Note: Descriptions are shown in the official language in which they were submitted.
2 ~ L/,~
T~e present invention relates ~o new solid for~ulations
based on agrochemical active compounds, to processes for
~he preparation of ~he solid formulations and ~o their
use as agen~s for ~rea~ing plants.
It has already been disclosed that agrochemical active
compounds can be used in the form of solid formula-ionsJ
such as granules or powders, However, the activity of
such preparations is not always entirely satisfactory.
For ex~mple, it is in some cases less powerful than ~ha~
of corresponding emulsifiable concentrates.
In particular, it has already been disclosed tha~ L-~4-
chlorophenyl1-4,4-dimethyl-3-(1,2,4-triazol-1-yl-meth-
yl)-pen~an-3-ol has fungicidal properties and can be
converted into cus~omary formulations tcf. EP-OS (Euro-
pean Published Specification1 0,040,345~. Thus, solid
formulaticns, such as granules or powders, which contain
the above-mentioned active compound, can also be pro-
duced, The activity and ~he compatibility of ~hese con-
ventional solid formulations, however, is no~ always
entirely satisfac~ory~
Fur~hermore, the produc~ion of granules containing
agrochemical acLive compou~ds by the fluidised-bed
process has also been described (cf. EP-OS (European
Published Specification) 0,163,836). Thus, it is also
possible using this method, to ob~ain granules in ~which
1-(4-chlorophenyl)-4~4-dimethyl-3-(1,2,4-~riazol-1-yl-
methyl1-pen~an-3-ol is present as ~he active component.
However, the activi~y of ~hese formulations too, leaves
something to be desired in some cases.
l2A 2 7 7 4 1 - 1 -
9 ~ ~ d
New solid formulations of
A) at least one agrochemical active compound,
B) at least one additive from the groups comprising
- polye~hoxy-isotridecylalcohol having an average of
6 ethylene oxide units per molecule, or
- alkylaryl-polyetho~ye~hanol phosphoric acid esters,
~ or
.~ 15
:i - the N-alkyl-lactams of the formula
~-( CH2 ) ~
~ N-R (II)
~llJ ,'
~:)
'' .
in which
~; R represents alkyl having S to 18 carbon atoms
and
n represents the numbers 3, 4 or 5, or
- the N,N-d;me~hyl-alkylcarboxamides of the ~ormula
~CH3
Rl-C0-N ~III)
~5 ~ CH3
l0A 2 7 7 4 1 - 2 -
.
: . .
- . .
- - , ; ~
in which
R1 represent~ alkyl having 5 tD 11 carbon a~oms,
C1 at least one dispersant,
D) at least one carrier and
E1 if appropr;ate, further active compounds andlor
additives,
have now been found.
Furth0more~ it has been found tha~ Lhe new solid
formula~ions c~n be prepared by either
a) - introducing a solution of a~ least one agrochemical
~ active compound and, if appropria~e, addi~ives in
- at least one additional compound from amongs~ the
groups mentioned under (B1 and
';~
: 2S - a mi~ure of at least one dispersant and at least
~ one carrier and, if appropr;a~e, fur~her agrochemi-
:~ cal ac~ive compounds and/or additives,
:
:3 0
L~A 2 7 7 4 1 3
.
.
.
)` ~ . :' :
separately in~o a fluidised-bed granulator, granu-
la~ing the mi~ture until a granular product has
formed, and discharging the granules frorn the
fluidised-bed granulator, if appropriat.e after
spraying with water followed by drying,
or
b) - introducing a mixture of at least one dispersant
and at least one carrier and~ if appropriate,
agrochemical-active compounds and/or additives into
a mixer,
- spraying intD the mixer a solution of at leas~ one
agrochemical active compound and, if appropriate,
additives in a~ least one additional compound from
amongst ~he groups mentioned under (B) until
a product having the desired particle
size is formed and
- discharging the resultin~ solid formulation from
the mixer, if appropriate, after previously spray-
ing with water followed by drying,
and, if appropriate, subsequently grinding the resulting
solid formulations.
; ~0
Furthermore, it has been found ~ha~ the solid forrnula-
tions according to the invention can be emplvyed very
successfully as agents for treating plants and have
excellent biological proper~ies.
3~
'~
I~A 2 7 7 4 1 - 4 -
-: - .. : ~ , ,
, .
- ~
2 ~
Finally, a new device for preparing the new granules has
been found. The device essentially consists of a flui-
dised-bPd granulaLor which comprises
- one or more feed pipes for feeding a solid phase
~o ~he fluidised bed,
- one or more two-fluid noz71es for feeding and for
atomising a liquid phaseg
- one or more feed pipes for feeding fluidising gas
and
~ - one or more counterflow gravity classif;ers for
: discharging granules.
It must be considered ex~remely surprising that ~he
solid formulations according Lo the invention in all
cases have superior biological proper~ies to ~he corre-
sponding solid formula~ions hi~herto known. Thus, for
example, the solid formulations according to the in-
: 25 vention, based on 1-(4-chlc,rophenyl)-4J4-dim~thyl-3-
~1,2,4-triazol-1-yl-methyl)-pentan-3-ol can be usF~d
considerably more effectively for ~ombaLing phytopatho-
genic fungi ~han the solid formulations known from ~he
prior art and which also contain the same active com-
pound,
Agrochemical active compounds which can be contained in
the solid formula~ions ac&ording ~o the invention are
all those subs~ances which are conventionally sui~able
l0A 2 7 7 4 1 5
~ . ` ' ` '
2 ~
for ~reating plants. Sui~a~le active compounds are no~
only substances which are solid at room temperature but
also those which are liquid at room ~emperature. The
only precondition for ~he use of liquid components i5
~hat they mus~ be capable of being applied to ~olid
carrier su`ostances, if appropriate, wi~h powdering. The
ac~ive components can be soluble or insoluble in wa~er.
They mus~ have such s~ability that they do not undergo
any major decomposition ~hile the process according ~o
the in~ention is being carried ouL or during ~he use
of the resulting solid formulations.
In the present case, agrochemical active compound!i are
to be understood to be active compounds which are
customarily usable in crop protection. They preferably
include insecticides/ acaricides, nematicides, fungi-
cides, herbicides, growth regulators and fertilisers.
