JPH027921B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a herbicidal composition containing a herbicidal quaternary bipyridylium salt and a phenyl urea compound as active ingredients.

More specifically, it contains a herbicidal quaternary bipyridylium salt that is a fast-acting foliage treatment agent, a soil treatment herbicidal phenyl urea compound that suppresses weed growth for a long period of time, and a polymer compound having a pyranose ring or a derivative thereof. The present invention relates to a solid particulate hydratable herbicide composition with high strength.

Originally, pesticides were devised and designed in such a way that if they were handled and used in accordance with the prescribed methods, they would hardly disturb the ecology or cause environmental pollution, much less lead to personal injury. .

However, it is usually commercially available in the form of an aqueous solution;
It is also true that paraquat, which is one of the herbicidal quaternary bipyridylium salts currently in use, is sometimes accidentally ingested, leading to serious consequences. In response, proposals have been made to add unpleasant taste agents or odorants to the aqueous solution to prevent accidental ingestion. In addition, consideration has been taken to include vomiting substances in order to ensure that even if the product is accidentally ingested, it will be immediately excreted from the body. Nevertheless, accidents caused by accidental ingestion, which occur because agricultural chemicals are in the form of aqueous solutions, cannot be completely avoided.

With these facts as a background, we conducted repeated studies to more proactively solve the problem, and aimed to create a solid-state agrochemical formulation that would be less likely to enter the human body.

In this case, it is not difficult to simply formulate a herbicidal quaternary pipyridylium salt into a solid preparation. Particularly during dispersion, it can be said that it is not very difficult to dissolve these solids in water because of the easy solubility of quaternary bipyridylium salts. That is, if it is in a solid state with an appropriate size that is difficult to scatter, it can be handled and used as a safe preparation that does not cause problems such as accidental ingestion or inhalation of dust.

However, the other herbicidal active ingredient, the phenyl urea compound, is generally not soluble in water and is usually provided in the form of a wettable powder, and exists in a suspended state in the spray solution. . In this way, as is clear from the reason for the selection of the dosage form, the size of the hydrating powder is 5 μm or less, and can be said to be a size that is relatively easy to scatter. On the other hand, if the herbicidal quaternary bipyridylium salt mentioned above is simply mixed, it is difficult to mix with the herbicidal phenylurea-based hydrating agent because it has a size that does not scatter, and it is difficult to mix the herbicidal quaternary bipyridylium salt with the herbicidal phenylurea-based hydrating agent. The distribution will be completely unpredictable.

One solution to this difficulty is to make both active ingredients approximately the same size. However, as mentioned above, reducing the size of the herbicidal quaternary bipyridylinium salt to the size of a wettable powder requires
Problems such as dust inhalation will occur, and this will not truly solve the problem. Therefore, the remaining direction to solve the problem is to change the apparent size of the herbicidal phenylurea compound,
It is essential to granulate the particles to a size that prevents them from scattering. At this time, if the herbicidal phenyl urea compound is simply increased in size, the suspension properties will naturally be poor, so simply increasing the apparent size with other bulking agents will reduce the original water content. It must be devised to maintain its shape as a small constituent unit as a Japanese additive. At this time, it is naturally possible to add an inert ingredient as a bulking agent, but in this case, in order to ensure disintegration in water, it is preferable to use a water-soluble substance. Focusing on the fact that the ingredients meet these requirements, we conducted extensive research into granulating herbicidal quaternary bipyridylium salts to fulfill the above role.

In particular, even when a hydrating agent with good elongation properties is kneaded with water to form large particles, the suspensibility often decreases significantly.Also, the coexistence of an electrolyte substance also causes a decrease in the suspensibility. It can be predicted that this method requires more ingenuity in manufacturing than ordinary hydrating agents.

Simply add a nonionic or cationic herbicidal quaternary bipyridylium salt (which does not need to be specially pulverized into fine particles as it is a relatively fragile crystal) and a pulverized product of a phenyl urea compound (less than 5 microns). Granules made by adding a surfactant and adding water lack strength, so inorganic carriers such as bentonite, diatomaceous earth, clay, and calcium carbonate were added according to conventional methods, but the strength of the granules Although this improved, the suspension performance was extremely reduced and it was found that it was not suitable for practical use.

