AU779666B2

AU779666B2 - Aqueous suspension pesticide preparation

Info

Publication number: AU779666B2
Application number: AU79420/01A
Authority: AU
Inventors: Yoshihiro Sato
Original assignee: Dainippon Ink and Chemicals Co Ltd
Current assignee: Nippon Soda Co Ltd
Priority date: 2000-10-30
Filing date: 2001-10-15
Publication date: 2005-02-03
Anticipated expiration: 2021-10-15
Also published as: BR0104887A; IL146103A0; TWI241162B; CN1212770C; KR100764044B1; CN1350788A; IL146103A; AU7942001A; KR20020033542A

Description

1

AUSTRALIA

Patents Act 1990 Dainippon Ink Chemicals, Inc.

COMPLETE SPECIFICATION STANDARD PATENT 9 9.

9 999 9o Invention Title: Aqueous suspension pesticide preparation The following statement is a full description of this invention including the best method of performing it known to us:- 1A TECHNICAL FIELD The present invention relates to a pesticide preparation of the aqueous suspension type (hereinafter referred to as an aqueous suspension pesticide preparation) which contains 1,1'iminiodi(octamethylene)diguanidinium tris(alkylbenzenesulfonate) as an active pesticide ingredient, the pesticide preparation having excellent stability even under fluctuating low temperature conditions.

o o BACKGROUND ART 1,1' -Iminiodi(octamethylene)diguanidinium tris(alkylbenzenesulfonate), which is the active pesticide Singredient of the preparation according to the present invention, is known (Japanese Examined Patent Application, Second Publication No. Hei 2-7564; U.S. Patent No. 4,659,739) as an excellent fungicide for agricultural and horticultural use. Among variants thereof, a Clo to C 13 1,1'iminiodi(octamethylene)diguanidinium tris(alkylbenzenesulfonate) (melting point: 92 to 96 0

C),

3o which contains as the major component a C 12 component of an alkyl chain of an alkylbenzene sulfonate, is called iminoctadine tris(albesilate), and they have already been put into practical use as broad-spectrum fungicides.

A pesticide proper, which is in the form of a solid at ordinary temperatures, may typically be processed into an aqueous suspension pesticide preparation by blending a watersoluble or water-suspendible synthetic polymer compound, an anionic surfactant, a nonionic surfactant, etc., therewith.

When the pesticide proper has a melting point of from to 100'C, however, there arises a problem in that if a suspension preparation which is a suspension of the pesticide proper is put under a condition in which the temperature fluctuates largely, the suspension breaks while crystals develop due to the melting or solidification of the solid pesticide proper which has been dispersed. In the case of an emulsified aqueous suspension prepared by dissolving the pesticide proper in a commonly used water-insoluble organic solvent and emulsifying in water, on the other hand, there arises another problem in that the emulsion breaks while crystals are precipitated because the pesticide proper crystallizes in fine liquid droplets dispersed in water.

According to a conventional known method of processing the pesticide proper into a preparation, it was difficult to process the pesticide into a stable aqueous suspension preparation because of severe crystal precipitation of 1,1'iminiodi(octamethylene)diguanidinium tris(alkylbenzenesulfonate), which is the active pesticide ingredient used in the present invention. In the aqueous suspension thus obtained, the suspension breaks due to solidification or crystallization of the active pesticide ingredient. It was difficult to emulsify the active pesticide ingredient because the active pesticide ingredient has very poor solubility in commonly used water-insoluble organic solvents.

To solve these problems, the present inventors developed an aqueous suspension pesticide preparation which includes (a) a 1,1'-iminiodi(octamethylene)diguanidinium tris(alkylbenzenesulfonate); a compound represented by the general formula

R-O-(CH

2

CH

2 0)n-H (wherein R represents an alkyl group or alkenyl group having 8 to 18 carbon atoms and n represents an integer of 0 to 4) as a suspension stabilizer, or a phospholipid; a surfactant having a C6 C20 alkyl or alkenyl group; and water, as 15 described in Japanese Unexamined Patent Application, First Publication No. Hei 8-225402 Patent No. 5,728,734).

It is believed that this aqueous suspension pesticide preparation is an aqueous suspension pesticide preparation *which has excellent stability and excellent safety for the S 20 environment and users, because it maintains a stable suspension state without separating and precipitating the active pesticide ingredient after long-term storage tests at 500C, long-term storage tests at and long-term storage tests for 12 weeks under conditions with severe fluctuations in temperature, specifically a long-term cycling storage test with a high temperature (500C) for 3 days and a low temperature for 3 days.

