Note: Descriptions are shown in the official language in which they were submitted.
~ ~ ~9 ~L~ ~
- 1 -
The present ;nvention relates to new suspension
concentrates which, in addition to an insoluble or spar-
ingly soluble pestic;de, contain a phospholipid and a
physiologically acceptable solvent or solvent mixture from
the alcohol or ether ~roup9 and to their preparation.
The use of plant protection a~ents for reducin0
losses in harvests due to diseases, pests and weeds can to-
day no longer be avoided in agriculture. Mos~ plant protec
tion agents are ~atRr-;nsoluble or very sparingly solub~e
in wa~er and must therefore be used in very d;lute concen
trat;on as a wettable powder or emulsion concentrate.
Because of the more favourable dosage, powder or
granule forms of emulsion concentrates are preferred in
agriculture. In use, the emulsion concentrates are emul-
sified in ~ater and appl;ed as so-called spray liquors.
Spray liquors are generally prepared from emulsion
concentrates of water-;nsoluble active compounds, ~hich
concentrates are anhydrous or have a low ~ater content.
The emulsion concentrates contain about 10 40X of the
active compounds, and ;n addit;on organic solvents and
emulsifiers and other 3UXi liaries, such as stab;lisers,
furth~r wetting agents~ anti foaming agents and the like.
To prepare the emulsion concentrates of these
water-;nsoluble ac~ive rompoundsD the active compounds are
dissolved in a sui~able organic solven~, such 35 alkyl~
benzenes, acetone, kerosene, toluene and the like, and a
suitable emulsifier or, in most cases, mixtures of such
&~3~
emulsif;ers are added. The emulsifiers used are prefer-
ably ~nionic~ cationic or non-ionic emuLsifiers or mix-
~ures of these emulsifiers. Many wett;ng agents and emul-
sif;ers can greatly ;nterfere w;th the osmo~is and water
balance of plantsD so that the plants treated are damaged.
Moreover, the solvents used are ;n most cases toxic them-
seLves, and can pollute the environment.
If a spray liquor is used9 the corresponding con-
centrates should emuls;fy spontaneously. The emulsion
formed should be sufficiently stable that no ;rreversible de-
mixing phenomena are observed e~en ~hen the emulsion is
left to stand for several ~ours. No stabLe foam should
forn when the emuls;on ;s st;rred or pumped~ The require-
~ents cf an ;deal spray l;cuor are, for example, the for-
mation of a continuous f;l~ of act;ve compound with good
adhes;on or wett;ng on the plant to be protected, and a
high res;stance to being ~3shed ~ff by rain or other
~eather influences. Furthermore~ accelerated penetration
of the active compound into the plant should be ensured.
Howe~er, most pest;cides are not only sparingly
soluble or insoluble in ~ater, but also insoluble in the
solvents acceptable for agriculture. Such agents can be
used only as granules or wettable powders. When used in
practice, difficwlties arise in exact dosing and appl;ca-
t;on. It is therefore desirable also to have a liqu;d
form for these act;ve compouncls~
It has now been found, surprisingly, that stable
suspension concentrates of plant protection agents are
obtained if insoluble or sparingly soluble pesticides are
93~
ground as a mixture with certain phospholipids in the
presence of a physiologically acceptable solvent or
solvent mixture from the alcohol or ethex group.
~he new suspension concentrates are distinguished
by the fact that the active compound is present in finely
divided form in a very finely ground form of average
particle size less than or equal to 1 ~I, as a result of
the addition of the phospholipids. The new suspension
concentrates have a high storage stability.
Thu~, according to one aspect of the invention
there is provided suspension concentrates of plant
protection agents based on an insoluble or sparingly
soluble pesticide, a phospholipid and an organic solvent
or solvent mixture, characterised in that the concentrate
consists of a) lS - 35% by weight of an insOluble or
sparingly soluble pesticide having a mel~ing point of
~40~C an~ a mean particle size of c 1~ , b) 15 - 35~
by weight of a phospholipid selected from the group
comprising phosphatidylcholine, phosphatidylethanol-
amine, N-acylphosphatidylethanolamine, phosphatidylino-
si~ol, phosphatidylserine, lysolecithin, phosphatidyl-
glycerol, hydrogenated phospholipids and mixtures thereof,
and c) 40 - 60% by weight of a solvent or solvent mixture
from the alcohol or ether group.
