Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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PATENT
Case D 6767/7128
AN EVAPORATION INHIBITOR
~ gricultural chemicals are widely used nowadays to
safeguard the growth and yield of crops, having to be
applied in particular by airplane to cover the large
areas under cultivation. To minimize the costs
involved, every effort is made to keep the quantities
of water required for diluting the commercial con-
centrates as small as possible and to apply high con-
centrations of active compound in small amounts.
Today, quantities of from 5 to 50 liters/ha are applied
by the low-volume (LV) method using known commercial
products, such as wettable powders (WP) suspended con-
centrates tSC~ or solvent-containing emulsif.iable con-
centrates (EC) which are normally sprayed in suspension
in 300 to 600 liters of water/ha using ground
appliances.
The smaller the quantities of spray mixture applied
per unit area, the finer the droplets applied have to
be to obtain satisfactory coverage of the crops. This
plus the high concentration oE the spray mixtures has
hitherto created the main obstacle to application of
the low-volume method, particularly under sub-tropical
and tropical climatic conditions, namely, the water
evaporates too quickly due to the large surface of the
fine droplets, so that increased drifting losses can
occur.
~ 3 ~
~ In addltion to drifting losses, damage may even be
caused to adjacent crops, depending on the plant treat-
ment agent used. Accordingly~ controlled application
Erom ~ircraft is diE~icult; and damage to the environ-
S ment or losses of harvest may have to be accepted.
In acldition, heavy Eoaming can occur during pre-
paration of the spray mix-ture with the greatly reduced
quantities of water, because the dispersants and
wetting agents in -the wettable powders or concentrated
dispersions are then present in correspondingly higher
concentrations. The product oams out o$ the spray
tanks unless the filling level is greatly reduced.
The above spray mixtures of agricultural chemicals
are prepared from commercial concentrates by dispersion
lS or emulsiiication in the desired quantity of water.
The concentrates are either self-emulsifying solutions
in an organic solvent (EC) or wettable powders tWP) or
suspended concentrates (SC).
The agricultural chemicals used may be insec-
ticides, fungicides, virucides, herbicides, acaricides,
dessicants, growth regulators, ripening accelerators,
repellents, pheromones, leaf fertilizers, defoliants,
etc. In addition, the concentrates optionally contain
dispersants, emulsifiers, wetting agents, defoamers,
~tickers, carriers and pigments for obtaining a rnarking
effect.
The object of the present invention is to reduce
the evaporation of water in the application by the low-
volume method of agricultural chemicals in the form oE
spray mixtures. Measures in that direction are the
subject oE German Application No. 22 05 590, although
the mineral-oil-based evaporation inhibitors claimed
therein are not suficiently effective under sub- !
tropical and tropical climatic conditions. In addi-
tion, it is known from U.S. Patent No. 3,791,839 that
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the release of water from living plants, particularly
during growth in dry climates, can be reduced by
applying to the sur~ace of the plants an aqueous
emulsion whichl in addition to paraffin wax and
emulsifier, contains Vaseline-like
hydrocarbons (petrolatum) as a required ingredient.
However, the function of these emulsions is not to
reduce the evaporation of spray mixtures of plant pro-
tection agents during spraying by the low-volume
method.
The present invention relates to an,evaporation
inhibitor ~I) for spray mixtures of agricultural che-
micals applied by the LV method in the form oE a wax-
- containing aqueous dispersion or self-emulsifyingsolution in an organic solvent, characterized by the
following composition:
from 15 to S0 % by weight of a wax or wax mixture,
from 4 to 20 % by weight of at least one nonionic
and/or anion.ic emulsifier,
from 19.5 to 81% by weight of water and/or one or more
organic solvents f rom the group
comprising hydrocarbons, esters and
ketones having boiling points of from
70 to 280C,
from 0 to 5.5~ by weight of auxiliaries,
from 0 to 5.0~ by weight of an amine or an alkali
metal hydroxide.
The inhibitor preferably has one of the following
compositions X or Y
Composition X:
from 15 to 40 % by weight of a paraffin wax or a
wax mixture containing at least one
--3--
~1 3 ~
paraffin wax having a dropping
point of from 35 to 80C,
from 4 to 20 % by weight of at least one nonionic
and/or anionic emulsifier,
from 35 to Rl ~ by weight oE water and/or one or
more organic solvents Erom the
group comprising hydrocarbons,
esters and ketones having boiling
points of from 70 to 280C,
from 0 to 5.5 % by weight of other auxiliaries.
Of inhi bi tors having the composition X, it is pre-
ferred to use those formulated as aqueous dispersions
having the following composition:
from 15 to 40 ~ by weight of at least one paraffin
wax or oE a mixture of paraffin
waxes having different dropping
points in the range of from 35 to
70C or of a mixture of those
paraffin waxes with
microcrystalline waxes having
dropping points of from 50 to 90C,
the paraffin waxes making up at
least 50~ by weight oE the wax
mixture,
from ~ to 20 % by weight and preferably from 4 to
14% by weight of at least one
nonionic emulsifier,
from 0 to 10 ~ by weight and preferably from 1 to
7% by weight of at least one
anionic emulsifier, the nonionic
emulsifiers making up at least 50%
by weight of the emusifiers,
.
' ' :
~ 3 ~
from 35 to 81 ~ by ~eight of water,
Erom 0 to 10 % by weight of xylene or cyclohexa-
none or petroleum fractions ha-~incJ
boil.ing points in the range from
145 to 210C or esters having
boiling points in the range from 70
to 280C,
from 0 to 5 % by weight of at .l.eas-t one
hydrotrope,0 from 0 to 0.5 ~ by weight of at least one inorganic
salt.