The following may be men~ioned as specific examples of
such active compounds.
1-(4-chlorophenyl)-4,4-dim~thyl-3-(1,2,4-~riazol-1-yl-
methyl)-pentan-3-ol (tebuconazole) J
4-chlorophenoxy)-~,3-dimethyl-1-(1,2l4-tria701-1-
yl)-butan-2-ol (triadimenol)~
1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-
butan-2-one (~riadimefon),
. ~
IBA 2 7 7 6 1 - 6 -
,~ .
~'~
. . .
, . . .
~ . . . ~ .
1-(4-phenyl-phenoxy)-3,3-dLmethyl-(1,2,4-triazol-1-yl)-
butane-2-ol (bitertanol),
N,N-dimethyl-N~-phenyl~(N~-fluorodichloromethylthio)-
sulphamide (dichlofluanid)~
N,N-dimethyl (N'-fluorodichloromethylthio) N'-(4-methyl-
phenyl)-sulphamide (tolylfluanid)~
N-trichloromethylmercap~o-4-cyclohexene-1/2-dicarboxamide
(captan),
N-(1,1,2,2-tetrachloroethyl-sulphenyl)~ci~-4-cyclohexene-
1,2-dicarboxamide ~captafol),
N-trichloromethylthio~phthalimide (folpet),
N-dodecyl-guanidine acetate (dodine),
tetrachloro-isophthalonitrile (chlorothalonil),
4,5,6,7-tetrachlorophthalide,
~inc ethylene-bis-dithiocarbamate ~zineb),
manganese ethylene-bis-dithiocarbamate (maneb),
zincethylene~bis~dithiocarbama~e/manganeseethylene-bis
: 20 dithiocarbamate (mancozeb),
zinc propylene-1,2-bis dithiocarbamat~ (propineb),
1 [3-(4-(l,l-dimethylethyl)-phenyl~-2-m~thylpropyl~-
piperidine (fenpropidin)/
N-tridecyl-2,6-dLmethyl-morpholine (tridemorph),
N-dodecyl-2l6-dimethyl-morpholine (aldimorph) r
~; 2 C2-(2,4-dichlorophenyl)-2-(2-propenyloxy)-ethyl]-
imidazole ~imazalil),
N-~2 (2,4,6~trichlorophenoxy)-ethyl]-N~propyl-lH-im-
idazole (prochloraz),
N-(3,$-dichlorophenyl)-1/2-dimethyl-cyclopropane-1,2
dicarboximide (procymidone),
2~methoxycarbamoyl-benzLmidazole (carbendazim),
LeA 2 7 7 ~ l _ 7 _
- . -- .. ......... .
2 ~
me~hyl 1-(butylcarbamoyl?-2-benzimidazolecarbama~s
(bPnomyl),
2,4-dichloro-6-(2~-chlorophenyl-amino)-1,3,4-~riazine
(anilazine),
bis-(8-guanidino-octyl)-amine ~riace~a~e Sguazatine),
1-(4-chlorobenzyl)-1-cyclopen~yl-3-phenyl-ursa
(pencycuron)~
6-methyl-2-oxD-1,3-di~hiolo-[4,5-b]-quino~aline (chino-
me~hiona~),
: trans-4-(4-chlorophenyl)-N-cyclohexyl-4-methyl-2-oxo-3-
~hiazolidin-carboxamide (hexy~hiazox),
: 15 1-(4-fluorophenyl)-1-(1,2,4-~riazol-1-yl-me~hyl)-2-(Z-
-~ chlorophenyl)-oxirane,
2-(2,4-dichlorophenyl)-1-(1~2~4-~riazol-1-yl)-pen~ane
:~ tpenconazole),
1-t2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-Z-yl-
methyl]-lH-(1,2,4-~riazole) (propiconazole),
; 1-[2-~2-chloro-4-(4-chlorophenoxy)-phenyl]-4-me~hyl-
(1,3-dioxolan-2-yl)-me~hyl]-lH-(1,2,4-~riazole),
(2,4-dichlorophenyl)-4,4-dimethyl-2-(1,2,4-~riazol-1-
yl)-pentan-3-ol (diclobutrazole), m
1-(2- hlorophenyl)-2-(1-chloro-cycloprop-1-yl)-3-(1,2,4-
triazol-1-yl)-propan-2-ol~
1-cyclohexyl-4,4-dimethyl-3-hydroxy-2-(1,2,4-triazol-1-
yl)-psn~-1-ene (triapen~henol),
2-;sopropoxy-phsnyl-N-ms~hyl-carbamate,
~0 4-amino-6-(1,1-dims~hyl-s~hyl)-3-me~hylthio-1,2,4-
~riazin-5(4H)-on (mstribuz;n)~
~-methyl-4-amino-6-phsnyl-1,2,4-tr;azin-5(4H)-on
(ms~ami~ron),
~5
l~A 2 7 7 4 1 - 8 -
.
.. . .
2 ~
N-benzthia~olyl-N-methyl-N~-methyl-urea,
3-mz~hoxycarbonyl-aminophenyl-N-(3 -methyl-phenyl~-
carbamate~
N-(4-trifluorome~hoxy-phenyl)-NJ-(2-chloro-benzoyl)-
urea,
l-e4-(2-chloro-1,1,2-trifluoroe~hoxy)-phenyl]-3-(4-
phenyl-112,5-oxadia~ol-3-yl)-urea,
2-e~hoxy-2~3-dihydro-3,3-dimethyl-5-benzofuraryl-
methansulfonate.
1-t4-Chlorophenyl)-4J4-dimethyl-3-(1,2,4-triazol-1-yl-
methyl)-pen~an-3-ol of the formula
o~ .
Cl ~ CH2-CH2-C-c(cH3)3 (I)
,.~ I
CH2
~1N`N
is particularly preferred.
: This active compound and its use as a fungicide are
known tcf. EP-OS ~European Published Specification~
0,040,345~.
The active compound of the formula (I) can be cen~ained
in the solid formulations according to ~he invention
ei~her as ~he sole ac~ive component or in admixture with
other agrochemical ac~ive compounds,
LeA 2 7 ? 4 1
............................ ....... . .. . .. ... ..
: ,~ .
