JPH02279607A - Aqueous suspension-like biocidal composition - Google Patents

Abstract

PURPOSE:To obtain an aqueous suspension-like biocidal composition excellent in preservation stability without causing breakage of emulsions or deposition of crystals by adding a specific compound as a crystal deposition inhibitor thereto. CONSTITUTION:An aqueous suspension-like biocidal composition obtained by adding a compound expressed by formula II (R1 is 2 to 4C alkylene; R2 is 6 to 18C alkyl or 6 to 18C alkenyl; (m) and (n) are 0 to 100), e.g. a polyoxyalkylene bisphenol A or di- or monoalkyl ester of bisphenol A, at 0.05 to 20, preferably 0.1 to 10 weight ratio based on a compound expressed by formula I (R is 6 to 18C alkyl or 6 to 18C alkenyl) to a composition prepared by suspending particles of the compound expressed by formula I which is a germicide having a wide range of spectrum in water. The abovementioned composition is prepared by adding a mixed melt of the compounds expressed by formulas I and II is water containing a water-soluble or water-suspendible synthetic polymer compound or/and surfactant dissolved therein and stirring the resultant mixture.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an aqueous suspension biocide composition, and more particularly to an aqueous suspension biocide composition that does not undergo crystal precipitation during storage. relating to things.

[Conventional technology and its problems]

When a biocidal drug substance having a melting point of 30 to 100' C is made into a fluid suspension with water as a continuous phase, - numerically water-soluble or water-suspended synthetic polymer compounds, anionic surfactants, 5 to 20 by combining nonionic surfactants, etc.
Suspensions having particle sizes of the order of m+ can be prepared.

However, when the melting point of the biocide drug substance is 30 to 100"C, crystal changes occur within the emulsified particles when a high temperature (60 °C)/low temperature (-20 °C) storage cycle test is performed. , crystal precipitation may occur along with emulsion damage.

For example, since the melting point of the compound represented by the following formula +I+ (wherein R represents an alkyl group or alkenyl group having 6 to 18 carbon atoms) is 92°C to 96°C, conventional methods cannot There was significant crystal precipitation, making it difficult to form an aqueous suspension biocide.

[Means to solve the problem]

As a result of various studies on emulsion stabilization methods, the present inventors have found that an aqueous suspension biocide composition containing a compound represented by the above formula -+I+ as a biocide has the following general formula flll (! (R1 is carbon (represents an alkyl or alkenyl group of numbers 6 to 18, m and n each represent a number of 0 to 100).
) and low temperature (-20''C) storage cycle test, it was found that an aqueous suspension biocide without emulsion breakage or crystal precipitation could be obtained, and the present invention was completed.

That is, the present invention provides an aqueous suspension biocide composition in which particles of a compound represented by the formula t1+ are suspended in water, and a compound represented by the formula ill is added to the compound represented by the general formula ill. The present invention provides an aqueous suspension biocide composition characterized in that the composition is added in a weight ratio of 0.05 to 20.

(In the formula, R represents an alkylene group having 2 to 4 carbon atoms. (In the formula, R represents an alkyl group or alkenyl group having 6 to 18 carbon atoms.) (In the formula, R represents an alkylene group having 2 to 4 carbon atoms. an alkylene group, R2 represents an alkyl or alkenyl group having 6 to 18 carbon atoms;
..., n each represent a number from 0 to 100. ) The compound represented by -a2fi+ is a fungicide with a wide spectrum. 1. The compound represented by formula il+ is improved in its adhesion to plants by changing the counter ion to alkylbenzenesulfonic acid. It has more stable bactericidal efficacy and has significantly improved the occurrence of phytotoxicity to plants.

As the crystal precipitation inhibitor represented by the general formula (■) used in the present invention, polyoxyalkylene bisphenol A
or di- or mono-alkyl esters of bisphenol A. These compounds represented by the formula (n) are present in an aqueous suspension film (V) in a weight ratio of 0.05 to 20, preferably 0. .1 to 10.

