KR100764044B1 - Aqueous suspension pesticide preparation - Google Patents

Abstract

It is not only excellent in storage stability in storage conditions with large temperature changes due to long periods between seasons, but also excellent for long-term storage of winter season when temperature changes in the range of 5 ° C to -10 ° C with short periods between day and night. An aqueous suspension type pesticide preparation of 1,1'-iminiodi (octamethylene) diguanidinium = tris (alkylbenzenesulfonate) having storage stability is represented by (b) general formula (1)

RO- (CH ₂ CH ₂ O) _n -H

(Wherein R represents an alkyl group having 8 to 18 carbon atoms and n represents an integer of 0 to 4), the compound represented by (c) phospholipid and (d) an alkyl group having 6 to 20 carbon atoms Branch contains a surfactant and (e) water,

Said (c) phospholipid is hydrogenated phospholipid whose iodide is 20 or less.

Aqueous suspended pesticide formulations, surfactants, phospholipids, water soluble proteins, iodide, dispersion stabilizers.

Description

Aqueous Suspension Pesticide Formulation {AQUEOUS SUSPENSION PESTICIDE PREPARATION}

The present invention provides an aqueous suspension pesticide formulation having excellent stability against cyclic temperature changes in the low temperature region, wherein 1,1'-iminiodi (octamethylene) diguanidinium = tris (alkylbenzenesulfonate) is an active ingredient. It is about.

Pesticide active ingredient 1,1'-iminiodi (octamethylene) diguanidinium = tris (alkylbenzenesulfonate) of the formulation according to the present invention is known as an excellent agricultural horticultural fungicide (Japanese Patent Publication No. 2-7564, U.S. Patent No. 4,659,739), in particular, 1,1'-iminiodi (octamethylene) diguanidinium = tris (alkylbenzene) having 10 to 13 carbon atoms as the main component of the alkyl chain of alkylbenzenesulfonate having 12 carbon atoms Sulfonate) (melting point 92 DEG C to 96 DEG C) is named iminottadine albesylate salt, and has been put to practical use as an agricultural horticultural fungicide having a broad spectrum.

In general, in the case of formulating a pesticide raw material which is solid at room temperature as an aqueous suspension pesticide, a suspension formulation is prepared by combining a water-soluble or water-suspendable synthetic polymer, an anionic surfactant, a nonionic surfactant, or the like. I can prepare it.

However, when the suspension-type preparation in which the pesticide element having a melting point of 30 ° C to 100 ° C is suspended under severe temperature difference conditions, the dispersed solid element melts or solidifies, so that the dispersed state collapses with crystal growth. In addition, suspending agents (emulsions) in which the pesticide raw material is dissolved in a commonly used water-insoluble organic solvent and emulsified in water also crystallize the pesticide raw material in minute droplets dispersed in water. There was problem that this occurred.

1,1'-iminiodi (octamethylene) diguanidinium = tris (alkylbenzenesulfonate), which is an active ingredient of the pesticide used in the present invention, also has a significant crystallization in a conventionally known method in the formulation processing of pesticide raw materials. It was difficult to make stable aqueous suspension preparation. That is, in the suspension suspension preparation, solidification or crystallization of the active ingredient of the pesticide occurs, and the dispersed state is destroyed. Moreover, since the said pesticide active ingredient is remarkably insoluble in the water-insoluble organic solvent normally used, emulsification was also difficult.

For this reason, the present inventors have described (a) 1,1'-iminiodi (octamethylene) diguanidinium as described in Japanese Patent Application Laid-Open No. 8-225402 (spec. US Patent No. 5,728,734). Tris (alkylbenzenesulfonate), (b) As a dispersion stabilizer, General formula (1)

RO- (CH ₂ CH ₂ O) _n -H

(Wherein R represents an alkyl group or alkenyl group having 8 to 18 carbon atoms, n represents an integer of 0 to 4), or a phospholipid, (c) an alkyl group having 6 to 20 carbon atoms, or An aqueous suspended pesticide formulation containing a surfactant having an alkenyl group, and (d) water was developed.

The aqueous suspension pesticide preparation is a long-term storage test at 50 ℃, a long-term storage test at -5 ℃, and under severe temperature difference, specifically three days of high temperature (50 ℃) and 3 days of low temperature (-10 ℃) As a result of a long-term preservation test for 12 weeks by the cycle preservation test, the active ingredient is not separated and precipitated, and a stable suspension state is maintained, so that the aqueous suspension has excellent stability and high safety for the environment and users. It was thought to be a type pesticide preparation.

However, it has been found that the formulation is weak against temperature changes at low temperatures. That is, in the cold region, day and night temperature changes occur periodically and day by day in the range of 5 ° C. to 10 ° C. in winter, but when the preparation is stored for a long period of 3 to 4 months in the winter period, the preparation Good fluidity was not restored until the viscosity became high or solidified into a creamy state while the suspension was maintained and the temperature rose to around 20 ° C in the spring. Moreover, even after the fluid state restoration, the suspension state deteriorated, the microparticles | fine-particles of the pesticide active ingredient generate | occur | produced in suspension, the sprayer etc. were clogged, and spraying became very difficult.

