JPH049307A - Suspension-like germicide composition for agriculture - Google Patents

Abstract

PURPOSE:To obtain the title composition having excellent storage stability, fluidity, dispersibility in water, becoming low viscosity when used and capable of readily discharging from a vessel by blending sulfur which is an active ingredient with two kinds of specific anionic surfactants and other compounds. CONSTITUTION:The aimed composition having thixotropic property and obtained by blending sulfur which is an active ingredient with a naphthalenesulfonic acid based anionic surfactant such as a beta-naphthalenesulfonic acid-formalin condensate, an unsaturate carboxylic acid polymer based anionic surfactant such as a copolymer of maleic acid and isobutylene, a colloidal water-containing aluminum silicate such as colloidal powder of sodium montmorillonite expressed by formula I and water or as necessary further a colloidal silicon oxide expressed by formula II such as minute amorphous grains having 3-100nm average grain size and consisting of a high-purity silicon oxide obtained by rapidly decomposing a vapor-phase or liquid-phase silicic acid source.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a suspended agricultural fungicide composition containing sulfur as an active ingredient.

[Conventional technology]

Conventionally, agrochemical ingredients that are sparingly soluble in water or organic solvents have been used in the form of preparations such as powders and water-containing agents because they are difficult to form into liquids or emulsions. Among these powders, powders have many advantages such as being able to be sprayed as is and being easy to formulate into formulations, but have drawbacks such as the fact that they are often scattered to areas other than the intended area by wind or the like during spraying. In addition, since hydrating agents are diluted in water and sprayed, they have the advantage of using water as a medium to uniformly and efficiently adhere pesticide active ingredients to crops. It has the disadvantage of being unfavorable in terms of safety and health for workers.

On the other hand, in recent years, a suspension agrochemical composition in which a micronized agrochemical active ingredient is dispersed and suspended in a dispersion medium such as water, that is, a liquid preparation form called a sol or a flowable has come to be widely used. Similar to wettable powders, this sol can be diluted with water or sprayed as a undiluted solution. Since this preparation is liquid, it does not form powder when diluted with water, and is easier to measure than wettable powders, making it an excellent preparation form.

By the way, regarding the 1IIfi cloudy pesticide combination pesticide, a fluid, water-insoluble biocide composition (
Japanese Patent Publication No. 53-46889), a fluid biocide composition containing a nonionic surfactant having an aromatic ring substituted with an aryl group or an aralkyl group as a lipophilic group (Japanese Patent Publication No. 55-1
No. 29201), a water-suspended agricultural chemical formulation containing polyoxyethylene alkyl phenol ether, a nonionic surfactant having an alkyl group or an aralkyl group-substituted aromatic ring as a lipophilic group, and a heteropolysaccharide gum (JP-A No. 60 -104002), unsaturated carboxylic acids or derivatives thereof, styrene sulfonates, formalin condensates of sulfonated polycyclic aromatic compounds, or salts thereof, for particle growth suppression. (Japanese Unexamined Patent Publication No. 126101/1983) and the like are known.

However, when producing a suspension agricultural chemical composition containing sulfur as an active ingredient based on these known techniques, since the true specific gravity of sulfur is large, high viscosity is required to maintain suspension uniformity over a long period of time. This makes it difficult to drain the container. In addition, if the viscosity is lowered in consideration of ease of discharge from the container, the fine particles of the active ingredient may settle to the bottom of the container and form a strong hard cake after a long period of time after production, or the dispersed particles may become hard and aggregate. However, there are various problems regarding storage stability, such as difficulty in redispersing it by simply shaking it by hand.

On the other hand, it is also known to use colloidal hydrous aluminum silicate to impart storage stability to suspended agricultural chemical compositions; used in combination with anionic surfactants such as , dialkyl sulfosuccinates, alkyl sulfates, and nonionic surfactants such as polyoxyethylene nonylphenyl ether, polyoxyethylene styrylphenyl ether, and polyoxyethylene sorbitan ester. In some cases, a high viscosity is required as in the case of other thickeners, and if a low viscosity is used in consideration of ease of discharge from the container, fine particles of the active ingredient will settle at the bottom of the container and become hard. There are various problems with storage stability, such as the formation of a cake or the dispersion particles being so hard that they cannot be dispersed simply by shaking them by hand.

[Problem to be solved by the invention]

The purpose of the present invention is to create a suspension agricultural fungicide composition containing sulfur as an active ingredient, which has excellent storage stability, fluidity, and dispersibility in water, in order to solve the above-mentioned problems when using sulfur as an active ingredient. It is about providing something.

