JPH0892005A - Solidified agricultural chemical - Google Patents

Abstract

PURPOSE: To obtain a solidified agricultural chemical high in the viscosity of a liquid agricultural chemical, provided with a thixotropic property, excellent in storage stability, and capable of being produced by a simple process. CONSTITUTION: The solidified agricultural chemical having a thixotropic property is prepared by mixing a liquid agricultural chemical, e.g. chloropicrin, 1,2-dichloropropane or dichlorodiisopropyl ether with ultra-fine particle silica. The ultra-fine particle silica is preferably anhydrous silica having an average particle diameter of 0.07-0.5μm for the primary particles, a surface area of 50-500m<2> /g by BET method, and an average particle diameter of 0.5-10μm for the secondary particles produced by the agglomeration of the primary particles. The agricultural chemical may be mixed with a water-soluble and/or biodegradable organic substance (e.g. starch or its degradation product) or natural soil and stones for improving the stability of the agricultural chemical. The agricultural chemical may further be mixed with an inorganic or organic filler for controlling the bulk density and furthermore with a multivalent metal compound for enhancing the activity of the agricultural chemical active ingredient. A gelling agent is preferably together used when the agricultural chemical is solidified.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to liquid pesticides containing synthetic organic pesticides in liquid form (including those that are liquids themselves or dissolved in solvents to form liquids), such as chloropicrin, 1,2 di-diamine. The present invention relates to a technique for solidifying a liquid pesticide having a peculiar irritating odor such as chloropropane and dichlorodiisopropyl ether, high vapor pressure, and strong skin irritancy.

[0002]

2. Description of the Related Art Conventionally, in order to prevent the peculiar irritating odor of liquid pesticides, high vapor pressure, and strong skin irritation,
It is known that these liquid pesticides may be coated directly with a water-soluble polymer. However, in such a formulation, when the water-soluble polymer that is the coating material is damaged during storage, transportation, application, etc., the liquid pesticide in the formulation may spill out and cause phytotoxicity. Therefore, in order to prevent such a phenomenon, dibenzylidene sorbitol (hereinafter abbreviated as DBS), which is a gelling agent, is added to the liquid pesticide to increase the thixotropy of the liquid pesticide, and after solidification, the water-soluble polymer film is added. A method of packaging (Japanese Patent Publication No. 47-1799 and Japanese Patent Laid-Open No. 63-230602) has been proposed.
Further, a method in which a liquid pesticide is absorbed into a porous granular material and coated with a water-soluble polymer (JP-A-1-172302).
Is also proposed.

[0003]

However, in the method described above, the DBS is used as the gelling agent.
In the publication No. 7-1799, N, N dimethylformamide (hereinafter abbreviated as DMF) is used as a solvent for DBS, and when addition is performed as a 25 wt% DBS-DMF solution, for example, 3 times the amount of DMF is added to DBS. There was a drawback that the pesticide active ingredient became low because it was added. In JP-A-63-230602, a polymeric substance is added instead of reducing the DBS amount, and the disadvantage that the pesticide active ingredient becomes low by adding the solvent amount of DBS and the solvent amount of the polymeric substance is disadvantageous. Had. In addition, although a gelling agent is not used in the above-mentioned method, (a) an agrochemical active ingredient is absorbed in a porous granular material, (b) filtration / separation is performed, and (c) a water-absorbing organic aqueous solution is coated, ( d)
It has the drawback of requiring a complicated and long process of forming a water-soluble organic layer on the surface of the porous granular material under relatively low temperature drying. Further, although it is characterized in that the water-soluble zirconium compound is added in the step (c) described above to enable relatively low temperature drying, it also has a drawback that the zirconium compound may be contaminated to the environment. It was Further, since a porous granular material having a large particle size of about 2 to 10 mm is used, there is a drawback that the agricultural chemical active ingredient absorbed (occluded) therein is not completely released but remains. Therefore, the present invention solves the above-mentioned disadvantages (1) and (2) and provides a solidified agrochemical in which the active ingredient of the agrochemical is increased and the environmental pollution is reduced with a simple process.

[0004]

Means for Solving the Problems In the present invention, as a result of intensive investigations for solving the above-mentioned drawbacks, (1) ultrafine particulate silica is mixed with a liquid pesticide to solidify it, and (2) the above ( (1) mixing with an inorganic filler to solidify, (3) mixing with (1) or (2) described above to solidify with an organic filler, (4) (1) to (3).
When solidifying with, use a gelling agent together to solidify,
(5) Adding a water-soluble and / or biodegradable organic substance to the solidified pesticide of (1) to (4), (6) (1) to (4)
Adding natural earth and stones to the solidified pesticide of (7), adding a metal compound to the liquid pesticide of (1) to (4) mixed with ultrafine particulate silica or the solidified pesticide having thixotropic properties, (8) The present invention was accomplished by finding that the pesticide solidified in (1) to (7) was packaged with a water-soluble or biodegradable polymer film.