According to another aspect of the invention
there is provided a process for the preparation of
3~
- 3a -
suspension concentrates of plant protection agents
characterised in that a mixture of a) 15 - 35% by
weight of an insoluble or sparingly soluble pesticide
having a melting point of ~ ~0C; b~ 15 - 35~ by
weight of phospholipid selected from the group com-
prising phosphatidylcholine, phosphatidylethanolamine,
N-acylphosphatidylethanolamine~ phosphatidylinositol,
phosphatidylserine, lysolecithin, phosphatidylglycerol,
hydrogenated phospholipids and mixtures thereof, and
c) 40 - 60% by weight of a solvent or solvent mixture
from ~he alcohol or ether group, is ground together in
a collid, ball, sand, stirred or grinding ball mill at
20 - 50C for 10 - 60 minutes so that the parti d e si~e
of the insoluble or sparingly soluble pesticide is < 1~ .
Atten~ion is directed ~o our co-pending Canadian
patent applications serial numbers 431,955 and 431,956
which claim embodiments of the invention disclosed in
this application.
When spray liquors obtained from these con-
centrates with water are used, the new compositions
spontaneously form suspensions. The suspensions formed
are very stable and display no irreversible demixing
phenomena even on relatively long storage. When applied,
the spray liquors produce a continuous film of active
compound with good adhesion and wetting on the parts of
the plants to be protected. Moreover, accelerated pene-
tration into the plant is ensured. They also display a
;?o~
- 3b -
high resistance to being washed off by rain or other
weather influences. In addition, as ubiquitous compo-
nents of living material, the phospholipids are completely
non-toxic and are no threat to ecological equilibrium.
- 4 --
To prepare these ne~ suspension concentra~es~ ~he
insoluble or spar;ngly soluble pestici des are mixed with
a phospholipid or phospholipid mixture and the mixture is
ground in th~ presence of an organic solvent or solvent
mixture from the alcohol or ether group~ in particular in
the mixing proportions of 15 - 35X of pesticide, 15 - 35X
of phosphvlipid and 40 - 60X of solYent9 in colloid, ball,
sand, stirred or grinding ball mills at 20 - 50C, prefer-
abLy continuously, for 10 - 60 minutes, in particular 10 -
30 minutes. It is not necessary to add other auxiliaries.
Stable suspension con~entrates with a mean particle size
of ~1 ~ are obtained.
Examples of possible phospholipids are the co~mer~
cially available phosphatidylcholines or phosphatidyl-
15 choline mixed products~ such as, for example,
PhospholiponR 25 (ZSX of phosphatidylcholine,
25X of phosphatidylethanolamine and
2U% of phosphatidylinositol),
Phospholipon 38 (38% of phosphatidylcholine,
16% of N-acetyl -phosphatidyle'hanol
amine,
4~ of pho~phatidylethanolamine),
3~gL
-- 5 --
Phosphol;ponR 55 (55X of phosphat;dylcholine,
25X of phosphatidylethanolamine and
2X of phosphatidylinosi~oL),
Phosphol;ponR 80 ~80X of phosphatidylcholine and
10% of phosphatidylethanolamine),
Phosphol;ponR 100 t96X of phosphatidylchol;ne~ and
Phosphol;ponR 100H t96% of hydrogenated phosphat;dyl-
choline).
Natural phosphat;dylchol;nes wh;ch can be obtained
by the processes described in the following patent speci-
fications are particularly preferred: German Pa~ent
Specification 1,047,579, German Patent Specification
1,053~299, German Patent Specification 1,617,679 and
German Patent Specif;cation 1,617,680, and German Patent
Of ~enlegungsschrif ~en 3 ,04 7 ,048, 3 ,04 7 ,012 and 3 ,04 7 ~01 1,
3~
Possible H~acyl~phosphatidyle~hanolamine5 are, in
particular, those in wh;ch the acyl group ;5 derived from
saturated or olefinically unsaturated fatty ac;ds w;th 2 -
20 carbon atoms, ;n particular saturated f~tty acids with
2 - 5 carbon atoms or saturated or monoolef;n;cally un-
saturated fatty acids with 14, 16, 18 or 20 carbon atoms~
Po55i ble physiologically acceptable organic solvents or
solvent mi~tures are alcohols and ethers, such as, for
exampLe, me~hanol, ethanol, propanoL, isopropanol, butan~
ol, isobutanol, tert~-butanol, sec~-butanol, ethylene gly-
coL, ethylene glycol monomethyl ether, ethylene glycol
monoethyl ether, ethylene glycol dimethyl ether, e~hylene
glycol d;ethyL ether, diethylene glycol d;methyl ether,
diethylene glycol monoethyl ether, diethylene glycol mono-
methyl ether, diethylene glycol propyl ether, diethylene
glycol diethyl ether~ polyethylene glycols, propylene
glycols, propylene glycol monomethyl ether, propylene
glycol monoethyl ether, propylene glycol dimethyl ether,
propylene ~lycol diethyl ether, butylene glycol~ ylycerol,
Solketal, tetrahydrofuran and dioxane Mixtures of C1-3-
alcohols, such as methanol, e~hanol, propanol or isopropan-
ol, and ethylene glycol monoalkyl or dialkyl ethers are
preferred~
Possible insoluble or sparingly soluble pesticides
are active compounds or act;ve compound m;xtures from the
herbicide, fungicide, insecticide, acaricide, nematicide
or plant growth regulator groups, uhich, because of their
insolubility or low solubility in water and in physiologic-
~ &~3gL~
- 7 ~
ally acceptable solvents~ especially in alcohols, it has
not yet been possible to employ in liquid form, for
example as a solut;on or emulsion concentrate.
Possible insoluble or sparingly soluble pesticides
are, for example, the following active compounds: from
the herbicide group, for example: N-tphosphonomethyl)glycine
tglyphosate), 3-~3-chloro-~-methylphenyl)-1~1-dimethylurea
~chlortoluron3, N-t4 methoxy-6-methyl-1,3~5-triaz;n-20yl)-
am;nocarbonyl~2-chlorophenylsulphonamide~ 3-t4-isopropyl-
phenyl)~ dimethylurea (isoproturon), 3~methyl-4-amino-
6 phenyl-1,2,4-triazin-5(4H)-one tmetamitron), 1,3-dime~hyl-
3-~2-benz~hiazolyl)-urea (methaben~thiazuron), Z-chloro-
4-ethyLamino 6 isopropylamino-s~triazine (atraz;ne), 3-
~3~4-dichlorophenyl)-1-methoxy-1-methylurea (linuron),
3,5-dibromo-4Nhydroxybenzaldehyde 0 t2,4-dinitrophenyl)-
oxime (bromofenoxim~, 3-C4-tchlorophenoxy)-phenyl~
d;methylurea (chloroxuron), 2,6-dichloro-thiobenzam;de
(chlorthiamid~, N~N-dimethyl-2~2-diphenylacetamide (diphen-
amid)~ 3-(3,4-d;chlorophenyl)-1,1-dimethylurea tdiuron),
2-(3,4-dichlorophenyl)-4-methyl-1,2,4-oxadiazolidine-3,5-
dione (methazole), 3-tp chlorophenyl3-1,1-dimethylurea
(monuron), 3~t3~4-dichlorophenyl)-1-methyl-1-n-butylurea
~neburon~ 2-chloro-4,6-bis ethylamino-s-triazine (si~azine)
and 3-tert.-butyl-S-chloro-6 methyluracil tterbaciL);
from the fungicide gro~p, for example: 1,3-dicyano-2,4,5,6-
tetrachlorobenzene (chlorthalonil)~ N-trichloromethylth;o-
phthalimide ~folpet), N-(trichloromethylthio)~tetrahydro-
phthalim-ide (captan), 1-(butylcarbamoyl)-benz;midazol-2~
yl carbamate tbenomyl), 2,4-dichloro-6-~2-chloroanil;ne)-
9~
1,3,5 triazine ~anilazine), Z-~methoxy-carbonylamino)-
benzimidazole ~carbendazim)~ 6-methyl-2~oxo-1,3-dithiol-
C4,5-b~-quinoxal;ne (chinomethionat), triphenyl-tin acetate
(fent;nacetate), iron dimethyldi~h70carbamate tferbam),
N-trichloromethylthiophthalimide tfolpet), copper oxy-
chlor;de, manganese zinc ethylenedianine-bisodithio-
carbamate ~manozeb), manganese-II CN,N -ethylene-bis-(di-
thiocarbamate)~ ~aneb) and tetramethyl-thiuram disulphide
tthiram); and the following insectic;des, for example:
2,3-dihydro-2,2-dimethyl-benzofuran-7~yl N-methylcarbama~e
tcarbofuran), 0,S-d;methyl N acetyl-am;nothiophosphate
~acephate~, 1-(4-chlorophenyl)-3-~2,6-difluorobenzoyl)-
urea (diflubenzuron), 6-chloro-3,4 xylyl N-methylGarbamate
tcarbanolate) and endrin.