Therefore, the present inventors developed a herbicidal quaternary bipyridylium salt (as it is a relatively fragile crystal, it is not necessarily necessary to specially grind it into fine particles) and a ground product of a phenyl urea compound (with a size of 5 microns or less). ), water is added to the mixture obtained by adding a polymer compound having a pyranose ring having a size similar to that of the phenyl urea compound, and if desired, a nonionic or cationic surfactant is also added. In addition, they discovered that a granular herbicide composition prepared by kneading and granulating the granules not only has good solid strength but also has good disintegration in water and suspension of the herbicidal active ingredient, leading to the completion of the present invention. Ivy.

Therefore, according to the present invention, 1,1'-ethylene-
At least one herbicidal quaternary bipyridylium salt selected from the group of 2,2'-bipyridylium salts and 1,1'-dimethyl-4,4'-bipyridylium salts
(a) and 1,1'-dimethyl-3-phenylurea, 3
-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-
1-methoxy-1-methylurea, 3-(p-chlorophenyl)-1,1-dimethylurea and 3-
(p-chlorophenyl)-1-methoxy-1-methylurea Particles (b) with a particle size of 5 microns or less obtained by pulverizing at least one herbicidal phenylurea compound selected from the group of 1-methoxy-1-methylurea, starch, cellulose, and carboxymethyl A mixture of particles (c) with a particle size of 5 microns or less obtained by pulverizing at least one pyranose ring-containing polymer compound selected from the group of cellulose salts or its derivatives is mixed with water and kneaded. The present invention provides a hydrating herbicide composition which is formed by granulating and drying, has a strong solid granular form, and has excellent disintegration in water.

In the composition of the present invention, the pyranose ring-containing polymer component (c) in the raw material mixture for making it, that is, a salt of starch, cellulose, or carboxymethylated cellulose, is pulverized to a particle size of 5 microns or less as described above. Although used in the form of fine particles, this (c) component substance is blended into the raw material mixture in the form of fine particles of 5 microns or less and subjected to a step of adding water to the raw material mixture and kneading the mixture. As a result of this, water-soluble (a) component substances that coexist in the raw material mixture and partially dissolve in water during kneading, i.e.
In cooperation with the grade bipyridylium salt, it is possible to not only give the composition of the present invention after granulation and drying a strong granule shape without generating dust, but also produce a granular composition in which each component is uniformly distributed. , and (b) which improves the disintegrability of the granules of the present composition in water and is sparingly soluble in water.
The component substances, ie, the phenyl urea compounds, also have the effect of making their suspension in water excellent. Therefore, in the composition of the present invention
(c) The component substances do not act merely as bulking agents, dispersants or disintegration promoters. On the other hand, commercially available starch is usually a powder consisting of particles with different sizes ranging from 3 to 100 microns, and typical commercially available cellulose powder has a particle size range that can pass through a mesh of 50 to 400 mesh. This is because the mesh size of 400 mesh is 37 microns.
Even commercially available cellulose fine powder products that pass 400 mesh
It has an average particle size of about 37 microns. In addition, commercially available carboxymethylated cellulose (CMC) has a particle size that is large enough to pass through a 80-mesh mesh, and even a fine powder product can pass through a 200-mesh mesh (74 micron mesh size). It has an average particle size of about 74 microns. Therefore, starch, cellulose and
CMC is not commercially available in the form of fine particles with a particle size of 5 microns or less.

The present invention will be explained in more detail below.

