JPS58213704A - Fungicidal composition having residual effect - Google Patents

Abstract

PURPOSE:A fungicidal composition having residual effect capable of controlling the volatilization and scattering of an active ingredient, showing residual effect quickly for a long time, obtained by blending a specific fungicidal compound having relatively high vapor pressure at room temperature at the active ingredient with a coumarone-indene resin. CONSTITUTION:A fungicidal compound such as compunds shown by the formula III, formula IV, formula V, etc. shown by the formula I (A is O, S, -CH2-, -CH2 CH2-, -CH=CH-, or group shown by the formula II; X is O or S; R1 is CH3, F, Cl, or Br; R2 is CH3; or R1 and R2 form ethylene or trimethylene) having a relatively high vapor pressure of 1X10<-3>-1X10<-5>mm.Hg (25 deg.C) as an active ingredient is blended with a coumarone-indene resin having compatibility with it in an amount to give >=0.1 as much as the active ingredient, properly 1-40 times as much as the active ingredient with respect to biological effect and economic efficiency. The mixture is blended with a carrier, auxiliary, etc., manufactured into a preparation, and can be applied to plants to control pathogenic fungi.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula
-1-CH,=, CH- or 1□ represents CH,, F, C4, Br, R2
represents CH. However, R1 and R2 may be bonded to each other to form an ethylene or trimethylene group. ] A sterilization method characterized by using a sterilizing compound with a relatively high vapor pressure as shown in the following as an active ingredient, and adding coumaron-indene resin (hereinafter abbreviated as coumaron resin) to this compound at least 0.1 times the amount of the active ingredient. The present invention relates to a composition (hereinafter referred to as the composition of the present invention).

Emulsions, flowables, powders, and wettable powders containing as active ingredients compounds that have a relatively high vapor pressure at room temperature as described in the present invention;
When fine granules or granules are applied to plants, there is a drawback that the active ingredients are volatilized and dissipated due to the rise in plant leaf surface temperature, especially in summer, and the period of residual effect of the solution is significantly shortened.

The present inventors have conducted various studies in order to compensate for the above-mentioned drawbacks of volatilization and dissipation with respect to sterilizing compositions containing sterilizing compounds with relatively high vapor pressure as active ingredients. The present invention has been completed based on the discovery that by adding coumaron resin to a sterilizing agent, a bactericidal composition can be obtained which can control the volatilization and dissipation of the active ingredient and exhibit an immediate and long-term residual effect.

The coumaron resin mentioned in the present invention is a polymerized product of coumaron, indene, styrene, etc. contained in the fraction of coal tar naphtha at a temperature of about 150 to 200°C, and the composition ratio of each component varies. Many properties such as average molecular weight, softening point, and viscosity vary depending on the polymerization conditions. Generally, those with an average molecular weight of about 300 or less are liquid and are called liquid coumaron resins, and those with an average molecular weight of about 300 or more are solid.

These coumaron resins are the active ingredients of the present invention.
Compatible with compounds. The amount of coumarone resin to be added may be 0.1 times or more relative to the active ingredient, but 1 to 40 times is appropriate from the viewpoint of biological effects and economical efficiency.

In addition, the sterilizing compound with relatively high vapor pressure as used in the present invention is
It is a compound having a vapor pressure in the range of 1×10-3 to 1×10-5 mm 1 g (25° C.), and examples of such compounds include JP-A-53-32117 and JP-A-53
++50329, JP 53-91134, JP 53-91135, JP 55-10589, JP 53-91136, JP 54-405
46 Publication, Special Publication No. 54-32787, Special Publication No. 54-
32788 Publication, Japanese Patent Publication No. 55-16585, Japanese Patent Publication No. 54-03087, Japanese Patent Publication No. 54-26553,
JP-A-54-90182, JP-A-54-90183
Publication, JP-A-54-105233, JP-A-54-1
Examples include compounds described in JP-A-54-132232, JP-A-54-132597, and JP-A-54-132,597.

When adding maron resin as described above, the active ingredient may be dissolved or dispersed in the liquid coumaron resin, or the solid coumaron resin and the active ingredient may be mixed under heating and then cooled and ground to form a fine powder. Alternatively, the active ingredient may be dissolved in various solvents, and then a liquid coumaron resin or a solid coumaron resin may be added thereto and dissolved therein. Formulations that increase the control effect against plant pathogenic bacteria as described in the present invention using these materials can be easily implemented as described below without any conventional methods.

