JPH03218304A - Enhancing agent of weeding effect and weeding granule applying to water surface containing thereof - Google Patents

Abstract

PURPOSE:To obtain weeding granules for applying to water surface having exceedingly enhanced weeding effect on barnyard grasses comprising thiol carbamate or dithiocarbamate containing phenolic, sulfuric or phosphoric antioxidant. CONSTITUTION:0.5-5wt.% a species of phenolic antioxidant, sulfuric antioxidant and phosphoric antioxidant is contained in granules containing a compound expressed by formula I (X1 is <=4C alkyl, chlorine-substituted allyl, benzyl or chlorine-substituted benzyl; Y1 and Z1 are same or different <=5C alkyl or cyclohexyl), a compound expressed by formula II (X2 is <=5C alkyl, chlorine- substituted alkyl or chlorine-substituted benzyl; Y2 is hexamethyleneimine) or a compound expressed by formula III (X3 is benzyl, chlorine-substituted allyl or Na; Y3 and Z2 are <=3C alkyl or H) as a weeding active component to afford the objective agent.

Description

DETAILED DESCRIPTION OF THE INVENTION Object of the Invention (1) Field of Industrial Application The present invention relates to a herbicidal effect enhancer and a herbicidal granule for water surface application containing the herbicidal effect enhancer.

(2) Prior Art Thiolcarhamate and dithiocarhamate compounds are widely used as non-hormonal herbicides that are highly effective against barnyard grass in rice fields.

The following are examples of techniques for using antioxidants in agricultural chemicals. That is, it is incorporated into juvenile hormone compositions to prevent deterioration due to air and sunlight (Japanese Patent Laid-Open No. 48-3632
No. 5), an insecticidal composition for electric mosquito repellent containing allethronil as an active ingredient and a specific antioxidant added as a stabilizer (Japanese Unexamined Patent Publication No. 1983-98324), and an anti-oxidant added to the antibacterial agent. Blend to make it stable against heat (Japanese Unexamined Patent Publication No. 165304/1983). When DDVP is mixed with nitrocellulose and solidified, the stability over time is increased by adding an antioxidant, etc. (Japanese Patent Application Laid-Open No. 108024/1983), and birethroid insecticides are mixed with hydrocarbons and oxidized. A method of increasing the volatilization rate of the insecticidal component and enhancing the insecticidal efficacy by adding an inhibitor (Japanese Patent Application Laid-Open No. 54-28818) has been tested. However, by incorporating antioxidants into herbicide granules for water surface application,
It is not previously known that the herbicidal effect can be increased.

(3) Problem to be solved by the invention Thiol carhamates and cythiocarhamates, as described below, are effective against barnyard grass when formulated into granules and applied to paddy fields in accordance with the formulation of ordinary agricultural chemicals. It exhibits fast-acting properties, but its residual effectiveness is poor. Therefore, if a residual effect is to be imparted, it is necessary to apply a high dose. The present invention aims to improve these conventional drawbacks, impart residual efficacy, and exhibit high herbicidal effects.

Structure of the Invention (1) Means for Solving Section The inventors of the present invention have conducted extensive research in order to solve the above-mentioned problems. As a result, by blending one type of phenol-based, sulfur-based, or phosphorus-based antioxidant into granules containing a thiol carbamate-based or dithiocarbamate-based compound represented by the following general formula as a herbicidal active ingredient, the above-mentioned The present invention was completed by discovering that the herbicidal active ingredient significantly enhances the herbicidal effect on barnyard grass.