4 However, it became apparent that the preparation has poor resistance to changes in temperature at low temperatures.

That is, in the winter in a cold district, the day and night temperatures fluctuate between 5 and -10°C, and the fluctuation continues cyclically from day to day; when the preparation was stored for a long period in this state in the winter, the viscosity of the preparation increased while the suspended state was maintained, or the preparation solidified into the form of a cream and did not recover a good flowable state until the temperature increased to about 20 0 C in the spring. Even though the preparation returned to a flowable state, the suspension state degraded. As a result, microprecipitates of the active pesticide ingredient are produced in the suspension, thereby causing clogging of 15 applicators, and thus making it difficult to spray the preparation.

As described above, it was difficult to say that the storage stability of the aqueous suspension pesticide preparation of 1,1'-iminiodi(octamethylene)diguanidinium :20 tris(alkylbenzenesulfonate), which has previously been S developed, is satisfactory in the winter when the temperature repeats cycles at low temperatures around 0°C.

4A Any discussion of documents, acts, materials, devices, articles or the like which has been included in the present specification is solely for the purpose of providing a context for the present invention. It is not to be taken as an admission that any or all of these matters form part of the prior art base or were common general knowledge in the field relevant to the present invention as it existed before the priority date of each claim of this application.

DISCLOSURE OF THE INVENTION The present inventors have recognised that a need exists for an aqueous suspension pesticide preparation of 1,1'-iminiodi (octamethylene) diguanidinium tris (alkyl- *e

S*

benzenesulfonate), which not only has excellent storage stability under storage conditions where the temperature changes drastically in a long cycle through the seasons, but also has excellent storage stability during storage in winter when the day and night short-cycle temperatures fluctuate between 5 and The present inventors have intensively researched to solve the problems described above and have found that it is possible to prepare an aqueous suspension pesticide preparation having excellent storage stability, which can maintain a stable suspension state and inhibit production of microprecipitates of the active pesticide ingredient not only under storage conditions where the temperature changes drastically in a long cycle through the seasons, but also under storage conditions where the temperature changes within a range from 5 to -10 0 C in a short cycle through day and night, by using a hydrogenated phospholipid having an iodine S value of 20 or less as the phospholipid in the formulation described previously. Thus, the present invention has been completed.

In one aspect, the present g S invention provides an aqueous suspension pesticide preparation which includes a 1,1'-iminiodi(octamethylene)diguanidinium tris(alkyl-benzenesulfonate); a compound represented by 5 the general formula

R-O-(CH

2

CH

2 0)n-H (wherein R represents a C 8

C

8 s alkyl group and n represents an integer of 0 to a phospholipid; a surfactant carrying an alkyl group having 6 to 20 carbon atoms; and (e) water; wherein the phospholipid is a hydrogenated phospholipid having an iodine value of 20 or less.

BEST MODE FOR CARRYING OUT THE INVENTION Each constituent ingredient in the aqueous suspension pesticide preparation of the present invention will be described below.

The l,l'-iminiodi(octamethylene)diguanidinium tris(alkylbenzenesulfonate) used in the present invention is an active pesticide ingredient of the aqueous suspension pesticide preparation (hereinafter referred to as an active 15 pesticide ingredient The alkylbenzenesulfonate, which constitutes the active pesticide ingredient used in the present invention, is preferably benzene sulfonate having a Ci C20 alkyl group, more preferably benzene sulfonate having a C4 C18 alkyl group, and most preferably benzene sulfonate having a Cio C13 alkyl group, in view of prevention of pesticide injury and in view of pesticidal effects. All active pesticide ingredients are substantially insoluble in water. The 1,1'iminiodi(octamethylene)diguanidinium tris(alkylbenzenesulfonate), which is a benzene sulfonate having a Cio C13 alkyl group as an alkyl benzene sulfonate, is an active pesticide ingredient referred to as "iminoctadine tris(albesilate)".

Next, the compound represented by the general formula will be described.

The compound represented by the general formula (1) used in the present invention acts as a suspension stabilizer in the aqueous suspension pesticide preparation of the present invention.

The compound of the general formula in which n is 0 is a C 8 -C18 saturated aliphatic alcohol having no oxyethylene group in the molecule.

The compound of the general formula in which n is 1 is an alcohol in which ethylene glycol is bonded to a C8 -C18 saturated aliphatic alcohol via an ether bond, and is generally called a polyoxyethylene (1 mol) monoalkyl ether or 15 simply called a polyoxyethylene (1 mol) alkyl ether. The alcohol of the general formula in which n is 3 means an •t alcohol in which triethylene glycol is bonded to a saturated aliphatic alcohol via an ether bond, and is generally called a polyoxyethylene (3 mol) alkyl ether.

The C8 -C18 saturated aliphatic alcohol may be either a linear or branched one, but a linear one is preferable. It is preferable that the number of carbon atoms of the alkyl group be one which is almost the same as that of the alkyl group of alkylbenzene sulfonate which constitutes the active pesticide ingredient It is more preferable that the number of carbon atoms be from 10 to 13.

