JP2970666B2 - Pesticide solid formulation - Google Patents

Description

Description TECHNICAL FIELD [0001] The present invention relates to an agricultural chemical solid preparation. [0002] Agrochemicals usually exert their effects with several tens to hundreds of g of active ingredient per hectare, but only a small amount of the pesticide drug substance is widely used in such low doses. Since it is very difficult to spray uniformly, the pesticidal drug substance is usually diluted with an appropriate diluent to make it easier to spray. This is a pesticide formulation whose primary purpose is to make the pesticide easy to use. It is also a major purpose of the pesticide formulation to maximize the efficacy of the pesticide, and to cover the disadvantages of the pesticide drug substance if it is defective, and to provide a pesticide without problems. [0003] One of the above pesticide preparations is a solid preparation, which is obtained in a solid form. Representative examples thereof include wettable powders, granules, powders and the like. is there. All of the solid preparations are prepared by diluting a pesticide drug substance in a solid form. The details are as follows. [0004] A wettable powder is a fine powder formulation obtained by pulverizing and mixing a pesticidal drug substance with a small amount of a surfactant and a fine powder carrier. When used, it is diluted with water like an emulsion when used, and used as a suspension in a sprayer. Therefore, particularly important physical properties of wettable powders include suspension, fineness, and hydration properties, and these physical properties are maintained after storage for a long period of time, along with the stability of the active agricultural chemical in the formulation. There must be. [0005] Dust is a preparation obtained by diluting a pesticidal drug substance with a fine powder carrier and, unlike a wettable powder, is not diluted with water at the time of use but sprayed as it is by a dusting machine. Therefore, it is required that the degree of fineness does not decrease even after long-term storage and that the powder has good dispersibility. For this purpose, it is not preferable that the powder solidifies during storage. Further, granules are mainly produced by a kneading extrusion granulation method, an impregnation method, a coating method, etc., all of which take a granular form and are often applied to the water surface or soil rather than directly sprayed on a target crop. . After being applied to the water surface or soil, the active ingredient elutes or volatilizes in water to reach the point of action and develops its efficacy, so even after long-term storage, it has the same water dispersibility and volatility as in the formulation. Is required to be maintained. [0006] Conventionally, when a pesticide drug substance having a melting point in the range of 0 ° C to 65 ° C is formed into such a solid preparation, there are cases where the pesticide drug substance is handled as a solid and when it is handled as a liquid. If it is handled as, for example, the melting of the agrochemical substance and the occurrence of agglomeration in a step involving heat generation, such as a pulverization step, must be taken into account. There are various problems such as the necessity of providing a heating facility, etc.
It was necessary to fully understand the production process in order to obtain a solid preparation having good initial physical properties as compared with a case where a pesticide bulk material exceeding 5 ° C and a pesticide bulk material not exceeding 0 ° C were formed into a solid preparation.
In addition, even if a solid preparation with good initial physical properties is obtained, in long-term storage, depending on the conditions, the pesticide drug substance may repeatedly change its liquid and solid states, resulting in deterioration of physical properties. In the case of wettable powders, the suspension ratio and the degree of fineness may be reduced. In the case of powdery agents, the amount may be changed during storage. SUMMARY OF THE INVENTION [0007] The present inventors have made it easier to formulate a solid pesticide having such a melting point in the range of 0 ° C. to 65 ° C., and furthermore, after long-term storage. As a result of intensive studies to obtain a preparation having satisfactory physical properties, it was found that a solid preparation meeting the above initial purpose can be obtained by adding the present hydrocarbon to the preparation. . [0008] That is, the present invention relates to a pesticidal drug substance having a melting point in the range of 0 ° C to 65 ° C (in the case of a mixture, the melting point of the mixture is 0 ° C to 6 ° C).