In the case of emulsions and oils, the active ingredient is dissolved in liquid coumaron resin and then a surfactant or various solvents are added if necessary, or the active ingredient is dissolved in various solvents and solid coumaron resin is added thereto. After dissolution, a surfactant may be added if necessary. In the case of a flowable system, the active ingredient, liquid coumaron resin, surfactant, and water-soluble polymer are ground and uniformly dispersed together with water using a colloid mill, sand mill, etc., or the active ingredient is mixed with solid coumaron resin by heating and then cooled. It can be obtained by pulverizing and uniformly dispersing a substance together with a surfactant, a water-soluble polymer, and water using a colloid mill or sand mill. For solid preparations such as powders, wettable powders, microgranules, and granules, the active ingredient is dissolved in liquid coumaron resin, or the active ingredient is heated and mixed with solid coumaron resin and then cooled to form a fine powder. The material can be expanded with mineral powder and, if necessary, a surfactant can be added.

Next, when formulating the composition of the present invention, it is possible to add the following as auxiliary agents, and this does not pose any hindrance to the present invention.

In other words, solvents include aromatic solvents such as benzene, toluene, xylene, solvent naphtha, etc., which are compatible with Coumaron resin, some alcohol solvents such as n-butyl alcohol and glycerin, chlorinated solvents such as chlorinated paraffin, and dioxane. , isophorone, and cyclohexane.

As carriers, there are many mineral fine powders such as kaolinite clay, pyrophyllite, sericite, acid clay, bentonite, talc, diatomaceous earth, calcium carbonate, and synthetic hydrated silicic acid. Dispersants, wetting agents, and emulsions are not particularly limited, but examples include alkylbenzene sulfonates, alkyl sulfate ester salts, polyoxyethylene alkylaryl sulfate ester salts, polyoxyethylene alkylaryl ether phosphate ester salts, and naphthalene sulfonates. Anionic surfactants such as sulfonic acid formalin conjugates, dialkyl sulfosuccinates, lignin sulfonates, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, sorbitan fatty acid esters, polyethylene glycol fatty acid esters, fatty acid monoglycerides, Nonionic surfactants such as sugar esters, polyoxyethylene, and polyoxybrobylene block copolymer can be used.

Examples of the stabilizer include antioxidants, ultraviolet absorbers, hydrolysis inhibitors, masking agents, and the like.

Further, other fungicides, insecticides, and herbicides may be mixed as necessary.

Next, examples of typical active ingredients used in the composition of the present invention and methods for preparing the composition will be shown, and some test examples will be compared with commonly used compositions to demonstrate the effectiveness of the composition of the present invention. do. However, the present invention is not limited to these embodiments. In addition, active ingredients will be indicated by numbers below.

\ \, ゝ-1, \ Table 1 Example 1 Active ingredient + 1) 10 parts, 30 parts of solid Coumaron resin (Mitsubishi Kumaron NG: Mitsubishi Kasei) with an average molecular weight of about 5oo, 50 parts of Kawakazole, 3 parts of dodecylbenzenesulfonic acid calcium salt A 10% emulsion is obtained by stirring and mixing 1 part and 7 parts of polyoxyethylene alkylaryl ether. Similarly, 10% emulsions of active ingredients (2) to (5) are obtained.

Test example! A rice blast control test was conducted using the five emulsions prepared in Example 1.

That is, rice grown in Qaa pots (variety Kinki 33)
At the 4th to 5th leaf stage), these compositions of the present invention in emulsion form were sprayed using a spray gun so that the chemical solution was sufficiently attached to the leaf surface.

10 days after spraying, this pathogenic bacterium (Pyricularia or
The plants were inoculated by spraying with a spore solution of A. yzae) and placed in a constant temperature room at 24 to 26° C. and a humidity of 90° C., and after 4 days, the degree of disease was determined by the percentage of lesion area and the control effect was investigated. I will show the results to my wife. The control value was calculated using the following formula.