The compounding amount of the compounds represented by formulas +I+ and +Il) in the aqueous suspension biocide composition of the present invention is 10 to 5, respectively.
Suitable amounts are 0% by weight and 5-50% by weight.

The biocide composition of the present invention is prepared by conventionally known methods. That is, - a mixed melt of a biocide compound represented by formula 111 and a crystal precipitation inhibitor compound represented by general formula ([l)] is mixed with a water-soluble or water-suspended synthetic polymer compound or/and an interface. Add the active agent to the water and stir.
An aqueous emulsion is obtained. Specific examples of such water-soluble or water-suspended polymer compounds include acrylic acid polymers, vinyl acetate polymers and saponified products thereof, copolymers of acrylic acid and acrylic acid methyl ester, and copolymers of acrylic acid and maleic acid. Examples include copolymers, copolymers of itaconic acid and vinyl acetate, and copolymers of styrene and maleic acid.

In addition, as surfactants, polyalkylene oxide nonionic surfactants such as polyoxyalkylene alkyl ether and polyoxyalkylene alkylaryl ether; alkyl sulfates, polyoxyalkylene alkyl sulfates, and polyoxyalkylene phosphate ester salts Examples include anionic surfactants such as; cationic surfactants such as alkyltrimethylammonium salts; and amphoteric surfactants such as alkylbetaine and alkyldimethylamine oxide.

Further, other optional components such as hydrophobic organic solvents such as kerosene and chili oil can be added to the aqueous suspension biocide composition of the present invention, if necessary.

(Effects of the Invention) By using the aqueous suspension biocide composition of the present invention, a biocide emulsilane with excellent storage stability can be obtained.

This is presumed to be because the crystal precipitation inhibitor in the biocide composition bleeds onto the surface of the biocide and modifies the surface of the biocide.

(Examples) The present invention will be explained in more detail in the following examples, but the present invention is not limited to these examples.

Example 1 10 parts by weight of compound (A) as a crystal precipitation inhibitor and a compound represented by the general formula +1+ (R=C+J
zs) and 20 parts by weight are mixed and melted.

Vinyl acetate polymer (molecular weight approximately 20,000, degree of saponification 40%) 1
Parts by weight of polyoxyethylene (10 mol) and 3 parts by weight of polyoxyethylene (10 mol) oleyl ether were dissolved in water, and the mixed melt of the crystal precipitation inhibitor and biocide active substance was gradually added while stirring with a homomixer. to obtain a suspension agent (a).

Example 2 15 parts by weight of compound (B) and 5 as a crystal precipitation inhibitor
As a biocidal drug substance, a compound represented by the general formula (1+ (R=C
+zHzs) and 30 parts by weight are mixed and melted.

Mix the crystal precipitation inhibitor and biocide active substance in a solution of 2 parts by weight of polyoxyethylene (15 mol) lauryl ether sodium sulfate and 1 part of polyoxyethylene (10 mol) nonylphenyl ether 3fK in water. The melt is gradually added to the homomixer while stirring to obtain a suspension (b).

Example 3 8 parts by weight of compound (C) as a crystal precipitation inhibitor and a compound represented by the general formula +1+ (R=CtzH
zs) and 40 parts by weight are mixed and melted.

A mixed melt of the crystal precipitation inhibitor and biocidal substance was gradually poured into a solution of 3 parts by weight of cetylmethylammonium chloride and 2 parts by weight of lauryl betaine in water while stirring with a homomixer. , to obtain a suspension (C).

Comparative Example 1 10 parts by weight of xylene as a crystal precipitation inhibitor and 20 parts by weight of a compound represented by the general formula +1+ as a biocidal raw material are mixed and melted.

Vinyl acetate polymer (molecular weight approximately 20,000, degree of saponification 40%) 1
Part by weight and 4 parts by weight of polyoxyethylene (10 mol) oleyl ether were dissolved in water, and the mixed melt of the crystal precipitation inhibitor and biocidal raw material was gradually added while stirring with a homomixer. to obtain a suspension (d).

