JPS6284004A - Improved herbicidal granular composition - Google Patents

Abstract

PURPOSE:The titled composition having improved stability of each herbicidal component, sufficiently showing characteristics of herbicidal components simultaneously, having no phytotoxicity to paddy rice plants, obtained by adding CaCO3, etc., to a granular composition containing saturn and another compound as active components. CONSTITUTION:Saturn[=S-(4-chlorobenzyl) N,N-diethylthiol carbamate] well- known as a herbicide showing improved effects on barnyard millet, main weed in paddy fields, is blended with 2-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonylaminosulfonylm-ethyl]benzoic acid methyl ester, a herbicidally active compound having excellent effects on perennial weeds, incorporated with CaCO3 and, if necessary, sodium tripolyphosphate, optionally a carrier and an auxiliary and molded into granular. EFFECT:The titled composition shows wide herbicidal spectrum on weeds and can reduce phytotoxicity to paddy rice plants of Japonica species.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a herbicidal granule composition useful for controlling various agriculturally harmful weeds.

(Prior art) S-(4-chlorobenzyl) N,N-diethylthiol carbamate (hereinafter abbreviated as compound (1)) is described in Pesticide Handbook 1981 edition, page 403,
This herbicide is already widely used under the name ``Saturn'' and is extremely effective against barnyard grass, a major weed in rice fields. On the other hand, 2-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonylaminosulfonylmethyl]benzoic acid methyl ester (hereinafter abbreviated as compound (II)) is described in JP-A-57-112379. ,
It is a herbicidal active compound that is highly effective against perennial weeds.

Mix compound (1) and compound (II).

By creating a composite formulation, it becomes a labor-saving herbicide with a wide herbicidal spectrum. Furthermore, compound (1) and compound (
The combination of II) not only broadens the herbicidal spectrum.

It is already known that compound (■) reduces the chemical damage caused to Japonica rice (Japanese Patent Application Laid-Open No. 59-82
No. 306).

(Problems to be Solved by the Invention) As described above, it is convenient to formulate a characteristic composite preparation consisting of compound (II) into granules, especially for spraying as a paddy field herbicide.

However, when the granules prepared using the technology described in JP-A-59-82306 were stored for a long period of time, compounds (■
) and degrade over time. or.

When this granule is applied to paddy fields, the effect of reducing phytotoxicity to paddy rice is insufficient, and in practice, phytotoxicity becomes an obstacle, making it difficult to apply in a dosage sufficient to obtain a sufficient herbicidal effect.

Techniques for stabilizing herbicidal components in herbicidal granules include methods of adding various stabilizers (for example, Japanese Patent Publication No. 45
-28398, 45-28399, 46-307
17, No. 47-24129.

47-37008) and a method of physically isolating herbicidal ingredients from substances that promote decomposition (Japanese Patent Publication No. 52-21059)
No.) etc. are known.

The granules of the present invention cannot be sufficiently effective by these methods, and there is a concern that adding a stabilizer may cause secondary problems such as environmental pollution after dispersion of the granules. . Furthermore, the method of coating the active ingredient with a waxy substance suppresses its effective release into water, resulting in a reduced herbicidal effect. Furthermore, a method for obtaining a stabilized aqueous composition of compound (■) using a water-soluble inorganic salt etc. (JP-A-59-205305
No.) is known, but according to this, compound (II) becomes a water-soluble salt, and the release properties of compound (II) required by the granules of the present invention as described later cannot be obtained.

Next, in order for compound (1) to stably reduce the phytotoxicity of compound (I[) to paddy rice, compound (+) must be absorbed into the rice body before compound (II) is absorbed into the rice body. It is necessary to be present.

Although the mechanism is not yet clear, it is presumed that the presence of the compound (11) in the rice body accelerates the metabolic rate of the incorporated compound (11), and as a result, the phytotoxicity of paddy rice is reduced.