General formula (1) 0 (However, X+ in the formula is an alkyl group having 4 or less carbon atoms,
A thiol represented by a chlorine-substituted allyl group, a pencil group, a chlorine-substituted benzyl group, and Y1 and Z, which may be the same or different, represent an alkyl group having 5 or less carbon atoms or a cyclohexyl group. Carbamate, general formula (2) 0 11 X2 S C Y2 (2
) (X゜2 in the formula represents an alkyl group having 5 or less carbon atoms, a chlorine-substituted alkyl group, a chlorine-substituted benzyl group,
Y2 represents hexamethyleneimine) or a thiol carhamate represented by the general formula (3) (where x3 in the formula represents a benzyl group, a chlorine-substituted allyl group, or sodium; Y3 and Z2 may be the same or different and represent an alkyl group having 3 or less carbon atoms or a hydrogen atom) Therefore, the present invention first provides phenolic oxidation The above general formulas (1) to (3), which are characterized by containing one type of inhibitor, sulfur-based antioxidant or phosphorus-based antioxidant
The present invention relates to a herbicidal effect enhancer for water-applied herbicidal granules containing a thiolcarhamate-based or dithiocarhamate-based herbicidal active ingredient as shown in the following. Second, agricultural chemicals containing thiol carbamate or dithiocarhamate herbicidal active ingredients as shown in the above general formulas (1) to (3) are added to phenolic antioxidants, sulfur antioxidants, or phosphorus. The present invention relates to a herbicidal granule for water surface application, characterized in that it contains one type of antioxidant.

Examples of the thiol carhamate and dithiocarbamate herbicidal active ingredients of the present invention represented by the above-mentioned general formula include the following compounds.

Examples of compounds of general formula (1) Compound cation(1)-13-ethyl-N,N-diisobutylthiolcarhamate (1)-23-probyl-N-ethyl-N-butylthiolcarhamate (1)- 3 3-Ethyl-N,N-cy n-probylthiol carbamate (1)-(1)-(1)-(1)-(1)-(l)-(1)-11 (1)-12 ( 1)-13 S-n-probyl-N,N-di-n-propylthiol carhamate S-tert-tutyl-N,N-di-n-propylthiol carhamate S-ethyl-N,N-diethylthiol carhamate S-ethyl-N-ethyl-N-cyclohexylthiolcarbamate S-2.3-dichloroaryl-N,N-cyisoprobylthiolcarbamate S-2.3.3-tricloaryl-N,N-diisoprobylthiolcarbamate Thiol carbamate S-benzyl-N-ethyl-N-(1,2-dimethylbutyl)thiol carbamate S-pencyl-N,N-disec-butylthiolcarbamate S-benzyl-N,N-dimethylthiolcarbamate S-(2 -Chlorobenzyl)-N,N-diq ethylthiol carbamate (1)-14 3-(4-chlorobenzyl)-N,
N-ethylthiol carhamate Example of compound of general formula (2) (2) -1s-ethyl-N,N-hexamethylenethiol carhamate (2) -23-isopro and ruhexahyto-IH- Azevin-l-carbolate (2)-33-1-ethyloup-N,N-hexamethylenethiol carbamate (2)-4 3-(p-chlorobenzyl)-N. N-
Hexamethylenethiol carhamate Example of compound of general formula (3) (3)-1 Benzyl-N,N-dimethyldithiocarbamate (3)-2 Benzyl-N,N-diethyldithiocarbamate (3)-3 Pencilyl N,N-diisopropyl dithiocarbamate (3)-4 S-2-chloroaryl N,N-diethyl 10 dithiocarbamate (3)-5 Sodium N-methylcythiocarhamate Phenol oxidation used in the present invention The inhibitor, sulfur negative type or phosphorus type antioxidant is not particularly limited, and for example, the following can be used.