Examples of the saturated aliphatic alcohol represented 8 by the general formula include linear alkanols such as octanol, decyl alcohol, lauryl alcohol, cetyl alcohol and stearyl alcohol; branched alkyl alcohols such as 2-ethyl-hexyl alcohol and 2-ethyl-hexyl diglycol (also known as diethylene glycol mono-2-ethylhexyl ether); and polyoxyethylene alkyl ethers in which the number of repetition of the polyoxyethylene moieties is 1 to 4, such as polyoxyethylene (1 4 mol) lauryl ethers and polyoxyethylene (1 4 mol) cetyl ethers.

Next, the hydrogenated phospholipid having an iodine value of 20 or less used in the present invention will be described.

The hydrogenated phospholipid having an iodine value of 20 or less used in the present invention acts as a S" 15 suspension stabilizer in the aqueous suspension pesticide preparation of the present invention.

The hydrogenated phospholipid is obtained by hydrogenating lecithin produced from oil seeds (such as soybean and rapeseed) or from animal lipids (such as egg yolk) until the iodine value reaches 20 or less, thereby converting almost all of the unsaturated fatty acid moieties of the phospholipids into saturated fatty acids. The hydrogenated phospholipid having an iodine value of 10 or less is a material which is particularly preferably used in the present invention.

Among these hydrogenated phospholipids, hydrogenated soybean lecithin is particularly preferable in view of cost and because the quality thereof does not greatly vary even though it is made from a natural product.

The hydrogenated phospholipid having an iodine value of 20 or less used in the present invention, especially a hydrogenated lecithin and a water-soluble protein have been widely used in the fields of cosmetics and foods, and it has already been confirmed that they are very safe to the environment and to humans. With respect to the compound represented by the general formula used in the present invention, the safety of the aqueous suspension pesticide preparation can be enhanced by selecting and using ingredients used in the fields of cosmetics and foods. Both of these types of ingredients function as suspension stabilizers in the aqueous suspension pesticide preparation of the active pesticide ingredient.

Next, the surfactant having a C6 C20 alkyl group •used in the present invention will be described.

The surfactant having a C 6 C20 alkyl group used in the present invention may be either an ionic surfactant or nonionic surfactant. The alkyl group, which is a part of the surfactant, may be either a linear or branched group, but a linear group is preferable. It is preferable that the number of carbon atoms of the alkyl group which is a part of the surfactant be one which is very similar to that of the alkyl group of the alkylbenzene sulfonate which constitutes the active pesticide ingredient An alkyl group having 10 to 18 carbon atoms is preferable, and an alkyl group having 10 to 13 carbon atoms is more preferable.

It is preferable that the number of carbon atoms of the alkyl group of the compound represented by the general formula used in the present invention and the alkyl group, which constitutes the surfactant having a C 6 C20 alkyl group, be those which are very similar to those of the alkyl group of the alkylbenzene sulfonate which constitutes the active pesticide ingredient An alkyl group having 10 to 13 carbon atoms is particularly preferable.

Since the raw material used in the surfactant having a C6 C20 alkyl group is generally made from natural products and the number of carbon atoms of the alkyl group has a distribution range, a surfactant having a C 6 C20 alkyl group can be used as long as it has a Clo Cis alkyl group within a 15 preferable distribution range.

The surfactant having a C6 C20 alkyl group used in the present invention is roughly classified into (d-l) nonionic surfactants of the polyalkylene oxide type, (d-2) nonionic surfactants of the fatty acid ester type, (d-3) 20 anionic surfactants, cationic surfactants, and ampholytic surfactants.

Examples of the nonionic surfactant of the polyalkylene oxide type 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) laurylamino ether.

11 Examples of the nonionic surfactant of fatty acid ester type include polyglycerin saturated fatty acid esters such as decaglycerin laurate, decaglycerin myristate and hexaglycerin stearate; polyalkylene glycol saturated fatty acid esters such as polyethylene glycol (average molecular weight: 600) laurate; and polyoxyalkylene polypropylene glycol saturated fatty acid esters such as polyoxyethylene polypropylene glycol block copolymer stearate.

Examples of the anionic surfactant include alkyl sulfates such as sodium lauryl sulfate; and polyoxyalkylene alkyl sulfates such as polyoxyethylene (20 mol) lauryl ether sulfate ammonium salt.

Examples of the cationic surfactant include eo alkylammonium salts such as cetyltrimethylammonium chloride; 15 and polyoxyalkylene alkylammonium salts such as polyoxyethylene (10 mol) stearylmethylammonium chloride.

Examples of the ampholytic surfactant include alkylbetaines such as lauryldimethylammoniobetaine; and alkylamine oxides such as lauryldimethylamine oxide.