2 ~ ~* ~ ~ LJ~
In the solid formulations according to the invention~
at least cne of the substances mentioned under (B) is
contained as an additional substance. The followin~ are
pref0rably suitable:
- polyethoxy-iso-tridec~l alrohol having an a~erage
1~ of 6 ethylene oxide units per molecule,
- alkylaryl-polyethoxyethanol phosphoric acid ester,
commercially availabla under the name "Blendex~
- N-alkyl-lactams of th~ formula (II) in which
R represents alkyI having 8 to 14 carbon atoms
and
: 20 n represents the numbers 3, 4 or 5, and
:
- moreover, individual N,N-dimethyl-a1kylcarboxamides
l of the formula ~III), or mixtures ~hereof.
.~ ~5 Particularly preferred N-a1kyl-lactams are those
substan~es of ~he formula (II) in which
R represents alkyl ha~ing 8, 10 or 12 carbon atoms
and
n represents ~he numbers 3, 4 or 5,
3~
'
~ - 1 0 -
~ .
2 ~
The following may be ~en~ioned as examples of N-alkyl-
lac~ams of ~he formula (II):
N-dodecyl-caprolac~am
N-decyl-caprolac~am
N-octyl-caprolactam
N-dodecyl-pyrrolidone
N-decyl-pyrrolidone
N-octyl-pyrrolidone
N-dode~yl-valerolactam
N-decyl-valerolac~am
N-octyl-valerolac~am,
Also particularly preferred is ~he mixLure of ~,N di-
methyl-alkylcarboxamides of the formula (III) which i5
known under the tradename Hallcomid and which comprises,
~ 20 on average, 5% NJN-dime~hyl-hexanecarboxamide, 50% N,N-
; dime~hyl-oc~anecarboxamide, 40'~. N,N-dimethyl-decanecarb-
oxamide and 5% N,N-dimP~hyl-dodecanecarboxamide.
The additional subs~ances present in ~he sol;d
formula~ions according to ~he inven~ion are known (cf~
~; J. Org. Chem. 18J 108? (1953); Ann. Chem. 596, 203
(1955); J. Amer. Chem. Soc. 69, 715 (1947)~ DE-AS
(German Published Specifica~ion) 1J16OJ268~ EP-OS
(European Published Specifica~ion) 0,077,07B, WO
30 8BlO0 184 and Farm Chemicals Handbook 1990, C 44).
Sui~able dispersan~s in ~he case of solid forrnula~ions
according ~o ~he inven~ion are all subs~ances which have
appropria~e surface-ac~ive proper~ies and which can
~ i
_eA 2 7 7 ~
,
.
2 ~
customarily be employed for such purposes. The following
are pre~erred: ligninsulphonates such as lithium salts,
sodium salts, potassium salts, magnesium salts, calcium
salts and ammonium salts of ligninsulphonic acid, fur-
thermore condensation products of aryl- or alkylaryl-
sulphonic acids and formaldehyde, such as condensation
products of sulphonated ditolyl ether and formaldehyde,
and salts thereof, as well as addition products of e~h-
yleneoxide and fatty acid esters and salts thereof.
Suitable carriers in the case of the solid formulations
according to the invention are all solid substances
which have a large surface area and/or high a~sorbency
and which can customarily be used in granules and
powders, The following are preferred: ground natural
minerals such as kaolins, clays, ~alc, chalk, quartz9
attapulgite, montmorillonite or diatomacious Parth, and
~ ground synthetic minerals such as highly-disperse sili-
:~ ca, alumina and silicates, and furthermore salts such
as potassium sulpha~, potassium carbonate and sodium
hydrogen carbonate.
Suitable additives which cari be contained in ~he solid
. formulations according to the inven~ion are binders,
preserva~ives, colorants, acids and granula~ion
. liquids.
~5
LeA 2 7 7 6 1 - 12 -
'' ~ ' ' ,
Binders which can be contained are all bind~rs
5 (~ac~ifiers) which are custom3rily pr~sent in water-
dispersible solid formula~ions. The following are
preferably suitablP in this conte~t: me~hylcellulose,
sugars, dextrin, starch, alginate~, glycols, polyvinyl
pyrrolidone, ligninsulphonate, gum arabic, polyvinyl
alcohol and polyvinyl ace~ate.
Examples of preservatives which can be contained in the
solid formulatior,s according to the invention are 2-
hydroxybiphenyl, sor~ic acid, p-hydroxybenzaldehyde,
methyl p-hydroxybenzoate, benzaldehyde, benzoic acid and
propyl p-hydroxybenzoate.
Colorants which may ~e mentioned as suitable additives
are inorganic pigmen~s such as iron oxide, titanium
dioxide and Prussian blue, and organic dyestuffs such
as alizarin, azo and metal phthalocyanine dyestuffs.
'
An example of an acid which may be mentioned as a sui~-
able additive is p-tolyl-sulphonic acid.
Examples of granulation liquids which can he conLained
in the solid formulations according to the invention are
water, organic solvents or mixtures of water and organic
solvents, Preferred organic solvents which are suiLable
in this conte)~t are alcohols such as ethanol and glycol,
halogenohydrocarbons such as methylene chloride, and
ethers such as dioxane and tetrahydrofuran. Water is
particularly preferred as granulation liquid,
~5
QA 2 7 7 4 1 - 13 -
.
: ~ :
:
2 ~
In the solid formulations according to the invention,
~he percentage con~ents of the componen~s can be varied
wi~hin substantial range, In general, thP conLent of
agrochemical active compounds i5 be~ween 5 and 90% by
weigh~, preferably br~tween 10 and 50% by weigh~. The
amount of additive is generally 5 to 75% by weight,
preferably 10 to 70% by weight, The amount of dispersant
is generally between 1 and 30-/0 by weight, preferably
between 5 and 25~/. by weight; and ~he amount of carrier
is generally between 10 and 50% by weight, preferably
between 15 and 45~/. by weight, ThP addi~ional compounds
are generally rontained in amounts of betwr~en 10 and 70%
by weight, preferably between 20 and 50% by weight, and
the amount of granulation liquid is generally between
0 and 3.5~/. by weigh~.
