Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
W093/0~6~2 ~ 7 3 3 PCT/F192/00258
A method of producing herbicidal granular products
The present invention relates to a method of producing herbi-
cidal granular produc~s which cantain carbamoyloxyphenyl-
carbamates and/or substituted benzofuranes, known per se, as
active ingredients, sur~actants, suspending agents, inert car-
riers, and possibly other auxiliary agents, such as stabi-
lizers, defoamers, coloring agents, and preservatives. The said
active ingredients are insoluble in water and in the main
foliage-acting, and they are thus sprayed, as water dilutions,
onto the plant s~and. For this reason the granules are made
water dispersible so that a homogenous suspension which will
not clog the sprayer will be obtained when the product is di-
luted with water.
Carbamoyloxyphenylcarbamate and benzofurane herbicides have
conventionally been formulated as emulsion concentrates in
which the active ingredient is dissolved in organic solvents
and can, with the help of solution emulsifiers, be caused to
mix with water to form an emulsion. These formulations have,
however, the drawbacks of toxicity of the products, due to the
organic solvents, inflammability of the products, as well as
difficulty of obtaining a stable uncrystallizing emulsion of
the product together with water. Crystallization is typical
specifically of methyl-3-tolylcarbamoyloxyphenylcarbamate.
Product forms in which the active ingredients are not in a dis-
solved form are as such advantageous, since then the problems
of toxicity, inflammability, packaging material, and storage
are usually avoided, since especi lly in the case of foliage~
acting herbicides, penetration and translocation abilities are
required in order to achieve sufficient biologic efficacy.
Hydrolytic decomposition is often also a disadvantage. An ac-
tive ingredient in molecular form is, in a true liquid, capable
of penetrating through the wax and cuticle layers much more
effectively ~han is a solid par~icle. For this reason, in-
W093~05652 PCT/F192/002S8
7 5 3 2
soluble particles of the active ingredient must be as finely
ground as possible, and their penetra~ion and translocation ~ -
abili~ies must be improved with oils, organic solvent addi~
tions r and surfactants. In the case of carbamoyloxyphenylcarba-
mates in particular, it is indispensable to add exceptionally -
large amounts of these auxiliary agents in order to achieve a-~- ~
sufficient biologic efficacy. Air-jet and suspension mills are ~ -
used for the grinding to produce a maximally finely divided ~-~
active ingredient, preferably in the order of magnitude of 1 - -~
5 microns, in order to achieve biologic efficacy and as stable
a suspension as possible when the granule is dispersed into
water. -
: .
In solid form, the active ingredient may be present in a water
dilutable formulation either as a li~uid suspension concentrate ~ -
or as a granular product dispersible in water. The disadvan~
tages of a liquid product form often include storage difficul-
ties, handling problems d~e to high viscosity, and the residues -
~
remaining in incompletely emptying containers. The last- ~
men~ioned disadvantage is becoming a significant environmental ;~
problem when the used containers are being disposed of. These
problems are avoided with solid granules dispersible in a li-
quid. In addition, a granular product can be packaged in mate-
rials, such as carton, which load the environment less, and
thus the empty packages are easier to dispose of.
The basic properties of water-dispersible granules include, in
addition to the chemical stability of the active ingredients,
also a good ability to be dispersed into water, sufficient
granule strength so that detrimental dust is not detached in
connection with storage or handling, free flow of the granules,
and an ability to remain uncaked during storage. In order to
achieve these properties, the granule may contain, in addition
to a water-insoluble carrier, also dispersing, suspending,
we~ing, preserving, defoaming, and anti-caking agents. ~`
W093/05652 PCT/Fl92/00258
5 3
3 ~`
It is known that carbamoyloxyphenylcarbamates, the most notable
of which are methyl-3-m-tolylcarbamoyloxyphenylcarbamate, gen-
erally named phenmedipham, and ethyl-3-phenylcaxbamoyloxy-
phenylcarbamate, generally named desmedipham (BP 679,283),
~ NHCOOR2 ~, ~
~ - NHCOo ~
where Rl and R2 = CH3 or Rl = H and R2 = CH2CH, are selective
and good by their herbicidal properties. These active ingredi-
ents can be used separately or as mixtures together with each
other and/or with other control agents, especially for weed
control in sugar beet cultivation.
Conventionally the above active ingredients have been formu-
lated as emulsion concentrates. But since the aim is to avoid
organic solvents, and since phenmedipham tends to crystallize
when these formulation forms are diluted with water, the object
has now been to produce water-dispersible granules of these
active ingredients. It is previously known to prepare water-
dispersible granules from herbicides (US 3.920.442), as also
dispersible triazine herbicidal granules, which contain a sur-
factant which improves the crystallization properties (US
4,197,112), or granules the physical properties of which are
improved by surfactants (EP 201,417). The obstacle to the com-
mercialization of dispersible carbamoyloxyphenylcarbamates has
been the difficulty of incorporating sufficient biologic ef-
ficacy in~o the product, since the amount of liquid oil and/or
surfactants is ~ery high in ratio to the amounts of the active
ingredients (approx. 1~ nd uneconomical to implement techni-
cally.
