HU199233B - Stabilized aqueous pesticidal suspension concentrate - Google Patents

Abstract

An aqueous pesticidal suspension concentrate comprises up to 50% by weight of a solid pesticide which is insoluble or only slightly soluble in water, 0.1 to 5% by weight of a non-ionic surfactant having an alkyl- or aralkyl-substituted aromatic ring as oleophilic group, 0.1 to 5% by weight of an alkylphenol polyglycol ether, a heteropolysaccharide thickener, and optionally other ingredients such as hydrophilic silica, propylene glycol and defoaming agent.

Description

The present invention relates to stabilized aqueous pesticide suspension concentrates. In particular, aqueous pesticidal suspension concentrates which are capable of maintaining a uniform dispersion for a long period of time and can be used not only in conventional applications, but also in high concentration formulations such as suspended solids (e.g., ULV formulation, ultra-low volume formulation, low volume formulation), formulation S (spray)], and other emulsifiable concentrates may also be used even in high concentration formulations due to a special surfactant and a water soluble heteropolysaccharide type filler.

Known types of agricultural pesticides include dusts, granules, wettable powders and emulsifiable concentrates. One disadvantage of these is that they are too dispersed in application. Wettable powders are highly dusty during the preparation of the liquid formulation, since they are composed of particles of very small particle size, which can cause inflammation of the skin of those working with these agents. A disadvantage of emulsifiable concentrates is that the emulsifiable pesticides have a small range because they are required to be well soluble in organic solvents. They also have the disadvantage that the formulations are unsafe and flammable due to the presence of the organic solvent, and that these emulsifiable formulations damage certain crops.

Floating formulations (ULV, LV and S formulations) have recently become popular because they can save time and work. However, conventional pesticides are not always capable of being formulated as such floating compositions, and a new formulation suitable for formulation into a floating formulation is therefore required. Suspension concentrates which are prepared by suspending particles of very small particle size, which are insoluble in water or have very little solubility in water or in a hydrophilic solvent with the addition of an emulsifier and dispersant, are known as formulations suitable for the formation of floating compositions.

However, the known suspension concentrates are not stable for long enough. When used in combination with other pesticidal emulsions in the form of floating formulations, flocculation of suspended particles can occur and flocculates may precipitate and settle, causing blockage in the dispenser. In addition, flocculants can cause phytotoxicity in crops. Conventional formulations thus do not possess the properties required to form floating formulations.

Japanese Patent Application Laid-open No. 129 201/80, 124 702/83 and Publication No. 24401/83 disclose methods for preparing suspension concentrates. Japanese Patent Application Publication No. 129 201/80 does not provide a suitable solution for wetting technical grade pesticides and thus for uniformly suspending non-or only slightly soluble water. This formulation, when used in combination with other pesticidal emulsions, exhibits a tendency to flocculate, causing clogging of the delivery device.

The suspension of Japanese suspension application No. 24401/83 is unstable for prolonged storage. Japanese Patent Application Laid-Open No. 124702/83 cannot be used in admixture with other pesticide formulations.

A common solution for controlling insects that have multiplied over a period of time is to mix the pesticides with other formulations and apply them together, saving time and labor. However, conventional suspension concentrates, when mixed with other formulations, tend to form cream-like flocculates, which cause clogging of the delivery device.

FIELD OF THE INVENTION The present invention relates to stabilized aqueous pesticidal suspension concentrates which contain as active ingredients at least one pesticide composition which is solid at normal temperature, insoluble in water or slightly soluble in water and which can be uniformly and stably suspended in water. The resulting pesticidal suspension concentrate is easy to handle, has excellent storage stability, suspensibility, and dispersibility in application, is suitable for use in floating formulations, and can be used in admixture with other pesticides. These excellent properties of the composition of the invention are due to the surfactant and water-soluble heteropolysaccharide filler present in the mixture.

