JP2692213B2 - Controlled Release Granules for Weeding Paddy Fields - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel controlled release granule for paddy field herbicides, and more specifically, it shows efficacy against sulfonylurea herbicidal active compounds and paddy herb fly. TECHNICAL FIELD The present invention relates to a controlled release granule for paddy field herbicides which simultaneously contains a herbicidal active compound in the same grain, and a method for producing the granular paddy field herbicide.

[Conventional technology and problems]

Conventionally, as a herbicide for paddy field weeding, there are various forms of lumber, but granules are generally used because of the ease of use.

In the paddy field herbicide, there are two techniques for controlling the release of the herbicidally active compound into water, one is to promote the release of the active compound into water, and the other is to control the release.

The former aims at killing the target weed by promoting the release of the herbicidally active compound into water as much as possible, and for example, contains the herbicidally active compound which is effective against the fly, which is one of the main weeds of paddy fields. There are granules.

The latter is, for example, a herbicidally active compound having a strong herbicidal effect, and is intended to kill the target weeds by controlling the release thereof, which is contrary to the former, to reduce the chemical damage to paddy rice.

However, in a granular rice paddy herbicide, two or more kinds of herbicidally active compounds are included in the granules so that the release of one kind of herbicidally active compound and the promotion of the release of another kind of herbicidally active compound are carried out. No controlled release herbicidal granules for paddy fields are known. In general, excellent granules for weed control in paddy fields have (1) no phytotoxicity against paddy rice, and (2) excellent weed control effect against all weeds in paddy fields including fly.

(3) Long residual effect. That is, the effect of (2) above is maintained for a long period of time.

(4) The active ingredient of the granule during storage does not decompose over a long period of time.

Granules having the above-mentioned effects at the same time are completely ideal and strongly desired.

[Means for solving the problem]

The present invention relates to a novel controlled release granule for paddy field herbicides, and more specifically, a release containing a sulfonylurea herbicidally active compound and a herbicidally active compound showing efficacy against paddy field weeds in the same grain at the same time. It relates to controlled paddy field herbicides.

In the present invention, the controlled release means that the controlled release of one of the two or more herbicidally active compounds and the accelerated release of the other compound are both provided.

That is, the paddy herbicidal granules of the present invention have both functions of suppressing the release of sulfonylurea herbicidal active compounds and promoting the release of herbicidal active compounds that are effective for the paddy field weeds in the same granule. It is a thing.

The sulfonylurea herbicidally active compound has a small content in the granules of the present invention, but its herbicidal activity is extremely high, and when it is applied as a normal granule, the active compound is rapidly dissolved in the paddy water, and therefore the phytotoxicity of paddy rice is caused. Or the active compound is washed away from the paddy field due to water leakage. Therefore, it is important to gradually release as little as possible into the paddy water.

Further, the sulfonylurea herbicidally active compound has a high herbicidal activity against most of the paddy field weeds even in an extremely small amount, but its efficacy is insufficient against the fly, which is the main weed of the paddy field. Therefore, a herbicidal granule that simultaneously contains a sulfonylurea herbicidal active compound and a herbicidal active compound having an effect on the fly in the same grain has been required.

From the viewpoint of controlling the time of controlling the fly in the paddy field, it is necessary to promptly promote the release of the herbicidally active compound that is effective against the fly into the paddy water.

That is, it is necessary to develop granules that have both the suppression of the release of one active compound and the promotion of the release of the other active compound within the paddy field herbicide granules. Is completed.

That is, the present invention relates to a controlled release granule for paddy field control and a method for producing the granular control paddy field control, containing the following substances.

Sulfonylurea herbicidal active compound, a clay mineral and a granulated product consisting of paraffin wax solid at room temperature Herbicidal active compound that is effective for fly of paddy weeds Clay mineral surfactant Surfactant The method for producing a paddy herb granule of the present invention is: It is as follows.

Paraffin wax that is solid at room temperature is heated and melted above its melting point, and a sulfonylurea herbicidally active compound and a clay mineral are uniformly mixed and granulated to obtain a fine granule,
Then, the granulated product is mixed with a herbicidal active compound having an effect on fly of paddy field weeding, a clay mineral, and a surfactant to granulate the mixture uniformly, and the release is controlled. Is the way.