That is, according to the present invention, (1) a solid pesticide characterized by mixing liquid pesticide with ultrafine particle silica to form a solid form having thixotropic properties, (2) ultrafine particle silica is ultrafine particle (1) The solidified pesticide described in (1), which is anhydrous silica, (3) The solidified pesticide described in (1) or (2), which is further mixed with an inorganic filler, (4) Organic substance (1) to (3) characterized by further mixing a filler, (5) characterized by using a gelling agent together when solidifying (1) to (4) Solidified pesticide described, (6) (1)
~ (5) solidified pesticide characterized by adding a water-soluble and / or biodegradable organic matter to the pesticide solidified by the method of (5), solidified by the method of (7) (1) ~ (5) The solidified pesticide characterized by adding natural earth and stones to the pesticide prepared in (8), (1) to (7), and the metal compound added to the pesticide solidified by the method to further increase the viscosity. And has a thixotropic property, or a solidified pesticide that has been gelled, (9) a liquid pesticide that is mixed with ultrafine particulate silica, to increase the viscosity by adding a metal compound, or has a thixotropic property, or The solidified pesticide that has been gelled, (10) the metal compound is one kind or two or more kinds selected from compounds having aluminum, iron, calcium, manganese, zinc, copper, magnesium and cobalt. (9 Or (10) to solidify pesticide according is (11), characterized in that packaged in water soluble or biodegradable polymer film (1) to (10) solidified pesticide according to a thing.

The liquid pesticide used in the present invention is a liquid pesticide mainly containing a liquid (including a liquid itself or a liquid dissolved in a solvent to be a liquid) and has a peculiar irritating odor. And liquid pesticides with high vapor pressure and strong skin irritation, eg chlorpicrin, 1,2
Dichloropropane, dichlorodiisopropyl ether, etc. can be used. These liquid pesticides may be used alone or in combination.

The present invention provides a solidified pesticide by mixing the above liquid pesticide with ultrafine particle silica. By solidifying the pesticide, the safety of the preparation during storage, application, and transportation, and the applicability are improved.

In contrast to the above liquid pesticides, the solidified pesticides to which the present invention is applied are apparently solid, but exhibit so-called thixotropy, which is easily fluid when stress is applied. The solid state having thixotropy means, for example, when an E-type viscometer is used at 25 ° C., the viscosity (P
1) is about 800 to 50,000 Poise, and viscosity (P2) when measured at a rotor rotation speed of 10 rpm as well.
Is about 200 to 6,000 Poise, and P1 is P2
The thixo index value indicating the solid state is 3 divided by
It indicates a degree or more.

The viscosity measured by an E-type viscometer at 25 ° C. is 800 Po when measured at a rotor rotation speed of 2.5 rpm.
If it is less than ise, the fluidity is too high to be apparently solid, and if it exceeds 50,000 Poise, the fluidity is not exhibited even if stress is applied. Similarly, the rotor speed is 10 rp
If it is less than 200 Poise, the fluidity is too high to be apparently a solid, and 6,000 Po is measured.
If it exceeds ise, it does not show fluidity even if stress is applied. Further, if the thixo index value as a parameter showing fluidity is a value of less than about 3, it becomes a liquid showing fluidity or becomes a solid showing no fluidity even when stress is applied.

When a pesticide formulation having a thirstotropic property is prepared by coating with a water-soluble and / or biodegradable polymer film, if a pesticide having thixotropy is used, it is water-soluble and / or raw It is effective in industrial production of pesticide formulations because it has the characteristic that it loses fluidity and solidifies after being mechanically transferred into a package of a degradable polymer film by a fixed amount and packaged.

When a solidified pesticide is produced by mixing ultrafine particle silica, the amount of the active ingredient of the pesticide does not increase when solidified by adding an amount of ultrafine particle silica having a thixotropic property or more. The pesticide and ultrafine silica are not mixed uniformly and are not suitable for industrial production. Further, in a pesticide formulation that has fluidity even after packaging, if the package is scratched, there is a problem with safety during storage, which is not preferable, and therefore a formulation having thixotropy,
Also effective in terms of safety.

The ultrafine particle silica used in the present invention is silicon dioxide represented by SiO _{2 in the} chemical formula containing no water in the molecule, and hydrous silicon dioxide represented by SiO ₂ .nH ₂ O in the chemical formula. What is called. The average particle size of the primary particles of the above-mentioned ultrafine particle silica is 0.07 μm or more and 0.5 μm or less, and the surface area by the BET method is 50 m ² / g or more and 500 m ² / g or less. Particles are generated, and the average particle size becomes 0.5 μ or more and 10 μ or less. Therefore, the average particle size of the ultrafine particle silica used in the present invention is
It is 0.07 μ or more and 10 μ or less. The ultrafine particle silica described above has a small average particle size, a large surface area, and silanol groups (SiOH) on the particle surface.
Has the property of forming a network structure by causing hydrogen bonds with silanol groups on the surface of other particles. Ultrafine particulate silica used for producing a solid pesticide having thixotropy can maintain the active ingredient of the pesticide at about 85% or more, and is a very effective carrier in terms of formulation cost.

