Note: Descriptions are shown in the official language in which they were submitted.
:~l'7~i6~
~ACI~GP~OVN~ O~ _~IE I~iVElJ'~ION
The present invention relates broadly to chemical
compounds and compositions suitable for agricultural
and/or pest control purposes. At the present time r materials
such as biocides and fertilizers must be applied in large
quantities and in high dosage form in order to ensure khat
an adequate amount, an adequate dosage, reaches the area
to be treated. This result has been increased cost in the
terms of the biocide material used and, more importantly,
1~ an overdosase in some areas and underdosage in others and
consequent unsatisfactory or ineffective action.
~lso, after being applied, such biocides and ferti-
lizers are often readily washed away or blown away by rain
and ~n~ and there~y rendered ineffective. This also
often results in polut~on of nearby watercourses into
~hich the cheMicals are washed.
~ ~urther problem has been the loss of effectiveness
of suGh chemicals due to degradation upon ex~osure lo the
enyironment. r~hus~ even if initially properly applied in
the right dosage they lose their necessary effectiveness
upon relati~ely short exposure to ambient conditiolls.
~fforts to lir~it the waste and to increase the
e~rectiveness of such chemicals included the use of coating
compounds to pre~ent the fertilizer, for e~ample, from
being rapidly leached from the soil, antidrifting com-
pounds to make aerially dispersed or sprayed chemicals
drop ra~i~dl~r and not drift a~ay from the desired area,
and, also, the electrostatic charging of chemical materials
by electrostatic treatrnent to have the~ adhere to the
33 area to be treated.
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One speciEic effort to improve trea~ment has involved
the use of emulsions in combination with pesticlde~i such
as ~et forth in U.S~ Patents Nos. 3,479,175 and 4,115,098.
While generally satisfactory and very sultable for many
uses they, of course, do require addition of water in
order to form emulsions and this i~ not sultable in some
instances. Al~o, such emulsions do not have the most
desired deposition and retention characteris~ics.
SUMMARY OF THE INVENTION
The present invention has overcome these problems by
providing a deposition and reten~ion agent for forming
substantive applied chemical compositions which more
readily adhere to surfaces ~o be treated, which are
resistant to removal therefrom after being applied, and
which retain their effectiveness for longer periods of
time.
According to one aspect of the invention there is
prov$ded a deposition and retention agent for Eorming
sub5tantive applied ~hemical compositions con~isting
essentially of the reac~ion produc~ of an acidic material
and a cationic amine ~urfac~ant, s~id agent capable of
giving sai.d composltions a Ze~a potential of a~ least
about +20 m~llivolts.
According to another aspect of the invention there i5
provided a substantive composition comprising an applied
chemical and the agent as defined above, ~aid agent being
present in an amount sufficient to give the applied
chemical when applied a bet~er deposition and retention
than without said agent.
According to yet another aspect of the inventlon there
is provided a substantive composition having a pH of from
.. .,
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about 4 to 6.g and a Zeta potential of at least ab~ut
+20 millivolts and consisting essentially of an applied
chemical, a deposition and retention agent, and a solvent
for said agent; said agent consisting of thQ reaction
product of an acidic material selected fLom a substituted
and unsubstituted aliphatlc monoamines, diamines, tertiary
amines, fatty amines, or mixtures ~hereo~; and sai~ agent
being present in an amount of from a~out 0.25 to 10% by
weight, based on the weight of the applied chemical.
According to yet another aspec~ of the lnvention
there is provided the method of making the deposition and
retention agent as defined above comprlsing reacting said
acidic material and said cationic surfactant under ambient
conditions for a time sufficient for the reaction to be
completed, the acidic material and surfactant being added
in an amount sufficient to give the reaction product a pH
of from a~out 4 to 6.9 and to give the compositions to
which said agent is added a Zeta potential of at least
about +20 millivolts.
~ccording to yet another aspect of the invention
there is provided the method of maklng the deposition and
retention agent as defined above comprising reacting said
acidic material and ~aid cationic surfactant under ambient
conditions for a time suf~icient for the reaction to be
completed, the acidic materlal being a mixture of equal
parts by weight of benzoic acid and tall oil and ~he
cationic surfactant being an etherified fatty amine and
there being reacted about 0~5 parts by weight o said
acidic ma~erial for each party by weight of said surfac-
tant to give to the compositions to which said agent is
added a Zeta potential Qf at least about ~20 milllvolts.
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DETAILED DESCRIPTION
The essential components of ~he presen~ novel reac~ion
product are an acidic material and a cationic surfactant
compound capable of giving the composition a positive zeta
potential of at least +20 millivolts. For practical com-
mercial utilization it is preferred to u~ilize a ~olvent
with the reaction product so it can be most sui~ably
admixed with the applied chemical.
