JPH01228904A - Herbicide composition - Google Patents

Abstract

PURPOSE: To obtain an inexpensive herbicidal composition reduced in toxicity to human health while retaining its excellent herbicidal activity by incorporating bipyridylium quaternary cationic salts having herbicidal activity with sulfuric ester(s) of monosaccharide and/or oligosaccharide. CONSTITUTION: This herbicidal composition comprises respective salts of bipyridylium quaternary cations of formula I R and R' are each a 1-4C alkyl, OH, a halogen or (carboxyl-, etc., substituted) 1-4C alkyl; [X]<m-> is an anion ((m) is 1-4)} and formula II and at least one kind of compound selected from sulfuric esters of monosaccharides of formula III (M is a metal cation, H ion or another cation; X is >=1) (including sugar alcohol) and salts thereof, glucose sulfuric esters of formula IV (R is H or SO3 M, at least one of Rs being SO3 M) and salts thereof, sucrose sulfuric esters of formula V and salts thereof and oligosaccharide sulfuric esters and salts thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a herbicidal composition comprising a salt of bipyridylium quaternary cation, and more specifically,
The present invention relates to a herbicidal composition which maintains the herbicidal activity of a herbicide comprising a salt of bipyridylium quaternary cation while significantly reducing its toxicity to animals.

[Prior Art] Bipyridylium quaternary cation salts are widely used worldwide as excellent herbicides. However, bipyridylium quaternary cation salts have relatively high toxicity to animals such as humans, and are therefore designated as non-pharmaceutical poisonous and deleterious substances. Although it does not cause any particular harm to the human body if used with sufficient care in accordance with the law, it cannot be denied that accidents resulting in poisoning and death due to accidental ingestion, misuse, or misuse of the concentrate concentrate (a-condensate) cannot be denied. By the way.

Therefore, in order to reduce and prevent poisoning accidents caused by bipyridylium quaternary cation salts, emetics are added to the stock solution of the preparation (Japanese Patent Publication No. 5B-35641), and in order to avoid misidentification, it is necessary to identify the product as a pesticide. Blue pigments and odorants are added to facilitate this process. However, these are only measures and proposals for preventing poisoning accidents, and the bipyridylium quaternary cation salt-containing herbicide composition itself is still toxic.

[Problems to be Solved by the Invention] Under these circumstances, there has been a desire for a herbicide that maintains an excellent herbicidal effect and is less toxic to the human body.

An object of the present invention is to provide, at a low cost, a herbicidal composition that maintains the long-desired excellent herbicidal effect and further reduces toxicity to the human body.

[Means for Solving the Problems] As a result of a tit study, the present inventor has found that the toxicity of bipyridylium quaternary salts having herbicidal activity is higher than that of monosaccharide (including sugar alcohol) sulfate esters, their ester salts, and oligosaccharides. It has been found that the effects can be significantly alleviated by adding at least one selected from sulfuric esters and ester salts thereof. The present invention was completed based on this knowledge.

The present invention provides bipyridylium quaternary salts having herbicidal activity, one or more selected from monosaccharide (including sugar alcohol) sulfate esters and ester salts thereof, oligosaccharide sulfate esters and ester salts thereof. The present invention relates to a herbicidal composition containing the compound. As monosaccharide (including sugar alcohol) sulfate esters or ester salts thereof, and oligosaccharide sulfate esters or ester salts thereof, Represents a cation. however,
At least one endogeneity of R is 503M. ] One or more compounds selected from the following are suitable.

In the various saccharide (including sugar alcohol) sulfuric acid esters or ester salts thereof, the preferable range of the substitution ratio of 503M is, for example, in the case of formula (n), 503M is on average 3. The number is 5 to 4.5, and in the case of formula (m), 503M is 5 to 7 on average compared to 28.

In addition, dicarboses, tricarbons, tetracarbons, pentoses, hexoses, heptoses (including their corresponding ketoses), their amino sugars, their derivatives such as uronic acids, and their Sulfuric esters of monosaccharides such as sugar alcohol derivatives or ester salts thereof can also be used.

