CS236860B2 - Plant protecting agents and theirs processing method - Google Patents

Abstract

1. Suspension concentrates of plant protection agents based on a pesticide insoluble or sparingly soluble in water or a physiologically acceptable solvent, a phospholipid and an organic solvent or solvent mixture, characterised in that the concentrate consists of a) 15-35% of a pesticide insoluble or sparingly soluble in water or a physiologically acceptable solvent at 2% or less and having a melting point of > 40 degrees C, b) 15-35% of a phospholipid from the group phosphatidylcholine, the hydrogenated phosphatidylcholines, phosphatidylethanolamine, the N-acylphosphatidylethanolamines, phosphatidylinositol, phosphatidylserine, and the mixtures of several of said phospholipides and c) 40-60% of a solvent or solvent mixture from the group of the alcohols and the ethers, the mean particle size being =< 1 mu m.

Description

(54) Suspensions of plant protection products and processes for their preparation

Г 2

Suspension concentrates - plant protection products - insoluble, resp. the solubility of the pesticide, the solubility of which, in water or in the physiologically acceptable organic solvent used, is equal to or less than 2% by weight, of phospholipid and of the organic solvent; solvent mixtures, characterized in that - the concentrate consists of:

a) from 15 to ^35:% '- weight - nerozpustné- him popříp. - difficult to - soluble pesticide with - melting point higher than - - 40 ° C,

b) 15 to -35% by weight of phospholipid-a

c) 40-60% by weight of a solvent or a mixture of solvents from the group of alcohols, optionally. ethers, - and medium - particle size is - equal to 1 gm · * - or · is less - than 1 - gm.

The concentrates according to the invention are prepared by co-grinding the individual components in a colloid mill, ball mill, sand mill, stirrer or friction ball mill for 10 to 60 minutes at a temperature of 20 to 50 ° C.

The present invention relates to novel suspension concentrates of plant protection products which contain, in addition to the insoluble or sparingly soluble pesticide, a phospholipid and a physiologically acceptable solvent or mixture of solvents from the group of alcohols or ethers, as well as a process for their preparation.

The use of plant protection products to reduce harvest losses caused by diseases, pests and weeds can no longer be abandoned in agriculture. Most plant protection products are insoluble in water, possibly. The compositions must be used in the form of a wettable powder or emulsion concentrate at a very dilute concentration.

In agriculture, emulsion concentrates are more preferred than powder forms or granules for more favorable dosing. Emulsion concentrates are emulsified in water and applied as spray suspensions.

Spray suspensions are generally prepared from anhydrous emulsion concentrates or emulsion concentrates containing a small amount of water of the non-water-soluble active ingredients. Emulsion concentrates contain about 10 to 40% of the active ingredients and additionally contain organic solvents and emulsifiers, as well as other additives such as stabilizers, other wetting agents, antifoams, etc.

In order to produce emulsion concentrates of these non-water-soluble active ingredients, the active ingredients are dissolved in a suitable organic solvent such as alkylbenzene, acetone, kerosene, toluene and the like, and a suitable emulsifier or mostly mixtures of such emulsifiers is added to the solution. . The emulsifiers used are preferably anionic, cationic or non-ionic emulsifiers, respectively. mixtures of these emulsifiers. Many surfactants and many emulsifiers can greatly disrupt the osmosis and water management of the plants, so that the treated plants are damaged. In addition *, the solvents used in these cases are mostly toxic themselves and may contribute to the environmental hazard.

When using the spray suspension, the corresponding concentrates should be spontaneously emulsified. The resulting emulsion should be so stable that, even after standing for several hours, irreversible decomposition of the mixture into components does not occur. Permanent foam should not be formed during mixing and transfer. The requirements for an ideal spray suspension are, for example, the formation of a continuous film of active substance with good adhesion or wetting of the plant to be protected, as well as high resistance to rain wash or other weathering effects. Furthermore, it is intended to ensure the rapid penetration of the active ingredient into the plant.

However, most pesticides are not only soluble or sparingly soluble in water, but are also not soluble in solvents acceptable for agricultural purposes. Such compositions can then only be used in the form of granules or wettable powder. In practical application, there are then difficulties in accurate dosing and application. It is therefore desirable to have a liquid form for such active substances.