□ Medium 2; Table 2 Comparative Example 1 A 10% emulsion is obtained by stirring and mixing 1110 parts of active ingredient + 80 parts of kawakazole, 3 parts of dodecylbenzenesulfonic acid calcium salt, and 7 parts of polyoxyethylene alkylaryl ethyl. . Similarly active ingredient (2)
~ (5) 1(1) emulsions are obtained. These emulsions also meet Test Example 1.
Table 3 Example 2 2 parts of active ingredient (1) were dissolved in 8 parts of liquid coumaron resin (Nippon Steel Rimaron L-20: Nippon Steel Chemical Co., Ltd.) having an average molecular weight of 200 to 300, and kaolinite clay (Fubasami Clay) was dissolved in this. x pieces;) 88 parts of Fuba Samiklay) and 2 parts of calcium lignosulfonate were added and mixed uniformly to obtain a 2-chi powder. Similarly active ingredient (2)
~(5) 2') Obtain a powder.

Test Example 2 A rice blast control test (residual effect) was conducted for each of the powders prepared in Example 2.

In other words, rice grown in a 9cm flower pot (variety: Kinki 33)
At the 4th to 5th leaf stage), these compositions of the present invention in powder form were applied using a midget duster at a rate of 3KF/101.

14 days after spraying, this pathogenic bacterium (Pyricularia o
ryzae) was spray inoculated at 24-26℃ and humidity 9.
The specimens were placed in a thermostatic chamber with a temperature of 0g6 or more, and after 4 days, the lesion area ratio was calculated as follows.

Table 4 Comparative Example 2 96 parts of kaolinite clay and 2 parts of calcium gutsulfonate were added to 2 parts of active ingredient (1) and mixed uniformly to obtain a 2-chi powder. Similarly, 2 of (2) to (5)
% powder is obtained. A rice blast control test (residual effect) was conducted on each of the powders thus prepared in the same manner as in Test Example 2, and the results are shown in Section 5s.

Table 5 Example 3 80 parts of water was added to 11,110 parts of the active ingredient, 3 parts of polyvinyl alcohol (Bonsenol KH20: Nippon Gosei), 2 parts of sorbitan triolate (Span 85: Kao Soap) and 5 parts of liquid coumaron resin, and the mixture was washed in a sand mill. By uniformly dispersing the mixture, a 10-thiefroutable agent is obtained. Similarly, a 10-tifluorophilic agent containing the active ingredient (3) is obtained.

Test Example 3 A rice blast control test was conducted using the two types of flowable agents formulated in Example 3.

In other words, rice grown in 91 flower pots (Kinki No. 33, 4-5)
Leaf stage) I The composition of the present invention in the form of a flowable preparation was sprayed using a spray gun so that the chemical solution sufficiently adhered to the leaf surface. After 10 days of spraying, this pathogenic bacterium (Pyricular
Ia oryzae) spore liquid was spray inoculated, and 2
6 Control Example 3 Add 85 parts of water to 11,110 parts of active ingredient, 3 parts of polyvinyl alcohol, and 2 parts of sorbitan triolate, and homogenize with a mill. A 101 flowable agent is obtained by dispersing. Similarly, a 10-tifluorophilic agent containing the active ingredient (3) is obtained.

Test table 7 for each powder prepared in this manner Example 4 5.0 parts of active ingredient (3) and 5 parts of liquid coumaron resin were mixed in a mortar. ) 5 parts, diatomaceous earth (Radiolite'
50 by uniformly mixing 41 parts of 200 (Showa Kagaku), 2 parts of calcium lignosulfonate (SanxP-201: Outumi pulp), and 2 parts of sodium lauryl sulfate.
Obtain a hydrating agent. Similarly, 501 hydrating agent (4) is obtained.

Test Example 4 A rice blast control test (residual effect) was conducted for each of the wettable powders prepared in Example 4.

In other words, rice grown in 91 pots (variety: Kinki 33)
No. 4 to 5 leaf stage) 1 The composition of the present invention in the form of a wettable powder was sprayed using a spray gun so that the leaf surface and the chemical solution were sufficiently attached.