The composition Y contains the following
components:
from 15 to 50 % by weight of a wax mixture con-
taining at least about 5% by
weight, based on the weight of the
wax mixtur~, oE a wax component
. having an acid number of from 10 to
95 mg KOH/g wax~
from 4 to 20 ~ by weight of at least one nonionic
and/or anionic emulsiEier,
from 19.5 to 81 ~ by weight of water and/or at least
one organic solvent from the group
comprising hydrocarbons, esters and
ketones having boiling points in
the range from 70 to 280C,
from G to 5.5 % by the weight of auxiliaries,0 from 0 to 5.0 % by weight of an amine or an alkalimetal hydroxide.
The wax mixture preferably has one of the
following compositions:
--5--
~ 3 1 ~
Mixture (A)
from 60 to 9S ~ by weight oE paraff.in wax and/or
microcrystalline paraffin wax
having a setting point oE from 40
to 70C,
from 5 to 40 ~ by weight of oxidized polyethylene
wax having a dropping point of from
95 to 140C and an acid number of
from 10 to 95 mg KOH/g wax.
Mixture (B)
from 60 to 95 % by weight of paraffin wax and/or
microcxystalline paraffin wax
having a setting point of from 40
to 70C,
from 5 to 40 % by weight of wax containing ester
bonds and having a dropping point
of from 75 to 100C and an acid
number of from 10 to 95 mg KOH/g
wax.
Mixture (C)
from 20 to 50 % by weight o paraffin wax having a
setting point of from 30 to 50~C,
from 50 to 80 % by weight of oxidized paraffin wax
having a setting point of from 60
to 9UC and a~ acid number of from
10 to 95 mg KOH/g wax.
Tbe present invention also relates to a process
for reducing the evaporation of water from spray mix-
tures of agricultural chemicals during application by
the LV method, characterized in that from 1 to 15~ by
weight and preferably from 5 to 10~ by weight of an
evaporation inhibitor of the invention is added to the
--6--
.
1 3~ ri
spray mixtures adjusted to ~he in use concentration.
In inhibitors having the composition X, the dropping
points oE the paraffin wax or wax mixture should pre-
ferably be 10 to 40C and more especially a~ least 15C
above the particular air temperature preva.iling during
application.
The inhibitors according to the invention may be
present in the form of solu-tions of the wax and
emulsifier constituents in the organic solvents.
Solutions such as these are temperature-stable and
storable and, when stirred into water or spray mixtures
adjusted to the in-use concentration, Eorm dispersions
which show high thermal stabili-ty under normal prac-
tical conditions.
However, the inhibitors are preferably used in the
form of concentrated aqueous dispersions because, in
that form, they are easier to incorporate in the spray
mixtures due to the absence or substantial absence of
solvents. The dispersions ar~ prepared, for example,
by mel-ting the constituents to be dispersed twax mix-
turer emulsifiers, optionally organic solvents)
together and then adding the clesired amount of water
and, optionally, other constituents. In the case of
relatively high melting wax mixtures, it can be more
suitable to stir the wax mixture melted togather with
the emulsifiers and organic solvents, if any, into the
water which has been heated to 60 - 100C and pre-
ferably to 80 - 100C and which optionally contains
further constituents, followed by rapid coolingO The
dispersion is distinguished by outstanding temperature
stability and high stability in storage, enabling it to
be used even under sub-tropical and tropical climatic
conditions.
More particularly, the claimed inhibitors are used
in the form of aqueous dispersions having the following
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composition:
from 15 to 40 % by weight o~ wax mixture ~A), (B) or
( C ) ,
from 4 to 20 ~ by weight and preferably ~rom 4 to
14~ by weight oE at least one
nonionic emulsifier,
from 0 to 10 % by weight and preerably from 1 to
7% by weight of at least one anionic
emulsifier, the nonionic emulsiEiers
making up at least 50%l by weight of
the emulsi~iers,
from 29.5 to 81 ~ by weight of water,
from 0 to 10 ~ by weight of xylene or cyclohexanone
or petroleum fractions having
boiling points in the range from 145
to 210C or esters having boiling
points in the range from 70 to
280C,0 from 0 to 5 4 by weight of at least one
hydrotrope,
from 0 to 0.5% by weight of at least one inorganic salt,
~rom 0 to 5.0~ by weight o an amine or an alkali
metal hydroxide.5
The a~ueous dispersions are particularly suitable
for use in spray mixtures based on solvent-containing
concentrates (EC) and wettable powders (WP). The
ready-to-use spray mixtures are prepared simply by
stirring the aqueous dispersion into the spray mixtures
adjusted to the in-use concentration.
In the treatment oE large areas, the spray mix-
tures are generally applied by airplane in the form of
a very fine spray mist, although portable or mobile
appliances may be used for smaller areas.
~ 3 ~
By virtue of the presence in them of wax mixtures
specifically adapted to the particular in-use con-
ditions, the claimed evaporation inhibitors greatly
inhibit the evaporation of water from the droplets of
spray mist during application. In th;s way, the
droplets largely retain their weight, resulting in an
increased rate of fall and less drifting under the
efect of windO This leads to a better eect o the
plant treatment agents and, hence, to increases in crop
yield. On the other hand, ~he quantities o active
ingre~ients may also be reduced. In addition, the fact
that the quantity of liquid is maintained in the
droplets of spray mixture avoids undesirable con-
centrations of the active ingredients, providing for
slow release which can have a positive ef~ect on the
phytotoxicity of the agents used.
Furt~ermore, the wax present in the inhibitors has
a foa~-damping effec~, thus preventing ~xcessive
foaming during preparation of the spray mixtures and
their introduction into tanks and t~e like.
