JPS5916805A - Herbicidal composition for paddy rice - Google Patents

Abstract

PURPOSE:The titled composition, prepared by incorporating a thiol compound with two three types of triazine compounds, etc. as active constituents, capable of exterminating annual and perennial weeds accurately with a small amount of the chemicals with low toxicity to rice plants and fishes, and having extended periods suitable to the application of the chamicals. CONSTITUTION:A herbicidal composition prepared by incorporating a thiolcarbamate compound of formula I (n is an integer 4-10), which is a nonhormonal migrative herbicide, known as a biosynthesis inhibitor for proteins, and exhibiting improved growth inhibition and killing action on Deccan grass by the treatment in the young bud period with a triazine compound of formula II (R is ethyl or isopropyl; R' is R or 1,2-dimethylpropyl) which is a photosynthesis inhibitor and capable of exhibiting high effects on annual broad-leaved weeds and a compound of formula III (n' is an integer 1-3; X is O or S) which is a plant hormone and if necessary 3-isopropyl-2,1,3-benzothiadiazin-4-one-2,2-dioxide which is a photosynthesis inhibitor as active constituents.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides at least one compound represented by the general formula (1) (wherein n represents an integer of 4 to 10) (hereinafter simply abbreviated as a thiol carbamate compound), Formula (II) (wherein R represents an ethyl or isopropyl group, R
'represents ethyl, isozolobyl or 1,2-methylzolobyl group)
Hereinafter, simply abbreviated as a dorianone compound, at least one compound represented by the general formula (llD (in the formula, n/ represents an integer from 1 to 3, and X represents an oxygen or sulfur atom) (hereinafter simply referred to as a phenolic compound) / compound), and, if necessary, 3-isopropyl-2,1,3-benzothiadiazine- represented by the following structural formula (IV)
The present invention relates to a herbicide composition for paddy rice containing 4-one-2,2'-soxide (hereinafter simply referred to as a benzothiacyanone compound) as an active ingredient.

In this composition, compounds (1), (II) and θ must always contain at least one compound from each group, but compound (IV) may also be included depending on the target of weeding. It may also not be included.

More specifically, the thiol carbamate compound (1
) as 5-(4-chlorobutyl)-N.

N-noethylthiol carbamate, 5-(5-chloropentyl)-N,N-diethylthiol carbamate, 5-(6-chlorohexyl)-N,N-diethylthiol carbamate, 5-(8-chlorooctyl) ) -N
, N-diethylthiol carbamate, etc., and triazine compounds include 2-methylthio-4,6-bis(ethylamino)-8-)riazine, 2-methylthio-
4-ethylamino-6-(112-dimethylzolobylamino)-8-triazine, 2-methylthio-4,6-bis(isopropylamino)-8-)riazine and 2-
Examples of phenoxy compounds include ethyl 2-methyl-4-chlorophenoxybutyrate and 2-methyl-4-chlorophenoxyacetic acid. Thioethyl etc.

The present invention provides these compound groups (1), (II), ω
D and, if necessary, a weed killer for water 1d containing a mixed composition obtained by selecting one or more compounds from compound (IV) and blending them in a specific ratio as an active ingredient. The present invention relates to a drug composition.

The purpose of the present invention is to exterminate not only annual weeds such as barnyard grass, Japanese grasshopper, cyperus, etc., but also barnyard grass, Japanese grasshopper, etc. in as small a quantity as possible by combining three or four types of compounds with various characteristics. It has the excellent features of accurately eradicating perennial weeds such as fireweed, grasshopper, weed, and waterweed, which have become conspicuous due to the use of chemicals, as well as reducing chemical damage to rice and expanding the period during which the chemical is suitable for treatment. The object of the present invention is to provide a herbicide composition for paddy rice that is also low in toxicity to fish.

The above-mentioned thiol carbamate compound is a non-hormonal transfer agent and is known as a protein biosynthesis inhibitor, and has excellent growth suppressing and killing effects on grass weeds, especially barnyard grass, if treated at the young bud stage. It is recognized that there is.

