JPH0257041B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to agrochemical granules that contain an active ingredient compound that is solid at room temperature, and that contain lactone to reduce and prevent caking over time. Pesticide granules are used in large quantities because they are easy to apply and have the advantage of being less prone to drifting and scattering during spraying. This not only deteriorates the spraying efficiency significantly, but also sometimes makes spraying impossible. One of the causes of agrochemical granules caking over time is that caking occurs frequently when the active ingredient compound contained is a solid drug substance, particularly a solid drug substance with a relatively low melting point. The mechanism by which solidification occurs over time is that the solid active ingredient compound in the sealed container repeats sublimation and condensation due to day/night temperature fluctuations and seasonal temperature changes, resulting in crystal growth and crosslinking, resulting in solidification. is possible. In addition, when containing both liquid and solid active ingredient compounds, crystal growth and crosslinking may occur during repeated dissolution and crystallization. However, even if the solid active ingredient compound has a low vapor pressure, and even if it contains two or more types of solid active ingredient compounds, solidification occurs over time, so melting point depression and sintering may be involved. Conceivable. Since such caking over time is a fatal defect of pesticide granules, there have been many studies on prevention of caking reduction. For example, as examples that utilize the melting point depression phenomenon in a broad sense, there are
Japanese Patent Publication No. 47-7919, Japanese Patent Publication No. 47-16634, and for adding additives, Japanese Patent Publication No. 48-52941, Japanese Patent Publication No. 48-52941,
48-96732, Unexamined Japanese Patent Application 1973-155632, Unexamined Japanese Patent Application 1972-1646,
JP-A-51-1648, JP-A-52-110832, JP-A-52-
38094, etc., but they are harmful to plants,
They have drawbacks such as not being able to expect significant effects or being effective only for specific active ingredient compounds. As a result of repeated studies to solve these drawbacks, the present inventors have found that there is no chemical damage and the effect is remarkable.
We also discovered lactone as a versatile additive. The present invention provides pesticide granules containing active ingredient compounds that are solid at room temperature, which contain lactone, reduce and prevent caking over time, and have good storage stability. be. Examples of the lactone used in the present invention include:
γ-butyrolactone, δ-valerolactone, γ-
Valerolactone, γ-octanoic lactone,
Examples include α-acetyl-γ-butyrolactone and ε-caprolactone. In particular, ε-caprolactone has a remarkable effect of preventing caking over time.
Since it is advantageous in terms of supplyability and price, it is most suitable for the purpose of the present invention. Furthermore, the amount of lactone used does not necessarily have to be sufficient to dissolve the active ingredient compound; it is usually used in an amount of 50 to 500 parts by weight, preferably 100 to 200 parts by weight, per 100 parts by weight of the active ingredient compound. Accordingly, the object of the present invention can be achieved. Although ε-caprolactam, which has a similar structure, has a similar effect, it is not preferred because it tends to accelerate the decomposition of the active ingredient compound over time. The agricultural chemical active ingredient compound used in the present invention may be solid at room temperature and other than organophosphorus insecticides, and is exemplified below, but is of course not limited thereto. ( ) indicates melting point. Amitraz (87-88℃), MIPC (88-93℃,
MPMC (79-80℃), MTMC (76-77℃), NAC
(160~161℃), XMC (99~100.5℃), BPMC (32
℃), PHC (91.5℃), Chlorpropylate (72~
74.5℃), binapacryl (65-67℃), proclonol (63℃), methomyl (78-79℃), isoprothiolane (50-51℃), eclomezole (20℃), probenazole (138℃), alachlor (40~41
℃), oxadiazone (89-90℃), chlormethoxynil (113-114℃), cymetrine (81-82.5
°C), promethrin (118-120 °C), bentazone (137-139 °C), hydroxyisoxazole (86
°C), 1,2,5,6-tetrahydro-4H-pyrrolo[3,2,1-i,j]quinolin-4-one (112 °C), methyl-N-(2-methoxyacetyl-
N-(2,6-xylin)-DL-alaninate (71.8-72.3°C), 3-(3,5-dichlorophenyl)-5-ethenyl-5-methyl-2,4-oxazoline-dione (108°C ), etc. can be exemplified. The frequency of caking of agricultural chemical granules over time is high when the melting point of the active ingredient compound is about 15 to 160°C, and becomes low when the melting point is higher or lower than that. Therefore, the present invention works most effectively in granules containing an active ingredient compound having a melting point of 15 to 160°C. There are no restrictions on the method for producing agricultural chemical granules according to the present invention, and conventional kneading granulation methods, coating granulation methods, adsorption granulation methods, etc. can be used. In the case of using the kneading granulation method, lactone is added and mixed to the raw material powder, an appropriate amount of water is added and kneaded, the product is molded by a method such as an extrusion granulation