2~ When carrying ou~ the proress according to ~he invention
by means of var;ants (a~ or (b), all those components
can preferably be used as being preferred which have
~- already been men~ioned ;n connection with ~he descrip-
tion of the solid formulations according to the in-
vention
For carrying ou~ the process according to the inven~ion
by means o~ variant (a), a solution of at least one
agrochemical active compound and, if appropriate, addi-
tional substances in at leas~ one additive is firs~prepared. For this purpose, the componen~s are stirred
with each other at temperatures between 10C and 100C,
preferably between 20C and 90C, so ~ha~ a liquid phase
results, Accordingly, ~he liquid phase is a melt or a
~5 ~rue solu~ion.
l~A 2 7 7 4
.'
i;
,~:
Furthermore, a solid mixture i 5 prepared by rnixing at
least one dispersant and, if appropriate, one or more
agroche~ical active compounds and/or additives with at
least one solid carrier in such a ratio that the re-
sulting mixture is in the solid phase. This mixture of
solid substances is homogenised using customary
processes.
For carrying out the process according to the invention
by means of variant (a), tha liquid and the solid phase
are introduced separately into a fluidised-bed granw-
lator. In general, a procedure is followed in which thesolidJ finely pulverulent phase i5 passed int~ the
granulator through one or more inlets and fluidised with
the aid of a stream of gas. The liquid phase i5 also
sprayed into the granulator through one or more separat~
nozzles~ The liquid phase i5 preferahly added via one
or more two-fluid nozzles which are constructed in such
; a way that the liquid phase is transported through a
first line and a stream of gas (a~omising gas) is fed
in through a second line. Both s~reams meet each other
at the end of the nozzle in such a way that, with the
aid of the atomising gas, the liquid phase is sprayed
into the fluidised bed in the form of small droplets~
and there meets the particles of ~he solid phase.
If appropriate9 post-granulation can be carried out by
spraying on water. To remove water andJor other sol-
~en~s, the granules can be dried wiLh the aid of the
stream of gas for fluidisation.
3~
LeA 2 7 7 6 1 - 1S -
,, . . . . - ~
. .
- : ' " . ~;
- .:
When carrying out ~he process according to the inven~ion
by means of varian~ (a), the Lemperatures can b~ varied
within a substantial range. For example, the process is
carried ou~ using a liquid phase whosP temperature is
between 10C and 100C, preferably between 20C and
90C. The solid phase is fed in at temperatures between
10 10C and 50~C, preferably between 20C and 40C. The
tempera~ure of the stream of gas for fluidisation i5
between 20C and 250nC, preferably between 40C and
200C. The temperature of the stream of gas for
atomisation, which enters through the ~wo-fluid noz~le,
i~ betwesn O~C and 100C J preferably between iO~C and
90C
To produce the fluidised bed, all gases which are
ustomarily employed for such purposes can be used. Air
or nitrogen are preferably sui~able.
For spraying in the liquid phase via one or more two-
fluid nozzles, i~ is also possible to use all gases
which are customary for such purposes. Air or nitrogen
are preferably suitable.
The finished granules can be discharged from the
uranulator via customary withdrawal devices. Coun~er-
; current gravity classifiers are preferably usedO
~oThe product ob~ained can subsequently be postgranulated
and/or dried and/or ground.
When variant (a) is used, the process according to the
~5 invention can be carried ou~ continuously or batchwise.
';
l~lA 2 7 7 /" - 16 -
, ~ .
... . ....... ... . ... .. . ... ..... .. .. . ... ... . . . .... ..
.
.: .
: .
. ~ .
f~
The devi~e for preparing the granules according o
S variant (a) of ~he invention is a fluidised-bed
granulator which differs from the previously known
apparatuses of this type essentially by the fact that
the liquid phase and the finely pulverulent solid phase
are fed separately into the fluidisecl bed,
1~
One or more feedpipss for the solid phase are located
in the lower area of the fl~idised bed, preferably in
the side wall of the apparatus, slightly above the
inlet-flow bottom, To feed the liquid phase, ~here exist
one or more two-fluid nozzles which are preferably
arranged at the inlet-flow bottom. The two-fluid nozzles
are constructed in such a way that the liquid phase is
transported ~hrough the first feedpipe and a stream of
gas ~atomising gas) is fed through a second feedpipe,
Ore or more feedpipes for introducing fluidised gas are
arranged below ~he inlet-flow bottom. Finally~ the
device contains one or more counterflow gravity classi-
fiers for diseharging granules, The counter~low gravity
classifiers are preferably built into the inlet-flow
bottom, Preferred counterflow gravity class;fiers which
are suitable are so-called zig-zag classifiers.
Variant (a) of the process ac~ording to the invention
is preferably carri d out in a fluidised-bed granulator
as showr, in Figure 1 in the form of a diagram, In this
figure,
LaA ~ 7 7 4 1 - 17 -
- . . . . . ~
- ' ' ',
.
-: . - ,
2 ~
1 denotes the wall of the gran~la~or vessel,
2 denotes ~he feed for the sDlid phase,
3 denotes the feed for ~he liquid phase,
4 deno~es the feed for ~he a~omising gas,
denotes ~he two-fluid nozzle,
6 denotes the feed for the fluidised gas,
7 denotes ~he fluidised bed,
8 deno~es the settling zone in the fluidised bed,
9 deno~es the counterflow gravi~y classifier, and
deno~es ~he withdrawal device for the granules.
For carrying out ~he process according to the invention
by means of varianL tb), a solid mixture is first pre-
pared ~y mixing at least one dispersant and, if
appropria~e, one or more agrochemical active compounds
andlor addi~io~al compounds with a~ least one solid
carrier in such a ratio that the resulting mixLure is
in the solid phase. This mixture of solid substances is
homogenised and ground using customary processes.
'
Furthermore, a solution of at least one agrochemical
active compound and, if appropriate, additional sub-
stances in at leas~ one additive is prepared. FDr thi~
purpose, ~he components are stirred with each oLher at
~emperatures between 10C and lOO~C, preferably between
20C and 90C, so that a liquid phase results. Accord-
ingly, the liquid phase is a melt or a true solution.
LaA 2 7 7 4 1 - 18 -
__
. ~ _ _~_.. . _ .. ... . .. ... .. .. . . . .
.'
~ . .