However, with the advanced growth of Japanese barnyard grass, Japanese oak, Japanese azalea, and water...
It is clear that it is less effective against broad-leaved weeds such as grasshopper and Japanese snail.

On the other hand, some thiolcarbamate herbicides with NNC8- as their backbone are highly subacutely toxic to animals around the field, especially fish, and in some cases have caused the death of farmed carp. , significant restrictions and precautions are taken regarding its use. However, the trianone compound (1) was found to be extremely safe and practical. Trianone compounds are generally referred to as photosynthesis inhibitors and have no effect on many annual broad-leaved weeds. Although expensive, it is a serious weed.
It has been reported that it is less effective against firefly, waterbug, etc.

Phenoxy compounds are generally called plant hormones, but their action is said to be auxin disturbance, which causes excessive production of proteins within the plant body, causing buds, stems, roots, etc. to expand and grow in a non-directional manner, causing cells and It is explained that it causes tissue abnormalities. However, because they elicit their effects at lower concentrations than other types of drugs, differences in their chemical structures may have a subtle effect on the process leading to the onset of their effects, which can lead to large differences in their effectiveness.

Originally, if these compounds were absorbed through the radicle of weeds,
It exerts considerable action and is effective against a wide range of weeds, from grasses to broad-leaved weeds. However, the absorption rate is slow for weeds with advanced leaf stages, and the concentration does not reach a lethal concentration, resulting in temporary effects. Even if damage is caused to the pest, it may recover later, and complete control may not be achieved.

2. 1,3-Benzothiacyanone compounds are said to be photosynthetic inhibitors like triazine compounds in terms of their herbicidal activity, and their herbicidal activity is generally low at the beginning of weed emergence, especially against barnyard grass. ``It is recognized that the effectiveness is low at any time.

In recent years, the control of weeds in rice fields has shifted from physical and mechanical methods that required a great deal of labor to chemical and labor-saving methods that involve simply spraying chemicals. Development research is actively being conducted.

However, due to changes in rice cultivation methods, changes in cultivation methods, rice planting by machines, insufficient cultivation management, and the annual use of herbicides that are less effective against perennial weeds, firefly, grasshopper, and grasshoppers have become scattered locally. Cyperus japonica, Omodaka japonica, etc. are multiplying and flourishing, and are becoming a major hindrance to rice cultivation. Therefore,
There is a need for the development of a herbicide that can simultaneously appropriately and efficiently control annual weeds such as Japanese barnyard grass, as well as perennial weeds such as grasshopper, grasshopper, grasshopper, and watermelon.

From this point of view, various attempts have been made to combine the above compounds as appropriate; for example, ■Special Publication No. 11066/1983@
It can be found in the known composition "Glasnon M@" (registered trademark of Kakan Kagaku Kogyo Co., Ltd. and Ishihara Sangyo Co., Ltd.).

However, the example of ■ is S-ethyl, ruhekizahydro-I H
-Azepine-1-thiol-Nonomate (hereinafter abbreviated as molinate) and 2-methylthio-4,6-bis(ethylamino)-8-triazine (hereinafter abbreviated as simetrine). Yes, it is highly effective against Japanese barnyard grass, Japanese grasshopper, and Japanese grasshopper.
It has been recognized that it is less effective against so-called perennial grasses such as Cyperus japonica. In addition, since it contains 1 to 2% cymetrine, there is concern that it may cause chemical damage to rice under high temperature conditions in warm regions and the Ike-Sunagawa soil region. In fact, in all areas where this composition has been applied, lower leaf blight, growth suppression, tillering suppression, and I placement accompanied by plant loss have occurred in rice plants. Furthermore, since it contains molinate, there are concerns that it may be toxic to carp, and many regulations have been put in place to prevent it from being sprayed around carp farms, and water is shut off after spraying to prevent it from moving beyond the sprayed field. restrictions are in place.