Surprisingly, it has now been found that stable suspension concentrates of plant protection agents are obtained if they are ground insoluble or possibly ground. sparingly soluble pesticides in admixture with a phospholipid selected from the group consisting of phosphatidylcholine, hydrogenated phosphatidylcholine, phosphatidylethanolamine, N-acylphosphatidylethanolamine, phosphatidylinositide, phosphatidylserine and phosphatidylglycerol or a solvent mixture of several such phospholipids or a solvent mixture of such phospholipids or .

SUMMARY OF THE INVENTION The present invention relates to suspension concentrates of plant protection agents on the basis of insoluble and / or non-soluble formulations. of a slightly soluble pesticide, the solubility of which in water or in the physiologically acceptable organic solvent used is equal to or less than 2% by weight, of phospholipids and of the organic solvent, respectively. a solvent mixture consisting of a concentrate consisting of

(a) 15 to 35% by weight of insoluble or difficultly soluble pesticide with a melting point of more than 40 ° C;

b) 15 to 35% by weight of phospholipids and 40 to 60% by weight of a solvent or solvent mixture of the group of alcohols or ethers, and the mean particle size is equal to or less than 1 µm.

In the concentrates according to the invention, the active substance is finely dispersed in the form of finely divided particles with an average diameter of ≥ 1 μΐη as a result of the addition of phospholipids. The new suspension concentrates show high storage stability.

When using spray suspensions with water obtained from these concentrates, these new formulations are self-suspended. The resulting suspensions are very stable and even after prolonged storage the mixture does not irreversibly decompose into individual components. Spray suspensions provide a continuous film of active ingredient with good adhesion when applied and parts of the plants to be protected are very well wetted. In addition, accelerated penetration into the plant is ensured. Furthermore, they exhibit high resistance to rain wash or other weather conditions. Furthermore, as ubiquitous building blocks of living matter, phospholipids are absolutely non-toxic and do not pose any ecological balance burden.

In order to produce these suspension concentrates, they are insoluble and, if necessary, soluble. the sparingly soluble pesticides are mixed with a phospholipid or a mixture of phospholipids, and the mixture is ground in the presence of an organic solvent or a mixture of solvents from the alcohol or ether group, especially in a ratio of 15-35% pesticide, 15-35% phospholipids and 40-60% solvent in colloid mills, ball mills, sand mills, stirrers or friction ball mills within 10 to 60 minutes, especially within 10 to 30 minutes, at a temperature of 20 to 50 ° C, preferably continuously. The addition of additional aids is not necessary. Stable suspension concentrates are obtained with a mean particle size · 1 дл.

Suitable phospholipids are, for example, commercially available phosphatidylcholines or mixed phosphatidylcholine products, such as e.g.

Phospholipon ^R 25 (25% phosphatidylcholine% phosphatidylethanolamine% phosphatidylinosit)

Phospholipon ^R 38 (38% phosphatidylcholine% N-acetylphosphatidylethauolamine% phosphatidylethanolamine)

Phospholipon® 55 (55% phosphatidylcholine% phosphatidylethanolamine% phosphatidylinosit)

Phospholipon ^R 80 (80% phosphatidylcholine% phosphatidylethanolamine)

Phospholipon ^R 100 (96% phosphatidylcholine)

Phospholipon® 100H (96% hydrogenated phosphatidylcholine).

Particularly preferred are natural phosphatidylcholines, which can be obtained by the processes described in the following patents: German Patent No. 1,047,579, German Patent No. 1,053,299, German Patent No. 1,617,679, German Patent No. 1 617 680, German publication Nos. 3,047,048, 3,047,012 or 3,047,011.

Suitable N-acylphosphatidylethanolamines are, in particular, those in which the acyl group is derived from saturated or olefinically unsaturated fatty acids having from 2 to 20 carbon atoms, in particular from saturated fatty acids having from 2 to 5 carbon atoms or from saturated or once olefinically unsaturated fatty acids. with 14, 16, 18 or 20 carbon atoms.

As physiologically acceptable organic solvents, resp. solvent mixtures, suitable are alcohols, resp. ethers, e.g., methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, sec-butanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene ether, diethylene ether, diethylene ether propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, butylene glycol, glycerin, solketal, tetarahydrofuran to dioxane.

Preference is given to mixtures of C 1 -C 3 alcohols, such as methanol, ethanol, propanol or isopropanol and ethylene glycol monoalkyl ether or ethylene glycol dialkyl ether.

As insoluble, possibly. · Poorly soluble pesticides are the active substances or mixtures of active substances from the groups of herbicides, fungicides, insecticides, acaricides, nematicides or plant growth regulators which, for insolubility, possibly. the low solubility in water and in physiologically acceptable solvents, especially in alcohols, has not yet been used in liquid form, eg as solutions or as emulsion concentrates.

As insoluble, possibly. For example, the following active substances may be considered as low-soluble pesticides:

from the group of herbicides, for example:

N-phosphonomethylglycine (Glyphosat), 3- (c-chloro-4-methylphenyl-1,1-dimethylurea (Chlortoluron)),

N- (4-Chloro-6-methyl-1,3,5-triazin-2-yl) aminocarbonyl-2-celphenylsulfonamide, 3- (C-isopropylphenyl) (1, 1,1-nimeth41 urea (Isoproturon),

3-Methyl-4-amino-1,1-phenoxy-1,1-dimethoxy-1,3-dimethyl-3- [ε-behzthiazolyl) urea (Methabenhthiazur on),

2-ethyl (r-ethylamino-6-isopropylamine) (S-

-triazine (Atrain),

3- (3,4-Dichlorophenyl) -1-methoxy-lomethyl. Urea (Lic-uron)

O- [2,4 · Ιϊ-ιϊϊ ι-ιΙ) hxim-3,5-librhm · (r (eydroxybenzaldehyde (jBromУenoxim J, 3- [4- [ЬЬ-огУпоху)) phenyl] -1,1- -1π44ϊ1-ure1urea (Chloroxuron), 1,6-dih-ohthinbedclmid (Chlorothiamide), N-dimethyl-Z-dienelecetamide (Diphenamid),

3- (3,4-Dichlorophenyl) -1,1-dimetheurea (Diuron),

2- (3,4-Dichlorophenyl) -4-methyl-1,2,4,3,3-quiniline-3,5-alcohol (Met-azo-),

3- (p-chlorophenyl) -1,1-dimethylurea (Monuron),

3- (3,4-dichlorophenyl) -1-methyl-1-n-butylmorea (Neburon),

2-chloro-4-bis-ethylamino-s-triazine (Simazine), or *

3-tert-butyl-5-chloro-G-methyluracil (Terbacil);

from the group of fungicides, for example:

1,3-dicyano-2,4,5,6-ethoquachlorobenzene (chlorothalonil),

N-trichloromethylthio * phthalimide (Folpet), N- (trichloromethylthioi) tetrahydro-phthalimide (Captan),

1- (butylcarbamoyl) bemzimidazol-2-ylcarbamate (Benomyl),

2,4-dichloro-6- (2-chloroanilim) -1,3,5-triazim (Anilazine),

2- (methoxycarbonylamino) benzimidazole (Carbemdazim),

6-N-methyl-4-oxo-1,3,3-trifluoro [4,5-13h] -2-oxo [theta] [thiophen] [theta], trienyltin tin acetate (Fe) (n-tert-butyl). dimethyldithiOcarbamate. ferric (Ferbam), N-trifluoromethylthiophthalimide · (Folpee), copper (II) erythyl chloride, ethylenediamine-bis-dithiocarba · mangamato-granulated (Manozeb),

N, N'-ethylene-bis (diphenyl) ^: mangamate cobbamate (Maneb), or tetramethylene sulfide (Thiram);

or * from the group of insecticides, for example:

2,3-chloro-2'-d, 2- (timetbylbonzO'furan17-yl-N-methylcarbamate (Carbofuran)),

O, S-dimetyl l-JN-acetyl i m iflOtIeiof phosphate (Acephat),

1- (4-chlorophenyl) -3- (2,6-difluorobemzoyl) urea (Diflubenzuron),

6-chloro-3,4-xylyl-N-methylcarbamate (Carbamolat), or

Endrim.

In principle, all pesticides whose solubility in water or in physiologically harmless solvents, in particular in the abovementioned alcohols, respectively, are suitable. etetreoh, is y2%.

The invention is illustrated by the following examples.

Example 1

Production of suspension concentrate. herbicide

It is dispersed for 1/2 hour in a 1000 liter stirrer

200 kg of 3-meteyl-4-amino-6-phenyl-1,2,4-triazin-5 (4H) -one (),

200 kg phospholipid (50% phosphatidylcholimus),

240 kg of propamol,

180 kg of polyethylene glycol 300, and then a 25 liter bead mill (ball mill) (manufactured by Drais, Mannheim) was added and the dispersion passed through the mill at a flow rate of 100 liters per hour. n is ground to an average particle size < 1 µm. The resulting suspension concentrate is a liquid with good fluidity which provides a spontaneous or spontaneous suspension in water spontaneously. This suspension is useful as a spray suspension.

