JPH06192009A - Stable foamable solid agent for agricultural chemical - Google Patents

Abstract

PURPOSE:To obtain an agricultural chemical composition having ready handleability, not having undesirable influence on an operator and environment, providing good result in terms of effect on organism and phytotoxicity. CONSTITUTION:This foamable solid agent for agricultural chemical is blended with magnesium oxide having 130-170mg/MgO (g) iodine absorption amount to give an agricultural chemical agent having stability with the elapse of time. The agent has improved moisture resistance, prevents expansion of the bag of the fomable solid agent for agricultural chemical with time, does not reduce foaming properties with time and is stable.

Description

Detailed Description of the Invention

[0001]

OBJECT OF THE INVENTION The object of the present invention is to keep the solid effervescent agricultural chemicals stable over time.

[0002]

BACKGROUND OF THE INVENTION The present invention allows the presence of special magnesium oxide in the same package or formulation.
The present invention also relates to a pesticide formulation which has improved moisture resistance by using a special moisture-proof packaging and is stable over time.

[0003]

Conventionally, agricultural chemicals for paddy fields have been formulated into various dosage forms, such as powders, wettable powders, emulsions, granules, etc., and sprayed on the surface of water or rice plants for convenient use. .

However, powders and wettable powders have health problems for users and producers due to dusting and environmental pollution.
In the case of emulsions, there are problems of toxicity of organic solvents and fire. Although granules have few such drawbacks, they are not only disadvantageous in terms of physical distribution and economical efficiency, but they are effective only after the active ingredient is once dissolved in water and absorbed by plants from roots or stems. Therefore, in the case of an active ingredient having a property of being poorly soluble in water, easily adsorbed to soil, or having no permeation transferability, sufficient control activity is often not obtained as compared with other dosage forms.

For these reasons, recently, floorable (hereinafter abbreviated as FL) and dry floorable (hereinafter abbreviated as DF)
A new dosage form has been developed. These are diluted with water and used as an aqueous solution, suspension or emulsion. These dosage forms called FL and DF can be said to be the dosage forms that have solved the above-mentioned drawbacks of wettable powders in that they are free from powdering and have fluidity, but since these preparations are dispersed including conventional dosage forms. First, after dissolving or dispersing in water,
You will enter the paddy field and spray it using a spraying tool. In this way, preparing diluting containers and spraying equipment and spraying them in paddy fields is not only an economic burden and a concern for safety for small-scale part-time farmers, but it also requires labor and time. The burden is heavy. Especially for modern farmers, who depend heavily on the elderly and women, such burdens are unbearable.

For this reason, recently, as a method that can be easily sprayed without requiring a special tool for spraying, there is a method in which the herbicide FL is put in a plastic bottle and sprinkled into the paddy field through a small hole formed in the cap portion. It has been developed. This method has the advantage that it can be sprayed easily without the need for special equipment for spraying, but the spraying of the chemical liquid may be necessary due to the fact that it is still necessary to enter the paddy field for spraying, and depending on the spraying method and wind direction. Has some drawbacks such as being
It cannot always be said that the drawbacks of the conventional method could be completely eliminated. In addition, disposal of used empty bottles may cause safety and environmental problems.

Further, recently, a herbicide for paddy field, which contains a surfactant and a foaming agent as active ingredients (Japanese Patent Laid-Open No. 128301/1993).
No.), an active ingredient, a surfactant, and a padding herbicide tablet or capsule containing a binder (JP-A-3-173).
No. 802) has been disclosed. In treating these preparations, it is preferable to wrap these preparations in water-soluble paper such as a film of polyvinyl alcohol (hereinafter abbreviated as PVA) and throw it into the paddy field from the viewpoint of the safety of the sprayer and environmental protection. This is an effective method (Japanese Patent Laid-Open No. 4-
No. 226901).

[0008]

Since such an injectable preparation does not uniformly disperse like conventional granules and powders, it is necessary to spread the active ingredient throughout the field as soon as possible. Blend so that the solids disintegrate and disperse as quickly as possible. At this time, the foaming agent,
A water-soluble solid acid and a carbonate are blended, and the mechanism in which both react in the presence of water to generate carbon dioxide is used.
In many cases, the moisture in the formulation and the air react with each other during storage, causing problems such as swelling of the packaging and no foaming during use. In particular, because the water temperature in the paddy field is relatively low, it is necessary to disperse the active ingredient in the paddy field by the foaming force and dissolve and diffuse it as quickly as possible to form a uniform treatment layer on the soil surface. When the foaming power is lowered, diffusion of the active ingredient becomes insufficient, which may cause insufficient drug effect or drug damage.

On the other hand, products containing a foaming agent have been commercialized in various fields such as medicines, bath salts, confectionery, disinfectants, and cleaning agents. In order to prevent gas generation due to reaction during storage,
Conventionally, a method of blending anhydrous sodium sulfate (Japanese Patent Publication Sho 58
No. 5695), a foaming bath agent containing magnesium oxide and / or sodium aluminate (JP-A-5959).
No. 70610), carbon dioxide gas is blown into the foaming agent to form bicarbonate from water and carbonate in the preparation (Japanese Patent Publication No. 22197/1992), PEG, etc. on the surface of the organic acid of the foaming agent. And a method of preventing direct contact between an organic acid and a carbonate (Japanese Patent Laid-Open No. 61-176519), a method of using coarse particles for the acid or the carbonate, and the like have been proposed. However, these methods have no practical effect, cannot be applied to agricultural chemicals because the process is complicated and the processing cost is high, and the expansion of the packaging with time can be prevented, but the foaming power at the time of use decreases. However, as described above, it was not practical to apply it to a pesticide throwing-in formulation that requires strong effervescence even at low temperatures.

In view of the above situation, the present inventors have aimed to develop an effervescent formulation of agricultural chemicals whose effervescence does not decrease with time and the bag does not expand, and in particular, JP-A-59-70610. Therefore, the inventors have conducted intensive research focusing on magnesium oxide for which the gas generation preventing effect of the effervescent bath agent is recognized.