10 days after spraying, this pathogenic bacterium (Pyricularia or
The spore liquid of S. yzae) was spray inoculated and placed in a constant temperature room at 24-26° C. and a humidity of 90° C., and after 4 days, the disease severity was determined based on the bed area ratio and the control effect was investigated. The results are shown in Table 8. The control value was calculated in the same manner as in Test Example 1.

Table 8 Comparative Example 4 13150 parts of active ingredient, 5 parts of synthetic hydrated silicic acid, 4 parts of diatomaceous earth
6 parts of calcium lignosulfonate, 2 parts of sodium lauryl sulfate, and 2 parts of sodium lauryl sulfate are uniformly mixed to obtain a 50-pound hydrating powder. Similarly, 50% of a hydrating powder containing the active ingredient (4) was obtained. The rice blast disease control test (residual effect) was conducted on each of the wettable powders prepared in this manner in the same manner as in Test Example 4, and the results are shown in Table 9.

Table 9 Example 5 8 parts of active ingredient (1) are added to 10 parts of solid coumaron having an average molecular weight of about 500, heated and mixed, then cooled and ground into a fine powder. After adding 79.8 parts of kaolinite clay, 0.2 parts of sodium lauryl sulfate, and 2 parts of polyvinyl alcohol (Gohsenol NL-Q5: Nippon Gosei) as a 10% aqueous solution, the mixture was mixed, granulated, dried, and sieved. Separate to obtain 8% granules. Similarly, 8% granules are obtained.

Test Example 5 A rice blast control test (residual effect) was conducted for each of the granules prepared in Example 5.

1150001 rice cultivated with water using Wagnerbot (
These compositions of the present invention in the form of granules were applied to the water surface during the early Asahi (5th to 6th leaf stage). Granules contain 10 active ingredients per 10 ares.
The water was applied uniformly to the water surface so that the temperature reached 0 F, and the water was kept at a depth of 4 to 5 depths in a greenhouse until the pathogen was inoculated. 7 and 40 days after application of the drug, this pathogenic bacterium (Pyricular
iaoryxae) spore liquid was spray inoculated.
It was placed in a constant temperature room at 26° C. and a humidity of 901 or more, and the calculation of the pesticidal value was performed in the same manner as in Test Example 1.

Table 10 Comparative Example 5 After mixing 8 parts of the active ingredient (1), 0.2 parts of sodium lauryl sulfate, and 89.8 parts of kaolinite clay, 10 parts of polyvinyl alcohol (Gohsenol NL-Q5: Nippon Gosei) was added. It is added as an aqueous solution, mixed, granulated, dried, and sieved to obtain 8% granules. Similarly, active ingredient (3) 81
Obtain granules. Each granule prepared in this manner is shown below.

Table 11 Example 6 1 part of active ingredient (2), 60 parts of liquid coumaron resin, and 37 parts of aromatic hydrocarbon solvent (Tsurupez-150=Etsuso Standard) are uniformly dissolved and mixed to obtain a 1% oil solution. Similarly, an oil preparation containing the active ingredient (3) is obtained.

Test Example 6 A rice blast control test (residual effect) was conducted for each oil prepared in Example 6.

Rice grown in 90 flowerpots (Kinki No. 33 = 4-5 leaf stage)
These compositions of the present invention in oil form were sprayed using a spray gun at a rate of 5 to 71 pots. 14 days after spraying, the spore liquid of this pathogen (Pyricularla oryzae) was spray inoculated, placed in a constant temperature room at 24-26℃ and humidity of 90ts or more, and after another 4 days, according to the lesion area ratio Table 1
2. A 1% oil solution is obtained by uniformly dissolving and mixing 1 part of the active ingredient (2) and 99 parts of an aromatic hydrocarbon solvent. Similarly, 11 oil preparations containing active ingredient (3) were obtained.

Test coat 1 for each oil prepared in this way.
3

Claims (1)

[Claims] General formula [wherein, A ha0 , S , -CH2, -CH2CH
2-. CH, , CH- or , k represents CH, , F , Q e Rr , and R2 represents α. In addition, ", * RQ may be combined with each other to form an ethylene or trimethylene group.] The active ingredient is a bactericidal compound with a relatively high vapor pressure, and coumarone-indene 1131N is added to this as an active ingredient. A sterilizing composition characterized in that 0.1 times or more of sterilization is added.