The above-mentioned ultrafine particle silica is, for example, Aerosil 130, 20 as ultrafine particle anhydrous silica.
0, 300, 380, OX50, TT600, MOX8
0, COK84, R982, Nippon Aerosil Co., Ltd., Leolosil QS-10, 20, 30, 40, 10
2, CP-102, and MT-10, which are commercially available from Tokuyama Corporation, and Carplex CS-5, 7, 8, 50, 500, 70 as ultrafine particulate hydrous silica.
It is marketed by Shionogi Pharmaceutical Co., Ltd. under the brand name 1,801.

In the present invention, the above-mentioned ultrafine particle silica is mixed with a liquid pesticide to increase the viscosity of the liquid pesticide and to impart the plastic viscosity with an increased thixotropic property to solidify the liquid pesticide. I am measuring. If the average particle size is too large, it is difficult to increase the viscosity of the liquid pesticide, the amount of ultrafine particle silica added for solidifying the liquid pesticide increases, and the pesticide active ingredient decreases, which is not preferable. These ultrafine silica particles may be used alone or as a mixture with different average particle diameters. The ultrafine particle silica used in the present invention has an average particle diameter of 0.07.
It is preferably in the range of μ or more and 10 μ or less, and when it is used substantially alone, the addition amount to the liquid pesticide depends on the type of the liquid pesticide, but for example, in the case of chloropicrin, 5.0 wt% relative to chloropicrin. Above 15 wt% or less (that is, 5.0 to 15 parts of ultrafine particle silica to 100 parts of chloropicrin. The same applies hereinafter.)
Is preferred. In the present invention, the influence of the addition amount of ultrafine particle silica on the liquid pesticide is extremely large. For example,
In the case of 2 to 3 parts, the properties of the liquid pesticide itself having an extremely low viscosity are exhibited, but when 5.5 parts are added, it becomes a sherbet form. It liquefies when stressed. The amount added is too large, and if it exceeds 15 wt%, the pesticide active ingredient decreases, which is not preferable.

When hydrous silica such as white carbon is used as the silica used in the present invention, since it contains water molecules in the molecule, there may be a problem with respect to the stability of pesticides. For example, in the case of using ultrafine particulate hydrous silica such as Carplex (manufactured by Shionogi Pharmaceutical Co., Ltd.), a carrier capable of adsorbing water molecules contained in the molecule, for example, water solubility of starch or a decomposition product thereof and / or It is preferable to use biodegradable organic matter or natural debris such as sintered diatomaceous earth in combination with ultrafine particulate silica.

In the present invention, ultrafine particulate silica is used as a main component, but since the bulk density may be too small by itself, if desired, a filler or the like is added to adjust the bulk density of the solidified pesticide. However, it is also possible to put it in the packaging etc. The fillers used are classified into inorganic fillers and organic fillers.

The inorganic filler used in the present invention is
It is preferable to have characteristics such as being close to a soil component, having little concern about environmental pollution, and having a small average particle size capable of increasing the viscosity of a liquid pesticide when mixed with a liquid pesticide. In this way, as the inorganic filler preferably used in the present invention, specifically, aluminum silicate, calcium silicate, magnesium silicate and the like can be used. You may use these inorganic fillers individually or in mixture. The average particle diameter of the inorganic filler used in the present invention is preferably in the range of 0.5 μ or more and 10 μ or less. If the particle size is too large, the pesticide active ingredient decreases, which is not preferable.

The organic filler used in the present invention is
It is preferable to have features such as low environmental pollution, biodegradation, and a small average particle size capable of increasing the viscosity of liquid pesticide when mixed with liquid pesticide. In this way, the organic filler preferably used in the present invention represents an organic polymer compound, and specifically, urea formaldehyde resin, melamine resin, polyester resin and the like can be used. You may use these organic fillers individually or in mixture. The organic filler used in the present invention preferably has an average particle size of 0.5 μ or more and 10 μ or less. If the particle size is too large, it is difficult to increase the viscosity of the liquid pesticide, the amount of filler required for solidifying the liquid pesticide increases, and the pesticide active ingredient decreases, which is not preferable.

It is preferable that the amount of the inorganic filler or the organic filler to be added at the time of mixing with the above-mentioned ultrafine particle silica is small in order to enhance the pesticide active ingredient. When the liquid pesticide is chloropicrin, the amount of the ultrafine silica added to the liquid pesticide when mixed with the ultrafine silica and the inorganic filler or the organic filler is 2.0 wt% or more and 7.0 wt% or less, preferably 4 wt% or less. 0.0 wt% or more 6.
It is 0 wt% or less. Further, the addition amount of the inorganic filler or the organic filler used in the present invention to the ultrafine particle silica is preferably 200 wt% or less. If it exceeds 200 wt%, the active ingredient of the pesticide becomes low, which is not preferable.

When ultrafine particle silica is used for the above-mentioned solidified pesticide, a small amount of alcohols, glycols, amines, diamines or the like as a solidification aid may be added to the liquid pesticide in advance for solidification.