[Means to solve the problem]

As a result of extensive research to solve these problems, the present inventors have developed a suspended agricultural fungicide composition containing sulfur as an active ingredient, with two specific anionic surfactants,
The present invention was completed based on the finding that the above object can be achieved by blending colloidal hydrous amyluminum silicate and water, or if necessary, further colloidal silicon oxide.

That is, the present invention is the following suspended agricultural fungicide composition.

(1) Contains sulfur as an active ingredient, and contains a naphthalene sulfonic acid-based anionic surfactant, an unsaturated carboxylic acid polymer-based anionic surfactant, colloidal hydrated aluminum silicate, and water. @ Planar agricultural fungicide composition characterized by:

(2) Contains sulfur as an active ingredient, in addition to naphthalene sulfonic acid-based anionic surfactants, unsaturated carboxylic acid polymer-based anionic surfactants, colloidal hydrated aluminum silicate, colloidal silicon oxide and A suspended agricultural fungicide composition characterized by containing water.

In the present invention, the sulfur used as an active ingredient is used in powder form, and the average particle size is 4 mm or less, preferably 0.1 mm.
~2I! m is desirable.

The naphthalene sulfonic acid-based anionic surfactant used in the present invention is an anionic surfactant derived from naphthalene sulfonic acid or a derivative thereof, such as β
- Naphthalenesulfonic acid formalin condensate, methylnaphthalenesulfonic acid formalin condensate, Schefferic acid formalin condensate.

Creosote oil sulfonic acid formalin condensate or alkylnaphthalene sulfonic acid salt, calcium salt, ammonium salt, triethanolamine salt, etc. may be mentioned.

Unsaturated carboxylic acid polymer-based anionic surfactants are anionic surfactants obtained from polymers of unsaturated carboxylic acids or derivatives thereof, such as acrylic acid polymers and methacrylic acid polymers.

Copolymers of acrylic acid and methacrylic acid, copolymers of acrylic acid and polyoxyethylene methacrylate, copolymers of acrylic acid and acrylic acid methyl ester, copolymers of acrylic acid and vinyl acetate Examples include sodium salts, potassium salts, ammonium salts, and triethanolamine salts of acrylic acid and maleic acid copolymers, maleic acid and isobutylene copolymers, maleic acid and styrene copolymers, etc. It will be done.

One or more types of naphthalene sulfonic acid-based anionic surfactants and unsaturated carboxylic acid polymer-based anionic surfactants can be used, and their blending ratio is determined based on the total amount of the composition. and 0.02 to 1 respectively
5% by weight, preferably 0.05-10% by weight is suitable.

The colloidal hydrated aluminum silicate used in the present invention is a colloidal powder of hydrated aluminum silicate, for example, a colloidal powder of sodium montmorillonite can be used, and as a commercially available product, a colloidal powder of sodium montmorillonite can be used. F (manufactured by Kunimine Kogyo Co., Ltd., trademark), etc. can be used. The blending ratio of colloidal hydrated aluminum silicate is 0.01 to 0.01 to the total amount of the composition.
10% by weight, preferably 0.05-5% by weight is suitable.

In the present invention, colloidal silicon oxide, which is blended as necessary, is a colloidal powder of silicon oxide represented by the formula 5in2·nH2O, which rapidly decomposes the silicic acid source that is normally in the gas or liquid phase. High purity silicon oxide obtained by this method can be used, and extremely small amorphous particles with an average particle size of 3 to OO nm are preferred. The appropriate blending ratio of colloidal silicon oxide is 10% by weight or less, preferably 0.05 to 5% by weight, based on the total amount of the composition.

In the present invention, in addition to the above-mentioned components, thickeners such as xanthan gum, gum tragacanth, guar gum, sodium alginate, sodium carboxymethyl cellulose, sodium carboxymethyl starch, hydroxyethyl cellulose, methyl cellulose and its derivatives, freezing ethylene glycol, etc. Other additives such as inhibitors, defoamers, organic solvents, preservatives and fungicides may be added.

To produce the suspended agricultural fungicide composition of the present invention, first, colloidal hydrated aluminum silicate and colloidal silicon oxide blended as necessary are added to a predetermined amount of water, and the mixture is vigorously stirred with a high-speed stirrer. Stir. Next, add a predetermined amount of coarsely pulverized sulfur to this, add naphthalene sulfonic acid-based anionic surfactants and unsaturated carboxylic acid polymer-based anionic surfactants, and add ethylene glycol, etc. as necessary. Other additives such as antifreeze and antifoaming agents are added and mixed and dispersed using a high speed stirrer. Next, these mixtures are milled using a wet grinder such as a sand grinder until the average particle size of the agricultural chemical ingredient is 4 or less, preferably 0.1 to 0.1.
2. Grind until smooth to obtain a product.

