Note: Descriptions are shown in the official language in which they were submitted.
2~:)8
HOE~HST AKTIENGESELLSCHAFT HOE 85/F 268 Dr.AU/je
New water-dispersible granules
-
The present invention relates to new water-dispers;ble
granules for use in plant protection and containing phos-
phorylated surfactants. These possess advantageous tech-
nical properties in use.
The plant protection agents on the market are ma;nly of-
fered in the form of wettable powders, emulsifiable con-
centrates or aqueous dispersions. Spray liquors are pre-
pared by stirring the agents into water. Handl;ng theseformulation forms is not free fr~m problelns. Thus the
preparation and use of wettable powder formulations fre-
quently result in nuisance caused by dust. Emulsifiable
cancentrates contain solvents which can be read;ly flam-
mable or irritant to the skin or cause an odor nuisance.On being stored for long periods, d;spersions can form
sediments which are diff;cult to shake up. In addition,
there are often problems with these formulations in re-
gard to disposal of the packaging materials.
~aeer-dispersible granules (described briefly as "WDG")
do not have these disadvantages, since they are free flo-
wing, of low dust content and readily meterable. They
can be packed without problems in polyethylene containers,
block-bottom sacks made of laminated film (paper/alumi-
num/plast;c) or cardboard drums, which can be d;sposed of
easily.
Numerous processes are available for the industrial pre-
paration of d;spersible granules (cf. H.~. Ries "Granu-
liertechnik und Granulierger~te" ("Granulation technology
and granulat;on equipment") in Aufbereitungstechnik No.3,
1970, page 147 and M. Rosch and R. Probst in Verfahrens-
techn;k 9 ~1975) pages 59 to 64). In particular, ;t is
known to prepare water-dispersible granules by the flu;dized
bed process~which can be operated in counter-current and
in co-current
o~
-- 2
The counter-current process, in which, in essence, finely
groùnd active compound powders, mixed with inert material
and formulation auxiliaries, are fluidized by means of a
stream of air enteriny from below and are agglomerated by
means of a tackifier solution sprayed from above, is des
cribed in Patent Specif;cations US-A 3,920,44~ and GB-A
1,401,304 and also by M. Rosch and R. Probst in Verfahrens-
technik 9 (1975) page 59.
In the co-current process, as described in EP-A 0,026,918
and in EP-A 141,436 and EP-A 141,437 and also in
Verfahrenstechnik 9 (1975), pages 61/62, a wet-ground dis-
persion of active compound is sprayed into the product con-
tainer of the granulation apparatus in co-current with the
air which fluidizes the solid.
The use of an active compound dispersion as the starting
material for granules is cheaper than the use of an active
compound powder, since wet grinding is technically simpler
to carry out than dry grinding.
A further method of preparing water-dispersible granules
is spray-drying aqueous dispersions of active compound,
which is described in EP-A 75,198 and EP-A 141,509.
In order to ensure fault-free use, water-dispersible gran-
ules must become thoroughly wetted when introduced into
water, must disintegrate as spontaneously as possible and
must form a suspension having good suspension pro~erty. In
the case of granules prepared by the fluidized bed Process
or by spray drying, the wettability and the breaking up are
determined by parameters relat;ng to process technology and
by the formulation auxiliaries used.
Thus round, abrasion-resistant granular grains which, how-
ever, only disintegrate sLowly in water, i.e. do not dis-
perse spontaneously, and only have a moderate to poor suspen-
sion property, are obtained in high yields by fluidized bed
granulation in accordance with the particularly advanta-
geous co-current process. In the preparation o~ granules
- 3 -
by spray drying, it is possible, in the selection of dry-
ing parameters which are particularly advantageous for
the process of preparation in regard to util;zation of
heat, particle size and yield, to produce, under certain
S circumstances~ a product which does not become wetted
adequately rapidly~
It has now been found, surprisingly, that, in both cases,
both in preparing granules by spray drying and in fluidized
bed granulation, the disadvan~ages in use of insufficient
dispersibility (poor "spontaneity") and of poor wettability
can be rectified by using special phosphorylated auxili-
aries.
The present invention therefore reLates to new water-
dispersible granules for use in plant protection which,
in addition to the active compound, contain a surfactant
belonging to the group comprising styryl-substituted,
ethoxylated and phosphorylated phenols, phosphorylated,
ethoxylated or propoxylated fatty alcohols, phosphorylated
ethylene oxide/propylene oxide block polymers or a salt
thereof or a mixture of these products.