The following effects are obtained by applying the paddy field herbicide of the present invention to a paddy field.

(1) Very little chemical damage to paddy rice.

(2) It has an excellent herbicidal effect on all weeds in paddy fields including fly.

(3) Long residual effect. That is, the effect of (2) above is maintained for a long period of time.

(4) The active ingredient of the granule during storage does not decompose over a long period of time.

The granules for paddy field herbicides having the above effects at the same time are completely ideal, and the granules for paddy field herbicides of the present invention can achieve this completely. When the paddy field herbicide of the present invention is applied to the paddy field, first, the herbicidal active compound having an effect on the fly is promptly promoted to be released from the granule into the paddy water, and kills the fly, which is one of the main weeds, and at the same time weeds. By suppressing the release of the sulfonylurea herbicidally active compound having high potency so that it is gradually released little by little, it is possible to prolong the period of herbicidal efficacy without causing chemical damage to paddy rice.

In the present invention, the clay mineral is not particularly limited, for example, clay, talc, bentonite, diatomaceous earth,
Usual solid carriers such as calcium carbonate, white carbon and the like can be mentioned.

The paraffin wax solid at room temperature is not particularly limited, and examples thereof include ordinary petroleum-based solid paraffin wax, wood wax, beeswax, carnauba wax, and the like, and preferably petroleum-based solid paraffin wax. ,
Isoparaffins, normal paraffins or mixtures thereof with melting points in the range 50 to 95 ° C. are suitable.

The sulfonylurea herbicidal active ingredient is not particularly limited, but is, for example, the following formula: Q-SO ₂ NHCONH-R (In the formula, Q is a phenyl group which may be substituted with various substituents, a benzyl group. Or represents a heterocyclic group, R
Represents a pyrimidyl group or a triazyl group which may be substituted with various substituents. ), Specifically, for example, N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -4-ethoxycarbonyl-1-methylpyrazole-5-sulfonamide (hereinafter , Compound A)), methyl-2-
[[[[[(4,6-dimethoxypyrimidin-2-yl)
Amino] carbonyl] amino] sulfonyl] methyl] benzoate (hereinafter abbreviated as compound B) and the like.

The content of the sulfonylurea herbicidal active ingredient in the granules of the present invention is not particularly limited, but usually 0.
The range of 01 to 1% by weight is preferred.

The surfactant in the granule of the present invention is necessary for the diffusion of the granule containing the sulfonylurea herbicidal active ingredient in water and the acceleration of the release of the herbicidal active compound having an effect on the fly, and examples thereof include alkylbenzene sulfonate. , Polyoxyethylene alkyl allyl ether, lignin sulfonate, alkyl sulfosuccinate, polyoxyethylene fatty acid ester, naphthalene sulfonate, polyoxyethylene alkyl allyl ether sulfate, alkylamino salt, tripolyphosphate and the like, The content of these surfactants in the granule is not particularly limited, but is preferably in the range of 0.05 to 10% by weight.

The herbicidally active compound having an effect on the fly of paddy weeds is not particularly limited, and examples thereof include the following compounds.