20 Among these surfactants, polyglycerin saturated fatty acid esters described above as examples of nonionic surfactant of fatty acid ester type are particularly preferred because of excellent stability at low temperatures of the aqueous suspension pesticide preparation.

Use of the water-soluble protein in the aqueous suspension pesticide preparation makes it possible to impart excellent storage stability. Examples of the water-soluble 12 protein include milk protein, vegetable protein, animal protein, or protein preparations made of these proteins, for example, one or more kinds selected from skim milk, whole milk powder, lactoalbumin hydrolysate, casein, alkali metal salt of casein sodium caseinate), whey protein, soybean powder, fish powder, gelatin, egg white powder, and egg yolk powder.

Among these water-soluble proteins, sodium caseinate is particularly preferred.

The amount of the active pesticide ingredient in the aqueous suspension pesticide preparation of the present invention is preferably within a range from 1 to 45% by weight, and is particularly preferably from 5 to 40% by weight. The amount of the compound represented by the general formula in the aqueous suspension pesticide S 15 preparation of the present invention is preferably within a range from 0.5 to 10% by weight, and is particularly preferably from 1 to 8% by weight. The amount of the hydrogenated phospholipid having an iodine value of 20 or less in the aqueous suspension pesticide preparation of the 20 present invention is preferably within a range from 0.5 to by weight, and is particularly preferably from 1 to 8% by weight. The amount of the surfactant having a C 6 alkyl group in the aqueous suspension pesticide preparation of the present invention is preferably within a range from 0.5 to 10% by weight, and is particularly preferably from 1 to 8% by weight. The amount of water in the aqueous suspension pesticide preparation of the present invention is preferably within a range 25 to 97.5% by weight, and is particularly preferably from 36 to 92% by weight. When using the watersoluble protein in combination in the aqueous suspension pesticide preparation of the present invention, the total amount of the hydrogenated phospholipid and the water-soluble protein is preferably within a range from 0.5 to 10% by weight, and is particularly preferably from 1 to 8% by weight.

The mixing ratio of the active pesticide ingredient (a) to the compound represented by the general formula in the aqueous suspension pesticide preparation is preferably within a range from 0.1:1 to 90:1, and is particularly preferably from 0.6:1 to 40:1. The mixing ratio of the active pesticide ingredient to the hydrogenated phospholipid (c) having an iodine value of 20 or less in the aqueous suspension 15 pesticide preparation is preferably within a range from 0.1:1 to 90:1, and is particularly preferably from 0.6:1 to 40:1.

The mixing ratio of the active pesticide ingredient to the surfactant having a C6 C20 alkyl group in the aqueous suspension pesticide preparation is preferably within a range S 20 from 0.1:1 to 90:1, and is particularly preferably from 0.6:1 to 40:1.

In the case in which the water-soluble protein is mixed with the aqueous suspension pesticide preparation, the mixing ratio of the active pesticide ingredient to the total of the hydrogenated phospholipid having an iodine value of 20 or less and the water-soluble protein is preferably within a range from 0.1:1 to 90:1, and is 14 particularly preferably from 0.6:1 to 40:1. The mixing ratio of the hydrogenated phospholipid having an iodine value of or less to the water-soluble protein is preferably within a range from 1:0.1 to 1:10.

As long as the effects of the present invention are not impaired, the aqueous suspension pesticide preparation of the present invention may further contain other arbitrary ingredients, and examples of the other arbitrary ingredient include antifreeze agents, preservatives, and pH adjustors.

Examples of the antifreeze agent include water-soluble organic solvents such as ethylene glycol, propylene glycol or propylene glycol monomethyl ether; and urea. When using the antifreeze agent, the antifreeze agent is preferably used in place of water in an amount within a range from about 1/50 to S 15 1/4 of the amount of water in the aqueous suspension pesticide preparation.

In the preparation of the aqueous suspension pesticide preparation, it is necessary to sufficiently mix the respective ingredients. Although the surfactant having a S 20 C 6

C

20 alkyl group is usually added at one time, a portion *thereof can be added to the active pesticide ingredient the compound represented by the general formula and the hydrogenated phospholipid having an iodine value of or less, and then the rest can be added to water (e) Although the mixing sequence is not specifically limited, it is preferable that the compound represented by the general formula and the hydrogenated phospholipid having an iodine value of 20 or less and, if necessary, the watersoluble protein be mixed, and then the active pesticide ingredient and the surfactant having a C6 C20 alkyl group be added, in order to easily prepare a homogeneous mixture.

In the case of mixing the active pesticide ingredient the compound represented by the general formula the hydrogenated phospholipid having an iodine value of or less and the surfactant having a C6 C20 alkyl group, it is not preferable that water be simultaneously added and mixed. In the case of mixing the active pesticide ingredient the compound represented by the general formula the hydrogenated phospholipid having an iodine value of 20 or less and the surfactant having a C6 C20 alkyl group, it is preferable that they be mixed by properly heating. In that case, since coloration occurs when treated at high temperature, the treatment temperature is preferably 80°C or lower, and is particularly preferably within a range from 50 to 700C.

