JP2617536B2 - Agricultural and horticultural fungicides - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an agricultural and horticultural fungicide, and more particularly, to an agricultural and horticultural fungicide which is excellent in persistence and has little phytotoxicity to plants.

[Problems to be solved by conventional technology and invention]

Generally, quaternary ammonium salts show strong bactericidal activity,
It has been used as a germicidal disinfectant because of the relatively low appearance of resistant bacteria.However, it is easily washed away by rainfall or running water, and its efficacy is significantly reduced. Therefore, it was not possible to utilize its excellent bactericidal activity as an agricultural and horticultural fungicide.

[Means for solving the problem]

The present inventors have conducted intensive studies to suppress runoff due to rainfall and the like without reducing the strong bactericidal activity of quaternary ammonium salts, and to reduce phytotoxicity to useful plants. By replacing the counter ion with an anionic residue of an anionic oligomer or a polymer acid having a degree of polymerization of 3 or more, it was possible to suppress the leaching property without impairing the medicinal effect and reduce the phytotoxicity, and completed the present invention. did.

That is, the present invention provides an agricultural and horticultural fungicide containing a quaternary ammonium salt represented by the general formula (I) as an essential component.

(Where R₁, R_Two, R_ThreeIs at least one straight chain having 8 to 30 carbon atoms
Or a branched-chain alkyl or alkenyl group, with the balance being-
CH_Three, −CH_TwoCH_Three, Wherein n is 1 to 5,
R_FourIs -CH_ThreeOr -CH_TwoCH_Three, Counter ion X Is a degree of polymerization of 3 or more
Anionic residue of the acid of the anionic oligomer or polymer
Group. The anionic oligomer or polymer of the present invention has the following
Compounds containing one or more selected from 1) to 3)
It is preferably an object.

1) A polymer containing, as an essential component, one or more members selected from the group consisting of unsaturated carboxylic acids and derivatives thereof.

2) A polymer containing styrene sulfonic acid as an essential constituent monomer.

3) A formalin condensate of a sulfonated polycyclic aromatic compound which may have a hydrocarbon group as a substituent.

 The quaternary ammonium represented by the general formula (I) according to the present invention
The um salt has a characteristic counter ion, and the counter ion X Is the degree of polymerization
Anilines of three or more anionic oligomeric or polymeric acids
It is important that it is an on residue, and it is basically a counter ion X
Anionic oryl having an anionic residue of a potential acid
It is important that they are sesame or polymer. In the present invention
The above 1) to 3) anionic oligomer or polymer
Will be described specifically.

1) A polymer containing, as an essential component, one or more members selected from the group consisting of unsaturated carboxylic acids and derivatives thereof.

Monomers used in the production of the polymer 1) include unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid;
There are unsaturated dicarboxylic acids such as maleic acid, and derivatives thereof, for example, alkyl esters (such as methyl esters) of the above acids or polyoxyethylene esters. In addition to these monomers, copolymerizable monomers such as vinyl acetate, isobutylene, diisobutylene, and styrene can be added as copolymer components.

The method of polymerizing these monomers is performed by a conventionally known method. The proportion of the monomer component and the degree of polymerization of the polymer are not particularly limited.

Specific examples include acrylic acid polymer, methacrylic acid polymer, copolymer of acrylic acid and methacrylic acid,
A copolymer of acrylic acid and polyoxyethylene methacrylate, a copolymer of acrylic acid and methyl acrylate, a copolymer of acrylic acid and vinyl acetate, a copolymer of acrylic acid and maleic acid, Examples include a copolymer of maleic acid and isobutylene, and a copolymer of maleic acid and styrene. Two or more of these polymers can be used. In addition, a salt with an alkali metal, ammonia, or an organic amine can be used to such an extent that the performance is not impaired.

2) A polymer containing styrene sulfonic acid as an essential constituent monomer.

The homopolymer of styrene sulfonic acid can be easily produced by polymerizing styrene sulfonic acid or sulfonating polystyrene. The styrene sulfonic acid polymer has a skeleton represented by the following formula.

The molecular weight is at least 1,000, preferably from 1,000 to 500,000.

Also, the copolymer of styrene sulfonic acid and other monomer is obtained by copolymerizing styrene sulfonic acid and other monomer or sulfonating the copolymer of styrene and other monomer. It can be easily manufactured. Copolymerization partners include hydrophobic monomers such as alkyl acrylate, alkyl methacrylate, vinyl alkyl ether, vinyl acetate, ethylene, propylene, butylene, butadiene, diisobutylene, vinyl chloride, vinylidene chloride, acrylonitrile, and styrene. Body, and acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride,
Hydrophilic monomers such as vinyl alcohol, acrylamide, methacrylamide, diacetone acrylamide, N-vinylpyrrolidone, 2-acrylamido-2-methylpropanesulfonic acid, methacrylsulfonic acid, xylenesulfonic acid, and naphthalenesulfonic acid are used. . Preferred copolymers include (meth) acrylic acid-styrene sulfonic acid copolymer. The molar ratio of (meth) acrylic acid to styrenesulfonic acid in the copolymer is from 1/10 to
It is 10/1, preferably 1/3 to 4/1. The average molecular weight is 10
It is 100 to 100,000, preferably 1,000 to 500,000. Also, sodium salt, potassium salt, ammonium salt, diethanolamine salt, triethanolamine salt, monoisopropanolamine salt, diisopropanolamine salt, triisopropanolamine salt, 2-amino-2-methylpropane-1 to the extent that performance is not impaired. There may be a neutralized portion of a salt such as 3,3-diol salt.