As a result, among many types of magnesium oxide, the iodine adsorption amount is 130 to 170 mg.
/ MgO (g) magnesium oxide has the effect of preventing the bag of the agricultural chemical solid agent containing a foaming agent from expanding over time, and when such magnesium oxide is added to the formulation, Since the solid agent does not harden, the decrease in foaming property can be prevented. Furthermore, the coexistence of calcium oxide in addition to magnesium oxide can further prevent the bag from expanding and the foaming property from decreasing. And completed the present invention.

[0012]

[Constitution of the invention]

[0013]

Means for Solving the Problems The present invention provides a pesticide formulation which is stable over time, in which magnesium oxide having an iodine adsorption amount of 130 to 170 mg / MgO (g) is allowed to coexist in a solid effervescent pesticide formulation, and further, A pesticide formulation in which calcium oxide coexists, and the pesticide formulation is a bag or box made of aluminum foil laminated film that is degassed by threading or perforation, or a bag or box made of aluminum vapor deposition or silica vapor deposition film. It is a pesticide packaging form that is moisture-proof packaged in.

Mainly as a desiccant and a carbon dioxide absorbent,
Special magnesium oxide is used in the present invention.

The quality of what is generally called magnesium oxide varies remarkably depending on the firing temperature when the raw material magnesium hydroxide or magnesium carbonate is baked. The one having a high firing temperature (1000 ° C. or higher) is called dead-burned magnesium oxide and is used as an electromelted magnesia and a magnesia clinker. These are characterized by their low bulk and low water content. On the other hand, those having a relatively low firing temperature (600 to 1000 ° C.) are fine powders having a high bulk and are called light burned magnesium oxide. There are various grades of light-burned magnesium oxide depending on the purity, particle size, difference in firing temperature or firing time. In general, those having a relatively low firing temperature and a relatively short firing time tend to have a large loss on ignition, a large specific surface area, a high bulk, and a high iodine adsorption amount. Among light burned magnesium oxide, it has a large specific surface area, high bulk, and high iodine adsorption (130
˜170 mg / MgO (g)) has a low bulk and a low iodine adsorption amount in a synthetic resin as a vulcanization aid (15).
-25 mg / MgO (g)) is used for cement, grindstone, and the like. There are light, heavy, and fine granules used for medicine, which are mainly used for suspension preparations, excipients, and preparations in hospitals, and the iodine adsorption amount is 30 to 50 mg / MgO (g). Degree or less. In addition, there are many grades for applications such as ceramics, special glass, dental materials, synthetic rubber and synthetic resins.

The magnesium oxide used in the present invention is
Iodine adsorption amount measured by the method described below is 130 to 170 m
g / MgO (g). It is said that even if the iodine adsorption amount is other than this, it absorbs moisture and carbon dioxide in the air, but the stabilizing effect on the solid effervescent pesticide preparation is insufficient, and the effect of the present invention cannot be achieved.

The magnesium oxide used in the present invention may be in the powder form or in the form of granules or lumps formed from the powder form as long as it has an iodine adsorption amount of 130 to 170 mg / MgO (g).

In the present invention, magnesium oxide is allowed to coexist in the solid agricultural chemical formulation of effervescent pesticide. Magnesium oxide is used as a breathable package such as paper, cloth or breathable resin film, or a laminated paper of these sheets. It may be any of a divided form enclosed in, a form in which a lump of magnesium oxide is directly mixed with a solid effervescent pesticide solid agent, and a form incorporated in the formulation of the effervescent pesticide solid agent.

In the case of the packaged form, the coexisting amount of magnesium oxide varies depending on the dosage form and formulation of the solid effervescent pesticide solid agent, but is 0.1 to 0.1% in the usual packing unit of the effervescent pesticide solid agent.
It is about 10 to 150 g in one package of 3 kg. The number of packages of magnesium oxide may be one or two or more per one packaging bag of the effervescent agricultural chemical solid agent.

In the case where magnesium oxide is added to the formulation of the solid effervescent pesticide formulation, magnesium oxide is pulverized with the agricultural chemical active ingredient (if wet pulverized, dried), effervescent agent and / or other auxiliary agent. After mixing with
If necessary, use a suitable molding machine to formulate into solid preparations such as powder, granules, tablets and briquettes. When the solid agent is a lump such as granules, tablets, briquettes, etc., it is crushed with an agrochemical active ingredient, a foaming agent and / or other auxiliary agents, if necessary, and then formulated into a desired dosage form. Dust is a mixture of an active ingredient pulverized product, magnesium oxide, a foaming agent component and other auxiliaries and pulverized, and a granule is obtained by granulating the above mixture using a dry granulator, and a tablet is prepared by mixing the above mixture. It can be obtained by tableting using a tableting machine, and a briquette can be obtained by compression molding the above mixture using a briquetting machine. Since the effervescent preparation reacts in the presence of water and foams, and magnesium oxide changes into magnesium hydroxide in the presence of water, wet molding must be avoided. When it is unavoidable to perform wet molding, the solid acid and the carbonate portion are separately wet granulated, dried, and magnesium oxide is added to the dried product, followed by dry molding. in this case,
The active ingredient and other auxiliaries will be added at any step during granulation of the acid part or carbonate part, or during dry molding.

The content of magnesium oxide in the formulation is
Although it depends on the formulation and formulation of the solid effervescent pesticide, caution should be exercised because if the blending amount is too large, the effervescence will decrease and the tabletability will tend to deteriorate. In general,
It is about 0.3 to 10%, preferably about 0.5 to 5%, more preferably 1 to 3%. With such a blending amount, the decrease in foamability can be sufficiently recovered by adjusting the blending amount of the solid acid.

Mixing magnesium oxide and / or sodium aluminate with the effervescent bath agent is disclosed in JP-A-59-59.
70610. However, even when this method is applied to pesticides, only magnesium oxide having the above iodine adsorption amount specifically shows a stabilizing effect, and other magnesium oxides have no stabilizing effect. It is considered that the expansion of the foaming agent package is caused by the reaction between the organic acid and the carbonate in the presence of water to generate carbon dioxide gas. As an inhibitor of such a reaction involving water, the iodine adsorption amount 1
30-170 mg / MgO (g) magnesium oxide,
That is, magnesium oxide, which has been burned at a relatively low temperature for a short time and has a higher ignition loss value than other grades, is more effective than magnesium oxide, which has been fired at a high temperature for a long time and has a low ignition loss value. Is amazing. It is not clear what causes such a difference in the stabilizing effect between the bath agent and the pesticide, but it is considered to be due to the difference in the active ingredient and the auxiliary agent mixed in both.