Example 2

Production of a fungicide suspension concentrate

In an analogous manner to Example 1, it is ground for 10 minutes

120 g of 1- (butylcarbamoyl) benzimidazol-2-ylcarbamate (Benomyl),

115 g phospholipid (78% phosphotatidylcholim),

228 g butanol,

108 g of ethylene glycol diethyl ether.

The resulting liquid product provides the desired spray suspension upon dilution with water.

Example 3

Production of suspension concentrate herbicide

It is dispersed for 30 minutes in a 750 liter solvent mixer

250 kg of 1,3-dimethyl-3- (2-benzthiazolyl) urea (Methabenzthfazuron),

220 kg of phospholipid (45% phosphatidylcholimus), 138 kg of isobutanol and kg of propyl glycol monomethyl ether.

The dispersion is then milled in a tandem mill (manufactured by Netzsch) with the dispersion being fed in at a rate of 90 kg / hour and the milling is carried out in two stages. By this grinding process, the particle size of the Methabemzteitzuroπ crystals was 50 proo. The resulting suspension concentrate is a liquid with good flowability which provides a spontaneous suspension in water spontaneously or after slight shaking. This suspension is useful as a spray suspension.

Example 4

Production of suspension concentrate herbicide

In the same manner as in Example 1, it is ground

368IH)

150 g of 2-chloro-4-ethylamino-6-isopropylamino-s-triazine (Atrazine), g of phospholipid (75% phosphatidylcholine), g of ethanol, g of ethylene glycol monomethyl ether, using 50 g of sand (1 mm diameter, standard sand) ASTM, a product of Ottawa Silica Corp.).

Example 5

Production of suspension concentrate herbicide

In a stirrer (manufacturer: Vollrath, Koln, VSME type, grinding element size 2.2 liters, 2820 m @ ^-1 ), containing 1.2 kg of sand (1 mm diameter, standard sand, 20-30 ASTM, Ottawa) Silica Corp.), was stirred at room temperature for 20 minutes g of 3- (3,4-dichlorophenyl) -1-methoxy-1-methylurea (Linuron),

146 g phospholipid (50% phosphatidylcholine),

114 g of methanol and g of ethylene glycol monomethyl ether, grinding Linuron crystals to a medium particle size

The following concentrates can be prepared analogously to Examples 1 to 5:

Example 6

Fungicide suspension concentrate

120 g 1,3-dicyano-2,4,5,6-tetrachlorobenzene (Chlorothalonil), g phospholipid (50% phosphatidylcholine),

120 g isopropanol, g ethylene glycol monomethyl ether.

Example 1 a d 7

Fungicide suspension concentrate

140 g of N-trichloromethylthiophthalimide (Folpet), g of phospholipid (75% phosphatidylcholine), g of ethanol and

120 g of diethylene glycol monomethyl ether.

Example 8

Fungicide suspension concentrate

115 g of N- (trichloromethylthio) tetrahydro-phthalimide (Captan),

120 g phospholipid (25% phosphatidylcholine),

230 g tetrahydrofuran, g diethylene glycol monoethyl ether.

Example 9

Production of suspension concentrate herbicide

In a stirrer (manufacturer: Vollrath, Koln, typ

VSME, size of grinding element 2.2 liters, speed 2820 m ¹ ), containing 1 kg of lead glass balls (3 mm diameter), is mixed together for 20 minutes at room temperature

100 g of 3- (4-isopropylphenyl) -1,1-dimethylurea (Isoproturon),

100 g phospholipid (95% phosphatidylcholine),

130 g of ethanol and g of ethylene glycol monoethyl ether, thereby grinding Isoproturon crystals to a mean particle size of 1 µm. The resulting suspension concentrate is a liquid with good fluidity which provides a spontaneous suspension in water spontaneously or with gentle shaking. This suspension is useful as a spray suspension.

Example 10

Suspension concentrate of herbicide

100 g N-phosphonomethylglycine (Glyphosat), g phospholipid [25% phosphatidylcholine],

150 g of tetrahydrofuran and

100 g of ethylene glycol monoethyl ether.

Example 11

Suspension concentrate of herbicide

100 g of 3- (3-chloro-4-methylphenyl) -1,1-dimethylurea (Chlortoluron), g of phospholipid (45% phosphatidylcholine), g of methanol and g of ethylene glycol monoethyl ether.