The thus obtained suspended agricultural fungicide composition of the present invention is sprayed as it is or after being diluted with water.

The suspended agricultural fungicide composition of the present invention contains sulfur, a naphthalene sulfonic acid-based anionic surfactant, an unsaturated carboxylic acid polymer-based anionic surfactant, colloidal hydrated aluminum silicate, and water. When blended, it has specific, moderate thixotropic properties, excellent long-term storage stability, low viscosity during use, and excellent container drainage, improving workability for spraying chemicals. Ru.

Furthermore, by adding colloidal silicon oxide to these ingredients, even better physicochemical properties can be obtained.
In particular, since it has excellent redispersibility after storage, the improvement in workability is even more remarkable.

〔Effect of the invention〕

As described above, the suspended agricultural fungicide composition of the present invention contains sulfur, a naphthalene sulfonic acid-based anionic surfactant, an unsaturated carboxylic acid polymer-based anionic surfactant, and a colloidal hydrated silicic acid. Contains aluminum, water, and if necessary colloidal silicon oxide for storage stability and
It has excellent fluidity and dispersibility in water, and also has appropriate thixotropy, so it has a low viscosity during use and can be easily discharged from a container.

[Example〕 Examples and comparative examples of the present invention will be described below.

In each example, % is by weight.

Example 1 Colloidal hydrated aluminum silicate 0.5% in a mixer
Disperse in 40.3% water. Coarsely crush this and f:ja
Add 52% yellow, 2% sodium salt of β-naphthalenesulfonic acid formalin condensate, 0.2% sodium salt of copolymer of maleic acid and isobutylene, and 5% ethylene glycol, and mix and disperse for 30 minutes with a high-speed stirrer. do. Next, the mixture was pulverized using a wet pulverizer to obtain a homogeneous suspended agricultural fungicide composition.

Example 2 Colloidal hydrated aluminum silicate 0.5% in a mixer
and 0.5% colloidal silicon oxide are dispersed in 39.8% water. To this, 52% of coarsely ground sulfur, 2% of the sodium salt of a β-naphthalenesulfonic acid formalin condensate, and 0.0% of the sodium salt of a copolymer of maleic acid and isobutylene.
2% and 5% ethylene glycol were added, and mixed and dispersed for 30 minutes using a high-speed stirrer.

Next, the mixture was pulverized using a wet pulverizer to obtain a homogeneous suspended agricultural fungicide composition.

Example 3 Colloidal hydrated aluminum silicate 0.4% in mixer
, colloidal silicon oxide 0.5% and xanthan gum 0.1
% is dispersed in 38.8% water. To this were added 52% of coarsely ground sulfur, 3% of the sodium salt of methylnaphthalenesulfonic acid formalin condensate, 0.2% of the sodium salt of the copolymer of maleic acid and isobutylene, and 5% of ethylene glycol. Mix and disperse for 30 minutes. Next, the mixture was pulverized using a wet pulverizer to obtain a homogeneous suspended agricultural fungicide composition.

Example 4 Colloidal hydrated aluminum silicate 0.5% in mixer
and 0.5% colloidal silicon oxide are dispersed in 40% water. To this were added 52% of coarsely ground sulfur, 1.5% of the sodium salt of Scheffer's acid formalin condensate, 0.5% of the sodium salt of the copolymer of maleic acid and acrylic acid, and 5% of ethylene glycol, and the mixture was stirred using a high-speed stirrer. Mix and disperse for 30 minutes. Next, the mixture was pulverized using a wet pulverizer to obtain a homogeneous suspended agricultural fungicide composition.

Example 5 1% of colloidal hydrated aluminum silicate is dispersed in 36.9% of water in a mixer. Coarsely crushed sulfur 52%
, 5% ammonium salt of β-naphthalenesulfonic acid formalin condensate, 0.1% sodium salt of copolymer of maleic acid and isobutylene, and ethylene glycol 5
% and mixed and dispersed for 30 minutes using a high speed stirrer. Next, the mixture was pulverized using a wet pulverizer to obtain a homogeneous suspended agricultural fungicide composition.

Example 6 Colloidal hydrated aluminum silicate 0.2% in mixer
is dispersed in 39.8% water. Coarsely crushed sulfur 5
2%, sodium salt of β-naphthalenesulfonic acid formalin condensate 1%, sodium salt of acrylic acid polymer 2%
, and 5% ethylene glycol were added, and the mixture was mixed and dispersed for 30 minutes using a high-speed stirrer. Next, finely pulverize using a wet pulverizer.
A homogeneous suspended agricultural fungicide composition was obtained.

