JPS6328042B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a new herbicide composition that exhibits remarkable above-ground killing power and regrowth-suppressing power when applied to annual weeds, perennial weeds, and shrubs. First, the inventors discovered (2-amino-4-[(hydroxy)(methyl)phosphinoyl]butyryl)-alanylalanine (hereinafter referred to as SF-1293) and its salts (hereinafter collectively referred to as SF-1293s). ), L
-2-amino-4-[(hydroxy)(methyl)phosphinoyl]butyric acid (hereinafter referred to as L-AMPB)
and its salts (hereinafter collectively referred to as L-AMPBs), and DL-2-amino-4-[(hydroxy)(methyl)phosphinoyl]butyric acid (hereinafter referred to as DL
-AMPB) and its salts (hereinafter referred to as DL-
Collectively called AMPBs. As a result of research into the biological activities and uses of these compounds, it was discovered that all of these compounds have extremely excellent herbicidal effects. In other words, SF-1293 is effective against annual weeds, perennial weeds, and shrubs, and has a strong inhibitory effect on their regeneration as well as killing the above-ground parts through foliage treatment. He discovered this and completed the invention of SF-1293 as a herbicide (see JP-A-54-67026). Furthermore, S.F.
- As a result of repeated research to take advantage of the characteristics of Class 1293, we found that its medicinal efficacy was significantly enhanced when mixed with a transitional herbicide, a substance with plant hormone activity, a nitrogen-containing compound, or a trace amount of paraquat. I got it. (Refer to the specifications of Japanese Patent Application Laid-open No. 119034/1980, Japanese Patent Application No. 172122/1980, Japanese Patent Application No. 33867/1982, and Japanese Patent Application No. 35398/1983). In addition, L-AMPBs and DL-AMPBs are both effective against perennial weeds and shrubs during the growing season, and have medicinal properties that kill the above-ground parts by treating them with foliage and strongly suppress their regeneration. has. Based on this fact, the inventors have completed the invention of L-AMPBs and DL-AMPBs as herbicides, and have already applied for patents for each (Japanese Patent Application Laid-Open No. 1989-1999).
92628 and JP-A-54-92626). Furthermore, the inventors have discovered L-AMPBs and DL-
As a result of repeated research to take advantage of the characteristics of AMPBs,
We discovered that the medicinal efficacy of these compounds is enhanced when mixed with transitional herbicides, etc., and have already applied for patents (Japanese Patent Application Laid-open Nos. 129127-1982 and
(See Publication No. 926927). Based on the above knowledge, the present inventors developed the SF
-1293s, L-AMPBs, or DL-AMPBs and mixtures with other compounds, it was completely unexpected that SF-1293s, L-AMPBs, or DL-AMPBs were mixed with other compounds.
-AMPBs or DL-AMPBs include sodium bisulfite, sodium sulfite, formaldehyde sodium sulfoxylate, and 2
-, 3- or 4-pyridylhydroxymethanesulfonic acid or their salts, SF-1293 class, L-
The present inventors have discovered that the herbicidal effects of AMPBs or DL-AMPBs are surprisingly improved, and have completed the present invention. The present invention aims to provide a new herbicide composition with high herbicidal effect. That is, the herbicide composition of the present invention has the following formula () as component (A): or the following formula (): (wherein M ₁ and M ₂ may be the same or different, hydrogen, alkali metals, especially sodium, potassium, lithium; alkaline earth metals, especially magnesium, calcium; copper, zinc, nickel, manganese cations, or Ammonium cation or mono-, di-, or tri-lower alkyl-substituted ammonium cation or mono-, di-, or tri-(hydroxylalkyl)-substituted ammonium, or mono-, di-, or tri-lower alkylene-substituted ammonium・Cation or choline cation, A means inorganic acid or organic acid, n means 0, 1/2 or 1), i.e. (2-
Amino-4-[(hydroxy)(methyl)phosphinoyl]butyryl)-alanylalanine (SF-
1293), L-2-amino-4-[(hydroxy)(methyl)phosphinoyl]butyric acid (L-AMPB) or DL-2-amino-4-[(hydroxy)(methyl)phosphinoyl]butyric acid (DL-AMPB) and at least one of their salts, and (B) component sodium hydrogen sulfite, sodium sulfite, formaldehyde sodium sulfoxylate represented by the formula HOCH ₂ SO ₂ Na・2H ₂ O, 2
-, 3- or 4-pyridylhydroxymethanesulfonic acid and salts thereof, especially alkali or alkaline earth metal salts. (A) In component compound () or ()
Alkali metal atoms that can constitute M ₁ and M ₂ are usually sodium, potassium, and lithium, and alkaline earth metals are usually magnesium and calcium. In addition, the lower alkyl of the lower alkyl-substituted ammonium includes methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl having 1 to 4 carbon atoms; the lower alkylene of the lower alkylene-substituted ammonium includes methylene, ethylene, , n-propylene, isopropylene, n-butylene, and isobutylene having 1 to 4 carbon atoms. Furthermore, inorganic or organic acids A include hydrochloric acid, sulfuric acid,
Inorganic acids such as hydrobromic acid, phosphoric acid, perchloric acid, nitric acid, acetic acid, propionic acid, citric acid, tartaric acid,
Organic acids such as monochloroacetic acid, trichloroacetic acid or trifluoroacetic acid may be mentioned. The compounds listed as component (B) do not themselves exhibit any herbicidal activity within the application amount range of the composition of the present invention. However, if the compound listed as component (B) is
When mixed with SF-1293s, L-AMPBs, or DL-AMPBs as ingredients and sprayed on the leaves of plants, SF-1293s, L-AMPBs, and DL-AMPBs
The herbicidal power of AMPBs is dramatically increased (synergistic effect). i.e. SF-1293, L-AMPB, DL
- Compared to the case of single agent AMPB, the dosage of SF-1293, L-AMPB, and DL-AMPB can be reduced to 1/2 or less to produce the same drug effect.
In the present invention, the blending ratio of component (A) and component (B) is
Generally, the weight ratio ranges from 1:0.05 to 1:150,
Preferably it is in the range of 1:0.1 to 1:100. SF-1293s, L-AMPBs, DL according to the present invention
- The synergistic effect of compositions of AMPBs and other compounds is evident from the biological test examples described below. In order to clarify that it is a synergistic effect, the widely applied Colby calculation method [“Calculation method for synergistic and antagonistic effects of herbicide mixtures”]
(“Calculation of synergistic and antagonistic
Weeds, 15 (1967) pp. 20-22] was used.
According to Colby, the expected value of the effect of a mixture of two drugs can be calculated as follows. E=X+Y−X・Y/100 In the above formula, X is herbicide A with a dosage of pgram/10a
Y means the killing rate due to the herbicide B at the dose of q grams/10a, and E means the killing rate due to the herbicide A at the dose of p grams/10a and the herbicide at the dose of q grams/10a. It means the kill rate expected by mixing with the amount of herbicide B. If the actual killing rate is greater than E, this indicates that the combination has a greater effect than an additive effect, that is, a synergistic effect. According to Colby's method, as is clear from Test Examples 1, 2, and 3, SF-1293 class of the present invention, L-
It is clear that mixtures of AMPBs, DL-AMPBs and other compounds have a significant synergistic effect against a wide variety of annual and perennial monocotyledonous and dicotyledonous weeds. Regarding the usage of the composition of the present invention, in agricultural land, it is used for weed control before sowing, in paddy field ridges and after mowing, weed control in orchards and mulberry orchards, etc., and in forest land, it is used for weed control. - Can be used for land preparation by controlling shrubs, and also for controlling weeds and shrubs in pastures. In addition, factory sites, around railroad tracks, parks, around public facilities, riverbeds, embankments,
It can also be used to control weeds and shrubs in non-agricultural lands such as highways, golf courses, and fallow land. Furthermore, aquatic weeds and algae can be killed by underwater treatment. The preferred range of the blending ratio of component (A) and component (B) in this composition and the application amount of active ingredients (A) and (B) per 10 ares are generally as shown in Table 1 below. When applying, it is common to dilute the amount shown in the table with water at 10 to 250 per 10 ares, but preferably 25 to 250 per 10 ares.
The amount of water is 150. The blending ratio within this range can be freely changed, and the formulation can be freely mixed with an appropriate liquid or solid carrier by the usual formulation method for herbicides.