The pesticide composition consists of a herbicidal quaternary bipyridylium salt and a herbicidal phenyl urea compound. Examples of herbicidal quaternary bipyridylium salts are as follows. 1,1-ethylene-2,2'-bipyridylium dibromide, 1,1'-dimethyl-4,4'-bipyridylium dichloride, 1,1'-di-2-hydroxyethyl-4, 4'-bipyridylium dichloride, 1,1'-bis-3,5-dimethylmorpholinocarbonylmethyl-4,4'-bipyridylium dichloride, 1-(2-hydroxyethyl)-1'-methyl- 4,4′-bipyridylium dichloride, 1,
1'-Dicarbamoylmethyl-4,4'-bipyridylium dichloride, 1,1'-bis-N,N-dimethylcarbamoylmethyl-4,4'-bipyridylium dichloride, 1,1'-bis -N,N-diethylcarbamoylmethyl-4,4'-bipyridylium dichloride, 1,1'-di-(piperidinocarbonylmethyl)-4,4'-bipyridylium dichloride,
1,1'-diacetonitrile-4,4'-bipyridylium dichloride, 1,1'-diethoxycarbonylmethyl-4,4'-bipyridylium dibromide,
1,1'-diaryl-4,4'-bipyridylium dibromide, etc. Further, examples of herbicidal phenylurea compounds are as follows. 1,
1'-dimethyl-3-phenylurea, 3-(P-chlorophenyl)-1,1-dimethylurea, 3-
(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 1,1-dimethyl-3-(α,α,α -trifluoro-m-tolyl)urea, 1-butyl-3-(3,4-dichlorophenyl)-1-methylurea, 3-(P-chlorophenyl)-1-methoxy-1-methylurea, 3
-(3,4-dichlorophenyl)-1-methoxy-1-methylurea and the like. The ratio of both active ingredients is 0.5 to 5 mol of the herbicidal phenyl urea compound to 1 mol of the herbicidal quaternary bipyridylium salt.
The amount is in moles, preferably 1 to 3 moles.

In addition, surfactants are preferred ingredients in order to fully exhibit the herbicidal effects of these herbicidal active ingredients, or to improve the dispersibility of phenylurea compounds added to water, but they are especially preferred for herbicidal In order to maintain the herbicidal performance of the quaternary bipyridylium salt, a nonionic surfactant or a cationic surfactant may be selected. These surfactants are preferably added in an amount of 1 to 50% based on the herbicidal substance.

In this way, a herbicidal quaternary bipyridylium salt, a phenyl urea compound, and a polymeric compound having a pyranose ring are mixed in solid form, and a liquid nonionic surfactant and water are added, kneaded, and granulated to form granular water. It can be used as a compatible substance. In this case, specific examples of polymer compounds having a pyranose ring include starch and cellulose, but also carboxymethylated derivatives (Na salt, Ca salt), etc.
It also means up to.

It is desirable that these polymeric compounds having a pyranose ring be added in an amount of 1 to 50% based on the herbicidal substance. Although it is possible to add additives for various other purposes, they are limited to types and amounts that do not impair the properties of the wettable granules. These additives include odorants, colorants, taste agents, emetics, and the like.

A method of implementing the present invention will be described. Although it is preferable that all components in the raw material mixture be finely ground, it is not necessary to specifically grind the herbicidal quaternary bipyridylium salt. However, in particular, it is essential that the phenyl urea compound be sufficiently pulverized in the pulverization process, and it is necessary that the size of the phenylurea compound be approximately 5 microns or less. Further, in the present invention, the polymer compound having an essential pyranose ring in the raw material mixture before kneading also has a particle size of about 5 microns or less. The amount of water to be added is appropriately determined depending on the amounts of the agricultural chemical active ingredient, the surfactant, and the selected polymeric compound having a pyranose ring, and the water is added and kneaded. During this kneading, a portion of the quaternary bipyridylium salt dissolves in water due to its easy water solubility. Once sufficiently kneaded, it is passed through a conventional granulator, granulator, etc. to form granules. Preferably, in a spherical sieving machine,
The shape should be rounded and the edges of the granules should be rounded to prevent the generation of fine dust.

In this case, the size of the granule should be cylindrical, with the diameter and height being approximately the same, and the absolute value
It is about 0.5 to 2 mm, and may be smaller, but
Basically, the bigger the better. Thereafter, water is removed in a drying process, and the final form of the preparation is obtained through a sifter. As with the main raw materials, the various additives described above are preferably pulverized to about 5 microns or finer and added during the solid mixing or kneading process.
These processes can be carried out either batchwise or continuously, and it goes without saying that ordinary manufacturing methods and combinations of manufacturing processes other than those described above can also be used.

The preparation obtained in the above manner is extremely safe in terms of use and handling, as it is difficult to generate dust with sufficient hardness that both the agricultural chemical active ingredient and other ingredients are uniformly distributed, and is difficult to spray. When it is then poured into a spray solution, it quickly disintegrates, dissolves or disperses, and the solution is no different from a normal wettable powder spray solution that meets the requirements for a spray solution.

