed, and the subsequent decomposition and detoxification are quick, making it a more preferable dosage form. Wettable powders have the active ingredient supported on a solid carrier and are in the form of a solid powder, so they are more convenient to handle than liquid solutions or emulsion concentrates. Therefore, as mentioned above, various attempts have been made to solidify liquid preparations or emulsion stock solutions with properties such as hydrating powders to make them easier to package and handle; for example, cellulose powder or cork powder. (Japanese Unexamined Patent Publication No. 54-26333, Unexamined Japanese Patent Application No. 56-18902), and a method using a water-soluble oligo or polysaccharide as a carrier (Unexamined Japanese Unexamined Patent Application No. 55-4336)
However, the present inventors have previously developed a material with "oil absorption rate" and "/8 emulsification rate" that is richer in resources and more advantageous in terms of quality and cost than these organic powders. are both 50
．． An invention has been made in which a liquid formulation 1 emulsion stock solution of an agricultural, horticultural or epidemic prevention agent is occluded and solidified in 0% or more inorganic silicate powder (
Special Publication No. 57-45402).

Further research was carried out, and when the inorganic silicates described in the patent were used, the rock powder particles were heated and expanded to increase the surface area, and when using powder particles with countless microscopic vents, the following excellent occlusion and elution properties were achieved. After discovering that it is possible to walk through objects, he completed this invention.

The present invention provides that the active ingredient of an agricultural or epidemic prevention drug is made into a liquid stock solution containing an emulsifier, and this liquid stock solution is occluded in thermally expandable rock powder having an oil absorption rate of 50% or more and a dissolution emulsification rate of 50% or more. The active ingredients of emulsifying powders and granules that are easily eluted in water and emulsifiers are used as a liquid stock solution containing an emulsifier. Easily dissolvable in water emulsification characterized by dispersing easily dissolvable emulsifiable powder in water obtained by occluded in granules as it is or as a solution and suspension or emulsified suspension by adding a required amount of water thereto. This is how to use powder and granules.

The present invention is applicable to solid liquid or emulsion obtained by solidifying liquid agricultural or epidemic prevention emulsion stock solution, which is diluted to a predetermined amount of water before being sprayed, and powder which is sprayed in its originally solid form ( It can also be applied to powders (regular powders, DL agents), powders (fine granules F, powders D1 granules (fine granules, fine granules), etc. In other words, the liquefied active ingredient is eluted with an emulsification rate of 50 %
As described above, the object of the present invention can be easily obtained even if it is occluded and solidified in a thermally expandable rock powder having an oil absorption rate of 50% or more and further diluted with an inorganic bulking agent that does not impair this characteristic value. . In addition, for powders or granules that require a certain particle size range, from this perspective, they are formulated in advance by taking into account the oil absorption rate and elution emulsification rate, and then the liquid components and The product of the present invention can also be efficiently obtained by impregnating it with a surfactant mixture. With these considerations, the elution of ingredients is microscopically accelerated by the moisture present in the air or in plants and animals after spraying, resulting in products that are far more effective than conventional products. It can be done. Next, the test method and display method for characteristic values to show the occlusion property of the thermally expandable rock powder used in the present invention and the rate at which the occluded substance is leached into water and emulsified when put into water are set as follows. did.

(1) Put 2 g of the test powder into a beaker with an oil absorption rate of 11, and add the low-toxic organophosphorus agent MPP (dimethyl-3-methyl-4-methylthiophenyl diophosphate - ship name "Hijint") to it.
(hereinafter simply referred to as MPP) Emulsion stock solution (composition below)
At 0±2°C, add dropwise from a buret while scraping with a spoon.

The maximum amount of oil added (Amβ) when the surface of the powder is uniformly smeared with oil and oil is added to the limit that maintains the fluidity of the powder is determined, and the oil absorption rate is calculated using the formula below.

However, α is the specific gravity at 20"c of the sample MPP emulsion stock solution = 1.127 MPP emulsion stock solution composition MPP (dimethyl-3 to methylthiophenyldiobosphene-1) 85.0% polyoxyethylene ( n = 20) styryl phenyl ether
9.3% Calcium dodecylbenzenesulfonate
It is manufactured by taking 5.7% or more and stirring uniformly.

(2) Elution emulsification rate (obtaining the oil absorption rate in 11) Add a constant (A Dissolve and emulsify the MPP component occluded in the beaker. 15 minutes after the start of stirring, add 10 ml! from the center of the beaker while continuing to stir; 37
- A certain amount of internal standard material for gas chromatography (tricresyl phosphate) collected with Lupivenoto
Add 10 m4 of an acetone solution containing 0 m (liquid) and apply this to a gas chromatograph. Separately, the eluted emulsion was centrifuged for 5 minutes (3500 rpm, r
= 12.5 cm), remove 10 ml of the supernatant, add the same internal standard solution $lOmβ, and apply it to a gas chromatograph. The area ratio of each MPP peak to the internal standard peak is determined, and the elution emulsification rate is determined using the following formula.

Elution emulsification rate (%) Thermally expanded rock powder (hereinafter referred to as Expande) used in the present invention
Abbreviated as d Rokles = E, R. ) include the following.

Thermal expansion conditions: 0.8 to 1.2 for each rock powder after crushing the raw ore
About 200 dragons are classified in advance so that they are 90% or more.
After preheating to ~300℃, place it in an electric furnace set at a specified temperature for 10 minutes.
Inflated for ~30 seconds.

Particle size adjustment: Each rock thermal expansion powder was sieved as it was or was crushed and classified.

E, R, -1 perlite from Saga Prefecture. It is a fatty lustrous glassy substance with a pearly structure and a small amount of feldspar. Swelling temperature: 950℃, 0.046m or less, 98.6% E, R, -2gite (obsid 1an) from Nagano Prefecture. It is black glassy and contains trace amounts of feldspar and magnetite. Swelling temperature 1000°C, 0.046 part, 99.1% E, l? , -3
Pi tchs tone 't=produced in Chi prefecture. It has a dark green vitreous pine resin luster and contains a small amount of phenocrysts.

Swelling temperature 850°C, 0.046 dragon or less 98.4% E, R, -4 chlorite or vermiculite from Fukushima Prefecture. It has a dark brown beady luster. Expansion temperature 1000'c, 0.111
11 or less 97.4% E, R, -5 granite from Ibaraki Prefecture. Contains quartz, feldspar, plagioclase, and biotite. Swelling temperature 630℃, 0.046 dragon or less 98.7% E, R, -6 semi-granite (apl'ite> produced in Iwate Prefecture. Potassium feldspar.