(Range of 5 ° C.) in the solid preparation of the general formula [I] (Wherein X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ and Z ₂ are the same or different and represent a hydrogen atom or an alkyl group having 2 or less carbon atoms, and R ₁ and R ₂ are the same or different , A hydrogen atom or a methyl group, and n represents 0 or 1) (hereinafter referred to as the present hydrocarbon). [0009] The present hydrocarbon has a low pungent odor,
In addition, it has an advantage that it has a high flash point and is easy to handle, and does not require special deodorizing and degassing equipment during use. And it was confirmed that even if these were added to the preparation, there was little occurrence of phytotoxicity to the crop, and it was possible to obtain a preparation having no odor, no deterioration in physical properties due to evaporation of the solvent, flammability, explosiveness, etc. It was completed. Next, specific examples of the present hydrocarbon and the pesticidal active substance having a melting point in the range of 0 ° C. to 65 ° C. are shown in Tables 1 and 2, respectively, but are not limited thereto. In addition, isomers may be present in both the present hydrocarbon and the pesticide drug substance, and in such a case, such isomers are, of course, included in the present invention. [Table 1] [Table 2] In practicing the present invention, one kind of the present hydrocarbon may be used alone, or two or more kinds thereof may be used as a mixture, and the melting point of these hydrocarbons is preferably 0 ° C. or less. . Further, other solvents that meet the purpose of the present invention, such as having a low irritating odor and a high flash point, such as indane derivatives, may be added at the same time. % Is desirable. [0014] Among the hydrocarbons, 1-phenyl-1-xylylethane is particularly preferred in that it is industrially available. Naturally, a combination of the pesticide raw material and the hydrocarbon is particularly preferably used. Is preferred. [0015] The stability of the physical properties of the solid preparation is improved depending on the amount of the present hydrocarbon added, and the amount of addition can vary depending on the type of the pesticidal drug substance. It is desirable that the content in combination with the pesticide is 20% by weight or more and 60% by weight or less in the solid preparation. In addition, the pesticide drug substance is 1
Needless to say, the kind may be used alone, but two or more kinds may be used as a mixture. In such a case, the melting point of the mixture is 0 ° C. to 65 ° C. regardless of the melting point of each single agent.
The temperature may be in the range of ° C. In the pesticidal solid preparation of the present invention, in addition to the present hydrocarbon and the pesticidal active substance, carriers, surfactants, synergists, stabilizers, antioxidants, etc., are generally used by those skilled in the art for preparing preparations. The auxiliary used may be used arbitrarily. EXAMPLES The present invention will be described in more detail with reference to Examples, Comparative Examples and Test Examples, but the present invention is not limited to these Examples. Example 1 5 parts of pesticide (b), 2.5 parts of hydrocarbon (3) and 2.5 parts of hydrocarbon (4)
Of the mixture, 3 parts of calcium ligninsulfonate, 4 parts of Solpol 5060 (a surfactant manufactured by Toho Chemical Industry Co., Ltd.), 15 parts of white carbon and 68 parts of diatomaceous earth were added to the mixture. After mixing, the mixture was mixed with a juice mixer to obtain a good pesticide (b) 5% wettable powder. Example 2 In a beaker, 20 parts of pesticide (f) and 10 parts of hydrocarbon (3) were mixed, and 6 parts of Solpol 5060 (same as above), 2 parts of calcium ligninsulfonate, and 30 parts of white carbon were used. Then, a mixture of 32 parts of diatomaceous earth was added to obtain a good 20% wettable powder of the pesticide (f) thereafter in the same manner as in Example 1. Example 3 20 parts of pesticide (a), 6 parts of hydrocarbon (3) and 6 parts of hydrocarbon (4)
And 25 parts of white carbon, 37 parts of diatomaceous earth, 2 parts of calcium ligninsulfonate, 3 parts of Solpol 2495G (a surfactant manufactured by Toho Chemical Industry Co., Ltd.) and 3 parts of Solpol 5080 (Toho Chemical Industry Co., Ltd.) Surfactant) 1
Part was dropped into the mixture with a ribbon mixer, and the whole was remixed. Then, the mixture was pulverized with a centrifugal pulverizer to obtain a good pesticide (a).
% Wettable powder was obtained. Example 4 5 parts of pesticide (e), 2.5 parts of hydrocarbon (3) and 2.5 parts of hydrocarbon (4)
In a beaker, 3 parts of calcium ligninsulfonate, 4 parts of solpol 5060 (same as described above), 15 parts of white carbon and 68 parts of diatomaceous earth were added. Good pesticide (e)
5% wettable powder was obtained. Example 5 Pesticide (d) 10 parts, hydrocarbon (3) 7.5 parts and hydrocarbon (4) 2.