Compositions containing petrolatum such as those
disclosed in U.S. 3,791,933 are ~ot useful for the pur-
poses oE the present invention, i.e., the necessary
reduction of evaporation of water from spray mixtures
o agricultural chemicals is not achieved during
spraying when petrolatum is a component o~ the com-
posi~ions. In addition, compositions as disclosed in U.S.
patent 3~791~938 are not generally suitable for mixing with
emulsion spray mixtures oE agricultural chemicals due
to inter~erence with the stability of the emulsions,
especially in hot climates. Furthermore, the presence
oE petrolatum adversely affects the storage stability oE
the evaporation inhibitors oE the invention, par-
ticularly during extended storage in hot climates.
The paraEEin waxes used in the evaporation inhibi-
'}~
'f ~
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tors of the invention consist essentially of linear
C20-C40 hydrocarbons having an average molecular
weight oE from 280 to 560. ParaEfin waxes such as
these have dropping points o~ from 35 to 80C or
setting points of from 30 to 70C. In order reliably
to obtain ~he evaporation-inhibiting effect even at
elevated air temperatures, it is best to combine paraf-
fin waxes having different dropping points or setting
points or paraffin waxes with microcrystalline waxes.
In either case, however, the paraffin waxes must make
up at least 50% by weight of the total wax mixture of
composition X.
Microcrystalline waxes consist mainly of naphthe-
nes with long side chains together with isoparaffins
and small quantities of other aliphatic and aromatic
hydrocarbons. The individual constituents contain from
30 to 60 carbon atoms in -~he molecule. The waxes have
av~rage molecular weights of from 580 to 700, dropping
points of from 50 to 90C or setting points of from 40
to 70C.
The following products are preferably used in wax
mixtures tA), (B) or (C) of the composition Y:
(a) Natural or synthetic paraffin waxes or
microcrystalline paraffin waxes having setting
poin~s in the above-mentioned ranges, for example
ozocerite, paraffin waxes from the distillation of
petroleum, microparaffins from crude oil residues
or synthetic paraffins obtained by the
Fischer-Tropsch synthesis.
(b) Oxidized polyethylene waxes having dropping points
oE from 95 to 140Cr of the type obtained by par-
tial oxidation of polyethylenes. The acid number
is preferably in the range from 10 to 70 mg KOH/g
wax~
--10--
:.~
i 3 ~
(c) Oxidi~ed paraEEill waxes having sett;ng points o~
from 60 to 90C and an acid numbec o~ from 10 to 95
mg.KO~/g wax, of the type obtained by partial oxi-
dation of parafins.
(d) Waxes containing ester bonds, pceferably emanating
from natural sources, such as for example montan
waxes in crude or refined form, vegetable waxes,
such as carnauba or candelilla wax, or insect
waxes, such as shellac wax. The ester waxes have
dropping points of from 75 to 100C and are
optionally used in prehydrolyzed form with an acid
number of from l0 to 95 mg KOH~g wax.
The emulsifiers used are preferably nonionic sur-
factants or surfactant mixtures, including for example -
the sorbitan esters of higher fatty acids and long-
chain alkyL glycosides and also alkylene oxide adducts
wi th higher, Cl0-C24 linear monofunctional and poly-
functional alcohols~ alky~lphenols, Iong chain carboxylic
a?ids, carboxyLic acid amides and hydroxy fatty acids,
as well as with fatty acid gylcerol or sorbitan esters
. and long-chain alkyl glycosicles. It is preferred ~o
use the adducts of from 2 to 50 moles oE ethylene oxide
with lo.n~-chain C12-Cla, more especially primary alcohols
and with f.atty acids. To improve the temperature
stability o the aqueous inhibitor dispecsions, it is
advi~able to co-nbine.two or more alkylene oxide adducts
differing in their degree of alkoxylation with one
anothe.. A mixture o~ et~lylene oxide ad~ucts with
C12 C18 fatty alcohols or alkylphenols consisting oE
~roln 10 to 40 ~ by weight o~ adducts containing from
1 to 4 moles oE ethylene oxide,
from 25 to 70 ~ by weight o~ adducts containing from
4 to 10 moles of ethylene o~ide,
` -11-
.
from 5 to 35 ~ by weight of adducts containing Erom
10 ~o 50 moles oE ethylene oxide
has proved to be particularly effective.
The dispersions may be further stabilized by
replacing part oE the nonionic emulsifiers by anionic
emulsifiers. Suitable anionic emulsi~iers are the
alkali, ammonium, amine and alkaline-earth salts of
long-chain alkyl sulfates, sul~onates and phosphoric
acid partial esters. Particularly suitable anionic
emulsifiers are the salts of sulfuric acid semiesters
or phosphoric acid partial esters of linear alcohols or
alkylphenols containing from 12 to 18 carbon atoms or
polyglycol monoalkylethers containing from 12 to 18
carbon atoms in the alkyl group and also olefin sulfo-
nates, ester sulfonates and alkane sulonates con-
taining from 12 to 20 carbon atoms, alkylbenzene
sulfonates containing -Erom 6 to 16 carbon atoms in the
alkyl groups, sulfonates of polyglycol monoalkylethers
and salts of polyglycol monoalkylether carboxylic acids
containing from 12 to 18 carbon atoms in the alkyl
groups. OE these surfactants, alkylbenzene sulfonates
and alkane sulfonates are preferably used.