The stabilized aqueous pesticidal suspension concentrate is not only suitable for use in agriculture but is also suitable for wood preservation, for example brown rot fungi such as Soniophova puteana, Serpula lacrymans, Tyromyces palustris; white rot fungi such as Coriolus versicolor; soft rot fungi such as Chaetomium by treating the trees or soil with the suspension concentrate. The suspension concentrate of the invention may also be used in the treatment of fungi (Puccinia spp.), Rhizoctonia solani Kühn, etc. phytotoxicity in lawns and pastures.

For the pesticidal suspension concentrates of the present invention, any known pesticidal active ingredient which is solid at normal temperature and is not or only slightly soluble in water may be used.

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For example, fungicides such as diisopropyl-1,3-dithiolan-2-ylidene malonate (isoprothiolane), 3'-isopropoxyl-10C0C trifluoro-o-toluoylide (flutolanyl), 3'-isopropoxy-2 -toluuanilide (mepronil), 4,5,6,7-tetrachlorophthalide (phthalide); insecticides such as 2- (tert-butylimino) -3-isopropyl-5-phenyl-3,4,5,6-tetrahydro-2H-1,3,5-thiadiazin-4-one (buprofezin), m- tolyl N-methylcarbamate (metolcarb); herbicides, for example. 2-chloro-4,6-bis (ethylamino) -1,3,5-triazine (simazine), 2-chloro-4- (ethylamino) -6- (isopropylanino) -1,3 , 5-triazine (atrazine). By way of illustration only examples are provided and other similar pesticides may be used as active ingredients in the preparation of the aqueous pesticidal suspension concentrate of the present invention.

Said pesticides may be used alone or in admixture in amounts of 10-50% by weight of the total composition.

The alkylphenol polyglycol ether used in the composition of the invention is preferably nonylphenol polyglycol ether in an amount of 1-5.0 tX, preferably 1-3 tX.

As the surfactant containing a nonionic oleophilic group, the condensation products of alkylphenol polyglycol ethers with formaldehyde and / or thyryl phenol polyglycol ethers can be used. These materials may be used alone or as a mixture of several of these materials. The amount of nonionic surfactant is preferably in the range of 1-5.0 tX.

The water-soluble filler is heteropolysaccharide. This polysaccharide, commonly known as Xanthan resin, is a high molecular weight linear extracellular substance produced by bacteria of the genus Xanthomonas. _w herein of such materials correspond to those having a molecular weight greater than 200 000, preferably between 200 000 and 3 000 000th The heteropolysaccharide is used in an amount such that the resulting pesticidal suspension concentrate exhibits at least a shear stress of 1.0 Pa at a shear rate of 0 sec ^-1 at 25 ° C. This amount is usually 0.05 and

0.5 tX.

The solvent used in the aqueous pesticidal suspension concentrate of the invention is essentially water. Water can be used as such, but may also be used, if necessary, with organic hydrophilic solvents such as methanol, ethanol, isopropanol, polyethylene glycol, ethylene glycol, propylene glycol, etc., in some cases hydrophobic solvents such as xylene, toluene, kerosene, mineral and vegetable oils, liquid paraffin, etc. When an organic solvent is used, it is mixed with water in an amount of 1-30 tX, preferably 10-20%.

The aqueous pesticidal suspension concentrate of the present invention may, if necessary, contain additional ingredients, in addition to those listed above, such as an antifoaming agent 4, such as a silicone based antifoam agent consisting mainly of dimethylpolysiloxene in amounts up to 5 tX.

It is also possible to use hydrophilic silica or other similar grinding additives up to 5 tX.

Other pesticides which may be used in admixture with the aqueous pesticidal suspension concentrate of the invention include phenitrothion emulsions, BPMC [2- (sec-butyl) phenyl-N-methylcarbamate] emulsion, phenitrothion-BPMC emulsion, diazinon [0,0-diethyl]. -0- (2-isopropyl-6-methylpyrimidin-4-yl) -phosphorothioeth] emulsion, pentate (ethyl 2- (dimethoxythiophosphorylthio) -2-phenylacetate) emulsion, isoprothiolane emulsion, mayonnone [ 0,0-dimethyl-5- (1,2-dicarbethoxyethyl) phosphorodithioate] emulsion, IBP (S-benzyl-OO-diisopropyl phosphorothioate) emulsion, etc.

For example, the aqueous pesticide suspension concentrates of the invention may be prepared as follows. A predetermined amount of alkylphenol polyglycol ether, a nonionic surfactant, antifoam agent, if necessary, and an organic solvent or solvents are suspended or dissolved in water in a mixer. The active ingredient is then added and the mixture is ground in a wet mill until the active ingredient has a particle size of less than 5 µm, preferably between 0.5 and 3.0 µm. A predetermined amount of the heteropolysaccharide is then added to the mixture, and the mixture is further blended until homogeneity is achieved.

The invention is illustrated by the following examples. In the examples, unless otherwise noted, the term .part * denotes a capital portion.

Example 1

Used materials:

Buprofezin (p. 42.00 part

104.5-105.5 ° C, Chemical Name Page 1 of 5)

Nonyl phenol polyglycol ether 1.40 (10 moles ethylene oxide per mole surfactant)

Styrylphenol Polyglycol Ether 2.00 (24 moles ethylene oxide per mole surfactant)

Propylene glycol 3.00

Antifoam 0.50

Heteropolysaccharides (200,000 - 0.15

-3,000,000 molecular weight)

Hydrophilic silica 3.00 (grinding additive)

Viz 47.95

To 47.95 parts of water are added 1.40 parts of nonylphenol polyglycol ether (10 EO), 2.00 parts of styrylphenol polyglycol ether (24 EO), 3.00 parts of propylene glycol, and 0.50 parts of foaming agent.

HU 199233 Β (Siclone KM-73, The Shin-Etsu Chemical Co.,

Ltd.), dissolve and mix for 20 minutes with a stirrer (Homomixer Model HV-M, Tokushukika Kogyo Co., Ltd.). Then, 42.0 parts of 5 buprofezin and 3.00 parts of hydrophilic silica (Carplex 80 Mesh, Shionogi and Co.,

Ltd.) and grind the mixture for three hours in a wet mill (Attritor, Mitsui Miike Machinery Co., Ltd. 10). Finally, 0.15 parts by weight of a heteropolysaccharide of 200,000 to 3,000,000 molar weights are added and the mixture is stirred for 20 minutes to obtain 100 parts of a homogeneous composition. 15

Prepared in the same manner as in Examples 2-9. Examples 1-10. Reference Example 10-14. and Examples 11-15. Reference example products. The composition of the compositions by weight is shown in Table I, II. and ΙΠ. table we included in her. 20

Table I

Example number Second Third 4th 5th 6th 7th 8th 9th Buprofezin (p. 104.5-105.5 ° C Chemical Name Page 1 of 5) 42.00 42.00 42.00 42.00 42.00 42.00 42.00 42.00 Nonyl phenol polyglycol ether (10 EO) 1:40 1:40 1:40 1:40 1:40 1:40 1:40 1:40 Styryl phenol polyglycol ether (24 EO) - 1:00 0.80 0.80 0.80 0.80 0.80 0.80 Condensates of formaldehyde and nonylphenol polyglycol ether (30 EO) 2:00 1:00 1:20 1:20 1:20 1:20 1:20 1:20 Propylene glycol 3:00 3:00 3:00 3:00 3:00 3:00 3:00 3:00 Dimethyl polysiloxane (KM - 73) 0:50 0:50 0:50 0:50 0:50 0:50 0:50 0:50 Heteropolysaccharide (MW 200,000-3,000,000; 0:15 0:15 0:08 0:10 0:12 0:14 0:16 0:18 Hydrophilic Silica (Carplex) 3:00 3:00 3:00 3:00 3:00 3:00 3:00 3:00 Water 47.95 47.95 48.02 48.00 47.98 47.96 47.94 47.92 altogether 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00