In solidifying liquid pesticides in the present invention, known biodegradable polymer substances such as polyester polyol, polyvinyl alcohol, polyvinyl acetate, polyethylene modified polyvinyl alcohol, and other thickening agents, Specifically, polylactic acid, poly (1,4-butanediol succinate), polycaprolactone, polyvinyl alcohol or the like may be added to the liquid pesticide to increase the viscosity of the liquid pesticide before solidifying the liquid pesticide. At this time, the liquid pesticide viscosity was 10 c. p [Centi Poise: c. abbreviated as p] and above 1,000 c. It is preferable to add a polymer substance having good biodegradability until p or less. Liquid pesticide viscosity is 1,000 c. If it exceeds p, the solidified pesticide is too hard and the diffusion of the pesticide active ingredient is delayed, which is not preferable. You may use these polymeric substances individually or in mixture.

In the present invention, a stabilizer may be used in combination when solidifying the liquid pesticide. In the present invention, the term "stabilizer" means a hydrolysis stabilizer for liquid agricultural chemicals. Hydrolysis occurs in the presence of water, and it is preferable that the liquid agricultural chemical component should not be contained as much as possible. A method for stabilizing halogen-based liquid pesticides such as chloropicrin and 1,2-dichloropropane will be described. For chlorpicrin, CCl ₃ · NO
_{In the} presence of H ₂ O, which is represented by the chemical structural formula ₂ , hydrolysis occurs and a mineral acid such as HCl or HNO ₃ is produced as a by-product.
Therefore, it is preferable to remove H ₂ O as much as possible. 1,2 In dichloropropane, CH ₂ Cl · CH ₂ represented by Cl · CH ₃ composed chemical formula H ₂ O cause When there hydrolysis HCl is by-produced. Therefore, it is preferable to remove H ₂ O as much as possible.

When the liquid pesticide described above contains a free mineral acid, it is possible to neutralize it by using a known base such as an inorganic base or an organic base as a hydrolysis stabilizer. preferable.

In the present invention, when solidifying the liquid agricultural chemical, a gelling agent may be used in combination. The gelling agent used in the present invention represents a known gelling agent that causes gelation when added to an organic solvent, and includes, for example, dibenzylidene sorbitol (trade name: EC-1), 12-hydroxystearic acid (trade name). Name: Castor oil hydrogenated fatty acid), N
-Lauroyl-L-glutamic acid-α, γ-di-N-butylamide (trade name: GP1) and the like can be used.

When the above gelling agent is used in combination, the addition amount of the gelling agent is preferably minimized to the necessary minimum in order to increase the pesticide active ingredient. In the case where the liquid pesticide is chloropicrin, when the gelling agent is used in combination with the ultrafine particle silica, the addition amount of the ultrafine particle silica is also used in the case where the gelling agent is also used in the mixed system of the ultrafine particle silica and the filler. Is 2.0 wt% or more and 7.0w in proportion to chloropicrin
t% or less, preferably 4.0 wt% or more and 6.0 wt%
The following is preferable, and the amount of ultrafine particle silica added can be reduced in this way. The addition amount of the above-mentioned gelling agent is preferably 5 wt% or less with respect to the pesticide active ingredient. If it exceeds 5 wt%, the solidified pesticide is too hard and the diffusion of the pesticide active ingredient is delayed, which is not preferable. The above gelling agents may be used alone or in combination.

When a solidified pesticide is prepared by using the above gelling agent, a liquid pesticide and ultrafine particle silica and a dispersion liquid of liquid pesticide and ultrafine particle silica and a filler are prepared in advance (in this case, It does not need to be solidified at this stage), or a gelling agent solution may be added to solidify it, and a solidified pesticide may be prepared by a known method. It is possible to shape by performing in a desired mold, for example, a tablet mold, a spherical mold, a cubic mold, or the like. The solidified pesticide thus formed, preferably shaped, unlike the solidified pesticide that does not add the gelling agent described above, does not show viscosity but has an appropriate hardness, a pudding or agar-like appearance. However, if a solidified pesticide is formed only with a gelling agent as in the prior art, it will also be pudding-like or agar-like, but it is too hard to be collapsed when buried in the soil. On the other hand, according to the present invention, basically, when ultrafine particle silica is contained, it becomes a pudding or agar form having an appropriate hardness as described above, and is smoothly disintegrated in the soil.

Further, in the case of producing a preparation with a solidified pesticide, in order to improve the stability with time, even in the case of a solid pesticide using ultrafine particulate anhydrous silica, a water-soluble organic substance and / or biodegradation is obtained. It is advisable to add natural organic matter or natural earth and stones. If the amount of the water-soluble organic substance and / or the biodegradable organic substance or the natural debris to be added is too small, the effect will not be obtained, and if it is too large, the concentration of the active ingredient of the preparation will not be increased, which is not preferable. Therefore, the addition amount depends on the substance to be added, but the weight ratio is 10 to 1000 with respect to the ultrafine particle silica.
% Is good, and more preferably 100 to 500
% Is good.