As described above, the previously-developed aqueous suspension formulation of 1,1'-iminiodi (octamethylene) diguanidinium = tris (alkylbenzenesulfonate) has a lot of low temperature cycles with a temperature of about 0 ° C. In winter, the storage stability was not sufficient.

 The problem to be solved by the present invention is not only excellent storage stability in the preservation conditions where the temperature change is large in the long cycle between seasons, but also in the winter range in which the temperature is changed in the range of 5 ℃ to -10 ℃ in a short cycle between day and night. It is an object to provide an aqueous suspension-type pesticide preparation of 1,1'-iminiodi (octamethylene) diguanidinium = tris (alkylbenzenesulfonate) having excellent storage stability even in long-term storage.

The present inventors have conducted various studies to solve the problem, and according to the above-described prescription, by using hydrogenated phospholipids having an iodide value of 20 or less as a phospholipid, not only a preservation condition having a large temperature change with a long period of season, but also a low Even in the case of storage conditions in which the temperature is changed in the range of 5 ° C to -10 ° C in a short period between the night and the night, the aqueous stability is excellent in the storage stability that can maintain a stable suspension state and suppress the generation of minute precipitates of the pesticide active ingredient. The discovery of being able to prepare suspended pesticide formulations has led to the completion of the present invention.

That is, this invention solves the said subject, (a) 1,1'-iminiodi (octamethylene) diguanidinium = tris (alkylbenzenesulfonate), (b) general formula (1)

RO- (CH ₂ CH ₂ O) _n -H

(Wherein R represents an alkyl group having 8 to 18 carbon atoms, n represents an integer of 0 to 4), a compound represented by (c) phospholipid and (d) an alkyl group having 6 to 20 carbon atoms An aqueous suspended pesticide preparation containing a surfactant and (e) water, wherein the (c) phospholipid is a hydrogenated phospholipid having an iodide of 20 or less, providing an aqueous suspended pesticide preparation.

Below, the structural component of the aqueous suspension pesticide formulation of this invention is demonstrated in order.

(A) 1,1'-iminiodi (octamethylene) diguanidinium = tris (alkylbenzenesulfonate) used by this invention is an agrochemical active ingredient of the aqueous suspension type agrochemical formulation of this invention. [Hereinafter referred to as (a) pesticide active ingredient]

The alkylbenzenesulfonate constituting the (a) agrochemical active ingredient used in the present invention is preferably a benzenesulfonate having an alkyl group having 1 to 20 carbon atoms, and in view of prevention of weakness and efficacy, a carbon atom It is especially preferable that it is benzenesulfonate which has a C4-C18 alkyl group, and it is still more preferable that it is benzenesulfonate which has a C10-C13 alkyl group. All of these (a) pesticide active ingredients are ingredients which are substantially insoluble in water. In addition, 1,1'-iminiodi (octamethylene) diguanidinium = tris (alkylbenzenesulfonate), in which the alkylbenzenesulfonate is a benzenesulfonate having an alkyl group having 10 to 13 carbon atoms, is referred to as "imnoctamine albeyl. Pesticides. "

Next, the compound represented by (b) General formula (1) is demonstrated.

(B) The compound represented by the said General formula (1) used by this invention acts as a dispersion stabilizer in the aqueous suspension pesticide formulation of this invention.

In general formula (1), the compound whose n = O is a saturated aliphatic alcohol of 8-18 carbon atoms which does not have an oxyethylene group in a molecule | numerator.

In the general formula (1), the compound of n = 1 is an alcohol in which ethylene glycol is ether-bonded to a saturated aliphatic alcohol having 8 to 18 carbon atoms, and is generally called polyoxyethylene (1 mol) monoalkyl ether and is usually mono Omitted simply, it is called like polyoxyethylene (1 mol) alkyl ether. For example, the alcohol represented by n = 3 represents an alcohol in which triethylene glycol is ether bonded to a saturated aliphatic alcohol, and is an alcohol generally called polyoxyethylene (3 mol) alkyl ether.

The saturated aliphatic alcohol having 8 to 18 carbon atoms may be linear or branched, but more preferably linear. The saturated aliphatic alcohol is preferably (a) an alcohol having the same carbon atom number as the carbon atom number of the alkyl group of the alkylbenzenesulfonate constituting the pesticide active ingredient, and a linear alcohol having 10 to 13 carbon atoms is particularly preferable. .

As a saturated aliphatic alcohol represented by the said General formula (1), For example, linear alkanol, such as an octanol, a decyl alcohol, a lauryl alcohol, a cetyl alcohol, a stearyl alcohol; Branched alkyl alcohols such as 2-ethyl-hexyl alcohol and 2-ethyl-hexyl diglycol (alias diethylene glycol mono-2-ethylhexyl ether); And polyoxyethylene alkyl ethers having a repeating number n of 1 to 4 of polyoxyethylene moieties such as polyoxyethylene (1 to 4 mol) lauryl ether and polyoxyethylene (1 to 4 mol) cetyl ether.