Furthermore, trehalose, lactose, maltose, isomaltose,
Trisaccharides such as cellobiose, nigerose, and chitobiose,
Trisaccharides such as raffinose and meletitose, tetrasaccharides such as stachyose, and oligosaccharide sulfate esters or ester salts thereof, whose main constituents are one or two to five of the above monosaccharides, or mixtures thereof can also be used.

By adding and mixing monosaccharide (including sugar alcohol) sulfate ester or oligosaccharide sulfate ester with bipyridylium quaternary cation salt, even if accidentally swallowed, significant poisoning symptoms may occur. There is no. Therefore, the present invention provides an extremely safe herbicidal composition that maintains herbicidal activity with almost no reduction and has significantly reduced toxicity.

In the present invention, the most preferable monosaccharide (including sugar alcohol) sulfate or ester salt thereof, or oligosaccharide sulfate or ester salt added to alleviate toxicity is the glucose sulfate ester of formula (n) or the formula It is a sucrose sulfate ester of (II[), and ester salts thereof include monovalent metals such as sodium and potassium, metal salts such as calcium, magnesium, and aluminum, or ammonium salts.

The sodium salt of glucose sulfate is the formula (■),
The sodium salt of sucrose sulfate has the formula (III)
These are compounds each represented by R is hydrogen or S O
s N a. These sodium salts are easily soluble in water and have no viscosity, and are suitable for producing liquid preparations or granular solid preparations with bipyridylium quaternary cation salts.

The herbicidal bipyridylium quaternary cation salt used in the composition of the present invention is a compound represented by the following formula.

In the above formula, R and R' may be the same or different, and each is an alkyl group having 1 to 4 carbon atoms, or hydroxy, halogen, carboxyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, carbamoyl, and N-substituted represents an alkyl group having 1 to 4 carbon atoms substituted with a group selected from albamoyl, (X)"- represents an anion, and m represents an integer of 1 to 4.

Bipyridylium quaternary cation salts having particularly preferable herbicidal activity are shown below.

1.1'-dimethyl-4,4'-bipyridylium di(
Methyl sulfate) [Balaquat dimethosulfate].

1.1'-ethylene-2,2'-bipyridylium dibromide [diquat dibromide].

1.1'-dimethyl-4,4'-bipyridylium dichloride [balaquat dichloride].

1-(2-hydroxyethyl)-1'-methyl-4,
4'-Bipyridylium dichloride.

1.1'-di-carbamoylmethyl-4,4'-bipyridylium dichloride.

1.1'-Bis-N,N-dimethylcarbamoylmethyl-4,4'-bipyridylium dichloride.

1.1'-dimethyl-4,4'-bipyridylium sulfate [balaquat sulfate].

1.1'-bis(3,5-dimethylmorpholinecarbonylmethyl)-4,4'-bipyridylium chloride [
Molham Court Dichloride].

1.1'-Bis-N,N-diethylcarbamoylmethyl-4,4'-bipyridylium dichloride.

1.1'-Diacetonitrile-4,4'-bipyridylium dichloride.

1.1'-Jethoxycarbonylmethyl-4,4'-bipyridylium dibromide.

The name within 0 in the above compound is its common name. For example, "Balaquat" is 1,1'-dimethyl-4,4'-
It is the common name for the bipyridylium cation.

A particularly preferred bipyridylium cation for use in the compositions of the invention is baraquat.

A particularly preferred anion (X)"- is the chloride ion for reasons of convenience and economy, but any anion that conveniently gives a water-soluble salt can be used if desired. Only the bipyridylium cation has herbicidal action. Because of this, the concentration of herbicidal bipyridylium salt compositions is often indicated only by its cation.