It is composed of quartz and contains small amounts of biotite and plagioclase. Swelling temperature 1
ooo℃, 0.046m+m or less 98.3% E, R, -7 Add 3% sodium carbonate fine powder as a flux to E, R, -6 and expand at 1000'C 1i 0.0
Pulverized to 46 ridges or less.

[Reference) E, l? , -1 to 3 rocks are heated and expanded to form a granular material (generally called burai) (Expanded P
It is currently used in large quantities as a building material, heat insulating agent, filter aid, etc. However, the name pearlite is originally the name of a glassy volcanic rock called pearlite, but it refers to the expanded powder particles of pearlite, obsidian, and pinestone. This type of glassy volcanic rock has been known for a long time, but its expansivity when fired was discovered in the United States in 1941, and from 1949 onwards, rapid development took place in the United States. In Japan, its production began in 1958, and the rhyolite (known as quartz trachyte) to which these raw stones belong is the same as quartz, feldspar, mica, and granite, which mainly has an inner surface. Shidereru is the sound of volcanic eruption, and chemically it contains up to 10% water. When this is heated and expanded, the outer glassy portion is softened, but at this time the remaining moisture is also rapidly vaporized and expanded. Rhyolite, a raw material, is widely found in reserves in Hokkaido, Honshu, and Kyushu, and it is one of the materials that will be useful in the future, with no problem in terms of reserves or resources. Also, E, R, -4 and calcined vermiculite (Vermuculi)
te) It is called vermiculite, and the raw stone is produced in the Tamura region of Fuku 1 - Prefecture. Porosil in the US, 5onot
It is called iteZonolite, etc., and is used in many fields like perlite because of its nonflammability, lightness, heat insulation, and electrical insulation properties.

In addition, the following silicates can be used in combination with the solid agent occluded in the thermally expandable rock powder of the present invention (8 no.
It is abbreviated as rganic 5ilicate-8, s.

).

8.S,-1 Siα85 produced by wet method using silicic acid water glass and sulfuric acid
．． 0% dry firing loss (105°C, 4hrs) 8.6
% particle size 0.046+n+ or less 100.0% A, S, -2
Natural aluminum silicate Yamaguchi Kaolin. S+0, 44.2%, AQ2033
Loss on drying of amorphous powder of 8.1%, Na200.8%1.
8%, 98.5% less than 0.046 S, -3 ceramic refractory powder bed leather porcelain powder. Siα74.6%, AQ20321.5%
, loss on drying 0.1%, 0.046 mm or less 99.2% 8S, -4 Calcined diatomaceous earth Diatomaceous earth raw material was dried, crushed and classified, and then calcined at 900°C. 0.046 Dragon or less 98.8% Hachihe S, -5 Calcium Hentonite Shimane Kagai. Moisture 6.2%, pH 7.0% (4x liquid) Swelling power 4.2mβ/2g0 Made of montmorinite, cristobalite, and quartz. 0.046mm or less 97.3% 8, S, -6 Talc Talc from Fukuoka Prefecture. 5i0262.3%, Mg0z30.
5%, AQ2031.2%, moisture 0.2%, 0.046
nr* or less 98.7% 8, S, -7 granular pumice Ishikawa Kengai natural pumice. 5iOz72.0%, AQ2031
5.2%, pale yellowish brown porous fine grains 0.5-0.3mm 9
5.2% 8, S, -8 silica sand Mountain sand from Fukuoka Prefecture. Fine particles mainly composed of SiO2 0.06~0
．． Table 1 shows the values of the oil absorption rate 2 and emulsification rate determined by the above measurements of the thermally expanded rock powder having a thermal expansion of 96.5% or more and the inorganic acid salts.

The thermally expandable rock powder particles E, R, -1 to E, R of the present invention.

-7 had an oil absorption rate and an elution emulsification rate of 50.0% or more. As described above, in order to produce a solid powder for agricultural or epidemic prevention use that is easily emulsifiable in water using thermally expandable rock powder that meets the purpose of the present invention, a liquid stock solution of a liquid agricultural or epidemic prevention agent is required. It can be produced by simply adding and stirring to a powder or granular material having the above-mentioned characteristic values, or by further pulverizing it if necessary.

In addition, when preparing the stock solution of agricultural and epidemic prevention drugs, if the active ingredient of the pesticide or epidemic prevention drug is water-soluble, dissolve it in water or an organic solvent, add an emulsifier to prepare a liquid stock solution, and prepare a water-insoluble liquid. If it is a water-insoluble solid, add an emulsifier to it to prepare the stock solution, and if it is a water-insoluble solid, dissolve it in a solvent and add an emulsifier to prepare the stock solution.

In some cases, as shown in Examples below, water may be added to the emulsion or solution to form a concentrated emulsion or solution for occlusion.

Operations such as drying these occluded emulsions are generally not only unnecessary but also sometimes harmful. This is because if the organic solvent is removed by drying, the active ingredient will precipitate, and there is a risk that a stable emulsion will not be formed when the flinted powder is diluted with water.

In addition to the above-mentioned components, the water-dissolvable emulsifiable powder or granule of the present invention may also contain decomposition inhibitors, potency enhancers, bulking agents, etc. in accordance with conventional formulation methods. As decomposition inhibitors, for example, acidodoposphere=1. -1, 2, 3
, 4', 5, 6, 7.8, or organic substances such as urea, # powder, sugar 1 synthetic resin powder, defatted vegetable powder, cellulose powder, cork powder, etc. I can do it.

Also, as a potency enhancer, piperonyl ptoxide<c+
qIr36os), isobornyl thiocyanoacetate (CI7H(qNO2S)) octachlorodipropyl ether (ceHeCl!zO).These decomposition inhibitors, potency enhancers, fillers and other additives include: Depending on the properties of the additive, it may be added to the liquid material containing the active ingredient before it is occluded in the thermally expandable rock powder, or it may be added after the liquid material has been occluded. The easily dissolvable emulsifiable powder in water thus produced can be obtained as a solid powder containing a high concentration of the active ingredient due to the high oil absorption property of the thermally expandable rock powder.

On the other hand, in water, the thermally expandable rock powder absorbs the active ingredient or its organic solvent solution, so the powder composition of the present invention is used in the field. When doing so, it is sufficient to simply add water necessary to produce the desired concentration, stir, and spray the liquid in a sprayer.