5 parts were mixed in a beaker, and 15 parts of white carbon, 3 parts of calcium ligninsulfonate, 6 parts of sorbol 2495G (same as above) and 56 parts of diatomaceous earth were mixed in another beaker, and then added. Hereinafter, Example 1
A good 10% wettable powder of the pesticide (d) was obtained in the same manner as described above. Example 6 5 parts of pesticide (b) and 5 parts of hydrocarbon (1) were mixed in a beaker, and 3 parts of calcium ligninsulfonate, 4 parts of Solpol 5060 (same as above), and 15 parts of white carbon And a mixture of 68 parts of diatomaceous earth were added to obtain a good 5% wettable powder of the pesticide (b) in the same manner as in Example 1. Example 7 Example 6 except that 5 parts of pesticide (b) and 5 parts of hydrocarbon (2) were used.
In the same manner as described above, a good 5% wettable powder of the pesticide (b) was obtained. Example 8 15 parts of white carbon and 70 parts of clay were added to 10 parts of pesticide (a) and 5 parts of hydrocarbon (3) in a beaker, and the mixture was premixed. It was pulverized to obtain a good pesticide (a) 10% powder. Example 9 10 parts of pesticide (e), 2 parts of hydrocarbon (1), 5 parts of hydrocarbon (2) and 10 parts of white carbon, 35 parts of bentonite 8,
15 parts of diatomaceous earth, 2 parts of Solpol 5060 (same as above) and 21 parts of clay were added, mixed uniformly, watered, kneaded evenly, and used a granulating machine to obtain a good pesticide.
10% granules of (e) were obtained. Example 10 10 parts of pesticide (b) and 2 parts of hydrocarbon (1) were mixed in a beaker, and 10 parts of white carbon and 35 parts of bentonite were added.
Parts, diatomaceous earth 15 parts, Solpol 5060 (same as above)
2 parts and 21 parts of clay were added to obtain good 10% granules of the pesticide (b) in the same manner as in Example 9. Example 11 5 parts of pesticide (b) and 3 parts of hydrocarbon (5) were mixed in a beaker, and 5 parts of Solpol 5060 (same as above), 3 parts of calcium ligninsulfonate, 15 parts of white carbon 15 And a mixture of diatomaceous earth and 69 parts of diatomaceous earth were added to obtain a good 5% wettable powder of the pesticide (b) in the same manner as in Example 1. Example 12 10 parts of pesticide (f), 1 part of pesticide (g), 7.5 parts of hydrocarbon (3), 1.8 parts of hydrocarbon (4) and 2-methyl-4-phenylindane
While mixing 0.6 parts in a beaker, Solpol 2495G
(Same as above) 6 parts, calcium lignin sulfonate 2
, A mixture of 20 parts of white carbon and 51.1 parts of diatomaceous earth was added to obtain a good wettable powder of a pesticide (f) and a pesticide (g) in the same manner as in Example 1. Comparative Example 1 20 parts of pesticide (f) were put into a beaker, and 6 parts of sorbol 5060 (same as above), 2 parts of calcium ligninsulfonate, 30 parts of white carbon and 4 parts of diatomaceous earth were placed in the beaker.
A mixture of 2 parts was added, and the mixture was premixed and then mixed with a juice mixer to obtain a 20% wettable powder of pesticide (f). Comparative Example 2 5 parts of pesticide (e) were placed in a beaker, and 3 parts of calcium ligninsulfonate, 4 parts of solpol 5060 (same as above), 15 parts of white carbon and 7 parts of diatomaceous earth were placed in a beaker.
A mixture of 3 parts was added, and a 5% wettable powder of pesticide (e) was obtained in the same manner as in Comparative Example 1. Comparative Example 3 A pesticide was prepared in the same manner as in Comparative Example 2 except that 5 parts of the pesticide (b) was used.
5% wettable powder of (b) was obtained. Comparative Example 4 10 parts of pesticide (a) were put into a beaker, and 15 parts of white carbon and 75 parts of clay were added thereto, followed by premixing, followed by grinding with a juice mixer, and 10% powder of pesticide (a). I got Comparative Example 5 10 parts of pesticide (e), 10 parts of white carbon, 35 parts of bentonite, 15 parts of diatomaceous earth, 2 parts of solpol 5060 (same as above) and 28 parts of clay were mixed, and water was added and uniformly kneaded. Of pesticide (e) by using
0% granules were obtained. Test Example 1 100 g of each of the wettable powders produced in Example 2, Example 4, Comparative Example 1 and Comparative Example 2 was sealed in an aluminum bag and stored at 0 ° C. for 60 days. Weigh it, conduct a wet sieving test using a 46μ sieve, transfer the residue on the sieve to an evaporating dish, dry it on a hot water bath and weigh it. Was calculated. The results are shown in Table 3 together with the results at the time of manufacture. [Table 3] [0036] The fineness of the wettable powder after storage for a long period of time is significantly higher than that of the non-added one by adding the present hydrocarbon, indicating that the storage stability is excellent. Test Example 2 With respect to each wettable powder stored at 0 ° C. for 60 days in Test Example 1, the suspension ratio was measured under the following conditions. That is, 250 ml of 3 ° hard water was placed in a thermostat at 30 ° C.