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-510

HU 199233 Β III. Spreadsheet

Example Reference example 10 11 12 11 12 13 14 15 Flutolanyl (m.p. 102-103 ° C; Chemical name, pages 1.5) 24.30 24.30 24.30 24.30 24.30 24.30 24.30 24.30 Phthalide (m.p. 209-210 ° C; Chemical Name Page 1 of 5) 18.60 18.60 18.60 18.60 18.60 18.60 18.60 18.60 t'-Ionyl-phenol-polyglycol ether (10 EO) 2:00 2:00 2:00 2:00 2:00 2:00 2:00 2:00 Styryl phenol polyglycol ether and (24 EO) 1:00 1:00 1:00 - - 1:00 1:00 1:00 Condensate of Honil Phenol Polyglycol Ether and Formaldehyde (30 EO) 1:00 1:00 1:00 - - 1:00 1:00 1:00 Condensate of naphthalenesulphonic acid and formaldehyde - - - 2:00 - - - - Calcium ligninsulfonate - - - - 2:00 - - - propylene 3:00 3:00 3:00 3:00 3:00 3:00 3:00 3:00 Polydimethylsiloxane (KM-73) 0:50 0:50 0:50 0:50 0:50 0:50 0:50 0:50 Hydrophilic Silica (Carplex) 2.70 2.70 2.70 2.70 2.70 2.70 2.70 2.70 heteropolysaccharide (Molecular weight: 200,000-3,000,000) 0:10 0:13 0:15 0:15 0:15 - - - Sodium alginate - - - - - - 0:15 0:25 Water 46.80 46.77 46.75 46.75 46.75 46.90 46.75 46.65 altogether: 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00

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HU 199233 Β

Example No. ________ composition —— -— 13 14 Flutolanyl (m.p. 102-103 ° C; chemical name 1.5) 11.80 21:50 Phthalide (m.p. 209-210 ° C; chemical name page 1.5) 8.76 - Nonyl phenol polyglycol ether (10 EO) 2:00 2:00 Styryl phenol polyglycol ether and (24 EO) 1:00 1:00 Condensate of nonyl phenol polyglycol ether and formaldehyde (30 EO) 1:00 1:00 Condensate of naphthalenesulphonic acid and formaldehyde - - Calcium ligninsulfonate - - propylene 3:00 3:00 Dimethyl polysiloxane (KM-73) 0:50 0:50 Hydrophilic Silica (Carplex) - - Heteropolysaccharide (MW 200,000-3,000,000) 0:35 0:35 Sodium alginate - - Water 71.59 70.65 Altogether 100.00 100.00 Apparent viscosity (Pa-s) 0092 0120 Voltage value Pa 3.4 4.1 Deposition volume ratio 100 100

Both formulations can be used with commercially available pesticides. In the assays of Test Example 2, a value of .0 'is given.

Test Example 1

The viscosity (apparent viscosity and tension value) and physical stability (settling volume / volume ratio) of the preparation prepared according to the corresponding examples and reference examples were determined as follows.

Viscosity:

A viscometer of this type (manufactured by Tokyo Keiki Ltd.) was measured maintaining the sample temperature at 25 ° C. Cone angle: Γ34. The apparent viscosity is the viscosity measured at a shear rate of 100 sec ' ¹ . The voltage value is the shear stress measured at 0 sec * ¹ shear rate.

Deposition rate:

ml aliquots were placed in 1.3 cm internal diameter, 20 ml measuring cylinders and 40 ^'b C was held for one month. The volume of V (ml) occupied by the sediment was then determined and the ratio of the volume to the total volume45 was calculated using the following formula:

V

Deposition volume ratio = - · 100 ⁵⁰

The value obtained can be expressed as an index of physical stability of the formulation.

The results are shown in Table IV. are summarized in Table.

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HU 19S233 b IV. spreadsheet.

Tested Voltage Deposition composition viscosity value by volume 1 (Pa-s) (Pa) Invention of Example 1. 0265 3.8 100 Example 2. 0265 4.0 100 Example 3. 0265 4.3 100 Example 4. 0130 1.4 99 Example 5. 0160 2.1 99 Example 6. 0210 2.8 100 Example 7. 0250 4.6 100 Example 8. 0280 5.8 100 Example 9. 0320 6.2 100 Example 10. 0192 1.3 89 Example 11. 0210 2.1 99 Example 12. 0185 3.0 100 control Reference Example 4. 0092 0 66 Reference Example 5. 0248 0 85 Reference Example 6. 0432 0 85 Reference Example 7. 0260 0 78 Reference Example 8. 0216 0 75 Reference Example 9. 0050 0 73 Reference Example. 0055 0 73 Reference Example 13. 0020 0 60 Reference example. 0230 0 60 Reference Example. 0280 0 60 -1

Test Example 2

In a 500 ml wide mouth bottle approx. 150 ml of water were added and weighed

62.5 ml of the usual pessicide emulsion was then suspended or dispersed. Subsequently, 31.3 ml of the pesticidal suspension concentrates of the invention were weighed, dispersed evenly, and the flask was filled with water to 500 ml. Similarly, samples were prepared with the preparations of the reference examples. These mixed liquid formulations were allowed to stand for 2 hours and passed through a sieve with 61 μαι. Based on the amount of residual residue, it can be judged which of the formulations tested can be used in admixture with conventional pesticidal emulsions. The results are

Table V below. In the table, '0' means no residue and this composition can be used in a mixture, while x * means that there is a cream-like residue, so this preparation cannot be used in a mixture.

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HU 19S233 Β

Table K

Phenitrophosphenophenitridazinone Fentate Isopropylation IBP was tested preparation thionane emulsion thiolane emulsion emulsion emulsion fenkarb emulsion emulsion According to the invention Example 1. She She She She She She She She Example 2. She She She She She 0 She She Example 3. She She She She She She She She Example 11. 0 0 She She She She She She Control] Reference eg. First X X X X X X X X Reference eg. Second X X X X X X X X Reference eg. Third X X X X X X X X Reference eg. 11th X X X X X X X X Reference eg. 12th X X X X X X X X

phenitrothion: 0.0-dimethyl-O- (4-nitro-m-tolyl) diazinon: 40X phosphorothioate, no. ²⁵ : 1.5528; 30 Oscencarb: 2- (sec-butyl) phenylmethyl carbamate, m.p. 31-32 ° C;

diazinon: 0.0-diethyl-O- (2-isopropyl-6-methyl-pyrimidin-4-yl) -phosphorothioate, No ²⁵ : 1.4978-1.4981; Phentate 35: Ethyl 2- (dimethoxythiophosphorylthio) -2-phenylacetate, No ²⁵ : 1.5550;

isoprothiolane: m.p. 50-54 ° C, chemical name 1. p. 5;

ISP: S-benzyl-0,0-diisopropyl phosphorothioate, 40 p.p. 126 ° C (5.33 Pascal);

malathion: 0,0-dimethyl-S- (1,2-dicarbethoxyethyl) phosphorodithioate; mp: 285 ° C.