N- (0,0-diisopropyl-dithiophosphoryl-acetyl) -2-methyl-piperidine (hereinafter referred to as piperophos) 3- (2,4-dichloro-5-isopropoxyphenyl) -5-tertiarybutyl- 1,3,4-oxadiazol-2 (3H) -one (hereinafter referred to as oxadiazone) 2,4-dichloro-3′-methoxy-4′-nitrodiphenyl ether (hereinafter referred to as chloromethoxynil) 2,4,6-Trichloro-4'-nitrodiphenyl ether (hereinafter referred to as CNP) 2,4-dichlorophenyl-3-methoxycarbonyl-
4'-nitrophenyl ether (hereinafter referred to as biphenox) 3- [2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) -phenoxy-tetrahydrofuran (hereinafter referred to as MT-124) S -(4-Chlorobenzyl) N, N-diethylthiolcarbamate (hereinafter referred to as "bentocarb") S-ethyl-N, N-hexamethylenethiocarbamate (hereinafter referred to as "molinate") S-1-ethyl-propyl- N-, N-hexamethylene thiol carbamate (hereinafter referred to as biram) S-isopropyl-N, N-hexamethylene thiol carbamate (hereinafter referred to as isopropylate) S- (1-methyl-1-phenethyl)- Piperidine-
1-Carbothioate (hereinafter referred to as dimepiperate) 1- (α, α-Dimethylbenzyl) -3-p-triurea (hereinafter referred to as Daimlon) 4-ethoxy-methoxy-benz-2 ′, 3 ′ -Dichloroanilide (hereinafter referred to as HW-52) S-benzyl-N-ethyl-N- (1,2-dimethylpropyl) thiolcarbamate (hereinafter referred to as esprocarb) S-benzyl-N-di- n-Propylthiol carbamate (hereinafter referred to as SC-5574) N-butoxymethyl-2,6-diethyl-α-chloroacetanilide (hereinafter referred to as butachlor) 2-chloro-2 ', 6'-diethyl- N- (n-propoxyethyl) acetanilide (hereinafter referred to as pretilachlor) N- [2 '-(3'-methoxy) -thienylmethyl]
-2,6-Dimethyl-α-chloroacetanilide (hereinafter, N
It is called SK-850. ) 2 ', 6'-diethyl-N- [2-cis-butenoxy)
Methyl] -2-chloroacetanilide (hereinafter, KH-218
Called. ) 4- (2,4-dichlorobenzoyl) -1--3-dimethylpyrazol-5-yl-p-toluenesulfonate (hereinafter referred to as pyrazolate) 1,3-dimethyl-4- (2,4-dichloro) Benzoyl)-
5-phenacyloxy-pyrazole (hereinafter referred to as pyrazoxifene) 2- [4- (2,4-dichloro-m-trioyl) 1,3-
Dimethylpyrazol-5-yloxy] -4'-methylacetophenone (hereinafter referred to as pyrazophenap) 3,7-dichloro-8-quinolinecarboxylic acid (hereinafter referred to as quinclorac) 0- (3-tertiarybutylphenyl ) -N- (6-
Methoxy-2-pyridyl) -N-methylthiocarbamate (hereinafter referred to as TSH-888) 1- (2-chlorobenzyl) -3- (α, α-dimethylbenzyl) urea (hereinafter referred to as JC-940). ) In the granule of the present invention, the herbicidally active compound having an effect on the fly of paddy field weeds may contain one kind or two or more kinds. This content is not particularly limited, but is usually preferably in the range of 0.01 to 15% by weight.

Further, in the herbicide for paddy field of the present invention, the content of the granulated product is not particularly limited, 0.1 ~ 10 wt%
Is preferable.

The particle size of the granulated product is preferably in the range of about 0.1 to 0.7 mm. If this particle size is smaller than this range, the active ingredient tends to come out and is released in a relatively short period, while if it is larger than this range, the release of the active ingredient is suppressed and it is difficult to obtain a sufficient herbicidal effect. Become.

Next, specific examples and test examples of the present invention will be described. However, the present invention is not limited only to these Examples and Test Examples.

 All parts below refer to parts by weight.

The active ingredient compounds used in the following Examples, Comparative Examples and Test Examples are as follows.

(1) N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -4-ethoxycarbonyl-1
-Methylpyrazole-5-sulfonamide (hereinafter abbreviated as Compound A) (2) Methyl-2-[[[[[(4,6-dimethoxypyrimidin-2-yl) amino] carbonyl] amino] sulfonyl] Methyl] benzoate (hereinafter abbreviated as compound B) (3) 3- (2,4-dichloro-5-isopropoxyphenyl) -5-tert-butyl-1,3,4-oxadiazole-2 ( 3H) -one (oxadiazone) (hereinafter, abbreviated as compound) (4) 2-chloro-2 ', 6'-diethyl-N- (n-propoxyethyl) acetanilide (pretilachlor) (hereinafter, abbreviated as compound) (5) 4- (2,4-dichlorobenzoyl) -1,3-dimethylpyrazol-5-yl-p-toluenesulfonate (hereinafter abbreviated as compound) (6) 3,7-dichloro-8. − Norinkarubon acid (quinclorac) (hereinafter, abbreviated as compound.) Compound A 7 parts of finely pulverized to approximately Example 1 about 5 microns, about
Petroleum paraffin wax melted at 80 ℃ (melting point 69-72
(° C) 100 parts by weight was added little by little, and the compound A was uniformly dispersed by mixing and stirring with a homomixer.