For ~arrying ou~ th~ process according to the inven~ion
by means of varian~ (b), the solid~ finely pulverulen~
phase is passed into a mixer and sprayed with the liquid
phase. In general, a prc,cedure is followed, in whi~h the
liquid phase is sprayPd irl~o the mixer Lhrough one or
more separate nozzles.
The liquid phase is preferably added via one or more
two-fluid nozzles which are constructed in such a way
that the liquid phase is ~ranspor~ed through a first
line and a s~ream of gas (a~omising gas) is fed in
~hrough ~ serond line~ Both s~reams mee~ each o~her at
~he end of the nozzle in such a way tha~J wi~h ~he aid
of the aLomising gasJ the liquid phase is sprayed in~o
the mixer in ~he form of small droplets, and ~here meP~s
~he par~icles of ~he solid phase.
If appropria~eJ a post-~rea~ment can be carried ou~ by
spraying on wa~er. To remove water andtor other sol-
vents~ the resulting solid formulation can be dried by
customary me~hods.
When carrying out the process acçording ~o ~he invention
;~ by means of varianL (b), the temperatures can also be
varied wi~hin a subs~an~ial range. For exampls, ~he
process is arried out using a liquid phase whose
tempera~ure is be~ween 10C and 100C, preferably
between 20C and 90C. The solid phase is kept at
temperatures be~ween 10C and 50C, preferably between
20C and 40C. The ~emperature of the stream of gas for
atomisation, which enters through the two-fluid nozzle,
is between 0C and 100 CJ preferably between 10C and
90C .
12A 2 77 b 1 - 19 -
'' , ' .~ ~ - ' ` -'
I
. . . . .
''...... . : ,
~J ~
For spraying ~he liquid phase in~o ~he mixer via one or
more no2zles, i~ is again possible to use all gases
which are customary for such purposes. Air or ni~rogen
are preferably suitable.
For carrying ou~ ~he process according ~o the invention
by means ef variant (b), all mi~ers are suitable which
are cus~omary for such purposes. The resul~ing solid
formulation can be discharged from the mixer via custo-
mary wlthdrawal devices. The pulverulent or granular
product obtained can subsequently be subjected to custo-
mary grinding or granulation.
When using varian~ (b), the process according to ~heinvention can also be carried out cantinuously or
discontinuously, In general, the process i5 carried out
discontinuously by in~roducing ~he required components
into the mixer in batches.
When carrying out the process according to ~he invention
by means of varianL (a), uniformly shaped granules are
obtained, whereas pulverulent or granular products are
obtained when using variant (b). These products can be
comminuted by grinding by using devices which are
customary for ~his purpose,
The solid formulations according to the invention have
a h;gh s~ability. They hava a compact, microporous
structure and are never~heless spontaneously dispers-
ible or soluble in water or other solvents. By spontane-
OU9 dispersibility~ or solubility, is to be understood
in the present case ~ha~ the particles disperse, or dis-
solve, comple~ely in generally 0.1 to 5 minutes, prefer-
ably in 0.2 to 3 minutes.
leA 2 7 7 4 ~ - 20 -
2 ~ ~ ~ $ ~ ~.r
The solid formula~ions according ~o the inven~ion
con~air. one or more agrochemical ac~ive compounds and
can ~herefore be employsd using customary me~hods for
~he treatment of plan~s in agricul~ure and hor~icul~ure.
The solid formula~ions according ~o the inven~ion are,
for example, dispersed in wa~er. The dispersions formed
in this process can be appliPd by cus~omary me~hods ~o
~he plants andlor ~heir environmen~, ~hat is ~o say, for
example, by spraying, a~omising or pouring, if appropri-
a~e af~er previous dilution, The application ra~es in
~his con~ex~ depend on the concen~ra~ion of ~he dis-
persion~ on ~he par~icular indica~ion and on ~he ac~ivecomponents employed.
The prepara~ion and ~he use of the solid formulat;ons
according ~o ~he inven~ion are illus~ra~ed by ~he
exampl~s which follow.
, . :
.~ , .
:'
~0
.,~
'~
: ' L~A 2 7 7 ~ ~ - 21 -
.~
,
-
Pre~aration exam~les
ExamDle 1
To prepare a liquid phase, 930 g of 1-(4-chlorophenyl)-
4,4-dimethyl-3-(1,2,4-triazol-1-yl-methyl)-pentan-3-ol
(97~) are dissolved completely at 60C in 2700 g of
polyethoxyisotridecyl alcohol having an average of 6
ethylene oxide uni~s per molecule, with stirring.
Moreover, a finely pulverulent, solid phase is prepared
by mixing 1200 g of a formaldehyde-crosslinked al~ylaryl-
sulphonate with 1170 g of highly disperse silica in a
small plough-bar mixer at room temperature, and the
mixture is homogenised.
The preparation of granules which follows is carried out
in a fluidised-bed granulator. For this purpose, the
solid phase is introduced into the granulator and fluid-
ised by blowing in air at a temperatuxe of 25C in an
amount of 300 to 500 m3Jh. At the same time, spraying of
the liquid phase at 60C in~o the fluidised bed via a
two-fluid nozzle with the aid of air commences. After 60
minutes, spraying-in of the liquid phase is complete.
After this, a post-granulation is carried out by spraying
on 1600 g of water at sODC, followed by drying to a
residual moisture of 1~ by weight of water by heating the
air which is passed in a~ 70Co The granules formed are
classified. In this way, S kg of granules of particle
sizes in the range between 200 and 1500 ~m are ohtained.
When 1 kg of these granules, which contain 1.5% by weight
of active compound, are added to 200 l of waterr spon
taneous wet~ing takes place, and the granules are dis-
sol~ed completely within L0 seconds.
l0A ~ 7 7 ~ 1 - 22 -
.
,: ~
.: :
~ f~:
Exam~le 2
To prepare a liquid phase, 1550 g of 1-(4-chlorophenyl)-
4,4-dime~hyl-3-(1,2,4-triazol-1-yl-methyl)-pentan-3-ol
(97%) 2re dissolved completely in a mixture of 900 g of
polyethoxy-iso-tridecyl alcohol having an average of 6
ethylene o~ide units per molecule and 1200 g of alkyl-
aryl-polyethoxy-ethanol phosphoric acid ester, which is
commercially available under the name ~Blendex~, a~ 60DC
with stirring.