It is known that a good biologic efficacy can be achieved with
wa~er dispersible granules made of certain active ingredien~s
W0931056S2 PCT/~92/00258
~ 3 4 ~`~
~ ~,
of herbicides. However, with carbamoyloxyphenylcarbamates,
sufficient efficacy cannot be reached by these methods.
' .~ -,.
Now it has been observed surprisingly that, with water dispers- -
ible granular products which contain carbamoyloxyphenylcarba-
mate, it is possible not only to achieve the above properties
of a granular product but also to enhance them significantly by ~;~
preparing a granular or tablet-form product in which an a~ti~
vator is impregnated into a carrier, which for its part is ~-
added, evenly distributed or as a layer on the surface of the -~
granule or the tablet or as a core inside the granule or the
tablet. On the other hand, a separate granule or tablet can be --
made of a liquid activator and the carrier. The granules,
mixed together with granules containing the acti~e ingredient,
can be packaged in one container, in one space within it, as a
sufficiently evenly distributed granular mix to form one prod~
uct, or can be used as a separately dispensed agent in a tank -~
mixture. A separate tablet can be dispensed to~ether with a
granular or tablet-form active ingredient to form a combined
mixture for use. - -
By using an activator impregnated into a carrie~, the enhancing
of the biologic efficacy of solid carbamoyloxyphenylcarbamate
has even been increased as compared with unimpregnated acti- -~
vator; this has been observed in both greenhouse and field
tests. ~ `~
As the carrier for the activator it i5 possible to use inorgan-
ic substances which adsorb large amounts of oily substances and
are of natural origin, such as silica-based substances, alumi-
num oxide based substances, attapulgite, montmorillonite, mica-
based substances, diatomite, bentonite, talcum, kaolin, lime,
gypsum, and water-insoluble or water-soluble salts.
..:
on the other hand, it is possible to use as the carrier porous
organic substances of natural origin, such as ground wood or
W093/05652 ~ /5 ~ PCT~F192/00258
corn cobs, ground coconut or almond shells, ground olive skins,
yround grain husks, cellulose, starch and alginates, or porous
structures which are based on polymeric initial substances of
natural origin which have been modified, such as liynin deriva-
tives, cellulose derivatives, starch derivatives, and cyclodex-
trins, or synthetic polymers such as polyacrylates, polyacryl-
amides, polyvinyl derivatives, polymers of maleic acid, poly-
urethanPs, polylactides, and polymers of glycolic acid.
The activa~or may be enclosed in the carrier material by coat-
ing the impregnated particles with a polymer, such as polyvinyl
alcohol, or wi~h sugar based or sugar alcohol based substances,
such as lactose, CMC and sorbitol. In this case the speed of
release of the activator can also be regulated~
A li~uid activator can also be enclosed in capsules, which can
further be used in a granular product. Encapsulation methods
are commonly known. The strength of the granules and their
resistance to abrasion can also be affected by means of coating
materials. On the other hand, the flow of the product can be
improved by them.
An activator which contains surfactants and/or oil is not im-
portant for the actual granulation; its main purpose is to
enhance the biologic action of the product.
'~' .
The proportion of activator may be in general 1 - 80 % of the
weight of the granular product, preferably O.5 - 5 times the
amount of carbamoyloxyphenylcarbamate in the product.
The activator may be in a solid or a liquid state (at 20 C~,
in which case it can be impregnated into a carrier or be mixed
with the mix to be granulated. Alternatively it may also be
impregnated into or be attached to the product in some other
~anner after the granulation.
W093/05652 PCT/Fl92/00258 ;
7 ~ 3 6
'.- - .
The activator may contain anionic, cationic, non-ionic or am- -
pholytic surfactants, or these together with a mineral oil, -
vegetable oil or animal oil. The proportion of surfactants in
the activator may be 2 - 100 %, preferably 50 - 100 %. The pro- -~
portion of oil may respectively be 0 - 98 %, preferably 0 - ~-
50 %.
The anionic surfac~ants may be alkyl sulfonates, alkylaryl ~ --
sulfonates, sulfate ethers, fatty alcohol sulfates, sulfate
ester sulfocarboxylic acids and their derivatives, alkyl-
glycerolether sulfonate-~, sulfoesters, sulfonamides and phos- --
phoric acid mono- and diesters, bile acids and their salts.
The cationic surfactants may be alkylamines or alkylarylamines,
alkyl or alkylaryl imidazolines, and alkylaminoamides.
The non-ionic surfactants may be fatty alcohol ethoxylates,
fatty acid ethoxylates, alkylaryl ethoxylates, alkyl sugar
ethoxylates or alkyl sugar alcohol ethoxylates, alkylamine or
alkylarylamine polyglycol ethers, fatty acid amide derivatives,
diethanolamides or polydiethanolamides of fatty acids, deriva-
tives of mono-, di-, and triglycerides, acetylene diols, and
silicon-based surfactants.