The degree of reduction in toxicity of the bipyridylium quaternary cation salt in the herbicidal composition of the present invention is determined by the degree of reduction in toxicity of monosaccharide (including sugar alcohol) sulfate esters and their ester salts, and oligosaccharide sulfate esters and their ester salts. If selected from! J or higher depending on the compound. If the addition rate of the above-mentioned IFJ or higher compound to the bipyridylium quaternary cation salt is increased, the toxicity will be greatly reduced, but on the other hand, the herbicidal effect of the bipyridylium quaternary salt will be affected. Therefore, the blending ratio of both components can be determined while taking into consideration the herbicidal effect and the degree of toxicity reduction. Generally, it is preferable to adjust the ratio to such a level that the toxicity of the bipyridylium quaternary cation salt exceeds the lethal dose and the herbicidal effect can be maintained. However, since the lethal dose in humans cannot be directly measured, it can only be estimated through animal tests.

A preferred composition ratio is one or more selected from monosaccharide (including sugar alcohol) sulfate esters and ester salts thereof, oligosaccharide sulfate esters and ester salts thereof, to 1 part by weight of bipyridylium quaternary cation salt. This is a case where the proportion of the compound is 1 to 5 parts by weight. Particularly preferably, one or more types selected from monosaccharide (including sugar alcohol) sulfate esters and ester salts thereof, oligosaccharide sulfate esters and ester salts thereof are added to 1 part by weight of bipyridylium quaternary cation salt. 2 to 4 compounds
Parts by weight.

A carrier or diluent may be included in the composition of the invention, and the composition may be solid, e.g. particulate or liquid.
For example, it can be an aqueous solution. The amount of herbicidal bipyridylium quaternary cation present in the aqueous solution is 50-400 g/l
is preferred.

Preferably, the composition of the present invention further contains a surfactant.

Surfactants that can be used are cationic, nonionic or anionic; anionic surfactants are
The bipyridylium quaternary cation salt in the composition and the cationic surfactant are monosaccharide (including sugar alcohol) sulfate esters and their ester salts and oligosaccharide sulfate esters and their ester salts in the composition. 1 selected from
Nonionic surfactants are generally preferred because they may interact undesirably with one or more compounds. Examples of nonionic surfactants that can be used in the compositions of the invention are condensation products of ethylene oxide and alkylphenols such as octylphenol, nonylphenol and octylcresol.

Examples of other nonionic surfactants are partial esters derived from long chain fatty acids and hexit anhydride, such as sorbitan monolaurate, condensation products of such partial esters with ethylene oxide, and lecithins.

In the composition of the present invention, all of the auxiliaries, diluents, etc. that are conventionally added to this type of herbicide can be present as necessary. For example, dyes, pigments, etc. for identification coloring can be added as necessary. An example of such a compound is “Monaetral Blue”.
BNV Pa5te” and “Llssamlne T
urquoise VN 150”.

The compositions of the invention may further contain odorants. Examples of such odorants are alkyl pyridine, n-valeric acid and tetrahydrothiophene as described in GB 1406881.

If desired, monosaccharide (including sugar alcohol) sulfate esters of formula (II) and ester salts thereof and formula (III)
A compound of IFi or higher selected from oligosaccharide sulfate esters and ester salts thereof can be included in a thixotropic composition of quaternary cation salts having herbicidal activity. In particular, one or more compounds selected from monosaccharide (including sugar alcohol) sulfates and their ester salts (II) and oligosaccharide sulfates and their ester salts (III) are disclosed in British Patent No. 139550.
It can be included in the composition of the herbicidal bipyridylium quaternary cation salt described in the specification of No. 2. Such compositions include an aqueous solution of a herbicidal bipyridylium quaternary cation salt containing a gelling agent, such as finely divided silica, a combination of xanthan gum and sodium metaborate, commercially available under the trade name Kelzan'. Xanthan gum is a complex polysaccharide.

The composition of the present invention was tested for herbicidal activity and acute toxicity. The results show that the herbicidal composition of the present invention is able to maintain herbicidal action while drastically reducing acute toxicity.

Test Example 1 Herbicidal effect Balaquat dichloride preparation [manufactured by I C1 [Gramoxone SJ (preparation containing 24% by weight of baraquat dichloride), trade name]] was added to 200p as baraquat ion.
Sodium salt of glucose sulfate (S content: 21.0%) and sodium salt of sucrose sulfate (S content: 120.3%) were added to an aqueous solution diluted to pm.
) at three concentrations (3000 ppm.