If calcium oxide is further added to the magnesium oxide, the stabilizing effect is further improved.

Although bag expansion can be prevented by using calcium oxide alone, when calcium oxide is added to the formulation of the solid agent, the hardness of the solid agent tends to deteriorate during storage, especially after storage at room temperature. Can not be mixed with. On the other hand, when a large amount of magnesium oxide is blended, as described above, the foamability tends to deteriorate, and in the case of tablets, the tableting property tends to deteriorate. By adding calcium oxide in addition to the above magnesium oxide, the drawbacks of both can be compensated for, and there is no swelling or hardness deterioration of the bag during storage, and there is no problem in terms of tabletability. You can

In the case where the magnesium oxide lump is directly mixed with the effervescent pesticide solid agent, a magnesium oxide lump is prepared separately from the effervescent pesticide solid agent, and both are mixed in the preceding step of subdivision, Enclose in moisture-proof packaging. This agglomerate may be in any form such as a grain, a tablet, a briquette, a sphere, a die, or a donut. If water is used to make magnesium oxide into such a lump, the magnesium oxide reacts and is deactivated, so that it is molded by a dry method. As a dry molding machine, a roller compactor, a tableting machine, a briquetting machine or the like is used. The size of the agglomerate is not particularly limited, but if it is too large, the handling becomes inconvenient, so it is desirable to set it to the same level as or smaller than that of the solid effervescent pesticide to be stabilized. In particular, it is convenient to use the same form and size as the effervescent pesticide solid agent, because problems such as classification are eliminated. The blending amount of these lumps with respect to the effervescent pesticide solid agent varies depending on the formulation and formulation of the effervescent pesticide solid agent, but is generally about 0.3 to 10%, preferably about 0.5 to 5%. Compared to the case of blending in the formulation, the effect on the foamability when cast in water is less, but in order to achieve the same effect, it is necessary to blend a little more than in the formulation. .

If calcium oxide is added to the above magnesium oxide to form a lump, the lump can be easily molded, and the stabilizing effect of the solid effervescent pesticide agent is further improved.

The iodine adsorption amount of magnesium oxide was measured by the following method.

1 g of the sample was precisely weighed and put in a 50 ml colorimetric tube, and 50 ml of 0.1N iodine reagent solution (carbon tetrachloride solution of iodine) was added and the container was sealed. Exactly 30 on shaker
Shake for 10 minutes, leave still for 10 minutes, take 10 ml of supernatant with a whole pipette so as not to inhale the sedimented sample, and put it in a 200 ml beaker containing 25 ml of 0.03N iodine solution (75% alcohol solution). , 0.
Titration with a 05N sodium thiosulfate solution until decolorization (V ₁ ml). Separately, 25m of 0.03N iodine solution
10 ml of 0.1N iodine test solution was placed in a beaker containing 1 and titrated with a 0.05N sodium thiosulfate solution (V ₂ ml). The iodine adsorption amount was calculated by the following.

[0029]

[Formula 1] Iodine adsorption amount (mg) / MgO (g) = (V ₂
-V ₁ ) × 127 × N ÷ 0.2 (where N is the normality of the sodium thiosulfate solution. 0.1N
The titer of the iodine test solution is in the range of 0.975 to 1.025) The effervescent pesticide solid agent to be stabilized in the present invention means an agricultural chemical active ingredient, a water-soluble solid acid and a carbonate. Means a solid preparation containing the following foaming agent as an essential component.
This solid effervescent pesticide is applied to the paddy field by a simple application method of throwing it into the paddy field.

The pesticidal active ingredient used in the present invention must be a compound that exerts a biological effect by being put into paddy fields. In the case of insecticides and fungicides, it is desirable that they have the property of being absorbed and transferred to the rice body (osmotic transferability), but even if they do not have the infiltration transferability, insects that live in water or on the water surface, or in water or on the water surface Effective against bacteria that are transmitted from In either case,
It is necessary for the compound to have low phytotoxicity. In the case of a herbicide, it is desirable to select a compound that is particularly harmless from the viewpoint of its original properties and the time of use.

The active ingredient, whether water-soluble or sparingly soluble in water,
It may be solid or liquid. In general, a solid compound is more suitable for the present invention, but a liquid drug substance can be sufficiently applied if it can be solidified by an appropriate method. The solid agent of the present invention may contain two or more kinds of active ingredients.

The active ingredient used in the present invention is an insecticide, preferably isoxathion, propaphos, DEP,
Diazinon, ethyl thiomethone, formothione, dimethoate, monocrotophos, acephate, carbosulfan, thiocyclam, cartap, benfuracarb, fratiocarb, carbaryl, buprofezin, B
PMC, PHC, imidacloprid, permeation-transfer insecticides such as TI304, and synthetic pyrethroids effective against insects living in water or near the surface of water such as rice weevil and rice dwarf beetle such as cycloprotoline and etofenprox.

Among the fungicides, preferably probenazole,
Blasting agents such as isoprothiolane, IBP, tricyclazole, pyroquilon, flutolanil, mepronil, MON
240, S658 and other rubs, tecloftalam, etc. may be mentioned.

Among the herbicides, preferably pyrazolate, benzophenap, pyrazoxifene, pyributycarb,
Bromobutide, mefenacet, bensulfuron-methyl, butachlor, pretilachlor, benchocarb, CNP, clomethoxynil, dimuron, bifenox, naproanilide, oxadiazone, bentazone, molinate, piperofos, dimepiperate, esprocarb, dithiopyr, imazosulfuron, B-frescine, MCP, acne, acne, acne, acne, acne , Pyrazosulfuron-ethyl, KPP314, N- [2
-(3-Methoxy) thienylmethyl] -N-chloroaceto-2,6-dimethylanilide (NSK850), 1-
Paddy field herbicides such as (2-chlorobenzyl) -3- (α, α-dimethylbenzyl) urea (JC940) can be mentioned.

Suitable plant growth regulators include inabenfide, paclobutrazol, uniconazole, triapentenol and the like.