The ampholytic surfactants may be alkyl and alkylaryl betaine
derivatives, alkyl and alkylaryl (poly)glycine derivatives,
alkylamide and alkylarylamide carboxylates, and alkylamine and
alkylarylamine sulfonates. Surfactants which contain fluorine
may also be used.
The oily substance may be a mineral oil, preferably having a
low viscosity so that it can easily become impregnated into the
carrier. On the other hand, the oil must not significantly
impede the crop plant. It is most advantageous to use low- ~-
aromatic paraffin oil, e.g. Neutral solvent 150, Exxon. The
oily substance may be a vegeta~le oil or its hydrolysis prod- ~-
W093/05652 ~ PCT/FI92/002~8
"~
uct, such as soy oil or a fatty acid mixture of soy oil. The
oil may also contain phospholipids and sterols.
The oily substance may be of animal origin, in which case it is
preferable if the oil contains a large amount of unsaturated
fatty acids and their glycerides.
It is a prerequisite for the granulation of the active in-
gredient, or of the active ingredient and its carrier which
contains an activator, or for the granulation of the carrier or
the active ingredient or the activator, that the material to be
granulated is finely divided.
The material can be comminuted, for example, while dry in an
air jet mill or as a suspension in a pearl mill. It is essen-
tial that the particle size of the solid is on average approx.
10 ~m and that of the active ingredient preferably in the order - :
of 5 ~m (measured by a Coulter apparatus), in order for the
biologic efficacy to be achieved.
In the granulation, auxiliary agents can be used which promote
granule formation, re-wetting of the granules, and rapid decom- ~-
~position and dispersion of the granules at the time the solu-
tion for use is being prepared, as well as agents which inhibit
the foaming of the solution for use. Since the active in-
gredient may decompose in a basic solution for use, inorganic
or organic pH control agents may be used in the mixture, such
as phosphoric acid or its acid salts and citric acid, so that
the pH of the solution for use will be below 7, preferably 3.5
- 5.5. -
~ '
Auxiliary granulation agents may be used in granules in which
the active ingredient and the activator are in the same granule
or in s~parate activç-ingredient granules and activator gran-
ules.
W093/056~2 PCr/F192/00258
7 S 3 8
Agents promoting the decomposition of the granule, which may be
polymers such as polyvinyl pyrrolidone and starch and its modi~
fied forms, or salts such as ammonium sulfa~e~ or organic ~-~
water-soluble compounds such as urea, or substances capable of ;~
liberating gas, such as carbonates.
As agents improving the suspension of the granules it is pos-
sible to use, as is commonly known, dispersants such as phenyl
sulfonates, alkylnaphthalene sulfonates and polymerized naph-
thalene sulfonates, polyacrylic acids and their salts, poly-
acrylamides, polyalkoxydiamine derivatives, polyethylene
oxides, polypropylene oxide, polybutylene oxide, taurine deriv-
ati~es and their mixtures, and sulfonated lignin derivatives.
Dispersants can be used at 0.1 - 50 %, preferably 5 - 20 % of
the granular product.
Similar products may also be used as agents promoting granula- -
~tion, such as polyethylene glycol, in which case it is advan-
tageous to add the activator-containing component at a propor-
tion of 1 - 20 % to the completed granule which contains the
active ingredient. -
The foaming of a mixture to be prepared for spraying can be -
controlled with defoamers such as silica-based agents. It is
preferable to use such agents at 0 - 0.5 % of the amount of the -
granular product.
Prior-known methods can be used for the granulation, such as -
disc granulation, spray drying (e.g. Niro), fluid-bed granula- -;
tion ~e.~. Glatt and Schugi), stir granulation using a vertical
mixer ~e.g. Fielder) or a blade mixer ~e.g. Forberg), extruder
granulation ~e.g. Nica) or compacting granulation ~e.g. Bepex
apparatus) or centrifugal granulation (e.g. CF-granulator,
Freund Indus~rial Co), or spray-bed granulatian.
The activat9r may be compressed into a water-~ispersible tab-
W0~3/0565~ 3 PCT/F192/00258
let, in which case its size may vary depending on the matrix..
Conventional tablet presses include rotation (Mansty) and ec-
c~ntric tablet presses ~Diaf).
It is also possible to use for the granulation and tabletting
two or more of the above methods in series. The granule sur-
face can be hardened mechanically by rounding the granule~
for example, by using a Spheronizer apparatus (Nica) or by
coating the granules with materials suitable for the purpose,
as mentioned above.
It is important that the granular product is dried. The pro-
duct may be dried either in the apparatus used for the granu-
lation or in a separate apparatus intended for drying (e.g. a ~ .
fluid-bed drier). It is advantageous if the moisture content
of the granular product is below 5 %, preferably below 1 %.