Next, the hydrogenated phospholipid whose (c) iodine value used by this invention is 20 or less is demonstrated.                     

Hydrogenated phospholipids of (c) iodide of 20 or less used in the present invention act as dispersion stabilizers in the aqueous suspension pesticide preparation of the present invention.

Hydrogenated phospholipids are hydrogenated by lecithin produced from the fruits of fats and oils such as soybeans and rapeseeds, and animal lipids such as egg yolk until the iodide is 20 or less, thereby saturating most of the unsaturated fatty acid portions of phospholipids Changed to Hydrogenated phospholipids having an iodine value of 10 or less are particularly preferably used in the present invention.

Among these hydrogenated phospholipids, hydrogenated soybean lecithin is particularly preferable in terms of low price and quality variation due to natural products.

Hydrogenated phospholipids having an iodide value of 20 or less, particularly hydrogenated lecithin and water-soluble proteins, used in the present invention are widely used in perfumes, cosmetics, foods, and the like, and have been confirmed to have high safety for the environment and human body. Moreover, also about the compound represented by General formula (1) used by this invention, by selecting and using the component used by the fragrance, cosmetics, a food field, etc., the safety of this aqueous suspension formulation can be improved more. They all function as dispersion stabilizers of aqueous suspension formulations of agrochemical active ingredients.

Next, the surfactant which has the alkyl group of (d) C6-C20 which is used by this invention is demonstrated.

The surfactant having an alkyl group having 6 to 20 carbon atoms (d) used in the present invention may be ionic or nonionic. Although the alkyl group which comprises the said surfactant may be linear or branched, it is more preferable that it is linear. The alkyl group constituting the surfactant is preferably (a) the same number of carbon atoms as the alkyl group of the alkylbenzenesulfonate constituting the agrochemical active ingredient, more preferably an alkyl group having 10 to 18 carbon atoms, and having 10 to 10 carbon atoms The alkyl group which is 13 is especially preferable.

In terms of dispersion stability, all of the alkyl groups constituting the surfactant having an alkyl group (b) an alkyl group having 6 to 20 carbon atoms with the alkyl group of the compound represented by the general formula (1) used in the present invention are (a) pesticides. It is preferable that it is an alkyl group of the same carbon atom as the alkyl group of the alkylbenzenesulfonate which comprises an active ingredient, and it is especially preferable that it is an alkyl group of 10-13 carbon atoms.

However, (d) Since the raw material used for surfactant which has an alkyl group of 6-20 carbon atoms originates from a natural thing, and the carbon atom number of this alkyl group has a distribution range, the carbon number of carbon atoms which is a preferable range is 10-10. If it contains the alkyl group which is 18, surfactant which has an alkyl group of 6-20 carbon atoms can be used.

Surfactants having an alkyl group having 6 to 20 carbon atoms (d) used in the present invention include (d-1) polyalkylene oxide nonionic surfactants, (d-2) fatty acid ester nonionic surfactants, and (d -3) broadly divided into anionic surfactant, (d-4) cationic surfactant, and (d-5) zwitterionic surfactant.

Examples of the (d-1) polyalkylene oxide nonionic surfactant include polyoxyalkylene alkyl ethers such as polyoxyethylene (20 mol) lauryl ether and polyoxyethylene (15 mol) cetyl ether; And polyoxyalkylene alkylamino ethers such as polyoxyethylene (12 mol) lauryl amino ether.

(d-2) As fatty acid ester type nonionic surfactant, For example, polyglycerol saturated fatty acid ester, such as decaglycerin lauric acid ester, decaglycerin myristic acid ester, hexaglycerin stearic acid ester; Polyalkylene glycol saturated fatty acid esters such as polyethylene glycol (average molecular weight 600) lauric acid ester; And polyoxyalkylene polypropylene glycol saturated fatty acid esters such as polyoxyethylene polypropylene glycol block copolymer stearic acid ester.

(d-3) As anionic surfactant, For example, alkyl sulfates, such as sodium lauryl sulfate; Polyoxyalkylene alkyl sulfates, such as polyoxyethylene (20 mol) lauryl ether sulfonate ammonium salt, etc. are mentioned.

(d-4) As cationic surfactant, For example, alkylammonium salts, such as cetyltrimethylammonium chloride; Polyoxyalkylene alkylammonium salts such as polyoxyethylene (10 mol) stearylmethylammonium chloride and the like.

(d-5) Cationic ionic surfactants include, for example, alkylbetaines such as lauryldimethylammoniobetaine; Alkylamine oxides, such as lauryl dimethylamine oxide, etc. are mentioned.

Among the above-mentioned surfactants, the polyglycerol saturated fatty acid esters exemplified as the (d-2) fatty acid ester nonionic surfactants are particularly preferable because they are excellent in low temperature stability of the aqueous suspension type pesticide preparation.