Further, it has been found that in order to increase the active ingredient of the pesticide, ultrafine particle silica and a polyvalent metal compound are added to the liquid pesticide to cause agglomeration, so that the solid pesticide gradually hardens into a pudding. At this time, the amount of ultrafine silica added is preferably 4 wt% or more and 15 wt% or less with respect to the pesticide. If the amount of ultrafine silica added is less than 4 wt%, it will not be a solid agricultural chemical and is not preferred.

The above-mentioned polyvalent metal compound is divalent or more as a metal component, exists in soil components, is less likely to pollute the environment, and is soluble in water or pesticides. There is no particular limitation. Specifically, as the inorganic metal compound, Ca, Mg, Zn, Fe, Al, Mn, C
Examples thereof include hydroxides such as u and Co, chlorides, sulfates, nitrates and the like. As the organometallic compound, Ca, Mg, Zn,
Examples thereof include acetates such as Fe, Al, Mn, Cu and Co, propionates, succinates, malates and naphthenates. You may use these polyvalent metal compounds individually or in mixture.

The above-mentioned polyvalent metal compound, depending on the amount of ultrafine particle silica added, is about 1,000 to liquid pesticide.
Addition of 20,000 ppm is preferred. 1,000 pp
If the addition amount is less than m, aggregation of the solidified pesticide is slow, which is not preferable.

Further, known nonionic or cationic polymer flocculants or surfactants may be used if necessary.

The solidified pesticide obtained as described above is preferably packaged in a water-soluble or biodegradable biopolymer film. In the present invention, the term “packaging” means that the solidified pesticide is hermetically sealed in a film to facilitate storage, transportation and workability. A known packaging method can be used as the packaging method used in the present invention. Further, since it is important to prevent alteration of the solidified preparation and hydrolysis of the active ingredient of the agricultural chemicals, vacuum packaging is preferred for the purpose of preventing the inclusion of water during packaging.

Particularly in the present invention, the above water-soluble or biodegradable biopolymer film is preferably used as a water-soluble polymer bag for packaging. As the film material, a well-known polyvinyl alcohol film having good water-solubility and biodegradability, a polyethylene-modified polyvinyl alcohol film, or the like is used, and the above-mentioned film is used to store the solidified preparation and deodorize the solidified preparation. To be

In the present invention, the minimum unit required for the solidified preparation is a liquid pesticide, ultrafine particle silica for obtaining thixotropy, a water-soluble and / or biodegradable organic substance which greatly contributes to the improvement of stability of the preparation over time, Alternatively, natural earth and stones, and it is preferable to add a filler or a metal compound as necessary.

The following is an example of a method for producing a solid agricultural chemical comprising the liquid agricultural chemical, the ultrafine particle silica and the stabilizer for stabilizing the preparation, and a packaging method. (A) Liquid pesticide, ultrafine particle silica, roll stabilizer, kneader,
A method in which a solidified pesticide is made by mixing with a mixer such as a raider or a stirrer, and a known water-soluble polymer bag is filled with a predetermined amount using an extruder, or (B) liquid pesticide or ultrafine particle form A mixed solution consisting of silica and a part of the time-dependent stabilizer is prepared in advance, and the remaining ultrafine particle silica and / or the time-dependent stabilizer and the above-mentioned mixed solution are rolled, a kneader, a raider, a stirrer, etc. Mixing with a mixing machine to make a solidified pesticide, and using an extruder to fill a predetermined amount of it in a known water-soluble polymer bag, (C) liquid pesticide, ultrafine particulate silica and stability over time Prepare a mixed solution consisting of a part of the agent in advance, and fill a known water-soluble polymer bag with the ultrafine particulate silica and / or the time-dependent stabilizer and a predetermined amount of the above-mentioned mixed solution, and then in a packaging bag. The method of making solid pesticide by mixing with Weigh the amount of liquid pesticide, ultrafine particle silica and stabilizer over time into a well-known water-soluble polymer bag, fill and mix the liquid agricultural chemical and ultrafine particle silica containing stabilizer over time in the packaging bag. It can be produced by the known methods (A) to (D) such as the method of producing a solidified agricultural chemical at least.

Further, when a solid pesticide composed of a liquid pesticide, ultrafine particle silica, a filler, a water-soluble metal compound, a water-soluble and / or biodegradable polymer compound, or natural earth and stones is prepared, It is produced by the above-mentioned known methods (A) to (D) by substituting fine particle silica with ultrafine particle silica, a filler, a metal compound, a water-soluble and / or biodegradable polymer compound, or natural earth and stone. be able to. At this time, a solidified pesticide can be prepared by dissolving a predetermined amount of the above-mentioned thickener in a liquid pesticide.

Further, in order to industrially produce such a solidified pesticide, a liquid automatic pesticide, ultrafine particulate silica, filler, metal compound, water-soluble and / or biodegradable polymer compound or The natural earth and stones are charged all at once, or are added separately, and the mixture is put into an automatic packaging machine to produce a solidified preparation.