1) Examples of monophenolic antioxidants Compound 1 2,6-di-tert-phthyl-4-methylphenol 2 3-tert-phthyl-4-hydroxyanisole 3 2,6-di-tert-phthyl-4-ethylphenol 4 Example 5 of stearyl-β-(3,5-tert-butyl-4-humanoxyphenyl)propionate 2) bisphenol antioxidant 2.2'-methylene-bis(4-methyl-6)
- tert-butylphenol)6 2.2'-
Methylenebis(4-ethyl116-tert-phthylphenol)7 4.4
'-Thiobis(3-methyl-6tert-butylphenol) 8 4.4'-Thylidenebis(3-methyl-
6-tert-butylphenol) 3) Example 9 of polymeric phenolic antioxidant 1,1,3-tris(
2-Methyl-4-hydroxy5-tert-tutylphenyl)butane 10 1,3,5-trimethyl-2,4-,6-tris(3,5-tert-tutil-4-hydroxybenzyl)benzene 11 Tetrakis [Methylene-3-(3'5'-di-tert-4'-human xyphenyl)propionate] methane 4) Examples of sulfur-based antioxidants 12 Dilaurylthiodipionate 13 Similystylthiodipionate 14 Distearyl Thiosib pionate 15 Citridecyl thiopionate l2 16 2-Mercabutobenzimidazole 5) Examples of phosphorous antioxidants 17 Triphenyl phosphite 18 Diphenylisodecyl phosphite 19 Phenyl diisodecyl phosphite 204.4'-thucylidene bis (3-Methyl-6-tert-butylphenyl-tridecyl) phosphite 2l Octadecyl phosphite 22 Tris(nonylphenyl) phosphite 23 Diisodecyl J leventaerythritol Phosphaphenanthrene-lO-oxide 25 10-(3
．． 5-tert-butyl-4-hydroxybenzyl)-9.10-cyhytro9-oxaphosphaphenathrene-10 oxite26 lO-decyloxy9,lO-dihytro-9oxa10-phosphaphenathrene l3 Examples (Method of carrying out the present invention) These antioxidants can be used alone or in combination of two or more as herbicidal effect enhancers.

The herbicidal effect enhancer of the present invention will be effective if incorporated in the herbicidal granule in an amount of 0.5% or more. However, in consideration of effectiveness and economy, it is desirable to mix the herbicide in an amount of 0.5 to 5% of the total amount of herbicide granules. In addition, there is no need for a special addition method; for example,
(1) Mixing the active ingredient and the herbicidal effect enhancer,
A method of adding and mixing other adjuvants and fillers (2)
) A method in which the herbicidal effect enhancer is simultaneously added and mixed with the active ingredient, adjuvant, and filler; or (3) the herbicidal effect enhancer and the active ingredient are mixed together and then sprayed onto a granular carrier for adsorption. Any method is fine.

The extender used to obtain the herbicidal granules of the present invention is not particularly limited, and any extender that is generally used in agricultural chemical formulations can be used. Examples of this include:

Namely, clay, tal, bentonite, diatomaceous earth, acid clay, activated clay, calcium carbonate, gypsum, hydrated silicic acid, calcium silicate, seekrite, zeolite, pearlite, attabulsheite, and the like.

Further, even if adjuvants commonly used in agricultural chemical formulations are added to obtain the herbicidal granules of the present invention, the herbicidal effect enhancement effect brought about by the present invention will not be impaired. Examples of this include: Namely, surfactants such as alkylaryl sulfonates, alkyl sulfates, polyoxyalkylene alkyl allyl ethers, polyvinyl alcohol (PVA), polyethylene oxide, lignin sulfonates, starch, cellulose, casboxymethyl cellulose (CMC), etc. binders, disintegrating agents, stabilizers for active ingredients, ultraviolet absorbers, etc.

The herbicidal active ingredient of the present invention may be used alone or in combination with other herbicides, such as (RS)-2-bromo N-(α,α-cymethylpencyl)-3,3-dimethyltutyramito, 2-
(2,4-dichloro3-15 methylphenoxy)propionanilito, 4-(2,4
-dichlorobenzoyl)-1,3-dimethyl-5-birazolyl-p-toluenesulfonate, methyl 2-{(
(4.6-dimethoxypyrimicin-2-yl)aminocarbonyl)aminosulfanylmethyl}penzoate,
2-(4(2.4-dichloride-m-trioyl)-1.
3-dimethylpyrazol-5-yloxy)-4'-methylacetophenone, 2-methylthio-4,6-bis(
ethylamino)-S-}lyasin, 2-methyl-4-chlorophenoxythioacetic acid S-ethyl ester, 5-(2.
Methyl 4-cyclophenoxy)-2-nitrobenzoate, ethyl 2-methyl-4-chlorophenoxy acetate, 5-
((4.6-dimethoxypyrimicin-2-yl)monaminocarbonylaminosulfonyl)-1-methylpyrazole-4-carboxylic acid ethyl ester, α-(2-naphthoxy)propionanilide, etc. I'll come. Furthermore, it is perfectly acceptable to formulate a formulation by mixing it with a bactericide, an insecticide, a plant growth regulator, etc., and use it as long as it does not adversely affect the herbicidal enhancement effect of the present invention. In some cases, a synergistic herbicidal effect can be expected by using these drugs in combination.