Therefore, in order to stably exhibit the effect of compound (+) on reducing phytotoxicity, compound (1) in one granule should be preferentially released into rice water, and after a certain period of time (preferably 2 to 5 days) compound (
■) It is necessary to release . However, compound (11) does not have sufficient herbicidal effect even if it is gradually released into water in small amounts, and a single compound granule must be given the ability to rapidly release compound (n) after a certain period of time. On the other hand, it is desirable to release the compound (+) into the rice water immediately.

Conventionally, various auxiliary agents have been used as techniques related to this.

Method for promoting disintegration of granules and speeding up elution of components (Japanese Patent Publication No. 40-25520, 4g-38858, 52-4
No. 7016, No. 53-46888), and conversely, a method of worsening the disintegration of granules as a technique for suppressing the elution of components (
Japanese Patent Publication No. 45-2200) and a method of suppressing release of components by coating with resin (Japanese Patent Publication No. 41-19080) are known. However, all of these techniques are aimed at promoting rapid release immediately after spraying or gradually releasing trace components over a long period of time, and all of these known techniques either promote or suppress release. It is intended for either one of the following.

On the other hand, in a single decomposition agent, the release of one component (compound (I) in the present invention) is promoted, the release of the other component (compound (II) in the present invention) is suppressed for a certain period of time, and then it is rapidly released. It is necessary to perfect the technology to control the rice, and it has not been possible to obtain composite granules containing the compound (■) that is highly safe for paddy rice using conventional technology.

The present inventors have stabilized the compound (II) that is easily decomposed in the granules, and the compound (I) in the granules is quickly released into paddy water after dispersion, and the compound (IN) is desirably released after a certain period of time. conducted repeated research with the aim of completing a formulation that would be rapidly released after 2 to 5 days. As a result, it was found that 5 compounds (II) were stabilized in the presence of calcium carbonate and the water solubility was suppressed, and furthermore, it was found that sodium tripolyphosphate reduced the elution of herbicidal components to WRj21 and reduced phytotoxicity. By paying attention to this phenomenon, we have completed the present invention.

(Means for solving the problems) The granule composition of the present invention comprises a compound (summer) and a compound (II).
and calcium carbonate or calcium carbonate and sodium tripolyphosphate.

Methods for producing the granule composition of the present invention include, but are not limited to, the following methods.

(j-) A method in which compound (+), compound (II), a surfactant, an extender, etc. are added to calcium carbonate or calcium carbonate and sodium tripolyphosphate, kneaded with water, and then extruded.

(2) A method in which compound (11), a surfactant, an extender, etc. are added to calcium carbonate or calcium carbonate and sodium tripolyphosphate, kneaded with water, extrusion formed, and compound (1) is adsorbed by eruption. .

(3) Add surfactant, filler, etc. to calcium carbonate or calcium carbonate and sodium tripolyphosphate.

After kneading with water, extrusion is performed, and compound (1) is added to this.
, a method of spraying a mixed solution of compound (ff).

(4) After spraying compound (1) onto granular calcium carbonate and uniformly wetting the surface, compound (11), surfactant, filler, etc. is added to calcium carbonate or calcium carbonate and sodium tribolyphosphate or sodium tripolyphosphate. A method in which the fine powder obtained by adding, mixing, and pulverizing is added little by little to make it adhere uniformly to the surface of granular calcium carbonate.

(5) Compound (+) is sprayed onto a natural base such as river sand, and after the surface is evenly wetted, compound (n), filler, surfactant, etc. are added to calcium carbonate or calcium carbonate and sodium tripolyphosphate. A method in which the fine powder obtained by mixing and pulverizing is added little by little to make it adhere uniformly to the surface of a natural base such as river sand.

Bulking agents used in the granule composition of the present invention include bentonite, clay, talc, diatomaceous earth, river sand, etc., and surfactants include alkylbenzenesulfonates, ligninsulfonates, alkylsulfosuccinates, naphthalenesulfonic acid, etc. salts, polyoxyethylene alkylaryl ether sulfates, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid alkyl esters, alkylamine salts, and the like. Furthermore, the granule composition of the present invention may contain starch, CMC, a sizing agent such as polyvinyl alcohol, an inorganic salt, and the like, if necessary.

