DD208537A5 - NEW PLANT PROTECTION SUSPENSION CONCENTRATES - 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

New pesticide suspension concentrates

Field of application of the invention:

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

Characteristics of the known technical solutions: The use of pesticides to reduce crop losses caused by diseases, harmful and weeds can not be dispensed with in agriculture today, Most pesticides are insoluble in water or very sparingly soluble in water and must therefore be used as a wettable powder or Emulsion concentrate can be applied in very dilute concentration.

In agriculture, emulsion concentrates are preferred over the powder or granule forms because of the more favorable dosage. The emulsion concentrates are emulsified in the application in water and discharged as so-called spray liquors.

2QDEi-1932 * 056 357

Spray mixtures are generally prepared from anhydrous or low-water emulsion concentrates of water-insoluble active ingredients. The emulsion concentrates contain about 10 to 40 % of the active ingredients and also organic solvents and emulsifiers as well as other auxiliaries, such as stabilizers, other wetting agents , antifoams and the like.

To prepare the emulsion concentrates of these water-insoluble active ingredients, these are dissolved in a suitable organic solvent, such as alkylbenzenes, acetone, kerosene, toluene and the like, and admixed with a suitable emulsifier or usually mixtures of such emulsifiers. As emulsifiers anionic, cationic or non-ionic emulsifiers or mixtures of these emulsifiers are preferably used, many wetting agents and emulsifiers can greatly disturb the osmosis and the water balance of the plants, so that the treated plants are damaged. In addition, the solvents used are usually themselves toxic and can be a burden on the environment.

Z e 1 of the fin ging ±

When applying a spray mixture, the corresponding concentrates should emulsify spontaneously. The resulting emulsion should be so stable that they show no irreversible segregation phenomena even after standing for several hours. When stirring and pumping should not produce a stable foam. The requirements for an ideal spray mixture are e.g. the emergence of a continuous drug film with good adhesion or wetting on the plant to be protected and a high resistance to washing by rain or other weather conditions. Furthermore, accelerated penetration of the active ingredient into the plant should be ensured.

27 4 5

However, most pesticides are not only insoluble in water or insoluble but are also insoluble in those acceptable to agriculture. Such agents can only be used as granules or wettable powders. When used in practice, there are difficulties in the exact dosage and application. It is therefore desirable to have a liquid form also for these agents.

Explanation of the essence of the invention;

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

The novel suspension concentrates are characterized in that the active ingredient is finely ground, average particle size <. 1 ρ is finely divided by the addition of phospholipids. The new suspension concentrates show a high storage stability.

When preparing spray liquors with water from these concentrates, the new compositions exhibit spontaneous suspending. The resulting suspensions are very stable and also show. prolonged storage no irreversible segregation phenomena. During application, the spray liquors give a continuous drug film with good adhesion and wetting on the parts of the plant to be protected.

In addition, an accelerated penetration into the plant is ensured. Also, they show a high resistance to washing by rain or other weather influences. "Furthermore, the phospholipids as ubiquitous building blocks of living matter are completely non-toxic and do not burden the ecological balance.

To prepare these new suspension concentrates, the insoluble or poorly soluble pesticides are mixed with a phospholipid or phospholipid mixture and in the presence of an organic solvent or solvent mixture from the group of alcohols or ethers, in particular in the mixing ratio of pesticide 15-35%, phospholipid 15-35% and solvent 40 - 60%, in colloid, ball, sand, Rührwerks- or Reibkugelmühlen 10-60 minutes, in particular 10 - 30 minutes, at 20 - 50 ° C, preferably continuously, ground. An addition of further aids is not necessary. Obtained are stable suspension concentrates with an average particle size of .5i 1 Ja.

As phospholipids, e.g. the commercially available phosphatidylcholines or phosphatidylcholine mixed products, e.g.

Phospholipon 25

Phospholipon ^R 38 Phospholipon ^R 55

(25% phosphatidylcholine 25 "% phosphatidyl ethanolamine 20% phosphatidylinositol)

(38% phosphatidylcholine 16% N-acetyl-phosphatidylethanol

amine 4% phosphatidyl ethanolamine)

(55% phosphatidylcholine 25% phosphatidylethanolamine 2% phosphatidylinositol

46274 5

Phospholipon ^R 80 (80% phosphatidylcholine

10% phosphatidyl ethanolamine)

R Phospholipon 100 (96% phosphatidylcholine)

Phospholipon ^R 100H (96% hydrogenated phosphatidylcholine) in question.