Salts ~hich should be singled out particularly are the
alkali metal or alkaline earth metal salts and also the
ammonium, monoalkylammon;um, dialkylammonium or trialkyl-
ammonium or monoalkanolammonium, dialkanolammon;um or
trialkanolammonium salts.
Su;table styryl-containing ethoxylated phenols are pre-
ferably those which contain two or three styrene radicals
and approx. 1~ to 20 mol of ethylene oxide and are in the
torm of monoesters or diesters of phosphoric ac;d. In
particular, it is possible to employ oxethylated and phos-
phorylated tristyrylphenols which have been neutralizedwith triethanolamine, such as ~Soprophor FL (Rhone Poulenc)
or HOE S 3475 (Hoechst AG).
Phosphorylated ethylene oxide/propylene oxide block polymers
6~)8
~ 4 ~ 232~1-4323
hh;ch can be used in accordance uith the ;nvent;on are,
in particular, the polymers of formulae I to I11 below:
O/ OH
Ho-(cH2-cH2-o)x ~ (CH-CH20)z \ (I)
CH3 OH
HO O O OH
~ (CH2 CH2)x ~ (CH-CH2o~y _ (CH~-CH20~z _ p/ (II)
HO C~3 OH
HO O
P - O(CH2-CH20)x - (CH C~20)y - (CH2-CH20)7
H ~ CH3 ~ O
P (III)
/ \ OH
HO O
O(CH~ CH20)X - (CH-CH20)~ - (CH2~CH20)
HO C~3
or mixtures thereof~
x, y and z in these formulae independently of one another
denoting a number from 2 to 200O
Amongst these, bis-monophosphor;c.acid esters of the
formula Il in which x and z have approximately equal
values are preferred.
The preparation of the block polymers of the formulae I to III is des-
cribed in published Japanese Patent Application 72-47982. Compared with
knoun granules, the ~ranules according to the invention
exhibit, surprisingly, an improved ~etting and dispersing
action. Thus, for example, granules based on a phosphoric
acid monoester and diester of tributylphenol tetraglycol
ether and nonYlPhenol diglycol and tetraglycol ether do
, . ~ .
.
6~3
not achieve the act;on of the surfactants of the granules
accord;ng to the invent;on.
The ;mproved wetting and d;spersing action of the granules
according to the invention manifests ;tself in an increased
spontaneity, improved suspension property and improved ~et-
tabil;ty.
Insufficient wettability becomes evident by the fact that
the granular particles still float for some time on the
surface of the water before they disperse. The particles
can then agglutinate to form larger units~ The result of
this is frequently incomplete dispersion of the granules.
In addition to the phosphorylated surfactants to be employ-
ed in accordance ~ith the invention, the ~ater-dispersible
granules can also contain the following additives:
customary dispersing agents, such as the Na salt of a sul-
fonic acid fo~med from m-cresol + formaldehyde ~ Na sul-
fite (Dispergiermittel 1494~),
sodium oleoylmethyltauride ~Arkopon T),
sodium methoxyligninsulfonate (~ anisperse CB), sodium lig-
ninsul~onate ~orresperse 3 A), sodium methylnaphthalene-
sulfonate ~Supragil MNS 90), the sodium salt of 3-nuclear-
nonylphenol-novolak-18E0-sulfosuccinic ac;d half-ester (dis-
~ persing agent 1728~)
the sod;um salt of a d;naphthylmethaned;sulfonic ac;d t~D;s-
persogen A, ~Tamol NN0) or the sodium salt of a sulfon;c
ac;d formed from cresol ~ formaldehyde + Na sulfite +
hydroxynaphthalenesulfon;c ac;d (dispers;ng agent SS~),
or sod;um polycarboxylate t~Sopropon T 36), potass;um poly-
carboxylate (~ ;spersant DG), sod;um phenylsulfonate ~Dis-
persant GN), sod;um alkylnaphthalenesulfonate ~ upragil WP)
-- 6
or condensed sodiu~ napthalenesulfonate ~Suprag;l NS 90).
Additionally, the granules contain inert materials, such
as SiO2, chalk, starch, kaol1nite, b;nders such as poly-
vinylpyrrolidone, a sacchar;de or polyv;nyl alcahol, ifappropriate, anti-foaming agents, such as trialkyl phos-
phates, or, if appropriate, agents which promote the break-
ing open of the granular particles in water, such as pen-
tasodium triphosphate.