The granule size of the final product may vary, depending on
the granulation method, on average up to 3 mm or considerably
higher, in the case of tablets dispersible in water. ~
It is self-evident that also other control agents can be :-
mixed together with carbamoyloxyphenylcarbamates (such as : `
phenmedipham and desmedipham) to form a granular product. The ~:~
control agents may be herbicides, agents for plant-disease
control, and insecticides, as well as growth control agents.
It is advantageous to use herbicides used particularly in the
cultivation of sugar beet, such as ethofumesate, methamitron, `~
chlorodazone, lenasil, pyridate, metholachlorine, trichloro- ~:
acetic acid, EPTC, quinmerac, cycloate, chlopyralide, flur- .
oxipyr, isocarbimide, propham, trifluraline, alloxydime so-
dium, cetoxydime, diallate, fluazifop-butyl~ triallate, dala- -~
pon or propaqizafob.
The products of the invention can be used after the emergence
,
W093/0~6~2 PCT/F192J002S8
7 5 3 `- ~
of seedlings of the crop plant, preferably in several rounds of
application during the growing season. A suitable amount of `--
active ingredient per one spraying is 0.1 - 1 kg per hectare,
depending on the number of rounds of application.
The invention is described below in greater detail with the
help of examples.
Example 1
A separate granular phenmedipham product can be prepared from a
raw-material mixture which contains:
phenmedipham 80 %
lignin sulfonates ` 7.4 ~
phenyl sulfonates 7.0 % -
diatomite 2.0 %
kaolin 3.6 %
The raw materials used for the preparation are pre-ground with -~-
an air-jet mill (Alpine) for granulation. The granulation can
be carried out by extrusion (Nica), in which case water is
mixed with the dry mix at 10 % of the mix. The diameter o~ the ~-
openings in the matrix is 1 mm. The e~truded mix is cut into ~ -
granules of approx. 2 mm in length, which can be further round-
ed in a Spheronizer apparatus. The product is dried in a fluid-
bed drier. The product obtained by the method disperses excel-
lently into water.
The suspension can be verified with an experiment in which 1 g
of product is dispensed into a 100 ml narrow-tipped graduated -
test tube containing 100 ml of distilled water ~25 C). After
the wetting of the granules has been noted, the tube is turned
30 times through 180 degrees. Sediment formation is observed
for 1 min, 5 min, and 10 min.
In the case of the above-men~ioned granules, the amount of
sediment separa~ed at 1 min after mixing is 0.05 ml, at 5 min
W0~3tO56~2 ~ 7 5 3 PCT/FI92/002~8
11
after mixing 0.05 ml, and at 10 min after mixing 0.05 rnl.
The average partic~e size in the suspension, determined using a
Coulter LS 130 apparatus, was approx. 2 ~m. ~
For comparison purposes, a determination of the suspension pro- ~ -
perties was performed on a commercial product called Goltix,
The values obtained were: 1 min) 0.01 ml; 5 min) 0.1 ml; and 10
min) 0.18 ml. `~ ;
Exarnple 2
A separate granular phenmedipham product can be prepared from a
pre~ground raw material mixture which contains: - -
phenmedipham 89 %
lignin sulfonate derivatîves 7.2 %
phenyl sulfonates 3.6 ~ -~
The mixture can be granulated by spray drying from a 50 % -~
aqueous suspension of the mixture (Niro). The average size of -;-
the granules depends on the size of the apparatus. The granules
are round in shape. Determined by the method described above,
the suspension results are: 1 min) 0.15 ml; 5 min) 0.9 ml;
10 min) 1.2 ml. The average particle size in the suspension is
3 ~n.
Example 3
A separate granular phenmedipham product can be prepared from
the raw materials mentioned in Example 1 by using disc granul-
ation, in which case the mix to be granulated is wetted using
water at 10 % by weight, calculated from the dry matter~ The ~-
suspension results are: 1 min) 0.02 ml; 5 min) 0.15 ml; 10 min)
0.25 ml. The average particle size in the suspension is approx.
3 ~n.
Ex~nple 4
Separate granules containing an activator can be prepared by
W093/05652 PCT/FI92/00258
r7 ~ 3 12
making from a pre-ground carrier mixture by disc granulation
granules which contain: -
silicic acid (precipitated, e.g. Zeolthix 265)85 %
ammonium sulfate 2 % -~`
sodium chloride 6 %
lignin sulfonates 2 %
phenyl sulfona~es 5 %
and by impregnating into it an activator solution ~mixture A)
which contains:
alkyl-sorbitol ethoxylate 42 %
fatty alcohol ethoxylate 21 % ~-
ethoxylated fatty acid esters 8 %
ethoxylated fatty acid phosphate esters 5 %
alkylaryl sulfonic acid 5 ~
alkylamine ethoxylate 4 %
paraffin oil 15 %
at the ratio 1 : 1.5
Separate granules containing an activator may also be mixed to
form a single granule mixture with the above-mentioned granule
formulations which contain active ingredients, or it can be
dispensed separately to form a tank mixture with them. The
granules disperse moderately into water.