The emulsifiers are used in a total quantity of
from 4 to 20% by weight and preerably in a total quan-
tity of from 4 to 14% by weight, based on the inhibitor
dispersion or solution. Where anionic emulsifiers are
present, they preferably make up at least 0.5~ by
weight and more especially at least 1.0~ by weight of
the inhibitor as a whole. The nonionic emulsifiers
should preferably make up at least 50% by weight of the
total quantity of emulsifiers.
The organic solvents optionally present in the
inhibitor formula-tions are liquid hydrocarbons, esters
or ketones having boiling points of from 70 to 280~C,
for example light mineral oils, toluene, liquid fatty
acid methyl esters and the like. PreEerred solvents
are xylene, cyclohexanone or petroleum ~Eractions
boiliny at temperatures in the range Erom ]45 to 210C.
Other auxiliaries which may be added as required
in a total quantity of up to 5.5% by weight, more espe-
cially to the inhibitor dispersions, include dyes,
viscosity regulators, foam regulators, preservativ~s,
inorganic salts, hydrotropes and other dispersion aids.
OE particular importance to the dispersions in this
respect are hydrotropes and salts which influence the
structure of the aqueous component of the dispersion
and thus enable ViSC08i ty and degree of dispersion to
be regulated. PreEerred hydrotropes are non-surface-
active salts of aromatic sulfonic acids, such as sodium
cumene sulfonate, and of sulfuric acid semiesters with
C6-C1o alcohols. The hydrotropes need only be used in
quantities of up to 5% by weight. Suitable inoxganic
salts, which may be added in quantities of up to 0.5%
by weight, are in partic~lar the sodium or potassium
salts of mineral acids. In addition, small quantities
of up to 5% by weight of amines or alkali are pre-
ferably used for adjusting the pH of the dispersion and
for neu-tralizing the oxidized polye-thylene or paraffin
waxes or ester waxes containing acidic groups.
Alkanolamines, such as diethanolamine, morpholine, and
sodium or potassium hydroxide are particularly
suitable.
The type of agricultural chemicals used in the
spray mixtures is not critical to the use of the eva-
poration inhibitors (EI) according to the invention.
For example, the inhibitors may be used for applying
the following plant protection agents ~the list of
which is not intended to limit the invention in any
way):
~ 3 ~ ~3~ 3
1 Pyrethroids, such as deltamethrin, cypermethrin, fenpropatllrin,
cyfluthrin, fenvalerate, permethrin; (thio)phosphoric acid
esters, such as triazophos, parathionmethyl, d~t~at,
heptenophos, pyrazophos, profenofos, sulprofos, dialifos,
S chlorpyrifos, anilofos; carbamates, such as ~PMC, carbaryl,
propoxur, methomyl, carbofuran, phenmedipham, desmedipham,
pririmicarb; chlorinated hydrocarbons, such as camphechlor,
dicofol; chitin synt-hesis inhibitors, such as di1ubenzuron,
trifluron, teflubenzuron (CME 134) or chlorfluazuron (IK~
7899); the aqents endosulfan, amitraz, clofentezine, phosethyl
AL, proehloraz. -
~lerbicides of ~he phenoxy or heteroaryloxy phenoxy propionic
acid derivati~e type, such as diclofop-methyl, fenoxaprop-
ethyl, fluazifop-b1ltyl, haloxyfopethoxy-ethyl (Dowco 453),
lS quinofop-ethyl; urea derivatives, such as diuron~ isopropturon,
linuron, monolinuron, chlortoluron, sulfonyl ur-_as, such as
chlorsulfuron, sulfometuron; triazines such as ametryn,
atrazine, simazine; halogenated phenoxy acetic acid or
propionic acid derivatives, such as MCPA, dichlorprop,
2,4,5-T, mecoprop, 2,4-D, esters or salts thereof; ~nili~e
derivatives, such as butachlor, propanil, benzoylprop-ethyl,
alaclllor, metolachlor; nitrophenol derivatives, such as
binapacryl or dinosebacetat, nitroaniline derivatives, such
as ~rifluralin or pendimethalin; benzothiadiazines, such as
bentazone: the agents ioxynil, bromoxynil, metamitron,
glufosinate or salts thereof, bialophos or salts thereof,
glyphosate or salts thereof, triazole derivatives, such as
triadimefon; the fungicidcs mctal axyl, iprodionc, fcnarimol,
triforine, propiconazol, tridemorph, pyracarbolid: agcllts
containing lleavy metals, suc~) as manel~, sineb, triphcnyl tir.
colnpouncls, such as fentin-acetate or fentin hydroxidc, azo-
cyclotin, cyl~exatill, copperoxy chloride; plant grohtllreglllators, 5ucll ~s mepiquatchloricle or c~llormcquatcllloridc
or silnilal- salts, anryl~lid<)l, tctcycla.sis or mcfluir1icl. ~urtllc~
inforlnali~n on tl~r!sc Ireatln~llt a~cn~.s rn~y bC! found in
14-
~31$~
1 CH.R. Worthing, S.B. Walker, The Pesticide Manual, 7th E~.,
British Crop Protection Council, London, 1985.
I. Formul.atlon ExamE~es for ev~eorati_n_ilh1bitors (EI)
All quantities are ~iven in percent by weicJht.
Dp. = dropping pOillt (as determined by DGF method III 3)
Sp. = setting point (as determined by DGF method lII 4a)
A No. = acid number (as determined by DGF method IV 2)
Br. = boiling range
EO = ethylene oxide
PO = propylene oxide.
Examples of composition X:
EXAMPLE 1
30.0 ~ paraffin, Dp. 50 - 52C
2-0 % C12-C18 fatty alcohol + 2 EO
6.0 % C16-C]8 fatty alcohol + 6 EO
2.0 % C16-C18 fatty alcohol + 12 EO
60.0 % water
EXAMPLE 2
26.0 % paraffin, Dp. 50 52C
4.0 % white spirit, Br. 180 - 210C
2.0 % C12-C18 fatty alcohol + 2 EO
8.0 % tallow fatty alcohol ~- 6 EO
2.0 % tallow fatty alcohol + 12 EO
58.0 % water
_AMPLE 3
23.0 ~ paraffin, Dp. 50 - 52C
2.0 ~ paraffin, Dp. 38 - 40C
10.0 ~O white spirit, Br. 145 - 200C
6.0 ~ tallow fatty alcohol + 6 EO
9.0 3 C12-C18 Eatty alcohol + 4 EO
l.0 ~ tallow Eatty alcohol -~ 25 EO
54.0 % water
: ~.
-15-
13 L ~
1 _XAMPLE` 4
40 ~ paraEEin, Dp. 40 - 42C
8 ~ oleyl/cetyl alcohol ~ 5 EO
52 % water
s
EXAMPLE 5
30.0 % paraE~in, Dp. 38 - 40C
55.0 % xylene
10.5 % dodecylbenzene sul~ona-te,
Ca salt (70%)
8 C10/Cl6-Cl.8 fatty alcohol mixture
+ 2 PO ~ 11 EO
EXAMPLE 6
30.0 % paraffin, Dp. 40 ~ 42C
55.0 % xylene
7.5 % petroleum sulfonate, Na salt
7.5 % olelc acid + 15 EO
EXAMPLE 7
20.0 % paraffin, Dp. 38 - 40C
65.0 % white spirit, Br. 145 - 200C
7.5 % dodecylbenzene sulfonate,
Ca sa] t (709s)
7.5 % oleic acid -~ 8 EO
_XAMPLE 8
15 % microwax, Dp. 68 - 72C
15 % parafEin/ Dp. 50 - 52C
2 % C12~C18 fatty alcohol + 2 EO
6 % C12-C18 Eatty alcohol + 6 EO
2 % C12-C18 fatty alcohol + 12 EO
60 ~ water
1 3 ~
1 EXAMPLE 9
15 % paraEfin, Dp. 57 - 60C
15 % paraffin, Dp. 50 - 52C
12 Cl~ fatty alcohol -~ 2 EO
6 ~O C12-C18 Eatty alcohol t 6 EO
2 ~ C12-C18 fatty alcohol -~ 12 EO
60 O water
EXAMPLE 10
30 % paraffin, Dp. 50 - 52C
3 %a C12-C14 fatty aleohol + 2 EO
5 ~ tallow aleohol ~ 6 EO
3 % tallow aleohol + 12 EO
3 % sodium fatty alcohol ether phosphate
(C12 C18 + 10 EO phosphate~ 30%)
56 % water
EXAMPLE 11
25.0 % paraffin, Dp. 57 - 60C
3.0 % teehnieal oleyl alcohol + 2 EO
5.0 % tallow aleohol -~ 6 EO
2.0 % tallow aleohol + 12 EO
0.1 ~ NaCl
64.9 ~ water
EXAMPLE 12
30 % paraffin, Dp. 50 - 52C
3 % C12-C18 fatty alcohol + 2 EO
5 % tallow aleohol + 6 EO
3 ~ tallow aleohol + 12 EO
1 % sodium fatty alcohol sulfate
(C8-C10 sulfate, 30~)
2 % sodium eumene sulfonate, 50%
56 a water
-17
~ 3 ~
1 Examples of composition Y:
EXAMPLE 13 (type: wax mixture (A))
.
20.0 % paraffin wax. Sp. 50 to 54C
10.0 ~ oxiclized polyethylene wax, Dp. 100 to 105C, A No. 23
to 28
0.5 % diethanol.arnine
2-0 ~O C12-C18 coconut oil fatty alcohol -~ 2 EO
6.0 % tallow fatty alcohol + 6 EO
2.0 % tallow fatty alcohol + 12 EO
:L0 59.5 % deionized water.
EXAMPLE_14 (type: wax mixture (A))
27.0 % paraffin wax, Sp. 50 to 54C
3.0 % oxid.ized polyethylene wax, Dp. 108 to 111C, A No. 20
to 30
0.1 % diethanolamine
2.0 %O C12-C18 coconut oil fatty alcohol + 2 EO
6.0 ~ tallow fatty alcohol + 6 EO
2.0 % tallow fatty alcohol + 12 ÆO
59.9 % deionized water.
EXAMPLE 15 (type: wax mixture (A))
25.0 % paraffin wax, Sp. 50 to 54C
2.5 ~ oxidized polyethylene wax, Dp. 100 to 105C, A No~ 23
to 28
2.5 ~ oleyl alcohol (iodine number 50 - 55) + 2 EO
4.2 % tallow fatty alcohol ~ 6 EO
2.5 % tallow fatty alcohol + 12 EO
0.1 % diethanolamine
2.0 % sodium cumene sulfonate (40%)
2.7 % octanol/ decanol sulfate, sodium salt
58.5 % deionized water.
EX~MPLE 16 (type: wax mixture (s))
27.0 o-O paraEfin wax, Sp. 50 to 53C
-18-
~ 3 ~
1 3.0 ~ cster wax (montall wax), Dp. 82 to 88C
A No. 25 to 35
0.1 ~ diethanolamine
2-0 ~ C12-C18 coconut oil fatty alcohol -~ 2 EO
6.0 ~ tallow fatty alcohol -~ 6 EO
2.0 % tallow fatty alcohol -~ 12 EO
59.9 ~ deionized water.