3) A formalin condensate of a sulfonated polycyclic aromatic compound which may have a hydrocarbon group as a substituent.

Specifically, it is a formalin condensate such as a petroleum sulfonic acid derivative, a signin sulfonic acid derivative, a naphthalene sulfonic acid derivative, a xylene sulfonic acid derivative, or an alkylbenzene sulfonic acid derivative.

The compound 3) according to the present invention includes, for example, naphthalene,
It is obtained by sulfonating alkyl-substituted benzene, alkyl-substituted naphthalene, anthracene, alkyl-substituted anthracene, lignin, and those having an aromatic ring in petroleum residue by a general method, followed by formalin condensation. In this case, the degree of condensation is preferably 3 or more, more preferably 3 to 30. Here, the degree of condensation is 2
In the following cases, the effect of the condensation is small, causing a problem in practical use.

As the aromatic compound to be used, various compounds can be used. Preferably, lignin, xylene, toluene, naphthalene or alialkylnaphthalene having 1 to 6 carbon atoms may be used. May be.

In addition, amines, ammonium salts, etc., as well as alkali metals such as sodium and potassium, alkaline earths such as calcium, and the like may be used to such an extent that the performance is not hindered.

The quaternary ammonium salt represented by the general formula (I) according to the present invention is obtained, for example, by previously converting a quaternary ammonium salt whose counter ion is a halogen atom into an OH-type quaternary ammonium using an ion exchange resin. It is easily produced by neutralization with an oligomer or polymer having an anionic residue of the above acid. Further, alkali metal salts, amine salts, organic amine salts, and the like may be partially contained to such an extent that the performance is not hindered.

The fungicide for agricultural and horticultural use of the present invention is applied directly or diluted to plants or soil. When spraying, the quaternary ammonium salt having the above counter ion is used as an active ingredient in an amount of 0.01 to 60% by weight.
Is preferably used.

When the compound of the present invention is applied, it may be used in any formulation type such as a water solvent, a wettable powder, a granule, a powder, an emulsion, an oil and a paste. Therefore, other additives such as salts, surfactants, thickeners, carriers and the like can be added according to the formulation type.

Examples of the salts include metal salts of carboxylic acids such as succinic acid, malonic acid, citric acid, gluconic acid, and glutaric acid; metal salts of phosphate compounds such as tripolyphosphoric acid, hexametaphosphoric acid, and phosphoric acid; Na ₂ SO ₄ , MgSO ₄ , and the like. And the like. These can be used alone or in combination.

As the surfactant, a nonionic surfactant and an anionic surfactant are used. As the nonionic surfactant and / or anionic surfactant, for example, polyoxyethylene (hereinafter referred to as POE) is used. ) Alkyl (C6 ~ 2
2) Non-ionic such as ether, POE alkyl (C4-18) phenol ether, polyoxypropylene polyoxyethylene (block or random) alkyl ether, POE phenyl phenol ether, POE styrenated phenol ether, POE tribenzyl phenol ether Surfactant, lignin sulfonate, alkyl benzene sulfonate, alkyl sulfonate, POE alkyl sulfonate, POE alkyl phenyl ether sulfonate, POE alkyl phenyl ether phosphate, POE phenyl phenol ether sulfonate POE phenyl phenol ether phosphate, naphthalene sulfonate, naphthalene sulfonic acid formalin condensate, POE tribenzyl phenol ether sulfonate, POE tribenzyl phenyl pheno Anionic surfactants such as ether phosphoric acid ester salts. These can be used alone or in combination.

Its content in the fungicide is 0 to 20% by weight, preferably 1 to 10% by weight.

As the water-soluble thickener, any of natural, semi-synthetic and synthetic water-soluble thickeners can be used.For natural mucilage, xanthan gum derived from microorganisms, xanflow, pectin derived from plants, gum arabic, guar gum, etc. In semi-synthetic mucilage, methylated product of cellulose or starch derivative, carboxyalkylated product, hydroxyalkylated product (including methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, etc.), sorbitol, etc.
Specific examples of the synthetic mucus include polyacrylate, polymaleate, polyvinylpyrrolidone, and pentaerythritol EO adduct. The water-soluble thickener is
About 0 to 3.0% by weight, preferably about 0.05 to 0.5% by weight is added to the fungicide.