Next, in order to concretely illustrate the content of the present invention, examples will be described below along with comparative examples. (In each example, parts indicate parts by weight).

Comparative Example 1 120 parts of 1,1-dimethyl-3-phenylurea of 5 microns or less and 100 parts of 1,1'-ethylene-2,2'-bipyridylium dibromide crushed in a high-speed swing hammer type crusher. Then, 30 parts of a nonionic surfactant (polyoxyethylene sorbitan monolaurate) and 30 parts of water were added and kneaded well, and then used in a granulator to form a mixture with a diameter of 0.8 mm and a length of 0.5 to 1.2 mm.
200 parts of the preparation were obtained by drying. Although this preparation rapidly disintegrated in water and was easily dispersed in liquid, many portions became quite powdery during handling, making it unsuitable for practical use.

Comparative Example 2 Compared to Comparative Example 1, more bentonite was added during solid mixing.
Add 250 parts (average particle size 5 microns) and add water.
The amount was increased from 30 parts to 40 parts to obtain 450 parts of a dry preparation of the same size as Comparative Example 1. The strength of the preparation was high, and there were very few parts that became powdery during transportation or other handling, which was an improvement over Comparative Example 1 in this respect. However, the disintegrability in water was significantly lowered, and among the pesticide active ingredients, the suspension of 1,1 dimethyl-3-phenylurea was significantly lower.

Comparative Example 3 About 5 microns in size crushed by a crusher,
1,1-dimethyl-3-phenylurea 120 parts, 1,
30 parts of a nonionic surfactant and 40 parts of water were added to a solid mixture of 80 parts of 1'-dimethyl-4,4'-bipyridylium dichloride and 250 parts of diatomaceous earth, followed by kneading, granulation, and drying steps. After that, 440 parts of granules with a diameter of 0.8 mm and a length of 1.0 mm were manufactured.

The granules were dropped into water and the physical properties were observed, but as in Comparative Example 2, the strength of the formulation was secured; however,
The suspension rate was extremely low. (The suspension rate was measured according to the official pesticide testing method and was about 20% for the 1,1-dimethyl-3-phenylurea.) Comparative Example 4 In Comparative Example 3, 1,1-dimethyl-3-phenylurea A preparation was obtained in the same manner as in Comparative Example 3 except that 120 parts of 3-(3,4-dichlorophenyl)-1,1-dimethylurea was used in place of 3-(3,4-dichlorophenyl)-1,1-dimethylurea, and 250 parts of clay was used in place of diatomaceous earth. After all, the pull-up rate is low,
Regarding 1,1-dimethyl-3-phenylurea, it was about 50% at most. The suspension rate of the bipyridylium salt was approximately 100%.

Comparative Example 5 3 pieces of 1-5μ size crushed with a crusher
-(3,4-dichlorophenyl)-1,1-dimethylurea 100 parts, 1,1'-dimethyl-4,4'-bipyridylium dichloride 100 parts, solid nonionic surfactant 30 parts, A solid mixture of 200 parts of urea and 20 parts of water
After adding parts, kneading, granulation and drying process, the diameter
350 copies of granules with a length of 0.8 mm and a length of 0.8 mm were manufactured. The granules were brittle, and the suspension rate of 3-(3,4 dichlorophenyl)-1,1-dimethylurea was just under 50%.

Example 1 Three particles were each crushed to a size of 5 microns or less by crushing with a high-speed swing hammer type crusher.
(3,4-dichlorophenyl)-1,1-dimethylurea 120 parts and starch 25 parts with unground 1,1'-
Dimethyl-4,4'-bipyridylium dichloride 80
and 30 parts of water in the mixture.
Spray 30 parts of liquid nonionic surfactant (polyoxyethylene sorbitan monolaurate),
After thoroughly kneading, it is passed through a granulator and dryer to form a powder with a diameter of 0.8 mm.
Cylindrical granules with a length of about 1 mm were obtained. The yield was 250 copies.