Moreover, a finely pulverulent solid phase is prepared by
mixing 1200 g of a formaldehyde crosslinked alkylaryl~ul-
phonate with 1150 g of highly disperse silica in a small
plough-bar mixer at room temperature and homogenising the
mixture.
The preparation of granules which follows is carried out
in a fluidised-bed granulator. For this purpose, the
solid phase is introduced into the granulator and fluid-
ised by blowing in air at a temperature of 25~C in an
amount of 300 to 500 m3/h. At the same time, spraying of
the liguid phase at 60C into the fluidised bed via a
two-fluid nozzle with the aid of air commences. Af~er 60
minutes, spraying-in of the liquid phase i5 complete.
After this, post-granulation is carried out by spraying
on 1600 g of waker at 50C, followed by drying to a
residual moisture of 1% by weight of water by heating the
air which is passed in at 70C. The granules formed are
classified. In this way, S kg of granules of particle
sizes in the range between 200 and 1500 ~m are obtained.
I~A 2 7 7 ~ ~ - z3 -
. _
.
:.
2 ~l~9 ~L~
When 1 Xg of these granules, which contain 2.5~ by weight
of acti~e compound, are added to 200 l of watex, spon-
taneous wetting takes place, and the granules are dis-
solved completely within 10 seconds.
.
Exam~le 3
To prepare a liquid phase, 4640 g of 1-(4-chlorophenyl)-
4,4-dimethyl-3-(1,2,4-triazol-1-yl-methyl)-pentan-3-ol
(97%) are dissolved completely in 13,360 g of polyethoxy-
isotridecyl alcohol with an average of 6 ethylene oxide
units per molecule, at 60~C with stirring.
Moreover, a fin~ly pulverulent solid phase is prepared by
mixing 6000 g of a formaldehyde-crosslinked alkylarylsul-
phonate ~-ith 6000 g of highly disperse silica in a small
plough-bar mixer at room temperature and homogenising the
mixture.
Gran~lation which then follo~s is carried out in a
granulation apparatus of. the type represented in ~igure
1. For this purpose, the solid phase is fed pneumatically
to the fluidised-bed re~ctor via eedpipes 2 and fluid-
ised by blowing in nitrogen at a temperature of 80C, in
an amount o 50 kg/h, via line 6. At the same time, theliquid phase at a temperature of 60~C, is sprayed in via
the two-fluid nozzlP 5 with the aid of nitrogen as ~he
atomising gas. ~he s~reams of produc~ are controll~d in
~0 such a way that the solid phase is fed to the reactor in
an amount of 1.2 kg/h and the liquid phase in an amount
of 1.8 kg/h. ~rom the fluidised bed 7 which forms, 3 kg/h
~ L~A 2 7 7 4 ~ - 2~ -
.:
.
'
,
of granules of an a~erage particle size of 0~4 mm are
continuously discharged via the counterflow gravity
classifier 9 and thP withdrawal device 10. In ~his
manner, 28 kg of granules of à content of 15.0% by
weight of 1-t4-chlorophenyl)-4,4-dimethyl-3-(1,2,4--
triazol-1-yl-methyl)-pentan-3-ol are obtained.
Exam~le 4
To prepare a liquid phase 130 g of 6^-methyl-2-oxo-1,3- `!
dithiolo-[4,5-b]-quinoxaline are dissolved co~pletely
in 2500 g of polyethoxy-isotridecyl alcohol with an ave-
rage of 6 e~hylene oxide uni~s per molecule and 2500 g ~-
of N-oc~yl-pyrrolidone, at 60C with stirring.
Moreover, a finely pulverulent solid phase i~ prepared
~ 20 by mixing 1000 9 of rice starch and 1~00 g of a form-
- aldehyde-crosslinked alkylarylsulphonate with 1900 9 of
highly disperse silica in a small plough-bar mi~er at
room temperature and homogenising ~he mixture.
.
~5 Granulation which then follows i5 carried out in a
granulation apparatus of the type represented in Figure
1. For th;s purpose~ ~he solid phase is fed pneumati-
cally to the fluidised-~ed reactor via feedpipes 2 and
fluidised ~ blowing in nitrogen at a tempera~ure of
30 80 CJ in an ~moun~ of 50 kg/h, via line 6. At ~he same
~ime, the liquid phase at a tempera~ure of 60C, is
sprayed in via the two-fluid nozzle 5 with the aid of
ni~rogen as ~he atDmising gas. The streams of product
::.i
~ - 25 -
`:
.:
'~
' ': : . .
are con~rolled in such a way tha~ ~he solid phase i5 fed
~o the reac~or in an amoun~ of 1.2 kg/h and ~he liquid
phase in an amoun~ of 1.8 kg/h. From ~he fluidised bed
7 which forms, 3 kg/h of granules of an average particle
size of 0.4 mrn are con~inuously discharged via the
coun~erflow gravi~y classifier 9 and the wi~hdrawal
10 device 10. In ~his manner, 9 kg of granules having a
con~en~ of 1.3% by weigh~ of 6-methyl-2-oxo-1,3-dithi-
olo-~4,5-b]-quinoxaline are ob~ained.
Example 5
To prepare a liquid phase, 101.56 g of 1-(4-chloro-
phenyl)-4,4-dime~hyl-3-(1,2,4-triazol-1-yl-me~hyl)-
pen~an-3-ol and 7.54 g of 6-methyl-2-oxo-1,3-di~hiolo-
[4,S-b]-quinoxaline, 104.5 g of a mixture of N,N-
dime~hyl-alkylcarboxamides which consis~s, on average,
of 5% of N,N-dimethyl-hexanecarboxamide, 50% of NJN-
dimethyl-oc~anecarboxamide, 40% of N,N-dime~hyl-decane-
carboxamide and 5~/~ of N,N-di~e~hyl-dodecanecarboxamide,
52,5 g of polyethoxy-iso~ridecyl alcohol with an average
of 6 ethylene oxide uni~s per molecule and 5 g of p-
~olyl-sulphonic acid are completely dissolved wi~h
stirring at 80~C.
