NO824342L - SUSPENSION CONCENTRATES OF PLANT Pesticides. - 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

The present invention relates to new suspension concentrates

which next to an insoluble or poorly soluble pesticide contains a phospholipid and a physiologically acceptable solvent or a mixture of such from the group of alcohols or ethers, as well as the preparation thereof.

Today, one can no longer renounce the use of plant protection products to reduce crop losses due to diseases, harmful organisms and weeds. Most plant protection agents are water insoluble or poorly soluble in water and must therefore be used as wettable powders or emulsion concentrates in very dilute concentrations.

In agriculture, emulsion concentrates are preferred over the powder or granule forms due to the more favorable dosage. The emulsion concentrates are spread when used in emulsified form in water, and as so-called spray compounds.

These spray compounds are generally produced from water-free or water-poor emulsion concentrates of water-insoluble active substances. The emulsion concentrates contain approximately 10 - 40%

of the active substances and in addition organic solvents and emulsifiers as well as further aids such as stabilisers, further wetting agents, anti-foaming agents and the like.

For the production of emulsion concentrates of these water-soluble active substances, these are dissolved in a suitable organic solvent, such as alkylbenzenes, acetone, kerosene, toluene and the like, and a suitable emulsifier or, most often, a mixture of such emulsifiers is added . Anionic, cationic or non-ionic emulsifiers are preferably used as emulsifiers, or mixtures thereof. Many wetting agents and emulsifiers can greatly disrupt the osmosis and water balance of the plants, so that the treated plants are damaged.

Beyond this are the solvents that find use

which are often toxic themselves and can lead to stress for the environment.

When preparing such a spray compound, the corresponding concentrates should emulsify spontaneously. The standing emulsion must

be so stable that it shows no irreversible separation tendency, even after several hours' standstill.. During stirring and repumping, no remaining foam must occur. The requirement for an ideal spray mass is e.g. that a continuous film of active substance is formed which adheres well to or adequately moistens what is to be protected and exhibits a high resistance to wash-off due to rain and other climatic influences. Furthermore, an accelerated penetration of the active substance into the plant must be ensured.

However, most pesticides are not only poorly soluble or insoluble in water, they are also often not soluble in the solvents acceptable for agriculture. Such agents can only be used as granules or wettable powder. When used in practice, there are difficulties with the exact dosage and spreading. It is therefore desirable that a liquid form is also obtained for these active substances.

It has now surprisingly been found that stable suspension concentrates of plant protection agents are obtained when grinding insoluble or poorly soluble pesticides in a mixture with a phospholipid from the phosphatidylcholine group, the hydrogenated phosphatidylcholines, phosphatidylethanolamine, N-acyl-phosphatidylethanolamines, phosphatidylinositol, phosphatidylserine and phosphatidyl-glycerol or a mixture of several such phospholipids in the presence of a physiological and acceptable solvent or a mixture of such from the group of alcohols or ether.

The new suspension concentrates are distinguished by the fact that the active substance with a very finely ground average particle size of equal to less than lum is very finely divided by the addition of phospholipids. The new suspension concentrates show a high storage stability.

When a spray mass with water is applied from these concentrates, the new compositions exhibit spontaneous suspension.

The resulting suspensions are therefore very stable and do not exhibit irreversible separation tendencies after a longer period of time. When applied, the spray compounds provide a continuous film of active substance with good adhesion and wetting on the plant parts to be protected. In addition to this, accelerated penetration into the plant is ensured. It also shows a high resistance to washing off due to rain or other climatic conditions.

Furthermore, the phospholipids, as ubiquitous building blocks in living matter, are absolutely non-toxic and show no strain on the ecological balance.

For the production of these new suspension concentrates, the insoluble or poorly soluble pesticides are mixed with a phospholipid or a mixture of phospholipids and ground in the presence of an organic solvent or a mixture of such from the group of alcohols or ethers, especially in the mixture ratio pesticide 15 - 35 %, phospholipid 15 - 35% and solvent 40 - 60%, in colloid, ball, sand, tube or friction ball mills for 10 - 60 minutes, preferably 10 - 30 minutes, at 20 - 50°C, preferably continuously.

The addition of additional aids is not necessary. Stable suspension concentrates are obtained with an average particle size equal to less than glue.