Example 5
A granular product containing phenmedipham and an activator can
be prepared from a raw-material mixture which contains:
phenmedipham 16.0 %
lignin sul~onates 2.6 %
phenyl sulfonates 5.5
urea 7.0 %
kaolin 5.5 %
diatomite 5.0 %
mix~ure B 50.4 %
W093/05652 ~ 7 5 3 PCT/FI92J00~58
~.
13 ~
~ ' -
polyethylene glycol 8.0 %
Mixture B contains:
silicic acid (precipitated) 37.5 %
bentonite 2.5 %
fatty alcohol ethoxylates 16.0 %
polyoxyethylene sorbitols 33.8 ~
paraffin oil 5.1 % .
alkylamine ethoxylates 5.1 % -~
The mixture is granulated in a disc in which the mix is heated
to ~70 C, and the formed granular product is cooled back to --
room temperature. The suspension properties of the product are
moderate.
Ex~mple 6
A layered granular product containing phenmedipham and an acti-
vator can be prepared from a mixture which contains:
phenmedipham 16.0 %
ligr.. in sul~onates 2.7 % .
phenyl sulfonates 5.3 %
kaolin 15.5 %
diatomite 5.0 % -
polyethylene glycol 5.0 %
mixture B 50.4 % ~as in Example S)
Mixture B is applied as a coating with the help o~ polyethylene
glycol to a granule prepared from the other raw materials, at -
~70 ~C in a disc granulator. The suspension properties of the .
granular-product are moderate.
Example 7 :
A ~ranular product containing phenmedipham and an activator can
be prepared by the extrusion technique from a raw-material
mixture which contains: ~
phenmedipham 32.0 % -
.-
W093/OS6~2 PCT/F192/00258
7~3 14
lignin sulfonates 7.4 % ~ ~:
phenyl sulfona~es 2.0 % -~
kaolin 1.1 %
diatomite 2.0 %
naphthene sulfonates 2.0 %
mixture C 50,0
~ .` '
Mix~ure C contains: `~
silicic acid (precipitated) 34.0 %
phenyl sulfonates 0.8 ~
ammonium sulfate 0.8 %
sodium chloride 1.6.%
lignin sulfona~es 0.8 %
naphthene sulfonates 2.0 %
mixture A 60.0 %
The suspension properties are: 1 min) 0.15 ml; S min~ 0.3 ml;
10 min) 0.4 ml.
Example 8
A granular product containing phenmedipham and desmedipham can
be prepared from a mixture which contains: ~
phenmedipham 60.0 % :
desmedipham 20.0 %
lignin sulfonates 5.9 %
phenyl sulfonates 5.6 % ~`
kaolin 4.0 ~ .
diatomite 2.0 %
The suspension properties of the granular product are: 1 min) .
0.01 ml; 5 min) 0.02 ml; 10 min) 0.03 ml. `
~xample 9
A granular product containing phenmedipham and etho~umesate can
be prepared by the disc granulation technique from a mixture
which contains:
7 ~ 3
W093/056~2 PCT/FI92/00258 ~-
1~
phenmedipham 32.0 % ~~;`
ethofumesate 40.0 % ::
lignin sulfonates 6.0 % ~:
phenyl sulfonates 5.0 %
naphthene sulfonates 9.0 %
ben~onite 0.2 %
urea 7.8 %
The suspension properties of the granular product are: 1 min)
0.01 ml; 5 min) 0.03 ml; 10 min) 0.04 ml.
Example 9 b .
Granules containing phenmedipham and ethofumesate can be pre-
pared by disc granulation from a mixture which contains:
phenmedipham 35.0 %
ethofumesate 34.7 %
lignin sulfonates 5.9 %
phenyl sulfonates 5.6 %
diatomite 2.0 % -
kaolin 16.8 % -:
The suspension properties were: 1 min) 0.15 ml; 5 min) 0.5 ml;: :~
10 min) 0.8 ml.
~ ~:
Example 10 -~
A gr~nular product containing phenmedipham and methamitron can
be prepared by disc granulation ~rom a mixture which contains:
phenmedipham 16.0 % ;
methamitron 64.0 %
lignin sulfona~es 5.9 %
phenyl sulfonates 5.6 %
diatomite 2.0 %
kaolin 6.5 %
The suspension properties of the granular product are: 1 min) ::~
0,01 ml; 5 min) 0.02 ml; 10 min) 0.03 ml.
:
., ,
W093/05652 PCT/FI92/00258
h )L 1 ~J 7 ~ 3 16
Example 11
A granular product containing phenmedipham and chlorodazone can : -
be prepared by disc granulation from a mixture which contains:
phenmedipham 25.0 %
chlorodazone 50.0 %
li~nin sulfonates 5.9 %
phenyl sulfonates 5.6 %
diatomite 1.1 %
kaolin 12.4 %
The suspension capacity of the granules is: 1 min~ 0.03 ml;
5 min) 0.10 ml; 10 min) 0.15 ml.