In addition, a finely pulverulent solid phase is pre-
~0 pared by mixing 156.5 g of highly disperse silica,
52.5 g of a diphenylsulphonic acid formaldehyde con-
densatQ and 19.9 g of sodium dialkylnaphthyl-sulphona~e
in a plough-bar mixer at room tempera~ure and homo-
genising ~he rnix~ure,
1~ 27 74 ~ - 26 -
.~ _
, . ~
The preparation of the solid formulation which Lhen
follows is carried ou~ in such a manner that ~he liquid
phase is sprayed at 80C via a nozzle in~o the mixer
on~o the solid phase, which has a Lemperature equal ~o
roorn temperature, while stirring. In this manner,
500 g of a granular solid formulation is obtained, which
is ground to a powder,
~'
Example 6
- To prepare a liquid phase, 136.64 g of ~-methyl-4-amino-
15 6-phenyl-1,2,4-triazin-5~4H)-one and 30.0 g of polye~h-
oxy-iso~ridecyl alcohol wi~h an average of 6 e~hylene
oxide units per molecule ore dissolved completely a~
80C wi~h stirring.
In addition, a finely pulverulent solid phase is pre-
pared by mixing 18.~2 g of 2-ethoxy ~,~-dihyclro-3,3-
dimethyl-5-benzofuranyl sulphona~e, 18,60 g of ~-
me~hoxycarbonyl-aminophenyl-N-l3 -methylphenyl)-
carbama~e~ 60.0 g of a diphenylsulphonic acid form-
;~ 25 aldehyde condensate, 30.0 g of highly disperse silica
and 6.44 g of kaolin in a plough-bar mixer a~ room
temperature and homogenising ~hs mix~ure.
,~
The prepara~ion of the solid ~ormula~ion which ~hen
follows is carried out in such a manner ~hat the liquid
phase is sprayed at 80C via a nozzle into ~he mixer
on~o ~he solid phase, which has a temperature equal to
roorn ~emperature, while s~irring, In Lhis manner,
300 g of a granular solid formula~ion is obtained, which
is ground to a powder,
I~A 2 7 7 4 1 - 27 -
'
~,
.
Example 7
To prepare a liquid phase, 53.2 g kg of 1-(4-chlorophen-
oxy~,3J:3-dimethyl-1-(1,1,4-triazol-1-yl)-buLan-2-one,
20 kg of polyeLhoxy-isoLridecyl alcohol wiLh an average
of 6 eLhylene oxide units per molecule, 20 kg of N-
ocLyl-pyrrolidone and 20 ~g of a mix~ure of N,N-
dimeLhyl-alkylcarbo~amides which consis~s, on average,
of 5% of N,N-dimeLhyl-hexanecarboxamide, 50/. of N,N-
dimethyl-octanecarboxamide, 40% of N,N-dimeLhyl~decane-
carboxamide and 5d/ of N,N-dimsthyl-dodecane~arboxamide,
are disso~ed completely aL 90C with sLirring.
In addiLior" a finely pulverulent solid phase is pre-
pared by mixing 4 kg of a weLLing agent ~ased on alkyl-
aryl-sulphonate, 20 kg of a diphenyl-sulphonic acid
formaldehyde condensate and 62.8 kg of highly disperse
silica in a plough-bar mixer 3L room LemperaLure and
homogenising the mixLurea
The prepara~ion of the solid formula~ion which then
Z5 follows is carried ou~ in such a manner LhaL Lhe liquid
phase is ~prayed aL 90C via a nozzle inLo the mixer
onto ~he solid phase, which has a tpmperaLure equal to
room temperaLure, while s~irring. In ~his manner, 200 kg
of a granular solid formulation i5 obLained~ whi~h is
ground Lo a powder.
leA 2 7 7 4 1 - 28 -
.:
Example 8
To prepare a liquid phase, 26~3 kg of 1-(4-chloro-
phenoxy)-~,3-dimethyl-1-(1,1,4-triazol-1-yl)-butan-2-ol,
10 kg of polyethoxy-isotridecyl alcohol with an average
of 6 ethylene oxide uni~s per molecu:le, 10 kg of N-
octyl-pyrrolidon2 and 10 kg of a mixture of N,N-
dimethyl-alkylcarboxamides which consists, on average5
of 5% of N,N-dimethyl-hexanecarboxamide, 50X of N,N-
dimethyl-octanecarboxamide, 40% of N,N-dimethyl-
decanecarboxamide and 5/~ of NJN-dime~hyl-dodecane-
carboxamide, are dissol~ed completely at gOC withstirring.
:~ In addition, a finely pulverulert solid phase is
~ prepared by mixing 2 kg of a we~ting agent based on
: 20 alkylaryl-sulphonate, 10 kg of a diphenyl-sulphon:ic acid
formaldehyde condensate and 31.7 kg of highly disperse
silica in a plough-bar mixer at room temperature and
homogenis;ng the mixture~
The preparation of the salid formulation which then
follows is carried out in such a manner that the liquid
phase is sprayed at 90 C via a no721e into the mixer
onto the solid phase, which has a tempe~ature equal to
: room ~emperature, while stirri~g~ In this manner,
100 kg of a granular solid formulation i5 obtained~
which is ground to a powder,
; 35
:
I~A 2 7 7 Go 1 - 29 -
~ ~3 i~
Exa~ple 2
s
To prepare a liquid phase, 25.5 kg of 1-(4-chloro-
phenyl)-4,4-dimethyl-3-(1,2~4-triazol-1-yl-methyl)-
pen~an-3-ol, 10 kg of polyethoxy-isotridecyl alcohol
with an average of 6 ethylene oxide units per molecule,
10 kg of N-octyl-pyrrolidonP and 10 kg of a mixture of
N,N-dimethyl-alkylcarbo~amides which consis~s, on
average, of 5% of N,N-dimPthyl-hexanecarboxamide, 50%
of N,N-dime~hyl-o~anecarboxamide, 40% of N,N-dime~hyl-
decanecarbo~amide and 5% of N,N-dime~hyl-dodecanecarb-
oxamide, are dissolved comple~ely at 90C withstirring.
In addition, a finely pulverulent solid phase is
prepared by mixing 2 kg of a we~ting agent basPd on
alkylaryl-sulphona~e, 10 kg of a diphenyl-sulphonic acid
';
;; formaldehyde condensa~e and 32.5 ks of highly disperse
silica in a plough-bar mixer at room temperature and
homogenising the mixture,
The prepara~ion of the solid formulation which then
follows is carried out in such a manner that the liquid
phase is sprayed at 90C via a nozzle in~o the mixer
onto the solid phase, which has a temperature equal to
room temperature, while stirring. In this manner,
~0 100 kg of a ~ranular solid formulation is obtained,
which is ground to a powder.