[Table] When actually applying the composition of the present invention, any conventional method can be used, but in most cases, a suitable diluent is used to form an aqueous solution, solution, wettable powder, emulsion, or powder. , microgranules and other formulations are mainly used. In preparing these preparations, octylphenyl polyoxyethanol, polyoxyethylene dodecyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylaryl The effectiveness can be ensured and improved by adding an appropriate amount of a nonionic surfactant such as ether, a cationic surfactant, and/or a nonionic surfactant. Next, the composition of the present invention will be specifically explained with reference to Examples and Test Examples, but the present invention is not limited to the following Examples and Experiment Examples unless the gist thereof is exceeded. In the examples, percentages are by weight unless otherwise specified. Example 1 (Liquid) SF-1293 monosodium salt (component A)
10.00% (weight) Sodium hydrogen sulfite (component B)
20.00 〃 Octylphenyl polyoxyethanol
15.00 〃 Methyl parahydroxybenzoate
0.15 〃 Water 54.85 〃 Mix and dissolve the above ingredients and dilute with water before use to prepare a liquid composition for use in foliage treatment. Example 2 (hydrate) L-AMPB mono(diethanolammonium) salt (component A) 15.0% (weight) Formaldehyde/sodium/
Sulfoxylate (component B) 30.0 〃 Diatomaceous earth 50.0 〃 Nonionic surfactant 5.0 〃 The above components are mixed uniformly and finely ground to make a wettable powder. When using it, dilute it with water and treat the foliage. In addition, in the above, L-AMPB mono(diethanolammonium) salt refers to L-AMPB
The carboxylic acid group hydrogen is di-(hydroxyethyl)
ammonium cation