By using (f) the water-soluble protein in the aqueous suspension-type pesticide preparation of the present invention, excellent storage stability can be imparted. (f) As the water-soluble protein, for example, milk protein, vegetable protein, animal protein, or the like, or a protein agent consisting thereof, for example, skim milk powder, whole milk powder, lactalbumin hydrolyzate, casein, casein sodium, casein One or more selected from alkali metal salts, whey proteins, soybean powders, fish meat powders, gelatin, egg white powders, egg yolk powders, etc. may be mentioned. Among these, sodium caseinate is particularly preferred.

The ratio of the (a) pesticide active ingredient in the aqueous suspension pesticide preparation of the present invention is preferably in the range of 1 to 45% by weight, particularly preferably in the range of 5 to 40% by weight. Moreover, the range of 0.5-10 weight% is preferable, and, as for the ratio of the compound represented by (b) General formula (1) in the aqueous suspension pesticide formulation of this invention, the range of 1-8 weight% is especially preferable. Moreover, the range of 0.5-10 weight% is preferable, and, as for the ratio of the hydrogenated phospholipid whose (c) iodine value is 20 or less in the aqueous suspension pesticide formulation of this invention, the range of 1-8 weight% is especially preferable. Moreover, the range of 0.5-10 weight% is preferable, and, as for the ratio of surfactant (d) which has an alkyl group of 6-20 carbon atoms in the aqueous suspension pesticide formulation of this invention, the range of 1-8 weight% is especially preferable. Do. Moreover, the range of 25 to 97.5 weight% is preferable, and, as for the ratio of (e) water in the aqueous suspension pesticide formulation of this invention, the range of 36 to 92 weight% is especially preferable. When (f) water-soluble protein is used in combination with the aqueous suspension pesticide formulation of the present invention, the ratio of (f) water-soluble protein in the aqueous suspension pesticide formulation of the present invention is 0.5-10% by weight of the total amount of hydrogenated phospholipid and water-soluble protein. The range which becomes becomes preferable, and the range which becomes 1 to 8 weight% is especially preferable.                     

The ratio of the (a) pesticide active ingredient and (b) the compound represented by the general formula (1) in the aqueous suspension pesticide preparation of the present invention is preferably in the range of 0.1: 1 to 90: 1 by weight, and preferably from 0.6: 1 to Particularly preferred is a range of 40: 1. Moreover, the ratio of the (a) pesticide active ingredient and (c) hydrogenated phospholipid whose iodide value is 20 or less in the aqueous suspension pesticide formulation of this invention has a weight ratio of the range of 0.1: 1-90: 1, It is 0.6: 1. The range of -40: 1 is especially preferable. Moreover, the ratio of the (a) pesticide active ingredient and (d) surfactant which has an alkyl group of 6-20 carbon atoms in the aqueous suspension pesticide formulation of this invention has a weight ratio of 0.1: 1-90: 1, and is preferable. , 0.6: 1 to 40: 1 is particularly preferred.

When (f) water-soluble protein is blended with the aqueous suspension-type pesticide preparation of the present invention, the ratio of the total amount of (a) agrochemical active ingredient, (c) hydrogenated phospholipid having an iodine value of 20 or less and (f) water-soluble protein is weight ratio. The range of 0.1: 1-90: 1 is preferable, and the range of 0.6: 1-40: 1 is especially preferable. In addition, the ratio of the hydrogenated phospholipid having a iodine value of 20 or less and the water-soluble protein (f) is preferably in the range of 1: 0.1 to 1:10 by weight ratio.

Moreover, you may add other arbitrary components to the aqueous suspension pesticide formulation of this invention in the range which does not impair the effect of this invention. As other arbitrary components, a cryoprotectant, a preservative, a pH adjuster, etc. are mentioned, for example.

Examples of the cryoprotectant include water-soluble organic solvents such as ethylene glycol, propylene glycol, and propylene glycol monomethyl ether, and iodine. When using a cryoprotectant, it is preferable to mix | blend about 1 / 50-1 / 4 of (e) water compounding quantity in the aqueous suspension type pesticide preparation of this invention instead of water.                     

At the time of preparation of the aqueous suspension type pesticide preparation of this invention, it is necessary to fully mix each component. (d) Surfactants having an alkyl group having 6 to 20 carbon atoms are usually added in their entirety, but part of (a) agrochemically active ingredient, (b) a compound represented by formula (1), and (c) iodine Is added to the hydrogenated phospholipid of 20 or less, and the remainder may be added to (e) water. Although there is no restriction | limiting in particular in the mixing order of each component other than water, In order to make a homogeneous mixture easily, (b) the compound represented by General formula (1), and (c) hydrogenated phospholipid whose iodide is 20 or less, Therefore, after mixing (f) a water-soluble protein, the order which adds (a) agrochemical active ingredient and (d) surfactant which has a C6-C20 alkyl group is preferable.