Particular preference is given to natural phosphatidylcholines which can be obtained by the processes described in the following patents: DE-PS 1 047 579, DE-PS 1 053 299, DE-PS 1 617 679, DE-PS 1 617 68o, DE-OS 3 O47 o48, DE-OS 3 o47 oil 2 or DE-OS 3 o47 o11.

Particularly suitable N-acyl-phosphatidyl ethanolamines are those in which the acyl group is derived from saturated or olefinically unsaturated fatty acids having 2-20 carbon atoms, in particular the saturated ones having 2-5 carbon atoms or the saturated or even olefinically unsaturated ones having 14, 16 , 18 or 20 carbon atoms derived. Suitable physiologically acceptable organic solvents or solvent mixtures are alcohols or ethers, such as, for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, sec-butanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether , Diethylenglykolraonomethylether, Diethylenglykolpropylether, Diethylenglykoldiethylether, polyethylene glycols , propylene glycols , Propylenglykolraonomethylether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, Propylenglykoldiethylether, butylene glycol, glycerol, Solketal, tetrahydrofuran or dioxane in question. Preference is given to mixtures of C 1 -C 4 -alcohols such as methanol, ethanol, propanol or isopropanol and ethylene glycol mono- or dialkyl ethers.

As insoluble or sparingly soluble pesticides come active ingredients or. Active substance mixtures from the groups of herbicides, fungicidal insecticides "acaricides, nematicides or plant growth regulators in question, which because of their insolubility or low solubility in haters and in physiologically acceptable solvents * especially in alcohols, not previously in liquid form, e.g. as a solution or emulsion concentrate, could be used ». '.

Insoluble or sparingly soluble pesticides are e.g. following active substances in question:

For example, from the group aer herbicides N-phosphonomethylglycine (glyphosate),

3- (3-chloro-1-methyl-4-methyl-1-yl) 1-trimethylurea (chioroxy)

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

3- (4-Isopr'opyl-phenyl) -l, 1-dimethylurea (isoproturon), 3-methyl-4-amino-6-phenyl-1,2,4-triazin-5 (4H) -one ( Metamitron), 1,3-dimethyl-3 »(2-benzthiazolyl) urea (methabenzothiazuron), 2-chloro-4-ethylamino-6-isopropylamino-s-triazine (atrazine), 3- ( _3t- 4 Di chlorophenyl) -1-methoxy-1-methylurea (Li Nurone), 3,5-dibromo-4 "hydroxybenzaldehyde 0- (2,4-dinitrophenyl) oxime

(Bromfenoxime), 3- / 4- (Ch 1 or phenoxy) -phenyl 17-1,1-dimethylurea

, (ChIoroxuron)

2,6-dichloro-thio-benzamide (chlorthiamide), N, N-dimethyl-2,2-diphenylacetamide (diphenamid), 3- (3, ₉ -dichlorophenyl) -1, 1-dimethylurea (diuron),

2- (3,4-dichlorophenyl) -4-methyl-l, 2,4-oxadi-azolidine-3,5-dione

(Methazole) -

3- (p-chlorophenyl) -1,1-dimethylurea (monuron), 3- (3,4-di-chlorophenyl) -l-meth-yl-n-butyl urea (Neburon), 2- Chloro-4 ₉ 6-bis-ethylal! IriO-s-triazine (simazine), or

S-tert-butyl-B-chloro-G-methyluracil (terbacil);

4 6 27 4 5

from the group of fungicides, for example:

3-dicyan-2,4,5,6-tetrachlorobenzene (chlorothalonil).

N-trichloromethylthiophthalifnid (folpet), N- (trichloromethylthio) -tetranydrophthalimide (captan), 1- (butylcarbamoyl) -benzimidazol-2-ylcarbamate (benomyl), 2,4-dichloro-6- (2-chloroaniline) -l _s 3,5-triazine (anilazine), 2- (methoxycarbonylamino) -benzimidazole (carbendazim), 6-methyl-1-oxo-1,3-dithiol / 4,5-b / -chi η ox al in (quinomethionate), triphenyltin acetate (fentin acetate), iron dimethyldithiocarbamate (Ferbam), N-trichloromethylthiopthalimide (folpet), copper oxychloride,

Manganese-zinc-ethylenediamine-bis-dithio-carbamate (manozeb), manganese (II) - / "N, N'-ethylene-bis (dithiocarbamate) / (maneb) y

TetraitiGthyl-thiuram-disulfide (Thiram);

or e.g. following insecticides:

2,3-dihydro-2- _t 2-dimethylbenzofuran-7-yl-N-methylcarbamate

(Carbofuran),

O.S-dimethyl-M-acetylaminothiophosphate (acephate), 1- (4-chlorophenyl) -3- (2,6-difluorobenzoyl) urea

(Diflubenzuron),

e-chloro-S ^ -xylyl-N-methylcarbamate (carboxide),

Endrin.