~5
0A 2 7 7 4 1 ~ 30 -
_
& ~ l~
Example 10
To prepare a liquid phase, 10 g of 1-~4-(2-chloro-1,1,2-
: ~rifluoroethoxy)-phenyl]-3-(4-phenyl-1,2,5-oxadia~ol-~-
yl)-urea, 30 9 of an emulsifier basecl on al~ylaryl-
polyglycol e~her, 6 g af an ethyleneoxide-dimeLhyl-
siloxane block copolymer with Si-C-bonds, 6 g of the
sodium salt of coconut fatty acid 2-sulfethylester
containing 10% of free coconut fa~ty acid are dissolved
tompletely at 90~C wi~h s~irring.
In addition, a finely pulverulent solid phase is
prepared by mixing 12 9 of a diphenyl-sulphonic acid
formaldehyde condensate and 36 g of highly disperse
silica in a mixer at room ~empera~ure and homogenising
~he mixture.
The preparation of the solid formulation whick then
follows is ~arried ou~ in such a manner ~hat the liquid
; phase is sprayed at 90~C via a nozzle into the mixer
onto the solid phase, which has a ~emperaturs equal Lo
room temperature~ while s~irrin~. In ~his manner,
: 100 g of a granular solid formulation is ob~ained, whi~h
is ground to a powder.
l~A 2 7 7 4 1 - 31 -
Comparison example A
A mixture of 2630 g of 1-(4-chlorophenyl)-4,4-dimethyl-
3-(1,2,4-triazol-1-yl-methyl)-pentan 3-ol, 2000 g of a
formaldehyde-cxosslinked alkylarylsulphonate, 300 g of
phospholipid and 5070 g of sodiu~ hydrogen carbonate is
comminuted in a plough-bar mixer to a particle size of
about 1 mm, and the mixture is homogenised. The mixture
is then ground with the aid of an air-jet mill to an
average particle size of about 7 ym and remixed.
:
The resulting premix is processed in a commercially
available fluidised-bed granulator to give granules by
moistening batches of 4.8 kg of powder in the fluidised
bed with 1.5 liters of water in the course of 21 minutes
at room tempera-ture and subsequen~ly drying the granules
by warming the inlet air to 70C in the eourse of 11
minutes, so tha~ the residual water content in the
granules is about 1% by weight. The temperature o the
granules in ~his procedure remains below 40C. The
resulting granules are classified using a cas~ade of
vibrating screens. In this manner, 4.5 kg of granules
having particle sizes in the range between 200 and 1500 ~m
are obtained per batch.
The suspension stability of the granules, measured by
CIPAC method MT 168, is 84%. The wet-screen test on
screens with mesh size 315, 250 and 160 ~m, respectively,
carried out by CIPAC method MT 167 gives screening
residues of less than 0.005~.
L~A 2 7 7 6 1 - 32 -
- - ~
,
Com~arison example B
A mixture of 2630 g of 1-(4-chlorophenyl)-4,4-dimethyl-
3-(1,2,4-~riazol-l-yl-methyl)-pentan--3-ol, 2000 g of a
formaldehyde-crosslinked alXyla~ylsulphonate, 300 g of
phospholipid and 5070 g of sodium hydrogen carbonate is
stirred into lO kg of water with the aid of a toothed-
dis~ stirrer and the mixture is precomminuted with a
toothed colloid mill. It is then ground finely on a bead
mill whose throughput is 25 kg/h. An aqueous suspension
of a solids content of S0% by weight is obtained. ~t a
shear gradient of lOOOtsec, the viscosity of the suspen-
sion is approx. 65 mPas; the average particle diameter is
approx. 4 ~m.
In an amount of 7 kg/h, the resulting suspens:ion is
sprayed through nozzles into a fluidised-bed reactor with
continuously classifying product discharge. A stream of
nitrogen in an amoun~ of 92 kg/h is used for fluidising.
The temperature of the stream of nitrogen is 90C. In the
fluidised bed which forms, a product tempera~ure of below
40C is established. The granules discharged have a
Z5 particle size of approx~ 0.4 mm. Tha residual moistuxe of
the granules is 2.1% by weight of water.
The suspension stability of the granules, measured by
CIPAC method MT 16~, is 98%. The wet-screen test on
~ screens with mesh size 315, 25~ and 160 ~m, respectively,
carried out ~y CIPAC method MT 167, gives no screening
residues.
~A 2 7 7 4 1 ~ 33 ~
. ~ .
:
.
~ :
2 ~ ~ ~ 6 .~ ~
In t~e use examples wh;ch f~llowJ ~he gra~ules prepared
were ~ested f~r their ~iological effec~iven~ss.
Use Example A
Erysiphe Test (barley)/curative
:10 To prepare a suitable pxeparation of active compound, 1
part by weight of the particular granules is mixed with
water, and the resulting concentrate is diluted with
water to the desired concentration.
~5 'rO test for curative effectiveness, young plants are
~;dusted with spores of Erysiphe graminis f.sp. hordei. 48
hours after the inoculation~ the plants are sprayed with
the preparation o active compound until dew-moist.
The plants are placed in a greenhouse at a ~emperature of
approx. 20C and a relative atmospheric humidity of
approx. 80% to allow the developmen~ of mildew pustules.
The evaluation is carried out 7 and 14 days after the
inoculation.
The formulations and concentrations of active compound,
;
1~ 2 7 7 ~ 1 ~ 34 ~
~ ` ' I`' ' . "' ` ' ~
7~
and the test results, can be seen from the table below.
Table A
Erysiphe Test (barley)/curative
Granules Active compound Degree of
0 of concentration in effective-
Example the spray mixture ness in %
in mg/l of the un~
treated
7d 14d
Known:
(A) 150 0 0
(B) 150 0 0
~ 20
: Accordina to the
~:~ invention
(1) 150 80 75
(2) 150 49 15
~5 (3) 150 ~8 60
: 35
l~ ~7 7 ~ 1
_
'^
:
