JPH09194301A - Aqueous suspension preparation of agrochemical - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare an aqueous suspension preparation excellent in long term storage stability and having high re-dispersibility by combining an alkylbenzene, a water soluble polymer compound, a surfactant and water with an agrochemical active ingredient and adjusting the viscosity of the preparation in a specific range. SOLUTION: This preparation consists of an agrochemical ingredient, an alkylbenzene of the formula ((n) is 4-9), a water soluble polymer compound, a surfactant and water and the viscosity of the preparation is set to 100-1000mPa.S at 25 deg.C. An insecticide, a microbicide, a berbicide, etc., is contained as the agrochemical active ingredient in amount of 0.1-60wt.% in the preparation. N-butylbenzene or n-amylbenzene is used as the alkylbenzene of the formula in the extent of 0.02-50 pts.wt. per 1 pt.wt. of the agrochemical active ingredient. Dextrin, carrageenan, guar gum, etc., is used as the water soluble polymer compound in the extent of 0.01-10wt.% in the preparation. Any surfactant capable of dispersing the above two ingredients in water is used in the extent of 0.2-10wt.% in the preparation.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aqueous suspension pesticide formulation, and more particularly to an aqueous suspension pesticide formulation which does not separate or settle during long-term storage.

[0002]

2. Description of the Related Art Conventionally, emulsions, wettable powders, etc. have been used as agrochemical formulations containing a high concentration of agrochemical active ingredients.
However, in recent years, due to safety issues such as flammability, odor, dusting, and environmental hygiene, the use of an aqueous suspension (also called a flowable agent) in which a pesticide active ingredient is dispersed in water as a solvent. Is increasing significantly. This suspension has advantages over emulsions in terms of safety and environmental hygiene, but on the other hand, dispersoids such as agrochemical active ingredients dispersed in water tend to settle out and separate during long-term storage of the preparation. At times, there is a demerit that the sedimentation layer hardens and redispersion becomes difficult.

Hitherto, various studies have been conducted on the types of auxiliary agents such as surfactants, thickeners and organic solvents and the amounts thereof in order to obtain a stable dispersion without such sedimentation or separation. I have been.

Studies using alkylbenzenes in aqueous suspension pesticide formulations include:

JP-A-5-132406 At least one herbicidally active compound from phenoxaprop-ethyl, sulphonylurea and / or phenylurea, aromatic solvents or solvent mixtures and ethoxylated tristyrylphenols and average chain lengths. A suspoemulsion comprising a surfactant composition of a C ₁₃ ethoxylated sterically modified synthetic alcohol, each of which can be neutralized with a phosphate or an alkali or amine.

[Patent Document 1] Japanese Unexamined Patent Publication No. 2-295903 A mixture of an oily substance in which a liquid herbicide active ingredient is dissolved in a petroleum-based aromatic solvent using water as a dispersion medium, a solid herbicide active ingredient, and a surfactant. , The surface tension at a temperature of 20 ° C. is 30 to 40 dyne / cm, and the contact angle of the rice leaf at the temperature of 20 ° C. with respect to the second leaf blade part is 105 degrees or less.

[0007]

As described above, the aqueous suspensions containing water as a dispersion medium should be improved in storage stability for a long period of time. However, although various improved technologies have been provided so far, they are still insufficient.

[0008] Therefore, the present invention is to provide an aqueous suspension preparation having long-term storage stability and high redispersibility.

[0009]

Means for Solving the Problems Accordingly, the present inventors have:
An intensive study was conducted for the purpose of developing a technique for preventing sedimentation of an aqueous suspension preparation. As a result, pesticide active ingredient, alkylbenzene,
Consists of a water-soluble polymer compound, a surfactant and water, 2
The inventors have found that an aqueous suspension pesticide formulation having a formulation viscosity at 5 ° C. of 100 to 1000 mPa · S has excellent suspension stability, and completed the present invention.

In practicing the present invention, a formulation viscosity of 10
If it is less than 0 mPa · S (25 ° C), sufficient formulation suspension stability cannot be obtained. In addition, 1000 mPa · S (25
If the temperature is higher than (° C.), The residual amount of the formulation adhered to the plastic container will be large, and it will take too long to discharge from the bottle. Therefore, the formulation viscosity is 100-1000 mPa · S (25 ° C)
Is most preferable for practical use.