These active ingredients are required to dissolve and diffuse in the paddy water as soon as possible after being introduced into the paddy field to exert their effects. Needless to say, the localization of the active ingredient over a long period of time causes inconvenience such as insufficient efficacy and drug damage. Therefore, even if the active ingredient is highly soluble in water, if it is a solid, it is better to pulverize it to some extent. Fine pulverization is especially necessary when the active ingredient has a low solubility in water. Therefore, it is preferable to carry out dry pulverization with a hammer mill, jet mill, etc., or wet pulverization with a sand mill, attritor, etc., but the solid agent of the present invention is a foaming preparation containing a water-soluble solid acid and a carbonate. Therefore, it reacts in the presence of water and foams,
The wet pulverized product has a drawback that it cannot be directly applied to a molding machine described later. Therefore, the wet-milled active ingredient must be dried in advance. Drying may be performed by directly drying the wet-milled slurry by using a spray dryer or the like, but it is mixed with some or all of other auxiliary agents described later in advance, and if necessary, granulated and then dried. May be. The obtained dry powder or granules are formulated into a target solid agent by using a molding machine or a crusher described below, as in the dry pulverized product. If it is a liquid drug, dissolve it in a suitable solvent or emulsifier, if necessary, and absorb it with a suitable oil-absorbing carrier such as amorphous silicon dioxide, diatomaceous earth, highly oil-absorbing dextrin, calcium silicate, etc. , Solid resin such as ester gum, coumarone resin, petroleum resin, etc., and solidified by forming a solid solution with other solid active ingredients or other chemical substances that are compatible with the liquid drug substance. If so, it can be treated in the same manner as a solid drug substance.

A foaming agent is added to the foaming agricultural chemical solid preparation of the present invention in order to disperse the active ingredient in the paddy field as widely as possible.

The foaming agents include carbonates such as sodium carbonate, sodium sesquicarbonate, sodium hydrogencarbonate, calcium carbonate, potassium carbonate, potassium sesquicarbonate, potassium hydrogencarbonate, citric acid, oxalic acid, succinic acid, malic acid,
A water-soluble solid acid such as maleic acid, fumaric acid, tartaric acid, or boric acid is used by mixing it as a solid.

In the paddy field thrown formulation, the strength of the foaming power is an important factor that influences the biological effect and the chemical damage. Therefore, it is preferable that the foaming power is strong and that the blending amount of the foaming agent is large, but there is a limit in terms of productivity, price, stability and the like of the solid preparation, and the kind of the pesticide active ingredient and other The amount of the foaming agent in the solid agent is usually about 20 to 80%, though it varies depending on the blending amount of the auxiliary agent and the dosage form.
The ratio of the solid acid to the carbonate varies depending on the type of the acid and the carbonate, so it cannot be said unconditionally. However, foaming is stronger when the amount of the acid is usually higher than the neutralization equivalent of the carbonate. Among carbonates, bicarbonate and sesquicarbonate are better than carbonate,
Among the solid acids, those with high solubility in water such as citric acid, malic acid, oxalic acid, maleic acid and tartaric acid are more foamable than those with slightly lower solubility such as succinic acid, fumaric acid and boric acid. Is strong. On the other hand, however, the stability of the formulation may be poor if bicarbonate or highly soluble acid is used.Therefore, select the type and blending amount of acid and carbonate depending on the active ingredient, other auxiliaries, and dosage form. There is a need to.

When the pesticide active ingredient is a compound which is hardly soluble in water, when the active ingredient particles float on the water surface for a long time,
Since it may be blown by the wind and the localization of the active ingredient may be accelerated, it is desirable to incorporate an appropriate wetting agent in the solid preparation to suspend the active ingredient in water. For this reason,
In the formulation, if necessary, a suitable filler, a disintegrating dispersant, a wetting agent, a lubricant, a binder, a particle growth inhibitor, a stabilizer, a spreading agent, and other components such as a water-mixing agent are added, The formulation should be such that it gets wet with water and easily disintegrates and disperses. In particular, spreading agents and water-generating agents float the solid agent on the surface of the water and spread it as wide as possible on the surface of the water, and disintegrating dispersants and wetting agents prevent the active ingredient from falling off from the suspended solid agent. Important in terms.

As the extender, polycarboxylic acid and polysulfonic acid type polymer surfactants, sodium lauryl sulfate,
Fluorine-based surfactants such as perfluoroalkyl carboxylates, polyoxyethylene alkylaryl ethers,
Polyoxyethylene alkyl ether, polyoxyethylene aryl ether surfactants such as polyoxyethylene tristyryl ether, polyoxyethylene alkyl ester, sorbitan alkyl ester, acetylene alcohol, acetylene diol, and alkylene oxide added to them. Various surfactants such as surfactants and silicone-based surfactants, oils such as paraffin oil and silicone oil, resins such as pine resin, camphor, and naphthalene are suitable. Among these, acetylene alcohol, acetylene diol, and surfactants obtained by adding alkylene oxide to them, silicon-based surfactants, fluorine-based surfactants, and polyoxyethylene aryl ethers such as polyoxyethylene tristyryl ether. A surfactant and the like are particularly useful as the spreader.

As the water-generating agent, fatty acid salts such as magnesium stearate, calcium stearate and sodium oleate, higher alcohols such as stearyl alcohol, higher fatty acids such as stearic acid, silicone oil and its derivatives, fluorine-based surface active agents. Agents, cationic surfactants, hydrophobic silica and the like are suitable. Of these,
Hydrophobic silica is particularly useful because it can make the solid agent water-repellent with a small amount of formulation.

Suitable disintegrating dispersants are, for example, lignin sulfonate, (alkyl) naphthalene sulfonate and its condensates, phenol sulfonate and its condensates, styrene sulfonate condensates, maleic acid and styrene. Salts of condensates with sulfonic acids, salts of carboxylic acid condensates such as acrylic acid and maleic acid, alkylbenzene sulfonates, dialkyl sulfosuccinates, salts of polyoxyethylene alkyl ether sulphates, polyoxyethylene alkyl aryl ether sulphates salt,
Examples thereof include anionic surfactants such as polyoxyethylene alkyl ether phosphate ester salt and polyoxyethylene alkylaryl ether phosphate ester salt. Among these, lignin sulfonate, (alkyl) naphthalene sulfonate and its condensate, phenol sulfonate and its condensate, styrene sulfonate condensate, and the salt of maleic acid and styrene sulfonic acid condensate. The salts of carboxylic acid condensates are particularly useful.