Comparative Example 1 0.1% xanthan gum is dispersed in 39.7% water in a mixer. Add to this 52% coarsely ground sulfur, 3% sodium salt of methylnaphthalenesulfonic acid formalin condensate, and 0 sodium salt of copolymer of maleic acid and isobutylene.
．． 2% and 5% ethylene glycol were added, and mixed and dispersed for 30 minutes using a high-speed stirrer.

Next, it was finely pulverized using a wet pulverizer to obtain a homogeneous W8 cloudy agricultural fungicide composition.

Comparative Example 2 0.2% xanthan gum is dispersed in 39.6% water in a mixer. Add to this 52% coarsely ground sulfur, 3% sodium salt of methylnaphthalenesulfonic acid formalin condensate, and 0 sodium salt of copolymer of maleic acid and isobutylene.
．． 2% and 5% ethylene glycol were added, and mixed and dispersed for 30 minutes using a high-speed stirrer.

Next, the mixture was pulverized using a wet pulverizer to obtain a homogeneous suspended agricultural fungicide composition.

Comparative Example 3 0.5% colloidal silicon oxide and 0.1% xanthan gum are dispersed in 39.2% water in a mixer. To this were added 52% of coarsely ground sulfur, 3% of the sodium salt of methylnaphthalenesulfonic acid formalin condensate, 0.2% of the sodium salt of the copolymer of maleic acid and isobutylene, and 5% of ethylene glycol. Mix and disperse for 30 minutes. Next, the mixture was pulverized using a wet pulverizer to obtain a homogeneous suspended agricultural fungicide composition.

Comparative Example 4 Colloidal hydrated aluminum silicate 0.5% in mixer
and 0.5% colloidal silicon oxide are dispersed in 39.0% water. To this were added 52% of coarsely ground sulfur, 3% of ammonium salt of polyoxyethylene styrenated phenyl ether sulfuric acid, and 5% of ethylene glycol, and mixed and dispersed for 30 minutes using a high-speed stirrer. Next, the mixture was pulverized using a wet pulverizer to obtain a homogeneous suspended agricultural fungicide composition.

Comparative Example 5 0.1% xanthan gum is dispersed in 38.9% water in a mixer. To this were added 52% of coarsely ground sulfur, 4% of polyoxyethylene styrenated phenyl ether, and 5% of ethylene glycol, and mixed and dispersed for 30 minutes using a high-speed stirrer. Next, the mixture was pulverized using a wet pulverizer to obtain a homogeneous suspended agricultural fungicide composition.

Comparative Example 6 0.1% xanthan gum is dispersed in 38.9% water in a mixer. 52% of coarsely ground sulfur, 4% of polyoxyethylene nonylphenyl ether, and 5% of ethylene glycol are added to this, and mixed and dispersed for 30 minutes using a high-speed stirrer.

Next, the mixture was pulverized using a wet pulverizer to obtain a homogeneous suspended agricultural fungicide composition.

Comparative Example 7 Colloidal hydrated aluminum silicate 0.5% in mixer
and 0.5% colloidal silicon oxide are dispersed in 39.8% water. Add to this 52% coarsely ground sulfur, 2% sodium salt of β-naphthalenesulfonic acid formalin condensate, and 0.2% sodium salt of dialkyl sulfosuccinate.
, and 5% ethylene glycol were added, and the mixture was mixed and dispersed for 30 minutes using a high-speed stirrer. Next, finely pulverize using a wet pulverizer.
A homogeneous suspended agricultural fungicide composition was obtained.

Comparative Example 8 0.2% xanthan gum is dispersed in 40.6% water in a mixer. To this were added 52% coarsely ground sulfur, 2% sodium salt of β-naphthalenesulfonic acid formalin condensate, 0.2% sodium salt of dialkylsulfosuccinic acid, and 5% ethylene glycol, and mixed and dispersed for 30 minutes using a high-speed stirrer. . Next, the mixture was pulverized using a wet pulverizer to obtain a homogeneous suspended agricultural fungicide composition.

The following tests were conducted on the suspended agricultural fungicide composition obtained as described above.

Test Example 1 (Viscosity) 50% of the suspended agricultural fungicide compositions produced in Examples 1 to 6 and Comparative Examples 1 to 8 were placed in a 500++Q transparent bottle.
I put in 00m12. Thereafter, the above composition was transferred to a beaker with a volume of 5 (1 mR), and the fluidity at that time was investigated according to the following criteria.