(a) a pesticide active ingredient, (b) a compound represented by the general formula (1), (c) a hydrogenated phospholipid having an iodide of 20 or less, and (d) a surfactant having an alkyl group having 6 to 20 carbon atoms. (E) It is not preferable to add and mix water simultaneously. (a) a pesticide active ingredient, (b) a compound represented by the general formula (1), (c) a hydrogenated phospholipid having an iodide of 20 or less, and (d) a surfactant having an alkyl group having 6 to 20 carbon atoms. In this case, it is preferable to add a suitable heat and mix. At this time, since it is easy to cause coloring at the time of high temperature process, 80 degreeC or less is preferable and the range of 50-70 degreeC is especially preferable.

As a method of adding water to a suspended state, a conventionally known method can be used.

That is, (1) the previously prepared (a) pesticide active ingredient, (b) the compound represented by General formula (1), (c) hydrogenated phospholipid whose iodide is 20 or less, (d) alkyl group of 6-20 carbon atoms Surfactant having a method, if necessary (f) adding water to the mixture containing a water-soluble protein and stirring with a homomixer,

(2) (d) an active ingredient of (a) pesticide prepared in advance, (b) a compound represented by the general formula (1), (c) a hydrogenated phospholipid having an iodine value of 20 or less, in water in which a part of the surfactant is dissolved, (d) the remainder of surfactant, the method containing (f) water-soluble protein, if needed, and the method of stirring with a homomixer etc. are mentioned.

The aqueous suspension pesticide preparation of the present invention can be made into fine particles further by a high-speed homogenizer, a high pressure emulsifier, or the like.

The dispersed particles in the aqueous suspension-type pesticide preparation of the present invention obtained as described above surround the (a) pesticide active ingredient insoluble in water to form dispersed particles having stable water dispersibility. I think that.

The average particle diameter of the dispersed particles in the aqueous suspension pesticide preparation of the present invention measured using a laser diffraction scattering particle size distribution analyzer is preferably in the range of 0.1 to 20 µm, particularly preferably in the range of 0.5 to 7 µm. Do. Considering that the laser diffraction scattering particle size distribution meter cannot measure particle diameters of 0.1 μm or less, and that there is no problem in use even when the average particle diameter of the dispersed particles in the aqueous suspension pesticide formulation is 0.1 μm or less. Therefore, the lower limit of the average particle diameter is not set in the aqueous suspension type pesticide preparation.

Moreover, the viscosity of the aqueous suspension type agrochemical formulation of this invention has the preferable range of 50-5000 mPa * s. (b) a compound represented by the general formula (1), (c) a hydrogenated phospholipid having an iodide of 20 or less, (d) a surfactant having an alkyl group having 6 to 20 carbon atoms, and (f) added as necessary. As the water-soluble protein is added, the viscosity of the aqueous suspension pesticide formulation tends to be higher, and in addition to stabilizing the dispersed particles, the sedimentation inhibiting effect of the dispersed particles due to viscosity is added, which is more advantageous by the stability of the suspending agent. . However, the viscosity of the aqueous suspension-type pesticide preparation is particularly preferably in the range of 100 to 100 mPa · s because of easy handling and dilution with water.

EXAMPLE

Next, although an Example and a comparative example demonstrate this invention, this invention is not limited to the range of these Examples originally. In addition, "part" and "%" shall represent "weight part" and "1 weight%", respectively, unless there is particular notice.

Example 1

30 parts of imintadine albesylate, 3.7 parts of lauryl alcohol, hydrogenated soy lecithin ("Basis LP-20H" manufactured by Nisshin Seyou Co., Ltd., Yodga = 7.7] 2 parts, casein 0.5 parts of sodium, 4 parts of hexaglycerin stearic acid ester, and 5 parts of ethylene glycol are mixed, heated to 70 ° C. to form a homogeneous mixture, and the mixture is further warmed to 50 ° C. while stirring and slowly added water to suspend 100 Got wealth. This suspension was stirred for 10 minutes at 3000 rpm with a homomixer to obtain an aqueous suspension pesticide preparation.

It was 4.4 micrometers as a result of measuring the average particle diameter of the obtained aqueous suspension type pesticide formulation using the laser diffraction scattering type particle size distribution meter. Moreover, it was 170 mPa * s when the viscosity was measured using the Brookfield viscometer (30 rpm / 20 degreeC).

Example 2

30 parts of imintadine albesylate, 3.7 parts of lauryl alcohol, 2 parts of hydrogenated soybean lecithin ("Basic LP-20H" by Nisshin Seiyu Co., Ltd., Yodga = 6.7), lactalbumin hydrolyzate [Wakkojanyaku 0.5 parts, decaglycerin lauric acid ester, 2 parts decaglycerin stearic acid ester, and 5 parts ethylene glycol were mixed, heated to 70 ° C. to obtain a homogeneous mixture. Furthermore, water was added gradually, keeping this mixture at 50 degreeC, stirring, and obtained 100 parts of suspensions. This suspension was stirred for 10 minutes at 3000 rpm with a homomixer to obtain an aqueous suspension pesticide preparation.