The blending ratio of calcium carbonate and sodium tripolyphosphate used in the present invention is not particularly limited, but preferably 10 to 90% by weight of calcium carbonate and 0 to 1% of sodium tripolyphosphate, based on the weight of one composition.
01i amount%.

Examples of the present invention are shown below in the margins, but the granulation method is not limited thereto.

(Examples) Example 1-1 0.25 parts of compound (U), 15 parts of powdered calcium carbonate, and 2.75 parts of talc are mixed and ground in a hammer mill to form a fine powder. Mix 75 parts of granular calcium carbonate sized to 14 to 32 meshes with 7 parts of the compound (seal), and after confirming that the surface of each granular calcium carbonate is uniformly wet, add 18 parts of the fine powder little by little. Mix.

The herbicidal granules of the present invention were obtained by uniformly adhering them to the surface of granular calcium carbonate.

Example 1-2 After mixing 0.25 parts of compound (II), 50 parts of powdered calcium carbonate, 36.75 parts of bentonite, 5 parts of calcium ligninsulfonate, and 1 part of sodium alkylnaphthalenesulfonate, the mixture was ground with a hammer mill. Make into a fine powder.

Appropriate water is added to the mixture, kneaded, extruded through a screen with a diameter of 1 square inch, dried at 80°C, and sieved through a 14-32 mesh to obtain granules. A compound (
(2) 7 parts were adsorbed with 11 sprays to obtain a herb granule of the present invention M.

Example 1-3 7 parts of compound (II), 0.25 parts of compound (II), 70 parts of powdered calcium carbonate, 3 parts of polyoxyethylene alkylaryl ether sulfate, and 19.75 parts of starch were mixed and ground in a hammer mill. This fine powder was kneaded with an appropriate amount of water, extruded through a screen with a diameter of 1 square centimeter, dried at 60°C, and sieved through a 14-32 mesh sieve to obtain the herbicidal granules of the present invention. .

Example 2-1 0.25 parts of compound (11), 5 parts of sodium tripolyphosphate, 10 parts of powdered calcium carbonate, and 2.75 parts of talc are mixed and ground in a hammer mill to form a fine powder. 14~
Mix 75 parts of river sand sized to 32 mesh and 7 parts of compound (f), and after confirming that the surface of the river sand is evenly wetted, add 18 parts of the fine powder little by little and mix. The herbicidal granules of the present invention were obtained by uniformly adhering the granules to the granules.

Example 2-2 Compound (n) 0.25 parts, powdered calcium carbonate 50 parts,
Sodium tripolyphosphate 5 parts, bentonite 31°7
5 parts of calcium lignin sulfonate, and 1 part of sodium alkylnaphthalene sulfonate were mixed and ground in a hammer mill to form a fine powder. The mixture is kneaded with an appropriate amount of water, extruded through a screen with a diameter of 1 square inch, dried at 80°C, and sieved through a 14-32 mesh screen to obtain granules.

7 parts of Compound (I) was adsorbed onto 93 parts of the granules to obtain a herbicidal granule of the present invention.

Example 2-3 Compound (■) 0.25 parts, powdered calcium carbonate 50 parts,
After mixing 10 parts of sodium tripolyphosphate, 26.75 parts of bentonite, 5 parts of calcium lignin sulfonate, and 1 part of sodium alkylnaphthalene sulfonate, the mixture was ground in a hammer mill to form a fine powder. Add appropriate water to this, knead it, and extrude it through a screen with a diameter of 11111 mm.

After drying at 80° C. for 11 tons, it is sieved through 14 to 32 meshes to obtain granules. 7 parts of the compound (■) was sprayed and adsorbed onto 93 parts of the granules to obtain herbicidal granules of the present invention.