In principle, all pesticides in question whose solubility in water or physiologically acceptable solvents, in particular in the abovementioned alcohols or ethers have a solubility of ^ 2%.

- 8th -

Preparation of a herbicidal suspension concentrate.

200 kg of 3-methyl-4-amino-6-ptoenyl-l _s 2,4 »triazine-5 {4H) -one

(Metamitron)

200 kg phospholipid (50% phosphatidylcholine) 240 kg propanol 180 kg polyethylene glycol 300

are dispersed in a 1000 liter solvent mixer for 1/2 hour. Subsequently, a 25 liter bead mill (agitator) of the Fa, Drais »Mannheim, zuqeschaltet and the flow rate through the mill at 100 liters / hour. Through this process, the metamitron crystals will be ground to an average of 1 ^ 1 μ. The resulting suspension concentrate is a readily pourable liquid which provides a stable suspension in water spontaneously or after gentle shaking. The suspension can be used as Spritzbriihe.

Ex iel 2

Preparation of a fungicide suspension concentrate.

120 g of (butylcarbamoyl) benzimidazol-2-yl-carbamate (benomyl) 115 g of phospholipid (78% phosphatidylcholine) 228 g of butanol

108 g of ethylene glycol diethyl ether

are ground analogously to Example 1 for 10 minutes. The resulting liquid product is diluted with water to give the desired spray mixture.

Example 3

Preparation of a herbicidal suspension concentrate.

250 kg l _l 3-Di'methyl-3- (2-benzth1azply1.) - urea

(Methabenzothiazuron),

220 kg phospholipid (45% phosphatidylcholine) 138 kg isobutanol 90 kg propylglycol monomethyl ether

-Β Q BM)

are dispersed in a 750 liter solvent mixer for 1/2 hour. A tandem mill from Netzsch was connected and the dispersion was ground in two stages at a throughput of 90 kg / h. By this Mahlvorganq a grain size of 50 % is achieved under I u to methabenzthiazuron crystal. The resulting suspension concentrate is a readily pourable liquid which provides a stable suspension in water spontaneously or after gentle shaking. The suspension can be used as a spray mixture.

Example "£.

Preparation of a herbicidal suspension concentrate.

150 g of 2-chloro-4-ethyl-amino-6-isopropylamino-s-triazine

(Atrazine)

45 α phospholipid (75% phosphate dylcholine) 95 g ethanol

90 g of ethylene glycol monoethyl ether

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

Example 5

Preparation of a herbicidal suspension concentrate.

50 g of 3- (3,4-dichlorophenyl) -1-methoxy-1-methylthiourea

(Linuron)

146 g phospholipid (50% phosphatidylcholine) 114 g methanol

90 g of ethylene glycol monomethyl ether are together in a stirred mill (manufacturer: Vollrath, Cologne, type VSHE ₈ Mahltopfgröße 2.2 liters, number of revolutions 2820 m ~) the 1.2 kg of sand (diameter 1 mm, standard sand, 20-30 ASTM ₃ Ottawa silica Corp.) was added and stirred for 20 minutes at room temperature, whereby the Linuron crystals are ground to an average particle size of = 1 ji .

The following concentrates can be prepared analogously to Examples 1:

Example 6 Fungicide Suspension Concentrate

120 gl ₈ 3 ~ dicyan-2 ₉ 4.5 _s 6-tetrachlorobenzene (chlorothalonil)

95 g phospholipid (Bü% phosphatidylcholine)

120 g of isopropanol

80 g ethylene glycol monomethyl ether

Example 7

Fungicide suspension concentrate

140 g of N-trichloromethylthiophthalimide (Folpet)

65 g phospholipid (75% phosphatidylcholine)

90 g of ethanol

120 g diethyl glycol monomethyl ether

Beispiel.8

Fungi -id suspension concentrate

115 g of N- (THehlormethylthio) tetrahydrophthalimide (Captan) /

120 g phospholipid (25% phosphatidylcholine)

230 g of tetrahydrofuran

60 g Diethytenglykolmonoethylether

Example 9

Preparation of a herbicidal suspension concentrate.