[0038]

The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. [Example 1] 20.0 g of chloropicrin [purity 99.5 wt%: manufactured by Mitsui Toatsu Chemicals, Inc.], and then 1.10 g of Aerosil [brand 300: manufactured by Nippon Aerosil Co., Ltd.] as ultrafine particulate anhydrous silica. [Addition amount 5.5 wt%] Weighed in a glass mortar and mixed for 5 minutes to prepare a solidified pesticide, which was designated as solidified pesticide (A). Viscosity of solidified pesticide by rotor speed is 25 ℃ E type viscometer [Tokyo Keiki Co., Ltd.
Manufactured]. Similarly, the amount of Aerosil 1.
The solidified pesticide (B) was prepared with 40 g [addition amount of 7.0 wt%], and the viscosity was measured by the rotation speed of the rotor. In addition, solidified pesticide (C) was prepared with 2.00 g of Aerosil [addition amount 10.0 wt%], and the viscosity was measured by the rotation speed of the rotor.
The results are shown in Table 1. All had thixotropy.

6.0 g of the solidified pesticide (A) was placed in a syringe [Terumo Co., Ltd., capacity: 10 ml], and Hyselon H211 was used as a polyvinyl alcohol film in the syringe.
The water-soluble polymer bag (4 cm × 6 cm) made of [25 μ: manufactured by Nigo Film Co., Ltd.] contains the solidified pesticide (A) 5.2.
After filling with g (showing fluidity that can be filled with a syringe), the mouth of the water-soluble polymer bag was melted by heating and closed to prepare a solidified preparation (Z). The solidified preparation (Z) was apparently solid in a room at room temperature and pressure.

[0040]

[Table 1] * 1 = 2.5 rpm viscosity / 10 rpm viscosity. * 2 = Extrapolated value (same below)

Comparative Example 1 100 g of the same chloropicrin as in Example 1 was placed in a 100 ml four-necked flask equipped with a stirrer.
Next, 2.00 g of Aerosil 300 [added amount 2.0 w
t%] was charged and sufficiently stirred, but solidification was not achieved, and a mixed solution (D) was obtained. The viscosity of the mixed liquid was measured using an E-type viscometer [manufactured by Tokyo Keiki Co., Ltd.] at 25 ° C. When the rotor speed is 2.5 rpm, 2 poise, 10 rpm,
It was 0.5 poise.

6.0 g of the mixed liquid pesticide (D) was placed in a syringe [Terumo Co., Ltd., capacity: 10 ml], and Hyselon H211 as a polyvinyl alcohol film was put in the syringe.
The mixed liquid pesticide (D) was added to a water-soluble polymer bag (4 cm × 6 cm) made from [25 μ: manufactured by Nigo Film Co., Ltd.
After filling with g (indicating fluidity that can be filled with a syringe), the mouth of the water-soluble polymer bag was melted by heating and closed to prepare a mixed liquid preparation (Y). The mixed liquid preparation (Y) was a liquid exhibiting fluidity at room temperature and pressure.

[Example 2] Aerosil 300 was added to 1.00
g [addition amount 5.0 wt%], the same as Example 1 except that 2.00 g [addition amount 10 wt%] of Microace L-1 [manufactured by Nippon Talc Co., Ltd.] was used as magnesium silicate (inorganic filler). Then, solidified pesticide (X) was prepared.
The solidified pesticide has a viscosity of 1,500 poise ^{* 2 at} a rotor speed of 2.5 rpm and 420 poi at 10 rpm.
It was se ^{* 2} . The solidified preparation (X) was apparently solid in a room at room temperature and pressure.

[Comparative Example 2] The same as in Example 2 except that Aerosil 300 was omitted, that is, 2.00 g of Microace L-1 was mixed using only the inorganic filler.
It did not solidify. The mixed liquid (W) was immediately measured using an E-type viscometer. Viscosity at rotor speed 2.5 rpm is 2 Poise, viscosity at 10 rpm is 0.5 Po
It was ise. The mixed liquid preparation (W) was a liquid showing fluidity in a room at room temperature and pressure.

[Example 3] Aerosil 300 was added to 1.00
Same as Example 1 except that g [addition amount 5 wt%] and U Pearl C122 [urea / formaldehyde resin, manufactured by Mitsui Toatsu Chemicals, Inc.] 1.20 g [addition amount 6 wt%] as organic filler were used. Then, a solidified pesticide (V) was prepared. The viscosity of the solidified pesticide is 1,800 Poise ^{* 2 at} a rotor speed of 2.5 rpm and 510 Po at 10 rpm.
was ^{* 2} . The solidified preparation (V) was apparently solid in a room at room temperature and pressure.

[Comparative Example 3] 1.20 g of a dry product of U-pearl C122 was mixed as an organic filler in the same manner as in Example 3 except that Aerosil 300 was removed, but it was not solidified. The mixed liquid (U) was immediately measured using an E-type viscometer. Viscosity at rotor speed 2.5 rpm is 2 Poise, viscosity at 10 rpm is 0.5 Pois
It was e. The mixed liquid preparation (U) was a liquid showing fluidity in a room at room temperature and pressure.