That is, when the solidified emulsion of the present invention is mixed with an appropriate amount of water, most of the active ingredients are immediately released into the water as droplets, and are suspended in thermally expandable rock powder that occludes a small amount of the active ingredients. A stable emulsion-suspension mixture system or solution-suspension mixture system in which particles are mixed can be obtained, and when used, it is diluted with water to the desired concentration, and it can be prepared from a general emulsion stock solution. An emulsion containing a suspended matter and a diluted solution containing a suspended matter can be sprayed from a liquid formulation. As described above, the water-dissolvable emulsifiable powder for agriculture or epidemic prevention according to the present invention has various advantageous properties when used with water, but the powder used is 60%
Since the treatment is carried out at a high temperature of 0 to 1000°C, the number of active sites (r), also known as catalytic activity, decreases, and as a result, the decomposition of active ingredients during storage of these preparations over time is secondary to fluorine. It also shows the advantage of having a small amount. In addition, by swelling, a material with a large total surface area having a large number of fine pores without blind pores, which is ideal as a carrier, can be obtained, and a material with a relatively high strength but a low specific gravity can be obtained.

Another major feature is that it can be obtained easily and economically. In other words, the raw material igneous rock is produced in relatively large quantities in Japan, and it is manufactured using a dry method until it is expanded and classified, so unlike white carbon, it does not require huge amounts of water and expensive wastewater treatment, and can be used for overall resource saving. This is a major feature.

In addition, by selecting fluxes such as pre-swollen sodium carbonate and borax, and their geothermal additives, it is possible to obtain products with physicochemical characteristics, and in particular, we have extensively incorporated cutting-edge research techniques from special ceramics departments. It can be said that there is a possibility that In addition, secondary surface modification techniques for thermally expanded rock powder, such as silane treatment with dihalomethylsilane, hexaalkyldisilazalane, etc., acid-alkali treatment, etc., can easily create unique properties by modifying the surface silanol groups. It can be added to and modified. The easily dissolvable emulsifiable powder in water of the present invention having such various characteristics can be made to have appropriate wettability, and will not generate dust when handled (hygienic and free from excess organic matter). Since there is no need to contain a solvent, there is little danger in terms of fire hazards and environmental health during storage and use.

In other words, conventional emulsions use a large amount of organic solvent to adjust the concentration during production, so when they are diluted with water and sprayed, a relatively large amount of solvent is scattered along with the active ingredient into the surrounding environment. worsen. In general, solvents are more or less toxic, flammable, and hygienic and fire hazards.

In particular, air pollution, water pollution, and soil pollution occur when large amounts of chemicals are handled at once, such as in aerial spraying for forest control.

Complex contamination such as foul odor contamination may increase unexpected risks, but the water-diluted solution of the emulsifiable powder and granules that are easily soluble in water of the present invention has almost no such risk. Normal storage containers for emulsions are airtight containers such as glass, yellowtail, iron 2 synthetic resin bottles, drums, etc. Disposal of empty containers after use involves difficulties such as cleaning and crushing. Also, sufficient care must be taken to avoid environmental pollution.

On the other hand, the most advantageous feature of the powder preparation of the present invention is that it can be stored in a so-called bag-like airtight container mainly made of paper, metal foil, synthetic resin sheet. It is convenient and economical to handle, and empty containers after use can be safely disposed of relatively easily, such as by burning or burying them in the ground. The powder and granule of the present invention thus has the characteristics of both an emulsion and a wettable powder.

As mentioned above, the product of the present invention has a completely unique dosage form and is excellent in terms of environmental pollution, fire disasters, insurance and hygiene.

In addition, the carrier of the present invention and additives such as inorganic silicates with an "emulsion dissolution rate" of 50% or more are also used for powders and powders that are generally sprayed in their original form without being diluted with water at the time of spraying. By using it, it becomes like a liquid agent.

Emulsions and wettable powders that have the same effect as diluted with water and sprayed can be used simply with a duster or granulator.Also, in the case of granules, It is also possible to manufacture carrier particles having a composition suitable for the purpose in advance and impregnating and oil-absorbing a liquid having a liquid emulsion composition suitable for the purpose.

In addition, the pesticides have the compounding ratios in the examples described below.

Or, unless otherwise specified for epidemic prevention drugs, emulsions made by adding water or organic solvents to the active ingredient, or further adding emulsifiers to these,
Alternatively, use the liquid agent stock solution as the thermally expandable rock powder E of the present invention.
, R, -1 to 7, or sometimes inorganic silicates powders A, S, -1 to 8 are added as auxiliary raw materials, and the solution is occluded and solidified by stirring using a Baulkpull kneader. be. %
Unless otherwise specified, the values are weight % (in addition, the comparison was a conventional emulsion, etc., and the difference in drug performance was shown).

The longitude ratio, emulsification ratio, suspension ratio, and elution ratio described in the Examples are measured by the following method.

Longitudinal ratio - Percentage of the initial concentration of the active ingredient decomposed during storage of the formulation in a sealed container (aluminum foil bag) at 40°C for 30 days Emulsification rate - Take 2.5g of the formulation in a 250mβ measuring cylinder and add water to 250m# Close and let stand for 15 minutes.

Next, repeat the inversion 30 times per minute to disperse and emulsify.

After standing still for another 15 minutes, take 30 mβ of the upper layer liquid and centrifuge (35'00 rpm, r = 12.5 cm centrifugal effect - 1747) for 2 minutes. Measure the amount of components in 10 mβ of the bilayer liquid by gas chromatography. . The percentage of this component amount to the component amount contained in 0.1 g of the blend is defined as the emulsification rate.

Dissolution rate - carried out for liquid-absorbable soluble solid compositions,
The dissolution rate is obtained by performing the same miscellaneous operations as the emulsification rate above.

Suspension ratio - 2.5g of formulation in 250ml! Transfer to a measuring cylinder, add water to make 250ml, and let stand for 15 minutes. Next, repeat the inversion 30 times per minute to disperse, emulse, and suspend. After leaving it for 2 hours, a voltage of 10 mA' is drawn from the center of the graduated cylinder to measure the amount of the component contained therein, and the ratio to the amount of the component contained in 0.1 g of this blend is defined as the side ratio.

In addition, the following E1 to E4 were used as emulsifiers (indicated by E) in the examples.

El Polyoxyalkylene alkylene phenyl ether, polyoxyalkylene alkylene phenyl ether, or a polymer thereof.

A mixture of polyoxyalkylene sorbitan alkylate, polyoxyalkylene allyl phenyl ether, or a polymer thereof, and an alkylbenzene sulfonate was selected at a composition ratio that gave the best emulsifying effect for various active ingredients.