It is a salt substituted with [Formula]. Example 3 (Powder) L-AMPB mono(isopropylammonium) salt (A component) 5.0% (weight) 2-pyridylhydroxymethanesulfonic acid (B component) 20.0 Talc 75.0 The above components were mixed uniformly and ground. and make a powder. L-AMPB mono (isopropylammonium)
Salt means that the carboxylic acid group hydrogen of L-AMPB is isopropylammonium

It is a compound substituted with [Formula]. Example 4 (Liquid) DL-AMPB monosodium salt (component A)
10.00% (weight) Sodium sulfite (component B) 20.00 Octylphenyl polyoxyethanol
15.00 〃 Methyl parahydroxybenzoate
0.15 〃 Water 54.85 〃 Mix and dissolve the above ingredients and dilute with water before use to prepare a liquid composition for use in foliage treatment. Example 5 (Wettable powder) SF-1293 mono(diethanolammonium) salt (A component) 15.0% (weight) 4-pyridylhydroxymethanesulfonic acid monosodium salt (B component) 30.0 〃 Diatomaceous earth 50.0 〃 Nonionic surfactant Agent 5.0 〃 The above ingredients are mixed uniformly and finely ground to make a wettable powder. When using it, dilute it with water and treat the foliage. Example 6 (Powder) DL-AMPB mono(isopropylammonium) salt (component A) 5.0% (weight) Formaldehyde, sodium,
Formaldehyde Sodium
Bisulfite) (Component B) 20.0 〃 Talc 75.0 〃 Mix the above ingredients uniformly and grind to make a powder. Next, the medicinal efficacy (synergistic effect) of the composition of the present invention was tested. Test Example 1 Fill pots with a diameter of 6 cm with field soil, sow 8 to 9 Novie seeds per pot, and add various salts of SF-1293, L-AMPB and DL-AMPB, and sulfite when the seeds have about 4 to 4.5 leaves. Sodium hydrogen and SF-
An aqueous solution containing a predetermined amount of a mixture of various salts of 1293, L-AMPB, and DL-AMPB and sodium bisulfite was sprayed over the entire stem and leaves at a spraying rate of 100 m/10 are. The survey was conducted on the 14th day after treatment, and the mortality rate was expressed as a percentage, which is shown in Table 2 (0
%: harmless to 100%: completely dead). In addition, the expected value of a two-drug mixture was calculated from the measured value of each single drug using Colby's equation, and the presence or absence of a synergistic effect was investigated.