The substantive applied chemical composition comprises
the reaction product and an applied chemical~
As used herein, ~he term "substantive" means more
readily adherent to ~he surface of ma~erial to which
the chemical is to be applied and resistant to removal
therefrom after being applied. Also, the term "applied
chemical", as used herein~ is meant to include all
chemical compounds or compositions useful for ayricultural
purposes and/or pest control purposes, including, but not
limited to, fertilizers and micronutrients; biocldes such
as herbicides, in~ecticides, fungicides, nemat~cides,
bactericides and the like and mixtures thereof; and other
agricultural chemlcals. Whil~ the invention is ~ully
applicable to all such applled chemlcals, it will be
described ln detail hereln with respect to biocides.
With respect to such biocldes, any commercially
available biocide is suitable, such as those sold under
the following trade marks: MALAT~ION, TRE~LAN, MILOGARD,
PAR~QUAT, DEF~ GUTHION, ~IPEL~ S~TAN, AATREX, KOCIDE,
BAYFOLAN, NUDRIN, MANZATE 20~, BENLATE t 2,4 D, PROPANIL,
BANVEL, RONEET, SENCOR, LORSBAN~ MANZATE, LASSO, or 2,4-5T.
With respect to the acidic material, it can be any
material capable of adjusting the pH of the composition to
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about 6.8 or 6~9, or below, preferably in the range of
about pH4 to 6.5. Preferred are the inexpensive and
readlly commercially available materials such as benzoic
acid, fatty acid compositions, and tall oil, although it
will be eviden~ to those skilled in thi~ art that any
other acidic material is suitable for use as long as it
does not degrade the other components of the composition
and has no or very limited toxicity. Benzoic acid is pre-
ferred because of its availabillty and lack of toxiclty.
In those ins~ances in which the applied chemical is
one having an acidic pH, such as PROPANIL* or certain
emulsifiable concentrate insecticides or chemical solu-
tions, the proportions of ~he acidic material and amine
are varied in order to give a sufficiently alkaline pH to
the reaction product; about 7.5 ~o 8, or higher. Then the
acidic chemical, when subsequently admxed wlth the alka-
line reaction product, will drop the ~H of the substantive
composition to abou~ 6.5 and gives the desired results as
to retention and deposition. Also in this instance it
is preferred So utilize as the amine an etherified Eatty
amine, such as ADOGEN 585. In this instance it has been
found that benzoic acid alone is not as effective in
giving the desired pH as is a combination of fifty percent
by weight benzoic acid and fifty percent by weight tall
oil as the acidic componen~ to be reacted with the ether-
ified fatty amine.
As ~o the surfactant compoundr it mu~t be a ca~ionic
compound capable oE giving the composition a high ~eta
potential, preferably about ~20 millivolts or higher.
,.
* Trade mark
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~lt~
Suitable surfactants can be determined ~imply by measUring
the zeta potential of a surfactant at a pH of about 6.5
with a Zeta Meter. It has been found that the cationic
amine surfactants, having a very strong positive charge,
are most suitable for this purpose, with substituted and
unsubstituted aliphati~ monoamines, diamines, tertiary
amines, fattv amines, mixtures thereof and the like
surfactants being suitable, Particularly preferred is
Armeen* DMS~, which is a mixture of dialkylated amino-
alkanes, dialkylated aminoalkenes, and dialkylatedaminoalkadiPnes, Broadly, all of the foregoing can be
designated as aliphatic amines.
* Trade mark
- 5b -
1a~tly, ~.~ith respect to proportions o the two
materials~ ordinarlly enough acidic material is utilized
to reac~ ith the amine and to give a p~ to the reaction
producti~n o~ 6.5 or below, as noted above, and in the
S case of reaction products to be used with acidic biocides,
enou~h aci~d is added to the cationic etherified fatty amine
to giVe a p~ o~ about 7.5 to 8. lt i3 preferred to use,
in thIs case, as the aci~dlc material consisting of eyual
parts by wei~g~t o~ benzoic acid and tall oil and to use
a~out 0.5 parts by wei~yht of this acidic composition for
each.part by wei~ht of etherified fatty amine.
In oxder to uti`l~ze the reaction product, it is
preferred to ~orm a solution th.ereo:E ~ith an oil-type solvent
~ucfi. as vegetable oils (soya oil and o~her vegetable oils)
c;trus o~ls, and aromatic and aliphatic petroleum base distillates,
preferably xylene or a ~ero~ene-type solvent, or others as
disclosed in Patents ilos. 3,47~,176, and 4,ll5,098, as referred
to above. It has ~een found that the most preferable con~
centrate .is formed by admixing the acid-amine reaction product
2~ an~. the solvent in oile containing forty-three percent by
volume of the solvent and fifty-seven percent by volume of the
reaction ~roduct.