E2 Sulfated castor oil E3 Polyoxyalkylene alkyl allyl ether E4 Henzalkonium chloride Example 1 Water-insoluble liquid insecticide MEP (dimethyl-3-methyl-4-nitrophenylphosphorothioate) This product, Control 2
is the conventional composition of the emulsion, MAL is a lauryl mechacrylate deodorant, PAP is isoprobil acid borosephate, an antidegradation agent, and CP is fine cellulose powder.

Example 2 Water-insoluble liquid disinfectant EDDP (ethyl diphenyl dithiophosphate) acid product.

Example 4 Water-insoluble liquid insecticide diazinon (2-isopropyl-
4-Methylpyrimidyl-6-ethyl-thiophosphate) (No. 1).

PVA in the table is polyvinyl alcohol.

Example 6 Water-insoluble liquid herbicide molinate (5-ethylhexahydroazepine-1-carbothioate), water-insoluble solid herbicide simetrine (2-methylthio-4,6bisethylamino-8-triazine), water-insoluble Liquid herbicide MCPB
(Ethyl 2-methyl-4-chlorophenoxybutyrate) In the middle corner 2 of the table and the control, the mixed powder from which the active ingredient had been removed was prepared using E.
(Itl)' was dissolved in water and extruded to a size of 0.5 to 1.21 to form granules, which were then impregnated with a solution obtained by mixing and dissolving the active ingredients in water. Floor 2 corresponds to emulsified granules.

Example 7 Water-insoluble liquid fungicide EDDP (ethyl-diphenyldithiophosphate-1-), water-insoluble liquid insecticide MPP (
Dimethyl-3-methylthiophenylthiophosphate-1-
) Tatsu ψ3 falls under the category of component emulsifying powder.

Example 8 Water-insoluble solid insecticide salithion (2-methoxy-41
-1-1,'3.2~Henzodionexaphosphorine-2
-Sulfil) Example 9 Water-soluble solid herbicide, gramoxone (1,1-dimethyl-4,4-bivirimidium dichloride), water-soluble liquid insecticide, nicotine sulfate (C,.N14 N2) 2 N2 S
04 Example 10 Water-insoluble liquid insecticide orthodichlorobenzene, water-insoluble liquid fungicide metacresol, water-soluble solid fungicide Benzalkonium chloride E (No. 4) Dye: Brilliant Blue FCF Example 11 Water-insoluble liquid insecticide Allethrin, water-insoluble solid insecticide fluthrin, water-insoluble liquid insecticide MEP (dimethyl-3
-Methyl-4-nitrophenylhumesphorothioate) Sinethrin (ethylhexyl-bicycloheptane-dicarboximide) is a potency enhancer.

Example 12 Liquid insecticide propafos (dipropyl-4-methylthiophenyl phosphate) Example 14 Water-insoluble liquid insecticide PAP (dithiophosphate-ethoxycarbonylbenzyl dimethyl) Floor 2. Control 2 is a Flow Dust (F, D,) type powder. PAP (improver) is isoprobil acid phosphate.

Example 15 Water-insoluble liquid insecticide MPP (dimethyl-methylthiophenylthiobosphate), water-insoluble solid insecticide XMC
(xylyl-methyl carbamate), water-insoluble liquid fungicide EDDP (ethyl-diphenyldithiophosphate), water-insoluble solid insecticide futhalide (tetrachlorophthalide) Example 16 Water-insoluble liquid insecticide spindle oil Water-insoluble solid insecticide water Cupric oxide S, B, P: Sucrose monostearate G, G
: Guar gum Example 17 Water-soluble spreading agent DO3S (Na-dioctyl sulfosuccinate), water-soluble solid spreading agent CaLG (Ca-ligninsulfone-1.), water-soluble solid spreading agent fFJPVA
(Polyvinyl alcohol) Commissioner of the Japan Patent Office Mr. Kazuo Wakasugi1, Indication of the case Immediately 5B Patent Application No. 50780 Relation to the case Patent applicant address Mikasa Kagakuko Ugyo Name Mikasa Chemical Industry woki company agent ■ Year and month Japanese Specification 1, Title of the Invention Easily dissolvable in water, emulsifiable powder and granules and method of using the same 2, Claims ■, The active ingredient of an agricultural or epidemic prevention drug is prepared as a liquid stock solution containing an emulsifier, and this liquid stock solution is An emulsifying powder agent that is easily eluted in water, characterized in that it is occluded in thermally expandable rock powder particles having an oil absorption rate of 50% or more and a dissolution emulsification rate of 50% or more.

2. The active ingredients of agricultural or epidemic prevention drugs are made into a liquid stock solution containing an emulsifier, and this liquid stock solution is occluded in thermally expandable rock powder with an oil absorption rate of 50% or more and an elution emulsification rate of 50% or more. Use the soluble emulsifying powder or granule as it is, or add the required amount of water to it to make a solution! ! ! ! A method of using emulsifiable powder and granules that are easily soluble in water, which comprises dispersing them as a suspension or an emulsified suspension.

3. If the liquid stock solution of the active ingredient of an agricultural or epidemic prevention drug is water-soluble, dissolve it in water or an organic solvent and add an emulsifier to it to prepare the liquid stock solution; if the ingredient is a water-insoluble liquid, The easily water-dissolvable emulsifying powder or granule according to claim 1, which is prepared by adding an emulsifier to the powder, and in the case of a water-insoluble solid, it is dissolved in a solvent and prepared by adding an emulsifier.

The present invention aims to achieve the above object economically and with improved quality when thermally expandable rock powder is particularly selected from among the inorganic silicates described in Japanese Patent Publication No. 57-454.02. The present invention relates to emulsifiable powder and granules that are readily soluble in water, which are obtained by solidifying a liquid or emulsion stock solution of an agricultural or epidemic prevention agent, and a method for using the same.

Agricultural chemicals here include chemicals in a broad sense, including horticultural chemicals and forestry chemicals.

In addition, the emulsifying powder that easily dissolves in water refers to an active ingredient liquid preparation or emulsion stock solution for agriculture or epidemic prevention that has an "oil absorption rate" of 50% or more and "?'g emulsification rate" as described below, which is specified in the present invention. 50%
It refers to powder occluded and retained by thermally expanded rock powder having the above characteristic values, and which easily forms a stable solution or emulsion of the active ingredient when added to water and stirred.