20 As the method of adding water to form a suspension, a conventionally known method can be used. Examples thereof include a method of adding water to a previously prepared mixture of the active pesticide ingredient the compound represented by the general formula the hydrogenated phospholipid having an iodine value of 20 or less and the surfactant having a C6 C20 alkyl group and, if necessary, the water-soluble protein and stirring with a homomixer, and a method of adding a previously prepared mixture of the active pesticide ingredient the compound (b) represented by the general formula the hydrogenated phospholipid having an iodine value of 20 or less and the rest of the surfactant and, if necessary, the watersoluble protein in water into which a portion of the surfactant has been dissolved.

The aqueous suspension pesticide preparation of the present invention can be further formed into fine particles by a high speed homogenizer or a high pressure emulsifying machine.

It is believed that suspension particles in the obtained aqueous suspension pesticide preparation of the present invention, which has stable water dispersibility, are formed 15 by surrounding the active pesticide ingredient with the ingredients to (d) The average particle size of suspension particles in the aqueous suspension pesticide preparation of the present invention as measured by a laser diffraction and scattering S 20 type particle size analyzer is preferably within a range from 0.1 to 20 pm, and is particularly preferably from 0.5 to 7 pm.

•The lower limit of the average particle size of suspension particles in the aqueous suspension pesticide preparation is not limited because the average particle size of 0.1 pm or less cannot be measured by the laser diffraction and scattering type particle size analyzer and dispersed particles having an average particle size of 0.1 pm or less can be used 17 without any obstacles.

The viscosity of the aqueous suspension pesticide preparation of the present invention is preferably within a range from 50 to 5000 mPa-s. The greater the amounts (with respect to water) of the compound represented by the general formula the hydrogenated phospholipid having an iodine value of 20 or less, the surfactant having a C6

C

20 alkyl group, and the water-soluble protein which is optionally added, the higher the viscosity tends to become.

Therefore, the inhibition effects against sedimentation of suspension particles due to the increased viscosity, in addition to the stabilization of the suspension particles, ***affect the stability of the suspension more advantageously.

However, the viscosity of the aqueous suspension pesticide 15 preparation of the present invention is preferably within a range from 100 to 1000 mPa-s in view of handling during application and easy dilution with water.

EXAMPLES

o S 20 The following Examples and Comparative Examples further illustrate the present invention in detail; however, the present invention is not limited by these Examples. In the following Examples and Comparative Examples, parts and percentages are by weight unless otherwise specified.

Example 1 Parts of iminoctadine tris(albesilate), 3.7 parts of lauryl alcohol, 2 parts of hydrogenated soybean lecithin (BasisTM LP-20H, manufactured by Nisshin Oil Mills, Ltd., iodine value: 0.5 parts of sodium casein, 4 parts of hexaglycerin stearate and 5 parts of ethylene glycol were mixed and heated to 70 0 C to yield a homogeneous mixture. To the obtained mixture maintained at 50°C was slowly added water while stirring to yield 100 parts of a suspension. This suspension was stirred in a homomixer at 3,000 rpm for minutes to obtain an aqueous suspension pesticide preparation.

The average particle size of the resulting aqueous suspension pesticide preparation was measured by using a laser diffraction and scattering type particle size analyzer. As a result, the average particle size was 4.4 pm. The viscosity was measured by using a B-type viscometer (30 rpm/20 0 As a 15 result, the viscosity was 170 mPa-s.

Example 2 30 Parts of iminoctadine tris(albesilate), 3.7 parts of 0. lauryl alcohol, 2 parts of hydrogenated soybean lecithin 20 (Basis T M LP-20H, manufactured by Nisshin Oil Mills, Ltd., iodine value: 0.5 parts of lactoalbumin hydrolysate (manufactured by Wako Pure Chemical Ind., Ltd.), 2 parts of decaglycerin laurate, 2 parts of decaglycerin stearate and parts of ethylene glycol were mixed and heated to 700C to yield a homogeneous mixture. To the obtained mixture maintained at 500C was slowly added water while stirring to yield 100 parts of a suspension. This suspension was stirred in a homomixer at 3,000 rpm for 10 minutes to obtain an aqueous suspension pesticide preparation.

In the same manner as in Example 1, the average particle size and the viscosity were measured. As a result, the average particle size was 5.2 pm and the viscosity was 780 mPa s.