EXAMPLE 17 (type: wax mixture (C))
14.0 % paraffin wax, Sp. 30 to 35C
16.0 ~ oxidized paraffin wax, Sp. 65 to 70C, A No. 30 to 35
3.5 ~ die-thanolamine
2.0 % C12-C18 coconut oil fatty alcohol + 2 EO
6.0 ~ tailow fatty alcohol + 6 EO
2.0 % tallow fatty alcohol + 12 EO
56.5 % deioni~ed water.
EXAMPLE 18 (type: wax mixture A))
25.0 % paraffin wax, Sp. 50 to 52C
2.5 ~ oxidized polyethylene wax, Dp. 108 to 111C, A No. 20
to 30
2.5 ~ oleyl alcohol + 2 EO
4.2 % tallow alcohol + 6 EO
2.5 % tallow alcohol + 12 EO
0.1 % diethanolamine
2.0 ~ C16-C18 alkane sulfonate, Na salt, 60%
1.5 % sodium cumene sulfonate, 40%
0.2 % preservative
59.7 % water.
EXAMPLE 19 (type: wax mixture A))
27.0 % paraffin wax, Sp. 50 to 54C
3.0 % oxidized polyethylene wax, Dp. 108 to 111C, A No. 20
to 30
10.0 ~O dodecyl benzene sulfonate, Ca salt, 70~ in xylene
-19--
~,3~
5 0 % nonionic surfactant of C8-C10/Cl6 C18 fa y
mixture ~ 2 PO + 11 EO
55.0 ~ xylene.
II. Production of the evaporation inhibitors
a) Production of the EI of Example 6
In a stirrer-equipped 460 1-vessel,75 ~q o~ paraææin wax
(Dp. 40 - 42C, in flake form), 18.75 kg of Na petroleum
sulfonate and 18.75 kg of oleic acid -~ 15 EO were
successively added wi-th stirring to 137.5 kg of xylene.
The mixture was stirred for 30 mins. at room temperature,
a homogeneous solution being formed.
b) Production of the EI of Example 1
A melt was prepared from 54 kg of paraffin (Dp. 50 - 52C),
3.6 kg of C12-C18 fatty alcohol + 2 EO, 10.~ kg of
C16-C18 fatty alcohol + 6 EO and 3.6 kg of C16-C18 fatty
alcohol + 12 EO by heating to 60C. 108 kg of water at
60C were then introduced into this melt over a period
of 15 minutes with stirring. After the addition, the
dispersion was cooled to below 30C over a period of
3 hours.
III. Measurement on evaporatinq water droplets
2S Water droplets 50 to 100 microns in diameter were sprayed
onto 12 micron diameter Perlon fibers and photographed at
short intervals under a microscope (500 x magnification) in
order to record their evaporation behavior at laboratory
temperature (22C). The diameter and volume of the droplets
after various evaporation times were calculated from the
micrographs.
Water and a 2.5% aqueous dilution of the evaporation
inhibitor of Example 1 were compared with one another.
Under the microscope, a water droplet approx. 70 micL-olls
in diameter evaporated cornpletely after 13 seconds at room
-20-
1 temperature. After the same time, a droplet of the same
cliameter containing 2.5~ of evaporation inhibitor according
to the invention has lost only about one quarter of its
original volume through evaporation.
The times aEter wllich the droplets had shrunk to half
their original volume or half their original diameter, as
cletermined by linear interpolation between the microscope
evaluation dots, are listed 1n Table l.
T ble
Measurement of evaporation on droplets
.
Initial Evaporation time to
diameter half initial volume half initial diameter
_ _
Water without
inhibitor 67 microns 5 seconds 10 seconds
. _
Water contain-
ing 2.5~ of 64 microns 18 seconds 70 seconds
inhibitor
IV. Testing the evaporation-inhibiting effect directly on
droplets of the test mixtures
. . _
Hemispherical droplets with a volume of approx. 0O01 ~l
were formed at the tip of a 1 ~1 Hamllton syringe arranged
horizontally under a microscope by carefully pushing in the
plunger. In order to measure evaporation, the size of the
droplets was measured after certain time intervals using a
graduated scaleincorporated in the eyepiece and the droplet
volume calculated therefrom. The tests were carried out
at 23C/55% relative air humidity.
The three spray mixtures tested contained 10% by weight
of Hostaquick(R), HOECilST AG (which contains the insecticide
6-chlorobicyclo(3,2,0)hepta-2,6-dien-6-yl dimethylphospha-te,
emulsifiers and xylene), the inhibitor of Example 15 and
standard water having a harclness of 342 ppm. The test
-21-
1 results are shown in TabLe 2 below in the form of average
values from five tests.
Table 2
I~ibitor Droplet volume in 1/1000 ~1 after..... seconds
content 0 20 40 60 80 100 120 140
.
0 % 11 2.8 0.0 - - - - -
2.5 ~ 11 S.3 3.2 2.1 1.3 0.5 0.0
5 % 11 7.0 6.1 5.4 4.6 3.9 3.1 2~4
1 0 . _ _ ___
Water 11 2.0 0.0
V. Comparative testing of EI using test mixtures free from
active substances AS) _
The following test mix-tures were used for testing
evaporation inhibition and foaming behavior:
EC - type A: 10 g of AS-free concentrate of 8 g of xylene
and 2 g of emulsifier mixture (1.2 g o
nonylphenol + 15 EO, 0.8 g of dodecylbenzene
sulfonate, Ca saltJ 70%)
were emulsified in
80 g o~ water,
followed by the addition of quantities of
10 g of the inhibitors o Examples 1,2,3,4,8
9~ 13, 14, 15, 16 or(Blankvalue: 10 g of concentrate without inhibitor in 90 g
of water)
EC-type B: 10 g of AS-free concentrate of 8 g of phthalic
acid diisooctyl ester and 2 g of emulsifier
mixture (1.6 g of castor oil + 12 EO, 0.4 g
of dodecylbenzene sulfonate, Ca salt, 70%)
we~re emulsiEied in
80 g of water,
-22-
1 followed by t.~le addition o~ quantities of
10 g of the inhibitors of Examples 5,6 and 7.