Example 4 20 g of chloropicrin used in Example 1 and 0.80 g of Aerosil 300 [added amount 4 wt%] were weighed in a 50 ml polybin and stirred for 10 minutes using a magnetic stirrer. Mixture viscosity is E
-Type viscometer gives 4 Po at a rotor speed of 2.5 rpm
It was 0.5 poise at 10 rpm. Then, 0.2 ml of 25% DBS-DMF solution [addition amount 1.0 wt%] was added as a gelling agent to 5.2 g of the mixed solution and immediately mixed to prepare a solidified pesticide (T). The solidified pesticide (T) was in a uniform agar form.

[Comparative Example 4] As a mixed solution of Example 4, 25 parts was added to 5.00 g of chloropicrin excluding Aerosil.
A solidified pesticide was prepared in the same manner as in Example 4 by using 0.2 ml of a DBS-DMF solution of%. However, the solidified pesticide could not be obtained because the DBS gel was scattered in the chloropicrin solution as lumps.

Example 5 20 g of chloropicrin used in Example 1 and 1.10 g of Carplex [brand CS50: manufactured by Shionogi Pharmaceutical Co., Ltd.] as ultrafine particle hydrous silica.
[Addition amount of 5.5 wt%] was weighed in 50 ml of polybin and stirred for 10 minutes using a magnetic stirrer. The viscosity of solidified pesticides is 1, when the rotor speed is 2.5 rpm.
It was 320 Poise at 100 Poise and 10 rpm.

After that, 5.2 g of the mixed solution was used as a polyvinyl alcohol film to prepare a water-soluble polymer bag (4c) made from Hycelon H211 [25μ: manufactured by Nigo Film Co., Ltd.].
m × 6 cm), 0.8 g of dextrin was further added to the filling bag and immediately mixed, and the mouth of the water-soluble polymer bag was melted by heating and closed to prepare a solidified preparation. After leaving the solidified preparation at room temperature for 3 months, the weight loss of the preparation was 0.
It was 08%.

[Comparative Example 5] 20 g of chloropicrin used in Example 1 and 1.10 g of Carplex [brand CS50: manufactured by Shionogi Pharmaceutical Co., Ltd.] as ultrafine hydrous silica.
[Addition amount of 5.5 wt%] was weighed in 50 ml of polybin and stirred for 10 minutes using a magnetic stirrer. The viscosity of solidified pesticides is 1, when the rotor speed is 2.5 rpm.
It was 320 Poise at 100 Poise and 10 rpm.

After that, 5.2 g of the mixed solution was used as a polyvinyl alcohol film to prepare a water-soluble polymer bag (4c) made from Hycelon H211 [25μ: manufactured by Nigo Film Co., Ltd.].
m × 6 cm) and the mouth of the water-soluble polymer bag was melted by heating and closed to prepare a solidified preparation. After leaving the solidified preparation at room temperature for 3 months, the weight loss of the preparation was 10.8%.

Example 6 20 g of chloropicrin used in Example 1 and 1.10 g of Carplex [brand CS50: manufactured by Shionogi Pharmaceutical Co., Ltd.] as ultrafine particle hydrous silica.
[Addition amount of 5.5 wt%] was weighed in 50 ml of polybin and stirred for 10 minutes using a magnetic stirrer. The viscosity of solidified pesticides is 1, when the rotor speed is 2.5 rpm.
It was 320 Poise at 100 Poise and 10 rpm.

After that, 5.2 g of the mixed solution was used as a polyvinyl alcohol film to prepare a water-soluble polymer bag (4c) made of Hycelon H211 [25μ: manufactured by Nigo Film Co., Ltd.].
m × 6 cm) and then 0.8 g of corn starch
Was further added to the filling bag and immediately mixed, the mouth of the water-soluble polymer bag was melted by heating and closed to prepare a solidified preparation. After leaving this solidified preparation at room temperature for 3 months, the weight loss of the preparation was 0.11%.

Example 7 20 g of chloropicrin used in Example 1 and 1.10 g of Carplex [brand CS50: manufactured by Shionogi Pharmaceutical Co., Ltd.] as ultrafine particle hydrous silica.
[Addition amount of 5.5 wt%] was weighed in 50 ml of polybin and stirred for 10 minutes using a magnetic stirrer. The viscosity of solidified pesticides is 1, when the rotor speed is 2.5 rpm.
It was 320 Poise at 100 Poise and 10 rpm.

After that, 5.2 g of the mixed solution was used as a polyvinyl alcohol film as a water-soluble polymer bag (4c) made of Hycelon H211 [25μ: manufactured by Nigo Film Co., Ltd.].
m.times.6 cm), 0.2 g of sintered diatomaceous earth was further added to the filling bag, and immediately mixed to melt and close the mouth of the water-soluble polymer bag by heating to form a solidified preparation. After leaving this solidified formulation at room temperature for 3 months, the weight loss of the formulation was 0.20%.

Example 8 20 g of chloropicrin and 0.80 g of Aerosil 300 [added amount 4 wt%] used in Example 1 were weighed in a 50 ml polybin and stirred for 10 minutes using a magnetic stirrer. When 30 mg of calcium chloride was added, it was confirmed that the above mixed solution viscosity obtained in Example 5 was obtained.

Example 9 20 g of chloropicrin used in Example 1 and 0.80 g of Aerosil 300 [added amount 4 wt%] were weighed in a 50 ml polybin and stirred for 10 minutes using a magnetic stirrer. When 20 mg of aluminum chloride was added, it was confirmed that the above mixed solution viscosity obtained in Example 5 was obtained.

Example 10 20 g of chloropicrin and 0.80 g of Aerosil 300 [added amount 4 wt%] used in Example 1 were weighed in a 50 ml polyvin and stirred for 10 minutes using a magnetic stirrer. When 28 mg of ferric chloride was added, it was confirmed that the above mixed solution viscosity obtained in Example 5 was obtained.

Example 11 20 g of chloropicrin and 0.80 g of Aerosil 300 [added amount 4 wt%] used in Example 1 were weighed in a 50 ml polybin and stirred for 10 minutes using a magnetic stirrer. When 25 mg of cobalt chloride was added, it was confirmed that the above mixed solution viscosity obtained in Example 5 was obtained.

Example 12 20 g of chloropicrin used in Example 1 and 0.80 g of Aerosil 300 [added amount 4 wt%] were weighed in a 50 ml polybin and stirred for 10 minutes using a magnetic stirrer. When 30 mg of magnesium chloride was added, it was confirmed that the above mixed solution viscosity obtained in Example 5 was obtained.

[Example 13] 20 g of chloropicrin and 0.80 g of Aerosil 300 [added amount 4 wt%] used in Example 1 were weighed in a 50 ml polybin and stirred for 10 minutes using a magnetic stirrer. When 10 mg of magnesium chloride and 12 mg of zinc hydroxide were added, it was confirmed that the above mixed solution viscosity obtained in Example 5 was obtained.

Example 14 20 g of the chloropicrin used in Example 1 and 0.80 g of Aerosil 300 [added amount 4 wt%] were weighed in a 50 ml polybin and stirred for 10 minutes using a magnetic stirrer. Magnesium chloride 5 mg, zinc hydroxide 5 mg and cupric hydroxide 5
When mg was added, it was confirmed that the above mixed solution viscosity obtained in Example 5 was obtained.

[Example 15] A water-soluble polymer bag (4 cm) made from Hycelon H211 [25μ: manufactured by Nigo Film Co., Ltd.] was used as a polyvinyl alcohol film, each containing 5.0 g of the solid agricultural chemicals prepared in Example 1. × 6c
m) was filled and heat-sealed. The odor of chloropicrin was measured using a gas detector tube [measurement range: 0.1 to 15 ppm, manufactured by Komei Rikagaku Co., Ltd.]. The solidified agricultural chemicals before packaging all had a chlorpicrin tear concentration of 2.4 ppm or less. The chloropicrin concentration after packaging was below the detection concentration of the gas detector tube. The results are shown in Table 2.

[0065]

[Table 2]

[0066]

INDUSTRIAL APPLICABILITY According to the present invention, a solidified pesticide having a high pesticide active ingredient, a liquid pesticide having a high viscosity, and a thixotropic property can be produced in a simple process, and the production of a solidified preparation excellent in storage stability is carried out. It provides a specific manufacturing method.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Nobuhiro Fukuda 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Masao Imai 1144, Togo, Mobara-shi, Chiba Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Hitoshi Shimotori 1144, Togo, Mobara-shi, Chiba Mitsui Toatsu Chemicals, Inc.

Claims (13)

[Claims] 1. A solid pesticide characterized by mixing liquid pesticide with ultrafine particulate silica to form a solid form having thixotropic properties. 2. The solidified pesticide according to claim 1, wherein the ultrafine particle silica is anhydrous ultrafine particle silica. 3. The solidified pesticide according to claim 1, wherein an inorganic filler is further mixed. 4. The solidified pesticide according to claim 1, wherein an organic filler is further mixed. 5. The solidified pesticide according to any one of claims 1 to 4, wherein a gelling agent is used together when solidifying. 6. The solidified pesticide according to claim 1, wherein a water-soluble organic substance and / or a biodegradable organic substance are mixed. 7. The solidified pesticide according to claim 6, wherein the water-soluble organic matter and / or biodegradable organic matter is starch and / or a decomposed product of starch. 8. A mixture of natural earth and stones.
The solidified pesticide according to any one of 1. 9. The solidified pesticide according to claim 8, wherein the natural debris is sintered diatomaceous earth. 10. A solidified pesticide having thixotropy according to any one of claims 1 to 9, which is further added with a metal compound to further increase the viscosity and has thixotropy or gelation. Pesticide. 11. A solid pesticide having a thixotropic property or a gel, which is obtained by adding a metal compound to a liquid pesticide mixed with ultrafine particle silica to increase the viscosity. 12. The metal compound is one kind or two kinds or more selected from compounds having aluminum, iron, calcium, manganese, zinc, copper, magnesium and cobalt. The solidified pesticide described. 13. The solidified pesticide according to claim 1, which is packaged with a water-soluble or biodegradable polymer film.