Example 12

Suspension concentrate of herbicide g N- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) aminocarbonyl-2-chlorophenylsulfonamide,

190 g phospholipid (78% phosphatidylcholine),

210 g of ethanol a

170 g of ethylene glycol monomethyl ether.

Example 13

Insecticide suspension concentrate g of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N-methylcarbamate (Carbofuran),

107 g phospholipid (95% phosphatidylcholine),

125 g of isobutanol and g of ethylene glycol.

Example 14

Insecticide suspension concentrate g 0, S-dimethyl-N-acetylamidothiophosphate (Acephat),

112 g phospholipids (45% phosphatidylcholine),

120 g ethanol, g ethylene glycol monoethyl ether.

Example 15

Insecticide suspension concentrate

124 g of 1- (4-chlorophenyl) -3- (2,6-difluorobenzoylurea (Diflubenzuron), g phospholipids (75% phosphatidylcholine),

210 g of ethanol, g of propyl glycol dimethyl ether.

Example 16

Insecticide suspension concentrate

100 g of N- (2-chlorobenzoyl) -1H- (4-trifluoromethoxyphenyl) urea,

100 g phospholipids (48% phosphatidylcholine)

130 g of ethanol, g of ethylene glycol dimethyl ether.

Example 17

Comparison of stability of suspension concentrates

(a) Method of production of standard preparations (suspension concentrates)

Folders:

- water - anti-freeze agent - dispersant - wetting agent - active ingredient ground to a particle size of 50 to 100 μΐη - anti-foaming agent - theological additive - preservative (only necessary if the component is based on polysaccharides) is mixed in order 1 , 2, 3, 4, 6 and 8, then add component 5 with stirring and grind the mixture to a particle size of 5 μΐη. After venting, component 7 is added.

b) Suspension suspendability concentrate in% ^υ

Example 1 87 Standard product to example 1 81 Example 2 90 Standard product to example 2 83 Example 3 89 Standard product to example 3 80 Example 5 87 Standard product to example 5 78

Example 689

Standard formulation of Example 679

Example 890

Standard preparation for example 883

Note:

ⁿ cf. CIPAC handbook (method 15.1)

From the above results, it is apparent that the suspension concentrates have a substantially higher stability than the suspension concentrates obtained by conventional methods.

Claims (7)

OBJECT OF THE INVENTION Suspension concentrates of plant protection products on the basis of insoluble, if necessary of a slightly soluble pesticide, the solubility of which in water or in the physiologically acceptable organic solvent used is equal to or less than 2% by weight of phospholipids and of the organic solvent; a solvent mixture, characterized in that the concentrate consists of (a) 15 to 35% by weight of insoluble; a sparingly soluble pesticide with a melting point above 40 ° C; (b) 15 to 35% by weight of phospholipids; and c) 40 to 60% by weight of a solvent or a mixture of solvents from the group of alcohols, optionally. and the mean particle size is equal to or less than 1 μΐη. Suspension concentrates according to claim 1, characterized in that they comprise as pesticides an active substance or a mixture of active substances from the group of herbicides, insecticides or fungicides. Suspension concentrates according to Claims 1 to 2, characterized in that they comprise at least one phospholipid from the group of phosphatidylcholine, phosphatidylethanolamine, N-acetylphosphatidylethanolamine, phosphatidylinositide, phosphatidylserine, lysolecithin, phosphatidylglycerol or hydrogenated phospholipid. 4. Suspension concentrates according to items 1 to 4 3, characterized in that they comprise as phospholipid phosphatidylcholine or mixtures of phosphatidylcholine and phosphatidylethanolamine. 5. Suspension concentrates according to items 1 to 2 4, characterized in that as the phospholipid, They contain a phospholipid containing from 20 to 98% phosphatidylcholine. Suspension concentrates according to Claims 1 to 5, characterized in that they comprise mixtures of C 1 -C 3 alcohols and ethylene glycol alkyl ether as solvents. 7. A process for the production of suspension concentrates of plant protection products according to claims 1 to 6, characterized in that the mixture consisting of: (a) an insoluble or sparingly soluble * pesticide whose solubility in water or * in the physiologically sound organic solvent used is equal to or less than 2% by weight and which has a melting point above 40 ° C; (b) phospholipids; and c) solvents or solvent mixtures from the group of alcohols; ethers, in a colloid mill, ball mill, sand mill, stirrer or friction ball mill for 10 to 60 minutes at 20 to 50 ° C.