Example C is a mixed composition of a phenoxy compound and a benzothiacyanone compound, which is highly effective against p11 weeds and perennial weeds, but has the disadvantage of being less effective against barnyard grass, which is the main species. In addition, phenoxy compounds 1.
Since it contains 5%, there are concerns about chemical damage at low temperatures, which naturally limits the brightness of its application, and has the disadvantage that the suitable period for chemical treatment is narrow.

Under these circumstances, the present inventors have made extensive research to develop a herbicide that meets the above-mentioned objectives.
We have developed a herbicide composition for paddy rice that is highly effective not only on barnyard grass and Japanese grasshopper, but also on Japanese grasshoppers, Japanese snails, fireflies, and cypresses. At the same time, it has extremely little toxicity to rice, and in addition, there is almost no concern about subacute toxicity to fish. led to completion.

That is, the group 1λ compound of the present invention compensates for the weak points of benzothiacyanone compounds and phenoxy compounds against barnyard grass with all-thiol carbamate compounds and triazine compounds within the range of medicinal reds that do not cause drug damage, and provides thiols against broad-leaved weeds and perennial weeds. By compensating for the drawbacks of carbamate compounds with benzothiacyanone compounds and phenoxy compounds, it is possible to efficiently control a wide range of rice field weeds.

In this way, it is possible to accurately exterminate weeds at different growth stages with a smaller amount than the medicinal herbs proposed in the past, and it is also advantageous from an economical point of view. Since the compound has no or very low toxicity to fish, the composition of the present invention has the advantage that there is no problem in terms of toxicity to fish.

The composition of the present invention can be produced by mixing all three of a thiol carbamate compound, a triazine compound, and a phenoxy compound, or by mixing four of them by adding a benzothyanoanone compound, and the mixing ratio thereof is 6 to 10 parts of a thiol carbamate compound in the "Oki part,"
Triazone compound 0.5-12 parts, phenoxy compound 0
It is desirable to have 2 to 8 parts of the benzothiacyanone compound and 4 to 1 part of the Fi, but this is the range of the mixing ratio in which the synergistic fruit can be obtained, which is defined based on experimental results. . Furthermore, considering safety for rice, 6 to 9 parts of a thiol carbamate compound, 0.8 to 1.0 parts of a triazine compound, and 0.2 to 0.0 parts of a phenoxy compound.
If the amount is 6 parts and 5 to 7 parts of the benzothiasoanone compound, there is very little concern about drug damage, and a remarkable synergistic and cooperative effect can be obtained. The therapeutic application amount of the drug varies depending on the area to be controlled, the field, and the state of weed growth, but it is appropriate to use 275 to 760 l Mu per 10 are as a mixed active ingredient. In order to increase the safety for rice, applying 330 to 500 g can produce good carpals.

As mentioned above, the herbicide composition for paddy rice of the present invention comprises a three-component composition consisting of compounds (1), (11), and (2), and compounds (1), (n), (Ill and (Incorporated)). Both three-component compositions have remarkable herbicidal effects on their own, but in history, as a systematic treatment, the initial agent was used before and after rice planting.
If the three-component straw composition of the present invention is applied between 15 and 25 days after rice transplantation, the full effect may be even more pronounced.

On the other hand, the latter four-component composition does not need to be used together with the initial agent at all, and can be used by itself from about 15 days to 3 days after rice transplantation.
By applying it within 0 days, it is possible to almost completely kill all weeds, that is, it is extremely effective as a pest control agent.

The herbicide composition for paddy rice according to the present invention is most effective when used in the form of granules by mixing the active ingredient described in II with an inert carrier, but it can also be used as an emulsion, hydrating agent, etc. as necessary. It is possible to freely choose its form.

Further, if necessary, it can be used in combination with other agricultural chemicals such as known herbicides, fungicides, and insecticides, fertilizers, and the like.