The agricultural chemical active ingredient according to the present invention is exemplified below. However, the present invention is not particularly limited as long as it is generally used as an aqueous suspension pesticide.

Examples of insecticides CYAP, MPP, MEP, ECP, pirimiphos-methyl, diazinon, isoxathion, pyridafenthion, chlorpyrifos-methyl, chlorpyrifos, quilvar, marathon, PAP, dimethoate, thiomethone, ethylthiomethone, phosalone, PMP, DMTP, sulprofos, prothion, Profenofos, pyraclofos,
DDVP, monocrotophos, BRP, CVMP, dimethylvinphos, propaphos, acephate, DEP, EP
N, Ethion, NAC, MTMC, MIPC, BPM
C, PHC, XMC, Ethiophenecarb, Pirimicarb, Carbosulfan, Benfracarb, Mesomyl, Oxamyl, Thiodicarb, Aresulin, Resmethrin,
Permethrin, cypermethrin, cyhalothrin, cyfluthrin, fenpropatrin, tralomethrin, cycloprothrin, fenvalerate, flucitrinate, fluvalinate, etofenprox, cartap, thiocyclam, bensultap, diflubenzuron, teflubenzuron, chlorfluazuron, flufenoc Sullon, tebufenozide, buprofezin, benzoepine,
Imidacloprid, machine oil, kelsen, amitraz,
Hexythiazox, fenbutatin oxide, fenpyroximate, debufenpyrad, pyridaben, etc.

Examples of bactericides Copper sulfate, quick lime, basic copper calcium sulfate, basic copper sulfate, basic copper chloride, cupric hydroxide, copper ammonium complex salt organic copper, nonylphenol sulfone copper, DBEDC, copper terephthalate, Sulfur, Zineb, Manneb, Manzeb, Ambam, Polycarbamate, Organic sulfur nickel salt, Propineb, Ziram, Thiuram, Thiadiazine, Captan, Sulfenic acid system, TPN, Fusalide, IBP, E
DDP, triclofosmethyl, pyrazophos, fosetyl,
Thiophanate methyl, thiabendazole, iprodione, vinclozolin, procymidone, fluoroimide,
Mepronil, Flutranil, Teclophthalam, Pencyclon, Metalaxyl, Oxazixyl, Triadimefon, Bitertanol, Microbutanil, Hexaconazole, Propiconazole, Difenoconazole, Ipconazole, Imibenconazole, Triflumizole, Proclaroz, Pefrazoate, Fenarimol, Pyrifenox, Pyrifenox Dithianon, quinoxaline, D
PC, dimethylimol, flusulfamide, benzazole, diclomedine, triazine, ferimzone, fluazinam, dimethofencarb, probenazole, isoprothiolane, tricyclazole, pyroquilon, oxolinic acid, iminoctadine acetic acid, blasticidin S, kasugamycin, polyoxin, validamycin A, streptomycin, PCNB, hydroxyisoxazole, echromezole, metasulfocarb, and the like.

Examples of herbicides 2,4-PA, MCP, MCPB, MCPP, phenothiol, clomeprop, naproanilide, phenoxapropethyl, fluazifop, quizalofop-ethyl, clomethoxynil, bifenox, IPC, fenmedipham, benchiocarb, Esprocarb, Molinate, Dimepiperate, Pyributicarb, DCP
A, arachlor, butachlor, pretilachlor,
Tenylchlor, bromobutide, mefenacet, napropamide, diphenamide, propizamide, isoxaben, ashram, DCMU, linuron, dymlone,
Methyldimuron, carbutyrate, isouron, tebuthiuron, bensulfuron-methyl, pyrazosulfuron-ethyl, furazasulfuron, thifensulfuron, imazosulfuron, CAT, atrazine, simethrin, promethrin, dimetamethrin, cyanazine, terbacil, bromacil, PAC, bentazon, oxazone, oxazone Pyrazolate, pyrazoxifene, benzofenap, trifluralin, besrosin, pendimethalin, picloram, imazapyr, DPA, piperophos, butahomis, glyphosate, bialaphos, glyphosinate, ioxynil, DBN, alloxydim, sethoxydim, ACN,
Sinmethylin, benfresate, etc.

In the present invention, one or more of these pesticidal active ingredients may be used in combination.

In the present invention, the content of the pesticidal active ingredient in the pesticidal formulation is usually 0.1 to 60% by weight, preferably 5 to 50% by weight. Is good.

The names of the above-mentioned pesticide active ingredients are the common names described in "Pesticide Handbook, 1994 Edition" (published by the Japan Plant Protection Association).

Next, the alkylbenzene used in the present invention will be shown. In the present invention, the following general formula

Embedded image And one or more selected from the group represented by.

A specific example of this is n-butylbenzene.
Benzene, iso-n-butylbenzene, n-amylben
Zen, iso-amylbenzene, n-hexylbenze
N, n-heptylbenzene, n-octylbenzene, etc.
These can be used alone or as a mixture.
May be. In addition, these alkylbenzenes are
Benzyl (or Bromobenzene) and Halogenated Alky
Condensation of sodium with sodium in ether, phenylene
Contact with ruquil ketone (or benzyl alkyl ketone)
Hydrogenation or other reduction, benzene and alkyl halides
Also manufactured by condensation of aluminum chloride with aluminum
May be used, or a commercially available product may be used. Commercially available
The product is a mixture having 4 to 5 carbon atoms in the alkyl group.
Hisol E (trade name of Nippon Petrochemical Co., Ltd.)
(“Hisol” is a registered trademark, the same applies hereinafter), alkyl group
Which has a carbon number of 4 to 9 F (Japanese stone
Yuka Kagaku Co., Ltd.) and the like.

The alkylbenzene referred to in the present invention may be by-produced with a di-substituted product in addition to the mono-substituted product in the production process, but these can be effectively used as they are without being separated. it can.

The amount added to these preparations is 0.02 to 50 parts by weight, preferably 0.05 to 30 parts by weight, based on 1 part by weight of the agrochemical active ingredient, and used in the aqueous suspension preparation. Is desirable.

The alkylbenzene usable in the present invention is not limited to the above examples.

The water-soluble polymer compound used in the present invention includes the following. However, the present invention is not limited to the following examples.

Starch potato starch, wheat starch, dextrin

Seaweed sodium alginate, caranagin

[0026]Plant mucilage Locust bean gum, guar gum, tara gum, tamari
Gum gum, gum arabic, gum tragacanth, karayaga
, Pectin, arabinogalactan, soybean okara
The released water-soluble polysaccharide (Soya Five )Such

Mucus xanthan gum, pullulan, lanzan gum by microorganisms

Protein casein, gelatin, soy protein, wheat gluten,
Plant protein degradation product

Fibrous microcrystalline cellulose

The amount of these polymer compounds added to the aqueous suspension pesticide formulation is in the range of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, and used in the aqueous suspension formulation. Is good. Further, the surfactant according to the present invention is not particularly limited as long as it has a function of dispersing the agrochemical active ingredient and alkylbenzene in water. As such a surfactant, conventionally known nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants and the like can be used.

(Example of Nonionic Surfactant) Polyoxyethylene alkylaryl ether (eg: polyoxyethylene nonylphenyl ether), polyoxyalkylene arylphenyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene alkyl ester, poly Oxyethylene sorbitan alkylate, polyoxyalkylene glycol, polyoxyethylene phenyl ether polymer, etc.

(Examples of anionic surfactant) Lignin sulfonate, alkylaryl sulfonate, dialkyl sulfosuccinate, polyoxyethylene alkylaryl phosphate, polyoxyethylene alkylaryl ether sulfate, alkylnaphthalene sulfonate, poly Oxyethylene styryl phenyl ether sulfate, etc.

(Examples of Cationic Surfactant and Amphoteric Surfactant) Alkyl amines, quaternary ammonium salts, alkyl betaines, amine oxides and the like.