In pr;nciple, all pesticides hav;ng a solubility
;n ~ater or phys;olog;cally acceptable solvents, in par-
t;cular ;n the abovement;oned alcohols and ethers, of
~ 2X ~ l.e. 2 per cent or less can be used.
Example 1
20 Preparation of a herbicide suspension concentrate.
200 kg of 3-methyl 4-am;no-6-phenyl-19294-tr;azin-
5~4H)-one ~metam;tron)~ 200 kg of phospholip;d (50X phos-
phatidylcholine), 240 kg of propanol and 189 kg of poly-
e~hylene glycol 30û are dispersed in a 1,000 litre dis-
25 solving mixer for 1/2 hour. A 25 litre bead mill (stirred
ball mill) from Messrs~ Dra;s, Mannheim is then connected
and the flow rate ~hrough the mill ;s adjusted to 100
l;tres/hour. The metam;tron crystals are ground to a mean
~ part;cle s;ze of less than 1 ~ by this grinding operat;on~
~&6~
9 -
The resul~;ng suspens;on concentrate is a read;ly pourable
liquid which ~ives a stable suspension ;n ~a~er spontane~
ously or after slight shakingq The suspension can be used
as 3 spray liquor.
Example 2
_,
Preparation of a fungicide suspension concentrate.
120 9 of 1-~butylcarbamoyl)-benzimidazol~2 yl
carbamate ~benomyl)~ 115 y of phospholipid ~78X phospha-
tidylcholine), 228 g of butanol and 108 ~ of ethylene
glycol d;ethyl ether are ground for 10 minutes analogously
to Example 1. The resul~ing l;quid product gives the
desired spray liquor ~hen diluted with water~
Exa~ple 3
Preparation of a herbicide suspension concentrate.
250 kg of 1,3-dimethyl-3-(2-ben~thiazolyl~-urea
~methabenzthiazuron), 220 kg of phospholipid ~45X phospha-
tidylcholine), 138 k~ of isobutanol and 90 kg of propyl-
glycol monomethyl ether are dispersed in a 750 litre dis-
qolving mixer for 1/2 hour. A tandem mill from Messrs.
20 Netzsch is connected~ and the dispersion is ground in two
stages with a throughput capacity of 90 kg/hour. A 50%
particle size of the metnabenzthiazuron crystals of less
~han 1 ~ is achie~ed by this grinding operationO The
resulting suspension concentrate is a readily pourable
25 liquid, which gives a stable suspension in water spontane
ously or after slight shaking. The suspension can be used
as a spray liquor.
33~L~
~10 _
Preparation of a herbic~de suspension concentrate
150 9 of 2-chloro~4-ethylam;no-6-isopropylam;no-
s-tr;azine Satrazine)~ 46 9 of phospholipid ~75X phospha-
tidylcholine~, 95 9 of ethanol and 90 9 of ethylene glycol
monoethyl ether are ground, as described in Example 1,
w;th the ald of SO g of sand ~d;ameter 1 mm, standard
sand, 20 - 30 ASTM, Ottawa Silica Corp.).
Example S
Preparat;on of a herbic;de suspens;on concentrate.
50 9 of 3-(3,4-dichlorophenyL)~1-methoxy-1-me~hyl-
urea ~linuron), 146 9 of phospholipid (50X phosphat;dyl-
choline), 114 9 of methanol and 90 9 o~ e~hylene glycol
monomethyl ether are together introduced into a stirred
m;ll (manufacturer: Vollrath, Cologne~ type VSM, grinding
pot s;ze 2.2 litres, speed of rotation 2,820 m 1) contain-
ing 1.2 k3 of sand tdiameter 1 mm., standard sand, 20-30 ASTM,
Ottawa S;lica Corp.), and are stirred at room temperature
for 20 minutes, whereupon the linuron crystals are ground
to a ~ean particle size of Less than or equal to 1 ~.