The shape is strong and disintegrates well in water (30
When measuring the suspension rate, the phenyl urea compound showed a suspension rate of 81%, and the quaternary bipyridylium salt compound showed a suspension rate of almost 100% (this quaternary bipyridylium salt is dissolved in water). However, in accordance with the above-mentioned "Official Test Method for Agricultural Chemicals," the value of "suspension ratio" defined in this test method was measured for quaternary bipyridylium salts. (In all Examples below, the suspension rate of the herbicidal quaternary bipyridylium salt was almost 100%, so the description was omitted.) Example 2 In Example 1, (size of 5 microns or less)
Granules were produced in accordance with Example 1 using 250 parts of 250 parts of water and 40 parts of water without changing the amounts of other ingredients.
The strength of the formulation is also quite satisfactory; it disintegrates within 1 minute when added to water, and the phenyl urea compound is 80%
It showed a suspension rate of several percent.

Example 3 In accordance with Example 1, 25 parts of sodium salt of carboxymethylcellulose (fine particles crushed to a size of 5 microns or less with a high-speed swing hammer type crusher) was used instead of 25 parts of starch in Example 1. Granules were produced.

The formulation has stable hardness and disintegrates extremely quickly when placed in water, achieving a suspension rate of 83% for the phenyl urea compound.

Example 4 Granules were produced according to Example 1, using 25 parts of crystalline cellulose (with a particle size of 3 microns or less) instead of 25 parts of starch.

The formulation is hard and disintegrates extremely quickly when placed in water, with a suspension rate of 83% for phenyl urea compounds.
showed that.

Examples 5 to 8 In Example 4, instead of 120 parts of 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 1,1-dimethyl-3-phenylurea (Example 5), 3 -(P-chlorophenyl)-1,1-dimethylurea (Example 6), 3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea (Example 7), 3-(P- Chlorophenyl)-1-
Using 120 parts of methoxy-1-methylurea (Example 8) (each having a size of 5 microns or less), granules were produced according to Example 4, and the suspension rate of each phenyl urea compound was 80%. Granules with sufficient strength were obtained.

Example 9 Granules were produced according to Example 1, using 250 parts of crystalline cellulose (with a particle size of 3 microns or less) instead of 25 parts of starch. In this case, although the formulation was extremely strong, it had good dispersibility in water, and the suspension rate of the phenyl urea compound was 84%.

Example 10 In Example 9, 1,1′-dimethyl-4,
Instead of 80 parts of 4′-bipyridylium dichloride,
Granules were produced according to Example 1 using 100 parts of 1,1'-ethylene-2,2'-bipyridylium dibromide. The granules had sufficient performance in terms of strength, disintegration in water, and suspension (suspension rate: 85%).

Comparative Example 6 In Comparative Example 2, 250 parts of cellulose (90% of cellulose powder passes through a 200 mesh mesh; the size of the 200 mesh mesh is 74 microns) was used instead of bentonite. Granules were manufactured according to the following.

However, when this granule was dissolved in water, the suspension rate of the phenyl urea compound did not improve.

Claims (1)

[Scope of Claims] 1. At least one herbicidal quaternary selected from the group of 1,1'-ethylene-2,2'-bipyridylium salts and 1,1'-dimethyl-4,4'-bipyridylium salts. Bipyridylium salt (a), 1,1'-dimethyl-3-phenylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3,4
-dichlorophenyl)-1-methoxy-1-methylurea, 3-(p-chlorophenyl)-1,1-
Dimethylurea and 3-(p-chlorophenyl)-
Particles (b) with a particle size of 5 microns or less obtained by pulverizing at least one herbicidal phenylurea compound selected from the group of 1-methoxy-1-methylurea, starch,
A mixture of particles (c) with a particle size of 5 microns or less obtained by pulverizing at least one pyranose ring-containing polymer compound or a derivative thereof selected from the group of cellulose and salts of carboxymethylated cellulose is added to water. What is claimed is: 1. A water-disintegrating herbicide composition with high strength, solid granules, and excellent disintegration in water, which is obtained by kneading, granulating and drying. 2. The composition according to claim 1, wherein the particles (c) of the pyranose ring-containing polymer compound or its derivative have a particle size of 3 microns or less. 3. The composition according to claim 1, wherein a nonionic surfactant or a cationic surfactant or both are further added to the mixture of particles (a), (b) and (c).