(Blankvalue: 10 g of concentrate without inhibitor in 90 g
of water).
WP-type: 5 g of AS-free wettable powder oE ~.4 g of
kaolin (b~lus alba la, ground) and 0.6 g
of emulsifier mixt~lre (C12-C14 fatty
alcohol sulfate, Na salt, inorganic salts)
were suspended in
85 g of water,
followed by the addi.tion of quantities of
10 g of the inhibitors of Examples 1,2,3,5,6
ar 7.5 (Blankvalue: 5 g of powder without inhibitor in 95 g of
water).
To test the inhibition of evaporation, quantities of 50 g
of the spray mixtures w.ere introduced into a plane-bottomed
glass dish (diameter 120 mm, height 20 mm) and, bY weighing
out, the evaporation produced by a steady stream of air was
determined as a ~unction oF time ~nd temperature . The
results are shown in Tables 3 to 7.
T le 3
Spray mi~ture EC-type A Evaporation loss in ~ by weight
at 20C
0.5h lh 2h 3h 4i
Blank va].ue 10 17 31 45 57
30 Example 1 0.4 0.4 0.4 0-4 0-5
Example 8 0.8 1.5 2.9 5.0 6.0
Example 9 0.6 0.6 0.6 0.7 0.8
-23-
Ta_le 4
Test mixture Evaporation loss in % by weight ak 25C
EC-type A1/2h :Lh 2h 3h 4h 24h
Blank value9.515.927.0 37.5 48.3 97.9
Example 1 0.40.4 0.4 0.4 0.5 0-9
Example 2 6.8L0.816.1 17.3 17.7 19.1
Example 3 0.10.1 0.1 0.2 0.3 1.2
Example 14 0.50.5 0.5 0.8~ 1.0 2.7
Example 15 0.70.8 1.0 1.1 1.3 3.1
Example 16 0.60.9 1.4 1.5 1.9 3.9
Table 5
Test mixture
EC-type A Evaporation loss in ~ by weight at 50C
1/2h lh 1.5h 2h 2.5h 3h
Blank value37 71 92 - - -
Example 1 20 36 48 53 58 62
Example 8 9 16 20 24 27 29
Example 9 14 24 31 37 40 42
Example 1317 19 21 23 24 25
Example 14 5 7 10 13 15 17
Example 15 6 9 12 15 21 26
Example 1611 16 20 24 27 30
Example 17 9 17 22 25 29 35
Table 6
Test mixture
EC-type B Evaporation loss in ~ by weight at 25~
1/2h lh 2h 3h 4h
Blank value9.915.929.9 42.6 64.9
Example 5 0.10.1 0.1 0.1 0.2
Example 6 0.20.3 0.5 0.8 1.0
Example 7 0.30.8 1.3 1.6 1.9
-24-
~ 3 ~
Table 7
____
Test mixture Evaporation loss in ~ by welght at 25~C
WP-type 1/2 lh 2h 3h 4h 5h
Blank value 5.910.620.2 31.241.8 95.0
Example 1 3.85.5 8.6 11.715.3 59.5
Example 2 1.12.2 4.3 6.69.2 44.2
Example 3 6.77.6 8.6 9.510.4 21.9
Example S 0.20.3 0.4 0.5~0.6
Example 6 0.70.9 1.5 1.821.0
Example 7 0.60.8 0.8 0.90~9
VI. _estinq of foaminq behav1or
To test foaming behavior, the spray mixtures were tested
and evaluated by the perforated-disc beating method (DIN 53902).
The results are shown in Table 8.
Table 8
(Working conditions: volume 200 ml, No. of strokes 30,
temperature 25~C)
Spray mixture Foam volume in ml
EC-type A
Time (minutes)0.5 2 10 30 120180
Blank value 100 80 40 30 10
Exampl e 1 0
Example 2 5 0
Example 4 0 - - - - -
Spray mixture
WP-type
Blank value 580 570 550 540 540540
Example 1 70 50 50 40 30 30
Example 2 0
Example 3 10 10 10 10 5 S
-25-
~ 3 ~
1 VII. Comparative testinq oE EI usin~ c mercial products
a) Using the same methods as in Section V, comparative
tests were carried out with spray mixtures prepared from
commercial concentrates.
The EC used was the insecticide concentrate, Hostaquick(R~
(a product of Hoechst), wh~ich contains 6-chlorobicyclo-(3,2,O)-
hepta-2,6-dien-6-yl dimethyl phosphate as its active constit-
uent. The WP used was the fungicide spraying powder,
Derosal(R) (a product of Hoechst), containing 2-(methoxy
carbonylamino)-benzimidazole as its active constituent.
Table 9 shows the results oE the evaporation tests at 25C.
Table 9
.
15 Spray mixture oE1/2h lh 2h 3h 4h 24h
Hostaquick (R)
(EC 50)
Blank value 6.310.320.333.741.7
Example 1 0.60.8 0.9 1.1 1.2 5.1
Derosal(R)
(WP 60~
Blank value 8.119.529.045~867.6 95.0
Example 6 0.10.1 0.1 0.1 0.2 0.7
b) Further tests were carried out as follows using a
thermobalance: _
10% test mixtures were prepared from three standard
commercial plant protection agent concentrates. The
- 30 inhibitor (EI~ of Example 15 was then added to the test
mixtures in quantities oE 0%, 5% and 10~.