The average particle diameter and the viscosity were measured in the same manner as in Example 1, and the results were 5.2 µm and 780 mPa · s, respectively.

Example 3

30 parts of imintadine albesylate, 4 parts of lauryl alcohol, 2 parts of hydrogenated soybean lecithin ("Basic LP-20H" manufactured by Nissin Seiyu Co., Ltd., iodga = 7.7), 4 parts of decaglycerine lauric acid ester And 5 parts of ethylene glycol were mixed, it heated at 70 degreeC, it was made into a homogeneous mixture, Then, this mixture was kept at 50 degreeC, and water was gradually added, stirring, and 100 parts of suspensions were obtained. This suspension was stirred for 10 minutes at 3000 rpm with a homomixer to obtain an aqueous suspension pesticide preparation.

The average particle diameter and the viscosity were measured in the same manner as in Example 1, and the results were 4.3 µm and 190 mPa · s, respectively.

Example 4

30 parts of imintadine albesylate, 5 parts of diethylene glycol mono-2-ethylhexyl ether, hydrogenated soybean lecithin ("Basic LP-20H" manufactured by Nissin Seyou Co., Ltd.), 2 parts of casein, casein 0.5 part of sodium, 4 parts of hexaglycerin stearic acid ester, and 5 parts of ethylene glycol are mixed, heated to 70 ° C. to obtain a homogeneous mixture, and then the mixture is further heated to 50 ° C. while stirring to gradually add water to suspending agent 100 Got wealth. This suspension was stirred for 10 minutes at 3000 rpm with a homomixer to obtain an aqueous suspension pesticide preparation.

The average particle diameter and the viscosity were measured in the same manner as in Example 1, and the results were 3.5 µm and 280 mPa · s, respectively.

Comparative Example 1

30 parts of imintadine albesylate, 2 parts of lauryl alcohol and 2 parts of oleyl alcohol, 2 parts of soy lecithin ("Basis LP-20", made by Nisshin Seiyu Co., Ltd., Iodine = 80), decaglycerin la Urinary acid ester 2 parts, decaglycerin olefinic acid ester 1 .5 parts and ethylene glycol 5 parts were mixed, heated to 70 ° C. to a homogeneous mixture, and then the mixture was kept at 50 ° C. and stirred to gradually add water. 100 parts of suspensions were added. This suspension was stirred for 10 minutes at 100 rpm with a homomixer to obtain an aqueous suspension-type pesticide preparation.

The average particle diameter and the viscosity were measured in the same manner as in Example 1, and the results were 3.2 µm and 480 mPa · s, respectively.

Comparative Example 2

30 parts of imintadine albesylate, 4 parts of lauryl alcohol, 2 parts of soy lecithin ("Basic LP-20", manufactured by Nissin Seyou Co., Ltd., Yodga = 80), 4 parts of decaglycerine lauric acid ester and ethylene 5 parts of glycol were mixed, heated to 70 ° C. to obtain a homogeneous mixture, and then the mixture was further added with water while keeping the mixture at 50 ° C. while stirring to obtain 100 parts of suspending agent. This suspension was stirred for 10 minutes at 100 rpm with a homomixer to obtain an aqueous suspension-type pesticide preparation.

The average particle diameter and the viscosity were measured in the same manner as in Example 1, and the results were 4.4 µm and 250 mPa · s, respectively.

Comparative Example 3

30 parts of imintadine albesylate, 4 parts of lauryl alcohol, 2 parts of egg yolk lecithin (Wakkoyaku Kogyo Co., Ltd., Yodga = 60), 4 parts of decaglycerine lauric acid ester, and 5 parts of ethylene glycol, After heating to 70 ° C. to make a homogeneous mixture, water was further added while keeping the mixture at 50 ° C. while stirring to obtain 100 parts of suspending agent. This suspension was stirred for 10 minutes at 100 rpm with a homomixer to obtain an aqueous suspension-type pesticide preparation.

The average particle diameter and the viscosity were measured in the same manner as in Example 1, and the results were 5.2 µm and 340 mPa · s, respectively.

[Comparative Example 4]                     

30 parts of imintadine albesylate, 5 parts of dipropylene glycol mono-butyl ether, 2 parts of soy lecithin ("Basic LP-20" from Nissin Seyou Co., Ltd., Iodine = 80), decaglycerin lauric acid ester 4 Part and 5 parts of ethylene glycol were mixed, heated to 70 ° C. to make a homogeneous mixture, and then the mixture was further heated to 50 ° C. while stirring to gradually add water to obtain 100 parts of suspending agent. This suspension was stirred for 10 minutes at 3000 rpm by a homomixer.