Then, 63 parts of finely powdered calcium carbonate was added little by little and dispersed by stirring.

Cool these mixtures to 60 ° C and apply a 0.5 mm diameter
The granules were extruded with a screen and granulated with a pin mill to obtain the granulated product of the present invention.

Example 2 1.70 having a particle diameter of 0.1 to 0.3 mm obtained in Example 1
Parts, 1.0 parts of finely pulverized compound, 5 parts of polyoxyethylene nonylphenyl ether, 1 part of sodium ligninsulfonate, 50 parts of bentonite, 41.3 parts of talc, and further kneaded by adding an appropriate amount of water to give a diameter of 0.9 mm. Extruded and granulated with a screen of 2 and dried at 50 ° C for 2 hours, then
The granules for paddy field control of the present invention containing the compound A and the compound were obtained by sieving with a 32 mesh sieve.

Example 3 Particles having a particle size of 0.1 to 0.3 mm obtained in Example 1 1.70
Parts and finely ground compound 5 parts polyoxyethylene nonylphenyl ether 2 parts, sodium tripolyphosphate 1
Part, bentonite 30 parts, clay 60.3 parts together,
Further, an appropriate amount of water is added and kneaded, and the mixture is extruded with a screen having a diameter of 0.9 mm to be granulated, dried at 50 ° C. for 2 hours, and then sieved with a mesh of 14 to 32 to remove the paddy field of the present invention containing compound A and the compound. A granule was obtained.

Example 4 Particles having a particle size of 0.1 to 0.3 mm obtained in Example 1 1.70
Parts, pulverized compound 1.0 parts, compound 2.0 parts, polyoxyethylene nonylphenyl ether 5 parts, sodium lignin sulfonate 1 part, bentonite 40 parts, talc 49.3
Part, mix with an appropriate amount of water, knead, and
The mixture was extruded and granulated with a 0.9 mm screen, dried at 50 ° C. for 2 hours, and sieved with a 14 to 32 mesh sieve to obtain compound A, a compound and a granule for paddy field weeding of the present invention containing the compound.

Example 5 The procedure of Example 1 was repeated except that 7 parts of compound A was replaced with 25 parts of compound B and 63 parts of calcium carbonate was replaced with 100 parts, to prepare a compound of the present invention containing compound B. Granules were obtained.

Example 6 Granules obtained in Example 5 having a particle size of 0.1-0.3 mm 2.25
Part, finely pulverized compound 1.0 part, dioctyl sulfosuccinate 0.5 part, bentonite 30 parts, lignin sulfonate soda 2 parts, talc 64.25 parts, and further add an appropriate amount of water and knead, 0.9 mm diameter screen The mixture was extruded and granulated at 50 ° C. for 2 hours, and then sieved with a 14 to 32 mesh sieve to obtain the granules for paddy field weeding of the present invention containing the compound B and the compound.

Comparative Example 1 0.07 part of finely ground compound A, 1.0 of finely ground compound
Part, polyoxyethylene nonyl phenyl ether 5 parts,
1 part of sodium lignin sulfonate, 50 parts of bentonite, 42.93 parts of talc and 42.93 parts of talc are mixed, and an appropriate amount of water is further added and kneaded.
After drying at 0 ° C. for 2 hours, it was sieved with 14 to 32 mesh to obtain a paddy herd granule containing compound A and the compound.

Comparative Example 2 0.07 part of finely ground compound A, 5.0 of finely ground compound
Part, polyoxyethylene nonylphenyl ether 2 parts,
Sodium tripolyphosphate 1 part, bentonite 30 parts, clay
Mix with 61.93 parts, add an appropriate amount of water and knead, extrude with a screen having a diameter of 0.9 mm, and granulate at 50 ° C.
After drying for 2 hours, the mixture was sieved with a 14-32 mesh to obtain a paddy herb granule containing compound A and the compound.