As an inert solid carrier, bentonite, clay, Merck, white carbon, gravel earth, activated clay, permiculite, etc. are used, and as a binder, sodium lignin sulfonate, ? Rivinyl alcohol, ethylene glycol, ethyl cellulose, vinyl acetate, etc., and anionic or nonionic (nonionic) thread as a surfactant.
[e] Can be made into granules by combining.

Formulation examples and examples of the herbicide composition for paddy rice according to the present invention will be described below, but it goes without saying that the scope of the present invention is not limited thereto. Note that the numbers used in the formulation examples and examples represent parts by weight unless otherwise specified.

Formulation example 1 (granules) S-(4'-chlorobutyl)-N as compound (1)
.

8 parts of N-diethylthiol carbamate, compound (11
) as cymetrine 1. Q 1riS, compound (II
T) as ethyl-4-, [(4-chloro-〇-tolyl)-oxy]butyrate (hereinafter abbreviated as MCPB)
0.6 parts plus 1 part sodium alkylbenzenesulfonate.
5 parts of clay, 26.9 parts of clay, and 60 parts of bentonite were mixed uniformly, and 2 parts of sodium lignin sulfone monoate was added to 2 parts of water.
Add the solution dissolved in 5 parts and knead with a kneader to make a diameter of 0.8
After extrusion through a screen and granulating it for 7 times, it is dried and sized using a sifter to form granules of 14 to 32 meshes.

Formulation Example 2 (Granules) Finely ground Compound 1m(II) is 2-methylthio-4-ethylamino-6-(1,2-tsumethylzolopylamino)-8-)ribusin (hereinafter abbreviated as dinotametrino) ) 0.9 parts, 2-methyl-4- as compound ωD
Chlorophenoki/thioethyl acetate (hereinafter abbreviated as phenothiol) 0.5 part, white carbon 5'ijB
Mix the premix uniformly with 24.5 parts of clay and 62 parts of tonite, add an appropriate amount of water, and kneader. - Knead in 111L of water and granulate with an extruder.Next, dry and granulate to obtain granules of 14 to 32 mesh sizes.Add 5-(4-talobutyl) to the granules as compound '1' (1). Add 7 parts of -N,N-diethylthiol carbamate to the granules and mix uniformly for impregnation to form granules.

Combination drug 3 (water agent) Compound (1) is 5-(5-chloropentyl)-N,
32 parts of N-noethylthiol methane, compound Q-
a (n) as 2-methylthio-4-ethylamino-
2.4 parts of 6-itupropylamino-s-trianone (hereinafter abbreviated as ametrine) and 2-methylthio-4,
6-bis(isopropylamino)-S-1-rianone (hereinafter abbreviated as promethrin) 2.4ti! , compound (32 parts of phenothiol as 11O, 133 parts of kaolin, 20 parts of diatomaceous earth, 276.7 parts of white car,
Tsurunol ■5080 (registered trademark name: Toho Chemical Industry Products)
133 parts of polyvinyl alcohol and 6.7 parts of polyvinyl alcohol were thoroughly mixed uniformly in a mixer, and ground three times in a hammer mill to obtain a Kimoto 1] agent.

When using the hydrating powder described above, it can be diluted and dispersed with any amount of water, used on a cloth, or applied by spreading. This is why the active ingredient content meter for this formulation example deviates from the range described in the main text of Specification 1.
The amount of active ingredient applied per 10 ares does not fall outside the scope of the present invention.

5-(4-chlorobutyl)-N as compound (1).

9 parts of N-noethylthiol carpamate, compound (n)
As shift 9f 12th part, conversion B! proboscis (r as ltD
, 4CP80.6 rL as compound (goods) 3-isopropyl-2,1,3-benzothianoanon-4-one-
6 parts of 2,2-nooxide (abbreviated as pentacine), 30.2 parts of further Punto 0 (B registered trademark, Toho Chemical Industries), Kuker ■■-1 (registered trademark, Toho Chemical Industries) Product) 35 parts, mixed with 15 parts clay,
Next, as a surfactant, Tsurupol"5073 (registered R
(trade name, manufactured by Toho Chemical Industries, Ltd.) and 2 parts of Tsurupol 9047K (trademark) as a solidifying agent.
Registered trademark name, Toho Chemical Industries product) 2 parts each 28
Add the polishing solution to the water and mix with a niegu to obtain an Iα diameter of 0.
After extrusion and granulation through a screen of .,8 mm, it is dried and sized using a sifter to form granules of 14 to 32 mesh size.