Example 11 b
A granular product containing phenmedipham and chlorodazone can
be prepared by disc granulation from a mixture which contains:
phenmedipham 20.0 % .-:
chlorodazone 60.0 % ~:
lignin sulfonates 5.9 %
phenyl su~fonates 5.6 %
diatomite 1.1 %
kaolin 7-4 %
The suspension properties of the product are: 1 min) 0.03 ml;
5 min) 0.10 ml; 10 min) Q.15 ml.
Example 12
A granular product containing phenmedipham, desmedipham and
chlorodazone can be prepared by disc granulation from a mixture
which contains:
phenmedipham 12.0 %
desmedipham 3.0 %
chlorodazone 45.0 %
lignin sulfonates 5.9 %
phenyl sulonates 7.0 %
W093/05652 PCT/Fl92/002~8
17
fluorinated surfactant 2.0 %
alkylaryl betaine 5.0 % ~-
diatomite 1.0 %
kaolin 19.1 %
The suspension capacity of the granules is: 1 min) 0.1 ml;
5 min) 0.35 ml; 10 min) 0.45 ml.
Example 13
A tablet containing phenmedipham and an activator can be pre- -
pared by compression using a pressure of 300 kg/cm2 from a
mixture which contains:
phenmedipham 24,0 % `:~
lignin sulfonates 5.9 % :~
phenyl sulfonates 3.0 %
naphthene sulfonates 4.5 %
potassium hydrogenphosphate 6~0 %
sodium carbonate 5.0 %
magnesium stearate 1.0 % ---
mixture C 50.0 %
kaolin 0.6 %
The tablet can be made in a mold having a diameter of 50 mm, in
which case 30 g of mixture is used.
The suspension properties of the tablet are moderate when the
dispersion of the tablet in a 500 ml decanter containing 300 ml ::~
of water is observed visually. -~
Biologic experiments: -
The activities of the formulations produced were tested in
action against weeds commonly encountered in sugar beet cul-
tivation, such as amaranth (Amaranthus retroflexus), rape
(Brassica naPus), goosefoo~ (Chenopodium album), and common
chickweed ~S~ellaria media). Four pots per weed species per
test specime~ were used in the experiments. The efficacies were
W093/0~652 PCT/FI92/00258
h 1 1 ~ 7 ~ 3
. ~8
evaluated in accordance with typical evaluation principles on a
scale of 0 - 10, the complete destruction of the plant being
described by 10. The mean of four pots was reported.
The sensitivity to injury of the sugar beet (Beta v_~aris) was
determined on the same scale.
Experiment 1
The biologic efficacy of a mix~ure of granular phenmedipham tas
in Example 1) and a granular activator ~as in Example 4) was
compared with a phenmedipham-containing emulsion concentrate
preparation (Kemifam) available on the market. The amounts of
active ingredient in the test specimens were the same, 640 g of
active ingredient per hectare. The efficacies were inspected 7
days after the spraying.
Active ingredient Efficacy :
product/ ama- rape goose- chick- sugar `
hectare ranth foot weed beet
Kemifam 4 1 5.7 7.8 9.8 7.0 1.0
Example 1 0.8 kg 0.7 0.0 0.0 3.0 0.0
Example 1 0.8 kg 4.0 8.0 8.3 7.7 0.3
+ Example 4 1.5 kg
Example 1 0.8 kg 7.3 8.2 8.7 7.2 1.0
+ Example 4 3.0 kg
The result shows that a granular phenmedipham product without
an activator is not biologically effective. On the other hand,
by means of the granular activator the granular phenmedipham
product can be activated so that with the same amount of the
product (3.8 kg as compared with 4 1) its action on amaranth,
rape and common chickweed is better than that of the reference,
and injury to the sugar beet is very little.
Experiment 2
In the experiment, the efficacies of granular products contain-
W093/05652 ~ 7 ~ 3 PCT/FI92/0025g
19
ing phenmedipham and an activa~or were compared with that of anemulsion concentrate product (Kemifam) available on the market
and of a suspension concentrate product (Betaflow) available on
the market. The amount of active ingredient per hectare was 640
g/ha in all the experiments. The evaluation was carried out 14 -`~
days after the spraying. ~-~
Test product Efficacy
ama- rape chick- sugar ~`
ranth weed beet
Kemifam 4 4 4 1 -
Betaflow 4 4 3
Example 5 3 3 4
Example 6 4 3 3
The results show that the granular formulations of phenmedipham
have biologic efficacies equal to those of both of the emulsion -
~and suspension concentrate references. The injury to the crop
plant is also the same. ~
. . : .
Experiment 3
In the experiment, the efficacy of a mixture of a granular
product Isuch as Example 8) containing phenmedipham (69 %) and
desmedipham (20 %) and a granular product (such as Example 4) ~
containing an activator was compared with a commercially avail-
able emulsion concentrate preparation containing phenmedipham
(129 g/l) and desmedipham (34 g/l). Thej1amounts of active in-
gredient per hectare were 652 g for Betanal Compact and 640 g
for Example 8 + Example 4, The efficacies were determined 14
days after the spraying.