A: Shows low viscosity and good fluidity, and the formulation is easily discharged from the packaging container.

B: Slightly high viscosity, slightly poor fluidity, and a portion of the formulation remains in the container.

C: It is pasty and has almost no fluidity, and the preparation is not discharged from the container.

Test Example 2 (Self-dispersion test) 200 mQ of 3 degree hard water is poured into a 250 m 12 volume graduated cylinder. Next, the suspended agricultural fungicide compositions produced in Examples 1 to 6 and Comparative Examples 1 to 8 were gradually dropped (approximately S drops) from the top of the cylinder using a Komagome pipette, and the formulations were self-dispersed in water. Dispersibility was investigated using the following criteria.

O: Droplets of the formulation are completely and quickly dispersed uniformly in water.

△: The droplets of the formulation were not well dispersed in water, and some of them fell to the bottom of the cylinder. Shaking and stirring are required for dispersion.

X: Droplets of the formulation are hardly dispersed in water and fall directly to the bottom of the cylinder.Test Example 3 (Heat Resistance Test) Examples 1 to 6 and Comparative Example 1 were placed in a 100 J candle bottle.
-80+n of the suspended agricultural fungicide composition produced in 8
After 30 days of storage in a thermostat at 40°C,
The 0-candle bottle was inverted to investigate redispersibility, and using microspertyl, it was observed whether a hard cake layer was formed at the bottom of the candle bottle.

The criteria for this judgment are as follows.

Redispersibility O: Good fluidity and does not require redispersion.

O: The liquid level does not move, but it is easily dispersed by shaking lightly.

Δ...The liquid level does not move, but is dispersed by strong vibration.

×...Does not disperse even if shaken strongly.

hard caking −・No hard cake.

+...Hard cakes less than 1+am available.

++...Hard cakes over 1m @ available.

Test Example 4 (Separation degree) 90 m of the suspended agricultural fungicide compositions produced in Examples 1 to 6 and Comparative Examples 1 to 8 were placed in a 100 mQ candle bottle.
After storing in a thermostat at 40℃ for 30 days,
The degree of separation was measured.

The degree of separation is expressed as the ratio (%) of the separation (clear part) volume (mQ) to the total sample volume (+n12).
It is expressed as

The results of the above Test Examples 1 to 4 are shown in the table, and it can be seen that even the six machines have excellent effects such as good dispersibility in water and marked improvement in workability for spraying chemical solutions.

Claims (5)

[Claims] (1) Contains sulfur as an active ingredient, and contains a naphthalene sulfonic acid-based anionic surfactant, an unsaturated carboxylic acid polymer-based anionic surfactant, colloidal hydrated aluminum silicate, and water. A suspended agricultural fungicide composition characterized by: (2) Contains sulfur as an active ingredient, in addition to naphthalene sulfonic acid-based anionic surfactants, unsaturated carboxylic acid polymer-based anionic surfactants, colloidal hydrated aluminum silicate, colloidal silicon oxide and A suspended agricultural fungicide composition characterized by containing water. (3) The naphthalene sulfonic acid-based anionic surfactant is a β-naphthalene sulfonic acid formalin condensate, a methylnaphthalene sulfonic acid formalin condensate, a Scheffuric acid formalin condensate, a creosote oil sulfonic acid formalin condensate, and an alkylnaphthalene sulfone. The agricultural fungicide suspension composition according to claim 1 or 2, which is one or more selected from the group consisting of acid sodium salts, calcium salts, ammonium salts, and triethanolamine salts. (4) The unsaturated carboxylic acid polymer anionic surfactant is acrylic acid polymer, methacrylic acid polymer, copolymer of acrylic acid and methacrylic acid, polyoxyethylene acrylic acid and methacrylate copolymer with ester,
Copolymer of acrylic acid and acrylic acid methyl ester,
Sodium salts, potassium salts, ammonium salts of copolymers of acrylic acid and vinyl acetate, copolymers of acrylic acid and maleic acid, copolymers of maleic acid and isobutylene, and copolymers of maleic acid and styrene. The suspended agricultural fungicide composition according to any one of claims (1) to (3), which is one or more selected from the group consisting of salts and triethanolamine salts. (5) The blending ratio of the naphthalene sulfonic acid-based anionic surfactant and the unsaturated carboxylic acid polymer-based anionic surfactant is 0.02 to 15% by weight, respectively, and the blending ratio of the colloidal hydrated aluminum silicate is 0.02 to 15% by weight. The suspended agricultural fungicide composition according to any one of claims (1) to (4), wherein the blending ratio of colloidal silicon oxide is 0.01 to 10% by weight and 10% by weight or less.