In the present invention, the content of these surfactants in the resulting aqueous suspension pesticide formulation is 0.2 to.
One kind or a combination of two or more kinds can be used in an amount of 30% by weight, preferably 0.5 to 20% by weight.

[0035]

BEST MODE FOR CARRYING OUT THE INVENTION In addition to the above-mentioned composition, an aqueous suspension pesticide formulation of the present invention comprises, if necessary, a synthetic or mineral-based thickener, an antifreezing agent, an antifoaming agent, an antifungal agent, It can be obtained by adding an auxiliary agent such as an antioxidant or an ultraviolet ray inhibitor and stirring the mixture to disperse it.

Specific examples of the synthetic or mineral thickeners include carboxymethyl cellulose,
Carboxymethyl starch sodium salt, hydroxyethyl cellulose, carboxyethyl cellulose, methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, polyacrylic acid and its derivatives, colloidal hydrous aluminum silicate, colloidal hydrous magnesium silicate, colloidal hydrous silicic acid. Aluminum magnesium etc. are mentioned.
In the present invention, one kind or a combination of two or more kinds may be used in such an amount that the content of these thickeners in the obtained aqueous suspension pesticide formulation is 0.05 to 10% by weight.

The thickener that can be used in the present invention is not limited to the above examples.

Further, as the antifreezing agent, specifically,
For example, ethylene glycol, propylene glycol, glycerin and the like can be mentioned, and as the antifoaming agent, a silicone-based or fatty acid-based one can be used, and an antifungal agent (antifungal / antiseptic preservative) Specifically, for example, sorbic acid, potassium sorbate, p-chloro-metaxylenol, butyl p-oxybenzoate and the like can be used. The auxiliary agents that can be used in the present invention are not limited to the above examples.

[0039]

[Examples] Next, regarding the aqueous suspension pesticide formulation of the present invention,
The present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples.

In the following examples and comparative examples, "part" means "part by weight".

[0041]Example 1 36 parts water, 20 parts pre-dissolved BPMC and polio
Xylethylene styryl phenyl ether 10 parts and al
4 parts calcium benzene sulfonate and Hisol
F  15 parts mixed solution, 2% xanthan gum aqueous solution 10
And 5 parts of ethylene glycol were added,
5000 rpm with Kisa (made by Tokushu Kika Kogyo Co., Ltd.)
Stir and mix for 10 minutes at a formulation viscosity of 25 ° C
An aqueous suspension pesticide formulation having 0 mPa · S was obtained.

[0042]Example 2 Hisol of Example 1 F 15 parts by n-amylbenzene
 Replaced with 15 parts and the formulation viscosity was 66 at 25 ° C.
An aqueous suspension pesticide formulation having 0 mPa · S was obtained.

Example 3 41 parts of water, 30 parts of NAC, 5 parts of pre-dissolved polyoxyethylene nonylphenyl ether, 3 parts of sodium lignin sulfonate and 3 parts of n-hexylbenzene.
Add 0 parts of mixed solution, 6 parts of gum arabic and 5 parts of ethylene glycol, and use TK homomixer for 5000 r
The mixture was stirred and mixed at pm for 10 minutes to obtain an aqueous suspension pesticide formulation having a formulation viscosity of 480 mPa · S at 25 ° C.

[0044]Example 4 49 parts water, 30 parts fusalide, pre-dissolved poly
Oxyethylene styryl phenyl ether 5 parts and high
Zor F 1 part mixed solution, 2% guar gum aqueous solution 10
And 5 parts of ethylene glycol were added,
Stir and mix at 5000 rpm for 10 minutes with a kisser to prepare a formulation
Aqueous suspension whose viscosity is 490 mPa · S at 25 ° C
A pesticide formulation was obtained.

[0045]Example 5 Hisol of Example 4 F 1 part is n-butylbenzene
Replaced by 1 part, the formulation viscosity is 480m at 25 ℃
An aqueous suspension pesticide formulation having Pa · S was obtained.