Examples of the carrier include inorganic mineral salts and water-insoluble polymers.Examples of the inorganic mineral salts include inorganic salts clay, talc, bentonite, calcium carbonate, diatomaceous earth, and white carbon.Examples of the water-insoluble polymer include styrene sulfonic acid. , 2-acrylamide, 2-methylpropane sulfonic acid, xylene sulfonic acid, naphthalene sulfonic acid, and the like, and polymers thereof and salts thereof, or these monomers and alkyl acrylate, alkyl methacrylate, vinyl alkyl ether, vinyl acetate, vinyl acetate, ethylene , Propylene, butylene, butadiene, diisobutylene, vinyl chloride, vinylidene chloride, acrylonitrile, hydrophobic monomers such as styrene, and acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride,
Examples include vinyl alcohol, acrylamide, methacrylamide, diacetone acrylamide, and a copolymer of N-vinylpyrrolidone.

Furthermore, the fungicide for agricultural and horticultural use of the present invention can be used by mixing one or more kinds of other plant growth regulators, fertilizers, insecticides, fungicides, preservatives and the like.

〔The invention's effect〕

The fungicide for agricultural and horticultural use of the present invention can be used for all agricultural activities. Compared with the conventional quaternary ammonium salt, it greatly suppresses runoff such as rainfall, extremely reduces phytotoxicity to plants, Effective against diseases.

〔Example〕

Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples.

Table 1 shows quaternary ammonium salts of the compound of the present invention.
Examples of prescription are shown below.

Formulation Example 1 Compound 10 parts by weight Polyoxyethylene (EO = 9 mol) nonylphenyl ether (Emulgen 909, manufactured by Kao Corporation) 5 Polyoxyethylene (EO = 18 mol) nonylphenyl ether sulfate sodium salt (Levenol WZ, Kao) (Made by Corporation)
2 Fine powder clay (manufactured by Kunimine Industries) 83 Formulation Example 2 20 parts by weight of compound Polyoxyethylene (EO = 18 mol) nonylphenyl ether sulfate sodium salt (Levenol WZ, manufactured by Kao Corporation)
5 White carbon (Shionogi Pharmaceutical Co., Ltd.) 20 Fine powder clay (manufactured by Kunimine Industries) 55 Formulation Example 3 Compound 10 parts by weight polyvinyl alcohol 5 Polyoxyethylene (EO = 9 mol) noniphenyl ether (Emulgen 909, manufactured by Kao Corporation) 5 Water 80 Formulation Example 4 Compound 50 parts by weight Diethylene glycol 40 Polyoxyethylene (EO = 9 mol) nonylphenyl ether (Emulgen 909, manufactured by Kao Corporation) 10 Test samples were prepared according to the above formulation. Compounds 2, 3, 5, 6, 7, and 8 in Table 1 are compounds of the present invention, and compounds 1 and 4 are control compounds.

Example 1 (Effluent test) The drug of each prescription was added to the 10 pots of the green leaf of the kidney at the second leaf stage.
The solution was diluted and sprayed so that the quaternary ammonium salt concentration became 1000 ppm. 24 hours after spraying, 200 ml of artificial rain was treated per pot, and after air drying, 200 ml of artificial rain was further processed. After the artificial rain treatment, the true leaves were collected, and the quaternary ammonium salts remaining on the leaf surface were extracted with chloroform, quantified by liquid chromatography, and the residual amount per leaf area was measured. The residual degree was calculated by the following equation.

Table 2 shows the results.

Example 2 (Pharmaceutical test) Each prescription drug having a quaternary ammonium salt concentration of 5000 ppm was sprayed on each of 10 pots at the two leaf stage of soybean true leaf, and the occurrence of phytotoxicity was examined 5 days after spraying. The degree of phytotoxicity was divided into four stages and indicated by the following indices. The results are shown in Table-3.

3 Leaf withering 2 Browning occurs 1 Slight browning 0 Healthy Example 3 (Efficacy test against gray mold disease) The cucumber was sprayed with the drug of each formulation during the second to third leaf stages so that the concentration of the quaternary ammonium salt became 250 ppm, air-dried, and then spore-suspended with the gray mold fungus. The suspension was sprayed. Humidity 98%,
After culturing at 25 ° C. for 24 hours, the cells were transferred into a greenhouse, and the number of lesions after 4 days was investigated to calculate a control value.

The results are shown in Table-4.

Claims (2)

(57) [Claims] 1. A quaternary ammonium represented by the general formula (I)
A fungicide for agricultural and horticultural use containing salt as an essential component.(Where R₁, R_Two, R_ThreeIs at least one straight chain having 8 to 30 carbon atoms
Or a branched-chain alkyl or alkenyl group, with the balance being-
CH_Three, −CH_TwoCH_Three, Wherein n is 1 to 5,
R_FourIs -CH_ThreeOr -CH_TwoCH_Three, Counter ion X Is a degree of polymerization of 3 or more
Anionic residue of the acid of the anionic oligomer or polymer
Group. ) 2. The fungicide for agricultural and horticultural use according to claim 1, wherein the anionic oligomer or polymer is a compound containing one or more selected from the following 1) to 3). 1) A polymer containing, as an essential component, one or more members selected from the group consisting of unsaturated carboxylic acids and derivatives thereof. 2) A polymer containing styrene sulfonic acid as an essential constituent monomer. 3) A formalin condensate of a sulfonated polycyclic aromatic compound which may have a hydrocarbon group as a substituent.