The ~ollowing are examples of plant protection agent active
compounds wh;ch can be employed in the granules according
to the invention: fungicides, such as tr;phenyltin com-
pounds, for example fent;n hydroxide or fent;n acetate,
benzimidazolecarbamates, such as carbendazim, h~rbicides,
such as urea derivatives, for example linuron, monolin-
uron, isoproturon or d;uron, or such as substituted phen-
oxypropionic acid esters, for example fenoxypropethyl,
insecticides, such as dinitrophenol ethers, for example
binapacryl, pyrethroids, such as deltamethrin, or chlorin-
ated bicyclic compounds, such as endosulfan. These plant
protection agents are described in Ch. R. Worthing, S.B.
Walker, The Pesticide Manual, British Crop Protect;on
Council.
The content of active compound in the granules according
to the invention is 1 ~o 95% by weight, in part;cular 40
to 90% by weight. The content of phosphorylated surfac-
tants can vary between 0.1% and 30%, ;n particular between
0.2% and 15~.
Examples of formulations
General data
A rating scale from 1 to 4 was taken as a bas;s for assess-
ing the spontaneity of the granular formulation. For this
purpose, 1 g of the granules was put into a 1 liter measur-
ing cyl;nder filled w;th standardized water (30C, 342 ppm
~32~
-- 7
water hardness). After 1 minute the measuring cylinder
was slowly turned through 180 and was returned to its
initial position. This procedure was repeated three
times.
Scale
1. All the granular particles have been dispersed.
2: All the granular particles have been dispersed on
repeating the shaking procedures described above
tinterval of two minutes).
3: Residues of non-dispersed granules have remained.
4: The major part of ~he granules had not been dispersed.
The suspension property was quoted as the amount of the
preparat;on (% by weight) which, after the expiry of a
sedimentation time of 30 minutes, is located in ~he upper
nine tenths of the parts by volume of a suspension~
The wettability was determined by the method described in
!
CIPAC Handbook Volume 1 (1970)~ page 967.
The granules described in Examples 1 to 4 were prepared
by the fluidized bed co-current process and ~ere obtained
by spraying an active compound dispersion into initially
taken granules. An STREA-1 laboratory flu;dized bed gran-
ulator made by Aeromatic AG, equipped with a roating attach-
ment, was used.
Larger batches were prepared using a Nauta or Glatt flui-
dized bed granulator of capacity approx. 20 kg. The gran-
ules used as the ;n;t;al charge were prepared by dry-
gr;nd;ng the active compound, mixing the latter with wet-
ting and dispersing agents and spraying the mixture ;n
the counter-current process w;th an aqueous tack;f;er sol-
ution. The composition of the granules is identical with
that of the dry material of the dispersion sprayed in.
~2~:6~
-- 8
The granules used as initial charge can also be obtained
by spray drying a part of the dispersion to be granulated.
Example 1
s
80.8% by weight of technical carbendazim t99% strength)
11.2% by weight of kaolin
2.0% by weight of wetting agent (see Table 1~
3.0% by ueight of the Na salt of a sulfonic acid formed
from m-cresol, formaldehyde and Na sulfite
(dispersing agent SS, Hoechst AG~
1.0% by weight of polyglycol 6000
2.û% by weight of water
Table 1
~etting agent Spontaneity Suspension
property
_ _ _
Fatty alcohol, ethoxylated 1 83%
20 and propoxylated and subse-
quently phosphorylated
HOE S 3475 1-2 83%
Comparison:
Sodium dibutylnaphthalene- 3-4 46%
25 sulfonate
The granules prepared in Example 1 have a particle size
of 0.25 - 2 mm and a wettability of <30 seconds.