100 g of 3 - (4-isopropyl-phenyl) -l, 1-dimethylurea

(Isoproturon)

100 g phospholipid (95% phosphatidylcholine) 13.0 g ethanol 90 g ethylene glycol monoethyl ether

are zussmmen in a stirred mill (manufacturer: Vollrath, Cologne, type VSME, pot size 2.2 liters, number of revolutions 2820 m ~) * containing 1 kg of lead glass balls (diameter 3 mm), added and stirred for 2.0 minutes at room temperature / whereby the Isoproturonkristaile be milled to an average particle size of = 1 μ . The resulting suspension concentrate is an out pourable liquid which provides a stable suspension in water spontaneously or after gentle shaking. The suspension is usable as a spray mixture,

Example 10 Herbicide Suspension Concentrate

100 g of N-phosphonomethylglycine (glyphosate),

70 g phospholipid (25% phosphatidylcholine)

150 g of tetrahydrofuran

100 g of ethylene glycol monoethyl ether

Example 11

Herbicide suspension concentrate

100 g of 3- (3-chloro-4-methylphenyl) -1,1-dimethylurea

(Chlorotoluron)

96 g phospholipid (45% phosphatidylcholine) 92 g methanol 90 g 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% phosphatidylcholine) 210 g ethanol 170 g ethylene glycol monomethyl ether

Insecticide suspension concentrate

95 % 2 "3-dihydro" · 2 ₉ 2-dune-thy! -Benzof uran-7-y IN-me thy! Carbamate (carbofuran)

107 g phospholipid (95% phosphatidylcholine) 125 g isobutanol

95% ethyl engiykol

In the case of s p_i e] H.

Insecticide suspension concentrate

49 g of 0jS-dimethyl-N-acetyl-amido-thiophosphate (acephate)

112 g phospholipid (45% phosphatidylcholine)

120 g of ethanol

75 g of ethylene glycol monoethyl ether

Example 15 Insecticide Suspension Concentrate

124 π l- (4-chlorophenyl) -3- (2 _t 6-difluorobenzoyl) urea

(Diflubenzuron)

98 g phospholipid (75% phosphatidylcholine) 210 g ethanol

9Og propyl glycol dimethyl ether

Beis piel jj>

Insekti ζid »suspension concentrate

100 g of N- (2-chlorobenzoyl) -N ⁵ - (4-trifluoromethoxyphenyl) urea

100 g phospholipid (48% phosphatidylcholine) 130 g ethanol 90 g ethylene glycol dimethyl ether

Claims (8)

_β Pflanzenschutzjßitfcelsuspensionskonzentrate based on an insoluble bsw "poorly soluble pesticide, a Phospholipiäes and an organic solvent or solvent mixture, characterized in that the concentrate of a) 15-35% of an insoluble or poorly soluble pesticide having a melting point of> 40 C, b) 15-35% of a phospholipid and c) 40-60% of a solvent or solvent mixture from the group of alcohols or ethers consists, 2. pesticide suspension concentrates according to item 1, characterized in that a drug or active ingredient mixture from the group of herbicides, insecticides or fungicides are used as the pesticide. 3. Pesticide suspension concentrates according to one or more of the items 1 to 2, characterized in that as phospholipid one or more phospholipids from the group phosphatidylcholine, phosphatidylethanolamine, N ~ Acylphosphatidy! Ethanolamine, phosphatidylinositol, phosphate idylserin, lysolecithin, phosphatidyl glycerol or hydrogenated phospholipids used become. 4. Pesticide suspension concentrates according to a or more of the items 1 to 3, characterized in that are used as the phospholipid phosphatidylcholine or mixtures of phosphatidylcholine and phosphatidylethanolamine ο  5 .. Pesticide suspension concentrates according to one or more of the items 1 to 4? characterized in that a phospholipid with a content of 20 - 98% phosphatidylcholine are used as the phospholipid. 6 * pesticide suspension concentrates according to one or more of the items 1 to 5, characterized in that are used as the solvent mixtures of C ^ _-- alcohols and EthylenglycoXalkylether. 7. Pflanzenschutzmittelsuspensionskonzentrate according to one or more of the items 1 to 6, characterized in that the average particle size jC 1 «is. 8 «A process for the preparation of pesticide suspension concentrates according to one or more of the items 1 to 7, characterized in that a mixture of a) an insoluble or poorly soluble pesticide with a melting point of> 40 ° C _r b) a phospholipid, c) a solvent or solvent mixture from the group of alcohols or ethers coarsened in a colloid, ball, sand, agitator or ball mill for 10-60 minutes at 20-50 ° C,