Example 2-4 7 parts of compound (I), 0.2 s part of compound (II), 20 parts of powdered calcium carbonate, 5 parts of sodium tripolyphosphate, 31.75 parts of talc f, 3 parts of polyoxyethylene alkylaryl ether, polyvinyl Mix 3 parts of alcohol and grind with a hammer mill to a fine powder. This fine powder was kneaded with an appropriate amount of water, extruded through a screen with a diameter of 1 m+, dried at 60°C, and sieved through a 14-32 mesh sieve to obtain the herbicidal granules of the present invention.

The effects of the present invention are shown below.

(Effect of the invention) The herbicidal granules of the present invention have good stability of each herbicidal component.

At the same time, it is an excellent granule that exhibits a wide herbicidal spectrum against weeds without causing any chemical harm to paddy rice because it fully develops the properties of its herbicidal ingredients.

Next, a test example will be given and explained. The following comparative granules were prepared and used in the test.

Comparative Example 1 (Conventional Method) 0.25 parts of compound (11), 5 parts of white carbon, and 12.75 parts of bentonite were mixed and ground in a hammer mill to form a fine powder. River sand sized to 14-32 mesh 7
5 parts of the compound (■) and 7 parts of the compound (■) were mixed, and after confirming that the surface of the river sand was evenly wetted, 18 parts of the fine powder was added little by little and mixed to make it adhere uniformly to the surface of the river sand to kill weeds. Granules were obtained.

Comparative Example 2 (Conventional Method) After mixing 0.25 parts of compound (11), 86.75 parts of bentonite, 5 parts of calcium ligninsulfonate, and 1 part of sodium alkylnaphthalenesulfonate, the mixture was ground in a hammer mill to form a fine powder. . This fine powder was kneaded with an appropriate amount of water, extruded through a 1-diameter screen, dried at 80°C, and sieved through a 14-32 mesh to obtain granules. 7 parts of compound (I) was sprayed and adsorbed onto 93 parts of the granules to obtain herbicidal granules.

Comparative Example 3 (Conventional method) 7 parts of compound (I), 0.25 parts of compound (11), 86.75 parts of hentonite, 5 parts of calcium lignin sulfonate
1 part and 1 part of sodium alkylnaphthalene sulfonate were mixed together and ground in a hammer mill to form a fine powder. This fine powder was kneaded with an appropriate amount of water, extruded through a screen with a diameter of 11 m, dried at 60°C, and sieved through a 14-32 mesh sieve to obtain herbicidal granules. - Comparative Example 4 (method described in Japanese Patent Publication No. 52-21059) 7 parts of compound (I), 77 parts of bentonite, 5 parts of calcium lignin sulfonate, and 1 part of sodium alkylnaphthalene sulfonate were mixed and ground in a hammer mill, Make into a fine powder. Add appropriate water to this fine powder and knead it to obtain a diameter of 1ll.
After extruding through the 11 screen and drying at 60'C.

Sieve through 16 to 32 mesh to obtain granules. Heat the granules to 90'C. Separately, compound (II) O
.

25 parts of paraffin wax (45°F), 9 parts of sorbitan monostearate and 0.75 parts of sorbitan monostearate were mixed, ground in a mortar, mixed uniformly with the heated granules, cooled, and sieved through a 14-mesh sieve. It was divided to obtain herbicide granules.

Comparative Example 5 (method described in JP-A-59-205305) 1.11 parts of sodium ligninsulfonate and 4.48 parts of sodium hydroxide were dissolved in 54.35 parts of water, and compound (11) 21. 3 parts were added in small portions and allowed to react to form a water-soluble sodium salt. Add 4.68 parts of sodium acetate to this solution and after 5 minutes add 4.68 parts of sodium acetate.
Added 8 parts. After about 15 minutes fR observed that precipitation of the sodium salt of compound (n) occurred rapidly.

Furthermore, 9.35 parts of sodium acetate was added. The resulting composition was ground in a sand mill to produce particles with a particle size of 5 microns or less. Polysancharide thickener was added a few minutes before completing the milling operation.