As phospholipids, e.g. the commercially available phosphatidylcholines, or phosphatidylcholine mixture products, such as

Particularly preferred are natural phosphatidylcholines which can be produced by the methods described in the following patents: DE-PS 10 4 7 579, DE-PS 10 53 299, DE-PS 16 17 679, DE-PS 16 17 680, German off. font 30 47 048, 30 47 012 or 30 47 011.

As N-acyl-phosphatidylethanolamines come into consideration especially those derived from saturated or olefinically unsaturated fatty acids with 2-20 carbon atoms, especially those saturated with 2-5 carbon atoms or those saturated or once olefinically unsaturated with 14, 16, 18 or 20 carbon atoms. As physiologically acceptable organic solvents or mixtures thereof, alcohols or ethers such as e.g. ethanol, methanol, propanol, isopropanol, butanol, isobutanol, tert.-butanol, sec.-butanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethyl glycol diethyl ether, diethyl glycol dimethyl ether, diethyl glycol monoethyl ether, diethyl glycol monomethyl ether, diethylene glycol propyl ether, diethylene glycol diethyl ether, polyethylene glycol, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, butylene glycol, glycerin, -sol ketal, tetrahydrofuran or dioxane. Mixtures of C^-C^ alcohols, such as methanol, ethanol, propanol or isopropanol and ethylene glycol mono-

or dialkyl ethers.

As insoluble or poorly soluble pesticides, active substances or mixtures of such from the group herbicides, fungicides, insecticides, acaricides, nematicides or plant growth regulators come into consideration which, due to their insolubility, or low solubility in water and the physiologically acceptable solvents, especially in alcohol will now not be able to be used in liquid form or as a solution or emulsion concentrate.

The following active substances come into consideration as insoluble or poorly soluble pesticides:

From the group of herbicides, for example:

N-phosphonomethylglycine (glyphosate),

3-(3-chloro-4-methyl-phenyl)-1,1-dimethylurea (chlorotoluron),

N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-aminocarbonyl-2-chlorophenylsulfonamide,

3-(4-isopropy1-phenyl)-1,1-dimethylurea (isoproturon), 3-methyl-4-amino-5-phenyl7l,2,4,-triazin-5(4H)-one (metamitrone),

1,3-dimethyl-3-(2-benzthiazoly)-urea (metabenzthiazuron),

2- chloro-3-ethylamino-6-isopropylamino-s-triazine (atrazine), 3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea (linuron), 3,5-dibromo-4-hydroxybenzaldehyde- 0-(2,4-dinitrophenyl)-oxime (bromophenozim),

3- £Å-(chlorophenoxy)-phenyl7-1,1-dimethylurea (chloroxuron),

2,6-dichloro-thio-benzamide (chlorothiamide),

N,N-dimethyl-2,2-diphenylacetamide (diphenamide), 3-(3,4-dichlorophenyl)-1,1-dimethylurea (diuron), 2-(3,4-dichlorophenyl)-4-methyl-1, 2,4-oxadiazolidine-3,5-dione (methazol),

3-(p-chlorophenyl)-1,1-dimethylurea (monuron), 3-(3,4-dichlorophenyl)-1-methyl-1-n-butylurea (neburon), 2-chloro-4 , 6-bis- ethylamino-s-triazine' (simazine),

or

3-tert-butyl-5-chloro-6-methyluracil (terbacil);

from the group of fungicides, e.g.: 1,3-diacyn-2,4,5,6-tetrachlorobenzene (chlorothalonil), N-trichloromethylthiophthalimide (folpet),

N-(trichloromethylthio)-tetrahydrophthalimide (captan), 1-(butylcarbamoy1)-benzimidazol-2-yl-carbamate (benomyl), 2,4-dichloro-6-(2-chloroaniline)-1,3,5-triazine (anilazine) , 2-phaethoxy-carbonylamino)-benzimidazole (carbendazim), 6-methyl-2-oxo-1, 3-dithiol Z~"4,5-bZ7~quinoxaline (quinome-thionate),

triphenyltin acetate (fentin acetate),

eisendimethyIdithiocarbamate (ferbam),

N-trichloromethylthiophthalimide (Folpet),

copper oxychloride,

manganese-zinc-ethylenediamine-bis-dithio-carbamate (manozeb), manganese- (II) -/~N,N 1-ethylene-bis(dithiocarbamate)_7 (maneb) , or

tetramethylthiurane disulfide (thiram),

or e.g. the following insecticides: 2,3-dihydro-2,2-dimethyl-benzofuran-7-yl-N-methylcarbamate (carbofuran),

0,S-dimethyl-N-acety 1-aminothiophosphate (acephate) , 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)-urea (diflubenzuron) ,

6-chloro-3,4-xyly1-N-methylcarbamate (carbanolate),

or

endrin.