As the wetting agent, a condensate of an alkylnaphthalene sulfonate, an alkylbenzene sulfonate, a dialkyl sulfosuccinate, a salt of polyoxyethylene alkyl ether sulfate, a salt of polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene alkyl. Anionic surfactants such as ether phosphate ester salt and polyoxyethylene alkylaryl ether phosphate ester salt, and nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, and polyoxyethylene alkyl ester Of these, condensates of alkylnaphthalene sulfonates and alkylbenzene sulfonates are particularly useful.

Many disintegrating dispersants and wetting agents can be used together.

The dispersant and the wetting agent are not limited to these, and any suitable cationic or zwitterionic agent can be used. Further, starch, carboxymethyl cellulose and salts thereof, carboxymethyl starch and salts thereof, cross-linked polyvinylpyrrolidone, crystalline cellulose, superabsorbent resins and the like having a property of absorbing water and swelling are also useful as disintegrating dispersants. Is.

Suitable extenders include minerals such as bentonite, talc, clay, diatomaceous earth, amorphous silicon dioxide, calcium carbonate and magnesium carbonate, which are commonly used as pesticide carriers, as well as glucose and sugar. Sugars such as lactose, carboxymethyl cellulose and salts thereof, starch and derivatives thereof, crystalline cellulose, organic substances such as wood flour, water-soluble inorganic salts such as sodium sulfate, ammonium sulfate and potassium chloride, urea and the like can be used. These fillers are used properly according to the purpose,
Among them, dry starch has a high hygroscopic ability and therefore has a capability as a desiccant, and therefore has an action as a stabilizer of a solid agent, and crystalline cellulose has an action as a tableting property improving agent, and thus is particularly useful. is there.

Suitable binders include low molecular weight dextrin, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose and the like. Lignin sulfonate is particularly useful because it can be used as a dispersant and can be used as a bulking agent because it is relatively inexpensive.

The form of the solid effervescent pesticide may be any of powder, granules, flakes, spheres, cylinders, cuboids, cubes, ovales, almonds, odon, donuts, bells and the like.

When two or more kinds of active ingredients are treated at the same time in a paddy field, when they are blended, decomposition may occur or disintegration dispersion may deteriorate. In such a case, since it can be solved by preparing two or more kinds of preparations separately and mixing them, it is possible to simultaneously treat a combination agent which is conventionally incompatible.

The solid agent thus obtained may be thrown into the paddy field as it is, or it may be packaged in a water-soluble paper such as PVA film and thrown into the paddy field.

When packaging in water-soluble paper, the weight of one package is about 30 to 120 g, which is the easiest to throw. With such a weight, even a child, a woman, or an elderly person can easily throw at a target point within 15 m. If it is heavier than this, throwing it will be a pain and it will not be easy to handle a large area. Also, below this, the target location will not be reached due to the influence of the wind.

If the number of inputs to the paddy field in the case of packaging is too small, the active ingredient will not spread over the entire paddy field, resulting in insufficient efficacy and phytotoxicity. On the other hand, if the number of inputs is too large, labor saving becomes meaningless. Therefore, a reasonable number of inputs should be selected. When the solid agent of the present invention is thrown into a paddy field, the number of inputs is about 3 to 30 per 10a, preferably 5 to 2.
It is about 0.

The thus obtained solid effervescent pesticide solid agent or the one obtained by encapsulating it in water-soluble paper has a moisture-proof property under the coexistence of magnesium oxide and, if necessary, calcium oxide, for storage and transportation. Must be packaged in a tall bag or box.

When magnesium oxide is used as a package, the foamable agricultural chemical solid agent prepared by removing magnesium oxide or a water-soluble paper packaged with magnesium oxide is packaged in a moisture-proof package. .

When encapsulating a mass of magnesium oxide together with a foaming pesticide solid agent in a moisture-proof package, the foaming pesticide solid agent prepared by removing magnesium oxide is packaged in water-soluble paper or in a moisture-proof package. When subdividing, the lumps are blended and the exterior is sealed.

In the case of an effervescent agricultural chemical solid agent containing magnesium oxide in the formulation, the effervescent agricultural chemical solid agent already containing magnesium oxide is sealed as it is or in a water-soluble paper in a moisture-proof package.

The moisture-proof package used in the present invention is a bag or box made of an aluminum foil laminated film, an aluminum foil laminated film which is degassed by threading or perforation, an aluminum vapor deposition film or a silica vapor deposition film.

The bag or box made of an aluminum foil laminated film is a bag or box made of a film obtained by laminating an aluminum foil and a resin film of polyethylene, nylon, polypropylene, polyethylene terephthalate, polystyrene or the like or kraft paper.

A bag or box made of a laminated aluminum foil film that has been degassed by threading is a thin film sandwiched between the aluminum foil and a resin film or kraft paper laminate film heat-sealed portion. is there. The thickness and the number of threads are not particularly limited, but if you insert too many threads, the moisture-proof effect decreases, so the diameter is usually 1 m.
The purpose can be sufficiently achieved by inserting one thread of m or less at one end of the seal portion.

A bag or a box made of an aluminum foil-bonded film that has been degassed by making holes is a part of the several films that make up the aluminum foil-bonded film and contains a part of the aluminum foil. It is a bag or box made of aluminum laminated film in which a small hole is made in the film. There are no particular restrictions on the size of the holes or the number of holes, but if the holes are too large or the number of holes is too large, the moisture-proof effect will be reduced, so leave one hole with a diameter of about 1 mm per bag. Can achieve the goal sufficiently.

It is necessary to note that if the through-holes are formed in all the films to be bonded, the moisture-proof effect is extremely lowered.

The thickness of the aluminum foil laminated on these aluminum laminate bags is usually several μm to several tens of μm.

The bag or box made of aluminum vapor-deposited film and silica vapor-deposited film is made of a film obtained by vapor-depositing aluminum or silica on the surface of the resin film as described above. In some cases, the same or different film or kraft paper is used. It is a bag or box formed by laminating multiple layers.