Agricultural or epidemic prevention drugs are usually sold and used as preparations containing active ingredients mixed with various auxiliaries. These preparations are usually classified into powders, 1 granule, 2 tablets, permanent formulations, liquid formulations, emulsions, etc., depending on their dosage form. Wettable powders, liquid formulations, and emulsion concentrates are generally diluted with water before use to form suspensions or solutions. , as an emulsion, which is generally sprayed using a sprayer. Therefore, hydrating agents,
Since liquid or emulsion stock solutions use water as a carrier, the spraying process itself is more complicated than for single powder powders, etc. However, the particle size of the spraying stock solution is larger than that of emulsions, so there is less chance of drifting and scattering, and it is a target for active ingredients. There is also less pollution outside of the environment. Among the products that use Kasagi as a carrier, liquid preparations and emulsion preparations are better than wettable powders because they dissolve in water, the molecular diameter of the emulsified active ingredient is microscopic, and the biological effect is expressed quickly and reliably, and the subsequent decomposition and detoxification are more rapid. This is a preferred dosage form. Wettable powders have the active ingredient supported on a solid carrier and are in the form of a solid powder, so they are more convenient to handle than liquid solutions or emulsion concentrates. Therefore, as mentioned above, various attempts have been made to solidify liquid solutions or emulsion stock solutions that have properties superior to wettable powders and the like to make them easier to package and handle. How to make it (
JP-A-54-26333, JP-A-56-18902)
There is also a method using a water-soluble oligo or polysaccharide as a carrier (Japanese Unexamined Patent Publication No. 55-4336), which is even richer in resources and more advantageous in terms of quality and cost than organic powders. As a method, the present inventors first occluded a liquid or emulsion stock solution of an agricultural, horticultural or epidemic prevention agent in an inorganic silicate powder having an "oil absorption rate" and "elution emulsification rate" of 50.0% or more and solidified it. (Special Publication No. 57-45402).

Further research was carried out, and when the inorganic silicates described in the patent were used, the rock powder particles were heated and expanded to increase the surface area, and when using powder particles with countless microscopic vents, the following excellent occlusion and elution properties were achieved. After discovering that it is possible to walk through objects, he completed this invention.

The present invention provides that the active ingredient of an agricultural or epidemic prevention drug is made into a liquid stock solution containing an emulsifier, and this liquid stock solution is occluded in thermally expandable rock powder having an oil absorption rate of 50% or more and a dissolution emulsification rate of 50% or more. The active ingredients of emulsifying powders and granules that are easily eluted in water and emulsifiers are used as a liquid stock solution containing an emulsifier. It is an emulsifiable powder that is easily dissolved in water and is made by occluded in granules, and is characterized by being sprayed as it is, or by adding a required amount of water to it as a solution, suspension, or emulsified suspension. This is a method of using dissolution emulsifying powder and granules.

The present invention is applicable to solid liquid or emulsion obtained by solidifying liquid agricultural or epidemic prevention emulsion stock solution, which is diluted to a predetermined amount of water before being sprayed, and powder which is sprayed in its originally solid form ( It can also be applied to powders (regular powders, ILL agents), powders (fine granules F, powders D), nine granules (fine granules, fine granules), etc. In other words, even if the liquefied active ingredient is occluded and solidified in a thermally expandable rock powder having an elution emulsification rate of 50% or more and an oil absorption rate of 50% or more, and further diluted with an organic/inorganic bulking agent that does not impair these characteristic values, it will still be effective. You can easily explore the object of the invention. In addition, for powders or granules that require a certain particle size range, from this perspective, they are formulated in advance by taking into account the oil absorption rate and elution emulsification rate, and then the liquid components and The product of the present invention can also be efficiently obtained by impregnating it with a surfactant mixture. With these considerations, the elution of ingredients is microscopically accelerated by the moisture present in the air or in plants and animals after spraying, resulting in products that are far more effective than conventional products. It can be done. Next, the test method and display method for the occlusion property of the thermally expandable rock powder used in the present invention and the characteristic value of the reservoir, which indicates the rate of elution and emulsification in water when the occluded substance is put into water, are set as follows. did.

(1) Put 2 g of the test powder into a beaker with an oil absorption rate of 1β, and add the low-toxic organophosphorus agent MPP (dimethyl-3-methyl-4-methylthiophenylthiophosphate - ship name "Hijit")
(hereinafter simply referred to as MPP) Emulsion stock solution (composition below)
Add dropwise from a burette at 0±2°C while stirring with a spoon.

Maximum addition amount (Amp) of 6 when added to the limit where the surface of the powder is uniformly smeared with oil and the fluidity of the powder is maintained.
Calculate the oil absorption rate using the formula below.

However, α is the specific gravity of the sample MPP emulsion stock solution at 20°C =
1.127 MPP emulsion stock solution composition MPP (dimethyl-3-methylthiophenyl thiophosphate) 85.0% polyoxyethylene (n=20) styryl phenyl ether
9.3% Calcium dodecylbenzenesulfonate
It is manufactured by taking 5.7% or more and stirring uniformly.

(2) Elution emulsification rate Add water at a constant temperature of 20 ± 2°C (AX 100mj2) to the oil-absorbing powder composition in a 1z beaker for which the oil absorption rate of (1) was determined, and stir with a magnetic cooler. The MPP components occluded are dissolved and emulsified. After 15 minutes of stirring, collect 10 ml from the center of the beaker using a Holbivent while stirring, and add a certain amount of internal standard material for gas chromatography (1 g of tricresyl phosphate to 100 ml of acetone).
Add 10 mj2 of an acetone solution containing #1 solution and apply it to a gas chromatograph. Separately, the eluted emulsion was centrifuged for 5 minutes (3500 rpm, r = 1
2.5 cm), take 10 mβ of the supernatant, add 10 mA of the same internal standard solution, and apply it to a gas chromatograph. The area ratio of each MPP peak to the internal standard peak is determined, and the elution emulsification rate is determined using the following formula.

Elution emulsification rate (%) Thermal expansion rock powder used in the present invention (hereinafter [1xpand
Abbreviated as ed Rocks = E, R. ) include the following.

Thermal expansion conditions: 0.8 to 1.2 for each rock powder after crushing the raw ore
About 200 m
After preheating to ~300°C, place it in an electric furnace set at a specified temperature.
It was inflated for 0 to 30 seconds.

Particle size adjustment: Each rock thermal expansion powder was sieved as it was or was crushed and classified.