In principle, all pesticides come into consideration if their solubility in water or in physiologically acceptable solvents, e.g. in the above-mentioned alcohols or ethers, exhibits a value equal to less than 2%.

Example 1

Preparation of a herbicide suspension concentrate.

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

200 kg phospholipid (50% phosfatidylcholine),

240 kg propanol

180 kg polyethylene glycol 300

dispersed in a 1000 liter dissolution mixer for half an hour. A 25 liter bead mill (pipework ball mill) from fa. is then connected. Drais, Munchen, and the flow rate through the mill is set to 100 1 per hour. With this grinding, a metamitron grinds the crystals to an average particle size of less than 1 um. The resulting suspension concentrate is a well-pourable liquid which in water gives a stable suspension spontaneously or after light shaking. The suspension can be used as a spray compound.

Example 2

Preparation of a fungicide suspension concentrate.

120 g 1-(butylcarbamoy 1)-benzimidazol-2-yl-carbamate (benomyl), 115 g phospholipid (78% phosphatidylcholine),

228 g of butanol,

108 g of ethylene glycol diethyl ether

is ground analogously to example 1 for ten minutes. The resulting liquid product, diluted with water, gives the desired spray mass.

Example 3

Preparation of a herbicide suspension concentrate.

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

220 kg of phospholipid (45% phosphatidylcholine),

138 kg isobutanol,

90 kg of propyl glycol monomethyl ether

dispersed in a 750 liter dissolution mixer for half an hour. It is then connected to a tandem mill from fa.Netzch, and the dispersion is ground in two stages with a throughput of 90 kg per hour. After this grinding, a grain size is obtained where 50% is below the glue for the metabenzthiazuron crystals. The resulting suspension concentrate is a well-pourable liquid which spontaneously or after light shaking gives a stable suspension. The suspension can be used as a spray compound.

Example 4

Preparation of a herbicide suspension concentrate.

150 g 2-chloro-4-ethylamino-6-isopropylamino-s-triazine (atrazine), 46 g phospholipid (75% phosphatidylcholine),

95 g of ethanol,

90 g ethylene glycol monoethyl ether,

is ground as in example 1 using 50 g of sand (diameter 1 mm, standard sand, 20 - 30 ASTM, Ottawa Silica Corp.).

Example 5

Preparation of a herbicide suspension concentrate.

50 g 3-(3,4-dichlorophenyl)-1-methoxy-methylurea (linuron), 146 g phospholipid (50% phosphatidylcholine)

114 g of methanol,

90 g of ethylene glycol monomethyl ether

is set to a mixer mill (Vollrat, Koln, type VSME, grinding container size 2.2 1, rotation speed 2820 per minute)

which contained 1.2 kg of sand (diameter 1 mm, standard sand, 20 - 30 ASTM, Ottawa Silica Corp.) and stirred for 20 minutes at room temperature whereby the linuron crystals are ground to a medium

particle size of equal to less than lym.

The following concentrates can be prepared analogously to examples 1-5:

Example 6

Fungicide suspension concentrate

120 g 1,3-dicyan-2,4,5,6-tetrachlorobenzene (chlorothalonil),

95 g phospholipid (50% phosphatidylcholine),

120 g of isopropanol

80 g of ethylene glycol monomethyl ether

Example 7

Fungicide suspension concentrate

140 g of N-trichloromethylthiophthalamide (Folpet),

65 g phospholipid (75% phosfatidylcholine),

90 g of ethanol,

120 g of diethyl glycol monomethyl ether

Example 8

.Fungizide suspension concentrate

115 g of B-(trichloromethylthio)-tetrahydrophthaamide (captan),

120 g phospholipid (25% phosfatidylcholine),

2 30 g tetrahydrofuran,

60 g diethylene glycol monoethyl ether

Example 9

Preparation of a herbicide suspension concentrate

100 g 3-(4-isopropyl-phenyl)-1,1-dimethylurea (isoproturon), 100 g phospholipid (95% phosphatidylcholine),

120 g ethanol,

90 g ethylene glycol monoethyl ether

is added to a mixer mill (Vollrath, Koln, type VSME, grinding container size 2.2 litres, rpm 2820 per minute) which contained lkg lead glass balls (diameter 3 mm), and

the whole is stirred for 20 minutes at room temperature, whereby the isoproturon crystals are brought to an average particle size of equal to less than lym. The resulting suspension concentrate is a well-pourable liquid which spontaneously or after light shaking gives a stable suspension. The suspension can be used as a spray compound.