Comparative Example 3 In Comparative Example 2, 0.07 part of compound A was replaced with 0.25 part of compound B, 5.0 parts of compound was replaced with 1 part of compound, and clay 61.
The same operations as in Comparative Example 2 were carried out except that 93 parts were replaced with 65.75 parts to obtain compound B and a granule for paddy field weeding containing the compound.

Next, an abuse test was conducted using each of the above-mentioned preparations to examine the stabilizing effect of the pesticide granules of the present invention.

Test Example 1 Abuse Test Each formulation obtained in Example 2, Example 3 and Comparative Example 1 was put in a glass sample bottle with an inner stopper and 50
It was placed in a constant temperature oven at ℃, stored for 14 days and subjected to an abuse test.

The content of each herbicidal active ingredient in each preparation sample before and after the test was measured to calculate the rate of change over time (decomposition rate).

R: content of active ingredient in sample before abuse test S: content of active ingredient in sample after abuse test The content of active ingredient was quantified by an internal standard method by liquid chromatography.

 The results of this test are shown in Table 1.

As is clear from the results shown in Table 1, in the granules of the present invention obtained in Examples 2 and 3, the decomposition of the compound A was almost stable and extremely stable, while the conventional one obtained in Comparative Example 1 It can be said that the above-mentioned granules are extremely unfavorable from a practical point of view because they are extremely decomposed.

Test Example 2 Measurement Test of Elution Concentrations of Preparations (Granules of Examples and Comparative Examples) in Water over Time A 5-unit constant temperature stirring tank (manufactured by Shinto Scientific Co., Ltd.) was used as a tester, and the water temperature was 30 ° C + 0.5 ° C. The stirring rotation speed was set to 30 rpm. The following tests were conducted using this tester.

Hard water (3 degrees) was put into 1 beaker, and 1 g of the test granule was put therein.

This one beaker was installed in the above tester. afterwards,
After one day, about 3 cc of water was sampled and the concentration of the active ingredient was measured by liquid chromatography.

After the above-mentioned water collection for one day, all the hard water in one beaker was drained out, and one new hard water was added. This operation was repeated every day. The purpose of this test is to assume repeated flooding and falling of water and leakage in actual paddy fields. The results are shown in Table 2.

 The release rate in Table 2 was calculated according to the following formula.

As is clear from the results in Table 2 above, in the granules of the present invention, the compound A and the compound B are controlled so as to be gradually eluted into water from the granules over a long period of time.
On the other hand, a compound, a compound, a compound, and a compound as a shaving agent are controlled so as to be rapidly dissolved in water.

On the other hand, in the granules of the comparative examples, the compound A and the compound B are eluted from the granules into water in a short time, and most of them are washed away after 2 days.

This is due to the fact that in the actual paddy field, the compound A and the compound B were used in the granules of the comparative example in which release was not controlled,
Meaning that phytotoxicity to rice is likely to occur and herbicidal efficacy is poorly sustained. On the other hand, the controlled release of the granules of the present invention means that there is little fear of phytotoxicity and long-lasting herbicidal efficacy. To do.

Test Example 3 Herbicidal effect test under static and free-flowing conditions 30 cm x 30 cm x 15 cm (length x width x depth) plastic pots were filled with paddy soil, filled with water, and scavenged,
The water depth was 4 cm.

The pot was treated with a predetermined amount of the granules of the above Examples and Comparative Examples.

In the test of the still water condition, after the granule treatment, the water was left standing for 6 days while maintaining the waterlogging depth of 4 cm, and thereafter seeds of the sea bream, eel and firefly were sown in the soil.
On the other hand, in the free-flowing condition test, from the day after the granule treatment, a fixed amount of water was sent into the pot with a metering pump, and the water was allowed to overflow from the pot so that all the water in the pot was replaced in one day. did. This operation was continued for 6 days. After this, seeds of lobster, eel and firefly were sown in the soil. Thirty days after sowing, the herbicidal effect was investigated according to the following criteria. The results are shown in Table 4.

 The herbicidal rate in Table 3 was measured by visual observation.