To measure evaporation behavior, quantities of 50 ~l
oE these spray mix-tures were introduced into a cylindrical
aluminium dish (diameter 6.5 mm, height 1.5 mm). The
evaporation as a ~unction of time produced by a stea(ly
-26-
1 stream of air (40 l/h) at 50C was measured by means o a
thermobalance (Du Pont Model TGA 951), the weight of the
sample beil-lg continuously recorded by a recorder. The
results are sllown in Table 10 below:
Table 10
Active Inhibitor Weight of the sample in mg after .. mins.
substance (% by
concentrateweight) 0 30 60 90 120 150
. . _ _ . ~
10 Hostathion(R) 0 % 50 8 3 3 ' 3 3
5 % 5041 35 30 25 20
10 ~ 5043 ~1 40 39 3
.. . _ .. _ . .. _ .... _ .. _
Afu~an () O % 50 9 2 2 2 2
5 ~ 5041 35 30 26 23
10 ~ 5042 40 38 37 36
Illoxan (R)0 % 50 9 3 3 3 3
5 % 5040 36 31 26 21
10 % 5041 ~6 32 29 26
.,
Water 0 % 5010 0 0 0 0
Hostathion(R) (HOECHST AG) contains the insecticide l-phenyl-
3-(O,O-diethylthionophosphoryl)-1,2,4-triazole, emulsifiers
and xylene.
Afugan(R) (~IOECHST AG) contains the ~ungicide 2-(O,O-diethyl-
thionophosphoryl)-5-methyl-6-carbethoxy-pyrazolo-(1,5-a)-
pyrimidine, emulsifiers and xylene.
Illoxan(R) (HOECIIST AG) contains the herbicide 2-(4-(2',4'-
dichlorophenoxy)-pllenoxy)-propiollic acid methylester,
emulsifiers, xylene A nd cyclohexanone.
-27-
~ 3 ~
1 c) In the same way as in b), tests were carried out with
a thermobalance at 50C on the variously concentrated spray
mixtures listed in Table 11 to whlch an ~I corresponding to
Example l had been added. Evaluation was based on the average
evaporation rate.
To calculate this value, the times required to evaporate
half the respective sample volumes were taken from the graphs.
The volume evaporated divided by the time, based on one
square centimeter of evapora-tion surface, is shown as the
average evaporation rate in Table 11. For simplification,
the curvature of the evaporation surface was not taken into
account in the calculation.
The magnitude of the evaporation-inhibiting effect
depends to a large extent on the type and concentration of
the surfactants in the spray mixture. The fact that the
various plant protection agents introduce varying amounts of
various surfactants into the spray mixture accounts for the
differences in the evaporation-inhibiting effect.
-28-
~ 3 ~
Tab_e 11
Commercial product Concentrations Evaporation rate
product inhibi-tor mg/min. per cm2
% %
Water 100 0 4.2
90` 10 0.8
... .... . .. .... _ _ . ... _ _ . . . .. .
Endosulfan 35 EC10 0 ~ 4.5
(insecticide) 20 10 1.9
0.8
2.5 1.5
... . . . ~ .. , _ _
Triazophos 40 EC10 0 4.4
(insecticide) 10 10 0O3
0.4
2.5 2.5 1.3
2.5 0.9
Heptenophos 50 EC10 0 3.6
(insecticide) 10 10 0.1
Diclofopmethyl 36 EC 10 0 4.0
(herbicide) 10 2.5 0.3
1 0.5
: Pyrazophos 30 EC10 0 4,4
(fungicide) 10 10 0.8
-29-
: ~ ,~
~ L~ 5 9 ~3
1 VIII. Open-air test
The effect in practice oE the reduction in evaporation
rate observed in the laboratory was studied in an open-air
test under subtropical climatic conditions. The pests
Heliothis ssp. and Anthonomus grand:is which attack cotton
plants were treated at average air temperatures of 38~C and
low humidity levels.
The tests were carried out on two identical 3-hectare
parcels planted with cotton which had been pretreated with
the usual plant protection agents according to the level of
infestation. For the next four applications, the inhibitor
of Example 1 was added to the spray mixture applied to parcel
1 whilst parcel 2 was sprayed without any inhibitor.
The followiny amounts of plant protection agents per
hectare were applied in each of the four sprayings:
Parcel 1
0 5 1 Decis(R) (2 5 Ec)l)
2.0 1 Thiodan(R) ~35 EC)2)
27.0 1 water
0.5 1 inhibitor
Parcel 2
0.5 1 Decis( ) (2.5 EC)
2.0 1 Thiodan~R) (35 EC)
27.5 1 water
1) EC-concentrate(R) Decis contains the insecticide (IR:3S)-
3-~2,2-dibromovinyl)-2,2-dimethylcyclopropane carboxylic
acid (aS) a-cyano-3~phenoxybenzyl ester
2) EC-concentrate(R) Thiodan contains the insecticide
6,7,8,9,10,10-hexachloro-1,5,5a,9a-tetrahydro-6,9-methano-
2,4,3-benzodioxathiepin oxide as its active constituent.
The two p~rcels were thell further treated in exactly the
.
-30-
~31~
same way. All application~ were rnade ~y airplatle.
At the end of the spraying season, the yields were
determinecl. Parcel 1 yieldecl another 200 kg of cotton per
hectare, correspondiny to an increase in yield of 5% over
Parcel 2.
-31-
~ .