method, and the powder is sized after drying. However, if the drying temperature is too high, lactone volatilization becomes a problem, and if the drying temperature is lowered, the efficiency of the drying operation decreases. Since it tends to be difficult to consolidate, there is less need to apply the present invention compared to other granulation methods. When using the coating granulation method, non-adsorptive base particles are placed in a mixer, and a liquid obtained by dissolving or dispersing the active ingredient compound in lactone and a binder are added to the base particles and mixed and coated. If necessary, the fluidity of the granules can be increased by mixing and coating with an appropriate amount of adsorbent powder such as white carbon. The active ingredient compound and the lactone may be added simultaneously or separately. Since granules produced by the coated granulation method have a high concentration of active ingredient compounds on the surface of the granules, they have a strong tendency to solidify over time, making the application of the present invention extremely useful. In addition, when using the adsorption granulation method, the adsorbent base particles are placed in a mixer, and a lactone solution of the active ingredient compound prepared in advance is added dropwise for mixing and adsorption. Furthermore, the solid active ingredient compound can be dissolved in a solvent and added separately from the lactone, and auxiliary agents such as stabilizers and emulsifiers can also be added. The particle size of the agricultural chemical granules of the present invention is not particularly limited;
It can be selected from the range of 0.04 to 2 mm, and there is no relationship between the particle size and the effect of the present invention. Next, examples, comparative examples, and test examples will be explained, and the parts shown are parts by weight. Example 1 90.66 parts of pumice [10 to 48 mesh, Kagalite #2 (manufactured by Silver Sangyo)] was placed in a Nauta mixer (conical screw mixer) and while stirring, ε-caprolactone [Plaxel-M] was added. A mixed solution of 4.34 parts of hydroxyisoxazole raw material (99.0%) was added to 50.0 parts of Daicel Chemical Co., Ltd.), and the mixture was mixed and adsorbed with stirring to obtain hydroxyisoxazole granules. Example 2 91.57 parts of pumice (same product as in Example 1) was placed in a Nauta mixer and while stirring, 3.43 parts of NAC raw material (96.6%) was added to 50.0 parts of ε-caprolactone (same product as in Example 1). The mixed and dissolved solution was added, stirred and adsorbed to obtain NAC granules. Example 3 Calcium carbonate crushed granules [10-48 mesh K-
2 (manufactured by Sankyo Seifun)] 83.26 parts was placed in a ribbon mixer, and while stirring, 4.34 parts of hydroxyisoxazole raw material (99.0%) was added to 5.00 parts of ε-caprolactone (same product as in Example 1) and mixed. The dissolved liquid was added, and 7.20 parts of white carbon [Carplex #80 (manufactured by Shionogi & Co., Ltd.)] was added in three portions. Next, 4.00 parts of methylene chloride was added to complete the coating, and then volatilized to obtain hydroxyisoxazole granules. Example 4 Calcium carbonate fine particles [65-250 mesh]
#65250 (manufactured by Nitto Funka Co., Ltd.)] 93.17 parts was placed in a ribbon mixer, and while stirring, 2.00 parts of ε-caprolactone (same product as in Example 1) and 1.73 parts of methomyl raw material (98.0%) were added and mixed and dissolved. Add the liquid,
Furthermore, white carbon (same product as Example 3)
3.10 parts were added in 4 parts. Next, 3.00 parts of methylene chloride was added to complete the coating, and then volatilized to obtain methomyl fine granules F. Example 5 Calcium carbonate fine particles (same product as Example 4)
Put 92.16 parts into a ribbon mixer and while stirring,
Add 2.24 parts of MTMC base material (98.0%) to 3.00 parts of ε-caprolactone (same product as in Example 1), mix and dissolve and pour, and then add 2.60 parts of white carbon (same product as in Example 3) three times. Added separately. Next, methylene chloride was added to complete the coating, and then volatilized to obtain MTMC fine granules F. Comparative Example 1 Hydroxyisoxazole granules were obtained in the same manner as in Example 1 except that 6.00 parts of diethylene glycol was added instead of ε-caprolactone. Comparative Example 2 Polyethylene glycol [#200 (manufactured by NOF Corporation)] was used instead of ε-caprolactone in Example 2.
NAC granules were obtained in the same manner by adding 5.00 parts. Comparative Example 3 Crushed calcium carbonate granules (same product as Example 3)
Put 85.82 parts into a ribbon mixer and while stirring,
After adding 2.00 parts of diethylene glycol, 5.38 parts of hydroxyisoxazole premix [a finely ground product of 80.8 parts of hydroxyisoxazole raw material (99.0%) and 19.2 parts of white carbon] was added in two portions. Furthermore, white carbon (same product as Example 3)
After adding 6.80 parts in 4 parts, methylene chloride
4.00 parts were added to complete the coating, and methylene chloride was volatilized to obtain hydroxyisoxazole granules. Comparative Example 4 Calcium carbonate fine particles (same product as Example 4)
Put 93.17 parts into a ribbon mixer and while stirring,
NE-560 [Nonionic activator (Nippon Nyukazai Co., Ltd.)]