Example 2
-
52.1X by weight of triphenyltin hydroxide (96% strength)
2.0% by weight of ~Soprophor FL
1.0% by weight of sodium oleoylmethyltauride ~Arkopon-T,
made by Hoechest AG)
b.O% by weight of sodium methoxyligninsulfonate
6.0% by weight of synthetic precipitated silicon dioxide
13.9% by weight of kaolin
14.0% by weight of glucose
3.0% by weight of polyvinylpyrrolidone
2.0% by weight of water
Particle size: 0.1 - 2 mm
Wettability: <10 seconds
Spontaneity: 1
Suspension property: 96%
Example 3
' - '
72.9% by weight of triphenyltin hydroxide (96% strength)
3.1% by weight of Soprophor FL
6.0% by weight of Na ligninsulfonate
3.0% by weight of polyvinylpyrrolidone
10.0% by weight of synthetic precipitated silicon dioxide
3.0% by weight of kaolin
2.0% by weight of water
Particle size: 0.2 - 2 mm
~ettability: <10 seconds
Spontaneity:
Suspension property: 95.2%
Example 4
88.30% by weight of linuron (90.6% strength)
0.25% by weight of Soprophor FL
2.25% by w~ight of sodium dibutylnapthalenesulfonate
2.90% by weight of sodium methylnaphthalenesulfonate
5.50% by weight of polyvinylpyrrolidone
0.80% by weight of synthet;c prec;pitated silicon dioxide
Particle size: OJ3 ~ 2 mm
Wettab;lity: ~10 seconds
Spontaneity: 1 - 2
Suspension property: 75%
- 10 -
Re Examples 5 - 7
The granules described ;n Examples 5 - 7 were obtained by
spray drying. They were prepared ;n a Nub;losa spray
eower using a model 118 Schlick single-substance pressure
nozzle.
Example 5
75.4% by weight of technical carbendazim (99.5% strength)
7.9% by weight of a condensation product formed from
naphthalenesulfonic acid and formaldehyde
2.0% by weight of polyvinyl alcohol containing acyl
groups, saponification number 83 + 0~8
6.9% by weight of starch, partly hydrolyzed
3.0% by weight of wetting agent, see Table 2
3.6% by weight of chalk
0.4% by weight of triisobutyl phosphate
0.8% by weight of water
Table 2
Wetting agent Wettability Spontaneity
, _
Soprophor FL 10 seconds
Forlanit P 10 seconds
_
Comparison: _
Sodium dibutylnaphthalene-
sulfonate >5 seconds 3
Particle size: 60 to 300 ~m
Suspension property: 75 - 85%
Example 6
,
80.8~ by weight of technical carbendazim (99% strength)
5.4% by ~eight of a condensation product formed from
naphthalenesulfonic acid and formaldehyde
2.9% by weight of polyvinyl alcohol containing acyl
groups, saponification number 83 ~ 0.8
. .
, .
2~
- 11 -
5.4% by weight of starch, partly hydrolyzed
3.6% by weight of Forlanit P
0.4% by weight of triisobutyl phosphate
1.5% by weight of water
Particle size: 60 to 300 ~m
Suspension property: 84%
Spontaneity: 1
~ettability: 10 seconds
Example 7
75.0% by weight of technical fentin hydroxide
5.9% by weight of the sodium salt of 3-nucLear-nonyl-
phenol novolak-18E0-sulfosucc;nic acid
half-ester
4.9% by weight of polyvinyl àlcohc,l containing acyl
groups, saponification number 83 ~ 0.8
2.0% by weight of wetting agent, see Table 3
10.5% by weight of pentasodium triphosphate
0.4% by weight of triisobutyl phosphate
1.3% by weight of water
Table 3
25 ~etting agent _ Wettabil;ty Spontaneity
~lock polymer of Type I con- 1 minute
taining 40% of ethylene oxide
in the end product
(can contain up to 30% of
30 polymer of Type III)
~lock polymer of Type I con 1 minute
taining 50% of ethylene oxide 20 seconds
in the end product
35 tcan contain up to 30% of
polymer of Type III)
~ , . ~ . ,
- 12 -
Continuation of Table 3
Wetting agent Wettability Spontaneity
8lock polymer of Type I con- 1 minute
taining 68% of E0 in the end
product
(can contain up to 30% of
polymer of Type III)
10 8lock polymer of Type II con- 1 minute
taining 40% of E0 in the end
product
(can contain up to 30% of
polymer of Type IIl)
Block polymer of Type II con- 1 minute
taining 50% of FO in the end 30 seconds
product
(can contain up to 30% of
20 polymer of Type III)
8lock polymer of Type II con- 1 minute
taining 68% of E0 in the end
product
25 (can contain up to 30% of
polymer of Type III)
Forlanit P 1 minute
30 seconds
Soprophor FL 1 minute
Comparison:
Sodium oleoyl methyltauride >10 minutes 2
The particle size of the granules in Example 7 is 60 to
300 ~m; the suspension property is 75 to 85%.