Example 3 Parts of iminoctadine tris(albesilate), 4 parts of lauryl alcohol, 2 parts of hydrogenated soybean lecithin (Basis T LP-20H, manufactured by Nisshin Oil Mills, Ltd., iodine value: 4 parts of decaglycerine laurate and parts of ethylene glycol were mixed and heated to 70 0 C to yield a homogeneous mixture. To the obtained mixture S 15 maintained at 500C was slowly added water while stirring to yield 100 parts of a suspension. This suspension was stirred in a homomixer at 3,000 rpm for 10 minutes to obtain an aqueous suspension pesticide preparation.

In the same manner as in Example 1, the average particle 20 size and the viscosity were measured. As a result, the average particle size was 4.3 pm and the viscosity was 190 mPa*s.

Example 4 30 Parts of iminoctadine tris(albesilate), 5 parts of dietylene glycol mono-2-ethyl hexyl ether, 2 parts of hydrogenated soybean lecithin (BasisT LP-20H, manufactured by Nisshin Oil Mills, Ltd., iodine value: 0.5 parts of sodium casein, 4 parts of hexaglycerin stearate and 5 parts of ethylene glycol were mixed and heated to 700C to yield a homogeneous mixture. To the obtained mixture maintained at 50°C was slowly added water while stirring to yield 100 parts of a suspension. This suspension was stirred in a homomixer at 3,000 rpm for 10 minutes to obtain an aqueous suspension pesticide preparation.

In the same manner as in Example 1, the average particle size and the viscosity were measured. As a result, the average particle size was 3.5 pm and the viscosity was 280 mPa-s.

Comparative Example 1 15 30 Parts of iminoctadine tris(albesilate), 2 parts of lauryl alcohol, 2 parts of soybean lecithin (BasisT manufactured by Nisshin Oil Mills, Ltd., iodine value: 80), 2 parts of decaglycerol laurate, 2 parts of decaglycerin laurate 1.5 parts of decaglycerin oleate and 5 parts of ethylene glycol were mixed and heated to 70 0 C to yield a homogeneous mixture. To the obtained mixture maintained at 50°C was slowly added water while stirring to yield 100 parts of a suspension. This suspension was stirred in a homomixer at 10,000 rpm for 10 minutes to obtain an aqueous suspension pesticide preparation.

In the same manner as in Example 1, the average particle size and the viscosity were measured. As a result, the average particle size was 3.2 pm and the viscosity was 480 mPa s.

Comparative Example 2 30 Parts of iminoctadine tris(albesilate), 4 parts of lauryl alcohol, 2 parts of soybean lecithin (Basis T M manufactured by Nisshin Oil Mills, Ltd., iodine value: 80), 4 parts of decaglycerin laurate and 5 parts of ethylene glycol were mixed and heated to 70 0 C to yield a homogeneous mixture.

To the obtained mixture maintained at 50 0 C was slowly added water while stirring to yield 100 parts of a suspension. This suspension was stirred in a homomixer at 10,000 rpm for minutes to obtain an aqueous suspension pesticide preparation.

In the same manner as in Example 1, the average particle 15 size and the viscosity were measured. As a result, the Saverage particle size was 4.4 pm and the viscosity was 250 mPa *s.

Comparative Example 3 30 Parts of iminoctadine tris(albesilate), 4 parts of lauryl alcohol, 2 parts of egg yolk lecithin (manufactured by Wako Pure Chemical Ind., Ltd., iodine value: 60), 4 parts of decaglycerin laurate and 5 parts of ethylene glycol were mixed and heated to 70 0 C to yield a homogeneous mixture. To the obtained mixture maintained at 50 0 C was slowly added water while stirring to yield 100 parts of a suspension. This suspension was stirred in a homomixer at 10,000 rpm for minutes to obtain an aqueous suspension pesticide preparation.

In the same manner as in Example 1, the average particle size and the viscosity were measured. As a result, the average particle size was 5.2 pm and the viscosity was 340 mPa s.

Comparative Example 4 Parts of iminoctadine tris(albesilate), 5 parts of dipropylene glycol monobutyl ether, 2 parts of soybean lecithin (BasisTM LP-20, manufactured by Nisshin Oil Mills, Ltd., iodine value: 80), 4 parts of decaglycerin laurate and parts of ethylene glycol were mixed and heated to 70 0 C to yield a homogeneous mixture. To the obtained mixture maintained at 50 0 C was slowly added water while stirring to 15 yield 100 parts of a suspension. This suspension was stirred in a homomixer at 3,000 rpm for 10 minutes to obtain an aqueous suspension pesticide preparation.

Immediately after preparation of the obtained aqueous suspension pesticide preparation, an average particle size and a viscosity were measured in the same manner as in Example 1.

As a result, the average particle size was 10.8 pm and the viscosity was 1090 mPa-s. However, after standing at 40 0 C for 3 days, an yellow viscous substance sedimented and was isolated. Therefore, the stable suspension state broke.