5-(8-chlorooctyl)-N as compound (1),
21 parts of N-diethylthiol carbamate, compound (I
After adding 3.0 parts of Aft 9F as compound I), 1.8 parts of phenothiol as compound aJD, 24 parts of pentacine as compound (incorporated), and 40 parts of xylene and dissolving them well, , Toho Chemical Industry Products) was added and mixed uniformly to form an emulsion.

Next, the excellent features of the herbicide composition for paddy rice according to the present invention will be explained in Examples.

Example 1 Herbicidal power test (pot test) Gravel was spread on the lower layer of a Wagner pot equivalent to 1/2000 are, and dry paddy soil was filled on top of the gravel. After filling the soil with paddy soil mixed with P. japonica and Firefly, overwintering tubers of Cyperus japonica and Oorikawa were planted shallowly, flooded with water to about 3 Crn, and left standing in a greenhouse. When the number of wildflowers reaches 2.5 to 3.0 leaves, mix example 1~
Predetermined amounts of the preparations prepared according to 5 were uniformly dispersed.

After the chemical treatment, water leakage treatment was carried out at a rate of 1 to 2 cm/day for 2 days, and thereafter, the water condition was maintained in 3CrIL. To investigate the herbicidal power, the remaining weeds were pulled out three weeks after the chemical treatment, washed with water to remove the attached soil, and their weight was immediately measured and compared with the weight of the remaining weeds in the untreated area. The test will be conducted in two series,
The numbers are averaged and according to the following criteria O ~ 5.0
It was evaluated on an 11-point scale.

Sides, bottom margin 5.0: Compared to the untreated area, the grass growth rate is 5 inches or less.

45... 〃 6～15 〃4.
0- 1/ 16-25 〃35・
・・26〜35 〃
3.0...36~4
5 〃2.5 ・ 〃
46～55 〃2.0...〃 5
6～65 〃15... 〃66～
75 〃1.0... 〃 76～8
5 〃05... 〃 Section 86 and above
〃0...No effect observed at all.

however The results are shown in Pouch 1.

As shown in Table 1 below, the herbicide composition for paddy rice of the present invention generally exhibits a remarkable herbicidal effect on wild grasses compared to known compositions, and has recently become a problem as a perennial weed. It is also extremely effective against the common firefly, urikawa, and water cyperus.

Furthermore, the compound (1) which is an important component of the composition of the present invention
) has a greater herbicidal effect on wild grasses than the corresponding known compound Morii, -.
Table 1 demonstrates the necessity that the composition of the present invention consists of three to four components, whereas the known compositions have two or three components.

Example 2 In order to confirm the results obtained in the herbicidal power and phytotoxicity test (field example) in an actual paddy field, the following test was conducted.

Paddy fields in the Tohoku region (Aomori Prefecture), where the proliferation and overgrowth of perennial weeds, especially fireflies and water palms, are a problem are covered with PVC corrugated ridge sheets of 2rr per ward. (1m x
On May 19th, Akinishiki (average leaf age 2.5 to 35 leaf age) was transplanted to a 2 m) section, and a test was conducted under flooded conditions using one drug twice.

On June 9th, granules prepared in the same manner as in Example 1 were sprayed at the prescribed i: (300, 400)/a), and on the 28th day after spraying, weeds were pulled out and immediately washed with water. After removing the attached soil, the weight of the animals was measured.