Comparative Example 2 In a solution of 2 parts by weight of polyoxyethylene (15 mol) lauryl ether sodium sulfate and 1 part of polyoxyethylene (10 mol) nonylphenyl ether 3fi dissolved in water, a biogenic substance represented by the formula -+11 was added. Add 30 parts by weight of the compound and stir with a homomixer to form a suspension agent (e)
Suspension rate (%) to obtain - These evaluation results are shown in Table 1.

Test Example 1 Suspension agent obtained in Examples 1, 2.3 and Comparative Example 1.2 (
a) to (e) at -20°C for 3 days at 50°
A storage test was conducted in which one cycle was 3 days, and changes in particle size, viscosity, presence or absence of crystal precipitation, and changes in suspension stability of each suspension were investigated after oral administration.

*Particle size: Measured using a Coulter counter.

*Viscosity Measured with a Type 2 B viscometer (30 rpm +/20″C).

*Crystal precipitation: Observation with an optical microscope (X400).

*Suspension stability: Put the suspension agent in a cylinder with an inner diameter of 2Ω and a height of 10cm.
Find the suspension rate using the following formula.

Furthermore, the following tests were conducted to examine the medicinal efficacy of the suspension, and it was confirmed that it is effective as a bactericidal agent.

Test Example 2 Control test against rice sesame leaf blight> Diameter 9c
Suspension agents (a) to (C) obtained in Examples 1 to 3 were sprayed on rice at the 3rd to 4th leaf stage (variety: Koshihikari) grown in m+ pots, and after air drying, the rice was infected with sesame leaf blight. The spore suspension was inoculated by spray.

Five days after inoculation, the number of lesions on the uppermost leaves at the time of chemical application was investigated, and the control value was calculated using the following formula.

Control value (%) = These evaluation results are shown in Table-2.

Note) 'l' I EDDP: Edifenfuos (-
(Ship name), 0-ethyl-3,S-diphenylphosphorodithioate (Chemical name) As shown in Table 2, the suspending agent of the present invention is different from the control EDD.
It showed a pest control effect 1000 times better than that of P emulsion.

Test Example 3 Apple Spot Leaf Disease Control Test> The suspension agents (a) to (C) obtained in Examples 1 to 3 were sprayed on a heavily pruned apple tree (variety Starking), and after air-drying, 3 drops were applied from the tip. Cut the parent shoot to a length of about 20 CTll with the leaves still attached.
I used a 100-inch Erlenmeyer flask as a water jug. This was spray-inoculated with a spore suspension of leaf spot fungus and placed in a greenhouse at 25°C for 2 hours.
After wearing it for 0 hours, it was left in a room at 25°C, and the number of lesions was examined 2 days later. The control value at this time was determined in the same manner as in Test Example 1.

The results are shown in Table-3.

As shown in Table 3, the suspension of the present invention was shown to be effective against apple leaf spot leaf disease with the same effect as the control cabtan/organic copper hydrating agent.

Test Example 4 <Peach gray star disease control test> Suspension agents (a) to (C) obtained in Examples 1 to 3 were applied to peach fruit.
), and after air-drying, the fruit was wounded in one place with a needle, and the spore suspension was inoculated by drip. Place this peach in a greenhouse at 25°C.
Five days later, the severity of disease onset was investigated, and the disease onset rate was determined. The test score was 20 in 1 ward.

The results are shown in Table-4.

Table note) '4'27PN: Tetrachlorophthalonitrile As shown in Table 4, the suspending agent of the present invention
It was shown to be superior to N-permanent agents and more effective against Haisei disease.

Claims (1)

[Claims] 1. A compound represented by the general formula (II) is added to an aqueous suspension biocide composition in which particles of the compound represented by the general formula (I) are suspended in water. An aqueous suspension biocide composition characterized in that it is added in a weight ratio of 0.05 to 20 relative to the compound represented by I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R represents an alkyl group or alkenyl group having 6 to 18 carbon atoms.) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula , R_1 is an alkylene group having 2 to 4 carbon atoms, R_1 is an alkylene group having 2 to 4 carbon atoms,
2 represents an alkyl group or alkenyl group having 6 to 18 carbon atoms, and m and n each represent a number from 0 to 100. )