A 50-ml stoppered measuring cylinder was put therein, and 500 mg of each wettable powder was suspended therein. After 15 minutes, 25 ml was sampled from the center to determine the suspension ratio. The results are shown in Table 4 together with the results at the time of manufacture. [Table 4] The suspension rate of the wettable powder after long-term storage is significantly higher by adding the present hydrocarbon than that without the addition, indicating that the storage stability is excellent. Test Example 3 A phytotoxicity test was performed on the wettable powders produced in Example 1 and Comparative Example 3. The test crop was Chinese cabbage (musou), and the dilution ratio of each test wettable powder was 250 times. The results are shown in Table 5 as the average degree of phytotoxicity in 3 groups per section. [Table 5] It can be seen that the phytotoxicity of the wettable powder with the present hydrocarbon added to Chinese cabbage is extremely low, similarly to the phytotoxicity of the non-added wettable powder. Test Example 4 100 g of each of the 10% powder of the pesticide (a) produced in Example 8 and the 10% powder of the pesticide (a) produced in Comparative Example 4 were sealed in aluminum bags at 60 ° C. at 0 ° C. Days saved. After weighing 50 g of each of the above powders at the time of production and after storage for 60 days, conducting a wet sieving test using a 46 μ sieve, transferring the residue on the sieve to an evaporating dish, and drying it on a hot water bath The sample was weighed and the percentage of on-screen residue of the sample was calculated in weight percent. Table 6 shows the results. [Table 6] [0045] The fineness of the powder after long-term storage becomes significantly higher by adding the present hydrocarbon than that without the addition, indicating that the storage stability is excellent. Test Example 5 100 g of each of the 10% granules of the pesticide (e) produced in Example 9 and the 10% granules of the pesticide (e) produced in Comparative Example 5 were sealed in aluminum bags, and placed at 5 ° C. for 30 days. And stored at 0 ° C. for 60 days.
The extensibility in water was tested and compared between the granules at the time of production and after storage at 5 ° C. for 30 days and at 0 ° C. for 60 days. Table 7 shows the results. [Table 7] -: No visual difference +: Visual difference [0048] It can be seen that the expandability of the granules to which the present hydrocarbon is added is stable even after long-term storage, unlike the granules without the addition.

──────────────────────────────────────────────────続 き Continued on the front page (72) Nobuyuki Hirano 3-1-1, Kasuganaka, Konohana-ku, Osaka-shi, Osaka Prefecture Within Sumitomo Chemical Co., Ltd. (72) Inventor Shozo Sakai Kishirocho, Kasai-shi, Hyogo (56) References JP-A-57-144208 (JP, A) JP-A-59-118701 (JP, A) JP-A-60-243001 (JP, A) JP-B-56-19841 (JP, B2) JP 37-10800 (JP, B1) International Publication No. 86/4214 (WO, A1) (58) Fields investigated (Int. Cl. ⁶ , DB names) A01N 25/08 A01N 25/14 A01N 25/22 CAPLUS (STN) REGISTRY (STN) WPIDS (STN)

Claims (1)

(57) [Claims] 1.0 In a solid preparation of an agrochemical substance having a melting point in the range of 1.0 to 65 ° C (in the case of a mixture, the melting point of the mixture is in the range of 0 to 65 ° C). And the general formula (Wherein X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ and Z ₂ are the same or different and represent a hydrogen atom or an alkyl group having 2 or less carbon atoms, and R ₁ and R ₂ are the same or different , Represents a hydrogen atom or a methyl group, and n represents 0 or 1.) Use of a water-diluted liquid of an agricultural chemical wettable powder containing a hydrocarbon for spraying on crops.