The method for producing the herbicidal granules of the present invention does not require any special method or equipment, and may be a conventional method for producing pesticide granules.

Examples are given below to specifically explain the present invention, but the present invention is not limited to these examples.

In addition, all parts in the examples indicate parts by weight.

10 parts of S-pencil-N-ethyl-N- (1,2-dimethylbutupyr)thiol carhamate and 2 parts of the compound Nbl of the present invention are mixed, and to this are added 10 parts of white carbon, and sodium todecylbenzenesulfonate. 1 part, 30 parts of bentonite and 47 parts of clay and mixed in a hammer mill. Add 15 parts of water to this, knead, and granulate using an extrusion granulator. Next, it is dried and further divided into sections (1
4 to 32 mesh) to obtain granules.

Example 2 (herbicidal component of general formula (1), bisphenonigenko S1 (2-chlorobenzyl)-N,N-ethylthiol keramate 10 parts, white carbon 10 parts,
Add 2 parts of compound No. 5 of the present invention to 2 parts of polyvinyl alcohol and 76 parts of clay, and mix with a hammer mill. 15 parts of water is added to this, kneaded, and granulated using an extrusion granulator. Next, it is dried and further sieved (14
~32 mesh) to obtain granules.

Example 3 (Compound of general formula (2), 10 parts of polymeric FeL-di-dotama-S-ethyl-N,N-hexamethylenethiol carbamate and 2 parts of compound No. 9 of the present invention were mixed; Add 10 parts of white carbon, 1 part of sodium lauryl sulfate, 50 parts of bentonite and 27 parts of talc and mix in a hammer mill. Add 17 parts of water and granulate in a transfer granulator. Then , dried, and further sieved (14
~32 mesh) to obtain granules.

▲ Negative A (compound of general formula (3), sulfur-based) Pencil-N,N-diethyl sithiocarbamate 10 parts, white carbon 10 parts, polyethylene oxide 1 part and clay 77 parts, compound No. 2 of the present invention 2 and mix using a V-type mixer. This and water
While adding 16 parts, it is granulated using a transfer granulator. Then, it is dried and further sieved (14 to 32 mesh) to obtain granules.

Example 5 88 parts (compound of general formula (2), phosphorus type) of granular attabulsheite (14 to 32 mesh) are placed in a V-type mixer. To this, 10 parts of S-isopropyl-hexahydro-IH-azepine-1-carbothioate and 2 parts of the compound No. 7 of the present invention, which had been warm-mixed, were sprayed and adsorbed to form granules. obtain.

Example 6 (Compound of general formula (1), phosphorus type) 10 parts of S-benzyl-N,N-g-tutylthiol carhamate and 2 parts of the compound of the compound of the present invention (compound 18) were mixed, and white 10 parts of carbon, 1 part of sodium lauryl sulfate, 30 parts of bentonite, and talc
Add 47 parts and mix using a hammer mill. Water 15 for this
1 part, knead, and granulate using an extrusion granulator. Then, it is dried and further sieved (14 to 32 mesh) to obtain granules.

Example 7 (Compound of general formula (3), polymeric phenol type) 10 parts of pencil N,N-cyisopropyl dithiocarhamate, 1 part of white carbon lf, 2 parts of polyethylene oxide and 76 parts of clay were added with the compound of the present invention. Compound chlorine. Add 2 parts of compound 9 and mix using a hammer mill. Add 15 parts of water to this, knead, and granulate using an extrusion granulator. Then, it is dried and further sieved (14 to 32 mesh) to obtain 20 granules.

Effects of the Invention When rice fields are treated with granules containing a thiolcarpamate or cythiocarhamate herbicidal active ingredient to which the herbicidal effect enhancer of the present invention has been added, the active ingredient maintains a high concentration in water. . As a result, the active ingredients can be used effectively, increasing the long-lasting effect and reducing the amount of drug used.