(Test Example 1) Storage test at high temperature conditions Each aqueous suspension pesticide preparation thus prepared was charged in a 500 ml glass bottle and was then allowed to stand in a temperature-controlled chamber at for 12 weeks. Various tests were carried out. The results are shown in Table i.

<Storage stability test> After the completion of the storage, the suspension state of each sample was observed. After the sample was allowed to stand at 200C for 24 hours, recovery of the suspension state was examined.

The test results are evaluated according to the following criteria.

r 15 suspension state is very good and active pesticide ingredient is satisfactorily dispersed 0: suspension state is very good and active pesticide ingredient is satisfactorily dispersed and, although slight water separation is observed in the upper layer, homogeneous suspension is easily achieved by shaking by hand A: suspension state is slightly poor and, although a portion of the suspension is deposited on the wall of the container, suspension is achieved by stirring with a stick X: suspension state is poor and nearly the entire suspension is in the form of a gel, while a portion thereof agglomerates but is not easily dispersed by stirring with a stick <Presence or absence of crystal precipitation> Samples, after standing for 12 weeks, were allowed to stand at 200C for 24 hours and, after 500-fold dilution, it IO was determined by an optical microscope whether or not crystal precipitates could be observed in the diluted solution.

<Measurement of residue on sieve> i Each sample, after standing for 12 weeks, was allowed to ,5 stand at 200C for 24 hours, and 50 g of each sample was diluted with 1 L of water. The total amount of the resulting diluted solution was passed through a sieve having holes of pm. Then, 1 L of water was poured onto the sieve, and the .sieve was moved horizontally. This operation of washing with &O water was repeated five times. After washing with water, the amount of the residue on the sieve was measured and the crystal precipitation was calculated by the following equation: ~(Amount of precipitate 0 Crystal precipitation by weight) (Amount of precipitate (Amount of in 50 g of sample) x 00 where denotes the weight of the active pesticide ingredient, denotes the weight of a compound represented by the general formula denotes the weight of a hydrogenated phospholipid having an iodine value of 20 or less, denotes the weight of a surfactant having a C 6 to C 20 alkyl group, and denotes the weight of a water-soluble protein.

**e o S S S *5 S S S S S S. S S S S S S 5*555 5 5 S S S S SS S 5.5 5 Table 1 Exapl 1Exmpe Eamle3 xapl 4 Comp. Comp. Comp.

Exaple1 Eampe 2Exaple3 Eampe ~Example 1 Example 2 Example 3 After completion 0 0 Storage of storage stability After recovery 0 at 20 0 Presence or absence of No No No No No No No crystal precipitates_____ Residue on sieve by0000000 weight) I_ I_ I_ I_ 27 (Test Example 2) Storage test under high temperature/low temperature cycle conditions Each aqueous suspension pesticide preparation thus prepared was charged in a 500 ml glass bottle, allowed to stand at a set temperature of 500C for 3 days, cooled to from 50'C over 12 hours, allowed to stand at a set temperature of -10°C for 3 days and heated to 500C from -10 0 C over 12 hours (one cycle per week), and then this cycle was repeated 12 times (12 weeks) and each sample was stored. In the same manner as in Test Example 1, the storage stability test, observation of presence or absence of crystal precipitates and measurement of residue on the sieve were carried out. The results are shown in Table 2.

After the completion of the storage test, the aqueous S 15 suspension pesticide preparation prepared in Comparative Example 3 was slightly deposited on the wall of the container at the upper portion of the liquid level in the form of a ring-shaped solid. After recovery at 200C, water separation was observed in the upper layer. The amount of the residue on the sieve was 1% by weight.

S S

S

Table 2 Example 1 Example 2 Example 3 Example 4 Comp. Comp. Comp.

_______Example 1 Example 2 Example 3 After completion 0A 0I Storage of storage stability After recovery 0 0 0 Presence or absence of No No No No No No No crystal precipitates sidu e on sieve by 0000001 29 (Test Example 3) Storage test under conditions at low temperature Each aqueous suspension pesticide preparation thus prepared was charged in a 500 ml glass bottle and was then allowed to stand at a set temperature of -5°C for 12 weeks.

In the same manner as in Test Example 1, the storage stability test, observation of presence or absence of crystal precipitates and measurement of residue on the sieve were carried out. The results are shown in Table 3. The aqueous suspension pesticide preparation prepared in Example 3 was in a creamy solidified state after the completion of the storage test and, after recovery at 20 0 C, it reverted to a suspension.

In contrast, the aqueous suspension pesticide preparation prepared in Comparative Example 1 was partially in the viscous 15 state after the completion of the storage test and, even after recovery at 200C, water separation was observed in the upper layer and clogging was caused by the residue on the sieve.

The amount of the residue on the sieve was 2% by weight.

