CA1173661A - Substantive applied chemical composition and method of making and using same - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
A high positive Zeta potential deposition and retention agent comprising the reaction product of an acidic material and a cationic surfactant, a substantive applied chemical composition comprising the deposition and retention agent and an applied chemical, and the method of making and using the agent and composition.

Description

:~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.

' .~! ' 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 .. ., ~ A';;~

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.

' 'l 3~
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 ~'1 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 - 5a -., .1 ~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 - G -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 ,~'' 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 ' !

7~

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.

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 ....

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.

~ ~Lt~

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.

Claims (15)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A deposition and retention agent for forming substan-tive applied chemical compositions consisting essentially of the reaction product of an acidic material and a cationic amine surfactant, said agent capable of giving said compositions a Zeta potential of at least about +20 millivolts.

2. The agent of Claim 1 wherein the pH of said agent is from about 4 to 6.9.

3. The agent of Claim 1 wherein the pH of said agent is above pH 7.

4. The agent of Claim 1, 2, or 3 wherein the acidic material is selected from benzoic acid, fatty acids, tall oil, or mixtures thereof and the cationic surfactant is selected from substituted and unsubstituted aliphatic monoamines, diamines, tertiary amines, fatty amines, or mixtures thereof.

5. A substantive composition comprising an applied chemical and the agent of Claim 1, said agent being present in an amount sufficient to give the applied chemical when applied a better deposition and retention than without said agent.

6. The composition of Claim 5 wherein said applied chemical is a biocide and the composition has a pH of about 4 to 6.9.

7. The composition of Claim 5 wherein said applied chemical is a biocide and the composition includes a solvent for said agent.

8. The composition of Claim 5, 6, or 7 wherein the acidic material is selected from benzoic acid, fatty acids, tall oil, or mixtures thereof, the cationic sur-factant is selected from substituted and unsubstituted aliphatic monoamines, diamines, tertiary amines, fatty amines, or mixtures thereof.

9. The composition of Claim 5 or 6 including an aromatic or aliphatic petroleum distillate selected from xylene, a kerosene-type, or mixtures thereof.

10. A substantive composition having a pH of from about 4 to 6.9 and a Zeta potential of at least about +20 millivolts and consisting essentially of an applied chemical, a deposition and retention agent, and a solvent for said agent; said agent consisting of the reaction product of an acidic material selected from a substituted and unsubstituted aliphatic monoamines, diamines, tertiary amines, fatty amines, or mixtures thereof; and said agent being present in an amount of from about 0.25 to 10% by weight, based on the weight of the applied chemical.

11. The method of making the deposition and retention agent of Claim 1 or 2 comprising 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 about 4 to 6.9 and to give the compositions to which said agent is added a Zeta potential of at least about +20 millivolts.

12. The method of making the deposition and retention agent of Claim 1 or 3 comprising reacting said acidic material and said cationic surfactant under ambient conditions for a time sufficient for the reaction to be completed, the acidic material being a mixture of equal parts by weight of benzoic acid and tall oil and the cationic surfactant being an etherified fatty amine and there being reacted about 0.5 parts by weight of said acidic material for each party by weight of said surfac-tant to give to the compositions to which said agent is added a Zeta potential of at least about +20 millivolts.

13. The method of applying the composition of Claim 5 comprising forming a suspension thereof in a sprayable liquid and spraying the same on an area.

14. The method of Claim 13 wherein the sprayable liquid is water and the composition consists of a biocide and the deposition and retention agent is the reaction product of an acidic material selected from benzoic acid, fatty acids, tall oil or mixtures thereof and the cationic sur-factant is a substituted or unsubstituted aliphatic amine.

15. The method of Claim 14 wherein the composition in-cludes a solvent for said agent.