The composition of commercial preparations is as follows:

Phenitrothion Emulsion 1 (Suroithion e.c., manufactured by Nihon Nohyaku Co., Ltd., Japan)

fenitrotion: 50% pharynx active substance, 50 organic solvent, etc .: 50X osfencarb emulsion (Bassa e.c., Nihon Nohyaku Co., Ltd., Japan) oszfenkarb: 50X surfactant, 55 organic solvent, etc .: 50% phenitrothion / osfencarb emulsion (Sumibassa e.c., Nihon Nohyaku Co., Japan nya) fenitrotion: 45X 60 oszfenkarb: 30X surfactant, organic solvent, etc .: 25X emulsion (Diazinon e.c., Nihon

Nohyaku Co., Ltd. Japan) 65 surfactants, organic solvents, etc .: 60X

5. Phentate emulsion (Elsan e.c., manufactured by Nihon Nohyaku Co., Ltd., Japan) Phentate: 50% surfactant, organic solvent, etc .: 50X

6. Isoprothiolane emulsion (Fuji-one e.c., manufactured by Nihon Nohyaku Co., Ltd., Japan) Isoprothiolane: 40X surfactant, organic solvent, etc.: 60X

7. Malathion emulsion (made by Malathon e.c., Rubber Chem. Ind. Co., Ltd., Japan) malathion: 50X surfactant, organic solvent, etc .: 50X

8. IBP Emulsion (Kitazin P e.c., made by Kumiai Chem., Ind. Co., Ltd., Japan)

IBP: 48X surfactant, organic solvent, etc .: 52X Comparative Example

1. The composition of the composition is the same as that of Example 1 of the present invention.

2. Composition according to U.S. Patent No. 1,145,252. U.S. Pat. No. 5, except that buprofezin was used as the active ingredient.

buprofezin 38 parts by weight polyoxyethylene phenyl phenol ether 7 parts by weight

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EN 199233 Β (12 moles ethylene oxide / mole polythoxyethylene surfactant) polyoxypropylene block polymer (KaO Co. Ltd., 2.5 parts Japan No. 7-1246) Silicone oil 0.2 parts by weight sprays 10 parts by weight heteropolysaccharide ( Molecular weight: 0.2 tm

200,000-3,000,000 water 42.1 portions of volume

The water is weighed into a 500 ml wide mouth flask, 62.5 ml of commercial liquid pesticidal emulsion is added and mixed until a uniform emulsion is obtained. Next, 31.1 ml of the aqueous pesticidal suspension concentrate of the invention is added and uniformly distributed to give a mixed liquid pesticide formulation in a diluted form (8 L / ha) for LV (low volume) application. Similar mixtures are prepared in the same manner using the literature suspensions. The liquid mixtures were allowed to stand for 2 hours and then passed through a sieve having a mesh size of 0.06 mm. Based on the amount and condition of the residue remaining on the screen, assess whether the sample can be used in admixture with commercially available emulsified pesticides. The results are shown in the table below. In the table, .o 'indicates no residue on the sieve and the concentrate can be used in admixture with commercial liquid pesticides, while .x' indicates that there is a creamy residue on the sieve and the concentrate cannot be used in admixture with commercial liquid pesticides.

VI. spreadsheet

Claims (1)

Stabilized aqueous pesticide suspension concentrates which: 5 - one or more non-water-soluble or poorly soluble pesticides at room temperature in an amount of 10-50% by weight, a heteropolysaccharide having an average molecular weight of 200,000-3,000,000 in an amount of 0.05-0.5% by weight, (C8-C10 alkyl) phenol-polyglycol ether in an amount of 1 to 5% by weight, water and other excipients, preferably organic solvents, antifoam, 15 excipients - in a total amount of 40-88% by weight, characterized in that the non-ionic surfactant containing an oleophilic group, preferably containing from 1 to 5% by weight of the condensation product of formaldehyde and a (C 8 -C 10) alkylphenol polyglycol ether and / or styrylphenol polyglycol ether. Commercial liquid pesticide First composition Second composition 45 Fenitrothion emulsion She X Osfencarb emulsion 0 X Phenitrothion osfencarb 50 emulsion She X Diazinon emulsion She X Fentoate Emulsion She X Isoprothiolane emulsion She X Malation emulsion She X 55 IBP Emulsion She X As can be seen from the table, the composition of the present invention did not form a sediment, whereas the prior art formed a creamy residue.