2ooopp■, 1500ppm), prepared three types of aqueous solutions, and poured them into small polystyrene bowls (
Novie (plant height 2cm) being cultivated in 20X15X5cm)
The above prepared solution was evenly sprayed onto wheat (plant height 10 cm) at a rate of 100 ml per coat. Herbicidal activity was evaluated based on mortality rate on the 7th day after treatment.

Concentration (ppm) □ Mortality rate Wheat PQ 200 5 5PQ
+GS 200+3000 1:15 4
4PQ+GS 200+2000 1:10
4 4PQ+GS 200+1500 1:
7.5 4 4PQ+5ucS 200+3
000 1:15 4 2PQ+5ucS
200+2000 1:10 4 2PQ+5
ucS 200+1500 1: 7.5 4
In Table 2, PQ represents paraquat ion, GS represents sodium salt of glucose sulfate, and 5ucS represents sodium salt of sucrose sulfate.

The herbicidal activity determination criteria for mortality rate are as follows.

(Standard) 5: 100% mortality 4: 80% mortality 3: 60% mortality 2: 40% mortality 1: 20% mortality 0: No effect Test Example 2 Herbicidal effect The formulation of Formulation Example 4 described below was mixed with water. Diluted 250 times,
A spray solution containing 400 ppm each of PQ and 5ucS was prepared. In addition, the formulation of Formulation Example 8 described below was diluted 375 times with water, and P Q 400 ppm and SucS8
A spray solution containing 0.00 ppm was prepared. The control spray liquid was a PQ preparation (“Gramoxone S” manufactured by IC1, PO24
% by weight) was diluted 600 times with water.

Each of the spray liquids obtained in this way was applied to small polystyrene pots (20 x 15 x 5 cm) on wild plants (
The mixture was evenly applied to wheat (plant height 10 cm) and wheat (plant height 2 gcI6) at a rate of 100 ml per plant. On the 6th day after treatment, herbicidal activity was evaluated based on mortality rate.

P Q 400pp-Ni to Sur Composition ratio Blight
Rate 5ucS concentration (ppm) Wildflower wheat 0 1:0 5 5 400 1:l 5 5800
1:2 3 4 In the table, PQ represents paraquat ion and 5ucS represents sodium salt of sucrose sulfate.

The herbicidal activity determination criteria for mortality rate are as follows.

(Standard) 5: 100% mortality 4: 80% mortality 3: 60% mortality 2: 40% mortality 1: 20% mortality 〇2 No effect test example 3 Acutely toxic baraquat dichloride and sodium salt of glucose sulfate (S FF (containing 121.0%) were mixed at various ratios, dissolved in distilled water, and orally administered to 4-week-old ddY strain mice (male, weight: 8-20 g). Feed is dose 2
They were removed 4 hours before and fed again 3-4 hours after administration. Ten mice were used in each group. Survival rates were shown on the 4th day and 144th day after administration.

Dose (mg/kg) Composition ratio survival rate (%) PQ +
GS PQ:GS 4th day 14th 1st 00+0 1:0 0 0 200÷100 1:0.5 50 20200+
200 1:l'yo 7020G+
300 1:1.5 70 70200+ 400
1:2 80 80200+ 800
1:4 100 100200+
1600 1:8 1G0 100 In the table, PQ represents baraquat dichloride and GS represents sodium salt of glucose sulfate.

Test Example 4 Acutely toxic baraquat dichloride and sodium salt of sucrose sulfate (S content: 120.3%) were mixed in various ratios, dissolved in distilled water, and prepared into 4-week-old ddY strain mice (female, weight 18%). ~20g) was administered orally. Feed is dose 2
They were removed 4 hours before and fed again 3-4 hours after administration. Ten mice were used in each group. Survival rates were shown on the 4th day and 144th day after administration.