In addition, in order to examine chemical damage to rice, five rice plants in one plot were harvested from the ground surface 3 (-In) on the 35th day after chemical treatment, and their living weight was measured and compared with that in the hand-removed plot. The results are shown in Table 2.

As shown in Table 2, the mixed composition of the present invention retains a high herbicidal effect against various weeds, and at the same time has very little chemical damage to rice, as shown in the reference example. The comparison is self-evident, and it can be fully understood that the composition of the present invention is advantageous both in terms of the labor involved in weeding work and in terms of economy.

Table 2: Herbicidal power and chemical damage test results Book *The compositional ratio of the test chemicals is the same as in Table 1. Test examples will be specifically shown to explain the excellent features of the herbicide composition for paddy rice according to the present invention.

Example 3 (Subacute Toxicity Test for Carp) 410 Japanese mackerel were placed in a 251 water tank equipped with an air blowing device and fed for 7 days to acclimate them. Although the water in the aquarium was replaced continuously, the average residence time in the aquarium was 0.25 days. After that, add the granules ①, ②, and ② used in Example 1゜2 to the supplied water to sufficiently dissolve the test compound, remove the carrier in the granules, and
[While maintaining the concentration of thiol carbamate at 0.2 PPM, rearing and edging were continued for 3 weeks. After 3 weeks, the hematocrit values of all surviving fish were measured.

The results are shown in Table 3.

As is clear from the results in Table 3, the carp maintained normal blood properties as in the case without the addition of the compound.

'; Mizuguchi Table 3 Subacute toxicity test results for carp that's all

Claims (1)

[Claims] 1. At least one compound represented by the following general formula (1) (wherein n represents an integer from 4 to 1O) and the following general formula (U) (wherein R is ethyl or represents an inglovir group, k
represents ethyl, inglovir or 1,2-dimethylpropyl group), and at least one compound represented by the following general formula (e) (wherein n' represents an integer of 1 to 3, and X represents oxygen or sulfur). 1. A herbicide composition for paddy rice, which contains as an active ingredient at least one compound represented by the following formula: 2. Compound (1) is 5-(4-chlorobutyl)-N,N
- diethylthiol carbamate, compound (n)
is 2-methylthio-4,6-bis(ethylamino)-8
-) riazine, and the compound ωD is 2-methyl-
The herbicidal composition for paddy rice according to claim 1, which is ethyl 4-chlorophenoxybutyrate. 3. Compound (1) is 5-(4-chlorobutyl)-N,
N-diethylthiol carbamate, compound (n
) is 2-methylthio-4-ethylamino-6-(1,2
-dimethylzolobylamino)-8-) with riazine,
and the herbicidal composition for paddy rice according to claim 1, wherein the compound is thioethyl 2-methyl-4-chlorophenoxyacetate. 4. Compound (I) 6 to 10 parts by weight, Compound (lI) 0
．． 5-1.2 parts by weight and compound Ql[) 0.2-0.
Water 41b according to claim 1 consisting of 8 parts by weight
Herbicide composition for use. 5. At least one compound that has a hydrogen bomb according to the following general formula (1) (wherein n represents an integer of 4 to 10), and the following general formula (n) (wherein R represents an ethyl or isopropyl group). C, R
'represents ethyl, isozorobyl or 1,2-methylzorobyl group), and at least one compound represented by the following general formula (2) (wherein n/ is an integer of 1 to 3, and A herbicidal composition for paddy rice, comprising at least one compound represented by the following formula (IV) as active ingredients. 6. Compound (1) is 5-(4-chlorobutyl)-N,N
-noethylthiol carbamate, compound (II
) is 2-methylthio-4-ethylamino-6-(1゜2
-dimethylglobylamino)-8-) riazine,
and the herbicidal composition for paddy rice described in item 5 of the patent, ii. 7. Compound (I) 6-10 parts by weight, Compound (II) 0
．． 5-1.2 parts by weight of the compound ωD, 0.2-0.8 parts by weight of the compound (■), and 4-10 parts by weight of the compound (■).