Judgment criteria 10 ……… The herbicidal rate is 100% 9 〃 90% or more 8 〃 80 to 90% 7 〃 70 to 80% 6 〃 60 to 70% 5 〃 50 to 60% 4 〃 40 to 50% 3 〃 30 to 40% 2 〃 20 to 10% 1 〃 10 to 20% 0 〃 0 to 10% As is clear from the results shown in Table 3, under the water-stopping condition, both the granules of Comparative Example and the granules of the present invention showed a strong herbicidal effect and there was no significant difference in the herbicidal activity. Under conditions close to the practical conditions in paddy fields, the granules of the present invention showed a sufficient herbicidal effect on all weeds, but the granules of the comparative examples have an insufficient herbicidal effect.

Test Example 4 Effect of phytotoxicity on transplanted paddy rice Wagner pots of 1/5000 are were filled with paddy soil, water was added, and water was scavenged to make a submerged condition at a water depth of 4 cm.

Two 2-leaf stage rice seedlings were planted in this pot per pot, and 3 days after planting, a prescribed amount of granules was treated. 2cm per day from the bottom of the pot for 2 days from the day after treatment
The water was gradually drained at the speed of, and thereafter, the water was flooded at a depth of 4 cm.

On the 30th day after the treatment, the fresh weight of the above-ground part of the rice was measured in order to investigate the effect of phytotoxicity on the rice.

The results are shown in Table 4. The values in Table 4 are 100 for untreated plots.
Indicates the relative value when.

As is clear from the results of Table 4, in the granules of the present invention,
Almost equal to the untreated plot, no phytotoxicity was observed. on the other hand,
With the granules of the comparative examples, phytotoxicity was observed, and especially at high doses, the phytotoxicity was remarkable.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Yuta Shirai 1470 Shiraoka, Shiraoka-cho, Minamisaitama-gun, Saitama Nissan Biotechnology Research Institute (72) Inventor Takashi Inokai 1470 Shiraoka, Shiraoka-cho, Minami-Saitama-gun, Saitama Sanraku Kagaku Kogyo Co., Ltd. Biological Sciences Research Laboratory Examiner Karaki Ichiyoshi (56) Reference JP 62-84004 (JP, A) JP 62-277306 (JP, A) JP 63-35504 (JP, A) JP-A-59-82306 (JP, A) JP-A-63-112504 (JP, A) JP-A-62-265207 (JP, A) JP-B-52-21059 (JP, B2)

Claims (7)

(57) [Claims] 1. A controlled release granule for paddy field control, which comprises the following substances and. Granules consisting of sulfonylurea herbicidal active compounds, clay minerals and paraffin wax solid at room temperature Herbicidal active compounds that are effective against fly in paddy weeds Clay minerals Surfactants 2. The herbicide for paddy fields according to claim 1, wherein the content of the sulfonylurea herbicidally active compound in the herbicide for paddy field herbicides is 0.01 to 1% by weight. 3. The herbicide for paddy field herbicides according to claim 1, wherein the content of the granulated product is 0.1 to 10% by weight. 4. The herbicide for paddy fields according to claim 1, wherein the granulated product has a particle size of about 0.1 to 0.7 mm. 5. A sulfonylurea herbicidally active compound is N
-[(4,6-Dimethoxypyrimidin-2-yl) aminocarbonyl] -4-ethoxycarbonyl-1-methylpyrazole-5-sulfonamide for controlled release controlled paddy field weeding according to claim 1. Granules. 6. A sulfonylurea herbicidally active compound is methyl-2-[[[[[(4,6-dimethoxypyrimidine-
2-yl) amino] carbonyl] amino] sulfonyl]
A controlled release granule for paddy field control according to claim 1, which is methyl] benzoate. 7. Paraffin wax which is solid at room temperature is heated and melted to a temperature equal to or higher than its melting point, and a sulfonylurea herbicidally active compound and a clay mineral are uniformly mixed and granulated to obtain fine granules, A method for producing a controlled release granule for paddy field weeds, which comprises uniformly mixing and granulating a granulated product, a herbicidal active compound which is effective against fly of paddy field weeds, a clay mineral and a surfactant.