The following concentrates can be prepared analo
gously to Examples 1 - S:
Example 6
Fungicide suspension concentrate
120 9 of 1~3-dicyano-2,4,5,~-tetrachlorobenzene
(chlorthalonil), 95 g of phospholipid ~50% phosphatidyl-
choline), 12~ 9 of isopropanol and 80 9 of ethylene glycol
monomethyl ether.
C33~
Fungicide suspension conc~ntrate
140 9 of N trichloromethylthiophthaLimide (folpet),
65 g of phospholipid (75X phosphatidylcholine), 90 g of
ethanol and 120 9 of diethylglycol monomethyl e~her.
Example 8
Fungicide suspension concentrate
115 9 of N-(~richloromethylthio)-tetrahydrophthal-
imide (captan), 120 9 of phospholipid S25X phosphatidyl-
choline)~ 230 9 of tetrahydrofuran and 60 g of d;ethylene
glycol monoethyl ether.
ExamQ~
Preparation of a herbicide suspension concentrate.
100 9 of 3-(4-isopropylphenyl)-1,1 dimethylurea
tisoproturon), 100 9 of phospholipid (95X phosphatidyl-
choline)r 130 9 of ethanol and 90 g of ethylene glycol
monoethyl ether are together introduced into a stirred
mill (manufacturer: Vollrath, Cologne, type VSME, grinding
pot s;ze 2.2 litres9 speed of rotation 2,820 m~1) contain-
ing 1 kg of lead glass balls (d;ameter 3 mm~, and are
stirred at room temperature for 20 m;nutes, whereupon the
isoproturon crystals are ground to a mean particle size of
less than or equal to 1 ~. The resulting suspension concen-
trate is a readily pourable liquid ~hich gives a stable sus-
pension in ~ater spontaneously or after slight shaking~ The
suspension can be used as a spray liquor.
Example 10
Herbicide suspension concentrate
100 g of N-phosphonomethylglycine ~glyphosate),
3~
- 12
70 ~ of phospholipid t25X phosphatidylcholine)~ 150 y of
tetrahydrofuran and 100 9 of ethylene glycol monoethyl
ether.
Example 11
Herb;c;de suspens;on concentrate
100 9 of 3 (3~chloro-4~methylphenyl)-191-dimethyl-
urea tchlortoluron), 96 9 of phospholip;d C45% phospha-
t;dylchol;ne~ 92 9 of methanol and 90 9 of ethylene gLy
col monoethyl ether~
~,
Herbicide suspens;on concentrate
30 9 of N-~4-methoxy-6 ~ethyl-1,3,5-triazin-2-yl)~
aminocarbonyl-2-chlorophenyl-sulphonamide~ 190 9 of phos-
phol;pid (78X phosphat;dylcholine), 210 9 of ethanol and
170 9 of ethylene glycol monomethyl ether.
Example 13
Insecticide suspension concentrate
95X of 2,3-dihydro 2~2-di~ethyl-benzofuran-7-yl
N-methylcarbamate tcarbofuran), 107 9 of phospholipid (95X
phosphatidylcholine), 125 9 of isobutanol and 95X of
ethylene glycol.
Example 14
Insecticide suspension concentrate
49 9 of 0,5-dimethyl-N-acetyl-amido-thiophosphate
~acephate), 112 9 of phospholipid (45X phosphatidylchol;ne)~
120 9 of ethanol and 75 9 of e~hylene glycol monoethyl
ether.
g3~
_ 13 _
Example 15
Insect;c;de suspens;on concentrate
1~4 9 of 1-(4-chlorophenyl)-3-~2~-d;fluoroben-
zoyl)-urea ~diflubenzuron)~ 9~ 9 of phospholip;d (?5X
S phosphat;dylchol;ne)~ 210 9 of ethanol and 90 9 of propyl-
~lycol dlmethyl ether.
Example 16
Insecticide suspension concentrate
100 9 of N-(2-chlorobenzoyl)-N'-(4~trifluoro-
methoxy~pher1yl~-ure2, 100 9 of phospholipid (48X phospha-
tidylcholine), 130 ~ of ethanol and 90 9 of ethylene
glycol dimethyl etherO