E, R, -1 Perlite Saga Kakeigai. It is a fatty lustrous glassy substance with a pearly structure and a small amount of feldspar. Swelling temperature 950℃, 0.046n or less 98.6% E, R, -2 Obsidian (obsfdfan) Nagano Kengai. It is black glassy and contains trace amounts of feldspar and magnetite. Swelling temperature 10
00℃, 0.046m11.99.1%E, R, -3
Pitches Tone Aichi Kengai. It has a dark green vitreous pine resin luster and contains a small amount of phenocrysts. Swelling temperature 8
50°C, 0.0461 or less 98.4% E, R, -4 Chlorite or vermiculite Fukushima Hangai. It has a dark brown pearlescent luster. Swelling temperature 1000℃, 0.1 dragon or less 97.
4% E, R, -5 granite Ibaraki cliff. Contains quartz, feldspar, plagioclase, and biotite. Swelling temperature 630℃, 0.046 Tsuru or less 98.7% E, R, -6 semi-granite (aplite) Iwate dust collection. Processed feldspar.

It is composed of quartz and contains small amounts of biotite and plagioclase. Swelling temperature 1
000℃, 0.046m1 or less 98.3% E, R, -7 Add 3% sodium carbonate fine powder to E, R, -6 as a flux 100 (0.046 after swelling at 1℃)
Pulverized to less than u.

[Reference] Powder material obtained by heating and expanding rocks of E, R, -1 to 3 is generally called perlite (Expanded Perlite).
lite) and is currently used in large quantities as building materials, heat insulating agents, filter aids, etc. However, the name pearlite is originally the name of a glassy volcanic rock called pearlite, but it refers to the expanded powder particles of pearlite, obsidian, and pinestone.

This type of glassy volcanic rock has been known for a long time, but its expansivity when fired was discovered in the United States in 1941, and from 1949 onwards, rapid development took place in the United States. In Japan, its production began in 1958, but the rhyolite (named quartz trachyte) to which these raw stones belong is the same as granite, which is mainly composed of quartz, feldspar, mica, and ashstone. However, it is the sound of volcanic eruptions and chemically contains up to 10% water. When this is heated and expanded, the outer glassy portion is softened, but at this time the remaining moisture is also rapidly vaporized and expanded. Raw material rhyolite is widely found in reserves in Japan, including Hokkaido, five main islands, and Kyushu, and it is one of the useful materials for the future, with no problem in terms of reserves or resources.

Also E, R, -4 and calcined vermuculite (Vermuculite)
It is called permiculite, and the raw stone is produced in the Tamura region of Fukushima Prefecture. Porosil +5onotite in the US
It is called +5onotite and is known for its nonflammability, lightweight, and heat insulation properties.

Because it only has electrical insulation properties, it is used in many ways like perlite.

In addition, the following silicates can be used in combination with the solid agent occluded in the thermally expandable rock powder of the present invention (8 no.
It is abbreviated as rganic 5ilicate-8,S.

).

^,s,-1 5i02B produced by wet method using silicic acid water glass and sulfuric acid
5.0% dry firing loss (105°C, 4 hrs)
8.6% particle size 0.046 fin or less 100.0% A, S, -2 natural aluminum silicate Yamaguchi dust collection kaolin. Sio, 44.2%, AQzO33
8.1%, Na200.8% amorphous powder loss on drying 1.
8%, 0.046w or less 98.5% A, S, -3 ceramic refractory powder bed leather pottery powder. Si0.74.6%, 8020321.5
%, loss on drying 0.1%, 99.2% less than 0.046 S, -4 Calcined diatomaceous earth Diatomaceous earth raw material was dried, crushed and classified, and then calcined at 900°C. 0.0461 or less 98.8% HachieS, -5 Calcium Bentonite Shimane Kagai. Moisture 6.2%, p) 47.0% (4x liquid) Swelling power 4.2ml! / 2g, made of montmorinite cristobalite and quartz. 0.046mm or less 97.3% A, S, -6 talc from Fukuoka Prefecture. 5iO262.3%, Mgo230.
5%, AQ20z 1.2%, moisture 0.2%, 0.0
46n+ or less 98.7% A, S, -7 granular pumice Ishikawa Kengai natural pumice. 5iOz72.0%, AQ2031
5.2%, pale yellowish brown porous fine grains 0.5-0.3m 95
．． 2% A, S, -8 silica sand Mountain sand from Fukuoka Prefecture. Fine particles mainly composed of SiO2 0.06~0
．． Table 1 shows the oil absorption and elution emulsification ratio values of the thermally expandable rock powder having a diameter of 96.5% or more and the inorganic silicates measured above.

-7 all had an oil absorption rate and an elution emulsification rate of 50.0% or more. As described above, in order to produce a solid powder for agricultural or epidemic prevention use that is easily emulsifiable in water using thermally expandable rock powder that meets the purpose of the present invention, a liquid stock solution of a liquid agricultural or epidemic prevention agent is required. It can be produced by simply adding and stirring to a powder or granular material having the above-mentioned characteristic values, or by further pulverizing it if necessary.

In addition, when preparing the stock solution of agricultural and epidemic prevention drugs, if the active ingredient of the pesticide or epidemic prevention drug is water-soluble, dissolve it in water or an organic solvent, add an emulsifier to prepare a liquid stock solution, and prepare a water-insoluble liquid. If it is a water-insoluble solid, add an emulsifier to it to prepare the stock solution, and if it is a water-insoluble solid, dissolve it in a solvent and add an emulsifier to prepare the stock solution.

In some cases, as shown in Examples below, water may be added to the emulsion or solution to form a concentrated emulsion or solution for occlusion.

Operations such as drying these occluded emulsions are generally not only unnecessary but also sometimes harmful. This is because if the organic solvent is removed by drying, the active ingredient will precipitate, and a stable emulsion may not be formed when the resulting powder is diluted with water.

In addition to the above-mentioned components, the water-dissolvable emulsifiable powder or granule of the present invention may also contain decomposition inhibitors, potency enhancers, bulking agents, etc. in accordance with conventional formulation methods. Examples of decomposition inhibitors used include acid phosphate and epichlorohydrin, and fillers include sulfates, carbonates, chlorides, phosphates, and 8, S, -1, 2, etc. in Table 1. 3,
Inorganic silicates powders such as No. 4, 5, 6, 7, and 8, or organic materials such as urea, starch, sugar 5 synthetic resin powders, defatted vegetable powders, cellulose powders, and cork powders can also be used. .