Tes~ product Efficacy
product/ ama- rape goose- total sugar
hec~are ranth foot beet
~etanal 4 l 5.~ 7.2 7.0 19.7 1.0
Compact
W093/056~2 PCT/Fl92/0025~
7 ~ 3 20
Example 8 0.8 kg 8.3 5~3 9.0 22.6 1.0
+ Example 4 3.8 kg
The experiment also shows that a mixture of phenmedipham and
desmedipham works even better than the corresponding emulsion
concentrate product which served as a re~erence. The injury to
sugar beet was the same with both products.
Experiment 4
In the experiment, the efficacy of granules (such as Example 9)
containing phenmedipham and ethofumesate and of granules (such
as Example 4) containing an activator was compared with that of
a commercially available emulsion concentrate product, Betaron,
which contains phenmedipham 80 g/l and ethofumesate 100 g/l.
The efficacies were determined 14 days after the spraying. The
total amount of active ingredients per experiment was 640 g/ha.
Test product Efficacy
product/ ama- rape chick- sugar
hectare ranth weed beet
Betaron 3.6 l 5 6 9
Example 9b 0.81 kg 4 5 8
Example 9b 0.81 kg 8 7 8
+ Example 4 0.67 kg
The experiment shows that a granular mixture of phenmedipham
and ethofumesate also requires the addition of an activator,
whereby a biologically at least equally good result is achieved
as with the reference. Injuries caused are identical.
Experiment 5
In the experiment, the efficacies of a granular product con-
taining phenmedipham and methamitron (such as Example 10) and
of that product and a granular activator (such as Example 4)
were compared with the efficacy of a tank mixture which con-
sisted of a phenmedipham suspension concentrate product which
W093/0~652 ~ 1 1 Y ~ ~ 3 PCTlFI92/00258
21 ~ -
contained active ingredient 160 g/l and of a granular
methamitron product (Goltix) having a concen~ration of 700 : :
g/kg. The amounts of active ingredients per hectare were the
same for all the test specimens. The efficacies were determined :;
14 days after the spraying~ ~
Test product Ef~icacy -;::
product/ ama- rape chick- sugar
hectare ranth weed beet ~
phenmedipham 1.5 1 9.5 9.5 10 0 ::
SC Goltix 1.37 kg :~
Example 10 1.5 kg 7.0 7.0 9.0 0 :
Example 10 1.5 kg 7.0 9.0 9.5 0 -::
+ Example 4 1.1 kg
Methamitron, which works both soil-applied and foliage-applied,
does not re~uire activators in the same way as does phen-
medipham; the relatively high efficacy of granular product 10
is an indication ~f this. However, even in this case a signif~
icant improvement of action on rape is achieved with an addi- -
tion of activator. Overall, using a granular product of phen-
medipham + methamitron ~ activator, an excellent selective :~
biologic action is achieved without any symptoms of injury in
the sugar beet.
Experiment 6
In the experiment, a comparison was made among the efficacies
of a granular product containing phenmedipham and chlorodazone,
such as Example 11 b, in which the concentrations were 20 and
60 % respectively, and it and a granular activator, such as Ex- -
~mple 4, and a suspension concentrate containing effective
phenmedipham and chlorodazone, the concentrations being 100 and
300 g/l~ on the other hand, the signîficance of the granular
acti~ator in a triple-mixture granular product which contained
phenmedipham, desmedipham and chlorodazone was investigated.
The amounts of activ~ ingredien~ per hectare are the same for
W093~05652 PCT/F192/00258
~1 t ~753 22
- '
all the test specimens. The efficacies were determined 14 days
after ~he spraying
Tes~ product Efficacy
- product/ chick- ama- rape sugar
hectare weed ranth beet
phenmedipham 4.8 1 6.0 8.0 8.0 0
SC chloro-
dazone
Example llb 2.4 kg 5.0 4.0 3.0 0
Example llb 2.4 kg 6.0 6.0 7.0 0
+ Example 4 2.3 kg .-
Example 12 3.2 kg 7.0 6.0 5.0 1.0
Example 12 3.2 kg 9.0 6.0 7.5 1.0
+ Example 4 2.3 kg
The experiment shows clearly how the increase in efficacy is
important also in the mixture formulation of foliage-acting
phenmedipham and soil-acting chlorodazone. The same applies to
the triple mixture which contains foliage-acting desmedipham in
addition to the two former.
Field experiments
Field experiment 1
The purpose of the experiment was to compare the biologic ac-
tion of granular products containing phenmedipham to the action -
of emulsion and suspension concentrate products already avail- -
able commercially,
The experiments were conducted in accordance with conventional
field experiment practices. There were three rounds of applica-
tion, all performed after the emergence of seedlings of sugar
beet, The efficacy was exæmined visually and evaluated in rela-
tion to an untreated plant stand, the value for which was 0.