~ n tlose instances in which the active cher,lical
composition is one alread~ containing a solvent, no
2~ solven~ need ~e used and the reaction product can simply
be added to the bioclde ln the amounts needed to give
tne desired effect. It is not unusual for xylene and
kerosene type solvents, SUCil as used in making the con-
centrate discusse~. above, to be used with various agri-
cultural chemicals.
The amount oE reaction product required LO ~e admixedwith the b-locide ~aries dependent upon -the use desired and
the particular active chemlcal. Thus, the percentaye by
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weight of reaction product based on the particular b~ocide
can vary from as low as 0.25 percent by weight o-f the
reactioil product up 'co ten or more percent by weight. While
larger amounts of tne reaction product can be utiliz~d,
S it is not economieally suitable to do so.
The method of for~ing the reaction product simply
requires admixing the requisite amounts of the acidic
material and the cationic material and permitting the
reaction to con~inue until it is substantially completed.
1~ ~he reaction is an exotller.~ic one, then when -the temperature
starts drop~ing it is an indication that the reaction is
completed. In forming the concentrate, one need only admix
the reaction product with the particular solvent in the
amoun-ts noted above in order to have a suitable concentrate.
lS A~ noted, in certain instances the reaction product alone
can De used where the ac-tive chemical composition has the
solvent already in it.
In preparing the substantive applied che~ical compo-
sitions, tlle reaction product per se, or in the form of
a coneentrate with a solvent, is admixed with the cllemical
and what is prepared is, in ef~ect, a suspension. In the
case of solid chemicals, one may take any of the conven-
tional mixin~ equipment, such as a rotating drum mixer, then
add both the active chemical and the concentrate thereto
and admix -to insure a uniform blend. The result ~s that
the active material is coated onto the solid particles
and gives tlle~n the ci.eposition ancl retention properties
desired.
In the case of liquid active chemicals, again there
is only need to add the c~ncentrate and the active chernical
to the active chemical solution to set the completed rnixing
'3~
and resultant suspension formation. In such instance~
where ~here is extensive agitation and due to the pr~sence
of the petroleum solvent and water, there may be some
limited amount of emulsification~
The composition is used in the manner conventional for
the active chemical contained therein. That is to say,
if it is in the form of a powder, then after it has been
compounded in accordance with the present invention, it
remains in the same form and applied in its usual manner
as if untreatedO Compositions with liquid active chemicals
are applied in the manner usual for such liquids.
It will be noted that with the instant invention no
water need be added in order to form emulsion as set forth
in Patents Nos~ 3,479,176 and 4,115,098; rather, what is
being formed in the case of liquid is a suspension. This
is true even in ~hose instances where wa~er is present as
i~ the case of such biocidic materials such as PROPANIL*
and/or the emulsifiable concentrates.
It has been found that the high zeta potential makes
the instant compositions adhere more uni~ormly and e~ect-
ively to the areas to be treated, and at the same time
make~ the biocide resistant to removal (substantive), as
by the action of wind, rain and the like. The resul~ has
been that smaller concentratio~s of the biocide can be
used, since what is ~sed is so much more effectively put
in contact wi~h the areas to be treated and retained in
such areas.
The present inven~ion will be described in connection
with the examples which follow that are set orth for
purposes of illustration only.
* Trade mark
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C ~
A series of substantive compositions were prepared
utilizing different applied (active) chemicals. In each
case the concen~rate was a mixture of 43~ by volume of
solvent (a mixture of aromatic and aliphatic distillate~
and 57~ by volume of an acid-amine reaction product
prepared by reacting 2000 parts by weight of benzoic
acid and 2400 of Armeen DMSD; the p~ being about 6.5.
In the table that follows giving the results, in each
case sufficient concentrate was added to give the concen-
tration of reaction product noted in percent by weight
ba~ed on the weight of the active chemical.
~ABLE I
Active Zeta Potential Conc. of Re- Zeta Potential
Chemical of Active action Product of Composition
Chemical in in % by Weight in Millivolts
Millivolts
._ ,. . .