1.2 parts of this sodium salt suspension of compound (II) (component content 21.1%), 17 parts of compound, 5 parts of calcium lignin sulfonate, 1 part of sodium alkylnaphthalene sulfonate, and 85.8 parts of bentonite were added. Add, mix, and grind with a hammer mill to make a fine powder. Appropriate water was added to the mixture, the mixture was kneaded, extruded through a diameter II screen, dried at 60°C, and sieved through a 14-32 mesh sieve to obtain herbicidal granules.

The following margin test example 1 (temporal stability test of active ingredients) The herbicidal granules were sealed in a glass bottle and stored in a thermostat at 50° C. for a predetermined period of time. After the abuse treatment, the herbicide granules were taken out and the content of compound (■) in each herbicide granule was measured by gas chromatography, and the content of compound (■) was measured by high performance liquid chromatography.Compounds before and after abuse treatment (summer), The decomposition rate was determined from the change in the content of compound (n).The results are shown in Table 1.

The following margin (Table 1) Test Example 2 (Water dissolution test of active ingredients) In a constant temperature room at 20°C, 800°C hard water was placed in a 115,000a Wagner pot.
mA was taken and left standing. Approximately 80 lbs each of herbicide granules were accurately weighed in it (equivalent to spraying 4 kg of granules per 108 cm).
was scattered.

1st, 3rd, and 5th day after spraying, water was collected from the center of each pot using a 50ml 11-hole pipette. After extraction with chloroform and concentration using a rotary evaporator, compound (1) was extracted with gas chromatography to obtain compound (I).
I) The content is determined by high performance liquid chromatography method,
The concentration in water was calculated from that value. The results are shown in Table 2.

Blank space below (Table 2) Test Example 3 (Medical efficacy/toxicity test) <Medical efficacy test> A 115,000a Wagner pot was filled with paddy soil in a greenhouse, and after watering, fertilizing, and raking for the first generation, seeds of Japanese millet were sown on the soil surface layer. Also, in another pot, 6 tubers of M'JP-treated Cyperus japonica were buried in water so that they would sprout. It was flooded to a depth of 30m.

For chemical treatment, when the leaf age of Japanese millet is 2 leaves and the leaf age of Japanese water cypress is 2 leaves (plant height 10 to 151), 15 Japanese millet plants and 3 water cypress plants are prepared per pot, and the specified amount of each herbicide (per 10 a. Granules (equivalent to 1.5 - spraying) were weighed out and sprayed in triplicate each.

The investigation was conducted by measuring the aboveground dry weight 30 days after the chemical treatment and comparing it with the untreated plot.

<Pharmaceutical damage test> Paddy soil was filled in a 115,000a Wagner pot in a greenhouse, and after watering, fertilizing, and puddling, transplanted seedlings (variety: Zennanfu,
Three plants (leaf age: 2 leaves) were transplanted to a transplant depth of 2 as, and submerged in water to a depth of 1.

For the chemical treatment, two days after transplanting, a predetermined amount of each herbicide granule (equivalent to spraying 6 kg per 108) was weighed out and sprayed in triplicate.

The leaf age at the time of treatment was 2.2 to 2.3 leaves.

In the investigation, the aboveground dry weight was measured 30 days after the chemical treatment and compared with the untreated plot.

The untreated area is crowded! To avoid damage, I removed the weeds completely by hand.

The results of the drug efficacy/toxicity tests are shown in Table 3.

Margin below (Table 3) Special rF applicant Kumiai Chemical Industry Co., Ltd.

Claims (2)

[Claims] (1) Contains S-(4-chlorobenzyl)N,N-diethylthiol carbamate and 2-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonylaminosulfonylmethyl]benzoic acid methyl ester as active ingredients. An improved herbicidal granule composition characterized in that calcium carbonate is added to the granular composition. (2) Contains S-(4-chlorobenzyl)N,N-diethylthiol carbamate and 2-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonylaminosulfonylmethyl]benzoic acid methyl ester as active ingredients. An improved herbicidal granule composition characterized in that calcium carbonate and sodium tripolyphosphate are added to the granular composition.