Among these, a bag or box made of a laminated aluminum foil film which has been degassed due to the presence of threads or holes has a terminal portion that is heat-sealed so that when the pressure inside the bag rises, Although it is possible to discharge the gas of the outside of the bag, it has a high moisture-proof effect, so unless the inside becomes negative pressure, the moisture of the outside air hardly enters the bag and accelerates the reaction of the foaming agent, which is especially useful. is there.

The formulation obtained by encapsulating the effervescent agricultural chemical solid agent thus obtained in the above moisture-proof packaging does not expand the package with time as described in detail below, and the effervescent agricultural chemical solid agent is also practically used. There is no deterioration over time that would cause problems.

The embodiments of the present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto.

[0068]

Examples 1 to 10 Newcol 2 in 36.15 parts of water
63.0 parts of the pyrazolate drug substance was suspended in 0.85 parts of 91PG (manufactured by Nippon Emulsifier Co., Ltd.). This suspension was pulverized with an Attritor 1S type (manufactured by Mitsui Miike Seisakusho) at 180 rpm for 45 minutes to obtain a pyrazolate slurry. To this slurry, 7.0 parts of calcium carbonate powder (manufactured by Adachi Lime Industry Co., Ltd.) and Vanillex N
(Sanyo Kokusaku Pulp Co., Ltd.) A solution prepared by suspending and dissolving 29.15 parts in 30 parts of water was added, stirred and mixed, and then spray-dried with a spray dryer L-8 type (manufactured by Okawara Kakoki Co., Ltd.). , Pyrazolate PM was obtained. Separately, 45 parts of pretilachlor base material and 5 parts of the following compounding emulsifier were mixed and dissolved, and Oil Q (manufactured by Nitto Chemical Co., Ltd., highly oil-absorbing dextrin)
Pretilachlor PM was obtained by mixing with 50 parts. Pyrazolate PM 28.57 parts, pretilachlor PM10.
0 parts, dried potato starch 5.0 parts, malic acid 15.0 parts, succinic acid 15.0 parts, sodium hydrogen carbonate 18.0 parts, sodium carbonate 5.43 parts are mixed, and a roller compactor mini type (Freund It was compressed and granulated by Sangyo Co., Ltd., and sieved with a sieve having an opening diameter of 2 mm to obtain granules. 97.0 parts of the obtained granules have talc (Pharmacopoeia)
After adding and mixing 3.0 parts, a tableting machine P-18 type (manufactured by Hata Tekko Co., Ltd.) was used to obtain a diameter of 1 cm and a weight of 1 tablet of 0.
Tableted to 5 g. The obtained tablets are pyrazolate 18.0.
%, Pretilachlor 4.5%. Half of the obtained tablets were divided into 50 g each of Hycelon C-200 (PVA film manufactured by Nigo Film Co., Ltd.) having a thickness of 40 μm and divided into individual sachets. 1 kg of tablets obtained here or 20 sachets of tablets and Kyowamag 150 (Iodine adsorption amount 130
~ 170 mg / MgO (g) magnesium oxide, manufactured by Kyowa Chemical Co., Ltd., iodine adsorption amount measured value 142 mg / MgO
50 g of (g)) was packaged in a package of High-Selon C-200 and the packaging materials listed in Table 1. still,
All the mouths were heat-sealed.

Compounded emulsifier composition Calcium dodecylbenzene sulfonate (manufactured by Nippon Emulsifier Co., Ltd.) 2.0 parts Newcol 2609 (manufactured by Nippon Emulsifier Co., Ltd.) 3.0 parts

[0070]

Example 11 Kyowamag 150 was tabletted to a diameter of 1 cm and a tablet weighing 0.5 g. 50 g of tablets containing 18.0% of pyrazolate obtained in Example 1 and 4.5% of pretilachlor and 5 g of tablets of Kyowamag 150 were mixed and divided into Hycelon C-200. The obtained sachets were each packaged in the packaging materials shown in Table 2 in 20 bags. The mouth was heat-sealed.

[0071]

Example 12 50 g of tablets of Kyowamag 150 of Example 11 and 1 kg of tablets containing 18.0% of pyrazolate obtained in Example 1 and 4.5% of pretilachlor were mixed,
It was packaged in the packaging materials listed in Table 2 and the mouth was heat-sealed.

[0072]

[Example 13] 50 parts of Kyowamag 150 and 50 parts of powdered quicklime A (manufactured by Iwahaku Co., Ltd.) were mixed to have a diameter of 1c.
A tablet was weighed to give a tablet weighing 0.5 g. 50 g of tablets containing 18.0% of pyrazolate and 4.5% of pretilachlor obtained in Example 1 were mixed with 150 g of Kyowamag 150 and 5 g of quicklime, and the mixture was divided into Hyceron C-200.
Each of the obtained sachets is packed into the packaging materials listed in Table 2 in an amount of 20
Wrapped in bags. The mouth was heat-sealed.

[0073]

Example 14 50 g of Kyowamag 150 obtained in Example 13 and 50 g of powder quicklime A and 1 kg of tablets containing 18.0% of pyrazolate and 4.5% of pretilachlor obtained in Example 1 were mixed, and shown in Table 2. It was packaged in the listed packaging material and the mouth was heat-sealed.

[0074]

Example 15 Of the tablet formulations containing 18.0% of pyrazolate and 4.5% of pretilachlor of Example 1,
Tablets were obtained in the same manner as in Example 1 except that 2 parts of Kyowamag 150 and 3.43 parts of succinic acid were used instead of sodium carbonate. The obtained tablets are packed in the packaging shown in Table 2 in an amount of 1 kg each.
Packaged one by one. The mouth was heat-sealed.

[0075]

Example 16 Of the formulation of tablets containing 18.0% of pyrazolate and 4.5% of pretilachlor in Example 1,
Example 1 was changed by changing the sodium carbonate to 1 part of Kyowamag 150, 1 part of powdered quicklime A, 3.43 parts of succinic acid.
A tablet was obtained in the same manner as in. The obtained tablets were packaged in the packages listed in Table 2 in an amount of 1 kg each. The mouth was heat-sealed.