In addition, piveronyl butoxide (C1
q) (30o5), isofornyl thiocyanoacetate (C
rj HIQ NO2S) octachlorodipropyl ether (Ce H8α30). Depending on the nature of the additives, these decomposition inhibitors, potency enhancers, bulking agents, and other additives may be added to the liquid containing the active ingredient before being stored in the thermally expandable rock powder, or added to the liquid may be added after occlusion. The emulsifiable powder that is easily dissolved in water thus produced can be obtained as a solid powder containing a high concentration of the active ingredient due to the high oil absorption property of the thermally expandable rock powder.

On the other hand, in water, the thermally expandable rock powder absorbs the active ingredient or its organic solvent/8 liquid, so the powder composition of the present invention cannot be used in the field. When used in the field, it is sufficient to simply add water necessary to produce the desired concentration, stir, and spray the liquid form using a sprayer.

That is, when the solidified emulsion of the present invention is mixed with 1 FjJit of water, most of the active ingredients are immediately released into the water as droplets, and are suspended in thermally expanded rock powder particles that occlude a small amount of the active ingredients. A stable liquid formulation of a mixture of emulsion and suspension or a mixture of solution and suspension in which particles are mixed is obtained,
When used, it is diluted with water to a desired concentration, and an emulsion containing a suspension can be sprayed from a general emulsion stock solution, and a diluted solution containing a suspension can be sprayed from a liquid formulation. As described above, the easily dissolvable emulsifiable powder for agriculture or epidemic prevention according to the present invention has various advantageous properties when used with water. Active point (also called catalytic activity)
r) is reduced, and thus also exhibits the secondary advantage that the decomposition of the active ingredient during storage of these preparations over time is very low. In addition, by swelling, a material with a large total surface area having a large number of fine pores without blind pores, which is ideal as a carrier, can be obtained, and a material with a relatively high strength but a low specific gravity can be obtained.

Another major feature is that it can be obtained easily and economically. In other words, the raw material igneous rock is produced in large quantities in Japan, and it is manufactured using a dry method until it is expanded and classified, so unlike white carbon, it does not require huge amounts of water and expensive wastewater treatment, and can be obtained with overall resource savings. is also a major feature. In addition, by selecting a flux such as pre-swollen sodium carbonate or borax, or a geothermal additive thereof, it is possible to obtain products with physicochemical characteristics, and in particular, advanced research techniques of special ceramics departments can be widely adopted. It can be said that there is a possibility. Further, secondary surface modification technology of thermally expanded rock powder,
For example, unique properties can be easily imparted through modification of surface silanol groups, such as treatment with silanes such as dihalomethylsilane and hexaalkyldisilazalane, and acid-alkali treatment. The easily dissolvable emulsifiable powder in water of the present invention having such various characteristics can be imparted with appropriate wettability, is hygienic as it does not generate dust when handled, and is free from excess organic solvent. Since there is no need to contain any substances, there is little danger in terms of fire hazards and environmental health when stored and used.

In other words, conventional emulsions use a large amount of organic solvent to adjust the concentration during production, so when they are diluted with water and sprayed, a relatively large amount of solvent is scattered along with the active ingredient into the surrounding environment. worsen. In general, solvents are more or less toxic, flammable, and hygienic and fire hazards.

In particular, air pollution, water pollution, and soil pollution occur when large amounts of chemicals are handled at once, such as in aerial spraying for forest control.

Complex contamination such as foul odor contamination may increase unexpected risks, but the water-diluted solution of the emulsifiable powder and granules that easily dissolve in ice according to the present invention has almost no such risk. Normal storage containers for emulsions are airtight containers such as glass, tin, iron 1 synthetic resin bottles, 2 cans, drums, etc. Disposing of empty containers after use is difficult due to cleaning, crushing, etc. Also, sufficient care must be taken to avoid environmental pollution.

On the other hand, the most advantageous feature of the powder preparation of the present invention is that it can be stored in a so-called bag-like airtight container mainly made of paper, metal foil, and synthetic resin sheets. It is convenient and economical to handle, and empty containers after use can be safely disposed of relatively easily, such as by burning or burying them in the ground. The powder and granule of the present invention thus has the characteristics of both an emulsion and a wettable powder.

As mentioned above, the product of the present invention has a completely unique dosage form and is excellent in terms of environmental pollution, fire disasters, insurance and hygiene.

In addition, the carrier of the present invention and additives such as inorganic silicates with an "emulsion dissolution rate" of 50% or more are also used for powders and powders that are generally sprayed in their original form without being diluted with water at the time of spraying. By using it, it becomes like a liquid agent.

The same effect as that obtained by diluting emulsions and wettable powders with water and spraying them can be efficiently used simply with a duster or granulator. In the case of granules, they can also be produced by preparing carrier particles having a composition suitable for the purpose in advance and impregnating and oil-absorbing a liquid having a liquid emulsion composition suitable for the purpose.

In addition, the pesticides have the compounding ratios in the examples described below.

Or, unless otherwise specified for epidemic prevention drugs, emulsions made by adding water or organic solvents to the active ingredient, or further adding emulsifiers to these,
Alternatively, use the liquid agent stock solution as the thermally expandable rock powder E of the present invention.
, R, -1 to 7, or sometimes inorganic silicates powders A, S, -1 to 8 are added as auxiliary raw materials, and the solution is occluded and solidified by stirring using a portal kneader. . %
is weight % unless otherwise specified (note that the comparison shows the difference in the amount of chemicals used using conventional emulsions, etc.).

The longitude ratio, emulsification ratio, suspension ratio, and elution ratio described in the Examples are measured by the following method.

Longitudinal ratio - Percentage of the initial concentration of the active ingredient decomposed during storage of the formulation in a sealed container (aluminum foil bag) at 40°C for 30 days Emulsification rate - Take 2.5 g of the formulation in a 250 m4 measuring cylinder and add water to make 250 mβ. , let stand for 15 minutes.

Next, repeat the inversion 30 times per minute to disperse and emulsify.

After standing still for another 15 minutes, 30 ml of the supernatant liquid was taken and centrifuged (3'500 rpm, r = 12.5 cm centrifugal effect -1747) for 2 minutes, and the amount of components in the supernatant 10 mβ was measured by gas chromatography. The percentage of this component amount to the component amount contained in 0.1 g of the blend is defined as the emulsification rate.

Dissolution rate - carried out for liquid-absorbable soluble solid compositions,
The elution rate is obtained by performing the same operation as the emulsification rate above.

Suspension Ratio - Take 2.5 g of the formulation in a 250 mβ graduated cylinder, add water to make 250 m A', and let stand for 15 minutes. Next, repeat the inversion 30 times per minute to disperse, emulse, and suspend. After leaving it as it is for 2 hours, take a 10 m 'II sample from the center of the Menu cylinder, measure the amount of ingredients contained therein, and take the ratio to the amount of ingredients contained in 0.1 g of this blend as the suspension ratio.