【table】

【table】

[Table] Test Example 2 Fill a plastic pot with a diameter of 6 cm with field soil, and sow 8 to 9 Novie seeds per pot.
SF-1293, L-AMPB and
Monosodium salt of DL-AMPB, sodium bisulfite, sodium sulfite, formaldehyde sodium bisulfite
Sodium Bisulfite), Formaldehyde Sodium Sulfoxylate
sulfoxylate) and the sodium salt of 2-, 3- or 4-pyridylhydroxymethanesulfonic acid, as well as SF-1293, L-AMPB or DL-
Monosodium salt of AMPB, sulfite, sodium bisulfite, sodium sulfite, Formaldehyde Sodium Bisulfite, Formaldehyde Sodium Sulfoxylate, 2-,
A predetermined amount of a mixture with the sodium salt of 3-pyridylhydroxymethanesulfonic acid or the sodium salt of 4-pyridylhydroxymethanesulfonic acid was sprayed over the entire foliage at a spraying rate of 100 per 10 are. The survey was conducted on the 14th day after treatment, and the kill rate was expressed as a percentage and shown in Table 3 (0%: harmless to
100%: completely dead). In addition, using Colby's equation, the expected value of a two-drug mixture was calculated from the measured value of each single drug, and the presence or absence of a synergistic effect was investigated. In addition, in Table 3, SF-1293, L-
The monosodium salts of AMPB and DL-AMPB were respectively SF-1293Na, L-AMPB Na and DL-
It was abbreviated as AMPB Na. Also, formaldehyde sodium bisulfite (formaldehyde sodium bisulfite)
Sodium Bisulfite), Formaldehyde Sodium Sulfoxylate
Table 3 shows the sodium salts of FSB, FSS, and 2-PHS, respectively.
Abbreviated as Na, 3-PHS Na and 4-PHS Na.

【table】

【table】

【table】

【table】

【table】

[Table] Test Example 3 In the field, the monosodium salts of SF-1293, L-AMPB and DL-AMPB, and hydrogen sulfite were applied to crabgrass, Japanese dogfish, Japanese knotweed, mugwort, halcyon, Japanese japonica, Japanese oak, and Quercus in the middle of the growing season. An aqueous solution containing a predetermined amount of each single sodium agent or a mixture of both agents was sprayed over the entire stem and leaves at a spraying rate of 100 water per 10 are. Investigation after processing 1
It is carried out every month, and the mortality rate is expressed as a percentage.
It is shown in Table 4 (0%: harmless to 100%: completely dead). Furthermore, the presence or absence of synergistic effects was examined using Colby's equation. In Table 4, E indicates an expected value, O indicates an actual value, and * indicates a synergistic effect.

【table】

【table】

[Table] As is clear from Table 4, the composition of the present invention has a synergistic effect on killing above-ground parts and inhibiting regeneration in the first month after treating perennial weeds and shrubs. found.

Claims (1)

[Claims] 1 (A) Formula (): or the following formula (): [In the formulas () and (), M ₁ or M ₂ may be the same or different and represent hydrogen, alkali metals, alkaline earth metals, copper, zinc nickel or manganese cations, or aluminum cations.
Cation, or mono-, di- or tri-
Lower alkyl-substituted ammonium cation; mono-di- or tri-(hydroxyalkyl)
Substituted ammonium cation or choline
cation, A means an inorganic acid or organic acid, and n means 0, 1/2 or 1]; (B) sodium bisulfite, sodium sulfite,
Formaldehyde sodium sulfoxylate, 2-, with the formula HOCH ₂ SO ₂ Na.2H ₂ O
A herbicidal composition comprising a mixture with at least one of pyridylhydroxymethanesulfonic acid, 3-pyridylhydroxymethanesulfonic acid, 4-pyridylhydroxymethanesulfonic acid, and salts thereof. 2. The composition according to claim 1, wherein component (A) is a compound represented by formula (). 3. The composition according to claim 1, wherein component (A) is a compound represented by formula (). 4 Among the compounds whose component (A) is represented by the formula (), L
- The composition according to claim 1, which is a symmetrical body.