[0076]

[Example 17] A mixture of the raw material premixes in Table 3 was mixed, and a jet Ohmizer type 0101 (manufactured by Seishin Enterprise Co., Ltd.)
, Air pressure 6kg / cm ² , supply rate 1.5kg
It was crushed twice with / hr. A foaming agent and an auxiliary agent portion were added to the crushed product, mixed, and then crushed with a hammer mill. The pulverized product was dry-granulated using a roller compactor mini type, coarsely crushed, and sized through a sieve having an opening diameter of 2 mm. A lubricant is added to the obtained granulated product and mixed, and a diameter of 1 c is obtained using a tableting machine.
Tablets were weighed to give one tablet weighing 0.5 g. The obtained tablets were bensulfuron-methyl 0.5%, pyributycarb 6.0.
%, Daimlon 4.5%. The obtained tablets were divided into 50 g each of Hycelon C-200, and 20 bags and 1 bag of the Kyowamag of Example 1 were subdivided into the packaging materials shown in Table 3 and hermetically packaged. The mouth was heat-sealed.

[0077]

Example 18 The raw material premixes shown in Table 3 were mixed and pulverized twice by using a jet Ohmizer 0101 under the same conditions as in Example 17. A foaming agent portion and an auxiliary agent portion were added to the pulverized product, and the mixture was mixed and then pulverized with a hammer mill. Using a briquetting machine type K102 (manufactured by Taiyo Corporation), the crushed product has a length of 24 mm, a width of 13 mm, and a thickness of 7.
mm, one piece was formed into an almond shape having a weight of 2.0 g.
The obtained molded product contains 0.5% bensulfuron methyl, 4.5% dimuron, and 10.0% mefenacet. 1 kg of the obtained molded product was subdivided into the packaging materials listed in Table 3, and the mouth was heat-sealed. In addition, the amount of iodine adsorbed was 150 mg /
Fine particle magnesium oxide of MgO (g) (manufactured by Kyowa Chemical Co., Ltd., actual iodine adsorption amount 157 mg / MgO)
(G)).

[0078]

Example 19 The raw material premix portion, the foaming agent portion, and the auxiliary agent portion in Table 3 were weighed, mixed, and then pulverized with a hammer mill. The crushed product was dry-granulated using a roller compactor mini-type, coarsely crushed, and sized through a sieve having an opening diameter of 2 mm. A lubricant was added to the obtained granulated product and mixed, and the mixture was tableted to a tablet having a diameter of 1 cm and a tablet weighing 0.5 g using a tableting machine. The tablets obtained contain 24% of pyroquilon. Separately, 1 part of Micromag 3-150 and 3 parts of powdered quicklime A were mixed and tableted to the same size. 0.5 kg of the tablets of pyroquilon obtained here, Micromag 3-150, and 20 g of powdered quicklime A tablets were mixed and hermetically packaged in the packaging materials shown in Table 3. The mouth was heat-sealed.

[0079]

[Example 20] Pyrazolate in the same moisture-proof bag as in Example 5 except that 20 g of Kyowamag 150 was used instead of 50 g of Kyowamu 150.
20 bags of pretilachlor tablets and 1 Kyowa mug
One bag of 50 sachets was packaged.

[0080]

[Example 21] 50 g of Kyowamag 150 instead of 50 g of Kyowamag 150 + 10 g of powder quicklime A
In the same moisture-proof bag, 20 packages of pyrazolate / pretilachlor tablets and 1 package of Kyowamag 150 / powdered quicklime were packaged in exactly the same manner as in Example 5 except that the above package was used.

[0081]

Example 22 50 g of the pyrazolate pretilachlor tablets obtained in Examples 1 to 10 and 1 g of the Kyowamag 150 tablet obtained in Example 11 were mixed to produce Hycelon C-20.
Divided into 0. The obtained sachets were each packaged in the same moisture-proof bag as that used in Example 5 in 20 bags, and the mouth was heat-sealed.

[0082]

Twenty-third sachets of pyrazolate pretilachlor tablet packaging were carried out in the same manner as in the twenty-second embodiment except that the Kyowamag 150 tablets obtained in Example 13 and the powdered quicklime A tablets were used in place of the Kyowamu150 tablets. A packaging bag containing was obtained.

[0083]

Example 24 Tablets were obtained in the same manner as in Example 1 except that sodium carbonate was replaced with 1 part of Kyowamag 150 and 4.43 parts of succinic acid. The obtained tablets were packaged in the same moisture-proof bag as in Example 5 by 1 kg each, and the mouth was heat-sealed.

[0084]

Example 25 Tablets were obtained in exactly the same manner as in Example 1 except that sodium carbonate was replaced with 1 part of Kyowamag 150, 1 part of powdered quicklime A, and 3.43 parts of succinic acid. The obtained tablets were packaged in the same moisture-proof bag as in Example 5 by 1 kg each, and the mouth was heat-sealed.

[0085]

Example 26 Tablets were obtained in exactly the same manner as in Example 1 except that 5 parts of Kyowamag 150 and 0.43 parts of succinic acid were used instead of sodium carbonate. The obtained tablets were packaged in the same moisture-proof bag as in Example 5 by 1 kg each, and the mouth was heat-sealed.

[0086]

[Comparative example]

[0087]

Comparative Examples 1 to 10 The tablets obtained in Example 1 and the tablet sachets were packaged in the same manner as in Example 1 in the packages shown in Table 4, together with the sachet of Kyowamag 150 of Example 1.

[0088]

Comparative Examples 11 to 15 Only the tablets obtained in Example 1 were subdivided into the same packaging materials as those used in Examples 1, 3, 5, 7, and 9 shown in Table 5 and sealed. All the mouths were heat-sealed.

[0089]

Comparative Examples 16 to 22 Magnesium oxide having a different iodine adsorption amount was used instead of the Kyowamag 150 in Example 1 to obtain 50g magnesium oxide tablets.
The obtained one sachet and the pyrazolate of Example 1 18.0
%, And 20 bags of pretilachlor 4.5% tablets were sealed and subdivided into the same packaging materials as in Example 1 listed in Table 6. The mouth was heat-sealed.

[0090]

[Comparative Example 23] Pyrazolate / pretilachlor tablets in 20 packets and powder in the same moisture-proof bag in the same manner as in Example 5 except that 20 g of powder quicklime A was used instead of 50 g of Kyowamag. One bag of quicklime was packaged.

[0091]

COMPARATIVE EXAMPLE 24 Pyrazolate pretilachlor tablets having the same formulation as in Example 1 were separately packaged in the same moisture-proof bag as in Example 5.