In addition, even when the herbicidal effect enhancer itself or when used in combination with the herbicides represented by the above general formulas (1) to (3), it does not cause any chemical damage to useful crops such as rice, nor does it cause harm to humans, livestock, etc. It has low toxicity to fish and shellfish, and there are no inconveniences when using it.

Next, test examples will be given to prove the above-mentioned usefulness of the present invention.

Test] 1 Example 1 Herbicidal effect under flooded conditions Fill alluvial soil in a cotton pot with a size of 1/5000 are, add water and mix, and raise the water depth to about 3 cm.
It was flooded to a depth of m. There, 100 seeds of 21.
It mixed well with about 5 cm of soil. Then, three rice seedlings (variety "Nipponbare") at the 2.5 leaf stage were transplanted as one plant to the center of the pot. The pots were kept in a greenhouse at 20-30'C. Then, two days after sowing (before the appearance of Japanese millet) and seven days after sowing (at the first leaf stage of Japanese millet), granules prepared according to Examples 1 to 7 were added in an amount of 100 g/10
The amount was processed to be equivalent to R. The fresh weight of the remaining Japanese millet was measured 21 days after the chemical treatment, and the herbicidal rate (%) was determined using the following formula.

At the same time, the transplanted paddy rice was also investigated for external chemical damage. The test was conducted using three bots per drug area, and the average weed killing rate was determined.

Comparative Examples 1 to 7 were prepared by replacing the additives in Examples 1 to 7 with extenders. The results are shown in Table 1.

2 2 Test Example 2 Sustainability test of herbicidal effect A Wagner pot with a size of 1/5000 are was filled with alluvial soil, and water was added to make it flooded to a depth of 3 cm.
I kept it. Granules prepared according to Examples 1 to 7 were pressed onto the water surface in an amount equivalent to 200 g/lO are as the active ingredient. 5th day, 10th day, 15th day, 20th day after drug treatment
On the 1st, 25th, 30th, and 35th days, 100 seeds of Japanese grass were sown. Then, the pot is 20~
It was maintained in a greenhouse at 30°C. 21 days after sowing, the fresh weight of the remaining Japanese millet was measured, and the herbicidal rate (%) was determined using the formula shown in Test Example 1.

This test was conducted using three bots per drug plot, and the average herbicide rate was determined. The results are shown in Table 2.

Claims (1)

[Claims] 1) General formula (1) characterized by containing one type of phenolic antioxidant, sulfur-based antioxidant, or phosphorus-based antioxidant ▲ Numerical formula, chemical formula, table, etc. ▼(1) (However, X_1 in the formula represents an alkyl group having 4 or less carbon atoms, a chlorine-substituted allyl group, a benzyl group, a chlorine-substituted benzyl group, and Y_1 and Z_1 are the same or different. General formula (2) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (2) (However, X_2 in the formula is Indicates an alkyl group having 5 or less carbon atoms, a chlorine-substituted alkyl group, a chlorine-substituted benzyl group, and Y
_2 represents hexamethyleneimine) or general formula (3) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (3) (However, X_3 in the formula is a benzyl group, chlorine-substituted allyl water surface application containing a dithiocarbamate as a herbicidal active ingredient; A herbicidal effect enhancer for herbicide granules. 2) General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) (However, X_1 in the formula is an alkyl group with 4 or less carbon atoms, a chlorine-substituted allyl group, a benzyl group, a chlorine-substituted benzyl group) and Y_1 and Z_1 may be the same or different and represent an alkyl group having 5 or less carbon atoms or a cyclohexyl group), General formula (2) ▲ Numerical formula, chemical formula, table, etc. ▼(2) (However, X_2 in the formula represents an alkyl group with 5 or less carbon atoms, a chlorine-substituted alkyl group, a chlorine-substituted benzyl group, and Y
_2 represents hexamethyleneimine) or general formula (3) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (3) (However, X_3 in the formula is a benzyl group, chlorine-substituted allyl (Y_3 and Z_2 may be the same or different and represent an alkyl group having 3 or less carbon atoms or a hydrogen atom) as a herbicidal active ingredient. , a phenolic antioxidant, a sulfur-based antioxidant, or a phosphorus-based antioxidant.