1. BANZEL* 0 2 t 40
2. 2,4-5T ~ 0 2 + 40
3. RONEET* + 0 1 + 80
4. SENCOR* -20 0~S ~100
(flowable)
5. LASSO* ~ 0 5 ~100
6. MANZATE* 200 t20 1 + 70
in water
7. TREFLAN* ~10 5 ~120
8. LORSBAN* 0 3.5 ~ 80
_ _ ........ . . . .. ._ . . . ~ .. _ v
In each case, when the compositions are appli~d they
do not drift and the active chemicals are retained for
longer periods of time than when not treated with the
concentrate~
* Trade Mark
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EXAMPLE 9
A substantive composition was prepared for aerial
spraying consisting of a mixture of the concentrate of
~xamples 1 to 8 admixed with DITHANE* in amounts of one-
half pint of concentrate to each two pounds of DITHANE*.
A 44 foot swath was sprayed using 40 nozzles (Whirl
Jet DS). A comparison run was made using NALCO-TROL* (10
ounces per 100 gallons) a~ the control agent in place of
the instant concentrate.
The run made with the concentrate of the instant
invention showed increased deposition, reduced evap-
oration, reduced drift, superior coverage, reduced
wash-off, and reduced leach-out as compared with the
control.
EXAMPLES 10 TO 12
Utilizing the concentrate of Examples 1 to 8 a series
of different mixes are prepared illustrating utility of
the substantive composition with different mixing styles,
with the concentrate being identified as BIVERT* and mix
one part concentrate to eleven parts solvent.
A . BATCH MI XING
To spray 40 acres with 1 quart Methyl Parathion
in five (5) gallons total volume per acre 7
1. Add 10 gallons Methyl Parathion (1 ~tO/ac)
2. Add 2-1/2 gallons BIVERT* (1/2 pt./ac)
BLEND ~IGHTLY
(This can be pumped into the spray hopper
without blending)
3. Add filler water to bring batch to 200
gallons total volume. Agitate and continue
agitation while spraying.
* Trade mark
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3~$:~ 1
B. SADDLE'rl'ANI~IlIXIIIG
To ~pray 20 acres with 2 lbs. ~-trazine 4L
in twenty (~0) ~allons total volume per
acre using two ~2) 200 gallon tanks.
Put 10~-150 gallons of filler water in each
of the two tanks.
In a separate container:
lQ 1. Add 10 gallons Atrazine 4L ~2 lbs./ac.)
lli~
2. Add 10 pints BIVEP~T (1/4 pt./l~.)
BLEiJD LIGIITLY
Put 1/2 of this mixture in eac}
saddle tank.
3. Add filler water to bring batch to 200
gallons in each saddle tank. Agitate and
continue agitation while spraying.
C I-fI~TI VOL~ AND I;I~APSACTl; MIXII;~G
.
1. ~o spray 1 qt. ilalathion in 100 gallons.
Fill spray tank about one-half (1/2) full
of water.
In a separate container:
a. Adcl 1 qt. Ilalathion.
b. Add 1/2 pt. 3IV~RT.
BLEilD LIGFfTLY
~dd to spray tank.5
c. Add filler ~ater to 100 gallons.
Agitate and continue agitation while
spraying.
2. ,o spray 2 oz. Irlalathion in 2 gallons.
F;ll sprayer about one-hal~ (1/2) full
of water.
In a separate container:
~5
a. Add 2 oz. ~lalathion.
. Add 1 oz. BIVBD~.
~L~I~ID LIG~TLY
5Q Add to-spray tank.
c. Add filler water to 2 gallons. ~gitate
and spray. It is advisa~le to snake
~he knapsack sprayer every few minutes
while spraying.
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L,X~PLE 13
~ or use with PP~OPAl~IL a concentrate is made
which comprises a reaction product of an acidic material
consisting of equal parts by weight of benzoic acid and
S tall oil and an etherified fatty amine (ADOGEN 58~).
In preparing the reaction product 0.5 parts by weight of
the acidic material is used for eacn part by weight of
the amine and the final reaction procluct has a pH of about
7.5
The reaction product formed is admixed with an
aror.latic and aliphatic petroleum distillates to form a
concentrate consisting of a% by ~Jeiyht reaction product
and 96% by weight of solvent.
To form a spray utilizing this concentrate and
L5 PROP~liIL~ the sprayer is c~narged with 1 part by volume
of coneentrat~ for each part by volume of PROPA m L with
sufficient water added to briny to the volume desire~
in accordance witn the manufacturer' 5 reco~endation for
usage o~ PI'.OPAiiIL. Agitation of the batch should be
'~ earriecl out and continued until spraying is completed.
~ hile the invention has been described in COIl-
nection uith a preferred em~odiment, it is not intended
to limit the scope of the invention to the particular
form set forth, but, on tle contrary~ it is intended to
'5 cover such alternatives, modifications, and equivalents
as may be included withill the spirit and scope of the
invention as defined by the appended claims.