[0092]

[Comparative Example 25] Tablets were obtained in exactly the same manner as in Example 24 except that Kyowamag 150 was replaced with powdered quicklime A, and the obtained tablets were subdivided and packaged in the same manner as in Example 24.

[0093]

Comparative Example 26 Sodium carbonate was added to powder quicklime A5.0
Parts, and tablets were obtained in exactly the same manner as in Example 1 except that 0.43 parts of succinic acid was used. The obtained tablets were packaged in the same moisture-proof bag as in Example 5 by 1 kg each, and the mouth was heat-sealed.

[0094]

[Test example]

[0095]

[Test Example 1] The packages obtained in Examples 1 to 19 and Comparative Examples 1 to 22 were respectively stored at 40 ° C. and RH 80% for 4 weeks and 50.
After storing at ℃ for 1 week, the swelling of the packaging and the foaming amount and hardness of the tablets were examined. The results are shown in Tables 1 to 6. still,
The foaming amount and hardness of the tablets were measured by the following test methods.

Method for measuring the amount of foaming: 10 ml of water at 20 ° C. is put into the round bottom flask of the apparatus shown in FIG. 2 g of the solid agent was added to this, and the gas generated immediately by plugging was received through a conduit into a graduated cylinder filled with water at 20 ° C.,
The amount of gas generated (ml) is read after 5 minutes. On this occasion,
Since the carbon dioxide gas generated dissolves in water and the solubility varies depending on the water temperature, special attention should be paid to the water temperature, the amount of water put in the flask, and the thickness of the conduit and the position of the conduit tip to receive the generated gas, in order to avoid errors. is necessary.

Hardness of solid agent: Measured with a digital force gauge MFG-50 type manufactured by Shinko Denshi Co., Ltd. (Unit: kgf) 20 solid agents are measured, and an average value is obtained.

[0098]

[Table 1]

[0099]

[Table 2]

[0100]

[Table 3]

[0101]

[Table 4]

[0102]

[Table 5]

[0103]

[Table 6]

In each of the compositions of the examples, no swelling of the packaging which would cause a practical problem was observed, and neither the decrease in the amount of foaming nor the change in the tablet hardness with time was observed, but the compositions of the comparative examples. In all cases, the expansion of the packaging was remarkable, and the decrease in the amount of foaming of the tablet and the change in hardness were remarkable with time.

[0105]

[Test Example 2] The packaging of the solid agents obtained in Examples 20 to 26 and Comparative Examples 23 to 26 was placed in a room without air conditioning for 1 year and 3 months including 2 summers from May to August of the following year. After storage, the expansion and foaming amount of the package and the hardness were examined. The results are shown in Table 7.

[0106]

[Table 7]

From the results of Examples 20 and 21 and Comparative Examples 23 and 24, Comparative Example 24 showed bag breakage, deterioration of foamability and deterioration of hardness. Compared with this, the deterioration over time of the samples of Examples 20 and 21 and Comparative Example 23 was much improved, but in Comparative Example 23, the swelling of the exterior that could be judged was observed, and the encapsulated powdered quicklime A was packaged. Swelled and was about to break. In Example 20, it was observed that the outer packaging tended to expand slightly,
There was no problem in practical use, and there was no effect on the physical properties of the tablet. In Example 21, no swelling of the outer packaging was observed and no deterioration of the physical properties of the tablet was observed.

In Examples 22 to 23, although the packaging of Example 22 showed a tendency of expansion to such an extent that there was no problem in practical use, deterioration of the physical properties of the tablets was not observed in any of the samples.

In Examples 24 to 26 and Comparative Examples 25 to 26, the bags of the samples of Comparative Example 26 were not swelled, but the hardness was significantly deteriorated and the hardness of many tablets could not be measured. In Comparative Example 25, the package was slightly expanded and the tablet hardness was slightly lowered. In Example 24, although the exterior had a tendency to expand slightly, there was no problem in practical use and no deterioration of the physical properties of the tablet was observed. In Example 26, although the foamability was reduced to such an extent that there was no practical problem, no change in hardness or expansion of the exterior was observed. However, this sample produced a squeaking sound when tableting. In Example 25, neither expansion of the outer package nor change in physical properties of the tablet was observed, and the tableting property of the tablet was also good.

As described above, in each of the samples of the examples, deterioration with time that would cause trouble in practical use was not observed. Above all, when magnesium oxide and quick lime were used together, the drawbacks of the single use were compensated, and the stabilizing effect was further improved.

[0111]

EFFECTS OF THE INVENTION The pesticide formulation of the present invention solves the problems that the foaming pesticide formulation expands when it is stored or transported, and that the pesticide formulation does not sufficiently foam during use. That is, the pesticidal preparation of the present invention has improved moisture resistance, prevents the bag of the solid effervescent pesticide solid from expanding over time, and is stable with no decrease in effervescence over time.

When magnesium oxide is added to the formulation, the solid agent does not harden with time, so that the foamability can be prevented from lowering.

Further, when calcium oxide is made to coexist in addition to magnesium oxide, the bag can be prevented from expanding and the foaming property can be prevented from lowering. The present invention can be easily processed and does not cause a harm to a sprayer or the environment. It provides an agricultural chemical composition, and contributes greatly to the development of agricultural chemicals and the agricultural chemical industry for which safety and labor saving are required.

[Brief description of drawings]

FIG. 1 shows a foaming amount measuring device.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuhiko Tsubota 1041 Sansu Yasu-cho, Yasu-cho, Yasu-gun, Shiga In-house (72) Inventor Hiroshi Sahi 1041 Yasu-cho Yasu-cho, Yasu-gun, Shiga In-house

Claims (3)

[Claims] 1. An iodine adsorption amount of 130 to 170 mg / Mg
A time-stable pesticide formulation in which O (g) magnesium oxide is allowed to coexist in a solid effervescent pesticide solid formulation. 2. The agricultural chemical formulation according to claim 1, which further contains calcium oxide in addition to magnesium oxide. 3. A bag or box made of an aluminum foil laminated film obtained by degassing the pesticide formulation according to claim 1 with a thread or a hole, or a bag made of an aluminum vapor deposition or silica vapor deposition film, Agrochemical packaging in a box that is moisture-proof packed.