The aqueous suspension pesticide preparation prepared in Comparative Example 2 was in a creamy solidified state after the completion of the storage test and, even after recovery at 200C, water separation was observed in the upper layer and clogging was caused by the residue on the sieve. The amount of the residue on the sieve was 2% by weight.

The aqueous suspension pesticide preparation prepared in Comparative Example 3 was in a creamy solidified state after the completion of the storage test and, even after recovery at 200C, water separation was observed in the upper layer and clogging was caused by the residue on the sieve. The amount of the residue on the sieve was 3% by weight.

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9** 0* too. Table 3 Example 1 Example 2 Example 3 Example 4 Camp. Camp. Camp.

Example 1 Example 2 Example 3 After completion 1* Storage of storage__ stability After recovery 0 0A at 20 0 Presence or absence of No No No No Yes Yes Yes crystal precipitates_____ Residue on sieve by 00002 2 3 eight) I_ I_ I_ I_ I_ creamy solidified state 32 (Test Example 4) Storage test under low temperature cycle conditions Each aqueous suspension pesticide preparation thus prepared was charged in a 500 ml glass bottle, was allowed to stand at a set temperature of 5 0 C for 6 hours, was cooled to 100C from 50C over 6 hours, was allowed to stand at a set temperature of -10*C for 6 hours, and was heated to from -10°C over 6 hours (one cycle), and then this cycle was repeated 84 times (12 weeks) and each sample was stored. In the same manner as in Test Example 1, the storage stability test, observation of presence or absence of crystal precipitates and measurement of residue on the sieve were carried out. The results are shown in Table 4.

After the completion of the storage test, the aqueous 15 suspension pesticide preparation prepared in Comparative Example 3 was in a creamy solidified state. After recovery at 200C, it reverted to a good suspension. In contrast, the aqueous suspension pesticide preparations prepared in Comparative Examples 1, 2 and 3 were in a creamy solidified state after the completion of the storage test and, even after recovery at 200C, they did not revert to a good suspension.

Therefore, clogging was caused by the residue on the sieve.

Since it is difficult to pass the residue through the sieve at one time by one operation, filtration was carried out in three portions. The amount of the residue on the sieve was 12% by weight in Comparative Example 1, 9% by weight in Comparative Example 2, or 18% by weight in Comparative Example 3.

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S* S. S S S S *SS S Table 4 Exapl 1Exmpe Eamle3 xapl 4Comp. Camp. Camp.

Exaple1 xamle Eampe 3Exmpl 4Example 1 Example 2 Example 3 After completion 1 1_* Storage of storage_____ stability After recovery x x at 20 0 Presence or absence of No No No No Yes Yes Yes crystal precipitates__________ Residue on sieve by 000 0 12 9 18 weight)__ creamy solidified state INDUSTRIAL APPLICABILITY The aqueous suspension pesticide preparation of the present invention not only has excellent storage stability under storage conditions where the temperature changes drastically in a long cycle through the seasons, but also excellent storage stability under storage conditions where the temperature changes within a range from 5 to -10°C in a short cycle through day and night.

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Claims

1. An aqueous suspension pesticide preparation which includes a 1,1-iminiodi(octamethylene)diguanidinium tris(alkyl-benzenesulfonate); a compound represented by the general formula R-O- (CH 2 CH 2 0) n-H wherein R represents a C8-C18 alkyl group and n represents an integer of 0 to 4; a phospholipid; a surfactant having a C6-C20 alkyl group; and water wherein the phospholipid is a hydrogenated phospholipid having an iodine value of 20 or less.

2. A pesticide preparation as claimed in claim 1, which further contains a water-soluble protein. o

3. An aqueous suspension pesticide preparation according r to claim 1 or 2, wherein the alkyl-benzenesulfonate 20 constituting the l,l'-iminiodi (octamethylene) diguanidinium tris(alkyl-benzenesulfonate) is benzene S. sulfonate having a Cio C13 alkyl group and the compound represented by the general formula is a compound having a Clo C13 alkyl group.

4. An aqueous suspension pesticide preparation according to any one of claims 1-3, wherein the surfactant is a surfactant having a Cio C 13 alkyl group.

An aqueous suspension pesticide preparation according to any one of claims 1-4, wherein each of the alkyl group of the alkyl-benzenesulfonate constituting the 1,1'- iminiodi (octamethylene) diguanidinium tris(alkyl- benzenesulfonate), the alkyl group of the compound represented by the general formula and the alkyl group constituting the surfactant is an alkyl group having the same number of carbon atoms.

6. An aqueous suspension pesticide preparation according to any one of claims 1-5, wherein an average particle size of suspension particles in the aqueous suspension ooo: 15 pesticide preparation as measured by a laser diffraction and scattering method of measuring the particle size is pm or less. Dated this thirtieth day of November 2004 Dainippon Ink Chemicals, Inc. Patent Attorneys for the Applicant: S' F B RICE CO