[0046]Example 6 Water 51.5 parts, imibenconazole 15 parts, previously dissolved
Dissolved polyoxyalkylene aryl phenyl ether
10 parts and Hisol E 10 parts mixture, 2% rum
8 parts of aqueous solution of Zan gum, colloidal hydrous aluminum silicate
Add 0.5 parts of um and 5 parts of ethylene glycol.
Well, with TK Homo Mixer (made by Tokushu Kika Kogyo Co., Ltd.)
Stir-mix at 5000 rpm for 10 minutes to give a formulation viscosity of 25
Aqueous suspension pesticide formulation that is 540 mPa · S at ℃
Obtained.

[0047]Example 7 Hisol of Example 6 10 parts of E is n-amylbenzene
 5 parts and 5 parts of n-hexylbenzene and 2% ramza
8 parts of aqueous gum solution and colloidal hydrous aluminum silicate
0.5 parts of 2% tara gum aqueous solution 4 parts and water 4.5 parts
The formulation viscosity is 110 mPas at 25 ° C.
-An aqueous suspension pesticide formulation of S was obtained.

Example 8 46 parts of water, 1 part of pre-dissolved phenothiol and 8 parts of polyoxyethylene styryl phenyl ether and i
So-amylbenzene 30 parts mixed solution, 2% caranagin aqueous solution 10 parts and ethylene glycol 5 parts were added, and the mixture was stirred and mixed at 5,000 rpm for 10 minutes with a TK homomixer, and the formulation viscosity was 470 mPa · s at 25 ° C.
An aqueous suspension pesticide formulation of S was obtained.

Example 9 30 parts of iso-amylbenzene of Example 8 was replaced with 30 parts of n-heptylbenzene, and the viscosity of the preparation was 25 ° C.
To obtain an aqueous suspension pesticide formulation of 480 mPa · S.

Example 10 Water 44 parts, DCMU 30 parts, pre-dissolved polyoxyethylene nonylphenyl ether 4 parts, n-heptylbenzene 3 parts and n-octylbenzene 2 parts mixed solution, 2% xanthan gum aqueous solution 12 parts And 5 parts of ethylene glycol were added, and 5,000 with TK homomixer
The mixture was stirred and mixed at rpm for 10 minutes to obtain an aqueous suspension pesticide formulation having a formulation viscosity of 960 mPa · S at 25 ° C.

Example 11 2% of 12 parts of 2% xanthan gum aqueous solution of Example 10
An aqueous suspension pesticide formulation having a formulation viscosity of 470 mPa · S at 25 ° C. was obtained by replacing the aqueous solution of gum arabic with 8 parts of water and 4 parts of water.

Example 12 3 parts of n-heptylbenzene and 2 parts of n-octylbenzene of Example 10 were replaced with 5 parts of iso-butylbenzene, and the formulation viscosity was 950 mPa · S at 25 ° C.
To obtain an aqueous suspension pesticide formulation.

Comparative Example 1 Hisol of Example 1 F 15 parts with 2% monat gum water
Aqueous suspension pesticide formulation with 5 parts solution and 10 parts water
I got

Comparative Example 2 10 parts of a 2% xanthan gum aqueous solution of Example 2 was added to water 1
An aqueous suspension pesticide formulation was obtained by substituting 0 part.

Comparative Example 3 10 parts of n-hexylbenzene of Example 3 was replaced with 2 parts of gum arabic and 8 parts of water to obtain an agricultural chemical suspension formulation.

Comparative Example 4 6 parts of gum arabic of Example 3 was replaced with 0.3 part of sodium carboxymethyl cellulose and 5.7 parts of water to obtain an aqueous suspension agricultural chemical preparation.

[0057]Comparative Example 5 Hisol of Example 4 1 part F to 1 part water 2% guar
-Gum aqueous solution 10 parts with 3% colloidal hydrous silicate
Aqueous suspension pesticide formulation was obtained by replacing Minium 10 parts.
Was.

Comparative Example 6 An aqueous suspension agricultural chemical preparation was obtained by replacing 1 part of n-butylbenzene of Example 5 with 1 part of water.

[0059]Comparative Example 7 Hisol of Example 6 E 10 parts with 2% rumzan gum water
Replace with 2 parts of solution and 8 parts of water to prepare an aqueous suspension pesticide formulation.
Obtained.