In addition, the following E1 to E4 were used as emulsifiers (indicated by E) in the examples.

El Polyoxyalkylene alkylene phenyl ether, polyoxyalkylene alkylene phenyl ether, or a polymer thereof.

Polyoxyalkylene sorbitan alkylate A mixture of polyoxyalkylene allyl phenyl ether, its polymer, and alkylbenzene sulfonate, the composition ratio of which was selected to give the best emulsifying ratio for various active ingredients.

El Sulfated castor oil E3 Polyoxyalkylene alkyl allyl ether E4 Benzalkonium chloride Example 1 Water-insoluble liquid insecticide MEP (dimethyl-3-methyl per diem-nitrophenyl phosphorothiony per diem product, Control 2
The conventional composition of the emulsion is MAL: lauryl methacrylate deodorant, PAP: isoprobil acid phosphate, an anti-decomposition agent, and CP: fine cellulose powder.

Example 2 Water-insoluble liquid disinfectant EDDP (ethyldiphenyldithiophosphate-1-) In the table, PGE is phenylglycidyl ether, Control 1.2
are conventional hydrating agents and emulsifying agents.

Example 3 Water-insoluble solid insecticide BPMC (2-secondary-butylphenyl-N-methylcarbamate) with a melting point of 30°C In the table, DB is dodecylbenzene, and column 2 is a livestock composition.

Example 4 Water-insoluble liquid insecticide diazinon (2-isopropyl-
4-methylpyrimidyl-6-ethyl-thiophosphate) and NaHCO3 to emulsify it.

(1) to absorb it.

Example 5 Water-insoluble liquid insecticide Marathon (dimethyl diurbethoxyethyl dithiophosphate) In the table, PVA is polyvinyl alcohol.

Example 6 Water-insoluble liquid herbicide molinate (5-ethylhexahydroazepine-1-carbothioate), water-insoluble solid herbicide cymetrine (2-methylthio-4,6bisethylamino-S-)riazine), water Insoluble liquid herbicide MCPB
(Ethyl 2-methyl-4-chlorophenoxybutyrate) In Table 2 and the control, the mixed powder from which the active ingredient had been removed was prepared using E.
(Nnl) water was added thereto and extruded to a size of 0.5 to 1.2 mm to make a uniform granulation product, which was then impregnated with a solution in which the active ingredients were mixed and dissolved. Floor 2 corresponds to emulsified granules.

Example 7 Water-insoluble liquid fungicide EDDP (ethyl-diphenyldithiophosphate), water-insoluble liquid insecticide MPP (dimethyl-3-methylthiophenylthiophosphate) 3 in the table corresponds to the component emulsifying powder.

Example 8 Water-insoluble solid insecticide salithion (2-methoxy-4H
-1,3,2-benzodionexaphosphorine-2-sulfide) Anone and infron are solvents.

Example 9 Water-soluble solid herbicide, gramoxone (1,1-dimethyl-4,4-bipyrimidium dichloride), water-soluble liquid insecticide, nicotine sulfate (CION14 N2) 2 N2 S
04 Example 0 Water-insoluble liquid insecticide orthodichlorobenzene, water-insoluble liquid fungicide metacresol, water-soluble solid fungicide benzalkonium chloride E (k4) Note) Fragrance di-synthetic pine needle fragrance dye: Brilliant Blue FCF Example 11 Water-insoluble liquid insecticide allethrin, water-insoluble solid insecticide fluthrin, water-insoluble liquid insecticide MEP (dimethyl-3
-Methyl-4-di1-lophenylphosphorothioate) Sinethrin (ethylhexylhcyclohebutane-dicarboximide) is a potency enhancer.

Example 12 Liquid insecticide propafos (dipropyl-4-methylthiophenyl phosphate) Approximately 4 million No. 2, Control 2 is E, 11. , A, S, from 0.6 to 1 by wet extrusion method using PEO as a binder.
．． Two fins were granulated and dried, and propaphos in which E (No. 1) was dissolved was added and oil absorbed.

Example 13 Water-insoluble liquid insecticide ethylthioethyl (dithiophosphoric acid-
Diethyl-2-ethylthioethyl) Example 14 Water-insoluble liquid insecticide PAP (Ethoxycarbonylbenzyldimethyl dithiophosphate) Arashi 2. Control 2 is a Flodus (F, D,) type powder. PAP (improver) is isoprobil acid phosphate.

Example 15 Water-insoluble liquid insecticide MPP (dimethyl-methylthiophenylthiophosphate), water-insoluble solid insecticide MMC
(xylyl-methyl carbamate), water-insoluble liquid fungicide EDDP (ethyl-diphenyldithiophosphate), water-insoluble solid insecticide fluoride (tetrachlorophthalide) Example 16 Water-insoluble liquid insecticide spindle oil water-insoluble solid fungicide Agent cupric hydroxide G, G: Guar gum Example 17 Water-soluble spreading agent DO3S (Na-dioctyl sulfosuccinate), water-soluble solid spreading agent CaL, G (Ca-
lignin sulfonate), water-soluble solid spreading agent PVA (
Polyvinyl alcohol) JP-A-59-175404 (7!2)

Claims (1)

[Claims] 1. The active ingredient of an agricultural or epidemic prevention agent is made into a liquid stock solution containing an emulsifier, and this liquid stock solution is occluded in thermally expandable rock powder having an oil absorption rate of 50% or more and an elution emulsification rate of 50% or more. An emulsifiable powder and granule that is easily soluble in water. 2. An underwater easy-to-use product made by storing the active ingredient of an industrial or epidemic prevention drug in a liquid stock solution containing an emulsifier, and absorbing this liquid stock solution into thermally expandable rock powder particles with an oil absorption rate of 50% or more and an elution emulsification rate of 50% or more. Use of emulsifiable powders and granules that are easily dissolvable in water, characterized in that they are sprayed as they are, or by adding a required amount of water to them as solutions and suspensions or emulsified suspensions. Method. 3. If the liquid stock solution of the active ingredient of the M industrial or epidemic prevention drug is water-soluble, dissolve it in water or an organic solvent and add an emulsifier to it to prepare it; if it is a water-insoluble liquid, Adjust by adding an emulsifier to this, and if it is a water-insoluble solid, dissolve it in a solvent, add an emulsifier, and make 8I? 1. The emulsifiable powder and granules that are readily soluble in water according to claim 1, which are obtained by preparing an illuminant.