Example 10

Herbicide suspension concentrate

100 g N-phosphonomethylglyein (glyphosate),

70 g phospholipid (25% phosfatidylcholine),

150 g tetrahydrofuran,

100 g of ethylene glycol monoethyl ether

Example 11

Herbi zid suspension concentrate

100 g 3-(3-chloro-4-methyl-phenyl)-1,1-dimethylurea (chlorotoluron),

96 g phospholipid (45% phosphatidylcholine),

9 2 g methanol,

90 g of ethylene glycol monoethyl ether

Example 12

Herbicide suspension concentrate

30 g of N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino-carbonyl-2-chlorophenyl-sulfonamide,

190 g phospholipid (78% phosfatidylcholine),

210 g of ethanol,

170 g of ethylene glycol monomethyl ether

Example 13

Insecticide suspension concentrate

95 g of 2,3-dihydro-2,2-dimethyl-benzofuran-7-yl-N-methyl-carbamate (carbofuran),

continued

107 g phospholipid (95% phosphatidylcholine),

125 g isobutanol,

9 5 g ethylene glycol

Example 14

Insecticide suspension concentrate

49 g Q,S-dime ty 1-N-acetyl-amido-thioph os fat. (acephate), 112 g phospholipid (45% phosphatidylcholine),

120 g ethanol,

75 g of ethylene glycol monoethyl ether

E xample 15i

Insecticide suspension concentrate

124 g 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)-urea (diflubenzuron),

98 g phospholipid (75% phosfatidylcholine),

210 g of ethanol,

90 g of propyl glycol dimethyl ether

Example 16

Insecticide suspension concentrate

100 g N-(2-chlorobenzoyl)-N<1->(4-trifluoromethoxy<y->phenyl)-urea

100 g phospholipid (48% phosfatidylcholine),

130 g of ethanol

90 g of ethylene glycol dimethyl ether.

Claims (8)

1. Leaf protection agent suspension concentrates based on an insoluble or heavily soluble pesticide, a phospholipid and an organic solvent, or a mixture of these, characterized in that the concentrate consists of a) 15 - 35% of an insoluble, respectively a heavily soluble pesticide, with a melting point greater than 40°C, b) 15 - 35% of a phospholipid and c) 40 - 60% of an op <p> solvent mixture or a mixture of such from the group of alcohols, respectively ethers. 2. Concentrate according to claim 1, characterized in that an active substance or a mixture of such from the group of herbicides, insecticides or fungicides is used as pesticide. 3. Concentrate according to claim 1 or 2, characterized in that the phospholipid used is one or more phospholipids from the group phosphatidylcholine, phosphatidylethanolamine, N-aculfos fatidylethanolamine, phosphatidylinositol, phosphatidylserine, lysolecithin, phosphatidylglycerol or hydrated phospholipids. 4. Concentrate according to claims 1-3, characterized in that phosphatidylcholine or mixtures of phosphatidylcholine and phosphatidylethanolamine are used as phospholipid. 5. Concentrate according to claims 1-4, characterized in that a phospholipid with a content of 20 - 98% phosphatidylcholine is used as phospholipid. 6. Concentrate according to claims 1-5, characterized in that mixtures of C 1 -C 2 -alcohols and ethylene glycol alkyl ethers are used as solvents. 7. Concentrate according to claims 1-6, characterized in that the average particle size amounts to less than lum. 8. Process for the production of plant protection agent suspension concentrates according to claims 1-7, characterized in that a mixture of a) an insoluble or poorly soluble pesticide with a melting point above 40°C, b) a phospholipid, c) a solvent or a mixture of such from the alcohol or ether group, grind together in a colloid, ball, sand, mixer line or friction ball mill for 10 to 60 minutes at 20 - 50°C.