Add 0.40 parts of NE-560SFC (anionic activator (Nippon Nyukazai product)) and 2.00 parts of methylene chloride, mix and dissolve, and pour. 2.43 parts (pulverized product) was added in two portions. Furthermore, white carbon (same product as Example 3)
After adding 3.60 parts in 3 parts, methylene chloride
2.00 parts were added to complete the coating, and methylene chloride was volatilized to obtain Methomil fine granules F. Comparative Example 5 Calcium carbonate fine particles (same product as Example 4)
Put 94.07 parts into a ribbon mixer and while stirring,
After adding 1.00 parts of polyethylene glycol,
MTMC Premix [MTMC bulk (98.0%)
Finely crushed product containing 76.8 parts and 23.5 parts of white carbon]
2.93 parts were added in two portions. Furthermore, white carbon (same product as Example 3)
After adding 2.00 parts in two parts, methylene chloride
3.00 parts were added to complete the coating, and methylene chloride was volatilized to obtain MTMC fine granules F. Test Example Granules produced by the methods of Examples 1 to 5 and Comparative Examples 1 to 5 were tested for crystal precipitation, caking, fluidity, and exfoliation of active ingredient amount. [Testing method for crystal precipitation] Zeolite granules (48 to 150 mesh) were placed in a 30φ x 30cmH, 5-volume heat-insulating jar, and approximately 50g of the granules were placed in the center of the jar and sealed in a 50ml glass bottle. This heat insulating jar was run for 3 cycles at 50℃ for 3 days, at room temperature for 3 days, at 0℃ for 3 days, at -20℃ for 3 days, and at room temperature for 3 days.
I went on a cycle. The presence or absence of crystal precipitation was determined using an 80x magnifying glass. The judgment criteria were as follows. (−): No crystal precipitation. (+): Slight acicular crystal precipitation. ( ): Significant acicular crystal precipitation. ( ): Numerous acicular crystals precipitate over the entire grain surface. The results are shown in Table 1. [Caking test method] Place 1 kg of granules into a 1 kg lactone double-layer bag, and
A weight of 1 kg (approximately 120 g/cm ² ) was placed thereon and left at 40° C. for 4 weeks and at room temperature for 4 weeks. (−): No caking. (+): Weak caking. It crumbles easily when you touch it with your hands. ( ): Block-shaped cake with a diameter of about 1 to 5 cm. (): Caking all over. The results are shown in Table 1. [Flowability test method] JIS-Z2502 (Method for measuring fluidity of metal powder) was applied mutatis mutandis. A sample (200 g of granules, 2 mm of fine granules F) was placed in a fluidity device (orifice diameter: 5 mm for granules, 2 mm for fine granules F).
(300g) was added, and the time required for the entire amount to fall was measured. The results are shown in Table 1. [Peelability Test Method] The measurement method and device were in accordance with the Zennogyo method. sample
Weigh 10g and transfer it onto a glass filter.
Make the surface of the sample as flat as possible. After setting the glass filter containing the sample in the fixed position and connecting all parts, the air volume is 30% from the compressor.
Air was bubbled through for exactly 2 minutes at a rate of 1/min. The sample remaining on the glass filter was collected, mixed, the active ingredient was quantified, and the peeling rate was determined from the following formula by comparing the active ingredient A (%) after peeling with the active ingredient B (%) before peeling. Peeling rate=(B-A)/B×100 The results are shown in Table 1.

[Table] From the above results, Examples 1 to 1 obtained by the present invention
In the granules of No. 5, no crystal precipitation or caking was observed, and no abnormalities in fluidity or peelability of the active ingredient were observed. On the other hand, crystal precipitation and caking were clearly observed in the granules of Comparative Examples 1 to 5. In addition, abnormalities were observed in fluidity and peelability of the active ingredient, resulting in loss of commercial value.

Claims (1)

[Scope of Claims] 1. A pesticide granule which is solid at room temperature and contains an active ingredient compound other than an organophosphorus insecticide, and which is characterized by containing lactone and which prevents caking over time. 2. The agricultural chemical granule according to claim 1, wherein the lactone is ε-caprolactone. 3. The agrochemical granule according to claim 2, wherein the content of ε-caprolactone is 100 to 300 parts by weight based on 100 parts by weight of the active ingredient compound. 4. The agricultural chemical granules according to claim 1, wherein the active ingredient compound has a melting point in the range of 15°C to 160°C.