Administration fi (g/kg) Composition ratio survival rate (%) PQ
+5ucS PQ:5ucS 4th day 14th day 1?00÷ 0 1:0 0 0 200+ 100 1:0.5 ao 402
00+ 200 1:l 6o 40200
+ 300 1:1.5 80 80200+ 4
00 1:2 too 1002004800
1:4 too 100200+1600
1:8 100 100 In the table, PQ represents baraquat dichloride and 5ucS represents sodium salt of sucrose sulfate.

Next, formulation examples of the composition of the present invention will be shown.

Formulation Example 1 10g of baraquat dichloride was dissolved in 20f of water. On the other hand, 20f of sucrose sulfate sodium salt was dissolved in 30i of water, and these solutions were mixed and stirred. Next, 5 g of polyoxyethylene nonylphenyl ether was added and diluted with water to a total amount of 100 g while stirring to prepare the composition of the present invention containing 0% baraquat dichlorite white and 20% sucrose sulfate ester sodium salt. Obtained. This composition can be further diluted 150 to 200 times for practical use.

Formulation Examples 2-8 Balaquat dichloride (PQ) is dissolved in twice the amount of water, diquat dibromide (DQ) is dissolved in the same mtst amount of water, and the monosaccharide sulfate ester salt or the oligosaccharide sulfate ester salt is Each was dissolved in the same weight of water to form a solution.

These were sequentially mixed and dissolved according to the table below, then a predetermined amount of surfactant was added, and finally diluted with water to obtain a predetermined dose of each herbicidal composition of the present invention.

These compositions can be used after being diluted 100 to 500 times with water.

table (unit nigerum) Note) The abbreviations represent the following compounds.

PQ: Paraquat dichloride DQ = diquat dibromide 5ucS Nisucrose sulfate ester sodium salt (320.3%) GS Nigelcose sulfate ester sodium salt (S 21.0%) XS: Beef sirose sulfate ester sodium salt (S 19.8%) ) POENP: Polyoxyethylene nonylphenyl ether POENO: Polyoxyethylene octylphenyl ether [Effects of the invention] Bipyridylium quaternary cation salts exhibit very excellent herbicidal effects but are highly toxic to animals such as humans.
By containing one or more compounds selected from monosaccharide (including sugar alcohol) sulfate esters and their ester salts, and oligo-1lfi sulfate esters and their ester salts, we maintain excellent herbicidal effects. Moreover, it has become possible to provide a herbicide composition with reduced toxicity to the human body at a low cost.

Claims (5)

[Claims] (1) One or more salts of bipyridylium quaternary cations having herbicidal activity, monosaccharide (including sugar alcohol) sulfate esters and their ester salts, and oligosaccharide sulfate esters and their ester salts. A herbicide composition containing the above compounds. (2) Salts of bipyridylium quaternary cations have the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R and R′ may be the same or different. each having 1 to 4 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms or a group selected from hydroxy, halogen, carboxyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, carbamoyl, and N-substituted carbamoyl; It represents four alkyl groups, [X]^m^- represents an anion, and m represents an integer of 1 to 4. The herbicidal composition according to claim 1, which is selected from the compounds represented by the following. (3) Monosaccharide (including sugar alcohol) sulfate esters and their ester salts, oligosaccharide sulfate esters and their ester salts are represented by the formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) [In the formula, M is a metal cation , represents a hydrogen ion or other cation. However, X represents a number of 1 or more. The herbicidal composition according to claim 1, which is a compound selected from the following. (4) Monosaccharide (including sugar alcohol) sulfuric acid ester or its ester salt, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) [In the formula, R represents hydrogen or SO_3M, and M represents a metal cation, hydrogen Represents an ion or other cation. however,
At least one of R is SO_3M. ] The herbicidal composition according to claim 3, which is a glucose sulfate ester or an ester salt thereof. (5) Oligosaccharide sulfate ester or its ester salt, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) [In the formula, R represents hydrogen or SO_3M, and M is a metal cation, hydrogen ion, or other cation represents. however,
At least one of R is SOM. ] The herbicidal composition according to claim 3, which is a sucrose sulfate ester or an ester salt thereof.