Value 100 describes complete control capacity. The amount of
W093/056~2 ~ 3 PCT/FI92~002~8 ;~
~3
phenmedipham used in each round of spraying was 480 g/ha.
Test product product/ha efficacy %
1 Kemifam 3 * 3 l 75 -~
(phenmedipham 160 g/l, EC)
2 Batanal Plus 3 * 3 l 83
(phenmedipham 160g/1, SC)
3 Example 1 3 * 0.6 kg 83
Example 4 3 * 1.15 kg
4 Example 1 3 * 0.6 kg 93
Example 4 3 * 2.3 kg
5 Example 1 3 * Q.6 kg 83
Example 4 mixture A 3 * 1.4 kg
6 Example 7 3 * 1.5 kg 55
7 Example 7 3 * 1.5 kg 81
Example 4 3 * 1.15 kg
~he efficacy of the granular product containing an active in-
gredient, used together with a granular activator, the total
amount of the material used being 1.75 kg/ha, is as good as the -
efficacy of ~he suspension product when used at 3 ltha. When a ~--
granular product containing more activator was used, in which
case the total amount of material used is 2.75 kg/ha, a sig-
nificantly better efficacy is obtained with the granular prod-
uct than with the suspension product. In the experiment, the
granules containing activator were dispensed separately for
reasons of test-performing techni~ues, but it i5 clear that a
granular mix containing an active ingredient and an activator
can be mixed in advance to form a single homogenous mix to be
dispensed as one.
Together with a granular product which contains active in-
gredient it is possible to use a liquid activator in the con-
ventional manner as a tanX. mixture, as in test specimen 5. The
activator granules of Example 4 contain mixture A 60 %, in
which case test specimens 4 and 5 contain equal amounts of the
W093/05652 ~ 5 3 PCT/F192/00258
24
liquid ingredient. However, it can be observed surprisingly
that the solid carrier material of the granular product in-
creases the effect of the ac~ivator granules on the efficacy of
the ac~ive ingredient by up to 10 %. It is also noteworthy that
this granular product is more than 10 % more effective than the
commercia~ su-~pension concentrate product and up to 20 % more
effec~ive than ~he commercial emulsion concentrate product.
Field experiment 2
In the experiment, the biologic efficacy of a granular product
containing phenmedipham and ethofumesate (Example 9 a) and an
activator (Example 4) was compared with the e~ficacy of an
emulsion concentrate product (Betaron) available on the market.
The overall test arrangements were as in field experiment 1.
The amount of active ingredient used was 540 g per ha per
spraying round.
Test product product/ha efficacy %
1 Betaron 3 * 3 1 95 -~
phenmedipham 80 g/l
etho~umesate 100 g/l
2 Example 9 a 3 * 0.75 kg 91
~xample 4 3 * 0.58 kg
3 Example 9 a 3 * O.75 kg 93
~xample 4 3 * 1.15 kg -~
With a total amount of 1.33 kg of the granular product, almost
the same efficacy was obtained as with 3 1 of the emulsion
concentrate. The handling of the product containing an active
ingredient and an activator in connection with the spraying did
not cause difficultie~. ;
Field experiment 3
In the experiment, the efficacies of a conventional spraying
pragram used in the cultivation of sugar beet and a sprayin~ `-
progr~m ba~ed on granules were compared. In practice, phen-
medipham, msthamitron or ethof~mesa~e is not generally used
r ~ 7 ~ 3
WOg3/056~2 PCT/F192/002~8
alone, but tank mixtures of these are used, in which the mixing ~:
ratios may vary~ depending on the weeds.
~' -'
Kemiron is an emulsion concentrate containing ethofumesa~e ~-
200 g per liter, and granular ethofumesate ~EFU granule) is a :~:
water dispersible granular product containing effective in-
gredient 65 %. The amounts of active ingredient per hectare
were the same with both the test specimens. ~-
Conventional program~
1st spraying 1.5 1 Kemifam ~ 1 kg Goltix + O.S 1 Kemiron
2nd spraying 1.5 1 Kemifam + 1 kg Goltix ~ 1.0 1 Kemiron
3rd spraying 1.5 l Kemifam + 0.5 kg Goltix + 1.0 l Kemiron :
Program based on granules:
1st spraying 0.2 kg Example 1 + 1 kg Goltix + 1.15 kg EFU-
granules ::
2nd spraying 0.2 kg Example 1 ~ 1 kg Goltix + 0.3 kg EFU-
granules ~`~
3rd spraying 0.2 kg Example 1 + 0.5 Xg Goltix + 0.3 kg E~U- ` -
granulés
each spraying containing 1.15 kg Example 4
Efficacies: conventional program 90 %
-: granule-based program 89 % :~
,;
The results show that the program based on granular products ~ :
has worked as well as has the program in which phenmedipham and --
ethofumesate are in liquid form as emulsion-emulsion concen-
trates. . : :~
~ ~ 3 ~ f