Comparative Example 8 4 parts of the 2% tara gum aqueous solution of Example 7 was reduced to 2 parts,
An aqueous suspension pesticide formulation was obtained by replacing with 2 parts of water.

Comparative Example 9 An aqueous suspension agricultural chemical preparation was obtained by replacing 10 parts of the 2% kalanergin aqueous solution of Example 8 with 10 parts of 3% colloidal hydrous aluminum magnesium silicate.

Comparative Example 10 30 parts of n-heptylbenzene of Example 9 was replaced with 10 parts of a 2% aqueous solution of caranagin and 20 parts of water to obtain an agricultural chemical suspension formulation.

Comparative Example 11 3 parts of n-heptylbenzene of Example 10 and 2 parts of n-octylbenzene were replaced with 5 parts of water to obtain an aqueous suspension pesticide formulation.

Comparative Example 12 12 parts of 2% xanthan gum aqueous solution of Example 10 was added to water.
An aqueous suspension pesticide formulation was obtained by substituting 12 parts.

Comparative Example 13 3 parts of n-heptylbenzene and 2 parts of n-octylbenzene of Example 10 were replaced with 2 parts of a 2% aqueous xanthan gum solution and 3 parts of water to obtain an agricultural chemical suspension formulation.

Comparative Example 14 8 parts of the aqueous solution of gum arabic of Example 11 was reduced to 2 parts, and the rest was replaced with 6 parts of water to obtain an agricultural chemical suspension formulation.

Comparative Example 15 An aqueous suspension agricultural chemical preparation was obtained by replacing 5 parts of n-butylbenzene of Example 12 with 2 parts of a 2% xanthan gum aqueous solution and 3 parts of water.

Comparative Example 16 25 parts of 2% xanthan gum aqueous solution of Example 12 was used.
% Polyvinyl alcohol aqueous solution was replaced with 12 parts to obtain an aqueous suspension pesticide formulation.

Next, the usefulness of the aqueous suspension pesticide formulation of the present invention will be shown by test examples.

Test Example 1 Suspension Agent Long-term Storage Stability Test The prepared aqueous suspension pesticide formulation had a volume of 30 ml (φ17 mm
(30 mm length 180 mm), put 30 ml in a test tube, seal the tube, and leave it in a thermostatic chamber at 20 ° C. or 40 ° C. And
The separation state after 3 months at 20 ° C and after 3 months at 40 ° C, respectively, shows that the suspension agent in the test tube settled in the lower layer and the water layer (upper layer) formed in the upper layer (Cm) was measured and calculated by the following formula.

[0071]

[Equation 1]

Test Example 2 Viscosity Measurement The viscosity of an aqueous suspension pesticide preparation immediately after preparation was measured using a B-type viscometer [manufactured by Tokimec Co., Ltd.], rotor No. 2, rotation speed 12 r. p. m at a temperature of 25 ° C.

The results are shown in Table 1.

Test Example 3 Discharge Test 450 ml of the aqueous suspension pesticide formulation immediately after preparation was placed in a plastic bottle having a capacity of 500 ml, allowed to stand at 25 ° C. for 1 day, and the container was inverted 20 times, and then the container was inverted. Discharge the aqueous suspension pesticide formulation. The interval between the drug drops from the container mouth is 1
The end time is 0 seconds or more. At this time, the weight of the drug discharged was measured and expressed as a percentage (%) with respect to the weight of the drug filled in the container.

The results are shown in Table 1.

[0076]

[Table 1]

[0077]

EFFECTS OF THE INVENTION The aqueous suspension pesticide formulation of the present invention maintains stability even when stored for a long period of time without causing separation and sedimentation of components suspended in water such as pesticide active ingredients.

Therefore, even when sprayed after being stored for a long period of time, there is no precipitate in the suspending agent and it can be easily sprayed.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area A01N 47/22 A01N 47/22 G 47/30 47/30 B

Claims (1)

[Claims] 1. A pesticide active ingredient, an alkylbenzene represented by the following formula, a water-soluble polymer compound, a surfactant and water, and has a formulation viscosity of 100 to 1000 m at 25 ° C.
Pa · S, Aqueous suspension agricultural chemical formulation characterized by the above. [Formula 1]