Immediately after the preparation of the obtained aqueous suspension-type preparation, the average particle diameter and the viscosity were measured in the same manner as in Example 1, and the results were 10.8 µm and 1090 mPa · s, respectively. However, at the point where it was fixed at 40 degreeC for 3 days, the yellow viscous substance sedimented and separated and the stable dispersion state was lost.

Test Example 1 Preservation Test at High Temperature

The prepared aqueous suspension-type pesticide formulation was put into a 500 ml glass bottle, and left standing for 12 weeks in a 50 degreeC thermostat and stored. Below, various tests were carried out and the results are shown in Table 1 below.

<Storage stability test>

The suspension state of the sample at the end of storage was observed. Furthermore, it preserve | saved for 24 hours at 20 degreeC, and investigated the stability of suspension state.

Test results were evaluated according to the following criteria.

(Double-circle): The suspension state is very favorable. Pesticide active ingredients are well dispersed in water.                     

: 현탁 상태가 양호. 상층에 약간의 물 분리가 인지되지만, 용기를 손으로 세게 흔들면 용이하게 균일 분산됨.

: Suspension is good. A slight separation of water is noticed in the upper layer, but the material is easily dispersed evenly by shaking the container hard.

(Triangle | delta): The suspension state is slightly bad. A portion of the suspension is adhered to the wall of the container in a viscous state, but it is dispersed by stirring with a rod or the like.

X: The suspension state is bad. Most of the suspension is in the form of a gel, and some of the suspension is agglomerated and is not easily dispersed even when stirred with a rod or the like.

<Presence or absence of crystal precipitation>

After 12 weeks of fixed storage, the sample was stored at 20 ° C. for 24 hours, and then diluted 500 times to observe the presence or absence of precipitation of crystals in the dilution liquid with an optical microscope.

<Measuring Residue on Sieve>

After the sample was fixed and stored for 12 weeks at 20 ° C. for 24 hours, 50 g of the sample was diluted with 1 liter of water. And the whole amount of this dilution liquid was passed through the sieve whose eye size is 45 micrometers. Next, 1 L of water was poured into a sieve, the sieve was shaken horizontally, and this water washing operation was repeated five times. After washing with water, the precipitate on the sieve net was measured and the crystal precipitation ratio was calculated according to the following equation.

Crystal precipitation rate (wt%) = [precipitated fraction (g)] / [injection (g) of (a) + (b) + (c) + (d) + (f)] x 100 in 50 g of sample] x 100

(Wherein (a) is the pesticide active ingredient weight, (b) is the weight of the compound represented by the general formula (1), (c) is the weight of hydrogenated phospholipid having an iodide value of 20 or less, and (d) is a carbon atom) The weight of the surfactant having an alkyl group of 6 to 20, (f) represents the weight of the water-soluble protein.)

Table 1

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3  Preservation stability  At the end of retention  ◎  ◎  ◎

 ◎  ◎

After 20 ℃ restoration                                           ◎  ◎  ◎  ◎  ◎  ◎

Precipitation radish radish radish radish radish radish radish  Remaining percentage of the sieve (% by weight)  0  0  0  0  0  0  0

(Test Example 2) Preservation test under high temperature and low temperature cycle conditions

The prepared aqueous suspension-type pesticide preparation was placed in a 500 ml glass bottle and stored at a constant temperature of 50 ° C. for 3 days, and then cooled from 50 ° C. to −10 ° C. for 12 hours, further 3 days at a constant temperature of −10 ° C. After storage, the temperature was raised from -10 ° C to 50 ° C for 12 hours, and 12 cycles (12 weeks) were performed for 1 cycle (1 week) and stored. In the same manner as in Test Example 1, the storage stability test, the presence or absence of crystal precipitation, and the residue on the sieve were measured. The results are shown in Table 2.

In the aqueous suspension pesticide preparation prepared in Comparative Example 3, the solids slightly adhered to the container wall on the upper surface of the liquid at the end of the storage test. After recovery at 20 ° C. water separation was noticed in the upper layer. The proportion of residue on the sieve was 1% by weight.

TABLE 2

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Preservation stability  At the end of retention  ◎  ◎  ◎

 △  After 20 ℃ restoration  ◎  ◎  ◎  ◎

 ◎

Precipitation radish radish radish radish radish radish radish  Remaining percentage of the sieve (% by weight)  0  0  0  0  0  0  One

Test Example 3 Preservation Test at Low Temperature Conditions

The prepared aqueous suspension-type pesticide formulation was put into a 500 ml glass bottle and stored at -5 ° C for 12 weeks. In the same manner as in Test Example 1, the storage stability test, the presence or absence of crystal precipitation, and the residue on the sieve were measured. The results are shown in Table 3. The aqueous suspension type pesticide preparation prepared in Example 3 exhibited a creamy solidified state at the end of the preservation test, but returned to a good suspended state after restoration at 20 ° C. In contrast, the aqueous suspension type pesticide preparation prepared in Comparative Example 1 exhibited a viscous state at the end of the preservation test, water separation was recognized in the upper layer even after restoration at 20 ° C, and clogging was caused by the residue on the sieve. Residual secretion on the sieve was 2% by weight.

The aqueous suspension-type pesticide preparation prepared in Comparative Example 2 exhibited a creamy solidified state at the end of the preservation test, water separation was observed in the upper layer even after restoration at 20 ° C, and clogging was caused by the residue on the sieve. The proportion of residue that passed through the sieve was 2% by weight.

The aqueous suspension type pesticide preparation prepared in Comparative Example 3 exhibited a cream solidified state at the end of the preservation test, and water separation was recognized in the upper layer even after restoration at 20 ° C, and clogging occurred due to the residue that passed through the sieve. The percentage of residue that passed through the sieve was 3% by weight.

TABLE 3

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Preservation stability  At the end of retention  ◎  ◎ - ^{* 1}  ◎  △ - ^{* 1} - ^{* 1}  After 20 ℃ restoration  ◎  ◎  ◎  ◎

 △ Precipitation radish radish radish radish U U U  Remaining percentage of the sieve (% by weight)  0  0  0  0  2  2  3

*One ; It shows a cyclic solidification state.

Test Example 4 Preservation Test in Low Temperature Cycle Conditions

The prepared aqueous suspension-type pesticide preparation was placed in a 500 ml glass bottle and stored at a constant temperature of 5 ° C. for 6 hours, then cooled from 5 ° C. to −10 ° C. for 6 hours, and further stored at −10 ° C. for 6 hours. Thereafter, the temperature was increased from −10 ° C. to 5 ° C. for 6 hours, and 84 cycles (12 weeks) were carried out and stored for 1 cycle 24 hours). In the same manner as in Test Example 1, the storage stability test, the presence or absence of crystal precipitation, and the residue on the sieve were measured. The results are shown in Table 4.

The aqueous suspension type pesticide preparation prepared in Example 3 exhibited a creamy solidified state at the end of the preservation test, but returned to a good suspended state after restoration at 20 ° C. In contrast, the aqueous suspension type pesticide preparations prepared in Comparative Examples 1, 2 and 3 had a creamy solidified state at the end of the storage test and did not return to a good suspended state even after restoration at 20 ° C. For this reason, clogging was caused by the residue that passed through the sieve, and it was difficult to filter the whole amount through a sieve in one operation, and filtration was divided into three times. The residual ratio which passed the sieve was 12 weight% in the comparative example 1, 9 weight% in the comparative example 2, and 18 weight% in the comparative example 3.

Table 4

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Preservation stability   At the end of retention  ◎  ◎ - ^{* 1}  ◎ - ^{* 1} - ^{* 1} - ^{* 1}  After 20 ℃ restoration  ◎  ◎  ◎  ◎  ×  ×  × Precipitation radish radish radish radish U U U  Remaining percentage of the sieve (% by weight)  0  0  0  0  12  9  18

*One ; A creamy state of solidification is indicated.

The aqueous suspension pesticide preparation of the present invention is not only excellent in storage stability in storage conditions in which the temperature change is large in the long period of the season, but also in the range of 5 ° C. to 10 ° C. in the short period between day and night. Even in the case of long term storage, excellent storage stability is shown.

Claims (6)

(a) 1,1'-iminiodi (octamethylene) diguanidinium = tris (alkylbenzenesulfonate), (b) general formula (1) RO- (CH ₂ CH ₂ O) _n -H (Wherein R represents an alkyl group having 8 to 18 carbon atoms, n represents an integer of 0 to 4), and the compound represented by (c) phospholipid and (d) alkyl group having 6 to 20 carbon atoms Eggplants are aqueous suspended pesticide formulations containing a surfactant and (e) water, The aqueous suspension-type pesticide preparation according to claim (c), wherein the phospholipid is a hydrogenated phospholipid having an iodide of 20 or less. The method of claim 1, (F) an aqueous suspended pesticide formulation containing a water soluble protein. The method of claim 1, The alkylbenzenesulfonate constituting (a) 1,1'-iminiodi (octamethylene) diguanidinium = tris (alkylbenzenesulfonate) is a benzenesulfonate having an alkyl group having 10 to 13 carbon atoms, Moreover, the aqueous suspension type pesticide preparation which is a compound which the said (b) compound represented by General formula (1) has a C10-C13 alkyl group. The method of claim 3, The aqueous suspension type pesticide preparation, wherein the surfactant (d) is a surfactant having an alkyl group having 10 to 13 carbon atoms. The method of claim 1, 1,1′-iminiodi (octamethylene) diguanidinium = an alkyl group of alkylbenzenesulfonate constituting tris (alkylbenzenesulfonate) and an alkyl group of a compound represented by the general formula (1) and a surfactant An aqueous suspension pesticide preparation wherein the alkyl group is an alkyl group having the same number of carbon atoms. The method of claim 1, An aqueous suspension pesticide formulation having an average particle diameter of 20 μm or less by a laser diffraction scattering particle size distribution measurement method of dispersed particles in an aqueous suspension pesticide formulation.